硫酸烷基化是工业生产烷基化油的主流工艺，但存在异丁烷在硫酸中溶解度低、副反应多、废酸量大等问题。本文以发展硫酸烷基化新工艺和新技术为目标，提出基于微化工技术发展硫酸烷基化新技术和过程强化新方法的思想，系统开展了微尺度下硫酸/烷烃体系分散和传质基本规律研究，揭示了微尺度下硫酸烷基化反应动力学和过程强化机制，开发了微尺度下烷基化反应新技术和过程强化新方法，为实现绿色、安全和高效的烷基化过程提供了基础。研究了微通道内硫酸/烷烃体系的分散规律，系统考察了Ca数、两相流量比、两相粘度比、通道放置方式等对分散过程的影响，在国际上首次发现重力对于微分散过程有着重要影响，建立了含重力参数的液滴尺寸预测模型。以硫酸/环己酮肟/烷烃为体系，研究了环己酮肟初始浓度及两相流量等对传质性能的影响规律，得到了该体系在微通道内的传质系数，其值在10-4~10-3 m/s量级。利用该体系的特殊性质，通过调节环己酮肟的初始浓度，首次测定了微通道内液液两相的分传质系数，并建立了分传质系数的预测公式。搭建了用于硫酸烷基化动力学测定的微化工系统，系统研究了硫酸烷基化反应基本规律，得到了微尺度条件下的动力学参数。以三甲基戊烷（TMP）、二甲基己烷（DMH）、高碳组分（HE）和低碳组分（LE）作为关键组分，建立了基于碳正离子－链式反应机理的微尺度下硫酸烷基化反应动力学模型，并利用COMSOL软件对该过程进行模拟，进一步验证了模型的准确性。提出了发展基于微化工系统的硫酸烷基化过程强化新技术的思想，在8.4 s反应时间下碳八组分的选择性高于70%，相对于搅拌釜烷基化过程（反应时间12.5 min，碳八组分选择性为36%）表现出了明显优势。系统研究了硫酸浓度、分散相流量、反应温度、烷烯比以及硫酸循环过程对反应性能的影响，发现通过改变分散尺寸、反应温度和酸烃比可有效调控反应的选择性。开发了分段进料的硫酸烷基化微反应新技术，显著提高了反应过程的选择性，辛烷值高达97.9。针对异丁烷在硫酸中溶解度低以及硫酸粘度大的问题，分别提出了以己内酰胺和三氟乙酸为助剂的硫酸烷基化过程强化新方法，碳八组分的选择性由36%分别提高到了62%和76%，实现了硫酸烷基化过程的强化。
H2SO4 alkylation is one of the main processes in industry to produce alkylates. In H2SO4 alkylation, the low isobutane solubility and side reactions lead to the high acid consumption. Thus, it is highly required to intensify the process. The objective of this work is to develop new microreaction technology of H2SO4 alkylation to intensify this process. The dispersion and mass transfer performances of H2SO4/alkane system were systematically investigated and the kinetics and process intensification mechanism of H2SO4 alkylation were revealed in the microchemical system. Finally, a microreaction technology was developed, and new methods were proposed to intensify the process, which laid the foundation for developing an environmentally friendly, more efficient, and safer process for H2SO4 alkylation.The droplet formation performance of H2SO4/alkane system was studied in a glass T-junction microchannel with H2SO4 as the continuous phase. The effects of capillary number, flow ratio, viscosity ratio, and the flow direction on the droplet formation were investigated. The significant effect of gravity on the dispersion in the microchannel was firstly discovered in the world. Finally, a mathematical model describing the droplet size containing gravity effect at different flow patterns has been established, and the model can predict droplet size very well. The mass transfer coefficients of H2SO4/cyclohexanone oxime/alkane system were determined, which is in the order of magnitude of 10-4 ~ 10-3 m/s. The influences of the initial concentration of cyclohexanone oxime and flow rates of two phases were studied. The mass transfer coefficient for each phase was obtained for the first time by adjusting the initial concentration of cyclohexanone oxime, as a result of the special properties. New mass transfer coefficient prediction models for each phase have been established, which could predict experimental results very well.A microstructured chemical system was established to determine the kinetics of H2SO4 alkylation. The concentration of key components, including trimethylpentane (TMP), dimethylhexane (DMH), light end (LE), and heavy end (HE), were obtained at different reaction temperatures. A kinetics model, containing kinetics parameters of both main and side reactions, was established to predict the alkylation process in the microstructured chemical system. The model fitted with the experimental data very well and further confirmed by the simulation results calculated with COMSOL software. New intensification technology of H2SO4 alkylation was proposed by designing and constructing a microstructured chemical system, and the C8 selectivity is higher than 70% at 8.4 s, showing obvious advantages than batch alkylation (C8 selecticity of 36% at 12.5 min). The reaction performance was determined, and the effect of acid concentration, phase ratio, reaction temperature, the ratio of isobutane to butene (I/O), and acid cycle times were investigated carefully. The results show that the selectivity of products can be effectively regulated by adjusting the droplet size, reaction temperature, and I/O. A two-step feeding technology was further invented to improve the C8 selectivity, and the RON could be increased to 97.9.In consideration of the low isobutane solubility in H2SO4 and the high H2SO4 viscosity, new methods for the intensification of sulfuric acid alkylation were proposed with the addition of caprolactam (CPL) and trifluoroacetic acid (TFA), and the C8 selectivity could be increased from 36% to 62% and 76%, respectively.
