Pollutant emissions of burners for steam reformers for residential power supply

The cogeneration of heat and power by means of a fuel cell based CHP unit is a promising option for efficient residential power supply. For most applications natural gas is used as fuel. One main component of such a CHP unit is a fuel processor in order to generate hydrogen from the natural gas with hydrogen thermal power output of about 6 kW. Usually the steam reforming process is used for hydrogen production. In order to meet the heat demand of the endothermic steam reforming process the fuel processor is equipped with a burner, which has to work with natural gas during start up phase and mainly with the low calorific anodic off gas of the fuel cell stack during normal operation.The presented work is focused on aspects of the main pollutant emissions (carbon monoxide and nitrogen oxide) of burners integrated into the reformer. Experimental investigations of two different burners, which were developed and adapted to the steam reformer requirements, in a real fuel processor environment show, that it is possible to operate both burner concepts with high and low calorific gases with very low pollutant emissions in order to compete with emissions of current heating boilers, which are in the range of 15 mg kWh⁻¹ for CO and of 20 mg kWh⁻¹ for NO_x by adjusting suitable excess air ratios in the range of 1.2-1.4.But it is also demonstrated, that the efficiency of the fuel processor is influenced by the excess air ratio. An increase of the air ratio from 1.05 to 1.45 leads to an decrease of the efficiency from 80% to 76%. This results in a conflict of objectives between low pollutant emissions and high system efficiencies. The choice of a suitable burner concept and the definition of a suitable operation strategy can be based on the presented results. Additionally, aspects like fuel processor geometry, flame monitoring, pressure drop in the burner feed gas line as well as in the flue gas duct, investment costs and safety items have also to be considered for the burner selection.     

Investigations on the behaviour of 2 kW natural gas fuel processor

In this paper, the first experimental investigations on a pre-commercial natural gas steam reformer have been presented. The fuel processor unit contains the elements as follows: desulfurizer, steam reformer reactor, CO shift converter, CO preferential oxidation (PROX) reactor, steam generator, burner and heat exchangers.The fuel processor produces 45 Nl/min of syngas in which the hydrogen concentration is about 75 vol.% and the other chemical species are nitrogen, carbon dioxide and methane. The CO concentration is below 1 ppmv, so that this reforming system is suitable for the integration with a PEM fuel cell stack.The experimental activity has been conducted in a test station, properly designed to measure the behaviour of the fuel processor. The laboratory test facility is equipped by a National Instruments Compact DAQ real-time data acquisition and control system running Labview™ software. Several measurement instruments and controlling devices have been installed. Furthermore, a gas chromatograph is used to measure the product gas composition during the tests.The aim of this work has been to analyze the behaviour of this pre-commercial steam reforming unit during its operation cycle in different operating conditions (full and partial loads) in order to study its integration with a PEM fuel cell for developing a high efficiency microcogeneration system for residential applications.     

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

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. In a membrane reactor process, the thermal energy needed for the endothermic hydrocarbon reforming may be provided by combustion of the membrane reject gas. The energy efficiency of the overall hydrogen generation is maximized by controlling the hydrogen product yield such that the heat value of the membrane reject gas is sufficient to provide all of the heat necessary for the integrated process. Optimization of the system temperature, pressure and operating parameters such as net hydrogen recovery is necessary to realize an efficient integrated membrane reformer suitable for compact portable hydrogen generation. This paper presents results of theoretical model simulations of the integrated membrane reformer concept elucidating the effect of operating parameters on the extent of fuel conversion to hydrogen and hydrogen product yield. Model simulations indicate that the net possible hydrogen product yield is strongly influenced by the efficiency of heat recovery from the combustion of membrane reject gas and from the hot exhaust gases. When butane is used as a fuel, a net hydrogen recovery of 68% of that stoichiometrically possible may be achieved with membrane reformer operation at 600 °C (873 K) temperature and 100 psig (0.791 MPa) pressure provided 90% of available combustion and exhaust gas heat is recovered. Operation at a greater pressure or temperature provides a marginal improvement in the performance whereas operation at a significantly lower temperature or pressure will not be able to achieve the optimal hydrogen yield. Slightly higher, up to 76%, net hydrogen recovery is possible when methanol is used as a fuel due to the lower heat requirement for methanol reforming reaction, with membrane reformer operation at 600 °C (873 K) temperature and 150 psig (1.136 MPa) pressure provided 90% of available combustion and exhaust gas heat is recovered.     

Numerical simulation on non-catalytic thermal process of methane reformation for hydrogen productions

The reformer that produces hydrogen from hydrocarbon is very important part of fuel cell system. One of the promising solutions has been recently considered as direct partial oxidation of hydrocarbon by excess enthalpy flame under rich and ultra-rich condition without a platinum catalyst. In this paper, excess enthalpy flame reforming process in the perforated silicon carbide tube reformer using a two dimensional approached with GRI mechanism 1.2 was investigated. The result shows that the stable excess enthalpy flame with temperature spike was observed in a perforated silicon carbide tube reformer under condition of higher equivalence ratio than rich flammability limit of methane. It is found that hydrogen rich gases could be produced through partial oxidation at very rich equivalence ratio by formation of excess enthalpy flame. The peak flame temperature of excess enthalpy flame was higher than the adiabatic flame temperature for a free laminar flame at identical conditions and excess enthalpy flame at ultra-rich equivalence ratio could become effective way to produce hydrogen rich gases from hydrocarbon. The conversion efficiency of hydrogen and carbon monoxide by partial oxidation of excess enthalpy flame was calculated as 37.64% and 60.62%, respectively at equivalence ratio of 2.0 and inlet velocity of 80 cm/s.     

Combustion characteristics of anode off-gas on the steam reforming performance

The combination of steam reforming and HT-PEMFC has been considered as a proper set up for the efficient hydrogen production. Recycling anode off-gas is energy-saving strategy, which leads to enhance the overall efficiency of the HT-PEMFC. Thus, the recycling effect of anode off-gas on steam-reforming performance needs to be further studied. This paper, therefore, investigated that the combustion of anode off-gas recycled impacts on the steam reformer, which consists of premixed-flame burner, steam reforming and water-gas shift reactors. The temperature rising of internal catalyst was affected by lower heating value of fuels when the distance between catalyst and burner is relatively short, while by the flow rate of fuels and the steam to carbon ratio when its distance is long. The concentration of carbon monoxide was the lowest at 180 °C of LTS temperature, while NG and AOG modes showed the highest thermal efficiency at LTS temperature of 220–300 °C and 270–350 °C, respectively. The optimum condition of thermal efficiency to maximize hydrogen production was determined by steam reforming rather than water gas shift reaction. It was confirmed that the condition to obtain the highest thermal efficiency is about 650 °C of steam reforming temperature, regardless of combustion fuel and carbon monoxide reduction. The difference of hydrogen yield between upper and lower values is up to 1.5 kW as electric energy with a variation of thermal efficiency. Hydrogen yield showed the linear proportion to the thermal efficiency of steam reformer, which needs to be further increased through proper thermal management.     

Stability characteristics of non-premixed turbulent jet flames of hydrogen and syngas blends with coaxial air

The stability characteristics of attached hydrogen (H₂) and syngas (H₂/CO) turbulent jet flames with coaxial air were studied experimentally. The flame stability was investigated by varying the fuel and air stream velocities. Effects of the coaxial nozzle diameter, fuel nozzle lip thickness and syngas fuel composition are addressed in detail. The detachment stability limit of the syngas single jet flame was found to decrease with increasing amount of carbon monoxide in the fuel. For jet flames with coaxial air, the critical coaxial air velocity leading to flame detachment first increases with increasing fuel jet velocity and subsequently decreases. This non-monotonic trend appears for all syngas composition herein investigated (50/50 → 100/0% H₂/CO). OH^∗ chemiluminescence imaging was performed to qualitatively identify the mechanisms responsible for the flame detachment. For all fuel compositions, local extinction close to the burner rim is observed at lower fuel velocities (ascending stability limit), while local flame extinction downstream of the burner rim is observed at higher fuel velocities (descending stability limit). Extrema of the non-monotonic trends appear to be identical when the nozzle fuel velocity is normalized by the critical fuel velocity obtained for the single jet cases.     

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.     

Non-premixed acoustically perturbed swirling flame dynamics

An investigation into the response of non-premixed swirling flames to acoustic perturbations at various frequencies (f_p = 0-315 Hz) and swirl intensities (S = 0.09 and 0.34) is carried out. Perturbations are generated using a loudspeaker at the base of an atmospheric co-flow burner with resulting velocity oscillation amplitudes |u′/U_avg| in the 0.03-0.30 range. The dependence of flame dynamics on the relative richness of the flame is investigated by studying various constant fuel flow rate flame configurations. Flame heat release rate is quantitatively measured using a photomultiplier with a 430 nm bandpass filter for observing CH∗ chemiluminescence which is simultaneously imaged with a phase-locked CCD camera. The flame response is observed to exhibit a low-pass filter characteristic with minimal flame response beyond pulsing frequencies of 200 Hz. Flames at lower fuel flow rates are observed to remain attached to the central fuel pipe at all acoustic pulsing frequencies. PIV imaging of the associated isothermal fields show the amplification in flame aspect ratio is caused by the narrowing of the inner recirculation zone (IRZ). Good correlation is observed between the estimated flame surface area and the heat release rate signature at higher swirl intensity flame configurations. A flame response index analogous to the Rayleigh criterion in non-forced flames is used to assess the potential for a strong flame response at specific perturbation configurations and is found to be a good predictor of highly responsive modes. Phase conditioned analysis of the flame dynamics yield additional criteria in highly responsive modes to include the effective amplitude of velocity oscillations induced by the acoustic pulsing. In addition, highly responsive modes were characterized by velocity to heat release rate phase differences in the ±π/2 range. A final observed characteristic in highly responsive flames is a Strouhal number between 1 and 3.5 based on the burner co-flow annulus diameter (St = f_pU_avg/d_m). Finally, wavelet analyses of heat release rate perturbations indicate highly responsive modes are characterized by sustained low frequency oscillations which accompany the high amplitude velocity perturbations at these modes. Higher intensity low frequency heat release rate oscillations are observed for lean flame/low pulsing frequency conditions.     

A direct-flame solid oxide fuel cell (DFFC) operated on methane,propane, and butane

This paper presents an experimental study of a direct-flame type solid oxide fuel cell (DFFC). The operation principle of this system is based on the combination of a combustion flame with a solid oxide fuel cell (SOFC) in a simple, no-chamber setup. The flame front serves as fuel reformer located a few millimeters from the anode surface while at the same time providing the heat required for SOFC operation. Experiments were performed using 13-mm-diameter planar SOFCs with Ni-based anode, samaria-doped ceria electrolyte and cobaltite cathode. At the anode, a 45-mm-diameter flat-flame burner provided radially homogeneous methane/air, propane/air, and butane/air rich premixed flames. The cell performance reaches power densities of up to 120 mW cm⁻², varying systematically with flame conditions. It shows a strong dependence on cell temperature. From thermodynamic calculations, both H₂ and CO were identified as species that are available as fuel for the SOFC. The results demonstrate the potential of this system for fuel-flexible power generation using a simple setup.     

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.     

Improvement of hollow cylinders on the conversion of coal mine methane to hydrogen in packed bed burner

Coal mine methane (CMM) combustion in the porous media burner (PMB) of boiler system contributes to the simultaneous production of hydrogen and heat, and the hydrogen can be used as the main raw materials for solid oxide fuel cell (SOFC). In this study, the double-layer burners were built by filling the downstream with the hollow cylinders of different sizes and pore numbers due to the high porosity of hollow-structure units compared with the common packed bed of pellets. The distributions of temperature, species concentration and reforming efficiency were obtained on the consideration of operating condition and preheating temperature. Results shows that the reforming efficiency of the 10-6-10 mm cylinder burner was optimal in all one-pore cylinder burners with the highest concentration of 12.3% (H₂) and 8.8% (CO). As for the packed bed of 8 mm cylinders, the four-pore cylinder burner showed the highest peak temperature and maximum yields of hydrogen. With the increasing of preheating temperature, the stabilization time of the flame propagating decreased. Moreover, the peak temperature and reforming efficiency increased with the increasing of the inlet velocity and the largest efficiency of 54.2% appeared at the velocity of 18 cm/s in the 10 mm cylinder burner.     

Experimental investigation of 1 kW solid oxide fuel cell system with a natural gas reformer and an exhaust gas burner

An experimental investigation is performed to establish the optimal operating conditions of a porous media after-burner integrated with a 1 kW solid oxide fuel cell (SOFC) system fed by a natural gas reformer. The compositions of the anode off-gas and cathode off-gas emitted by the SOFC when operating with fuel utilizations in the range 0-0.6 are predicted using commercial GCTool software. The numerical results are then used to set the compositions of the anode off-gas and cathode off-gas in a series of experiments designed to clarify the effects of the fuel utilization, cathode off-gas temperature and excess air ratio on the temperature distribution within the after-burner. The experimental results show that the optimal after-burner operation is obtained when using an anode off-gas temperature of 650 °C, a cathode off-gas temperature of 390 °C, a flame barrier temperature of 700 °C, an excess air ratio of 2 and a fuel utilization of U_f = 0.6. It is shown that under these conditions, the after-burner can operate in a long-term, continuous fashion without the need for either cooling air or any additional fuel other than that provided by the anode off-gas.     

Ethanol internal steam reforming in intermediate temperature solid oxide fuel cell

This study investigates the performance of a standard Ni-YSZ anode supported cell under ethanol steam reforming operating conditions. Therefore, the fuel cell was directly operated with a steam/ethanol mixture (3 to 1 molar). Other gas mixtures were also used for comparison to check the conversion of ethanol and of reformate gases (H₂, CO) in the fuel cell. The electrochemical properties of the fuel cell fed with four different fuel compositions were characterized between 710 and 860 °C by I-V and EIS measurements at OCV and under polarization. In order to elucidate the limiting processes, impedance spectra obtained with different gas compositions were compared using the derivative of the real part of the impedance with respect of the natural logarithm of the frequency.Results show that internal steam reforming of ethanol takes place significantly on Ni-YSZ anode only above 760 °C. Comparisons of results obtained with reformate gas showed that the electrochemical cell performance is dominated by the conversion of hydrogen. The conversion of CO also occurs either directly or indirectly through the water-gas shift reaction but has a significant impact on the electrochemical performance only above 760 °C.     

Effect of hydrogen percentage and air jet Reynolds number on fuel lean flame stability of LPG-fired inverse diffusion flame with hydrogen enrichment

The flame type studied in this paper is a circumferential-fuel – jet inverse diffusion flame, and the fuel is liquefied petroleum gas enriched with hydrogen gas. Fuel lean flame stability limit regarding to the volumetric percentage of hydrogen and the air jet Reynolds number was investigated. There were three flame stable-related limits examined: local extinction limit, restore limit, and complete extinction limit. Global Energy Consumption Rate of fuel, fuel jet velocity, and overall equivalence ratio of the air/fuel mixture at the three stable-related limits were presented. Experimental results indicate that with hydrogen addition, the inverse diffusion flame can sustain burning with a lower global energy than without it. The most significant stabilization effect was obtained with 30% hydrogen addition for complete extinction limit and 30%–90% for local extinction limit. The corresponding fuel jet velocity at complete extinction limit also decreases with hydrogen addition. However, fuel jet velocities at local extinction limit and restore limit increase significantly, when hydrogen percentage is larger than 70%. Air jet Reynolds number does not show notable influence on Global Energy Consumption Rate or fuel jet velocity at the three stability limits. In addition, overall equivalence ratio, which is an important parameter of inverse diffusion flame combustion dropping dramatically with air jet Reynolds number when it is less than 2000.     

Experimental study of industrial gas turbine flames including quantification of pressure influence on flow field,fuel/air premixing and flame shape

A commercial swirl burner for industrial gas turbine combustors was equipped with an optically accessible combustion chamber and installed in a high-pressure test-rig. Several premixed natural gas/air flames at pressures between 3 and 6 bar and thermal powers of up to 1 MW were studied by using a variety of measurement techniques. These include particle image velocimetry (PIV) for the investigation of the flow field, one-dimensional laser Raman scattering for the determination of the joint probability density functions of major species concentrations, mixture fraction and temperature, planar laser induced fluorescence (PLIF) of OH for the visualization of the flame front, chemiluminescence measurements of OH^* for determining the lift-off height and size of the flame and acoustic recordings. The results give insights into important flame properties like the flow field structure, the premixing quality and the turbulence–flame interaction as well as their dependency on operating parameters like pressure, inflow velocity and equivalence ratio. The 1D Raman measurements yielded information about the gradients and variation of the mixture fraction and the quality of the fuel/air mixing, as well as the reaction progress. The OH PLIF images showed that the flame was located between the inflow of fresh gas and the recirculated combustion products. The flame front structures varied significantly with Reynolds number from wrinkled flame fronts to fragmented and strongly corrugated flame fronts. All results are combined in one database that can be used for the validation of numerical simulations.     

GC-MS determination of low hydrocarbon species (C1–C6) from a diesel partial oxidation reformer

The partial oxidation (POx) reforming of Ultra Low Sulphur-Diesel (ULSD), rapeseed methyl ester (RME) - biodiesel and Fischer–Tropsch synthetic diesel fuels (SD) were studied by using a fixed-bed reactor. The ease of reforming the three fuels was first examined at different O/C feed ratios at constant gas hourly space velocity (GHSV) of 35 k h⁻¹ over a prototype monolith catalyst (1%Rh/CeO₂–ZrO₂). The hydrocarbon species (C₁–C₆) produced in the reformer were analyzed using direct gas injection gas chromatography mass spectrometry (GC-MS). Under the same O/C ratios for 35 k h⁻¹ the fuels conversion and process efficiency was dependent on the fuel type, and followed the general trend: SD > biodiesel > ULSD. The GC-MS analysis shows that both, biodiesel and ULSD diesel produced significantly higher amounts of alkenes compared to SD fuel. Fuel with relatively high aromatics content such diesel can be efficiently reformed to syngas over the catalyst used in this study but the reformer operating range (e.g. O/C ratio and space velocity) is limited compared to paraffinic fuels such as FT-SD. At increased GHSV of 45 k h⁻¹ and O/C = 1.75, the diesel fuel conversion efficiency to syngas (H₂ and CO) was improved significantly and the formation of intermediate species such as methane, ethylene, and propylene was reduced considerably as a result of the increased peak reaction temperatures. The reduced HC species and increased H₂ concentration in the reactor product gas from the reforming of FT-SD fuel can provide significant advantages to the IC engine applications.     

Integrated fuel cell APU based on a compact steam reformer for diesel and a PEMFC

This paper presents experimental results of a diesel steam reforming fuel processor operated in conjunction with a gas cleanup module and coupled operation with a PEM fuel cell. The fuel processor was operated with two different precious-metal based reformer catalysts, using diesel surrogate with a sulfur content of less than 2 ppmw as fuel. The first reformer catalyst entails an increasing residual hydrocarbon concentration for increasing reformer fuel feed. The second reformer catalyst exhibits a significantly lower residual hydrocarbon concentration in the reformate gas.     

Stable negative edge flame formation in a counterflow burner

In nonpremixed combustion, edge flames can form as a region of flame propagation or flame recession. Forwardly propagating edge flames, as occur in lifted flames, have a local gas velocity at the flame edge that is from unburned partially premixed fuel and air into the flame. These flames represent an ignition process, and permit the flame itself to either stabilize against an incoming gas stream or propagate into unburned fuel and air. Negative edge flames represent the opposite case of a local gas velocity from burned products through the flame edge. The negative edge flame represents a local extinction process, and occurs, for example, during vortex-induced extinction of a nonpremixed flame sheet. A technique for generating steady negative edge flames in a standard counterflow burner is presented, which permits detailed examination of their properties. A coannular counterflow burner is used to create a strain gradient that quenches a central diffusion flame. Unlike previous research on strain-induced flame edges, the axisymmetric flow field ensures gas flow from products through the edge. Measurements of the edge flame's sensitivity to global strain rates and fuel mixtures are presented, along with measurements of the edge flame structure using OH fluorescence and CH emission imaging.     

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.     

Development and CFD analysis for determining the optimal operating conditions of 250 kg/day hydrogen generation for an on-site hydrogen refueling station (HRS) using steam methane reforming

The objective of this study to develop and undertake a comprehensive CFD analysis of an effective state-of-the-art 250 kg/day hydrogen generation unit for an on-site hydrogen refueling station (HRS), an essential part of the infrastructure required for fuel cell vehicles and various aspects of hydrogen mobility. This design consists of twelve reforming tubes and one newly designed metal fiber burner to ensure superior emission standards and performance. Experimental and computational modeling steps are conducted to investigate the effects of various operating conditions, the excess air ratio (EAR) at the burner, the gas hourly space velocity (GHSV), the process gas inlet temperature, and the operating pressure on the hydrogen production rate and thermal efficiency. The results indicate that the performance of the steam methane reforming reactor increased significantly by improving the combustion characteristics and preventing local peak temperatures along the reforming tube. It is shown that EAR should be chosen appropriately to maximize the hydrogen production rate and lifetime operation of the reformer tube. It is found that high inlet process gas temperatures and low operating pressure are beneficial, but these parameters have to be chosen carefully to ensure proper efficiency. Also, a high GHSV shortens the residence time and provides unfavorable heat transfer in the bed, leading to decreased conversion efficiency. Thus, a moderate GHSV should be used. It is shown that heat transfer is an essential factor for obtaining increased hydrogen production. This study addresses the pressing need for the HRS to adopt such a compact system, whose processes can ensure greater hydrogen production rates as well as better durability, reliability, and convenience.