LAPPEENRANTA UNIVERSITY OF TECHNOLOGY Faculty of Technology LUT Chemistry

Marja Neuvonen

PRETREATMENT PROCESSES IN GOLD RECOVERY BY THIOSULPHATE LEACHING

Examiners:

Professor Ilkka Turunen D.Sc. (Tech.) Arto Laari

Supervisor:

M.Sc. (Tech.) Matti Lampinen

ALKUSANAT Tm diplomity tehtiin Lappeenrannan teknillisell yliopistolla, LUT kemialla. Kiitos professori Ilkka Turuselle mahdollisuudesta tehd tm diplomity ja haluan samalla kiitt kaikkia muitakin projektissa mukana olleita ihmisi. Tmn diplomityn myt ers pisimmist aikakausista elmssni loppuu. Samalla luovun ikiopiskelijan leimasta otsassani ja joudun kohtaamaan todellisen maailman. Jokaisen aikakauden loppu on uuden kauden alku. Haluan nostaa hattua niille ihmisille, jotka eivt uskoneet minun tekevn koskaan tt diplomityt, sill ilman heit minulla ei olisi ollut tarvetta todistaa pystyvni thn. itini ja veljeni tukivat minua tmn tyn eri vaiheissa ja antoivat minulle voimia jaksaa lpi tmn hermoja raastavan prosessin. Erityiskiitokset haluan esitt Helille, Sannalle ja Antille ilman teit tm diplomity ei olisi koskaan valmistunut. Tm ty todisti Matin ja Tepon kappaleen sanat vrksi, kissankulta ei ollutkaan arvotonta. Tm diplomity on omistettu Islleni thtien tuolle puolen.

Savitaipaleella

TIIVISTELM Lappeenrannan teknillinen yliopisto Teknillinen tiedekunta LUT Kemia Marja Neuvonen
ESIKSITTELYMENETELMT KULLAN TIOSULFAATTILIUOTUKSESSA

Diplomity 2013 62 sivua, 12 kuvaa, 28 taulukkoa ja 6 liitett

Tarkastajat: Professori Ilkka Turunen TkT Arto Laari

Hakusanat: Esiksittely, kulta, refraktorinen, tiosulfaatti, liuotus

Tm diplomity ksittelee erilaisia esiksittelymenetelmi kultakonsentraateille ja -malmeille. Teoriaosassa selvitetn erilaisten esiksittelymenetelmien toimintaperiaatteet ja niiden mahdollinen soveltuvuus tiosulfaattiliuotukseen. Teoriaosassa esitelln mys kokonaisuudessaan kullan pelkistysprosessi malmista alkuaineeksi. Kokeellisessa osassa tutkittiin rikkipitoisen refraktorisen konsentraatin esiksittely sek sen vaikutusta kullan liuotukseen. Esiksittelymenetelmin kytettiin mekaanista aktivointia ja alkalisissa olosuhteissa tapahtuvaa kemiallista hapetusta. Kokeellisessa osassa testattiin mys konsentraatille kaksiosaista prosessia, jossa kemiallinen hapetus ja tiosulfaattiliuotus suoritettiin perkkin samoissa olosuhteissa. Suurimman osan refraktorisen malmin rikkipitoisista mineraaleista muodostivat pyriitti (49,4 %) ja arsenopyriitti (27,7 %). Kultaa konsentraatti sislsi 11,3 ppm ja hopeaa 90 ppm. Ilman esiksittelymenetelmn kytt kullan liuotuksen konversio oli 30 %, joka analysoitiin yhdeksn tunnin kohdalla tiosulfaattiliuotuskoetta. Hopean konversio tss kokeessa oli 17 %. Mekaanisella aktivoinnilla saavutettiin 59 % kullan konversio ja 26 % hopean konversio. Kemialliselle hapetukselle alkalisissa olosuhteissa, jossa kemiakaalina toimi natriumhydroksidi, paras konversio kullalle oli 72 % ja hopealle 31 %. Yhdistetyiss kemiallisen hapetuksen ja tiosulfaattiliuotuksen kokeissa saavutettiin vain kullan konversio 49 % ja hopean konversio 18 %.

ABSTRACT
Lappeenranta University of Technology Faculty of Technology LUT Chemistry Marja Neuvonen PRETREATMENT PROCESSES IN GOLD RECOVERY BY THIOSULPHATE LEACHING Thesis for the Degree of Master of Science in Technology 2013 62 pages, 12 figures, 28 tables and 6 appendices
Examiners: Professor Ilkka Turunen D.Sc. (Tech.) Arto Laari

Keywords: pretreatment, gold, refractory, thiosulphate, leaching

This thesis describes several different pretreatment processes for gold concentrates and ores. The thesis is divided to theoretical part and experimental part. The theoretical part presents the operating principle of the main pretreatment methods and their suitability for thiosulphate leaching. In the theoretical part also the whole recovery process for gold from ore to elemental gold is presented. In the experimental part the study is focused on pretreatment of sulphidic refractory concentrates with mechanical activation and chemical oxidation under alkaline environment; and their effect on leachability in the thiosulphate leaching. In the experimental part a combined 2-step process, where chemical oxidation under ammoniacal environment is cascaded with thiosulphate leaching in the same conditions, is also tested. The main sulphuric mineral components in the studied refractory concentrate are pyrite (49.4 %) and arsenopyrite (27.7 %). The gold content in the concentrate is 11.3 ppm and silver content is 90 ppm. Without pretreatment the gold conversion in thiosulphate leaching was 30 %, which was analyzed at the time point of 9 hours. At that time the silver conversion was 17 %. By using mechanical activation the gold conversion reached was 59 % and silver conversion 26 %. With chemical oxidation under alkaline environment, where the used chemical was sodium hydroxide, the reached conversion of gold was 72 % and 31 % for silver. In the combined oxidation and leaching experiment the conversion of gold remained at 49 % and 18 % for silver.

LIST OF SYMBOLS

c cm d50 t

concentration, mol/L mass concentration, g/L median diameter, m temperature, C volume flow rate, L/min

Table of Contents INTRODUCTION

............................................................................................... 1

1 PROPERTIES OF GOLD ORES ......................................................................... 3 2 ORE CONCENTRATES ...................................................................................... 5 2.1 Flotation ......................................................................................................... 6 2.2 Gravity concentration .................................................................................... 7 3 PRETREATMENT OF GOLD CONCENTRATES ............................................ 8 3.1 Mechanical pretreatment ............................................................................. 12 3.2 Roasting ....................................................................................................... 13 3.3 Pressure oxidation........................................................................................ 15 3.4 Bio-oxidation ............................................................................................... 18 3.5 Chemical oxidation ...................................................................................... 19 3.6 Electro-oxidation ......................................................................................... 22 4 LEACHING OF GOLD ...................................................................................... 23 4.1 Methods for gold leaching ........................................................................... 24 4.2 Thiosulphate leaching .................................................................................. 26 4.3 Recovery of gold from leaching solution .................................................... 27 5 EXPERIMENTAL STUDY ............................................................................... 29 5.1 Concentrate .................................................................................................. 30 5.2 Treatment of the sample and storage before experiments ........................... 31 5.3 Testing equipment ....................................................................................... 31 5.3.1 Reactor .................................................................................................. 31 5.3.2 Planetary ball mill ................................................................................. 33 5.4 Analytics ...................................................................................................... 33 5.4.1 Laser diffraction particle size analyzer (LD) ........................................ 33 5.4.2 Atomic absorption spectroscopy (AAS) ............................................... 33 5.4.3 Ion chromatography (IC) ...................................................................... 34 5.5 Sampling ...................................................................................................... 35 6 EXPERIMENTS, RESULTS AND DISCUSSION ........................................... 35 6.1 Pretreatment with mechanical activation ..................................................... 35 6.2 Chemical oxidation in alkaline environment ............................................... 41 6.3 2-step combined oxidation and leaching with ammonia and copper ........... 46 6.4 Comparison of the results ............................................................................ 53 7 CONCLUSIONS ............................................................................................. 55 LITERATURE ............................................................................................. 58 LIST OF APPENDIXES ....................................................................................... 62

INTRODUCTION Gold is a periodical element, which is the most noble of the noble metals. It is widely used in jewelry, medal and coin industry. Other common uses for gold are in electronic and medical field. The roots of gold recovery can be traced back to 1700-century when solubility of gold in cyanide where found. Gold has been leached out from ore body by using this method since 1887 published patent by John Stewart McArthur, Robert Forrest and William Forrest (Habashi, 1999). The problem in this cyanidation process is the toxicity and hazard to the environment caused by cyanide. For this reason search for safer process for recovery of gold is current. Thiosulphate is an alternative to cyanide and a more secure choice for gold leaching processing. Accordingly, a number of studies have been carried out to develop a useful and economically profitable process for gold leaching by thiosulphate. Concentrate pretreatment is necessary in thiosulphate leaching process when gold appears in company with sulphidic or carbonaceous ores. They both have the ability to prevent partially golds leaching process. Carbonaceous matter adsorbs the gold complex from pregnant solution inside of it and sulphidic ore locks the submicroscopic gold inside the sulphide fraction. To make thiosulphate leaching economically profitable the recovery state of gold needs to be over 80 % (Vaughan, 2004). If gold ore is in refractory form, pretreatment is necessary before leaching to make the process, economically profitable and also to make the leaching process possibly in general for recovery of gold. There are several suitable pretreatment methods that are used before leaching with cyanide. The difference in cyanidation and thiosulphate processes is the chemical environment. For this reason, it is necessary to study conditions which are chemically similar both in the pretreatment process and in the thiosulphate leaching. In this case the pretreatment and the leaching process could be joined together and separate neutralization would be unnecessary between these two processes. This study deals with pretreatment methods for various gold ores in the theoretical part where used and studied pretreatment methods for various gold ores are presented. The main goal in the experimental study is to find an effective way to

break the sulphide structure and to release gold for interaction with leaching chemicals. Another target in the experimental part is to study chemical pretreatment under conditions that are less severe than what are commonly used in industrial processes. In this study the tested pretreatment methods are: mechanical activation and chemical oxidation under ammoniacal and alkaline environment.

PROPERTIES OF GOLD ORES

Gold is found in earths crust widely spread. The average content has been estimated to be 3.5 ppb (part per billion). (Kirk-Othmer Encyclopedia of chemical technology, 1992) Gold is recovered from sources such as: alluvial and placer deposits, veins associated with quartz and various sulfides; also from refining residues of nonferrous metals. Local concentrations of gold in metallic state can usually be found with quartz. Other chemical compounds that occur with gold are silver, base metal sulfides, selenides and tellurides (Habashi,1999). At the oceans, the amount of gold is depending on location. Based on reports, the range of concentration is from 40 ppb to 3 ppt (part per trillion), the average value in oceans is 10 ppt. (Kirk-Othmer Encyclopedia of chemical technology, 1992) When gold ores gold content cannot be efficiently recovered by standard leaching techniques, they are called refractory ores. The refractory nature of gold ores are affected by presence of sulfuric compounds or/and carbonaceous matter in gangue. Gold usually appears in native form or in several different alloys mainly with silver. Gold alloys and minerals that are processed in gold recovery processes are native gold, Au-Ag tellurides, aurostibite (AuSb2), maldonite (Au2Bi) and auricupride (AuCu3). The common gold minerals are presented in Table I. (Vaughan, 2005). Table I Common gold minerals (Vaughan, 2005)
Mineral Native gold Electrum Calaverite Krennerite Sylvanite Petzite Aurostibite Maldonite Auricupride Composition Au (Au,Ag) (20-50 % Ag) AuTe2 (Au,Ag)Te2 AuAgTe4 Ag3AuTe2 AuSb2 Au2Bi AuCu3

According to Vaughan (2005) gold appears as a trace element in several common sulphide and sulpharsenide minerals. This kind of gold is called submicroscopic or invisible gold. Gold is present as extremely finely grained inclusions or bound

in to the crystal lattice of the sulphide. Gold concentration in common gold minerals is presented in Table II. Table II Concentrations of gold in common minerals (Vaughan, 2005)
Mineral Arsenopyrite Loellingite Pyrite Tetrahedrite Pyrrhotite Marcasite Chalcopyrite FeAsS FeAs2 FeS2 Cu12As4S13 Fex-1S FeS2 CuFeS2 Gold concentration < 0.3 ppm-1.7 wt-% 1.5 1.087 ppm < 0.25 800 ppm < 0.25 59 ppm 0.006 1.8 ppm 0.05 4.1 ppm 0.01 20 ppm

Arsenopyrite (FeAsS) and pyrite (FeS2) are usually present in gold ore. They have the chemical or physical properties for locking submicroscopic gold inside the sulfide fraction, which complicates gold separation from the ore body. In case of highly refractory ores, the processed gold ore should be pretreated before leaching. Without pretreatment process the gold recovery degree can remain under 50 % or for moderately refractory ores in the range of 50-80 %. In these cases, to increase the recovery degree to acceptable levels (over 80 %), pretreatment methods like roasting, pressure oxidation, bio-oxidation or chemical oxidation can be used. (Vaughan, 2005) Carbonaceous matter is another effecting factor that lowers the recovery state of gold ores in gold recovery process. Vaughan (2005) has categorized the carbonaceous ores in two groups by how the gangue is affecting the leaching process. The categories for gangues are: preg-robbing carbonaceous ores that adsorb leached gold from solution; and ores in which the gold is associated with minerals that consume unacceptable quantities of leaching reagents. The carbonaceous matter may occur as hydrocarbons, humic acid and/or activated elemental carbon. (Nanthakumar et al., 2007) Active carbon components possess the ability to adsorb gold chloride or its complexes from solutions, usually the active carbon components associates with a mixture of high molecular weight hydrocarbons. Carbonaceous matter can also include organic acid which is either humic acid or similar to it. The acid component has the ability to interact with gold complexes to form organic gold complexes. (Mason et al., 1985) The carbonaceous matter can be treated before leaching with addition of kerosene, to saturate the carbon; or by roasting, to oxidize the carbon and other components. (Vaughan, 2005)

ORE CONCENTRATES

Before the actual leaching process can start, gold ores are treated by removal of the main part of gangue to form the concentrate for the leaching process. The gangue removal treatment can be done by using breakers, wet ball mills and classifiers. The purpose of this treatment is to reduce particle size of the ore and to decrease the amount of gangue in the ore. Another purpose of this is to increase the concentration of gold in the ore structure. Figure 1 presents a block diagram of a gold recovery process. (Ullmans Encyclopedia of Industrial Chemistry a, 1990)
ORE

Grinding

Gold content <10 ppm

Gold content >10 ppm

Concentrate pretreatment process Flotation Gravity concentration

Refractory ore

Pretreatment process Mechanical activation Roasting Pressure oxidation Bio-oxidation Chemical oxidation

Gold content >10 ppm

Leaching

Recovery

GOLD

Figure 1

Recovery process of gold (drawn from sources: Vaughan, 2004; Ullmans Encyclopedia of Industrial Chemistry e, 2000; Abrantes and Costa, 1996; Fireciov and Bal, 2002)

After the main gangue separation, the ore body is either moved to leaching stage or treaded in concentrate pretreatment process. Ore concentration is necessary if the amount of gold in ore body is under acceptable limit for leaching process (<10 ppm). Pretreatment of ores that contain excessive amounts of sulfur, arsenic or carbonaceous material and possess refractory nature are described in chapter 3.

Ore concentration is normally carried out by flotation and/or gravity concentration. (Ullmans Encyclopedia of Industrial Chemistry a, 1990)

2.1

Flotation

Flotation is a physicochemical separation process where hydrophobic particles are separated from hydrophilic particles in aqueous slurry with air bubbles. The suitable particle size range for flotation process lies in range of 1-200 m. (Allan and Woodcock, 2001) Flotations working principle is that hydrophobic particles in aqueous environment are attached on the introduced air bubbles. Solid-air aggregates rise to the surface and form a froth layer. The froth layer can be removed manually or mechanically from the top of the flotation chamber. By this way the hydrophobic and hydrophilic particles are separated from each other. The main part of naturally occurring metallic compounds possess hydrophilic nature. To make metal compounds suitable for flotation separation, the nature of particles can be changed by addition of adsorption chemicals. (Ullmans Encyclopedia of Industrial Chemistry e, 2000) Flotation suits for gold concentration process when gold occurs as native gold, electrum and/or auricupride composition. The size for native gold and electrum varies from large lumps (nuggets) to fine particles (0.1 m) in nature. Some of gold deposits are naturally hydrophobic, but pure gold is not. The floatability depends on combinations of alloys. The hydrophilic nature of gold surface can be changed by collectors from hydrophilic to hydrophobic. Suitable collectors for that are xanthates and dithiophosphates. The most commonly used collector for flotation of gold is sodium ethyl xanthate (NaC2H5OCSS) which ionizes in aqueous environment to sodium (Na+) and ethyl xanthate (X-) ions. The ethyl xanthate ion forms hydrophobic coatings on gold in electrochemical reaction in aqueous solution in the presence of oxygen. The overall reaction is shown in Equation 1 (Allan and Woodcock, 2001). 4X- + O2 + 2H2O 4Xads + 4OHXXads ethyl xanthate ion X-ion chemisorbed on gold surface (1)

All the factors that effect on flotation process are reliant on the consistency of gold component and also on the shape and size of gold in particles. Native gold appears in nature usually with silver, which is easier to float by using ethyl xanthate than gold. The reaction with silver and gold is reliant on redox potential in the process. At lower redox potentials silver chemisorbs with ethyl xanthate and at higher potentials the reaction happens with gold. The physical conditions are specific for every case dependent on the composition of the solid material. Flotation is usually carried out either in acidic or alkaline conditions, although gold can be floated in pH range from 3 to 11. Acidic environment is used when solid phase includes pyrite or similar matter. Alkaline environment is used in similar combinations, but when the addition of collectors is wanted to be kept low. Other physical conditions, like temperature and slurrys solid content and aeration, depend on particles and adsorption chemicals. (Allan and Woodcock, 2001)

2.2

Gravity concentration

Gravity concentration is an environmentally friendly concentration process where minerals are separated from gangue. The separated minerals have different density than gangue and for that reason particles response in a different way to gravity and/or other forces. Usually, the affecting forces include resistance to motion which is offered by viscosity of liquid. There are several mechanisms used in gravity concentration. The working principle of density, stratification, flowing film and shaking mechanisms are presented in Figure 2.

Figure 2

Mechanisms in gravity concentration A) Density, B) Stratification, C) Flowing film, D) Shaking. =heavy particle =light particle. (Ullmans Encyclopedia of Industrial Chemistry f)

The density mechanism (Figure 2, A) utilizes the properties of viscous fluid having a density or apparent density between the minerals to be separated. Viscosity provides buoyancy for the other mineral when the other one sinks and in that way the particles with different density are separated. The stratification mechanism (Figure 2, B) uses periodic pulsation for fluid in a vertical plain to create layers of different minerals. The flowing film (Figure 2, C) uses the mechanism where the slurry flows down along a plane by action of gravity. The relative movement includes the separation between the light and the heavy constituents. The shaking mechanism (Figure 2, D) works by using a horizontal shear force to stratify the mineral components. (Ullmans Encyclopedia of Industrial Chemistry f, 2000) The factors which are relevant for particles movement in fluid are particles density, mass, size and shape. Usually, the size of mineral components in gravity concentration is in the range from 6 m to 500 mm. Equipment that are suitable for gold ores gravity concentration are jigs, shaking tables, spirals and centrifugal concentrations. (Gekko systems, 2012)

PRETREATMENT OF GOLD CONCENTRATES

Pretreatment for gold concentrate is needed when the ores are characterized as refractory. In refractory ores the gold particles are in company with carbonaceous matter or completely encased by sulphidic matrix minerals, such as pyrite and

arsenopyrite. Both of these types of refractoriness can be treated by a pretreatment process using fine grinding, roasting, pressure oxidation, chemical oxidation or bio-oxidation to increase gold recovery degree. The reaction equations for pyrite, arsenopyrite and elemental carbon are shown in Equations 2, 3 and 4. (Nanthakumar et al., 2007) 4FeS2 + 11O2 = 2Fe2O3 + 8SO2 (2)

The oxidation of pyrite is a complex electrochemical process which requires transfer of several electrons from sulfur atom through semiconducting crystal to an oxidant. The oxidation takes place in aqueous environment in the presence of an oxidant which can be for example the Fe3+ ion. The oxidation of pyrite process consists of three steps: cathodic reaction, electron transport and anodic reaction. The factors that influence oxidation are the stoichiometry and the particle size of the ore. The other factors that influence the reaction are the conditions such as pH, temperature and pressure. The principle of oxidation, which is shown in Equation 2, should apply (with the variation) for most sulfide minerals, for example for the reaction of sulfide to sulfate. (Rimstidt and Vaughan, 2003) 4FeAsS + 13O2 + 6H2O 4H3AsO4 + 4FeSO4 (3)

The oxidation of arsenopyrite is a similar reaction than oxidation of pyrite. The difference between these two relies in the presence of arsenic. In air and water arsenopyrite is slow to oxidize, but the oxidation process can be performed with a range of inorganic oxidants such as ammonium hydroxide, hydrogen peroxide or sulfuric acid. The oxidation process can provide several forms of iron oxides and hydroxides; and also arsenic oxides (Ullmans Encyclopedia of Industrial Chemistry b, 2008). Richardson and Vaughan (1989) have studied the presence of forms of iron and arsenic ions in oxidation reactions. From their results it can be seen that the formed ionic charges are dependent on the used oxidant and the Eh/pH conditions. Arsenic ionizes to form As5+ only at acidic conditions and the ionic form As3+ is formed in all conditions. Iron ionizes to form Fe3+ and Fe2+ during the process under chemical environment. (Richardson and Vaughan, 1989) The oxidation of carbonaceous matter (Equation 4) to transform it to passive form or to eliminate it from the solution can be done in several ways. The most

10

common way is to oxidize it by roasting to a form where it would not adsorb gold complex. The difficulty for treatment of carbonaceous matter is the nature of the material. Usually carbonaceous matter is in finely ground form and consisting of several carbon components. (Nanthakumar et al.,2007) C + O2 CO2 (4)

Several studies of pretreatment methods and their influence on leaching are published. Table III presents a few studies of pretreatment methods used for refractory gold ores/concentrates and their effect on the leaching ability.

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Table III/a

Studies of several different pretreatment methods

Researchers

Ficeriov et al. 2002

Smith et al. 1990 Nanthakumar et al. 2007 Nanthakumar et al. 2007

Pretreatment method + Leaching chemical Mechanical activation + Thiosulphate Roasting + Cyanide Roasting + Cyanide Microwave roasting + Cyanide Pressure oxidation + Thiosulphate Pressure oxidation + Thiosulphate

Ore type

Gold content

temperature

pressure

time

Chemicals

recovery before pretreatment 54 %

recovery after pretreatment 99 %

Sulphidic

170 g/t

25 C

atm

30 min

sulphidic and carbonaceous sulphidic and carbonaceous sulphidic and carbonaceous Double refractory Double refractory 1.52 g/t 1.52 g/t

590 C 580 C 50-750 C 26 h 40 min

oxygen feed 0% susceptor: magnetite H2SO4 81 kg/t of ore NaCl 0,05 kg/ton of ore 0%

85.6 % 98 % 98 %

Thomas et al. 1998

3.48 g/t

225 C

Thomas et al. 1998

9.79 g/t

225 C

700 kPa O2 over pressure 700 kPa O2 over pressure

1.25 h

78.3 %

1h

81.2 %

11 Table III/b Studies of several different pretreatment methods

Researchers

Feng and van Denver, 2010 Li et al. 2009

Pretreatment method + Leaching chemical Chemical oxidation + Thiosulphate Chemical oxidation + Cyanide Chemical oxidation + Cyanide Electrooxidation + Thiourea

Ore type

Gold content

temperature

pressure

time

Chemicals

recovery before pretreatment 69 %

recovery after pretreatment 99 %

Sulphidic

4.3 g/t

25 C

atm

22 h

high-arsenic refractory Antimonial refractory Sulphuric

48.03 g/t

100 C

atm

8h

0.8 M NH3 6mM Cu2+ Air feed Fe2(SO4)3 0.7 M O3 54 ppm Na2S 4.1 M NaOH 1.8 M 1.9 M NaCl 0.1 M HCl

19.5 %

96.5 %

Celep et al. 2011

20.2 g/t

70 C

2.5 h

49 %

78 %

Abrantes and Costa 1996

420 g/t

atm

atm

1.5 h

21 %

90 %

12

3.1

Mechanical pretreatment

Mechanical pretreatment is a process where the fraction of fine particles and specific surface area is increased by mechanical grinding. Smaller particle size increases the surface area to react with leaching chemicals. With larger surface area the fractioned gold is exposed for leaching reaction. The forces that affect on particles to make them break are crushing, attrition and shearing. There are several options available to grind particles smaller than 74 m of average particle size. Grinding of particles can be done by dry or wet grinding. Usually wet grinding produces smaller particles than dry grinding. Suitable equipment for dry grinding include: ball, pebble, roller and hammer mills. By dry grinding the produced size is such that 99.8 % penetrates 44 m mesh. Wet grinding can be carried through with ball and pebble mills; stirred and vibratory media mills and pug mills. A schematic figure of a vertical ball mill is shown in Figure 3. (Perry,1997)

Figure 3

A schematic view of a vertical ball mill (Metalworking machines, 2012)

Mechanical activation changes the structure of reacting surface area of the particles. Also the structure of sulfide minerals changes in the bulk in the grinding process. Ficeriov et al. (2002) studied that a change of particle size distribution affects the leaching of gold by thiosulphate method. The sample which was mechanically activated consisted of chalcopyrite, galena, sphalerite, tetrahedrite, pyrite and quartz. The gold content in the sample was 170 g/t. The originally

13

concentrate was of size 100 % < 100 m and d50 = 25 m. From leaching of the original sample the conversion of gold was 54 %. The concentrate was mechanically activated with a ball mill to achieve a particle size distribution were 100 % of particles were smaller than 40 m and 83 % < 10 m. The mean particle size was d50 = 4.5 m. The leaching of this mechanically activated concentrate gave 99 % conversion of gold in thiosulphate leaching. The leaching liquor content used in the experiments was 0.5 M (NH3)2S2O3 and 10 g/L of CuSO4, mass of concentrate was 1 g in 500 mL of leaching solution. Temperature was 70 C and pH in the range of 6-7. Mechanochemical pretreatment is also an option for destruction of sulphidic structure. Mechanochemical pretreatment combines the mechanical activation and chemical agent in high-intesity milling. Ficeriova et al. (2005) studied the leaching of silver with thiosulphate using a mechanochemical pretreatment method where the chemical agents were Na2S and NaOH. Without pretreatment the recovery of silver was 6 % from the whole amount in the sample. After mechanochemical pretreatment the conversion of silver was over 90 %. The used sample was a silver-bearing complex sulphide concentrate.

3.2

Roasting

Roasting is a process where refractory gold concentrate is oxidized at fluidized bed roaster at high temperature with oxygen or air. The refractory nature of gold concentrate is mainly sulphidic when roasting is used. In a fluidized bed roaster the bed of particles is flowing above tuyere heads and air or oxygen flows through the bed to provide oxidation reaction with concentrate. (Shu et al., 1999) The working principle of fluidization is that the bed of solid particles converts into suspended and expanded mass which have similar properties than liquids. Gas phase is fed through the particle bed at velocity of 0.15-6 m/s. Flow influences the increase of porosity in the bed. The bed is made up of particles which have distribution in the range of 1 m-6 cm, but usually the best smooth fluidization is achieved with particles with size between 150 m and 10 m. In industrial scale, the bed height is from 0.3-15 m. The affecting factors for the bed height are the gas contact time and the solids retention time. In a high temperature process, the bed can include heavy oils, natural gas or fine coal. With these ingredients the

14

combustion inside the bed takes place at below flame temperatures without atomization. Combustion also provides an increase of temperature inside the reactor. The normal temperature for oxidation is in the range of 600-1000 C. Usually, the used shape for the fluidized bed reactor is a vertical cylinder, but the shape of the vessel is not limited. (Perry, 1997) In Figure 4 a schematic view of a fluidized bed roaster is shown.

Figure 4

Schematic view of a fluidized bed roaster (Modified from source: McGraw-Hill's AccessScience)

The fluidized bed technology is widely used in gold recovery industry. For the oxidation reaction roasting provides excellent heat and mass transfer characteristics. Also, the efficiency of process temperature control is a benefit for this process. The roasting provides very effective mechanism for destruction of the refractory components in the process. The factors that impact the efficiency of roasting are: particle size distribution, temperature, amount of sulfide compounds; presence of carbonaceous matter and rate of oxygen feed in combustion and oxidation reaction. The reactions with sulfides can be divided in to two categories: the reaction with concentrate that includes over 20 % of sulfide compounds; and

15

the reaction of concentrate with low sulfide concentration. For processes with sulfide content over 20 % the reaction is exothermic and autogenous with oxygen. When the sulfide content is low the process is endothermic and requires external heat or fuel input. The reaction of oxygen with sulphide material produces SO2 gas. To prevent any release of this gas to environment the gas can be transferred through gas cleaning process. (Smith et al., 1990) Microwave roasting have been studied as an alternative for conventional roasting. The largest benefit in case of refractory ore is that gold-bearing minerals have the ability to be good microwave absorbers, whereas gangue minerals are microwave transparent. The properties that affect on materials are dielectric and magnetic properties of the medium. Microwave roasting heats selectively the gold-bearing minerals, which cause chemical activation for reaction to oxidize minerals to forms that reveal gold from sulphide structure. Also, the heating is more rapid compared to conventional roasting process. Microwave roasting is carried out in powdered sample or in liquid environment with chemicals. The environment and the phase of environment can be selected depending on the wanted products. In some cases the formation and volatilization of SO2 gas is avoided by the presence of nitric acid or sodium hydroxide in liquid environment process. (Nanthakumar et al., 2007) According to literature research made by Al-Harahsheh and Kingman (2004) the operating costs for microwave pretreatment method are substantially lower compared to costs of autoclaving, roasting or bio-oxidation.

3.3

Pressure oxidation

Pressure oxidation, also called as autoclaving, is a process where the concentrate slurrys sulfides and carbonaceous matter is oxidized under high pressure and temperature in autoclave. There are several different shapes of autoclaves such as vertically mounted cylinders, horizontally laid cylinders or long horizontal tubes. The autoclaves are agitated either by injecting high pressure steam to the system, by mechanically using electrically driven impellers or rotating the whole autoclave around its axel. In industrial scale the autoclaves have volume in the range of 10-70 m3 and the operating pressure is ranged 2 500-5 000 kPa. For pressure oxidation of gold concentrate the most used autoclave is a horizontal

16

autoclave. Usually autoclaves are part of the continuous process. (Habashi, 1999) In Figure 5 is shown a schematic plan of a horizontal autoclave.

Figure 5

A schematic figure of a horizontal acid leach autoclave, where 1.Motor drive assembly for agitator, 2.Compartment divider, 3.Agitator shaft, 4.Service nozzles, 5.Support saddle 6.Carbon steel shell/lead and brick lined (Metallurgy and Materials Society, 2012)

Horizontal autoclaves have high efficiency of gas-liquid interaction. They are, as shown in Figure 5, cylindrical vessels which are horizontally laid and are divided in several chambers. Every chamber has a mechanical electrically driven turbine mixer on the top. An average filling degree for this kind of autoclave is 65-70 % of the total volume. Feed of gaseous material is performed by injecting the matter in under the bottom impeller to utilize the impeller for dispersion. Solid and liquid material is fed in the system with slurry. (Habashi, 1999) Pressure oxidation of gold concentrate can be carried through under acidic conditions or under neutral/alkaline conditions. In acidic conditions the slurry is oxidized in the presence of sulphuric acid. In this case ferric(III)ion can be used as the oxidizing agent to advance the oxidation reaction. The acidic pressure oxidation is problematic for thiosulphate leaching process, because the slurry needs to be neutralized before the leaching process can be started. For this reason neutral/alkaline conditions are more suitable for pressure oxidation when the leaching agent is a thiosulphate salt. In neutral/alkaline oxidation soda ash (Na2CO3), burnt lime (CaO), caustic soda (NaOH) or limestone (CaCO3) is added in to the slurry. These alkaline chemical compounds react with protons and

17

sulphuric compounds and prevent the formation of sulphuric acid in the slurry. After alkaline/neutral pressure oxidation the slurry can be moved straight to the leaching stage without a separate neutralization stage (Marchbank et al., 1996). In Figure 6 is shows the block diagram of a process where ore is oxidized in autoclave, leached with thiosulphate and recovered with ion exchange resins.
NaOH/NaCl Or Na2CO3/NaCl O2 Steam H2O

NH4+

(NH4)2S2O3

Ore

Grinding

Autoclave pressure oxidation

Leach

CuSO4

Water treatment Liquid (optional) Liquid/Solid separation Solids Tailings disposal Potassium thiosyanate Cu Eluation Ammonium thiosulphate

Resin-inleach

Water

Electrowinning or Precipitation

Au Eluation

Resin

Au

Figure 6

Process description of pressure oxidation under alkaline/neutral conditions in thiosulphate leaching process (modified from source: Thomas et al., 1998)

Several patents have been published about the conditions for pressure oxidation. For instance Marchbank et al. (1996) studied pressure oxidation of sulphidic and carbonaceous ore in acidic and neutral/alkaline conditions. The oxidation was tailored for thiosulphate leaching. The particles were in the size range where 6585 % of them passed 200 mesh. Pressure oxidation was carried through at temperature of 185-235 C and at pressure of 27.5-34.5 bar. The used reaction time was 30-100 minutes. In alkaline conditions in the slurry 5-40 kg sodium hydroxide per ton of ore was added to keep the pH value in the range of 6-8. The alkaline compound prevents mainly the formation of sulphuric acid in the solution.

18

3.4

Bio-oxidation

Bio-oxidation is a process where micro-organisms like Thiobacillus thiooxidans or thiobacillus ferrooxidans accelerate the rate of dissolution of sulfide minerals. Bacteria are minute unicellular organisms and they are widely distributed in soil, water and air. Bacteria can be divided in two groups by energy source: autotrophic bacteria lives in inorganic matter and heterotrophic in organic matter. The other categorization is by the utilization of oxygen: Aerobic bacteria utilize oxygen for growth but anaerobic bacteria do not need oxygen for growth. Bacteria can operate in reaction in two ways. In enzymic process the bacterial cells are responsible for catalyzing the reaction with minerals; nonenzymic process uses bacteria as metabolic products. (Habashi, 1999) Thiobacillus thiooxidans and thiobacillus ferrooxidans are autotrophic and aerobic bacteria which live in strongly acidic environment at pH range of 1.5-3. They are destroyed by light, but have high resistance for high concentrations of metal ions in the solution, for instance Cu2+. (Habashi, 1999) Thiobacillus ferrooxidans acts in temperature of 35-85 C and manufactures enzymes which catalyze the oxidation process for sulfide minerals. The reaction equations for bio-oxidation of pyrite in acidic media with the Fe(III)ion are presented in Equations 5-9. In Equations 5 and 6 the reaction mechanisms are for direct oxidation. Instead in equations 7, 8 and 9 the mechanism is indirect. (Sand et al., 2001)
2FeS2 + 7O2 + 2H2O 2Fe2+ +4H+ + 4SO424Fe2+ + O2 + 4H+ 4Fe3+ + 2H2O FeS2 + 8H2O + 14Fe 15Fe + 16H + 2SO4
3+ 2+ + 2-

(5) (6) (7) (8) (9)

MS + 2Fe M +S + 2Fe
3+ 2+ 0

2+

2S0 + 3O2 + 2H2O 4H+ + 2SO42-

The process of oxidizing sulfides by bio-oxidation is cheap to use, but the reaction is slow. The disadvantage is also the generation of sulfuric acid, which need to be neutralized before leaching. (Habashi, 1999)

19

3.5

Chemical oxidation

Chemical oxidation is a process where the oxidation process is carried through under inorganic conditions with a presence of oxidative agent. Possible inorganic conditions are: neutral/alkaline and acidic conditions. Oxidative agents are used to solubilize minerals that will not dissolve otherwise. Commonly used oxidative agents are: air/oxygen (O2), ozone (O3), hydrogen peroxide (H2O2), ferric(III)ion (Fe3+), cupric(II)ion (Cu2+), manganese dioxide (MnO2), sodium nitrate (NaNO3) and sodium chlorate (NaClO3). (Habashi, 1999) Oxygen is commonly used in alkaline and acidic mediums as an oxidant. The benefit for oxygen is that regeneration in not needed after reaction. (Habashi, 1999) Solubility of oxygen in water at temperature 20 C and under atmospheric pressure is 0.049 dm3/(1 dm3 of water). The reactions of oxygen and water are shown in Equations 10, 11 and 12. The redox potential for equation 12 is 1.23 V at temperature 25 C; for equation 13 is 0.70 V and for equation 14 0.40 V (Maol taulukot, 2006). O2 + 4H+ + 4e- 2H2O O2 + 2H+ + 2e- H2O2 O2 + 2H2O + 4e- 4OH(10) (11) (12)

Ozone decomposes readily to form oxygen with thermal activation, which is shown in Equation 13. Relative oxidation potential for ozone is 2.07 V. Ozones solubility in water at temperature 20 C and atmospheric pressure is 0.57 kg/(m3 of water) (Ullmans Encyclopedia of Industrial Chemistry c,2000; 1999). O3 + e- O + O2 + e(13) Habashi,

Hydrogen peroxide is weakly acidic in aqueous conditions, for this feature it forms salts with several metals. It decomposes readily to form oxygen in aqueous solutions because the reaction, shown in Equation 14, is highly exothermic. The oxidation potential for hydrogen peroxide is 1.77 V. (Ullmans Encyclopedia of Industrial Chemistry c, 2000; Ullmans Encyclopedia of Industrial Chemistry d, 2007)

20

H2O2 H2O + O2

(14)

Ferric(III)ion is used to oxidize sulfide minerals under acidic conditions. The reaction equation for oxidation of pyrite with ferric ion is shown in Equation 8. Ferric ion works at low pH range, normally the used range is under pH=3. At higher pH it starts to form hydroxyl ferric salts and precipitate. Ferric ions need regeneration during the oxidation which is a disadvantage of the process. The regeneration can be done by oxygen, chloride (Cl2) or by manganese dioxide. (Habashi, 1999) The conditions for chemical oxidation can be basic or acidic. It is also possible to add alkaline compounds to the slurry to avoid large changes in pH values. In basic conditions oxidation of refractory sulfide ore can be done with ammonia in company of cupric ion and oxygen. The simplified reaction equation for oxidation of pyrite with ammonia and cupric ion is shown in Equation 15 (Feng and van Deventer, 2010) and 16; oxidation of arsenopyrite in Equation 17 (Feng and van Deventer, 2002). Feng and van Deventer (2010) made the study of chemical oxidation under ammoniacal environment. In the study experiment was done in a two step process, where the oxidation product from the first part was connected to the leaching part by only adding the needed amount of thiosulphate to the solution. With this method the recovery of leached gold was increased from 69 % to 94 %. The oxidative conditions were 400 g of sulphide ore in 1 L of ammoniacal solution which included 0.8 M of ammonia and 6 mM of copper. The leaching process was carried out with addition of thiosulphate salt of 0.1 M and with air flow of 0.2 L/min. (Feng and van Deventer, 2010)
2FeS2 + 7.5O2 + 8NH3 + (4+n)H2O Fe2O3nH2O + 4(NH4)2SO4 2FeS2 + 6.5O2 + 4(Cu(NH3)4+ (6+n)H2O Fe2O3nH2O + 4(NH4)2SO4 + Cu(NH3)2+ + 4H+ 4FeAsS + (23/2)O2 + 6Cu(NH3)42+ + 9H2O 4(NH4)3AsO4 + 4FeSO4 + 6Cu(NH3)2+ + 6H+ (17) (16) (15)

Acidic media for chemical oxidation can be provided by addition of several inorganic acids. The common acids are sulfuric acid (H2SO4), nitric acid (HNO3)

21

and hydrochloric acid (HCl). In acidic media the pH range is kept low (below 3) to avoid precipitation of amorphous Fe hydroxides. All oxidation reactions with sulfides produce protons which make the solution acidic. The main oxidant agent in these reaction conditions is the Fe3+-ion. Li et al. (2009) studied the feasibility of ferric(III) ion with ozone as an oxidizing agent in acidic conditions to oxidize sulphidic refractory ore (sample containing 20 % of pyrite and 16 % of arsenopyrite). The acidic media was provided by addition of sulphuric acid (pH=1). By the use of these oxidative agents an increase in conversion of gold extraction from 19.5 % to 96.5 % in cyanide leaching was achieved. The most suitable conditions for oxidation were temperature 100 C, time 8 h, solid/mass ratio 20 %, ozone concentration of 54 ppm and concentration of Fe2(SO4)3=0.7 mol/L. (Li et al.,2009) In reaction Equations 5, 7 and 18 the reactions of pyrite in acidic conditions are shown when the oxidation agent in the reaction is either oxygen (Eq. 5), ferric(III)ion (Eq 7) or hydrogen peroxide (Eq18)(Mihaljevi et al., 2004). FeS2 + 15/2H2O2 Fe3+ + 7H2O + H+ + 2SO42(18)

In alkaline/neutral conditions the production of protons is buffered by alkaline compounds. The combination of sodium sulfide (Na2S) and sodium hydroxide (NaOH) have been studied by Celep et al. (2011) for antimonial refractory ores. In their study the alkaline sulphide pretreatment was carried through with 4.1 M sodium sulfide and 1.8 M sodium hydroxide solutions which reacted with the concentrate (gold content 20.2 g/t). The conditions in this pretreatment experiment were: temperature 70 C and time 2.5 h. Without pretreatment the recovery of gold was 49 % and after the pretreatment the recovery of gold increased to 78 %. The leaching method used in these experiments was the cyanidation process. (Celep et al., 2011) The reaction equations for sodium hydroxides reaction with pyrite and arsenopyrite are shown below. (Zhang, 2004)
12FeS2 + 25O2 + 32NaOH + 2H2O 12Fe(OH)3 + 8Na2S2O3 + 8Na2SO3 6FeAsS + 13O2 + 22NaOH 6Fe(OH)3 + 2Na3AsO3S + 4Na3AsO4 + 2Na2S2O3 + 2H2O (20) (19)

22

Other suitable alkaline compounds for chemical oxidation process are calcium and sodium carbonates. They are also suitable for buffering the formation of sulfuric acid during oxidation of sulphidic concentrates like pyrite and arsenopyrite. The reaction equation for calcium carbonate reaction with proton is shown in Equation 21. Equation 22 shows the reaction of bicarbonate with pyrite. And in Equation 23 the reaction of bicarbonate with arsenopyrite is shown. The arsenopyrite reaction with bicarbonate is quite similar to the reaction of carbon trioxide with pyrite. The difference between these two reactions is the formation of arsenate ion (AsO43-). (Mihaljevi et al., 2004)
CaCO3 + H+ Ca2+ + HCO3FeS2 + 15/4O2 +7/2H2O + 4CO32- Fe(OH)3 + 2SO42- + 4HCO3 FeAsS + 7/2O2 + 4H2O + 5CO32- Fe(OH)3 + AsO43- + 2SO42- + 5HCO3(23) (22) (21)

3.6

Electro-oxidation

Electro-oxidation is a pretreatment process which advantages the electrochemical creation of hypochlorite ion (ClO-) for oxidation of sulphuric refractory gold concentrates. Several studies are published from this possibility to modify sulphidic matrix into a more porous form by using electrochemical cells. Arslan and Duby (1997) studied the electro-oxidation of pyrite in sodium chloride solutions. Their study focused on hypochlorite production and oxidation of pyrite by hypochlorite. The reaction equation for oxidation of pyrite with hypochlorite is presented below.
2FeS2 + 15 ClO- + H2O + 2H+ 2Fe3+ +4HSO4- + 15Cl(24)

Arslan and Duby (1997) reached 97 % current efficiency in their experiments where the pyrite was oxidized in 10 % NaCl electrolyte at temperature 35-40 C and pH 6.5. The used experimental arrangement is presented in Figure 7.

23

Figure 7

Experimental arrangement in electro-oxidation. C=cathode, A=anode, 1=copper, 2=nitrogen gas tank, 3=saturated calomel electrode, 4=pH electrode, 5=sampling, 6=0.5 M NaOH solution, 7= catholyte, 8=glass frit, 9=anolyte, 10=saturated CaO solution, 11= thermometer (Arslan and Duby, 1997).

Abrantes and Costa (1996) studied the effect of electro-oxidation on the leaching ability of gold. Their sample consisted of sulphidic refractory ore where the main components were pyrite (40.28 %) and arsenopyrite (30.41 %), gold content in the sample was 420 mg/kg. Without pretreatment the recovery of gold was 21 %. Electro-oxidation was carried through in 10 % slurry in electrolyte solution (1.9 M NaCl + 0.1 M HCl) and the process time was 1.5 h. After electro-oxidation gold recovery of 90 % was accomplished with the thiourea leaching method. (Abrantes and Costa, 1996)

LEACHING OF GOLD

The thiosulphate leaching process is modified from the cyanide leaching process where the leaching dissolvent is changed from cyanide to thiosulphate ion. Currently there is no industrial application which uses thiosulphate method in large-scale. For that reason the process description rests on cyanide leaching process and on laboratory scale experimental studies. The thiosulphate leaching method suits also for cases where the amount of gold in the concentrate is low. In Figure 8 the general outline for hydrometallurgical recovery process is shown.

24

OXIDANT

ORE

LEACHING AGENT

LEACHING

SOLID-LIQUID SEPARATION SOLUTION

SOLID TO WASTE

CONCENTRATION PURIFICATION

PRECIPITANT OR ELECTRIC CURRENT

PRECIPITATION

PURE COMPOUNDS

METALS

Figure 8

General outline of hydrometallurgical process. (Habashi, 1999)

According to Habashi (1999) leaching is a process of extracting a soluble constituent from a solid by means of solvent. The purpose of this process is to recover valuable metals soluble from ore, concentrate or metallurgical products. In cyanidation process for gold, suitable leaching methods are: heap or dump leaching; percolation or vat leaching; or agitation or pulp leaching. The selection of the method is dependent on particle size and the golds mode of occurrence in the concentrate. (Habashi, 1999)

4.1

Methods for gold leaching

For lump form ores the leaching can be carried out using heap or dump leaching methods. In these methods crushed ore is piled on a slightly inclined base, and the base is covered with asphalt or plastic sheet. A suitable height for ore piles is from 10 to 15 m. After the ore is piled, the leaching agent is sprayed on the top of the heap and let to flow though the pile. The leaching agent reacts with the gold in the

25

pile and removes it from the ore body. When the leaching solution is saturated and found its way through the pile, the leach solution can be collected from the bottom of the heap. Leaching time for this method is several months and it happens in ambient environmental temperature and pressure. (Habashi, 1999) Percolation or vat leaching is suitable for ores that include sandy and porous material. In these methods the material is placed in tank, which is equipped with a false bottom. The false bottom is covered with filtering medium. The leach solution is added in the tank from the top of it and the solution is allowed to flow through the material. Under the false bottom is an outlet for the leach solution where it can be collected. The leaching time in this method varies between 2-4 days, the temperature and pressure conditions for leaching are at ambient conditions. (Habashi, 1999) Agitation or pulp leaching is used for finely ground ores. The leaching agent is added to the raw material so that they form a pulp inside the reactor or autoclave. The used vessel is equipped with mechanical agitation. This method is used in conditions where the raw material is moderate or high grade or when the metal is in fine grain size and disseminated in host rock and also for cases when the metal is difficult to dissolve. The leaching is carried out in the shortest possible time and high pressure and temperature can be used as booster for the reaction. Agitation for the process can be provided mechanically or pneumatically. The equipment used in agitation or pulp leaching can be ambient pressure leaching reactors or autoclaves in high pressure conditions. (Habashi, 1999) The main charasteristics of different leaching methods are present in Table IV. Table IV
Method Heap or dump leaching Percolation or vat leaching Agitation or pulp leaching

Leaching method and equipments for gold ores. (Habashi, 1999)

Pressure [kPa] Ambient Temperature [C] Ambient Agitation Ore size Time of leaching Month Equipment

None

Lumps

None Vats with false bottom Pachuca tanks, Dorr agitators, tanks

Ambient

Ambient

None

Sandy

Days

Ambient

< 100

Mechanical, compressed air

Fine

Hours

26

4.2

Thiosulphate leaching

In thiosulphate leaching process gold is dissolved from concentrate in ammoniacal environment by thiosulphate in the presence of Cu(II)ion. The electrochemical leaching reaction between gold and thiosulphate is presented below (Aylmore and Muir, 2001). Au + 5S2O32- + Cu(NH3)42+ Au(S2O3)23- + Cu(S2O3)35- + 4NH3 (25)

Thiosulphate (S2O32-) has the ability to form a complex with gold in alkaline or neutral conditions. The complex ions formed are [Au(S2O3)2]3- and [Au(S2O3)]-, where the latter form is not as stable as the first one. Thiosulphate is a metastable anion, which have a tendency to decompose in aqueous solutions. The stability of thiosulphate can be increased with alkaline conditions as especially in ammoniacal conditions. Without ammonia in the solution, thiosulphate forms a passive layer on gold surface. Sulphur coatings on gold surface can be avoided when ammonia is adsorbed on gold surface instead of sulphur. Ammonia forms a complex ion with gold (Au(NH3)2+) and brings it into the solution. In the solution the ammonia complex ion reacts with thiosulphate ion and a substitution reaction takes place in according to Equation 26. According to several studies gold dissolution in ammonia happens only above 80 C, when copper ion is not present in the reaction. (Aylmore and Muir, 2001) Au(NH3)2+ + 2S2O32- Au(S2O3)23- + 2NH3 (26)

Copper carries a role of a catalyst in thiosulphate leaching. It has been studied that Cu(II)ion can speed up gold dissolution by 18 to 20 times. In catalytic reaction the cupric ion forms a complex ion with ammonia (Cu(NH3)42+) which reacts with gold. The reaction equation for catalysis is present below. (Aylmore and Muir, 2001) Au + Cu(NH3)42+ Au(NH3)2+ + Cu(NH3)2+ (27)

27

The factors that influence the reaction are time, cupric ion concentration, temperature, thiosulphate concentration, ammonia concentration and pH. Several studies have been published about thiosulphate leaching. Breuer and Jeffrey (2000) studied that optimal leaching conditions should be at temperature 30 C, pH value should be over 11.4; optimal concentration for ammonia is 0.4 mol/L and for thiosulphate 0.1 mol/L. Their conclusion was that the reaction rate decreases with degreasing copper concentration. Abbruzzese et al. (1995) studied conditions for thiosulphate leaching, and discovered that in lower temperature (20 C) the gold recovery rate was 12 % higher than at temperature 60 C. The most satisfactory gold recovery degree was accomplished in concentrations of c(S2O32-) = 2 mol/L, c(NH3) = 4 mol/L and c(CuSO4) = 0.1 mol/L After leaching the slurry moves on to filtration stage. In filtration process the solution is separated mechanically to liquid and solid phases. The liquid phase is moving on to the recovery step where it can be concentrated and purified in several ways. The filtration stage can be bypassed if the recovery method does not require clarified, solid particle free solution.

4.3

Recovery of gold from leaching solution

In literature several methods have been introduced for recovery of gold from thiosulphate solution. Carbon adsorption is widely used in cyanidation process for recovery of gold from leach solution. The benefits for this process are high selectivity, efficiency, relatively low costs and purity in product. In carbon adsorption method porous granules of activation carbon are exposed to the gold solution and then recovered with adsorbed gold. (Grosse et al., 2003) Activated carbon adsorbs more selectively the gold complex when stoichiometric quantity of cyanide is added in to the solution. Without cyanide activated carbon adsorbs also small amounts of copper, silver and zinc from the solution. (Muir and Aylmore, 2004) After adsorption stage the gold bearing carbon is usually eluted with a hot caustic cyanide solution under pressure to remove gold from it. There are several ways how the adsorption process can be carried through. The most commonly used method is when the adsorption occurs in mineral pulp (carbon-in-pulp). Other

28

possibility it to adsorb gold out from other minerals in clarified solution (Grosse et al., 2003). If the gold ore includes refractory carbonaceous matter, which is characterized as preg-robbing nature, the whole leaching process can be performed in the presence of activated carbon (carbon-in-leach). The presence of activated carbon prevents the carbonaceous matter from adsorbing gold. (Ullmans Encyclopedia of Industrial Chemistry, g, 2000) Precipitation is one of the possible processes for removal of metal compounds from leach solution. The suitable chemicals for precipitating gold ion are sodium sulphate and Zn, Cu, Al or Fe powder with borohydride. (Muir and Aylmore., 2004) A redox reaction happens between the zero valence base metals and the target noble metals. The disadvantage in precipitation is the formation of deleterious effect of reducing thiosulphate ions from the solution. This affects to reduce the amount of returnable thiosulphate back to the process. (Grosse et al., 2003) Electrowinning is a process for recovery of gold. In this process electric current is directed into the solution which forces the migration of aurothiosulphate ion to the cathode and in there the ion forms a metallic deposit. This process is problematic if the solution includes large amounts of unwanted cations like Cu(I) or Cu(II), because these ions form also a metallic deposit on cathode and for this reason the metallic product is contaminated and need further purification. Another disadvantage in electrowinning process is the side reaction of oxidation or reduction of thiosulphate. (Grosse et al., 2003) Resin adsorption has been also introduced for recovery of gold from thiosulphate leaching solution. The working principle is the same as in carbon adsorption. Resin adsorption process can be done in solution at the same time as the leaching process is performed. This process is called resin-in-leach (RIL). Other option is to use adsorption resins after leaching and this is called resin-in-pulp (RIP) process. Both of these methods can be performed in mineral pulp and do not require separation before it. After adsorption, the resin is separated from pulp and chemically stripped. (Grosse et al., 2003) Adsorption resins can be characterized as strong or weak base resins, depending on the nature of the functional group in them. Problems that are involved in this method are that the strong base resins

29

have limited selectivity; they upload copper as well as gold. Weak base resins instead have low loading capacity at the range of pH (9-10) where the leaching is carried out so the recovery degree is unprofitable. (Muir and Aylmore, 2004) Solvent extraction is a technique where an immiscible organic phase is contacted with the leach solution. The gold complex from the leach solution reacts with the organic phase and moves into the organic side. In ideal situation the other metallic compounds stay in water solution. Organic and water phases are separated from each other and the organic phase in moved on to the stripping stage. In the stripping stage gold is removed from the organic phase by stripping it with sodium hydroxide. Several organic compounds have been tested in laboratory scale for solvent extraction of gold from thiosulphate leaching solution. Suitable solvents for this purpose are benzene, kerosene and 1- or 2-octanol. Several problems are involved in this method. Organic phase might degrade chemically in contact with the leach solution. Also evaporation might appear. Dissolution of solvent in the aqueous phase is also one reason for the loss of the organic phase. The largest obstacle for industrial application of solvent extraction of gold might be the requirement for clarified leach solutions. Solvent extraction process is impossible for mineral pulps. (Grosse et al., 2003)

EXPERIMENTAL STUDY

The basic idea in this experimental study was to find a pretreatment method which operates at similar conditions than the thiosulphate leaching process. At similar pH conditions the neutralization step between oxidation and leaching processes could be prevented. The most promising pretreatment methods according to literature for this purpose are mechanical activation, oxidation under alkaline environment and integration of oxidation and leaching process under ammoniacal environment with the presence of copper. Another point of view for this experimental study was to find conditions for oxidation processes that are not as extreme as the ones usually used in oxidation processes, such as in roasting: temperature 600-1000 C (Perry, 1997) or pressure oxidation: operating pressure 2 500-5 000 kPa (Habashi, 1999).

30

5.1

Concentrate

A sample of gold ore concentrate was obtained from a gold mining company. According to the analytical results, the sample contains several different sulphide minerals and gangue. The amount of free gold in the sample has been estimated to be in the range of 25-30 % but the main part of gold is locked inside the sulphuric structure of arsenopyrite and pyrite. Analytical data from the samples mineralogy are present in Table V. Table V Gold ore sample mineral content
Mineral Pyrite (Pyrrhotite) Arsenopyrite Sphalerite Galena Chalcopyrite Arsenides Antimonides Other sulphides Quarz Feldspars/mica Other silicates Fe-oxides/hydroxides All others SiO2 Chemical compound [mass-%] FeS2 (FeS) FeAsS (Zn,Fe)S PbS CuFeS2 49.4 27.7 5.6 0.7 1.1 0.2 0.1 0.7 4.9 3.6 1.8 2.3 2

The sample consists of two different groups: sulphides and gangue. The main part of the minerals in the sample has sulphidic structure. The total percentual value of sulphides in the sample is 85.4 %. The smaller part of the sample consists of several kinds of gangue minerals, which form the rest 14.6 % of the sample. The company gave also the basic data of elements that exist in the sample. The elements percentual mass distribution is presented in Table VI. Table VI Elemental contents of gold concentrate sample
Element Fe S-2 As Cu Zn Pb Si Au Ag Amount [mass-%] 35.6 34.0 10.2 0.6 3.7 0.7 4.0 Amount [ppm]

11.3 90.0

31

The elemental analysis extends also to the presence of carbonaceous matter which was not found in the sample according to the results. According to the mineralogy of the sample and the experimental estimate of free gold content, the sample can be classified as an arsenic and sulphuric refractory concentrate.

5.2

Treatment of the sample and storage before experiments

The sample which was used in the experiments was concentrated in the plant with flotation to accomplish the required gold content level. After the flotation process about 300 kg of the head concentrate was storaged in water in a 200 liter plastic drum in a non-heated magazine. Before dividing the head concentrate in subsamples, the concentrate was defrosted. The concentrate pulp was agitated before the samples were taken out from the mixed pulp by pumping it to bottles. The bottles were filled by distributing a small portion of the pumped slurry randomly. Since the concentrate is rather fine the assumption is that each sub-sample is representative. 20 kg of the sample was delivered to LUT for the use in the study. The solid particles were separated from the slurry by drying them in oven at temperature 60 C over 24 h. After drying the particle size distribution was measured with laser diffraction analyzer (Beckman Coulter LS 13 320).

5.3

Testing equipment

Oxidation and leaching experiments were performed in a mixed reactor. The other used equipment for pretreatment was a planetary ball mill which was used for particle size reduction.

5.3.1

Reactor

Oxidation and leaching tests were carried out in a heat jacketed vessel which was equipped with mechanical agitation. A schematic drawing of the testing equipment is presented in Figure 9.

32

Figure 9

A schematic drawing of the testing equipment

The material of the reactor was steel and its volume was 1 L. As lid for the vessel a plexiglass cover was used, which was attached to the reactor with bolts and nuts. The agitation for the vessel was provided by mechanical overhead stirrer (Heidolph RZR 2041), which had a stirring shaft including two pitched blade impellers. During the experiments temperature and gas feed were controlled. Constant temperature for the experiments was provided by a heat exchanger (Lauda master) which used thermal oil circulation. Oxygen or air was fed to the reactor during the experiments and the flow metering device (Bronkhorst) controlled the input. The other documented parameters from the experiments were the content of dissolved oxygen, redox potential and pH. The amount of oxygen in the slurry was determined by dissolved oxygen meter (Marvet). The redox potential/pHsensors were manufactured by Emerson. Values from the redox potential electrode were converted to the form of standard hydrogen electrode (SHE).

33

5.3.2

Planetary ball mill

Mechanical activation of the sample was made with a planetary ball mill (Retsch). The material of the milling chamber and the balls was stainless steel. The volume of the beater chamber was 250 mL and the mass of the grinding balls was 345.5 g.

5.4

Analytics

Several analytical methods were used to determine results from the experiments. To determine particle size before and after the grinding process with planetary ball mill laser diffraction particle size analyzer was used. In leaching experiments the content of copper, gold and silver was determined with atomic absorption spectroscopy. The content of sulphide and thiosulphate was analyzed using ion chromatography. Elemental analysis from solid samples was performed in external laboratory (Labtium Oy) which used inductively coupled plasma optical emission spectrometry (IC-OES) for the analysis.

5.4.1

Laser diffraction particle size analyzer (LD)

The particle size of the solid samples was determined with laser diffraction particle size analyzer (Beckman Coulter LS 13 320). The slurry to be analyzed was manufactured by adding random amount (approximately two teaspoons) of solid sample to water (approximately 50 mL). The slurry was mixed with magnetic mixer approximately 30 minutes before running the analysis. The settings used during the analysis are listed below: Pump speed: Number of runs: Waiting time between runs: Used model: Solvent: 5.4.2 80 % 25 30 s Fraunhofer.rf water

Atomic absorption spectroscopy (AAS)

The content of copper, gold and silver was determined with atomic absorption spectroscopy (Thermo fisher scientific iCE 3000). For burning process a mixture

34

of air and acetylene gases was used. The dilution ratios and standard lines used are explained in a case basis for different elements. Gold determination was performed with a standard line between 0 mg/L to 2 mg/L. The specific contents of standards were 0.25, 0.5, 1 and 2 mg/L. The dilution ratio of the gold sample was: 10 mL of sample diluted to 100 mL constant volume in a volumetric flask with pure water. The gold content was analyzed from every sample in the leaching experiment. Silver content was measured with standards between 0 mg/L to 3 mg/L. The specific contents of the standards were 0.5, 1, 2 and 3 mg/L. The dilution ratio of silver sample was: 10 mL of sample diluted to 100 mL constant volume in a volumetric flask with pure water. The silver content was analyzed from the last sample in the leaching experiment. Copper determination was performed with a standard line between 0 mg/L to 5 mg/L. The specific content of the standards were 0.5, 1.5, 3 and 5 mg/L. The dilution ratio of copper sample was: 120 L of sample diluted to 100 mL constant volume in a volumetric flask with pure water. The copper content was analyzed from every sample in the leaching experiment.

5.4.3

Ion chromatography (IC)

Ion chromatography (Metrohm) was used for determination of sulphate and thiosulphate concentration in the leaching experiments. In analysis an anionic column was used and as an eluent a mixture of sodium carbonate (cNa2CO3=3.2 mM) and sodium hydrogen carbonate (cNaHCO3=1.0 mM) diluted to pure water. The conditions used in IC analysis were flow rate of 0.7 mL/min and pressure in the range of 4.85 MPa. To determine the sulphate and thiosulphate content in the liquid phase of the slurry, the sample size of 120 L was diluted to 100 mL constant volume in a volumetric flask with pure water. The sample size fed into the analyzer was in the range of 2-4 mL. In the beginning of the oxidation experiments IC was also used to determine the concentration of oxidized sulphate and thiosulphate in the liquid phase. To

35

confirm that the sulphur is in the sulphate phase hydrogen peroxide was added to the sample to complete chemical reaction. Because the degradation of hydrogen peroxide was not complete in the used conditions the method was discovered to be unsuitable for IC analyzer. After that observation the measuring of sulphate and thiosulphate were left out in the oxidation experiments, because the analysis cannot identify the other sulphur compounds.

5.5

Sampling

Sampling was performed from the valve drain under the vessel. The volume of the taken sample was in the range of 40 to 70 mL. The slurry samples weight and volume was measured and after that the sample was filtrated. The filtration was carried out with a vacuum filtration unit using a Buchner funnel and filtration paper. The weight and volume of the filtrate was measured and part of the sample was analyzed with IC and AAS. The solid cake from the filtration was dried in oven 12 h at 65-70 C.

EXPERIMENTS, RESULTS AND DISCUSSION

This experimental study is divided to three parts to test how different pretreatment methods affect the leaching ability. The conversions of gold and silver are calculated from the initially added solids ratio to the analyzed mass concentrations in the taken samples. The analyzed (IC) contents of sulphate and thiosulphate in leaching experiments are presented in Appendix I.

6.1

Pretreatment with mechanical activation

Mechanical activation was carried out by grinding the concentrate sample with a planetary ball mill. The decrease of particle size was achieved first by dry grinding the sample then followed by wet grinding. Both of these grindings were done in several batches. The used parameters for grindings are shown in Table VII. The results are compared to the study of Ficeriov et al. (2002), their study was about mechanical activation of gold from gold bearing sulfide concentrate which was leached with thiosulphate.

36

Table VII

Parameters used for milling of gold concentrate with planetary ball mill
Dry grinding 150 5 450 250 345.5 Wet grinding 100 50 5 450 250 345.5

mass of concentrate [g] mass of water [g] time [min] rotation speed [1/min] volume of beater chamber [mL] mass of grinding balls [g]

After mechanical activation the wet ground sample was filtrated with vacuum filtration using Buchner funnel and filtration paper. After filtration the sample was dried in oven at temperature 60-70 C over 12 hours. The particle sizes of both ground samples were analyzed with laser diffraction particle size analyzer to determine the size distribution change in the samples. The results from the particle size analysis of the original, dry ground and wet ground samples are presented in Table VIII. Table VIII Particle size distributions for the original, dry ground and wet ground samples
Original sample [m] 36.67 25.22 3.46 10.02 25.22 51.52 86.47 Dry ground sample [m] 11.46 9.71 1.70 4.13 9.71 17.37 25.12 Wet ground sample [m] 8.51 7.29 1.45 3.01 7.29 12.85 17.73

Mean Median Volume distribution: < 10 % < 25 % < 50 % < 75 % < 90 %

From the particle size distribution results it can be seen that in the original sample 90 % of particles were sized under 86.47 m, when similar sizes for dry ground sample was 25.12 m and for wet ground sample 17.73 m. The mean particle size decreased from the original samples size 36.67 m to the dry ground samples size 11.46 m and the wet ground samples 8.51 m. The size difference between the dry and wet ground samples were quite small considering the heat formation during the milling. The temperatures were not measured but by bare hand the heat formation could be felt in the dry ground sample after milling. The heat formation was not noticed in the wet grinding experiment. The dry and wet ground samples were leached with thiosulphate at conditions were the temperature was 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. The leaching solutions components were c(Na2O3S2)= 0.2 M; c(NH3) = 0.2 M

37

and cm(Cu2+)= 1 g/L. For comparison, the results from the leaching of the original samples are presented also. The observed pH and redox potential values from the thiosulphate leaching experiments are presented in Appendix II (Table I) and Appendix III (Table I). The pH conditions were varied in the leaching of the original, dry ground and wet ground samples. In the leaching experiments the original samples pH values varied in the range of 11.18-11.67. The comparable values for the dry ground and wet ground samples were in the range of 10.17-10.75. The difference between the pH values of the original, dry ground and wet ground samples during the experiments come from the reaction rate of the leaching reaction. With smaller particles the reaction is faster than with the larger ones, because the surface area of the particles is larger than in the original sample. Also the volatilization of ammonia during the time when the reactor was warmed for operation temperature might affect the measured pH values at the beginning of experiments. Redox potential was also observed during the experiments. In all experiments the redox potentials varied in the range of 129-216 mV. The smallest change in the redox potential during 9 hours of leaching was discovered in the original sample leaching experiments (+31 mV) and the largest change in the dry ground sample experiments (+64 mV). The diluted liquid part of each sample was analyzed with AAS to detect the amount of diluted copper and gold. The gold conversion of the samples is presented in Figure 10 and the copper content during the experiments in Appendix IV (Table I). The copper content in all mechanically activated leaching experiments and in the original sample leaching experiments varied between the mass concentrations of 0.75 g/L to 1.03 g/L. The copper content was not detected to have stable content in any of these leaching experiments. The added amount of copper in every thiosulphate leaching experiment was 1 g/L. The variation of the copper content analyzed from the liquid phase during the experiments, were probably caused by precipitation and dissolution of copper sulphide. The leaching of copper from the concentrate was not detected in these experiments.

38

70 60

gold conversion [%]

50 40 30 20 10 0 0 3 time [h] 6 9
dry ground sample w et ground sample original sample

Figure 10

Gold conversion from the leaching of the original sample and the mechanically activated dry and wet ground samples with parameters: temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. Slurrys solid content was 20 %. Leaching solutions components were c(Na2O3S2)= 0.2 M; c(NH3) = 0.2 M and cm(Cu2+)= 1 g/L.

Conversions of leached silver at the end of the experiments are presented in Table IX. Table IX Conversion of the leached silver at the end of the experiment in the leaching of original sample, and mechanically activated dry and wet grinded samples, with parameters temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. Slurrys solid content was 20 %. Leaching solutions components were c(Na2O3S2)= 0.2 M; c(NH3) = 0.2 M and cm(Cu2+)= 1 g/L.
dry ground sample [%] 30.45 wet ground sample [%] 23.41 original sample [%] 20.81

The gold and silver content from the thiosulphate leaching experiments was analyzed from filtrated and diluted liquid samples. The highest gold content in the liquid was measured from the dry ground sample at point of time 9 hours, when conversion was 64 %. In the leaching of the original sample gold conversion of 36 % was reached and with the wet ground sample the highest measured conversion was 61 %. Both of these results were reached in time 9 hours. Variation in the samples was observed when the content of silver was measured. In the original sample the conversion of silver was 21 %, the dry ground sample reached a

39

conversion of 30 % and from the wet ground samples leaching experiment a conversion of 23 % was detected. The solid samples were sent to external laboratory (Labtium Oy) for elemental analysis. The main interest from the solid samples lied on the chemical changes of sulphur, iron, arsenic, copper, gold and silver in the experiments. Partial results from the contents in samples before and after the thiosulphate leaching process are presented in Table X. The complete results are presented in Appendix V. Because the results from the original concentrate were not supporting totally other samples elemental contents, a reference value was used for the comparison of the samples. Reference is the maximum analyzed content of element from the pretreatment experiments. Table X
Sample Original Reference Leached original Dry ground Leached dry ground Wet ground Leached wet ground

Content of the main elements in the solid samples before and after leaching
S [g/kg] 319 330 304 330 325 319 312 Fe [g/kg] 333 349 324 343 342 340 342 As [g/kg] 97.3 100.0 100.0 99.4 98.2 96.6 93.8 Cu [g/kg] 6.88 7.11 9.72 7.10 6.70 6.84 6.79 Au [mg/kg] 10.5 11.2 10.3 10.6 8.4 10.4 8.1 Ag [mg/kg] 89 92 90 90 60 88 63

Sulphur and iron were not reacting during mechanical activation; also the leaching did not affect exceedingly their amount in the samples. Only in the leaching of original concentrate the content of sulphur decreased 8 % and iron decreased 7 % from the reference value. From the results of elemental analysis it can be seen that the overall changes in elements are quite small. The reason for that can be the precipitation of oxidized components back to solid form. Changes in arsenic content were detected in dry ground leaching when the content of arsenic decreased during milling and leaching. In both of the mechanically activated experiments the content of chromium increased significantly during milling and leaching. With dry ground sample the content was 1.350 g/kg when the same content for wet ground sample was 0.96 g/kg, as compared to original concentrate where chromium content was in the range of 0.013 g/kg. The cause for this effect can be found from the transfer of chromium from the milling chamber and milling balls to the solid sample. The increase of copper content after the leaching experiments is caused by precipitation of added copper sulphate. According to

40

these results copper was not leached from the concentrate. The silver contents which were detected from the solid samples were very similar to what was detected from the liquid samples with AAS. According to the results from the solid samples the conversion of silver after leaching of dry ground sample was 33.3 % and after wet ground sample 28.4 %. In the leaching of the original concentrate the main part of gold and silver were precipitated according to the results from AAS, the results from solid sample support this. The conversion from the solid sample was 2.17 % when similar conversion measured from the liquid sample was 2.27 %. Comparison of gold content in liquid and solid samples in presented in section 6.4. The complete elemental analysis after oxidation and leaching is presented in Appendix V. From these contents the mineralogical change in the samples is calculated by making assumption that certain elements only appear in particular mineralogical form. Simplifications are listed below: Cu Chalcopyrite (CuFeS2) As Arsenopyrite (FeAsS) Zn Spharelite ((Zn,Fe)S) Pb Galena (PbS) From the rest of sulphur in the sample 95 % is supposed to be in the form of pyrite (FeS2). The results from these calculations are presented in Table XI. Table XI Calculated percentual contents of the minerals in the solid samples before and after leaching.
FeS2 [%] FeAsS [%] CuFeS2 [%] PbS [%] (Zn,Fe)S [%]

Sample Reference Leached original Dry ground Leached dry ground Wet ground Leached wet ground

46.2 41.2 46.4 45.6 44.7 43.7

21.7 21.7 21.6 21.3 21.0 20.4

2.1 2.8 2.1 1.9 2.0 2.0

0.8 0.8 0.7 0.8 0.7 0.8

5.7 5.7 5.6 5.7 5.4 5.5

From the results of the calculated mineral contents it can be noticed that the amounts of them are staying quite stable. This can be caused by the variation of compounds in the samples and also the precipitation of compounds after oxidation of minerals. According to the results the mechanical activation did not affect the form of minerals.

41

Comparison between The Fireciova et al.s (2002) study and the obtained results show that in the Fireciova et al.s (2002) study the mechanically activated particle median size was smaller (d50=4.5 m) than what was produced with the planetary ball mill in these experiments (dry ground d50 = 9.71 m; wet ground d50= 7.29 m). Also, the particle size distribution was narrower in their study than in the performed experiments. Ficeriov et al. (2002) used ammonium thiosulphate for their leaching when this studys leaching experiments were carried out with sodium thiosulphate with the presence of ammonia and copper. The temperature in their experiments was 70 C and pH was in the range of 6-7, whereas in the performed research the used temperature was 30 C and pH was over 10. In the Fireciova el al. (2002) study the gold conversion was elevated with mechanical activation from 54 % to 99 %. In the current experiments gold conversion of the dry ground sample rose from 36 % to 64 %. From these results one can come to the conclusion that other factors also influence the leaching ability of gold and silver than just the particle size or its distribution.

6.2

Chemical oxidation in alkaline environment

In chemical oxidation in alkaline environment the purpose was to reach suitable conditions to decompose the sulfuric structure of pyrite and arsenopyrite during the oxidation experiments. For this sake several amounts of sodium hydroxide and different conditions were tested in the oxidation. The chemically oxidized samples were leached with thiosulphate to study the effect of oxidation for gold recovery from the concentrate. Chemical oxidation was done by using sodium hydroxide (NaOH) to provide an alkaline environment for the oxidation process. During the experiments air was fed into the reactor. Also the use of hydrogen peroxide was tested as an oxidative agent. The parameters for the oxidation experiments are listed in Table XII.

42

Table XII

Experimental conditions for chemical oxidation in alkaline environment. Solid content in slurry was 30 %, the mass of solid sample 300 g, mass of liquid phase 700g, mixing speed 700 rpm.
NaOH HO
2 2

(air) [L/min] 0.6 0.6 0.6 0.6

time [h] 6 6 9 9

temperature [C] 302 302 502 302

[mol/L] 0.125 0.2 1 1

[mol/L] 0.2

During the oxidation pH and redox potential values were recorded. The pH and the redox potential values are presented in Appendix II (Table II) and Appendix III (Table II). The variations in measured pH values were quite wide in different oxidations, which is a result of the amount of sodium hydroxide used in the oxidation solution. From the changed pH values the consumption of sodium hydroxide during oxidation experiment can be calculated. In the consumption calculations the change of hydroxide ions concentrations is provided by the reaction of sodium hydroxide or by autoprotolysis of water during the reactions. The consumption is calculated from the added amount of sodium hydrogen to reach the final measured pH value. The concentrations of hydroxide ion in solutions are presented in Table XIII. Table XIII pH values and hydroxide ion concentrations in chemical oxidation experiments under alkaline environment
NaOH=0.125M; H2O2=0.2M 13.10 13.58 12.98 0.38 0.10 0.03 NaOH=0.2M 13.30 13.79 13.41 0.62 0.26 -0.06 NaOH=1M (t=50 C) 14.00 13.37 12.64 0.23 0.04 0.96 NaOH=1M (t=30 C) 14.00 14.00 13.79 1.00 0.62 0.38

pH (caused by NaOH) pH (0 h) pH (end) c(OH-, 0 h) c(OH-, end) c(consumed OH-)

From Table XIII it can be seen that with lower concentrations (cNaOH = 0.125 M and cNaOH = 2 M) the slurry provides more hydroxide ion that what was added to the liquid phase at the beginning of the experiment. When the concentration of sodium hydroxide was raised to 1 M in the liquid phase, the consumption of hydroxide ion also increased. The effect of temperature on the reaction rate can also be seen from these pH results. At temperature 50 C 0.96 M of hydroxide reacted with solids when the same value at temperature 30 C was only 0.38 M.

43

The redox potential during the chemical oxidation processes varied quite a lot. From oxidation with (NaOH= 0.2 M) and (NaOH= 0.125 M, H2O2 = 0.2 M) the measured values were in the range of 78 to 120 mV. Instead, in oxidation of (NaOH = 1 M, t=30 C) the measured redox potential values were quite close to zero, the values varied from 5 to -8 mV. The higher temperature (50 C) affected to redox potential of sample (NaOH = 1 M), by lowering it to negative values. The measured values were in the range of -34 mV to -83 mV. All the values from redox potential measurements from chemical oxidation under alkaline environment are presented in Appendix III (Table II). After the oxidation experiments the solid sample was filtrated and dried at oven at temperature 65-70 C over 12 hours. The oxidized samples were leached and/or sent for elemental analysis. The leaching experiments were performed under conditions: temperature 30 2 C, mixing speed 700 rpm and with air flow of 0.2 L/min. Chemical content in the liquid phase during the leaching experiments was: c(Na2O3S2)= 0.2 M; c(NH3) = 0.2 M and cm(Cu2+)= 1 g/L. The solid content in leaching was 20 %, mass of liquid phase was 800 g and mass of sample 200 g. pH and redox potential values from leaching experiments are presented in Appendix II (Table III) and Appendix III (Table III). The liquid part of each sample was prepared and analyzed with AAS to detect the amount of diluted copper and gold. Gold conversion of the samples is presented in Figure 11 and copper content during the experiments in Appendix IV (Table II). The added amount of copper in every thiosulphate leaching experiment was 1 g/L. From the measured results it can be seen that in leaching of the sample (cNaOH=0.2 M) and (cNaOH=0.125 M; cH2O2=0.2 M) the content of copper in the liquid phase decreased during the leaching. The only exception in these experiment was the sample (cNaOH=1 M, t=50 C). In that sample the amount of measured copper stayed quite stable (0.89-1.01g/L) compared to other contents varying between (0.640.98 g/L). The variation in the copper content measured from the liquid phase during experiments, was probably caused by precipitation and dissolution of copper sulphide. Leaching of copper from the concentrate was not detected in these experiments.

44

90 80

gold conversion [%]

70 60 50 40 30 20 10 0 0 3 time [h] 6 9
NaOH=0.125M; H2O2=0.2M NaOH=0.2M NaOH=1M (T=50 C)

Figure 11

Gold conversions from leaching of alkaline oxidized samples with parameters: temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. Slurrys solid content was 20 %. Leaching solutions components were c(Na2O3S2)= 0.2 M; c(NH3) = 0.2 M and cm(Cu2+)= 1 g/L.

Conversions of leached silver at the end of the experiments are presented in Table XIV. Table XIV Silver conversions at the end of the experiment, from leaching of alkaline oxidized samples with parameters: mixing speed 700 rpm, air flow 0.2 L/min. Slurrys solid content was 20 %. Leaching solutions components were c(Na2O3S2)= 0.2 M; c(NH3) = 0.2 M and cm(Cu2+)= 1 g/L.
NaOH=0.2M (t=30 C) [%] (not measured) NaOH=1M (t=50 C) [%] 35.40 [%] 25.41

NaOH=0.125M;H2O2=0.2M (t= 30 C)

Gold and the silver content from the thiosulphate leaching experiments was analyzed from filtrated and diluted liquid samples. The highest gold content in the liquid phase was measured from (cNaOH=1 M, t=50 C) sample at point of time 9 hours, when conversion was 78 %. By leaching of (cNaOH=0.125 M; cH2O2=0.2 M) sample gold conversion of 52 % was reached and with (cNaOH=0.2 M) sample the highest measured conversion was also 52 %. Silvers conversions in these leaching experiments were 35.4 % in sample (cNaOH=1 M, t=50 C) and 25.4 % in sample (cNaOH=0.125 M; cH2O2=0.2 M) for sample (cNaOH=0.2 M) silvers content in liquid sample was not measured.

45

Some of the solid samples were sent to external laboratory (Labtium Oy) for elemental analysis after leaching or oxidation experiment. The main interest from the solid samples was on the chemical changes of sulphur, iron, arsenic, copper, gold and silver in the experiments. Partial results from the analyzed samples are presented in Table XV and the complete elemental analysis in Appendix V. For comparison the original samples contents is also presented in Table XV. Table XV
Sample Original Reference NaOH=0.125M; H2O2=0.2M NaOH=1M (30 C) NaOH=1M (50 C) Leached NaOH=1M (50 C)

Content of main elements in solid samples before and after leaching

S [g/kg] 319 330 320 322 318 315 Fe [g/kg] 333 349 334 346 341 347 As [g/kg] 97.3 100.0 98.7 90.6 88.9 88.8 Cu [g/kg] 6.88 7.11 6.8 7.07 7.11 7.22 Au [mg/kg] 10.5 11.2 11.2 10.9 10.7 7.2 Ag [mg/kg] 89 92 89 92 90 55

According to the results from the solid samples the sulphur content in the samples was not chancing a lot during the oxidation and leaching experiments. Also the iron content was stable during all these experiments. The reason for the stability of these elements is the precipitation of them in alkaline environment after oxidation from the original mineral form. The most notable change in the elements is the change of arsenic amount during the oxidation experiments. In both oxidation experiments where sodium hydroxide concentration was 1 M the decrease of arsenic content was 9.4 % at temperature 30 C and 11.1 % at temperature 50 C. In other oxidation experiments the arsenic content was stable. From gold and silver contents it can be seen that both of these noble metals are stable under alkaline environment during oxidation experiment. The silver conversion according to the solid samples was similar to what was get from AAS analysis. The conversion of silver in sample NaOH = 1 M (50 C) after leaching was 38.9 % from the solid sample when the same value from the liquid phase was 35.4 %. The difference between these conversions is influenced by changes of liquid volume in sampling and AAS analysis. From these elemental contents the mineralogical change in the samples was calculated by assuming that certain elements appear only in particular mineralogical form (explained in section 6.1). The calculated mineral contents in the samples are presented in Table XVI.

46

Table XVI
Sample

Percentual contents of the calculated minerals in the solid samples after the oxidation in alkaline environment and after the leaching.
FeS2 [%] 46.2 44.7 45.6 45.0 44.4 FeAsS [%] 21.7 21.5 19.7 19.3 19.3 CuFeS2 [%] 2.1 2.0 2.0 2.1 2.1 PbS [%] 0.8 0.7 0.7 0.7 0.8 (Zn,Fe)S [%] 5.7 5.5 5.6 5.6 5.7

Reference NaOH=0.125M; H2O2=0.2M NaOH=1M (30 C) NaOH=1M (50 C) Leached NaOH=1M (50 C)

With all oxidation experiments the decreasing content of pyrite and arsenopyrite was detected. Otherwise the content of minerals stayed quite stable. The precipitation of elements in experiments may be caused by side reactions between components in the oxidation experiments.

6.3

2-step combined oxidation and leaching with ammonia and copper

One part of the experiments was to combine the oxidation and the leaching parts. These experiments were done by performing first the oxidation in certain conditions and after that adding the leaching chemicals to the slurry to begin the leaching experiment. Several oxidation conditions were tested to find suitable concentrations for combined oxidation and leaching. The results are compared to the study of Feng and Deventers (2010) where they combined oxidation and leaching under ammoniacal environment with the presence of copper. Preliminary tests Before the actual combined oxidation and leaching process, several oxidations for the concentrate were done to get more information about the behavior of the concentrate during oxidation. These oxidation experiments and their samples are called here preliminary tests. The preliminary tests conditions in the oxidation experiments are presented in Table XVII. Table XVII The preliminary tests: chemical oxidation of the gold concentrates under ammoniacal environment.
Chemical environment NH3 NaOH Cu2+ [mol/L] [mol/L] [g/L] 0.2 0.075 0.8 0.1 0.05 0.4 0.2 0.125 Oxidation temp. [C] 302 302 302 Gas in oxidation Oxidation time [h] 6 9 9

air (0.4 L/min) air (0.6 L/min) air (0.6 L/min)

47

The pH and the redox potential values from the preliminary oxidation experiments are presented in Appendix II (Table IV) and Appendix III (Table IV). After oxidation the preliminary samples were sent to external laboratory (Labtium Oy) for elemental analysis to find the most suitable conditions for the combined process. Preliminary tests results from the elemental analysis after oxidation are present partially in Table XVIII. Total elemental analysis is presented in Appendix V. For comparison the values of the original sample and reference are also presented in the same table. Reference is the maximum analyzed content from the pretreatment experiments. Table XVIII Elemental analysis after oxidation experiments
Sample Original Reference NH3=0.2 M; NaOH=0.075 M; Cu2+=0.8 g/L NH3=0.1 M; NaOH=0.05 M; Cu2+=0.4 g/L NH3=0.2 M; NaOH=0.125 M S [g/kg] 319 330 266 264 316 Fe [g/kg] 333 349 301 298 342 As [g/kg] 97.3 100.0 92.6 94.7 97.9 Cu [g/kg] 6.88 7.11 8.90 7.68 6.82 Au [mg/kg] 10.5 11.2 11.0 11.2 10.9 Ag [mg/kg] 89 92 89 86 89

In the preliminary tests the results show that combination of ammonia and sodium hydroxide with the presence of copper decomposes the sulphidic mineral structure. When copper is present the decreasing of sulphur and iron is more effective than without it. In the experiments copper is always partially precipitated to the solid form. Only in the oxidation of sample (cNH3 = 0.2 M; cNaOH = 0.125 M) a small decrease of copper content was detected. In the preliminary tests the main point was to research mineralogical changes in the concentrate after oxidation. From these contents the mineralogical change in the samples was calculated assuming that certain elements appear only in particular mineralogical form (explained in section 6.1). The results from these calculations are presented in Table XIX. Table XIX
Samples
NH3=0.2 M; NaOH=0.075 M; Cu2+=0.8 g/L NH3=0.1 M; NaOH=0.05 M; Cu2+=0.4 g/L NH3=0.2 M; NaOH=0.125 M

The percentual change of minerals after oxidations under ammoniacal environment.

FeS2 [%] 35.1 34.9 44.1 FeAsS [%] 20.1 20.6 21.3 CuFeS2 [%] 2.6 2.2 2.0 PbS [%] 0.7 0.7 0.7 (Zn,Fe)S [%] 5.6 5.5 5.5

48

The most effective change in mineral form was detected with sample (cNH3 = 0.1 M; cNaOH = 0.05 M; cCu2+ = 0.4 g/L) where the content of pyrite decreased 11.3 %. Other mineral components stayed quite stable according to these assumptions. Other relevant factors in these experiments were also the amount of air flow and time, which need to be considered in these experiments. From these results it can be seen that part of sulphide minerals are leached to the ammonia and copper solution. Combined oxidation and leaching tests Combined oxidation and leaching tests were executed in two steps, where the first was the oxidation part and the second was the leaching part. The selected chemical conditions for the experiments are presented in table XX. Also the effect of temperature and feed of pure oxygen was tested in the experiments. Table XX Chemical oxidation of gold concentrate in conditions where: solid content in slurry was 22.2 %, the mass of solid sample 200 g, mass of liquid phase 700g, mixing speed 700 rpm.
Oxidation temp. [C] 502 502 302 Gas in oxidation Oxidation time [h] 6 6 18

Chemical environment NH3 NaOH Cu2+ [mol/L] [mol/L] [g/L] 0.6 1 1 1 1 0.05 1

O2 (0.4 L/min) O2 (0.4 L/min) air (0.6 L/min)

The oxidation experiments were carried out as a blind test, which means that no samples were taken during that part. Only the pH and the redox potential values were observed in the oxidation experiment part. The measured values of pH and redox potential are presented in Appendix II (Table V) and Appendix III (Table V). The pH values varied in oxidation and leaching tests. The values at the beginning and at end of the oxidation part, and also at the beginning and at end of the leaching part, are presented in Table XXI. Table XXI The pH values from the combined oxidation and leaching tests under ammoniacal environment with the presence of copper.
Oxidation 0h end 10.7 9.1 10.8 9.7 12.5 10.3 Leaching 0h end 10.0 10.5 10.4 11.0 10.5 11.3

NH3=0.6 M; Cu2+=1 g/L NH3=1 M; Cu2+= 1g/L NH3=1 M; NaOH=0.05 M; Cu2+= 1g/L

49

From the pH values it can see that, after the addition of thiosulphate pH increased in every experiment. That can be caused by substitution reaction of gold from the complex ammonia (Au(NH3)2+) to thiosulphate (Au(S2O3)23-). In this case part of ammonia would be released from that reaction. That claim also supports the theory (present by Aylmore and Muir, 2001) that gold reacts with ammonia complex under 80 C if the ammonia is initially in the complex form with copper. The redox potential during chemical oxidation under ammoniacal environment with presence of copper had the similar behavior in every experiment. The noticed trend in every experiment was a slow increase of redox potential during time. The initial value for every experiment can be assumed to be dependent on pH, which was reliant of the concentration of ammonia. After the oxidation step the temperature of the reactor was cooled from 50 C to 30 C in experiments (cNH3= 0.6 M; cCu2+ = 1 g/L) and (cNH3 = 1 M; cCu2+= 1g/L). Also the source and flow rate of gas was changed to air in these two cases. Into the reactor 100 mL of sodium thiosulphate solution was added to form suitable conditions for the leaching reaction. The amount of thiosulphate was calculated to have a concentration of 0.2 mol/L after addition to the oxidation solution. The pH and the redox potential conditions from the leaching part of experiment are presented in Appendix II (Table VI) and Appendix III (Table VI). In results, the experiments are named by using the oxidation concentrations. The concentrations of the component are listed in Table XXII after volume change. Table XXII The concentrations of chemicals after addition of thiosulphate in combined oxidation and leaching experiments.
Oxidation concentrations/ Sample NH3 = 0.6 M; Cu2+= 1 g/L NH3 = 1 M; Cu2+= 1g/L NH3 = 1 M; NaOH = 0.05 M; Cu2+ = 1g/L Real concentrations in leaching c(NH3) cm(Cu2+) [mol/L] [g/L] 0.53 0.88 0.88 0.88 0.88 0.88

After the oxidation process, the reactions were continued by the thiosulphate leaching process. Changes in redox potential were observed in the experiments. The detected redox potential values at the beginning and end of the oxidation, and also at the beginning and the end of leaching part, are presented in Table XXIII.

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Table XXIII The redox potentials from the combined oxidation and leaching experiments under ammoniacal environment in presence of copper.
Oxidation 0h end [mV] [mV] 258 304 241 274 187 265 Leaching 0h end [mV] [mV] 194 202 206 187 243 199

NH3=0.6 M; Cu2+=1 g/L NH3=1 M; Cu2+= 1g/L NH3=1 M; NaOH=0.05 M; Cu2+= 1g/L

The biggest change in the redox potential was noticed in experiment (NH3=1 M; NaOH=0.05 M; Cu2+= 1g/L), where the change during the oxidation was 78 mV and in the leaching 44 mV. The reason for this might be that this experiment had the longest reaction time (18 h oxidation and 9h leaching) compared to the other experiments at similar conditions, where the experiment times were: 6 hours of oxidation and 6 hours of leaching. Other differences between these experiments were the gas and also the gas feed rate in the oxidation part. In the experiments with (NH3=0.6 M; Cu2+=1 g/L) and (NH3=1 M; Cu2+= 1g/L) the oxidizing agent was pure oxygen compared to experiment (NH3=1 M; NaOH=0.05 M; Cu2+= 1g/L) where the fed gas was air. Also, the feed rate was different, when pure oxygen was fed the feed rate to reactor was 0.4 L/min and with air it was 0.6 L/min. These factors might also affect the change in the redox potential in the experiments, because pure oxygen in the reactor forms higher content of oxygen concentration than what happens with air. The liquid part of each sample was prepared and analyzed with AAS to detect the amounts of dissolved copper and gold from the samples. Gold conversion of the samples is presented in Figure 12 and the copper content during the experiments in Appendix IV (Table III). The copper content in the leaching experiments varied in every experiment. The initial content in the leaching phase was 0.88 g/L, in every experiment. With chemical conditions (NH3=1 M; NaOH=0.05 M; Cu2+= 1g/L) the copper content was quite stable and changed between the limits 0.90-0.96 g/L. According to these contents, it can be seen that a small part of copper was leached out from the concentrate. In the sample (NH3=0.6 M; Cu2+=1 g/L) the analyzed copper content was also very stable, the values were between 0.57-0.64 g/L. The greatest variations in the copper content were detected in the sample (NH3=1 M; Cu2+=

51

1g/L). In that experiment the smallest detected copper content was 0.69 g/L and the largest 0.83 g/L.

60 50
gold conversion [%]

40 30 20 10 0 0 3 time [h] 6 9
NH3=0.6 M; Cu2+=1 g/L NH3=1 M; Cu2+= 1g/L NH3=1 M; NaOH=0.05 M; Cu2+= 1g/L

Figure 12

Gold conversions from the leaching of ammoniacal oxidized samples with parameters: temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. Slurrys solid content was 20 %. Leaching solutions thiosulphate concentration after addition was c(O3S2-2)= 0.2 M.

Conversions of leached silver at the end of the experiments are presented in Table XXIV. Table XXIV Silver conversions at the end of the experiment, from leaching of ammoniacal oxidized samples with parameters: temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. Slurrys solid content was 20 %. Leaching solutions thiosulphate concentration after addition was c(O3S2-2)= 0.2 M.
NH3=0.6 M; Cu2+=1 g/L [%] 20.24 NH3=1 M; Cu2+= 1g/L [%] 26.33 NH3=1 M; NaOH=0.05 M; Cu2+=1g/L [%] 19.54

The gold and the silver content in the liquid samples got quite different results in the leaching. The leaching of the (NH3=0.6 M; Cu2+=1 g/L) sample give gold conversion of 55 % and silver conversion of 20 %. The sample (NH3=1 M; Cu2+= 1g/L), where the oxidation was done in similar conditions reached conversions 52 % for gold and 26 % for silver. From these results it can be seen that a rise in the ammonia concentration in the oxidation phase increases the leaching ability of silver and decreases the leaching ability of gold. The final experiment was done in

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conditions where in the ammonia and copper solution a small amount of sodium hydroxide was added and the reaction time was lengthened in both steps. From the combined 2-step experiments (NH3=1 M; NaOH=0.05 M; Cu2+= 1g/L) the conversion for gold was 52 % and 20 % for silver. The solid sample from the combined oxidation and leaching tests, which chemical conditions were: c(NH3) = 1 M; c(NaOH) = 0.05 M; c(Cu2+) = 1g/L, was sent to external laboratory (Labtium Oy) for elemental analysis after the leaching experiments. The main interest from the solid sample was on chemical changes of sulphur, iron, arsenic, copper, gold and silver in the experiments. Partial results from the analyzed samples are presented in Table XXV and the total results from the analysis in Appendix V. For comparison results from reference values are also presented in the same table. Table XXV Content of main elements in reference and after leaching
Sample Original Reference NH3=1M;NaOH=0.05M;Cu2+=1g/L S [g/kg] 319 330 324 Fe [g/kg] 333 349 349 As [g/kg] 97,3 100.0 100 Cu [g/kg] 6,88 7.11 8,85 Au [mg/kg] 10.5 11.2 8.7 Ag [mg/kg] 89 92 78

From the results of the elemental analysis it can be seen that the only changes in element concentrations were the precipitation of copper and decreasing of gold and silver during the leaching experiment. From these elemental contents the mineralogical change in the samples was calculated by assumption that certain elements are appearing only in the particular mineralogical form (explained in section 6.1). The calculated mineral contents in samples are presented in Table XXVI. Table XXVI Percentual contents of the calculated minerals in the solid samples after leaching.
Sample Reference NH3=1M;NaOH=0.05M;Cu2+=1g/L FeS2 [%] 46.2 45.1 FeAsS [%] 21.7 21.7 CuFeS2 [%] 2.1 2.6 PbS [%] 0.8 0.7 (Zn,Fe)S [%] 5.7 5.4

From mineralogical point of view with the made assumptions the content of minerals do not change. This is misleading because the oxidation affects gold leaching rate. Without oxidation the conversion of gold is lower than what was achieved with these experiments.

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Feng and Deventers (2010) studied also the combination of oxidation and leaching experiments. Feng and Deventers (2010) ore contained only 2.9 % of sulphur, when in this study the concentrate contained 35.6 % of sulphur. The main part of their sample consisted of gangue minerals (Albite 23.5 %, Dolomite 21.2 % and Quartz 41.3 %), also the content of gold was very low (4.3 ppm) in their ore. The sulphidic minerals in their study were arsenopyrite (0.1 %), chalcopyrite (0.1 %) and pyrite (5.4 %), when in this study the amounts of minerals were 27.7 % arsenopyrite, 1.1 % chalcopyrite and 49.4 % pyrite according to the mineral analysis. Feng and Deventer (2010) received the best conversion of gold by using concentrations: 0.8 M ammonia and 6 mM copper in the pretreatment phase. pH was kept at value 11 by addition of ammonia during the oxidation. The reaction time in this experiment was 22 hours. After the oxidation part 0.1 M of thiosulphate was added to the solution and the leaching part was started. By using this pretreatment method the conversion of gold increased from 69 % to 94 % in Feng and Deventers (2010) experiment. The best conversion of gold (55 %) was achieved in the presented study with concentration of 0.6 M ammonia and 1 g/L of copper (15.7 mM). Without pretreatment the gold conversion was 36 %. The combined experiments were stopped, because the method was not producing good enough gold conversions from the experiments. From these experiments it was noticed that the chemical conditions were quite difficult to tailor for both of the parts. Feed of pure oxygen and higher temperature (50 C) increased the oxidation processes reaction rate, but also the temperature rise increased the vaporization of ammonia during the experiments. The ammonias escape from the reaction caused lower pH and difficulties for the leaching part.

6.4

Comparison of the results

Gold content in the leaching was analyzed with AAS from the liquid phase and from the solids after leaching in external laboratory by ICP-OES (Labtium Oy). The results of the liquid samples gave divergent results compared to the results from elemental analysis of the solid samples. Comparison between these results is presented in Table XXVII. In this table the gold content in the concentrate before leaching is also taken into account. The results from AAS are converted to solid phase concentration (similar to ICP-OES results) using the known volume of

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liquid phase in the reactor at the sampling time and the initial mass of concentrate in slurry. Table XXVII Gold content and golds percentual difference in the solid samples after the thiosulphate leaching.
before leaching [mg/kg] 11.2 10.6 10.4 10.7 10.6 AAS after leaching [mg/kg] [%] 9.9 11.9 4.3 59.0 4.5 57.1 3.0 71.5 5.4 49.2 ICP-OES after leaching [mg/kg] [%] 10.3 8.0 8.4 20.8 8.1 22.1 7.2 32.7 8.7 17.9

original dry ground wet ground NaOH=1M (t=50 C) NH3=1 M; NaOH=0.05 M; Cu2+=1g/L

From Table XXVII it can be seen that the results are quite different from the liquid samples (analyzed with AAS) and the solid samples (ICP-OES, analyzed by Labtium Oy). Almost systematic deviation is presence between these two results. The analyzed gold content in the solid samples is a lot higher than what was analyzed from the liquid phase and transformed to solid concentrations. The differences in the gold content vary from 2.5 to 4.2 mg/kg which is a large difference when the total amount of gold in the sample was in the range of 10.4 11.2 mg/kg. The reason for this variation can be in the preparation of liquid samples for AAS. With these liquid samples some precipitation was detected during analysis. The strongest theory to explain the gold content difference is the precipitation of gold on the concentrate surface. This precipitation most likely happened during the filtration after the leaching test has been finished. The chemical conditions changed after the slurry was removed from reactor. The change happened when gas feed and mixing were stopped. The filtration of slurry took some time which probably caused the precipitation of gold on the solids. The detected value from the original concentrates leaching supports this theory. In this 18 hour leaching the gold started to precipitate before the leaching was finished. Comparison of the results of these samples shows similar behavior in both of the obtained results. To confirm the effect of possible precipitation to the AAS result comparison of silver conversions between the results was also made. The silver contents analyzed with AAS from liquid and solid samples in external laboratory (ICPOES, analyzed by Labtium Oy) gave results which are presented in Table

55

XXVIII. For comparison the silver content of concentrate is also considered in the calculated conversions.

Table XXVIII Silver contents in solids before and after leaching and also the percentual changes of it.
before leaching [mg/kg] 92 90 88 90 90 AAS after leaching [mg/kg] [%] 90 1.9 66 26.3 70 20.8 62 30.7 74 17.5 ICP-OES after leaching [mg/kg] [%] 90 2.2 60 33.3 63 28.4 55 38.9 78 13.3

original dry ground wet ground NaOH=1M (t=50 C) NH3=1 M; NaOH=0.05 M; Cu2+=1g/L

Comparison of the silver contents in the solid samples gives confirmation about the validity of the AAS analysis. The results are not exactly the same but close enough to remove suspicion from the golds AAS analysis accuracy. The conclusions from these results are that the gold precipitates on the solid phase but the silver stays in the liquid phase. Other factor that came out from the elemental analysis was the elemental stability during the oxidation experiments. Because, from the leaching experiments it can be seen that gold is exposed during the oxidation experiments the explanation for the elemental stability must be in the form where the compounds appear in the slurry. The specific chemical compound in slurry cannot be known from the obtained results, but possible insoluble compound in oxidation and leaching environment can be assumed. For instance, if iron from pyrite and other minerals forms oxides or hydroxides the possible chemical compounds of them FeO, FeO(OH) or Fe(OH)3 are all insoluble in alkaline or neutral environment. Possible side reactions and their products in slurry would require more research to explore realistic contents and forms of chemicals after experiments. Also, mineralogical research about the products would give perspective for the results.

CONCLUSIONS

This experimental study was carried out to find a pretreatment method which operates at similar conditions than the thiosulphate leaching process. The used pretreatment methods were mechanical activation, oxidation under alkaline

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environment and integration of oxidation and leaching process under ammoniacal environment with the presence of copper. The main sulphuric mineral components in the refractory concentrate were pyrite (49.4 %) and arsenopyrite (27.7 %). The gold content in the concentrate was in the range of 10.4-11.2 ppm and silver content in the range of 88-92 ppm. Without pretreatment the highest gold conversion in thiosulphate leaching was 30 %, which was analyzed at the time point of 9 hours. At that time the silver conversion was 17 %. In mechanical activation the particle size was decreased by using planetary ball mill. The milling was done by dry grinding and wet grinding. Originally the mean particle size for the concentrate was 36.67 m and with dry grinding it decreased to 11.46 m and with wet grinding to 8.51 m. By using mechanical activation in leaching of the dry ground sample the gold conversion was 59 % and silver conversion 26 % in thiosulphate leaching. With wet ground sample the gold conversion 57 % and silver conversion 21 % were achieved with thiosulphate leaching. From these results it can be seen that plain mechanical activation was not providing enough exposure of gold in the leaching experiments. If this kind of experiment is wanted to do in future for this concentrate the mechanochemical activation would be worth of trying. For instance grinding the wet ground sample with alkaline solution might give suitable results from this kind of pretreatment method. In pretreatment of chemical oxidation under alkaline environment where the used chemical was sodium hydroxide, the highest reached conversion of gold was 72 % and for silver 31 % in thiosulphate leaching. These results were obtained from pretreatment where the concentration of sodium hydroxide was 1 M, the used oxidation agent was air, temperature was 50 C and experiment time 9 hours. The reached conversion from this experiment was quite close to the target lower limit (conversion 80 %). For reaching that limit the experiment and conditions need to be optimized. If possible the temperature could be raised up to 70 C to improve oxidation reaction rate. As an oxidizing agent oxygen is more effective than air, so with this gas the experiment could be improved. If the temperature is wanted to keep at 50 C increasing sodium hydroxide concentration might also be an alternative. With concentration 1 M the achieved conversion was close to the

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target so the rise of it to 1.5 M might possibly be a suitable amount to reach the target. In the combined chemical oxidation and thiosulphate leaching experiment the conversion of gold remained at 49 % and 18 % for silver. The result were achieved at conditions where the chemical oxidation was carried out with ammonia concentration 1 M, sodium hydroxide concentration 0.05 M and with mass concentration of copper 1 g/L. The chemical oxidation time was 18 hours and temperature 30 C. The problem with these experiments was the vaporization of ammonia. At temperature 50 C ammonia escapes from the reactor by vaporization or as a consequence of gas feed. Optimization and additional research are needed for this integrated chemical oxidation and leaching experiments, so that it could provide results where the gold conversion is over 80 %. From the results it can be seen that the reached gold conversion was not at acceptable level in any experiment. Plain decreasing of particle size was not providing the wanted answer for the pretreatment need. The most promising results came from oxidation under alkaline conditions with sodium hydroxide. From those experiments it can be seen that temperature is important factor in oxidation experiments. The increasing of temperature from 30 C to 50 C raised the reaction rate according to the consumption of sodium hydroxide. Also the concentration of sodium hydroxide played important role in those experiments. From experiment where initial concentration was cNaOH = 1 M (t=50 C) the chemical oxidation process was providing good results as long as chemical requirements in reactions are optimized. With this amount of concentrate the concentration of sodium hydroxide was not sufficient. From the results of the combined chemical oxidation and thiosulphate leaching experiments one can come to the conclusion that oxygen as an oxidizing agent is more effective than air. Also temperature increase improved the reaction rate. More experimental research is needed to reach acceptable results from pretreatment and thiosulphate leaching. Also, optimization of both methods is needed.

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Gekko systems, , http://www.gekkos.com/documents/025MaximizingGravity Recovery ThroughTheApplicationOfMultipleGravityDevices.pdf, 30.5.2012 Grosse A. C., Dicinoski G. W., Shaw M. J., Haddad P. R., Leaching and recovery of gold using ammoniacal thiosulfate leach liquors (a review), Hydrometallurgy, vol. 69, pp. 1-21, 2003 Habashi F., Textbook of Hydrometallurgy, 2. edition, pp. 14, 65-66, 97-99, 128-130, 138, 140-156, 161, 195-199; 1999 Quebec City Kirk-Othmer Encyclopedia of chemical technology, vol 12, ed. Kroschwitz J., Howe-Grant M., 4. edition, pp. 743-744, 1992 New York Li Q., Li D., Qian F., Pre-oxidation of high-sulfur and high-arsenic refractory gold concentrate by ozone and ferric ions in acidic media, Hydrometallurgy, vol. 97, pp. 61-66, 2009 Maol taulukot, Seppnen R., Kervinen M., Parkkila I., Karkela L., Merilinen P., 2. edition, Keuruu 2006 Marchbank A. R., Thomas K. G., Dreisinger D., Fleming C., Gold recovery from refractory carbonaceus ores by pressure oxidation and thiosulfate leaching, U.S. Patent No.5536297, July 16 1996 Mason P. G., Wicks F. D., Gathje J. C., Process for the recovery of gold from refractory ores by pressure oxidation, U.S. Patent No.4552589, November 12 1985 McGraw-Hill's AccessScience, http://accessscience.com/content/Pyrometallurgy,%20nonferrous/559700 15.5.2012 Metallurgy and Materials Society, http://www.metsoc.org/virtualtour/processes/acid-leech/autoclave.asp, 11.5.2012 Metalworking machines, http://metalworkingmachine.net/2011/02/15/ballmilling/ 23.5.2012 Mihaljevi M., Sisr L., Ettler V., ebek O., Pra J., Oxidation of As-bearing gold ore-a comparison of bach and colum experiments, Journal of geochemical exploration, vol. 81, pp. 59-70, 2004

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Muir D.M., Aylmore M. G., Thiosulphate as an alternative to cyanide for gold processing- issues and implediments. Mineral Prosessing and Extractive Metallurgy, vol. 13, pp. 2-12, March 2004 Nanthakumar B., Pickles C. A., Kelebek S., Microwawe pretreatment of a double refractory gold ore, Minerals Engineering, vol. 20, pp.1109-1119, 2007 Perry R. H., edit. Green D. W., Perrys chemical engineers handbook, 7 th edition. pp. 17-2 17-16; 20-22, 20-50, 1997 New York Richardson S., Vaughan D. J., Arsenopyrite: a spectroscopic investigation of altered surfaces, Mineralogical Magazine, Vol. 53, pp. 223-229, April 1989 Rimstidt J.D., Vaughan D. J., Pyrite oxidation: A state-of-the-art assessment of the reaction mechanism, Geochimica et Cosmochimica Acta, vol. 67, pp. 873880, March 2003 Sand W., Gehrke T., Jozsa P-G., Schippers A., (Bio)chemistry of bacterial leaching-direct vs. indirect bioleaching, Hydrometallurgy, vol. 59, pp. 159175, 2001 Shu J., Lakshmanan V. I., Convey J., Sintering and ferrite formation during high temperature roasting of sulfide concentrates, Canadian Metallurgical Quarterly, vol. 38, No.4, pp. 215-225, 1999 Smith J.C., McCord T. H., ONeil G. R., Treating refractory gold ores via oxygen-enriched roasting, U.S. Patent No. 4919715, April 24 1990 Thomas K.G., Fleming C., Marchbank A. R., Dreisinger D., Gold recovery from refractory carbonaceous ores by pressure oxidation, thiosulfate leaching and resin-in-pulp adsorption, U.S. Patent No. 5785736, July 28 1998 Ullmans Encyclopedia of Industrial Chemistry a, vol. A12, ed. Elvers B., Hawkins S., Ravenscraft M., Rounsaville J. F., Schulz G., 5. edition, Weinheim 1990 Ullmans Encyclopedia of Industrial Chemistry b, vol. 4, ed. Grund S. C., ed. Hanusch K., ed. Wolf H. U., Arsenic and arsenic compounds, 210, Published online: 15 October 2008 Ullmans Encyclopedia of Industrial Chemistry c, vol. 25, ed. Kirchner M. J., Ozone, pp. 638-639, Published online: 15 June 2000

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Ullmans Encyclopedia of Industrial Chemistry d, vol. 18, ed. Goor G., Glenneberg J., Jacobi S., Hydrogen peroxide, pp. 396-397, Published online: 15 April 2007 Ullmans Encyclopedia of Industrial Chemistry e, vol. 15, ed.Yarar B., Flotation, pp. 237-240, Published online: 15 June 2000 Ullmans Encyclopedia of Industrial Chemistry f, vol. 17, ed.Burt R. O.,., Gravity concentration, pp. 167-168, Published online: 15 June 2000 Ullmans Encyclopedia of Industrial Chemistry g, vol. 17, ed. Renner H., Schlamp G., Hollman D., Lschow H. M., Tews P., Rothaut J., Dermann K., Kndler A., Hecht C., Schlott M., Drieselmann R., Peter C., Schiele R., Gold, Gold alloys, and gold compounds, pp. 103-105, Published online: 15 september 2000 Vaughan J.P., The process mineralogy of gold: The classification of ore types, Journal of metals, vol. 56, pp. 46-48, July 2004 Zhang S., Oxidation of refractory gold concentrates and simultaneous dissolution of gold in aerated alkaline solutions, Ph.D. dissertation, Murdoch
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LIST OF APPENDIXES Appendix I: Contents of sulphate and thiosulphate during the leaching experiments Appendix II: pH values in the oxidation and the leaching experiments Appendix III: Redox potential values in the oxidation and the leaching experiments Appendix IV: Appendix V: Appendix VI: Copper content in the leaching experiments Results from elemental analysis of solid samples Gold content in the leaching experiments at liquid phase (AAS)

Appendix I, 1(3) Contents of sulphate and thiosulphate during leaching experiments 1 Table I Thiosulphate and sulphate in leaching of the mechanically activated samples and the original sample Thiosulphate (S2O32-)content in liquid phase from leaching of original sample, mechanically activated dry and wet ground samples with parameters temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. Slurrys solid content was 20 %. Leaching liquors components were c(O3S22-)= 0.2 M; c(NH3) = 0.2 M and cm(Cu2+)= 1 g/L.
time [h] initial in liquid phase 0 3 6 9 20 dry ground sample [g/L] 22.43 not measured not measured not measured not measured wet ground sample [g/L] 22.43 19.82 16.51 12.81 10.82 10.53 0.00 original sample [g/L] 22.43 19.37 16.25

Table II

Sulphate (SO42-) content in liquid phase from leaching of original sample and mechanically activated dry and wet grinded samples with parameters temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. Slurrys solid content was 20 %. Leaching liquors components were c(O3S22-)= 0.2 M; c(NH3) = 0.2 M and cm(Cu2+)= 1 g/L.
time [h] dry ground sample [g/L] not measured not measured not measured not measured wet ground sample [g/L] 1.52 1.95 3.50 3.42 4.17 5.15 9.30 original sample [g/L] 1.52 2.92 3.84

initial in liquid phase 0 3 6 9 20

Appendix I, 2(3) 2 Table III Thiosulphate and sulphate in the leaching of chemically oxidized sample under alkaline environment Thiosulphate (S2O32-) contents in liquid samples from leaching experiments with parameters: temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. Slurrys solid content was 20 %. Leaching liquors components were c(O3S22-)= 0.2 M; c(NH3) = 0.2 M and cm(Cu2+)= 1 g/L.
time [h] initial in liquid phase 0 3 6 9 NaOH=0.125M; H2O2=0.2M [g/L] 22.43 19.83 17.35 15.19 12.39 NaOH=0.2M [g/L] 22.43 19.42 17.39 14.86 11.21 NaOH=1M (T=50 C) [g/L] 22.43 19.17 18.64 16.02 14.94

Table IV

Sulphate (SO42-) content in samples from leaching experiments with parameters: temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. Slurrys solid content was 20 %. Leaching liquors components were c(O3S22-)= 0.2 M; c(NH3) = 0.2 M and cm(Cu2+)= 1 g/L.
NaOH=0.125M; H2O2=0.2M [g/L] 1.52 2.71 2.36 3.25 2.07 NaOH=0.2M [g/L] 1.52 3.67 4.53 5.21 3.99 NaOH=1M (T=50 C) [g/L] 1.52 2.08 2.51 2.49 3.37

time [h] initial in liquid phase 0 3 6 9

Appendix I, 3(3) 3 Table V Thiosulphate and sulphate in combinated oxidation and leaching experiments under ammoniacal environment with copper. Thiosulphate (S2O32-) content in samples from leaching of ammoniacal oxidized samples with parameters: temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. Slurrys solid content was 20 %. Leaching liquors components after addition to slurry were c(O3S2-2) = 0.2 M.
time [h] initial in liquid pahse 0 3 6 9 NH3=0.6 M; Cu2+=1 g/L [g/L] 22.43 20.72 14.88 10.80 NH3=1 M; Cu2+= 1g/L [g/L] 22.43 19.98 16.40 10.73 NH3=1 M; NaOH=0.05 M; Cu2+ = 1g/L [g/L] 22.43 not measured not measured not measured not measured

Table VI

Sulphate content (SO42-) in liquid samples from leaching of ammoniacal oxidized samples with parameters: temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. Slurrys solid content was 20 %. Leaching liquors components after addition to slurry were c(O3S2-2) = 0.2 M.
time [h] NH3=0.6 M; Cu2+=1 g/L [g/L] 1,52 5,73 8,15 8,73 NH3=1 M; Cu2+= 1g/L [g/L] 1,52 5,73 8,54 9,92 NH3=1 M; NaOH=0.05 M; Cu2+ = 1g/L [g/L] 1,52 not measured not measured not measured not measured

initial in liquid pahse 0 3 6 9

Appendix II, 1(3) pH values in the oxidation and the leaching experiments 1. Table I pH from leaching of mechanically activated samples and the original sample pH in the leaching experiments of the original sample and the mechanically activated dry and wet grinded samples with parameters temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. Slurrys solid content was 20 %. Leaching liquors components were c(O3S22-)= 0.2 M; c(NH3) = 0.2 M and cm(Cu2+)= 1 g/L.
time [h] 0 3 6 9 dry ground sample 10.32 10.17 10.53 10.75 wet ground sample 10.65 10.29 10.47 10.50 11.67 original sample 11.18 11.15

2. Table II

pH from chemical oxidation under alkaline environment and thiosulphate leaching of them. pH values from chemical oxidation process of gold concentrate at conditions: Solid content in slurry was 30 %, the mass of solid sample 300 g, mass of liquid phase 700g, mixing speed 700 rpm and air feed 0.6 L/min.
NaOH=0.125M; H2O2=0.2M 13.58 13.34 13.21 NaOH=0.2M 13.79 13.81 13.52 13.53 13.17 12.98 12.98 13.33 13.41 NaOH=1M (T=50 C) 13.37 13.31 13.11 13.08 12.93 12.85 12.81 12.73 12.65 12.64 NaOH=1M (T=30 C) 14.12 14.05 14.00 13.98 13.92 13.94 13.87 13.90 13.83 13.79

time [h] 0 1 2 3 4 5 6 7 8 9

Appendix II, 2(3) Table III pH from the leaching of chemically oxidized samples under alkaline environment. The experiments were carried out with parameters: temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. Slurrys solid content was 20 %. Leaching liquors components were c(O3S2-2)= 0.2 M; c(NH3) = 0.2 M and cm(Cu2+)= 1 g/L.
time [h] 0 11.46 3 11.54 6 11.71 9 11.83 10.89 11.71 10.77 11.52 10.60 NaOH=0.125M; H2O2=0.2M 11.34 NaOH=0.2M 11.80 NaOH=1M (T=50 C) 10.77

3.

pH from combinated oxidation and leaching experiments under ammoniacal environment with copper

Preliminary tests Table IV pH values during chemical oxidation process of gold concentrate under ammoniacal environment. The experiments were carried out at conditions: Solid content in slurry was 30 %, the mass of solid sample 300 g, mass of liquid phase 700g, mixing speed 700 rpm.
time [h] 0 3 6 9 NH3=0.2 M; NaOH=0.075 M; Cu2+=0.8 g/L 13.18 11.35 10.49 NH3=0.1 M; NaOH=0.05 M; Cu2+=0.4 g/L 12.60 10.80 10.40 9.60 NH3=0.2 M; NaOH=0.125 M 13.62 13.36 12.98 12.66

Combined oxidation and leaching tests Table V pH values from chemical oxidation of gold concentrate under ammoniacal environment and with presence of copper. The experiment were carried out in conditions where: solid content in slurry was 22.2 %, the mass of solid sample 200 g, mass of liquid phase 700g, mixing speed 700 rpm.
time [h] 0 1 2 3 NH3=0.6 M; Cu2+=1 g/L 10.70 10.16 9.75 9.52 NH3=1 M; Cu2+= 1g/L 10.80 10.40 10.18 10.00 NH3=1 M; NaOH=0.05 M; Cu2+ = 1g/L 12.45 11.80 11.56 11.44

4 5 6 18

9.34 9.27 9.11

9.89 9.70 9.67

11.30

10.27

Appendix II, 3(3) Table VI pH from leaching of ammoniacal oxidized samples with parameters: temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. Slurrys solid content was 20 %. Leaching solutions components after addition to slurry were c(O3S2-2)= 0.2 M.
time [h] 0 10.24 3 10.45 6 11.31 9 10.98 10.90 10.57 10.73 NH3=0.6 M; Cu2+=1 g/L 9.96 NH3=1 M; Cu2+= 1g/L 10.42 NH3=1 M; NaOH=0.05 M; Cu2+ = 1g/L 10.52

Appendix III, 1(3) Redox potential values in the oxidation and the leaching experiments 1. Table I The leaching of mechanically activated samples and the original sample Redox potentials in the leaching experiments of the original sample, the mechanically activated dry and wet ground samples with parameters temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. Slurrys solid content was 20 %. Leaching liquors components were c(O3S22-)= 0.2 M; c(NH3) = 0.2 M and cm(Cu2+)= 1 g/L.
time [h] 0 3 6 9 dry ground sample [mV] 129 163 182 193 wet ground sample [mV] 165 173 188 199 216 original sample [mV] 185 205

2.

Redox potential values in the oxidation and the leaching experiments, where the chemical oxidation was carried out under alkaline environment Redox potentials in chemical oxidation process under alkaline environment. The oxidation were carried out at conditions: solid content in slurry was 30 %, the mass of solid sample 300 g, mass of liquid phase 700g, mixing speed 700 rpm and air feed 0.6 L/min.
NaOH=0.125M; H2O2=0.2M [mV] 88 96 93 NaOH=0.2M [mV] 78 89 80 89 97 100 102 92 92 NaOH=1M (T=50 C) [mV] -37 -43 -34 -43 -76 -83 -56 -66 NaOH=1M (T=30 C) [mV] 5 -6 -5 -7 0 -2 -6 -6

Table II

time [h] 0 1 2 3 4 5 6 7

8 9

-58 -59

-5 -8

Appendix III, 2(3) Table III Redox potentials in the leaching experiments for chemically oxidized sample under alkaline environment. The leaching experiments were carried out with parameters: temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. Slurrys solid content was 20 %. Leaching liquors components were c(O3S22-)= 0.2 M; c(NH3) = 0.2 M and cm(Cu2+)= 1 g/L.
time [h] 183 0 203 3 212 6 212 9 211 204 218 191 209 178 195 172 NaOH=0.125M; H2O2=0.2M [mV] NaOH=0.2M [mV] NaOH=1M (T=50 C) [mV]

3.

The redox potentials in the combinated oxidation and leaching experiments under ammoniacal environment with copper

Preliminary tests Table IV Redox potentials in chemical oxidation process of the gold concentrate under ammoniacal environment. The oxidation experiments were carried out at conditions: Solid content in slurry was 30 %, the mass of solid sample 300 g, mass of liquid phase 700g, mixing speed 700 rpm.
time NH3=0.2 M; NaOH=0.075 M; Cu2+=0.8 g/L [mV] 109 191 246 NH3=0.1 M; NaOH=0.05 M; Cu2+=0.4 g/L [mV] 131 204 253 268 NH3=0.2 M; NaOH=0.125 M [mV] 72 102 118 129

[h] 0 3 6 9

Appendix III, 3(3) Combined oxidation and leaching tests Table V Redox potentials in chemical oxidation process under ammoniacal environment. The experiments were carried out at conditions: solid content in slurry was 30 %, the mass of solid sample 300 g, mass of liquid phase 700g, mixing speed 700 rpm.
NH3=0.6 M; Cu2+=1 g/L time [mV] [h] 0 1 2 3 4 5 6 18 258 278 282 289 294 300 304 [mV] 241 244 252 258 262 269 274 265 NH3=1 M; Cu2+= 1g/L NH3=1 M; NaOH=0.05 M; Cu2+ = 1g/L [mV] 187 203 217 224 227

Table VI

Redox potentials in leaching of ammoniacal oxidized samples. The experiments were carried out with parameters: temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. The solid content of slurry was 20 %. Leaching solutions components after addition to slurry were c(O3S2-2)= 0.2 M.
time [h] 194 0 197 3 202 6 199 9 187 207 175 190 206 243 NH3=0.6 M; Cu2+=1 g/L [mV] NH3=1 M; Cu2+= 1g/L [mV] NH3=1 M; NaOH=0.05 M; Cu2+ = 1g/L [mV]

Appendix IV, 1(2) The copper content in the leaching experiments 1. Table I Copper content from leaching of mechanically activated samples and the original sample Copper content in the leaching experiments of the original sample, the mechanically activated dry and wet ground samples with parameters: temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. Slurrys solid content was 20 %. Leaching liquors components were c(O3S22-)= 0.2 M; c(NH3) = 0.2 M and cm(Cu2+)= 1 g/L.
time [h] 0 3 6 9 dry ground sample [g/L] 0.75 0.89 1.03 0.97 wet ground sample [g/L] 0.89 0.79 0.84 0.80 0.77 original sample [g/L] 0.88 0.99

2. Table II

Copper content from leaching of chemically oxidized sample under alkaline environment Copper content in the leaching experiments of chemically oxidized samples under alkaline environment. The experiments were carried out with parameters: temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. Slurrys solid content was 20 %. Leaching liquors components were c(O3S22-)= 0.2 M; c(NH3) = 0.2 M and cm(Cu2+)= 1 g/L.
time [h] 0 3 6 9 NaOH=0.125M; H2O2=0.2M [g/L] 0.98 0.97 0.85 0.67 NaOH=0.2M [g/L] 0.83 0.81 0.76 0.64 NaOH=1M (T=50 C) [g/L] 0.96 0.99 1.01 0.89

Appendix IV, 2(2) 3. Copper content from leaching of combinated oxidation and leaching experiments under ammoniacal environment with copper

Table III

Copper content in leaching of ammoniacal oxidized samples with parameters: temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. The solid content of slurry was 20 %. Leaching solutions components after addition to slurry were c(O3S2-2)= 0.2 M.
time [h] 0 3 6 9 NH3=0.6 M; Cu2+=1 g/L [g/L] 0.60 0.64 0.57 NH3=1 M; Cu2+= 1g/L [g/L] 0.78 0.83 0.69 NH3=1 M; NaOH=0.05 M; Cu2+ = 1g/L [g/L] 0.90 0.90 0.96 0.91

APPENDIX V 1(2) Results from elemental analysis of solid samples Table I Solid samples elemental analysis from several samples after oxidation and/or after leaching (Labtium Oy).
Ag mg/kg Original Leached original Dry ground Leached dry ground Wet ground Leached wet ground NaOH=0.125M; H2O2=0.2M NaOH=1M (30 C) NaOH=1M (50 C) Leached NaOH=1M (50 C) NH3=0.2 M; NaOH=0.075 M; Cu =0.8 g/L NH3=0.1 M; NaOH=0.05 M; Cu =0.4 g/L NH3=0.2 M; NaOH=0.125 M oxd. and leach. NH3=1M; NaOH=0.05M; Cu2+=1g/L
2+ 2+

As mg/kg 97300 93800 100000 99400 98200 96600 98700 90600 88900 88800 92600 94700 97900 100000

Cd mg/kg 155 161 159 151 156 154

Co mg/kg 104 99 108 106 108 107 104

Cr mg/kg 10 33 92 96 1350 1420 9 10 12 13 10 9 10 13

Cu mg/kg 6880 9720 7010 6700 6840 6790 6800 7070 7110 7220 8900 7680 6820 8850

Fe mg/kg 333000 324000 343000 342000 340000 342000 334000 346000 341000 347000 301000 298000 342000 349000

Mn mg/kg 202 232 212 216 249 269 208 209 215 226 202 204 206 212

Mo mg/kg 7 8 7 7 12 12 6 6 6 7 5 5 7 6

89 90 90 60 88 63 89 92 90 55 89 86 89 78

160 158 162

109 108 108 95 97 102

155

107

APPENDIX V 2(2) Table II Solid samples elemental analysis from several samples after oxidation and/or after leaching (Labtium Oy).
Ni mg/kg Original Leached original Dry ground Leached dry ground Wet ground Leached wet ground NaOH=0.125M; H2O2=0.2M NaOH=1M (30 C) NaOH=1M (50 C) Leached NaOH=1M (50 C) NH3=0.2 M; NaOH=0.075 M; Cu =0.8 g/L NH3=0.1 M; NaOH=0.05 M; Cu =0.4 g/L NH3=0.2 M; NaOH=0.125 M oxd. and leach. NH3=1M; NaOH=0.05M; Cu =1g/L
2+ 2+ 2+

Pb mg/kg 6260 7080 6420 6530 6330 6550 6330 6350 6380 6680 6460 6300 6260 6460

S mg/kg 319000 304000 330000 325000 319000 312000 320000 322000 318000 315000 266000 264000 316000 324000

Sb mg/kg 3460 3750 3520 3570 3450 3490 3640 3530 3410 3490 3540 3550 3570 3570

Zn mg/kg 35200 36200 35800 36400 34900 35300 35500 35700 36000 36700 36100 35500 35300 34500

Au g/kg 10500 10300 10600 8410 10400 8060 11100 10900 10700 7190 11000 11200 10900 8700

Pd g/kg

Pt g/kg

28 40 30 29 60 61 40 27 27 29 40 39 39 28

27

< 20

33 31 28

< 20 < 20 < 20

Appendix VI, 1(2) Gold content in the leaching experiments at liquid phase (AAS) 1. Table I Gold content from leaching of mechanically activated samples and the original sample Gold content in the leaching experiments of the original sample, the mechanically activated dry and wet ground samples with parameters: temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. Slurrys solid content was 20 %. Leaching liquors components were c(O3S22-)= 0.2 M; c(NH3) = 0.2 M and cm(Cu2+)= 1 g/L. Maximum gold content in sample was 2.87 mg/L.
time [h] 0 0.88 3 1.33 6 1.38 9 1.81 1.71 1.04 1.55 1.48 1.03 1.11 0.76 dry ground sample [mg/L] wet ground sample [mg/L] original sample [mg/L]

2. Table II

Gold content from leaching of chemically oxidized sample under alkaline environment Gold content in the leaching experiments of chemically oxidized samples under alkaline environment. The experiments were carried out with parameters: temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. Slurrys solid content was 20 %. Leaching liquors components were c(O3S22-)= 0.2 M; c(NH3) = 0.2 M and cm(Cu2+)= 1 g/L. Maximum gold content in sample 2.87 mg/L.
time [h] 0 3 6 9 0.78 1.32 1.48 1.50 0.73 0.74 1.48 1.40 1.08 1.93 2.14 2.21 NaOH=0.125M; H2O2=0.2M [mg/L] NaOH=0.2M [mg/L] NaOH=1M (T=50 C) [mg/L]

Appendix VI, 2(2) 3. Gold content from leaching of combinated oxidation and leaching experiments under ammoniacal environment with copper Gold content in leaching of ammoniacal oxidized samples with parameters: temperature 30 2 C, mixing speed 700 rpm, air flow 0.2 L/min. The solid content of slurry was 20 %. Leaching solutions components after addition to slurry were c(O3S2-2)= 0.2 M. Maximum gold content in sample was 2.87 mg/L.
time [h] 0 3 6 9 1.18 1.35 1.55 1.05 1.26 1.46 1.05 1.38 1.44 1.46 NH3=0.6 M; Cu2+=1 g/L [mg/L] NH3=1 M; Cu2+= 1g/L [mg/L] NH3=1 M; NaOH=0.05 M; Cu2+ = 1g/L [mg/L]

Table III