Improved mass transport efficiency in copper solvent extraction

Abstract

This thesis considers methods which can be employed to increase the mass of copper transferred into and out of the organic phase during the load and strip stages of commercial solvent extraction processes. Conventional 5-alkylsalicylaldoxime reagents transfer 1 mol of divalent copper per 2 mol of ligand in a neutral complex of the type [Cu(L-H)2] via a pH-swing process. New triacidic ligands have been designed which triple the molar transport of copper to form [Cu3(L-3H)2]. Until recently copper recovery by solvent extraction has been confined to oxidic ores which are leached with sulfuric acid. New leaching technologies generate high tenor copper sulfate feed streams from sulfidic ores. The conventional 5- alkylsalicylaldoxime reagents do not work effectively in conjunction with these leach processes as they do not consume the acid which is generated on loading the oxime. To address this problem ditopic zwitterionic ligands have been designed which can transfer both metal cation and attendant anion. These new metal salt reagents are diacidic, therefore not only transfer metal salts but also increase the molar transport relative to the conventional reagents. Equilibrium-modifiers are often added to improve the mass transport efficiency of conventional solvent extraction processes. The nature of their interaction with the species in solution is poorly understood. This thesis investigates their interaction with the free ligands and copper complexes to gain an understanding of their mode of action in order to rationalise the design of future modifiers to optimise recovery efficiencies. Increased molar transport is addressed in Chapter 2. The diacidic ligand 5- methylsalicylaldehyde-pivaloylhydrazide (L2) and its dinuclear copper complex [Cu2(L2-2H)2] were synthesised and characterised to gain an understanding of their speciation in solution. X-ray structural analysis of [Cu2(L2-2H)2] confirmed that the phenolate oxygen atoms bridge the copper centres rather than the amidato oxygen atoms of the hydrazone. Variable temperature magnetic susceptibility data confirm that the copper centres are antiferromagnetically coupled as expected for the Cu-OCu angle (99.6(2)°). An understanding of the coordination geometry of the dinuclear systems lead to design of triacidic ligands. A series of 3-hydrazono- and 3- hydroxyanil- 5-alkylsalicylic acids were synthesised. The prototype ligand 5-methyl 3-octanoylhydrazonosalicylic acid (L6) was demonstrated to triple molar transport and increase mass transport by 2.5 fold. Solvent extraction results indicate that copper is sequentially loaded as pH is increased. The plateaux observed in loading curves suggest formation of stable mono-, di-, and tri-nuclear copper complexes within the pH-ranges 1.75 - 2.75, 3.25 - 4.0 and > 4.25 respectively. The triacidic ligands were also demonstrated to double the molar transport of the conventional salicylaldoximes when used in 1:1 blends by formation of a ternary complex. Chapter 3 describes the incorporation of two tertiary amine groups into diacidic salicylaldehydehydrazone ligands to form dinucleating metal salt extractants. Piperidinomethyl, piperazinomethyl and dihexylamino groups were incorporated into various positions of the ligand including 3- and/or 5- positions of the salicylaldehyde or incorporated into the hydrazone. Solvent extraction results obtained for 3,5- bis((dihexylamino)methyl)salicylaldehyde-octanoic hydrazone (L20) are consistent with transfer of 1 mol of copper sulfate per mol of ligand in the organic phase between pH 2.0 and 2.5. This result is indicative of the formation of [Cu2(L20)2(SO4)2]. Conventional salicylaldoximes are “strong” copper extractants which require concentrated acid electrolyte to efficiently strip the copper from the organic phase. However, as the use of concentrated acid affects the quality of the copper cathodes, oxygen-containing equilibrium modifiers are often added. These facilitate copper stripping without adversely affecting the loading. The affect of 2-ethylhexanol (2- EH) and trioctylphosphine oxide (TOPO) on the extractive ability of 5-toctylsalicylaldoxime (19) in n-heptane is reported. Both are found to decrease copper extraction more under stripping conditions than loading conditions. 2-EH shows little affect at pH greater than 2.5. TOPO does not significantly affect copper loading at pH greater than 3.0. Evidence for the formation of the adduct [Cu(19-H)2)(TOPO)] was obtained from UV/Vis, IR, EPR and sonic spray mass spectrometry.