Thermal Decomposition of Olive-Mill Byproducts: A TG-FTIR Approach
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials
- Small twigs (OW1), (diameter > 5 mm) separated at the first step of olive-oil production when the olives were cleaned prior to milling;
- Leaves (OW2), separated on sieves before olive cleaning. It also must be taken into consideration that leaves represented 5% of the weight of olives in the oil extraction;
- Solid olive-mill residue from the two-phase decanting method (OW3), which was a mixture of kernels and pulp from the olive fruit.
- Olive-mill wastewater liquid fraction with oil from the three-phase decanting method (OW4).
2.2. Methods
2.2.1. Physico-Chemical Parameters
2.2.2. TG-DTA and TG-FTIR Analyses
2.2.3. Combustion Parameters—Indexes
- Comprehensive combustion index:
- Ignition index:
- Burnout index:
- Flammability index:
2.2.4. Kinetic Models
3. Results and Discussion
3.1. Physico-Chemical Parameters
3.2. Thermogravimetric Analysis and Combustion Parameters
3.3. Kinetic Models
3.4. FTIR Spectra Analysis
4. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Samples | Proximate Analysis (wt %) | Ultimate Analysis (wt %) | LHV d.m. MJ/kg | |||||||
---|---|---|---|---|---|---|---|---|---|---|
Moisture w.b. | Ash d.m. | Volatile Matter d.m. | Fixed Carbon d.m. | C | H | N | S | O | ||
d.m. | ||||||||||
OW1 | 19.16 | 5.10 | 55.32 | 39.58 | 45.11 | 6.34 | 0.89 | 0.08 | 47.58 | 16.49 |
OW2 | 19.55 | 5.69 | 55.00 | 39.31 | 48.41 | 6.85 | 1.64 | 0.16 | 42.94 | 18.63 |
OW3 | 53.49 | 3.03 | 51.57 | 45.4 | 51.37 | 6.62 | 0.85 | 0.05 | 41.11 | 19.44 |
OW4 | 84.24 | 14.19 | 65.66 | 20.15 | 46.23 | 6.12 | 1.06 | 0.17 | 46.42 | 17.37 |
Sample | Stage IIa °C | Stage IIb °C | Stage IIc °C | Stage III °C |
---|---|---|---|---|
6 K/min | ||||
OW1 | - | - | 175–367 | 367–520 |
OW2 | - | 166–267 | 267–371 | 371–506 |
OW3 | 139–203 | 203–284 | 284–371 | 371–540 |
OW4 | - | - | 154–347 | 347–476 |
10 K/min | ||||
OW1 | - | - | 177–380 | 380–550 |
OW2 | - | 168–272 | 272–385 | 385–542 |
OW3 | 139–205 | 205–292 | 292–378 | 378–570 |
OW4 | - | - | 157–352 | 352–519 |
14 K/min | ||||
OW1 | - | - | 180–385 | 385–580 |
OW2 | - | 170–282 | 282–390 | 390–573 |
OW3 | 141–209 | 209–297 | 297–384 | 384–606 |
OW4 | - | - | 160–374 | 374–536 |
Stage IIa | Stage IIb | Stage IIc | Stage IIc | ||||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Sample | Ti | Tb | tb | DTGmax | Tmax | DTGmax | Tmax | DTGmax | Tmax | DTGmax | Tmax | S·107 | Di·102 | Db·104 | C·104 |
°C | °C | min | %/min | °C | %/min | °C | %/min | °C | %/min | °C | %2/(min2K3) | %/min3 | %/min4 | %/(minK2) | |
6 K/min | |||||||||||||||
OW1 | 222 | 520 | 48.3 | - | - | - | - | −2.89 | 303.8 | −2.19 | 454.2 | 0.83 | 0.14 | 0.15 | 0.59 |
OW2 | 198 | 506 | 49.7 | - | - | −2.07 | 247.9 | −2.60 | 299.9 | −2.27 | 456.2 | 0.98 | 0.13 | 0.15 | 0.66 |
OW3 | 208 | 540 | 53.8 | −0.89 | 182.0 | −2.53 | 269.7 | −2.92 | 316.3 | −2.24 | 459.9 | 0.95 | 0.13 | 0.13 | 0.67 |
OW4 | 230 | 476 | 39.8 | - | - | - | - | −4.14 | 270.3 | −2.41 | 382.9 | 1.27 | 0.23 | 0.27 | 0.78 |
10 K/min | |||||||||||||||
OW1 | 224 | 550 | 30.8 | - | - | - | - | −4.50 | 305.7 | −2.79 | 469.1 | 2.07 | 0.52 | 0.89 | 0.90 |
OW2 | 199 | 542 | 32.3 | - | - | −3.68 | 253.0 | −4.13 | 405.0 | −3.02 | 463.7 | 2.46 | 0.49 | 0.82 | 1.04 |
OW3 | 209 | 570 | 34.3 | −1.69 | 185.3 | −4.23 | 264.0 | −4.65 | 319.9 | −2.70 | 479.1 | 2.43 | 0.50 | 0.75 | 1.06 |
OW4 | 234 | 519 | 26.8 | - | - | - | - | −7.15 | 268.7 | −3.45 | 399.2 | 3.32 | 0.91 | 1.59 | 1.31 |
14 K/min | |||||||||||||||
OW1 | 226 | 580 | 23.2 | - | - | - | - | −6.33 | 302.0 | −3.15 | 474.5 | 3.09 | 1.24 | 2.79 | 1.24 |
OW2 | 206 | 573 | 24.1 | - | - | −5.31 | 259.5 | −5.49 | 303.9 | −3.43 | 469.2 | 4.15 | 1.11 | 2.46 | 1.29 |
OW3 | 210 | 606 | 26.1 | −2.20 | 188.8 | −5.99 | 268.8 | −6.38 | 325.9 | −2.95 | 482.5 | 4.46 | 1.18 | 2.29 | 1.45 |
OW4 | 235 | 536 | 19.7 | - | - | - | - | −10.06 | 269.2 | −3.67 | 430.7 | 6.42 | 2.28 | 5.27 | 1.81 |
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Wzorek, M.; Junga, R.; Yilmaz, E.; Bozhenko, B. Thermal Decomposition of Olive-Mill Byproducts: A TG-FTIR Approach. Energies 2021, 14, 4123. https://doi.org/10.3390/en14144123
Wzorek M, Junga R, Yilmaz E, Bozhenko B. Thermal Decomposition of Olive-Mill Byproducts: A TG-FTIR Approach. Energies. 2021; 14(14):4123. https://doi.org/10.3390/en14144123
Chicago/Turabian StyleWzorek, Małgorzata, Robert Junga, Ersel Yilmaz, and Bohdan Bozhenko. 2021. "Thermal Decomposition of Olive-Mill Byproducts: A TG-FTIR Approach" Energies 14, no. 14: 4123. https://doi.org/10.3390/en14144123