Maolin Li

The vast seabed holds tremendous resource potential that can provide necessary materials for future human societal development. This study focuses on the mineralogy of seafloor manganese nodules off the coast of China in the Western Pacific and the primary techniques for extracting valuable metal elements from manganese nodules. The research indicates that the main valuable metal elements in the manganese nodules from this region include Cu, Co, Ni, Mn, Fe, etc. The key to extracting these valuable metals lies in reducing Mn(IV) to Mn(II) to disrupt the structure of the nodules, thereby releasing the valuable elements. The extraction processes for the main valuable metal elements of manganese nodules are mainly divided into two categories: pyrometallurgical–hydrometallurgical and solely hydrometallurgical. In order to cope with the challenges of environmental change and improve utilization efficiency, bioleaching, hydrogen metallurgy, and co-extraction are gaining increasing attention. For promoting commercialization, the future development of manganese nodule resources can refer to the technical route of efficient short-process extraction technology, the comprehensive recovery of associated resources, and tail-free utilization.

In order to separate fluorite and calcite inhibited in tungsten tailings, the effect and mechanism of using ultrasonic external field activation to separate fluorite and calcite inhibited by sodium hexametaphosphate in a sodium oleate system were investigated. After pretreatment with an ultrasonic external field with a frequency of 40 kHz and sound intensity of 0.56, 0.50 and 0.40 W/cm², the flotation recovery of calcite could be increased from 16.08% to about 80%, while the flotation recovery of fluorite was only increased from 7.5% to about 20%, with a difference of 60% between the two flotation recoveries, and the larger the sound intensity, the shorter the pretreatment time and the smaller the ultrasonic input energy. The contact angle of the calcite surface increased, sodium oleate adsorption increased, and zeta potential decreased after ultrasonic pretreatment, while the contact angle, sodium oleate adsorption, and zeta potential of fluorite surface were less changed. The results of heat of adsorption and XPS measurements showed that more heat was released from the interaction between sodium hexametaphosphate and fluorite, and the Ca2p peaks on the surface of fluorite were shifted to a greater extent after the interaction, which inferred that the adsorption of fluorite and sodium hexametaphosphate was relatively easier and stronger. It is presumed that the ultrasonic pretreatment can bring the mineral surface to different degrees of desorption according to the adsorption strength of sodium hexametaphosphate, exposing Ca²⁺ active sites for sodium oleate adsorption, while expanding the floatability difference between fluorite and calcite.

Sulfidization xanthate flotation remains the most promising method for the beneficiation of malachite. In this study, L-arginine (LA) was first used to modify the malachite surface and improve the efficiency of sulfidization flotation. The performance of LA was evaluated by the flotation experiments. The mechanism of interaction between LA and the malachite surface was investigated by adsorption experiments, zeta potential measurements, scanning electron microscopy (SEM-EDS) and X-ray photoelectron spectroscopy (XPS) analysis. Flotation experiments showed that LA had a significantly promoting effect on malachite sulfidization flotation. Adsorption experiments and SEM-EDS results indicated that LA improved the adsorption of S (II) species into the malachite surface and promoted the formation of sulfides. This finding was further confirmed by the XPS analysis. The XPS measurements results determined that S (II) species reacted with Cu (II) on the malachite surface and form polysulfides, adding LA promoted the reaction. The zeta potential measurements showed that LA increased the positive electrical properties of the mineral surface, which was conducive to S (II) species adsorption and the sulfidization reaction. This work sheds new light on the development of sulfidization activation.

Grinding, an essential procedure for size reduction and fresh surface exposure of mineral particles, plays an important role in mineral flotation. The grinding media are the key factors for effective grinding and thus for successful flotation. In this study, ceramic ball (CB) and cast iron ball (CIB), two representative grinding media, were chosen to investigate the effects and mechanisms of grinding media on the flotation behavior of scheelite. The results of pure scheelite flotation show that scheelite ground by CB has a better floatability than that ground by CIB. Scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and X-ray photoelectron spectroscopy (XPS) analyses indicate that there are Fe species, namely, elemental iron (Fe), ferrous oxide (FeO), and iron oxyhydroxide (FeOOH), coated on the surfaces of scheelite ground by CIB but not in the case of scheelite ground by CB. The dissolved oxygen (DO) and inductively coupled plasma-atomic emission spectroscopy (ICP-AES) tests show that Fe ions exist in the CIB grinding slurry but not in the case of CB grinding slurry. Compared with the CB grinding slurry, the CIB grinding slurry has a lower DO content and higher Ca ion concentration. Zeta potential results reveal that the Fe species in the CIB grinding reduce the NaOl adsorption on the scheelite surfaces. Finally, the deleterious effect of CIB grinding on the flotation behavior of scheelite is verified by the actual scheelite ore flotation experiments.