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1、Sodium Hydroxide Digestion of Scheelite by Reactive Extrusion反应挤出法氢氧化钠分解白钨矿 Zhongwei Zhaoa,b* Corresponding author. Tel: +86 0731 8830476; fax: +86 0731 8830477. E-mail address: , Yong Lianga, Xuheng Liu a,c, Ailiang Chena, Honggui LiaaSchool of Metallurgical Science and Engineering, Central South U
2、niversity, Changsha 410083, Hunan, Chinab Hunan Key Laboratory of Hunan Province for Metallurgy and Material Processing of Rare Metals, Changsha 410083, Hunan, Chinac National Engineering Lab for High Efficiency Recovery of Refractory Non-ferrous Metal Resources, Changsha 410083, Hunan, ChinaAbstrac
3、t: According to the thermodynamic analysis, scheelite can be decomposed（被分解） as long as the NaOH concentration is high enough, even at relatively low temperatures. 根据热力学分析，只要氢氧化钠浓度足够高，即使在相对低的温度下，白钨矿也能被分解。As for the approaches of increasing NaOH concentration, it is more economical reducing the water
4、 dosage at fixed NaOH dosage than increasing the NaOH dosage at a fixed ratio of liquid to solid. 至于提高氢氧化浓度的方法，在固定的氢氧化钠用量的情况下减少水的用量要比在固定的液固比取得情况下增加氢氧化钠的用量更经济。But the viscosity of slurry will be increased with the solid to liquid ratios increased, 但是随着液固比的增加矿浆的粘度也会上升，which will make the mass transfer
5、 more difficult if the conventional stirring equipment is still employed. 这使得使用传统的搅拌设备会使传质变得困难。Twin screw extruder is a kind of equipment suitable to work with highly viscous macromolecular materials, and good mass transfer can be easily obtained by it. 双螺旋杆挤压机十分适合于高黏性高分子材料的实验，同时传质也非常好。Therefore, it
6、 is considerable to apply this equipment to treat the highly viscous scheelite slurry.因此，可以考虑将此设备应用于处理高粘度的白钨矿矿浆。 Based on these, a novel technology of sodium hydroxide digestion of scheelite is proposed. 基于此，提出一项新颖的氢氧化钠分解白钨矿技术。Under the conditions at temperature 120, screw rotating speed at 160rpm,
7、reaction time for 3.5h and the NaOH dosage 2.2 times to that of the stoichiometry, the content of WO3 in the residue and the WO3 extraction are 1.54% and 99.18%, respectively. 在温度为120，螺杆旋转速度为160rpm，反应时间为3.5h，氢氧化钠用量是理论量的2.2倍的实验条件下，残渣WO3 含量和WO3浸出率分别为1.54%和99.18%。The results indicate that scheelite can
8、 be decomposed with sodium hydroxide by reactive extrusion at a lower temperature.结果表明，在较低的温度下，用反应挤出法就能够使氢氧化钠分解白钨矿。Key words: Scheelite; Digestion; Sodium hydroxide; Reactive extrusion关键字：白钨矿；消化；氢氧化钠；1. IntroductionApproximately two-thirds of tungsten reserves consist of scheelite in the world1. 世界上
9、大约三分之二的钨储存在白钨矿中。Currently, with the consumption of wolframite, scheelite has become a kind of major industrial raw material. 目前，随着黑钨矿的消耗，白钨矿已经成为工业上的主要原材料。Scheelite was mainly digested by soda autoclaving 2,3, hydrochloric acid leaching 4, and soda roasting 5. 白钨矿分解的主要方法有碳酸钠高压分解法，盐酸浸出法和碳酸钠焙烧法。Traditi
10、onally, it was considered that scheelite can not be decomposed by NaOH under commercial conditions 6. 人们认为，在commercial conditions下，白钨矿是不可能被氢氧化钠分解的。However, in the 1980s, Li et al. 7 developed the caustic thermomilling process which can treat not only the high-calcium-content wolframite but also the
11、scheelite-wolframite concentrate blends and even the scheelite concentrates directly. 然而在十九世纪八十年代，李等人研制出一种the caustic thermomilling process，这种方法不仅能够直接处理高钙含量的黑钨矿，而且还能处理黑白钨混合矿，甚至白钨矿。The process has been successfully applied on a commercial scale in fifteen tungsten plants in China 8. 这一方法已经成功的应用于中国的a
12、commercial scale in fifteen tungsten plants。In addition to the mechanical activation, high NaOH concentration is another beneficial contribution to decompose the tungsten ores in this process.除了机械活化的作用，该方法中的高浓度氢氧化钠也有利于分解钨矿石。 Recently, the thermodynamics of NaOH digestion of scheelite was reanalyzed
13、9.最近，研究人员重新分析了氢氧化钠分解白钨矿的热力学。 The results indicate that temperature is not the decisive factor for the NaOH digestion of scheelite and scheelite can be decomposed as long as the NaOH concentration is high enough, even at a relatively lower temperature. 结果表明，氢氧化钠分解白钨矿时，温度并不是起决定性因素，只要碱浓度足够高，哪怕是在一个相对较低的
14、温度，白钨矿依然能够被分解。The increase of NaOH concentration can cause the increase of boiling point of solution which makes it possible that the process can be carried out under the atmosphere pressure;之所以该过程能在常压下进行，是因为高浓度的氢氧化钠是的溶液的沸点增加了。 and it can also provide a powerful driving force for the digestion react
15、ion dynamically.同时还动态地为分解反应提供了一个推动了。 There are two approaches to obtain high concentration of NaOH solution.有两种方法可以获得高浓度的氢氧化钠溶液。 It seems that it is more economical reducing the water dosage at the fixed NaOH dosage than increasing the NaOH dosage at a fixed ratio of liquid to solid.从表面上看，似乎在一定氢氧化钠用
16、量的情况下减少水的用量要比在一定液固比的情况下增加氢氧化钠的用量更经济。Buttheviscosityofslurrywillbe increased with thesolidtoliquidratios increased, which makes the steel balls in the reactor adhere each other and the mass transfer difficult in the thermomilling process.但是，随着液固比的增加，矿浆的粘度也会随之增大，这使得反应容器中的钢球会相互粘附，传质也变得困难了。 Therefore, in order to cut the cost of r
