Minerals Engineering 54 (2013) 14–20

Contents lists available at SciVerse ScienceDirect

Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Recovery of nickel and cobalt from laterite leach tailings through resin-in-pulp
scavenging and selective ammoniacal elution
Patrick Littlejohn ⇑, James Vaughan 1
School of Chemical Engineering, Level 3, Chemical Engineering Building (74), College Road, St. Lucia, Queensland 4072, Australia

a r t i c l e i n f o a b s t r a c t

Article history: In the hydrometallurgical processing of nickel laterite ore, a significant amount of dissolved nickel and
Available online 18 March 2013 cobalt can be lost to neutralized tailings slurry during counter current decantation. Resin-in-pulp (RIP)
scavenging using ion exchange resin functionalized with iminodiacetic acid (IDA) has been proposed
Keywords: as an effective way to recover lost metal value. However, the tendency of this resin to co-load impurities
Ion exchange makes integration of metal value back into the plant challenging. In this paper, the application of bis-pic-
Resin-in-pulp olylamine functionalized resin to RIP scavenging is explored. Both types of resin load the valuable metals
Nickel laterite
effectively but bis-picolylamine functionalized resin has a much lower affinity for unwanted impurities.
Nickel and cobalt
Picolyl
After loading, selective elution of nickel and cobalt from the new resin was carried out using an ammonia
Ammonia based eluent. The resultant eluate was high in nickel and cobalt with ppm levels of impurities, making it
appropriate for downstream integration in existing nickel/cobalt refineries.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction
Every nickel laterite processing flow sheet is different, but in
general, a leaching stage is employed to dissolve valuable nickel
and cobalt followed by separation of the solution from unwanted
solids using counter current decantation. Counter current decanta-
tion (CCD) of this material is challenging with the process residence
time being long requiring large CCD tanks, occupying a large plant
footprint and requiring high capital investment (Adams 2007; Tay-
lor and Jansen, 2000). Depending on the settling characteristics of
the precipitate, 5% or more of the leached nickel and cobalt can
be lost to the slurry underflow through solution entrainment,
co-precipitation, and sorption processes on the high surface area
solids. For a site producing 40,000 tonnes per annum nickel and
2500 tonnes per annum cobalt this represents yearly losses of
approximately $40 million USD, given current LME spot prices (as
of August 2012). The use of ion exchange resin and resin-in-pulp
loading has been suggested as a method of scavenging this other-
wise lost nickel and cobalt value from CCD tailings (Adams, 2007;
Duyvesteyn et al., 2002; Mendes, 2010; Wassink et al., 2006;
Wyethe et al., 2002; Zainol, 2005; Zontov, 2001). Ion exchange resin
has been used to recover value metal in the uranium and gold
industry through resin-in-pulp/leach and similar carbon-in-leach/
pulp processes for decades (Fleming and Nicol, 1980; Prasad
⇑ Corresponding author. Tel.: +61 (07) 3365 8398; fax: +61 (07) 3365 4199.
E-mail addresses: p.littlejohn@uq.edu.au (P. Littlejohn), james.vaughan@uq.
edu.au (J. Vaughan).
1
Tel.: +61 (07) 3365 3850; fax: +61 (07) 3365 4199.
et al., 1991). However, the authors are unaware of any commercial
application of resin-in-pulp in the base metal industry.
The goal of resin-in-pulp scavenging is to selectively recover va-
lue metal from slurry by contacting the slurry with relatively large
bead chelating ion exchange resin. After value metal has loaded
onto the resin, the resin can be physically separated from the slurry
by sieving. Once the resin is isolated, it is placed into columns
where the metal value is eluted from the resin through contact
with an appropriate solution. By reducing losses of metal value
to tailings, overall metal recovery is improved and CCD throughput
can potentially be increased.
Previous researchers have evaluated potential ion exchange res-
ins for this process on the basis of resin capacity, resin selectivity and
loading/elution kinetics (McKevitt and Dreisinger, 2011; Mendes
and Martins, 2004, 2005). Resin capacity and selectivity work in tan-
dem to dictate the amount of resin required to load a given amount
of nickel and cobalt. In a scavenging process, only small amounts of
nickel and cobalt are present against a complex background of un-
wanted impurities. As a result, the useful resin capacity is deter-
mined not only by the number of sorption sites on the resin, but
also by the tendency of those sorption sites to load unwanted impu-
rities instead of the desired nickel and cobalt (Littlejohn and Vaugh-
an, 2012). Resin particle size distribution is important for both
separation of resin from pulp as well as for kinetics – larger average
bead size with narrow particle size distribution makes resin sieving
easier but slows down resin kinetics by requiring longer intraparti-
cle mass transfer. A final requirement is for the resin to have a high
backbone strength to reduce resin breakage and attrition in the
aggressive resin-in-pulp environment (Halle and Rossoni, 2005).

0892-6875/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.mineng.2013.02.002
 P. Littlejohn, J. Vaughan / Minerals Engineering 54 (2013) 14–20
Several researchers have investigated potential resins for this
process and have concluded that a large bead resin functionalized
with iminodiacetic acid (IDA) (Adams, 2007; McKevitt and Drei-
singer, 2011; Zainol and Nicol, 2009) is the most appropriate for
scavenging nickel and cobalt from laterite tailings. Examples of
commercially products using this functional group are Lanxess
MonoPlus TP 207 XL, Purolite S930, or Dow Amberlite IRC748. Each
of these resins has a high particle size and narrow particle size dis-
tribution. The backbone structure is macroporous which enhances
the ion exchange kinetics compared with gel type resin. Addition-
ally, all have the high resin capacity characteristic of IDA function-
alized resin. IDA functionalized resin is available at relatively low
cost, on the order of $10,000 USD per cubic meter.
IDA functionalized resin seems the natural choice for nickel lat-
erite resin-in-pulp. However, several characteristics of the resin
make integration of an IDA resin-in-pulp unit into existing nickel
laterite flow sheets difficult. First, while IDA resin is relatively
selective for nickel and cobalt over impurities, in scavenging re-
sin-in-pulp the concentration of impurities is orders of magnitude
higher than that of base metal value. As a result, IDA resin from
scavenging circuits is typically only 30–50% loaded with nickel
and cobalt. Many functional groups are filled with undesirable
impurities such as iron, aluminium, manganese, calcium and mag-
nesium (Littlejohn and Vaughan, 2012; Littlejohn et al., 2012; Was-
sink et al., 2006; Zainol, 2005; Zainol and Nicol, 2009). Secondly,
IDA resin is most readily eluted using strong sulphuric acid. The
quantitative nature of this elution recovers not only the nickel
and cobalt, but also the significant amounts of impurities co-
loaded onto the resin. This solution can be difficult to integrate into
the flow sheets of existing nickel refineries. Residual acid adds sig-
nificant neutralization cost to the process of refining contained
nickel into mixed hydroxide precipitate, and high impurity content
makes the solution inappropriate for downstream integration close
to final metal production. More sophisticated elution configura-
tions involving multiple columns or pachuca columns can help
overcome these challenges, but add complexity and cost of the cir-
cuit. Due to the incompatibility of acidic eluate with most down-
stream nickel refining methods, scavenged value must be
integrated back into existing flow sheets through upstream recycle
(Littlejohn et al., 2012).
Downstream integration of scavenged metal value would im-
prove the commercial viability of nickel–cobalt resin-in-pulp. As
several nickel refineries use ammonia based processes, one
possibility is to take advantage of nickel and cobalt’s affinity for
ammonia relative to impurity metals to elute resin into ammoni-
acal solutions. Some success in this area has been achieved by
eluting scavenge loaded IDA resin with solutions of ammonia-
ammonium sulphate-magnesium sulphate (Littlejohn and Vaugh-
an, 2010; Littlejohn et al., 2012). While technically feasible, the
presence of magnesium in a ‘‘pure’’ solution is unwelcome at
best.
One alternative to IDA functionalized resin for scavenging resin-
in-pulp is bis-picolylamine (BPA) resin. BPA resin was first devel-
oped to remove small amounts of copper and nickel from cobalt
electrolytes (Grinstead, 1984; Rosato et al., 1984). At first glance
BPA resin seems unsuitable for nickel/cobalt resin-in-pulp as it
has a lower capacity than IDA resin (Littlejohn and Vaughan,
2012). However, while the total capacity of BPA resin is roughly
half that of IDA, BPA is orders of magnitude more selective for base
metals such as nickel, cobalt, copper and zinc over important later-
ite impurities. As a result, the useful capacity of BPA resin under re-
sin-in-pulp scavenging conditions is similar to that of IDA resin.
The use of BPA resin to recover nickel from nickel heap leach liquor
has been successfully trialled (Marston and Rodgers, 2009). Addi-
tionally, BPA resin has been proven to be amenable to ammonia
based elution (Grinstead, 1984).
15
The goal of this research is to investigate the possibility of using
BPA resin for resin-in-pulp scavenging, followed by ammoniacal
elution to recover nickel and cobalt in an eluate compatible with
existing downstream nickel refining processes. Two primary ques-
tions drove this research:
 Can bis-picolylamine functionalized resin effectively scavenge
nickel and cobalt from laterite tailings?
 Can nickel and cobalt be selectively recovered through ammoni-
acal elution?
2. Experimental methods
2.1. Resin characteristics
The resin used in this work is Lewatit MonoPlus TP 220 (hereaf-
ter referred to as TP 220) made by Lanxess ION in Germany. TP 220
uses a bis-picolylamine functional group and a backbone of poly-
styrene crosslinked with divinylbenzene. The mean particle diam-
eter of the spherical shaped resin is 0.6 mm with 90% of the
particles in the range of 0.55–0.65 mm. The capacity of the resin
depends on solution composition, but previous research has shown
the operational capacity of TP 220 to be 0.9–1.1 mol of equivalent
charge per liter of tapped wet settled resin (Littlejohn and Vaugh-
an, 2012) (note: all future resin volumes refer to tapped wet settled
resin). Resin was received protonated with sulphuric acid and was
subsequently rinsed with de-ionized water prior to use. The selec-
tivity order of the resin is as follows (Lanxess, 2011; Littlejohn and
Vaughan, 2012):
Cu  Ni > FeðIIIÞ > Co > Mn  K > Ca > Na > Mg > Al
2.2. Resin handling and synthetic resin loading
To explore resin elution chemistry, samples of TP 220 were
loaded with nickel and cobalt from solutions containing these met-
als prepared in the laboratory. This loading was carried out by con-
tacting a known volume of tapped wet settled resin in the
protonated form with 10 times the amount of solution containing
5 g/L Ni or Co as dissolved sulphate salts. The resin and solution
were gently agitated at room temperature and the pH was adjusted
through addition of 2 M NaOH until it remained stable at pH 4, typ-
ically requiring 4–6 h to reach equilibrium. Once loaded, the resin
was placed in a column and washed with 20–30 bed volumes of
de-ionized water to remove any solution entrained in resin pores.
This process yielded resin loaded with 30 g Ni or 19 g of Co per liter
of metal form resin.
Determination of loaded resin composition was carried out by
quantitatively eluting 2–5 mL of resin. This small volume of resin
was wet filtered and contacted with 100 mL of 200 g/L H2SO4 in
in a baffled Erlenmeyer flask. The flask was set in a shaking incuba-
tor at 25 °C rotating at 150 rpm for 24 h. The efficacy of different
eluate compositions was tested in a similar fashion. To determine
the kinetics of the elution reaction, samples of the solution were
taken at regular intervals.
2.3. Tailings material – industrial and synthetic
Resin-in-pulp loading experiments were carried out in batch
reactors using both synthetically generated pulp and tailings from
an industrial nickel refinery employing a high pressure acid leach-
ing process. Synthetic pulp was prepared from a starting solution
of 20 g/L Fe(III), 4 g/L Al, 2 g/L Mn, and 20 g/L Mg with 0.5–1 g/L
Ni and 50–500 mg/L Co in a sulphate matrix. The initial pH of this
solution was adjusted to 1.5 using sulphuric acid. This solution was
heated to 80 °C on a hotplate in a baffled batch reactor with vigor-
16 P. Littlejohn, J. Vaughan / Minerals Engineering 54 (2013) 14–20
ous stirring via overhead impeller. The pH was increased to precip-
itate iron through addition of CaCO3 as slurry (20% w/w). Iron pre-
cipitation was carried out over 5 h with a terminal pH of 3.9–4 and
an extent of reaction of greater than 99.5%. The composition of the
resultant solution phase in the slurry (20% w/w solids) is shown in
Table 1. Resin-in-pulp contact with this slurry was carried out
immediately after precipitation was complete and the slurry had
cooled to 60 °C.
The industrial plant samples used in this study came from three
points in the process. The first was slurry from after the acid leach
but before final neutralization. The second was slurry from after fi-
nal neutralization before discharge to tailings pond. The third was
decant solution from the overflow of the tailings pond to the evap-
oration pond. Fig. 1 shows the source of each sample in the process
schematic.
The composition of these materials is summarized in Table 2.
Slurries 1 and 2 are 38% and 41% w/w solids respectively, while
the decant solution contained only 0.1% w/w solids.
2.4. Resin-in-pulp scavenging tests
The same experimental method was used to test resin-in-pulp
scavenging on both the industrial and synthetic material. Once
the slurry was heated to the desired temperature, wet filtered TP
220 resin was added to the slurry. Resin was contacted with slurry
for 3 h under moderate mixing to ensure homogenous distribution
of the resin while avoiding resin breakage. No significant resin
breakage was observed, but particle size distribution was not
explicitly measured. The pH of the reactor was monitored inline
and was controlled through addition of 20% w/w CaCO3 slurry.
The slurry reached the pH set point of 4.0 within 20–30 min and
was stable for the duration of the 3 h resin loading experiment.
On completion, final slurry and solution was sampled while resin
was separated from slurry via sieves and washed thoroughly with
water. The resin was sub-sampled and assayed using the acid elu-
tion procedure described in Section 2.2, while the rest was set
aside for column elution or further reloading.
2.5. Column procedures
Column contacting was used for ammonia elution of loaded re-
sin. The column used was 15 mm in diameter. Depending on the
bed volume size and elution flow rate, the linear velocity of flow
ranged from 0.8 to 1.6 m/h. In any case, eluent was pumped into
the top of the column using a peristaltic pump, passed over the re-
sin, and eluate was collected and sampled. As this was ammonia
based elution, care was taken to keep the eluent reservoir, column,
and eluate reservoir air tight to prevent excess volatilization of
ammonia. Additionally, the column was water jacketed to allow
temperature control when necessary.
Column contacting was also used to scavenge metal from the
decant solution described in Table 2. This decant solution con-
tained roughly 0.1% solids on receiving, which were removed from
solution via vacuum filtration using quantitative cellulose filter pa-
per. As a result, this material was suitable for use in columns. In
this case, the tailings decant solution was passed over 50 mL of re-
sin at a rate of 5 bed volumes per hour at 25 °C. For this volume of
resin and flow rate, the linear velocity of flow was 1.4 m/h. Solution
samples of permeate were collected periodically.
Table 1
Composition of solution in synthetic pulp, sulphate matrix.
mg/L Ni Co Fe Al Mg Mn
Synth L 480 63 68 28 13,000 1459
Synth H 1212 151 120 33 16,461 2044
After every stage of both elution and loading, the resin was
rinsed in the column with 20 bed volumes of de-ionized water to
remove entrained solution. Particular care was necessary during
the second pass of metal bearing decant solution resin that had
been eluted with ammonia. One bed volume of 1 g/L H2SO4 was
passed through the column to insure that the metals in the decant
solution would not immediately precipitate on contact with the
high pH resin.
3. Results and discussion
3.1. Eluent composition – synthetic batch flasks and resin columns
To determine the optimal composition of the eluent, solutions
containing various amounts of ammonia and ammonium sul-
phate/carbonate were equilibrated with the resin. The results of
these batch experiments are presented in Table 3. It can be seen
that nickel is readily eluted by even dilute ammonia solutions, with
or without ammonium sulphate or carbonate. The extent of nickel
elution is proportional to ammonia concentration. The presence of
ammonium sulphate in solution did not significantly affect nickel
elution but the presence of ammonium carbonated appears to sup-
press the elution slightly.
To investigate the kinetics of ammonia elution, samples of resin
were contacted with ammonia solution using the batch flask resin-
solution contact methodology described in Section 2.2, with fre-
quent samples taken for the first 2 h and a final sample after
24 h to show equilibrium behaviour. The kinetic curves generated
are shown in Fig. 2. It is clear that the ammonia elution reaction is
considerably faster than acidic elution of the same resin, though at
equilibrium all three solutions recover greater than 95% of the
nickel on the resin. Increasing the concentration of ammonia im-
proved reaction kinetics, but not drastically so.
Next, experiments were carried out to determine the elution
behaviour of nickel and cobalt in the continuous flow column reac-
tor configuration. Two columns were run, one with pure nickel
loaded resin and the other cobalt. Samples of resin were eluted
with 6.8% w/w NH4OH solution at 25 °C. As the previous kinetic
tests indicated a relatively rapid rate of resin elution, a relatively
high elution flow rate of 10 BV/h was chosen. The results of these
column tests are shown in Fig. 3. This figure shows that a high
recovery of nickel and cobalt from TP 220 resin can be achieved
in a small number of bed volumes at a relatively high elution flow
rate. Previous researchers have tended to elute IDA resin in sulphu-
ric acid at 2 BV/h (Nicol and Zainol, 2003; Wassink et al., 2006; Zai-
nol, 2005; Zainol and Nicol, 2009) whereas in this work 5 BV/h was
found to be adequate. Grinstead identified that nickel is amenable
to elution from bis-picolylamine resin with ammonia, but found
that cobalt was not (Grinstead, 1984). These results demonstrate
the contrary – that both metals can be recovered effectively with
ammoniacal elution.
3.2. Resin-in-pulp loading
Resin-in-pulp scavenging of metal from both the synthetic and
industrial samples described in Tables 1 and 2 was evaluated. The
results of these resin loading experiments are shown in Tables 4
and 5. In every case, recovery of nickel was greater than 95% and
recovery of cobalt greater than 80%. While not shown in these ta-
bles, resin-in-pulp contact at 25 °C yielded similarly high recovery.
However, the higher temperature changed the slurry rheology and
facilitated resin-slurry mixing and subsequent sieving.
Ca
In each test, resin-slurry contact time was 3 h. While the kinet-
612
ics of resin loading were not rigorously studied, solution samples
725
were taken at the 0.5 and 1.5 h mark. In each test the solution
 P. Littlejohn, J. Vaughan / Minerals Engineering 54 (2013) 14–20 17

Fig. 1. Schematic flow sheet of material sampling points.

Table 2
Composition of solution in industrial pulp and decant solution.

Samples Solution Concentration (mg/L) Solids (mg/kg) pH

Ni Co Fe Al Cr Mg Mn Ca Cu Zn Ni Co
Slurry 1 489 46 3043 944 102 21409 1505 747 17 1.3 641 1.3 1.9
Slurry 2 478 45 2136 67 4 19069 1349 731 0.2 2.6 695 0.3 4.5
Decant 549 60 4928 799 44 31797 2251 991 2 7.9 – – 2.4

Table 3
Equilibrium recovery of nickel from synthetic loaded resin with various solutions, 5 mL resin, 100 mL solution, 25 °C.

Test NH4OH (% w/w) (NH4)2SO4 (g/L) (NH4)2CO3 (g/L) [Ni] (mg/L) % Ni recovery
1 2.80 – – 890 75
2 5.60 – – 1027 84
3 8.43 – – 1132 92
4 11.24 – – 1187 99
5 5.60 289 – 1089 91
6 5.60 198 – 1091 89
7 5.60 99 – 1097 90
8 5.60 – 218 1073 85
9 5.60 – 152 1083 86
10 5.60 – 76 1128 91

Fig. 2. Kinetics of eluting synthetic nickel loaded TP 220 in batch flasks, ammonia
vs. sulphuric acid, 25 °C.
concentration of nickel at 30 min was 20–40 ppm, indicating that
the majority of nickel was recovered in the first 30 min of contact.
Cobalt followed a similar profile.
Evidence of the high selectivity of TP 220 for nickel and cobalt
can be seen in Table 5, which shows that the useful capacity of
the resin (defined as mass of nickel and cobalt per liter resin over
mass of all loaded metals) ranges from 75% to 90%. The most signif-
icant impurity loaded by TP 220 was ferric iron. However, this
loading is not irreversible – it can be seen from the resin selectivity
order presented in Section 2.1 that nickel is higher than ferric iron.
Fig. 3. Column recovery of synthetic loaded pure nickel and pure cobalt resin.
As a result, ferric is exchanged for nickel as the resin undergoes
successive loading stages. This was demonstrated with tests 4a/
4b. The resin in test 4a was loaded with 10.3 g/L Ni and 2.94 g/L
Fe. A portion of this resin was assayed and the remainder was con-
tacted with another batch of tailings slurry (4b). After the second
contact the loaded resin contained 15.2 g/L Ni and 1.3 g/L Fe. These
results indicate that ferric iron can be displaced by nickel in resin-
in-pulp contact. Marston and Rodgers observed similar behaviour
during recovery of nickel from laterite heap leach liquor (Marston
and Rodgers, 2009). Despite nickel being ahead of iron in the BPA
selectivity order a certain amount of iron will co-load with nickel
on the resin.
18 P. Littlejohn, J. Vaughan / Minerals Engineering 54 (2013) 14–20

Table 4
Resin-in-pulp scavenging of Ni and Co from synthetic and industrial materials, pH 4, 60 °C, 3 h contact time.

# Starting slurry Vol % resin (v/v) Initial Sol’n (ppm) Final Sol’n (ppm) Overall recovery (%)
Ni Co Ni Co Ni Co
1 Slurry 1 2.1 489 46 8 6 98.4 87.0
2 Slurry 1 2.9 489 46 18 9 96.3 80.4
3 Slurry 2 2.0 478 45 9 9 98.1 80.0
4a Slurry 2 3.0 478 45 13 10 97.1 77.8
4b Slurry 2 2.8 478 45 12 8 97.5 82.2
5 Synthetic 220L 4.4 480 63 7 1.8 98.5 97.1
6 Synthetic 220H 5.3 1212 151 14 6.6 98.8 95.6

Table 5
Composition of loaded resin from resin-in-pulp tests in Table 4.

Resin # Ni (g/L) Co (g/L) Fe (g/L) Al (g/L) Cr (g/L) Mg (g/L) Mn (g/L) Ca (g/L) Cu (g/L) Zn (g/L)
1 12.35 0.70 2.78 0.10 0.06 0.21 0.02 0.13 0.01 0.29
2 12.49 0.54 3.60 0.18 0.15 0.09 0.01 0.04 0.01 0.26
3 12.17 0.91 1.88 0.02 0.01 0.07 0.01 0.06 0.00 0.65
4a 10.25 0.71 2.94 0.10 0.04 0.46 0.07 0.03 0.00 0.59
4b 15.24 0.58 1.27 0.05 0.01 0.14 0.03 0.12 0.00 0.64
5 2.91 0.51 0.08 0.08 – 0.07 0.07 0.05 – –
6 6.67 0.97 0.10 0.12 – 0.51 0.45 0.09 – –

After being loaded through resin-in-pulp contact, resin was

eluted from the resin with 6.8% w/w aqueous ammonia. Fig. 4
shows the elution response of the combined resin from tests 1
and 2. Only Ni, Co, Cu and Zn are shown in the figure, as the elution
of other metals was minimal. Peak concentrations of Al, Fe, Cr, Mg,
Mn, and Ca in the eluate were 1 ppm or less. After 4 bed volumes of
eluent, recovery of nickel and cobalt to the solution phase was 94%
and 83% respectively. This level of selectivity and nickel and cobalt
recovery was achieved in all columns of resin-in-pulp loaded resin.

3.3. Column loading from tailings decant solution

Recovery of nickel and cobalt value from tailings pond decant

solution was investigated. The industrial sample used was taken Fig. 5. Column loading of TP 220 with tailings decant solution, first contact.
from tailings decant en route to crystallization ponds, and as such
contained virtually no solids. As a result, nickel and cobalt could be
recovered onto resin from this solution using simpler column ion
exchange rather than resin-in-pulp. The column contacting took
the following form: TP 220 resin in the proton form was first con-
tacted with decant solution, then resin was eluted using aqueous
ammonia, followed by a second contact with decant solution.
Figs. 5 and 6 show breakthrough curves for Ni, Co, and Fe for each
contact. Breakthrough curves for Al, Ca, Cr, Mg, Mn and Na are ne-
glected, as these elements showed no affinity for the resin in these
tests. The small amount of Zn and Cu in solution followed the same
curve as that of Ni.

Fig. 6. Column loading of TP 220 with tailings decant solution, second contact.

The results indicate that nickel and cobalt load preferentially

Fig. 4. Ammonia elution response of resin-in-pulp loaded TP 220.
onto the resin despite the solution being at pH 2.4. Subsequent
ammonia elution of the column loaded resin showed the same high
selectivity and recovery as with the resin loaded from pulp. It can
be seen that the resin is less selective for cobalt than nickel, indi-
cated by the earlier breakthrough curve of cobalt. Towards the
end of each column experiment, cobalt concentration in the per-
meate was greater than that of the head solution, indicating that
cobalt loads early but is displaced by nickel.
 P. Littlejohn, J. Vaughan / Minerals Engineering 54 (2013) 14–20
Table 6
Composition of resin after column loading from decant solution and elution with 6.8% w/w aqueous ammonia.
Resin (g/L) Al Ca Co Cr
1st Load 0.11 0.23 0.41 0.01
1st Elution 0.05 0.20 0.09 0.01
2nd Load 0.02 0.30 0.40 0.03
2nd Elution 0.01 0.19 0.16 0.02
Of note is the behaviour of iron. The total concentration of iron
in the head solution was 5.8 g/L; however, most of this was present
as ferrous iron, indicated by the relatively low potential recorded
between a platinum electrode and a Ag/AgCl reference electrode
(373 mV Pt vs. Ag/AgCl). Ferrous iron does not bond strongly with
BPA resin, but ferric is second only to nickel and copper in the
selectivity order. As a result, it can be seen from iron levels in
the permeate in Figs. 5 and 6 that iron loads onto the resin. How-
ever, by the end of the second contact with resin the amount of
iron in the permeate is greater than that of the head, indicating
that iron is being displaced off the resin by nickel. This result sug-
gests that the ratio of nickel to iron on the final loaded resin is
dependent on the number of bed volumes passed and the flow rate
of solution, with higher bed volumes passed leading to higher nick-
el to iron ratio on the loaded resin.
After each contact with decant solution, resin was eluted with
6.8% w/w aqueous ammonia in the same fashion as the resin-in-
pulp loaded resin. The results of elution were similar to that of
the resin-in-pulp loaded resin. Nickel and cobalt recovery in 2
bed volumes of eluate was 90% and 75% respectively, with ppm
levels of impurities. A summary of resin compositions at each stage
of the sequential column loading is presented in Table 6.
3.4. Resin fouling
As the ammoniacal elution method described above necessarily
involves contact of a high pH solution with resin loaded with met-
als that are not soluble in ammonia, potential exists for resin foul-
ing via hydroxide precipitation. Aluminium and chromium are
unlikely to cause issues as they have a very low affinity for the re-
sin during loading and thus only minimal amounts are present dur-
ing elution. Iron may be more problematic as BPA resin displays
affinity for ferric iron and thus significant amounts of iron may
be present on the resin during ammoniacal elution. This issue
could be managed in several ways. If resin-in-pulp contact with
tailings slurry is used, dissolved ferric iron in the initial slurry
can be minimized through neutralization of the load slurry. Addi-
tionally, ferric iron loading on the resin can be minimized through
contacting loaded resin with fresh slurry, as shown in tests 4a/4b
in Section 3.2. In practice this would require counter-current RIP
operation. A second method of managing ferric iron would be to re-
duce it to ferrous iron using a suitable reductant, such as sodium
sulphite. As BPA resin displays very low affinity for ferrous iron
compared to ferric, once reduced iron can be rinsed off the resin
(Marston and Rodgers, 2009). Finally, a periodic wash with sulphu-
ric acid could be employed to dissolve hydroxide precipitates
should they form.
4. Conclusions
This program of experimental work aimed to answer the fol-
lowing questions:
 Can BPA resin scavenge nickel and cobalt from laterite tailings?
 Can nickel and cobalt be selectively recovered through ammoni-
acal elution?
19
Cu Fe Mg Mn Na Ni Zn
0.03 4.26 0.29 0.01 0.41 13.78 1.44
0.00 4.20 0.18 0.01 0.20 1.36 0.08
0.01 5.80 0.09 0.01 0.04 12.41 1.60
0.00 5.70 0.06 0.01 0.03 1.53 0.16
The technical feasibility of scavenging nickel and cobalt from
laterite leach tailings was demonstrated on both synthetic material
and samples from an industrial nickel refinery. BPA functionalized
TP 220 resin was found to be effective at recovering nickel and co-
balt both in batch resin-in-pulp tests on industrial neutralized tails
slurry as well as in column contact with clarified tailings decant
solution. The resin’s high selectivity for nickel and cobalt over
impurities lead to useful resin capacity of 75–90%, considerably
higher than that of iminodiacetic acid functionalized resin. Ferric
iron was the most significant impurity to be loaded, but does not
overwhelm the resin. Instead, iron on the resin is gradually dis-
placed by nickel due to its rank in the resin selectivity order. Re-
sin-in-pulp loading kinetics were rapid, with over 95% of the
metal ultimately loaded being taken up by the resin in the first
30 min of contact. The scavenging of nickel and cobalt from tailings
decant offers a potential method to recover value metals that
would otherwise be lost to waste while obviating the need for
more complicated resin-in-pulp contact.
Selective elution of nickel and cobalt from BPA functionalized
resin was effective. 90–95% of nickel and 75–85% of cobalt was
eluted using 2–4 bed volumes of 6.8% w/w NH4OH solution. Elution
kinetics were rapid and the elution response curve was sharp, with
the majority of metal being recovered in the first 0.5–1 bed volume
of eluate. Impurities such as iron, aluminium, chromium, manga-
nese, magnesium and sodium demonstrate low affinity for ammo-
nia solutions, and are limited to 5 ppm or less in the eluate. Due to
their affinity for both BPA resin and ammonia solutions, zinc and
copper follow nickel and cobalt throughout the process. Further re-
search investigating the possibility of resin fouling via hydroxide
precipitation during ammoniacal elution is warranted.
Resin-in-pulp scavenging of nickel and cobalt from laterite tail-
ings has not been commercialized to date, in part due to the diffi-
culty of integrating acidic eluate from IDA resin into existing nickel
refining flow sheets. The use of BPA resin and ammonia elution of
nickel and cobalt offers new possibilities for the integration of re-
sin-in-pulp into existing refinery flow sheets. As the eluate con-
tains high concentrations of nickel and cobalt and trace amounts
of impurities, downstream integration of value metal recovered
from tailings may be possible.
Acknowledgements
The authors would like to acknowledge Lanxess ION for provid-
ing resin samples. The help of Chen Han during experimentation is
appreciated. The support of UniQuest is also recognized.
References
Adams, M.A., 2007. Towards a virtual metallurgical plant – CCD vs RIP case study.
In: Proceedings of ALTA Ni/Co/Cu 2007, Perth, Australia.
Duyvesteyn, W., Neudorf, D., et al., 2002. Resin-in-pulp method for recovery of
nickel and cobalt. US Patent No. 6350420. Washington, DC: U.S.
Fleming, C.A., Nicol, M., 1980. A comparative study of kinetic models for the
extraction of uranium by strong-base anion-exchange resins. J. S. Afr. Inst. Min.
Metall. 80 (2), 89–99.
Grinstead, R., 1984. 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, 387–400.
20 P. Littlejohn, J. Vaughan / Minerals Engineering 54 (2013) 14–20
Halle, O., Rossoni, D., 2005. A new (monodisperse) chelating resin designed for
mining application: Lewatit Monoplus TP 207. ALTA Ni/Co/Cu 2005, Perth,
Australia.
Lanxess, 2011. Lewatit TP 220 Technical Sheet, viewed September 11th, 2012 http://
www.lewatit.com/common/
download.php?file=e8a10ef8026615d3c32a955b1612e16f.
Littlejohn, P., Vaughan, J., 2010. Selective ammoniacal elution of nickel and cobalt
from iminodiacetate cation exchange resin. ALTA Ni/Co/Cu 2010, Perth,
Australia.
Littlejohn, P., Vaughan, J., 2012. Selectivity of commercial and novel mixed
functionality cation exchange resins in mildly acidic sulfate and mixed
sulfate–chloride solution. Hydrometallurgy 121–124, 90–99.
Littlejohn, P., Vaughan, J., et al., 2012. Elution strategies for recovery of nickel and
cobalt from laterite tails through scavenging resin-in-pulp. ALTA Ni/Co/Cu
2012, Perth Australia.
Marston, C., Rodgers, M., 2009. Nickel recovery from lateritic ore in the presence of
ferric iron using bispicolylamine chelating resin. Conference of Metallurgists. J.
Budac. Sudbury, Canada, CIM.
McKevitt, B., Dreisinger, D., 2011. A comparison of large bead ion exchange resins
for the recovery of base metals in a resin-in-pulp (RIP) circuit. In: Proceedings of
the South African Institute of Mining and Metallurgy Base Metals Conference.
Mendes, F., Martins, A., 2004. Selective sorption of nickel and cobalt from sulphate
solutions using chelating resins. Int. J. Min. Proc. 75, 359–371.
Mendes, F., Martins, A., 2005. Recovery of nickel and cobalt from acid leach pulp by
ion exchange using chelating resin. Min. Eng. 18, 945–954.
Mendes, F., 2010. Resin-in-leach process to recover nickel and/or cobalt in ore
leaching pulps. US Patent No. 2010/0196190. Washington, DC: U.S.
Nicol, M., Zainol, Z., 2003. The development of a resin-in-pulp process for the
recovery of nickel and cobalt from laterite leach slurries. Int. J. Min. Procss. 72,
407–415.
Prasad, M.S., Mensah-Biney, R., et al., 1991. Modern trends in gold processing –
overview. Min. Eng. 4 (12), 1257–1277.
Rosato, L., Harris, G.B., et al., 1984. Separation of nickel from cobalt in sulphate
medium by ion exchange (XFS 4195 resin). Hydrometallurgy 13, 33–44.
Taylor, Jansen, 2000. Future Trends in PAL Plant Design for Ni/Co Laterites. ALTA Ni/
Co/Cu 2000. Perth, Australia.
Wassink, B., Neufeld, M., et al., 2006. Towards a resin-in-pulp process for recovery
of nickel and cobalt from laterite leach tailings: an iminodiacetic acid ion
exchange resin as a prospective resin. International Water Conference 2006.
Wyethe, J.P., Kotze, M.H., et al., 2002. Cobalt, Nickel and Copper Recovery with
Resin-in-Pulp. ALTA Ni/Co/Cu 2002, Perth, Australia.
Zainol, Z., 2005. The development of a resin-in-pulp process for the recovery of
nickel and cobalt from laterite leach slurries. Perth, Murdoch University. Ph.D.
Zainol, Z., Nicol, M., 2009. Comparative study of chelating ion exchange resins for
the recovery of nickel and cobalt from laterite leach tailings. Hydrometallurgy
96 (4), 283–287.
Zontov, N., 2001. Potential Benefits of Resin-in-Pulp for PAL Plants. ALTA Ni/Co/Cu
2001, Perth, Australia.