*Article* **Recovery of Gold from the Refractory Gold Concentrate Using Microwave Assisted Leaching**

**Kanghee Cho 1, Hyunsoo Kim 2, Eunji Myung 2, Oyunbileg Purev 2, Nagchoul Choi 1,\* and Cheonyoung Park 2,\***


Received: 23 March 2020; Accepted: 27 April 2020; Published: 28 April 2020

**Abstract:** Microwave technology has been confirmed to be suitable for use in a wide range of mineral leaching processes. Compared to conventional leaching, microwave-assisted leaching has significant advantages. It is a proven process, because of its short processing time and reduced energy. The purpose of this study was to enhance the gold content in a refractory gold concentrate using microwave-assisted leaching. The leaching efficiencies of metal ions (As, Cu, Zn, Fe, and Pb) and recovery of gold from refractory gold concentrate were investigated via nitric acid leaching followed by microwave treatment. As the acid concentration increased, metal ion leaching increased. In the refractory gold concentrate leaching experiments, nitric acid leaching at high temperatures could limit the decomposition of sulfide minerals, because of the passive layer in the refractory gold concentrate. Microwave-assisted leaching experiments for gold recovery were conducted for the refractory gold concentrate. More extreme reaction conditions (nitric acid concentration > 1.0 M) facilitated the decomposition of passivation species derived from metal ion dissolution and the liberation of gangue minerals on the sulfide surface. The recovery rate of gold in the leach residue was improved with microwave-assisted leaching, with a gold recovery of ~132.55 g/t after 20 min of the leaching experiment (2.0 M nitric acid), according to fire assays.

**Keywords:** recovery; gold; refractory; nitric acid; microwave

#### **1. Introduction**

Gold has excellent physical and chemical properties, and is one of the most important noble metals. The current rapid decline in high-grade gold ores and readily available low-grade gold ores has made the mineral processing industry increasingly reliant on complex and refractory gold ores [1,2]. Consequently, mineral processing challenges related to the complexities of ore mineralogy and the process parameters, such as the impacts of associated minerals, are important research questions [3]. Mineralogical studies aim to characterize complex sulfides and show the interrelations of the target minerals in the refractory minerals. In addition, these studies usually analyze gold-bearing sulfide minerals for follow-up processes and efficient gold recovery. Gold can be found in complex sulfide minerals, not only due to the presence of invisible gold, but also due to the existence of solid solutions [4]. Gold is commonly associated with sulfide minerals, particularly pyrite and arsenopyrite [5]. A refractory gold ore typically contains different sulfide minerals with various gold concentrations [6]. Gold is highly encapsulated in the sulfide matrix in refractory gold ores. Pretreatment is an important process to recover gold from sulfide minerals. Gold-bearing ores ordinarily contain complex or refractory ores of sulfide minerals that interfere with gold recovery efficiency. It is necessary to remove sulfide minerals prior to leaching, and the most appropriate pretreatment is flotation and roasting. However, most of

the sulfide minerals in a refractory gold concentrate react to form a harmful gas during roasting and the iron oxide produced during roasting encapsulates invisible or fine gold [7]. Pyrite is the most abundant sulfide mineral in refractory gold ore and its oxidation is thermodynamically favorable in the environment [8].

The surface oxidation of pyrite is a particularly important step for leaching valuable metals from sulfide minerals. The presence of invisible gold has been established in pyrite, which is a common type of gold-bearing sulfide mineral that is mostly found in association with other sulfide minerals. The gold present in sulfide minerals can be divided into visible gold and invisible gold. While visible gold can be observed with an optical microscope, invisible gold is very difficult to observe with these microscopes. The size of invisible gold may be on the order of nanometers, its presence is indicated by significant refractory imposed by the sulfide minerals (e.g., arsenopyrite, pyrite) [9]. The hindrance of gold recovery from complex sulfide minerals has been attributed to the formation of a passive layer on the mineral surface. Recent studies [10–14] have been conducted on the passive layer effect in sulfide minerals and the role played by sulfur in leaching solutions. In particular, the leaching of galena (PbS) has some problems, due to the low solubility of galena without the presence of an oxidant, the formation of precipitation, and the disposal of a large amount of iron that dissolves along with the lead. Therefore, leaching of the galena has been investigated by many researchers, who have proposed different nitric acid based leaching systems, including HNO3 [10], H2O2-HNO3 [13] and Fe(III)-HNO3 [14]. The kinetics of lead dissolution from galena are slow, due to the formation of the passivation layer on the surface of sulfide by oxidation of sulfide, to form elemental sulfur under oxidative conditions. It is known that a partial dissolution or decomposition of sulfide minerals by the leaching solution lowers the leaching rate by forming a passive layer [11].

Unfortunately, the contributions of reactive sulfur species and the mechanisms of interaction with the leach residue surface are unclear. Therefore, studying the effects of relational minerals on gold is important. The processing of intractable substances presents challenges related to their complexity or refractory minerals. Increasing concerns regarding environmental protection has triggered efforts to identify alternatives that are environmentally friendly. Due to environmental concerns over cyanidation in hydrometallurgy, considerable attention has been dedicated to alternative non-cyanide solutions for refractory gold mineral leaching. Nitric acid has been recognized as one of the most promising reagents to pre-treatment process, and reduce cyanide consumption by refractory gold concentrates. The nitric acid leaching process is advantageous in that it can produce highly oxidizing conditions and is therefore an effective leaching agent for most sulfides [10]. However, a disadvantage of the nitric acid leaching process is the oxidation of sulfide, both to elemental sulfur and sulfate, in many cases in almost equal parts. This results in an increase in reagent consumption and the necessity of handling sulfate [10,13].

The use of microwave-assisted leaching processes has several advantages, including reduced energy consumption and elevated reproducibility [15,16]. These characteristics are the main drivers of metal ions in complex sulfide minerals. For example, selective leaching was successfully applied to lead smelting residues. Kim et al. (2017) reported that, when microwave assisted extraction (MAE) and autoclave leaching were performed to solubilize other valuable metals (Cu, Ni, Zn) from the matte, MAE has higher oxidation power than autoclave leaching [11]. This can explain the higher conversion of Fe sulfides to Fe oxides compared to autoclave leaching, as well as the higher leaching efficiency of Cu, Ni and Zn from their sulfides. Moreover, MAE is a simple process that can save energy and processing costs. Microwave heating has also been applied by Choi et al. [17] to perform pre-treatment, followed by a thiourea leaching step for gold extraction from gold concentrate. Due to the many advantages of microwaves, they have been widely used in mineral pretreatment. The main purpose of this work is to investigate the leaching behavior of the metals As, Cu, Fe, Zn, and Pb and passive layer decomposition in the refractory gold concentrate associated with nitric acid leaching under various conditions, using a microwave system. Furthermore, to increase the recovery of gold, nitric acid was used during microwave-assisted leaching.

#### **2. Materials and Methods**

#### *2.1. Refractory Gold ore and Concentrates*

The refractory gold ore and concentrate were obtained from a gold mine in Haenam, Korea. Refractory gold ores, including sulfide minerals such as pyrite and chalcopyrite, were used to investigate the influence of mineralogical characteristics on nitric acid leaching. A polished section of the ore mineral was prepared and studied microscopically under reflected light, to identify mineralogical properties. Polished sections were prepared by placing refractory gold ore in an epoxy resin which, after curing, was polished to ensure flatness. The textures of pyrite in the gold ore were investigated using nitric acid etching. The etching method involves the application of a few drops of 65% nitric acid on the polished mounts.

The refractory gold concentrate was obtained through a flotation process. The mineral composition of the refractory gold concentrate was analyzed using XRD. The chemical characterization of the surface species was performed using X-ray photoelectron spectroscopy (XPS). Gold is an element with a severe nugget effect [7,18], which may cause errors in the analysis based on the sampling process. To minimize this, the whole sample was sufficiently mixed and the sample was prepared using the cone and quartering method. To determine the chemical composition of the refractory gold concentrate, the sample was digested with aqua regia. The solution chemistry was analyzed using ICP-OES. The content of gold was analyzed using a fire assay [19,20].

#### *2.2. Leaching Experiment*

#### 2.2.1. Microwave-Assisted Leaching: Effect of Nitric Acid Concentration and Temperature

The samples were sieved through a < 170 mesh screen. For the leaching experiment of the refractory gold concentrate, a microwave system (2.45 GHz, MARS 6, CEM Corporation, Matthews, NC, USA) was used. The microwave system was equipped with a digital temperature control sensor, which allowed the temperature to be accurately measured in real-time. The leaching experiments were conducted at different temperatures (40, 80, and 120 ◦C) and nitric acid concentrations (0.1, 0.5, and 1.0 M). Each leaching experiment consisted of several heating steps to reach a set temperature. A 100 mL disposable Teflon vessel containing 20 mL of HNO3 at various concentrations and 1.0 g of the refractory gold concentrate was heated in the microwave. At the end of the reaction, the microwave system was switched off and the reactor was allowed to cool to room temperature. The oxidation and reduction potentials of the leaching solution were measured using an ORP (Orion 3-Star, Thermo Fisher Scientific, Santa Clara, CL, USA) meter. The leaching solution was filtered through a syringe filter. The weight of the leach residue was measured after leaching. The solution was analyzed by ICP-OES. Each experiment was performed in duplicate. The amount of metal ions leached was calculated using the following equation:

$$\mathcal{L} = \frac{\mathcal{M}\_1}{\mathcal{M}\_0} \times 100\tag{1}$$

where L is the leaching percentage of metal ions, *M*<sup>0</sup> is the metal ion content of the sample before leaching, and *M*<sup>1</sup> is the metal ion content of the sample after leaching.

The rate of metal ion leaching was determined using the following equation [17]:

$$\mathbf{E} = E\mathbf{i}\left(\mathbf{1} - e^{-kt}\right) \tag{2}$$

where E (%) is the metal ion concentration in the leaching solution at time t, *E*<sup>I</sup> (%) is the maximum concentration of metal ions, and *K* (min<sup>−</sup>1) is the leaching rate constant.

## 2.2.2. Microwave-Assisted Leaching: Recovery of Gold

Microwave-assisted leaching was performed by heating a 500 mL Pyrex glass containing 200 mL of nitric acid (1.0, 3.0, and 5.0 M) and 20 g of the refractory gold concentrate. Figure 1 shows the schematic of the laboratory-scale microwave-assisted leaching developed in this study. The flask was placed in the center of the microwave oven and heated. The processing time was set to 15 min for all experiments. After the reaction period was over, the contents were cooled to ambient temperature and removed for solid-liquid separation. After each leaching experiment, the leach residue was filtered through filter paper and the content of gold in the leach residue was analyzed by fire assay. The weight of the leach residue was measured after leaching.

**Figure 1.** Schematic diagram of microwave-assisted leaching system.

#### *2.3. Characteristics of the Residue*

The leach residues obtained were analyzed by XPS and XRD to determine the surface arsenic, sulfur, and iron species and the mineralogical composition, respectively. Morphological studies were carried out on the leach residue using SEM-EDS (Scanning Electron Microscopy-Energy-dispersive X-ray spectroscopy) (S4800, Hitachi, Matsuda, Japan).
