Density Functional Theory Study on Flotation Performance of O-isopropyl-N-propyl Thionocarbamate
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摘要:
采用密度泛函理论计算O-异丙基-N-丙基硫氨酯（IPP）和O-异丙基-N-乙基硫氨酯（Z-200）的电子结构，结合Klopman的普遍化微扰理论，预测新型硫氨酯IPP的浮选性能。计算结果表明，IPP的最高占据轨道能量（EHOMO）、最低空轨道能量（ELUMO）均高于Z-200，电负性比Z-200小。由此推测IPP的捕收能力比Z-200强，选择性弱于Z-200。之后合成目标分子，并运用核磁共振波谱（NMR）进行结构表征。通过铜硫矿石的单矿物及实际矿石的浮选试验，试验结果与前期预测吻合。研究结果表明：O-异丙基-N-烃基硫氨酯分子中N原子上连接的烃基由丙基替代乙基时，EHOMO、ELUMO增大，则该分子的捕收能力强，选择性弱。前线轨道能量等性质参数可用于预测硫氨酯捕收剂的浮选性能。
Abstract:The electronic structures of O-isopropyl-N-propyl thionocarbamate (IPP) and O-isopropyl-N-ethyl thionocarbamate (Z-200) were calculated by density functional theory. In combination with Klopman's generalized perturbation theory, the collecting performance of the new thionocarbamate IPP was predicted. The results showed that the energy of the highest occupied molecular orbital (EHOMO) and the energy of the lowest unoccupied molecular orbital (ELUMO) of IPP were higher than those of Z-200, and the electronegativity was lower than that of Z-200. It could be predicted that the collecting ability of the new thionocarbamate IPP was stronger than that of Z-200, and the selectivity was weaker than that of Z-200. Then, the target molecules were synthesized and characterized by nuclear magnetic resonance spectroscopy (NMR). The flotation tests of pure minerals and actual ore were conducted, and the results were in good agreement with the preliminary prediction. The results showed that when the hydrocarbon group attached to the N atom in the molecule is replaced by a propyl group, the EHOMO and ELUMO increase, and the molecule has a strong collection ability and weak selectivity. The frontier orbital properties such as the energy can be used to predict the flotation performance of thionocarbamate.
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表 1 实际矿石的化学成分
Table 1. Chemical compositions of the actual ore
成分 Cu TFe S Zn Mn Pb SiO2 Al2O3 CaO 含量/% 0.67 13.56 10.69 0.62 0.15 0.03 52.19 7.70 4.54 
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表 2 IPP、Z-200及丁基黄药(BX)的性质参数
Table 2. Property parameters of IPP、Z-200 and butyl xanthate (BX)
捕收剂种类 原子NPA电荷 能量/eV 电负性/eV S N HOMO LUMO ΔE(H-L) IPP -0.379 -0.627 -6.332 -0.593 5.739 3.463 Z-200 -0.378 -0.630 -6.336 -0.599 5.738 3.466 丁基黄药 -0.409 (S1) -0.383 (S2) -5.301 -0.949 4.352 3.124 注：S1、S2分别表示丁基黄药离子的单键、双键S原子。
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表 3 实际矿石浮选试验结果
Table 3. Flotation experiment results of the actual ore
捕收剂 产品名称 产率
/%品位/% 回收率/% Cu/S回收率比 Cu S Cu S IPP 粗精矿 16.16 4.37 14.29 71.91 15.02 4.78 尾矿 83.84 0.329 15.58 28.09 84.98 原矿 100.00 0.67 10.69 100.00 100.00 Z-200 粗精矿 14.51 4.74 14.57 71.61 14.01 5.11 尾矿 85.49 0.319 15.18 28.39 85.99 原矿 100.00 0.67 10.69 100.00 100.00 丁基
黄药粗精矿 29.16 2.69 30.69 76.83 56.47 1.36 尾矿 70.84 0.33 9.74 23.17 43.53 原矿 100.00 0.67 10.69 100.00 100.00
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