Use of Pd membranes in catalytic reactors for steam methane reforming for pure hydrogen production

This review analyzes publications on experimental studies and mathematical modeling in the field of development of a catalytic reformer (mainly, steam methane conversion) with a fixed catalytic bed. The specific feature of such a reformer is its integration with a Pd membrane for the purpose of producing high-purity hydrogen to power a low-temperature fuel cell battery.     

FLOX® Steam Reforming for PEM Fuel Cell Systems

Primary energy savings and CO₂ reduction is one of the key motivations for the use of fuel cell systems in the energy sector. A benchmark of domestic cogeneration by PEMFC with existing large scale power production systems such as combined steam‐gas turbine cycle, clearly reveals that only fuel cell systems optimising overall energy efficiency (> 85%) and electrical efficiencies (> 35%) show significant primary energy savings, about 10%, compared with the best competing technology. In this context, fuel processing technology plays a dominant role. A comparison of autothermal and steam reforming concepts in a PEMFC system shows inherent advantages in terms of efficiency at low complexity for the latter. The main reason for this is that steam reforming allows for the straightforward and effective use of the anode‐off gas energy in the reformer burner. Consequently, practical electrical system efficiencies over 40% seem to be achievable, most likely by steam reformers. FLOX®‐steam reforming technology has reached a high state of maturity, offering diverse advantages including: compact design, stable anode off‐gas usage, high efficiency, as well as simple control behaviour. Scaling of the concept is straightforward and offers an opportunity for efficient adaptation to smaller (1 kW) and larger (50 kW) units.     

Simulation of autothermal reforming in a staged‐separation membrane reactor for pure hydrogen production

Steam methane reforming with oxygen input is simulated in staged‐separation membrane reactors. The configuration retains the advantage of regular membrane reactors for achieving super‐equilibrium conversion, but reaction and membrane separation are carried out in two separate units. Equilibrium is assumed in the models given the excess of catalyst. The optimal pure hydrogen yield is obtained with 55% of the total membrane area allocated to the first of two modules. The performance of the process with pure oxygen input is only marginally better than with air. Oxygen must be added in split mode to reach autothermal operation for both reformer modules, and the oxygen input to each module depends on the process conditions. The effects of temperature, steam‐to‐carbon ratio and pressure of the reformer and the area of the membrane modules are investigated for various conditions. Compared with a traditional reformer with an ex situ membrane purifier downstream, the staged reactor is capable of much better pure hydrogen yield for the same autothermal reforming operating conditions.     

固定式质子交换膜燃料电池的天然气重整制氢

介绍了固定式质子交换膜燃料电池用氢气的各种天然气重整方法,其中包括水蒸气重整法、自热重整法和化学闭合燃烧法。同时简述了氢气进一步纯化的水煤气变换反应、选择氧化、变压吸附和气体膜分离脱一氧化碳的方法。通过上述重整和提纯的处理,最终能制备出满足固定式质子交换膜燃料电池要求的氢气。     

A Multi‐Function Compact Micro‐Channel Reactor Coated with Sulphur Tolerant Catalyst for LPG Steam Reforming

Hydrogen fuelled polymer electrolyte fuel cells (PEFC) offer clear environmental benefits. Lack of viable hydrogen infrastructure in the near future means that a key issue is availability of hydrogen at the point of use. Liquefied petroleum gas (LPG) offers advantages as a fuel over other hydrocarbons because there is already an infrastructure in place for remote areas. Hydrogen supply via steam reforming of LPG is therefore a feasible avenue of achieving the environmental benefits. Commercial grade LPG unavoidably contain sulphur as an odorant, the sulphur needs to be removed from the fuel stream before it reaches the reformer catalyst and fuel cell. Utilizing sulphur tolerant catalysts in the reformer leads to a simpler fuel processor design. Thermal management and reforming efficiency has been a challenge for the sulphur tolerant catalysts. In this paper, a multi‐function compact micro‐channel reactor designed for hydrocarbon steam reforming was evaluated for use with LPG. A sulphur tolerant catalyst was wash‐coated on to the reforming layers. The reformer was tested over a wide range of reactor temperatures, steam to carbon ratios and fuel flow rates. Over 60% of H₂ composition can be achieved at high reforming temperatures with a LPG supply rate of 0.75 dm³ min⁻¹ (STP) and a S/C ratio of 4.     

Performance Research on a Methane Compact Reformer Integrated with Catalytic Combustion

A multichannel reformer integrated with catalytic combustion was investigated for methane steam reforming to produce hydrogen. In this system, the main portion of the required heat was supplied by methane oxidation in the catalytic combustor located on two sides of the reformer. In the compact multichannel reactor, the methane conversion rate is high enough compared to the equilibrium values at different temperatures. The performance of the multichannel reformer was investigated under various operating conditions, such as the reformer temperature and the feed stream ratios in both the reformer and the catalytic combustor. The best feed flow rate ratio of reforming to combustion ranged from 1.3 to 1.5, with > 95 % methane conversion. It is anticipated that this multichannel reformer can generate enough hydrogen for a 30‐W fuel cell system, due to its small volume.     

Current Status of and Recent Developments in the Direct Methanol Fuel Cell

The direct methanol fuel cell (DMFC) has been discussed recently as an interesting option for a fuel‐cell‐based mobile power supply system in the power range from a few watts to several hundred kilowatts. In contrast to the favoured hydrogen‐fed fuel cell systems (e.g. the polymer electrolyte membrane fuel cell, PEMFC), the DMFC has some significant advantages. It uses a fuel which is, compared to hydrogen, easy to handle and to distribute. It also comprises a fairly simple system design compared to systems utilising liquid fuels (like methanol) to produce hydrogen from them by steam reforming or partial oxidation to finally feed a standard PEMFC. Nevertheless, many severe problems still exist for the DMFC, hindering its competitiveness as an option to hydrogen‐fed fuel cells. This work reviews the major research activities concerned with the DMFC by highlighting the problems (slow kinetics of the anodic methanol oxidation, methanol permeation through the membrane, carbon dioxide evolution at the anode) and their possible solutions. Special attention is devoted to the steady state and dynamic simulation of these fuel cell systems.     

A dynamic model of the fuel processor for a residential PEM fuel cell energy system

A dynamic numerical model describing an experimental methane fuel processor for a residential PEMFC energy system is presented. In contrast to previous simulation studies of steam reforming of methane, this model includes the various energetic couplings due to spatial proximity and constructive layout of the components. Thus, all significant energy flows inside the system are taken into account, including those caused by unintended conduction and radiation. Steady-state simulations were carried out to investigate the effect of a constructional modification in the reformer, which clearly reveal the significant influence of thermal couplings on the reformer efficiency. Furthermore, dynamic simulations were performed for the start-up procedure of the fuel processor and compared to experimental data. The results demonstrate that the dynamic model is a useful tool for further investigations of unsteady operating conditions and for optimisation with respect to both construction and system operation.     

Enhancing the Efficiency of SOFC‐Based Auxiliary Power Units by Intermediate Methanation

Fuel‐cell‐based auxiliary power units benefit from the high power density and fuel flexibility of solid oxide fuel cells (SOFCs), facilitating straightforward onboard fuel processing of diesel or jet fuel. The preferred method of producing the fuel gas is autothermal reforming, which to date has shown the best practical applicability. However, the resulting reformate is poor in methane, so that cell cooling is not supported by internal methane steam reforming. Accordingly, large flow rates of excess air are required to cool the stack. Hence, the power demand of the cathode air blower significantly limits the net electrical power output of the system and large cathode flow channels are required. The present work examines attempts to further increase the system efficiency in middle‐distillate‐fueled SOFC systems by decreasing the cathode air flow rates. The proposed concept is generally based on inducing endothermic methane steam reforming (MSR) inside the cells by augmenting the methane content in an upstream methanation step. Methanation, however, can only yield significant methane production rates if the reaction temperature is limited. Therefore, four process layouts are presented that include different cooling measures. Based on these setups, the general feasibility and the benefit of intermediate methanation are demonstrated.     

Kinetic simulation of a compact reactor system for hydrogen production by steam reforming of higher hydrocarbons

A bubbling fluidized bed membrane reactor for steam reforming of higher hydrocarbons is modelled, using n‐heptane as a model component to represent steam reforming of naphtha. The reformer is modelled as a bubbling fluidized bed reactor, consisting of two pseudo phases, a dense phase and a bubble phase, both in plug flow. In situ H₂ permselective membranes remove H₂ continuously as a pure product, greatly enhancing the H₂ yield per mole of heptane fed. A fluidized bed membrane reformer for higher hydrocarbons could give a very compact reactor system combining all the units from the pre‐reformer to the hydrogen purification system in a traditional steam reforming plant into a single unit.     

Enhancement of Hydrogen Production by Fluidization in Industrial-Scale Steam Reformers

In this paper, the effect of the fluidization concept on the performance of methane steam reforming has been investigated by comparing a fluidized-bed steam reformer (FBSR) with an industrial-scale conventional steam reformer (CSR). Also, a fluidized-bed thermally coupled steam reformer (TCFBSR) and a fixed-bed thermally coupled steam reformer (TCSR) have been compared. In thermally coupled reactors, the hydrogenation of nitrobenzene to aniline exothermic reaction is employed. A steady state one dimensional heterogeneous model is applied to analyze methane conversion and hydrogen production for steam reforming of methane in different reactors (CSR, FBSR, TCSR, and TCFBSR). The modeling results show that, in FBSR, hydrogen production and methane conversion are increased by 2.13 and 0.52%, respectively, in comparison with CSR. Also, by using fluidized catalysts instead of fixed ones in TCSR, methane conversion and hydrogen yield are increased from 0.2776 to 0.2934 and from 0.9649 to 0.9836, respectively. These improvements represent the appropriate effect of the fluidization concept on the enhancement of hydrogen production in different steam reformers.     

电解重整式甲醇燃料电池系统

为解决直接甲醇燃料电池中甲醇氧化活性低及甲醇穿透问题,提出一种新型的电解重整式甲醇燃料电池系统。在系统中,高温电解重整器重整甲醇为常温燃料电池供氢,燃料电池的部分电能供给电解重整器使用。通过对系统的物料流、焓流、有效能流的分析,确定了系统中的不可逆因素。结果表明:电解重整器电压是影响系统效率的重要参数;升高重整器温度可以显著降低其电压,但必须采用合理的压力、甲醇溶液浓度以抑制甲醇溶液的蒸发,降低热量损失。与传统的直接甲醇燃料电池系统以及高温甲醇热重整联合质子交换膜燃料电池系统相比,该系统性能较高、结构紧凑。     

Advances on methane steam reforming to produce hydrogen through membrane reactors technology: A review

Methane steam reforming is the most common industrial process used for almost the 50% of the world’s hydrogen production. Commonly, this reaction is performed in fixed bed reactors and several stages are needed for separating hydrogen with the desired purity. The membrane reactors represent a valid alternative to the fixed bed reactors, by combining the reforming reaction for producing hydrogen and its separation in only one stage. This article deals with the recent progress on methane steam reforming reaction, giving a short overview on catalysts utilization as well as on the fundamentals of membrane reactors, also summarizing the relevant advancements in this field.     

Sorption enhanced steam reforming (SESR): a direct route towards efficient hydrogen production from biomass‐derived compounds

OVERVIEW: Efficient conversion of biomass to hydrogen is imperative in order to realize sustainable hydrogen production. Sorption enhanced steam reforming (SESR) is an emerging technology to produce high purity hydrogen directly from biomass‐derived oxygenates, by integrating steam reforming, water‐gas shift and CO₂ separation in one‐stage. Factors such as simplicity of the hydrogen production process, flexibility in feedstock, high hydrogen yield and low cost, make the SESR process attractive for biomass conversion to fuels. IMPACT: Recent work has demonstrated that SESR of biomass‐derived oxygenates has greater potential than conventional steam reforming for hydrogen production. The flexibility of SESR processes resides in the diversity of feedstocks, which can be gases (e.g. biogas, syngas from biomass gasification), liquids (e.g. bioethanol, glycerol, sugars or liquid wastes from biomass processing) and solids (e.g. lignocellulosic biomass). SESR can be developed to realize a simple biomass conversion process but with high energy efficiency. APPLICATIONS: Hydrogen production by SESR of biomass‐derived compounds can be integrated into existing oil refineries and bio‐refineries for hydrotreating processing, making the production of gasoline and diesel greener. Moreover, hydrogen from SESR can be directly fed to fuel cells for power generation. Copyright © 2012 Society of Chemical Industry     

A dual functional staged hydrogen purifier for an integrated fuel processor–fuel cell power system

This paper describes the operation of a dual functional, membrane/catalytic CO_x methanator, hydrogen purifier that is well-suited for an integrated fuel processor/fuel cell power system. In combination with a pressure swing reformer (PSR) and a PEMFC, the system provides high overall efficiency and portability for distributed power or onboard vehicle use. Gas testing results illustrate the ability of the purifier to produce fuel cell purity hydrogen at peak power flux. The durability of this purifier is shown by its ability to meet target hydrogen purity even with a membrane that permeates >3000 ppm CO. Gas purge streams from both fuel cell electrodes are combined with the membrane retentate and combusted in the PSR combustion cycle to provide heat for the reforming reaction leading to high thermal efficiency. Most significantly, it is shown that staging of this purifier, enables recovery of some fraction of the purified hydrogen at pressures substantially approaching that of the feed hydrogen partial pressure. This creates an onboard source of high pressure hydrogen to be optionally fed to a storage device for use during vehicle startup, or to the fuel cell, either directly or via the storage device, under high power load conditions. The beneficial impact of this two-stage, dual functional purifier on membrane cost, dependability and fuel processor/fuel cell integration, will be discussed.     

Low-level CO in hydrogen-rich gas supplied by a methanol processor for PEMFCs

The present study developed a low-CO methanol processor for the online supply of hydrogen to a proton exchange membrane fuel cell (PEMFC) composed of a steam reformer, a catalytic combustor and a reactor for the removal of CO. Commercial Cu/ZnO/Al₂O₃- and Pt/Al₂O₃-based catalysts were used in the methanol steam reforming and the preferential oxidation (PROX) reactor, respectively. The steam reformer was successfully heated with a catalytic combustor at room temperature without any additional electrical power supply. Hydrogen gas was obtained at a flow rate of 43.0 L h⁻¹ using a feed flow rate of 39.5 ml h⁻¹ (S/C=1.1) and an operation temperature of 250 °C, corresponding to a power output of 59 W_e. The CO concentration could be maintained at 4–5 ppm for stable operation.     

二甲醚水蒸气重整制氢催化剂的研究进展

高品质氢气的在线稳定供给是质子交换膜燃料电池（PEMFC）商业化的瓶颈和亟待解决的关键问题,以二甲醚为原料经水蒸气重整制取氢气是近中期最为现实和有效的氢源供给方案之一。本文总结和评述了近期二甲醚水蒸气重整制氢催化剂的研究进展,主要集中在固体酸催化剂中氧化铝和HZSM-5分子筛酸强度、酸类型以及结构的调变对性能的影响,同时对金属催化剂特别是Pd基贵金属催化剂和Zn基催化剂的研究现状、整体式催化剂以及催化剂的失活与再生的相关研究进行了重点介绍。根据对相关研究结果的总结,提出今后该领域的重要研究方向为：开发新型In₂O₃催化剂;构建具有多级孔、纳米结构的催化剂体系;创制具有特殊结构的催化剂（以多级孔分子筛/氧化铝为核,连续无缺陷的金属催化剂为壳）。     

Biofuels as a promising source of hydrogen for fuel cell power plants

The state of the art in biomass conversion into liquid hydrocarbon biofuels aimed at obtaining synthesis gas and hydrogen for duel elements is analyzed. The most promising liquid hydrocarbon and oxygencontaining fuels for synthesis gas production are vegetable oils, diesel fuel, and biodiesel. Mathematical models are developed for the autothermal reforming, steam reforming and pre-reforming of biodiesel into synthesis gas and for the steam reforming of pre-reforming products integrated with the membrane separation of hydrogen. The results of calculations are verified against experimental data. The solution suggested here ensures 93.5% efficiency of the membrane separation of hydrogen from the reaction mixture and a theoretical hydrogen yield of 128 mol per kilogram of biodiesel.     

Sorbent-enhanced/membrane-assisted steam-methane reforming

Thermodynamic equilibrium and kinetic reactor models are used to simulate a fluidized bed membrane reactor with in situ or ex situ hydrogen and/or CO₂ removal for production of pure hydrogen by steam methane reforming. In the equilibrium model, the membranes and CO₂ removal are located in separate vessels downstream of the reformer. As the recycle ratio increases, the overall performance approaches that where membranes are located inside the reactor. Whether located in situ or ex situ, hydrogen removal by membranes and CO₂ capture by sorbents both enhance hydrogen production. In the kinetic reactor model, a circulating fluidized bed membrane reformer is coupled with a catalyst/sorbent regenerator. Sorbent enhancement combined with membranes could provide very high hydrogen yields. In addition, since carbonation is exothermic, with its heat of reaction similar in magnitude to the endothermic heat of reaction of the net reforming reactions, sorbent enhancement can provide much of the heat needed in the reformer. The overall heat needed for the process would then be provided in a separate calciner, acting as a sorbent regenerator. While the technology is promising, several practical issues need to be examined.     

Multi‐fuel scaled‐down autothermal pure H2 generator: Design and proof of concept

This article presents experimental results of an autothermal scaled‐down system for H₂ production. Pure atmospheric pressure H₂, separated in situ by Pd–Ag membranes, is produced by steam reforming (SR) of methane, ethanol, or glycerol. Oxidizing the SR effluents in a separate compartment supplies the heat. The oxidation feed is axially distributed to avoid hotspots. The 1.3 L system, comprises 100 cm² of membrane area, and generates H₂ flow rate equivalent to 0.15 kW at an efficiency of ～25%. This process leads to comparable performance when different fuels are used. A mathematical model, validated by the measurements, predicts that increasing the membrane area relative to the outer surface area will substantially increase the efficiency and power output. This design serves as proof of concept for on‐board pure H₂ generators, with flexible fuel sources, and holds a great promise to reduce the need for special H₂ transport and storage technologies for portable or stationary applications. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2112–2125, 2016