ENVE 303

UNIT OPERATIONS AND PROCESSES OF WATER

TREATMENT

ION EXCHANGE
Ion Exchange
• Ion exchange is the reversible interchange of
ions between a liquid and solid, in which there
are no permanent changes in the structure of
the solid.
• Certain ions in solution are preferentially sorbed
by the ion exchanger solid, and because
electroneutrality must be maintained, the
exchanger solid releases replacement ions back
into the solution.
• For instance: Ca & Mg in water replace Na ions
in the exchanger solid.
Ion Exchange
• Ion exchangers are insoluble solid materials,
which carry exchangeable cations or anions.
When the ion exchanger is in contact with an
electrolyte solution, these ions are exchanged
with an equivalent amount of other ions of the
same sign.
• Cation and anion
exchangers are the
materials that carry cations
and anions, respectively.
Ion Exchange
• Ion exchange is similar in many ways to
adsorption treatment but chemical mechanism is
ion exchange rather than adsorption.
• Ion exchange is a sorption phenomenon where
the mechanism of sorption 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.
Applications of Ion Exchange

• Ca, Mg (hardness removal)

• 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+3
• Radioactive waste treatment
(Cation Exchange) Softening

2 R – Na+ + Ca+2 R2-Ca + 2 Na+

Cation Exchange
Softening
Water Softener
Demineralization
• Demineralisation is a process by
which inorganic salts, often referred
to as Total Dissolved Solids (TDS),
are removed from water.
• Demineralised water contains hardly
any cations and anions, therefore, the
conductivity is very low ( < 0.2
µS/cm).

• Two-column systems, where the water first passes through a cation

exchange column and then passes through an anion exchange
column.
• Demineralized water is used;
• In steam boilers
• In food industries
• As process water
Demineralization
• Water is first passed through cation exchange
resins charged with H+ (cation removal) ;

M+x + xH.R  M.Rx + xH+

• Water is then passed through the anion exchange

resin charged with OH- (anion removal);

A-x + xR.OH  Rx.A + xOH-

Ion Exchange Resins
Two types of ion exchangers;
• Naturally occurring ion exchangers
– Many natural minerals, such as clays (e.g. bentonite)
and zeolites (e.g. clinoptilolite), are capable of
exchanging ions. However, crystalline aluminosilicates
are principally the common natural minerals with
cation-exchange properties (Hellferich, 1995).
Amongst natural inorganic ion exchangers, zeolites
and clays are the most common materials. Other
natural aluminosilicate materials, such as green sand,
are also found in specific waste-treatment
applications.
Two types of ion exchangers;
• Synthetic ion exchangers
– Synthetic inorganic ion exchangers Zeolites:
Synthetic resins are available as powder, pellet, or
bead. The greatest advantage of synthetic resins
against natural zeolites is that they can be
manufactured with a wide variety of physicochemical
properties.
– Synthetic organic ion exchangers The largest group
of ion exchangers available today is synthetic organic
resins. The resin matrix is a flexible network of
hydrocarbon chains (polymers), where fixed ionic
charges at various fixed positions are contained.
Polymeric resins are made in 3-D networks by cross-
linking hydrocarbon chains. The resulting resin is
insoluble, inert and relatively rigid.
Two types of ion exchangers;

• Most ion exchange materials used in water

treatment are synthetic resins made by the
polymerization of organic compounds into a
porous three-dimensional structure.
Resin Classification
Resins are classified based on the type of functional
group they contain and their % of cross-linkages.
Resin Classification
Cationic Exchangers:
- Strongly acidic

- Weakly acidic

Anionic Exchangers:
- Strongly basic

- Weakly basic
Resin Classification
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).
Anionic Exchangers:
- Strongly basic

- Weakly basic
Resin Classification
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).
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’-
Typical Ion-Exchange Reactions
• Ion exchange reactions are stoichiometric and
reversible, similar to other solution phase
reactions.

For Zeolites (Z)

Ca+2 Ca+2
ZNa2 + Mg+2 Z Mg+2 + 2Na
Fe+2 Fe+2
Typical Ion-Exchange Reactions
For Synthetic Resins (R)

Strong-acid cation exchange (SAC)

Acid form RSO3H + Na+  RSO3Na + H+

Salt form 2RSO3Na + Ca+2  (RSO3)2Ca + 2Na+
R: organic portion of the resin
Typical Ion-Exchange Reactions
For Synthetic Resins (R)

Weak-acid cation exchange (WAC)

Ionizable group: COOH or SO3H

RCOOH + Na+  RCOONa + H+

2RCOONa + Ca+2  (RCOO)2Ca + 2Na+
Typical Ion-Exchange Reactions
For Synthetic Resins (R)

Strong-base anion exchange (SBA)

RR3′NOH + Cl-  RR3′NCl + OH-

Weak-base anion exchange (WBA)

RNH3OH + Cl-  RNH3Cl + OH-

2RNH3Cl + SO4-2  (RNH3)2SO4 + 2Cl-
Typical Ion-Exchange Reactions
• SAC resins;
 degree of ionization is analogous to that of a strong acid
(low pKa)
 ready to exchange over a wide pH range
• WAC resins;
 useful only within a fairly narrow pH range

• SBA resins;
 useful over a wide pH range
• WBA resins;
 useful over a narrow pH range
Properties of Ion Exchange
Resins
• 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).
Properties of Ion Exchange
Resins
• Total capacity: Total # of ionic sites available for
exchange per unit mass ( meq/g dry weight)
2-10 meq/g Typical SAC 3.6-5.5 meq/g
Typical wet volume capacity
1.8-2.0 meq CaCO3/ mL

• Effective Capacity: # of sites that can be

exchanged under a specific set of conditions.
(It is affected by the total capacity, level of
regeneration, solution composition & conditions
in the exchange column).
Properties of Ion Exchange
Resins
• Selectivity: Refers to the relative preference of
resins for different types of ions ( is affected by
concentration, ionic charge, ionic size)

• Selectivity Coefficient: Preference for ions of

particular resins is often expressed through an
equilibrium relationship using the selectivity
coefficient.
 For the exchange of A+ on the
resin for Bn+ in solution
n[R]A+ + Bn+ ↔ [nR]Bn+ + nA+

An operational equilibrium constant can be defined;

KAB =

KAB = Selectivity coefficient

• The superscript and subscript on the selectivity
coefficient indicate the direction of the reaction. The
superscript is the reaction side and the subscript is the
product side of the exchange reaction.
For the exchange of A+ on the
resin for Bn+ in solution
Neglecting activity corrections we can write:

KAB =

Where:
[A+], [Bn+] = mole A+, B+ per liter of liquid
[RA], [RBn+]= mole of A+, B+ on resin per liter of
resin (bulk volume basis).
Selectivity Coefficient
• The greater the selectivity coefficient, the
greater the preference is.
• Selectivity coefficients are reported for various
resins and various exchangeable ions.
Selectivity coefficients can be combined to give
a variety of new selectivity coefficients.

=
Also note that: =
Selectivity Coefficient
• 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.
Selectivity Coefficient

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.
Selectivity Coefficient

• The selectivity coefficient is only applicable

over a narrow range of concentrations
because the activity coefficients vary with
concentration.
Separation Factor
• The preference of an ion exchange material for
one ion over another is often expressed in terms
of separation factor, Qs:

Qs =

= Qs []

In the instance of monovalent exchange, n =1;

K = Qs
Separation Factor
• ∝B or Qs > 1  ion Bn+ is preferred over A+

• ∝B or Qs < 1  ion A+ is preferred over Bn+

• ∝B or Qs = 1  equal preference for each ion

1.0
Qs > 1
Equivalent ion
fraction in solid Qs = 1
phase
Qs < 1

1.0
Equivalent ion fraction in solution
Preference Series
• In general, ions of high valance are preferred
over ions of low valance.
Since electrostatic forces between
Fe+3 > Mg+2 > Na+ ions and resin increases with
increasing charge, ions with higher
PO4 > SO4 > NO3
-3 -2 -
valances are usually preferred.

• This preference increases with a decrease in the

total ionic concentration.

• At high ionic concentrations, the magnitude of

charge becomes less important.
Preference Series
• For ions of the same valance, the extent of the
exchange reaction increases with decreasing
hydrated radius and increasing atomic number.
Ca+2 > Mg+2 > Be+2 K+ > Na+ > Li+

• Typical preference series for the usual cation

exchangers (SAC resins)
Ba+2 > Sr+2 > Ca+2 > Cu+2 > Co+2 > Zn+2 >
Mg+2 > Ag+ > K+ > NH4+ > Na+ > H+ > Li+
Preference Series

• For the usual anion exchangers (strong base

resins), the preference series is:

PO4-3 > SO4-2 > ClO4- > NO3- > CrO4-2 > Br - >
Cl- > HCO- > F- > OH-
Preference Series
• These series are to be used as a guide,
exceptions can occur!
• Test (either column or batch) should be
performed!
• For a solution with a high ionic concentration,
the extent follows no general rule & is often
reversal.
Equilibrium & Kinetics
• Equilibrium in ion exchange systems is
described by adsorption isotherm expressions,
such as Langmuir and Freundlich equations.
• Ion exchange resins are generally used in
columns operating under non-equilibrium
conditions. The principal steps in exchange
mechanism are:
– transfer of ions through the boundary at the external
surface
– diffusion of ions through the porous internal structure
– exchange of ions at the sites of functional groups
Exchange Isotherms
• Isotherms are an alternative to describe
equilibrium by selectivity coefficients. These
isotherms have the same format as those for
carbon adsorption, i.e., Langmuir, Freundlich,
etc.
Kinetics versus equilibrium

• Ion exchange adsorption is much faster than

carbon adsorption and as a result we can use
equilibrium assumption in design calculations.
Regeneration
• Spent or exhausted columns must be
regenerated because the cost of the resin would
make one-time use prohibitive. Since ion
exchange is a very reversible process,
regeneration can be accomplished by
manipulation of solution composition.
Applications
Softening
• Strong acid cation resins  for water softening
• Since they have good physical & chemical
stability & effectively remove Ca+2 and Mg+2 over a
wide range of pH.

2 RSO3Na + Ca+2  (RSO3)2Ca + 2Na+

For regeneration, 5-20% solution of NaCl is

applied at a level of 5-10 lb NaCl / ft 3 resin (80-
160 kg/m3)
Applications
Softening Feed water
• The capacity and efficiency Ca+2, Mg+2 M+.A-
of an ion-exchange softener
vary with: Strong
acid
– type of solid medium
cation
– type of exchange material resin
used for coating charge
– quantity of regeneration d with
Na+
materials
– regeneration contact time
– flow rate Na+, M+.A-
– degree of regeneration
Applications
Softening
• Generally, the capacity of ion-exchange
materials ranges from 2 to 10 meq/q or 15-100
kg/m3
Na+ + Na+ + Na+ + resin w/ Na+-R
Na+ +
Anion Anion adsorbed
Anion Anion
resin w/ Ca+2-
R adsorbed

active
exchange zone

Ca+2 + Anion Ca+2 + Anion Ca+2 + Anion Ca+2 + Anion

System operation
1. Service: The raw water is passed downward
through the column until the hardness exiting the
column exceeds the design limit.
2. Backwashing with the product water
to remove SS
to eliminate gas pockets
to restratify the resin bed
3. Regeneration
System operation (cont’d)
4. Slow rinse
(to push the regenerant through the bed)

5. Fast rinse ( final rinse step)

6. Return to service
Column Configuration
• Pressurized usually downflow

• Gravity downflow or upflow (expanded bed)

Upflow rate restricted by size and density of
resin.
Downflow restricted by headloss and available
head.
Typical design for water
softening
• Sulfonated polystyrene cation exchange resin
with exchange capacity of about 2 eq/L
(5 meq/g dry wt).
Softening cycle:
1. soften to exhaustion
2. backwash to loosen particulate matter (not
needed in upflow)
3. regeneration (downflow)
4. rinse (downflow)
5. return to forward flow
Operating parameters
Typical EBCT 1.5 – 7.5 min Brine contact time 25 – 45 min

Flowrate 200-1000 m3/d or 8-40 Salt dose 48 – 160 kg/m3 (3 -10

BV/h lb/ft3 resin brine)
Operating exchange 0.6 – 1.2 eq/L Concentration 8 - 16 % (by wt)
capacity
Bed depth 0.6 – 1.8 m Rinsing 50 – 100 gal/ft3 of
requirements resin
Head loss 0.3 – 0.6 m of water Rinse flow 0.68 – 3.4 L / m2.s (1
- 5 gpm/ft2 )
Freeboard 50 – 70% of the bed Rinse volume 2.8 – 5.6 m3/m2 (20 -
depth 40 gal/ft3 resin)
Softening flow 3.4 – 6.8 L / m2.s (5 - 10 Regeneration td = 30 min
gpm/ft2)
Backwash 50 – 75% expansion 1-2 gpm/ft2

Backwash flow 3.4 - 4.1 L / m2.s (5 - 6 2-10% regenerant

gpm/ft2) solution