As a promising alternative to HgCl₂ for acetylene hydrochlorination, a novel catalyst of Ru/ammonium oxalate (NCO)-activated carbon (AC) was developed, which shows approximately 90% conversion of acetylene and over 99% selectivity for the vinyl chloride monomer (VCM). In comparison to the conventional Ru/AC catalyst, the amount of ruthenium chloride in Ru/NCO-AC was reduced to less than 0.2 wt %. In addition, the coke deposition and Ru(0) generation were decreased by approximately 18% and 50%, respectively. Characterizations indicated that the N-doped AC could inhibit the over-reduction of active Ru species and decrease the coke deposition on the catalyst. Density functional theory calculations revealed that NCO-AC could provide a synergistic environment for the Ru-based catalyst. Acetylene molecules tend to be adsorbed on carbon atoms adjacent to nitrogen atoms, which protects Ru(IV) from being reduced to Ru(0) and stabilizes the reactivity. The 0.95 eV energy barrier of Ru/NCO-AC was much lower than that of a catalyst without N atoms (1.50 eV). Moreover, the low Ru content catalyst was placed in an industrial reactor and showed excellent activity during a 500 h industrial experiment. These results may be helpful for designing efficient nonmercury catalysts and replacing existing HgCl₂ for the commercial application of acetylene hydrochlorination.

中文翻译：

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用于非汞乙炔盐氯化法的低 Ru/铵草酸盐催化剂的增强催化性能


作为乙炔盐氯化的 HgCl₂ 的有前途的替代品，开发了一种新型 Ru/草酸铵 （NCO） -活性炭 （AC） 催化剂，其乙炔转化率约为 90%，对氯乙烯单体 （VCM） 的选择性超过 99%。与传统的 Ru/AC 催化剂相比，Ru/NCO-AC 中氯化钌的量降低到 0.2 wt % 以下。此外，焦炭沉积和 Ru（0） 生成分别减少了约 18% 和 50%。表征表明，N 掺杂 AC 可以抑制活性 Ru 物种的过度还原并减少催化剂上的焦炭沉积。密度泛函理论计算表明，NCO-AC 可以为 Ru 基催化剂提供协同环境。乙炔分子倾向于吸附在与氮原子相邻的碳原子上，这保护了 Ru（IV） 不被还原成 Ru（0） 并稳定了反应性。Ru/NCO-AC 的 0.95 eV 能垒远低于不含 N 原子的催化剂 （1.50 eV）。此外，将低 Ru 含量的催化剂置于工业反应器中，并在 500 h 的工业实验中表现出优异的活性。这些结果可能有助于设计高效的非汞催化剂和替代现有的 HgCl₂ 用于乙炔盐氯化法的商业应用。