Study on Design, Synthesis and Floation Experiment of a Novel O-Isopropyl-N-Benzyl Thionocarbamate

"The research applies the density functional theory and molecule design technology to design and synthesize the novel flotation collectors for copper-sulphur separation. Density functional theory (DFT) was applied to investigate the electronic properties of O-isopropyl-N-benzyl thionocarbamate (IP-BIAN) and O-isopropyl-N-ethyl thionocarbamate (Z-200). The calculation results show that both the energy of highest occupied molecular orbital (EHOMO) and the lowest unoccupied molecular orbital (ELUMO) of IP-BIAN are smaller than that of Z-200, electronegativity of IP-BIAN is higher than that of Z-200. According to the Klopman’s generalized perturbation theory, the collecting power of the two compounds is predicted to be Z-200 > IP-BIAN, the selectivity of IP-BIAN is better than that of Z-200. Then the thionocarbamate molecular is synthesized, and the compounds are characterized by nuclear magnetic resonance (NMR). It turns out that the test result identifies the prediction after the flotation verified test of pure mineral and actual mineral. The results demonstrate that the EHOMO and ELUMO are smaller in the thionocarbamate after a nitrogen atom is bound to benzyl, the thionocarbamate has strong selectivity and low collecting power. The lower the LUMO energy of thionocarbamate is, the stronger the back donation covalent p-bond between collectors and chalcopyrite is, thus improving flotation power for chalcopyrite and selectivity against pyrite. The result proves the feasibility of design and synthesis of the novel thionocarbamate through the frontier orbital properties of the collectors.1. INTRODUCTION Thiocarbamate is a kind of nonionic polar collector and is now widely used as flotation collector for copper-sulphur separation. The flotation power of thiocarbamate to chalcopyrite is stronger than pyrite, so it has high selectivity against pyrite. The frontier orbital theory and density functional theory (DFT) has been widely applied to study the structure-activity relationship of flotation collectors [1-6]. The flotation test results can be interpreted by using the reaction energy criteria and quantum-chemical parameters, such as the energy of the highest occupied molecular orbital (EHOMO) and the energy of the lowest unoccupied molecular orbital (ELUMO) of collector [7-11]. In turn, there are rarely reports about screening the novel flotation collector, by the frontier orbital properties such as HOMO and LUMO of flotation collectors. In this thesis, we apply the density functional theory and molecule design technology to design and synthesize the novel flotation collectors for copper-sulphur separation. Based on the previous findings of the structure-activity relationship of xanthogen formats [12], it has stronger collecting ability to chalcopyrite while the xanthogen formats after a nitrogen atom is bound to benzyl. Thus, in this study, a novel thionocarbamate molecule O-isopropyl-N-benzyl thionocarbamate (IP-BIAN) will be constructed, when the group structure connected with N atom in the known collector O-isopropyl-N-ethyl thionocarbamate (Z-200) is replaced with ethyl by propyl. The collectors (IP-BIAN and Z-200) have been calculated by DFT methods in quantum chemistry. By analyzing the reaction energy criteria and the frontier orbital properties (HOMO and LUMO), this research predicts flotation performance of novel collectors (IP-BIAN), then the synthetic experiments and flotation verified tests are conducted. The research provides a new theory reference for screening out the high-effective flotation collectors of copper-sulphur separation. This technology adoption will contribute to the sustainable development of mineral resources as it shortens the research cycle of new collector molecules and reduces the investment."