Influence of NiO/La2O3 Catalyst Preparation Method on Its Reactivity in the Oxy-Steam Reforming of LNG Process
Abstract
:1. Introduction
2. Results and Discussion
2.1. Catalytic Activity Tests
2.2. Reduction Behavior of the Investigated Catalysts
2.3. Specific Surface Area Measurements of Investigated Catalysts
2.4. Acidity Measurements of Investigated Catalysts
2.5. Phase Composition Studies of Investigated Catalysts
2.6. SEM-EDS Measurements of Investigated Catalysts
3. Materials and Methods
3.1. Supports and Catalysts Preparation
3.2. Characterization of the Catalytic Materials
3.3. Catalytic Activity Measurements in Oxy-Steam Reforming of the Liqufied Natural Gas Reaction (OSR-LNG)
- —the moles of hydrocarbon at the reactor inlet;
- —the moles of hydrocarbon at the reactor outlet;
- —the moles of the CO at the reactor outlet;
- —the moles of the CO2 at the reactor outlet;
- —the moles of the H2 at the reactor outlet;
- —the sum of the moles of the hydrocarbons the reactor inlet;
- —the sum of the moles of the hydrocarbons at the reactor outlet.
4. Conclusions
Author Contributions
Funding
Conflicts of Interest
References
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Catalysts | Temp [°C] | Methane Conversion [%] | Ethane Conversion [%] | Propane Conversion [%] | Butane Conversion [%] |
---|---|---|---|---|---|
NiO/La2O3 calc. 700 °C CP | 400 | 31 | 34 | 37 | 44 |
500 | 37 | 60 | 78 | 91 | |
600 | 43 | 68 | 85 | 95 | |
700 | 45 | 70 | 88 | 100 | |
900 | 60 | 93 | 100 | 100 | |
NiO/La2O3 calc. 900 °C CP | 400 | 34 | 36 | 38 | 36 |
500 | 31 | 38 | 44 | 48 | |
600 | 38 | 64 | 79 | 91 | |
700 | 46 | 69 | 86 | 93 | |
900 | 57 | 86 | 99 | 100 | |
NiO/La2O3 calc. 700 °C IMP | 400 | 33 | 34 | 40 | 44 |
500 | 35 | 43 | 55 | 68 | |
600 | 38 | 57 | 73 | 87 | |
700 | 64 | 87 | 96 | 100 | |
900 | 100 | 100 | 100 | 100 | |
NiO/La2O3 calc. 900 °C IMP | 400 | 33 | 36 | 39 | 46 |
500 | 35 | 44 | 54 | 68 | |
600 | 38 | 60 | 77 | 83 | |
700 | 39 | 62 | 81 | 100 | |
900 | 100 | 100 | 100 | 100 |
Catalysts | Temp [°C] | CO Selectivity [%] | CO2 Selectivity [%] | H2 Yield [%] |
---|---|---|---|---|
NiO/La2O3 calc. 700 °C CP | 400 | 0 | 100 | 0 |
500 | 0 | 100 | 4 | |
600 | 0 | 100 | 4 | |
700 | 0 | 100 | 11 | |
900 | 71 | 29 | 46 | |
NiO/La2O3 calc. 900 °C CP | 400 | 0 | 100 | 0 |
500 | 0 | 100 | 0 | |
600 | 0 | 100 | 3 | |
700 | 0 | 100 | 2 | |
900 | 74 | 26 | 39 | |
NiO/La2O3 calc. 700 °C IMP | 400 | 0 | 100 | 0 |
500 | 0 | 100 | 0 | |
600 | 0 | 100 | 0 | |
700 | 65 | 35 | 29 | |
900 | 90 | 10 | 56 | |
NiO/La2O3 calc. 900 °C IMP | 400 | 0 | 100 | 0 |
500 | 0 | 100 | 0 | |
600 | 0 | 100 | 1 | |
700 | 0 | 100 | 20 | |
900 | 98 | 2 | 54 |
Catalysts | Peak Contribution to the Overall TPR Peak Area (%) | |||||
---|---|---|---|---|---|---|
I-Peak (Tmax) | II-Peak (Tmax) | III-Peak (Tmax) | IV-Peak (Tmax) | V-Peak (Tmax) | VI-Peak (Tmax) | |
NiO/La2O3 calc. 700 °C CP | 0.16 (325 °C) | 0.02 (360 °C) | 0.11 (487 °C) | 0.47 (585 °C) | 0.18 (656 °C) | 0.06 (807 °C) |
NiO/La2O3 calc. 900 °C CP | - | 0.14 (371 °C) | 0.43 (506 °C) | 0.43 (614 °C) | - | - |
NiO/La2O3 calc. 700 °C IMP | 0.14 (311 °C) | 0.14 (369 °C) | 0.49 (548 °C) | 0.09 (626 °C) | 0.10 (807 °C) | 0.04 (862 °C) |
NiO/La2O3 calc. 900 °C IMP | 0.04 (355 °C) | 0.14 (377 °C) | 0.44 (512 °C) | 0.36 (582 °C) | 0.02 (713 °C) | - |
Materials | BET Surface Area [m2/g] | Monolayer Capacity [cm3/g] | Average Pore Radius [nm] |
---|---|---|---|
La2O3 calc. 700 °C | 0.44 | 0.002 | 19.93 |
NiO/La2O3 calc. 700 °C CP | 24.41 | 0.144 | 11.94 |
NiO/La2O3 calc. 900 °C CP | 7.89 | 0.034 | 8.43 |
NiO/La2O3 calc. 700 °C IMP | 4.99 | 0.035 | 16.31 |
NiO/La2O3 calc. 900 °C IMP | 3.05 | 0.016 | 13.08 |
Materials | Total Acidity [mmol/g] | Weak Centers [mmol/g] | Medium Centers [mmol/g] | Strong Centers [mmol/g] |
---|---|---|---|---|
180–600 °C | 180–300 °C | 300–450 °C | 450–600 °C | |
La2O3 calc. 700 °C | 0.15 | 0.02 | 0.11 | 0.02 |
NiO/La2O3 calc. 700 °C CP | 3.20 | 0.33 | 1.23 | 1.64 |
NiO/La2O3 calc. 900 °C CP | 3.73 | 0.02 | 1.24 | 2.47 |
NiO/La2O3 calc. 700 °C IMP | 3.14 | 0.47 | 1.06 | 1.61 |
NiO/La2O3 calc. 900 °C IMP | 2.12 | 0.16 | 1.28 | 0.68 |
Materials | Percentage Contribution of the Phases [wt.%] | ||
---|---|---|---|
After calcination | NiO/La2O3 calc. 700 °C CP | La(OH)3 | 93 |
NiLa2O4 | 7 | ||
NiO/La2O3 calc. 900 °C CP | La(OH)3 | 88 | |
NiLa2O4 | 12 | ||
NiO/La2O3 calc. 700 °C IMP | La(OH)3 | 69 | |
LaNiO3 | 31 | ||
NiO/La2O3 calc. 900 °C IMP | La(OH)3 | 45 | |
NiLa2O4 | 55 | ||
After OSR-LNG reaction | NiO/La2O3 calc. 700 °C CP | La(OH)3 | 60 |
La2O3 | 40 | ||
NiO/La2O3 calc. 900 °C CP | La(OH)3 | 45 | |
La2O3 | 55 | ||
NiO/La2O3 calc. 700 °C IMP | La(OH)3 | 34 | |
La2O3 | 59 | ||
Ni | 7 | ||
NiO/La2O3 calc. 900 °C IMP | La(OH)3 | 55 | |
La2O3 | 39 | ||
Ni | 6 |
Catalysts | The Size of Crystallites [nm] | ||
---|---|---|---|
Ni | La2O3 | La(OH)3 | |
NiO/La2O3 calc. 700 °C IMP after OSR-LNG reaction | 22 | 48 | 27 |
NiO/La2O3 calc. 900 °C IMP after OSR-LNG reaction | 27 | 58 | 26 |
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Mosinska, M.; Maniukiewicz, W.; Szynkowska-Jozwik, M.I.; Mierczynski, P. Influence of NiO/La2O3 Catalyst Preparation Method on Its Reactivity in the Oxy-Steam Reforming of LNG Process. Catalysts 2021, 11, 1174. https://doi.org/10.3390/catal11101174
Mosinska M, Maniukiewicz W, Szynkowska-Jozwik MI, Mierczynski P. Influence of NiO/La2O3 Catalyst Preparation Method on Its Reactivity in the Oxy-Steam Reforming of LNG Process. Catalysts. 2021; 11(10):1174. https://doi.org/10.3390/catal11101174
Chicago/Turabian StyleMosinska, Magdalena, Waldemar Maniukiewicz, Malgorzata I. Szynkowska-Jozwik, and Pawel Mierczynski. 2021. "Influence of NiO/La2O3 Catalyst Preparation Method on Its Reactivity in the Oxy-Steam Reforming of LNG Process" Catalysts 11, no. 10: 1174. https://doi.org/10.3390/catal11101174