Table 1 The effect of temperature on direct methane oxidation to methanol in near supercritical acetonitrile.

From: Partial oxidation of methane to methanol on boron nitride at near critical acetonitrile

Cut off

T (°C)

MeOH yield (%)

CH4 based

S.D. 0.4 × 10–1

MeOH yield (%)

O2 based

S. D. 0.2

CO2 yield (%)

O2 based

MeOH

Selectivity %

CO2

Selectivity %

O2

Conversion%

250

0.4 × 10–1

0.3

0.6

50

50

0.9

275

0.5

4.6

1.6

85

15

6.2

300†

0.8

6.6

53

20

80

59

275*

2.0

17

4.6

88

12

22

  1. *With 400 mg h-BN (2.30: 1 h-BN: oxygen molar ratio), all other runs were conducted with 3 mL acetonitrile, 7 mmol of O2, 118 mmol of CH4, and 163 mmol He. All gases were cold fed to a total of ~ 1570 psi at − 30 °C. The reactor was heated at a 2.5 °C/min ramp rate to 275 °C. The heater cut off was set at 275 °C (no dwell time). The stirring speed was set at 60 rpm. The reactor was cooled to ambient at the natural convection rate. Standard deviations (S. D.) were based on deviations in loading pressure. Methanol yield was calculated based on a GC peak area calibration plot and reconfirmed with NMR. The standard deviation of the yield was calculated by replicating one experiment and comparing those data to NMR data. Small amounts of acetamide and acetic acid were formed as hydration products of acetonitrile and for simplicity purposes those products were excluded from the calculations.
  2. †Higher tendency towards formation of acetamide and acetic acid relative to other reaction conditions was observed. As based on the GC traces these products were formed in negligible amounts for entries 1, 2 and 4.
Back to article page