TiO_2/Ni-ZSM-5催化剂的光催化氧化脱硫性能研究
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摘要
通过过饱和浸渍法制备TiO_2/Ni-ZSM-5光催化剂,并利用XRD、N_2吸附-脱附、UV-Vis、EIS、PL等方法对其进行表征,结果表明,镍高度分散在ZSM-5表面上,镍的引入能够加快电子迁移速率,有效降低光生电子空穴的复合几率,拓宽光的响应范围,提高光催化活性。考察了光催化剂的钛与镍负载量、焙烧温度、焙烧时间与光催化剂脱硫性能的关系,结果表明,焙烧温度为550℃、焙烧时间为4 h、TiO_2负载量(质量分数)为15%和NiO质量分数为1. 2%时,光催化剂脱硫效果最佳,对模拟柴油的脱硫率最高达88. 36%。该催化剂具有很好的稳定性和再使用性。
TiO_2/Ni-ZSM-5 catalyst is synthesized by the supersaturation impregnation method. The samples are characterized by XRD,N_2 adsorption-desorption,UV-Vis,EIS and PL. Characterization results show that nickel is only highly dispersed on the surface of ZSM-5,and the addition of nickel can accelerate the migration rate of electrons,effectively reduce the composite probability of photo-generated electron holes,widen the response range of light and improve the photocatalytic activity. It is shown that O_2 and holes play an important role in photocatalytic oxidation desulfurization,which further proves the photocatalytic desulfurization mechanism. The photocatalytic desulfurization effects of photocatalyst are investigated in terms of the loading amount of titanium and nickel,the roasting temperature and the roasting time.The catalyst that is made at a calcination temperature of 550℃,a roasting time of 4 h,15%( w) of TiO_2 loading amount and 1. 2%( w) of Ni O loading amount can give the best desulfurization effect that the highest desulfurization rate for simulated diesel can reach 88. 36%.The catalyst also exhibits good stability and reusability.
TiO_2/Ni-ZSM-5 catalyst is synthesized by the supersaturation impregnation method. The samples are characterized by XRD,N_2 adsorption-desorption,UV-Vis,EIS and PL. Characterization results show that nickel is only highly dispersed on the surface of ZSM-5,and the addition of nickel can accelerate the migration rate of electrons,effectively reduce the composite probability of photo-generated electron holes,widen the response range of light and improve the photocatalytic activity. It is shown that O_2 and holes play an important role in photocatalytic oxidation desulfurization,which further proves the photocatalytic desulfurization mechanism. The photocatalytic desulfurization effects of photocatalyst are investigated in terms of the loading amount of titanium and nickel,the roasting temperature and the roasting time.The catalyst that is made at a calcination temperature of 550℃,a roasting time of 4 h,15%( w) of TiO_2 loading amount and 1. 2%( w) of Ni O loading amount can give the best desulfurization effect that the highest desulfurization rate for simulated diesel can reach 88. 36%.The catalyst also exhibits good stability and reusability.
引文
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[2]Subhan F,Liu B S,Zhang Y,et al. High desulfurization characteristic of lanthanum loaded mesoporous MCM-41 sorbents for diesel fuel[J].Fuel Processing Technology,2012,97(3):71-78.
[3]Wang W Y,Pan M X,Qin Y C,et al.Effects of surface acidity on the adsorption desulfurization of Cu(Ⅰ)Y zeolites[J]. Acta Physico-ChimicaSinica,2011,27(5):1175-1180.
[4]Song C.An overview of new approaches to deep desulfurization for ultra-clean gasoline,diesel fuel and jet fuel[J]. Catalysis Today,2003,86(1):211-263.
[5]王超,陈达,刘姝,等.TiO2光催化还原CO2研究进展[J].材料导报,2011,25(7):38-46.
[6]谢明政,冯玉杰,栾鹏,等.N,S共掺杂纳米Ti O2水解-溶剂热法合成及可见光催化活性[J].无机化学学报,2014,30(9):2081-2086.
[7]Yao S H,Wang X X,Guo M,et al.Preparation and photocatalytic activity of mesoporous Ti O2photocatalyst Co-doped with Fe and H3PW12O40[J].Journal of the Chinese Chemical Society,2015,62(2):163-169.
[8]Wu J C,Chen C H.A visible-light response vanadium-doped titaniananocatalyst by sol-gelmethod[J]. Journal of Photochemistry and Photobiology A,2004,163(3):509-515.
[9]Zhang J,Zhao D,Wang J,et al.Photocatalytic oxidation of dibenzothiophene using Ti O2/bamboo charcoal[J]. Journal of Materials Science,2009,44(12):3112-3117.
[10]吉向飞,赵娇娇,安转转,等.不同形貌ZSM-5分子筛的制备及其催化甲醇转化制烯烃性能[J].燃料化学学报,2015,43(6):747-753.
[11]Na J,Liu G,Zhou T,et al.Synthesis and catalytic performance of ZSM-5/MCM-41 zeolites with varying mesopore size by surfactantdirected recrystallization[J].Catalysis Letters,2013,143(3):267-275.
[12]Li X,Wang D,Cheng G,et al.Preparation of polyaniline-modified Ti O2nanoparticles and their photocatalytic activity under visible light illumination[J].Applied Catalysis B Environmental,2008,81(3):267-273.
[13]Wang Lei,Cai Haijun,Li Shuzhen,et al.Ultra-deep removal of thiophene compounds in diesel oil over catalyst Ti O2/Ni-ZSM-5assisted by ultraviolet irradiating[J]. Fuel,2012,105(2):752-756.
[14]王俊丰,沈健,任铁强.Ce-SBA-15的制备及其苯酚甲醇烷基化性能[J].分子催化,2016,30(6):523-531.
[15]陈诵英,陈平,李永旺,等.催化反应动力学[M].北京:化学工业出版,2006:79-89.
[16]熊晶晶,李可心,黄黎明,等.介孔电气石Ti O2复合材料的制备及其模拟太阳光光催化性能[J].复合材料学报,2014,31(6):1481-1489.
[17]Scanlon D O,Dunnill C W,Buckeridge J,et al.Band alignment of rutile and anatase Ti O2[J].Nature Materials,2013,12(9):798-801.
[18]Xu Y,Xu H,Wang L,et al. The CNT modified white C3N4composite photocatalyst with enhanced visible-light response photoactivity[J].Dalton Trans,2013,42(41),7604-7613.
[19]Zhang Xiaodong,Xie Xiao,Wang Hui,et al.Enhanced photoresponsiveultrathin graphitic-phase C3N4nanosheets for bioimaging[J].Journal of the American Chemical Society,2013,135(1):18-21.
[20]张璐璐,詹金友,孙尧,等.WO3-Ti O2/SBA-15的制备及其光催化氧化脱硫性能[J].燃料化学学报,2016,44(6):754-762.
[21]陈英,刘宝生,李建忠.低含量Ni掺杂Ti O2光催化剂及其在水溶液体系中的重复使用性能[J].工业催化,2009,17(7):59-65.
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