介孔磷酸盐分子筛上钒物种的引入方式及其对丙烷氧化脱氢催化性能的影响
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摘要
以溶剂挥发诱导自组装法(evaporation–induced self–assembly,EISA)合成的有序磷酸盐介孔分子筛Na_(0.1)Zr_(0.9)PO为载体,分别采用掺杂和浸渍两种方式引入过渡金属钒作为活性物种,制备了一系列不同钒含量的催化剂样品。通过小角X射线衍射、N_2吸附-脱附和透射电镜表征了所制备样品的孔道结构,采用Raman光谱着重研究了不同方式引入的钒物种在Na_(0.1)Zr_(0.9)PO上的存在状态,并将催化剂上钒物种的存在状态与其在丙烷氧化脱氢反应中的催化性能相关联,探讨在介孔磷酸盐分子筛上构筑丙烷氧化脱氢活性位的合适方法。研究结果表明:掺杂方式引入的钒物种不仅可以同时以孤立态和聚集态存在,并且当钒含量高于8%时仍能保持高度分散状态,不容易出现导致催化性能下降的结晶态V_2O_5,与浸渍负载相比,本文采用掺杂方式制备的钒基催化剂样品普遍显示出更好的丙烷氧化脱氢活性和更高的丙烯选择性。此外,以碱金属Na掺杂的介孔磷酸盐分子筛Na_(0.1)Zr_(0.9)PO作为钒基催化剂的载体,虽然丙烷氧化脱氢反应的活性受到一定程度的抑制,但却可以使丙烯的选择性有所提升。
A series of catalyst samples were prepared by incorporating or impregnating of different amounts of active vanadium species on the phosphate mesoporous sieves Na_(0.1)Zr_(0.9)PO which was synthesized in advance by evaporation–induced self–assembly. The pore structure of the prepared samples was characterized by N_2 adsorption-desorption and small angle X-ray diffraction as well as transmission electron microscope. Meanwhile, the state of vanadium species on the Na_(0.1)Zr_(0.9)PO was explored by Raman spectrum, which was used to interpret their catalytic performance with an eye toward properly building the catalytic active sites on the phosphate mesoporous sieves. The experimental results showed that the vanadium species introduced by incorporating exist in both isolation and aggregation states. Furthermore,the vanadium species are highly dispersed without the formation of crystalline V_2O_5 even with more than8% of vanadium loading. In summary, the catalyst samples prepared by incorporating vanadium species into the phosphate mesoporous sieves showed better catalytic activity and selectivity for oxidative dehydrogenation of propane to propylene than the samples obtained by impregnating. Furthermore, the activity of oxidative dehydrogenation of propane to propylene declined over the vanadium catalysts supported on phosphate mesoporous sieves doped with Na, but the selectivity was increased.
A series of catalyst samples were prepared by incorporating or impregnating of different amounts of active vanadium species on the phosphate mesoporous sieves Na_(0.1)Zr_(0.9)PO which was synthesized in advance by evaporation–induced self–assembly. The pore structure of the prepared samples was characterized by N_2 adsorption-desorption and small angle X-ray diffraction as well as transmission electron microscope. Meanwhile, the state of vanadium species on the Na_(0.1)Zr_(0.9)PO was explored by Raman spectrum, which was used to interpret their catalytic performance with an eye toward properly building the catalytic active sites on the phosphate mesoporous sieves. The experimental results showed that the vanadium species introduced by incorporating exist in both isolation and aggregation states. Furthermore,the vanadium species are highly dispersed without the formation of crystalline V_2O_5 even with more than8% of vanadium loading. In summary, the catalyst samples prepared by incorporating vanadium species into the phosphate mesoporous sieves showed better catalytic activity and selectivity for oxidative dehydrogenation of propane to propylene than the samples obtained by impregnating. Furthermore, the activity of oxidative dehydrogenation of propane to propylene declined over the vanadium catalysts supported on phosphate mesoporous sieves doped with Na, but the selectivity was increased.
引文
[1]张睿.丙烷脱氢制丙烯技术进展[J].工业催化,2010,18(2):150-152.ZHANG R.Technical progress of oxidative dehydrogenation of propane to propene[J].Industrial Catalysis,2010,18(2):150-152.
[2]特日格乐,阿古拉,照日格图.丙烷氧化脱氢制丙烯介孔催化材料[J].工业催化,2012,20(3):1-6.TERIGELE L,AGULA B,ZHAORIGETU B,et al.Mesoporous catalytic materials for oxidative dehydrogenation of propane to propene[J].Industrial Catalysis,2012,20(3):1-6.
[3]EVANS O R,BELL A T,TILLEY T D.Oxidative dehydrogenation of propane over vanadium-based catalysts supported on high-surfacearea mesoporous MgAl2O4[J].Journal of Catalysis,2004,226:292-300.
[4]JOSE M,LOPZ N.The selective oxidation activation of light alkanes:from supported vanadium to multicomponent bulk V-containing catalysts[J].Topics in Catalysis,2006,41:3-15.
[5]LIU W,MOHAMED F,SAUER J.Selective oxidation of propene by vanadium oxide monomers supported on silica[J].Journal of Catalysis,2014,317:75-82.
[6]LEMONIDOU A A,NALBANDIAN L,VASALOS I A.Oxidative dehydrogenation of propane over vanadium oxide based catalysts effect of support and alkali promoter[J].Catalysis Today,2000,6:333-341.
[7]繆建文,宋国华,范以宁.不同孔道结构的氧化硅负载钒氧化物催化丙烷氧化脱氢[J].催化学报,2009,30(11):1143-1149.LIAO J W,SONG G H,FAN Y N.Propane oxidative dehydrogenation over vanadia catalysts supported on silicas with different pore structures[J].Chinese Journal of Catalysis,2009,30(11):1143-1149.
[8]汪玉,谢颂海,贺鹤勇,等.介孔氧化铝负载钒催化剂上丙烷氧化脱氢制丙烯[J].催化学报,2010,31(8):1054-1060.WANG Y,XIE S H,HE H Y,et al.Oxidative dehydrogenation of propane to propene over mesoporous alumina-supported vanadium oxide catalyst[J].Chinese Journal of Catalysis,2010,31(8):1054-1060.
[9]SAMEER A,GHAMDI A,HUGO I,et al.Propylene production via propane oxidative dehydrogenation over VOx/c-Al2O3catalyst[J].Fuel,2014,128:120-140.
[10]张帆,聂颖颖,华伟明,等.Cr/NaZSM-5催化剂上CO2氧化丙烷脱氢反应[J].高等学校化学学报,2012,33(1):96-101.ZHANG F,NIE Y Y,HUA W M,et al.Oxidative dehydrogenation of propane to propylene with CO2over Cr/NaZSM-5 catalysts[J].Chemical Journal of Chinese Universities,2012,33(1):96-101.
[11]PIOTR M,PIOTR P,JAN O.Preparation and characterization of SBA-1-supported chromium oxide catalysts for CO2assisted dehydrogenation of propane[J].Microporous and Mesoporous Materials,2012,161:56-66.
[12]CHEN B,LI F,HUANG Z,et al.Integrated catalytic process to directly convert furfural to levulinate ester with high selectivity[J].ChemSusChem,2014,7(1):202-209.
[13]MIAO Z,SONG H,ZHAO H,et al.One-pot synthesis of mesoporous ZrPW solid acid catalyst for liquid phase benzylation of anisole[J].Catalysis Science&Technology,2014,4(3):838-842.
[14]LIU B,CONG B,JIN M M,et al.Effective conversion of carbohydrates into biofuel precursor 5-hydroxymethylfurfural(HMF)over Crincorporated mesoporous zirconium phosphate[J].Industrial Crops&Products,2015,76:781-786.
[15]MIAO Z,ZHAO H,YANG J,et al.One-pot synthesis of ordered mesoporous transition metal-zirconium phosphate composites with excellent textural and catalytic properties[J].New Journal of Chemistry,2015,39(2):1322-1329.
[16]KAPOOR M P,ANUJ R.Synthesis of mesoporous hexagonal titanium aluminophosphate molecular sieves and their catalytic applications[J].Applied Catalysis A:General,2000,203(2):311-319.
[17]陈颜龙,祝琳华,司甜.非水溶液中有序介孔磷酸盐分子筛M-ZrP-O(M=Ca,Al)合成及表征[J].硅酸盐学报,2017,45(1):20-28.CHEN Y L,ZHU H L,SI T.Synthesis and characterization of ordered mesoporous phosphates MZrPO(M=Ca、Al)in nonaqueous solution[J].Journal of The Chinese Ceramic Society,2017,45(1):20-28.
[18]方智敏,翁维正,万惠霖,等.载体酸碱性对钒基催化剂丙烷氧化脱氢性能的影响及其IR和EPR研究[J].天然气化工,1998,23(2):25-29.FANG Z M,WENG W Z,WAN H L,et al.Effects of acidity and baslcity of supports on the performance of V-based catalysts for oxidative dehydrngenation of propane and their IR and EPR studies[J].Natural Gas Chemical Industry,1998,23(2):25-29.
[19]KNOTEK P,?APEK L,BULANEK R,et al.Vanadium supported on hexagonal mesoporous silica:active and stable catalysts in the oxidative dehydrogenation of alkanes[J].Topics in Catalysis,2007,45(1/2/3/4):51-55.
[20]LIU Y M,CAO Y,YI N,et al.Vanadium oxide supported on mesoporous SBA-15 as highly selective catalysts in the oxidative dehydrogenation of propane[J].Journal of Catalysis,2004,224(2):417-428.
[21]LIU Q L,LI J M,ZHAO Z,et al.Design,synthesis and catalytic performance of vanadium-incorporated mesoporous silica KIT-6catalysts for the oxidative dehydrogenation of propane to propylene[J].Catalysis Science&Technology,2016,6(15):123-128.
[22]TIAN H J,ROSS E I,WACHS I E.Quantitative determination of the speciation of surface vanadium oxides and their catalytic activity[J].Journal of Physical Chemistry B,2006,110(19):9593-9600.
[23]KHODAKOV A,OLTHOFl B,BELL A T,et al.Structure and catalytic properties of supported vanadium oxides:support effects on oxidative dehydrogenation reactions[J].Journal of Catalysis,1999,181(2):205-216.
[24]BULANEK R,?APEK L,SETNICKA M,et al.DR UV-vis study of the supported vanadium oxide catalysts[J].Journal of Physics and Chemistry of Solids,2011,115(25):197-199.
[25]方智敏,翁维正,万惠霖,等.丙烷氧化脱氢VMgO催化剂活性位的研究[J].厦门大学学报(自然科学版),1998,37(4):525-531.FANG Z M,WENG W Z,WAN H L,et al.Study on active sites of VMgO catalysts for oxidative dehydrogenation of propane[J].Journal of Xiamen University(Natural Science),1998,37(4):525-532.
[26]SASIKALA R,SUDARSAN V,SAKUNTALA T,et al.Nanoparticles of vanadia-zirconia catalysts synthesized by polyol-mediated route:enhanced selectivity for the oxidative dehydrogenation of propane to propene[J].Applied Catalysis A:General,2008,350(2):252-258.
[27]BARBERO B P,CADUS L E,HILAIRE L.XPS studies for vanadium pentoxide along the catalytic bed:oxidative dehydrogenation of propane[J].Applied Catalysis A:General,2003,246(2):237-242.
[2]特日格乐,阿古拉,照日格图.丙烷氧化脱氢制丙烯介孔催化材料[J].工业催化,2012,20(3):1-6.TERIGELE L,AGULA B,ZHAORIGETU B,et al.Mesoporous catalytic materials for oxidative dehydrogenation of propane to propene[J].Industrial Catalysis,2012,20(3):1-6.
[3]EVANS O R,BELL A T,TILLEY T D.Oxidative dehydrogenation of propane over vanadium-based catalysts supported on high-surfacearea mesoporous MgAl2O4[J].Journal of Catalysis,2004,226:292-300.
[4]JOSE M,LOPZ N.The selective oxidation activation of light alkanes:from supported vanadium to multicomponent bulk V-containing catalysts[J].Topics in Catalysis,2006,41:3-15.
[5]LIU W,MOHAMED F,SAUER J.Selective oxidation of propene by vanadium oxide monomers supported on silica[J].Journal of Catalysis,2014,317:75-82.
[6]LEMONIDOU A A,NALBANDIAN L,VASALOS I A.Oxidative dehydrogenation of propane over vanadium oxide based catalysts effect of support and alkali promoter[J].Catalysis Today,2000,6:333-341.
[7]繆建文,宋国华,范以宁.不同孔道结构的氧化硅负载钒氧化物催化丙烷氧化脱氢[J].催化学报,2009,30(11):1143-1149.LIAO J W,SONG G H,FAN Y N.Propane oxidative dehydrogenation over vanadia catalysts supported on silicas with different pore structures[J].Chinese Journal of Catalysis,2009,30(11):1143-1149.
[8]汪玉,谢颂海,贺鹤勇,等.介孔氧化铝负载钒催化剂上丙烷氧化脱氢制丙烯[J].催化学报,2010,31(8):1054-1060.WANG Y,XIE S H,HE H Y,et al.Oxidative dehydrogenation of propane to propene over mesoporous alumina-supported vanadium oxide catalyst[J].Chinese Journal of Catalysis,2010,31(8):1054-1060.
[9]SAMEER A,GHAMDI A,HUGO I,et al.Propylene production via propane oxidative dehydrogenation over VOx/c-Al2O3catalyst[J].Fuel,2014,128:120-140.
[10]张帆,聂颖颖,华伟明,等.Cr/NaZSM-5催化剂上CO2氧化丙烷脱氢反应[J].高等学校化学学报,2012,33(1):96-101.ZHANG F,NIE Y Y,HUA W M,et al.Oxidative dehydrogenation of propane to propylene with CO2over Cr/NaZSM-5 catalysts[J].Chemical Journal of Chinese Universities,2012,33(1):96-101.
[11]PIOTR M,PIOTR P,JAN O.Preparation and characterization of SBA-1-supported chromium oxide catalysts for CO2assisted dehydrogenation of propane[J].Microporous and Mesoporous Materials,2012,161:56-66.
[12]CHEN B,LI F,HUANG Z,et al.Integrated catalytic process to directly convert furfural to levulinate ester with high selectivity[J].ChemSusChem,2014,7(1):202-209.
[13]MIAO Z,SONG H,ZHAO H,et al.One-pot synthesis of mesoporous ZrPW solid acid catalyst for liquid phase benzylation of anisole[J].Catalysis Science&Technology,2014,4(3):838-842.
[14]LIU B,CONG B,JIN M M,et al.Effective conversion of carbohydrates into biofuel precursor 5-hydroxymethylfurfural(HMF)over Crincorporated mesoporous zirconium phosphate[J].Industrial Crops&Products,2015,76:781-786.
[15]MIAO Z,ZHAO H,YANG J,et al.One-pot synthesis of ordered mesoporous transition metal-zirconium phosphate composites with excellent textural and catalytic properties[J].New Journal of Chemistry,2015,39(2):1322-1329.
[16]KAPOOR M P,ANUJ R.Synthesis of mesoporous hexagonal titanium aluminophosphate molecular sieves and their catalytic applications[J].Applied Catalysis A:General,2000,203(2):311-319.
[17]陈颜龙,祝琳华,司甜.非水溶液中有序介孔磷酸盐分子筛M-ZrP-O(M=Ca,Al)合成及表征[J].硅酸盐学报,2017,45(1):20-28.CHEN Y L,ZHU H L,SI T.Synthesis and characterization of ordered mesoporous phosphates MZrPO(M=Ca、Al)in nonaqueous solution[J].Journal of The Chinese Ceramic Society,2017,45(1):20-28.
[18]方智敏,翁维正,万惠霖,等.载体酸碱性对钒基催化剂丙烷氧化脱氢性能的影响及其IR和EPR研究[J].天然气化工,1998,23(2):25-29.FANG Z M,WENG W Z,WAN H L,et al.Effects of acidity and baslcity of supports on the performance of V-based catalysts for oxidative dehydrngenation of propane and their IR and EPR studies[J].Natural Gas Chemical Industry,1998,23(2):25-29.
[19]KNOTEK P,?APEK L,BULANEK R,et al.Vanadium supported on hexagonal mesoporous silica:active and stable catalysts in the oxidative dehydrogenation of alkanes[J].Topics in Catalysis,2007,45(1/2/3/4):51-55.
[20]LIU Y M,CAO Y,YI N,et al.Vanadium oxide supported on mesoporous SBA-15 as highly selective catalysts in the oxidative dehydrogenation of propane[J].Journal of Catalysis,2004,224(2):417-428.
[21]LIU Q L,LI J M,ZHAO Z,et al.Design,synthesis and catalytic performance of vanadium-incorporated mesoporous silica KIT-6catalysts for the oxidative dehydrogenation of propane to propylene[J].Catalysis Science&Technology,2016,6(15):123-128.
[22]TIAN H J,ROSS E I,WACHS I E.Quantitative determination of the speciation of surface vanadium oxides and their catalytic activity[J].Journal of Physical Chemistry B,2006,110(19):9593-9600.
[23]KHODAKOV A,OLTHOFl B,BELL A T,et al.Structure and catalytic properties of supported vanadium oxides:support effects on oxidative dehydrogenation reactions[J].Journal of Catalysis,1999,181(2):205-216.
[24]BULANEK R,?APEK L,SETNICKA M,et al.DR UV-vis study of the supported vanadium oxide catalysts[J].Journal of Physics and Chemistry of Solids,2011,115(25):197-199.
[25]方智敏,翁维正,万惠霖,等.丙烷氧化脱氢VMgO催化剂活性位的研究[J].厦门大学学报(自然科学版),1998,37(4):525-531.FANG Z M,WENG W Z,WAN H L,et al.Study on active sites of VMgO catalysts for oxidative dehydrogenation of propane[J].Journal of Xiamen University(Natural Science),1998,37(4):525-532.
[26]SASIKALA R,SUDARSAN V,SAKUNTALA T,et al.Nanoparticles of vanadia-zirconia catalysts synthesized by polyol-mediated route:enhanced selectivity for the oxidative dehydrogenation of propane to propene[J].Applied Catalysis A:General,2008,350(2):252-258.
[27]BARBERO B P,CADUS L E,HILAIRE L.XPS studies for vanadium pentoxide along the catalytic bed:oxidative dehydrogenation of propane[J].Applied Catalysis A:General,2003,246(2):237-242.