活性组分对羰基硫水解效率与脱硫效果的影响  

Effects of active component on hydrolysis efficiency and desulfurization efficiency of carbonyl sulfur

作　　者：王宏涛 潘程 何子祥 陈倍倍 孟庆民 龙红明 WANG Hongtao;PAN Cheng;HE Zixiang;CHEN Beibei;MENG Qingmin;LONG Hongming(School of Metallurgical Engineering,Anhui University of Technology,Maanshan 243032,Anhui,China;MCC Baosteel Technology Services Co.,Ltd.,Shanghai 201999,China;Key Laboratory of Metallurgical Emission Reduction and Resources Recycling(Anhui University of Technology),Ministry of Education,Maanshan 243002,Anhui,China)

机构地区：[1]安徽工业大学冶金工程学院,安徽马鞍山243032 [2]中冶宝钢技术服务有限公司,上海201999 [3]冶金减排与资源综合利用教育部重点实验室(安徽工业大学),安徽马鞍山243002

出　　处：《钢铁》2024年第8期189-199,共11页Iron and Steel

基　　金：国家自然科学基金资助项目(52004001,52074080);国家级大学生创新创业训练计划资助项目(202310360012)。

摘　　要：高炉煤气前端精脱硫技术已成为当前研究的热点,其关键在于开发低温高活性长寿命有机硫(主要为羰基硫COS)水解催化剂。以活性炭为载体、金属氧化物为活性组分,采用共浸渍法制备活性炭基催化剂,研究金属氧化物种类与负载量对催化剂脱硫率和COS水解率的影响规律,同时利用现代分析测试技术揭示脱硫过程中硫化物的转化机理。研究结果表明,纯活性炭催化剂对COS的脱除效果较差,脱硫率和COS水解率均低于30%。负载金属氧化物可以改善催化剂的脱硫性能,当铁氧化物负载量为3%时,催化剂高活性脱硫(脱硫率大于99%)时间为48 min,穿透硫容为63.72 mg/g。随着铁氧化物负载量的增加,催化剂比表面积、总孔容和微孔体积均有所减小,但仍具有丰富的孔隙结构,且脱硫率、COS水解率和穿透硫容均呈现先增加后降低的趋势,当铁氧化物负载量为16%时,催化剂的脱硫性能较好,高活性脱硫时间和高活性水解(COS水解率大于99%)时间约为78 min,穿透硫容达到104.21 mg/g。通过BET、XRD、XPS和SEM等表征手段发现在催化剂的作用下,COS首先发生水解反应转化为H2S,然后在氧化官能团和金属离子的作用下H2S转化为硫酸盐和单质硫,并附着在催化剂孔隙中,从而实现硫化物的脱除。Front-end fine desulphurization technology of blast furnace gas has become the focus of current research,and the key point is to develop low-temperature,high-activity and long-life catalyst for the hydrolysis of organic sulfur(mainly carbonyl sulfur COS).Activated carbon(AC)-based catalyst was prepared by co-impregnation method with AC as the carrier and metal oxide as the active component.Furthermore,the effects of the type and the loading amount of metal oxide on the desulfurization ratio and COS hydrolysis ratio of the catalyst were experimentally investigated.Simultaneously,the transformation mechanism of sulfide during the desulfurization process was revealed by utilizing modern analysis and testing technology.The results showed that the removal effect of COS by pure AC catalyst is poor,and the desulfurization ratio and the COS hydrolysis ratio were lower than 30%.The desulfurization property of catalyst can be improved by loading metal oxides.As the loading amount of iron oxide is about 3%,the high-active desulfurization(desulfurization ratio>99%)time is approximately 48 min,and the breakthrough sulfur capacity is 63.72 mg/g.With increasing the loading amount of iron oxide,the specific surface area,total pore volume,and micropore volume of the catalyst are decreased,and the catalyst still has abundant pore structure.Meanwhile,the desulfurization ratio,COS hydrolysis ratio,and breakthrough sulfur capacity are all increased firstly and then decreased with increasing the iron oxide loading amount.When the loading amount of iron oxide is 16%,the desulfurization performance of the catalyst is better,and the high active desulfurization time and the high active hydrolysis(COS hydrolysis ratio>99%)time are about 78 min,and the breakthrough sulfur capacity reaches 104.21 mg/g.By means of BET,XRD,XPS,and SEM,it was found that under the action of the catalyst,COS is firstly hydrolyzed into H2S,and then H2S is converted into sulfate and elemental sulfur under the action of oxidation functional groups and metal ions,whi

关 键 词：高炉煤气 羰基硫 活性炭 金属氧化物 催化水解 

分 类 号：TF53[冶金工程—钢铁冶金]