γ-Al_(2)O_(3)基催化剂上高炉煤气COS的水解活性研究  

Investigation on the catalytic hydrolysis activity of COS from blast furnace gas over the γ-Al_(2)O_(3)-based catalysts

作　　者：高攀婷 李玉然[2] 林玉婷 曹强 常丽萍[1] 王建成[1] 朱廷钰[2] Panting GAO;Yuran LI;Yuting LIN;Qiang CAO;Liping CHANG;Jiancheng WANG;Tingyu ZHU(State Key Laboratory of Clean and Efficient Coal Utilization,Taiyuan University of Technology,Taiyuan,Shanxi 030024,China;Institute of Process Engineering,Chinese Academy of Sciences,Innovation Academy for Green Manufacturing,Beijing 100190,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,山西太原030024 [2]中国科学院过程工程研究所,中国科学院绿色过程制造创新研究院,北京100190

出　　处：《过程工程学报》2023年第2期301-310,共10页The Chinese Journal of Process Engineering

基　　金：河北省重点研发计划项目(编号:21373702D);河钢集团重点科技项目(编号:HG2021117)。

摘　　要：高炉煤气脱硫是实现钢铁行业多工序全流程超低排放的关键。高炉煤气中主要含硫组分是羰基硫(COS),常用γ-Al_(2)O_(3)基催化剂水解脱除,但是其水解活性及抗氧能力有待提高。本工作采用浸渍法制备了添加Fe和La活性组分的催化剂,通过ICP,XRD和TPD等手段表征了催化剂的理化性质,并在固定床-气相色谱联用装置考察了空速、粒径对催化剂催化水解COS过程的扩散效应,研究了催化剂的理化性质与COS水解活性的构效关系以及O_(2)的作用机制。结果表明,催化剂在80℃,160000h^(-1)条件下,活性组分Fe和La的添加可明显提高γ-Al_(2)O_(3)基催化剂的碱性位点;同时,丰富的孔隙结构降低了内扩散阻力,增强了H_(2)S从催化剂表面到气相的传质。Fe/Al_(2)O_(3)催化剂在保持较高的水解活性的同时能够协同脱除H_(2)S,但是O_(2)的存在增强了H_(2)S的吸附及其与Fe的硫化反应;而La/Al_(2)O_(3)催化剂的COS水解活性及稳定性较好,活性组分La可明显提高H_(2)S从催化剂表面到气相的脱附,进而提高抗氧中毒能力。Desulfurization for blast furnace gas is one of the keys to achieve ultra-low emissions for the multi-process in the iron and steel industry.The sulfur component in blast furnace gas is mainly organic sulfur-carbonyl sulfur(COS),which is usually removed by the catalytic hydrolysis method with γ-Al_(2)O_(3)based catalyst,but its hydrolysis activity and antioxidant capacity need to be improved.In this work,three kinds of catalysts with Fe or La as an active component were prepared by the impregnation method.The physical and chemical properties of the catalysts were characterized by ICP,XRD and TPD.The diffusion effect of gas hourly space velocity(GHSV)and particle size on the catalytic hydrolysis of COS were investigated on a fixed bed-gas chromatography combined device.The structure-activity relationship between the physicochemical properties of the catalysts and the hydrolysis activity of COS and the action mechanism of O_(2)were also analyzed.The results showed that the addition of Fe or La as active components can obviously improve the COS hydrolysis activity on the catalyst,due to the much more alkaline sites on the surface of theγ-Al_(2)O_(3)based catalyst at conditions of 80℃ and 160000 h^(-1).The abundant pore structure and suitable pore size can also reduce the internal diffusion resistance of COS and H_(2)S,enhance the mass transfer process of H_(2)S from the catalyst surface to the gas phase.Fe/Al_(2)O_(3)catalyst can collaboratively remove H_(2)S and simultaneously maintain a high hydrolytic activity.But the presence of O_(2)enhanced the adsorption of H_(2)S on the catalyst surface and the sulfidation reaction between H_(2)S and metal Fe.While La/Al_(2)O_(3)catalyst had better activity and stability for COS hydrolysis,and the active component La can significantly improve the desorption of H_(2)S from the catalyst surface to the gas phase,and then improve the anti-oxygen toxicity ability of the catalyst.

关 键 词：高炉煤气 羰基硫水解 氧化铝催化剂 硫化氢 铁和镧添加剂 

分 类 号：O643.36[理学—物理化学] TF53[理学—化学]