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1.
This work presents the characteristics of catalytic dimethyl ether (DME)/steam reforming based on a Cu–Zn/γ-Al2O3 catalyst for hydrogen production. A kinetic model for a reformer that operates at low temperature (200 °C–500 °C) is simulated using COMSOL 5.2 software. Experimental verification is performed to examine the critical parameters for the reforming process. During the experiment, superior Cu–Zn/γ-Al2O3catalysts are manufactured using the sol-gel method, and ceramic honeycombs coated with this catalyst (1.77 g on each honeycomb, five honeycombs in the reactor) are utilized as catalyst bed in the reformer to enhance performance. The steam, DME mass ratio is stabilized at 3:1 using a mass flow controller (MFC) and a generator. The hydrogen production rate can be significantly affected depending on the reactant's mass flow rate and temperature. And the maximum hydrogen yield can reach 90% at 400 °C. Maximum 8% error for the hydrogen yield is achieved between modeling and experimental results. These experiments can be further explored for directly feeding hydrogen to proton exchange membrane fuel cell (PEMFC) under the load variations.  相似文献   

2.
The method of Computational Fluid Dynamics is used to predict the process parameters and select the optimum operating regime of a methanol reformer for on-board production of hydrogen as fuel for a 3 kW High-Temperature Proton Exchange Membrane Fuel Cell power system. The analysis uses a three reactions kinetics model for methanol steam reforming, water gas shift and methanol decomposition reactions on Cu/ZnO/Al2O3 catalyst. Numerical simulations are performed at single channel level for a range of reformer operating temperatures and values of the molar flow rate of methanol per weight of catalyst at the reformer inlet. Two operating regimes of the fuel processor are selected which offer high methanol conversion rate and high hydrogen production while simultaneously result in a small reformer size and a reformate gas composition that can be tolerated by phosphoric acid-doped high temperature membrane electrode assemblies for proton exchange membrane fuel cells. Based on the results of the numerical simulations, the reactor is sized, and its design is optimized.  相似文献   

3.
The catalytic steam reforming of acetic acid over both Ni/ and Co/Ce0·75Zr0·25O2 (CZO) catalysts in the temperature range of 450–650 °C and steam-to-carbon molar ratios of 3–9 was studied. It was found that the complete acetic acid conversion was achieved for all the conditions investigated. Nevertheless, the C–C bond cleavage conversion was attained less than the acetic acid conversion at a given condition due to carbon deposition on the catalyst. However, hydrogen yield was obtained in the same trend as C–C bond cleavage conversion as well. The results revealed that the CZO as an active support prefers to promote the ketonization reaction to the C-C bond cleavage reaction at a lower temperature, and vice versa at a higher temperature. The Ni/CZO catalyst exhibits higher C–C bond cleavage conversion than the Co/CZO catalyst particularly at 650 °C whereas the Co/CZO catalyst is more active for ketonization reaction at low temperatures. However, as an increase in reaction temperature, the Co/CZO catalyst promotes ketonization reaction more pronouncedly toward aldol-condensation reaction thus giving rise to the carbon deposition. The results deduced from the effect of space velocity on the activity and product distribution suggested that the steam reforming of acetic acid over Ni/CZO catalyst is dominated by decomposition of acetic acid, while that of Co/CZO catalyst by ketonization reaction.  相似文献   

4.
On-site produced hydrogen from ammonia decomposition can directly fuel solid oxide fuel cells (SOFCs) for power generation. The key issue in ammonia decomposition is to improve the activity and stability of the reaction at low temperatures. In this study, proton-conducting oxides, Ba(Zr,Y) O3-δ (BZY), were investigated as potential support materials to load Ni metal by a one-step impregnation method. The influence of Ni loading, Ba loading, and synthesis temperature, of Ni/BZY catalysts on the catalytic activity for ammonia decomposition were investigated. The Ni/BZY catalyst with Ba loading of 20 wt%, Ni loading of 30 wt%, and synthesized at 900 °C attained the highest ammonia conversion of 100% at 600 °C. The kinetics analysis revealed that for Ni/BZY catalyst, the hydrogen poisoning effect for ammonia decomposition was significantly suppressed. The reaction order of hydrogen for the optimized Ni/BZY catalyst was estimated as low as ?0.07, which is the lowest to the best of our knowledge, resulting in the improvement in the activity. H2 temperature programmed reduction and desorption analysis results suggested that a strong interaction between Ni and BZY support as well as the hydrogen storage capability of the proton-conducting support might be responsible for the promotion of ammonia decomposition on Ni/BZY. Based on the experimental data, a mechanism of hydrogen spillover from Ni to BZY support is proposed.  相似文献   

5.
Tierga and Ilmenite Fe-based ores are studied for the first time in the catalytic decomposition of methane (CDM) for the production of carbon dioxide-free hydrogen and carbon nanomaterials. Tierga exhibits superior catalytic performance at 800 °C. The effect of the reaction temperature, space velocity and reducing atmosphere in the catalytic decomposition of methane is evaluated using Tierga. The highest stability and activity (70 vol% hydrogen concentration) is obtained at 850 °C using methane as a reducing agent. Reduction with methane causes the fragmentation of the iron active phase and inhibits the formation of iron carbide, improving its activity and stability in the CDM. Hybrid nanomaterials composed of graphite sheets and carbon nanotubes with a high degree of graphitization are obtained. Considering its catalytic activity, the carbon quality, and the low cost of the material, Tierga has a competitive performance against synthetic iron-catalysts for carbon dioxide-free hydrogen and solid carbon generation.  相似文献   

6.
Low-temperature polymer electrolyte membrane fuel cell (PEMFC) acts as a promising energy source due to the non-pollution and high-energy density. However, as hydrogen supply is a major constraint limiting the wide spread of fuel cell vehicles, a dimethyl ether (DME)-steam on-board reformer (SR) based on catalytic reforming via a catalytic membrane reactor with a channel structure is a possible solution to a direct hydrogen supply. The DME-SR reaction scheme and kinetics in the presence of a catalyst of CuO/ZnO/Al2O3+ZSM-5 are functions of the temperature and hydrocarbon ratio in the hydrogen-reforming reaction. An electric heater is provided to keep the temperature at a demanded value to produce hydrogen. As there is no available analysis tool for the fuel cell battery hybrid vehicle with on-board DME reformer, it is necessary to develop the tool to study the dynamic characteristics of the whole system. Matlab/Simulink is utilized as a dynamic simulation tool for obtaining the hydrogen production and the power distribution to the fuel cell. The model includes the effects of the fuel flow rate, the catalyst porosity, and the thermal conductivity of different subsystems. A fuel cell model with a battery as a secondary energy storage is built to validate the possible utilization of on-board reformer/fuel cell hybrid vehicle. In consideration of time-delay characteristic of the chemical reactions, the time constant obtained from the experiment is utilized for obtaining dynamic characteristics. The hydrogen supplied by the reformer and the hydrogen consumed in the PEMFC prove that DME reformer can supply the adequate hydrogen to the fuel cell hybrid vehicle to cope with the required power demands.  相似文献   

7.
Small-size cobalt nanoparticles (NPs) distributed on nitrogen doped carbon support (Co/NC-X) were prepared by pyrolysis of ZIF-67 at various temperatures (X = 500, 600,700 and 800 °C) in nitrogen atmosphere and utilized as catalysts for hydrogen production through ammonia decomposition. Characterizations of the catalysts including XRD, HRTEM, XPS, H2-TPR, CO2-TPD, etc., were conducted for structure analysis. The N–C plate obtained from pyrolysis was coated with Co NPs to hinder its aggregation, which made the Co NPs dispersed evenly and increased their dispersion. The calcination temperature and the strong base of the support can adjust the strength of Co–N bond. The activity of the Co/NC-X catalysts is attributed to the high content of Co0 and the moderate Co–N bond strength. The ammonia decomposition activity of Co/NC-X catalysts in this paper is higher than many reported Co-based catalysts. Co/NC-600 catalyst demonstrates an ammonia conversion of 80% at 500 °C with a space velocity of 30,000 ml gcat?1 h?1, corresponding to a hydrogen production rate of 26.8 mmol H2 gcat?1 min?1. The work provides insight for the development of highly active cobalt-based catalysts for hydrogen production through ammonia decomposition.  相似文献   

8.
《Journal of power sources》2005,145(2):702-706
An integrated microchannel methanol processor was developed by assembling unit reactors, which were fabricated by stacking and bonding microchannel patterned stainless steel plates, including fuel vaporizer, heat exchanger, catalytic combustor and steam reformer. Commercially available Cu/ZnO/Al2O3 catalyst was coated inside the microchannel of the unit reactor for steam reforming. Pt/Al2O3 pellets prepared by ‘incipient wetness’ were filled in the cavity reactor for catalytic combustion. Those unit reactors were integrated to develop the fuel processor and operated at different reaction conditions to optimize the reactor performance, including methanol steam reformer and methanol catalytic combustor. The optimized fuel processor has the dimensions of 60 mm × 40 mm × 30 mm, and produced 450sccm reformed gas containing 73.3% H2, 24.5% CO2 and 2.2% CO at 230–260 °C which can produce power output of 59 Wt.  相似文献   

9.
The catalytic methane decomposition is the leading method for COx-free hydrogen and carbon nanomaterial production. In the present study, calcium-silicate based bimetallic Ni–Fe catalysts have been prepared and used to decompose the methane content of the ‘product gas’ obtained in the biomass gasification process for increasing total hydrogen production. Al2O3 was used as secondary support on calcium silicate based support material where Ni or Ni–Fe were doped by co-impregnation technique. The activity of catalysts was examined for diluted 6% methane-nitrogen mixture in a tubular reactor at different temperatures between 600 °C and 800 °C under atmospheric pressure, and data were collected using a quadrupole mass spectrometer. Catalysts were characterized by XRD, SEM/EDS, TEM, XPS, ICP-MS, BET, TPR, and TGA techniques. The relation between structural and textural properties of catalysts and their catalytic activity has been investigated. Even though the crystal structure of catalysts had a significant effect on the activity, a direct relation between the BET surface area and the activity was not observed. The methane conversion increased by increasing temperature up to 700 °C. The highest methane conversion has been obtained as 69% at 700 °C with F3 catalyst which has the highest Fe addition, and the addition of Fe improved the stability of catalysts. Moreover, carbon nanotubes with different diameter were formed during methane decomposition reaction, and the addition of Fe increased the formation tendency.  相似文献   

10.
The combination of steam reforming and HT-PEMFC has been considered as a proper set up for the efficient hydrogen production. Recycling anode off-gas is energy-saving strategy, which leads to enhance the overall efficiency of the HT-PEMFC. Thus, the recycling effect of anode off-gas on steam-reforming performance needs to be further studied. This paper, therefore, investigated that the combustion of anode off-gas recycled impacts on the steam reformer, which consists of premixed-flame burner, steam reforming and water-gas shift reactors. The temperature rising of internal catalyst was affected by lower heating value of fuels when the distance between catalyst and burner is relatively short, while by the flow rate of fuels and the steam to carbon ratio when its distance is long. The concentration of carbon monoxide was the lowest at 180 °C of LTS temperature, while NG and AOG modes showed the highest thermal efficiency at LTS temperature of 220–300 °C and 270–350 °C, respectively. The optimum condition of thermal efficiency to maximize hydrogen production was determined by steam reforming rather than water gas shift reaction. It was confirmed that the condition to obtain the highest thermal efficiency is about 650 °C of steam reforming temperature, regardless of combustion fuel and carbon monoxide reduction. The difference of hydrogen yield between upper and lower values is up to 1.5 kW as electric energy with a variation of thermal efficiency. Hydrogen yield showed the linear proportion to the thermal efficiency of steam reformer, which needs to be further increased through proper thermal management.  相似文献   

11.
Hydrogen on-board fuel reforming has been identified as a waste energy recovery technology with potential to improve Internal combustion engines (ICE) efficiency. Additionally, can help to reduce CO2, NOx and particulate matter (PM) emissions. As this thermochemical energy is recovered from the hot exhaust stream and used in an efficient way by endothermic catalytic reforming of petrol mixed with a fraction of the engine exhaust gas. The hydrogen-rich reformate has higher enthalpy than the petrol fed to the reformer and is recirculated to the intake manifold, which will be called reformed exhaust gas recirculation (rEGR).The rEGR system has been simulated by supplying hydrogen (H2) and carbon monoxide (CO) into a conventional Exhaust Gas Recirculation (EGR) system. The hydrogen and CO concentrations in the rEGR stream were selected to be achievable in practice at typical gasoline exhaust temperatures (temperatures between 300 and 600 °C). A special attention has been paid on comparing rEGR to the baseline ICE, and to conventional EGR. The results demonstrate the potential of rEGR to simultaneously increase thermal efficiency, reduce gaseous emissions and decrease PM formation.Complete fuel reformation can increase the calorific value of the fuel by 28%. This energy can be provided by the waste heat in the exhaust and so it is ideal for combination with a gasoline engine with its high engine-out exhaust temperatures.The aim of this work is to demonstrate that exhaust gas fuel reforming on an engine is possible and is commercially viable. Also, this paper demonstrates how the combustion of reformate in a direct injection gasoline engine via reformed Exhaust Gas Recirculation (rEGR) can be beneficial to engine performance and emissions.  相似文献   

12.
Nickel-based catalysts used for dry reforming of methane (DRM) suffer from coking and sintering, which hinders the broad application of the process in the industry. Thermogravimetric analysis was employed to investigate coking on a commercial nickel catalyst with an anti-coking additive (CaO). It was found that the catalyst sintered at temperatures between 850 and 900 °C, which resulted in permanent catalyst deactivation. For the tested Ni/CaO–Al2O3 catalyst, the coking and carbon gasification rates are equal at the temperatures of 796–860 °C, depending on the heating rate (5–20 K/min). Significant differences in the temperatures related to the maxima on TG curves for various heating rates follow from DRM kinetics. This work reveals that the coking rate is lower at higher temperatures. After 50 min, the weight gains amount to about 20% and 40% at 800 °C and 600 °C, respectively. Lower sample weight gains were observed at higher temperatures for a methane decomposition reaction over the Ni/CaO catalyst, unlike for the second tested catalyst – activated carbon. For the nickel catalyst, the reaction order for methane decomposition is 0.6 in the temperature range 640–800 °C, while the sign of the activation energy changes at 700 °C. The elaborated kinetic equation predicts the initial CH4 decomposition rate with 15% accuracy.  相似文献   

13.
《Journal of power sources》2005,145(2):691-696
A glass multi-layered microreactor with a methanol reformer that could provide power to portable electronic devices was developed to supply hydrogen to a small proton exchange membrane fuel cell (PEMFC). The microreactor consisted of four units: a methanol reformer with a catalytic combustor, a CO remover and two vaporizers. The dimensions of the microreactor were estimated by thermal simulation in order to achieve the required reaction temperature of each unit.In this study, the glass multi-layered microreactor was produced using anodic bonding. The number of glass pieces of which the microreactor was composed was 13. The experimental temperature of each unit, as well as the heat loss, for a methanol reformer of temperatures at 280 °C was measured and compared with the results from thermal simulation.  相似文献   

14.
The decarbonization of hydrocarbons is explored in this work as a method to produce hydrogen and mitigate carbon dioxide (CO2) emissions. An integrated process for power generation and carbon capture based on a hydrocarbon fueled-decarbonization unit was proposed and simulated. Ethane and propane were used as fuels and subjected to the thermal decomposition (decarbonization) process. The system is also composed of a carbon fuel cell (CFC) and hydrogen fuel cell (HFC) for the production of power and a pure CO2 stream that is ready for sequestration. The HFC is a high-temperature proton exchange membrane fuel cell operating at 200 °C. Simulations were performed using ASPEN HYSYS V.10 for the entire process including the CFC and HFC being operated at various operating temperatures (200–800 °C). The power output from the CFC and the HFC as well as the overall process efficiency were calculated. The model incorporates an energy recovery system by adopting a counter-current shell and tube heat exchangers and a turbine. The water produced from the fuel cell system can be utilized in the plant to recover the heat from the furnace. The results showed a 100% carbon capture with a nominal plant capacity of 108 MWe produced when propane fuel was fed to the decarbonizer. The CFC theoretical efficiency is 100% and the practical efficiency was taken as 70% when all internal polarizations were considered. The results showed that, in the case of propane, the CFC power output was 89 MWe when the CFC operated at 650 °C, and the HFC power output was around 45 MWe at 200 °C with an overall actual plant efficiency of 35% and 100% carbon capture. Sensitivity analysis recommends a hydrocarbon fuel cost of 0.011 $/kW as the most feasible option. The results reported here on the decarbonization of hydrocarbon fuels are promising toward the direct production of hydrogen with full carbon dioxide sequestration at a potentially lower cost especially in rural areas. The overall actual efficiencies are very competitive to those of conventional power plants operated without carbon capture.  相似文献   

15.
Reactive Flash Volatilization (RFV) is an emerging thermochemical method to produce tar free hydrogen rich syngas from waste biomass at relatively lower temperature (<900 °C) in a single stage catalytic reactor within a millisecond residence time. Here, we show catalytic RFV of bagasse using Ru, Rh, Pd, or Re promoted Ni/Al2O3 catalysts under steam rich and oxygen deficient environment. The optimum reaction conditions were found to be 800 °C, steam to carbon ratio = 1.7 and carbon to oxygen ratio = 0.6. Rh–Ni/Al2O3 performed the best, resulting in highest hydrogen concentration in the synthesis gas at 54.8%, with a corresponding yield of 106.4 g-H2/kg bagasse. A carbon conversion efficiency of 99.96% was achieved using Rh–Ni, followed by Ru–Ni, Pd–Ni, Re–Ni and mono metallic Ni catalyst in that order. Alkali and Alkaline Earth Metal species present in the bagasse ash and char, that deposited on the catalyst, was found to enhance its activity and stability. The hydrogen yield from bagasse was higher than previously reported woody biomass and comparable to the microalgae.  相似文献   

16.
Catalytic direct decomposition of dimethyl sulfide (DMS) was performed using solid acid catalysts to develop an on-site hydrogen-free desulfurization system for utilization in small systems, such as fuel cells. DMS was decomposed to CH3SH and H2S at 500 °C on SiO2–Al2O3 and various zeolite catalysts. Among the catalysts, H-BEA zeolite with Si/Al = 18.5 (H-BEA-18.5) showed the highest performance for DMS decomposition at 500 °C. While the catalytic activity at 500 °C maintained a DMS conversion of greater than 30% for up to 114 h, a large amount of carbon deposition caused gradual deterioration. At a low temperature of 400 °C, DMS decomposition to CH3SH on H-BEA-18.5 continued for 100 h with a stable conversion of approximately 30%, although the adsorption of DMS on the catalyst surface was also confirmed. To achieve a high performance for the DMS decomposition, high temperatures were required to avoid the adsorption of sulfur species.  相似文献   

17.
In this study, the ammonia decomposition reaction to produce COx-free hydrogen is investigated in a microwave reactor system using nickel-based catalysts supported by different materials. Unlike the activated carbon supported catalyst (Ni@AC), the alumina supported catalyst (Ni@Alumina) is mixed with carbon in a 1:1 ratio to reach the necessary reaction temperature in the microwave reactor. Ni@Alumina gives an overall hydrogen production rate of 73 mmol/min.gcat with 99% conversion at 400 °C under pure ammonia flow (60 ml/min). Ni@Alumina outperforms Ni@AC under microwave reactor conditions, but underperforms Ni@AC under the conventional testing, which is done for comparison. It is suggested that selective heating of nickel species in Ni@Alumina enables better performance in the microwave reactor in comparison to Ni@AC. On the other hand, high surface area and small nickel particles present in the Ni@AC structure in comparison to the Ni@Alumina structure, causes higher activity in the conventional reactor at temperatures over 550 °C. Between 400 and 550 °C, both Ni@Alumina and Ni@AC have substantially lower activity under conventional heating than microwave heating when compared at the same temperatures. Hot spot formation and microwave selective catalytic effect are considered as possible reasons for the improved performance of microwave reactor system.  相似文献   

18.
HIx processing section of Iodine-Sulphur (IS) thermochemical cycle dictates the overall efficiency of the cycle, which poses extremely corrosive HI–H2O–I2 environment, coupled with a very low equilibrium conversion (~22%) of HI to hydrogen at 450 °C. Here, we report the fabrication, characterization and operation of a 4-tube packed bed catalytic tantalum (Ta) membrane reactor (MR) for enhanced HI decomposition. Gamma coated clay-alumina tubes were used as supports for fabrication of Ta membranes. Clay-alumina base support was fabricated with 92% alumina (~8 μm particle size) and 8% clay (~10 μm particle size), sintered at a temperature of 1400 °C. An intermediate gamma alumina coating was provided with 4% polyvinyl butyral as binder for a 10% solid loading. Composite alumina tubes were coated with thin films of Ta metal of thickness <1 μm using DC magnetron sputter deposition technique. The 4-tube Ta MR assembly was designed and fabricated with integration of Pt-alumina catalyst for carrying out the HI decomposition studies, which offered >80% single-pass conversion of HI to hydrogen at 450 °C. The hydrogen throughput of the reactor was ~30 LPH at a 2 bar trans-membrane pressure, with >99.95% purity. This is the first time a muti-tube MR is reported for HIx processing section of IS process.  相似文献   

19.
Bubble reactors using molten metal alloys (e.g, nickel-bismuth and copper-bismuth) with strong catalytic activity for methane decomposition are an emerging technology to lower the carbon intensity of hydrogen production. Methane decomposition occurs non-catalytically inside the bubbles and catalytically at the gas-liquid interface. The reactor performance is therefore affected by the hydrodynamics of bubble flow in molten metal, which determines the evolution of the bubble size distribution and of the gas holdup along the reactor height. A reactor model is first developed to rigorously account for the coupling of hydrodynamics with catalytic and non-catalytic reaction kinetics. The model is then validated with previously reported experimental data on methane decomposition at several temperatures in bubble columns containing a molten nickel-bismuth alloy. Next, the model is applied to optimize the design of multitubular catalytic bubble reactors at industrial scales. This involves minimizing the total liquid metal volume for various tube diameters, melt temperatures, and percent methane conversions at a specified hydrogen production rate. For example, an optimized reactor consisting of 891 tubes, each measuring 0.10 m in diameter and 2.11 m in height, filled with molten Ni0·27Bi0.73 at 1050 °C and fed with pure methane at 17.8 bar, may produce 10,000 Nm3.h?1 of hydrogen with a methane conversion of 80% and a pressure drop of 1.6 bar. The tubes could be heated in a fired heater by burning either a fraction of the produced hydrogen, which would prevent CO2 generation, or other less expensive fuels.  相似文献   

20.
Catalytic reforming is a technology to produce hydrogen and syngas from heavy hydrocarbon fuels in order to supply hydrogen to fuel cells. A lab-scale 2.5 kWt autothermal reforming (ATR) system with a specially designed reformer and combined analysis of balance-of-plant was studied and tested in the present study. NiO–Rh based bimetallic catalysts with promoters of Ce, K, and La were used in the reformer. The performance of the reformer was studied by checking the hydrogen selectivity, COx selectivity, and energy conversion efficiency at various operating temperatures, steam to carbon ratios, oxygen to carbon ratios, and reactants' inlet temperatures. The experimental work firstly tested n-dodecane as the surrogate of Jet-A fuel to optimize operating conditions. After that, desulfurized commercial Jet-A fuel was tested at the optimized operating conditions. The design of the reformer and the catalyst are recommended for high performance Jet-A fuel reforming and hydrogen-rich syngas production.  相似文献   

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