Copper oxide reduction with methane

The difference to the copper process is, that the reduction of nickel oxide with methane is an endothermic process, thus a heat engine could be employed. Figures 9 and 10 show the enthalpy, entropy diagrams of the reactions outlined in equations (8) and (9). (A metallurgist will not favor the reoxidation of nickel since it is very difficult, but equilibrium thernodynamic considerations do allow it.)... 

Photochemical reduction of C02 was also achieved in the presence of the p-type semiconductor (copper oxide) or silicon carbide electrodes [97]. Irradiation of this system generates methanol and methane as the main products in the case of CuO electrode whereas hydrogen (with efficiency about 80%), methanol (16%), methane, and carbon monoxide in the case of SiC electrode. Also Ti02/CuO systems appeared relatively efficient (up to 19.2% quantum yield) in photocatalytic C02 to CH3OH reduction [98]. 

Table 1 shows activity of catalysts obtained from ZSM-5 zeolite modified with copper at which the ion exchange level of the copper varied from 55% to 126% in the reduction reaction of NOx with methane. The catalysts with a 100-126% degree of ion exchange of the copper have been found to show a higher conversion of the nitrogen oxide to nitrogen, especially at lower temperatures (300-400°C). 

Copper-based catalysts are of considerable importance for industrial reactions, e. g. partial oxidation reactions. This contribution reports on a broad study of the catalytic activity of copper in model redox reactions, e. g. methanol oxidation and oxidative coupling of methane. In addition the interaction of Cu with these reactive gases was investigated by thermoanalytic techniques (TG/DTA, DSC), temperature programmed oxidation and reduction (TPO/tpR) and thermal desorption spectroscopy (TDS). Scanning electron microscopy (SEM) and electron backscattering diffraction (EBSD) was additionally used to characterise the copper catalyst before and after catalytic action. 

How the experimental panorama is influenced by parameters still to be defined was demonstrated by Shibata et al. [86]. Here, preliminary results obtained in aqueous media using a specific brand of high-purity commercial copper cathode were positive with regards to hydrocarbons C3+, provided that no electropolishing was performed before the electrochemical process. If electropolishing preceded the C02 reduction, the cathodes behaved similarly to any other copper cathode, leading essentially (besides hydrogen) only to methane end ethylene. A tentative explanation of this behavior was proposed which referred to the polycrystalline matrix of this brand of copper, which made it particularly adaptable to be covered by oxide layers active in the formation of C3+. However, further experimental evidence on the surface structure, composition and modifications with electrolysis time will be required to substantiate this hypothesis. 

In tlie process of nitric oxide selective reduction, two main reactions are involved NO to N2 reduction, and tlie oxidation of tlie hydrocarbon with oxygen. Wlien the hydrocarbon employed is methane, the copper exchanged in ZSM5 is ineffective to reduce NO since CH preferably reacts with oxygen due to the great oxidating activity of the extralattice oxygens in CuZSMS [9]. 

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