Thermodynamic analysis of fossil fuels reforming for fuel cell application

At present, the infrastructure of hydrogen production, storage and transportation is poor. Fuel reforming for hydrogen production from liquid fossil fuels such as kerosene, petrol and diesel is of great significance for wide application of on-board fuel cell and distributed energy resources. In this work, the produced and heat released of kerosene, petrol and diesel reformed by different reforming methods (autothermal reforming, partial oxidation, steam reforming) were studied by means of thermodynamic analysis. Based on the thermodynamic analysis, the effect of reforming methods on the system's ideal thermal efficiency are analysed. The results show that the hydrogen concentration of syngas obtained from steam reforming is highest regardless of the fuel types. The hydrogen yielded by per unit volume of diesel is largest under same reforming method. Autothermal reforming has the largest ideal thermal efficiency among three reforming methods.     

Efficient operation of autothermal microchannel reactors for the production of hydrogen by steam methane reforming

Efficient conversion of methane to hydrogen has emerged as a significant challenge to realizing fuel cell-based energy systems. Autothermal microchannel reactors, coupling of exothermic and endothermic reactions in parallel channels, have become one of the most promising technologies in the field of hydrogen production. Such reactors were utilized as an intensified design for conducting the endothermic steam methane reforming reaction. The energy required by the endothermic process is supplied directly through the separating plates of the reactor structure from the exothermic process occurring on the opposing side. Optimal design problems associated with transport phenomena in such an autothermal system were analyzed. Various methods for designing and operating autothermal reactors employed in steam methane reforming were discussed. Computational fluid dynamics simulations were performed to identify the underlying principles of process intensification, and to delineate several design and operational features of the intensified reforming process. The results indicated that the autothermal reactor is preferable to be thermally conductive to ensure its structural integrity and maximum operating regime. However, the thermal properties of the reactor structure are not essential due to efficient heat transfer existing between endothermic and exothermic process streams. A reactor design which minimizes the mass transfer resistance is highly required, and the channel dimension is of critical importance. Furthermore, the challenges presented by the efficient operation of the autothermal system were identified, along with demonstrating the implementation of transport management in order to improve overall reactor performance and to mitigate extreme temperature excursions.     

An experimental study of methanol autothermal reformation as a method of producing hydrogen for transportation applications

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.     

Hydrogen production from bio-oil: A thermodynamic analysis of sorption-enhanced chemical looping steam reforming

The steam reforming of pyrolysis bio-oil is one proposed route to low carbon hydrogen production, which may be enhanced by combination with advanced steam reforming techniques. The advanced reforming of bio-oil is investigated via a thermodynamic analysis based on the minimisation of Gibbs Energy. Conventional steam reforming (C-SR) is assessed alongside sorption-enhanced steam reforming (SE-SR), chemical looping steam reforming (CLSR) and sorption-enhanced chemical looping steam reforming (SE-CLSR). The selected CO₂ sorbent is CaO(s) and oxygen transfer material (OTM) is Ni/NiO. PEFB bio-oil is modelled as a surrogate mixture and two common model compounds, acetic acid and furfural, are also considered. A process comparison highlights the advantages of sorption-enhancement and chemical looping, including improved purity and yield, and reductions in carbon deposition and process net energy balance.The operating regime of SE-CLSR is evaluated in order to assess the impact of S/C ratio, NiO/C ratio, CaO/C ratio and temperature. Autothermal operation can be achieved for S/C ratios between 1 and 3. In autothermal operation at 30 bar, S/C ratio of 2 gives a yield of 11.8 wt%, and hydrogen purity of 96.9 mol%. Alternatively, if autothermal operation is not a priority, the yield can be improved by reducing the quantity of OTM. The thermodynamic analysis highlights the role of advanced reforming techniques in enhancing the potential of bio-oil as a source of hydrogen.     

Thermodynamic analysis and heat integration for hydrogen production from bio-butanol for SOFC application: Steam reforming vs. autothermal reforming

Thermodynamic analysis of hydrogen production by steam reforming and autothermal reforming of bio-butanol was investigated for solid oxide fuel cell applications. The effects of reformer operating conditions, e.g., reformer temperature, steam to carbon molar ratio, and oxygen to carbon molar ratio, were investigated with the objective to maximize hydrogen production and to reduce utility requirements of the process and based on which favorable conditions of reformer were proposed. Process flow diagram for steam reforming and autothermal reforming integrated with solid oxide fuel cell was developed. Heat integration with pinch analysis method was carried out for both the processes at favorable reformer conditions. Power generation, electrical efficiency, useful energy for co-generation application, and utility requirements for both the processes were compared.     

Thermodynamic study of hydrogen production from crude glycerol autothermal reforming for fuel cell applications

This study presents a thermodynamic analysis of hydrogen production from an autothermal reforming of crude glycerol derived from a biodiesel production process. As a composition of crude glycerol depends on feedstock and processes used in biodiesel production, a mixture of glycerol and methanol, major components in crude glycerol, at different ratios was used to investigate its effect on the autothermal reforming process. Equilibrium compositions of reforming gas obtained were determined as a function of temperature, steam to crude glycerol ratio, and oxygen to crude glycerol ratio. The results showed that at isothermal condition, raising operating temperature increases hydrogen yield, whereas increasing steam to crude glycerol and oxygen to crude glycerol ratios causes a reduction of hydrogen concentration. However, high temperature operation also promotes CO formation which would hinder the performance of low-temperature fuel cells. The steam to crude glycerol ratio is a key factor to reduce the extent of CO but a dilution effect of steam should be considered if reforming gas is fed to fuel cells. An increase in the ratio of glycerol to methanol in crude glycerol can increase the amount of hydrogen produced. In addition, an optimal operating condition of glycerol autothermal reforming at a thermoneutral condition that no external heat to sustain the reformer operation is required, was investigated.     

Equilibrium model validation through the experiments of methanol autothermal reformation

This study investigates autothermal reforming (ATR) of fuel cell-grade methanol as a method for producing hydrogen for transportation applications. From previous work in autothermal reformation, it is clear that while the steam-to-carbon ratio (S/C) may somewhat affect the efficiency of ATR, the oxygen-to-carbon ratio (O₂/CH₃OH) is a more significant parameter in ATR of higher hydrocarbons. According to 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. This study presents experimental data that shows how ATR reactor efficiency varies with O₂/CH₃OH. Reactor efficiency data is compared to equilibrium model outputs in order to quantify the effect of O₂/CH₃OH as well as validate the equilibrium model. The results from this study serve as a baseline for future research of autothermal reforming of hydrocarbon fuels as a method for producing hydrogen in real applications.     

Thermodynamic analysis of hydrogen production via autothermal steam reforming of selected components of aqueous bio-oil fraction

From a technical and economic point of view, autothermal steam reforming offers many advantages, as it minimizes heat load demand in the reformer. Bio-oil, the liquid product of biomass pyrolysis, can be effectively converted to a hydrogen-rich stream. Autothermal steam reforming of selected compounds of bio-oil was investigated using thermodynamic analysis. Equilibrium calculations employing Gibbs free energy minimization were performed for acetic acid, acetone and ethylene glycol in a broad range of temperature (400–1300 K), steam to fuel ratio (1–9) and pressure (1–20 atm) values. The optimal O₂/fuel ratio to achieve thermoneutral conditions was calculated under all operating conditions. Hydrogen-rich gas is produced at temperatures higher than 700 K with the maximum yield attained at 900 K. The ratio of steam to fuel and the pressure determine to a great extent the equilibrium hydrogen concentration. The heat demand of the reformer, as expressed by the required amount of oxygen, varies with temperature, steam to fuel ratio and pressure, as well as the type of oxygenate compound used. When the required oxygen enters the system at the reforming temperature, autothermal steam reforming results in hydrogen yield around 20% lower than the yield by steam reforming because part of the organic feed is consumed in the combustion reaction. Autothermicity was also calculated for the whole cycle, including preheating of the organic feed to the reactor temperature and the reforming reaction itself. The oxygen demand in such a case is much higher, while the amount of hydrogen produced is drastically reduced.     

Comparison of steam and autothermal reforming of methanol using a packed-bed low-cost copper catalyst

Small-scale reformers for hydrogen production via steam and autothermal reforming of hydrocarbon feedstocks can be a solution to the lack of hydrogen distribution infrastructure. A packed-bed reactor is one possible design for such purpose. However, the two reforming processes of steam and autothermal methods have different characteristics, thus they have different and often opposite design requirements. In implementing control strategy for small-scale reformers, understanding the overall chemical reactions and the reactor physical properties becomes essential. This paper presents some inherent features of a packed-bed reactor that can both improve and/or degrade the performance of a packed-bed reactor with both reforming modes.The high thermal resistance of the packed bed is disadvantageous to steam reforming (SR), but it is beneficial to the autothermal reforming (ATR) mode with appropriate reactor geometry. The low catalyst utilization in steam reforming can help to prevent the unconverted fuel leaving the reactor during transient by allowing briefly for higher reactant fuel flow rates. In this study, experiments were performed using three reactor geometries to illustrate these properties and a discussion is presented on how to take advantages of these properties in reactor design.     

Reforming of natural gas—hydrogen generation for small scale stationary fuel cell systems

The reforming of natural gas to produce hydrogen for fuel cells is described, including the basic concepts (steam reforming or autothermal reforming) and the mechanisms of the chemical reactions. Experimental work has been done with a compact steam reformer, and a prototype of an experimental reactor for autothermal reforming was tested, both containing a Pt-catalyst on metallic substrate. Experimental results on the steam reforming system and a comparison of the steam reforming process with the autothermal process are given.     

Modeling and analysis of miniaturized methanol reformer for fuel cell powered mobile applications

In this paper a miniaturized packed bed reactor is analyzed, in which autothermal reforming of methanol occurs to produce sufficient hydrogen for generating 100 W of power. Mass balance equations are developed for each species in the reactor and an energy balance is developed for modeling non-isothermal operation. The pressure drop is modeled via the Ergun equation. Simulations are conducted in MATLAB to determine the effect of process parameters (e.g. steam to methanol ratio, inlet pressure, inlet temperature) on the production of hydrogen. It is shown that the pressure drop is negligible. Simulation results are compared with experimental results from the literature and it shown that there is excellent agreement between the simulation results and experimental results. Process conditions that lead to the generation of sufficient hydrogen for generating 100 W of power are developed.     

A combined methanol autothermal steam reforming and PEM fuel cell pilot plant unit: Experimental and simulation studies

An integrated system for hydrogen production via autothermal steam reforming of methanol and consequent power generation in a polymer electrolyte membrane (PEM) fuel cell has been developed and operated at C.P.E.R.I. The pilot plant comprises an autothermal reforming reactor to produce hydrogen, a preferential oxidation reactor (PROX) to reduce CO concentration below 50 ppm and a PEM fuel cell for power generation.The present paper deals with the study of this system, both from an experimental and a theoretical point of view. The experimental work aims to: (a) examine the effect of the reforming temperature on methanol conversion and on the effluent stream concentration, (b) investigate the effect of reaction temperature and O₂/CO ratio on the performance of the PROX reactor, and (c) evaluate the operation of a 10-cell PEM fuel cell, using pure hydrogen and air at three temperature levels. The experimental data are subsequently utilized for the validation of one-dimensional pseudo-homogeneous models that have been developed for the two reactors and also for the identification of the voltage–current characteristic curve of the PEM fuel cell. The validated models are then used to investigate the behavior and explore the interactions, both static and dynamic, among the various process subsystems.     

Industrial scale production of hydrogen from natural gas,naphtha and coal

This paper reviews the three major routes for the production of hydrogen from fossil fuels.Today there is considerable interest in the production of hydrogen via the gasification of coal. Existing processes and developments are listed.The partial oxidation processes which utilize feedstocks ranging from light hydrocarbons to heavy fuel oil are attractive due to feedstock flexibility.Hydrogen production based on the steam reforming of light hydrocarbons has become the most widely used process as a result of, in general, better economics.     

Micro methanol reformer combined with a catalytic combustor for a PEM fuel cell

This paper presents the development of a micro methanol reformer for portable fuel cell applications. The micro reformer consists of a methanol steam reforming reactor, catalytic combustor, and heat exchanger in-between. Cu/ZnO was selected as a catalyst for a methanol steam reforming and Pt for a catalytic combustion of hydrogen with air. Porous ceramic material was used as a catalyst support due to the large surface area and thermal stability. Photosensitive glass wafer was selected as a structural material because of its thermal and chemical stabilities. Performance of the reformer was measured at various test conditions and the results showed a good agreement with the three-dimensional analysis of the reacting flow. Considering the energy balance of the reformer/combustor model, the off-gas of fuel cell can be recycled as a feed of the combustor. The catalytic combustor generated the sufficient amount of heat to sustain the steam reforming of methanol. The conversion of methanol was 95.7% and the hydrogen flow of 53.7 ml/min was produced including 1.24% carbon monoxide. The generated hydrogen was the sufficient amount to operate 4.5 W polymer electrolyte membrane fuel cells.     

Catalytic steam reforming of tar for enhancing hydrogen production from biomass gasification: a review

Presently, the global search for alternative renewable energy sources is rising due to the depletion of fossil fuel and rising greenhouse gas (GHG) emissions. Among alternatives, hydrogen (H₂) produced from biomass gasification is considered a green energy sector, due to its environmentally friendly, sustainable, and renewable characteristics. However, tar formation along with syngas is a severe impediment to biomass conversion efficiency, which results in process-related problems. Typically, tar consists of various hydrocarbons (HCs), which are also sources for syngas. Hence, catalytic steam reforming is an effective technique to address tar formation and improve H₂ production from biomass gasification. Of the various classes in existence, supported metal catalysts are considered the most promising. This paper focuses on the current researching status, prospects, and challenges of steam reforming of gasified biomass tar. Besides, it includes recent developments in tar compositional analysis, supported metal catalysts, along with the reactions and process conditions for catalytic steam reforming. Moreover, it discusses alternatives such as dry and autothermal reforming of tar.     

煤基液体燃料生产技术的评价

本文介绍了采用CCTM模型对于煤基液体燃料生产技术(包括煤炭直接液化、煤炭间接液化、煤制甲醇、煤制二甲醚)的评价结果。结果表明,相对于生产单位能量的产品,能效以煤炭直接液化为最高,在55%～58%,其次为煤制甲醇,在45%～48%,煤炭间接液化在40%～42%,煤制二甲醚能效与煤炭间接液化相当;煤耗以间接液化最高,煤制二甲醚次之,再次为煤制甲醇和直接液化;水耗依次为煤制二甲醚、煤制甲醇、煤炭间接液化和煤炭直接液化;投资以间接液化高温合成为最高,二甲醚次之,以下为低温合成、煤炭直接液化和煤制甲醇;产品成本依次为煤制二甲醚、间接液化高温合成、低温合成、煤制甲醇、煤炭直接液化;污染物排放几项技术均很低。利用我国比较丰富的煤炭生产煤基液体燃料,是解决液体燃料不足的重要途径。当前国家应进一步加强煤基液体燃料生产技术的全生命周期比较论证,合理布局各项技术的示范和发展规模。     

Heat exchanger design for autothermal reforming of diesel

The increasing electrification of vehicles for passenger and heavy duty transport requires the deployment of efficient, low-emission power sources. Auxiliary Power Units (APUs) based on fuels cells offer an excellent solution, especially for supplying power during idling mode. For urban transport applications, gaseous hydrogen appears to be the best fuel option, whereas long-distance applications are better served by a liquid energy carrier. The autothermal reforming of liquid fuels such as diesel presents a simple and efficient method for producing hydrogen for fuel cell APUs. Heat integration for steam generation and air pre-warming are the key elements to a compact autothermal reformer design. With the aid of intense CFD simulations, a reformer construction was achieved with the high power density of 3.3 kW_th/l. Experimental validation indicates high hydrogen concentrations of between 32 and 36%, depending on diesel quality. In combination with already existing results, the newest autothermal reformer (ATR) generation enables the set-up of a complete APU system, fulfilling the U.S. Department of Energy (DOE) targets for fuel cell-based APUs.     

Biogas as hydrogen source for fuel cell applications

In the last decade, production of biogas from biomass degradation has attracted the attention of several research groups. The interest on this hydrogen source is focused on the potential use of this gas as raw material to supply high temperature fuel cells (HTFC). This paper reports a wide research investigation carried out at CNR-ITAE on biogas reforming processes (steam reforming, autothermal reforming and partial oxidation). A mathematical model was developed, in Aspen Plus, and an experimental validation was made in order to confirm model results. Simulations were performed to determine the reformed gas composition and the system energy balance as a function of process temperature and pressure. The value of Gas Hour Space Velocity (GHSV) was selected for calculating compositions at full equilibrium, as it is expected in operative large scale plant. To obtain a realistic evaluation of the reforming processes efficiency, the energy balance for each examined process was developed as available energy of outlet syngas on inlet required energy ratio. The comparison between values of efficiency process gives useful indication about their reliability to be integrate with fuel cell systems.     

Optimization of hydrogen production from three reforming approaches of glycerol via using supercritical water with in situ CO2 separation

A pathway for hydrogen production from supercritical water reforming of glycerol integrated with in situ CO₂ removal was proposed and analyzed. The thermodynamic analysis carried out by the minimizing Gibbs free energy method of three glycerol reforming processes for hydrogen production was investigated in terms of equilibrium compositions and energy consumption using AspenPlus™ simulator. The effect of operating condition, i.e., temperature, pressure, steam to glycerol (S/G) ratio, calcium oxide to glycerol (CaO/G) ratio, air to glycerol (A/G) ratio, and nickel oxide to glycerol (NiO/G) ratio on the hydrogen production was investigated. The optimum operating conditions under maximum H₂ production were predicted at 450 °C (only steam reforming), 400 °C (for autothermal reforming and chemical looping reforming), 240 atm, S/G ratio of 40, CaO/G ratio of 2.5, A/G ratio of 1 (for autothermal reforming), and NiO/G ratio of 1 (for chemical looping reforming). Compared to three reforming processes, the steam reforming obtained the highest hydrogen purity and yield. Moreover, it was found that only autothermal reforming and chemical looping reforming were possible to operate under the thermal self-sufficient condition, which the hydrogen purity of chemical looping reforming (92.14%) was higher than that of autothermal reforming (52.98%). Under both the maximum H₂ production and thermal self-sufficient conditions, the amount of CO was found below 50 ppm for all reforming processes.     

Well-to-Wheels analysis of hydrogen production from bio-oil reforming for use in internal combustion engines

The environmental profile of hydrogen depends greatly on the nature of the feedstock and the production process. In this Well-to-Wheels (WTW) study, the environmental impacts of hydrogen production from lignocellulosic biomass via pyrolysis and subsequent steam reforming of bio-oil were evaluated and compared to the conventional production of hydrogen from natural gas steam reforming. Hydrogen was assumed to be used as transportation fuel in an internal combustion engine vehicle. Two scenarios for the provision of lignocellulosic biomass were considered: wood waste and dedicated willow cultivation. The WTW analysis showed that the production of bio-hydrogen consumes less fossil energy in the total lifecycle, mainly due to the renewable nature of the fuel that results in zero energy consumption in the combustion step. The total (fossil and renewable) energy demand is however higher compared to fossil hydrogen, due to the higher process energy demands and methanol used to stabilize bio-oil. Improvements could occur if these are sourced from renewable energy sources. The overall benefit of using a CO₂ neutral renewable feedstock for the production of hydrogen is unquestionable. In terms of global warming, production of hydrogen from biomass through pyrolysis and reforming results in major GHG emissions, ranging from 40% to 50%, depending on the biomass source. The use of cultivated biomass aggravates the GHG emissions balance, mainly due to the N₂O emissions at the cultivation step.