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1.
The methane dry-reforming and steam reforming reactions were studied as a function of pressure (1–20 atm) at 973 K in conventional packed-bed reactors and a membrane reactors. For the dry-reforming reaction in a conventional reactor the production yield of hydrogen rose and then decreased with increasing pressure as a result of the reverse water-gas shift reaction in which the hydrogen reacted with the reactant CO2 to produce water. For the steam reforming reaction the production yield of hydrogen kept increasing with pressure because the forward water-gas shift reaction produced additional hydrogen by the reaction of CO with water. In the membrane reactors the methane conversion and the hydrogen production yields were higher for both the dry-reforming and steam reforming reactions, but for the dry reforming at high pressure half of the hydrogen was transformed into water. Thus, the dry-reforming reaction is not practical for producing hydrogen.  相似文献   

2.
On the basis of the Gibbs free energy minimization principle, the dry autothermal reforming performance of crude glycerol in situ hydrogen separation is investigated via thermodynamic analysis. The impact of hydrogen separation fraction on gas composition in product, carbon formation and reaction heat is studied. It can be found that the hydrogen separation promotes the hydrogen production and hinders methane formation. The hydrogen removal is selective to the reduction of carbon deposition, which improves the carbon formation at a low feed CO2 to glycerol molar ratio and the impact is reverse for high feed CO2 to glycerol molar ratio. When the reaction temperature varies from 850 K to 900 K, the required oxygen to glycerol molar ratio of thermal neutral condition is obviously increased from 0.15 to 0.4 with hydrogen removal. Meanwhile, the glycerol impurities evaluation indicates that the syngas yield is significantly reduced with the increase of the glycerol impurities. At a high temperature, the hydrogen removal is in favor of the achievement of autothermal process.  相似文献   

3.
A recent techno-economic study (Spallina et al., Energy Conversion and Management 120: p. 257–273) showed that the membrane assisted chemical looping reforming (MA-CLR) technology can produce H2 with integrated CO2 capture at costs below that of conventional steam methane reforming. A key technical challenge related to MA-CLR is the achievement of reliable solids circulation between the air and fuel reactors at large scale under the high (>50 bar) operating pressures required for optimal performance. This work therefore presents process modelling and economic assessments of a simplified alternative; membrane assisted autothermal reforming (MA-ATR), that inherently avoids this technical challenge. The novelty of MA-ATR lies in replacing the MA-CLR air reactor with an air separation unit (ASU), thus avoiding the need for oxygen carrier circulation. The economic assessment found that H2 production from MA-ATR is only 1.5% more expensive than MA-CLR in the base case. The calculated cost of hydrogen (compressed to 150 bar) in the base case was 1.55 €/kg with a natural gas price of €6/GJ and an electricity price of €60/MWh. Both concepts show continued performance improvements with an increase in reactor pressure and temperature, while an optimum cost is achieved at about 2 bar H2 permeate pressure. Sensitivities to other variables such as financing costs, membrane costs, fuel and electricity prices are similar between MA-ATR and MA-CLR. Natural gas prices represent the most important sensitivity, while the sensitivity to membrane costs is relatively small at high reactor pressures. MA-ATR therefore appears to be a promising alternative to achieve competitive H2 production with CO2 capture if technical challenges significantly delay scale-up and deployment of MA-CLR technology. The key technical demonstration required before further MA-ATR scale-up is membrane longevity under the high reactor pressures and temperatures required to minimize the cost of hydrogen.  相似文献   

4.
Autothermal reforming of methane includes steam reforming and partial oxidizing methane. Theoretically, the required endothermic heat of steam reforming of methane could be provided by adding oxygen to partially oxidize the methane. Therefore, combining the steam reforming of methane with partial oxidation may help in achieving a heat balance that can obtain better heat efficacy. Membrane reactors offer the possibility of overcoming the equilibrium conversion through selectively removing one of the products from the reaction zone. For instance, only can hydrogen products permeate through a palladium membrane, which shifts the equilibrium toward conversions that are higher than the thermodynamic equilibrium. In this study, autothermal reforming of methane was carried out in a traditional reactor and a Pd/Ag membrane reactor, which were packed with an appropriate amount of commercial Ni/MgO/Al2O3 catalyst. A power analyzer was employed to measure the power consumption and to check the autothermicity. The average dense Pd/Ag membrane thickness is 24.3 μm, which was coated on a porous stainless steel tube via the electroless palladium/silver plating procedure. The experimental operating conditions had temperatures that were between 350 °C and 470 °C, pressures that were between 3 atm and 7 atm, and O2/CH4 = 0–0.5. The effects of the operating conditions on methane conversion, permeance of hydrogen, H2/CO, selectivities of COx, amount of power supply, and the carbon deposition of the catalyst after the reaction is thoroughly discussed in this paper. The experimental results indicate that an optimum methane conversion of 95%, with a hydrogen production rate of 0.093 mol/m2. S, can be obtained from the autothermal reforming of methane at H2O/CH4 = 1.3 and O2/CH4 near 0.4, at which the reaction does not consume power, and the catalysts are not subject to any carbon deposition.  相似文献   

5.
This paper reports the results obtained in a techno-economic analysis of the Steam Methane Reforming (SMR) technology aided with solar heat, developed and demonstrated in the European FCH JU project CoMETHy: a compact membrane reformer heated with molten salt up to 550 °C allowed to simultaneously carry out methane steam reforming, water-gas-shift reaction and hydrogen separation. This reactor can be integrated with new generation Concentrating Solar Thermal (CST) systems to supply the process heat. Experimental validation of the technology has been successfully achieved in a pilot scale plant and the results recently published. In this paper, we introduce a fully-integrated scheme and operation strategies of a plant on the 1500 Nm3/h hydrogen production scale. Then, techno-economic analysis of this new solar-driven process is presented to evaluate its competitiveness. Considering a plant capacity of 1500 Nm3/h (pure hydrogen production) and today's costs for the methane feed and the CST technology, obtained Hydrogen Production Cost (HPC) are in the range of 2.8–3.3 €/kg for a “solar-hybrid” system with high capacity factor (8000 h/year operation) and 4.7 €/kg for a “solar-only” case, while HPC≅1.7 €/kg can be obtained with the conventional route under equivalent assumptions. However, a sensitivity analysis shows that the expected drop of the cost of the CST technology will bring the HPC around 2.4 €/kg for the “solar-hybrid” case and close to 3.4 €/kg for the “solar-only” case, thus making the cost of solar reforming closer to conventional SMR with CO2 capture and with wind/solar electrolysis in the future. In the “solar-hybrid” case total CO2 production can be reduced by 13–29% with 58–70% of produced CO2 recovered as pure stream (at 1.3 bar); in the “solar-only” case total CO2 production can be reduced by 52% and 100% of produced CO2 recovered as pure stream (at 1.3 bar). However, compared to the conventional route, CO2 avoidance costs are still relatively high (≥137 €/tonCO2) and process optimization measures required. Therefore, optimization measures have been outlined to increase the overall process efficiency and further reduce the HPC.  相似文献   

6.
In this experimental work, methane steam reforming (MSR) reaction is performed in a dense Pd-Ag membrane reactor and the influence of pressure on methane conversion, COx-free hydrogen recovery and COx-free hydrogen production is investigated. The reaction is conducted at 450 °C by supplying nitrogen as a sweep gas in co-current flow configuration with respect to the reactants. Three experimental campaigns are realized in the MR packed with Ni-ZrO catalyst, which showed better performances than Ni-Al2O3 used in a previous paper dealing with the same MR system. The first one is directed to keep constant the total pressure in both retentate and permeate sides of the membrane reactor. In the second case study, the total retentate pressure is kept constant at 9.0 bar, while the total permeate pressure is varied between 5.0 and 9.0 bar. As the best result of this work, at 450 °C and 4.0 bar of total pressure difference between retentate and permeate sides, around 65% methane conversion and 1.2 l/h of COx-free hydrogen are reached, further recovering 80% COx-free hydrogen over the total hydrogen produced during the reaction. Moreover, a study on the influence of hydrogen-rich gas mixtures on the hydrogen permeation through the Pd-Ag membrane is also performed and discussed.  相似文献   

7.
Four ethanol-derived hydrogen production processes including conventional ethanol steam reforming (ESR), sorption enhanced steam reforming (SESR), chemical looping reforming (CLR) and sorption enhanced chemical looping reforming (SECLR) were simulated on the basis of energy self-sufficiency, i.e. process energy requirement supplied by burning some of the produced hydrogen. The process performances in terms of hydrogen productivity, hydrogen purity, ethanol conversion, CO2 capture ability and thermal efficiency were compared at their maximized net hydrogen. The simulation results showed that the sorption enhanced processes yield better performances than the conventional ESR and CLR because their in situ CO2 sorption increases hydrogen production and provides heat from the sorption reaction. SECLR is the most promising process as it offers the highest net hydrogen with high-purity hydrogen at low energy requirement. Only 12.5% of the produced hydrogen was diverted into combustion to fulfill the process's energy requirement. The thermal efficiency of SECLR was evaluated at 86% at its optimal condition.  相似文献   

8.
In this study a numerical analysis of hydrogen production via an autothermal reforming reactor is presented. The endothermic reaction of steam methane reforming and the exothermic combustion of methane were activated with patterned Ni/Al2O3 catalytic layer and patterned Pt/Al2O3 catalytic layer, respectively. Aiming to achieve a more compacted process, a novel design of a reactor was proposed in which the reforming and the combustion catalysts were modeled as patterned thin layers. This configuration is analyzed and compared with two configurations. In the first configuration, the catalysts are modeled as continuous thin layers in parallel, while, in the second configuration the catalysts are modeled as continuous thin layers in series (conventional catalytic autothermal reactor). The results show that the pattern of the catalyst layers improves slightly the hydrogen yield, i.e. 3.6%. Furthermore, for the same concentration of hydrogen produced, the activated zone length can be decreased by 38% and 15% compared to the conventional catalytic autothermal reforming and the configuration where the catalysts are fitted in parallel, respectively. Besides, the oxygen consumption is lowered by 5%. The decrement of the catalyst amount and the oxygen feedstock in the novel studied design lead to lower costs and compact process.  相似文献   

9.
In order to improve the hydrogen production efficiency by glycerol steam reforming, a membrane-assisted fluidized bed reactor with carbon dioxide sorption is developed to enhance the reforming process. Low-temperature operation in a membrane reactor is necessary considering the thermal stability of membrane. In this work, the sorption-enhanced glycerol steam reforming process in a fluidized bed membrane reactor under the condition of low temperature is numerically investigated, where the hydrotalcite is employed as CO2 sorbents. The impact of operating pressure on the reforming performance is further evaluated. The results demonstrate that the integration of membrane hydrogen separation and CO2 sorption can effectively enhance the low-temperature glycerol reforming performance. The fuel conversion above 95% can be achieved under an elevated pressure.  相似文献   

10.
This paper focuses on investigating that the influence of O2, CO2 and H2O on characteristics of autothermal reforming of methane in micro premix chamber on Ni catalysts. In addition, the effect of catalytic wall temperature on autothermal reforming reaction of methane under a certain ratio of CH4/CO2/H2O/O2 is simulated. The results indicate that appropriately increasing O2 concentration can increase the conversion efficiency of CH4, so does adding CO2 or H2O. The positive effect of O2, CO2 and H2O is more pronounced at the higher temperature. The temperature range of 650–750 K is the important transitional region in the reactions of CH4/O2, CH4/H2O and CH4/CO2. It also gives a guide to the available range of parameters in the high efficiency reforming process of micro-reactor.  相似文献   

11.
In this work, a synthetic mixture of natural gas is considered in a steam reforming process for generating hydrogen by using a membrane reactor housing a composite membrane constituted of a Pd-layer (13 μm) supported on alumina. The Pd/Al2O3 membrane separates part of the produced hydrogen through its selective permeation, although it shows a relatively low H2/N2 ideal selectivity (>200 at 0.5 bar of trans-membrane pressure and T = 425 °C).The steam reforming reaction is performed at 420 °C, by varying the gas hourly space velocity between 4400 h?1 and 6900 h?1 and by using two different mixtures containing some common impurities found within natural gas pipeline. Specifically, the effect of N2 and CO2 as impurities in the feed line is analyzed. The reaction pressure and steam-to-carbon ratio (S/C) are kept constant at 3.0 bar (abs.) and 3.5/1, respectively.The best performance of the Pd-based membrane reactor is obtained at 420 °C, 3.0 bar and 100 mL/min of sweep-gas, yielding a methane conversion of 55% and hydrogen recovery >90%.  相似文献   

12.
Herein, a methane steam reforming (MSR) reaction was carried out using a Pd composite membrane reactor packed with a commercial Ru/Al2O3 catalyst under mild operating conditions, to produce hydrogen with CO2 capture. The Pd composite membrane was fabricated on a tubular stainless steel support by the electroless plating (ELP) method. The membrane exhibited a hydrogen permeance of 2.26 × 10?3 mol m2 s?1 Pa?0.5, H2/N2 selectivity of 145 at 773 K, and pressure difference of 20.3 kPa. The MSR reaction, which was carried out at steam to carbon ratio (S/C) = 3.0, gas hourly space velocity (GHSV) = 1700 h?1, and 773 K, showed that methane conversion increased with the pressure difference and reached 79.5% at ΔP = 506 kPa. This value was ~1.9 time higher than the equilibrium value at 773 K and 101 kPa. Comparing with the previous studies which introduced sweeping gas for low hydrogen partial pressure in the permeate stream, very high pressure difference (2500–2900 kPa) for increase of hydrogen recovery and very low GHSV (<150) for increase hydraulic retention time (HRT), our result was worthy of notice. The gas composition monitored during the long-term stability test showed that the permeate side was composed of 97.8 vol% H2, and the retentate side contained 67.8 vol% CO2 with 22.2 vol% CH4. When energy was recovered by CH4 combustion in the retentate streams, pre-combustion carbon capture was accomplished using the Pd-based composite membrane reactor.  相似文献   

13.
The long-term stability at autothermal reforming of diesel fuel and kerosene was studied using Juelich's autothermal reformer ATR 9.2, which is equipped with a commercial proprietary RhPt/Al2O3–CeO2 catalyst. The experiment was run for 10,000 h of time on stream at constant reaction conditions with an O2/C molar ratio of 0.47, a H2O/C molar ratio of 1.9, and a gas hourly space velocity of 30,000 h−1. Kerosene produced via the gas-to-liquid process and diesel fuel synthesized via the bio-to-liquid route were used. Both fuels were almost free of mass fractions of sulfur and aromatics. The trends for the desired main products of autothermal reforming H2, CO, CO2, and CH4 were almost stable when kerosene was used. When the fuel mass flow was switched to diesel fuel however, different modes of catalyst deactivation occurred (active sites blocked by carbonaceous deposits, sintering processes), leading to a decrease in the concentrations of H2 and CO2 with a simultaneous increase in the CO content. This paper defines carbon conversion as the decisive criterion for evaluating the long-term stability during autothermal reforming of kerosene and diesel fuel. Carbon conversion was diminished via three different pathways during the long-term experiment. Undesired byproducts found in the gas phase leaving the reactor had the strongest impact on carbon conversion. These byproducts included ethene, propene, and benzene. Furthermore, a liquid oily residue was detected floating on the condensed unconverted mass flow of water. This happened once during the whole experiment. Finally, undesired organic byproducts were dissolved in the mass flow of unconverted water. These were found to be straight-chain and branched paraffins, esters, alcohols, acids, aldehydes, ketones, etc. Nevertheless, at the end of the long-term experiment, carbon conversion still amounted to more than 98.2%.  相似文献   

14.
Hydrogen-fueled plants can play an important role in the field of carbon capture and storage, because they facilitate the mitigation of harmful emissions. In this paper, two combined-cycle power plants with pre-combustion CO2 capture are examined, in which natural gas is converted into a hydrogen-rich fuel through reforming. The first plant considered operates with a hydrogen-separating membrane and the second with an autothermal reformer. The two plants are compared to a reference plant without CO2 capture and briefly to alternative oxy-fuel and post-combustion capture technologies. It is found that both plants suffer high penalties caused by the high energy requirements of the reforming components and the CO2 compression units. Additionally, both plants appear inferior to alternative capture technologies. When comparing the two reforming plants, the plant with the hydrogen-separating membrane operates somewhat more efficiently. However, in order to make these technologies more attractive, their thermodynamic efficiency must be enhanced. The potential for improving the efficiencies of these plants is revealed by an exergetic analysis.  相似文献   

15.
A porous medium-catalyst hybrid reformer for hydrogen-rich syngas production by dry autothermal reforming (DATR) was investigated in this study. In the reforming process, the reaction under excess enthalpy was explored by visualization in packed-bed catalyst reactor. The hybrid design was arranged with a porous medium (PM) in the upstream of the catalyst packed-bed. In the arrangement, the reactants were preheated by internal heat recirculation and the selectivity of H2-rich syngas was enhanced by the catalyst surface reaction. Controlled parameters included CO2/CH4 and O2/CH4 ratios, gas hourly space velocity (GHSV) with or without porous medium. The experimental results demonstrated that the reforming reaction with the hybrid reformer could achieve excess enthalpy under the tested parameters. The excess enthalpy ratio was between 0.15 and 0.55. The temperature measurement along the axial position and image observation of the catalyst packed-bed indicated that the flame was stably held at the interface of the PM and the catalyst bed, and this enhanced fuel conversion and reforming efficiencies, especially in the low methane conversion condition. In the dry autothermal reforming process, part of the chemical energy released from the reaction supplies the energy required for a self-sustaining reaction. Therefore, the selection of the parameters was determined to achieve high reforming efficiency and low energy loss percentage. The results showed that the energy loss percentage was between 12.7 and 24.6% and reforming efficiency was between 64.4 and 79.5% with the best reforming parameter settings (O2/CH4 = 0.7–0.9 and CO2/CH4 = 0.0–2.0).  相似文献   

16.
This study investigates autothermal reforming (ATR) of methanol as a method of producing fuel cell-grade hydrogen for transportation applications. From the previous works in autothermal reformation, it is known that while the steam-to-carbon ratio (S/C) may somewhat affect the efficiency of ATR, the oxygen-to-methanol ratio (O2/CH3OH) is a more significant parameter in ATR of higher hydrocarbons. Methanol differs from higher hydrocarbons in that it is reformed at relatively low temperatures and, therefore, may respond to O2/CH3OH differently from higher hydrocarbons. According to the past studies, the optimum O2/CH3OH for ATR of methanol is equal to 0.23. However, this conclusion is based on models which utilize assumptions that are not necessarily accurate, such as complete fuel conversion and ideal reaction products. This study presents experimental data that shows how the ATR reactor efficiency varies with O2/CH3OH. The results from this study may serve as a baseline for future research of autothermal reforming of hydrocarbon fuels as a method of producing hydrogen in transportation applications.  相似文献   

17.
The use of renewable biomass, such as ethylene glycol (EG), for hydrogen production offers a more sustainable system compared to natural gas and petroleum reforming. For the first time, the reaction thermodynamics of steam reforming and sorption enhanced steam reforming of EG have been investigated. Gibbs free energy minimization method was used to study the effect of pressure (1-5 atm), temperature (500-1100 K) and water to EG ratio (WER 0-8) on the production of hydrogen and the formation of associated by-products (CH4, CO2, CO, C). The results suggest that hydrogen production is optimum when steam reforming occurs at atmospheric pressure, 925 K and with a WER of 8. Moreover, working at high temperature (>900 K) and with a WER above 6 inhibits almost entirely the production of methane and carbon. The main source of hydrogen in the system is found to be steam reforming of methane and water gas shift reaction by the analysis of the response reactions (RERs). Hydrogen production is governed by the former reaction at low temperatures while the latter one comes into prominence as temperature increases. By coupling with in situ CO2 capture using CaO, the formation of CO2 and CO can be avoided and high purity of hydrogen (>99%) can be achieved.  相似文献   

18.
In this study, the H2-rich syngas (H2 + CO) production from biomass derived gas (BDG) by dry autothermal reforming (DATR) is investigated. Methane and carbon dioxide is the major composition of biomass derived gas. DATR reaction combined benefits of partial oxidation (POX) and dry reforming (DR) reaction was carried out in this study. The reforming parameters on the conversion of methane and syngas selectivity were explored. The reforming parameters included the fuel feeding rate, CO2/CH4 and O2/CH4 molar ratios. The experimental results demonstrated that it not only supplied the energy required for self-sustained reaction, but also avoided the coke formation by dry autothermal reforming. It has a wide operation region to maintain the moderate production of the syngas. During the reforming process, the reformate gas temperature was between 650 and 900 °C, and energy loss percentage in reforming process was between 15 and 30%. Further, high CO2 concentration in the reactant had a considerable influence on the heat release of oxidation, and thereby decreased the reformate gas temperature. It caused the reduction of synthesis gas concentration and assisting/impeding combustion composition (A/I) ratio. However, it was favorable to CO selectivity because of the reverse water-gas shifting reaction. The H2/CO molar ratio between 1 and 2 was achieved by varying CO2/CH4 molar ratio. However, the syngas concentrations were affected by CO2/CH4 and O2/CH4 molar ratio.  相似文献   

19.
Chemical looping steam reforming (CLSR) of ethanol using oxygen carriers (OCs) for hydrogen production has been considered a highly efficient technology. In this study, NiO/MgAl2O4 oxygen carriers (OCs) were employed for hydrogen production via CLSR with and without CaO sorbent for in-situ CO2 removal (sorption enhanced chemical looping steam reforming, SE-CLSR). To find optimal reaction conditions of the CLSR process, including reforming temperatures, the catalyst mass, and the NiO loadings on hydrogen production performances were studied. The results reveal that the optimal temperature of OCs for hydrogen production is 650 °C. In addition, 96% hydrogen selectivity and a 'dead time' (the reduced time of OCs) less than 1 minute is obtained with the 1 g 20NiO/MgAl2O4 catalysts. The superior catalytic activity of 20NiO/MgAl2O4 is due to the maximal quantity of NiO loadings providing the most Ni active surface centers. High purity hydrogen is successfully produced via CLSR coupling with CaO sorbent in-situ CO2 removal (SE-CLSR), and the breakthrough time of CaO is about 20 minutes under the condition that space velocity was 1.908 h?1. Stability CLSR experiments found that the hydrogen production and hydrogen selectivity decreased obviously from 207 mmol to 174 mmol and 95%–85% due to the inevitable OCs sintering and carbon deposition. Finally, stable hydrogen production with the purity of 89%~87% and selectivity of 96%~93% was obtained in the modified stability SE-CLSR experiments.  相似文献   

20.
In this work, the performance of an industrial dense PdAg membrane reformer for hydrogen production with methane mixed reforming reaction was evaluated. The rate parameters of mixed reforming reaction on a Ni based catalyst optimized by using the experimental results. One-dimensional models have been considered to model the steam reforming industrial membrane reformer (SRIMR) and mixed reforming industrial membrane reformer (MRIMR). The models are validated by experimental data.The proficiency of MRIMR and SRIMR at similar conditions used as a basis of comparison in terms of temperature, methane conversion, hydrogen yield, syngas production rate and CO2 flow rate. Results revealed that the methane conversion, hydrogen yield and syngas production rate in MRIMR is considerably higher than SRIMR. Furthermore, the operation temperature of MRIMR could be 195 °C lower than that for SRIMR. This would contribute to a major decrease in process costs as well as a reduction in catalyst sintering. On the other hand, although MRIMR consumes CO2, the exited CO2 flow rate at the SRIMR is three times more than that of at the MRIMR, which is a main advantage of MRIMR from the environmental issues point of view.  相似文献   

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