Achieving Efficient and Low Content Ru‐Based Catalyst for Acetylene Hydrochlorination Based on N,N’‐Dimethylpropyleneurea

Abstract

A new Ru-based catalyst system based on N,N'-Dimethylpropyleneurea (DMPU) was developed for the acetylene hydrochlorination reaction in this study. The optimal 1 % Ru-10 %DMPU/AC catalyst exhibits the best activity with the acetylene conversion of 87.6 % under 170 8C and the GHSV (C 2 H 2 ) of 900 h À1 . Additionally, the Ru-10 %DMPU/AC with lower Ru content (0.2 wt%) displayed excellent activity and stability with acetylene conversion of 81.3 % after 200 h under the conditions of 170 8C and C 2 H 2 GHSV of 180 h À1 . The character-ization results indicate that the presence of DMPU could improve the dispersion of the catalytic species and provide full protection to prevent the sintering of the ruthenium particles and to inhibit the reduction of active ruthenium oxide component. Moreover, the catalytic property, characterizations and theoretical calculation results reveal that the ability to adsorb and activate HCl reactant with the addition of DMPU via its strong hydrogen bonding plays a significant role on the high stability of the Ru-DMPU/AC catalyst system.

Carbon with Surface‐Enriched Nitrogen and Sulfur Supported Au Catalysts for Acetylene Hydrochlorination

“…The reducibility and adsorption property of the substrates on catalysts could be affected via the changing microenvironment of active sites. H 2 ‐temperature programed reduction (H 2 ‐TPR) was a powerful technique for characterizing and analyzing heterogeneous catalysts ,. The reduction peaks at 300 °C for Au/AC and 352 °C for Au/N, S‐AC‐700 were attributed to the reduction of cationic Au 3+ species (Figure a) ,.…”

Carbon-supported ruthenium catalysts prepared by a coordination strategy for acetylene hydrochlorination

“…It has been reported that acetylene rather than HCl is more inclined to adsorption on metal sties [22,23]. The adsorption state of acetylene is inevitably affected by the electronic structure of metal ions in the ruthenium catalyst.…”

“…To improve the stability of the ruthenium catalyst, researchers have taken many approaches to suppress the deactivation of the catalyst. Recently, some researchers have proposed that the coke deposition can be suppressed by activating HCl [22][23][24], which can suppress the polymerization of acetylene by accelerating the reaction between HCl and acetylene. Our research group found that the acidic site of the ruthenium catalyst can induce the polymerization of acetylene, which would result in the deactivation of the catalyst [25].…”

Design of choline chloride modified USY zeolites for palladium-catalyzed acetylene hydrochlorination

“…Ionic liquids (ILs) have attracted much attention due to their unexpected catalytic activity in many heterogeneous reactions in recent years, 15,33–35 especially in the acetylene hydrochlorination reaction. 34–42 Li et al synthesized pyridinic N-rich aromatic ladder structure catalysts through controlling the self-assembly of polyacrylonitrile polymer chains and the prepared catalysts showed ∼93.0% acetylene conversion and exhibited a satisfying stability during 200 h. 36 Zhao et al prepared nitrogen–phosphorus doped carbon catalysts using 1-ethylsulfonic acid-3-methylimidazolium dihydrogen phosphate [ESO 3 HMim + H 2 PO 4 − ] and 1-ethyl-3-methylimidazolium dicyandiamide [[EMim] + N(CN) 2 − ] as phosphorus and nitrogen sources, and the catalyst also has an excellent activity for acetylene hydrochlorination. 34 Zhang et al successfully synthesized Ru-10% DMPU/AC catalysts and suggested the anchoring effect of the N-containing ligand can increase the dispersion of Ru species and decrease the coke deposition during reaction.…”