Oxidative dehydrogenation propane

Catalytic testings have been performed using the same rig and a conventional fixed-bed placed in the inner volume of the tubular membrane. The catalyst for isobutane dehydrogenation [9] was a Pt-based solid and sweep gas was used as indicated in Fig. 2. For propane oxidative dehydrogenation a V-Mg-0 mixed oxide [10] was used and the membrane separates oxygen and propane (the hydrocarbon being introduced in the inner part of the reactor). 

Most of the results have been already partly presented in [9] (isobutane dehydrogenation) and [10] (propane oxidative dehydrogenation). Let us recall that the membrane presented in this paper has been associated with a fixed bed catalyst placed within the tube. 

In the propane oxidative dehydrogenation, where the membrane separates the two reactants, a 20% increase in the yield was observed with respect to a conventional reactor working at isoconversion [10]... 

Comparison of promoted alkaline-earth oxide catalysts prepared through evaporation and sol-gel methods by their catalytic performance in propane oxidative dehydrogenation... 

Alkaline earth oxides (AEO = MgO, CaO, and SrO) doped with 5 mol% Nd203 have been synthesised either by evaporation of nitrate solutions and decomposition, or by sol-gel method. The samples have been characterised by chemical analysis, specific surface area measurement, XRD, CO2-TPD, and FTIR spectroscopy. Their catalytic properties in propane oxidative dehydrogenation have been studied. According to detailed XRD analyses, solid solution formation took place, leading to structural defects which were agglomerated or dispersed, their relative amounts depending on the preparation procedure and on the alkaline-earth ion size match with Nd3+. Relationships between catalyst synthesis conditions, lattice defects, basicity of the solids and catalytic performance are discussed. 

Jibril, B.Y. Propane oxidative dehydrogenation over chromium oxide-based catalysts. Appl. Catal. A General 2004, 264, 193-202. 

Propane Oxidative Dehydrogenation on V-containing Silicalite. Reported in... 

Figure 1 is the catalytic behavior of VSU545 in propane oxidative dehydrogenation to propylene. Selectivities to propylene in the range of60-80% are obtained up to propane conversions of about 20-25% and reaction temperatures up to around 450- 500 C. For higher reaction temperatures and conversions the selectivity decreases due both to the formation of carbon oxides and of aromatics. As compared to pure silicalite, a significant increase in both the selectivity to propylene and the activity in propane conversion is observed. 

Figure 1. Propane oxidative dehydrogenation to propylene on VSil545. Exp. conditions flow reactor tests with 2.8% C3, 8.4% O2 in helium. 4.2 g of catalyst with a total flow rate of 3.1 L/h (STP conditions).

Figure 2. Comparison of the catalytic behavior of VSil samples in propane oxidative dehydrogenation to propylene. Conversion of propane and selectivity to propylene at 470 C. Exp. conditions as in Fig. 1.

Figure 4. Comparison of the behavior of VSil545 in propane oxidative dehydrogenation using N2O or O2 as oxidizing agents. Exp. conditions as in Fig. 1. The dotted lines represent the propane conversion and propylene selectivity observed in the absence of the catalyst (homogeneous gas phase). The activity of the catalyst in the absence of O2 or N2O is similar to that observed in the homogeneous gas phase, but the selectivity to propylene (around 50-60%) is lower.

The good catalytic behavior of V-containing silicalite may be associated with the presence of the tetrahedral V species stabilized by the interaction with the zeolite framework as regards both redox and coordination changes. In fact, ESR and TPR data indicate the lower rate of reduction of this species as compared to that of supported vanadium-oxide, and V-NMR data indicate the stability against changes in the coordination environment. Catalytic data (Fig.s 2 and 3) indicate the better catalytic performances of this species in propane oxidative dehydrogenation as compared to supported polynuclear vanadium-oxide which can be removed by treatment with an ammonium acetate solution. 

The role of adsorbed oxygen species in the mechanism of alkane transformation, on the contrary, is more questionable. The effect induced by the substitution of O2 with N2O and IR indications are in agreement with this interpretation, but, on the other hand, activated electrophilic oxygen species form on reduced sites, preferably in tetrahedral coordination (79). The partial reduction of tetrahedral V =0 with formation of tetrahedral v after propane oxidative dehydrogenation can be observed using UV-Visible diffuse reflectance, ESR and V-NMR spectroscopies. It is thus not possible to assign unequivocally the active species in propane selective activation to a tetrahedral V =0 species or to or V -0-0 species formed in the... 

Further studies are necessary to clarify these aspects and the details of the mechanism of propane oxidative dehydrogenation on V-containing silicalite. However, it should be noted that the amount of sites which appears to be stabilized... 

Vanadium species in V-containing silicalite in propane oxidative dehydrogenation— Continued... 

The additional requirement of the size of molecule with respect to the V — V distance in the active site is perhaps the reason behind the fact that propane and butane show not only different selectivity behavior, but also different dependence of the selectivity on the reducibility of the catalyst the selectivity for dehydrogenation in butane oxidation decreases rapidly with increasing reducibility of the catalyst (Figs. 6 and 7), but the selectivity in propane oxidation is much less dependent on it (31). 

The multifunctionality is achieved through either the combination of two different compounds (phase-cooperation) or the presence of different elements inside a single crystalline structure. In antimonates-based systems, cooperation between the metal antimonate (having a rutile crystalline structure), employed for propane oxidative dehydrogenation and propene activation, and the dispersed antimony oxide, active in allylic ammoxidation, is made more efficient through the dispersion of the latter compound over the former. In metal molybdates, one single crystalline structure contains both the element active in the oxidative dehydrogenation of the hydrocarbon (vanadium) and those active in the transformation of the olefin and in the allylic insertion of the N H2 species (tellurium and molybdenum). 

Cortez, G.G. Banares, M.A. A Raman Spectroscopy Study of Alumina-Supported Vanadium Oxide Catalyst During Propane Oxidative Dehydrogenation with Online Activity Measurement /. Catal. 2002, 209, 197-201. 

Molecular strucmre and reactivity of vanadia-based catalysts for propane oxidative dehydrogenation smdied by in sim Raman spectroscopy and catalytic activity measurments. Journal of Catalysis, 111 (2), 293-306. 

The TPD/XPS results indicated that CO, propane and propene bind stronger to a reduced V-terminated 203(000 ) surface than to an oxidized V = 0 terminated surface. Nevertheless, vanadyl groups are probably required in the course of catalytic reactions. However, rates of propane oxidative dehydrogenation (ODH) to propene at atmospheric pressure are rather low and no reaction products were observed by gas chromatography, both for oxidized and reduced V Oj model surfaces at temperatures up to 500 K [12]. 

We shall first show that it is still far fiom clear which are the families of catalysts to be used for the various reactions mainly oxidative dehydrogenation or oxidation to oxygen-containing molecules of ethane, propane or isobutane. Much research is still necessary for understanding the mechanisms leading to high selectivity. In this context, we shall suggest that many concepts inherited from the development in selective oxidation and ammoxidation of olefins are probably of little use. 

Hydrolytic and non-hydrolytic sol-gel routes are implemented to prepare various pure and silica-dispersed vanadium- or niobium-based oxide catalysts corresponding to the compositions Nb-V, Sb-V and Nb-V-M (M = Sb, Mo, Si). Starting reagents in the hydrolytic procedure are isopropanol solutions of the metal alkoxides. The non-hydrolytic route is based on reactions between metal and Si alkoxides and hexane suspensions of niobium(V) chloride. The catalysts are tested in propane oxidative dehydrogenation. NbVOs, SbV04 and Nb2Mo30n are the major crystalline phases detected in the fresh catalysts, but structural modifications are in some cases observed after the use in the catalytic tests. At 500 C, propane conversions of 30 % and selectivities to propene between 20 and 40 % are attained. When the space velocity is decreased, acrolein is in some cases found as by-product. 

In this work, pure or silica-dispersed Nb-V systems were prepared by either the hydrolytic or the non-hydrolytic procedures. Moreover, the hydrolytic sol-gel route was extended to the preparation of pure or silica-dispersed Sb-V and Nb-V-M (M = Sb, Mo) oxide systems. The catalytic performances of these mked-oxide systems in propane oxidative dehydrogenation were investigated. 

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