Partial oxidation of methane

The main reaction occurring in the secondary reformer is the partial oxidation of methane with a limited amount of air. The product is a mixture of hydrogen, carhon dioxide, carhon monoxide, plus nitrogen, which does not react under these conditions. The reaction is represented as follows ... 

The second principle was the great defensive strength of an established, capital intensive procedure. In the overall process for making acrylonitrile via acetylene, very big plants were needed for making the acetylene either by partial oxidation of methane or from carbide furnaces. Manufacture of HCN from methane involved further expense ... 

The catalytic partial oxidation of methane into CO and H2 according to... 

For the partial oxidation of methane a catalytic membrane system under development by researchers at the Argonne National laboratory [8] effectively... 

Partial oxidation of methane to synthesis gas over Ru/Ti02 catalysts... 

The catalytic partial oxidation of methane for the production of synthesis gas is an interesting alternative to steam reforming which is currently practiced in industry [1]. Significant research efforts have been exerted worldwide in recent years to develop a viable process based on the partial oxidation route [2-9]. This process would offer many advantages over steam reforming, namely (a) the formation of a suitable H2/CO ratio for use in the Fischer-Tropsch synthesis network, (b) the requirement of less energy input due to its exothermic nature, (c) high activity and selectivity for synthesis gas formation. 

Concerning the reaction pathway, two routes have been proposed the sequence of total oxidation of methane, followed by reforming of the unconverted methane with CO2 and H2O (designated as indirect scheme), and the direct partial oxidation of methane to synthesis gas without the experience of CO2 and H2O as reaction intermediates. The results obtained by Schmidt and his co-workers [4, 5] indicate that the direct reaction scheme may be followed in a monolith reactor when an extremely short contact time is employed at temperatures in the neighborhood of 1000°C. However, the majority of previous studies over numerous types of catalysts show that the partial oxidation of methane follows the indirect reaction scheme, which is supported by the observation that a sharp temperature spike occurs near the entrance of the catalyst bed, and that essentially zero CO and H2 selectivity is obtained at low methane conversions (<25%) where oxygen is not fully consumed [2, 3]. A major problem encountered... 

Controlled elimination of mass and heat transport resistances is an important prerequisite for obtaining intrinsic kinetic parameters of the fast exothermic reaction of partial oxidation of methane to synthesis gas. It has been demonstrated that under conditions of strong transport limitations erroneous conclusions concerning the reaction scheme can be derived [7-9]. It was determined in this laboratory that transport limitations are practically absent over a wide range of operating conditions if one portion of the catalyst (< 40 pm) is diluted with -5 portions of an... 

The Ru/Ti02 catalyst is unique, among many catalysts investigated, in promoting the direct partial oxidation of methane. 

Effects of Li content on the catalytic behaviors and structures of LiNiLaOx catalysts The dpendence of performance of LiNiLaOx catalysts on Li content at 1073K was shown in Fig.l. When D/Ni mole ratio was 0, the relatively acidic LaNiOx had the highest CH4 conversion(92.0%), but no C2 yielded. The products were CO, CO2 and H2, and CO selectivity was 98.3%. It is not an OCM catalyst but a good catalyst for partial oxidation of methane(POM). With Li content and the baric property of LiNiLaOx catalysts increasing, CH4 conversion and CO selectivity decreased, but there was still no C2 formed imtil Li/Ni mole ratio was 0.4. There was a tumpoint of catalytic behavior between 0.2 and 0.4 (Li/Ni mole... 

The two mechanisms proposed to account for the partial oxidation of methane to syngas may be dedgnated as the IPO (Indirect Partial Oxidation) mechanism and the DPO (Direct Partial Oxidation) mechanism. The IPO mechanism was proposed by Prette et al [16] and Lunsford et al [12]. They think CO and H2 are the products of indirect reaction, the overall reaction of the POM reaction is composed of three different reactions... 

Two conqiletely different behaviors of oxidative transformation of methane, namely the Oxidative Coupling of Methane to C2 Hydrocarbons(OCM) and the Partial Oxidation of Methane to Syngas(POM), were performed and related over the nickel-based catalysts due to different modification and different supports. It is concluded that the acidic property favors keeping the reduced nickel and the reduced nickel is necessary for POM reaction, and the bade property frvors keeping the oxidized nickel and the oxidized mckel is necessary for OCM reaction. POM and OCM reactions proceed at different active sites caused by different... 

Tonkovich, A. L. Y, Zilka, J. L., Powell, M. R., Gall, C. J., The catalytic partial oxidation of methane in a micro-channel chemical reactor, in Ehrfeld, W, Rinard, I. H., Wegeng, R. S. (Eds.), Process Miniaturization 2nd International Conference on Microreaction Technology, IMRET 2, Topical Conf. Preprints, pp. 45-53, AIChE, New Orleans (1998). 

Gas-phase reaction 8 [CP 8] Syngas generation by partial oxidation of methane... 

T. Ito and J. H. Lunsford, Synthesis of ethylene and ethane by partial oxidation of methane over lithium-doped magnesium oxide, Nature, 1985, 314, 721. 

Many attempts had been made to solve this problem. One is partial oxidation of methane over a special catalyst capable of inhibiting further oxidation into CO and C02 during the transformation. The reactions in question are shown in Scheme 10.14. 

Partial oxidation of methane to syngas over Ni and Co catalysts was effected by use of microwave irradiation, and compared with conventional heating [73]. Although the same conversion levels and H2/CO ratio (2.0 0.2) were observed, the temperature of the catalyst bed was much lower (200 K) when microwave irradiation was used than with conventional heating. Under both activation modes the Ni-based... 

Direct partial oxidation of methane to produce methanol and other oxygenates... 

Oxidative coupling of methane to yield C2 and higher hydrocarbons 358 Direct partial oxidation of methane to produce methanol and other oxygenates 360... 

Dissanayake, M. et al., Partial oxidation of methane to carbon monoxide and hydrogen over Ni/Al203 catalyst,/. Catal., 132,117,1991. 

Voutetakis, S. et al., Catalytic partial oxidation of methane in a spouted bed reactor, in Natural Gas Conversion V, Studies in Surface Science and Catalysis, vol. 119, Parmaliana, A. et al., Eds., Elsevier, Amsterdam, 807 1998. 

Balachandran, U. et al., Dense ceramic membranes for partial oxidation of methane to syngas, Appl. Catal, 133, 19, 1995. 

Lesuer, H., Czernichowski, A., and Chapelle, J., Electrically assisted partial oxidation of methane, Int.. Hydrogen Energ., 19, 139,1994. 

Hibernia A process for making formaldehyde by the partial oxidation of methane by ozonized oxygen. The catalyst is barium peroxide activated with silver oxide. Developed in Germany during World War II but not commercialized. 

In their study of the kinetics of the partial oxidation of methane to HCHO, along with CO, CO and H20 (Example 5-1), Spencer and Pereira (1987) observed the following ... 

Develop the energy equation as an enthalpy balance for the partial oxidation of methane to formaldehyde, occurring nonisothermally in a PFR, according to the reaction network of Spencer and Pereira (1987) in Example 5-8. 

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