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SEPARATION PROCESS II

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

A reversible chemical reaction where


an ion from an aqueous phase is
exchanged for a similarly charged ion
attached to an immobile solid phase
(resin)
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WATER SOFTENING
• In ion exchange, certain ions are removed by ion-exchange
solid.
• This is done due to the maintenance of electroneutrality,
where the solid releases replacement ions to the solution.
• For example, hardness in water, caused by Ca2+, is
removed by exchange with the Na+ ions in the solid.

Ca2+ + Na2R  CaR + 2 Na+ (12.4-1)


(solution) (solid) (solid) (solution)

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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-

Resin Charged functional


lattice groups on resin lattice 8
Properties of synthetic resins
Type of resin Characteristics
Strong-acid cation resins (SAC) • Behave like strong acid
• Highly ionised
• Acid form – (R-SO3H)
• Salt form – (R-SO3Na)
Weak-acid cation resins (WAC) • Have weak-acid functional group (-COOH)

Strong-base anion resins (SBA) • Highly ionised


• Have strong-base functional group (OH)

Weak-base anion resins (WBA) • Have weak based functional group

Heavy-metal selective chelating resins • Similar to weak-acid cation


• But have a high degree of selectivity for
heavy-metal cations.
• Functional group – EDTA
• R-EDTA-Na 9
SYNTHETIC ION EXCHANGE RESIN
• Made from
– Styrene
– Divinylbenzene
– Cross-linked polystyrene
• Important properties
– Exchange capacity
– Particle size
– Stability

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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,

R = [NaR] + [HR] = constant


K R Na  

[ 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+

Na+, Mg2+, Ca2+

Conductivity

Throughput

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Typical selectivity: Cation Exchanger
Fe3+>Al3+>Ca2+>Cu2+>Zn2+> Mg2+>Ag+>K+>
NH4+>Na+>H+>Li+

Na+, Mg2+, Ca2+

Ca2+ Conductivity

Mg2+

Na+
Throughput

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Typical Selectivity: Anion Exchange
I->NO3->HSO4->NO2->Cl->HCO3->HSiO3-
>CH3COO->SO42->OH-

HSiO3-, HCO3-, NO3-

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

Strong-Base Anion Exchange Strong-Acid Cation Exchanger


(Relative to Cl- as 1.0) (Relative to Li+ as 1.0)
Cl- 1.0 Li+ 1.0
I- 8.7 H+ 1.27
NO3- 3.8 Na+ 1.98
CH3COO- 0.2 NH4+ 2.55
SO42- 0.15 K+ 2.90
OH- 0.05 – 0.07 Mg2+ 3.29
Cu2+ 3.85
Ca2+ 5.16

DVB = divinyl benzene


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Example
A + BR  AR + B
K+ + HR  KR + H+
KA
K A, B 
KB
2.90
  2.28
1.27

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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

qKR & qHR = equivalents/L of bulk bed volume of


water-swelled resin
cH+ & cK+ = equivalents/L of volume of solution

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Equilibrium constant for dilute
solutions
• Total concentration in liquid solution, C
C = cA + cB

• Total concentration in the resin, Q


Q = qAR + qBR

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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

• Mass transfer ions from bulk to particle surface

• Diffusion in the pores of solid to surface

• Exchange of ions at the surface

• Diffusion of the exchange ion back to the bulk


solution.
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Operating cycles
1. Downflow loading of the process feed.
2. Displacement of the feed solution with
upward flow of the regeneration solution.
3. Regeneration of the bed with continued
upward flow of the regeneration solution.
4. Rinse upward to remove the adsorbed
regenerant from the bed.

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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