12 CEMENTATION AND REDUCTION 421 Introduction 12.2 Cementation 12.2.1 Thermodynamics Kinetics 12.3 Reduction by dissolved gas 12.3.1 Thermodynamics 12.3.2 Kinetics 12.3.3 Practicalities 12.3.4 Sherritt-Gordon process 12.4 — Some problems 12.4.1 Questions 12.4.2 Worked solutions12 CEMENTATION AND REDUCTION 12.1 Introduction he direct recovery of metal from solution can be achieved by reduction cither using electrical power ot a chemical reagent. ‘The former is a major topic and will be covered in the next module. The use of ts will be examined in this module. There are two different forms of chemical redu reagent that can be used and each has its advantages and drawbacks, A soluble chemical reductant may be introduced into the solution in which a homogeneous reaction occurs, or a solid reagent may be added leading to heterogeneous kinetics. “The major process where a soluble reductant is used is in the Shertitt-Gordon process in which nickel and cobalt solutions are reduced to metal powder by s hydrogen, The use of a solid reagent is usually limited to situations where a more reactive metal is used to displace a less reactive metal from its solution, examples of this are recovery of gold using zine dust and recovery of copper onto scrap iron. "This latter process is called cementation. chemi 12.2 Cementation cementation is the process whereby a metal is precipitated from solution by reduction with the simultaneous dissolution of a less-noble metal. Practical examples are the recovery of copper from dilute leach solutions using scrap iron, the cementation of gold from cyanide leach solutions by zine and the purification of zinc sulphate solutions before electrowinning by cementation with zine. 12.2.1 Thermodynamics ‘The thermodynamic requirement for spontancous cementation is that the equilibrium, potential (E,) for the metal being reduced must be greater than that for the sacrificial metal. This is illustrated in the E,,/pH diagram in Figure 12.1 for the gold/zinc/cyanide system which shows that the Zn(CN),°/Zn couple is about 0,7V less noble than that for the Au(CN),/:Au couple(shown as the bold line) in alkaline solutions. Note that zine is unstable in aqueous solutions in the pH region (10-11) in which cementation is casried out and that, at low cyanide concentrations Zn(OH), can precipitate in the pH region 11-12 2Zn(OH); ZH(CN), IM Wao, pH Figure 12.1 Combined Ey,/pH diagrams for the Au and Zn systems in unit activity cyanide ‘This has, until the advent of the carbon-in-pulp process, been the conventional route for the recovery of gold from cyanide leach solutions. The process is carried out in the pH range 10 to 11 with zine dust in de-aerated solutions, In the absence of other reducible species (in practice this is not true with Ag, Cu, Ni and other metals being co-precipitated with the gold), one can schematically draw the relevant i/E, curves as shown in Figure 12.2. At the zine metal surface, both anodic and cathodic reactions are occutting at equal rates. This is satisfied at the mixed potential Em, and the rate of cementation is given by the partial current density at that potential. As drawn, this potential occurs in the mass-transport controlled region of the cathodic process and the overall rate will therefore be controlled by mass transport of the aurocyanide ion to the surface of the zinc dust particlesZn + ACN’ = Zn(CN),? + 20 AulGN}y # 0 = Au * 2CN" ie Figure 12.2. Schematic current potential curves relevant to the cementation of gold by zine ry valuable in intexpreting the behaviour of such processes. ‘This mixed-potential theory is ve 12.2.2 Kinetics For a cementation process controlled by the rate of mass transport of the more noble metal to the surface of the reducing metal, -dC/dt = kL A.C where Kl. is the mass transport coefficient, A the surface area (per unit volume of solution) of the reducing metal and C the concentration of the metal being reduced. A is usually assumed constant with time (.e. replacing one metallic surface with anothet) . This first-order rate equation can be integeated to give the relationship InfC,/C]=kKLAt which is often observed in the initial stages of the reaction. For reasons to be discussed below, deviations from this expected behaviour can occur. The mass transfer constant, KL. can be estimated from Stoke's Law for a freely suspended condition and, for metallic particles of diameter less than about 50jim can be approximated to KL = D/r where 1D is the diffusivity of the metal being cemented and ris the particle radius, In many cases (particulatly with reducible metals having low exchange current densities), the less-noble metal surface area is reduced to such an extent by the depositing metal that the mixed potential shifts anodically into the region where the reaction is no longer mass-transport controlled and, in extreme cases, the rate decreases to almost zero. ‘This is illustrated in Figuee 123 for the cementation of copper on iron at various initial copper concentrations.cy log{C,/C] 0. al 0 6 30 45 60 time, min Figure 12.3 Effect of initial copper concentration on rate of cementation on iron, In other cases (particularly with depositing metals having high exchange current densities) the deposit becomes tough and dendritic with the result that the surface area increases with time and the above tate expression is no longer appropriate. An example of both of these phenomena is given in Figure 12.4 which summarizes the results of kinetic experiments of the cementation of copper on iron from sulphate solutions. At low concentrations of copper, the first-order rate constant derived from the above theory, increases with increasing copper concentration due to an increasing toughening of the surface with resulting increased mass transport to the iron surface. However, at much higher concentrations, the rate decreases due to blocking of the iron surface and reduction of the area available for anodic dissolution of the iron with the tesult that the reaction is no longer mass transport controlled. 0.04 k, cm/s 0.02 20 200 2000 [Cu],mg/t Figure 124 Effect of copper concentration on rate constant for cementation on iron‘Table 12.1 summarizes the results of investigations of a number of systems. ‘Table 12.1 Effect of initial concentration on rate of cementation. Effect of increased ‘Concentration System cone. on rate Range, g/1 Cu" 7Al GO.) decreased 0.06- 0.6 Cu" 7Fe (Ch) ‘no change 025-27 Cu’*/Fe (SO/) decreased 05-15, Cu" /Fe 60.) increased 001-02 | decreased — 02-20 Cu"/Ni (SO) decreased 0.5-3.0 Cu" /Zn (SO) ‘increased 0.005 - 0.1 Ca" /Zn (SO;) decreased 50-100 increased 0005-01 ‘Ag’/Cu (NO,) increased 0.003 =4 ‘Ag’ /Zn (NO,) increased 0.003 -3 Many of the above observations are predictable in terms of our understanding of the electrocrystallization of metals and of the exchange current densities for the anodic dissolution of the less noble metal. Thus, metals having a high exchange current density such as Ag tend to produce highly porous, dendtitic deposits which will not significantly reduce the surface area available for anodic dissolution of the less noble metal, In these cases, increased rates are observed at high deposit masses. Conversely, metals with low exchange current densities tend to produce dense, compact deposits which will rapidly cover the surface of the corroding metal resulting in decreased and, in extreme cases, negligible rates of cementation even at very low concentrations, Microscopic examination of the cemented surface have confirmed the above conclusions which are also supported by measurements of the activation energy of the rate of cementation which is of the order of 15-20 kJ/mol at low concentrations where the mate is controlled by a mass transfer process but 40-50 kJ/mol under conditions where the rate is inhibited by the reduced surface area and becomes controlled by the rate of the anodic dissolution reaction. Cementation as a metal recovery process has largely been replaced by methods such as solvent extraction (for copper) and activated carbon (for gold). However, the use of zine dust is still the accepted method for the purification of zinc electrolytes and some attention should be devoted to this problem. The major impurities which are removed by cementation are copper, cadmium, nickel, cobalt and traces of other metal ions such as germanium, chromium, lead. In addition to contaminating the final zine metal and often having deleterious effects on the morphology of the zine deposit, the major effect that these impurities have on the electrowinning process is to reduce the cutrent efficiency by promoting the simultaneous evolution of hydrogen at the cathode.‘This is a result of the fact that the exchange current density for hydrogen evolution is orders of ‘magnitude greater on the surfaces of these metals than on a pure zine susface. Depending on other factors such as deposition cycle time, current density and the presence of other impurities such as germanium and antimony, the cobalt concentration must be reduced to values as low as O.1mg/| for efficient zine deposition. The purification process is generally cartied out in two stages. In the first which is conducted at about 70°C, cadmium and copper are cemented using atomized zine powder from the leach solution which contains about 150g/1 zinc at a pH of 4 to 5. The cemented product is removed by filtration and the filtrate is subjectedl to a second stage of cementation at a higher temperature 80°Q). In this stage, the other impurities such as cobalt and nickel are removed. In some operations, the sequence of impurity removal is reversed and, in other cases, an additional Purification stage is used to recover copper. Schematic flowsheets for these optional routes are shown in Figure 12.5, impure solution Zn $0103 79 dust Cold Stage Cu, Cd removal Hot Stage puriied Co removal Solution return acid Y o Cu, Cd cake to further processing “o leaching ¥ Cocake impure solution purified Zn dust Sonuton Cu removal Co removal Cd comoval Y Cu cake Co cake Cd cake Figure 12.5 Flowsheets for the purification of zine solutions by cementation‘The B,-pH diagram for zinc(shown with the bold lines for a 1M solution) can be superimposed on that for cobalt(shown with the lighter ines for a 10M solution), as shown in Figure 12.6. 20 0 2 4 6 8 10 pH 12 Figure 12.6 Combined E,,/pH diagram for the Zn (IM, bold)) and Co (10“M, light) systems ‘The important features of the diagram from the point of view of the cementation of cobalt by * the reaction is thermodynamically favourable at all pH values because the line for the Co" /Co reaction lies above that for the Zn /Z.n couple. ‘* precipitation of zine as the hydroxide or basic sulphate will occur at pH values above about 5 while cobale will only precipitate at higher pH values. © zinc is unstable with respect to the reduction of water by hydrogen evolution (Zn™*/Za line lies below line “2” ‘Thus, although the thermodynamics predicts that the cementation reaction should readily proceed at pH values from 4 to 5, experience shows that the rate of cobalt cementation is extremely slow in the absence of “activators” which are generally copper and arsenic ions or copper and antimony ions. These additives are added as their soluble salts in amounts which will produce solutions containing of the order of 10 to 100 mg/l of each. The exact mechanism of the action of these inhibitors is still not clear with vatious theories involving the formation of copper arsenides or antimonides on the zinc surface which promote in some way the reduction of cobalt ions being the most favoured12.3 Reduction by dissolved gas he Sherritt-Gordon process for tecovering nickel and cobalt is the only [ major process to use hydrogen as a reductant. Although these metals could be cemented using a mote reactive metal, such as zine or iron, the purity of the product would be decreased due to the presence of some unoxidised metal. Acid washing of the cemented mass would also redissolve some of the valuable metal, thus requiring further separation and recovery steps. The use of hydrogen removes the problem with contamination since it oxidises to protons. ‘This has two advantages, no contamination is introduced into the solid product and the pH of the solution decreases thereby increasing the solubility of the metals in solution. Other gases can also be used as reductants, you will already have noted the use of sulphur dioxide as a reduetant in the leaching of manganese dioxide for the production of electrolytic MnO, but it can also be used to reduce dissolved gold complex ions to gold. 12.3.1 Thermodynamics ‘The oxidation of gaseous hydrogen is simply... H, = 2H’ +2¢ for which the Nernst equation is given by Es E+ RT/F dnay,-RV/2F Jnayy, By definition F,,, = 0, since all redox potentials are compared to that of the standard hydrogen electrode SHE). Also, since pH = ig, the equation becomes E = -2303RT/F pH-RT/2F la ayy ‘Thus the redox potential is a function of both the solution pH and the activity of dissolved H.. ‘The data in Figure 12.7 shows the solubility of hydrogen is linear function of pressure, 0.007 a 0.08 | oc 25 50"c dissolved Hy! 8 2 E oon oF ee ° 50 100 160 200 250 H, pressure / atm Figure 12.7. Solubility of hydrogen as a function of partial pressure at different temperaturesthus the equation becomes E 2,303RT/F pH -RT/2F InP, At 28°C, E 0.05916 pH — 0.02968 fog Py, ‘The oxidation of carbon monoxide is given by CO + H,O = CO, + 2H! +26 For which the Nemst equation is E = E'- 2.303R1T/F pH -RT/2F la (aco / aco.) At 25°C, B® = 0.12 V, which makes CO a more powerful reductant than H,. ‘The decrease in reversible potential with pH is the same as that for hydrogen ie, 59mV/pH. A high CO/CO, ratio would give an even more powerful reducing capability but still with a 59mV/pH decrease. Unfortunately, the rates of reduction of coppet and silver by CO are considerably slower than, when hydrogen is used. ‘Thus, although feasible, there seems to be little to be gained by using CO instead of H, For sulphur dioxide, the reaction is HSO, + H,0 = SO? + 4H" +2e And the Nemst equation is E = B°—2,303*4*RT/2F pH - 2.308RT/2F log (aynsos / Asow) at 25°C, = +017 V which suggests that it is a less effective reductant than hydrogen but the greater dependence of potential on pH makes it an interesting system. E = 0.17 — 0.1183 pH ~ 0.02958 Jog (aypso3 / son.) Despite this, litle work has been reported using SO, as a reductant for production of pure elements. It has been used to recover gold from acid chloride solution and produce selenium, and telhirium. Indeed, selenium can be selectively reduced in the presence of tellutium by controlling the pH. ‘The solubility of the relevant gases are shown in Table 12.2. ‘Table 12.2 Solubility of reducing gases Solubility (25°C, 1 atm), M 2: (| 990" 0.034 1.40 10‘The relatively high solubility of SO, and the ease of handling the gas (its a liquid at 25°C under ~4atm pressure) compared with H, or CO make SO, an interesting possibility for application as a reductant in the furure, If the solubility problem is ignored, the reversible potential of the three gaseous systems is plotted in Figure 12.8 as a funetion of pF. Clearly, the most important factor governing the reductive potential of hydrogen is the pH since a 100-fold increase in the pressure of hydrogen above the solution produced a dectease in potential equal to an increase of 1 pH unit. 0.2 E/V vs. S.H.E. H,S0,/SO,?" | 01234567 8 9 1011121314 pH Figure 12.8 E,,/pH diagram for reducing gases Due to the practical application of hydrogen, only this pas will be considered, ‘The generalised equation of the reduction of a divalent metal ion is given by M* +2e=M. Is associated Nemnst equation is given by E=B'+RT/F Ina, —RT/E nay, ‘The activity of a metal is unity, so the equation becomes E=E'+RT/2F nay, which at 25°C E? + 0.02968 log as, "Fora single metal such as cobalt, the reversible hydrogen potential diagram can be ovetlaid by plots of the above equation to give the diagram in Figure 12.9. ui xz oO 9-03 g 7 57 [eoa=0.01 Ww [Co a=0.0001 “0.4 0.5 20.6 Hon pe 0123456789 pH Figure 12.9 Combined E,,/pH diagrams for the Co and H systems ‘The diagram shows that to reduce the cobalt activity in solution to 0.01 using 1 atm hydrogen requires the pH to be maintained at ~5.7. ‘This can also be determined by equating the hydrogen and metal half reactions since at equilibrium the half cell potentials are equal -0.05916 pH ~ 0.02968 log Py. = E? + 0.02968 loge aya. and rearranging PH = (0.02968 fog Py + E° + 0.02968 log ayy.) /-0.05916 for cobalt, E' = -0.277V, so. pH = 4.682 -0.5/og Pry 0.5 log aye at Py = Latm and ay..=0.01 .682.— 0.5 fog 1— 5 log 0.01 = 4.682 + 1= 5.682\ more convenient diagram for many metals ean be drawn by combining the Eh-pH diagram for hydrogen with an Eh-activity diagram for a range of metals as shown in Figure 12.10. log ayas 0.1 100 0.2! py Sn | 03) Co E/Vvs S.H.E. 04 -0.5_d oe) Fe “07 Figure 12.10 Diagram summarizing the thermodynamics of the reduction of metal ions by H, ‘The dashed lines show the determination of the pH at which a 10* cobalt solution is in equilibrium with atm of hydrogen (~pH 6.8). This diagram also gives an indication of the levels of imputities present in the system that can be tolerated prior to coreduction. For 10 cobalt the horizontal line can be extended to intercept other metals which may also be present in solution, Where these lines intersect is the maximum concentration of the impurity remaining in solution after cobalt precipitation. Thus, there would be 10°" Ni, 10" Cd and 10° Fe xemaining in solution so cadmium and iron are unlikely to be present in the cobalt product, unless they were present at very high concentrations in the feed solution. Nickel is however likely to be a major contaminant as itis more readily reducible than cobalt. A similar calculation can be made for nickel precipitation in the presence of cobalt, if the nickel is to be reduced to 10* chen the maximum cobalt remaining in solution is 10°”. Clearly, these metals are difficult to separate by selective reduction and operational practice requires the separation of these elements prior to reduction, typically by solvent extraction. Even more problematical is copper which reduces under all conditions where hydrogen is present, when the nickel in solution is reduced to 10" the copper in solution is 10°. Thus copper must be removed before either nickel or cobalt are reduced. Whilst this can be achieved by hydrogen reduction at low pH (<4) 43it is practically achieved by precipitating copper sulphide (by heating the solution and adding HS) under conditions where the nickel and cobalt remain in solution. ‘The problem with selectivity is also true of any metals with similar E", ‘The minimum E? Aifference to give a 10° difference in final metal concentration in solution can be calculated. At equilibrium Ey + RT/F Inay = E’y + RT/F nay Rearranging gives Ey - Ely = RT/F Inay- RT/F Inay = RT/P In (ay/ay) = 0.2366 V for (ay/ay)=10" The necessity to operate at relatively high pH to reduce some metals presents a significant practical problem - metals precipitating as their hydroxide, For unwanted metals this may provide a route to separation but must be avoided for the desired metal. Module 9 has examined the use of hydrolytic precipitation as a recovery/ separation method and this topic will not be covered here. Clearly, the use of high pH presents some problems and steps need to be taken to avoid the hydrolytic precipitation of the desired metals under conditions where reduction occurs. ‘The simplest way of doing this is to complex the metal ion and for nickel, cobalt and copper the ligand used is ammonia. However, stabilization of the metal ion by complexation results in a decrease in the FE for the reduction of the metal ion, thereby making the reduction less favourable. Thus, for example, the E° for the reaction Ni?" +20 = Ni is -0.24V while that for the reaction Ni(NHL,)," + 2e = Ni + 6NH, is -0.50V. For a given ammonia concentration, the predominant Ni ammine species will be a function of pH and so is the E,, for oxidation of hydrogen. It turns out that the maximum thermodynamic driving force for reduction of nickel in ammoniacal solutions occurs close to a ratio NHy/Ni = 2i.e. the diammine complex. This ratio is also important because there will be no change in pH by operating the reduction under these conditions, Ni(NH,);* + H, = Ni+2NH," 12.3.2 Kinetics ‘The overall reaction for the reduction of divalent metal ions by hydrogen is given by M™ +H,=M+2H" 14‘The rate of the forward reaction is a function of metal ion, hydrogen gas and proton activities in solution. If the reverse reaction is significant, itis a function of the proton activity and the sutface atea of the metal formed. Although the thermodynamic appreciation above shows that reduction of many metals by hydrogen is possible at 25°C the reality is that bubbling hydrogen through solution does not result in metal production. ‘Thus, although thermodynamically favourable the rate determining step is kineticaly limited. Data ftom cementation shows that the activation energy was typically of the order of 15-20 k]/mol at low concentrations when the rate is mass transfer controlled but 40-50 k]/mol when anodic dissolution is rate detetmining. Clearly, there is a different rate determining step operating when hydrogen is used as the reductant. Hydrogen is not very soluble and the solubility decteases with temperatute, as shown in the plot above. Clearly, the low solubility of hydrogen suggests that the mte determining step may be limited by its diffusion to a metal ion, If this is the case then the activation energy would be similar to that of cementation. Cementation of nickel by iron has an activation energy of 29 KJ ‘mol’ but the activation energy for reduction of nickel by hydrogen has not been reported at 25°C due to the slowness of reaction, even under elevated pressures. ‘Thus, the solubility of hydrogen is not the tate determining step. ‘Thus, it is necessary to inctease the temperature to increase the tate, the plot in Figure 12.11 shows the effect of activation energy on the rate of reaction, the rates have all been normalised to the rate at 100°C. Clearly, ifthe activation energy is low then only a relatively small change in rate is observed with temperature. As the activation encrgy increases, the rate at low temperature is negligible, however, once the reaction becomes noticeable small increases in temperance result in large increases in rate. ‘Thus, itis reasonable to expect that the hydrogen reduction of nickel and cobalt has a high activation energy. 0 ® 160 kJ mot rate Eee 0 100 150 200 temperature 1°C Figure 12.11 Effect of temperature on kinetics for various activation energies 15‘The molecular hydrogen used has no tendency to patticipate in aqueous reactions and needs to be dissociated before it becomes highly active. To dissociate hydrogen requires 430 kJ mol’, fortunately reactions involving hydrogen can be catalysed by both aqueous and solid substances. In aqueous solution, homogeneous hydrogenation catalysts include Ag’, Hg,", Cu’* and PdCl? , under normal circumstances these are unlikely to be present in any significant quantity in a nickel or cobalt solution (remember that copper is removed prior to hydrogen reduction as it would contaminate the metallic product), Since none of the soluble catalysts are present it is necessary to examine solid (heterogenous) hydrogenation catalysts. This group of catalysts includes metals from the iron and platinum metals groups, oxides and some sulphides. Fortunately, within these catalysts are both nickel and cobalt. ‘Thus, once the reduction has started it is to some extent autocatalytic since the surface area of catalyst increases as the extent of reduction increases. The initial reduction to metal is either by disect splitting of hydrogen molecules by metal ions or homogeneous catalysis by the minute amounts of the soluble catalysts present. Since these are relatively slow processes it is normal to add a small amount of recycled metal particles which act as seed catalytic nuclei and speed the initial stages of reduction. In both homo and heterogenous catalysis the rate of precipitation increases with temperature and, usually, the partial pressure of hydrogen. 412,3.3 Practical Application ‘The solubility of hydrogen in water as a function of temperature and pressure is shown in Figure 12.12. Clearly, ambient temperature and pressure result in extremely low solubilities of Hi, As for most gases, increasing the temperature results in a decrease in solubility (minimum at ~50°C), however, somewhat oddly hydrogen solubility then increases with temperature Clearly, it is advantageous to operate at elevated temperatures and pressures. 160.0088 0.004 0.0035 0.008. 0.0025 (HJ/M 0.002 0.0015 001 0.0005 100 180 200 250 temperature /°C Figure 12.12 Solubility of hydrogen as a function of temperature and pressure Unfortunately, increasing temperature results in decreased solubility of many metal salts, with many sulphates having solubility maxima in the range 80-150°C. Complex ions also become less stable with temperature making the maintainence of reasonable concentrations of metal in solution at neuttal and alkaline pH difficult, For these reasons, hydrogen reduction typically operates at 140-200°C. with sufficient pressure of hydrogen to elevate the boiling point of the solution. In light of the high temperatures and pressures required the reaction takes place in an autoclave. 12.3.4 Sherritt-Gordon process ‘The Shestitt-Gorclon process is the only process which produces commercial quantities of metal by hydrogen reduction - small quantities of copper powder are also produced by this method. ‘The ore is initially leached in an oxidising atmosphere (94°C, ~Batm air), the slutty is filtered With the solution going to purification and the solids transferred to a second autoclave where ammonia is used (80°C, ~9 atm), the solids are sent to tailings and the filtrate is passed back to the oxidative leach. During leaching, the sulphide in the ore is oxidised and a range of sulphoxy anions (0,7, $,0,* +5;O,*, etc) are formed along with sulphamate SO,NH;. Other than sulphate, these anions are reduced by hydrogen precipitating sulphur and cteating major problems. Consequently, these anions have to be oxidised to sulphate. Prior to oxidation, excess ammonia is distilled off at atmospheric pressure and is recovered and recycled. During the distillation most of the copper present is precipitated out as the sulphide as the sulphoxy anions $,0,, $,0,, 8,0, disproportionate at high temperatute to sulphate and sulphide. Hydrogen sulphide is also addled 7{o remove any remaining, copper, some nickel also precipitates and the solid is recycled to the leach stage. ‘The sulphoxy anions remaining in solution ate then oxidised to sulphate at 240°C under 40atm of ait At this stage the solution typically contains 45gpl Ni, 1gpl Co, 0.002gpl Cu, 350gp! ammonium sulphate, and 30gpl ammonia. ‘The concentration of free ammonia is adjusted to give a 2:1 ‘molar ratio with Ni+Co. ‘This solution is fed batchvwise into the reduction autoclave where itis heated to 200°C under M4atm of hydrogen and the nickel precipitates, once the reaction is completed the metal powder is allowed to settle, the depleted solution pumped out and fresh solution added. This allows the powder in the autoclave to act as a seed for the next batch, thereby aiding the kinetics of the process. The nickel powder is finally removed with the depleted solution after up to 40 eycles, when the agitation system has problems suspending the metal. Metal is also deposited on the walls of the vessel and is removed by adding ammonia solution and pressurising with air, this wash solution is recycled to the reduction plant. ‘The nickel powder is washed to remove salt, dried in an inert atmosphere to prevent oxidation and ro briquettes for sale. cither packed as powder or sintered ‘The solution after nickel reduction contains 1gpl each of Ni and Co, these are precipitated with HS and filtered, the solution being processed to recover the ammonium sulphate. The mixed sulphides are redissolved in sulphutic acid at 120°C under Tatm of air to oxidise the sulphide The pH is adjusted to 5.1 and any iron remaining in solution is removed by further oxidation to ferric which precipitates. ‘The cobalt is then selectively oxidised to Co" in the presence of excess ammonia using air at 70°C and forms Co(NH)),", nickel remains divalent. ‘The solution is acidified using sulphuric acid and the nickel crystallises out as a double sulphate with ammonium, this salt is filtered and returned to the nickel circuit, The residual cobalt rich solution is then reduced to divalent cobalt using cobalt metal and then reduced to metal using, hydrogen under similar conditions to that for nickel. 12.4 Some problems 12.4.1 Questions QUESTION 1 An ammoniacal sulphate solution resulting from the ammonia leaching of a nickel sulphide concentrate contains 58.7 g/l Ni’ and 5.89 g/l Co”, Nickel is recovered by reduction using hydrogen gas at 100 atmospheres(bar) at 25°C. Assuming that nickel and cobalt are are present as the aquo-ions, AG" (Ni) = -46.6 kJ/mol, Atomic mass Ni = $8.7 AG"(Co*) = -51.5 kJ/mol Atomic mass Co = 58.9 R=8314] K" mol! Assume unit activities for all dissolved species. 1) Calculate the values for the equilibrium constants for each reaction at 25°C. 1b) Calculate the maximum recovery of nickel free of cobalt that can achieved from this solution. 9 culate the minimum pH which can be used to achieve this recovery. 18) If the stability constant for the Ni(NH,),"' ion is 10° and that for the Co(NH)),”* is 10’, describe qualititatively the effect of such complexation on the results of the calculations (ji) and (i) above. QUESTION 2 Nickel metal is produced in WA by the reduction of the tetrammine complex Ni(NH)2* by hydrogen gas under pressure. Calculate the equilibrium hydrogen pressure(in atmospheres) required to precipitate 90% of the nickel from a solution containing 1.0 mol/l nickel as the above complex and 1,0 mol/l free ammonia(NH,) ata pH of 11 at 25°C. Assume ideal solutions and gases. Ni* + 2e = Ni E" = -0.26 V vs NHE Ni" +4NH,=Ni(NH)2" — loggk = 7.7 RI/F = 0.059 V/decade Suggest two changes to the operating conditions which would increase the degree of QUESTION 3 A scrap processor plans to leach impure gallium metal using a stoichiometric quantity of ferric ions to give a solution containing 34.85 gpl Ga’. ‘The processor wants to produce a high purity 99.99% Ga powder and after some preliminary research decides that hydrogen reduction is the way to go. To obtain a loan to install the new process he needs a report by a consultant metallurgist as to the feasibility of the process and the operating conditions. **) = -0.44,V, Atomic mass Fe Ga") = 0.53 V, Atomic mass Ga 12.4.2 Worked solutions QUESTION 1 An ammoniacal sulphate solution resulting from the ammonia leaching of a nickel sulphide concentrate contains 58.7 g/1 Ni’' and 5.89 g/l Co”. Nickel is recovered by reduction using hydrogen gas at 100 atmospheres(bar) at 25°C. Assuming that nickel and cobalt are are present as the aquo-ions, AG"(NE AG'(Co™) = -51.5 kJ/mol Atomic mass Ci R=8314] K' mol! Assume unit activities for all dissolved species. = -46.6 kJ/mol, Atomic mass Ni = 58.7 58.9 a) Calculate the values for the equilibrium constants for each reaction at 25°C. 19Write down the reactions involved NF + Hy = N+ 2H"... Co" + H, = Co+ 2H"... cecsesseseessee(I) sevssneeeesee(Q) Caleulate AG? for each reaction AG'(1) = AGNI) + 2AG"(H') - AG"(NF") - AGH) = 0 + 0- (46.6) — 0 = 46.5 kjf mal Similar AG'Q) 1.5 k]/ ol Write down the equilibrium quotients and caleutate the eguilibriumy constants. K, = [°F LINE YP yg} = p-AG(1)/ RT) = 6.78 x 10? veeeereeceeee Ke = fF f {{Co*).P yg} = exp(-AG'2)/ RT) = 9.39 x 10 0) b) Calculate the maximum recovery of nickel free of cobalt that can achieved from this solution. At equilibrium, INF*// (Co? ] = K,/K, 1.138 Ths, for no reduction of Ca , [Co?*] = 5.89 g/4= 0.1 molf Thus, [NP*] = 0.138 [Co?*} = 0.0138 malf ie, 1— 0.0138 = 0.986 mol] 1N#* is reduced or 98.6% recovery of nickel, ©) Calculate the minimum pH which ean be used to achieve this recovery. Rearranging K, = [H*P / {Ni*}.Pyo} = = 6.78 x 10” Gives [HP = K, [NP*].Pg = 6.78 x 10” x 0.0138 x 100 = 9.36 x 10° or [H] = 0.97 10" or pk 4. 4) If the stability constant for the Ni(NH)_" ion is 10° and that for the Co(NH,),” is 10°, describe qualititatively the effect of such complexation on the results of the calculations (i) and (ii) above. ‘The larger stability constant for the Ni complesc would reduce the concentration of the NF* ion to a larger extent than that of the Co°* ion with the resull thatthe recovery of the Ni would be lover Similarly, reduction of the N?* ion concentration would decrease the maximum [H"] or increase the inion pH required. QUESTION 2 Nickel metal is produced in WA by the reduction of the tetrammine complex Ni(NH),* by hydrogen gas under pressure. Calculate the equilibrium hydrogen pressure (in atmospheres) required to precipitate 90% of the nickel from a solution containing 1.0 mol/l nickel as the above complex and 1.0 mol/l free ammonia(NH,) at a pH of 11 at 25°C, Assume ideal solutions, and gases. Nit + 2e = Ni B = -0.26 V vs NHE,Ni +4.NH,=Ni(NH)2* logy = 7.7 RT/F = 0.059 V/decade The overall reaction is {Ni(NH,)/*] + H, = Ni + 4NH, + 2H* Por the reaction, NP + 2e= Ni Diy, = 0.26 ~ 0.0591/2, lg (1/ (NF) Out can substitute (NF*} = 107. JNHj/ IN(NH)) remembering, that at equilibrium, [Ni(NH )7°] = 1.0 x 0.1 = 0.1 molf Land INH} = 1.0 + 4 x 0.9) = 4.6 mol]! becanse each (Ni(NH,)/*} reduced to metal will release 4 NH, molecules, Thns, B 0.26 — 0.0591/ 2. log (10"" . (4.6) | 0.1) 595 V ‘This reaction will be in equilibrium with the reaction 2H" + 2e= HU, for which, By = 0- 0.0591/2 log Py. f (HP) when Ex, = By ie, whem, 0.0591 /2 log Pys f 10?) = 0.595 from which Phys = 0.136 atm. Suggest two changes to the operating conditions which would inctease the degree of precipitation. Increase pl - lowers the resible potential of the Hf HT conple Tnerease pressive of H1,— aso lowers the rersble potential ofthe Fa/ H? couple Increase temperature — deoreases stability of Ni(NH);* Decrease je ammonia concentration ~ increases reerible potential for nickel reduetion QUESTION 3 A scrap processor plans to leach impute gallium metal using a stoichiometric quantity of ferric ions to give a solution containing 34.85 gpl Ga". ‘The processor wants to produce a high purity 99.99% Ga powder and after some preliminary research decides that hydrogen reduction is the way t0 go. However, to obtain a Joan to install the new process he needs a report by a consultant merallurgist as to the feasibility of the process. Comment on the process and make suggestions for any improvements. E\(Fe*) E\Ga") -0.440 V, Atomic mass Fi -0.529 V, Atomic mass Ga = 69.7 Firth, what exactly isn solution? Ga+ 3Fe" = Gal* + 3FF 21“Tins, the final solution comtains 34.859pl = 34.85/69.7 = 0.5M Ga tt abo contains 0.5%3 = 1.5M Fé Fé" + 20= I B= 0.440 + 0.02598 logit?) Gal* + 3e= Gia, B= 0,529 + 0.01972 logiGa"*] 2H + 205 Hy B= 0.05916 pH - 0.02968 log, Phy plotting these on a stable diagram. og aye mak} 24 6 ye 1 Bm Charly, iron mud be expected to reduce before galluen so the inital intention of redcing the galliom and nat the iron is wo} feasible. There may be the passbilty fo have a two stage process were the iron is reduced and removed ‘hen the gall is redweed, Sf no loses of galxnr are avceplable in the irom product it is neestary to maintain the gallon at 05M. ASSUME the atvtycofients are unity i, concentration = axtvity. Thus E: = 0.529 + 0.01972 logiGa"*} = 0.529 + 0.01972 log(0.5} 0.529-0.006 = 0.535 V -0,529- 0.01972%0,301 = - Alt this potential the von concentration in solution is given by E= 0.535 = 0440 + 0.02598 logiF?"] logfte*} = (0.535-+0.440)/0.02598 = -0.095 (0.02958 = iA BMI *SS. 50 [FE"] = 6.143510" = ASSUME the fist stage removes only iron ging a feed solution of 0.5M Gal* and 6.143¢810°M Pe* .0343 gpl Lot the second stage derease the Ga"* to 10°M, ie, 10°*69.7 = 6.97*10" gpl As above, E. = 0.529 + 0.01972 log(10"} = 0.529 - 0.11832 = 0.647 V Asai, log/Fe*) = (0.647+0,440)/0.02598 1207 (0.02958 = 6,998 So (PE*] = 1.005*10°M = 1.005*107*55.9 = 5.616*10° gpl 22‘Tihusfom every lire of solution, gallm metal produced = (V.5-10°}%69,7 = 34.850 g Iron metal prodcrd = (6.143e10"-1.005%10"F*55.9 = 0.0343 g So the metal produced is 34.850) (34.850--0.0343)*100 = 99.90% Ga THUS, the proves as enuisaged is not feasible as the levels of iron in the gallon are too high. To make the process work it is necessary ta increase the potential digerence betveen the reduetion ennples, the sigplest wy of doing this isto use reagent which destabilives ferrous or stabilses Gia" by forming complexes, 23