Flotation separation of wolframite from calcite using a new trisiloxane surfactant as collector

Since wolframite is usually associated with calcite,the separation and enrichment of wolframite by froth flotation remains a great challenge.Herein,a novel trisiloxane surfactant N-(2-aminoethyl)-3-ami nopropyltrisiloxane(AATS)was successful synthesized,which was used for the separation of wolframite from calcite for the first time.The flotation separation performance of AATS was studied by flotation test,and its adsorption mechanism was explored based on contact angle,infrared spectrum analysis(FTIR),zeta potential and density functional theory(DFT)calculation.The results of microflotation test and binary mixed ore flotation test pointed that AATS had excellent selectivity and more prominent collection capacity for the flotation of wolframite when compared with industrial reagent sodium oleate(NaOL).The measurement results of contact angle proved that AATS improved the hydrophobicity of the wolframite surface.The highly selective adsorption mechanism of AATS surfactant on mineral surfaces were further researched and analyzed by FTIR and zeta potential.The results revealed that AATS surfactant had significant adsorption effect on wolframite,yet almost no adsorption on calcite.DFT calculation indicated that AATS produced electrostatic adsorption with wolframite surface through—N+H3 group.

Decomposing scheelite and scheelite-wolframite mixed concentrate by caustic soda digestion

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.

Effect of temperature on floatability and adsorption behavior of fine wolframite with sodium oleate

The influence of pulp temperature on the floatability and adsorption behavior of fine wolframite with sodium oleate was investigated by microflotation experiments, electric conductivity tests, adsorption measurements, and FT-IR analysis. Microflotation results show that fine wolframite with sodium oleate exhibits a good floatability at pH 8–9. Electric conductivity tests indicate that the high temperature enhances the ionization degree and electric mobility of oleate species, then the flotation recovery of fine wolframite and the adsorption amount of sodium oleate are observed to increase with the rise in pulp temperature. The results of adsorption experiments are found to meet Freundlich isotherms successfully, and the isosteric enthalpy （ΔH^Θ） is in conformity with the chemical bonding. The changes in FT-IR analysis provide sufficient evidence that sodium oleate interacts with the metal cations of wolframite surface, and the increase in pulp temperature clearly promotes the chemisorption intensity. These findings will be beneficial to strengthen the flotation behavior of fine wolframite.

Flotation behavior and adsorption mechanism of fine wolframite with octyl hydroxamic acid

Flotation behavior and adsorption mechanism of octyl hydroxamic acid(OHA)on wolframite were investigated through flotation experiments,adsorption tests,zeta-potential measurements,infrared spectroscopy and solution chemistry calculations.Results of flotation and adsorption experiments show that the maximum values of flotation recovery and adsorption capacity occur around p H 9.In term of the solution chemistry calculations,the concentration of metal hydroxamate is greater than that of metal tungstate and metal hydroxyl,and metal hydroxamate compounds are identified to be the main species on wolframite surface at p H region of 8-10,contributing to the increase of OHA adsorption and flotation performance.Results of zeta-potential and IR spectra demonstrate that OHA adsorbs onto wolframite surface by chemisorptions.Hydroxamate ions can bond with Mn_2+/Fe_2+cations of wolframite surface,forming metal hydroxamate compounds,which is a key factor in inducing the hydrophobicity of wolframite under the conditions of maximum flotation.

Flotation evaluation and adsorption mechanism of medialan collector to wolframite

Medialan has preferable flotation performance to wolframite,under the conditions of the best flotation pH value 7.0 and low dosage,wolframite recovery is up to80%.Medialan shows poor flotation performance to quartz,but better to fluorite and calcite.However,fluorite and calcite are inhibited in a certain degree by adding medialan mixed with sodium silicate.Adsorption mechanism of medialan collector on wolfram surface was also studied by using infrared(IR)radiation spectrum,adsorption volume,and zeta potential.The results show that medialan can adsorb on wolfram surface in the form of chemistry adsorption,and as medialan collector dosage changes,change law of adsorption volume is similar with that of wolfram pure mineral flotation.Zeta potential results prove that zeta potential of wolfram surface moves negatively after adsorbing medialan collector.

Electrochemical Study on FXL-I4 Collecting Wolframite without Pb^(2+) Flotation

In this paper,FXL-14 (tetradecyl iminobimetyl phosphonic acid) as a collector for floating wolframite without Pb^(2+) and its adsorption mechanism were studied by electrochemical method.Flotation experiment results showed that in the wide range of pH value activation of FXL-14 collecting wolframite with Pb^(2+) was not needed.Wolframite—carbon paste electrode and small-amplitude triangular potential sweep were used to measure the electro-double-layer capacitance of wolframite in the FXL-14 solution (with and without of the presence of 1×10^(-4)MPb^(2+)).It is showed that in spite of concentration of Pb^(2+) in the flotation processing,with FXL-14 (800mg/l) the electro-double-layer capacitance was bigger than with FXL-14 (800mg/l) and Pb^(2+).

Kinetics and mechanism of natural wolframite interactions with sodium carbonate

The kinetics and mechanism of natural wolframite interactions with sodium carbonate during air heating were studied.X-ray phase and X-ray microanalysis were used to establish that the initial monocrystalline wolframite consists of Fe0.5 Mn0.5 WO4 and Fe0.3 Mn0.7 WO4.Differential thermal analysis showed that the interaction of wolframite with sodium carbonate begins above 450°C with the formation of tungstate,sodium ferrite,iron oxides,and manganese.Model experiments on sintering with the subsequent removal of water-soluble compounds(leaching)tracked the change in the structure of wolframite.The atomic ratio of Fe/Mn in wolframite does not change up to 600°C,and subsequently decreases to 0.2 during heating,which allows the mechanism of the process to be identified and indicates the greater reactivity of wolframites with an increased proportion of iron.Thermal analysis with data processing using non-isothermal kinetics established that the interaction of wolframite with sodium carbonate in an air stream proceeds via a two-stage mechanism,wherein the first stage is limited by diffusion(activation energy,E=243 kJ/mol)and the second stage is limited by autocatalysis(activation energy,E=212 k J/mol)due to the formation of a Na2 WO4–Na2 CO3 eutectic.

SYNERGISM OF WOLFRAMITE FLOTATION WITH BENZYL ARSONIC ACID AND SODIUM BUTYL XANTHATE

Wolframite notation with benzyl arsonic acid and sodium butyl xanthate is studied,at first.It shows the efficiency of mineral processig is good when the two agents are added together.Then the synergism of sodium butyl xanthate and benzyl arsonic acid is studied also by HPLC.

In situ LA-ICP-MS analyses of mica and wolframite from the Maoping tungsten deposit,southern Jiangxi,China

The Maoping tungsten deposit is located in the Nanling W-Sn metallogenic belt in South China.Greisen and quartz vein types of mineralization developed in this deposit.Protolithionite occurs in the granite.Zinnwaldite is occurs mainly in greisen and wolframite-quartz veins whereas phengite is found in the underground quartz veinlets.In granite and greisen,protolithionite,and zinnwaldite are partly replaced by Li-phengite.LA-ICP-MS trace element analyses of micas and wolframite are employed to characterize the ore-forming source and evolution of ore forming fluids.Micas show compositional variation trend in vertical directions with a decrease of W,Sn,Nb,and Ta and an increase of MgO,V,Ni,and Co.Wolframite in greisen has higher Mo,Sn,Nb,Ta,and REEs than those in quartz veins.All wolframites show similar REE patterns with enrichment of HREE.Wolframites in greisen and quartz veins have negative Eu anomalies,while wolframites in quartz veinlet display positive Eu anomalies.Compositions of mica and wolframite from different mining levels of the Maoping deposit suggest that the ore-forming fluids are dominated by magmatic hydrothermal fluids in the deep with a slight addition of meteoric water in the shallow.Brittle fractureinduced depressurization and fluid mixing controlled the evolution of ore-forming fluids and possibly lead to the wolframite deposition.

Oxygen Isotope Studies of Wolframite in Tungsten Ore Deposits of South China

Based on the oxygen isotopic compositions of 133 wolframite samples and 110 quartz sampleseollected from 30 tungsten ore deposits in south China,in conjunction with δD values and other data,thesc deposits can be divided into four types. （l）Reequilibrated magmatic water-hydrothermal tungsten ore deposits. The δ18O values ofwolframite and quartz samples from this type of tungsten ore deposits are about +5-+12‰,respectively.The calculated δ（18）OH2O values of ore fluids in equilibrium with quartz are about+65‰,and the δDH2O values of fluid inclusions in quartz range from -40 to-70‰. （2）Meteoric water-hydrothermal tungsten ore deposits.Theδ18O values of wolframite in this type oftungsten dePosits are around-1‰. （3）Stratiform tungsten ore deposits.In these deposits,theδ18O values of quartz and wolframite areabout+17 and+3‰,respectively.It is considered that these stratiform tungsten ore deposits aregenetically related to submarine hot—spring activities。 （4）Complex mid-hydrothermal tungsten ore deposits.These tungsten ore deposits arecharacterized by multi-staged mineralization.The δ18O values of early wolframite are around+5‰,butof later wolframite are lower than+4‰,indicating that the early wolframite was precipitated fromreequilibrated magmatic water-hydrothermal solutions and the late one from the mixture ofhvdrothermal solutions with meteoric waters or mainly from meteoric waters, Based on the δ18O values of the coexisting quartz and wolframite and temperature data,twocalibration equilibrium curves have been constructed,and the corresponding equations have beenObtained: 1000 lnaQ-Wf=2.565×107T-2—7.28×l04T-1+57.27 1000 In aWf-H20=-2.285×107T-2+7.49×104T-1-61.79.

New Technologies of Combined Agglomeration-separationfor Wolframite Fines

The new technology of combined agglomeration-separation and conditions for treating wolframite fineswere discussed. A mixture of wolframite and four kinds of gangue fines (quartz , fluorite, garnet and calcite)can be separated by this new technology. At high feed grade (wolframite : gangue = 1: 1) , wolframite con-centrate obtained by sedimentation assays 6 1 . 22 % ￣ 68. 33 % WO_3 with a recovery of 84. 4 % ￣93. 4 %. Atlow feed grade (wolframite : gangue =1 : 5) , wolframite ocncentrate obtained by combined agglomeration-separation and low-intensity magnetic separation assays 51 . 5% WO_3 with a recovery of 92. 0%. The majorfactors influencing these processes are the dosage of reagents and magnetite used, the time and the speed of agitation.

CARRIER FLOTATION OF ULTRAFINE PARTICLE WOLFRAMITE

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Flotation performance of anisic hydroxamic acid as new collector for tungsten and tin minerals

In order to improve the recovery of tungsten ores containing tin minerals,anisic hydroxamic acid(p-methoxy benzohydroxanic acid,PMOB)was synthesized and introduced as novel collector in the flotation of scheelite,wolframite and cassiterite.The flotation performance and adsorption mechanism were investigated by micro/batch flotation,zeta potential measurements and density functional theory(DFT).The micro flotation results showed that the recoveries of scheelite,wolframite and cassiterite using PMOB as collector are 97.45%,95.77% and 90.08%,respectively,and the corresponding recoveries are 91.00%,84.30% and 84.67% for benzohydroxamic acid(BHA).The batch flotation results revealed that the collector dosage could be reduced by about 45% for PMOB compared with BHA,in the case of similar flotation indicators.Zeta potential measurements indicated that PMOB could be adsorbed on the mineral surfaces by chemisorption.Moreover,density functional theory(DFT)calculation results showed that the substituent group—OCH_(3)endues PMOB stronger electron donation ability and hydrophobicity compared with benzohydroxamic acid(BHA),pmethyl benzohydroxamic acid(PMB)and p-hydroxyl benzohydroxamic acid(PHB).

Energy Consumption in Tungsten Extractive Metallurgy

The energy consumption figures of tungsten extractive metallurgy are discussed. The tungsten powderis produced from wolframite and / or scheelite. The energy consumption in mining, beneficiation, digestion,blue oxide production and reduction is calculated respectively. The accuracy of calculation is within a rangeof ±15%.

Robust Timing Constraints for Granitic Magmatism and Hydrothermal Mineralization in the Tieshanlong W-Sn Ore Field,Eastern Nanling Range,South China

The Tieshanlong ore field is an important part of the Nanling Range,which is famous worldwide for its W-Sn mineralization.Notably,the mineralization age of the Tieshanlong ore field is not well constrained,and our field investigation reveals that granitic emplacement occurred at different stages.However,previous studies have not distinguished these multiple stages of magmatism.The Tieshanlong granite complex is closely related to the Huangsha quartz vein-type W-Sn deposit and Tongling skarn-type Cu-W-Sn deposit in this field.Through field investigations and isotopic age analyses,this work studies the relationship between multistage magmatic activity and mineralization in the Tieshanlong ore field.LA-ICP-MS zircon U-Pb isotope analyses revealed that the first-and second-staged granites formed at 154.2±0.6 Ma(MSDW=1.4)and 151.2±0.4 Ma(MSDW=1.5),with zirconε_(Hf)(t)values ranging from-13.1 to-10.5 and from-14.7 to-11.1,respectively.These data suggest that the Tieshanlong granite complex was derived from the partial melting of ancient crustal material.LA-ICP-MS U-Pb dating of wolframite and cassiterite reveals that W-Sn mineralization occurred at 160-150 Ma,which agrees well with the U-Pb dating results of the second-staged granite within analytical errors.The magmatic activity in this ore field can be divided into three stages:175-154 Ma,154-150 Ma and 150-145 Ma.The quartz vein-and skarn-type W-Sn mineralization is closely related to second-staged fine-grained twomica granite,and formed earlier than skarn-type Cu-mineralization.This study establishes a metallogenic model for the Tieshanlong ore field,and this model has important practical significance for identifying concealed W-Sn(-Cu)deposits around other granitic complexes in the Nanling Range.

Structural deformation, metallogenic epoch and genetic mechanism of the Woxi Au-Sb-W deposit, Western Hunan Province, South China

The remobilization,migration,precipitation,and enrichment of ore-forming elements are closely related to structures.Therefore,detailed regional and ore-field structural analyses are critical for determining the genesis of a mineral deposit.The Jiangnan Orogenic Belt(JOB)is an important gold polymetallic metallogenic belt in South China,which is characterized by multiple periods of gold mineralization in the Paleozoic and Mesozoic.However,the genesis of these gold polymetallic deposits is still not well understood due to a lack of systematic research on the regional geology,ore-controlling structures and metallogenic mechanism.In this study,a detailed structural survey at the surface and in the subsurface tunnels was conducted on the Woxi Au-Sb-W deposit,the genesis of which is relatively controversial among the gold polymetallic deposits in the JOB due to poor structural constraints.In addition,a wolframite U-Pb dating was carried out to further constrain the relationship between structures and mineralization.Based on the results of these studies,together with those from previous studies,it is proposed that the Woxi deposit and surrounding areas likely underwent six periods of regional deformation,which are constrained in time and geodynamic setting.Furthermore,we present a systematic discussion on the roles of ore-controlling structures in the transportation,distribution,and deposition of ore-forming elements and localization of orebodies.According to the wolframite dating results,structural analyses,and previous data,we propose that the Woxi Au-Sb-W deposit was formed in two stages during the Yanshanian:a W(wolframite)-Au mineralization stage at ca.140 Ma and an Au-Sb-W(scheelite)mineralization stage at<130 Ma.These mineralizing events are interpreted to have a tight relationship with tectonic reactivation,and the ore-forming fluids were derived from deep sources,including those of magmatic or metamorphic origins.The Woxi deposit can therefore be classified as an“intracontinental reactivation-type”,and the mineralization is related to lithospheric extension caused by plate retreat,retention,and delamination following the cessation of westward subduction of the Paleo-Pacific Plate beneath the East Asian continent.