PEM – Fuel Cell System for Residential Applications

Viessmann is developing a PEM fuel cell system for residential applications. The uncharged PEM fuel cell system has a 2 kW electrical and 3 kW thermal power output. The Viessmann Fuel Processor is characterized by a steam‐reformer/burner combination in which the burner supplies the required heat to the steam reformer unit and the burner exhaust gas is used to heat water. Natural gas is used as fuel, which is fed into the reforming reactor after passing an integrated desulphurisation unit. The low temperature (600 °C) fuel processor is designed on the basis of steam reforming technology. For carbon monoxide removal, a single shift reactor and selective methanisation is used with noble metal catalysts on monoliths. In the shift reactor, carbon monoxide is converted into hydrogen by the water gas shift reaction. The low level of carbon monoxide at the outlet of the shift reactor is further reduced, to approximately 20 ppm, downstream in the methanisation reactor, to meet PEM fuel cell requirements. Since both catalysts work at the same temperature (240 °C), there is no requirement for an additional heat exchanger in the fuel processor. Start up time is less than 30 min. In addition, Viessmann has developed a 2 kW class PEFC stack, without humidification. Reformate and dry air are fed straight to the stack. Due to the dry operation, water produced by the cell reaction rapidly diffuses through the electrolyte membrane. This was achieved by optimising the MEA, the gas flow pattern and the operating conditions. The cathode is operated by an air blower.     

Novel compact steam reformer for fuel cells with heat generation by catalytic combustion augmented by induction heating

The overall objective of the project is to investigate, design and test an improved steam reformer for fuel cell power plants.

Catalytic combustion is used to minimise the disadvantages of conventional external reforming. By integrating various technologies, smaller-scale reformer, lower emission levels and reduced start-up time along with improved temperature control can be achieved.

Catalytic combustion is used to generate the heat required for the reforming reaction, thus avoiding NO_x formation. The heat can be generated locally and made available for the reforming reaction using a thermally conductive substrate.

The first results of the catalytic test reactor show good conversion rates for both the combustion and the reforming reaction. Based on the hydrogen production rate, the initial objectives for the volume of the reformer have proven to be feasible.

The results are used to build a 20 kW integrated test reactor.     

Transient modeling of combined catalytic combustion/CH4 steam reforming

This paper presents an investigation into the complex interactions between catalytic combustion and CH₄ steam reforming in a co-flow heat exchanger where the surface combustion drives the endothermic steam reforming on opposite sides of separating plates in alternating channel flows. To this end, a simplified transient model was established to assess the stability of a system combining H₂ or CH₄ combustion over a supported Pd catalyst and CH₄ steam reforming over a supported Rh catalyst. The model uses previously reported detailed surface chemistry mechanisms, and results compared favorably with experiments using a flat-plate reactor with simultaneous H₂ combustion over a γ-Al₂O₃-supported Pd catalyst and CH₄ steam reforming over a γ-Al₂O₃-supported Rh catalyst. Results indicate that stable reactor operation is achievable at relatively low inlet temperatures (400 °C) with H₂ combustion. Model results for a reactor with CH₄ combustion indicated that stable reactor operation with reforming fuel conversion to H₂ requires higher inlet temperatures. The results indicate that slow transient decay of conversion, on the order of minutes, can arise due to loss of combustion activity from high-temperature reduction of the Pd catalyst near the reactor entrance. However, model results also show that under preferred conditions, the endothermic reforming can be sustained with adequate conversion to maintain combustion catalyst temperatures within the range where activity is high. A parametric study of combustion inlet stoichiometry, temperature, and velocity reveals that higher combustion fuel/air ratios are preferred with lower inlet temperatures (≤500 °C) while lower fuel/air ratios are necessary at higher inlet temperatures (600 °C).     

Heat-Integrated Concepts for Automotive Exhaust Purification

Novel heat-integrated concepts for efficient automotive exhaust gas purification are presented. The general design consists of a counter-current heat exchanger coupled with purification devices. Transient and steady state experiments were carried out both in lab scale and on an engine test bench. The results show effective heat recovery at acceptable pressure drop. Comparative simulation studies show the advantages of the system under drive cycle conditions.     

A fluidized bed membrane reactor for the steam reforming of methane

In the present investigation a realistic two-phase model accounting for the change in the total number of moles accompanying the reaction is utilized to explore a novel reactor configuration suggested for the methane steam reforming process. The suggested design is basically a fluidized bed reactor equipped with a bundle of membrane tubes. These tubes remove the main product, hydrogen, from the reacting gas mixture and drive the reaction beyond its thermodynamic equilibrium. The proposed novel design is also equipped with sodium heat pipes which act as a thermal flux transformer to provide the large amount of heat needed by the endothermic reaction through a relatively small heat transfer surface, assuring better reactor compactness. Two options for fluid routing through the membrane tubes are proposed; each is suitable for a certain industrial application. The performance of this novel configuration is compared with that of an industrial fixed bed steam reformer and the comparison shows the potential advantages of the suggested configuration.     

1kW SOFC-CHP系统用催化燃烧耦合蒸汽重整反应器的实验研究

针对1 kW 固体氧化物燃料电池热电联供(SOFC-CHP)系统开发了集成催化燃烧、换热及蒸汽重整的反应器,搭建了性能评价系统,系统研究了燃烧侧气体组分及工艺参数对该反应器性能的影响规律。实验结果表明:在反应器燃烧侧气体入口温度为300℃、空燃比为10:1、电堆燃料利用率为65%、水碳比为3 的条件下,重整侧转化率达到73.6%,重整尾气中H₂ 含量为67.5%。电堆燃料利用率对重整反应转化效率影响较大,其值大于80%时,采用尾气燃烧的余热回收方式无法有效为蒸汽重整提供所需热量。在150~350℃范围内,降低燃烧侧气体入口温度对重整反应效率影响较小,建议采用尾气先换热再进行催化燃烧的流程设计,保证重整效率的前提下可有效提升系统热效率。空燃比的降低可小幅度提升重整效率,在保证电堆反应温度稳定的前提下,适当降低空燃比可减少空气压缩机的功耗,从而提升整个系统的效率。研究成果对SOFC-CHP 系统的优化和整体效率提升具有指导意义。     

板翅式反应器中甲醇水蒸气重整制氢

研制了一种高效板翅式反应器,其特点是体积相对较小,便于放置,便于扩大规模;集预热、气化、重整、催化燃烧于一体;板翅式反应器内部热量利用合理,放热反应与吸热反应、气化与冷却之间实现了较好的热量耦合;可实现完全自供热.在反应器中进行了一系列甲醇水蒸气重整的实验,考察了不同条件对甲醇重整制氢过程的影响、对反应器床层温度分布的影响,及反应器的稳定性.另外,由于板翅式结构的良好传热性,甲醇水蒸气重整在获得较高转化率的同时重整气中CO浓度较低,且反应器的稳定性良好.     

Modeling of a metal monolith catalytic reactor for methane steam reforming-combustion coupling

A novel metal monolith reactor for coupling methane steam reforming with catalytic combustion is proposed in this work, the metal monolith is used as a co-current heat exchanger and the catalysts are deposited on channel walls of the monolith. The transport and reaction performances of the reactor are numerically studied utilizing heterogeneous model based on the whole reactor. The influence of the operating conditions like feed gas velocity, temperature and composition are predicted to be significant and they must be carefully adjusted in order to avoid hot spots or insufficient methane conversion. To improve reactor performance, several different channel arrangements and catalyst distribution modes in the monolith are designed and simulated. It is demonstrated that reasonable reactor configuration, structure parameters and catalyst distribution can considerably enhance heat transfer and increase the methane conversion, resulting in a compact and intensified unit.     

ONBOARD FUEL CONVERSION FOR HYDROGEN-FUEL-CELL-DRIVEN VEHICLES

Increasingly stringent legislation controls emissions from internal combustion engines to the point where alternative power sources for vehicles are necessary. The hydrogen fuel cell is one promising option, but the nature of the gas is such that the conversion of other fuels to hydrogen on board the vehicle is necessary.

The conversion of methanol, methane, propane, and octane to hydrogen is reviewed. A combination of oxidation and steam reforming (indirect partial oxidation) or direct partial oxidation are the most promising processes. Indirect partial oxidation involves combustion of part of the fuel to produce sufficient heat to drive the endothermic steam reforming reaction. Direct partial oxidation is favored only at high temperatures and short residence times but is highly selective. However, indirect partial oxidation is shown to be the preferred process for all fuels.

The product gases can be taken through a water–gas shift reactor, but still retain ～2% carbon monoxide, which poisons fuel-cell catalysts. Selective oxidation is the preferred route to removal of residual carbon monoxide. Low-temperature oxidation in the absence and presence of an excess of hydrogen is reviewed. Au-based catalysts show much promise, but precious metal catalysts such as Pt/zeolite have some advantages.     

ONBOARD FUEL CONVERSION FOR HYDROGEN-FUEL-CELL-DRIVEN VEHICLES

Increasingly stringent legislation controls emissions from internal combustion engines to the point where alternative power sources for vehicles are necessary. The hydrogen fuel cell is one promising option, but the nature of the gas is such that the conversion of other fuels to hydrogen on board the vehicle is necessary.

The conversion of methanol, methane, propane, and octane to hydrogen is reviewed. A combination of oxidation and steam reforming (indirect partial oxidation) or direct partial oxidation are the most promising processes. Indirect partial oxidation involves combustion of part of the fuel to produce sufficient heat to drive the endothermic steam reforming reaction. Direct partial oxidation is favored only at high temperatures and short residence times but is highly selective. However, indirect partial oxidation is shown to be the preferred process for all fuels.

The product gases can be taken through a water-gas shift reactor, but still retain ∼2% carbon monoxide, which poisons fuel-cell catalysts. Selective oxidation is the preferred route to removal of residual carbon monoxide. Low-temperature oxidation in the absence and presence of an excess of hydrogen is reviewed. Au-based catalysts show much promise, but precious metal catalysts such as Pt/zeolite have some advantages.     

物流分布对板翅式制氢反应器性能的影响

建立了板翅式制氢反应器中的三维数学模型,并采用此模型对反应器内部的温度分布进行了数值计算,并且和实验结果相结合,对不同方式的燃烧气流分布的效果进行分析。计算和分析结果均表明:燃烧气流分布均匀与否对反应器性能的影响较大,通过改进气体分布可以有效地改善反应器内部的温度分布及反应性能。     

A novel laboratory bench for practical evaluation of catalysts useful for simultaneous conversion of NOx and soot in diesel exhaust

This study deals with the development of a laboratory bench for the practical evaluation of catalysts that are useful for the direct conversion of NO_x and soot in the exhaust of diesel engines. The employed model exhaust is generated by using a diffusion burner with additionally dosing some gaseous components to the burner gas to obtain a realistic feed composition. The produced soot is extensively characterized by employing thermogravimetry, transmission electron microscopy, N₂ physisorption and temperature programmed techniques. The results of the different characterization methods show that the present soot is suitable for the intended catalytic investigations. The simultaneous conversion of NO_x and soot is examined like in practice, i.e. the soot is separated from the tail gas by a diesel particulate filter (DPF) that is coated with the catalyst. The deposited soot is then catalytically converted by NO_x and O₂ to form N₂ and CO₂. The conversions of NO_x and soot are measured by exclusively applying gas analysers, whereby a special experimental procedure is developed to determine the soot removal. Hence, additional soot related analytics are not required. To show the suitability of the constructed bench a Pt/Fe₂O₃/β-zeolite sample is taken as test catalyst that is reported to be very active in NO_x/soot reaction. The measurements performed with and without catalyst clearly show the effect of the used sample in simultaneous NO_x/soot conversion. We therefore consider the constructed laboratory bench to be a useful tool for testing and ranking catalytic materials.     

Recuperative coupling of exothermic and endothermic reactions

Coupling energy intensive endothermic reaction systems with suitable exothermic reactions improves the thermal efficiency of processes and reduces the size of the reactors. One type of reactor suitable for such a type of coupling is the heat exchanger reactor. In this work, a one-dimensional pseudo-homogeneous plug flow model is used to analyze and compare the performance of co-current and counter-current heat exchanger reactors. A parametric analysis is carried out to address the vital issues, such as the exit conversion of the endothermic reaction, the temperature peak (hot spot) of the exothermic reaction and the reactor volumetric productivity. The measures to reduce the hot spot by different catalyst profiling techniques are also addressed. Some features of the dynamic behavior exhibited by these reactors, which are important from design, operational and control point of view, are presented.     

Scale-up of sulphur resistant promoted-vanadium oxide catalysts for self-regenerating catalytic filters in off-road diesel engines and domestic apparatus

Wall-flow catalytic filters were prepared by impregnation of porous cordierite honeycombs with Cs-Fe-V catalysts. The catalytic filters were tested at the exhaust of a gas-oil burner. Results reported indicate that the trapped soot begin to burn at a temperature around 300–320 °C allowing the self-regeneration of the filter. Performances were found to remain stable also under high SO₂ concentrations, making these catalytic filters suitable for soot removal in off-road diesel engines and domestic apparatus.     

Syngas production by biomass gasification using Rh/CeO2/SiO2 catalysts and fluidized bed reactor

We have been developed novel catalysts for gasification of biomass with much higher energy efficiency than conventional methods (non-catalyst, dolomite, commercial steam reforming Ni catalyst). From the result of the gasification of cellulose over novel Rh/CeO₂/SiO₂ catalysts, it is found that the gasification process consists of the reforming of tar and the combustion of solid carbon. We also tested novel Rh/CeO₂/SiO₂ in the gasification with air, pyrogasification, and steam reforming of cedar wood. As a result, Rh/CeO₂/SiO₂ gave higher yield of syngas than the conventional steam reforming Ni catalyst. Furthermore, we compared the performance between single and dual bed reactors. Single bed reactor was effective in the gasification of cedar, however, it was not suitable for the gasification of rice straw since a rapid deactivation was observed. Gasification of rice straw, jute stick, baggase using the fluidized dual-bed reactor and Rh/CeO₂/SiO₂ was also investigated. Especially, the catalyst stability in the gasification of rice straw clearly was enhanced by using the fluidized dual bed reactor.     

甲烷催化燃烧反应工艺研究进展

甲烷催化燃烧是一种清洁高效的甲烷燃烧技术,在节能减排中具有重要的应用价值。从催化剂、反应工艺和过程强化等方面对近年来甲烷催化燃烧技术进行综述,重点介绍颗粒催化剂固定床反应工艺、整体式催化剂反应工艺、流化床反应工艺和吸放热耦合反应工艺研究进展。用于固定床反应器的颗粒催化剂主要为负载型贵金属催化剂和非贵金属氧化物催化剂。贵金属催化剂活性好,起燃温度低,适合低浓度甲烷的催化燃烧。非贵金属氧化物催化剂耐高温性好,适合较高浓度甲烷燃烧体系。整体式催化剂的甲烷催化燃烧反应工艺中,最常用的是蜂窝陶瓷和金属合金等整体式催化剂的多段式催化燃烧反应器的设计。设计直接采用多段式整体催化剂,催化剂的位置不同,发挥的催化作用也不同。流化床催化燃烧装置具有燃烧过程接触面积广、热容量大和换热效率高等特点,可有效避免传统的固定床催化燃烧反应工艺存在的问题,非常适合应用于低浓度甲烷的催化燃烧过程。利用甲烷催化燃烧强放热的特点,将催化燃烧产生的热量进行时间或空间的耦合,可以开发出吸-放热耦合反应工艺。其中,固定床催化反应器中的流向变换强制周期操作作为一种高效的过程强化技术,在节约反应器成本的同时,可以提高反应热量的利用率。     

操作参数对余热回收甲醇水蒸气重整制氢过程的影响

以模拟汽车尾气供热的甲醇水蒸气重整（MSR）制氢反应为研究对象,设计了集余热加热与MSR制氢反应于一体的肋式微反应器,考察了反应器进口热风速度、温度,反应物进口速度、温度、水醇比及顺逆流情况对MSR制氢过程的影响。计算结果表明,逆流、水醇比1.3、热风进口速度1.1 m/s、温度773 K、反应物进口速度0.1 m/s、温度493 K为该反应过程的最佳工况参数,此时甲醇转化率为99.4%,模拟汽车尾气余热的热效率为28%,反应器出口氢气的体积分数为69.6%。研究结果对开展余热综合利用及发动机尾气重整制氢掺氢燃烧的研究有借鉴意义。     

Simultaneous removal of soot and nitrogen oxides from diesel engine exhausts

In this paper, previously reported findings and new results presented here are discussed with the main objective of establishing the reaction mechanism for soot oxidation on different supports and catalysts formulations. Catalysts containing Co, K and/or Ba supported on MgO, La₂O₃ and CeO₂ have been studied for diesel soot catalytic combustion. Among them, K/La₂O₃ and K/CeO₂ showed the best activity and stability for the combustion of soot with oxygen. A reaction mechanism involving the redox sites and the surface-carbonate species takes place on these catalysts. On the other hand, Co,K/La₂O₃ and Co,K/CeO₂ catalysts display activity for the simultaneous removal of soot and nitric oxide. The soot–catalyst contacting phenomenon was also addressed. A synergic La–K effect was observed in which the mechanical mixtures of soot with K–La₂O₃ showed higher combustion rates than those observed when K and La were directly deposited on the soot surface. The effect of the addition of Ba was explored with the aim of promoting the interaction of the solid with NO₂, thus combining the NO_x catalytic trap concept with the soot combustion for filter regeneration. Ba/CeO₂ and Ba,K/CeO₂ were effective in NO_x absorption as shown in the microbalance experiments. However, the formation of stable nitrate species inhibits the soot combustion reaction.     

Robust autothermal microchannel reactors

Autothermal microchannel reactors are intensified process units that bring significant energy efficiency benefits over their conventional counterparts. Efficiency gains are obtained, however, at the cost of operational challenges. These stem from the loss of control handles that is inherent to combining several unit operations in a single physical device. In this paper, we investigate the impact of two recently proposed reactor design concepts (a segmented catalyst macromorphology and an embedded layer of phase change material) aimed at improving the steady state energy distribution and, respectively, preventing the advent of hotspots during transient operation, on reactor dynamics and control. Using an autothermal microchannel reactor coupling steam methane reforming with methane catalytic combustion as a prototype system, we demonstrate through rigorous simulations that these design innovations have a synergistic effect, resulting in superior steady-state performance and excellent disturbance rejection ability.     

Analysis of a novel reverse-flow reactor concept for autothermal methane steam reforming

One of the main shortcomings of existing multifunctional reactor concepts for the autothermal coupling of endothermic and exothermic reactions is inefficient heat integration leading to excessive maximum temperatures or poor reactor performance. For the asymmetric operation of a reverse-flow steam reforming reactor, conditions under which these shortcomings can be overcome are proposed. The asymmetric process is based on the formation of travelling reaction zones. The features of these transient phenomena are analysed by means of a simplified model.During the endothermic semicycle, the heat consumption forms a temperature wave with an expansive low-temperature and a compressive high-temperature part. During the exothermic semicycle a proper axial distribution of the heat supply is necessary in order to maintain a favourable temperature profile in the cyclic operation mode.The results obtained with the simplified model are verified by direct dynamic simulation.