Butane, oxidative dehydrogenation product selectivity

Fig. 7. Differential heat of reoxidation and selectivity for oxidative dehydrogenation of butane on V2Ov y -AFO, samples. For the 2.9 V/nm2 sample, the selectivity was calculated for the detected gaseous products, (a) 8.2 V/nm2 sample, reaction at 400°C (b) 2.9 V/ntn2 sample, reaction at 480°C (c) 8.2 V/nm2 sample, reduction by CO at 530°C, butane reaction at 400°C and (d) 2.9 V/nm2 sample, reduction by CO at 400°C, butane reaction at 480°C. (a) and (b) are from Ref. 50 (c) and (d) and from P. J., Andersen, Ph D. thesis, Northwestern University, 1992.

For the 8.2 V/nm2 sample, the products observed for the pulse reaction at 400°C consisted of only dehydrogenation products (butenes and butadiene) and carbon oxides. No oxygenates were observed, and the carbon balance for each pulse was satisfied within experimental error. The selectivity for dehydrogenation is shown in Fig. 7a as a function of . It was very low when the catalyst was in a nearly fully oxidized state, but increased rapidly when the catalyst was reduced beyond = 0.15. It should be noted that the dependence of selectivity for dehydrogenation on shown in the figure was not a result of changes in conversion of butane in the pulse since these data were for experiments of about the same conversion. 

To promote both the conversion of reactants and the selectivity to partial oxidation products, many kinds of metal compounds are used to create catalytically active sites in different oxidation reaction processes [4]. The most well-known oxidation of lower alkanes is the selective oxidation of n-butane to maleic anhydride, which has been successfully demonstrated using crystalline V-P-O complex oxide catalysts [5] and the process has been commercialized. The selective conversions of methane to methanol, formaldehyde, and higher hydrocarbons (by oxidative coupling of methane [OCM]) are also widely investigated [6-8]. The oxidative dehydrogenation of ethane has also received attention [9,10],... 

The Cg alkylaromatics fraction is formed by ethylbenzene and the three xylene isomers. Ethylbenzene is used as a raw material to produce styrene by dehydrogenation, or oxidative dehydrogenation. Para-xylene and ortho-xylene are catalytically oxidized to give terephthalic and phthalic acid. The meta-xylene isomer can also be oxidized to give isophthalic acid. The major industrial source of these products is the catalytic reforming of naphthas. The Cyclar process, can also produce xylenes from propane and butane. However, using this process, xylenes are formed less selectively than toluene or benzene in the BTX. 

A detailed kinetic study of oxidative dehydrogenation of propane, isobutane, n-butane (23 runs) and LPG (27 runs) was conducted over a wide range of partial pressures of pure and mixed hydrocarbons (0-0.3 atm), oxygen (0-0.2 atm) and steam (0.2-0.7) atm and temperature 600-670°C. Oxidation of Hj, CjHg, C H, CH and CO was also tested at 600-650°C. A set of reactions was selected based on the distribution of products ... 

Ml phase " represents the clearest example of a multifunctional catalyst in which each element, in close geometrical and electronic synergy with the surrounding elements, plays a specific role in turn, as an isolated active site, in every reaction step for the alkane transformation into the partial oxidation product desired. The flexibility of the structure allows modification of the catalyst composition and hence its catalytic behavior. Moreover, this type of mixed-metal oxide catalyst has the ability to catalyze other different oxidation reactions starting from alkanes, such as propane oxidation to acrylic acid, " oxidative dehydrogenation of ethane to ethylene, and n-butane selective oxidation. ... 

The best olefin yields were observed over Pt-coated monoliths. In the case of ethane/02 mixtures, selectivities to ethylene up to 65% at 70% ethane conversion and complete O2 conversion were reported." The oxidative dehydrogenation of propane and -butane produced total olefin select vies of about 60% (mixtures of ethylene and propylene) with high paraffin conversions." " Mixtures of ethylene, propylene and 1-butene were observed by the partial oxidation of -pentane and n-hexane ethylene, cyclohexene, butadiene and propylene were the most abundant products of the partial oxidation of cyclohexane." ... 

Urlan et al. [38] showed that the ODH of -butane over titanium pyrophosphate (TiP207) can be successfully improved by co-feeding CO2 in the system. However, when CO2 was used as the sole oxidant, the -butane conversion was lower. Similarly, when CO2 partial pressures were increased over V—Mg-O catalysts, the yield and selectivity of C4 dehydrogenation products were foimd to show... 

The oxidation of butane on these orthovanadates were tested at 500°C in a flow reactor using a butane oxygen helium ratio of 4 8 88. The observed products were isomers of butene, butadiene, CO, and CO2. The carbon balance in these experiments were within experimental errors, thus the amount of any undetected product if present should be small. The selectivity for dehydrogenation (butenes and butadiene) was found to depend on the butane conversion and be quite different for different orthovanadates. Fig. 4 shows the selectivity for dehydrogenation at 12.5% conversion of butane [15,18,19]. Its value ranged from a high of over 60% for Mg3(V04)2 to a low of less than 5% for... 

The low cost of light alkanes and the fact that they are generally environmentally acceptable because of their low chemical reactivity have provided incentives to use them as feedstock for chemical production. A notable example of the successful use of alkane is the production of maleic anhydride by the selective oxidation of butane instead of benzene (7). However, except for this example, no other successful processes have been reported in recent years. A potential area for alkane utilization is the conversion to unsaturated hydrocarbons. Since the current chemical industry depends heavily on the use of unsaturated hydrocarbons as starting material, if alkanes can be dehydrogenated with high yields, they could become alternate feedstock. 

Thus dehydrogenation is the primary reaction in the oxidation of alkane, and most of the degradation products are formed from secondary reactions. This has been demonstrated experimentally (8). For example, butenes and butadiene are formed with high selectivities at low conversions in the oxidation of butane. 

The first industrial plant for the dehydrogenation of butane to butenes was built by COP I Universal Oil Products) on the iCl (Imperial Chemical Industries) complex at Billingham (United Kingdom) in 1939/1940. The UOP process featured a multitube reactor operating with a chromium oxide/aloinma catalyst, at 570°C and 0.8.10 Pa absolute at the inlet, with a pressure drop of 0l5.10 Pa absolute in the tubes (5 m long, 7.5 cm diameter). Once-through conversion was 215 per cent with a molar selectivity of 80 to 90 per cent... 

---