State Key Laboratory of Clean and Efficient Coal Utilization,Taiyuan University of Technology
Key Laboratory of CoalScience and Technology,Ministry of Education,Taiyuan University of Technology

中高温煤气脱硫是实现煤炭清洁高效利用的关键技术之一。由金属氧化物脱硫反应动力学中硫化物生长扩散机理可知,保持脱硫剂活性组分高分散和小尺寸有利于减小脱硫反应扩散传质阻力,提高活性相利用率。采用不同种类锌盐和六亚甲基四胺(HMTA)在负载有MnO2种子层的纳米纤维载体上水热合成了一系列锌锰复合氧化物脱硫剂。通过探讨反离子与锌锰氧化物晶粒尺寸的内在关系,阐明了活性相晶体成核及生长机制。研究表明,水热溶液中反离子对Zn2+与OH−络合缩合反应有显著的抑制作用,反离子分别为NO3−和SO42−相比,脱硫剂中Mn3O4晶相平均晶粒尺寸减小39.2%,活性相颗粒粒径减小24.7%。同时,脱硫测试表明,脱硫剂ZN@MCNFs的总体活性组分利用率比ZS@MCNFs提高7%。研究所阐明的锌锰基脱硫剂晶体生长机制,为开发性能优异的金属氧化物脱硫剂提供了理论支撑。

Medium and high temperature gas desulfurization is one of the key technologies to realize the clean and efficient utilization ofcoal. The mechanism of sulfide growth and diffusion in the kinetics of metal oxide desulfurization reaction indicates that keeping the activecomponent of desulfurization sorbent with high dispersion and small size is beneficial to reduce the diffusive and mass transfer resistanceof the desulfurization reaction and to improve the utilization of the active phase. A series of zinc-manganese composite oxidedesulfurization sorbent were hydrothermally synthesized using different types of zinc salts and hexamethylenetetetramine (HMTA) onnanofiber supporter loaded with MnO2 seed layer,and the nucleation and growth mechanisms of the active-phase crystals were elucidatedby exploring the interrelationships between the type of counter-ion and the grain size of zinc-manganese oxides. It was shown that thecounter-ion in hydrothermal solution have a significant inhibitory behavior for the complexation and condensation reaction of Zn withOH. Compared with NO3and SO4,the average grain size of Mn3O4 crystal phase in the desulfurization sorbent decreased by 39.2%,andthe particle size of the active phase decreased by 24.7%. Meanwhile,desulfurization tests showed that the overall active componentutilization of the desulfurization sorbent ZN@MCNFs was 7% higher than that of ZS@MCNFs. The crystal growth mechanism of zinc-manganese-based desulfurization sorbent elucidated by the research provides theoretical support for the development of metal oxidedesulfurization sorbent with excellent performance.

国家自然科学基金资助项目(22378292、21908156);青年人才托举工程资助项目(2023QNRC001);山西省应用基础研究计划资助项目(202303021211072)

武帅山,孙阳杰,牛芳芳,等.水热合成锌锰基脱硫剂中晶体生长机制研究[J].洁净煤技术,2025,31(2):49−58.

WU Shuaishan,SUN Yangjie,NIU Fangfang,et al. Study of crystal growth mechanism in hydrothermal synthesis of zinc-manganese based desulfurization sorbent[J].Clean Coal Technology,2025,31(2):49−58.