Search

Four deciduous woody feedstocks (Casuarina equisetifolia L., Eucalyptus globulus, Wrightia tinctoria, and Neolamarika cadamba) were subjected to the Hydrothermal Carbonization (HTC) process inside a 50 mL stainless steel hydrothermal reactor at varying temperatures (180°C, 215°C, and 250°C), while keeping water-to-feedstock ratio (6:1 v/w%) and residence time (1.5 h) constant. The mass yield and energy yield of the resulting biomass were calculated as parameters for energy intensification. Characterization of the biomass, biochar, and bio-oil was conducted using elemental analysis, SEM, and GC-MS. Interestingly, the mass yield of biochar decreased with increasing temperature, but it significantly improved the energy densification ratio, with a minimum of 1.06 observed for Neolamarika cadamba biomass at 180°C and a maximum of 1.23 observed for Eucalyptus globulus biomass at 250°C. Moreover, detailed analysis of the bio-oil obtained at 250°C using GC-MS revealed the presence of a diverse range of fine chemicals, including benzyl, carboxylic acid, ester, methyl, phenol, pyrrole, nitro, and aliphatic hydrocarbons. These findings suggest that the HTC process can be optimized to tailor the production of specific value-added chemicals from lignocellulosic woody biomass. [ABSTRACT FROM AUTHOR]

The characteristics of hydrothermal carbonization hydrochar derived from cattle manure including excrements and lignocellulosic biomass were analyzed. The effects of hydrothermal carbonization were evaluated by varying the reaction temperatures in the range of 180~240 °C. The hydrochars were evaluated with respect to their usefulness as renewable fuels via physicochemical analysis and pyrolysis processes. As reaction temperatures increased, the fractions of fixed carbon in proximate analyses, carbon elements in ultimate analyses, and higher heating values of hydrothermally carbonized biochars increased in correlation with the primary reactions of coalification. Various correlations were derived with the characteristics of hydrochars in order to be utilized for operating and designing HTC reactors for cattle manure. The correlation between the O/C and H/C ratios was deduced on the basis of a van Krevelen diagram. The interaction equation was represented with the increased fraction of HHV compared to the reaction temperature of hydrothermal carbonization. The ultimate correlation for the estimation of higher heating values was suggested for HTC hydrochars. Moreover, the pyrolysis characteristics and kinetic parameters of the cattle manure and hydrochar were deduced by utilizing a multi-step kinetic model scheme. As the HTC reaction temperature increased, the global activation energy and the pre-exponential factors of hydrochars decreased in the low-temperature section and increased in the high-temperature section. [ABSTRACT FROM AUTHOR]

Wastes from recycled paper industry (WRP) was hydrothermally carbonized to remove impurities to produce alternative biofuel. The chlorine behaviors during hydrothermal carbonization (HTC) and the fuel properties of the generated hydrochar were evaluated. The degradation of lignocellulosic components improved free -OH bond and small free cellulosic fragments facilitating dechlorination. Meanwhile, dechlorination process stimulated degradation of biomass. The carbon content and density of WRP were improved by HTC resulting in high heating value increasing from 5044.40 MJ/m³ to 17,004.88 MJ/m³. Pollutants emission from hydrochar combustion would be effectively controlled because of the removal of sulfur and chlorine. Hydrochar enjoyed higher ignition temperature and average combustion rate while lower burnout temperature, indicating that the combustion range has been narrowed, thus improving the combustion efficiency. The increase of HTC temperature facilitated hydrochars combustion and reduce energy consumption during hydrochar combustion. Mild HTC operating conditions (220 °C for 90 min and 240 °C for 60 min) were supposed to effectively improve the combustion intensity with stability meanwhile reached the highest dechlorination efficiency. These results evidence the feasibility of converting WRP to clean biofuel via HTC. [ABSTRACT FROM AUTHOR]

A remarkable number of scientific papers are available in the literature about the process of hydrothermal carbonization (HTC), also called wet or hydrous pyrolysis, applied to biomass substrates. However, the biggest share of it focuses on the characterization of HTC products obtained from different feedstocks. Only a few works are available on the process thermodynamics, particularly about the determination of the enthalpy change and the related heat release or absorption during HTC, which is a key parameter to understand the nature of the process and to evaluate the heat requirements for the design of industrial scale HTC plants. The present review summarizes the research carried out with the aim of assessing the process enthalpy for HTC. Two main approaches have been identified and described, and the research works are sorted into two categories: enthalpy calculation based on the direct application of the Hess's law and enthalpy evaluation based on differential heat measurement. The hypotheses and results obtained by the different authors are critically analysed and discussed, and directions for further research are proposed. [ABSTRACT FROM AUTHOR]

Abstract This review aims at summarizing the literature for the coupling of the biological process of anaerobic digestion (AD) with one of three thermal processes: gasification (Gs), pyrolysis (Py), and hydrothermal carbonization (HTC). These thermal processes are investigated as pre and/or post treatments for AD, aiming at reducing its main drawbacks. The different cases are considered separately, based on the thermal treatment that is coupled with the AD process: AD-Gs, AD-Py, and AD-HTC. For each group, up to three sub-cases are discussed: the thermal treatment of the digestate, the use of char from the thermal treatment as stabilizer and enhancer in the AD reactor, and the AD of the aqueous products of the thermal treatment (this last case is not available with Gs). When possible, the result of the different researches for each configurations are grouped for comparison. Finally, an overview of the most promising future research investigations is given. Highlights • Biological and thermo-chemical processes towards the bio-refinery concept. • Anaerobic Digestion coupled with Gasification. • Anaerobic Digestion coupled with Pyrolysis. • Anaerobic Digestion coupled with Hydro-Thermal Carbonization. • Main challenges, points of interest and suggested future research focus. [ABSTRACT FROM AUTHOR]

BACKGROUND Carbon is the raw material for many commercial products; conventionally their production is from non‐renewable sources such as petroleum coke, pitch and coal. Recently carbon has been obtained from bioresources because of their renewability and high lignocellulosic content. This article details the synthesis of carbon microspheres from rubber wood, which is one of the largest commodity plants, via hydrothermal carbonization (hydrothermal rubber wood carbon; HTRW carbon) and evaluation of their characteristics. RESULTS: Two sets of carbon were synthesized: (i) in the first set, excess of water (20–40 × weight of biomass) was used in the hydrothermal process at 180–260 °C for 3–9 h; and (ii) in the second set, water ratio was 25–35 × weight of biomass and the hydrothermal carbonization (HTC) reaction temperature was fixed at 260 °C. The H/C and O/C ratios of starting rubber wood were ∼1.78 and ∼0.85, respectively, which upon processing through the first strategy resulted in H/C ∼0.78 and O/C ∼0.29; thereby suggesting increased condensation under HTC. On the other hand, the carbonization process was accelerated by water when the temperature was maintained at 260 °C; Fourier transform infrared (FTIR) studies show that this carbon has a different chemical structure from the starting rubber wood. Scanning electron microscopy (SEM) images showed that HTRW carbon was in the form of microspheres (size ∼1.5–5 µm). CONCLUSION: HTRW carbon with carbon content as high as 68% was developed from rubber wood biomass by hydrothermal processing of a mixture containing 35 times more water than the solid raw biomass at a temperature of 260 °C for 7 h. © 2018 Society of Chemical Industry [ABSTRACT FROM AUTHOR]

Hydrothermal carbonization (HTC) is a promising technology to convert wet biomass into carbon-rich materials. Until now, the chemical processes occurring and their influence on the product properties are not well understood. Therefore, a target-oriented production of materials with defined properties is difficult, if not impossible. Here, model compounds such as cellulose and lignin, as well as different definite biomasses such as straw and beech wood are converted by hydrothermal carbonization. Following this, thermogravimetic (TGA) and FTIR measurements are used to get information about chemical structure and thermal properties of the related hydrochars. Some of the isolated materials are thermally post-treated (490 °C and 700 °C) and analyzed. The results show that at "mild" HTC conversion, the cellulose part in a lignocellulose matrix is not completely carbonized and there is still cellulose present. Thermal post-treatment makes the properties of product materials more similar and shows complete carbonization with increase aromatic cross-linking, proven by TGA and FTIR results. [ABSTRACT FROM AUTHOR]

Herein, the valorization of vegetable and fruit waste was assessed via hydrothermal carbonization (HTC) and anaerobic digestion (AD) in terms of product characterization and energy requirements. HTC was conducted at reaction temperatures between 150 ºC and 190 ºC, and residence times between 20 min and 40 min. The increase in the process severity resulted in hydrochars with higher carbon contents and higher energy densification ratios. AD was performed in two different ways. i.e., batch and semi-continuous reactions. From the batch experiments a methane yield of 300 L CH 4 /kg VS was obtained, while for the semi-continuous, the average specific methane production estimated (for HRTs from 75 to 50 days) was 213 ± 32 L CH 4 /kg VS. To estimate the energy requirements, mass and energy balances were performed considering the basic stages of each process to obtain a suitable biofuel material. In this sense, it was concluded that for this specific waste, AD was a more suitable process with a positive energy net balance. On the contrary, HTC presented a negative energy net balance being required 1.29 MJ/kg of fresh food waste. A combined HTC-AD treatment may be an efficient method to take advantage of both technologies leading to higher energy efficiencies and other valuable products. [Display omitted] • A carbon-rich solid product is obtained from HTC of fruit and vegetable waste. • The higher the severity of the HTC, the better the fuel properties of the hydrochars. • The energy recovered by HTC is higher than that of AD (923 MJ vs. 867.1 MJ). • Batch and semi-continuous anaerobic digestion experiments were performed. • AD presented a positive energy balance, while HTC showed negative outputs. [ABSTRACT FROM AUTHOR]

The electrochemical oxygen evolution reaction (OER) is a fundamental anodic semi-reaction used in the hydrogen energy industry. Herein, we report a novel NiFe-layered double hydroxide (NiFe-LDH)-based hybrid catalyst for the OER, which is promoted by the two-step hydrothermal loading of carbon sphere (CS) onto NiFe-LDH sheets, named as NiFe-LDH@CS. The effects of hydrothermal carbonization (HTC) parameters (such as hydrothermal time and glucose concentration) and the loading ratio of CSs on NiFe-LDH@CS were investigated. The results showed that the two-step hydrothermal synthesis significantly inhibited the interference of the carbonized substances on the lattice formation of NiFe-LDH and successfully achieved a firm combination. By adjusting the HTC process, the surface characteristics and graphitization degree of the carbonized microspheres can be effectively controlled, leading to increased OER performance of NiFe-LDH@CS. Thus, under the optimal process parameters (5 h, 0.6 M, and 5 mL), NiFe-LDH@CS exhibited an excellent overpotential of 292 mV at 50 mA cm-2 and 372 mV at 100 mA cm-2 for the OER. The outstanding OER performance of NiFe-LDH@CS is attributed to the excellent morphology control of the composite, abundant functional groups, and suitable graphitization degree of the hydrothermally carbonized CS, as well as the synergistic effect between the CSs and NiFe-LDH. • NiFe-LDH@CS composite is synthesized by novel two-step hydrothermal method. • Glucose hydrothermal carbonization is employed to control characteristics of CS. • Balanced properties of CS promote OER performance of NiFe-LDH significantly. • The Ni sites of NiFe-LDH are obviously activated by CS effective combination. [ABSTRACT FROM AUTHOR]

Hydrothermal carbonization (HTC) of carbohydrates in general has been reported as a sustainable and green technique to produce novel carbon materials. Traditional HTC of carbohydrates leads to irregular carbonaceous particles with low porosity due to inevitable aggregation induced by the high surface energy and the failure of classical templates. The accrescent understanding of the reaction mechanism in the HTC "dark box" provides possibilities of engineering HTC carbonaceous materials in a refined way. In the past decades, some unprecedented carbonaceous structures were achieved via modified HTC processes. Those progresses reflect the mightiness of HTC for precise synthesis however the last specialized review on this topic is over a decade old. In this review, we summarize the advances in the precise engineering of carbonaceous materials with specific morphologies and structures by the bottom-up HTC of carbohydrates, especially monosaccharides and disaccharides. This review elucidates the HTC set screws for the shaping of and/or the pore-creation within the targeted nanostructured carbonaceous materials. The benefits for applications arised from the special control of HTC carbon are also discussed. This review could inspire further insight into the HTC process and broader application of carbon nanostructures made from renewable resources. [ABSTRACT FROM AUTHOR]

Abstract: The difference between hydrothermal carbonization and vapothermal carbonization for the densification of the energy content of biomass has been investigated systematically for the first time. Vapothermal carbonization allows for higher solid content (solid biomass mass (dry basis) per total mass of feedstock) in the reactor because the biomass is subject to saturated steam instead of liquid water. Results from the experiments show that the process efficiency can be increased due to two reasons: the carbon losses in the liquid phase are decreased and less water needs to be heated up during carbonization. It was also observed that the carbon content of the solid product is significantly lower than that of hydrothermal carbonization at the same process conditions. As it is even lower for dry torrefaction, it is concluded that liquid water facilitates the carbonization process. Calculations based on these experimental results reveal that a mechanical dewatering of wet biomass increases the process efficiency of hydrothermal processes and should be considered in practice. Due to the low efficiency of state of the art drying, torrefaction is less efficient than vapothermal carbonization. [Copyright &y& Elsevier]

Biochar is discussed as an option for climate change mitigation via C sequestration and may promote sustainable resource efficiency. Large-scale field trials and commercial business with char materials have already started. Therefore char materials have to be assessed for toxic compounds. We tested genotoxic effects of different hydrochars and biochars with the Tradescantia micronucleus test. For this purpose chromosomal aberrations in pollen cells of Tradescantia in the form of micronuclei were evaluated microscopically after defined exposition to extracts from char materials. Hydrochars from hydrothermal carbonization mostly exhibited significantly negative results. Additional germination experiments with hydrochar showed total germination inhibition at additions above five percent v/v in comparison to biochar. However, biological post-treatment of previously toxic hydrochar was successful and toxic effects were eliminated completely. Some post-treated hydrochars even showed growth stimulating effects. Our results clearly demonstrate the necessity of risk assessment with bioindicators. The chosen tests procedures can contribute to biochar and hydrochar characterization for safe application. [Copyright &y& Elsevier]

• HTC processing upgraded waste straw LHV from 17.04 to 26.17 MJ/kg. • HTC processing above 225 °C removes inorganic ash combustion activity. • WS biomass released 254.9 ± 48.8 kJ/kg of heat during HTC transient period. • The time-correction factor determination method of the HTC processing time is presented. In this study, HTC impact on the waste straw fuel properties and waste straw hydrochars combustion kinetics have been presented. HTC experiments were carried out at Parr 4650 250 ml batch reactor, at temperatures of 225, 250, and 275 °C. Each temperature was investigated at 4 residence times: 10, 20, 30, and 40 min. Denoted hydrochars yields were more influenced by temperature than residence time, with different decomposition patterns observed at 275 °C compared to 225 and 250 °C, with final solid yields of 42.0%, 66.9%, and 65.3% at 40 min residence times respectively. The study of the transient HTC period resulted in the determination of the exothermal WS activity with the heat release of the 254.9 ± 48.8 kJ/kg of biomass. LHV values of the obtained hydrochars were 18.7–20.2 MJ/kg, 19.9–22.2 MJ/kg, and 23.1–26.2 MJ/kg for HTC temperatures of 225, 250, and 275 °C respectively. TGA analysis of the hydrochar combustion highlighted significant changes in the kinetic interpretation of the combustion profiles throughout investigated temperature ranges. The influence of residence time was only significant in the case of the 275 °C HTC samples, where a major shift of the combustion reactivity towards higher-temperature char oxidation was denoted. Hydrochars combustion kinetics were modeled with the implementation of Fraser-Suzuki deconvolution, and model-fitting of nth-order Arrhenius equation, with R2 values within 0.98–0.99. [ABSTRACT FROM AUTHOR]

An efficient method of synergetic dechlorination and reduction of heavy metals risk is crucial for the clean resource utilization of sewage sludge (SS) and polyvinyl chloride (PVC). In this work, SS was upgraded to hydrochar using co-hydrothermal carbonization (HTC) with PVC at different mixing ratio (30─70%) at 230 °C. Transformation behaviors of chlorine and heavy metals in hydrochars, along with fuel properties, were evaluated. The results illustrated that Mn and Zn could be effectively removed during co-HTC and low ratio addition of PVC was beneficial for reducing the toxicity of Ni and As. Meanwhile, compared with the HTC of single PVC, co-HTC with SS could further improve the dechlorination efficiency (69.49─81.35%). Particularly, the blending ratio of SS to PVC at 7:3 showed high fuel ratio and HHV (13.58 MJ/kg) with desirable combustion performance. These findings offered a potential approach to convert SS and PVC into clean solid fuel. [Display omitted] [ABSTRACT FROM AUTHOR]

Hydrothermal carbonization (HTC) reactor systems used to convert wet organic wastes into value-added hydrochar are generally classified in the literature as liquid water-based (HTC) or vapor-based (VTC). However, the distinction between the two is often ambiguous. In this paper, we present a methodological approach to analyze process conditions for hydrothermal systems. First, we theoretically developed models for predicting reactor pressure, volume fraction of liquid water and water distribution between phases as a function of temperature. The reactor pressure model predicted the measured pressure reasonably well. We also demonstrated the importance of predicting the condition at which the reactor system enters the subcooled compression liquid region to avoid the danger of explosion. To help understand water–feedstock interactions, we defined a new solid content parameter %S(T) based on the liquid water in physical contact with feedstock, which changes with temperature due to changes in the water distribution. Using these models, we then compared the process conditions of seven different HTC/VTC cases reported in the literature. This study illustrates that a large range of conditions need to be considered before applying the label VTC or HTC. These tools can help in designing experiments to compare systems and understand results in future HTC research. [ABSTRACT FROM AUTHOR]

In this study, the hydrothermal carbonization (HTC) technology at low temperature was applied to convert the wasted sludge into biochar, by establishing the correlation between the operation conditions and biochar characteristics. The contents of C, H, O, N and S, and the values of (O + N)/C and O/C in biochar were negatively correlated to the temperature, retention time and initial pH conditions. This implies that increasing temperature and retention time are beneficial for sludge dewatering and reduction. The maximum high heating value of biochar at 15.21 MJ/kg was achieved, which is similar to the cellulosic biochar and lignite surface known as the primary renewable fuel. The typical macromolecules such as proteins and lipids still existed on the biochar surface after low temperature HTC treatment. Decreasing the initial pH enforced the protonation effect and structural stability of the organic macromolecules in sludge, resulting in a diverse morphology with more compact microspheres on the biochar surface. Particularly, the catalytic ability to generate the carbon-centered persistent radicals was enhanced with g-factor at 2.01138–1.98428. In terms of environmental safety, the detected concentrations of heavy metals (Zn, Pb, Cu and Al) during the secondary dissolution of biochar were below 0.25 mg/L, indicating the low leaching risk for the land application. In addition, some humic acid and fulvic acid analogues were also detected in the secondary dissolution liquid, which can facilitate the redox reaction in soil microenvironment. In sum, this study confirmed that the low temperature HTC is a feasible method for sludge treatment and resource recovery. Image 1 [ABSTRACT FROM AUTHOR]

• Hydrothermal carbonization through high-pressure differential scanning calorimetry. • Kinetic parameters assessed based on calorimetric results. • nth-order reaction and autocatalytic reaction models investigated. • Very good fits obtained: R2 of 0.86 and 0.94 for digestate and sludge. Assessing kinetic parameters of hydrothermal carbonization still requires several tests and time-consuming analyses, usually relying on few data points. With a view to containing the experimental effort and testing the accuracy of models based on continuum curves, high-pressure differential scanning calorimetry was used for the first time to assess the heat release profile, the overall enthalpy change, and the kinetic parameters of a hydrothermal carbonization process in two substrates: digestate and sludge. The process-related thermal effect was established from the difference between the calorimetric curves for the unreacted samples during a first run and for the reacted samples obtained through a second run. The parameters of a kinetic model built on the Arrhenius reaction were adjusted on the basis of the calorimetric curves, adopting an nth-order and an autocatalytic reaction model. Activation energy values of 139.16 and 161.68 kJ/mol, pre-exponential factors around 2.15 × 1011 and 2.52 × 1014 s−1, reaction orders of about 2.68 and 2.46, and R 2 values of 0.86 and 0.94 were obtained for digestate and sludge, respectively. Results were consistent with the available literature. Autocatalysis was negligible for both substrates, so the process could be modeled effectively as a single Arrhenius nth-order reaction with significant loss of precision. Coupled with more traditional approaches, this newly-proposed method may pave the way to describing the set of reactions taking place during hydrothermal carbonization by means of their enthalpy values, improving our knowledge of the process's chemistry and kinetics. [ABSTRACT FROM AUTHOR]

Porous carbon materials are currently subjected to strong research efforts mainly due to their excellent performances in energy storage devices. A sustainable process to obtain them is hydrothermal carbonization (HTC), in which the decomposition of biomass precursors generates solid products called hydrochars, together with liquid and gaseous products. Hydrochars have a high C content and are rich with oxygen-containing functional groups, which is important for subsequent activation. Orange pomace and orange peels are considered wastes and then have been investigated as possible feedstocks for hydrochars production. On the contrary, orange juice was treated by HTC only to obtain carbon quantum dots. In the present study, pure orange juice was hydrothermally carbonized and the resulting hydrochar was filtered and washed, and graphitized/activated by KOH in nitrogen atmosphere at 800 °C. The resulting material was studied by transmission and scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and nitrogen sorption isotherms. We found porous microspheres with some degree of graphitization and high nitrogen content, a specific surface of 1725 m2/g, and a pore size distribution that make them good candidates for supercapacitor electrodes. [ABSTRACT FROM AUTHOR]

Peat moss and miscanthus were hydrothermally carbonized (HTC) either individually or co-processed in a different ratio to produce hydrochar. The hydrochar and pelletized hydrochar were then characterized to determine if hydrochar can be used as an alternative to coal to produce bioenergy from existing coal-fired power plants in Ontario that have already been shut down. The properties of carbonized biomass (either hydrochar or pellets) reveal that fuel grade hydrochar can be produced from peat moss or from the blend of peat moss and miscanthus (agricultural biomass/energy crops). Hydrochar either produced from peat moss or from the blend of peat moss and miscanthus was observed to be hydrophobic and porous compared to raw peat moss or raw miscanthus. The combustion indices of carbonized biomass confirmed that it can be combusted or co-combusted to produce bioenergy and can avoid slagging, fouling, and agglomeration problems of the bioenergy industry. The results of this study revealed that HTC is a promising option for producing solid biofuel from undervalued biomass, especially from high moisture biomass. Co-processing of peat moss with rural biomass, a relatively novel idea which can be a potential solution to heat and power for the rural communities/agri-industry that are not connected with national grids and alleviate their waste management problems. In addition, the hydrochar can also be used to run some of the existing coal-fired power plants that have already been shut down in Ontario without interrupting investment and employment. [ABSTRACT FROM AUTHOR]