CHE5077Z Introduction to Hydrometallurgy Assignment 2011 5 t/hr of a mixed sulphide mineral concentrate, containing by mass 60% NiS, 20%

CoS, 10% FeS, and 2% CuS with the rest being gangue, is pulped with 30 m3/hr of fresh process water containing 5 g/L H2SO4. The slurry is leached in a pressure autoclave with oxygen to dissolve 96% of all the sulphide minerals. The leach li quor is subsequently processed to selectively recover Ni and Co values according to the flow sheet below, while Fe and Cu are rejected as wastes. The primary ex it route for the sulphur is a relatively pure stream of Na2SO4. The Neutralisation and Fe/Cu removal stage employs a solution of Ca(OH)2 as reag ent. Fe3+ and Cu2+ are rejected as their hydroxides and the Ca is quantitatively removed as gypsum (CaSO4 2 H2O). The leach residue is also removed in this stage. T he cobalt SX unit employs a novel extractant, which is highly selective to Co an d achieves 98% extraction of the incoming Co. The organic is stripped with a mil dly acidic solution and CoSO4 is recovered quantitatively from the strip liquor by evaporative crystallisation. The impurities removal stage removes all remaini ng Co and Cu and other impurities still in the solution before it enters the Ni tank house. The Ni electrowinning feed stream is mixed with the re-dissolved Ni( OH)2 from the sulphur removal section. Electrowinning recovers about 50% of the incoming Ni as cathode. The Ni in the spent solution is then quantitatively prec ipitated with NaOH as Ni(OH)2 in the sulphur removal section. The solid is filte red off and then re-dissolved with a fresh stream of 1M (98 g/L) sulphuric acid, controlled at a flow rate such that the re-dissolved Ni solution is at pH 5, be fore recycle to the Ni tank-house. The Na2SO4 in the filtrate is quantitatively recovered by evaporative crystallisation.

Tasks: 1. Write balanced reaction equations for the sulphide leach reactions (assu me sulphate is formed, assume all Fe is oxidised to Fe3+), the acid neutralisati on and precipitation of Cu and Fe hydroxides and gypsum and the electrowinning r eactions (assume oxidation of water at the anode). 2. Establish a complete mass balance for Ni, Co, Cu, Fe, SO42- and H+ in th is process, including information about the annual production of CoSO4, Ni catho de, and Na2SO4, annual requirement for Ca(OH)2, NaOH and make-up H2SO4 in tons, hourly stoichiometric requirement for oxygen, and annual tonnage of waste genera ted in the neutralisation and precipitation stage (ignore the impurity removal s tage). You can assume that all filter cakes are dry, i.e. no water or solution i s lost. Assume 350 production days per annum. 3. Some laboratory data for the rate of re-dissolution of the Ni(OH)2 parti cles (50 m in diameter) in 1 M H2SO4 solution is given in the table below. Show by calculation that the dissolution reaction follows shrinking sphere kinetics. Pla nt practice has shown that the Ni(OH)2 crystal size is closer to 80 m, Determine wh ether the volume of the installed reactor of 25 m3 is still sufficient given the larger particle size at the operating flow rate of 32 m3/hr. Time (min) Conversion 0 0.0 % 2 23.1 % 4 42.2 % 6 58.8 % 8 71.0 %

12 16 20 24

87.9 % 96.0 % 99.5 % 100 %

4. In the neutralisation and precipitation reactor, hydrated lime (Ca(OH)2) is added to neutralise the acid and precipitate Cu and Fe as hydroxides. The ad ded calcium is quantitatively precipitated as gypsum (CaSO4). a. determine the maximum pH to avoid any Ni or Co precipitation b. if the reactor is operated at 1 pH unit below this maximum, determine th e residual concentrations of both Fe3+ and Cu2+ in the solution. metal Fe(III) Cu Ni Co pKs 38.8 19.32 15.2 14.9

5. Determine the operating voltage for the Ni electroplating process if the operating concentration in the tanks is 30 g/L Ni, and water is oxidised at the anode at pH 1, the operating current density is 350 A/m2 and he voltage drop ac ross the electrolyte is 250 mV. The tank house operates at 40C. Assuming a current efficiency of 92%, determine the total cathode area required to achieve the des ign Ni production. Indicate in a sketch how the electrodes would be configured. 6. The partition coefficient for the new solvent extractant under the preva iling operating conditions has been determined to be 2.3 and is more or less con stant. Determine the number of stages required for the extraction circuit, if th e stripped incoming organic has a residual Co concentration of 0.5 g/L and the r atio of aqueous to organic flow rates is around 1.5. Do this by stage-to-stage c alculation and verify by McCabe-Thiele construction (careful this is difficult to do accurately in this case as O/L and equilibrium lines will come very close). W hat should the exact aqueous to organic flow rate be to match the estimated numb er of stages exactly for the given performance? 7. Engineer Clevachap suggests that the Ni(OH)2 re-dissolution stage should be integrated with the pressure leach effluent as sketched below. Comment, with reasons, on whether this is a good or bad suggestion, but you don t need to repeat the entire mass balance calculation.

Present your assignment as a MS Excel file with separate sheets for the calculat ions for each question, where relevant. Comment and colour-code your spreadsheet as much as possible so I can follow your calculations. Further, summarise the p roject brief, all answers and salient data in a separate short (5 pages max.) wr itten report in MS Word (or pdf). Make sure you submit both report and spreadshe et together and upload these onto the VULA site by Fri 13 May 2011. Late submiss ions will be penalised. You are welcome to collaborate on this assignment, but y ou must identify your collaborators in the report and make individual submission s. Blatant copying will not be tolerated.