H_2等离子体制备免焙烧Ce改性的MoP加氢脱硫催化剂
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摘要
采用免焙烧法制备催化剂前驱体,用H_2等离子体还原制备免焙烧的MoP(NC-MoP)催化剂和Ce改性的MoP(Ce-MoP(n))催化剂。对制备的催化剂进行XRD和N_2物理吸附表征,并用质量分数为0.8%的二苯并噻吩/十氢萘(DBT)溶液来考察催化剂的加氢脱硫(HDS)反应活性。与焙烧的MoP(C-MoP)催化剂相比,NC-MoP具有较小的颗粒尺寸和较大的比表面积,从而具有较高的DBT加氢脱硫反应活性;引入Ce后,催化剂的颗粒尺寸降低,比表面积增加,反应活性提高;Ce含量较低时,助催化效果随着Ce含量的增加而增强,Ce-MoP(0.3)具有最高的反应活性。
Non-calcinated MoP(NC-MoP)and Ce promoted MoP(Ce-MoP(n))catalysts were prepared by a non-calcination procedure,in which the precursors were directly converted to the active phosphide phase using the H_2 plasma reduction(PR)method.The morphologies of the catalysts were characterized by XRD and N_2 physical adsorption,and the hydrodesulfurization(HDS) performances were studied with a model fuel containing 0.8%(mass fraction)dibenzothiophene(DBT)in decalin.Compared with the calcinated MoP(C-MoP),NC-MoP possessed smaller particle size and larger specific surface area,leading to higher HDS activity.The introduction of Ce promoted the HDS activity,caused by the decrease of the particle size.At lower content of Ce,the promotion effect increased with the increase of Ce content,and Ce-MoP(0.3)expressed the highest HDS performance.
Non-calcinated MoP(NC-MoP)and Ce promoted MoP(Ce-MoP(n))catalysts were prepared by a non-calcination procedure,in which the precursors were directly converted to the active phosphide phase using the H_2 plasma reduction(PR)method.The morphologies of the catalysts were characterized by XRD and N_2 physical adsorption,and the hydrodesulfurization(HDS) performances were studied with a model fuel containing 0.8%(mass fraction)dibenzothiophene(DBT)in decalin.Compared with the calcinated MoP(C-MoP),NC-MoP possessed smaller particle size and larger specific surface area,leading to higher HDS activity.The introduction of Ce promoted the HDS activity,caused by the decrease of the particle size.At lower content of Ce,the promotion effect increased with the increase of Ce content,and Ce-MoP(0.3)expressed the highest HDS performance.
引文
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[3]STINNER C,PRINS R,WEBER T.Preparation and catalytic performance of transition metal phosphides[J].Journal of Catalysis,2001,202(1):187-194.
[4]孙福侠,李灿.过渡金属磷化物的加氢精制催化性能研究进展[J].石油学报(石油加工),2005,21(6):1-11.(SUN Fuxia,LI Can.Advance in the research on hydrodesulfurization and hydrodentirogenation on transition metal phosphides[J].Acta Petrolei Sinica(Petroleum Processing Section),2005,21(6):1-11.)
[5]WANG R,SMITH K J.The effect of preparation conditions on the properties of high-surface area Ni2P catalysts[J].Applied Catalysis A:General,2010,380(1-2):149-164.
[6]GOTT T,OYAMA S T.A general method for determining the role of spectroscopically observed species in reaction mechanisms:Analysis of coverage transients(ACT)[J].Journal of Catalysis,2009,263(2):359-371.
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[8]PRINS R,BUSSELL M E.Metal phosphides:preparation,characterization and catalytic reactivity[J].Catalysis Letter,2012,142(12):1413-1436.
[9]WANG W,LI X,SUN Z C,et al.Influences of calcination and reduction methods on the preparation of Ni2P/SiO2and its hydrodenitrogenation performance[J].Applied Catalysis A:General,2016,509(1):45-51.
[10]WANG A J,QIN M L,GUAN J,et al.The synthesis of metal phosphides:reduction of oxide precursors in a hydrogen plasma[J].Angewandte Chemie International Edition,2008,47(32):6052-6054.
[11]KAUR B,SRIVASTAVA R,SATPATI B.Highly efficient CeO2 decorated nano-ZSM-5 catalyst for electrochemical oxidation of methanol[J].ACS Catalysis,2016,6(4):2654-2663.
[12]YAN L J,LIU Y Y,HU H,et al.Antimony promotional effect on CeO2-WO3/TiO2 for selective catalytic reduction of NOxwith NH3[J].Chemcatchem,2016,8(13):2267-2278.
[13]WANG W Y,WU K,LIU P L,et al.Hydrodeoxygenation of p-cresol over Pt/Al2O3catalyst promoted by ZrO2,CeO2and CeO2-ZrO2[J].Industrial&Engineering Chemistry Research,2016,55(28):7598-7603.
[14]SUN Z C,LI X,WANG A J.The effect of CeO2on the hydrodenitrogenation performance of bulk Ni2P[J].Topic in Catalysis,2012,55(14-15):1010-1021.
[15]YE L M,DUAN X,LIN H Q,et al.Improved performance of magnetically recoverable Ce-promoted Ni/Al2O3catalysts for aqueous-phase hydrogenolysis of sorbitol to glycols[J].Catalysis Today,2012,183(1):65-71.
[16]孙志超.金属磷化物催化剂制备、改性及加氢脱硫(氮)反应性能[D].大连:大连理工大学,2014.