Sulfuric acid Roasting

It is the currently industrialized method. It requires an ore with a LiO2 concentration of

6.05% upwards for its effectiveness. The roasting is done with 93% H2SO4 at a temperature
of 250oC for 30 minutes.

β-Li2O.Al2O3.4SiO2(s) + H2SO4(l)→ H2O.Al2O3.4SiO2(s) +Li2SO4(s)

Li2SO4(aq) + Na2CO3(l) → Li2CO3(s) + Na2SO4(aq)

Advantages

 Low temperatures required

 Has proven to be work efficiently at a large scale
Disadvantages

 Has SO2 gas emissions

 Uses high concentration reagents

Chlorination Roasting

This method used an ore with LiO2 concentration that is 7.20% upwards with CaCl2 to ore
ratio of 1:2 at 900oC for 120 minutes. The process can also be done by roasting the
concentrate with pure Cl2 at 110oC for 150 minutes.

Advantages

 Recovery of up to 90.2%
 More than one reagent can be chosen for the process
Disadvantages

 High leaching temperature required

 Corrosion resistant equipment required
Sodium Carbonate Leaching

This is done for an ore with LiO2 concentration of 6.06% with Na2CO3 at liquid to solid ratio
of 4mL/g and Na to Li ratio of 1.25 at 225oC for 60minutes. It can be done as a closed loop
process therefore giving high recoveries for example the first step giving 94% recover and the
second step giving 91% recovery.
Advantages

 High recoveries can be achieved

Disadvantages

 Complex steps
 High reagent costs

Hydrometallurgy
Leaching

Leaching is a complex heterogeneous process whereby there is interaction between dissolved

reagents with solid substances. It’s a process of mass transfer from the solid phase to the
liquid phase by a liquid. Leaching is a procedure where the metal is rendered soluble salt and
impurities are insoluble.

Factors Affecting Leaching

1) The physical properties such as particle size
Particle size determines the extent of exposure of the concentrate to the lixiviate. Small
particle size enhances the leaching rate since larger surface area is exposed to chemical
attack.
2) The extent of liberation required
For this purpose, a recovery of 99.6% is required
3) Concentration of reagent
Leaching rate increases with increase in reagent concentration
4) Stirring or agitation rate
Stirring is required to keep solids in suspension and eliminate the influence of external
mass transfer.Agitation or stirring rate affects dissolution of lithium.
5) Temperature
In lithium extraction temperature has very little effect.
6) Leaching time
Leaching extent is increased by increasing residence time.
7) Solid to liquid ratio
Increasing solid to liquid ratio decreases the percentage lithium extracted.This is because
solid to liquid ratio is related to viscocity.Increasing solid to liquid ratio increases
viscocity increasing mass transfer resistance.
Water Leaching
Water leaching is a subsequent process of roasting or acid digestion. that renders the petalite
ore Leaching of petalite concentrate is not entirely selective as co-dissolution of impurities
also occurs. The highest extraction of for water leaching is around 97.30% and is realized
after a leaching time of 60 minutes. To avoid significant loses of the liquid by evaporation, a
lower temperature should be used for water leaching.

Process operation

1) Particle size of < 75µm

2) Stirring speed 320 rpm
3) Temperature range of 50oC to 90oC
4) Solid to liquid ratio of 1/7.5 g/mL
Advantages

 High recoveries are achieved

 There are no chemicals used hence the process is cheaper
 Low temperatures are used hence low energy consumption
 Does not produce toxic by-products
Disadvantages

 High pressure agitation is used hence high investment costs

 Process does not give recoveries of above 99%
Advantages

 Lixiviant is Na2CO3

 Temperatures between 190oC to 235oC

Sodium Carbonate Leaching

This is done for an ore with LiO2 concentration of 6.06% with Na2CO3 at liquid to solid ratio of 4mL/g
and Na to Li ratio of 1.25 at 225oC for 60 minutes. It can be done as a closed loop process therefore
giving high recoveries for example the first step giving 94% recover and the second step giving 91%
recovery.

Advantages Disadvantages
High recoveries can be achieved High reagent cost
Lithium loses may occur
Complex steps hence causing the leaching
process to become complex
Hydrochloric Acid Leaching

Mineral acids such as HCL and HNO3 can not be used in acid digestion due to their relative volatility
thus alternatively these acids are used as leachants in aqeous solutions of up to 100 oC in order for
the lithium to dissolute from calcined state (Margarido, et al., 2014)

Disadvantages

 A highly contaminated solution is produced

 The process is less effective than acid digestion and water leaching

 Reaction is slow

 HCl is a volatile liquid

 Consumption of acid is high

 Process is less selective of the compounds in the silicate ore hence more impurities are found in
the product

Alternative Process Routes

1) Alternative route 1
 H2SO4 Digestion

Filtration

Precipitation

Advantages

 Simpler and fewer

Disadvantages

 Reagent is acid which requires more expensive handling

2) Alternative Route 2
 Re-grinding

+ 75µm

Screening

-75µm

Water Leaching

Ion Exchange

Advantages

 May be considered more thorough

Disadvantages

 Energy intensive

3) Alternative Route 3
 β spodumene

H2SO4 Digestion

Re-grinding

+75µm

Screening

-75µm

Water Leaching

Precipitation

Advantages

 Much more effective

Disadvantages

 Energy demanding

Precipitation of Lithium Carbonate

Lithium carbonate with high purity is an important raw material for the fabrication of lithium
rechargeable batteries and medical components. Recrystallization is an important step to way to
produce Lithium carbonate with high purity from commercial Li2CO3 containing by the treatment of
the commercial lithium sulfate in sodium carbonate solution. Lithium carbonate exists only in the
anhydrous form. Relative to other lithium salts, its solubility in water is low. The isolation of lithium
from lithium ores capitalizes on this property of poor solubility.

Figure Error! No text of specified style in document..1: Chemical Structure of Lithium Carbonate
(PubChem, 2016)

Higher temperatures of up to 90◦C favor the recrystallization of Li2CO3 in Na2CO3 solution and
promote the removal of sulfuric acid ions adsorbed on or in the commercial lithium carbonate. The
acid content is reduced and lithium carbonate produced. The process may last up to 10 hours.
(Abraham, 1986)

Lithium sulfate is water soluble , though it does not follow the usual trend of solubility versus
temperature its solubility in water decreases with increasing temperature. Its dissolution is an
endothermic process. Lithium sulfate it has hygroscopic properties, the most common form of
lithium sulfate is lithium sulfate monohydrate. Anhydrous Lithium sulfate has density of 2.22 g/cm3.
Weighing lithium sulfate anhydrous can become rigorous as it must be done in a water lacking
atmosphere. Although lithium sulfate can be used to treat bipolar disorder, it is not until its further
processing as the lithium sulfate from the digestion still contains free sulfate ions from the acid.
Hence the need to precipitate to lithium carbonate first.