Cross-upgrading of biomass hydrothermal carbonization and pyrolysis for high quality blast furnace injection fuel production:Physicochemical characteristics and gasification kinetics analysis

The paper proposes a biomass cross-upgrading process that combines hydrothermal carbonization and pyrolysis to produce high-quality blast furnace injection fuel.The results showed that after upgrading,the volatile content of biochar ranged from 16.19%to 45.35%,and the alkali metal content,ash content,and specific surface area were significantly reduced.The optimal route for biochar pro-duction is hydrothermal carbonization-pyrolysis(P-HC),resulting in biochar with a higher calorific value,C=C structure,and increased graphitization degree.The apparent activation energy(E)of the sample ranges from 199.1 to 324.8 kJ/mol,with P-HC having an E of 277.8 kJ/mol,lower than that of raw biomass,primary biochar,and anthracite.This makes P-HC more suitable for blast furnace injection fuel.Additionally,the paper proposes a path for P-HC injection in blast furnaces and calculates potential environmental benefits.P-HC of-fers the highest potential for carbon emission reduction,capable of reducing emissions by 96.04 kg/t when replacing 40wt%coal injec-tion.

Hydrochar Pelletization towards Solid Biofuel from Biowaste Hydrothermal Carbonization

Hydrothermal carbonization is highly applicable to high moisture biomass upgrading due to the fact that moist-ure involved can be directly used as reaction media under the subcritical-water region.With this,value-added utilization of hydrochar as solid fuel with high carbon and energy density is one of the important pathways for biomass conversion.In this review,the dewatering properties of hydrochar after the hydrothermal carbonization of biowaste,coalification degree with elemental composition and evolution,pelletization of hydrochar to enhance the mechanical properties and density,coupled with the combustion properties of hydrochar biofuel were discussed with various biomass and carbonization parameters.Potential applications for the co-combustion with coal,cleaner properties and energy balance for biowaste hydrothermal carbonization were presented as well as the challenges.

Preparation and Characterization of Carbon Microspheres From Waste Cotton Textiles By Hydrothermal Carbonization

Carbon microspheres were prepared from waste cotton fibers by hydrothermal carbonization(HTC)with the addition of copper sulphate in this work.The important influence factors,temperature,concentration of copper sulphate,resident time were explored here.The smooth and regular carbon microspheres could be formed at 330°C with 0.15 wt%copper sulphate after 6 h from waste cotton fibers.The crystal structures of cotton fibers were destructed in a short resident time with 0.15 wt%copper sulphate from SEM images and XRD patterns of solid products.This strategy provides a new,mild and efficient method to prepare carbon microspheres from waste cotton fibers by HTC.FTIR spectra verified that the abundant functional groups existed on the surface of synthesized carbon microspheres.From XPS and element analysis results,the copper sulphate participated in the forming process of carbon microspheres indeed.The presence of copper sulphate in the carbon microspheres provided a possibility for the application in antibacterial field.Besides,the catalytic mechanism of copper sulphate on the hydrolysis and carbonization of waste cotton fibers were also discussed.In conclusion,the copper sulphate is an efficient agent for preparing carbon microspheres by HTC from waste cotton fibers.

NMR studies of stock process water and reaction pathways in hydrothermal carbonization of furfural residue

Hydrothermal carbonization(HTC) is a valuable approach to convert furfural residue(FR) into carbon material. The prepared biochars are usually characterized comprehensively, while the stock process water still remains to be studied in detail. Herein, a NMR study of the main components in stock process water generated at different HTC reaction conditions was reported. Various qualitative and quantitative NMR techniques(~1H and ^(13)C NMR,~1H-~1H COSY and ~1H-^(13)C HSQC etc.) especially 1D selective gradient total correlation spectroscopy(TOCSY NMR) were strategically applied in the analysis of HTC stock process water. Without separation and purification, it was demonstrated that the main detectable compounds are 5-hydroxymethylfurfural, formic acid, methanol, acetic acid, levulinic acid, glycerol, hydroxyacetone and acetaldehyde in this complicate mixture. Furthermore, the relationship between the concentration of major products and the reaction conditions(180-240 ℃ at 8 h, and 1-24 h at 240 ℃) was established. Finally, reasonable reaction pathways for hydrothermal conversion of FR were proposed based on this result and our previously obtained characteristics of biochars. The routine and challenging NMR methods utilized here would be an alternative other than HPLC or GC for biomass conversion research and can be extended to more studies.

Hydrothermal Carbonization of Deciduous Biomass(Alnus incana)and Pelletization Prospects

Thermal treatment of biomass has been attracting attention for a decade or so, especially torrefaction. However, for the past few years, wet pyrolysis, also known as hydrothermal carbonization (HTC), has been getting some attention. Hydrothermal carbonization is a thermal treatment of biomass in the presence of water in a temperature range of 180°C - 260°C. This method of treating biomass has some benefits which others do not, such as it can handle extremely wet biomass. However, treating biomass may not be enough for practical use. It may need to be transported and stored. Thus, this study explored the idea of pelletizing the HTC biomass. The mechanical strength of the HTC pellets was found to be 93%, whereas, higher heating value (HHV) (dry basis) was found to be 4% higher than the corresponding white pellets. The initial results with some limited parameters indicated that it would be possible to pelletize without binder. However, extensive research on energy balance and economic assessment would be necessary to achieve economic feasibility.

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 coproduction 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.

ASSESSMENT OF HEAVY METALS IN HYDROCHAR PRODUCED BY HYDROTHERMAL CARBONIZATION OF DAIRY MANURE

Hydrochar produced from dairy manure is a regulated biosolid if being promoted for agricultural applications thus must have the properties that comply with all environmental standards and government regulations,including the levels of heavy metals(HMs).In this study,systematic research was conducted on HM levels in hydrochar from dairy manure and on the effects of processing conditions,including processing temperature(180–255℃),holding time(30–120 min)and solid content of manure slurry(2%–15%),through a central composite design and statistical analyses.It was found that HMs can be retained in hydrochar,ranging from 40%to 100%.The processing temperature and solid content in the feed were the most influential process parameters that affected HMs retention in hydrochar.Statistical analysis showed that there was no single optimal point to minimize HMs retained in hydrochar,but there were minimization points at given processing time and solid content.Most HMs concentrations were higher in hydrochar than those initially in dairy manure but were greatly below the thresholds as set by the US government regulations.Thus,hydrochar is feasible for use as a phosphorus-enriched organic fertilizer and/or soil amendment for agricultural applications without serious concerns about HMs it might contain.

Hydrothermal carbonization of agricultural residues:A case study of the farm residues-based biogas plants

Hydrothermal carbonization(HTC)of biomass is a promising method to produce carbonaceous materials.The work presented in this article addresses the application of hydrothermal carbonization(HTC)to produce a solid fuel named HTC-Biochar,whose characteristics are comparable to lignite coal.Biogas sludge(SD),maize silage(MS),and barley silage(BS)as a substrates were hydrothermally carbonized in a 1.5 L batch reactor at 200
C for 6 h.The effect of mixing ratios of different substrates on HTC was investigated.Chemical compositions and combustion characteristics of hydro-chars obtained from mono-and co-carbonization were evaluated.Result showed that HTC increased carbon contents and higher heating values(HHV)by 1.4–14.4%and 13–36%,respectively.The evolution of the H/C and O/C atomic ratios indicated that dehydration and decarboxylation occurred during hydrothermal carbonization for all samples.Furthermore,a significant synergistic enhancement was observed for HHV and carbon content.A mixing ratio of 1:1 for BS and SD showed the best performance for co-HTC.In summary,hydrothermal co-carbonization is a promising strategy to tailor high-performance hydro-char for energy applications.

Preparation of porous carbon directly from hydrothermal carbonization of fructose and phloroglucinol for adsorption of tetracycline

Hydrothermal carbonization of biomass is a promising method to prepare carbonaceous materials.Generally,post physical or chemical activation is necessary to increase surface area and porosity of the carbon.Herein,porous carbonaceous material（FPC） with large surface area（481.7 m^2/g） and pore volume（0.73 cm^3/g） was prepared directly from hydrothermal carbonization of fructose and phloroglucinol in hydroalcoholic mixture.Structure characteristics of the FPC and its adsorption capacity for a representative antibiotic tetracycline in aqueous solution were investigated.This work provides a green and efficient method to fabricate porous carbonaceous adsorbent that has great potential applications in chemical and environmental fields.

Ni/Carbon Hybrid Prepared by Hydrothermal Carbonization and Thermal Treatment as Support for PtRu Nanoparticles for Direct Methanol Fuel Cell

Ni/Carbon was prepared in two steps： initially cellulose as carbon source and NiCl2·6H2O as catalyst of the carbonization process were submitted to hydrothermal treatment at 200 ℃ and further to thermal treatment at 900 ℃ under argon atmosphere. The obtained material contains Ni nanoparticles with face-centered cubic （fcc） structure dispersed on amorphous carbon with graphitic domains. PtRu/C electrocatalysts （carbon- supported PtRu nanoparticles） were prepared by an alcohol-reduction process using Ni/Carbon as support. The materials were characterized by thermogravimetric analysis, energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy and tested as anodes in single direct methanol fuel cell （DMFC）. The performances of PtRu/C electrocatalysts using Ni/Carbon as support were superior to those obtained for PtRu/C using commercial carbon black Vulcan XC72 as support.

Treatment of wastewater from food waste hydrothermal carbonization via Fenton oxidization combined activated carbon adsorption

Hydrothermal carbonization(HTC)of food waste can produce hydrochar for further utilization as high-quality fuel or carbon materials,but the by-product of liquid effluent,named HTC wastewater,has a high chemical oxygen demand(COD)content and other organic pollutants.This study focused on the feasibility of Fenton oxidation combined with activated carbon(AC)to reduce COD in HTC wastewater.The effects of different parameters including pH,dosage of hydrogen peroxide,molar ratio of Fe^(2+)/H_(2)O_(2),and reaction time were tested and discussed.Eventually,through the optimized Fenton oxidation(pH=3,H_(2)O_(2)dosage=1.5 mol/L,Fe^(2+)/H_(2)O_(2)=1:15,reaction time=60 min)combined optimized AC adsorption process(AC dosage=30 g/L),the COD value reduced from 42,000 mg/L to 3075 mg/L,indicating a COD removal efficiency of 92.7%and a color removal ratio of 91.9%,respectively.The comparison of GC/MS(gas chromatography mass spectrometer)and FTIR(Fourier transform infrared spectrometer)of liquid residual from different treatment methods also indicated that the types of organic substances in HTC wastewater were significantly reduced through Fenton oxidation and AC adsorption.

Removal of Dyes in Aqueous Media with Hydrochar Base of Solid Tanneries Waste: Optimization Process and Application

The Response Surface Methodology (RSM) was used to optimise the conditions of preparation of activated hydrochar from tannery solid waste by hydrothermal carbonisation (HTC). The main factors such as residence time, moisture content and final carbonisation temperature were investigated during the optimisation of hydrochar preparation conditions. The three responses investigated are hydrochar yield, iodine and methylene blue indices. The results of experimental analyses showed that the yield of hydrochar decreases with increasing final temperature, leading to the formation of micropores inside the carbonaceous solid. The optimum conditions for preparing the following hydrochar were obtained: 83.10%, 390.44 mg∙g−1 and 259.63 mg∙g−1 respectively for the hydrochar yield, the iodine and methylene blue indices. The specific surface area of prepared hydrochar is 849.160 m2/g, SEM micrographs showed a porous heterogeneous surface and particularly, the hydrochar surface also revealed external pores on the hydrochar surface which acted as a pathway to the micropores. Fourier transform infrared (FTIR), however, showed a predominance of acid functions on the surface of the carbonaceous solids. Tests were carried out to eliminate indigo carmine in aqueous media. Activated hydrochar showed a high level of activity, with the Langmuir and Freundlich isotherms giving an adsorption quantity of 354.610 mol/g and a KF constant of 468.2489, respectively. The findings of the research revealed that hydrochar produced is well adapted for dyes removal.

The Hydrochar Characters of Municipal Sewage Sludge Under Different Hydrothermal Temperatures and Durations

Innovative measure is a urgent requirement for managing the huge volume of municipal sewage sludge. The hydrothermal carbonation （HTC） shows some potential advantages for using hydrochar as a soil conditioner. The aim of this work was to investigate the properties of hydrochars, by means of the HTC of municipal sewage sludge under different temperatures （190 and 260~C） and reaction hours （1, 6, 12, 18 and 24 h）. The HTC led to the decreases of N, O and H contents by more than 54.6, 37.9 and 10.0%, respectively, and slight changes of C content. The Py-GC-MS analysis showed that a large proportion of fatty acids, in particular hexadecanoic acid, transferred into alkenes, olefins and aromatic compounds. The 13C-NMR and fourier transform infrared spectra （FTIR） confirmed the transformation and changes in chemical structure in which hydrochar contained lower oxygen-containing organic C of O-alkyl, carboxylic and carbonyl C and aliphaticity, but higher aromatic C and aromaticity. The rich hydrophobic functions induced in high positive charges in the charred sludge. The HTC facilitated the pore structure development, proved by higher specific surface area and specific pore volume, with a maximum of 17.30 and 0.83 cm^3 g^-1, respectively. The availabilities of N, P and K markedly reduced during HTC treatment. The activities of most heavy metals were depressed though they accumulated in the hydrochar. Further work is required to investigate the values and risk of the charred sludge amended to soil.

Hydrothermal conversion of lignocellulosic biomass into high-value energy storage materials

Preparation of hierarchically porous, heteroatom-rich nanostructured carbons through green and scalable routes plays a key role for practical energy storage applications. In this work, naturally abundant lignocellulosic agricultural waste with high initial oxygen content, hazelnut shells, were hydrothermally carbonized and converted into nanostructured ‘hydrochar’. Environmentally benign ceramic/magnesium oxide（Mg O） templating was used to introduce porosity into the hydrochar. Electrochemical performance of the resulting material（HM700） was investigated in aqueous solutions of 1 M H;SO;, 6 M KOH and1 M Na;SO;, using a three-electrode cell. HM700 achieved a high specific capacitance of 323.2 F/g in 1 M H;SO;（at 1 A/g,-0.3 to 0.9 V vs. Ag/Ag Cl） due to the contributions of oxygen heteroatoms（13.5 wt%）to the total capacitance by pseudo-capacitive effect. Moreover, a maximum energy density of 11.1 Wh/kg and a maximum power density of 3686.2 W/kg were attained for the symmetric supercapacitor employing HM700 as electrode material（1 M Na;SO;, E = 2 V）, making the device promising for green supercapacitor applications.

Highly electroactive N–Fe hydrothermal carbons and carbon nanotubes for the oxygen reduction reaction

Glucose-derived carbons were prepared by hydrothermal carbonization of glucose followed by carbonization or activation to obtain carbon materials with different microporosities. These microporous carbons and carbon nanotubes(CNTs) were functionalized with melamine and/or iron(Ⅱ) phthalocyanine(FePc)following three different methodologies:(i) Functionalization with melamine via thermal treatment,(ii)incorporation of the lowest amount of FePc reported in the literature via incipient wetness impregnation followed by thermal treatment and(iii) functionalization with melamine followed by Fe Pc incorporation.The chemical and textural characterization of the prepared materials and their electrochemical assessment allowed to understand the role of microporosity in the incorporation of FePc and its effect on the oxygen reduction reaction(ORR). It was observed that FePc was preferentially incorporated inside the porous structure, especially in samples with more developed microporosity. However, functionalization with melamine modified the textural properties and the surface chemistry, favoring the incorporation of FePc on the surface. Regarding the electrochemical performance, the presence of FePc greatly enhanced the electroactivity of the microporous catalysts. An onset potential of 0.88 V and a four-electron pathway were obtained for glucose-derived carbons, whereas the limiting current densities and kinetic current densities rose by 126% and 222%, respectively, in comparison to the base sample. Notwithstanding, the highest electrochemical activity was observed for the sample prepared with CNTs, due to the synergy between the active metal centers and their highly graphitic carbon structure. The electrochemical parameters of CNTFeP csurpass the commercial Pt/C. The half-wave potential is 40 mV higher, the limiting current density increases by 17%, and a negligible production of by-products(< 1%) was observed.

Improving ORR activity of carbon nanotubes by hydrothermal carbon deposition method

Nitrogen doped carbons are an important family of materials with ideal activity for oxygen reduction reaction(ORR). It is always interesting to search functional carbons with high heteroatom contents and desirable structure for ORR. Within this study, the surface modification of carbon nanotubes(CNTs) via hydrothermal carbonization(HTC) technique in the presence of glucose and urea was reported, where the surface of CNTs is successfully coated by nitrogen containing hydrothermal carbon layers. The resulting composite combines both advantages of the outstanding electrical conductivity of CNTs and the effective ORR active sites provided by doped nitrogen in the HTC carbon layers. By controlling the ratio of glucose and urea, the nitrogen contents coated on the surface of CNTs can reach up to 1.7 wt%. The resulting materials show outstanding electrochemical activity towards ORR in alkaline electrolyte, making it one of the valuable metal-free electrode materials and a competent alternative to the state-of-the-art Pt/C catalyst.

Microwave-assisted Hydrothermal Synthesis of Carbon Materials with Tunable Microstructure

A facile microwave-assisted hydrothermal route has been developed for a synthesis of versatile carbon materials. The monosaccharide fructose aqueous solution was adopted as the starting material, and the p H of the solution was adjusted to be in acidic（pH 4）, neutral（pH 7） and basic（pH 10.5） conditions. The p H buffered fructose solutions were treated at different temperatures by a microwave-assisted hydrothermal technique. As-prepared carbon materials displayed p H and temperature dependent multi-morphologies（porous, spherical or core-shell）, which were determined by transmission and scanning electron microscopic analyses（TEM and SEM）. And the hypothesis of dehydration mechanism of hydrothermal synthesis was analyzed by ultraviolet extinction and Fourier transform infrared spectroscopy. It was found that as compared with normal hydrothermal synthesis, microwave assistance could efficiently increase the production yield and improve the spherical geometry of the carbon particles in neutral condition. By changing the p H of the system, acidic p H induces aggregation of the spheres, while basic p H produces more trends toward core-shell or sponge-like porous structure. The study opens a novel route to the production of polytropic carbon materials and suggests a potential niche market established from the green synthesis.

Nitrogen-Doped Carbon Nanotube-Supported Pd Catalyst for Improved Electrocatalytic Performance toward Ethanol Electrooxidation

In this study, hydrothermal carbonization(HTC)was applied for surface functionalization of carbon nanotubes(CNTs) in the presence of glucose and urea. The HTC process allowed the deposition of thin nitrogen-doped carbon layers on the surface of the CNTs. By controlling the ratio of glucose to urea, nitrogen contents of up to 1.7 wt%were achieved. The nitrogen-doped carbon nanotube-supported Pd catalysts exhibited superior electrochemical activity for ethanol oxidation relative to the pristine CNTs.Importantly, a 1.5-fold increase in the specific activity was observed for the Pd/HTC-N1.67%CNTs relative to the catalyst without nitrogen doping(Pd/HTC-CNTs). Furtherexperiments indicated that the introduction of nitrogen species on the surface of the CNTs improved the Pd(0)loading and increased the binding energy.

Kinetic analysis and modeling of maize straw hydrochar combustion using a multi-Gaussian-distributed activation energy model

Combustion kinetics of the hydrochar was investigated using a multi-Gaussian-distributed activation energy model(DAEM)to ex-pand the knowledge on the combustion mechanisms.The results demonstrated that the kinetic parameters calculated by the multi-Gaussian-DAEM accurately represented the experimental conversion rate curves.Overall,the feedstock combustion could be divided into four stages:the decomposition of hemicellulose,cellulose,lignin,and char combustion.The hydrochar combustion could in turn be divided into three stages:the combustion of cellulose,lignin,and char.The mean activation energy ranges obtained for the cellulose,lignin,and char were 273.7-292.8,315.1-334.5,and 354.4-370 kJ/mol,respectively,with the standard deviations of 2.1-23.1,9.5-27.4,and 12.1-22.9 kJ/mol,re-spectively.The cellulose and lignin contents first increased and then decreased with increasing hydrothermal carbonization(HTC)temperature,while the mass fraction of char gradually increased.

Synthesis of Humin-based Carbon Quantum Dots and Luminescent Properties

The unique properties of carbon quantum dots （CQDs） make them promising materials in many ？elds. Herein, we present a facile method for the preparation of photo-luminescent CQDs using humins as the carbon precursor for the purpose of providing a high value-added solution for this “biomass conversion process waste”. The structure of the CQDs was analyzed, and the effects of reaction temperature and time on the CQDs’ ？uorescence were investigated. The results showed that humins were effectively carbonized during the reaction. The ？uorescence intensity of humin-based CQDs initially increased with reaction temperature and time, and subsequently decreased beyond 200℃ and 4 h. Polyaromatic structures and hydrophilic groups such as O-H, C-O, -COOH and C==O groups exist in the CQDs. The humin-based CQDs have the dimension of 3~7 nm with an average size of about 5.5 nm. The highest emission intensity of blue/cyan ？uorescence light at 440 nm is achieved on the excitation with UV light at the wavelength of 330 nm.