Faculty of Engineering and the Built Environment

Department of Chemical Engineering

CHE2005W
PRACTICAL 2 (Online mode)
SOLVENT EXTRACTION FROM COBALT FROM AQUEOUS SOLUTION

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 prac objectives and experimental design and procedure. Instructions for the
pre-submission and presentation submission tasks follow. You can select the links below to access various
sections of the manual.

Content
1. Background
2. Solvent Extraction
3. Factors affecting separation by solvent extraction
4. Analysis of solvent extraction performance
5. Objectives
6. Experimental design and procedure
7. Sample analysis
8. Safety considerations
9. References
10. Additional reading

Pre-submission task

Submission task

Plagiarism
In all outputs you produce, whether a written document, presentation or poster, you must reference ideas,
thoughts, images, etc. of the original author/s appropriately, using in-text (direct or indirect) citations and
have included a list of references. Aside from the obvious forms of plagiarism such as copying and pasting
portions of text from the web or previous and current peers, the most common form is due to poor
paraphrasing. Information on what constitutes plagiarism can be found using this link:
http://www.uct.ac.za/sites/default/files/image_tool/images/328/about/policies/Guide_StudentGuideOn
AvoidingPlagiarism.pdf
Failure to reference appropriately constitutes an ethical breach and is considered plagiarism, which is a
serious offence and will result in disciplinary action being taken against students who plagiarise.

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 Faculty of Engineering and the Built Environment
Department of Chemical Engineering

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.

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Department of Chemical Engineering

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.
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.
Q O
CH3

P Q = CH3 C CH2 CH CH2

CH3 CH3
Q OH
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:

(M n+ )aq + ((n + m)RH)org ↔ (MR n . 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:

(M n+ )aq + ((n + m)RH)org + (nNaOH)aq ↔ (MR n . mRH)org + (nH2 O)aq + (nNa+ )aq (2)

More specifically, for the system under consideration, the extraction reactions for Co 2+

(Co2+ )aq + (3 RH)org + (2NaOH)aq ↔ (CoR 2 . (RH)org ) + (2H2 O)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:

[𝑀𝑛+ ]𝑎𝑞,0 ∙ 𝑉𝑎𝑞,0 − [𝑀𝑛+ ]𝑎𝑞 ∙ 𝑉𝑎𝑞 (4)

% 𝐸𝑥𝑡𝑟𝑎𝑐𝑡𝑖𝑜𝑛 =
[𝑀𝑛+ ]𝑎𝑞,0 ∙ 𝑉𝑎𝑞,0

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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Department of Chemical Engineering

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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A: Separation funnel

B: pH and temperature probes

C: Magnetic stirrer

D: pH probe stand

E: pH meter display

Figure 2: Main experimental set-up: pH meter, magnetic stirrer and separation funnel.

A: 100 mL Measuring cylinder

B: 50 mL Measuring cylinder
(50ml)
C: 500 mL Beaker
(500ml)
D: 200 mL Volumetric flask

E: Funnel

F: Cyanex 272 in Kerosene

Figure 3: General glassware and consumables

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Department of Chemical Engineering

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.

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.

Factor Levels

Extractant concentration 15 vol% Cyanex 272 in Kerosene

Aqueous to organic ratio (A/O) 2:1 (100 mL A: 50 mL O) 1:1 (75 mL A: 75 mL O)

pH of aqueous solution* 3.5 4.5 5.5

* sulphuric acid or sodium hydroxide is added to adjust the pH to the required level for extraction.

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Department of Chemical Engineering

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.
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.

Steps i – v: Step viii: Step ix:

Aqueous (pink colour) and organic Mixture transferred to 20 ml aqueous sample
(blue colour) solutions added in separation funnel. collected for analysis.
500mL beaker.
Figure 6: Flow diagram of Cobalt extraction.

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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)
• 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.

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Ritcey, G.M. and Ashbrook, A.W. (1979) Solvent extraction: principles and applications to process
metallurgy, Elsevier Science, Amsterdam, Netherlands.
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

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Pre-submission task instructions

In a single page A4 document, answer the following questions. These questions are aimed at
preparing you for the analysis of your data (which will follow). State all your assumptions clearly.
1. Calculate the mass of CoSO4·7H2O required to achieve the standard solution concentration
of 4 g/L of Co2+ for a total solution volume of 200 mL. Show all workings.
2. Given the volume of organic phase used, calculate the mass of extractant supplied to the
system for each A/O ratio. Compare this with the stoichiometric amount of extractant
required for complete extraction in each case.
3. Determine if the extractant has been provided in excess and if so, discuss why?

Individual presentation submission task instructions

Please submit a 5 to 7-minute video presentation with accompanying PowerPoint presentation

slides, where you provide:
• A brief background describing the use of solvent extraction for the separation of cobalt
from aqueous solution and your understanding of why pH and A/O ratio impact on
extraction performance.
• The results of your data analysis and discuss your findings, ensuring that you speak to the
prac objectives.
• Your conclusions and recommendations.
Be sure to discuss your findings with respect to your pre-submission task and conclude on the
importance of stage extraction.
Note: If a video recording is not possible, please provide the PowerPoint presentation along with
a voice note.

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