Leaching and Solution Preparation

PURPOSE
The objective of the leaching operation is to dissolve zinc as selectively as possible
to form a solution suitable for electrowinning following appropriate purification
procedures. Electrolytic zinc processe almost exclusively use sulfate solutions and
hence the leaching operation involves the dissolution of zinc from calcine using
sulfuric acid in the form of spent electrolyte. It is also possible to leach zinc directly
from sulfide concentrates without prior roasting and this is detailed late in this
chapter. However the leaching process generally uses calcine as the primary feed
and is simply based on the acid-base reaction as shown in Equation 5.1.

Sulfuric acid is supplied in the form of spent electrolyte after electrowinning and
commonly
containing around 150 g/L sulfuric aci and 50 g/L zinc, although these levels will
vary from one plant to another.
Equation 5.1 describes the Primary Leaching operation. In addition, the presence of
zinc ferrites requires more severe leaching conditions and a Secondary Leaching
step is needed to extract residual zinc from the Primary Leach Residue.

LEACHING OF CALCINE
Although calcine contains zinc mostly in the form of zinc oxide, it also contains zinc
in the form of zinc ferrite, zinc silicate and to a minor extent as residual sulfide (see
Chapter 4). The attack on the various compounds during leaching and the
dissolution of zinc is determined by the acidity of the leach solution and its
temperature. Four broad leaching regimes are commonly employed:
neutral leaching in the pH range of 4.0 to 5.5 and at around 60 oC,
weak acid leaching from 10 g/L H2SO4 to pH 4.0 and at around 60oC,
hot acid leaching from 30 to 80 g/L H2SO4 and at over 90oC, and
strong acid leaching at acidities above 120 g/L H2SO4 and at over 90oC.
These regimes are applied in a multi-stage countercurrent format. The first two
stages of neutral leach and weak acid leach are often referred to as primary
leaching and leave a residue essentially containing zinc ferrites. The hot acid leach
and strong acid leach are referred to as secondary leaching and are integrated
with an iron removal stage as detailed in this chapter. The primary and secondary
leaching sequence is illustrated in Figure 5.1.

It was not until the development in the late 1960s of suitable methods of separation
of significant amounts of iron from solution in a form which could be readily filtered
and washed, that secondary leaching of zinc ferrite (or primary leach residues) was
practical. Such iron separation methods were the jarosite, goethite and hematite
processes that are detailed below. Prior to the development of those processes the
only precipitation method available for iron was simple neutralisation to give ferric
hydroxide. This precipitate is gelatinous and difficult to separate by settling and
filtration. It also tends to entrain large quantities of zinc sulfate and therefore
contributes little advantage to the leaching of zinc ferrites. Consequently it is only
useful for separation of small quantities of iron, limited to about 2 g/L.

FIG 5.1 - Primary and secondary leaching flow sheets.

There are many variants of the generalised flow sheet given in Figure 5.1,
depending on the nature and grade of the calcine processed, the presence of critical
impurities and the method of integration with the iron removal stage. Recovery of a
lead-silver residue is also a key issue in flow sheet design and may not be justified if
lead and silver values in the concentrate are low. In that case, hot acid leach pulp
may flow directly to the iron removal stage without solids separation, and leaching
and iron separation may be closely integrated.
Primary Leaching
Neutral leaching will dissolve any zinc sulfate and basic zinc sulfates as well as a
significant proportion of the zinc oxide content in accordance with Equation 5.1.
At pH levels above five, there is potential to form basic zinc sulfate according to
Equation 5.2.

The equilibrium position is controlled by the concentration of zinc and sulfate and
the solution pH, but zinc can remain in solution up to a pH range of between 4.8 and
6.0. At higher pH levels, zinc hydroxide will form according to Equation 5.3.
The hydroxide is stable in solutions with a pH range of six to seven. At higher pH
levels the
hydroxide will redissolve and form a zincate ion ZnO2 In normal practice the pH at
which basic zinc sulfate will begin to appear is normally around 5.1.
The operating pH range through a series of neutral leach tanks is commonly 4.2
rising to 5.0 to 5.2. A residence time for the neutral leach stage is normally of the
order of five hours and depending on the reactivity of the calcine will give a zinc
extraction from zinc oxide of the order of 70 per cent. The weak acid leach
commonly operates in the pH range of 2.5 to 3.5 and will extend the extraction of
zinc from zinc oxide, but this will depend critically on operating pH levels. In usual
circumstances, where the flow sheet incorporates a secondary leaching stage, the
degree of zinc extraction from free zinc oxide is not critical and may be of the order
of 85 per cent. However, if the iron levels in feed are low the flow sheet may not
include a secondary leaching stage, in which case higher acidities may be used
within the Weak Acid Leach to maximise the zinc extraction from oxide.
Any iron present in the zinc oxide lattice (derived from marmatitic iron) will be
dissolved in the
weak acid leach as ferrous iron. The weak acid leach will also dissolve zinc silicates
according to Equation 5.4.
Orthosilicic acid is unstable in aqueous solution and decomposes according to
Equation 5.5. That stability is a function of solution pH and orthosilicic acid is highly
unstable in extreme ranges of acidity or alkalinity. Maximum stability is usually
encountered in the range of pH 3 to 3.5.

Silica precipitates from solution as a polymer, and according to conditions of pH,

temperature and dissolved silica concentration, can form either pseudo-crystalline
material or highly hydrated gels. If gel formation occurs the separation of leach
residues by settling and filtration will become difficult, and as a consequence, the
selection of leaching conditions to avoid this situation can be of critical importance.
Silica will precipitate under neutral leach conditions and care must be taken to limit
the level of soluble silica contained in input solution to that stage. Generally most
standard primary leach circuits can handle silica if its level in calcine is below 2.5
per cent. Above this level special flow sheet requirements are usually needed.

Silica precipitation in a condensed or pseudo-crystalline form is favoured by low

precipitation rates requiring low concentrations of silica in solution and by certain
pH ranges. An insight into the stability of silica in solution is given in Figure 5.2
(Wood, 1963), which shows the stability in solution, expressed as the log of the time
taken for the solution to form a gel (as indicated by viscosity), in relation to solution
pH. In this case, maximum stability (corresponding with maximum gel time) occurs
around pH 2 and minimum stability occurs under strong acid conditions or at a pH of
around five to six. Silica stability can also be influenced by the species in solution,
such as the presence of ferric iron and aluminium ions, which aid precipitation, and
the presence of fluorine, which can promote gelation.

If solutions containing relatively high and stable concentrations of silica are

produced under certain leaching conditions (such as weak acid leaching), then it is
important to take care with sharp changes in conditions promoting gel formation
(such as the addition of these solutions to the neutral leach stage). Where it is
necessary to precipitate silica from such solutions, then in order to promote
formation of a more crystalline silica and avoid gelation, it is necessary to ensure
sufficient dilution to hold silica at low levels in solution for the precipitation reaction.
This will favour the use of large single stage reaction tanks rather than multistage
operation for silica precipitation, or for combined zinc silicate dissolution and silica
precipitation if operating in an unstable regime.

FIG 5.2 - Stability of silica in solution (Fugelberg and Poijarvi, 1979).