SX Development at Dos Amigos in Northern Chile

Dagoberto Ibaceta, Operations Manager Juan Garrido, Plant Superintendent Dos Amigos, CEMIN Hurfanos 1178 Of. 401 Santiago, Chile Hans Hein, International Consultant Gabriel Araya, Metallurgical Consultant COGNIS Alonso Crdova 5151 Of. 703 Santiago, Chile

Abstract
Dos Amigos started to operate in January 1997 at Domeyko Chile by applying heap leaching on secondary copper sulphide ore, solvent extraction and electrowinning at a small scale of 5 000 tons of copper per year. Based on a successful start up, the plant was expanded to 10 000 tons of copper cathode production per year, being the first operation in Chile by using the series parallel SX configuration. A new SX reagent was evaluated at pilot plant scale and a decision was taken in late 2002 for replacing LIX 984N by LIX 9790N as make up reagent to the single SX train. Low SX reagent consumption and benefits observed in leaching by operating at reduced copper concentration in pregnant leach solution enabled Dos Amigos to pilot a triple parallel flow scheme. In the meanwhile a special series parallel configuration with increased copper recovery was applied successfully at commercial scale.

Plant description Dos Amigos plant, owned by Compaa Explotadora de Minas SCM (CEMIN), is located 2 km east of the Panamerican Highway, 5 km south of Domeyko and 610 km north of Santiago, the capital of Chile.

FIGURE 1 - OVERALL PLANT VIEW

The mine began its operation several years before the bacterial leaching/solvent extraction/electrowinning plant was commissioned in 1997. Copper production started at a level of 5000 tons Cu per year, treating oxide ore during the first four months. After twelve months of operation the plant doubled its production to 10000 tons Cu per year. The plant has been successful in achieving its production goal, obtaining high quality cathodes since start up. An overall plant view is shown in Figure 1 . Copper sulphide ore from an open pit is crushed to 98 % below . The ore is agglomerated with water and sulfuric acid in a rotating drum and by truck it is transported to a stacking device, as indicated in Figures 2 and 3.

FIGURE 2 - ORE PROCESSING FROM MINE TO HEAPS

FIGURE 3 - AGGLOMERATION UNIT

FIGURE 4 - SIMPLIFIED LEACHING SCHEME

Bacterial leaching is carried out in heaps 3.8 m high. In a 400 days leach cycle 78 % of the copper is usually recovered from digenite ore, a cuprous sulphide copper ore. Since start up leaching is done by using an on/off scheme with one day rest period every second day. During irrigation, the specific flow rate is 10 liters/hour-m2 . Heap leaching considers three stages shown in Figure 4 . Fresh ore is leached with raffinate, then intermediate liquor is applied in a second leaching step and finally raffinate is used again. Total sulfuric acid consumption in leaching is 16 kg / ton of ore and approximately 50 % is added to the curing drum. A typical copper extraction curve in leaching is shown on Figure 5 .

FIGURE 5 - TYPICAL RECOVERY CURVE IN LEACHING

FIGURE 6 - SOLVENT EXTRACTION PLANT VIEW

Solvent extraction started with four mixer settlers on a E1/E2 x S2/S1 configuration. Six months after plant commissioning, construction activities began for building a fifth mixer settler. The expansion program was completed in a six months time period. In early 1998 Dos Amigos became the first SX plant operating a series parallel configuration in Chile. The SX circuit was based on a flow scheme of E1/E2 x EP x S2/S1. The single SX train considered a particular arrangement in reference to mixer settler location shown in Figures 6 and 7. Additional piping and valves were included to by pass any mixer settler being repaired. FIGURE 7 - SOLVENT EXTRACTION FLOW DIAGRAM

All mixer settlers have an equivalent size of three minutes retention time in mixers and a specific flow of 3.6 m3/hour-m2 in settlers. Electrowinning is operating at current density of 278 A/m2 in 64 electrolytic cells, whereby 10 cells belong to a cleaner circuit. Each electrolytic cell contains 30 cathodes and 31 anodes. Current efficiency is around 91 % and commonly 100 % high grade cathodes are being stripped from stainless steel blanks, at a cathode weight around 40 kg each. Cobalt concentration in electrolyte is kept slightly above 100 ppm Co and guar is added at a rate of 200 g/ton Cu. FIGURE 8 - ELECTROWINNING TANK HOUSE VIEW

Total man power is 57 persons in leaching/solvent extraction/electrowinning and the plant operates with its own staff without contractor personnel.

Brief SX plant history By January 1997 CEMIN commissioned Dos Amigos solvent extraction plant at a production level of 5000 metric tons of copper per year. The original plant design considered a reagent blend for initial fill of C-9 / C-12 aldoxime and C-9 ketoxime, a single SX train of two extraction / two strip stages, whereby one of the strip stages could be converted into a wash stage, whenever needed. A wash stage alternative was justified in view of an uncertain chloride level in pregnant leach solution during plant design, obtaining 1.5 g/l chloride during the first months of operation. In past years Dos Amigos never needed to convert one of the strip stages into a wash stage, as the chloride level in electrolyte was kept below 15 ppm. After a year of operation Dos Amigos commissioned an additional mixer settler by adopting a conventional series parallel configuration at a production capacity of 10000 tons Cu per year. The expected copper production rate was achieved soon and the conventional series parallel scheme was in force during the following five years, using LIX 984N for make up quantities. In 2002 a new reagent called LIX 9790N was piloted and by the end of the year CEMIN decided to replace the LIX 984N reagent inventory gradually through make up quantities of LIX 9790N. In the year 2002 CEMIN also evaluated a triple parallel flow configuration for maintaining the copper production level at reduced copper tenor in pregnant leach solution. CEMIN observed a copper recovery increase in leaching and further benefits by reducing copper concentrations in leach solutions. A final decision for increasing the pumping capacity in leaching is pending. In 2003 a special series parallel SX configuration was applied at commercial scale and based on the new process concept, copper recovery in SX increased above three percent. Topics of interest at Dos Amigos Several aspects or features are worthwhile to be mentioned in reference to Dos Amigos plant operation: 8

Secondary sulphide ore leaching is done in heaps at total iron concentration of 1.2 g/l Fe, obtaining copper recoveries of 78 % in 200 days of effective irrigation time and 400 days of total leach cycle. The special series parallel configuration performs at copper recoveries above 95 % and at net copper transfer in organic of 0.35 g/l Cu /% LIX 984N. The unit reagent consumption since plant commissioning in 1997 was 1.2 kg LIX 984N/ton Cu, operating during one year conventional 2Ex2S and during five years series parallel of 2Ex1EPx2S. Total electrolyte bleed, including measured bleed plus electrolyte entrainments in stripped organic and others, considers a recycle of 1.1 % copper. A rather critical Fe/Mn ratio of 3/1 in pregnant leach solution is generating a Fe/Mn ratio as high as 90/1 in electrolyte, due to low aqueous entrainments in loaded organic. The pregnant leach solution contains 0.45 g/l chloride, obtaining less than 8 ppm chloride in electrolyte, without using coalescers and/or any wash stage. The average organic entrainment in raffinate is 12 ppm and aqueous in loaded organic reaches 125 ppm. The global copper/iron selectivity, considering chemical transfer and physical entrainments is 1250/1 at high pH above 2.1 in pregnant leach solution. During the first three years of plant operation the average reagent half life exceeded 15 years. Dos Amigos produces 100 % high grade copper cathodes with sulphur below 5 ppm and lead below 3 ppm , at 278 A/m2 of current density.

SX operation until 2002 When CEMIN decided to expand its production capacity from 5 to 10000 tons Cu per year, the lowest capital investment in solvent extraction was prefered, without converting the second strip stage into a wash stage. The suggestion was to build an additional mixer settler for converting the plant into a conventional series parallel configuration. The decision was taken 9

once Dos Amigos confirmed that reasonable organic entrainments in raffinate were achievable. The selected flow diagram is shown in Figure 9 .

FIGURE 9 - SERIES PARALLEL CONFIGURATION

PLS

Spent Pregnant Electrolyte

E1

E2

EP

S2

S1

Raffinate

Stripped Organic

Loaded organic

Table 1 illustrates a summary of typical solution analyses. The pregnant leach solution has a low total iron concentration, the chloride level is significant and total iron / manganese ratio is rather high for an operation without coalescer and/or wash stage in solvent extraction. Due to low aqueous entrainments in loaded organic the electrolyte is generating a high Fe/Mn ratio and minimum chloride concentration.

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TABLE 1

- TYPICAL SOLUTION ANALYSES Pregnant leach solution 3.6 - 4.3 2.1 2.2 1.18 0.48 450 390 23 92 Electrolyte 30 33 170 180 44 47 2.30 0.46 7 20 102 228 680

Copper in SX feed (g/l) SX feed pH Cu in spent (g/l) Acid in spent (g/l) Cu in preg. electr. (g/l) Total iron (g/l) Ferrous iron (g/l) Chloride (ppm) Manganese (ppm) Cobalt (ppm) Total sulfate (g/l) Electrol. potential (mV)

Typical SX parameters and results between 1998 and 2002 are summarized in Table 2 . Usually Dos Amigos is maintaining flows as constant as possible and the PLS copper tenor has minor fluctuations, mainly related to the leaching performance. Phase continuity is similar to common practice and the mixer settler size is the same for all stages. After-settlers are available for both, raffinate and electrolyte flows. The organic tank as designed is a sort of additional settler. A Spintek electrolyte filter of 60 m3/h was replaced in recent years by an Eimco filter of 90 m3/h . The SX plant started to operate with a mixture of C9 aldoxime, C12 aldoxime and ketoxime. For the purpose of make up only LIX 984N had been used in its concentrate version LIX 984NC. Conventional series parallel operated from 1998 until 2002. High copper net transfer, low electrolyte bleed and low entrainments in general were the most outstanding parameters during that period. Copper recovery in SX had been above 91 % and Cu/Fe selectivity was kept at reasonable level by operating at high pH range of 2.1 2.2 in PLS. 11

The average reagent consumption in those five years of conventional series parallel operation had been extremely competitive. Temperature fluctuations in solvent extraction were significant, as high as 10C . TABLE 2 - TYPICAL PARAMETERS ON SERIES PARALLEL SX CONFIGURATION ( From 1998 to 2002 ) SX configuration Total PLS flow (m3/h) PLS flow to series stages (m3/h) PLS flow to parallel stage (m3/h) Organic flow (m3/h) Electrolyte flow (m3/h) Aqueous continuity (stages) Organic continuity (stages) Mixer retention time (min) Specific flow in settlers (m3/h-m2) Copper in PLS (g/l) Copper in combined raffinate (g/l) SX recovery (%) LIX concentration (v/v %) Stripped organic (g/l Cu) Loaded organic (g/l Cu) Net Cu transfer (g/l Cu / % reag.) Reag. consumption (kg LIX/ton Cu) Chemical Cu / Fe selectivity Global Cu / Fe selectivity Total electrolyte bleed (m3/day) Cu recycled in electrolyte bleed (%) Temperature range in extraction (C) 2E x 1EP x 2S 320 - 330 140 150 170 180 180 90 E1 / S2 E2 / EP / S1 3.0 (all) 3.6 (all) 3.6 4.2 0.28 0.38 91 93 18.5 19.5 1.8 2.0 8.2 8.8 0.34 0.36 0.9 1.3 1200 1500 1150 1450 9.0 11.0 1.0 1.2 15 - 25

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LIX 9790N a new SX reagent In 2002 a new reagent called LIX 9790N was successfully pilot tested and the replacement of LIX 984N was decided by the end of 2002. In early 2003 Dos Amigos started to use LIX 9790N as make up reagent to Dos Amigos solvent extraction plant. The main characteristics of the new reagent are increased reagent stability and improved copper net transfer in organic. In addition the reagent has excellent characteristics, which should be an important factor, whenever a single strip stage is necessary for a triple parallel flow operation, sometimes in the future. In Table 3 the most significant pilot test results are indicated. By comparing LIX 984N with LIX 9790N, the latter is achieving similar metallurgical results at significant less reagent inventory. The difference between both reagents concentrations as needed is roughly 5 % by volume.

TABLE 3 Fresh organic

LIX 9790N / LIX 984N COMPARISON SERIES PARALLEL PILOT OPERATION PLS flow ratio E1-E2/EP 1.38 1.38 0.72 0.72 PLS g/l Cu 4.21 4.21 4.25 4.21 Raffinate, g/l Cu E2 E1P Combined 0.43 0.31 0.37 0.37 0.30 0.33 0.38 0.30 0.34 0.39 0.24 0.32 SX Recovery % 91.2 92.1 92.2 92.4

20% LIX 984N 19% LIX 9790N 20% LIX 984N 19% LIX 9790N

Triple parallel SX configuration By leaching at high raffinate flow Dos Amigos is expecting an improvement of copper recovery in leaching. A possible SX flow scheme, as shown in Figure 10 , was piloted during the second semester of 2002 . 13

The new SX configuration converted the stripping stage S2 into a fourth extraction stage, maintaining the original concept of conventional series parallel and adding a third PLS flow to extraction stage number four. In view of positive results obtained with LIX 9790N in a series parallel configuration of two strip stages and knowing that the new reagent had advantages over other reagents by using a single strip stage, several blends of LIX 9790N were pilot tested, showing the results obtained in Table 4 . A graph on extraction efficiencies is plotted in Figure 11 . The pilot test work confirmed the technical feasibility of operating a triple parallel SX configuration and a final decision will be based on economics and definitive conditions in leaching.

FIGURE 10 - TRIPLE PARALLEL CONFIGURATION

PLS

Spent

E1

E2

E3

E4

Raffinate Pregnant Electrolyte

Loaded organic

14

TABLE 4 - TRIPLE PARALLEL PILOT TEST RESULTS BY USING A BLEND OF FRESH LIX 9790N AND PLANT ORGANIC LIX 9790N /circuit organic ratio 1/3 1/1 3/1 LIX concentration (v/v %) 20.4 19.6 20.0 PLS g/l Cu E2 3.00 3.01 3.02 0.40 0.30 0.19 Raffinate , g/l Cu E3 0.41 0.35 0.26 E4 0.21 0.18 0.17 Combined 0.33 0.20 0.17 SX recovery % 89.0 91.0 93.4

FIGURE 11 - PILOT EXTRACTION EFFICIENCIES FOR TRIPLE PARALLEL FLOW

Special series parallel configuration In 2003 Dos Amigos improved its solvent extraction operation at plant scale by applying a new concept of series parallel configuration, developed by Cognis. The special series parallel arrangement presented in Figure 12 differs from conventional series parallel, as stripped organic is transferred to extraction stage E2 instead of extraction stage EP. 15

Typical plant data is summarized on Table 5. In the first column operating results are given on conventional series parallel as obtained in the past and in the second column results on special series parallel generated in early 2003 are presented. The most significant difference between both columns is the increased SX recovery for the special series parallel configuration. TABLE 5 - SPECIAL AND CONVENTIONAL SERIES PARALLEL COMMERCIAL PLANT COMPARISON Conventional Series Parallel E1/E2/EP/S2/S1 330 150 180 180 90 E1 / S2 E2 / EP / S1 0.9 / 1 1.2 / 1 1/1 3.90 0.39 0.27 0.32 91.7 18.6 0.352 2.0 8.6 1400 30 177 44 Special Series Parallel E1/EP/E2/S2/S1 330 180 150 180 90 E1 / S2 E2 / EP / S1 0.9 / 1 1/1 1.2 / 1 3.80 0.11 0.27 0.18 95.2 18.6 0.357 1.9 8.5 1450 31 175 45

SX configuration Total PLS flow (m3/h) PLS flow to series stages (m3/h) PLS flow to parallel stage (m3/h) Organic flow (m3/h) Electrolyte flow (m3/h) Aqueous continuity (stages) Organic continuity (stages) Mixer O/A E1 Mixer O/A E2 Mixer O/A EP Copper in PLS (g/l) Copper in series raffinate (g/l) Copper in parallel raffinate (g/l) Copper in average raffinate (g/l) Recovery (%) LIX reagent concentration (v/v %) Cu net transfer (g/l Cu/% reag.) Copper in stripped organic (g/l) Copper in loaded organic (g/l) Chemical Cu / Fe selectivity Copper in spent electrolyte (g/l) Acid in spent electrolyte (g/l) Copper in pregnant electrolyte (g/l)

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FIGURE 12 - SPECIAL SERIES PARALLEL CONFIGURATION

PLS
Spent Pregnant Electrolyte

E1

EP

E2

S2

S1

Stripped Organic

Raffinate Loaded organic

Once the SX plant confirmed its expectations on special series parallel, Dos Amigos decided to continue using the new configuration, achieving potential improvements in aspects like extraction efficiency, net copper transfer, increased copper production and/or equivalent copper production at lower copper tenor in PLS. Conclusions In six years of operation Dos Amigos had demonstrated that a small sulphide leaching, solvent extraction, electrowinning plant is capable to generate competitive operating data, to produce excellent copper cathodes and to innovate in new technology. Acknowledgements The authors wish to thank Juan Rassmuss and Compaa Explotadora de Minas SCM CEMIN for their assistance and great support in preparing the present publication. 17