ELECTRO-MEMBRANE SALT SPLITTING

PROCESS TO PRODUCE LITHIUM

HYDROXIDE
Electrochemical salt splitting process
 A membrane process
 1) Electric potential difference => Reax. & Driv. force
 2) Ion exchange membranes => Selective transport

 Electrochemical salt splitting = Anodic-cathodic water

splitting reax. + Membrane counter-ion selectivity
𝟏
 Anodic => 𝐇𝟐 𝐎 → 𝟐𝐇 +
+
𝟐
𝐎𝟐 + 𝟐𝐞−

 Cathodic => 𝟐𝐇𝟐 𝐎 + 𝟐𝐞− → 𝟐𝐎𝐇 − + 𝐇𝟐

 Applications => Alkali/acid production/regeneration ;

Recovery of salts.
 Electrochemical salt splitting process
HY acid HY acid X+Y- Salt XOH base
XOH base
+ (concentrate) (diluate) (concentrate)
(concentrate)
XY salt CEM AEM CEM

O2 cations H2 O2 cations H2 -
+ - +
+ + + +
H+ OH- H+ anions OH-

X+Y- XOH base

salt (diluate) HY acid X+Y- Salt XOH base
(diluate) (concentrate) (diluate)

(a) (b)
LiOH
 Raw mat. for lithum salts ; Dye addit. ; CO2 adsorber
 Conventional LiOH production
𝐋𝐢𝟐 𝐂𝐎𝟑 + 𝐂𝐚(𝐎𝐇)𝟐 → 𝐂𝐚𝐂𝐎𝟑 + 𝟐𝐋𝐢𝐎𝐇
 Electromembrane process => Li2SO4 splitting
 No solid residue (CaCO3).
 Higher purity

 Understanding electrochemical LiOH production

process
Anolyte preparation and purification
 Anolyte needs to be purified to prevent membrane blockage
 Reaction + Purification (Removal of suspended + hardness)
𝐋𝐢𝟐 𝐂𝐎𝟑 + 𝐇𝟐 𝐒𝐎𝟒 → 𝐋𝐢𝟐 𝐒𝐎𝟒 + 𝐂𝐎𝟐 + 𝐇𝟐 𝐎
10% H2SO4

Resin,
Resin, H+ form
Na+ form
4% LiOH
Lithium carbonate
Sulphuric acid Resin, Li+ form
Demin. water

PRESSURE ION
REACTION
FILTRATION EXCHANGE

Residues Pure Lithium

Sulphate Solution
Conductivity/pH v.s. Concentration
Relation of Electrolytes
 Experimental (Preliminary conductivity measurements)
 Solutions at certain concentrations in 150 ml erlenmeyer flasks
=> placed into a pre-set shaking water bath & measured.

Preliminary conductivity measurements

Li2SO4 Temperature
Factors: LiOH %
% °C
5 1 30
10 3 45
Levels: 15 5 60
20 7
23

 Preliminary conductivity measurements => optimum point

Conductivity/pH v.s. Concentration
Relation of Electrolytes
 Results (Preliminary conductivity measurements)
600

500

400
Conductivity, mS/cm

300

200

100
30°C 45°C 60°C

0
0 1 2 3 4 5 6 7 8
Lithium hydroxide, %

Conductivity-concentration regression for catholyte (LiOH) solution

Conductivity/pH v.s. Concentration
Relation of Electrolytes
160

140

120
Conductivity, mS/cm

100

80

60

40

20 30°C 45°C 60°C

0
0 5 10 15 20 25
Lithium sulphate concentration, %

Conductivity-concentration regression for anolyte (Li2SO4) solution

General Membrane Behaviour in The
Electrochemical Production of LiOH
 To investigate the general membrane behaviour membrane in
the electrochemical production of lithium hydroxide in a two-
compartment membrane electrolysis cell under different process
parameters (temperature, current density, catholyte
concentration)
 To compare the performance with similar previous studies.
 To recommend optimum membrane electrolysis parameters for
this process based on a production cost estimation realized
using the results of this study.
General Membrane Behaviour in The
Electrochemical Production of LiOH
 Experimental

8 7

6
4
5

1
10
pH pH
Temp - + Temp
Cond Cond

2 3

The diagram of the experimental set-up (batch process)

General Membrane Behaviour in The
Electrochemical Production of LiOH
 Parameters:
 Nafion®N-424 membrane
 Circulation flowrate of 500 mL/min;
 Temperature of 30-60°C
 Anolyte initial concentration: 22% Li2SO4
 Catholyte initial concentration: 4, 6, 8% LiOH
 Current density of 4, 8, 12, 16 A/dm2.
General Membrane Behaviour in The
Electrochemical Production of LiOH
 Outputs:
 Currrent efficiency

CE (%) =100×
∆Lireal MWLi ×I×t×3600
∆Litheory ∆Litheory =
96484

 Unit power consumption (P)

𝐕×𝐈×𝐭
𝐏=
∆𝐋𝐢𝐫𝐞𝐚𝐥

 Production rate (R)

∆𝐋𝐢𝐫𝐞𝐚𝐥
𝐑=
𝐒×𝐭