TiO_2改性对α-Al_2O_3负载型磷化镍(Ni_2P)催化植物油加氢脱氧的影响
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摘要
Ni_2PRu/α-Al_2O_3是一种新型的催化加氢催化剂。该催化剂可以通过TiO_2进行改性。所得TiO_2-Ni2PRu/α-Al_2O_3中Ni2P晶粒的尺寸约为18nm,明显小于Ni2PRu/α-Al_2O_3中Ni2P晶粒的尺寸(24nm)。这可能与前驱体的还原性能有关。H2-TPR研究表明:Ni2PRu/α-Al_2O_3前驱体的峰顶还原温度位于500℃左右,而TiO_2-Ni2PRuO/α-Al_2O_3前驱体的中峰顶还原温度分别位于380℃和467℃左右。此外,H2-TPD的研究发现,TiO_2-Ni2PRu/α-Al_2O_3和Ni2PRu/α-Al_2O_3催化剂表面都具有丰富的解离氢。但TiO_2-Ni2PRu/α-Al_2O_3对植物油具有更优异的加氢脱氧性能。催化加氢性能的研究表明:Ni2PRu/α-Al_2O_3催化植物油加氢反应液相产物中未完全反应产物的质量分数小于5%,TiO_2-Ni2PRu/α-Al_2O_3对应的液相产物中未完全反应产物的质量分数则小于1%。
Ni_2PRu/α-Al_2O_3 is a new type catalyst for hydrodeoxygenation.Modification of Ni2 PRu/α-Al_2O_3 with TiO_2 is investigated.Crystal size of Ni2 P in the obtained catalysts,labelled as TiO_2-Ni2 PRu/α-Al_2O_3,is estimated to be 18 nm,which is smaller than that(24 nm)in Ni2 PRu/α-Al_2O_3.This behavior may be related with the reductionability of precursor.It is demonstrated by H2-TPR characterization that the reduction peak temperature of TiO_2-Ni2 PRu/α-Al_2O_3 precursor are located around 380℃and 467℃,being lower than that(500 ℃)of Ni2 PRu/α-Al_2O_3 precursor.Abundant dissociative hydrogen on the surface of TiO_2-Ni2 PRu/α-Al_2O_3 and Ni2 PRu/α-Al_2O_3 are proved by H2-TPD characterization.However,TiO_2-Ni2 PRu/α-Al_2O_3 shows better catalytic hydrodeoxygenation performance for vegetable oil.During its catalytic hydrodeoxygenation test,mass content of residual reactants in liquid products is calculated to be less than 1%.Such a value for Ni2 PRu/α-Al_2O_3 is estimated to be less than 5%.
Ni_2PRu/α-Al_2O_3 is a new type catalyst for hydrodeoxygenation.Modification of Ni2 PRu/α-Al_2O_3 with TiO_2 is investigated.Crystal size of Ni2 P in the obtained catalysts,labelled as TiO_2-Ni2 PRu/α-Al_2O_3,is estimated to be 18 nm,which is smaller than that(24 nm)in Ni2 PRu/α-Al_2O_3.This behavior may be related with the reductionability of precursor.It is demonstrated by H2-TPR characterization that the reduction peak temperature of TiO_2-Ni2 PRu/α-Al_2O_3 precursor are located around 380℃and 467℃,being lower than that(500 ℃)of Ni2 PRu/α-Al_2O_3 precursor.Abundant dissociative hydrogen on the surface of TiO_2-Ni2 PRu/α-Al_2O_3 and Ni2 PRu/α-Al_2O_3 are proved by H2-TPD characterization.However,TiO_2-Ni2 PRu/α-Al_2O_3 shows better catalytic hydrodeoxygenation performance for vegetable oil.During its catalytic hydrodeoxygenation test,mass content of residual reactants in liquid products is calculated to be less than 1%.Such a value for Ni2 PRu/α-Al_2O_3 is estimated to be less than 5%.
引文
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[2]赵阳,吴佳,王宣,等.植物油加氢制备高十六烷值柴油组分研究进展[J].化工进展,2010,26(10):1391-1394.ZHAO Yang,WU Jia,WANG Xuan,et al.Advance in hydroprocessing technology of manufacturing diesel with high cetane number from vegetable oil[J].Chemical Industry and Engineering Progress,2010,26(10):1391-1394.
[3]SATYARTHI J K,CHIRANJEEVI T,GOKAK D T,et al.An overview of catalytic conversion of vegetable oils/fats into middle distillates[J].Catalysis Science&Technology,2013,3(1):70-80.
[4]ALEXANDER A M,HARGREAVES J S.Alternative catalytic materials:Carbides,nitrides,phosphides and amorphous boron alloys[J].Chemical Society Reviews,2010,39(11):4388-4401.
[5]GUAN Q X,LI W.A novel synthetic approach to synthesizing bulk and supported metal phosphides[J].Journal of Catalysis,2010,271(2):413-415.
[6]DA SILVA V T,SOUSA L A,AMORIM R M,et al.Lowering the synthesis temperature of Ni2P/SiO2by palladium addition[J].Journal of Catalysis,2011,279(1):88-102.
[7]LIU X G,ZHANG B Q,XU L.Noble metal catalyzed preparation of Ni2P/alpha-Al2O3[J].Physical Chemistry Chemical Physics,2013,15(25):10510-10514.
[8]LIU X G,XU L,ZHANG B Q.Essential elucidation for preparation of supported nickel phosphide upon nickel phosphate precursor[J].Journal of Solid State Chemistry,2014,212(4):13-22.
[9]KENICHI K,WATARU O,SATORU T,et al.Hydrodeoxygenation of fatty acids and triglycerides by Pt-loaded Nb2O5catalysts[J].Catalysis Science&Technology,2014,4(10):3705-3712.
[10]XIA Q N,CUAN Q,LIU X H,et al.Pd/NbOPO4multifunctional catalyst for the direct production of liquid alkanes from aldol adducts of furans[J].Angewandte Chemie International Edition,2014,53(37):9755-9760.
[11]PENG B X,YUAN X G,ZHAO C,et al.Stabilizing catalytic pathways via redundancy:Selective reduction of microalgae oil to alkanes[J].Journal of the American Chemical Society,2012,134(22):9400-9405.
[12]SONG H,DAI M,GUO Y T,et al.Preparation of composite TiO2-Al2O3supported nickel phosphide hydrotreating catalysts and catalytic activity for hydrodesulfurization of dibenzothiophene[J].Fuel Processing Technology,2012,96:228-236.
[13]CHEN T,YANG B L,LI S S,et al.Ni2P catalysts supported on titania-modified alumina for the hydrodesulfurization of dibenzothiophene[J].Industrial&Engineering Chemistry Research,2011,50(19):11043-11048.
[14]CHEN J X,ZHOU S H,CI D H,et al.Influence of supports on structure and performance of nickel phosphide catalysts for hydrodechlorination of chlorobenzene[J].Industrial and Engineering Chemistry Research,2009,48(8):3812-3819.
[15]LI X,SUN Z C,WANG A J,et al.Effect of TiO2 on the hydrodesulfurization performance of bulk Ni2P[J].Applied Catalysis A:General,2012,417/418:19-25.
[16]WANG A J,RUAN L F,TENG Y,et al.Hydrodesulfurization of dibenzothiophene over siliceous MCM-41-supported nickel phosphide catalysts[J].Journal of Catalysis,2005,229(2):314-321.
[17]LIU X G,CHEN J X,ZHANG J Y.Hydrodechlorination of chlorobenzene over silica-supported nickel phosphide catalysts[J].Industrial&Engineering Chemistry Research,2008,47(15):5362-5368.
[18]LI K L,WANG R J,CHEN J X.Hydrodeoxygenation of anisole over silica-supported Ni2P,MoP,and NiMoP catalysts[J].Energy&Fuels,2011,25(3):854-863.
[19]WANG C X,LIU Q H,SONG J,et al.High quality dieselrange alkanes production via a single-step hydrotreatment of vegetable oil over Ni/zeolite catalyst[J].Catalysis Today,2014,234(10):153-160.
[20]ZHAO S,LI M F,CHU Y,et al.Hydroconversion of methyl laurate as a model compound to hydrocarbons on bifunctional Ni2P/SAPO-11:Simultaneous comparison with the performance of Ni/SAPO-11[J].Energy&Fuels,2014,28(11):7122-7132.
[21]陈伦刚,刘勇,龙金星,等.丙酸水相加氢反应中Ru负载量对C—C键断裂的影响[J].分子催化,2014,28(1):29-38.CHEN Lungang,LIU Yong,LONG Jinxing,et al.The effect of Ru loading on the cleavage of C—C bond for propanoic acid aqueous-phase hydrogenation[J].Journal of Molecular Catalysis(China),2014,28(1):29-38.
[22]吕恩静,张怀科,杨永宁,等.助剂Mo对Ni基催化剂加氢脱氧催化作用机理的影响[J].分子催化,2012,26(4):333-339.LYU Enjing,ZHANG Huaike,YANG Yongning,et al.Effect of Mo promoter on catalysis mechanism of hydrodeoxygenation over nickel-based catalyst[J].Journal of Molecular Catalysis(China),2012,26(4):333-339.
[23]张超,聂红,高晓冬,等.棕榈油加氢脱氧反应的规律[J].石油学报(石油加工),2014,30(4):587-594.ZHANG Chao,NIE Hong,GAO Xiaodong,et al.Hydrodeoxygenation rules of palm oil[J].Acta Petrolei Sinica(Petroleum Processing Section),2014,30(4):587-594.