Table 2. Conditions and Performances of the Two-Step Stoichiometric Methane-to-Methanol Reaction on Various Cu Modified Zeolites.
| O2 | CH4 | CH4 | methanol | methanol | |||||||
|---|---|---|---|---|---|---|---|---|---|---|---|
| entry | zeolite | Si/Al ratio | Cu/Al ratio | preparation | activation T (°C) | reaction T (°C) | pressure (bar) | productivity (μmol g–1) | selectivity (%) | extraction method | ref |
| 1 | ZSM-5 | 12 | 0.1 | IE | 450 | 175 | 1 | 0 | a | (335) | |
| 2 | ZSM-5 | 12 | 0.22 | IE | 450 | 175 | 1 | 1.27 | a | (335) | |
| 3 | ZSM-5 | 12 | 0.25 | IE | 450 | 175 | 1 | 3.8 | a | (335) | |
| 4 | ZSM-5 | 12 | 0.32 | IE | 450 | 175 | 1 | 8.9 | a | (335) | |
| 5 | ZSM-5 | 12 | 0.42 | IE | 450 | 175 | 1 | 9 | a | (335) | |
| 6 | ZSM-5 | 12 | 0.54 | IE | 450 | 175 | 1 | 8.2 | a | (335) | |
| 7 | ZSM-5 | 12 | 0.58 | IE | 450 | 175 | 1 | 8.2 | 98 | a | (335) |
| 8 | ZSM-5 | 12 | 0.54 | IE | 450 | 150 | 1 | 8.19 | a | (336) | |
| 9 | ZSM-5 | 25 | 0.51 | IE | 450 | 150 | 1 | 4.1 | a | (336) | |
| 10 | ZSM-5 | 30 | 0.47 | IE | 450 | 150 | 1 | 2.7 | a | (336) | |
| 11 | ZSM-5 | 77.5 | 0.55 | IE | 450 | 150 | 1 | 0.9 | a | (336) | |
| 12 | ZSM-5 | 120 | 0.88 | IE | 450 | 150 | 1 | 0.66 | a | (336) | |
| 13 | ZSM-5 | 11.5 | 0.34 | IE | 450 | 200 | 1 | 16 | b | (337) | |
| 14 | ZSM-5 | 11.6 | 0.53 | IE | 400 | 200 | 8 | 31 | 52 | a | (338) |
| 15 | ZSM-5 | 11.6 | 0.53 | IE | 400 | 360 | 8 | 0 | a | (338) | |
| 16 | Na-ZSM-5 | 14 | 0.65 | IE | 450 | 200 | 1 | 9 | a | (339) | |
| 17 | MOR | 5.3 | 0.39 | IE | 450 | 150 | 1 | 3.6 | a | (336) | |
| 18 | MOR | 5.3 | 0.39 | IE | 450 | 200 | 1 | 13 | a | (336) | |
| 19 | MOR | 8.8 | 0.5 | IE | 450 | 150 | 1 | 6 | a | (336) | |
| 20 | MOR | 8.8 | 0.43 | IE | 450 | 175 | 1 | 11.34 | a | (335) | |
| 21 | MOR | 8.8 | 0.5 | IE | 450 | 200 | 1 | 16 | a | (336) | |
| 22 | MOR | 5 | 0.34 | IE | 450 | 200 | 1 | 31 | b | (337) | |
| 23 | MOR | 10.5 | 0.39 | IE | 400 | 200 | 8 | 119 | 91 | a | (338) |
| 24 | MOR | 10.5 | 0.39 | IE | 400 | 360 | 8 | 5 | a | (338) | |
| 25 | MOR | 10 | 0.27 | SSIE | 450 | 200 | 1 | 37.3 | a | (340) | |
| 26 | MOR | 10 | 0.27 | SSIE | 550 | 200 | 1 | 55.3 | a | (340) | |
| 27 | MOR | 10 | 0.27 | SSIE | 650 | 200 | 1 | 65.2 | a | (340) | |
| 28 | Na-MOR | 5 | 0.3 | IE | 450 | 200 | 1 | 21 | a | (339) | |
| 29 | Na-MOR | 8.5 | 0.38 | IE | 450 | 200 | 1 | 25.8 | a | (339) | |
| 30 | Y | 2.7 | 0.05 | IE | 450 | 175 | 1 | <1 | a | (335) | |
| 31 | Y | 2.7 | 0.29 | IE | 450 | 175 | 1 | <1 | a | (335) | |
| 32 | Y | 2.7 | 0.45 | IE | 450 | 200 | 1 | <1 | a | (336) | |
| 33 | Na-Y | 3 | 0.32 | IE | 450 | 200 | 1 | <1 | a | (339) | |
| 34 | Y | 2.6 | 0.41 | IE | 400 | 360 | 1 | 90 | 91 | a | (338) |
| 35 | Y | 2.6 | 0.41 | IE | 400 | 360 | 1 | 88 | 92 | b | (338) |
| 36 | Y | 2.6 | 0.41 | IE | 400 | 360 | 8 | 303 | 93 | b | (338) |
| 37 | Y | 2.6 | 0.41 | IE | 400 | 360 | 15 | 360 | 93 | b | (338) |
| 38 | USY | 27.5 | 0.32 | IE | 450 | 200 | 1 | <1 | a | (336) | |
| 39 | EMT | 4 | 0.36 | IE | 450 | 150 | 1 | <1 | a | (336) | |
| 40 | FER | 6.2 | 0.42 | IE | 450 | 150 | 1 | 1.6 | a | (336) | |
| 41 | FER | 6.2 | 0.42 | IE | 450 | 200 | 1 | 12 | a | (336) | |
| 42 | Na-FER | 8.9 | 0.38 | IE | 450 | 200 | 1 | 10.4 | a | (339) | |
| 43 | BEA | 9.8 | 0.5 | IE | 450 | 150 | 1 | 1.6 | a | (336) | |
| 44 | BEA | 9.8 | 0.5 | IE | 450 | 200 | 1 | 4.2 | a | (336) | |
| 45 | BEA | 12.4 | 0.4 | IE | 400 | 200 | 8 | 55 | 98 | a | (338) |
| 46 | BEA | 12.4 | 0.4 | IE | 400 | 360 | 8 | 8 | a | (338) | |
| 47 | SSZ-13 | 6 | 0.35 | IE | 450 | 200 | 1 | 28 | b | (337) | |
| 48 | SSZ-13 | 12 | 0.35 | IE | 450 | 200 | 1 | 31 | b | (337) | |
| 49 | Na-SSZ-13 | 15.8 | 0.84 | IE | 450 | 200 | 1 | 30 | a | (339) | |
| 50 | SSZ-16 | 6.5 | 0.34 | IE | 450 | 200 | 1 | 39 | b | (337) | |
| 51 | SSZ-36 | 10 | 0.26 | IE | 450 | 200 | 1 | 36 | b | (337) | |
| 52 | SAPO-34 | 6 | 0.6 | IE | 450 | 200 | 1 | 15 | b | (337) | |
| 53 | OME | 3.2 | 0.07 | IE | 450 | 200 | 1 | 1.9 | a | (339) | |
| 54 | Na-OME | 3.2 | 0.12 | IE | 450 | 200 | 1 | 17.7 | a | (339) | |
| 55 | Na-OME | 3.2 | 0.29 | IE | 450 | 200 | 1 | 86.1 | a | (339) | |
| 56 | Na-OME-fast | 4.3 | 4.78 wt % | IE | 450 | 200 | 1 | ca. 100 | a | (341) | |
| 57 | Na-OME-slow | 4.3 | 4.64 wt % | IE | 450 | 200 | 1 | 150.9 | a | (341) | |
| 58 | ECR | 3.5 | 0.09 | IE | 450 | 200 | 1 | 2.6 | a | (340) | |
| 59 | Na-ECR | 3.5 | 0.14 | IE | 450 | 200 | 1 | 9 | a | (340) | |
| 60 | Na-ECR | 3.5 | 0.33 | IE | 450 | 200 | 1 | 19.7 | a | (340) |
a
Extraction of methanol with water at ambient temperature.
b
Desorption of methanol in a stream of wet inert gases at an elevated temperatures ≥200 °C.