Chinese Journal of Catalysis ›› 2022, Vol. 43 ›› Issue (3): 731-754.DOI: 10.1016/S1872-2067(21)63802-0
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Junhui Liua,*(), Yakun Songa, Xuming Guoa, Chunshan Songb,c,#(), Xinwen Guoc,$()
Received:
2021-01-30
Revised:
2021-01-30
Online:
2022-03-18
Published:
2022-02-18
Contact:
Junhui Liu, Chunshan Song, Xinwen Guo
Junhui Liu, Yakun Song, Xuming Guo, Chunshan Song, Xinwen Guo. Recent advances in application of iron-based catalysts for COx hydrogenation to value-added hydrocarbons[J]. Chinese Journal of Catalysis, 2022, 43(3): 731-754.
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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63802-0
Fig. 2. Qualitative interpretation of an ab initio atomistic thermodynamics study of the iron carbide structures. Reproduced from Ref. [76] with permission from the American Chemical Society.
Fig. 3. Schematic illustration of the formation mechanism of Fe5C2 nanoparticles. Reproduced from Ref. [78] with permission from the American Chemical Society.
Fig. 4. Catalytic activity of iron carbide phases (ε-Fe2C, Fe7C3, and χ-Fe5C2) in FTS. Reproduced from Ref. [91] with permission from the American Chemical Society.
Fig. 6. Schematic illustration of CO2 hydrogenation over Fe and Co catalysts. Reproduced from Ref. [118] with permission from Royal Society of Chemistry.
Catalyst | H2/CO | T (°C) | P (MPa) | GHSV (mL h-1 g-1) | CO conv. (%) | CO2 sel. (%) | Product distribution (%) | Ref. | |||
---|---|---|---|---|---|---|---|---|---|---|---|
CH4 | C2‒C4= | C2‒C40 | C5+ | ||||||||
FeSi | 2 | 260 | 1.5 | 2000 | 53.0 | 32.4 | 24.9 | 0.46 a | 0.46 a | 23.7 | [ |
LiFeSi | 2 | 260 | 1.5 | 2000 | 36.1 | 25.4 | 17.5 | 0.59 a | 0.59 a | 31.3 | [ |
NaFeSi | 2 | 260 | 1.5 | 2000 | 50.1 | 32.0 | 16.9 | 0.63 a | 0.63 a | 35.4 | [ |
KFeSi | 2 | 260 | 1.5 | 2000 | 69.2 | 43.3 | 14.0 | 0.63 a | 0.63 a | 46.1 | [ |
RbFeSi | 2 | 260 | 1.5 | 2000 | 79.0 | 43.7 | 15.9 | 0.61 a | 0.61 a | 45.3 | [ |
CsFeSi | 2 | 260 | 1.5 | 2000 | 73.3 | 46.3 | 15.1 | 0.64 a | 0.64a | 45.4 | [ |
Fe/rGO | 1 | 340 | 2.0 | 42000 | 342 b | 49.7 | 42.3 | 33.2 | 23.4 | 1.1 | [ |
FeK2/rGO | 1 | 340 | 2.0 | 60000 | 545 b | 49.0 | 22.0 | 63.7 | 6.4 | 7.9 | [ |
FeMg/rGO | 1 | 340 | 2.0 | 24000 | 247 b | 40.7 | 35.6 | 33.0 | 26.9 | 4.5 | [ |
FeMgK2/rGO | 1 | 340 | 2.0 | 132000 | 1338 b | 40.8 | 20.3 | 65.0 | 6.2 | 8.5 | [ |
6 wt% Mn/Fe3O4 | 2 | 320 | 1.0 | 5 c | 41.5 | 37.8 | 9.7 | 60.1 | 6.5 | 23.7 | [ |
FeZn | 65:24 | 350 | 2.0 | 3000 | 95.09 | 15.79 | 25.60 | 53.32 | 7.72 | 13.36 | [ |
KFe/KIT-6(B5) | 2 | 350 | 2.0 | 4000 | 70.8 | — | 16.0 | 6.7 | 8.4 | 68.9 | [ |
Fe/CNF | 1 | 340 | 2.0 | — | 29.8 b | — | 13 | 52 | 12 | 18 | [ |
Fe/α-Al2O3 | 1 | 340 | 2.0 | — | 13.5 b | — | 11 | 53 | 6 | 21 | [ |
FexN-in-450(CNT) | 1 | 300 | 0.5 | 15000 | 960.6 b | 38.0 | 27.7 | 35.2 | 13.5 | 22.5 | [ |
Fe/NG-16.4 | 1 | 340 | 0.5 | 600 | 21.1 | 35.1 | 21.4 | 49.6 | 5.4 | 19.8 | [ |
Fe/α-Al2O3-H-8S | 1 | 350 | 0.1 | 9000 | 0.9 | 43 | 29 | 68 | 2 | ~1 | [ |
Table 1 Summary of catalytic performance over iron-based catalysts with various promoters and supports for FTS.
Catalyst | H2/CO | T (°C) | P (MPa) | GHSV (mL h-1 g-1) | CO conv. (%) | CO2 sel. (%) | Product distribution (%) | Ref. | |||
---|---|---|---|---|---|---|---|---|---|---|---|
CH4 | C2‒C4= | C2‒C40 | C5+ | ||||||||
FeSi | 2 | 260 | 1.5 | 2000 | 53.0 | 32.4 | 24.9 | 0.46 a | 0.46 a | 23.7 | [ |
LiFeSi | 2 | 260 | 1.5 | 2000 | 36.1 | 25.4 | 17.5 | 0.59 a | 0.59 a | 31.3 | [ |
NaFeSi | 2 | 260 | 1.5 | 2000 | 50.1 | 32.0 | 16.9 | 0.63 a | 0.63 a | 35.4 | [ |
KFeSi | 2 | 260 | 1.5 | 2000 | 69.2 | 43.3 | 14.0 | 0.63 a | 0.63 a | 46.1 | [ |
RbFeSi | 2 | 260 | 1.5 | 2000 | 79.0 | 43.7 | 15.9 | 0.61 a | 0.61 a | 45.3 | [ |
CsFeSi | 2 | 260 | 1.5 | 2000 | 73.3 | 46.3 | 15.1 | 0.64 a | 0.64a | 45.4 | [ |
Fe/rGO | 1 | 340 | 2.0 | 42000 | 342 b | 49.7 | 42.3 | 33.2 | 23.4 | 1.1 | [ |
FeK2/rGO | 1 | 340 | 2.0 | 60000 | 545 b | 49.0 | 22.0 | 63.7 | 6.4 | 7.9 | [ |
FeMg/rGO | 1 | 340 | 2.0 | 24000 | 247 b | 40.7 | 35.6 | 33.0 | 26.9 | 4.5 | [ |
FeMgK2/rGO | 1 | 340 | 2.0 | 132000 | 1338 b | 40.8 | 20.3 | 65.0 | 6.2 | 8.5 | [ |
6 wt% Mn/Fe3O4 | 2 | 320 | 1.0 | 5 c | 41.5 | 37.8 | 9.7 | 60.1 | 6.5 | 23.7 | [ |
FeZn | 65:24 | 350 | 2.0 | 3000 | 95.09 | 15.79 | 25.60 | 53.32 | 7.72 | 13.36 | [ |
KFe/KIT-6(B5) | 2 | 350 | 2.0 | 4000 | 70.8 | — | 16.0 | 6.7 | 8.4 | 68.9 | [ |
Fe/CNF | 1 | 340 | 2.0 | — | 29.8 b | — | 13 | 52 | 12 | 18 | [ |
Fe/α-Al2O3 | 1 | 340 | 2.0 | — | 13.5 b | — | 11 | 53 | 6 | 21 | [ |
FexN-in-450(CNT) | 1 | 300 | 0.5 | 15000 | 960.6 b | 38.0 | 27.7 | 35.2 | 13.5 | 22.5 | [ |
Fe/NG-16.4 | 1 | 340 | 0.5 | 600 | 21.1 | 35.1 | 21.4 | 49.6 | 5.4 | 19.8 | [ |
Fe/α-Al2O3-H-8S | 1 | 350 | 0.1 | 9000 | 0.9 | 43 | 29 | 68 | 2 | ~1 | [ |
Fig. 7. Schematic illustration of syngas conversion over (a) the core-shell Fe3O4@MnO2 catalyst. Reproduced from Ref. [134] with permission from the American Chemical Society. (b) The Fe2O3@MnO2 spindle catalyst. Reproduced from Ref. [135] with permission from Elsevier.
Catalyst | H2/CO2 | T (°C) | P (MPa) | GHSV (mL h-1 g-1) | CO2 conv. (%) | Product sel. (%) | O/P | Ref. | ||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
CO | CH4 | C2‒C4= | C2‒C40 | C5+ | ||||||||
Fe/ZrO2 | 3 | 340 | 2.0 | 1200 | 32 | 25 | 52.5 | 0.1 | 21.8 | 0.7 | — | [ |
FeNa/ZrO2 | 3 | 340 | 2.0 | 1200 | 39 | 21 | 12.4 | 28.9 | 5.2 | 12.5 | — | [ |
FeCs/ZrO2 | 3 | 340 | 2.0 | 1200 | 39 | 16 | 17.4 | 28.8 | 6.4 | 14.3 | — | [ |
FeK/ZrO2 | 3 | 340 | 2.0 | 1200 | 42 | 15 | 11.9 | 29.0 | 6.1 | 19.0 | — | [ |
FeK/SiO2 | 3 | 340 | 2.0 | 1200 | 7.1 | 92 | 5.8 | 1.5 | 0.7 | 0.1 | — | [ |
FeK/Al2O3 | 3 | 340 | 2.0 | 1200 | 33 | 17 | 12.9 | 27.4 | 4.6 | 31.2 | — | [ |
FeK/TiO2 | 3 | 340 | 2.0 | 1200 | 21 | 55 | 8.4 | 16.3 | 2.7 | 10.6 | — | [ |
FeK/Meso-C | 3 | 340 | 2.0 | 1200 | 33 | 31 | 18.6 | 17.4 | 15.1 | 7.0 | — | [ |
FeK/CNT | 3 | 340 | 2.0 | 1200 | 35 | 12 | 19.2 | 27.4 | 4.6 | 31.2 | — | [ |
Fe3O4 | 3 | 320 | 3.0 | 2000 | 29.3 | 16.6 | 50.3 | 0.1 | 30.4 | 2.6 | 0.0 | [ |
FeNa(1.18) | 3 | 320 | 3.0 | 2000 | 40.5 | 13.5 | 13.7 | 40.3 | 6.5 | 26.0 | 6.2 | [ |
1Na/Fe | 3 | 320 | 3.0 | 2040 | 36.8 | 10.1 | 7.0 | 23.4 | 2.1 | 56.9 | 11.0 | [ |
5Mn-Na/Fe | 3 | 320 | 3.0 | 2040 | 38.6 | 11.7 | 11.8 | 30.2 | 4.0 | 42.1 | 7.5 | [ |
CuFeO2-24 | 3 | 300 | 1.0 | 1800 | 16.7 | 31.4 | 1.6 | 22.4 | 22.4 | 44.5 | 7.7 | [ |
ZnFe2O4 | 3 | 340 | 1.0 | 1800 | 34.0 | 11.7 | 8.6 | 28.1 | 28.1 | 51.6 | 11.3 | [ |
Fe-Cu-K-La | 3 | 300 | 1.1 | 3600 | 23.2 | 33 | 13 | 25 | 25 | 29 | 0.52 | [ |
Fe-Co-K(0.1)/P25 | 3 | 300 | 1.1 | 3600 | 23.9 | 31 | 23 | 11 | 11 | 35 | 0.20 | [ |
Fe-Cu-K(0.1)/P25 | 3 | 300 | 1.1 | 3600 | 19.9 | 49 | 12 | 8 | 8 | 31 | 0.38 | [ |
Table 2 Summary of catalytic performance over iron-based catalysts with various promoters and supports for CO2 hydrogenation.
Catalyst | H2/CO2 | T (°C) | P (MPa) | GHSV (mL h-1 g-1) | CO2 conv. (%) | Product sel. (%) | O/P | Ref. | ||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
CO | CH4 | C2‒C4= | C2‒C40 | C5+ | ||||||||
Fe/ZrO2 | 3 | 340 | 2.0 | 1200 | 32 | 25 | 52.5 | 0.1 | 21.8 | 0.7 | — | [ |
FeNa/ZrO2 | 3 | 340 | 2.0 | 1200 | 39 | 21 | 12.4 | 28.9 | 5.2 | 12.5 | — | [ |
FeCs/ZrO2 | 3 | 340 | 2.0 | 1200 | 39 | 16 | 17.4 | 28.8 | 6.4 | 14.3 | — | [ |
FeK/ZrO2 | 3 | 340 | 2.0 | 1200 | 42 | 15 | 11.9 | 29.0 | 6.1 | 19.0 | — | [ |
FeK/SiO2 | 3 | 340 | 2.0 | 1200 | 7.1 | 92 | 5.8 | 1.5 | 0.7 | 0.1 | — | [ |
FeK/Al2O3 | 3 | 340 | 2.0 | 1200 | 33 | 17 | 12.9 | 27.4 | 4.6 | 31.2 | — | [ |
FeK/TiO2 | 3 | 340 | 2.0 | 1200 | 21 | 55 | 8.4 | 16.3 | 2.7 | 10.6 | — | [ |
FeK/Meso-C | 3 | 340 | 2.0 | 1200 | 33 | 31 | 18.6 | 17.4 | 15.1 | 7.0 | — | [ |
FeK/CNT | 3 | 340 | 2.0 | 1200 | 35 | 12 | 19.2 | 27.4 | 4.6 | 31.2 | — | [ |
Fe3O4 | 3 | 320 | 3.0 | 2000 | 29.3 | 16.6 | 50.3 | 0.1 | 30.4 | 2.6 | 0.0 | [ |
FeNa(1.18) | 3 | 320 | 3.0 | 2000 | 40.5 | 13.5 | 13.7 | 40.3 | 6.5 | 26.0 | 6.2 | [ |
1Na/Fe | 3 | 320 | 3.0 | 2040 | 36.8 | 10.1 | 7.0 | 23.4 | 2.1 | 56.9 | 11.0 | [ |
5Mn-Na/Fe | 3 | 320 | 3.0 | 2040 | 38.6 | 11.7 | 11.8 | 30.2 | 4.0 | 42.1 | 7.5 | [ |
CuFeO2-24 | 3 | 300 | 1.0 | 1800 | 16.7 | 31.4 | 1.6 | 22.4 | 22.4 | 44.5 | 7.7 | [ |
ZnFe2O4 | 3 | 340 | 1.0 | 1800 | 34.0 | 11.7 | 8.6 | 28.1 | 28.1 | 51.6 | 11.3 | [ |
Fe-Cu-K-La | 3 | 300 | 1.1 | 3600 | 23.2 | 33 | 13 | 25 | 25 | 29 | 0.52 | [ |
Fe-Co-K(0.1)/P25 | 3 | 300 | 1.1 | 3600 | 23.9 | 31 | 23 | 11 | 11 | 35 | 0.20 | [ |
Fe-Cu-K(0.1)/P25 | 3 | 300 | 1.1 | 3600 | 19.9 | 49 | 12 | 8 | 8 | 31 | 0.38 | [ |
Fig. 8. In situ XRD patterns for the (a) Fe/ZrO2 catalyst, (b) K-Fe/ZrO2 catalyst under (H2 + CO2) (H2/CO2 = 3) gas flow at 345 °C for different times, and (c) Fe/ZrO2 catalysts with different alkali metals after reaction. Reproduced from Ref. [155] with permission from Elsevier.
Fig. 9. Effects of Na promoter on Fe-based catalyst for CO2 hydrogenation to alkenes. Reproduced from Ref. [166] with permission from the American Chemical Society.
Fig. 10. Catalytic performance of 10FexCu1K/Al2O3 at 400 °C (a), 10Fe3K/Al2O3 and 10Fe3Cu3K/Al2O3 at 400 °C (b), 10Fe1K/Al2O3 and 10Fe3Cu1K/ Al2O3 at 320 °C (c), and 10Fe3Cu1K/Al2O3 at different temperatures (d). Reproduced from Ref. [172] with permission from the American Chemical Society.
Fig. 11. N2 physisorption isotherms and pore-size distribution (a), SEM image (b), HAADF-STEM image (c), and TEM image and particle distribution histogram (d) of the as-prepared FeK1.5/HSG catalyst. Inset in (d) shows the lattice fringes of the nanoparticle on the catalyst. Reproduced from Ref. [252] with permission from the American Chemical Society.
Catalyst | H2/CO | T (°C) | P (MPa) | GHSV (mL h-1 g-1) | CO conv. (%) | CO2 sel. (%) | Product distribution (%) | Ref. | ||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
CH4 | C2‒C4= | C2‒C40 | C5+ | |||||||||
FeZr(0.3) | 2 | 300 | 2.0 | 8000 | 82.1 | 41.2 | 4.6 | 5.3 | 4.5 | 85.6 | [ | |
Fe/PANI | 1 | 350 | 2.0 | 9000 | 79 | 44 | 24 | 47 | 14 | 15 | [ | |
IO-CAT | 1 | 275 | 1.5 | 2800 a | 75.4 | 42.6 | 9.05 | 20.0 | 20.0 | 71 | [ | |
Fe@C-400 | 1 | 340 | 2.0 | 30000 | 74 | 47 | 28.3 | 30.2 b | 26.4 b | — | [ | |
Fe@C-500 | 1 | 340 | 2.0 | 30000 | 76 | 46 | 27.8 | 25.9 b | 27.8 b | — | [ | |
Fe@C-600 | 1 | 340 | 2.0 | 30000 | 74 | 46 | 25.9 | 24.1 b | 31.5 b | — | [ | |
Fe@C-900 | 1 | 340 | 2.0 | 30000 | 53 | 45 | 23.6 | 30.9 b | 23.6 b | — | [ | |
38Fe@C | 1 | 340 | 1.5 | 3300 c | 70 | 43 | — | 24.6 | 22.8 | — | [ | |
33Fe@C/Al | 1 | 340 | 1.5 | 3300 c | 68 | 43 | — | 28.1 | 22.8 | — | [ | |
Fe-MIL-88B-NH2/C d | 1 | 300 | 2.0 | 36000 | 81.8 | 42.9 | 15.1 | 21.4 | 12.8 | 50.7 | [ | |
Fe-MIL-88B-NH2/C d | 1 | 300 | 2.0 | 180000 | 27.8 | 25.5 | 18.7 | 17.5 | 9.4 | 54.4 | [ | |
R-Fe@HZSM-5 | 2 | 270 | 2.0 | 2240 | 93 | 12 | 7.5 | 21.5 | 21.5 | 71 | [ | |
Fe3O4@H-ZSM-5 | 1 | 270 | 2.0 | 960 | 87 | — | 16 | 36.2 | 36.2 | 47.8 | [ | |
FeCuK/ZSM-5 | 2 | 300 | 1.0 | 2000 | 81.1 | 35.6 | 19.6 | 30.3 | 12.3 | 37.8 | [ | |
FeCuK/Mordenite | 2 | 300 | 1.0 | 2000 | 72.9 | 37.7 | 32.2 | 18.8 | 25.4 | 23.6 | [ | |
FeCuK/Beta-zeolite | 2 | 300 | 1.0 | 2000 | 63.9 | 25.2 | 31.5 | 29.2 | 21.6 | 17.7 | [ | |
FeZnNa | 8:3 | 340 | 2.0 | 10000 | 74.9 | 27.3 | 10.9 | 25.5 | 4.4 | 58.1(1.1) e | [ | |
FeZnNa@HZSM-5 | 8:3 | 340 | 2.0 | 10000 | 88.3 | 27.7 | 11.3 | 1.4 | 38.6 | 28.9(19.8) e | [ | |
FeZnNa@0.1-HZSM-5 | 8:3 | 340 | 2.0 | 10000 | 84.2 | 26.5 | 9.9 | 0.7 | 35.6 | 22.7(30.9) e | [ | |
FeZnNa@0.6-HZSM-5 | 8:3 | 340 | 2.0 | 10000 | 89.2 | 26.9 | 9.8 | 1.0 | 26.8 | 21.8(40.5) e | [ | |
FeZnNa@0.6-HZSM-5-a | 8:3 | 340 | 2.0 | 10000 | 88.8 | 27.5 | 9.6 | 1.0 | 25.6 | 13.2(50.6) e | [ | |
FeMn | 1 | 320 | 1.0 | 3600 | 58.7 | 42.4 | 19.6 | 26.9 | 11.1 | 42.4(0) e | [ | |
FeMn-HZSM-5 (particle mixing) | 1 | 320 | 1.0 | 3600 | 49.4 | 39.8 | 19.9 | 0.3 | 41.5 | 9.6(28.7) e | [ | |
FeMn&HZSM-5 (layered, h = 3 cm) | 1 | 320 | 1.0 | 3600 | 59.4 | 41.7 | 19.2 | 0.2 | 42.2 | 8.2(30.2) e | [ | |
FeMn-HZSM-5@Si-1 | 1 | 320 | 1.0 | 3600 | 60.0 | 42.7 | 22.5 | 1.0 | 31.5 | 11.4(33.6) e | [ | |
Fe/Ni-HZMS-5 | 2 | 330 | 4.0 | 1813 | 99.2 | 3.2 | 9.2 | 9.2 | 9.2 | 39.6(48.0) e | [ |
Table 3 Summary of catalytic performance over novel iron-based catalysts for FTS.
Catalyst | H2/CO | T (°C) | P (MPa) | GHSV (mL h-1 g-1) | CO conv. (%) | CO2 sel. (%) | Product distribution (%) | Ref. | ||||
---|---|---|---|---|---|---|---|---|---|---|---|---|
CH4 | C2‒C4= | C2‒C40 | C5+ | |||||||||
FeZr(0.3) | 2 | 300 | 2.0 | 8000 | 82.1 | 41.2 | 4.6 | 5.3 | 4.5 | 85.6 | [ | |
Fe/PANI | 1 | 350 | 2.0 | 9000 | 79 | 44 | 24 | 47 | 14 | 15 | [ | |
IO-CAT | 1 | 275 | 1.5 | 2800 a | 75.4 | 42.6 | 9.05 | 20.0 | 20.0 | 71 | [ | |
Fe@C-400 | 1 | 340 | 2.0 | 30000 | 74 | 47 | 28.3 | 30.2 b | 26.4 b | — | [ | |
Fe@C-500 | 1 | 340 | 2.0 | 30000 | 76 | 46 | 27.8 | 25.9 b | 27.8 b | — | [ | |
Fe@C-600 | 1 | 340 | 2.0 | 30000 | 74 | 46 | 25.9 | 24.1 b | 31.5 b | — | [ | |
Fe@C-900 | 1 | 340 | 2.0 | 30000 | 53 | 45 | 23.6 | 30.9 b | 23.6 b | — | [ | |
38Fe@C | 1 | 340 | 1.5 | 3300 c | 70 | 43 | — | 24.6 | 22.8 | — | [ | |
33Fe@C/Al | 1 | 340 | 1.5 | 3300 c | 68 | 43 | — | 28.1 | 22.8 | — | [ | |
Fe-MIL-88B-NH2/C d | 1 | 300 | 2.0 | 36000 | 81.8 | 42.9 | 15.1 | 21.4 | 12.8 | 50.7 | [ | |
Fe-MIL-88B-NH2/C d | 1 | 300 | 2.0 | 180000 | 27.8 | 25.5 | 18.7 | 17.5 | 9.4 | 54.4 | [ | |
R-Fe@HZSM-5 | 2 | 270 | 2.0 | 2240 | 93 | 12 | 7.5 | 21.5 | 21.5 | 71 | [ | |
Fe3O4@H-ZSM-5 | 1 | 270 | 2.0 | 960 | 87 | — | 16 | 36.2 | 36.2 | 47.8 | [ | |
FeCuK/ZSM-5 | 2 | 300 | 1.0 | 2000 | 81.1 | 35.6 | 19.6 | 30.3 | 12.3 | 37.8 | [ | |
FeCuK/Mordenite | 2 | 300 | 1.0 | 2000 | 72.9 | 37.7 | 32.2 | 18.8 | 25.4 | 23.6 | [ | |
FeCuK/Beta-zeolite | 2 | 300 | 1.0 | 2000 | 63.9 | 25.2 | 31.5 | 29.2 | 21.6 | 17.7 | [ | |
FeZnNa | 8:3 | 340 | 2.0 | 10000 | 74.9 | 27.3 | 10.9 | 25.5 | 4.4 | 58.1(1.1) e | [ | |
FeZnNa@HZSM-5 | 8:3 | 340 | 2.0 | 10000 | 88.3 | 27.7 | 11.3 | 1.4 | 38.6 | 28.9(19.8) e | [ | |
FeZnNa@0.1-HZSM-5 | 8:3 | 340 | 2.0 | 10000 | 84.2 | 26.5 | 9.9 | 0.7 | 35.6 | 22.7(30.9) e | [ | |
FeZnNa@0.6-HZSM-5 | 8:3 | 340 | 2.0 | 10000 | 89.2 | 26.9 | 9.8 | 1.0 | 26.8 | 21.8(40.5) e | [ | |
FeZnNa@0.6-HZSM-5-a | 8:3 | 340 | 2.0 | 10000 | 88.8 | 27.5 | 9.6 | 1.0 | 25.6 | 13.2(50.6) e | [ | |
FeMn | 1 | 320 | 1.0 | 3600 | 58.7 | 42.4 | 19.6 | 26.9 | 11.1 | 42.4(0) e | [ | |
FeMn-HZSM-5 (particle mixing) | 1 | 320 | 1.0 | 3600 | 49.4 | 39.8 | 19.9 | 0.3 | 41.5 | 9.6(28.7) e | [ | |
FeMn&HZSM-5 (layered, h = 3 cm) | 1 | 320 | 1.0 | 3600 | 59.4 | 41.7 | 19.2 | 0.2 | 42.2 | 8.2(30.2) e | [ | |
FeMn-HZSM-5@Si-1 | 1 | 320 | 1.0 | 3600 | 60.0 | 42.7 | 22.5 | 1.0 | 31.5 | 11.4(33.6) e | [ | |
Fe/Ni-HZMS-5 | 2 | 330 | 4.0 | 1813 | 99.2 | 3.2 | 9.2 | 9.2 | 9.2 | 39.6(48.0) e | [ |
Fig. 12. TEM images of fresh Fe2O3-ZrO2(0.3) (a) and used Fe2O3-ZrO2(0.3) (b); (c) XPS spectra of C 1s of the used FeZr catalysts; (d) 57Fe Mo?ssbauer spectra of Fe2O3-ZrO2(0.3). Reproduced from Ref. [268] with permission from the American Chemical Society.
Fig. 13. Schematic diagrams showing the preparation of Fe-MIL-88B-NH2/C nanocomposites from isostructural iron-MOF precursors (a) and the generation of the Fe3O4@χ-Fe5C2 core-shell catalysts and surface chemistry during FTS (b). Reproduced from Ref. [275] with permission from the American Chemical Society.
Fig. 14. Images of Fe3O4@ZSM-5 (Si/Fe = 11) microspheres. (a) SEM; (b) FESEM of a single microsphere; (c) SEM of a crushed microsphere; (d) TEM of a microsphere edge. Inset in (d) is an HRTEM image of the Fe3O4 nanoparticles around a ZSM-5 NR (scale bar = 5 nm); (e) The formation mechanism of functional Fe3O4@ZSM-5 microspheres through in situ crystallization from surface to core. Reproduced from Ref. [278] with permission from the American Chemical Society.
Catalyst | H2/CO2 | T (°C) | P (MPa) | GHSV (mL h-1 g-1) | CO2 conv. (%) | Product sel. (%) | O/P | Ref. | |||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
CO | CH4 | C2‒C4= | C2‒C40 | C5+ | |||||||||||||||||
Fe2O3-CT600 | 3 | 350 | 1.5 | 1140 | 40 | 15 | 12 | 37 | 37 | 36 | 2.7 | [ | |||||||||
Fe/K(0.3) | 3 | 300 | 1.1 | 3600 | 27.0 | 21 | 15 | 64 | 64 | 64 | 1.1 | [ | |||||||||
Fe-Co(0.17)/K(0.3) | 3 | 300 | 1.1 | 3600 | 33.7 | 14 | 18 | 68 | 68 | 68 | 0.7 | [ | |||||||||
Fe-Co(0.17)/K(1.0) | 3 | 300 | 1.1 | 3600 | 31.0 | 18 | 13 | 69 | 69 | 69 | 5.2 | [ | |||||||||
10Fe0.8K a | 3 | 300 | 2.5 | 560 | 41.7 | 6.0 | 10.3 | 21.6 | 6.2 | 56.0 | 3.5 | [ | |||||||||
10Fe0.8K0.53Co a | 3 | 300 | 2.5 | 560 | 54.6 | 2.0 | 18.9 | 24.4 | 7.7 | 47.0 | 3.2 | [ | |||||||||
10Fe0.8K0.53Ru a | 3 | 300 | 2.5 | 560 | 47.1 | 3.1 | 16.4 | 19.7 | 7.4 | 53.4 | 2.8 | [ | |||||||||
N-600-0 | 3 | 400 | 3.0 | 3600 | 46.0 | 17.5 | 26.6 | 19.2 | 14.5 | 22.2 | 1.3 | [ | |||||||||
N-K-600-0 | 3 | 400 | 3.0 | 3600 | 43.1 | 26.1 | 26.2 | 27.3 | 5.0 | 15.4 | 5.5 | [ | |||||||||
FeZn-NC | 3 | 320 | 3.0 | 7200 | 29.3 | 19.9 | 16.6 | 30.0 | 6.1 | 27.4 | 4.92 | [ | |||||||||
FeZnK-NC | 3 | 320 | 3.0 | 7200 | 34.6 | 21.2 | 19.1 | 32.0 | 5.6 | 22.1 | 5.71 | [ |
Table 4 Summary of catalytic performance over novel iron-based catalysts for CO2 hydrogenation.
Catalyst | H2/CO2 | T (°C) | P (MPa) | GHSV (mL h-1 g-1) | CO2 conv. (%) | Product sel. (%) | O/P | Ref. | |||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
CO | CH4 | C2‒C4= | C2‒C40 | C5+ | |||||||||||||||||
Fe2O3-CT600 | 3 | 350 | 1.5 | 1140 | 40 | 15 | 12 | 37 | 37 | 36 | 2.7 | [ | |||||||||
Fe/K(0.3) | 3 | 300 | 1.1 | 3600 | 27.0 | 21 | 15 | 64 | 64 | 64 | 1.1 | [ | |||||||||
Fe-Co(0.17)/K(0.3) | 3 | 300 | 1.1 | 3600 | 33.7 | 14 | 18 | 68 | 68 | 68 | 0.7 | [ | |||||||||
Fe-Co(0.17)/K(1.0) | 3 | 300 | 1.1 | 3600 | 31.0 | 18 | 13 | 69 | 69 | 69 | 5.2 | [ | |||||||||
10Fe0.8K a | 3 | 300 | 2.5 | 560 | 41.7 | 6.0 | 10.3 | 21.6 | 6.2 | 56.0 | 3.5 | [ | |||||||||
10Fe0.8K0.53Co a | 3 | 300 | 2.5 | 560 | 54.6 | 2.0 | 18.9 | 24.4 | 7.7 | 47.0 | 3.2 | [ | |||||||||
10Fe0.8K0.53Ru a | 3 | 300 | 2.5 | 560 | 47.1 | 3.1 | 16.4 | 19.7 | 7.4 | 53.4 | 2.8 | [ | |||||||||
N-600-0 | 3 | 400 | 3.0 | 3600 | 46.0 | 17.5 | 26.6 | 19.2 | 14.5 | 22.2 | 1.3 | [ | |||||||||
N-K-600-0 | 3 | 400 | 3.0 | 3600 | 43.1 | 26.1 | 26.2 | 27.3 | 5.0 | 15.4 | 5.5 | [ | |||||||||
FeZn-NC | 3 | 320 | 3.0 | 7200 | 29.3 | 19.9 | 16.6 | 30.0 | 6.1 | 27.4 | 4.92 | [ | |||||||||
FeZnK-NC | 3 | 320 | 3.0 | 7200 | 34.6 | 21.2 | 19.1 | 32.0 | 5.6 | 22.1 | 5.71 | [ |
Fig. 15. Proposed reaction mechanisms over FeAlOx-5 catalyst containing the three active phases of Fe3O4, Fe5C2, and AlOx. Reproduced from Ref. [284] with permission from the American Chemical Society.
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