Development of an Energy Biorefinery Model for Chestnut (Castanea sativa Mill.) Shells
Abstract
:1. Introduction
2. Results and Discussion
2.1. Chemical Characterization of Crude and Pretreated CS
2.2. Saccharification of CS and Detoxification with Activated Charcoal
2.3. Desorption of Phenolic Compounds from Activated Charcoal and Radical Scavenging Activity
2.4. Fermentative Hydrogen and Butyrate Production
2.5. CS Biorefinery Model
- ENERGY 1: Biomass can be converted into energy (heat or electricity) through combustion, a process which is the most widely applied because of its low cost. The gross calorific values of chestnut shell and chestnut shell biochar are 15.49 and 25.86 MJ/kg, respectively [56]. Although it is expected that the chemical composition of spent CS, namely the final residue obtained after pretreatment and saccharification of CS, is somewhat different from crude CS or CS biochar, its use can be taken in consideration for energy production. As spent CS represent 32.5% (w/w) of the initial CS biomass (Figure 3), about 6100–9140 tons/year could be obtained from the total shell waste solid residue produced in 2014 in the Mediterranean basin.
- ENERGY 2: The price of conventionally produced H2 in 2016 averaged 4.0 USD/kg H2 in the USA, whereas the costs for the fermentative H2 production are currently estimated on 578 USD/kg H2 [57]. According to this reference, the high costs of the fermentative process are associated with a low molar yield and a low concentration of carbohydrates in the fermentation broth, which is adequate for research scale but not to scale-up to an industrial process. In fact, assuming the production yield obtained in the present work (63.9 mL H2/g), the total amount of CS generated in 2014 in the Mediterranean region would only correspond to 106,975–160,463 kg of H2. The feedstock cost and the capital cost for the industrial production are also critical to the high projected cost of hydrogen generated via DF of biomass. However, in the case of CS as waste biomass, the negative feedstock cost would impact positively on the process economic balance, so as the co-production of bioactive molecules. Considering an optimized scenario modeled with a fermentation broth concentration of 300 g/L and the conversion of excess lignin and biogas to thermal energy and further to electrical energy, a more competitive cost of 3.78 to 5.47 USD/kg H2 can be achieved [57].
- PRODUCT 1: Phenolic compounds belong to the wide class of phytonutrients, and find application in a variety of sectors such as food, feed, pharmaceutical and cosmetic industry. As they originate from natural sources, the diversity of biomolecules that can be obtained and the respective prices vary greatly, also depending on their purity and biological activity. The price of gallic and ellagic acids, two phenolic compounds present in chestnut extracts, is approximately 645 and 52,000 USD/kg, respectively (Sigma-Aldrich Company, Milano, Italy). The market of phenolic compounds is much diversified as they can be commercialized either as pure compounds or mixture of natural origin. In 2014, the global market of phytonutrients was estimated at 3.05 Billion USD and it is foreseen to reach 4.63 Billion USD within 2020, with Europe expecting to be the fastest-growing market in the near future [58]. As the amount of the phenolic compounds recovered from the hydrolyzate corresponds to the 0.74% (w/w) of the crude CS, it would be expected that about 138,600–207,900 kg/year could be obtained from CS.
- PRODUCT 2: The price of butyric acid is currently approximately 2000–2500 (USD/ton) [53], which represents an attractive income when transposed to the potential butyrate production from CS. Due to the variety of industrial applications for this organic acid, to the need to set aside petrochemicals based production processes, along with the newly explored pathways for the production of drop-in biofuels, the market size for butyrate was estimated in 30,000 (ton/year) in 2015 and in general “green” volatile fatty acids production exhibits a tendency to expand [59]. Using the butyrate production yield obtained in the present work (10.7 mM) and the amount of shell residues generated by the Mediterranean chestnut industry in 2014 (18,750–28,125 tons), it is possible to estimate a potential of 353,541–530,312 kg for butyrate production.
- REUSE 1: To become economically attractive, a detoxification process based on the use of an adsorbent matrix must foresee the reutilization of the adsorbent for additional cycles. As such, after the phenols desorption stage, AC can be reused for detoxification of a fresh hydrolyzate followed by phenolic compounds elution. This practice provides an environmental gain by avoidance of AC disposal. Additionally, the prospect of selectively recovering CS phenolic compounds with different antioxidant activities, as suggested by the RSA of the eluates from Elution I and II, is of major interest and deserves further investigation.
3. Materials and Methods
3.1. Chemicals
3.2. Biorefinery Stages
3.3. Pretreatment and Saccharification of CS
3.4. Detoxification of the CS Hydrolyzate
3.5. Desorption of Phenolic Compounds from the Charcoal
3.6. Fermentation of the Detoxified CS Hydrolyzate
3.7. Characterization of the samples
4. Conclusions
Acknowledgments
Author Contributions
Conflicts of Interest
References
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Sample | Adsorbed Phenolic Compounds (mg GAE/L) | Desorbed Phenolic Compounds (mg GAE/L) | RSA (%) |
---|---|---|---|
CS hydrolyzate | - | - | 21.0 ± 1.1 |
Activated charcoal | 525.8 ± 15.6 | - | - |
Elution I | 182.5 ± 6.2 | 343.4 ± 13.2 | 51.8 ± 1.6 |
Elution II | 156.2 ± 8.8 | 26.3 ± 2.3 | 26.0 ± 0.9 |
Total (Elution I + II) | - | 369.6 ± 11.5 | - |
Parameter | Result |
---|---|
Cumulative H2 production (mL/L) | 1598 ± 100 |
Hydrogen yield (mL/g CS) | 63.9 ± 4.0 |
H2/CO2 ratio (mol/mol) | 1.4 ± 0.1 |
Acetate production (mM) | 13.3 ± 1.6 |
Butyrate production (mM) | 10.7 ± 0.2 |
Formate production (mM) | 6.9 ± 0.2 |
Total sugars consumption (%) | 96.8 ± 0.7 |
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Morana, A.; Squillaci, G.; Paixão, S.M.; Alves, L.; Cara, F.L.; Moura, P. Development of an Energy Biorefinery Model for Chestnut (Castanea sativa Mill.) Shells. Energies 2017, 10, 1504. https://doi.org/10.3390/en10101504
Morana A, Squillaci G, Paixão SM, Alves L, Cara FL, Moura P. Development of an Energy Biorefinery Model for Chestnut (Castanea sativa Mill.) Shells. Energies. 2017; 10(10):1504. https://doi.org/10.3390/en10101504
Chicago/Turabian StyleMorana, Alessandra, Giuseppe Squillaci, Susana M. Paixão, Luís Alves, Francesco La Cara, and Patrícia Moura. 2017. "Development of an Energy Biorefinery Model for Chestnut (Castanea sativa Mill.) Shells" Energies 10, no. 10: 1504. https://doi.org/10.3390/en10101504