氯苯硝化产物是重要的化工原料和中间体，被广泛应用于染料、农药、军工、医药等领域。氯苯硝化速率快、放热强、粘度高，传统的硝化工艺存在反应控制困难、安全隐患大、时空收率低、能耗高等问题。本论文通过研究微反应器内氯苯硝化液-液过程的分散规律、流动特性，传质性能和反应规律，发展基于微化工系统的安全、高效、绿色的氯苯硝化工艺。揭示了微通道内硫酸-氯苯体系的分散、流动规律。考察了流量和物性对液滴尺寸和液滴运动速度的影响，液滴尺寸随Cac的增大和Wed的减小而减小，液滴速度UD大于两相平均流速UTP，二者的偏差随流量和硫酸浓度的增加而增大。建立了适用于该体系的液滴尺寸预测模型和液滴运动速度预测模型，为预测微通道中相含率、比表面积并计算传质系数提供了基础。考察了微尺度下硫酸-氯苯体系的传质性能。揭示了溶质初始浓度、流量和相比对传质过程的影响规律，微通道中硫酸-氯苯体系的传质系数比填料塔、搅拌釜等传统化工装备高1-3个数量级。相比小于2时，为滴内传质控制，相比大于8时，为滴外传质控制。通过改变相比，获得了滴内和滴外分传质系数随关键参数的变化规律，建立了滴内和滴外的分传质系数模型。建立了氯苯硝化反应动力学模型。搭建了快速、准确测量硝化动力学的连续流动研究平台，将氯苯溶于浓硫酸，消除相间传质的影响，获得了氯苯硝化表观速率常数。基于Mc活度系数和硝酸在硫酸中的解离平衡，建立了可预测不同硫酸浓度下氯苯硝化反应的动力学模型，获得了基于NO2+的动力学参数k*和n。温度升高，k*的数值增大，n与芳香烃种类特征相关，本研究范围内n约为0.71。明确了微化工系统内氯苯硝化反应的基本规律。温度升高，邻硝基氯苯的选择性增加，二硝化合物的含量增加。氯苯硝化反应中，酚类物质的含量低于气相色谱对其的检测限（~5 ppm）。反应过程中，Ha均小于0.3，表明在微化工系统内，相间传质不是氯苯硝化过程的速率控制步骤，有效强化了氯苯硝化过程。提出了混酸作为分散液滴的连续流操作模式，设计了阶梯式T型微设备以实现混酸作为分散相的硝化过程。混酸用量方面，由原来的混酸/氯苯相比为5：1减小到1：3，有效强化了反应过程。

Chlorobenzene nitration products are important chemical raw materials and intermediates, which are widely used in dyes, pesticides, military industry, medicine and other fields. Chlorobenzene nitration has the characteristics of fast rate, highly exothermic and high viscosity, the traditional nitration process has problems, such as difficult reaction control, high safety hazards, low space-time yield, and high energy consumption. In this paper, the liquid-liquid dispersion and flow characteristics, mass transfer and reaction performances of chlorobenzene nitration in the microreactor were studied. A safe, efficient and green chlorobenzene nitration process based on microchemical system has been developed.The rules of droplet formation and droplet flow of H2SO4-chlorobenzene system in the microchannel were revealed. The effects of flow rate, flux ratio and physical properties on droplet size and droplet velocity were investigated. The droplet size decreased with the increase of Cac and the decrease of Wed. The droplet velocity UD was larger than the two-phase average velocity UTP, and the deviation increased with the increase of flow rate and sulfuric acid concentration. A droplet size prediction model and a droplet velocity prediction model suitable for this system were established, which provided a basis for predicting the phase holdup, specific surface area and mass transfer coefficient in the microchannel.The mass transfer performance of H2SO4-chlorobenzene system in microscale was investigated. The effects of initial solute concentration, flow rate and flux phase ratio on the mass transfer process were investigated. The mass transfer coefficient of H2SO4-chlorobenzene system in the microchannel is 1-3 orders of magnitude higher than that of traditional chemical equipment such as packed column and stirred tank. When the flux phase ratio was less than 2, the mass transfer was controlled by the resistance inside the droplet, and when the flux phase ratio was greater than 8, the mass transfer was controlled by the resistance outside the droplet. By changing the flux phase ratio, the variation of partial mass transfer coefficient with key parameters was obtained, and the prediction models of partial mass transfer coefficient inside and outside the droplet were established.The kinetic model of chlorobenzene nitration was established. A continuous flow platform for rapid and accurate measurement of nitration kinetics was built. By dissolving chlorobenzene in the concentrated sulfuric acid solution, the effect of mass transfer between the two phases was eliminated, and the apparent rate constants of chlorobenzene nitration were obtained. Based on the Mc activity coefficient and the dissociation equilibrium of nitric acid in sulfuric acid, a kinetic model for predicting the chlorobenzene nitration at different sulfuric acid concentrations was established, and the kinetic parameters k* and n based on NO2+ were obtained. The value of k* increases with the increase of temperature. n is a specific thermodynamic parameter that is characteristic of different aromatic compounds, and n is about 0.71 in the scope of this studyThe basic rules of chlorobenzene nitration in the microchemical system were clarified. The effects of key parameters such as temperature, molar ratio and sulfuric acid concentration on the chlorobenzene nitration were explored, With the increase of temperature, the selectivity of o-nitrochlorobenzene (o-NCB) and the content of 2,4-dinitrochlorobenzene (DNCB) increased. The amount of phenolics in the chlorobenzene nitration reaction was below the detection limit of gas chromatography (~5 ppm). In the reaction process, Ha is always less than 0.3, indicating that mass transfer was no longer the rate-controlling step of chlorobenzene nitration in the microreactor.The continuous nitration mode with the mixed acid as the dispersed droplets was proposed. A step T-junction microreactor was designed to realize the nitration process with the mixed acid as the dispersed phase. In terms of the amount of mixed acid, the flux phase ratio (mixed acid/chlorobenzene) was reduced from 5:1 to 1:3. The reaction process has been effectively intensified.