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This research aimed to synthesise an effective hydrochar adsorbent from vineyard pruning wastes to remove emerging contaminants as a potential valorisation product. The adsorption capacity of the hydrochar was optimised using the Taguchi method. Four synthesis variables were evaluated: hydrothermal reaction temperature, use of H3PO4 as a catalyst, number of acetone washes, and type of chemical cold activation. The simultaneous adsorption of five model pesticides (clothianidin (CTD), acetamiprid (ACE), 2,4-D, metalaxyl (MET), and atrazine (ATZ)) at an initial pH of 7 was studied. At optimum conditions, the hydrochar presented a total adsorption capacity of 22.7 µmol/g, representing a 2.7-fold improvement with respect to pristine hydrochar performance. High percentage removals were achieved for all pollutants (85 % CTD, 94 % ACE, 86 % MET, and 95 % ATZ) except for 2,4-D (4 %). This research provides a valuable reference for developing hydrochar adsorbents for pollution control and the valorisation of biomass wastes.

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This study investigates the formic acid-mediated hydrothermal carbonisation (HTC) of microalgae biomass to enhance green hydrogen production. The effects of combined severity factor (CSF) and feedstock-to-suspension ratio (FSR) are examined on HTC gas formation, hydrochar yield and quality, and composition of the liquid phase. The hydrothermal conversion of Chlorella vulgaris was investigated in a CSF and FSR range of -2.529 and 2.943; and 5.0 wt.% - 25.0 wt.%. Artificial neural networks (ANNs) were developed based on experimental data to model and analyse the HTC process. The results show that green hydrogen formation can be increased up to 3.04 mol kg-1 by applying CSF 2.433 and 12.5 wt.% FSR reaction conditions. The developed ANN model (BR-2-11-9-11) describes the hydrothermal process with high testing and training performance (MSEz = 1.71E-06 & 1.40E-06) and accuracy (R2 = 0.9974 & R2 = 0.9781). The enhanced H2 yield indicates an effective alternative green hydrogen production scenario at low temperatures using high-moisture-containing biomass feedstocks.

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A calcium-pyro-hydrochar (Ca-PHC) can be distinguished as a novel sorbent of Pb2+ and Cd2+ from an aqueous solution. It was obtained using hydrothermal treatment of the spent mushroom substrate (SMS), followed by a CaCl2·5H2O activation and pyrolysis. The characterisation of chars before and after modifications was done by scanning electron microscope (SEM), Brunauer-Emmett-Teller (BET) and Fourier transform infrared (FTIR). Batch experiments were performed to examine Ca-PHC's sorption properties and binding mechanisms to selected metal ions. The maximum sorption capacities of Ca-PHC for Pb2+ and Cd2+ were 297 mg g-1, and 131 mg g-1, respectively. The obtained results demonstrated that the sorption of Pb2+ and Cd2+ by Ca-PHC follows a pseudo-second kinetic model and Freundlich isotherm. The binding of the selected metals onto Ca-PHC was enabled by the ion-exchange mechanism, surface complexation, mineral precipitation and cation-π interaction. Thermodynamic parameters indicate that metal ions binding by Ca-PHC are spontaneous and endothermic. Due to the high adsorption capacities, the obtained Ca-PHC has good potential for application in industrial wastewater treatment. In addition, the demonstrated use of SMS highlights another possibility of applying this specific biomass relevant to sustainable and economical waste management in the growing mushroom industry.

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This study aims to use landfill leachate (LL) as an aqueous medium during hydrothermal carbonisation (HTC) of food waste to produce hydrochar (FWH-LL-C), which could be used as an electrode material in energy storage devices. The structural properties and electrochemical performance of the hydrochar were compared to that obtained using distilled water as a reaction medium (FWH-DW-C). The results showed that there is a difference in Brunauer-Emmett-Teller (BET) surface area of FWH-LL-C (220 m2 gm-1) and FWH-DW-C (319 m2 gm-1). The electrochemical properties were comparable, with FWH-LL-C having 227 F g-1 specific capacitance at 1 A g-1 current density and FWH-DW-C having 235 F g-1 specific capacitance at 1 A g-1 current density. Furthermore, at a power density of 634 W kg-1, FWH-DW-C achieved the highest energy density of 14.4 Wh kg-1. The energy retention capacity of the electrode was 98% which indicate that the material has an excellent energy storage capacity. The findings suggested that LL could be used as an alternative source of aqueous media during the HTC of food waste to produce hydrochar which could be used as an effective electrode material in supercapacitors.

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Hydrothermal carbonisation (HTC) can transform wet lignocellulosic biomass, which is not considered an effective biofuel for energy production at the industrial level, into a carbonaceous product called hydrochar (HC) that is suitable for combustion and a process water (PW). PW is an interesting by-product that can be valorised for biogas production via anaerobic digestion (AD). This study presents a new approach for the valorisation of garden and park wastes (GPW) by integrating HTC to generate HC for energy production, while PW is subjected to AD for biogas production. The hydrothermal treatment was performed at 180, 210, and 230 °C, yielding HC with improved physicochemical properties, such as an elevated higher heating value (21-25 MJ kg-1); low ash (<5 wt.%), nitrogen (1.3 wt.%), and sulphur (0.2 wt.%) contents; better fuel ratio (0.4-0.6); and a broad comprehensive combustibility index (8.0×10-7 to 9.6×10-7 min-2 °C-3). AD of the generated PW was conducted under mesophilic conditions (35 °C), resulting in a methane production in the range of 253-326 mL g-1 CODadded and COD removal of up to 65%. The combination of HTC and AD allowed the recovery of 91% and 94% of the energy content feedstock, as calculated from the combustion of HC and methane, respectively.

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This study investigates the long-term performance of the mesophilic (35 °C) anaerobic mono-digestion of process waters (PW) from the hydrothermal carbonisation (HTC) of spent coffee grounds. At an organic loading rate (OLR) of 0.4 gCOD L-1 d-1, initial instability was seen, but after 40 days and supplementary alkalinity, the digestion stabilised with the chemical oxygen demand (COD) in the untreated PW degraded with 37.8-64.6% efficiency and the yield of methane at 0.16 L gCOD-1. An increase in OLR to 0.8 gCOD L-1 d-1 caused a collapse in biogas production, and resulted in severe instability in the reactor, characterised by falling pH and an increasing volatile fatty acid concentration. Comparatively, the digestion of a treated PW (concentrated in nanofiltration and reverse osmosis after removal of the fouling fraction), at OLR between 0.4 and 0.8 gCOD L-1 d-1, was stable over the entire 117 days of treated PW addition, yielded methane at 0.21 L gCOD-1 and the COD was degraded with an average efficiency of 93.5% - the highest efficiency the authors have seen for HTC PW. Further anaerobic digestion of untreated PW at an average OLR of 0.95 gCOD L-1 d-1 was stable for 38 days, with an average COD degradation of 69.6%, and methane production between 0.15 and 0.19 L gCOD-1. The digestion of treated PW produced significantly higher COD degradation and methane yield than untreated PW, which is likely to be related to the removal of refractory and inhibitory organic material in the post-HTC treatment by adsorption of hydrophobic material.

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Anaerobic digestion (AD) is a widely used technology to valorise food waste for biogas production yet a considerable amount of digestate remains under-utilised. Sustainable management and recycling of the nutrient-rich food waste anaerobic digestate (FWD) is highly desirable for closing resource loop and actualising circular economy. This work reviews the distinct properties of FWD and the existing treatment technologies. FWD shows great prospects as a nutrient source for microalgal cultivation and biofuel production. Emerging technologies such as thermal conversion (e.g., pyrolysis and hydrothermal treatment) of FWD into value-added products such as functionalised biochar/hydrochar with diverse applications would be attractive and warrant further research investigation. Integrated AD with subsequent valorisation facilities is highly encouraged to achieve complete utilisation of resources and reduce carbon emissions.

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This study aimed to assess the role of hydrothermal carbonisation (HTC) in digestate processing in centralised biogas plants receiving dewatered sludge from regional wastewater treatment plants and producing biomethane and fertilisers. Chemically conditioned and mechanically dewatered sludge was used as such (total solids (TS) 25%) or as diluted (15% TS) with reject water in 30 min or 120 min HTC treatments at 210 °C, 230 °C or 250 °C, and the produced slurry was filtered to produce hydrochars and filtrates. The different hydrochars contributed to 20-55% of the original mass, 72-88% of the TS, 74-87% of the energy content, 71-92% of the carbon, above 86% of phosphorous and 38-64% of the nitrogen present in the original digestates. The hydrochars' energy content (higher heating values were 11.3-12.2 MJ/kg-TS) were similar to that of the digestates, while the ash contents increased (from 43% up to 57%). HTC treatments produced filtrates in volumes of 42-76% of the dewatered digestate, having a soluble chemical oxygen demand (SCOD) of 28-44 g/L, of which volatile fatty acids (VFAs) contributed 10-34%, and methane potentials of 182-206 mL-CH4/g-SCOD without any major indication of inhibition. All 32 pharmaceuticals detected in the digestates were below the detection limit in hydrochars and filtrates, save for ibuprofen and benzotriazole in filtrate, while heavy metals were concentrated in the hydrochars but below the national limits for fertiliser use, save for mercury. The integration of HTC to a centralised biogas plant was extrapolated to enhance the annual biogas production by 5% and ammonium recovery by 25%, and the hydrochar was estimated to produce 83 GJ upon combustion or to direct 350 t phosphorous to agriculture annually.

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This study investigates the integration of hydrothermal carbonisation (HTC) with anaerobic digestion (AD) as a valorisation route for two macroalgae species; S. latissima (SL) and F. serratus (FS). HTC reactions were conducted at temperatures of 150 °C, 200 °C and 250 °C, with resulting hydrochars, process waters and hydrothermal slurries assessed for biomethane potential yields. Un-treated SL generated similar biomethane levels compared to all SL slurries. Whereas all FS slurries improved biomethane yields compared to un-treated FS. Hydrochars represent a greater energy carrier if used as a solid fuel, rather than a feedstock for anaerobic digestion. Integrating HTC and AD, through hydrochar combustion and process water digestion has a greater energetic output than anaerobic digestion of the un-treated macroalgae. Treatment at 150 °C, with separate utilisation of products, can improve the energetic output of S. latissima and F. serratus by 47% and 172% respectively, compared to digestion of the un-treated macroalgae.

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This study evaluates and compares the environmental impacts arising from the disposal of different carbonaceous sorbents used for wastewater treatment. Three different adsorption materials were considered, i.e. activated carbon, biochar and hydrochar, and three end-of-life management approaches, i.e. incineration, regeneration and landfilling. The highest overall environmental impact was of Carcinogenic effects and Freshwater Ecotoxicity due to emissions of heavy metals during production of all types of sorbents. The use of materials with higher adsorption capacities and regeneration of carbonaceous materials were considered and shown to be an efficient way for reducing the overall environmental impacts of the different adsorbents. The compensation of fossil fuel incineration by using recovered heat led to negative impacts in all categories. Recirculation of HTC process water reduced the impact on Freshwater Ecotoxicity and Eutrophication.

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Mesoporous carbons containing up to 3.6 at.% N and 4.4 at.% O and exhibiting graphitic character have been prepared from Ni(II) and Fe(II) phthalocyanines by direct pyrolysis or by HTC + pyrolysis, and subsequently applied as supercapacitor materials. No mesoporous templates or doping post-treatments were used, and the catalytic effect of Ni(II) and Fe(II), naturally present in the precursor molecules, allowed obtaining graphitic carbons at temperatures ≤ 900 °C. Metals were encapsulated in the core of onion-like structures with no contact with the electrolyte, so that electrodes were prevented from degradation during device operation. The materials exhibited high rate capabilities up to 1 V s-1, higher interfacial capacitances than a wide variety of materials possessing higher surface areas, and high capacitance retentions up to 99% at 5 A g-1 current density throughout 10 000 charge-discharge cycles. The electrochemical performances of the phthalocyanine-derived carbons are due to their graphitic character and to the pseudocapacitance contribution of the surface groups through Faradaic reactions. This work opens a new way to obtain carbon materials from a great family of metal phthalocyanines, since the central metal and the radicals of the latter can be varied to tune the carbon properties for specific applications.

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This study investigates the recovery of phosphorus from the process water obtained through hydrothermal carbonisation (HTC) of a 'wet' biomass waste, namely spent coffee grounds. HTC was shown to liberate more than 82% of the total phosphorus in the grounds in the form of dissolved ortho-phosphate. Nanofiltration was used to concentrate the inorganic nutrients of the HTC process water, achieving a mass concentration factor of 3.9 times. The natural stoichiometry of phosphorus, magnesium and ammoniacal nitrogen in the nanofiltration retentate was favourable for struvite precipitation. 92.8% of aqueous phosphorus was recovered as struvite through simple pH adjustment, yielding a total phosphorus recovery of 75% from the feedstock spent coffee grounds.

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Food waste constitutes a remarkable portion of municipal solid waste. About one-third of the global food waste produced is lost with the food supply chain. Food waste in many countries is still dumped of in landfill or incinerated simultaneously with other municipal wastes. Food waste requires proper management and recycling techniques in order to minimise its environmental burden and risk to human life. Despite considerable research on food waste conversion still, there is a shortage of comprehensive reviews of the published literature. In this review, we provide a mini global perspective of food waste with special emphasis on New Zealand and their conversion into the useful material through hydrothermal carbonisation (HTC). Other thermal technologies such as incineration and pyrolysis are also briefly discussed. The review discusses why HTC is more suitable thermal technology than others, which are currently available. Recognising the importance of techno-economic feasibility of HTC, we present a cost analysis on the production of value-added products via HTC with examples taken from the literature to gather information in the feasibility assessment process. Finally, key challenges and future directions for a better productive way of handling food waste are being suggested.

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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.

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The effect of phosphoric acid addition to the feed-water on the speciation and transformation behaviour of potentially toxic elements (PTEs) in the hydrothermal carbonisation (HTC) of sewage sludge was explored. Over 70% of each of the PTEs (As, Cd, Cr, Cu, Mn, Ni, Pb and Zn) was in the directly bioavailable and potentially bioavailable fraction in the raw sludge, and especially Cu and Zn at 97.5 and 98.6%, respectively. Through the HTC process the directly bioavailable and potentially bioavailable fractions of PTEs in the sludge hydrochar clearly decreased, and the residual fraction in the hydrochar showed an observable increase. Further stabilisation of PTEs in hydrochar occurred during HTC with the addition of phosphoric acid solution to the feed-water. As the concentration of phosphoric acid in the feed-water increased the percentages of the residual fraction of Cd, Cr, Ni, Pb and Zn in hydrochars each exceeded 80%, but different PTEs behaved differently with increasing phosphate molar ratio in the feed-water. When the molar ratio of phosphate was 15%, the percentages of the residual fractions of Cd, Mn and Zn reached their maximum values in accordance with the changing trend in aromaticity of the hydrochar. Moreover, a large number of phosphate mineral crystals effectively occluded the PTEs in hydrochar. In conclusion, the addition of phosphoric acid to the feed-water during HTC further deactivated PTEs leading to a substantial decline in the potential environmental risk associated with the land application of the sewage sludge.

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A solid carbon-rich product hydrochar, was prepared using hydrothermal carbonisation of food waste at temperatures of 200, 250 and 300 °C. To acquire detailed insight into physicochemical and structural properties, hydrochar samples were characterised using a range of techniques. The carbon content and higher heating value of food waste increased considerably from 39 to 73% and 15 to 31 MJ/kg corresponding to the heating temperature. The blends of hydrochar and coal prepared in three different ratios (5%, 10% and 15%) exhibited different thermal behaviour. The overall results of co-combustion study showed that the activation energy of hydrochar samples decreased from 56.78 KJ/mol to 29.80 KJ/mol with increase in temperature. Hydrochar prepared at 300 °C with coal blending ratio of 10% exhibited the lowest activation energy of 19.45 KJ/mol. Additionally thermal gravimetric analysis of the samples showed that high temperature carbonization can increase the combustion properties of hydrochar.

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This study is an assessment of the hydrothermal carbonisation of poultry slaughterhouse wastes sludge for the solid recovered fuel. The effects of hydrothermal carbonisation were evaluated by varying the reaction temperatures in the range of 170 °C-220 °C. After hydrothermal carbonisation was completed, the capillary suction time, time to filter, and particle size decreased by ranges of 170.4 to 25.9 s, 40 to 7.0 s, and 220 to 98 um, respectively, with increasing hydrothermal carbonisation temperature. This effect improved the dewaterability to release additional free water from the sludge. Moreover, hydrothermal carbonisation increased the heating value though the reduction of the hydrogen and oxygen content of solid fuel in addition to investigating drying performance. As shown in the Van Krevelen diagram, the H/C and O/C ratios decreased, in correlation with primary reactions of coalification. These results suggest that the hydrothermal carbonisation process is an advantageous technology in improving the properties of poultry slaughterhouse wastes as an alternative solid recovered fuel by converting the physical and chemical structure of the poultry slaughterhouse wastes in addition to also providing other benefits to treat organic and biomass waste.

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The main purpose of this study was to understand the effect of time and temperature during the hydrothermal carbonisation (HTC) of olive stones (OS). For that purpose, the severity factor was introduced, by which the effect of the HTC conditions on the resultant products could be described. HTC was carried out at various temperatures (160, 180, 200, 220 and 240 °C) and times (3, 6, 12, 24 and 48 h) for producing 25 hydrochars. The yield to hydrochar varied from 70 to 50%. Hydrochars were all submitted to thermogravimetric and elemental analysis. The liquid fractions were also recovered and analysed in order to valorise OS as completely as possible. Thus, highly added-value products such as furfural and 5-hydroxymethylfurfural were detected. At the highest temperature and time, the hydrochar elemental composition was similar to that of lignite coals. Hydrochars were further carbonised at 900 °C, leading to materials with surface areas as high as 1200 m2 g-1 and with narrow pore size distributions centred on 0.5 nm. The severity factor allowed finding clear tendencies in the production of hydrochars and derived carbons in terms of yield, composition, and surface area, which would have been hardly analysed if the effects of temperature and time had to be considered separately. We proved that the severity factor, which use is quite uncommon in studies dealing with materials production, is a valuable tool for studying the effects of HTC experimental conditions.

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In this study, hydrothermal carbonisation (HTC) of poultry litter (PL) was carried out to evaluate the impact of initial pH using acetic acid (CH3COOH) or sulfuric acid (H2SO4) on the yields and properties of hydrochar (HC). The PL samples were treated by HTC at various initial pH and at 250°C for 2h. The HCs produced were characterized by ultimate, proximate and fibre analyses as well as heating value and surface area measurements. The results indicated that undertaking HTC in the presence of acids (CH3COOH, H2SO4) significantly affects the yields and properties of HC. The C content and HHV of the HC increased with decreasing initial pH. In the presence of H2SO4, the hydrochar yield (HY) increased while the ash content was significantly reduced. The lowest ash content and the highest HY were measured in the HC produced from the suspension with an initial pH of 2 using H2SO4.

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It has recently been shown that waste biomass can be converted into a wide range of functional materials, including those with desirable optical and electronic properties, offering the opportunity to find new uses for these renewable resources. Photovoltaics is one area in which finding the combination of abundant, low-cost and non-toxic materials with the necessary functionality can be challenging. In this paper the performance of carbon nanodots derived from a wide range of biomaterials obtained from different biomass sources as sensitisers for TiO2 -based nanostructured solar cells was compared; polysaccharides (chitosan and chitin), monosaccharide (d-glucose), amino acids (l-arginine and l-cysteine) and raw lobster shells were used to produce carbon nanodots through hydrothermal carbonisation. The highest solar power conversion efficiency (PCE) of 0.36 % was obtained by using l-arginine carbon nanodots as sensitisers, whereas lobster shells, as a model source of chitin from actual food waste, showed a PCE of 0.22 %. By comparing this wide range of materials, the performance of the solar cells was correlated with the materials characteristics by carefully investigating the structural and optical properties of each family of carbon nanodots, and it was shown that the combination of amine and carboxylic acid functionalisation is particularly beneficial for the solar-cell performance.

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