An efficient and stable heterogeneous Zeolite Supported Ionic Liquid Catalyst (IL/CaX) has been explored in acetylene hydrochlorination reaction. The IL/CaX catalyst exhibits excellent space time yields of vinyl chloride (VCM), when compared to the benchmark of Au/C systems. Through characterization and kinetic studies, the reaction follows a two-site mechanism, which is described as the adsorbed hydrogen chloride on the Ca2+ in zeolite, reacting with the adsorbed acetylene on the cation of ionic liquid to form vinyl chloride. The catalytic reaction takes place at the IL/CaX interface, whilst the upper interphase IL/CaX is not active. The deactivation of the catalyst is caused by the dissolving byproducts in the ionic liquid layer, which can be reactivated by a simple vacuum procedure. It is of great significance to study and develop green non-mercury catalysts, in acetylene hydrochlorination.
Adsorption and activation for substrates and the stability of Pd species in Pd-based catalysts are imperative for their wider adoption in industrial and practical applications. However, the influence factor of these aspects has remained unclear. This indicates a need to understand the various perceptions of the structure–function relationship that exists between microstructure and catalytic performance. Herein, we revisit the catalytic performance of supported-ionic-liquid-phase stabilized Pd-based catalysts with nitrogen-containing ligands as a promoter for acetylene hydrochlorination, and try to figure out their regulation. We found that the absolute value of the differential energy, |Eads(C2H2)-Eads(HCl)|, is negative correlated with the stability of palladium catalysts. These findings imply that the optimization of the electron structure provides a new strategy for designing highly active yet durable Pd-based catalysts.
Development of a sustainable process for designing and synthesising an active and stable catalyst for hydrochlorination of acetylene is challenging, yet crucial, for industrial vinyl chloride monomer (VCM) production. Herein, direct synthesis of bimetallic AuCu catalysts using organic aqua regia (OAR) preparation methods was investigated. In comparison with conventional aqua regia (AR), bimetallic AuCu catalysts synthesised from OAR exhibit enhanced activity and stability. After careful characterisation of the catalyst samples using X-ray diffraction patterns (XRD), Scanning transmission electron microscopy (STEM), X-ray photoelectron spectroscopy (XPS), and Temperature-programmed desorption (TPD), this observation was justified for the following reasons: 1) the existence of sulphur and nitrogen atoms stabilised the cationic Au active sites, and 2) OAR helped to sustain the function of the Cu promotor by stabilising it. Advanced understanding on the importance of promoter stability has unveiled new perspectives for this research area.