【摘要】 采用浸渍法和H2气流中磷化还原法制备了一系列负载30%WO3和各种不同含量Ni、Co、V助剂的WP/γ-Al2O3,并采用XRD、NH3-TPD、XPS手段和高压微反装置对它们进行表征和催化活性评价,考察助剂Ni、Co和V对WP/γ-Al2O3催化剂物化性质和催化性能的影响。结果表明,加入适量的助剂Ni(3%～5%)、Co(5%～7%)和V(1%～3%)能够改善WP/γ-Al2O3催化剂表面上活性组分的分散性和增加WP/γ-Al2O3催化剂的比表面积。助剂Ni和Co的加入使WP/γ-Al2O3催化剂表面上低价W物种数量增多,而助剂V的加入使WP/γ-Al2O3催化剂表面上低价W物种数量减少。在高温(360℃)下的咔唑加氢脱氮(HDN)反应中和低温(300℃)下的二苯并噻吩(DBT)加氢脱硫(HDS)反应中,WP/γ-Al2O3催化剂分别具有优良的HDN和HDS活性。含3%Ni(质量分数,下同)的Ni-WP/γ-Al2O3催化剂和含3%Co的Co-WP/γ-Al2O3催化剂比WP/γ-Al2O3催化剂具有更高的DBT的HDS活性。在较高温度(360℃)下DBT的HDS反应中,含1%V的V-WP/γ-Al2O3催化剂的HDS活性高于WP/γ-Al2O3催化剂。助剂Co和Ni明显促进了WP/γ-Al2O3催化剂在咔唑HDN反应中的活性,Ni助剂的助催化作用比Co更明显。含7%Ni的Ni-WP/γ-Al2O3催化剂和含5%Co的Co-WP/γ-Al2O3催化剂在300℃咔唑HDN反应中的HDN活性很高。加入1%的V可以提高WP/γ-Al2O3催化剂在咔唑HDN反应中尤其在360℃下咔唑HDN反应中的HDN活性。更多还原

【Abstract】 The WP/γ-Al2O3 catalysts containing 30% mass fraction of WO3 and different mass fractions of promoter Ni,Co and V,respectively,were synthesized by the methods of impregnation and reduction-phosphiding with H2,and characterized by XRD,NH3-TPD and XPS.Their performances of desulfurization and denitrogenation(HDS and HDN)were evaluated in a high pressure micro-reactor.The effects of the promoter Ni,Co and V on physico-chemical properties and catalytic performance of WP/γ-Al2O3 catalyst were investigated.The results indicated that a suitable amount addition of Ni(mass fraction 3%-5%,the same below),Co(5%-7%)and V(1%-3%)into WP/γ-Al2O3 could increase the dispersity of W species on the support and the BET surface area of the WP/γ-Al2O3 catalyst.The addition of Ni or Co into WP/γ-Al2O3 catalyst could increase the amount of active W species on the surface of catalyst,whereas the addition of V could decrease the amount of active W species.The WP/γ-Al2O3 catalyst possessed a high HDS activity in DBT HDS reaction at lower reaction temperature(300℃)and a high HDN activity of carbazole HDN reaction at higher reaction temperature(360℃).In DBT HDS reaction the Ni-WP/γ-Al2O3 catalyst with 3%Ni and Co-WP/γ-Al2O3 catalyst with 3%Co had higher HDS activities than WP/γ-Al2O3 catalyst.In DBT HDS reaction at 360℃,the V-WP/γ-Al2O3 catalyst with 1%V possessed higher HDS activity than WP/γ-Al2O3 catalyst.In carbazole HDN reaction at 300℃,Co-WP/γ-Al2O3 and Ni-WP/γ-Al2O3 possessed obviously higher HDN activities than WP/γ-Al2O3 catalyst,in which Ni showed more effect than Co.The Ni-WP/γ-Al2O3 catalyst with 7%Ni and Co-WP/γ-Al2O3 catalyst with 5%Co had high activities in carbazole HDN reaction.The V-WP/γ-Al2O3 catalyst with 1%V had higher HDN activity than WP/γ-Al2O3 catalyst in carbazole HDN reaction,especially at the reaction temperature of 360℃.更多还原