冷态德士古气化炉流场与停留时间分布的研究

测定了德士古气化炉的冷态速度分布和停留时间分布。结果表明：德士古气化炉内在轴向２．５～３．０倍直径范围内存在回流，最大回流量为射流量的３．５倍左右；在平均停留时间之前，已有５０％左右的物料逸出炉外。本文指出，德士古气化炉中存在的问题，如结渣、耐火砖寿命短、有效气体成分偏低均与炉内流场有关。     

两段式气流床煤气化炉内气固流动数值模拟研究

建立了两段式气流床煤气化炉内气固两相流动的三维计算流体力学（CFD）模型，将气体视为连续介质，在Euler坐标系下考察气相的运动；将颗粒视为离散体系，在Lagrange坐标系下研究颗粒的运动。利用所建CFD模型对基本设计尺寸和操作条件下的两段式气流床煤气化炉内气固两相流动进行了模拟，给出了两段式气流床煤气化炉内的气固两相流动的规律和颗粒的分布规律。在此基础上，针对不同的结构(喉口直径变化)和不同的操作条件（两段气固进料量变化）进行了一系列的模拟比较。结果表明，喉口直径的变化对于炉内气固两相流动及颗粒分布有重要影响。随着喉口直径减小，喉口附近区域的气相回流增强，颗粒运动轨线变得更加曲折，颗粒分布发生明显变化。两段气固流量的改变可以明显改变炉内气固流动，随着一段反应区的气固流量增加和二段反应区气固流量减小，一段反应区内的气相回流更加显著， 二段反应区气相回流减弱，颗粒螺旋上升运动增强，反应器边壁处颗粒浓度增大，颗粒沉积现象减弱。     

理想反应器的时空特性和内在联系

以理想反应器时间和空间特性为出发点,探讨了间歇操作釜式反应器(BR)、平推流反应器(PFR)和全混流反应器(CSTR)等理想反应器之间的内在联系,推导了循环操作PFR反应器的停留时间分布函数,分析了多段串联全混流反应器和循环操作PFR反应器在各理想反应器之间的桥梁和纽带作用。在此基础上,简要归纳了各理想反应器之间的联系。     

射流携带床反应器液体停留时间分布及模拟

对射流携带床液体停留时间分布进行了研究，考察了液体流量、气体流量和气体动量对液体停留时间分布的影响。结果表明，增加液体流量使停留时间分布密度曲线变得高而窄，且平均停留时间变短；气体流量增大使得停留时间出峰略有提前，气体流量大于4L/min时，继续增大气体流量对液体停留时间分布影响较小；当液体流量小于60L/h时，气体动量对液体停留时间的影响较明显，主要表现气体动量越大液体平均停留时间越长。基于实验结果分析及实验中观测的现象，将射流携带床内液体流动结构分为中心区和壁面区进行研究，建立了描述射流携带床内液体停留时间分布的数学模型，模型模拟结果和实验数据吻合良好。     

急倾斜煤层地下气化数学模型的研究

煤炭地下气化产气过程与气化炉体的温度分布和渗流条件密切相关。根据急倾斜煤层赋存条件和气化过程的特点，建立了急倾斜煤层地下气化数学模型。介绍了模型参数的确定方法，采用控制容积方法对模型进行了求解，并在模型实验的基础上，对计算结果进行了分析。从温度场分布来看，计算值略高于实测值，各测点相对误差基本均在10%以内。根据模拟计算结果，随着气化通道长度增加，煤气热值提高，但在还原区以后，提高的幅度减小，温度场对煤气热值产生显著影响。由于受温度的影响，在高温区，煤气组分浓度场实测值的变化梯度大于计算值。结果表明，模拟值与实验值能够较好地相吻合，说明对急倾斜煤层地下气化温度场和浓度场的数值模拟是合理的。     

表面活性剂与高分子链混合体系的模拟

计算机模拟了高分子链对表面活性剂胶束形成过程的影响，以及高分子链构象性质随胶束化过程的变化.结果表明,当高分子链与表面活性剂之间的相互作用强度超过临界值后，高分子链的存在有利于表面活性剂胶束的形成.临界聚集浓度（CAC）与临界胶束浓度（CMC）的比值CAC/CMC随高分子链长的增大和相互吸引作用的增强而减小.在CAC之前，高分子链与表面活性剂分子只有动态的聚集；但在CAC之后，表面活性剂胶束随表面活性剂浓度X的增加而增大，并静态地吸附在高分子链上，形成表面活性剂/高分子聚集体.随着表面活性剂分子的加入，高分子链的均方末端距和平均非球形因子先保持恒定；从X略小于CAC开始， 和快速减小，至极小值后又逐渐增大.模拟结果支持高分子链包裹在胶束表面的实验模型.     

烷基芳基磺酸盐结构对微乳液相行为的影响

用Winsor相图法研究了自制的6种不同结构的烷基芳基磺酸盐/不同醇/正癸烷/NaCl/水体系在不同温度下所形成的微乳液。 探讨了烷基芳基磺酸盐结构对微乳液相行为的影响。 同时考察了温度和醇对微乳液相行为的影响。 结果表明,随着烷基芳基磺酸盐长烷基链的增长,中相形成盐度S1、中相消失盐度S2、中相盐宽ΔS和最佳盐浓度S*值均减小,最佳中相体积V*M和最佳增容量σ*值均增大;随着烷基芳基磺酸盐分子的芳环向长烷基链中间位置移动,S1、S2、ΔS、S*值均减小,V*M和σ*值均增大;随着温度升高,V*M和σ*值均减小,S1、S2、ΔS、S*值均增大,在25 ℃时,体系无中相微乳液形成;随着正构醇碳原子数的增加,V*M和σ*值均增大,S1、S2、ΔS、S*值均减小。     

水煤浆气化炉的数学模拟

本文以水煤 浆气化炉气化过程的三区模型为基础，提出了计算气化炉出口煤气组成的混合模型，计算值与工厂测定值吻合良好。以A、M、N三种不同组成的煤为例，预测了煤种、气化压力、氧碳比、水煤浆浓度、热损失等因素对气化结果的影响。模拟结果表明，气化炉热损失显著影响煤气出口温度与级,适宜的氧碳比约为0.88左右，适宜的水煤浆浓度约为65％。     

煤灰矿物质在炉内的迁徙分布规律及其对沾污结渣的影响

在0.25 MW试验炉上进行热态试验，对新汶矿务局黑液水煤浆和常规水煤浆进行对比燃烧试验，从炉膛不同部位的灰渣成分分析炉内的结渣机理。研究了煤中钠、钾、钙、铝、硅、铁等矿物质元素沿烟气行程的分布，着重研究了不同成分对结渣的形成及分布的影响。结果表明，沿火焰行程，煤中各矿物质的分布是不一样的，其中碱金属质量分数炉壁渣比空间颗粒明显减小，呈先减小后增大趋势，炉壁渣的铝质量分数明显超过空间颗粒物，呈先增大后减小趋势，硅则和铝恰恰相反，使得硅铝比先增大后减小，其它各元素的附着机理也有各自的规律，其矿物质元素分布与煤灰熔融性基本一致。     

高分子链构象性质和溶解性的Monte Carlo模拟

运用Monte Carlo方法对线型高分子链格点模型的构象进行了模拟,研究了单链体系的构象的尺寸（采用均方末端距,均方回转半径来表征）、形状（采用平均非球形因子来表征）和溶解性随溶剂与链段间相互作用能的变化情况.结果表明,、和随着εPS的增大而减小,具有相同的变化规律;随着Δε增大,溶剂变得越来越不利于溶解,高分子链的形状蜷曲为椭球形,高分子线团相互穿插交叠.     

气流床煤气化炉内流动、混合与反应过程的研究进展

气流床气化过程涉及高温高压下湍流多相流动与复杂化学反应过程的相互作用,涵盖喷嘴雾化与弥散、复杂多相射流流动、炉内湍流混合、复杂气化反应、火焰结构及温度分布等诸多方面,是世界各国研究的热点.对近年来世界各国在气流床气化过程研究上取得的进展进行了综述,包括喷嘴雾化与颗粒弥散机理与雾化过程的影响因素、撞击流驻点偏移规律和撞击面振荡规律、撞击火焰结构与炉内三维温度场、典型煤种气化反应特性与石油焦气化特性以及气流床气化过程模拟.对气流床气化过程未来的研究重点进行了展望.     

Mean residence time of Markov processes for particle transport in fludized bed reactors

A new approach for studying the particle dynamics and RTD (residence time distribution) in processes is to formulate stochastic models. A common question to all models for RTD is whether Danckwerts’ law for mean residence time holds. In this paper we revisit a Markov process that has been proposed by Dehling et al. (1999) as a stochastic model for particle transport in fluidized bed reactors. Under the volumetric flow balance conditions, we deduce different boundary conditions at the entrance and the exit of the reactor, and in both discrete model and continuous model we show that processes satisfy Danckwerts’ law, stating that the mean residence time of particle transport in fluidized bed reactors equals V/v, where V denotes the volume of the reactor occupied by the fluid and v the volumetric inflow rate.     

Development of an Unsteady-State Model for Control of Polymer Grade Transitions in Ziegler-Natta Catalyzed Reactor Systems

The dynamics of the activity and polymer growth in Ziegler-Natta catalysts has been well established in the literature. 1 , 2 The corresponding dynamic behaviour of the reactor system is predicted using a segregation model approach and the unsteady state model of residence time distribution previously developed. 3 The model is therefore able to predict reactor performance for a time-varying catalyst flow rate through the reactor, as well as time-varying concentrations of monomer, co-catalyst and chain termination agent. A method of determining grade transition policies by the use of the developed reactor models is then presented. It is demonstrated that the reactor productivity, catalyst efficiency, average chain length and polydispersity can be controlled by the catalyst flow rate and reactor monomer and hydrogen concentrations. The relationship between the required polymer product properties and the system flow rates is determined. Case studies are presented that evaluate various transition strategies for a specific polymer grades.     

Free‐Radical Polymerization with Long‐Chain Branching and Scission in a Continuous Stirred‐Tank Reactor

Free‐radical polymerization that involves the polymer transfer reactions leading to both long‐chain branching and scission, as in the cases of high‐pressure olefin polymerization, is considered. In CSTR, the residence time distribution is broad and the primary polymer chain, whose residence time is large, is subjected to polymer transfer reaction for a longer time, leading to a larger number of branching and scission points. The distributions of both branching and scission density are much broader in a CSTR than in a batch, or equivalently, a PFR. The radius of gyration for larger sized polymers formed in a CSTR tends to be much smaller than that for randomly branched polymers.

     

水煤浆气化炉气化过程的三区模型

本文提出了水煤浆气化过程的三区模型，即燃烧区、二次反应区、回流化学反应区。在燃烧 区中，首先进行反应的是回流流股中的可燃组分，其次是煤中的挥发分及碳等；二次反应区主要是燃烧产物的均相或非无相反应；回流区的化学反应则与喷咀结构，射流速度密切相关。各区的反应既不受热力学限制，也不为动力学控制，反应结果完全依赖于喷咀与护体匹配形成的流场；其中回流是一个重要的工程因素，适当的回流量有利于二次反应的进行。     

Extending potential flow modelling of flat-sheet geometries as applied in membrane-based systems

The efficiency of chemical reactors can be analysed using the residence time distribution. This research focusses on flat-sheet geometries applied in membrane-based systems. The residence time distribution depends mainly on the 2D velocity field, parallel to the membrane. The velocity average over the transversal direction is calculated using potential flow theory. A combination of real and virtual sources and sinks are used to model the internal inlets and outlets. Furthermore, a novel method is presented to calculate the residence time distribution. By ignoring diffusion and dispersion, every streamline is modelled to have a fixed residence time, which can be calculated with a simple quadrature based on a coordinate transformation. The model predicts the impact of the two-dimensional geometry on the residence time distribution, but it is demonstrated that large zones of nearly stagnant flow have only a limited impact on the residence time distribution. The new model can predict the travelling time from the inlet to each interior location, providing a better tool to analyse spatially distributed chemical reactions. The models agreed highly with pressure measurements (R² = 0.94–0.98) and they agreed well with tracer experiments for the residence time (R² = 0.73–0.99).     

Residence time distribution and heat/mass transfer performance of a millimeter scale butterfly-shaped reactor

A millimeter scale butterfly-shaped reactor was proposed based on sizing-up strategy and fabricated via femtosecond laser engraving. An improvement of mixing performance and residence time distribution was realized by means of contraction and expansion of the reaction channel. The liquid holdup was greatly increased through connection of multiple mixing units. Structure optimization of the reactor was carried out by computational fluid dynamics simulation, from which the effect of reactor internals on mixing and the influence of parallel branching structure on heat transfer were discussed. The UV–vis absorption spectroscopy was used to determine the residence time distribution in the reactor, and characteristic parameters such as skewness and dimensionless variance were obtained. Further, a chained stagnant flow model was proposed to precisely describe the trailing phenomenon caused by fluid stagnation and laminar flow in small scale reactors, which enables a better fit for the experimental results of the asymmetric residence time distribution. In addition, the heat transfer performance of the reactor was investigated, and the overall heat transfer coefficient was 110–600 W m^-2 K^-1 in the flow rate range of 10–40 mL/min.     

Effect of thermal degradation on rheological properties for poly(3-hydroxybutyrate)

Thermal degradation at processing temperature and the effect on the rheological properties for poly(3-hydroxybutyrate) have been studied by means of oscillatory shear modulus and capillary extrusion properties, with the aid of molecular weight measurements. Thermal history at processing temperature depresses the viscosity because of random chain scission. As a result, gross melt fracture hardly takes place with increasing the residence time in a capillary rheometer. Moreover, it was also found that the molecular weight distribution is independent of the residence time, whereas the inverse of the average molecular weight is proportional to the residence time. Prediction of average molecular weight with a constant molecular weight distribution makes it possible to calculate the flow curve following generalized Newtonian fluid equation proposed by Carreau as a function of temperature as well as the residence time.