VO_x/SiO_2催化剂上正丁烷氧化脱氢Oxidative Dehydrogenation of n-butane on VO_x/SiO_2 Catalyst
陆江银,杨朋坤
摘要(Abstract)：
采用浸渍法制备了系列VOx/SiO2催化剂,研究了VOx负载量、反应温度、n-butane/O2,空速及反应时间对反应的影响.在反应温度为550℃,VOx负载为3%,n-butane/O2/N2=4/4/42(摩尔比),原料气重时空速为1.5×104mol.h-1.(g.cat)-1时最佳,此时正丁烷转化率和C4烯烃收率分别为40.1%和18.8%,并通过BET、XRD、NH3-TPD、H2-TPR、FT-IR对催化剂进行了表征,XRD,H2-TPR表征结果表明,在低负载量下,VOx能在载体上分散,高负载量时V2O5晶体出现.NH3-TPD表征结果说明,催化剂表面的酸性以弱酸位为主,催化剂活性钒物种表面的酸性增加会提高催化剂的活性,同时也会加剧正丁烷深度氧化反应的程度.
关键词(KeyWords)： VOx/SiO2催化剂;正丁烷;氧化脱氢
基金项目(Foundation): 新疆大学博士科研启动基金(BS060101)资助
作者(Author): 陆江银,杨朋坤
参考文献(References)：
- [1]Rubio O,Herguido J,Men′endez M.Oxidative dehydrogenation of n-butane on V/MgO catalysts—kineticstudy in anaerobicconditions[J].Chem Eng Sci,2003,58:4619-4627.
- [2]Lemonidou A A.Oxidative dehydrogenation of C4 hydrocarbons over VMgO catalyst—kinetic investigations[J].ApplCatal A,2001,216:277-284.
- [3]Chesnokov V V,Bedilo A F,Heroux D S,et al.Oxidative dehydrogenation of butane over nanocrystalline MgO,Al2O3,and VOx/MgO catalysts in the presence of small amounts of iodine[J].J Catal,2003,218:438-446.
- [4]Ge S H,Liu C H,Zhang S C,et al.Effect of carbon dioxide on the reaction performance of oxidativedehydrogenation ofn-butane over V-Mg-O catalyst[J].Chem Eng J,2003,94:121-126.
- [5]刘尧飞,王新平,田福平,等.正丁烷在金属钼酸盐催化剂上的氧化脱氢[J].催化学报,2004,25(9):721-726.
- [6]刘睿,王新平,贾翠英,等.正丁烷在VMgO和Ni2VMgO催化剂上氧化脱氢[J].催化学报,2005,26(8):650-654.
- [7]Nieto J M L,Concepci′on P,Dejoz A,et al.Oxidative dehydrogenation of n-butane and 1-butene on undoped and K-dopedVOx/Al2O3 catalysts[J].Catal Today,2000,61:361-367.
- [8]Harlin M E,Niemi V M,Krause A O I,et al.Effect of Mg and Zr Modification on the Activity of VOxAl2O3 Catalysts inthe Dehydrogenation of Butanes[J].J Catal,2001,203:242-252.
- [9]Wu Z L,Stair P C,UV Raman spectroscopic studies of V/θ-Al2O3 catalysts in butane dehydrogenation[J].J Catal,2006,237:220-229.
- [10]Liu W,Lai S Y,Dai H X,et al.MgO-modified VOx/SBA-15 as catalysts for the oxidative dehydrogenation of n-butane[J].Catal today,2008,131:450-456.
- [11]Blasco T,L′opez Nieto J M,Dejoz A,et al.Inuence of the Acid-Base Character of Supported Vanadium Catalysts onTheir Catalytic Properties for the Oxidative Dehydrogenation of n-Butane[J].J Catal,1995,157:271-282.
- [12]胥月兵,陆江银,钟梅,等.VOx/SiO2催化剂上正丁烷催化脱氢制正丁烯[J].天然气化工,2008,33(3):26-30.
- [13]Parler C M,Ritter J A,Amiridis M D.Infrared spectroscopic study of sol–gel derived mixed-metal oxides[J].J Non-CrystSolids,2001,279:119-125.
- [14]Haoudi A,Dhamelincourt P,Mazzah A,et al.Vanadium and tellurium siloxane compounds as precursors of vanadiumoxide and tellurium oxide silica material[J].Int J Inorg Mater,2001,3(4/5):357-366.
- [15]Wildberger MD,Mallat T,Gobel U,et al.Oxidation of butane and butadiene to furan over vanadia–silica mixed oxides[J].Appl Catal A:Gen,1998,168,69-80.
- [16]Baltes K,Cassiers K,Van Der Voort P,et al.MCM-48-Supported Vanadium Oxide Catalysts,Prepared by the MolecularDesigned Dispersion of VO(acac)2:A detailed study of the highly reactive MCM-48 surface and the structure and activityof the deposited VOx[J].J Catal,2001,197:160-171.
- [17]Adamski A,Sojka Z,Dyrek K.Surface Heterogeneity of Zirconia-Supported V2O5 Catalysts.The Link between Structureand Catalytic Properties in Oxidative Dehydrogenation of Propane[J].Langmuir,1999,15:5733-5741.
- [18]Owens L,Kung H H,The Effect of Loading of Vanadia on Silica in the Oxidation of Butane[J].J Catal,1993,144:202-213.
- [19]Das N,Eckert H,Hu H,et al.Bonding states of surface vanadium oxide phases on silica:Structural characterization by51V-NMR and Raman spectroscopy[J].J Phys Chem,1993,97(31):8240–8243.