Upgrading Pyrolytic Oil via Catalytic Co-Pyrolysis of Beechwood and Polystyrene
Abstract
:1. Introduction
1.1. Catalyst Characterization
1.2. Catalytic Pyrolysis of Individual Biomass and Plastic
1.3. Catalytic Co-Pyrolysis of Biomass and Plastic
1.4. Catalytic Co-Pyrolysis under Fe/Ni-ZSM-5
2. Experimental Section
2.1. Materials
2.2. Catalyst Preparation
2.3. Catalyst Characterization
2.4. Experimental Methods
2.4.1. Pyrolysis Experimental Setup
2.4.2. GC-MS Analysis for Liquid Products
2.4.3. GC-FID Analysis for Liquid Products
2.4.4. GC-FID/TCD Analysis of Non-Condensable Gases
2.4.5. Lower Heating Value (LHV) and Synergism between Biomass and Plastic
3. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Abbreviations
Abbreviations | Definition | |
FID | Flame-ionization detector | |
TCD | Thermal conductivity detector | |
GC-MS | Gas chromatography–mass spectroscopy | |
PS PAH | Polystyrene Polycyclic aromatic hydrocarbon | |
ECN | Effective carbon number | |
TGA | Thermogravimetric analysis | |
n.a. | Not applicable | |
Symbols | Symbol name | Unit |
m | Mass | [g] |
z | Charge number | |
(m/z) | Mass-to-charge ratio | [g·mol−1] |
wt.% | Weight percentage | [%] |
LHV | Lower heating value | [MJ·kg−1] |
HHV | Higher heating value | [MJ·kg−1] |
r2 | Pearson’s coefficient of determination | |
I.D./O.D. | Inner and outer diameter | [m] |
a.u | Arbitrary unit |
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ZSM-5 | Fe-ZSM-5 | Fe/Ni-ZSM-5 | Ni-ZSM-5 | |
---|---|---|---|---|
SiO2/Al2O3 | 38.0 | 38.4 | 38.9 | 38.5 |
Fe (wt.%) a | 0.04 | 1.46 | 1.32 | 0.04 |
Ni (wt.%) a | - | - | 1.22 | 1.21 |
BET surface area (m2/g) b | 282.0 | 299.1 | 284.9 | 274.0 |
Micropore surface area (m2/g) c | 109.5 | 135.5 | 123.8 | 126.8 |
External surface area (m2/g) c | 172.5 | 163.6 | 161.1 | 147.3 |
Specific pore volume (cm3/g) c | 0.24 | 0.24 | 0.23 | 0.22 |
Micropore volume (cm3/g) c | 0.05 | 0.06 | 0.06 | 0.06 |
RT (min) * | Chemical Family | Reference Compound |
---|---|---|
6.63 | Furans | Furan |
11.15 | Carboxylic acids | Acetic acid |
12.13 | Aromatics | Toluene |
18.39 | Esters & Ethers | Allyl butyrate |
19.52 | Aldehydes | Furfural |
21.63 | Ketones | 2-methyl-2-cyclopenten-1-one |
31.82 | Phenols | p-cresol |
40.76 | PAH | Bibenzyl |
41.74 | Guaiacols | 4-methylcatechol |
42.74 | Nitrogenates | Benzamide |
49.58 | Carbohydrates | Levoglucosan |
Concentrations (wt.%) | |||||
---|---|---|---|---|---|
No Catalyst | ZSM-5 | Fe-ZSM-5 | Fe/Ni-ZSM-5 | Ni-ZSM-5 | |
Carboxylic acids | 35.3 | 35.7 | 33.5 | 36.1 | 35.3 |
Ester | 5.8 | 4.5 | 4.4 | 4.7 | 4.4 |
Ether | 0.7 | 1.0 | 0.9 | 0.9 | 0.9 |
Nitrogenates | 4.4 | 3.5 | 3.8 | 4.3 | 4.1 |
Ketones | 15.0 | 14.0 | 14.0 | 13.8 | 14.7 |
Furans | 9.8 | 8.8 | 8.5 | 8.8 | 9.6 |
Aldehydes | 2.4 | 0.5 | 0.5 | 0.7 | 0.8 |
Carbohydrates | 17.3 | 9.5 | 11.7 | 12.5 | 12.4 |
Phenols | 2.8 | 7.7 | 8.0 | 5.0 | 3.9 |
Guaiacols | 5.2 | 6.3 | 7.0 | 6.6 | 6.9 |
Aromatics | - | 2.8 | 2.6 | 2.6 | 2.7 |
PAH | - | 3.9 | 3.3 | 2.3 | 2.1 |
Oxygen content | 41.3 | 36.4 | 37.3 | 39.0 | 38.9 |
LHV (MJ/kg) | 18.4 | 20.4 | 20.3 | 19.4 | 19.4 |
Liquid yield | 65.0 | 56.2 | 56.0 | 47.9 | 56.3 |
Char yield | 20.0 | 21.3 | 20.7 | 21.3 | 20.0 |
Coke | - | 3.0 | 3.3 | 3.3 | 2.3 |
Gaz yield | 15.0 | 19.5 | 20.0 | 27.5 | 21.4 |
Concentrations (wt.%) | |||||
---|---|---|---|---|---|
No catalyst | ZSM-5 | Fe-ZSM-5 | Fe/Ni-ZSM-5 | Ni-ZSM-5 | |
Aromatics | 76.7 | 82.2 | 77.7 | 81.7 | 77.8 |
PAH | 23.3 | 17.8 | 22.3 | 18.3 | 22.2 |
LHV (MJ/kg) | 40.6 | 40.6 | 40.0 | 40.6 | 40.5 |
Liquid yield | 99.9 | 96.2 | 96.1 | 96.6 | 96.3 |
Char yield | 0.0 | 0.0 | 0.0 | 0.0 | 0.0 |
Coke | 0.0 | 3.3 | 3.1 | 3.0 | 3.3 |
Gaz yield | 0.1 | 0.5 | 0.8 | 0.4 | 0.4 |
Name | LHV (MJ/kg) | LHV Change (%) | O% (wt.%) | O% Change (%) | Ref. |
---|---|---|---|---|---|
BW (No cat.) | 18.4 | n.a | 41.3 | n.a | This work |
BW (ZSM-5) | 20.4 | +10.9 a | 36.4 | −11.9 a | |
BW-PS 50-50 (No cat.) | 36.5 | +98.4 | 7.8 | −81.1 | |
BW-PS 50-50 (Fe/Ni-ZSM-5) | 38.8 | +110.9 | 3.2 | −92.3 | |
BW-PS 75-25 (No cat.) | 30.0 | +63.0 | 19.6 | −52.5 | |
BW-PS 75-25 (Fe/Ni-ZSM-5) | 35.8 | +94.6 | 8.8 | −78.7 | |
PS | 40.6 | n.a | - | n.a | |
Gasoline | 43.4–46.5 | ~2.7 | [40,41,42] | ||
Kerosene | 43.0–46.2 | n.a. | |||
Diesel | 42.8–45.8 | ~1.8 |
Chemical Families | Operating Temperature (°C) ± 5 °C | |||
---|---|---|---|---|
450 | 500 | 550 | 600 | |
Carboxylic acids | 3.6 | 2.9 | 4.1 | 5.6 |
Ketones | 1.3 | 0.9 | 1.5 | 2.1 |
Furans | 0.7 | 0.8 | 1.2 | 1.5 |
Carbohydrates | 1.3 | 1.7 | 2.7 | 3.0 |
Aromatics | 68.9 | 66.2 | 68.4 | 74.0 |
PAH | 22.5 | 25.8 | 20.3 | 12.2 |
Gas yield | 14.5 | 16.1 | 17.9 | 23.0 |
Liquid yield | 70.2 | 69.9 | 66.1 | 61.0 |
Char yield | 12.7 | 10.3 | 10.0 | 9.0 |
Coke | 2.7 | 3.6 | 6.0 | 7.0 |
O% | 3.6 | 3.2 | 4.7 | 6.0 |
LHV * | 38.7 | 38.8 | 38.0 | 37.5 |
Name | Ultimate Analysis | Proximate Analysis | |||||
---|---|---|---|---|---|---|---|
% C | % H | % O * | Moisture | Fixed Carbon | Volatile | Ash | |
PS | 92.6 | 7.4 | - | - | 0.3 | 99.7 | - |
BW | 47.4 | 6.1 | 46.5 | 5.7 | 17.5 | 75.9 | 0.9 |
Reaction | Catalyst | BW-PS Percentage (wt.%) | Temperature (°C) |
---|---|---|---|
Biomass pyrolysis | No catalyst | 500 | |
ZSM-5 | |||
Fe-ZSM-5 | 100-0 | ||
Fe/Ni-ZSM-5 | |||
Ni-ZSM-5 | |||
Plastic pyrolysis | No catalyst | 500 | |
ZSM-5 | |||
Fe-ZSM-5 | 0-100 | ||
Fe/Ni-ZSM-5 | |||
Ni-ZSM-5 | |||
Co-pyrolysis | No catalyst | 25-50-75 | 500 |
No catalyst | 50 | 450-500-550-600 | |
ZSM-5 | 50 | 500 | |
Fe-ZSM-5 | 50 | ||
Fe/Ni-ZSM-5 | 25-50-75 | ||
Ni-ZSM-5 | 50 | ||
Fe/Ni-ZSM-5 | 50 | 450-500-550-600 |
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Jaafar, Y.; Ramirez, G.C.A.; Abdelouahed, L.; El Samrani, A.; El Hage, R.; Taouk, B. Upgrading Pyrolytic Oil via Catalytic Co-Pyrolysis of Beechwood and Polystyrene. Molecules 2023, 28, 5758. https://doi.org/10.3390/molecules28155758
Jaafar Y, Ramirez GCA, Abdelouahed L, El Samrani A, El Hage R, Taouk B. Upgrading Pyrolytic Oil via Catalytic Co-Pyrolysis of Beechwood and Polystyrene. Molecules. 2023; 28(15):5758. https://doi.org/10.3390/molecules28155758
Chicago/Turabian StyleJaafar, Yehya, Gian Carlos Arias Ramirez, Lokmane Abdelouahed, Antoine El Samrani, Roland El Hage, and Bechara Taouk. 2023. "Upgrading Pyrolytic Oil via Catalytic Co-Pyrolysis of Beechwood and Polystyrene" Molecules 28, no. 15: 5758. https://doi.org/10.3390/molecules28155758