Swine manure management by hydrothermal carbonization: Comparative study of batch and continuous operation.

Hydrothermal carbonization (HTC) is considered a promising technology for biomass waste management without pre-drying. This study explores the potential for swine manure management by comparing batch and continuous processes, emphasizing the benefits of the continuous mode, particularly for its potential full-scale application. The continuous process at low temperature (180 °C) resulted in a hydrochar with a lower degree of carbonization compared to the batch process, but similar characteristics were found in both hydrochars at higher operating temperatures (230-250 °C), such as C content (∼ 52 wt%), fixed carbon (∼ 24 wt%) and higher calorific value (21 MJ kg-1). Thermogravimetric and combustion analyses showed that hydrochars exhibited characteristics suitable as solid biofuels for industrial use. The process water showed a high content of organic matter as soluble chemical oxygen demand (7-22 g L-1) and total organic carbon (4-10 g L-1), although a high amount of refractory species such as N- and O-containing long aromatic compounds were detected in the process water from the batch process, while the process water from the continuous process presented more easily biodegradable compounds such as acids and alcohols, among others. The longer time required to reach operating temperature in the case of the batch system (longer heating time to reach operating temperature) resulted in lower H/C and O/C ratios compared to hydrochar from the continuous process. This indicates that the dehydration and decarboxylation reactions of the feedstock play a more important role in the batch process. This study shows the efficiency of the continuous process to obtain carbonaceous materials suitable for use as biofuel, providing a solution for swine manure management.

Hydrothermal carbonisation of polyvinyl chloride in ethanol-water/water system for solid fuels: Dechlorination, characteristics analysis of hydrochar, and reaction path.

Polyvinyl chloride (PVC) waste plastic is a typical solid waste. In this paper, the dechlorination and carbonization behavior of PVC in ethanol-water/water system under different process parameters (temperature, residence time, solid-liquid ratio) was studied, and hydrothermal carbon was characterized by SEM, elemental analysis, TG-DTG, XPS, Py-GC/MS. The results show that temperature is the key to the hydrothermal dechlorination of PVC, and the dechlorination efficiency of PVC is the highest by parameter optimization (220°C-90 min-10% S/D-80% E/D), which can reach 96.33 %. With the removal of Cl, the surface of the PVC matrix changed from full and smooth flocculent to honeycomb with uniform pore size distribution. Thermogravimetric analysis shows that the combustion of hydrochar can be divided into three stages: HCl precipitation and volatile combustion, semi-coke and coke combustion, and fixed carbon combustion. The combustion parameters and kinetic parameters of hydrochar were measured, and it was found that the hydrothermal carbonization of PVC at higher temperatures and ethanol-water ratio could improve the combustion performance of hydrochar. The highest calorific value can reach 36.68 MJ/mol. Py-GC/MS analyzed the distribution of the pyrolysis products, and alkylbenzene and aliphatic were the main products of pyrolysis. The structural analysis of hydrochar showed that C-C and CC accounted for the largest proportion, accompanied by a small amount of C-O and CO and trace C-Cl. The possible reaction mechanism of the hydrothermal carbonization of PVC was analyzed based on the distribution of functional groups and compound composition. This work provides an effective and sustainable method for the recycling of refractory chlorinated plastics.

Unlocking the potential of Chinese herbal medicine residue-derived biochar as an efficient adsorbent for high-performance tetracycline removal.

This study employed hydrothermal carbonization (HTC) in conjunction with ZnCl2 activation and pyrolysis to produce biochar from one traditional Chinese medicine astragali radix (AR) residue. The resultant biochar was evaluated as a sustainable adsorbent for tetracycline (TC) elimination from water. The adsorption performance of TC on two micropore-rich AR biochars, AR@ZnCl2 (1370 m2 g-1) and HAR@ZnCl2 (1896 m2 g-1), was comprehensively evaluated using adsorption isotherms, kinetics, and thermodynamics. By virtue of pore diffusion, π-π interaction, electrostatic attraction, and hydrogen bonding, the prepared AR biochar showed exceptional adsorption properties for TC. Notably, the maximum adsorption capacity (930.3 mg g-1) of TC on HAR@ZnCl2 can be achieved when the adsorbent dosage is 0.5 g L-1 and C0 is 500 mg L-1 at 323 K. The TC adsorption on HAR@ZnCl2 took place spontaneously. Furthermore, the impact of competitive ions behavior is insignificant when coexisting ion concentrations fall within the 10-100 mg L-1 range. Additionally, the produced biochar illustrated good economic benefits, with a payback of 701 $ t-1. More importantly, even after ten cycles, HAR@ZnCl2 still presented great TC removal efficiency (above 77%), suggesting a good application prosperity. In summary, the effectiveness and sustainability of AR biochar, a biowaste-derived product, were demonstrated in its ability to remove antibiotics from water, showing great potential in wastewater treatment application.

Study of two approaches for the process water management from hydrothermal carbonization of swine manure: Anaerobic treatment and nutrient recovery.

Hydrothermal carbonization (HTC) is a promising alternative to transform biomass waste into a solid carbonaceous material (hydrochar) and a process water with potential for material and energy recovery. In this study, two alternatives for process water treatment by conventional and acid-assisted HTC of swine manure are discussed. Process water from conventional HTC at 180 °C showed high biodegradability (55% COD removal) and methane production (∼290 mL STP CH4 g-1 CODadded) and the treatment in an upflow anaerobic sludge blanket reactor allowed obtaining a high methane production yield (1.3 L CH4 L-1 d-1) and COD removal (∼70%). The analysis of the microbiota showed a high concentration of Synergistota and Firmicutes phyla, with high degradation of organic nitrogen-containing organic compounds. Acid-assisted HTC proved to be a viable option for nutrient recovery (migration of 83% of the P to the process water), which allowed obtaining a solid salt by chemical precipitation with Mg(OH)2 (NPK of 4/4/0.4) and MgCl2 (NPK 8/17/0.5), with a negligible content of heavy metals. The characteristics of the precipitated solid complied with the requirements of European Regulation (2019)/1009 for fertilizers and amendments in agricultural soils, being a suitable alternative for the recycling of nutrients from wastes.

Biocrude extraction from human-excreta-derived hydrochar for sustainable energy and agricultural applications.

Hydrothermal carbonization may be a sustainable sanitary treatment for wet organic waste including human excreta. Human-excreta-derived hydrochar properties differ from those of typical wet biomass due to the formation of a biocrude-like phase at low reaction temperatures. This study characterized the importance of this phase in terms of hydrochar combustion properties and potential agricultural use. Hydrothermal carbonization of raw human excreta was undertaken at 180, 210, and 240 °C, after which the biocrude phase was extracted with dichloromethane. Physicochemical properties, surface-area parameters, combustion profiles, and gas emissions of non-extracted hydrochar, biocrude, and extracted hydrochar were compared. The potential agricultural use of extracted hydrochar was assessed in germination experiments. Biocrude comprised up to 49.5% of hydrochar mass with a calorific value of >60% that of extracted hydrochar. Biocrude combustion properties were better than those of hydrochar, before and after extraction as demonstrated by higher combustion index value (Si). The extracted hydrochar surface area (34.7 m2 g-1) was greater than that of non-extracted hydrochar (<2 m2 g-1), and seeds germinated more readily due to the lower phytotoxin content. Most macro and micronutrients required for plant growth were retained in the extracted hydrochar. The extraction of biocrude from human-excreta-derived hydrochar not only provided a higher-quality fuel with enhanced combustion properties but also improved hydrochar characteristics, suggesting its potential as a soil additive for enhanced plant growth.

Synthesis of hydrochar from date palm seeds using microwave-enhanced hydrothermal carbonization and its application in dyes removal.

This work reports new findings on the preparation of hydrochar from date palm (Phoenix dactylifera) seeds through the application of the microwave hydrothermal carbonization (HTC) method. Optimization investigations involving temperatures and reaction times were conducted to establish the highest yield, achieving a maximum yield of 60.87%. The prepared material was then impregnated in phosphoric acid and carbonized in the tube furnace at 550 °C for 1.5 h with a nitrogen flow of 50 CCM. The samples were characterized via scanning electron microscopy (SEM), Brunauer-Emmet-Teller (BET) and Fourier transform infrared (FTIR). The samples showed remarkable BET surface areas following activation, reaching up to 992 m2·g-1. The substance was subsequently used to absorb methylene blue with good fitting to the Freundlich and Redlich-Peterson isotherm and achieved a peak adsorption capacity of 196.6 ± 3.9 mg·g-1.

This study involves the preparation of hydrochar through microwave-assisted hydrothermal carbonization (HTC) of date palm seeds. It explores the impact of different process parameters, such as power, reaction temperatures, and timing on the mass yield and BET surface area of the hydrochars. Additionally, the prepared material undergoes chemical activation with phosphoric acid, and its efficacy in extracting methylene blue (MB) from an aqueous solution is assessed. This research is particularly novel as it represents the first comprehensive investigation into the use of microwave-derived and phosphoric acid-activated hydrochar for MB extraction.

The effect of an acidic environment during the hydrothermal carbonization of sewage sludge on solid and liquid products: The fate of heavy metals, phosphorus and other compounds.

The pH of sewage sludge is a crucial factor during the hydrothermal carbonization process that influences the characteristics of the resulting products and migration of certain compounds from the solid to liquid phase. Accordingly, this work is focused on examining the pH impact during the HTC process, in particular, pH equals 2, 3, 4, 5 and 6 on the individual hydrothermally carbonized products generated at 200 °C and 2 h residence time. For this reason, the chemical and physical indicators describing the post-processing liquid and hydrochar were determined. For instance, it was observed that the phosphorus content detected in the liquid, derived at pH2, rose significantly by 80%. Furthermore, decreasing the pH of sewage sludge had a significant impact on the ash content and the calorific value of the hydrochar. Additionally, changes in the specific surface area of hydrochar were noticed: pH = 5 and pH = 6 showed an increase of 20-30%, while for lower pH values a decrease of c.a. 26% was achieved. The distribution of heavy metals between the obtained fractions in the HTC process (solid and liquid) indicated that 92 to almost 100% of the tested heavy metals were transferred to the hydrochar. A significant effect of pH on the distribution between these fractions was observed only for Zn and Ni. For instance, for pH = 2, Zn and Ni in post-processing liquid were 34% and 29%, respectively. In addition, the sequential extraction of heavy metals from hydrochar was also performed in order to identify mobile and non-mobile phases. It was noticed that the acidic environment favours a higher amount of mobile heavy metals in hydrochar. The largest effect was observed for Cd, Pb, Cr and Cu, for which, at pH = 2, their respective amounts in the mobile fraction were 2.7; 3.6; 1.8; 6.2 times higher, compared to the hydrochar without pH correction.

Microalgal-based carbon encapsulated iron nanoparticles for the removal of pharmaceutical compounds from wastewater.

This study evaluates the effectiveness of microalgal-based carbon-encapsulated iron nanoparticles (ME-nFe) in the removal of pharmaceutical compounds (PhACs) from water solutions and real municipal effluent at a laboratory scale. The investigated PhACs were chosen to represent different classes of synthetic drugs: antibiotics, anti-inflammatory drugs, antihypertensives, antiepileptics, neuroprotectors, and antidepressants. The adsorbent material was produced through hydrothermal carbonization (225 °C for 3 h), using microalgae grown on wastewater as the carbon source. ME-nFe showed heterogeneity in terms of porosity (with both abundance of macro and mesopores), a total pore volume of 0.65 mL g-1, a specific surface area of 117 m2 g-1 and a total iron content of 40%. Laboratory scale adsorption tests (1 g L-1 of nanoparticles with 2 min contact time) showed high removal for the most hydrophobic compounds. Removal efficiencies were high (over 98%) for Irbesartan, Ofloxacin and Diclofenac, promising (over 65-80%) for Clarithromycin, Fluoxetine, Lamotrigine and Metoprolol, but low for Gabapentin-Lactam and Propyphenazone (<20%). Electrostatic interactions between the drugs and the surface of the nanoparticles may account for the observed data, although additional removal mechanisms cannot be ruled out.

Nutrient-rich hydrothermal carbon production by exogenous nutrients combined with seaweed internal water.

As a product of hydrothermal carbonization (HTC) technology, hydrothermal carbon has shown excellent application potential in soil improvement, greenhouse gas reduction and pollution remediation. Since a large amount of water and biomass are directly used as reaction media, hydrothermal carbon produced by traditional HTC possesses poor nutrient properties and accompanied by the generation of toxic and hazardous wastewater. Here, a versatile and easily scalable strategy has been demonstrated for the one-step production of industrial nutrient-rich hydrothermal carbon (NRHC) by combining the exogenous nutrients with seaweed internal water. During the reaction process, exogenous nutrients (NH4H2PO3, KNO3, CO(NH2)2) participated in the HTC reaction and were uniformly distributed on the surface of hydrothermal carbon through surface complexation precipitation, ion exchange, and electrostatic interactions. Simulations based on density functional theory revealed that NRHC produced in presence of exogenous nutrients possessed more active sites and surface charges. Moreover, the adsorbent and adsorbate were simultaneously affected by intermolecular forces, electrostatic forces, and internal energy of the system, and the thermodynamics of adsorption process was more stable. Compared with no exogenous nutrient involvement, NRHC produced by exogenous nutrients showed 2.12, 18.56, and 25.69 times increase in the N, P, and K content. The length of the seed germination root system increased by 4.3-5.9 times, which met the standards set for agricultural fertilizer. Due to increased yield per unit volume and reduced wastewater generation, the cost of NRHC production reduced by 47.83-58.23 per cent and profit enhanced by 1.56-1.68 times, as compared to traditional HTC. This low-cost streamlined process provides a new strategy for large-scale production and direct application of hydrothermal carbon.

Elevating clean energy through sludge: A comprehensive study of hydrothermal carbonization and co-gasification technologies.

This study explores the recycling challenges of industrial sludge, owing to its non-recyclable properties and associated environmental problems. To promote sustainable energy utilization, a novel approach combining hydrothermal carbonization and co-gasification was employed to facilitate the conversion from waste to energy. The industrial sludge was pretreated in the batch-type hydrothermal treatment unit at 180-220 °C, followed by co-gasification. The experimental results indicate that pretreating the sludge at the hydrothermal temperature of 200 °C maximized its thermal decomposition, leading to a rougher structure with obvious cracks, eventually transforming into numerous fragmented small particles. At 1100 °C with a blending mass ratio of 1:1, the sludge hydrochar at 200 °C significantly enhanced the reactivity of coal char, exhibiting the gasification reactivity index R0.9 of 1.57 times higher than that of untreated char. Using the in-situ technique with the heating stage microscope, it was first observed that the addition of pretreated sludge coal chars underwent gasification in the shrinking core mode, displaying a significant ash melt flow phenomenon. Based on the in-situ X-ray diffraction, it was discovered that more amorphous structures were formed by the reaction of Fe with other minerals in the sludge-coal blended char after hydrothermal carbonization at 200 °C. With pretreatment at the hydrothermal temperature of 200 °C, the sludge can increase the specific surface area of the blended char and facilitate the cracking of carbon crystals during co-gasification. Its specific surface area and the Raman spectroscopic ratio ID1/IG were 1.76 and 1.17 times that of coal char, respectively. Collectively, this study highlights the potential for energy recovery from industrial sludge, contributing to sustainable waste management in the chemical industry.

Comprehensive assessment of cow manure hydrothermal treatment products for land application and energy recovery.

In this study, cow manure was hydrothermally treated in a 2-litre reactor for 1 h at temperatures between 100 °C and 260 °C. Both the raw manure and the solid and liquid products of the hydrothermal treatment were characterized to understand the fate of the inorganic elements and to assess the suitability of the products for land applications and energy recovery. Satisfactory elemental balances were obtained for the organic and most inorganic elements and indicated that most inorganic elements were incorporated into the solids with lower solubility, with the exception of potassium and sodium, which were mostly solubilized in the process water; calcium and chlorine were also solubilized to a lesser extent in the process water. Elemental composition and surface functional groups showed that hydrochar produced within the hydrothermal carbonization range (180-260 °C) seemed better suited for utilization as a soil amendment than raw cow manure. The potential for energy recovery lies in the anaerobic digestion of the process water, from which higher methane yields can be obtained than from raw cow manure. Lower temperatures in hydrothermal carbonization are considered a compromise for the safe land applications of cow manure, energy recovery from the process water, and enhanced dewaterability. These findings can help to eliminate bottlenecks in the upscaling of cow manure hydrothermal treatment and promote the circular bio-economy.

Unveiling drastic influence of cross-interactions in hydrothermal carbonization of spirulina with cellulose, lignin or poplar on nature of hydrochar and activated carbon.

Spirulina platensis contains abundant nitrogen-containing organics, which might react with derivatives of cellulose/lignin during hydrothermal carbonization (HTC), probably affecting yield, property of hydrochar, and pore development in activation of hydrochar. This was investigated herein by conducting co-HTC of spirulina platensis with cellulose, lignin, and sawdust at 260 °C and subsequent activation of the resulting hydrochars with K2C2O4 at 800 °C. The results showed that cross-condensation of spirulina platensis-derived proteins with cellulose/lignin-derived ketones and phenolics did take place in the co-HTC, forming more π-conjugated heavier organics, retaining more nitrogen species in hydrochar, reducing yields of hydrochar, making the hydrochar more aromatic and increasing the thermal stability and resistivity towards activation. This enhanced the yield of activated carbon (AC) by 7 %-20 % and significantly increased specific surface area of the AC from activation of hydrochar of spirulina platensis + lignin to 2074.5 m2/g (859.3 m2/g from spirulina platensis only and 1170.1 m2/g from lignin only). Furthermore, more mesopores from activation of hydrochar of spirulina platensis + cellulose (47 %) and more micropores from activation of hydrochar of spirulina + sawdust (93 %) was generated. The AC from spirulina platensis + lignin with the developed pore structures generated sufficient sites for adsorption of tetracycline from aqueous phase and minimized steric hindrance for mass transfer with the abundant mesopores (43 %).

Hydrochar from Pine Needles as a Green Alternative for Catalytic Electrodes in Energy Applications.

Hydrothermal carbonization (HTC) serves as a sustainable method to transform pine needle waste into nitrogen-doped (N-doped) hydrochars. The primary focus is on evaluating these hydrochars as catalytic electrodes for the oxygen reduction reaction (ORR) and carbon dioxide reduction reaction (CO2RR), which are pivotal processes with significant environmental implications. Hydrochars were synthesized by varying the parameters such as nitrogen loading, temperature, and residence time. These materials were then thoroughly characterized using diverse analytical techniques, including elemental analysis, density measurements, BET surface area analysis, and spectroscopies like Raman, FTIR, and XPS, along with optical and scanning electron microscopies. The subsequent electrochemical assessment involved preparing electrocatalytic inks by combining hydrochars with an anion exchange ionomer (AEI) to leverage their synergistic effects. To the best of our knowledge, there are no previous reports on catalytic electrodes that simultaneously incorporate both a hydrochar and AEI. Evaluation metrics such as current densities, onset and half-wave potentials, and Koutecky-Levich and Tafel plots provided insights into their electrocatalytic performances. Notably, hydrochars synthesized at 230 °C exhibited an onset potential of 0.92 V vs. RHE, marking the highest reported value for a hydrochar. They also facilitated the exchange of four electrons at 0.26 V vs. RHE in the ORR. Additionally, the CO2RR yielded valuable C2 products like acetaldehyde and acetate. These findings highlight the remarkable electrocatalytic activity of the optimized hydrochars, which could be attributed, at least in part, to their optimal porosity.

Hydrochar and synthetic natural gas co-production for a full circular economy implementation via hydrothermal carbonization and methanation: An economic approach.

Herein we study the economic performance of hydrochar and synthetic natural gas co-production from olive tree pruning. The process entails a combination of hydrothermal carbonization and methanation. In a previous work, we evidenced that standalone hydrochar production via HTC results unprofitable. Hence, we propose a step forward on the process design by implementing a methanation, adding value to the gas effluent in an attempt to boost the overall process techno-economic aspects. Three different plant capacities were analyzed (312.5, 625 and 1250 kg/hr). The baseline scenarios showed that, under the current circumstances, our circular economy strategy in unprofitable. An analysis of the revenues shows that hydrochar selling price have a high impact on NPV and subsidies for renewable coal production could help to boost the profitability of the process. On the contrary, the analysis for natural gas prices reveals that prices 8 times higher than the current ones in Spain must be achieved to reach profitability. This seems unlikely even under the presence of a strong subsidy scheme. The costs analysis suggests that a remarkable electricity cost reduction or electricity consumption of the HTC stage could be a potential strategy to reach profitability scenarios. Furthermore, significant reduction of green hydrogen production costs is deemed instrumental to improve the economic performance of the process. These results show the formidable techno-economic challenge that our society faces in the path towards circular economy societies.

Treatment of hydrothermal carbonization process water by electrochemical oxidation: Assessment of process performance.

Herein electrochemical oxidation (EO) is proposed as a novel path to treat the process water obtained from hydrothermal carbonization of olive tree pruning. The aim of this work is to analyze the organic matter removal achieved by the treatment along with the identification of the chemical species formed after the electro-oxidation process at different experimental conditions. Three different tests were performed in a boron doped diamond cell, using Na2SO4 and NaCl as supporting electrolytes to compare the results obtained with the raw process water. The organic matter removal was evaluated by means of total organic carbon and chemical oxygen demand, while Gas Chromatography Mass Spectrometry was used to determine the chemical species present before and after the treatment. The addition of a promoter considerably increased the organic matter removal. In fact, the experiments performed using supporting electrolytes showed the best results in terms of organic matter removal compared to the control experiment (30-40% vs. 17%); This reduction agrees with the volatile fatty acids' measurements. Almost all the chemical species identified in the different feedstocks were partially or totally removed after the EO treatment depending on the experimental conditions. The specific energy consumption and the cost calculated for the treatment is highly dependent on the time of electro-oxidation and the supporting electrolyte used, obtaining values from 1 to 45 €/kg CODremoved. All in all, this work suggests an interesting path towards a further utilization of process water from hydrothermal carbonization processes.

Hydrothermal carbonization of Typha australis: Influence of stirring rate.

According to existing literature, there are no conclusive results on the impact of stirring on hydrothermal carbonization (HTC); some studies report a significant impact on the product's properties, while others indicate no influence. This study investigates the influence of stirring rate on several responses and properties of HTC products, including solid mass yield, solid carbon fraction, surface area, surface functional groups, morphology, and the fate of inorganic elements during HTC. Waste biomass was introduced as a feedstock to a 2 L HTC reactor, where the effects of temperature (180-250 °C), residence time (4-12 h), biomass to water (B/W) ratio (1-10%), and stirring rate (0-130 rpm) were investigated. The findings of this study conclusively indicated that the stirring rate does not influence any of the studied responses or properties of hydrochar under the selected experimental conditions used in this study. Nevertheless, the results indicated that a low-stirring rate (5 RPM) is enough to slightly enhanced the heating-up phase of the HTC reactor. For future research, it is recommended to examine the impact of stirring rate on the HTC of other types of biomass using the methodology developed in this study.

Natural Nitrogen-Doped Carbon Dots Obtained from Hydrothermal Carbonization of Chebulic Myrobalan and Their Sensing Ability toward Heavy Metal Ions.

Chebulic Myrobalan is the main ingredient in the Ayurvedic formulation Triphala, which is used for kidney and liver dysfunctions. Herein, natural nitrogen-doped carbon dots (NN-CDs) were prepared from the hydrothermal carbonization of Chebulic Myrobalan and were demonstrated to sense heavy metal ions in an aqueous medium. Briefly, the NN-CDs were developed from Chebulic Myrobalan by a single-step hydrothermal carbonization approach under a mild temperature (200 °C) without any capping and passivation agents. They were then thoroughly characterized to confirm their structural and optical properties. The resulting NN-CDs had small particles (average diameter: 2.5 ± 0.5 nm) with a narrow size distribution (1-4 nm) and a relatable degree of graphitization. They possessed bright and durable fluorescence with excitation-dependent emission behaviors. Further, the as-synthesized NN-CDs were a good fluorometric sensor for the detection of heavy metal ions in an aqueous medium. The NN-CDs showed sensitive and selective sensing platforms for Fe3+ ions; the detection limit was calculated to be 0.86 µM in the dynamic range of 5-25 µM of the ferric (Fe3+) ion concentration. Moreover, these NN-CDs could expand their application as a potential candidate for biomedical applications and offer a new method of hydrothermally carbonizing waste biomass.

Bottom-Up Synthesis of De-Functionalized and Dispersible Carbon Spheres as Colloidal Adsorbent.

Recent innovative adsorption technologies for water purification rely on micrometer-sized activated carbon (AC) for ultrafast adsorption or in situ remediation. In this study, the bottom-up synthesis of tailored activated carbon spheres (aCS) from sucrose as renewable feedstock is demonstrated. The synthesis is based on a hydrothermal carbonization step followed by a targeted thermal activation of the raw material. This preserves its excellent colloid properties, i.e., narrow particle size distribution around 1 µm, ideal spherical shape and excellent aqueous dispersibility. We investigated the ageing of the freshly synthesized, highly de-functionalized AC surface in air and aqueous media under conditions relevant to the practice. A slow but significant ageing due to hydrolysis and oxidation reactions was observed for all carbon samples, leading to an increase of the oxygen contents with storage time. In this study, a tailored aCS product was generated within a single pyrolysis step with 3 vol.-% H2O in N2 in order to obtain the desired pore diameters and surface properties. Adsorption characteristics, including sorption isotherms and kinetics, were investigated with monochlorobenzene (MCB) and perfluorooctanoic acid (PFOA) as adsorbates. The product showed high sorption affinities up to log (KD/[L/kg]) of 7.3 ± 0.1 for MCB and 6.2 ± 0.1 for PFOA, respectively.

Improved solid/liquid separation performance of hydrochar from sludge via hydrothermal carbonization.

A solid-liquid separation process is crucial for the utilization of hydrochar from biomasses through hydrothermal carbonization (HTC). This study aimed to evaluate the separation performance of hydrochar from coking sludge (CS) and municipal sludge (MS) via HTC and propose its mechanistic insights. The results indicated that the separation performance of hydrochar was enhanced, and relatively severe hydrothermal temperatures exerted a relatively stronger dewatering effect (53.25% and 77.05% reductions in the total water contents in CS and MS, respectively) and a superior separation efficiency (the specific resistance to filtration of products obtained from CS and MS decreased form 7.21 × 1011 and 2.46 × 1012 to 1.92 × 1010 m/kg and 2.14 × 1011 m/kg, respectively). Mechanism investigation involved analyzing the surface functional groups of hydrochar and changes in organic components. It was demonstrated that the improvement in dewatering effect predominantly resulted from the release of bound water due to the decomposition of carbohydrates and proteins. Specifically, the release of bound water depended on the decomposition of carbohydrates at 180 °C, while it relied on the decomposition of proteins in the 210-300 °C range. Compared with particle size, the hydrophilicity of the particle played a more important role in improving the separation efficiency. The HTC reaction eliminated hydrophilic groups, such as hydroxyl and carboxyl groups, and induced the formation of aromatic structures, thus reducing the hydrophilicity of hydrochar particles. Moreover, it was found that the lower heating value of hydrochar from CS and MS increased from 3.51 to 1.94 to 8.32 and 4.60 MJ/kg due to the improvement of the separation efficiency. These comprehensive findings provide valuable mechanistic insights into the solid-liquid separation process and controlling the dewaterability of hydrochar.

Nitrogen-doped hydrochar prepared by biomass and nitrogen-containing wastewater for dye adsorption: Effect of nitrogen source in wastewater on the adsorption performance of hydrochar.

Dye wastewater has become one of the main risk sources of environmental pollution due to its high toxicity and difficulty in degradation. Hydrochar prepared by hydrothermal carbonization (HTC) of biomass has abundant surface oxygen-containing functional groups, and therefore is used as an adsorbent to remove water pollutants. The adsorption performance of hydrochar can be enhanced after improving its surface characteristics through nitrogen-doping (N-doping). In this study, wastewater rich in nitrogen sources such as urea, melamine and ammonium chloride were selected as the water source for the preparation of HTC feedstock. The N atoms were doped in the hydrochar with a content of 3.87%-5.70%, and mainly in the form of pyridinic-N, pyrrolic-N and graphitic-N, which changed the acidity and basicity of the hydrochar surface. The N-doped hydrochar adsorbed methylene blue (MB) and congo red (CR) in wastewater through pore filling, Lewis acid-base interaction, hydrogen bond, and π-π interaction, and the maximum adsorption capacities of those were obtained with 57.52 mg/g and 62.19 mg/g, respectively. However, the adsorption performance of N-doped hydrochar was considerably affected by the acid-base property of the wastewater. In a basic environment, the surface carboxyl of the hydrochar exhibited a high negative charge and thus an enhanced electrostatic interaction with MB. Whereas, the hydrochar surface was positively charged in an acid environment by binding H+, resulting in an enhanced electrostatic interaction with CR. Therefore, the adsorption efficiency of MB and CR by N-doped hydrochar can be tuned by adjusting the nitrogen source and the pH of the wastewater.