基于多酸的绿色可再生液相氧化脱硫与硫回收新方法研究

In response to the national practical needs in H2S removal and sulfur recovery from industrial and waste gases and based on the preliminary research of the applicants, this proposal outlined an effective and economical method of H2S removal and sulfur recovery using the heteropoly compounds(HPC) of the so-called rich elements of W and Mo of China as main desulfurizers, in forms of both inorganic acids and their corresponding ionic liquids, with the addition of catalytic species, if necessary, to adjust the activity of the main desulfurizer. Using water and ionic liquid as green solvents, new liquid redox scrubbers of HPC will be formulated, which are suitable for H2S removal and sulfur recovery at ambient and high temperatures, e.g. 150-250 C. Furthermore, researches concerning the relevant mechanisms governing the redox process as well as the macro-kinetic behavior of the overall process will be conducted. The outcome of the results from this project will lay a solid foundation for its further application in H2S removal and sulfur recovery from the purification of industrial gases, such as natural gas, coke oven gas, and semi-water gas, as well as exhaust gases from other processes.

本项目结合当前我国工业气及多种过程废气的脱硫净化与硫磺资源化回收的实际应用需求，在前期工作基础上，采用我国丰产元素钨、钼的多元杂多化合物及其对应的离子液体为脱硫主剂，辅配以必要的活性催化组分对其脱硫及再生性能进行调变。分别采用水溶液和绿色溶剂－离子液体构建并优选出分别适于常温和高温（150-250℃）的气体脱硫且均能同时回收硫磺的绿色可再生液相氧化脱硫新体系。在此基础上，通过系统、深入的宏观反应动力学及过程机理研究，为实现天然气、焦炉煤气、半水煤气等工业气体的脱硫精制与硫资源回收以及多种过程废气的脱硫净化奠定工业应用基础。

针对当前我国工业气及多种过程废气的脱硫净化与硫资源回收的实际应用需求，项目采用我国丰产元素钨、钼的不同结构多元杂多化合物及其对应的离子液体为脱硫主剂，辅配以必要的增效环境或添加剂对其脱硫及再生性能进行了调变。分别采用水溶液和离子液体构建了有工业应用前景的性能优良的常温及高温脱硫与硫资源回收可再生液相氧化新体系。首次实现了电化学方法对多酸脱硫液的再生。揭示了脱硫剂的结构、组成与性能之间的关系及脱硫再生的主要机制。通过宏观反应动力学研究，得到了过程动力学方程， 为工业气体的脱硫精制与硫资源回收以及多种过程废气的脱硫净化奠定了理论基础。核心技术申报国家发明专利2项。迄今共发表学术论文12篇，其中SCI收录8篇，EI收录1篇。有3篇发表在SCI一区高影响力期刊Chemical Engineering Journal (IF=5.310)和Journal of Hazardous Materials (IF=4.836)上，有1篇发表在SCI能源领域top期刊（二区）Fuel Processing Technology (IF=3.847)上。基于本项目的研究成果，应邀在国际知名出版公司Nova Science Publishers, Inc.出版的学术著作“Polyoxometalates: Properties, Structure and Synthesis”中撰写了第三章。项目执行期间，培养博士生2人（其中1人已经毕业并获博士学位，另外1人即将毕业并申请博士学位），硕士生2人（在读）。