多相反应体系的微界面强化简述

加氢、氧化等气液慢反应过程广泛存在于现代过程工业之中,这些反应过程一般受传质速率控制。因此,对这类多相反应体系的传质强化一直是研究热点之一。但总体而言,除外场和微通道（微流控）强化等一类强化反应器外,以往的研究大多集中于界面尺度为毫-厘米级的传统反应器的搅拌与混合方式、气泡分布状态、流体流型、构效关系等方面,而鲜有将研究视角投放到传统以米为直径计量单位的反应器平台上如何构建尺度为微米级的界面体系及其特殊效应方面。探讨了多相反应体系的微界面反应强化理念,并简述了微界面的涵义、微界面反应强化与构效调控方法、微界面反应器的结构与形成原理、微界面体系的微颗粒测试与相界面表征技术、微界面反应强化面临的问题与挑战等,以与本领域同行共同研讨。     

Study on the characteristics of micro-interface intensified oxidation of ammonium sulfite

The process intensification of interfacial area and reaction conditions in multi-phase systems are important issues in industrially scaled reactors. In order to investigate the intensifying effect of micro-interface system on gas-liquid mass transfer and reaction rate, the ammonium sulfite oxidation was selected as the research object. A systematic air forced oxidation experiment was carried out through the micro-interface intensification reactor (MIR) and the traditional bubble column reactor (BCR) under the same experiment platform and operating conditions. The bubble size distribution and overall gas holdup were measured by high-speed camera technology and differential pressure measurement, respectively. The experimental results showed that MIR obtained higher gas holdup because of the micro-interface structure, the interfacial area was increased by more than 10 times, the reaction rate increased by 56.8% averagely compared with BCR. The experimental conclusions provide certain data support for the industrial application of the multiphase reaction system of the micro-interface intensification reactor.     

亚硫酸铵微界面强化氧化特性研究

以亚硫酸铵水溶液的空气氧化为研究对象，考察了微界面强化对该体系传质与氧化过程的影响。在同一实验平台和操作工况下，对微界面强化与传统鼓泡塔氧化过程的传质和反应性能进行了实验研究。利用高速摄像与压差测量技术，分别对反应过程的空气气泡分布与气含率变化进行了测定。结果表明，相较于传统鼓泡塔空气氧化反应器，微界面强化氧化反应器以微界面体系取代了传统毫-厘米级宏界面，在不同盐离子浓度与氧化气量工况下均表现出了良好的强化效能。在微界面体系强化下，亚硫酸铵氧化过程气含率大幅提升，相界面积增加十余倍，反应速率平均提升56.8%，实验结论为微界面强化反应器的多相反应体系工业应用提供了一定的数据支撑。     

第二液相对气液二相体系传质的影响

以CO2气体-K2CO3/KHCO3水溶液吸收过程为研究体系,用酸解法测量气体被吸收的速率,通过对比试验考察了加入第2液相(有机相)对体系传质速率的影响。经过试验研究证明,第2液相的加入对气液传质过程的影响程度与加入的物质有关,在试验条件下甲苯对体系强化作用高于异辛醇和庚烷对体系的强化作用。当第2液相加入量较小时,随加入量的增加,其对气液传质过程的促进作用增强,但当第2液相加入量较大时,这种作用则不明显。同时第2液相对传质作用的影响与流动场有关,增加流动场的搅动有助于强化气液传质作用。     

Mass transfer and selectivity of ozone reactions

The present research concerns the behavior of mass transport in absorption of ozone accompanied by decomposition and ozonation reactions in aqueous solutions. On the basis of the film theory, a mathematical model has been formulated for the transport process taking into account molecular diffusion and the simultaneous decomposition and ozonation reactions of different orders. Analytical approximate and finite difference methods have been employed to predict concentration profiles, enhancement factor and selectivity of the chemical mass transfer in gas-liquid systems. The rate of mass transfer is enhanced by the chemical reactions as well as the availability of liquid reactant in the aqueous phase. When the ozonation reaction is much faster than the decomposition reaction, a large fraction of the absorbed ozone is utilized effectively in reacting with the liquid constituent and a high selectivity of the gas-liquid reactions can be obtained. Calculated results indicate that removal of certain organic pollutants by the oxidation process may be effective only in acidic or neutral solutions where a high mass transfer rate and selectivity is achieved.     

超声微反应器内气液传质过程的介尺度强化机制

采用CFD方法对超声微反应器内的Taylor气液两相流的传质过程进行了模拟。针对传质过程中主要的介尺度结构,包括气泡表面波、空化声流、液相内的局部浓度,分析了其空间分布和时间演化规律。模拟结果有效捕捉了实验难以观测的液膜区域,并将液膜厚度与气泡表面波振动进行了关联,阐释了气液界面附近的空化声流对传质过程的强化作用。根据超声微反应器内Taylor流的传质特点,分别研究了不同流动和超声条件对液弹内和液膜处传质过程的影响,比较了各局部传质对整体传质效率的贡献。通过分析整体/局部Sherwood数与Peclet数间的关系,研究了超声效应对气液传质速率的影响。分析结果从介尺度角度验证了文献关于超声微反应器传质系数的计算,完善了超声微反应器内气液传质过程的强化理论。     

发泡剂ADC生成过程动力学分析

在玻璃搅拌反应器中进行了固体联二脲与氯气液相氧化反应生成发泡剂 ADC过程的传质与动力学实验, 提出了基于双膜理论的数学模型,以描述这一反应系统所涉及的气液和固液传质、固体溶解以及溶解物在液相中发生瞬间反应,特别是随反应进行固体反应物粒径变小导致固液传质速率减小的复杂过程. 模型能很好地描述实验结果. 依据模型估测的气液与固液传质系数值比较表明,气相反应物氯气的溶解传质过程是影响整个过程速率的主要控制步骤.     

ON THE MECHANISM OF CO2 ABSORPTION AND DESORPTION

Recent work by Thomas et al. (1982) showed a significant difference in mass transfer rates between absorption and desorption for a CO₂-water system in a film flow, and attributed the phenomena to density-driven convection. Our experiment with a flat-surface stirred cell shows no enhancement of oxygen absorption in simultaneous absorption with CO₂ under a turbulent flow condition. Also, a comparison of liquid velocities measured extremely close to the gas-liquid interface with a laser doppler anemometer reveals negligible difference between absorption of air and that of CO₂. These results indicate that there is practically no detectable density-driven convection in CO₂ absorption.     

基于微吸收器的CO2吸收过程研究进展

微化工技术在流体流动、过程强化、传质与反应过程等领域备受关注,本文归纳整理了3种不同类型的微吸收器（微降膜吸收器、微通道吸收器和微网格吸收器）捕集CO₂过程中的水力学性质和传质过程及其机理研究进展,并对3种微吸收器吸收CO₂过程中存在的问题进行分析总结,同时对微吸收器能快速工业化提出展望。其中重点介绍了微通道泰勒流吸收器的水力学流动特性,包括泰勒流气泡的生成机制、气泡和液弹的长度、气泡的输运和运动速度、气泡截面形状及液膜厚度和气液两相流压降;归纳了微通道泰勒流吸收过程的传质过程机理和传质系数的模型以及不同影响因素（通道截面尺寸,通道长度,主通道结构及入口形状,气、液相组成及其流速,吸收剂和系统压力）作用下CO₂吸收效率和传质系数的研究进展。     

邻二甲苯液相氧化动力学的研究

在搅拌釜（φ107×350mm）中进行邻二甲苯液相氧化动力学的研究,其结果表明,在本试验条件下（搅拌釜转速为1200rpm空釜线速≥1.5cm/s,氧化温度在130℃以下）可以消除传质影响。 本研究建立了邻二甲苯（OX）氧化的动力学方程式（在 OX的转化率<50％时适用）,为气液反应器放大提供计算氧化速度的动力学 模型。 本工作还对邻二甲苯氧化七组分的主副反应动力学进行研究,测定了不同温度下各反应的速率常数和活化能。其数值与采用鼓泡塔氧化的结果相一致,再次表明邻二甲苯氧化为串、并联一级反应。     

微孔射流毛细管反应器内液-液两相传质和反应选择性

微反应技术在化工过程强化领域已得到广泛应用,尤其适用于快速复杂竞争反应体系。对于液-液两相快速竞争反应,反应过程受传质限制,显著影响反应转化率和收率。本文开发了一种新型的微孔射流毛细管反应器（MJCM）,采用微孔射流强化进口处液-液两相传质性能,分别采用水-苯甲酸-煤油体系和水-氢氧化钠-甲苯-苯甲酸-氯乙酸乙酯体系研究了不同操作参数（流量、流量比、表面活性剂浓度、温度）和结构参数（孔径、管长）下液-液两相传质特性和反应选择性,并获得了舍伍德数Sh的关联式。结果表明：随着两相流量的增加,传质效率E呈下降趋势,总体积传质系数k_La呈增加趋势,反应选择性指数X_s则先减小后增大;孔径的增大则会减弱液液传质和反应选择性;随着毛细管长的增加,E和X_s逐渐增大,k_La则逐渐减小;水相-有机相流量比的变化对E和k_La会产生不同影响,而温度的适当升高则可以提升反应选择性,表面活性剂的加入降低了传质和反应选择性。与其他液液传质设备对比,MJCM在液-液两相传质、反应选择性方面性能良好,可以用于工业生产进行液液传质与反应过程的强化。     

精馏技术研究进展与工业应用

精馏是化学工业中应用最广泛的关键共性技术,广泛应用于石油、化工、化肥、制药、环境保护等行业。精馏具有应用广泛、技术成熟等优点,但存在设备投资大、分离能耗高等问题,因此研究开发新型高效传质元件、开发新型节能精馏技术,具有重要的社会意义和经济价值。本文从精馏塔类型、流体力学性能、传质性能、塔器大型化、过程节能、过程强化等方面,介绍了精馏技术的研究进展与工业应用。对于板式塔,从气液两相流动状态、压降、漏液和雾沫夹带方面研究了塔板的流体力学性能;对于填料塔,从压降、液泛和持液量方面研究了填料塔的流体力学性能,但目前的研究仍以经验关联式为主,缺乏严谨的的理论模型。对于气液两相的传质性能研究,简述了气液两相传质理论,但科学、精准的传质模型尚未提出。对于塔器大型化的应用研究,介绍了塔板、气液分布器和支撑装置等大型化关键技术的工业应用。从精馏过程典型节能技术、耦合节能技术、流程节能技术、低温余热回收和特殊精馏等方面,介绍了精馏过程节能与强化的应用进展。文章最后对精馏过程的传质、强化和集成进行了展望。     

Kinetic parameters using an immobilized tetrahexylammonium chloride catalyst in glycidyl methacrylate reaction with carbon dioxide

A soluble copolymer-supported catalyst containing pendant tetrahexylammonium chloride was synthesized by the radical copolymerization of p-chloromethylated styrene with styrene followed by the addition reaction of the resulting copolymer with trihexylamine. Initial absorption rate of carbon dioxide into glycidyl methacrylate (GMA) solutions containing the catalyst was measured in a semi-batch stirred tank with a plane gas-liquid interface at 101.3 kPa. The reaction rate constants of the elementary reaction between carbon dioxide and GMA were evaluated from analysis of the mass transfer mechanism accompanied by the elementary reactions based on film theory. Solvents such as toluene, N-methyl-2-pirrolidinone, and dimethyl sulfoxide influenced the reaction rate constants. Furthermore, this catalyst was compared to monomeric tetrahexylammonium chloride under the same reaction conditions.     

对二甲苯氧化过程控制步骤分析

实验测定了对二甲苯高温氧化各步反应动力学数据。结合反应器中的气液传质数据以及有关的混合时间数据,比较了反应、传质和混合速率的相对大小。结果表明,工业反应器中的混合速率远大于反应速率,反应器可以作为理想混合反应器考虑。在典型的工业条件下,对二甲苯氧化过程为液相化学反应控制,控制步骤为对甲基苯甲酸生成对羧基苯甲醛的反应步骤。     

Absorption of carbon dioxide into glycidyl methacrylate solution containing the triethylamine immobilized ionic liquid on MCM-41 catalyst

An ionic liquid (TEA-MS41), triethylamine-immobilized on chloropropyl-functionalized MCM-41, was synthesized by a grafting technique through a co-condensation method and used as a catalyst in the reaction of carbon dioxide with glycidyl methacrylate (GMA). CO₂ was absorbed into the heterogeneous system of the GMA solution and dispersed with solid particles of the catalyst in a batch stirred tank with a plane gas-liquid interface at 101.3 kPa. The absorption of CO₂ was analyzed by using mass transfer accompanied by chemical reactions based on film theory. The proposed model fits the measured data of the enhancement factor to obtain the reaction rate constants. Solvents such as N,N-dimethylacetamide, N-methyl-2-pyrrolidinone, and dimethyl sulfoxide influenced the reaction rate constants.     

The effect of mass transfer on selectivity for heterogeneous reactions

A simple model based on existing penetration theory solutions is proposed to predict the selectivity for consecutive reactions in gas-liquid systems. The model is limited to cases of moderate to high selectivity, where the first reaction is much faster than the second. When the reaction greatly increases the mass transfer rate, the model gives about the same selectivity as the film theory, but predicts higher selectivities than the film theory when the enhancement factor ø is small and the reaction is rapid. When ø is small, an appreciable fraction of the gas that is absorbed reacts after surface elements are mixed with the bulk, and this contribution is neglected in the film theory. The model can also be applied to estimate the effect of diffusion on parallel reactions.     

An analysis of complex gas-liquid reactions in an isothermal CSTR

A mathematical model was developed for complex gas-liquid reactions with general-order kinetics in a continuously stirred tank reactor. The model equations were solved by the method of orthogonal collocation from which component concentration profiles in both the bulk and film liquid were computed. A parametric study revealed several interesting relationships between the chemical and physical parameters describing the reaction system. Specifically, the effects of mass transfer on the formation of reaction intermediates were analyzed for the case of two consecutive gas-liquid reactions over a wide range of reactor conditions.     

Study on the reaction rate of sulfite oxidation with cobalt ion catalyst

Wet limestone scrubbing is the most common flue gas desulfurization process for control of sulfur dioxide emissions from the combustion of fossil fuels, and forced oxidation is a key past of the reaction. In the present work the oxidation rate was experimentally studied by contacting pure oxygen with a sodium sulfite solution. The sulfite oxidation reaction rate was then measured photographically for various sodium sulfite and Co²⁺ concentrations. The sulfite oxidation reaction rate was affected by the mass transfer characteristics of the gas-liquid absorbers with the cobalt ion catalyst as well as the reaction kinetics. The sulfite oxidation reaction rate controlled by the reaction kinetics was first order with respect to the sulfite. When the sulfite oxidation reaction rate was controlled by the gas-liquid rate of mass transfer characteristics, the reaction was zeroth order with respect to the sulfite.     

超重力多相催化反应器的研究进展

针对本征反应速率为快速反应的多相催化过程,其宏观反应速率一般受限于相间传质速率。基于超重力技术良好的传质强化特征,以及超重力装备关键机械部件在高温高压条件下稳定运行的突破,超重力反应器应用于多相催化反应,逐步展现了反应过程强化的潜力。本文主要对近年来本中心研制的超重力多相催化反应器在气液、气固以及气液固体系的研究进行综述,并对超重力多相催化反应器的发展前景进行了展望。     

排气管直径与深度对水力喷射空气旋流器传质性能的影响

对水力喷射空气旋流器(WSA)的中心排气管直径D_e和排气管插入深度S进行了设计优化研究,实验考察了不同D_e和S对WSA脱氨传质系数K_La和气相压降的影响,提出了综合评价传质过程效率的概念——单位压降传质效率η_p,讨论了D_e和S的设计取值。研究表明,当D_e增大时,K_La和气相压降均随之降低,较小D_e的WSA具有较高的气液传质性能,但气相压降比较大,而K_La和气相压降均随S增大而增大。综合能效关系表明,随着D_e的增大η_p增大,随着S的增大η_p出现先增大后降低的趋势,WSA设计中D_e与WSA直径D之比D_e/D宜为0.42～0.53,S与WSA筒体长度H之比S/H适宜取值约为0.70。