Table 4. Catalytic Conversion of Bioethanol over Metal-Modified Zeolitesa.
| Aromatic
distribution (selectivity) (%) |
||||||||||
|---|---|---|---|---|---|---|---|---|---|---|
| Entry | Catalyst (Si/Al ratio) | WHSV (h–1) | TOS (h) | T (°C) | Ethanol concn (%) | Aromatics sel. (%) | Benzene | Toluene | Xylene | Ref |
| 1 | H-ZSM-5 (14.5) | 7.3 | – | 400 | 92.2 | 52.9b | 3.1 | 18.9 | 30.9 | (46) |
| 2 | Metal-H-ZSM-5 (14.5)c | 7.3 | – | 400 | 91.5–98.4 | 4.5–75.6b | 0.9–4.3 | 5.4–24.5 | 17.0–46.6 | (46) |
| 3 | H-ZSM-5 (14.5)d | 60e | – | 400 | 100 | 53.7–53.9 | – | – | – | (47) |
| 4 | Fe-H-ZSM-5 (14.5)d | 60e | – | 400 | 92.3–100 | 8.5–41.8 | – | – | – | (47) |
| 5 | 2% Mo2C/ZSM-5 (40) | 40e | – | 500–600 | 100 | 20.2–23.6 | 4.3–8.8 | 7.4–9.2 | 3.4–7.7 | (48) |
| 6 | 2% Ga2O3/ZSM-5 (40) | 40e | – | 500–600 | 100 | 35.0–43.2 | 9.3–22.4 | 14.7–16.1 | 4.0–9.1 | (48) |
| 7 | 2% ZnO/ZSM-5 (40) | 40e | – | 500 | 100 | 21.6 | 5.8 | 9.2 | 4.9 | (48) |
| 8 | ZSM-5 (40) + 2% Mo2C/ZSM-5 (40) | 40e | – | 500 | 100 | 24.8 | 3.8 | 9.8 | 8.5 | (48) |
| 9 | ZSM-5 (40) + 2% Ga2O3/ZSM-5 (40) | 40e | – | 500–600 | 100 | 44.9–46.7 | 4.4–11.0 | 17.9–20.5 | 12.6–18.6 | (48) |
| 10 | ZSM-5 (40) + 2% ZnO/ZSM-5 (40) | 40e | – | 500 | 100 | 36.3 | 10.2 | 14.6 | 9.6 | (48) |
| 11 | 1.7% Ga-ZSM-5 (11.5) | 1.6 | – | 300–500 | 100 | 5.5–40.9f | – | – | – | (49) |
| 12 | H-ZSM-5 (11.5) | 0.4–3.2 | – | 450 | 100 | 16.8–26.0f | – | – | – | (49) |
| 13 | 6.2% Ga-ZSM-5 (11.5) | 0.4–3.2 | – | 450 | 100 | 29.5–55.3f | 10–20 | 18–24 | 11–14 | (49) |
| 14 | H/ZSM-5 (21)g | 0.5–3.5 | 90 | 300–400 | 84–88 | 17–43 | – | – | – | (50) |
| 15 | 1% Ni/ZSM-5 (21)g | 0.5–3.5 | 90 | 300–400 | 90–92 | 17–41 | – | – | – | (50) |
| 16 | H-ZSM-5 (21)h | 1.0 | 60 | 360j | – | 23.2i | 1.1i | 7.5i | 11.7i | (52) |
| 17 | 3 wt% Zn-ZSM-5 (21)h | 1.0 | 140 | 360j | – | 30.6i | 1.5i | 11.5i | 13.8i | (52) |
| 18 | 3 wt% Ga-ZSM-5 (21)h | 1.0 | 240 | 360j | – | 27.5i | 1.1i | 8.9i | 13.8i | (52) |
| 19 | CaO-H-ZSM-5 (25) | 3.0 | 1 | 300–500k | 100 | 9–32i | – | – | – | (51) |
| 20 | MgO-H-ZSM-5 (25) | 3.0 | 1 | 300–500k | 100 | 8–25i | – | – | – | (51) |
| 21 | Ni2+-ZSM-5 (25) | 3.0 | 1 | 400k | 100 | 42.5i | – | – | – | (51) |
| 22 | Cr3+-ZSM-5 (25) | 3.0 | 1 | 400k | 100 | 34.1i | – | – | – | (51) |
| 23 | 0.7% Pd-0.4% Zn/MFI/Al2O3 (30)l | 0.6 | 50 | 330m | 100 | 42i | – | – | – | (53) |
| 24 | 0.1% Au-0.06% Pd/MFI/Al2O3l | 0.6 | 4 | 330m | 100 | 30i | 0.8 | 3.7 | 8.2 | (54) |
a
All reactions were carried on a fixed bed reactor; product was analyzed by GC.
b
Carbon selectivity of BTX.
c
H-ZSM-5 (14.5) incorporated with various metals.
d
With or without water.
e
Flow rate (mL/min).
f
BTX yield (wt%).
g
Products were analyzed by GC and GC-MS.
h
Blended on an extra 50 wt% of Al2O3.
i
Yield (wt%).
j
Pressure = 10 bar.
k
ρ(ethanol) = 0.2 bar.
l
Reactions were performed in a fixed bed microreactor; products were analyzed by GLC.
m
Pressure = 5 bar.