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Catalytic Behaviors for Isobutene Selective Oxidation of MoVBi-AlPO4 Catalysts

Author: JiangShi
Tutor: WangXiTao
School: Tianjin University
Course: Industrial Catalysis
Keywords: Sol-gel method MoVBi-AlPO4 Catalyst Isobutylene Selective Oxidation Methacrolein
CLC: O643.32
Type: Master's thesis
Year: 2010
Downloads: 25
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Abstract


Selective oxidation of isobutene to methacrolein（MAL） is a key step for methylmethacrylate product using isobutene as raw materials. In this paper, the MoV-AlPO4and MoVBi-AlPO4 catalysts were prepared by the Sol-Gel method. The surfacecomposition and structure, physical and chemical properties, lattice oxygen activityand selective oxidation of isobutene of the catalysts were systemically studied byusing the techniques of XRD, BET, Raman, TPR, IR, UV-Vis DRS and micro-reactor.MoV-AlPO4 is mainly composed of MoO3, V2O5 and AlPO4. The loading amountof molybdenum, vanadium and calcination temperature has a great effect on thedispersion and coordination of molybdenum and vanadium oxides, activity of latticeoxygen species. With the increase of the loading amount of molybdenum, vanadiumand calcination temperature, the molybdenum oxide and vanadium oxide intetrahedral coordination which is highly dispersed on the surface of bulk phase AlPO4was gradully transformed into octahedral coordination, crystal MoO3 and V2O5, andthe reduction temperature of lattice oxygen decreases firstly and then increases.Theaddition of Bi to the MoV-AlPO4 had great influence on the structure of catalysts. Theaddition of Bi oxide obviously improved the dispersion of molybdenum oxide on thesurface through the strong chemical interaction between the molybdenum oxide andBi oxide, and a new phase Bi2Mo3O12 was formed. Furthermore, Bi significantlyenhanced lattice oxygen activity of the MoV-AlPO4 catalyst.The mainly products of selective oxidation of isobutene over MoV-AlPO4 catalystswere MAL, acetone, acetic acid and COx. The active component loading amount andcalcining temperature of catalysts has a major impact on isobutene conversion andselectivity of MAL. The catalyst pore structure, dispersion of Molybdenum speciesand the redox properties were responsible for the catalytic properties, which were alsorelated to the coordination of Mo active species. For MoV-AlPO4 catalysts, under theoptimum reaction conditions （360℃, i-C4H8:O2=1:2）, the isobutene conversion33.88% and MAL selectivity 49.06% can be obtained. Own to better dispersion ofmolybdenum oxide and the formation of a new crystalline phase Bi2Mo3O12 whichaccelerated the transfer rate of gas active oxygen and lattice oxygen, the addition ofBi significantly improved MAL selectivity of the MoV-AlPO4 catalyst. For MoV0.3Bi0.3-AlPO4 catalysts, under the optimum reaction conditions （360℃,i-C4H8:O2=1:2）, the results of isobutene conversion 45.65% and MAL selectivity75.82% can be obtained.

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CLC: > Mathematical sciences and chemical > Chemistry > Physical Chemistry ( theoretical chemistry ),chemical physics > Chemical kinetics,catalysis > Catalytic > Catalytic reaction
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