光热驱动多孔氧化铈热化学循环解水制氢非热质平衡模型

热化学循环太阳燃料技术过程所涉及的多孔介质中复杂反应及热质传递过程,尚未建立较为完善的数学模型。以多孔氧化铈热化学循环解水过程为研究对象,将颗粒尺度的氧输运与宏观尺度的热质输运相耦合,提出完整的光热驱动条件下多孔介质非热质平衡模型,实验数据对比验证了动力学及热质输运模型的可靠性,分析了两种尺度(颗粒及床层)下,非热平衡效应、入射辐射热流、反应物浓度对动态过程的影响。入射辐射在床层的体积效应下,轴向的温度梯度使得缺陷反应的热力学平衡控制最大氧空位浓度出现在床层前侧,在缺陷反应的动态过程中,氧化过程相较于还原反应更快,提高多孔载氧体反应器的产物H₂浓度应主要从还原阶段中反应过程及条件出发。可为该类问题的建模和过程设计提供较为完整的理论基础和参考路径。     

气固反应多孔填充床反应特性的多尺度模拟

采用孔隙网络方法建立了颗粒堆积多孔填充床内细观孔隙结构、微观气固反应及宏观传输过程交互耦合的多尺度孔道网络数学模型.以铁矿石间接还原反应为例,计算分析了床层孔道结构特征及颗粒孔结构对传递过程和反应特性的影响规律.结果表明,床层孔道结构特征对流动气体浓度分布和固体物料转化程度影响显著,正态分布的孔结构孔径沿气体流动方向降低时,床层各横截面的平均固体转化率最高,与均匀分布的孔结构计算结果的最大相对误差为29.5%;计算粒级分布范围较窄的颗粒物料时,可采用均匀分布孔结构近似代替实际正态分布孔结构.颗粒孔结构变化引起的转化率最大相对误差随反应进行持续增大,固体转化率为0.5时,颗粒两种孔结构分布的最大相对误差达14.6%.     

颗粒直径对吸附分离影响的数值模拟

基于Fluent的多孔介质模型,建立了变压吸附制氧发生器的立式填充床模型。采用用户自定义函数功能,以反映吸附传质、传热,并将多孔介质单相模型整合为更精确的气固两相耦合模型。在此基础上,模拟了吸附颗粒直径对气相压力、速度、床层压降以及氧气分离浓度、回收率等参数的影响情况。结果表明：床层压降随颗粒直径的增大而减小;床层对入口急流的抗穿透性能随颗粒直径的增大而减小;相同条件下,采用较小颗粒直径能够提高氧气分离浓度、回收率,原因在于小颗粒直径降低了床层内气体的流速,增加了吸附时间,促进了吸附的进行。     

化学链燃烧铁基载氧体还原反应积炭趋势

利用热重分析仪对采用机械混合法自行制备的铁基载体还原过程中的积炭现象进行了实验研究。根据实验获得的热重曲线对铁基载氧体的CH₄还原特性进行了分析,实验结果表明,CH₄与铁基载氧体的还原反应过程中存在较为严重的积炭影响,且气体的浓度对反应有较大的影响。通过检测载氧体氧化过程中生成的CO₂量对这种影响进行了定量分析,结果表明积炭随着循环次数的增多而略有下降。XRD和SEM分析结果显示还原反应生成的C部分与载体反应生成Fe₃C,另一部分以碳丝的形式存在于载体表面以及颗粒之间。     

多孔石墨烯基酞菁铁复合物的制备及其电催化氧还原性能研究

利用溶剂热法制备多孔石墨烯,然后超声处理将酞菁铁修饰在多孔石墨烯表面,制备出多孔石墨烯基酞菁铁复合物用于碱性介质氧还原。利用循环伏安法和线性扫描伏安法考察该复合物的催化氧还原的能力,结果显示:多孔石墨烯基酞菁铁复合物修饰电极比多孔石墨烯修饰电极表现出更正的还原电位,具有更高的催化活性。     

真空变压吸附制氧径向流吸附器的流动特性模拟

真空变压吸附制氧是一个复杂的动态过程,深入了解真空变压吸附制氧过程中吸附器内的流动特性是吸附器设计与完善的基础。基于Fluent中的多孔介质模型,通过用户自定义函数功能,建立了真空变压吸附制氧用径向流吸附器的二维轴对称模型,研究了真空变压吸附首次和第二次循环中径向流吸附器的流动特性,对比分析了吸附剂颗粒直径、流道截面积比和流道多孔板开孔率对吸附器流动特性的影响。结果表明,中心流道和外流道空间体积均会影响吸附器的流场分布和制氧效率,在设计径向流吸附器时需要兼顾内外流道空间体积的影响;减小吸附剂颗粒直径能改善吸附器气体分布状况,提高氧气分离浓度和回收率;增大中心流道与外流道截面积比有利于提升床层气体均布效果;中心流道和外流道多孔板开孔率减小均有利于降低床层径向速度不均匀性,中心流道多孔板开孔率的影响比外流道更大。     

MTP固定床反应器床层-颗粒双尺度耦合数学模型

针对甲醇制丙烯(MTP)体系反应快,内扩散影响显著的特点,考察了催化剂颗粒大小对反应的影响,提出了床层-颗粒双尺度耦合模型。模型同时考虑了床层及颗粒内的流动、热量和物质传递、以及化学反应在不同尺度上的物理化学过程,较好反映了整个反应器床层不同位置处催化剂粒径对反应结果的影响规律。模拟结果表明,反应器的进料端甲醇浓度高,反应速率快,适合选用小尺寸催化剂颗粒,以减少内扩散的限制;而在反应器床层的中后段,大颗粒催化剂对提高丙烯的选择性更有利。据此提出了MTP反应器不同尺寸颗粒的催化剂组合填充方式。     

REV尺度多孔介质格子Boltzmann方法的数学模型及应用的研究进展

综述了多孔介质表征体元尺度(REV)格子Boltzmann模型的研究进展,根据对多孔介质处理方式主要分为部分反弹模型和阻力模型两类,分析归纳了各类模型的优缺点。由于阻力模型中渗流的广义格子Boltzmann方程(GLBE)的作用力是基于GUO等的作用力模型,可以准确得到宏观方程,不存在离散误差,且模型的平衡分布函数和作用力项中都包含反应介质特性的孔隙率,因而应用最为广泛。本文还重点介绍了REV尺度多孔介质LBE模型在流动、传热、传质、化学反应及相变等过程中的具体应用,认为REV尺度多孔介质内的三传一反数学模型中需要加入孔隙尺度因素,在更大工程尺度上应该考虑过程参数的各向异性,展望了REV尺度多孔介质LBE模型的发展和应用前景。     

制氢CB-5型低变催化剂还原技术刍议

介绍了CB-5型低变催化剂的理化性质和还原原理,总结了12 000 m3/h制氢装置低变催化剂CB-5的还原过程和技术要点。结果表明,以99.8%的循环氮气作载体,选择99.9%的氢气作为还原介质,依靠配氢阀门开度控制氢气浓度,将反应器入口温度控制在170℃左右,还原过程中反应器床层温度最高不超过230℃,且床层温度变化平稳。     

水泥熟料换热模型的研究

针对高温水泥熟料具有堆积颗粒多孔质特性,将多孔介质渗流换热理论引入到熟料换热研究中,并考虑到热弥散效应对多孔介质强化换热的影响,建立了适用于高温水泥熟料冷却过程的气-固换热三维物理数学模型,在满足工程精度要求前提下,简化为更易求解和适于工业应用的一维非稳态换热模型.同时对其解法进行了相关研究,并通过模拟仿真验证了所建物理数学模型的正确性.     

非热平衡多孔介质内反应与传热传质耦合过程

采用局部热不平衡假设,对发生强吸热化学反应的多孔介质体系建立了反应与传热、传质耦合问题的数学模型,采用Ergun-Forchheimer-Brinkman方程描述多孔介质中的流体流动.运用交替方向隐式(ADI)方法对模型离散求解,并采用文献中的实验数据对模型进行验证.计算了不同条件下颗粒物料层内气体和固体骨架的温度场、产物气体浓度场以及固体转化率分布,以得到多孔介质体系内固有化学反应时的传热、传质规律.结果表明,不能忽略固体骨架与流体间的温度差.入口渗流速度、入口气体温度以及固体颗粒尺寸是影响系统反应特性的重要参数.研究结果对具有强吸热反应的固定床反应器的设计和运行具有一定的参考作用.     

Heat and mass transfer in granular potash fertilizer with a surface dissolution reaction

Potash is a widely used granular fertilizer and when exposed to high humidities it readily adsorbs water vapour forming a liquid electrolyte solution on each particle. Heat and mass transfer due to air flow through granular potash beds is studied experimentally and numerically. A one dimensional experimental setup is used to measure the temperature and air humidity response and mass gain of a potash bed subjected to a change in air flow. A porous media mathematical model is developed to predict the transient temperature and moisture content distributions. The processes are modelled as nonequilibrium heat and mass transfers between the porous solid and air flow gaseous phases. The state of the surface electrolyte solution is modelled by the thermodynamics of electrolyte solutions. Experimental and numerical results show non‐equilibrium internal moisture and heat transfer processes exist with significant differences in the pore air and particle temperature and surface relative humidity.     

移动颗粒床中高温气体渗流传热数值计算

针对移动颗粒床中物料层内的高温气体渗流传热现象 ,考虑渗流与传热的相互作用 ,采用局部非热平衡假设建立了多孔介质渗流传热物理数学模型并进行了数值计算 .研究了不同情况下床内填充多孔介质中的流速、气固温度和床层压力损失 .计算结果表明 ,高温热气对移动床颗粒料层的热渗透主要发生在渗流入口端区域 ,增大入口渗流速度以及减小床层物料下移速度将导致物料温度沿床高慢速下降 ,热渗透深度扩大 ,热渗透作用区域内的物料温度水平提高 .在热渗透作用区域 ,孔隙率对流场和压力损失有很大的影响 .研究结果对于移动颗粒床反应器的设计与运行具有一定的参考作用     

Melting of a Semitransparent Bed of Particles by Convection and Radiation

A theoretical model has been developed to study heating and melting of porous media comprised of semitransparent particles. The heating and melting phases are treated by two different models. Heat transfer by conduction and radiation in the bed of particles is approximated using the effective thermal conductivity concept. The melt is assumed to accumulate at the top of the unmelted bed and not to run off after the melting has started. Radiative transfer in the one-dimensional melt layer is treated rigorously, and the spectral nature of radiation is accounted for. The convective and radiative heating of the bed and the melt layer are treated parametrically. The results of calculations for different bed thicknesses are reported, and sensitivity studies involving the heat transfer coefficient, surroundings temperature, porosity, and particle diameter are presented and discussed.     

Modelling wood combustion under fixed bed conditions

A computer model describing the conversion of wood under packed-bed conditions is presented. The packed bed is considered to be an arrangement of a finite number of particles, typically sized between 5 and 25 mm, with a void space left between them. Each particle is undergoing a thermal conversion process, which is described by a one-dimensional and transient model.Within the single-particle model, heating, drying, pyrolysis, gasification and combustion are considered, whereby each particle exchanges energy due to conduction and radiation with its neighbours. Because of the one-dimensional discretization of the particles, heat transfer and mass transfer is taken into account explicitly. Therefore, no macrokinetic data are needed within the model. For ease of implementation and access, kinetic data and property data are stored in a database. The global conversion of the packed bed is represented by the contributions of single particles, where each particle is coupled to the surrounding gas phase by heat and mass transfer. For gas phase flow through the porous bed, the conservation equations for mass, momentum and energy are solved on a Cartesian mesh by a Finite Volume method.Experiments have been performed to validate the single particle model for the conversion of beech wood during pyrolysis and char combustion. Agreement between experimental and predictions obtained by the model is very satisfactory. However, for wet wood, changes in structure seem to enhance the heat transfer to the solid which is not yet covered in the model.     

Analysis of solar‐driven gasification of biochar trickling through an interconnected porous structure

The efficient transfer of high‐temperature solar heat to the reaction site is crucial for the yield and selectivity of the solar‐driven gasification of biomass. The performance of a gas‐solid trickle‐bed reactor constructed from a high thermal conductivity porous ceramic packing has been investigated. Beech char particles were used as the model feedstock. A two‐dimensional finite‐volume model coupling chemical reaction with conduction, convection, and radiation of heat within the packing was developed and tested against measured temperatures and gasification rates. The sensitivity of the gasification rate and reactor temperatures to variations of the packing's pore diameter, porosity, thermal conductivity, and particle loading was numerically studied. A numerical comparison with a moving bed projected a more uniform temperature distribution and higher gasification rates due to the increased heat transfer via combined radiation and conduction through the trickle bed. © 2014 American Institute of Chemical Engineers AIChE J, 61: 867–879, 2015     

A Quasi‐Steady State Shell and Shrinking Core Approach to the Drying of Porous Particles and an Example of Parameter Identification

A quasi‐steady state shell and shrinking core approach which recognizes heat and mass transfer resistances in both the gas and particle phases for drying of a porous particle is proposed. A mean field model (constant properties) using this approach was embedded in a spreadsheet combined with a genetic algorithm for parameter identification to provide an easy means of characterizing the drying process from drying data. In drying, assuming a mean field, four major parameters are typically unknown: two related to the process (heat and mass transfer coefficients) and two which incorporate porous particle properties (shell thermal conductivity and vapour diffusivity). It is shown how these four parameters may be determined from experimental drying data. The model was applied to data for spouted bed drying of rice. For the particular case studied, external heat transfer was found to be the controlling mode, although resistance to moisture diffusion within the particle is important. The approach presented admits of future refinements to improve its scope and utility.