Dynamic modeling of a three-stage low-temperature ethanol reformer for fuel cell application

A low-temperature ethanol reformer based on a cobalt catalyst for the production of hydrogen has been designed aiming the feed of a fuel cell for an autonomous low-scale power production unit. The reformer comprises three stages: ethanol dehydrogenation to acetaldehyde and hydrogen over SnO₂ followed by acetaldehyde steam reforming over Co(Fe)/ZnO catalyst and water gas shift reaction. Kinetic data have been obtained under different experimental conditions and a dynamic model has been developed for a tubular reformer loaded with catalytic monoliths for the production of the hydrogen required to feed a 1 kW PEMFC.     

Hydrogen production from ethanol over Co/ZnO catalyst in a multi-layered reformer

A Co/ZnO catalyst was prepared by coprecipitation method, and was applied for ethanol steam reforming. The effect of reaction conditions on the ethanol steam reforming performance was studied in the temperature ranges from 400 °C to 600 °C and the space velocity ranges from 10,000 h⁻¹ to 120,000 h⁻¹ in a fixed bed reactor. The Co/ZnO showed high activity with an ethanol conversion of 97% and a H₂ concentration of 73% at a gas hourly space velocity of 40,000 h⁻¹ and a moderately low temperature of 450 °C. EXAFS analysis for fresh and spent samples confirms that Co phase maintains during reaction. The catalyst was then loaded into a multi-layered reformer of which the design concept allows for integrating endothermic steam reforming, exothermic combustion and evaporation in a reactor. The performance of the compact reformer demonstrated that the hydrogen production rate satisfy a PEMFC stack power level of 540 W suitable for portable power supplies.     

Thermodynamic analysis of ethanol steam reforming using Gibbs energy minimization method: A detailed study of the conditions of carbon deposition

In this paper, a thermodynamic analysis of ethanol/water system, using the Gibbs energy minimization method, has been carried out. A mathematical relationship between Lagrange's multipliers and carbon activity in the gas phase was deduced. From this, it was possible to calculate carbon activities in both stable and metastable systems. For the system that corresponds to ethanol steam reforming at very low contact times, composed mainly of ethylene and acetaldehyde, carbon activities were always much greater than unity over the whole temperature range, changing from 1.2 × 10⁷ at 400 K to 1.1 × 10⁴ at 1200 K. Furthermore, there was practically no effect of the inlet steam/ethanol ratio on carbon activity values. These results indicate that such a system is highly favorable to carbon formation. On the other hand, by considering a more stable system, in order to represent high contact times, it was observed that carbon activities are much lower and depend greatly on the inlet steam/ethanol ratio employed. Besides, the complete conversion of ethylene and acetaldehyde into other species, such as CO, CO₂, CH₄ and H₂, lowers the total Gibbs energy of the system. By computing carbon activities in experimental systems, it was also possible to explain deviations between thermodynamic analysis and experimental results regarding carbon deposition.     

Energy efficiency analysis of an integrated glycerin processor for PEM fuel cells: Comparison with an ethanol-based system

The aim of this work is to analyze energetically the use of glycerin as the primary hydrogen source to operate a proton exchange membrane fuel cell. A glycerin processor system based on its steam reforming is described departing from a previous process model developed for ethanol processing. Since about 10% w/w of glycerin is produced as a byproduct when vegetable oils are converted into biodiesel, and due to the later is increasing its production abruptly, a large glycerin excess is expected to oversaturate the market. The reformed stream contains mainly H₂ but also CO, CO₂, H₂O and CH₄. As CO is a poison for PEM fuel cell type, a stream purification step is previously required. The purification subsystem consists of two water gas shift reactors and a CO preferential oxidation reactor to reduce the CO levels below 10 ppm. The reforming process is governed by endothermic reactions, requiring thus energy to proceed. Depending on the system operation point, the energy requirements can be fulfilled by burning an extra glycerin amount (to be determined), which is the minimal that meets the energy requirements. In addition a self-sufficient operation region can be distinguished. In this context, the water/glycerin molar ratio, the glycerin steam reformer temperature, the system pressure, and the extra glycerin amount to be burned (if necessary) are the main decision variables subject to analysis. Process variables are calculated simultaneously, updating the composite curves at each iteration to obtain the best possible energy integration of the process. The highest net system efficiency value computed is 38.56% based on the lower heating value, and 34.71% based on the higher heating value. These efficiency values correspond to a pressure of 2 atm, a water/glycerin molar ratio of 5, a glycerin steam reformer temperature of 953 K, and an extra glycerin amount burned of 0.27 mol h⁻¹. Based on the main process variables, suitable system operation zones are identified. As in practice, most PEM fuel cells operate at 3 atm, optimal variable values obtained at this condition are also reported. Finally, some results and aspects on the system performance of both glycerin and ethanol processors operated at 3 atm are compared and discussed.     

Towards a rechargeable alcohol biobattery

This research focused on the transition of biofuel cell technology to rechargeable biobatteries. The bioanode compartment of the biobattery consisted of NAD-dependent alcohol dehydrogenase (ADH) immobilized into a carbon composite paste with butyl-3-methylimidazolium chloride (BMIMCl) ionic liquid serving as the electrolyte. Ferrocene was added to shuttle electrons to/from the electrode surface/current collector. The bioanode catalyzed the oxidation of ethanol to acetaldehyde in discharge mode. This bioanode was coupled to a cathode that consisted of Prussian Blue in a carbon composite paste with Nafion 212 acting as the separator between the two compartments. The biobattery can be fabricated in a charged mode with ethanol and have an open circuit potential of 0.8 V in the original state prior to charging or in the discharged mode with acetaldehyde and have an open circuit potential of 0.05 V. After charging it has an open circuit potential of 1.2 V and a maximum power density of 13.0 μW cm⁻³ and a maximum current density of 35.0 μA cm⁻³, respectively. The stability and efficiency of the biobattery were studied by cycling continuously at a discharging current of 0.4 mA and the results obtained showed reasonable stability over 50 cycles. This is a new type of secondary battery inspired by the metabolic processes of the living cell, which is an effective energy conversion system.     

Experimental and computational investigations of a compact steam reformer for fuel oil and diesel fuel

The present work describes the optimisation of a compact steam reformer for light fuel oil and diesel fuel. The reformer is based upon a catalytically coated micro heat exchanger that thermally couples the reforming reaction with a catalytic combustion. Since the reforming process is sensitive to reaction temperatures and internal flow patterns, the reformer was modelled using a commercial CFD code in order to optimise its geometry. Fluid flow, heat transfer and chemical reactions were considered on both sides of the heat exchanger. The model was successfully validated with experimental data from reformer tests with 4 kW, 6 kW and 10 kW thermal inputs of light fuel oil. In further simulations the model was applied to investigate parallel flow, counter flow and cross flow conditions along with inlet geometry variations for the reformer. The experimental results show that the reformer design allows inlet temperatures below 773 K because of its internal superheating capability. The simulation results indicate that two parallel flow configurations provide fast superheating and high fuel conversion rates. The temperature increase inside the reactor is influenced by the inlet geometry on the combustion side.     

Economic analysis of hydrogen production through a bio-ethanol steam reforming process: Sensitivity analyses and cost estimations

In this study, the hydrogen selling price from ethanol steam reforming has been estimated for two different production scenarios in the United States, i.e. central production (150,000 kg H₂/day) and distributed (forecourt) production (1500 kg H₂/day), based on a process flowchart generated by Aspen Plus^® including downstream purification steps and economic analysis model template published by the U.S Department of Energy (DOE) [1]. The effect of several processing parameters as well as catalyst properties on the hydrogen selling price has been evaluated. $2.69/kg is estimated as the selling price for a central production process of 150,000 kg H₂/day and $4.27/kg for a distributed hydrogen production process at a scale of 1500 kg H₂/day. Among the parameters investigated through sensitivity analyses, ethanol feedstock cost, catalyst cost, and catalytic performance are found to play a significant role on determining the final hydrogen selling price.     

Electrophoretic deposition of Co–Me/ZnO (Me = Mn,Fe) ethanol steam reforming catalysts on stainless steel plates

A procedure for coating metal plates with powder catalysts was developed based on electrophoretic deposition (EPD), and tested to deposit three different Co-based catalysts for the steam reforming of ethanol on stainless steel plates. The catalysts contained 10 wt% Co and 1 wt% of Mn or Fe supported on ZnO, and were prepared by co-precipitation (Co–Mn/ZnO–P and Co–Fe/ZnO–P) and impregnation (Co–Mn/ZnO–I). EPD was performed suspending the powder catalysts in isopropanol, using a voltage of 100 V and a distance between electrodes of 2 cm. Polyethyleneimine (PEI, 1 g/L) was used as binder. Deposition time was fixed at 5 min, which gave a thickness of the catalyst layer from around 30–45 μm, depending on the catalyst. The activity of the catalyst plates was tested at 773 K using steam to carbon ratios of 3 and 4, under incomplete conversion conditions. All catalysts favored ethanol dehydrogenation to acetaldehyde, and steam reforming. Ethanol dehydration to ethylene and acetaldehyde cracking to methane and carbon monoxide were not favored, and the selectivity towards those products was very low.     

Performance of a miniaturized silicon reformer-PrOx-fuel cell system

A fuel cell made with silicon is operated with hydrogen supplied by a reformer and a preferential oxidation (PrOx) reactor those are also made with silicon. The performance and durability of the fuel cell is analyzed and tested, then compared with the results obtained with pure hydrogen. Three components of the system are made using silicon technologies and micro electro-mechanical system (MEMS) technology. The commercial Cu-ZnO-Al₂O₃ catalyst for the reformer and the Pt-Al₂O₃ catalyst for the PrOx reactor are coated by means of a fill-and-dry method. A conventional membrane electrode assembly composed of a 0.375 mg cm⁻² PtRu/C catalyst for the anode, a 0.4 mg cm⁻² Pt/C catalyst for the cathode, and a Nafion™ 112 membrane is introduced to the fuel cell. The reformer gives a 27 cm³ min⁻¹ gas production rate with 3177 ppm CO concentration at a 1 cm³ h⁻¹ methanol feed rate and the PrOx reactor shows almost 100% CO conversion under the experimental conditions. Fuel cells operated with this fuel-processing system produce 230 mW cm⁻² at 0.6 V, which is similar to that obtained with pure hydrogen.     

Simulation of detonation after an accidental hydrogen release in enclosed environments

An accidental hydrogen release in equipment enclosures may result in the presence of a detonable mixture in a confined environment. To assess the value of CFD techniques as a tool for damage assessment, numerical simulation of detonation was performed for two realistic scenarios. The first scenario starts with a pipe failure in an electrolyzer, resulting in a leak of 42 g of hydrogen. The second scenario deals with a failure in a reformer where 84 g of hydrogen is released. Dispersion patterns were first obtained from separate numerical simulation and detonative ignition was simulated by adding energy to a narrow region. Impulse values reached 600 Ns/m² in the electrolyzer scenario while they reached 1100 Ns/m² in the reformer. For all cases studied, the consequences are more serious in the reformer than the electrolyzer.     

Direct ethanol fuel cells using an anion exchange membrane

Direct ethanol fuel cells (DEFCs) with a PtRu anode and a Pt cathode were prepared using an anion exchange membrane (AEM) as an electrolyte instead of a cation exchange membrane (CEM), as in conventional polymer electrolyte fuel cells. The maximum power density of DEFCs significantly increased from 6 mW cm⁻² to 58 mW cm⁻² at room temperature and atmospheric pressure when the electrolyte membrane was changed from CEM to AEM. The anode and cathode polarization curves showed a decrease in the anode potential and an increase in the cathode potential for AEM-type DEFCs compared to CEM-type. This suggests that AEM-type DEFCs have superior catalytic activity toward both ethanol oxidation and oxygen reduction in alkaline medium than in acidic medium. The product species from the exhausted liquid from DEFCs operated at a constant current density were identified by enzymatic analysis. The main product was confirmed to be acetic acid in AEM-type, while both acetaldehyde and acetic acid were detected in 1:1 ratio in CEM-type. The anodic reaction of AEM-type DEFCs can be estimated to be the oxidation of ethanol to acetic acid via a four-electron process under these experimental conditions.     

The role of surface reactions on the active and selective catalyst design for bioethanol steam reforming

In order to study the role of surface reactions involved in bioethanol steam reforming mechanism, a very active and selective catalyst for hydrogen production was analysed. The highest activity was obtained at 700 °C, temperature at which the catalyst achieved an ethanol conversion of 100% and a selectivity to hydrogen close to 70%. It also exhibited a very high hydrogen production efficiency, higher than 4.5 mol H₂ per mol of EtOH fed. The catalyst was operated at a steam to carbon ratio (S/C) of 4.8, at 700 °C and atmospheric pressure. No by-products, such as ethylene or acetaldehyde were observed. In order to consider a further application in an ethanol processor, a long-term stability test was performed under the conditions previously reported. After 750 h, the catalyst still exhibited a high stability and selectivity to hydrogen production. Based on the intermediate products detected by temperature programmed desorption and reaction (TPD and TPR) experiments, a reaction pathway was proposed. Firstly, the adsorbed ethanol is dehydrogenated to acetaldehyde producing hydrogen. Secondly, the adsorbed acetaldehyde is transformed into acetone via acetic acid formation. Finally, acetone is reformed to produce hydrogen and carbon dioxide, which were the final reaction products. The promotion of such reaction sequence is the key to develop an active, selective and stable catalyst, which is the technical barrier for hydrogen production by ethanol reforming.     

Development of membrane reformer system for highly efficient hydrogen production from natural gas

A membrane reformer is composed of a steam reformer equipped with palladium-based alloy membrane modules and can perform steam reforming reaction of natural gas and hydrogen separation processes simultaneously, without shift converters and purification systems. We have developed a membrane reformer system with nominal hydrogen production capacity of 40 Nm³/h. The system has demonstrated the potential advantages of the membrane reformer: simple system configuration as benefited by single-step production of high-purity hydrogen (99.999% level), compactness, and high-energy efficiency of 70–76%. We are promoting development towards commercialization of the membrane reformer technology, focusing on further improvement of energy efficiency, proof of long-term durability and reliability, and establishment of system engineering technologies. The target of our current project is to develop a membrane reformer system that can produce 99.99% or higher-purity hydrogen from natural gas at a rate of 40 Nm³/h with hydrogen production energy efficiency of over 80%.     

Comparison of compact reformer configurations for on-board fuel processing

Two compact reformer configurations in the context of production of hydrogen in a fuel processing system for use in a Proton Exchange Membrane Fuel Cell (PEMFC) based auxiliary power unit in the 2–3 kW range are compared using computer-based modeling techniques. Hydrogen is produced via catalytic steam reforming of n-heptane, the surrogate for petroleum naphtha. Heat required for this endothermic reaction is supplied via catalytic combustion of methane, the model compound for natural gas. The combination of steam reforming and catalytic combustion is modeled for a microchannel reactor configuration in which reactions and heat transfer take place in parallel, micro-sized flow paths with wall-coated catalysts and for a cascade reactor configuration in which reactions occur in a series of adiabatic packed-beds, heat exchange in interconnecting microchannel heat exchangers being used to maintain the desired temperature. Size and efficiency of the fuel processor consisting of the reformer, hydrogen clean-up units and heat exchange peripherals are estimated for either case of using a microchannel and a cascade configuration in the reforming step. The respective sizes of fuel processors with microchannel and cascade configurations are 1.53 × 10⁻³ and 1.71 × 10⁻³ m³. The overall efficiency of the fuel processor, defined as the ratio of the lower heating value of the hydrogen produced to the lower heating value of the fuel consumed, is 68.2% with the microchannel reactor and 73.5% with the cascade reactor mainly due to 30% lower consumption of n-heptane in the latter. The cascade system also offers advanced temperature control over the reactions and ease of catalyst replacement.     

Design of linear controllers applied to an ethanol steam reformer for PEM fuel cell applications

This paper focuses on the design of a controller for a low temperature ethanol steam reformer for the production of hydrogen to feed a protonic exchange membrane (PEM) fuel cell. It describes different control structures for the reformer and treats the control structure selection of this multiple input multiple output (MIMO) system. For each considered control structure, decentralised 2 × 2 controllers with proportional integral (PI) control actions in each control loop are implemented. The tuning of the PI parameters and the performance evaluation of the different controllers are based on a non-linear simulation model. For the validation and comparison of the considered controllers, the dynamic response for different setpoint changes and initial conditions is analysed, as well as the behaviour of the controlled system against disturbances.     

Ethanol oxidation on PtRuMo/C catalysts: In situ FTIR spectroscopy and DEMS studies

The electrooxidation of ethanol on carbon supported PtRuMo nanoparticles of different Mo compositions has been studied in the temperature range of 30–70 °C. Current–time curves have shown an increase of the current density with the Mo introduction during the ethanol oxidation at 0.5 V in a whole temperature range. The incorporation of different amount of MoO_x (∼Mo⁵⁺) like species over PtRu systems produces ternary catalyst with similar structural characteristics as particle size or crystal phases, but the catalytic behavior depended on both the surface amount of Mo and on the applied potential. In situ spectroelectrochemical studies have been used to identity adsorbed reaction intermediates and products (in situ Fourier transform infrared spectroscopy, FTIR) and volatile reaction products (differential electrochemical mass spectrometry, DEMS). For all catalysts, incomplete ethanol oxidation to C2 products (acetaldehyde and acetic acid) prevails under the conditions selected in this study. The higher CO tolerance of PtRuMo/C catalysts at very low potentials (<0.3 V) results to minimum or no CO poisoning of the Pt and Ru surfaces, in contrast to the PtRu/C catalyst, which are rapidly blocked by CO. Therefore, catalyst with higher amount of Mo allows a fast “replenishment” of the active sites leading to the formation of acetaldehyde and, especially, acetic acid at potentials above 0.3 V.     

Development and evaluation of a microreactor for the reforming of diesel fuel in the kW range

The development and evaluation of a reactor based on microchannel technology for the reforming of diesel fuel is reported. The reactor itself was based on an integrated reformer/burner heat exchange reactor concept. 38 h of diesel reforming was performed at temperatures above 750 °C and at various S/C ratios, down to a minimum of 3.17, up to an electrical power equivalent of 5 kW. Over 98% total diesel conversion was observed at all times over the testing period. Variation of experimental parameters such as O/C and S/C ratios are critical for optimum operation of the reformer.     

Efficiency gain of solid oxide fuel cell systems by using anode offgas recycle - Results for a small scale propane driven unit

The transfer of high electrical efficiencies of solid oxide fuel cells (SOFC) into praxis requires appropriate system concepts. One option is the anode-offgas recycling (AOGR) approach, which is based on the integration of waste heat using the principle of a chemical heat pump.The AOGR concept allows a combined steam- and dry-reforming of hydrocarbon fuel using the fuel cell products steam and carbon dioxide. SOFC fuel gas of higher quantity and quality results. In combination with internal reuse of waste heat the system efficiency increases compared to the usual path of partial oxidation (POX).The demonstration of the AOGR concept with a 300 Wel-SOFC stack running on propane required: a combined reformer/burner-reactor operating in POX (start-up) and AOGR modus; a hotgas-injector for anode-offgas recycling to the reformer; a dynamic process model; a multi-variable process controller; full system operation for experimental proof of the efficiency gain.Experimental results proof an efficiency gain of 18 percentage points (η·POX = 23%, η·AOGR = 41%) under idealized lab conditions. Nevertheless, further improvements of injector performance, stack fuel utilization and additional reduction of reformer reformer O/C ratio and system pressure drop are required to bring this approach into self-sustaining operation.     

Thermodynamic assessment of solid oxide fuel cell system integrated with bioethanol purification unit

A solid oxide fuel cell system integrated with a distillation column (SOFC–DIS) has been proposed in this article. The integrated SOFC system consists of a distillation column, an EtOH/H₂O heater, an air heater, an anode preheater, a reformer, an SOFC stack and an afterburner. Bioethanol with 5 mol% ethanol was purified in a distillation column to obtain a desired concentration necessary for SOFC operation. The SOFC stack was operated under isothermal conditions. The heat generated from the stack and the afterburner was supplied to the reformer and three heaters. The net remaining heat from the SOFC system (Q_SOFC,Net) was then provided to the reboiler of the distillation column. The effects of fuel utilization and operating voltage on the net energy (Q_Net), which equals Q_SOFC,Net minus the distillation energy (Q_D), were examined. It was found that the system could become more energy sufficient when operating at lower fuel utilization or lower voltage but at the expense of less electricity produced. Moreover, it was found that there were some operating conditions, which yielded Q_Net of zero. At this point, the integrated system provides the maximum electrical power without requiring an additional heat source. The effects of ethanol concentration and ethanol recovery on the electrical performance at zero Q_Net for different fuel utilizations were investigated. With the appropriate operating conditions (e.g. C_EtOH = 41%, U_f = 80% and EtOH recovery = 80%), the overall electrical efficiency and power density are 33.3% (LHV) and 0.32 W cm⁻², respectively.