难处理白钨矿常温浮选新工艺研究
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摘要
白钨矿与萤石、方解石等含钙脉石矿物的分离是矿物加工领域世界性难题之一。彼得罗夫法是白钨浮选的传统方法。这种工艺采用高水玻璃用量加温至90℃以上,在高碱度条件下对高浓度矿浆进行长时间搅拌,然后稀释矿浆进行浮选。该法能耗高,生产成本高,工作环境恶劣。采用新工艺实现白钨常温浮选是时代发展的客观需要和必然趋势。
本论文通过浮选试验和机理研究两方面对石灰法常温浮选白钨进行了研究。得出的主要结论如下：
单矿物试验结果表明：分别用CaO+Na2CO3、Na2CO3、NaOH调pH值,水玻璃作抑制剂时：白钨矿与萤石、方解石在石灰法条件下可浮性差异最大,在Na2C03作用下,分离效果最差。实验结果表明,在浮选分离白钨-萤石型白钨时,上述三种调整剂作用下,水玻璃均能选择性抑制萤石,实现白钨优先浮选。在浮选分离白钨-方解石和白钨-萤石-方解石型白钨时,石灰法效果最好。
实际矿石试验结果表明：733氧化石蜡皂与苯甲羟肟酸(10：1)作为白钨浮选捕收剂,具有良好的捕收和选择性能；石灰法粗选小型闭路试验得到了品位(WO3)3.25%,回收率76.08%的白钨粗精矿；常温条件下,石灰法开路常温精选得到了(W03)37.80%,回收率38.74%的白钨精矿,对原矿富集比高达100。通过对粗精矿和精矿XRD分析,石灰法条件下,萤石在粗选段大量被抑制,方解石在精选段被很好地抑制。试验结果表明：石灰法常温条件下,可以实现白钨与含钙脉石矿物的浮选分离,取代现有的彼得罗夫法,具有非常重要的实际价值。
机理研究表明,在高碱度条件下,白钨、萤石、方解石表面带负电,阴离子捕收剂主要通过表面溶解的钙离子发生反应,三者可浮性很相近。动电位、水玻璃吸附量及溶液化学研究表明,添加石灰,萤石、方解石表面吸附大量Ca2+离子,表面有很高的正电荷,而白钨矿则保持了较低的表面动电位。添加碳酸钠后,萤石、方解石表面动电位明显负移,白钨负移不明显。继续添加水玻璃,萤石、方解石表面动电位发生显著负移,白钨矿则变化不明显。表明水玻璃在萤石、方解石表面的吸附量远大于在白钨矿的吸附量。这通过水玻璃与三种矿物的溶液化学研究和在三种矿物表面的吸附量得到证实。
Seperation of scheelite from fluorite and calcite has been a difficulty research program in the mineral processing field all over the world. Petrov Method is the traditional way for scheelite flotation, during which high quantity of water glass is added to the high concentrate slurry of scheelite in the higher alkalinity condition with long time continual stirring at 90℃. It has been considered as a adverse processing method, according to its high energy cost, high expense and adverse working environment. All these conditions call for a new technic which can put the scheelite normal temprature flotation into reality.
This paper investigated the scheelite normal temprature flotation through flotation experiments and mechanism research. The main results are showed as follows:
Single mineral tests indicated that:With CaO+Na2CO3、Na2CO3、NaOH as the PH modifiers separately and water glass as the depresant, the flotability differences between scheelite, fluorite and calcite were big and best; while with Na2CO3 the differences were worst. During the flotation of scheelite from scheelite-fluorite ore with those modifiers discussed above, water glass had brilliant selective depression effect on fluorite, achieving scheelite precedence flotation; while in the flotation scheelite from scheelite-fluorite-calcite ore, lime method showed the best result.
Actual flotation tests results showed that:733 oxidized paraffin soap and benzyl hydroxamic acid (ratio 10:1) was proved to be an excellent collector as it had outstanding collectibility and selectivity; With lime method in laboratory closed circuit experiment, the concentration of rough concentrate scheelite (WO3) reached 3.25% with recovery of 76.08%. At normal tempratur with lime method in open circuit process, the concentration of concentrate scheelite (WO3) of 37.8%, recovery of 38.74% and the enrichment ration was as high as 100. It was proved by the XRD analyse that with lime method most of the fluorite was well depressed in the coughing flotation period, and calcite was well depressedin at the cleaning period. In conclusion, as the replacement of the Petrov method, the lime method actualized the seperation of scheelite from calcium-bearing Gangue minerals at normal temprature.
Mechanism investation showed that:in the higher alkalinity condition, the surfaces of scheelite, fluorite and calcite wore negative charge, so the collector reacted with these three minerals through the dissolved Ca2+ on its surface, accordingly resulted the similar flotability. On the other side, by adding lime, fluorite and calcite could charged high positive charge since it absorbed big amount of Ca2+,while the scheelite remained negative charge. After adding Na2CO3, the Zata potial of the surface of the fluorite and calcite changed to negative obviously, while the scheelite did not change too much, and this trend increased by adding water glass continously, which indicated that the absorption amount of water glass on the surface of fluorite and calcite was much higher than that of the scheelite, and this was also improved by the solvent chemistry investigation and absorption amount experiments.
本论文通过浮选试验和机理研究两方面对石灰法常温浮选白钨进行了研究。得出的主要结论如下：
单矿物试验结果表明：分别用CaO+Na2CO3、Na2CO3、NaOH调pH值,水玻璃作抑制剂时：白钨矿与萤石、方解石在石灰法条件下可浮性差异最大,在Na2C03作用下,分离效果最差。实验结果表明,在浮选分离白钨-萤石型白钨时,上述三种调整剂作用下,水玻璃均能选择性抑制萤石,实现白钨优先浮选。在浮选分离白钨-方解石和白钨-萤石-方解石型白钨时,石灰法效果最好。
实际矿石试验结果表明：733氧化石蜡皂与苯甲羟肟酸(10：1)作为白钨浮选捕收剂,具有良好的捕收和选择性能；石灰法粗选小型闭路试验得到了品位(WO3)3.25%,回收率76.08%的白钨粗精矿；常温条件下,石灰法开路常温精选得到了(W03)37.80%,回收率38.74%的白钨精矿,对原矿富集比高达100。通过对粗精矿和精矿XRD分析,石灰法条件下,萤石在粗选段大量被抑制,方解石在精选段被很好地抑制。试验结果表明：石灰法常温条件下,可以实现白钨与含钙脉石矿物的浮选分离,取代现有的彼得罗夫法,具有非常重要的实际价值。
机理研究表明,在高碱度条件下,白钨、萤石、方解石表面带负电,阴离子捕收剂主要通过表面溶解的钙离子发生反应,三者可浮性很相近。动电位、水玻璃吸附量及溶液化学研究表明,添加石灰,萤石、方解石表面吸附大量Ca2+离子,表面有很高的正电荷,而白钨矿则保持了较低的表面动电位。添加碳酸钠后,萤石、方解石表面动电位明显负移,白钨负移不明显。继续添加水玻璃,萤石、方解石表面动电位发生显著负移,白钨矿则变化不明显。表明水玻璃在萤石、方解石表面的吸附量远大于在白钨矿的吸附量。这通过水玻璃与三种矿物的溶液化学研究和在三种矿物表面的吸附量得到证实。
Seperation of scheelite from fluorite and calcite has been a difficulty research program in the mineral processing field all over the world. Petrov Method is the traditional way for scheelite flotation, during which high quantity of water glass is added to the high concentrate slurry of scheelite in the higher alkalinity condition with long time continual stirring at 90℃. It has been considered as a adverse processing method, according to its high energy cost, high expense and adverse working environment. All these conditions call for a new technic which can put the scheelite normal temprature flotation into reality.
This paper investigated the scheelite normal temprature flotation through flotation experiments and mechanism research. The main results are showed as follows:
Single mineral tests indicated that:With CaO+Na2CO3、Na2CO3、NaOH as the PH modifiers separately and water glass as the depresant, the flotability differences between scheelite, fluorite and calcite were big and best; while with Na2CO3 the differences were worst. During the flotation of scheelite from scheelite-fluorite ore with those modifiers discussed above, water glass had brilliant selective depression effect on fluorite, achieving scheelite precedence flotation; while in the flotation scheelite from scheelite-fluorite-calcite ore, lime method showed the best result.
Actual flotation tests results showed that:733 oxidized paraffin soap and benzyl hydroxamic acid (ratio 10:1) was proved to be an excellent collector as it had outstanding collectibility and selectivity; With lime method in laboratory closed circuit experiment, the concentration of rough concentrate scheelite (WO3) reached 3.25% with recovery of 76.08%. At normal tempratur with lime method in open circuit process, the concentration of concentrate scheelite (WO3) of 37.8%, recovery of 38.74% and the enrichment ration was as high as 100. It was proved by the XRD analyse that with lime method most of the fluorite was well depressed in the coughing flotation period, and calcite was well depressedin at the cleaning period. In conclusion, as the replacement of the Petrov method, the lime method actualized the seperation of scheelite from calcium-bearing Gangue minerals at normal temprature.
Mechanism investation showed that:in the higher alkalinity condition, the surfaces of scheelite, fluorite and calcite wore negative charge, so the collector reacted with these three minerals through the dissolved Ca2+ on its surface, accordingly resulted the similar flotability. On the other side, by adding lime, fluorite and calcite could charged high positive charge since it absorbed big amount of Ca2+,while the scheelite remained negative charge. After adding Na2CO3, the Zata potial of the surface of the fluorite and calcite changed to negative obviously, while the scheelite did not change too much, and this trend increased by adding water glass continously, which indicated that the absorption amount of water glass on the surface of fluorite and calcite was much higher than that of the scheelite, and this was also improved by the solvent chemistry investigation and absorption amount experiments.
引文
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[3]孙延绵.论我国白钨矿资源现状及其开发利用.中国有色金属学会第五届学术年会论文集.矿业研究与开发,2003,(08)：69～72
[4]杨晓峰,刘全军.我国白钨矿的资源分布及选矿的现状和进展.矿业快报2008,24(4)：6～9
[5]胡为柏.浮选.北京：冶金工业出版社,1990：350～353
[6]宫中贵.用放射性同位素方法研究瑶岗仙矿床的白钨矿浮选.
[7]叶雪均.白钨常温浮选工艺研究.中国钨业,1999,14(5～6)：113～117
[8]邓丽红,周晓彤.白钨矿常温浮选工艺研究.中国钨业,2008,23(5)：20～22
[9]陈景桂.常温浮选白钨矿试验和实践.有色金属,1979(02)：1～6
[10]V.M.Love Ⅱ,Flotation,A.M.Gaudin Memorial Volume,1976,(01):587-621
[11]L.J.Warren,Trrans,Inst.Min.Metal1,1977,(86):94-95
[12]刘建远,陈荩.国外白钨矿的浮选和剪切絮凝.湖南冶金,1984,(03)：45～48
[13]L.T.Warren, Ⅹ Ⅲ Int.Miner.Process.Cong.,1979,(1):229
[14]K.Mattson,Ⅹ Ⅲ Int.Miner.Process.Cong.,1979,(1):133
[15]王淀佐.浮选理论的新进展.科学出版社,1992：210～216
[16]杨思孝.浮选白钨矿的捕收剂选择.江西冶金,1984,(02)：23～28
[17]苏仲平.氧化石钠皂的结构分析和浮选性能的研究.有色金属,1964(11)：19～23
[18]H. S. Hanna,Flotation A. M. Caudin Memorial Volume,1976(1):197
[19]胡岳华.溶液化学计算及图解法与盐类矿物浮选行为研究.[博士学位论文]长沙：中南大学,1989
[20]Noborit,Mining Engineering,1980, Vol.36,No 8.556～575
[21]C.Hicvilmaz,胺对白钨矿及方解石表面性质的影响.国外金属矿选矿,1992,(7)：11～14.
[22]胡岳华,王淀佐.烷基胺对盐类矿物捕收性能的溶液化学研究.中南矿冶学院 学报,1990,(01)：31～38.
[23]许时,盂书青,郭德曼.两性捕收剂浮选白钨矿.有色金属,1986(04)：24-28.
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