碳化钼的合成表征与喹啉加氢脱氮性能研究
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摘要
随原油劣质化趋势加大和环保法规的日益严格,开发新型高效加氢脱硫、脱氮催化剂已成为加氢精制领域新的研究热点。本文采用程序升温还原碳化反应制备了碳化钼催化剂,并用TG-DTA技术对氧化钼的还原碳化机理进行了研究,借助XRD、BET、GEM、XPS等技术对制备的催化剂进行了表征,以喹啉/环己烷溶液为模型化合物,在高压微反装置上对制备的碳化钼催化剂的喹啉加氢脱氮性能进行了评价。
结果表明,MoO_3可在程序升温条件下于CH_4/H_2气氛中还原碳化为β-Mo_2C,其适宜的还原碳化温度675℃,恒温保持180min。Ni助剂的加入可降低MoO_3的还原碳化始、终点温度,增大催化剂的比表面积.Co助剂的可降低MoO_3的还原碳化起始温度,但对还原碳化终点温度影响不大,并能抑制Mo_2C颗粒的生长,从而有利于提高碳化钼催化剂的比表面积。Mo_2C催化剂表现出了较高的加氢脱氮活性,其在反应压力3.0MPa,反应液时空速8h~(-1),H_2/原料液体积比500:1,340℃反应温度下的喹啉加氢脱氮活性达到了41.3%,比相应MoS_2和MoO_3分别提高了约8和28个百分点。Ni、Co助剂的加入对Mo_2C喹啉加氢脱氮活性有明显的促进作用,在上述反应条件下,Ni/Mo比为0.3和Co/Mo原子比为0.4制得的Ni-Mo_2C和Co-Mo_2C催化剂的喹啉脱氮率分别达到了98.2%和98.0%,相应都提高了约47百分点。Ni-Mo_2C催化剂合成条件以还原碳化温度625℃、还原碳化时间为180min较为适宜;而Co-Mo_2C催化剂合成条件以还原碳化温度650℃、还原碳化时间为180min较为适宜。
With the petroleum becoming inferior and environmental regulations growing stringent,new high-performance hydrodesulfurization and hydrodenitrogenation catalysts in hydrotreating field has become a new hotspot.Molybdenum carbide catalysts were prepared by temperatureprogrammed reaction and characterized by XRD、BET、SEM、XPS techniques.TG-DTA in-situ was used to investigate the synthesis mechanism of molybdenum carbide catalysts.The hydrodenitrogenation(HDN) performance of the catalysts were evaluated by using of quinoline/cyclohexane as model reactants.The results were as follows:
MoO_3 could be carburized intoβ-Mo_2C in CH_4/H_2 mixture at carburizing temperature 675℃.The promoters Ni and Co could change the process of carburization,decrease the carburizing temperature and increase the surface area of Mo_2C.Ni could reduce it's initial and terminal carburizing temperature,while Co could merely increase the initial temperature,but couldn't effect the terminal carburizing temperature.Mo_2C had a higher activity of quinoline HDN than MoS_2 and MoO_3.Under the reaction conditions of 340℃,3.0MPa,space velocity 8h~(-1),and H_2 / liquid volume ratio 500:1,the quinoline HDN activity of Mo_2C reached 41.3 percent,which was about 8 percent point and 24 percent point higher than that of MoS_2 and MoO_3,respectively. The quinoline HDN activity of Ni-Mo_2C at 0.3 of Ni/Mo atom ratio and Co-Mo_2C at 0.4 of Ni/Mo atom ratio reached 98.2%and 98.0%under the same reaction conditions,which was about 47 percent point higher than that of Mo_2C.It was found that Ni and Co promoters could significantly improve the quinoline HDN activity of Mo_2C.The optimal preparation conditions for Ni-Mo_2C were that the carburizing temperature was about 625℃,while for Co-Mo_2C that was 650℃,and the carburizing time was 180 min for both.
结果表明,MoO_3可在程序升温条件下于CH_4/H_2气氛中还原碳化为β-Mo_2C,其适宜的还原碳化温度675℃,恒温保持180min。Ni助剂的加入可降低MoO_3的还原碳化始、终点温度,增大催化剂的比表面积.Co助剂的可降低MoO_3的还原碳化起始温度,但对还原碳化终点温度影响不大,并能抑制Mo_2C颗粒的生长,从而有利于提高碳化钼催化剂的比表面积。Mo_2C催化剂表现出了较高的加氢脱氮活性,其在反应压力3.0MPa,反应液时空速8h~(-1),H_2/原料液体积比500:1,340℃反应温度下的喹啉加氢脱氮活性达到了41.3%,比相应MoS_2和MoO_3分别提高了约8和28个百分点。Ni、Co助剂的加入对Mo_2C喹啉加氢脱氮活性有明显的促进作用,在上述反应条件下,Ni/Mo比为0.3和Co/Mo原子比为0.4制得的Ni-Mo_2C和Co-Mo_2C催化剂的喹啉脱氮率分别达到了98.2%和98.0%,相应都提高了约47百分点。Ni-Mo_2C催化剂合成条件以还原碳化温度625℃、还原碳化时间为180min较为适宜;而Co-Mo_2C催化剂合成条件以还原碳化温度650℃、还原碳化时间为180min较为适宜。
With the petroleum becoming inferior and environmental regulations growing stringent,new high-performance hydrodesulfurization and hydrodenitrogenation catalysts in hydrotreating field has become a new hotspot.Molybdenum carbide catalysts were prepared by temperatureprogrammed reaction and characterized by XRD、BET、SEM、XPS techniques.TG-DTA in-situ was used to investigate the synthesis mechanism of molybdenum carbide catalysts.The hydrodenitrogenation(HDN) performance of the catalysts were evaluated by using of quinoline/cyclohexane as model reactants.The results were as follows:
MoO_3 could be carburized intoβ-Mo_2C in CH_4/H_2 mixture at carburizing temperature 675℃.The promoters Ni and Co could change the process of carburization,decrease the carburizing temperature and increase the surface area of Mo_2C.Ni could reduce it's initial and terminal carburizing temperature,while Co could merely increase the initial temperature,but couldn't effect the terminal carburizing temperature.Mo_2C had a higher activity of quinoline HDN than MoS_2 and MoO_3.Under the reaction conditions of 340℃,3.0MPa,space velocity 8h~(-1),and H_2 / liquid volume ratio 500:1,the quinoline HDN activity of Mo_2C reached 41.3 percent,which was about 8 percent point and 24 percent point higher than that of MoS_2 and MoO_3,respectively. The quinoline HDN activity of Ni-Mo_2C at 0.3 of Ni/Mo atom ratio and Co-Mo_2C at 0.4 of Ni/Mo atom ratio reached 98.2%and 98.0%under the same reaction conditions,which was about 47 percent point higher than that of Mo_2C.It was found that Ni and Co promoters could significantly improve the quinoline HDN activity of Mo_2C.The optimal preparation conditions for Ni-Mo_2C were that the carburizing temperature was about 625℃,while for Co-Mo_2C that was 650℃,and the carburizing time was 180 min for both.
引文
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[2]Song C S.An overview of new approaches to deep desulfurization for ultra-clean gasoline,diesel fuel and jet fuel[J].Catal.Today,2003,86(1-4):211-263
[3]Gates B C,Topsoe H.Reactivities in deep catalytic hydrodesulfurization:challenges,opportunities,and the importance of 4-methyldibenzothiophene and 4,6-dimethyl -dibenzothiophene[J].Polyhedron,1997,16(18):3213-3217
[4]屈锦华,李建伟,李成岳,等.Co-Mo/Al_2O_3催化剂上噻吩催化加氢脱硫的动力学研究[J].北京化工大学学报.2001,28(4):7-11
[5]EPA,Control of Air Pollution from New Motor Vehicles Amendment to the Tier-2/Gasoline Sulfur Regulations[R].US Environmental Protection Agency,April 13,2001
[6]EPA-Diesel RIA,Regulatory Impact Analysis:Heavy-duty Engine and Vehicle Standards and Highway Diesel Fuel Sulfur Control Requirements[R].United States Environment Protection Agency,Air and Radiation,EPA420-R-00-026,December 2000
[7]EPA,EPA Gives the Green light on Diesel Sulfur Rule,Press Release[R].United States Environmental Protection Agency,February28,2001
[8]Service RF.Hydrogen power:Bringing fuel cells down to earth[J].Science.1999,285,682-685.
[9]Xiao T C,Wang H T,Da J W,et al.Study of the preparation and catalytic perfo-rmance of molybdenum carbide catalysts prepared with C_2H_2/H_2 carburizing mixture[J].J.Catal.,2002,211(1):183-191
[10]Szymanska A,Lewandowski M,Sayag C,et al.Kinetic study of the hydrodenitrogenation of carbazole over bulk molybdenum carbide[J].J.Catal.,2003,218(1):24-31
[11]Nino Rinaldi,Usman,Khalida Al-Dalama,et al.Preparation of Co--Mo/B_2O_3 / Al_2O_3 catalysts for hydrodesulfurization:Effect of citric acid addition[J].Applied Catalysis A:General,2009,360(2):130-136
[12]S.Sigurdson,V.Sundaramurthy,A.K.Dalai,J.Adjaye.Phosphorus promoted trimetallic NiMoW/γ-Al_2O_3 sulfide catalysts in gas oil hydrotreatin.g[J].Journal of Molecular Catalysis A:Chemical,2008,191(1-2):30-37
[13]王瑶,王安杰,陈永英,等.以MCM241为载体担载Co2Mo硫化物制备柴油深度加氢脱硫催化剂[J].石油学报(石油加工).2003,19(6):24-28
[14]柴永明,安高军,柳云骐,等.过渡金属硫化物催化剂催化加氢作用机理[J].化工进展,2007,19(2/3):234-239
[15]刘大鹏,李永丹.加氢脱氮催化研究的新进展[J].化学进展,2006,18(4):417-427
[16]S.K.Bej,L.T.Thompson.Acetone condensation over molybdenum nitride and carb-ide catalysts[J].Applied Catalysis A:General,2004,264:141-150
[17]沈强,卢春山,马磊,等.过渡金属氮化物的制备及其在催化中的应用[J].化工生产与技术,2004,11(1):33-36
[18]刘维桥,刘杰,赵琳,等.Mo_2N催化剂的研究进展[J].抚顺石油学院学报,2003,23(3):18-21
[19]葛晖,李学宽,秦张峰,等.油品深度加氢脱硫催化研究进展[J].化工进展,2008,27 (10):1490-1497
[20]Costa P D,Potvin C,Manoli J M,et al.Deep hydrodesulfurization and hydrogenation of diesel fuels on alumina-supported and bulk molybdenum carbide catalysts[J].Fuel,2004,83:1717-1726
[21]徐彤,李雄男,王海彦,等.MoP/TiO_2-ZrO_2催化荆制备及加氢脱氮性能考察[J].工业催化,2008,16(12):47-52
[22]王洪学,李翠清,徐景峰,等.加氢精制磷化钨催化剂的合成与活性[J].炼油技术与工程,2004,34(5):39-41
[23]董振国,余夕志,李凯,等.工业NiW/Al_2O_3催化剂上喹啉的加氢脱氮宏观动力学[J].高校化学工程学报,2006,20(5):717-722
[24]李矗,王安杰,鲁墨弘,等.加氢脱氮反应与加氢脱氮催化剂的研究进展[J].化工进展,2003,22(6):583-588
[25]Liu,Chenguang;Yu,Yingmin;Zhao,Huiji,Hydrodenitrogenation of quinoline over Ni-Mo/Al_2O_3 catalyst modified with fluorine and phosphorus[J].Fuel Processing Technology,2005,86(4):449-460
[26]Patt J,Jumoon D,Phillips C,et al.Molybdenum carbide catalysts for water-gas shift[J].Catal.Lett.,2000,65:193-195
[27]T.Christofoletti,J.M.Aaasf.Methane steam reforming on supported and nonsuppor-tted molybdenum carbides[J].Chemidal Engineering Journal,2005,106:97-103
[28]Miyao T,Shishikura I,Matsuoka M,Nagai M.CVD synthesis of alumina-supported molybdenum carbide catalyst[J].Chem.Lett.,1996,7:561-562
[29]Pham-Huu C,Bouchy C,Dintzer T,et al.High surface area silicon carbide doped with zirconium for use as catalyst support:Preparation,characterization and catalytic application[J].Appl.Catal.,A,1999,180(1-2):385-397
[30]王广建,柳荣展,常俊石.新型催化剂-碳化钼和碳化钨的现状和展望[J].青岛大学学报,2001,16(3):51-53
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