Pyrolysis Kinetics of Hydrochars Produced from Brewer’s Spent Grains
Abstract
:1. Introduction
2. Results and Discussion
2.1. Feedstocks Characteristics
2.2. Pyrolysis Char Characteristic
2.3. Analysis of TG–DTG Curves
2.4. Pyrolysis Kinetics
2.5. Heat Flow during Pyrolysis Reaction
3. Materials and Methods
3.1. Materials
3.2. Pyrolysis Procedure
3.3. Proximate and Ultimate Analysis
3.4. Mathematical Model for Pyrolysis Kinetics
3.5. Calculation of Pyrolysis Kinetics
4. Conclusions
Author Contributions
Funding
Conflicts of Interest
Appendix A
Material | Heating Rate °C min−1 | T1, T1,* °C | DTG1 DTG1,* % °C−1 | T2 °C | DTG2 % °C−1 | T3, T3* °C | DTG3 % °C−1 | Final Residue wt.% |
---|---|---|---|---|---|---|---|---|
BSG | 5 | 281.2 | −0.687 | 340.5 | −0.523 | 367.5 | −0.198 | 18.98 |
10 | 289.4 | −0.736 | 349.6 | −0.503 | 378.3 | −0.202 | 19.24 | |
20 | 298.6 | −0.776 | 357.9 | −0.515 | 388.3 | −0.211 | 20.99 | |
40 | 304.4 | −0.887 | 358.3 | −0.630 | 402.5 | −0.228 | 20.44 | |
average | 293.4 | −0.771 | 351.6 | −0.543 | 384.2 | −0.210 | 19.91 | |
HTC-180-4 | 5 | 211.2 | −0.285 | 339.8 | −0.592 | 404.2 | −0.169 | 24.97 |
10 | 223.9 | −0.267 | 349.4 | −0.556 | 412.1 | −0.165 | 29.78 | |
20 | 236.0 | −0.320 | 358.6 | −0.543 | 422.3 | −0.172 | 29.37 | |
40 | 251.6 | −0.317 | 362.2 | −0.633 | 419.9 | −0.183 | 29.08 | |
average | 230.7 | −0.297 | 352.5 | −0.581 | 414.6 | −0.172 | 28.30 | |
HTC-220-2 | 5 | 213.0 | −0.268 | 340.1 | −0.411 | 410.0 | −0.168 | 38.71 |
10 | 225.8 | −0.276 | 353.3 | −0.414 | 415.8 | −0.162 | 39.54 | |
20 | 243.3 | −0.325 | 359.5 | −0.370 | 427.0 | −0.167 | 41.32 | |
40 | 269.1 | −0.326 | 378.3 | −0.426 | 423.7 | −0.155 | 43.17 | |
average | 237.8 | −0.298 | 357.8 | −0.405 | 419.1 | −0.163 | 40.68 | |
HTC-220-4 | 5 | 209.2 | −0.171 | 342.8 | −0.298 | 410.3 | −0.193 | 44.62 |
10 | 221.3 | −0.175 | 353.9 | −0.302 | 427.4 | −0.194 | 45.60 | |
20 | 243.9 | −0.216 | 361.8 | −0.279 | 436.4 | −0.192 | 46.13 | |
40 | 269.4 | −0.236 | 378.9 | −0.340 | 441.1 | −0.176 | 46.66 | |
average | 236.0 | −0.199 | 359.4 | −0.305 | 428.8 | −0.189 | 45.75 |
α− | EA kJ mol−1 | R2− | A s−1 | TA K × 103 | EA kJ mol−1 | R2− | A s−1 | TA K × 103 |
---|---|---|---|---|---|---|---|---|
Material | BSG | HTC-180-4 | ||||||
0.05 | 186.50 | 0.81 | 1.17 × 1012 | 22.43 | 62.89 | 0.79 | 9.05 × 102 | 7.56 |
0.10 | 227.85 | 0.88 | 1.66 × 1018 | 27.41 | 79.24 | 0.87 | 2.72 × 104 | 9.53 |
0.15 | 240.19 | 0.93 | 1.34 × 1020 | 28.89 | 84.80 | 0.91 | 8.50 × 104 | 10.20 |
0.20 | 242.52 | 0.95 | 3.54 × 1020 | 29.17 | 82.86 | 0.89 | 5.68 × 104 | 9.97 |
0.25 | 243.15 | 0.97 | 4.64 × 1020 | 29.25 | 76.83 | 0.79 | 1.57 × 104 | 9.24 |
0.30 | 246.34 | 0.98 | 9.45 × 1020 | 29.63 | 88.18 | 0.74 | 1.37 × 105 | 10.61 |
0.35 | 252.30 | 0.98 | 3.44 × 1021 | 30.35 | 116.50 | 0.76 | 3.77 × 107 | 14.01 |
0.40 | 267.98 | 0.98 | 9.68 × 1022 | 32.23 | 154.98 | 0.81 | 7.6 × 1010 | 18.64 |
0.45 | 288.12 | 0.98 | 8.09 × 1024 | 34.65 | 190.25 | 0.87 | 9.41 × 1013 | 22.88 |
0.50 | 305.07 | 0.98 | 3.14 × 1026 | 36.69 | 208.11 | 0.90 | 3.57 × 1015 | 25.03 |
0.55 | 317.36 | 0.98 | 3.92 × 1027 | 38.17 | 213.69 | 0.93 | 1.12 × 1016 | 25.70 |
0.60 | 323.89 | 0.98 | 1.60 × 1028 | 38.96 | 210.42 | 0.93 | 6.01 × 1015 | 25.31 |
0.65 | 315.99 | 0.98 | 2.96 × 1027 | 38.01 | 198.37 | 0.91 | 5.78 × 1014 | 23.86 |
0.70 | 338.78 | 0.96 | 3.64 × 1029 | 40.75 | 167.24 | 0.77 | 1.15 × 1012 | 20.12 |
0.75 | 482.71 | 0.82 | 4.30 × 1043 | 58.06 | 170.34 | 0.72 | 1.38 × 1012 | 20.49 |
0.80 | 331.10 | 0.59 | 3.34 × 1069 | 39.82 | 191.85 | 0.74 | 5.42 × 1013 | 23.08 |
0.85 | 239.62 | 0.59 | 1.72 × 10166 | 28.82 | 204.37 | 0.77 | 2.15 × 1014 | 24.58 |
average | 285.26 | 0.90 | − | 34.31 | 147.11 | 0.83 | − | 17.69 |
Material | HTC-220-2 | HTC-220-4 | ||||||
0.05 | 85.19 | 0.98 | 9.98 × 104 | 10.25 | 78.39 | 0.99 | 4.25 × 104 | 9.43 |
0.10 | 87.22 | 0.99 | 1.30 × 105 | 10.49 | 82.98 | 0.99 | 1.10 × 105 | 9.98 |
0.15 | 86.77 | 0.99 | 1.15 × 105 | 10.44 | 91.69 | 0.98 | 6.47 × 105 | 11.03 |
0.20 | 89.62 | 0.98 | 2.06 × 105 | 10.78 | 112.46 | 0.95 | 4.14 × 107 | 13.53 |
0.25 | 104.21 | 0.96 | 4.43 × 106 | 12.53 | 142.34 | 0.91 | 1.56 × 1010 | 17.12 |
0.30 | 137.92 | 0.93 | 5.40 × 109 | 16.59 | 167.08 | 0.92 | 2.07 × 1012 | 20.10 |
0.35 | 170.20 | 0.93 | 3.53 × 1012 | 20.47 | 183.23 | 0.95 | 5.01 × 1013 | 22.04 |
0.40 | 188.88 | 0.96 | 1.14 × 1014 | 22.72 | 189.07 | 0.97 | 1.60 × 1014 | 22.74 |
0.45 | 193.33 | 0.98 | 2.05 × 1014 | 23.25 | 191.74 | 0.98 | 2.75 × 1014 | 23.06 |
0.50 | 190.65 | 0.98 | 1.09 × 1014 | 22.93 | 194.98 | 0.97 | 5.26 × 1014 | 23.45 |
0.55 | 189.12 | 0.98 | 7.75 × 1013 | 22.75 | 208.77 | 0.94 | 7.90 × 1015 | 25.11 |
0.60 | 191.91 | 0.98 | 1.39 × 1014 | 23.08 | 235.17 | 0.88 | 1.40 × 1018 | 28.29 |
0.65 | 205.44 | 0.89 | 5.49 × 1015 | 24.71 | 251.28 | 0.89 | 3.31 × 1019 | 30.22 |
0.70 | 222.05 | 0.76 | 3.69 × 1017 | 26.71 | 258.15 | 0.91 | 1.29 × 1020 | 31.05 |
0.75 | 244.16 | 0.74 | 5.03 × 1019 | 29.37 | 263.15 | 0.92 | 3.51 × 1020 | 31.65 |
0.80 | 255.68 | 0.73 | 1.31 × 1021 | 30.75 | 273.82 | 0.92 | 2.88 × 1021 | 32.93 |
0.85 | 239.95 | 0.63 | 2.18 × 1021 | 28.86 | 279.40 | 0.90 | 8.81 × 1021 | 33.61 |
average | 169.55 | 0.90 | − | 20.39 | 188.45 | 0.94 | − | 22.67 |
Reaction Mechanism | Integral Form, g(α) | Range I α = 0.10−0.40 | Range II α = 0.45−0.85 | ||
---|---|---|---|---|---|
EA kJ mol−1 | R2− | EA kJ mol−1 | R2− | ||
Reaction Order | |||||
Zero order F0 | α | 77.58 | 0.98 | 9.39 | 0.74 |
First order F1 | −ln (1−α) | 89.76 | 0.98 | 26.11 | 0.95 |
Second order F2 | [1/(1−α)] −1 | 103.21 | 0.99 | 51.11 | 0.99 |
Third order F3 | [1/(1−α)2] −1 | 117.93 | 0.99 | 83.16 | 0.99 |
Diffusion | |||||
One-dimensional diffusion D1 | α 2 | 164.46 | 0.98 | 29.44 | 0.88 |
Two-dimensional diffusion D2 | (1−α) ln (1−α) +α | 172.17 | 0.99 | 38.12 | 0.92 |
Three-dimensional diffusion D3 | [1− (1−α)1/3]2 | 180.42 | 0.99 | 49.91 | 0.95 |
Ginstling–Brouns D4 | 1− (2α/3) − (1−α)2/3 | 174.92 | 0.99 | 41.98 | 0.93 |
Geometrical Contraction Models | |||||
Contracting area (cylinder) R2 | 1− (1−α)1/2 | 83.51 | 0.99 | 10.76 | 0.86 |
Contracting volume (sphere) R3 | 1− (1−α)1/3 | 85.56 | 0.99 | 13.60 | 0.90 |
Nucleation Models | |||||
Power law P1 | α 1/4 | 12.41 | 0.95 | −5.65 | 0.93 |
Power law P2 | α 1/3 | 19.65 | 0.97 | −3.98 | 0.79 |
Power law P3 | α 1/2 | 34.13 | 0.98 | −0.64 | 0.05 |
Power law P4 | α 3/2 | 48.62 | 0.98 | 2.70 | 0.34 |
Avrami–Erofeev (m = 2) A2 | [−ln (1−α)]1/2 | 40.22 | 0.99 | 7.72 | 0.85 |
Avrami–Erofeev (m = 3) A3 | [−ln (1−α)]1/3 | 23.71 | 0.98 | 1.59 | 0.34 |
Avrami–Erofeev (m = 4) A4 | [−ln (1−α)]1/4 | 15.46 | 0.97 | −1.47 | 0.42 |
Average EA Obtained Using KAS Method | 245.76 | − | 326.96 | − |
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Analysis | BSG | HTC-180-4 | HTC-220-2 | HTC-220-4 | ||||
---|---|---|---|---|---|---|---|---|
Moisture, wt.% | 3.75 | ± 0.65 | 4.06 | ± 0.41 | 3.42 | ± 0.75 | 3.25 | ± 0.83 |
Proximate analysis, db, wt.% | ||||||||
Ash | 4.32 | ± 0.05 | 4.40 | ± 0.05 | 4.40 | ± 0.13 | 4.83 | ± 0.13 |
Volatile Matter | 79.22 | ± 0.07 | 70.59 | ± 0.17 | 68.06 | ± 0.57 | 63.93 | ± 1.03 |
Fixed Carbon | 16.46 | ± 0.76 | 25.01 | ± 0.24 | 27.54 | ± 0.63 | 31.25 | ± 0.57 |
Ultimate analysis, daf, wt.% | ||||||||
C | 53.50 | ± 0.40 | 66.29 | ± 0.33 | 68.82 | ± 0.75 | 70.17 | ± 0.77 |
H | 7.27 | ± 0.09 | 7.39 | ± 0.04 | 7.62 | ± 0.05 | 7.21 | ± 0.06 |
N | 4.89 | ± 0.27 | 4.54 | ± 0.06 | 4.61 | ± 0.06 | 4.67 | ± 0.14 |
S | 0.30 | ± 0.02 | 0.46 | ± 0.01 | 0.45 | ± 0.01 | 0.45 | ± 0.02 |
O | 34.04 | ± 0.80 | 21.33 | ± 0.45 | 18.51 | ± 0.65 | 17.51 | ± 1.00 |
HHV, daf, MJ kg−1 | 23.53 | ± 0.16 | 29.54 | ± 0.11 | 30.89 | ± 0.25 | 31.06 | ± 0.23 |
Pyrolysis Temperature (°C) | Feedstock | Char Yield * | Ash | VM | FC | HHV MJ kg−1 |
---|---|---|---|---|---|---|
wt.% | ||||||
db | daf | |||||
300 | BSG | 78.5 | 5.31 | 56.45 | 38.24 | 27.26 |
HTC-180-4 | 79.4 | 5.31 | 51.13 | 43.56 | 29.49 | |
HTC-220-2 | 81.0 | 5.26 | 43.59 | 51.15 | 30.99 | |
HTC-220-4 | 85.8 | 5.44 | 40.05 | 54.51 | 31.12 | |
500 1 | BSG | 25.9 | 13.08 | 6.89 | 80.03 | 32.22 |
HTC-180-4 | 35.8 | 11.78 | 7.50 | 80.72 | 31.59 | |
HTC-220-2 | 46.2 | 9.21 | 8.83 | 81.96 | 31.11 | |
HTC-220-4 | 52.0 | 8.98 | 6.21 | 84.80 | 31.88 | |
700 | BSG | 22.3 | 18.67 | 0.29 | 81.03 | 33.09 |
HTC-180-4 | 30.9 | 13.64 | 2.63 | 83.74 | 32.34 | |
HTC-220-2 | 41.2 | 10.34 | 3.79 | 85.87 | 31.48 | |
HTC-220-4 | 46.2 | 10.11 | 0.43 | 89.46 | 33.13 | |
900 | BSG | 22.0 | 18.92 | − | 81.08 | 32.72 |
HTC-180-4 | 28.3 | 14.90 | − | 85.10 | 31.94 | |
HTC-220-2 | 37.4 | 11.39 | − | 88.61 | 30.73 | |
HTC-220-4 | 45.8 | 10.20 | − | 89.80 | 30.75 |
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Olszewski, M.P.; Arauzo, P.J.; Maziarka, P.A.; Ronsse, F.; Kruse, A. Pyrolysis Kinetics of Hydrochars Produced from Brewer’s Spent Grains. Catalysts 2019, 9, 625. https://doi.org/10.3390/catal9070625
Olszewski MP, Arauzo PJ, Maziarka PA, Ronsse F, Kruse A. Pyrolysis Kinetics of Hydrochars Produced from Brewer’s Spent Grains. Catalysts. 2019; 9(7):625. https://doi.org/10.3390/catal9070625
Chicago/Turabian StyleOlszewski, Maciej P., Pablo J. Arauzo, Przemyslaw A. Maziarka, Frederik Ronsse, and Andrea Kruse. 2019. "Pyrolysis Kinetics of Hydrochars Produced from Brewer’s Spent Grains" Catalysts 9, no. 7: 625. https://doi.org/10.3390/catal9070625