Propane combustion in non-adiabatic microreactors: 2. Flow configuration in posted microreactors

The aim of this paper is to analyze cross-flow operation in a microreactor with posted catalytic inserts for Pt-catalyzed propane combustion under fuel-lean conditions. The insert consists of 150 posts arranged in-line in six rows. The posts are static pillar-like structures in the flow channel, which act as static mixers and provide higher catalytic surface area. Computational Fluid Dynamics (CFD) simulations are used to compare the post microreactors for axial- and cross-flow configurations. In cross-flow case, where the bulk flow is in transverse direction across the six rows of posts, significant flow mal-distribution is observed. Tapering of the inner walls of the microreactor solid structure, at an angle of 5.766°, is proposed for obtaining more uniform flow distribution. For the cross-flow microreactors with tapered inner walls (referred to as “tapered-post”), the flow distribution becomes more uniform as the flow rate is decreased. The axial- and tapered-post microreactors show similar propane conversion for a wide range of operating conditions. Tapered-post microreactors have lower pressure drop and more uniform wall temperatures because the reaction zone is spread over the entire length of the catalytic insert. We also show that tapered-post microreactors have lower heat losses, and therefore are more stable towards device extinction. Consequently, the primary advantages of tapered-post microreactors are better thermal management and ability to operate at more fuel-lean conditions.     

Detection of Multiple Blockages in Parallelized Microreactors

In a plant consisting of parallelized microreactors (MRs), the product quality is lowered because of a lack of flow uniformity among them when blockage occurs. It is not practical to install sensors in every MR from the viewpoint of cost when detecting the blocked MRs. In the previous study, the multiple blockage detection (MBD) method using a small number of sensors was proposed, but its performance became low when the number of sensors decreased. Here, the conventional algorithm for MBD is improved by considering the process behavior on blockage occurrence, and the effectiveness of the improved algorithm is demonstrated through a numerical case study. The effects of flow distributor types and sensor types on the MBD performance are numerically investigated.     

Propane combustion in non-adiabatic microreactors: 1. Comparison of channel and posted catalytic inserts

The reduction in size of catalytic microreactors results in high heat and mass transfer rates and a significant increase in the surface area to volume ratio. A further increase in the catalytic surface area can be achieved in a scaled-down version of fixed bed reactors. Since micro-fixed bed reactors are often deemed impractical due to their large pressure drops, one could use precisely structured inserts to increase the surface area, enhance mixing and manipulate the flow distribution. Catalytic propane combustion in microreactors with multi-channel and posted inserts, which consist of multiple static structures (walls separating various channels and pillar-like structures, respectively) in the flow channel of a microreactor, is considered in this series of two papers. In this first paper, we present numerical comparison of multi-channel and posted catalytic inserts for non-adiabatic self-sustained propane combustion. The inserts are oriented axially along the flow direction. We show that channel and post microreactors have similar performance for low thermal conductivity of the inserts. The in-line arrangement of the posted structures is preferred over a staggered arrangement because the former provides higher propane conversion and more stable combustion. The role of thermal conductivity of the microreactor wall structure and the catalytic inserts is investigated. The thermal conductivity of the microreactor structure affects the performance of the posts but not the channels; this is contrary to the effect of catalyst insert thermal conductivity where it is vice-versa. The channel microreactor is more stable towards high flow-rate blowout limit, whereas the post microreactor is significantly more stable at the lower flow-rate extinction limit. This results in stable operation of the post microreactor under more fuel-lean mixtures than the channel microreactor.     

Intensification of liquid–liquid two-phase mass transfer in a capillary microreactor system

A convenient strategy to intensify the liquid–liquid mass transfer performance in a capillary microreactor system was developed by narrowing the inlet channel of T-micromixer or adding baffles into the capillary. Various geometrical parameters such as the inlet mode and diameter of the modified T-micromixer, the number of baffles and interval distance between baffles in the modified capillary were investigated to elaborate the mass transfer intensification mechanism. The liquid–liquid two-phase flow patterns in new capillary microreactors were captured by a high-speed camera. Moreover, pressure drops and specific energy dissipation of these modified microreactor systems were studied and a new parameter indicating the ratio of the mass transfer coefficient to the energy dissipation was proposed. This work highlights the modified capillary microreactor systems with embedding baffle units for achieving high mass transfer rates with its advantages over other types of reactors or microreactors considering specific energy dissipation and effective energy utilization efficiency. © 2018 American Institute of Chemical Engineers AIChE J, 65: 334–346, 2019     

微反应器制备催化材料的研究进展及展望

近年来,微化工技术作为化学合成中的一个新兴领域、过程强化的有效手段,引起了人们的广泛关注。微反应器在微尺度通道下具有高比表面积/体积比、优良的传质传热性能,能够实现反应物的快速混合,对反应过程实现精确控制。概述了微通道反应器的特点。总结了近年来部分类型微反应器在制备催化材料方面的研究进展,包括撞击流微反应器、膜分散微反应器、微孔管式微反应器。同时参照微反应器近年来在工业生产中的应用实例,提出了结合计算机模拟系统,设计高效、稳定、低成本、多功能的连续流微反应器将是开发新型高性能催化材料及其工业化应用的重要保障。     

3D打印在微反应器制造中的应用

3D打印技术具有自由设计、生产时间短、节约材料、无需模具、易于制造复杂结构等优点,使其在微反应器设计和制造方面能够发挥巨大作用。本文对比了几种常用微反应器的制造工艺,重点综述了3D打印技术在微反应器制造中的应用进展。     

TiO2平板微反应器设计优化及光催化性能研究

光流体学可以将光催化反应与微流控技术结合,大幅提高光利用率和反应速率,实现对光催化水处理的高效强化,其中微反应器结构的设计与优化是研究重点之一。首先利用流体力学模拟分析优化通道级数,设计了5级树状通道平板反应器。进而,通过调控通道高度,研究不同高度的微通道对其光催化性能的影响。研究发现50 μm微反应器的降解性能及连续操作性能均优于100 μm。同时以亚甲基蓝为模拟废水对微反应器及釜式反应器的反应动力学、微反应器污染问题、连续操作性能等进行研究。研究表明,微反应器在不同流速下对亚甲基蓝均能实现连续高效降解,降解率远高于釜式反应器。当流速为55 μl/min时对5×10^-5 mol/L亚甲基蓝可达到95%的降解率并保持较好的连续操作性能及重复使用性能。     

Gas-liquid flow mass transfer in a T-shape microreactor stimulated with 1.7 MHz ultrasound waves

This paper describes the application of ultrasound waves on hydrodynamics and mass transfer characteristics in the gas-liquid flow in a T-shape microreactor with a diameter of 800 μm.A 1.7 MHz piezoelectric transducer (PZT) was employed to induce the vibration in this microreactor.Liquid side volumetric mass transfer coefficients were measured by physical and chemical methods of CO2 absorption into water and NaOH solution.The approach of absorption of CO2 into a 1 mol· L-1 NaOH solution was used for analysis of interfacial areas.With the help of a photography system,the fluid flow patterns inside the microreactor were analyzed.The effects of superficial liquid velocity,initial concentration of NaOH,superficial CO2 gas velocity and length of microreactor on the mass transfer rate were investigated.The comparison between sonicated and plain microreactors (microreactor with and without ultrasound) shows that the ultrasound wave irradiation has a significant effect on kLa and interfacial area at various operational conditions.For the microreactor length of 12 cm,ultrasound waves improved kLa and interfacial area about 21％ and 22％,respectively.From this study,it can be concluded that ultrasound wave irradiation in microreactor has a great effect on the mass transfer rate.This study suggests a new enhancement technique to establish high interfacial area and kLa in microreactors.     

Modeling,Simulation and Optimized Design of a Microreactor for a Two‐Step Reaction

A two‐step microreactor for the investigation of glucose oxidation is presented. A model is created to pre‐judge the changes in concentrations of the reactants in the straight channels of the microreactor. The structure of the rapid mixing‐reaction units of the microreactor was optimized, and the optimal parameters were found to be p = 1:3, r = 1:1, and w_s = 60 μm. The model and the optimization method can facilitate the design of microreactors.     

Pressure drop and mixing in single phase microreactors: Simplified designs of micromixers

Continuous flow microreactors can greatly improve the safety and product yields of processes in the pharmaceutical and fine chemical industry by overcoming many of the drawbacks of traditional batch and semi-batch stirred reactors. This study compares on a common scale the pressure drop and mixing performance of different size commercial microreactor plates composed of a tangential, SZ-shaped or caterpillar mixer followed by a rectangular serpentine main channel. The pressure drop was fitted to a friction factor model, which suggests that the mixing zone had significant chaotic secondary flow patterns, whereas the main channel did not. Moreover, the mixing zone was the main contributor to the overall pressure drop. Mixing performance was then characterized using competitive parallel reactions. Upon the formation of chaotic secondary flows, typically due to the interactions of artificially induced vortices, the mixer performance was found to be independent of geometry for a given energy dissipation rate. However, the mixer geometry will affect the critical Reynolds number that induces chaotic advection and changes the mixing time scale.     

The measurement and characterisation of residence time distributions for laminar liquid flow in plastic microcapillary arrays

Residence time distributions (RTDs) for a thermoplastic microreactor system were experimentally measured using fibre optic probes and step change concentration inputs. The distributions were then compared to models assuming plug flow superimposed by axial dispersion. The disc-shaped plastic microreactors contained microcapillary arrays of up to 19 parallel channels with diameters around 230 μm and lengths of 10 m. Two different systems were investigated, with either 1 or 19 active capillaries. The magnitude of axial dispersion in those two systems was characterised using Peclet numbers, which were in the range of 15-221 depending on flow rate, demonstrating that molecular dispersion along a single 10 m capillary can provide near plug flow characteristics. The multiple-capillary array showed small perturbations of this plug flow like RTD behaviour as the 19 microcapillaries displayed slight variations in diameter. These results confirm that the flow inside the presented plastic multiple capillary device provides a near plug flow behaviour for the use in continuous microreactors.     

微反应器中费托合成的研究进展

目前费托合成常用的固定床、浆态床和流化床三种反应器存在不同程度的传质和传热问题,同时反应物/产物与催化剂难以分离,而微反应器因其可在接近等温和很小压降条件下进行反应,从而有望改善费托合成的反应性能,提高所用催化剂的活性和选择性。本文首先介绍了微反应器的结构和特性,然后从催化剂种类及其在微反应器中颗粒装填式和器壁涂覆式两种形式简述了微反应器中费托合成的实验研究,并从计算流体力学和动力学研究等方面简述了微反应器中费托合成的模拟计算。     

光化学微反应技术的基础及研究进展

光化学转化是有效利用光能实现化学反应的重要途径,微反应技术为提高其过程效率提供了一个强有力的平台。本文首先指出微反应器相比于传统釜式光反应器,在光强分布、过程放大、光能利用效率等诸多方面存在明显的优势,能够实现光化学反应过程的高效强化。简要地介绍了光化学转化及光化学微反应技术的基本特征,然后系统地综述了光化学微反应器的设计构建及其在有机合成、聚合等方面的应用,并详细介绍了自动化控制的光化学微反应系统及应用。重点介绍了微反应技术在紫外光、可见光辐照下的光化学合成进展及其过程放大。最后,对光化学微反应技术的研究进展进行总结,并对其发展趋势进行了展望。     

不同结构微反应器下甲烷水蒸气重整制氢性能对比

微通道反应器是便携式制氢领域目前最有发展前景的技术之一。为了提高甲烷水蒸气重整在微反应器内制氢的效果,设计了三种不同结构的微反应器几何模型,分别为直管(Pipe)模型、平板圆弧弯道(FCC)模型和三纹内螺旋枪管(Tri-g ISB)模型,利用Ansys Fluent流体仿真软件结合甲烷水蒸气重整制氢的CHEMKIN反应机理文件对三种不同结构的微反应器进行了数值模拟分析。通过研究不同条件下微反应器出口气体组分变化可知,入口速度越小,CH4转化率和H2体积分数越高;S/C>3时,CH4转化率增大至80%以上、H2含量增加至73vol%以上;壁面温度越大,CH4转化率可稳定在99.9%,几乎完全转化,H2含量增大到77vol%以上,但温度过高会降低H2产量,增加CO含量。通过计算不同条件下微反应器达到稳定所需时间可知,随入口速度和S/C增加稳定时间均逐渐减小并趋于稳定,随壁面温度增加,稳定时间先减小后增加。通过对比三种微反应器可知,复杂结构可以强化微反应器的性能,但会增加微反应器达到稳定所需的时间。在微反应器性能方面：FCC模型最优,Pipe模型最差;而在稳定时间方面：随着结构复杂性增加稳定时间反而增长,Pipe模型最短,Tri-g ISB模型最长;微反应器结构的复杂程度不同,对性能的提升也不同,过于复杂的结构反而会抑制微反应器的性能。     

Application of direct fluid flow oscillations to improve mixing in microbioreactors

This article describes an active mixing method for a microbioreactor that was designed, simulated, tested, and successfully implemented. By applying a varying pressure to a microchannel looping tangentially into a cylindrical microreactor an oscillating fluid flow was shown to occur. Such an oscillating fluid flow improved mixing, both by diffusion and convection. The oscillating fluid flow has a large impact on the ratio between the diffusion domain and the convection domain. A good match was obtained between experimental mixing results, computational fluid dynamics simulation results and the results of a simplified mixing model thus demonstrating the potential of simulation on improving the design of microreactors. © 2009 American Institute of Chemical Engineers AIChE J, 2009     

铜离子掺杂二氧化钛光催化板式微反应器

将微反应器技术应用于光催化反应是一项新兴且极具潜力的技术创新.采用金属蚀刻技术制造了板式微反应器,并通过溶胶-凝胶法在微反应器中负载了铜离子掺杂改性的TiO₂光催化剂涂层.使用X射线衍射分析、扫描电子显微镜以及紫外-可见漫反射吸收光谱对催化剂进行表征,并以甲基橙的降解反应来评价微反应器的光催化效果.结果表明,铜离子掺杂能够有效提高微反应器的光催化性能,掺杂浓度为0.04%(摩尔比于Ti)时效果最优,能够在90 s的停留时间内使初始浓度为10 mg·L^-1的甲基橙溶液降解45%;光催化微反应器中甲基橙的降解过程为不完全氧化的动力学一级反应,其反应速率常数(k)远高于常规反应器体系,并随着甲基橙溶液初始浓度(C₀)的减小而增大,且lnk-lnC₀具有良好的线性关系.     

Facile Preparation of an Enzyme‐Immobilized Microreactor using a Cross‐Linking Enzyme Membrane on a Microchannel Surface

The enzyme microreactor has considerable potential for use in biotechnological syntheses and analytical studies. Simplifying the procedure of enzyme immobilization in a microreactor is attractive, and it is achievable by utilizing enzyme immobilization techniques and taking advantage of the characteristics of microfluidics. We previously developed a facile and inexpensive preparation method for an enzyme‐immobilized microreactor. The immobilization of enzymes can be achieved by the formation of an enzyme‐polymeric membrane on the inner wall of the microchannel through cross‐linking polymerization in a laminar flow. However, this method is unsuitable for use in conjunction with electronegative enzymes. Therefore, a novel preparation method using poly‐L ‐lysine [poly(Lys)] as a booster and an adjunct for the effective polymerization of electronegative enzymes was developed in this study. Using aminoacylase as a model for an electronegative enzyme, the reaction conditions for the enzyme‐cross‐linked aggregation were optimized. On the basis of the determined conditions, an acylase‐immobilized tubing microreactor was successfully prepared by cross‐linking polymerization in a concentric laminar flow. The resulting microreactor showed a higher stability against heat and organic solvents compared to those of the free enzyme. The developed method using poly(Lys) was applicable to various enzymes with low isoelectric points, suggesting that this microreactor preparation utilizing a cross‐linked enzyme in a laminar flow could be expanded to microreactors in which a broad range of functional proteins are employed.     

Data-based and model-based blockage diagnosis for stacked microchemical processes

One of the critical problems in the operation of microchemical processes is blockage in microchannels. Therefore, a process monitoring system which can detect and diagnose blockage is indispensable for effective and stable operation of microchemical processes. In the present research, two types of diagnosis systems, a data-based blockage diagnosis system (DB-BDS) and a model-based blockage diagnosis system (MB-BDS), are proposed. To realize efficient diagnosis for various degrees of blockage, the proposed DB-BDS uses the ratios of temperature differences between normal and abnormal operating conditions at one sensor to those at the other sensor. On the other hand, MB-BDS, which uses simple physical models of the process, diagnoses blockage by calculating the correlation coefficients between the prepared temperature distribution vectors and the actual temperature distribution vector when blockage is detected. The performance of the proposed systems is evaluated with their applications to a stacked microreactor. DB-BDS and MB-BDS are applied to various types of blockage, i.e., various locations and degrees. The results show that both DB-BDS and MB-BDS can diagnose the blockage location successfully even when blockage degree is less than 10%.     

微反应器在聚合反应中的应用

微反应器因其良好的混合和传热性能近年来开始应用到聚合反应中,并表现出巨大潜力。本文对微反应器在自由基聚合、离子聚合和逐步聚合中的应用进行了系统综述。相比于传统的釜式反应器,微反应器可以更好地调节聚合产物分子量和分子量分布、控制共聚组成和分子结构。在强放热聚合反应中,利用微反应器可以获得窄分子量分布的聚合产物;在扩散控制的聚合反应中,利用微反应器可以大大缩短反应所需时间。微反应器在聚合反应领域中的拓展依赖于对反应机理和微反应器特点的深入理解,相关的基础研究将成为这一领域发展的关键。     

Numerical investigation of the hydrodynamics of split‐and‐recombination and multilamination microreactors

The hydrodynamics and residence time distribution (RTD) of two microreactors based on the split‐and‐recombination (SAR), and multilamination mixing mechanisms, respectively were investigated. It was found that the design of the distribution manifolds of the SAR mechanism produces an unbalanced flow distribution. For feeding ratios different than one, bypassing and recirculation occur within the SAR manifolds. For equal flow rates the SAR flow behavior can be accurately described by the pure convection model. The manifold used in the multilamination microreactor achieves a homogeneous distribution of flow and its interdigital mixing structure generates an alternated pattern of fluid layers which is maintained for Re < 140. After this point the ordered arrangement is broken and two large segregated zones are formed. In the absence of molecular diffusion both microreactors reach limiting values of scale and intensity of segregation that were found to be independent of the energy applied to the system. © 2012 American Institute of Chemical Engineers AIChE J, 59: 988–1001, 2013