METALLURGICAL ENGINEERING HYDROMETALLURGY- Ill (EYHYD3A) Test 1: The Elsner Equation for gold leaching can be written as: 4Au + SCN’ + Op + 2H20 = 4 Au(CN)y + 40H From this equation, explain why cyanide ions is a common challenge for the adsorption of gold cyanide complex on activated charcoal. How does the cyanide ion actually affect the adsorption? (10 marks) ‘Answer: Why? From the Elsner equation, cyanide ions is needed to complex the gold. During gold leaching, some free cyanide ions is always needed to keep gold complex in solution. If there is no such free CN-, some of the gold cyanide complex can dissociate and the gold is lost from solution. This free cyanide ions remains in solution and pose a challenge during the adsorption on activated carbon. How? The free cyanide ions, CN-, being of the same charge, much smaller and therefore more mobile compared with the gold cyanide complex Au(CN) ions, are able to compete with the gold cyanide complex for adsorption on site on the activated carbon. They respond to smaller surface polarity on the carbon compared to the gold complex. Briefly give the main motivation for carbon in leach over carbon in pulp during recovery of {gold from leach solution, and how the carbon in leach is carried out in plant operations. (10 marks) Answer: ‘The motivation for carbon in leach over carbor matter in some ores. ‘These carbonaceous matters are able to absorb gold ions from the leach liquor. ClL in plant Operation: the granular activated carbon is added during the leaching stage. {As the gold complex is formed, it is immediately adsorbed on the activated carbon. Gold ion will adsorb to the activated carbon preferentially compared to the organic matter because the activated carbon is stronger to adsorb the gold complex compared to the carbonaceous pulp is the presence of carbonaceous matter in such ores. Presence of organic compound such as ethanol in the solution hinders adsorption of ions on activated carbon. Explain why this is so. How is this effect applied to the advantage of the whole process of solution purification by adsorption over activated carbon? (10 marks) Answer: Ethanol has a lower dielectric constant compared to water. When in solution, it lowers the lectric constant of the solution. Hence oppositely charged ions are able to attract overall di more, and similar charges repulse more. This causes increased repulsion which prevent easy passage to adsorption sites. Adsorption ions can be repelled out of its site. Advantage: Organic solvents such:as ethanol can be used to bring about desorption of adsorbed ions. A solution of 20% ethanol with at about 90°C desorbs gold readily from charcoal. During adsorption of gold ions on activated carbon, comment on the effectiveness of the operation if the distribution ratio, D lesser than one, equal to one or greater one. (8 marks)Answer: During the adsorption stage, Distribution ratio, D = (Concentration of gold adsorbed on activated carbon/ Concentration of metal ion in the aqueous phase) Dis lesser than 1- the metal solid phase, hence metal adsorption is not effective If tis equal to one, the concentration is equal in the two phases. This is also ineffective Ifitis greater than one, the metal ions is effectively being absorbed unto the carbon. Explain the source of the force of adsorption of anions on activated charcoal suspended in higher in the aqueous phase than in the aqueous solution. (10 marks) Answer: ‘When Oxygen is bubbled through a suspen: by the reaction: 02 + H:0 + 2e”= H:02 +20H" ‘The electrons for the oxygen reduction are supplied by the charcoal, making the charcoal, surface to be positively charged. ‘The positively charged charcoal surface makes adsorption of anions such as Au(CN): possible. Itemise the operational steps involved in adsorption of gold from leach solution, the elution step that follow, and the regeneration of carbon. (12marks) Answer: In general, Adsorption takes about 24 hours for a solution contaii One ton of activated carbon adsorbs about 10 Kg gold ‘About 1 Kg carbon is used to treat about 4 litres of solution Desorption of gold from act Desorption of gold is typi hydroxide at 900C. The carbon is recovered first by a washing with water to remove entrained solutions, followed by dewatering. ‘The carbon is re-activated by heating for 30 minutes at 700°C in absence of ai quenching. reduced water, the oxyger jing about 10 ppm gold washing to remove calcium carbonate precipitate, followed byMETALLURGICAL ENGINEERING Hydrometallurgy - Ill (EYHYD3A) Test Il: Mar. 28, 2019 Marking Guide 60 Marks 1. With relevant diagrams, describe the four types of synthetic organic ion exchange materials 28 Marks * Weak acid cation exchangers, containing -COOH groups W ¥ VII ‘* Strong acid cation exchangers W containing -SOH groups, V obtained by sulfonation of addition polymers with divinyl benzene. W s-—-CH—CH—CH—CH,—CH—CH — -—CH—CHy i S057 WIIG © Weak base anion exchangers, W containing amino groups VIVNMETALLURGICAL ENGINEERING Hydrometallurgy - Ill (EYHYD3A) Strong base anion exchanger, W where the base strength of the resin can be increased by using substituted amines WV HyC-N*-CHs cH; cr GH: HyC-Y"-CHy CH co WIV 2. Elution and regeneration can be carried out in a single step. Explain with relevant example an instance of such, 12 Marks © This is elution using an eluate having high concentration of initial counter ions. WW * Example: A resin in the Na* form can exchange its Na* ion for Ca®* and Mg* from a dilute solution of these ions. WY © The mechanism here is based on the high charges of the Ca’ and Mg’. WW * To elute these ions, a concentrated solution of sodium chloride can be used. WW * The solution will penetrate the resin structure and the high concentration gradient of the Na* will cause the free Ca** and Mg”* counter ions to be exchanged for Na* WW ‘* The process achieves the elution of Ca®* and Mg** and regenerate the resin in that single step. VW 3. Astrong anion exchange in the SO.* form can be used to deacidify a solution. Explain the applicable ion exchange mechanism in such case with an example of such application. 12 Marks In a strong anion exchanger in the $Os* form, the SO.” can be attached to two alkyl group sites onaresin. WW 4 In acid solution, a site sharing process of uptake of H2SOs ions can occur WWW as:METALLURGICAL ENGINEERING Hydrometallurgy ~ Ill (EYHYD3A) Ge RTHSO > $04? + 2H2S0, ——> Rt RYHSO VVV The H2S0s ions being in solution as H* and HSOs ions. 7 By this process, H2SOx can be removed from a solution of sodium sulphate by passing the solution over a strong anion exchanger in SO. form. VW 4, Itemise factors that can affect swelling of resin in ion exchange columns. 10 Marks © Low degree of cross linking - high solubility “~ * High exchange capacity, WW when more ionic group in the resin are active for ion exchange * Such as in complete ionization inside the resin WW © When larger counter ions are strongly solvated WW ‘© When solution is relatively dilute WW 5. Describe the operation of a semi-permeable membrane as a ion exchange material. 8 Marks Membrane exchangers are synthetic organic resin prepared in the form of sheets. WW The membrane is able to allow counter ions pass through, while co-ions are prevented. VV Hence, counter ions can be selectively removed from a solution using the membrane. W This is an ideal semi-permeable membrane, which allow only a type of ions pass through. VV 6. Hydrochloric acid and trioxonitrate (V) acid are not used in leaching of uranium in the hydrometallurgical purification to obtain the yellow cake. Which acids are used instead. Explain the reason for this considering the purification of leach solution. 8 Marks HCI or HNO is not used to regulate the pH because uranium ions may not be sorbed from dilute solution of these acids. WW Sulphuric acid is used instead. WWMETALLURGICAL ENGINEERING Hydrometallurgy ~ Ill (EYHYD3A) The distribution coefficient of uranium ions in the resins is very low, below 1, at very low concentrations of this acid. WW For sulphuric acid, as such low concentration, the distribution coefficient is above 1000. WWMETALLURGICAL ENGINEERING Hydrometallurgy — III (EYHYD3A) Test Ill: May. 02, 2019 Marking Guide 54 Marks SECTION I: DESIGN AND SYNTHESIS A pregnant leach solution at 4 g/I copper was treated via solvent extraction. The solution goes through three mixer-settler tanks during the extraction stage and two mixer-settler tanks in the stripping stage. The chelating reaction representing the extraction stage can be written as: : [- te where R is the unsaturated linear hydrocarbon chain. es + Cur= + 2H The metal concentration of the leach liquor reduce from 4.0 to 2.5 to 1.25 and finally to 0.6 g/l at each step of the extraction, while the organic increase from 0.6 to 1.25 to 2.5 and finally to 4.0 g/I, at corresponding steps of the extraction stage. The phase ratio during the extraction is 1, while the phase ratio during stripping is 0.2. During the stripping stage, the concentration of the loaded organic phase decreased from 4.0 to 2.25, then to 0.6 g/l to give the stripped organic phase, while the concentration of the spent electrolyte increased from 35 g/I to 44.5, g/l and then 53 g/l during the two steps of the stripping stage to give the advanced electrolyte. 1. Draw the schematic diagram showing the extraction tanks and the stripping tanks, in circuit including the leaching and the electrowinning operation. 5 marks Stripping 5° | se ayeMETALLURGICAL ENGINEERING Hydrometallurgy — III (EYHYD3A) 2. Inthree sentences, using the extraction stage of your diagram, describe the design of the flow of the aqueous phase and the organic phases. 8 marks In the extraction stage, the organic solvent is flowing from point H in tank 1 to tank 2 to tank 3 and out at point B. “ The aqueous phase is effectively flowing opposite to the organic “ “ from point A in tank 3 to tank 2 to tank 1 and out at point 6. This is the counter current flow design * “ always employed in this operation. 3. The concentration of the final raffinate can be reduced from that 0.6 g/I to a lower say 0.25 g/l If the extraction goes further to four steps and the stripped organic comes in at a lower concentration of about 0.25 g/I instead of the 0.6 g/l a. Itemise extra facilities that will be needed to achieved this. 6 marks One more extraction mixer settler tank must be built. One more stripping mixer settler tank must be built. Plant foot print will increase by about a quarter. “ b. In practice, the extraction may not try to reduce the final raffinate concentration to this lower value. Discuss the reason. 6 marks The increased recovery of 0.35 g/I metal may not justify the capital and maintenance costs of the additional facilities. ’ “ The process will increase metal recovery from the pregnant leach liquor by less than 10 %, but facilities will increase from three steps to four; 33 % increase in capacity. ““ The cost benefit analysis will be unfavourable. ““ Hence, this little amount of leached copper is kept in the recycling stream to the leaching circuit. 4. If 250 I/min of pregnant leach liquor flows through the extraction stage, what is the equivalent advance electrolyte produced to feed the electrowinning circuit in litre/min? 4 marks Given the phase ratio of 1/5 during the stripping stage. Hence, 1/5 of 250 ml/min = 50 ml/min “~ That is, the stripping solution will be 50 ml/min The volume of the advance electrolyte produced = 50 mi/min 5. Ina mixer-settler design, the mixers are tall cylindrical columns, while the settlers are shallow rectangular tank. What is the rational for this structural difference? 8 marksMETALLURGICAL ENGINEERING Hydrometallurgy ~ Ill (EYHYD3A) In the mixer, the aqueous flows down the column while the organic flows up the column. “~ This enables thorough mixing. ° In the shallow tanks of the settler, the stream flows in a direction down the rectangular tank horizontally into layers. ““ This allows effective separation. 6. Write the chemical reaction for the stripping stage of this solvent extraction operation. S marks where R is the unsaturated linear hydrocarbon chain. ” SECTION II: Effect of equilibrium distribution on percentage extraction: Graphical illustration In a solvent extraction operation, the phase ratio is kept constant at 1, while the equilibrium distribution ratio vary as a function of x as D = 10%, where x values ranges from -3 to 3, including zero. 7. Plot graph of percentage extraction (PE) versus distribution coefficient, D, using logarithmic scale on D axis. Ensure you show the data table of D and PE. 8 Marks 8. Use this plot to explain how the distribution co-efficient affects possible percentage extraction. 4 MarksMETALLURGICAL ENGINEERING Hydrometallurgy — Ill (EVHYD3A) € Vaut Unive 100 D PE s 0.001 | 0.0999 0.98009 oo 9 9.08080 oa 8 0 1 50 30.3090 8 300 | 99,0099 1000 | 99.9001 2 10 1002000 tlon Coefficient, D Data Table ~ 4 marks; Plots 4 marks Explanation: Distribution coeff determine achievable PE. High D gives high PE, and vise-versa, ‘The axes can also be interchanged to give alternative chart orientation shown: 0 20 40 60 60 100 Extraction, %