MULTI MIX SYSTEMS

Multi Mix Systems Pty Ltd 27 Barbican Street West Shelley WA 6148 Australia ACN: 087 869 994 Phone: 08 9457 9944 FAX: 08 9457 9668 Mobile: 0417 961 897 E-mail: bjellis@one.net.au ABN 78 905 723 254

Technical Bulletin
2. Optimising the Operation of Gold Electrowinning Cells
As a service to our clients and prospective clients, MMS will periodically review the information available on a particular subject and distribute summaries of our research. We would like these technical bulletins to generate some interaction and discussion. If you have any comments or questions relating to any of the MMS technical bulletins, or any suggestions for future bulletins, please contact Brad Ellis or Paul Dalley on 08 9457 9944 (phone), 08 9457 9668 (fax), or E-mail bjellis@one.net.au. 1. Introduction As the short to medium outlook for the gold mining industry continues to worsen, most operations are looking for ways to reduce the cost to produce an ounce of gold. The obvious answer increase the ore grade and tonnes treated. Easy! As operations strive to increase ore throughput and grade, it is becoming increasingly common for plant personnel to find plant solution tails rising. Often, this is a result of not moving the carbon through the adsorption circuit quickly enough. Inadequate stripping capacity, particularly in circuits using the Zadra elution process, is sometimes the limiting step. Within the stripping process it is often electrowinning performance that is determining maximum stripping frequency. With this in mind, we thought it may be useful if we reviewed gold electrowinning and offered some suggestions as to how electrowinning efficiency may be improved. In this technical bulletin we will: Present some electrowinning theory, Describe how to monitor an electrowinning circuit and calculate standard design criteria Discuss the factors that can effect electrowinning efficiency, and Offer some ideas on how to improve the efficiency of your electrowinning circuit. To a great extent, the calculations made to size gold electrowinning cells are based on data and models reported by Roger Paul of Mintek. In Australia, extensive plant data collected and interpreted by Mike Costello has been used to further develop the methodology used to size gold electrowinning cells. Discussion presented in this bulletin is based on the Mintek type cell. However, most comments are relevant to other cell types.

2. Some Theory Electrowinning involves the exchange of electrons between a solid electrode and ions or molecules dissolved in solution. The rate of the reactions involved depends on the electrode potential, the electrode area and the rate of mass transport of the electroactive species to the electrode surface. If the cathode potential is sufficiently negative, all of the electroactive species undergo reduction to metal as soon as they reach its surface. The current at which this point is reached is known as the limiting current. Increasing the cathode potential further, results in the depletion at the cathode surface of the metal salt being reduced. At this point the transport of the ionic species through the Nernst boundary layer to the cathode surface becomes the rate determining step. That is, the rate of metal reduction at the cathode has moved from electrochemical (kinetic) control to mass transport control. To increase the rate of the electrowinning process under these conditions it is necessary to increase either the electrode area or the rate at which the electroactive species are delivered to the cathode. For the conditions noted, Table 1 presents the equilibrium electrode potential (Eeq) for a number of reactions of the general form: M(CN) xy-x + ye- = M + xCNTable 1 Equilibrium Potential for the Reduction of Metal Cyanide Ions (Metal ion concentration = 10-4 mol/litre, Free cyanide concentration = 0.2%) Metal Reaction Metal Eeq Concentration Valence (V) (g/m3) 2H2O + O2 + 4e- = 4OHpH = 13 +0.45 20 Hg(CN) 42- + 2e- = Hg + 4CN2 -0.33 20.7 Pb(CN) 42- + 2e- = Pb + 4CN2 -0.38 10.7 Ag(CN) 2- + e- = Ag + 2CN1 -0.45 19.7 Au(CN) 2- + e- = Au + 2CN1 -0.63 6.3 Cu(CN) 32- + e- = Cu + 3CN1 -0.75 2H2O + 2e- = H2 (g) + 2OHpH = 13 -0.78 5.5 Fe(CN) 64- + 2e- = Fe + 6CN2 -0.99 5.9 Ni(CN) 42- + 2e- = Ni + 4CN2 -1.07 6.5 Zn(CN) 42- + 2e- = Zn + 4CN2 -1.22 Eeq is calculated using the Nernst equation; Eeq = E0 + 0.059 log {M(CN) xy-x / [CN-]x} The standard reduction potential E0 is calculated from the standard reduction potentials of the reaction; My+ + ye- = M and the equilibrium constant for the reaction; My+ + xCN- = M(CN) xy-x As indicated in Table 1, cyanide complexes of mercury, lead and silver will be electrodeposited in preference to gold. This is a very important point to note if you are electrowinning gold from an eluate with a high silver content as silver will be deposited (and hence consume current) in preference to gold. The reduction potentials for copper, nickel, iron and zinc are more negative than gold. However, at the potential used in gold electrowinning, the deposition of copper in particular is possible depending on the copper concentration in the eluate. Paul and Costello have noted that every tenfold increase in copper concentration causes a positive shift of 0.06V in the copper equilibrium potential. Consequently, the equilibrium potential for 630ppm copper in eluate will be approximately 0.63V, the same as gold at 20ppm. As would be expected, copper recovery increases as the voltage applied increases.

During the electrowinning of gold from an alkali cyanide electrolyte, the following reactions occur at the cathode and anode. Cathode: Au(CN) 2- + e- = Au + 2CN2H2O + 2e- = H2 + 2OHO2 + 2H2O + 4e- = 4OH2H2O = O2 + 4H+ + 4e(a) (b) (c) (d)

Anode:

Oxygen solubility in hot eluate (electrolyte) is very low. Consequently, cathodic reaction (c) should not consume very much current. However, if the eluate linear flowrate is too high (see section 5.1), oxygen generated at the anode may be carried into the cathode bed. Marsden and House report that the reduction of oxygen at the cathode can account for up to 50% of the applied current in some electrowinning cells. Under conditions when gold electrowinning from alkali cyanide electrolytes is mass transport controlled (that is, when the cathode potential is sufficiently negative), cathodic reaction (b) also occurs and hydrogen is evolved. It can be seen that both reactions (b) and (c) generate hydroxide ion resulting in a localised increase in electrolyte pH at the cathode. The current potential curve for gold deposition from a cyanide solution is presented in Figure 1.

Potential
02 + 2H2O + 4e = 4OHMass Transport Control Region

Au(CN) 2- + e = Au + 2CN2H2O + 2e = H2 + 2OH-

Current
Figure 1 General Form of the Current Potential Curve for Gold Deposition from Cyanide Solution Gold deposition, reaction (a), is electrochemically controlled to a cathode potential of approximately 1.0V. At more negative cathode potential, the rate of gold reduction is typically mass transport controlled. The area of mass transport control is indicated on Figure 1. Figure 1 also indicates that hydrogen evolution and gold reduction occur together until the limiting current is reached and the rate of gold deposition becomes mass transport controlled. Above the limiting current the predominant reaction at the cathode is the evolution of hydrogen. When electrical energy is passed through a solution containing a metal salt, deposition of metal at an electrode will occur. The mass of metal deposited is dependent on the quantity of electrical energy passed through the solution. The quantity of electrical energy applied is measured in coulombs, where one coulomb is equal to one amp flowing for one second.

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Assuming perfect current efficiency, the mass of metal deposited can be calculated using: M =(I x t x A) / (Z x F) where, M = mass of metal (grams) I = current (amps) t = time (seconds) A = atomic mass of the metal Z = metal valency in solution F = Faradays constant (96,500 coulombs) In the case of gold, this formula indicates that the passage of 96,500 ampere seconds of electrical energy should result in the deposition of 197g of gold. However, the generation of hydroxide, evolution of hydrogen and reduction of other metals such as silver and copper that also occur at the cathode consume most of the current applied. To take account of the inefficiency of the system, the term current efficiency is introduced. Data reported by Costello indicates that current efficiency decreases as gold concentration in the eluate decreases. Based on operating plant data, Costello estimates that current efficiency in a typical gold electrowinning cell is equal to approximately 15% of the mean eluate gold grade. However, it is important to note that current efficiency is also a function of current density. If the current density is too high, the current efficiency will be poor regardless of the electrolyte gold concentration. In Australia, the current required by a gold electrowinning system is generally calculated assuming an average current efficiency in the range 8 12.5%. As noted in previously, the silver cyanide complex is more electropositive than gold. Consequently, it is reduced at the cathode in preference to gold during electrowinning. Current efficiency for silver deposition is generally assumed to be approximately 20%. The design of most electrowinning cells used in the Australian gold mining industry has been derived from the Mintek cell. The Mintek cell is rectangular and consists of a series of alternately placed anodes and cathodes arranged parallel to each other. In this type of cell the direction of eluate flow is parallel to the direction of current flow. Typically, the anodes used are fabricated from stainless steel wire mesh or punched plate. The cathodes consist of a porous packed bed of very fine mild steel wire, or wool made by winding the steel wool around a cathode former (current feeder). Layers of woven stainless steel wire are also used as cathode material. Packed cathodes of steel wool or stainless steel wire provide a very high cathode surface area while maintaining good cathode porosity. In Mintek type cells, the potential drop that occurs across the cathode bed limits its thickness. The rate at which the potential falls as the distance from the anode increases is dependent on the conductivity of the electrolyte. As the potential falls, the rate of gold reduction at the cathode surface moves from mass transport control to electrochemical (kinetic) control. If the cathode bed is too thick, the potential continues to fall until gold deposition stops and electrical bypassing occurs. Paul et al have noted that in the range 1.0V to 1.3V the deposition rate is determined by the electrode potential, while at potentials more negative than 1.3V the rate is mass transport controlled. This concept is illustrated in Figure 2. A cathode is at its most electronegative on the two sides that face an anode (points A and F on Figure 2). In the regions AB and EF the rate of gold reduction is mass transport controlled, while in the regions BC and DE the rate of reduction is electrochemically controlled. In the region CD deposition does not occur. To ensure the region of mass transport control is maximised, the thickness of most packed bed cathodes is limited to between four and six centimetres. It is worth noting that there is a cathodic shift in the equilibrium potential for gold deposition of 0.12V for every tenfold decrease in gold concentration in the eluate. As a result, as gold concentration in the eluate decreases an increasing proportion of the cathode becomes inactive for the reduction of aurocyanide ions to metallic gold. Equation 1

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-2.0 A

Mass Transport Control

B E

E,V (vs sce)

Kinetic Control
-1.0 C D

No Deposition

0.5

Distance across cathode

Figure 2 Potential distribution across a packed bed cathode. For a gold electrowinning cell utilising packed bed cathodes, the cell design revolves around the single pass extraction, E. Single pass extraction is defined as the fraction of an electroactive species removed from the eluate in a single pass through an electrowinning cell. Single pass extraction is defined as; E= 1 cout / cin = 1 exp (-L/ ) where: Equation 2

cout and cin are the concentrations of the electroactive species entering and leaving the electrowinning cell respectively, L is the total length of packed bed cathode, and is known as the characteristic length.

Paul has presented an equation for the calculation of characteristic length () that is dependant on the cathode surface area, the diffusion coefficient of aurocyanide, eluate linear flowrate, diffusion layer thickness and voidage in the packed bed cathode. The characteristic length can be determined experimentally and varies proportionally with eluate linear flow velocity (u) and the thickness of the diffusion layer ( ) at the electrode surface. The value of is inversely proportional to the linear flow velocity raised to some power. As a result the value of the characteristic length can be expressed according to the equation = kux where k, the mass transfer coefficient, is a constant. The value of the power, x, has been reported by various sources as having a value between 0.5 and 0.65. By assuming; constant void space in the cathode bed, constant cathode surface area, and an eluate flowrate approaching the practical flow limit (approximately 400 litres/m2/min), Paul has calculated a typical characteristic length to be approximately 31cm. From a practical viewpoint, it is important to note that characteristic length increases with the square root of flowrate (approximately).

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3. Required Elution Cycles When optimising your electrowinning circuit, a good starting point is to determine the number of elution cycles you need to do each month. A sample calculation is presented below. Mean Dry Tonnes per Hour Mean Head Grade Mean Au Recovery Recovered Gold Flow Mean Loaded Carbon Grade Mean Barren Carbon Grade Incremental Carbon Loading Required Carbon Movement Rate Stripping Circuit Batch Size Strips Required per Day t/h g/t Au % g/h Au g/t Au g/t Au g/t Au t/day t A B C D=AxBxC E F G=EF H = D x 24 / G I J=H/I

If your ore contains a lot of silver, dont forget to take this into account. Use the total precious metal loading to determine the required rate of carbon movement instead of relying solely on a gold balance. 4. Circuit Measurements To check the performance of your electrowinning circuit you will need to make the following measurements: volume of eluate produced per strip (not relevant to Zadra circuits), electrowinning cell dimensions, eluate flowrate per cell (if more than one cell is operating in parallel), cathode dimensions, average weight of steel wool or stainless steel wire per cathode, grade of steel wool or stainless steel wire diameter, operating eluate level (in each of the EW cell), and cell current and potential. This information is used to calculate the current density and eluate linear velocity in each electrowinning cell. Sample calculations are presented below. To determine the volume o f eluate produced per strip (v) from an AARL elution circuit, isolate the water flow into your elution water tank and measure how far the water level drops over a measured period of time. Using the known dimensions of the tank you can calculate the elution water flowrate. Multiply the elution water flowrate by the elution time (including the cool down period) to determine the volume of eluate produced per strip. To calculate the eluate flowrate per cell (U), measure the cell dimensions and calculate the cell volume up to the base of the cell overflow weir. Remove all the cathodes and anodes from the cell, start the eluate circulation pump and time how long it takes to fill the cell to the base of the cell overflow arrangement. Measure cathode dimensions and eluate operating level in the electrowinning cell with a tape measure. To determine the mass of steel wool per cathode, wind steel wool onto several cathode formers. Cut the steel wool off each cathode former, weigh the wool from each cathode and average the results. The steel wool grade is written on the carton the wool is supplied in. If you use stainless steel wire cathodes, remove the hanger bar from several cathodes and determine the average weight of stainless steel wire per cathode. Check the last cathode purchase order to determine the wire diameter used. Current draw per cathode can be checked with a suitable tester and potential across each cathode / anode pair can be measured using a multimeter.

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Sample Electrowinning Cell Calculations Carbon mass per strip Incremental carbon loading, Au Incremental carbon loading, Ag Desorbed gold per strip (1.5 x 3100) Desorbed silver per strip (1.5 x 620) Elution water flowrate (as measured) Elution Cycle Time (AARL circuits only) Cool Down Time (AARL circuits only) Batch eluate volume (AARL) (6.5 x (130/60 + 23/60) i. Eluate Linear Velocity Number of EW cells in parallel Eluate flowrate (measured) Cell width (measured) Eluate depth (measured) Submerged cell area Eluate linear velocity tonnes g/t g/t g g m3/h min min m3 1.5 3,100 620 4,650 930 6.5 130 23 16.6 1 5.55 0.605 0.500 0.303 0.306

(0.500 x 0.605) (5.55 / 60 / 0.303)

m3/h m m m2 m/min

In this example the eluate linear velocity is at the lower end of the target range of 0.25 0.50 m/minute. The eluate flowrate in this case does not exceed the volumetric capacity of a single, standard 0.36 m2 cell. A linear velocity in excess of 0.5 m/min may indicate the need for two cells operating in parallel. See Sections 5.1 and 6.2 for comments on how eluate flowrate influences electrowinning performance. ii. Current Required Gold desorbed per cycle (from above) Silver desorbed per cycle (from above) Assumed gold current efficiency Assumed silver current efficiency Target electrowinning cycle time Current required by Au (4,650 x 96,500 x 1) (197 x 12 x 3600 x 0.12) Current required by Ag (930 x 96,500 x 1) (108 x 12 x 3600 x 0.2) Total current required g g % % h A A A 4,650 930 12 20 12 439 96 535

The calculation of current requirement is discussed in Section 2. In this example a standard 600A rectifier would be adequate for the duty. However, a small increase in total precious metal loading would increase current requirement beyond rectifier capacity. What if calculations indicate current demand well in excess of a single rectifier? Assuming the eluate flowrate was within the volumetric capacity of a single cell, two cells could operate in series to ensure the current demand was satisfied. iii. Current Density a) For Stainless Steel Wire Cathodes Average cathode width (measured) mm Total cathode length (measured) mm Cathode length under hanger bar (measured) mm Average cathode weight (measured) kg Eluate level below hanger bar (measured) mm Submerged cathode area (0.56 x (0.565-0.08)) m2 Weight of cathode submerged (0.272/(0.56 x 0.6) x 1.28) kg Cathode wire diameter m Density of stainless steel g/cm3 Volume of SS wire submerged (1.035 x 1000 / 8.02) cm3 2 Wire cross sectional area ( x (0.0152/2) ) cm2 Submerged wire length (129/0.0001815/100) m

560 600 565 1.28 80 0.272 1.035 152 8.02 129.0 0.0001815 7,110

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Submerged wire surface area per cathode Cathodes per cell Current applied (measured) Current density

(535 / (9 x 3.395))

( x 2 x 0.000152/2 x 7110) m2 3.395 9 A 535 A/m2 17.5 mm mm mm kg kg m2/g m2 A A/m2 600 550 500 0.5 0.45 0 0.0173 9 70.06 535 7.6

b) For Steel Wool Cathodes Cathode width Total cathode length Submerged cathode length Steel wool weight per cathode Weight of steel wool submerged Grade of steel wool Surface area of steel wool (see Table 4) Number of cathodes Total cathode surface area (9 x 450 x 0.0173) Current applied Current density

The target current density range is between 5 and 15 A/m2. Higher current densities tend to decrease gold deposition quality and increase sludging. The preceding calculations highlight the importance of the steel wool grade used (or stainless steel wire diameter). The fine wire diameter of Grade 0 steel wool generates a very high plating area per unit weight. The high surface area enables more current to be carried while maintaining a reasonable current density. If your calculations indicate that current density is too high, change to a finer grade of steel wool. If this is not possible, consider modifying your electrowinning cell to incorporate additional cathodes. iv. Current Efficiency Desorbed gold per strip (1.5 x 3100) g For the sake of this example, assume no silver is present. Current applied A Current required at 100% current efficiency A Current efficiency (52.7/600 x 100) % 4,650 600 52.7 8.8

If silver is present, calculate the overall current efficiency based on total precious metals loading. 5. Optimising Electrowinning in AARL Elution Circuits At operations using the AARL elution system, the concentration of gold in the eluate at time t can be related to the initial gold concentration using the following equation; Ct = Ci exp (UEt/v) Equation 3

where Ct = gold concentration in the eluate after t minutes Ci = initial gold concentration in the eluate U = eluate flowrate through the electrowinning cell (m3/min) E = fraction of gold removed from the eluate per pass (single pass extraction) t = recirculation time (minutes) v = total eluate volume (m3) Initial eluate grade (Ci) can be determined by sampling (assuming you do not start electrowinning until after the completion of stripping). Alternatively it can be calculated by multiplying the incremental carbon grade (loaded carbon grade barren carbon grade) by the carbon batch size and then dividing by the volume of eluate produced per strip. Substituting for E in equation 3 (from equation 2) allows a design engineer to cross check the length of cathode material required to achieve a target single pass extraction (assuming =31

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cm). It is then possible to check the number of cathodes required by assuming an individual cathode thickness, typically between 4 and 6cm. Equation 1 implies that the gold concentration in the eluate at time t will be minimised by increasing eluate flowrate through the electrowinning cell, single pass extraction and eluate recirculation time, and by decreasing eluate volume. Of course, there are practical limits. From an operators perspective, single pass extraction can be calculated using the gold concentration of the eluate entering and exiting the cell. It is then possible to predict Ct using equation 3. If your eluate contains silver, you will need to take this into account. A sample calculation is shown below. Batch eluate volume (AARL) m3 16.6 Desorbed gold per strip (1.5 x 3100) g 4,650 Desorbed silver per strip (1.5 x 620) g 930 Moles of gold (4650/197) moles 23.6 Moles of silver (930/108) moles 8.6 Consider 1 mole of silver to be equivalent to 1 mole of gold in electrowinning terms. Mole equivalents of gold to EW 32.2 Gram equivalents of gold to EW 6,343.4 Initial precious metal concentration (Ci) ppm 382 Use the gram equivalents of gold as the initial gold concentration (CI) in equation 3. Now, lets say you want to calculate the required eluate flowrate to reduce the total precious metals concentration in the eluate to less than 5ppm in 12 hours. Assuming single pass extraction (from cell in/out sampling data) is approximately 75%, equation 3 indicates that an eluate flowrate of 0.13 m3/min is required. 5.1 Eluate Flowrate Once you know the eluate flowrate per cell, you can calculate the eluate linear velocity (u) as per the example in Section 4. The maximum eluate linear velocity recommended for gold electrowinning is 0.5 metres per minute. Most engineers use a linear velocity of 0.4 m/min in electrowinning design calculations. If the eluate linear velocity is significantly less than 0.4 m/min, it may be possible to reduce Ct by increasing the eluate flowrate (U). Increasing the eluate flowrate will increase the number of times (plug flows) each batch of eluate is circulated through the electrowinning cell in a given electrowinning cycle time. Similarly, increasing the electrowinning time generally results in a lower spent eluate grade as a result of increasing the number of eluate plug flows through the electrowinning cell. However, often cell pass efficiency and the quality of gold attachment to the cathode decrease as eluate flowrate is increased. In spite this, total gold extraction is generally higher at the higher eluate flowrate because of the larger number of eluate plug flows achieved in a given period of time. Another point to note regarding eluate flowrate. If the flowrate through the electrowinning cell is too low, the eluate may not sufficiently cool the thin wires that make up the cathode. This can lead to the cathode wires burning through at the air / eluate interface. 5.2 Single Pass Extraction During the late 1980s Mike Costello collated information from a number of mine sites in an effort to develop a relationship for single pass extraction (cell pass efficiency), E. Based on his analysis of data collected from a number of Australian operations, and using the equation; F = 1 (B/P) 1/n where, F = fraction of gold removed per cathode, B = barren eluate grade at cell outlet, P = pregnant eluate grade at cell inlet, and n = number of cathodes, Equation 4

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Costello calculated the typical single pass extraction per cathode to be approximately 14%. Based on this empirical data, single pass extraction can be estimated for a given number of cathodes in an electrowinning cell. Results published by Costello are presented in Table 1. Please note that this data is valid for cells using singly wound mild steel wool cathodes (1390 g steel wool per square meter of cathode area) operating with a current density of 5 15 A/m2, an eluate linear flowrate of 0.4 m/min and an eluate caustic concentration of 0.5% w/v. Table 2 Single Pass Extraction Number of cathodes 6 9 12 16 18 27 Single Pass Extraction 0.59 0.74 0.84 0.91 0.93 0.98

This empirical relationship indicates that, for a typical nine cathode electrowinning cell, it should be possible to achieve a single pass extraction of approximately 70%. In reality single pass extraction can be effected by a number of factors including the concentration of the electroactive species entering the electrowinning cell. However, for the electrowinning of gold rich eluates single pass extraction is generally considered to be independent of Cin between 10 and 200ppm Au. A number of electrical and mechanical factors will effect single pass extraction. A brief discussion of some of these factors is presented in Section 7. The discussion presented in Section 7 is relevant to cells associated with both AARL and Zadra elution circuits. 6. Optimising Electrowinning in Zadra Elution Circuits In Zadra elution circuits, gold rich pregnant eluate from the elution column is cooled to below boiling point and passed through an electrowinning cell where gold is deposited on the cathodes. On leaving the electrowinning cell, the now gold poor eluate is re-heated before it is circulated back into the elution column. For rapid carbon stripping using a pressure Zadra system, elution circuit design is typically based on the circulation of 30 bed volumes (BV) of eluant at a flowrate of approximately 2.5 BV/h and a temperature of 125oC. Under these conditions it should be possible to complete an elution cycle in 12 hours assuming reasonable electrowinning efficiency. It is possible to accelerate the rate of gold elution in a Zadra system through the controlled use of additive chemicals such as hydrazine. Hydrazine hydrate is used in Elf Atochems patented Actired Process. However, there is little point in accelerating the rate of gold elution if installed electrowinning capacity is incapable of recovering the gold from the eluate. 6.1 Single Pass Extraction For a Zadra elution circuit, a design engineer would typically target an average electrowinning single pass extraction of approximately 90%. Achieving the design electrowinning single pass extraction in a Zadra elution circuit is critical. Unlike the AARL elution system, poor single pass extraction in a Zadra system has a direct impact on the elution efficiency. Testwork and plant experience has shown that high residual gold grades in eluate returning to the elution column will reduce the rate of carbon stripping. A reduction in elution kinetics will result in longer strip cycle times or higher residual gold loadings on barren carbon. Costello notes that work by Zadra indicated that the rate of carbon elution is reduced significantly if the eluate returning to the elution column contains more than 10ppm gold. Paul notes that work by Adams has also demonstrated the link between single pass efficiency and the rate of elution. Based on an elution model developed by Paul, Figure 3 indicates the influence of single pass extraction on elution efficiency.

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10

2000

1500 1500

Average loading, g/t

1000 1000

500 500

0,7

0,8

0,9

1,0

Electrowinning efficiency
Figure 3 Predicted Performance of a Zadra Elution Circuit at 95 oC after 20 BV at 4BV/h However, when compared to cells in an AARL elution circuit, single pass efficiency achieved by electrowinning cells in a Zadra circuit is generally higher. This is due to the higher eluate conductivity (higher sodium hydroxide concentration) and, possibly, lower dissolved oxygen levels in the eluate due to the higher eluate temperature. As noted in Sections 2, 4 and 5, silver is eluted from loaded carbon before gold and the silver cyanide complex is reduced at the cathode before gold. In the presence of silver, gold single pass extraction will remain low until most of the silver has been reduced to metal. By way of example, if your bullion contains approximately 20% Ag, it is likely that gold single pass extraction during the first several hours of the elution cycle will be low. As discussed above, high gold concentration in the eluate returning to the column slows gold elution kinetics. In turn, decreasing elution kinetics causes elution cycle time to increase. Given the link between elution efficiency and the gold grade of eluate returning to the elution column, it is very important to ensure that sufficient current is applied to the electrowinning cell for both gold and silver deposition. Other factors that influence single pass extraction are discussed in Section 7. 6.2 Eluate Flowrate As noted above, a number of Zadra elution circuits are designed to operate at an eluate flowrate of 2.5 BV/hour. Work reported by Paul indicates that increasing the eluate recirculation flowrate can increase elution kinetics in a Zadra circuit assuming single pass extraction can be maintained. As discussed in Section 5.1, the maximum cell eluate linear velocity is generally accepted to be 0.5 metres per minute. Larger Zadra elution circuits often operate at an eluate flowrate of 2 BV/hour in an effort to limit the size and number of electrowinning cells required. However,

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the number of cathodes in series is normally increased to offset decreased elution flowrate with higher single pass extraction. 6.3 Additives During the last 15 years a number of additives have been used in a n effort to accelerate elution kinetics in Zadra circuits. Recently, Elf Atochem have achieved success with their patented Actired Process. In the Actired Process hydrazine hydrate is injected at the beginning of the elution cycle into the spent eluate before it is pumped into the elution column. Testwork at several West Australian operations has confirmed that the use of hydrazine hydrate can significantly reduce elution cycle time. MMS has been involved with two operations using hydrazine. Operating results over 8 months consistently demonstrated that the effective use of hydrazine reduced the elution cycle time from approximately 12 14 hours to 8 10 hours. However, to effectively reduce elution cycle time sufficient electrowinning capacity must be available to efficiently remove the solubilised metal from the circulating eluate. Recycling high grade barren eluate to the elution column largely negates the benefits associated with more rapidly eluting the gold from the carbon. Before considering an Actired Process trial, check that you have sufficient installed electrowinning capacity. One final note. Hydrazine hydrate is classified as a Class 8 product. Strict safety precautions are necessary for its handling and use. Contact Elf Atochem for details. 7. Electrical and Mechanical Factors Effecting Single Pass Extraction 7.1 Electrical Factors Effecting Single Pass Extraction Cell Current The calculation of required cell current is discussed in Sections 2 & 4. The actual calculation of current requirement is not discussed further here. The rate of gold deposition will increase as cell current increases until the limiting current is reached. Above the limiting current the rate of reduction of gold becomes mass transport controlled (see Figure 1). Most of the current applied in excess of the limiting current is consumed in the reduction of water to hydrogen. Aside from wasting power, excessive hydrogen evolution at the cathode will decrease the quality of gold deposition and increase sludge formation. For gold electrowinning design engineers typically aim to achieve a current density between 5 and 15 A/m2. If your calculations indicate that increasing cell current may benefit the electrowinning operation, check the main cell bus bars and the temperature of electrical connections before increasing it. Most cells use copper bus bars. However, some operations have replaced the original copper bus bars with stainless steel bus bars. Be aware that stainless steel does not conduct current as efficiently as copper. Increasing current passed along a relatively high resistance conductor may result in the bus bar overheating. Over the years there have been serious cell fires at operations such as Fimiston and Sansu. Bottom line if you are going to increase cell current, do it gradually (50A increments) and monitor the heat of bus bar and electrode connections. Finally, it is worth noting that when cathodes are left submerged in eluate without current being applied to the cell, a cathodic gold : anodic mild steel corrosion reaction occurs. This results in the fairly rapid dissolution of mild steel. This can result in breakage of the thin mild steel wool wires at the air / eluate interface. Corrosion of the mild steel can be prevented by emptying the eluate from the cell at the end of each electrowinning cycle, or by applying a small, trickle current. If you intend to maintain a trickle current flow, ensure that the current is not so high that it depletes the caustic from the eluate in the cell. Caustic depletion will result in rapid anode corrosion. This is discussed further below.

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 Anode Condition The predominant anode reaction (see Section 2) is the oxidation of water to oxygen (reaction (d)). This reaction results in a decrease in eluate pH adjacent to the anode. Stainless steel anodes will corrode if eluate pH falls below pH 12.5. Anode corrosion generates Fe and Cr ions. These ions can be reduced at the cathode thereby reducing current efficiency. Chromate ions in particular can significantly inhibit gold reduction kinetics due to the formation of an insoluble chromium hydroxide layer on the cathode. Chromium hydroxide also catalyses the evolution of hydrogen at the cathode, further reducing current efficiency. The concentration of chlorides in the eluate also has a significant effect on anode corrosion. If the caustic concentration of your eluate is high enough and yet anode corrosion remains a problem, check the eluate chloride concentration. High chloride concentration in eluate derived from the AARL system is unusual due to the requirement to use high quality water in the AARL process. However, failure to rinse the carbon sufficiently after the acid wash stage may result in a high chloride concentration in the eluate. Make sure the pH of the solution leaving the column at the end of the water rinse phase is greater that pH 4.0 (approximately). If it isnt, consider increasing the water rinse cycle time. Given the closed eluate loop that defines the Zadra elution process, high chloride levels in the eluate can be present, particularly in circuits with salty process water. Anodes can also become coated with various deposits, resulting in much higher electrical resistance in the electrowinning cell. Depending on the severity of the coatings formed, regular buffing of the anodes with a wire brush can be used to restore electrical efficiency. Keep an eye on the anode wire diameter at the air / solution interface. If the anode wires corrode preferentially at this point, necking will occur. As the degree of necking increases, resistance to current flow down the anode will increase. As this occurs more of the current will be discharged across the surface of the cell and the cathode current density at the air / eluate will interface increase. Ultimately this can lead to the overheating of the thin steel wool wires at the top of the cathode. In the worst case, the cathode wires can burn through. Electrical Connections Loose or dirty electrical connections cause high resistance joints. High resistance joints get hot. Several operations have had serious fires in the gold room as a result of poor maintenance of electrical connections. Even if the hot joints dont lead to a fire that burns down your gold room, they will decrease the single pass extraction achieved by the electrowinning cell by increasing the resistance to current flow. To check the electrical integrity of cell connections, carry out regular cell potential and current surveys. A proforma table for recording survey results is presented in Table 3. The sum of the current drawn by each cathode should be compared to the current output indicated on the rectifier. If they dont match reasonably well, the reason for the disparity needs to be established. If the current draw and potential of a cathode are low, check t he connection and make sure it is tight and clean. If the connections are OK, make sure that sufficient steel wool has been wound onto the cathode. If the cathode potential is OK when coupled with the anode on one side, but low when coupled with the anode on the other side, check the anode connections. If the connections are OK, ensure there is no build up on the anode, check the anode wire diameter and ensure there is no necking at the air / eluate interface.

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Table 3 Cell Survey Proforma Cathode Number 1 2 3 4 5 6 7 8 9 Total Amps = Rectifier Indication V V A Cathode Voltage 1 Cathode Voltage 2 Cathode Current

Electrical Short Circuiting Electrical short circuiting occurs when a direct connection is made between an anode and a cathode. Electrical short circuiting can also occur when cathodes and anodes (not the cathode or anode insulators) become submerged in cell slimes. When current is carried by the cell slimes instead of the eluate (electrolyte), the rate of gold deposition at the cathode will decrease and single pass extraction will fall. You can minimise this problem by more frequent, partial gold removal from the EW cells. Cathode Surface Area Cathode surface area is determined by the weight of steel wool (or stainless steel wire) that forms the cathode bed and the diameter of the wire strands. Table 4 indicates the approximate surface area of different grades of steel wool and stainless steel wire. Table 4 Surface Area Comparison of Different Cathode Materials Material Mild Steel Wool Grade 0 Mild Steel Wool Grade 1 Stainless Steel Wire Stainless Steel Wire Stainless Steel Wire Wire Diameter (m) 30 75 125 152 274 Surface Area (cm2/g) 173 69 41 34 19

Table 4 makes the effect of increasing cathode wire diameter on cathode surface area very obvious. If your elution cycle time is being extended by poor electrowinning efficiency, simply increasing cathode area by using a finer grade steel wool can make a significant difference. Some operations report problems with fine wool cathodes blocking or burning off at the air / eluate interface. If this effects you, calculate the number of cathodes that would become fully laden with gold each day assuming a 5:1 gold : steel wool ratio. Remove this number of cathodes from the feed end of the cell each day and advance the remaining cathodes toward the feed end. Add fresh cathodes to the discharge end of the cell.

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As a general rule, aim for 500 grams of steel wool per cathode in a typical 0.36 m2 electrowinning cell. Less will limit cathode surface area, thereby reducing the ability of the cathode to carry current. Excessive current density can cause cathodes to burn off at the solution line if current is carried from an overhead hanger bar only. When you are calculating operating current density, ensure you use the wetted cathode surface area. Electrode Spacing For optimum cell efficiency, even electrode (anode to cathode) spacing is required. Figure 2 clearly indicates the reason for this. If anode to cathode spacing is uneven, some cathode faces will be closer to an anode than others. As a result, the potential drop across the cathode will not be even. The potential drop through the packed bed from cathode faces farthest from an anode may cause the potential at a certain point within the packed bed to fall below the level necessary to maintain deposition by mass transport control. Depending on the severity of the problem, dead zones (no gold deposition due to low potential) may occur in some cathodes particularly as the eluate gold concentration drops. Remember, for every tenfold decrease in eluate gold concentration there is a cathodic shift in the equilibrium potential for gold deposition of 0.12V. Current will flow preferentially along the past of least resistance, ie the shortest path. Cathode surfaces closest to an anode will receive preferential current flow. This may result in these cathode surfaces blinding from excess gold deposition. If you dont have some form of mechanical electrode spacing, screw in some polypropylene stops along the top edge of the cell to ensure the correct positioning of each electrode hanger bar. To optimise cell efficiency, aim to minimise electrode spacing (while preventing anode to cathode contact) while at the same time maintaining an even gap between alternate anodes and cathodes. Common 0.36 m2, 9 cathode cells are typically between 1350 and 1450mm long and have a standard electrode spacing of approximately 60mm. If you use cathode enclosures, removing them will allow you to decrease electrode spacing to 40mm. By decreasing the electrode spacing to 40mm it is possible to install 12 cathodes and 13 anodes per cell. Before installing additional electrodes, check with the cell manufacturer to ensure the installed bus bars are suitable. To insulate each anode / cathode pair, attach the base from a typical polypropylene breadbasket to each side of each anode using cable ties. Installing additional cathodes will: reduce the electrode spacing resulting in lower cell potential (shorter current flow path), reduce current density for a given cell current thereby reducing cell sludging, and increase single pass extraction. Cathode Bed Thickness The influence of cathode bed thickness on potential drop within the cathode is discussed in Section 2 and depicted graphically in Figure 2. Typical cathode bed thickness is between 4 and 6cm. Cathode Loading As gold is deposited on a cathode, the surface area of the cathode increases. As the cathode surface area increases, the rate of water and oxygen reduction at the cathode also increases. Increased hydrogen evolution at the cathode increases the potential drop across the cathode that may result in dead areas within the cathode packed bed (see Section 2). Above a certain gold loading on a cathode, single pass

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extraction drops dramatically. A general rule of thumb is that mild steel wool cathodes can be loaded to approximately five times their original weight. If you find that the first one or two cathodes in the electrowinning cell block rapidly with gold, review the current being applied to the cell (see section 4 for sample calculations). Reducing the applied current may spread gold deposition more evenly across all of the cathodes. Alternatively, calculate the number of cathodes that will become fully laden with gold each day assuming a 5:1 gold : steel wool ratio. Remove this number of cathodes from the feed end of the cell each day and advance the remaining cathodes toward the feed end. Add fresh cathodes to the discharge end of the cell. Excessive gold loading will reduce the permeability of the packed bed cathode and may result in eluate overflowing the electrowinning cell. Eluate Composition As noted above, single pass extraction is generally considered to be independent of eluate gold concentration between 10 and 200ppm Au. However, as gold concentration decreases the limiting current also decreases. Below 10ppm Au, decreasing single pass extraction can be explained in terms of the cathodic shift in the equilibrium potential of the aurocyanide gold couple that occurs with decreasing aurocyanide concentration. This has been quantified as approximately 0.12V for every tenfold decrease in gold concentration. Obviously, this cathodic shift also has implications for the deposition of copper from eluate. The ohmic potential drop across an electrowinning cell is determined by the conductivity of the eluate. As eluate conductivity increases, the electrical loss in solution decreases. Eluate conductivity can be increased via the addition of sodium hydroxide. For operations using the AARL elution procedure, the concentration of hydroxide in the eluate should be greater than 0.5% to ensure adequate eluate conductivity. If you are attempting to run a pass out electrowinning system, the caustic concentration will probably need to be approximately 1.0% w/v. Remembering that hot caustic solutions can solubilise silica, it may be wise to add the additional caustic to the eluate tank, not via the elution column. Marsden and House note that increasing cyanide concentration in the eluate increases the voltage at which the cell must be operated to ensure the cell operates at or above the limiting current. The ore treated at a number of operations contains mica and other forms of potassium - alumino silicates. Micas in particular are flat and platey and can often report to the cyclone overflow and ultimately find their way into the stripping circuit. Hot caustic solutions will dissolve silica. The solubilised silica may then reprecipitate in pipework, heat exchangers and on electrowinning cell electrodes. When silica deposition occurs in an electrowinning cell, electrical resistance increases dramatically. Eluate Temperature It has been demonstrated experimentally that increasing eluate temperature increases eluate conductivity and thereby cell efficiency. However work undertaken in Australia has shown that cell efficiency is not severely retarded at eluate temperatures of 50 55oC. Silver Silver generally elutes before gold. As noted earlier, the silver cyanide complex is more electropositive than the gold cyanide complex. Consequently, it is reduced at the cathode in preference to gold. It is important to recognise the current required for silver deposition and to allow for this during the calculation of current requirement. A current calculation example is presented in Section 4.

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In Zadra elution circuits, gold single pass efficiency is often very low until a significant proportion of the silver in the eluate has been deposited. 7.2 Mechanical Factors Effecting Single Pass Extraction Solution Short Circuiting Solution short circuiting occurs when there are gaps between the edge of the cathode and the sides or base of the electrowinning cell. Due to the lower resistance to flow in these areas, eluate will flow preferentially through the gaps, bypassing the cathode. If the gaps are large, a significant proportion of the total eluate flow may bypass a given cathode resulting in lower overall single pass extraction. Consider an electrowinning cell with a wetted cross sectional area of 0.30m2. A 40mm gap between the cell wall and the cathode over a wetted length of 500mm is equivalent to approximately 7% of the wetted cross sectional area. Given the low resistance to flow in this area, the volume of eluate bypassing the cathode will be significantly higher than 7%. Photograph 1 presents an example where the removal of cathode enclosures has resulted in a significant gap between the edge of the cathode and the wall of the electrowinning cell.

Photograph 1 Utilisation of Available Cathode Area

Most electrowinning cells are equipped with overflow weir bars that enable regulation of the depth of eluate in the cell. Often it is possible to increase the depth of eluate in the cell by approximately 20mm simply by adjusting the overflow weir bars or fitting hungry boards to the cell outlet. At some operations we have found it possible to increase eluate depth by up to 80mm. 8. Conclusion As operations strive to lower gold production costs, ore throughput and head grade are typically increased to limits imposed by the nature of the orebody and the capacity of plant equipment. Unless matched by an increase in the rate of gold removal, increased gold input results in elevated carbon loadings and a flattening of the carbon loading profile through the adsorption circuit. Ultimately, soluble gold losses tend to increase. To control soluble gold losses it is necessary to increase the rate of carbon advance through the adsorption and

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stripping circuits. frequency.

It is not uncommon to find electrowinning cycle time dictating elution

In this bulletin we have attempted to identify and explain a number of issues that can impact on electrowinning efficiency. Our aim is to enable you to: Define the carbon movement rate required at you operation, and hence the elution cycle time required, Define current electrowinning circuit operating conditions, Identify opportunities to improve electrowinning efficiency, and Make the procedural or equipment changes necessary to realise improved electrowinning efficiency and, as a result, reduce elution cycle time and increase the rate of carbon advance. 9. References i. ii. iii. iv. v. vi. vii. viii. ix. The Chemistry of Gold Extraction Marsden and House The Recovery of Gold from Concentrated Aurocyanide Solutions Paul, Filmer and Nicol Gold from Eluates Paul The Kinetics of the Elution of Gold from Activated Carbon Adams and Nicol Practical Experience of Gold Electrowinning in Australia Costello Experience with the Use of Electrowinning Gold from Pregnant Eluates in the Gold Mining Industry in Australia Costello Actired Process New Industrially Tested Process which Economically Improves Gold Elution Duparque, Louis, Harvey and Van Lierde Electrometallurgy and Electrochemistry Workshop Paul, Costello, Ritchie and Spencer The Electrowinning of Gold from Carbon-In-Pulp Eluates Filmer

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