Faculty of Engineering and the Built Environment

Department of Chemical Engineering

SOLVENT EXTRACTION FROM COBALT FROM AQUEOUS

SOLUTION

2024 CHE2005W PRACTICAL 2

This document presents the information on the solvent extraction practical. Here you will find a
brief background presenting the scenario, description of the solvent extraction process and factors
affecting separation, followed by the practical objectives and experimental design and procedure.

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1. BACKGROUND
Metals of value are extracted from minerals using various techniques. In hydrometallurgy, base
metals such as cobalt, copper, nickel and zinc, are extracted through the dissolution of minerals
using chemical reagents, into aqueous solution. Hydrometallurgy is the preferred route for the
production of cobalt from cobalt sulphide mattes and precipitates in stirred tank reactors.
In the process of dissolving the solid mineral particles, the metals ions are leached into solution.
Typically, the mineral is composed of more than one metal resulting in multiple metals present in
the aqueous solution. In addition to cobalt, the other metals that could report to solution are copper,
nickel, iron, zinc and trace amounts of impurities such as lead and manganese.
The aqueous solution containing the multiple dissolved metals is referred to as the pregnant leach
solution. Downstream processing of the pregnant leach solution is required to recover the metal of
value, cobalt, and separate it from the unwanted components. This separation process may involve
unit operations such as precipitation, crystallisation, adsorption, solvent extraction, ion exchange,
or a combination of these technologies.
The separation process will produce multiple solution product streams, each composed of a single
dissolved metal at a concentration higher than in the original pregnant leach solution and containing
low concentrations of impurities or secondary metals. The final process is referred to as product
refinement and involves the production of saleable products from the single-metal solutions. This
may be achieved through unit operations such as precipitation (e.g. chemical reduction),
crystallisation, and electrowinning.
In this practical, cobalt ion will be removed from a synthetic, pregnant leach solution composed of
a cobalt sulphate leach solution, using solvent extraction as the method of separation.

2. SOLVENT EXTRACTION
Solvent extraction is a separation process that exploits the relative solubility of a component in two
different immiscible liquid phases. The component from the aqueous liquid mixture is selectively
removed by dissolving it in an organic phase. In this prac, metal ion will be extracted from the
pregnant leach solution (aqueous phase) by mixing with extractant (organic phase). The process of
mixing allows for interaction/contacting between specific aqueous species and the extractant to
form organometallic complexes that are soluble in the organic phase.
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The chemical mechanism by which this occurs can involve ion pair transfer, ion exchange, or
chelation (Habashi, 1999). The selected organic phase should not be miscible with the aqueous
phase, and this would then allow separation of the two phases by gravity settling. Typically, the
aqueous phase has a higher density than the organic phase, and hence reports to the bottom of the
settling unit.
The preferred extractant for the separation of cobalt from a pregnant cobalt sulphate leach solution
is bis (2,4,4-trimethyl pentyl) phosphinic acid, which trades under the commercial names of
Cyanex 272 and Lix 272 (Crundwell et al., 2011). The structure of this extractant is shown in Figure
1.

Figure 1. Cyanex 272 structure

Olivier (2011) presented an overview of the chemistry describing cobalt extraction with Cyanex
272. Reaction 1 is the general reaction describing the ion exchange reaction between Cyanex 272
and metallic cations in aqueous solutions:

(Mn+)aq + ((n + m)RH)org ↔ (MRn. mRH)org + (nH+)aq (1)

where Mn+ is an n-valent metal cation, RH refers to the extractant with proton H+, and the subscripts
aq and org refer to species in the aqueous and organic phases, respectively. It can thus be seen that
the capacity of an extractant for extracting specific ions will depend on the stoichiometry of the
extraction reaction.
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3. FACTORS AFFECTING SEPARATON BY SOLVENT EXTRACTION

pH of aqueous solution
The extraction behaviour of different metallic cations is highly dependent on the pH of the aqueous
solution. For the system under consideration, it has been reported that cobalt extraction increases
from approximately 10% at pH 3 to almost complete extraction at pH 6 (Habashi, 1999).
Considering Reaction 1, the exchange of hydrogen ions from the organic phase to the aqueous
phase during the extraction reaction will increase the acidity of the aqueous solution, thereby
shifting the reaction equilibrium to the left and decreasing the extent of extraction achievable. For
this reason, the pH of the extraction process (or aqueous feed solution) is usually controlled by the
addition of a base such as NaOH to neutralise the H+ formed:

(Mn+)aq + ((n+m)RH)org + (nNaOH)aq ↔ (MRn.mRH)org + (nH2O)aq+(nNa+)aq (2)

More specifically, for the system under consideration, the extraction reactions for Co2+

(Co2+)aq + (3 RH)org + (2NaOH)aq ↔ (CoR2.(RH)org) + (2H2O)aq + (2Na+)aq (3)

The extractants (e.g. Cyanex 272) are usually mixed with organic solvents (referred to as the
diluents) in order to manipulate the physical properties of the organic phase to allow good
extraction and phase separation. In this study, kerosene is used as the diluent.

Other variables affecting solvent extraction performance

Apart from the pH of the aqueous solution and the extractant type, which affects the stoichiometry,
various other operating variables can affect the extent of extraction and the degree of separation.
The most important variables include:
• A/O volumetric ratio: this refers to ratio of the volumetric amount of aqueous phase in the
system to the volumetric amount of organic phase in the system. Variation of the A/O ratio
while maintaining the remainder of the variable’s constant will generate data that can be
used to construct extraction isotherms.
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• Temperature: various effects of temperature on the extraction behaviour have been reported
in literature (Olivier, 2011). In general, temperature could affect the stability of
organometallic complexes, but the largest effect will be that of temperature on the physical
properties of the organic phase, which could influence the rate and extent of phase
separation achieved.
• Diluent type: the effect of the type of organic solvent used as diluent on the solvent
extraction will depend on the extractant type. Interaction between the diluent and the
extractant, and hence extraction performance, is possible. Olivier (2011) has shown that
organic solvents typically used as diluent all yield similar results during the extraction of
cobalt and iron from a cobalt sulphate solution when using Cyanex 272 as extractant.
• Extractant concentration: extractant concentration refers to the composition of the organic
phase and gives an indication of the amount of extractant relative to the amount of diluent.
Typically, the distribution coefficient increases with an increase in the concentration of the
extractant in the organic phase (Habashi, 1999). An upper limit exists above which the
physical properties of the organic phase (e.g. viscosity) will not allow satisfactory
extraction and phase separation.
• Agitation time: sufficient mixing time should be allowed for equilibrium to be achieved
between the aqueous and the organic phases.

4. ANALYSIS OF SOLVENT EXTRACTION PERFORMANCE

The performance of the solvent extraction process can be determined by calculating the percentage
extraction. The percentage extraction of a particular component refers to the percentage of the
component originally present in the aqueous phase that was transferred to the organic phase and is
described using this equation:

where [Mn+]aq,0 is the initial concentration of the component in the aqueous phase, [Mn+]aq is the
concentration in the aqueous phase after extraction, and Vaq,0 and Vaq are the volume of the aqueous
phase before and after extraction, respectively.
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5. OBJECTIVES
The objectives of the practical are to:
• Perform solvent extraction in stages to assess the effectiveness of separation of cobalt ions
from the aqueous phase.
• To establish the relevance of stage processing in solvent extraction

6. EXPERIMENTAL DESIGN AND PROCEDURE

6.1. Experimental set-up
The main experimental set-up is displayed in Figure 2, while the general consumables used are
depicted in Figure 3. The list of supporting equipment required to complete the practical include
the following:
• laboratory mass balance
• magnetic stirrer plates [Fig. 2.C]
• magnetic stirrer bars
• pH and temperature probe and meter [Fig 2.B and E]
• separation funnels [Fig 2.A]
• sample bottles
• glass transfer pipettes
• general glassware and consumables (measuring cylinders, beakers, etc.)
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Figure 2: Main experimental set-up: pH meter, magnetic stirrer and separation funnel.
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Figure 3: General glassware and consumables

6.2. Chemicals required

The chemicals necessary to conduct the practical experiments include the following:
• Cobalt sulphate hydrate (CoSO4·7H2O) powder, depicted in Figure 4 below.
• The base solution (NaOH) provided in a solution of 0.3M concentration.
• The acid solution (H2SO4) provided as a prepared concentration of 0.6M.
• The organic phase provided contains 15 vol% Cyanex 272 diluted in kerosene. Commercial
Cyanex 272 used to prepare the organic phase has a specific gravity of 0.92 and a purity of
85% (each 100 g of Cyanex 272 contains 85 g of the active extractant, bis (2,4,4-trimethyl
pentyl) phosphinic acid). The Cyanex 272 in kerosene solution is depicted in Figure 3.F
above.
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Figure 4: Cobalt sulphate hydrate powder.

6.3. Preparation of synthetic leach solution

Prepare a 200 mL volume of a synthetic leach solution composed of 4 g/L Co (II) by following the
steps outlined below.
I. Weigh off the appropriate amount of CoSO4·7H2O to achieve the desired Co2+
concentration in 200 mL of the solution. (Note: This must be calculated by student)
II. Measure 100 mL demineralised water and decant into a 200mL volumetric flask.
III. Add the CoSO4·7H2O to the water measured off in step ii.
IV. Ensure that all the base metal salts are dissolved.
V. Add demineralised water to make up a total solution volume of 200 mL.
VI. Measure out 20mL sample and decant into labelled sample container. This will be referred
to as the standard sample.
VII. Transfer rest of sample to a 500mL beaker and add sulphuric acid or sodium hydroxide to
adjust the pH of the solution to a value of 3.
VIII. Transfer sample back to 200mL volumetric flask.
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Figure 5: Flow diagram of synthetic leach solution preparation.

6.4.Cobalt extraction conditions

Cobalt extraction from the aqueous phase to the organic phase is performed across factors and at
different levels as highlighted in the table below.

6.5.Procedure for Cobalt extraction

The following steps are followed to achieve extraction of cobalt from the aqueous mixture (also
depicted in images provided in Figure 6 below.
I. Add the required amount of aqueous solution to the mixing beaker.
II. Add the required amount of organic solution to the mixing beaker
III. Ensure that a constant temperature at about 25°C is maintained before and after mixing the
solutions.
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IV. Place the pH probe into the mixing beaker (careful not to contact the probe with the
magnetic stirrer.
V. Switch on the magnetic stirrer and set the stirrer speed at an appropriate value to achieve
good mixing of the phases without causing liquid losses due to splashing (make sure that
the stirrer bar does not hit the pH probe).
VI. Using a glass transfer pipette, gradually add NaOH or H2SO4 to the aqueous-organic
mixture to achieve the desired pH (chosen from Table 1).
VII. Mix the aqueous and organic phases until a constant pH is obtained.
VIII. Transfer the mixture to a separation funnel and allow the phases to separate.
IX. Collect about 20mL of the aqueous phase and transfer to a clearly labelled sample container.
X. Measure the volume of the remaining aqueous phase and transfer it to a 500ml beaker.
XI. Discard the loaded organic phase into the appropriate waste container.
XII. Repeat steps i to x for the 2nd stage of extraction.

Figure 6: Flow diagram of Cobalt extraction.

7. SAMPLE ANALYSIS
All samples are submitted to the analytical lab for atomic absorption spectroscopy analysis (AAS).
The 3 samples are:
• 1 sample from the synthetic leach solution used as feed for the solvent extraction (this is
the standard sample)
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• 2 aqueous phase samples collected from the 2-stage extraction process.

8. SAFETY CONSIDERATIONS
In addition to the general laboratory safety rules, which include the wearing of safety glasses,
closed shoes, and a laboratory coat, the following safety hazards are of particular importance:
• The practical involves working with both aqueous and organic liquids close to electrical
connections. Care should be taken to avoid spillage of liquids; any spillage must be
contained and cleaned immediately.
• Kerosene is a toxic flammable liquid and should be handled with the necessary care. All
waste material must be placed in the containers provided.

9. REFERENCES
Crundwell, F.K., Moats, M.S., Ramachandran, V., Robinson, T.G. and Davenport, W.G. (2011)
Extractive metallurgy of Cobalt, cobalt and platinum-group metals, Elsevier, Oxford, United
Kingdom (Available electronically: http://www.sciencedirect.com/science/book
/9780080968094).
Habashi, F. (1999) Textbook of Hydrometallurgy, Métallurgie Extractive Québec, Québec,
Canada.
Olivier, M.C. (2011) Developing a solvent extraction process for the separation of cobalt and iron
from Cobalt sulfate solutions, MScEng Thesis, Department of Process Engineering, Stellenbosch
University, South Africa.

10. ADDITIONAL READING

Flett, D.S. (2005) Solvent extraction in hydrometallurgy: the role of organophosphorus extractants,
Journal of Organometallic Chemistry, 690(10):2426-2438.
Nogueira, C.A., Oliveira, P.C. and Pedrosa, F.M. (2009) Separation of cadmium, cobalt, and Cobalt
by solvent extraction using the Cobalt salts of the extractants, Solvent Extraction and Ion Exchange,
27(2):295-311.
Ritcey, G.M. and Ashbrook, A.W. (1979) Solvent extraction: principles and applications to process
metallurgy, Elsevier Science, Amsterdam, Netherlands.
 Faculty of Engineering and the Built Environment
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Rydberg, J. (2004) Solvent extraction principles and practice, Marcel Dekker Inc., New York,
United States of America.
Tsakiridis, P. and Agatzini-Leonardou, S. (2004) Process for the recovery of cobalt and Cobalt in
the presence of magnesium from sulfate solutions by Cyanex 272 and Cyanex 302, Minerals
Engineering, 17(7-8):913-923.
Yu, X., Gu, G., Fu, X., Su, B. and Zhang, H. (2001) Thermochemistry study on the extraction of
Co(II) and Ni(II) with Cyanex 272 in kerosene, Solvent Extraction and Ion Exchange, 19(5):939-
943