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DOWNSTREAM PROCESSING OPTIONS FOR NICKEL LATERITE HEAP LEACH

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Conference Paper · May 2007

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 DOWNSTREAM PROCESSING OPTIONS FOR NICKEL LATERITE
HEAP LEACH LIQUORS

By

Boyd Willis
Aker Kvaerner Australia Pty Ltd

Presented by

Boyd Willis
boyd.willis@akerkvaerner.com

CONTENTS

ABSTRACT ............................................................................................................................... 2
1. INTRODUCTION ............................................................................................................... 2
2. ESTABLISHED FLOWSHEETS ........................................................................................ 2
2.1. MIXED HYDROXIDE PRECIPITATION (MHP) ROUTE 2
2.2. MIXED SULPHIDE PRECIPITATION (MSP) ROUTE 9
3. CONCEPTUAL HYBRID FLOWSHEETS........................................................................ 15
3.1. NICKEL AND COBALT RECOVERY BY MOLECULAR RECOGNITION TECHNOLOGY
(MRT) 15
3.2. MIXED SULPHIDE PRECIPITATION WITH IRON REMOVAL BY MOLECULAR
RECOGNITION TECHNOLOGY (MRT) 18
3.3. MIXED SULPHIDE PRECIPITATION WITH IRON REMOVAL BY ION EXCHANGE (IX) 20
3.4. MIXED SULPHIDE PRECIPITATION WITH IRON REMOVAL BY RESIN-IN-PULP (RIP) 22
4. COMPARISON OF FLOWSHEET STRENGTHS AND WEAKNESSES......................... 25
5. ACKNOWLEDGEMENTS................................................................................................ 26
6. REFERENCES ................................................................................................................ 26
 ABSTRACT

Growing worldwide interest in the application of heap leaching technology to nickel laterite ores heralds
a need to explore compatible nickel recovery flowsheets. Alternative approaches to downstream
processing of nickel laterite heap leach liquors are described and reviewed. Block flowsheets for
established and conceptual processes are presented and each flowsheet is assessed in terms of
strengths, weaknesses and product quality. The impact of ore type and grade on process selection is
examined. Considerations related to project location and infrastructure needs are also discussed.
Generic examples are given where appropriate.

1. INTRODUCTION

The arrival of nickel laterite heap leaching on the world stage, largely through the endeavours of
European Nickel in Turkey, has generated much interest. As more and more projects assess the
amenability of their ores to heap leaching, it has become evident, as it did with high pressure acid
leaching (HPAL), that different ore bodies and locations lend themselves to different downstream
recovery processes. While generally speaking any downstream nickel recovery flowsheet can be
adapted to any nickel laterite heap leach, there will always be an option which optimises the project
economics.
In recent years there has been substantial refinement of process flowsheets for the downstream
recovery of nickel from HPAL discharge slurries. However, the same cannot be said for heap leach
liquors. The pregnant leach solution (PLS) obtained from a nickel laterite heap leach exhibits some
significant differences to a HPAL discharge slurry. HPAL produces a hot slurry, at 20-25% solids,
containing typically 4-6 g/L nickel, 40-60 g/L sulphuric acid, <8 g/L iron and <3 g/L aluminium. Heap
leaching produces an essentially solids-free solution, at ambient temperature, containing typically
2-4 g/L nickel, 30-50 g/L sulphuric acid, 15-30 g/L iron and 2-5 g/L aluminium. The key differences that
have to be considered when treating a heap leach PLS stream are: lower temperature, lower nickel
tenor and higher iron tenor. These factors can have a significant impact on the downstream recovery of
nickel and the quality of the desired intermediate product.
This paper aims to establish some general principles to guide preliminary selection of the right nickel
recovery flowsheet. Established downstream processing options are reviewed with particular emphasis
given to the influence of heap leach PLS composition on recovery and product quality. A number of
conceptual hybrid processing options, tailored specifically for treating heap leach PLS, are introduced.

2. ESTABLISHED FLOWSHEETS

For the purposes of this paper, flowsheets that have previously been applied to downstream nickel
recovery from leach liquors are defined as established flowsheets. The flowsheets that fall into this
category are mixed hydroxide precipitation and mixed sulphide precipitation. Only flowsheets that
produce an intermediate product are discussed, as the main driver for selecting heap leaching over
HPAL is considered to be the prioritisation of lower capital cost over higher nickel extraction. On that
basis options that require an integrated metal refinery, such as direct solvent extraction, are excluded.

2.1. MIXED HYDROXIDE PRECIPITATION (MHP) ROUTE

2.1.1. Overview
Mixed hydroxide precipitation (MHP) lacks selectivity for nickel and cobalt over iron, aluminium,
chromium and manganese. Iron, aluminium and chromium can be removed prior to nickel and cobalt
precipitation, although some collateral loss of nickel and cobalt with these elements is unavoidable.
Manganese cannot be removed prior to nickel and cobalt precipitation, and some manganese
contamination of the MHP product must be tolerated. Copper and zinc will report to the MHP product,
however these are usually very minor contaminants that can be tolerated.

2
The MHP flowsheet is therefore not suited to ores with high manganese content (generally limited to
certain limonites). High nickel and cobalt losses will be experienced with ores having higher than
average iron or aluminium content. The flowsheet is best applied to ores with low manganese content
(nickel to manganese ratio >3:1). The flowsheet will generally be well suited to saprolitic ores, which
tend to have higher nickel content and low iron content.
The flowsheet steps, as depicted by Figures 2-1 and 2-2, are:
• Recycle Leach
• Iron Removal Stage 1
• Iron Removal Stage 2 (optional)
• Nickel Cobalt Precipitation Stage 1
• Nickel Cobalt Precipitation Stage 2
• Manganese Removal (if required)

2.1.2. Recycle Leach

The function of recycle leach is to utilise the residual acid in the heap leach PLS to recover, by
re-dissolution, any nickel and cobalt co-precipitated as hydroxides in 2nd stage iron removal and 2nd
stage nickel-cobalt precipitation.

Chemistry
Nickel and cobalt hydroxides contained in process precipitates can be dissolved by sulphuric acid
solutions. An operating temperature of >50°C is favoured to facilitate high recoveries of nickel and
cobalt. Operation at low or ambient temperature is not recommended as dissolution extents are low.
By maintaining a terminal sulphuric acid concentration after recycle leaching of >20 g/L, nickel and
cobalt recoveries from the precipitates of 95-100% can be achieved. Significant quantities of any iron,
aluminium and other hydroxides present also re-dissolve.

Process Description
The solids produced in 2nd stage iron removal and 2nd stage nickel-cobalt precipitation are thickened
and directed to the Recycle Leach, where they are contacted with incoming heap leach PLS. Typically
1 or 2 tanks in series are used, operating at >50°C, with between 60 and 120 minutes combined
residence time. The discharge stream is forwarded to iron removal. The recycle streams increase the
hydraulic throughput of the downstream processes.

2.1.3. Iron Removal

The function of iron removal is to neutralise excess acid in the heap leach PLS and to remove iron and
aluminium from solution prior to nickel and cobalt precipitation.

Chemistry
Iron, as Fe(III), can be removed from leach liquors to a residual concentration of <200 mg/L at pH
2.5-3.0. (Fe(III) precipitation commences at as low as pH 1.8). Under these pH conditions chromium is
removed to very low levels, however aluminium is only removed to around 2 g/L. Gypsum is
precipitated as a product of the acid neutralisation reaction. An operating temperature of 70-90°C is
favoured to facilitate fast reaction kinetics and to lower slurry viscosity. Operation at ambient
temperature is possible however the kinetics are slow. Co-precipitation of nickel and cobalt in this pH
range is minimal, typically <0.5%, so the precipitates formed may be washed to recover soluble nickel
and cobalt and then discarded.
The residual aluminium, when allowed to report to the mixed hydroxide product, is a low concentration
but very troublesome contaminant. The presence of aluminium in the MHP product at levels as low as
0.5% has been demonstrated to reduce nickel/cobalt dissolution in subsequent ammonia leaching by
10-30%. It is believed that an amorphous and gelatinous aluminium hydroxide precipitate entraps
some of the nickel/cobalt precipitates. As aluminium hydroxide is insoluble in ammonia solutions, the

3
associated nickel and cobalt are rendered unrecoverable. It is therefore desirable to precipitate
aluminium in the iron removal process. Removal of aluminium to <50 mg/L requires a pH of the order
of 4.4-4.8. In this pH range co-precipitation of nickel and cobalt is significant, typically 4-10%.

ORE

SULPHURIC
ACID

HEAP LEACH

PLS

RECYCLE LEACH

FILTRATE

WASH
SOLUTION
LIMESTONE
~3.5 pH

SOLIDS BELT FILTER

AIR IRON REMOVAL
OR CCD

SOLUTION SOLIDS TO
MAGNESIA DISPOSAL
~4.5 pH

NICKEL SOLIDS
MIXED
PRECIPITATION HYDROXIDE
STAGE 1 PRODUCT

LIME SOLUTION

NICKEL SOLIDS
PRECIPITATION
STAGE 2

SOLUTION

MANGANESE SOLIDS TO
LIME
REMOVAL DISPOSAL

BARREN SOLUTION
(RECYCLE WATER)

Figure 2-1: Mixed Hydroxide Precipitation with One Stage Iron Removal

4
 ORE

SULPHURIC
ACID

HEAP LEACH

PLS

RECYCLE LEACH

FILTRATE

WASH
SOLUTION
LIMESTONE
~3.5 pH

IRON REMOVAL SOLIDS BELT FILTER

AIR
STAGE 1 OR CCD

SOLUTION SOLIDS TO
LIMESTONE 2.5-3.0 pH DISPOSAL

IRON REMOVAL SOLIDS

STAGE 2

SOLUTION
MAGNESIA
~4.5 pH

MIXED HYDROXIDE MIXED

SOLIDS
PRECIPITATION HYDROXIDE
STAGE 1 PRODUCT

LIME SOLUTION

MIXED HYDROXIDE SOLIDS

PRECIPITATION
STAGE 2

LIME SOLUTION

MANGANESE SOLIDS SOLIDS TO

REMOVAL DISPOSAL

BARREN SOLUTION
RECYCLE WATER

Figure 2-2: Mixed Hydroxide Precipitation with Two Stage Iron Removal

5
If the pH adjustment to 4.4-4.8 is performed as a discrete second stage, the quantity of precipitates is
relatively small (typically <10% of the solids precipitated in stage 1) and these can be contacted with
acidic leach liquor (PLS) to re-dissolve the co-precipitated nickel and cobalt hydroxides. However, if
iron removal is performed in a single stage the quantity of precipitates is such that there is no practical
means to recover the co-precipitated nickel and cobalt, and these values are lost from the circuit. Iron
removal is therefore ideally performed in two stages, with terminal pHs of 2.5-3.0 and 4.4-4.8
respectively.

Process Description
In first stage iron removal excess acid is neutralised by limestone addition to pH 2.5-3.0, precipitating
gypsum. Much of the iron and chromium, and some aluminium, are precipitated. Typically 3 or 4 tanks
in series are used, operating at 70-90°C, with between 90 and 180 minutes combined residence time.
Air is normally injected to (i) sweep the carbon dioxide produced by the limestone reaction from
solution, preventing bicarbonate buffering, and (ii) oxidise any aqueous Fe(II) present to Fe(III). In
single stage iron removal the pH is stepped up progressively to pH 4.4-4.8, precipitating the remaining
iron and chromium, and most of the aluminium. The discharge slurry is thickened and soluble nickel
and cobalt are recovered either by counter-current decantation (CCD) washing (1-2 stages) or counter-
current washing on a belt filter. The washed solids are disposed of, either as a slurry or a filter cake. In
order to generate a precipitate with good settling and filtration properties, thickener underflow is
recycled as seed at a rate of 100-300% of fresh precipitates.
The overflow solution from the stage 1 thickener is directed to stage 2, where the solution is further
neutralised by limestone addition to pH 4.4-4.8. Typically 3 or 4 tanks in series are used, operating at
70-90°C, with between 60 and 120 minutes combined residence time. The remaining iron and
chromium, and most of the aluminium, are precipitated, along with some of the nickel and cobalt. The
target terminal pH is governed by the desired residual aluminium concentration in solution. The
discharge slurry is thickened and directed to the recycle leach circuit for recovery of the co-precipitated
nickel and cobalt. In order to generate a precipitate with good settling properties, thickener underflow is
recycled as seed at a rate of 100-300% of fresh precipitates.

2.1.4. Mixed Hydroxide Precipitation

The function of mixed hydroxide precipitation (MHP) is to recover nickel and cobalt from solution as
hydroxide precipitates.

Chemistry
MHP is not highly selective for nickel and cobalt over manganese. It is therefore best performed in two
stages in order to control the extent of manganese deportment to the mixed hydroxide product.
In the first stage MHP the solution is typically adjusted to pH 7.2-7.5 in order to obtain the maximum
practical nickel and cobalt precipitation achievable while limiting the manganese content of the product
solids to <5%. This is somewhat dependent upon the nickel to manganese ratio in the feed stream.
Approximately 90-95% of the nickel, cobalt, copper and zinc are precipitated along with any residual
iron, aluminium and chromium present. An operating temperature of >60°C is favoured to facilitate fast
reaction kinetics. Operation at ambient temperature is possible however the kinetics are slow. The co-
precipitation of manganese is typically in the range 15-35%. When magnesia is used for pH adjustment
some magnesium reports to the MHP product, generally in the form of unreacted magnesium oxide.
The MHP product is washed to remove soluble impurities and dewatered for onward shipment.
Magnesia may be substituted with caustic soda (sodium hydroxide), hydrated lime (calcium hydroxide)
or soda ash (sodium carbonate). Caustic soda eliminates the magnesium content of the MHP product
that is associated with unreacted magnesia, and offers slightly improved selectivity for nickel over
manganese through faster mixing and more precise pH control, yielding a higher quality product,
however it is generally very expensive. Lime introduces calcium which results in gypsum precipitation
and therefore contamination of the MHP product. The use of soda ash results in the precipitation of
basic carbonates along with hydroxides, however the solubility of manganese carbonate is lower than
that of nickel carbonate, thus the selectivity for nickel over manganese is further reduced.
The depleted solution is forwarded to second stage MHP where residual nickel and cobalt are
recovered by adjusting the pH to 7.5-8.0. Nearly all of the residual nickel and cobalt are precipitated,
along with 20-30% of the remaining manganese. The precipitates typically contain 10-20%

6
manganese. Terminal nickel and cobalt concentrations in solution are reduced to <5 mg/L. The nickel
and cobalt hydroxides contained in the precipitates can be re-dissolved by contact with acidic leach
liquor (PLS). Manganese hydroxide also re-dissolves, establishing a recirculating load of manganese in
the flowsheet.
A low grade mixed hydroxide product can be produced by employing single stage precipitation at pH
7.5-8.0. This approach will lower the project capital expenditure however the product may contain
>10% manganese, limiting marketing options.

Process Description
In first stage MHP the solution is adjusted to pH 7.2-7.5 by the addition of freshly prepared magnesia
slurry. Typically 3 or 4 tanks in series are used, operating at 60-80°C, with between 120 and 180
minutes combined residence time. The discharge slurry is thickened and soluble impurities are
removed by wash filtration. The washed solids are recovered as a filter cake. In order to generate a
precipitate with good settling and filtration properties, thickener underflow is recycled as seed at a rate
of 100-200% of fresh precipitates.
The overflow solution from the stage 1 thickener is directed to stage 2, where the solution is adjusted to
pH 7.5-8.0 by the addition of hydrated lime slurry. Typically 2 or 3 tanks in series are used, operating at
60-80°C, with between 60 and 120 minutes combined residence time. Soda ash can be used but a
more quantitative recovery of nickel and cobalt is achieved using lime. The terminal pH is governed by
the desired residual nickel concentration in the depleted solution. The discharge slurry is thickened and
directed to the recycle leach circuit for recovery of nickel and cobalt from the hydroxide precipitates by
re-dissolution. In order to generate a precipitate with good settling properties, thickener underflow is
normally recycled as seed at a rate of 100% of fresh precipitates.
Thickener overflow solution is either recycled to heap leaching or forwarded to manganese removal.

2.1.5. Manganese Removal (Optional)

The function of manganese removal is to eliminate manganese from the process and/or discharge
liquors. The requirement for a manganese removal circuit is project specific. Generally more than 50%
of the manganese remains in solution following two stages of nickel-cobalt precipitation. When it is
necessary for any of the depleted solution to be discarded, environmental regulations will probably
stipulate removal of aqueous manganese, necessitating the inclusion of manganese removal. Where
any of the depleted solution is recycled within the process, or as make-up water to heap leaching,
manganese will accumulate in the circuit until the soluble losses in spent ore moisture and iron removal
filter cake balance the inputs. If the equilibrium concentration of manganese in the circuit does not
adversely affect product quality, then manganese removal can be excluded.

Chemistry
A residual manganese concentration of <100 mg/L can be achieved by adjusting the solution pH to
8.5-9.0, precipitating manganese hydroxide. If a lower residual concentration is required, oxidation by
air injection to form manganese dioxide may be included. Oxygen utilisation of 10-20% is achieved. A
residual concentration of about 10 mg/L is achievable through this approach.

Process Description
The solution is adjusted to pH 8.5-9.0 by the addition of hydrated lime slurry. Typically 2 or 3 tanks in
series are used, operating at 50-60°C, with between 30 and 120 minutes combined residence time. Air
may be injected for manganese oxidation if required. The discharge slurry is thickened and, if desired,
the thickener overflow is recycled to heap leaching and other process consumers. Depending on the
project requirements, the thickener underflow may be disposed of as a slurry or dewatered to produce a
solid waste product. A proportion of the thickener underflow may be recycled as seed to improve the
settling and filtration properties of the precipitates.

2.1.6. Product Quality and Downstream Processing Alternatives

The mixed hydroxide product generally contains <40% nickel (dry basis). Manganese and magnesium
are the main impurity metals, along with co-precipitated copper and zinc. The product is difficult to
dewater and moisture levels of 35-45% are typical. Approximately 4.5 wet tonnes of product must be
shipped to transport one tonne of contained nickel.

7
Table 2-1 summarises typical composition data for MHP product.

Table 2-1: Typical MHP Product Composition

Component Unit Value
Nickel wt% (dry) 30 - 39
Cobalt wt% (dry) 2-5
Zinc wt% (dry) 1-4
Copper wt% (dry) 1-4
Manganese wt% (dry) 4-9
Magnesium wt% (dry) 3-5
Iron wt% (dry) < 0.5
Aluminium wt% (dry) < 0.5
Sulphur wt% (dry) 3-5
Moisture wt% 35 - 45

Atmospheric or low pressure leaching is suitable for the MHP product, with options including
ammonia/ammonium carbonate leaching, ammonium sulphate leaching and acid leaching. Applicable
refining flowsheets include:
• Ammonia leach, ammoniacal SX (ASX), electrowinning.
• Ammonium sulphate leach, cobalt SX, hydrogen reduction.
• Acid leach, cobalt SX, electrowinning.

2.1.7. Location and Infrastructure Considerations

Precipitation of nickel and cobalt as a mixed hydroxide is the least sophisticated process for recovery of
nickel and cobalt from heap leach liquors. All process steps are performed in atmospheric tanks and
simple pH adjustment and precipitation chemistry are applied. Due to the low selectivity of MHP for
nickel and cobalt over other elements, good quality fresh water is preferred. There are no significant
environmental or OH&S concerns associated with the process, particularly if no sulphuric acid plant is
installed. The process plant has low energy demands, so the need to source waste heat energy from a
sulphuric acid plant is diminished. The process reagents are common, relatively inexpensive, and can
usually be regionally sourced.

2.1.8. Summary of Factors Favouring Selection of MHP

Selection of the MHP flowsheet is favoured where several of the following factors prevail:
• ore to be treated has a high Ni:Mn ratio and/or low iron or aluminium content, low manganese
saprolites are well suited;
• product market is reasonably close (offsets higher transport costs);
• the region is environmentally sensitive;
• the site is remote with minimal existing infrastructure;
• the local workforce has a low educational standard;
• the project will not include a sulphuric acid plant;
• the local power supply is inadequate, unreliable or non-existent;
• there is no readily accessible fossil fuel supply;
• there is no readily available hydrocarbon feedstock to produce hydrogen sulphide for MSP;
• good quality fresh water is available;

8
• there is access to inexpensive local supplies of lime and magnesia, caustic soda or soda ash.

2.2. MIXED SULPHIDE PRECIPITATION (MSP) ROUTE

2.2.1. Overview
Precipitation of nickel and cobalt as a mixed sulphide is highly selective for nickel and cobalt over iron,
aluminium, chromium and manganese. The reaction of Fe(III) with hydrogen sulphide produces
undesirable elemental sulphur, and it must therefore be removed or reduced prior to sulphide
precipitation The removal of aluminium, chromium and manganese prior to nickel and cobalt
precipitation is unnecessary. Copper and zinc1 will report to the mixed sulphide product, however these
are usually very minor contaminants that can be tolerated. Copper can be removed prior to nickel and
cobalt precipitation if required.
The MSP flowsheet is therefore particularly well suited to limonitic ores, which typically have low nickel
and high iron content. Due to its selectivity for nickel over manganese, it is also a better alternative to
the MHP flowsheet for ores which have higher than average manganese content, or a nickel to
manganese ratio of less than 3:1.
The flowsheet steps, as depicted by Figures 2-4 and 2-5, are:
• Pre-Reduction (optional)
• Partial Neutralisation
• Nickel Cobalt Precipitation
• Iron Removal and/or Final Neutralisation (if required)

2.2.2. Pre-Reduction (Optional)

Pre-reduction may be employed if exclusion of copper from the mixed sulphide product is desirable.
Selective precipitation of copper as copper sulphide can be achieved by contacting the PLS with
hydrogen sulphide gas under carefully controlled redox conditions. Pre-reduction will also reduce a
significant amount of aqueous Fe(III) to Fe(II). This is undesirable as the iron to nickel ratio is high in
heap leach PLS, and iron present as Fe(II) will largely remain in solution through the subsequent
process steps. Consequently the depleted solution after mixed sulphide precipitation will have a high
iron content, rendering it unsuitable for recycle as water make-up for heap leaching. An additional iron
removal / final neutralisation step will be necessary.

Chemistry
Copper can be removed from acidic leach liquors by contacting the solution with hydrogen sulphide at a
redox potential of about 380 mV. Under these conditions selective precipitation of copper sulphide is
achieved. Simultaneously, approximately 75% of the aqueous Fe(III) present is reduced to Fe(II). Any
Cr(VI) present is quantitatively reduced to Cr(III).

Process Description
Heap leach PLS and hydrogen sulphide gas are contacted in a static mixer and pipe reactor, with a
total residence time of about 30 seconds. The product slurry discharges to a de-gassing tank which is
vented to a gas scrubber. The de-gassed slurry is then directed to partial neutralisation.

2.2.3. Partial Neutralisation

The function of partial neutralisation is to adjust the feed liquor pH ahead of sulphide precipitation to
establish the optimum conditions for nickel and cobalt precipitation.

1
Sumitomo Metal Mining Co Ltd has developed a proprietary method for selective precipitation of zinc sulphide.

9
Chemistry
AMAX data (1) plotted in Figure 2-3 illustrates that there is a significant decrease in the residual nickel
concentration in MSP as the feed liquor pH increases.

250
Residual Nickel Conc.

200

150
(mg/L)

100

50

0
1 2 3 4
MSP Feed Liquor pH

Figure 2-3: Feed Liquor pH and Nickel Precipitation in MSP

MSP is selective for nickel over iron, with the selectivity reported at 23.3:1 by AMAX (1). However the
iron to nickel ratio in laterite heap leach PLS is sufficiently high (ranging between 6:1 and 10:1) that
some iron removal is warranted. By comparison, the iron to nickel ratio in HPAL leach liquors is <1:1.
In addition, the reduction of Fe(III) to Fe(II) during sulphide precipitation could potentially consume
significantly more hydrogen sulphide than the actual nickel and cobalt precipitation reactions, adding to
the capital and operating costs for hydrogen sulphide production. The recommended approach is
therefore to neutralise the PLS to pH 2.5-3.0, precipitating most of the iron present. An operating
temperature of 70-90°C is favoured to facilitate fast reaction kinetics and avoid viscosity problems.
Operation at ambient temperature is possible however the kinetics are slow.
Iron, as Fe(III), can be removed from leach liquors to a residual concentration of <200 mg/L at pH
2.5-3.0. Under these pH conditions chromium is removed to very low levels, however aluminium is only
removed to around 2 g/L. Gypsum is precipitated as a product of the acid neutralisation reaction. At
this pH co-precipitation of nickel and cobalt is minimal, typically <0.5%, so the precipitates formed may
be washed to recover soluble nickel and cobalt and then discarded.

Process Description
Excess acid is neutralised by limestone addition to pH 2.5-3.0, precipitating gypsum. Much of the iron
and chromium, and some aluminium, are precipitated. Typically 3 or 4 tanks in series are used,
operating at 70-90°C, with between 90 and 180 minutes combined residence time. Air is normally
injected to (i) sweep the carbon dioxide produced by the limestone reaction from solution, preventing
bicarbonate buffering, and (ii) oxidise any aqueous Fe(II) present to Fe(III).
The discharge slurry is thickened, and soluble nickel and cobalt are recovered either by counter-current
decantation (CCD) washing (1-2 stages) or counter-current washing on a belt filter. The washed solids
are disposed of, either as a slurry or as a filter cake. In order to generate a precipitate with good
settling and filtration properties, thickener underflow is recycled as seed at a rate of 100-300% of fresh
precipitates. The overflow solution from the partial neutralisation thickener is directed to mixed sulphide
precipitation.

10
2.2.4. Mixed Sulphide Precipitation
The function of mixed sulphide precipitation (MSP) is to recover nickel and cobalt from solution as
sulphide precipitates.

Chemistry
MSP is selective for nickel and cobalt over manganese, iron, aluminium, chromium and magnesium.
Nickel can be precipitated from a feed liquor with pH >2.5 to a residual concentration in barren solution
of <30 mg/L by reaction with hydrogen sulphide gas. Hydrogen sulphide injection is controlled to
maintain a pre-determined hydrogen sulphide overpressure in the reactor vessel. Under these
conditions nickel and cobalt precipitate as sulphides, along with any copper and zinc present. A small
amount of Fe(II) also precipitates. Iron (III), aluminium, chromium, manganese and magnesium are not
precipitated. Any Cr(VI), Mn(IV) and Fe(III) present are reduced to Cr(III), Mn(II) and Fe(II)
respectively. Alternative precipitants are sodium sulphide (Na2S) or sodium hydrosulphide (NaHS).
Precipitation takes place predominantly on the surface of existing particles. Provision of seed surface
area in the form of fine mixed sulphide particles is therefore essential. If insufficient seed surface area
is available, significant scaling of the process equipment results. High shear areas such as agitator
blades are particularly susceptible.

ORE

SULPHURIC
ACID

HEAP LEACH

PLS

FILTRATE

WASH
SOLUTION
LIMESTONE
~3.0 pH

PARTIAL SOLIDS BELT FILTER

AIR
NEUTRALISATION OR CCD

SOLUTION SOLIDS TO
H2S DISPOSAL
2.5-3.0 pH

SOLIDS
MIXED
MIXED SULPHIDE
PRECIPITATION
SULPHIDE
PRODUCT

SOLUTION
~2 pH

Figure 2-4: Mixed Sulphide Precipitation

11
 ORE

SULPHURIC
ACID

HEAP LEACH

H2S PLS

PRE-REDUCTION

FILTRATE

WASH
SOLUTION
LIMESTONE ~2.5 pH

PARTIAL SOLIDS BELT FILTER

AIR
NEUTRALISATION OR CCD

SOLUTION SOLIDS TO
H2S DISPOSAL
~2.5 pH

MIXED
MIXED SULPHIDE SOLIDS
PRECIPITATION
SULPHIDE
PRODUCT

LIMESTONE

SOLIDS TO
AIR IRON REMOVAL
DISPOSAL

BARREN SOLUTION
2.0-2.5 pH

Figure 2-5: Mixed Sulphide Precipitation with Pre-Reduction

Sulphuric acid is produced as a chemical reaction product, slowing the reaction kinetics and increasing
the solubility of the nickel and cobalt sulphide precipitates. The pH of the feed liquor is therefore
normally controlled to maintain the terminal pH within a satisfactory range to obtain optimal recovery

12
(refer to Figure 2-3). An alternative approach is to add magnesia slurry or caustic soda solution to the
MSP reactors in order to maintain constant pH conditions during precipitation.

Process Description
The MSP feed solution is pre-heated to the desired reaction temperature and then blended with
recycled seed slurry. The mixture containing this pre-conditioned seed is then pumped to the reaction
vessel/s where it is contacted with hydrogen sulphide gas. Metal sulphides precipitate onto the active
surface of the seed particles. Precipitation may be performed using either horizontal autoclaves or
multiple vertical reactor vessels:
• Autoclaves: This is the Moa Bay approach. A 3 or 4 compartment autoclave is used, operating at
up to 121°C and 1034 kPa, with between 10 and 30 minutes residence time.
• Multiple Reactors: This is the AMAX approach. 4 or 5 reactors in series are used, operating at
80-95°C and 200-400 kPa, with between 60 and 90 minutes combined residence time.
The product slurry is discharged to a pressure letdown vessel, where steam and dissolved hydrogen
sulphide are flashed off. The vent gas is cooled to condense steam and the hydrogen sulphide rich
non-condensables are re-compressed and returned to the MSP reactor vessel/s. The discharge slurry
is thickened and soluble impurities are removed by wash filtration. The washed solids are recovered as
a filter cake. In order to minimise scaling and to generate a precipitate with good settling and filtration
properties, thickener underflow is recycled as seed at a rate of 300-500% of fresh precipitates.
Thickener overflow (barren solution) at pH 1.5-2.0 is either recycled as make-up water to heap leaching
or, if pre-reduction has been employed, forwarded to iron removal.

2.2.5. Iron Removal and/or Final Neutralisation (Optional)

If pre-reduction has been employed, the barren solution will contain a significant amount of Fe(II). As
the iron tenor in heap leach PLS is already sufficiently high to create some viscosity issues, the recycle
of any aqueous iron to heap leaching is impractical. Treatment of the barren solution by an iron
removal circuit is therefore warranted.
The requirement for a final neutralisation circuit is project specific and should usually be unnecessary.
Most of the manganese and magnesium remain in the barren solution after nickel-cobalt precipitation.
When it is necessary for any of the barren solution to be discarded, environmental regulations will
probably stipulate removal of aqueous manganese, necessitating the inclusion of final neutralisation for
manganese removal. In circumstances where the solution is recycled within the process, magnesium
and manganese will accumulate in the circuit until soluble losses in spent ore moisture and partial
neutralisation filter cake balance the inputs. As these species are essentially “inerts” in MSP, it is
unlikely that the equilibrium concentrations will reach any level that will be of concern.

Chemistry
Iron Removal: Quantitative iron removal is not necessary. As any residual iron is present in barren
solution as Fe(II), air/oxidant injection, heat and residence time are required to achieve substantial
oxidation to Fe(III). Iron, as Fe(III), can be removed from barren solution to residual concentrations of
<500 mg/L at pH 2.0-2.5. Gypsum is precipitated as a product of the acid neutralisation reaction.
Final Neutralisation: A residual manganese concentration of <100 mg/L can be achieved by adjusting
the solution pH to 8.5-9.0, precipitating manganese hydroxide. If a lower residual concentration is
required, oxidation by air injection to form manganese dioxide may be included. Oxygen utilisation of
10-20% is achieved. A residual concentration of about 10 mg/L is achievable through this approach.
Separation of the precipitates by thickening or filtration produces a satisfactory recycle water stream.

Process Description
Iron Removal: Excess acid is neutralised by limestone addition to pH 2.0-2.5, precipitating gypsum. Air
is injected to (i) oxidise Fe(II) to Fe(III), and (ii) sweep the carbon dioxide produced by the limestone
reaction from solution, preventing bicarbonate buffering. A supplementary oxidant may be required. To
provide residence time for Fe(II) oxidation, 3 or 4 tanks in series are probably required, operating at 80-
90°C, with between 120 and 180 minutes combined residence time. The discharge slurry is thickened
and the thickener overflow is recycled to heap leaching and other process users if desired, or forwarded
to final neutralisation. Depending on the project requirements, the thickener underflow may be

13
disposed of as a slurry or dewatered to produce a solid waste product. Thickener underflow may be
recycled as seed to improve settling and filtration properties.
Final Neutralisation: Excess acid is neutralised by limestone addition to pH 4.5-5.5, precipitating
gypsum. Air is injected to (i) sweep the carbon dioxide produced by the limestone reaction from
solution, preventing bicarbonate buffering, and (ii) oxidise manganese, if required. The solution is then
further adjusted to pH 8.5-9.0 by the addition of hydrated lime slurry. Typically 3 or 4 tanks in series are
used, operating at 50-60°C, with between 60 and 120 minutes combined residence time. The
discharge slurry is thickened and the thickener overflow is recycled to heap leaching and other process
users if desired. Depending on the project requirements, the thickener underflow may be disposed of
as a slurry or dewatered to produce a solid waste product. Thickener underflow may be recycled as
seed to improve settling and filtration properties.

2.2.6. Product Quality and Downstream Processing Alternatives

The mixed sulphide product generally contains >55% nickel (dry basis). There are no significant
impurity metals apart from co-precipitated zinc and copper. The product de-waters well and moisture
levels of <15% are typical. Approximately 2 wet tonnes of product must be shipped to transport one
tonne of contained nickel.
Table 2-2 summarises typical composition data for MSP product.

Table 2-2: Typical MSP Product Composition

Component Unit Value
Nickel wt% (dry) 55 - 61
Cobalt wt% (dry) 3-6
Zinc wt% (dry) 2-6
Copper wt% (dry) 1-5
Manganese wt% (dry) < 0.1
Magnesium wt% (dry) < 0.1
Iron wt% (dry) < 0.8
Aluminium wt% (dry) < 0.1
Sulphur wt% (dry) 34 - 36
Moisture wt% 10 - 15

To achieve quantitative recovery of nickel and cobalt, a pressure oxidation (POX) autoclave is required
for re-leaching of the MSP product. Applicable refining flowsheets include:
• POX, cobalt SX, hydrogen reduction.
• POX, cobalt SX, nickel hydroxide precipitation / anolyte re-leach, electrowinning.
The MSP product can also be treated similarly to a sulphide concentrate as a smelter feed.

2.2.7. Location and Infrastructure Considerations

The flowsheet for precipitation of nickel and cobalt as a mixed sulphide involves a higher degree of
complexity and sophistication. Parts of the process feature pressurised reactor vessels, redox
chemistry and gas-liquid equilibria. A number of environmental and OH&S concerns exist due to the
use of pressurised reactors and toxic and flammable gases.
The sulphide precipitation reactions require process heat input. This can be sourced as waste heat
energy from a sulphuric acid plant. Sources of a hydrocarbon and sulphur for hydrogen sulphide
production must be identified. Where a sulphuric acid plant is installed, the sulphur supply can be
shared. Alternatively a readily available, low cost supply of sodium hydrosulphide or sodium sulphide
may be substituted for hydrogen sulphide. As MSP is highly selective for nickel and cobalt, high salinity
waters can be tolerated to some extent.

14
2.2.8. Summary of Factors Favouring Selection of MSP
Selection of the MSP flowsheet is favoured where several of the following factors prevail:
• ore to be treated has a low nickel grade, low Ni:Mn ratio and/or high iron or aluminium content,
most limonites are well suited (high Fe), NB: the flowsheet is good for all laterite ores;
• distant product market (lower transport costs than MHP product);
• established environmental benchmarks exist;
• a low cost hydrocarbon is readily available;
• the local workforce is reasonably well educated;
• the project will include a sulphuric acid plant (synergistic with process plant sulphur and energy
requirements);
• there is no readily available magnesia, caustic soda or lime for MHP;
• raw water quality is poor.

3. CONCEPTUAL HYBRID FLOWSHEETS

For the purposes of this paper, conceptual flowsheets that combine alternative technologies with some
of the process steps used in the established flowsheets are defined as hybrid flowsheets. These
technologies offer opportunities to improve metal recovery and intermediate product quality, and to
obtain by-product credits for impurities previously disposed of as waste.

3.1. NICKEL AND COBALT RECOVERY BY MOLECULAR RECOGNITION TECHNOLOGY (MRT)

3.1.1. Overview
An MRT SuperLig® product is available (3) that selectively loads nickel and cobalt at an acid
concentration of approximately pH 1. The nickel loaded can be preferentially eluted using a 5M
sulphuric acid solution, producing an acidic nickel sulphate solution. Cobalt (when the SuperLig®-
cobalt complex is oxidized to Co(III) via Fe(III) or another oxidant) does not elute with the nickel, and
must be eluted using hot sulphur dioxide and 2-3M sulphuric acid, producing an acidic cobalt sulphate
solution.
By adding concentrated sulphuric acid to the nickel sulphate eluate to approach sulphate saturation,
nickel sulphate can be crystallised and recovered by centrifuging, yielding a high purity product. The
mother liquor, containing about 40% sulphuric acid, can be recycled to heap leaching. Cobalt could be
recovered in a similar manner from the cobalt sulphate eluate, or precipitated as a cobalt sulphide,
cobalt carbonate or cobalt hydroxide.

3.1.2. Process and Chemistry

The flowsheet steps, as depicted by Figure 3-1, are:
• Partial Neutralisation
• MRT (Nickel and Cobalt Recovery)
• Nickel Sulphate Hexahydrate (NiSO4.6H2O) Crystallisation
• Cobalt Recovery
• Iron Removal

15
 ORE

SULPHURIC
ACID MAKE-UP

HEAP LEACH

PLS

FILTRATE

WASH
LIMESTONE SOLUTION
<2.0 pH

PARTIAL SOLIDS FILTRATION OR

AIR
NEUTRALISATION WASH CCD

SOLUTION SOLIDS TO
~1 pH DISPOSAL

LIMESTONE

AIR

SOLUTION IRON RAFFINATE Ni / Co

WASH
3.0 pH REMOVAL ~1 pH LOADING

RINSE
SOLIDS TO
DISPOSAL

Ni Co 2-3 M H2SO4
5M H2SO4
ELUTION ELUTION SO2

MRT

SOLUTION
NiSO4 / H2SO4 COBALT
RECOVERY

SULPHURIC ACID SOLUTION

CRYSTALLISATION
ACID

NICKEL SULPHATE
HEXAHYDRATE CRYSTALS

Figure 3-1: Nickel and Cobalt Recovery by MRT

16
In partial neutralisation, the acidity of the PLS is adjusted by limestone slurry addition to approximately
pH 1, precipitating gypsum as an acid neutralisation reaction product. Negligible nickel or cobalt co-
precipitation occurs under these conditions. The partial neutralisation discharge slurry is thickened and
soluble nickel and cobalt are recovered either by counter-current decantation (CCD) washing (1-2
stages) or counter-current washing on a belt filter. The washed solids are disposed of, either as a
slurry or as a filter cake. The overflow solution from the partial neutralisation thickener is directed to the
MRT circuit.
Nickel and cobalt in solution are quantitatively loaded by the MRT columns. The loading cycle is
followed by a pre-elution wash using weak acid solution. The nickel is then eluted as nickel sulphate
using 5M sulphuric acid. Finally the MRT columns receive a post-elution wash and the cycle re-
commences. Cobalt does not strip with the nickel and is permitted to concentrate up. Periodically the
cobalt is eluted using sulphur dioxide and 2-3M sulphuric acid.
The sulphate concentration of the nickel sulphate eluate is adjusted by the addition of concentrated
sulphuric acid, crystallising high purity nickel sulphate hexahydrate, which is recovered by centrifuging.
The mother liquor, containing about 40% sulphuric acid (~540 g/L) and some nickel sulphate, is
recycled to heap leaching. Consequently, a recirculating load of nickel will be established.
Cobalt may be recovered in much the same way as nickel. However, as the cobalt stream is much
smaller, flexibility exists to precipitate cobalt sulphide, cobalt carbonate or cobalt hydroxide.
The raffinate (spent solution) from the MRT process contains iron, chromium, aluminium, manganese,
magnesium and other elements. If the spent solution is recycled to the heap leach as make-up water,
these species will accumulate in the circuit until soluble losses in spent ore moisture and partial
neutralisation filter cake balance the inputs. The majority of these species will not reach significant
equilibrium concentrations. However, as the iron concentration in PLS is high, an iron removal step is
required. The acidity of the raffinate stream is adjusted by limestone slurry addition to pH 2.5-3.0
precipitating gypsum and most of the iron. Air is injected to oxidise any Fe(II) to Fe(III). If desired,
aluminium may also be removed by further adjustment to approximately pH 4.5.
The iron removal discharge slurry is thickened and the solids are disposed of, either as a slurry or as a
filter cake. No washing is required. The overflow solution from the iron removal thickener is recycled to
the heap leach and process plant.

3.1.3. Discussion
The following table summarises the key advantages and disadvantages of this flowsheet.

Table 3-1: Advantages and Disadvantages of Nickel / Cobalt MRT Flowsheet

Advantages Disadvantages
Potential to supply a large proportion of heap leach acid Low nickel and cobalt concentrations in feed stream
via nickel elution and crystallisation circuit impact on size of MRT circuit
Entire circuit is at pH 3.0 or below - no full neutralisation Exotic materials of construction in crystallisation
of acid required circuit
Simplified recovery circuit
Negligible nickel and cobalt losses
Low sensitivity to iron, aluminium and manganese
Neutralisation of PLS only to ~1 pH required
Very high quality nickel and cobalt products

The economics of this flowsheet relative to the established options discussed in this paper have not
been established. Laboratory and/or pilot testwork and a preliminary project evaluation to establish
order of magnitude capital and operating costs are required.

17
3.2. MIXED SULPHIDE PRECIPITATION WITH IRON REMOVAL BY MOLECULAR
RECOGNITION TECHNOLOGY (MRT)

3.2.1. Overview
Although MSP selectively precipitates nickel and cobalt over iron, the iron concentration in heap leach
PLS is generally sufficiently high that (a) some iron reports to the mixed sulphide product and (b) some
Fe(III) reduces to Fe(II), consuming hydrogen sulphide and precipitating elemental sulphur.
An MRT product is available (3) that selectively loads Fe(III) over nickel and cobalt over a range of acid
concentrations from 2M sulphuric acid to pH 2.5. The iron loaded resin can subsequently be eluted
using a reductive strip, producing an acidic ferrous sulphate solution. By adding concentrated sulphuric
acid to this solution to approach sulphate saturation, ferrous sulphate can be crystallised and recovered
by centrifuging, yielding a saleable by-product. The mother liquor, containing about 40% sulphuric acid,
can be recycled to heap leaching.
Nickel and cobalt can be precipitated from the MRT raffinate by MSP.

3.2.2. Process and Chemistry

The flowsheet steps, as depicted by Figure 3-2, are:
• Partial Neutralisation
• MRT (Iron Removal)
• Ferrous Sulphate Monohydrate (FeSO4.H2O) Crystallisation
• Mixed Sulphide Precipitation

In partial neutralisation, the acidity of the PLS is adjusted by limestone slurry addition. Air is injected to
oxidise any Fe(II) to Fe(III). The flowsheet provides flexibility to tailor the size of the MRT circuit to suit
project economics. If the solution acidity is adjusted to approximately pH 1.8, all of the contained iron
can be forwarded to MRT. Alternatively, the pH can be adjusted between pH 2 and 2.5 to partially
precipitate iron to varying extents, downsizing the MRT circuit. The partial neutralisation pH can
therefore be selected to optimise project economics, based on the extent of nickel and cobalt co-
precipitation, heap leach circuit acid make-up, reduced limestone consumption, and by-product (ferrous
sulphate) credits versus the MRT circuit costs.
The partial neutralisation discharge slurry is thickened and soluble nickel and cobalt are recovered
either by counter-current decantation (CCD) washing (1-2 stages) or counter-current washing on a belt
filter. The washed solids are disposed of, either as a slurry or as a filter cake. The overflow solution
from the partial neutralisation thickener is directed to the MRT circuit.
Any remaining iron is loaded by the MRT columns. The loading cycle is followed by a pre-elution wash
using weak acid solution. The iron is then eluted as Fe(II) by a heated reductive strip using 2M
sulphuric acid and sulphur dioxide or another reductant such as Cu(I). Finally the MRT columns
receive a post-elution wash and the cycle re-commences.
The sulphate concentration of the eluate is adjusted by the addition of concentrated sulphuric acid,
crystallising ferrous sulphate monohydrate, which is recovered by centrifuging. The mother liquor,
containing about 40% sulphuric acid (~540 g/L) and some ferrous sulphate, is recycled to heap
leaching. A recirculating load of Fe(II) will be established. Depending on the final Fe(II) concentration
in the mother liquor stream, it may be necessary for a bleed to a secondary iron removal step.
The raffinate from the MRT process is directed to the MSP circuit. If the feed pH is below 2, the
addition of a small quantity of magnesia slurry may be required to control the terminal pH and maximise
nickel and cobalt precipitation.

18
 ORE

SULPHURIC
ACID MAKE-UP

HEAP LEACH

PLS

FILTRATE

WASH
LIMESTONE SOLUTION
~2.5 pH

PARTIAL SOLIDS FILTRATION OR

AIR
NEUTRALISATION WASH CCD

SOLIDS TO
DISPOSAL
SOLUTION
2M Acid to 2.5 pH

H2S

SOLUTION MIXED SULPHIDE RAFFINATE Fe (III)

WASH
~2 pH PRECIPITATION ~2.5 pH LOADING

SULPHURIC
ACID
RINSE ELUTION
SO2

MRT
SOLIDS

SOLUTION
FeSO4 / H2SO4

MIXED
SULPHIDE
PRODUCT ACID
SULPHURIC SOLUTION
CRYSTALLISATION
ACID

FERROUS
SULPHATE
MONOHYDRATE
CRYSTALS

Figure 3-2: Mixed Sulphide Precipitation with Iron Removal by MRT

19
3.2.3. Discussion
The following table summarises the key advantages and disadvantages of this flowsheet.

Table 3-2: Advantages and Disadvantages of the MSP / Iron MRT Flowsheet

Advantages Disadvantages
Very low nickel and cobalt losses (0 - 0.5%) possible Relatively low iron concentration in feed stream
depending on partial neutralisation pH impacts on size of MRT circuit
Size of MRT circuit can be tailored to optimise project Secondary iron removal from crystallisation mother
economics liquor may be required
Potential to supply ALL heap leach acid via iron elution Exotic materials of construction in crystallisation
and crystallisation circuit circuit
Low sensitivity to aluminium and manganese
Higher purity mixed sulphide product
Saleable ferrous sulphate by-product
Entire circuit is at pH 2.5 or below, no full neutralisation
of acid required

The economics of this flowsheet relative to the established options discussed in this paper have not
been established. Laboratory and/or pilot testwork and a preliminary project evaluation to establish
order of magnitude capital and operating costs are required.

3.3. MIXED SULPHIDE PRECIPITATION WITH IRON REMOVAL BY ION EXCHANGE (IX)

3.3.1. Overview
Although MSP selectively precipitates nickel and cobalt over iron, the iron concentration in heap leach
PLS is generally sufficiently high that (a) some iron reports to the mixed sulphide product, (b) some
Fe(III) reduces to Fe(II), consuming hydrogen sulphide and precipitating elemental sulphur. In addition,
any copper in the PLS will report to the mixed sulphide product.
An ion exchange resin is available (4) that selectively loads Fe(III) and Cu(II) over nickel and cobalt
over a range of acid concentrations up to pH 2.5. It is understood that copper can be preferentially
eluted before iron using 1M sulphuric acid solution. The iron loaded can subsequently be eluted using
a reductive strip, producing an acidic ferrous sulphate solution. By adding concentrated sulphuric acid
to this solution to approach sulphate saturation, ferrous sulphate can be crystallised and recovered by
centrifuging, yielding a saleable by-product. The mother liquor, containing about 40% sulphuric acid,
can be recycled to heap leaching.
Nickel and cobalt can be precipitated from the ion exchange raffinate by MSP.

3.3.2. Process and Chemistry

The flowsheet steps, as depicted by Figure 3-3, are:
• Partial Neutralisation
• Ion Exchange (Iron Removal)
• Copper Recovery (optional)
• Ferrous Sulphate Monohydrate (FeSO4.H2O) Crystallisation
• Mixed Sulphide Precipitation

In partial neutralisation, the acidity of the PLS is adjusted to pH 1.8-2.5 by limestone slurry addition. Air
is injected to oxidise any Fe(II) to Fe(III). The flowsheet provides flexibility to tailor the size of the ion
exchange circuit to suit project economics. If the solution acidity is adjusted to approximately pH 1.8,
most of the contained iron can be forwarded to ion exchange. Alternatively, the pH can be adjusted

20
between pH 1.9 and 2.5 to partially precipitate iron to varying extents, downsizing the ion exchange
circuit. The partial neutralisation pH can therefore be selected to optimise project economics, based on
the extent of nickel and cobalt co-precipitation, heap leach circuit acid make-up, reduced limestone
consumption, and by-product (ferrous sulphate) credits versus the ion exchange circuit costs.

ORE

SULPHURIC
ACID MAKE-UP

HEAP LEACH

PLS

FILTRATE

WASH
LIMESTONE SOLUTION
~2.5 pH

PARTIAL SOLIDS FILTRATION OR

AIR
NEUTRALISATION WASH CCD

<2.5 pH SOLUTION SOLIDS TO

DISPOSAL

RESIN WASH ION EXCHANGE LOADED RESIN

Fe(III) Removal

H2S SOLUTION SO2

SOLUTION MIXED SULPHIDE RESIN ELUTION

1.5-2.0 pH PRECIPITATION (REDUCTIVE STRIP)

SOLIDS SOLUTION
FeSO4 / H2SO4

ACID
SULPHURIC SOLUTION
CRYSTALLISATION
ACID

MIXED FERROUS
SULPHIDE SULPHATE
PRODUCT MONOHYDRATE
CRYSTALS

Figure 3-3: Mixed Sulphide Precipitation with Iron Removal by Ion Exchange

21
The partial neutralisation discharge slurry is thickened and soluble nickel and cobalt are recovered
either by counter-current decantation (CCD) washing (1-2 stages) or counter-current washing on a belt
filter. The washed solids are disposed of, either as a slurry or as a filter cake. The overflow solution
from the partial neutralisation thickener is directed to the ion exchange columns.
Any remaining iron is loaded by the ion exchange resin. After rinsing, copper may be eluted separately,
if desired, using 1M sulphuric acid solution. The iron is then eluted as Fe(II) by a reductive strip using
sulphur dioxide and 2M sulphuric acid.
The sulphate concentration of the ferrous sulphate eluate is adjusted by the addition of concentrated
sulphuric acid, crystallising ferrous sulphate monohydrate, which is recovered by centrifuging. The
mother liquor, containing about 40% sulphuric acid (~540 g/L) and some ferrous sulphate, is recycled to
heap leaching. A recirculating load of Fe(II) will be established. Depending on the final Fe(II)
concentration in the mother liquor stream, it may be necessary for a bleed to the partial neutralisation
circuit.
The raffinate from the ion exchange columns is directed to the MSP circuit. If the feed pH is <2, the
addition of a small quantity of magnesia slurry may be required to control the terminal pH and maximise
nickel and cobalt precipitation.

3.3.3. Discussion
The following table summarises the key advantages and disadvantages of this flowsheet.

Table 3-3: Advantages and Disadvantages of the MSP / Iron IX Flowsheet

Advantages Disadvantages
Very low nickel and cobalt losses (0 - 0.5%) possible Relatively low iron concentration in feed stream
depending on partial neutralisation pH impacts on size of ion exchange circuit
Size of ion exchange circuit can be tailored to optimise Exotic materials of construction in crystallisation
project economics by modifying partial neutralisation pH circuit
Potential to supply ALL heap leach acid via iron elution
and crystallisation circuit
Low sensitivity to aluminium and manganese
Saleable iron (and possibly copper) by-products
Higher purity mixed sulphide product
Combination of proven and established processes
Entire circuit is at pH 2.5 or below, no full neutralisation
of acid required

The economics of this flowsheet relative to the established options discussed in this paper have not
been established. Laboratory and/or pilot testwork and a preliminary project evaluation to establish
order of magnitude capital and operating costs are required.

3.4. MIXED SULPHIDE PRECIPITATION WITH IRON REMOVAL BY RESIN-IN-PULP (RIP)

3.4.1. Overview
Although MSP selectively precipitates nickel and cobalt over iron, the iron concentration in heap leach
PLS is generally sufficiently high that (a) some iron reports to the mixed sulphide product, (b) some
Fe(III) reduces to Fe(II), consuming hydrogen sulphide and precipitating elemental sulphur. In addition,
any copper in the PLS will report to the mixed sulphide product.
A resin suitable for RIP is available (4) that selectively loads Fe(III) and Cu(II) over nickel and cobalt
over a range of acid concentrations up to pH 2.5. It is understood that copper can be preferentially
eluted before iron using 1M sulphuric acid solution. The iron loaded can subsequently be eluted using
a reductive strip, producing an acidic ferrous sulphate solution. By adding concentrated sulphuric acid
to this solution to approach sulphate saturation, ferrous sulphate can be crystallised and recovered by

22
centrifuging, yielding a saleable by-product. The mother liquor, containing about 40% sulphuric acid,
can be recycled to heap leaching.
Nickel and cobalt can be precipitated from the RIP raffinate by MSP.
3.4.2. Process and Chemistry
The flowsheet steps, as depicted by Figure 3-4, are:
• Partial Neutralisation
• Resin-in-Pulp (Iron Removal)
• Copper Recovery (optional)
• Ferrous Sulphate Monohydrate (FeSO4.H2O) Crystallisation
• Mixed Sulphide Precipitation

In partial neutralisation, the acidity of the PLS is adjusted to pH 1.8-2.5 by limestone slurry addition. Air
is injected to oxidise any Fe(II) to Fe(III). The flowsheet provides flexibility to tailor the size of the RIP
circuit to suit project economics. If the solution acidity is adjusted to approximately pH 1.8, most of the
contained iron can be forwarded to RIP. Alternatively, the pH can be adjusted between 1.9 and 2.5 to
partially precipitate iron to varying extents, downsizing the RIP circuit. The partial neutralisation pH can
therefore be selected to optimise project economics, based on the extent of nickel and cobalt co-
precipitation, heap leach circuit acid make-up, reduced limestone consumption, and by-product (ferrous
sulphate) credits versus the RIP circuit costs. The partial neutralisation discharge slurry is directed to
the RIP circuit.
Any remaining Fe(III), along with Cu(II), is loaded in the RIP circuit. The resin is washed and screened
to separate the spent slurry and recover aqueous nickel and cobalt. After rinsing, copper may be eluted
separately, if desired, using 1M sulphuric acid solution. The iron is then eluted as Fe(II) by a reductive
strip using sulphur dioxide and 2M sulphuric acid. The washed spent slurry is thickened and the solids
are disposed of, either as a slurry or as a filter cake.
The sulphate concentration of the ferrous sulphate eluate is adjusted by the addition of concentrated
sulphuric acid, crystallising ferrous sulphate monohydrate, which is recovered by centrifuging. The
mother liquor, containing about 40% sulphuric acid (~540 g/L) and some ferrous sulphate, is recycled to
heap leaching. A recirculating load of Fe(II) will be established. Depending on the final Fe(II)
concentration in the mother liquor stream, it may be necessary for a bleed to the partial neutralisation
circuit.
The raffinate from the RIP circuit is directed to the MSP circuit. If the feed pH is <2, the addition of a
small quantity of magnesia slurry may be required to control the terminal pH and maximise nickel and
cobalt precipitation.

23
 ORE

SULPHURIC
ACID MAKE-UP

HEAP LEACH

PLS
LIMESTONE

PARTIAL
AIR
NEUTRALISATION

<2.5 pH SOLUTION

RESIN WASH RESIN-IN-PULP LOADED RESIN RESIN WASH

Fe(III) Removal & SCREEN

SOLIDS TO
H2S SOLUTION SO2 DISPOSAL

SOLUTION MIXED SULPHIDE RESIN ELUTION

~2 pH PRECIPITATION (REDUCTIVE STRIP)

SOLUTION
FeSO4 / H2SO4

SOLIDS
ACID
SULPHURIC SOLUTION
CRYSTALLISATION
ACID

MIXED FERROUS
SULPHIDE SULPHATE
PRODUCT MONOHYDRATE
CRYSTALS

Figure 3-4: Mixed Sulphide Precipitation with Iron Removal by RIP

24
3.4.3. Discussion
The following table summarises the key advantages and disadvantages of this flowsheet.

Table 3-4: Advantages and Disadvantages of the MSP / Iron RIP Flowsheet

Advantages
Very low nickel and cobalt losses (0 - 0.5%) possible
depending on partial neutralisation pH
Size of RIP circuit can be tailored to optimise project
economics by modifying partial neutralisation pH
Potential to supply ALL heap leach acid via iron elution
and crystallisation circuit
Low sensitivity to aluminium and manganese
Saleable iron (and possibly copper) by-products
Higher purity mixed sulphide product
Entire circuit is at pH 2.5 or below, no full neutralisation
of acid required
Disadvantages
Relatively low iron concentration in feed stream
impacts on size of RIP circuit
RIP circuit is somewhat complex – difficulty handling
counter-current resin and slurry flows
Exotic materials of construction in crystallisation
circuit
Resin losses can be high
Water balance problems due to high resin wash rates

The economics of this flowsheet relative to the established options discussed in this paper have not
been established. Laboratory and/or pilot testwork and a preliminary project evaluation to establish
order of magnitude capital and operating costs are required.

4. COMPARISON OF FLOWSHEET STRENGTHS AND WEAKNESSES

Category MHP MSP Hybrid Options

No selectivity over Fe, Cr, Al, Selective over Fe, Cr, Al, Mn,
Selectivity for Cu, Zn; limited selectivity Mg, Ca, Na; option to Improved selectivity in most
Ni/Co over Mn; selective over Mg, exclude Cu; no selectivity cases
1
Ca, Na over Zn
High Ni grade Low to high Ni grade
Amenable Ore High Ni:Mn ratio High Mn, Fe, Al grades Potential to tailor to any ore
Types Low Fe, Al grades Best choice for limonites type
Good choice for saprolites (high Fe content)
Nickel Up to 10% Ni losses in Negligible Ni losses in
<1% Ni losses in process
Recovery process process
Potential ambient Complete neutralisation of Supply of acid to heap leach
Synergies with
temperature process (e.g. acid not required – recycle via recovery or purification
Heap Leaching
European Nickel) water at 2.0-2.5 pH stages
Other On-site sulphuric acid plant Remote location, low grade
Remote location
Synergies (sulphur and energy) ores
Lower quality product High purity product
Ni 30-39 % Ni 56-61 % Expect to achieve higher
Product Quality Mn 4-9 % S 34-36% quality product than MHP or
Mg 3-5 % Mn, Mg <0.1% MSP flowsheets
35-45% moisture 10-15 % moisture
Recycles Up to 20% of PLS flow Minor Minor
Approx 25,000-30,000 tpa
Unknown at this stage, but
per train based on MSP
Economies of Capacity of up to 60,000 tpa expect large throughout
autoclaves; higher capacity
Scale in a single train capacity possible in a single
for multiple reactors by
train
adding extra units

1
Sumitomo Metal Mining Co Ltd has developed a proprietary method for selective precipitation of zinc sulphide.

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 Category MHP MSP Hybrid Options

Limestone, hydrocarbon for

Limestone, magnesia / hydrogen production, sulphur Vary with flowsheet options,
Major caustic / soda ash, lime. for H2S production. but fewer reagents required
Reagents
* Relatively inexpensive * Expensive / oil price than MHP or MSP
dependency
LP steam used by sulphide
Energy No significant heat inputs to Expect lower heat demand
precipitation circuit; energy
Demand process. than MSP
demand for H2S production
No exotics, pH >4 after first Exotic materials required,
Materials of stage iron removal, generally max pH ~3.5, dissolved H2S, Exotic materials required in
Construction rubber lined carbon steel Alloy 31 / Hastelloy around crystallisation circuits
and/or 316 stainless steel sulphide precipitation
Relatively simple,
Gas-liquid reaction systems,
Atmospheric tanks, pH atmospheric tanks, pH
pressurised reactor vessels,
Complexity control, simple precipitation control, adsorption / elution
gas scrubbing, hydrogen and
chemistry chemistry, established
H2S plant technology
crystallisation technology
Alkaline reagents, hot Alkaline reagents,
Alkaline reagents, slurries, pressurised process
OH&S hot slurries,
hot slurries, equipment, flammable gases,
Concerns strong acid solutions,
nickel salts toxic gases, sulphur, nickel
salts, pyrophoric product nickel salts
Shipping Approx 4.5 tonnes per tonne Approx 2 tonnes per tonne
Various
Quantity nickel nickel
Downstream Atmospheric or low pressure POX re-leach of product, or Various, opportunities to
Refining re-leach of product can be fed to a smelter tailor process to suit refinery

5. ACKNOWLEDGEMENTS

The author wishes to thank Stuart Bradbury of Process Plant Technology (Pty) Ltd for advice on
crystallisation technology, Neil Izatt of IBC Advanced Technologies, Inc. for technical advice on MRT
products, and Duilio Rossoni of Lanxess Deutschland GmbH for technical advice on ion exchange and
resin-in-pulp.
The author would also like to thank Aker Kvaerner Australia’s clients for the opportunity to contribute to
and learn from several interesting nickel laterite heap leach studies, and the management of Aker
Kvaerner Australia for permission to present this paper.

6. REFERENCES

1. M.C. Jha, G.A. Meyer, and G.R. Wicker, AMAX Extractive Research & Development, Inc., “An
Improved Process for Precipitating Nickel Sulfide From Acidic Laterite Leach Liquors”, Journal of
Metals, November 1981.
2. R.R. Matos, General Nickel Co., “Industrial Experience with the Ni/Co Sulphides Precipitation
Process”, Nickel-Cobalt 97 International Symposium, Proceedings of the 27th Annual
Hydrometallurgical Meeting of CIM, Sudbury, Ontario, Canada, August 1997.
3. S.R. Izatt, J.B. Dale, N.E. Izatt, and R.L. Bruening, IBC Advanced Technologies, Inc., “Recent
Advances in the Application of MRT to Nickel and Cobalt Separations from Primary and Secondary
Process Streams”, Proceedings of ALTA 2006 Nickel/Cobalt Conference, ALTA Metallurgical
Services, Perth, Australia, May 2006.
4. O. Halle and D. Rossoni, “A New (Monodisperse) Chelating Resin Designed for Mining Application:
Lewatit® Monoplus TP 207”, Proceedings of ALTA 2005 Nickel/Cobalt Conference, ALTA
Metallurgical Services, Perth, Australia, May 2005.

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