Multi-Scale Analysis of Integrated C1 (CH4 and CO2) Utilization Catalytic Processes: Impacts of Catalysts Characteristics up to Industrial-Scale Process Flowsheeting, Part I: Experimental Analysis of Catalytic Low-Pressure CO2 to Methanol Conversion
Abstract
:1. Introduction
2. State-of-the-Art and Literature Review
3. Results and Discussion
3.1. Catalyst Characterizations
3.2. Catalytic Performance
3.3. Equilibrium-Limited Achievable Performance
3.4. Stability Test and Analysis
4. Material and Methods
4.1. Selected Catalysts and Synthesis Methods
4.1.1. Co-Precipitation Method for Preparation of Cu/ZnO/Al2O3 Catalyst
4.1.2. Hydrolysis Method for Preparation of Cu/ZnO/Al2O3 Catalyst
4.1.3. Coprecipitation Method for Preparation of Cu/ZnO/Al2O3 Catalyst
4.1.4. Gel-Coprecipitation Method for Preparation of Cu/ZnO/Al2O3 Catalyst
4.1.5. Conventional Carbonate Coprecipitation Method for Preparation of Cu/ZnO/Al2O3 Catalyst
4.1.6. Citrate and Impregnation Method for Preparation of Cu/ZnO Catalyst
4.2. Catalyst Characterization
5. Experimentation for Catalyst Testing
Experimental Setup
6. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
Abbreviations
BET | Measuring the specific surface based on Brunauer–Emmett–Teller theory |
BJH | Barrett–Joyner–Halenda |
Cat | Catalyst |
CCSU | Carbon capture separation utilization |
Dilu. | Dilution |
DME | Dimethyl ether (Methoxymethane) |
EDX | Energy-dispersive X-ray spectroscopy |
FESEM | Field emission scanning electron microscopy |
Gas | Gas phase |
GC | Gas chromatography |
In | Inlet stream |
MeOH (CH3OH) | Methanol |
MET | Methanol catalysts prepared with different methods |
Out | Outlet stream |
PC-ILS | Process control system—integrated lab solution |
RWGS | Reverse water gas shift |
UniCat | “Unifying Concepts in Catalysis” (a research group in Berlin) |
XRD | X-ray diffraction |
Nomenclature
A | Ambient | - |
Cb | catalytic bed | - |
D | Diameter or equivalent diameter | nm |
F | Molar flow rate | mol/min |
GHSV | Gas hourly space velocity | L/h |
P | Pressure | bar |
Q | Total flow rate | Nml/min |
S (Selectivity) | Portion of the whole consumed carbon dioxide which appears in the (desired) products | - |
T | Temperature | °C |
V | Volume | ml |
X (CO2 Conversion) | Portion of the inlet carbon dioxide converted to the desired and undesired products | - |
X | Mole fraction | - |
Y (Yield) | Amount of the converted carbon dioxide appears in each product per whole total amount of the inlet carbon dioxide | - |
ΔHR | Reaction enthalpy | kJ/mol |
Ρ | Density | kg/m³ |
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Catalyst | SBET (m2 g−1) | Mean Pore Size (nm) |
---|---|---|
MET1 | 79 | 7 |
MET2 | 45 | 6 |
MET3 | 19 | 5.5 |
MET4 | 22 | 5.5 |
MET5 | 52 | 5 |
MET6 | 11 | 6.5 |
MET7 | 28 | 6 |
H2/CO2 | 3 | 6 | 9 | 3 | 6 | 9 | 3 | 6 | 9 |
---|---|---|---|---|---|---|---|---|---|
T(°C) | Coprecipitation method Cu/ZnO/Al2O3 (MET1) | ||||||||
200 | 7.9 | 14.5 | 18.6 | 66.1 | 77.6 | 77.6 | 5.2 | 11.3 | 14.4 |
230 | 16.9 | 25.4 | 31 | 33.7 | 38.8 | 43.7 | 5.7 | 9.9 | 13.5 |
260 | 17.1 | 24.7 | 29.3 | 0 | 0.2 | 0 | 0.0 | 0.0 | 0.0 |
T(°C) | Hydrolysis method-Cu/ZnO/Al2O3 (MET2) | ||||||||
200 | 9.6 | 14.7 | 18.4 | 74.3 | 79.4 | 82.5 | 7.1 | 11.7 | 15.2 |
230 | 15.7 | 21.4 | 25.9 | 43.2 | 52.7 | 52.8 | 6.8 | 11.3 | 13.7 |
260 | 19 | 23.8 | - | 13.4 | 17.4 | - | 2.5 | 4.1 | - |
T(°C) | Coprecipitation method-Cu/ZnO/Al2O3 (MET3) | ||||||||
200 | 8 | 11.9 | 16.8 | 80.3 | 76.8 | 79.2 | 6.4 | 9.1 | 13.3 |
230 | 15.2 | 22.8 | 29.6 | 39 | 46.5 | 44.7 | 5.9 | 10.6 | 13.2 |
260 | 20.6 | 26.9 | 34.3 | 18.8 | 15.1 | 14.9 | 3.9 | 4.1 | 5.1 |
T(°C) | Gel coprecipitation method-Cu/ZnO/Al2O3 (MET4) | ||||||||
200 | 8.8 | 13.4 | 18.6 | 74 | 75.6 | 78.6 | 6.5 | 10.1 | 14.6 |
230 | 16.1 | 24.8 | 31.2 | 37.8 | 41.9 | 45.1 | 6.1 | 10.4 | 14.1 |
260 | 19.8 | 27.5 | 34.2 | 10.6 | 12.5 | 16.1 | 2.1 | 3.4 | 5.5 |
T(°C) | Carbonate coprecipitation method-Cu/ZnO/Al2O3 (MET5) | ||||||||
200 | 11 | 18 | 24.7 | 66.2 | 73.8 | 73.3 | 7.3 | 13.3 | 18.1 |
230 | 17.2 | 24.8 | 33.6 | 33.6 | 42.2 | 38.9 | 5.8 | 10.5 | 13.1 |
260 | 20.8 | 30.2 | 37.5 | 11.6 | 13.3 | 16.8 | 2.4 | 4.0 | 6.3 |
T(°C) | Citric and impregnation method-Cu/ZnO (MET6) | ||||||||
200 | 3.3 | 4.9 | 4.4 | 97.4 | 98 | 100 | 3.2 | 4.8 | 4.4 |
230 | 4.4 | 7.1 | 15.3 | 78.8 | 80 | 63.2 | 3.5 | 5.7 | 9.7 |
260 | 14.5 | 20.6 | 22.6 | 21.8 | 26.4 | 14.6 | 3.2 | 5.4 | 3.3 |
T(°C) | Impregnation method-Cu/YAG (MET7) | ||||||||
200 | 1.4 | 2.7 | 3.7 | 96.9 | 98.3 | 87.2 | 1.4 | 2.7 | 3.2 |
230 | 3.7 | 6.3 | 8.7 | 64.9 | 68.2 | 69.7 | 2.4 | 4.3 | 6.1 |
260 | 8.8 | 14.2 | 18.3 | 33.6 | 37.4 | 40.3 | 3.0 | 5.3 | 7.4 |
Cat | T(°C) | S MeOH | Y MeOH | |||||||
---|---|---|---|---|---|---|---|---|---|---|
H2/CO2 | 3 | 6 | 9 | 3 | 6 | 9 | 3 | 6 | 9 | |
MET1 | 200 | 11 | 17.1 | 21.1 | 51.2 | 65.4 | 69.2 | 5.6 | 11.2 | 14.5 |
230 | 18.5 | 25.5 | 31.9 | 32.3 | 38.7 | 39.1 | 6 | 9.8 | 12.5 | |
MET2 | 200 | 15.4 | 25 | 31.1 | 60.3 | 66.1 | 67.9 | 9.3 | 16.5 | 21.1 |
230 | 17.5 | 25.8 | 32.7 | 33.7 | 41 | 47.3 | 5.9 | 10.6 | 15.5 | |
MET3 | 200 | 14.6 | 21.5 | 28.2 | 54.5 | 63.4 | 65.6 | 7.9 | 13.6 | 18.5 |
230 | 18.2 | 26 | 31.5 | 33.4 | 39.2 | 45.1 | 6.1 | 10.2 | 14.2 | |
MET4 | 200 | 14.7 | 22.5 | 29.1 | 53.4 | 60.7 | 63.4 | 7.8 | 13.6 | 18.4 |
230 | 16.5 | 24.6 | 30.8 | 26.9 | 32.7 | 39.7 | 4.4 | 8 | 12.2 | |
MET5 | 200 | 5.6 | 8.7 | 11.5 | 75.9 | 79.7 | 80.5 | 4.2 | 6.9 | 9.3 |
230 | 11 | 16.4 | 20.7 | 36.8 | 41 | 43 | 4 | 6.7 | 8.9 |
Used Basic Material | CAS-Number | Supplier |
---|---|---|
Copper II nitrate trihydrate | 10031-43-3 | Sigma-Aldrich (Darmstadt, Germany) |
Zinc nitrate hexahydrate | 10196-18-6 | Sigma-Aldrich(Taufkirchen, Germany) |
Citric acid anhydrous | 77-92-9 | Sigma-Aldrich (Taufkirchen, Germany) |
Oxalic acid | 144-62-7 | Sigma-Aldrich (Taufkirchen, Germany) |
Aluminium nitrate | 7784-27-2 | Sigma-Aldrich (Darmstadt, Germany) |
Sodium carbonate | 497-19-8 | Sigma-Aldrich (Taufkirchen, Germany) |
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Godini, H.R.; Khadivi, M.; Azadi, M.; Görke, O.; Jazayeri, S.M.; Thum, L.; Schomäcker, R.; Wozny, G.; Repke, J.-U. Multi-Scale Analysis of Integrated C1 (CH4 and CO2) Utilization Catalytic Processes: Impacts of Catalysts Characteristics up to Industrial-Scale Process Flowsheeting, Part I: Experimental Analysis of Catalytic Low-Pressure CO2 to Methanol Conversion. Catalysts 2020, 10, 505. https://doi.org/10.3390/catal10050505
Godini HR, Khadivi M, Azadi M, Görke O, Jazayeri SM, Thum L, Schomäcker R, Wozny G, Repke J-U. Multi-Scale Analysis of Integrated C1 (CH4 and CO2) Utilization Catalytic Processes: Impacts of Catalysts Characteristics up to Industrial-Scale Process Flowsheeting, Part I: Experimental Analysis of Catalytic Low-Pressure CO2 to Methanol Conversion. Catalysts. 2020; 10(5):505. https://doi.org/10.3390/catal10050505
Chicago/Turabian StyleGodini, Hamid Reza, Mohammadali Khadivi, Mohammadreza Azadi, Oliver Görke, Seyed Mahdi Jazayeri, Lukas Thum, Reinhard Schomäcker, Günter Wozny, and Jens-Uwe Repke. 2020. "Multi-Scale Analysis of Integrated C1 (CH4 and CO2) Utilization Catalytic Processes: Impacts of Catalysts Characteristics up to Industrial-Scale Process Flowsheeting, Part I: Experimental Analysis of Catalytic Low-Pressure CO2 to Methanol Conversion" Catalysts 10, no. 5: 505. https://doi.org/10.3390/catal10050505
APA StyleGodini, H. R., Khadivi, M., Azadi, M., Görke, O., Jazayeri, S. M., Thum, L., Schomäcker, R., Wozny, G., & Repke, J. -U. (2020). Multi-Scale Analysis of Integrated C1 (CH4 and CO2) Utilization Catalytic Processes: Impacts of Catalysts Characteristics up to Industrial-Scale Process Flowsheeting, Part I: Experimental Analysis of Catalytic Low-Pressure CO2 to Methanol Conversion. Catalysts, 10(5), 505. https://doi.org/10.3390/catal10050505