反应物溶解对阿加曲班催化加氢反应动力学的影响

IF 3.1 3区 化学 Q2 CHEMISTRY, APPLIED
Filippo Nanto*, Dario Ciato, Mariano Stivanello and Paolo Canu, 
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引用次数: 0

摘要

对加料间歇催化加氢生产阿加曲班进行了实验研究。排在第二位的昂贵且难以获得的中间体的特点是溶解速度缓慢,与反应过程平行发展。研究了反应与溶解动力学之间的耦合关系。在这种情况下,发现HPLC中的标准面积百分比方法具有误导性,需要校准,然后进行绝对峰面积测量才能正确确定溶出率,从而确定实际的化学动力学。实验量化了温度、搅拌速率和催化剂负载的作用。从40°C切换到80°C可以减少58%的批处理时间,尽管更高的温度会促进不需要的杂质的形成。搅拌速率控制了初始反应阶段,当试剂溶解至关重要时。催化剂装载是减少批处理时间的关键。催化剂负载的增加通过增加试剂和催化剂颗粒之间的碰撞频率来影响试剂的溶解速率。一个改进的第一性原理模型,考虑了催化剂用量对溶解传质系数的影响,显著提高了溶解预测的准确性,并能更好地识别本征反应动力学。微动力学描述的加入进一步改善了中间体和产物的预测。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Impact of Reactant Dissolution in the Kinetics of a Catalytic Hydrogenation for the Production of Argatroban

An experimental study was performed for a fed-batch catalytic hydrogenation for the production of Argatroban. The penultimate expensive and scarcely available intermediate is characterized by a slow dissolution rate that evolves in parallel with the reaction process. The study investigated the coupling between the reaction and dissolution kinetics. In these circumstances, the standard Area Percentage method in HPLC was found to be misleading, requiring calibration and then absolute peak area measurements to correctly identify the dissolution rate and thus the actual chemical kinetics. Experiments quantified the role of the temperature, stirring rate, and catalyst loading. Shifting from 40 to 80 °C reduced the batch time by 58%, although higher temperatures promoted the formation of undesired impurities. Stirring rate controlled the initial reaction phases when reagent dissolution is critical. Catalyst loading is key in reducing batch time. The increase in catalyst loading was proved to affect the reagent dissolution rate, by increasing the collision frequency between reagent and catalyst particles. A refined first-principles model, incorporating the effect of the catalyst amount on the dissolution mass transfer coefficient, significantly improved the accuracy of dissolution predictions and enabled better identification of the intrinsic reaction kinetics. The addition of a microkinetic description further improved the predictions of intermediates and products.

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来源期刊
CiteScore
6.90
自引率
14.70%
发文量
251
审稿时长
2 months
期刊介绍: The journal Organic Process Research & Development serves as a communication tool between industrial chemists and chemists working in universities and research institutes. As such, it reports original work from the broad field of industrial process chemistry but also presents academic results that are relevant, or potentially relevant, to industrial applications. Process chemistry is the science that enables the safe, environmentally benign and ultimately economical manufacturing of organic compounds that are required in larger amounts to help address the needs of society. Consequently, the Journal encompasses every aspect of organic chemistry, including all aspects of catalysis, synthetic methodology development and synthetic strategy exploration, but also includes aspects from analytical and solid-state chemistry and chemical engineering, such as work-up tools,process safety, or flow-chemistry. The goal of development and optimization of chemical reactions and processes is their transfer to a larger scale; original work describing such studies and the actual implementation on scale is highly relevant to the journal. However, studies on new developments from either industry, research institutes or academia that have not yet been demonstrated on scale, but where an industrial utility can be expected and where the study has addressed important prerequisites for a scale-up and has given confidence into the reliability and practicality of the chemistry, also serve the mission of OPR&D as a communication tool between the different contributors to the field.
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