Direct Oxidation of Saturated Hydrocarbons at High Pressures

Abstract

Effect of Pressure. Blank runs made at 400°to 700°C.at atmospheric pressure showed only traces of methanol and formaldehyde. As would be expected, the effect of increased pressure is to increase the amount of methyl alcohol in the product. However, although the yield of methyl alcohol still continued to rise, the rate of increase of the total oxygen efficiency and carbon conversion to desirable products (methyl alcohol, formaldehyde, and formic acid) fell off with increasing pressure. Most of the experiments were made at 135 atmospheres.

The direct conversion of methane to methanol by controlled oxidation

“…Similar results were obtained when reactions 13,16, 20, and 24 were omitted. Including reaction 13' or increasing its value to [10][11] did not improve the results. On the other hand, reactions 10, 11, 12, and 25 were shown to be essential to the overall reaction scheme.…”

“…(2) CH30-+ 02 -* CH20 + H02-(20 CH30--CH20 + H-(3) CH4 + -OH (4) CH4 + H02--(5) CH20 + -OH - (6) CH20-+ H02-(7) CH20 + 02 - 1013 exp(-30000/RT) 10~10 exp(-8500/RT) 10"10 exp(-23 000/RT) 1.6 x 10'lal exp(-2500/RT) 1.9 x 10'11 exp(-13 000/RT) 7.5 x 10'11 exp(-41000/RT) lO'13 (9) H202 + M --20Hc + M 7 = 2.83 x 10'7 exp(-46 300/RT) (10) CH302-+ CH4 -CH3OOH + -CH3 k10 = 10'10 exp(-19700/RT) (11) CH302-+ CH20 -CH3OOH + -CHO kn = 10-13 (12) CH3OOH -CH30-+ -OH kl2 = 1012-65 exp(-40500/RT) (13) CH302-+ H02--CH3OOH + 02 7a = 1.6 X 10'115 (130 CH302-+ CH302--2CH30-+ 02 73. = 1.75 x 10'13 (14) CHsO-+ CH4 -CH3OH + -ch3 74 = lO'12,2 exp(-ll 000/RT) (15) CH30-+ CHsO -CH3OH + -CHO 75 = 1.6 X 10'14 4 exp(-3000/RT) ( 16) CO + -OH -C02 + -H 7e = 1.6 X 10125 exp(-810/RT) (17) CO + H02--* C02 + -OH kl2 = 2.2 x 10'10 exp(~23 000/RT) (18) H-+ CH20 -H2 + -CHO 7s = 1.6 x lO'1008 exp(-4330/RT) (19) H-+ CH4 -H2 + -CH3 7 = 5X 10"9 exp(-ll 900/R70 (20) H-+ O, + M -H02-+ M 7o = lO'32 (21) ho2-72H20 + 3/4o2 7i -1 (22) H02-+ H02--H202 + 02 !!…”

The Oxidations of Hydrocarbons at High Pressure.

“…The increase in the methylphenylcarbinol with increase of reaction temperature affords evidence that it constitutes the initial product of the oxidation. The above experiments also show that with rise of temperature there is an increasing tendency for the nucleus TABLE 14 Products from the combustion of a 20:7.S ethylbenzene-air medium, at 27.5 atm. to undergo direct oxidation, the distribution of oxygen between the side chain and the nucleus at the three temperatures being as follows: Although the formation of benzaldehyde and benzoic acid has been attributed to further oxidation of acetophenone, they might equally well arise from ethylbenzene by successive hydroxylations of the hydrogen attached to the carbon in the beta position.…”

Die direkte katalytische Oxidation von Methan zu Methanol – eine kritische Beurteilung

“…Allerdings war die Effizienz dieser Hochdrucksysteme unbefriedigend, da die Methanolselektivitätf ür1 .6 %u mgewandeltes Methan niedriger als 60 %w ar. Wiezevich und Frolich [38] [43] Diese grundlegenden Ergebnisse ebneten den Wegfürein aufstrebendes Forschungsgebiet. Boomer und Thomas [35] schrieben die Bildung von Methanol einer Oberflächenreaktion von Methan mit Sauerstoff zu.…”