Flotation separation of chalcopyrite and molybdenite by externally controlled potential method
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摘要: 利用自制外控電位浮選槽研究了礦物粒度、礦漿pH值、外控電位大小等因素對黃銅礦和輝鉬礦浮選行為的影響, 從而找到二者分離的條件并進行了銅鉬混合精礦的外控電位浮選分離, 采用循環伏安測試和腐蝕電偶測試驗證了上述試驗結論. 研究結果表明, -150+31 μm的黃銅礦受外控電位影響大, 容易被抑制, 而輝鉬礦則不容易被抑制. -31 μm的黃銅礦和輝鉬礦可浮性均較差, 受外控電位影響較小. 外控電位浮選在堿性條件下進行有利于實現抑銅浮鉬. 在pH值11的條件下, 抑銅浮鉬的最佳分離外控電位為-1100~-700 mV(vs Ag/AgCl). 在pH值為11、外控電位-800 mV(vs Ag/AgCl)的條件下對多寶山銅鉬混合精礦進行浮選分離, 經過一次浮選分離可得到鉬回收率80.57%、銅回收率10.19%的鉬粗精礦, 輝鉬礦和黃銅礦的浮游差達到70.38%, 這使外控還原電位下浮選分離黃銅礦和輝鉬礦成為可能. 另外, 腐蝕電偶測試結果表明: 黃銅礦和輝鉬礦間的電偶腐蝕對于抑銅浮鉬浮選有促進作用.Abstract: Chalcopyrite-molybdenite separation has always been a major difficulty in mineral processing. At present, chemical agents are commonly used to regulate the pulp potential. However, the air flowing into the flotation process easily destroys the reducing atmosphere, resulting in the increase in reagent dosage. Externally controlled potential flotation can reduce the consumption of reagents by adding electrodes to the pulp to control the pulp potential. The effects of mineral size, pulp pH, and externally controlled potentials on the flotation behavior of chalcopyrite and molybdenite were investigated in the present work using a self-made externally controlled potential flotation cell. Under the optimal conditions, the separation test of Cu-Mo concentrate was conducted using the externally controlled potential flotation. The results were verified by cyclic voltammetry and galvanic corrosion tests. The results show that chalcopyrite with -150+31 μm fraction is considerably affected by externally controlled potentials and is easily inhibited, whereas molybdenite with -150+31 μm fraction is not easily inhibited. Chalcopyrite and molybdenite with -31 μm fraction have poor floatability and are less affected by externally controlled potentials. Externally controlled potential flotation is conducted under alkaline conditions to facilitate the inhibition of chalcopyrite and the flotation of molybdenite. In the case of pH 11, the optimal externally controlled potential for chalcopyrite-molybdenite separation is -1100 to -700 mV (vs Ag/AgCl). Under the conditions of pH 11 and externally controlled potential of -800 mV (vs Ag/AgCl), the Duobaoshan chalcopyrite-molybdenite mixed concentrate was separated by flotation. After one flotation cycle, the primary molybdenum concentrate with 80.57% recovery of molybdenum and 10.19% recovery of copper can be obtained. The flotation difference between molybdenite and chalcopyrite reaches 70.38%, which makes it possible to separate chalcopyrite and molybdenite by externally controlled reduction potential. In addition, galvanic corrosion between chalcopyrite and molybdenite promoted the flotation of molybdenite and the inhibition of chalcopyrite.
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圖 3 外控還原電位下，不同粒級黃銅礦的浮選行為(vs Ag/AgCl)
Figure 3. Effect of externally controlled reduction potential on the flotation of chalcopyrite with different particle sizes
圖 4 外控還原電位下，不同粒級輝鉬礦的浮選行為(vs Ag/AgCl)
Figure 4. Effect of externally controlled reduction potential on the flotation of molybdenite with different particle sizes
圖 5 外控還原電位下，礦漿pH對黃銅礦和輝鉬礦浮選行為的影響(vs Ag/AgCl)
Figure 5. Effect of pulp pH on the externally controlled reduction potential flotation of chalcopyrite and molybdenite
圖 6 外控電位大小對黃銅礦和輝鉬礦浮選行為的影響(pH值為11)
Figure 6. Effect of externally controlled potential on the flotation behavior of chalcopyrite and molybdenite (pH 11)
圖 7 銅鉬混合精礦浮選流程圖
Figure 7. Chalcopyrite-molybdenite mixed concentrate flotation flowchart
圖 8 黃銅礦和輝鉬礦在pH值為11的緩沖溶液中的循環伏安曲線. (a)黃銅礦；(b)輝鉬礦
Figure 8. Cyclic voltammetry of chalcopyrite and molybdenite in a buffer solution at pH 11: (a) chalcopyrite; (b) molybdenite
表 1 單礦物化學多元素分析結果
Table 1. Results of single mineral chemical multielement analysis
礦物 元素質量分數/% Cu Fe Mo S 純度 黃銅礦 33.18 30.75 — 31.66 96.01 輝鉬礦 0.65 0.55 57.52 34.90 95.96 
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表 2 pH緩沖溶液的主要成分
Table 2. Main component of the pH buffer solution
pH值 成分1 成分2 3.00 CH3COOH HCl 4.50 CH3COONa CH3COOH 6.00 Na2HPO4 KH2PO4 7.50 Na2HPO4 KH2PO4 9.00 NaHCO3 Na2CO3 10.00 NaHCO3 Na2CO3 11.00 NaHCO3 NaOH 12.00 Na2CO3 NaOH
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表 3 銅鉬混合精礦外控電位浮選分離結果
Table 3. Results of chalcopyrite-molybdenite mixed concentrate by externally controlled potential flotation separation
產品名稱 產率/% 鉬品位/% 銅品位/% 鉬回收率/% 銅回收率/% 鉬粗精礦 10.73 4.13 16.52 80.57 10.19 銅粗精礦 89.27 0.12 17.51 19.48 89.83 銅鉬混合精礦 100.00 0.55 17.40 100.00 100.00
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表 4 研究電極的Tafel參數
Table 4. Tafel parameters of the electrode
工作電極 腐蝕電位，Ecorr/mV(vs Ag/AgCl) 腐蝕電流，icorr/(μA·cm-2) 黃銅礦 -173 114.82 輝鉬礦 -55 1.74
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