Heat flux analysis of a cylindrical steam reformer by a modified Nusselt number

A numerical method is used to investigate a steam reformer. The reactor is assumed as a porous medium, because it is filled with catalysts of a packed-bed type, and a pseudo-homogeneous model is incorporated for a chemical reaction model. The steam reforming (SR) reaction, water–gas shift (WGS) reaction, and direct steam reforming (DSR) reaction are assumed to be dominant reactions in the steam reformer. The difference in temperature between the inside and outside of the reactor is a driving force in heat transfer, and is affected by the amount of heat adsorption by an endothermic reaction. A modified Nusselt number (Nu_M) can represent the heat transfer rate of the endothermic reactor, and thus Nu_M can be used to describe the performance of the steam reformer. The SR reaction rate is sufficiently activated when Nu_M around the inlet region is greater than 10, and fuel conversion exceeds 0.9 when the difference in Nu_M value between the inlet area and outlet area is greater than 5. The correlation between fuel conversion and operating conditions has also been studied by using Nu_M.     

Water-gas shift reactor for fuel cell systems: Stable operation for 5000 hours

The water-gas shift reactor in the fuel processing unit of a fuel cell system has the vital function of reducing the concentration of CO in the reforming reactor's product gas to values of between 1.0 and 1.5 vol% in order to protect the anodic catalyst from becoming irreversibly poisoned. This paper presents Jülich's recent development in this field, specifically the WGS 6 in the 5 kW_e class. The WGS 6 is characterized by a fundamentally new concept for arranging high temperature and low temperature shift stages. Both stages are now coaxially integrated in one joint casing to provide higher values for the power density and specific power, whereas in earlier reactor generations, these stages are arranged in two separate, parallel housings. In addition, this contribution presents results from a long-term experiment for 5000 h on stream with WGS 6 and discusses the temporal trends of the product gas composition and reactor temperatures across this timespan. For this experiment, the inlet gas stream is produced by an autothermal reformer, which is installed upstream of the WGS 6.     

Hydrogen production by reforming of liquid hydrocarbons in a membrane reactor for portable power generation—Experimental studies

One of the most promising technologies for lightweight, compact, portable power generation is proton exchange membrane (PEM) fuel cells. PEM fuel cells, however, require a source of pure hydrogen. Steam reforming of hydrocarbons in an integrated membrane reactor has potential to provide pure hydrogen in a compact system. Continuous separation of product hydrogen from the reforming gas mixture is expected to increase the yield of hydrogen significantly as predicted by model simulations. In the laboratory-scale experimental studies reported here steam reforming of liquid hydrocarbon fuels, butane, methanol and Clearlite^® was conducted to produce pure hydrogen in a single step membrane reformer using commercially available Pd–Ag foil membranes and reforming/WGS catalysts. All of the experimental results demonstrated increase in hydrocarbon conversion due to hydrogen separation when compared with the hydrocarbon conversion without any hydrogen separation. Increase in hydrogen recovery was also shown to result in corresponding increase in hydrocarbon conversion in these studies demonstrating the basic concept. The experiments also provided insight into the effect of individual variables such as pressure, temperature, gas space velocity, and steam to carbon ratio. Steam reforming of butane was found to be limited by reaction kinetics for the experimental conditions used: catalysts used, average gas space velocity, and the reactor characteristics of surface area to volume ratio. Steam reforming of methanol in the presence of only WGS catalyst on the other hand indicated that the membrane reactor performance was limited by membrane permeation, especially at lower temperatures and lower feed pressures due to slower reconstitution of CO and H₂ into methane thus maintaining high hydrogen partial pressures in the reacting gas mixture. The limited amount of data collected with steam reforming of Clearlite^® indicated very good match between theoretical predictions and experimental results indicating that the underlying assumption of the simple model of conversion of hydrocarbons to CO and H₂ followed by equilibrium reconstitution to methane appears to be reasonable one.     

Fast starting fuel processor for automotive fuel cell systems

A fuel processor was constructed which incorporated two burners with direct steam generation by water injection into the burner exhaust. These burners with direct water vaporization enabled rapid fuel processor start-up for automotive fuel cell systems. The fuel processor consisted of a conventional chain of reactors: auto-thermal reformer (ATR), water gas shift (WGS) reactor and preferential oxidation (PrOx) reactor. The criticality of steam to the fuel reforming process was illustrated. By utilizing direct vaporization of water, and hydrogen for catalyst light-off, excellent start performance was obtained with a start time of 20 s to 30% power and 140 s to full power.     

Analysis of reformer furnace tubes for hydrogen production using radiative zonal model

Reformer tubes are commonly used in furnaces to produce hydrogen and synthesis gas in the refining, petrochemical and fertilizer industries. An optimum arrangement and dimensions of the reformer tubes could be obtained from a mathematical modeling. In the present study, a comparison of different tube sizes is presented based on the well-established radiation zonal analysis in the furnace beside mass, momentum, and energy balance in the reactor tubes. For the practical case studies, three Cr–Ni alloy stainless steel tubes were selected to analyze different tube dimensions including diameter, thickness and tube spacing with the same inlet process feed, fuel consumption and catalyst weight. It is shown that for three industrial tube materials a 20% increase in the tube diameter causes a 20% increase in the tube thickness, 10–20% decrease in furnace length (according to the design procedure) and 3–6% decrease in methane conversion. The results of another analysis show that a 5–9% decrease in the fuel consumption is followed by a 20% decrease in the tube diameter for the same amount of hydrogen production for three cases. Moreover, the three tube materials were compared in accordance to the fuel consumption. In all cases minimum tube thickness is desirable.     

Mini CHP based on the electrochemical generator and impeded fluidized bed reactor for methane steam reforming

The paper presents a configuration of mini CHP with the methane reformer and planar solid oxide fuel cell (SOFC) stacks. This mini CHP may produce electricity and superheated steam as well as preheat air and methane for the reformer along with cathode air used in the SOFC stack as an oxidant. Moreover, the mathematical model for this power plant has been created. The thermochemical reactor with impeded fluidized bed for autothermal steam reforming of methane (reformer) considered as the basis for the synthesis gas (syngas) production to fuel SOFC stacks has been studied experimentally as well. A fraction of conversion products has been oxidized by the air fed to the upper region of the impeded fluidized bed in order to carry out the endothermic methane steam reforming in a 1:3 ratio as well as to preheat products of these reactions. Studies have shown that syngas containing 55% of hydrogen could be produced by this reactor. Basic dimensions of the reactor as well as flow rates of air, water and methane for the conversion of methane have been adjusted through mathematical modelling.The paper provides heat balances for the reformer, SOFC stack and waste heat boiler (WHB) intended for generating superheated water steam along with preheating air and methane for the reformer as well as the preheated cathode air. The balances have formed the basis for calculating the following values: the useful product fraction in the reformer; fraction of hydrogen oxidized at SOFC anode; gross electric efficiency; anode temperature; exothermic effect of syngas hydrogen oxidation by air oxygen; excess entropy along with the Gibbs free energy change at standard conditions; electromotive force (EMF) of the fuel cell; specific flow rate of the equivalent fuel for producing electric and heat energy. Calculations have shown that the temperature of hydrogen oxidation products at SOFC anode is 850 °C; gross electric efficiency is 61.0%; EMF of one fuel cell is 0.985 V; fraction of hydrogen oxidized at SOFC anode is 64.6%; specific flow rate of the equivalent fuel for producing electric energy is 0.16 kg of eq.f./(kW·h) while that for heat generation amounts to 44.7 kg of eq.f./(GJ). All specific parameters are in agreement with the results of other studies.     

Thermal resistance effect on methanol-steam reforming performance in micro-scale reformers

We numerically investigate hydrogen production based on methanol-steam reforming (MSR) using a micro-scale cylindrical packed bed reformer. The reformer wall is included in the physical model. The heat required for the reforming reaction is supplied either internally using a heating rod placed along the center of the reformer or externally by a heat flux applied at the reformer outer wall. Our results show that the thermal resistance from the heat source to the reformer environment plays an important role in the reformer performance. This thermal resistance depends on the reformer geometry, wall material and heat transfer coefficients inside the catalyst bed and outside the reformer. Based on our numerical results, it is suggested that better methanol conversion and hydrogen yield can be obtained using reformer wall material with low thermal conductivity and thin thickness. For both internal and external heating under the same heat rate supply, no significant difference in reformer performance was found.A water gas shift (WGS) reaction model was included in the present numerical model. In the reformer low-temperature zone the forward WGS reaction was clearly demonstrated, resulting in a decrease in carbon monoxide (CO) selectivity. In the high temperature zone the backward WGS reaction was also clearly demonstrated in which CO selectivity increases with the increase in temperature. For both internal and external heating under the same heat rate supply, our results indicated that CO selectivity is about thirty times lower when the WGS reaction is neglected.     

Modeling and simulation of water-gas shift in a heat exchange integrated microchannel converter

The aim of this study is to analyze the operation of a heat exchange integrated, Pt-CeO₂/Al₂O₃ washcoated microchannel water-gas shift (WGS) reactor under fuel processing conditions by mathematical modeling techniques. In this context, operation of a single microchannel is modeled, whose outcomes are compared with experimental data obtained from the literature. Simulations show good agreement with the experimental data, with an error below 4%. Upon its validation, single channel model is used to simulate a heat exchange integrated microchannel reactor, which involves periodically located groups of reaction and air-fed cooling channels. The integrated reactor is modeled by 2D Navier-Stokes equations together with reactive transport of heat and mass. Incorporation of heat exchange function minimizes the impact of thermodynamic limitations on WGS by precise regulation of reaction temperature and gives 77.6% CO conversion, which is 67.4% in the absence of cooling. Improvement in conversion from 69.2% to 77.6% is observed upon increasing feed temperature of the reaction stream from 565 to 595 K, above which the reaction is controlled by equilibrium. Coolant feed temperature, however, changes conversion only by <1%. Isothermal conditions are obtained upon feeding reaction and coolant channels at 595 K and 587 K, respectively. Changes in the thickness and material of the wall between the channels give limited deviations in conversion. An integrated reactor with 2.37 L volume is sufficient for supplying H₂ necessary to drive a 1 kW PEMFC unit.     

Modeling and optimization of a 1 kWe HT-PEMFC-based micro-CHP residential system

A high temperature-proton exchange membrane (HT-PEMFC)-based micro-combined-heat-and-power (CHP) residential system is designed and optimized, using a genetic algorithm (GA) optimization strategy. The proposed system consists of a fuel cell stack, steam methane reformer (SMR) reactor, water gas shift (WGS) reactor, heat exchangers, and other balance-of-plant (BOP) components. The objective function of the single-objective optimization strategy is the net electrical efficiency of the micro-CHP system. The implemented optimization procedure attempts to maximize the objective function by variation of nine decision variables. The value of the objective function for the optimum design configuration is significantly higher than the initial one, with a 20.7% increase.     

Thermally integrated fuel processor design for fuel cell applications

Effective thermal integration could enable the use of compact fuel processors with PEM fuel cell-based power systems. These systems have potential for deployment in distributed, stationary electricity generation using natural gas. This paper describes a concept wherein the latent heat of vaporization of H₂O is used to control the axial temperature gradient of a fuel processor consisting of an autothermal reformer (ATR) with water gas shift (WGS) and preferential oxidation (PROX) reactors to manage the CO exhaust concentration. A prototype was experimentally evaluated using methane fuel over a range of external heat addition and thermal inputs. The experiments confirmed that the axial temperature profile of the fuel processor can be controlled by managing only the vapor fraction of the premixed reactant stream. The optimal temperature profile is shown to result in high thermal efficiency and a CO concentration less than 40 ppm at the exit of the PROX reactor.     

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.     

A complete miniaturized microstructured methanol fuel processor/fuel cell system for low power applications

A complete miniaturized methanol fuel processor/fuel cell system was developed and put into operation as compact hydrogen supplier for low power application. The whole system consisting of a micro-structured evaporator, a micro-structured reformer and two stages of preferential oxidation of CO (PROX) reactor, micro-structured catalytic burner, and fuel cell was operated to evaluate the performance of the whole production line from methanol to electricity. The performance of micro methanol steam reformer and PROX reactor was systematically investigated. The effect of reaction temperature, steam to carbon ratio, and contact time on the methanol steam reformer performance is presented in terms of catalytic activity, selectivity, and reformate yield. The performance of PROX reactor fed with the reformate produced by the reformer reactor was evaluated by the variation of reaction temperature and oxygen to CO ratio. The results demonstrate that micro-structured device may be an attractive power source candidate for low power application.     

Noble metal water gas shift catalysis: Kinetics study and reactor design

Based on the water gas shift (WGS) catalytic mechanism on precious metal catalyst, a Langmuir–Hinshelwood (LH) kinetics model was derived for the operating conditions of syngas from natural gas reforming at near-ambient pressure. A power law kinetics model was also presented for comparative purpose. These two kinetics models were integrated in a dynamic distributed reactor model for design of full-scale WGS reactors for a natural gas fuel processing system. Modeling results indicated that the LH kinetics model gives predictions of reactor performance closer to the experimental data. Using the LH kinetics model, optimization of operating conditions for the high-temperature shift (HTS) and low-temperature shift (LTS) reactors was also attempted.     

An experimental study on the reaction characteristics of a coupled reactor with a catalytic combustor and a steam reformer for SOFC systems

Steam reforming performance in a coupled reactor that consists of a steam reformer and a catalytic combustor is experimentally investigated in this study. Endothermic steam reforming can occur through the absorption of heat from the catalytic combustion of the anode offgas in a heat-exchanging coupled reactor. The reaction characteristics were observed by varying parameters such as the inlet temperature of the catalytic combustor, the excess air ratio for the catalytic combustion, the fuel utilization rate in the fuel cells, and the steam-to-carbon ratio in the steam reformer. The reactor temperature and reformate composition were measured to analyze the performance of the reactor. The results show the potential applicability and design technologies of the coupled reactor for the fuel processing of high temperature fuel cells using an external reformer.     

Modeling and Analysis of a Hydrogen Reformer for Fuel Cell Applications

Fuel cells that utilize hydrogen and oxygen to produce energy are promising power sources. However, there are operational difficulties in storing hydrogen. One way to alleviate this problem is to generate hydrogen in situ from a liquid fuel via steam reforming. In this paper, an ethanol reformer was modeled as a tubular non-isothermal, non-isobaric packed-bed reactor with an annular heat transfer jacket, operating at unsteady state. A suitable heat transfer jacket was designed that provides heat to the reformer by combustion of ethanol. The partial differential equations of the reformer model were solved numerically and model predictions of hydrogen generation were shown to be in good agreement with experimental data available in the literature for a laboratory-scale reformer. A commercial-scale reformer was designed using this high-fidelity model that can produce sufficient hydrogen to generate up to 5 kW of power when used in conjunction with a Ballard Mark V fuel-cell stack. Experimental data from the dynamic power consumption in a 3-bedroom house were used to validate the size of the reformer as well as a back-up battery that supplies power when the reformer is unable to meet the power demand.     

Technical design and economic evaluation of a PEM fuel cell system

The main objectives of this study are to develop the economic models and their characterization trends for the common unit processes and utilities in the fuel cell system. In this study, a proton electrolyte membrane fuel cell (PEMFC) system is taken as a case study. The overall system consists of five major units, namely auto-thermal reformer (ATR), water gas shift reactor (WGS), membrane, pressure swing adsorber (PSA) and fuel cell stack. Besides that, the process utilities like compressor, heat exchanger, water adsorber are also included in the system. From the result, it is determined that the specific cost of a PEM fuel cell stack is about US$ 500 per kW, while the specific manufacturing and capital investment costs are in the range of US$ 1200 per kW and US$ 2900 per kW, respectively. Besides that the electricity cost is calculated as US$ 0.04 kWh. The results also prove that the cost of PEM fuel cell system is comparable with other conventional internal engine.     

Experimental and theoretical analysis of a natural gas fuel processor

In this study, a natural gas fuel processor was experimentally and theoretically investigated. The constructed 2.0 kWth fuel processor is suitable for a residential-scale high temperature proton exchange membrane fuel cell. The system consists of an autothermal reformer; gas clean-up units, namely high and low-temperature water-gas shift reactors; and utilities including feeding unit, burner, evaporator and heat exchangers. Commercial monolith catalysts were used in the reactors. The simulation was carried out by using ASPEN HYSYS program. A validated kinetic model and adiabatic equilibrium model were both presented and compared with experimental data. The nominal operating conditions which were determined by the kinetic model were the steam-to-carbon ratio of 3.0, the oxygen-to-carbon ratio of 0.5 and the inlet temperatures of 450 °C for autothermal reformer, 400 °C for high-temperature water-gas shift reactor and 310 °C for low-temperature water-gas shift reactor. Experimental results at the nominal condition showed that the performance criteria of the hydrogen yield, the fuel conversion and the efficiency were 2.53, 93.5% and 82.3% (higher heating value-HHV), respectively. The validated kinetic model was further used for the determination of 2–10kWthermal fuel processor efficiency which was increasing linearly up-to 86.3% (HHV).     

Analysis of design variables for water-gas-shift reactors by model-based optimization

This work analyzes the water-gas-shift reactor design as component of the CO clean-up system of the ethanol processor for H₂ production applied to PEM fuel cells. The WGS reactor constitutes the element of greater volume of the processor motivating its optimization. A model-based reactor optimization for different reactor configurations permits to obtain both designs for reducing volumes and optimal operating conditions. The heterogeneous model used allows computing the optimal reactor length and diameter, and the optimal catalyst particle diameter. The model computes the constraints required for catalyst, such as maximum and minimum operation temperature. The volume is sensitive to the CO outlet concentration. According to the required CO conversion it is necessary more than one reactor unit for the case study analyzed. When considering the insulating material, there exists an optimal thickness that affects the final volume and the design variables. These results are useful for estimating the minimum and relative sizes that allows conventional reactor technology.     

Methanol reformer integrated phosphoric acid fuel cell (PAFC) based compact plant for field deployment

Naval Material Research Laboratory (NMRL), based on the firm confidence of her core competence on material development, started an ambitious program on development of fuel cells for various Defense and non-Defense application in early nineties. The primary emphasis of this program is to develop phosphoric acid fuel cell (PAFC) based power plants integrated with hydrogen generators along with other accessories. In the process of development, it is understood that online generation of hydrogen from a liquid fuel is the key to success. Methanol, a liquid fuel, can be reformed easily with few side products and the resultant hydrogen rich reformer gas can be directly fed to a PAFC. Such configuration keeps the basic system simple and free of complicated filters and instrumentation.NMRL has developed a series of catalytic burners with high efficiency as the primary heat transfer source from the hot catalytic surface is based on conduction rather than convection as is done normally. Vaporizer is a coiled arrangement and reformer is hollow sections filled with Cu/Al₂O₃/ZnO catalyst, and the same is integrated with catalytic burners. Such arrangement is modular in nature and each reformer has hydrogen generation capacity of 90 lpm and start-up time is around half an hour. Modular design of reformer reactor allow them to used in different capacity plants such as a 2 kW plant configured with a reformer reactor with two vaporizer and 15 kW plant configured with seven nos. of reformer reactors and seven no. of vaporizer. The waste heat of the fuel cell and the same from the reformer burner flue is used to meet most of the reformer heat load. The catalytic burner of the reformer burns both waste hydrogen and methanol with very little excess air. PAFC being tolerant to CO (up to 1%) can be directly operated with the hydrogen rich reformer gas and the lean gas from the fuel cell is burnt into the reformer system.The raw DC output power is converted into either 100 VDC or 220 V single phase, 50 Hz sinusoidal AC power through appropriate power electronics. These configurations give overall efficiency of the plant to around 35-40 % based on LHV of Hydrogen. A battery bank is also incorporated to cater for the plant start-up and other temporary auxiliary power which get charged from the fuel cell output. Such configuration lead to the development of methanol reformer integrated PAFC based power plants of capacity ranging from 2 kW to 15 kW. The system is designed for continuous power production in the field. These plants are suitable for remote area, distributed power generation and application such as battery charging, domestic load etc.