Construction of Highly Dispersed Cu-P/Cl Active Sites Using Methyldiphenyloxophosphine for Efficient Acetylene Hydrochlorination

ACS SUSTAINABLE CHEMISTRY & ENGINEERING(2023)

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Abstract
To overcome the disadvantages of Cu-based catalysts, such as the low dispersion of active components and insufficient active species, several 15% Cu-Lx/AC catalysts for acetylene hydrochlorination were synthesized based on strong interactions between a ligand and CuCl2 precursors. The introduction of the methyldiphenyloxophosphine (MDPO) ligand effectively modulated the electronic properties of the metal centers, which contributed to the construction of a highly dispersed Cu- P/Cl local structure with Cu1+/Cu2+ as a plausible active center. The sintering of active components in the catalyst may be one of the main reasons for the decrease in catalytic performance. Meanwhile, the enhanced adsorption and activation of the catalyst for C2H2 and HCl molecules resulted in improved coking resistance. The most active catalyst (15% Cu8MDPO1/AC) could achieve a stable acetylene conversion of 97% at 180 degrees C, a gas hourly space velocity (GHSV) (C2H2) of 180 h-1, and a feed volume ratio (VHCl/ VC2H2) of 1.15, outperforming the benchmark catalyst. The excellent activity and stability in a 300 h laboratory test at a high GHSV and a 3414 h industrial sideline test at an industrial GHSV render the 15% Cu8MDPO1/AC catalyst as a reference for the construction of other catalysts from an environmental, economic, and application prospect perspective.
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Key words
copper-based catalysts,MDPO ligand,Cu-P,Cl active sites,acetylene hydrochlorination,improved performance
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