Optimisation of Propane Production from Hydrothermal Decarboxylation of Butyric Acid Using Pt/C Catalyst: Influence of Gaseous Reaction Atmospheres
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials
2.2. Method
2.2.1. Batch Reactor Procedure
2.2.2. Product Collection
2.2.3. Analysis of Gaseous Phase
2.2.4. Analysis of Aqueous Phase
- S = volume of HCl used in titration (mL)
- B = volume of HCl used in blank titration (mL)
- C = concentration of HCl (mol/L)
- V = volume of aqueous phase collected (mL)
- m = mass of butyric acid feed
- 88.11 is the mol. wt% of butyric acid (g/mol)
2.2.5. Analysis of Pt/C Catalyst and Solid Residue
2.2.6. Statistical Analysis
3. Results and Discussions
3.1. Product Yields
3.1.1. Effect of Nitrogen Atmosphere at Different Temperatures
3.1.2. Effect of Hydrogen Atmosphere at Different Temperatures
3.1.3. Effect of Hydrogen Pressure at 300 °C
3.1.4. Effect of Compressed Air with Varying Temperature
3.2. Statistical Analysis Results
3.2.1. Optimisation of Reaction Conditions
3.2.2. Fitting the Surface Response Models
3.3. Catalyst and Solid Residue Characterisation by XRD
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Wt % | Temperature (°C) | |||
---|---|---|---|---|
200 | 250 | 300 | 350 | |
Conversion | 24 | 98 | 97 | 96 |
Hydrogen | - | 0.3 | 0.7 | 1.3 |
Methane | - | 0.2 | 1.0 | 4.7 |
Ethane | 0.5 | 1.7 | 3.6 | 5.3 |
Propane | 9.8 | 53.2 | 53.5 | 41.6 |
Butane | - | 0.1 | 0.1 | 0.1 |
CO2 | 14.5 | 41.5 | 43.1 | 46.1 |
* Propane selectivity | 94 | 96 | 92 | 80 |
Wt % | Temperature (°C) | |||
---|---|---|---|---|
200 | 250 | 300 | 350 | |
Conversion | 37 | 77 | 100 | 99 |
Hydrogen | 3.3 | 3.7 | 4.3 | 5.7 |
Methane | 0.0 | 0.1 | 0.5 | 12.8 |
Ethane | 0.4 | 0.7 | 1.9 | 5.0 |
Propane | 7.8 | 36.0 | 44.4 | 32.3 |
Butane | 0.1 | 0.4 | 0.1 | 0.1 |
CO2 | 25.4 | 36.2 | 48.7 | 42.8 |
* Propane selectivity | 94 | 97 | 94 | 64 |
Wt % | Pressure (bar) | ||
---|---|---|---|
2.5 | 5.0 | 10.0 | |
Conversion | 96 | 100 | 100 |
Hydrogen | 3.1 | 4.3 | 7.3 |
Methane | 2.5 | 0.5 | 0.4 |
Ethane | 3.5 | 1.9 | 2.1 |
Propane | 45.8 | 44.4 | 48.5 |
Formaldehyde | - | - | 12 |
Butane | 0.1 | 0.1 | 0.1 |
CO2 | 40.6 | 48.7 | 29.3 |
* Propane Selectivity | 88.3 | 94.7 | 95 |
Wt % | Temperature (°C) | |||
---|---|---|---|---|
200 | 250 | 300 | 350 | |
Conversion | 33 | 98 | 97 | 98 |
Hydrogen | 0.0 | 0.0 | 0.4 | 1.5 |
Methane | 0.2 | 0.4 | 4.6 | 7.4 |
Ethane | 0.4 | 2.9 | 4.7 | 3.2 |
Propane | 1.5 | 50.6 | 38.9 | 32.0 |
Butane | 0.0 | 0.1 | 0.1 | 0.1 |
CO2 | 31.0 | 44.8 | 50.3 | 53.6 |
* Propane selectivity | 60 | 94 | 79 | 74 |
Parameters | Model Equations Based on Coded Factors under Nitrogen Atmosphere | Minimum (X = −1) | Central Point (X = 0) | Maximum (X = +1) | Optimum Temperature (°C) |
---|---|---|---|---|---|
Conversion (%) | 23.6 (24.0) | 98.2 (97.0) | 95.5 (96.0) | 300 (290) | |
Propane Yield (%) | 9.81 (10.2) | 50.8 (53.5) | 40.6 (41.6) | ||
CO2 Yield (%) | 16.7 (14.5) | 42.8 (43.1) | 41.6 (46.1) | ||
Parameters | Model Equations Based on Coded Factors under Hydrogen Atmosphere | Minimum (X = −1) | Central Point (X = 0) | Maximum (X = +1) | Optimum Temperature (°C) |
Conversion (%) | 37.2 (37.1) | 87.6 (100) | 99.2 (99.0) | 320 (300) | |
Propane Yield (%) | 7.61 (7.80) | 38.8 (36.0) | 32.1 (32.0) | ||
CO2 Yield (%) | 25.1 (25.4) | 44.4 (48.7) | 42.6 (42.8) | ||
Parameters | Model Equations Based on Based Coded Factors under Compressed Air Atmosphere | Minimum (X = −1) | Central Point (X = 0) | Maximum (X = +1) | Optimum Temperature (°C) |
Conversion (%) | 31.8 (33.0) | 98.0 (97.0) | 98.7 (98.0) | 270 (250) | |
Propane Yield (%) | 0.32 (1.50) | 46.0 (50.6) | 30.4 (32.0) | ||
CO2 Yield (%) | 29.9 (31.0) | 46.4 (44.8) | 54.0 (53.6) |
Models | Statistics | Response | ||
---|---|---|---|---|
Conversion | Propane | CO2 | ||
Linear | R2 | 0.68 | 0.28 | 0.81 |
R2-adj. | 0.65 | 0.22 | 0.79 | |
R2-pred. | 0.56 | 0.1 | 0.74 | |
Sdv. | 15.8 | 14 | 4.01 | |
Linear Square | R2 | 0.93 | 0.9 | 0.95 |
R2-adj. | 0.94 | 0.88 | 0.94 | |
R2-pred. | 0.92 | 0.85 | 0.93 | |
Sdv. | 6.4 | 5.4 | 2.06 | |
Full quadratic | R2 | 0.97 | 0.98 | 0.98 |
R2-adj. | 0.96 | 0.97 | 0.97 | |
R2-pred. | 0.93 | 0.94 | 0.94 | |
Sdv. | 5.1 | 2.6 | 1.5 | |
Cubic | R2 | 0.95 | 0.96 | 0.95 |
R2-adj. | 0.93 | 0.95 | 0.94 | |
R2-pred. | 0.9 | 0.93 | 0.91 | |
Sdv. | 6.7 | 3.2 | 2.2 |
Response | Factors | DF | Mean of Square | F-Value | p-Value |
---|---|---|---|---|---|
Conversion | Model | 4 | 2124.9 | 81.63 | 0.0001 |
A | 1 | 434.6 | 16.7 | 0.0035 | |
A2 | 1 | 563.5 | 21.65 | 0.0016 | |
A3 | 1 | 4.7 | 0.18 | 0.68 | |
A4 | 1 | 203 | 7.80 | 0.02 | |
Residual | 8 | 26.03 | - | - | |
Lack of fit | 3 | 69.4 | 13013.3 | 0.0001 | |
Pure error | 5 | 0.005 | - | - | |
Total | 12 | - | - | - | |
Propane | Model | 4 | 749.75 | 105 | 0.0001 |
A | 1 | 15.16 | 2.14 | 0.18 | |
A2 | 1 | 218.1 | 30.85 | 0.0001 | |
A3 | 1 | 200.9 | 28.4 | 0.0007 | |
A4 | 1 | 36.9 | 5.2 | 0.05 | |
Residual | 8 | 7.57 | - | - | |
Lack of fit | 3 | 8.4 | 1.3 | 0.36 | |
Pure error | 5 | 6.29 | - | - | |
Total | 12 | - | - | - | |
CO2 | Model | 4 | 235.9 | 105.04 | 0.0001 |
A | 1 | 71.1 | 31.7 | 0.0005 | |
A2 | 1 | 51.3 | 22.9 | 0.0014 | |
A3 | 1 | 0.12 | 0.05 | 0.8 | |
A4 | 1 | 24.67 | 10.72 | 0.01 | |
Residual | 8 | 2.2 | - | - | |
Lack of fit | 3 | 5.9 | 117.3 | 0.0001 | |
Pure error | 5 | 0.05 | - | - | |
Total | 12 | - | - | - |
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Onwudili, J.A.; Razaq, I.; Simons, K.E. Optimisation of Propane Production from Hydrothermal Decarboxylation of Butyric Acid Using Pt/C Catalyst: Influence of Gaseous Reaction Atmospheres. Energies 2022, 15, 268. https://doi.org/10.3390/en15010268
Onwudili JA, Razaq I, Simons KE. Optimisation of Propane Production from Hydrothermal Decarboxylation of Butyric Acid Using Pt/C Catalyst: Influence of Gaseous Reaction Atmospheres. Energies. 2022; 15(1):268. https://doi.org/10.3390/en15010268
Chicago/Turabian StyleOnwudili, Jude A., Iram Razaq, and Keith E. Simons. 2022. "Optimisation of Propane Production from Hydrothermal Decarboxylation of Butyric Acid Using Pt/C Catalyst: Influence of Gaseous Reaction Atmospheres" Energies 15, no. 1: 268. https://doi.org/10.3390/en15010268