The kinetic characteristics of plasma-assisted oxidative pyrolysis of ammonia are studied by using the global/fluid models hybrid solution method.Firstly,the stable products of plasma-assisted oxidative pyrolysis of a...The kinetic characteristics of plasma-assisted oxidative pyrolysis of ammonia are studied by using the global/fluid models hybrid solution method.Firstly,the stable products of plasma-assisted oxidative pyrolysis of ammonia are measured.The results show that the consumption of NH_(3)/O_(2)and the production of N_(2)/H_(2)change linearly with the increase of voltage,which indicates the decoupling of nonequilibrium molecular excitation and oxidative pyrolysis of ammonia at low temperatures.Secondly,the detailed reaction kinetics mechanism of ammonia oxidative pyrolysis stimulated by a nanosecond pulse voltage at low pressure and room temperature is established.Based on the reaction path analysis,the simplified mechanism is obtained.The detailed and simplified mechanism simulation results are compared with experimental data to verify the accuracy of the simplified mechanism.Finally,based on the simplified mechanism,the fluid model of ammonia oxidative pyrolysis stimulated by the nanosecond pulse plasma is established to study the pre-sheath/sheath behavior and the resultant consumption and formation of key species.The results show that the generation,development,and propagation of the pre-sheath have a great influence on the formation and consumption of species.The consumption of NH_(3)by the cathode pre-sheath is greater than that by the anode pre-sheath,but the opposite is true for OH and O(1S).However,within the sheath,almost all reactions do not occur.Further,by changing the parameters of nanosecond pulse power supply voltage,it is found that the electron number density,electron current density,and applied peak voltages are not the direct reasons for the structural changes of the sheath and pre-sheath.Furthermore,the discharge interval has little effect on the sheath structure and gas mixture breakdown.The research results of this paper not only help to understand the kinetic promotion of non-equilibrium excitation in the process of oxidative pyrolysis but also help to explore the influence of transport and chemical reaction kinetics on the oxidative pyrolysis of ammonia.展开更多
The recycling of spent lithium-ion batteries(LIBs) is crucial for environmental protection and resource sustainability.However,the economic recovery of spent LIBs remains challenging due to low Li recovery efficiency ...The recycling of spent lithium-ion batteries(LIBs) is crucial for environmental protection and resource sustainability.However,the economic recovery of spent LIBs remains challenging due to low Li recovery efficiency and the need for multiple separation operations.Here,we propose a process involving mixed HCl-H_(2)SO_(4) leaching-spray pyrolysis for recycling spent ternary LIBs,achieving both selective Li recovery and the preparation of a ternary oxide precursor.Specifically,the process transforms spent ternary cathode(LiNi_(x)Co_yMn_(2)O_(2),NCM) powder into Li_(2)SO_(4) solution and ternary oxide,which can be directly used for synthesizing battery-grade Li_(2)CO_(3) and NCM cathode,respectively.Notably,SO_(4)^(2-) selectively precipitates with Li^(+) to form thermostable Li_(2)SO_(4) during the spray pyrolysis,which substantially improves the Li recovery efficiency by inhibiting Li evaporation and intercalation.Besides,SO_(2) emissions are avoided by controlling the molar ratio of Li^(+)/SO_(4)^(2-)(≥2:1),The mechanism of the preferential formation of Li_(2)SO_(4) is interpreted from its reverse solubility variation with temperature.During the recycling of spent NCM811,92% of Li is selectively recovered,and the regenerated NCM811 exhibits excellent cycling stability with a capacity retention of 81.7% after 300 cycles at 1 C.This work offers a simple and robust process for the recycling of spent NCM cathodes.展开更多
Oxidative-exfoliation methods were in vogue in the production of rGO from graphite.Processing of such synthetic graphite needs high temperatures(2500℃).Thus,such process is not cost-effective.The present study is mad...Oxidative-exfoliation methods were in vogue in the production of rGO from graphite.Processing of such synthetic graphite needs high temperatures(2500℃).Thus,such process is not cost-effective.The present study is made on the dry leaves of sugarcane(Saccharum officinarum)as an alternative raw material so as to be economical and environmentally benign.The dry leaves are subjected to two-step pyrolysis without any catalyst or reducing agent in far divergent temperatures to produce as prepared and acid treated rGOs.They were evaluated by UV–Vis.,FTIR,XRD,Raman spectroscopy,TGA/DTG,BET,FESEM-EDS and TEM.The as prepared rGO has few layers with irregular and folded architecture whereas acid-treated rGO has thinly stacked crumpled sheets with many wrinkles on its surface.The prepared rGOs have multilayered graphitic structure due to the unique ratio between G and D bands.Acid treated rGO has poor thermal stability as compared to that of as-prepared rGO at high temperatures due to the variation in the oxygen-containing functional groups.Acid treated rGO has low antibacterial activity as compared to that of the as-prepared rGO due to the paucity of the functional groups.展开更多
The efficient pyrolysis and conversion of organic matter in organic-rich shale,as well as the effective recovery of pyrolysis shale oil and gas,play a vital role in alleviating energy pressure.The state of carbon diox...The efficient pyrolysis and conversion of organic matter in organic-rich shale,as well as the effective recovery of pyrolysis shale oil and gas,play a vital role in alleviating energy pressure.The state of carbon dioxide(CO_(2))in the pyrolysis environment of shale reservoirs is the supercritical state.Its unique supercritical fluid properties not only effectively heat organic matter,displace pyrolysis products and change shale pore structure,but also achieve carbon storage to a certain extent.Shale samples were made into powder and three sizes of cores,and nitrogen(N_(2))and supercritical carbon dioxide(ScCO_(2))pyrolysis experiments were performed at different final pyrolysis temperatures.The properties and mineral characteristics of the pyrolysis products were studied based on gas chromatography analysis,Xray diffraction tests,and mass spectrometry analysis.Besides,the pore structure characteristics at different regions of cores before and after pyrolysis were analyzed using N_(2) adsorption tests to clarify the impact of fracturing degree on the pyrolysis effect.The results indicate that the optimal pyrolysis temperature of Longkou shale is about 430℃.Compared with N_(2),the oil yield of ScCO_(2) pyrolysis is higher.The pyrolysis oil obtained by ScCO_(2) extraction has more intermediate fractions and higher relative molecular weight.The ScCO_(2) can effectively improve the pore diameter of shale and its effect is better than that of N_(2).The micropores are produced in shale after pyrolysis,and the macropores only are generated in ScCO_(2) pyrolysis environments with temperatures greater than 430℃.The pore structure has different development characteristics at different pyrolysis temperatures,which are mainly affected by the pressure holding of volatile matter and products blocking.Compared to the surface of the core,the pore development effect inside the core is better.With the decrease in core size,the pore diameter,specific surface area,and pore volume of cores all increase after pyrolysis.展开更多
Ammonia is gaining increasing attention as a green alternative fuel for achieving large-scale carbon emission reduction. Despite its potential technical prospects, the harsh ignition conditions and slow flame propagat...Ammonia is gaining increasing attention as a green alternative fuel for achieving large-scale carbon emission reduction. Despite its potential technical prospects, the harsh ignition conditions and slow flame propagation speed of ammonia pose significant challenges to its application in engines. Non-equilibrium plasma has been identified as a promising method, but current research on plasma-enhanced ammonia combustion is limited and primarily focuses on ignition characteristics revealed by kinetic models. In this study, low-temperature and low-pressure chemistry in plasma-assisted ammonia oxidative pyrolysis is investigated by integrated studies of steady-state GC measurements and mathematical simulation. The detailed kinetic mechanism of NH_(3) decomposition in plasma-driven Ar/NH_(3) and Ar/NH_(3)/O_(2) mixtures has been developed. The numerical model has good agreements with the experimental measurements in NH_(3)/O_(2) consumption and N_(2)/H_(2) generation, which demonstrates the rationality of modelling. Based on the modelling results, species density profiles, path flux and sensitivity analysis for the key plasmaproduced species such as NH_(2), NH, H_(2), OH, H, O, O(^(1)D), O_(2)(a^(1)△_(g)), O_(2)(b^(1)∑_(g)^(+)), Ar^(*), H^(-), Ar^(+), NH_(3)^(+), O_(2)^(-) in the discharge and afterglow are analyzed in detail to illustrate the effectiveness of the active species on NH_(3) excitation and decomposition at low temperature and relatively higher E/N values. The results revealed that NH_(2), NH, H as well as H_(2) are primarily generated through the electron collision reactions e + NH_(3)→ e + NH_(2)+ H, e + NH_(3)→ e + NH + H_(2) and the excited-argon collision reaction Ar^(*) + NH_(3)+ H → Ar + NH_(2)+ 2H, which will then react with highly reactive oxidative species such as O_(2)^(*), O^(*), O, OH, and O_(2) to produce stable products of NOx and H_(2)O. NH_(3)→ NH is found a specific pathway for NH_(3) consumption with plasma assistance, which further highlights the enhanced kinetic effects.展开更多
A novel design of micro-aluminum(μAl)powder coated with bi-/tri-component alloy layer,such as:Ni-P and Ni-P-Cu(namely,Al@Ni-P,Al@Ni-P-Cu,respectively),as combustion catalysts,were introduced to release its huge energ...A novel design of micro-aluminum(μAl)powder coated with bi-/tri-component alloy layer,such as:Ni-P and Ni-P-Cu(namely,Al@Ni-P,Al@Ni-P-Cu,respectively),as combustion catalysts,were introduced to release its huge energy inside Al-core and promote rapid pyrolysis of ammonium perchlorate(AP)at a lower temperature in aluminized propellants.The microstructure of Al@Ni-P-Cu demonstrates that a three-layer Ni-P-Cu shell,with the thickness of~100 nm,is uniformly supported byμAl carrier(fuel unit),which has an amorphous surface with a thickness of~2.3 nm(catalytic unit).The peak temperature of AP with the addition of Al@Ni-P-Cu(3.5%)could significantly drop to 316.2℃ at high-temperature thermal decomposition,reduced by 124.3℃,in comparison to that of pure AP with 440.5℃.It illustrated that the introduction of Al@Ni-P-Cu could weaken or even eliminate the obstacle of AP pyrolysis due to its reduction of activation energy with 118.28 kJ/mol.The laser ignition results showed that the ignition delay time of Al@Ni-P-Cu/AP mixture with 78 ms in air is shorter than that of Al@Ni-P/AP(118 ms),decreased by 33.90%.Those astonishing breakthroughs were attributed to the synergistic effects of adequate active sites on amorphous surface and oxidation exothermic reactions(7597.7 J/g)of Al@Ni-P-Cu,resulting in accelerated mass and/or heat transfer rate to catalyze AP pyrolysis and combustion.Moreover,it is believed to provide an alternative Al-based combustion catalyst for propellant designer,to promote the development the propellants toward a higher energy.展开更多
Coal pyrolysis is a fundamental reaction in the thermal processing and utilization of coal.Investigating the behavior and kinetics of coal pyrolysis is crucial for optimizing,designing,and developing a composite riser...Coal pyrolysis is a fundamental reaction in the thermal processing and utilization of coal.Investigating the behavior and kinetics of coal pyrolysis is crucial for optimizing,designing,and developing a composite riser for the staged pyrolysis gasification process of pulverized coal.In this study,the non-isothermal pyrolysis behavior and kinetics of coal were examined at different heating rates(30,50,100,300,500,700,and 900℃/min)using thermogravimetry(TG)coupled with Fourier-transform infrared spectroscopy.Analysis of the TG/derivative TG(TG/DTG)curves indicated that coal pyrolysis mainly occurred between 300℃ and 700℃.Higher heating rates led to more volatiles being released from the coal,and a higher temperature was required to achieve rapid pyrolysis.Kinetic analysis showed that both the model-free methods(Friedman,Flynn-Wall-Ozawa,and Kissinger-Akahira-Sunose)and the model-based method(Coats-Redfern)effectively describe the coal pyrolysis process.The change in the Ea values between the two kinetic models was consistent throughout the pyrolysis process,and the most probable mechanism was the F2 model(secondary chemical reaction).In addition,the heating rate did not change the overall reaction order of the pyrolysis process;however,a higher heating rate resulted in a decrease in the Ea value during the initial pyrolysis stage.展开更多
The composition and sequence distribution of monomeric units in polyester polyether multiblock copolymer were studied by pyrolysis? gas chromatography (PGC) and pyrolysis gas chromatography/mass spectrometry (PGC/M...The composition and sequence distribution of monomeric units in polyester polyether multiblock copolymer were studied by pyrolysis? gas chromatography (PGC) and pyrolysis gas chromatography/mass spectrometry (PGC/MS). PGC was applied to study the F t curve of the multiblock copolymer and PGC/MS was used to separate and identify the pyrolyzates. DTA experiment was used to study the decomposition temperature. The results show that the beginning point of elastomer’s decomposition was about 300?℃ and the decomposition temperature of most of the sample was 550?℃. Many pyrolyzates were produced because of the breaking of weak bonds in the sample. The possible microstructure was verified and the pyrolysis pathway of the copolymer was investigated.展开更多
Lignocellulosic biomass can be convert to a condensable liquid named bio-oil,a solid product named as char and a mixture of gaseous products comprising CO2,CO,H2,CH4,etc.In recent years,much effort has been made on th...Lignocellulosic biomass can be convert to a condensable liquid named bio-oil,a solid product named as char and a mixture of gaseous products comprising CO2,CO,H2,CH4,etc.In recent years,much effort has been made on the investigation of conversion of biomass through pyrolysis.However,commercialisation of the biomass pyrolysis technology is still challenging due to various issues such as the deleterious properties of bio-oil including the low heating value and the high instability at elevated temperatures.To overcome such issues,many processes,reactors and catalysts have been developed for pyrolysis and catalytic pyrolysis of biomass.A state to the art of pyrolysis or catalytic pyrolysis of biomass need to be summarised to have an overall evaluation of the technologies,in order to provide a useful reference for the further development of pyrolysis technology.This study reviews the various pyrolysis process,especially focus on the effects of essential parameters,the process design,the reactors and the catalysts on the pyrolysis process.In addition,progress in commercialisation of pyrolysis technology was also reviewed and the remaining issues in the process of commercialisation were discussed.展开更多
Pyrolysis characteristics of a North Korean oil shale and its pyrolysates were investigated in this paper. The pyrolysis experiments were conducted below 600 ℃ at a heating rate of 10, 15, 20 and 25 ℃/min, respectiv...Pyrolysis characteristics of a North Korean oil shale and its pyrolysates were investigated in this paper. The pyrolysis experiments were conducted below 600 ℃ at a heating rate of 10, 15, 20 and 25 ℃/min, respectively. The kinetics data were calculated using both integral and differential methods with the assumption of first order kinetics. The results show that the averaged oil content of the North Korean oil shale is about 12.1 wt% and its heat value is 13,400 kJ/kg. The oil yields at different retorting temperatures show that the higher the retorting temperature the greater the oil and retorting gas yields. The optimal retorting temperature for the North Korean oil shale is about 500 ℃. The properties of the North Korean shale oil including density, viscosity, flash point and freezing point are found to be relatively low compared with those of shale oil from FuShun, China. The gasoline fraction, diesel fraction and heavy oil fraction account for 11.5 wt%, 41.5 wt% and 47 wt%, respectively. The major pyrolysis gases are ca4 （the most abundant）, H2, CO2, H2S, CO, and C2-C5 hydrocarbons. The heat value of retorting gas is more than 900 kJ/mol, and the retorting gas has high sulfur content.展开更多
The chemical thermodynamic equilibrium of acetylene production by coal pyrolysis in hydrogen plasma was studied. The thermodynamic equilibrium is obtained by using the method of free energy. Calculated results show th...The chemical thermodynamic equilibrium of acetylene production by coal pyrolysis in hydrogen plasma was studied. The thermodynamic equilibrium is obtained by using the method of free energy. Calculated results show that the hydrogen concentration in the equilibrium system is very important for the acetylene production by coal conversion and the energy consumption for the production of acetylene per-kilogram strongly depends on the hydrogen concentration and the temperature.展开更多
To get deep understanding of the reaction mechanism of coal pyrolysis in hydrogen plasma, the decomposition reaction pathways of aliphatic hydrocarbons and cycloalkanes, which are two main components in volatiles from...To get deep understanding of the reaction mechanism of coal pyrolysis in hydrogen plasma, the decomposition reaction pathways of aliphatic hydrocarbons and cycloalkanes, which are two main components in volatiles from coal, were investigated. Methane and cyclohexane were chosen as the model compounds. Density functional theory was employed, and many reaction pathways were involved. Calculations were carried out in Gaussian 09 at the B3LYP/6-31G（d,p） level of the theory. The results indicate that the main pyrolysis products of methane and cyclohexane in hydrogen plasma are both hydrogen and acetylene, and the participation of active hydrogen atoms makes dehydrogenation reactions more favorable. H2 mainly comes from dehydrogenation process, while many reaction pathways are responsible for acetylene formation. During coal pyrolysis in hydrogen plasma, three main components in volatiles like aliphatic hydrocarbons, cycloalkanes and aromatic hydrocarbons lead to the formation of hydrogen and acetylene, but their contributions to products distribution are different.展开更多
A series of char samples were derived from pyrolysis of two typical low-rank coals in China （Shengli lig- nite and Shenmu bituminous coal） at low, medium and fast heating rates, respectively, to the same pyrol- ysis...A series of char samples were derived from pyrolysis of two typical low-rank coals in China （Shengli lig- nite and Shenmu bituminous coal） at low, medium and fast heating rates, respectively, to the same pyrol- ysis temperature 750℃. Then these chars were characterized by means of thermogravimetric analysis and Fourier transform infrared spectrometer with the aim to investigate the influence of heating rate in pyrolysis process on gasification reactivity and surface chemistry of them. Besides, a homogeneous model was used to quantitatively analyze the activation energy of gasification reaction. The results reveal that Shengli lignite and its derived chars behave higher gasification reactivity and have less content of oxygen functional groups than Shenmu coal and chars. Meanwhile, chars derived from Shengli lignite at 50℃/min and Shenmu coal at 200℃/min have the greatest gasification reactivity, respectively. The oxygen functional groups in Shengli lignite are easily thermo-decomposed, and they are less affected by the heating rate, while that in Shenmu coal have a significant change with the variation of heating rate. In addition, there is no good correlation between the change of oxygen functional groups and that of the gasification reactivity of the derived chars from pyrolysis at different heating rates.展开更多
The pyrolysis kinetics of three different kinds of fresh biomass (grass: triple A, wheat straw, corn straw) in nitrogen flow were studied by thermogravimetric analysis at five different heating rates. The kinetic para...The pyrolysis kinetics of three different kinds of fresh biomass (grass: triple A, wheat straw, corn straw) in nitrogen flow were studied by thermogravimetric analysis at five different heating rates. The kinetic parameters of the pyrolysis process were calculated using the method of Ozawa-Flynn-Wall and the mechanism of reactions were investi- gated using the method of Popescu. It was found that the values of activation energy varied in different temperature ranges. The pyrolysis processes are well described by the models of Zhuravlev (Zh) and valid for diffusion-controlled between 200 ℃ and 280 ℃, by Ginstling-Brounshtein (G-B), valid for diffusion-control between 280 ℃ and 310 ℃, for first-order chemical reaction between 310℃ and 350 ℃, by Zhuravlev (Zh) valid for diffusion-control between 350 ℃ and 430 ℃ and by the one-way transport model when temperatures are over 430 ℃.展开更多
The pyrolysis characteristics of PVC were systematically investigated using a Netzschne TG thermo-balance coupled to a quadrupole mass spectrometer. The pyrolysis conditions were 0.1 MPa of Ar, a heating rate of 10 ℃...The pyrolysis characteristics of PVC were systematically investigated using a Netzschne TG thermo-balance coupled to a quadrupole mass spectrometer. The pyrolysis conditions were 0.1 MPa of Ar, a heating rate of 10 ℃/min and a final temperature of 1000℃. Both the thermogravimetric properties and the simultaneous evolution of gaseous products during pyrolysis were studied. The TG/DTG results showed that as the pyrolysis temperature increases the weight loss and weight loss rate of PVC increases. Near 412℃ the weight loss rate attained its peak value. At higher temperatures the rate of loss gradually decreases. The gases evolved during thermogravimetric analysis were analyzed by a mass spectrometer, monitoring the relative intensity of HC1, C6H6, light hydrocarbon and chlorine-containing gases The evolution curves showed that HC1, C6H6, light hydrocarbon and chlorine-containing gases all peak at about 416℃. This is consistent with the fact that the weight loss curves also peak at about 412℃. The extensive HCl evolution is consistent with the high chlorine content of PVC. The formation of these gases can be explained by considering these reactions： dehydrochlorination, intramolecular cyclization and the addition of HCl to unsaturated hydrocarbons.展开更多
A comparison between conventional pyrolysis and a novel developed low-temperature microwave-assisted pyrolysis methodology has been performed for the valorisation of a range of biomass feedstocks including waste resid...A comparison between conventional pyrolysis and a novel developed low-temperature microwave-assisted pyrolysis methodology has been performed for the valorisation of a range of biomass feedstocks including waste residues. Microwave pyrolysis was found to efficiently deliver comparable evolution of bio-gases in the system as compared with conventional pyrolysis at significantly reduced temperatures （120-180 ℃vs 250-400 ℃）. The gas obtained from microwave-assisted pyrolysis was found to contain CO2, CH4 and CO as major components as well展开更多
Fractional pyrolysis and one-step pyrolysis of natural algae Cyanobacteria from Taihu Lake were comparatively studied from 200 to 500 ℃. One-step pyrolysis produced bio-oil with complex composition and low high heati...Fractional pyrolysis and one-step pyrolysis of natural algae Cyanobacteria from Taihu Lake were comparatively studied from 200 to 500 ℃. One-step pyrolysis produced bio-oil with complex composition and low high heating value （HHV〈30.9 MJ/kg）. Fractional pyrolysis separated the degradation of different components in Cyanobacteria and improved the selectivity to products in bio-oil. That is, acids at 200 ℃, amides and acids at 300 ℃, phenols and nitriles at 400 ℃, and phenols at 500 ℃, were got as main products, respectively. HZSM-5 could promote the dehydration, cracking and aromatization of pyrolytic intermediates in fractional pyrolysis. At optimal HZSM-5 catalyst dosage of 1.0 g, the selectivity to products and the quality of bio-oil were improved obviously. The main products in bio-oil changed to nitriles （47.2%） at 300 ℃, indoles （51.3%） and phenols （36.3%） at 400 ℃. The oxygen content was reduced to 7.2 wt% and 9.4 wt%, and the HHV was raised to 38.1 and 37.3 MJ/kg at 300 and 400 ℃, respectively. Fractional catalytic pyrolysis was proposed to be an efficient method not only to provide a potential solution for alleviating environmental pressure from water blooms, but also to improve the selectivity to products and obtain high quality bio-oil.展开更多
Sesquiterpanes are ubiquitous components of crude oils and ancient sediments.Liquid saturated hydrocarbons from simulated pyrolysis experiments on immature organic-rich mudstone collected from the Lower Cretaceous Hes...Sesquiterpanes are ubiquitous components of crude oils and ancient sediments.Liquid saturated hydrocarbons from simulated pyrolysis experiments on immature organic-rich mudstone collected from the Lower Cretaceous Hesigewula Sag were analyzed by gas chromatography-mass spectrometry(GC-MS).C14 bicyclic sesquiterpanes,namely,8β(H)-drimane,8β(H)-homodrimane,and 8 a(H)-homodrimane were detected and identified on basis of their diagnostic fragment ions(m/z123,179,193,and 207),and previously published mass spectra data,and these bicyclic sesquiterpanes presented relatively regular characteristics in their thermal evolution.The ratios 8β(H)-drimane/8β(H)-homodrimane,8β(H)-homodrimane/8 a(H)-homodrimane,and 8β(H)-drimane/8 a(H)-homodrimane all show a clear upward trend with increasing temperature below the temperature turning point.Thus,all these ratios can be used as evolution indexes of source rocks in the immature-lowmaturity stage.However,the last two ratios may be more suitable than the first ratio as valid parameters for measuring the extent of thermal evolution of organic matter in the immature-low-maturity stage because their change amplitude with increasing temperature is more obvious.展开更多
Co-pyrolysis of lignin and waste plastics,for example polyethylene(PE),has been studied,but related reports are basically on condition optimizations.This study revealed a new perspective on PE-promoted lignin pyrolysi...Co-pyrolysis of lignin and waste plastics,for example polyethylene(PE),has been studied,but related reports are basically on condition optimizations.This study revealed a new perspective on PE-promoted lignin pyrolysis to phenolic monomers with mass transfer and radical explanation.Lignin and PE were first pyrolyzed individually to identify pyrolysis characteristics,pyrolytic products,as well as the suitable copyrolysis temperature.Then,co-pyrolysis of blended lignin/PE with various ratios was investigated.Yields of lignin products reached the maximum under lignin/PE ratio of 1:1,but blended approach always inhibited the production of lignin phenols.This resulted from the poor mass transfer and interactions between lignin and PE,in which PE pyrolysates could easily escape from the particle gaps.While in layered approach,PE pyrolysates had to pass through the lignin layer which contributed to the good interactions with lignin pyrolysis intermediates,thus the yields of lignin-derived products were significantly improved.Interactions between lignin and PE(or their pyrolysates)were mainly radical quenching reactions,and X-ray photoelectron spectrum(XPS)and electron paramagnetic resonance(EPR)of pyrolytic chars were conducted to verify these interactions controlled by mass transfer.The percentage of C]C(sp^(2))and concentration of organic stable radicals in layered lignin/PE char were both the lowest compared with those in blended lignin/PE and lignin char,indicating the stabilization of lignin-derived radicals by PE pyrolysates.Moreover,the spin concentration of radicals in the char from layered char/PE was lower than that in lignin char,which further affirmed the quenching of radicals by PE in the layered co-pyrolysis mode.展开更多
The synergistic pyrolysis has been increasingly used for recycling spent lithium-ion batteries(LIBs)and organic wastes(hydrogen and carbon sources),which are in-situ transformed into various reducing agents such as H_...The synergistic pyrolysis has been increasingly used for recycling spent lithium-ion batteries(LIBs)and organic wastes(hydrogen and carbon sources),which are in-situ transformed into various reducing agents such as H_(2),CO,and char via carbothermal and/or gas thermal reduction.Compared with the conventional roasting methods,this“killing two birds with one stone”strategy can not only reduce the cost and energy consumption,but also realize the valorization of organic wastes.This paper concluded the research progress in synergistic pyrolysis recycling of spent LIBs and organic wastes.On the one hand,valued metals such as Li,Co,Ni,and Mn can be recovered through the pyrolysis of the cathode materials with inherent organic materials(e.g.,separator,electrolyte)or graphite anode.During the pyrolysis process,the organic materials are decomposed into char and gases(e.g.,CO,H_(2),and CH_(4))as reducing agents,while the cathode material is decomposed and then converted into Li_(2)CO_(3) and low-valent transition metals or their oxides via in-situ thermal reduction.The formed Li_(2)CO_(3) can be easily recovered by the water leaching process,while the formed transition metals or their oxides(e.g.,Co,CoO,Ni,MnO,etc.)can be recovered by the reductant-free acid leaching or magnetic separation process.On the other hand,organic wastes(e.g.,biomass,plastics,etc.)as abundant hydrogen and carbon sources can be converted into gas(e.g.,H_(2),CO,etc.)and char via pyrolysis.The cathode materials are decomposed and subsequently reduced by the pyrolysis gas and char.In addition,the pyrolysis oil and gas can be upgraded by catalytic reforming with the active metals derived from cathode material.Finally,great challenges are proposed to promote this promising technology in the industrial applications.展开更多
基金Fundamental Research Funds for the Central Universities(M23JBZY00050)National Natural Science Foundation of China(22278032)。
文摘The kinetic characteristics of plasma-assisted oxidative pyrolysis of ammonia are studied by using the global/fluid models hybrid solution method.Firstly,the stable products of plasma-assisted oxidative pyrolysis of ammonia are measured.The results show that the consumption of NH_(3)/O_(2)and the production of N_(2)/H_(2)change linearly with the increase of voltage,which indicates the decoupling of nonequilibrium molecular excitation and oxidative pyrolysis of ammonia at low temperatures.Secondly,the detailed reaction kinetics mechanism of ammonia oxidative pyrolysis stimulated by a nanosecond pulse voltage at low pressure and room temperature is established.Based on the reaction path analysis,the simplified mechanism is obtained.The detailed and simplified mechanism simulation results are compared with experimental data to verify the accuracy of the simplified mechanism.Finally,based on the simplified mechanism,the fluid model of ammonia oxidative pyrolysis stimulated by the nanosecond pulse plasma is established to study the pre-sheath/sheath behavior and the resultant consumption and formation of key species.The results show that the generation,development,and propagation of the pre-sheath have a great influence on the formation and consumption of species.The consumption of NH_(3)by the cathode pre-sheath is greater than that by the anode pre-sheath,but the opposite is true for OH and O(1S).However,within the sheath,almost all reactions do not occur.Further,by changing the parameters of nanosecond pulse power supply voltage,it is found that the electron number density,electron current density,and applied peak voltages are not the direct reasons for the structural changes of the sheath and pre-sheath.Furthermore,the discharge interval has little effect on the sheath structure and gas mixture breakdown.The research results of this paper not only help to understand the kinetic promotion of non-equilibrium excitation in the process of oxidative pyrolysis but also help to explore the influence of transport and chemical reaction kinetics on the oxidative pyrolysis of ammonia.
基金Fund of University of South China (201RGC013 and 200XQD052)。
文摘The recycling of spent lithium-ion batteries(LIBs) is crucial for environmental protection and resource sustainability.However,the economic recovery of spent LIBs remains challenging due to low Li recovery efficiency and the need for multiple separation operations.Here,we propose a process involving mixed HCl-H_(2)SO_(4) leaching-spray pyrolysis for recycling spent ternary LIBs,achieving both selective Li recovery and the preparation of a ternary oxide precursor.Specifically,the process transforms spent ternary cathode(LiNi_(x)Co_yMn_(2)O_(2),NCM) powder into Li_(2)SO_(4) solution and ternary oxide,which can be directly used for synthesizing battery-grade Li_(2)CO_(3) and NCM cathode,respectively.Notably,SO_(4)^(2-) selectively precipitates with Li^(+) to form thermostable Li_(2)SO_(4) during the spray pyrolysis,which substantially improves the Li recovery efficiency by inhibiting Li evaporation and intercalation.Besides,SO_(2) emissions are avoided by controlling the molar ratio of Li^(+)/SO_(4)^(2-)(≥2:1),The mechanism of the preferential formation of Li_(2)SO_(4) is interpreted from its reverse solubility variation with temperature.During the recycling of spent NCM811,92% of Li is selectively recovered,and the regenerated NCM811 exhibits excellent cycling stability with a capacity retention of 81.7% after 300 cycles at 1 C.This work offers a simple and robust process for the recycling of spent NCM cathodes.
文摘Oxidative-exfoliation methods were in vogue in the production of rGO from graphite.Processing of such synthetic graphite needs high temperatures(2500℃).Thus,such process is not cost-effective.The present study is made on the dry leaves of sugarcane(Saccharum officinarum)as an alternative raw material so as to be economical and environmentally benign.The dry leaves are subjected to two-step pyrolysis without any catalyst or reducing agent in far divergent temperatures to produce as prepared and acid treated rGOs.They were evaluated by UV–Vis.,FTIR,XRD,Raman spectroscopy,TGA/DTG,BET,FESEM-EDS and TEM.The as prepared rGO has few layers with irregular and folded architecture whereas acid-treated rGO has thinly stacked crumpled sheets with many wrinkles on its surface.The prepared rGOs have multilayered graphitic structure due to the unique ratio between G and D bands.Acid treated rGO has poor thermal stability as compared to that of as-prepared rGO at high temperatures due to the variation in the oxygen-containing functional groups.Acid treated rGO has low antibacterial activity as compared to that of the as-prepared rGO due to the paucity of the functional groups.
基金supported by the National Natural Science Foundation of China (Nos.U22B6004,51974341)State Key Laboratory of Deep Oil and Gas (No.SKLDOG2024-ZYTS-14)the Fundamental Research Funds for the Central Universities (No.20CX06070A)。
文摘The efficient pyrolysis and conversion of organic matter in organic-rich shale,as well as the effective recovery of pyrolysis shale oil and gas,play a vital role in alleviating energy pressure.The state of carbon dioxide(CO_(2))in the pyrolysis environment of shale reservoirs is the supercritical state.Its unique supercritical fluid properties not only effectively heat organic matter,displace pyrolysis products and change shale pore structure,but also achieve carbon storage to a certain extent.Shale samples were made into powder and three sizes of cores,and nitrogen(N_(2))and supercritical carbon dioxide(ScCO_(2))pyrolysis experiments were performed at different final pyrolysis temperatures.The properties and mineral characteristics of the pyrolysis products were studied based on gas chromatography analysis,Xray diffraction tests,and mass spectrometry analysis.Besides,the pore structure characteristics at different regions of cores before and after pyrolysis were analyzed using N_(2) adsorption tests to clarify the impact of fracturing degree on the pyrolysis effect.The results indicate that the optimal pyrolysis temperature of Longkou shale is about 430℃.Compared with N_(2),the oil yield of ScCO_(2) pyrolysis is higher.The pyrolysis oil obtained by ScCO_(2) extraction has more intermediate fractions and higher relative molecular weight.The ScCO_(2) can effectively improve the pore diameter of shale and its effect is better than that of N_(2).The micropores are produced in shale after pyrolysis,and the macropores only are generated in ScCO_(2) pyrolysis environments with temperatures greater than 430℃.The pore structure has different development characteristics at different pyrolysis temperatures,which are mainly affected by the pressure holding of volatile matter and products blocking.Compared to the surface of the core,the pore development effect inside the core is better.With the decrease in core size,the pore diameter,specific surface area,and pore volume of cores all increase after pyrolysis.
基金the grant support from the National Natural Science Foundation of China (No. 21975018, 22278032)。
文摘Ammonia is gaining increasing attention as a green alternative fuel for achieving large-scale carbon emission reduction. Despite its potential technical prospects, the harsh ignition conditions and slow flame propagation speed of ammonia pose significant challenges to its application in engines. Non-equilibrium plasma has been identified as a promising method, but current research on plasma-enhanced ammonia combustion is limited and primarily focuses on ignition characteristics revealed by kinetic models. In this study, low-temperature and low-pressure chemistry in plasma-assisted ammonia oxidative pyrolysis is investigated by integrated studies of steady-state GC measurements and mathematical simulation. The detailed kinetic mechanism of NH_(3) decomposition in plasma-driven Ar/NH_(3) and Ar/NH_(3)/O_(2) mixtures has been developed. The numerical model has good agreements with the experimental measurements in NH_(3)/O_(2) consumption and N_(2)/H_(2) generation, which demonstrates the rationality of modelling. Based on the modelling results, species density profiles, path flux and sensitivity analysis for the key plasmaproduced species such as NH_(2), NH, H_(2), OH, H, O, O(^(1)D), O_(2)(a^(1)△_(g)), O_(2)(b^(1)∑_(g)^(+)), Ar^(*), H^(-), Ar^(+), NH_(3)^(+), O_(2)^(-) in the discharge and afterglow are analyzed in detail to illustrate the effectiveness of the active species on NH_(3) excitation and decomposition at low temperature and relatively higher E/N values. The results revealed that NH_(2), NH, H as well as H_(2) are primarily generated through the electron collision reactions e + NH_(3)→ e + NH_(2)+ H, e + NH_(3)→ e + NH + H_(2) and the excited-argon collision reaction Ar^(*) + NH_(3)+ H → Ar + NH_(2)+ 2H, which will then react with highly reactive oxidative species such as O_(2)^(*), O^(*), O, OH, and O_(2) to produce stable products of NOx and H_(2)O. NH_(3)→ NH is found a specific pathway for NH_(3) consumption with plasma assistance, which further highlights the enhanced kinetic effects.
基金supported by the National Natural Science Foundation of China,China(Grant Nos.U20B2018,U21B2086,11972087)。
文摘A novel design of micro-aluminum(μAl)powder coated with bi-/tri-component alloy layer,such as:Ni-P and Ni-P-Cu(namely,Al@Ni-P,Al@Ni-P-Cu,respectively),as combustion catalysts,were introduced to release its huge energy inside Al-core and promote rapid pyrolysis of ammonium perchlorate(AP)at a lower temperature in aluminized propellants.The microstructure of Al@Ni-P-Cu demonstrates that a three-layer Ni-P-Cu shell,with the thickness of~100 nm,is uniformly supported byμAl carrier(fuel unit),which has an amorphous surface with a thickness of~2.3 nm(catalytic unit).The peak temperature of AP with the addition of Al@Ni-P-Cu(3.5%)could significantly drop to 316.2℃ at high-temperature thermal decomposition,reduced by 124.3℃,in comparison to that of pure AP with 440.5℃.It illustrated that the introduction of Al@Ni-P-Cu could weaken or even eliminate the obstacle of AP pyrolysis due to its reduction of activation energy with 118.28 kJ/mol.The laser ignition results showed that the ignition delay time of Al@Ni-P-Cu/AP mixture with 78 ms in air is shorter than that of Al@Ni-P/AP(118 ms),decreased by 33.90%.Those astonishing breakthroughs were attributed to the synergistic effects of adequate active sites on amorphous surface and oxidation exothermic reactions(7597.7 J/g)of Al@Ni-P-Cu,resulting in accelerated mass and/or heat transfer rate to catalyze AP pyrolysis and combustion.Moreover,it is believed to provide an alternative Al-based combustion catalyst for propellant designer,to promote the development the propellants toward a higher energy.
基金the financial support from the National Natural Science Foundation of China(Grant No.21576293 and 21576294)。
文摘Coal pyrolysis is a fundamental reaction in the thermal processing and utilization of coal.Investigating the behavior and kinetics of coal pyrolysis is crucial for optimizing,designing,and developing a composite riser for the staged pyrolysis gasification process of pulverized coal.In this study,the non-isothermal pyrolysis behavior and kinetics of coal were examined at different heating rates(30,50,100,300,500,700,and 900℃/min)using thermogravimetry(TG)coupled with Fourier-transform infrared spectroscopy.Analysis of the TG/derivative TG(TG/DTG)curves indicated that coal pyrolysis mainly occurred between 300℃ and 700℃.Higher heating rates led to more volatiles being released from the coal,and a higher temperature was required to achieve rapid pyrolysis.Kinetic analysis showed that both the model-free methods(Friedman,Flynn-Wall-Ozawa,and Kissinger-Akahira-Sunose)and the model-based method(Coats-Redfern)effectively describe the coal pyrolysis process.The change in the Ea values between the two kinetic models was consistent throughout the pyrolysis process,and the most probable mechanism was the F2 model(secondary chemical reaction).In addition,the heating rate did not change the overall reaction order of the pyrolysis process;however,a higher heating rate resulted in a decrease in the Ea value during the initial pyrolysis stage.
文摘The composition and sequence distribution of monomeric units in polyester polyether multiblock copolymer were studied by pyrolysis? gas chromatography (PGC) and pyrolysis gas chromatography/mass spectrometry (PGC/MS). PGC was applied to study the F t curve of the multiblock copolymer and PGC/MS was used to separate and identify the pyrolyzates. DTA experiment was used to study the decomposition temperature. The results show that the beginning point of elastomer’s decomposition was about 300?℃ and the decomposition temperature of most of the sample was 550?℃. Many pyrolyzates were produced because of the breaking of weak bonds in the sample. The possible microstructure was verified and the pyrolysis pathway of the copolymer was investigated.
基金University of Tabriz for their supportsupported by the Strategic International Scientific and Technological Innovation Cooperation Special Funds of National Key R&D Program of China(No.2016YFE0204000)+2 种基金the Program for Taishan Scholars of Shandong Province Government,the Recruitment Program of Global Young Experts(Thousand Youth Talents Plan)the Natural Science Foundation of Shandong Province(ZR2017BB002)the Key R&D Program of Shandong Province(2018GSF116014)
文摘Lignocellulosic biomass can be convert to a condensable liquid named bio-oil,a solid product named as char and a mixture of gaseous products comprising CO2,CO,H2,CH4,etc.In recent years,much effort has been made on the investigation of conversion of biomass through pyrolysis.However,commercialisation of the biomass pyrolysis technology is still challenging due to various issues such as the deleterious properties of bio-oil including the low heating value and the high instability at elevated temperatures.To overcome such issues,many processes,reactors and catalysts have been developed for pyrolysis and catalytic pyrolysis of biomass.A state to the art of pyrolysis or catalytic pyrolysis of biomass need to be summarised to have an overall evaluation of the technologies,in order to provide a useful reference for the further development of pyrolysis technology.This study reviews the various pyrolysis process,especially focus on the effects of essential parameters,the process design,the reactors and the catalysts on the pyrolysis process.In addition,progress in commercialisation of pyrolysis technology was also reviewed and the remaining issues in the process of commercialisation were discussed.
基金the National Basic Research Program of China (973 programs, No. 2014CB744302)Taishan Scholar Constructive Engineering Foundation of Shandong province, China (No. ts20120518)
文摘Pyrolysis characteristics of a North Korean oil shale and its pyrolysates were investigated in this paper. The pyrolysis experiments were conducted below 600 ℃ at a heating rate of 10, 15, 20 and 25 ℃/min, respectively. The kinetics data were calculated using both integral and differential methods with the assumption of first order kinetics. The results show that the averaged oil content of the North Korean oil shale is about 12.1 wt% and its heat value is 13,400 kJ/kg. The oil yields at different retorting temperatures show that the higher the retorting temperature the greater the oil and retorting gas yields. The optimal retorting temperature for the North Korean oil shale is about 500 ℃. The properties of the North Korean shale oil including density, viscosity, flash point and freezing point are found to be relatively low compared with those of shale oil from FuShun, China. The gasoline fraction, diesel fraction and heavy oil fraction account for 11.5 wt%, 41.5 wt% and 47 wt%, respectively. The major pyrolysis gases are ca4 （the most abundant）, H2, CO2, H2S, CO, and C2-C5 hydrocarbons. The heat value of retorting gas is more than 900 kJ/mol, and the retorting gas has high sulfur content.
文摘The chemical thermodynamic equilibrium of acetylene production by coal pyrolysis in hydrogen plasma was studied. The thermodynamic equilibrium is obtained by using the method of free energy. Calculated results show that the hydrogen concentration in the equilibrium system is very important for the acetylene production by coal conversion and the energy consumption for the production of acetylene per-kilogram strongly depends on the hydrogen concentration and the temperature.
基金supported by the National High Technology Research and Development Program of China(2009AA044701)the Program for Zhejiang Leading Team of S&T Innovation(2013TD07)
文摘To get deep understanding of the reaction mechanism of coal pyrolysis in hydrogen plasma, the decomposition reaction pathways of aliphatic hydrocarbons and cycloalkanes, which are two main components in volatiles from coal, were investigated. Methane and cyclohexane were chosen as the model compounds. Density functional theory was employed, and many reaction pathways were involved. Calculations were carried out in Gaussian 09 at the B3LYP/6-31G（d,p） level of the theory. The results indicate that the main pyrolysis products of methane and cyclohexane in hydrogen plasma are both hydrogen and acetylene, and the participation of active hydrogen atoms makes dehydrogenation reactions more favorable. H2 mainly comes from dehydrogenation process, while many reaction pathways are responsible for acetylene formation. During coal pyrolysis in hydrogen plasma, three main components in volatiles like aliphatic hydrocarbons, cycloalkanes and aromatic hydrocarbons lead to the formation of hydrogen and acetylene, but their contributions to products distribution are different.
基金financial support from the Basic Fund for the Scientific Research and Operation of Central Universities of China (No. 2009KH10
文摘A series of char samples were derived from pyrolysis of two typical low-rank coals in China （Shengli lig- nite and Shenmu bituminous coal） at low, medium and fast heating rates, respectively, to the same pyrol- ysis temperature 750℃. Then these chars were characterized by means of thermogravimetric analysis and Fourier transform infrared spectrometer with the aim to investigate the influence of heating rate in pyrolysis process on gasification reactivity and surface chemistry of them. Besides, a homogeneous model was used to quantitatively analyze the activation energy of gasification reaction. The results reveal that Shengli lignite and its derived chars behave higher gasification reactivity and have less content of oxygen functional groups than Shenmu coal and chars. Meanwhile, chars derived from Shengli lignite at 50℃/min and Shenmu coal at 200℃/min have the greatest gasification reactivity, respectively. The oxygen functional groups in Shengli lignite are easily thermo-decomposed, and they are less affected by the heating rate, while that in Shenmu coal have a significant change with the variation of heating rate. In addition, there is no good correlation between the change of oxygen functional groups and that of the gasification reactivity of the derived chars from pyrolysis at different heating rates.
基金Project 50474056 supported by the National Natural Science Foundation of China
文摘The pyrolysis kinetics of three different kinds of fresh biomass (grass: triple A, wheat straw, corn straw) in nitrogen flow were studied by thermogravimetric analysis at five different heating rates. The kinetic parameters of the pyrolysis process were calculated using the method of Ozawa-Flynn-Wall and the mechanism of reactions were investi- gated using the method of Popescu. It was found that the values of activation energy varied in different temperature ranges. The pyrolysis processes are well described by the models of Zhuravlev (Zh) and valid for diffusion-controlled between 200 ℃ and 280 ℃, by Ginstling-Brounshtein (G-B), valid for diffusion-control between 280 ℃ and 310 ℃, for first-order chemical reaction between 310℃ and 350 ℃, by Zhuravlev (Zh) valid for diffusion-control between 350 ℃ and 430 ℃ and by the one-way transport model when temperatures are over 430 ℃.
基金Project 2005BS09003 supported by Shandong Province Foundation for Distinguished Young Scholars
文摘The pyrolysis characteristics of PVC were systematically investigated using a Netzschne TG thermo-balance coupled to a quadrupole mass spectrometer. The pyrolysis conditions were 0.1 MPa of Ar, a heating rate of 10 ℃/min and a final temperature of 1000℃. Both the thermogravimetric properties and the simultaneous evolution of gaseous products during pyrolysis were studied. The TG/DTG results showed that as the pyrolysis temperature increases the weight loss and weight loss rate of PVC increases. Near 412℃ the weight loss rate attained its peak value. At higher temperatures the rate of loss gradually decreases. The gases evolved during thermogravimetric analysis were analyzed by a mass spectrometer, monitoring the relative intensity of HC1, C6H6, light hydrocarbon and chlorine-containing gases The evolution curves showed that HC1, C6H6, light hydrocarbon and chlorine-containing gases all peak at about 416℃. This is consistent with the fact that the weight loss curves also peak at about 412℃. The extensive HCl evolution is consistent with the high chlorine content of PVC. The formation of these gases can be explained by considering these reactions： dehydrochlorination, intramolecular cyclization and the addition of HCl to unsaturated hydrocarbons.
基金supported by the Gobierno de Espaa for the Provision of a Ramon y Cajal Contract (RYC-2009-04199),Projects P10 FQM-6711(Consejeria de Ciencia e Innovacion,Junta de Andalucia) and CTQ2011 28954-C02-02 (MICINN)
文摘A comparison between conventional pyrolysis and a novel developed low-temperature microwave-assisted pyrolysis methodology has been performed for the valorisation of a range of biomass feedstocks including waste residues. Microwave pyrolysis was found to efficiently deliver comparable evolution of bio-gases in the system as compared with conventional pyrolysis at significantly reduced temperatures （120-180 ℃vs 250-400 ℃）. The gas obtained from microwave-assisted pyrolysis was found to contain CO2, CH4 and CO as major components as well
基金supported by the National Basic Research Program of China(973 Program,No.2013CB228103)
文摘Fractional pyrolysis and one-step pyrolysis of natural algae Cyanobacteria from Taihu Lake were comparatively studied from 200 to 500 ℃. One-step pyrolysis produced bio-oil with complex composition and low high heating value （HHV〈30.9 MJ/kg）. Fractional pyrolysis separated the degradation of different components in Cyanobacteria and improved the selectivity to products in bio-oil. That is, acids at 200 ℃, amides and acids at 300 ℃, phenols and nitriles at 400 ℃, and phenols at 500 ℃, were got as main products, respectively. HZSM-5 could promote the dehydration, cracking and aromatization of pyrolytic intermediates in fractional pyrolysis. At optimal HZSM-5 catalyst dosage of 1.0 g, the selectivity to products and the quality of bio-oil were improved obviously. The main products in bio-oil changed to nitriles （47.2%） at 300 ℃, indoles （51.3%） and phenols （36.3%） at 400 ℃. The oxygen content was reduced to 7.2 wt% and 9.4 wt%, and the HHV was raised to 38.1 and 37.3 MJ/kg at 300 and 400 ℃, respectively. Fractional catalytic pyrolysis was proposed to be an efficient method not only to provide a potential solution for alleviating environmental pressure from water blooms, but also to improve the selectivity to products and obtain high quality bio-oil.
基金supported by the National Natural Science Foundation of China (Grant Nos. 41672117 and 41503034)the Hubei Provincial Natural Science Foundation of China (Project No. 2017CFA027)+1 种基金the Open Subject of Shandong Provincial Key Laboratory of Depositional Mineralization & Sedimentary Mineral (Baojun Liu Geoscience Science Foundation) (DMSM2017084)the Open Subject of the State Key Laboratory of Petroleum Resources and Prospecting (PRP/open-1509)
文摘Sesquiterpanes are ubiquitous components of crude oils and ancient sediments.Liquid saturated hydrocarbons from simulated pyrolysis experiments on immature organic-rich mudstone collected from the Lower Cretaceous Hesigewula Sag were analyzed by gas chromatography-mass spectrometry(GC-MS).C14 bicyclic sesquiterpanes,namely,8β(H)-drimane,8β(H)-homodrimane,and 8 a(H)-homodrimane were detected and identified on basis of their diagnostic fragment ions(m/z123,179,193,and 207),and previously published mass spectra data,and these bicyclic sesquiterpanes presented relatively regular characteristics in their thermal evolution.The ratios 8β(H)-drimane/8β(H)-homodrimane,8β(H)-homodrimane/8 a(H)-homodrimane,and 8β(H)-drimane/8 a(H)-homodrimane all show a clear upward trend with increasing temperature below the temperature turning point.Thus,all these ratios can be used as evolution indexes of source rocks in the immature-lowmaturity stage.However,the last two ratios may be more suitable than the first ratio as valid parameters for measuring the extent of thermal evolution of organic matter in the immature-low-maturity stage because their change amplitude with increasing temperature is more obvious.
基金support of the National Key R&D Program of China(Grant no.2018YFB1501402)the Natural Science Foundation of Jiangsu Province(Grant no.BK20190363)the Fundamental Research Funds for the Central Universities(Grant no.2242020R20009).
文摘Co-pyrolysis of lignin and waste plastics,for example polyethylene(PE),has been studied,but related reports are basically on condition optimizations.This study revealed a new perspective on PE-promoted lignin pyrolysis to phenolic monomers with mass transfer and radical explanation.Lignin and PE were first pyrolyzed individually to identify pyrolysis characteristics,pyrolytic products,as well as the suitable copyrolysis temperature.Then,co-pyrolysis of blended lignin/PE with various ratios was investigated.Yields of lignin products reached the maximum under lignin/PE ratio of 1:1,but blended approach always inhibited the production of lignin phenols.This resulted from the poor mass transfer and interactions between lignin and PE,in which PE pyrolysates could easily escape from the particle gaps.While in layered approach,PE pyrolysates had to pass through the lignin layer which contributed to the good interactions with lignin pyrolysis intermediates,thus the yields of lignin-derived products were significantly improved.Interactions between lignin and PE(or their pyrolysates)were mainly radical quenching reactions,and X-ray photoelectron spectrum(XPS)and electron paramagnetic resonance(EPR)of pyrolytic chars were conducted to verify these interactions controlled by mass transfer.The percentage of C]C(sp^(2))and concentration of organic stable radicals in layered lignin/PE char were both the lowest compared with those in blended lignin/PE and lignin char,indicating the stabilization of lignin-derived radicals by PE pyrolysates.Moreover,the spin concentration of radicals in the char from layered char/PE was lower than that in lignin char,which further affirmed the quenching of radicals by PE in the layered co-pyrolysis mode.
基金supported by the National Key Research and Development Program of China(Grant 2022YFC3701504)。
文摘The synergistic pyrolysis has been increasingly used for recycling spent lithium-ion batteries(LIBs)and organic wastes(hydrogen and carbon sources),which are in-situ transformed into various reducing agents such as H_(2),CO,and char via carbothermal and/or gas thermal reduction.Compared with the conventional roasting methods,this“killing two birds with one stone”strategy can not only reduce the cost and energy consumption,but also realize the valorization of organic wastes.This paper concluded the research progress in synergistic pyrolysis recycling of spent LIBs and organic wastes.On the one hand,valued metals such as Li,Co,Ni,and Mn can be recovered through the pyrolysis of the cathode materials with inherent organic materials(e.g.,separator,electrolyte)or graphite anode.During the pyrolysis process,the organic materials are decomposed into char and gases(e.g.,CO,H_(2),and CH_(4))as reducing agents,while the cathode material is decomposed and then converted into Li_(2)CO_(3) and low-valent transition metals or their oxides via in-situ thermal reduction.The formed Li_(2)CO_(3) can be easily recovered by the water leaching process,while the formed transition metals or their oxides(e.g.,Co,CoO,Ni,MnO,etc.)can be recovered by the reductant-free acid leaching or magnetic separation process.On the other hand,organic wastes(e.g.,biomass,plastics,etc.)as abundant hydrogen and carbon sources can be converted into gas(e.g.,H_(2),CO,etc.)and char via pyrolysis.The cathode materials are decomposed and subsequently reduced by the pyrolysis gas and char.In addition,the pyrolysis oil and gas can be upgraded by catalytic reforming with the active metals derived from cathode material.Finally,great challenges are proposed to promote this promising technology in the industrial applications.
