ION EXCHANGE COLUMN DESIGN FOR SEPARATION OF NICKEL TRACES FROM COBALT ELECTROLYTE By A.G. Pavlides and J.

Wyethe SYNOPSIS Base metal impurities normally associated with cobalt include chrome, copper, iron, manganese, nickel and zinc. Because of the similarity in the chemical behaviour of nickel and cobalt, strategies designed to separate cobalt from other base metal impurities will generally also recover whatever nickel is present. DOWEX M4195 is a macroporous resin with covalently bonded weakly basic chelating functional groups. The attached functional groups allow a relatively high selectivity for nickel over cobalt in sulphate media and the resin is used industrially for the removal of nickel traces from cobalt sulphate electrolytes. Equilibrium and kinetic data measured for the cobalt / nickel sulphate system are reviewed and discussed. A mathematical approach used to model nickel breakthrough curves from fixed bed ion exchange contactors is presented and evaluated. Practical application of the approach is demonstrated in a case study where two designs for an ion exchange facility for a 1000 tpa cobalt producing plant are compared.
Senior Process Engineer Bateman Engineering Level 6, 189 Kent St. Sydney, NSW, 2001 E-mail: tony.pavlides@bbr.com.au Principal Engineer Council for Mineral Technology 200 Hans Strydom Drive Randburg, South Africa E-mail: jwyethe@mintek.co.za

1. INTRODUCTION DOWEX M4195 is a macroporous resin with covalently bonded, weakly basic chelating functional groups. The functional groups exhibit a relatively high selectivity for nickel over cobalt. This selectivity allows the resin to be used for separation of nickel from cobalt sulphate electrolytes. INCO at Port Colborne1 in Canada and Chambishi Metals2 and ZCCMs Nkana operation in Zambia make use of fixed bed ion exchange contactors, containing DOWEX M4195 resin, for the purpose of removing nickel from cobalt sulphate electrolyte prior to electrowinning. In all applications, nickel (and cobalt) are loaded onto the protonated form of the resin, and are subsequently eluted with dilute sulphuric acid solution. Development of several projects that include some form of cobalt production (Bulong Nickel, Malborough Nickel, Chambishi Metals Expansion and Nkomati Polymetallic Refinery) has generated interest in this technology and led to a closer examination of some of the design parameters, which are discussed in this document.

2. BULONG LABORATORY TESTWORK DATA Testwork conducted for Resolute Resources by Mintek for the Bulong Nickel Project3 is discussed in the following sections. The testwork data has been made available by kind permission of Preston Resources. 2.1 BATCH STIRRED TANK REACTOR The rate of adsorption (kinetic response) of nickel onto the DOWEX M4195 resin, at ambient temperature and 60oC, was evaluated in a batch stirred tank. The stirring rate was such that the effect of film diffusion was eliminated. The resin was pre-screened between 600 and 850 micron. One liter of synthetic solution (cobalt = 67 g/l; nickel = 250 mg/l) was contacted with 120 milliliters of resin over a period of 24 hours. The solution and resin pH values were set to 2.3 before contact. Solution samples were taken at pre-determined intervals and analysed for nickel. Results are shown in Figure 1.

Figure 1

Kinetic Response of Nickel with DOWEX M4195 Resin

250

200 Nickel (mg/l)

150

100

50

0 0 60 120 180 240 Time (min) Ambient 60 oC 300 360 420 480

Results indicated a significant improvement in the kinetic response at elevated temperature with a time requirement of less than 90 minutes to reduce the batch solution concentration from 250 mg/l to less than 50 mg/l. A contact time of 240 minutes was required for the same reduction in solution concentration at ambient temperature. The improvement in reaction rate with increasing temperature is consistent with a chemical rate-controlling step for the adsorption reaction.

2.2 FIXED BED BREAKTHROUGH CURVE The removal of nickel from a feed electrolyte containing 67 g/l cobalt and 270 mg/l nickel was investigated by passing the feed down through a fixed, 1 m, resin bed. The experiment was done at ambient temperature at a flowrate of 4 BV/h (BV a bedvolume is the solution volume equivalent to the resin volume in a column). The breakthrough curve that was measured is shown in Figure 2.
2

Figure 2

Fixed Bed Breakthrough Curve

250

200 Nickel (mg/l)

150

100

50

0 0 2 4 6 Time (h) Ambient 8 10 12

The adsorption of nickel on DOWEX M4195 resin is relatively slow at ambient temperature, which results in nickel breakthrough occurring within the first few bedvolumes of solution treated.

2.3 LABORATORY SCALE COUNTER-CURRENT-ION-EXCHANGE EXPERIMENTS Laboratory scale counter-current-ion-exchange (CCIX) experiments were conducted on electrolyte feed containing 67 g/l cobalt and 290 mg/l nickel. Each column contained 10 ml of resin pre-conditioned to a pH of 2.3. Experiments were done at ambient temperature at a flowrate of 4 BV/h. A resin residence time (transfer time) of 3 hours was allowed. At transfer, profile samples (solution and resin) were collected from each column. Results for nickel are shown in Table 1.

Table 1

Results from Laboratory CCIX Experiments Column 1 Column 2 140 48% 2400 Column 3 90 31% 1400 Column 4 50 17% 520 Column 5 17 6% 280

Solution concentration (mg/l) NiEffluent/NiFeed (%) Resin loading (mg/l)

210 72% 3800

Results indicated that 4 columns in the adsorption circuit should be sufficient to allow a relatively high degree of nickel breakthrough (72%) through the first column, maintaining the nickel concentration in the barren solution below 50 mg/l. Thus, 3 columns in series are required to contain the mass transfer zone (section of bed where loading gradient exists) at a flowrate of 4 BV/h.

This is equivalent to an overall flowrate of 1.25 BV/h based on the resin volume in 3 columns, which agrees with the findings of Rosato et al7 who showed that the mass transfer zone could be contained in a single column tested at a flowrate of 1.2 BV/h.

2.4 EQUILIBRIUM DATA The equilibrium loading of nickel from a solution containing around 55 g/l cobalt was established by contacting resin and solution in a stirred batch reactor over a period of 7 to 8 hours. The pH was maintained at a value of 2. The resin loading was calculated by stripping the resin and analysing the eluate. Results are shown in Table 2.

Table 2

Results from Batch Equilibrium Tests Resin loading g/l Ni 1.7 2.5 3.1 3.6 Co 28.2 27 25.8 25.6 Selectivity Ni/Co 62 70 68 64

Equilibrium solution composition g/l Ni Co 0.055 0.079 0.099 0.117 55.3 58.5 55.6 53.4

An average selectivity coefficient of 66 for DOWEX M4195 for nickel over cobalt was calculated from the batch equilibrium results. Results from the transfer during the continuous CCIX campaign, as discussed in section 2, are listed in Table 3.

Table 3

Results from a Transfer During Continuous CCIX Campaign Resin loading g/l Ni 1.2 2.3 6.2 Co 27.9 25.8 22 Selectivity Ni/Co 47 30 42

Equilibrium solution composition g/l Ni Co 0.058 0.184 0.422 63.2 63.2 63.2

During the CCIX campaign a nickel loading of 1.2 g/l was obtained from a solution containing 58 mg/l nickel, as opposed to a nickel loading of 1.7 g/l from a solution containing 55 mg/l nickel during batch contact. This suggests that equilibrium conditions were not achieved in the lead column during the counter current test. Selectivity coefficients between 30 and 47 were calculated from the CCIX transfer results. These are closer to selectivity coefficients calculated from data for column tests, published by Rosato et al7, of 40 58. Selectivity coefficients, published by Grinstead 8, varied between 28 and 52.

3. MATHEMATICAL APPROACH 3.1 BATCH KINETICS 3.1.1 Shrinking Core Model Ion exchange adsorption kinetics have been modeled with some success using the unreacted core model, originally proposed by Levenspiel4 to describe heterogeneous reaction kinetics. The model may be written to assume film diffusion, intra-particle diffusion or chemical reaction (or some linear combination) to be the rate-controlling step(s). The functional forms for the intra-particle diffusion and chemical rate control models are shown below:

Cdt =
0

2 QpR 2 1 3(1 X ) 3 + 2(1 X ) 6bD e

(1)

Cdt =
0

1 QpR 1 (1 X ) 3 bk s

(2)

The symbols in the equations are unimportant for the purposes of the discussion that follows, apart from C which represents solution concentration, X which represents fractional resin loading and t which represents time. All other parameters are assumed constant. The above equations show the expected functional dependence of resin loading on solution concentration for the alternative rate controlling steps. A plot is made of the batch kinetic data, measured for the Bulong test work (Figure 1 in section 2.1), in the form of equation 1, which is shown in Figure 3.

Figure 3

Test for Intra-particle Diffusion Control

1.00 0.90 0.80 1 - 3(1-X)2/3 + 2(1-X) 0.70 0.60 0.50 0.40 0.30 0.20 0.10 0.00 0 400 800 1200 Cdt (kg/m .s)
3

1600

2000

2400

Ambient

60 oC

A linear correlation would indicate that the intra-particle diffusion model correctly approximates the measured data, however the curves show that this is not the case for either data set (ambient and 60oC). This seems reasonable from the discussion in section 2.1 on the slow nature of the adsorption reaction, on which basis the adsorption reaction is expected to play an important role in the overall reaction rate. A second plot constructed for the batch data in the form of equation 2 is shown in Figure 4. The plot again shows no correlation for the high temperature data while the correlation for the data measured at ambient temperature is approximately linear during the initial period of the experiment (< 120 minutes).

Figure 4
1.00 0.90 0.80 1 - 3(1-X)2/3 + 2(1-X) 0.70 0.60 0.50 0.40 0.30 0.20 0.10 0.00 0

Test for Chemical Reaction Control

400

800

1200 Cdt (kg/m .s)

3

1600

2000

2400

Ambient

60 oC

(Ambient)

Based on both sets of curves presented, it seems that neither of the shrinking core models provides an adequate approximation of the loading kinetics over the entire experimental period. Both the shrinking core models assume that a sharp reaction front moves through the resin particle. In the case of the chemical rate control model, Hellferich5 disputes this representation of the processes occurring within a resin bead, noting that this model requires that diffusion proceed at significantly different rates through the section that is fully loaded as compared to the unreacted section. For this reason, a kinetic representation is favoured which considers diffusion to proceed in parallel with the loading reaction. 3.1.2 Ion Exchange Kinetics Following Thomas6 Thomas6 has described the kinetics of an ion exchange reaction analogously with a homogeneous chemical reaction. Implicit in his approach is the assumption that all available exchange sites are in contact with the solution at all times. The rate of the ion exchange reaction is expressed as:

k dC1 = k 1 C1 (Q q 1 ) + 1 C 2 q 1 12 dt rxn

(3)

where C1 is solution concentration of metal species (kg/m3) C2 is solution concentration of counter species (kg/m3) q1 is metal loading on resin (kg/m3) Q is total resin capacity (kg/m3) 12 is selectivity coefficient k1 is forward reaction rate constant (m3/(kg.s)) The above reaction kinetics may be incorporated into a shell balance treatment for the resin particle, to yield the final kinetic equation incorporating diffusion and chemical reaction.

C1 1 2 C1 k 1 = 2 r De C 2 q 1 k 1 C1 (Q q 1 ) + t r 12 r r
where r is resin bead radius (m) De is effective diffusivity (m2/s)

(4)

The kinetic approach is valid for a binary ion exchange system, whereas the system under discussion is initially a ternary system involving H+ (or Na+), Co++ and Ni++ ions. However the counter ions which initially occupy the exchange sites are rapidly displaced by cobaltous ions, which are present in large excess, and the exchange system may be considered to be binary once this has occurred. A Crank-Nicholson discrete scheme, incorporating the appropriate initial and boundary conditions, is used to generate a numerical solution to equation (4). The results of the equation fits for the data measured in the Bulong testwork are shown in Figure 5 and the parameters used for the best fit are listed in the table below.

Table 4

Kinetic Parameters for Bulong Batch Tests k1 m3/(kg.s) 242x10-6 150x10-6 2160x10-6 805x10-6 De m2/s 6 x 10-11 15 x 10-11

Ambient 60 oC

The kinetic parameters presented in Table 4 for the experiment conducted at ambient temperature show that the value for the rate constant is relatively insensitive to the value chosen for the diffusivity. This is not the case for the experimental data measured at the higher temperature. The correction to the model when diffusion effects are accounted for at the higher temperature is apparent from the comparison of the two model curves in Figure 6. While the two models describe the measured data equally well in the initial stages of the experiment, the tail of the curve is more fully described by the mixed control model, while the chemical control model predicts a more rapid approach to equilibrium conditions than is measured.
7

Figure 5
250

Model Fits for Batch Kinetic Data

200

Nickel (mg/l)

150

100

50

0 0 60 120 180 240 Time (min) Ambient 60 oC 300 360 420 480

Figure 6
250

Comparison of Mixed and Chemical Rate Control Models

200

Nickel (mg/l)

150

100

50

0 0 60 120 180 240 Time (min) 60 oC Mixed Chemical 300 360 420 480

3.2 FIXED BED KINETICS 3.2.1 Bulong Breakthrough Test The kinetic formulation of Thomas6 (equation 3, section 3.1.2) can be solved together with the mass balance for a plug flow reactor (equation 5) to develop a model for a fixed bed ion exchange contactor. The model is strictly only applicable at ambient temperature since M4195 loading kinetics are more properly described using a mixed kinetic control model at higher temperatures. The loss in accuracy at higher temperatures due to using the chemical rate control model is not considered significant for the purposes of the present study.

C1 F C1 = r + ((1 r ) p C1 + q1 ) A x t t
where F/A is superficial linear velocity (m/s) r is resin bed voidage p is fraction resin pore volume C1 is average solution concentration in resin bead (kg/m3)

(5)

q1 is average metal loading on resin bead (kg/m3)

Equation 5 has been reformulated in terms of a discrete model and is solved simultaneously with the chemical rate equation (equation 3) to develop an expected breakthrough curve, based on the ambient Bulong batch data, at a flow of 4 BV/h (see section 2.2). The resulting curve is shown in Figure 7.

Figure 7
275 250 225 200 Nickel (mg/l) 175 150 125 100 75 50 25 0 0

Breakthrough Curve for Bulong Nickel

6 Time (h)

10

12

Ambient

1.50E-04

2.20E-04

The first curve presented in Figure 7 is generated using a rate constant of 150E-6 m3/(kg.s), measured from the batch testwork described in section 3.1.2. The second curve shown has been fitted to the data points and the value of the fitted rate constant is slightly greater at 220E-6 m3/(kg.s).

3.2.2 Bulong Counter Current Ion Exchange The equations for fixed bed ion exchange developed in the previous section may be solved to simulate a counter current ion exchange treatment process, where the resin bed is divided up into a number of stages and resin transfers occur counter to the flow of solution (see section 2.3). This simulation has been completed for a system of 6 columns, and compared with data measured during the Bulong test program for a feed containing 290 mg/l Ni and 67 g/l Co, at ambient temperature. The value of the reaction constant used is that determined from the single column breakthrough test discussed in section 3.2.1. The predicted exit concentration from each of the six columns is shown in Table 5, along with the measured concentrations. The model data shows good agreement with the exit concentrations measured during the test.

Table 5

Counter Current Ion Exchange Model Col. 1 (mg/l) 210 218 Col. 2 (mg/l) 140 142 Col. 3 (mg/l) 90 84 Col. 4 (mg/l) 50 46 Col. 5 (mg/l) 17 22 Col. 6 (mg/l) 8 9

Actual Model

3.2.3 Rosato, Harris and Stanley7 Rosato et al7 have presented a number of breakthrough curves, for nickel loading onto M4195 resin. The mathematical formulation for a fixed bed contactor, described in section 3.2.1, was fitted to the breakthrough curve measured for a feed flow of 1.2BV/h at 25oC, the feed solution containing 0.5 g/l Ni and 24.0 g/l Co. The value of the fitted rate constant, 125E-6 m3/(kg.s), compares well with the value measured for the Bulong batch test (see section 3.2.1) at ambient conditions, but is lower than the value determined from the single breakthrough curve and counter current experiments. This rate constant was used to generate expected nickel breakthrough curves at the different feed flows and compositions tested by Rosato et al7 at ambient temperature. The results of this exercise are presented in Figure 8. The curves shown in Figure 8 show that the mathematical formulation allows useful approximations of the measured data to be made. Since the experimental loading of cobalt and nickel on the resin (Q) varied between 25 and 40 g/l, the value for Q was set to the measured value for each of the curves in Figure 8. The reason for the variation in measured loading is not clear since it shows no correlation with solution conditions, and it is not discussed in the original text7. Rosato et al7 present two more breakthrough curves, measured at 50oC. The equation set was fitted to the breakthrough curve measured for a feed solution containing 2.1 g/l Ni and 25.9 g/l Co, and the measured rate constant was used to generate the second curve. These curves are shown in Figure 9. The rate constant measured for the test at 50oC is 410E-6 m3/(kg.s), which lies between the values measured for the Bulong batch tests at ambient (150E-6 m3/(kg.s)) and 60oC (806E-6 m3/(kg.s)).

10

Figure 8
2500

Nickel Breakthrough Curves at 25oC

2000

Nickel (mg/l)

1500

1000

500

0 0.0 12.0 24.0 36.0 48.0 60.0 Time (h) 1.2 BV/h 3.6 BV/h 7.2 BV/h 3.6 BV/h 7.2 Bv/h

Figure 9

Nickel Breakthrough Curves at 50oC

2500

2000

Nickel (mg/l)

1500

1000

500

0 0 6 Time (h) 3.6 BV/h 3.6 BV/h 12 18

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4. CASE STUDY 4.1 NICKEL ION EXCHANGE IN COBALT METAL PRODUCTION FLOWSHEETS Base metal impurities normally associated with cobalt include chrome, copper, iron, manganese, lead, nickel and zinc. Apart from manganese, these impurities will all codeposit with cobalt in an electrowinning cell. Removal of the various impurities is guided by the purity specification that the final metal product is required to meet. Because of the similarity in the chemical behaviour of nickel and cobalt in sulphate systems, strategies designed to separate cobalt from the other base metal impurities in sulphate systems will generally also retain whatever nickel is present. As the previous sections have shown, separation of nickel from the main cobalt stream is possible using DOWEX M4195 resin. Cobalt-refining flowsheets generally consist of a refinery front-end, in which the bulk of the purification work is completed in a single pass and the electrowinning circuit where a circulating load of cobalt electrolyte passes through the tankhouse. The nickel ion exchange purification operation may form part of the refinery front-end, or it may be located in the electrolyte circuit. The most appropriate position for the ion exchange step will depend on the relative solution flows in the two sections, total nickel concentration in each section, the ratio of nickel to cobalt in each section and on the final purity requirements. For the discussion that follows, cobalt-refining flowsheets are separated into two broad categories, according to the strength of the cobalt liquors in the front-end of the refinery. The first category includes flowsheets that treat concentrated cobalt liquors arising from leaching of impure intermediate cobalt solids. Examples include the Bulong Nickel operation in Western Australia that treats a concentrated cobalt stream arising from a pressure leach of impure cobalt sulphide and INCOs Port Colborne plant where the cobalt-bearing liquor is produced by leaching impure cobalt hydrate. Into the second category are grouped those flowsheets which treat dilute cobalt bearing liquors to remove impurities, prior to transfer of cobalt to the electrowinning circuit. The cobalt refining plants in Zambia (ZCCMs Nkana and Chambishi Metals RLE plants) and the Democratic Republic of the Congo (Gecamines Shituru and Luilu plants) fall into this category. These plants all treat bleed solutions from the main copper electrowinning plant, prior to precipitation of cobalt hydroxide cake which is leached in spent cobalt electrolyte.

4.2 NICKEL ION EXCHANGE IN REFINERY FRONT-END 4.2.1 Process Specification The flowsheet considered is for a refinery producing 1000 tpa of cobalt cathode. From this information, the flow of cobalt through the refinery front-end is calculated to be approximately 125 kg/h. The assumed ratio of Ni :Co in the feed to the refinery is 1:200. The nickel in the purified solution fed to the electrolyte circuit must be sufficiently reduced so that the nickel concentration in the cobalt cathode does not exceed 500 mg/l. Since all the nickel which enters the electrolyte circuit will leave in the cobalt cathode, this means that the ratio of Ni to Co in the refinery liquor must be reduced to 1:2000, i.e. 90% of the nickel must be removed in the refinery front-end. The design strategy has two main goals; to minimise the inventory of DOWEX M4195 resin and to maximise the utilisation of the resin capacity for nickel. The first objective impacts on the capital cost of the ion exchange installation, since the resin is expensive (US $90/l) and for large inventories, the reagent first fill cost overshadows the cost of the contacting equipment.
12

The second objective affects operating expenditure. The resin capacity for nickel and cobalt is fixed at about 30 g/l (see section 2.4). Higher nickel loadings are achieved at the expense of cobalt loading, which results in reduced cobalt losses during elution and lower elution frequency (for a fixed resin volume) which reduces reagent consumption. Since discussion on resin elution and regeneration requirements is not included, the designs presented in section 4.2.2 and section 4.2.3 assume an offline time of 4h for each resin bed, which is typical for this application2. To accommodate the time spent offline, the minimum duration of the loading sequence is set at 6h for each resin bed.

4.2.2 Concentrated Cobalt Liquor in Refinery Front End The concentration of cobalt in the front-end of the refinery for the first flowsheet is assumed to be 50 g/l. This sets the solution flow through the refinery front-end at 2.5 m3/h, and the nickel concentration ahead of the ion exchange step at 250 mg/l. The limit on the nickel concentration in the feed to the electrolyte circuit is 25 mg/l. The temperature of the cobalt leach liquor is assumed to be 50oC. Because of the low limit on allowable nickel breakthrough and the need to maximise resin capacity utilisation, two designs using two and three columns operating in series have been considered. Operation of two or three columns in series is typically referred to as lead-lag operation. Once the resin in the lead column is exhausted, the column is taken off-line, eluted and regenerated, and returned to operation behind the other column(s). Designs parameters for two and three column systems of the type described above, which limit average nickel breakthrough to 25 mg/l, are presented in Table 6 below. The parameters have been determined by using the mathematical description for a fixed bed contactor, developed in section 4.2, to simulate lead-lag operation and calculate expected nickel breakthrough curves. The solution feed rate, expressed in equivalent resin bed volumes per hour (BV/h), was chosen to ensure an average nickel breakthrough below 25 mg/l. The calculated nickel breakthrough curves for the two-column design are presented in figure 10.

Table 6 No. of Columns 2 3

Design Parameters for Two and Three Columns in Series Feed Rate (BV/h) 2.5 3.3 Resin Inventory Per Column Total (m3) (m3) 1.0 2.0 0.8 2.3 Resin Utilisation Ni Loading Fraction of (g/l) Equilibrium 3.3 65% 4.4 88%

The data in Table 6 indicates that by using three columns rather than two, resin utilisation is increased from 65% to approximately 90%. The increase in utilisation, together with the reduced resin volume eluted per cycle results in a reduction in cobalt losses of approximately 0.3 kg/h (approximately 25% of the cobalt loaded on the resin will be lost during the elution cycle). The associated penalty is the cost of the additional column and the overall increase in resin inventory (250L). The dimensions of a suitable column for the second option are calculated using a resin bed height to diameter ratio of 3. The required column measures 0.7m in diameter by 3.1m in height (1m freeboard allowed above the resin bed). From these dimensions, the superficial linear velocity through the column is calculated to be 6.8 m/h, which is well within industrial practice.

13

The cost of the additional column is estimated to be of the order of US $85 000 (including US $ 22 500 for resin inventory) based on Bateman Engineering database costs. If cobalt is valued at US $ 18 / kg, the payback period on the additional equipment cost is approximately 2 y. This excludes installation cost (likely to double the overall cost) and interest charges. Based on this rough analysis, the third column appears worth the additional investment, for a plant life likely to exceed 10y.

Figure 10

Breakthrough Curves for Two Columns in Series

70 60 50 Nickel (mg/l) 40 30 20 10 0 0 60 120 180 Time (h) Col 1 Col 2 240 300 360

4.2.3 Dilute Liquor in Refinery Front End The concentration of cobalt in the front-end of the refinery for the second flowsheet is assumed to be 10 g/l. This sets the solution flow through the refinery front-end at 12.5 m3/h, and the nickel concentration ahead of the ion exchange step at 50 mg/l. The limit on the nickel concentration in the feed to the electrolyte circuit is 5 mg/l. The temperature of the cobalt leach liquor is assumed to be 50oC. Following the procedure outlined in section 4.2.2, three designs using two, three and four columns operating in series have been considered. Design parameters for the various systems, which limit average nickel breakthrough to 5 mg/l, are presented in Table 7.

Table 7 No. of Columns 2 3 4 5

Design Parameters for Two and Three Columns in Series Feed Rate (BV/h) 4.3 7.4 9.7 11.4 Resin Inventory Per Column Total (m3) (m3) 2.9 5.8 1.7 5.0 1.3 5.2 1.1 5.5
14

Resin Utilisation Ni Loading Fraction of (g/l) Equilibrium 1.2 24% 2.0 41% 2.6 53% 3.1 62%

The data presented in table 7 shows that the minimum resin inventory is achieved using three columns, however the four column system is calculated to be the most cost-effective option when cobalt losses are accounted for.

4.3 NICKEL ION EXCHANGE IN ELECTROLYTE CIRCUIT 4.3.1 Process Specification The cobalt tankhouse is assumed to produce 125 kg/h of cobalt metal in undivided electrowinning cells. The per pass conversion of cobalt (or cobalt bite ) for electrowinning in undivided cells is typically 5 g/l, thus the circulating flow of electrolyte is calculated to be 25 m3/h. The cobalt concentration in the feed to the electrowinning cells is assumed to be 50 g/l. In order that the maximum allowable nickel concentration in the metal (500 mg/l) is not exceeded, the nickel concentration in the feed to the electrowinning cells should be maintained at 150 mg/l2. Based on the flow to the ion exchange columns, the feed nickel concentration is calculated to be 175 mg/l.

4.3.2 Ion Exchange Process Design Following the procedure outlined in section 4.2.2, two designs using two and three columns operating in parallel have been considered. The mode of operation is changed from series to parallel, because for this process specification, a relatively high nickel breakthrough is allowed. The calculated design parameters that limit the average nickel breakthrough to 150 mg/l are shown in table 8. Resin utilisation figures are not shown, as these are high for all options.

Table 8 No. of Columns 2 2 3

Design Parameters for Two and Three Columns in Parallel Feed Rate (BV/h) 22 10 10 Transfer Time (h) 6 12 12 Resin Inventory Per Column Total (m3) (m3) 1.1 2.3 2.4 4.8 1.3 3.8

The data in table 8 shows that for a transfer time of 6h, the optimum design for 2 columns requires an extremely high feed rate (28 BV/h). For a resin bed height to diameter ratio of 2:1, the resulting linear velocity through the column is approximately 40m/h, which is significantly higher than typical industry practice. Reducing the feed rate reduces the linear velocity, however this is done at the expense of increasing the resin inventory by the reciprocal proportion. The second option in table 8 is calculated by constraining the linear velocity to 24 m/h. A more economic solution is to split the feed flow between two duty columns operating in parallel, which is the last option shown in table 8. For the last option there is no lag column and this design allows the overall resin inventory to be reduced compared with the second option.

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4.4 EVALUATION OF OPTIONS The optimal designs for each of the flowsheet options covered in sections 4.2 and 4.3 are summarised in table 9.

Table 9 No. of Columns 3 4 3

Design Options for Nickel Removal by Ion Exchange (Flowsheet I) Position Front-end (conc.) Front-end (dilute.) EW Circuit Column Dimensions D (m) H (m) 0.7 3.1 0.8 0.8 3.7 3.7 Resin (m3) 2.3 5.2 3.8 Resin Utilisation 88% 53% 100%

The data in table 9 shows that for flowsheets where the cobalt liquor in the front-end of the refinery is fairly concentrated, the preferred location for the nickel ion exchange step is in the front-end of the refinery, ahead of the electrolyte circuit. This option reduces both resin inventory and cobalt losses during the elution step. Where the front-end of the refinery treats dilute cobalt liquor, the preferred location for the nickel ion exchange step is within the electrolyte circuit.

16

5. CONCLUSIONS The mathematical formulation presented provides a useful description of the kinetics of nickel adsorption onto DOWEX M195 resin. The approach makes it possible to use kinetic data measured in stirred batch adsorption tests to estimate nickel breakthrough curves for a fixed bed contactor and can be extended to simulate counter current ion exchange. Breakthrough curves for changing operating conditions may also be calculated from a single measured curve. A case study presented demonstrates the application of the mathematical formulation and highlights considerations that are relevant to the design exercise. Determination of rate data from various published sources shows some variability. In addition, it appears that the nickel adsorption rate-controlling step changes from chemical reaction to mixed intra-particle diffusion / chemical reaction as the process temperature is increased above 25 oC. A detailed kinetic test program is required to verify the kinetic model used, to provide more reliable rate information and to elucidate the change in rate controlling mechanism with temperature.

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6. ACKNOWLEDGEMENTS The contribution that Preston Resources have made by allowing publication of testwork data measured by Mintek for the Bulong Nickel Project3, is gratefully acknowledged.

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7. REFERENCES 1. Agnew R.G. and Krause E., Electrolytic Cobalt Production at INCO, paper presented at Minemetal, Havana, Cuba, 20-22 November, 1990. 2. Rao A.S., Minango R., Nkhoma J. and Singh H.P., Process Developments in the Cobalt Purification Circuit at Chambishi RLE Cobalt Plant of ZCCM, Zambia, in Extractive Metallurgy of Copper, Nickel and Cobalt. Vol 1, Eds. Reddy R.G. and Weizenbach R.N., The Minerals and Metals Society, 1993. 3. Cole P.M., Megaw D.C. and Engelbrecht J.P., Private Communication, 1997. 4. Levenspiel O., Chemical Reaction Engineering, John Wiley and Son, Inc., New York, 1972 5. Helfferich F.G., Models and Physical Reality in Ion-Exchange Kinetics, Reactive Polymers, 13 (1990) 191-194. 6. Thomas H.C., Heterogenous Ion Exchange in a Flowing System, J. Am. Chem. Soc. 66 (1944), pp.1644. 7. Rosato L., Harris G.B. and Stanley R.W., Separation of Nickel from Cobalt in Sulphate Medium by Ion Exchange, Hydrometallurgy, 13 (1984), pp. 33-44. 8. Grinstead R.R., Selective absorption of copper, nickel, cobalt and other transition metal ions from sulphuric acid solutions with the chelating ion exchange resin XFS 4195., Hydrometallurgy, 12 (1984), pp387 400.

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