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

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Journal of Environmental Sciences 2024年第6期140卷 69-78页

作者： Judith González-Arias Guillermo Torres-Sempere Miriam González-Castaño Francisco MBaena-Moreno Tomás RReina Inorganic Chemistry Department and Materials Sciences Institute University of Seville-CSICSevilleSpain Materials Sciences Institute(ICMSE) CSIC-University of SevilleSevilleSpain Department of Chemistry and Chemical Engineering Chalmers University of TechnologyGothenburgSE 41296Sweden

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.

关键词： hydrothermal carbonization CO_(2)waste valorization Methanation Profitability analysis

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

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International Journal of Minerals,Metallurgy and Materials 2024年第2期31卷 268-281页

作者： Han Dang Runsheng Xu Jianliang Zhang Mingyong Wang Jinhua Li State Key Laboratory of Advanced Metallurgy University of Science and Technology BeijingBeijing 100083China School of Chemical Engineering The University of QueenslandQueensland 4072Australia

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.

关键词： blast furnace injection biomass cross-upgrading hydrothermal carbonization pyrolysis physicochemical properties gasific-ation properties

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

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Waste Disposal and Sustainable Energy 2022年第3期4卷 205-218页

作者： Tianchi Shen Mi Yan Yuhao Xia Ruixiong Hu Yayong Yang Cheng Chen Feng Chen Dwi Hantoko Institute of Energy and Power Engineering College of Mechanical EngineeringZhejiang University of TechnologyHangzhou310014China

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.

关键词： Food waste hydrothermal carbonization Fenton Adsorption Wastewater

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Hydrochar Pelletization towards Solid Biofuel from Biowaste hydrothermal carbonization

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Journal of Renewable Materials 2023年第1期11卷 411-422页

作者： Ao Li Kai Jin Jinrui Qin Zhaowei Huang Yu Liu Rui Chen Tengfei Wang Junmin Chen Faculty of Geosciences and Environmental Engineering Southwest Jiao Tong UniversityChengdu611756China

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.

关键词： Biomass hydrothermal carbonization hydrochar pelletization

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ASSESSMENT OF HEAVY METALS IN HYDROCHAR PRODUCED BY hydrothermal carbonization OF DAIRY MANURE

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Frontiers of Agricultural Science and Engineering 2023年第3期10卷 437-447页

作者： B.Brian HE Zheting BI Lide CHEN Chemical&Biological Engineering College of EngineeringUniversity of Idaho875 Perimeter Drive MS 0904MoscowID 83844USA. Shape Therapeutics 700 Dexter Avenue NorthSL15SeattleWA 98109USA Soil and Water Systems Twin Falls Research and Extension CenterUniversity of Idaho315 Falls Ave.Twin FallsID 83303USA

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.

关键词： heavy metals dairy manure hydrochar hydrothermal carbonization waste management

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

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Carbon Resources Conversion 2018年第1期1卷 81-85页

作者： Samar Seyedsadr Rafat Al Afif Christoph Pfeifer University of Natural Resources and Life Sciences Institute of Chemical and Energy EngineeringMuthgasse 1071190 ViennaAustria

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 200C 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.

关键词： hydrothermal carbonization Biomass Hydro-char Energy yield

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

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Journal of Materials Science & Technology 2013年第8期29卷 747-751页

作者： Marcelo Marques Tusi Michele Brandalise Nataly Soares de Oliveira Polanco Olandir Vercino Correa Antonio Carlos da Silva Juan Carlo Villalba Fauze Jaco Anaissi Almir Oliveira Neto Estevam Vitorio Spinac Universidade Regional Integrada do Alto Uruguai e das Missoes-URI Av.Batista Bonoto Sobrinhos/nSao Vicente97700-000 SantiagoRSBrazil Instituto de Pesquisas Energticas e Nucleares-IPEN/CNEN-SP Av.Prof.Lineu Prestes2242Cidade Universitria05508-900 Sao PauloSPBrazil Universidade Estadual do Centro-Oeste-UNICENTRO R.Simeao Varela de S 03Vila Carli85040-080 GuarapuavaPRBrazil

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.

关键词： Cellulose hydrothermal carbonization Alcohol-reduction process PtRu/C electrocatalysts Direct methanol fuel cell

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Preparation and Characterization of Carbon Microspheres From Waste Cotton Textiles By hydrothermal carbonization

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Journal of Renewable Materials 2019年第12期7卷 1309-1319页

作者： Yongfang Zhang Wensheng Hou Hong Guo Sheng Shi Jinming Dai College of Textile Engineering Taiyuan University of TechnologyTaiyuan030024China College of Materials Science and Engineering Taiyuan University of TechnologyTaiyuan030024China

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.

关键词： Carbon microsphere waste cotton fiber copper sulphate hydrothermal carbonization

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

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Green Energy & Environment 2018年第2期3卷 163-171页

作者： Fen Yue Christian Marcus Pedersen Xiuyin Yan Yequn Liu Danlei Xiang Caifang Ning Yingxiong Wang Yan Qiao Institute of Coal Chemistry Chinese Academy of Sciences Institute of Process Engineering Chinese Academy of Sciences Department of Chemistry University of Copenhagen Taiyuan Supervision and Testing Station for Quality of Grain Department of Applied Biology and Chemical Technology The Hong Kong Polytechnic University

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.

关键词： NMR hydrothermal carbonization Furfural residue Stock process water

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hydrothermal carbonization of Deciduous Biomass(Alnus incana)and Pelletization Prospects

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Journal of Sustainable Bioenergy Systems 2017年第3期7卷 138-148页

作者： Raghu Kc Indu Babu Sara Alatalo Jarno Fohr Tapio Ranta Ismo Tiihonen Laboratory of Bioenergy Lappeenranta University of TechnologyMikkeliFinland Laboratory of Green Chemistry LappeenrantaUniversity of TechnologyMikkeliFinland Riihikatu 3 11100RiihimakiFinland Tiihonen Ismo Olavi Saahkarintie 176 77700 Rautalampi Finland

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.

关键词： Sustainable Bioenergy hydrothermal carbonization Hydrochar Pelletization

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