Dynamics and control of autothermal reactors for the production of hydrogen

Autothermal reactors, coupling endothermic and exothermic reactions in parallel channels, represent one of the most promising technologies for hydrogen production. The bulk of existing research work concerning their operation refers, however, to steady state conditions. In the present work, the dynamic behavior of autothermal reactors is analyzed. It is demonstrated that such systems are modeled by systems of equations that are stiff, their dynamics consequently featuring two time scales. Within the framework of singular perturbations, reduced-order, nonstiff models are derived for the transient evolution in each time scale. Furthermore, the challenges posed by the transient operation of autothermal reactors are identified, along with demonstrating the implementation of feedback control in order to improve transient performance and to avoid severe issues (such as reactor extinction) that can arise in the course of operating the reactor. All theoretical concepts are illustrated with numerical simulations performed using the model of a hydrogen production reactor.     

Modelling and simulation of a coal gasification process in pressurized fluidized bed

A coal gasification mathematical model that can predict temperature, converted fraction and particle size distribution for solids have been developed for a high pressure fluidized bed. For gases in both emulsion and bubble phase, it can predict temperature profiles, gas composition, velocities and other fluid-dynamic parameters. In the feed zone, it could be considered a Gaussian distribution or any other distribution for the solid particle size. Experimental data from literature have been used to validate the model. Finally, the model can be used to optimize the gasification process changing several parameters, such as excess of air, particle size distribution, coal type and reactor geometry.     

Thermal sintering studies of an autothermal reforming catalyst

This paper describes a novel approach to life studies on catalysts used in non-isothermal reactors, using a single long-term experiment. Temperature dependence of catalyst aging is determined by comparing the activity reduction of portions of the catalyst from different sections of the reactor, subjected to different temperatures. Time dependence is determined by fitting the drift in catalyst temperatures to a time-dependent reaction rate via a thermodynamic reactor model. Experimentally, a monolithic autothermal reforming catalyst was subjected to thermally accelerated aging under reforming conditions in an adiabatic laboratory mini-flow reactor for 1000 h. Methane was used as the fuel. The axial temperature profile of the catalyst was monitored using thermocouples placed at various locations along the catalyst. A gradual change in temperature profile, with increasing temperatures due to decreasing steam-reforming activity, was observed. The aged monolith was cut up into short pieces centered on the thermocouple locations. The pieces, each aged at a different temperature due to its location, were tested individually for activity. The reduced activities were correlated with the aging temperature to obtain the temperature dependence of thermal sintering rates. A generalized power-law equation (GPLE) model for sintering was fit to the activity data. A plug flow reactor (PFR) model describing the reaction was built and the sintering kinetics were incorporated. The PFR model was used to predict changes in catalyst performance due to sintering under normal operating conditions. Thermal sintering deactivation for this catalyst was found to be within acceptable limits for commercial applications.     

Synthesis of model-based controllers for an autothermal reactor

Model-based controllers for a bench scale autothermal tubular packed-bed reactor have been formulated using the Internal Model Control (IMC) approach. The Structural Dominance Analysis technique has been used in developing the reduced-order models. Controller performance at robust and sensitive steady states have been assessed through simulations and experiments. Both PI and model-based controllers can regulate reactor operation at robust steady states, but only third order IMC controllers are able to regulate reactor operation at the sensitive steady state.     

Model‐based optimization of hydrogen generation by methane steam reforming in autothermal packed‐bed membrane reformer

An autothermal membrane reformer comprising two separated compartments, a methane oxidation catalytic bed and a methane steam reforming bed, which hosts hydrogen separation membranes, is optimized for hydrogen production by steam reforming of methane to power a polymer electrolyte membrane fuel cell (PEMFC) stack. Capitalizing on recent experimental demonstrations of hydrogen production in such a reactor, we develop here an appropriate model, validate it with experimental data and then use it for the hydrogen generation optimization in terms of the reformer efficiency and power output. The optimized reformer, with adequate hydrogen separation area, optimized exothermic‐to‐endothermic feed ratio and reduced heat losses, is shown to be capable to fuel kW‐range PEMFC stacks, with a methane‐to‐hydrogen conversion efficiency of up to 0.8. This is expected to provide an overall methane‐to‐electric power efficiency of a combined reformer‐fuel cell unit of ～0.5. Recycling of steam reforming effluent to the oxidation bed for combustion of unreacted and unseparated compounds is expected to provide an additional efficiency gain. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Operation of an industrial steam reformer under severe condition: A simulation study

A rigorous two‐dimensional model is developed for simulating the operation of a less‐investigated type steam reformer having a considerably lower operating Reynolds number, higher tube diameter, and non‐availability of extra steam in the feed compared with conventional steam reformers. Simulation results show that reasonable predictions can only be achieved when certain correlations for wall to fluid heat transfer equations are applied. In all cases, strong radial temperature gradients inside the reformer tubes have been found. Furthermore, the results show how a certain catalyst loading profile will affect the operation of the reformer.     

Machine learning-assisted multiscale modeling of an autothermal fixed-bed reactor for methanol to propylene process

The current commercial multistage reactor for methanol to propylene (MTP) process suffers from poor propylene selectivity and catalyst efficiency, mainly because of the low inlet methanol concentration and long residence time. In this work, we proposed an autothermal co-current flow reactor for MTP process, where the reaction heat is continuously removed through heat exchange with cold reactants, thus single-stage reactor can be used with higher methanol inlet concentration. The reactor feasibility was investigated by a three-dimensional multiscale model, in which the diffusion–reaction interaction inside catalyst particle was described by a neural network model trained by machine learning. With the feeding methanol fraction increasing to 30%, propylene selectivity reaches 82.27% while the space velocity approaches 2.68 g_MeOH g_cat⁻¹ h⁻¹ at 99.97% methanol conversion, about 1.4 and 3.8 times those of a commercial multibed reactor, respectively. With proper catalyst bed dilution, the reaction temperature is well controlled between 700 and 754 K.     

Characterization and optimization of an autothermal diesel and jet fuel reformer for 5 kWe mobile fuel cell applications

The present paper describes the characterization of an autothermal reformer designed to generate hydrogen by autothermal reforming (ATR) from commercial diesel fuel (～10 ppm S) and jet fuel (～200 ppm S) for a 5 kW_e polymer electrolyte fuel cell (PEFC). Commercial noble metal-based catalysts supported on 900 cpsi cordierite monoliths substrates were used for ATR with reproducible results. Parameters investigated in this study were the variation of the fuel inlet temperature, fuel flow and the H₂O/C and O₂/C ratios. Temperature profiles were studied both in the axial and radial directions of the reformer. Product gas composition was analyzed using gas chromatography.It was concluded from the experiments that an elevated fuel inlet temperature (≥60 °C) and a higher degree of fuel dispersion, generated via a single-fluid pressurized-swirl nozzle at high fuel flow, significantly improved the performance of the reformer. Complete fuel conversion, a reforming efficiency of 81% and an H₂ selectivity of 96% were established for ATR of diesel at P = 5 kW_e, H₂O/C = 2.5, O₂/C = 0.49 and a fuel inlet temperature of 60 °C. No hot-spot formation and negligible coke formation were observed in the reactor at these operating conditions. The reforming of jet fuel resulted in a reforming efficiency of only 42%. A plausible cause is the coke deposition, originating from the aromatics present in the fuel, and the adsorption of S-compounds on the active sites of the reforming catalyst.Our results indicate possibilities for the developed catalytic reformer to be used in mobile fuel cell applications for energy-efficient hydrogen production from diesel fuel.     

煤等离子气化反应器优化模拟

介绍了煤等离子气化的工艺过程及煤等离子气化反应器装置的结构形式,建立了等离子体反应器的热流场计算流体力学模型,将此模型应用于单入口、双入口及带保护气的双入口等离子反应器模拟,采用不完全乔勒斯基共轭梯度法对热流体耦合场进行求解。结果表明,采用双入口结构,可提高反应器负荷,在等离子反应器的等离子入口周边设置保护气可降低壁面结焦,当保护气的入口流速为70 m/s左右时,效果较好。     

Numerical simulation of elastic recovery for uncured rubber compound with a multi-mode Simhambhatla-Leonov model

Transient squeeze flow and recovery experiments are simulated for a rubber compound. The rheological behaviour of the selected compound is described with a multi-mode Leonov model developed for filled uncured elastomers. The calculation is performed with the finite element software POLYFLOW. In particular, we focus on the deformation undergone under the application of a load, and on the subsequent recovery that develop upon cessation of the squeezing force. We also try to establish a possible empirical relationship between the applied squeeze force and time interval (input data) and the resulting deformation and recovery (output quantities).     

自热制氢反应器研究进展

介绍了同心圆式反应器、板式反应器、壁反应器、微通道反应器在自热重整反应制氢中的特点。同心圆式反应器的传热是控制步骤,为强化传热而开发了空间形状不同和流体经过反应器不同腔体的先后顺序不同的反应器;板式反应器易于组装、拆卸和放大,而且热效率也比较高,是目前十分活跃的研究领域,重点在于操作参数和设计的优化及其高效壁载制氢催化剂的研制;壁反应器的反应表面和换热表面不分离,具有较高的热量耦合效果;微通道反应器具有优越的传热性能,但对加工和流体的性质有比较苛刻的要求。另外,不同燃料制氢机理的研究及其过程参数的稳态、瞬态模拟,为反应器的设计提供了理论依据。而制氢过程并行单元的研究为系统的集成奠定了基础。最后,指出开发板式壁反应器以及开展其在CO变换、净化方面的研究有较好的发展前景。     

Transient operation of a catalytic liquid-liquid plug flow reactor for kinetics measurements

A centrifugal partition chromatograph (CPC) was used as a liquid-liquid catalytic reactor for the isomerisation of hexen-3-ol into ethylpropylketone with a water soluble rhodium catalyst. Global mass transfer coefficients were measured and shown to depend on both the nature of the solute and the flow rate. Liquid-liquid partition isotherms were also determined with the CPC using elution chromatography. Finally, a reactor model was derived to account for the experimental results obtained both under stationary and transient (pulse) conditions. A parameter sensitivity evaluation is also presented.     

焦炉煤气制合成气反应器数值模拟

采用CFD软件F luent模拟计算焦炉煤气(COG)非催化局部氧化制合成气反应器,其中湍流模型选择标准k-ε模型,热辐射选择P-1模型,用非预混模型计算化学输运和反应。反应器内组分与温度场的数值模拟结果与实验测定结果基本吻合,说明模拟结果是可信的。通过模拟可预测,当氧气与焦炉煤气进气体积比达到0.14左右时,可以获得最好的焦炉煤气的转化效果。本数值模拟可为COG非催化局部氧化制合成气进一步的工程研究与应用提供可靠的理论参考依据。     

Dynamic behavior of a continuous autothermal isobutylene polymerization reactor

Industrial autothermal cationic isobutylene polymerization reactors may present very complex dynamic behavior and difficult operation. A mathemathical model was developed to describe the operation of an autothermal solution industrial reactor, and some possible sources of complex dynamical behavior were analyzed. The results obtained indicate that the most probable source of the complex behavior observed industrially is the existence of adventitious impurities in the feeed stream. The effects caused by the presence of adventitious impurities on process operation and product properties were investigated for both polymerization and oligomerization. In the first case, impurities influence the reactor productivity but do not change the polymer quality. In the oligomerization, both the polymer quality and the reactor productivity are seriously affected by the existence of impurities in the feed stream. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1403–1413, 1997     

基于双组分PDF模型的GSP气化炉数值模拟

GSP气化炉是国内最近引进的西门子公司开发的粉煤气化技术,由于对其炉膛内气固反应流动特性认识不足,运行中出现耐火砖烧穿、合成气含灰过高等问题。利用数值模拟方法,采用双组分PDF模型耦合湍流-化学反应、随机轨道法耦合湍流-颗粒运动,针对GSP气化炉内多相反应流场建立三维数值模型。计算结果与实验值及文献计算结果一致,表明该模型可用于GSP气化炉的模拟计算。研究发现,炉膛内流场主要分为旋转射流区、内回流区、外回流区和管流区。高温区位于发生氧化反应的旋转射流区和内回流区上部,而外回流区和管流区主要发生还原反应,温度较为均匀;炉膛高度1/3位置处为高温火焰直接冲刷处,在运行时需重点考虑该位置的热防护。     

Modelling of packed bed membrane reactors for autothermal production of ultrapure hydrogen

The conceptual feasibility of a packed bed membrane reactor for the autothermal reforming (ATR) of methane for the production of ultrapure hydrogen was investigated. By integrating H₂ permselective Pd-based membranes under autothermal conditions, a high degree of process integration and intensification can be accomplished which is particularly interesting for small scale H₂ production units. A two-dimensional pseudo-homogeneous packed bed membrane reactor model was developed that solves the continuity and momentum equations and the component mass and energy balances. In adiabatic operation, autothermal operation can be achieved; however, large axial temperature excursions were seen at the reactor inlet, which are disadvantageous for membrane life and catalyst performance. Different operation modes, such as cooling the reactor wall with sweep gas or distributive feeding of O₂ along the reactor length to moderate the temperature profile, are evaluated. The concentration polarisation because of the selective hydrogen removal along the membrane length was found to become significant with increasing membrane permeability thereby constraining the reactor design. To decrease the negative effects of mass transfer limitations to the membrane wall, a small membrane tube diameter needs to be selected. For a relatively small ratio of the membrane tube diameter to the particle diameter, the porosity profile needs to be taken into account to prevent overestimation of the H₂ removal rate. It is concluded that autothermal production of H₂ in a PBMR is feasible, provided that the membranes are positioned outside the inlet region with large temperature gradients.     

Domain evolution and phase transition dynamics of BaTiO3 ferroelectric single crystal under high pressure with various loading methods: Phase field simulation

The microstructure and macroscopic properties of ferroelectric materials at high pressure are of great interest in both the engineering and scientific arenas. The effect ofthe pressure value, loading time (the time taken for the pressure to increase from atmospheric pressure to the highest pressure) and loading direction on the evolution of domains and the ferroelectric phase transition for a BaTiO₃ single crystal was investigated using a phase field approach. It was found that under symmetrical compression loading the pressure loading time affected the phase transition path and rate but did not affect the phase transition pressure or the ultimate stable phase. For example, at room temperature, even when the loading time increased from 1 ns to 10 μs, the phase transition pressure remained stable at 2.1 GPa, but the phase transition time was prolonged. At −70 °C the orthorhombic–cubic phase transition was induced when the loading pressure was 5 GPa and the loading time was 1 ns, whereas the orthorhombic–tetragonal–cubic phase transition occurred when the loading time increased to 10 μs. In addition, it was found that the application of symmetrical pressure tended to reduce the degree of ferroelectricity, while one-dimensional compression favored the ferroelectric phase.     

MODELING OF THE TRANSIENT AND STEADY STATE OPERATION OF A FLUIDIZED BED REACTOR WITH ADAPTIVE CONTROL OF TEMPERATURE

This paper concerns modeling of the transient and the steady state operation of a fluidized bed reactor for the catalytic ammoxidation of propylene to acrylonitrile. To maintain constant the temperature of the reaction in order to facilitate the phenomenological study as well as to avoid risks of destruction of the catalyst, a self tuning P.I.D. controller has been used. The controller derived from a discrete P.I.D. regulator is based on pole assignment. It uses a recursive parameter estimator based on the least square method. The reactor has been interfaced with an Apple II micro-computer. The results obtained illustrates the inherent capability of self adaptive control to adapt the change of the environment where conventional control fails

Modeling of the reactor is based on the Kato and Wen bubble assemblage model corrected by including the wake of the bubbles with their clouds, as proposed hy Stergiou. This modified model gives good predictions of the operation of the reactor for steady as well as transient operation.     

数学模拟硬质沥青气化的气体成分

对于一个日产１０００吨合成氨装置，原料使用硬质沥青与某一比例的渣油．在德士古炉中气化．通过模拟计算得出气体成分，并预测工艺条件改变时的最佳操作条件。