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1.
Compact natural gas reforming process using high-performance and long-lived CO preferential oxidation (PROX) over an activated Ru/Al 2O 3 catalyst has been developed for residential polymer electrolyte fuel cell (PEFC) systems. The long-term durability of the catalyst was demonstrated for more than 40,000 h. After 40,000 h operation, CO was removed from a reformed gas to below 1 ppm on the activated Ru/Al 2O 3 catalyst at [O 2]/[CO] = 1.5. The high activity and selectivity of the catalyst were maintained for more than 40,000 h. Moreover, the start–stop durability for more than 3,000 cycles of the activated Ru/Al 2O 3 catalyst was also demonstrated without N 2 purge. 相似文献
2.
Pt-Fe/mordenite catalysts coated on ceramic straight-channel monoliths were evaluated for the preferential oxidation of carbon monoxide (PROX) in hydrogen-rich gas streams. In a feed gas containing 1% CO, 1% O 2, with the balance H 2, CO conversion reached almost 100% at temperatures ranging from 100 to 130 °C, i.e., an outlet CO concentration of less than 10 ppm. Even in a synthetic reformate gas (1% CO, 1% O 2, 15% H 2O, 20% CO 2, balance H 2), the monolithic catalyst exhibited excellent activity, reducing the CO concentration to less than 100 ppm. In particular, under optimized conditions, an outlet CO concentration of less than 10 ppm was realized. This is the first report that has demonstrated that monolithic catalysts could achieve the 10-ppm target level at a low O 2/CO ratio and a high space velocity in a single-stage reactor. Excellent durability of the monolithic catalyst is expected, based on a lack of deterioration in performance during 500 h of operation. 相似文献
3.
Ru/C catalysts promoted, or not, by cerium were prepared by impregnation of an active carbon (961 m 2 g −1) with chlorine-free precursors of Ru and Ce. They were characterized by chemisorption of H 2 and of CO and by electron microscopy. TEM and H 2 chemisorption gives coherent results while CO chemisorption overestimates Ru dispersion. In Ru–Ce/C, Ce is in close contact with Ru and decreases Ru accessibility. Catalytic wet air oxidation (CWAO) of phenol and of acrylic acid (160°C and 20 bar of O2) was investigated over these catalysts and their performance (activity, selectivity to intermediate compounds) compared with that of a reference Ru/CeO2 catalyst. Carbon-supported catalysts were very active for the CWAO of phenol but not for acrylic acid. Although high conversions were obtained, phenol was not totally mineralized after 3 h. It was shown that acrylic acid was more strongly adsorbed than phenol. Moreover, the number of contact points between Ru particles and CeO2 crystallites constitutes a key parameter in these reactions. A high surface area of ceria is required to insure O2 activation when the organic molecule is strongly adsorbed. 相似文献
4.
Micro-channel plates with dimension of 1 mm × 0.3 mm × 48 mm were prepared by chemical etching of stainless steel plates followed by wash coating of CeO 2 and Al 2O 3 on the channels. After coating the support on the plate, Pt, Co, and Cu were added to the plate by incipient wetness method. Reaction experiments of a single reactor showed that the micro-channel reactor coated with CuO/CeO 2 catalyst was highly selective for CO oxidation while the one coated with Pt-Co/Al 2O 3 catalyst was highly active for CO oxidation. The 7-layered reactors coated with two different catalysts were prepared by laser welding and the performances of each reactor were tested in large scale of PROX conditions. The multi-layered reactor coated with Pt-Co/Al 2O 3 catalyst was highly active for PROX and the outlet concentration of CO gradually increased with the O 2/CO ratio due to the oxidation of H 2 which maintained the reactor temperature. The multi-layered reactor coated with CuO/CeO 2 showed lower catalytic activity than that coated with Pt catalyst, but its selectivity was not changed with the increase of O 2/CO ratios due to the high selectivity. In order to combine advantages (high activity and high selectivity) of the two individual catalysts (Pt-Co/Al 2O 3, CuO/CeO 2), a serial reactor was prepared by connecting the two multi-layered micro-channel reactors with different catalysts. The prepared serial reactor exhibited excellent performance for PROX. 相似文献
5.
NO removal using CH 4 as a reductant in a dual-bed system has been investigated with Co-NaX and Ag-NaX catalysts, which were prepared by Co 2+-, Ag +-ion exchange into zeolite NaX, respectively, and activation for 5 h at 500 °C. The experimental result has been compared with that of a Co-NaX-CO catalyst, additionally pre-treated under CO flow for the Co-NaX catalyst. The cobalt crystal structure of a Co-NaX-CO catalyst is Co 3O 4, which promotes NO oxidation to NO 2 by excess O 2 at a low temperature (523 K). The mechanical mixture of Co-NaX-CO and Ag-NaX catalysts shows a synergy effect on NO reduction to N 2 by CH 4 in the presence of excess O 2 and H 2O, but the NO reduction decreases quickly as time passes. However, the NO reduction to N 2 in a deNO bed at 523 K and a deNO 2 bed at 423 K, which are relatively lower than the reaction temperatures for common SCR systems, still remained at 67% even in a H 2O 10% gas mixture after 160 min. 相似文献
6.
CO preferential oxidation on a novel Ru catalyst greatly improved in activity and selectivity over a wide temperature range by the pre-treatment of H 2 reduction was characterized. The high performance was obtained by increasing the population of surface Ru(0) which improved O 2 activation at low temperatures. Methanation of CO on the catalyst can also contribute to the final CO clean-up from ca. 100 to <1 ppm at low temperatures where the influence of CO 2 methanation can be ignored. 相似文献
7.
New oxidation methods for the partial oxidation of alkenes at low temperatures (<373 K) using gaseous alkene–O 2 fuel cell systems and for hydroxylation of alkanes and aromatics applying H 2–O 2 fuel cell reactions are shown. Catalytic oxidation systems can be converted into electrochemical cells which control the reaction rate and selectivity by a variable resister or potentiostat in the outer circuit, as shown for the Wacker type and π-allyl type oxidations. The hydroxylation of benzene to phenol and of light alkanes could be realized at room temperature by applying H 2–O 2 fuel systems. The reverse H 2–O 2 cell reaction enables the epoxidation of propylene into porpylene oxides. It is also possible to combine the two reactions for the cogeneration of phenol and epoxide. Some problems to develop these processes on a commercial scale are also discussed. 相似文献
8.
In situ time-resolved FTIR spectroscopy was used to study the reaction mechanism of partial oxidation of methane to synthesis gas and the interaction of CH 4/O 2/He (2/1/45) gas mixture with adsorbed CO species over SiO 2 and γ-Al 2O 3 supported Rh and Ru catalysts at 500–600°C. It was found that CO is the primary product for the reaction of CH 4/O 2/He (2/1/45) gas mixture over H 2 reduced and working state Rh/SiO 2 catalyst. Direct oxidation of methane is the main pathway of synthesis gas formation over Rh/SiO 2 catalyst. CO 2 is the primary product for the reaction of CH 4/O 2/He (2/1/45) gas mixture over Ru/γ-Al 2O 3 and Ru/SiO 2 catalysts. The dominant reaction pathway of CO formation over Ru/γ-Al 2O 3 and Ru/SiO 2 catalysts is via the reforming reactions of CH 4 with CO 2 and H 2O. The effect of space velocity on the partial oxidation of methane over SiO 2 and γ-Al 2O 3 supported Rh and Ru catalysts is consistent with the above mechanisms. It is also found that consecutive oxidation of surface CO species is an important pathway of CO 2 formation during the partial oxidation of methane to synthesis gas over Rh/SiO 2 and Ru/γ-Al 2O 3 catalysts. 相似文献
9.
Two supported Ru catalysts were prepared by the chemical vapor deposition of Ru 3(CO) 12 on MgO and SiO 2 (MOCVD). TEM, XRD, and static H 2 chemisorption measurements confirmed that the Ru particle size was about 2 nm on both supports. Using in situ DRIFT (diffuse reflectance infrared Fourier transform) spectroscopy at atmospheric pressure it was found that the adsorption of CO on the reduced samples is clearly influenced by the supports whereas the adsorption of CO on the oxidized Ru catalysts is essentially independent of the support. O 2 chemisorption measurements showed that a thin RuO 2 surface layer was formed on both catalysts under oxidizing conditions at room temperature. The observed C–O stretching frequencies were found to be in good agreement with HREELS and LEED data reported for the RuO 2(1 1 0) single crystal surface. The catalytic activity was assessed under high-vacuum conditions using the TAP (temporal analysis of products) reactor by co-feeding CO and O 2. These conditions ensured that heat and mass transfer limitations were absent. Both supported Ru catalysts were found to be highly active and stable under the CO oxidation conditions even down to room temperature. The deactivation of the catalysts observed at room temperature was reversible and independent of the support. The turnover frequencies (number of CO 2 molecules per metal surface site per second) derived from steady-state measurements are in good agreement with data reported for the RuO 2(1 1 0) single crystal surface under UHV conditions. Based on the results of the DRIFTS (diffuse reflectance infrared Fourier transform spectroscopy) and the kinetic measurements supported RuO 2 is identified as the catalytically active phase. In addition, the turnover frequencies are in good agreement with data reported for Ru/SiO 2 at atmospheric pressure. Thus, both the materials and the pressure gap were bridged successfully. 相似文献
10.
The importance of the hydrodearomatisation (HDA) is increasing together with tightening legislation of fuel quality and exhaust emissions. The present study focuses on hydrogenation (HYD) kinetics of the model aromatic compound naphthalene, found in typical diesel fraction, in n-hexadecane over a NiMo (nickel molybdenum), Ni (nickel) and Ru (ruthenium) supported on trilobe alumina (Al 2O 3) catalysts. Kinetic reaction expressions based on the mechanistic Langmuir–Hinshelwood (L–H) model were derived and tested by regressing the experimental data that translated the effect of both naphthalene and hydrogen concentration at a constant temperature (523.15 and 573.15 K over the NiMo catalyst and at 373.15 K over the Ni and Ru/Al 2O 3 catalysts) on the initial reaction rate. The L–H equation, giving an adequate fit to the experimental data with physically meaningful parameters, suggested a competitive adsorption between hydrogen and naphthalene over the presulphided NiMo catalyst and a non-competitive adsorption between these two reactants over the prereduced Ni and Ru/Al 2O 3 catalysts. In addition, the adsorption constant values indicated that the prereduced Ru catalyst was a much more active catalyst towards naphthalene HYD than the prereduced Ni/Al 2O 3 or the presulphided NiMo/Al 2O 3 catalyst. 相似文献
11.
A catalytically assisted low NO x combustor has been developed which has the advantage of catalyst durability. This combustor is composed of a burner section and a premixed combustion section behind the burner section. The burner system consists of six catalytic combustor segments and six premixing nozzles, which are arranged alternately and in parallel. Fuel flow rate for the catalysts and the premixing nozzles are controlled independently. The catalytic combustion temperature is maintained under 1000°C, additional premixed gas is injected from the premixing nozzles into the catalytic combustion gas, and lean premixed combustion at 1300°C is carried out in the premixed combustion section. This system was designed to avoid catalytic deactivation at high temperature and thermal or mechanical shock fracture of the honeycomb monolith. In order to maintain the catalyst temperature under 1000°C, the combustion characteristics of catalysts at high pressure were investigated using a bench scale reactor and an improved catalyst was selected for the combustor test. A combustor for a 20 MW class multi-can type gas turbine was designed and tested under high pressure conditions using LNG fuel. Measurements of NO x, CO and unburned hydrocarbon were made and other measurements were made to evaluate combustor performance under various combustion temperatures and pressures. As a result of the tests, it was proved that NO x emission was lower than 10 ppm converted at 16% O 2, combustion efficiency was almost 100% at 1300°C of combustor outlet temperature and 13.5 ata of combustor inlet pressure. 相似文献
12.
A series of Ag-doped manganese oxide catalyst were synthesized by the reflux method in an acid medium. The surface structure of the catalysts was characterized by N 2 adsorption, XRD and TEM experiments. The catalysts showed excellent catalytic activity for CO oxidation. The adsorption and oxidation of CO on a 1.0% Ag/MnO x catalyst between 393 and 493 K were studied by means of single pulse experiments in a TAP reactor. The adsorption of CO was reversible at these temperatures and CO 2 was formed in an oxidation reaction of CO and lattice oxygen. Curve fitting to the experimental TAP response curves of the reactant and product was used to determine the kinetic parameters for the elementary steps. The activation energies were 83 kJ/mol for CO desorption, 31 kJ/mol for CO 2 desorption, and 116 kJ/mol for the surface CO oxidation by lattice oxygen. In addition, the effect of coadsorbed O 2 on CO adsorption was studied by the TAP technique. Below 353 K, there was a sharp increase, by about one order of magnitude, in the rate constant of CO adsorption promoted by the presence of coadsorbed O 2. 相似文献
13.
Short contact time catalytic partial oxidation (SCT-CPO) of natural gas is a promising technology for syngas production, representing an appealing alternative to existing processes. The high conversion and selectivity observed since the earlier works in this field can make this process attractive. Moreover, the SCT-CPO reactors can be autothermally operated and the possibility to use air as oxidant appears a feasible route to reduce syngas production costs: these two issues make possible the use of a SCT-CPO reactor as the reformer of a fuel processor for H 2 production for fuel cells. The present work refers to an experimental study of syngas production from CH4 and O2 via a SCT-CPO reactor made of a fixed bed of Rh/-Al2O3 spheres. The main obtained results are: (i) an increase in GHSV produces an enhancement of transport rates and this in turn determines an improvement in CH4 conversion, despite the reduction in residence time; (ii) the catalyst pellets get hotter than the gas phase thus favouring the H2 and CO production; syngas formation is in fact both thermodynamically and kinetically promoted at high temperatures; (iii) a similar improvement of conversion was obtained with a reduction of the catalyst particle size, thanks once again to an increase in the heat transport and a higher geometrical surface area of the catalyst itself. By a slight increase of the O2 fed to the reactor, H2 and CO yields can be maximised and a complete CH4 conversion achieved. 相似文献
14.
The Ru/C catalyst prepared by impregnation method was used for hydrogenation of 3,5-dimethylpyridine in a trickle bed reactor. Under the same reduction conditions (300 °C in H 2), the catalytic activity of the non- in-situ reduced Ru/C-n catalyst was higher than that of the in-situ reduced Ru/C-y catalyst. Therefore, an in-situ H 2 reduction and moderate oxidation method was developed to increase the catalyst activity. Moreover, the influence of oxidation temperature on the developed method was investigated. The catalysts were characterized by Brunauer–Emmett–Teller method, hydrogen temperature programmed reduction H 2-TPR, hydrogen temperature-programmed dispersion (H 2-TPD), X-ray diffraction, energy dispersive spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, O 2 chemisorption and oxygen temperature-programmed dispersion (O 2-TPD) analyses. The results showed that there existed an optimal Ru/RuO x ratio for the catalyst, and the highest 3,5-dimethylpyridine conversion was obtained for the Ru/C-i1 catalyst prepared by in-situ H 2 reduction and moderate oxidation (oxidized at 100 °C). Excessive oxidation (200 °C) resulted in a significant decrease in the Ru/RuO x ratio of the in-situ H 2 reduction and moderate oxidized Ru/C-i2 catalyst, the interaction between RuO x species and the support changed, and the hard-to-reduce RuO x species was formed, leading to a significant decrease in catalyst activity. The developed in-situ H 2 reduction and moderate oxidation method eliminated the step of the non- in-situ reduction of catalyst outside the trickle bed reactor. 相似文献
15.
A catalytically assisted low NO x combustor has been developed which has the advantage of catalyst durability. Combustion characteristics of catalysts at high pressure were investigated using a bench scale reactor and an improved catalyst was selected. A combustor for multi-can type gas turbine of 10 MW class was designed and tested at high-pressure conditions using liquefied natural gas (LNG) fuel. This combustor is composed of a burner system and a premixed combustion zone in a ceramic type liner. The burner system consists of catalytic combustor segments and premixing nozzles. Catalyst bed temperature is controlled under 1000°C, premixed gas is injected from the premixing nozzles to catalytic combustion gas and lean premixed combustion is carried out in the premixed combustion zone. As a result of the combustion tests, NO x emission was lower than 5 ppm converted at 16% O 2 at a combustor outlet temperature of 1350°C and a combustor inlet pressure of 1.33 MPa. 相似文献
16.
On-board fuel processors are being developed to provide hydrogen-rich gas to the polymer electrolyte fuel cell automotive propulsion systems. Whereas the anode catalyst in the fuel cell has low tolerance for carbon monoxide, 10–100 ppm, reforming of gasoline and other hydrocarbon fuels generally produces 1–2% of CO. Of the many methods of removing CO from the reformer gas, preferential oxidation (PrOx) of CO over noble-metal catalysts is practiced most frequently. In this paper, we present experimental data for CO conversion on a Pt-based catalyst that is active at room temperature and was coated on a ceramic monolith. The data is used to develop an empirical correlation for selectivity for CO oxidation as a function of CO concentration and oxygen stoichiometry at 30,000–80,000/h space velocity. The selectivity correlation is used in a model to analyze the performance of multi-stage, adiabatic PrOx reactors with heat exchange between the stages to cool the reformate to 100 °C. An optimization algorithm is used to determine the operating conditions that can reduce CO concentration to 10 ppm while minimizing parasitic loss of H 2 in the reformate stream. It is found that the 10 ppm constraint limits the maximum inlet CO concentration to 1.05% in a single-stage reactor and to 3.1% in a two-stage reactor. The results clearly show the incremental reduction in parasitic H 2 loss by addition of second and third stages. 相似文献
17.
From the viewpoint of environmental protection, the polymer electrolyte fuel cell (PEFC) cogeneration system, which contributes to the reduction of CO 2 and NO x emission, is drawing attention as the next‐generation residential power source. In recent years, automobile manufacturers have been energetically developing PEFC as the energy source of electric vehicles on account of its good start‐up performance due to a relatively low operating temperature and its high power density [1–3]. PEFC is also promising for residential cogeneration systems when combined with a small‐scale natural gas fuel processor [4]. In this review, the current status of the development of PEFC cogeneration systems for residential use including the fuel processor is reported. 相似文献
18.
Noble metal (Rh, Pt, Pd, Ir, Ru, and Ag) and Ni catalysts supported on CeO 2–Al 2O 3 were investigated for water gas shift reaction at ultrahigh temperatures. Pt/CeO 2–Al 2O 3 and Ru/CeO 2–Al 2O 3 demonstrated as the best catalysts in terms of activity, hydrogen yield and hydrogen selectivity. At 700 °C and steam to CO ratio of 5.2:1, Pt/CeO 2–Al 2O 3 converted 76.3% of CO with 94.7% of hydrogen selectivity. At the same conditions, the activity and hydrogen selectivity for Ru/CeO 2–Al 2O 3 were 63.9% and 85.6%, respectively. Both catalysts showed a good stability over 9 h of continuous operation. However, both catalysts showed slight deactivation during the test period. The study revealed that Pt/CeO 2–Al 2O 3 and Ru/CeO 2–Al 2O 3 were excellent ultrahigh temperature water gas shift catalysts, which can be coupled with biomass gasification in a downstream reactor. 相似文献
19.
The effect of the Pd addition method into the fresh Pd/(OSC + Al 2O 3) and (Pd + OSC)/Al 2O 3 catalysts (OSC material = Ce xZr 1−xO 2 mixed oxides) was investigated in this study. The CO + NO and CO + NO + O 2 model reactions were studied over fresh and aged catalysts. The differences in the fresh catalysts were insignificant compared to the aged catalysts. During the CO + NO reaction, only small differences were observed in the behaviour of the fresh catalysts. The light-off temperature of CO was about 20 °C lower for the fresh Pd/(OSC + Al 2O 3) catalyst than for the fresh (Pd + OSC)/Al 2O 3 catalyst during the CO + NO + O 2 reaction. For the aged catalysts lower NO reduction and CO oxidation activities were observed, as expected. Pd on OSC-containing alumina was more active than Pd on OSC material after the agings. The activity decline is due to a decrease in the number of active sites on the surface, which was observed as a larger Pd particle size for aged catalysts than for fresh catalysts. In addition, the oxygen storage capacity of the aged Pd/(OSC + Al 2O 3) catalyst was higher than that of the (Pd + OSC)/Al 2O 3 catalyst. 相似文献
20.
Pt supported on CeO 2 and 10 wt.% La 3+-doped CeO 2 catalysts have been prepared, characterised and tested for soot oxidation by O 2 in TGA. The reaction mechanism has been studied in a TAP reactor with labelled O 2. Isotopic oxygen exchange between molecular O 2 and ‘O’ on the support/catalyst was observed and soot oxidation is being carried out by lattice oxygen. TAP studies further show that Pt improves O 2 adsorption and, therefore, 5 wt.% Pt-containing catalysts are more active for soot oxidation than the counterpart supports. In addition, CeO 2 doping by La 3+ leads to an improved support, since La 3+ stabilises the structure of CeO 2 when calcined at high temperature (1000 °C) and minimises sintering. In addition, La 3+ improves the Ce 4+/Ce 3+ reduction as deduced from H 2-TPR experiments and favours oxygen mobility into the lattice. A synergetic effect of Pt and La 3+ is observed, Pt-containing La 3+-doped CeO 2 being the most active catalyst for soot oxidation by O 2 among the samples studied. 相似文献
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