Solvent extraction is the most widely used method for separation and purification of rare earth elements, and organic extractants such as di(2-ethylhexyl) phosphoric acid (P204) and di(1-methyl-heptyl) methyl phosphonate (P350) are most commonly used for industrial applications. However, the presence of impurity ions in the feed liquid during extraction can easily emulsify the extractant and affect the quality of rare earth products. Aluminum ion is the most common impurity ion in the feed liquid, and it is an important cause of emulsification of the extractant. In this study, the influence of aluminum ion was investigated on the extraction of light rare earth elements by the P204-P350 system in hydrochloric acid medium. The results show that Al3+ competes with light rare earths in the extraction process, reducing the overall extraction rate. In addition, the Al3+ stripping rate is low and there is continuous accumulation of Al3+ in the organic phase during the stripping process, affecting the extraction efficiency and even causing emulsification. The slope method and infrared detection were utilized to explore the formation of an extraction compound of Al3+ and the extractant P204-P350 that entered the organic phase as AlCl[(HA)2]2P350(o).
The refractory lead oxide ore has become an important source of lead metal with the continuous depletion of lead sulfide minerals. Lead oxide ore is of poor floatability and there are few cases to concentrate it successfully. In this study, the sulfidization-xanthate flotation method is applied for the beneficiation of lead oxide ore in Yunnan Province (China) with sodium hexametaphosphate and carboxymethyl cellulose as depressant. Chemical analysis and phase analysis was performed to explore the physicochemical property of raw ore, which provides a research basis for process design and operational control. The main influencing factors during the process, including grinding fineness, reagent types, and dosage, etc., have been studied through flotation tests. Zeta potential measurements and Fourier transfer-infrared spectrometry (FTIR) analysis were conducted to reveal the function mechanism of the reagents. Based on the determined experimental conditions, open circuit tests and closed circuit tests with one stage rougher, three-stage scavenger, and two-stage cleaner flotation, were carried out with the run-of-mine ore with a lead grade of 4.57%. Through close circuit bench test, the lead concentrate with a lead grade of 64.08% and recovery of 92.30% was obtained. This study is of special value, as it provides referencing significance for economically exploiting lead oxide ore.
Most hydrophobic clay minerals, such as clinochlore, are known to cause problems in the recovery of cassiterite. In this study, a new reagent scheme, i.e., sodium oleate (NaOL) as a collector and Al (III) ions as a depressant, for reverse flotation separation of cassiterite and clinochlore was investigated. The flotation performance and interaction mechanism were studied by microflotation tests, adsorption tests, contact angle measurements, and X-ray photoelectron spectroscopy (XPS) analysis. Results of single mineral flotation experiments showed that NaOL had a different flotation performance on cassiterite and clinochlore, and the addition of Al (III) ions could selectively inhibit the floatability of cassiterite. Reverse flotation tests performed on mixed minerals indicated that the separation of cassiterite and clinochlore could be achieved in the presence of NaOL and Al (III) ions. Adsorption experiments demonstrated that Al (III) ions hindered the adsorption of NaOL on cassiterite surfaces but exerted little influence on the adsorption of NaOL on clinochlore surfaces. Results of contact angle measurements indicated that Al (III) ions could impede the hydrophobization process of cassiterite in NaOL solution. XPS results showed that aluminum species were adsorbed onto the cassiterite surfaces through the interaction with O sites.
Zinc sulfide minerals are the primary choice for zinc extraction and marmatite is one of the two most common zinc sulphide minerals (sphalerite and marmatite), therefore it is of great significance to study and optimize the flotation of marmatite. To improve the activation of copper sulfate on marmatite, a method involving the addition of ammonium chloride is devised. The method has been proven to be an effective way of improving the activation efficiency of copper sulfate towards marmatite under alkaline conditions. The strengthening mechanism was studied using micro-flotation, adsorption test, X-ray photoelectron spectroscopy, and by analyzing changes in solution composition. Flotation test results show that the activation effect of the copper sulfate towards marmatite is enhanced with the addition of ammonium chloride. According to the results of the adsorption measurements and X-ray photoelectron spectroscopy analysis, when the marmatite surface is activated using copper sulfate with added ammonia chloride, it adsorbs more copper sulfide and less copper hydroxide and zinc hydroxide. These changes in surface composition are believed to occur via the following process: NH3(aq) promotes the dissolution of zinc hydroxide and then facilitates the conversion of surface copper hydroxide to copper sulfide. In addition, the occurrence of Cu(NH3)n2+ can promote the adsorption of copper ions (Cu2+ can be stored as Cu(NH3)n2+ via complexation, and then, when the concentration of copper ions decreases, Cu2+ can be released through the decompositionof Cu(NH3)n2+. Hence, the copper ion concentration can be maintained and this can facilitate the adsorption of Cu2+ on marmatite). Based on a comprehensive analysis of all our results, we propose that adding ammonium chloride to the copper sulfate changes the solution components (i.e., the presence of NH3(aq) and Cu(NH3)n2+) and then regulates the surface composition of marmatite. The change in surface composition improves the hydrophobicity of mineral surface and this leads to an improvement in activation of marmatite.