Search Results (23)

5-Hydroxymethylfurfural (HMF) is a versatile platform molecule with the potential to replace many fossil fuel derivatives. It can be obtained through the dehydration of carbohydrates. In this study, we present a simple and cost-effective microwave-assisted method for producing HMF. This method involves the use of readily available sucrose as a substrate and glucose-derived bifunctional hydrochars as carbocatalysts. These catalysts were produced via hydrothermal carbonisation using thiourea and urea as nitrogen and sulphur sources, respectively, to introduce Brønsted acidic and basic sites into the materials. Using a microwave reactor, we found that the S, N-doped hydrochars were active in sucrose dehydration in water. Catalytic results showed that HMF yield depended on the balance between acidic and basic sites as well as the types of S and N species present on the surfaces of these hydrochars. The best-performing catalyst achieved an encouraging HMF yield of 37%. The potential of N, S-co-doped biochar as a green solid catalyst for various biorefinery processes was demonstrated. A simple kinetic model was developed to elucidate the kinetics of the main reaction pathways of this cascade process, showing a very good fit with the experimental results. The calculated rate constants revealed that reactions with a 5% sucrose loading exhibited significantly higher fructose dehydration rates and produced fewer side products than reactions using a more diluted substrate. No isomerisation of glucose into fructose was observed in an air atmosphere. On the contrary, a limited rate of isomerisation of glucose into fructose was recorded in an oxygen atmosphere. Therefore, efforts should focus on achieving a high glucose-to-fructose isomerisation rate (an intermediate reaction step) to improve HMF selectivity by reducing humin formation. Full article

Poultry litter was converted to biochar by torrefaction and to hydrochar by hydrothermal carbonisation. Many parameters were measured for the resulting chars, to investigate the effects of the production method and production temperature. SEM showed the presence of large quantities of crystalline material on the surface of the biochars. The elemental composition of some crystals was determined as 35% K and 31% Cl. This was confirmed as sylvite (KCl) crystals, which explains the high levels of water-extractable potassium in the biochar and may also be important in germination inhibition. Biochars almost totally inhibited germination, whilst hydrochars decreased germination. Although germination occurred on hydrochar, root growth was severely inhibited. Consequently, the germination index may be better to determine total phytotoxicity as it measures both effects and could be used as a bioassay for chars used as soil amendments. Washing removed germination inhibition in a low-temperature char (350 °C), possibly by removing KCl; however, root toxicity remained. There were very low levels of heavy metals, suggesting they are not the source of toxicity. In biochars, pore mean size decreased with temperature from 350 °C to 600 °C, due to changes in pore size distribution. The mean pore size was measured directly using SEM. The merits of this method are discussed. Low-temperature biochars seem best suited for fuel as they have a high calorific value, high hydrophobicity, a low ash content and a high yield. Higher temperatures are better for soil amendment and sequestration applications with a smaller mean pore size, higher surface area, and higher pH. Full article

The presented case study evaluates the environmental and economic effects of carbon bio pellet production from orchard grass by Farmutil HS Inc. through the hydrothermal carbonisation method, using obtained biofuel as a substitute for natural gas for heat production. Hydrothermal carbonisation is a zero-waste technology that produces renewable bioenergy by substituting fossil fuels for non-renewable resources. Processing 60,000 t/y of orchard grass with this method resulted in a total amount of heat production of 456,780 GJ/y. This means that over 60% of the energy produced from natural gas could be substituted by renewable bioenergy. It is also very important that the estimated cost of heat produced from carbon bio pellets is 29% lower in comparison to the cost of heat produced from natural gas Full article

The valorisation of sewage sludge for sustainable agricultural use and biofuel production proposes an effective and beneficial management of sewage sludge in a closed-loop cycle. The management of sewage sludge biowaste is a rising problem due to increasing waste storage expenses. In this sense, the use of circular economy principles in sewage sludge management creates opportunities to develop new technologies for processing. The biorefinery model allows the application of wasteless technologies via sewage sludge valorisation in terms of agricultural use and biofuel production, especially with the hydrothermal carbonisation method. Applying hydrothermal carbonisation in the treatment of biosolid sewage sludge has numerous benefits due to processing highly hydrated organic waste into carbon hydro char, a high-quality solid biofuel. The direct use of sewage sludge in the soil does not allow for full use of its functional properties. However, the hydrothermal carbonisation of sewage sludge results in biocarbon pellets, making it a viable approach. This work also discusses the barriers (legal, chemical, biological, and technical) and possibilities related to sewage sludge biorefining processes. Full article

Biochar (BC) and hydrochar (HC) have attracted considerable attention owing to their versatile characteristics and proven effectiveness in diverse technical fields. Solid BC is generated as a result of the dry carbonisation process of pyrolysis, in contrast to the slurry HC, which is produced during the hydrothermal carbonisation process. In this study, we evaluated the adsorption potential of two hydrochar samples (HCs) and three biochar samples (BCs) produced from sugar cane bagasse. The adsorption capacity of these samples was tested for ammonium, nitrate, and phosphate ions under various conditions. The BCs and HCs were subjected to characterisation using a CHNS/O analyser, the zeta potential, and Fourier transform infrared (FTIR). Elevating the pyrolysis temperature of the biochar resulted in changes in the fixed carbon and ash contents, while the volatile matter and H/C and O/C atomic ratios decreased. As the residence time increased, the H/C ratio and volatile matter content of the hydrochars (HCs) decreased. However, the fixed carbon content, ash content, and O/C and C/N ratios exhibited an increase. Thermodynamics, adsorption isotherms, and pH were also taken into consideration. The FTIR spectra analysis indicated that the carboxyl and ester functional groups present in both the BCs and HCs displayed reduced peak intensities subsequent to the adsorption of the three ions. While the adsorption was exothermic, we noticed that the adsorption capacity increased with temperature. The results indicate that sorption was homogenous across all binding sites, as evidenced by the optimal fit to the Langmuir isotherm. The research findings indicate that the adsorption capacity of various BC and HC adsorbents is significantly influenced by the surface area of the adsorbents in the case of nitrate and phosphate, but in the case of ammonia, adsorption is dictated by the functional polar groups present on the adsorbent surface. Full article

Mass Sargassum inundations have created opportunities for readily available biomass to be used as a crop enrichment application. However, the heavy metal contents of Sargassum pose serious concerns for crop administration and subsequent human consumption. Hydrothermal processing can break the feedstock components, allowing heavy metals to be partitioned, through the utilisation of high temperatures and pressures. As a result, seemingly nutrient-rich phases can be produced. Elemental analyses showed that Sargassum-derived fractions contain important macro- and micronutrients for plants, particularly ammonium, orthophosphate, and potassium, making them potential nutrient sources for plant growth. To date, no research has investigated the plant growth potential of hydrothermally processed Sargassum products from a bioavailability or biotoxicity perspective. We seek to determine if the aqueous phase products derived following Sargassum processing by hydrothermal carbonisation and liquefaction are toxic to higher plants, and if they can support plant growth. Aqueous phase products in ≥1% concentrations inhibit root growth and lateral root formation in Arabidopsis plants, likely from the presence of inhibitory compounds. However, aqueous phase products in ≤0.1% concentrations paired with an established nutrient mix may provide improved leaf and root growth. Both HTC and HTL were capable of eliciting improved foliage growth, while only HTC induced improved root growth. Conclusively, aqueous phase products lack nutrient potency to allow high dilutions for fertiliser application on their own and may contain inhibitory compounds that deter plant growth at high concentrations. However, they might have a purpose as an additive extract. The recovery of important elements needed for plant growth draws a promising path for future applications of hydrothermal processing with different feedstocks. Full article

Large amounts of hydrochar have been produced during the last decade by various hydrothermal carbonisation (HTC) processes. While the products of HTC seem to have widespread acceptance as valuable and efficient materials with advantages in their energy and environmental applications, which include soil improvement, heavy metal recovery, and many more, a comprehensive framework for the assessment of the different hydrochars based on their characteristics is missing. In this study, a framework for the assessment of hydrochars is proposed with the utilisation of Multi-Criteria Decision-Aiding (MCDA) methodologies. A hierarchical structure of independent criteria is established on a comprehensive level including three lines of evidence (LoE), i.e., Environmental, Economic, and Social LoE, which further include the assessment criteria. Hierarchical-SMAA-PROMETHEE is proposed as the most suitable MCDA methodology to be applied for assessing hydrochars based on the proposed framework. A case study is performed to demonstrate the utility of the framework and the advantages it offers to analysts and decision-makers. Hierarchical-SMAA-PROMETHEE is a non-compensatory method that enables exploring the decision problem on more than one level (comprehensive vs. LoE) and includes robust recommendations on the preference model and the elicitation of weights. Full article

One of the processes that can serve to valorise low-quality biomass and organic waste is hydrothermal carbonization (HTC). It is a thermochemical process that transpires in the presence of water and uses heat to convert wet feedstocks into hydrochar (the solid product of hydrothermal carbonization). In the present experimental study, an improvement consisting of an increased hydrophobic character of HTC-treated biomass is demonstrated through the presentation of enhanced mechanical dewatering at different pressures due to HTC valorisation. As part of this work’s scope, flashing-off of low-quality steam is additionally explored, allowing for the recovery of the physical enthalpy of hot hydrochar slurry. The flashing-off vapours, apart from steam, contain condensable hydrocarbons. Accordingly, a membrane system that purifies such effluent and the subsequent recovery of chemical energy from the retentate are taken into account. Moreover, the biomethane potential is calculated for the condensates, presenting the possibility for the chemical energy recovery of the condensates. Full article

Adsorption of methylene blue (MB) dye from an aqueous solution onto hydrochars produced from brown seaweed (Fucus Serratus) (FS-HC), coconut shell (CS-HC), and oak wood (Oak-HC) at different temperatures (200–250 °C) was investigated in a batch system. Response surface modelling (RSM) was used to investigate the effect of initial MB concentration (50–300 mg/L), contact time (0–240 min), and solution pH (2–12) on the adsorption process. RSM was also used to model and optimise these parameters for efficient adsorption. Kinetic and isotherms studies were carried out to study the adsorption mechanism onto the hydrochars. It was found that the best adsorbent from the RSM model was FS-HC200, and the optimal conditions for greater MB dye uptake were lower initial MB concentration (50 mg/L), pH 6 and contact time of 84 min; removing >99% of MB. Langmuir and Redlich–Peterson isotherm models fitted the adsorption of MB onto hydrochars prepared at 200 and 250 °C. Freundlich and Redlich–Peterson isotherms were suitable for hydrochars produced at 220 °C. FS-HCs have the highest maximum adsorption capacity of MB of about (8.60–28.57) mg/g calculated from the Langmuir isotherm. The adsorption process for all the hydrochars followed a pseudo-second-order model (R² = 0.96–1.00), and film diffusion and intraparticle diffusion were the rate-determining steps. Therefore, this work identifies cheap adsorbents from biowaste that are effective for the removal of cationic pollutants from wastewater. Full article

Pig manure currently results in sizeable greenhouse gas emissions, during storage and spreading to land. Anaerobic digestion and hydrothermal carbonisation could provide significant greenhouse gas mitigation, as well as generate renewable heat and power (with anaerobic digestion), or a peat-like soil amendment product (with hydrothermal carbonisation). The greenhouse gas mitigation potential associated with avoidance of pig manure storage and spreading in the UK, EU, and China, as well as the potential to provide heat and power by anaerobic digestion and soil amendment products by hydrothermal carbonisation was herein determined. In each case, the mono-conversion of pig manure is compared to co-conversion with a 50:50 mixture of pig manure with grass. Anaerobic digestion displayed a greater greenhouse gas mitigation potential than hydrothermal carbonisation in all cases, and co-processing with grass greatly enhances greenhouse gas mitigation potential. China has the largest greenhouse gas mitigation potential (129 MT CO₂ eq), and greatest mitigation per kg of pig manure (1.8 kgCO₂/kg pig manure volatile solids). The energy grid carbon intensity has a significant impact on the greenhouse gas mitigation potential of the different approaches in the different regions. Pig manure is generated in large amounts in China, and the energy generated from biogas offsets a higher carbon intensity grid. Greenhouse gas savings from the anaerobic digestion of pig manure and grass have been calculated to provide a significant potential for reducing total greenhouse gas emissions representation in China (1.05%), the EU (0.92%), and the UK (0.19%). Overall, the utilisation of pig manure could bring about substantial greenhouse savings, especially through co-digestion of pig manure with grass in countries with large pig farming industries and carbon intense energy mixes. Full article

Hydrochars are an alternative form of biochar produced by hydrothermal carbonisation (HTC), a potentially cheaper and greener method. In this paper, the effect of multiple variables on hydrochar properties was investigated. Waste biomass was converted to hydrochar via microwave-assisted hydrothermal carbonisation. The variables were temperature, solution ratio (water-biomass ratio), time, particle size, pH and acetone washing. The measured properties were yield, carbon, oxygen and ash content, higher heating value (HHV), carbon and energy recovery and dye and water adsorption. Feedstock significance was investigated using apple, wheat, barley, oat and pea straw. The investigation into this specific combination of variables and feedstock has not been done before. HTC increased carbon content (~60%), HHV (~24 MJ/kg) and water adsorption and reduced oxygen content and dye adsorption. Thermal analysis suggested hydrochars were not suitable for sequestration. Decreasing the solution ratio was the most significant factor in increasing yield, carbon recovery and energy yield. Increasing the temperature was the most significant factor in increasing carbon and decreasing oxygen content. This affected HHV, with higher temperatures producing a higher energy material, surpassing brown coal. Hydrochars produced at a high solution ratio, temperature and times showed the best carbonisation. Smaller particle size increased yield and carbonisation but increased ash content. Low solution pH increased carbon content, HHV and water adsorption but lowered yield, carbon recovery, energy yield, dye adsorption and oxygen and ash content. High pH increased ash content and dye adsorption but lowered yield, carbon recovery, energy yield and dye adsorption. Acetone decreased yield, carbon recovery, energy yield, carbon content and HHV but increased oxygen, ash content and dye and water adsorption. Barley biomass showed the highest yield and carbon recovery, and pea showed the highest energy yield and HHV. Apple showed the highest carbon content. All the hydrochars showed promise as solid fuels, a soil additive and a precursor for activated carbon but lacked high adsorption for pollutant adsorbents and stability for carbon sequestration. Full article

The integration of hydrothermal carbonisation (HTC) and anaerobic digestion (AD) can overcome some of the disadvantages of thermal or biological processing alone. This study aims to investigate integrated HTC-AD across a range of integration strategies and HTC processing temperatures (150 °C, 200 °C and 250 °C) to improve the energy conversion efficiency (ECE) of grass, compared to AD alone. The separation of hydrochars (HCs) for combustion and process waters (PWs) for digestion appears to be the most energetically feasible HTC-AD integration strategy, compared to HC or HTC-slurry AD. Hydrochars represent the greater energy carrier with between 81–85% of total energy output. The ECE of grass was improved from 51% to 97% (150 °C), 83% (200 °C) and 68% (250 °C) through integrated HTC-AD. Therefore, lower HTC processing temperatures yield more favourable energetics. However, higher HTC temperatures favour more desirable HC properties as a combustion fuel. The hydrochar produced at 250 °C (HC-250) displayed the highest HHV (25.8 MJ/kg) and fixed carbon: volatile matter ratio (0.47), as well as the greatest reduction in slagging and fouling potential (ash flow temperature > 1550 °C). Overall, integrated HTC-AD is an effective energy valorisation strategy for grass. A compromise exists between the quality of hydrochar and the energetic balance. However, at 250 °C the process remains energetically feasible (EROI = 2.63). Full article

The presence of inorganic salts either as part of the substrate or added to the reaction medium are known to significantly affect the reaction pathways during hydrothermal carbonisation (HTC) of biomass. This work aims to understand the influence of salts on hydrothermal carbonisation by processing cellulose in the presence of one or more inorganic salts with different valency. Batch experiments and Differential Scanning Calorimetry were used to investigate the change in reaction pathways during hydrothermal conversion. The effect of salts on the rate of HTC of cellulose can be correlated with the Lewis acidity of the cation and the basicity of the anion. The effect of the anion was more pH-dependent than the cation because it can protonate during the HTC process as organic acids are produced. The introduction of salts with Lewis acidity increases the concentration of low molecular weight compounds in the process water. The addition of a second salt can influence the catalytic effect of the first salt resulting in greater levulinic acid yields at the expense of hydrochar formation. Salts also play an important role in cellulose dissolution and can be used to modify the yield and composition of the hydrochars. Full article

Hydrothermal carbonisation (HTC) can be integrated with anaerobic digestion (AD) for the treatment of digestate, resulting in a solid hydrochar or bio-coal and a process water, which can be recirculated back into AD to produce biogas. The properties of digestate-derived hydrochars do not lend themselves to producing high quality bio-coal and blending with lignocellulosic feedstocks can improve its properties. This study investigates the co-processing of sewage sludge (SS) digestate with three lignocellulosic biomass (grass, privet hedge, and woodchip). The calorific value of the resulting bio-coal is increased following co-processing, although feedstock interactions result in non-additive behaviour. The largest increase in calorific value was observed for co-processing with woodchip. There is evidence for non-additive partitioning of metals during co-processing resulting in only moderate improvements in ash chemistry during combustion. Co-processing also effects the composition of process waters, influencing the potential for biogas production. Experimental biomethane potential (BMP) tests indicate that grass clippings are the most suitable co-feedstock for maintaining both calorific value and biogas production. However, above 200 °C, BMP yields appear to decrease, suggesting the process water may become more inhibitory. Co-processing with wood waste and privet hedge produce the higher CV bio-coal but significantly reduced BMP. Full article

Hydrothermal carbonisation is a promising technology for greenhouse gas (GHG) mitigation through landfill avoidance and power generation, as it can convert high-moisture wastes into bio-coal which can be used for coal substitution. The GHG mitigation potential associated with landfill avoidance of high-moisture food waste (FW) generated in India, China and the EU was calculated and the potential for coal substitution to replace either grid energy, hard coal, or lignite consumption were determined. Different HTC processing conditions were evaluated including temperature and residence times and their effect on energy consumption and energy recovery. The greatest mitigation potential was observed at lower HTC temperatures and shorter residence times with the bio-coal replacing lignite. China had the greatest total mitigation potential (194 MT CO₂ eq), whereas India had the greatest mitigation per kg of FW (1.2 kgCO₂/kg FW). Significant proportions of overall lignite consumption could be substituted in India (12.4%) and China (7.1%), while sizable levels of methane could be mitigated in India (12.5%), China (19.3%), and the EU (7.2%). GHG savings from conversion of high-moisture FW into bio-coal and subsequent coal replacement has significant potential for reducing total GHG emissions and represents in India (3%), China (2.4%), and the EU (1%). Full article