Copper recovery using leach/solvent extraction/electrowinning technology: Forty years of innovation, 2.2 million tonnes of copper annually by G.A. Kordosky* small scale in analytical chemistry3 and on a large scale for the recovery of uranium from Synopsis sulphuric acid leach solutions4. Generally Mills had already developed and commercialized The concept of selectively extracting copper from a low-grade dump Alamine® 336 as an SX reagent for the leach solution followed by stripping the copper into an acid recovery of uranium from sulphuric acid leach solution from which electrowon copper cathodes could be produced liquors5 and believed that a similar technology occurred to the Minerals Group of General Mills in the early 1960s. for copper recovery would be welcome. This simple, elegant idea has resulted in a technology by which However, an extensive market survey showed about 2.2 million tonnes of high quality copper cathode was produced in year 2000. The growth of this technology is traced over that the industry reception for copper recovery time with a discussion of the key plants, the key people and the by L/SX/EW technology was almost hostile. important advances in leaching, plant design, reagents and The R&D director of a large copper producer electrowinning that have contributed to the growth of this predicted at an AIME annual meeting that technology. Some thoughts on potential further advances in the there would never be a pound of copper technology are also given. recovered using solvent extraction and his comment prompted applause5. Fortunately, the Minerals Development Group of General Mills, in the person of Joe House, Don Agers and Ronald Swanson, Introduction believed so much in the copper L/SX/EW process that they kept the development of this A keynote paper for solvent extraction (SX) technology alive as a ‘bootleg’ project, that is, applications in hydrometallurgy should ‘set the a project where the three individuals had other stage’ for the papers that follow by discussing primary work duties and could only work on a commercially successful application of SX in this project when they found time or on their hydrometallurgy. In addition the paper needs own time. By late 1962 this group had to discuss a complete metal recovery process identified and formulated an organic soluble for the simple reason that an SX process for molecule containing a hydroxy-oxime metal recovery does not stand alone, it is functionality as the reagent LIX®63. While always part of an overall metal recovery LIX 63 had many of the properties required for process. The SX process must be compatible a reagent to be successful in the proposed with, and complimentary to, the metal leaching L/SX/EW flow sheet, LIX 63 was not process that precedes it and the metal recovery compatible with the copper leaching process process that follows. The paper should because it did not extract copper below pH~36. acknowledge that most of the advances in a Technically this problem could be solved metal recovery technology are made for by neutralizing the acid leach liquor or by economic reasons. This discussion of the leaching oxide copper with ammonia, but leach/solvent extraction/electrowinning neither solution was economical. a molecule (L/SX/EW) process for copper recovery, that extracted copper well from typical dump considered by some to be one of the great leach liquors (pH ~1.8) had to be built. The advances in copper recovery technology of the reagent LIX 64, containing the ketoxime LIX past 100 years1, satisfies these criteria. Historical background * Cognis Corporation, Tucson, USA When the sulphuric acid copper L/SX/EW flow © The South African Institute of Mining and sheet (Figure 1) was put forth by the Minerals Metallurgy, 2002. SA ISSN 0038–223X/3.00 + Development Group of General Mills in 1960 0.00. This paper was first presented at: ISEC solvent extraction had been known for over 2002, International Solvent Extraction Conference, 100 years2. It was used extensively on a very Cape Town, South Africa, 17–21 Mar. 2002. The Journal of The South African Institute of Mining and Metallurgy NOVEMBER/DECEMBER 2002 445 ▲ Copper recovery using leach/solvent extraction/electrowinning technology Figure 1— Conceptual leach/solvent extraction/electrowinning flow sheet 65 (Figure 2) and a catalytic amount of LIX 63, was Ranchers’ Bluebird sulphuric acid leach/solvent introduced in 19657 and in March 1968 the first commercial extraction/electrowinning plant copper L/SX/EW operation, the Bluebird plan of Ranchers Ranchers leached run of mine copper oxide ore (> 0.5% Cu) Exploration and Development Corporation, came on line1. placed in a sealed canyon in 20-foot layers (heaps) by distributing dilute sulphuric acid over the fresh ore via spray Copper recovery by L/SX/EX in 1968 emitted from needle valves with pipes and needle valves In 1968 there were only two widely practiced copper leaching placed to ensure complete coverage of the ore. New heaps processes using dilute sulphuric acid. The first process, vat were built over old heaps. Pregnant leach solution flowing leaching of high-grade copper oxide ore followed by EW of from the bottom of the heap was collected in a pond created by placing a dam downstream from the leach area. The copper from the leach solution, produced low quality copper Bluebird copper SX plant was built similar to existing cathode at relatively high cost. In 1968 the tonnage of high- uranium SX plants with tall, single baffled mixers and long grade oxide ores was decreasing and vat leaching was on the narrow settlers. Dispersion exiting the mixer was pumped to decline. the opposite end of the settler and the phases flowed back The second process, heap and dump leaching of low- toward the mixers. grade oxide and/or sulphide ore followed by precipitation of In electrowinning rich electrolyte with ~36 g/l Cu, 3 g/l Fe low quality copper from the leach solution on scrap iron, was and 145 g/l H2SO4 entered one end of the EW cells and spent practiced on oxide ore that was too low-grade for vat electrolyte with ~32 g/l Cu and 151 g/l H2SO4 exited the leaching, or low grade sulphide ore that had to be mined in other end. Cathodes weighing 60 kilograms were grown on order to expose the underlying high grade sulfide ore. Copper copper starter sheets at a current density of about 180 A/m2 recovered from leaching low grade copper ores was with a current efficiency of 80 to 85%. The anode was 6% Sb considered a bonus and little effort had been made to fully in Pb. understand the leaching process or to maximize copper Design production at Ranchers was 30,000 pounds of recovery. While some fundamental leaching studies had copper daily. In its first fiscal year of operation, July taken place8,9, on the whole leaching was a poorly practiced 1968–June 1969, the Bluebird plant produced 9 million art and little had been done to make it a well-practiced pounds of copper (82% of design), a remarkable achievement science. for a metallurgical plant using new technology. By later Solvent extraction for copper was not yet proven commer- adding only rectifier capacity the plant often exceeded its cially so most copper companies were taking a wait and see design production by 50%. attitude. Furthermore LIX 64, the only reagent available, had Ranchers’ Bluebird plant proved that L/SX/EW significant limitations with respect to extractive strength, technology could produce large quantities of good quality 1 metal transfer kinetics and copper/iron selectivity and it could cathode copper on a consistent day to day basis at a profit . This raised the awareness and sparked the interest of the only be used up to a maximum copper loading of about 3 g/l industry in copper L/SX/EW. Improvements in the technology because of entrainment problems. These properties restricted quickly followed from many sources including consultants, copper leach solutions which could be effectively treated by copper producers, engineering companies, chemical SX using LIX 64 to ≤ 3 g/l Cu at a pH ≥ 1.8. companies and metallurgical testing laboratories. In 1968 the copper industry as a whole did not believe large quantities of high quality copper could be produced by Improvements in copper L/SX/EW technology hydrometallurgy and at the time the Ranchers plant came on line, expectations for the eventual success of copper L/SX/EW Solvent extraction reagents technology were rather modest. The first improvement in copper SX reagents came when LIX ▲ 446 NOVEMBER/DECEMBER 2002 The Journal of The South African Institute of Mining and Metallurgy Copper recovery using leach/solvent extraction/electrowinning technology Figure 2—General structure of oxime molecules used for copper recovery 64N was added as makeup to the Ranchers plant in late of the ketoximes, without the detrimental properties of added 1968. LIX 64N had greater extractive strength, faster modifier17. The addition of LIX 860-1 (Figure 2) to existing kinetics, faster phase separation, lower entrainment, plants using LIX 64N allowed these plants to quickly upgrade increased copper/iron selectivity and lower viscosity than LIX their plant performance and flexibility if needed or desired. 6410. These improved reagent properties broadened the range Today aldoxime/ketoxime blends are widely used in copper of copper leach liquors which could be successfully treated by SX. solvent extraction, for less staging thereby reducing the Henkel purchased the SME 529 technology from Shell in capital cost of the SX plant, and lowered operating costs by late 1984 and 2 years later, using a new manufacturing decreasing organic losses and tankhouse bleeds. LIX 64N is process, began producing LIX 84-1, a much improved version LIX 65N (Figure 2) with a catalytic amount of LIX 63.