ZnO/MCM-41煤气脱硫剂脱硫过程COS生成行为及Co助剂的影响  

COS formation behavior and influence of Co additive of ZnO/MCM-41 coal gas desulfurizer in desulfurization process

作　　者：杨梦滋 段新伟 冯宇[1] 武蒙蒙[1] 米杰[1] YANG Mengzi;DUAN Xinwei;FENG Yu;WU Mengmeng;MI Jie(State Key Laboratory of Clean and Efficient Coal Utilization,Key Laboratory of Coal Science and Technology,Ministry of Education,Taiyuan University of Technology,Taiyuan 030024,Shanxi,China)

机构地区：[1]太原理工大学,省部共建煤基能源清洁高效利用国家重点实验室,煤科学与技术教育部重点实验室,山西太原030024

出　　处：《低碳化学与化工》2023年第4期55-62,共8页Low-Carbon Chemistry and Chemical Engineering

基　　金：国家自然科学基金(22278294,21978188,21908156);山西省自然科学基金(20210302123191)。

摘　　要：在金属氧化物脱硫过程中,普遍存在部分硫化氢(H_(2)S)转化为羰基硫(COS)的现象,而COS具有与H_(2)S相似的危害性,且脱除难度更大。采用溶胶凝胶法制备了具有良好脱硫性能的ZnO/MCM-41煤气脱硫剂(以下简称“脱硫剂”),在固定床装置上探究了COS在煤气脱硫过程中的生成行为,并提出采用Co助剂对脱硫剂进行改性的方法来抑制COS的形成,然后结合XRD和XPS等表征手段对脱硫剂的物相组成和结构进行分析。通过研究不同脱硫气氛中COS的生成行为,发现COS主要来源于CO/CO_(2)与H_(2)S之间的反应,且ZnS对CO_(2)与H_(2)S之间的反应起催化作用;CO-H_(2)S反应与CO_(2)-H_(2)S反应之间不存在协同作用;H_(2)对COS的形成有抑制作用。向脱硫剂中添加Co质量分数为1%、3%和5%的Co助剂时,分别使脱硫过程中的COS产生量降低了69.0%、94.9%和98.4%,这主要与Co助剂对COS加氢反应的催化作用有关。此外,添加Co质量分数为3%的Co助剂使脱硫剂的硫容提升了0.32%。In the process of metal oxide desulfurization,partial hydrogen sulfide(H_(2)S) is commonly converted into carbonyl sulfide(COS),and COS has similar harm to H_(2S) and is more difficulty to remove.ZnO/MCM-41 coal gas desulfurizer(hereinafter referred to as“desulfurizer”) with good desulfurization performance was prepared by sol-gel method.The formation behavior of COS in desulfurization process was studied on a fixed bed device,and the method of inhibiting COS formation by modification of Co additive was proposed.Then the phase composition and structure of desulfurizer were analyzed by XRD,XPS and other characterization methods.By comparing COS formation behaviors in different desulfurization atmospheres,it is found that COS mainly derives from the reaction of CO/CO_(2) with H_(2)S,and ZnS catalyzes the reaction of CO_(2) with H_(2)S.Meanwhile,there is no synergistic effect between the reaction of CO-H_(2S) and CO_(2)-H_(2)S.The presence of H_(2) inhibits the formation of COS.When the Co additive with the mass fraction of Co of 1%,3%and 5%are added to the desulfurizer,the COS production in the desulfurization process can be reduced by 69.0%,94.9%and 98.4%,which is mainly related to the catalytic effect of additive Co on COS hydrogenation.In addition,the sulfur capacity of desulfurizer is increased by 0.32%by adding the Co additive with 3%Co mass fraction.

关 键 词：羰基硫 ZnO/MCM-41 高温煤气 脱硫剂 加氢脱硫 

分 类 号：TQ546.5[化学工程—煤化学工程]