Chemical Processing of Ore Minerals

Prof.Dr. Ahmed A.S. Seifelnassr

Professor of Mineral Processing
Dept. of Mining Engineering
Faculty of Petroleum and Mining Engineering
Suez University
Suez, Egypt
E-mail:[email protected]
Leaching Systems
Chapter 5
Chemical Leaching System
• In most ores elements occur as mineral compounds which are insoluble in water;
therefore, leaching involves chemical reaction to convert the element to a water-
soluble form followed by dissolution.
• The choice of a leaching agent depends on the following factors:
• Solubility. Large and rapid solubility of the material to be leached in the leaching
agent.
• Cost. An expensive reagent is undesirable because any traces lost during handling
will represent a large economic loss.
• Materials of construction. If the leaching agent is corrosive and must be handled in
tanks made of stainless steel, titanium, the capital cost will be high, and therefore
its use will be less desirable.
• Selectivity. An ideal reagent will extract only the desired component.
• Regeneration. Ability of regenerating the reagent for recycle is also an important
criteria.
Leaching Agents
• Water is an ideal leaching agent because it is cheap and noncorrosive, but
its action is only limited to few minerals.
• Leaching agents commonly used other than water are, Acids, bases, and
aqueous salt solutions
• Leaching agents may be used either alone or in combination with oxidizing
agents.
• An oxidizing or a reducing agent is sometimes needed during leaching to
solubilize certain minerals which do not dissolve otherwise.
• Commonly used oxidizing agents are oxygen (or air), ozone, hydrogen
peroxide, ferric ion, manganese dioxide, sodium nitrate, and sodium
chlorate
• commonly used reducing agents are ferrous ion, hydrogen and sulphur
dioxide.
• Important factors to be considered during the leaching process
• Percent recovery is a major concern rate of a leaching process - the percent
recovery as a function of time
• Related factors: particle size, concentration of leaching agent, temperature,
pulp density, agitation intensity.
• compromise is always made between the increased rate of leaching and the
negative effect of any of the factors influencing this increase.
• 1- Water Leaching
• Leaching with water only is feasible when the mineral as-mined is water-
soluble, or when the ore or concentrate has been pretreated to convert
certain elements to a water-soluble form.
• Examples of the latter include sulfation roasting of sulphide concentrates
(zinc, copper, cobalt).
• Some compounds, e.g., CuSO4, ZnSO4, most compounds of alkali metals
(Na, K, Li,….) dissolve in water readily.
• Heating always accelerates leaching. Some poor grade copper sulphide ores
transform slowly into water soluble sulphate under atmospheric condition
and can be recovered by simple leaching.
• In commercial practice, however, water is rarely employed as a solvent.
• 2 - Acid Leaching
• Sulfuric acid is the most common leaching agent.
• Dilute: used for leaching copper oxide ores, zinc oxide, phosphate rock,
and a variety of other ores.
• In combination with an oxidizing agent: used for leaching uranium ores
and sulphides.
• Concentrated: used for treating more resistant minerals such as sulfide
concentrates, laterites, monazite, and titanium slag.
• Examples of reagent are:-
• ✓ Acids (H2SO4,HCl)
• ✓ alkalies (NaOH,Na2CO3,NH4OH)
• ✓ oxidising agent (NaClO3, MnO2, KMnO4, FeCl3)
• ✓ reducing agent(SO2,H2)
• Examples
• Copper ores.
• Atmospheric Pressure.
• Several copper minerals containing the copper in the divalent
state (e.g., azurite Cu3 (C03)2(OH)2 , malachite Cu2 (OH) 2 C03 ,
tenorite CuO, and chrysocolla CuSi02 .2H20), are completely
soluble in sulfuric acid at room temperature:
• Cu3 (C03)2 (OH) 2 + 3H2S04 = 3CuSO4 + 2CO2 + 4H2O. (I-1)
• CuO + H2SO4 = CuSO4 + H2O. (1-2)
• CuSiO3 .2H2O + H2SO4 = CuSO4 + SiO2 + 3H2O. (1-3)
• Elevated Pressure.
• Sulfuric acid leaching under oxidizing conditions at elevated
temperatures and pressure can be used for copper, nickel, cobalt,
zinc, and lead sulphides. Thus, the use of this technique offers a
variety of selective leaching processes for bulk sulfide
concentrates. The general equation can be written
• MS+ 1/202 + H2SO4 = MSO4 + H2O + S
• 3- Alkaline Leaching.
• It is generally more selective than acid leaching and is particularly appropriate for ores
containing large amounts of acid-consuming carbonate gangue.
• NaOH solution or NH4OH, are routinely employed in many leaching operations.
• While bauxite is leached by hot concentrated NaOH solution under pressure, ammonia
solution is used in the leaching of native copper, copper ores, NiS and Cu2S.

A12O3 (s) + NaOH (aq.) = 2NaA1O2 (aq.) + H2O (aq.)

Cu2(OH)2 CO3 (s) + (NH4)2 CO3 (aq.) + 6NH4OH (aq.) = 2Cu(NH3)4 CO3
(aq.) + 8H2O (aq.)

NiS (s) + 2O2 (g) + 6NH4OH (aq.) = Ni(NH3)6 SO4 (aq.) + H2O (aq.)
• Tungsten can be extracted from wolframite (Fe, Mn)WO4 , or ferberite,
FeWO4 , by pressure leaching with NaOH and from scheelite, CaWO4 ,
by pressure leaching with N2CO3 •
• 2FeWO4 + 4NaOH + 1/202 = Fe2O3 + 2N2 WO4 + 2H2O. (I-20)
• CaWO4 + N2CO3 = CaCO3 + N2 WO4
• 4- Cyanidation
• Leaching with cyanide has been applied almost exclusively to gold
and silver. With oxygen as the oxidant. The use of cyanide in leaching
depends upon the ability of the cyanide ion to form stable complexes
with the majority of transition metals. These complexes are
sufficiently strong to overcome the relative inertness of gold and silver
and the insolubility of minerals, such as chalcocite, Cu S, and
argentite, Ag S.
• Since HCN is a weak acid (pKa = 9.31) leaching should be carried out under
conditions sufficiently alkaline (pH > 10) to ensure that the concentration of
the cyanide ion, which is the active form, is not reduced by hydrolysis:
• Alkaline conditions also minimize the loss of hazardous HCN by
vaporization. Cyanide can also be lost from solution by reaction with
oxygen (to form cyanate), with sulphur and sulphide (to form thiocyanate),
or with metal ions (to form complexes, e.g., Fe(CN)6).
• Gold: In most gold ores the values occur as the metal which must be
oxidized during the process of dissolution. With oxygen as the oxidant, the
leaching reaction is:
• 2Au + 4CN +O2 + 2H2O = 2Au(CN)-2 + 2O2H2
• The oxygen is supplied as air, which often also serves to aid pulp
agitation. The cyanide is supplied as its sodium or calcium salt, and
lime is used for the control of alkalinity. The dissolution is adversely
affected by the presence, not only of cyanicides which reduce the
concentration of available cyanide, but also of other minerals and
chemicals that act as specific poisons, e.g., sulfides.
• Silver: Silver occurs both in the metallic and, more commonly, in
combined form. The metal reacts with cyanide in the presence of
oxygen:
• Ag + 4CN + O2 + 2H2O = 2Ag(CN)2- + H2O2 + 20H- (1-27)
‘-

• but silver in combination dissolves without further oxidation, e.g.,

Ag2S + 4CN- = 2Ag(CN)-2 +S-2
5- Other Chemical Leaching Systems:
a)- Sodium Sulfide:. Alkaline solutions of sodium sulfide or sodium
hydrosulfide react with the sulfides of arsenic, antimony, tin, and mercury to
form soluble polysulfides:
Sb2S3+ 3NaHS + 3NaOH = Na6Sb2S6+ 3H20. This process was used for the
treatment of argentiferous tetrahedrite, (Cu, Ag) 3(Sb, As)S3.
b)- Hydrosulfite: Certain hydrosulfites or dithionites are effective reducing
agents and are used as additives to promote the removal of traces of iron from
glass sands, etc., by acid leaching. In one process glass is leached with dilute
hydrofluoric and sodium dithionite.
• Na2SO4 + 6Fe3+ +4H20 = 2NaHS04+ 6Fe2+ + 6H+
Similarly, the brightness of kaolin products can be upgraded by leaching with
zinc dithionite.
c)- Hypochlorite: The hypochlorite ion can be used for the oxidative
leaching of molybdenite, cinnabar, and silver ores.
MoS2 + 9OCl- + 6OH- = MoO4-2 + 9Cl- + 2 SO4-2 + 3H2O
The hypochlorite ion can be conveniently generated from chloride
solution electrolytically in the dissolution cell, thus avoiding the necessity
of storing and handling chlorine gas.
d)- Anodic Dissolution: Many leaching reactions involve oxidation and,
in some instances, the oxidation can be carried out electrolytically by
making the material to be dissolved the anode of an electrolytic cell. Thus,
impure metals, e.g., Cu, are anodically dissolved in electrorefining
processes. Metal sulfides and mattes of copper and nickel are also
dissolved anodically with simultaneous deposit ion of metal at the cathode
in the same cell.