The use of peat for the removal of nickel from aqueous solutions has been investigated at various pH values by means of static conditions. The present research shows that the ability of Ni to bind to peat increases as...The use of peat for the removal of nickel from aqueous solutions has been investigated at various pH values by means of static conditions. The present research shows that the ability of Ni to bind to peat increases as the pH value increases. The solutions reach adsorption equilibrium rapidly. A reasonable kinetic model, first-order in nickel concentration, has been developed and fitted to the adsorption of nickel （Ⅱ） onto peat. The first-order model provides a good correlation to the experimental data. The characteristic parameters of the Langmuir isotherm were determined at various temperatures. The relationship between kinetics and equilibrium isotherms was established through the forward- and backward-rate-constants, k~ and k2, and the equilibrium constant, K.展开更多
This investigation was carried out to establish a new domestic landfill gas(LFG)generation rate model that takes into account the impact of leachate recirculation.The first-order kinetics and two-stage reaction(FKTSR)...This investigation was carried out to establish a new domestic landfill gas(LFG)generation rate model that takes into account the impact of leachate recirculation.The first-order kinetics and two-stage reaction(FKTSR)model of the LFG generation rate includes mechanisms of the nutrient balance for biochemical reaction in two main stages.In this study,the FKTSR model was modified by the introduction of the outflow function and the organic acid conversion coefficient in order to represent the in-situ condition of nutrient loss through leachate.Laboratory experiments were carried out to simulate the impact of leachate recirculation and verify the modified FKTSR model.The model calibration was then calculated by using the experimental data.The results suggested that the new model was in line with the experimental data.The main parameters of the modified FKTSR model,including the LFG production potential(L0),the reaction rate constant in the first stage(K1),and the reaction rate constant in the second stage(K2)of 64.746 L,0.202 d^(–1),and 0.338 d^(–1),respectively,were comparable to the old ones of 42.069 L,0.231 d^(–1),and 0.231 d^(–1).The new model is better able to explain the mechanisms involved in LFG generation.展开更多
This work reveals the significant effects of cobalt(Co)on the microstructure and impact toughness of as-quenched highstrength steels by experimental characterizations and thermo-kinetic analyses.The results show that ...This work reveals the significant effects of cobalt(Co)on the microstructure and impact toughness of as-quenched highstrength steels by experimental characterizations and thermo-kinetic analyses.The results show that the Co-bearing steel exhibits finer blocks and a lower ductile-brittle transition temperature than the steel without Co.Moreover,the Co-bearing steel reveals higher transformation rates at the intermediate stage with bainite volume fraction ranging from around 0.1 to 0.6.The improved impact toughness of the Co-bearing steel results from the higher dense block boundaries dominated by the V1/V2 variant pair.Furthermore,the addition of Co induces a larger transformation driving force and a lower bainite start temperature(BS),thereby contributing to the refinement of blocks and the increase of the V1/V2 variant pair.These findings would be instructive for the composition,microstructure design,and property optimization of high-strength 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
Hydrogen desorption kinetics and characteristics,residual hydrogen content and activation energy of TC21 alloy were investigated by the constant volume method.Results show that hydrogen desorption temperature and init...Hydrogen desorption kinetics and characteristics,residual hydrogen content and activation energy of TC21 alloy were investigated by the constant volume method.Results show that hydrogen desorption temperature and initial hydrogen pressure affect hydrogen desorption characteristics of TC21 alloy.The hydrogen desorption process is mainly dominated by nucleation and growth process(kt=[-ln(1-α)]^(2/3)),chemical reaction process(kt=(1-α)^(-1/2))and three-dimensional diffusion process(kt=[1-(1-α)^(1/3)]^(1/2))when the hydrogenated TC21 alloy is dehydrogenated at temperatures of 700-940°C.When the hydrogenated TC21 alloy releases hydrogen,the following relationship exists among the rate constants of each process:k(chemical reaction process)>k(nucleation and growth process)>k(three-dimensional diffusion process).The residual hydrogen content of the hydrogenated TC21 alloy after hydrogen desorption decreases gradually with the increase in hydrogen desorption temperature,and increases gradually with the increase in the initial hydrogen pressure.The activation energy of TC21 alloy in the process of hydrogen desorption is about 26.663 kJ/mol.展开更多
In this paper,we present a novel first-order digitalΣΔconverter tailored for digital-to-analog applications,focusing on achieving both high yield and reduced silicon estate.Our approach incorporates a substantial le...In this paper,we present a novel first-order digitalΣΔconverter tailored for digital-to-analog applications,focusing on achieving both high yield and reduced silicon estate.Our approach incorporates a substantial level of dithering noise into the input signal,strategically aimed at mitigating the spurious frequencies commonly encountered in such converters.Validation of our design is performed through simulations using a high-level simulator specialized in mixed-signal circuit analysis.The results underscore the enhanced performance of our circuit,especially in reducing spurious frequencies,highlighting its efficiency and effectiveness.The final circuit exhibits an effective number of bits of 13.展开更多
Hexafluoropropylene oxide(HFPO)is a crucial fluorinated chemical mainly synthesized from hexafluoropropylene(HFP)through the oxidation of oxygen.However,the reaction network and kinetic characteristics are not fully u...Hexafluoropropylene oxide(HFPO)is a crucial fluorinated chemical mainly synthesized from hexafluoropropylene(HFP)through the oxidation of oxygen.However,the reaction network and kinetic characteristics are not fully understood yet,resulting in a lack of theoretical basis for synthesis process improvement.Here,the free radical reaction mechanism and complete reaction network involved in the noncatalytic oxidation of HFP to synthesize HFPO was explored by density functional theory.Transition state theory was employed to calculate the intrinsic reaction rate constants for elementary reactions.Based on theoretical reaction rate ratios,reaction pathways were selected,and a simplified reaction network was derived.It was found that byproducts were formed owing to the decomposition of HFPO and subsequent reactions with excessive oxygen while oxygen tended to participate more in the main reaction under oxygen-deficient conditions.The variations in reaction pathways occurring at different HFP/oxygen molar ratios was well elucidated by comparing with experimental data.This research establishes a robust theoretical foundation for optimizing and regulating the synthesis of HFPO.展开更多
Intuitively,the solvation structure featuring stronger interacted sheath in deep eutectic solution(DES)electrolyte would result in sluggish interfacial charge transfer and intense polarization,which obstructs its prac...Intuitively,the solvation structure featuring stronger interacted sheath in deep eutectic solution(DES)electrolyte would result in sluggish interfacial charge transfer and intense polarization,which obstructs its practical application in emerging Zn based batteries.Unexpectedly,here we discover a Zn‖organic battery with exceptional kinetics properties enabled by a hydrated DES electrolyte,which can render higher discharge capacity,smaller voltage polarization,and faster kinetics of charge transfer in comparison with conventional aqueous 3 M ZnCl_(2)electrolyte,though its viscosity is two orders of magnitude higher than the latter.The improved kinetics of charge transfer and ion diffusion is demonstrated to originate from the local electron structure regulation of cathode in hydrated DES electrolyte.Furthermore,the DES electrolyte has also been shown to restrict parasitic reaction associated with active water by preferential urea-molecular adsorption on Zn surface and stronger water trapping in solvation structure,giving rise to long-term stable dendrite-free Zn plating/stripping.This work provides a new rationale for understanding electrochemical behaviors of organic cathodes in DES electrolyte,which is conducive to the development of high-performance Zn‖organic batteries.展开更多
The erosion process and kinetics of PbTe particles in a selenium melt were investigated.The results reveal that the limiting step of the reaction is controlled by product layer diffusion and the interfacial chemical r...The erosion process and kinetics of PbTe particles in a selenium melt were investigated.The results reveal that the limiting step of the reaction is controlled by product layer diffusion and the interfacial chemical reaction at low temperatures(573,583,and 593 K),but the limiting step is controlled by boundary layer diffusion at high temperatures(603 and 613 K).The Se-and Te-atom diffusion in the product layer becomes unbalanced as the product layer thickens,with Kirkendall voids generating in the product layer accelerating PbTe particle erosion.After the PbTe impurities in the selenium melt evolve into PbSe and Te,Te is evenly distributed in the selenium melt owing to the solubility of Se and Te.This study serves to clarify the evolution behavior of PbTe impurities in the selenium melt and the reason that Te often occurs in Se.展开更多
Al_(2)O_(3)and MgO serve as the primary gangue components in sintered ores,and they are critical for the formation of CaO-Fe_(2)O_(3)-xAl_(2)O_(3)(wt%,C-F-xA)and CaO-Fe_(2)O_(3)-xM gO(wt%,C-F-xM)systems,respectively.I...Al_(2)O_(3)and MgO serve as the primary gangue components in sintered ores,and they are critical for the formation of CaO-Fe_(2)O_(3)-xAl_(2)O_(3)(wt%,C-F-xA)and CaO-Fe_(2)O_(3)-xM gO(wt%,C-F-xM)systems,respectively.In this study,a nonisothermal crystallization thermodynamics behavior of C-F-xA and C-F-xM systems was examined using differential scanning calorimetry,and a phase identification and microstructure analysis for C-F-xA and C-F-xM systems were carried out by X-ray diffraction and scanning electron microscopy.Results showed that in C-F-2A and C-F-2M systems,the increased cooling rates promoted the precipitation of CaFe_(2)O_(4)(CF)but inhibited the formation of Ca_(2)Fe_(2)O_(5)(C2F).In addition,C-F-2A system exhibited a lower theoretical initial crystallization temperature(1566 K)compared to the C-F system(1578 K).This temperature further decreases to 1554 K and 1528 K in the C-F-4A and C-F-8A systems,respectively.However,in C-F-xM system,the increased MgO content raised the crystallization temperature.This is because that the enhanced precipitation of MF(a spinel phase mainly comprised Fe_(3)O_(4)and MgFe_(2)O_(4))and C2F phases suppressed the CF precipitation reaction.In kinetic calculations,the Ozawa method revealed the apparent activation energies of the C-F-2A and C-F-2M systems.Malek's method revealed that the crystallization process in C-F-2A system initially followed a logarithmic law(lnαor lnα2),later transitioning to a reaction order law((1-α)-1or(1-α)^(-1/2),n=2/3)or the lnα2function of the exponential law.In C-F-2M system,it consistently followed the sequencef(α)=(1-α)^(2)(αis the crystallization conversion rate;n is the Avrami constant;?(α)is the differential equations for the model function of C_(2)F and CF crystallization processes).展开更多
Iron ore pellets,as one of the main charges of blast furnaces,have a greater impact on the CO_(2)emission reduction and stable operation of blast furnaces.The isothermal reduction behavior of the pellets obtained from...Iron ore pellets,as one of the main charges of blast furnaces,have a greater impact on the CO_(2)emission reduction and stable operation of blast furnaces.The isothermal reduction behavior of the pellets obtained from a Chinese steel plant was studied in the gas mixtures of CO and N_(2).The results showed the reduction process is divided into two stages.The reduction in the initial stage(time t≤40 min)is cooperatively controlled by internal diffusion and interface chemical reactions with the activation energy of 30.19 and 16.67 kJ/mol,respectively.The controlling step of the reduction in the final stage(t>40 min)is internal diffusion with the activation energy of 34.60 kJ/mol.The reduction process can be described by two equations obtained from kinetic calculations.The reduction degree can be predicted under different temperatures and time,and the predicted results showed an excellent correlation with the experimental results.The reduction mechanisms were confirmed by the analysis of the scanning electron microscope equipped with an energy dispersive spectrometer and optical microscope.展开更多
Silicomanganese dust contains large amounts of valuables,such as Si and Mn,which can be used as raw materials for the smelting of silicomanganese.However,the direct addition of dust to the submerged arc furnace can in...Silicomanganese dust contains large amounts of valuables,such as Si and Mn,which can be used as raw materials for the smelting of silicomanganese.However,the direct addition of dust to the submerged arc furnace can influence the permeability of burden due to the fine particle size of dust,which results in incomplete reduction reactions during the smelting process.In this paper,silicomanganese dust,graphite powder,and other additives were pressed to form carbon-containing dust briquettes,and the self-reduction process of the dust briquettes was investigated through the isothermal thermogravimetric method with different carbon–oxygen (C/O) molar ratios,contents of fluxing agents,and reduction temperatures.Various reduction kinetic models for dust briquettes at different temperatures were established.The results show that the reaction fraction of the dust briquettes was about 90%at a C/O molar ratio of 1.2 with optimal reduction efficiency.The addition of CaF_(2)contributed to the decrease in the melting point and viscosity of dust briquettes,which increased their reduction rate.As the reduction temperature increased,the reduction rate of dust briquettes increased.The reduction reaction rate of dust briquettes was controlled through gas-phase diffusion.Meanwhile,their reduction process was analyzed kinetically,with the reaction time of 5 min as the dividing line.The apparent activation energies for the two diffusion stages were 56.10 and 100.52 kJ/mol,respectively.The kinetic equations are expressed as[1-(1-f)^(1/3)]^(2)=0.69e^(-56100/(RT))t and [1-(1-f)^(1/3)]^(2)=2.06e^(-100520/(RT))t.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
As a refractory iron ore,the clean and efficient beneficiation of limonite is crucial for ensuring a sustainable long-term supply of iron metal.In this study,the microwave fluidization magnetization roasting of limoni...As a refractory iron ore,the clean and efficient beneficiation of limonite is crucial for ensuring a sustainable long-term supply of iron metal.In this study,the microwave fluidization magnetization roasting of limonite was explored.The micromorphology,microstructure,and mineral phase transformation of the roasted products were analyzed using a scanning electron microscope,an automatic surface area and porosity analyzer,an X-ray diffractometer,and a vibrating sample magnetometer.Kinetic analysis was also conducted to identify the factors limiting the roasting reaction rate.Microwave fluidization roasting significantly increased the specific surface area of limonite,increased the opportunity of contact between CO and limonite,and accelerated the transformation from FeO(OH)toα-Fe_(2)O_(3)and then to Fe_(3)O_(4).In addition,the water in the limonite ore and the newly formed magnetite exhibited a strong microwave absorption capacity,which has a certain activation effect on the reduction roasting of limonite.The saturation magnetization and maximum specific magnetization coefficient increased to 23.08 A·m^(2)·kg^(-1)and 2.50×10^(-4)m^(3)·kg^(-1),respectively.The subsequent magnetic separation of the reconstructed limonite yielded an iron concentrate with an Fe grade of 59.26wt%and a recovery of 90.07wt%.Kinetic analysis revealed that the reaction mechanism function model was consistent with the diffusion model(G(α)=α^(2)),with the mechanism function described as k=0.08208exp[-20.3441/(R_(g)T)].Therefore,microwave fluidization roasting shows significant potential in the beneficiation of limonite,offering a promising approach for the exploitation of refractory iron ores.展开更多
Designing catalysts with high catalytic activity and stability is the key to achieve the commercial application of MgH_(2).Herein,the sulfur doped Ti_(3)C_(2)(S-Ti_(3)C_(2))was successfully prepared by heat treatment ...Designing catalysts with high catalytic activity and stability is the key to achieve the commercial application of MgH_(2).Herein,the sulfur doped Ti_(3)C_(2)(S-Ti_(3)C_(2))was successfully prepared by heat treatment of Ti_(3)C_(2)MXene under Ar/H_(2)S atmosphere to facilitate the hydrogen release and uptake from MgH_(2).The S-Ti_(3)C_(2)exhibited pleasant catalytic effect on the hydriding/dehydriding kinetics and cyclic stability of MgH_(2).The addition of 5 wt%S-Ti_(3)C_(2)into MgH_(2)resulted in a reduction of 114℃in the starting dehydriding temperature compared to pure MgH_(2).MgH_(2)+5 wt%S-Ti_(3)C_(2)sample could quickly release 6.6 wt%hydrogen in 17 min at 220℃,and 6.8 wt%H_(2)was absorbed in 25 min at 200℃.Cyclic testing revealed that MgH_(2)+5 wt%S-Ti_(3)C_(2)system achieved a reversible hydrogen capacity of 6.5 wt%.Characterization analysis demonstrated that Ti-species(Ti0,Ti^(2+),Ti-S,and Ti^(3+))as active species significantly lowered the dehydrogenation temperature and promoted the re-/dehydrogenation kinetics of MgH_(2),and sulfur doping can effectively improve the stability of Ti0 and Ti^(3+),contributing to the improvement of cyclic stability of MgH_(2).This study provides strategy for the construction of catalysts for hydrogen storage materials.展开更多
Accurate prediction of the composition of pyrolysis products is the prerequisite for achieving directional regulation of organic-rich shale pyrolysis and conversion products.In this paper,the classical segmented pyrol...Accurate prediction of the composition of pyrolysis products is the prerequisite for achieving directional regulation of organic-rich shale pyrolysis and conversion products.In this paper,the classical segmented pyrolysis kinetics model and a new refined pyrolysis kinetics model were used to forecast the composition distribution of hydrocarbon generation products co-heated by supercritical water and medium and low maturity organic-rich shale.The prediction accuracy of the two reaction kinetics models for the composition of pyrolysis products of organic-rich shale was compared.The reaction path of hydrocarbon generation in centimeter sized organic-rich shale under the action of supercritical water was identified.The results show that the prediction accuracy of the classical segmented pyrolysis kinetics model was poor at the initial stage of the reaction,and gradually increased with increasing time.The prediction error can reach less than 25%when the reaction time was 12 h.The new refined model of reaction kinetics established is better than the classical reaction kinetics model in predicting the product distribution of pyrolysis oil and gas,and its prediction error is less than 14%in this paper.The reaction paths of hydrocarbon generation in centimeter sized organic-rich shale under supercritical water conversion mainly include organic-rich shale directly generates asphaltene and saturated hydrocarbon,asphaltene pyrolysis generates saturated hydrocarbon,aromatic hydrocarbon and resin,saturated hydrocarbon,aromatic hydrocarbon and resin polymerization generates asphaltene,and saturated hydrocarbon,resin and asphaltene generates gas.The reason for the difference of centimeter sized and millimeter sized medium and low maturity organic-rich shales hydrocarbon generation in supercritical water is that the increase of shale size promotes the reaction path of polymerization of saturated hydrocarbon and aromatic hydrocarbon to asphaltene.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
Long-term responses of floating structures pose a great concern in their design phase. Existing approaches for addressing long-term extreme responses are extremely cumbersome for adoption. This work aims to develop an...Long-term responses of floating structures pose a great concern in their design phase. Existing approaches for addressing long-term extreme responses are extremely cumbersome for adoption. This work aims to develop an approach for the long-term extreme-response analysis of floating structures. A modified gradient-based retrieval algorithm in conjunction with the inverse first-order reliability method(IFORM) is proposed to enable the use of convolution models in long-term extreme analysis of structures with an analytical formula of response amplitude operator(RAO). The proposed algorithm ensures convergence stability and iteration accuracy and exhibits a higher computational efficiency than the traditional backtracking method. However, when the RAO of general offshore structures cannot be analytically expressed, the convolutional integration method fails to function properly. A numerical discretization approach is further proposed for offshore structures in the case when the analytical expression of the RAO is not feasible. Through iterative discretization of environmental contours(ECs) and RAOs, a detailed procedure is proposed to calculate the long-term response extremes of offshore structures. The validity and accuracy of the proposed approach are tested using a floating offshore wind turbine as a numerical example. The long-term extreme heave responses of various return periods are calculated via the IFORM in conjunction with a numerical discretization approach. The environmental data corresponding to N-year structural responses are located inside the ECs, which indicates that the selection of design points directly along the ECs yields conservative design results.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
Tantalum nitride is widely considered as a promising photoanode material for its suitable band structure as well as the high theoretical conversion efficiency in solar water splitting.However,it is limited to ineffici...Tantalum nitride is widely considered as a promising photoanode material for its suitable band structure as well as the high theoretical conversion efficiency in solar water splitting.However,it is limited to inefficient photoinduced electron–hole pair separation and interfacial dynamics in the photoelectrochemical oxygen evolution reaction.Herein,multiple layers including Ti_(x)Si_(y) and NiFeCoO_(x) were fabricated based on band engineering to regulate tandem electric states for efficient transfer of energy carriers.Besides,photothermal local surface plasmon resonance was introduced to accelerate the kinetics of photoelectrochemical reactions at the interface when the special Ag nanoparticles were loaded to extend the absorbance to near infrared light.Consequently,a recordable photocurrent density of 12.73 mA cm^(-2) has been achieved at 1.23 V versus RHE,approaching a theoretical limit of the tantalum nitride photoanode with full-spectrum solar utilization.Meanwhile,compared to the applied bias photon-to-current efficiency of 1.36%without photothermal factor,a high applied bias photonto-current efficiency of 2.27%could be raised by applying local surface plasmon resonance to photoelectrochemical oxygen evolution reaction.The efficient design could maximize the use of solar light via the classification of spectrum and,therefore,may spark more innovative ideas for the future design and development of the next-generation photoelectrode.展开更多
基金Projects [2006]331 supported by the Scientific Research Foundation for the Returned Overseas Chinese Scholars070712 by the Key Laboratory ofNuclear Resources and Environment,Ministry of Education of China
文摘The use of peat for the removal of nickel from aqueous solutions has been investigated at various pH values by means of static conditions. The present research shows that the ability of Ni to bind to peat increases as the pH value increases. The solutions reach adsorption equilibrium rapidly. A reasonable kinetic model, first-order in nickel concentration, has been developed and fitted to the adsorption of nickel （Ⅱ） onto peat. The first-order model provides a good correlation to the experimental data. The characteristic parameters of the Langmuir isotherm were determined at various temperatures. The relationship between kinetics and equilibrium isotherms was established through the forward- and backward-rate-constants, k~ and k2, and the equilibrium constant, K.
基金the Specialized Research Fund for the Doctoral Program of Higher Education(No.20050027002)。
文摘This investigation was carried out to establish a new domestic landfill gas(LFG)generation rate model that takes into account the impact of leachate recirculation.The first-order kinetics and two-stage reaction(FKTSR)model of the LFG generation rate includes mechanisms of the nutrient balance for biochemical reaction in two main stages.In this study,the FKTSR model was modified by the introduction of the outflow function and the organic acid conversion coefficient in order to represent the in-situ condition of nutrient loss through leachate.Laboratory experiments were carried out to simulate the impact of leachate recirculation and verify the modified FKTSR model.The model calibration was then calculated by using the experimental data.The results suggested that the new model was in line with the experimental data.The main parameters of the modified FKTSR model,including the LFG production potential(L0),the reaction rate constant in the first stage(K1),and the reaction rate constant in the second stage(K2)of 64.746 L,0.202 d^(–1),and 0.338 d^(–1),respectively,were comparable to the old ones of 42.069 L,0.231 d^(–1),and 0.231 d^(–1).The new model is better able to explain the mechanisms involved in LFG generation.
基金supported by the National Natural Science Foundation of China(No.52271089)the financial support from the C hina Postdoctoral Science Foundation(No.2023M732192)。
文摘This work reveals the significant effects of cobalt(Co)on the microstructure and impact toughness of as-quenched highstrength steels by experimental characterizations and thermo-kinetic analyses.The results show that the Co-bearing steel exhibits finer blocks and a lower ductile-brittle transition temperature than the steel without Co.Moreover,the Co-bearing steel reveals higher transformation rates at the intermediate stage with bainite volume fraction ranging from around 0.1 to 0.6.The improved impact toughness of the Co-bearing steel results from the higher dense block boundaries dominated by the V1/V2 variant pair.Furthermore,the addition of Co induces a larger transformation driving force and a lower bainite start temperature(BS),thereby contributing to the refinement of blocks and the increase of the V1/V2 variant pair.These findings would be instructive for the composition,microstructure design,and property optimization of high-strength 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National Natural Science Foundation of China(52275328,51875157)。
文摘Hydrogen desorption kinetics and characteristics,residual hydrogen content and activation energy of TC21 alloy were investigated by the constant volume method.Results show that hydrogen desorption temperature and initial hydrogen pressure affect hydrogen desorption characteristics of TC21 alloy.The hydrogen desorption process is mainly dominated by nucleation and growth process(kt=[-ln(1-α)]^(2/3)),chemical reaction process(kt=(1-α)^(-1/2))and three-dimensional diffusion process(kt=[1-(1-α)^(1/3)]^(1/2))when the hydrogenated TC21 alloy is dehydrogenated at temperatures of 700-940°C.When the hydrogenated TC21 alloy releases hydrogen,the following relationship exists among the rate constants of each process:k(chemical reaction process)>k(nucleation and growth process)>k(three-dimensional diffusion process).The residual hydrogen content of the hydrogenated TC21 alloy after hydrogen desorption decreases gradually with the increase in hydrogen desorption temperature,and increases gradually with the increase in the initial hydrogen pressure.The activation energy of TC21 alloy in the process of hydrogen desorption is about 26.663 kJ/mol.
文摘In this paper,we present a novel first-order digitalΣΔconverter tailored for digital-to-analog applications,focusing on achieving both high yield and reduced silicon estate.Our approach incorporates a substantial level of dithering noise into the input signal,strategically aimed at mitigating the spurious frequencies commonly encountered in such converters.Validation of our design is performed through simulations using a high-level simulator specialized in mixed-signal circuit analysis.The results underscore the enhanced performance of our circuit,especially in reducing spurious frequencies,highlighting its efficiency and effectiveness.The final circuit exhibits an effective number of bits of 13.
基金supported by the National Key Research&Development Program of China(2021YFB3803200)the National Natural Science Foundation of China(22288102).
文摘Hexafluoropropylene oxide(HFPO)is a crucial fluorinated chemical mainly synthesized from hexafluoropropylene(HFP)through the oxidation of oxygen.However,the reaction network and kinetic characteristics are not fully understood yet,resulting in a lack of theoretical basis for synthesis process improvement.Here,the free radical reaction mechanism and complete reaction network involved in the noncatalytic oxidation of HFP to synthesize HFPO was explored by density functional theory.Transition state theory was employed to calculate the intrinsic reaction rate constants for elementary reactions.Based on theoretical reaction rate ratios,reaction pathways were selected,and a simplified reaction network was derived.It was found that byproducts were formed owing to the decomposition of HFPO and subsequent reactions with excessive oxygen while oxygen tended to participate more in the main reaction under oxygen-deficient conditions.The variations in reaction pathways occurring at different HFP/oxygen molar ratios was well elucidated by comparing with experimental data.This research establishes a robust theoretical foundation for optimizing and regulating the synthesis of HFPO.
基金financial support from the National Natural Science Foundation of China(NSFC No.52202253,52072173)Natural Science Foundation of Jiangsu Province(No.BK20220914)+1 种基金Fundamental Research Funds for the Central Universities(No.ILA22061,ILA22075)Large Instrument and Equipment Sharing Fund of NUAA.
文摘Intuitively,the solvation structure featuring stronger interacted sheath in deep eutectic solution(DES)electrolyte would result in sluggish interfacial charge transfer and intense polarization,which obstructs its practical application in emerging Zn based batteries.Unexpectedly,here we discover a Zn‖organic battery with exceptional kinetics properties enabled by a hydrated DES electrolyte,which can render higher discharge capacity,smaller voltage polarization,and faster kinetics of charge transfer in comparison with conventional aqueous 3 M ZnCl_(2)electrolyte,though its viscosity is two orders of magnitude higher than the latter.The improved kinetics of charge transfer and ion diffusion is demonstrated to originate from the local electron structure regulation of cathode in hydrated DES electrolyte.Furthermore,the DES electrolyte has also been shown to restrict parasitic reaction associated with active water by preferential urea-molecular adsorption on Zn surface and stronger water trapping in solvation structure,giving rise to long-term stable dendrite-free Zn plating/stripping.This work provides a new rationale for understanding electrochemical behaviors of organic cathodes in DES electrolyte,which is conducive to the development of high-performance Zn‖organic batteries.
基金National Key Research and Development Program of China(No.2022YFC2904900)the National Natural Science Foundation of China(No.U1902221).
文摘The erosion process and kinetics of PbTe particles in a selenium melt were investigated.The results reveal that the limiting step of the reaction is controlled by product layer diffusion and the interfacial chemical reaction at low temperatures(573,583,and 593 K),but the limiting step is controlled by boundary layer diffusion at high temperatures(603 and 613 K).The Se-and Te-atom diffusion in the product layer becomes unbalanced as the product layer thickens,with Kirkendall voids generating in the product layer accelerating PbTe particle erosion.After the PbTe impurities in the selenium melt evolve into PbSe and Te,Te is evenly distributed in the selenium melt owing to the solubility of Se and Te.This study serves to clarify the evolution behavior of PbTe impurities in the selenium melt and the reason that Te often occurs in Se.
基金financially supported by the National Natural Science Foundation of China(Nos.52204331 and 52374315)the Major Industrial Innovation Plan of Anhui Provincial Development and the Reform Commission,China(No.AHZDCYCX-LSDT2023-01)。
文摘Al_(2)O_(3)and MgO serve as the primary gangue components in sintered ores,and they are critical for the formation of CaO-Fe_(2)O_(3)-xAl_(2)O_(3)(wt%,C-F-xA)and CaO-Fe_(2)O_(3)-xM gO(wt%,C-F-xM)systems,respectively.In this study,a nonisothermal crystallization thermodynamics behavior of C-F-xA and C-F-xM systems was examined using differential scanning calorimetry,and a phase identification and microstructure analysis for C-F-xA and C-F-xM systems were carried out by X-ray diffraction and scanning electron microscopy.Results showed that in C-F-2A and C-F-2M systems,the increased cooling rates promoted the precipitation of CaFe_(2)O_(4)(CF)but inhibited the formation of Ca_(2)Fe_(2)O_(5)(C2F).In addition,C-F-2A system exhibited a lower theoretical initial crystallization temperature(1566 K)compared to the C-F system(1578 K).This temperature further decreases to 1554 K and 1528 K in the C-F-4A and C-F-8A systems,respectively.However,in C-F-xM system,the increased MgO content raised the crystallization temperature.This is because that the enhanced precipitation of MF(a spinel phase mainly comprised Fe_(3)O_(4)and MgFe_(2)O_(4))and C2F phases suppressed the CF precipitation reaction.In kinetic calculations,the Ozawa method revealed the apparent activation energies of the C-F-2A and C-F-2M systems.Malek's method revealed that the crystallization process in C-F-2A system initially followed a logarithmic law(lnαor lnα2),later transitioning to a reaction order law((1-α)-1or(1-α)^(-1/2),n=2/3)or the lnα2function of the exponential law.In C-F-2M system,it consistently followed the sequencef(α)=(1-α)^(2)(αis the crystallization conversion rate;n is the Avrami constant;?(α)is the differential equations for the model function of C_(2)F and CF crystallization processes).
基金support from the National Natural Science Foundation of China(No.52174300)Natural Science Foundation of Chongqing,China(Nos.cstc2020jcyj-msxmX0583 and cstc2021jcyj-msxmX1004)+1 种基金Chongqing Talent Plan Project(No.cstc2021ycjh-bgzxm0211)Chongqing Doctoral"Through Train"Project(No.sl202100000343).T。
文摘Iron ore pellets,as one of the main charges of blast furnaces,have a greater impact on the CO_(2)emission reduction and stable operation of blast furnaces.The isothermal reduction behavior of the pellets obtained from a Chinese steel plant was studied in the gas mixtures of CO and N_(2).The results showed the reduction process is divided into two stages.The reduction in the initial stage(time t≤40 min)is cooperatively controlled by internal diffusion and interface chemical reactions with the activation energy of 30.19 and 16.67 kJ/mol,respectively.The controlling step of the reduction in the final stage(t>40 min)is internal diffusion with the activation energy of 34.60 kJ/mol.The reduction process can be described by two equations obtained from kinetic calculations.The reduction degree can be predicted under different temperatures and time,and the predicted results showed an excellent correlation with the experimental results.The reduction mechanisms were confirmed by the analysis of the scanning electron microscope equipped with an energy dispersive spectrometer and optical microscope.
基金financially supported by the Hubei Provincial Key Laboratory for New Processes of Ironmaking and Steelmaking (No. KF-20-3)Shandong Postdoctoral Science Foundation, China (No. SDCX-ZG-202301014)。
文摘Silicomanganese dust contains large amounts of valuables,such as Si and Mn,which can be used as raw materials for the smelting of silicomanganese.However,the direct addition of dust to the submerged arc furnace can influence the permeability of burden due to the fine particle size of dust,which results in incomplete reduction reactions during the smelting process.In this paper,silicomanganese dust,graphite powder,and other additives were pressed to form carbon-containing dust briquettes,and the self-reduction process of the dust briquettes was investigated through the isothermal thermogravimetric method with different carbon–oxygen (C/O) molar ratios,contents of fluxing agents,and reduction temperatures.Various reduction kinetic models for dust briquettes at different temperatures were established.The results show that the reaction fraction of the dust briquettes was about 90%at a C/O molar ratio of 1.2 with optimal reduction efficiency.The addition of CaF_(2)contributed to the decrease in the melting point and viscosity of dust briquettes,which increased their reduction rate.As the reduction temperature increased,the reduction rate of dust briquettes increased.The reduction reaction rate of dust briquettes was controlled through gas-phase diffusion.Meanwhile,their reduction process was analyzed kinetically,with the reaction time of 5 min as the dividing line.The apparent activation energies for the two diffusion stages were 56.10 and 100.52 kJ/mol,respectively.The kinetic equations are expressed as[1-(1-f)^(1/3)]^(2)=0.69e^(-56100/(RT))t and [1-(1-f)^(1/3)]^(2)=2.06e^(-100520/(RT))t.
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financially supported by the National Key Research and Development Program of China(No.2021YFC2901000)the National Natural Science Foundation of China(No.52104249)+1 种基金the Liaoning Joint Fund General Support Program Project(No.2023-MSBA-126)the Fundamental Research Funds for the Central Universities(No.N2401019)。
文摘As a refractory iron ore,the clean and efficient beneficiation of limonite is crucial for ensuring a sustainable long-term supply of iron metal.In this study,the microwave fluidization magnetization roasting of limonite was explored.The micromorphology,microstructure,and mineral phase transformation of the roasted products were analyzed using a scanning electron microscope,an automatic surface area and porosity analyzer,an X-ray diffractometer,and a vibrating sample magnetometer.Kinetic analysis was also conducted to identify the factors limiting the roasting reaction rate.Microwave fluidization roasting significantly increased the specific surface area of limonite,increased the opportunity of contact between CO and limonite,and accelerated the transformation from FeO(OH)toα-Fe_(2)O_(3)and then to Fe_(3)O_(4).In addition,the water in the limonite ore and the newly formed magnetite exhibited a strong microwave absorption capacity,which has a certain activation effect on the reduction roasting of limonite.The saturation magnetization and maximum specific magnetization coefficient increased to 23.08 A·m^(2)·kg^(-1)and 2.50×10^(-4)m^(3)·kg^(-1),respectively.The subsequent magnetic separation of the reconstructed limonite yielded an iron concentrate with an Fe grade of 59.26wt%and a recovery of 90.07wt%.Kinetic analysis revealed that the reaction mechanism function model was consistent with the diffusion model(G(α)=α^(2)),with the mechanism function described as k=0.08208exp[-20.3441/(R_(g)T)].Therefore,microwave fluidization roasting shows significant potential in the beneficiation of limonite,offering a promising approach for the exploitation of refractory iron ores.
基金supported by the National Natural Science Foundation of China(U22A20120,52071135,51871090,U1804135,and 52301269)the Natural Science Foundation of Hebei Province for Innovation Groups Program(C2022203003)Fundamental Research Funds for the Universities of Henan Province(NSFRF220201).
文摘Designing catalysts with high catalytic activity and stability is the key to achieve the commercial application of MgH_(2).Herein,the sulfur doped Ti_(3)C_(2)(S-Ti_(3)C_(2))was successfully prepared by heat treatment of Ti_(3)C_(2)MXene under Ar/H_(2)S atmosphere to facilitate the hydrogen release and uptake from MgH_(2).The S-Ti_(3)C_(2)exhibited pleasant catalytic effect on the hydriding/dehydriding kinetics and cyclic stability of MgH_(2).The addition of 5 wt%S-Ti_(3)C_(2)into MgH_(2)resulted in a reduction of 114℃in the starting dehydriding temperature compared to pure MgH_(2).MgH_(2)+5 wt%S-Ti_(3)C_(2)sample could quickly release 6.6 wt%hydrogen in 17 min at 220℃,and 6.8 wt%H_(2)was absorbed in 25 min at 200℃.Cyclic testing revealed that MgH_(2)+5 wt%S-Ti_(3)C_(2)system achieved a reversible hydrogen capacity of 6.5 wt%.Characterization analysis demonstrated that Ti-species(Ti0,Ti^(2+),Ti-S,and Ti^(3+))as active species significantly lowered the dehydrogenation temperature and promoted the re-/dehydrogenation kinetics of MgH_(2),and sulfur doping can effectively improve the stability of Ti0 and Ti^(3+),contributing to the improvement of cyclic stability of MgH_(2).This study provides strategy for the construction of catalysts for hydrogen storage materials.
基金support by the Basic Science Center Program of the Ordered Energy Conversion of the National Nature Science Foundation of China(NO.52488201)is gratefully acknowledged.
文摘Accurate prediction of the composition of pyrolysis products is the prerequisite for achieving directional regulation of organic-rich shale pyrolysis and conversion products.In this paper,the classical segmented pyrolysis kinetics model and a new refined pyrolysis kinetics model were used to forecast the composition distribution of hydrocarbon generation products co-heated by supercritical water and medium and low maturity organic-rich shale.The prediction accuracy of the two reaction kinetics models for the composition of pyrolysis products of organic-rich shale was compared.The reaction path of hydrocarbon generation in centimeter sized organic-rich shale under the action of supercritical water was identified.The results show that the prediction accuracy of the classical segmented pyrolysis kinetics model was poor at the initial stage of the reaction,and gradually increased with increasing time.The prediction error can reach less than 25%when the reaction time was 12 h.The new refined model of reaction kinetics established is better than the classical reaction kinetics model in predicting the product distribution of pyrolysis oil and gas,and its prediction error is less than 14%in this paper.The reaction paths of hydrocarbon generation in centimeter sized organic-rich shale under supercritical water conversion mainly include organic-rich shale directly generates asphaltene and saturated hydrocarbon,asphaltene pyrolysis generates saturated hydrocarbon,aromatic hydrocarbon and resin,saturated hydrocarbon,aromatic hydrocarbon and resin polymerization generates asphaltene,and saturated hydrocarbon,resin and asphaltene generates gas.The reason for the difference of centimeter sized and millimeter sized medium and low maturity organic-rich shales hydrocarbon generation in supercritical water is that the increase of shale size promotes the reaction path of polymerization of saturated hydrocarbon and aromatic hydrocarbon to asphaltene.
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Supported by the National Natural Science Foundation of China (Grant Nos.52088102 and 51879287)National Key Research and Development Program of China (Grant No.2022YFB2602301)。
文摘Long-term responses of floating structures pose a great concern in their design phase. Existing approaches for addressing long-term extreme responses are extremely cumbersome for adoption. This work aims to develop an approach for the long-term extreme-response analysis of floating structures. A modified gradient-based retrieval algorithm in conjunction with the inverse first-order reliability method(IFORM) is proposed to enable the use of convolution models in long-term extreme analysis of structures with an analytical formula of response amplitude operator(RAO). The proposed algorithm ensures convergence stability and iteration accuracy and exhibits a higher computational efficiency than the traditional backtracking method. However, when the RAO of general offshore structures cannot be analytically expressed, the convolutional integration method fails to function properly. A numerical discretization approach is further proposed for offshore structures in the case when the analytical expression of the RAO is not feasible. Through iterative discretization of environmental contours(ECs) and RAOs, a detailed procedure is proposed to calculate the long-term response extremes of offshore structures. The validity and accuracy of the proposed approach are tested using a floating offshore wind turbine as a numerical example. The long-term extreme heave responses of various return periods are calculated via the IFORM in conjunction with a numerical discretization approach. The environmental data corresponding to N-year structural responses are located inside the ECs, which indicates that the selection of design points directly along the ECs yields conservative design results.
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financially supported by the Zhejiang Provincial Natural Science Foundation of China under Grant No.LQ24E060001the National Key Research and Development Project(2023YFC3710800)+2 种基金the National Natural Science Foundation of China under Grant No.52341602supported by funding from the Canada First Research Excellence Fund(CFRER-2015-00001)the University of Alberta’s Future Energy Systems research initiative(FES-T02-P03)。
文摘Tantalum nitride is widely considered as a promising photoanode material for its suitable band structure as well as the high theoretical conversion efficiency in solar water splitting.However,it is limited to inefficient photoinduced electron–hole pair separation and interfacial dynamics in the photoelectrochemical oxygen evolution reaction.Herein,multiple layers including Ti_(x)Si_(y) and NiFeCoO_(x) were fabricated based on band engineering to regulate tandem electric states for efficient transfer of energy carriers.Besides,photothermal local surface plasmon resonance was introduced to accelerate the kinetics of photoelectrochemical reactions at the interface when the special Ag nanoparticles were loaded to extend the absorbance to near infrared light.Consequently,a recordable photocurrent density of 12.73 mA cm^(-2) has been achieved at 1.23 V versus RHE,approaching a theoretical limit of the tantalum nitride photoanode with full-spectrum solar utilization.Meanwhile,compared to the applied bias photon-to-current efficiency of 1.36%without photothermal factor,a high applied bias photonto-current efficiency of 2.27%could be raised by applying local surface plasmon resonance to photoelectrochemical oxygen evolution reaction.The efficient design could maximize the use of solar light via the classification of spectrum and,therefore,may spark more innovative ideas for the future design and development of the next-generation photoelectrode.
