Catalytic partial oxidation reactions

Vaidyanathan and Doraiswamy [Chem. Eng. Sci., 23 (537), 1966] have studied the catalytic partial oxidation of benzene in a composition range where the reactions of interest all follow pseudo first-order kinetics. The pertinent stoichiometric equations are... 

Vanadia catalysts exhibit high activity and selectivity for numerous oxidation reactions. The reactions are partial oxidation of methane and methanol to formaldehyde, and oxidative dehydrogenation of propane to propene and ethane to ethcnc.62 62 The catalytic activity and selectivity of... 

In addition to SMR, other technologies are used for syngas production from natural gas that involve addition of oxygen or air. The catalytic partial oxidation (CPO) reaction is given in Reaction (3) and in autothermal reforming (ATR) this reaction is combined with Reactions (1) and (2). 

Catalytic Activity. The world-wide interest focused in the catalytic partial oxidation of methane to formaldehyde has led to a great variety of conflicting results (9), The main reason of such discrepancies lies in the lack of a generally valid rule for evaluating and comparing the proposed catalytic systems. In effect, this reaction involves a very complex pathway since the desired partial oxidation product, HCHO, exhibits a limited thermal stability at T>4(X)°C and can be oxidized to more easily than CH itself. Hence, a suitable reactor device and appropriate operating conditions result to be of fundamental importance in order to attain reliable data unaffected by experimental artefacts. 

The results of catalytic partial oxidation of methanol over the spinel catalysts derived from CoAl- and CoAISn-LDH are presented in Table 2. A methanol conversion of 30 to 50 mol % was obtained over catalyst derived from CoAI-LDH. The products obtained were H2, H20, CO and C02. Other products such as formaldehyde, methyl formate or dimethyl ether was not observed under the present experimental conditions. The selectivity of H20 was very high (= 40 to 60 %), probably because of the involvement of the complete oxidation of methanol over these catalysts. It is interesting to note from the Table that the methanol conversion rate and the selectivity of CO2 increased over the catalyst derived from the Sn-containing analogue. The observation that only traces of CO is produced in the Sn-containing catalyst, is attractive for the development of catalyst for POM reaction to produce H2 for fuel cell applications. The only inconvenience is the higher selectivity of H2O by complete oxidation, probably because of the higher Co content in the sample. 

To check this assumed isothermal behavior, one first has to examine the temperature rise in a single well due to the chemical reaction [38], As test reaction, the catalytic partial oxidation of methane was selected ... 

J. J., Ryley, J. F., Micromachined reactors for catalytic partial oxidation reactions, AIChEJ. 1997, 43, 3059-3069. 

A related effort is FORSiM (Fast Oxidation Reaction in Si-technology-based Microreactors) which is funded by the Dutch Technology Foundation and is a cooperative venture between the University of Twente and the Technical University of Eindhoven. The objective of this work is to build and operate the first microreactor for catalytic partial oxidation for small-scale and on-demand hydrogen production61. 

The conditions are substantially more favorable for the microporous catalytic membrane reactor concept. In this case the membrane wall consists of catalyti-cally active, microporous material. If a simple reaction A -> B takes place and no permeate is withdrawn, the concentration profiles are identical to those in a catalyst slab (Fig. 29a). By purging the permeate side with an inert gas or by applying a small total pressure difference, a permeate with a composition similar to that in the center of the catalyst pellet can be obtained (Fig. 29b). In this case almost 100% conversion over a reaction length of only a few millimeters is possible. The advantages are even more pronounced, if a selectivity-limited reaction is considered. This is shown with the simple consecutive reaction A- B- C where B is the desired product. Pore diffusion reduces the yield of B since in a catalyst slab B has to diffuse backwards from the place where it was formed, thereby being partly converted to C (Fig. 29c). This is the reason why in practice rapid consecutive reactions like partial oxidations are often run in pellets composed of a thin shell of active catalyst on an inert support [30],... 

Equally important are structural changes on the micrometer and the millimeter length scales, and eventually real reactors on a centimeter or even meter scale. In the first cases, full-field XAS is a well-matched method for in situ monitoring [6, 13, 25], An illustrative example is the catalytic partial oxidation (CPO) of methane to synthesis gas, a relevant reaction in the future s solid-oxide fuel cells. In Figure 4.3.4, it was... 

Figure 4.3.10 Full-field X-ray microscopy on a 5 wt% Rh/Al2C>3 catalyst during catalytic partial oxidation of methane (A) amount of oxidized Rh species (corresponds to XANES species 1 in [D]), (B) reduced Rh species (reduced species 2 in [D]), (C) the distribution of other elements that show a featureless absorption spectrum in the given energy range, and (D) spectra used for X-ray absorption contrast (original image taken by X-ray camera was 3.0 mm x 1.5 mm the reaction gas mixture 6% CH4/3% ()2/I Ie enters from the left) (reproduced with permission from ref. [69], Copyright ACS, 2006).

The discovery in the early 80 s of titanium silicalites [62-64] opened the new application perspective of zeolitic materials as oxidation catalysts. Several reactions of partial oxidation of organic reactants using dilute solutions of hydrogen peroxide could for the first time be performed selectively in very mild conditions. Other elements inserted in the lattice of silicalites have since been shown to have similarly interesting catalytic properties including, vanadium, zirconium, chromium and more recently tin and arsenic [65]. Titanium silicalites with both MFI (TS-1) and MEL (TS-2) structures have however been the object of more attention and they still seem to display unmatched properties. Indeed some of these reactions like the oxyfunctionalization of alkanes [66-69] by H2O2 are not activated by other Ti containing catalysts (with the exception of Ti-Al-Beta [70]). The same situation... 

Burke, N. and David, T. Coke formation during high pressure catalytic partial oxidation of methane to syngas. Reaction Kinetics and Catalysis Letters, 2005, 84, 137. 

Gardner et al. reported that H2S catalytic partial oxidation technology with an AC catalyst is a promising method for the removal of H2S from fuel cell hydrocarbon feedstocks.206 Three different fuel cell feedstocks were considered for analysis sour natural gas, sour effluent from a liquid middle distillate fuel processor, and a Texaco 02-blown coal-derived synthesis gas. Their experimental results indicate that H2S concentration can be removed down to the part per million level in these plants. Additionally, a power-law rate expression was developed and reaction kinetics compared with prior literature. The activation energy for this reaction was determined to be 34.4 kJ/g mol with the reaction being first order in H2S and 0.3 order in 02. 

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