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摘要: 浮選藥劑的結構對其性能具有重要影響，向現有藥劑中引入適宜的取代基，基于取代基效應實現藥劑浮選性能的改變，已成為高性能浮選藥劑開發的重要手段。為明確甲基對陽離子捕收劑浮選性能的影響，以十二胺（DDA）、N—十二烷基甲胺（MDA）、N,N—十二烷基二甲基叔胺（DMDA）、十二烷基三甲基氯化銨（DTAC）為樣本，通過浮選試驗考察了甲基取代基引入對藥劑捕收能力和浮選選擇性的影響規律，并基于藥劑靜電勢圖和極性基范德華體積的計算，明確了甲基對陽離子捕收劑浮選性能的影響機制。浮選試驗結果表明，隨著陽離子捕收劑中心原子中甲基的引入，石英和赤鐵礦單礦物的浮選回收率逐漸降低，但人工混合礦的分離指數升高。給電子基團甲基的引入，改變了陽離子捕收劑的電荷分布密度，促使中心原子上的電荷數增加，削弱了藥劑與礦物表面的靜電吸附強度，從而導致浮選回收率下降。同時，甲基引入后，陽離子捕收劑中極性基尺寸變大，從而增加了藥劑與礦物表面作用的空間位阻，增強了陽離子捕收劑的浮選選擇性。Abstract: With the implementation of carbon peak and carbon neutrality vision, an amine collector has been extensively applied in reverse flotation of bauxite, iron, and phosphate ores for desiliconization. Previous research indicates that the molecular structure of flotation reagents has a significant influence on their collecting performance and flotation selectivity. Regarding the substituent effect of organics, a method wherein a suitable substituent is inserted into existing reagents has been used to develop new high-performance flotation reagents. To clarify the effect of methyl on collection ability and flotation selectivity of cationic collectors, flotation separation of quartz and hematite has been conducted. C12 alkyl cationic surfactants such as dodecyl amine, dodecyl methylamine, N,N—dimethyl dodecyl amine, and dodecyl trimethyl ammonium chloride were selected as collectors. The active mechanism of methyl on the flotation performance of cationic collectors was also determined by calculating the electrostatic potential of the collectors and the van der Waals volume of its polar group. The collection abilities of cationic collectors were investigated by single mineral flotation. The results indicate that flotation recoveries of quartz and hematite are decreased with the insertion of a methyl group into central atom of a cationic collector. Further, the effect of methyl on selectivity of cationic collectors was investigated by flotation separation of artificially mixed quartz and hematite. The results revealed that the separation efficiency of artificially mixed quartz/hematite is increased gradually due to the drastic reduction in hematite flotation recovery rate. A methyl group is an electron donating group. The calculation and diagramming of electrostatic potential for selected collectors reveal that the charge distribution density of the cationic collector is varied by the introduction of an electron donating group. Consequently, the charge number of central atom is increased, thereby weakening the positive electrostatic potential of the atom and making the electrostatic adsorption strength between collector and mineral surface lower. Therefore, the flotation recovery rate decreased. Meanwhile, the size of a polar group for cationic collectors is enlarged by introducing the methyl group, thus increasing the steric hindrance of reagents and mineral surface interaction and resulting in an increase in flotation selectivity. With an increase in the methyl group number, the flotation separation efficiency of artificially mixed quartz and hematite becomes increasingly high. In the future, obtaining and quantifying correlation parameters of substituents and then explicating the relationship between substituent parameters and flotation performance of cationic collectors would be beneficial to establish a new design method for cationic collectors.
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圖 1 礦樣的XRD譜圖. (a)石英; (b)赤鐵礦
Figure 1. X-ray diffraction pattern of the sample: (a) quartz; (b) hematite
圖 2 礦漿pH值(a)和捕收劑用量(b)對石英和赤鐵礦浮選回收率的影響
Figure 2. Effect of slurry pH (a) and collector concentration (b) on flotation recoveries of quartz and hematite
圖 3 甲基取代基對陽離子捕收劑浮選性能的影響
Figure 3. Methyl effect on collecting ability of cationic collectors
圖 4 甲基取代基對陽離子捕收劑浮選選擇性的影響
Figure 4. Methyl effect on flotation selectivity of cationic collectors
圖 5 樣本捕收劑的靜電勢圖. (a) DDA+; (b) MDA+; (c) DMDA+; (d) DTAC+
Figure 5. Electrostatic potential structures of selected collectors: (a) DDA+; (b) MDA+; (c) DMDA+; (d) DTAC+
表 1 礦樣的化學成分（質量分數）
Table 1. Chemical composition of the sample
% Samples SiO2 Fe2O3 P2O5 CaO Al2O3 K2O MgO Quartz 99.72 0.15 0.01 0.01 0.08 0.01 0.02 Hematite 0.93 99.02 0.01 0.01 0.02 — 0.01 
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表 2 樣本捕收劑對人工混合礦分選結果
Table 2. Flotation separation results of the selected cationic collectors on artificially mixed minerals
Collectors Iron grade for concentrate/% Iron recovery for concentrate/% SE/% DDA 42.40 49.27 3.20 MDA 45.83 53.59 12.98 DMDA 52.03 61.03 30.73 DTAC 53.19 76.61 41.80
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表 3 藥劑中心原子的電荷數
Table 3. Charge number of the central atom of the collectors
Collector DDA MDA DMDA DTAC Charge number of central atom (e) 0.307 0.328 0.344 0.347
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表 4 元素范德華體積（VW）及共價鍵對體積的補正值（
$\Delta V_{\rm{W}}$ ）Table 4. Van der Waals volume for some elements and its correction value of covalent
Element (covalent bond) C N H C—N C—H N—H VW(△VW)/nm3 0.0206 0.0141 0.0056 0.0065 0.0043 0.0038
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