An Experimental Investigation of Hydrogen Production from Biomass

In gaseous products of biomass steam gasification, there exist a lot of CO, CH4 and other hydrocarbons that can be converted to hydrogen through steam reforming reactions. There exists potential hydrogen production from the raw gas of biomass steam gasification. In the present work, the characteristics of hydrogen production from biomass steam gasification were investigated in a small-scale fluidized bed. In these experiments, the gasifying agent (air) was supplied into the reactor from the bottom of the reactor and the steam was added into the reactor above biomass feeding location. The effects of reaction temperature, steam to biomass ratio, equivalence ratio (ER) and biomass particle size on hydrogen yield and hydrogen yield potential were investigated. The experimental results showed that higher reactor temperature, proper ER, proper steam to biomass ratio and smaller biomass particle size will contribute to more hydrogen and potential hydrogen yield.     

SBR工艺除磷过程与种群结构在线监测

For efficient energy consumption and control of effluent quality, the cycle duration for a sequencing batch reactor (SBR) needs to be adjusted by real-time control according to the characteristics and loading of wastewater. In this study, an on-line information system for phosphorus removal processes was established. Based on the analysis for four systems with different ecological community structures and two operation modes, anaerobic-aerobic process and anaerobic-anaerobic process, the characteristic patterns of oxidation-reduction potential (ORP) and pH were related to phosphorous dynamics in the anaerobic, anoxic and aerobic phases, for determination of the end of phosphorous removal. In the operation mode of anaerobic-aerobic process, the pH profile in the anaerobic phase was used to estimate the relative amount of phosphorous accumulating organisms (PAOs) and glycogen accumulating organisms (GAOs), which is beneficial to early detection of ecology community shifts. The on-line sensor values of pH and ORP may be used as the parameters to adjust the duration for phosphorous removal and community shifts to cope with influent variations and maintain appropriate operation conditions.     

Steady-state operation analysis of an ideal heat integrated distillation column

A systematic approach for the steady-state operation analysis of chemical processes is pro-posed.The method affords the possibility of taking operation resilience into consideration during thestage of process design.It may serve the designer as an efficient means for the initial screening ofalternative design schemes.An ideal heat integrated distillation column(HIDiC),without any reboileror condenser attached,is studied throughout this work.It has been found that among the various va-riables concerned with the ideal HIDiC,feed thermal condition appears to be the only factor exertingsignificant influences on the interaction between the top and the bottom control loops.Maximuminteraction is expected when the feed thermal condition approaches 0.5.Total number of stages andheat transfer rate are essential to the system ability of disturbance rejection.Therefore,more stagesand higher heat transfer rate ought to be preferred.But,too many stages and higher heat transfer ratemay increase the load of the compres     

Simulation of hydrocarbons pyrolysis in a fast-mixing reactor

Currently, thermal decomposition of hydrocarbons for the production of basic petrochemicals (ethylene, propyl-ene) is carried out in steam-cracking processes. Aside from the conventional method, under consideration are alternative ways purposed for process intensification. In the context of these activities, the method of high-temperature pyrolysis of hydrocarbons in a heat-carrier flow is studied, which differs from previous ones and is based on the ability of an ultra-short time of feedstock/heat-carrier mixing. This enables to study the pyrolysis process at high temperature (up to 1500 K) at the reactor inlet. A set of model experiments is conducted on the lab scale facility. Liquefied petroleum gas (LPG) and naphtha are used as a feedstock. The detailed data are obtain-ed on temperature and product distributions within a wide range of the residence time. A theoretical model based on the detailed kinetics of the process is developed, too. The effect of governing parameters on the pyrolysis process is analyzed by the results of the simulation and experiments. In particular, the optimal temperature is detected which corresponds to the maximum ethylene yield. Product yields in our experiments are compared with the similar ones in the conventional pyrolysis method. In both cases (LPG and naphtha), ethylene selectivity in the fast-mixing reactor is substantial y higher than in current technology.     

An Investigation of Error Sources in Computational Fluid Dynamics Modelling of a Co-current Spray Dryer

The paper is focused on identifying error sources in computational fluid dynamics(CFD) predictions of a spray drying process. Seven groups of drying and atomisation parameters were selected for analysis and 13 simulation trials were performed. The theoretical results were compared with experimental data and sensitivity of the simulation results to the analysed factors was determined. The following parameters affecting the accuracy of CFD spray modelling were found: gas turbulence model, particle dispersion, atomising air, initial parameters of atomisation and heat losses to the environment. A major difference in the errors committed during modelling of spray drying process for fine and coarse sprays was observed.     

计算流体力学在顺流喷雾干燥器模拟中的误差源研究

The paper is focused on identifying error sources in computational fluid dynamics(CFD) predictions of a spray drying process. Seven groups of drying and atomisation parameters were selected for analysis and 13 simulation trials were performed. The theoretical results were compared with experimental data and sensitivity of the simulation results to the analysed factors was determined. The following parameters affecting the accuracy of CFD spray modelling were found: gas turbulence model, particle dispersion, atomising air, initial parameters of atomisation and heat losses to the environment. A major difference in the errors committed during modelling of spray drying process for fine and coarse sprays was observed.     

Fractal Geometry of Particle Aggregates Formed in Calcium Sulfite Slurry

The solid-liquid separation is an important operation for the regenerated slurry of dual-alkali FGD system, and calcium sulfite could predominate in particle aggregates of the slurry. The settling velocity of calcium sulfite particles is a key parameter for the solid-liquid separation design. However, the settling velocity predicted by Stokes' Law could be suitable only for a spherical aggregate, but not for the irregular one. In this work, fractal geometry was introduced in order to characterize highly irregular geometric shapes. The sizes of calcium sulfite particle aggregates were analyzed using a metallographic phase microscope and image analysis. The results showed that particle aggregates had fractal features. The fractal dimensions could reveal the characteristics of the aggregates' geometry and aggregation process. An exponential relation between the fractal dimension D2 and the particle size l was determined as AμlD2. According to fractal theory, a parameter can be used to modify Stokes settling velocity close to actual settling velocity. The results could be valuable for the design of solid-liquid separation processes.     

基于精细自由基反应机理的丙烷裂解炉炉管CFD模拟(英文)

In the radiant section of cracking furnace, the thermal cracking process is highly coupled with turbulent flow, heat transfer and mass transfer. In this paper, a three-dimensional simulation of propane pyrolysis reactor tube is performed based on a detailed kinetic radical cracking scheme, combined with a comprehensive rigorous computational fluid dynamics（CFD） model. The eddy-dissipation-concept（EDC） model is introduced to deal with turbulence-chemistry interaction of cracking gas, especially for the multi-step radical kinetics. Considering the high aspect ratio and severe gradient phenomenon, numerical strategies such as grid resolution and refinement, stepping method and relaxation technique at different levels are employed to accelerate convergence. Large scale of radial nonuniformity in the vicinity of the tube wall is investigated. Spatial distributions of each radical reaction rate are first studied, and made it possible to identify the dominant elementary reactions. Additionally, a series of operating conditions including the feedstock feed rate, wall temperature profile and heat flux profile towards the reactor tubes are investigated. The obtained results can be used as scientific guide for further technical retrofit and operation optimization aiming at high conversion and selectivity of pyrolysis process.     

基于硫酸钙固体燃料化学链气化过程制备合成气的研究(英文)

Chemical-looping gasification (CLG) is a novel process for syngas generation from solid fuels,sharing the same basic principles as chemical-looping combustion (CLC).It also uses oxygen carriers (mainly metal oxide and calcium sulfate) to transfer heat and oxygen to the fuel.In this paper,the primary investigation into the CLG process with CaSO4 as oxygen carrier was carried out by thermodynamic analysis and experiments in the tube reactor.Sulfur-contained gas emission was mainly H2S rather than SO2 in the CLG process,showing some different features from the CLC.The mass and heat balance of CLG processes were calculated thermodynamically to determinate the auto-thermal operating conditions with different CaSO4/C and steam/C molar ratios.It was found that the CaSO4/C molar ratio should be higher than 0.2 to reach auto-thermal balance.The effect of temperature on the reactions between oxygen carrier and coal was investigated based on Gibbs free energy minimum method and experimental results.It indicated that high temperature favored the CLG process in the fuel reactor and part of syngas was consumed to compensate for auto-thermal system.     

Dimensional modelling of wood pyrolysis using a nodal approach

New gasification installations and techniques are being tested today but they all struggle with mainly the same drawbacks such as removal of various pollutants in the producer gas or clogging of material pathways.This work is oriented on developing a new model for the non-oxidative pyrolysis step of a gasification process as a part of a wider research conducted on the overall gasification of wood waste. A batch reactor is modelled by means of nodal modelling, a technique widely used for simple heat transfer processes. Additionally to the heat transport inside the batch reactor the model uses a simple and versatile generic chemistry and simplified mass transfer principles. Thermal data from modelling is compared with data obtained from an experimental batch pyrolysis reactor using wood sawdust and cutter shavings. Experimental and theoretical results regarding thermal phenomena are in good agreement.     

Characteristics of fast pyrolysis of biomass in a free fall reactor

Fast pyrolysis of four kinds of biomass (legume straw, tobacco stalk, pine sawdust and apricot stone) was conducted in a free fall reactor. Interest is focused on hydrogen-rich gas production. The experimental results verify the occurrence of the in-situ steam reforming of tar, the steam gasification of char and the water–gas shift reaction with the primary pyrolysis of the biomass at higher heating rate in the free fall reactor. These reactions influence greatly the products' distribution and dry gas compositions in fast pyrolysis, especially at higher temperature. The pyrolysis is mass and heat transfer controlled for biomass particle size of above 0.20 mm but kinetically controlled in the case of particle size smaller than 0.20 mm. Biomass composed of higher cellulose and hemicellulose favors hydrogen-rich gas production in fast pyrolysis than that composed of higher lignin. The pyrolysis characteristics of each type of biomass can be explained according to its chemical compositions.     

CFD modelling of the fast pyrolysis of biomass in fluidised bed reactors. Part B: Heat, momentum and mass transport in bubbling fluidised beds

The fluid-particle interaction inside a 150 g/h fluidised bed reactor is modelled. The biomass particle is injected into the fluidised bed and the heat, momentum and mass transport from the fluidising gas and fluidised sand is modelled. The Eulerian approach is used to model the bubbling behaviour of the sand, which is treated as a continuum. Heat transfer from the bubbling bed to the discrete biomass particle, as well as biomass reaction kinetics are modelled according to the literature. The particle motion inside the reactor is computed using drag laws, dependent on the local volume fraction of each phase. FLUENT 6.2 has been used as the modelling framework of the simulations with the whole pyrolysis model incorporated in the form of user-defined function (UDF). The study completes the fast pyrolysis modelling in bubbling fluidised bed reactors.     

Coupling particle scale model and SuperDEM-CFD for multiscale simulation of biomass pyrolysis in a packed bed pyrolyzer

An efficient biomass pyrolysis process requires a comprehensive understanding of the chemical and physical phenomena that occur at multi-length and time scales. In this study, a multiscale computational approach was developed and validated for biomass pyrolysis in a packed-bed reactor by integrating pyrolysis kinetics, a particle scale model, and Superquadric Discrete Element Method-Computational Fluid Dynamics (SuperDEM-CFD) in open-source code MFiX. A one-dimensional particle–scale model that discretizes the characteristic length of biomass particle into layers was developed to predict the intraparticle phenomena inside a single particle. The 1D model was validated by comparing it with a single biomass particle pyrolysis experiment. A recently developed SuperDEM-CFD model was employed to simulate the non-spherical particle–particle contact and fluid-particle interaction. The coupled model was applied to simulate the pyrolysis of cubic biomass particles in a packed bed and validated by comparing with experimental data. Simulation with and without particle–scale model was compared, and the effect of the gas–solid heat transfer models was also investigated.     

Computational modelling of the impact of particle size to the heat transfer coefficient between biomass particles and a fluidised bed

The fluid-particle interaction and the impact of different heat transfer conditions on pyrolysis of biomass inside a 150 g/h fluidised bed reactor are modelled. Two different size biomass particles (350 μm and 550 μm in diameter) are injected into the fluidised bed. The different biomass particle sizes result in different heat transfer conditions. This is due to the fact that the 350 μm diameter particle is smaller than the sand particles of the reactor (440 μm), while the 550 μm one is larger. The bed-to-particle heat transfer for both cases is calculated according to the literature. Conductive heat transfer is assumed for the larger biomass particle (550 μm) inside the bed, while biomass-sand contacts for the smaller biomass particle (350 μm) were considered unimportant. The Eulerian approach is used to model the bubbling behaviour of the sand, which is treated as a continuum. Biomass reaction kinetics is modelled according to the literature using a two-stage, semi-global model which takes into account secondary reactions. The particle motion inside the reactor is computed using drag laws, dependent on the local volume fraction of each phase. FLUENT 6.2 has been used as the modelling framework of the simulations with the whole pyrolysis model incorporated in the form of User Defined Function (UDF).     

Influence of Operating Conditions for Fast Pyrolysis and Pyrolysis Oil Production in a Conical Spouted‐Bed Reactor

Fast pyrolysis experiments of larch sawdust were conducted in a conical spouted‐bed reactor to study the influences of reaction temperature, inlet gas velocity, feeding rate, and particle size on the product yield and pyrolysis oil quality. For the first time, the optimal conditions were determined for various pyrolysis operations of such reactor to increase the yield and quality of pyrolysis oil. The results demonstrate that the biomass particle size, reaction temperature, biomass feeding rate, and inlet gas velocity all affected the quality and yield of the pyrolysis oil, in this order.     

循环流化床作为生物质热解液化反应器的实验研究

总结了固体生物质热解液化装置－一套循环流化床反应器冷态实验的结果。以空气为介质,石英砂为床料,着重考察了循环量与气速、储料量、吹风量、吹风口位置及物料间的关系,得出在一定范围内,循环量随操作气速、Ｌ阀吹风量及储料量的增加而增加;随物料密度、粒径的增大和吹风位置的提高而减小。为热态实验寻找到最佳的操作条件和控制手段。对以木粉为物料的生物质热解油的产率和物性进行了分析。     

云南松热解及其热解产物的研究

采用自制固定床反应器对云南松木粉进行热解,探讨了热解温度、原料颗粒尺寸和氮气流速对云南松热解特性的影响,并采用GC-MS对生物油的组分含量进行分析。结果表明:在热解温度为500 ℃,原料颗粒尺寸为0.250~0.420 mm,氮气流速为150 mL/min条件下,生物油的产率最高为50%,液体组分主要以2,6-二叔丁基对甲酚、2-甲氧基-4-甲基苯酚、异丁香酚、愈创木酚为主,占液体总量的39.24%。     

Evaluation of global biomass devolatilization kinetics in a drop tube reactor with CFD aided experiments

A procedure coupling experimental characterization and computational fluid dynamics (CFD) is developed for providing valuable global kinetic parameters to large applications of biomass fuels (fast pyrolysis, co-combustion and gasification). This is based on an advanced lab-scale apparatus (drop tube reactor), reproducing high heating rates and low residence times at different nominal temperatures (400-800 °C) for particle size of practical interest. Although the relative simplicity of the operation, a detailed and accurate evaluation of the particle residence time and effective thermal history is needed to elaborate suitable global devolatilization kinetics, which differ significantly from low heating rate kinetics (for instance in thermogravimetric balance) and also from those obtained assuming strong hypotheses (e.g. constant particle temperature in the reactor). The developed procedure gives kinetic parameters which are not the intrinsic devolatilization kinetics but global kinetics at high heating rates. These global kinetic parameters are useful to simulate practical systems (characterised by high heating rate) with comprehensive codes (CFD), since detailed particle kinetics require additional sub-models (e.g. of external and internal heat transfer) which may be time consuming and need many data, often known only with uncertainty. In this work CFD is used as both diagnostic and predictive tool; its potentials and drawbacks in aiding advanced experimentation on biomass/coal pyrolysis are discussed.     

生物质快速热解流化床反应器气力进料特性

为探究不同工况下热解流化床反应器的气力进料特性,设计并搭建了流化床反应器气力进料冷态试验装置。生物质原料和床料分别采用落叶松颗粒和石英砂颗粒,通过试验测得了本装置的最小流化速度,研究了流化气速、喷动气速、流量比、初始静床高、石英砂粒径、落叶松粒径对流化床反应器气力进料特性的影响。试验结果表明：流化气速和喷动气速的增加均会提高进料率;流化气使床料流化并为落叶松颗粒提供进料空间,喷动气为落叶松颗粒提供动能,并平衡一部分床层压力;落叶松与石英砂粒径的增加对进料效果不利;流量比在1.9~2.7范围内进料率高且稳定性好。本文构建了生物质、床料与气体的三相流物理及数学模型,开展试验对模型进行验证,结果表明其预测误差为±13%。