Ex Situ Catalytic Pyrolysis of Invasive Pennisetum purpureum Grass with Activated Carbon for Upgrading Bio-Oil
Abstract
:1. Introduction
2. Experimental
2.1. Biomass Sample Preparation
2.2. Preparation of Activated Carbon (Catalyst)
2.3. Characterization of the Activated Carbon (SEM, BET, FTIR)
2.4. Regeneration of Activated Carbon (Catalyst)
2.5. Biomass to Catalyst Ratio
2.6. Non-Catalytic and Catalytic (Ex Situ) Pyrolysis Setup
2.7. Bio-Oils Analysis (GC–MS)
3. Results and Discussions
3.1. Characterizations
3.2. Product Yield (Catalytic and Non-Catalytic Pyrolysis)
3.3. Bio-Oil Analysis by GC–MS
3.3.1. Non-Catalytic Pyrolysis Process
3.3.2. Catalytic Pyrolysis Process (AC, RAC-1, and RAC-2)
3.4. Comparison of Major Bio-Oil Chemicals from Catalytic and Non-Catalytic Pyrolysis
3.4.1. Comparison of Major Chemical Groups of Bio-Oils
3.4.2. Comparison of Some Specific Chemicals of Bio-Oils
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Catalyst Name | Catalyst Code | Biomass (wt.):Catalyst (wt.) |
---|---|---|
No catalyst | -- | 25 (g):0 (g) |
Activated Carbon | AC | 25 (g):1 (g) |
First-Time Regenerated Activated Carbon | RAC-1 | 25 (g):1 (g) |
Second-Time Regenerated Activated Carbon | RAC-2 | 25 (g):1 (g) |
Catalyst | Biochar (wt.%) | Bio-Oil (wt.%) | Syngas (wt.%) | ||||||
---|---|---|---|---|---|---|---|---|---|
Mean | σ | Mean | σ | Mean | σ | ||||
No catalyst | 27.40 | 0.35 | 0.25 | 36.70 | 0.61 | 0.43 | 35.90 | 0.67 | 0.47 |
AC | 27.76 | 0.46 | 0.33 | 34.72 | 0.29 | 0.21 | 37.52 | 0.81 | 0.57 |
RAC-1 | 27.65 | 0.51 | 0.36 | 34.98 | 0.53 | 0.37 | 37.37 | 0.34 | 0.24 |
RAC-2 | 27.53 | 0.39 | 0.28 | 35.27 | 0.48 | 0.34 | 37.20 | 0.57 | 0.40 |
Ret. Time (min) | Chemical Name | MW | Formula | Peak Area (%) | Chemical Group |
---|---|---|---|---|---|
3.027 | Acetic acid, ethoxy- | 104 | C4H8O3 | 0.61 | Acid |
3.172 | 1H-Pyrazole, 3,5-dimethyl- | 96 | C5H8N2 | 4.45 | Nitrogenous |
3.34 | 2-Furanmethanol | 98 | C5H6O2 | 3.01 | Furans |
3.391 | 2-Propanone, 1-(acetyloxy)- | 116 | C5H8O3 | 4.29 | Misc. Oxygenated |
3.758 | 2-Cyclopenten-1-one, 3-methyl- | 96 | C6H8O | 0.82 | Ketones |
3.841 | Butanoic acid, 4-hydroxy- | 104 | C4H8O3 | 2.52 | Acid |
3.977 | Cyclohexanone | 98 | C6H10O | 2.82 | Ketones |
4.067 | 2-Hexanone, 6-hydroxy- | 116 | C6H12O2 | 1.13 | Misc. Oxygenated |
4.266 | 2-Furancarboxaldehyde, 5-methyl- | 110 | C6H6O2 | 0.88 | Furans |
4.308 | 2-Cyclopenten-1-one, 3-methyl- | 96 | C6H8O | 0.83 | Ketones |
4.47 | Phenol | 94 | C6H6O | 3.02 | Phenolic |
4.629 | Octanoic acid, 2-amino- | 159 | C8H17NO2 | 2.54 | Nitrogenous |
4.775 | Triethylenediamine | 112 | C6H12N2 | 0.64 | Nitrogenous |
4.916 | 2-Cyclopenten-1-one, 2-hydroxy-3-methyl- | 112 | C6H8O2 | 2.58 | Ketones |
5.038 | 2-Propenoic acid, 2-methyl-, 1,2-ethanediyl Ester | 142 | C8H14O2 | 0.86 | Ester |
5.112 | Phenol, 2-methyl- | 108 | C7H8O | 1.80 | Phenolic |
5.293 | Phenol, 4-methyl- | 108 | C7H8O | 2.56 | Phenolic |
5.384 | Butanoic acid, 2-propenyl ester | 128 | C7H12O2 | 0.93 | Ester |
5.428 | Phenol, 2-methoxy- | 124 | C7H8O2 | 1.62 | Phenolic |
5.606 | Cyclopropyl carbinol | 72 | C4H8O | 7.24 | Alcohol |
5.683 | Maltol | 126 | C6H6O3 | 0.80 | Acid |
5.724 | 2-Cyclopenten-1-one, 3-ethyl-2-hydroxy- | 126 | C7H10O2 | 1.90 | Ketones |
5.929 | Phenol, 2,5-dimethyl- | 122 | C8H10O | 1.23 | Phenolic |
5.999 | Pentanoic acid, 5-bromo- | 181 | C5H9BrO2 | 0.32 | Bromide |
6.095 | Phenol, 4-ethyl- | 122 | C8H10O | 1.04 | Phenolic |
6.152 | Benzamide, N-hydroxy- | 137 | C7H7NO2 | 0.23 | Nitrogenous |
6.206 | n-Decanoic acid | 172 | C10H20O2 | 0.46 | Acid |
6.276 | Benzyl alcohol | 108 | C7H8O | 0.34 | Alcohol |
6.346 | Phenol, 2-methoxy-4-methyl- | 138 | C8H10O2 | 0.56 | Phenolic |
6.506 | 1,2-Benzenediol | 110 | C6H6O2 | 3.98 | Phenolic |
6.578 | Benzofuran, 2,3-dihydro- | 120 | C8H8O | 3.68 | Furans |
6.748 | 2-Furancarboxaldehyde, 5-(hydroxymethyl)- | 126 | C6H6O3 | 1.63 | Furans |
6.874 | Furan, 2,5-dimethyl- | 96 | C6H8O | 0.22 | Furans |
6.945 | 2,5-Hexanedione | 114 | C6H10O2 | 0.52 | Ketones |
7.061 | 1,2-Benzenediol, 3-methoxy- | 140 | C7H8O3 | 1.38 | Misc. Oxygenated |
7.151 | Phenol, 4-ethyl-2-methoxy- | 152 | C9H12O2 | 1.00 | Phenolic |
7.19 | Hydroquinone | 110 | C6H6O2 | 1.66 | Phenolic |
7.295 | 3,3,5,5-Tetramethylcyclohexanol | 156 | C10H20O | 0.34 | Alcohol |
7.348 | 1,2-Benzenediol, 3-methyl- | 124 | C7H8O2 | 0.89 | Phenolic |
7.393 | 1,5-Diacetoxypentane | 188 | C9H16O4 | 0.51 | Misc. Oxygenated |
7.502 | 2-Propenal, 3-phenyl- | 132 | C9H8O | 1.29 | Aldehyde |
7.743 | 2H-Pyran, tetrahydro-2-methyl- | 100 | C6H12O | 0.85 | Misc. Oxygenated |
7.86 | Phenol, 2,6-dimethoxy- | 154 | C8H10O3 | 1.92 | Phenolic |
7.922 | Benzene, 1-methyl-2-(methylthio)- | 138 | C8H10S | 0.73 | Sulfide |
8.02 | 2-Heptanone, 6-methyl- | 128 | C8H16O | 1.00 | Ketones |
8.088 | 1-Pentyn-3-ol, 3,4-dimethyl- | 112 | C7H12O | 0.56 | Misc. Oxygenated |
8.172 | 3-Decanone | 156 | C10H20O | 0.48 | Ketones |
8.229 | 1,3-Benzenediol, 4-ethyl- | 138 | C8H10O2 | 1.11 | Phenolic |
8.362 | 3-Buten-2-one, 4-(2,5,6,6-tetramethyl-2-cyclohexen-1-yl)- | 206 | C14H22O | 0.31 | Ketones |
8.413 | 2-Propenoic acid, 2-methyl-, 1,2-ethanediyl ester | 142 | C8H14O2 | 0.67 | Ester |
8.486 | 1,3-Benzenediol, 4,5-dimethyl- | 138 | C8H10O2 | 0.26 | Phenolic |
8.636 | Acetic acid, ethoxy- | 104 | C4H8O3 | 1.62 | Acid |
8.832 | 3,4-Dimethylanisole | 136 | C9H12O | 0.62 | Ether |
9.139 | Bicyclo [2.2.1]heptan-2-one, 5-(acetyloxy)-4,7,7-trimethyl-, endo- | 210 | C12H18O3 | 0.21 | Ketones |
9.667 | 5-tert-Butylpyrogallol | 182 | C10H14O3 | 1.39 | Misc. Oxygenated |
9.743 | Benzene, 1,2-dimethoxy- | 138 | C8H10O2 | 1.61 | Ether |
9.788 | 2(3H)-Naphthalenone,4,4a,5,6,7,8-hexahydro-4a-methyl- | 164 | C11H16O | 3.16 | Misc. Oxygenated |
10.002 | 11-Heneicosanone | 310 | C21H42O | 0.82 | Ketones |
10.099 | 3’,5’-Dimethoxyacetophenone | 180 | C10H12O3 | 0.22 | Phenolic |
10.598 | Pentanoic acid, 4-oxo-, ethyl ester | 144 | C7H12O3 | 0.45 | Ester |
10.978 | 4-Acetylbutyric acid | 130 | C6H10O3 | 0.19 | Acid |
11.522 | Glucitol, 6-O-nonyl- | 308 | C15H32O6 | 0.19 | Misc. Oxygenated |
12.356 | 2-Propanone, 1,1-diphenyl- | 210 | C15H14O | 0.23 | Ketones |
12.45 | 4-Methyldaphnetin | 192 | C10H8O4 | 0.19 | Misc. Oxygenated |
14.161 | n-Hexadecanoic acid | 256 | C16H32O2 | 0.21 | Acid |
15.951 | cis-13-Octadecenoic acid | 282 | C18H34O2 | 1.59 | Acid |
16.129 | Octadecanoic acid | 284 | C18H36O2 | 0.35 | Acid |
Ret. Time (min) | Chemical Name | MW | Chemical Formula | AC | RAC-1 | RAC-2 | Chemical Group |
---|---|---|---|---|---|---|---|
Area (%) | Area (%) | Area (%) | |||||
3.029 | Propanoic acid | 74 | C3H6O2 | 1.43 | 5.40 | 1.42 | Acid |
3.146 | 2-Cyclopenten-1-one | 82 | C5H6O | 5.05 | 1.88 | 0.92 | Ketones |
3.245 | Furan, tetrahydro- | 72 | C4H8O | 1.26 | 2.70 | 2.85 | Furans |
3.337 | 2-Furanmethanol | 98 | C5H6O2 | 3.36 | 2.40 | 3.99 | Furans |
3.407 | 2-Butene-1,4-diol | 88 | C4H8O2 | 2.84 | 2.51 | 0.00 | alcohol |
3.524 | 3-Hepten-1-ol | 114 | C7H14O | 1.32 | 4.42 | 3.85 | alcohol |
3.618 | Furan, 2-methyl- | 82 | C5H6O | 0.10 | 3.44 | 0.00 | Furans |
3.675 | 2-Furanmethanol | 98 | C5H6O2 | 0.33 | 1.85 | 2.06 | Furans |
3.781 | 2-Cyclopenten-1-one, 3-methyl- | 96 | C6H8O | 0.86 | 0.89 | 3.37 | Ketones |
3.847 | Phenol, 2-methyl- | 108 | C7H8O | 2.34 | 2.04 | 1.84 | Phenolic |
3.917 | Phenol | 94 | C6H6O | 0.87 | 1.51 | 0.00 | Phenolic |
3.962 | 2-Cyclopenten-1-one, 2-methyl- | 96 | C6H8O | 1.94 | 1.48 | 1.80 | Ketones |
4.141 | Butyrolactone | 86 | C4H6O2 | 0.36 | 2.69 | 1.98 | Ketones |
4.276 | Cyclohexanone | 98 | C6H10O | 0.85 | 1.01 | 3.53 | Ketones |
4.313 | 2-Cyclopenten-1-one, 3-methyl- | 96 | C6H8O | 0.93 | 2.24 | 1.51 | Ketones |
4.449 | Phenol | 94 | C6H6O | 12.83 | 12.19 | 2.68 | Phenolic |
4.664 | 2-Propanone, 1-(acetyloxy)- | 116 | C5H8O3 | 0.59 | 3.37 | 2.83 | Misc. Oxygenated |
4.883 | 1,2-Cyclopentanedione, 3-methyl- | 112 | C6H8O2 | 2.01 | 0.89 | 1.03 | Ketones |
4.984 | 2-Cyclopenten-1-one, 2-hydroxy-3-methyl- | 112 | C6H8O2 | 0.20 | 2.13 | 1.91 | Ketones |
5.025 | 2-Cyclopenten-1-one, 2,3-dimethyl- | 110 | C7H10O | 0.12 | 0.68 | 1.03 | Ketones |
5.091 | Benzyl alcohol | 108 | C7H8O | 2.32 | 2.19 | 2.44 | Alcohol |
5.339 | Phenol, 2-methyl- | 108 | C7H8O | 4.86 | 4.15 | 2.55 | Phenolic |
5.408 | 2-Cyclopenten-1-one, 3-ethyl-2-hydroxy- | 126 | C7H10O2 | 0.11 | 2.40 | 1.04 | Ketones |
5.466 | Phenol, 2-ethyl- | 122 | C8H10O | 0.28 | 1.45 | 3.27 | Phenolic |
5.671 | 2-Cyclopenten-1-one, 3-ethyl-2-hydroxy- | 126 | C7H10O2 | 1.89 | 1.23 | 2.25 | Ketones |
5.798 | Phenol, 2-ethyl- | 122 | C8H10O | 0.20 | 0.80 | 0.80 | Phenolic |
5.907 | Phenol, 2,5-dimethyl- | 122 | C8H10O | 0.95 | 1.96 | 2.25 | Phenolic |
6.059 | Phenol, 4-ethyl- | 122 | C8H10O | 2.54 | 1.85 | 1.73 | Phenolic |
6.177 | Phenol, 2,6-dimethyl- | 122 | C8H10O | 0.13 | 1.04 | 0.85 | Phenolic |
6.243 | 2,4-Imidazolidinedione, 5,5-dimethyl- | 128 | C5H8N2O2 | 0.10 | 0.78 | 0.62 | Nitrogenous |
6.39 | Benzofuran, 2,3-dihydro- | 120 | C8H8O | 10.06 | 2.57 | 3.89 | Furans |
6.533 | 1,2-Benzenediol | 110 | C6H6O2 | 4.62 | 1.84 | 2.09 | Phenolic |
6.685 | Resorcinol monoacetate | 152 | C8H8O3 | 2.40 | 1.22 | 1.74 | Misc. Oxygenated |
6.852 | 2-Coumaranone | 134 | C8H6O2 | 0.27 | 0.57 | 0.56 | Furans |
6.95 | 1,2-Benzenediol, 4-methyl- | 124 | C7H8O2 | 1.89 | 1.34 | 0.92 | Phenolic |
7.01 | Caprolactam | 113 | C6H11NO | 1.40 | 1.56 | 2.27 | Nitrogenous |
7.068 | Hydroquinone | 110 | C6H6O2 | 2.61 | 0.84 | 1.39 | Phenolic |
7.243 | 4-Methylcatechol | 124 | C7H8O2 | 3.63 | 1.45 | 1.99 | Alcohol |
7.395 | Phenol, 4-ethyl-2-methoxy- | 152 | C9H12O2 | 0.48 | 0.46 | 1.02 | Phenolic |
7.535 | Benzoic acid, 2-hydroxy-5-methyl-, methyl ester | 166 | C9H10O3 | 0.34 | 0.97 | 0.71 | Ester |
7.602 | 2-Nonen-1-ol | 142 | C9H18O | 0.18 | 0.27 | 0.99 | Alcohol |
7.648 | 1,3-Benzenediol, 2-methyl- | 124 | C7H8O2 | 0.57 | 0.27 | 0.35 | Phenolic |
7.74 | 3-Methoxybenzyl alcohol | 138 | C8H10O2 | 1.31 | 0.26 | 0.44 | alcohol |
7.849 | 1,4-Benzenediol, 2-methyl- | 124 | C7H8O2 | 0.39 | 0.43 | 2.10 | Phenolic |
7.899 | Benzofuran, 2-methyl- | 132 | C9H8O | 0.26 | 0.80 | 0.66 | Furans |
7.938 | Benzaldehyde, 4-hydroxy- | 122 | C7H6O2 | 0.21 | 0.40 | 0.51 | Aldehyde |
8.153 | 1,3-Benzenediol, 4-ethyl- | 138 | C8H10O2 | 2.15 | 0.24 | 1.84 | Phenolic |
8.281 | Ethanone, 1-(3-hydroxyphenyl)- | 136 | C8H8O2 | 0.18 | 0.46 | 0.57 | Ketones |
8.413 | 1,3-Benzenediol, 4,5-dimethyl- | 138 | C8H10O2 | 0.07 | 0.22 | 0.53 | Phenolic |
8.558 | Benzoic acid, ethyl ester | 150 | C9H10O2 | 0.44 | 0.15 | 1.70 | Ester |
8.752 | Phenol, 2,3,6-trimethyl- | 136 | C9H12O | 0.76 | 0.10 | 0.47 | Phenolic |
8.846 | Isoborneol | 154 | C8H10O2 | 0.17 | 0.01 | 0.53 | Alcohol |
8.942 | Phenol, 2,3,6-trimethyl- | 136 | C9H12O | 0.13 | 0.00 | 1.19 | Phenolic |
9.155 | Benzeneacetic acid, 3,4-dihydroxy- | 168 | C8H8O4 | 0.10 | 0.00 | 1.03 | Acid |
9.256 | Nonanoic acid | 158 | C9H18O2 | 1.70 | 0.00 | 2.72 | Acid |
9.668 | 2(3H)-Naphthalenone,4,4a,5,6,7,8-hexahydro-4a-methyl- | 164 | C11H16O | 0.48 | 0.01 | 0.84 | Misc. Oxygenated |
10.18 | 4-Acetylbutyric acid | 130 | C6H10O3 | 0.23 | 0.00 | 0.58 | Acid |
Chemical Groups | No Catalyst | Activated Carbon (AC) | 1st Regenerated AC (RAC-1) | 2nd Regenerated AC (RAC-2) |
---|---|---|---|---|
Acid | 8.34 | 3.46 | 5.40 | 5.75 |
Alcohol | 7.91 | 11.78 | 11.10 | 10.23 |
aldehyde | 1.29 | 0.21 | 0.40 | 0.51 |
Ester | 2.91 | 0.78 | 1.12 | 2.41 |
Ether | 2.23 | - | - | - |
Furans | 9.42 | 15.65 | 14.33 | 14.01 |
Ketones | 12.51 | 14.49 | 17.99 | 20.94 |
Nitrogenous | 7.86 | 1.50 | 2.34 | 2.90 |
Misc. Oxygenated | 13.65 | 3.47 | 4.60 | 5.41 |
Phenolic | 22.88 | 38.66 | 32.72 | 27.84 |
Bromide | 0.32 | - | - | - |
Sulfide | 0.73 | - | - | - |
Total (%) | 90.05 | 90.00 | 90.00 | 90.00 |
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Reza, M.S.; Afroze, S.; Kuterbekov, K.; Kabyshev, A.; Zh. Bekmyrza, K.; Taweekun, J.; Ja’afar, F.; Saifullah Abu Bakar, M.; Azad, A.K.; Roy, H.; et al. Ex Situ Catalytic Pyrolysis of Invasive Pennisetum purpureum Grass with Activated Carbon for Upgrading Bio-Oil. Sustainability 2023, 15, 7628. https://doi.org/10.3390/su15097628
Reza MS, Afroze S, Kuterbekov K, Kabyshev A, Zh. Bekmyrza K, Taweekun J, Ja’afar F, Saifullah Abu Bakar M, Azad AK, Roy H, et al. Ex Situ Catalytic Pyrolysis of Invasive Pennisetum purpureum Grass with Activated Carbon for Upgrading Bio-Oil. Sustainability. 2023; 15(9):7628. https://doi.org/10.3390/su15097628
Chicago/Turabian StyleReza, Md Sumon, Shammya Afroze, Kairat Kuterbekov, Asset Kabyshev, Kenzhebatyr Zh. Bekmyrza, Juntakan Taweekun, Fairuzeta Ja’afar, Muhammad Saifullah Abu Bakar, Abul K. Azad, Hridoy Roy, and et al. 2023. "Ex Situ Catalytic Pyrolysis of Invasive Pennisetum purpureum Grass with Activated Carbon for Upgrading Bio-Oil" Sustainability 15, no. 9: 7628. https://doi.org/10.3390/su15097628