RECOVERY OF METAL IONS FROM LEACH LIQUOR

When metals are extracted from an ore bydissolution, usually more than one kind of metal
ion is dissolved in the solution. Therefore, these metals are indiviaually recovered from
the solution. There are many ways to achieve this goal:

▪ Solvent extraction
▪ Ion exchange
▪ Electrowinning
▪ Cementation
▪ Chemical precipitation
SOLVENT EXTRACTION
Is common method of recovering metal ions from liquor. In this process, organic chemical
are introduced into solution. These organic chemicals should have a chemical affinity for
the metal ion to be separated. The organic chemical are taken out the solution by adding
water-immiscible oil such as kerosene, which will then absorb the organic chemical.
Chelation of uranyl ion, with monoalkyl phosphoric acid
Selecting ithe right organic solvent is key to effective separtion of the desired metal
element form leach liquor. The criteria used to select the most desirable solvent are based
on:

• Selectivity
• High extraction capacity
• Ease of stripping
• Ease of water separation
• Safety in handing-notoxic and nonflammable
• Cost

Selectivity of a desired metal ion is frequently the key to the success of the solvent
extracction process. The selectivity is often described using the term distribution ratio. The
distribution ratio, D, is defined by Eq. 2.102.

Where w represents the original weight of the solute in the aqueous phase and w1
represents the final weight of the solute phase.
Since percent extraction can be described by

When solvent extraction takes palce in series, the following analysis is valid:
In the first tank, the final weight of the solute w1 would have the following expresion,
according to Eq. 2.103.
 The final weight in the second tank could be expressed similarly,

And, for the nth tank, the final weight of the solute, wn could be evaluated as

Note that the ultimate recovery of metal ions in the nth tank can be calculated using
Eq 2.108
Let´s take an example where D for a metal ion is 10, V0 is 10 liters. How many tanks
would be requiered to extract this metal ion to at least 99%?

𝑤𝑛 𝑛
= 0.01 = 1ൗ1 + 10
𝑤

𝑛 = 1.91

McCabe-Thiel Diagram. Solvent extraction operations are often run continuosly in a

countercurrent mode, as shown in figure 2.11.
Where A and O represent, respectively, flow rates of aqueous and organic phases; x0 and
xn represent the fractional composition of the ion in the aqueous phase entering and
exiting the countercurrent extraction operation; and y n+1 and y1 represent the fractional
composition of the ion in the organic phase entering and exiting the countercurrent
extraction process:
ION EXCHANGE
Ions can be removed and recovered from solution using ion-exchange
technology. The recovery mechanism is very similar to that of solvent
extraction. The major difference is that in ion exchange, solid ion-exchange
resins are as the recovery medium.
Two types of ion exchanges are used-the inorganic exchanger and the
organic exchanger. Inorganic exchanger includes cationic types such analite
𝑁𝑎 𝑆𝑖4 𝐴𝑙𝑂6 𝐻2 𝑂 ,
𝑐ℎ𝑎𝑏𝑎𝑧𝑖𝑡𝑒 𝐶𝑎, 𝑁𝑎 𝑆𝑖2 𝐴𝑙𝑂6 ]2 6𝐻2 𝑂 , 𝑚𝑜𝑛𝑡𝑚𝑜𝑟𝑖𝑙𝑙𝑜𝑛𝑖𝑡𝑒
𝐴𝑙2 𝑆𝑖4 𝑂14 𝑂𝐻 2 𝑛𝐻2 𝑂 and anionic types such as kaolinite
𝐴𝑙4 𝑆𝑖4 𝑂10 𝑂𝐻 8 and hydroxyapatite 𝐶𝑎2 𝑃𝑂4 2 𝐶𝑎2 𝑂𝐻 . Inorganic
ion exchanger can be synthesized. Another form of inorganic exchanger
includes gelatinous precipates that are formed from aluminum sulfate-
sodium silicates solutions with sodium hydroxide. Organic exchanger are
usually synthesized. Typical examples include phenol formaldehyde resins
and polystyrene resins.
ELECTROWINNING

Metal ions can be recovered from leach liquor by applying an electromotive force to
the system. Positively charged metal ions will migrate toward a negatively charged
pole. It should be noted that by adjusting the potential, selective deposition of
metal ions is possible. For example, if the electrical potential is gradually increased
in a solution containing zinc ion and copper ion will be deposited first at lower
electrical potential because copper is a more noble metal than zinc.
The deposition efficiency of any metal can be evaluated if the amount of electricity
drawn for the deposition of the metal and the total current consumed are known.
The current efficiency, η, is defined as:
In electrowinning of zinc, the cathodic and anodic reactions are:

Cathodic reaction:

If the activity of the zinc ion is known, the required potential, E, can be calculated.

Anodic reaction:
If the activity of hydrogen ion and the partial pressure of oxygen are known, the required
potential, E, can be calculated. Therefore, the total voltage required to deposit zinc would be
𝐸𝑎𝑛𝑜𝑑𝑖𝑐 − 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑖𝑐 . However, there are other factors to consider, such as IR drop from the
solution and the loss of potential, including anodic overpotential. Let´s examine a real
situation for recovering copper by electrowinning. Leach solutions of copper usually contain
30 to 60 kg/m3 of copper dissolved in the leach liquor.
However, the solution may laso contain other metal ions such as Mn2+, Ni2+, Zn2+, Co2+ and
Fe2+.
Therefore, the total voltage for the reactions of five metals can be calculated by:

Total voltage = anodic - cathodic

CEMENTATION

Cemenation is one of the oldest technologies used to recover metal ions from solution.
When relatively noble metals such as copper ion or gold cyanide are present in solution,
the elemental state of a less noble metal or active metal such as zinc or iron is added to
this solution to remove the noble metal. For example, copper ion in a heap leaching
solution is subjected to cementatio by iron scrap or zinc powder. The chemistry of this
process is as follows:

For copper deposition on iron substrate or for copper deposition on zinc substrate.
The equilibrium constants for these reactions at 25°C are 1.9 x 1026 and 1.57 x 1037,
respectively, for Eqs. 2.113 and 2.114. Thses reations have been found to be mass transfer
controlled, and both reactions are equally effective. As noted here, more noble metal ions in
solutions are easily subjected to deposition on less noble, or more reactive, metal substrate
in the cementation reaction. Therfore, theoretically, all the metals below Cu/Cu2+ and
Fe/Fe2+ are the ones most frequently used, not Pb/Pb2+ or Ni/Ni2+. This because when the
former two metals are used, mass transfer is the limiting step, which means fast depostion is
possible; when the latte metals are used, chemical reactions is teh limiting step. Therefore,
the overall reactions is slower than in the case of mass transfer limiting.
In Figure 2.13, a cathodic curve for copper is plotted for potential versus log current density.
In addition, three anodic curves for nickel, iron, and zinc are pltted for potential versus log
current density. As exoected, sopper is the most noble metal of the four listed here and
therefore copper metal ions in solution can be deposited on any of the other three metals.
However, the anodic curve of nickel corosses at the Tafel region of the copper cathodic
curve, inidcating that ithe overal cemenattion reaction is chemically controlled. However,
the cathodic curves. As a result, both metals will give nearly the same rate of cementation
dictated by copper-limiting current.

Industrially dissolved copper is usually recovered from solution by adding zinc powder or
scrap iron from a relatively dilute solution. The process, Known as the MerillCrowe process,
is well known and widely used to recover gold-cyanide from cyanide leach liquor.

The overall reaction is: