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1.
Liquid hydrocarbons (LC) are considered as fuel cells feed and, more particularly, as solid oxide fuel cell feed. Cost-effective LC-reforming catalysts are critically needed for the successful commercialization of such technologies. An alternative to noble metal catalysts, proposed by the authors in a previous publication, has been proven efficient for diesel steam reforming (SR). Nickel, less expensive and more readily available than noble metals, was used in a form that prevents deactivation. The catalyst formulation is a Ni-alumina spinel (NiAl2O4) supported on alumina (Al2O3) and yttria-stabilized zirconia (YSZ).SR of commercial diesel was undertaken for more than 15 h at high gas hourly space velocities and steam-to-carbon ratios lower than 2. Constant diesel conversion and high hydrogen concentrations were obtained. Ni catalyst characterization revealed no detectable amounts of carbon on the spinel catalyst surface Ni. The effect of catalyst composition (Ni concentration and YSZ presence) was studied to understand and optimize the developed catalyst. Two phenomena were found to be influenced by relative catalyst composition: water-gas-shift vs reforming reaction extent, and concentration of light hydrocarbons in products.  相似文献   

2.
Production of hydrogen by methanol steam reforming has been studied over a series of Ni/Al layered double hydroxide catalysts prepared by the co-precipitation method, with the aim to develop a stable catalyst that can be used in a membrane-joint performer at temperatures greater than 300 °C. H2, CO and CO2 are generally the major products together with trace amounts of CH4. The presence of potassium and/or sodium cations was found to improve the activity of methanol conversion. The selectivity for CO2 rather than CO was better with K ions than Na ions, especially at higher temperatures (e.g. 390–400 °C). Methanol steam reforming over a K-promoted Ni/Al layered double hydroxide catalyst resulted in better activity and similar stability compared to a commercial Cu catalyst.  相似文献   

3.
Mesoporous nickel-M-alumina aerogel catalysts (denoted as NiMAE) with different second metal (M = Ni, Ce, La, Y, Cs, Fe, Co, and Mg) were prepared by a single-step sol-gel method and a subsequent CO2 supercritical drying method. The effect of second metal of mesoporous nickel-M-alumina aerogel catalysts on their physicochemical properties and catalytic activity for steam reforming of simulated liquefied natural gas (LNG) was investigated. Textural and chemical properties of NiMAE catalysts were strongly influenced by the identity of second metal. Nickel species were highly dispersed on the surface of NiMAE catalysts through the formation of nickel aluminate phase. In the steam reforming of LNG, both LNG conversion and hydrogen yield decreased in the order of NiLaAE > NiCeAE > NiYAE > NiCsAE > NiNiAE > NiFeAE > NiCoAE > NiMgAE. Average nickel diameter of NiMAE catalysts was well correlated with LNG conversion and hydrogen yield over the catalysts. Among the catalysts tested, NiLaAE catalyst exhibited the best catalytic performance due to its smallest average nickel diameter. Furthermore, NiLaAE catalyst exhibited a strong capability of facilitating heat and mass transfer of reactant and product during the steam reforming of LNG. Water-gas shift reaction governed the steam reforming reaction over NiLaAE catalyst under the steam-rich reaction condition (steam/carbon > 2).  相似文献   

4.
A commercial Ni-based catalyst is wash-coated on a monolith made of 50 μm-thick fecralloy plates. Compared with the same volume of coarsely powdered Ni catalysts, the monolith wash-coated Ni catalysts give higher methane conversion in the steam reforming reaction, especially at gas hourly space velocities (GHSV) higher than 28,000 h−1, and with no pressure drop. A higher conversion of the monolith catalyst is obtained, even though it contains a lower amount of active catalyst (3 g versus 17 g for a powdered catalyst), which indicates that the heat-transfer capability of the wash-coated Ni catalyst is significantly enhanced by the use of a metal monolith. The efficacy of the monolith catalyst is tested using a shell-and-tube type heat-exchanger reactor with 912 cm3 of the monolith catalyst charged on to the tube side and hot combusted gas supplied to the shell side in a counter-current direction to the reactant flow. A methane conversion greater than 94% is obtained at a GHSV of 7300 h−1 and an average temperature of 640 °C. Nickel catalysts should first be reduced to become active for steam reforming. Doping a small amount (0.12 wt.%) of noble metal (Ru or Pt) in the commercial Ni catalyst renders the wash-coated catalyst as active as a pre-reduced Ni catalyst. Thus, noble metal-doped Ni appears useful for steam reforming without any pre-reduction procedure.  相似文献   

5.
Mesoporous alumina xerogel (AX) supports prepared by a sol–gel method were calcined at various temperatures. Ni/mesoporous alumina xerogel (Ni/AX) 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 of calcination temperature of AX supports on the catalytic performance of Ni/AX catalysts in the steam reforming of LNG was investigated. Physical and chemical properties of AX supports and Ni/AX catalysts were strongly influenced by the calcination temperature of AX supports. Crystalline structure of AX supports was transformed in the sequence of γ-alumina → (γ + θ)-alumina → θ-alumina → (θ + α)-alumina with increasing calcination temperature from 700 to 1000 °C. Nickel species were strongly bonded to the divalent vacancy of γ-alumina, (γ + θ)-alumina, and θ-alumina through the formation of nickel aluminate phase. In the steam reforming of LNG, both LNG conversion and hydrogen composition in dry gas showed volcano-shaped curves with respect to calcination temperature of AX supports. Among the catalysts tested, Ni/AX-900 (nickel catalyst supported on AX that had been calcined at 900 °C) showed the best catalytic performance. The smallest nickel crystalline size and the strongest nickel–alumina interaction were responsible for high catalytic performance of Ni/AX-900 catalyst in the steam reforming of LNG.  相似文献   

6.
In this study, methane and methanol steam reforming reactions over commercial Ni/Al2O3, commercial Cu/ZnO/Al2O3 and prepared Ni–Cu/Al2O3 catalysts were investigated. Methane and methanol steam reforming reactions catalysts were characterized using various techniques. The results of characterization showed that Cu particles increase the active particle size of Ni (19.3 nm) in Ni–Cu/Al2O3 catalyst with respect to the commercial Ni/Al2O3 (17.9). On the other hand, Ni improves Cu dispersion in the same catalyst (1.74%) in comparison with commercial Cu/ZnO/Al2O3 (0.21%). A comprehensive comparison between these two fuels is established in terms of reaction conditions, fuel conversion, H2 selectivity, CO2 and CO selectivity. The prepared catalyst showed low selectivity for CO in both fuels and it was more selective to H2, with H2 selectivities of 99% in methane and 89% in methanol reforming reactions. A significant objective is to develop catalysts which can operate at lower temperatures and resist deactivation. Methanol steam reforming is carried out at a much lower temperature than methane steam reforming in prepared and commercial catalyst (275–325 °C). However, methane steam reforming can be carried out at a relatively low temperature on Ni–Cu catalyst (600–650 °C) and at higher temperature in commercial methane reforming catalyst (700–800 °C). Commercial Ni/Al2O3 catalyst resulted in high coke formation (28.3% loss in mass) compared to prepared Ni–Cu/Al2O3 (8.9%) and commercial Cu/ZnO/Al2O3 catalysts (3.5%).  相似文献   

7.
Thermodynamics equilibrium analysis of carbon dioxide reforming of methane combined with steam reforming to synthesis gas was studied by Gibbs free energy minimization method to understand the effects of process variables such as temperature, pressure and inlet CH4/H2O/CO2 ratios on product distributions. For this purpose, the calculations were carried out at total pressures of 1 and 20 bar, and at ranges of temperature and steam-to-carbon ratios of 200–1200 °C and 0–0.50, respectively. The results revealed that carbon dioxide reforming of methane combined with steam reforming process was controlled by different reactions with regard to the operating temperature, pressure and varying feed compositions. The H2/CO product ratio could be modified by changing the relative concentration of steam and CO2 in the feed, temperature and pressure, depending on the downstream application.  相似文献   

8.
Catalytic activity of a ceria-supported Iridium (Ir/CeO2) catalyst was investigated for steam reforming of ethanol within a temperature range of 300–500 °C. Three types of ceria were chosen to prepare the catalyst: commercial [assigned as CeO2(C)] and prepared [using a simple reduction–oxidation method, CeO2(R), and another combined with ultrasonic irradiation, CeO2(U)] ceria. The Ir/CeO2 catalyst with Ir loading of 2 wt.% was prepared by deposition–precipitation using iridium chloride (IrCl3) as a precursor at 75 °C and pH = 9 (adjusted with 0.25 M Na2CO3). Catalytic activities toward the steam reforming of ethanol (SRE) were tested in a fixed-bed reactor. In order to better understand the effect of activation conditions of a catalyst on the reforming of ethanol, reduction pretreatment at 200 and 400 °C (assigned as H2 and H4) were conducted. The results indicated that only less sintering influences the catalytic activities for high temperature reduction. The ethanol conversion approached completion around 450 °C via reduction pretreatment for Ir/CeO2(U) and Ir/CeO2(C) samples under H2O/EtOH molar ratio of 13 and 22,000 h−1 GHSV. Not only was a high dispersion of both catalysts present but also no impurities (e.g., boron) interfered with the catalytic activities. The hydrogen yield (H2 mole/EtOH mole) exceeds 5.0 with less content of CO and CH4 (<2%).  相似文献   

9.
The partial oxidation (POx) reforming of Ultra Low Sulphur-Diesel (ULSD), rapeseed methyl ester (RME) - biodiesel and Fischer–Tropsch synthetic diesel fuels (SD) were studied by using a fixed-bed reactor. The ease of reforming the three fuels was first examined at different O/C feed ratios at constant gas hourly space velocity (GHSV) of 35 k h−1 over a prototype monolith catalyst (1%Rh/CeO2–ZrO2). The hydrocarbon species (C1–C6) produced in the reformer were analyzed using direct gas injection gas chromatography mass spectrometry (GC-MS). Under the same O/C ratios for 35 k h−1 the fuels conversion and process efficiency was dependent on the fuel type, and followed the general trend: SD > biodiesel > ULSD. The GC-MS analysis shows that both, biodiesel and ULSD diesel produced significantly higher amounts of alkenes compared to SD fuel. Fuel with relatively high aromatics content such diesel can be efficiently reformed to syngas over the catalyst used in this study but the reformer operating range (e.g. O/C ratio and space velocity) is limited compared to paraffinic fuels such as FT-SD. At increased GHSV of 45 k h−1 and O/C = 1.75, the diesel fuel conversion efficiency to syngas (H2 and CO) was improved significantly and the formation of intermediate species such as methane, ethylene, and propylene was reduced considerably as a result of the increased peak reaction temperatures. The reduced HC species and increased H2 concentration in the reactor product gas from the reforming of FT-SD fuel can provide significant advantages to the IC engine applications.  相似文献   

10.
A water–gas shift (WGS) Pt/Ce0.6Zr0.4O2 catalyst has been prepared, which exhibits much faster kinetics than conventional high-temperature ferrochrome catalysts in the temperature range most suitable for operation of WGS Pd membrane reactors, i.e. above 623 K. The performance of the Pt catalyst was tested in a reactor furnished with a supported, 1.4 μm thick high-flux Pd membrane using feeds obtained by autothermal reforming of natural gas. CO conversion remained above thermodynamic equilibrium up to feed space velocities of 9100 l kg−1 h−1 at 623 K, Ptotal = 1.2 MPa and steam-to-carbon ratio S/C = 3, but H2 recovery decreased from 84.8% at GHSV = 4050 l kg−1 h−1 to 48.7% at the highest space velocity. This rapid decline of separation performance is attributed to slow H2 diffusion through the catalyst bed, suggesting that external mass flow resistance has a significant impact on the H2 permeation rate in such membrane reactors. This could be minimized by the development of WGS catalysts with even faster kinetics which would allow further reduction of the catalyst bed height.  相似文献   

11.
A Co/ZnO catalyst was prepared by coprecipitation method, and was applied for ethanol steam reforming. The effect of reaction conditions on the ethanol steam reforming performance was studied in the temperature ranges from 400 °C to 600 °C and the space velocity ranges from 10,000 h−1 to 120,000 h−1 in a fixed bed reactor. The Co/ZnO showed high activity with an ethanol conversion of 97% and a H2 concentration of 73% at a gas hourly space velocity of 40,000 h−1 and a moderately low temperature of 450 °C. EXAFS analysis for fresh and spent samples confirms that Co phase maintains during reaction. The catalyst was then loaded into a multi-layered reformer of which the design concept allows for integrating endothermic steam reforming, exothermic combustion and evaporation in a reactor. The performance of the compact reformer demonstrated that the hydrogen production rate satisfy a PEMFC stack power level of 540 W suitable for portable power supplies.  相似文献   

12.
A procedure for coating metal plates with powder catalysts was developed based on electrophoretic deposition (EPD), and tested to deposit three different Co-based catalysts for the steam reforming of ethanol on stainless steel plates. The catalysts contained 10 wt% Co and 1 wt% of Mn or Fe supported on ZnO, and were prepared by co-precipitation (Co–Mn/ZnO–P and Co–Fe/ZnO–P) and impregnation (Co–Mn/ZnO–I). EPD was performed suspending the powder catalysts in isopropanol, using a voltage of 100 V and a distance between electrodes of 2 cm. Polyethyleneimine (PEI, 1 g/L) was used as binder. Deposition time was fixed at 5 min, which gave a thickness of the catalyst layer from around 30–45 μm, depending on the catalyst. The activity of the catalyst plates was tested at 773 K using steam to carbon ratios of 3 and 4, under incomplete conversion conditions. All catalysts favored ethanol dehydrogenation to acetaldehyde, and steam reforming. Ethanol dehydration to ethylene and acetaldehyde cracking to methane and carbon monoxide were not favored, and the selectivity towards those products was very low.  相似文献   

13.
In order to reduce the coke formation over a conventional Ni/γ-Al2O4 catalyst and increase the activity at low temperature, we used the impregnation approach to synthesize MgO (30.0 wt.%)/Zeolite Y catalysts loaded with bimetallic Ni(10.0 wt.%)/Ga(10.0–30.0 wt.%) and study the steam-reforming reactions of ethanol. The Ga-loaded catalyst impregnated between the Ni and Mg components exhibits significantly higher reforming reactivity compared to the conventional Ni/Mg/Zeolite Y catalyst. The main products from steam reforming over the Ni/Ga/Mg/Zeolite Y catalyst are only H2 and CH4 at above 550 °C, and the catalytic performances differ according to the amount of Ga. The H2 production and ethanol conversion are maximized at 87% and 100%, respectively, over Ni(10)/Ga(30)/Mg(30)/Zeolite Y at 700 °C for 1 h at CH3CH2OH:H2O = 1:3 and a gas hourly space velocity (GHSV) of 6740 h−1, and the high performance is maintained for up to 59 h.  相似文献   

14.
Tars in biomass gasification systems need to be removed to avoid damaging and clogging downstream pipes or equipment. In this study, Ni-based catalysts were made by mechanically mixing NiO and char particles at various ratios. Catalytic performance of the Ni/char catalysts was studied and compared with performance of wood char and coal char without Ni for syngas cleanup in a laboratory-scale updraft biomass gasifier. Reforming parameters investigated were reaction temperature (650–850 °C), NiO loading (5–20% of the weight of char support), and gas residence time (0.1–1.2 s). The Ni/coalchar and Ni/woodchar catalysts removed more than 97% of tars in syngas at 800 °C reforming temperature, 15% NiO loading, and 0.3 s gas residence time. Analysis of syngas composition indicated that concentrations of H2 and CO in syngas significantly. Furthermore, performance of the Ni/coalchar catalyst was continuously tested for 8 h. There was slight deactivation of the catalyst in the early stage of tar/syngas reforming; however, the catalyst was able to stabilize soon after. It was concluded that chars especially coal char can be an effective and inexpensive support of NiO for biomass gasification tar removal and syngas conditioning.  相似文献   

15.
This work investigates the catalytic performance of nanocomposite Ni/ZrO2-AN catalyst consisting of comparably sized Ni (10–15 nm) and ZrO2 (15–25 nm) particles for hydrogen production from the cyclic stepwise methane reforming reaction with either steam (H2O) or CO2 at 500–650 °C, in comparison with a conventional Ni/ZrO2-CP catalyst featuring Ni particles supported by large and widely sized ZrO2 particles (20–400 nm). Though both catalysts exhibited similar activity and stability during the reactions at 500 and 550 °C, they showed remarkably different catalytic stabilities at higher temperatures. The Ni/ZrO2-CP catalyst featured a significant deactivation even during the methane decomposition step in the first cycle of the reactions at ≥600 °C, but the Ni/ZrO2-AN catalyst showed a very stable activity during at least 17 consecutive cycles in the cyclic reaction with steam. Changes in the catalyst beds at varying stages of the reactions were characterized with TEM, XRD and TPO–DTG and were correlated with the amount and nature of the carbon deposits. The Ni particles in Ni/ZrO2-AN became stabilized at the sizes of around 20 nm but those in Ni/ZrO2-CP kept on growing in the methane decomposition steps of the cyclic reaction. The small and narrowly sized Ni particles in the nanocomposite Ni/ZrO2-AN catalyst led to a selective formation of filamentous carbons whereas the larger Ni particles in the Ni/ZrO2-CP catalyst a preferred formation of graphitic encapsulating carbons. The filamentous carbons were favorably volatilized in the steam treatment step but the CO2 treatment selectively volatilized the encapsulating carbons. These results identify that the nature but not the amount of carbon deposits is the key to the stability of Ni/ZrO2 catalyst and that the nanocomposite Ni/ZrO2-AN would be a promising catalyst for hydrogen production via cyclic stepwise methane reforming reactions.  相似文献   

16.
Novel Co (10%) catalysts supported on ZnO and promoted with Fe and Mn (1%) were synthesized and characterized by high-resolution transmission electron microscopy (HRTEM), electron energy-loss spectroscopy (EELS), X-ray diffraction (XRD) and X-ray photoelectron spectra (XPS). Their catalytic activity for steam reforming of ethanol was compared with that of Ni catalysts supported on La2O3-Al2O3. Experiments at 400 and 500 °C, steam to carbon ratios of 2 and 4, and a wide interval of contact time were analyzed following a multifactorial experimental design. At 500 °C and a steam to carbon molar ratio of 4, complete conversion of ethanol was achieved above a contact time of 200 g min mol−1 for all catalysts. The ratio of selectivity between hydrogen and methane was around 23 molH2/molCH4 in the Co catalysts, while it approached the thermodynamic equilibrium (5.7 molH2/molCH4) in the Ni catalysts. The Co catalysts do not promote methane-forming reactions like ethanol cracking and acetaldehyde decarbonilation, nor do they facilitate the reverse methane steam reforming reaction. The catalytic behavior of cobalt is enhanced by promotion with iron or manganese through the formation of bimetallic particles, which facilitates cobalt reducibility. This suggests that Co-Mn/ZnO and Co-Fe/ZnO catalysts have a good potential for their use for ethanol reforming at moderate temperature.  相似文献   

17.
Integrating PEM fuel cells effectively with liquid hydrocarbon reforming requires careful system analysis to assess trade-offs associated with H2 production, purification, and overall water balance. To this end, a model of a PEM fuel cell system integrated with an autothermal reformer for liquid hydrocarbon fuels (modeled as C12H23) and with H2 purification in a water–gas-shift/membrane reactor is developed to do iterative calculations for mass, species, and energy balances at a component and system level. The model evaluates system efficiency with parasitic loads (from compressors, pumps, and cooling fans), system water balance, and component operating temperatures/pressures. Model results for a 5-kW fuel cell generator show that with state-of-the-art PEM fuel cell polarization curves, thermal efficiencies >30% can be achieved when power densities are low enough for operating voltages >0.72 V per cell. Efficiency can be increased by operating the reformer at steam-to-carbon ratios as high as constraints related to stable reactor temperatures allow. Decreasing ambient temperature improves system water balance and increases efficiency through parasitic load reduction. The baseline configuration studied herein sustained water balance for ambient temperatures ≤35 °C at full power and ≤44 °C at half power with efficiencies approaching ∼27 and ∼30%, respectively.  相似文献   

18.
The development and evaluation of a reactor based on microchannel technology for the reforming of diesel fuel is reported. The reactor itself was based on an integrated reformer/burner heat exchange reactor concept. 38 h of diesel reforming was performed at temperatures above 750 °C and at various S/C ratios, down to a minimum of 3.17, up to an electrical power equivalent of 5 kW. Over 98% total diesel conversion was observed at all times over the testing period. Variation of experimental parameters such as O/C and S/C ratios are critical for optimum operation of the reformer.  相似文献   

19.
Preferential oxidation (PROX) of CO over noble-metal-containing monolith catalysts is one of the most promising approaches for removing CO to generate low temperature fuel cell quality H2. The monolith-supported washcoated catalyst comprising Cu and Fe promoted with Pt is highly effective in reducing the CO in practical reformates to less than 10 ppm over a broad range of feed compositions, inlet temperatures and turn down ratios. It is speculated that Pt dissociates the H2 which then reduces the CuO to its active state. Pt may also act as a cocatalyst for CO adsorption with metal oxides supplying oxygen for PROX reaction. The catalytic system is operated adiabatically with an inlet temperature between roughly 65–120 °C reaching an exit temperature close to 150 °C with no evidence of reverse water gas shift or methanation. The goal was to find the proper operating conditions to achieve <10 ppm CO. Turn down ratios (varying space velocities) at a factor of 4–5 are routinely achieved up to at least 34,000 h−1 with high steam levels of up to 45%. The wide operating window simplifies the control of the PROX reactor and improves the fuel processor’s performance for fast startup and shutdown and responses to transient loads. The catalyst also retains its performance after multiple start and stops modes of operation in reformate.  相似文献   

20.
The objective of this work was to explore the benefits of high-pressure steam reforming of ethanol for the production of hydrogen needed to refuel the high-pressure tanks of fuel cell (polymer electrolyte) vehicles. This paper reports on the potential efficiency benefits and challenges of pressurized reforming and options for dealing with the challenges; it reports the results from experiments in a micro-reactor, followed by a modeling study of the reactor to project the dependence of the hydrogen yields on process parameters. The experiments were conducted in the range of approximately 7–70 atm, 600–750 °C, steam-to-carbon molar ratios of 3–12, and gas hourly space velocities of 8500–83,000 per hour. By placing a hydrogen-transporting palladium-alloy membrane within the catalyst zone, this study quantified the beneficial effect of hydrogen extraction from the reforming zone. The model was used to explore the parameter space to define the reactor and conditions that would be needed to approach the efficiency targets for distributed hydrogen production plants. The results indicate that the tested catalyst was sufficiently active, and the hydrogen yield achieved with the experimental membrane reactor was limited by the low hydrogen flux of the tested membrane. The reactor model predicts that a membrane with at least 20 times higher flux than currently evaluated would be sufficient to generate hydrogen yields to match efficiency targets of 72%.  相似文献   

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