Abstract: As the world′s easily beneficiated copper sulfide resources become increasingly depleted,the efficient development
and utilization of copper oxide ores,particularly malachite,have become a research hotspot in mineral processing. Flotation
is the core technique for malachite separation,and the selection and application of collectors directly determine the flotation
performance. Starting from the crystal structure and surface characteristics of malachite,this paper systematically reviews
the research progress of collectors used in malachite flotation. Based on the flotation process,collectors are divided into two major
categories:direct flotation collectors and sulfidization flotation collectors. They are further classified by functional groups into
fatty acids,fatty amines,oxyacid collectors,chelating collectors,and combined collectors. This review highlights the structural
features,interaction mechanisms with the malachite surface,and application scopes of each collector type. It analyzes the chemisorption
mechanism of fatty acid collectors,the electrostatic-hydrogen bonding synergy of fatty amines,the electrostatic and coordination
adsorption of oxyacid collectors,the multidentate coordination behavior of chelating collectors,and the synergistic
effects of combined collectors. In view of the limitations of direct flotation and sulfidization flotation processes,the paper summarizes
the molecular design strategies and modification research progress of typical collectors such as hydroxamic acids,xanthates,
and thiol compounds. Additionally,novel systems including hydrophobic particle collectors and bifunctional collectors in
malachite flotation are introduced. Finally,current challenges for collectors—including insufficient selectivity,high reagent cost,and significant environmental impact-are identified,and future directions are proposed:design of highly selective collectors
via molecular engineering,development of green and environmentally friendly reagents,deeper understanding of synergistic
mechanisms in combined collectors,and their industrial application in complex ore systems. This review aims to provide a theoretical
basis for the molecular design and process optimization of malachite flotation collectors and to serve as a technical reference
for the efficient recovery of copper oxide resources.