Flotation is the most common method to recover valuable minerals by selective adsorption of collectors on target mineral surfaces.However,in subsequent hydrometallurgy of mineral flotation concentrates,the adsorbed co...Flotation is the most common method to recover valuable minerals by selective adsorption of collectors on target mineral surfaces.However,in subsequent hydrometallurgy of mineral flotation concentrates,the adsorbed collectors must be desorbed since it can adversely affect the efficiency of metallurgical process and produce wastewater.ZL,as a fatty acid mixture,is a typical industrially used collector for scheelite flotation in China.Sodium oleate(NaOL)has similar fatty acid group as ZL.In this study,the desorption behavior of NaOL/ZL from scheelite surface by a physical method of stirring at a low temperature was investigated.NaOL desorption tests of single mineral showed that a desorption rate of 77.75% for NaOL from scheelite surface into pulp was achieved in a stirring speed of2500 r/min at 5℃in a neutral environment.Under the above desorption condition,in the pulp containing desorbed collector by adding extra 30% normal NaOL dosage,the scheelite recovery reached about 95% in the single mineral flotation test.Desorption and reuse of ZL collector for the flotation of real scheelite ore showed only a 75%normal dosage of ZL could produce a qualified rough concentrate.The atomic force microscope(AFM)tests showed that after desorption treatment of low temperature and strong stirring,the dense strip-like structure of NaOL on the scheelite surface was destroyed to be speck-like.Molecular dynamics simulations(MDS)demonstrated that the adsorption energy between NaOL and scheelite surface was more negative at 25℃(-13.39 kcal/mol)than at 5℃(-11.50 kcal/mol)in a neutral pH,indicating that a low temperature was beneficial for the desorption of collector from mineral surface.Due to its simplicity and economy,the method we proposed of desorption of collector from mineral surface and its reuse for flotation has a great potential for industrial application.展开更多
This study investigated the effect of konjac glucomannan(KGM)on the flotation separation of calcite and scheelite.Micro-flotation tests showed that under the action of 50 mg/L KGM,the floatability of calcite notably d...This study investigated the effect of konjac glucomannan(KGM)on the flotation separation of calcite and scheelite.Micro-flotation tests showed that under the action of 50 mg/L KGM,the floatability of calcite notably decreased,while the impact on scheelite was negligible,resulting in a recovery difference of 82.53%.Fourier transform infrared(FTIR)spectroscopy and atomic force micro-scopy(AFM)analyses indicated the selective adsorption of KGM on the calcite surface.Test results of the zeta potential and UV-visible absorption spectroscopy revealed that KGM prevented the adsorption of sodium oleate on the calcite surface.X-ray photoelectron spec-troscopy(XPS)analysis further confirmed the chemical adsorption of KGM on the calcite surface and the formation of Ca(OH)_(2).The density functional theory(DFT)simulation results were consistent with the flotation tests,demonstrating the strong adsorption perform-ance of KGM on the calcite surface.This study offers a pathway for highly sustainable and cost-effective mineral processing by utilizing the unique properties of biopolymers such as KGM to separate valuable minerals from gangue minerals.展开更多
The Gejiu tin-copper-(tungsten)(Sn-Cu-(W))polymetallic district is located in the southwest of the W-Sn metallogenic belt in the western Youjiang Basin,Yunnan,Southwest China.Abundant W minerals have been identified i...The Gejiu tin-copper-(tungsten)(Sn-Cu-(W))polymetallic district is located in the southwest of the W-Sn metallogenic belt in the western Youjiang Basin,Yunnan,Southwest China.Abundant W minerals have been identified in the region via exploration.However,metallogenic sources and evolution of W remain unclear,and the existing metallogenic model has to be updated to guide further ore prospecting.Elemental and Sr-Nd isotopic data for scheelites assist in the determination of sources and evolution of the W-mineralizing fluids and metals in the district.Based on field geological survey,the scheelites in the Gejiu district can be categorized into three types:altered granite(Type Ⅰ),quartz vein(Type Ⅱ)from the Laochang deposit,and skarn(Type Ⅲ)from the Kafang deposit.Types Ⅰ and Ⅱ scheelites have low molybdenum(Mo)and strontium(Sr)contents,and Type Ⅱ scheelite has lower Sr contents than Type Ⅰ as well as higher Mo and Sr contents than Type Ⅲ scheelites.Varying Mo contents across the scheelite types suggests that the oxygen fugacity varied during ore accumulation.Type Ⅰ and Type Ⅱ scheelites exhibit similar rare earth elements(REE)patterns;Type Ⅲ scheelite contains lower REE content,particularly HREE,compared with the other scheelites.All scheelites exhibit negative Eu anomalies in the chondrite-normalized REE patterns.As the W-mineralization and two-mica granite share close spatial and temporal relationships,the negative Eu anomalies were likely inherited from the two-mica granite.Type Ⅰ and Type Ⅱ scheelites display varied(^(87)Sr/^(86)Sr)_(82 Ma)(0.7090-0.7141)andε_(Nd)(82 Ma)(from−9.9 to−5.4)values,similar to those of granite.However,Type Ⅲ scheelite exhibits lower(^(87)Sr/^(86)Sr)_(82 Ma)(0.7083-0.7087)and lowerε_(Nd)(82 Ma)(from−10.5 to−6.9)values than the two-mica granite.This indicates that the two-mica granite alone did not provide the ore-forming fluids and metals and that the Type Ⅲ scheelite ore-forming fluids likely involved external fluids that were probably derived from carbonate rocks.The implication is that highly differentiated two-mica granites were the source of primary W-bearing metals and fluids,which is consistent with earlier research on the origin of Sn ore-forming materials.展开更多
The Guanfang large-scale W deposit is located in the W polymetallic ore concentration area of Bozhushan in southeastern Yunnan,China.Despite extensive research,the fluid evolution process of the deposit remains ambigu...The Guanfang large-scale W deposit is located in the W polymetallic ore concentration area of Bozhushan in southeastern Yunnan,China.Despite extensive research,the fluid evolution process of the deposit remains ambiguous,leading to controversy regarding its genesis.This study conducted a detailed field geological survey,with systematic sampling of the KT6 orebody,to delineate mineralization stages.Fine mineralogy work,including the use of CL images of scheelite,in-situ LA-ICP-MS trace elements,and Sr isotopes,was carried out on diff erent generations of scheelite formed in various stages.The findings identified the evolution of fluids in the mineralization process,shedding light on the genesis of the deposit.The study revealed four mineralization stages at the Guanfang W deposit:prograde skarn stage,retrograde skarn stage,quartz-sulfide stage,and carbonate-fluorite stage.Diff erent generations of scheelite(Sch I,Sch II,Sch III)were observed in the first three stages,displaying distinct chondrite-normalized REE patterns.The REE of Sch I mainly substituted into the Ca site by REE^(3+)+□_(Ca),and there may be a similar substitution of Nb for REE,whereas it is not the main substitution method.The REE of Sch II mainly enter the scheelite lattice in the form of REE 3++Na+,and there may be a substitution of Nb for REE isomorphism.In the early stage,The REE of Sch III was mainly replaced by Nb for REE isomorphism,while in the later stage,the replacement mode of REE^(3+)+□_(Ca)coexisted with it.The Mo content in scheelite,along with the corresponding Eu anomalies in both scheelite and garnet,collectively imply that the ore-forming fluids during various mineralization stages were predominantly oxidizing,with only slight reducibility observed in Sch II.The in-situ Sr isotope ratios of scheelite concentrates ranged from 0.7093 to 0.7153,resembling those of the Bozhushan granite,indicating a relationship between W mineralization and granite.In addition,the Y/Ho ratios of scheelite from various mineralization stages exhibit a narrow range(19-31),with a pronounced correlation between the contents of Y and Ho and a similar trend in their variation.This consistency suggests that the Guanfang deposit has undergone a uniform or comparable evolutionary process,implying a stable ore-forming fluid across diff erent mineralization stages.展开更多
Surface energies of five different surfaces of scheelite crystal were calculated using density functional theory （DFT）. Based on the calculation results, the predominantly exposed surfaces in the morphologies of sch...Surface energies of five different surfaces of scheelite crystal were calculated using density functional theory （DFT）. Based on the calculation results, the predominantly exposed surfaces in the morphologies of scheelite crystals were predicted. {112} and {001} cleavage surfaces and {112} crystal surface are the commonly exposed surfaces, which are consistent with both previous literatures and the present experimental observations based on the XRD. Cleavage generates more easily along {112} surfaces than along {001} surfaces due to their different interlayer spacings. The surface roughness and appearance of different predominantly exposed surfaces were then investigated using AFM. The roughness of smooth {112} cleavage surface is the lowest among these three surfaces. On {001} cleavage surface, terraces are flat and separated by steps of about 10 nm in height. Subsequently, contact angle measurements were adopted to evaluate the wettability and surface energies of these surfaces. The surface energies evaluated directly correspond to the trend calculated with DFT.展开更多
Effects of size distribution (particle size and content of fine fraction (<10μm)) on scheelite flotation were studied using flotation tests and theoretical calculations. The results show that particle size influen...Effects of size distribution (particle size and content of fine fraction (<10μm)) on scheelite flotation were studied using flotation tests and theoretical calculations. The results show that particle size influences the scheelite recovery and the performance of combined reagents. The scheelite recovery is lowered by adding fine particles (<10μm) into the pulp containing coarse particles. Extended DLVO (EDLVO) theory confirms that the fine fractions (<10μm) could interface with the coarse fractions. The interaction energy and fluid forces are relative to the particle size, which might explain why the fine fractions influence the scheelite flotation. The highest recovery of scheelite using combined reagents as collector and optimum ratio of combined reagents were determined by scheelite particle size and reagent performance. However, the optimum adding order was only determined by reagent performance, which has nothing to do with particle size.展开更多
The effect of different decomposition conditions on tungsten recovery forscheelite concentrate has been examined. The results show that tungsten recovery can be more than98% under decomposing conditions as follows: th...The effect of different decomposition conditions on tungsten recovery forscheelite concentrate has been examined. The results show that tungsten recovery can be more than98% under decomposing conditions as follows: the amount of caustic soda is 2.2 and 3.2 times oftheoretical respectively, ratio of water and ore is 0.7-0.8, temperature is 160℃, and preservationtime is 2.0 h for scheelite concentrate (63.21 % WO_3) and low grade scheelite concentrate (55.17%WO_3).展开更多
Scheelite and scheelite-wolframite mixed concentrates with different grades were decomposed by caustic soda digestion, and the effects of caustic soda（NaOH） dosage, the ratio of water to ore and the stirring rate on...Scheelite and scheelite-wolframite mixed concentrates with different grades were decomposed by caustic soda digestion, and the effects of caustic soda（NaOH） dosage, the ratio of water to ore and the stirring rate on tungsten recovery were studied. The results show that under the conditions that the ratio of water to ore is （0.8,） stirring rate is 500 r·min-1 and the heating time is 2.0 h at （160 ℃,） the recovery of tungsten reaches 98% for scheelite （w（WO3） is （65.04%）） and wolframite containing high proportion of calcium （w（WO3） is 65.58%, w（Ca） is （7.53%）,） when caustic soda dosage is 2.2 and 2.0 times of theoretical value, respectively; the recovery of tungsten can be more than 98%,98% and 96% respectively for low-grade scheelite-wolframite mixed concentrate with （55.78%,） 45.32% and 25.21% WO3, when caustic soda dosage is 2.6,3.2 and 5.5 times of theoretical value, respectively.展开更多
Froth flotation of scheelite has regained new focus since the 2010s and research regarding floatability and reagents has made great progress over the years. The main objective was and remains the selective flotation o...Froth flotation of scheelite has regained new focus since the 2010s and research regarding floatability and reagents has made great progress over the years. The main objective was and remains the selective flotation of scheelite from other calcium-bearing minerals, in particular calcite, fluorite and apatite. Due to similar properties, most attempts have limited success or only specific application(linked to a type of ore or a location). This article aims at reviewing all general physical-chemical information on froth flotation of scheelite, including electrokinetic properties, influence of p H and already existing reagents as well as ones still under examination. It appears that chelating or mixed collectors and modified versions of sodium silicate and quebracho hold great promise for scheelite flotation, while the use of said depressants and/or promoters seems inevitable.展开更多
Luanchuan area is one of the regions with the largest scale of scheelite beneficiation and the largest output of scheelite concentrate in the world. After years of innovation and progress, the beneficiation technology...Luanchuan area is one of the regions with the largest scale of scheelite beneficiation and the largest output of scheelite concentrate in the world. After years of innovation and progress, the beneficiation technology of low-grade scheelite associated with molybdenum tailings in Luanchuan area is becoming more and more perfect. In this study, the development process of low-grade scheelite recycling technology in Luanchuan area was reviewed, including raw ore properties, beneficiation process, flotation equipment and flotation reagents. Meanwhile, taking Luoyang Yulu Mining Co., Ltd. as an example, the effects of various technical transformations such as the optimization of the beneficiation process, the column-machine combined process, and the high-efficiency flotation reagents were elucidated in detail. However, the recycling technology of low-grade scheelite of Luanchuan area is still possible to be improved. As a result, coupled with the latest research progress, the development direction of low-grade scheelite beneficiation in Luanchuan area was also prospected. It is of great significance to further improve the recovery efficiency of low-grade scheelite resources in Luanchuan area and this can provide technical reference for other scheelite plants.展开更多
Polyaspartic acid(PASP)was used as a novel environmental-friendly depressant,and its inhibition effect on flotation performance of scheelite and calcite using sodium oleate(NaOL)as a collector was investigated by ways...Polyaspartic acid(PASP)was used as a novel environmental-friendly depressant,and its inhibition effect on flotation performance of scheelite and calcite using sodium oleate(NaOL)as a collector was investigated by ways of flotation experiments,zeta potential measurement,contact angle measurement and infrared spectroscopic analysis(IR).The results show that PASP exhibits stronger inhibition capability and selectivity than acidified water glass,and the flotation separation of scheelite from calcite can be realized in the presence of 6 mg/L PASP and 20 mg/L NaOL at pH>6.In the presence of PASP,the zeta potential of calcite surface almost keeps unchanged after adding NaOL,and the contact angle decreases sharply.Therefore,it is indicated that PASP significantly decreases the adsorption of NaOL on calcite surface.By contrast,it has no distinct effect on the adsorption of NaOL on the scheelite surface,which is further confirmed by IR results.展开更多
In this study, the innovative use of ethylenediamine tetramethylene phosphonic sodium(EDTMPS) as a calcite depressant in scheelite flotation was investigated by flotation experiments, and its selective depression mech...In this study, the innovative use of ethylenediamine tetramethylene phosphonic sodium(EDTMPS) as a calcite depressant in scheelite flotation was investigated by flotation experiments, and its selective depression mechanism was revealed by contact angle measurement, FTIR analysis, Zeta potential test and XPS analysis. The flotation experiment results showed that scheelite and calcite could be efficiently separated under the following conditions: pulp p H=9.5, Na OL concentration of 1.5×10^(-4)mol/L, EDTMPS concentration of 3.0×10^(-5)mol/L, a scheelite concentrate with WO3grade of 65.49%, recovery of 83.29%and separation efficiency of 65.29% could be obtained from the artificially mixed minerals. The analysis results of mineral surface properties demonstrated that EDTMPS was strongly adsorbed onto the calcite surface through the reaction between the phosphonate group and the calcium ions, which hindered Na OL adsorption and increased the hydrophilicity of calcite. However, EDTMPS had weak adsorption strength on the scheelite surface, which didn’t affect further adsorption of Na OL, hence, the scheelite remained hydrophobic. Consequently, the selective adsorption of EDTMPS on the two minerals’ surfaces increased a difference in wettability and thus enabling them to be separated by flotation. Finally, the mechanism model of this flotation separation process was established.展开更多
For further comprehending the mechanism of the intensification of ultrasound for extraction,the difference of leaching kinetics between the ultrasound-assisted and conventional sodium carbonate leaching of scheelite w...For further comprehending the mechanism of the intensification of ultrasound for extraction,the difference of leaching kinetics between the ultrasound-assisted and conventional sodium carbonate leaching of scheelite was studied,and the corresponding kinetic equations were established.The results indicate that the obtained apparent activation energy with or without ultrasound is same 72 kJ/mol,and both reactions are controlled by surface chemical reaction.By comparing the leaching kinetics of scheelite by Na2CO3,NaOH and Na3PO4 reactants with or without ultrasound,a general conclusion for scheelite hydrometallurgy is obtained.For the process with the formation of compact product layer,the intensification of the tungsten extraction with ultrasound mainly reflects in the stripping and elimination of product layer,corresponding to the transformation of kinetic controlling step from diffusion controlling step and reduction of apparent activation energy.For the one without compact product layer or with a loose and porous product layer,the intensification mainly embodies in the increase of frequency factor,and the controlling step and apparent activation energy of the reaction always remain constant.展开更多
The depression behavior and mechanism of guar gum on talc-type scheelite flotation were systematically investigated by flotation experiments, adsorption tests, zeta-potential measurements, and infrared spectroscopic a...The depression behavior and mechanism of guar gum on talc-type scheelite flotation were systematically investigated by flotation experiments, adsorption tests, zeta-potential measurements, and infrared spectroscopic analyses. The flotation results for monominerals, mixed minerals, and actual mineral samples indicated that guar gum exhibited much higher selective depression for talc than for scheelite. Bench-scale closed-circuit tests showed that a tungsten concentrate with a WO_3 grade of 51.43% and a WO_3 recovery of 76.18% was obtained. Adsorption tests, zeta-potential measurements, and infrared spectral analyses confirmed that guar gum absorbed more strongly onto the talc surface than onto the scheelite surface because of chemisorption between guar gum and talc. This chemisorption is responsible for the guar gum's highly selective depression for talc and small depression for scheelite. The flotation results provide technical support for talc-type scheelite flotation.展开更多
The composition of a collector directly affects its collecting performance in mineral flotation.In this study,three vegetable oils were used as the collectors,the flotation performance of scheelite and the differentia...The composition of a collector directly affects its collecting performance in mineral flotation.In this study,three vegetable oils were used as the collectors,the flotation performance of scheelite and the differential analysis were studied through flotation experiments,zeta potential,contact angle measurement and Fourier transform infrared spectrum(FTIR)analysis.Flotation results show that the recovery of scheelite increases in the order of oleic acid<rapeseed oil<rice bran oil<soybean oil,especially in the pH range of 5-8.The distinction in the scheelite recovery is due to the different compositions of these collectors.The addition of LA,LNA and PA(<5%)can increase the recovery of scheelite with OA,but the addition of SA deteriorates the scheelite flotation.Results of zeta potential,contact angle measurement and FTIR analysis indicate that the collector adsorption on scheelite surface is enhanced when using the three vegetable oils.For the raw ore with 0.086%WO3,a rough concentrate containing 1.423%WO3 with the recovery of 84.22%is obtained using soybean oil as the collector.展开更多
The reaction kinetics for the leaching of low-grade scheelite concentrate was investigated in an autoclave with sodium hydroxide in the presence of phosphate. The effects of stirring speed (300-600 r/min), reaction te...The reaction kinetics for the leaching of low-grade scheelite concentrate was investigated in an autoclave with sodium hydroxide in the presence of phosphate. The effects of stirring speed (300-600 r/min), reaction temperature (353-383 K), sodium hydroxide concentration (1.69-6.76 mol/L) and phosphate concentration (0.68-1.69 mol/L) on the WO3 dissolution ratio were studied. The results showed that the WO3 dissolution ratio was practically independent of stirring speed, while it increased with increasing the reaction temperature, and the concentrations of sodium hydroxide and phosphate. The experimental data were consistent with the shrinking core model, with a surface chemical reaction as the leaching rate-determining step. The apparent activation energy was calculated as 49.56 kJ/mol, and the reaction orders with respect to the concentrations of sodium hydroxide and phosphate were determined as 0.27 and 0.67, respectively. The kinetics equation of the leaching process was established.展开更多
Effects of carboxylic acid collector, benzohydroxamic acid (BHA), sodium hexametaphosphate (SHAP), sodium silicate, and oxalic acid on scheelite flotation were studied through flotation tests, quantum chemical calcula...Effects of carboxylic acid collector, benzohydroxamic acid (BHA), sodium hexametaphosphate (SHAP), sodium silicate, and oxalic acid on scheelite flotation were studied through flotation tests, quantum chemical calculation, and flotation solution computational chemistry. In terms of the calculation results, the relationship between chemical reactions occurring on the scheelite surface and molecular structures of the reagents were analyzed. The results show that BHA and carboxylic acid collectors interact with scheelite in different forms and the recovery of scheelite using sodium oleate as collector declines successively from SHAP, sodium silicate, to oxalic acid. Moreover, it is found that the performance of depressant in scheelite flotation is directly related to the group electronegativity, indicating that the latter is a dominant factor that determines the former. These findings will be helpful to the academic research communities of scheelite flotation.展开更多
In this paper,using methyl cinnamate as raw material,the new cinnamic hydroxamic acid collector(CIHA)was synthesized by the hydroxylamine method.The collector performance of hydroxamic acid was investigated for scheel...In this paper,using methyl cinnamate as raw material,the new cinnamic hydroxamic acid collector(CIHA)was synthesized by the hydroxylamine method.The collector performance of hydroxamic acid was investigated for scheelite and gangue calcite,and the flotation separation test of scheelite and calcite was carried out with CIHA as the collector.The interaction mechanism between hydroxamic acid and scheelite minerals has also been investigated through zeta potential,Fourier transform infrared spectroscopy(FTIR)experiments,X-ray photoelectron spectroscopy(XPS)experiments,and density functional theory(DFT)calculation.The single mineral flotation test and artificially mixed ore showed that CIHA had an excellent collection effect and selectivity.Zeta potential,FTIR,and XPS showed that CIHA was adsorbed on the scheelite surface by strong chemical adsorption.The active group of CIHA was analyzed through quantum chemical calculation.It was speculated that C=O and N-O bonds could synthesize a five-membered chelated hydroxamic acid group with Ca element chelate on scheelite surface,changing hydrophobicity and making it more likely to emerge from the pulp.展开更多
Based on physicochemical study of the reaction between scheelite and NaOH, a new decomposition process for scheelite and scheelitewolframite concentrate, i. e., mechenically activating caustic decomposition has bee...Based on physicochemical study of the reaction between scheelite and NaOH, a new decomposition process for scheelite and scheelitewolframite concentrate, i. e., mechenically activating caustic decomposition has been developed, and it has been successfu展开更多
The extraction of tungsten from scheelite was carried out using a sulfuric acid solution with oxalic acid as the chelating agent.Tungsten was obtained in the form of highly soluble hydrogen aqua oxalato tungstate H_(2...The extraction of tungsten from scheelite was carried out using a sulfuric acid solution with oxalic acid as the chelating agent.Tungsten was obtained in the form of highly soluble hydrogen aqua oxalato tungstate H_(2)[WO_(3)(C_(2)O_(4))·H_(2)O] during the leaching process,while calcium remained in the residue as calcium sulfate dihydrate(CaSO4·2H2O).About 99.2%of the tungsten was leached at 70℃,1.5 mol/L sulfuric acid,1 mol/L oxalic acid,a liquid/solid ratio of 25:1(mL/g),an oxalic acid to sulfuric acid molar ratio of 1:1,a stirring speed of 300 r/min and a leaching time of 2 h.H_(2)[WO_(3)(C_(2)O_(4))·H_(2)O]was thermally decomposed into tungstic acid(H_(2)WO_(4)),and tungsten trioxide(WO_(3))was directly produced by calcining H_(2)WO_(4) at 700℃ for 2 h.The surface chemical reaction was determined to be the controlling step during tungsten leaching,and the apparent activation energy was calculated to be 51.43 kJ/mol.展开更多
基金financially supported by the National Natural Science Foundation of China(Nos.52304314 and U23A20602)the Open Fund of the Key Laboratory of Mineral Metallurgical Resources Utilization and Pollution Control,Ministry of Ecology and Environment+3 种基金China(No.HB202406)the Fundamental Research Funds for the Central Universities of Central South University,China(Nos.CX20240021 and 2024ZZTS0008)the Innovation and Entrepreneurship Funding Project for College Students of Central South UniversityChina(No.S202410533166)。
文摘Flotation is the most common method to recover valuable minerals by selective adsorption of collectors on target mineral surfaces.However,in subsequent hydrometallurgy of mineral flotation concentrates,the adsorbed collectors must be desorbed since it can adversely affect the efficiency of metallurgical process and produce wastewater.ZL,as a fatty acid mixture,is a typical industrially used collector for scheelite flotation in China.Sodium oleate(NaOL)has similar fatty acid group as ZL.In this study,the desorption behavior of NaOL/ZL from scheelite surface by a physical method of stirring at a low temperature was investigated.NaOL desorption tests of single mineral showed that a desorption rate of 77.75% for NaOL from scheelite surface into pulp was achieved in a stirring speed of2500 r/min at 5℃in a neutral environment.Under the above desorption condition,in the pulp containing desorbed collector by adding extra 30% normal NaOL dosage,the scheelite recovery reached about 95% in the single mineral flotation test.Desorption and reuse of ZL collector for the flotation of real scheelite ore showed only a 75%normal dosage of ZL could produce a qualified rough concentrate.The atomic force microscope(AFM)tests showed that after desorption treatment of low temperature and strong stirring,the dense strip-like structure of NaOL on the scheelite surface was destroyed to be speck-like.Molecular dynamics simulations(MDS)demonstrated that the adsorption energy between NaOL and scheelite surface was more negative at 25℃(-13.39 kcal/mol)than at 5℃(-11.50 kcal/mol)in a neutral pH,indicating that a low temperature was beneficial for the desorption of collector from mineral surface.Due to its simplicity and economy,the method we proposed of desorption of collector from mineral surface and its reuse for flotation has a great potential for industrial application.
基金supported by the National Natural Science Foundation of China(No.52164022).
文摘This study investigated the effect of konjac glucomannan(KGM)on the flotation separation of calcite and scheelite.Micro-flotation tests showed that under the action of 50 mg/L KGM,the floatability of calcite notably decreased,while the impact on scheelite was negligible,resulting in a recovery difference of 82.53%.Fourier transform infrared(FTIR)spectroscopy and atomic force micro-scopy(AFM)analyses indicated the selective adsorption of KGM on the calcite surface.Test results of the zeta potential and UV-visible absorption spectroscopy revealed that KGM prevented the adsorption of sodium oleate on the calcite surface.X-ray photoelectron spec-troscopy(XPS)analysis further confirmed the chemical adsorption of KGM on the calcite surface and the formation of Ca(OH)_(2).The density functional theory(DFT)simulation results were consistent with the flotation tests,demonstrating the strong adsorption perform-ance of KGM on the calcite surface.This study offers a pathway for highly sustainable and cost-effective mineral processing by utilizing the unique properties of biopolymers such as KGM to separate valuable minerals from gangue minerals.
基金financed by Yunnan Major Scientific and Technological Projects(Grant No.202202AG050006)the National Natural Science Foundation of China(Grant No.42462011)Projects of Yunnan Province Technology Hall(Grant No.202305AT350004).
文摘The Gejiu tin-copper-(tungsten)(Sn-Cu-(W))polymetallic district is located in the southwest of the W-Sn metallogenic belt in the western Youjiang Basin,Yunnan,Southwest China.Abundant W minerals have been identified in the region via exploration.However,metallogenic sources and evolution of W remain unclear,and the existing metallogenic model has to be updated to guide further ore prospecting.Elemental and Sr-Nd isotopic data for scheelites assist in the determination of sources and evolution of the W-mineralizing fluids and metals in the district.Based on field geological survey,the scheelites in the Gejiu district can be categorized into three types:altered granite(Type Ⅰ),quartz vein(Type Ⅱ)from the Laochang deposit,and skarn(Type Ⅲ)from the Kafang deposit.Types Ⅰ and Ⅱ scheelites have low molybdenum(Mo)and strontium(Sr)contents,and Type Ⅱ scheelite has lower Sr contents than Type Ⅰ as well as higher Mo and Sr contents than Type Ⅲ scheelites.Varying Mo contents across the scheelite types suggests that the oxygen fugacity varied during ore accumulation.Type Ⅰ and Type Ⅱ scheelites exhibit similar rare earth elements(REE)patterns;Type Ⅲ scheelite contains lower REE content,particularly HREE,compared with the other scheelites.All scheelites exhibit negative Eu anomalies in the chondrite-normalized REE patterns.As the W-mineralization and two-mica granite share close spatial and temporal relationships,the negative Eu anomalies were likely inherited from the two-mica granite.Type Ⅰ and Type Ⅱ scheelites display varied(^(87)Sr/^(86)Sr)_(82 Ma)(0.7090-0.7141)andε_(Nd)(82 Ma)(from−9.9 to−5.4)values,similar to those of granite.However,Type Ⅲ scheelite exhibits lower(^(87)Sr/^(86)Sr)_(82 Ma)(0.7083-0.7087)and lowerε_(Nd)(82 Ma)(from−10.5 to−6.9)values than the two-mica granite.This indicates that the two-mica granite alone did not provide the ore-forming fluids and metals and that the Type Ⅲ scheelite ore-forming fluids likely involved external fluids that were probably derived from carbonate rocks.The implication is that highly differentiated two-mica granites were the source of primary W-bearing metals and fluids,which is consistent with earlier research on the origin of Sn ore-forming materials.
基金suppor ted by Yunnan Major Scientific and Technological Projects(Grant No.202202AG050006)the Personnel Training Project of Kunming University of Science and Technology(Grant No.KKZ3202221022)。
文摘The Guanfang large-scale W deposit is located in the W polymetallic ore concentration area of Bozhushan in southeastern Yunnan,China.Despite extensive research,the fluid evolution process of the deposit remains ambiguous,leading to controversy regarding its genesis.This study conducted a detailed field geological survey,with systematic sampling of the KT6 orebody,to delineate mineralization stages.Fine mineralogy work,including the use of CL images of scheelite,in-situ LA-ICP-MS trace elements,and Sr isotopes,was carried out on diff erent generations of scheelite formed in various stages.The findings identified the evolution of fluids in the mineralization process,shedding light on the genesis of the deposit.The study revealed four mineralization stages at the Guanfang W deposit:prograde skarn stage,retrograde skarn stage,quartz-sulfide stage,and carbonate-fluorite stage.Diff erent generations of scheelite(Sch I,Sch II,Sch III)were observed in the first three stages,displaying distinct chondrite-normalized REE patterns.The REE of Sch I mainly substituted into the Ca site by REE^(3+)+□_(Ca),and there may be a similar substitution of Nb for REE,whereas it is not the main substitution method.The REE of Sch II mainly enter the scheelite lattice in the form of REE 3++Na+,and there may be a substitution of Nb for REE isomorphism.In the early stage,The REE of Sch III was mainly replaced by Nb for REE isomorphism,while in the later stage,the replacement mode of REE^(3+)+□_(Ca)coexisted with it.The Mo content in scheelite,along with the corresponding Eu anomalies in both scheelite and garnet,collectively imply that the ore-forming fluids during various mineralization stages were predominantly oxidizing,with only slight reducibility observed in Sch II.The in-situ Sr isotope ratios of scheelite concentrates ranged from 0.7093 to 0.7153,resembling those of the Bozhushan granite,indicating a relationship between W mineralization and granite.In addition,the Y/Ho ratios of scheelite from various mineralization stages exhibit a narrow range(19-31),with a pronounced correlation between the contents of Y and Ho and a similar trend in their variation.This consistency suggests that the Guanfang deposit has undergone a uniform or comparable evolutionary process,implying a stable ore-forming fluid across diff erent mineralization stages.
基金Project(50831006)supported by the National Natural Science Foundation of ChinaProject(CX2011B122)supported by Hunan Provincial Innovation Foundation for Postgraduate,ChinaProject(2012BAB10B05)supported by the National Key Technologies R&D Program of China
文摘Surface energies of five different surfaces of scheelite crystal were calculated using density functional theory （DFT）. Based on the calculation results, the predominantly exposed surfaces in the morphologies of scheelite crystals were predicted. {112} and {001} cleavage surfaces and {112} crystal surface are the commonly exposed surfaces, which are consistent with both previous literatures and the present experimental observations based on the XRD. Cleavage generates more easily along {112} surfaces than along {001} surfaces due to their different interlayer spacings. The surface roughness and appearance of different predominantly exposed surfaces were then investigated using AFM. The roughness of smooth {112} cleavage surface is the lowest among these three surfaces. On {001} cleavage surface, terraces are flat and separated by steps of about 10 nm in height. Subsequently, contact angle measurements were adopted to evaluate the wettability and surface energies of these surfaces. The surface energies evaluated directly correspond to the trend calculated with DFT.
基金Project(51074037)supported by the National Natural Science Foundation of China
文摘Effects of size distribution (particle size and content of fine fraction (<10μm)) on scheelite flotation were studied using flotation tests and theoretical calculations. The results show that particle size influences the scheelite recovery and the performance of combined reagents. The scheelite recovery is lowered by adding fine particles (<10μm) into the pulp containing coarse particles. Extended DLVO (EDLVO) theory confirms that the fine fractions (<10μm) could interface with the coarse fractions. The interaction energy and fluid forces are relative to the particle size, which might explain why the fine fractions influence the scheelite flotation. The highest recovery of scheelite using combined reagents as collector and optimum ratio of combined reagents were determined by scheelite particle size and reagent performance. However, the optimum adding order was only determined by reagent performance, which has nothing to do with particle size.
文摘The effect of different decomposition conditions on tungsten recovery forscheelite concentrate has been examined. The results show that tungsten recovery can be more than98% under decomposing conditions as follows: the amount of caustic soda is 2.2 and 3.2 times oftheoretical respectively, ratio of water and ore is 0.7-0.8, temperature is 160℃, and preservationtime is 2.0 h for scheelite concentrate (63.21 % WO_3) and low grade scheelite concentrate (55.17%WO_3).
文摘Scheelite and scheelite-wolframite mixed concentrates with different grades were decomposed by caustic soda digestion, and the effects of caustic soda（NaOH） dosage, the ratio of water to ore and the stirring rate on tungsten recovery were studied. The results show that under the conditions that the ratio of water to ore is （0.8,） stirring rate is 500 r·min-1 and the heating time is 2.0 h at （160 ℃,） the recovery of tungsten reaches 98% for scheelite （w（WO3） is （65.04%）） and wolframite containing high proportion of calcium （w（WO3） is 65.58%, w（Ca） is （7.53%）,） when caustic soda dosage is 2.2 and 2.0 times of theoretical value, respectively; the recovery of tungsten can be more than 98%,98% and 96% respectively for low-grade scheelite-wolframite mixed concentrate with （55.78%,） 45.32% and 25.21% WO3, when caustic soda dosage is 2.6,3.2 and 5.5 times of theoretical value, respectively.
基金the financial support of the Optim Ore projectthe European Union’s Horizon 2020 research and innovation programme under grant agreement No. 642201
文摘Froth flotation of scheelite has regained new focus since the 2010s and research regarding floatability and reagents has made great progress over the years. The main objective was and remains the selective flotation of scheelite from other calcium-bearing minerals, in particular calcite, fluorite and apatite. Due to similar properties, most attempts have limited success or only specific application(linked to a type of ore or a location). This article aims at reviewing all general physical-chemical information on froth flotation of scheelite, including electrokinetic properties, influence of p H and already existing reagents as well as ones still under examination. It appears that chelating or mixed collectors and modified versions of sodium silicate and quebracho hold great promise for scheelite flotation, while the use of said depressants and/or promoters seems inevitable.
基金the financial support from the National Natural Science Foundation of China (No. 51974364)Postgraduate Independent Exploration and Innovation Project of Central South University, China (No. 2018zzts224)the Key Laboratory of Hunan Province for Clean and Efficiency Utilization of Strategic Calcium-containing Mineral Resources, China (No. 2018TP1002)。
文摘Luanchuan area is one of the regions with the largest scale of scheelite beneficiation and the largest output of scheelite concentrate in the world. After years of innovation and progress, the beneficiation technology of low-grade scheelite associated with molybdenum tailings in Luanchuan area is becoming more and more perfect. In this study, the development process of low-grade scheelite recycling technology in Luanchuan area was reviewed, including raw ore properties, beneficiation process, flotation equipment and flotation reagents. Meanwhile, taking Luoyang Yulu Mining Co., Ltd. as an example, the effects of various technical transformations such as the optimization of the beneficiation process, the column-machine combined process, and the high-efficiency flotation reagents were elucidated in detail. However, the recycling technology of low-grade scheelite of Luanchuan area is still possible to be improved. As a result, coupled with the latest research progress, the development direction of low-grade scheelite beneficiation in Luanchuan area was also prospected. It is of great significance to further improve the recovery efficiency of low-grade scheelite resources in Luanchuan area and this can provide technical reference for other scheelite plants.
基金financial support from the Youth Science Foundation of China(No.52004333)。
文摘Polyaspartic acid(PASP)was used as a novel environmental-friendly depressant,and its inhibition effect on flotation performance of scheelite and calcite using sodium oleate(NaOL)as a collector was investigated by ways of flotation experiments,zeta potential measurement,contact angle measurement and infrared spectroscopic analysis(IR).The results show that PASP exhibits stronger inhibition capability and selectivity than acidified water glass,and the flotation separation of scheelite from calcite can be realized in the presence of 6 mg/L PASP and 20 mg/L NaOL at pH>6.In the presence of PASP,the zeta potential of calcite surface almost keeps unchanged after adding NaOL,and the contact angle decreases sharply.Therefore,it is indicated that PASP significantly decreases the adsorption of NaOL on calcite surface.By contrast,it has no distinct effect on the adsorption of NaOL on the scheelite surface,which is further confirmed by IR results.
基金the National Natural Science Foundation of China(Nos.51604302 and 51574282)the Key Laboratory of Hunan Province for Clean and Efficient Utilization of Strategic Calcium-containing Mineral Resources(No.2018TP1002).
文摘In this study, the innovative use of ethylenediamine tetramethylene phosphonic sodium(EDTMPS) as a calcite depressant in scheelite flotation was investigated by flotation experiments, and its selective depression mechanism was revealed by contact angle measurement, FTIR analysis, Zeta potential test and XPS analysis. The flotation experiment results showed that scheelite and calcite could be efficiently separated under the following conditions: pulp p H=9.5, Na OL concentration of 1.5×10^(-4)mol/L, EDTMPS concentration of 3.0×10^(-5)mol/L, a scheelite concentrate with WO3grade of 65.49%, recovery of 83.29%and separation efficiency of 65.29% could be obtained from the artificially mixed minerals. The analysis results of mineral surface properties demonstrated that EDTMPS was strongly adsorbed onto the calcite surface through the reaction between the phosphonate group and the calcium ions, which hindered Na OL adsorption and increased the hydrophilicity of calcite. However, EDTMPS had weak adsorption strength on the scheelite surface, which didn’t affect further adsorption of Na OL, hence, the scheelite remained hydrophobic. Consequently, the selective adsorption of EDTMPS on the two minerals’ surfaces increased a difference in wettability and thus enabling them to be separated by flotation. Finally, the mechanism model of this flotation separation process was established.
基金Project(51604160)supported by the National Natural Science Foundation of ChinaProject(2016zzts037)supported by the Fundamental Research Funds for the Central Universities of China
文摘For further comprehending the mechanism of the intensification of ultrasound for extraction,the difference of leaching kinetics between the ultrasound-assisted and conventional sodium carbonate leaching of scheelite was studied,and the corresponding kinetic equations were established.The results indicate that the obtained apparent activation energy with or without ultrasound is same 72 kJ/mol,and both reactions are controlled by surface chemical reaction.By comparing the leaching kinetics of scheelite by Na2CO3,NaOH and Na3PO4 reactants with or without ultrasound,a general conclusion for scheelite hydrometallurgy is obtained.For the process with the formation of compact product layer,the intensification of the tungsten extraction with ultrasound mainly reflects in the stripping and elimination of product layer,corresponding to the transformation of kinetic controlling step from diffusion controlling step and reduction of apparent activation energy.For the one without compact product layer or with a loose and porous product layer,the intensification mainly embodies in the increase of frequency factor,and the controlling step and apparent activation energy of the reaction always remain constant.
基金financially supported by the National Natural Science Foundation of China (No.51404218)the National Key Technology R&D Program (No.2015BAB12B02)the Science and Technology Planning Project of Guangdong Province, China (No.2013B090800016)
文摘The depression behavior and mechanism of guar gum on talc-type scheelite flotation were systematically investigated by flotation experiments, adsorption tests, zeta-potential measurements, and infrared spectroscopic analyses. The flotation results for monominerals, mixed minerals, and actual mineral samples indicated that guar gum exhibited much higher selective depression for talc than for scheelite. Bench-scale closed-circuit tests showed that a tungsten concentrate with a WO_3 grade of 51.43% and a WO_3 recovery of 76.18% was obtained. Adsorption tests, zeta-potential measurements, and infrared spectral analyses confirmed that guar gum absorbed more strongly onto the talc surface than onto the scheelite surface because of chemisorption between guar gum and talc. This chemisorption is responsible for the guar gum's highly selective depression for talc and small depression for scheelite. The flotation results provide technical support for talc-type scheelite flotation.
基金Project(2016RS2016) supported by Provincial Science and Technology Leader Program,Hunan,ChinaProject(2017zzts807) supported by Postgraduate Innovative Research Projects of Central South University,China
文摘The composition of a collector directly affects its collecting performance in mineral flotation.In this study,three vegetable oils were used as the collectors,the flotation performance of scheelite and the differential analysis were studied through flotation experiments,zeta potential,contact angle measurement and Fourier transform infrared spectrum(FTIR)analysis.Flotation results show that the recovery of scheelite increases in the order of oleic acid<rapeseed oil<rice bran oil<soybean oil,especially in the pH range of 5-8.The distinction in the scheelite recovery is due to the different compositions of these collectors.The addition of LA,LNA and PA(<5%)can increase the recovery of scheelite with OA,but the addition of SA deteriorates the scheelite flotation.Results of zeta potential,contact angle measurement and FTIR analysis indicate that the collector adsorption on scheelite surface is enhanced when using the three vegetable oils.For the raw ore with 0.086%WO3,a rough concentrate containing 1.423%WO3 with the recovery of 84.22%is obtained using soybean oil as the collector.
基金Projects(51674067,51422402) supported by the National Natural Science Foundation of ChinaProjects(N150101001,N160106004,N170106005) supported by the Fundamental Research Funds for the Central Universities,China
文摘The reaction kinetics for the leaching of low-grade scheelite concentrate was investigated in an autoclave with sodium hydroxide in the presence of phosphate. The effects of stirring speed (300-600 r/min), reaction temperature (353-383 K), sodium hydroxide concentration (1.69-6.76 mol/L) and phosphate concentration (0.68-1.69 mol/L) on the WO3 dissolution ratio were studied. The results showed that the WO3 dissolution ratio was practically independent of stirring speed, while it increased with increasing the reaction temperature, and the concentrations of sodium hydroxide and phosphate. The experimental data were consistent with the shrinking core model, with a surface chemical reaction as the leaching rate-determining step. The apparent activation energy was calculated as 49.56 kJ/mol, and the reaction orders with respect to the concentrations of sodium hydroxide and phosphate were determined as 0.27 and 0.67, respectively. The kinetics equation of the leaching process was established.
基金financially supported by the National Natural Science Foundation of China(No.51074037)
文摘Effects of carboxylic acid collector, benzohydroxamic acid (BHA), sodium hexametaphosphate (SHAP), sodium silicate, and oxalic acid on scheelite flotation were studied through flotation tests, quantum chemical calculation, and flotation solution computational chemistry. In terms of the calculation results, the relationship between chemical reactions occurring on the scheelite surface and molecular structures of the reagents were analyzed. The results show that BHA and carboxylic acid collectors interact with scheelite in different forms and the recovery of scheelite using sodium oleate as collector declines successively from SHAP, sodium silicate, to oxalic acid. Moreover, it is found that the performance of depressant in scheelite flotation is directly related to the group electronegativity, indicating that the latter is a dominant factor that determines the former. These findings will be helpful to the academic research communities of scheelite flotation.
基金the National Nature Science Foundation of China(No.51774152)Jiangxi Provincial Education Department(GJJ200816)+1 种基金“Double height project”in Jiangxi province(No.[2022]223)the National Nature Science Foundation of China(No.52264023).
文摘In this paper,using methyl cinnamate as raw material,the new cinnamic hydroxamic acid collector(CIHA)was synthesized by the hydroxylamine method.The collector performance of hydroxamic acid was investigated for scheelite and gangue calcite,and the flotation separation test of scheelite and calcite was carried out with CIHA as the collector.The interaction mechanism between hydroxamic acid and scheelite minerals has also been investigated through zeta potential,Fourier transform infrared spectroscopy(FTIR)experiments,X-ray photoelectron spectroscopy(XPS)experiments,and density functional theory(DFT)calculation.The single mineral flotation test and artificially mixed ore showed that CIHA had an excellent collection effect and selectivity.Zeta potential,FTIR,and XPS showed that CIHA was adsorbed on the scheelite surface by strong chemical adsorption.The active group of CIHA was analyzed through quantum chemical calculation.It was speculated that C=O and N-O bonds could synthesize a five-membered chelated hydroxamic acid group with Ca element chelate on scheelite surface,changing hydrophobicity and making it more likely to emerge from the pulp.
文摘Based on physicochemical study of the reaction between scheelite and NaOH, a new decomposition process for scheelite and scheelitewolframite concentrate, i. e., mechenically activating caustic decomposition has been developed, and it has been successfu
基金financial supports from the National Natural Science Foundation of China (Nos.51564019, 51674125)Science and Technology Project of Jiangxi Provincial Education Department,China (No.GJJ181501).
文摘The extraction of tungsten from scheelite was carried out using a sulfuric acid solution with oxalic acid as the chelating agent.Tungsten was obtained in the form of highly soluble hydrogen aqua oxalato tungstate H_(2)[WO_(3)(C_(2)O_(4))·H_(2)O] during the leaching process,while calcium remained in the residue as calcium sulfate dihydrate(CaSO4·2H2O).About 99.2%of the tungsten was leached at 70℃,1.5 mol/L sulfuric acid,1 mol/L oxalic acid,a liquid/solid ratio of 25:1(mL/g),an oxalic acid to sulfuric acid molar ratio of 1:1,a stirring speed of 300 r/min and a leaching time of 2 h.H_(2)[WO_(3)(C_(2)O_(4))·H_(2)O]was thermally decomposed into tungstic acid(H_(2)WO_(4)),and tungsten trioxide(WO_(3))was directly produced by calcining H_(2)WO_(4) at 700℃ for 2 h.The surface chemical reaction was determined to be the controlling step during tungsten leaching,and the apparent activation energy was calculated to be 51.43 kJ/mol.
