First-principles Study on the Effect of N, O, S Substituted 2-Mercaptophenyl Collectors
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摘要:
采用密度泛函理论分析了2-巯基苯并噻唑(MBT)、2-巯基苯基恶唑(MBO)和2-巯基苯基咪唑(MBI)三种螯合捕收剂的电子结构, 系统地研究了分别取代N、O、S原子对捕收剂的性质的影响。研究结果表明: MBO费米能级附近主要由硫原子贡献组成, S1、S2原子具有较高活性, 表现出更强的电子活性, 说明MBO的捕收性和选择性比其他两种捕收剂的都强。通过前线轨道计算可知MBO与矿物的相互作用最强, 其结果很好地解释了三种螯合捕收剂发生作用的差别。试验中三种螯合捕收剂浮选黄铜矿和黄铁矿时, MBO、MBT、MBI对黄铜矿的回收率依次为88%、63%、42%, 对黄铁矿的回收率都小于20%, 浮选回收率最好的药剂为MBO。因此取代O原子的捕收剂MBO对黄铜矿的选择性最好, 捕收能力更强, 浮选回收率也更高。研究结果为进一步认清黄铜矿和黄铁矿的可浮性差异及新药剂开发提供了理论指导参考。
Abstract:The electronic structures of 2-mercaptobenzothiazole (MBT), 2-mercaptobenzothiazole (MBO) and 2-mercaptobenzothiazole (MBI) chelated collectors were analyzed by density functional theory. The effects of substituting N, O and S atoms on the properties of the collectors were systematically studied. The results show that MBO is composed of sulfur atoms near the Fermi level. S1 and S2 atoms are highly active and exhibit stronger electronic activity, indicating that MBO has stronger collection and selectivity than other two kinds of collectors. The interaction between MBO and minerals is the strongest through frontier orbit calculation, which can well explain the difference of the three chelating collectors. In the experiment, when three chelating collectors flotation chalcopyrite and pyrite, the recovery of chalcopyrite by MBO, MBT and MBI is 88%, 63% and 42% respectively, and the recovery of pyrite is less than 20%. The best flotation recovery reagent is MBO. Therefore, the collector MBO replacing O atom has the best selectivity for chalcopyrite, with stronger collecting ability and higher flotation recovery. The results provide theoretical guidance for further understanding the difference of flotation ability between chalcopyrite and pyrite and the development of new reagents.
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Key words:
- collector /
- first principles /
- electronic properties /
- chalcopyrite /
- pyrite /
- flotation
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表 1 三种捕收剂几何结构优化后的性质参数
Table 1. Property parameters of the three collectors after geometric structure optimization
COLLECTOR Bond length/Å Bond angle/Å R(C—S1) R(C—S2) R(C—X) ∠(S1-C-S2) ∠(S1-C-X) ∠(S2-C-X) MBT(X=N) 1.799 1.809 1.527 124.990 110.042 124.917 MBO(X=O) 1.830 1.810 1.536 111.099 113.059 111.181 MBI(X=S3) 1.824 1.810 1.824 113.820 111.168 113.821 
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表 2 三种捕收剂部分原子的Mulliken电荷布居的变化局部图
Table 2. Local plot of Mulliken charge placement of partial atoms of three traps
捕收剂 原子 价轨道电子数 总电
子数电荷/e s p 
H 0.70 0.00 0.70 0.30 C 1.26 2.90 4.16 -0.16 N 1.72 3.64 5.36 -0.36 S1 1.79 3.87 5.66 0.34 S2 1.81 4.21 6.02 -0.02 
H 0.66 0.00 0.66 0.34 C 1.33 2.92 4.25 -0.25 O 1.86 4.59 6.45 -0.45 S1 1.81 3.99 5.80 0.20 S2 1.81 4.26 6.07 -0.07 
H 0.71 0.00 0.71 0.29 C 1.40 3.20 4.60 -0.60 S3 1.81 4.29 6.11 -0.11 S1 1.80 3.99 5.79 0.21 S2 1.80 3.99 5.79 0.21
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表 3 MBT、MBO和MBI前线轨道系数
Table 3. Front-line track coefficients of MBT, MBO and MBI
螯合剂 前线轨道 轨道系数 MBT HOMO 0.000001H 1s，0.000231C 2p，
0.00006N 2p，0.669883S 2pLUMO 0.013480H 1s，0.308336C 2s，
0.516410N 2s，0.172697S 3sMBO HOMO 0.000014H 1s，0.000364C 2p，
0.000416O 2s，0.816765S 2pLUMO 0.002155H 1s，0.027024C 1s，
0.122496O 2p，0.014348S 3pMBI HOMO 0.00003H 1s，0.000449C 2p，0.860291S 2p LUMO 0.027894H 1s，0.035461C 2p，0.040072S 3p
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表 4 矿物及三种捕收剂的前线轨道能量
Table 4. Frontier orbital energies of minerals and three collectors
前线轨道能量/eV 黄铜矿轨道能量差/eV 黄铁矿轨道能量差/eV HOMO LUMO ΔE1 ΔE2 ΔE1 ΔE2 MBT -5.481 -1.797 3.825 0.598 4.498 0.442 MBO -4.999 -1.382 4.24 0.116 4.913 0.924 MBI -4.359 -3.758 1.864 0.524 2.537 1.564 黄铜矿 -5.622 -4.883 - - - - 黄铁矿 -6.295 -5.923 - - - - 注：ΔE1=|E(HOMOMINERAL) -E(LUMOCOLLECTOR)|; ΔE2=|E(HOMOCOLLECTOR) -E(LUMOMINERAL)|。
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