SOME PRACTICAL ASPECTS FOR IMPURITY AND CRUD CONTROL

IN SOLVENT-EXTRACTION PROCESSES

H. Laitala, E. Ekman and G. Karcas

Outotec Oyj, Riihitontuntie 7 C, PO Box 86, FI-02201 Espoo, Finland

Corresponding author email address: hannu.laitala@outotec.com

ABSTRACT

Solids or precipitating compounds can greatly disturb a solvent-extraction process. For some
solvent-extraction plants crud and impurity entrainments are one of the main reasons for serious
process disturbances, production losses and increased operating costs. Lost revenue due to loss of
production or decreased production quality may be several million dollars per annum. This paper
presents a short list of activities which can be tried, or have been tried, by several plants when
crud or precipitating solids have been a major problem to a solvent-extraction process.

INTRODUCTION

In solvent-extraction (SX) processes the problems associated with crud and

impurity deportment can cause significant process disturbances resulting in economic
losses. In this paper the authors draw on extensive interaction with operations around the
world to compile a list of solutions applied to the problems encountered. Operations
include Finnish nickel (Harjavalta), cobalt (Kokkola) and zinc (Kokkola) plants, the
Bulong nickel and cobalt plant in Australia and the Skorpion zinc plant in Namibia. Each
SX process is unique and no universal solutions for the problem of crud and impurity
control can be given.

IMPURITY AND CRUD CONTROL BEFORE SX PROCESSES

The simplest way to reduce impurity and crud problems in an SX process is to

ensure that solids and impurities are removed before the pregnant leach solution (PLS)
enters the SX process. It is sensible to carefully examine the process during the design
phase to identify potential problems and allow space in the plant layout for additional
equipment to be installed at a later date. In this way it is easy to install the equipment in
the right location when required.
Ore Treatment and Leaching
Milling and Ore Pre-Treatment
Effective grind control and ore feed blending stabilizes leaching conditions
maintaining stable downstream process conditions like control of PLS concentrations and
solids removal.
Leaching Temperature and Agitation
High process temperature maximizes leach recoveries but can increase the
leaching of impurities. Control of leach temperature is an optimization balance between
recovery of the valuable metal and impurities transfer to the PLS. Reactor agitation with
variable speed drives assists in optimizing and stabilizing the process conditions in the
leaching reactors. Effective agitation speed and gas flow control have been applied at the
Harjavalta nickel and Kokkola zinc plants in Finland. These operational principles will
be applied at Cobre Las Cruces in Spain in 2008.
When the agitation level is high enough leaching recovery is acceptable, solids
are suspended and gas dispersion in the reactor is effective. In this way local
concentration variations are avoided [1,2].

Leach pH and pH Profile

Mechanically agitated leaching processes usually contain several reactors in
series. How the leach liquid and solids are fed to the reactors is an important
consideration. If all the liquid and solids are fed to the first reactor, the pH of that reactor
may drop significantly. A low pH with high or moderate leaching temperature
accelerates the leaching of impurities. Dividing leach liquid between the first two or three
reactors can help to make the leaching pH low enough for the main leaching reaction, but
without promoting the leaching of impurities. Illustrated in Figure 1, this type of leaching
pH control has been used at Harjavalta nickel plant and Kokkola zinc plant.

Divided reactor feed

pH

No dividing of feed
1R 2R 3R Neutr.
Process Unit

Figure 1. Stabilizing the pH profile in a reactor cascade by staging reactor feed.

Solids and Impurity Removal From PLS
Thickener and Clarifiers
Thickeners and clarifiers are effective separation equipment for solids, being
quite inexpensive and simple to use. Downsides are that a large footprint and heavy
foundations are required and the overflow from a thickener is never totally free of solids.
Since the particle size of these solids tends to be small they cause significant problems in
SX processes. Problems include phase separation difficulties, crud formation and
impurity transfer from the extraction to the stripping stages through the loaded organic
tank and washing stage. Clarifiers are usually not good with precipitating solids because
they contain small internal flow channels that can be easily blocked with precipitants like
gypsum. Thickeners are robust against precipitating solids but produce a dirtier
overflow than clarifiers.

Filtration
Filters are effective for removing solids from the PLS. Filtration is not usually
used alone since filtration capacity is expensive and operating and maintenance costs are
higher than for thickeners or clarifiers. Filters are more automated and filter cloths and
belts need to be changed regularly. Any type of solids in the PLS can be removed with
the right type of thickener and filter combination.

PLS Temperature Control

If a PLS stream contains a significant quantity of precipitants changes to the PLS
temperature prior to the SX process can be used to either accelerate or slow down
precipitation reactions. Cooling the stream before entering a cooling tower will promote
precipitation in the cooling tower and subsequent thickener. If thickener overflow is used
for the cooling duty the PLS flow entering the SX process will be heated and the
precipitation reaction in the SX will be minimized as concentrations are below saturation
limits. The process scheme described has several advantages:
PLS from leaching or neutralization is cooled and compounds like gypsum
start to precipitate.
PLS leaving the cooling tower thickener as overflow will be heated. Heating
will increase the solubility of the precipitating compounds and stop or
minimize the precipitation in the SX equipment.
Precipitated matter from cooling tower thickener underflow can be sent to the
preceding process step to be used as seeds in a neutralization process.
A cooling tower will have a positive effect on plant water balance and PLS
metal concentrations.
Since precipitation can start quickly in the PLS heat exchanger the unit must be
specially designed for this kind of service. The process scheme will be applied at the
Cobre Las Cruces copper plant. If solids precipitation from the PLS is intermittent the
PLS line can be equipped with a solids collector trap. When precipitation is continuous a
solids trap in the PLS line is not effective because the area needed for the trap is large
and the trap would need to be equipped with a constantly operating crud removing
device.

CRUD AND IMPURITY CONTROL IN SX PROCESSES

Solids and Impurity Washing SX Stage

Usually the first SX stage is the most affected with the incoming solids causing
crud in an SX process. In some SX plants the first stage is designed to circulate diluent in
a closed loop with incoming PLS. This diluent loop is separate from the main organic
circulation in the SX process [3].
With this design most of the crud formed in the SX process is formed in the first
diluent-wash step before solids can enter the extraction circuit. Therefore organic lost in
the crud formed will be cheap diluent and crud formation will not interfere with the
primary SX process. A crud removal system can be specially designed to deal with crud
from this SX stage and cleaning of the diluent wash stage will not interfere with the main
production process. This type of process has been used since 1990 at Kokkola and
Harjavalta nickel and cobalt plants in Finland. The Bulong nickel plant in Australia also
used a diluent wash stage [4]. Diluent wash stages to recover reagents like Versatic 10,
D2EHPA and CYANEX 272 have been used in the Harjavalta and Kokkola plants and
at Bulong.

Impurity SX

A separate impurity SX can be installed prior to the main SX circuit. This is

commonly practiced when producing cobalt and nickel but is not common in copper SX
processes. Fe3+ removal from a copper SX PLS could in some cases be an interesting
solution to associated problems encountered. There are copper SX processes in North
and South America where iron content in the incoming PLS is 30 to 60 g/L. These plants
usually experience low current efficiencies in EW (75 to 85 %) and have significant crud
problems in SX. Ferric iron control in the incoming PLS streams are vital for these
plants.

SX Equipment

Important design considerations that affect crud formation, entrainment and

impurity transfer in SX equipment are mixing, air intake and materials of construction.
Controlled and gentle mixing increases the SX process solids handling capability. To
minimize the organic phase degradation and crud formation, air intakes to the SX
equipment can be minimized using covers and air locks. All SX plants delivered by
Outotec have covered pumps, mixers and settlers.
With different construction materials or liners like FRP, HDPE or Teflon, solids
build-up on the settler and pipe walls can be controlled or minimized. If precipitation
occurs in an SX plant the use of stainless steel can be problematic because scaling can be
severe on these surfaces.
 A water spray in the settlers can effectively compact loose crud in the organic
phase. Compacted crud is more easily removed from the settler. A water spray combined
with controlled mixing produces compact crud. Bulong reported very fluffy crud formed
in the diluent wash stages and it can only be assumed that no crud compacting method
was used [4]. Water spray can also be used to remove dissolved impurities like chloride
(Na2SO4 solution / Cl-). These methods have been used in Finish and in South American
plants.

Extractants, Diluents and Modifiers

Crud and impurity transfer in an SX process can be controlled with proper

extractant, diluent and phase modifier selection. High flashpoint non-aromatic diluents
will be favoured in the future because of environmental, process, and work safety issues.
In some cases in copper SX, if crud is present, ester-based modifiers are preferred over
alcohol-based ones. In practice reagent selection has grown to satisfy changes in copper
SX processes. Different extractant and extractant/modifier mixtures like M5640, M5774,
M5910, LIX973 and LIX984 are readily available from suppliers.

Active Process Control

On-line analysers like Outotecs Courier have been used in nickel and cobalt SX
processes. The Courier analyses the SX process streams on a constant basis and results
are used directly in the process control system to change the controlled parameters (PLS
and organic flows, pH and phase continuity) automatically without human intervention.
This automated process principle has been applied at Outotecs nickel and cobalt SX
processes for over 20 years with very good results. Increased capacity, higher production
quality and less operating staff are needed to run the process. Capacity increase in these
cases has varied from 3 % to 20 %. Impact on production quality has been usually greater
especially for Ni and Co SX processes.
With the use of an on-line analyser loading of the organic phase and rich
electrolyte metal concentrations can be controlled. The on-line analyser can be used to
control the feed to the EW circulation tank. Poor quality electrolyte can be automatically
rejected from the EW circuit. The authors predict that these automatic control principles
including on-line analysers and high level process production models will see
applications in large copper, zinc, and uranium SX processes (PLS > 500 m3/h) during
the next few years. This automated control differs significantly from the more simple
PID control and represents a substantial improvement to the process.

Some General Solutions

In a number of processes anti-scalents have worked well to control and reduce

precipitation problems. Since anti-scalents are usually organic compounds they could
potentially have a negative influence on the overall performance of an SX process and
careful consideration is needed before their use. The Bulong operation used anti-scalents
very successfully to resolve a gypsum precipitation problem [4].
 For economic reasons the use of a three-phase centrifuge for treating crud and
returning associated organic and aqueous solutions to the plant is becoming a popular
choice in copper SX operations [5]. Some plants in North and South America have used
cyclones to remove organic and crud from the aqueous streams with variable degrees of
success.
Electrolyte filters positioned prior to the electrolyte circulation tank should not be
used for crud removal. Solids entering the electrolyte filter decrease the time to
breakthrough of organics impacting negatively on EW production quantity and quality.

CONCLUSIONS

There are a number of techniques that can be used to solve the problems caused
by crud and impurity transfer in an SX process. Treating the symptom can be easy but
can also be very expensive for an operating plant.
It is recommended to try find out as much as possible about the main process
operating conditions, to then isolate the reasons for the main process disturbances, and
then work towards eliminating these. Fast, easy solutions should be avoided as they
either dont help or have been attempted previously.

REFERENCES

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Chemical Engineering, 19 July 1976, 141 148.
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Solids in Liquids, Chemical Engineering, 24 May 1976, 144 150.
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Production at Outokumpu Harjavalta Metals Oy, Finland, ALTA Nickel/Cobalt
Pressure Leaching & Hydrometallurgy Forum 1997, ALTA Metallurgical Services,
Melbourne, 1997.
4. S. Donegan, Direct Solvent Extraction of Nickel at Bulong Operations, Min. Eng.,
19(12), 1234 1245 (2006).
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403.