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A RESIN-IN-PULP PROCESS FOR THE RECOVERY OF

COPPER FROM BIOLEACH CCD UNDERFLOWS



by

I.P. Greager
*
, J.P. Wyethe
*
, M.H. Kotze
*
, D.Dew

and D. Miller


* Mintek Billiton Process Research
Private bag X3015 Private Bag X10014
Randburg Randburg
South Africa 2125 South Africa 2125


ABSTRACT
The resin-in-pulp (RIP) process was developed primarily for the recovery of metals
from high volumes of low-grade pulps, as is the case in the gold processing industry.
However, this technology can also be applied to the recovery of soluble metals from
solid residues on base metal plants. Applications for the RIP process include the
scavenging of valuable metals from leach and precipitation residues, especially where
the solids have poor filterability or settling characteristics. The RIP process will
improve overall plant recoveries, and it may be possible to decrease the filter duties or
the degree of washing on the filters. In addition, the barren stream from the RIP
operation may reduce any environmental impact significantly.

Billiton Process Research (BPR) commissioned Mintek to investigate the
metallurgical and economic feasibility of a resin-in-pulp process for the recovery of
copper from bioleach counter-current decantation (CCD) underflows. Batch
laboratory testwork and a continuous mini-plant campaign was conducted in order to
optimise the process parameters. The results were used to conduct a preliminary
sizing and costing study, in order to evaluate the economic viability of the RIP
technology for this application.
A RIP process for the recovery of copper from bioleach CCD underflows.
1
1. INTRODUCTION
The development of the resin-in-pulp (RIP) process at Mintek was initially targeted
primarily at the recovery of metals from large volumes of low-grade leach pulps, as is
the case in the gold processing industry. Minteks RIP expertise culminated in the
development of a resin-in-pulp process, MINRIP
TM
, for the recovery of gold from
leached slurries. Mintek has subsequently evaluated the applicability of this
technology to the in-pulp extraction of copper, zinc, nickel, cobalt, vanadium and
manganese [1,2].

The main application of the RIP process in the base metal industry will be the
scavenging of soluble metals from leach residues, precipitation residues and other
solid wastes that have poor filterability or settling characteristics. However, this
technology can also be applied to the recovery of metals from the leach slurry when
low-grade materials are treated.

A schematic layout of the resin-in-pulp process configuration is given in Figure 1.


FEED SLURRY
REPULP TANK
ADSORPTION
RESIN-PULP SEPARATION
ELUTION
WASH
S1 PULP
RECYCLED AT
TRANSFER
ELUANT
H
2
O
RECYCLE
RECYCLE RESIN
BARREN PULP
denotes RESIN FLOW
denotes PULP/SOLUTION FLOW


Figure 1 : Schematic representation of the resin-in-pulp circuit

A RIP process for the recovery of copper from bioleach CCD underflows.
2
During the adsorption stage, the feed pulp is contacted with resin in a multi-stage,
counter-current plant. After the resin has been passed counter-currently through the
adsorption plant, the resin will be loaded predominantly with the valuable metal
together with lower concentrations of other metals. The barren pulp from the last
stage could be discarded to the slimes dam, after a pH adjustment, or alternatively the
barren pulp could be thickened, and the thickener overflow could be returned to the
plant for use as process water.

The loaded resin exiting the adsorption circuit is separated from the pulp by means of
a linear belt, sieve bend or vibrating screen, and the pulp is returned to the feed. The
loaded resin is then rinsed with water to remove any particulates, after which the resin
is transferred into an elution column. During elution, the metals are stripped from the
resin with sulphuric acid (this could be fresh acid or an acid-bearing stream),
producing a concentrated metal sulphate eluate. The excess acid is then washed from
the resin bed with water, and the eluate, and possibly the wash water, are returned to
the relevant unit operation in the process flowsheet. The eluted, washed resin is
transferred back to the adsorption circuit for the next transfer.

The major advantages of the resin-in-pulp process include :
It is effective for the recovery of soluble metals from pulps with poor filterability
or settling characteristics. The fact that the process operates in a pulp medium
means that the solid-liquid requirements may be reduced or possibly eliminated.
In addition, it may be possible to significantly reduce wash water requirements ;
The RIP process may be able to achieve lower discharge metal concentrations
than those achieved with the more conventional filtration or solid-liquid
separation systems, hence reducing the problems associated with the disposal of
wastes containing soluble metals ;
The overall metal recoveries on the plant can be improved ; and
Co-precipitated and adsorbed metal species may be recovered with the RIP
process, which will further improve the overall metal recovery.

Billiton Process Research (BPR) commissioned Mintek to evaluate the feasibility of a
RIP process for the recovery of soluble copper from a bioleach thickener underflow.
A RIP process for the recovery of copper from bioleach CCD underflows.
3
This paper outlines the process development, from the batch laboratory testwork to
the continuous mini-plant campaign. Based on the results of this testwork, a full-scale
plant was sized and a preliminary techno-economic study was conducted.


2. LABORATORY TESTWORK PROGRAMME
The resin that was selected for the purposes of this investigation was a commercially
available chelating resin. The resin selectivity, for metals in the feed solution under
consideration over sodium, is given by the following selectivity series :

H
+
> Fe
3+
> Cu
2+
> Fe
2+
> Ca
2+
> Mg
2+
> Na
+


A number of potential commercial resins were compared, on a techno-economic
basis, during an earlier study at Mintek. The chelating resin that was used during this
study was found to be the most cost-effective resin option.

2.1 Effect of pH
The effect of pH on the copper loading of the resin was investigated to determine the
minimum pH at which maximum copper loading could be achieved. Results are
shown in Figure 2.

0
20
40
60
80
100
0.0 1.0 2.0 3.0 4.0
pH
C
o
p
p
e
r

l
o
a
d
i
n
g

(
g
/
L
)

* Final copper concentration > 0.01M
Figure 2 : Effect of pH on copper loading.

A RIP process for the recovery of copper from bioleach CCD underflows.
4
The pH dependence was measured using a synthetic copper sulphate solution, at a
concentration high enough to eliminate potential interference from equilibrium
constraints. It is evident, from Figure 2, that the copper loading profile levelled off at
approximately pH 2.5, and hence it would be beneficial if the recovery of copper can
be conducted at a pH of 2.5 or higher.

2.2 Iron removal
The resin is selective for ferric over copper. Consequently it is necessary to conduct
iron removal, prior to RIP, in order to reduce the degree of iron co-loading on the
resin. This is critical so that the capital (CAPEX) and operating expenditure (OPEX)
associated with the co-loading of iron is limited.

Iron removal was effected by the hydrolytic precipitation of ferric as an iron
hydroxide, by addition of 100g/L limestone slurry at a temperature of 40C. The iron
precipitation is conducted in a pulp medium, and no solid-liquid separation is required
prior to iron removal. The filterability of the iron precipitate formed is not a critical
consideration as no solid-liquid separation takes place. The crystalline form of the
ferric hydroxide precipitate is of importance only from the point of view that it is
undesirable to produce a highly cross-linked ferric hydroxide gel that may result in
metal loss due to chemical and physical inclusion.

The results of the iron precipitation experiments are given in Table 1.

Table 1 : Results from iron removal testwork.
Parameter pH 2.5 pH 3.0
Solids before iron precipitation (%) 31.1 31.2
Solids after iron precipitation (%) 31.7 33.5
[Fe]
T
before iron precipitation (g/L) 5.6 5.3
[Fe]
T
after iron precipitation (g/L) 0.31 0.04


No attempt was made to remove ferrous from solution as the resin is selective for
copper over ferrous. In addition, in order to effect the quantitative oxidation of ferrous
A RIP process for the recovery of copper from bioleach CCD underflows.
5
ions at a pH of 3.0, an elevated temperature and a strong oxidant, such as oxygen-
enriched air, will be required in order to increase the oxidation rate. Any attempt to
increase the rate of ferrous oxidation by increasing the pulp pH will result in increased
copper losses. Consequently the quantitative oxidation and removal of ferrous ions, at
relatively low pH, will result in increased CAPEX and OPEX. A techno-economic
analysis will have to be conducted, however, to ascertain whether there is an
economic incentive to implement a ferrous oxidation step.

2.3 Ion exchange equilibrium isotherm
An ion exchange equilibrium isotherm was measured at a pH value of 2.5 and at a
solids concentration of 30%. The composition of the feed pulp used for the
measurement of the ion exchange equilibrium isotherm is given in Table 2.

Table 2 : Composition of feed pulp for the ion exchange equilibrium isotherm.
Metal in solution (g/L)
Copper Total iron Calcium Magnesium Aluminium
5.7 0.31 0.55 0.03 0.03


The ion exchange equilibrium isotherm obtained is shown in Figure 3.

0
10
20
30
40
50
60
0 1 2 3 4 5
Copper in aqueous phase (g/L)
C
o
p
p
e
r

l
o
a
d
i
n
g

o
n

r
e
s
i
n

(
g
/
L
)
Data
Freundlich model

Figure 3 : Ion exchange equilibrium isotherm for copper loading.
A RIP process for the recovery of copper from bioleach CCD underflows.
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The Freundlich isotherm model was fitted to the experimental data. The fitting
parameters and correlation coefficients are shown Table 3.

Table 3 : Freundlich isotherm model fitting parameters.
Parameter pH 2.5
a 12.09
b 0.18
r
2
0.95


Copper and iron were the main species loaded onto the resin. The resin loading, in
equilibrium with 2g/L copper in solution, is given in Table 4. The resin capacity
utilisation under these conditions was 75%.

Table 4 : Equilibrium resin loading.
Metal on resin (g/L)
Copper Total iron Calcium Magnesium Aluminium
47 6.1 1.3 < 0.1 < 0.1


3. CONTINUOUS MINI-PLANT CAMPAIGN
The intention of the RIP plant is to recover copper from a CCD thickener underflow.
However, the feed to the RIP plant may be drawn from any of the CCD underflows in
the CCD train. Hence, the metallurgical response of the resin to three different feeds,
namely 0.5, 1.0 and 4.0g/L copper, was evaluated. These three concentrations span
the entire expected concentration range of the various CCD underflows, for this
specific operation. The optimum plant configuration, however, has to be based on
detailed metallurgical and techno-economic considerations.

During the design of a RIP plant, the selection of the mode of operation is important.
The plant could either be operated in a carousel counter-current mode where resin
handling can be limited and the resin inventory is more accurately controlled in each
stage, or in a continuous counter-current mode. Although inventory control might
A RIP process for the recovery of copper from bioleach CCD underflows.
7
prove more difficult during continuous operation, a substantial CAPEX saving is
possible. However, since relatively low upgrading ratios can be expected, inaccurate
control of the resin volume in each stage might lead to large fluctuations in the barren
stream exiting the plant. Consequently, a carousel mode of operation was chosen for
the mini-plant evaluation. The counter-current flow of resin and pulp in a multistage
carousel adsorption circuit is shown in Figure 4. Feed slurry is pumped into the first
contacting stage. At transfer, the feed is re-directed to the second stage and the resin
and pulp from the first contacting stage is separated. The loaded resin is then sent to
the elution column. After elution, the stripped resin is fed back into the last stage of
the adsorption circuit, hence completing the resin cycle.

S2 S3 S4
S1 S2 S3 S4 S5
FEED
S5
BARREN
FEED
BARREN
S1
T R A N S F E R


Figure 4 : Schematic diagram of the counter-current flow of pulp and resin in a
carousel RIP cascade.

The mini-plant consisted of a four-stage cascade of contactors, each with an active
volume of 960mL. The resin-pulp mixing in each stage was achieved with mechanical
overhead stirrers. Resin was retained in the contactor by means of a 200m peripheral
screen, and pulp gravitated through the screens from one stage to the next. During
adsorption, the pH was controlled at the desired set-point in all the stages. Lime
slurry, limestone slurry or any other alkali may be used for pH control.
A RIP process for the recovery of copper from bioleach CCD underflows.
8
After preparation of the feed pulps, ferric ions were neutralised by the addition of
100g/L limestone slurry, at ambient temperature. The pH was adjusted to 2.9. No
attempt was made to oxidise the residual ferrous ions to ferric. The feed pulp
compositions evaluated during this study, after iron precipitation, are shown in Table
5.

Table 5 : Average feed pulp compositions for the mini-plant campaign (after iron
removal).
Parameter 4.0g/L Cu 1.0g/L Cu 0.5g/L Cu
Solids (%) 20 27 25
pH 2.9 2.9 2.9
Copper (g/L) 4.4 0.98 0.49
Zinc (g/L) 0.14 0.16 0.01
Nickel (g/L) < 0.01 < 0.01 < 0.01
Cobalt (g/L) < 0.01 < 0.01 < 0.01
Total iron (g/L) 0.70 0.35 0.12
Manganese (g/L) 0.01 < 0.01 0.03
Aluminium (g/L) 0.02 < 0.01 < 0.01
Calcium (g/L) 0.46 0.50 0.53
Magnesium (g/L) 0.03 0.01 0.05


During the mini-plant campaign the following parameters were evaluated :
Copper feed concentration ;
Pulp residence time ; and
Pulp pH.

3.1 Effect of copper feed tenor
The effect of the copper feed concentration on the process performance was
investigated. For these tests, the pulp residence time per stage was maintained at 1
hour, the resin residence time per stage was 3.1 hours, and the pH was controlled at
3.0. The operating parameters evaluated are presented in Table 6.

A RIP process for the recovery of copper from bioleach CCD underflows.
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Table 6 : Operating parameters to evaluate the effect of copper feed tenor.
Copper in feed
(g/L)
Resin concentration
(vol. %)
4.4 20
1.0 5.0
0.5 3.2


As the resin residence time was maintained constant, it was necessary to vary the
resin concentration per stage, in order to process the various feeds. The average metal
loadings of the major metals onto the resin removed from the first adsorption stage at
transfer are presented in Table 7.

Table 7 : Average metal loadings and resin capacity utilisation.
Copper in feed (g/L) 4.4 1.0 0.5
Resin loading (g/L)
Copper 49.5 39.8 32.2
Calcium 0.39 1.32 2.56
Total iron 4.95 7.50 5.20
Resin capacity utilisation (%)
Stage 1 86.5 80.8 63.5


Results indicated that with a decrease in the copper feed tenor, the copper loading on
the resin also decreased, whilst the calcium co-loading increased. The average copper
solution profiles across the mini-plant cascade, at transfer, for all three copper feed
concentrations are presented in Figure 5.

A RIP process for the recovery of copper from bioleach CCD underflows.
10
4400
2570
487
37 11 4
0
500
1000
1500
2000
2500
3000
3500
4000
4500
5000
Feed S1 S2 S3 S4 Comp.
Barren
C
o
p
p
e
r

i
n

s
o
l
u
t
i
o
n

(
m
g
/
L
)

(i) Copper feed tenor ~ 4.0g/L

980
670
305
85
10 8
0
200
400
600
800
1000
1200
Feed S1 S2 S3 S4 Comp.
Barren
C
o
p
p
e
r

i
n

s
o
l
u
t
i
o
n

(
m
g
/
L
)

(ii) Copper feed tenor ~ 1.0g/L

490
325
152
49
9 7
0
100
200
300
400
500
600
Feed S1 S2 S3 S4 Comp.
Barren
C
o
p
p
e
r

i
n

s
o
l
u
t
i
o
n

(
m
g
/
L
)

(iii) Copper feed tenor ~ 0.5g/L

Figure 5 : Average copper solution profile across the RIP mini-plant cascade

A RIP process for the recovery of copper from bioleach CCD underflows.
11
The average copper concentration in the composite barren stream for all three feed
concentrations was less than 0.01g/L.

It is evident from Figure 5(i) and Table 7 that it is possible to reduce the copper
concentration from 4g/L to below 0.05g/L in three adsorption stages, whilst
maintaining a high resin loading in stage 1. The operating parameters employed
resulted in a relatively large extraction efficiency of 42% across the first stage.
However, as the feed concentration was relatively high, a high resin loading of
49.5g/L could still be attained.

At the lower feed concentrations, the extraction efficiencies across stage 1 were
decreased to approximately 30%, to allow a higher copper tenor in the stage 1
effluent, hence maximising the copper loading on the resin within the equilibrium and
kinetic constraints. Consequently four stages were required in order to reduce the
composite barren to less than 0.05g/L (see Figure 5(ii) and (iii)).

The effect of the number of stages on the overall copper recovery, under the operating
parameters employed, is shown in Table 8.

Table 8 : Effect of number of stages on overall copper recovery.
Copper in feed (g/L) Recovery 3 stages (%) Recovery 4 stages (%)
4.4 > 99 > 99
1.0 > 91 ~ 99
0.5 ~ 90 > 98


3.2 Effect of pulp residence time
Tests were conducted at varying pulp residence times in order to ascertain whether a
reduced pulp residence time had a detrimental effect on the process performance.
Provided the reduced residence time results in a negligible impact on the process
performance, it may be possible to reduce the volume of the adsorption vessels, which
translates into a CAPEX saving.

A RIP process for the recovery of copper from bioleach CCD underflows.
12
The important operating parameters for the investigation into the effect of pulp
residence time (
pulp
) per stage on process performance, for the 1.0g/L copper feed,
are given in Table 9. For these tests, resin residence time per stage was 3.2 hours, and
the pH was controlled at 3.0.

Table 9 : Operating parameters to evaluate the effect of pulp residence time.
Test
pulp

(minutes)
Resin concentration
(vol. %)
1 60 5.0
2 30 11.7
3 20 17.9


It was possible to maintain a constant resin transfer time by altering the resin
concentration per stage according to changes in the mass of copper introduced with
the feed.

The average resin loading and capacity utilisation achieved on the stage 1 resin, at the
different residence times, are summarised in Table 10.

Table 10 : Average metal loadings and resin capacity utilisation.
Parameter Test 1 Test 2 Test 3
Experimental conditions

pulp
(minutes) 60 30 20
Resin loading (g/L)
Copper 39.8 42.3 39.4
Calcium 1.32 1.18 1.15
Total iron 7.50 6.10 6.20
Resin capacity utilisation (%)
Stage 1 80.8 81.7 77.9


A RIP process for the recovery of copper from bioleach CCD underflows.
13
From the data in Table 10 there seems to be no significant difference in the copper
loading or total resin capacity utilisation for the pulp residence times evaluated. The
behaviour of the iron loadings during the mini-plant trial was somewhat erratic, and
will have to be confirmed during a more extensive mini or pilot-plant campaign.

The normalised average aqueous phase copper profiles across the CCIX cascade, for
the different pulp residence times at a copper feed concentration of 1.0g/L, are
presented in Figure 6. The data was normalised with respect to the feed concentration
in order to eliminate small variations in the copper feed analysis for the three tests.

0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Feed S1 S2 S3 S4 Comp.
Barren
[
C
u
]
/
[
C
u
]
f
e
e
d
Test 1 - 60 minutes
Test 2 - 30 minutes
Test 3 - 20 minutes

Figure 6 : Comparison of the normalised average copper solution profiles.

It is evident that the solution profiles for the three tests are similar. Four adsorption
stages were required to reduce the copper concentration in the aqueous phase to less
than 0.05g/L for all pulp residence time tests.

3.3 Effect of pulp pH
The sensitivity of the process to relatively small variations in pH was tested. The
motivation behind conducting a mini-plant trial at a lower pH was that both the level
of copper loss during iron precipitation and the level of impurity co-loading may be
reduced at a lower pH set-point.

A RIP process for the recovery of copper from bioleach CCD underflows.
14
The important operating parameters for the investigation into the effect of pulp pH on
process performance, for the 1.0g/L copper feed, are given in Table 11.

Table 11 : Operating parameters to evaluate the effect of pulp pH.
Test pH Resin concentration
(vol. %)
1 3.0 5.0
4 2.5 5.0


In order to elucidate the effect of reduced pulp pH, the pulp and resin residence times
were kept constant, at 1 hour and 3.2 hours respectively.

The average resin loading and capacity utilisation achieved on the stage 1 resin, at the
different pH values, are summarised in Table 12.

Table 12 : Average metal loadings and resin capacity utilisation.
Parameter Test 1 Test 4
Experimental conditions
Pulp pH 3.0 2.5
Resin loading (g/L)
Copper 39.8 37.5
Calcium 1.32 0.67
Total iron 7.52 7.03
Resin capacity utilisation (%)
Stage 1 80.8 72.1


From the data in Table 12 it would appear that the lower pH of 2.5 resulted in a
slightly lower copper loading. The change in the co-loading of the impurities was
minimal. The normalised average copper solution profiles across the CCIX mini-plant
cascade, for the different pH values at a copper feed tenor of 1.0g/L, are shown in
Figure 7.
A RIP process for the recovery of copper from bioleach CCD underflows.
15
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Feed S1 S2 S3 S4 Comp.
Barren
[
C
u
]
/
[
C
u
]
f
e
e
d
Test 1 - pH 3.0
Test 4 - pH 2.5

Figure 7 : Comparison of the average copper solution profiles.

It is evident from Figure 7 that the copper solution profile is somewhat higher for test
4 (pH 2.5) than test 1 (pH 3.0). The reason is that the reduced pH set-point in test 4
resulted in a slightly reduced copper loading, compared to the copper loading
achieved in test 1. Hence, the concentration profile shifted, resulting in a slight
increase in the composite barren copper concentration from 0.01g/L (pH 3.0) to
0.016g/L (pH 2.5). However it was still possible to reduce the copper concentration to
less than 0.02g/L in the composite barren using four stages.

These results indicate that pH variations between pH 2.5 and 3.0 should not have a
major impact on the overall plant performance.

4. PLANT SIZING & PRELIMINARY ECONOMIC ANALYSIS
4.1 Plant sizing
Slurry flowrates of 100m
3
/h were chosen for the economic comparison of streams
containing a solution phase concentration of 0.5, 1.0 and 4.0g/L copper respectively.
The resin concentration was maintained below 25% to limit resin loss through
attrition. A four hour resin transfer time was used to allow adequate time for resin
handling and elution.

The total resin inventory comprised :

A RIP process for the recovery of copper from bioleach CCD underflows.
16
The required resin volume in each adsorption stage to allow for adsorption of the
total load of copper in the feed; and
Two equivalent resin volumes in the elution circuit to allow sufficient time for
resin handling, and the elution and wash steps, so that fluctuations in the copper
feed tenor can be handled, within the design limits.

Although only four active adsorption stages were required for the effective recovery
of copper, a fifth adsorption stage had to be incorporated during the design of the
carousel RIP plant to make provision for resin handling.

The principal results of the plant sizing are shown in Table 13.

Table 13 : Summary of important sizing parameters for a copper RIP plant treating
100m
3
/h pulp, at different copper feed tenors.
Feed:
Cu

Flowrate
% solids

g/L
tonne/annum
m
3
/h

A
0.5
330
100
35
B
1.0
700
100
35
C
4.0
2 900
100
35
RIP:
Pulp residence time per stage
Number of stages
Active volume
Resin volume

h

m
3

m
3
/stage

0.5
5
70
5

0.5
5
70
8

1.0
5
160
27


4.2 CAPEX calculation
A CAPEX estimate was prepared (to within 15% accuracy) by LTA Process
Engineering, Minteks partners in resin-in-pulp technology, during February/March
2001, for a RIP plant employing adsorption tanks with an active volume of 80m
3
. This
CAPEX was scaled using the six-tenths factor rule, using the adsorption tank active
volumes as a basis, in order to obtain an indication of the CAPEX requirement for the
current RIP application.
A RIP process for the recovery of copper from bioleach CCD underflows.
17
It is evident from Table 13, that the LTA CAPEX estimate was conducted for a plant
that is similar in size to options A and B. Option C, however, is significantly larger
than the plant costed by LTA plant. Consequently it is anticipated that the error due to
the scaled calculation of the CAPEX calculation will be larger for option C, than for
options A and B. The resin inventory requirement was based on the resin loadings
obtained during the mini-plant campaign. The scaled CAPEX figures for the three
design scenarios are presented in Table 14.

Table 14 : Scaled CAPEX for the three proposed copper RIP plants.
CAPEX item A
0.5g/L Cu
330 tpa
B
1.0g/L Cu
700 tpa
C
4.0g/L Cu
2900 tpa
Scaled plant CAPEX (Rands, million) 18.4 18.4 31.4
Actual resin CAPEX (Rands, million) 2.0 3.2 9.7
TOTAL CAPEX (Rands, million) 20.4 21.6 41.1


4.3 OPEX calculation
The following components were considered for the OPEX calculations :

Eluant consumption
Resin could be eluted with fresh H
2
SO
4
, spent electrolyte or solvent extraction
raffinate. For this evaluation a consumption of 1.2 moles of fresh sulphuric acid per
litre of resin was used at a cost of R360/tonne (as 98% sulphuric acid).

However, it may be argued that acid consumption for copper elution may not be
considered an operating expense, owing to the fact that each mole of copper returned
to a solvent extractionelectrowinning plant would produce an equivalent amount of
acid. Thus in this case, the sulphuric acid cost is that associated with the stripping of
co-loaded impurities only.



A RIP process for the recovery of copper from bioleach CCD underflows.
18
Limestone consumption
The limestone consumption for neutralisation during adsorption was taken to be 1.2
moles/L resin at a price of R110/tonne. It can also be argued that the neutralising
agent may be omitted as an OPEX, owing to the fact that the CCD underflow,
assuming that no resin-in-pulp plant was installed, would have to be neutralised and
the metals precipitated prior to disposal.

Labour
It is envisaged that the complex valve and flow sequencing that is required for a RIP
operation will result in a reasonably high level of automation. The labour component
of the OPEX, assuming three eight hour shifts per day, was based on a staff of eight
operators (R90 000/annum/operator) and 2 shift supervisors (R190 000/annum/
supervisor).

Resin replacement
During the operation of the RIP plant, resin will be lost due to degradation and
handling. Resin losses should be determined on a relatively large scale for a specific
application. A replacement figure of 50% of the inventory per annum was used for the
purposes of the OPEX calculations.

Copper losses
A copper loss of 0.05g/L in the barren stream exiting the adsorption cascade was
assumed. A copper price of R13 624.98/tonne was used for calculations [3].

The OPEX associated with the RIP operation is shown in Table 15. It is evident from
Table 15 that the OPEX is highly dependent on the amount of copper produced. The
labour component is dependent on the production level. The OPEX associated with
the eluant, limestone and resin replacement is a function of the level of resin loading,
which in turn is dependent on the feed concentration.



A RIP process for the recovery of copper from bioleach CCD underflows.
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Table 15 : OPEX breakdown for proposed copper RIP plants
Parameter OPEX (Rand/tonne copper)
A
0.5g/L Cu
330 tonne/annum
B
1.0g/L Cu
700 tonne/annum
C
4.0g/L Cu
2900 tonne/annum
Eluant
Limestone
Labour
Resin replacement
Copper loss (barren)

TOTAL OPEX
1 520
460
3 310
3 000
1 510

9 800
1 160
350
1 570
2 280
720

6 080
900
270
380
1 770
170

3 490


4.4 Revenue
The revenue was calculated using a copper price of R13 624.98/tonne [3]. It was
decided that, because the copper eluate produced by the resin-in-pulp circuit must
undergo further treatment before a saleable copper product is formed, the copper
revenue should be discounted. The total copper revenue was thus discounted by 10%.
The revenue, after discounting, was calculated to be R12 262.48/tonne of recovered
copper.

4.5 Cash flow analysis
Cash flow analysis was conducted in order to get an indication of the payback periods
and the internal rates of return of the proposed RIP plants. For the purposes of the
cash flow analysis, the scaled CAPEX was broken down into three categories,
namely:

1. Buildings ;
2. Productive plant ; and
3. Permanent works.

A RIP process for the recovery of copper from bioleach CCD underflows.
20
The composition of the breakdown of the total CAPEX, as well as the associated
depreciation schedule, is shown in Table 16.

Table 16
CAPEX composition and depreciation schedule
CAPEX item Percentage of total Depreciation schedule
Buildings 10% Not depreciated
Productive plant 80% Written off at 20% per annum over 5 years
Permanent works 10% Written off at 5% per year over 20 years


In addition, the cash flow analysis was subject to the following assumptions :

The tax rate was taken as 35% ;
Discount factor was taken as 10% ;
Life of plant was taken as 10 years ;
No variation in the metal and reagents prices was taken into account ; and
Working capital was calculated as 10% of the total CAPEX [4].

The results of the cash flow analysis, carried out for each feed scenario, based on the
OPEX figures from section 4.3, are presented in Table 17. In addition, a cash flow
analysis was conducted for the case in which the OPEX was modified as follows :

Sulphuric acid : Although it may be argued that the cost associated with the
stripping of copper is not an operating expense (owing to the production of a
stoichiometric quantity of acid during copper electrowinning), elution of co-
loaded impurities from the resin remains an operating cost. Thus the sulphuric
acid consumption component of the OPEX was modified to include the cost of
stripping off the impurities only, which translates to 20% of the operating capacity
of the resin ; and
Limestone : The limestone was excluded entirely from the OPEX calculation, for
reasons discussed in section 4.3.

A RIP process for the recovery of copper from bioleach CCD underflows.
21
Table 17 : Cash flow analysis of the proposed copper RIP plants.
Parameter A
0.5g/L Cu
330 tonne/annum
B
1.0g/L Cu
700 tonne/annum
C
4.0g/L Cu
2900 tonne/annum
Sulphuric acid and limestone consumption @ 1.2mol/L resin
Payback period (years) > 10.0 9.7 2.8
IRR (%) -9 11 42
Sulphuric acid consumption @ 20% operating capacity; no limestone consumption
Payback period (years) > 10.0 7.4 2.5
IRR (%) -7 14 47


It is evident from the data in Table 17 that the payback period and IRR are highly
dependent on the mass of copper recovered in the RIP unit operation.
For a greenfield application, the RIP plant may result in a reduction in the number of
CCD stages required. Consequently a techno-economic study comparing the process
economics of the CCD circuit versus the RIP circuit would have to be conducted for
each application, in order to determine the economically optimum process
configuration.

In addition, the environmental benefits of the RIP process have not been factored into
the process economics.


5. CONCLUSIONS
During the laboratory testwork, the effect of pH on copper loading and capacity
utilisation was determined, and an ion exchange equilibrium isotherm was measured
at a pH value of 2.5. Maximum copper loading was achieved at pH values of 2.5 and
higher and at copper concentrations greater than 0.7g/L (at pH 2.5).

Based on the laboratory testwork, the metallurgical response of the resin to the
bioleach slurry was evaluated on a continuous mini-plant scale, at three different
copper concentrations, namely 4.0, 1.0 and 0.5g/L copper.
A RIP process for the recovery of copper from bioleach CCD underflows.
22
For the 4.0g/L copper feed, a pulp residence time per stage of 60 minutes and a pulp
pH of 3.0 were tested. A copper composite barren tenor of less than 0.05g/L was
attained using three adsorption stages. A copper loading of ~ 50g/L was attained in
the first stage, with an iron co-loading of ~ 5.0g/L.

For the 1.0 and 0.5g/L copper feeds, the sensitivity of the process performance to
changes in the pulp residence time and pulp pH was evaluated. Pulp residence times
were varied in order to ascertain the degree to which the reduced residence time
would impact on the process performance. As the pulp residence time per stage was
reduced from 60 minutes to 20 minutes, no significant changes in the copper loading
or composite barren were observed. Consequently it is evident that the adsorption
vessels may be sized for a 20 minutes pulp residence time, depending on the
flexibility required. Variations in the pulp pH between 2.5 and 3.0 had negligible
impact on copper loading and impurity co-loading.

Mini-plant data was used to conduct a preliminary techno-economic evaluation for
three feed concentrations, based on an assumed pulp flowrate of 100m
3
/h. It was
evident that the process economics are extremely sensitive the copper tonnage, but it
is possible for the process to realise a high internal rate of return (IRR). No
environmental benefits were factored into the process economics.

This paper has illustrated that RIP can be an attractive technology for the recovery of
valuable metals from low-grade leach slurries or waste streams. However its potential
has to be evaluated for each individual application.


6. ACKNOWLEDGEMENTS
This paper is published by permission of Mintek and Billiton Process Research
(BPR).

A RIP process for the recovery of copper from bioleach CCD underflows.
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7. REFERENCES
1. Green B.R., Kotze M.H., and Engelbrecht J..P. (1998) Resin-in-pulp - After gold,
where next? EPD Congress, San Antonio, Texas. B. Mishra (ed.). The Minerals,
Metals and Materials Society, Warrendale, Pennsylvania. (Pages 119-136)
2. Taylor M.J.C., Green B.R., Wyethe J.P., Padayachee D.P. and Mdlalose K.E.
(2000) Recovery of vanadium from waste solids and solutions using an ion
exchange process. MINPREX 2000, Melbourne, Victoria.
3. Standard Bank Daily Base Metals Report (22 May 2001)
4. Peters M.S. and Timmerhaus K.D. (1991) Plant design and economics for
chemical engineers. Mc-Graw-Hill Book Company. Fourth edition.