Hughes Rory, Lennon David
School of Chemistry, University of Glasgow Joseph Black Building Glasgow G12 8QQ UK
RSC Adv. 2025 Jul 16;15(31):25178-25186. doi: 10.1039/d5ra04045k. eCollection 2025 Jul 15.
The authors have recently refined a model for phosgene synthesis over industrial grade activated carbons that involves two classes of active sites: type-I and type-II. This article looks to further validate the model by examining kinetic aspects of the reaction. The work focuses on a single formulation of activated carbon, Norit RX3 Extra, and extends the applicability of the previous analysis undertaken on the Donau Supersorbon K40 formulation of activated carbon; both materials are representative industrial grade catalysts active for phosgene synthesis. The orders of this reaction, with respect to reagents and products CO, Cl and COCl are 1.04 ± 0.02, 0.46 ± 0.02, 0.04 ± 0.01 respectively. These findings reproduce the observations over Donau Supersorbon K40 and further validate the proposed reaction model. However, non-competitive adsorption studies over fresh catalyst reveal the following order of adsorption coefficients (): > ≫ . This contrasts with the studies over Donau Supersorbon K40, suggesting a different distribution of active sites. Studies that regenerate the catalyst and re-adsorb chlorine show the concentrations of type-I and type-II Cl adsorption sites are 3.2 and 0.32 mMol Cl per g, respectively; the retention on type I sites being 3.5 times greater for the Norit material than is observed for the Donau sample. Mass balance profiles endorse these findings. Temperature-programmed breakthrough measurements are interpreted as indicating a degree of surface etching of the carbonaceous substrate. Whilst this work reports some distinct differences between the two catalysts, the recently amended phosgene synthesis reaction model is validated over Norit RX3 Extra, enhancing the model's credentials as being representative for phosgene synthesis over activated carbon formulations.
作者们最近改进了一种在工业级活性炭上合成光气的模型,该模型涉及两类活性位点:I型和II型。本文旨在通过研究反应的动力学方面进一步验证该模型。这项工作聚焦于一种单一配方的活性炭Norit RX3 Extra,并扩展了先前对Donau Supersorbon K40配方活性炭所做分析的适用性;这两种材料都是对光气合成有活性的典型工业级催化剂。该反应对于试剂以及产物CO、Cl和COCl的反应级数分别为1.04±0.02、0.46±0.02、0.04±0.01。这些发现重现了在Donau Supersorbon K40上的观察结果,并进一步验证了所提出的反应模型。然而,对新鲜催化剂的非竞争性吸附研究揭示了以下吸附系数顺序(): > ≫ 。这与对Donau Supersorbon K40的研究形成对比,表明活性位点的分布不同。对催化剂进行再生并重新吸附氯的研究表明,I型和II型Cl吸附位点的浓度分别为每克3.2和0.32 mMol Cl;对于Norit材料,I型位点上的保留量比Donau样品中观察到的大3.5倍。质量平衡曲线支持了这些发现。程序升温突破测量结果被解释为表明碳质底物存在一定程度的表面蚀刻。虽然这项工作报告了两种催化剂之间的一些明显差异,但最近修正的光气合成反应模型在Norit RX3 Extra上得到了验证,增强了该模型作为活性炭配方上光气合成代表性模型的可信度。