HEAP AND DUMP LEACH PROCESS AT THE BUCHIM COPPER PROJECTMETALLURGICAL TESTWORK

G. Savov, T. Angelov, V. Tsekov, I. Grigorova, I. Nishkov

Directior Recearch and Development, Iontech Engineering Ltd., 1113 Sofia, Bulgaria, phone: +359 2 8164431, fax: +359 2 8164461, e-mail: savov@ionteching.com Senior Technologist, Iontech Engineering Ltd., 1113 Sofia, Bulgaria, phone: +359 2 8164431, fax: +359 2 8164461, email: savov@ionteching.com Chief Executive Officer, Iontech Engineering Ltd., 1113 Sofia, Bulgaria, phone: +359 2 8164431, fax: +359 2 8164461, e-mail: savov@ionteching.com Asst. Prof. Dr., University of Mining and Geology St.Ivan Rilski, Department of Mineral Processing and Recycling, 1700 Sofia, Bulgaria, phone: +359 02 8060253, e-mail: irena_mt@abv.bg Vice Dean of Faculty of Mines, Professor, University of Mining and Geology St.Ivan Rilski, Department of Mineral Processing and Recycling, 1700 Sofia, Bulgaria, phone: +359 02 8060253, e-mail: inishkov@gmail.com

ABSTRACT The Buchim Copper Project, now under construction, is located in eastern Macedonia, 95 km from the Skopje capital and 170 kilometers from the nearest port Thessaloniki (Republic of Greece) at an altitude of 620 m above sea level. The mineralization of Buchim ore deposit is porphyry. Extensive metallurgical testwork was carried out to determine the effect on the projects feasibility and to provide information needed for the plant design. Ore body/reserve data, basic mineralogy and lithology are defined from representative sample for each ore category prior to planning the metallurgical test program. The metallurgical test program including detailed determination of physical and mechanical properties, mineralogy, size distribution, total and acid soluble copper and conducting of elemental analysis (standard ICP scan), acid consumption and acid cure tests as well as bottle-roll tests was performed. A series of column leach tests represent the most important part of the testing program. Operating parameters such as particle size, leach time, flow rate, heap height and acid addition are evaluated. Physical tests and water tests are also was conducted to provide additional design information. A dump leach-ion exchange-solvent extraction-electrowinning process was selected to treat the Buchim ore to produce 2500 tpy of cathode copper. The results obtained as well as the design criteria selected for the process are discussed in this paper. Keywords: hydrometallurgy, copper ore, metallurgical test program, leaching, column tests.

1. INTRODUCTION The Buchim Copper Project, scheduled for construction and operation in 2011 is a leaching and treatment facility at the Buchim mine site in Macedonia. The facility is envisaged to organize leaching of low grade ore from Bucim dump and oxide heap of Vrsnik orebody and treat the pregnant leach solutions via combination of Ion Exchange, Solvent Extraction and Electrowinning to recover copper into high grade copper cathodes (Jergensen, 1999). To ensure the success of copper leaching project, the metallurgical characteristics of the subjected ores must be well defined. An extensive

test program, which involves a sequence of bottle roll tests and column tests, was carried out in the early stages of development in order to determine the effect on the projects feasibility, and to provide information needed for the basic and detailed design. Subject of this paper is testwork on a representative sample of ore from old dump. The testwork is aimed at determining the amenability of this ore to leaching, which depends on the characteristic of the ore with respect to porosity and permeability to leach liquor, percolation, acid consumption, and metal recovery.

2. BUCHIM COPPER DEPOSIT 2.1. General Buchim copper mine is situated near the village of Buchim and in the south borders of Plachkovitsa Mountain, in Republic of Macedonia. Dominating top in the immediate surrounding is Versnik, on 720 meters above the sea level, while 620 meters is the average above the sea altitude of the ore deposit. Buchim mine territorially and administratively belongs to the municipality of Radovis. It is 14 kilometers away from the city of Radovis, and 30 kilometers from Stip. The mine has good communication lines. Asphalt road, about 3.5 kilometers long, is connecting the mine with Veles Stip - Radovis regional road. The climate in the region is Mediterraneancontinental. The specific geographical and topographical situation of the region provides for its specific landmark: long and warm summers with high average daily temperatures and reduced precipitation, low winter temperatures and occurrence of winds from all directions. 2.2. Geology Buchim mining field is occupying the northern parts of Buchim-Damjan-Borov Dol mining region, created between two major geotectonic units: the SerbianMacedonian massif and the Vardar zone. According the positioning of the tectonic plate this is a place of depositing i.e. place of contact of the two geotectonic units, at which point the Vardar zone is sinking under the Serbian-Macedonian massif. This mining field is defined with lower rank fault planes, alkaline fractions of the tertiary intermediary magmatic and copper porphyry mineralization. The geologic structure of this region is quite complex with explicit tectonics. Buchim ore deposit occupies the southern parts of Buchim mining field. The geologic structure of Buchim ore deposit features mainly Precambrian metamorphic rocks (gneisses, micashists and amphibolites) and tertiary volcanic rocks. The gneisses are the most frequent lithologic members in the ore deposit, and they are at the same time the most favorable lithologic environment for disposal of ore mineralization. The mineralization of Buchim ore deposit is porphyric. The copper mineralization is connected with the process of silification, and it occurs in the gneisses and the amphibolites and biotitic schist, as well as at the point of their contact with the andesites. In the rifts of these rocks there are mineralized quartz ledges with presence of fine impregnation at the same time. The copper minerals are also present in the andesites, but their content is considerably decreasing proportionally with the increase of the andesite distance from the contact with gneisses.

The kaolinization and the chloritization are connected with the hydrothermal activity in the ore deposit. Main mining phenomena occur in the primary zones, where the chalcopyrite occurs as basic copper mineral. Other minerals present are: pyrite, hematite, magnetite, and seldom molybdenite. The precious metals, gold and silver, occur in smaller concentrations, but though enough for their valorization. The zone of secondary sulphide enrichment is insignificantly developed. Besides the minerals from the primary zone, chalcosine and small quantity of copper carbonates occur. Low grade ore stored on old dump is from mining activities on the Central ore body of Bucim mine. This orebody is characterized of primary copper mineralization and it is created around the latitic dike. The ore mineralization mainly occurs in the gneisses, but as a ring around the latitic burst. The ore body is in The Central ore body is a typical representative of the primary copper mineralization and it is created around the latitic dike. The ore mineralization mainly occurs in the gneisses, but as a ring around the latitic burst. The ore body is in shape of upturned, cut cone and morphologically it is following the shape of the volcanic body. Its mine mineral is the chalcopyrite, accompanied by pyrite, magnetite, hematite, cubanite, valerite, natural gold, borite, etc. Bucim mine consist also of Bunardzik, Vrsnik and Cukar ore bodies which are well investigated and are of subject for further exploration.

Figure 1. Bucim dump 3. EXPERIMENTAL 3.1. Sampling For the metallurgical testwork, approximately 2 tons of samples were taken from Bucim dump Figure 1, according the following procedure: (1) determination of ten pre-selected places spread across a large areal extent of the mine area; (2) excavation of ten

different pits (5 meters deep) at each of the preselected places; (3) collection of 200 kg sample of each pit, simply excavating a full sample at once. Each pit sample is collected into separate steel drum with the sample locations clearly identified on the drums with sample identification numbers; (4) shipment of the 10 pit samples, to the laboratory for further preparation, assay and characterization. 3.2. Metallurgical Testwork Program The metallurgical testwork program typically involves a sequence of the following stages, namely mineralogical examinations, bottle roll tests and column tests, optionally followed by piloting on test heaps. Mineralogical examinations are fundamental to the metallurgical behavior, and therefore to the technical and economic amenability of an ore to exploitation. They are normally performed first, to obtain information about mineralized zones within the ore body and the potential recovery. By additional examination of the ore samples, the type and location of valuable minerals in the ore can be determined and the gangue minerals can be characterized. Bottle roll tests are the second stage of the metallurgical program. In these tests on a bottle roll apparatus all the material remains in continuous motion and a pulp air interface is created for aeration of the pulp. The main variables to be considered are pulp density, acid concentration, ferric concentration, retention time and temperature. Generally bottle roll tests give an indication of metal recovery and acid consumption. On the other hand the column leach tests give much more accurate information about metal recovery and acid consumption in the trickle bed conditions as well as an initial indication of the possible percolation problems (Miller and Newton, 1999). Metallurgical test work with the Buchim ore was carried out at the Iontech laboratory, based in the University of Mining and Geology "St. Ivan Rilski", Sofia. Tests were done using bottle-rolling and column leaching techniques. 3.3. Laboratory Facility Description The laboratory facility consists of a leaching, ion exchange, solvent extraction and electrowining section. It also has a sample preparation and analytical laboratory. The leaching sections include standard bottle roll apparatus and 4 leach columns, each 10 diameter and 1m high. The laboratory facility is closed with a ion exchange, solvent extraction and electrowining sections. 4. RESULTS AND DISCUSION 4.1. Sample Preparation

The total quantity of ore is dumped carefully on a clean, concrete surface so as not to break the larger particles. A 200 kg representative sample is prepared and then crushed to -20 mm. The representative sample are coned and quartered in the classic fashion to produce a 15 kg head sample. Part of it is further crushed to -2 mm, and another part is ground to -150 (-0.15 mm). These samples are designed to determine the physical and mechanical properties and chemical composition of the ore, as well as for conducting of phase and mineralogical analysis, acid consumption and bottleroll tests. From the remaining crushed ore, 60 kg are taken for the column leach tests. 4.2. Sample Characterization In Tables 1, 2 and 3 are shown physical and mechanical properties, analysis of ore sample by elements and phase analysis. Table 1. Physical and mechanical tests results. No 1 2 3 Parameter Volume density, Specific density,s Water absorption, W Unit g/cm3 g/cm3 % Value 2.57 2.67 1.21

Table 2. AES-ICP results. No 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 Parameter Cr Fe Co Ni Cu Zn Ga As Mo Cd Sn Sb Te Pb Bi Unit % % % % % % % % % % % % % % % Value 0.006 3.7 0.0023 0.0026 0.4 0.49 0.0009 0.0074 0.0017 0.0007 0.0064 0.0006 0.0002 0.007 0.0007

Table 3. Phase analysis results. Fraction Fraction I (Cu in oxidized minerals) Fraction II (Cu in secondary sulphides) Fraction III (Cu in primary sulphides chalcopyrite) TOTAL for ore sample Cu % 0.204 0.069 0.124 0.397

As can be seen from the table above most of the copper presented is in oxide form (0.204%), the content of primary sulphides-chalcopyrite is also

relatively high (0.124%), while the content of secondary sulphides is only 0.069%. 4.2.1. Mineralogy Main minerals are limonite, cuprite, tenorite, native copper, goethite, malachite, azurite, but relicts from pyrite, chalcopyrite, chalcocite, specularite, rutile, magnetite, etc also occurs According the complex X-ray thermal analysis the sample is represented by Quartz-25%; Labradorit 25%; Mikrocline 22%; Ortho-chamosite 12%, Muscovite 9%; Pyrite 3% and Calcite 2%. From this analysis can be concluded the following: (1) The main gangue minerals are silicates, inorganic compounds with high chemical and structural complexity, which are the most significant acid consuming component. However, they react incompletely with sulfuric acid and with most of them the rate of chemical reaction acid-gangue is a function of the acid strength in the leach solution. The moderate reactivity to acid of these minerals limits the acid consumption; (2) The content of calcite, mineral which reacts violently even with very dilute sulfuric acid solutions is only 2%, that suggesting moderate levels of acid consumption during leaching process; (3) The content of the main acid generating mineral pyrite is 3%,which means that effective leaching cou ld be achieved only by adding of a sufficient amount of sulfuric acid from the outside. 4.3 Acid Consumption In general, acid consumption depends mainly on the occurrence of acid-consuming minerals and crush size of the ore, but also from the increased contact time lixiviant - ore and the acid strength of the leach solution. Determined by The Acid Consumption Procedure-Short method, the gross acid consumption is 22.3 kg / ton ore, while the net acid consumption is 21.7 kg / ton ore. In the same time according to the standard methodology Typical Acid Consumption Procedure-the gross acid consumption is 28.6 kg / ton ore, while the net acid consumption is 27.1 kg / ton ore. 4.4. Bottle Roll Tests Bottle roll tests are conducted on a bottle roll apparatus under standard procedure and provide initial information for copper extraction and acid consumption. The obtained copper recovery is low -31, 9%, while the acid consumption of 29.3 kg / ton (gross) and 27.4 kg / ton (net) is relatively high, so these results should rather be treated as semi-quantitative. 4.5. Column Leach Tests

Column leach tests are the most important part of the metallurgical testwork program. The two key results which can be determinate from the column tests are the maximum copper extraction and acid consumption under percolation-contact mode. Leach tests are carried out using four 1 m columns (2 sets x 2 columns) in closed-cycle. Leach cycle in the first columns set (columns 1-1 and 1-2) is 103 days, and the leach cycle in second columns set (columns 2-1 and 2-2) is 73 days. The main conditions of the column tests are given in the table below: Table 4. Column tests conditions. Acid concentration in the leach solutions(g/l) first 14 days Acid concentration in the leach solutions(g/l) after14th day 6-8 6-8 6-8 6-8 Application rate (l/h.m2) 6 6 12 12 8.68 8.15 9.05 13.12 Acid/Copper kg/kg

1-1 1-2 2-1 2-2

Ore quantity (kg) 13 13 13 13

Column No

6-8 12-14 6-8 12-14

The results after 103 days and 73 days of leaching are summarized in Table 5. Table 5. Column leach tests results. Net acid consumption kg/t 34.45 32.34 35.93 52.08 0.453 0.513 0.398 0.512 Copper recovery,% 53.66 44.29 49.65 66.10 Column No 1-1 1-2 2-1 2-2

Copper recovery and net acid consumption for both sets are presented in Figures 2 and 3. Copper tenor in Pregnant Leach Solutions (PLS) of the four columns is presented in Table 6. Table 6. PLS Copper tenor. Column No 1-1 1-2 2-1 2-2 PLS Copper tenor g/l

5. PROJECT DESIGN CRITERIA The project designs criteria are selected based on the metallurgical testwork carried out at the lab facility, and are summarized in Table 7. Table 7. Project design criteria. Process LEACHI NG (L) Parameter,unit Design ore grade, Application rate,l/h.m2 Acid concentration in the leach solution(first 2 weeks),g/l Acid concentration in the leach solution,g/l PLS copper tenor,g/l PLS pH Process Parameter,unit ION IX feed copper tenor,g/l EXCHAN IX feed pH GE Filtrate copper tenor,g/l (IX) Filtrate acid concentration, g/l Regenerate copper tenor,g/l Regenerate acid concentration,g/l Process Parameter,unit SOLVEN Configuration (Extr. x T Strip.) EXTRAC SX feed copper tenor,g/l -TION SX feed acid (SX) concentraion,g/l Raffinate copper tenor,g/l Rafinate acid concentration, g/l Process Parameter,unit ELECTR Strong electrolyte copper Otenor,g/l WINNIN Strong electrolyte acid G concentraion,g/l (EW) Spent electrolyte copper tenor,g/l Spent electrolyte acid concentraion,g/l Current density,A/m2 Cathode quality Cathode production,t/y Value 0.25 12 15

6-8 0.5 1.8-2.2 Value 0.5 1.8-2.2 0.02 3 15.6 20 Value 3Ex2S 10.4 14 1.04 29 Value 44 160 32 180 280-300 LME Grade A 2400

Figure 2. Copper recovery and net acid consumption for columns 1-1 (blue line) and 1-2 (red line)

The block flow diagram for the Buchim Copper project is given in Figure 4. Figure 3. Copper recovery and net acid consumption for columns 2-1 (green line) and 22 (black line)

REERENCES Radovish municipality, FYR Macedonia, RfP 21/2008, Feasibility assessment and Development of a main technical design for water protection measure Buchim mine. Bartlett, R. (1992). Solution Mining: Leaching and Fluid Recovery of Materials, Second Edition, Gordon and Breach Science Publishers, p. 443. Jergensen, V. G. (1999). Copper Leaching, Solvent Extraction and Electrowinning Technology, SME, p. 296. Tsekov, V., Savov, G., Kanev, V., Garvanov, T., Angelov, T., & Kovacheva, V. (2003). Production of copper cathode by leaching-SX/EW method in Tzar Asen, Proceeding of the X Balkan Mineral Processing Congress, p. 4. Tsekov, V., Savov, G., Angelov, T., Kovacheva, V. (2005). Practical Aspects of Economically Proven Copper Cathode Production by Ion Exchange Technologies. Proceeding of the XI Balkan Congress of Mineral Processing, Albania, p. 7. Bayer, A. G., (1997). Instructions for laboratory trials with selective resin. Technical Information, Edition, p. 8. Miller, G., Newton, T. (1999). Copper heap leach testing, interpretation and scale-up. ALTA Copper Hydrometallurgy Forum, QLD, p. 27. Kordosky, G., Virnig, M., Mackenzie, M., (2006), Solvent extraction reagents and selectivity control, Cognis Corporation, p. 20. Kordosky, G, (2000), Copper Solvent Extraction Reagents, Past, Present and Future, Cognis Corporation, p. 13. Spence J. R., Soderstrom M.D., (1999), Practical Aspects of Copper Solvent Extraction from Acidic Leach Liquors, p.17.

Figure 4. Process flowsheet Figure 4 depicts the overall process whereas Lleaching, IX-ionexchange, SX-solvent extraction, EW electrowinning, O-ore, W-spent ore, PLSpregnant leach solution, F-filtrate, LR-loaded resin, SR-regenerated resin, RF-raffinate, RS-regenerate, LO-loaded organic, SO-stripped organic, PEpregnant electrolyte, SE-spent electrolyte, Ccharging, R-regeneration, E-extraction, S-stripping. 6. CONCLUSIONS Extensive metallurgical testwork has been conducted to define the process for the Buchim Copper Project. Bottle roll tests and column tests were carried out at laboratory scale during the conceptual study and ion exchange, solvent extraction and electrowinning tests were run at lab facility. Effects of particle size, application rate and acid strength of the leach solutions were evaluated and basic parameters like application rate, acid consumption and copper recovery were selected. A new combined Leach-Ion Exchange-Solvent Extraction-Electrowinnig (L-IX-SX-EW) process (Tsekov et al., 2005) has been selected to treat the Buchim ore and to produce 2400 tpy of copper cathodes. The Buchim Copper project is now under construction and is scheduled to come on stream in late 2011.