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and temperature to decrease at a given discharge current, which reduces the evaporation rate of the insert with time. The life of the LaB6 insert for three different cathode diameters versus discharge current was calculated based on the evaporation rate at the temperature required to produce the discharge current in the thermally limited regime [ 181. Assuming that 90% of the insert can be evaporated, the cathode life is shown in Fig. 6-47 as a function of the discharge current. Lifetimes of tens of thousands of hours are possible, and the larger cathodes naturally tend to have longer lives. While other mechanisms, such as temperature variations along the insert, LaB6 surface removal, or material build-up due to impurities in the gas, can potentially reduce the life, redeposition of the evaporated LaB6 material will tend to extend the cathode life. Therefore, these life estimates for the different cathode sizes are mostly valid relative to each other, and the actual lifetime of the cathode can be considered to be on the order of the values shown in Fig. 6-47. To obtain an idea of the lifetime of a LaB6 cathode relative to a conventional dispenser cathode, the predictions from a dispenser cathode life model [47] applied to the NSTAR cathode are compared with the 0.8-cm LaB6 cathode life predictions in Fig. 6-48. These two cathodes have similar insert diameters and lengths, and so a direct comparison is possible. The dispenser cathode calculation assumes that barium evaporation from the insert surface causes depletion of nearly all of the barium impregnate at the end of life in the NSTAR dispenser cathode at the measured [33] insert temperature and temperature gradient. This provides an upper limit to the dispenser cathode life if other



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In order to increase the conversion level of methane to the oxygenated products, the concentration of oxygen in the reaction mixture has to be raised This can be done if temperature and pressure are lowered to remain outside the upper explosion limit of the methane-oxygen mixture In a comparative study45 the only catalyst that allowed substantial temperature decrease compared to the homogeneous gasphase process was Sn02, which, however, readily deactivated In contrast, considerable reduction of reaction temperature in homogeneous oxidation could be achieved by using different sensitizers High methanol selectivity under such conditions appears to be associated with the reduced operating temperature A promising development in methane oxidation is the use of N 20 as an oxidant in the presence of Mo0 3 and V 20 5 on silica,43,46-50 Bi203-Sn02,51 or heteropoly acids 52,53 In the presence of water at 600 C, a 65.

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8% combined selectivity of methanol and formaldehyde at 164% conversion was observed over Mo0 3 on silica 46 An even higher selectivity was reported later,47 but at a conversion level of only 3% Kinetic studies indicated that on the same catalyst at temperatures below 540 C, methanol and formaldehyde were probably formed in parallel reactions from the same intermediate Above this temperature, however, consecutive oxidation of methanol is the major route to the formation of formaldehyde 48 The 0- ion formed by surface decomposition of N 20 was postulated as the active species initiating the activation process via hydrogen abstraction 47 The generation of 0 2- via two-electron oxidation accounted for nonselective oxidation An ozone-sensitized oxidative conversion of methane to methanol has been reported.

Unless otherwise stated, the models in Tables E.1, E.2 and E.3 have been applied to all the simulations in this book.

54 A double-layered Sr on La203 then Mo0 3 on a silica catalyst bed exhibited significantly higher yields of formaldehyde from a methane-air mixture than did Mo0 3 on silica alone 55 The photocatalytic activation of methane to yield oxygen-containing compounds is possible by carrying out the reaction in the presence of water 56-58 Addition of oxygen at 100 C enhances the formation of methanol and formaldehyde 57 Hydroxyl radicals formed by the photolysis of water vapor [Eq (923)] activate methane by hydrogen abstraction 56,57 to form methyl radicals [Eq (924)], which react further with water in the product-forming step [Eq (925)] Formation of methyl radicals in a different route may be important depending on temperature and methane concentration 58 [Eq (926)]:.

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