Investigation of the selectivity of ethoxylcarbonyl thionocarbametes during the flotation of copper sulfides

Abstract

In this study, the flotation performances of ethoxycarbonyl thionocarbamate (ECTC), dialkyl thionocarbamate (DATC) and xanthate copper sulfide collectors are compared by the structure-reactivity relationship using generalized perturbation theory and density functional calculation at the B3PW91/6-31G(D) level. The electron-donating power of xanthates is strong and, therefore, xanthates can strongly react with metal cation on the surfaces of copper and iron sulfide minerals through the formation of normal covalent bonds. This explains the poor selectivity of xanthates and also the high pH levels (above 13) required for the flotation separation of copper/iron sulfide minerals. DATC’s are more selective for copper sulfide flotation, particularly against gangue iron sulfides. Although less powerful than xanthates, DATCs can perform copper/iron flotation separation at lower operating pH (commonly at pH levels below 11.5). ECTCs use an ethoxycarbonyl replacing an alkylN-substituent in DATCs. The presence of the ethoxycarbonyl group effectively changes the functional group of collector from -C(=S)NH- to -C(=S)NHC( = O)-. The strong electron-withdrawing ethoxycarbonyl group adjacent to the C=S group decreases the electron density of the sulfur atom, which improves ECTC’s selectivity against iron sulfide minerals at slightly alkaline conditions. The lowest unoccupied molecular orbit (LUMO) of ECTC, which is constituted by the pz-orbit of every atoms in the conjugate -O-C(=O)-N-C(=S)-O- group and which is pleased with accepting richly d-orbital electrons (feedback electrons) from the (t2g)6(eg)3Cu(II) or t6e4Cu(I) configuration of copper cation on the surfaces of copper sulfide minerals, resulted in the formation of dative π-bond. The iron atom, which has a (t2g)6Fe(II) or (t2ga)3(ega)2 Fe(III) configuration on the surfaces of iron sulfide minerals (Fe(III) is the predominant composition at alkaline conditions), has difficulty in offering its d-orbital electrons (feedback electrons) to ECTC’s LUMO. ECTC collectors are powerful for copper sulfide minerals and very selective against iron sulfides, which has been further confirmed by UV spectra and bench-scale and industrial-scale flotation tests.