伴生银铅锌矿浮选药剂的设计、合成与浮选机理研究
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摘要
论文在对南京栖霞山伴生银铅锌矿工艺矿物学研究的基础上，运用密度泛函理论（DFT）计算、研究了银矿物及主要载银矿物的电子结构性质与可浮性的关系，基于量子化学计算和研究的结果设计了新型巯基苯并咪唑类捕收剂，选择合成了其中三种理论活性较高的捕收剂（EMBI、PMBI和BMBI）；试验研究了合成药剂对方铅矿、闪锌矿、黄铁矿、辉银矿单矿物和人工混合矿物的浮选分离行为；借助紫外光谱分析了EMBI、PMBI和BMBI在溶液中对金属离子的选择性以及与银离子结合的化学计量比和络合常数；通过吸附量、红外光谱测试、分子动力学模拟和热力学分析探讨了合成药剂与矿物表面的作用机理。
结果表明：方铅矿和闪锌矿为银的主要载体矿物，银矿物分布颗粒较细，增加磨矿细度有利于提高银回收率；主要载银矿物和银矿物氧化顺序由易到难为：方铅矿、辉银矿、淡红银矿、脆银矿、银黝铜矿、闪锌矿；与黄药作用由易到难的顺序为脆银矿、辉银矿、银黝铜矿、淡红银矿、闪锌矿和方铅矿；通过调节pH值，合成捕收剂可以有效地浮选分离方铅矿（或闪锌矿）-黄铁矿，捕收能力BMBI>PMBI>EMBI，对银离子具有较好的选择性，与银离子按照1:1的方式结合，结合常数按照EMBI、PMBI和BMBI依次增大；吸附量测试、红外光谱分析、分子动力学模拟计算表明，该类捕收剂通过-SH、-NH与矿物表面的金属离子形成四元螯合环吸附在矿物表面，相互作用能BMBI>PMBI>EMBI，实验结果与理论计算一致。论文研究结果为实现我国量大、难选含银铅锌矿的综合利用、特别是浮选药剂分子设计与合成提供了指导。
To realize comprehensive utilization of silver containing lead-zinc ore, deposit and occurrence statewas determined by the study of process mineralogy. The relationship between electronic structre and theflotability was explained by using DFT theory, some new mercaptobenzo flotation reagents were designed,and three of them (EMBI, PMBI and BMBI) which have higher theory collectivity were synthesized on thebasis of quantum calculation. The flotation behavior of new collectors on the single mineral (galena,sphalerite and pyrite) and artificial mixed mineral was tested by flotation and separation performance. Theselectivity of new collectors on metal ions as well as well as stoichiometric and binding constant with Ag+was determined by UV-Vis analysis. The adsorption mechanism of collectors on the mineral was explainedby adsorption capacity, FT-IR analysis and molecular dynamics simulation modeling.
The results show that galena and sphalerite are the main carrier minerals of silver, the distribution ofsilver particles is finer, and increasing the grinding fineness is helpful to improve the recovery of silver.Oxidized order as follows: galena>argentite>proustite>stephanite>freibergite>sphalerite; andinteraction ability with xanthate from easy to hard follows the order ofstephanite>argentite>freibergite> proustite>sphalerite and galena. By adjusting the pH value,galena or sphlerite can be separated from pyrite effectively by using the synthetic collectors, the collectingability follows the order BMBI>PMBI>EMBI. All of them have good selectivity on Ag+and the bindingconstant following the same order as collecting ability. Adsorption test, FT-IR analysis and moleculardynamics simulation show that these collectors adsorbed on the minerals through–SH,-NH and with metalions forming chelate four member ring, and the interaction energy follows the order ofBMBI>PMBI>EMBI, the calculation results are identical with the experimental. All the results provide usgood guidance for designing collectors reasonablely.
结果表明：方铅矿和闪锌矿为银的主要载体矿物，银矿物分布颗粒较细，增加磨矿细度有利于提高银回收率；主要载银矿物和银矿物氧化顺序由易到难为：方铅矿、辉银矿、淡红银矿、脆银矿、银黝铜矿、闪锌矿；与黄药作用由易到难的顺序为脆银矿、辉银矿、银黝铜矿、淡红银矿、闪锌矿和方铅矿；通过调节pH值，合成捕收剂可以有效地浮选分离方铅矿（或闪锌矿）-黄铁矿，捕收能力BMBI>PMBI>EMBI，对银离子具有较好的选择性，与银离子按照1:1的方式结合，结合常数按照EMBI、PMBI和BMBI依次增大；吸附量测试、红外光谱分析、分子动力学模拟计算表明，该类捕收剂通过-SH、-NH与矿物表面的金属离子形成四元螯合环吸附在矿物表面，相互作用能BMBI>PMBI>EMBI，实验结果与理论计算一致。论文研究结果为实现我国量大、难选含银铅锌矿的综合利用、特别是浮选药剂分子设计与合成提供了指导。
To realize comprehensive utilization of silver containing lead-zinc ore, deposit and occurrence statewas determined by the study of process mineralogy. The relationship between electronic structre and theflotability was explained by using DFT theory, some new mercaptobenzo flotation reagents were designed,and three of them (EMBI, PMBI and BMBI) which have higher theory collectivity were synthesized on thebasis of quantum calculation. The flotation behavior of new collectors on the single mineral (galena,sphalerite and pyrite) and artificial mixed mineral was tested by flotation and separation performance. Theselectivity of new collectors on metal ions as well as well as stoichiometric and binding constant with Ag+was determined by UV-Vis analysis. The adsorption mechanism of collectors on the mineral was explainedby adsorption capacity, FT-IR analysis and molecular dynamics simulation modeling.
The results show that galena and sphalerite are the main carrier minerals of silver, the distribution ofsilver particles is finer, and increasing the grinding fineness is helpful to improve the recovery of silver.Oxidized order as follows: galena>argentite>proustite>stephanite>freibergite>sphalerite; andinteraction ability with xanthate from easy to hard follows the order ofstephanite>argentite>freibergite> proustite>sphalerite and galena. By adjusting the pH value,galena or sphlerite can be separated from pyrite effectively by using the synthetic collectors, the collectingability follows the order BMBI>PMBI>EMBI. All of them have good selectivity on Ag+and the bindingconstant following the same order as collecting ability. Adsorption test, FT-IR analysis and moleculardynamics simulation show that these collectors adsorbed on the minerals through–SH,-NH and with metalions forming chelate four member ring, and the interaction energy follows the order ofBMBI>PMBI>EMBI, the calculation results are identical with the experimental. All the results provide usgood guidance for designing collectors reasonablely.
引文
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