HYDROMETALLURGY

Hydrometallurgy can be used for low grade ore, it deals with production of metals or pure metal compounds
with the help of reactions in aqueous and organic solution.

Objectives of hydrometallurgy
 To produce a pure compound which can be later processed to a metal by
Pyrometallurgical methods
 To produce a metal from either crude meta or compound which has been prepared
earlier by other methods
 To produce a metal directly from an ore or concentrate
Hydrometallurgical process involves:
1. Leaching: During leaching the desired metal in the ore are selectively dissolved in a solvent known as the
leaching reagent or leachant.
2. Separation of leach liquor: Leach liquor is separated from solid residues and the solid is washed.
3. Recovery of metallic values from leach liquor: The desired solute or the metal in elemental form is
obtained in the recovery step. Methods employed are evaporation, distillation, precipitation, cementation,
electrolysis, ion exchange, solvent extraction etc.
4. Reduction and reagent recovery: Reduction is done by pyro or electro metallurgical processes. The
leaching agent is generally recycled after purification and readjustment of composition.
 Low grade ore

Ground ore Comminution

Leaching Concentrate Physical separation Gangue

Treated concentrate Pyro-treatment Gangue

Leach Liquor

Separation Gangue

Solution Purification Pure aqueous solution

Precipitation of metal Metal

Advantages to hydrometallurgy
1. It gives high extraction of the valuable metals
2. It is mainly used as a methods of beneficiation
3. It requires very little fuel
4. The equipments needed are relatively simple and inexpensive
5. The process is most efficient for low grade ore of non ferrous metals
6. It gives very less environmental pollution

Disadvantages to hydrometallurgy
1. Large volume of solutions are to be handled for relatively smaller output
2. Some of the reagents are expensive and must be regenerated and recycled for economy
3. Reaction rates are lower at room temperature as compare to that of high temperature
Leaching: Leaching is a process which selectively dissolves the feed materials. [Selective dissolution of
minerals using reagent in the solution]

The choice of a leaching agent depends on the following factors:

1. Chemical and physical character of the materials to be leached
2. Cost of the reagent
3. Corroding action of the reagent and the materials of construction required
4. Ability to be regenerated

Some of common reagents are

i. Acids : H2SO4 snd HCL
ii. Alkilies : NaOH, NaCO3 and NH4OH
iii. Oxiding agents : O2, NaClO3, MnO3 KMnO4 and FeCl3
iv. Reducing agents : SO2 and H2
Leaching Techniques:
 In situ leaching employs water circulation through actual ore bodies and collects the solution
 Dump leaching is the application of the leach solutions to dumps consisting of off-grade ore rejects during
normal mining operation
 In percolation leaching, the leach solution is percolated upward or downward through an ore which has
already been crushed and bedded into tanks
 In agitation leaching, stirring is used to aid the dissolution process
Theory of Leaching
During leaching, a mineral decomposes in an aqueous environment. The mineral may dissolved completely,
leaving behind the gangue as a residue.

Simple dissolution: CuSO4 + nH2O = CuSO4.nH2O

Acid leaching: ZnO + H2SO4 = ZnSO4 + H2O, ZnO + 2H+ = Zn2+ + H2O
Alkali Digestion: Al2O3 + 2NaOH = 2NaAlO2 + H2O
Radical Exchange: CaWO4 + CO2-3 = CaCO3 + WO2-4
Leaching with oxidation or reduction: CuS + 2Fe3+ = Cu2+ + 2Fe2+ + S (oxidation)
MnO2 +SO2 = Mn2+ + SO2-4 (reduction)
LEACHING PROCESSES: Leaching processes are subdivided into oxidative and non oxidative processes

Non oxidative processes leaching processes

Sulphuric acid leaching of oxidized copper ores: Many copper sulphide ore have undergone partial weathering over long
periods of time and the deposits are frequently capped by oxidized minerals that may include – azurite (2CuCO3.Cu(OH)2),
malachite (CuCO3.Cu(OH)2), brochantite (CuSO4.3CU(OH)2) and other compound.
Chemical solutions of these minerals occurs readily in dilute sulphuric acid and leaching of oxidized copper ores is carried
out at a number of locations utilizing heap leaching, percolation or agitation leaching methods.

Pressure leaching of bauxite: Bauxite consist of one or minerals gibbsite (Al(OH)3), diaspore (AlO(OH) with silica and oxides
of iron as the major impurities. The Bayers process involves the dissolution of the aluminium minerals in aqueous sodium
hydroxide:
Al(OH)3 + NaOH = NaAlO2 + 2H2O
AlO(OH) + NaOH = NaAlO2 + H2O
After separation of the red mud, the solution is further diluted and seeded with fresh Al(OH)3 to bring about hydrolytic
precipitation of the aluminium.
NaAlO2 + 2H2O = Al(OH)3 + NaOH + NaOH
The precipitate is filtered and calcined to Al2O3 at 1000oC and the sodium hydroxide is recirculated for further leaching.

Reductive dissolution of pyrolusite: Non-oxidative leaching comprises both chemical and reductive dissolution processes, but
very few commercial metal extraction processes are reductive dissolution. The process may be regarded as electrochemical
dissolution.
Oxidative processes leaching processes

Oxidizing agents are required for the aqueous dissolution of many minerals and secondary materials. The most important

oxidizing agents are oxygen and iron(III) salts; but copper (II) chloride and chlorine are sometimes also employed.

Oxygen may participate directly in the oxidation process, or it may be involved in secondary role of re-oxidizing iron(II) in

reactions where FeIII + e = FeII is the primary cathodic process sustaining dissolution.

(i) Other oxidizing agents such as MnO2 and NaClO3

(ii) The action of certain autotropic bacterial which in turn required oxygen for their metabolism; the process is then

termed bacterial leaching

(iii) Electrolytic anodic oxidation; the process is termed electro-oxidative leaching

Oxidative leaching processes directly utilized oxygen: The application of oxygen directly in oxidative leaching may be simply

contrived by the use of air or oxygen at normal atmospheric pressure. Alternatively, pure oxygen or air may be used at

elevated temperatures to promote higher rates of dissolution. Elevated pressure can be attained in Autoclave.

Cyanide leaching of gold: Here oxygen participates via the atmosphere involves the dissolution of gold by alkaline cyanide

solutions.

4Au + 8CN- + O2 + 2H2O = 4Au(CN)2- + 4OH-

Pressure leaching of uranium ores: Certain uranium minerals of mixed type are difficult to treat by conventional sulphuric

acid- manganese dioxide leaching. Pressure leaching has enhanced the extent and rate of leaching.

High recoveries are achieved in 2 hours using a temperature of 200oC and oxygen at 14 atmoshpheric pressure, whereas

treatment for 16 hours in Pachuca tank by the conventional methods give at best only 80 % dissolution. Although, some acid

is introduced initially to start the reaction, the pressure leaching process itself provides the major amount of sulphuric acid

requirement by oxidation of the pyrite incidentally present in the ore.

Bacterial leaching: Several types of bacteria can accelerate some leaching reactions selectively to increase both rate of

dissolution as well as recovery of metallic values. These bacteria (Ferro-bacillus ferrooxidans, Thiobacillus ferroxidants and

Thiobacillus thiooxidans) are capable of growing on pure inorganic media obtaining their energy requirements by oxidizing

inorganic substances like Sulphur, thiosulphate and ferrous ion.

Principles of extractive metallurgy by H. S. Ray

Electro-oxidative Leaching: Where leaching is carried out in an electrolytic cell by an oxidant that is regenerated at an

insoluble anode under the influence of an external potential, the process has been termed electro-oxidative leaching. The

powder plate process utilizes this technique. It is clamed to capable of direct recovery of copper from sulphide concentrates,

copper scrap and copper slurries. In the powder plate cell, leaching and electro-deposition of copper occur simultaneously at

high current densities. The anodic processes consist of oxygen generation as well as oxidation of iron(II).
 PURIFICATION OF LEACH LIQUOR

Ion Exchange: Ion exchange is a phenomenon that occurs readily in nature with alumino-silicates providing the
solid, three-dimensional networks with which the exchangeable ions are associated. The principle of ion exchange
is a solid resin exchanges ions on its surface from another ions in solutions. Absorption is the result of an exchange
of ions between the solution and the solid. The solid phase is made initially absorb a suitable ion of the desired
metal through an ion exchange reaction. This is called elution ie. A methods by which the absorbed ion is brought
into solution. The metal is finally recovered from the solution by precipitation.

• During ion exchange leach liquor is brought into contact with an organic resin containing an active compound, RX which

exchange a radical with an anion in solution.

• The solid organic resin used is in the form of hard, insoluble granular solid or porous beaded form, so that it can be easily

packed in long columns.