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"Fiori, Luca"
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Hydrothermal Carbonization of Waste Biomass: Process Design, Modeling, Energy Efficiency and Cost Analysis
2017
In this paper, a hydrothermal carbonization (HTC) process is designed and modeled on the basis of experimental data previously obtained for two representative organic waste materials: off-specification compost and grape marc. The process accounts for all the steps and equipment necessary to convert raw moist biomass into dry and pelletized hydrochar. By means of mass and thermal balances and based on common equations specific to the various equipment, thermal energy and power consumption were calculated at variable process conditions: HTC reactor temperature T: 180, 220, 250 °C; reaction time θ: 1, 3, 8 h. When operating the HTC plant with grape marc (65% moisture content) at optimized process conditions (T = 220 °C; θ = 1 h; dry biomass to water ratio = 0.19), thermal energy and power consumption were equal to 1170 kWh and 160 kWh per ton of hydrochar produced, respectively. Correspondingly, plant efficiency was 78%. In addition, the techno-economical aspects of the HTC process were analyzed in detail, considering both investment and production costs. The production cost of pelletized hydrochar and its break-even point were determined to be 157 €/ton and 200 €/ton, respectively. Such values make the use of hydrochar as a CO2 neutral biofuel attractive.
Journal Article
Full-Scale Sewage Sludge Reduction Technologies: A Review with a Focus on Energy Consumption
2023
In recent years, increasing attention has been paid to the problem of sewage sludge management and the relevant energy consumption, which represent the main cost items in wastewater treatment plants. Therefore, implementation of technologies that can reduce sludge production and ensure a positive impact on the energy of the entire sewage treatment plant has gained considerable importance in the scientific and technical community. The objective of this study was thus to screen full-scale sludge reduction technologies integrated into both the water line and the sludge line of a municipal sewage treatment plant with a sustainable impact on the overall balance of the plant. The results showed that, within the water line, ultrasound in the recirculation line of the activated sludge allowed for greater reductions in sludge production than the Cannibal and UTN systems, despite the higher energy consumption. CAMBITM, BioThelysTM, ExelysTM and TurboTec® enabled the greatest reductions in sludge production among the technologies integrated into the sludge line, and although they required a large amount of energy, this was partially offset by energy recovery in terms of additional biogas production.
Journal Article
Hydrothermal Carbonization Kinetics of Lignocellulosic Agro-Wastes: Experimental Data and Modeling
by
Lucian, Michela
,
Volpe, Maurizio
,
Fiori, Luca
in
activation energy
,
agro-wastes
,
Biodiesel fuels
2019
Olive trimmings (OT) were used as feedstock for an in-depth experimental study on the reaction kinetics controlling hydrothermal carbonization (HTC). OT were hydrothermally carbonized for a residence time τ of up to 8 h at temperatures between 180 and 250 °C to systematically investigate the chemical and energy properties changes of hydrochars during HTC. Additional experiments at 120 and 150 °C at τ = 0 h were carried out to analyze the heat-up transient phase required to reach the HTC set-point temperature. Furthermore, an original HTC reaction kinetics model was developed. The HTC reaction pathway was described through a lumped model, in which biomass is converted into solid (distinguished between primary and secondary char), liquid, and gaseous products. The kinetics model, written in MATLABTM, was used in best fitting routines with HTC experimental data obtained using OT and two other agro-wastes previously tested: grape marc and Opuntia Ficus Indica. The HTC kinetics model effectively predicts carbon distribution among HTC products versus time with the thermal transient phase included; it represents an effective tool for R&D in the HTC field. Importantly, both modeling and experimental data suggest that already during the heat-up phase, biomass greatly carbonizes, in particular at the highest temperature tested of 250 °C.
Journal Article
Coupling Hydrothermal Carbonization with Anaerobic Digestion for Sewage Sludge Treatment: Influence of HTC Liquor and Hydrochar on Biomethane Production
by
Fiori, Luca
,
Andreottola, Gianni
,
Ferrentino, Roberta
in
Alternative energy sources
,
anaerobic digestion
,
biochemical methane potential
2020
The present study addresses the coupling of hydrothermal carbonization (HTC) with anaerobic digestion (AD) in wastewater treatment plants. The improvement in biomethane production due to the recycling back to the anaerobic digester of HTC liquor and hydrochar generated from digested sludge is investigated and proved. Mixtures of different compositions of HTC liquor and hydrochar, as well as individual substrates, were tested. The biomethane yield reached 102 ± 3 mL CH4 g−1 COD when the HTC liquor was cycled back to the AD and treated together with primary and secondary sludge. Thus, the biomethane production was almost doubled compared to that of the AD of primary and secondary sludge (55 ± 20 mL CH4 g−1 COD). The benefit is even more significant when both the HTC liquor and the hydrochar were fed to the AD of primary and secondary sludge. The biomethane yield increased up to 187 ± 18 mL CH4 g−1 COD when 45% of hydrochar, with respect to the total feedstock, was added. These results highlight the improvement that the HTC process can bring to AD, enhancing biomethane production and promoting a sustainable solution for the treatment of the HTC liquor and possibly the hydrochar itself.
Journal Article
Prickly Pear Seed Oil Extraction, Chemical Characterization and Potential Health Benefits
by
Al-Naqeb, Ghanya
,
Ciolli, Marco
,
Fiori, Luca
in
biological activity
,
chemical characterization
,
Cold
2021
Prickly pear (Opuntia ficus-indica L.) is a member of the Cactaceae family originally grown in South America, and the plant is now distributed to many parts of the world, including the Middle East. The chemical composition and biological activities of different parts of prickly pear, including cladodes, flowers, fruit, seeds and seed oil, were previously investigated. Oil from the seeds has been known for its nutritive value and can be potentially used for health promotion. This review is an effort to cover what is actually known to date about the prickly pear seeds oil extraction, characteristics, chemical composition and potential health benefits to provide inspiration for the need of further investigation and future research. Prickly pear seeds oil has been extracted using different extraction techniques from conventional to advanced. Chemical characterization of the oil has been sufficiently studied, and it is sufficiently understood that the oil is a high linoleic oil. Its composition is influenced by the variety and environment and also by the method of extraction. The health benefits of the prickly pear seed oil were reported by many researchers. For future research, additional studies are warranted on mechanisms of action of the reported biological activities to develop nutraceutical products for the prevention of various chronic human diseases.
Journal Article
Sewage Sludge Hydrochar: An Option for Removal of Methylene Blue from Wastewater
by
Ceccato, Riccardo
,
Marchetti, Valentina
,
Andreottola, Gianni
in
adsorption
,
Chemical properties
,
hydrochar
2020
Municipal sewage sludge was subjected to a hydrothermal carbonization (HTC) process for developing a hydrochar with high adsorption capacity for water remediation in terms of dye removal. Three hydrochars were produced from municipal sewage sludge by performing HTC at 190, 220 and 250 °C, with a 3 h reaction time. Moreover, a portion of each hydrochar was subjected to a post-treatment with KOH in order to increase the adsorption capacity. Physicochemical properties of sludge samples, raw hydrochars and KOH-modified hydrochars were measured and batch adsorption studies were performed using methylene blue (MB) as a reference dye. Data revealed that both raw and modified hydrochars reached good MB removal efficiency for solutions with low MB concentrations; on the contrary, MB in high concentration solutions was efficiently removed only by modified hydrochars. Interestingly, the KOH treatment greatly improved the MB adsorption rate; the modified hydrochars were capable of capturing above 95% of the initial MB amount in less than 15 min. The physicochemical characterization indicates that alkali modification caused a change in the hydrochar surface making it more chemically homogeneous, which is particularly evident for the 250 °C hydrochar. Thus, the adsorption process can be regarded as a complex result of various phenomena, including physi- and chemi-sorption, acid–base and redox equilibria.
Journal Article
Thermal Analysis and Kinetic Modeling of Pyrolysis and Oxidation of Hydrochars
2022
This study examines the kinetics of pyrolysis and oxidation of hydrochars through thermal analysis. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) techniques were used to investigate the decomposition profiles and develop two distributed activation energy models (DAEM) of hydrochars derived from the hydrothermal carbonization of grape seeds produced at different temperatures (180, 220, and 250 °C). Data were collected at 1, 3, and 10 °C/min between 30 and 700 °C. TGA data highlighted a decomposition profile similar to that of the raw biomass for hydrochars obtained at 180 and 220 °C (with a clear distinction between oil, cellulosic, hemicellulosic, and lignin-like compounds), while presenting a more stable profile for the 250 °C hydrochar. DSC showed a certain exothermic behavior during pyrolysis of hydrochars, an aspect also investigated through thermodynamic simulations in Aspen Plus. Regarding the DAEM, according to a Gaussian model, the severity of the treatment slightly affects kinetic parameters, with average activation energies between 193 and 220 kJ/mol. Meanwhile, the Miura–Maki model highlights the distributions of the activation energy and the pre-exponential factor during the decomposition.
Journal Article
Hydrothermal Carbonization as a Strategy for Sewage Sludge Management: Influence of Process Withdrawal Point on Hydrochar Properties
by
Mimmo, Tanja
,
Volpe, Maurizio
,
Andreottola, Gianni
in
Alternative energy sources
,
Chemical oxygen demand
,
Emissions
2020
Conventional activated sludge systems, still widely used to treat wastewater, produce large amounts of solid waste that is commonly landfilled or incinerated. This study addresses the potential use of Hydrothermal Carbonization (HTC) to valorize sewage sludge residues examining the properties of hydrochars depending on HTC process conditions and sewage sludge withdrawal point. With increasing HTC severity (process residence time and temperature), solid yield, total Chemical Oxygen Demand (COD) and solid pH decrease while ash content increases. Hydrochars produced from primary (thickened) and secondary (digested and dewatered) sludge show peculiar distinct properties. Hydrochars produced from thickened sludge show good fuel properties in terms of Higher Heating Value (HHV) and reduced ash content. However, relatively high volatile matter and O:C and H:C ratios result in thermal reactivity significantly higher than typical coals. Both series of carbonized secondary sludges show neutral pH, low COD, enhanced phosphorous content and low heavy metals concentration: as a whole, they show properties compatible with their use as soil amendments.
Journal Article
Cationic Dye Adsorption on Hydrochars of Winery and Citrus Juice Industries Residues: Performance, Mechanism, and Thermodynamics
2020
With the increasing needs of clean water supplies, the use of biomass wastes and residues for environmental remediation is essential for environmental sustainability. In this study, the residues from winery and citrus juice industries, namely grape skin and orange peel, respectively, were first converted to hydrochars by hydrothermal carbonization (HTC) and then a cationic dye (methylene blue) adsorption was studied on hydrochars. Hydrochars from both feedstocks were produced at three different temperatures (180, 220, and 250 °C) and a fixed residence time (1 h) to evaluate the hydrochar’s performance on the dye adsorption. The hydrochars were characterized in terms of their pH, pH at point of zero charge (pHPZC), surface functionalities, and surface area. A batch adsorption study of the dye was carried out with variable adsorbate concentration, pH, and temperature. Two adsorption isotherms namely Langmuir and Freundlich models were fitted at 4, 20, and 36 °C. The thermodynamic properties of adsorption (Gibbs free energy (ΔG), enthalpy (ΔH) and entropy (ΔS)) were evaluated from the isotherms fittings. Results showed that the dye adsorption on both hydrochars was significant and followed Langmuir isotherm. The maximum adsorption capacity on citrus waste hydrochar was higher than the winery waste hydrochar at any corresponding HTC temperature. Although hydrochars showed the lowest surface area (46.16 ± 0.11 and 34.08 ± 1.23 m2/g for citrus and winery wastes, respectively) at 180 °C, their adsorption was the highest, owing to their maximum density of total oxygen functional groups (23.24 ± 0.22 and 32.69 ± 1.39 µmol/m2 for citrus and winery wastes, respectively), which decreased with the increase in HTC temperature. This research shows a sustainable route for the production of highly effective adsorbent materials at lower HTC temperatures from citrus and winery wastes.
Journal Article
Supercritical Water Gasification of Biomass in a Ceramic Reactor: Long-Time Batch Experiments
by
Rolli, Birgit
,
Fiori, Luca
,
Kruse, Andrea
in
Alternative energy sources
,
Alumina
,
alumina reactor
2017
Supercritical water gasification (SCWG) is an emerging technology for the valorization of (wet) biomass into a valuable fuel gas composed of hydrogen and/or methane. The harsh temperature and pressure conditions involved in SCWG (T > 375 °C, p > 22 MPa) are definitely a challenge for the manufacturing of the reactors. Metal surfaces are indeed subject to corrosion under hydrothermal conditions, and expensive special alloys are needed to overcome such drawbacks. A ceramic reactor could be a potential solution to this issue. Finding a suitable material is, however, complex because the catalytic effect of the material can influence the gas yield and composition. In this work, a research reactor featuring an internal alumina inlay was utilized to conduct long-time (16 h) batch tests with real biomasses and model compounds. The same experiments were also conducted in batch reactors made of stainless steel and Inconel 625. The results show that the three devices have similar performance patterns in terms of gas production, although in the ceramic reactor higher yields of C2+ hydrocarbons were obtained. The SEM observation of the reacted alumina surface revealed a good resistance of such material to supercritical conditions, even though some intergranular corrosion was observed.
Journal Article