本文選題：白鎢礦 + 方解石��； 參考：《東北大學(xué)》2015年博士論文

【摘要】：白鎢礦與方解石和螢石的浮選分離以及微細(xì)粒白鎢礦的有效回收一直是選礦工作者研究的熱點,其難點在于白鎢礦與含鈣脈石礦物的可浮性相近,浮選過程中不同粒度的同類礦物之間、不同種類的礦物之間存在相互干擾,這些嚴(yán)重影響浮選精礦的回收率和抑制劑的選擇性,基于此,本文通過浮選化學(xué)計算、浮選試驗和多種檢測手段研究了疏水性聚團、固液界面性質(zhì)以及礦物溶解對白鎢礦浮選的影響,在此基礎(chǔ)上,通過強化白鎢礦疏水性團聚、消除(減弱)含鈣脈石礦物對抑制劑選擇性的影響、設(shè)計和合成高選擇性的捕收劑等方法強化了白鎢礦的浮選分離。首先,本文提出和驗證了基團電負(fù)性新公式和誘導(dǎo)共軛指數(shù)研究浮選藥劑結(jié)構(gòu)性能關(guān)系的可行性,并在此基礎(chǔ)上提出了“基團電負(fù)性-誘導(dǎo)共軛指數(shù)法”,研究表明,使用該方法計算浮選藥劑結(jié)構(gòu)性能關(guān)系所得出的結(jié)論與量子化學(xué)計算結(jié)果一致,且兩種計算方法具有互補性。其次,研究了含鈣礦物表面性質(zhì)以及礦物浮選特性,結(jié)果表明,三種含鈣礦物的動電位、表面鈣離子的相對含量以及晶格陰離子的基團電負(fù)性均存在明顯差異,這些是能夠?qū)崿F(xiàn)礦物分離的主要原因；捕收劑的組合使用是強化白鎢礦浮選的有效方法,且白鎢礦粒度影響組合藥劑的最佳配比,但不影響最佳添加順序;藥劑添加順序明顯影響組合藥劑的性能,并與藥劑結(jié)構(gòu)、pH值、藥劑用量及組分配比有關(guān)；浮選試驗還表明,碳酸根離子對白鎢礦有活化作用,但鈣離子可降低白鎢礦的回收率,方解石在碳酸鈉消除鈣離子影響中具有重要作用,此外,方解石及其溶解的鈣離子可顯著降低白鎢礦回收率和抑制劑的選擇性。在上述研究的基礎(chǔ)上,針對微細(xì)粒白鎢礦含量容易過高的特點,通過浮選化學(xué)計算新方法、浮選試驗和多種檢測手段,研究了細(xì)粒白鎢礦對粗粒白鎢礦浮選的影響以及疏水性團聚在白鎢礦浮選中的重要作用,揭示了碳酸鈉對白鎢礦浮選回收的強化作用。研究表明,油酸鈉為捕收劑時白鎢礦的可浮性與粒度呈正相關(guān)關(guān)系；疏水性作用是白鎢礦顆粒發(fā)生團聚的主要原因,且顆粒粒度影響顆粒間的相互作用能、流體剪切力以及兩種作用力的相對大小關(guān)系,使得細(xì)粒(-10μm)與中間粒級(10-38.5μm)白鎢礦易于發(fā)生疏水性團聚,與粗粒級(38.5-125μm)白鎢礦難于發(fā)生疏水性團聚,從而導(dǎo)致了細(xì)粒對粗粒級白鎢礦回收率有不同程度的降低作用,而對中間粒級白鎢礦回收率的影響較��；碳酸根離子置換白鎢礦表面的鎢酸根離子后,有利于促進作用能力比碳酸根/碳酸氫根強的捕收劑的吸附,而捕收劑吸附量增加后有利于促進白鎢礦顆粒間的疏水性團聚,因此,碳酸鈉可強化微細(xì)粒白鎢礦的回收和消除(減弱)微細(xì)粒白鎢礦對粗粒白鎢礦浮選的影響,從而提高了白鎢礦的回收率和浮選速度。針對白鎢礦與方解石和螢石可浮性相近、礦物之間存在相互干擾的特點,研究了消除(減弱)含鈣脈石礦物對抑制劑選擇性的影響的方法,以及設(shè)計和合成了高選擇性捕收劑,使白鎢礦和含鈣脈石礦物的分離得到了強化。研究表明,硅酸鈉可有效分離白鎢礦與螢石,且好于白鎢礦與方解石的分離效果,若通過比較簡單的浮選工藝實現(xiàn)白鎢礦與方解石的分離還需尋找其它抑制劑；浮選試驗和理論計算表明,礦物溶解是方解石降低抑制劑選擇性的主要原因,但碳酸鈉可抑制方解石的溶解,從而可消除(減弱)方解石對抑制劑選擇性的影響；白鎢礦與方解石的混合礦分離時碳酸鈉可強化CMC的選擇性,但碳酸鈉用量過高不利于提高精礦品位,基于此,在適量碳酸鈉的作用下,以CMC為抑制劑實現(xiàn)了白鎢礦與方解石的分離,且分離效果好于硅酸鈉,從而使白鎢礦與方解石的分離得到了強化；通過“基團電負(fù)性-誘導(dǎo)共軛指數(shù)法”和量子化學(xué)計算設(shè)計并合成了十二烷基丙二酸(DCA),試驗表明,以CMC為抑制劑,組合使用DCA和油酸鈉可成功分離白鎢礦與方解石,且效果明顯好于單獨使用油酸鈉；DCA為捕收劑分離白鎢礦與方解石時不需添加碳酸鈉,因為碳酸鈉會降低精礦品位,但是加入鈣離子可以減弱碳酸鈉對品位的影響,而且進一步強化了白鎢礦與方解石的分選效果。云南麻栗坡某白鎢礦礦石含W03僅為0.15-0.18%,且微細(xì)粒白鎢礦含量多,根據(jù)前期的基礎(chǔ)研究,本文使用碳酸鈉調(diào)節(jié)pH值、消除含鈣脈石對白鎢礦浮選的影響、活化白鎢礦和提高自載體浮選回收率,以及使用水玻璃抑制硅酸鹽礦物,利用組合捕收劑的協(xié)同效應(yīng)提高了粗精礦的品位和回收率；湖南某白鎢礦礦石中含大量的含鈣脈石礦物,以DCA和油酸鈉的組合藥劑代替731后,可明顯降低鎢粗精礦中的含鈣脈石礦物的含量以及提高粗精礦的品位。本論文研究成果豐富了白鎢礦浮選的理論體系,對微細(xì)粒白鎢礦富集和白鎢礦與含鈣脈石礦物的分離具有參考價值。
[Abstract]:The flotation separation of scheelite and calcite and fluorite and effective recovery of fine scheelite is always the research focus in mineral processing workers, the difficulty of scheelite and calcic gangue mineral floatability between similar Their natures are much the same., minerals of different particle size in flotation process, mutual interference between different kinds of minerals, which seriously affect the rate and recovery of flotation inhibitor concentrate the selectivity, based on this, this paper through flotation chemistry calculation, flotation tests and various detection methods of hydrophobic clusters, effects of solid-liquid interface properties and mineral dissolution of Scheelite Flotation, on this basis, through strengthening the hydrophobic aggregation of scheelite, eliminate the influence (weaken) the selective inhibitor of calcic gangue mineral collector, methods of design and synthesis of high selectivity and strengthen the flotation separation of scheelite. Firstly, this paper proposed and verified in groups The feasibility of the new formula and the electronegativity index of flotation reagent induced conjugate structure performance relationship, and on the basis of the "group electronegativity - induced conjugate index method, research shows that using the method to calculate the conclusion and quantum chemistry the relationship between structure and properties of flotation reagent, the calculation results are consistent, and two kinds of calculation the method is complementary. Secondly, study the surface properties of calcium minerals and mineral flotation characteristics, the results show that the dynamic potential of three kinds of minerals containing calcium, calcium content and relative surface lattice anion group electronegativity difference, which is the main reason to achieve the separation of minerals; collector combination is an effective method to strengthen the Scheelite Flotation, and the influence of particle size of scheelite best combination agent, but does not affect the optimal adding order of reagent addition order; significantly affect the drug combination Agent performance and chemical structure, pH value, dosage and ratio; flotation tests also show that carbonate ions scheelite has activation, but calcium can reduce the rate of recovery of scheelite, calcite in sodium carbonate to eliminate the effects of calcium ion plays an important role, in addition, calcium ion and calcite dissolution can significantly reduce the selectivity of scheelite recovery and inhibitors. Based on the above research, according to the characteristics of fine scheelite content to high, a new calculation method by flotation chemistry, flotation tests and various methods, studied the influence of coarse fine scheelite Scheelite Flotation and hydrophobic aggregation plays an important role in the selection of floating scheelite that reveals the strengthening effect of sodium carbonate on Scheelite Flotation. Research shows that sodium oleate as collector, the floatability of scheelite and grain size was positively related. Department of; hydrophobic interaction is the main reason for the occurrence of agglomeration of scheelite particles, and the particle size effects of interaction between particles and fluid shear stress and relative size of the two forces, makes the fine (-10 m) and middle grade (10-38.5 m) is easy to occur scheelite hydrophobic aggregation, and coarse grain grade (38.5-125 m) on the occurrence of white tungsten mine hydrophobic aggregation, resulting in a fine to coarse scheelite recovery rate decreases in different degrees, but had little influence on the intermediate recovery of scheelite particles; carbonate ion tungstate ion replacement of scheelite surface, is conducive to the promotion of ability than the carbonate / bicarbonate strong adsorption of the collector, and the collector adsorption increased after promoting hydrophobic scheelite agglomeration of particles, therefore, sodium carbonate can enhance the recovery of fine scheelite and eliminate fine (weakened) Effect of coarse scheelite Scheelite Flotation of scheelite, so as to improve the recovery rate and speed. The flotation of scheelite and calcite and fluorite flotation characteristics of Their natures are much the same., mutual interference between minerals, the elimination of influence (weaken) method for selective inhibitors of calcium gangue minerals, as well as the design and high selective collector prepared, so that the separation of scheelite and calcareous gangue minerals has been strengthened. The results show that sodium silicate can effectively separate scheelite and fluorite, and good separation effect on Scheelite and calcite, if separated by flotation process is relatively simple to achieve scheelite and calcite has yet to find other inhibitors; flotation tests and theoretical calculations show that mineral dissolution is the main reason for reducing calcite and selective inhibitor of sodium carbonate dissolved, but inhibits calcite, which eliminates calcite (weakened) Effect of selective inhibitors; scheelite and calcite mixed ore separation of sodium carbonate can enhance the selectivity of CMC, but the amount of sodium carbonate is too high is not conducive to improve the concentrate grade, based on this, the amount of sodium carbonate under the action of CMC inhibitors to achieve the separation of scheelite and calcite, and the separation effect is better than sodium silicate thus, the separation of scheelite and calcite has been strengthened; twelve alkyl malonic acid were designed and synthesized by the group electronegativity - induced conjugate index method and quantum chemistry calculation (DCA), experiments show that with CMC inhibitor, DCA and sodium oleate can be successfully combined scheelite and calcite separation, and the effect of better than using sodium oleate as collector alone; DCA separation of scheelite and calcite without the addition of sodium carbonate, because sodium carbonate will reduce the concentrate grade, but calcium carbonate can be weakened Effect of sodium on the grade, and further strengthen the effect of separation of scheelite and calcite. Yunnan Malipo scheelite ore containing W03 is only 0.15-0.18%, and the micro fine scheelite content, according to the previous research, this paper using sodium carbonate to adjust the pH value, eliminate the influence of calcic gangue Scheelite Flotation of scheelite, activation and improve the autogenous carrier the flotation recovery rate, and the use of water glass inhibition of silicate minerals, using a combination of collecting agent synergies and improve the crude concentrate grade and recovery rate; with a large number of calcareous gangue minerals scheelite ore in Hunan, with a combination of chemical DCA and sodium oleate instead of 731, can significantly reduce the content of tungsten coarse concentrate in calcium the gangue minerals and improve the rough concentrate grade. The achievements of this thesis enrich the theory system of Scheelite Flotation, fine scheelite enrichment and scheelite ore and water The separation of calcium gangue minerals is of reference value.

【學(xué)位授予單位】：東北大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2015
【分類號】：TD923;TD954

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