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芳伯胺重氮化及偶氮染颜料合成反应微型化研究

Diazotization of Primary Aromatic Amines and Synthesis of Azo Dyes and Pigments in a Microchemical System

作者:王法军
  • 学号
    2017******
  • 学位
    博士
  • 电子邮箱
    faj******com
  • 答辩日期
    2022.05.13
  • 导师
    徐建鸿
  • 学科名
    化学工程与技术
  • 页码
    189
  • 保密级别
    公开
  • 培养单位
    034 化工系
  • 中文关键词
    微反应器, 重氮化反应, 偶合反应, 动力学模型, 偶氮染颜料
  • 英文关键词
    microreactor, diazotization reaction, coupling reaction, kinetic model, azo dye and pigment

摘要

芳伯胺的重氮化反应及芳基重氮盐的偶合反应是两类典型的危险有机反应,在偶氮染/颜料合成领域有广泛的应用。传统间歇或者半间歇工艺存在反应效率低、污染大、运行能耗高和安全性差等诸多问题。对于芳伯胺重氮化反应过程,现有研究主要以条件优化为主,缺乏微反应器内反应过程的基础理论研究。而对于偶合反应,现有研究缺乏针对不同偶合反应特点的微反应器结构设计及反应工艺优化。本论文以实现芳伯胺重氮化反应及偶氮染/颜料合成过程高效安全为目标,深入研究微反应器内芳伯胺重氮化反应动力学规律,并以此指导红色基KD盐酸盐浆料的连续重氮化反应过程。接着选取了染颜料市场有代表性的三种偶氮染/颜料产品,根据其偶合反应特点分别设计了不同结构的微筛孔反应器,并在微反应器内进行连续化合成,发展了高效、安全和绿色的连续偶合反应新工艺。 微反应器内芳伯胺重氮化反应的动力学研究是微化工系统设计和过程优化的基础。以重氮化反应和重氮盐的热分解反应为基础建立了重氮化主副反应的动力学模型,研究了含有不同吸电子基团的芳伯胺对于重氮化反应速率的影响规律,揭示了重氮化反应及芳基重氮盐热分解反应特点。在利用上述方法得到的动力学模型的指导下,实现了微反应器内红色基KD盐酸盐浆料的连续重氮化反应过程,在反应时间为21.2 s时,重氮盐收率在99%以上,实现了重氮化反应过程的效、安全和可控。 对于偶氮染/颜料的连续化合成。一方面,针对色酚衍生类单偶氮颜料-颜料红146与联苯胺系双偶氮颜料-颜料黄14,分别在结构优化后的微筛孔反应器内进行连续化合成,优化条件下偶合转化率在99%以上,颜料产品纯度在95%以上。通过微反应新工艺所得到的颜料产品粒径小于间歇工艺,粒度分布也更窄。将产品与市售标样进行对比,产品色光与标样基本一致,而其透明度与着色强度两个性能与标样相比均有了显著的提高。在多通道微筛孔反应器内进行颜料红146连续化合成的初步放大研究,产量从单通道的110.0 g/h提升到660.0 g/h,而反应效果及产品性能均没有显著降低,初步验证了工艺放大的可靠性。另一方面,针对含有H酸结构的双偶氮染料-酸性黑10B的合成过程,设计了从酸性偶合到碱性偶合的微反应连续合成新工艺,在优化反应条件下连续合成新工艺所得产品收率达到95%。微反应器技术实现了偶氮染/颜料高效、安全和绿色的连续合成过程,相关技术指标及产品性能远优于传统间歇釜式生产工艺。

The diazotization reaction of primary aromatic amines and the coupling reaction of primary aromatic amine diazonium salts are two typical dangerous reactions, which are widely used in the synthesis of azo dyes and pigments. Traditional batch and semi-batch processes have many problems such as low reaction efficiency, high pollution, high energy consumption and poor safety. For the diazotization reaction of the primary aromatic amines, current researches mainly focused on the optimization of reaction conditions, and lacked the basic theoretical research on the reaction process in the microreactor. For the coupling reaction, the current researches lacked the design and optimization of the microreactor structures according to the characteristics of the coupling reaction. In this thesis, for realizing the high efficiency and safety of diazotization reaction and azo dyes and pigments synthesis process, the kineticof the diazotization reaction of the aromatic primary amines in the microreactor wasdeeply studied, and under the guidance of the above theoretical model, the continuous-flow diazotization of hydrochloride slurry was completed. Then, three representative products in the dye and pigment market were synthesized in the microreactor. Meanwhile, the micro-sieve dispersion mixers with different structures were designed according to the characteristics of the different coupling reactions. A new process of efficient, safe and green continuous-flow coupling reaction has been developed. The study on the kinetic of the primary aromatic amines diazotization reaction in the microreactor was the basis for the design and process optimization of the microchemical system. Based on the diazotization reaction and the thermal decomposition reaction of diazonium salts, the kinetic models for the main and side reactions of the diazotization reaction of the primary aromatic amine were established. The effects of the aromatic primary amines with different electron-withdrawing groups on the diazotization reaction rate were studied and the characteristics of the diazotization reaction and the thermal decomposition reaction of different kinds of the primary aromatic amines were revealed. Under the guidance of the kinetic model obtained by the above method, the continuous-flow diazotization reaction of the red base KD hydrochloride slurry in a microreaction system was established. When the reaction time was 21.2 s, the yield of the red base KD diazonium salt was above 99%. Finally, the high efficiency, safety and controllability of the diazotization reaction process was realized. For the continuous-flow synthesis of azo dyes and pigments, the typical naphthol-based monoazo pigment-Pigment Red 146 and benzidine-based disazo pigment-Pigment Yellow 14 were carried out in the micro-sieve dispersion mixers with optimized structures, and under the optimized conditions, the coupling reaction conversion was above 99 % and the purity of the pigment product was above 95%. The particle size of the pigment product was smaller than that was synthesized by batch process, and the particle size distribution was also narrower. Comparing to the pigment products with the pigment standard sample, the products synthesized by the continuous-flow process had basically the same shade as the standard sample, while the transparency and coloring strength were significantly improved. Then, a preliminary study on the scale-up of the continuous-flow synthesis of Pigment Red 146 was carried out in a multi-channel micro-sieve mixer. The output was increased from 110.0 g/h to 660.0 g/h, while the reaction conversion and product performance were not significantly reduced. The reliability of scale-up of synthesis process was preliminarily verified. For the synthesis process of typical bisazo dyes containing H acid structure-Acid Black 10B, a microreaction system from acid coupling reaction to basic coupling reaction was developed. Under the optimized reaction conditions, the yield of the whole coupling reaction process could reach 95%. The microreaction technology realized an efficient, safe and green continuous-flow synthesis process of azo dyes and pigments, and the relevant technical indicators and product performance were far superior to the traditional batch process.