Desulfurization of hexyl sulfide and hexanethiol using supercritical water (SCW) was investigated by combining experimental and computational methods to study the desulfurization of alkyl sulfides and thiols in SCW. Desulfurization was conducted for 0 ∼ 30 min at 400 °C using thermal decomposition and SCW decomposition (24.7 ∼ 25.6 MPa), and the reaction pathways were built using the automated Reaction Mechanism Generator (RMG) and Gaussian 09. In thermal decomposition, C6-hydrocarbons (hexane, hexene) are main products, but in SCW, C5-hydrocarbon (pentane) in addition to C6-hydrocarbons are main products with higher alkane to alkene ratio. For the reaction pathways, in SCW, water participates as catalysts and reactants donating hydrogens with inhibited production of cyclic sulfides while in thermal decomposition, the hydrogen was deficient producing aromatic sulfur compounds such as thiophenes and alkyl-thiacycloalkanes. This study is expected to clarify the decomposition reactions of alkyl sulfides and alkyl thiols in SCW.

结合实验和计算方法，研究了超临界水（SCW）对己基硫醚和己硫醇的脱硫作用，研究了SCW中烷基硫醚和硫醇的脱硫作用。使用热分解和SCW分解（24.7〜25.6 MPa）在400°C下进行0到30分钟脱硫，并使用自动反应机理发生器（RMG）和高斯09建立反应路径。在热分解中，C6-碳氢化合物（己烷，己烯）是主要产品，但在SCW中，除C6-碳氢化合物外，C5-碳氢化合物（戊烷）是烷烃与烯烃比更高的主要产品。对于反应路径，在SCW中，水作为催化剂和反应物参与氢的提供，而在热分解过程中，环硫化物的生成受到抑制，氢不足以产生芳族硫化合物，例如噻吩和烷基-硫代环烷烃。预期该研究将阐明SCW中烷基硫化物和烷基硫醇的分解反应。