• Energy Research

In this contribution, we successfully applied demineralization (i.e., solvent-assisted separation and acid washing) for the removal of carbonaceous solids and inorganics from a biocrude obtained from the catalytic hydrothermal liquefaction (HTL) of Miscanthus. The experimental results of all six employed acids showed that 0.1 M H2SO4 was the most effective and significantly reduced metallic (Fe by 93.9%, <15 µg/g and Mg by 95.6%, 2.1 µg/g) and ash content (by 92.7% to 337 µg/g) from the already filtered biocrude. The utilized demineralizing agents caused a loss of nitrogen and of organic carbon (1% total organic carbon (TOC) and 0.058% total nitrogen (TN) in 0.1 M H2SO4). Gas chromatography-mass spectrometry (GC–MS) results clarified the nature of this loss, showing that 54% of ketones and 39% of alcohols were removed when 0.1 M H2SO4 was employed. Furthermore, FT-IR spectra remained the same before and after acid washing without affecting any functional groups. This work therefore proposes demineralization as a viable route for the removal of high inorganic content from lignocellulosic HTL biocrudes.

In this contribution, we successfully applied demineralization (i.e., solvent-assisted separation and acid washing) for the removal of carbonaceous solids and inorganics from a biocrude obtained from the catalytic hydrothermal liquefaction (HTL) of Miscanthus. The experimental results of all six employed acids showed that 0.1 M H2SO4 was the most effective and significantly reduced metallic (Fe by 93.9%, <15 µg/g and Mg by 95.6%, 2.1 µg/g) and ash content (by 92.7% to 337 µg/g) from the already filtered biocrude. The utilized demineralizing agents caused a loss of nitrogen and of organic carbon (1% total organic carbon (TOC) and 0.058% total nitrogen (TN) in 0.1 M H2SO4). Gas chromatography-mass spectrometry (GC–MS) results clarified the nature of this loss, showing that 54% of ketones and 39% of alcohols were removed when 0.1 M H2SO4 was employed. Furthermore, FT-IR spectra remained the same before and after acid washing without affecting any functional groups. This work therefore proposes demineralization as a viable route for the removal of high inorganic content from lignocellulosic HTL biocrudes.

In this paper, the use of grape marc for energy purposes was investigated. Grape marc is a residual lignocellulosic by-product from the winery industry, which is present in every world region where vine-making is addressed. Among the others, hydrothermal carbonization was chosen as a promising alternative thermochemical process, suitable for the treatment of this high moisture substrate. Through a 50 mL experimental apparatus, hydrothermal carbonization tests were performed at several temperatures (namely: 180, 220 and 250 °C) and residence times (1, 3, 8 h). Analyses on both the solid and the gaseous phases obtained downstream of the process were performed. In particular, solid and gas yields versus the process operational conditions were studied and the obtained hydrochar was evaluated in terms of calorific value, elemental analysis, and thermal stability. Data testify that hydrochar form grape marc presents interesting values of HHV (in the range 19.8-24.1 MJ/kg) and physical-chemical characteristics which make hydrochar exploitable as a solid biofuel. In the meanwhile, the amount of gases produced is very small, if compared to other thermochemical processes. This represents an interesting result when considering environmental issues. Statistical analysis of data allows to affirm that, in the chosen range of operational conditions, the process is influenced more by temperature than residence time. These preliminary results support the option of upgrading grape marc toward its energetic valorisation through hydrothermal carbonization.

In this paper, the use of grape marc for energy purposes was investigated. Grape marc is a residual lignocellulosic by-product from the winery industry, which is present in every world region where vine-making is addressed. Among the others, hydrothermal carbonization was chosen as a promising alternative thermochemical process, suitable for the treatment of this high moisture substrate. Through a 50 mL experimental apparatus, hydrothermal carbonization tests were performed at several temperatures (namely: 180, 220 and 250 °C) and residence times (1, 3, 8 h). Analyses on both the solid and the gaseous phases obtained downstream of the process were performed. In particular, solid and gas yields versus the process operational conditions were studied and the obtained hydrochar was evaluated in terms of calorific value, elemental analysis, and thermal stability. Data testify that hydrochar form grape marc presents interesting values of HHV (in the range 19.8-24.1 MJ/kg) and physical-chemical characteristics which make hydrochar exploitable as a solid biofuel. In the meanwhile, the amount of gases produced is very small, if compared to other thermochemical processes. This represents an interesting result when considering environmental issues. Statistical analysis of data allows to affirm that, in the chosen range of operational conditions, the process is influenced more by temperature than residence time. These preliminary results support the option of upgrading grape marc toward its energetic valorisation through hydrothermal carbonization.

Abstract Supercritical water gasification (SCWG) is an interesting technology for the production of energy from wet and residual biomass. To date, the complete understanding of the fundamental phenomena involved in SCWG is still an open issue. An interesting aspect to be investigated is represented by the interactions among the single constituents of biomass, such as cellulose and lignin. This can be accomplished by using glucose and phenol as model compounds. In the present study, four glucose/phenol mixtures were utilized. All mixtures presented a constant organics mass fraction of 5%, where the relative fraction of phenol ranged from 0% (pure glucose) to 30%. The mixtures were gasified at 400 °C and 25.0 MPa in a continuous tubular reactor, with a residence time between 10 and 240 s. Results showed that, at the considered reaction conditions, phenol mostly behaves as a sort of inert in terms of total gas production, although it plays an inhibitory action towards H 2 . The analysis of the liquid phase revealed that phenol likely inhibits Cannizzaro and de-carbonylation reactions and it advantages the pathways involving de-hydration reactions.

Abstract Supercritical water gasification (SCWG) is an interesting technology for the production of energy from wet and residual biomass. To date, the complete understanding of the fundamental phenomena involved in SCWG is still an open issue. An interesting aspect to be investigated is represented by the interactions among the single constituents of biomass, such as cellulose and lignin. This can be accomplished by using glucose and phenol as model compounds. In the present study, four glucose/phenol mixtures were utilized. All mixtures presented a constant organics mass fraction of 5%, where the relative fraction of phenol ranged from 0% (pure glucose) to 30%. The mixtures were gasified at 400 °C and 25.0 MPa in a continuous tubular reactor, with a residence time between 10 and 240 s. Results showed that, at the considered reaction conditions, phenol mostly behaves as a sort of inert in terms of total gas production, although it plays an inhibitory action towards H 2 . The analysis of the liquid phase revealed that phenol likely inhibits Cannizzaro and de-carbonylation reactions and it advantages the pathways involving de-hydration reactions.

In this study, hydrothermal co-liquefaction of restaurant waste for biocrude production was conducted. The feedstock was resembled using the organic fraction of restaurant waste and low-density polyethylene, polypropylene, polystyrene, and polyethylene terephthalate, four plastic types commonly present in municipal solid waste. Using design of experiment and a face-centered central composite design, three factors (feedstock plastic fraction, temperature, time) were varied at three levels each: feedstock plastic fraction (0, 0.25, 0.5), temperature (290 °C, 330 °C, 370 °C), and reaction time (0 min, 30 min, 60 min). The literature reports positive synergistic interactions in hydrothermal co-liquefaction of biomass and plastics; however, in this work, only negative synergistic interactions could be observed. A reason could be the high thermal stability of produced fatty acids that give little room for interactions with plastics. At the same time, mass might transfer to other product phases.