Understanding the relationship between the chemical composition and pyrolysis performance of endothermic hydrocarbon fuel(EHF) is of great significance for the design and optimization of advanced EHFs. In this work, t...Understanding the relationship between the chemical composition and pyrolysis performance of endothermic hydrocarbon fuel(EHF) is of great significance for the design and optimization of advanced EHFs. In this work, the effect of deep hydrogenation on the pyrolysis of commercial RP-3 is investigated.Fuels with different hydrogenation degrees were obtained by the partially and completely catalytic hydrogenation and their pyrolysis performances were investigated using an apparatus equipped with an electrically heated tubular reactor. The results show that with the increase of hydrogenation degree, fuel conversion almost remains constant during the pyrolysis process(500-650°C, 4 MPa);however, the heat sink increases slightly, and the anti-coking performance significantly improves, which are highly related to their H/C ratios. Detailed characterisations reveal that the difference of the pyrolysis performance can be ascribed to the content of aromatics and cycloalkanes: the former are prone to initiate secondary reactions to form coking precursors, while the latter could act as the hydrogen donor and release hydrogen, which will terminate the radical propagation reactions and suppress the coke deposition. This work should provide the guidance for upgrading EHFs by modulating the composition of EHFs.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
Biochar and bio-oil are produced simultaneously in one pyrolysis process,and they inevitably contact and may interact,influencing the composition of bio-oil and modifying the structure of biochar.In this sense,biochar...Biochar and bio-oil are produced simultaneously in one pyrolysis process,and they inevitably contact and may interact,influencing the composition of bio-oil and modifying the structure of biochar.In this sense,biochar is an inherent catalyst for pyrolysis.In this study,in order to investigate the influence of functionalities and pore structures of biochar on its capability for catalyzing the conversion of homologous volatiles in bio-oil,three char catalysts(600C,800C,and 800AC)produced via pyrolysis of poplar wood at 600 or 800℃or activated at 800℃,were used for catalyzing pyrolysis of homologous poplar wood at 600℃,respectively.The results indicated that the 600C catalyst was more active than 800C and 800AC for catalyzing cracking of volatiles to form more gas(yield increase by 40.2%)and aromatization of volatiles to form more light or heavy phenolics,due to its abundant oxygen-containing functionalities acting as active sites.The developed pores of the 800AC showed no such catalytic effect but could trap some volatiles and allow their further conversion via sufficient aromatization.Nevertheless,the interaction with the volatiles consumed oxygen on 600C(decrease by 50%),enhancing the aromatic degree and increasing thermal stability.The dominance of deposition of carbonaceous material of a very aromatic nature over 800C and 800AC resulted in net weight gain and blocked micropores but formed additional macropores.The in situ diffuse reflectance infrared Fourier transform spectroscopy characterization of the catalytic pyrolysis indicated superior activity of 600C for removal of -OH,while conversion of the intermediates bearing C=O was enhanced over all the char catalysts.展开更多
This study developed a numerical model to efficiently treat solid waste magnesium nitrate hydrate through multi-step chemical reactions.The model simulates two-phase flow,heat,and mass transfer processes in a pyrolysi...This study developed a numerical model to efficiently treat solid waste magnesium nitrate hydrate through multi-step chemical reactions.The model simulates two-phase flow,heat,and mass transfer processes in a pyrolysis furnace to improve the decomposition rate of magnesium nitrate.The performance of multi-nozzle and single-nozzle injection methods was evaluated,and the effects of primary and secondary nozzle flow ratios,velocity ratios,and secondary nozzle inclination angles on the decomposition rate were investigated.Results indicate that multi-nozzle injection has a higher conversion efficiency and decomposition rate than single-nozzle injection,with a 10.3%higher conversion rate under the design parameters.The decomposition rate is primarily dependent on the average residence time of particles,which can be increased by decreasing flow rate and velocity ratios and increasing the inclination angle of secondary nozzles.The optimal parameters are injection flow ratio of 40%,injection velocity ratio of 0.6,and secondary nozzle inclination of 30°,corresponding to a maximum decomposition rate of 99.33%.展开更多
This work investigated the pyrolysis reaction of waste resin in a fluidized bed reactor.It was found that the pyrolysis-generated ash would adhere to the surface of ceramic particles,causing particle agglomeration and...This work investigated the pyrolysis reaction of waste resin in a fluidized bed reactor.It was found that the pyrolysis-generated ash would adhere to the surface of ceramic particles,causing particle agglomeration and defluidization.Adding kaolin could effectively inhibit the particle agglomeration during the fluidized pyrolysis reaction through physical isolation and chemical reaction.On the one hand,kaolin could form a coating layer on the surface of ceramic particles to prevent the adhesion of organic ash generated by the pyrolysis of resin.On the other hand,when a sufficient amount of kaolin(-0.2%(mass))was added,the activated kaolin could fully contact with the Na+ ions generated by the pyrolysis of resin and react to form a high-melting aluminosilicate mineral(nepheline),which could reduce the formation of low-melting-point sodium sulfate and thereby avoid the agglomeration of ceramic particles.展开更多
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
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
The current energy crisis could be alleviated by enhancing energy generation using the abundant biomass waste resources. Agricultural and forest wastes are the leading organic waste streams that can be transformed int...The current energy crisis could be alleviated by enhancing energy generation using the abundant biomass waste resources. Agricultural and forest wastes are the leading organic waste streams that can be transformed into useful alternative energy resources. Pyrolysis is one of the technologies for converting biomass into more valuable products, such as bio-oil, bio-char, and syngas. This work investigated the production of bio-oil through batch pyrolysis technology. A fixed bed pyrolyzer was designed and fabricated for bio-oil production. The major components of the system include a fixed bed reactor, a condenser, and a bio-oil collector. The reactor was heated using a cylindrical biomass external heater. The pyrolysis process was carried out in a reactor at a pressure of 1atm and a varying operating temperature of 150˚C, 250˚C, 350˚C to 450˚C for 120 minutes. The mass of 1kg of coconut fiber was used with particle sizes between 2.36 mm - 4.75 mm. The results show that the higher the temperature, the more volume of bio-oil produced, with the highest yield being 39.2%, at 450˚C with a heating rate of 10˚C/min. The Fourier transformation Infrared (FTIR) Spectroscopy analysis was used to analyze the bio-oil components. The obtained bio-oil has a pH of 2.4, a density of 1019.385 kg/m<sup>3</sup>, and a calorific value of 17.5 MJ/kg. The analysis also showed the presence of high-oxygenated compounds;carboxylic acids, phenols, alcohols, and branched oxygenated hydrocarbons as the main compounds present in the bio-oil. The results inferred that the liquid product could be bestowed as an alternative resource for polycarbonate material production.展开更多
Catalytic pyrolysis of digestate to produce aromatic hydrocarbons can be combined with anaerobic fermentation to effectively transform and utilize all biomass components,which can achieve the meaningful purpose of tra...Catalytic pyrolysis of digestate to produce aromatic hydrocarbons can be combined with anaerobic fermentation to effectively transform and utilize all biomass components,which can achieve the meaningful purpose of transforming waste into high-value products.This study explored whether catalytic pyrolysis of digestate is feasible to prepare aromatic hydrocarbons by analyzing the thermogravimetric characteristics,pyrolysis characteristics,and catalytic pyrolysis characteristics of digestate.For digestate pyrolysis,an increase in temperature was found to elevate the CO,CH_4,and monocyclic aromatic hydrocarbon(benzene,toluene,and xylene;BTX)content,whereas it decreased the contents of phenols,acids,aldehydes,and other oxygenates.Furthermore,the catalytic pyrolysis process effectively inhibited the acids,phenols,and furans in the liquid,whereas the yield of BTX increased from 25.45%to 45.99%,and the selectivity of xylene was also increased from 10.32%to 28.72%after adding ZSM-5.ZSM-5 also inhibited the production of nitrogenous compounds.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
Over the past half-century, plastic consumption has grown rapidly due to its versatility, low cost, and unrivaled functional properties. Among the diff erent implemented strategies for recycling waste plastics, pyroly...Over the past half-century, plastic consumption has grown rapidly due to its versatility, low cost, and unrivaled functional properties. Among the diff erent implemented strategies for recycling waste plastics, pyrolysis is deemed the most economical option. Currently, the wax obtained from the pyrolysis of waste plastics is mainly used as a feedstock to manufacture chemicals and fuels or added to asphalt for pavement construction, with no other applications of wax being reported. Herein, the thermal pyrolysis of three common waste polyolefin plastics: high-density polyethylene(HDPE), low-density polyethylene(LDPE), and polypropylene(PP), was conducted at 450 ℃. The waste plastics-derived waxes were characterized and studied for a potential new application: phase change materials(PCMs) for thermal energy storage(TES). Gas chromatography–mass spectrometry analysis showed that paraffin makes up most of the composition of HDPE and LDPE waxes, whereas PP wax contains a mixture of naphthene, isoparaffin, olefin, and paraffin. Diff erential scanning calorimetry(DSC) analysis indicated that HDPE and LDPE waxes have a peak melting temperature of 33.8 ℃ and 40.3 ℃, with a relatively high latent heat of 103.2 J/g and 88.3 J/g, respectively, whereas the PP wax was found to have almost negligible latent heat. Fourier transform infrared spectroscopy and DSC results revealed good chemical and thermal stability of HDPE and LDPE waxes after 100 cycles of thermal cycling. Performance evaluation of the waxes was also conducted using a thermal storage pad to understand their thermoregulation characteristics for TES applications.展开更多
Light olefins,particularly ethylene and propylene,are the most important building blocks for the petrochemical industry,and demand for their production has been increasing.The catalytic pyrolysis process(CPP)and the c...Light olefins,particularly ethylene and propylene,are the most important building blocks for the petrochemical industry,and demand for their production has been increasing.The catalytic pyrolysis process(CPP)and the corresponding catalyst,developed by SINOPEC Research Institute of Petroleum Processing Co.,Ltd.,are designed to maximize the light olefin yield from catalytic cracking of heavy feedstocks.However,owing to the continuing degradation of feedstocks,the original catalyst can no longer maintain its activity.Herein,we describe the rational design of the new catalyst,Epylene,from a new metal-modified hierarchical ZSM-5 zeolite and matrix.Epylene was tested in the CPP unit of Shaanxi Yanchang Coal Yulin Energy and Chemical Company.A test run and base run were conducted to demonstrate the better performance of Epylene compared with the original catalyst.The properties of the feedstocks and the operating conditions in both runs were similar.The light olefin yield was increased from 33.95%to 36.50%and the coke yield was only 9.58%in the test run,which was lower than that in the base run.展开更多
The critical issue in developing mature Oxy-Coal Combustion Steam System technology could be the reactivity of deminer-alized coal which,is closely related to its chemical structure.The chemical structures of Liupansh...The critical issue in developing mature Oxy-Coal Combustion Steam System technology could be the reactivity of deminer-alized coal which,is closely related to its chemical structure.The chemical structures of Liupanshui raw coal(LPS-R)and Liupanshui demineralized coal(LPS-D)were analyzed by FTIR and solid-state 13C-NMR.The pyrolysis experiments were carried out by TG,and the pyrolysis kinetics was analyzed by three iso-conversional methods.FTIR and 13C-NMR results suggested that the carbon structure of LPS coal was not altered greatly,while demineralization promoted the maturity of coal and the condensation degree of the aromatic ring,making the chemical structure of coal more stable.The oxygen-containing functional groups with low bond energy were reduced,and the ratio of aromatic carbon with high bond energy was increased,decreasing the pyrolysis reactivity.DTG curve-fitting results revealed that the thermal weight loss of LPS coal mainly came from the cleavage of aliphatic covalent bonds.By pyrolysis kinetics analysis of LPS-R and LPS-D,the apparent activation energies were 76±4 to 463±5 kJ/mol and 84±2 to 758±12 kJ/mol,respectively,under different conversion rates.The reactivity of the demineralized coal was inhibited to some extent,as the apparent activation energy of pyrolysis for LPS-D increased by acid treatment.展开更多
The chemical composition,structural and plastometric properties of different-ranked coals from Mongolia deposits were studied.The non-isothermal iso-conversion Ozawa-Flynn-Wall and Friedman model-free methods were use...The chemical composition,structural and plastometric properties of different-ranked coals from Mongolia deposits were studied.The non-isothermal iso-conversion Ozawa-Flynn-Wall and Friedman model-free methods were used to assess kinetic parameters and to differentiate decomposition steps.Key peculiarities of the pyrolysis kinetics of brown and bituminous coals were revealed and discussed in terms of the composition and plastometric properties.Brown coal was shown to undergo three decomposition steps with ever increasing activation energy as temperature increased because of the decomposition of thermally more and more stable molecular fragments.The pyrolysis of bituminous coals occurred in four steps,the activation energy having extreme mode of temperature dependence.An important new finding was that the temperature range of the second,major pyrolysis step well corresponded to that between the softening and re-solidification temperatures according to Gieseler plastometry.The yield and composition of the pyrolysis products obtained under isothermal conditions were also characterized depending on coal rank and temperature,and the ways for qualified utilizations were offered.展开更多
Silica aerogels have promising applications in thermal insulation,but their flammability and reaction mechanisms have rarely been investigated.The pyrolysis kinetics and thermodynamics of hydrophobic silica aerogels u...Silica aerogels have promising applications in thermal insulation,but their flammability and reaction mechanisms have rarely been investigated.The pyrolysis kinetics and thermodynamics of hydrophobic silica aerogels under N_(2) environment were studied.The kinetic and thermodynamic parameters were obtained by three model-free methods.Based on the calculated kinetic parameters,the pyrolysis mechanism of silica aerogels was discussed by the master plots method.The results indicate that the reactions of the whole pyrolysis phase can be characterized by a random nuclear model.In addition,FTIR test results show that the volatile products of silica aerogel pyrolysis are mainly hydrocarbons generated by the decomposition of hydrophobic groups(methyl groups)on the surface.Finally,the effects of pyrolysis on the properties of silica aerogels Finally,the effects of pyrolysis on the properties of silica aerogels were investigated based on the analysis results of SEM,specific surface area,pore size distribution,X-ray diffraction,XPS and infrared spectroscopy.展开更多
Soybean soapstock(SS) is one of the main solid wastes produced in the refinery of edible oil processing. In this study, the co-pyrolysis of SS with iron slag(IS) and aluminum scrap(AS) was carried out in a tubular fur...Soybean soapstock(SS) is one of the main solid wastes produced in the refinery of edible oil processing. In this study, the co-pyrolysis of SS with iron slag(IS) and aluminum scrap(AS) was carried out in a tubular furnace. The gas, liquid and solid products were characterized and the char yield decreased with increasing IS/AS ratio. IS and AS can improve the gas yield, and when the ratio of SS/IS was 1:0.25, the total pyrolysis gas and hydrogen contents were significantly increased. The content of oxygen compounds in pyrolysis oil decreased during co-pyrolysis, while AS promoted the content of polycyclic aromatic hydrocarbons in pyrolysis oil. The co-pyrolysis reaction can be divided into four stages, the mass loss rate reaches the maximum at the third stage(390–575 ℃). The molar ratio of H/C was lower for pyrolysis,indicating good stability of pyrolysis char owing to the high degree of carbonization and aromaticity.The possible co-pyrolysis reaction mechanism was explored.展开更多
Cyclotriphosphazene derivatives can effectively improve the flame retardancy and fire safety of epoxy resins(EPs)via their influence on the pyrolysis process.In this work,the effects of hexa(5-methyl-2-pyridinoxyl)cyc...Cyclotriphosphazene derivatives can effectively improve the flame retardancy and fire safety of epoxy resins(EPs)via their influence on the pyrolysis process.In this work,the effects of hexa(5-methyl-2-pyridinoxyl)cyclotriphosphazene(HMPOP)incorporation on the initial pyrolysis of an EP at 500–3500 K were studied using the ReaxFF method.The pyrolysis fragments,initial reaction pathways,and main products were identified for the EP and EP/HMPOP composites.The activation energies were derived by fitting the weight percentage curves for solid species during the pyrolysis reactions and the obtained values were in good agreement with experimental data.The initial EP pyrolysis reactions included four major decomposition modes,which primarily involved the cleavage of C–O and C–N bonds.The main pyrolysis products were H_(2)O,CO,C_(2)H_(4),and CH_(2)O.HMPOP bonded with the oxygen-containing fragments to form larger molecular fragments and reduced the amounts of C_(0)–C_(4) products,especially that of the harmful gas CH_(2)O.Thus,HMPOP promoted the formation of carbon clusters and reduced the generation of combustible gases,ultimately decreasing the capacity for fire propagation.展开更多
When converting C_(5) hydrocarbons to light olefins by catalytic pyrolysis,the generation of low value-added methane will affect the atomic utilization efficiency of C_(5) hydrocarbons.To improve the atomic utilizatio...When converting C_(5) hydrocarbons to light olefins by catalytic pyrolysis,the generation of low value-added methane will affect the atomic utilization efficiency of C_(5) hydrocarbons.To improve the atomic utilization efficiency,different generation pathways of light olefins and methane in the catalytic pyrolysis of C_(5) hydrocarbons were analyzed,and the effects of reaction conditions and zeolite types were inves-tigated.Results showed that light olefins were mainly formed by breaking the C_(2)-C_(3) bond in the middle position,while methane was formed by breaking the C_(1)-C_(2) bond at the end.Meanwhile,it was discovered that the hydrogen transfer reaction could be reduced by about 90%by selecting MTT zeolite with 1D topology and FER zeolite with 2D topology under high weight hourly space velocity(WHSV)and high temperature operations,thus leading to the improvement of the light olefins selectivity for the catalytic pyrolysis of n-pentane and 1-pentene to 55.12% and 74.60%,respectively.Moreover,the fraction ratio of terminal C_(1)-C_(2) bond cleavage was reduced,which would reduce the selectivity of methane to 6.63%and 1.83%.Therefore,zeolite with low hydrogen transfer activity and catalytic pyrolysis process with high WHsV will be conducive to maximize light olefins and to decrease methane.展开更多
The pyrolysis of cyclohexane,methylcyclohexane,and ethylcyclohexane have been studied behind reflected shock waves at pressures of 5 and10 bar and at temperatures of 930-1550 K for 0.05%fuel diluted by Argon.A single-...The pyrolysis of cyclohexane,methylcyclohexane,and ethylcyclohexane have been studied behind reflected shock waves at pressures of 5 and10 bar and at temperatures of 930-1550 K for 0.05%fuel diluted by Argon.A single-pulse shock tube(SPST)is used to perform the pyrolysis experiments at reaction times varying from 1.65 to 1.74 ms.Major products are obtained and quantified using gas chromatography analysis.A flame ionization detector and a thermal conductivity detector are used for species identification and quantification.Kinetic modeling has been performed using several detailed and lumped chemical kinetic mechanisms.Differences in modeling results among the kinetic models are described.Reaction path analysis and sensitivity analysis are performed to determine the important reactions controlling fuel pyrolysis and their influence on the predicted concentrations of reactant and product species profiles.The present work provides new fundamental knowledge in understating pyrolysis characteristics of cyclohexane compounds and additional data set for detailed kinetic mechanism development.展开更多
The pyrolysis behaviors of Qingdao vacuum residue(QD-VR)and its SARA(saturates,aromatics,reins,and asphaltenes)fractions were evaluated by thermo-gravimetric with mass spectrometer(TG-MS).The pyrolysis kinetics were d...The pyrolysis behaviors of Qingdao vacuum residue(QD-VR)and its SARA(saturates,aromatics,reins,and asphaltenes)fractions were evaluated by thermo-gravimetric with mass spectrometer(TG-MS).The pyrolysis kinetics were determined by Friedman,one-parallel and four-parallel distributed activation energy model(DAEM),respectively.The results indicated that the pyrolysis behavior of QD-VR was similar to that of aromatics.For saturates,the release of H_(2),CH_(4),CO,and CO_(2) occurred in 80-400℃,while the temperature range for QD-VR and other fractions is 200-800℃.The average activation energy(Ea)via Friedman method was 179.72 kJ/mol and increased with the conversion ratio.One-parallel Gaussian DAEM was more suitable to describe the pyrolysis process of the single SARA fractions,while four-parallel Gaussian DAEM was more suitable to describe the pyrolysis process of heavy oil.Furthermore,comparing the weighted E_(a) from one-parallel(227.64 kJ/mol)and four-parallel Gaussian DAEM(204.63 kJ/mol),the results suggested that during pyrolysis process of heavy oil,there was an interaction between the SARA fractions,which could reduce the E_(a) of heavy oil pyrolysis.Specifically,during heavy oil pyrolysis,resins and asphaltenes could increase the E_(a) of saturates and aromatics,while saturates and aromatics could decrease the E_(a) of resins and asphaltenes.展开更多
基金support from National Key Research and Development Program of China(2021YFC2103701)the National Postdoctoral Program of China(GZB20230630)the National Natural Science Foundation of China(22208295).
文摘Understanding the relationship between the chemical composition and pyrolysis performance of endothermic hydrocarbon fuel(EHF) is of great significance for the design and optimization of advanced EHFs. In this work, the effect of deep hydrogenation on the pyrolysis of commercial RP-3 is investigated.Fuels with different hydrogenation degrees were obtained by the partially and completely catalytic hydrogenation and their pyrolysis performances were investigated using an apparatus equipped with an electrically heated tubular reactor. The results show that with the increase of hydrogenation degree, fuel conversion almost remains constant during the pyrolysis process(500-650°C, 4 MPa);however, the heat sink increases slightly, and the anti-coking performance significantly improves, which are highly related to their H/C ratios. Detailed characterisations reveal that the difference of the pyrolysis performance can be ascribed to the content of aromatics and cycloalkanes: the former are prone to initiate secondary reactions to form coking precursors, while the latter could act as the hydrogen donor and release hydrogen, which will terminate the radical propagation reactions and suppress the coke deposition. This work should provide the guidance for upgrading EHFs by modulating the composition of EHFs.
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.
基金supported by the National Natural Science Foundation of China(51876080)the Program for Taishan Scholars of the Shandong Province Government。
文摘Biochar and bio-oil are produced simultaneously in one pyrolysis process,and they inevitably contact and may interact,influencing the composition of bio-oil and modifying the structure of biochar.In this sense,biochar is an inherent catalyst for pyrolysis.In this study,in order to investigate the influence of functionalities and pore structures of biochar on its capability for catalyzing the conversion of homologous volatiles in bio-oil,three char catalysts(600C,800C,and 800AC)produced via pyrolysis of poplar wood at 600 or 800℃or activated at 800℃,were used for catalyzing pyrolysis of homologous poplar wood at 600℃,respectively.The results indicated that the 600C catalyst was more active than 800C and 800AC for catalyzing cracking of volatiles to form more gas(yield increase by 40.2%)and aromatization of volatiles to form more light or heavy phenolics,due to its abundant oxygen-containing functionalities acting as active sites.The developed pores of the 800AC showed no such catalytic effect but could trap some volatiles and allow their further conversion via sufficient aromatization.Nevertheless,the interaction with the volatiles consumed oxygen on 600C(decrease by 50%),enhancing the aromatic degree and increasing thermal stability.The dominance of deposition of carbonaceous material of a very aromatic nature over 800C and 800AC resulted in net weight gain and blocked micropores but formed additional macropores.The in situ diffuse reflectance infrared Fourier transform spectroscopy characterization of the catalytic pyrolysis indicated superior activity of 600C for removal of -OH,while conversion of the intermediates bearing C=O was enhanced over all the char catalysts.
基金the financial support for this work provided by the National Key R&D Program of China‘Technologies and Integrated Application of Magnesite Waste Utilization for High-Valued Chemicals and Materials’(2020YFC1909303)。
文摘This study developed a numerical model to efficiently treat solid waste magnesium nitrate hydrate through multi-step chemical reactions.The model simulates two-phase flow,heat,and mass transfer processes in a pyrolysis furnace to improve the decomposition rate of magnesium nitrate.The performance of multi-nozzle and single-nozzle injection methods was evaluated,and the effects of primary and secondary nozzle flow ratios,velocity ratios,and secondary nozzle inclination angles on the decomposition rate were investigated.Results indicate that multi-nozzle injection has a higher conversion efficiency and decomposition rate than single-nozzle injection,with a 10.3%higher conversion rate under the design parameters.The decomposition rate is primarily dependent on the average residence time of particles,which can be increased by decreasing flow rate and velocity ratios and increasing the inclination angle of secondary nozzles.The optimal parameters are injection flow ratio of 40%,injection velocity ratio of 0.6,and secondary nozzle inclination of 30°,corresponding to a maximum decomposition rate of 99.33%.
基金support and encouragement of the Joint Funds of the National Natural Science Foundation of China(No.U21B2095)the Major Research Project of National Natural Science Foundation of China(No.91834303).
文摘This work investigated the pyrolysis reaction of waste resin in a fluidized bed reactor.It was found that the pyrolysis-generated ash would adhere to the surface of ceramic particles,causing particle agglomeration and defluidization.Adding kaolin could effectively inhibit the particle agglomeration during the fluidized pyrolysis reaction through physical isolation and chemical reaction.On the one hand,kaolin could form a coating layer on the surface of ceramic particles to prevent the adhesion of organic ash generated by the pyrolysis of resin.On the other hand,when a sufficient amount of kaolin(-0.2%(mass))was added,the activated kaolin could fully contact with the Na+ ions generated by the pyrolysis of resin and react to form a high-melting aluminosilicate mineral(nepheline),which could reduce the formation of low-melting-point sodium sulfate and thereby avoid the agglomeration of ceramic particles.
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.
文摘The current energy crisis could be alleviated by enhancing energy generation using the abundant biomass waste resources. Agricultural and forest wastes are the leading organic waste streams that can be transformed into useful alternative energy resources. Pyrolysis is one of the technologies for converting biomass into more valuable products, such as bio-oil, bio-char, and syngas. This work investigated the production of bio-oil through batch pyrolysis technology. A fixed bed pyrolyzer was designed and fabricated for bio-oil production. The major components of the system include a fixed bed reactor, a condenser, and a bio-oil collector. The reactor was heated using a cylindrical biomass external heater. The pyrolysis process was carried out in a reactor at a pressure of 1atm and a varying operating temperature of 150˚C, 250˚C, 350˚C to 450˚C for 120 minutes. The mass of 1kg of coconut fiber was used with particle sizes between 2.36 mm - 4.75 mm. The results show that the higher the temperature, the more volume of bio-oil produced, with the highest yield being 39.2%, at 450˚C with a heating rate of 10˚C/min. The Fourier transformation Infrared (FTIR) Spectroscopy analysis was used to analyze the bio-oil components. The obtained bio-oil has a pH of 2.4, a density of 1019.385 kg/m<sup>3</sup>, and a calorific value of 17.5 MJ/kg. The analysis also showed the presence of high-oxygenated compounds;carboxylic acids, phenols, alcohols, and branched oxygenated hydrocarbons as the main compounds present in the bio-oil. The results inferred that the liquid product could be bestowed as an alternative resource for polycarbonate material production.
基金partially funded by the GTCLC-NEG project,which received funding from the European Union’s Horizon 2020 Research and Innovation Programme under the Marie Sklodowska-Curie Grant Agreement (101018756)the Brisk 2 European project (731101)for funding this project.The project acronym was B2PB-SIN2-1001,and the project title was“Optimization of catalytic pyrolysis of digestate and sewage sludge.”。
文摘Catalytic pyrolysis of digestate to produce aromatic hydrocarbons can be combined with anaerobic fermentation to effectively transform and utilize all biomass components,which can achieve the meaningful purpose of transforming waste into high-value products.This study explored whether catalytic pyrolysis of digestate is feasible to prepare aromatic hydrocarbons by analyzing the thermogravimetric characteristics,pyrolysis characteristics,and catalytic pyrolysis characteristics of digestate.For digestate pyrolysis,an increase in temperature was found to elevate the CO,CH_4,and monocyclic aromatic hydrocarbon(benzene,toluene,and xylene;BTX)content,whereas it decreased the contents of phenols,acids,aldehydes,and other oxygenates.Furthermore,the catalytic pyrolysis process effectively inhibited the acids,phenols,and furans in the liquid,whereas the yield of BTX increased from 25.45%to 45.99%,and the selectivity of xylene was also increased from 10.32%to 28.72%after adding ZSM-5.ZSM-5 also inhibited the production of nitrogenous compounds.
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.
基金financial support from Individual Research Grant (Grant reference No.: A20E7c0109) of the Agency for Science,Technology and Research of Singapore (A*STAR)。
文摘Over the past half-century, plastic consumption has grown rapidly due to its versatility, low cost, and unrivaled functional properties. Among the diff erent implemented strategies for recycling waste plastics, pyrolysis is deemed the most economical option. Currently, the wax obtained from the pyrolysis of waste plastics is mainly used as a feedstock to manufacture chemicals and fuels or added to asphalt for pavement construction, with no other applications of wax being reported. Herein, the thermal pyrolysis of three common waste polyolefin plastics: high-density polyethylene(HDPE), low-density polyethylene(LDPE), and polypropylene(PP), was conducted at 450 ℃. The waste plastics-derived waxes were characterized and studied for a potential new application: phase change materials(PCMs) for thermal energy storage(TES). Gas chromatography–mass spectrometry analysis showed that paraffin makes up most of the composition of HDPE and LDPE waxes, whereas PP wax contains a mixture of naphthene, isoparaffin, olefin, and paraffin. Diff erential scanning calorimetry(DSC) analysis indicated that HDPE and LDPE waxes have a peak melting temperature of 33.8 ℃ and 40.3 ℃, with a relatively high latent heat of 103.2 J/g and 88.3 J/g, respectively, whereas the PP wax was found to have almost negligible latent heat. Fourier transform infrared spectroscopy and DSC results revealed good chemical and thermal stability of HDPE and LDPE waxes after 100 cycles of thermal cycling. Performance evaluation of the waxes was also conducted using a thermal storage pad to understand their thermoregulation characteristics for TES applications.
基金This research was financially supported by the National Key R&D Program of China(grant number 2022YFB3504000)the Contract Projects of China Petroleum&Chemical Corporation(SINOPEC Corp.)(grant number ST22005).
文摘Light olefins,particularly ethylene and propylene,are the most important building blocks for the petrochemical industry,and demand for their production has been increasing.The catalytic pyrolysis process(CPP)and the corresponding catalyst,developed by SINOPEC Research Institute of Petroleum Processing Co.,Ltd.,are designed to maximize the light olefin yield from catalytic cracking of heavy feedstocks.However,owing to the continuing degradation of feedstocks,the original catalyst can no longer maintain its activity.Herein,we describe the rational design of the new catalyst,Epylene,from a new metal-modified hierarchical ZSM-5 zeolite and matrix.Epylene was tested in the CPP unit of Shaanxi Yanchang Coal Yulin Energy and Chemical Company.A test run and base run were conducted to demonstrate the better performance of Epylene compared with the original catalyst.The properties of the feedstocks and the operating conditions in both runs were similar.The light olefin yield was increased from 33.95%to 36.50%and the coke yield was only 9.58%in the test run,which was lower than that in the base run.
基金supported by the National Natural Science Foundation of China (51536002)the Fundamental Research Funds for the Central Universities (2015QNA12)the Open Sharing Fund for the Large-scale Instruments and Equipments of China University of Mining and Technology (CUMT).
文摘The critical issue in developing mature Oxy-Coal Combustion Steam System technology could be the reactivity of deminer-alized coal which,is closely related to its chemical structure.The chemical structures of Liupanshui raw coal(LPS-R)and Liupanshui demineralized coal(LPS-D)were analyzed by FTIR and solid-state 13C-NMR.The pyrolysis experiments were carried out by TG,and the pyrolysis kinetics was analyzed by three iso-conversional methods.FTIR and 13C-NMR results suggested that the carbon structure of LPS coal was not altered greatly,while demineralization promoted the maturity of coal and the condensation degree of the aromatic ring,making the chemical structure of coal more stable.The oxygen-containing functional groups with low bond energy were reduced,and the ratio of aromatic carbon with high bond energy was increased,decreasing the pyrolysis reactivity.DTG curve-fitting results revealed that the thermal weight loss of LPS coal mainly came from the cleavage of aliphatic covalent bonds.By pyrolysis kinetics analysis of LPS-R and LPS-D,the apparent activation energies were 76±4 to 463±5 kJ/mol and 84±2 to 758±12 kJ/mol,respectively,under different conversion rates.The reactivity of the demineralized coal was inhibited to some extent,as the apparent activation energy of pyrolysis for LPS-D increased by acid treatment.
基金funded by the framework of the State Assignment (FWES-2021-0014)for the Institute of Chemistry and Chemical Technology SB RAS using the instruments of the Krasnoyarsk Regional Research Equipment Centre of SB RAS.
文摘The chemical composition,structural and plastometric properties of different-ranked coals from Mongolia deposits were studied.The non-isothermal iso-conversion Ozawa-Flynn-Wall and Friedman model-free methods were used to assess kinetic parameters and to differentiate decomposition steps.Key peculiarities of the pyrolysis kinetics of brown and bituminous coals were revealed and discussed in terms of the composition and plastometric properties.Brown coal was shown to undergo three decomposition steps with ever increasing activation energy as temperature increased because of the decomposition of thermally more and more stable molecular fragments.The pyrolysis of bituminous coals occurred in four steps,the activation energy having extreme mode of temperature dependence.An important new finding was that the temperature range of the second,major pyrolysis step well corresponded to that between the softening and re-solidification temperatures according to Gieseler plastometry.The yield and composition of the pyrolysis products obtained under isothermal conditions were also characterized depending on coal rank and temperature,and the ways for qualified utilizations were offered.
基金financially supported by the National Natural Science Foundation of China(52074201&51706165)China Postdoctoral Science Foundation(2021M703082)。
文摘Silica aerogels have promising applications in thermal insulation,but their flammability and reaction mechanisms have rarely been investigated.The pyrolysis kinetics and thermodynamics of hydrophobic silica aerogels under N_(2) environment were studied.The kinetic and thermodynamic parameters were obtained by three model-free methods.Based on the calculated kinetic parameters,the pyrolysis mechanism of silica aerogels was discussed by the master plots method.The results indicate that the reactions of the whole pyrolysis phase can be characterized by a random nuclear model.In addition,FTIR test results show that the volatile products of silica aerogel pyrolysis are mainly hydrocarbons generated by the decomposition of hydrophobic groups(methyl groups)on the surface.Finally,the effects of pyrolysis on the properties of silica aerogels Finally,the effects of pyrolysis on the properties of silica aerogels were investigated based on the analysis results of SEM,specific surface area,pore size distribution,X-ray diffraction,XPS and infrared spectroscopy.
基金supported by China-Central and Eastern Europe Universities Joint Education Project(2021128).
文摘Soybean soapstock(SS) is one of the main solid wastes produced in the refinery of edible oil processing. In this study, the co-pyrolysis of SS with iron slag(IS) and aluminum scrap(AS) was carried out in a tubular furnace. The gas, liquid and solid products were characterized and the char yield decreased with increasing IS/AS ratio. IS and AS can improve the gas yield, and when the ratio of SS/IS was 1:0.25, the total pyrolysis gas and hydrogen contents were significantly increased. The content of oxygen compounds in pyrolysis oil decreased during co-pyrolysis, while AS promoted the content of polycyclic aromatic hydrocarbons in pyrolysis oil. The co-pyrolysis reaction can be divided into four stages, the mass loss rate reaches the maximum at the third stage(390–575 ℃). The molar ratio of H/C was lower for pyrolysis,indicating good stability of pyrolysis char owing to the high degree of carbonization and aromaticity.The possible co-pyrolysis reaction mechanism was explored.
基金the National Natural Science Foundation of China(51901209).
文摘Cyclotriphosphazene derivatives can effectively improve the flame retardancy and fire safety of epoxy resins(EPs)via their influence on the pyrolysis process.In this work,the effects of hexa(5-methyl-2-pyridinoxyl)cyclotriphosphazene(HMPOP)incorporation on the initial pyrolysis of an EP at 500–3500 K were studied using the ReaxFF method.The pyrolysis fragments,initial reaction pathways,and main products were identified for the EP and EP/HMPOP composites.The activation energies were derived by fitting the weight percentage curves for solid species during the pyrolysis reactions and the obtained values were in good agreement with experimental data.The initial EP pyrolysis reactions included four major decomposition modes,which primarily involved the cleavage of C–O and C–N bonds.The main pyrolysis products were H_(2)O,CO,C_(2)H_(4),and CH_(2)O.HMPOP bonded with the oxygen-containing fragments to form larger molecular fragments and reduced the amounts of C_(0)–C_(4) products,especially that of the harmful gas CH_(2)O.Thus,HMPOP promoted the formation of carbon clusters and reduced the generation of combustible gases,ultimately decreasing the capacity for fire propagation.
基金supported by Program of China National Petroleum Corporation(2020B-20122022zS27)the General Program of National Natural Science Foundation of China(22178385).
文摘When converting C_(5) hydrocarbons to light olefins by catalytic pyrolysis,the generation of low value-added methane will affect the atomic utilization efficiency of C_(5) hydrocarbons.To improve the atomic utilization efficiency,different generation pathways of light olefins and methane in the catalytic pyrolysis of C_(5) hydrocarbons were analyzed,and the effects of reaction conditions and zeolite types were inves-tigated.Results showed that light olefins were mainly formed by breaking the C_(2)-C_(3) bond in the middle position,while methane was formed by breaking the C_(1)-C_(2) bond at the end.Meanwhile,it was discovered that the hydrogen transfer reaction could be reduced by about 90%by selecting MTT zeolite with 1D topology and FER zeolite with 2D topology under high weight hourly space velocity(WHSV)and high temperature operations,thus leading to the improvement of the light olefins selectivity for the catalytic pyrolysis of n-pentane and 1-pentene to 55.12% and 74.60%,respectively.Moreover,the fraction ratio of terminal C_(1)-C_(2) bond cleavage was reduced,which would reduce the selectivity of methane to 6.63%and 1.83%.Therefore,zeolite with low hydrogen transfer activity and catalytic pyrolysis process with high WHsV will be conducive to maximize light olefins and to decrease methane.
文摘The pyrolysis of cyclohexane,methylcyclohexane,and ethylcyclohexane have been studied behind reflected shock waves at pressures of 5 and10 bar and at temperatures of 930-1550 K for 0.05%fuel diluted by Argon.A single-pulse shock tube(SPST)is used to perform the pyrolysis experiments at reaction times varying from 1.65 to 1.74 ms.Major products are obtained and quantified using gas chromatography analysis.A flame ionization detector and a thermal conductivity detector are used for species identification and quantification.Kinetic modeling has been performed using several detailed and lumped chemical kinetic mechanisms.Differences in modeling results among the kinetic models are described.Reaction path analysis and sensitivity analysis are performed to determine the important reactions controlling fuel pyrolysis and their influence on the predicted concentrations of reactant and product species profiles.The present work provides new fundamental knowledge in understating pyrolysis characteristics of cyclohexane compounds and additional data set for detailed kinetic mechanism development.
基金the financial support of the National Natural Science Foundation(22278423,U1862107)Science Foundation of China University of Petroleum,Beijing(2462021QNXZ007).
文摘The pyrolysis behaviors of Qingdao vacuum residue(QD-VR)and its SARA(saturates,aromatics,reins,and asphaltenes)fractions were evaluated by thermo-gravimetric with mass spectrometer(TG-MS).The pyrolysis kinetics were determined by Friedman,one-parallel and four-parallel distributed activation energy model(DAEM),respectively.The results indicated that the pyrolysis behavior of QD-VR was similar to that of aromatics.For saturates,the release of H_(2),CH_(4),CO,and CO_(2) occurred in 80-400℃,while the temperature range for QD-VR and other fractions is 200-800℃.The average activation energy(Ea)via Friedman method was 179.72 kJ/mol and increased with the conversion ratio.One-parallel Gaussian DAEM was more suitable to describe the pyrolysis process of the single SARA fractions,while four-parallel Gaussian DAEM was more suitable to describe the pyrolysis process of heavy oil.Furthermore,comparing the weighted E_(a) from one-parallel(227.64 kJ/mol)and four-parallel Gaussian DAEM(204.63 kJ/mol),the results suggested that during pyrolysis process of heavy oil,there was an interaction between the SARA fractions,which could reduce the E_(a) of heavy oil pyrolysis.Specifically,during heavy oil pyrolysis,resins and asphaltenes could increase the E_(a) of saturates and aromatics,while saturates and aromatics could decrease the E_(a) of resins and asphaltenes.