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12 HYDROMETALLURGICAL PROCESSES

Here will be given a description of a few important hydrometallurgical processes to exemplify


applications of the unit processes dealt with in this compendium, which are pretreatment,
leaching, leaching equipment, solution purification and metal extraction.

• Hydrometallurgical production of copper from oxide and secondary sulphide ores.


• Hydrometallurgical production of zinc from zinc concentrates.

12.1 Production of copper from oxide and secondary sulphide


ores

Heap leaching of oxide copper ores was treated in Chapter 6, LEACHING EQUIPMENT.

Since the first SX-EW plant was commissioned in 1968 at the Ranchers Bluebird plant in
Arizona production of copper through heap leaching followed by SX-EW has steadily
increased. Bioheap leaching of secondary sulphide ores has is steadily increasing since the
beginning of the 1990’s. Approximately 35% of worlds copper production in 2005 was
produced through SX-EW where 5-10% originates from heap bioleaching of secondary
sulphides.

The most important oxide copper minerals are malachite (CuCO3 ⋅ Cu(OH)2), azurite,
(2CuCO3 ⋅ Cu(OH)2) and crysocolla (CuSiO3 ⋅ H2O). They can all be leached with sulphuric
acid. Below is shown, as an example, the leaching of crysocolla with sulphuric acid:

CuSiO3 ⋅ H2O + H2SO4 Î Cu2+ + SO42- + 3H2O + SiO2

Thus, the leaching consumes sulphuric acid and this consumption does not only depend on the
copper oxide content but also on other minerals present in the ore such as calcite, dolomite
and others. If the ore has a high content of such minerals, the costs of sulphuric acid may
become prohibitive for the process economy.

In the case of heap bioleaching of secondary sulphides the minerals chalcocite (CuS2) and
covellite (CuS) are the most important. In bioleaching of sulphides an oxidant is needed to
oxidise the sulphur to sulphate which is accomplished by blowing air into the heap.
Bioleaching of covellite proceeds according to the following sum formula:

CuS + 2O2 Î Cu2+ + SO42-

The oxidation is mediated by ferric iron and the ferrous iron and elemental sulphur obtained is
oxidised by the bacteria, as is discussed in chapter 8, BIOLEACHING.

As described previously, a dilute sulphuric acid solution is sprinkled over the ore heaps and
copper is leached according to the reaction formulas above. The pregnant copper bearing
leach solution that is collected on the bottom of the heap usually contains between 1 and 6
grams of copper per litre with a pH value of between 1.5 and 2.2. Impurities in the leach
solution consist mainly of iron (1-10 g/l) and minor amounts of nickel, cobalt, zinc and others.

Before copper can be recovered from the solution, usually by means of electrowinning, the
solution must be purified and concentrated. Nowadays, this is done almost exclusively
through solvent extraction. The principle of such a solvent extraction plant is shown in Figure
12-1.

Figure 12-1 Solvent extraction plant for the purification and concentration of copper leach
solution.

As can be seen in the figure the organic phase with the extractant circulates between the
extraction and stripping stages. The aqueous phases are also circulating, the raffinate after
copper extraction is recycled back to the heap, eventually after replenishment with acid, for
leaching while the barren and the pregnant electrolyte circulate between the stripping and
electrowinning stage. Copper is extracted and stripped according to the following formula:

2RH(o) + CuSO4(aq) ⇔ R2Cu(o) + H2SO4(aq)

There are a fairly great number of possible reagents for the extraction of copper from leach
solutions. One condition for such a reagent is that it should have a high extraction capacity
while also being easy to strip, two rather conflicting properties. In addition, it should extract
copper selectively over iron and have a low water-solubility and a number of other properties.

The only extraction reagents for copper with all these properties are those that contain
hydroxyoximes. These are therefore used exclusively in commercial plants for the solvent
extraction of copper in sulphate solutions. There are two modifications of such extraction
reagents with adequate properties, namely aldoximes and ketoximes, whose general structures
are shown in Figure 12-2.
Figure 12-2 General structure of the hydroxyoximes used for copper extraction.

The aldoximes have strong extraction strength for copper, which means that it is easy to
extract copper from the aqueous phase to the organic phase, but also that it is difficult to strip
the copper back into the aqueous phase. The properties of ketoximes are more moderate in
this respect. To reach a good compromise, it is therefore common to use mixtures of
ketoximes and aldoximes. In the table below are shown the properties of some commercial
reagents based on aldoximes, ketoximes and mixtures of the two.

Table 12.1 Commercial copper extraction reagents


Reagent Extraction agent Extraction strength
Acorga P 5100 Aldoxime Strong
Acorga PT 5050 Aldoxime Strong
Acorga M 5640 Aldoxime Strong
LIX 84 Ketoxime Moderately
LIX 984 Mixture Strong
LIX 622 Aldoxime Strong
LIX 860 Aldoxime Very strong

After stripping, the copper content in the aqueous phase is about 40 g/l, while the iron content
is only 1-3 g/l with additional low concentrations of other impurities. The sulphuric acid
content in the solution is about 170 g/l. The solution is sent for electrowinning where the
electrolysis is done with anodes of lead and cathodes of titanium, acid proof steel or copper
metal (so-called starting-plates). Copper in solution is deposited at the cathode, and at the
anode, oxygen is generated according to the formulas:

Cathode reaction: Cu2+ + 2e- Î Cu


Anode reaction: SO42- + H2O Î H2SO4 + 1
2 O2 + 2e-
Sum reaction: CuSO4 + H2O Î Cu + 1
2
O2 + H2SO4

The solution leaving the electrowinning, the spent electrolyte, has a copper content of 20-30
g/l and a sulphuric acid content of about 200 g/l. This solution is recycled to the stripping
stage in the solvent extraction plant.
12.2 Production of zinc from zinc concentrates

The majority of the worlds zinc ore reserves are in the form of sphalerite (ZnS). However, the
zinc ores almost always also contain a mineral called marmatite, (Zn,Fe)S to varying extent.
In general, the zinc concentrates produced from these types of ores contain 50-58% zinc, 1-
10% iron and 33-35% sulphur. The great problem when producing zinc from zinc sulphide
concentrates is the separation of iron and the deposition of the iron-bearing waste. Zinc
production from zinc sulphide ores is mainly done through the roast – leach – electrowin
(RLE) process and this process route constitutes approximately 80% of the worlds zinc
production. Since the early 1980’s direct leaching of zinc sulphide concentrates has been
commercialised. Direct leaching is applied both as pressure leaching operations in autoclaves
and as atmospheric leaching in stirred tanks.

In Namibia at the Scorpion zinc mine there is one operation where zinc is produced from an
ore containing zincite (ZnO). The zinc is recovered through a process involving leaching with
sulphuric acid, solvent extraction and electrowinning.

12.2.1 Zinc production through the roast – leach – electrowin (RLE)


route

In the roasting process the zinc sulphide is converted into zinc oxide according to the
following formula:

ZnS + 3/2O2 Î ZnO + SO2

The sulphur dioxide that forms in the process is collected and used for production of sulphuric
acid. The iron content from marmatite present in the concentrate is also oxidised into hematite
which reacts further with zinc oxide and forms zinc ferrite (ZnFe2O4). The calcine produced
thus contains free zinc oxide and a certain amount, depending on the iron content in the
concentrate, of zinc that is bound into zinc ferrite.

The calcine is then leached in two stages, that is, the neutral leaching stage and the hot acid
leaching stage. In the neutral leaching stage the main part of the more easily leached zinc
oxide is dissolved at a pH of 4-5 using spent electrolyte from the electrowinning, with a zinc
concentration of about 50 g/l and a sulphuric acid concentration of ~200 g/l (2M), according
to:

Neutral leaching: ZnO + H2SO4 Î ZnSO4 + H2O

After leaching there is a solid liquid separation step and the leachate is sent to solution
purification and zinc recovery while the leach residue goes to the hot acid leaching. The hot
acid leaching is performed at a pH of 1-1.5 and at a temperature of about 90º C also with the
spent electrolyte. Under these conditions also the zinc ferrite dissolves:

Hot acid leaching: ZnO ⋅ Fe2O3 + 4H2SO4 Î ZnSO4 + Fe2(SO4)3 + 4H2O

The dissolved iron now has to be removed before the zinc in solution can be recovered. This
is done by precipitation after a solid liquid separation step. Eventually the residue is treated
for silver and lead recovery before disposal. There are three different procedures through
which this is achieved where iron is either precipitated as jarosite (NH4Fe3(SO4)2(OH)6),
goethite (FeOOH), or hematite (Fe2O3). Before these precipitation processes were invented
only the neutral leaching was done and the zinc in zinc ferrite was deposited at landfills. The
advantage with these precipitates is that they all are crystalline and easy to filter. Precipitation
of amorphous ferric hydroxide (Fe(OH)3) caused massive losses of zinc in the precipitate. The
different precipitates has also given their names to the process they are applied.

The jarosite process was first discovered and is also the most frequently used method.
Ammonia or potassium ions are added to the leachate and jarosite is then obtained through the
following reaction:

3Fe2(SO4)3 + 5ZnO + 2NH3 + 7H2O Î 2NH4Fe3(SO4)2(OH)6 + 5ZnSO4

To keep pH at the desired value of 1.5 calcine (ZnO) is added during the precipitation. The
kinetics for the reaction is slow at lower temperatures and is therefore done at a temperature
of 90-95° C. Solid liquid separation follows and the precipitate is disposed while the
remaining zinc sulphate solution is recycled to the neutral leaching step.

In the goethite process the ferric iron in the leachate is first reduced with zinc concentrate:

2Fe3+ + ZnS Î 2Fe2+ + Zn2+ + S°

Calcine is then added in a pre-neutralisation step to a pH of 3. Goethite is then precipitated by


blowing air into the solution at a temperature of 80° C and calcine is added to maintain the pH
at 3.

2Fe2+ + 1/2O2 + H2O + 2ZnO Î 2FeOOH + 2Zn2+

The goethite precipitate is less bulky than the jarosite and the zinc losses are also smaller.

The hematite process starts with reduction of ferric iron and pre-neutralisation as in the
goethite process. Hematite is then precipitated in an autoclave at 200° C in an oxygen
atmosphere.

2Fe2+ + 1/2O2 + 2H2O Î Fe2O3 + 4H+

In this case the acid produced during precipitation is not needed to be neutralised with calcine.
The precipitate obtained has a high iron content with the lowest zinc losses but the process is
also the most costly because of the equipment needed.

In all processes the solution leaving the neutral leaching step is sent for solution purification.
The zinc concentration is normally 150 g/l with mainly copper, cadmium, nickel and cobalt as
impurities. Since zinc is among the least noble metals the requirements on solution
purification is very high. The impurities are removed by cementation with zinc dust in several
stages. In the first stages copper and cadmium are removed. Nickel and cobalt is more
difficult to remove and cementation is therefore carried out at elevated temperatures with
activators added and with over-stoichiometric amounts of zinc dust.
After solution purification the solution goes on to electrowinning step for the precipitation of
zinc metal according to the formulas:

Cathode reaction: Zn2+ + 2e- Î Zn


Anode reaction: H2O + SO42- Î H2SO4 + 1/2O2 + 2e-
Sum reaction: ZnSO4 + H2O Î Zn + 1/2O2 + H2SO4

The sulphuric acid that is generated is recycled to the leaching stage to dissolve the zinc
calcine. The electrowinning is done with anodes of lead and cathodes of aluminium at current
densities between 350 and 550 A/m2 with a cell voltage of about 3 volts. The electrical energy
requirement is about 3000 kWh/ton of zinc produced. The precipitated zinc metal is stripped
from the aluminium cathode in special machines. After washing, the zinc is generally smelted
in an induction kiln and is cast into ingots of standard format.

The hydrometallurgical production of zinc from zinc concentrate with the jarosite process is
summed up schematically in figure 12-3.

Figure 12-3 The jarosite process for zinc production


12.2.1 Zinc production through the direct leaching routes

In many places in the world where base metals are produced there is an oversupply of
sulphuric acid. It can therefore in certain cases be beneficial to produce elemental sulphur
instead. It is also a relatively cheap method to increase the zinc production capacity since
there is no need to build a new roaster and sulphuric acid plant but only to increase the
electrowinning facilities and of course a new leaching plant. Direct leaching of zinc
concentrates are done through two different routes, that is, through pressure leaching or
atmospheric leaching.

Pressure leaching was developed in the early 1980’s in Comincos zinc refinery in Trail,
Canada and was integrated with an existing RLE process. The process utilises dilute sulphuric
acid at oxygen pressures of 16 atmospheres and at temperatures above 120° C, i.e. above the
melting point of sulphur. Direct oxidation of zinc sulphide by oxygen is a relatively slow
process but the process is speeded up by the presence of iron in solution. Enough iron is
normally present in the concentrates in the form iron substitution in sphalerite or in marmatite,
pyrrhotite (FeS) or pyrite (FeS2). The process is therefore catalysed by iron according to the
following reactions:

ZnS + Fe2(SO4)3 Î ZnSO4 + 2FeSO4 + S°

2FeSO4 + H2SO4 + 1/2O2 Î Fe2(SO4)3 +H2O

Depending on the acidity in the process which usually is either low or high the iron can then
be either precipitated or remaining in the solution. In the case of a low acid process the iron
precipitates either as hematite or jarosite during leaching or stays in solution in the case of a
high acid leach process.

The process has later been developed for stand alone production with different flowsheets
where iron can be deported in different forms depending on actual requirements at the plant or
local environmental legislations.

Atmospheric leaching was later developed by Outokumpu in Kokkola, Finland. The process
operates at ~90° C in tall reactors supplied with oxygen. During leaching iron is precipitated
as jarosite and the sulphuric acid concentration is maintained at a level of 10-40 g/l. The
process in Kokkola and later also in Odda, Norway which utilises Outokumpu technology
were expansions to existing RLE plants. A new stand alone plant producing 100 000 tons of
zinc per year is planned to be started in Iran.