NiO含量对NiMo/Al_(2)O_(3)催化剂在焦炉煤气中噻吩加氢脱硫性能的影响  

Effect of NiO content on thiophene hydrodesulfurization performance of NiMo/Al_(2)O_(3)catalyst in coke oven gas

作　　者：李姣姣 秦志峰[1,2] 李晓红 杜朕屹[1,2] 于峰 翟志强 吴琼笑[4] LI Jiaojiao;QIN Zhifeng;LI Xiaohong;DU Zhengyi;YU Feng;ZHAI Zhiqiang;WU Qiongxiao(State Key Laboratory of Clean and Efficient Coal Utilization,Taiyuan University of Technology,Taiyuan 030024,Shanxi,China;College of Chemical Engineering and Technology,Taiyuan University of Technology,Taiyuan 030024,Shanxi,China;Shanxi Dongyi Coal Power Aluminum Group Coal Chemical Co.,Ltd.,Xiaoyi 032200,Shanxi,China;Dongguan Energy Investment Group Co.,Ltd.,Dongguan 523000,Guangdong,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]太原理工大学化学工程与技术学院,山西太原030024 [3]山西东义煤电铝集团煤化工有限公司,山西孝义032200 [4]东莞市能源投资集团有限公司,广东东莞523000

出　　处：《低碳化学与化工》2025年第4期71-79,共9页Low-Carbon Chemistry and Chemical Engineering

基　　金：山西省科技重大专项(MJH2016-03);山西浙大新材料与化工研究院研发项目(2021ST-AT-002);东莞市能源投资集团有限公司攻关项目(RH2000004464)。

摘　　要：焦炉煤气作为气体资源,常被用作化工原料,然而其中噻吩(C_(4)H_(4)S)等硫化物杂质的存在对催化剂具有较强毒害作用,工业上常通过二级镍钼加氢脱硫对噻吩进行深度脱除。为探究金属负载量对催化剂性能的影响,采用浸渍法制备了不同NiO含量(5%、10%、15%和20%,质量分数)的NiMo/Al_(2)O_(3)催化剂;在反应温度250~390℃、压力1 MPa和原料空速4500 h^(-1)条件下,对催化剂焦炉煤气噻吩加氢脱硫性能进行了测试;并通过N2吸/脱附、XRD、H_(2)-TPR和XPS等表征手段,探究了NiO含量对NiMo/Al_(2)O_(3)催化剂性能的影响。结果表明,在270~370℃区间内,催化剂的C_(4)H_(4)S转化率从大到小依次为Ni_(5)Mo_(15)/Al_(2)O_(3)、Ni_(10)Mo_(15)/Al_(2)O_(3)、Ni_(15)Mo_(15)/Al_(2)O_(3)和Ni_(20)Mo_(15)/Al_(2)O_(3)。其中,Ni_(5)Mo_(15)/Al_(2)O_(3)催化剂,290℃时C_(4)H_(4)S转化率达到70%,330℃时达到90%,明显高于其他3种催化剂。这归因于该催化剂在预硫化过程中,生成了更多活性物种MoS2,硫化程度较高。但随着NiO含量增大,可能发生NiO包覆MoO3的现象,导致催化剂硫化程度下降,催化性能减弱。Coke oven gas,as a valuable gaseous resource,is often used as a chemical raw material.However,sulfur impurities such as thiophene(C_(4)H_(4)S)in the gas exhibit strong poisoning effects on catalysts.Industrially,deep removal of thiophene is typically achieved via secondary Ni-Mo hydrodesulfurization.To investigate the effect of metal loading on catalyst performance,NiMo/Al_(2)O_(3)catalysts with varying NiO contents(5%,10%,15%and 20%,mass fraction)were prepared using the impregnation method.The hydrodesulfurization performance of these catalysts in coke oven gas was tested under conditions of reaction temperatures from 250℃to 390℃,the pressure of 1 MPa,and the gas hourly space velocity of 4500 h^(-1).The effects of NiO content on the catalyst performance were analyzed using characterization techniques such as N2 adsorption/desorption,XRD,H_(2)-TPR,and XPS.The results show that in the temperature range of 270℃to 370℃,the C_(4)H_(4)S conversion rates of the catalysts decrease in the order of Ni_(5)Mo_(15)/Al_(2)O_(3),Ni_(10)Mo_(15)/Al_(2)O_(3),Ni_(15)Mo_(15)/Al_(2)O_(3)and Ni_(20)Mo_(15)/Al_(2)O_(3).Among them,the Ni_(5)Mo_(15)/Al_(2)O_(3)catalyst achieves a C_(4)H_(4)S conversion rate of 70%at 290℃and 90%at 330℃,significantly outperforming the other three catalysts.This is attributed to the formation of more active MoS2 species during the presulfurization process,resulting in a higher degree of sulfuration.However,with increasing NiO content,the phenomenon of NiO encapsulating MoO3 likely occurres,resulting in decreased sulfuration and diminished catalytic performance.

关 键 词：NiO含量 焦炉煤气 噻吩 加氢脱硫 NiMo/Al_(2)O_(3) 

分 类 号：TQ426[化学工程]