Competing commercial catalysts: Unprecedented catalyst activity and stability of Mizoroki-Heck reaction in a continuous packed bed reactor

Nemanja Vucetic,Jyri-Pekka Mikkola,Pasi Virtanen,Tapio Salmi,Andrey Shchukarev

doi:10.1016/j.cej.2021.134432

Nemanja Vucetic, Jyri-Pekka Mikkola + Show 3 more

Open Access

https://doi.org/10.1016/j.cej.2021.134432

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Abstract

• Supported Ionic Liquid Catalyst (SILCA) for the continuous Mizoroki-Heck reaction. • On-line UV–VIS spectrometry analysis for monitoring metal leaching. • Simple and long-performing processes for Mizoroki-Heck reaction in a continuous flow. Main obstacle for adopting continuous processes as a standard technology for Mizoroki-Heck reaction usually lies in its specific reaction mechanism. Here we present an important step forward answering the challenges unraveled through a comprehensive study that provides deeper understanding on the Mizoroki-Heck reaction, in particular the case when iodobenzene and butyl acrylate react in a continuous packed bed reactor in the presence of a Pd Supported Ionic Liquid Catalyst (SILCA). On-line UV–VIS spectrometry supported by ICP-OES, TEM and XPS measurements were carried out and the catalyst leaching was minimized. Finally, simple continuous flow process was proposed resulting in a high catalytic activity (up to 1470 mol ArI mol Pd −1 h −1 ) and reaching productivity in the range of 12,000 to 16,000 mol ArI mol Pd −1 thus competing with the performance of commercial catalysts.

Highlights

The growing interest in the production of fine chemicals, pharma ceuticals and agrochemicals by continuous process technology is re flected by several studies found in open literature [1,2,3,4,5,6,7,8,9]
The presented study discussed the utilization of continuous packed bed reactor technology for the Mizoroki-Heck reaction of iodobenzene and butyl acrylate with the use of Pd supported ionic liquid catalyst (SILCA)
For the optimization of the reaction conditions and investiga tion of the catalyst stability, on-line UV–VIS spectrometry was used, allowing correlation of Pd leaching with temperature, flow rate, the amount of reactants and catalyst loading

Summary

Introduction

The growing interest in the production of fine chemicals, pharma ceuticals and agrochemicals by continuous process technology is re flected by several studies found in open literature [1,2,3,4,5,6,7,8,9]. The main driving force is the advantage of the processes that valorise the benefits of continuous flow technologies, i.e. better production economy, good heat and mass transfer, waste reduction and enhanced product purity, higher throughput, safety and lower environmental impact [8]. The main obsta cles appeared to be the additional economical investments, namely, the small production volumes cannot justify additional investments into utilisation of continuous flow technologies. Other issues are related to the safety and break-down of the equipment, availability of sufficiently active reactants and their cost, as well as the development of the reliable downstream process for continuous separation since strict regulations on purity and metal contamination are valid for pharmaceuticals (0.5 to 5 ppm) [11,12,13,14]. Is why many efforts have been put in designing highly active and stable catalysts and developing simple technical solutions

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