微型流化床中萘裂解生成小分子气体的反应动力学研究

气化是煤、生物质以及其他含碳燃料高值化利用的有效途径之一。为了考察气化过程中焦油的反应转化特性,选取萘作为焦油模型化合物,以流化催化裂化（fluid catalytic cracking,FCC）催化剂及褐煤热解焦作为接触裂解载体,利用微型流化床考察流化条件下萘催化裂解反应规律,并采用Friedman法和积分法计算萘裂解生成CH₄和H₂等典型气体组分的动力学参数。结果表明,FCC催化剂与褐煤焦均对萘裂解有明显的催化效果,褐煤焦用于萘裂解的反应活化能整体数值低于FCC催化剂。FCC催化剂裂解萘生成H₂符合三维扩散（球形对称）模型,生成CH₄符合成核与生长（n=2/3）模型。相应地,褐煤焦裂解萘反应生成H₂和CH₄分别采用收缩几何形状（圆柱形对称）和三维扩散（圆柱形对称）具有较好的拟合度。     

Voidage profiles in magnetically fluidized beds

Voidage profiles in a fluidized bed of iron particles (230 μm) were investigated under the influence of an external uniform axial magnetic field. Passing a direct current through five solenoids generated uniform magnetic field. The five solenoids were arranged elaborately to get larger uniform magnetic space than that generated by Helmholtz electromagnet coils. A sensitive optical measuring system, based on detection of light reflected by particles, was used to measure local voidage in both dense and dilute phases.

Local voidage was measured as a function of superficial fluidizing air velocity, magnetic field intensity and the position in the bed. At a given magnetic field intensity and at the same position in the bed, the voidage was constant for a low air velocity range (in a fixed bed). The local voidage changed irregularly with increasing air velocity for an intermediate air velocity range (in a magnetically stabilized fluidized bed, MSFB). The local voidage changed linearly with increasing air velocity for a slightly high air velocity range (in a magnetized bubbling fluidized bed, MBFB). A general correlation was developed to predict the local solids fraction at the arbitrary position in the bed: (1−)=(1−)_c+[(1−)_w−(1−)_c](r/R)^B where (1−), (1−)_c and (1−)_w represent the local solids fraction at arbitrary position in the bed, at the bed center and on the bed wall; and B, (1−)_c and (1−)_w are the function of air velocity, distance from the distributor and magnetic field intensity.     

Experimental study of sawdust and coal particle mixing in sand or catalyst fluidized beds

This paper presents an experimental study in order to establish mixing and segregation conditions of wood sawdust and coal particles in a fluidized bed of sand or alumina particles. Experiments were performed at room temperature under atmospheric pressure. Simple equipment was used to divide the bed into layers and useful results could be obtained in a short period of time. The influence of fluidization velocity, time of an experiment, size and concentration of sawdust or coal particles was investigated. Uniformity of mixing was found to increase with an increase in the fluidization velocity. For u/u_mf less than 2.5, strong segregation occurred between sawdust and sand particles. Determination of good mixing conditions will be useful in gasification studies of sawdust and coal.     

Devolatilization of large coal particles in fluidized beds

Analysis of devolatilization of predried large coal particles in fluidized beds requires consideration of both the chemical kinetics of coal decomposition and transport processes. Models available either assume the devolatilization particle to be isothermal (whereas it may be shown that, in general, large temperature gradients may exist within the particle) or require extensive numerical integration procedures. This Paper describes a model which permits formulation of analytical and easy-to-use equations for the estimation of the devolatilization history of a large predried coal particle in a fluidized bed. The model predictions are compared with experimental data collected for Mississippi lignite. A correlation is proposed for the estimation of the total devolatilization time. The analytical solutions presented may be used with ease in coupling the devolatilization process to the other phenomena, such as drying and/or combustion of volatiles and residual char, occuring during fluidized bed combustion of coal.     

Secondary coking and cracking of shale oil vapours from pyrolysis or hydropyrolysis of a Kentucky Cleveland oil shale in a two-stage reactor

It is widely recognized that secondary reactions which are mainly associated with minerals during oil shale retorting have a marked influence on the product yields and compositions. To understand these phenomena more clearly, the secondary reactions of shale oil vapours from the pyrolysis (or hydropyrolysis) of Kentucky Cleveland oil shale were examined in a two-stage, fixed-bed reactor in flowing nitrogen or hydrogen at pressures of 0.1–15 MPa. The vapours from pyrolysis (first stage) were passed through a second stage containing combusted shale, upgrading catalyst or neither. Carbon conversion to volatile products in the first stage increased from 49% during thermal pyrolysis to 81% at 15 MPa H₂ partial pressure. During thermal pyrolysis, total pressure had only a slight effect on carbon removal from the raw shale and subsequent deposition on to the porous solids in the second stage. Carbon deposition on to the combusted shale in the second stage was reduced to zero at 15 MPa H₂ partial pressure. The n-alkane distributions of the oils as determined by gas chromatography clearly demonstrated that higher hydrogen pressure, contact with combusted shale, or both contributed to lower-molecular-weight products.     

Attrition and abrasion models for oil shale process modelling

As oil shale is processed, fine particles, much smaller than the original shale, are created. This process is called attrition or, more accurately, abrasion. In this paper, models of abrasion are presented for oil shale processed in several unit operations. Two of these unit operations, a fluidized bed and a lift pipe, are used in the Lawrence Livermore National Laboratory hot recycle solid (HRS) process being developed for the above-ground processing of oil shale. Abrasion occurs so commonly in the handling and processing of paniculate materials that numerous studies have been conducted to characterize the phenomenon and to attempt to minimize it. In the review of the literature, materials which have been studied for attrition potential are examined, as are the specific unit operations for which either experimental or modelling studies have been conducted. Several papers are discussed in which attrition in fluidized beds or lift pipes is addressed. In this paper, empirical models are derived for the processes occurring in the HRS process from the experimental studies conducted on oil shale. The derived models are presented, as are comparisons with experimental results.     

The behaviour of segregating fluidized beds and its relevance to ash management

Visual observation of the movement of particles across a transparent, drilled plate distributor allowed their directional and RMS velocities to be determined. Particles too big and/or dense to be lifted by bubble wakes are moved towards collection zones by the circulating bed material. The minimum fluidizing velocity has to be exceeded by an amount which increases with increasing density and/or number of particles before there is significant transport. Direct and RMS velocities increase linearly with the gas velocity. Circulation is controllable by producing imbalance in the air supplies to different zones of the distributor; tilting the distributor (flow is then up the slope); or use of a spout as a pump. Spouts can remix large/dense particles back into the bulk of the bed. Particles can be selectively withdrawn through a pneumatic off-take tube.     

Hydrodynamic characteristics of magnetically stabilized fluidized admixture beds of iron and copper particles

Hydrodynamic characteristics of fluidized beds of pure iron (1416 μm), copper (934 μ) and their admixture (25, 50 and 75 mass %) particles when exposed to a uniform magnetic field collinear with the gas flow are investigated. Bed pressure-drop data taken as a function of increasing and decreasing gas velocities (up to about 8 m/s) for different values of magnetic-field intensity over a wide range (0 to 17 272 A/m) are employed to determine the superficial minimum bubbling and fluidization gas velocities at ambient temperature and pressure. The minimum bubbling velocity is found to increase with an increase in the value of the magnetic-field intensity, as well as with the mass fraction of magnetizable particles in the bed. These data are correlated with an empirical relation, as well as with a semi-theoretical expression. The bed voidage data are also generated and analyzed, as also the bed quality fluidization in terms of interparticle magnetic forces. These hydrodynamic properties of magnetically stabilized fluidized-bed reactors are useful in their design and operation for a variety of chemical and biochemical applications.     

Prediction of heat transfer to liquid-solid fluidized beds

Heat transfer coefficients to a liquid-solid fluidized bed in a cylindrical tube have been measured using water as liquid phase and three types of cylindrical steel particles, as well as glass, nickel, copper and lead spheres of different sizes as solid phase. The independent varaibles included heat flux, liquid velocity and particle physical properties. The experimental results as well as a data bank containing a large number of measured heat transfer coefficients for solid-liquid fluidization over a wide range of operational parameters have been compared with the predictions of most published correlations. A model for the prediction of heat transfer coefficients is proposed which predicts the present experimental data and the data of other investigators with good accuracy.     

Solids motion and holdup profiles in liquid fluidized beds

Non-invasive gamma rays-based techniques, computer tomography and computer-aided radioactive particle tracking, were used to measure solid holdup and solid velocity profiles in liquid-solid fluidized beds. The time averaged velocity measurements indicated that multiple circulation cells exist in the column. The solid motion was upward in the center and downward near the walls in the fully developed part of the column. The flow pattern is reversed in the entry region of the column. The solid holdup values increase slightly with the increase in radial position in the fully developed region. The average values of holdup in the column were in agreement with other measurements and with the modified Richardson-Zaki equation. The solids mean velocities and eddy diffusivities increase with increase in liquid superficial velocity, column size, particle size and density. Distributor-type affects the mean velocity and turbulence parameters while the column height has a relatively minor effect. The solids motion and turbulence parameters presented here are useful for validation of CFD models.     

鼓泡流化床离散模拟中的一个局部空隙率模型

气固流化床离散颗粒模拟中通常采用面积加权平均法计算局部空隙率,不能较好地反映流化床中显著的非均匀结构特性.为了考虑非均匀结构对局部空隙率的影响,文中提出一个适用鼓泡流化床的局部空隙率模型.将流场划分为稀区(气泡区)和密区(乳相区);非均匀结构对密区局部空隙率的影响通过引入局部空隙率下限和非均匀影响系数描述;将提升管流动...     

温度对循环流化床双床气化中热解炉产物的影响

在循环流化床双床煤高温热解气化试验台上,以神木烟煤为燃料在不同温度下进行了热解气化试验,该试验台利用上下返料器将热解炉和气化炉耦合在一起,其中热解炉为N2气氛,气化炉通入空气作为气化剂,试验主要研究热解炉底部温度对热解煤气及热解炉底渣的影响。试验结果表明:随热解炉底部温度升高,热解煤气中H2体积分数升高,CH4,CO2体积分数降低,CO体积分数先降低后升高,热解煤气主要组分气体的收率增加。试验所取热解炉底渣样品的孔比表面积分布和孔比体积分布主要集中于中小孔(0—50 nm),其总比表面积和总孔体积大小顺序为在817℃最大,844℃次之,766℃最小,在N2气氛、1 200℃条件下,CO2反应的活性大小顺序为817℃最大,766℃次之,844℃最小。     

Particle scale study of heat transfer in packed and bubbling fluidized beds

The approach of combined discrete particle simulation (DPS) and computational fluid dynamics (CFD), which has been increasingly applied to the modeling of particle‐fluid flow, is extended to study particle‐particle and particle‐fluid heat transfer in packed and bubbling fluidized beds at an individual particle scale. The development of this model is described first, involving three heat transfer mechanisms: fluid‐particle convection, particle‐particle conduction and particle radiation. The model is then validated by comparing the predicted results with those measured in the literature in terms of bed effective thermal conductivity and individual particle heat transfer characteristics. The contribution of each of the three heat transfer mechanisms is quantified and analyzed. The results confirm that under certain conditions, individual particle heat transfer coefficient (HTC) can be constant in a fluidized bed, independent of gas superficial velocities. However, the relationship between HTC and gas superficial velocity varies with flow conditions and material properties such as thermal conductivities. The effectiveness and possible limitation of the hot sphere approach recently used in the experimental studies of heat transfer in fluidized beds are discussed. The results show that the proposed model offers an effective method to elucidate the mechanisms governing the heat transfer in packed and bubbling fluidized beds at a particle scale. The need for further development in this area is also discussed. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

Geometrical and hydrodynamical study of gas jets in packed and fluidized beds using magnetic resonance

Magnetic resonance (MR) was used to image the motion of particles and gas just above the distributor of 3D beds of particles fluidized by air. Three different distributors were used: (i) a single‐orifice distributor, with orifice diameters 1.0–4.0 mm, (ii) a plate, drilled with a triangular array of 79 holes, each of 0.35 mm diameter, with a central nozzle containing a single hole of diameter 1.0, 2.5, or 9.0 mm, (iii) distributors with two or three orifices and diameters of 1.0 or 2.5 mm. It proved possible to extract geometrical information, such as the length of a jet, from MR images, each averaged over ～5 min. Also, light was shed on the question of why is there such a discrepancy between reported jet‐lengths. The fluidization state, the “start‐up” procedure and also the number of holes all play a significant role in determining the measured distance a jet penetrates into a bed. The question as to whether the observed voids represent permanent jets or streams of bubbles was considered. The evidence from ultra‐fast MR measurements strongly suggests that only the lower part of a jet from an orifice in a multi‐orifice distributor is permanent; bubbles form at the top of the jet. Consequently, the top of each jet is transient. However, most of the jet from a single orifice is a permanent cavity when the bed of particles is not fluidized. The length of a jet was successfully correlated with operating variables using dimensional analysis. Finally, the flow of particles around a single jet was measured with high resolution MR.     

Novel technologies of VOC decontamination in fixed,moving and fluidized catalyst-adsorbent beds

Some findings are reported on theoretical and experimental research studies of mechanical, structural, physical and chemical properties, micro-and macrokinetic adsorptive, catalytic and regenerative characteristics of heterogeneous alumina catalyst-adsorbents used for decontamination of individual volatile organic compounds (VOC) and their multicomponent mixtures. Data on fluid dynamics, heat and mass transfer in fixed, gravity-moving and fluidized beds in novel energy-saving (i) adsorptive, (ii) adsorptive-catalytic, (iii) thermocatalytic with a quasistationary fluidized and (iiii) with a fixed catalyst beds and deep intercyclic heat recovery of purification systems are obtained and discussed. Correlations are suggested to calculate a number of investigated parameters, and the schematics and operating principles of these technologies are described.     

Wall-to-bed heat transfer in three-phase fluidized beds of low density particles

Bed-to-wall heat transfer was measured in three-phase fluidized beds under conditions typical of biochemical process applications. The thermal resistance of the fluidized bed, which was significant in the absence of gas, became negligible when gas was introduced. Decreasing the particle density at constant gas and liquid velocity increased the bed-to-wall heat transfer coefficient. Previously published heat transfer correlations were used and gave poor predictions of our data. A new correlation was developed which predicted very well all the heat transfer coefficient results in this paper.     

Circulating fluidized bed combustion of pitches derived from heavy oil upgrading

Combustion trials were conducted with two pitch materials in the University of British Columbia pilot scale (152 mm × 152 mm × 7.3 m) circulating fluidized bed combustion unit. The pitches, which were bottom end by-products of heavy oil upgrading processes containing high concentrations of sulphur, heavy metals and asphaltenes, were fed to the combustor in liquid form and atomized in the combustion chamber. Limestone was fed also to capture sulphur in situ. The combustion efficiency was always above 99%. NO_x emissions increased as the Ca:S ratio increased. The heavy metal elements present in the pitch were found to remain essentially in the solid residue.     

基于气固流态化原理的油页岩干燥动力学

为了考察气固流化床干燥器能否使油页岩含水质量分数达到要求,以柳树河油页岩颗粒为原料,研究进口气体温度和颗粒直径对油页岩干燥性能的影响,采用薄层干燥模型,对油页岩干燥实验数据进行模拟,确定油页岩干燥方程和干燥速率方程,建立油页岩干燥速率特征常数和有效扩散系数之间的关联式。研究结果表明:薄层干燥模型中修正Page模型Ⅰ适合描述油页岩的干燥过程;油页岩在流化床内干燥过程主要发生在降速干燥阶段,进口气体温度越高,油页岩颗粒直径越小,所需干燥时间越短,进口气体温度为350℃时,使2.4 mm油页岩含水质量分数低于5%,所需干燥时间为2.5 min。     

Modelling the kinetics of fast catalytic cracking reactions

Instantaneous kinetic constants and gasoline selectivities have been determined for catalytic cracking of n-hexadecane. The pulse technique was used in order to model the sequential build-up of coke which occurs on cracking catalyst within a riser transport-line reactor. The total amount of hydrocarbon injected per unit weight of catalyst was between 0 and 10. The mathematical model used to analyze the data was based on the unsteady state mass balance of the microcatalytic reactor with the assumption of plug flow. Results suggest a fast deactivation process during the run with fresh catalyst, while regenerated catalyst showed a slower deactivation. The catalyst regenerated three times evidenced a low apparent activation energy when temperature was increased from 500°C to 550°C.