Energy analysis of ethanol steam reforming for hybrid electric vehicle

Thermodynamic equilibrium of ethanol steam reforming is studied using the Gibbs free energy minimization method. The reaction paths of ethanol steam reforming are simulated using Chem‐CAD software. Appropriate optimization of reactants ratio and reaction conditions is performed, to achieve the composition of ethanol steam reforming products, which will be favorable as an internal combustion engine (ICE) fuel. The effects of process variables, such as temperature and water : ethanol molar ratio are discussed. Numerical investigations are conducted to analyze energy performance of steam reforming of ethanol for ICE. Realization of ethanol steam reforming at high temperature leads to an increase in efficiency of the process. The optimal conditions are obtained as follows: 1100 K, water : ethanol molar ratio of 1.2. Copyright © 2011 John Wiley & Sons, Ltd.     

Thermodynamic characteristics of reactants and energy conversion in steam reforming of calcium carbide furnace off-gas to produce hydrogen

In this study, to reveal the thermodynamic reaction mechanism and the conversion characteristics of material and energy for the steam reforming of multi-component materials, a chemical equilibrium model was constructed, and the reaction mechanism of the steam reforming of calcium carbide furnace off-gas (CCFG) was also identified. The conversion characteristics of material and energy were ascertained by assessing four independent reactions and their reverse reactions. And the effects of temperature, pressure and steam-to-gas ratio on the conversion ratios of CO and CH₄, the yield of H₂ and the reaction heat were investigated. In addition, a method for determining the process parameters of steam reforming based on the follow-up utilization scheme of CCFG was proposed; the method involves using a four-panel diagram that plots parameters of the steam reforming process. Thus, the range of H₂/CO mole ratio that could be obtained from the equilibrium system of steam reforming of CCFG was determined.     

Methanol steam reforming microreactor with novel 3D-Printed porous stainless steel support as catalyst support

In order to study the methanol steam reforming performance of the 3D-printed porous support for hydrogen production, three dimensional (3D) printing technology was proposed to fabricate porous stainless steel supports with body-centered cubic structure (BCCS) and face-centered cubic structure (FCCS). Catalyst loading strength of the 3D-printed porous stainless steel supports was studied. Moreover, methanol steam reforming performance of different 3D-printed porous supports for hydrogen production was experimentally investigated by changing reaction parameters. The results show that the 3D-printed porous stainless steel supports with BCCS and FCCS exhibit better catalyst loading strength, and can be used in the microreactor for methanol steam reforming for hydrogen production. Compared with 90 pores per inch (PPI) Fe-based foam support, 3D-printed porous stainless steel supports with FCCS and BCCS show the similar methanol steam reforming performance for hydrogen production in the condition of 6500 mL/(g·h) gas hourly space velocity (GHSV) with 360 °C reaction temperature. This work provides a new idea for the structural design and fabrication of the porous support for methanol steam reforming microreactor for hydrogen production.     

How to choose endothermic process for thermochemical waste-heat recuperation?

The thermochemical waste-heat recuperation (TCR) systems by steam reforming of various hydrocarbon fuels are considered. A method for determining the TCR systems efficiency is proposed. The methodology is based on the determination of the heat recuperation rate and heat transformation coefficient. TCR due to steam reforming of methanol, ethanol, glycerol, propane, and methane was analyzed. To obtain the initial data for energy analysis of TCR systems, the thermodynamic analysis was performed. With the help of Aspen HYSYS was determined the synthesis gas composition and reaction enthalpy for all investigated variants. The investigation was performed for a wide temperature range from 400 to 1200 K, for the steam-to-fuel ratio of 1, and pressures of 1 bar. It was established that TCR due to the steam reforming of ethanol, glycerol, and propane in the temperature range above 800 K, it is possible to achieve complete recuperation of the exhaust after the furnace. As a results of investigation, the practical recommendations were given for choosing endothermic reaction for the thermochemical waste-heat recuperation systems: in the temperature range up to 600 K for TCR it is necessary to choose a methanol steam reforming reaction; in the temperature range from 600 to 1000 K - the reaction of steam reforming of ethanol and glycerol; in the temperature range above 1000 K - the reaction of steam reforming propane and methane.     

Analysis of phase change heat transfer with annulus 1 kW class methanol steam reforming reaction under high-pressure operation

A fuel cell air independent propulsion (AIP) system of underwater vehicle requires a hydrogen storage system. The methanol steam reforming system is a candidate of hydrogen storage which can produce hydrogen from chemical reaction. Different from reforming system for station fuel cell system, the methanol steam reformer (MSR) for underwater vehicle requires high-pressure operation.Since the longitudinal temperature uniformity is a core parameter of conversion efficiency of steam reforming system, this study is focused on computational analysis of phase change heat transfer through the annulus for methanol steam reforming reaction. The annulus MSR using phase change material was developed to improve the temperature uniformity. The simulation model is verified with safety and performance analysis code (SPACE). The performance parameters of MSR were flow arrangement, steam to carbon ratio (SCR), and gas hourly space velocity (GHSV). The results were analyzed in terms of the hydrogen yield, heat flux, liquid mass flow rate, and methanol conversion rate. The flow arrangement varied the methanol conversion rate to a minor extent of approximately 0.1% because wall temperature was maintained uniformly. In the case of SCR, the hydrogen yield at SCR 2.5 was 0.637 (dry basis), which was the highest yield rate. Also, if GHSV was increased, hydrogen yield decreased from 0.690 (dry basis) to 0.527 (dry basis). The heat transfer pattern was also analyzed and it was found that steam is interactively condensed along with the progress of the reforming reaction.     

Dry reforming of methane has no future for hydrogen production: Comparison with steam reforming at high pressure in standard and membrane reactors

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.     

Structural design of self-thermal methanol steam reforming microreactor with porous combustion reaction support for hydrogen production

To replace the traditional electric heating mode and increase methanol steam reforming reaction performance in hydrogen production, methanol catalytic combustion was proposed as heat-supply mode for methanol steam reforming microreactor. In this study, the methanol catalytic combustion microreactor and self-thermal methanol steam reforming microreactor for hydrogen production were developed. Furthermore, the catalytic combustion reaction supports with different structures were designed. It was found that the developed self-thermal methanol steam reforming microreactor had better reaction performance. Compared with A-type, the △T_max of C-type porous reaction support was decreased by 24.4 °C under 1.3 mL/min methanol injection rate. Moreover, methanol conversion and H₂ flow rate of the self-thermal methanol steam reforming microreactor with C-type porous reaction support were increased by 15.2% under 10 mL/h methanol-water mixture injection rate and 340 °C self-thermal temperature. Meanwhile, the CO selectivity was decreased by 4.1%. This work provides a new structural design of the self-thermal methanol steam reforming microreactor for hydrogen production for the fuel cell.     

Thermochemical waste‐heat recuperation by steam methane reforming with flue gas addition

The process flow schematic of fuel‐consuming equipment with thermochemical waste‐heat recuperation by steam methane reforming with an addition of flue gas to the reaction mixture is suggested. The advantages of such a thermochemical recuperation (TCR) system compared with the TCR system by steam methane reforming are shown and justified. Based on the first law energy analysis, the heat inputs and outputs of the TCR system were determined. To determine the exhaust gases heat transformed into chemical energy of a new synthetic fuel, the thermodynamic analysis by minimizing Gibbs energy via Aspen HYSYS was performed. It was found that with an increase in the mole fraction of combustion products in the reaction mixture, the enthalpy of the methane reforming reaction increases, especially noticeable at the temperature range above 1000 K. Based on the heat, balance of the TCR system was established that the addition of combustion products to the reaction mixture has the following effects: reducing the heat input for steam production in a steam generator; reduction of the steam generator size because of the need to produce a smaller amount of steam in comparison with TCR by pure steam methane reforming; and reducing the amount of heat transferred through the wall of the reformer and, as a consequence, reduction in size of the reformer.     

Reaction mechanism of naphtha steam reforming on nickel-based catalysts,and FTIR spectroscopy with CO adsorption to elucidate real active sites

To improve the understanding of the hydrocarbon steam reforming reaction mechanism and the nature of the active sites, different nickel-based catalysts have been synthesized and studied under several reaction conditions. Catalysts from hydrotalcite precursors show better activity and higher coking resistance than traditionally prepared samples. Furthermore, introducing additives (Ce, Li or Co) in the hydrotalcite structure produces no blockage of the nickel active sites. Different structural and physical–chemical properties have been analyzed by XRD, TPR, BET and elemental analysis. FTIR spectroscopy with CO adsorption reveals interesting catalyst structure–catalytic behavior relationships; oxygen release through the catalyst surface is key parameter to improve steam reforming activity and coking resistance; and, highly unsaturated Ni surface atoms located on the metal–support interphase are relevant structures to the catalysis and most active sites for the steam reforming reaction. Steam reforming reaction proposed sequence involves: 1) hydrocarbon preferably activation on active Ni surface sites and steam preferred activation on basic support surface sites, 2) oxygen spill-over from the support to the metal phase, and 3) reaction between carbon and oxygen species occurring on the metal–support interphase.     

Factors influencing methanol steam reforming inside the oriented linear copper fiber sintered felt

A kind of oriented linear copper fiber sintered felt as a catalyst support for methanol steam reforming is briefly introduced in this work. The sintered felt porosity, sintered felt length and manifold shape as three fundamental influencing factors are experimental investigated their effects on the performances of methanol steam reforming. Experimental results indicate that the sintered felt with moderate porosity and long sintered felt length can effectively enhance the reaction performances of methanol steam reforming. The sintered felt with symmetric triangle manifold can achieve better reaction performances than the one with oblique triangle manifold. However, it is also found that the structural parameters of sintered felt and manifold shape show little influence on the methanol steam reforming at low GHSVs and reaction temperatures. Among these influencing factors, the sintered felt length showed much more influences on the performances of methanol steam reforming than the sintered felt porosity and manifold shape at high reaction temperature.     

The mechanism characterizations of methane steam reforming under coupling condition of temperature and ratio of steam to carbon

To elucidate the coupling effects of temperature and ratio of steam to carbon on the methane steam reforming process, the characterizations of methane steam reforming at different temperature and ratio of steam to carbon in term of distribution of H₂ and CO, and the elementary reaction rate were investigated. Meanwhile, the formation mechanisms of H₂ and CO via sensitivity analysis and reaction path analysis were obtained. The results showed that the coupling effects of temperature and ratio of steam to carbon on the methane steam reforming were higher than that of individual factor. The effects of temperature on the methane steam reforming were higher than that of the ratio of steam to carbon. The adsorption and desorption reaction of CH₄ on the surface of Ni-based catalyst had the most obvious effect on the sensitivity of H₂, CH₄ and CO. Besides, the effects of adsorption and desorption reaction of H₂O on the sensitivity of H₂ were higher than that of CH₄ and CO. Hydrogen was generated by the desorption reaction of H(s) in the adsorbed state and from three generating paths: a) CH₄(s) dissociated directly or reacted with O(s) to form H(s); b) The dissociation reaction of H₂O(s) produced H(s); c) OH(s) dissociated directly or reacted with C(s) to form H(s). Carbon monoxide was generated from single path: CH₄(s)→CH₃(s)→CH₂(s)→CH(s)→C(s)→CO(s)→CO(g).     

Bimetallic catalysts performance during ethanol steam reforming: Influence of support materials

Ni–Cu catalysts supported on different materials were tested in ethanol steam reforming reaction for hydrogen production. These catalysts were evaluated at reaction temperature of 400 °C under atmospheric pressure. The reagents, with a water/ethanol molar ratio equal to 10, were fed at 70 dm³/(h g_cat) (after vaporization). Analysis of the ethanol conversion, as well as evaluation and quantification of the reaction products, indicated the catalyst 10% Ni–1% Cu/Ce_0.6Zr_0.4O₂ as the most appropriate for the ethanol steam reforming under investigated reaction conditions, among the studied catalysts. During 8 h of reaction this catalyst presented an average ethanol conversion of 43%, producing a high amount of H₂ by steam reforming and by ethanol decomposition and dehydrogenation parallel reactions. Steam reforming, among the observed reactions, was quantified by the presence of carbon dioxide. About 60% of the hydrogen was produced from ethanol steam reforming and 40% from parallel reactions.     

Electrochemical reforming of methane using SrZr0.5Ce0.4Y0.1O3-δ proton-conductor cell combined with paper-structured catalyst

Reforming of hydrocarbon which is an important hydrogen production method proceeds in two steps, i.e. steam reforming and shift reaction. Due to different thermodynamics, the two reactions are conventionally conducted at different temperatures. This study examines one step methane reforming by use of proton-conducting electrochemical cell in combination with a reforming catalyst. Promotion of the reforming reaction was intended by extracting hydrogen via electrochemical hydrogen pumping with a proton conductor cell. In order to compensate for the slow kinetics of the steam reforming, a paper catalyst loaded with Ni was placed in front of the electrochemical cell. Electrolyte support cells were used to verify this concept, and the effect of the electrochemical hydrogen pump was investigated from the composition of the outlet gas. Electrode support cells using a thin film electrolyte was used to reduce overvoltage. It is demonstrated that the steam reforming reaction and the shift reaction take place in one electrochemical cell. Effective catalyst placement and energy efficiency is discussed.     

Modeling and simulation of hydrogen production from dimethyl ether steam reforming using exhaust gas

In this paper, hydrogen production from steam reforming of DME (dimethyl ether) has been modeled and simulated using a CFD (computational fluid dynamics) method. The reformation chemistry occurs in a porous catalytic bed where exhaust gas is supplied through the EGR (exhaust gas recycling) valve of the engine to drive the endothermic reaction system. The tightly coupled system of mass, energy, and momentum equations are used to describe the complex physical and chemical process of DME steam reforming. The global reaction kinetics for the reforming is adopted in the CFD model. The mathematical models are introduced into the commercial software Comsol, and then numerical simulations are also performed based on this model. The model predictions are quantitatively validated by experiment data. The simulation results indicate the temperature distribution, mass distribution, DME conversion, and hydrogen production from steam reforming of DME. In addition, the fuel to steam ratio and velocity of exhaust gas are manipulated as operating parameters. These simulation results will provide helpful data to design and operate a bench scale catalytic fluidized bed reactor. Copyright © 2015 John Wiley & Sons, Ltd.     

Tar removal on dolomite and steam reforming catalyst: Benzene,toluene and xylene reforming

Tar removal performance of dolomite and commercial precious metal based steam reforming catalyst have been investigated by using the surrogated compounds of tar, namely benzene, toluene and xylene at changing tar loads and temperatures. Hydro- and steam dealkylation of alkyl aromatic hydrocarbons have been observed on dolomite and precious metal based catalyst. Gaseous products like H₂ and CO₂, started to be measured at 563 °C, and detection of benzene and toluene in case of xylene reforming proved the presence of selective reforming reaction on alkyl groups. Total steam reforming of aromatic rings has not been observed as sub-stoichiometric formation of reforming products meaning that selective steam reforming was only applied onto the alkyl groups of aromatics. Steam dealkylation reaction favorably occurred at 500–600 °C whereas thermal degradation and/or polymerization of aromatic compounds became the prevailing reaction with increasing the operation temperatures beyond 700 °C. Tar conversion was found to be independent on inlet tar load unless excess steam was present. Co-existence of tar and methane seemed beneficial as proved by enhanced methane reforming activity and complete tar removal. This improvement has been explained by the polymerization reaction of tar compounds and formation of unmeasurable soot particles.     

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.     

Sustainable hydrogen production for fuel cells by steam reforming of ethylene glycol: A consideration of reaction thermodynamics

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.     

Review of methanol reforming-Cu-based catalysts,surface reaction mechanisms,and reaction schemes

Recent development in proton-exchange membrane fuel cell technology has stimulated research in fuel processing for hydrogen production. Hydrogen can be produced from four different types of methanol reforming processes, namely methanol decomposition, partial oxidation of methanol, steam reforming of methanol and oxidative steam reforming of methanol. This review paper discusses commonly used Cu-based catalysts including their kinetic, compositional, and morphological characteristics in methanol reforming reactions. Although research exploring surface reaction mechanism over various Cu-based catalysts was first attempted about three decades ago, the scheme remains controversial. This technical discussion will focus on the commonly reported surface intermediate species, which are methoxy, formaldehyde, dioxymethylene, formate and methyl formate. The surface reaction mechanism could be complicated by the introduction of reactants such as oxygen and steam, into the system as they would subsequently initiate secondary reactions. Different reaction schemes of methanol reforming are presented.     

Simultaneous production of two types of synthesis gas by steam and tri‐reforming of methane using an integrated thermally coupled reactor: mathematical modeling

In this work, tri‐reforming and steam reforming processes have been coupled thermally together in a reactor for production of two types of synthesis gases. A multitubular reactor with 184 two‐concentric‐tubes has been proposed for coupling reactions of tri‐reforming and steam reforming of methane. Tri‐reforming reactions occur in outer tube side of the two‐concentric‐tube reactor and generate the needed energy for inner tube side, where steam reforming process is taking place. The cocurrent mode is investigated, and the simulation results of steam reforming side of the reactor are compared with corresponding predictions for thermally coupled steam reformer and also conventional fixed‐bed steam reformer reactor operated at the same feed conditions. This reactor produces two types of syngas with different H₂/CO ratios. Results revealed that H₂/CO ratio at the output of steam and tri‐reforming sides reached to 1.1 and 9.2, respectively. In this configuration, steam reforming reaction is proceeded by excess generated heat from tri‐reforming reaction instead of huge fired‐furnace in conventional steam reformer. Elimination of a low performance fired‐furnace and replacing it with a high performance reactor causes a reduction in full consumption with production of a new type of synthesis gas. The reactor performance is analyzed on the basis of methane conversion and hydrogen yield in both sides and is investigated numerically for various inlet temperature and molar flow rate of tri‐reforming side. A mathematical heterogeneous model is used to simulate both sides of the reactor. The optimum operating parameters for tri‐reforming side in thermally coupled tri‐reformer and steam reformer reactor are methane feed rate and temperature equal to 9264.4 kmol h^?1 and 1100 K, respectively. By increasing the feed flow rate of tri‐reforming side from 28,120 to 140,600 kmol h^?1, methane conversion and H₂ yield at the output of steam reforming side enhanced about 63.4% and 55.2%, respectively. Also by increasing the inlet temperature of tri‐reforming side from 900 to 1300 K, CH₄ conversion and H₂ yield at the output of steam reforming side enhanced about 82.5% and 71.5%, respectively. The results showed that methane conversion at the output of steam and tri‐reforming sides reached to 26.5% and 94%, respectively with the feed temperature of 1100 K of tri‐reforming side. Copyright © 2013 John Wiley & Sons, Ltd.