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ION EXCHANGE
Overview
• By the end of this topic, students should be
able to
– Explain the ion-exchange process and the
regeneration process
– Estimate the concentration of removed ions.
– Estimate the length of the ion-exchange column.
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DEFINITION
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OPERATION MODE
• Batch
– Resin is stirred with solution to be treated in a
reactor until the reaction is complete.
– Spent resin is removed by settling.
– Regenerated and reused.
• Continuous
– Exchanged material is placed in a bed or packed
column.
– Solution to be treated is passed through it.
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ION EXCHANGE RESIN
• Natural occurring resin –
zeolites
• Synthetic resins
– Strong-acid cation (SAC)
– Weak-acid cation (WAC)
– Strong-base anion (SBA)
– Weak-base anion (WBA)
– Heavy-metal selective
chelating resins
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Example: Cation exchange
Pore Aqueous-
space phase ions to
be exchanged
B+ X- A+ X-
B+ X- A+ X-
A+ B+ X- B+ A+ X-
- - - -
A+ - A+ - A+ Resin B+ - B+ - B+
A+ - phase ion B+ -
- -
A+ B+ X- B+ A+ X-
A+ - A+ B+ - B+
- -
B+ X- A+ X-
A+ B+
- - A+ - - B+
A+ - B+ -
B+ X- B+ X- A+ X- A+ X-
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Stability
• Important for performance of the resin
• Parameters:
– Excessive osmotic swelling and shrinking
– Chemical degradation
– Structural changes caused by physical stresses
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EQUILIBRIUM RELATIONS
• Difference with adsorption:
– Exchange of ion
• The exchange is governed by a reversible,
stoichiometric chemical-reaction equation.
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Equilibrium Relations
Na+ + HR NaR + H+ (12.4-2)
(solution) (solid) (solid) (solution)
[ NaR][H ] (12.4-4)
K
[ Na ][HR]
Total ionic concentration in the resin,
[ NaR ]
[H ] K [ Na ]
(12.4-6)
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Regeneration of resin
• Shifting of the reversible chemical reaction
equation.
Cu2+ + 2HR CuR2 + 2H+
• To regenerate the resin (HR), need to shift the
equilibrium to the left.
• Done by increasing the concentration of H+
ions.
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Selectivity/ Affinity
• Depends on
– Nature and valence of ion
– Type of resin
– Ion concentration in solution
– pH
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Typical selectivity: Cation Exchanger
Fe3+>Al3+>Ca2+>Cu2+>Zn2+> Mg2+>Ag+>K+>
NH4+>Na+>H+>Li+
Conductivity
Throughput
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Typical selectivity: Cation Exchanger
Fe3+>Al3+>Ca2+>Cu2+>Zn2+> Mg2+>Ag+>K+>
NH4+>Na+>H+>Li+
Ca2+ Conductivity
Mg2+
Na+
Throughput
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Typical Selectivity: Anion Exchange
I->NO3->HSO4->NO2->Cl->HCO3->HSiO3-
>CH3COO->SO42->OH-
NO3- Conductivity
HCO3-
HSiO3-
Throughput
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Relative-Molar-Selectivity Coefficients
(K)
The equilibrium constant or selectivity
coefficient for exchange of any two ions A and B
can be approximated formula below:
KA
K A, B
KB
A + BR AR + B
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Relative-Molar-Selectivity Coefficients K for Polystyrene
Cation and Anion Exchangers with 8% DVB Cross-Linking
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Equilibrium constant for dilute
solutions
A + BR AR + B
K+ + HR KR + H+
cB q AR cH qKR
c A qBR cK qHR
K A,B
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Equilibrium constant for dilute
solutions
• Total concentration in liquid solution, C
C = cA + cB
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Example
Cu2+ + 2HR CuR2 + 2H+
• Relative-molar-selectivity coefficent is
c q
H
2
c q
CuR 2
K Cu 2 , H
Cu 2 HR
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Example
A waste acidic stream contains copper in solution
which is being removed by a strong acid-cation
resin. The cation Cu2+ (A) is displacing the cation H+
(B) in the resin. A polystyrene resin similar to the
table given is being used. The total resin capacity Q
is approximately 1.9 equivalents/l of wet bed
volume. For a total concentration C of 0.10 N (0.10
equivalents/L) in the solution, calculate at
equilibrium the total equivalents of Cu2+ in the resin
when the concentration is Cu2+ in solution is 0.02
M.
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Concentration profiles and
breakthrough curves
• Basic models in ion exchange – similar to
adsorption. Design methods are similar to
adsorption.
• Concentration profiles in packed bed – typical
S-shaped curve (similar to adsorption).
• Mass-transfer zone – MTZ travels down the
column (similar to adsorption).
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Scale-up design methods
• Capacity of column: Similar to adsorption
• Typical process variables:
– Laboratory: 2.5 cm dia. and 0.3 L.
– Commercial: 1 – 3 m in height
– Freeboard of 50% or more space is required to
accommodate bed expansion during the
regeneration process.
• Swelling of resin gel – 10 to 20%
• Size: 0.2 mm – 10 mm
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Scale-up design methods
• Regeneration flowrate – low (0.5 to 5 bed
volumes/h).
• Pressure drop – can be predicted by using
equations for flow in packed beds 13.6 – 20.4
kPa/m height).
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Design Considerations
Fixed-Bed Ion-Exchange Columns
- Rate depends on
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Industrial Applications
- Water softening
- Recovery of antibiotics/vitamin
from fermentation broth
- Decolourisation of sugar
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Demineralisation
• Removal of total dissolved solids.
• Uses both anionic and cationic resins.
raw water
Ca Mg Na
Degasifier
HCO3 Cl
Cation Anion
Acid exchanger exchanger Alkali
Storage tank
regenerant regenerant
treated water
H H2O
HCO3 Cl demineralised
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water