Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting t...Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting two greenhouse gases(methane and carbon dioxide)into syngas and its promising industrial applications.Nickel(Ni)-based catalysts,with high catalytic activity,low cost,and abundant resources,are considered ideal candidates for industrial applications.In this article,three reaction kinetic models were briefly introduced,namely the Power-Law(PL)model,the Eley-Rideal(ER)model,and the Langmuir-Hinshelwood-Hougen-Watson(LHHW)model.Based on the LHHW model,the reaction kinetics and mechanisms of different catalytic systems were systematically discussed,including the properties of supports,the doping of noble metals and transition metals,the role of promoters,and the influence of the geometric and electronic structures of Ni on the reaction mechanism.Furthermore,the kinetics of carbon deposition and elimination on various catalysts were analyzed.Based on the reaction rate expressions for carbon elimination,the reasons for the high activity of transition metal iron(Fe)-doped catalysts and core-shell structured catalysts in carbon elimination were explained.Based on the detailed collation and comparative analysis of the reaction mechanisms and kinetic characteristics across diverse Ni-based catalytic systems,a theoretical guidance for the designing of high-performance catalysts was provided in this work.展开更多
Selective laser melting(SLM)is a cost-effective 3 D metal additive manufacturing(AM)process.However,AM 316 L stainless steel(SS)has different surface and microstructure properties as compared to conventional ones.Bori...Selective laser melting(SLM)is a cost-effective 3 D metal additive manufacturing(AM)process.However,AM 316 L stainless steel(SS)has different surface and microstructure properties as compared to conventional ones.Boriding process is one of the ways to modify and increase the surface properties.The aim of this study is to predict and understand the growth kinetic of iron boride layers on AM 316 L SS.In this study,the growth kinetic mechanism was evaluated for AM 316 L SS.Pack boriding was applied at 850,900 and 950℃,each for 2,4 and 6 h.The thickness of the boride layers ranged from(1.8±0.3)μm to(27.7±2.2)μm.A diffusion model based on error function solutions in Fick’s second law was proposed to quantitatively predict and elucidate the growth rate of FeB and Fe_(2)B phase layers.The activation energy(Q)values for boron diffusion in FeB layer,Fe_(2)B layer,and dual FeB+Fe_(2)B layer were found to be 256.56,161.61 and 209.014 kJ/mol,respectively,which were higher than the conventional 316 L SS.The findings might provide and open new directions and approaches for applications of additively manufactured steels.展开更多
Hydrogen-enriched ironmaking presents a promising approach to mitigate coke consumption and carbon emission in blast furnace(BF)operations.This work investigated the relationship between the structural features of cok...Hydrogen-enriched ironmaking presents a promising approach to mitigate coke consumption and carbon emission in blast furnace(BF)operations.This work investigated the relationship between the structural features of cokes and their reactivity towards solution loss(SL),especially under hydrogen-enriched atmospheres.Six cokes were characterized,and their SL behaviors were examined under varying atmospheres to elucidate the effects of hydrogen enrichment.The results indicate that an increase in fixed carbon content leads to a decrease in the coke reactivity index(CRI)and an increase in coke strength after reaction(CSR),in the CO_(2) atmosphere,the CSR of coke increases from 35.76%−62.83%,while in the 90CO_(2)/10H_(2) atmosphere,the CSR of coke increases from 65.67%−84.09%.There is a good linear relationship between CRI and microcrystalline structure parameters of coke.Cokes with larger crystalline size,lower amorphous content,and smaller optical texture index(OTI)values show enhanced resistance to degradation and maintain structural integrity in BF.Kinetic analysis performed with the shifted-modified-random pore model(S-MRPM)reveals that alterations in pore structure and intrinsic mineral composition significantly influence the reaction rate.The introduction of a small amount of water vapor raises SL rates,whereas a minor addition of hydrogen(<10%)decelerates SL due to its incomplete conversion to water vapor and the reduced partial pressure of the gasifying agent.Thermodynamic calculations also indicate that the introduced hydrogen does not convert into the same fraction of water vapor.The shift from chemical reaction control to gas diffusion control as the rate-determining step with rising temperatures during SL process was confirmed,and the introduction of hydrogen does not notably alter SL behavior.This result demonstrated that introducing a small amount of hydrogen(<10%)can mitigate SL rates,thereby enhancing coke strength and reducing coke consumption and carbon emissions.展开更多
In response to the fact that the presence of manganese dithionate(MnS_(2)O_(6))leads to a series of adverse impacts,especially lower purity of manganese sulfate(MnSO_(4))and disruption of its recovery,advanced oxidati...In response to the fact that the presence of manganese dithionate(MnS_(2)O_(6))leads to a series of adverse impacts,especially lower purity of manganese sulfate(MnSO_(4))and disruption of its recovery,advanced oxidation methods such as ozonation system are used to manage MnS_(2)O_(6)in the leaching solution,replacing conventional methods.To ascertain the conversion rate and kinetics of MnS_(2)O_(6)during the ozonation process,we explored the factors influencing its removal rate,including ozone dosage,manganese dithionate concentration,sulfuric acid concentration,and reaction temperature.Batch experiments were conducted to determine the reaction rate constant of ozone(k)and activation energy(Ea)obtained from intermittent experimental data fitting,revealing a least-squares exponential conversion relationship between k and the MnS_(2)O_(6)removal amount,wherein an increase in the aforementioned factors led to an enhanced MnS_(2)O_(6)conversion rate,exceeding 99.3%.The formation mechanism of the ozone products proposed during the experiment was summarized and proposed as follows:1)Mn^(2+)was directly oxidized to MnO_(2),and 2)SO_(4)2−was obtained by the catalytic oxidation of S_(2)O_(6)^(2−)with HO•from O3 decomposition.According to the kinetics analysis,the pre-exponential factor and total activation energy of the ozonation kinetics equation were 1.0×10^(23) s^(−1) and 177.28 kJ/mol,respectively.Overall,the present study demonstrates that O_(3) as an oxidizing agent can effectively facilitate MnS_(2)O_(6)disproportionation while preventing the release of the secondary pollutant,SO_(2)gas.展开更多
This study prepared a class of RDX-based composite microspheres(RAF)containing ADN and FKM2602.The reaction kinetics of RAF composite microspheres were effectively improved by maintaining the system's high energy ...This study prepared a class of RDX-based composite microspheres(RAF)containing ADN and FKM2602.The reaction kinetics of RAF composite microspheres were effectively improved by maintaining the system's high energy and safety performance.In the close packing state,when the heating rate is rapid,the thermal stability of RAF composite microspheres is better than that of RDX;the close packing state will reduce the degree of freedom of RDX and ADN reaction but will increase the degree of freedom of RAF composite microsphere reaction.The thermal conductivity of RAF composite microspheres is close to that of RDX.In the ignition experiment,the flame of RAF composite microspheres can be maintained without the external heat source.Regarding safety,the H50of RAF composite microspheres was 274.04%higher than that of RDX.The detonation velocity of RAF composite microspheres is slightly higher than that of raw material RDX.Overall,these findings highlight the effectiveness of ADN in enhancing the reaction kinetics of RDX-based composites.展开更多
This study investigates the combustion characteristics of reactive aluminium alloys in combination with fluoropolymer oxidizers. Aluminium-magnesium(Al-Mg) and aluminium-titanium(Al-Ti) alloys were selected as metalli...This study investigates the combustion characteristics of reactive aluminium alloys in combination with fluoropolymer oxidizers. Aluminium-magnesium(Al-Mg) and aluminium-titanium(Al-Ti) alloys were selected as metallic fuels, while polyvinylidene fluoride(PVDF) was employed as the oxidizer. Composite samples were prepared using two methods: electrostatic spraying(ES) and physical mixing(PM). The ES method yielded samples with a PVDF-coated structure, whereas the PM method produced simple mixtures. The samples and their combustion products were characterized using scanning electron microscopy(SEM), X-ray diffraction(XRD), combustion experiments, and thermal analysis. The results indicate that compared to the PM samples, the ES-coated samples exhibited more effective dispersion of metallic particles, reduced particle agglomeration, increased combustion heat release temperature, decreased maximum flame area and height, and mitigated or eliminated explosive or micro-explosive phenomena during combustion, thereby achieving stable combustion. Additionally, the ES samples demonstrated a significant reduction in the particle size of condensed-phase products after combustion, alleviated sintering and agglomeration, decreased the formation of metal oxides, and minimized residual metallic fuel, allowing for the full release of combustion heat. Thermal analysis revealed that the coating structure of the ES samples lowered the activation energy for the reaction between the metallic fuel and PVDF, thereby enhancing the chemical reactivity.展开更多
Selenium distillation slag(SDS)is a high-value-added secondary resource with a high recovery value.This paper aims to investigate the leaching behavior and kinetics of selenium,tellurium,and copper in the SDS acid oxi...Selenium distillation slag(SDS)is a high-value-added secondary resource with a high recovery value.This paper aims to investigate the leaching behavior and kinetics of selenium,tellurium,and copper in the SDS acid oxidation leaching process with H_(2)SO_(4) and H_(2)O_(2).The experimental results showed that under the optimum conditions,the contents of selenium,tellurium,and copper in the SDS were reduced from 22.13 wt%,3.58 wt%,and 6.42 wt%to 3.06 wt%,0.27 wt%,and 0.33 wt%,respectively.Correspondingly,the recovery rates are 87.08%,97.15%and 99.7%.The leaching processes of selenium and tellurium were controlled by diffusion and chemical reactions,and the leaching behavior of copper was controlled by chemical reactions.Below 45℃,the activation energies for selenium,tellurium,and copper were found to be 26.47,62.18 and 19.67 kJ/mol,respectively.In addition,the contents of lead,silver and gold in the leaching residue are increased to 46.8 wt%,8.35 wt%and 0.27 wt%,respectively.These substances can be utilized as raw materials for the recovery of these valuable metals.Importantly,the entire process does not generate toxic or harmful waste,making it a green and environmentally friendly method for resource recovery.展开更多
A partial substitution of Ni by Mn was implemented in order to improve the hydriding and dehydriding kinetics of the Mg2Ni-type alloys. The nanocrystalline and amorphous MgzNi-type Mg2Nil-xMnx （x=0, 0. 1, 0.2, 0.3, ...A partial substitution of Ni by Mn was implemented in order to improve the hydriding and dehydriding kinetics of the Mg2Ni-type alloys. The nanocrystalline and amorphous MgzNi-type Mg2Nil-xMnx （x=0, 0. 1, 0.2, 0.3, 0.4） alloys were synthesized by the melt-spinning technique. The structures of the as-cast and spun alloys were studied by X-ray diffractometry （XRD）, scanning electron microscopy （SEM） and high resolution transmission electron microscopy （HRTEM）. The hydrogen absorption and desorption kinetics of the alloys were measured with an automatically controlled Sieverts apparatus. The results show that the as-spun Mn-free alloy holds a typical nanocrystalline structure, whereas the as-spun alloys containing Mn display a nanocrystalline and amorphous structure, confirming that the substitution of Mn for Ni intensifies the glass forming ability of the Mg2Ni-type alloy. The hydrogen absorption and desorption capacities and kinetics of the alloys increase with increasing the spinning rate, for which the nanocrystalline and amorphous structure produced by the melt spinning is mainly responsible. The substitution of Mn for Ni evidently improves the hydrogen desorption performance. The hydrogen desorption capacities of the as-cast and spun alloys rise with the increase in the percentage of Mn substitution.展开更多
As a newly deVeloped method,high temperature in situ observation method can be used to observe directly the interface changes and study the kinetics mechanism during crystal growth.By our newly designed high temperatu...As a newly deVeloped method,high temperature in situ observation method can be used to observe directly the interface changes and study the kinetics mechanism during crystal growth.By our newly designed high temperature in situ observation equiPment,the interface changes of Bi_(12)SiO_(20) crystal growth from melt were studied.展开更多
The fluorine-based chemical method shows great potential in leaching lithium(Li) from lepidolite. Leaching kinetics of Li in a mixture of sulfuric acid and hydrofluoric acid, which is a typical lixivant for the fluori...The fluorine-based chemical method shows great potential in leaching lithium(Li) from lepidolite. Leaching kinetics of Li in a mixture of sulfuric acid and hydrofluoric acid, which is a typical lixivant for the fluorine-based chemical method, was carried out under crucial factors such as different HF/ore ratios(1:1-3:1 g/mL) and leaching temperatures(50-85℃). The kinetics data fit well with the developed shrinking-core model, indicating that the leaching rate of Li was controlled by the chemical reaction and inner diffusion at the beginning of leaching(0-30 min) as a calculated apparent activation energy(Ea) of 20.62 kJ/mol. The inner diffusion became the rate-limiting step as the leaching continues(60-180 min). Moreover, effects of HF/ore ratio and leaching temperature on selective leaching behavior of Li, Al and Si were discussed. 90% of fluorine mainly existed as HF/F-in leaching solution, which can provide theoretical guidance for further removal or recovery of F.展开更多
The kinetic behavior of leaching copper from low grade copper oxide ore was investigated. The effects of leaching temperature, H2SO4 concentration, particle size of crude ore and agitation rate on the leaching efficie...The kinetic behavior of leaching copper from low grade copper oxide ore was investigated. The effects of leaching temperature, H2SO4 concentration, particle size of crude ore and agitation rate on the leaching efficiency of copper were also evaluated. And the kinetic equations of the leaching process were obtained. The results show that the leaching process can be described with a reaction model of shrinking core. The reaction can be divided into three stages. The first stage is the dissolution of free copper oxide and copper oxide wrapped by hematite-limonite ore. At this stage, the leaching efficiency is very fast （leaching efficiency is larger than 60%）. The second stage is the leaching of diffiuent copper oxides, whose apparent activation energy is 43.26 kJ/mol. During this process, the chemical reaction is the control step, and the reaction order of H2SO4 is 0.433 84. The third stage is the leaching of copper oxide wrapped by hematite-limonite and silicate ore with apparent activation energy of 16.08 kJ/mol, which belongs to the mixed control.展开更多
In this work,the bioleaching process of pyrite,chalcocite and covellite which were the main phase compositions for Zijin copper mineral was comprehensively studied.The influence parameters,such as leaching temperature...In this work,the bioleaching process of pyrite,chalcocite and covellite which were the main phase compositions for Zijin copper mineral was comprehensively studied.The influence parameters,such as leaching temperature,Fe^(3+)concentration,pH of solution and bacteria concentration were investigated.The leaching kinetics of the pyrite,chalcocite and covellite under the studied conditions was successfully modeled by an empirical diffusion-like equation,respectively.The apparent activity energy of pyrite leaching,chalcocite leaching(stage Ⅱ)and covellite leaching was calculated to be 69.29,65.02 and 84.97 kJ/mol,respectively.展开更多
This work describes thermal decomposition behaviour of plastic bonded explosives(PBXs) based on mixture of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX) and 2,4,6-triamino-1,3,5-trinitrobenzene(TATB)with Viton A as poly...This work describes thermal decomposition behaviour of plastic bonded explosives(PBXs) based on mixture of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX) and 2,4,6-triamino-1,3,5-trinitrobenzene(TATB)with Viton A as polymer binder. Thermal decomposition of PBXs was undertaken by applying simultaneous thermal analysis(STA) and differential scanning calorimetry(DSC) to investigate influence of the HMX amount on thermal behavior and its kinetics. Thermogravimetric analysis(TGA) indicated that the thermal decomposition of PBXs based on mixture of HMX and TATB was occurred in a three-steps. The first step was mainly due to decomposition of HMX. The second step was ascribed due to decomposition of TATB, while the third step was occurred due to decomposition of the polymer matrices. The thermal decomposition % was increased with increasing HMX amount. The kinetics related to thermal decomposition were investigated under non-isothermal for a single heating rate measurement. The variation in the activation energy of PBXs based on mixture of HMX and TATB was observed with varying the HMX amount. The kinetics from the results of TGA data at various heating rates under non-isothermal conditions were also calculated by Flynn—Wall—Ozawa(FWO) and Kissinger-Akahira-Sunose(KAS)methods. The activation energies calculated by employing FWO method were very close to those obtained by KAS method. The mean activation energy calculated by FWO and KAS methods was also a good agreement with the activation energy obtained from single heating rate measurement in the first step decomposition.展开更多
Phosphogypsum(PG)is a potential resource for rare earth elements(REEs).Several studies have been carried out on REE leaching from PG.However,few in-depth studies have investigated the kinetics of this leaching process...Phosphogypsum(PG)is a potential resource for rare earth elements(REEs).Several studies have been carried out on REE leaching from PG.However,few in-depth studies have investigated the kinetics of this leaching process.In this study,the leaching kinetics of REEs from PG in nitric acid at different temperatures were explored in depth.The experiments show that the maximum leaching recovery for ΣREE was 58.5%,75.9%and 83.4%at 30,60 and 80℃,respectively.Additionally,among La,Ce,Y and Nd,Y had the highest leaching rate.A new shrinking core model(SCM)based on the dissolution reaction of a cylindrical solid particle with interfacial transfer and diffusion across the product layer as the rate-controlling step was deduced and could well fit the leaching process of REEs from PG.The activation energies for the leaching of La,Ce,Y and Nd were determined on the basis of the new cylindrical SCM.In summary,the cylindrical SCM was a more suitable fitting model than the spherical SCM,and the interfacial transfer and diffusion across the product layer were the rate-controlling step for REE leaching from the PG sample.展开更多
A novel process was proposed for the utilization of potash feldspar by roasting in the presence of sodium carbonate. The effects of roasting temperature, granularity, molar ratio of sodium carbonate to potash feldspar...A novel process was proposed for the utilization of potash feldspar by roasting in the presence of sodium carbonate. The effects of roasting temperature, granularity, molar ratio of sodium carbonate to potash feldspar and roasting time on the silica extraction rate were investigated. Under the optimal roasting conditions, the silica extraction rate was 98%. The optimal conditions, determined using an orthogonal experiment, were found to be roasting temperature of 875 A degrees C, potash feldspar granularity of 74-89 mu m, molar ratio of sodium carbonate to potash feldspar of 1.2:1, and roasting time of 80 min. The kinetics of potash feldspar roasting in the presence of sodium carbonate was described by the shrinking core model and the reaction rate was found to be controlled by the chemical reaction at the particle surface. According to the Arrhenius expression, the activation energy was 164.99 kJ/mol, and the process could be expressed as [1-(1-alpha)(1/3)]=2.66x10(5) exp[-164990/(RT)] t.展开更多
Surface roughness of quartz particles was determined by measuring the specific surface area of particles.The wettability characteristics of particles were determined by measuring the flotation rate using a laboratory ...Surface roughness of quartz particles was determined by measuring the specific surface area of particles.The wettability characteristics of particles were determined by measuring the flotation rate using a laboratory flotation cell.Experimental results show that the rod mill product has higher roughness than the ball mill product.For the particles with larger surface roughness,the flotation kinetics constant is also higher.Finally,empirical relationships between surface roughness(r) and the flotation kinetics constant(k) of quartz particles as k=A+Br+Cr0.5lnr+D/lnr+E/r and k=A+Br are presented,in which A,B,C,D and E are constants related to experimental conditions and mineralogical properties of mineral.展开更多
The kinetics of the thermal decomposition for a naturally ageing ammonium perchlorate(AP) and hydroxyl-terminated-polybutadiene(HTPB) base bleed composite propellant were investigated using a differential scanning cal...The kinetics of the thermal decomposition for a naturally ageing ammonium perchlorate(AP) and hydroxyl-terminated-polybutadiene(HTPB) base bleed composite propellant were investigated using a differential scanning calorimetry(DSC). The naturally ageing AP/HTPB base bleed propellant samples have been stored in a sealed plastic bag at room temperature(5-25 ℃) for more than 20 years. The experimental DSC results were obtained by placing samples(each about 1.5 mg) in a sealed pan under non-isothermal condition under different heating rates, 5.0, 10.0, 15.0, 20.0 and 30.0 ℃·min^(-1). The activation energy and pre-exponential factor were estimated based on the relationship between the exothermic peak temperature and the heating rate by Ozawa and Kissinger methods, respectively. The decomposition kinetic parameters is lower the values under laboratorial aging condition.展开更多
Siderite,as an abundant iron ore,has not been effectively utilized,with a low utilization rate.In this study,the in-situ kinetics and mechanism of siderite during suspension magnetization roasting(SMR)were investigate...Siderite,as an abundant iron ore,has not been effectively utilized,with a low utilization rate.In this study,the in-situ kinetics and mechanism of siderite during suspension magnetization roasting(SMR)were investigated to improve the selective conversion of siderite to magnetite and CO,enriching the theoretical system of green SMR using siderite as a reductant.According to the gas products analyses,the peak value of the reaction rate increased with increasing temperature,and its curves presented the feature of an early peak and long tail.The mechanism function of the siderite pyrolysis was the contraction sphere model(R_(3)):f(α)=3(1−α)2/3;E_(α)was 46.4653 kJ/mol;A was 0.5938 s^(−1);the kinetics equation was k=0.5938exp[−46.4653/(RT)].The in-situ HT-XRD results indicated that siderite was converted into magnetite and wüstite that exhibited a good crystallinity in SMR under a N_(2) atmosphere.At 620℃,the saturation magnetization(M_(s)),remanence magnetization(Mr),and coercivity(Hc)of the product peaked at 53.63×10^(-3)A·m^(2)/g,10.23×10^(-3)A·m^(2)/g,and 12.40×10^(3)A/m,respectively.Meanwhile,the initial particles with a smooth surface were transformed into particles with a porous and loose structure in the roasting process,which would contribute to reducing the grinding cost.展开更多
The leaching kinetics of low grade zinc oxide ore in NH3-NH4Cl-H2O system was studied. The effects of ore particle size, reaction temperature and the sum concentration of ammonium ion and ammonia on the leaching effic...The leaching kinetics of low grade zinc oxide ore in NH3-NH4Cl-H2O system was studied. The effects of ore particle size, reaction temperature and the sum concentration of ammonium ion and ammonia on the leaching efficiency of zinc were examined. The leaching kinetics of low-grade zinc oxide ore in NH3-NH4Cl-H2O system follows the kinetic law of shrinking-core model. The results show that diffusion through the inert particle pores is the leaching kinetics rate controlling step. The calculated apparent activation energy of the process is about 7.057 kJ/mol. The leaching efficiency of zinc is 92.1% under the conditions of ore particle size of 69 μm, holding at 80 ℃ for 60 min, sum ammonia concentration of 7.5 mol/L, the molar ratio of ammonium to ammonia being 2-1, and the ratio (g/mL) of solid to liquid being 1-10.展开更多
The kinetics of reductive leaching of manganese from a low-grade manganese oxide ore were studied using cellulose as reductant in dilute sulfuric acid medium.It was found that when the stirring speed was higher than 2...The kinetics of reductive leaching of manganese from a low-grade manganese oxide ore were studied using cellulose as reductant in dilute sulfuric acid medium.It was found that when the stirring speed was higher than 200 r/min,the effect of gas film diffusion on manganese extraction efficiency could be neglected,and the kinetic behavior was investigated under the condition of elimination of external diffusion influence on the leaching process.Effects of leaching temperature,mass ratio of cellulose and ore,and the sulfuric acid concentration on manganese extraction efficiency were discussed.The kinetic data were analyzed based on the shrinking core model,which indicated that the leaching process was dominated by both ash layer diffusion and chemical reaction at the initial stage,with the progress of leaching reaction,the rate-controlling step switched to the ash layer diffusion.It was also concluded that the sulfuric acid concentration had the most significant influence on the leaching rate,the reaction orders with respect to the sulfuric acid concentration were 2.102 in the first 60 min,and 3.642 in the later 90 min,while the reaction orders for mass ratio of cellulose and ore were 0.660 and 0.724,respectively.An Arrhenius relationship was used to relate the temperature to the rate of leaching,from which apparent activation energies were calculated to be 46.487 kJ/mol and 62.290 kJ/mol at the two stages,respectively.Finally,the overall leaching rate equations for the manganese dissolution reaction with cellulose in sulphuric acid solution were developed.The morphological changes and mineralogical forms of the ore before and after the chemical treatment were discussed with the support of SEM and XRD analyses.展开更多
基金Supported by Innovation Capability Support Program of Shaanxi(2024RS-CXTD-53,2024ZC-KJXX-096)the Key R&D Program of Shaanxi Province(2022QCY-LL-69)Xi’an Science and Technology Project(24GXFW0089)。
文摘Under the backdrop of“Carbon Peak and Carbon Neutrality”(dual carbon)goal in China,the methane-carbon dioxide reforming reaction has attracted considerable attention due to its environmental benefits of converting two greenhouse gases(methane and carbon dioxide)into syngas and its promising industrial applications.Nickel(Ni)-based catalysts,with high catalytic activity,low cost,and abundant resources,are considered ideal candidates for industrial applications.In this article,three reaction kinetic models were briefly introduced,namely the Power-Law(PL)model,the Eley-Rideal(ER)model,and the Langmuir-Hinshelwood-Hougen-Watson(LHHW)model.Based on the LHHW model,the reaction kinetics and mechanisms of different catalytic systems were systematically discussed,including the properties of supports,the doping of noble metals and transition metals,the role of promoters,and the influence of the geometric and electronic structures of Ni on the reaction mechanism.Furthermore,the kinetics of carbon deposition and elimination on various catalysts were analyzed.Based on the reaction rate expressions for carbon elimination,the reasons for the high activity of transition metal iron(Fe)-doped catalysts and core-shell structured catalysts in carbon elimination were explained.Based on the detailed collation and comparative analysis of the reaction mechanisms and kinetic characteristics across diverse Ni-based catalytic systems,a theoretical guidance for the designing of high-performance catalysts was provided in this work.
文摘Selective laser melting(SLM)is a cost-effective 3 D metal additive manufacturing(AM)process.However,AM 316 L stainless steel(SS)has different surface and microstructure properties as compared to conventional ones.Boriding process is one of the ways to modify and increase the surface properties.The aim of this study is to predict and understand the growth kinetic of iron boride layers on AM 316 L SS.In this study,the growth kinetic mechanism was evaluated for AM 316 L SS.Pack boriding was applied at 850,900 and 950℃,each for 2,4 and 6 h.The thickness of the boride layers ranged from(1.8±0.3)μm to(27.7±2.2)μm.A diffusion model based on error function solutions in Fick’s second law was proposed to quantitatively predict and elucidate the growth rate of FeB and Fe_(2)B phase layers.The activation energy(Q)values for boron diffusion in FeB layer,Fe_(2)B layer,and dual FeB+Fe_(2)B layer were found to be 256.56,161.61 and 209.014 kJ/mol,respectively,which were higher than the conventional 316 L SS.The findings might provide and open new directions and approaches for applications of additively manufactured steels.
基金supported by National Natural Science Foundation of China(22178002,22178001)Natural Science Foundation of Anhui Province(2308085Y19)Excellent Youth Research Project of Anhui Provincial Department of Education(2022AH030045).
文摘Hydrogen-enriched ironmaking presents a promising approach to mitigate coke consumption and carbon emission in blast furnace(BF)operations.This work investigated the relationship between the structural features of cokes and their reactivity towards solution loss(SL),especially under hydrogen-enriched atmospheres.Six cokes were characterized,and their SL behaviors were examined under varying atmospheres to elucidate the effects of hydrogen enrichment.The results indicate that an increase in fixed carbon content leads to a decrease in the coke reactivity index(CRI)and an increase in coke strength after reaction(CSR),in the CO_(2) atmosphere,the CSR of coke increases from 35.76%−62.83%,while in the 90CO_(2)/10H_(2) atmosphere,the CSR of coke increases from 65.67%−84.09%.There is a good linear relationship between CRI and microcrystalline structure parameters of coke.Cokes with larger crystalline size,lower amorphous content,and smaller optical texture index(OTI)values show enhanced resistance to degradation and maintain structural integrity in BF.Kinetic analysis performed with the shifted-modified-random pore model(S-MRPM)reveals that alterations in pore structure and intrinsic mineral composition significantly influence the reaction rate.The introduction of a small amount of water vapor raises SL rates,whereas a minor addition of hydrogen(<10%)decelerates SL due to its incomplete conversion to water vapor and the reduced partial pressure of the gasifying agent.Thermodynamic calculations also indicate that the introduced hydrogen does not convert into the same fraction of water vapor.The shift from chemical reaction control to gas diffusion control as the rate-determining step with rising temperatures during SL process was confirmed,and the introduction of hydrogen does not notably alter SL behavior.This result demonstrated that introducing a small amount of hydrogen(<10%)can mitigate SL rates,thereby enhancing coke strength and reducing coke consumption and carbon emissions.
基金Project(2022M710619)supported by the Postdoctoral Science Foundation of ChinaProjects(2020YFH0213,2020YFG0039)supported by the Sichuan Science and Technology Program,China+1 种基金Projects(XJ2024001501,KCXTD2023-4)supported by the Basic Scientific Foundation and Innovation Team Funds of China West Normal UniversityProject(CSPC202403)supported by the Open Project Program of Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province,China。
文摘In response to the fact that the presence of manganese dithionate(MnS_(2)O_(6))leads to a series of adverse impacts,especially lower purity of manganese sulfate(MnSO_(4))and disruption of its recovery,advanced oxidation methods such as ozonation system are used to manage MnS_(2)O_(6)in the leaching solution,replacing conventional methods.To ascertain the conversion rate and kinetics of MnS_(2)O_(6)during the ozonation process,we explored the factors influencing its removal rate,including ozone dosage,manganese dithionate concentration,sulfuric acid concentration,and reaction temperature.Batch experiments were conducted to determine the reaction rate constant of ozone(k)and activation energy(Ea)obtained from intermittent experimental data fitting,revealing a least-squares exponential conversion relationship between k and the MnS_(2)O_(6)removal amount,wherein an increase in the aforementioned factors led to an enhanced MnS_(2)O_(6)conversion rate,exceeding 99.3%.The formation mechanism of the ozone products proposed during the experiment was summarized and proposed as follows:1)Mn^(2+)was directly oxidized to MnO_(2),and 2)SO_(4)2−was obtained by the catalytic oxidation of S_(2)O_(6)^(2−)with HO•from O3 decomposition.According to the kinetics analysis,the pre-exponential factor and total activation energy of the ozonation kinetics equation were 1.0×10^(23) s^(−1) and 177.28 kJ/mol,respectively.Overall,the present study demonstrates that O_(3) as an oxidizing agent can effectively facilitate MnS_(2)O_(6)disproportionation while preventing the release of the secondary pollutant,SO_(2)gas.
基金supported by the Natural Science Foundation of Shanxi Province(Grant No.202203021221120)The Open Fund of MCRI-Shannxi Laboratory of Energetic Materials(Grant No.204-J-2024-2622)。
文摘This study prepared a class of RDX-based composite microspheres(RAF)containing ADN and FKM2602.The reaction kinetics of RAF composite microspheres were effectively improved by maintaining the system's high energy and safety performance.In the close packing state,when the heating rate is rapid,the thermal stability of RAF composite microspheres is better than that of RDX;the close packing state will reduce the degree of freedom of RDX and ADN reaction but will increase the degree of freedom of RAF composite microsphere reaction.The thermal conductivity of RAF composite microspheres is close to that of RDX.In the ignition experiment,the flame of RAF composite microspheres can be maintained without the external heat source.Regarding safety,the H50of RAF composite microspheres was 274.04%higher than that of RDX.The detonation velocity of RAF composite microspheres is slightly higher than that of raw material RDX.Overall,these findings highlight the effectiveness of ADN in enhancing the reaction kinetics of RDX-based composites.
基金National Natural Science Foundation of China (NSFC,Grant Nos.52176114 and 52306145)Natural Science Foundation of Jiangsu Province (Grant No.BK20230929)+2 种基金China Postdoctoral Science Foundation (Grant No.2024M764222)Fundamental Research Funds for the Central Universities (Grant No.30924010505)Jiangsu Funding Program for Excellent Postdoctoral Talent。
文摘This study investigates the combustion characteristics of reactive aluminium alloys in combination with fluoropolymer oxidizers. Aluminium-magnesium(Al-Mg) and aluminium-titanium(Al-Ti) alloys were selected as metallic fuels, while polyvinylidene fluoride(PVDF) was employed as the oxidizer. Composite samples were prepared using two methods: electrostatic spraying(ES) and physical mixing(PM). The ES method yielded samples with a PVDF-coated structure, whereas the PM method produced simple mixtures. The samples and their combustion products were characterized using scanning electron microscopy(SEM), X-ray diffraction(XRD), combustion experiments, and thermal analysis. The results indicate that compared to the PM samples, the ES-coated samples exhibited more effective dispersion of metallic particles, reduced particle agglomeration, increased combustion heat release temperature, decreased maximum flame area and height, and mitigated or eliminated explosive or micro-explosive phenomena during combustion, thereby achieving stable combustion. Additionally, the ES samples demonstrated a significant reduction in the particle size of condensed-phase products after combustion, alleviated sintering and agglomeration, decreased the formation of metal oxides, and minimized residual metallic fuel, allowing for the full release of combustion heat. Thermal analysis revealed that the coating structure of the ES samples lowered the activation energy for the reaction between the metallic fuel and PVDF, thereby enhancing the chemical reactivity.
基金Project(2022YFC2904900) supported by the National Key Research and Development Program of ChinaProject(U1902221) supported by the National Natural Science Foundation of China。
文摘Selenium distillation slag(SDS)is a high-value-added secondary resource with a high recovery value.This paper aims to investigate the leaching behavior and kinetics of selenium,tellurium,and copper in the SDS acid oxidation leaching process with H_(2)SO_(4) and H_(2)O_(2).The experimental results showed that under the optimum conditions,the contents of selenium,tellurium,and copper in the SDS were reduced from 22.13 wt%,3.58 wt%,and 6.42 wt%to 3.06 wt%,0.27 wt%,and 0.33 wt%,respectively.Correspondingly,the recovery rates are 87.08%,97.15%and 99.7%.The leaching processes of selenium and tellurium were controlled by diffusion and chemical reactions,and the leaching behavior of copper was controlled by chemical reactions.Below 45℃,the activation energies for selenium,tellurium,and copper were found to be 26.47,62.18 and 19.67 kJ/mol,respectively.In addition,the contents of lead,silver and gold in the leaching residue are increased to 46.8 wt%,8.35 wt%and 0.27 wt%,respectively.These substances can be utilized as raw materials for the recovery of these valuable metals.Importantly,the entire process does not generate toxic or harmful waste,making it a green and environmentally friendly method for resource recovery.
基金Projects(50871050,50961001) supported by the National Natural Science Foundation of ChinaProject(2010ZD05) supported by the Natural Science Foundation of Inner Mongolia,ChinaProject(NJzy08071) supported by the High Education Science Research Program of Inner Mongolia,China
文摘A partial substitution of Ni by Mn was implemented in order to improve the hydriding and dehydriding kinetics of the Mg2Ni-type alloys. The nanocrystalline and amorphous MgzNi-type Mg2Nil-xMnx （x=0, 0. 1, 0.2, 0.3, 0.4） alloys were synthesized by the melt-spinning technique. The structures of the as-cast and spun alloys were studied by X-ray diffractometry （XRD）, scanning electron microscopy （SEM） and high resolution transmission electron microscopy （HRTEM）. The hydrogen absorption and desorption kinetics of the alloys were measured with an automatically controlled Sieverts apparatus. The results show that the as-spun Mn-free alloy holds a typical nanocrystalline structure, whereas the as-spun alloys containing Mn display a nanocrystalline and amorphous structure, confirming that the substitution of Mn for Ni intensifies the glass forming ability of the Mg2Ni-type alloy. The hydrogen absorption and desorption capacities and kinetics of the alloys increase with increasing the spinning rate, for which the nanocrystalline and amorphous structure produced by the melt spinning is mainly responsible. The substitution of Mn for Ni evidently improves the hydrogen desorption performance. The hydrogen desorption capacities of the as-cast and spun alloys rise with the increase in the percentage of Mn substitution.
文摘As a newly deVeloped method,high temperature in situ observation method can be used to observe directly the interface changes and study the kinetics mechanism during crystal growth.By our newly designed high temperature in situ observation equiPment,the interface changes of Bi_(12)SiO_(20) crystal growth from melt were studied.
基金Project(51474237)supported by the National Natural Science Foundation of China
文摘The fluorine-based chemical method shows great potential in leaching lithium(Li) from lepidolite. Leaching kinetics of Li in a mixture of sulfuric acid and hydrofluoric acid, which is a typical lixivant for the fluorine-based chemical method, was carried out under crucial factors such as different HF/ore ratios(1:1-3:1 g/mL) and leaching temperatures(50-85℃). The kinetics data fit well with the developed shrinking-core model, indicating that the leaching rate of Li was controlled by the chemical reaction and inner diffusion at the beginning of leaching(0-30 min) as a calculated apparent activation energy(Ea) of 20.62 kJ/mol. The inner diffusion became the rate-limiting step as the leaching continues(60-180 min). Moreover, effects of HF/ore ratio and leaching temperature on selective leaching behavior of Li, Al and Si were discussed. 90% of fluorine mainly existed as HF/F-in leaching solution, which can provide theoretical guidance for further removal or recovery of F.
基金Project(2005BA639C) supported by the National Science and Technology Development of China
文摘The kinetic behavior of leaching copper from low grade copper oxide ore was investigated. The effects of leaching temperature, H2SO4 concentration, particle size of crude ore and agitation rate on the leaching efficiency of copper were also evaluated. And the kinetic equations of the leaching process were obtained. The results show that the leaching process can be described with a reaction model of shrinking core. The reaction can be divided into three stages. The first stage is the dissolution of free copper oxide and copper oxide wrapped by hematite-limonite ore. At this stage, the leaching efficiency is very fast （leaching efficiency is larger than 60%）. The second stage is the leaching of diffiuent copper oxides, whose apparent activation energy is 43.26 kJ/mol. During this process, the chemical reaction is the control step, and the reaction order of H2SO4 is 0.433 84. The third stage is the leaching of copper oxide wrapped by hematite-limonite and silicate ore with apparent activation energy of 16.08 kJ/mol, which belongs to the mixed control.
基金Project(51574036)supported by the National Natural Science Foundation of China。
文摘In this work,the bioleaching process of pyrite,chalcocite and covellite which were the main phase compositions for Zijin copper mineral was comprehensively studied.The influence parameters,such as leaching temperature,Fe^(3+)concentration,pH of solution and bacteria concentration were investigated.The leaching kinetics of the pyrite,chalcocite and covellite under the studied conditions was successfully modeled by an empirical diffusion-like equation,respectively.The apparent activity energy of pyrite leaching,chalcocite leaching(stage Ⅱ)and covellite leaching was calculated to be 69.29,65.02 and 84.97 kJ/mol,respectively.
基金DRDO(TBR-1251)for funding and awarding the Project
文摘This work describes thermal decomposition behaviour of plastic bonded explosives(PBXs) based on mixture of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX) and 2,4,6-triamino-1,3,5-trinitrobenzene(TATB)with Viton A as polymer binder. Thermal decomposition of PBXs was undertaken by applying simultaneous thermal analysis(STA) and differential scanning calorimetry(DSC) to investigate influence of the HMX amount on thermal behavior and its kinetics. Thermogravimetric analysis(TGA) indicated that the thermal decomposition of PBXs based on mixture of HMX and TATB was occurred in a three-steps. The first step was mainly due to decomposition of HMX. The second step was ascribed due to decomposition of TATB, while the third step was occurred due to decomposition of the polymer matrices. The thermal decomposition % was increased with increasing HMX amount. The kinetics related to thermal decomposition were investigated under non-isothermal for a single heating rate measurement. The variation in the activation energy of PBXs based on mixture of HMX and TATB was observed with varying the HMX amount. The kinetics from the results of TGA data at various heating rates under non-isothermal conditions were also calculated by Flynn—Wall—Ozawa(FWO) and Kissinger-Akahira-Sunose(KAS)methods. The activation energies calculated by employing FWO method were very close to those obtained by KAS method. The mean activation energy calculated by FWO and KAS methods was also a good agreement with the activation energy obtained from single heating rate measurement in the first step decomposition.
基金Project(51904104) supported by the National Natural Science Foundation of ChinaProject(2020JJ5174) supported by the Natural Science Foundation of Hunan Province,China+2 种基金Project(2019M662780) supported by China Postdoctoral Science FoundationProject(19C0746) supported by Scientific Research Fund of Hunan Provincial Education Department,ChinaProject(2021-2843) supported by College Student Innovation and Entrepreneurship Training Program of Hunan Province,China。
文摘Phosphogypsum(PG)is a potential resource for rare earth elements(REEs).Several studies have been carried out on REE leaching from PG.However,few in-depth studies have investigated the kinetics of this leaching process.In this study,the leaching kinetics of REEs from PG in nitric acid at different temperatures were explored in depth.The experiments show that the maximum leaching recovery for ΣREE was 58.5%,75.9%and 83.4%at 30,60 and 80℃,respectively.Additionally,among La,Ce,Y and Nd,Y had the highest leaching rate.A new shrinking core model(SCM)based on the dissolution reaction of a cylindrical solid particle with interfacial transfer and diffusion across the product layer as the rate-controlling step was deduced and could well fit the leaching process of REEs from PG.The activation energies for the leaching of La,Ce,Y and Nd were determined on the basis of the new cylindrical SCM.In summary,the cylindrical SCM was a more suitable fitting model than the spherical SCM,and the interfacial transfer and diffusion across the product layer were the rate-controlling step for REE leaching from the PG sample.
基金Project(51204054)supported by the National Natural Science Foundation of ChinaProject(2007CB613603)supported by the National Basic Research Program of ChinaProject(N140204011)supported by the Ministry of Education Basic Scientific Research Business Expenses,China
文摘A novel process was proposed for the utilization of potash feldspar by roasting in the presence of sodium carbonate. The effects of roasting temperature, granularity, molar ratio of sodium carbonate to potash feldspar and roasting time on the silica extraction rate were investigated. Under the optimal roasting conditions, the silica extraction rate was 98%. The optimal conditions, determined using an orthogonal experiment, were found to be roasting temperature of 875 A degrees C, potash feldspar granularity of 74-89 mu m, molar ratio of sodium carbonate to potash feldspar of 1.2:1, and roasting time of 80 min. The kinetics of potash feldspar roasting in the presence of sodium carbonate was described by the shrinking core model and the reaction rate was found to be controlled by the chemical reaction at the particle surface. According to the Arrhenius expression, the activation energy was 164.99 kJ/mol, and the process could be expressed as [1-(1-alpha)(1/3)]=2.66x10(5) exp[-164990/(RT)] t.
文摘Surface roughness of quartz particles was determined by measuring the specific surface area of particles.The wettability characteristics of particles were determined by measuring the flotation rate using a laboratory flotation cell.Experimental results show that the rod mill product has higher roughness than the ball mill product.For the particles with larger surface roughness,the flotation kinetics constant is also higher.Finally,empirical relationships between surface roughness(r) and the flotation kinetics constant(k) of quartz particles as k=A+Br+Cr0.5lnr+D/lnr+E/r and k=A+Br are presented,in which A,B,C,D and E are constants related to experimental conditions and mineralogical properties of mineral.
文摘The kinetics of the thermal decomposition for a naturally ageing ammonium perchlorate(AP) and hydroxyl-terminated-polybutadiene(HTPB) base bleed composite propellant were investigated using a differential scanning calorimetry(DSC). The naturally ageing AP/HTPB base bleed propellant samples have been stored in a sealed plastic bag at room temperature(5-25 ℃) for more than 20 years. The experimental DSC results were obtained by placing samples(each about 1.5 mg) in a sealed pan under non-isothermal condition under different heating rates, 5.0, 10.0, 15.0, 20.0 and 30.0 ℃·min^(-1). The activation energy and pre-exponential factor were estimated based on the relationship between the exothermic peak temperature and the heating rate by Ozawa and Kissinger methods, respectively. The decomposition kinetic parameters is lower the values under laboratorial aging condition.
基金Projects(51874071,52022019,51734005)supported by the National Natural Science Foundation of ChinaProject(161045)supported by the Fok Ying Tung Education Foundation for Yong Teachers in the Higher Education Institutions of China。
文摘Siderite,as an abundant iron ore,has not been effectively utilized,with a low utilization rate.In this study,the in-situ kinetics and mechanism of siderite during suspension magnetization roasting(SMR)were investigated to improve the selective conversion of siderite to magnetite and CO,enriching the theoretical system of green SMR using siderite as a reductant.According to the gas products analyses,the peak value of the reaction rate increased with increasing temperature,and its curves presented the feature of an early peak and long tail.The mechanism function of the siderite pyrolysis was the contraction sphere model(R_(3)):f(α)=3(1−α)2/3;E_(α)was 46.4653 kJ/mol;A was 0.5938 s^(−1);the kinetics equation was k=0.5938exp[−46.4653/(RT)].The in-situ HT-XRD results indicated that siderite was converted into magnetite and wüstite that exhibited a good crystallinity in SMR under a N_(2) atmosphere.At 620℃,the saturation magnetization(M_(s)),remanence magnetization(Mr),and coercivity(Hc)of the product peaked at 53.63×10^(-3)A·m^(2)/g,10.23×10^(-3)A·m^(2)/g,and 12.40×10^(3)A/m,respectively.Meanwhile,the initial particles with a smooth surface were transformed into particles with a porous and loose structure in the roasting process,which would contribute to reducing the grinding cost.
基金Project(2007CB613604) supported by the Major State Basic Research Development Program of ChinaProject(50674104) supported by the National Natural Science Foundation of ChinaProject(GJJ08279) supported by the Department of Education of Jiangxi Province
文摘The leaching kinetics of low grade zinc oxide ore in NH3-NH4Cl-H2O system was studied. The effects of ore particle size, reaction temperature and the sum concentration of ammonium ion and ammonia on the leaching efficiency of zinc were examined. The leaching kinetics of low-grade zinc oxide ore in NH3-NH4Cl-H2O system follows the kinetic law of shrinking-core model. The results show that diffusion through the inert particle pores is the leaching kinetics rate controlling step. The calculated apparent activation energy of the process is about 7.057 kJ/mol. The leaching efficiency of zinc is 92.1% under the conditions of ore particle size of 69 μm, holding at 80 ℃ for 60 min, sum ammonia concentration of 7.5 mol/L, the molar ratio of ammonium to ammonia being 2-1, and the ratio (g/mL) of solid to liquid being 1-10.
基金Project(2010FJ1011)supported by the Major Project of Science and Technology of Hunan Province,China
文摘The kinetics of reductive leaching of manganese from a low-grade manganese oxide ore were studied using cellulose as reductant in dilute sulfuric acid medium.It was found that when the stirring speed was higher than 200 r/min,the effect of gas film diffusion on manganese extraction efficiency could be neglected,and the kinetic behavior was investigated under the condition of elimination of external diffusion influence on the leaching process.Effects of leaching temperature,mass ratio of cellulose and ore,and the sulfuric acid concentration on manganese extraction efficiency were discussed.The kinetic data were analyzed based on the shrinking core model,which indicated that the leaching process was dominated by both ash layer diffusion and chemical reaction at the initial stage,with the progress of leaching reaction,the rate-controlling step switched to the ash layer diffusion.It was also concluded that the sulfuric acid concentration had the most significant influence on the leaching rate,the reaction orders with respect to the sulfuric acid concentration were 2.102 in the first 60 min,and 3.642 in the later 90 min,while the reaction orders for mass ratio of cellulose and ore were 0.660 and 0.724,respectively.An Arrhenius relationship was used to relate the temperature to the rate of leaching,from which apparent activation energies were calculated to be 46.487 kJ/mol and 62.290 kJ/mol at the two stages,respectively.Finally,the overall leaching rate equations for the manganese dissolution reaction with cellulose in sulphuric acid solution were developed.The morphological changes and mineralogical forms of the ore before and after the chemical treatment were discussed with the support of SEM and XRD analyses.
