H_2S/H_2硫化温度对MoP/SiO_2催化剂硫醚化性能的影响
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摘要
以负载磷酸钼为前驱体,采用程序升温还原法制备了MoP/SiO_2催化剂,以体积分数3%H_2S/H_2对其进行了硫化处理,利用XRD、CO化学吸附、NH_3-TPD、HRTEM-EDX、ICP-AES以及XPS等手段对催化剂进行了表征,研究了硫化温度对MoP/SiO_2催化剂结构和异戊二烯与正丁硫醇硫醚化性能的影响。结果表明,即使在400℃硫化处理也未改变MoP/SiO_2催化剂中MoP体相结构;随着硫化温度提高,催化剂表面酸量增加、金属位数量减少,降低了催化剂C-S键氢解及异戊二烯深度加氢活性,但同时也提高了催化剂烯烃聚合活性。经120℃硫化处理的MoP/SiO_2兼具较佳硫醚化及异戊二烯选择加氢性能。
The MoP/SiO_2 catalyst was prepared from the supported M o phosphate by the H_2-TPR method and treated with 3% H_2S/H_2 at different temperatures. The as-prepared catalysts were characterized by means of XRD,HRTEM-EDX,XPS,NH3-TPD,ICP-AES and CO chemisorption and tested for the thioetherification of isoprene and n-butylmercaptan. The effects of sulfuration temperature on the MoP/SiO_2 catalyst structure and thioetherification performance were investigated. The results showed that the M oP phase was still stable even at the sulfuration temperature of 400 ℃. As the sulfuration temperature increased,the acid amount of the catalysts increased while the surface metal site density decreased. As a result,in the thioetherification of isoprene and nbutylmercaptan,the C-S bond hydrogenolysis and the over-hydrogenation of isoprene were suppressed on the sulfurized catalysts,while the olefin polymerization was promoted. Relatively,the MoP/SiO_2 catalyst sulfurized at 120 ℃ had better performance for the thioetherification and the selective hydrogenation of isoprene.
The MoP/SiO_2 catalyst was prepared from the supported M o phosphate by the H_2-TPR method and treated with 3% H_2S/H_2 at different temperatures. The as-prepared catalysts were characterized by means of XRD,HRTEM-EDX,XPS,NH3-TPD,ICP-AES and CO chemisorption and tested for the thioetherification of isoprene and n-butylmercaptan. The effects of sulfuration temperature on the MoP/SiO_2 catalyst structure and thioetherification performance were investigated. The results showed that the M oP phase was still stable even at the sulfuration temperature of 400 ℃. As the sulfuration temperature increased,the acid amount of the catalysts increased while the surface metal site density decreased. As a result,in the thioetherification of isoprene and nbutylmercaptan,the C-S bond hydrogenolysis and the over-hydrogenation of isoprene were suppressed on the sulfurized catalysts,while the olefin polymerization was promoted. Relatively,the MoP/SiO_2 catalyst sulfurized at 120 ℃ had better performance for the thioetherification and the selective hydrogenation of isoprene.
引文
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[21]SUN F X,WU W C,WU Z L,GUO J,WEI Z B,YANG Y X,JIANG Z X,TIAN F P,LI C.Dibenzothiophene hydrodesulfurization activity and surface sites of silica-supported M oP,Ni2P,and NiM oP catalysts[J].J Catal,2004,228(2):298-310.
[22]WU Z L,SUN F X,WU W C,FENG Z C,LIANG C H,WEI Z B,LI C.On the surface sites of MoP/SiO2catalyst under sulfiding conditions:Ir spectroscopy and catalytic reactivity studies[J].J Catal,2004,222(1):41-52.
[23]BAI J,LI X,WANG A J,PRINS R WANG Y.Different role of H2S and dibenzothiophene in the incorporation of sulfur in the surface of bulk M oP during hydrodesulfurization[J].J Catal,2013,300(3):197-200.
[24]SHEN Z B,KE M,YU P,HU H Q,SONG Z Z,JIANG Q Z.Reaction mechanisms of thioetherification for mercaptans and olefins over sulfided M o-Ni/Al2O3catalysts[J].J M ol Catal A:Chem,2015,396:120-127.
[25]WILSON R L,KEMBALL C.Catalytic reactions of methyl mercaptan on disulfides of molybdenum and tungsten[J].J Catal,1964,3(5):426-437.
[26]周志远,黄星亮,张燕,李健.二烯硫醚化酸性催化剂研究[C]//全国青年催化学术会议.北京:中国石化出版社,2007.(ZHOU Zi-yuan,HUANG Xing-liang,ZHANG Yan,LI Jian.Study on the acid catalysts for diene thioetherification[C]//National Youth Catalysis Conference.Beijing:China Petrochemical Press,2007.)
[2]SONG C.An overview of new approaches to deep desulfurization for ultra-clean gasoline,diesel fuel and jet fuel[J].Catal Today,2003,86(1):211-263.
[3]PETTITI I,BOTTO I L,CABELLO C I,COLONNA C,FATICANTI M,MINELLI G,PORTA P,THOMAS H J.Anderson-type heteropolyoxomolybdates in catalysis 2.EXAFS study onλ-Al2O3-supported M o,Co and Ni sulfided phases as HDS catalysts[J].Appl Catal A:Gen,2001,220(1):113-121.
[4]孟祥东,周洪涛,孙守华.催化裂化汽油选择性加氢脱硫装置的工艺选择[J].石化技术与应用,2014,32(4):332-336.(MENG Xiang-dong,ZHOU Hong-tao,SUN Shou-hua.Process selection of selective hydrodesulfurization unit of catalytic cracking gasoline[J].Petrochem Technol Appl,2014,32(4):332-336.)
[5]肖招金,黄星亮.镍基催化剂上硫醇与异戊二烯硫醚化反应的研究[J].分子催化,2005,19(4):280-284.(XIAO Zhao-jin,HUANG Xing-liang.Study of mercaptans and isoprene thioetherfication reaction on nickel catalyst[J].J Mol Catal(China),2005,19(4):280-284.)
[6]肖招金,黄星亮.制备条件对Ni/Al2O3催化剂二烯硫醚化性能的研究[J].石油化工,2004,33(s1):381-382.(XIAO Zhao-jin,HUANG Xing-liang.Effect of preparation conditions on the catalytic properties of Ni/Al2O3catalyst in the diene thioetherfication reaction[J].Petrochem Technol,2004,33(s1):381-382.)
[7]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-jin,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.)
[8]申志兵,柯明,张君涛,张智平,梁生荣.Mo-Ni/Al2O3催化剂对FCC汽油硫醚化反应的催化性能[J].石油学报(石油加工),2015,31(6):1269-1274.(SHEN Zhi-bing,KE Ming,ZHANG Jun-tao,ZHANG Zhi-ping,LIANG Sheng-rong.Catalytic performance of Mo-Ni/Al2O3for thioetherfication of FCC gasoline[J].Acta Pet Sin(Pet Process Sect),2015,31(6):1269-1274.)
[9]SHEN Z B,KE M,YU P,HU H Q,SONG Z Z,JIANG Q Z.Reaction mechanisms of thioetherification for mercaptans and olefins over sulfided M o-Ni/Al2O3catalysts[J].J M ol Catal A:Chem,2015,396:120-127.
[10]SHEN Z B,KE M,YU P,LIU S D,SONG Z Z,JIANG Q Z.Catalytic activities of mo-modified Ni/Al2O3catalysts for thioetherification of mercaptans and di-olefins in fluid catalytic cracking naphtha[J].Transition M et Chem,2012,37(6):587-593.
[11]HUANG D Q,KE M,BAO X J,LIU H Y.Fe-promoted Ni/Al2O3thioetherification catalysts w ith enhanced low temperature activity for removing mercaptans from liquefied petroleum gas[J].Ind Eng Chem Res,2016,55(5):1192-1201.
[12]OYAMA S T.Novel catalysts for advanced hydroprocessing:Transition metal phosphides[J].J Catal,2003,216(1):343-352.
[13]OYAMA S T,GOTT T,ZHAO H Y,LEE Y K.Transition metal phosphide hydroprocessing catalysts:A review[J].Catal Today,2009,143(1):94-107.
[14]LEE Y K,OYAMA S T.Bifunctional nature of a SiO2-supported Ni2P catalyst for hydrotreating:EXAFS and FTIR studies[J].J Catal,2006,239(2):376-389.
[15]CHEN J X,SHI H,LI L,LI K L.Deoxygenation of methyl laurate as a model compound to hydrocarbons on transition metal phosphide catalysts[J].Appl Catal B:Environ,2014,144(2):870-884.
[16]REN T Y,LI M F,CHU Y,CHEN J X.Thioetherification of isoprene and butanethiol on transition metal phosphides[J].J Energy Chem,2018,27(3):930-939.
[17]PHILLIPS D C,SAWHILL S J,SELF R,BUSSELL M E.Synthesis,characterization,and hydrodesulfurization properties of silica-supported molybdenum phosphide catalysts[J].J Catal,2002,207(2):266-273.
[18]CHEN J X,YANG Y,SHI H,LI M F,CHU Y,PAN Z Y,YU X B.Regulating product distribution in deoxygenation of methyl laurate on silica-supported Ni-M o phosphides:Effect of Ni/M o ratio[J].Fuel,2014,129(7):1-10.
[19]LI K L,WANG R J,CHEN J X.Hydrodeoxygenation of anisole over silica-supported Ni2P,M oP,and NiM oP catalysts[J].Energy Fuels,2011,25(3):854-863.
[20]ZHANG Z N,TANG M X,CHEN J X.Effects of P/Ni ratio and Ni content on performance ofλ-Al2O3-supported nickel phosphides for deoxygenation of methyl laurate to hydrocarbons[J].Appl Surf Sci,2016,360(4):353-364.
[21]SUN F X,WU W C,WU Z L,GUO J,WEI Z B,YANG Y X,JIANG Z X,TIAN F P,LI C.Dibenzothiophene hydrodesulfurization activity and surface sites of silica-supported M oP,Ni2P,and NiM oP catalysts[J].J Catal,2004,228(2):298-310.
[22]WU Z L,SUN F X,WU W C,FENG Z C,LIANG C H,WEI Z B,LI C.On the surface sites of MoP/SiO2catalyst under sulfiding conditions:Ir spectroscopy and catalytic reactivity studies[J].J Catal,2004,222(1):41-52.
[23]BAI J,LI X,WANG A J,PRINS R WANG Y.Different role of H2S and dibenzothiophene in the incorporation of sulfur in the surface of bulk M oP during hydrodesulfurization[J].J Catal,2013,300(3):197-200.
[24]SHEN Z B,KE M,YU P,HU H Q,SONG Z Z,JIANG Q Z.Reaction mechanisms of thioetherification for mercaptans and olefins over sulfided M o-Ni/Al2O3catalysts[J].J M ol Catal A:Chem,2015,396:120-127.
[25]WILSON R L,KEMBALL C.Catalytic reactions of methyl mercaptan on disulfides of molybdenum and tungsten[J].J Catal,1964,3(5):426-437.
[26]周志远,黄星亮,张燕,李健.二烯硫醚化酸性催化剂研究[C]//全国青年催化学术会议.北京:中国石化出版社,2007.(ZHOU Zi-yuan,HUANG Xing-liang,ZHANG Yan,LI Jian.Study on the acid catalysts for diene thioetherification[C]//National Youth Catalysis Conference.Beijing:China Petrochemical Press,2007.)
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