Department of Materials Science and Metallurgical Engineering

Hydrometallurgy NHM 411

Assignment 1

C.J. van Niekerk

25156773

cjsexybeast@gmail.com
Table of Contents

1. Introduction.......................................................................................................................2

2. Discussion: Copper removal from nickel and cobalt circuits.........................................2

2.1 Direct Electrolysis of Matte........................................................................................2

2.2 Chloride Leach Processes.........................................................................................3

2.3 Ammonia pressure leach...........................................................................................4

2.4 Atmospheric Acid Leach............................................................................................5

2.5 Acid Pressure Leach..................................................................................................6

2.6 Pressure Carbonyl. Process.......................................................................................8

3. Discussion: Solvent extraction and ion exchange as alternative Cu extractants..........9

4. References...........................................................................................................................10

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 1. Introduction

The method used for copper and nickel extraction in various industries from Co-rich Cu-Ni mattes depends
on the actual copper content of the specific matte being treated. The mattes are divided into two categories
according to their copper content, i.e. high copper mattes and low copper mattes. High copper mattes
contain over 25% Cu and the low copper mattes contain up to 7% Cu. In summary, the high copper mattes
are treated through an acid chloride leach process, and by atmospheric and pressure sulphuric acid leach
processes. Low copper mattes are treated through direct nickel matte electrolysis, a ferric chloride leach
and an ammoniacal pressure leach process [1]. The subsequent discussion will investigate the copper
removal from nickel leaching methods in some of the above mentioned processes and, if applicable,
suggest alternatives.

2. Discussion: Copper removal from nickel and cobalt circuits

2.1 Direct Electrolysis of Matte

Figure 1 shows the copper and arsenic removal step from the Inco Thompson Refinery flow sheet for the
direct electrolysis of Co rich Cu-Ni mattes as it has been used by the Thompson Refinery since 1961 [1].

Figure 1: Copper/Arsenic removal step from the Direct Electrolysis process [1].

The electrolyte from the tank house where electrolysis is carried out is sent to the copper/arsenic removal
step. When the copper concentration in the anolyte is low (as with low copper mattes), the copper may be
precipitated from the solution as a sulphide [2]. Hydrogen sulphide is used in figure 1 for this purpose.
Equation 1 displays the reaction that takes place between copper and hydrogen sulphide to produce
copper sulphide.

H2S + Cu2+ → CuS + 2H+ (1)

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Evident from equation 1 is that acid is generated at two moles for every mole of CuS formed. To neutralise
this acid, crushed spent anode material is added to the solution. It also contains some nickel which acts as
a catalyst for the reaction [1, 2].

A disadvantage of using H 2S is that it is a poisonous and corrosive gas. It is advantageous, though, to use
this step in the process as is, because it acts as a purification and recovery step in one process block on
the flowsheet [2]. It also renders the plant more cost effective by extracting copper in a single processing
step.

2.2 Chloride Leach Processes

Figure 2 shows the copper removal steps from the nickel matte chloride leach process used at
Falconbridge in Kristiansand. Falconbridge in Sudbury implements a similar circuit [1].

Figure 2: Copper removal steps from the Chloride Leach Process [1].

Cu is precipitated out of the slurry in the copper removal block on the above flow diagram by cementation
to less than 1g/L [1]. Equation 2 represents this reaction [2].

Ni3S2 + 3Cu2+ → 3Ni2+ + CuS + Cu2S (2)

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Elemental Cu0 and S0 are also formed during this step. In the copper removal step, Cu and Ni are
solubilised. It is then brought into contact with fresh Cu-Ni matte, which solubilises more Ni and forms a
copper sulphide which precipitates out through cementation [1, 2].

The chlorine leach residue of equation 2 is then sent to a roaster to extract copper where, with a
combination of high temperatures and oxygen, the elemental sulphur and sulphides are converted to
sulphur dioxide [1]. Copper is converted to a calcine as in the following exemplar equations.

Roaster equations: 2CuS + 2O2 → 2CuO + SO2 (3)

S0 + O2 → SO2 (4)

The calcine is then leached in sulphuric acid and is finally precipitated out by conventional electrowinning.
The following equations are that of Cu leaching and the anodic and cathodic reactions of electrowinning [2].

Final leach Reaction: CuO + H2SO4 → CuSO4 + H2O (5)

Electrowinning: Anodic: H2 → 2H+ + 2e- (6)

Electrowinning: Cathodic: CuSO4 + 2e- → Cu + SO42- (7)
Final Electrowinning reaction: CuSO4 + H2 → Cu + H2SO4
(8)

The copper leaves the process as Cu cathodes.

An advantage of this particular copper extraction circuit compared to any single stage copper extraction is
that pure saleable copper cathodes are produced as supposed to other circuits where a copper concentrate
is sent to a smelter. A disadvantage is that the size of the plant has to be able to incorporate such a long
process line and preferably be able to do all of the extraction steps on one plant. Cost might be an issue
with regards to power consumption at each step in the process in comparison with a plant that extracts
copper in a single stage.

2.3 Ammonia pressure leach

Figure 3 shows the so called Copper Boil stage of the Sherritt Refinery process implemented in their plant
at Fort Saskatchewan, Alberta [1]. The nickel solution enters the copper boil from the adjustment leach
stage. In this solution, copper is present as copper ammine from the reaction that took place in the
adjustment leach [2]:
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 CuS + nNH3 + 2O2 → [M(NH3)n]2+ + SO42- (9)

Figure 3: Copper Boil from the Ammonia Pressure Leach process [1].

In the copper boil equation 9 is reversed to extract copper from the solution as copper sulphide through the
addition of elemental sulphur, producing ammonia gas [2].

[Cu(NH3)n]2+ + S0 → CuS + NH3 (10)

CuS is sent for further refinement through smelting.

An advantage of this circuit is that it would be lower in cost than the chloride leach for example, due to a
lower power input – seeing that the copper boil is single stage extraction whereas in chloride leach, it is a
four stage process including roasting. The process also has minimum corrosion problems as compared to
a plant dealing with sulphuric acid. Because of the nature of copper ammine, a major disadvantage is that
only low copper mattes can be treated in this manner as high copper mattes would consume excessively
large amounts of the NH3 reagent.

2.4 Atmospheric Acid Leach

Figure 4 shows the copper extraction stages during the atmospheric acid leach of the Outokumpu
Harjavalta Nickel Refinery in Finland [1]. Copper is leached during the second and third stages of the
subsequent flow diagram according to the following reactions.

Anodic: O2 + 4H+ + 4e- → 2H2O (11)

Cathodic: Cu → Cu2+ + 2e- (12)
Final Reaction: 2Cu + O2 + 4H+ → 2Cu2+ + 2H2O (13)

In the first stage some copper is cemented out of solution on nickel during the first few minutes of leaching
when copper is contacted by metallic nickel [1, 3]. Equation 14 illustrates this.

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 Cu2+ + Ni → Cu + Ni2+ (14)

Figure 4: Copper extraction stages during the atmospheric pressure leach process [1].

The leaching is carried out in an acid sulphate solution with air being sparged through the system [1].

Copper containing solution leaves the three-stage, counter-current leaching process from stage 2 for
electrowinning. Equation 15 illustrates the reaction of electrowinning.

Cu2+ + H2 → 2H+ + Cu (15)

An advantage of this process is that it can treat high copper mattes cost effectively, solubilising the copper
through two leaching stages and precipitating copper out as copper powder in one electrowinning step. Cu
is produced as copper powder due to a low current density on the electrowinning cell which also renders
the process cheaper than the copper extraction in a chloride leach process for example.

A disadvantage is that not all the copper is removed in the electrowinning step. Electrolyte from the third
leaching stage goes to a pressure leach where CuS residue is formed for further refinement through
smelting.

2.5 Acid Pressure Leach

Figure 5 shows the copper extraction stages of the acid pressure leach process as implemented by the
Impala Platinum Nickel-Copper Refinery [1].

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During the initial leaching of the Ni-Cu matte, copper is cemented as CuS as Ni is solubilised from Ni 3S4 as
follows:

Ni3S4 + 3Cu2+ + H2O + 3/2O2 → 3Ni2+ + 3CuS + 2H+ + SO42- (16)

CuS is then oxidised with oxygen to form Cu 2+ and SO42- ,

CuS + 2O2 → Cu2+ + SO42- (17)

which passes through to the next stage of Copper Removal [3]. Some Cu 2S and Cu0 also forms in the
process.

Figure 5: Copper Removal stages during the Acid Pressure Leach Process [1].

Nickel powder is added as a catalyst for the reaction with sodium hydrosulphide to precipitate copper. The
Residue is passed through a second leaching stage where copper is leached and subsequently treated
with sulphur dioxide to precipitate copper and selenium as a copper (I) selenide. Copper is finally extracted
via electrowinning into copper cathodes [1].

Selenium removal takes place according to the following equation.

Cu2+ + SO2 → Cu+ + SO42- (18)

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The copper (I) then reacts to form copper (I) selenide according to equation 19.

Cu+ + Se2- → Cu2Se (19)

During electrowinning, copper is precipitated out and the Fe 3+ and Ni2+ that is still in solution are recirculated
back in the process with the spent electrolyte. Electrowinning takes place according to equation 20.

Cu2+ + H2 → Cu + 2H+ (20)

This process will be fairly expensive compared to other one stage copper removal circuits and will need a
large plant area to accommodate all the steps in the extraction of copper. An advantage is that copper is
refined on the same plant as Ni and no additional smelting of copper is necessary after the
hydrometallurgical treatment of the matte.

2.6 Pressure Carbonyl. Process

Figure 6 below shows the copper extraction step in the pressure carbonyl process of Inco at Copper Cliff
(CCNR) [1].

Figure 6: Copper extraction step in the Pressure Carbonyl Process [1].

Although the Inco Pressure Carbonyl Process is not exclusively Hydrometallurgical, the copper removal is.
The copper removal stage takes place in a two stage hydrometallurgical acid pressure leach followed by an
electrowinning step for copper recovery.

3. Discussion: Solvent extraction and ion exchange as alternative Cu extractants

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Solvent extraction is mainly used in the above mentioned circuits, where applicable, for cobalt extraction
[1]. Yet, solvent extraction might be a good alternative in some of these circuits for use in copper
extraction.

Ion exchange is done in batch processes, where solvent extraction is carried out continuously [2]. Solvent
extraction also has a high capacity for metal loading and subsequent stripping. Solvent extraction is a good
choice for the recovery of a metal from a leach solution as in the case of copper removal from the nickel
leach residue where ion exchange is used more often in uranium extraction [2].

In deciding which process might be amiable to solvent extraction, one has to consider the pH of the
operation. Solvent extraction will not be plausible in too acidic leaching circuits as H + takes part in the
reaction (Le Chatelier’s principle):

Cu2+ + H2X ↔ CuX + 2H+ (21)

Therefore, solvent extraction might be possible in the chloride leach process and in the ammonium
pressure leach.

Copper may be extracted from the ammoniacal leach solution by using the extractant LIX84_40 vol%
diluted with kerosene. Nickel and copper are co-extracted in this process. The ammonia that is also
absorbed by the extractant is removed prior to nickel stripping, which takes place before copper is stripped

An advantage of using solvent extraction in the ammonium process would be a minimising of the circuit
size and optimising floor area available to the rest of the plant and maybe even elimination of the roasting
stage. It would be less power intensive, considering the amounts of electricity consumed by the roaster.

Solvent extraction might be possible in the atmospheric acid leach process with Keelex with an organic to
aqueous ratio of 1:1 provided that the aqueous H 2SO4 concentration remains as low as possible, in the
range of, or below 20g/L [2], or with Kerosene at a pH of about 2.6 [4]. A major disadvantage on any of the
above mentioned solvent extraction examples is that the pH has to change almost drastically from one
processing step to another and tight control needs to be exerted on the pH and also the temperature.

References
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[1] Kerfoot, G.E., Weir, D. R. The hydro and electrometallurgy of nickel and cobalt. Sherritt Gordon Mines
l ltd. Fort Saskatchewan, Alberta, Canada.

[2] Habashi, F. Textbook of Hydrometallurgy. 2nd edition, 1999, Laval University, Quebec City, Canada,
p p. 303, 470, 507, 623, 624

[3] Rademan, J.A.M., Lorenzen, L., van Deventer, J.S.J. The Leaching characteristics of Ni-Cu matte in t
h the acid-oxygen pressure leach process at Impala . 1999. Department of Chemical Engineering, U ni
v University of Stellenbosch, South Africa.

[4] X. Zhang, X. Li, H. Cao, Y. Zhang. 2009. Separation of copper, iron (III), zinc and nickel from nitrate s
ol solution by solvent extraction using LK-C2. Department of Chemical Engineering, Tianjin University, T
ia Tianjin 300072, China.

[5] C. Parija, P.V.R., B. Sarma. 1999. Separation of nickel and copper from ammoniacal solutions through
c co-extraction and selective stripping using LIX84 as the extractant. Regional Research Laboratory ( C S
IR (CSIR), Bhubaneswar 751013, Orissa, India.

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