Analysis of parameter effects on transport phenomena in conjunction with chemical reactions in ducts relevant for methane reformers

Various transport phenomena in conjunction with chemical reactions are strongly affected by reformer configurations and properties of involved porous catalyst layers. The considered composite duct is relevant for a methane steam reformer and consists of a porous layer for the catalytic chemical reactions, the fuel gas flow duct and solid plate. In this paper, a fully three-dimensional calculation method is developed to simulate and analyze reforming reactions of methane, with purpose to reveal the importance of design and operating parameters grouped as three characteristic ratios. The reformer conditions such as mass balances associated with the reforming reactions and gas permeation to/from the porous catalyst reforming layer are applied in the analysis. The results show that the characteristic ratios have significant effects on the transport phenomena and overall reforming reaction performance.     

On reaction coupled transport phenomenon in reformer ducts

In compact steam reformer the probability of component degradation and failure depends strongly on the local temperature gradients coupled by various transport processes and chemical reactions in multi-functional materials. In this paper, the modeling and analysis of coupled mass transport and heat transfer processes are conducted for compact design steam reformer duct, which consists of a porous layer for the reforming reactions of methane, the fuel gas flow duct and solid plate. A fully three-dimensional computational fluid dynamics (CFD) approach is applied to calculate transport processes and effects of thermal conductivities of the involved multi-functional materials on reforming reaction rates and heat transfer/temperature distributions, in terms of surface temperatures/heat fluxes and Nusselt numbers. The steam reformer conditions such as mass balances associated with the chemical reactions and gas permeation to/from the porous layer are implemented in the calculation. The results reveal that a small thermal conductivity of the porous layer and solid plates promote high reforming reaction rates, and the convective heat transfer at the top interface varies more significantly along the main flow reformer duct.     

中温固体氧化物燃料电池阳极通道中气体流动和传热分析

采用三维计算方法模拟和分析内重整反应和电化学反应及其在厚阳极层中对不同输运过程的影响。该文所研究的复合管道包括一个多孔阳极层、流道和金属双极板,利用基于燃料气体混合物的可变热物性参数(例如密度、粘度、比热等)及其耦合源项求解不同气体种类的动量和热量传递方程。模拟结果表明．内重整反应和电化学反应及其操作条件对阳极中的气体输运和热传递过程都有较大影响。     

A numerical analysis of heat and mass transfer processes in a macro-patterned methane/steam reforming reactor

The presented paper focuses on a numerical analysis of a heat and mass transfer process in a novel type of methane/steam reforming reactor. The novelty of the macro-patterned reactor design lies in dividing a reformer into segments of various lengths and reactivity. Precisely, splitting the catalyst and filling the created empty volume with porous, non-reactive, thermal conducting material such as metallic foam. This approach allows for moderating a sharp temperature drop at the inlet of the reactor typical for the endothermic methane/steam reforming process. To analyze the considered system, the mathematical and numerical models of transport phenomena and the reaction kinetics were developed and implemented into an in-house solver. The kinetics of methane/steam reforming was taken from the literature. The outlet composition obtained from the kinetic model was compared with the experimental measurements and good agreement was found. The conducted numerical analysis includes cases that differ from a number and lengths of catalytic and non-catalytic segments. The obtained results indicate that the macro-patterned design is a promising strategy that allows for a significant improvement of temperature distribution in a reforming reactor. It was shown that the proposed approach could help to cut the cost of the catalyst material by allowing for the conversion of methane with a smaller amount of the catalyst close to the reference case.     

Modeling and simulation of methane steam reforming in a thermally coupled membrane reactor

A distributed mathematical model for thermally coupled membrane reactor that is composed of three channels is developed for methane steam reforming. Methane combustion takes place in the first channel on a Pt/δ–Al₂O₃$\text{Pt}/\delta \text{–}{\text{Al}}_2{\text{O}}_3$ catalyst layer that supplies the necessary heat for the endothermic steam reforming reaction. In the second channel, catalytic steam reforming reactions take place in the presence of Ni/MgO–Al₂O₃ catalyst. The combustion catalyst forms a thin layer next to the reactor wall to minimize the heat transfer resistance. Selective permeation of hydrogen through the palladium membrane is achieved either by co-current or counter-current flow of sweep gas through the third channel. The burner is modeled as a monolith reactor and the reformer is assumed to behave as a pseudo-homogenous reactor. The mass and energy balance equations for the thermally coupled membrane reactor form a set of 22 coupled ordinary differential equations. With the application of appropriate boundary conditions, the distributed reactor model for steady-state operation is solved as a boundary value problem. The model equations are discretized using spline collocation on finite elements. The discretized nonlinear modeling equations, along with the boundary conditions, form a system of algebraic equations that are solved using the trust region dogleg method. The performance of the reactor is numerically investigated for various key operating variables such as inlet fuel concentration, inlet steam/methane ratio, inlet reformer gas temperature and inlet reformer gas velocity. Simulations for both the co-current and the countercurrent flow modes are also performed using different sweep gas flow rates. For each case, the reactor performance is analyzed based on methane conversion and hydrogen recovery yield.     

A numerical study of the effectiveness factors of nickel catalyst pellets used in steam methane reforming for residential fuel cell applications

A numerical study is performed to evaluate the effectiveness factors of commercial nickel catalyst pellets commonly used in small-scale steam methane reformers for residential fuel cell applications. Based on the intrinsic reaction kinetics of the steam reforming process, the standard composition of the partially reformed gas mixture is determined as a function of the methane conversion. The heterogeneous reforming reactions inside the spherical catalyst pellets are then modeled by considering the distributed reaction, multi-component diffusion and permeation, and conductive and convective heat transfer in the porous media. Various operating conditions, including the reforming temperature, steam-to-carbon (S/C) ratio, operating pressure, and geometrical parameters, such as the pellet diameter and mean pore size, are simulated. The effectiveness factors calculated for each condition are presented as a function of the methane conversion. Finally, simple correlations for the effectiveness factors are presented, and their accuracies are assessed.     

Thermochemical waste‐heat recuperation by steam methane reforming with flue gas addition

The process flow schematic of fuel‐consuming equipment with thermochemical waste‐heat recuperation by steam methane reforming with an addition of flue gas to the reaction mixture is suggested. The advantages of such a thermochemical recuperation (TCR) system compared with the TCR system by steam methane reforming are shown and justified. Based on the first law energy analysis, the heat inputs and outputs of the TCR system were determined. To determine the exhaust gases heat transformed into chemical energy of a new synthetic fuel, the thermodynamic analysis by minimizing Gibbs energy via Aspen HYSYS was performed. It was found that with an increase in the mole fraction of combustion products in the reaction mixture, the enthalpy of the methane reforming reaction increases, especially noticeable at the temperature range above 1000 K. Based on the heat, balance of the TCR system was established that the addition of combustion products to the reaction mixture has the following effects: reducing the heat input for steam production in a steam generator; reduction of the steam generator size because of the need to produce a smaller amount of steam in comparison with TCR by pure steam methane reforming; and reducing the amount of heat transferred through the wall of the reformer and, as a consequence, reduction in size of the reformer.     

Simultaneous production of two types of synthesis gas by steam and tri‐reforming of methane using an integrated thermally coupled reactor: mathematical modeling

In this work, tri‐reforming and steam reforming processes have been coupled thermally together in a reactor for production of two types of synthesis gases. A multitubular reactor with 184 two‐concentric‐tubes has been proposed for coupling reactions of tri‐reforming and steam reforming of methane. Tri‐reforming reactions occur in outer tube side of the two‐concentric‐tube reactor and generate the needed energy for inner tube side, where steam reforming process is taking place. The cocurrent mode is investigated, and the simulation results of steam reforming side of the reactor are compared with corresponding predictions for thermally coupled steam reformer and also conventional fixed‐bed steam reformer reactor operated at the same feed conditions. This reactor produces two types of syngas with different H₂/CO ratios. Results revealed that H₂/CO ratio at the output of steam and tri‐reforming sides reached to 1.1 and 9.2, respectively. In this configuration, steam reforming reaction is proceeded by excess generated heat from tri‐reforming reaction instead of huge fired‐furnace in conventional steam reformer. Elimination of a low performance fired‐furnace and replacing it with a high performance reactor causes a reduction in full consumption with production of a new type of synthesis gas. The reactor performance is analyzed on the basis of methane conversion and hydrogen yield in both sides and is investigated numerically for various inlet temperature and molar flow rate of tri‐reforming side. A mathematical heterogeneous model is used to simulate both sides of the reactor. The optimum operating parameters for tri‐reforming side in thermally coupled tri‐reformer and steam reformer reactor are methane feed rate and temperature equal to 9264.4 kmol h^?1 and 1100 K, respectively. By increasing the feed flow rate of tri‐reforming side from 28,120 to 140,600 kmol h^?1, methane conversion and H₂ yield at the output of steam reforming side enhanced about 63.4% and 55.2%, respectively. Also by increasing the inlet temperature of tri‐reforming side from 900 to 1300 K, CH₄ conversion and H₂ yield at the output of steam reforming side enhanced about 82.5% and 71.5%, respectively. The results showed that methane conversion at the output of steam and tri‐reforming sides reached to 26.5% and 94%, respectively with the feed temperature of 1100 K of tri‐reforming side. Copyright © 2013 John Wiley & Sons, Ltd.     

Experimental and numerical studies on chemically reacting gas flow in the porous structure of a solid oxide fuel cells internal fuel reformer

This paper presents experimental and numerical studies on the fuel reforming process on an Ni/YSZ catalyst. Nickel is widely known as a catalyst material for Solid Oxide Fuel Cells. Because of its prices and catalytic properties, Ni is used in both electrodes and internal reforming reactors. To optimize the reforming reactors, detailed data about the entire reforming process is required. In the present paper kinetics of methane/steam reforming on the Ni/YSZ catalyst was experimentally investigated. Measurements including different thermal boundary conditions, the fuel flow rate and the steam-to-methane ratios were performed. The reforming rate equation derived from experimental data was used in the numerical model to predict synthetic gas composition at the outlet of the reformer.     

Interactive heat transfer characteristics of 5 kW class shell-and-tube methane steam reformer with intermediate temperature heat source

A 5 kW class shell and tube methane steam reformer (MSR) with intermediate temperature heat source was evaluated to find a correlation between the methane conversion and heat transfer performance. First, performance evaluation of MSR1 was conducted by varying experimental conditions such as reformer reactant flow rate, steam to carbon ratio (SCR), inlet temperature of reforming zone, and inlet temperature of heat source. Sensitivity study of overall heat transfer coefficient was also carried out to find the major parameter affecting the heat transfer. Next, the heat transfer performance and methane conversion rate of MSR1 and 2 were compared. Both reformers have the same gas hourly space velocity (GHSV) in the form of shell and tube heat exchangers, but are designed to compare the heat transfer characteristics of the reformer by designing with the different heat transfer areas. The results show that the main factors affecting the performance of the reformer are load, heat source inlet temperature, and heat transfer area.     

Comparison of compact reformer configurations for on-board fuel processing

Two compact reformer configurations in the context of production of hydrogen in a fuel processing system for use in a Proton Exchange Membrane Fuel Cell (PEMFC) based auxiliary power unit in the 2–3 kW range are compared using computer-based modeling techniques. Hydrogen is produced via catalytic steam reforming of n-heptane, the surrogate for petroleum naphtha. Heat required for this endothermic reaction is supplied via catalytic combustion of methane, the model compound for natural gas. The combination of steam reforming and catalytic combustion is modeled for a microchannel reactor configuration in which reactions and heat transfer take place in parallel, micro-sized flow paths with wall-coated catalysts and for a cascade reactor configuration in which reactions occur in a series of adiabatic packed-beds, heat exchange in interconnecting microchannel heat exchangers being used to maintain the desired temperature. Size and efficiency of the fuel processor consisting of the reformer, hydrogen clean-up units and heat exchange peripherals are estimated for either case of using a microchannel and a cascade configuration in the reforming step. The respective sizes of fuel processors with microchannel and cascade configurations are 1.53 × 10⁻³ and 1.71 × 10⁻³ m³. The overall efficiency of the fuel processor, defined as the ratio of the lower heating value of the hydrogen produced to the lower heating value of the fuel consumed, is 68.2% with the microchannel reactor and 73.5% with the cascade reactor mainly due to 30% lower consumption of n-heptane in the latter. The cascade system also offers advanced temperature control over the reactions and ease of catalyst replacement.     

Simulation of steam reforming of biogas in an industrial reformer for hydrogen production

The paper aims to investigate the steam reforming of biogas in an industrial-scale reformer for hydrogen production. A non-isothermal one dimensional reactor model has been constituted by using mass, momentum and energy balances. The model equations have been solved using MATLAB software. The developed model has been validated with the available modeling studies on industrial steam reforming of methane as well as with the those on lab-scale steam reforming of biogas. It demonstrates excellent agreement with them. Effect of change in biogas compositions on the performance of industrial steam reformer has been investigated in terms of methane conversion, yields of hydrogen and carbon monoxide, product gas compositions, reactor temperature and total pressure. For this, compositions of biogas (CH₄/CO₂ = 40/60 to 80/20), S/C ratio, reformer feed temperature and heat flux have been varied. Preferable feed conditions to the reformer are total molar feed rate of 21 kmol/h, steam to methane ratio of 4.0, temperature of 973 K and pressure of 25 bar. Under these conditions, industrial reformer fed with biogas, provides methane conversion (93.08–85.65%) and hydrogen yield (1.02–2.28), that are close to thermodynamic equilibrium condition.     

Three-dimensional computational analysis of gas and heat transport phenomena in ducts relevant for anode-supported solid oxide fuel cells

Various transport phenomena occurring in an anode duct of medium temperature solid oxide fuel cell (SOFC) have been simulated and analyzed by a fully three-dimensional calculation method. The considered composite duct consists of a thick porous layer, the gas flow duct and solid current interconnector. Unique fuel cell boundary and interfacial conditions, such as the combined thermal boundary conditions on solid walls, mass transfer associated with the electrochemical reaction and gas permeation across the interface, were applied in the analysis. Based on three characteristic ratios proposed in this study, gas flow and heat transfer were investigated and presented in terms of friction factors and Nusselt numbers. It was revealed that, among various parameters, the duct configuration and properties of the porous anode layer have significant effects on both gas flow and heat transfer of anode-supported SOFC ducts. The results from this study can be applied in fuel cell overall modeling methods, such as those considering unit/stack level modeling.     

Autothermal reforming over a Pt/Gd-doped ceria catalyst: Heat and mass transport limitations in the steam reforming section

Autothermal reforming (ATR) has several advantages for fuel cell applications, such as a compact reactor structure and fast response. Using oxidation reactions inside the reactor, ATR does not have the external heat transfer limitations associated with steam reforming. However, mass and heat transfer limitations inside and outside the catalyst particles are still anticipated. In this study, transport limitations in the steam reforming section of ATR over a Pt/Gd-doped ceria catalyst are analyzed by numerical simulations based on a reaction rate equation in which parameters are adjusted to measured kinetic data. The simulation results show that significant transport limitations characterize the steam reforming section of packed-bed ATR reactors. The activity per catalyst bed volume is highly dependent on the particle size, and only the thin exterior layer of the particles is involved in catalyzing the reactions. Based on the results, it is shown that an eggshell type catalyst particle could reduce catalyst material significantly without a considerable decline in the activity per catalyst bed volume.     

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.     

Millisecond methane steam reforming for hydrogen production: A computational fluid dynamics study

The potential of methane steam reforming to produce hydrogen in thermally integrated micro-chemical systems at short contact times was theoretically explored. Methane steam reforming coupled with methane catalytic combustion in microchannel reactors for hydrogen production was studied numerically. A two-dimensional computational fluid dynamics model with detailed chemistry and transport was developed. To provide guidelines for optimal design, reactor behavior was studied, and the effect of design parameters such as catalyst loading, channel height, and flow arrangement was evaluated. To understand how steam reforming can happen at millisecond contact times, the relevant process time scales were analyzed, and a heat and mass transfer analysis was performed. The importance of energy management was also discussed in order to obtain a better understanding of the mechanism responsible for efficient heat exchange between highly exothermic and endothermic reactions. The results demonstrated the feasibility of the design of millisecond reforming systems, but only under certain conditions. To achieve this goal, process intensification through miniaturization and the improvement in catalyst performance is very important, but not sufficient; very careful design and implementation of the system is also necessary to enable high thermal integration. The channel height plays an important role in determining the efficiency of heat exchange. A proper balance of the flow rates of the combustible and reforming streams is an important design criterion. Reactor performance is significantly affected by flow arrangement, and co-current operation is recommended to achieve a good energy balance within the system. The catalyst loading must be carefully designed to avoid insufficient reactant conversion or hot spots. Finally, operating windows were identified, and engineering maps for designing devices with desired power were constructed.     

A novel integrated thermally coupled configuration for methane-steam reforming and hydrogenation of nitrobenzene to aniline

In this work, a novel thermally coupled reactor containing the steam reforming process in the endothermic side and the hydrogenation of nitrobenzene to aniline in the exothermic side has been investigated. In this novel configuration, the conventional steam reforming process has been substituted by the recuperative coupled reactors which contain the steam reforming reactions in the tube side, and the hydrogenation reaction in the shell side. The co-current mode is investigated and the simulation results are compared with corresponding predictions for an industrial fixed-bed steam reformer reactor operated at the same feed conditions. The results show that although synthesis gas productivity is the same as conventional steam reformer reactor, but aniline is also produced as an additional valuable product. Also it does not need to burn at the furnace of steam reformer. The performance of the reactor is numerically investigated for different inlet temperature and molar flow rate of exothermic side. The reactor performance is analyzed based on methane conversion, hydrogen yield and nitrobenzene conversion. The results show that exothermic feed temperature of 1270 K can produce synthesis gas with 26% methane conversion (the same as conventional) and nitrobenzene conversion in the outlet of the reactor is improved to 100%. This new configuration eliminates huge fired furnace with high energy consumption in steam reforming process.     

Heat and mass transfer in a reforming catalyst bed: Analytical prediction of distributions in the catalyst bed

Heat and mass transfer characteristics within a reforming catalyst bed have been analytically investigated. A numerical analysis was carried out in a two‐dimensional steady‐state model of a reforming catalyst bed. The reforming tube was filled with catalyst and the tube wall was uniformly heated; a mixture of steam and methane was reformed through the catalyst bed. The predicted distributions of temperature, formed gas composition, methane conversion rate, and heat transfer coefficient in the catalyst bed are in good agreement with the experimental data. The effects of space velocity, steam carbon molar ratio, and wall temperature on the heat transfer coefficient were analytically presented. From temperature and composition distributions simulated by the two‐dimensional analysis, the effects of the above‐mentioned factors and diffusion on both heat and mass transport phenomena were qualitatively predicted. © 2003 Wiley Periodicals, Inc. Heat Trans Asian Res, 32(4): 367–380, 2003; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/htj.10101     

Exploring the opportunities for carbon capture in modular,small-scale steam methane reforming: An energetic perspective

Small-scale steam methane reforming units produce more than 12% of all the CO₂-equivalent emissions from hydrogen production and, unlike large-scale units, are usually not integrated with other processes. In this article, the authors examine the hitherto under-explored potential to utilise the excess heat available in the small-scale steam methane reforming process for partial carbon dioxide capture. Reforming temperature has been identified as a critical operating parameter to affect the amount of excess heat available in the steam methane reforming process. Calculations suggest that reforming the natural gas at 850 °C, rather than 750 °C, increases the amount of excess heat available by about 28.4% (at 180 °C) while, sacrificing about 1.62% and 1.09% in the thermal and exergetic efficiency of the process, respectively. Preliminary calculations suggest that this heat could potentially be utilised for partial carbon capture from reformer flue gas, via structured adsorbents, in a compact capture unit. The reforming temperature can be adjusted in order to regulate the amount of excess heat, and thus the carbon capture rate.     

Thermodynamic optimization of a reheat chemically recuperated gas turbine

The feasibility of integrating a commercially available reheat gas turbine with a methane steam reformer is analyzed. A slight modification to the original reheat design is proposed to improve the methane conversion rate in the reforming process and, consequently, the efficiency in recovering waste exhaust heat from the gas turbine.Two solutions are proposed for the heat recovery scheme: a first reformer has a single pressure level while the second has two in order to match the different pressures of the combustors. While the single pressure scheme gives good performance with respect to the stand alone gas turbine, the dual pressure reformer can give a further benefit, as far as an accurate optimization of the steam management is performed.