Autothermal Reforming Process Research Articles

Optimization of autothermal reforming of ultrasonic methanol sprays over Cu/ZnO catalyst for hydrogen production via a statistical approach

Autothermal reforming (ATR) is a highly efficient process for hydrogen production. This study uses the Taguchi method to optimize the hydrogen production from methanol via the ATR process. The Cu/ZnO particle is used as the catalyst, and an ultrasonic spray system is used to generate aqueous methanol sprays for ATR. A Taguchi L9 orthogonal array is used to assess the effects of preheating temperature, oxygen/carbon (O2/C) ratio, steam/carbon (S/C) ratio, and gas hourly space velocity (GHSV) on H2 yield. The results show that the O2/C ratio has the most significant influence on the objective function, H2 yield, followed by preheating temperature, S/C ratio, and GHSV, with the most negligible impact. The optimal conditions for maximizing the H2 yield from signal/noise ratio analysis are a preheating temperature of 350 °C, an O2/C ratio of 0.65, an S/C ratio of 1.5, and a GHSV of 7000 h−1. The analysis of variance (ANOVA) indicates that the model has a good fit with a high R2 value (=0.9735). The contribution to H2 yield is 40.22 % by the O2/C ratio, 37.80 % by the preheating temperature,19.34 % by the S/C ratio, and 2.54 % by the GHSV. The H2 yields from ATR, steam reforming, and partial oxidation are also compared. The results indicate that ATR is the optimal choice for producing hydrogen from methanol while maintaining the proper reaction temperature range without generating extra energy.

Layered perovskite-derived Ni/La2-2xPr2xO3 catalysts for hydrogen production via auto-thermal reforming of acetic acid

Auto-thermal reforming (ATR) is an effective route to extract hydrogen from acetic acid (HAc) from bio-oil. Nickel-based catalysts were found active for conversion of HAc via the ATR process. However, the main concerns, such as carbon deposition and sintering, led to deactivation of catalysts. Herein, to address these issues, a series of (La,Pr)2NiO4 layered perovskites and the derived catalysts of Ni/La2-2xPrxO3 were prepared, and evaluated by ATR. It was found that with Pr entering the La2O3 lattice, the reduction temperature of Ni oxide was decreased with improved dispersion of Ni0; meanwhile, lattice defects were found within La2-2xPr2xO3, and oxygen vacancies were formed with more reactive oxygen species, promoting gasification of coking precursors. The lower formation energy of oxygen vacancy over Pr-doped La2O3 support was further proved by DFT, confirming the improved oxygen vacancies. Therefore, the Ni0·8La1.35Pr0.73O3.92±δ catalyst exhibited excellent catalytic performance along with a stable HAc conversion near 100% and a hydrogen yield around 2.49 mol-H2/mol-HAc, while no coking was detected.

Hybrid systems design for blue and green hydrogen co-production: Integration of autothermal reforming with solid oxide electrolysis

Hydrogen is a clean and sustainable energy alternative to fossil fuels. Current hydrogen production methods are carbon intensive; hence, developing low-carbon hydrogen production methods is important. Among various production technologies, autothermal reforming (ATR) and solid oxide electrolysis (SOEC) are considered promising in terms of energy efficiency. However, there are several limitations: (i) ATR requires an air separation unit that consumes a large amount of energy, and (ii) SOEC, high-temperature steam electrolysis requires an electric resistance heater. To address these limitations, this study proposes a hybrid system of ATR integrated with SOEC. In the hybrid system, waste steam and heat in the ATR process are provided for the SOEC process, whereas the oxygen by-product in the SOEC process is supplied to the ATR process. In particular, the hybrid system where SOEC-generated oxygen completely satisfies the ATR reaction’s oxygen demand exhibits the best thermodynamic and economic performance. This system represents a 28.6% reduction in power consumption compared to a stand-alone system that independently produces blue and green hydrogen. In addition, it exhibits enhanced economic performance with a levelized cost of hydrogen of 5.28 $/kg, which is 1.22 $/kg lower than that of the stand-alone system.

Techno-economic comparison of ammonia production processes under various carbon tax scenarios for the economic transition from grey to blue ammonia

Ammonia synthesis is a carbon-intensive process, with significant volumes of carbon dioxide produced during the preliminary production of hydrogen from a fossil fuel feedstock. Since carbon emissions vary significantly depending on the hydrogen production method, the impact of carbon capture and storage (CCS) implementation on the overall economic performance of the ammonia synthesis process differs. Therefore, it is crucial to (1) integrate cost-effective CCS into various ammonia synthesis processes and (2) conduct a comprehensive comparison of grey and blue ammonia systems together, considering the economic costs of the carbon emissions. This study aims to investigate the economic feasibility of large-scale ammonia processes under various carbon tax scenarios and suggest carbon-efficient options for the ammonia industry. Three ammonia synthesis processes are designed that differ in their hydrogen production method – steam methane reforming (SMR), autothermal reforming (ATR), and hybrid SMR-ATR – and these three options also have grey ammonia and blue ammonia production versions. The grey ammonia production systems do not include a carbon capture procedure, while the blue ammonia systems ensure that the CO2 emissions are below 0.065 t CO2/t NH3. In the present study, both the grey and blue versions of the three ammonia production processes are subjected to techno-economic evaluation under various carbon tax scenarios. For the grey ammonia systems, economic feasibility varies depending on the carbon tax scenario under consideration. Grey ATR becomes the most cost-effective option within a carbon tax of 95 $/ton to 115 $/ton. In contrast, the economic viability of the blue ammonia systems is unaffected by the carbon tax policy environment. In particular, blue ATR exhibits 6% and 14% lower levelized cost of ammonia (LCOA) compared to the blue SMR and blue Hybrid SMR-ATR, respectively. Overall, the results indicate that, below a carbon tax threshold of 62 $/ton, the SMR process without carbon capture is economically favorable. However, for carbon tax above 62 $/ton, the ATR process with carbon capture has greater economic feasibility than other options. A minimum carbon tax of 62 $/ton is required to promote the transition to blue ammonia. These findings thus provide valuable insight into the establishment of effective carbon regulations in response to the global demand to tackle the climate crisis.

Soot production in high pressure inverse diffusion flames with enriched oxygen in the oxidizer stream

Catalyst degradation due to soot formation is one of the main issues in the autothermal reforming (ATR) process, which is widely regarded as the future technology for hydrogen production from natural gas. In this work, soot formation under conditions similar to ATR was systematically investigated, focusing specifically on the effects of pressure on soot formation in inverse diffusion flames (IDFs) under oxygen rich conditions. Methane was diluted with carbon dioxide; the oxygen content in the oxidizer stream varied from 55 to 70%-by-mol. Polycyclic aromatic hydrocarbon (PAH) and soot concentrations in the flames were measured by laser-induced fluorescence (LIF) and laser-induced incandescence (LII) respectively. Flame images showed that, as the pressure increased, the luminous region of the IDFs moved downward to mask the blue reaction region, and the flames became narrower. The degree of flame narrowing in the IDFs was milder than normal diffusion flames (NDFs). LIF measurements showed that increasing the pressure promoted PAH formation, which also subsequently promoted soot formation. Both PAH and soot formation increased linearly with pressure. The linear relationship was different from that of the NDFs. Flame simulations suggested that the promotion of soot formation with pressure was largely driven by PAH adsorption. Under the conditions of this study, lowering the oxygen content promotes soot formation in the IDFs. The results of this work contribute to the understanding of soot formation in IDFs at elevated pressures and the optimization of the ATR process.

Hydrogen production using piston reactor technology: Process design and integration for CO2 emission reduction

The piston reactor is emerging as a simple, inexpensive, and compact technology to carry out chemical reactions. Potential piston reactor advantages include high temperature and pressure conditions at short residence times, large throughput, and fast quenching steps. Published research related to hydrogen production using piston reactors has almost exclusively focused on the POX route for hydrogen production and on exploring reactor performance as opposed to overall process performance in terms of specific production costs and emissions. This study provides a process-level understanding of the techno-economics of hydrogen production using piston reactor technology via the three prominent routes for grey and blue hydrogen production: methane partial oxidation (POX), auto-thermal reforming (ATR), and steam methane reforming (SMR). A piston reactor model is initially used to screen the reactor performance in terms of methane conversion and hydrogen production, revealing underperformance for the SMR route. Next, stand-alone hydrogen production processes embedding the piston reactors for the remaining POX and ATR routes are synthesized and specific production costs and CO2 emissions for ‘grey’ hydrogen production determined. Next, the piston reactor processes are integrated with CO2 capture and compression steps for subsequent sequestration and the impact of such CO2 emission mitigation on ‘blue’ hydrogen production costs is evaluated. The obtained results show that the piston-reactor ATR process significantly outperforms the piston-reactor POX process for both grey and blue hydrogen production. For a 100 TPD plant capacity and a natural gas price of $3.3/GJ, blue hydrogen production costs for the piston reactor-based ATR processes are observed to be 1.6/kg H2, which is competitive with reported blue hydrogen production costs using the conventional SMR route. A sensitivity study reveals that the plant capacity has significant impact while piston reactor useful life had low impact hydrogen production costs.

ZrxPr1–xOy Solid Solution‐Supported Cobalt‐Based Catalysts for Hydrogen Production

AbstractTo obtain high yields of hydrogen, a series of ZrxPr1–xOy‐supported cobalt catalysts were synthesized by the sol‐gel method and tested in autothermal reforming (ATR) of acetic acid (HAc) derived from bio‐oil. X‐ray diffraction, nitrogen physisorption, H2‐temperature‐programmed reduction, and thermogravimetric analysis were conducted to investigate the factors affecting the activities of the catalysts. Over the Co‐Zr‐Pr‐O catalyst, a ZrxPr1–xOy solid solution was formed after calcination; meanwhile, the active component of Co0 was highly dispersed over the solid solution after reduction in hydrogen for 1 h at 700 °C. As a result, stable reactivity was recorded in the ATR process of HAc: the hydrogen yield reached 2.58 with near 100 % HAc conversion, while better resistance to coking was observed.

Biogas reforming integrated with PEM electrolysis via oxygen storage process for green hydrogen production: From design to robust optimization

The oxygen gas produced from electrolysis is both a good heat supplier and an oxidizing agent for the autothermal reforming (ATR) process. Thus, green hydrogen production could be achieved by integrating the biogas ATR and electrolysis processes directly with renewable power sources. Under the natural fluctuation of renewable power, the oxygen produced from electrolysis can be stored in a compressed or liquid state in an intermittent storage tank to buffer its production rate for steady-state operation of biogas ATR process. In this study, integrated systems have been newly proposed using compressed gas and liquid oxygen storage methods, which are denoted as PEMCOAR and PEMLOAR systems, respectively. Using the surrogate model based on polynomial chaos expansion methodology (PCE), the statistical moments of levelized cost of hydrogen (LCOH) of both proposed systems were optimized considering the uncertainties of renewable power, biogas composition, and electricity tariff. As a result, the mean and variance of LCOH is reduced by 11.9% and 37.8%, respectively. In case of renewable power and biogas price of 0.06 $/kWh and 5.58 $/MMBTU, it was observed that the average LCOH below the current green hydrogen market price at a renewable power scale of over 55 MW. In conclusion, the study suggests the optimal operating condition under uncertainties and simultaneously, prove the economic feasibility of integrating electrolysis and biogas ATR systems.

Hydrogen production and temperature control for DME autothermal reforming process

This study focuses on the control of dimethyl ether (DME) autothermal reforming (ATR) process integrated with proton exchange membrane fuel cells to provide adequate external power for an on-board reformer hydrogen vehicle. ATR reaction was made over Pd–Zn/γ-Al2O3 catalyst, which provides higher selectivity to the hydrogen due to its good oxidation and reforming activities. Catalyst activity was tested experimentally by varying the temperature. The hydrogen volume fraction is close to 45% at the optimal temperature of 400 °C. The objective of the process control scheme was to control the ATR reactor's temperature and the hydrogen production rate. A combination of the feedforward control and the closed-loop control (based on PID control) was applied wherein the DME, and air flow rates were adjusted automatically, and steam was supplied excessively to promote reactions. Due to its good oxidation and reforming activity, it had a high selectivity to hydrogen. The experimental results showed that the volume fraction of hydrogen in the hydrogen-rich gas is close to 45% at the optimum temperature of 400 °C. The control strategy could ensure that the hydrogen production rate changed with the change of fuel cell load and did not affect the temperature of the autothermal reformer. In this way, the stable operation of the reformer was realized, and the fuel cell had a sufficient supply of hydrogen.

Modeling of hydrogen production by diesel reforming over Rh/Ce0.75Zr0.25O2‐δ‐ƞ‐Al2O3/FeCrAl wire mesh honeycomb catalytic module

The work is devoted to experimental studies and construction of a mathematical model of n-hexadecane (as the simplest diesel surrogate) reforming over Rh/Ce0.75Zr0.25O2-δ-ƞ-Al2O3/FeCrAl wire mesh honeycomb catalytic module in auto-thermal reforming (ATR) and steam reforming (SR) modes. Experiments were performed using the scalable catalytic modules with recurrent meshy channeled internal geometrical structure. This provided the accurate reproduction of mass transfer limitations and accompanying homogeneous reactions, thus significantly simplifying the following scale-up procedures. Impossibility to apply simple isothermal reactor models was compensated by application of CFD modelling for reproduction of internal distribution of temperature, fluid velocities and composition inside the catalyst module.The earlier proposed reaction scheme was supported by additional reactions to account for the formation of light C2-C5 hydrocarbons. The proposed model provides good description of both ATR and SR process modes, at the same time demonstrating significant difference between them.The proposed model may be used for development, scale-up and optimization of catalytic reformers using SR and ATR modes and their combination for processing diesel and similar liquid hydrocarbon fuels.

Hydrogen production from partial oxidation and autothermal reforming of methanol from a cold start in sprays

Hydrogen is a noticeable clean fuel that can be applied in power generation and transport. Hydrogen production from methanol via thermochemical methods has been widely studied and used. In these methods, autothermal reforming (ATR) simultaneously contains endothermic steam reforming and exothermic partial oxidation of methanol (POM), The latter can help start the experiment and provide heat for the former. This study aims to perform methanol ATR by sprays via an h-BN-Pt catalyst without preheating, mainly focusing on the effects of operating conditions on hydrogen production and methanol conversion. Meanwhile, the comparison between ATR and POM of methanol is also carried out. The results of POM indicate that the highest H2 and CO concentrations are obtained at the air-to-methanol molar ratio (O2/C) of 0.7, and the CH3OH conversion can reach 100%. However, through the ATR process, the methanol conversion reaches 60% at O2/C = 0.7 with steam-to-methanol molar ratio (S/C) of 1.5. At S/C = 0.5, it is observed that the CH3OH conversion is up to 100% with increasing the O2/C ratio, and the H2 yield is higher than that of POM. The effects of S/C and O2/C ratios on ATR indicate that the CH3OH conversion and reaction temperature are significantly increased with decreasing the S/C ratio and increasing the O2/C ratio. Overall, the H2 yield from ATR at S/C of 0.5 and O2/C of 0.7 is highest with 1.697 mol (mol CH3OH)−1.

Mechanism of the autothermal reforming reaction of methane on Pt(1 1 1) surfaces: A density functional theory study

Density functional theory calculations were carried out to better understand the reaction mechanism for the autothermal reforming of methane on Pt(1 1 1) surfaces. Particular focus was placed upon gaining a more complete understanding of the adsorption, oxidation, combination, and dehydrogenation processes involved in the autothermal reforming reaction. The adsorption energies for various species on the (1 1 1) surface were computed, and the preferred adsorption geometry for various species was determined. The primary reaction pathways were determined based on the reaction barriers and energies for all the elementary steps involved in the processes. The results indicated that the preferred adsorption oxygen-containing species is formyl due to its lowest adsorption energy on the (1 1 1) surface. Methane can be dissociated on the (1 1 1) surface to generate methyl and then further oxidatively dehydrogenated to form carbon. The elementary reaction pathways involving hydroxyl radicals play a minor role in the overall autothermal reforming process due to the low coverage of hydroxyl radicals on the (1 1 1) surface. The reaction pathways involving hydroxyl radicals may be relevant only to the formation process of methanol fragments from carbon adsorbed on the (1 1 1) surface due to its low reaction barrier. Finally, the primary reaction pathways are the oxidation of methane on the (1 1 1) surface: CH4 → CH3,adsorbed → CH2,adsorbed → CHadsorbed → Cadsorbed → COadsorbed.

Comparative study of gasoline, diesel and biodiesel autothermal reforming over Rh-based FeCrAl-supported composite catalyst

Catalytic autothermal reforming (ATR) of a number of hydrocarbon fuels was studied over composite RhCZ-S catalyst (0.24 wt% Rh supported on structured Ce0.75Zr0.25O2-δ-ƞ-Al2O3/FeCrAl carrier). Iso-octane and n-hexadecane as model compounds of gasoline and diesel fuel, respectively, showed similar properties in ATR process, indicating weak influence of molecular weight and branching degree of liquid alkanes on catalyst performance. Biodiesel ATR characteristics were similar to those of n-hexadecane ATR, as the utilized biodiesel predominantly contained alkanes, being products of fatty acid tail fragments hydrogenation. Even in the case of gasoline ATR, sufficient amount of monoaromatics did not influence a lot on the catalyst performance. Diesel ATR showed rather different situation: the catalyst tended to lose activity due to coking, and incomplete fuel conversion was observed. Analysis of unreacted fuel revealed bi- and polyaromatic compounds (mainly naphtalenes and antracenes) were difficult to convert.

Development of a robust and efficient biogas processor for hydrogen production. Part 1: Modelling and simulation

The present work deals with the modelling and simulation of a biogas Demo-processor for green hydrogen production via Autothermal reforming (ATR) process aimed at covering a wide span of potential applications, from fuel cells feed up to the production of pure hydrogen. The biogas ATR unit is composed of a structured catalyst support close coupled to a wall-flow filter that retain soot particles that can be formed during the ATR reaction. Modelling and simulation (CFD and FEM) were carried out to select the innovative catalyst support with promising results for the fuel processor. 3D digital sample reconstruction was performed for the selection of the appropriate porous structures commercially available for the soot filtration and furthermore, 2D CFD analysis was also used to examine flow uniformity issues due to soot trap integration downstream to the ATR. Moreover, the inherent flexibility of the model performed allowed its application in the assessment of the Demonstration plant operating in real conditions. Besides, Aspen simulation has demonstrated that the ATR process is the most promising process to hydrogen production compared to other types of reforming process.

Analysis of di-methyl ether production routes: Process performance evaluations at various syngas compositions

This paper investigates direct di-methyl ether (DME) production based on dry methane reforming (DMR-to-DME) and on bireforming (BiR-to-DME). Technically, DMR-to-DME is preferred to BiR-to-DME because the former produces synthesis gas (syngas) with a hydrogen to carbon monoxide molar ratio (H2/CO) of 1 which is the ideal ratio for DME synthesis. Whereas the latter produces a H2/CO close to 2 and consequently suffers from two apparent drawbacks: (1) lack of the so-called ‘synergy effect’ – a feature that enhances DME yield when operating at H2/CO close to 1, and (2) generation of a high heat capacity by-product (H2O) which makes DME recovery energy intensive. In this paper, we find that those two disadvantages actually enhance the performance of BiR compared to DMR across a range of performance metrics. Although the presence of water increases the cooling/heating duty and the distillation columns’ reboiler duty in the BiR route, more heat released from DME synthesis reactor can be utilized in the reboilers to make BiR techno-economically compatible. To assess the sustainability of DMR and BiR, evaluations are carried out against an existing industrial scale DME production route (auto-thermal-reforming (ATR)). By utilizing the carbon in the CO2 from an attached post-combustion carbon capture plant, DMR and BiR can save 22.3% methane feed uptake on average compared to the ATR process, which results in the DMR and BiR reducing CO2 emissions by at least 6.5% on average.

Autothermal reforming of impure glycerol for H2 production: Thermodynamic study including in situ CO2 and/or H2 separation

In the present work, thermodynamics was applied to study the autothermal reforming (ATR) of impure glycerol (mixture of glycerol and methanol) to generate pure hydrogen. The equilibrium compositions were calculated using the Gibbs free energy minimization method and simulations were performed in a wide range of conditions of pressure (1–20 atm), temperature (600–1000 K), oxygen to glycerol feed molar ratio (0.0–3.0), and water to glycerol feed molar ratio (3–12). The effect of in situ CO2 and/or H2 removal was investigated as well, in the perspective of reaction/separation process integration in a hybrid multifunctional reactor. Whatever the composition of the glycerol fed, the in situ separation of H2 and CO2 in ATR process maximizes the hydrogen yield and completely eliminates methane, carbon monoxide and carbon dioxide formation. At 700 K, it is possible to improve the H2 yield, with respect to the traditional reactor, up to 186% when CO2 removal is considered, up to 152% when only H2 removal is implemented, and by 195% when both H2 and CO2 removal are considered in the hybrid reactor.From the investigation of the energetically neutral conditions, it was found that in the sorption-enhanced process, with or without in situ H2 separation, no partial oxidation reactions are needed to provide the required heat to maintain the isothermal reformer at the desired temperature, and consequently the yield of hydrogen can be improved up to 6.93, which is close to the stoichiometric theoretical value of 7.

Internal Model Control Design for Autothermal Reforming System

This paper focuses on the control system design for a process of autothermal reforming (ATR) of ethanol. The targeted application is within an on-board fuel processor of ATR operating at the adiabatic reaction temperature for hydrogen production. An internal model control (IMC) method is designed for controlling the adiabatic reaction temperature of ATR reactor by manipulating the input air flow rate. Two strategies of controller design with and without the feed temperature control of the preheater unit are proposed in order to determine the suitable controller system as the surrounding temperature is a major disturbance for cold weather. Theoretical analysis demonstrates that IMC strategy can achieve desired performance. Two loops of control system of the ATR process combined with the feed temperature control can compensate the surrounding temperature better than without the feed temperature control.

Energy and exergy analysis as tools for optimization of hydrogen production by glycerol autothermal reforming

In this work, various assessment tools were comprehensively applied to investigate hydrogen production via glycerol autothermal reforming. These tools are used to study the chemical reactions, design and simulate the entire hydrogen production process, investigate the energetic and exergetic performances of the processes and perform parametric analyses (using intuitive and design of experiment-based methods).Investigating the chemical reactions of autothermal reforming (ATR) of glycerol reveals that the optimal conditions, based on maximizing the hydrogen production, minimizing the methane and carbon monoxide contents and eliminating coke formation at thermoneutral conditions, can be achieved at a water–glycerol feed ratio (WGFR), reforming temperature (T) and oxygen–glycerol feed ratio (OGFR) of 9, 900 K and 0.35, respectively. The energetic study of the resulting process indicates that approximately two-thirds of the energy fed to the process is recovered in the useful product (H2) and that the remaining incoming process energy is exhausted in the off-gas. The exergetic investigation reveals that the exergetic efficiency of the ATR process is 57% and that 152 kJ are destroyed to generate 1 mol of hydrogen. The process operating conditions recommended by the chemical reaction investigation suffers from low performance because energetic and exergetic efficiencies are comparatively lower than values previously reported in literature for other reformates. The parametric investigation indicates that more accurate conditions are needed to convert glycerol–hydrogen. These conditions ensure the lowest consumption of energy to generate a given amount of hydrogen. This paper recommends WGFR = 5.5, T = 900 K and OGFR = 0.96 as the optimum conditions for the entire glycerol-to-hydrogen process. For this configuration, the thermal and exergetic efficiencies are 78.7% and 67.8%, respectively.

Autothermal Reforming of Ethanol for Hydrogen Production: Modeling and Simulation

Autothermal reforming (ATR), which is the combination of endothermic steam reforming and exothermic partial oxidation, is an attractive process to produce hydrogen using for transportation fuel cell because of its moderate size. ATR is considered to be thermally self-sustaining that the external heat source is not required. In order to keep the adiabatic temperature of ATR reactor, the process control strategy needs in understanding the dynamic characteristics of the ATR system. Thus, the modeling and simulation of ATR process for hydrogen production fueled by ethanol is carried out in this work. The open loop responses of the feed and ATR temperatures are simulated by the dynamic models of ATR system. The simulation results showed the predominantly influence of the electrical power of preheater on the feed and ATR temperatures while the air flowrate has an inverse effect on the feed temperature and a direct effect on the ATR temperature. As a result, the match of control loop is very sensible for an effective control strategy in the development of control system design for maintaining the adiabatic temperature of ATR reactor for sustaining the effectiveness of hydrogen production.

A comparative study on energetic and exergetic assessment of hydrogen production from bioethanol via steam reforming, partial oxidation and auto-thermal reforming processes

Three known types of ethanol reforming processes, ethanol steam reforming (ESR), partial oxidation (POX) and auto-thermal reforming (ATR), are investigated. Favorable operating conditions are identified for each reaction system to maximize the production of hydrogen from bioethanol. Each process consists of three sections: the main reactor (ESR, POX or ATR), the CO clean-up section comprised of the water gas shift reactor and preferential CO oxidation reactor and finally, the purification section. The performances of these processes are evaluated through mass, energy and exergy analyses.The material balances show that the total amount of ethanol required to generate 1mol of hydrogen is 0.23mol for the ATR, 0.24mol for the POX and 0.25mol for the ESR. The ATR reforming process is shown to have the highest energetic efficiency, i.e., the lowest amount of energy is consumed to produce the same amount of hydrogen from ethanol. Moreover, the ATR process has the best exergetic performance, as it presents the highest ratio of exergy recovered in the hydrogen stream to the total exergy supplied to the system. For all three of the systems, the exergy destruction occurs mainly in the reformer due to the high irreversibility of the reaction.