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 con...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.展开更多
In order to obtain liquefied products with higher yields of aromatic molecules to produce mesophase pitch,a good understanding of the relevant reaction mechanisms is required.Reactive molecular dynamics simulations we...In order to obtain liquefied products with higher yields of aromatic molecules to produce mesophase pitch,a good understanding of the relevant reaction mechanisms is required.Reactive molecular dynamics simulations were used to study the thermal reactions of pyrene,1-methylpyrene,7,8,9,10-tetrahydrobenzopyrene,and mixtures of pyrene with 1-octene,cyclohexene,or styrene.The reactant conversion rates,reaction rates,and product distributions were calculated and compared,and the mechanisms were analyzed and discussed.The results demonstrated that methyl and naphthenic structures in aromatics might improve the conversion rates of reactants in hydrogen transfer processes,but their steric hindrances prohibited the generation of high polymers.The naphthenic structures could generate more free radicals and presented a more obvious inhibition effect on the condensation of polymers compared with the methyl side chains.It was discovered that when different olefins were mixed with pyrene,1-octene primarily underwent pyrolysis reactions,whereas cyclohexene mainly underwent hydrogen transfer reactions with pyrene and styrene,mostly producing superconjugated biradicals through condensation reactions with pyrene.In the mixture systems,the olefins scattered aromatic molecules,hindering the formation of pyrene trimers and higher polymers.According to the reactive molecular dynamics simulations,styrene may enhance the yield of dimer and enable the controlled polycondensation of pyrene.展开更多
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-adde...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.展开更多
Decarbonization is a critical issue for peaking CO_(2) emissions of energy-intensive industries,such as the iron and steel industry.The decarbonization options of China’s ironmaking and steelmaking sector were discus...Decarbonization is a critical issue for peaking CO_(2) emissions of energy-intensive industries,such as the iron and steel industry.The decarbonization options of China’s ironmaking and steelmaking sector were discussed based on a systematic three-dimensional low-carbon analysis from the aspects of resource utilization(Y),energy utilization(Q),and energy cleanliness which is evaluated by a process general emission factor(PGEF)on all the related processes,including the current blast furnace(BF)-basic oxygen furnace(BOF)integrated process and the specific sub-processes,as well as the electric arc furnace(EAF)process,typical direct reduction(DR)process,and smelting reduction(SR)process.The study indicates that the three-dimensional aspects,particularly the energy structure,should be comprehensively considered to quantitatively evaluate the decarbonization road map based on novel technologies or processes.Promoting scrap utilization(improvement of Y)and the substitution of carbon-based energy(improvement of PGEF)in particular is critical.In terms of process scale,promoting the development of the scrap-based EAF or DR-EAF process is highly encouraged because of their lower PGEF.The three-dimensional method is expected to extend to other processes or industries,such as the cement production and thermal electricity generation industries.展开更多
Hydrothermal carbonization(HTC) of lignocellulosic biomass is a promising technology for the production of carbon materials with negative carbon emissions. However, the high reaction temperature and energy consumption...Hydrothermal carbonization(HTC) of lignocellulosic biomass is a promising technology for the production of carbon materials with negative carbon emissions. However, the high reaction temperature and energy consumption have limited the development of HTC technology. In conventional batch reactors, the temperature and pressure are typically coupled at saturated states. In this study, a decoupled temperature and pressure hydrothermal(DTPH) reaction system was developed to decrease the temperature of the HTC reaction of lignocellulosic biomass(rice straw and poplar leaves). The properties of hydrochars were analyzed by scanning electron microscopy(SEM), Fourier transform infrared(FTIR) spectroscopy, X-ray photoelectron spectroscopy(XPS), Raman spectroscopy, X-ray diffraction(XRD), thermogravimetric analyzer(TGA), etc. to propose the reaction mechanism. The results showed that the HTC reaction of lignocellulosic biomass could be realized at a low temperature of 200℃ in the DTPH process, breaking the temperature limit(230℃) in the conventional process. The DTPH method could break the barrier of the crystalline structure of cellulose in the lignocellulosic biomass with high cellulose content, realizing the carbonization of cellulose and hemicellulose with the dehydration, unsaturated bond formation, and aromatization. The produced hydrochar had an appearance of carbon microspheres, with high calorific values, abundant oxygen-containing functional groups, a certain degree of graphitization, and good thermal stability. Cellulose acts not only as a barrier to protect itself and hemicellulose from decomposition, but also as a key precursor for the formation of carbon microspheres. This study shows a promising method for synthesizing carbon materials from lignocellulosic biomass with a carbon-negative effect.展开更多
Propylene is a significant basic material for petrochemicals such as polypropylene,propylene oxide,etc.With abundant propane supply from shale gas,propane dehydrogenation(PDH)becomes extensively attractive as an on-pu...Propylene is a significant basic material for petrochemicals such as polypropylene,propylene oxide,etc.With abundant propane supply from shale gas,propane dehydrogenation(PDH)becomes extensively attractive as an on-purpose propylene production route in recent years.Nitrogen-doped carbon(NC)nanopolyhedra supported cobalt catalysts were synthesized in one-step of ZIF-67 pyrolysis and investigated further in PDH.XPS,TEM and N_(2) adsorption-desorption were used to study the influence of carbonization temperature on as-prepared NC supported cobalt catalysts.The temperature is found to affect the cobalt phase and nitrogen species of the catalysts.And the positive correlation was established between Co0 proportion and space time yield of propylene,indicating that the modulation of carbonization temperature could be important for catalytic performance.展开更多
Greenhouse gas emissions from waste plastics have caused global warming all over the world,which has been a central threat to the ecological environment for humans,flora and fauna.Among waste plastics,waste polyethyle...Greenhouse gas emissions from waste plastics have caused global warming all over the world,which has been a central threat to the ecological environment for humans,flora and fauna.Among waste plastics,waste polyethylene terephthalate(PET)is attractive due to its excellent stability and degradation-resistant.Therefore,merging China’s carbon peak and carbon neutrality goals would be beneficial.In this review,we summarize the current state-of-the-art of carbon emission decrease from a multi-scale perspective technologically.We suggest that the carbon peak for waste PET can be achieved by employing the closed-loop supply chain,including recycling,biomass utilization,carbon capture and utilization.Waste PET can be a valuable and renewable resource in the whole life cycle.Undoubtedly,all kinds of PET plastics can be ultimately converted into CO_(2),which can also be feedstock for various kinds of chemical products,including ethyl alcohol,formic acid,soda ash,PU,starch and so on.As a result,the closed-loop supply chain can help the PET plastics industry drastically reduce its carbon footprint.展开更多
High-performance carbonaceous electrode materials for supercapacitors were synthesized by subjecting corn starch to a simple molten salt activation process with K<sub>2</sub>CO<sub>3</sub> at a...High-performance carbonaceous electrode materials for supercapacitors were synthesized by subjecting corn starch to a simple molten salt activation process with K<sub>2</sub>CO<sub>3</sub> at a temperature of 850˚C. The resulting carbon material, obtained after activating for 1 hour, displayed excellent capacitive properties due to the synergistic effects of its porous structure. Utilizing these electrodes, the supercapacitor exhibited a high discharge capacitance (248 F g<sup>−1</sup> at 1 A g<sup>−1</sup>), which is 2.4 times higher than that of activated carbon without K<sub>2</sub>CO<sub>3</sub> activation. The enhancement in electrical performance was analyzed through SEM and XRD analysis, revealing that the porous and disordered structure provides a greater number of charge storage sites, resulting in improved capacitive performance.展开更多
To overcome the ever-growing organic pollutions in the water system,abundant efforts have been dedicated to fabricating efficient Fenton-like carbon catalysts.However,the rational design of carbon catalysts with high ...To overcome the ever-growing organic pollutions in the water system,abundant efforts have been dedicated to fabricating efficient Fenton-like carbon catalysts.However,the rational design of carbon catalysts with high intrinsic activity remains a long-term goal.Herein,we report a new N-molecule-assisted self-catalytic carbonization process in augmenting the intrinsic Fenton-like activity of metal-organic-framework-derived carbon hybrids.During carbonization,the N-molecules provide alkane/ammonia gases and the formed iron nanocrystals act as the in situ catalysts,which result in the elaborated formation of carbon nanotubes(in situ chemical vapor deposition from alkane/iron catalysts)and micro-/meso-porous structures(ammonia gas etching).The obtained catalysts exhibited with abundant Fe/Fe-Nx/pyridinic-N active species,micro-/meso-porous structures,and conductive carbon nanotubes.Consequently,the catalysts exhibit high efficiency toward the degradation of different organic pollutions,such as bisphenol A,methylene blue,and tetracycline.This study not only creates a new pathway for achieving highly active Fenton-like carbon catalysts but also takes a step toward the customized production of advanced carbon hybrids for diverse energy and environmental applications.展开更多
Coal due to its relatively large quantities and wide distribution worldwide has generated renewed interest in research and development with the aim of establishing coal conversion technologies that are technically rel...Coal due to its relatively large quantities and wide distribution worldwide has generated renewed interest in research and development with the aim of establishing coal conversion technologies that are technically reliable,envi-ronmentally and economically feasible.It has proved to be a prominent energy source in emerging markets with increasing energy demand by accounting for the largest increase in the demand of energy amongst all other energy sources.Fur-thermore,with its higher mesophase content,coal tar is an appropriate raw material for precursors in the production of carbon fiber.However,whenever a material is put to use,it is important to be able to associate its properties to the behavioral characteristics during a conversion process so as to have a basis for opting for the material in a given process or adjusting the operating conditions in order to optimize the material utilization.Therefore,as with any other material,it is important to be able to relate the properties of coal to its utilization.A review was carried out on the influence of coal properties on four main utilization technologies:gasification,carbonization,liquefaction and carbon fibre production.Among several properties rank,type,mineral matter content,distribution of trace elements,structural composition and pore structure were found to be most influential on the behavior of coal during conversion processes.展开更多
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 sulpha...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.展开更多
The state-of-the-art approaches for adjusting the structural characteristics of porous carbons are the aftertreatments, which are complicated and time consuming. In this work, a facile approach was developed, i.e., co...The state-of-the-art approaches for adjusting the structural characteristics of porous carbons are the aftertreatments, which are complicated and time consuming. In this work, a facile approach was developed, i.e., controlling the initial oxygen concentration in-situ during the direct carbonization of zeolitic imidazole framework-8(ZIF-8), to adjust the pore structure and prepare hierarchically porous carbons. The introduction of oxygen can significantly affect the crystalline and pore structures of porous carbons, and promote the pore widening and the formation of mesopores. An appropriate initial oxygen concentration can notably enhance the surface area and mesopore volume of porous carbon, and then improve the adsorption capacity toward methylene blue(MB) dye from water by 3.4 times. The developed approach is more efficient at lower carbonization temperature.Moreover, the introduction of oxygen can increase the ratio of HO\\C_O groups on the carbon surface, leading to enhanced interaction with MB molecules and higher adsorption capacity toward MB. The as-prepared porous carbons exhibit superior adsorption capacities toward MB dye as compared to the reported ZIF-8 derived carbons. These findings would aid the development of porous carbon materials with high performance.展开更多
A binder-free Ir-dispersed ordered mesoporous carbon(Ir-OMC) catalytic electrode has been prepared through a designed in-situ carbonization method, which involves coating resorcinol and formaldehyde mixtures with irid...A binder-free Ir-dispersed ordered mesoporous carbon(Ir-OMC) catalytic electrode has been prepared through a designed in-situ carbonization method, which involves coating resorcinol and formaldehyde mixtures with iridium precursors onto the three-dimensional nickel foam framework, followed by insitu calcination in N_2 atmosphere at 800 ℃ for 3 h. This electrode shows a large surface area, ordered mesoporous structure and homogeneous distribution of metal nanoparticles. It presents good activity and stability towards hydrogen evolution reaction, which is attributed to the efficient mass and electron transport from the intimate contact among Ir nanoparticles, ordered mesoporous carbon matrix and 3 D conductive substrate. We hope that this in-situ carbonization synthetic route can also be applied to design more high-performance catalysts for water splitting, fuel cells and other clean energy devices.展开更多
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...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.展开更多
Based on the drilling data of the Silurian Longmaxi Formation in the Sichuan Basin and periphery, SW China, the Ro lower limits and essential features of the carbonization of organic matter in over-high maturity marin...Based on the drilling data of the Silurian Longmaxi Formation in the Sichuan Basin and periphery, SW China, the Ro lower limits and essential features of the carbonization of organic matter in over-high maturity marine shale were examined using laser Raman, electrical and physical property characterization techniques. Three preliminary conclusions are drawn:(1) The lower limit of Ro for the carbonization of Type I-II1 organic matter in marine shale is 3.5%; when the Ro is less than 3.4%, carbonization of organic matter won't happen in general; when the Ro ranges from 3.4% to 3.5%, non-carbonization and weak carbonization of organic matter may coexist; when the Ro is higher than 3.5%, the carbonization of organic matter is highly likely to take place.(2) Organic-rich shale entering carbonization phase have three basic characteristics: log resistivity curve showing a general "slender neck" with low-ultralow resistance response, Raman spectra showing a higher graphite peak, and poor physical property(with matrix porosity of only less than 1/2 of the normal level).(3) The quality damage of shale reservoir caused by the carbonization of organic matter is almost fatal, which primarily manifests in depletion of hydrocarbon generation capacity, reduction or disappearance of organic pores and intercrystalline pores of clay minerals, and drop of adsorption capacity to natural gas. Therefore, the lower limit of Ro for the carbonization of Type I-II1 organic matter should be regarded as the theoretically impassable red line of shale gas exploration in the ancient marine shale formations. The organic-rich shale with low-ultralow resistance should be evaluated effectively in area selection to exclude the high risk areas caused by the carbonization of organic matter. The target organic-rich shale layers with low-ultralow resistance drilled during exploration and development should be evaluated on carbonization level of organic matter, and the deployment plan should be adjusted according to the evaluation results in time.展开更多
Unusual carbonaceous matter, termed here chiemite, composed of more than 90% C from the Alpine Foreland at Lake Chiemsee in Bavaria, southeastern Germany has been investigated using optical and atomic force microscopy...Unusual carbonaceous matter, termed here chiemite, composed of more than 90% C from the Alpine Foreland at Lake Chiemsee in Bavaria, southeastern Germany has been investigated using optical and atomic force microscopy, X-ray fluorescence spectroscopy, scanning and transmission electron microscopy, high-resolution Raman spectroscopy, X-ray diffraction and differential thermal analysis, as well as by δ13 C and 14 C radiocarbon isotopic data analysis. In the pumice-like fragments, poorly ordered carbon matter co-exists with high-ordering monocrystalline α-carbyne, and contains submicrometersized inclusions of complex composition. Diamond and carbyne add to the peculiar mix of matter. The required very high temperatures and pressures for carbyne formation point to a shock event probably from the recently proposed Holocene Chiemgau meteorite impact. The carbon material is suggested to have largely formed from heavily shocked coal, vegetation like wood, and peat from the impact target area. The carbonization/coalification high PT process may be attributed to a strong shock that instantaneously caused the complete evaporation and loss of volatile matter and water, which nevertheless preserved the original cellular structure seen fossilized in many fragments. Relatively fresh wood encapsulated in the purported strongly shocked matter point to quenched carbon melt components possibly important for the discussion of survival of organic matter in meteorite impacts, implying an astrobiological relationship.展开更多
The regularity of the carbonization process in alumina production has been summarized by thepattern recognition and regression.A mathematical model has been proposed to describe thefactors affecting the silica content...The regularity of the carbonization process in alumina production has been summarized by thepattern recognition and regression.A mathematical model has been proposed to describe thefactors affecting the silica content of aluminium hydroxide product.The high concentration ofaluminate ions in solution will produce aluminium hydroxide with low content of SiO<sub>2</sub> underthe condition of Al<sub>2</sub>O<sub>3</sub>/SiO<sub>2</sub> ratio kept unchanged.This was confirmed by certain scaleexperiments.展开更多
The regularity of the carbonization process in alumina production has been summarized by thepattern recognition and regression.A mathematical model has been proposed to describe thefactors affecting the silica content...The regularity of the carbonization process in alumina production has been summarized by thepattern recognition and regression.A mathematical model has been proposed to describe thefactors affecting the silica content of aluminium hydroxide product.The high concentration ofaluminate ions in solution will produce aluminium hydroxide with low content of SiO<sub>2</sub> underthe condition of Al<sub>2</sub>O<sub>3</sub>/SiO<sub>2</sub> ratio kept unchanged.This was confirmed by certain scaleexperiments.展开更多
Ni-doped phenol resin was prepared with 1∶100 mass ratio of Ni( NO_3)_2·6H_2O to thermosetting phenol resin to optimize the structure and properties of pyrolytic carbon derived from phenol resin and increase its...Ni-doped phenol resin was prepared with 1∶100 mass ratio of Ni( NO_3)_2·6H_2O to thermosetting phenol resin to optimize the structure and properties of pyrolytic carbon derived from phenol resin and increase its carbon yield. The specimens were cured at 200 ℃ and carbonized under different atmospheres( carbon-embedded atmosphere and Ar atmosphere) and at different temperatures( 600,800,1000 and 1200 ℃) for3 h,respectively. The carbon yield was measured. Thermal decomposition characteristics of Ni-doped phenol resin,and the oxidation resistance,phase composition and microstructure of pyrolytic carbon were characterized by differential scanning calorimetry,X-ray diffraction,energy dispersive spectroscopy, scanning electron microscopy and transmission electron microscopy. The results show that the carbon yield of Ni-doped phenol resin carbonized at800 or 1 000 ℃ is increased significantly,compared with that without any dopants. The graphitization degree of pyrolytic carbon structure derived from Ni-doped phenol resin increases with the increase of carbonization temperature. The massive multi-wall carbon nanotubes of 50-100 nm in diameter and of micrometre scale in length are generated at 1000 ℃. Compared with the carbonembedded atmosphere,carbon nanotubes can be more easily generated in Ar atmosphere,resulting in higher carbon yield and degree of crystallinity of the pyrolyticcarbon derived from Ni-doped phenol resin. The oxidation resistance of the pyrolytic carbon derived from Ni-doped phenol resin at 1200 ℃ is improved significantly and its highest oxidation temperature is increased by about 84℃,compared with that from Ni free phenol resin.展开更多
The carbonized structures of Mo La 2O 3 cathode specimens have been investigated by means of FESEM and XRD, respectively. The substructure of carbonized layer in the Mo La 2O 3 cathode has been found for the first tim...The carbonized structures of Mo La 2O 3 cathode specimens have been investigated by means of FESEM and XRD, respectively. The substructure of carbonized layer in the Mo La 2O 3 cathode has been found for the first time. The results showed that the carbonized layer with uniform Mo 2C was helpful to emission, while the demixing carbonized layer with a compact MoC outside layer was harmful to emission. The uniform Mo 2C layer consists of coarse particles with lots of grain boundary crevices as well as holes arranging perpendicular to the wire axle and up to surface, which was beneficial to the migration of activated rare earth in activation and operating.展开更多
基金the National Key R&D Program of China(No.2022YFE0208100)the National Natural Science Foundation of China(No.5274316)+1 种基金the Key Research and Development Plan of Anhui Province,China(No.202210700037)the Major Science and Technology Project of Xinjiang Uygur Autonomous Region,China(No.2022A01003).
文摘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.
基金financially supported by the National Natural Science Foundation of China(Approval No.42172168).
文摘In order to obtain liquefied products with higher yields of aromatic molecules to produce mesophase pitch,a good understanding of the relevant reaction mechanisms is required.Reactive molecular dynamics simulations were used to study the thermal reactions of pyrene,1-methylpyrene,7,8,9,10-tetrahydrobenzopyrene,and mixtures of pyrene with 1-octene,cyclohexene,or styrene.The reactant conversion rates,reaction rates,and product distributions were calculated and compared,and the mechanisms were analyzed and discussed.The results demonstrated that methyl and naphthenic structures in aromatics might improve the conversion rates of reactants in hydrogen transfer processes,but their steric hindrances prohibited the generation of high polymers.The naphthenic structures could generate more free radicals and presented a more obvious inhibition effect on the condensation of polymers compared with the methyl side chains.It was discovered that when different olefins were mixed with pyrene,1-octene primarily underwent pyrolysis reactions,whereas cyclohexene mainly underwent hydrogen transfer reactions with pyrene and styrene,mostly producing superconjugated biradicals through condensation reactions with pyrene.In the mixture systems,the olefins scattered aromatic molecules,hindering the formation of pyrene trimers and higher polymers.According to the reactive molecular dynamics simulations,styrene may enhance the yield of dimer and enable the controlled polycondensation of pyrene.
基金supported by the Fundamental Research Funds for the Central Universities of Southwest Jiaotong University,supported by Sichuan Science and Technology Program(2021YFS0284).
文摘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.
基金supported by the State Key Laboratory of Advanced Metallurgy,China(Project Code:41603006).
文摘Decarbonization is a critical issue for peaking CO_(2) emissions of energy-intensive industries,such as the iron and steel industry.The decarbonization options of China’s ironmaking and steelmaking sector were discussed based on a systematic three-dimensional low-carbon analysis from the aspects of resource utilization(Y),energy utilization(Q),and energy cleanliness which is evaluated by a process general emission factor(PGEF)on all the related processes,including the current blast furnace(BF)-basic oxygen furnace(BOF)integrated process and the specific sub-processes,as well as the electric arc furnace(EAF)process,typical direct reduction(DR)process,and smelting reduction(SR)process.The study indicates that the three-dimensional aspects,particularly the energy structure,should be comprehensively considered to quantitatively evaluate the decarbonization road map based on novel technologies or processes.Promoting scrap utilization(improvement of Y)and the substitution of carbon-based energy(improvement of PGEF)in particular is critical.In terms of process scale,promoting the development of the scrap-based EAF or DR-EAF process is highly encouraged because of their lower PGEF.The three-dimensional method is expected to extend to other processes or industries,such as the cement production and thermal electricity generation industries.
基金The financial support from the Key-Area Research and Development Program of Guangdong Province (2020B1111380001)the Beijing Municipal Natural Science Foundation (2222012)+1 种基金the National Natural Science Foundation of China (Grant No.52070116)the Tsinghua University-Shanxi Clean Energy Research Institute Innovation Project Seed Fund。
文摘Hydrothermal carbonization(HTC) of lignocellulosic biomass is a promising technology for the production of carbon materials with negative carbon emissions. However, the high reaction temperature and energy consumption have limited the development of HTC technology. In conventional batch reactors, the temperature and pressure are typically coupled at saturated states. In this study, a decoupled temperature and pressure hydrothermal(DTPH) reaction system was developed to decrease the temperature of the HTC reaction of lignocellulosic biomass(rice straw and poplar leaves). The properties of hydrochars were analyzed by scanning electron microscopy(SEM), Fourier transform infrared(FTIR) spectroscopy, X-ray photoelectron spectroscopy(XPS), Raman spectroscopy, X-ray diffraction(XRD), thermogravimetric analyzer(TGA), etc. to propose the reaction mechanism. The results showed that the HTC reaction of lignocellulosic biomass could be realized at a low temperature of 200℃ in the DTPH process, breaking the temperature limit(230℃) in the conventional process. The DTPH method could break the barrier of the crystalline structure of cellulose in the lignocellulosic biomass with high cellulose content, realizing the carbonization of cellulose and hemicellulose with the dehydration, unsaturated bond formation, and aromatization. The produced hydrochar had an appearance of carbon microspheres, with high calorific values, abundant oxygen-containing functional groups, a certain degree of graphitization, and good thermal stability. Cellulose acts not only as a barrier to protect itself and hemicellulose from decomposition, but also as a key precursor for the formation of carbon microspheres. This study shows a promising method for synthesizing carbon materials from lignocellulosic biomass with a carbon-negative effect.
基金This work is supported by the National Natural Science Foundation of China(Grant Nos.21802167,21961132026,92034302,21878331,91645108)the National Key Research and Development Program Nanotechnology Specific Project(No.2020YFA0210903).
文摘Propylene is a significant basic material for petrochemicals such as polypropylene,propylene oxide,etc.With abundant propane supply from shale gas,propane dehydrogenation(PDH)becomes extensively attractive as an on-purpose propylene production route in recent years.Nitrogen-doped carbon(NC)nanopolyhedra supported cobalt catalysts were synthesized in one-step of ZIF-67 pyrolysis and investigated further in PDH.XPS,TEM and N_(2) adsorption-desorption were used to study the influence of carbonization temperature on as-prepared NC supported cobalt catalysts.The temperature is found to affect the cobalt phase and nitrogen species of the catalysts.And the positive correlation was established between Co0 proportion and space time yield of propylene,indicating that the modulation of carbonization temperature could be important for catalytic performance.
基金The authors acknowledge the financial support provided by the Key R&D Program of Shaanxi Province(No.2022SF-168)Xi’an Programs for Science and Technology Plan(Nos.2020KJRC0090 and 21XJZZ0045)+5 种基金Xi’an Beilin District Programs for Science and Technology Plan(No.GX2247)the Outstanding Chinese and Foreign Youth Exchange Program of China Association for Science and Technology(CAST)in 2019the Opening Project of Shanxi Key Laboratory of Advanced Manufacturing Technology(No.XJZZ202001)the Scientific Research Project of Shaanxi Education Department(No.20JS108)Open Foundation of Key Laboratory of Auxiliary Chemistry and Technology for Chemical Industry,Ministry of Education,Shaanxi University of Science and Technology(No.KFKT2021-01)Shaanxi Collaborative Innovation Center of Industrial Auxiliary Chemistry and Technology,Shaanxi University of Science and Technology(No.KFKT2021-01).
文摘Greenhouse gas emissions from waste plastics have caused global warming all over the world,which has been a central threat to the ecological environment for humans,flora and fauna.Among waste plastics,waste polyethylene terephthalate(PET)is attractive due to its excellent stability and degradation-resistant.Therefore,merging China’s carbon peak and carbon neutrality goals would be beneficial.In this review,we summarize the current state-of-the-art of carbon emission decrease from a multi-scale perspective technologically.We suggest that the carbon peak for waste PET can be achieved by employing the closed-loop supply chain,including recycling,biomass utilization,carbon capture and utilization.Waste PET can be a valuable and renewable resource in the whole life cycle.Undoubtedly,all kinds of PET plastics can be ultimately converted into CO_(2),which can also be feedstock for various kinds of chemical products,including ethyl alcohol,formic acid,soda ash,PU,starch and so on.As a result,the closed-loop supply chain can help the PET plastics industry drastically reduce its carbon footprint.
文摘High-performance carbonaceous electrode materials for supercapacitors were synthesized by subjecting corn starch to a simple molten salt activation process with K<sub>2</sub>CO<sub>3</sub> at a temperature of 850˚C. The resulting carbon material, obtained after activating for 1 hour, displayed excellent capacitive properties due to the synergistic effects of its porous structure. Utilizing these electrodes, the supercapacitor exhibited a high discharge capacitance (248 F g<sup>−1</sup> at 1 A g<sup>−1</sup>), which is 2.4 times higher than that of activated carbon without K<sub>2</sub>CO<sub>3</sub> activation. The enhancement in electrical performance was analyzed through SEM and XRD analysis, revealing that the porous and disordered structure provides a greater number of charge storage sites, resulting in improved capacitive performance.
基金supported by the National Key R&D Program of China(2019YFA0110600 and 2019YFA0110601)National Natural Science Foundation of China(Nos.51603134,51903178,51803134,and 51703141)+1 种基金Sichuan Province’s Science and Technology Planning Project(No.2016GZ0350)the Postgraduate Course Construction Project of Sichuan University(No.2017KCSJ036)and for their financial support.
文摘To overcome the ever-growing organic pollutions in the water system,abundant efforts have been dedicated to fabricating efficient Fenton-like carbon catalysts.However,the rational design of carbon catalysts with high intrinsic activity remains a long-term goal.Herein,we report a new N-molecule-assisted self-catalytic carbonization process in augmenting the intrinsic Fenton-like activity of metal-organic-framework-derived carbon hybrids.During carbonization,the N-molecules provide alkane/ammonia gases and the formed iron nanocrystals act as the in situ catalysts,which result in the elaborated formation of carbon nanotubes(in situ chemical vapor deposition from alkane/iron catalysts)and micro-/meso-porous structures(ammonia gas etching).The obtained catalysts exhibited with abundant Fe/Fe-Nx/pyridinic-N active species,micro-/meso-porous structures,and conductive carbon nanotubes.Consequently,the catalysts exhibit high efficiency toward the degradation of different organic pollutions,such as bisphenol A,methylene blue,and tetracycline.This study not only creates a new pathway for achieving highly active Fenton-like carbon catalysts but also takes a step toward the customized production of advanced carbon hybrids for diverse energy and environmental applications.
基金I would like to express my heart felt gratitude to the management,academic and support staff of Botswana International University of Science and Technology for providing access to the resources of the institution during the study carried out for this review.
文摘Coal due to its relatively large quantities and wide distribution worldwide has generated renewed interest in research and development with the aim of establishing coal conversion technologies that are technically reliable,envi-ronmentally and economically feasible.It has proved to be a prominent energy source in emerging markets with increasing energy demand by accounting for the largest increase in the demand of energy amongst all other energy sources.Fur-thermore,with its higher mesophase content,coal tar is an appropriate raw material for precursors in the production of carbon fiber.However,whenever a material is put to use,it is important to be able to associate its properties to the behavioral characteristics during a conversion process so as to have a basis for opting for the material in a given process or adjusting the operating conditions in order to optimize the material utilization.Therefore,as with any other material,it is important to be able to relate the properties of coal to its utilization.A review was carried out on the influence of coal properties on four main utilization technologies:gasification,carbonization,liquefaction and carbon fibre production.Among several properties rank,type,mineral matter content,distribution of trace elements,structural composition and pore structure were found to be most influential on the behavior of coal during conversion processes.
基金by the National Nature Science Foundation of the People’s Republic of China(No.51703153).
文摘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.
基金Supported by the National Key R&D Program of China(2016YFB0301503)the National Natural Science Foundation of China(91534110,21776127)+1 种基金the Jiangsu Province Natural Science Foundation for Distinguished Young Scholars(BK20150044)the Jiangsu Province Natural Science Foundation(BK20160978)
文摘The state-of-the-art approaches for adjusting the structural characteristics of porous carbons are the aftertreatments, which are complicated and time consuming. In this work, a facile approach was developed, i.e., controlling the initial oxygen concentration in-situ during the direct carbonization of zeolitic imidazole framework-8(ZIF-8), to adjust the pore structure and prepare hierarchically porous carbons. The introduction of oxygen can significantly affect the crystalline and pore structures of porous carbons, and promote the pore widening and the formation of mesopores. An appropriate initial oxygen concentration can notably enhance the surface area and mesopore volume of porous carbon, and then improve the adsorption capacity toward methylene blue(MB) dye from water by 3.4 times. The developed approach is more efficient at lower carbonization temperature.Moreover, the introduction of oxygen can increase the ratio of HO\\C_O groups on the carbon surface, leading to enhanced interaction with MB molecules and higher adsorption capacity toward MB. The as-prepared porous carbons exhibit superior adsorption capacities toward MB dye as compared to the reported ZIF-8 derived carbons. These findings would aid the development of porous carbon materials with high performance.
基金support of the National Natural Science Foundation of China (21403218, 21476226, 21403029)Ministry of Science and Technology of the People’s Republic of China under contact of 2016YFA0202800+2 种基金the Youth Innovation Promotion Association of the CASthe Scientific Research Project of the Education Department of Liaoning Province (L2014022)the Fundamental Research Funds for the Central Universities (DUT15ZD225)
文摘A binder-free Ir-dispersed ordered mesoporous carbon(Ir-OMC) catalytic electrode has been prepared through a designed in-situ carbonization method, which involves coating resorcinol and formaldehyde mixtures with iridium precursors onto the three-dimensional nickel foam framework, followed by insitu calcination in N_2 atmosphere at 800 ℃ for 3 h. This electrode shows a large surface area, ordered mesoporous structure and homogeneous distribution of metal nanoparticles. It presents good activity and stability towards hydrogen evolution reaction, which is attributed to the efficient mass and electron transport from the intimate contact among Ir nanoparticles, ordered mesoporous carbon matrix and 3 D conductive substrate. We hope that this in-situ carbonization synthetic route can also be applied to design more high-performance catalysts for water splitting, fuel cells and other clean energy devices.
基金Supported by Shanxi Scholarship Council of China (2015-123)the Natural Science Foundation of China (51602322)the Key Research and Development Program of Shanxi Province (International Cooperation) (201703D421041) for financial support
文摘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.
基金Supported by the CAS Strategic Pilot Project(XDA14010101)National Science and Technology Major Project(2017ZX05035001)PetroChina Exploration&Production Shale Gas Resource Evaluation and Strategic Selection Project(kt2017-10-02)
文摘Based on the drilling data of the Silurian Longmaxi Formation in the Sichuan Basin and periphery, SW China, the Ro lower limits and essential features of the carbonization of organic matter in over-high maturity marine shale were examined using laser Raman, electrical and physical property characterization techniques. Three preliminary conclusions are drawn:(1) The lower limit of Ro for the carbonization of Type I-II1 organic matter in marine shale is 3.5%; when the Ro is less than 3.4%, carbonization of organic matter won't happen in general; when the Ro ranges from 3.4% to 3.5%, non-carbonization and weak carbonization of organic matter may coexist; when the Ro is higher than 3.5%, the carbonization of organic matter is highly likely to take place.(2) Organic-rich shale entering carbonization phase have three basic characteristics: log resistivity curve showing a general "slender neck" with low-ultralow resistance response, Raman spectra showing a higher graphite peak, and poor physical property(with matrix porosity of only less than 1/2 of the normal level).(3) The quality damage of shale reservoir caused by the carbonization of organic matter is almost fatal, which primarily manifests in depletion of hydrocarbon generation capacity, reduction or disappearance of organic pores and intercrystalline pores of clay minerals, and drop of adsorption capacity to natural gas. Therefore, the lower limit of Ro for the carbonization of Type I-II1 organic matter should be regarded as the theoretically impassable red line of shale gas exploration in the ancient marine shale formations. The organic-rich shale with low-ultralow resistance should be evaluated effectively in area selection to exclude the high risk areas caused by the carbonization of organic matter. The target organic-rich shale layers with low-ultralow resistance drilled during exploration and development should be evaluated on carbonization level of organic matter, and the deployment plan should be adjusted according to the evaluation results in time.
基金supported for the Russian team members by the RFBR, Project # 17-05-00516
文摘Unusual carbonaceous matter, termed here chiemite, composed of more than 90% C from the Alpine Foreland at Lake Chiemsee in Bavaria, southeastern Germany has been investigated using optical and atomic force microscopy, X-ray fluorescence spectroscopy, scanning and transmission electron microscopy, high-resolution Raman spectroscopy, X-ray diffraction and differential thermal analysis, as well as by δ13 C and 14 C radiocarbon isotopic data analysis. In the pumice-like fragments, poorly ordered carbon matter co-exists with high-ordering monocrystalline α-carbyne, and contains submicrometersized inclusions of complex composition. Diamond and carbyne add to the peculiar mix of matter. The required very high temperatures and pressures for carbyne formation point to a shock event probably from the recently proposed Holocene Chiemgau meteorite impact. The carbon material is suggested to have largely formed from heavily shocked coal, vegetation like wood, and peat from the impact target area. The carbonization/coalification high PT process may be attributed to a strong shock that instantaneously caused the complete evaporation and loss of volatile matter and water, which nevertheless preserved the original cellular structure seen fossilized in many fragments. Relatively fresh wood encapsulated in the purported strongly shocked matter point to quenched carbon melt components possibly important for the discussion of survival of organic matter in meteorite impacts, implying an astrobiological relationship.
文摘The regularity of the carbonization process in alumina production has been summarized by thepattern recognition and regression.A mathematical model has been proposed to describe thefactors affecting the silica content of aluminium hydroxide product.The high concentration ofaluminate ions in solution will produce aluminium hydroxide with low content of SiO<sub>2</sub> underthe condition of Al<sub>2</sub>O<sub>3</sub>/SiO<sub>2</sub> ratio kept unchanged.This was confirmed by certain scaleexperiments.
文摘The regularity of the carbonization process in alumina production has been summarized by thepattern recognition and regression.A mathematical model has been proposed to describe thefactors affecting the silica content of aluminium hydroxide product.The high concentration ofaluminate ions in solution will produce aluminium hydroxide with low content of SiO<sub>2</sub> underthe condition of Al<sub>2</sub>O<sub>3</sub>/SiO<sub>2</sub> ratio kept unchanged.This was confirmed by certain scaleexperiments.
基金financial supports from the National Natural Science Foundation of China(51174152)National Basic Research Program of China(973 Program)(2012CB722702)
文摘Ni-doped phenol resin was prepared with 1∶100 mass ratio of Ni( NO_3)_2·6H_2O to thermosetting phenol resin to optimize the structure and properties of pyrolytic carbon derived from phenol resin and increase its carbon yield. The specimens were cured at 200 ℃ and carbonized under different atmospheres( carbon-embedded atmosphere and Ar atmosphere) and at different temperatures( 600,800,1000 and 1200 ℃) for3 h,respectively. The carbon yield was measured. Thermal decomposition characteristics of Ni-doped phenol resin,and the oxidation resistance,phase composition and microstructure of pyrolytic carbon were characterized by differential scanning calorimetry,X-ray diffraction,energy dispersive spectroscopy, scanning electron microscopy and transmission electron microscopy. The results show that the carbon yield of Ni-doped phenol resin carbonized at800 or 1 000 ℃ is increased significantly,compared with that without any dopants. The graphitization degree of pyrolytic carbon structure derived from Ni-doped phenol resin increases with the increase of carbonization temperature. The massive multi-wall carbon nanotubes of 50-100 nm in diameter and of micrometre scale in length are generated at 1000 ℃. Compared with the carbonembedded atmosphere,carbon nanotubes can be more easily generated in Ar atmosphere,resulting in higher carbon yield and degree of crystallinity of the pyrolyticcarbon derived from Ni-doped phenol resin. The oxidation resistance of the pyrolytic carbon derived from Ni-doped phenol resin at 1200 ℃ is improved significantly and its highest oxidation temperature is increased by about 84℃,compared with that from Ni free phenol resin.
文摘The carbonized structures of Mo La 2O 3 cathode specimens have been investigated by means of FESEM and XRD, respectively. The substructure of carbonized layer in the Mo La 2O 3 cathode has been found for the first time. The results showed that the carbonized layer with uniform Mo 2C was helpful to emission, while the demixing carbonized layer with a compact MoC outside layer was harmful to emission. The uniform Mo 2C layer consists of coarse particles with lots of grain boundary crevices as well as holes arranging perpendicular to the wire axle and up to surface, which was beneficial to the migration of activated rare earth in activation and operating.
