DME conversion using high flux tubular membrane reactors

High flux tubular membrane reactors were designed for dimethyl ether (DME) steam reforming. Considering the facile scale-up and high flux of hydrogen, tubular stainless steel supports were employed for the membrane reactors. At 500°C, DME conversion reached ~100%, while hydrogen recovery reached 20%. However, contamination by CO was rather high (>1%), making this process unsuitable for proton exchange membrane fuel cell applications, which require a CO concentration of <100 ppm. This result showed that an additional polishing step was needed to reduce the CO concentration. Membrane reactors were further modified to perform an water–gas shift reaction on the permeate of the membrane reactors by employing a fixed bed reactor, which yielded high-purity hydrogen (~99%) along with a low CO content (<20 ppm).     

ON THE EFFECTS OF SYNGAS COMPOSITION AND WATER-GAS-SHIFT REACTION RATE ON FT SYNTHESIS OVER IRON BASED CATALYST IN A SLURRY REACTOR

Water gas shift reaction plays an important role in the Fischer-Tropsch synthesis reaction over iron-based catalysts. A slurry reactor model which accounted for the kinetics of both Fischer-Tropsch synthesis and water gas shift reaction was used to investigate the effects of hydrogen to carbon monoxide ratio, water vapor concentration and reactor temperature on synthesis gas conversion. The model was used to determine optimum concentration of water in the feed gas. For a given reactor temperature, the optimum concentration of water in the feed gas was found to increase with decreasing hydrogen to carbon monoxide ratio. The optimum concentration of water in the feed gas was found to decrease with increasing reactor temperature. Increasing the water gas shift reaction rate improved syngas conversion for low reaction temperatures.     

净化黄磷尾气CO变换制氢最佳工艺条件选择

为选择含高体积分数CO净化黄磷尾气变换制氢最佳工艺条件,对影响其变换率的反应温度、空速、汽气体积分数比、CO2体积分数几个主要因素进行了综合研究。采用均匀设计方法,以B112型高温变换催化剂为例,对含高体积分数CO净化黄磷尾气变换工艺条件进行了系统研究。研究结果表明:影响其变换效率的因素由大到小依次为反应温度、空速、汽气体积分数比、CO2体积分数;通过模型优化及实验验证,结合工业实际,得到优化的工艺条件为反应温度490℃,空速为1 000 h-1,汽气体积分数比为2.5,CO2体积分数为1%,可得CO变换率为88.9%;回归方程模型高度显著可信。     

Effects of system parameters on the performance of CO2-selective WGS membrane reactor for fuel cells

Performing water gas shift (WGS) reaction efficiently is critical to hydrogen purification for fuel cells. In our earlier work, we proposed a CO₂-selective WGS membrane reactor, developed a one-dimensional non-isothermal model to simulate the simultaneous reaction and transport process and verified the model experimentally under an isothermal condition. Further modeling investigations were made on the effects of several important system parameters, including inlet feed temperature, inlet sweep temperature, feed-side pressure, feed inlet CO concentration, and catalyst activity, on membrane reactor performance. The synthesis gases from both autothermal reforming and steam reforming were used as the feed gas. As the inlet feed temperature increased, the required membrane area reduced because of the higher WGS reaction rate. Increasing the inlet sweep temperature decreased the required membrane area more significantly, even though the required membrane area increased slightly when the inlet sweep temperature exceeded about 160 °C. Higher feed-side pressure decreased the required membrane area as a result of the higher permeation driving force and reaction rate. A potentially more active catalyst could make the membrane reactor more compact because of the enhanced reaction rate. The modeling results have shown that a CO concentration of less than 10 ppm is achievable from syngases containing up to 10% CO.     

Upgrading of a syngas mixture for pure hydrogen production in a Pd-Ag membrane reactor

Water gas shift (WGS) is a thermodynamics limited reaction and CO equilibrium conversion of a traditional reactor is furthermore reduced owing to the presence of H₂ (ca. 50%) in the feed stream coming from a reformer.The upgrading of a simulated reformate stream was experimentally investigated as a function of temperature (280-320 °C), feed pressure (up to 600 kPa), gas hourly space velocity (GHSV), etc. using a Pd-alloy membrane reactor (MR) packed with a commercial catalyst CuO/CeO₂/Al₂O₃; no sweep gas was used. The MR performance was also evaluated using new parameters such as conversion index, H₂ recovery and extraction index, etc., which evidence the advantages with respect to a traditional reactor.A Pd-based MR operated successfully overcoming the thermodynamic constraints of a traditional reactor and, specifically, the drawback introduced by the hydrogen presence. In fact, a CO conversion of 90% significantly exceeded (three times) the thermodynamics upper limit (<36%) of a traditional reactor owing to ca. 80% of hydrogen permeated through the membrane.The overall process performance was significantly improved by the presence of the Pd-based membrane and, thus, by the high reaction pressure which allowed and drove the hydrogen permeation.     

Water Gas Shift Reaction in a Membrane Reactor Using a High Hydrogen Permselective Silica Membrane

A membrane reactor (MR) for the water gas shift (WGS) reaction was developed by integrating a highly hydrogen permselective silica membrane. The membrane was prepared using an extended counter-diffusion chemical vapor deposition (CVD) method. A tetramethylorthosilicate (TMOS) silica source was fed from one side of the membrane support and oxygen gas fed from the other. The dense silica film was deposited on a porous support by pressurizing the side that TMOS is supplied. A high hydrogen permselective silica membrane was obtained by this method. A commercial Pt catalyst was used in the WGS reaction. Efficacy of the silica membrane toward the WGS reaction was investigated as a function of temperature (523-623 K), steam/carbon monoxide (S/C) ratio (1-3), differential pressure (0-100 kPa), and gas hourly space velocity (GHSV; 1800-5400 h^?1). The CO conversion in the MR was higher than that for a fixed bed reactor (FBR) under all experimental conditions, and was also higher than the thermodynamic equilibrium conversion under almost all experimental conditions. This was due to the selective abstraction of hydrogen from the product stream by the silica membrane. At an S/C of 1.0, the CO conversion in the MR was superior to that in a FBR by 16.8%.     

Ethanol steam reforming in a membrane reactor with Pt-impregnated Knudsen membranes

An ethanol reforming membrane reactor (ERMR) with Pt-impregnated Knudsen membranes was investigated to achieve the improvement of ethanol conversion and hydrogen yield. The prepared Pt-impregnated membranes have high permeabilities and reaction activities for the water-gas shift (WGS) reaction. The ethanol reforming-membrane reactor showed ethanol conversion improvement of 7.4–14.4% in comparison with a conventional reactor (CR). Hydrogen yield improvement of 4.2–10.5% was also observed in ERMR with Pt-impregnated SKM in whole reaction temperature range. In addition, CO concentration was considerably reduced via water-gas shift reaction during the permeation.     

一氧化碳等温变换技术进展

对现代合成氨CO变换技术中发展起来的不同种类的固定床等温反应器进行了比较 ,从转化率、操作稳定性、结构复杂程度及发展前景等方面进行了论述。特别分析了另一类等温反应器———流化床反应器的特点 ,并结合其在传热、传质、处理量及操作等方面的优势和流态化技术的发展。流化床反应器在CO变换过程中的工业化应用很有前景     

Kinetic and CFD Modeling of Exhaust Gas Reforming of Natural Gas in a Catalytic Fixed-Bed Reactor for Spark Ignition Engines

Fuel reforming is an attractive method for performance enhancement of internal combustion engines fueled by natural gas, since the syngas can be generated inline from the reforming process. In this study, 1D and 2D steady-state modeling of exhaust gas reforming of natural gas in a catalytic fixed-bed reactor were conducted under different conditions. With increasing engine speed, methane conversion and hydrogen production increased. Similarly, increasing the fraction of recirculated exhaust gas resulted in higher consumption of methane and generation of H₂ and CO. Steam addition enhanced methane conversion. However, when the amount of steam exceeded that of methane, less hydrogen was produced. Increasing the wall temperature increased the methane conversion and reduced the H₂/CO ratio.     

Production and Isolation of n‐Butyl Acrylate Using Pervaporation‐Aided Esterification Reaction: Kinetics and Optimization

Synthesis of n‐butyl acrylate by esterification of acrylic acid with n‐butyl alcohol was carried out in a batch membrane reactor. Optimization and design of the experiment was accomplished by response surface methodology with Box‐Behnken experimental design. The effects of different parameters like reaction temperature, catalyst concentration, molar ratio of alcohol to acid, and ratio of membrane surface to initial volume on water flux and conversion of acrylic acid were evaluated. A kinetic model for the esterification‐coupled pervaporation process was developed. Kinetic parameters were estimated by a nonlinear optimization technique in the MATLAB optimization toolbox. The experimental and simulation results were applied for developing a concept to effectively conduct a pilot‐scale esterification‐pervaporation experiment.     

Theoretical investigation of a water‐gas‐shift catalytic membrane for diesel reformate purification

The novel application of a catalytic water‐gas‐shift membrane reactor for selective removal of CO from H₂‐rich reformate mixtures for achieving gas purification solely via manipulation of reaction and diffusion phenomena, assuming Knudsen diffusion regime and the absence of hydrogen permselective materials, is described. An isothermal, two‐dimensional model is developed to describe a tube‐and‐shell membrane reactor supplied with a typical reformate mixture (9% CO, 3% CO₂, 28% H₂, and 15% H₂O) to the retentate volume and steam supplied to the permeate volume such that the overall H₂O:CO ratio within the system is 9:1. Simulations indicate that apparent CO:H₂ selectivities of 90:1 to >200:1 at H₂ recoveries of 20% to upwards of 40% may be achieved through appropriate design of the catalytic membrane and selection of operating conditions. Under these conditions, simulations predict an apparent hydrogen permeability of 2.3 × 10^?10 mol m^?1 Pa, which compares favorably against that of competing hydrogen‐permselective membranes. © 2013 American Institute of Chemical Engineers AIChE J, 59: 4334–4345, 2013     

Variants of the organization of a controlled-temperature-profile catalyst bed in a tubular reactor for the single-step water gas shift reaction

The possibility of bringing the actual temperature profile along the catalyst bed to the profile maximizing the CO conversion in the water gas shift (WGS) reaction in a tubular reactor is considered for new, highly efficient catalysts as heat-conducting composite plates (HCCPs). It is demonstrated by the example of a controlled-temperature-profile (CTP) tubular reactor integrated into an experimental model of a fuel cell of a 5-kW power plant that the efficiency of the WGS process can be raised by using the catalyst as HCCPs. Use of these catalysts in CTP apparatuses can markedly increase the efficiency of the WGS stage of natural gas reforming for ammonia synthesis, hydrogen production, and the production of fuel gas for fuel cells.     

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。     

铜基低变催化剂H_2S中毒机理热力学分析

为掌握CO变换制氢过程中催化剂中毒机理,采用热力学非均相反应体系中G ibbs自由能最小原理,分析了铜基低温变换催化剂在463.15—523.15 K内H2S中毒过程中可能发生的化学反应及其产物,并结合文献实验结果综合讨论了铜基低温变换催化剂的H2S中毒机理。结果表明:催化剂的H2S中毒过程中,硫酸盐和积碳会造成催化剂的暂时性中毒,生成Cu2S和CuS化合物造成永久性中毒;O2的存在会加快催化剂的中毒反应;铜基低温变换催化剂不适合用于含高体积分数CO原料气的变换反应过程。     

CO‐Free Hydrogen Production by Ethanol Steam Reforming in a Pd–Ag Membrane Reactor

In this work, the ethanol steam reforming (ESR) reaction has been studied by using a dense Pd–Ag membrane reactor (MR) by varying the water/ethanol molar ratio between 3:1 and 9:1 in a temperature range of 300–400 °C and at 1.3 bar as reaction pressure. The MR was packed with a commercial Ru‐based catalyst and a constant sweep gas flow rate in counter current mode was used. The influence of the temperature and the feed molar ratio on different parameters such as the ethanol conversion, the hydrogen production, the hydrogen yield and the CO‐free hydrogen recovery has been evaluated.     

用多孔金属—SiO2复合膜反应器进行CO水蒸汽变换反应

用自制的多孔金属－ＳｉＯ２复合膜组装成一种新颖的膜反应器，利用ＣＯ变换反应考察该膜反应器的性能实验系统地考察了反应温度，空速、水／气比和只发气流量对ＣＯ转化率的影响。结果表明，在相同的反应条件下，膜反应器的转化率比固定床反应器的转化率提高４－１１％左右，最高可达２０％。     

Membrane reactors for hydrogen production

Fuel cell powered vehicles with on board reforming need compact and lightweight components. A membrane reactor, that combines hydrogen permeable membranes with a methanol steam reformer promises considerable weight and space savings. Its dense metal membranes produce high purity hydrogen over a wide range of pressure and load. The selective removal of hydrogen yields methanol- and CO-conversions that are higher than the equilibrium conversion in a conventional reactor. Results with three different metal membranes in a membrane reactor for steam reforming of methanol are presented. A mathematical model accurately describes the measured performance of the membrane reactor and allows predictions for other values of the process parameters.     

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.     

Hydrogen generation in a Pd membrane fuel processor: assessment of methanol-based reaction systems

The feasibility of a Pd membrane fuel processor that integrates several methanol-based chemistries and hydrogen purification steps is assessed. The assessment involves membrane reactor simulations to determine the effects of operating and design parameters on performance metrics including hydrogen utilization, hydrogen productivity, device volume, and Pd requirements. Methanol decomposition (direct and oxidative) on Pd/SiO₂, methanol steam reforming (MSR) on Cu/ZnO/Al₂O₃, and methanol partial oxidation (MPOX) on Cu/Al₂O₃ are evaluated. The membrane reactor model includes detailed treatments of the catalytic kinetics from the literature, accounts for reaction on the Pd membrane and hydrogen permeation inhibition by site blockage, among other features. The simulations reveal that a maximum in the hydrogen productivity occurs at an intermediate value of the space velocity, implying a trade-off between reactor size, methanol conversion and hydrogen utilization. The assessment involves a determination of the Pd membrane surface to reactor volume ratio that maximizes productivity and the requisite Pd to realize that productivity. We show that MSR on Cu/ZnO and MPOX on Cu are promising reaction systems to practice the membrane concept for fuel processing, whereas direct methanol decomposition is reaction limited, making it infeasible. Several approaches for improving membrane fuel processor performance are evaluated and discussed. We show that oxygen addition can increase the hydrogen productivity in the Pd system, while water addition is beneficial for the MPOX system. The extent of enhancement in both cases depends on supply rate and kinetic factors.     

Thermodynamics of Hydrogen Generation from Methane for Domestic Polymer Electrolyte Fuel Cell Systems

Low temperature fuel cells such as the Polymer Electrolyte Fuel Cell (PEFC) are preferably used for domestic applications because of their moderate operating conditions. Using the existing distribution system, natural gas is used as a source for a hydrogen rich gas to power this fuel cell type. The high requirements on the fuel gas quality as well as high conversion efficiencies for the small local gas processing units are critical aspects in the evaluation of decentralized fuel cell systems. In the present paper, three typical gas processing methods are evaluated for the supply of a hydrogen rich gas for PEFCs: steam reforming, partial oxidation, and autothermic conversion. All three processes are studied in detail by varying the relevant process parameters: temperature, pressure, steam to fuel ratio, and oxygen to fuel ratio. The results are graphically displayed in numerous nomograms. With the help of these graphs, regions of stable operation and the sensitivity to the operational parameters are discussed. For all three gas processing methods, the graphs generated display methane conversion, the hydrogen yield, and the yields of unwanted components, i.e., carbon monoxide and solid carbon. Although only steady‐state operating conditions were simulated, critical modes of operation, which might occur during start‐up or transient operation can easily be identified. For instance, operating conditions where soot is generated have to be avoided under all circumstances. All simulations were done with the Gibb's reactor model of a commercial simulation program. The Gibb's reactor model was found to be a suitable tool, since the simulated results compared well with reported literature data. According to the simulation results, the methane‐steam‐reforming process appears to be favorable for application to PEFCs. Methane conversion and hydrogen yields are highest for this process while the yield of CO is relatively low.