焦炉煤气常量含碳气氛对加氢脱硫催化剂活性、选择性和积炭的影响

Effects of constant carbon atmosphere on the activity, selectivity and coking of catalysts in hydrodesulfurization of coke oven gas

利用微型固定床反应装置对工业Fe-Mo预加氢脱硫催化剂进行加氢脱硫(HDS)评价,研究焦炉煤气中不同常量含碳原料组分(CH_(4)、C_(2)H_(4)、C_(2)H_(6)、CO、CO_(2))对催化剂加氢活性、选择性以及积炭的影响,并采用红外碳硫分析仪、N_(2)吸附-脱附、Raman以及TPRS-MS对催化剂进行表征。结果表明:在N_(2)气氛下,COS、CS_(2)和C_(4)H_(4)S加氢转化由易到难顺序为:COS>CS_(2)>C_(4)H_(4)S,但COS加氢转化受含碳气氛影响最明显,致使焦炉煤气加氢脱硫中COS难以完全脱除;不同气氛对硫化物加氢选择性都会产生影响,其中C_(2)H_(4)气氛对选择性影响最明显,而对H2S收率影响最明显的是CO_(2)和CO;不同含碳气氛在410℃下稳定反应11h后催化剂均发生积炭,主要以石墨化炭为主,其中C_(2)H_(4)气氛下积炭最严重,气氛对积炭影响顺序为:C_(2)H_(4)>CO_(2)>CO>CH_(4)>N_(2)>C_(2)H_(6)。

Hydrodesulfurization (HDS) evaluation of the industrial Fe-Mo catalyst was carried out by using a micro fixed bed reactor.The influence of constant carbon components (CH_(4)、C_(2)H_(4)、C_(2)H_(6)、CO、CO_(2)) in coke oven gas on the hydrogenation activity,selectivity and carbon deposition were studied.The catalyst was characterized by infrared carbon sulfur analyzer,N_(2)adsorption desorption,Raman and TPRS-MS.The results showed that the order of COS,CS_(2)and C_(4)H_(4)S hydrogenation conversion from easy to difficult was COS>CS_(2)>C_(4)H_(4)S under the carbon-free atmosphere,but the hydroconversion of COS was obviously affected by the carbonaceous atmosphere,which made it difficult to completely remove COSs.The atmosphere also had an impact on the hydrogenation selectivity of sulfide,among which C_(2)H_(4)had the most obvious effect,while CO_(2)and CO had the most obvious effect on the yield of H2S.After 11h stable reaction at 410℃in different carbonaceous atmospheres,carbon deposition took place on the catalyst,mainly as graphitized carbon,and carbon deposition was the most serious in C_(2)H_(4)atmosphere.The influence order of atmosphere on carbon deposition was C_(2)H_(4)>CO_(2)>CO>CH_(4)>N_(2)>C_(2)H_(6).