Britschgi Joel, Kersten Wolfgang, Waldvogel Siegfried R, Schüth Ferdi
Department of Heterogeneous Catalysis, Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470, Mülheim, Germany.
Department Chemie, Johannes Gutenberg-Universität Mainz, Duesbergweg 10-14, 55128, Mainz, Germany.
Angew Chem Int Ed Engl. 2022 Oct 10;61(41):e202209591. doi: 10.1002/anie.202209591. Epub 2022 Aug 31.
The direct sulfonation of methane to methanesulfonic acid was achieved in an electrochemical reactor without adding peroxide initiators. The synthesis proceeds only from oleum and methane. This is possible due to in situ formation of an initiating species from the electrolyte at a boron-doped diamond anode. Elevated pressure, moderate temperature and suitable current density are beneficial to reach high concentration at outstanding selectivity. The highest concentration of 3.7 M (approximately 62 % yield) at 97 % selectivity was reached with a stepped electric current program at 6.25-12.5 mA cm , 70 °C and 90 bar methane pressure in 22 hours. We present a novel, electrochemical method to produce methanesulfonic acid, propose a reaction mechanism and show general dependencies between parameters and yields for methanesulfonic acid.
在不添加过氧化物引发剂的情况下，通过电化学反应器实现了甲烷直接磺化生成甲磺酸。该合成反应仅以发烟硫酸和甲烷为原料进行。这是由于在掺硼金刚石阳极处，电解质原位形成了引发物种。高压、适中的温度和合适的电流密度有利于在高选择性下达到高浓度。在6.25 - 12.5 mA cm²的阶梯电流程序、70°C和90 bar甲烷压力条件下，经过22小时，可达到最高浓度3.7 M（产率约62%），选择性为97%。我们提出了一种生产甲磺酸的新型电化学方法，提出了反应机理，并展示了参数与甲磺酸产率之间的一般关系。
