金属改性β/SBA-15光催化氧化脱硫及其动力学研究
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摘要
采用过饱和浸渍法制备了TiO_2改性的β/SBA-15复合分子筛,通过XRD、N_2吸附-脱附和FT-IR等表征手段对合成的试样进行表征。结果表明TiO_2-β/SBA-15同时兼具微-介双孔孔道结构,活性TiO_2纳米颗粒高度均匀地分散在复合分子筛表面。提出了光催化氧化脱硫反应的反应机理,考察了TiO_2-β/SBA-15在模拟柴油中的静态光催化氧化脱硫性能并对其进行了动力学研究。动力学研究表明,脱硫行为符合动力学一级反应模型,相关系数R~2大于0.99,反应表观活化能E——a为12.45kJ/mol。
TiO_2 modifiedβ/SBA-15 composite molecular sieves was prepared by supersaturation impregnation method.The synthesized samples were characterized by XRD,N_2 adsorption-desorption and FT-IR.The results show that TiO_2-β/SBA-15 can maintain micro-mediated double pore structure,and the active TiO_2 nanoparticles are uniformly dispersed on the surface of the composite molecular sieve.The reaction mechanism of photocatalytic oxidation desulfurization reaction was proposed.The photocatalytic oxidation desulfurization performance of TiO_2-β/SBA-15 in diesel fuel was investigated and studied.Kinetic studies show that the desulfurization behavior is consistent with the kinetic first-order reaction model,the correlation coefficient R~2 is greater than 0.99,and the E_a is 12.45 kJ/mol.
TiO_2 modifiedβ/SBA-15 composite molecular sieves was prepared by supersaturation impregnation method.The synthesized samples were characterized by XRD,N_2 adsorption-desorption and FT-IR.The results show that TiO_2-β/SBA-15 can maintain micro-mediated double pore structure,and the active TiO_2 nanoparticles are uniformly dispersed on the surface of the composite molecular sieve.The reaction mechanism of photocatalytic oxidation desulfurization reaction was proposed.The photocatalytic oxidation desulfurization performance of TiO_2-β/SBA-15 in diesel fuel was investigated and studied.Kinetic studies show that the desulfurization behavior is consistent with the kinetic first-order reaction model,the correlation coefficient R~2 is greater than 0.99,and the E_a is 12.45 kJ/mol.
引文
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[17]程俊杰,李振荣,赵亮富.Hβ/Al-SBA-15介微孔复合分子筛负载Ni-W催化剂对萘加氢裂化制BTX的催化性能[J].燃料化学学报,2017,45(1):93-99.
[18]陈杨英,韩秀文,包信和.W-SBA-15介孔分子筛的直接合成及其对环己烯环氧化反应的催化性能[J].催化学报,2005,26(5):412-416.
[19]Erdem B,Erdem S,Citak A,et al.Preparation Characterization and Catalytic Properties of SBA-15-SO3H Supported Tungstophosphoric Acid for Esterification Reaction[J].Acta Physica Polonica,A,2017,132(3):1041-1044.
[20]张书翠,姜东,唐涛等.高分散TiO2/SBA-15的制备及光催化性能[J].物理化学学报,2010,26(5):1330-1336.
[21]Zhang X,Wang J W,Zhong J,et al.Characterization and catalytic performance of SAPO-11/Hβcomposite molecular sieve compared with the mechanical mixture[J].Microporous&Mesoporous Materials,2008,108(1-3):13-21.
[2]王艳平.国内外柴油加氢精制催化剂的研究进展[J].炼油与化工,2017,5(28):1-3.
[3]Hürdogan E.Thermodynamic analysis of a diesel engine fueled with diesel and peanut biodiesel[J].Environmental Progress&Sustainable Energy,2016,35(3):891-897.
[4]Fu W,Zhang L,Tang T,et al.Extraordinarily high activity in the hydrodesulfurization of 4,6-dimethyldibenzothiophene over Pd supported on mesoporous zeolite Y[J].Journal of the American Chemical Society,2011,133(39):15346-15349.
[5]Wu Q,Li Y,Hou Z.Synthesis and characterization of Beta-FDU-12 and the hydrodesulfurization performance of FCC gasoline and diesel[J].Fuel Processing Technology,2018,172:55-64.
[6]Wang L,Wang W Y,Mominou,et al.Ultra-deep desulfurization of gasoline through aqueous phase in-situ hydrogenation and photocatalytic oxidation[J].Applied Catalysis B:Environmental,2016,193(9):180-188.
[7]Li S W,Li Y Y,Yang F,et al.Photocatalytic oxidation desulfurization of model diesel over phthalocyanine/La0.8Ce0.2NiO3[J].Journal of Colloid&Interface Science,2015,460(10):8-17.
[8]Wang X,Li F,Liu J,et al.Preparation of TiO2in ionic liquid via microwave radiation and in situ photocatalytic oxidative desulfurization of diesel oil[J].Energy&Fuels,2012,26(11):6777-6782.
[9]Parnicka P,Mazierski P,Grzyb T,et al.Influence of the preparation method on the photocatalytic activity of Ndmodified TiO2[J].Beilstein Journal of Nanotechnology,2018,9(1):447-459.
[10]Zhang J,Zhao D S,Wang J,et al.Photocatalytic oxidation of dibenzothiophene using TiO2/bamboo charcoal[J].Journal of Materials Science,2009,44(12):3112-3117.
[11]范立,沈健.Ti-USY催化剂光催化氧化汽油脱硫[J].石油化工,2014,43(5):582-586.
[12]张璐璐,孙悦,王喆,等.TiO2/SBA-15的制备及光催化氧化脱硫性能[J].硅酸盐学报,2016,44(1):56-62.
[13]Guo L,Zhu W P,Li F.Research advances in micro/mesopore composite molecular sieves[J].Nature Gas Chemical Industry,2014,39(4):68-70.
[14]赵瑞玉,刘静,刘益,等.介孔-微孔复合分子筛的制备与加氢脱硫性能评价[J].石油学报:石油加工,2010,26(5):657-665.
[15]吴淑杰,黄家辉,吴通好,等.SBA-15介孔分子筛的合成、表征及其在苯酚叔丁基化反应的催化性能[J].催化学报,2005,26(5):412-416.
[16]徐新龙,沈健.β/SBA-15复合分子筛的制备及其催化合成叔丁基苯酚的性能[J].石油化工,2014,43(7):767-773.
[17]程俊杰,李振荣,赵亮富.Hβ/Al-SBA-15介微孔复合分子筛负载Ni-W催化剂对萘加氢裂化制BTX的催化性能[J].燃料化学学报,2017,45(1):93-99.
[18]陈杨英,韩秀文,包信和.W-SBA-15介孔分子筛的直接合成及其对环己烯环氧化反应的催化性能[J].催化学报,2005,26(5):412-416.
[19]Erdem B,Erdem S,Citak A,et al.Preparation Characterization and Catalytic Properties of SBA-15-SO3H Supported Tungstophosphoric Acid for Esterification Reaction[J].Acta Physica Polonica,A,2017,132(3):1041-1044.
[20]张书翠,姜东,唐涛等.高分散TiO2/SBA-15的制备及光催化性能[J].物理化学学报,2010,26(5):1330-1336.
[21]Zhang X,Wang J W,Zhong J,et al.Characterization and catalytic performance of SAPO-11/Hβcomposite molecular sieve compared with the mechanical mixture[J].Microporous&Mesoporous Materials,2008,108(1-3):13-21.
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