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Mining, Metallurgy & Exploration

, Volume 36, Issue 1, pp 199–213 | Cite as

A Review of Nickel, Copper, and Cobalt Recovery by Chelating Ion Exchange Resins from Mining Processes and Mining Tailings

  • Amilton Barbosa Botelho JuniorEmail author
  • David B. Dreisinger
  • Denise C. R. Espinosa
Review Article
  • 56 Downloads

Abstract

Copper and cobalt can be found on nickel laterite ores, and cobalt can be found also on copper ores, and many contaminants such as iron, aluminum, and magnesium are associated with these ores. In hydrometallurgical process, a purification step is necessary after leaching due to the presence of these impurities. Chelating resins are more selective for some metals than others, making them more efficient than cationic resins. This overview discusses chelating resin applications to recover copper, nickel, and cobalt from mining process and mining tailings and the effect of contaminants in leach solution. Chelating resins with iminodiacetate functional group can be used for selective copper recovery, and both iminodiacetate and bis-picolylamine resins are highly selective for nickel and cobalt. Chelating resins with the same functional group can have different performances on the kinetics of loading, because of variations of structure, the density of functional group, and degree of cross-linking. This article reviews commercial chelating resins that can be applied in leach solutions with different compositions, and also possible innovations for uses of chelating resins to recover metals from mining process and mining tailings.

Keywords

Iminodiacetate bis-Picolylamine Resins 

1 Introduction

Hydrometallurgical processes consist of extraction of metals by heterogeneous reactions (leaching process), which in solid phase interacts with liquid (leaching agent), and the solid is dissolved [1, 2, 3]. The term can be applied for dissolution of secondary materials such as scrap, residues, and wastes. After initial preparation of resources, which may involve crushing or grinding to desired size, the dissolution step comprises addition of leaching agent, that in most cases are acids. For mining processes, most impurities can be removed from concentrates or ores by leaching (hydrometallurgical beneficiation). Many different leaching processes can be applied for each resource; generally, sulfuric acid is used as leaching agent. A purification step is used to remove impurities present in solution; then, a separation step is necessary to recover the desired metal or metals, because leaching step is neither selective nor perfect and many contaminant constituents are present in solution [1, 4, 5, 6, 7, 8, 9].

The best method to recover metals from leach solution depends on conditions of leach solution (pH, composition, concentration of metals). Among these processes can be cited chemical precipitation [10], electrowinning [11], solvent extraction [12, 13], and ion exchange resin [14, 15]. Considering precipitation reactions, hydroxides are used due to the low price and easy application; however, as Jimenez Correa et al. (2016) presented, iron removal to purify the solution from nickel laterite leaching using KOH, copper, and cobalt is also precipitated with iron (coprecipitation). Iron hydroxides reacted with copper and cobalt due to its high concentration and chemical affinity [16]. Chang et al. (2010) studied iron removal from liquor of nickel laterite by goethite precipitation using air as oxidant agent, whose losses of nickel were identified in all pH studied [17]. Other options of precipitation can be also used, as Botelho Junior et al. (2018) studied the recovery of copper from nickel laterite leach solution, where in reducing the potential using sodium dithionite as reducing agent, it was possible to perform a selective precipitation [18]; however, sodium dithionite can dissociate in acidic medium to sulfur and hydrogen sulfide, the latter being extremely toxic [19, 20, 21, 22]. For this reason, for solutions with high presence of contaminants, losses of valuable metals such as nickel, copper, and cobalt must be considered.

Solvent extraction is a classic separation of cobalt from nickel-rich solution, after a purification process. In hydrometallurgical process of nickel laterite from limonite ore, purification by precipitation and concentration of the solution is required before solvent extraction separation, and then electrowinning is used to produce 99.9% pure nickel and cobalt [11, 23].

Ion exchange process using resins can be explained as a reversible process involving an exchange of ions between an electrolyte solution (aqueous phase) and resin (solid phase). The most important difference between ion exchange resins and solvent extraction is that the first is a solid-liquid separation, and the second is a liquid-liquid separation. In industrial processes, solvent extraction is used when other separation processes are not enough to recover metals in solution. Both must have similar charges to be changed [24]. Equation 1 presents the reaction of ion exchange, where the cation A+ in the functional group of cationic resin exchange with the cation M+ in the solution. For anionic resins, anion present in solution will exchange with anion present in the functional group of resin [25].
$$ {\mathrm{R}}^{-}{\mathrm{A}}^{+}+{\mathrm{M}}^{+}\leftrightarrow {\mathrm{R}}^{-}-{\mathrm{M}}^{+}+{\mathrm{A}}^{+} $$
(1)
The functional groups give the characteristics to the resins, such as acid, basic, or chelating. There are four main types differing in their functional groups, strongly acid, strongly basic, weakly acid, and weakly basic [24], as presented in Table 1. These functional groups are mostly used for ion exchange resins. These polymeric resins must be insoluble and can swell to a very high degree, where ions migrate within the polymeric network. Different polymer chains have to be cross-linked with each other forming a three-dimensional polymeric structure. The cross-linking is usually performed with short hydrocarbon bridges [29].
Table 1

Functional groups of ion exchange resins and their molecules

Within the group of ion exchange resins, there are the chelating or ligand exchange resins, as a subgroup of ion exchange resins. These resins are similar with common ion exchange resins: insoluble in water by cross-linked matrix and functional groups. The functional groups of these resins representing the ligands required for metal complexation coordinate bond interaction or electrostatic interactions. Nitrogen, oxygen, sulfur, and phosphorous are the most common atoms in functional groups. Transition metal ions tend to surround themselves with molecules or ions having a lone pair of electrons. These ligand species donate their electron pairs to the central ion, establishing covalent-like bonds, called coordination bonds [29]. The advantage of using a chelating resin is the high selectivity for some metal in comparison to another, that is based on the different stabilities of metal complex at appropriate pH value [24, 30, 31]. Figure 1 shows three different chelating resins (iminodiacetate, aminophosphonic, and bis(2-pyridylmethil)amino) complexing a metal M (II). Nitrogen and oxygen react with the metal in solution establishing coordination bonds.
Fig. 1

Complexing metal (II) of functional groups: iminodiacetate group (a); aminophosphonic group (b); bis(2-pyridylmethyl) amine (c) [32, 33]

For industrial processes, batch or column operations are mainly used. For batch process, resin and solution are mixed in a tank, and after exchange reaction reach the equilibrium, the resin is separated from solution by filtration; however, the resin’s capacity is limited, because the ion exchange is limited, which limits the potential for industrial applications. In column process, a fixed-bed column is the most used for industrial operations, because it works on the limitation of selectivity of the resin. More than um stages, or columns, can be used to obtain a high selectivity (multicolumn system), where the output of the first column is the input of the second, and successively. There are three column operation modes are available: down and up flow and counterflow [24].

There are two main models that can be used to understand the equilibrium metal adsorption: fitted to Langmuir and Freundlich models of adsorption [24]. Langmuir isotherm assumes that a resin’s surface is a finite of equivalent adsorption sites and the maximum adsorption is obtained when all sites are filled, applicable to the homogeneous system. Freundlich isotherm is an empirical equation, which describes adsorption based on heterogeneous surface, applicable to the heterogeneous system and not restricted to the formation of the monolayer [30, 32].

Due to the advantages of ion exchange resins and chelating resins applications—high capacity for the metal species of interest, fast reaction kinetics, efficient elution, and service life durability [34]—they are being applied to recover metals in the mining process, both in process from ores and tailings in many different mining areas [7, 34, 35, 36, 37, 38, 39, 40, 41]. The goal of this work was to offer an overview of nickel, copper, and cobalt recovery using chelating resins from different types of solution, mainly in hydrometallurgical applications from ores and tailings. For each metal, an overview about resources, mine production, and hydrometallurgical process is discussed. A review about chelating resin applications and new technologies developed is presented; furthermore, kinetics and the importance of contaminants, which decreases the efficiency of resin, are also described.

2 Nickel

2.1 Nickel Resources and Production

Nickel and cobalt can be recovered at the same time from nickel ores. For some of them, it is also possible to recover copper, depending on the resource. There are two main types of nickel resources in nature: laterites and sulfides. Laterite ores consist of 70% of all resources, while nickel production from this ore represents only 40% [23]. Nickel production from laterite ores is more complex than that from sulfides that requires extensive treatment to extract nickel, and has been more expensive that from than sulfide ores, which also needs a drying step due to high moisture content [42, 43, 44]. Despite these differences, there are mining processes that have been developed to extract nickel from laterite ores, in which total costs are getting equal to and being more competitive than sulfide ores [45], and with demand for this metal increasing and declining discovery/production of sulfide deposits, it will be necessary to increase production from laterite ores [46].

Production from sulfide ores is by pyrometallurgical process [23]. Laterite ores can be divided into three main layers: limonite, transition, and saprolite. Limonite and transition are processed by hydrometallurgical processes, and saprolite by pyrometallurgical process due to the low iron content [23, 47]. There are two main hydrometallurgical processes: high-pressure leaching (HPAL) and atmospheric acid leaching (AAL). HPAL is applied for limonite layers that are leached with hot sulfuric acid in titanium autoclaves at temperatures of 245–250 °C and 40 bar, and nickel and cobalt are recovered from solution by precipitation and concentration of solution and, then, by purification process, where can be used ion exchange resin. The difference between HPAL and AAL is the last one occurs on atmospheric pressure. Caron process is both pyrometallurgical and hydrometallurgical and can be applied on limonite and transition layers. This process comprises a drying and calcine/reduction step first (pyrometallurgy), and then a leaching process using ammoniacal solution. Ion exchange technique can be applied in the next step, when the purification process is required [5, 23, 42, 47, 48, 49, 50].

2.2 Chelating Resin Applications

Chelating Functional Group Iminodiacetate

The main advantage of the use of chelating resins is the selective metal recovery in a solution with the presence of many different metals. The choice of the better resin depends on the metal that would like to be recovered, and also the metals present in solution. Iminodiacetate chelating resins are widely used due to the high selectivity for Cu(II), Ni(II), Co(II), and Zn(II) [51], and this functional group had same behavior of ethylenedi-aminetetraacetic acid (EDTA) chelating agents [26]. Stefan and Meghea (2014) studied adsorption mechanism of Ca(II), Ni(II), Pb(II), and Al(III) using Purolite S930. In pH 6.5, it was verified higher recovery of metals than in pH acid (3.03) for mono-elementary system, and Freundlich isotherm better represents Ni(II) adsorption mechanism for pH 6.5. In experiments with multi-elementary system, maximum adsorption was verified at pH 4.45, and the order of selectivity was Ni(II) > Pb(II) > Al(III) > Ca(II) [52].

Kuz’min and Kuz’min (2014) studied the metal adsorption from the Kingashsky low-grade non-ferrous metal sulfide ore leach pulps using Purolite S930, in order to assess the conditions for Ni(II) recovery, comparing the results obtained from synthetic solutions. Ni(II) recovery reached equilibrium after 60 min, and pH 2.5 had better result to recover this metal (92–95%) for synthetic solutions. Comparing with solution after leaching process of sulfide ore, Ni(II) recovery reached 99%, as well as other metals like Cu(II) and Co(II), due to the chelating resin selectivity; however, impurities such as Zn(II), Mg(II), Ca(II), and Na(I) were practically not adsorbed, indicating that most impurities are not adsorbed by this resin [53].

Zainol and Nicol (2009) studied five different chelating resins with iminodiacetate functional group: Amberlite IRC748, Lewatit TP 207, Lewatit TP 208, Purolite S 930, and Lewatit TP 207 Monoplus to recover Ni(II) from leach mining tailings of nickel laterite. Effect of impurities was analyzed in batch experiments, and column experiments were performed to study continuum process of Ni(II) recovery. According to the results obtained, the performance of the five resins was not identical, in spite of all of them having the same functional group. These differences were possibly caused by variations occurring in the synthesis procedure, resulting in variations in the structure of the matrix, degree of cross-linking, density, proportion of functional group, and particle size. The resin that had better performance was Lewatit TP 207 MonoPlus for loading capacity of Ni(II) and also the kinetics of adsorption [54].

Littlejohn and Vaughan (2014) studied the selective elution of Ni(II) using ammoniacal solution and effect of impurities as iron, aluminum, chromium, manganese, calcium, and magnesium. Chelating resin used was Lewatit MonoPlus TP 207 XL. An important step on the column process is the elution, where acid solutions are used to remove the ions previously adsorbed by the resin. The authors investigated the difference of ammonium sulfate and ammonium carbonate as eluents, and results showed ammonium sulfate results in higher efficiency on elution process than carbonate, probably due to the overall lower solubility of nickel carbonate and other metal carbonates compared to their sulfate counterparts. Studying the influence of cations in elution process, all three cations analyzed (Ca(II), Mg(II), and Mn(II)) improved the Ni(II) elution. Comparing desorption with sulfuric acid, the reaction with ammoniacal solution was slower than using sulfuric solution (120 min for ammoniacal solution and 30 min for sulfuric solution), even using ammoniacal solution and Mg(II). Experiments to test selectivity of elution step were realized in order to simulate the real solutions of nickel laterite leach with the presence of other metals as contamination. Despite the presence of Al(III) and Fe(III) in loaded solution, solution after elution step had less than 10 mg L−1 of Al(III) and less than 1 mg L−1 of Fe(III), while Ni(II) recovery reached 89%. Authors verified in this study the importance of each component of elution solution: ammonia to complex the desorbed Ni(II) and Co(II), Mg(II) sulfate to act as a more favorable counter ion for exchange, and ammonium sulfate to maintain the pH [55].

Zainol and Nicol (2009) studied the Amberlite IRC748 resin selectivity in a solution with Ni(II), Co(II), Mn(II), and Mg(II)—metal ions involved in the AAL system—in three different pH values. Langmuir and Freundlich isotherm models were analyzed and results showed that Langmuir isotherms had R2 better in all pH values studied than Freundlich, indicating that metal adsorption was monolayer. The Langmuir equilibrium constant K, which reflects quantitatively the affinity between the resin and metal ions, had the resin selectively at pH 5: Ni(II) (58000) > Co(II) (16800) > Mn(II) (37) > Mg(II) (17), which suggests that resin can easily recover nickel selectively from solution containing cobalt, manganese, and magnesium [30].

Mendes and Martins (2005a, 2005b) studied the selective nickel adsorption using Amberlite IRC748 from HPAL solution of nickel laterite ore. Batch experiments were performed to study the effect of pH, time, stirring speed, and temperature for nickel adsorption. Nickel recovery was maximum at pH 4; a similar result was obtained by Zainol and Nicol (2009), where maximum nickel recovery was at pH 5 [30]. Metal adsorption by ion exchange resins has higher efficiency for higher pH values, due to the competition with H+ and metal ions in solution for the functional groups. However, these studies showed that the resin had high affinity for iron and copper, which should be removed from the solution before ion exchange process [56]. In column experiments, effects of metal concentration in the feed solution and flow rate on resin loading were analyzed. In these experiments, metals such as Ni(II), Co(II), Al(III), Mn(II), and Mg(II) were rapidly adsorbed by the resin and then displaced to the solution (Cf/C0 > 1). Results showed that chelating resin had high affinity for Fe(III) and, mainly, Cu(II). Elution experiments were also performed in order to study the selective nickel removal from the resin, where experiments performed using hydrochloric acid were able to obtain a solution with Ni(II) concentration 12 times higher than feed solution, while using sulfuric acid, Ni(II) concentration on elution step was 3 times than feed solution, and impurities such as Al(III) and Mg(II) were presented in concentration higher than using hydrochloric acid [57].

Chelating Functional Group bis-Picolylamine

In another study, Mendes and Martins (2004) compared three resins with iminodiacetate group (Amberlite IRC748, Ionac SR-5, and Purolite S930) with others with bis-picolylamine group (Dowex M4195) to study Ni(II) and Co(II) adsorption from HPAL synthetic solution. Among metals in solution, Al(III), Mg(II), Cu(II), and Zn(II) were also present. Results show that all resins presented high selectivity for nickel. Dowex M4195 was better for Ni(II) recovery than iminodiacetate resins in all pH values studied. Although three resins had the same functional group, they present different results on metal adsorption [58].

Besides that, Dowex M4195 can be more selective for copper than for nickel. Jimenez Correa et al. (2017) studied Ni(II) adsorption using Dowex M4195 in synthetic solution in order to simulate solution of AL process with sulfuric acid. Batch experiments were performed to study the effect of pH, time, metal concentration, and temperature. In mono-elementary experiments, nickel adsorption equilibrium was reached after 4 h, and ion exchange reaction was favorable with temperature increase. The loading of nickel increased with solution concentration until resin saturation. As present in studies before [30, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62], increasing pH also increases recovery of metals, due to less competition with H+. Comparing mono-elementary results with AL synthetic solution, the presence of other metals decreased resin’s efficiency [63]. The main problem of this solution is the high presence of iron, that it is not possible to increase pH above 2, in as much as it will precipitate with cobalt and copper [16]. A solution for this problem could be the chemical reduction of iron and then increase pH value in order to increase metal recovery [64, 65, 66].

Other Chelating Functional Groups

Li et al. (2012) studied the nickel recovery efficiency using resin NDC-984 with functional group polyamine. The effects of pH and adsorption isotherms were analyzed. As well as studies presented before, nickel adsorption increases with increasing pH. Among isotherm models, the Langmuir model was better fitted than Freundlich model, as well as Zainol and Nicol study (2009) [30]. Experiments performed using mono-elemental solutions showed that resin was more selective for nickel than for cobalt, as well as in multi-elemental Ni(II)–Co(II) experiments, in both batch and column experiments [67]. The chelating resin CuWRAM, which has the functional group 2-(aminomethyl)pyridine, was studied to verify the selectivity for Ni(II) in a solution with the presence of Zn(II) as contaminant. Results obtained showed that nickel adsorption decreased in the presence of zinc [68].

Deepatana, Tang, and Valix (2006) studied two different chelating resins: Purolite S930, with iminodiacetate group, and Purolite S950, with aminophosphonic acid functional group for nickel and cobalt recovery from solution obtained after bioleaching process of low grade of nickel laterite ore. Despite studies using Purolite S930 for those metal recovery [52, 53, 54, 58], the solution contained also chelating agents citric, dl-malic, and lactic acids due to the bioleaching process. Langmuir and Freundlich isotherms indicate that nickel adsorption was a combination of mono- and multi-layer mechanisms for both resins. The nickel adsorption using Purolite S950 was higher than that using Purolite S930, maybe because the chelating reaction with nickel-chelating agent was more stable with aminophosphonic group than with iminodiacetate [69].

3 Copper

3.1 Copper Resources and Production

Copper can be found as oxides or sulfides, but is mainly produced from sulfides, which are, in general, present in deeper deposits and are more expensive to extract and treat, which explain why most companies plan to exploit sulfites after oxide ores are exhausted [23]. Chile is the main mine producer with one third of world production. In 2015, Chile’s production was 5.5 Mt and almost 3 Mt more than second-ranked producer, Peru. China is the third-ranked producer with 1.7 Mt, and the USA is the fourth-ranked producer, 1.4 Mt. The 10 leading producers accounted for 81% of production, and the 20 leading producers accounted for 94% of production [70, 71].

Chile has also the largest amount of copper ore reserves (210 Mt), followed by Australia (89 Mt) and Peru (81 Mt). One tenth of mineral reserves of copper in the world is from Copperbelt, localized in Zambia and Democratic Republic of Congo [70], and studies show several socio-environmental problems of these mines [72, 73, 74, 75, 76, 77, 78, 79, 80, 81]. Hydrometallurgical processes for copper extraction account are performed for the remaining portion of 20% and are commonly used when processing copper oxides [82].

The hydrometallurgical process can be applied for low-grade oxides and also some sulfide ores, and this process comprises the following steps: reductive leaching, where sulfur dioxide gas or sodium metabisulfite can be used as a reducing agent; solid/liquid separation and clarification of the solution; separation of copper and cobalt by ion exchange technique; purification of aqueous solution; precipitation of cobalt hydroxide or electrowinning of cobalt; and copper electrowinning [23, 82, 83]. Sulfuric acid is commonly used as leaching agent [84, 85], but studies had been developed to use hydrochloric acid as leaching agent [86, 87, 88]. After leaching step, ion exchange technique is used to recover copper selectively from solution. The main technique used is solvent extraction, but ion exchange resins are also applicable. Biohydrometallurgical process is also studied [89].

3.2 Chelating Resin Applications

Chelating Functional Group Iminodiacetate

Studies using chelating resins with functional group iminodiacetate are largely used due to the high selectivity for copper, as well as for nickel as presented before. Ma et al. (2014) [90] and Siu et al. (2015) [91] studied copper recovery using D401 chelating resin. In both studies, at pH 4, copper adsorption was maximum after reaction reached the equilibrium. Among isotherms studied, Langmuir model, which indicated maximum monolayer copper ion exchange capacity of the resin, and Sips model (or Langmuir–Freundlich) were the best fitted.

Siu et al. (2015) studied the following kinetic models: pseudo-first-order equation, pseudo-second-order equation, Elovich equation (which depicts an exponential decay of the adsorption rate with time), and Ritchie equation (which assumes that the rate of adsorption depends only on the fraction of sites unoccupied). Results showed that copper adsorption reached the equilibrium after 500 min and pseudo-second-order model gave better correlation to the experimental data curves than other kinetic models. Results of effect of resin mass, performed between 0.9 and 1.7 g, showed that model curves were very close to each other [91].

Moreover, Ma et al. (2012) [90] studied copper adsorption in fixed bed column breakthrough curves. Results showed that adsorption capacity decreases more significantly for large flow rates, due to the residence time available for this ion exchange process to take place is less. Gando-Ferreira et al. (2011) studied selective recovery of copper using Diaion CR11 for copper adsorption, where chromium was also present in solution as contaminant. Copper adsorption was higher at pH 5 than at pH 2 and 3, as expected—the maximum capacity, qmax, increased 2.3 times when the pH changed from 2 to 5 at 25 °C, where Cu(II) recovery was 97% with 1 g of resin. In this study, temperature increased copper adsorption. In column experiments, saturation curves show Cu(II) was strongly adsorbed by the resin, more selectively than Cr(III), as mathematical model showed [92].

Bleotu et al. (2015) studied chelating resin S930 to recover copper from sulfuric medium in aqueous solution. In this study, effect of stirring speed was analyzed, and no difference was detected between 200 and 400 rpm, but in 500 rpm, copper adsorption was higher than in other stirring speeds. As well as presented in studies before, at pH 4, the metal adsorption was maximum. Temperatures between 25 and 50 °C had no influence in ion exchange reaction. The isotherm that better fitted was Langmuir isotherm, and results indicated that copper adsorption can be explained by pseudo-second-order kinetic model. The influence of Ni(II), Zn(II), and Fe(II) was studied and, according to the authors, S930 resin had results comparable with other chelating resins with iminodiacetate group following the selective order: Cu(II) > Ni(II) > Zn(II) >> Fe(II) [93].

In another study using resin S930, Kuz’min and Kuz’min (2014) studied copper recovery from pulps derived from the leaching of low-grade sulfide ores by hydrochlorination. Results using synthetic and real solutions were compared (metals such as Fe(III), Co(II), Mg(II), and Ni(II) were also present), and results indicated that Cu(II) had more exchange capacity by the resin than nickel, and at pH 2.5, copper was recovered in 99%. Cu(II) and Ni(II) were recovered selectively, and a few percentage of Co(II), Fe(III), and Zn(II) were also recovered. Mg(II) was practically not adsorbed by the resin [53].

Fadel et al. (2016) studied Cu(II) recovery from solution with Ni(II), Hg(II), and Co(II). In this study, the chelating resin was synthesized by acrylamide—N,N-methylenebisacry-lamide (CPM) copolymers. Anion exchangers with the primary amine groups were obtained by the transamidation reaction of CPM resin with ethylenediamine. Then, the chelating resin was prepared by the reaction of the primary amine groups with sodium monochloroacetate. Experiments to study the effect of pH were performed between 2 and 6, which at pH 5.5 there was maximum adsorption of copper. Experiments to study the equilibrium isotherm models showed that the metal ion adsorption order was Cu(II) > Ni(II) > Co(II) > Hg(II), that maybe it was related to the difference in ionic radius of these ions, where Cu(II) is the smallest radius of the other ions. The Langmuir isotherm had better correlation coefficient to explain metal adsorption. Copper adsorption reached the equilibrium after 35 min, and temperature had slight influence in copper adsorption, indicating that the reaction is endothermic [94].

Chelating Functional Group bis-Picolylamine (or 2-(Aminomethyl)pyridine)

Due to the electron withdrawing effect of the aromatic group, the nitrogen atoms of this functional group remain deprotonated even at pH of 1.5 [33]. Neto et al. (2016) used Dowex M4195 to recover selectively copper from electronic waste (e-waste). Synthetic solution containing Cu(II), Ni(II), Fe(III), Pb(II), Al(III), Zn(II), Ag(I), and Sn(II) was prepared to study the selectivity of chelating resin using adsorption isotherms and kinetics in batch and column systems. In isotherm studies, Langmuir isotherm fitted better than Freundlich, indicating that copper adsorption was a monolayer adsorption. Adsorption kinetics experiments indicated that copper adsorption was described by a pseudo-second-order kinetics and suggest that chemisorption is probably the rate-determining step. According to the authors, copper recovery by column process is possible because it is a simple and low-cost operation, fast and with high recovery percentage [95].

The same resin M4195 was compared with Lewatit TP 220 for copper recovery. Results showed that there was no difference between both resins in pH range 1–5, and reaction reached the equilibrium after 10 min. Copper adsorption was fast twice in sulfate medium using Lewatit MonoPlus TP 220 and three times using Dowex M 4195 than chloride medium, which is important for mining processes, since sulfuric acid is used for leaching process [33]. In another study, Wołowicz and Hubicki (2012) studied selective recovery between noble metals (Pd(II), Pt(IV), and Au(III)) and base metals (Cu(II), Co(II), Ni(II), and Zn(II)) using resin Lewatit MonoPlus TP 220. Results showed that noble metals were recovered more selectively than base metals. However, considering only the base metals, resin was more selective for copper. The selectivity order was Pd(II) > Au(III) > Pt(IV) > Cu(II) > Zn(II) > Co(II) > Ni(II) [28].

Laatikainen et al. (2010) studied chelating adsorbent CuWRAM to recover copper from hydrometallurgical zinc extraction process. Results showed high efficiency for Cu(II) recovery in the presence of Zn(II) excess and presence of other contaminations, such as Mg(II), Mn(II), Cd(II), Ni(II), and Fe(III). In fixed-bed experiments, Zn(II), Ni(II), Co(II), and Cd(II) reached rapidly the equilibrium (breakthrough), while Cu(II) had been recovered until reaching equilibrium [96].

Other Chelating Functional Groups

Chen et al. (2007) synthesized a porous chelating resin cross-linked poly(glycidyl methacrylate-glycine) (PGLY) to recover Cu(II), Ni(II), and Cd(II). Results showed that the reaction reached the equilibrium after 40 min, and the equilibrium was higher for Cu(II) than for Ni(II) and Cd(II), attributed to the hydrophilic nature of hydroxyl (−OH−), amine (−NH−), and carboxylate (COO−) groups in PGLY, which had an adequate affinity for metal ions. Freundlich isotherm fitted better for Cu(II). The metal adsorption increased while pH increased until pH 4, when reaching equilibrium. The selectivity order was Cu(II) > Ni(II) > Cd(II) [97].

Lutfor and Mashitah (2011) synthesized chelating resin with poly(hydroxamic acid)-poly(amidoxime) group in order to remove metals (Cu(II), Co(II), Cr(III), Mn(II), Fe(III), Ni(II), Zn(II), Pb(II), and Cd(II)) from two industrial wastewaters: chromium plating wastewater and cyanide process. The adsorption results showed that chelating resin was more selective for copper than for other metals (Cu(II) > Fe(III) > Zn(II) > Cr(III) > Ni(II) > Co(II) > Cd(II) > Pb(II)). Column experiments using chromium wastewater showed that chromium was recovered in 99.0%, while copper, cobalt, manganese, iron, nickel, zinc, lead, and cadmium were in 99.0, 99.1, 99.6, 94.0, 94.0, 90.0, 80.2, and 88.1%, respectively, at pH 4. For cyanide wastewater, nickel and zinc recoveries were 94.0 and 88.1%, respectively, and copper, cobalt, chromium, manganese, iron, lead, and cadmium were 99.4, 99.6, 96.0, 95.0, 92.0, 92.1, and 93.2%, respectively [98].

Diogo et al. (2011) synthesized four resins with amidoxime chelating group. According to the authors, concentration and distribution of amidoxime groups in the polymer matrix influenced the copper adsorption, as well as studies comparing different resins [54]. The metal was clustered by the resin and improved by two factors: high pore diameter and high amidoxime group content of the chelating resins [99]. Meanwhile, Shaaban et al. (2014) synthesized a resin with amidoxime chelating group and studied Cu(II), Ni(II), and Pb(II) adsorption. The resin was more selective for Cu(II) than for Ni(II) and Pb(II), where maximum copper adsorption was at pH 5.4, reaching the equilibrium after 40 min. Langmuir isotherms better fitted for all metal adsorption [100]. In another study, El-Bahy and El-Bahy (2016) synthesized a polyamidoxime chelating resin and studied the adsorption of Ni(II), Cu(II), and Mn(II). For this new resin, the same feature was observed, and Cu(II) was more selective than Ni(II) and Mn(II) [101].

Liebenberg et al. (2013) studied the metal adsorption using resin Dow XUS43605 with hydroxypropylpicolylamine (HPPA) chelating group from a leach solution obtained from a heap bioleach of nickel low-grade ore. Resins Dowex M4195 (bis-picolylamine), Amberlite IRC748, Purolite S930 (iminodiacetate), and Purolite S991 (amine/carboxylic) were also studied. A synthetic solution was prepared in order to simulate the real conditions: Cu(II), Ni(II), Co(II), Fe(III), Zn(II), Mn(II), and Al(III). Resin was more selective for Cu(II), where temperature had no effect on metal adsorption. Langmuir isotherm fitted better for copper adsorption than Freundlich. Column experiments showed that there is no difference between flow rates studied, but at increasing temperature, the breakthrough of copper occurred at a higher BV (bed volume) at 60 °C than at 25 °C, indicating that this resin operates better at elevated temperature. Sulfuric acid (200 g L−1) was better for elution step to remove Cu(II) from resin [102].

Edebali and Pehlivan (2016) compared four different resins for copper adsorption: two chelating resins (Dow XUS43578 and Diaion CR11 with bis-picolylamine and iminodiacetic acid as functional group, respectively) and two strong acid cation exchanges (Dowex HCR W2 and Purolite C160 with sulfonic acid and sulfonate as functional group, respectively). For all resins, copper adsorption reached the equilibrium in 80 min, and resins had the same feature for different pH values, except XUS 43578 at pH 1.5 that it had more copper recovery than other resins. The maximum metal adsorption was at pH 5 with 97% of copper adsorption. All resins fitted better for Langmuir isotherm, indicating copper adsorption was monolayer. Chelating resins were more efficient for copper recovery than cationic resins, probably due to the strong affinity for copper ions [26].

4 Cobalt

4.1 Cobalt Resources and Production

Cobalt is used globally for rechargeable batteries, increasing battery life and stability and reducing corrosion, which are used in mobile cellphones and portable computers, and in hybrid and electric vehicles. In 2010, about one half of the cobalt consumed in the USA was used in the manufacture of superalloys, used in gas turbine and for aircraft, space vehicles, chemical and petroleum plants, and power plants. Another cobalt property is impressive magnetism that is retained at temperatures over 1121 °C, which is applied in computer disc drives and in electric motors, for operations more efficiently at high temperatures [103]. There are also cobalt applications for military uses [104].

Cobalt is extracted as by-product from copper and nickel mining: more than 90% of cobalt is from cobalt–copper and cobalt–nickel mines, and 5–10% comes from cobalt–copper–nickel mines [105]. There are three main cobalt deposits: sediment-hosted stratiform copper deposits (African Copperbelt, Democratic Republic of the Congo (DRC) and Zambia), magmatic nickel sulfide deposits (Sudbury, Canada, and Norilsk, Russia), and nickel laterite deposits (tropical regions such as New Caledonia) [103, 106, 107].

In 2008, almost 50% of cobalt production came from mines where nickel was the main product; 35% where copper was main product; and 15% where cobalt was main product recovered from mining operations, metal scrap, and slag. Between 1995 and 2008, cobalt production almost tripled due to increased demand for cobalt in rechargeable batteries and super alloys. Much of increased production came from Congo, after cessation of regional conflict, leading to an increase in non-traditional artisanal mining of heterogenite ore after 1999 [104].

The largest cobalt reserves occur in the Copperbelt of Congo (Kinshasa) (3400 Mt), supplying one half of world cobalt mine production, and Australia is the second largest (1000 Mt). The largest producer is Congo (Kinshasa) (66 Mt), and second China (7.7 Mt) [108], being the last had increased refine cobalt production capacity from 1% in 1995 to 31% in 2008 of world capacity, inducing high dependency of imported sources in various forms of concentrate and intermediate products [104].

Between 1999 and 2008, cobalt production from Congo increased from 7 to 41% of global production, while Zambia decreased from 24 to 9%, Canada from 22 to 11%, and Russia from 14 to 8%. By 2013, it was expected that about 40% of copper supply will come from the African Copperbelt; 38%, from Australia and the South Pacific countries of the Philippines, Indonesia, New Caledonia, and Papua New Guinea; 11%, from other African countries; 5%, from North America; and 6%, from other areas. Chinese companies are increasingly becoming involved in copper and cobalt exploration and mining in Congo (Kinshasa) and Zambia, as well as nickel, copper, and other mining in Australia and the South Pacific [104].

Since cobalt had high end-of-life recycling rate and because in-use stocks of cobalt have been growing continuously, rising amounts are expected of Co-containing scrap in the future [105]. Studies have been developed to understand the risks of human exposure of cobalt in mining processes, mainly in Congo and Zambia [109, 110]. As the extraction of cobalt is associated with nickel and copper, ion exchange resins, as well as solvent extraction, can be applied to recover cobalt selectively [23].

4.2 Chelating Resin Applications

Chelating Functional Group Iminodiacetate

Dinu and Dragan (2008) studied the synthesis of chelating resin with iminodiacetate group. Adsorption experiments for Cu(II), Ni(II), and Co(II) were compared with commercial iminodiacetate resin Amberlite IRC748. Acrylonitrile-divinylbenzene copolymers were prepared in the presence of toluene as porogen, by suspension polymerization technique. Two chelating resins were synthesized: CR-10, being characterized by smaller specific surface area and pore total volume than CR-15, another resin synthesized. Co(II) adsorption model isotherm was more fitted by Freundlich model than by Langmuir, and adsorption decreased if temperature increased. Among metals studied, Co(II) was less selective for resins than Ni(II) and Cu(II) [111].

In another study, Dragan et al. (2009) synthesized chelating resin with iminodiacetate functional group and studied the complex forming with the same metals. The resin was derived from acrylonitrile-divinylbenzene copolymers and prepared using anion exchangers with primary amine groups obtained by the aminolysis–hydrolysis reaction of the nitrile groups with ethylene diamine, and then the chelating resin with iminodiacetate ligand was prepared by the reaction of the primary amine groups with sodium monochloroacetate. Adsorption experiments were performed at room temperature, pH 5.5 during 24 h. Results indicated that Cu(II) was the metal with which resin had more selectively, followed by Co(II) and Ni(II) [112].

The studies performed using iminodiacetate chelating resins from laterite leach tailings indicated that those resins were more selectively for Ni(II) than for Co(II). For this reason, the first step to recover both metals selectively could be recover nickel and, then, recover cobalt [30, 54]. McKevitt and Dreisinger (2012) studied chelating resin Lewatit TP 207 for Ni(II), Co(II), and Cu(II) adsorption, in order to develop an engineering model to describe the rate of loading of metals onto an iminodiacetic ion exchange resin. The resin had more selectivity for Cu(II), followed by Ni(II) and, then, Co(II) [113].

Chelating Functional Group Aminophosphonic

Deepatana et al. (2006) studied two resins with different functional groups (iminodiacetate and aminophosphonic) for Ni(II) and Co(II) recovery from bioleaching of nickel laterite ores. As presented before, both resins were more selective for Ni(II) than for Co(II) [69]. In another study using chelating resin with aminophosphonic functional group, Deepatana and Valix (2006) studied metal adsorption mechanisms of metal–organic complexes (citrate, malate and lactate) onto Purolite S950 resin, generated by bioleaching nickel laterite ores. Results showed that adsorption isotherm for Co(II) fitted better by Langmuir isotherm, while for Ni(II) fitted better by Freundlich isotherm. Adsorption of these metals complexed with citrate, malate, and lactate ligands was generally low in comparison to metals complexed with sulfate or hydrated metals from aqueous solutions, attributed to the bulky organic ligands which promoted crowding effects or steric hindrance to adsorption sites [114]; similar results were obtained in another study developed by the same authors [115].

Other Chelating Functional Groups

Badawy et al. (2013) used chelating resin with amidoxime functional group to recover Co(II) from waste mobile phone batteries. At pH 5.5, a maximum recovery of Co(II) (~ 100%) was possible in comparison of other pH values, reaching the equilibrium after 30 min [116]. Littlejohn and Vaughan (2013) studied resin TP 220 with bis-picolylamine functional group in a solution from ammoniacal elution of Ni(II) laterite ore, in order to reduce impurities also adsorbed by iminodiacetate resins. Ni(II) recovery was greater than 95% and Co(II) over than 80%, evidencing higher selectivity for Ni(II) than for Co(II). The most significant impurity was Fe(III), due to the resin selectivity for iron is higher than cobalt, but lower than nickel. However, during loading step, Fe(III) can be displaced by Ni(II) [117].

Vaughan et al. (2016) studied Co(II) and Ni(II) adsorption using chelating resin Lewatit TP 272 with bis(2,4,4-trimethylpentyl) phosphinate functional group. The TP 272 is called “solvent impregnated resin,” which combines the engineering advantages of ion exchange resin with the enhanced chemical separation factors of solvent extraction. This kind of resin is a macroporous polymeric bead with a solvent adsorbed on the surface and within the pores. The main disadvantage is the high sensitivity for degradation by solvation or leaking of the organic if exposed to aqueous solution at neutral or alkaline pH, resulting in a more rapid loss in capacity than conventional cation exchange resin and can cause practical challenges around pH control in the system if the operating pH is near neutral. The highest recovery of Co(II) was at pH 6, and results show that resin is more selective for Co(II) than for Ni(II) in pH 4.8–6.0 [118].

5 Discussion

Table 2 presents a summary of functional groups presented before. The leaching process could be applied in the mining process to obtain nickel, copper, and cobalt from ores, where purification step is required due to the presence of impurities. Among these complex mixtures of several metals, a selective recovery is the key for a suitable separation process. One of the advantages of chelating separation materials is the high selectivity [96]. Nickel and copper ores have high concentrations of iron, aluminum, manganese, and magnesium, and they are also present in solution obtained after the leaching process. So, the use of chelating resins to recover metals has a great advantage [14, 56, 57, 63].
Table 2

Summary of functional groups discussed for nickel, copper, and cobalt recovery

For solution with the presence of different metals, chelating resins are better than cationic ion exchange resins, which prefers ions of high charge and small hydrated volume, as well as interacts strongly with the functional groups of the exchangers [61, 120]. In a study developed by Revathi et al. (2012), cationic resin Ceralite IR 120 with sulfonic functional group was used to study the recovery process of Ni(II), Cu(II), and Zn(II), and results showed that the presence of Zn(II) decreased Ni(II) adsorption, due to the competition between both ions for functional group of resin, while Cu(II) had no difference [59]. Kuz’Min and Kuz’Min (2014) showed that it was possible to recover 99% of Ni(II), Cu(II), and Co(II) from leach pulps of low-grade sulfide ores using chelating resin [53]. Li et al. (2012) showed that it was also possible to separate Ni(II) and Co(II), obtaining a super high-purity cobalt solution using NDC-984 chelating resin [67].

In all articles reviewed, pH had high influence on metal recovery in both adsorption capacity and selectivity. Cationic chelating resins can be present with H+ in the functional group, so high presence of H+ in solution decreases resin efficiency. However, metals react with OH– forming precipitate (Mex(OH)y), and each metal can precipitate at different pH [9]. For this reason, there is a pH limit that is possible to increase. In a solution with the presence of other metals, pH limit could be low. This is what happens with iron, once it can be precipitated at pH 2 and, then, copper and cobalt precipitate with it [16].

The selectivity of the resin has been also analyzed by means of structural characteristics of metal ions. Stefan and Meghea (2014) verified that the best selectivity for Al(III) and Ni(II) was attributed for the reason of smallest hydrated radius, ionic radius, and covalent radius, and nickel ion has the smallest Van der Vaals radius between studied metals (Al(III), Ni(II), Ca(I), and Pb(II)) [52]. Iminodiacetate resins are largely used to recover Ni(II) and Cu(II), and for the reason of their selectively, Cu(II) is first recovered. In the studies reviewed, these resins are, in general, more fitted by Langmuir isotherms, indicating that the metals are adsorbed in the surface of resins and the maximum coverage is obtained when all sites are filled. The preference for Cu(II) ions is also verified in resins with bis-picolylamine functional group [28]. In studies that there was low concentration or no presence of Cu(II) ions, Ni(II) and Co(II) can be recovered using bis-picolylamine resins; it has higher efficiency than iminodiacetate resins [117].

6 Conclusion

An overview about chelating resins applied for Ni(II), Co(II), and Cu(II) recovery was discussed. Solutions obtained after leaching process of nickel and copper ores have high concentration of metal contamination; the main is iron. For this reason, selective recovery is important in order to increase industrial process efficiency. Chelating resins are important due to its selectivity, while cationic ion exchange resins are not selective. Therefore, a review about chelating resins studied for this metal recovery is important, as well as better conditions and variables that can decrease the process efficiency. Among metals discussed, cobalt is important due to high application on renewable batteries, and it might be scarce in the next few years.

Notes

Funding Information

The authors received financial support from the University of Sao Paulo, the University of British Columbia, and the FAPESP/Capes grants 012/51871-9, 2016/05527-5, and 2017/06563-8, Sao Paulo Research Foundation (FAPESP).

Compliance with Ethical Standards

Conflict of Interest

The authors declare that they have no conflict of interest.

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Copyright information

© The Society for Mining, Metallurgy & Exploration 2018

Authors and Affiliations

  1. 1.Department of Chemical EngineeringUniversity of Sao PauloSao PauloBrazil
  2. 2.Department of Materials EngineeringThe University of British ColumbiaVancouverCanada

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