Structure controlling and process scale-up in the fabrication of nanomaterials

Nanotechnology is already having a significant commercial impact, and will very certainly have a much greater impact in the future. The research on process engineering and scale-up will be very important for the commercial production and application of nanomaterials, because the properties and structure of nanomaterials are not only determined by the nucleation and growth process, but also strongly affected by the engineering properties, such as the mixing, the heat and mass transfer, and also the distribution of temperature, concentration, etc. This paper will present some research work in our laboratory on the fabrication of nanomaterials. Based on the chemical engineering principle and methods, many kinds of novel nanomaterials can be synthesized and their structure can be easily controlled through adjusting the parameters of the fluid mixing, and the distribution of temperature, residence time and concentration, etc. By using the micro-mixing, heat and mass transfer and reaction control methods, the host-guest nanocomposites have been assembled and assumed as the novel electroanalytical sensing nanobiocomposite materials. Based on the principles of chemical engineering, the manufacturing technologies for magnetic powders, calcium carbonate, and titanium dioxide have been developed for commercial-scale production, and the largest production scale has reached 15 kt/year.     

聚合与混合

以化学反应工程观点对聚合物制造过程进行工程分析。着重阐述了聚合过程中粘度变化对物系传热传质状态和反应动力学的影响,以及对聚合反应器性能,以至对聚合物产品性能的影响。针对增粘过程的搅拌,异粘流体的调匀、粘稠物系的微观混合和非均相体系的产品粒度分布这4类典型的聚合过程课题,分析了各自的混合规律、提出了改进聚合反应器性能,提高产品质量的控制因素及其控制对策。     

一维纳米硼酸盐研究进展：从基础热力学到工程实践

纳米线/棒/管/带/晶须等纳米材料由于其独特的一维（1D）结构及在电子、光学、催化、能源、环境和医药等领域的广泛应用前景而成为研究的热点之一,而硼酸盐则由于其多变的组成及其在众多领域内的独特性能及应用受到了广泛关注。重点围绕碱/碱土金属硼酸盐,从基础热力学、控制合成、应用开发、工程实践等方面对1D纳米硼酸盐材料的最新研究成果进行了综述。此外,对1D纳米硼酸镁的熔融盐（MSS）、化学气相沉积（CVD）等传统高温工艺及本课题组多年来所致力的水热-热转化（HTC）法制备进行了客观比较,结果表明,HTC法在形貌控制合成乃至中试放大等方面具有一定优势。最后以硼酸镁纳米晶须为例,从前述4个方面对目前1D纳米硼酸盐研究中所存在的问题、尤其是针对腐蚀性技术瓶颈的绿色水热合成及其工程实践对策进行了分析和展望。     

Fluidized bed catalytic chemical vapor deposition synthesis of carbon nanotubes—A review

Carbon nanotubes (CNTs) are pure carbon in nanostructures with unique physico-chemical properties. They have brought significant breakthroughs in different fields such as materials, electronic devices, energy storage, separation, sensors, etc. If the CNTs are ever to fulfill their promise as an engineering material, commercial production will be required. Catalytic chemical vapor deposition (CCVD) technique coupled with a suitable reactor is considered as a scalable and relatively low-cost process enabling to produce high yield CNTs. Recent advances on CCVD of CNTs have shown that fluidized-bed reactors have a great potential for commercial production of this valuable material. However, the dominating process parameters which impact upon the CNT nucleation and growth need to be understood to control product morphology, optimize process productivity and scale up the process. This paper discusses a general overview of the key parameters in the CVD formation of CNT. The focus will be then shifted to the fluidized bed reactors as an alternative for commercial production of CNTs.     

反应过程中的污染削减方法

To implement the strategy of pollution prevention in the development of reaction processes, studying the effects of reaction conditions such as temperature, pressure and concentration as well as various engineering factors, such as back- mixing, heat and mass transfer, on environmental performance of the reaction processes is very important. In this paper, potential environmental impact balance, proposed in the waste reduction algorithm, and PEI rate equation are recommended as a useful tool to be used to carry out this work. The application of the method is illustrated with the reaction of allyl chloride production.     

新型热法磷酸燃磷塔传热分析与计算

在介绍新型燃磷塔结构的基础上,提出了计算其理论燃烧温度和烟气排放温度的工程方法。同时分析了燃磷量、过剩空气系数及燃磷塔结构型式等因素对其传热特性的影响。结果表明,在空气过剩系数或空气量不变时,最高燃烧温度和烟气排放温度随燃磷量增加呈单调递增趋势;而在燃磷量一定时,过剩空气系数越大,最高燃烧温度越低,烟气排放温度越高。     

三甘醇水溶液池沸腾传热

Boiling of water/triethyleneglycol (TEG) binary solution has a wide-ranging application in the gas processing engineering. Design, operation and optimization of the involved boilers require accurate prediction of boiling heat transfer coefficient between surface and solution. In this investigation, nucleate pool boiling heat transfer coef-ficient has been experimentally measured on a horizontal rod heater in water/TEG binary solutions in a wide range of concentrations and heat fluxes under ambient condition. The present experimental data are correlated using major existing correlations. In addition a correlation is presented for prediction of pool boiling heat transfer for the system in which the vapour pressure of one component is negligible. This model is based on the mass transfer rate equation for prediction of the concentration at the bubble vapor/liquid interface. Based on this prediction, the temperature of the interface and accordingly, the boiling heat transfer coefficient could be straightforwardly calculated from the known concentration at the interface. It is shown that this simple model has sufficient accuracy and is acceptable below the medium concentrations of TEG when the vapor equilibrium concentration of TEG is almost zero. The presented model excludes any tuning parameter and requires very few physical properties to apply.     

超重力反应沉淀法合成纳米材料及其应用

纳米材料的合成与制备技术已成为全球的研究热点.介绍了一种独创性的纳米材料合成方法即超重力反应沉淀法.从成核动力学、传质、多相体系中分子或原子尺度上的混合机理等方面对该方法进行了理论阐述,依此为指导,成功地制备出粒度分布窄化的纳米粉体.介绍了目前合成的碳酸钙、氢氧化铝、碳酸钡、碳酸锂及碳酸锶等纳米粉体的应用情况.     

溶气过程原理、技术特征及其水处理工程应用

化工、能源和环保等领域都存在气液混合、反应与分离的不同原理的技术应用,涉及多相混合传质及其反应器的工程/工业化生产需求,其中,溶气过程原理与技术特征对应用技术具有重要支撑作用。综合文献及技术报道,从气泡特征、絮体特征来讨论溶气气浮技术,从传质过程、反应过程与能耗评价方面来讨论废水生物处理好氧技术,从O₃发生与性质、传质与催化过程来讨论生物处理尾水的O₃催化氧化深度净化技术。在回顾原理以及分析技术特征的基础上,结合工程案例总结和讨论了溶气原理的废水处理技术/工程实践的发展与潜力。     

固定床吸附过程传热传质耦合影响数值模拟

引言 多孔介质中物质传递与热量传递相互影响,这种现象最早由Soret和Dufour提出[1].由温度梯度作用产生的传质效应称为Soret效应(热附加扩散效应),它代表由温度场的不均匀性而导致的传质现象;由浓度梯度作用产生的传热效应称为Dufour效应(扩散附加热效应),它代表由浓度场的不均匀性而导致的传热现象.     

聚丙烯环形反应器模拟与分析——(Ⅰ)定态特性和可操作域

以工业装置为背景,建立了聚丙烯环形反应器数学模型,经模拟计算,研究了聚丙烯环形反应器的工艺特性,工艺参数对反应器操作状态的影响,并对反应器的可操作域作了分析。     

Thermodynamic optimization of energy transfer in (bio)chemical reaction systems

The engineering science literature on energy-transfer processes (heat engines, heat pumps, etc.) for the production of mechanical energy, electricity, cold or heat has produced some remarkable results on maximum power and efficiency optimization. We have wondered in how far these results can be extended to include chemical reaction systems to describe living and possibly future-industrial energy-transfer systems. With elements of non-linear irreversible thermodynamics and chemical kinetics, we have arrived at some interesting results on optimizing the performance of chemical energy transfer. We discuss thermodynamic efficiency, energy-transfer rate, entropy-generation rate, and optimum-performance characteristics of (bio)chemical energy transfer.     

微化工过程中的传递现象

微化学工程是现代化学工程学科前沿,主要研究微时空尺度下流体流动、传热、传质现象与反应规律。着重介绍近十年来微通道内气-液、液-液两相流体流动、混合与传质的理论和实验的最新研究进展,并对微化工技术的发展进行展望。     

分离式可变热导热管实验研究

根据热能工程及化工领域中的某些实际需要 ,提出了一种新型分离式可变热导热管并进行了实验研究。该种热管能够在保持传热温度变化很小的情况下 ,自动改变传热量来适应负荷变化的需要。实验结果表明 ,当温控热管传热功率增加 2 0 0 %时 ,热管工作温度变化小于 5 %。     

Scale-up concept for modular microstructured reactors based on mixing, heat transfer, and reactor safety

Microstructured reactors are characterized by rapid mixing processes and excellent temperature control of chemical reactions. These properties allow the safe operation of hazardous chemistry in intensified processes. Problems occur during scale-up of these processes, where heat transfer becomes the limiting effect. With high flow rates and transitional or even turbulent flow regimes in small channels, rapid mixing and excellent heat transfer can be maintained up to high production rates. For exothermic reactions, limits for parametric sensitivity and safe operation are shown from literature and combined with convective heat transfer for consistent scale-up. Good knowledge of reaction kinetics, thermodynamics and heat transfer is essential to determine runaway regions for exothermic reactions. From these correlations, consistent channel design and continuous-flow reactor setup is shown.     

Novel Gas-Liquid-Solid Reactors

Multiphase reactors involving gas, liquid, and solid phases have several important applications in the chemical industry, particularly in catalytic processes. Some of the well-known examples are: hydrogenation and oxidation of organic compounds, hydro-processing coal-derived and petroleum oils, Fischer-Tropsch synthesis, and methanation reactions. Due to the presence of three phases, the problem of reactor design is often important to achieve effective mass and heat transfer as well as a mixing pattern favorable to the particular process. The reactors are mainly of two types: (a) solid catalyst is suspended either by mechanical agitation or gas-induced agitation and (b) solid catalyst is in a fixed bed with concurrent or countercurrent feed of gas and liquid re-actants. The reactor types conventionally used in industry are: (a) mechanically agitated or bubble column slurry reactors and (b) trickle-bed or packed-bed bubble reactor. The various design and modeling aspects of these reactors have been reviewed by Satterfield [1], Chaudhari and Ramachandran [2], Shah [3,4], Ramachandran and Chaudhari [5], Shah et al. [6], and Herskowitz and Smith [7]. In several industrial processes these reactor designs are modified to achieve a certain specific objective, such as better heat or mass transfer, higher catalyst efficiency, better reactor performance and selectivity, etc. Similarly, specially designed reactors are often used for laboratory kinetic studies or to understand a certain phenomenon. Thus, novel multiphase reactors are becoming important from both academic and industrial viewpoints. Some of the recently introduced novel gas-liquid-solid reactor types are: (a) loop recycle slurry reactors, (b) basket-type reactors, (c) ebullated-bed reactors, (d) internal or external recycle reactors, (e) multistage slurry or packed-bed reactors, (f) column reactors with sieve trays or multiple agitators, (g) gas-induced agitated reactors, and (h) horizontal-packed-bed reactors. are being used in several new commercial processes, and various design aspects, such as hydrodynamics and mass and heat transfer, have been the subject of investigations in the last few years. However, no attempt to review the scattered information on these novel gas-liquid-solid reactors has been made. Therefore, the main objective of this paper is to review important developments in novel gas-liquid-solid reactors. For each type of reactor, advantages, disadvantages, and applications are discussed. Further, the status of information on hydrodynamics and mass transfer parameters and scale-up considerations is reviewed. These novel reactor designs are being used in several new commercial processes, and various design aspects, such as hydrodynamics and mass and heat transfer, have been the subject of investigations in the last few years. However, no attempt to review the scattered information on these novel gas-liquid-solid reactors has been made. Therefore, the main objective of this paper is to review important developments in novel gas-liquid-solid reactors. For each type of reactor, advantages, disadvantages, and applications are discussed. Further, the status of information on hydrodynamics and mass transfer parameters and scale-up considerations is reviewed.     

Novel Gas-Liquid-Solid Reactors

Multiphase reactors involving gas, liquid, and solid phases have several important applications in the chemical industry, particularly in catalytic processes. Some of the well-known examples are: hydrogenation and oxidation of organic compounds, hydro-processing coal-derived and petroleum oils, Fischer-Tropsch synthesis, and methanation reactions. Due to the presence of three phases, the problem of reactor design is often important to achieve effective mass and heat transfer as well as a mixing pattern favorable to the particular process. The reactors are mainly of two types: (a) solid catalyst is suspended either by mechanical agitation or gas-induced agitation and (b) solid catalyst is in a fixed bed with concurrent or countercurrent feed of gas and liquid re-actants. The reactor types conventionally used in industry are: (a) mechanically agitated or bubble column slurry reactors and (b) trickle-bed or packed-bed bubble reactor. The various design and modeling aspects of these reactors have been reviewed by Satterfield [1], Chaudhari and Ramachandran [2], Shah [3,4], Ramachandran and Chaudhari [5], Shah et al. [6], and Herskowitz and Smith [7]. In several industrial processes these reactor designs are modified to achieve a certain specific objective, such as better heat or mass transfer, higher catalyst efficiency, better reactor performance and selectivity, etc. Similarly, specially designed reactors are often used for laboratory kinetic studies or to understand a certain phenomenon. Thus, novel multiphase reactors are becoming important from both academic and industrial viewpoints. Some of the recently introduced novel gas-liquid-solid reactor types are: (a) loop recycle slurry reactors, (b) basket-type reactors, (c) ebullated-bed reactors, (d) internal or external recycle reactors, (e) multistage slurry or packed-bed reactors, (f) column reactors with sieve trays or multiple agitators, (g) gas-induced agitated reactors, and (h) horizontal-packed-bed reactors. are being used in several new commercial processes, and various design aspects, such as hydrodynamics and mass and heat transfer, have been the subject of investigations in the last few years. However, no attempt to review the scattered information on these novel gas-liquid-solid reactors has been made. Therefore, the main objective of this paper is to review important developments in novel gas-liquid-solid reactors. For each type of reactor, advantages, disadvantages, and applications are discussed. Further, the status of information on hydrodynamics and mass transfer parameters and scale-up considerations is reviewed. These novel reactor designs are being used in several new commercial processes, and various design aspects, such as hydrodynamics and mass and heat transfer, have been the subject of investigations in the last few years. However, no attempt to review the scattered information on these novel gas-liquid-solid reactors has been made. Therefore, the main objective of this paper is to review important developments in novel gas-liquid-solid reactors. For each type of reactor, advantages, disadvantages, and applications are discussed. Further, the status of information on hydrodynamics and mass transfer parameters and scale-up considerations is reviewed.     

Efficiencies of Sieve Tray Distillation Columns by CFD Simulation

A 3‐D two‐fluid CFD model in the Eulerian‐Eulerian framework was developed to predict the hydrodynamics and heat and mass transfer of sieve trays. Interaction between the two phases occurs via interphase momentum and heat and mass transfer. The tray geometries are based on the large rectangular tray of Dribika and Biddulph and FRI commercial‐scale sieve tray of Yanagi and Sakata. In this work a CFD simulation is developed to give predictions of the fluid flow patterns, hydraulics, and mass transfer efficiency of distillation sieve trays including a downcomer. The main objective has been to find the extent to which CFD can be used as a design and prediction tool for real behavior, concentration and temperature distributions, and efficiencies of industrial trays. Despite the use of simple correlations for closure models, the efficiencies obtained are very close to experimental data. The results show that values of point efficiency vary with position on the tray because of variation of affecting parameters, such as velocities, temperature and concentration gradients, and interfacial area. The simulation results show that CFD can be used as a powerful tool in tray design and analysis, and can be considered as a new approach for efficiency calculations and as a new tool for testing mixing models in both phases. CFD can be used as a “virtual experiment” to simulate tray behavior under operating conditions.     

微通道内CO2吸收与传质及资源化利用的研究进展

由于在流体流动、传质、传热及反应等方面良好的调控能力,微化工技术成为化工学科重要的发展领域。综述了近年来以CO₂应用为背景的微化工系统中的多相流与传质的研究进展。从流体流动和传质机理出发,分别介绍了物理吸收和化学吸收过程的传质规律。总结了二氧化碳资源化利用的应用进展。展望了微化工技术在二氧化碳吸收与传质方面的发展前景。     

场协同对PP/PS复合体系传热传质性能的影响

从动量和能量守恒方程出发,提出速度场与温度场的协同耦合作用对聚合物流动与换热具有重要影响,并以此为依据设计了新型扭转螺杆结构和场协同螺杆。以聚丙烯(PP)和聚苯乙烯(PS)为原料制备PP/PS复合材料体系,通过挤出试验对比研究了常规螺杆与场协同螺杆的传热传质性能。结果表明,相对于常规螺杆,设置有扭转螺杆结构的场协同螺杆的数均粒径更小、粒径分布密度和平均停留时间更大,提高了挤出机的混合能力;场协同螺杆的对流换热系数更大、径向温差更小,提高了挤出机的换热能力。