THE RECOVERY OF NICKEL

FROM PAL DISCHARGE LIQUORS

By
Peter Dickson,
Kvaerner E&C
 THE RECOVERY OF NICKEL
FROM PAL DISCHARGE LIQUORS

By
Peter Dickson
Kvaerner E&C

Table of Contents

1. INTRODUCTION 1

2. ECONOMIC CRITERIA 2

3. SULPHIDE PRECIPITATION 3

4. HYDROXIDE PRECIPITATION 6

5. DIRECT SOLVENT EXTRACTION 9

6. CONCLUSION 12

7. ACKNOWLEDGEMENTS 13

ABSTRACT

As a guide for new projects, the methods for recovery nickel from pressure acid leach
(PAL) discharge liquors are described and reviewed. The methods are grouped into
three generic processing routes; sulphide precipitation, hydroxide precipitation and direct
solvent extraction. The processes are reviewed individually with respect to their inherent
strengths, weaknesses and their potential for improvements. The processes are
assessed in terms of their sensitivity to ore type, the refining approach, capacity
restrictions and occupational health and safety issues.

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 1. INTRODUCTION

When contemplating PAL processing, the question is often asked, “Which is the best way
to convert the PAL slurry discharge to final product?” In answer to this question, there
are three generic processing routes available to a project; sulphide precipitation,
hydroxide precipitation and direct solvent extraction.
• Sulphide precipitation involves the very selective precipitation of a mixed metal
sulphide from the counter current decantation (CCD) overflow liquor with hydrogen
sulphide. The mixed sulphide is then re-leached under oxidising conditions, any
remaining iron removed, the zinc, copper and cobalt selectively removed and
processed to a cobalt product. Under current proposals, the high purity nickel
raffinate is processed by either hydrogen reduction or electrowinning to produce the
final nickel product.
• Hydroxide precipitation requires the precipitation of the majority of the iron, aluminium
and chromium from the counter current decantation overflow liquor by neutralisation
of the solution with limestone. The low iron liquor is then neutralised by further
alkaline addition (magnesia or lime), precipitating the nickel and cobalt over the
manganese as selectively as is possible. This nickel/cobalt hydroxide is then
selectively leached into an ammoniacal solution and the nickel product generated by
solvent extraction and electrowinning. Either sulphiding or hydrolysis is employed to
precipitate the cobalt from the raffinate. The resultant solids must then be further
refined (on or off-site) to a suitable cobalt product.
• Direct solvent extraction requires the majority of the iron, aluminium and chromium to
be precipitated from the counter current decantation overflow liquor by neutralisation
of the solution with limestone and lime. The remaining metals, excluding nickel and
half the magnesium are extracted from this low iron liquor by solvent extraction,
stripped into an acidic sulphate solution and precipitated as an impure cobalt
sulphide. The resultant solids must then be further refined (on or off-site) to a suitable
cobalt product. The nickel product is then generated from this raffinate by solvent
extraction and electrowinning.

All three generic routes start with a pre-CCD acid kill stage, often referred to as primary
neutralisation. This is always followed by a standard CCD stage to produce a medium
acidity clarified PLS liquor. The reviews and flowsheets presented in this paper primarily
deal with how these clarified PLS liquors are treated to produce nickel and cobalt
products.
The assessment of the process options is not so much a matter of direct comparison as a
review highlighting the inherent strengths, weaknesses and potential for improvement of
each process. To maintain the generality, even qualitative comparisons are avoided for a
significant advantage at one site may only be of minor interest at another. The opinions
presented here are based upon experience, testwork trends, theoretical chemistry and
are, by the nature of the paper, general and approximate.
The criteria used for any project to select the recovery process will include the ore
characteristics, refining and product marketing strategy, environmental and occupational
health concerns, by-product credits and site specific cost elements. Where significant,
these issues have been addressed in the following sections.

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 2. ECONOMIC CRITERIA

Numerous studies have been performed comparing the three generic processing routes
in a number of different guises. These studies have generated capital and operating
costs and, for each study in isolation, a preferred processing route for that particular
project. However, when these studies are looked at together, the recommended
processing route is project specific and none of the routes have at this stage shown
themselves to have inherently superior economics.

2.1 CAPITAL COST

The project sensitivity to the capital cost of the process route selected is typically dwarfed
by the capital requirements of the pressure acid leaching portion of the plant and the
infrastructure requirements of the project.
The capital cost is obviously reduced if the final cobalt product is an impure sulphide
rather than a purified metal or chemical product, but the revenue from this resource is
also reduced.

2.2 OPERATING COST

The operating cost is more sensitive to the process route selection than the capital cost,
depending chiefly on the supply cost of reagents such as power, natural gas, limestone,
magnesia and ammonia.
The by-product credit available for ammonium sulphate production is a unique sensitivity
for the sulphide precipitation route.

2.3 REVENUE
The revenue obtained by a project, for any given production rate, is chiefly dictated by the
purity and form of the nickel and cobalt products produced. These aspects are
significantly affected by the choice of the metal production processes and the marketing
strategy adopted.
The nickel production processes can produce nickel metal as cathode (cut or uncut),
nickel oxide powder or a combination of powder and briquettes. While all processes are
capable of producing to the LME Primary Nickel specification (ASTM B39-79 reapproved
1993), each process has a tendency towards higher impurities levels with some elements
and lower with other elements. This tendency is most pronounced in the choice of final
nickel metal production, electrowinning versus hydrogen reduction. For example, lead
has a tendency to be high for electrowinning, while carbon, sulphur and oxygen tend to
be high for hydrogen reduction.
Cobalt can be produced as a chemical (sulphate salt or oxide hydroxide), metal cathode
(broken or rounds/crowns) or as combination of metal powder and briquettes. More
pronounced than with nickel, the process route selection will alter the cobalt quality
produced as well as the form.

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 3. SULPHIDE PRECIPITATION

This route is similar to the combination operating at the Moa Bay, Cuba and Fort
Saskatchewan, Canada plants. The processing route has also been adopted by
Anaconda and is proposed by Comet, Philnico, Black Range Minerals, Weda Bay,
Mindoro, Moneo and Mighty Beaut. Freeport originally developed this route in the 1950’s
and the sulphide precipitation portion of the recovery process has been in operation for
40 years at Moa Bay. Dynatec, (formerly Sherritt), generally favour this route due to their
knowledge of Moa Bay and the similarities to their Fort Saskatchewan sulphide refinery.
The detractors of this processing route will point to the toxicity of hydrogen sulphide as its
drawback. The other installed PAL processing routes use some form of sulphiding
reagent (sodium sulphide or hydrosulphide), but at a tenth of the rate. More importantly,
because of the different sulphiding form, the other routes would only have the potential to
generate hydrogen sulphide gas at less than one hundredth of the rate possible from the
sulphide precipitation route. Recent incidents have added to this concern, however,
hydrogen sulphide is and has been produced at nickel processing facilities for decades
with only minor incidents, until recently.

Barren Liquor
M
Neutralisation
Sulphide Precipitation M M

Impurity
M Removal
Sulphide Leach

Ni/Co Hydrogen Reduction

(NH4)2SO4
Plant

Nickel Briquettes Cobalt Powder

Figure 3.1 Sulphide Precipitation Flowsheet

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3.1 ORE SENSITIVITIES
The sulphide processing route is relatively insensitive to nickel feed tenor and thus
performs well on low grade nickel ores with poor CCD washing characteristics still
operating at over 99% precipitation. It is sensitive to copper as a potential cobalt
contaminant. It is insensitive to zinc levels, potentially recovering zinc as a by-product
and is also insensitive to iron, aluminium and chromium levels as these are not required
to be removed from nickel/cobalt bearing solutions, eliminating co-precipitation losses
and recycles.
The route has a synergistic relationship with reducing ores where the oxygen used
leaching the sulphides, can also be employed to adjust PAL conditions to maintain
oxidising conditions in the leach. The oxygen supply gives low iron solution tenors and
minimises acid consumption while also minimising the effect upon the steam
consumption.
It has the potential to provide the best scenario for the recovery of scandium from the
leach liquors by the neutralisation of barren liquor after nickel/cobalt removal. The
resultant hydroxide precipitate would contain iron, aluminium, chromium and scandium
and would require further purification.

3.2 REFINING
The most commonly quoted advantage of this route is its ability to produce the best
intermediate product for storage and shipment, and the existence of facilities for further
treatment of this intermediate product. Associated with this advantage is the ability of the
refinery section to accept other sulphides produced from similar plants. It may also be
possible to toll refine sulphides and high grade concentrates from other processing routes
with further development and modification of the generic processing route.
Of specific interest in the refining area is the ability to efficiently toll refine cobalt
sulphides produced by any of the processing routes in parallel to the existing mixed
sulphide refining plant providing a flexible cobalt refining facility. The cobalt can be
produced (by design or retrofit) as sulphate crystals, cathode or a combination of powder
and briquettes.
Being an intrinsic part of the nickel refinery, this cobalt refinery is the most capital
efficient, but all of the processes would benefit from a centralised cobalt toll refinery. A
centralised toll refiner could provide the economies of scale for capital and operating cost
reductions and a greater marketing penetration of the product.

3.3 CAPACITY
The processing route takes maximum advantage of economies of scale with a significant
concentration of the nickel and cobalt in the refinery. This allows significant throughputs
to be accommodated through the refinery, with the equipment remaining relatively small.
The most significant jump in capital cost is required when the sulphide precipitation area
requires two trains to operate. Unfortunately the nickel throughput is difficult to determine
due to its dependence on ore properties, the selection of precipitation conditions and the
descaling philosophy adopted.
In one case, a Moa Bay autoclave approach (120°C, 10 bar), a second train was required
around 30,000 tpa nickel. In another case, the AMAX multiple reactor vessel approach
(less than 100°C, 2 bar), significantly higher nickel throughputs were accommodated
without a quantum jump in capital cost by gradually increasing the size and number of
vessels in series.

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3.4 ENVIRONMENTAL/OCCUPATIONAL HEALTH & SAFETY ISSUES
This process requires the most technologically sophisticated work force. It has the most
poisonous and flammable chemicals and operates the hottest and most consistently
acidic circuit after the PAL area. These issues are handled in other industries, but are not
commonly combined together, especially in the metallurgical industry. Together, they
should be viewed as a risk demanding a highly trained and skilled work force.
Both metal production methods have occupational health and safety drawbacks.
Electrowinning has its nickel salt aerosol problems, (minimised with anode bags
technology), and material handling difficulties. Hydrogen reduction involves significant
class 1 zone 1 hazardous areas.

3.5 OTHER
Associated with the route’s technological complexity is its requirement for the most
demanding materials of construction. Equipment is required to withstand under elevated
temperatures and pressures; highly acidic solutions, highly variable Emf solutions,
nascent hydrogen, metallic scale and highly errosive particles, to name the more
demanding applications.
A multiple effect ammonium sulphate plant integrates well with the more energy efficient
sulphuric acid plant designs (HRS, HEROS and Monarch) in its ability to consume large
quantities of low pressure steam. Unfortunately, even with this integration, mechanical
vapour recompression crystallisers are often lower in capital and operating costs.
This is the only route compatible with nickel (and cobalt) production by hydrogen
reduction. As such, in areas of natural gas supply and a market for ammonium sulphate
fertiliser there is a compelling economic argument for this process route. While this
technology is not considered commonplace, it is more established than anode bag
electrowinning. However, both technologies are available through engineering
contractors with low process technology fees and unrestricted by exclusivity agreements.
The electrowinning approach has obvious advantages on projects with access to the
electrical grid, but requires a further relatively unproved element to the processing route
and added occupational health issues associated with soluble nickel aerosols.

3.6 FUTURE IMPROVEMENTS

While no of quantum improvements in the chemical process are expected, each step is
capable of significant optimisation. The sulphide precipitation step requires optimisation
of the low temperature (AMAX) reaction conditions and seed system. The sulphide leach
requires optimisation of oxygen leaching with waste heat recovery and possibly a two
stage counter current leach to minimise the oxygen usage. Solvent extraction could
benefit from some rearrangement of stages and possibly from liquid-liquid extraction
columns. Hydrogen reduction could benefit from higher nickel tenors, lower ammonium
sulphate levels and even continuous ammonia addition.
Alternative destinations for the sulphur would probably be the most dramatic change to
this circuit and this is being examined in some of the electrowinning proposals for this
processing route.

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 4. HYDROXIDE PRECIPITATION

This processing route has been adopted by Centaur and is proposed by Preston
(Marlborough), Highlands, Argosy and possibly a Comet-Billiton joint venture. The
groundwork was laid for this process by QNI in its ASX development in the late 1980’s.
The flowsheet concept was introduced by some proactive sales work by Murdoch
Mackenzie of Henkel and this development carried on by Centaur.
The detractors of this processing route will point to the lack of selectivity of the
precipitation and the handling difficulties with the magnesia used for neutralisation. The
lack of selectivity does lead to significant internal recycles within the processing facility,
but it is coupled with a highly selective leach and solvent extraction, so the quality of the
product is not compromised.

M M M M

Nickel/Cobalt
Precipitation
M M M M
Iron/Chromium/Aluminium
Removal

Hydroxide Leach
M M

M M

Nickel Co Sulphide
SX/EW Precipitation

Nickel Cathode Cobalt Sulphide Cake

Figure 4.1 Hydroxide Precipitation Flowsheet

6
4.1 ORE SENSITIVITIES
The hydroxide precipitation processing route prefers high nickel feed tenors to maximise
recoveries. More critical to the efficiency of this process is the nickel to manganese ratio
to minimise recycles. A high ratio can substantially decrease manganese recycles,
decreasing operating costs and increasing nickel and cobalt recoveries.
The process is sensitive to aluminium, lowering the ammonia leach nickel recoveries and
increasing recycles if it is not adequately controlled in the iron removal steps. Due to this
sensitivity, there are possible advantages in performing the PAL in saline water to help
suppress the aluminium levels in solution by encouraging the precipitation of alunite.
It is insensitive to copper, assuming that a dedicated step is provided for its removal, but
sensitive to zinc as a contaminant of the cobalt sulphide intermediate. It is also sensitive
to iron, aluminium and chromium levels as these contribute to nickel and cobalt co-
precipitation losses.
Of the three generic processing routes the hydroxide precipitation is probably the most
tolerant of chromate formation in the leach.

4.2 REFINING
The route produces a satisfactory intermediate product capable of storage and shipment
with some external refining facilities available for further treatment. The refinery section
of the route is more flexible than the sulphide precipitation route in that it can accept
hydroxides produced from any other processing route without significant modification.
However, recoveries could be significantly lower with imported hydroxides when
compared with freshly generated precipitate and this may require small modifications to
rectify.
The cobalt refinery for this route is not coupled to the nickel refinery, requiring nickel to be
sent back to the hydroxide precipitation step. No cobalt refinery is currently in operation
associated with this route, however, there are cobalt refineries around the world operating
upon similar feedstock (i.e. QNI’s cobalt plant). The cobalt can be produced as oxide
hydroxide, sulphate crystals or cathode.

4.3 CAPACITY
The processing route takes advantage of economies of scale with the first significant
jump in capital cost expected at about 60,000 tpa nickel production, although there is
large flexibility in this required. This is expected as PLS rates increase and thickener
diameters increase, at some stage justifying two trains of precipitation.
Greater production rates in the refinery area can enable significant capital savings by
allowing a more capital effective cleaning philosophy for the ammonia columns and
absorbers.

4.4 ENVIRONMENTAL/OCCUPATIONAL HEALTH & SAFETY ISSUES

While each of the processing routes use ammonia, this route contains the largest
inventory of volatile ammonium within the processing circuit. This is not a major issue
and is handled without problems in many industries, including at the QNI refinery in
Townsville. However, care must be taken to ensure this is minimised.

7
4.5 OTHER
The steam stripping of ammonia in this process integrates well with the more energy
efficient sulphuric acid plant designs (HRS, HEROS and Monarch) in its ability to
consume large quantities of low pressure steam.
The ammonium sulphate route developed by Highlands and Hydrometallurgical Research
Laboratory (HRL) is a variant upon the generic hydroxide precipitation route with
advantages over the ammonium carbonate route when remote magnesia supply is out
priced by local limestone deposits. Unfortunately, a lime boil is required to recover the
ammonia for recycled within this process and this introduces an additional technical risk
to the processing route.

4.6 FUTURE IMPROVEMENTS

Capital reductions are possible throughout this circuit with the possible integration of the
CCD and neutralisation circuits and increased efficiencies in ammonia leaching and
recovery. Another improvement would be a sulphide free cobalt refining method.
The ammonium sulphate route has potential for improved operation by exploring
alternative sulphate disposal methods.

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 5. DIRECT SOLVENT EXTRACTION

This processing route was been adopted by Resolute (Bulong) and a variant is proposed
by Inco (Goro). The development of this route has been the sole province of these two
companies.
The detractors of the PAL process in general have always pointed out that the leach
conditions result in slurries characterised by poor settling fines, high dissolved silica levels
and, later calcium saturation of solutions. This combination represents one of the worst
feed scenarios for a solvent extraction system. This does not mean that the direct
solvent extraction process route is flawed, however it does add to the risk, operating cost
and demands close operational control for this processing approach.
The detractors of the direct solvent extraction processing route have always pointed to
the lack of intermediate product as a disadvantage, while the supporters have pointed to
it as an advantage. The best description of it is that it is a risk. If this circuit is designed
and operated well, then it is an advantage in reducing the complexity of the plant, but if it
is not then there could be significant problems.

Iron/Chromium/Aluminium Removal
M M M M

Nickel SX/EW Impurity Removal SX

M M

Co Sulphide
Precipitation

Nickel Cathode Cobalt Sulphide Cake

Figure 5.1 Direct Solvent Extraction Flowsheet

9
5.1 ORE SENSITIVITIES
This processing route prefers high nickel and cobalt feed tenors to maximise recovery,
thus favours ores with high grades and with good CCD washing characteristics.
The process is sensitive to magnesium, manganese, copper and zinc. All of these
elements are extracted with the cobalt in the first solvent extraction step, thus the
equipment size and volume of cobalt barren liquor is dependent upon the levels of these
elements. The magnesium and the majority of the manganese, however, do not report to
the impure cobalt sulphide intermediate as contaminants.
It is also sensitive to iron, aluminium and chromium levels as these contribute to nickel
and cobalt co-precipitation losses. Of the three generic processing routes the direct
solvent extraction is probably the least tolerant of chromate formation in the leach.

5.2 REFINING
The cobalt refinery for this route is not integral to the nickel refinery. However, the
nickel/cobalt separation prior to cobalt refining is typically sufficient to not require any
further separation of nickel from cobalt.

5.3 CAPACITY
The processing route minimises its capital cost impact, by minimising the processing
steps, and thus equipment. From the capacity examples set in copper SX/EW plants
around the world, a single train of mixer settlers is limited to the vicinity of 2000 m3/h. At
a PLS concentration of 3.5 g/L Ni, an additional nickel extraction mixer settler train is
required every 60,000 tpa Ni and an additional cobalt mixer settler train approximately
every 100,000 tpa Ni.

5.4 ENVIRONMENTAL/OCCUPATIONAL HEALTH & SAFETY ISSUES

This process involves a continuous nitrogenous and organic release to the tailings
system. The organic release is typically small as a soluble component, but runs the risk
of surges of large quantities of entrained or soluble organic.
This process has the largest inventory of petroleum products as a part of the process.
While the organic diluent is tailored as a low flash point product, a significant capital
portion of the plant is held as combustibles. Similarly, if a solvent extraction diluent with
significant aromatic content is used, this could represent a larger carcinogen risk than the
other routes due to the inventory.

5.5 OTHER
Inco is proposing a more efficient variant of the Bulong processing route that selectively
extracts the nickel and cobalt from the low iron PLS liquor. This is then stripped into a
chloride media, the cobalt separated and produces a nickel oxide by pyrolysis of
crystallised nickel chloride. Unfortunately, the organic reagent is expensive and prone to
degradation when exposed to oxygen, especially in the presence of the metal ions
contained in the PLS. This significantly increases the technical risk and operational
problems with this approach.

10
5.6 FUTURE IMPROVEMENTS
This generic route has the most potential of achieving a quantum reduction in capital and
operating costs through developments in the solvent extraction steps. The “Holy Grail” of
this processing route is a single stable reagent to selectively remove nickel and cobalt
from the PLS. If the reagent were inexpensive, this could be sufficient to ensure the
economic superiority of this route.
The use of liquid-liquid exchange columns (i.e. pulse or rotating disc contactors) may be
more suited to cope with the gypsum crystallisation.
Capital reduction is possible with the increased integration of the CCD and neutralisation
circuits. Other encouraging improvements would be the selective removal of manganese
from the cobalt solvent extraction and a sulphide free cobalt refining method, but
development work is required.

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 6. CONCLUSION

The jury is still out on the best way to recover nickel and cobalt from PAL discharge
liquors. There is insufficient operating data from existing operations and they are all not
stable enough to provide a confirmation of predicted costs. Generally, reagent
consumption is still unstable and capable of reduction, while long-term maintenance costs
are as yet undetermined.
There is still a long road to travel before it is determined if one processing route will show
itself to be superior, and it is still not clear that one will. A single process may become
generally accepted as the preferred approach, but it is similarly unclear if this preference
will be based upon the issues discussed in this paper, upon perceptions or other non-
engineering issues.

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 7. ACKNOWLEDGEMENTS

The author particularly wishes to acknowledge and thank David Crook of Heron
Resources for asking me to write a paper that was almost finished, but probably would
never have been finished without the invitation.
I also wish to thank the existing WA laterite operations for any comments received prior to
publishing, Kvaerner E&C for allowing me time to prepare this paper and other Kvaerner
personnel for the assistance provided in the preparation of this paper.

13