Ion Exchange 101

Donna DeFlavis

Content
Introduction to Ion Exchange

What is IX?
Types of resins
Applications
Manufacturing

Chemical and Physical Characteristics

Particle Size
Ionic Form
Total Exchange Capacity
Water retention Capacity
Mechanical Stability
Thermal and Oxidative Stability

Dynamic Properties

IX reactions
IX kinetics
Selectivity
Regenerability
Operating capacity

Introduction to Ion Exchange

Introduction

What is IX?

Types of resins

Applications

Manufacturing

What is IX?
-Definition of ion exchange
Ion exchange is the reversible exchange of ions between a solid and
a liquid in which there is no substantial change in the structure of the
solid.

Exhaustion
Na+
H+
H+
H+

Regeneration

Na+

H+

H+
Cation
resin
bead

Na+
H+
Na+

H+

H+

H+
Na+
Cation
resin
bead

H+
H+
Na+

H+

H+
5

H+

Type of Resins
-Resin Polymer structure
Composition

Polystyrene (85% of all resins)

Polyacrylate (10%)
Phenol-formaldehyde

Crosslinking

We introduce cross-linking to our copolymers in the form of divinyl

benzene abbreviated as DVB.
The amount of DVB determines the level of cross-linking which is in
effect the tightness or looseness of the finished ion exchange resin.
Production of the copolymer is very important as it determines many of
the physical properties of the final product such as bead size and bead
strength.

Types of Resin
-Polymer matrix
Gel matrix

Macroporous matrix

Gel matrix

Macroporous matrix

Gel resins
Continuous polymer with low pore size 5-15
Translucent
Good regeneration/ highest capacity

Macroporous resins
Void volumes with large pore size 50-200
Opaque
Good bead strength/organic removal

Types of resins
-functional groups

Cation Exchange Resins

Strong Acid (SAC)
Weak Acid (WAC)
Anion Exchange Resins
Strong Base (SBA)
Type 1
Type 2
Weak Base (WBA)
other special chemical groups, such as chelating resins

Types of resins
-Cation exchange resin

Strong Acid Cation (SAC)

Exchange Resin

SO3-

H+

Weak Acid Cation (WAC)

Exchange Resin

O
H+

C
O-

SO3Removes: Na+, Ca2+

Mg2+, Fe2+ etc.

High total exchange capacity

High chemical efficiency

Removes:
Cations present with alkalinity

Types of resins
-Strong base anion exchange resin
Type 2 anion
exchange resin

Type 1 anion
exchange resin

CH3

CH3
N+ CH3

OH-

N+ CH3

OH-

CH2 CH2 OH

CH3
High Chemical Stability
High Silica Removal

Lower basicity than Type 1

High Operating Capacity/ regeneration
Lower Silica Removal than Type 1
Sensitive to temperature

Remove: Cl-, SO42-, HCO3-, HSiO3-, etc

Types of resins
-Weak base anion exchange resin (WBA)

CH3

N:

HCl

Only Removes Acids:

HCl, H2SO4, Formic acid, etc.

CH3
High Operating Capacity
High Regeneration Efficiency
Good for organics removal

Applications
WATER TREATMENT
Industrial water softening
Industrial water demineralization
Condensate polishing
Ultra-pure water production
FOOD & PHARMACEUTICAL APPLICATIONS
Sugar juice treatment
Brewery, Fruit juices
Pharmaceutical
CHEMICAL INDUSTRY
Electroplating
Hydrometallurgy
Catalysis

POLLUTION CONTROL
Nitrate removal
Heavy metals removal
Cl-solvent removal
Waste water

NUCLEAR INDUSTRY

12

Manufacturing steps

Cation

CO-POLYMERIZATION

Anion

DRYING
SIEVING
SULFONATION
HYDRATION

CHLOROMETHYLATION
AMINATION
WASHING
DEWATERING
PACKAGING

13

Polymerization (Gaussian Beads)

MONOMERS
STYRENE
DIVINYLBENZENE
CATALYSTS
(POROGENIC CHEM.)

CONTROL
TEMPERATURE

STIRRING
SUSPENSION MEDIUM
WATER + STABILISER

HEATING

Jetting Polymerization (Uniform Beads)

Dynamic formulation of the droplets

Resin beads are jetted
Bead size is uniform

Chemical and Physical Characteristics

Content

Particle Size Characterization

Uniformity Coefficient

Mean Size

Ionic Form of resin

Total Exchange Capacity

Water Retention Capacity (%)

Mechanical stability

Thermal and oxidative stability

17

Particle Size

Conventional (Gausssian) resins typically 0.3-1.2 mm

bead size range
UPS resin typically ~0.6mm (600 m)
18

Particle Size
-Uniformity Coefficient
Uniform
(Marathon/Monosphere/Amberjet)

Number of beads

Gaussian
(Dowex/Amberlite)

300

600

900

1200

How do you Measure Uniformity?

Uniformity Coefficient (UC)

screen size passing 90%

------------------------------screen size passing 40%

90%

90%
40%

200

400

Volume Percent

V o lu m e P e rce n t

40%

600

800

1000

1200

1400

200

400

600

800

1000

1200

Bead Size, microns

Bead Size, microns

UC = 1010 m / 650 m = 1.6

UC = 580 m / 540 m = 1.07

20

1400

Type of Resins
-Bead uniformity
AMBERJET, MARATHON, MONOSPHERE
Very uniform UC* 1.1 to 1.2

Highest performance
Mandatory for AMBERPACK & packed bed systems requesting NO FINES
Very useful in mixed beds (no need for interface)
DOWEX UPCORE for UPCORE plants & designs
Block reverse flow and co-flow systems

Specially graded resins

UC* 1.1 to 1.5

RF for AMBERPACK & other Reverse Flow systems

SB, LB for STRATABED , Layered Bed units

Number
of beads

Uniform

AMBERLITE, DOWEX
Gaussian UC* 1.3 to 1.8

Gaussian

For co-flow systems

300

*UC = Uniformity Coefficient

600

900

1200m

Other particle size definitions

Vol. (%)

A = Effective Size = 90% volume of beads retained

B = Volume Median Diameter = 50% volume of beads passed

B
0

Bead diameter
50%
90%

22

Ionic form-Change of resin volume

INDUCES A CHANGE
IN VOLUME

STRONG ACID CATION RESIN

GEL
Na to H + 7%
MACRO Na to H + 5%
WEAK ACID CATION RESIN
MACRO
MACRO
GEL

H to Ca + 15%
H to Na + 60%
H to Na + 90%

STRONG BASE ANION RESIN

Cl to OH + 15-20%
Cl to OH + 10-12%
WEAK BASE ANION RESIN
FB to HCl + 20-35%

Total exchange capacity

Defined as theoretical total exchangeable ions from the resin

Expressed,
either volume unit : eq/l wet
or

weight

unit : eq/kg dry

With reference to a specified ionic form

24

Total exchange capacity

CATION EXCHANGE RESINS

EQ/L (Na)
EQ/L (H)
EQ/KG (Na)
EQ/KG (H)

ANION EXCHANGE RESINS

EQ/L (Cl)
EQ/L (OH)
EQ/KG (Cl)
EQ/KG (OH)

STRONG ACID
GEL MACRO

WEAK ACID
GEL MACRO

2.00
1.85
4.50
5.00

2.35
4.40
9.00

1.85
1.75
4.50
4.90

STRONG BASE
GEL MACRO
1.40
1.15
1.15
1.00
3.90
4.00
4.20
4.30

25

2.65
4.20
9.00

WEAK BASE
MACRO
1.05
1.40
3.80
4.40

Water Retention Capacity (WRC)

-Ion Exchange Resins Hold Water
After functional charges are added:
resins become hydrophilic, absorbing water (40-60%
water)
functional charges are repelled from one another,
causing resin swelling
the presence of water is critical for transport of ions into
and out of the resin bead

26

Water retention capacity vs. ionic form

STRONG ACID CATION EXCHANGE RESINS
H FORM

Na/NH4 FORM

GEL TYPE 8% DVB

50-55%

44-48%

GEL TYPE 10% DVB

46-50%

38-43%

MACROPOROUS TYPE

50-55%

44-50%

STRONG BASE ANION EXCHANGE RESINS

OH FORM

Cl FORM

GEL TYPE

55-65%

43-48%

MACROPOROUS TYPE

65-72%

56-64%

27

Water Retention Capacity (WRC)

-WRC vs. degree of cross-linkage

28

Mechanical Stability

FRIABILITY (Crush)

Pressure on:
The resin bed surface
The resin beads

ATTRITION

Shear forces exerted by one bead

on another during:
Backwashing
Resin transfer
Air cleaning/mixing
Shrink and swell stress exerted on
a bed during:
Loading/regeneration
Resin cleaning
Cross-regeneration (mixed
beds)

OSMOTIC SHOCK

29

Thermal Stability
CATIONS:
Can operate up to 150C (300F) in the Na form.
Degrade through loss of sulfonate functional group at >120C in the H
form.
Cation resin stability dependent on pH: cleavage of carbon-sulfur bond
increases at lower pH: up to 120 C in the H form.

ANIONS:
Degrade through conversion of strong base groups into weak base
groups.
Type 2 also lose ethanol group and form weak base groups (max 35C)
Can operate up to 60C (140F) recommended for OH cycle (Type 1).
Anion resin stability dependent on pH: cleavage of carbon-nitrogen bond
increases at higher pH.

Thermal Stability

Strong acid cation

150 C in Na form
120 C in H+ form

Weak base anion and strong base anion type I

80 - 100 C in loaded form
50 - 60 C in regenerated form

Strong base anion type II

35 C in regenerated form

Oxidative Stability

Strong acid cation

Structure more sensitive than active group
Loss of crosslinking, increase of water content
Lower volume capacity, density and mechanical stability

Strong base anion

Active group more sensitive than structure
Loss of TVC

Weak base anion

Loss of active groups
Increase of rinse requirements: formation of COOH

Oxidative Stability

Following levels of free chlorine can be tolerated

Weakly acidic cation exchanger

< 0.5 ppm

Strong acid cation exchanger gel

< 0.20 ppm

Weakly basic anion exchanger

< 0.05 ppm

Strong base anion exchanger

< 0.05 ppm

Dynamic properties

Content

IX reactions

IX kinetics

Selectivity

Regenerability

Operating capacity

35

Ion exchange reactions

-Strong acid cations

Splits salts/neutralize bases:

R-H + Na+Cl R-Na+ + HCl

Strong Acid Cation
In the neutral (sodium) form, they can be used for
softening:

2R-Na + Ca2+Cl2 R2-Ca + 2 Na+Cl

Ion exchange reactions

-Weak acid cations
High capacity for alkaline earth metals associated with
alkalinity:

2R-H + Ca2+(HCO3)2 R2-Ca2+ + 2CO2 + 2H2O

No significant salt splitting occurs with neutral salts, due
to equilibrium with HCl:

R-H + Na+Cl R-Na+ + HCl

However, if resin is neutral (Na form), softening can be
performed:

2R-Na + Ca2+Cl2 R2-Ca2+ + 2NaCl

Weak Acid Cation

Ion exchange reactions

-Weak base anions
Weak base anion resins are capable of adsorbing strong acids onto the
electron pair on the free amine group:

R-N: + H+Cl- R-N: HCl

Weak Base Anion

Ion exchange reactions

-Strong base anions
Splits salts/neutralize acids:
R-OH + NaCl- R-Cl- + NaOH
2R-OH + H2SO4 R2-SO4 + 2H2O
R-OH + HSiO3- R-HSiO3 + OHIn the neutral (chloride) form, they can be
used for nitrate or anionic metal complex
removal:
R-Cl + NaNO3 R-NO3 + NaCl

Strong Base Anion Type 1

Ion exchange resin kinetics

Kinetic Rate governs the speed of ion exchange
Selectivity governs the preference for a particular ion
In some applications, speed of ion exchange is critical
RESIN BEAD

LIQUID FILM
( boundary layer )

A+
A+
SOLUTION

H+

H+

A+

H+

Kinetics: Rate of Ion Exchange

The diffusion rate is a function of:

In the resin:
In the film :
In the solution :

1/R2
1/R
not influenced
by bead size

Ion exchange selectivity

Selectivity Increases with Increasing Charge

Al3+ > Ca2+ > Na+
SO42- > Cl
Selectivity Increases with Atomic Number (Size)
Ba2+ > Sr2+ > Ca2+ > Mg2+
Br- > Cl- > F-

Ion exchange selectivity

Resin selectivity creates

chromatographic exhaustion:
loosely held ions travel
quickly
tightly held ions travel
slowly
moving ionic wave fronts
are established

Ca2+
Mg2+
Na+
H+

Strong acid cation exchange resins

-Resins selectivity coefficient
ION VALENCE
MONOVALENT IONS
H
Li
Na
NH4
K
Cs
Ag
DIVALENT IONS
Mn
Mg
Zn
Cu
Ca
Pb
Ba

DEGREE OF CROSS-LINKAGE
4% DVB
1.0
0.90
1.3
1.6
1.75
2.0
6.0
2.2
2.4
2.6
2.7
3.4
5.4
6.15

8% DVB
1.0
0.85
1.5
1.95
2.5
2.7
7.6
2.35
2.5
2.7
2.9
3.9
7.5
8.7

16% DVB
1.0
0.7
1.9
2.5
3.3
3.4
17.0
2.7
2.8
3.0
3.6
5.8
14.5
16.5

Strong base anion exchange resins

-Resins selectivity coefficient

TYPE 1

TYPE 2

OH

1.0

1.0

FLUORIDE
ACETATE
BICARBONATE
CHLORIDE
BISULFITE
NITRATE
CITRATE
SALICYLATE
LIGNOSULFONATE

1.6
3.2
6.0
22
27
65
220
450
>500

0.3
0.5
1.2
2.3
3
8
23
65
75

Resin operating capacity and total capacity

Ionic leakage (as % of feed)

100

Inlet feed concentration

90
80
70

<---Operating

Capacity---> <--Over-run-->

60
50

Total capacity = A + B

40
30
20

Ionic leakage

Ionic breakthrough

10
0
0

50

100

150

Feed water passed

200

250

Operating vs. total capacity

-Typical figures
Comparison of Operating and Total Capacity
5

Total capacity (area A+B)

Operating capacity (area A)

4.5

Typical capacity (eq/l)

4
3.5
3
2.5
2

Weak
cation

Strong
cation

Weak
anion

1.5
1
0.5
0

46

Strong
anion
type 1

Strong
anion
type 2

Regenerability

Regeneration efficiency

Resin capacity achieved (eq/l)

100% = [1.3/2] x 100 = 65%
Regenerant added

Stoichiometric ratio = [2/1.3] x 100 = 154%

47

Factors affecting regenerability and operating

capacity

Regenerant level: High amount of regenerant gives higher

operating capacity.

Matrix cross-linking: High DVB content slows ion diffusion due to

tight matrix structure and gives lower regenerability and operating
capacity. Macroporous worse than gel.

Ionic form: High selectivity ions (e.g. calcium) more difficult to

regenerate off the resin, so operating capacity lower.

48

Effect of matrix structure on performance

Total capacity
Selectivity
Physical stability
Chemical stability

IF % DVB

Water retention
Swelling
Kinetics
Regenerability/Operating capacity
Organic desorption ability

Thank You!

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