Abstract:

The aqueous wet oxidation desulfurization process has been widely used in the screening of industrial process gas containing H₂S, but there are common problems such as easy degradation of desulfurizer, poor sulfur quality, high output of by-salts and serious secondary pollution. The non-aqueous wet oxidation process constructed with dissolution of inorganic iron salt in organic solvents can not only realize oxidative desulfurization performance, but also has the advantages of eliminating the interference of CO₂ and avoiding the overoxidation of desulfurizer by reactive oxygen species. However, due to the low solubility of iron salts in organic solvents, the development of non-aqueous wet oxidative desulfurization of iron salts is restricted. In recent years, the non-aqueous ionic liquid wet oxidative desulfurization process (Nasil) based on metal-based ionic liquids with good oxidation ability, redox reversibility, chemical thermal stability and super solubility in organic solvents has achieved rapid development. This paper states the necessity and development opportunities of wet oxidation desulfurization aiming at the causes of the problems of aqueous wet oxidation desulfurization process and the current development trend of energy environment. The principle of non-aqueous wet oxidative desulfurization reaction and process intensification with application of iron-based ionic liquids is introduced, and its theoretical developments and application exploration process in the past ten years are summarized from the point of the structural design and composition optimization of metal based ionic liquid desulfurizer. In view of the challenges faced by the current wet oxidative desulfurization technology, it should focus on the urgency of developing new desulfurization ideas. Finally, the prospects for the integration and development of hydrocarbon resources in the desulfurization purification process are put forward.

Key words: non-aqueous phase, metal-based ionic liquids, hydrogen sulfide, wet oxidation desulfurization, sulfur separation

摘要：

水相湿法氧化脱硫工艺在含硫化氢的工业过程气净化中得到广泛应用，但普遍存在脱硫剂易降解、硫磺品质差和副盐产量高等二次污染严重的难题。将无机铁盐溶于有机溶剂构建的非水相湿法氧化工艺不仅能实现氧化脱硫，而且具有消除CO₂酸性气干扰和避免活性氧过度氧化作用而产生大量副盐的优势。但由于铁盐在有机溶剂中的溶解度小而制约了铁盐非水相湿法氧化脱硫工艺的发展。近年来，基于金属基离子液体良好的氧化性、氧化还原可逆性和稳定性，及在有机溶剂中的超溶解性而构建的非水相离子液体湿法氧化脱硫工艺(Nasil)取得了快速发展。通过剖析水相湿法氧化脱硫工艺的问题成因，结合当前能源环境的发展趋势，阐述了湿法氧化脱硫的必要性和发展机遇。从金属基离子液体脱硫剂结构设计和组成优化出发，介绍非水相离子液体湿法氧化脱硫反应和过程强化原理，归纳总结新工艺十多年来的理论发展和应用探索历程。最后，针对现阶段湿法氧化脱硫技术所面临的挑战，强调开拓新型脱硫思路的重要性，为脱硫净化过程中碳氢资源的整合发展提出展望。

关键词: 非水相, 金属基离子液体, 硫化氢, 湿法氧化脱硫, 硫磺分离