5.3 SOLVENT EXTRACTION OR PRECIPITATION Solvent extraction means to remove the dissolved metal from the leaching solution. Several techniques are available for recovering metals from leaching solution. The most important industrial process is (a) electrolytic deposition, but other methods include (b) gaseous reduction, (c) precipitation, (d) solvent extraction and (e) ion exchange. Electrolytic Deposition Many metals are conveniently recovered from solution by cathodic reduction in an electrolytic cell. This usually has the advantage of producing the metal as a coherent solid deposit, it mayoften be obtained in the form of a powder by using a high current density. The maximum current that can be drawn per unit area of an electrode is known as the current density (j) for that electrode. Theoretically, cathodic reduction of any metal is possible but more reactive metals require a fused salt electrolyte. The electrolyte is then generally at a temperature above the melting point of the depositing metal which is consequently produced in a molten condition. Foran electrolytic cell reaction involving stoichiometric quantities of reactants and products, the quantity of electricity required is nF, where 1 is the number of electrons required (i.e. valency) for the cell reaction to occur and F is the Faraday’s constant. The amount of electrical work done when n electrons are involved in the cell reaction is Fe joules, where é is the potential or emf of the cell in volts. Therefore, AG = -nFe (5.36) When all the reactants and products that take part in a reaction in a reversible cell are in their standard states and the standard free energy of metal deposits is given by: p AG (5.37) ~ ‘The overall free energy change of the reaction can be written as: AG = AG? + RT Ink (5.38) Putting the values from Eqs. (5.36) and (5.37) into Eq. (5.38): -nFe = -nFé + RT Ink or e= 2 —[(RT In kyinF] (5.39) If the electrode consists of a metal M whose valency is n’, reversible with respect to M™ ions, so that electrode reaction is as follows: M™+ne=M (5.40) ‘The equation for the cell potential becomes: @= 2 ((RTInF) In (ay/ayin+)) (5.41) If the metal deposited is pure, at standard state: ayy = 1 So, €= 2) + [(RTnF) In (ayin+)] (5.42) ‘The equilibrium or reversible potential of a metal ion/metal system is calculated by this Nernst equation (Eq. 5.42). Detail can be seen in Section 6.4. ‘At equilibrium the activation energies for the anodic and cathodic processes are identical, AG, = AG‘, and the anodic and cathodic current densities are equal: ic = in =i» the exchange current density For an overall cathodic process to occur the potential of the cathode must assume a value more negative than the equilibrium potential of the depositing system. The change of potential decreases the activation energy for the cathodic process, allowing it to take place more readily, and raises it for the anodic reaction. This results in a net flow of cathodic current (jc > ja). The converse holds for overall anodic process, producing a net flow of anodic current (j, > jc)-Gaseous reduction: _ It is carried out at elevated temperature (above 100 °C) and at high pressure. Although the principal reducing agent in these processes is hydrogen gas, other reducing gases, such as CO, H3S can also be used. This technique has been applied in the production of Co and Ni, e.g. M™ + n/2 Hy =M + nH* (5.43) The gold or silver is precipitated from cyanide solution by using zine dust: 2NaAu(CN); + Zn = NazZn(CN), + 2Au (3.44) The copper is recovered from dilute solution by addition of iron scrap. The copper precipitates as finely divided loosely adherent spongy particles, according to the reaction: CuSO, + Fe = FeSO, + Cu (5.45) Solvent extraction: Solvent extraction or liquid-liquid extraction is the separation of one or more components from a liquid by preferential dissolution in an extracting solvent. This method is first used in 1945 for metallurgical application for processing of nuclear fuels which require a high degree of purity. Solvent extraction is used to separate tantalum from niobium; zirconium from hafnium; vanadium from uranium; cobalt from nickel; and to purify compounds of Cu, U, Th and the rare earth metals. The bas (i) Dissolution: The impure compound or the ore is dissolved in a suitable acid or alkaline aqueous medium. (ii) Extraction: Usually an organic liquid is brought into contact with an aqueous solution containing the desired metal ions as well as impurity ions. Metal ions enter the organic phase preferentially. Partition: Organic and the aqueous layers are separated by employing suitable techniques. (iv) Stripping: The loaded solvent containing the product is introduced into another extracting unit where the metallic values are removed by contacting with another aqueous phase. steps, in solvent extraction (Figure 5.3), are as follows: lon Exchange The solid organic resin used is in the form of hard, insoluble granular solid or porous beads form, so that it can be easily packed in long columns. Resins are complex organic acids or bases which are insoluble in water and contains an active organic compound, RX (where R is polymer and X is —ve ions, e.g., Cl- or NO3). Jon exchange is a phenomenon that occurs readily in nature with alumino-silicates providing the solid, three-dimensional networks with which the exchangeable ions are associated. The principal of ion exchange is a solid resin exchanges ions on its surface from another ions in solution. Absorption is the result of an exchange of ions between the solution and the solid. The solid phase is made to initially absorb a suitable ion of the desired metal through an ion exchange reaction. This is called elution, i.e., a method by which the absorbed ion is brought into solution. The metal is finally recovered from the solution by precipitation through further treatment of the leach solution.; |Loaded organic solvent} Organic solvent (Containing (e.9. EHPA) miter cORBOURAT ‘Organic § aqueous 2 Vessel-I 8 § | [Leached solution iiekaed aqueous solution (ie. Tailings) Unloaded organic solvent} Organic aqueous Vessel-l! i [Aqueous stripping Loaded aqueous ae ait metal compound) (e.g. Na,CO,) [To chemical precipitation] FIGURE 5.3 Basic scheme of solvent extraction. ‘An ion exchange medium that is commonly used consists of synthetic resins which are in the form of small but hard porous beads so that they can be easily packed in long columns. Resins are complex organic acids or bases which are insoluble in water. The salts of resins are also insoluble in water, Basically resins are large molecules that comprise interconnected and cross linked chains. For simplicity, the structure may be written as RX, where R is the polymer backbone and X is the ion exchange site. Most ion exchange reactions are written as: RA + B-=RB+A (Anion exchange) (5.46) CR + D*= DR + C* (Cation exchange) (6.47) where A, B, C and D are radicals. For example, in the recovery of uranium from H,SO, acid leactied solutions, low grade ores containing only about 0.2% U3Ox can be leached by anion exchange resins for subsequent uranium recovery. 4[RN(CH3)4J° Cl + [UO,(SO,)3]* = [RN(CH5)4]4 UO(SO4)3 + 4Cl- (5.48) or with another resin: [UO,(SO,);]* + 4RNO; = R,UO,(SO,); + 4 (NO3)- (5.49)Columns A and B are initially used for absorption, while those in column C are used for elution (as shown in Figure 5.4). When columns A and B get sufficiently saturated with the metallic values, eluant is introduced through A. The original liquor feed is now introduced into column B and then passed through column C. When this is done columns B and C are used for absorption and column A for elution. Gradually, when column C also gets saturated with the metallic values, artother change over is done. Ore Eluting solution Reagent lon exchange columns: Acid Leach Residue Concentrate FIGURE 5.4 _lon-exchange columns. Under following conditions, ion exchange is performed more effectively: 1. At low concentrations of the aqueous solutions, the extent of ion exchange increases as the valency of the exchanging ion increases. (e.g. Na* < Ca** < Al < Th**) At low concentration and for the elements having the same valency, the efficiency of ion exchange increases as the atomic number increases. {e.g. Li(3) < Na(11) < K(19); Mg(12) < Ca(20) < Ba(56)] The difference in the efficiencies of ion exchange process seems to disappear at higher solution concentration and at higher temperatures. 4. Organic ions having high molecular weight and complex metallic anionic complexes are usually better suited to ion exchange.11.5 Eh-pH DIAGRAMS Reduction of metallic ions from aqueous solution to the elemental metal is generally accomplished by any of the three following methods. (a) Cementation or contact reduction (b) Gaseous reduction (c) Electrolysis We have discussed electrolysis in the preceding chapter. Discussions on cementation and gaseous reduction are given in the next two sections in this chapter. In this section, we propose to briefly discuss Eh-pH diagrams which present the equilibria at various pH values and electrical potentials between the metal, metal ions, solid oxides and hydroxides for systems in which the only reactants are metal, water, hydrogen and hydroxyl ions. These diagrams, which are analogous to the phase diagrams of alloy systems, provide a thermodynamic basis for understanding the stability of phases under various conditions of pH and potential values. These were first prepared and proposed by Pourbaix” and, accordingly they are also called Pourbaix diagrams. These diagrams provide thermodynamic basis not only for cementation but also for leaching of minerals. As an example, consider dissolution of zinc in aqueous solution. In a reducing acid of pH 4, the metal dissolves to form Zn**, But at a higher pH, the thermodynamically stable phase is Zn (OH), and the equilibrium activity of Zn** will be governed by thesolubility product of Zn (OH), and the pH of the solution. A still higher pH, ZnO; ions become stable and both Zn?* and Zn (OH), are unstable. The exact conditions can be obtained from the Eh-pH diagram for Zn/H,O system shown in Fig. 11.3. The method of construction may be briefly described as follows. The general equation for a half cell reaction is aA + mH" + 2e° = bB + cH,O (11.33) From the Nernst equation (Ch.10, Eq.10.15) and substituting—log a+ = pH we obtain at 298 K, 59 a5 E (volts) = E° — 0.059 pH - 2959 jog (11.34) z z a It follows that for any constant ratio or ap \ a4, the Evs pH relationship will be linear with a slope—0.059 m/z and that when ag = a, = 1, the intercept of the curve on the E axis (i.e. pH = 0) will be £° , the standard potential. For drawing the diagram for Zn/H,O system one has to consider the reactions such as (a) Zn?* + 2e° = Zn; E = E° + 0.030 log (azq2) © = 0,763 + 0.03 log (aq) (11.35) (b) Zn (OH), + 2H* + 2e = Zn + 2H,0; E = E° — 0.059 pH (11.36) (c) ZnO} + 4H" 2e = Zn (OH), + H,O E=E-0.118 pH + 0.03 log (az,03 ) (11.37) and other relevant ones. The Nernst equations for the individual equilibria help establish the Pourbaix diagram. These diagrams have been extensively used in the study of corrosion reactions. They, however, are also of significant interest in hydrometallurgy. Subsequently we shall use similar diagrams, generally considering rather simple solution equilibria. 11.6 CEMENTATION OR CONTACT REDUCTION Cementation may be defined as precipitation of a metal from an aqueous solution of its salts by another metal. Since precipitation generally occurs on the surface of the added metal, it is called cementation. The mutual contact of metals has also given rise to the terminology for this process. The process can be predicted in terms of electrode potentials. The metal with more positive oxidation potential (see Table 10.2) of the electromotive series will pass into solution and displace a metal with a less positive potential. The basic mechanism is electrochemical in nature. However, the overall phenomenon would comprise of several steps including nonelectrochemical phenomena such as diffusion processes and sequential chemical reactions. So far as the overall stoichiometry is concerned, the process can be complex because the reducible ion may be present as hydrated cations e.g. Cu (H,0,)2° or complex ions e.g. Ni (NH3)?", Au (CN))- ete.2n03-(aq) Zn?* (aq) *znt* = 10 EV = Rao Fig. 11.3 Simplified potential-pH diagram for Zn/H,O system [Source: L.L. Shreir Ed. Corrosion Vol. 1, Newnes-Butterworths, Lond (1963) p 1 : 68) [Here the unit of activity is g.ion/| because this is the unit used by Pourbaix, In the S.I. unit, the relative activity is dimensionless.