ALTA SX/IX 2003

Solvent Extraction Entrainment Control Needs and Strategies

Graeme Miller – Manager Process Engineering Sinclair Knight Merz Australia

David Readett – Group Process Manager Straits Resources

Table of Contents

1.0 ABSTRACT .................................................................................................... 1

2.0 INTRODUCTION ............................................................................................ 2
3.0 FACTORS IN POOR ENTRAINMENT CONTROL......................................... 3
4.0 OUTCOMES OF POOR ENTRAINMENT CONTROL .................................... 4
5.0 DOWNSTREAM PROCESS ISSUES............................................................. 5
6.0 ENTRAINMENT CONTROL OPTIONS .......................................................... 6
7.0 ORGANIC REHABILITATION...................................................................... 16
8.0 PROCESS COMBINATIONS ....................................................................... 16
9.0 PLANT OPERATIONAL RESULTS ............................................................. 18
10.0 CONCLUSIONS ........................................................................................... 22
11.0 ACKNOWLEDGMENTS............................................................................... 22
12.0 REFERENCES ............................................................................................. 22
 1.0 ABSTRACT

Entrainment control in solvent extraction plants is an absolute requirement to meet the

dual needs of efficient and steady operation. A number of plant upset conditions can
contribute to a lack of entrainment control including low temperature, organic degradation,
high flow rates and poor equipment design.

Results of poor entrainment control include high solvent losses, poor mixer ‘efficiencies’,
poor stage efficiencies, progression of deleterious species such as Mn, Fe and Cl into
electrolytes and production of crud in units that are susceptible to upset.

Other issues with entrainment control are related to the contamination of one SX reagent
with that from an upstream SX plant. Some examples have been seen in Cu-U circuits
where the uranium extractant (tertiary amine) has transferred to the Cu SX and transferred
significant amounts of chloride to the EW. Some Ni/Co circuits have suffered similar
problems with interference and transfer of calcium in the Ni SX after contamination with Co
extractant.

Entrainment can effect down stream process as well as the SX performance. Wide spread
examples are organic burn and chloride attack on cathodes in copper EW, and high
electrolyte Eh from Mn entrainment. In Ni EW any organic is deleterious and high
entrainment can totally foul the electrolyte activated carbon filters. Carry over of carboxylic
acids (ie Versatic acid) can also severely corrode lead anodes by forming a soluble lead
salt.

The selection of entrainment control processes has generally been on an ad hoc basis with
only superficial science attached. Recently a number of studies and plant operating
experiences have shown that there is a good solid basis to be able to minimise
entrainment due to equipment design, select entrainment control hardware processes and
to customise the control system to the chemistry in the PLS and electrolyte.

Better design has arisen from the application of CFD to both mixers and settlers. The
dynamic modelling of settlers has shown that there are a significant number of macro
eddies that can form from the interaction of the phase separation process and the settler
internal geometry. Selection and design procedures to minimise these are straightforward.

In-settler coalescing systems are now gaining favour particularly where fouling is not too
large an issue and where operating in organic continuity is needed for control of secondary
silica issues. A number of systems have been proposed but only a couple have operated
successfully for long periods. Stream specific coalescing has a wide field of hardware
available but again with only a few successful applications.

Wash or scrub stages can act as entrainment control systems as well as chemical removal
of deleterious species from the organic. Operating the wash stage with little or no acidity
can physically remove the entrained species but leave any chemically attached species.
This can be used to change the chemistry of the transfer to the strip solution so that is
different to the PLS.

The use of both coalescing and wash stages shows that there is benefit in having the
coalescer before the wash. Significant benefits are evident from both modelling and field
experience.

1
Diluent scrubbing is a technique to replace the high concentration of organic typically in the
raffinate with lower concentration diluent. The technique is straightforward when the
diluent make up is at a high rate. However it needs a re-concentration step to extract the
reagent from the scrub diluent if the make up rates are low. One operation has developed
a technique for recovery of Cyanex 272 from a diluent scrub.

Eventually most control systems rely on the organic surface characteristics. As such
operations that regularly treat the organic to maintain its ‘pristine’ surface activity have
lower entrainments and fewer plant operating issues than those that do not. Prevention is
better than cure.

2.0 INTRODUCTION

The issue of entrainment control in solvent extraction plants is not trivial, as many
operators have found to their cost. Even a well run plant can have unexpected
entrainment issues that are not obvious. It is really only when entrainment gets to a level
where there are effects on: SX plant transfer efficiency, upstream and downstream
processes or economic loss, that operators tend to take action.

It is considered unusual to have entrainment issues. However it has been found that most
plants suffer at some time in their operating lives and that the issues (when present) are
extremely important. A process focus on entrainment control is not a luxury but a
necessity to maintain good operating conditions, efficiencies and economic production.
Steady operation of the SX plant is the key to the successful operation of the entire
process.

A lack of SX plant control gives poor operations and results in poor efficiency measures.
These measures may be the chemical transfer of the desired or undesired species, the
mixer efficiency, the stage efficiency, the tolerance to temperature or other changes in
plant physical conditions. In all cases the key to maintaining high efficiency is to maintain
control over the entrainments. These are often the prime measured variable. However
they are seldom the real underlying ‘cause’. Entrainment is often a symptom of a deeper
set of causative factors that have upset the chemical and/or physical characteristics of the
organic phase.

Most operators believe that their SX plant runs smoothly and with little change in
entrainment on a day to day basis. On average this is true. However the short term
entrainment levels are often up to an order of magnitude greater than the longer term
operating averages. It is these peaks (Miller, Readett and Hutchinson) as shown in Figure
1.0 that can initiate a significant period of poor plant operation.

2
 S e ttle r E x it E n tr a in m e n ts w ith D e e p E m u ls io n B a n d a t
th e D is c h a r g e

25000

20000
Aqueous Entrainment
in loaded Organic

15000
ppm

10000

5000

0
6/1 7/1 8/1 11/1 13/1 16/1 20/1
1

13

17

21

25

29

33

37

41

45

49

53

57

61

65

69

73
D a te

Figure 1.0 Peak Entrainment Levels from a Copper Mixer-Settler

Many other entrainment production processes have similar temporal patterns. The
ubiquitous “crud rush” that transfers crud throughout the circuit is actually an uncontrolled
entrainment peak. Crud (particularly fluffy crud from an aqueous continuous mixing
operation) is transferred all the time via the organic phase. It becomes a major issue when
the level of crud production increases or the settler performance decreases to an extent
that allows the crud to flow to the following part of the SX train.

3.0 FACTORS IN POOR ENTRAINMENT CONTROL

There are a large number of factors that are involved in high level, symptomatic
entrainment. Many of these also interact symbiotically to produce not only high
entrainment but also the erratic levels of entrainment shown in Figure 1.0. The underlying
reasons for the entrainment presence needs to be identified properly in order to select the
appropriate control or prevention measures that will address the real situation.

3.1 Low temperature effects the organic reagent and aqueous phase viscosity. This is
a significant factor in determining the ability of the settler to coalesce the emulsion and
separate the two phases. With higher viscosity the finer bubbles will take longer to
coalesce and travel to the interface

3.2 Reagent degradation has multiple effects on entrainment levels. The most obvious
is the reduction in the interfacial surface tension (IST). With lower IST levels the emulsion
is more stable and separation is slower, leading to higher entrainments. Degraded reagent
also tends to produce greater quantities of crud. This crud also to tends to be more
mobile, contributing to greater levels of entrainment via this mechanism.

3.3 High Flow Rates through the settler (or column) decrease the residence time for
coalescence and separation. With lower available times the level of entrainment increases
until it is no longer acceptable. Another aspect of high flow rates is the use of variable
organic depths for process management reasons. Shallow organic depths can exceed the
maximum design space velocity. This in turn provides the conditions for high and erratic
entrainment levels of aqueous in the organic.

3.4 Equipment Design has a significant effect on the level of entrainment that can be
achieved. Poor feed distribution can produce large vertical and horizontal eddy flows
(Girialco et al). Poor distribution can also decrease the total settler area that is actually
being used for separation. In some plants this can be as much as 50% of the settler area.

3
Entrainment of air into a mixer can occur particularly from a previous stage using gravity
flow for the transfer. The design of the unit discharge system and / or the mixer inlet can
be significant factors in the level of air entrainment experienced.

3.5 Slow Phase Separation can be a result of other factors (temperature, reagent
degradation) but can also be symptomatic of other factors involved with the emulsion
stability: eg. crud stability, low actual interfacial intension, excessive mixing phase ratio
and excessive energy input to the mixing process. All of these factors need to be
considered when identifying the underlying causative factors.

3.6 Fast phase separation can also lead to high entrainments (Miller). Fast phase
break leads to a lack of emulsion band to filter the primary and secondary haze in the
settler. It can be a result of low mixing intensity, highly efficient pump mixers, or reagent
selection that interacts with the PLS chemistry. This latter is particularly evident with ester
modified copper reagents in warm or very clean PLS solutions.

3.7 PLS Chemistry can also significantly effect the level of entrainment and the
intensity of the down stream effects. The most widespread is silica (Readett and Miller
1995) with its issues of fluffy crud and stable emulsion formation. Other ions that can be
involved in entrainment production include Zr in U SX, Mo in Cu SX. Other ions have
secondary effects such as Mn in Cu SX which can be oxidised in the EW and degrade the
reagent in the SX via the return electrolyte (Miller 1995).

4.0 OUTCOMES OF POOR ENTRAINMENT CONTROL

Outcomes of poor entrainment control are generally seen as economic costs (reagent loss)
or lowered efficiency of production. These tend to be the symptoms that are first identified.
It is important to then analyse the total situation in the entire SX plant to make a
determination of the real contributing factors. It is often seen that the outcomes are so
important that they are addressed without the proper analysis of the causes. Unless the
actual cause is addressed the results will be severe plant disruption and wasted effort in
addressing the wrong things.

4.1 Solvent Loss is a significant economic cost issue particularly with high cost
reagents. With uranium SX the reagent cost is modest and the concentrations generally
low. As a result the attention paid to the minimisation of organic loss was less than for
other extractants. Much of the progress in minimisation of solvent loss has been
generated by the copper hydrometallurgy industry. Other SX systems eg Co & Ni have
benefited from this progress. The cost of solvent loss needs to be considered in light of all
the loss points in the system: entrainment in raffinate and electrolyte, loss to stable crud
and housekeeping. As will be discussed in later sections these are actually interrelated
and need to be addressed with an holistic approach to the problem.

4.2 Mixer Efficiency can be adversely effected by the entrainment of the aqueous in the
advance organic or organic in the advance aqueous. In either case the determination of
the ‘real’ level of entrainment is difficult (and very seldom done when checking mixer
efficiency). With high entrainment levels the mixer efficiency calculated from the advance
and discharge streams will be lowered by the presence of entrainment.

4.3 Stage Efficiency can be calculated similarly to mixer efficiency. In this case the
settler exit streams are used rather than the mixer exit emulsion. If entrainment in the exit
streams is high there will be an increase in the transfer of the economic ion to an SX stage
where it will decrease the efficiency of that stage. In this case the entrainment is a loss of
‘product’ to a subsequent stage that may not be able to recover it: eg electrolyte entrained
to the final extraction stage.

4.4 Ionic Species Transfer is an extremely important issue with all SX operations. It
can be the start of severe circuit upsets and / or downstream process upsets. The ions of

4
interest have been identified in a number of circuits (Readett, Miller and Holle). In all
cases control of the SX plant entrainment is a prime step in minimising the transfer and
effects of the ions.

 Iron is the most widespread particularly in the copper industry where it decreases
the current efficiency in EW. Generally the larger transfer mechanism is chemical
rather than the physical entrainment. However when the PLS entrainment in loaded
organic is high (perhaps due to effects from silica) the physical transfer can be even
greater than the chemical mechanism. Under these circumstance the control of
entrainment is the prime goal rather than trying to increase the Cu:Fe selectivity.

 Chloride (particularly in Australia and Chile) is an ion that has the potential to
inflict very severe problems in the EW. Except for special circumstance discussed in
the next section, chloride is only transferred via entrainment. It can be the sole driver
for selection of entrainment control measures (Miller, Readett and Hutchinson 1996).

 Manganese transfer via entrainment has been the underlying issue with a number
of operations (Miller 1995). When combined with a low iron concentration in electrolyte
(eg during early commissioning and operation) a very high Eh can develop that will
oxidise the Mn2+ to Mn4+ and Mn7+. The permanganate will oxidise the organic reagent
and destroy its chemical and interfacial characteristics; leading to higher entrainments,
more manganese transfer, more organic degradation and a catastrophic reduction in
SX performance.

 Silica has subtle effects when transferred to later SX stages via the organic. In
aqueous continuity it forms fluffy crud that stays in the organic phase rather than
accumulate at the organic-aqueous interface. As fluffy crud it is transferred to the strip
stages and precipitates as polymerised silica in the higher acidity of this stage. The
high surface area silica solids form both fluffy and compacting crud giving issue with
transfer of electrolyte to the extraction and loss of electrolyte and organic in the crud
produced.

4.5 Circuit Cross Contamination in multiple SX circuits is also an important

consideration in the selection of the overall SX plant hardware. The cross contamination
can be direct via two SX circuits in series or via a raffinate recycle to leach with
subsequent return to the SX plant(s). If the cross contamination is not addressed the
transferred extractant can accumulate and cause severe problems in the ‘wrong’ SX plant.
Some of the more significant experiences that have been reported include:

 U SX amine reagent in a copper SX giving major chemical transfer of chloride to the

copper electrolyte.

 Co SX Cyanex 272 transfer to the subsequent Ni SX giving large Ca chemical

transfer from extraction to strip and massive gypsum precipitation.

4.6 Air Entrainment Issues are not well understood by many operators. The air in the
pump -mixer can cause cavitation and loss of hydraulic capacity as well as a reduction in
the head produced. Entrained air can also accelerate organic oxidation in susceptible
extractants. It can also serve as a third phase stabiliser and create an ‘air crud’. This very
fluffy crud can be a real problem with capture and can lead to significant crud transfer of
other entrainments. Air in the separating phases can also create quite significant vertical
turbulence and re-mixing of the partially separated phases.

5.0 DOWNSTREAM PROCESS ISSUES

Some of the downstream process issues have already been mentioned in the previous
section. The prime initiation of many secondary and tertiary symptoms is the entrainment

5
transfer of a species that continues to travel through the circuit; until it can accumulate to a
level that has significant effects on the process.

The most common is the entrainment transfer of iron into copper EW operations. Figure
2.0 shows the reduction in current efficiency with increasing iron concentration in
electrolyte.

Plant Survey (1998) Current Efficiency

100
Current Efficiency %

90

80
0.00 1.00 2.00 3.00 4.00 5.00 6.00
Total Fe g/L

Figure 2.0 Iron effect on Current Efficiency.

Other significant effects are the transfer of chloride and the corrosion of 316 stainless steel
cathodes. This has been an issue with a large number of copper projects especially
Olympic Dam, Nifty and Girilambone in Australia and El Abra and Ivan Zar in Chile.

The uncontrolled entrainment of organic in electrolyte can lead to organic burn in copper
and nickel EW and the total fouling of carbon adsorption columns in Ni EW. Organic burn
can reduce the whole of the tankhouse production to less than LME “A” particularly for
sulphur, and iron. The entrainment of organic in cobalt EW has led to accelerated anode
corrosion from entrained Vesatic acid. This forms soluble lead carboxylates and leads to
massive lead loss from the anodes.

The most catastrophic entrainment issue is that of manganese in copper electrolyte. A

number of operations have experienced this including Girilambone and Nifty in Australia,
Bwana Mkubwa in Zambia and Chuquicamata and Ivan Zar in Chile. With low levels of
iron in the electrolyte (particularly during the early commissioning phase) the Mn2+ can
oxidise to Mn4+ and Mn7+. The permanganate returns to the strip stage and oxidises the
organic. The degraded organic has lower phase separation characteristics; entrains more
PLS and manganese to the electrolyte and a self reinforcing spiral of accelerating
degradation forms. The whole SX operation can collapse in a single shift of operation
(Miller 1995).

6.0 ENTRAINMENT CONTROL OPTIONS

6.1 OPTIONS AVAILABLE

There are a number of entrainment control options that can be used to both eliminate the
problem and / or to address the symptoms and continue operating the plant.

In general the prevention measures start with keeping the organic in the best possible
condition to minimise phase separation issues. Rehabilitation and maintenance of the
organic properties is also a good part of this approach.

6
Equipment (especially settler) design can increase separation performance and minimise
entrainment in the separated phases. Other devices can be included in the settler to assist
this performance. Minimisation of air entrainment is also a settler design issue particularly
in the discharge launders and nozzles.

Stream specific treatment can be incorporated to eliminate the entrainment before it is

passed to the next process step. This can take a number of forms using a wide range of
process equipment and approaches.

Combinations of the above approaches are a low risk method of continuing the plant
operation even during periods of high risk conditions. Some approaches are significantly
better than others in achieving the results of low entrainment and low risk under upset
conditions.

6.2 EQUIPMENT DESIGN OPTIONS

Good equipment design can be the most effective means of achieving low entrainment
operation risk. In recent times it has been shown (Miller 2000, Miller 2001) the operation
of a commercial settler is a dynamic system with the potential for high circulation flow rates
and macro eddies formed from the phase separation process itself. Figure 3. Shows the
dynamic flow patterns that can be observed in many settlers without other internal
hardware.

Figure 3.0 Settler Dynamic Flow Patterns

7
Other studies (Girialco, Stanbridge and Sullivan) have shown that the feed end
hydrodynamcis of the settler (even with only a single phase present) is also a major
contributor to poor performance. The feed with any sort of “spout’ in either the vertical or
horizontal planes can induce large flow eddies that can fill the depth of the settler. They
can also effect a very large proportion of the settler area and lead to low unit capacities.
Figure 4.0 (from Stanbridge and Sullivan) illustrates the full depth eddy at a vertical feed
spout.

Figure

4.0 Settler Feed Spout CFD Model.

Better feed presentation and distribution can eliminate many of the issues with hydraulic
eddy formation. Figure 5.0 shows a full depth feed system with turning and distribution
vanes. The settler feed is gentle over the full depth and each section of the picket fence is
presented with a flow volume that is the same for all.

8
 Figure 5.0 Full Depth and Width Settler Feed Distribution
A number of detailed design issues are also important in minimising the loss of one stream
in another during operating transients. This is especially the case during start up and shut
down. In some operations the failure of the raffinate valve to close properly can cause the
entire contents of the settler or pulsed column to flow to the raffinate pond or tank, with
consequent loss of the organic.

Simple hydrostatic legs can prevent this situation from occurring in pulsed columns but it is
not a common feature of their installations. For settlers the situation is easily addressed
with full length overflow weirs but can be a significant issue with level control columns or
interface level control valves. Simple issues such as this can effect the total organic loss
by +200% if not taken.

Air entrainment can be minimised with proper attention to detail in the discharge launder
and nozzles. Anti vortex baffles should be used in all nozzles. Discharges from settlers to
collection launders should have a shaped profile to prevent the flow stream free falling into
the launder surface. The launder itself should have the valving and control to operate at
high levels (even close to flooding) to minimise the hydraulic drop between settler
discharge and launder operating levels. To achieve a surface impingement velocity of <1
m/s requires a drop of <51mm.

6.3 IN-SETTLER ENHANCEMENTS

Further enhancement of settler operation can be achieved with coalescing systems.

These can take various physical forms such as: trays (IMI system), baffles (Lewis), random
packed media (Miller, Readett and Dudley) extra picket fences or ordered media. In all
cases the hardware is installed to increase the settler unit capacity and to minimise the
entrainment. This is accomplished by the media performing a number of activities, that all
help to reduce the entrainment in the exit stream.

 Improves the flow distribution across and in the depth of the settler

 Eliminates eddies and other macro flow patterns induced from the hydraulics or
phase separation

 Provides a surface for coalescing of droplets

9
 Holds back a deep emulsion band layer for filtration of fine haze

As a result of these actions the entrainment is controlled and other operating scenarios
can be successfully implemented:

 Allows operation of mixers in any continuity

 Eliminates peak entrainment and shock loads to down stream processes

 Increase the total hydraulic capacity of the settler.

Figure 6.0 shows a typical random packed media installation in a large conventional
settler.

Figure 6.0 In-Settler Coalescing Media

In many cases the phase separation is fast and no emulsion band can form as there is no
emulsion left after the settler feed system. In these cases the coalescing function of the
media becomes an important aspect of the settler enhancements. As a result the large
surface area systems perform better than those with low specific surface areas.

Figure 7.0 shows entrainment of organic in electrolyte from a very large settler where the
break times were extremely short. The entrainment is at a very high level compared to the
design basis of 50 ppm. The high levels are also extremely erratic and lead to shock
loading on the multi media filters. Figure 8.0 shows the immediate effect of installation of a
high specific surface random packed media (Miller 2000). The entrainment is lowered
below the level design and the erratic peaks have been eliminated.

10
Organic Entrainment in Strong Shift Average Design Criteria
700.00

600.00
Electrolyte (ppm)

500.00

400.00

300.00

200.00

100.00

0.00
1/5/99 0:00 1/10/99 0:00 1/15/99 0:00 1/20/99 0:00 1/25/99 0:00 1/30/99 0:00
Date

Figure 7.0 Settler Operation with No Emulsion Band

11
 Effect of In-settler Medium on Exit Entrainments
with no Dispersion Band
Daily Sample Running Average Design Criteria

500.00

Srong Electrolyte (ppm)

Organic Entrainment in
400.00

300.00

200.00

100.00

0.00
14-Feb 19-Feb 24-Feb 1-Mar 6-Mar 11-Mar
Date

Figure 8.0 Effect of In-Settler Coalescing Media with No Emulsion Band Operation
The increase in hydraulic capacity can be quite dramatic. The Girilambone operation
monitored the settler performance over many years. They found that the settler capacity
could be increased and the entrainment decreased when using the random in-settler
coalescing media system. Table I illustrates the results that they have obtained.

T a b le 1 – T y p ic a l G C C S e ttle r E n tr a in m e n t V a lu e s

O r g a n ic in A q u e o u s A q u e o u s in O r g a n ic

S e t t le r F lu x S e t t le r (p p m ) (p p m )
3 2
(m /m /H r) B e fo re A fte r B e fo re A fte r

E1 110 40 800 100

5 -6 E2 180 50 >1000 120

E3 250 70 >1000 120

S1 140 25 250 50

E1 80 30 200 60

3 -5 E2 120 40 500 80

E3 150 50 500 80

S1 100 15 80 30

6.4 STREAM SPECIFIC TREATMENT.

Stream Specific Treatment can take a number of forms.

 Gravity coalescing

 Pressure (pumped) coalescing

 Organic wash or scrub stage

12
 Diluent scrubbing

 Organic flotation

 Crud de-emulsification

The selection of the appropriate equipment to be used depends on the SX process

selected and the other hardware installed in the plant. It is not too much of an impost on
capital or operating cost if there is sufficient head available to install a gravity unit.
Likewise if there are high pump heads involved (such as in a pulsed column plant) some
extra head for a pump fed unit is not a big increase either.

The selection of the stream to be treated is also an important issue. In some quarters
there is debate as to whether control of entrainment in loaded organic is more important
than in stripped organic. In uranium SX both are important for proper pH control in the
subsequent stage. Here it is not unusual to have both loaded and stripped organic tanks
to enable both surge and entrainment control. In copper SX however the use of an
electrolyte bleed for control of EW chemistry means that the absolute control of
entrainment in the stripped organic is not necessary as this forms part of the overall bleed
volume. However the control of PLS transfer to the electrolyte is very important and has
resulted in most copper SX plants using loaded organic tanks and entrainment control
systems.

6.4.1 Gravity coalescing is used when the total pressure drop for the unit is modest. This
arrangement has been used for random packed media particularly on loaded
organic coalescing duties. The media needs regular cleaning (every two or three
months) to remove the crud accumulation. Figure 9.0 shows a coalescer ready for
quarterly cleaning. The performance of the unit had deteriorated from 200 ppm to
400 ppm aqueous entrainment in the advance stream. The pressure loss increase
was not measurable on the plant.

Figure 9.0 Loaded Organic Coalescer prior to Cleaning

The effectiveness of these types of units is illustrated by Figure 10.0. The incoming
entrainment is highly variable up to 2,000 ppm. The exit entrainment is much less
variable with consistent levels of 200 ppm rising to 400 ppm over a considerable time
frame.

13
 Loaded Organic Coalescer
Aq Entrainment in Feed & Discharge

2500 600

500
2000
Aq Ent in Feed (ppm)

400
1500
300
1000
200

500
100

0 0
1 1 8 7 8 1 2 2 1 2 7 5 5 5 2 9 4 1 5 1 1 2 2 1 4
0 0 0 0 6 0 0 0 6 0 0 5 5 0 5 5 0 5 0 0 6 5 0 8 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0

January 1994
Series1
Series2
Series3

Figure 10.0 Operating Results for Loaded Organic Coalescer

Structured packing has been used on raffinate recovery of entrained organic
(Schoenburn and Keyser1999). Anecdotal evidence is that the operation of these
units is not reliable in the longer term due to fouling of the packing.

Sand bed filters using anthracite and garnet for recovery of organic from electrolyte
have been installed in a few installations. These appear to have good operating
results due to the regular (once or twice per day) cleaning cycles used. Successful
application has been at Andacollo in Chile.

6.4.2 Pressure (pumped) coalescing is used extensively in multi media filtration of

organic from the strong ‘electrolyte’. It is almost universally used as the final
polishing before copper EW. Further organic removal (including dissolved organic)
as required for Ni and Co EW. An activated carbon filter is effective in adsorbing
the organic. The carbon needs to be taken off line for regeneration generally by
furnace re-activation.

The use of pressure coalescing on organic streams has not been generally used in
the minerals processing industries. The reasons for this are not clear. However it
is a generally used application in removing water from crude and refined oil
products. One application in the USA did not meet the pilot plant operating results
and was a disappointment to the operators.

6.4.3 Organic wash or scrub stage is used to both remove any chemically bound ionic
species from the organic and also to dilute entrained aqueous and remove
deleterious ions. It can also be used as an intermediate step to change the pH
between extraction and stripping. The selection of a wash/scrub stage can be
based on a number of criteria all of which could be addressed by the one unit.

Chemical scrubbing is generally used for removal of iron in copper SX and Si, Mo
and Zr in uranium SX. It is also used in uranium SX to remove (saponify)
deleterious species contained ion the organic such as carboxylic acids etc. The
ability to change chemistry allows this stage to be included for this reason alone.

14
 When treatment of entrained aqueous in the organic is the main aim, a wash stage
can be set up to provide almost any proportional removal that is required. The
main control variable is the aqueous bleed (=new aqueous wash solution feed).
This is the most effective means of providing positive control in the circuit for
entrained species. Specific applications of washing include the control of chloride
and manganese transfer into copper electrolytes, and control of chloride and
molybdenum in uranium precipitation plants.

One special application uses a very ‘ineffective’ chemical iron scrub to change the
Fe:Mn ratio from 1:6 in PLS to 10:1 in the electrolyte. This relies on an efficient
washing of the entrained manganese while the inefficient scrub allows the chemical
transfer of the iron to the electrolyte. This has minimised a high EW bleed and
eliminated the addition of ferrous sulphate into to the electrolyte to maintain the
10:1 Fe:Mn ratio needed to keep the Eh low.

6.4.4 Diluent scrubbing is used when the value of the extractant is sufficiently high that it
warrants this sort of intense recovery. It is also used when the downstream effect of
the extractant is so severe that the costs of recovery are offset by the benefit in
improved subsequent operation.

The process essentially replaces the high extractant concentration organic entrained
in the SX raffinate, with a lower extractant concentration entrained in the exit from
the scrub stage. If this process is to work there must be either a use (or disposal) of
a low extractant concentration bleed stream; or a process to recover the extractant
from the bleed stream- with recycle of the diluent. One process developed for the
diluent scrubbing of Cyanex 272 also included an innovative method of recovering
the 272 from a diluent side stream.

Generally diluent scrubbing is one aspect of an overall total entrainment control

scheme that will most likely include further organic removal prior to raffinate delivery
to subsequent processes.

6.4.5 Organic flotation is used to recover organic from electrolyte and raffinate streams for
both process and economic reasons. One of the issues with organic flotation is that
the organic loss is preferentially with the more degraded material. This implies that
its surface characteristics are less than the average and the resultant recovery by
flotation is not as high as generally expected. The hydro-phobicity of the organic is
reduced as more polar degradation molecules are included in it. This reduces the
organic / bubble contact attachment and the overall recovery drops.

However the process can provide recovery of large volumes of organic that might
otherwise escape during upset conditions. It has been used ahead of multimedia
filtration to relieve high and erratic loads; providing a more reliable low organic
electrolyte stream. Recovery from raffinate is widely practiced particularly where the
plant entrainment loss is high. Recovered organic should be rehabilitated if possible
to remove degradation products and return a ‘pristine’ organic to the circuit.

The total recovery, even with ultra fine bubble systems (eg Jamseon Cell) is not
100%. The operating model for the column generally is one of a ‘constant’ tails
concentration of around 10 ppm. This gives high recoveries of 90% with a 100 ppm
feed but much lower recoveries of 50% with a 20 ppm feed. Knowledge of this
operating characteristic will allow proper economic evaluation of the process
depending on the feed characteristics.

6.4.6 Crud de-emulsification is a stream specific treatment that releases tightly bound
(emulsified) entrainment through breaking down the emulsion. A large number of
treatment methods have been developed over the years with the most successful
being one or a combination of:
15
  Gentle agitation
 Gentle agitation in organic continuity with an aqueous spray (Codleco system)
 Centrifuging using either stacked disc or decanter type units
 Pressure filtration through a number of media including diatomaceous earth, clay,
fine filter cloths etc.

The most successful in terms of ease of operation is the pressure filtration. This has
now taken over as the most widespread technique from centrifuging.

7.0 ORGANIC REHABILITATION

The rehabilitation of the organic phase is primarily aimed at removing species that interfere
with the interfacial characteristics of the solvent phase. These tend to be polar
degradation products of the extractant and to a less extent the diluent. Other species may
be attached to the extractant and interfere with its ability to perform either chemical or
physical activities. By removing the interfering polar molecules the interfacial tension and
hydrophobicity are returned close to the original.

When considering the organic degradation it is often easy to overlook how little is required
to have a dramatic effect. To completely cover the entire interfacial area of emulsion of a
‘standard’ SX requires only 1000 ppm of contaminant. This relates to less than 0.1% of
the organic having to be degraded. It is no wonder that an oxidation event (such as Mn
contamination of electrolyte) can have such a catastrophic effect on SX performance.

The effect of a degraded organic can be seen in both the physics and chemistry aspects.

A low chemical transfer capacity or a decreased stage efficiency can be an initial indicator
of contamination. Other physical symptoms could include:
 a lower interfacial tension,
 slower phase separation rates,
 higher entrainment from more stable emulsions,
 reduced hydraulic capacity of settlers
 higher rates of crud formation
 formation of more stable crud
Copper and Cyanex 272 SX use a clay treatment to adsorb the polar contaminants.
Uranium SX uses a caustic scrub to remove ions such as Zr and Mo. The caustic also
saponifies any fatty acids that may be present in the organic.

By maintaining the organic in top condition:

 the direct entrainment loss is minimised
 the recovery of entrained losses is improved
 the amount of crud produced is minimised

For these reasons the use of on-going organic treatment as a preventative / maintenance
measure in increasing in popularity. Those plants using this technique tend to experience
the lowest overall entrainment loss profile and have high quality and stable operations

8.0 PROCESS COMBINATIONS

Combinations of entrainment control processes have the lowest risk of entrainment under
severe upset conditions; and the lowest overall entrainment. In particularly critical
situations it is not unusual to see two or even three stages of entrainment control to
minimise the effects on downstream processes.

16
The most obvious initial step is the low cost alterations to the settler feed distribution and
internal macro flow controls. Appropriate full depth feed distribution has shown major
benefit in-settler operation. A second picket fence shows benefit in holding back a deep
emulsion band. However a third picket fence has actually been shown (at Nifty and Bwana
Mkubwa) to upset the flow patterns again with higher entrainments. Further in-settler
media or structured packing is useful if it does not itself set up other macro flow eddies and
channels.

The position of any in-settler systems needs to be targeted at those units that have the
greatest impact on the process. Stages where exit streams progress to other processes
are most important such as the first extraction stage (giving loaded organic) and the first
strip stage (producing electrolyte).

A common discussion point is whether to install stream specific (loaded organic)

coalescing or a wash stage. This depends on whether the ion of interest is entrained
(chloride, manganese) or chemically bound (iron and chloride in some instances).
Physical entrainment can be addressed with coalescing while chemical attachment needs
a wash stage. If the entrained species is in high concentration (generally > 2 g/l in PLS)
there is a need for both coalescing and a wash stage to limit the total transfer of entrained
species. The question then arises as to whether it is better to install one before the other
or visa versa. In both cases they must be between the extraction and stripping stages.
The two alternatives are:

EXTRACT => LOADED ORGANIC COALESCING => WASH => STRIP

EXTRACT => WASH => LOADED ORGANIC COALESCING => STRIP

Both are viable solutions and both have been utilised to good advantage. Figure 11.0
shows an analysis of the total transfer of chloride to electrolyte with both systems.

Chloride Transfer to EW
(300 ppm ex LO Coalescer, 3 m 3/h Scrub bleed)

LOC =>Scrub Scrub =>LOC

0.25

0.2
Chloride to EW kg/h

0.15

0.1

0.05

0
0 500 1000 1500 2000 2500 3000
Aqueous in Organic ex Scrub or E1- ppm

Figure 11.0 Transfer of Chloride to Electrolyte with two Control Arrangements.

17
The analysis shows that there is little difference at ‘normal’ levels of entrainment. However
under high entrainment events the system with coalescing followed by washing has
significantly lower transfer via entrainment. For this reason it should be used in preference
to the other arrangement wherever it is practical to implement.

In all cases inclusion of regeneration or rehabilitation of the organic pays significant

dividends to the operation. Whether any other entrainment control is used regeneration
should form an integral part of the normal operating procedure.

9.0 PLANT OPERATIONAL RESULTS

A number of operating plants have had significant entrainment control systems retro-fitted
as a result of PLS chemistry changes from the original design basis. In most cases the
control outcomes were for the minimisation of chloride and manganese transfer with a
controlled iron transfer to produce the optimum Fe:Mn ratio in electrolyte.

The Nifty copper operation underwent a staged process (Dudley et al 2002) with the
following steps:

1. Conversion of original SX train (Train A) from 2 series extraction stages (2E-1W-2S) to

3 stage series-parallel extraction (1Ep-2E-1W-1S)

2. Improved settler feed and internal design combined with optimised “in-settler
coalescing” for Train A.

3. Installation of a second SX train (Train B) and a combined loaded organic coalescer

(unlike Train A, Train B only consisted of 2E-1S circuit with no wash stage. The
revised internal design and optimised in-settler coalescing was utilised for Train B.
(Figure 12.0)
SX Train A
SX Train B

Strip E3 E2 E1 Wash E1 E2 Strip

Loaded
Raffinate PLS Organic Loaded
Coalescer Organic
Tank

Figure 12.0 Original Train A +Train B Configuration

4. Reconfiguration of the two trains and installation of a washing stage of the combined
loaded organic stream after the loaded organic coalescer (Figure 13).

18
 SX Train A
SX Train B

Strip E3 E2 E1 E1 E2 E3 Strip

Raffinate

PLS

Loaded
Wash Organic Loaded
Coalescer Organic
Tank

Figure 13.0 Optimised Train A +Train B Configuration with Combined Wash pre LO
Coalescer

The results of the various stages of the implementation programme are shown in Figure 14.0
and 15.0.

Nifty SX Plant Performance Improvements

70.00 1200.00
Train A Picket
Train A Series Train A + B + Train A + B +
Fence &
LO Coalescer LO Coalescer 1100.00
In-Settler
+ Wash
Coalescer
60.00 1000.00
Cl
Concentration Train A Parallel 900.00
PLS Flow
Chloride in Electrolyte (ppm)

50.00 800.00
PLS Flow (m3/hr)

700.00

40.00 600.00

500.00

30.00 400.00

300.00

20.00 200.00

100.00

10.00 0.00
0 200 400 600 800 1000 1200 1400 1600
Days

Figure 14.0 Chloride Transfer to Electrolyte

19
 Nifty SX Plant Performance Improvements
240.00 1200.00
Train A Series Train A Parallel Train A Picket Train A + B + Train A + B +
Fence & LO Coalescer LO Coalescer
220.00 1100.00
In-Settler + Wash
Coalescer
200.00 1000.00
Mn in Electrolyte (ppm)& in PLS (g/L x 10)

PLS Flow
180.00 900.00

160.00 800.00

PLS Flow (m3/hr)

140.00 700.00

120.00 600.00
Electrolyte Mn
Concentration
100.00 500.00

80.00 400.00

60.00 300.00

40.00 200.00
PLS Mn
20.00 Concentration 100.00

0.00 0.00
0 200 400 600 800 1000 1200 1400 1600
Days

Figure 15.0 Manganese Transfer to Electrolyte

It is evident that each stage improved the chloride transfer. Initially there was a concurrent
improvement in manganese transfer also however, after day 800 manganese
concentration in electrolyte continued to increase beyond levels previously seen. In reality
the volume of transfer of impurities had decreased but after day 800 there was a significant
increase in the manganese concentration in PLS. By day 1300 the manganese
concentration in PLS had increased almost three fold. On this basis if the coalescer and
wash stage had not been installed electrolyte concentrations would have exceeded
250ppm.

The chloride control is now at a stage where its has been necessary at times to dose the
electrolyte with chloride to maintain chloride in the range of 20-35ppm to generate good
EW cathode deposit morphology.

Electrolyte bleed has been reduced to a minimum for iron control. The modelling
undertaken to justify the projects was replicated in practice and in most cases bettered
under adverse operating conditions. When combined with an on-going organic treatment
programme the total flow rate exceed design.

The added advantage of the positioning of the combined wash stage and loaded organic
coalescer has been the significant reduction in requirement to clean both in-settler and
loaded organic coalescing media. Prior to the wash stage installation cleaning of
coalescing media was required almost monthly. This resulted in a need to clean at least
two sets of media every week. This requirement has reduced to irregular cleaning of media
on a 3 to 6 month cycle.

The Girilambone Copper project has been described by a number of papers (Readett,
Miller and Hutchinson 1996, Miller, Readett Webb and Miller, Dudley, etal). It is currently
undergoing a run down phase of the operation while treating residual copper in the heaps.

20
In order to optimise the operation of the SX-EW plant a number of scenarios were
analysed to determine how best to configure the plant. The result relied heavily on good
entrainment control in the SX to provide the conditions for minimum operating cost.
 Use of in-settler coalescing plus
 Loaded organic coalescing plus
 A wash stage.

This produced a situation that required minimal (to zero) electrolyte bleed – just enough for
to acidify the wash stage for iron removal. The saving in the cost of cobalt is considerable.
The electrolyte was high in iron but low in chloride so the current efficiency dropped.
However the Mn and Eh were in control. The SX used the lowest reagent concentration so
raffinate organic loss costs were minimised. Again modelling of the ‘real’ entrainments in
an SX plant were an integral part of determining the outcomes.

Bwana Mkubwa Mining Limited operate an agitation leach SX-EW plant in Zambia. The
new ore supply has higher levels of soluble silica and manganese with low levels of
soluble iron. As a result the plant PLS has silica saturation and a Mn:Fe ratio of up to 6:1.
Once the new ore source became a significant proportion of the feed, the plant crud
production increased significantly with large amounts of fluffy crud leading to massive crud
runs. The resultant entrainment loss transferred large amounts of manganese into the
electrolyte and a significant loss of electrolyte to raffinate. Production was limited and SX
recovery reduced dramatically.

The symptoms were extremely severe with permanganate forming in the EW and the
organic at high risk of oxidation and degradation. A multi pronged approach was
implemented to address the short and long term operating issues.
 It was evident that all SX stages needed to be operated in organic continuity to
eliminate the production of fluffy crud. In order to do this the resultant high
entrainment of PLS in the loaded organic needed to be reduced.
 In-settler coalescing was introduced to minimise the amount of entrainment in
advance streams as the settler designs were not the best. As well as this the interface
level control was improved along with better settler feed distribution and removal of
the third row of picket fences.
 A loaded organic tank was converted to an upflow coalescer.
 A replacement mixer-settler unit was partially built on site (to allow repairs on the
existing units while maintaining production). This was converted to a low acid wash
stage for removing residual entrained manganese while retaining chemically bound
iron.
 A large plate and frame filter was taken from another part of the circuit and converted
for use as crud and organic clay treatment use.

The result of the changes was a significant improvement in plant operation with:
 The elimination of crud from the circuit except for some minor production of a
compacting interfacial type
 Change in the electrolyte Mn:Fe ratio that has all but eliminated the addition of ferrous
sulphate to electrolyte for Eh control
 SX recovery at target isotherm levels
 Overall improved operating stability with the minimisation of inter-stage entrainment
and settler interface level excursions.

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 10.0 CONCLUSIONS

Entrainment control is an integral part of the design and successful operation of SX plants.
This aspect is generally poorly appreciated in many design offices to the detriment of the
project. Sequential SX plants have shown that entrainment is the most important aspect of
overall operating control due to cross contamination. The practical level of entrainment is
generally a lot higher than most operators or designers realise or acknowledge.

There are a large number of conditions that can lead to high entrainment levels. It is
important to understand the true drivers behind the particular entrainment so that the
proper action can be taken. In many cases the upset condition seen in the plant is a
second or third level symptom of an upstream entrainment event.

Action plans for addressing entrainment issues need to consider not just the immediate
relief of symptoms but the holistic SX and other plant sections that interact together. The
hard ware and operating condition changes that result from this approach generally
indicate a multiple number of activities with combinations of control points and systems
providing the low risk high efficiency outcomes.

When a new plant design is contemplated there is generally little cost difference between a
‘normal’ plant and one that will have low entrainment risks. Some small amount of extra
hardware will be provided but integrated with the unit designs to minimise cost impacts.

11.0 ACKNOWLEDGMENTS

The authors wish to acknowledge the co-operation of Straits Resources and First Quantum
Minerals management and personnel, and SKM in the preparation of this paper. Without this
corporate support much of the work undertaken in developing the concepts implemented on
these plants would not have seen the public domain.
12.0 REFERENCES

Dudley KA, Readett DJ and Weston JL, 2000 “Heap Leach, Solvent Extraction and
Electrowinning at the Girilambone Copper Company”, Minprex 2000, September 2000, AusIMM.

Dudley K.A., Readett D.J. and Moore, A. 2002 “Organic Growth of the Nifty Copper Operation
Solvent Extraction Plant” ALTA Copper Conference 2002, Perth, Australia

Giralico, M A, Post, T A, Greaves, M and Stevenson, E, 1998. “Introducing Lightnin’s Optimised

Integrated SX/EW Mixer-settler unit”, ALTA 1998 Copper Hydrometallurgy Forum, Brisbane.

Lewis, I. E., 1977, “Design of Mixer Settlers to Achieve Low Entrainment Losses and Reduce
Capital Costs”, Proceedings International Solvent Extraction Conference 1977, Vol 21, pp325-
333, CIM.

Miller, G., "The Problems of Manganese and its Effects on Copper SX-EW Operations", Copper
95 - Cobre 95, Vina del Mar, Chile.

Miller, G.M, “Modelling and Control of Transients in Solvent Extraction Mixer-Settlers”

Minprex 2000, September 2000, AusIMM.

Miller, G.M., “Mixer Aqueous Locking and Dynamic Settler Operation under Quasi Steady
State Conditions”, ALTA Copper Hydrometallurgy Conference 2000, Surfer’s Paradise,
October 2000.

Miller, G., Readett, D., Hutchinson, P., "Entrainment Coalescing in Copper SX Circuits", Isec '96,
Melbourne.

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Miller, G., Readett, D., Hutchinson, P., “Experience in Operating the Girilambone Copper SX-EW
Plant in Changing Chemical Environments”, Minerals Engineering `96, Brisbane.

Readett DJ and Marks CJ, 1989, “Optimisation of the Copper Electrowinning at BHAS”, Non
Ferrous Smelting Symposium, Port Pirie, AusIMM pp175-180.

Readett, D.J. and Miller, G.M., "The Impact of Silica on Solvent Extraction: Girilambone Copper
Company, Case Study", Copper 95 - Cobre 95, Vina del Mar, Chile.

Readett, D.J., Miller, G.M. and Hutchinson, P, (1996) “Process Development at GCC”
Proceedings of Minerals Engineering ‘96, Brisbane, Australia.

Readett, D.J., Miller, G.M. and Holle, H (1996) “Solvent Extraction Process Development at
Girilambone Copper Company - Predicted v Plant Practice” Proceedings of Chemeca ‘96,
Sydney, Australia.

Scheonbrunn F and Keyser P, 1999, “Loaded Organic Entrainment Reduction using a

Pacesetter Separator”, in ALTA 1999 Copper Hydrometallurgy Forum, Gold Coast.

Stanbridge D and Sullivan J, “One Example Of How Offshore Oil & Gas Industry
Technology Can Be Of Benefit To Hydrometallurgy”, Second International Conference on
CFD in the Minerals and Process Industries, CSIRO, Melbourne, December 1999.

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