It is important to understand the effects of demineralization on the reactivity of coal pyrolysis for demineralization coal in OCCSS systems.The molecular dynamics of the pyrolysis of ZD-R and ZD-D was investigated us...It is important to understand the effects of demineralization on the reactivity of coal pyrolysis for demineralization coal in OCCSS systems.The molecular dynamics of the pyrolysis of ZD-R and ZD-D was investigated using the ReaxFF MD method.It is indicated that the pyrolysis reactivity of ZD-D is enhanced.Acid demineralization treatment helps to enhance the cross-linking reaction of light tar C5-14 molecules in the main pyrolysis stage,generating light tar fragments with higher molecular mass.In the polycondensation pyrolysis stage,the acid demineralization treatment promotes the polycondensation reaction at high temperatures.The generation of H2 in ZD-R pyrolysis is primarily attributed to the N-H bond breaking in pyrrole at low temperatures.At high temperatures,it is predominantly associated with the hydrogen abstraction reaction between carboxyl functional groups and the dehydrogenation reaction of hydrogen bond breaking in the aliphatic hydrocarbon structures.H2O is primarily attributed to the reaction of the hydroxyl group on the carboxyl group.CO_(2) is always related to the carboxyl group.CO is mainly related to the reduction reaction of carbonyl group,carboxyl group,and CO_(2).During the initial pyrolysis stage of ZD-D after acid demineralization treatment,the hydrogen abstraction reaction of the carboxyl functional group and the generation of CO molecules by the methoxy group are enhanced.The generation of H2 by the aliphatic structure is enhanced in the main pyrolysis stage.The ring-opening reaction of the phenoxy group to generate CO in the polycondensation pyrolysis stage is also facilitated.展开更多
This paper presents findings of a study on solid wastes conversion into fuels through pyrolysis of plastic materials, presenting an alternative renewable approach for waste management. Investigations were conducted on...This paper presents findings of a study on solid wastes conversion into fuels through pyrolysis of plastic materials, presenting an alternative renewable approach for waste management. Investigations were conducted on conversion of polypropylene (PP), low-density polyethylene (LDPE) and high-density polyethylene (HDPE) under normal and catalyst mediated process conditions. Plastic wastes were collected from various dumpsites in Nairobi and segregated using plastic resin codes to various classes. Samples were cleaned, dried and shredded to 2 mm and fed into a pyrolysis reactor. The pyrolysis process was conducted at between 220˚C and 420˚C. Pyrolysis gases were condensed in a shell and coil condenser and the incondensable gases were stored in gasbags. Liquid fuels were analysed using Gas chromatograph with a mass spectroscopic detector and Fourier Transform Infrared Spectrometry. The results revealed that the most optimal process conditions were a temperature range of 220˚C - 420˚C at a heating rate of 10˚C per minute. Under these conditions, the oil yields were 53.72% for PP, 62.10% for LDPE, and 64.14% for HDPE. As the heating rate increased from 10˚C/min to 20˚C/min, gas yields increased, rising from 28.05% to 31.12% in PP, 14.96% to 30.62% in LDPE, and 18.51% to 29.49% in HDPE. The introduction of Fe2O3 and Al2O3 catalyst significantly enhanced gas production during pyrolysis, increasing yields from 18% to 61% and 47% respectively.展开更多
This study explores,for the first time,the influence of various C1 gases,such as methane(CH_(4)),carbon dioxide(CO_(2)),and biogas(CH4+CO_(2)),on catalytic pyrolysis of plastic waste(polypropylene)to evaluate their po...This study explores,for the first time,the influence of various C1 gases,such as methane(CH_(4)),carbon dioxide(CO_(2)),and biogas(CH4+CO_(2)),on catalytic pyrolysis of plastic waste(polypropylene)to evaluate their potential in producing aromatic hydrocarbons.Also,this study used the 0.5 wt%,1 wt%,3 wt%,and 5 wt%Ga-modified ZSM-5 catalyst and its reduction-oxidation processed catalysts owing to their promising catalytic properties.According to the results,the highest yield(39.5 wt%)of BTEX(benzene,toluene,xylene,and ethylbenzene)was achieved under CH4 over RO-GHZ(1)catalyst among all tested conditions.The reduction-oxidation process not only promotes a significant reduction of the Ga-size but also induces its diffusion inside the pore,compared to GHZ(1).This leads to the formation of highly active GaO^(+)ionic species,balancing the Lewis/Brönsted ratio,thereby accelerating the aromatization reaction.The effect of Ga loading on the RO-GHZ catalyst was also evaluated systematically,which showed a negative impact on the BTEX yield owing to the lowering in the concentration of active GaO+species.A detailed catalyst characterization supports the experimental results well.展开更多
The biomass and coal co-pyrolysis (BCP) technology combines the advantages of both resources, achieving efficient resource complementarity, reducing reliance on coal, and minimizing pollutant emissions. However, this ...The biomass and coal co-pyrolysis (BCP) technology combines the advantages of both resources, achieving efficient resource complementarity, reducing reliance on coal, and minimizing pollutant emissions. However, this process still encounters numerous challenges in attaining optimal economic and environmental performance. Therefore, an ensemble learning (EL) framework is proposed for the BCP process in this study to optimize the synergistic benefits while minimizing negative environmental impacts. Six different ensemble learning models are developed to investigate the impact of input features, such as biomass characteristics, coal characteristics, and pyrolysis conditions on the product profit and CO_(2) emissions of the BCP processes. The Optuna method is further employed to automatically optimize the hyperparameters of BCP process models for enhancing their predictive accuracy and robustness. The results indicate that the categorical boosting (CAB) model of the BCP process has demonstrated exceptional performance in accurately predicting its product profit and CO_(2) emission (R2>0.92) after undergoing five-fold cross-validation. To enhance the interpretability of this preferred model, the Shapley additive explanations and partial dependence plot analyses are conducted to evaluate the impact and importance of biomass characteristics, coal characteristics, and pyrolysis conditions on the product profitability and CO_(2) emissions of the BCP processes. Finally, the preferred model coupled with a reference vector guided evolutionary algorithm is carried to identify the optimal conditions for maximizing the product profit of BCP process products while minimizing CO_(2) emissions. It indicates the optimal BCP process can achieve high product profits (5290.85 CNY·t−1) and low CO_(2) emissions (7.45 kg·t^(−1)).展开更多
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 absence of humic vitrinite complicates the determination of thermal maturity in pre-Devonian sediments.Lower Paleozoic shales contain structured zooclasts,solid bitumen,and vitrinite-like materials,and their refle...The absence of humic vitrinite complicates the determination of thermal maturity in pre-Devonian sediments.Lower Paleozoic shales contain structured zooclasts,solid bitumen,and vitrinite-like materials,and their reflectances have been found to be valid maturity proxies.Yet there remains much controversy as to the degree of evolution of reflectances.The current work aims to investigate the reflectance of dispersed organic matter(DOM),as well as their transformation degree and organic pore development.To this end,this study evaluated an Upper Ordovician zooclasts-bearing shale and a Middle Jurassic coal sample via anhydrous-pyrolysis to compare differences in the maturation pathways between marine-derived DOM and terrigenous vitrinite.These two original samples were cut into small blocks and placed in an identical vacuum stainless vessel simultaneously.The pyrolysis was carried out at isothermal temperatures ranging from 250 to 550℃ for 48 h.The morphologic and reflectance changes of DOM in pyrolysis residues were studied and compared with previous pyrolysis results.Adopting the combined use of optical reflectance and scanning electron microscope(SEM)techniques,the study shows that DOM in the shale components consists of solid bitumen(SB),bituminite,chitinozoans,a few graptolites,vitrinite-like particles(VLP),alginate and liptodetrinite.The reflectance sequence,from high to low,is zooclasts,VLP and SB.Their reflectances gradually increases as the pyrolysis temperature rises,although the rate of growth is slower than that of co-heating coal vitrinite.Notably,zooclasts yield significantly higher reflectance values than those of VLP and SB at each pyrolysis temperature.However,the VLP undergoes two distinct phases in reflectance development,despite gradual morphology changes similar to vitrinite.Based on evidence of the optical texture and organic pore evolution,we argue that a fair amount of VLP in studied Upper Ordovician shale does not consist of graptolite-type fragments.Consequently,the VLPRo serves as a reliable indicator for assessing organic matter maturity in Ordovician shales with a reflectance value of less than 2.0%.This investigation enhances scholarly understandings of marine-derived DOM evolution issues,providing clearer correlations among reflectances of different DOM and reducing uncertainties in thermal maturity determination.展开更多
High density polyethylene(HDPE)pyrolysis and in-line oxidative steam reforming was carried out in a two-step reaction system consisting of a conical spouted bed reactor and a fluidized bed reactor.Continuous plastic p...High density polyethylene(HDPE)pyrolysis and in-line oxidative steam reforming was carried out in a two-step reaction system consisting of a conical spouted bed reactor and a fluidized bed reactor.Continuous plastic pyrolysis was conducted at 550℃ and the volatiles formed were fed in-line to the oxidative steam reforming step(space-time 3.12 gcat min gHDPE−1;ER=0.2 and steam/plastic=3)operating at 700℃.The influence Ni based reforming catalyst support(Al_(2)O_(3),ZrO_(2),SiO_(2))and promoter(CeO_(2),La_(2)O_(3))have on HDPE pyrolysis volatiles conversion and H_(2) production was assessed.The catalysts were prepared by the wet impregnation and they were characterized by means of N_(2) adsorption-desorption,X-ray fluorescence,temperature-programmed reduction and X-ray powder diffraction.A preliminary study on coke deposition and the deterioration of catalysts properties was carried out,by analyzing the tested catalysts through temperature programmed oxidation of coke,transmission electron microscopy,and N_(2) adsorption-desorption.Among the supports tested,ZrO_(2) showed the best performance,attaining conversion and H_(2) production values of 92.2% and 12.8 wt%,respectively.Concerning promoted catalysts,they led to similar conversion values(around 90%),but significant differences were observed in H_(2) production.Thus,higher H_(2) productions were obtained on the Ni/La_(2)O_(3)-Al_(2)O_(3) catalyst(12.1 wt%)than on CeO_(2) promoted catalysts due to La_(2)O_(3) capability for enhancing water adsorption on the catalyst surface.展开更多
Utilizing calcium aluminate(CaAlO)as a catalyst in lignocellulosic biomass pyrolysis offers dual advantages of cost saving and mitigating environmental pollution from industrial waste.This study employs kinetic analys...Utilizing calcium aluminate(CaAlO)as a catalyst in lignocellulosic biomass pyrolysis offers dual advantages of cost saving and mitigating environmental pollution from industrial waste.This study employs kinetic analysis to validate the catalytic effect of CaAlO on biomass pyrolysis.Thermalgravimetric analysis of walnut shell pyrolysis was conducted,incorporating CaAlO,CaO,and Al_(2)O_(3) additives to examine catalytic pyrolysis and gas release characteristics.The results reveal that CaAlO exhibits a catalytic effect similar to that of CaO and Al_(2)O_(3),suggesting its potential as an effective catalyst.Activation energies obtained without additive and with CaAlO,CaO,and Al_(2)O_(3) by Friedman method are 184,178,158,and 176 kJ·mol^(-1),while by Flynn-Wall-Ozawa(FWO)method are 186,179,160,177 kJ·mol^(-1).Finally,distributed activation energy model(DAEM)analysis was performed,and the obtained parameters were successfully coupled into three-dimensional numerical simulation with some simplifications in the DAEM integration to reduce calculation cost,showing its potential applicability in biomass pyrolysis investigation.展开更多
Polystyrene(PS)waste was depolymerized using a low-temperature pyrolysis treatment(LTPT)to increase its caking index.The mechanism of caking index modification was revealed by using Fourier transform infrared spectros...Polystyrene(PS)waste was depolymerized using a low-temperature pyrolysis treatment(LTPT)to increase its caking index.The mechanism of caking index modification was revealed by using Fourier transform infrared spectroscopy,thermogravimetric(TG)analysis,pyrolysis-gas chromatography with mass spectrometric detection,and solid-state^(13)C nuclear magnetic resonance spectroscopy.The crucible coal-blending coking tests were carried out using an industrial coal mixture and the treated-PS with the highest caking index(PS300)or raw PS.Some properties of the resultant cokes were also analyzed.It was demonstrated that the caking index of PS dramatically increased by LTPT;however,exceeding 300℃ did not yield any benefit.The caking index increased due to the formation of the caking components,whose molecules are medium in size,caused by LTPT.Additionally,the coke reactivity index of the coke obtained from the mixture containing PS300 decreased by 5.1%relative to that of the coke made from the mixture with PS and the coke strength after reaction index of the former increased by 7.3% compared with that of the latter,suggesting that the ratio of depolymerized PS used for coal-blending coking could increase relative to that of PS.展开更多
Coal pillars are critical supporting structures between underground coal gasification gasifiers.Its bearing capacity and structural stability are severely threatened by high-temperature environments.To elucidate the h...Coal pillars are critical supporting structures between underground coal gasification gasifiers.Its bearing capacity and structural stability are severely threatened by high-temperature environments.To elucidate the high-temperature deterioration mechanism of coal pillars at multiple scales,coal strength features as a function of temperature were investigated via uniaxial compression and acoustic emission equipment.The pyrolysis reaction process and microstructure evolution were characterized via X-ray diffractometer(XRD),scanning electron microscope(SEM),thermogravimetric(TG),Fourier transform infrared spectroscopy(FTIR),and computed tomography(CT)tests.Experimental results reveal a critical temperature threshold of 500℃for severe degradation of the coal bearing capacity.Specifically,both the strength and elastic modulus exhibit accelerated degradation above this temperature,with maximum reductions of 45.53%and 61.34%,respectively.Above 500℃,coal essentially undergoes a pyrolysis reaction under N_(2)and CO_(2)atmospheres.High temperatures decrease the quantity of O_(2)-based functional groups,growing aromaticity and the degree of graphitization.These changes induce dislocation and slip inside the coal crystal nucleus and then lead to deformation of the coal molecular structural units and strain energy generation.This process results in a great increase in porosity.Consequently,the stress deformation of coal increases,transforming the type of failure from brittle to ductile failure.These findings are expected to provide scientific support for UCG rock strata control.展开更多
Roasting bastnaesite concentrates is a crucial process in extracting rare earths.This study explored an efficient suspension roasting technology and investigated the bastnaesite pyrolysis and cerium(Ce)oxidation.Relev...Roasting bastnaesite concentrates is a crucial process in extracting rare earths.This study explored an efficient suspension roasting technology and investigated the bastnaesite pyrolysis and cerium(Ce)oxidation.Relevant analytical tests were applied to evaluate the phase and surface property variations of bastnaesite,and isothermal kinetic analysis of bastnaesite pyrolysis and Ce oxidation was performed.The results revealed that bastnaesite decomposed rapidly and accompanied by Ce oxidation,and the gas-solid products were identified as CO_(2),Ce_(7)O_(12),La_(2)O_(3),CeF_(3) and LaF_(3),with Ce oxidation restricted by bastnaesite pyrolysis.As roasting time prolonged,cracks and pores appeared on bastnaesite surface;the BET specific surface and pore diameter increased.In later roasting period,the pore diameter continued to increase but the specific surface decreased,assigned to particle fusion agglomeration and pore consolidation.Additionally,the surface C content reduced and Ce(Ⅳ)content increased gradually as roasting progressed.The reaction kinetics all followed Avrami-Erofeev equations,the reaction orders of bastnaesite pyrolysis and Ce oxidation decreased with decreasing reaction temperature.The calculated activation energies at lower temperatures were higher than those calculated at higher temperatures.This study analyzed the bastnaesite reaction mechanism to supply a reference for the application of suspension roasting technology in bastnaesite smelting.展开更多
This paper focuses on the preparation of rare earth oxide products from rare earth chloride solutions during the rare earth extraction and separation processes,as well as the recycling of magnesium chloride solutions....This paper focuses on the preparation of rare earth oxide products from rare earth chloride solutions during the rare earth extraction and separation processes,as well as the recycling of magnesium chloride solutions.It proposes the idea of introducing spray pyrolysis technology into the rare earth extraction and separation processes.This paper briefly describes the development history of chloride spray pyrolysis technology,focusing on the research status and application progress of rare earth chloride solution and magnesium chloride solution spray pyrolysis technology,as well as spray pyrolysis equipment.The paper also analyzes the challenges and technical intricacies associated with applying spray pyrolysis technology to chloride solutions in the rare earth extraction and separation processes.Additionally,it explores future trends and proposes strategies to facilitate the full recycling of acids and bases,streamline the process flow,and enhance the prospects for green and low-carbon rare earth metallurgy.展开更多
To accurately investigate the evolution characteristics and generation mechanism of retained oil,the study analyzed organic-rich lacustrine shale samples from the Paleogene Kongdian Formation in Cangdong Sag,Bohai Bay...To accurately investigate the evolution characteristics and generation mechanism of retained oil,the study analyzed organic-rich lacustrine shale samples from the Paleogene Kongdian Formation in Cangdong Sag,Bohai Bay Basin.This analysis involves Rock-Eval pyrolysis,pyrolysis simulation experiments,Gas Chromatograph Mass Spectrometer(GC-MS),and reactive molecular dynamics simulations(ReaxFF).The results revealed the retained oil primarily consisted of n-alkanes with carbon numbers ranging from C14 to C36.The generation of retained oil occurred through three stages.A slow growth stage of production rate was observed before reaching the peak of oil production in Stage Ⅰ.Stage Ⅱ involved a rapid increase in oil retention,with C12-C17 and C24-C32 serving as the primary components,increasing continuously during the pyrolysis process.The generation process involved the cleavage of weak bonds,including bridging bonds(hydroxyl,oxy,peroxy,imino,amino,and nitro),ether bonds,and acid amides in the first stage(Ro=0.50%-0.75%).The carbon chains in aromatic ring structures with heteroatomic functional groups breaks in the second stage(R_(o)=0.75%-1.20%).In the third stage(R_(o)=1.20%-2.50%),the ring structures underwent ring-opening reactions to synthesize iso-short-chain olefins and radicals,while further breakdown of aliphatic chains occurred.By coupling pyrolysis simu-lation experiments and molecular simulation technology,the evolution characteristics and bond breaking mechanism of retained oil in three stages were revealed,providing a reference for the for-mation and evolution mechanism of retained oil.展开更多
In this paper,the pyrolysis characteristics of waste tire rubber with catalyst addition were experimentally studied.Pyrolysis experimentations of waste tire rubber with either base,acid or Zeolite catalysts were perfo...In this paper,the pyrolysis characteristics of waste tire rubber with catalyst addition were experimentally studied.Pyrolysis experimentations of waste tire rubber with either base,acid or Zeolite catalysts were performed in a Thermal Gravimetric Analyzer,a one-stage test rig and a two-stage test rig respectively.This is followed by analysis into the rates of pyrolysis reactions and the yields and distribution of the three-phase products using thermogravimetric infrared spectroscopy(TG-IR)and gas chromatographymass spectrometry(GC-MS).Results indicated that the transition metal chloride catalysts improved the reaction rate and were overall effective than the solid acid-base catalysts.Benzene and toluene yields were improved by all three catalysts in the primary pyrolysis,and the best performance was achieved at 550℃ and 600℃ with 30%NaOH.With ZSM-5 in the secondary pyrolysis,proportion of high calorific gases components as H2 and CH4 were increased,and the arylation and isomerization reactions were also promoted.The optimum aromatics yield was achieved at 600℃ and 50%ZSM condition.This study would provide a reference for resourceful utilization of waste tires.展开更多
Nickel-rich cathode materials have received widespread attention due to their high energy density.However,the poor rate capability and inferior cycle stability seriously hinder their large-scale application.The tradit...Nickel-rich cathode materials have received widespread attention due to their high energy density.However,the poor rate capability and inferior cycle stability seriously hinder their large-scale application.The traditional co-precipitation method for preparing them has a long process and easily arises agglomeration leading to inhomogeneous element distribution.Here,a novel precursor containing Li element was prepared by ultrafast spray pyrolysis(SP)in 3–5 s.Then the precursor was used to synthesize pristine LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)(NCM90)and 1%Mg modified LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)(NCM90-Mg1).This method gets rid of mixing Li/Mg source and the precursor prepared by common co-precipitation,thus could achieve homogeneous lithiation and Mg2+doping.The cell parameter c is expanded,and the cation disorder is reduced after Mg2+doping.Furthermore,the harmful H2-H3 phase transition in NCM90-Mg1 is also well suppressed.As a result,the obtained NCM90-Mg1 shows better electrochemical performance than NCM90.Within 2.8–4.3 V(25℃),the specific discharge capacity of NCM90-Mg1 at 5 C is as high as 169.1m Ah/g,and an outstanding capacity retention of 70.0%(10.0%higher than NCM90)can be obtained after400 cycles at 0.5 C.At 45℃,a capacity retention of 81.9%after 100 cycles at 1 C is recorded for NCM90-Mg1.Moreover,the NCM90-Mg1 also exhibits superior cycle stability when cycled at high cut-off voltage(4.5 V,25℃),possessing the capacity retention of 79.2%after 200 cycles at 1 C.Therefore,SP can be proposed as a powerful method for the preparation of multi-element materials for next-generation high energy density LIBs.展开更多
The pyrolysis process of Shendong coal(SD)was first studied by combining the characteristics of thermal gravimetric(TG),pyrolysis-gas chromatography/mass spectrometry(Py-GC/MS)and Gray-King assay(GK).The results show ...The pyrolysis process of Shendong coal(SD)was first studied by combining the characteristics of thermal gravimetric(TG),pyrolysis-gas chromatography/mass spectrometry(Py-GC/MS)and Gray-King assay(GK).The results show that the order of coke yields is G-K(76.35%(mass))>TG(73.11%(mass))>Py(70.03%(mass)).G-K coke yield caused by condensation reaction and secondary reaction accounts for 3.08%(mass)and 3.24%(mass),respectively.Compared with slow pyrolysis,fast pyrolysis has stronger fracture ability to coal molecules and can obtain more O-compounds,mono-ring aromatics and aliphatics.Especially,the content of phenolics increases significantly from 15.49%to 35.17%,but the content of multi-ring aromatics decreases from 23.13%to 2.36%.By comparing the compositions of Py primary tar and G-K final tar,it is found that secondary reactions occurred during G-K pyrolysis process include the cleavage of alkane and esters,condensation of mono-ring aromatics with low carbon alkene,ring opening,isomerization of tri-ring aromatics,hydrogenation of aromatics and acids.展开更多
Hazardous waste stream needs to be managed so as not to exceed stock-and rate-limited properties of its recipient ecosystems.The co-pyrolysis of Chinese medicine residue(CMR)and textile dyeing sludge(TDS)and its bio-o...Hazardous waste stream needs to be managed so as not to exceed stock-and rate-limited properties of its recipient ecosystems.The co-pyrolysis of Chinese medicine residue(CMR)and textile dyeing sludge(TDS)and its bio-oil,biochar,and ash quality and quantity were characterized as a function of the immersion of K_(2)CO_(3),atmosphere type,blend ratio,and temperature.Compared to the mono-pyrolysis of TDS,its co-pyrolysis performance with CMR(the comprehensive performance index(CPI))significantly improved by 33.9%in the N_(2)atmosphere and 33.2%in the CO_(2)atmosphere.The impregnation catalyzed the co-pyrolysis at 370℃,reduced its activation energy by 77.3 kJ/mol in the N_(2)atmosphere and 134.6 kJ/mol in the CO_(2)atmosphere,and enriched the degree of coke gasification by 44.25%in the CO_(2)atmosphere.The impregnation increased the decomposition rate of the co-pyrolysis by weakening the bond energy of fatty side chains and bridge bonds,its catalytic and secondary products,and its bio-oil yield by 66.19%.Its bio-oils mainly contained olefins,aromatic structural substances,and alcohols.The immersion of K_(2)CO_(3)improved the aromaticity of the copyrolytic biochars and reduced the contact between K and Si which made it convenient for Mg to react with SiO_(2)to form magnesium-silicate.The co-pyrolytic biochar surfaces mainly included-OH,-CH_(2),C=C,and Si-O-Si.The main phases in the co-pyrolytic ash included Ca_(5)(PO_(4))_(3)(OH),Al_(2)O_(3),and magnesium-silicate.展开更多
In recent years, the effective conversion of organic wastes into valuable products has been a focus and difficulty in sustainable energy and environmental management. Organic wastes come from a wide range of sources, ...In recent years, the effective conversion of organic wastes into valuable products has been a focus and difficulty in sustainable energy and environmental management. Organic wastes come from a wide range of sources, and industrial and agricultural sources are the main sources of organic waste in China, which can be controlled by microwave pyrolysis technology. In microwave pyrolysis treatment, catalysts have been the key material, microwave absorber, and catalyst of the research hotspot in recent years. This paper summarises the typical influencing parameters of microwave pyrolysis (including microwave power, pyrolysis temperature and microwave absorber), and also summarises the various catalysts applied in microwave pyrolysis, and looks forward to the potential application prospect of pyrolysis products, and the future development direction.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
When high-temperature steam is used as a medium to pyrolyze organic-rich shale,water steam not only acts as heat transfer but also participates in the chemical reaction of organic matter pyrolysis,thus affecting the g...When high-temperature steam is used as a medium to pyrolyze organic-rich shale,water steam not only acts as heat transfer but also participates in the chemical reaction of organic matter pyrolysis,thus affecting the generation law and release characteristics of gas products.In this study,based on a long-distance reaction system of organic-rich shale pyrolysis via steam injection,the effects of steam temperature and reaction distance on gas product composition are analyzed in depth and compared with other pyrolysis processes.The advantages of organic-rich shale pyrolysis via steam injection are then evaluated.The volume concentration of hydrogen in the gas product obtained via the steam injection pyrolysis of organic-rich shale is the highest,which is more than 60%.The hydrogen content increases as the reaction distance is extended;however,the rate of increase changes gradually.Increasing the reaction distance from 800 to 4000 mm increases the hydrogen content from 34.91%to 69.68%and from 63.13%to 78.61%when the steam temperature is 500℃ and 555℃,respectively.However,the higher the heat injection temperature,the smaller the reaction distance required to form a high concentration hydrogen pyrolysis environment(hydrogen concentration>60%).When the steam pyrolysis temperature is increased from 500℃ to 555℃,the reaction distance required to form a high concentration of hydrogen is reduced from 3800 to 800 mm.Compared with the direct retorting process,the volume concentration of hydrogen obtained from high-temperature steam pyrolysis of organic-rich shale is 8.82 and 10.72 times that of the commonly used Fushun and Kivite furnaces,respectively.The pyrolysis of organic-rich shale via steam injection is a pyrolysis process in a hydrogen-rich environment.展开更多
文摘It is important to understand the effects of demineralization on the reactivity of coal pyrolysis for demineralization coal in OCCSS systems.The molecular dynamics of the pyrolysis of ZD-R and ZD-D was investigated using the ReaxFF MD method.It is indicated that the pyrolysis reactivity of ZD-D is enhanced.Acid demineralization treatment helps to enhance the cross-linking reaction of light tar C5-14 molecules in the main pyrolysis stage,generating light tar fragments with higher molecular mass.In the polycondensation pyrolysis stage,the acid demineralization treatment promotes the polycondensation reaction at high temperatures.The generation of H2 in ZD-R pyrolysis is primarily attributed to the N-H bond breaking in pyrrole at low temperatures.At high temperatures,it is predominantly associated with the hydrogen abstraction reaction between carboxyl functional groups and the dehydrogenation reaction of hydrogen bond breaking in the aliphatic hydrocarbon structures.H2O is primarily attributed to the reaction of the hydroxyl group on the carboxyl group.CO_(2) is always related to the carboxyl group.CO is mainly related to the reduction reaction of carbonyl group,carboxyl group,and CO_(2).During the initial pyrolysis stage of ZD-D after acid demineralization treatment,the hydrogen abstraction reaction of the carboxyl functional group and the generation of CO molecules by the methoxy group are enhanced.The generation of H2 by the aliphatic structure is enhanced in the main pyrolysis stage.The ring-opening reaction of the phenoxy group to generate CO in the polycondensation pyrolysis stage is also facilitated.
文摘This paper presents findings of a study on solid wastes conversion into fuels through pyrolysis of plastic materials, presenting an alternative renewable approach for waste management. Investigations were conducted on conversion of polypropylene (PP), low-density polyethylene (LDPE) and high-density polyethylene (HDPE) under normal and catalyst mediated process conditions. Plastic wastes were collected from various dumpsites in Nairobi and segregated using plastic resin codes to various classes. Samples were cleaned, dried and shredded to 2 mm and fed into a pyrolysis reactor. The pyrolysis process was conducted at between 220˚C and 420˚C. Pyrolysis gases were condensed in a shell and coil condenser and the incondensable gases were stored in gasbags. Liquid fuels were analysed using Gas chromatograph with a mass spectroscopic detector and Fourier Transform Infrared Spectrometry. The results revealed that the most optimal process conditions were a temperature range of 220˚C - 420˚C at a heating rate of 10˚C per minute. Under these conditions, the oil yields were 53.72% for PP, 62.10% for LDPE, and 64.14% for HDPE. As the heating rate increased from 10˚C/min to 20˚C/min, gas yields increased, rising from 28.05% to 31.12% in PP, 14.96% to 30.62% in LDPE, and 18.51% to 29.49% in HDPE. The introduction of Fe2O3 and Al2O3 catalyst significantly enhanced gas production during pyrolysis, increasing yields from 18% to 61% and 47% respectively.
文摘This study explores,for the first time,the influence of various C1 gases,such as methane(CH_(4)),carbon dioxide(CO_(2)),and biogas(CH4+CO_(2)),on catalytic pyrolysis of plastic waste(polypropylene)to evaluate their potential in producing aromatic hydrocarbons.Also,this study used the 0.5 wt%,1 wt%,3 wt%,and 5 wt%Ga-modified ZSM-5 catalyst and its reduction-oxidation processed catalysts owing to their promising catalytic properties.According to the results,the highest yield(39.5 wt%)of BTEX(benzene,toluene,xylene,and ethylbenzene)was achieved under CH4 over RO-GHZ(1)catalyst among all tested conditions.The reduction-oxidation process not only promotes a significant reduction of the Ga-size but also induces its diffusion inside the pore,compared to GHZ(1).This leads to the formation of highly active GaO^(+)ionic species,balancing the Lewis/Brönsted ratio,thereby accelerating the aromatization reaction.The effect of Ga loading on the RO-GHZ catalyst was also evaluated systematically,which showed a negative impact on the BTEX yield owing to the lowering in the concentration of active GaO+species.A detailed catalyst characterization supports the experimental results well.
基金support from the National Natural Science Foundation of China(22108052).
文摘The biomass and coal co-pyrolysis (BCP) technology combines the advantages of both resources, achieving efficient resource complementarity, reducing reliance on coal, and minimizing pollutant emissions. However, this process still encounters numerous challenges in attaining optimal economic and environmental performance. Therefore, an ensemble learning (EL) framework is proposed for the BCP process in this study to optimize the synergistic benefits while minimizing negative environmental impacts. Six different ensemble learning models are developed to investigate the impact of input features, such as biomass characteristics, coal characteristics, and pyrolysis conditions on the product profit and CO_(2) emissions of the BCP processes. The Optuna method is further employed to automatically optimize the hyperparameters of BCP process models for enhancing their predictive accuracy and robustness. The results indicate that the categorical boosting (CAB) model of the BCP process has demonstrated exceptional performance in accurately predicting its product profit and CO_(2) emission (R2>0.92) after undergoing five-fold cross-validation. To enhance the interpretability of this preferred model, the Shapley additive explanations and partial dependence plot analyses are conducted to evaluate the impact and importance of biomass characteristics, coal characteristics, and pyrolysis conditions on the product profitability and CO_(2) emissions of the BCP processes. Finally, the preferred model coupled with a reference vector guided evolutionary algorithm is carried to identify the optimal conditions for maximizing the product profit of BCP process products while minimizing CO_(2) emissions. It indicates the optimal BCP process can achieve high product profits (5290.85 CNY·t−1) and low CO_(2) emissions (7.45 kg·t^(−1)).
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supported by National Natural Science Foundation of China(Nos.42202172,U24B6001,41830424)the Fundamental Research Funds for the Central Universities,CHD(300102274202).
文摘The absence of humic vitrinite complicates the determination of thermal maturity in pre-Devonian sediments.Lower Paleozoic shales contain structured zooclasts,solid bitumen,and vitrinite-like materials,and their reflectances have been found to be valid maturity proxies.Yet there remains much controversy as to the degree of evolution of reflectances.The current work aims to investigate the reflectance of dispersed organic matter(DOM),as well as their transformation degree and organic pore development.To this end,this study evaluated an Upper Ordovician zooclasts-bearing shale and a Middle Jurassic coal sample via anhydrous-pyrolysis to compare differences in the maturation pathways between marine-derived DOM and terrigenous vitrinite.These two original samples were cut into small blocks and placed in an identical vacuum stainless vessel simultaneously.The pyrolysis was carried out at isothermal temperatures ranging from 250 to 550℃ for 48 h.The morphologic and reflectance changes of DOM in pyrolysis residues were studied and compared with previous pyrolysis results.Adopting the combined use of optical reflectance and scanning electron microscope(SEM)techniques,the study shows that DOM in the shale components consists of solid bitumen(SB),bituminite,chitinozoans,a few graptolites,vitrinite-like particles(VLP),alginate and liptodetrinite.The reflectance sequence,from high to low,is zooclasts,VLP and SB.Their reflectances gradually increases as the pyrolysis temperature rises,although the rate of growth is slower than that of co-heating coal vitrinite.Notably,zooclasts yield significantly higher reflectance values than those of VLP and SB at each pyrolysis temperature.However,the VLP undergoes two distinct phases in reflectance development,despite gradual morphology changes similar to vitrinite.Based on evidence of the optical texture and organic pore evolution,we argue that a fair amount of VLP in studied Upper Ordovician shale does not consist of graptolite-type fragments.Consequently,the VLPRo serves as a reliable indicator for assessing organic matter maturity in Ordovician shales with a reflectance value of less than 2.0%.This investigation enhances scholarly understandings of marine-derived DOM evolution issues,providing clearer correlations among reflectances of different DOM and reducing uncertainties in thermal maturity determination.
文摘High density polyethylene(HDPE)pyrolysis and in-line oxidative steam reforming was carried out in a two-step reaction system consisting of a conical spouted bed reactor and a fluidized bed reactor.Continuous plastic pyrolysis was conducted at 550℃ and the volatiles formed were fed in-line to the oxidative steam reforming step(space-time 3.12 gcat min gHDPE−1;ER=0.2 and steam/plastic=3)operating at 700℃.The influence Ni based reforming catalyst support(Al_(2)O_(3),ZrO_(2),SiO_(2))and promoter(CeO_(2),La_(2)O_(3))have on HDPE pyrolysis volatiles conversion and H_(2) production was assessed.The catalysts were prepared by the wet impregnation and they were characterized by means of N_(2) adsorption-desorption,X-ray fluorescence,temperature-programmed reduction and X-ray powder diffraction.A preliminary study on coke deposition and the deterioration of catalysts properties was carried out,by analyzing the tested catalysts through temperature programmed oxidation of coke,transmission electron microscopy,and N_(2) adsorption-desorption.Among the supports tested,ZrO_(2) showed the best performance,attaining conversion and H_(2) production values of 92.2% and 12.8 wt%,respectively.Concerning promoted catalysts,they led to similar conversion values(around 90%),but significant differences were observed in H_(2) production.Thus,higher H_(2) productions were obtained on the Ni/La_(2)O_(3)-Al_(2)O_(3) catalyst(12.1 wt%)than on CeO_(2) promoted catalysts due to La_(2)O_(3) capability for enhancing water adsorption on the catalyst surface.
基金the financial support of the National Natural Science Foundation of China(22278432)National Key Research&Development Program of China(2022YFB3805602)Science Foundation of China University of Petroleum-Beijing(2462021BJRC001,2462021QNXZ007)。
文摘Utilizing calcium aluminate(CaAlO)as a catalyst in lignocellulosic biomass pyrolysis offers dual advantages of cost saving and mitigating environmental pollution from industrial waste.This study employs kinetic analysis to validate the catalytic effect of CaAlO on biomass pyrolysis.Thermalgravimetric analysis of walnut shell pyrolysis was conducted,incorporating CaAlO,CaO,and Al_(2)O_(3) additives to examine catalytic pyrolysis and gas release characteristics.The results reveal that CaAlO exhibits a catalytic effect similar to that of CaO and Al_(2)O_(3),suggesting its potential as an effective catalyst.Activation energies obtained without additive and with CaAlO,CaO,and Al_(2)O_(3) by Friedman method are 184,178,158,and 176 kJ·mol^(-1),while by Flynn-Wall-Ozawa(FWO)method are 186,179,160,177 kJ·mol^(-1).Finally,distributed activation energy model(DAEM)analysis was performed,and the obtained parameters were successfully coupled into three-dimensional numerical simulation with some simplifications in the DAEM integration to reduce calculation cost,showing its potential applicability in biomass pyrolysis investigation.
基金supported by the National Natural Science Foundation of China(22308006 and 22278001)the Natural Science Foundation of Anhui Provincial Education Department(KJ2021A0407).
文摘Polystyrene(PS)waste was depolymerized using a low-temperature pyrolysis treatment(LTPT)to increase its caking index.The mechanism of caking index modification was revealed by using Fourier transform infrared spectroscopy,thermogravimetric(TG)analysis,pyrolysis-gas chromatography with mass spectrometric detection,and solid-state^(13)C nuclear magnetic resonance spectroscopy.The crucible coal-blending coking tests were carried out using an industrial coal mixture and the treated-PS with the highest caking index(PS300)or raw PS.Some properties of the resultant cokes were also analyzed.It was demonstrated that the caking index of PS dramatically increased by LTPT;however,exceeding 300℃ did not yield any benefit.The caking index increased due to the formation of the caking components,whose molecules are medium in size,caused by LTPT.Additionally,the coke reactivity index of the coke obtained from the mixture containing PS300 decreased by 5.1%relative to that of the coke made from the mixture with PS and the coke strength after reaction index of the former increased by 7.3% compared with that of the latter,suggesting that the ratio of depolymerized PS used for coal-blending coking could increase relative to that of PS.
基金supported by Young Scholar Program(Category A Continuation Funding)of National Natural Science Foundation of China(No.52525401)General Program of National Natural Science Foundation of China(No.52174125)+4 种基金Outstanding Youth Cultivation Project in Shanxi Province(No.202103021222008)Major Program of National Natural Science Foundation of China(No.52334005)New Cornerstone Science Foundation through the XPLORER PRIZEShanxi-Zheda Institute of Advanced Materials and Chemical Engineering(No.2022SX-TD010)Shanxi Science and Technology Major Project(No.20201102004).
文摘Coal pillars are critical supporting structures between underground coal gasification gasifiers.Its bearing capacity and structural stability are severely threatened by high-temperature environments.To elucidate the high-temperature deterioration mechanism of coal pillars at multiple scales,coal strength features as a function of temperature were investigated via uniaxial compression and acoustic emission equipment.The pyrolysis reaction process and microstructure evolution were characterized via X-ray diffractometer(XRD),scanning electron microscope(SEM),thermogravimetric(TG),Fourier transform infrared spectroscopy(FTIR),and computed tomography(CT)tests.Experimental results reveal a critical temperature threshold of 500℃for severe degradation of the coal bearing capacity.Specifically,both the strength and elastic modulus exhibit accelerated degradation above this temperature,with maximum reductions of 45.53%and 61.34%,respectively.Above 500℃,coal essentially undergoes a pyrolysis reaction under N_(2)and CO_(2)atmospheres.High temperatures decrease the quantity of O_(2)-based functional groups,growing aromaticity and the degree of graphitization.These changes induce dislocation and slip inside the coal crystal nucleus and then lead to deformation of the coal molecular structural units and strain energy generation.This process results in a great increase in porosity.Consequently,the stress deformation of coal increases,transforming the type of failure from brittle to ductile failure.These findings are expected to provide scientific support for UCG rock strata control.
基金Projects(2022YFC2905800,2021YFC2901000)supported by the National Key R&D Program of ChinaProject(52174242)supported by the National Science and Technology of ChinaProject(52130406)supported by the National Science and Technology Major Project of China。
文摘Roasting bastnaesite concentrates is a crucial process in extracting rare earths.This study explored an efficient suspension roasting technology and investigated the bastnaesite pyrolysis and cerium(Ce)oxidation.Relevant analytical tests were applied to evaluate the phase and surface property variations of bastnaesite,and isothermal kinetic analysis of bastnaesite pyrolysis and Ce oxidation was performed.The results revealed that bastnaesite decomposed rapidly and accompanied by Ce oxidation,and the gas-solid products were identified as CO_(2),Ce_(7)O_(12),La_(2)O_(3),CeF_(3) and LaF_(3),with Ce oxidation restricted by bastnaesite pyrolysis.As roasting time prolonged,cracks and pores appeared on bastnaesite surface;the BET specific surface and pore diameter increased.In later roasting period,the pore diameter continued to increase but the specific surface decreased,assigned to particle fusion agglomeration and pore consolidation.Additionally,the surface C content reduced and Ce(Ⅳ)content increased gradually as roasting progressed.The reaction kinetics all followed Avrami-Erofeev equations,the reaction orders of bastnaesite pyrolysis and Ce oxidation decreased with decreasing reaction temperature.The calculated activation energies at lower temperatures were higher than those calculated at higher temperatures.This study analyzed the bastnaesite reaction mechanism to supply a reference for the application of suspension roasting technology in bastnaesite smelting.
基金supported by the National Key Research and Development Program of China(2022YFB3504501)the National Natural Science Foundation of China(52274355)。
文摘This paper focuses on the preparation of rare earth oxide products from rare earth chloride solutions during the rare earth extraction and separation processes,as well as the recycling of magnesium chloride solutions.It proposes the idea of introducing spray pyrolysis technology into the rare earth extraction and separation processes.This paper briefly describes the development history of chloride spray pyrolysis technology,focusing on the research status and application progress of rare earth chloride solution and magnesium chloride solution spray pyrolysis technology,as well as spray pyrolysis equipment.The paper also analyzes the challenges and technical intricacies associated with applying spray pyrolysis technology to chloride solutions in the rare earth extraction and separation processes.Additionally,it explores future trends and proposes strategies to facilitate the full recycling of acids and bases,streamline the process flow,and enhance the prospects for green and low-carbon rare earth metallurgy.
基金financially supported by the National Natural Science Foundation of China (Grant No. 42072150)
文摘To accurately investigate the evolution characteristics and generation mechanism of retained oil,the study analyzed organic-rich lacustrine shale samples from the Paleogene Kongdian Formation in Cangdong Sag,Bohai Bay Basin.This analysis involves Rock-Eval pyrolysis,pyrolysis simulation experiments,Gas Chromatograph Mass Spectrometer(GC-MS),and reactive molecular dynamics simulations(ReaxFF).The results revealed the retained oil primarily consisted of n-alkanes with carbon numbers ranging from C14 to C36.The generation of retained oil occurred through three stages.A slow growth stage of production rate was observed before reaching the peak of oil production in Stage Ⅰ.Stage Ⅱ involved a rapid increase in oil retention,with C12-C17 and C24-C32 serving as the primary components,increasing continuously during the pyrolysis process.The generation process involved the cleavage of weak bonds,including bridging bonds(hydroxyl,oxy,peroxy,imino,amino,and nitro),ether bonds,and acid amides in the first stage(Ro=0.50%-0.75%).The carbon chains in aromatic ring structures with heteroatomic functional groups breaks in the second stage(R_(o)=0.75%-1.20%).In the third stage(R_(o)=1.20%-2.50%),the ring structures underwent ring-opening reactions to synthesize iso-short-chain olefins and radicals,while further breakdown of aliphatic chains occurred.By coupling pyrolysis simu-lation experiments and molecular simulation technology,the evolution characteristics and bond breaking mechanism of retained oil in three stages were revealed,providing a reference for the for-mation and evolution mechanism of retained oil.
基金the Chongqing Municipal Education Commission Research Project(KJZD-K202401502)Chongqing Municipal Science&Technology Commission Research Project(CSTB2022NSCQ-LZX0071)to the research work.
文摘In this paper,the pyrolysis characteristics of waste tire rubber with catalyst addition were experimentally studied.Pyrolysis experimentations of waste tire rubber with either base,acid or Zeolite catalysts were performed in a Thermal Gravimetric Analyzer,a one-stage test rig and a two-stage test rig respectively.This is followed by analysis into the rates of pyrolysis reactions and the yields and distribution of the three-phase products using thermogravimetric infrared spectroscopy(TG-IR)and gas chromatographymass spectrometry(GC-MS).Results indicated that the transition metal chloride catalysts improved the reaction rate and were overall effective than the solid acid-base catalysts.Benzene and toluene yields were improved by all three catalysts in the primary pyrolysis,and the best performance was achieved at 550℃ and 600℃ with 30%NaOH.With ZSM-5 in the secondary pyrolysis,proportion of high calorific gases components as H2 and CH4 were increased,and the arylation and isomerization reactions were also promoted.The optimum aromatics yield was achieved at 600℃ and 50%ZSM condition.This study would provide a reference for resourceful utilization of waste tires.
基金supported by the National Natural Science Foundation of China(No.52122407)the Science and Technology Innovation Program of Hunan Province(No.2022RC3048)。
文摘Nickel-rich cathode materials have received widespread attention due to their high energy density.However,the poor rate capability and inferior cycle stability seriously hinder their large-scale application.The traditional co-precipitation method for preparing them has a long process and easily arises agglomeration leading to inhomogeneous element distribution.Here,a novel precursor containing Li element was prepared by ultrafast spray pyrolysis(SP)in 3–5 s.Then the precursor was used to synthesize pristine LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)(NCM90)and 1%Mg modified LiNi_(0.9)Co_(0.05)Mn_(0.05)O_(2)(NCM90-Mg1).This method gets rid of mixing Li/Mg source and the precursor prepared by common co-precipitation,thus could achieve homogeneous lithiation and Mg2+doping.The cell parameter c is expanded,and the cation disorder is reduced after Mg2+doping.Furthermore,the harmful H2-H3 phase transition in NCM90-Mg1 is also well suppressed.As a result,the obtained NCM90-Mg1 shows better electrochemical performance than NCM90.Within 2.8–4.3 V(25℃),the specific discharge capacity of NCM90-Mg1 at 5 C is as high as 169.1m Ah/g,and an outstanding capacity retention of 70.0%(10.0%higher than NCM90)can be obtained after400 cycles at 0.5 C.At 45℃,a capacity retention of 81.9%after 100 cycles at 1 C is recorded for NCM90-Mg1.Moreover,the NCM90-Mg1 also exhibits superior cycle stability when cycled at high cut-off voltage(4.5 V,25℃),possessing the capacity retention of 79.2%after 200 cycles at 1 C.Therefore,SP can be proposed as a powerful method for the preparation of multi-element materials for next-generation high energy density LIBs.
基金financed by the Department of Education of Gansu Province:Young Doctor Fund Project(2022QB-029)the Fundamental Research Funds for the Central Universities(31920240059,3192024125-06)+1 种基金the Scientific Research Project of Introducing Talents of Northwest Minzu University(xbmuyjrc202215)the National Natural Science Foundation of China(22178289).
文摘The pyrolysis process of Shendong coal(SD)was first studied by combining the characteristics of thermal gravimetric(TG),pyrolysis-gas chromatography/mass spectrometry(Py-GC/MS)and Gray-King assay(GK).The results show that the order of coke yields is G-K(76.35%(mass))>TG(73.11%(mass))>Py(70.03%(mass)).G-K coke yield caused by condensation reaction and secondary reaction accounts for 3.08%(mass)and 3.24%(mass),respectively.Compared with slow pyrolysis,fast pyrolysis has stronger fracture ability to coal molecules and can obtain more O-compounds,mono-ring aromatics and aliphatics.Especially,the content of phenolics increases significantly from 15.49%to 35.17%,but the content of multi-ring aromatics decreases from 23.13%to 2.36%.By comparing the compositions of Py primary tar and G-K final tar,it is found that secondary reactions occurred during G-K pyrolysis process include the cleavage of alkane and esters,condensation of mono-ring aromatics with low carbon alkene,ring opening,isomerization of tri-ring aromatics,hydrogenation of aromatics and acids.
基金National Natural Science Foundation of China (Nos.51978175,42177196,and 22006015)the Scientific and Technological Planning Project of Guangzhou,China (No.202103000004)+2 种基金the Guangdong Province Science and Technology Planning Project,China (No.2022A0505050076)the Dongguan Science and Technology of Social Development Program (No.20211800904662)the Dongguan Sci-tech Commissioner Program (No.20221800500282)。
文摘Hazardous waste stream needs to be managed so as not to exceed stock-and rate-limited properties of its recipient ecosystems.The co-pyrolysis of Chinese medicine residue(CMR)and textile dyeing sludge(TDS)and its bio-oil,biochar,and ash quality and quantity were characterized as a function of the immersion of K_(2)CO_(3),atmosphere type,blend ratio,and temperature.Compared to the mono-pyrolysis of TDS,its co-pyrolysis performance with CMR(the comprehensive performance index(CPI))significantly improved by 33.9%in the N_(2)atmosphere and 33.2%in the CO_(2)atmosphere.The impregnation catalyzed the co-pyrolysis at 370℃,reduced its activation energy by 77.3 kJ/mol in the N_(2)atmosphere and 134.6 kJ/mol in the CO_(2)atmosphere,and enriched the degree of coke gasification by 44.25%in the CO_(2)atmosphere.The impregnation increased the decomposition rate of the co-pyrolysis by weakening the bond energy of fatty side chains and bridge bonds,its catalytic and secondary products,and its bio-oil yield by 66.19%.Its bio-oils mainly contained olefins,aromatic structural substances,and alcohols.The immersion of K_(2)CO_(3)improved the aromaticity of the copyrolytic biochars and reduced the contact between K and Si which made it convenient for Mg to react with SiO_(2)to form magnesium-silicate.The co-pyrolytic biochar surfaces mainly included-OH,-CH_(2),C=C,and Si-O-Si.The main phases in the co-pyrolytic ash included Ca_(5)(PO_(4))_(3)(OH),Al_(2)O_(3),and magnesium-silicate.
文摘In recent years, the effective conversion of organic wastes into valuable products has been a focus and difficulty in sustainable energy and environmental management. Organic wastes come from a wide range of sources, and industrial and agricultural sources are the main sources of organic waste in China, which can be controlled by microwave pyrolysis technology. In microwave pyrolysis treatment, catalysts have been the key material, microwave absorber, and catalyst of the research hotspot in recent years. This paper summarises the typical influencing parameters of microwave pyrolysis (including microwave power, pyrolysis temperature and microwave absorber), and also summarises the various catalysts applied in microwave pyrolysis, and looks forward to the potential application prospect of pyrolysis products, and the future development direction.
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Basic research program of Shanxi Province(20210302124136 and 20210302123177)National Key R&D Program of China(2019YFA0705501)+1 种基金Key R&D and promotion projects in Henan Province(212102310010)National Natural Science Foundation of China(52104144,U23B2088).
文摘When high-temperature steam is used as a medium to pyrolyze organic-rich shale,water steam not only acts as heat transfer but also participates in the chemical reaction of organic matter pyrolysis,thus affecting the generation law and release characteristics of gas products.In this study,based on a long-distance reaction system of organic-rich shale pyrolysis via steam injection,the effects of steam temperature and reaction distance on gas product composition are analyzed in depth and compared with other pyrolysis processes.The advantages of organic-rich shale pyrolysis via steam injection are then evaluated.The volume concentration of hydrogen in the gas product obtained via the steam injection pyrolysis of organic-rich shale is the highest,which is more than 60%.The hydrogen content increases as the reaction distance is extended;however,the rate of increase changes gradually.Increasing the reaction distance from 800 to 4000 mm increases the hydrogen content from 34.91%to 69.68%and from 63.13%to 78.61%when the steam temperature is 500℃ and 555℃,respectively.However,the higher the heat injection temperature,the smaller the reaction distance required to form a high concentration hydrogen pyrolysis environment(hydrogen concentration>60%).When the steam pyrolysis temperature is increased from 500℃ to 555℃,the reaction distance required to form a high concentration of hydrogen is reduced from 3800 to 800 mm.Compared with the direct retorting process,the volume concentration of hydrogen obtained from high-temperature steam pyrolysis of organic-rich shale is 8.82 and 10.72 times that of the commonly used Fushun and Kivite furnaces,respectively.The pyrolysis of organic-rich shale via steam injection is a pyrolysis process in a hydrogen-rich environment.
