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Thermodynamic theory of flotation for a complex multiphase solid -liquid system and high-entropy flotation

International Journal of Minerals,metallurgy and Materials 2024年第6期31卷 1177-1197页

作者： Shuming Wen state key laboratory of complex nonferrous metal resources clean utilization Faculty of Land Resource EngineeringKunming University of Science and TechnologyKunming 650093China

The flotation of complex solid–liquid multiphase systems involve interactions among multiple components,the core problem facing flotation theory.Meanwhile,the combined use of multicomponent flotation reagents to improve mineral flotation has become an important issue in studies on the efficient use of refractory mineral resources.However,studying the flotation of complex solid–liquid systems is extremely difficult,and no systematic theory has been developed to date.In addition,the physical mechanism associated with combining reagents to improve the flotation effect has not been unified,which limits the development of flotation theory and the progress of flotation technology.In this study,we applied theoretical thermodynamics to a solid–liquid flotation system and used changes in the entropy and Gibbs free energy of the reagents adsorbed on the mineral surface to establish thermodynamic equilibrium equations that de-scribe interactions among various material components while also introducing adsorption equilibrium constants for the flotation reagents adsorbed on the mineral surface.The homogenization effect on the mineral surface in pulp solution was determined using the chemical potentials of the material components of the various mineral surfaces required to maintain balance.The flotation effect can be improved through synergy among multicomponent flotation reagents;its physical essence is the thermodynamic law that as the number of compon-ents of flotation reagents on the mineral surface increases,the surface adsorption entropy change increases,and the Gibbs free energy change of adsorption decreases.According to the results obtained using flotation thermodynamics theory,we established high-entropy flotation theory and a technical method in which increasing the types of flotation reagents adsorbed on the mineral surface,increasing the adsorption entropy change of the flotation reagents,decreasing the Gibbs free energy change,and improving the adsorption efficiency and stability of the flotation reagents improve

关键词： multicomponent flotation reagent adsorption entropy change equations of thermodynamic equilibrium adsorption equilibri-um constant high-entropy flotation

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Numerical investigation of sinusoidal pulsating gas intake to intensify the gas-slag momentum transfer in the top-blown smelting furnace

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International Journal of Minerals,metallurgy and Materials 2024年第2期31卷 301-314页

作者： Zhanghao Wan Shiliang Yang Desong Kong Dongbo Li Jianhang Hu Hua Wang state key laboratory of complex nonferrous metal resources clean utilization Kunming University of Science and TechnologyKunming 650093China Southwest Copper Branch Yunnan Copper Co.Ltd.Kunming 650102China

The variation characteristics of bubble morphology and the thermal-physical properties of bubble boundary in the top-blown smelting furnace were explored by means of the computational fluid dynamics method.The essential aspects of the fluid phase(e.g.,splashing volume,dead zone of copper slag,and gas penetration depth)were explored together with the effect of sinusoidal pulsating gas intake on the momentum-transfer performance between phases.The results illustrated that two relatively larger vortices and two smaller vortices appear in the bubble waist and below the lance,respectively.The expansion of larger ones as well as the shrinking of smaller ones combine to cause the contraction of the bubble waist.Compared to the results of the case with a fixed gas injection velocity(V_(g)=58 m/s),the splashing volume and dead zone volume of the slag under the V_(g)=58+10sin(2πt)condition are reduced by 24.9%and 23.5%,respectively,where t represents the instant time.Gas penetration depth and slag motion velocity of the latter are 1.03 and 1.31 times high-er than those of the former,respectively.

关键词： top-blown smelting furnace pulsed flow volume of fluid penetration depth splashing volume

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Advances in depressants for flotation separation of Cu–Fe sulfide minerals at low alkalinity:A critical review

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International Journal of Minerals,metallurgy and Materials 2024年第1期31卷 1-17页

作者： Qicheng Feng Wenhang Yang Maohan Chang Shuming Wen Dianwen Liu Guang Han state key laboratory of complex nonferrous metal resources clean utilization Faculty of Land Resource EngineeringKunming University of Science and TechnologyKunming 650093China Yunnan key laboratory of Green Separation and Enrichment of Strategic Mineral resources Kunming University of Science and TechnologyKunming 650093China

The flotation separation of Cu–Fe sulfide minerals at low alkalinity can be achieved using selective depressants.In the flotation system of Cu–Fe sulfide minerals,depressants usually preferentially interact with the pyrite surface to render the mineral surface hydrophilic and hinder the adsorption of the collector.This review summarizes the advances in depressants for the flotation separation of Cu–Fe sulfide minerals at low alkalinity.These advances include use of inorganic depressants (oxidants and sulfur–oxygen compounds),natural polysaccharides (starch,dextrin,konjac glucomannan,and galactomannan),modified polymers (carboxymethyl cellulose,polyacrylamide,lignosulfonate,and tricarboxylate sodium starch),organic acids (polyglutamic acid,sodium humate,tannic acid,pyrogallic acid,salicylic acid,and lactic acid),sodium dimethyl dithiocarbamate,and diethylenetriamine.The potential application of specific inorganic and organic depressants in the flotation separation of Cu–Fe sulfide minerals at low alkalinity is reviewed.The advances in the use of organic depressants with respect to the flotation separation of Cu–Fe sulfide minerals are comprehensively detailed.Additionally,the depression performances and mechanisms of different types of organic depressants on mineral surfaces are summarized.Finally,several perspectives on depressants vis-à-vis flotation separation of Cu–Fe sulfide minerals at low alkalinity are proposed.

关键词： Cu–Fe sulfide minerals flotation separation selective depressants depression mechanism

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Numerical simulation of granular silicon growth and silicon fines formation process in polysilicon fluidized bed

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Particuology 2024年第4期87卷 74-86页

作者： Guangkai Gu Guoqiang Lv Wenhui Ma Shanlin Du Boqiang Fu Faculty of metallurgical and Energy Engineering Kunming University of Science and TechnologyKunming 650093China state key laboratory of complex nonferrous metal resources cleaning utilization in Yunnan Province Kunming 650093China

Operating conditions strongly affect the yield and quality of polysilicon in a polysilicon fluidized bed.In this study,a new model of polysilicon fluidized bed was established using the Euler-Euler model coupled with population balance model(PBM),which was combined with fluid flow,heat,and mass transfer models,while considering the scavenging effect of silicon fines.The effects of different operating conditions on the deposition and formation rates of silicon fines were investigated.Results show that the model can correctly describe the particle growth process in the fluidized bed of polysilicon.The silicon fines and the interphase velocity difference show"N"-and"M"-shaped distributions along the axial direction,respectively.The particle temperature and concentration near the wall are higher than those in the central region.The decomposition of silane in the bottom region of the bed is dominated by het-erogeneous deposition.The scavenging of silicon fines occurs in the dilute-phase region.The effects of operating conditions,i.***.inlet gas temperature,silane composition,and gas velocity,on the reactor performance were also explored comprehensively.Increasing the inlet gas composition and velocity enhances the formation rates of solid silicon and fines.Increasing the inlet gas temperature promotes the growth of solid silicon and inhibits the formation of silicon fines.High fluidization ratio,low inlet silane concentration,and high inlet gas temperature enhance the selectivity of silicon growth.

关键词： Polysilicon fluidized bed Particle growth Fines CFD Population balance model(PBM)

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Flotation separation of scheelite from calcite using luteolin as a novel depressant

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International Journal of Minerals,metallurgy and Materials 2024年第3期31卷 462-472页

作者： Xiaokang Li Ying Zhang Haiyang He Yu Wu Danyu Wu Zhenhao Guan Faculty of Land and resources Engineering Kunming University of Science and TechnologyKunming 650093China state key laboratory of clean utilization of complex Non-Ferrous metal resources Kunming University of Science and TechnologyKunming 650093China

This paper proposes luteolin(LUT)as a novel depressant for the flotation-based separation of scheelite and calcite in a sodium oleate(NaOL)system.The suitability of LUT as a calcite depressant is confirmed through micro-flotation testing.At pH=9,with LUT concentration of 50 mg·L^(-1) and NaOL concentration of 50 mg·L^(-1),scheelite recovery reaches 80.3%.Calcite,on the other hand,exhibits a recovery rate of 17.6%,indicating a significant difference in floatability between the two minerals.Subsequently,the surface modifica-tions of scheelite and calcite following LUT treatment are characterized using adsorption capacity testing,Zeta potential analysis,Fourier transform infrared spectroscopy(FT-IR),X-ray photoelectron spectroscopy(XPS),and atomic force microscopy(AFM).The study in-vestigates the selective depressant mechanism of LUT on calcite.Adsorption capacity testing and Zeta potential analysis demonstrate sub-stantial absorption of LUT on the surface of calcite,impeding the further adsorption of sodium oleate,while its impact on scheelite is min-imal.FT-IR and XPS analyses reveal the selective adsorption of LUT onto the surface of calcite,forming strong chemisorption bonds between the hydroxyl group and calcium ions present.AFM directly illustrates the distinct adsorption densities of LUT on the two miner-al types.Consequently,LUT can effectively serve as a depressant for calcite,enabling the successful separation of scheelite and calcite.

关键词： scheelite calcite luteolin flotation depressant separation

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Promoting effect of FeOx addition on the mechanochemically prepared vanadium-based catalyst for real PCDD/Fs removal and mechanism insight

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Journal of Environmental Sciences 2024年第3期137卷 478-487页

作者： Minghui Tang Ling Wang Hongxian Li Xinlei Huang Cuicui Du Shengyong Lu state key laboratory for clean Energy utilization Institute for Thermal Power EngineeringZhejiang UniversityHangzhou 310027China

Industrial-use VOx-based catalysts usually have a higher active temperature window (>250-300℃),which becomes a“bottleneck”for the practical application of PCDD/Fs catalytic degradation technology.In this work,VO_(x)-FeO_(x)/TiO_(2) catalyst prepared via mechanochemically method was investigated for the catalytic removal of PCDD/Fs.The removal efficiency of 1,2-DCBz,pure PCDD/Fs gas generated in the lab,PCDD/Fs from actual fue gas,long-term were studied,and the degradation mechanism was explored using FTIR and TOFMS.The degradation efficiency of 1,2-DCBz and PCDD/Fs on VO_(x)-FeO_(x)/TiO_(2) were higher than that of VO_(x)/TiO_(2)catalyst,and the optimal FeOx addition ratio was 3 wt.%.The characterization results show that the addition of FeOx can effectively improve the pore structure,surface acidity,and VOx dispersion of the catalyst,thus contributing to increasing the V^(5+)content and surface-active oxygen,which is conducive to the improvement of adsorption and redox performance of the catalyst.Under the actual MSWI (municipal solid waste incineration)fue gas,the PCDD/Fs removal efficiency over VTi-3Fe-MC maintained long-term stability,higher than 85%for 240 min.This result was not significantly reduced compared with the data obtained in the laboratory.According to the analysis results of intermediate products by FTIR and GC-TOFMS,it can be inferred that the epoxidation fracture of benzene ring is the rate-limiting step of dioxin catalytic degradation reaction.This work gives an in-depth view into the PCDD/Fs removal over VO_(x)-FeO_(x)/TiO_(2) catalysts and could provide guidelines for the rational design of reliable catalysts for industrial applications.

关键词： PCDD/F removal MSWI fue gas VO_(x)-FeO_(x)/TiO_(2) Mechanochemical GC-TOFMS

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Recent advances in cobalt phosphide-based materials for electrocatalytic water splitting:From catalytic mechanism and synthesis method to optimization design

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Nano Materials Science 2024年第2期6卷 139-173页

作者： Rongrong Deng Mengwei Guo Chaowu Wang Qibo Zhang key laboratory of Ionic Liquids metallurgy Faculty of Metallurgical and Energy EngineeringKunming University of Science and TechnologyKunming650093PR China state key laboratory of complex nonferrous metal resources cleaning utilization in Yunnan Province Kunming650093PR China

Electrochemical water splitting has long been considered an effective energy conversion technology for trans-ferring intermittent renewable electricity into hydrogen fuel,and the exploration of cost-effective and high-performance electrocatalysts is crucial in making electrolyzed water technology commercially viable.Cobalt phosphide(Co-P)has emerged as a catalyst of high potential owing to its high catalytic activity and durability in water splitting.This paper systematically reviews the latest advances in the development of Co-P-based materials for use in water splitting.The essential effects of P in enhancing the catalytic performance of the hydrogen evolution reaction and oxygen evolution reaction are first outlined.Then,versatile synthesis techniques for Co-P electrocatalysts are summarized,followed by advanced strategies to enhance the electrocatalytic performance of Co-P materials,including heteroatom doping,composite construction,integration with well-conductive sub-strates,and structure control from the viewpoint of experiment.Along with these optimization strategies,the understanding of the inherent mechanism of enhanced catalytic performance is also discussed.Finally,some existing challenges in the development of highly active and stable Co-P-based materials are clarified,and pro-spective directions for prompting the wide commercialization of water electrolysis technology are proposed.

关键词： Co-P electrocatalysts Water splitting Hydrogen production Catalytic mechanism Synthesis technique Optimization design

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Growth and inhibition of zinc anode dendrites in Zn-air batteries:Model and experiment

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Chinese Journal of Chemical Engineering 2024年第3期67卷 268-281页

作者： Cuiping He Qingyi Gou Yanqing Hou Jianguo Wang Xiang You Ni Yang Lin Tian Gang Xie Yuanliang Chen Kunming University of Science and Technology State Key Laboratory of Complex Nonferrous Metal Resources Clean UtilizationKunming 650093China Kunming University of Science and Technology Faculty of Metallurgical and Energy EngineeringKunming 650093China China Copper Co.Ltd KunmingYunnan 650051China state key laboratory of Advanced metallurgy for Non-ferrous metals Kunming 650051China Sichuan Shunying Power Battery Materials Co.Ltd Sichuan 620076China

Zinc(Zn)-air batteries are widely used in secondary battery research owing to their high theoretical energy density,good electrochemical reversibility,stable discharge performance,and low cost of the anode active material Zn.However,the Zn anode also leads to many challenges,including dendrite growth,deformation,and hydrogen precipitation self-corrosion.In this context,Zn dendrite growth has a greater impact on the cycle lives.In this dissertation,a dendrite growth model for a Zn-air battery was established based on electrochemical phase field theory,and the effects of the charging time,anisotropy strength,and electrolyte temperature on the morphology and growth height of Zn dendrites were studied.A series of experiments was designed with different gradient influencing factors in subsequent experiments to verify the theoretical simulations,including elevated electrolyte temperatures,flowing electrolytes,and pulsed charging.The simulation results show that the growth of Zn dendrites is controlled mainly by diffusion and mass transfer processes,whereas the electrolyte temperature,flow rate,and interfacial energy anisotropy intensity are the main factors.The experimental results show that an optimal electrolyte temperature of 343.15 K,an optimal electrolyte flow rate of 40 ml·min^(-1),and an effective pulse charging mode.

关键词： Zn-air battery Zinc anode Zinc dendrite Simulated dendrite growth Inhibit dendrite growth Phase-field model

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Improving anammox activity and reactor start-up speed by using CO_(2)/NaHCO_(3) buffer

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Journal of Environmental Sciences 2024年第5期139卷 60-71页

作者： Shaoan Cheng Huahua Li Xinyuan He Hua Chen Longxin Li state key laboratory of clean Energy utilization College of Energy EngineeringZhejiang UniversityHangzhou 310027China

Anammox bacteria grow slowly and can be affected by large pH fluctuations.Using suitable buffers could make the start-up of anammox reactors easy and rapid.In this study,the effects of three kinds of buffers on the nitrogen removal and growth characteristics of anammox sludge were investigated.Reactors with CO_(2)/NaHCO_(3)buffer solution(CCBS)performed the best in nitrogen removal,while 4-(2-hydroxyerhyl)piperazine-1-ethanesulfonic acid(HEPES)and phosphate buffer solution(PBS)inhibited the anammox activity.Reactors with 50 mmol/L CCBS could start up in 20 days,showing the specific anammox activity and anammox activity of 1.01±0.10 gN/(gVSS·day)and 0.83±0.06 kgN/(m^(3)·day),respectively.Candidatus Kuenenia was the dominant anammox bacteria,with a relative abundance of 71.8%.Notably,anammox reactors could also start quickly by using 50 mmol/L CCBS under nonstrict anaerobic conditions.These findings are meaningful for the quick start-up of engineered anammox reactors and prompt enrichment of anammox bacteria.

关键词： Anammox bacteria Buffer solution CO_(2)/NaHCO_(3) Physiological characteristics Microbial community shift

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Experimental Investigation and X-Ray Computed Microtomography Simulation on Thermal Physical Properties of Foundation Materials after Molten Salt Leakage in the Storage Tank

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Journal of Thermal Science 2024年第2期33卷 591-601页

作者： WANG Zhaowen ZHOU Hao LUO Jiawei LI Yawei FANG Hao LIU Tianxiao state key laboratory of clean Energy utilization Institute for Thermal Power EngineeringZhejiang UniversityHangzhou310027China

This paper studied the thermal physical properties of foundation materials in the molten salt tank of thermal energy storage system after molten salt leakage by Transient plane source experiment and X-ray computed microtomography simulation methods.The microstructure,thermal properties and pressure resistance with different particle diameters were addressed.The measured heat conductivities from Transient plane source experiment for three cases are 0.49 W/(m·K),0.48 W/(m·K),and 0.51 W/(m·K),and the porosity is 30.1%,30.7%,and 31.2% respectively.The heat conductivity simulating results of three cases are 0.471 W/(m·K),0.482W/(m·K),and 0.513 W/(m·K).The ratio of difference between the results of simulation and Transient plane source measurement is as low as 1.2%,verifying the reliability of experimental and simulation results to a certain degree.Compared with the heat conductivity of 0.097-0.129 W/(m·K) and porosity of 71.6%-78.9% without leaking salt,the porosity is reduced by more than 50% while the heat conductivity increased by 4 to 5 times after molten salt leakage.This significant increase in heat conductivity has a great impact on security operation,structure design,and modeling of the tank foundation for solar power plants.

关键词： heat conductivity X-ray computed microtomography foundation materials three-phase threshold algorithm molten salt leakage

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