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.

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.

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.

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.

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+).

A new collector for wolframite slime flotation

With aniline and salicylaldehyde as main materials, a new collector for wolframite slime was synthesized. In a pulp of natural pH value, this collector can collect wolframite effectively. Its selectivity is similar to that of benzyl arsenic acid and better than that of sodium oleate.With this collector, a wolframite rough concentrate with grade 30.12% WO 3 and recovery 91.50%, and a concentrate with grade 58.66% WO 3 and recovery 85.00% were obtained respectively from a wolframite ore containing 4.08% WO 3.

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.

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.

CARRIER FLOTATION OF ULTRAFINE PARTICLE WOLFRAMITE

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An Experimental Study of Oxygen Isotope Fractionation in the Quartz-Wolframite-Water System

Oxygen isotope fractionation was experimentally studied in the quartz-wolframite-water systemf rom 200 to 420℃.The starting wolframite was synthexized in aqueous solutions of Na2WOR·2H2O+FeCl2·4H2O or MnCl2·4H2O.The starting solutions range in salinity from 0 to 10 equivalent wt.% NaCl.Experiments were conducted in a gold-lined stainless steel autoclave,with filling degrees of about 50%.The results showed no significant difference in dquilibrium isotope fractionation between water and wolframite,ferberite and huebnerite at the same temperature(310℃）.The equilibrium oxygen isotope fractionation factors of wolframite and water tend to be equal with increasing temperature above 370℃.but to increase significantly with decreasing temperature below 370℃.

苯甲羟肟酸-椰油胺组合捕收剂对钨矿浮选行为及机理研究

通过纯矿物浮选试验、吸附量测试和红外光谱分析,详细探讨了苯甲羟肟酸-椰油胺组合捕收剂对钨矿物的浮选行为及其在钨矿物表面的吸附机理。结果表明:在pH=2.0~12.0,苯甲羟肟酸-椰油胺组合捕收剂对钨矿物的捕收能力明显强于单一使用苯甲羟肟酸;组合捕收剂浮选钨矿物的综合较优pH值为10.0,此时黑钨矿浮选回收率为79.80%,白钨矿浮选回收率为76.68%,远高于单独使用苯甲羟肟酸时黑钨矿浮选回收率37.09%和白钨矿浮选回收率53.96%;经浮选药剂吸附量测试和红外光谱分析可知,苯甲羟肟酸-椰油胺组合捕收剂在黑钨矿和白钨矿表面产生了较强的化学吸附,椰油胺能够增大苯甲羟肟酸在钨矿物表面的吸附量。

淘锡坑石英脉型钨矿床找矿新突破及“台阶式”勘查模型启示

淘锡坑钨矿床是目前赣南地区可采规模最大的石英脉型黑钨矿矿床,主要由宝山、棋洞、烂埂子和枫林坑矿段组成。近年通过深边勘查,在矿区南东侧东峰矿段又取得了重要找矿突破,新增优质黑钨矿资源量(WO_(3))超1.4万吨。文章系统对比了淘锡坑各类矿体地质特征,重点对东峰矿段Ⅰ号脉带黑钨矿开展了矿物学研究,结合矿物微区原位微量元素分析,系统总结了石英脉内带型黑钨矿与外带型黑钨矿的地球化学差异。结果显示,内带型黑钨矿具有更低的Zr/Hf、Nb/Ta和LREE/HREE比值,反映其成矿热液演化程度更高,与其更低的成矿温度相对应。东峰矿段黑钨矿由浅至深具有从外带型向内带型过渡的特征,其深部仍具有重要找矿潜力。结合赣南地区石英脉型钨矿发育特征,在“五层楼”模型基础上,笔者提出了适用于石英脉型钨矿深边部找矿的“台阶式”勘查模型,并建立了相应的勘查技术方法及黑钨矿矿物化学标志,为矿床-矿田尺度的钨矿勘查提供了新的理论依据。

瑶岗仙黑钨矿采矿废石资源化利用研究

湖南瑶岗仙黑钨矿采选历史悠久,近百年的开采产生了大量的废石,不仅造成了资源浪费,还存在环境风险。本文针对瑶岗仙黑钨矿采矿废石资源综合利用开展了系统研究:采用两段一闭路制砂工艺可以得到–31.5 mm+20 mm、–20 mm+10 mm、–10 mm+5 mm三个粒级的粗骨料和–5 mm+1 mm粒级的细骨料,其物理化学性能均能满足国家标准中各类砂石骨料的技术要求;对制砂过程产的–1 mm次生细泥采用强磁粗选—摇床精选联合工艺,可以得到合计品位为55.75%、回收率为58.39%的钨精矿产品。该技术基本实现了黑钨废石的资源化利用和有价金属的综合回收。

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.

黑白钨混合矿的苏打连续浸出工艺研究

采用卧式连续加压浸出釜进行了苏打连续分解黑白钨混合矿的实验研究,考察了各工艺参数对混合矿分解率的影响。结果表明,在黑白钨混合矿磨矿细度-0.050 mm、浸出温度200℃、液固比2.1∶1、苏打用量为理论量4倍、氢氧化钠用量25 kg/t矿、进料速度10 m^(3)/h条件下,钨分解率达99.55%,渣中WO_(3)含量仅0.28%。连续浸出方式相对间歇浸出方式具有操作简单、生产效率高、综合能耗低、分解率稳定、自动化程度高等优点。

某变质砂岩石英细脉带钨矿石的可选性试验研究

某变质砂岩石英细脉带钨矿石原矿品位低,WO_(3)品位0.15%左右,黑钨矿占钨总量的96.09%。矿石中金属硫化物种类繁多但含量少,属易选黑钨矿石。为了回收该矿石中的钨资源,首先进行了系统的工艺矿物学研究,明确了影响钨矿选矿指标的矿物学因素;然后在此基础上采用先重后浮流程进行了矿石可选性试验研究,并对方案的效果进行了详细的分析,试验获得钨精矿产率0.204%,WO_(3)品位48.88%,WO_(3)回收率72.315%;铜精矿产率0.098%,Cu品位23.35%,Cu回收率51.99%的良好选别指标。最后推荐“摇床粗选+粗精矿浮选收铜”流程回收该矿石中钨、铜资源,并给出合理化建议。