Co-hydrothermal carbonization with process water recirculation as a valuable strategy to enhance hydrochar recovery with high energy efficiency.

This study aims at valorizing the residual aqueous phase from hydrothermal carbonization (HTC) of Sicilian agro-wastes in order to enhance the hydrochar recovery, positively affecting the process energy balance. Process waters (PW) obtained from HTC and co-HTC using orange peel waste and fennel plant residues were used as recycled solvent in experiments carried out at the temperatures of 180 and 230 °C. The results showed that an additional hydrochar formation was promoted during recirculation of solvent, leading to average increments of solid mass yield of 10.5 wt% for tests conducted at 180 °C and 3.9 wt% for 230 °C. After five consecutive recirculation phases in co-HTC runs, the hydrochar yield increased up to 18.2 wt%. The low H/C and O/C atomic ratios values, found after recirculation, indicate that organic acids, accumulated in the PW, may catalyze the process and promote the biomass deoxygenation by boosting dehydration and decarboxylation. The recovered PWs from conversion steps with deionized water were also carbonized in absence of the solid feedstock in order to quantify their contribution in hydrochar formation during recirculation and thus the synergistic interactions. After recirculation, energy recovery averagely augmented by more than threefold, showing that the proposed strategy could significantly improve the sustainability of HTC.

Role of acidic hydrochar on dechlorination of waste PVC in high temperature hydrothermal treatment and fuel properties enhancement of solid residues.

In this study, the chlorine mitigation from waste polyvinyl chloride (WPVC) during high temperature co-hydrothermal treatment (co-HTT) and the properties of the generated solid products were assessed. WPVC was co-fed with acidic hydrochar (AHC), which was produced via hydrothermal carbonization of pineapple waste in the presence of citric acid water solution. High temperature co-HTT experiments were performed at 300-350 °C, 0.25-4 h of reaction time, and 0-20 wt% AHC loading. Co-HTT solid products (co-HTT_SP) were characterized via proximate analysis, ultimate analyses, combustion analysis, and ash analysis. The results show that the addition of 5% AHC enhances the dechlorination efficiency (DE) of WPVC from 89.35% to 97.66% at 325 °C and 0.5 h. The highest DE, reaching 99.46%, was achieved at 350 °C and 1 h in the presence of 5 wt% AHC. Furthermore, loading 5% AHC improved the higher heat value (HHV) of the solid products from 23.09 to 31.25 MJ/kg at 325 °C and 0.5 h. The maximum HHV (34.77 MJ/kg) of a solid product was achieved at 350 °C, 4 h, in the presence of 5 wt% of AHC. The co-HTT solids shown low slagging indices, fouling indices, alkali indices, and medium chlorine contents. These findings support the viability of WPVC conversion into clean solid fuel via co-HTT.

Highly ordered CaO from cuttlefish bone calcination for the efficient adsorption of methylene blue from water.

The aim of this study is to synthesize cheap and highly ordered CaO from cuttlefish bone (CFB) as a green alternative to conventional adsorbents such as activated carbon. This study focuses on the synthesis of highly ordered CaO via calcination of CFB, at two different temperatures (900 and 1000°C) and two holding times (0.5 and 1 h), as a potential green route for water remediation. The as-prepared highly ordered CaO was tested as an adsorbent using methylene blue (MB) as a model compound for dye contaminants in water. Different CaO adsorbent doses (0.05, 0.2, 0.4, and 0.6 g) were used, keeping the MB concentration fixed at 10 mg/L. The morphology and crystalline structure of the CFB before and after calcination was characterized via scanning electron microscope (SEM) and X-ray diffraction (XRD) analyses, while the thermal behavior and surface functionalities were characterized by thermogravimetric analysis (TGA) and Fourier transform infrared (FTIR) spectroscopy, respectively. Adsorption experiments using different doses of CaO synthesized at 900°C for 0.5 h showed an MB removal efficiency as high as 98% by weight using 0.4 g (adsorbent)/L(solution). Two different adsorption models, the Langmuir adsorption model and the Freundlich adsorption model, along with pseudo-first-order and pseudo-second-order kinetic models, were studied to correlate the adsorption data. The removal of MB via highly ordered CaO adsorption was better modeled by the Langmuir adsorption isotherm giving (R2 =0.93), thus proving a monolayer adsorption mechanism following pseudo-second-order kinetics (R2= 0.98), confirming that chemisorption reaction occurs between the MB dye molecule and CaO.

Phytotoxicity and genotoxicity of agro-industrial digested sludge hydrochar: The role of heavy metals.

Hydrochar is a new carbonaceous product obtained via hydrothermal carbonization of wet biomass, such as sludges or digested sludges, which often have disposal problems, also due to the presence of contaminants such as heavy metals. The properties of the hydrochar led to an interest in using it as an amendment, but the agro-environmental properties must be considered for its safe use. Raw hydrochar produced by agro-industrial digestate and relative three acidic post-treated hydrochars (for heavy metals removal) have been assessed considering their effect on phytotoxicity, soil, plant growth, mutagenicity, and genotoxicity. The chemical characterization showed the effect of post-treatment on heavy metals contents reduction, except for Cu content (hydrochar, 650 mg/kg; post-treated hydrochars, 940 mg/kg, 287 mg/kg, and 420 mg/kg). The acidic post-treatment also reduces the phytotoxicity compared to raw hydrochar (the germination index at 16 % of hydrochar concentration was: hydrochar, 61.48 %; post-treated hydrochars, 82.27 %, 58.28 %, and 82.26 %), but the low pH and the impact on N-cycle probably have caused the detrimental effect on plant growth of post-treated hydrochar. No mutagenic activity was observed in bacteria using Ames test, while all the samples induced chromosomal aberrations in plant cells (Allium cepa test). The approach adopted, which considers phytotoxicity, plant growth-soil effects, and mutagenicity/genotoxicity bioassays has been proven effective for a proper evaluation of organic products derived from waste to promote a sustainable and circular recovery of materials.

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.

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.

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%.

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.

Social skills and neurocognitive individualized training in schizophrenia: comparison with structured leisure activities.

Cognitive impairment and deficits in social skills have been largely documented in patients with schizophrenia and are increasingly recognized as rate-limiting factors for recovery. Evidence has been provided that cognitive training and social skills training (SST) are effective to treat cognitive and social skills impairment in schizophrenia; however, the translation of improved performance on cognitive or social skills tasks into improved functional outcome is controversial. According to recent reviews, interventions providing cognitive training in conjunction with psychosocial rehabilitation have a greater impact on functional outcome than either intervention alone suggesting that the two treatment approaches may work together in a synergistic fashion. The present pilot study was designed to test the hypothesis that an integrated rehabilitation program, including individualized cognitive and SST, is more effective than the structured leisure activities (SLA) carried out in many Italian Mental Health Departments. The primary outcome measure was subjects' personal and social functioning as assessed by the Interview for the assessment of disability. The study is based on a controlled design including randomization to treatment groups, blind assessments and stable pharmacological treatment. Subjects were recruited among patients attending three psychiatric facilities located in the Italian region Campania. Thirty patients were randomized to the experimental program "social skills and neurocognitive individualized training" (SSANIT), and 30 to SLA. The two programs were matched for the overall duration as well as frequency and duration of the sessions. The two groups of patients did not differ at baseline on psychopathology, neurocognitive and personal/social functioning. After 6 months of treatment, personal and social functioning was significantly better in patients assigned to SSANIT than in those assigned to usual rehabilitation activities practiced in Mental Health Departments. No advantage was observed for either program on psychopathological and cognitive outcome indices. As for other integrated programs, also for SSANIT further studies are needed to verify generalization and persistence of the observed gains, and to clarify most adequate length and doses of the therapeutic intervention as well as the relative contribution of each program component to its impact on subjects' disability.

Photochemical and time resolved spectroscopic studies of intermediates relevant to iridium-catalyzed methanol carbonylation: photoinduced CO migratory insertion.

Photoreaction, time-resolved infrared (TRIR), and DFT studies were utilized to probe transformations between iridium complexes with possible relevance to the mechanisms of the iridium/iodide-catalyzed methanol carbonylation to acetic acid. Solution-phase continuous and laser flash photolysis of the tetraphenylarsonium salt of the fac-[CH3Ir(CO)2I3]- anion (1a) under excess carbon monoxide resulted in migratory insertion to give the acyl complex ion mer,trans-[Ir(C(O)CH3)(CO)2I3]- (2a). The latter was isolated as its AsPh4+ salt, and its X-ray crystal structure was determined. TRIR spectra indicate that several transients are generated upon flash photolysis of 1a. The principal photoreaction is CO dissociation, and this is proposed to generate the isomeric complexes fac-[CH3Ir(CO)(Sol)I3]- (I(CO)(fac), Sol = solvent) and mer,trans-[CH3Ir(CO)(Sol)I3]- (I(CO)(mer)). I(CO)(fac) reacts with CO to regenerate 1a with a second-order rate constant (k(CO)) approximately 2.5 x 10(7) M(-1) s(-1) in ambient dichloroethane, while I(CO)(mer) is the apparent precursor to 2a. Kinetics studies indicate the photoinduced formation of a third intermediate (I(M)), hypothesized to be the anionic acyl complex fac-[Ir(C(O)CH3)(CO)(Sol)I3]-. In the absence of added CO, these intermediates undergo dimerization to form a mixture of isomers with the apparent formula [Ir(C(O)CH3)(CO)I3]2(2-). One of these dimers was isolated as the AsPh4+ salt, and the crystal structure was determined. Addition of excess pyridine to a solution of the dimers gave the neutral complex mer,trans-[Ir(C(O)CH3)(CO)(py)2I2], which was characterized by FTIR, NMR, and X-ray crystallography. These transformations, especially the unprecedented photoinduced CO insertion reaction, are discussed and interpreted in terms of the factors favoring migratory insertion dynamics.

Assembling process of charged nonanuclear cationic lanthanide(III) clusters assisted by dichromium decacarbonyl hydride.

The reaction of Ln(acac)(3).3H(2)O (Ln = Sm, Eu, Gd, Dy, Yb) with K[Cr(2)(CO)(10)(micro-H)] at different molar ratios and solvents leads to the formation of nonanuclear lanthanide hydroxo acetylacetonate complexes of general formula [Ln(9)(OH)(10)(acac)(16)][HCr(2)(CO)(10)]. The compounds are isomorphous, and the common cationic cluster core consists of a novel square antiprismatic arrangement of nine Ln atoms connected by micro(3), micro(4) hydroxo bridges and/or by acetylacetonate ligands as it results from the single-crystal X-ray analysis of the Sm derivative for which the most suitable crystals were obtained.