A sulphuric acid bake–leach method for the treatment of mixed copper-cobalt oxide minerals was investigated as an alternative to the reductive leaching method. Sulphuric acid bake-leach process of the mixed copper-co...A sulphuric acid bake–leach method for the treatment of mixed copper-cobalt oxide minerals was investigated as an alternative to the reductive leaching method. Sulphuric acid bake-leach process of the mixed copper-cobalt oxide ore was carried out by mixing the sample with sulphuric acid followed by baking of the mixture in a muffle furnace. Baking tests were conducted at different conditions such as temperature, time, and varying amounts of acid. The reacted samples were then subjected to water leaching at room temperature to determine the leachability of copper and cobalt from the baked material. The dissolutions of copper and cobalt were dependent on acid concentration with cobalt showing more sensitivity to the amount of acid. Both copper and cobalt were extracted from the baked material within short leaching times and without the addition of reducing agents. The outcome of this work has shown that the sulphuric acid bake-leach process is a possible alternative to the reductive leaching method for copper-cobalt oxide ores.展开更多
Electrochemical conversion of nitrate(NO_(3)~-) to ammonia(NH_(3)) can target two birds with one stone well, in NO_(3)^(-)-containing sewage remediation and sustainable NH_(3) production. However, single metalbased ca...Electrochemical conversion of nitrate(NO_(3)~-) to ammonia(NH_(3)) can target two birds with one stone well, in NO_(3)^(-)-containing sewage remediation and sustainable NH_(3) production. However, single metalbased catalysts are difficult to drive high-efficient NO_(3)~- removal due to the multi-electron transfer steps.Herein, we present a tandem catalyst with simple structure, Cu-Co binary metal oxides(Cu-Co-O), by engineering intermediate phases as catalytic active species for NO_(3)~- conversion. Electrochemical evaluation,X-ray photoelectron spectroscopy, and in situ Raman spectra together suggest that the newly-generated Cu-based phases was prone to NO_(3)~- to NO_(2)~- conversion, then NO_(2)~- was reduced to NH_(3) on Co-based species. At an applied potential of -1.1 V vs. saturated calomel electrode, the Cu-Co-O catalyst achieved NO_(3)~- -N removal of 90% and NH_(3) faradaic efficiency of 81% for 120 min in 100 m L of 50 mg/L NO_(3)~- -N,consuming only 0.69 k Wh/mol in a two-electrode system. This study provides a facile and efficient engineering strategy for developing high-performance catalysts for electrocatalytic nitrate conversion.展开更多
Manganese oxide ores from Gabon and Xiangxi were leached with waste tea as reductant in dilute sulfuric acid solution. The effects of waste tea dosage, concentration of sulfuric acid, liquid-to-solid ratio, leaching t...Manganese oxide ores from Gabon and Xiangxi were leached with waste tea as reductant in dilute sulfuric acid solution. The effects of waste tea dosage, concentration of sulfuric acid, liquid-to-solid ratio, leaching temperature and reaction time on leaching process were explored. The leaching efficiency of Gabonese manganese oxide ore reached almost 100% under the optimal condition which was determined as follows： manganese oxide ore to waste tea mass ratio of 10：1, sulfuric acid concentration of 2.5 molFL, liquid-to-solid ratio of 7.5：1, leaching temperature of 368 K, time of 8 h. The leaching efficiency of Xiangxi manganese oxide ore reached 99.8% under the optimal condition which was determined as follows： manganese oxide ore to waste tea mass ratio of 10：1, sulfuric acid concentration of 1.7 mol/L, liquid-to-solid ratio of 7.5：1, leaching temperature of 368 K, time of 8 h. The leaching process followed the internal diffusion controlled kinetic model, and the apparent activation energies of Gabonese manganese oxide ore and Xiangxi manganese oxide ore were calculated to be 38.2 kJ/mol and 20.4 kJ/mol, respectively. The morphological changes and mineralogical forms of the ore before and after the chemical treatment were discussed with the support of XRD analysis and SEM analysis.展开更多
Ida2--H2O system（iminodiacetate aqueous solution） was used to leach a low grade zinc oxide ore for Zn extraction.The effects of leaching time,liquid-solid ratio（L/S）,total concentration of Ida2-（[Ida2-]T）,leachi...Ida2--H2O system（iminodiacetate aqueous solution） was used to leach a low grade zinc oxide ore for Zn extraction.The effects of leaching time,liquid-solid ratio（L/S）,total concentration of Ida2-（[Ida2-]T）,leaching temperature and pH on Zn leaching recovery and the dissolution of impurities such as Ca,Mg,Cu,Ni,Fe,Pb and Cd were investigated.Results show that Ca,Mg and Fe in ores were hardly dissolved in alkalescent iminodiacetate aqueous solution,while valuable metals such as Cu,Ni,Pb and Cd were partly dissolved into leaching liquor with Zn.The recovery of Zn reaches 76.6% when the ores were leached for 4 h at 70 ℃ by 0.9 mol/L iminodiacetate aqueous solution with pH of 8 and L/S of 5：1.展开更多
The extraction of manganese from low-grade manganese oxide ores using Ca S derived from Ca SO4 as reductant was investigated. The effects of mass ratio of Ca S to ore, reduction temperature, reduction time, liquid to ...The extraction of manganese from low-grade manganese oxide ores using Ca S derived from Ca SO4 as reductant was investigated. The effects of mass ratio of Ca S to ore, reduction temperature, reduction time, liquid to solid ratio（L/S ratio）, stirring speed, leaching temperature, leaching time and H2SO4 concentration on the leaching rates of Mn and Fe during the reduction–acid leaching process were discussed. The leaching rates of 96.47% for Mn and 19.24% for Fe were obtained under the optimized conditions of mass ratio of Ca S to manganese oxide ore 1：6.7, L/S ratio 5：1, stirring speed 300 r/min, reduction temperature of 95 °C for 2.0 h in the reduction process and leaching stirring speed of 200 r/min, H2SO4 concentration of 1.5 mol/L, leaching temperature of 80 °C for 5 min in the leaching process. In addition, this process can be employed in the recovery of manganese from various manganese oxide ores, and Mn leaching rate above 95% is obtained.展开更多
To obtain the appropriate conditions for eliminating Fe3＋from NiSO4 solution, the digestion solution of the clinker was used as raw material, which was obtained from roasting the nickel oxide ore with （NH4）2SO4. Th...To obtain the appropriate conditions for eliminating Fe3＋from NiSO4 solution, the digestion solution of the clinker was used as raw material, which was obtained from roasting the nickel oxide ore with （NH4）2SO4. The ammonium jarosite was successfully synthesized from the solution with analytic grade NH4HCO3. The effects of reaction temperature, reaction time, end pH value of reaction on the removal rate of iron were investigated, and the effect of the initial concentration of Fe3＋was also discussed. All of those factors had significant effects on the removal rate of Fe3＋, among which the reaction temperature was the most prominent. The appropriate reaction conditions were concluded as follows： reaction temperature 95 ℃ reaction time 3.5 h, end pH value of reaction 2.5 at initial concentration of Fe3＋19.36 g/L. The physical aspect of （NH4）2Fe6（SO4）4（OH）12 was cluster figure composed of sheet or prismatic particles with smooth surface.展开更多
The reduction process of manganese dioxide in low-grade manganese ore by biomass roasting was investigated.The calcine of manganese oxide ore was further leached by sulphuric acid, the manganese in ore can be converte...The reduction process of manganese dioxide in low-grade manganese ore by biomass roasting was investigated.The calcine of manganese oxide ore was further leached by sulphuric acid, the manganese in ore can be converted into manganese sulfate.Effects of the mass ratio of manganese ore to sawdust, roasting temperature and time, leaching temperature and time, leaching agent concentration and liquid-solid ratio were studied.97.71% of manganese recovery can be achieved under the optimal conditions：the mass ratio of manganese ore to sawdust of 5：1, roasting temperature at 500℃ for 40 min, leaching temperature at 60℃ for 40 min, sulphuric acid concentration of 1 mol/L and liquid-solid ratio of 10：1.Other types of low-grade manganese ore like Guilin ore, Nanning ore and Gongcheng ore were tested and the same results were obtained.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
Mexican copper ore is a mixed ore containing mainly copper oxide and some copper sulfide that responds well to flotation. The joint techniques of flotation and leaching were studied. The results indicate that an ore c...Mexican copper ore is a mixed ore containing mainly copper oxide and some copper sulfide that responds well to flotation. The joint techniques of flotation and leaching were studied. The results indicate that an ore containing 19.01% copper could be obtained at a recovery ratio of 35.02% by using sodium sulfide and butyl xanthate flotation. Over 83.33% of the copper oxide can be recovered from the railings by leaching in suitable conditions, such as 1 h stirring at a temperature around 25 ℃with a mixing speed of S00 r/min, an H2SO4 concentration of 1.0 mol/L and a mass ratio of the ore-slurry-liquid to solid （mL/ms） of 3. The overall yield of refined ore after flotation and leaching is over 89.18% of the copper, which is much better than sole flotation or leaching. A copper product containing more than 99.9% copper was obtained by using the process： flotation-agitation leaching- solvent extraction-electro-winning.展开更多
Mechanochemical sulfidization of a mixed sulfide/oxide copper ore by co-grinding with sulfur and additives including Mg(NO3)2 and Fe(NO3)3 salts and iron,aluminum and magnesium powders was investigated for the first t...Mechanochemical sulfidization of a mixed sulfide/oxide copper ore by co-grinding with sulfur and additives including Mg(NO3)2 and Fe(NO3)3 salts and iron,aluminum and magnesium powders was investigated for the first time.Also,the influence of sulfidization during the wet-milling process was examined on the separation efficiency and recovery of copper in detail.The results demonstrated that co-grinding with sulfur solely had the best flotation performance at the value of 0.5 wt.%and it was attributed to the possible existence of S\\O bonding on copper oxides surfaces.In addition,adding magnesium nitrate salt,magnesium powder,iron nitrate salt and aluminum powder as additive associated with 0.5 wt%sulfur into ball milling caused the flotation improvement at the amounts of 0.2 wt%,0.2 wt%,0.5 wt%and 0.5 wt%,respectively.Also,the effect of grinding time and sulfidization pH with 0.5 wt%sulfur solely was determined and pH s of 7.5 to 8.5 gave the best results.The highest recovery(75.76%)and separation efficiency(63.44%)were achieved at pH of 7.5 and 8.5,respectively.展开更多
An environmentally friendly and resource-conserving route to the clean production of electrolytic manganese was developed,in which the electrolytic manganese residue(EMR)was initially calcined for cement buffering;the...An environmentally friendly and resource-conserving route to the clean production of electrolytic manganese was developed,in which the electrolytic manganese residue(EMR)was initially calcined for cement buffering;then the generated SO2-containing flue gas was managed using manganese oxide ore and anolyte(MOOA)desulfurization;at last,the desulfurized slurry was introduced to the electrolytic manganese production(EMP).Results showed that 4.0 wt%coke addition reduced the sulfur of calcined EMR to 0.9%,thereby satisfying the cement-buffer requirement.Pilot-scale desulfurization showed that about 7.5 vol%of high SO2 containing flue gas can be cleaned to less than 0.1 vol%through a five-stage countercurrent MOOA desulfurization.The desulfurized slurry had 42.44 g·L-Mn2+and 1.92 g·L-1 S2 O62-,which was suitable for electrowinning after purification,and the purity of manganese product was 99.93%,satisfy the National Standard of China YB/T051-2015.This new integrated technology fulfilled 99.7%of sulfur reutilization from the EMR and 94.1%was effectively used to the EMP.The MOOA desulfurization linked the EMP a closed cycle without any pollutant discharge,which promoted the cleaner production of EMP industry.展开更多
The effect of temperature on leaching behavior of copper minerals with different occurrence states in complex copper oxide ores was carried out by phase analysis means of XRD, optical microscopy and SEM-EDS. The resul...The effect of temperature on leaching behavior of copper minerals with different occurrence states in complex copper oxide ores was carried out by phase analysis means of XRD, optical microscopy and SEM-EDS. The results indicated that at ambient temperature, the easily leached copper oxide minerals were completely dissolved, while the bonded copper minerals were insoluble. At lukewarm temperature of 40℃, it was mainly the dissolution of copper in isomorphism state. With increasing temperature to 60℃, the copper leaching rate in the adsorbed state was significantly accelerated. In addition, when the temperature increased to 80℃, the isomorphic copper was completely leached, leaving 11.2% adsorbed copper un-leached. However, the copper in feldspar-quartz-copper-iron colloid state was not dissolved throughout the leaching process. Overall, the leaching rates of copper in different copper minerals decreased in the order: malachite, pseudo-malachite > chrysocolla > copper-bearing chlorite > copper-bearing muscovite > copper-bearing biotite > copper-bearing limonite > feldspar-quartz-copper-iron colloid.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
An investigation on reducing low-grade manganese dioxide ore pellets was carried out by using wheat stalk as reductant. The main impact factors of reduction percent such as particle size, biomass/ore ratio, heating ra...An investigation on reducing low-grade manganese dioxide ore pellets was carried out by using wheat stalk as reductant. The main impact factors of reduction percent such as particle size, biomass/ore ratio, heating rate, nitrogen flow rate, temperature and time in reduction process were discussed. The morphology and component of manganese dioxide ore particle at different stages were also analyzed by scanning electron microscopy （SEM） and energy dispersive X-ray spectroscopy （EDS）. The results show the increase of the reduction temperature and time, biomass/ore ratio, and the decrease of particle size, heating rate and nitrogen flow rate can significantly enhance reduction efficiency. The reduction kinetic of the manganese ore is controlled by three-dimensional mass diffusion of gaseous reductive volatiles passing from the surface to the core of the ore particles. The activation energy E and frequency factor A were calculated to be 24.15 kJ.mol^-1 and 166 min^-1, respectively. Biomass pyrolysis volatiles adsorbed onto the surface of the ore particle leads to serious variation of the microstructures and chemical composition of the manganese ore particles.展开更多
The artificial neural network(ANN)and hybrid of artificial neural network and genetic algorithm(GANN)were appliedto predict the optimized conditions of column leaching of copper oxide ore with relations of input and o...The artificial neural network(ANN)and hybrid of artificial neural network and genetic algorithm(GANN)were appliedto predict the optimized conditions of column leaching of copper oxide ore with relations of input and output data.The leachingexperiments were performed in three columns with the heights of2,4and6m and in particle size of<25.4and<50.8mm.Theeffects of different operating parameters such as column height,particle size,acid flow rate and leaching time were studied tooptimize the conditions to achieve the maximum recovery of copper using column leaching in pilot scale.It was found that therecovery increased with increasing the acid flow rate and leaching time and decreasing particle size and column height.Theefficiency of GANN and ANN algorithms was compared with each other.The results showed that GANN is more efficient than ANNin predicting copper recovery.The proposed model can be used to predict the Cu recovery with a reasonable error.展开更多
The orthogonal test was used to optimize the reaction conditions of roasting zinc oxide ore with NaOH aiming to comprehensively utilize zinc oxide ore.The optimized reaction conditions were molar ratio of NaOH to zinc...The orthogonal test was used to optimize the reaction conditions of roasting zinc oxide ore with NaOH aiming to comprehensively utilize zinc oxide ore.The optimized reaction conditions were molar ratio of NaOH to zinc oxide ore 6:1,roasting temperature 450°C,holding time 150 min.The molar ratio of NaOH to zinc oxide ore was the most predominant factor affecting the extraction ratios of zinc oxide and silica.The mineral phase transformations were investigated by testing the phases of specimens obtained at different temperatures.The process was that silica reacted with molten NaOH to form Na_2SiO_3 at first,then transformed into Na_4SiO_4 with temperature rising.ZnCO_3 and its decomposing product ZnO reacted with NaOH to form Na_2ZnO_2.Na_2ZnSiO_4was also obtained.The reaction rate was investigated using unreacted shrinking core model.Two models used were chemical reaction at the particle surface and diffusion through the product layer.The results indicated that the reaction rate was combine-controlled by two models.The activation energy and frequency factor were obtained as 24.12 k J/mol and 0.0682,respectively.展开更多
Rotary kiln process for iron ore oxide pellet production is hard to detect and control.Construction of one-dimensional model of temperature field in rotary kiln was described.And the results lay a solid foundation for...Rotary kiln process for iron ore oxide pellet production is hard to detect and control.Construction of one-dimensional model of temperature field in rotary kiln was described.And the results lay a solid foundation for online control.Establishment of kiln process control expert system was presented,with maximum temperature of pellet and gas temperature at the feed end as control cores,and interval estimate as control strategy.Software was developed and put into application in a pellet plant.The results show that control guidance of this system is accurate and effective.After production application for nearly one year,the compressive strength and first grade rate of pellet are increased by 86 N and 2.54%,respectively,while FeO content is 0.05% lowered.This system can reveal detailed information of real time kiln process,and provide a powerful tool for online control of pellet production.展开更多
Grate process is an important step in grate-kiln pellet production.However,as a relatively closed system,the process on grate is inaccessible to direct detection,therefore,it is hard to control.As a result,mathematica...Grate process is an important step in grate-kiln pellet production.However,as a relatively closed system,the process on grate is inaccessible to direct detection,therefore,it is hard to control.As a result,mathematical models of temperature distribution,moisture distribution and oxidation degree distribution in pellet bed,with good universality,computation speed and calculation accuracy,are presented based on analysis of heat transfer and physical-chemical reactions during grate process.And real-time visualization of temperature,moisture and oxidation degree distribution in pellet bed during grate process is realized.Model validation is displayed,and the similarity of 91% is proved.The results can reveal real time status on grate,and provide a solid foundation for the subsequent study of artificial intelligence control system of pellet production.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 recovery of zinc from low-grade zinc oxide ores with solvent extraction-electrowinning technique was investigated by using D2EHPA as extractant and 260 # kerosene as diluent. The results show that it is possible t...The recovery of zinc from low-grade zinc oxide ores with solvent extraction-electrowinning technique was investigated by using D2EHPA as extractant and 260 # kerosene as diluent. The results show that it is possible to selectively leach zinc from the ores by heap leaching. The zinc concentration of leach solution in the first leaching cycle is 32.57 g/L, and in the sixteenth cycle the zinc concentration is 8.27g/L after solvent extraction. The leaching solution is subjected to solvent extraction, scrubbing and selective stripping for enrichment of zinc and removal of impurities. The pregnant zinc sulfate solution produced from the stripping cycle is suitable for zinc electrowinning. Extra-pure zinc metal was obtained in the electrowinning test under conventional conditions.展开更多
文摘A sulphuric acid bake–leach method for the treatment of mixed copper-cobalt oxide minerals was investigated as an alternative to the reductive leaching method. Sulphuric acid bake-leach process of the mixed copper-cobalt oxide ore was carried out by mixing the sample with sulphuric acid followed by baking of the mixture in a muffle furnace. Baking tests were conducted at different conditions such as temperature, time, and varying amounts of acid. The reacted samples were then subjected to water leaching at room temperature to determine the leachability of copper and cobalt from the baked material. The dissolutions of copper and cobalt were dependent on acid concentration with cobalt showing more sensitivity to the amount of acid. Both copper and cobalt were extracted from the baked material within short leaching times and without the addition of reducing agents. The outcome of this work has shown that the sulphuric acid bake-leach process is a possible alternative to the reductive leaching method for copper-cobalt oxide ores.
基金supported by National Natural Science Foundation of China (Nos.52131003 and 42007180)Special Research Assistant Program of Chinese Academy of Science, Natural Science Foundation of Chongqing (No.cstc2020jcyj-msxm X0775)+1 种基金Scientific Research Instrument Development Project of Chinese Academy of Sciences (No.YJKYYQ20200044)Outstanding Scientist of Chongqing Talent Program (No.CQYC20210101288)。
文摘Electrochemical conversion of nitrate(NO_(3)~-) to ammonia(NH_(3)) can target two birds with one stone well, in NO_(3)^(-)-containing sewage remediation and sustainable NH_(3) production. However, single metalbased catalysts are difficult to drive high-efficient NO_(3)~- removal due to the multi-electron transfer steps.Herein, we present a tandem catalyst with simple structure, Cu-Co binary metal oxides(Cu-Co-O), by engineering intermediate phases as catalytic active species for NO_(3)~- conversion. Electrochemical evaluation,X-ray photoelectron spectroscopy, and in situ Raman spectra together suggest that the newly-generated Cu-based phases was prone to NO_(3)~- to NO_(2)~- conversion, then NO_(2)~- was reduced to NH_(3) on Co-based species. At an applied potential of -1.1 V vs. saturated calomel electrode, the Cu-Co-O catalyst achieved NO_(3)~- -N removal of 90% and NH_(3) faradaic efficiency of 81% for 120 min in 100 m L of 50 mg/L NO_(3)~- -N,consuming only 0.69 k Wh/mol in a two-electrode system. This study provides a facile and efficient engineering strategy for developing high-performance catalysts for electrocatalytic nitrate conversion.
基金Project(2010FJ1011)supported by the Major Project of Hunan Science and Technology,ChinaProject(cstc2012ggB90002)supported by the Chongqing Key Science and Technology Program,China
文摘Manganese oxide ores from Gabon and Xiangxi were leached with waste tea as reductant in dilute sulfuric acid solution. The effects of waste tea dosage, concentration of sulfuric acid, liquid-to-solid ratio, leaching temperature and reaction time on leaching process were explored. The leaching efficiency of Gabonese manganese oxide ore reached almost 100% under the optimal condition which was determined as follows： manganese oxide ore to waste tea mass ratio of 10：1, sulfuric acid concentration of 2.5 molFL, liquid-to-solid ratio of 7.5：1, leaching temperature of 368 K, time of 8 h. The leaching efficiency of Xiangxi manganese oxide ore reached 99.8% under the optimal condition which was determined as follows： manganese oxide ore to waste tea mass ratio of 10：1, sulfuric acid concentration of 1.7 mol/L, liquid-to-solid ratio of 7.5：1, leaching temperature of 368 K, time of 8 h. The leaching process followed the internal diffusion controlled kinetic model, and the apparent activation energies of Gabonese manganese oxide ore and Xiangxi manganese oxide ore were calculated to be 38.2 kJ/mol and 20.4 kJ/mol, respectively. The morphological changes and mineralogical forms of the ore before and after the chemical treatment were discussed with the support of XRD analysis and SEM analysis.
基金Project (2007CB613604) supported by the National Basic Research Program of China
文摘Ida2--H2O system（iminodiacetate aqueous solution） was used to leach a low grade zinc oxide ore for Zn extraction.The effects of leaching time,liquid-solid ratio（L/S）,total concentration of Ida2-（[Ida2-]T）,leaching temperature and pH on Zn leaching recovery and the dissolution of impurities such as Ca,Mg,Cu,Ni,Fe,Pb and Cd were investigated.Results show that Ca,Mg and Fe in ores were hardly dissolved in alkalescent iminodiacetate aqueous solution,while valuable metals such as Cu,Ni,Pb and Cd were partly dissolved into leaching liquor with Zn.The recovery of Zn reaches 76.6% when the ores were leached for 4 h at 70 ℃ by 0.9 mol/L iminodiacetate aqueous solution with pH of 8 and L/S of 5：1.
基金Project(21376273)supported by the National Natural Science Foundation of ChinaProject(2010FJ1011)supported by the Key Program of Science and Technology of Hunan Province,China
文摘The extraction of manganese from low-grade manganese oxide ores using Ca S derived from Ca SO4 as reductant was investigated. The effects of mass ratio of Ca S to ore, reduction temperature, reduction time, liquid to solid ratio（L/S ratio）, stirring speed, leaching temperature, leaching time and H2SO4 concentration on the leaching rates of Mn and Fe during the reduction–acid leaching process were discussed. The leaching rates of 96.47% for Mn and 19.24% for Fe were obtained under the optimized conditions of mass ratio of Ca S to manganese oxide ore 1：6.7, L/S ratio 5：1, stirring speed 300 r/min, reduction temperature of 95 °C for 2.0 h in the reduction process and leaching stirring speed of 200 r/min, H2SO4 concentration of 1.5 mol/L, leaching temperature of 80 °C for 5 min in the leaching process. In addition, this process can be employed in the recovery of manganese from various manganese oxide ores, and Mn leaching rate above 95% is obtained.
基金Project(51204054)supported by the National Natural Science Foundation of ChinaProject(N110402012)supported by Fundamental Research Funds for the Central Universities,ChinaProject(2007CB613603)supported by the National Basic Research Program of China
文摘To obtain the appropriate conditions for eliminating Fe3＋from NiSO4 solution, the digestion solution of the clinker was used as raw material, which was obtained from roasting the nickel oxide ore with （NH4）2SO4. The ammonium jarosite was successfully synthesized from the solution with analytic grade NH4HCO3. The effects of reaction temperature, reaction time, end pH value of reaction on the removal rate of iron were investigated, and the effect of the initial concentration of Fe3＋was also discussed. All of those factors had significant effects on the removal rate of Fe3＋, among which the reaction temperature was the most prominent. The appropriate reaction conditions were concluded as follows： reaction temperature 95 ℃ reaction time 3.5 h, end pH value of reaction 2.5 at initial concentration of Fe3＋19.36 g/L. The physical aspect of （NH4）2Fe6（SO4）4（OH）12 was cluster figure composed of sheet or prismatic particles with smooth surface.
基金supported by the National Natural Science Foundation of China (No.50874067)
文摘The reduction process of manganese dioxide in low-grade manganese ore by biomass roasting was investigated.The calcine of manganese oxide ore was further leached by sulphuric acid, the manganese in ore can be converted into manganese sulfate.Effects of the mass ratio of manganese ore to sawdust, roasting temperature and time, leaching temperature and time, leaching agent concentration and liquid-solid ratio were studied.97.71% of manganese recovery can be achieved under the optimal conditions：the mass ratio of manganese ore to sawdust of 5：1, roasting temperature at 500℃ for 40 min, leaching temperature at 60℃ for 40 min, sulphuric acid concentration of 1 mol/L and liquid-solid ratio of 10：1.Other types of low-grade manganese ore like Guilin ore, Nanning ore and Gongcheng ore were tested and the same results were obtained.
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Projects 50604016 supported by the National Natural Science Foundation of China2007BAB22B01 by the 11th Five-Year Plan of National Science and Technology of China
文摘Mexican copper ore is a mixed ore containing mainly copper oxide and some copper sulfide that responds well to flotation. The joint techniques of flotation and leaching were studied. The results indicate that an ore containing 19.01% copper could be obtained at a recovery ratio of 35.02% by using sodium sulfide and butyl xanthate flotation. Over 83.33% of the copper oxide can be recovered from the railings by leaching in suitable conditions, such as 1 h stirring at a temperature around 25 ℃with a mixing speed of S00 r/min, an H2SO4 concentration of 1.0 mol/L and a mass ratio of the ore-slurry-liquid to solid （mL/ms） of 3. The overall yield of refined ore after flotation and leaching is over 89.18% of the copper, which is much better than sole flotation or leaching. A copper product containing more than 99.9% copper was obtained by using the process： flotation-agitation leaching- solvent extraction-electro-winning.
基金the AbbasAbad copper mineShahrood University of Technology for their financial support during this research。
文摘Mechanochemical sulfidization of a mixed sulfide/oxide copper ore by co-grinding with sulfur and additives including Mg(NO3)2 and Fe(NO3)3 salts and iron,aluminum and magnesium powders was investigated for the first time.Also,the influence of sulfidization during the wet-milling process was examined on the separation efficiency and recovery of copper in detail.The results demonstrated that co-grinding with sulfur solely had the best flotation performance at the value of 0.5 wt.%and it was attributed to the possible existence of S\\O bonding on copper oxides surfaces.In addition,adding magnesium nitrate salt,magnesium powder,iron nitrate salt and aluminum powder as additive associated with 0.5 wt%sulfur into ball milling caused the flotation improvement at the amounts of 0.2 wt%,0.2 wt%,0.5 wt%and 0.5 wt%,respectively.Also,the effect of grinding time and sulfidization pH with 0.5 wt%sulfur solely was determined and pH s of 7.5 to 8.5 gave the best results.The highest recovery(75.76%)and separation efficiency(63.44%)were achieved at pH of 7.5 and 8.5,respectively.
基金supported by the National Key R&D Program of China(No.2018YFC0213405)。
文摘An environmentally friendly and resource-conserving route to the clean production of electrolytic manganese was developed,in which the electrolytic manganese residue(EMR)was initially calcined for cement buffering;then the generated SO2-containing flue gas was managed using manganese oxide ore and anolyte(MOOA)desulfurization;at last,the desulfurized slurry was introduced to the electrolytic manganese production(EMP).Results showed that 4.0 wt%coke addition reduced the sulfur of calcined EMR to 0.9%,thereby satisfying the cement-buffer requirement.Pilot-scale desulfurization showed that about 7.5 vol%of high SO2 containing flue gas can be cleaned to less than 0.1 vol%through a five-stage countercurrent MOOA desulfurization.The desulfurized slurry had 42.44 g·L-Mn2+and 1.92 g·L-1 S2 O62-,which was suitable for electrowinning after purification,and the purity of manganese product was 99.93%,satisfy the National Standard of China YB/T051-2015.This new integrated technology fulfilled 99.7%of sulfur reutilization from the EMR and 94.1%was effectively used to the EMP.The MOOA desulfurization linked the EMP a closed cycle without any pollutant discharge,which promoted the cleaner production of EMP industry.
基金Project(U1608254) supported by the Special Fund for the National Natural Science Foundation of ChinaProjects(ZJKY2017(B)KFJJ01,ZJKY2017(B)KFJJ02) supported by Zijin Mining Group Co.,Ltd.,China
文摘The effect of temperature on leaching behavior of copper minerals with different occurrence states in complex copper oxide ores was carried out by phase analysis means of XRD, optical microscopy and SEM-EDS. The results indicated that at ambient temperature, the easily leached copper oxide minerals were completely dissolved, while the bonded copper minerals were insoluble. At lukewarm temperature of 40℃, it was mainly the dissolution of copper in isomorphism state. With increasing temperature to 60℃, the copper leaching rate in the adsorbed state was significantly accelerated. In addition, when the temperature increased to 80℃, the isomorphic copper was completely leached, leaving 11.2% adsorbed copper un-leached. However, the copper in feldspar-quartz-copper-iron colloid state was not dissolved throughout the leaching process. Overall, the leaching rates of copper in different copper minerals decreased in the order: malachite, pseudo-malachite > chrysocolla > copper-bearing chlorite > copper-bearing muscovite > copper-bearing biotite > copper-bearing limonite > feldspar-quartz-copper-iron colloid.
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.
基金supported by the National Natural Science Foundation of China(No.50874067)
文摘An investigation on reducing low-grade manganese dioxide ore pellets was carried out by using wheat stalk as reductant. The main impact factors of reduction percent such as particle size, biomass/ore ratio, heating rate, nitrogen flow rate, temperature and time in reduction process were discussed. The morphology and component of manganese dioxide ore particle at different stages were also analyzed by scanning electron microscopy （SEM） and energy dispersive X-ray spectroscopy （EDS）. The results show the increase of the reduction temperature and time, biomass/ore ratio, and the decrease of particle size, heating rate and nitrogen flow rate can significantly enhance reduction efficiency. The reduction kinetic of the manganese ore is controlled by three-dimensional mass diffusion of gaseous reductive volatiles passing from the surface to the core of the ore particles. The activation energy E and frequency factor A were calculated to be 24.15 kJ.mol^-1 and 166 min^-1, respectively. Biomass pyrolysis volatiles adsorbed onto the surface of the ore particle leads to serious variation of the microstructures and chemical composition of the manganese ore particles.
文摘The artificial neural network(ANN)and hybrid of artificial neural network and genetic algorithm(GANN)were appliedto predict the optimized conditions of column leaching of copper oxide ore with relations of input and output data.The leachingexperiments were performed in three columns with the heights of2,4and6m and in particle size of<25.4and<50.8mm.Theeffects of different operating parameters such as column height,particle size,acid flow rate and leaching time were studied tooptimize the conditions to achieve the maximum recovery of copper using column leaching in pilot scale.It was found that therecovery increased with increasing the acid flow rate and leaching time and decreasing particle size and column height.Theefficiency of GANN and ANN algorithms was compared with each other.The results showed that GANN is more efficient than ANNin predicting copper recovery.The proposed model can be used to predict the Cu recovery with a reasonable error.
基金Projects(51774070,51204054)supported by the National Natural Science Foundation of ChinaProject(N150204009)supported by the Ministry of Education Basic Scientific Research Business Expenses,ChinaProject(2007CB613603)supported by the National Basic Research Program of China
文摘The orthogonal test was used to optimize the reaction conditions of roasting zinc oxide ore with NaOH aiming to comprehensively utilize zinc oxide ore.The optimized reaction conditions were molar ratio of NaOH to zinc oxide ore 6:1,roasting temperature 450°C,holding time 150 min.The molar ratio of NaOH to zinc oxide ore was the most predominant factor affecting the extraction ratios of zinc oxide and silica.The mineral phase transformations were investigated by testing the phases of specimens obtained at different temperatures.The process was that silica reacted with molten NaOH to form Na_2SiO_3 at first,then transformed into Na_4SiO_4 with temperature rising.ZnCO_3 and its decomposing product ZnO reacted with NaOH to form Na_2ZnO_2.Na_2ZnSiO_4was also obtained.The reaction rate was investigated using unreacted shrinking core model.Two models used were chemical reaction at the particle surface and diffusion through the product layer.The results indicated that the reaction rate was combine-controlled by two models.The activation energy and frequency factor were obtained as 24.12 k J/mol and 0.0682,respectively.
基金Project(NCET-05-0630) supported by Program for New Century Excellent Talents in University of China
文摘Rotary kiln process for iron ore oxide pellet production is hard to detect and control.Construction of one-dimensional model of temperature field in rotary kiln was described.And the results lay a solid foundation for online control.Establishment of kiln process control expert system was presented,with maximum temperature of pellet and gas temperature at the feed end as control cores,and interval estimate as control strategy.Software was developed and put into application in a pellet plant.The results show that control guidance of this system is accurate and effective.After production application for nearly one year,the compressive strength and first grade rate of pellet are increased by 86 N and 2.54%,respectively,while FeO content is 0.05% lowered.This system can reveal detailed information of real time kiln process,and provide a powerful tool for online control of pellet production.
基金Project(NCET050630) supported by Program for New Century Excellent Talents in University,China
文摘Grate process is an important step in grate-kiln pellet production.However,as a relatively closed system,the process on grate is inaccessible to direct detection,therefore,it is hard to control.As a result,mathematical models of temperature distribution,moisture distribution and oxidation degree distribution in pellet bed,with good universality,computation speed and calculation accuracy,are presented based on analysis of heat transfer and physical-chemical reactions during grate process.And real-time visualization of temperature,moisture and oxidation degree distribution in pellet bed during grate process is realized.Model validation is displayed,and the similarity of 91% is proved.The results can reveal real time status on grate,and provide a solid foundation for the subsequent study of artificial intelligence control system of pellet production.
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.
文摘The recovery of zinc from low-grade zinc oxide ores with solvent extraction-electrowinning technique was investigated by using D2EHPA as extractant and 260 # kerosene as diluent. The results show that it is possible to selectively leach zinc from the ores by heap leaching. The zinc concentration of leach solution in the first leaching cycle is 32.57 g/L, and in the sixteenth cycle the zinc concentration is 8.27g/L after solvent extraction. The leaching solution is subjected to solvent extraction, scrubbing and selective stripping for enrichment of zinc and removal of impurities. The pregnant zinc sulfate solution produced from the stripping cycle is suitable for zinc electrowinning. Extra-pure zinc metal was obtained in the electrowinning test under conventional conditions.
