EKB3143: SEPARATION

PROCESSES
ION EXCHANGE
Muhammad Syafiq Alias
e-mail: [email protected]

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Definition of Ion Exchange

A reversible chemical reaction where

an ion from a solution is exchanged
for a similarly charged ion attached to
an immobile solid particle
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 Ion Exchange
• Ion exchange is like an adsorption phenomenon
where the mechanism is electrostatic.
• Electrostatic forces hold ions to charged functional
groups on the surface of the ion exchange resin.
• The adsorbed ions replace ions that are on the
resin surface on a 1:1 charge basis.
• Chemical reactions between ions in solution and
ions in an insoluble solid phase
• Example: Water softening (to remove calcium
ions)
General ion exchange reactions and regeneration
reactions:
(1) Cation Exchange:
Cation exchange is employed in two modes,
(a) Hydrogen cycle exchange
The exchange reaction is,

where,
M2+ = metal cation (also M3+or M+)
Ex = exchanger solid matrix
The regeneration reaction is,

A large excess of H+ ions are provided for

regeneration by a strong acid solution (2%
to 10% by weight) usually H2SO4 or HCl.
(b) Sodium Cycle Exchange
Commonly used for water softening.
2 Na+ ions are exchanged for each metal
M2+ ion in solution (or 3 Na+ exchanged for
each M3+, and etc.). The exchange and
regeneration reactions can be represented
together as,
 Exchange

Regeneration

An excess of Na+ ions are provided for

regeneration via a concentrated NaCl brine
(2% to 10% by weight).
(2) Anion exchange
Anion exchange usually involves exchange of
OH- ions in two modes:
(a) Salt Splitting
The exchange and regeneration reactions
can be represented together as,
 Exchange
Regeneration

A large excess of OH- ions are provided for

regeneration using a concentrated NaOH
solution (2% to 10% by weight).
(b) Acid Removal
The exchange and regeneration reactions
are,
Exchange
Regeneration

A large excess of OH- ions are provided for

regeneration using water.
Mechanism of Ion Exchange
• The techniques used in ion exchange so closely
resemble those used in adsorption that for the
majority of engineering purposes ion exchange can
be considered as a special case of adsorption.

• Applications of Ion Exchange: Water softening

• Hardness in water, caused by calcium and
magnesium ions, which form insoluble compounds,
is removed by ion exchange.

Ca2+ + Na2 R  Ca R + 2 Na+ (12.4-1)

(solution) (solid) (solid) (solution)
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Water softening

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 Water softening (contd.)
• Hard water is filtered through an artificial zeolite
(cation exchange resin) , such as Permutite.
• The sodium in the zeolite replaces the
undesirable ions that are in the water.
• The positively charged ions in solution such as
Ca2+ diffuse into the pores of the solid and
exchange with the Na+ ions in the mineral.
• When the zeolite is saturated with these metallic
ions, it is washed with salt solution, which
restores the sodium.

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Common applications of ion exchange include:
• water softening
• demineralization
• deoxygenation
• desalination
• recovery of valuable metals
• recovery of acids
• chemical manufacture
• treatment of hazardous and radioactive wastes
Applications of ion exchange in water &
wastewater

•  Ca, Mg (hardness removal) exchange with Na or H.

•  Fe, Mn removal from groundwater.
•  Recovery of valuable waste products Ag, Au, U
•  Demineralization (exchange all cations for H all
anions for OH)
•  Removal of NO3, NH4, PO4 (nutrient removal).
Ion Exchange Media
• The ion exchange process depends upon the ability of certain solid
substances (called exchange media) to exchange ions bound to the
surface of the solid with inorganic ions of another species dissolved
in water.
• The process must be both selective for the ions to be removed and
reversible.
• Once the ion exchange sites on the solid medium have been
exhausted, the medium is removed from service and chemically
regenerated.
• Ion exchange media have a finite number of exchange sites
available and the total solid-phase concentration of ions is called the
ion exchange capacity of the medium (meq ions/gm of medium).
 Ion Exchange Media types
•  Natural: Proteins, Soils, Lignin, Coal, Metal
oxides, Aluminosilicates (zeolites) (NaOAl2O3.4SiO2).
•   Synthetic
• Synthetic resins are polymers that are manufactured in
the form of pellets or beads with a size of approximately
0.5 mm.
• zeolite gels and most common -polymeric resins
(macroreticular, large pores).
• Polymeric resins are made in 3-D networks by cross-
linking hydrocarbon chains. The resulting resin is
insoluble, inert and relatively rigid. Ionic functional
groups are attached to this framework.
 These resins are generally manufactured by
polymerizing neutral organic molecules such as
sytrene (to form polystrene) and then cross-linked
with divinyl benzene (DVB).
 Functional groups are then added according to the
intended use. For example the resin can be
sulfonated by adding sulfuric acid.
Ion Exchange Resin:
 Resin classification:

Resins are also classified based on the type of

functional group they contain and their % of cross-
linkages

A) Cationic Exchangers:
- Strongly acidic – functional groups derived from
strong acids e.g., R-SO3H (sulfonic).

-  Weakly acidic – functional groups derived from

weak acids, e.g., R-COOH (carboxylic).
B) Anionic Exchangers:

- Strongly basic – functional groups derived

from quaternary ammonia compounds, R-N-
OH.

- Weakly basic - functional groups derived

from primary and secondary amines, R-NH3OH
or R-R’-NH2OH.
 Ion Exchange Resins
Commercial ion exchangers

• Amberlite
• Duolite
• Dowex
• Ionac
• Purolite

Form of spherical beads from about 40m to

1.2mm diameter.

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Ion exchange capacities of Various materials:
Exchange Ion Exchange
Medium Capacity (meq/gm)
Clay 0.03 - 1.1
Glauconite (green sand) 0.09 - 0.18
Zeolite (aluminosilicates) ~ 1.4
Sulfonated Coal ~ 1.7
Synthetic Resins 3 - 10

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 Selectivity Coefficients
Preference for ions of particular resins is often expressed
through an equilibrium relationship using the selectivity
coefficient. The coefficient is described below.
For the exchange of A+ in solution for B+ on the resin:

The barred terms indicate location on the resin (resin phase)

as opposed to solution phase. For this exchange an
operational equilibrium constant can be defined as
Selectivity coefficients are reported for various resins and
various exchangeable ions. Selectivity coefficients can be
combined to give a variety of new selectivity coefficients.
For example:
Neglecting activity corrections we can write:

Where:
[A+], [B+] = moles A+, B+ per liter of liquid

= moles of A+, B+on resin per liter of

resin (bulk volume basis).

This selectivity coefficient is not quite a thermodynamically

defined equilibrium constant because of the strange choice of
concentration units and the lack of activity corrections. So it
is clearly an operational equilibrium constant.
Factors which affect the selectivity coefficient:
 For a given resin type, ion selectivity is a function of ionic
charge and hydrated radius and functional group-ion
chemical interactions. In most cases the higher the ionic
charge the higher the affinity for a site.
 The smaller the hydrated radius of the ion the greater the
affinity. This depends on the % cross-linkage of the resin.
 The reason that hydrated radius has an effect on selectivity is
that macro-reticular pore spaces have limited volume as
determined by % cross-linkage.
 Some exchanged ions can actually cause a swelling of the
resin (it’s relatively deformable). The swelling causes a
backpressure that reduces the preference for ions with larger
hydrated radii.
 The selectivity coefficient is only applicable over a narrow
range of concentrations because the activity coefficients
vary with concentration.
 Because we need to maintain a charge balance during the
ion exchange process it is more convenient to express
concentration of ions as equivalents instead of molar
concentration. Therefore, we define:
C = total concentration of exchangeable ions in the liquid
phase (eq/L).
For example, if Ca2+ and Na+ are the only exchanged ions.
C = [Na+] + 2[Ca2+]
 Equilibrium Relations
Na+ + HR  Na R + H+ (12.4-2)
(solution) (solid) (solid) (solution)

(12.4-4)

Total ionic concentration,

= [NaR] + [HR] = constant

(12.4-6)

(Ref. 1)
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 Equilibrium and Regeneration
• Ion-exchange process for strong acid or strong base
exchangers by replacing ions in a solution with either:
– H+
Originally in the resin
– OH-
• Regeneration: small amount of solution with high
concentration of:
– H+ for cation exchangers
– OH- for anion exchangers
Regeneration shifts the equilibrium to the left, making
the regeneration process more favorable

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 Relative-Molar-Selectivity Coefficients (K)
• The equilibrium constant or selectivity coefficient for exchange
of any two ions A&B
• Table 12-4-1: Relative molar selectivity coefficient for
polystyrene with 8 % DVB for strong acid/base resins
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

Iodide 8.7 H+ 1.27
Nitrate 3.8 Na+ 1.98
Acetate 0.2 NH4+ 2.55
Sulfate 0.15 K+ 2.90
Hydroxide 0.05 – 0.07 Mg2+ 3.29
Cu2+ 3.85
Ca2+ 5.16
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 Relative-Molar-Selectivity Coefficients
(K)
A + BR  AR + B
(solution) (solid) (solid) (solution)

KA,B = KA/KB KA,B = cBqAR/cAqBR

(c = ion concentration in equivalents/L volume of solution)

(q = ion concentration in equivalents/L of bulk bed volume)

C = cA + cB (total ion concentration in liquid solution)

Q = qA + qB (total ion concentration in resin)

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 Kinetics versus Equilibrium.
• Ion exchange is much faster than carbon
adsorption and as a result we can use
equilibrium assumption in design
calculations.

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 Example 12.4-1
• 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
of Cu2+ in solution is 0.02M (0.04 N).

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Solution to Example 12.4-1 part1

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Solution to Example 12.4-1 part2

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 Design Considerations:
Fixed-Bed Ion-Exchange
Columns
• Rate depends on
– Mass transfer of ions from bulk to particle
surface
– Diffusion of ions 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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Modes of Operation (Similar to adsorption)
a) Continuous countercurrent: packed bed

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Modes of Operation b) Continuous
Countercurrent: fluidized-bed

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Advantages of Ion Exchange
• Increased value of a product because of
improved properties.
• Recovery of valuable components
• Recovery of water for re-use
• Better quality control due to elimination of
process variability.
• Reduced waste disposal costs due to elimination
of objectionable components or reduced volume.
• Reduction of corrosion or scaling in subsequent
equipment

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 Disadvantages

• Capital cost of equipment.

• Resin costs which may be either capitalised or
expensed depending on resin life.
• Cost of chemical regenerants.
• Operating labour.
• Disposal costs for regenerant wastes

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 References

1. Geankoplis C. J., Transport Processes and Unit

Operations, 4th Edition, Prentice Hall, 2003.
2. Seader J. D. and Henley E. J., Separation Process
Principles, John Wiley, 1998
3.
http://pasture.ecn.purdue.edu/~eql/H2Oanalyseanio
n

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