活性金属不同浸渍顺序对Mo-Ni/Al_2O_3催化剂硫醚化反应性能的影响
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摘要
针对硫醚化反应过程使用的Mo-Ni/Al_2O_3催化剂,考察了不同浸渍方法对其催化性能和表面结构性质的影响。结果表明,通过同步浸渍和分步浸渍方法制得Mo-Ni/Al_2O_3催化剂的活性顺序为:先浸渍Mo后浸渍Ni的催化剂(SI-mn)≈Ni和Mo共同浸渍的催化剂(MN)>先浸渍Ni后浸渍Mo的催化剂(SI-nm)。对于SI-mn催化剂,先负载Mo后减弱了二次浸渍的Ni金属与载体间的相互作用,有利于负载金属的活化,并在二次浸渍后焙烧过程显现出显著的电子效应,形成新的Mo-Ni前体物种,有利于在预硫化过程形成适宜硫醚化和二烯烃选择性加氢的活性中心相,促进硫醚化反应和二烯烃选择性加氢。对于共同浸渍的MN催化剂也有类似的性质,因而也具有较好的催化性能。
Mo-Ni/Al_2O_3 catalysts were prepared by different impregnation sequences of Mo and Ni; the effect of impregnation sequence on the performance of Mo-Ni/Al_2O_3 catalysts in thioetherification was investigated.The results showed that the activity of the catalyst obtained by first impregnating Mo and then Ni(SI-mn) is close to that prepared by co-impregnation of Mo and Ni(MN); both are much more active than the catalyst obtained by first impregnating Ni and then Mo(SI-nm). For the SI-mn catalyst,Mo loaded on Al_2O_3 at the first stage can weaken the interaction between Ni and supporter,leading to a strong electronic effect between Ni and Mo,which can promote the formation of active phase in the presulfidation process and then enhance the catalytic performance of Mo-Ni/Al_2O_3 in thioetherification and selective hydrogenation of diene. Similar phenomena are observed for the MN catalyst obtained by co-impregnation,which also exhibits high activity in thioetherification.
Mo-Ni/Al_2O_3 catalysts were prepared by different impregnation sequences of Mo and Ni; the effect of impregnation sequence on the performance of Mo-Ni/Al_2O_3 catalysts in thioetherification was investigated.The results showed that the activity of the catalyst obtained by first impregnating Mo and then Ni(SI-mn) is close to that prepared by co-impregnation of Mo and Ni(MN); both are much more active than the catalyst obtained by first impregnating Ni and then Mo(SI-nm). For the SI-mn catalyst,Mo loaded on Al_2O_3 at the first stage can weaken the interaction between Ni and supporter,leading to a strong electronic effect between Ni and Mo,which can promote the formation of active phase in the presulfidation process and then enhance the catalytic performance of Mo-Ni/Al_2O_3 in thioetherification and selective hydrogenation of diene. Similar phenomena are observed for the MN catalyst obtained by co-impregnation,which also exhibits high activity in thioetherification.
引文
[1]ROCK K.Producing low sulfur gasoline reliably[C]//San Antonio:NPRA Annual Meeting,2003.
[2]ROCK K,FOLEY R,PUTNAM H.Improvements in FCC gasoline desulfurization via catalytic distillation[C]//San Francisco:NPRA Annual M eeting,1998.
[3]GARDNER R,SCHWARZ E,ROCK K.Start-up of CDHydro/CDHDS unit at Irving oil’s Saint John,New Brunswick refinery[C]//New Orleans:NPRA Annual M eeting,2001.
[4]NOCCA J,DEBUISSCHERT Q.Prime-G+:From pilot to startup of world’s first commercial 10μg·g-1FCC gasoline[C]//San Antonio:NPRA Annual M eeting,2002.
[5]向永生,黄金刚,石冈,刘肖飞,吴杰,王廷海.GARDES工艺在FCC汽油加氢装置的工业应用[J].工业催化,2015,23(2):131-135.(XIANG Yong-sheng,HUANG Jing-gang,SHI Gang,LIU Shao-fei,WU Jie,WANG Ting-hai.Commercial application of GARDES process in FCC gasoline hydrogenation unit[J].Ind Catal,2015,23(2):131-135.)
[6]石冈,范煜,鲍晓军,王廷海.催化裂化汽油加氢改质GARDES技术的开发及工业试验[J].石油炼制与化工,2013,44(9):66-72.(SHI Gang,FAN Yu,BAO Xiao-jun,WANG Ting-hai.Development and application of Gardes technology for fluid catalytic cracking gasoline hydro-upgrading[J].Petrol Process Petrochem,2013,44(9):66-72.)
[7]刘晓步,夏少青,刘瑞萍,胡耀强,王佩瑜.采用DSO技术催化汽油加氢装置的首次工业应用[J].炼油技术与工程,2014,44(7):28-31.(LIU Xiao-bu,XIA Shao-qing,LIU Rui-ping,HU Yao-qiang,WANG Pei-yu.First commercial application of DSO technology in FCC gasoline hydrodesulfurization[J].Petrol Refinery Eng,2014,44(7):28-31.)
[8]SHEN Z,KE M,YU P,LIU S,SONG Z,JIANG Q.Catalytic activities of Mo-modified Ni/Al2O3catalysts for thioetherification of mercaptans and di-olefins in fluid catalytic cracking naphtha[J].Transit M etal Chem,2012,37(6):587-593.
[9]SHEN Z,KE M,REN T,ZHANG J,LIANG S.Effect of sulfurization temperature on thioetherification performance of Mo-Ni/Al2O3catalyst[J].China Pet Process Petro Chem Technol,2015,17(4):55-61.
[10]肖招金,黄星亮,童宗文.制备条件对二烯硫醚化催化剂Ni/Al2O3催化性能的影响[J].石油炼制与化工,2006,37(5):24-28.(XIAO Zhao-jun,HUANG Xing-liang,TONG Zong-wen.Effect of preparation conditions on the catalytic properties of Ni/Al2O3catalyst in the diene thioetherfication reaction[J].Pet Process Petrochem,2006,37(5):24-28.)
[11]AKSOYLU A,ISLI A,ONSAN Z.Interaction between nickel and molybdenum in Ni-Mo/Al2O3catalysts:III:Effect of impregnation strategy[J].Appl Catal A:Gen,183(2):357-364.
[12]SALERNO P,MENDIOROZ S,AGUDO A.Al-pillared montmorillonite-based Ni Mo catalysts for HDS and HDN of gas oil:Influence of the method and order of M o and Ni impregnation[J].Appl Catal A:Gen,2004,259(1):17-28.
[13]FARAG H.Synthesis of Co Mo-based carbon hydrodesulfurization catalysts:Influence of the order of metal impregnations on the activity[J].Appl Catal B:Environ,2008,84(1/2):1-8.
[14]申志兵,柯明,刘基扬.Ni/Al2O3对硫醇与异戊二烯硫醚化反应的催化性能[J].石油炼制与化工,2010,41(11):37-42.(SHEN Zhi-bing,KE Ming,LIU Ji-yang.Catalytic performance of Ni/A12O3catalyst on mercaptan and isoprene thioetherifation[J].Pet Process Petrochem,2010,41(11):37-42.)
[15]张雅洁.硫醇醚化及二烯烃饱和双功能催化剂的研究[D].北京:中国石油大学,2010.(ZHANG Ya-jie.Di-functional catalysts for thioetherification and hydrogenation of diene[D].Beijing:China University of Petroleum,2010.)
[16]UOP INC.Diene value by Maleic Anhydride addition reaction[S].UOP Method 326-82,1982.
[17]任靖.以MCM-41-Y混合分子筛为载体担载Ni-Mo制备深度加氢脱硫催化剂[D].大连:大连理工大学,2006.(REN Jing.Preparation Ni-Mo Catalyst Supported on a mixture of MCM-41 and Y zeolite deep hydrodesulfurization[D].Dalian:Dalian University of Technology,2006.)
[18]QU L,ZHANG W,KOOYMAN P,PRINS R.MAS NMR,TPR and TEM studies of the interaction of Ni Mo with alumina and silica-alumina supports[J].J Catal,2003,215(1):7-13.
[19]LIU B,AU C.Carbon deposition and catalyst stability over La2Ni O4/γ-Al2O3during CO2reforming of methane to syngas[J].Appl Catal A:Gen,2003,244(1):181-195.
[20]ZNAK L,ZIELINSKI J.Effects of support on hydrogen adsorption/desorption on nickel[J].Appl Catal A:Gen,2008,334(1/2):268-276.
[21]Al-DALAMA K,STANISLAUS A.Temperature programmed reduction of Si O2-Al2O3supported Ni,M o and Ni M o catalysts prepared w ith EDTA[J].Thermochim Acta,2011,520(1/2):67-74.
[22]ZIELI'N SKI J.M orphology of nickel/alumina catalysts[J].J Catal,1982,76(1):157-163.
[23]YANG R,LI X,WU J,ZHANG X,ZHANG Z,CHENG Y,GUO J.Hydrotreating of crude 2-ethylhexanol over Ni/Al2O3catalysts:Surface Ni species-catalytic activity correlation[J].Appl Catal A:Gen,2009,368(1/2):105-112.
[24]WANG R,LI Y,SHI R,YANG M.Effect of metal-support interaction on the catalytic performance of Ni/Al2O3for selective hydrogenation of isoprene[J].J M ol Catal A:Chem,2011,344(1/2):122-127.
[25]张玉红,熊国兴,盛世善,刘盛林,杨维慎.Ni O/γ-Al2O3催化剂中Ni O与γ-Al2O3间的相互作用[J].物理化学学报,1999,15(8):735-741.(ZHANG Yu-hong,XIONG Guo-xing,SHENG Shi-shan,LIU Sheng-lin,YANG Wei-shen.Interaction of Ni O withγ-Al2O3supporter of Ni O/γ-Al2O3catalysts[J].Acta Phys-Chim Sin,1999,15(8):735-741.)
[26]ZIELI'N SKI J.M orphology of nickel/alumina catalysts[J].J Catal,1982,76(1):157-163.
[27]LAI W,PANG L,ZHENG J,LI J,WU Z,YI X,FANG W,JIA L.Efficient one pot synthesis of mesoporous Ni Mo-Al2O3catalysts for dibenzothiophene hydrodesulfurization[J].Fuel Process Technol,2013,110(1):8-16.
[28]DING L,ZHENG Y,YANG H.LCO hydrotreating with Mo-Ni and W-Ni supported on nano-and micro-sized zeolite beta[J].Appl Catal A:Gen,2009,353(1):17-23.
[29]WANG X,OZKAN U.Effect of pre-treatment conditions on the performance of sulfided Ni-Mo/γ-Al2O3catalysts for hydrogenation of linear aldehydes[J].J M ol Catal A:Chem,2005,232(1/2):101-112.
[30]LI D,SATO T,IMAMURA M,SHIMADA H,NISHIJIMA A.Spectroscopic characterization of Ni-Mo/γ-Al2O3-B2O3catalysts for hydrodesulfurization of dibenzothiophene[J].J Catal,1997,170(2):357-365.
[31]ANDONOVA S,VLADOV C,PAWELEC B,SHTEREVA I,TYULIEV G.Effect of the modified supportγ-Al2O3-Ca O on the structure and hydrodesulfurization activity of M o and Ni-M o catalysts[J].Appl Catal A:Gen,2007,328(2):201-209.
[32]NINH T,MASSIN D,LAURENTI D,VRINAT M.A new approach in the evaluation of the support effect for Ni Mo hydrodesulfurization catalysts[J].Appl Catal A:Gen,2011,407:29-39.
[2]ROCK K,FOLEY R,PUTNAM H.Improvements in FCC gasoline desulfurization via catalytic distillation[C]//San Francisco:NPRA Annual M eeting,1998.
[3]GARDNER R,SCHWARZ E,ROCK K.Start-up of CDHydro/CDHDS unit at Irving oil’s Saint John,New Brunswick refinery[C]//New Orleans:NPRA Annual M eeting,2001.
[4]NOCCA J,DEBUISSCHERT Q.Prime-G+:From pilot to startup of world’s first commercial 10μg·g-1FCC gasoline[C]//San Antonio:NPRA Annual M eeting,2002.
[5]向永生,黄金刚,石冈,刘肖飞,吴杰,王廷海.GARDES工艺在FCC汽油加氢装置的工业应用[J].工业催化,2015,23(2):131-135.(XIANG Yong-sheng,HUANG Jing-gang,SHI Gang,LIU Shao-fei,WU Jie,WANG Ting-hai.Commercial application of GARDES process in FCC gasoline hydrogenation unit[J].Ind Catal,2015,23(2):131-135.)
[6]石冈,范煜,鲍晓军,王廷海.催化裂化汽油加氢改质GARDES技术的开发及工业试验[J].石油炼制与化工,2013,44(9):66-72.(SHI Gang,FAN Yu,BAO Xiao-jun,WANG Ting-hai.Development and application of Gardes technology for fluid catalytic cracking gasoline hydro-upgrading[J].Petrol Process Petrochem,2013,44(9):66-72.)
[7]刘晓步,夏少青,刘瑞萍,胡耀强,王佩瑜.采用DSO技术催化汽油加氢装置的首次工业应用[J].炼油技术与工程,2014,44(7):28-31.(LIU Xiao-bu,XIA Shao-qing,LIU Rui-ping,HU Yao-qiang,WANG Pei-yu.First commercial application of DSO technology in FCC gasoline hydrodesulfurization[J].Petrol Refinery Eng,2014,44(7):28-31.)
[8]SHEN Z,KE M,YU P,LIU S,SONG Z,JIANG Q.Catalytic activities of Mo-modified Ni/Al2O3catalysts for thioetherification of mercaptans and di-olefins in fluid catalytic cracking naphtha[J].Transit M etal Chem,2012,37(6):587-593.
[9]SHEN Z,KE M,REN T,ZHANG J,LIANG S.Effect of sulfurization temperature on thioetherification performance of Mo-Ni/Al2O3catalyst[J].China Pet Process Petro Chem Technol,2015,17(4):55-61.
[10]肖招金,黄星亮,童宗文.制备条件对二烯硫醚化催化剂Ni/Al2O3催化性能的影响[J].石油炼制与化工,2006,37(5):24-28.(XIAO Zhao-jun,HUANG Xing-liang,TONG Zong-wen.Effect of preparation conditions on the catalytic properties of Ni/Al2O3catalyst in the diene thioetherfication reaction[J].Pet Process Petrochem,2006,37(5):24-28.)
[11]AKSOYLU A,ISLI A,ONSAN Z.Interaction between nickel and molybdenum in Ni-Mo/Al2O3catalysts:III:Effect of impregnation strategy[J].Appl Catal A:Gen,183(2):357-364.
[12]SALERNO P,MENDIOROZ S,AGUDO A.Al-pillared montmorillonite-based Ni Mo catalysts for HDS and HDN of gas oil:Influence of the method and order of M o and Ni impregnation[J].Appl Catal A:Gen,2004,259(1):17-28.
[13]FARAG H.Synthesis of Co Mo-based carbon hydrodesulfurization catalysts:Influence of the order of metal impregnations on the activity[J].Appl Catal B:Environ,2008,84(1/2):1-8.
[14]申志兵,柯明,刘基扬.Ni/Al2O3对硫醇与异戊二烯硫醚化反应的催化性能[J].石油炼制与化工,2010,41(11):37-42.(SHEN Zhi-bing,KE Ming,LIU Ji-yang.Catalytic performance of Ni/A12O3catalyst on mercaptan and isoprene thioetherifation[J].Pet Process Petrochem,2010,41(11):37-42.)
[15]张雅洁.硫醇醚化及二烯烃饱和双功能催化剂的研究[D].北京:中国石油大学,2010.(ZHANG Ya-jie.Di-functional catalysts for thioetherification and hydrogenation of diene[D].Beijing:China University of Petroleum,2010.)
[16]UOP INC.Diene value by Maleic Anhydride addition reaction[S].UOP Method 326-82,1982.
[17]任靖.以MCM-41-Y混合分子筛为载体担载Ni-Mo制备深度加氢脱硫催化剂[D].大连:大连理工大学,2006.(REN Jing.Preparation Ni-Mo Catalyst Supported on a mixture of MCM-41 and Y zeolite deep hydrodesulfurization[D].Dalian:Dalian University of Technology,2006.)
[18]QU L,ZHANG W,KOOYMAN P,PRINS R.MAS NMR,TPR and TEM studies of the interaction of Ni Mo with alumina and silica-alumina supports[J].J Catal,2003,215(1):7-13.
[19]LIU B,AU C.Carbon deposition and catalyst stability over La2Ni O4/γ-Al2O3during CO2reforming of methane to syngas[J].Appl Catal A:Gen,2003,244(1):181-195.
[20]ZNAK L,ZIELINSKI J.Effects of support on hydrogen adsorption/desorption on nickel[J].Appl Catal A:Gen,2008,334(1/2):268-276.
[21]Al-DALAMA K,STANISLAUS A.Temperature programmed reduction of Si O2-Al2O3supported Ni,M o and Ni M o catalysts prepared w ith EDTA[J].Thermochim Acta,2011,520(1/2):67-74.
[22]ZIELI'N SKI J.M orphology of nickel/alumina catalysts[J].J Catal,1982,76(1):157-163.
[23]YANG R,LI X,WU J,ZHANG X,ZHANG Z,CHENG Y,GUO J.Hydrotreating of crude 2-ethylhexanol over Ni/Al2O3catalysts:Surface Ni species-catalytic activity correlation[J].Appl Catal A:Gen,2009,368(1/2):105-112.
[24]WANG R,LI Y,SHI R,YANG M.Effect of metal-support interaction on the catalytic performance of Ni/Al2O3for selective hydrogenation of isoprene[J].J M ol Catal A:Chem,2011,344(1/2):122-127.
[25]张玉红,熊国兴,盛世善,刘盛林,杨维慎.Ni O/γ-Al2O3催化剂中Ni O与γ-Al2O3间的相互作用[J].物理化学学报,1999,15(8):735-741.(ZHANG Yu-hong,XIONG Guo-xing,SHENG Shi-shan,LIU Sheng-lin,YANG Wei-shen.Interaction of Ni O withγ-Al2O3supporter of Ni O/γ-Al2O3catalysts[J].Acta Phys-Chim Sin,1999,15(8):735-741.)
[26]ZIELI'N SKI J.M orphology of nickel/alumina catalysts[J].J Catal,1982,76(1):157-163.
[27]LAI W,PANG L,ZHENG J,LI J,WU Z,YI X,FANG W,JIA L.Efficient one pot synthesis of mesoporous Ni Mo-Al2O3catalysts for dibenzothiophene hydrodesulfurization[J].Fuel Process Technol,2013,110(1):8-16.
[28]DING L,ZHENG Y,YANG H.LCO hydrotreating with Mo-Ni and W-Ni supported on nano-and micro-sized zeolite beta[J].Appl Catal A:Gen,2009,353(1):17-23.
[29]WANG X,OZKAN U.Effect of pre-treatment conditions on the performance of sulfided Ni-Mo/γ-Al2O3catalysts for hydrogenation of linear aldehydes[J].J M ol Catal A:Chem,2005,232(1/2):101-112.
[30]LI D,SATO T,IMAMURA M,SHIMADA H,NISHIJIMA A.Spectroscopic characterization of Ni-Mo/γ-Al2O3-B2O3catalysts for hydrodesulfurization of dibenzothiophene[J].J Catal,1997,170(2):357-365.
[31]ANDONOVA S,VLADOV C,PAWELEC B,SHTEREVA I,TYULIEV G.Effect of the modified supportγ-Al2O3-Ca O on the structure and hydrodesulfurization activity of M o and Ni-M o catalysts[J].Appl Catal A:Gen,2007,328(2):201-209.
[32]NINH T,MASSIN D,LAURENTI D,VRINAT M.A new approach in the evaluation of the support effect for Ni Mo hydrodesulfurization catalysts[J].Appl Catal A:Gen,2011,407:29-39.