OPERATING EXPERIENCE FROM THE BUCHIM COPPER PROJECT Todor Angelov, Georgy Savov, Aleksander Tsekov, Ivanka Valchanova

Iontech Engineering LTD, e-mail: iontech@abv.bg Abstract. The Buchim Copper Project has been producing cathode copper since January 2012, using a unique L/IX/SX/EW process, developed by IONTECH .The process recovers copper from sulphide and oxide ores and has a number of novel features, that have been integrated into a efficient operations. The original process design has been refined through a process of continual optimization. Expansion of the existing ion exchange circuit and construction of new facility for treatment of excess drainage waters are in progress. Original operations as well as changes and additions within the plant, which lead to improved plant throughput, recovery and availability, are described. 1. Introduction Buchim Copper Project comprises a process plant, situated near the village of Buchim and in the south borders of Plachkovitsa Mountain, in Republic of Macedonia. Territorially and administratively the project belongs to the municipality of Radovis. It is 95 kilometers away from the Skopje capital, and 170 kilometers from the nearest port Thessaloniki (Republic of Greece).The process plant was designed to produce 2400 tpa of cathode copper, however as a result of a planned upgrade, the plant will produce copper cathode at a rate of 2800 tpa. The process plant comprises a leach operation for treatment of the oxide and sulfide ores, together with associated ion exchange, solvent extraction, and electrowinning circuits to separate and recover copper dissolved from the ores. The project construction was completed in December 2011 and reached steady copper production in August 2012 after an extended commissioning, related largely to mechanical issues. Further changes and additions to a number of the original unit operations within the plant has led to changes in operational procedures, and recovery, as well as to plant availability levels routinely above 95%. 2. Operations The Buchim Copper Project includes the following operations: Leaching , Ion Exchange, Solvent Extraction and Electrowining [1]. The main structures at the mine complex are sulfide ore dump, oxide ore heap, pregnant leach solution ponds, plant feed pond, raffinate pond , IX facility and SX/EW plant.(Figure 1) The piping network for dump and heap comprises main lines at ground level and heap supply header pipes along the heaps, which distribute solution over the surface through a series of dripper lines. All piping networks are HDPE throughout, and are installed manually using special equipment. Leach solution percolates down through the ore until it reaches the base of the leach pad. The pad is built on a slight slope towards a series of solution drains. Oxide ore is leached at application rates between 4 to 6 l/h/m2 ,and sulphide ore between 6 to 9 l/h/m2[2]. In a leach operation, the barren solution from the ion exchange facility (filtrate) and solvent extraction plant (raffinate) which has a high acid concentration, is fed to the old dump and oxide heap to produce a pregnant leach solution (PLS) suitable for subsequent treatment. The flow regime is regulated according the existing conditions by directing dump and heap effluent stream to individual PLS ponds.

Figure 1. Buchim Copper Project Flowsheet

From the PLS ponds, solutions are directed to IX facility with a design feed flow rate of approximately 650 m3/h. The facility consists of 8 ionexchange columns-4 IONTIX units (Iontech Design )[3]. The obtained IX regenerant is pumped to plant feed pond, where it is mixed with pregnant leach solution from the leach operation. Feed solution from the plant feed pond flows into a conventionally designed solvent extraction plant (SX) at a rate between 35-40 m 3/h .The SX plant using a 3E x 2S configuration, with conventional flow design. The feed is depleted of copper and returned to leaching as a raffinate solution along with the filtrate from IX facility, thus forming a very environmentally responsible process by not allowing any discharge into the environment. The SX plant recover 90% of the feed copper. The use of a selective copper extractant (LIX 84I),which operates in a closed circuit inside the plant, allows the copper to be transferred to an electrolyte operating in a closed circuit with the electrowinning plant. The copper is captured from the strong electrolyte in the electrowinning plant. The electrowinning process uses a common design. Cells are connected in series to a current transformer rectifier with hydraulic feeding of electrolyte to cells connected in parallel. Scavenger cells are not included. The operation uses stainless steel permanent cathodes and Pb/Ca/Sn alloy anodes, assembled in combinations of 25 and 26 units per cell, respectively, contained in a total of 24 cells. The cathodes are removed from the cells and transported for manually stripping by hammer and chisel in order to separate the deposited copper from the mother plate. The copper cathodes with 99.99% purity are weighed and banded and the mother plates are rinsed and returned to the cells for the next loading cycle.The main operational parameters are summarized in Table 1.
Table 1.Buchim Copper Project Main Operational parameters

Leaching PLS IX resin SX feed Organic

Dump Leaching :Leach Area-75000 m2,Solution Application Rate -6-9 l/h/ m2;Heap Leaching: Heap Height-60m,Leach Area-77628 m 2,Solution Application Rate - 4-6 l/h/ m2 Dump PLS:300- 440 m3/h; Heap PLS:160-210m3/h;PLS Grade-0.64gpl Cu av. 64 m3(H+ form);Lewatit TP 207 M+ 35-40 m3/h; 8-10 gpl Cu, 15 gpl H+ 45 m3/h;20 v/v% LIX 84-I diluted in ShellSol D100

Lean Electrolyte Strong Electrolyte Electrowinning Productivity Product Quality

22,5 m3/h,37 gpl Cu ,175 gpl H+ 110 m3/h,49 gpl Cu,160 gpl H+ Permanent Cathodes,280 A/ m2,24 cells,92% Current Efficiency 2400 tpa copper cathodes LME (High Purity Grade) Copper 3. Operational Issues

The Buchim Copper Project has been operating continuously since early 2012 and considerable operational data has been gained, which has resulted in a better understanding of the process operation of this type of unique circuit. However, despite the overall very successful operation at the site, some operational issues were identified. Several process modifications and upgrade works have been undertaken and these will be discussed below. 3.1 Leaching 3.1.1. Leach Chemistry After approximately a year of successful leaching operations, the pregnant leach solution chemistry has changed dramatically-solution copper grade decrease, while acidity and ferric iron concentration increase. This lead to poor performance of the subsequent ionexchange processes and hence a reduction in the total plant productivity. The analysis of the leaching operations has shown that this issue was due to improper leach management plan and incorrect application rates. Desirably, application rates for leach solution should be low enough to provide efficient leaching, but if they are too low or too infrequently applied the ore heaps may partially dry out, which will stop mineral oxidation and bacterial activity. With copper ores and mine waste, the rate of copper solubilization usually steadily decreases over the months and years and short applications periods should be followed by rest periods, during which aeration and oxidation of copper minerals will continue. An orderly leach management plan, with properly designed application and rest periods and application rates are developed and enforced. Compliance with the plan will lead to the restoration of copper and ferric iron grade and the acidity of solution to the optimal levels. The leach management plans both for dump and heap leach operations of the Buchim Copper Project are given below: Dump Leach Operation Application Period -3 months Rest Period-6 months Application Rate-6-9 l/h/m2 3.2. Ion Exchange 3.2.1. Ferric Iron As a result from the improper leach operations ,increased iron concentrations in PLS were encountered and this lead to some negative impacts on the resin performance .Ferric iron is contributing with copper in uptake on the resin and this reduces its operating capacity significantly .Besides this, ferric iron can cause damage of the resin by precipitation as iron(III) hydroxide(Figure 2), which act as a catalyst for oxidation by oxygen.Therefore to compensate the effects of iron the following modifications in ionexchange process were undertaken: working with high specific flowrates during the exhaustion cycle Heap Leach Operation Application Period -2 months Rest Period-2 months Application Rate-4-6 l/h/m2

feed solution pH maintaining below 3 (namely 2.6-2.8) to prevent precipitation of iron(III) resin regeneration with high specific acid dosage(18-20%) resin soaking in acid solution for 1 to 2 hours, before rinse out.

Figure 2. Plant Ion Exchange Resin

3.3. Solvent Extraction 3.3.1Crud The commissioning of SX/EW plant was followed by a catastrophic collapse in the operation of the SX section. The phase disengagement times increased and the settlers filled with stable emulsion-crud. The extraction kinetics and the reagent capacity decreased, resulting in a major limitation on the copper transfer to the EW plant. On-site investigation of the cause of the situation determined that it was due to enormous quantities of suspended solids in solutions exiting dump leaching .Those effects were eliminated by crud removing from the settlers with air operated diaphragm pump and by application of a rehabilitation process for the SX organic. The rehabilitation of the organic was achieved using a treatment with acid activated clay. The procedure was implemented to the plant organic on a batch basis. Cycle times for the treatment were 1 to 2 hours by using a plate and frame filter to remove the clay, before returning the treated organic to the circuit. The benefit of this treatment was obvious, as the plant organic returned toward the original extraction capacity, kinetics and phase disengagement times. 3.4. Electrowining 3.4.1. Contaminant Elements Build Up o Iron In most SX/EW operations, iron is the primary contaminant element and is transferred into the electrolyte both by entrainment of pregnant leach solution and by chemical extraction. This build up of iron in electrolyte result in a loss of current efficiency in the electrowinning process due to the continuous oxidation/reduction of Fe 2+ to Fe3+. The method used for controlling the iron concentration in EW section of the Buchim Copper Project is periodically bleed a portion of the iron-rich, copper-depleted electrolyte from the circuit and replace it with fresh electrolyte. This bleed flow at the Buchim site is 6 cubic meters daily.

o Manganese Manganese as Mn2+ in the electrowining is not a problem, however the Mn 2+ rapidly becomes oxidized to MnO4- , which is a powerful oxidizing agent and which rapidly degrade both diluents and the extractant in solvent extraction. This degradation may not initially have a great effect on the maximum copper loading of the organic, but will reduce extraction kinetics and increase phase disengagement times and entrainment. The development of the manganese problem at Buchim Copper Project occurred quickly after commissioning and was recognized by purple coloration and increased Eh of the electrolyte. The rehabilitation process was done successfully with the addition of ferrous sulfate to the electrolyte and with contacting of the electrolyte with mild steel and iron wire. 3.4.2 Electrolyte Distribution The flow distribution of electrolyte within the cells is very important. At the Buchim site this is accomplished by using a PVC manifolds with 200 distribution holes (100 on each side) at 45 degrees from vertical, placed in the bottom of the cells.(Figure 3).The use of this type of distribution system increases the velocity of electrolyte across the face of the cathode plate allowing electrowining operation at higher current densities as well as a proper growth ,orientation and morphology of copper deposit.

Figure 3. Electrolyte Distribution System

3.4.3 Acid Mist Control Consistent with Buchims strong commitment to the environment and its workers, the most modern method for the control of acid mist generated in the electrowinning cells are employed. The method consists of a hood located over each electrolyte cell that collects the mist and processes it in a countercurrent scrubber with a water shower. The acid mist is recovered and acid-free air is expelled into the environment. This acid mist control method guarantee a clean and safe environment in the working place, thus protecting the health of workers and also reducing acid damage to equipment. The summary of operational issues at the Buchim Copper Project and its resolutions are given in Table 2.
Table 2. Operational Issues Summary

Process Leaching Ionexchange

perational issues Resolution Changed Leach Chemistry Orderly leach management plan Ferric Iron Effects Working with high specific flow rates during exhaustion

Solvent Extraction Electr wining

Crud Contaminant Build Up

Electrolyte Distribution Acid Mist Control

Maintain the PLS pH 2.6-2.8 Resin regeneration with high acid concentration Resin soaking in acid solution Organic treatment with acid activated clay Electrolyte Bleed(for Fe and Mn) Addition of ferrous sulfate to the electrolyte and contacting of the electrolyte with mild steel and iron wire(for Mn) Specially designed PVC manifolds in the EW cells bottom Cells hoods and scrubber

4.Buchim Copper Project Expansion In 2013 was decided to expand the Buchim Copper Project in order to increase the nominal production up to 2800 tpa of copper cathodes and to handle the excess drainage waters. The expansion project will be completed in late 2013 or early 2014, with the commissioning of the expanded ion exchange circuit and newly constructed ionexchange facility for treatment of excess drainage waters. The main components of the expansion project included: o installation of the four new columns within the existing ionexchange facility o extractant addition of in SX organic up to 25 v/v% o revision of contact busbar system in the electrowinning o construction of new ionexchange facility with two columns for excess drainage waters treatment 5. Conclusions The Buchim Copper Project provides a valuable case study in all aspects of plant operations for future implementations of this type of technology. There are a number of copper deposits worldwide that are amenable to treatment by this type of circuit and the lessons learnt will be valuable in eliminating some of the issues that will inevitably arise during the design and commissioning of plants treating copper oxide and/or sulphide ores. References 1. Savov G., Angelov T., Tsekov V., Nishkov I., Nikolov N.,.Konzulov G.,. Combined Ion Exchange - Solvent Extraction Process for Copper Recovery, In: Proc. of XIV th Balkan Mineral Processing Congress, Tuzla, Bosna and Herzegovina ,2011,pp.620-623 2. Savov G., Angelov T., Tsekov V., Grigorova I., Nishkov I. Heap and Dump Leach Process at the Buchim Cooper Project Metallurgical Testwork. In: Proc. of XXII World Mining Congress, Vol. II, Istanbul, Turkey, 2011, pp. 271-276. 3. Savov G., Angelov T., Tsekov V., Nishkov I., Development and Applications of Iontech Ion Exchange (Iontix ) Process, In: Proc. of XXII World Mining Congress, Vol. II, Istanbul, Turkey, 2011,pp.319-322