Study on a compact methanol reformer for a miniature fuel cell

A compact methanol reformer for hydrogen production has been successfully fabricated, which integrated one reforming chamber, one water gas shift reaction chamber, two preheating chambers and two combustion chambers. It can be started-up at room temperature by the combustion of liquid methanol in the combustion chamber within 7 min without any external heating. The cold start response of the methanol reformer has been investigated using different parameters including methanol and air supply rate, and the experiments revealed that the optimum methanol and air flow rate were 0.55 mL/min and 3 L/min respectively. The results indicated that this methanol reformer can provide a high concentration of hydrogen (more than 73%) and the system efficiency is always maintained above 74%. It is further demonstrated in more than 1600 h continuous performance that the reformer could be operated autothermally and exhibited good test stability.     

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.     

Control and experimental characterization of a methanol reformer for a 350 W high temperature polymer electrolyte membrane fuel cell system

This work presents a control strategy for controlling the methanol reformer temperature of a 350 W high temperature polymer electrolyte membrane fuel cell system, by using a cascade control structure for reliable system operation. The primary states affecting the methanol catalyst bed temperature is the water and methanol mixture fuel flow and the burner fuel/air ratio and combined flow. An experimental setup is presented capable of testing the methanol reformer used in the Serenergy H3 350 Mobile Battery Charger; a high temperature polymer electrolyte membrane (HTPEM) fuel cell system. The experimental system consists of a fuel evaporator utilizing the high temperature waste gas from the cathode air cooled 45 cell HTPEM fuel cell stack. The fuel cells used are BASF P1000 MEAs which use phosphoric acid doped polybenzimidazole membranes. The resulting reformate gas output of the reformer system is shown at different reformer temperatures and fuel flows, using the implemented reformer control strategy. The gas quality of the output reformate gas is of HTPEM grade quality, and sufficient for supporting efficient and reliable HTPEM fuel cell operation with CO concentrations of around 1% at the nominal reformer operating temperatures. As expected increasing temperatures also increase the dry gas CO content of the reformate gas and decreases the methanol slip. The hydrogen content of the gas was measured at around 73% with 25% CO₂.     

Design of a methanol reformer for on-board production of hydrogen as fuel for a 3 kW High-Temperature Proton Exchange Membrane Fuel Cell power system

The method of Computational Fluid Dynamics is used to predict the process parameters and select the optimum operating regime of a methanol reformer for on-board production of hydrogen as fuel for a 3 kW High-Temperature Proton Exchange Membrane Fuel Cell power system. The analysis uses a three reactions kinetics model for methanol steam reforming, water gas shift and methanol decomposition reactions on Cu/ZnO/Al₂O₃ catalyst. Numerical simulations are performed at single channel level for a range of reformer operating temperatures and values of the molar flow rate of methanol per weight of catalyst at the reformer inlet. Two operating regimes of the fuel processor are selected which offer high methanol conversion rate and high hydrogen production while simultaneously result in a small reformer size and a reformate gas composition that can be tolerated by phosphoric acid-doped high temperature membrane electrode assemblies for proton exchange membrane fuel cells. Based on the results of the numerical simulations, the reactor is sized, and its design is optimized.     

Concept design of a novel reformer producing hydrogen for internal combustion engines using fuel decomposition method: Performance evaluation of coated monolith suitable for on-board applications

Hydrogen addition effectively reduces the fuel consumption of spark ignition engines. We propose a new on-board reformer that produces hydrogen at high concentrations and enables multi-mode operations. For the proposed reformer, we employ a catalytic fuel decomposition reaction via a commercial NiO–CaAl₂O₄ catalyst. We explore the physical and chemical aspects of the reforming process using a fixed bed micro-reactor operating at temperatures of 550–700 °C. During reduction, methane is decomposed to form hydrogen and carbon. Carbon formation is critical to hydrogen production, and free space for carbon growth is essential at low temperatures (≤600 °C). We define a new accumulated conversion ratio that quantitatively measures highly transient catalytic decomposition. The free space of the coated monolith clearly aided low-temperature decomposition with negligible pressure drop. The coated substrate is therefore suitable for on-board applications considering that our reformer concept also utilizes the catalytic fuel decomposition reaction.     

The performance evaluation of an industrial membrane reformer with catalyst-deactivation for a domestic methanol production plant

Methane reforming is the most important and economical process for hydrogen and syngas generation. In this work, the dynamic simulation of methane steam reforming in an industrial membrane reformer for synthesis gas production is developed. A novel deactivation model for commercial Ni-based catalysts is proposed and the monthly collected data from an existing reformer in a domestic methanol plant is used to optimize the model parameters. The plant data is also employed to check the model accuracy. It was observed that the membrane reformer could compensate for the catalyst deactivating effect.In order to assure the long membrane lifetime and decrease the unit price, the membrane reformer with 5 μm thick Pd on stainless steel supports is modeled at the temperature below the maximum operating temperature of Pd based membranes (around 600 °C). The dynamic modeling showed that the methane conversion of 76% could be achieved at a moderate temperature of 600 °C for an industrial membrane reformer. The cost-effective generation of syngas with an appropriate H₂/CO ratio of 2.6 could be obtained by membrane reformer. This is while the conventional reformer exhibits a maximum conversation of 64 at 1200 °C challenging due to its high syngas ratio (3.7). On the other hand, the pure hydrogen from membrane reformer can supply part of the ammonia reactor feed in an adjacent ammonia plant.     

Numerical and experimental study on hydrogen production via dimethyl ether steam reforming

This work presents the characteristics of catalytic dimethyl ether (DME)/steam reforming based on a Cu–Zn/γ-Al₂O₃ catalyst for hydrogen production. A kinetic model for a reformer that operates at low temperature (200 °C–500 °C) is simulated using COMSOL 5.2 software. Experimental verification is performed to examine the critical parameters for the reforming process. During the experiment, superior Cu–Zn/γ-Al₂O₃catalysts are manufactured using the sol-gel method, and ceramic honeycombs coated with this catalyst (1.77 g on each honeycomb, five honeycombs in the reactor) are utilized as catalyst bed in the reformer to enhance performance. The steam, DME mass ratio is stabilized at 3:1 using a mass flow controller (MFC) and a generator. The hydrogen production rate can be significantly affected depending on the reactant's mass flow rate and temperature. And the maximum hydrogen yield can reach 90% at 400 °C. Maximum 8% error for the hydrogen yield is achieved between modeling and experimental results. These experiments can be further explored for directly feeding hydrogen to proton exchange membrane fuel cell (PEMFC) under the load variations.     

Low temperature operation and influence parameters on the cold start ability of portable PEMFCs

The start up behaviour of PEM fuel cells below 0 °C is one of the most challenging tasks to be solved before commercialisation. The automotive industry started to develop solutions to reduce the start up time of fuel cell systems in the middle of the nineties. The strategies varied from catalytic combustion of hydrogen on the electrode catalyst to fuel starvation or external stack heating via cooling loops to increase the stack temperature.Beside the automotive sector the cold start ability is as well important for portable PEMFC applications for outdoor use. But here the cold start issue is even more complicated, as the fuel cell system should be operated as passive as possible.Below 0 °C freezing of water inside the PEMFC could form ice layers in the electrode and in the gas diffusion layer. Therefore the cell reaction is limited or even inhibited. Product water during the start up builds additional barriers and leads to a strong decay of the output power at isothermal operating conditions.In order to find out which operational and hardware parameters affect this decay, potentiostatic experiments on single cells were performed at isothermal conditions. These experiments comprise investigations of the influence of membrane thickness and different GDL types as well as the effect of gas flow rates and humidification levels of the membrane. As pre stage to physical based models, empirical based prediction models are used to gain a better understanding of the main influence parameters during cold start. The results are analysed using the statistical software Cornerstone 4.0.The experience of single cell investigations are compared to start up behaviour of portable fuel cell stacks which are operated in a climate chamber at different ambient temperatures below 0 °C. Additional flow sharing problems in the fuel cell stack could be seen during cold start up experiments.     

Process simulation of hydrogen production by steam reforming of diluted bioethanol solutions: Effect of operating parameters on electrical and thermal cogeneration by using fuel cells

The possibility to exploit diluted bioethanol streams is discussed for hydrogen production by steam reforming. An integrated unit constituted by a steam reformer, a hydrogen purification section with high- and low-temperature water gas shift, a methanator reactor and a fuel cell were simulated to achieve residential size cogeneration of 5 kW electrical power + 5 kW thermal power as target output.Process simulation allowed to investigate the effect of the reformer temperature, of bioethanol concentration and of catalyst loading on the temperature and concentration profiles in the steam reformer. The net power output was also calculated on the basis of 27 different operating conditions.P_electrical output ranging from 3.3 to 6.0 kW were obtained, whereas the total heat output P_{thermal, total} ranged from 3.9 to 7.2 kW. The highest overall energy output corresponded to P_electrical = 4.8 kW, P_{Thermal, FC} = 3.1 kW, P_{heat recovery} = 4.1 kW, for a total 12 kW energy output. This was achieved by feeding a mixture with water/ethanol ratio = 11 (mol/mol), irrespectively of the catalyst mass, and setting the ref split temperature so to have an average temperature of 635 °C in the ESR reactor.     

Biodiesel synthesis from Hevea brasiliensis oil employing carbon supported heterogeneous catalyst: Optimization by Taguchi method

The present work illustrates the parametric effects on biodiesel production from Hevea brasiliensis oil (HBO) using flamboyant pods derived carbonaceous heterogeneous catalyst. Activated carbon (AC) was prepared maintaining 500 °C for 1 h and steam activated at optimised values of activation time 1.5 h and temperature 350 °C. Carbonaceous support was impregnated with KOH at different AC/KOH ratios. The transesterification process was optimized and significant parameters affecting the biodiesel yield was identified by Taguchi method considering four parameters viz. reaction time, reaction temperature, methanol to oil ratio and catalyst loading. The physicochemical properties of Hevea brasiliensis methyl ester (HBME) were examined experimentally at optimised condition and found to meet the global American standards for testing and materials (ASTM). The optimum condition observed to yield 89.81% of biodiesel were: reaction time 60 min, reaction temperature 55 °C, catalyst loading 3.5wt% and methanol to oil ratio 15:1. Contribution factor revealed that among four parameters considered, catalyst loading and methanol to oil ratio have more prominent effect on biodiesel yield. The cost for preparing carbonaceous catalyst support was estimated and observed to be fairly impressive. Thus, Hevea brasiliensis oil (HBO) could be considered as suitable feedstock and flamboyant pods derived carbon as effective catalyst for production of biodiesel.     

Investigation of synthesized Fe2O3 and CuO–Fe2O3 for pure hydrogen production by chemical-loop reforming of methanol in a micro-channel reactor

Production of pure hydrogen from methanol was investigated by the chemical looping method in the presence of 0.1CuO–Fe2O3 and Fe2O3 at 350 °C in a micro-channel reactor. The x-ray diffraction and atomic absorption spectroscopy analysis confirmed the formation phases and the values of Fe2O3 and CuO.Considering the formation of coke due to methanol conversion reactions and as a result, the production of CO together with H2, the time of the reduction step (2 hours-11 min) has been controlled to minimize coke deposition. The results show that coke deposition was prevented by optimizing the reduction time to 11 min for both samples and the pure H2 flow was generated for fuel cell applications, which was 231.1% higher for the 0.1CuO–Fe2O3. Although the results show that improving the Cu content and the reduction temperature increases the reduction degree of the catalyst and yield of H2, but coke deposition cannot be prevented.     

Development of multi-layered microreactor with methanol reformer for small PEMFC

A glass multi-layered microreactor with a methanol reformer that could provide power to portable electronic devices was developed to supply hydrogen to a small proton exchange membrane fuel cell (PEMFC). The microreactor consisted of four units: a methanol reformer with a catalytic combustor, a CO remover and two vaporizers. The dimensions of the microreactor were estimated by thermal simulation in order to achieve the required reaction temperature of each unit.In this study, the glass multi-layered microreactor was produced using anodic bonding. The number of glass pieces of which the microreactor was composed was 13. The experimental temperature of each unit, as well as the heat loss, for a methanol reformer of temperatures at 280 °C was measured and compared with the results from thermal simulation.     

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

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

Micro methanol reformer combined with a catalytic combustor for a PEM fuel cell

This paper presents the development of a micro methanol reformer for portable fuel cell applications. The micro reformer consists of a methanol steam reforming reactor, catalytic combustor, and heat exchanger in-between. Cu/ZnO was selected as a catalyst for a methanol steam reforming and Pt for a catalytic combustion of hydrogen with air. Porous ceramic material was used as a catalyst support due to the large surface area and thermal stability. Photosensitive glass wafer was selected as a structural material because of its thermal and chemical stabilities. Performance of the reformer was measured at various test conditions and the results showed a good agreement with the three-dimensional analysis of the reacting flow. Considering the energy balance of the reformer/combustor model, the off-gas of fuel cell can be recycled as a feed of the combustor. The catalytic combustor generated the sufficient amount of heat to sustain the steam reforming of methanol. The conversion of methanol was 95.7% and the hydrogen flow of 53.7 ml/min was produced including 1.24% carbon monoxide. The generated hydrogen was the sufficient amount to operate 4.5 W polymer electrolyte membrane fuel cells.     

Effect of fuel blend composition on hydrogen yield in co-gasification of coal and non-woody biomass

In this study, torrefaction of sunflower seed cake and hydrogen production from torrefied sunflower seed cake via steam gasification were investigated. Torrefaction experiments were performed at 250, 300 and 350 °C for different times (10–30 min). Torrefaction at 300 °C for 30 min was selected to be optimum condition, considering the mass yield and energy densification ratio. Steam gasification of lignite, raw- and torrefied biomass, and their blends at different ratios were conducted at downdraft fixed bed reactor. For comparison, gasification experiments with pyrochar obtained at 500 °C were also performed. The maximum hydrogen yield of 100 mol/kg fuel was obtained steam gasification of pyrochar. The hydrogen yields of 84 and 75 mol/kg fuel were obtained from lignite and torrefied biomass, respectively. Remarkable synergic effect exhibited in co-gasification of lignite with raw biomass or torrefied biomass at a blending ratio of 1:1. In co-gasification, the highest hydrogen yield of 110 mol/kg fuel was obtained from torrefied biomass-lignite (1:1) blend, while a hydrogen yield from pyrochar-lignite (1:1) blend was 98 mol/kg. The overall results showed that in co-gasification of lignite with biomass, the yields of hydrogen depend on the volatiles content of raw biomass/torrefied biomass, besides alkaline earth metals (AAEMs) content.     

An onboard hydrogen generator for hydrogen enhanced combustion with internal combustion engine

Hydrogen enhanced combustion (HEC) for internal combustion engine is known to be a simple mean for improving engine efficiency in fuel saving and cleaner exhaust. An onboard compact and high efficient methanol steam reformer is made and installed in the tailpipe of a vehicle to produce hydrogen continuously onboard by using the waste heat of the engine for heating up the reformer; this provides a practical device for the HEC to become a reality. This use of waste heat from engine enables an extremely high process efficiency of 113% to convert methanol (8.68 MJ) for 1.0 NM of hydrogen (9.83 MJ) and low cost of using hydrogen as an enhancer or as a fuel itself. The test results of HEC from the onboard hydrogen production are presented with 2 gasoline engine vehicles and 2 diesel engines; the results indicate a hike of engine efficiency in 15–25% fuel saving and a 40–50% pollutants reduction including 70% reduction of exhaust smoke. The use of hydrogen as an enhancer brings about 2–3 fold of net reductions in energy, carbon dioxide emission and fuel cost expense over the input of methanol feed for hydrogen production.     

Numerical analysis of performance enhancement and non-isothermal reactant transport of a cylindrical methanol reformer wrapped with a porous sheath under steam reforming

This paper accomplished a three-dimensional computational analysis of the methanol reformer with steam reforming by the Arrhenius form of reaction model and SIMPLE-C algorithm. The performance enhancement and non-isothermal reactant transport of the cylindrical reformer wrapped with a porous sheath were investigated. The parameters, including temperature of internal heater (T_H), porosity (ε), and thickness of porous sheath (R_P), on methanol conversion, hydrogen, carbon monoxide, carbon dioxide productions, temperature and velocity fields with the same inlet conditions have been investigated. The results present that higher methanol conversion and richer hydrogen production occur as temperature of heater, porosity, and porous sheath thickness increase. As temperature of internal heater is equal to 250 °C, employing a porous sheath with ε = 0.9 and R_P = 10 mm to wrap a reformer results in the maximum enhancements of 35.71% in methanol conversion and 21.18% in hydrogen production. Besides, a porous sheath with ε = 0.5 and R_P = 10 mm leads to the maximum reduction of 2.23% in carbon monoxide produced from the reformer at T_H = 300 °C.     

Hydrogen generation by alcohol reforming in a tandem cell consisting of a coupled fuel cell and electrolyser

The performance of a novel electro-reformer for the production of hydrogen by electro-reforming alcohols (methanol, ethanol and glycerol) without an external electrical energy input is described. This tandem cell consists of an alcohol fuel cell coupled directly to an alcohol reformer, negating the requirement for external electricity supply and thus reducing the cost of operation and installation. The tandem cell uses a polymer electrolyte membrane (PEM) based fuel cell and electrolyser. At 80 °C, hydrogen was generated from methanol, by the tandem PEM cell, at current densities above 200 mA cm⁻², without using an external electricity supply. At this condition the electro-reformer voltage was 0.32 V at an energy input (supplied by the fuel cell component) of 0.91 kWh/Nm³; i.e. less than 20% of the theoretical value for hydrogen generation by water electrolysis (4.7 kWh/Nm³) with zero electrical energy input from any external power source. The hydrogen generation rate was 6.2 × 10⁻⁴ mol (H₂) h⁻¹. The hydrogen production rate of the tandem cell with ethanol and glycerol was approximately an order of magnitude lower, than that with methanol.     

Copper zinc oxide nanocatalysts grown on cordierite substrate for hydrogen production using methanol steam reforming

Hydrogen production from methanol rather than the traditional source, methane, is considered to be advantageous in ease of transportation and storage. However, the current copper-based catalysts utilized in methanol steam reforming are associated with challenges of sintering at high temperature and production of CO which could poison fuel cells. In addressing these challenges, ZnO nanorods were grown hydrothermally on the surface of cordierite and impregnated with Cu to produce catalysts for methanol steam reforming. The catalysts were characterized using SEM, XRD, FTIR, XPS, BET and Raman Spectroscopy. A fixed-bed reactor was used for testing the catalysts while the reaction products were characterized using a GC fitted with FID and TCD. The effects of temperature, methanol concentration and particle size of catalysts on methanol steam reforming were investigated. The experiments were carried out between 180 and 350 °C. CO selectivity of 0% was observed for temperatures between 180 and 230 °C for 0.8 MeOH:1H₂O with an average H₂ selectivity of 98% for that temperature range. XPS showed that the catalyst was relatively unchanged after reaction while Raman spectroscopy revealed coke formation on the catalyst surface for reactions carried out above 300 °C. This shows that the catalyst is active and selective for the reaction.     

Thermo-chemical conversion of waste rubber seed shell to produce fuel and value-added chemicals

Rubber seed shell (RSS), comprises of 96.67 wt% organic content and 38.6% crystallinity index, was used for the production of biofuel and value-added chemicals through semi-batch pyrolysis. Thermogravimetric analysis (TGA) of RSS at heating rate of 20 °C/min showed R50 value as 12.72%/min at 376.5 °C. The gaseous product evolved during the decomposition of RSS were analyzed through inline Fourier transform infrared (FT-IR) coupled with TGA instrument. The effects of pyrolysis temperatures (350°C-600 °C) and heating rates (10°C/min–40 °C/min) on the product distribution (liquid, gas and bio-char) were investigated. The maximum yield of liquid product (46.14 wt%) and the carbon-rich bio-char (31.92 wt%) were obtained at 550 °C temperature for heating rate of 30 °C/min. The fuel characteristics of produced bio-char such as higher calorific value (34.5 MJ/kg), higher fixed carbon (79.74 wt%), lower ash (1.87 wt%) and lower moisture content (2.11 wt%) suggested its potential to be used as solid fuel. Value-added organic compounds such as acetic acid, phenolic compounds, creosol, pilocarpine, benzene and levoglucosan were identified in the liquid product using gas chromatography. The pH values of liquid products (2.55–3.0) support the presence of organic acids and phenolic fraction. The presence of various functional groups was also identified using FT-IR spectroscopy. In depth analysis of physico-chemical-thermal properties of RSS and obtained products (liquid and bio-char) suggested that RSS can be considered as a suitable feedstock for the production of value added chemicals including fuel.