Hydrochar and hydrochar co-compost from OFMSW digestate for soil application: 1. production and chemical characterization.

The best available technique (BAT) for managing the organic fraction of municipal solid waste (OFMSW) is represented by anaerobic digestion (AD) and subsequent composting. This research explored a new industrial model in the framework of the C2Land international project, with the insertion of hydrothermal carbonization (HTC) as a post-treatment for OFMSW digestate. The reaction was set for 3 h at three different temperatures (180 ÷ 220 °C); the wet solid hydrochar obtained after filtration was then co-composted with greenery waste as a bulking agent and untreated OFMSW digestate in four different proportions in bench-scale bioreactors. The hydrochars and the hydrochar co-composts were suitable for agro-industrial applications, while the HTC liquors were tested in biochemical methane potential (BMP) for internal recirculation to AD. The scenarios proposed can be beneficial for plant enhancement and increased biogas production. This study reports results connected to the production phase. Mass balances confirmed that, during HTC, phosphorus precipitated into the solid products, organic nitrogen partially mineralized into ammonium, and oxidizable organic matter solubilized. The selected hydrochar obtained at 200 °C had mean (dry) solid, liquid, and gaseous yields equal to 77, 20, and 3 %db, respectively. The dynamic respirometric index (DRI) confirmed that the reproduced BAT for the composting process was effective in producing high-quality hydrochar co-composts in terms of biological stability. The BMP tests on HTC liquors showed some inhibitory effects, suggesting the need for future studies with inoculum adaptation and co-digestion, to dilute toxic compounds and enhance biogas production. Part 2 of this study describes the agro-environmental properties of hydrochars and hydrochar co-composts, including the beneficial effect of composting on hydrochars phytotoxicity.

Valorization of cow manure via hydrothermal carbonization for phosphorus recovery and adsorbents for water treatment.

The increased quantities of manure being generated by livestock and their extensive agronomic use have raised concerns around run-off impacting soil and groundwater quality. Manure contains valuable nutrients (especially phosphorus) that are critical to agriculture, but when directly land-applied the run-off of such nutrients contributes to eutrophication of waterways. This study investigates the hydrothermal carbonization of cow manure at two industrially feasible process extremes: 190 °C, 1 h and 230 °C, 3 h, to concentrate and then recover phosphorus from the solid hydrochar via acid leaching and precipitation. Up to 98 wt% of phosphorus initially present in the hydrochar (88% in the raw manure) can be recovered, with the dominant crystalline species being hydroxyapatite. Acid leached hydrochars were subsequently pyrolyzed at 600 °C for 30 min, and then evaluated as adsorbent materials for water remediation by using methylene blue as a model adsorbate. Although pyrolyzed hydrochars have surface areas an order of magnitude higher (160-236 m2/g) than the non-pyrolyzed acid leached hydrochars (11-23 m2/g), their adsorption capacity is three times lower. Furthermore, while the higher carbonization temperature leads to greater recovery of phosphorus, it likewise leads to higher heavy metal concentrations in the precipitate (ranging from 0.1 to 100 mgmetal/gppt). As such, lower temperature carbonization followed by acid-extraction - without further solid processing - is a potential pathway to recover phosphorus and adsorbent materials.

Hydrochar and hydrochar co-compost from OFMSW digestate for soil application: 3. Toxicological evaluation.

Modern societies produce ever-increasing amounts of waste, e.g. organic fraction of municipal solid waste (OFMSW). According to the best available techniques, OFMSW should be treated through anaerobic digestion to recover biogas and subsequently composted. An innovative scheme is under investigation, where anaerobic digestion is combined with hydrothermal carbonization (HTC) and composting. The final product, referred to as hydrochar co-compost (HCO), is under study to be used as an unconventional soil improver/fertilizer. Recent studies showed that HCO is not phytotoxic. However, nothing is known about the toxicity of HCO on cells as part and organisms as a whole. This study aims to investigate in vitro genotoxicity and cytotoxicity of the HCO and its precursors in the production process. In particular, we tested water and methanolic extracts of HCO (WEHCO and MEHCO) from one side and methanolic extracts of hydrochar (MEH) and OFMSW digestate (MED) as well as liquor produced downstream HTC (HTCL) from the other side. Genotoxicity was investigated using cytokinesis-block micronucleus assay in Chinese Hamster Ovarian K1 (CHO-K1) cells. Cytotoxicity was tested in vitro against a panel of human cells line. Zebrafish embryo toxicity upon MEH treatment was also investigated. Results show that incubation of CHO-K1 cells with all the tested samples at different concentrations did not cause any induction of micronucleus formation compared to the vehicle-treated control. Treatment of cells with MEH, MED, HTCL and MEHCO, but not WEHCO, induced some degree of cytotoxicity and MEH showed to be more cytotoxic against tested cells compared to the MEHCO. Toxicity effect at the highest tested concentrations of MEH on zebrafish embryos resulted in coagulation, induction of pericardial edema and death. In conclusion, the hydrochar co-compost cytotoxicity is similar to standard compost cytotoxicity. Hence composting the hydrochar from OFMSW digestate is a good step to eliminate the cytotoxicity of hydrochar.

Hydrochar and hydrochar co-compost from OFMSW digestate for soil application: 2. agro-environmental properties.

The work concerns the study of the hydrochar from digestate and hydrochar co-compost characterization as amendments. The processes for hydrochar and co-compost production were described in Part 1 of this work (Scrinzi et al., 2022). The amendment properties of hydrochar (produced at 180-200-220 °C for 3 h) and co-composts (25%, 50%, and 75% hydrochar percentage of digestate substitution) were assessed by phytotoxicity, plant growth bioassay, and soil effect. Different seeds species (Lepidium sativum, Cucumis sativus, and Sorghum bicolor sp.) were dosed at increased concentrations using both wet raw amendments and their water extracts. The chemical characterization showed phytotoxic compounds content depending on both the initial feedstock (digestate) and the HTC process; at the same time, the analysis highlighted the reduction of these compounds by composting (organic acid, polyphenols, salt concentration). The dose-response was analyzed by the Cedergreen-Streibig-Ritz model and the half-maximal effective concentration (EC50) was calculated based on this equation. The soil properties and GHG emissions measurements (CH4, CO2, N2O, and NH3) highlighted the effect on N dynamics and on soil respiration induced by substrates. The HC200 soil application determined a significant impact on CO2 and N2O emission and NH3 volatilization (10.82 mol CO2/m2; 51.45 mmol N2O/m2; 112 mol NH3/m2) and a significant reduction of total N and TOC (46% of TKN and 49% of TOC). The co-compost (75%) showed specific effects after soil application compared to other samples an increase of available P (48%), a greater content of nitrogen (1626 mg/kg dry basis), and a reduction of organic carbon (17%). Our results demonstrate the good quality of co-compost and at the same time the validity of this post-treatment for addressing many issues related to hydrochar use in the soil as an amendment, confirming the suitability of HTC process integration for digestate treatment in anaerobic digestion plants.

Coupling hydrothermal carbonization and anaerobic digestion for sewage digestate management: Influence of hydrothermal treatment time on dewaterability and bio-methane production.

Hydrothermal carbonization (HTC) technology is addressed in the framework of sewage digestate management. HTC converts digestate into a stabilized and sterilized solid (the hydrochar) and a liquor (HTCL) rich in organic carbon. This study aims to optimize the HTC operating parameters, namely the treatment time, in terms of hydrochar production, HTC slurry dewaterability, HTCL bio-methane yields in anaerobic digestion (AD), and process energy consumption. Digestate slurry was processed through HTC at different treatment times (0.5, 1, 2 and 3 h) at 190 °C, and the dewaterability of the treated slurries was addressed through capillary suction time and centrifuge lab-testing. In addition, biochemical methane potential (BMP) tests were conducted for HTCL under mesophilic conditions. Results show that by increasing the HTC treatment time the dewaterability was further improved, ammonium concentration in HTCL increased, and methane potential of HTCL decreased. 0.5 h HTCL had the highest bio-methane potential of 142 ± 3 mL CH4/g COD yet the treatment time was not sufficient for improving the slurry's dewaterability. HTC treatment time of 1 h at 190 °C was identified as the optimum trade-off for improved dewaterability and utilisation of HTCL for biogas production. 1 h HTCL bio-methane potential can cover around 25% of the HTC and AD thermal and electrical energy needs without considering the eventual use of the hydrochar as a biofuel.

Prickly Pear Seed Oil Extraction, Chemical Characterization and Potential Health Benefits.

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.

Realization of a solar hydrothermal carbonization reactor: A zero-energy technology for waste biomass valorization.

Research around hydrothermal carbonization (HTC) has seen a huge development in recent years, materializing in the first pilot and industrial plants. Even though HTC reactions are slightly exothermic, the overall process entails energy consumption to both reach operating conditions and tackle heat losses. To face this issue and to develop a zero-energy process, this work proposes an innovative solution: the coupling of an HTC reactor with a solar concentrator, designed to fully cover the HTC energy needs. A 300 ml stainless steel HTC reactor was constructed and positioned on the focus of a parabolic dish concentrator (PDC), consisting of one parabolic mirror of 0.8 m2. To maximize the light absorption, the illuminated side of the HTC reactor was coated with a thin layer of nanostructured copper oxide, realized via electron beam deposition. Then, the effectiveness of the hybrid solar-HTC solution was demonstrated by carrying out an experimental campaign on a residual agro-biomass (grape seeds), which was treated at 180, 220, and 250 °C for 2 h. The coating confers excellent absorbing performances to the system, exhibiting an absorptance of up to 95.6% (at 300 nm wavelength). Heating times, yields, composition, and energy properties of "solar hydrochars" resemble those of studies performed in traditional HTC systems. This research work proves the feasibility of the solar-HTC prototype apparatus and opens the way to the development of a zero-energy solar-HTC technology.

Hydrothermal Conversion of Spent Sugar Beets into High-Value Platform Molecules.

The growing importance of bio-based products, combined with the desire to decrease the production of wastes, boosts the necessity to use wastes as raw materials for bio-based products. A waste material with a large potential is spent sugar beets, which are mainly used as animal feeds or fertilizers. After hydrothermal treatment, the produced chars exhibited an H/C ratio of 1.2 and a higher heating value of 22.7 MJ/kg, which were similar to that of subbituminous coal and higher than that of lignite. Moreover, the treatment of 25 g/L of glucose and 22 g/L of fructose by heating up to 160 °C led to a possible application of spent sugar beets for the production of 5-hydroxymethylfurfural. In the present study, the maximum concentration of 5-hydroxymethylfurfural was 3.4 g/L after heating up to 200 °C.

Green solvents to enhance hydrochar quality and clarify effects of secondary char.

Several limitations hinder the industrial-scale implementation of hydrothermal carbonization (HTC) of biomass, especially the quality of as-carbonized hydrochar. This work investigates solvent extraction of hydrochars to enhance their potential applications. Hydrochars were produced at several HTC temperatures (190, 220, 250 °C) from cellulose and extracted using combinations of green polar solvents (ethyl acetate, acetone, and methanol). Results show that the composition of the extractable fraction resembles that of the HTC liquor, rich in carboxylic acids and furan derivatives, while the non-extractable solid phase shows improved thermal profiles devoid of highly volatile compounds. Carbon microspheres (non-dissolvable secondary char) are unaffected by extraction. The organics adsorbed on the hydrochar surface comprise highly volatile species and solvent washing effectively removes them.

Anaerobic degradation of digestate based hydrothermal carbonization products in a continuous hybrid fixed bed anaerobic filter.

This study investigates the suitability of continuous hybrid fixed bed anaerobic filter reactor for treating sewage and agro-industrial digestate hydrothermal carbonization (HTC) products; hydrochar and HTC liquor (HTCL). The reactor was operated for 300 days under mesophilic conditions at different organic loading rates (OLR); maximum OLRs of 7.4 and 10 gCOD/L/d were reached while treating HTC liquor and slurry, respectively. 15 g/L hydrochar were added to the reactor as a supplement while treating HTCL solely thus increasing the biogas production up to 153%. The reactor was fed with HTCL and hydrochar with an increasing mixing ratio, and the co-digestion impact was dependent on hydrochar concentrations. The results of the study indicate that the hybrid fixed bed anaerobic filter reactor is a promising anaerobic digestion configuration for treating HTCL and overcoming the HTC upscaling challenges, and the suitability of digestate hydrochar utilization as supplement material for anaerobic digestion.

Integrated thermochemical conversion process for valorizing mixed agricultural and dairy waste to nutrient-enriched biochars and biofuels.

Hydrothermal carbonization (HTC) and pyrolysis are two promising thermochemical conversion strategies to valorize agricultural wastes, yet neither process can be implemented alone to sustainably upgrade both wet and dry feedstocks. HTC is ideal for wet feedstocks, such as manure, but its solid hydrochars suffer from low surface area and stability. Pyrolysis is well suited to dry agricultural residues, but pyrolysis biochars have low nutrient contents and bio-oils are often highly oxygenated. We propose an integrated process that co-pyrolyzes a nutrient-rich cow manure hydrochar with raw agricultural residues, which effectively reduces the environmental impact of these wastes while producing value-added bioproducts. Biochars produced from the proposed process are more suitable for soil amendments due to their enhancement in bioavailable nutrients and surface area than the manure hydrochars and raw biomass. Co-pyrolysis of blends enriched with cow manure yield oils higher in alkanes and alkenes with fewer oxygenated compounds.

Hydrothermal carbonization coupled with anaerobic digestion for the valorization of the organic fraction of municipal solid waste.

Hydrothermal carbonization (HTC) was evaluated as a promising treatment to enhance the biomethane potential during anaerobic digestion (AD) of the organic fraction of municipal solid waste (OFMSW). The OFMSW was carbonized at different conditions and HTC products were tested for biomethane potential into AD. Results proved that the use of HTC liquid and slurry into AD led to an increase in biomethane production up to 37% and 363%, respectively, compared to OFMSW. Methane production increased as the HTC process severity decreased, reaching its maximum at 180 °C, 1 h for both HTC products. Energy assessment demonstrated that the combustion of biogas produced by AD of HTC liquid and slurries covers up to 30% and 104% of the HTC thermal demand, respectively. When the energy from hydrochar and biogas combustion was recovered, the process efficiency reached 60%. Hence, HTC coupled with AD demonstrates to be an efficient way to valorize OFMSW.

Hydrothermal carbonization of Opuntia ficus-indica cladodes: Role of process parameters on hydrochar properties.

Opuntia ficus-indica cladodes are a potential source of solid biofuel from marginal, dry land. Experiments assessed the effects of temperature (180-250°C), reaction time (0.5-3h) and biomass to water ratio (B/W; 0.07-0.30) on chars produced via hydrothermal carbonization. Multivariate linear regression demonstrated that the three process parameters are critically important to hydrochar solid yield, while B/W drives energy yield. Heating value increased together with temperature and reaction time and was maximized at intermediate B/W (0.14-0.20). Microscopy shows evidence of secondary char formed at higher temperatures and B/W ratios. X-ray diffraction, thermogravimetric data, microscopy and inductively coupled plasma mass spectrometry suggest that calcium oxalate in the raw biomass remains in the hydrochar; at higher temperatures, the mineral decomposes into CO2 and may catalyze char/tar decomposition.

One stage olive mill waste streams valorisation via hydrothermal carbonisation.

An olive waste stream mixture, coming from a three phase-continuous centrifugation olive oil mill industry, with a typical wet basis mass composition of olive pulp 39 wt%, kernels 5 wt% and olive mill waste water 56 wt%, was subjected to hydrothermal carbonisation (HTC) at 180, 220 and 250 °C for a 3-hour residence time in a 2-litre stainless steel electrically heated batch reactor. The raw feedstock and corresponding hydrochars were characterised in terms of proximate and ultimate analyses, higher heating values and energy properties. Results showed an increase in carbonisation of samples with increasing HTC severity and an energy densification ratio up to 142% (at 250 °C). Hydrochar obtained at 250 °C was successfully pelletised using a lab scale pelletiser without binders or expensive drying procedures. Energy characterisation (HHV, TGA), ATR-FTIR analysis, fouling index evaluation and pelletisation results suggested that olive mill waste hydrochars could be used as energy dense and mechanical stable bio-fuels. Characterisation of HTC residues in terms of mineral content via induced coupled plasma optical emission spectroscopy (ICP-OES) as well as Total and Dissolved Organic Carbon enabled to evaluate their potential use as soil improvers. Nutrients and polyphenolic compounds in HTC liquid fractions were evaluated for the estimation of their potential use as liquid fertilisers. Results showed that HTC could represent a viable route for the valorisation of olive mill industry waste streams.

Spent coffee enhanced biomethane potential via an integrated hydrothermal carbonization-anaerobic digestion process.

This study reports the implications of using spent coffee hydrochar as substrate for anaerobic digestion (AD) processes. Three different spent coffee hydrochars produced at 180, 220 and 250 °C, 1 h residence time, were investigated for their biomethane potential in AD process inoculated with cow manure. Spent coffee hydrochars were characterized in terms of ultimate, proximate and higher heating value (HHV), and their theoretical bio-methane yield evaluated using Boyle-Buswell equation and compared to the experimental values. The results were then analyzed using the modified Gompertz equation to determine the main AD evolution parameters. Different hydrochar properties were related to AD process performances. AD of spent coffee hydrochars produced at 180 °C showed the highest biomethane production rate (46 mL CH4/gVS.d), a biomethane potential of 491 mL/gVS (AD lasting 25 days), and a biomethane gas daily composition of about 70%.

Agro-industrial waste to solid biofuel 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.

Hydrothermal carbonization of off-specification compost: a byproduct of the organic municipal solid waste treatment.

The possibility to apply the hydrothermal carbonization (HTC) process to off-specification compost (EWC 19.05.03) at present landfilled was investigated in this work. The aim was to produce a carbonaceous solid fuel for energy valorization, with the perspective of using HTC as a complementary technology to common organic waste treatments. Thus, samples of EWC 19.05.03 produced by a composting plant were processed through HTC in a batch reactor. Analytical activities allowed to characterize the HTC products and their yields. The hydrochar was characterized in terms of heating value, thermal stability and C, H, O, N, S and ash content. The liquid phase was characterized in terms of total organic carbon and mineral content. The composition of the gas phase was measured. Results show that the produced hydrochar has a great potentiality for use as solid fuel.

Supercritical water gasification of biomass for H2 production: process design.

The supercritical water gasification (SCWG) of biomass for H(2) production is analyzed in terms of process development and energetic self-sustainability. The conceptual design of a plant is proposed and the SCWG process involving several substrates (glycerol, microalgae, sewage sludge, grape marc, phenol) is simulated by means of AspenPlus™. The influence of various parameters - biomass concentration and typology, reaction pressure and temperature - is analyzed. The process accounts for the possibility of exploiting the mechanical energy of compressed syngas (later burned to sustain the SCWG reaction) through expansion in turbines, while purified H(2) is fed to fuel cells. Results show that the SCWG reaction can be energetically self-sustained if minimum feed biomass concentrations of 15-25% are adopted. Interestingly, the H(2) yields are found to be maximal at similar feed concentrations. Finally, an energy balance is performed showing that the whole process could provide a net power of about 150 kW(e)/(1000 kg(feed)/h).

Modeling of the devolatilization kinetics during pyrolysis of grape residues.

Thermo-gravimetric analysis (TGA) was performed on grape seeds, skins, stalks, marc, vine-branches, grape seed oil and grape seeds depleted of their oil. The TGA data was modeled through Gaussian, logistic and Miura-Maki distributed activation energy models (DAEMs) and a simpler two-parameter model. All DAEMs allowed an accurate prediction of the TGA data; however, the Miura-Maki model could not account for the complete range of conversion for some substrates, while the Gaussian and logistic DAEMs suffered from the interrelation between the pre-exponential factor k0 and the mean activation energy E0--an obstacle that can be overcome by fixing the value of k0 a priori. The results confirmed the capabilities of DAEMs but also highlighted some drawbacks in their application to certain thermodegradation experimental data.

Supercritical water gasification of biomass: Thermodynamic constraints.

In the present work, the supercritical water gasification (SCWG) of biomass is analyzed with a view to outlining the possible thermodynamic constraints that must be taken into account to develop this new process. In particular, issues concerning the formation of solid carbon and the process heat duty are discussed. The analysis is conducted by means of a two-phase non-stoichiometric thermodynamic model, based on Gibbs free energy minimization. Results show that char formation at equilibrium only occurs at high biomass concentrations, with a strong dependence on biomass composition. As regards the process heat duty, SCWG is mostly endothermic when biomass concentration is low, although a very small amount of oxidizing agent is able to make the process exothermic, with only a small loss in the heating value of the syngas produced.