CHAPTER2 LITERATURE SURVEY

2.1 Hydrometallurgy
2. 2 Leaching
2.3 Sulphide minerals containing nickel, copper and cobalt
2.4 Familiar extracting and refining processes for nickel sulphides
2.5 Fundamentals of sulphide leaching
2.6 Previous investigation on nickel, copper and cobalt sulphide leachinig
2:7 Moss bauer spectroscopy

2.1 Hydrometallurgy

Hydrometallurgy will have an increasing role to play in the future regarding the
extraction of valuable metals from sulphide minerals. It is unique in its application to
low-grade ores, which cannot be beneficiated economically. It should be viewed as an
alternative technology having high chemical specificity. In the following section the
basic principles and fundamentals of hydrometallurgy are explained (Osseo-Asare &
Miller, 1982:6).

2.1.1 Hydrometallurgy versus Pyrometallurgy

Whether a metal is extracted in a water environment or at high temperatures 1s, in

principle, immaterial. Each extractive situation must be assessed on its own merits by the
consideration of such factors as capital and operating costs and the environmental impact
of the two different options that are available (Woollacott & Eric, 1994:213).

The more general characteristics of hydrometallurgy, which differ from pyrometallurgy

are parameters such as low operating temperatures, low reaction rates, more
environmental friendly, larger plant size for a given throughput of material, low unit costs
and selective chemical reactions (Hayes, 1993:227).

According to Bautista (1984:v) the hydrometallurgical route for the recovery of a metal,
where dissolution (leaching), separation, concentration and reduction to the metal is
carried out at near ambient temperature, is becoming more competitive with the
conventional high temperature processes used in the smelting of metals.
D.S. SMIT 4
CHAPTER2 LITERATURE SURVEY

2.1.2 The basic principles of hydrometallugry

When the chemical processing of metals is conducted in an aqueous environment, the

technology employed is termed hydrometallurgy, which involves three distinct stages
(Woollacott & Eric, 1994:321):

> The metal of interest must first be transferred from the solid feed material (ores,
concentrates, etc.) into an aqueous solution.
> The condition of this metal-bearing solution (or solutions formed from it) must then
be concentrated and purified.
> The metal must then be recovered from the purified solution in the solid state.

The transfer of the targeted metal from the solid feed material into an aqueous solution is
accomplished by leaching. The dissolution of the solid material is more selective than
the conventional smelting process, and the metal-bearing components dissolve, while the
other components do not. A subsequent separation of the solution from the unaffected
solids will then result in a separation of the metal from the unwanted components in the
feed material.

The solution from a leaching process invariably contains impurities that need to be
removed or reduced to as low as possible levels. In some cases, the concentration of the
metal of interest is too low, and some form of concentration needs to be applied before
the metal can be extracted economically. The concentration and/or purifying process of a
metal-bearing solution can be accomplished in one of three ways.

> Evaporation. Boiling of a solution under reduced pressure achieves an increase in

the concentration of the metal, because it removes water from the solution. Often this
process is not economical on a large scale, and it does not purify the 'solution in any
way.

> Precipitation process. The precipitation of one of the components from the solution
occurs, which is then followed by the separation of the precipitate and the solution.

D.S. SMIT 5
CHAPTER2 LITERATURE SURVEY

The extraction of nickel, copper and cobalt from a sulphide ore by means of pressure-acid
leaching is viable under specific conditions. Copper dissolution from chalcopyrite,
however, requires longer retention times and higher temperatures to ensure complete
extraction due to the passivation of the mineral surface. The leaching efficiency depends
greatly on the specific process variables such as temperature, pressure, pH, particle grain
size and leach reagent. An increase in temperature and pressure enhances the reaction
rate which leads to smaller retention times required for complete dissolution. High leach
reagent concentrations such as sulphuric acid, does not greatly improve the extraction of
the valuable metal but only influences the by-product formation. Mechanical activation
by means of ultra fine milling offers significant advantages for the extraction of the
valuable metals from sulphide ores.

The oxidising of the minerals pyrrhotite (Fe 1_xS), pentlandite (Ni,Fe) 9Ss and chalcopyrite
(CuFeS 2), at a oxygen partial pressure of 10 bar and a temperature of ll0°C in the
presence of sulphuric acid, can be described by means of the following process reactions:

.......... (12)

.......... (13)

.......... (14)

The iron hydrolysis and precipitation that occur during the leaching of these minerals can
be described by the following reactions:

......... (15)

......... (16)

The activation energy deduced for the extraction of nickel and copper from the sulphide
ore ranged between 20 and 100 kJ/mol K, and no apparent activation energy value was
found for the extraction of cobalt from pentlandite.

D.S. SMIT 27
CHAPTER2 LITERATURE SURVEY

2. 7 Moss bauer spectroscopy

The recoilless emission of gamma radiation, followed by its resonant absorption by a

sample, was discovered by Rudolf Mossbauer in 1958 and is now known as the
Mossbauer Effect.

2.7.1 An introduction to Mossbauer spectroscopy

According to Cohen (1976:2), the Mossbauer effect is the recoilless emtsston by

radioactive nuclei and resonant reabsorption of y-rays, which arises from the nuclear
excited states. These y-rays are electromagnetic radiation and have no electrical charge
and are absorbed or scattered by energetic collisions when passing through matter. The
very small energy changes can be measured by the Mossbauer effect to give information
about the surroundings of the nucleus. In Figure 2.8, a schematic representation of the
nuclear decay and excitation process is given.

In Figure 2.8 the horizontal lines represent nuclear energy levels of the source and
absorber. The source nucleus decays from the excited state to the ground state, emitting a
y-ray. The y-ray is subsequently absorbed in the absorber, thus raising the absorber
nucleus to its excited state. Since every isotope has absorption energy in a different
energy region, y-rays of each nucleus (e.g. 57Fe) can only be reabsorbed by nuclei of the
same type.

D.S. SMIT 28
CHAPTER2 LITERATURE SURVEY

I Source
I t-1___Absorber ----11
Source nucleus A

~oactive decay
_Exited state
y-rays ----~---~-~~~--~~~~-~

-----•_J•'-Ground state

Stable daughter nucleus B Stable nucleus B

bsorptioa line J1\ Eadssioa liae

Inte01ity /r.!
.I
/
....*'

Count rat.

+
Eaergy dilplaeement 4E

Figure 2.8 Schematic representation of the events occurring in Mossbauer

spectroscopy (Cohen, 1976:3)

Small perturbations in the energy of nuclear levels in the absorber can be measured by
observing the change in y-ray energy required for they-ray to be resonantly absorbed.
These measurements are usually performed by scanning the gamma-ray energy, using the
Doppler shift, produced by moving the source with known velocities.

The resultant spectrum is normally displayed as a spectrum of count rate versus y-ray
energy shift (see Figure 2.8). The nuclear resonance will cause an increased absorption at
y-ray energies, matching the possible excitation energies in nuclei in the absorber and
will result in an absorption line. This dip (or series of dips) is known as a Mossbauer
spectrum. The energy shifts, at which resonant absorption occurs, as well as the relative
D.S. SMIT 29
CHAPTER2 LITERATURE SURVEY

line intensities, are the principal measured parameters in most Mossbauer spectroscopy
experiments and are determined by electronic effects on the nuclear energy levels.

The energy shift arises from the interactions of electrons with the nuclei, and these
measurements allow various conclusions to be drawn about the electronic structure of the
material being studied. These effects, called "hyperfine parameters", are the isomer
(chemical) shift, (), (electric) quadrupole splittings, Ll, and the magnetic hyperfine
Zeeman splitting. The isomer shift and quadrupole splitting are expressed as a value with
units of mm.s-1 and the magnetic hyperfine Zeeman splitting in terms of the magnetic
field strength measured in Tesla.

57
In the present investigation use was made of a Co-source emitting A.-rays of 14.4 keV
energy, decaying to 57Fe, of which the energy level diagram is shown in Figure 2.9

- 2XIO"'W
'l
r-•c>7ev
•
I=i
j_ -ICS.._v
t t
,
-
Y"'
' ~ It
14keV j

LIO.....V /
/
BARE a..ECrbTATIC
EfiERGY SHFT DUE
0\MI:lftUPOLE
' MAGNETIC HFS
NUCl.£US HI'SOX1LI!L.ET) {SO< OR EIGHT LINES)
10 S ELECTRONS
(ISOMER SHIFT)

Figure 2.9 Energy level diagram for 57Fe (Cohen, 1976:5)

2. 7.2 Isomer shift (0)

The total electron density on the Mossbauer atom is measured by the isomer shift (see
Figure 2.1 0). Strictly, it is the electron density at the nucleus that is important and it is
measured relative to that in a standard material. The nucleus interacts with the electrons
in a manner, which raises the energy levels by an amount that is proportional, both to the
size of the nucleus and to the magnitude of the electron density.
D.S. SMIT 30
CHAPTER2 LITERATURE SURVEY

cpmt-----.

Velocity

Figure 2.10 Characteristic parameter of a Mossbauer spectra: isomer shift (singlet)

According to Greenwood (1967:56), the isomer shift is determined by the interaction

between the nucleus and the charge distribution of electrons in the region of the nucleus.
The isomer shift depends on the fact that the spacing of the nuclear energy levels depend
on the chemical environment of the nucleus.

2.7.3 Quadrupole interactions (A)

Cohen (1976:10) stated that a Mossbauer nucleus can be used as an 'observer' or probe to
get information about site symmetries and field gradients within a crystal and to give
details of imbalance of p and d electrons. The nuclear energy levels, represented by the
electric quadrupole and magnetic dipole hyperfine interactions, may be split, in addition
to energy level changes, produced by the isomer shift. This splitting leads to a number of
possible absorption energies, resulting in a number of absorption lines. According to
Armstrong et al. (1981:515), a split between the nuclear excited state (1=3/2) and ground
state (I=l/2) of 57Fe-nucleas results in the formation of two absorption lines, namely a
doublet. This type of interaction is illustrated in Figure 2.11.

D.S. SMIT 31
CHAPTER2 LITERATURE SURVEY

cpm

Figure 2.11 Characteristic parameter ofMossbauer spectra: electric quadrupole

splitting (doublet)

2.7.4 Hyperfine magnetic interactions (Zeeman splitting)

The third of the major types of interaction that can be investigated by Mossbauer
spectroscopy is the hyperfine magnetic interactions (Zeeman splitting) of the nuclear
energy levels in a magnetic field, resulting in a sextet (six lines) as illustrated in Figure
2.12. Cohen (1976:13) stated that the magnetic hyperfine interaction arises from the
coupling of the nuclear magnetic moment with effective magnetic fields at the nucleus
and results in splitting of the nuclear ground and excited states if they have a nuclear spin
larger than zero.

cpm

0 Velocity

Figure 2.12 Characteristic parameter ofMossbauer spectra: nuclear Zeeman splitting

(sextet)

D.S. SMIT 32
CHAPTER2 LITERATURE SURVEY

The extraction of nickel, copper and cobalt from a sulphide ore by means of pressure-acid
leaching is viable under specific conditions. Copper dissolution from chalcopyrite,
however, requires longer retention times and higher temperatures to ensure complete
extraction due to the passivation of the mineral surface. The leaching efficiency depends
greatly on the specific process variables such as temperature, pressure, pH, particle grain
size and leach reagent. An increase in temperature and pressure enhances the reaction
rate which leads to smaller retention times required for complete dissolution. High leach
reagent concentrations such as sulphuric acid, does not greatly improve the extraction of
the valuable metal but only influences the by-product formation. Mechanical activation
by means of ultra fine milling offers significant advantages for the extraction of the
valuable metals from sulphide ores.

The oxidising of the minerals pyrrhotite (Fe 1_xS), pentlandite (Ni,Fe) 9Ss and chalcopyrite
(CuFeS 2), at a oxygen partial pressure of 10 bar and a temperature of ll0°C in the
presence of sulphuric acid, can be described by means of the following process reactions:

.......... (12)

.......... (13)

.......... (14)

The iron hydrolysis and precipitation that occur during the leaching of these minerals can
be described by the following reactions:

......... (15)

......... (16)

The activation energy deduced for the extraction of nickel and copper from the sulphide
ore ranged between 20 and 100 kJ/mol K, and no apparent activation energy value was
found for the extraction of cobalt from pentlandite.

D.S. SMIT 27
CHAPTER2 LITERATURE SURVEY

2. 7 Moss bauer spectroscopy

The recoilless emission of gamma radiation, followed by its resonant absorption by a

sample, was discovered by Rudolf Mossbauer in 1958 and is now known as the
Mossbauer Effect.

2.7.1 An introduction to Mossbauer spectroscopy

According to Cohen (1976:2), the Mossbauer effect is the recoilless emtsston by

radioactive nuclei and resonant reabsorption of y-rays, which arises from the nuclear
excited states. These y-rays are electromagnetic radiation and have no electrical charge
and are absorbed or scattered by energetic collisions when passing through matter. The
very small energy changes can be measured by the Mossbauer effect to give information
about the surroundings of the nucleus. In Figure 2.8, a schematic representation of the
nuclear decay and excitation process is given.

In Figure 2.8 the horizontal lines represent nuclear energy levels of the source and
absorber. The source nucleus decays from the excited state to the ground state, emitting a
y-ray. The y-ray is subsequently absorbed in the absorber, thus raising the absorber
nucleus to its excited state. Since every isotope has absorption energy in a different
energy region, y-rays of each nucleus (e.g. 57Fe) can only be reabsorbed by nuclei of the
same type.

D.S. SMIT 28
CHAPTER2 LITERATURE SURVEY

I Source
I t-1___Absorber ----11
Source nucleus A

~oactive decay
_Exited state
y-rays ----~---~-~~~--~~~~-~

-----•_J•'-Ground state

Stable daughter nucleus B Stable nucleus B

bsorptioa line J1\ Eadssioa liae

Inte01ity /r.!
.I
/
....*'

Count rat.

+
Eaergy dilplaeement 4E

Figure 2.8 Schematic representation of the events occurring in Mossbauer

spectroscopy (Cohen, 1976:3)

Small perturbations in the energy of nuclear levels in the absorber can be measured by
observing the change in y-ray energy required for they-ray to be resonantly absorbed.
These measurements are usually performed by scanning the gamma-ray energy, using the
Doppler shift, produced by moving the source with known velocities.

The resultant spectrum is normally displayed as a spectrum of count rate versus y-ray
energy shift (see Figure 2.8). The nuclear resonance will cause an increased absorption at
y-ray energies, matching the possible excitation energies in nuclei in the absorber and
will result in an absorption line. This dip (or series of dips) is known as a Mossbauer
spectrum. The energy shifts, at which resonant absorption occurs, as well as the relative
D.S. SMIT 29
CHAPTER2 LITERATURE SURVEY

line intensities, are the principal measured parameters in most Mossbauer spectroscopy
experiments and are determined by electronic effects on the nuclear energy levels.

The energy shift arises from the interactions of electrons with the nuclei, and these
measurements allow various conclusions to be drawn about the electronic structure of the
material being studied. These effects, called "hyperfine parameters", are the isomer
(chemical) shift, (), (electric) quadrupole splittings, Ll, and the magnetic hyperfine
Zeeman splitting. The isomer shift and quadrupole splitting are expressed as a value with
units of mm.s-1 and the magnetic hyperfine Zeeman splitting in terms of the magnetic
field strength measured in Tesla.

57
In the present investigation use was made of a Co-source emitting A.-rays of 14.4 keV
energy, decaying to 57Fe, of which the energy level diagram is shown in Figure 2.9

- 2XIO"'W
'l
r-•c>7ev
•
I=i
j_ -ICS.._v
t t
,
-
Y"'
' ~ It
14keV j

LIO.....V /
/
BARE a..ECrbTATIC
EfiERGY SHFT DUE
0\MI:lftUPOLE
' MAGNETIC HFS
NUCl.£US HI'SOX1LI!L.ET) {SO< OR EIGHT LINES)
10 S ELECTRONS
(ISOMER SHIFT)

Figure 2.9 Energy level diagram for 57Fe (Cohen, 1976:5)

2. 7.2 Isomer shift (0)

The total electron density on the Mossbauer atom is measured by the isomer shift (see
Figure 2.1 0). Strictly, it is the electron density at the nucleus that is important and it is
measured relative to that in a standard material. The nucleus interacts with the electrons
in a manner, which raises the energy levels by an amount that is proportional, both to the
size of the nucleus and to the magnitude of the electron density.
D.S. SMIT 30
CHAPTER2 LITERATURE SURVEY

cpmt-----.

Velocity

Figure 2.10 Characteristic parameter of a Mossbauer spectra: isomer shift (singlet)

According to Greenwood (1967:56), the isomer shift is determined by the interaction

between the nucleus and the charge distribution of electrons in the region of the nucleus.
The isomer shift depends on the fact that the spacing of the nuclear energy levels depend
on the chemical environment of the nucleus.

2.7.3 Quadrupole interactions (A)

Cohen (1976:10) stated that a Mossbauer nucleus can be used as an 'observer' or probe to
get information about site symmetries and field gradients within a crystal and to give
details of imbalance of p and d electrons. The nuclear energy levels, represented by the
electric quadrupole and magnetic dipole hyperfine interactions, may be split, in addition
to energy level changes, produced by the isomer shift. This splitting leads to a number of
possible absorption energies, resulting in a number of absorption lines. According to
Armstrong et al. (1981:515), a split between the nuclear excited state (1=3/2) and ground
state (I=l/2) of 57Fe-nucleas results in the formation of two absorption lines, namely a
doublet. This type of interaction is illustrated in Figure 2.11.

D.S. SMIT 31
CHAPTER2 LITERATURE SURVEY

cpm

Figure 2.11 Characteristic parameter ofMossbauer spectra: electric quadrupole

splitting (doublet)

2.7.4 Hyperfine magnetic interactions (Zeeman splitting)

The third of the major types of interaction that can be investigated by Mossbauer
spectroscopy is the hyperfine magnetic interactions (Zeeman splitting) of the nuclear
energy levels in a magnetic field, resulting in a sextet (six lines) as illustrated in Figure
2.12. Cohen (1976:13) stated that the magnetic hyperfine interaction arises from the
coupling of the nuclear magnetic moment with effective magnetic fields at the nucleus
and results in splitting of the nuclear ground and excited states if they have a nuclear spin
larger than zero.

cpm

0 Velocity

Figure 2.12 Characteristic parameter ofMossbauer spectra: nuclear Zeeman splitting

(sextet)

D.S. SMIT 32