About Ion Exchange

Marc Slagt
Technical Support Specialist
EMEA

The Dow Chemical Company

Ion Exchange Fundamentals

I. INTRODUCTION
1.What is ion exchange?
2.Resins
1.Structure
2.Matrix
3.Functionality
4.Particle size

3.The system
4.Exchange reactions
5.Ion exchange process
6.Safety and Awareness

1. What is ion exchange?

The mechanism
OH-

Cl-

resin

IEX

resin

H+

+ H2O
Na+

chemicals
Na+
Drinking water
(water + ions)

Cl

Na+ + Cl-

RO

H2O
pressure

membrane

1. What is ion exchange

H

H
H

FUNCTIONAL
GROUP

H
H

H
H

H
H

H
H

H
H

H
H

H
H

CARBON CHAINS
NETWORK

H
H

H
H

H
H

SOLVENT (WATER)
IN THE POROSITY

1. What is ion exchange

Na+
Drinking water
(water + ions)

Cl-

Cl-

Static
RESIN
bed

Na+

The IER System

H 2O

2. Resins
What are ion exchange resins?
CH=CH2

A. Chemical structure

Styrene

B. Matrix

C. Functionality
SO3-H+

2. Resins: Chemical structure

Polystyrene structure
CH=CH2
Styrene

CH

CH2

CH

CH2

CH

CH2

CH

CH2

CH

CH2

CH

CH2

CH

CH2

CH

CH2

2. Resins: Chemical structure

Styrene Divinylbenzene (DVB) Copolymer
CH=CH2

CH=CH2

Styrene

Divinylbenzene
CH=CH2

CH

CH2

CH

CH2

CH

CH2

CH

CH2

CH

CH2

CH

CH2

CH

CH2

CH

CH2

Cross linkage

2. Resins: DVB cross linkage

Total capacity
Selectivity
Physical stability
Chemical stability

IF % DVB

Water retention
Swelling
Kinetics
Regenerability/Operating capacity
Organic desorption ability

2. Resins : Acrylic structure

CH2

CH2

CH2

CH

COOCH3

COOCH3 COOCH3 COOCH3

CH
COCH3

CH

CH

CH2

CH2

CH2

Polymerisation

+ NH2CH2CH2CH2N

CH3

+ CH3OH

CH

Amidation

CH3

Dimethylaminopropylamine

Same
polymerisation
as WAC !

C NHCH2CH2CH2N
O

WBA
Amberlite IRA67

CH3
CH3

2. Resins: Cation manufacture

Styrene
Polymerization
/ catalyst

(I)

Sulfonating acid
/ swelling
(II)

Styrene-DVB copolymer
Divinylbenzene

SO3-H+
Strong Acid Cation Resin

2. Resins: Anion manufacture

Styrene
Polymerization
/catalyst

(I)

ClCH2OCH3
(II)

CH2Cl
Styrene-DVB copolymer
:N(CH3)2R
(III)

Divinylbenzene
R = CH3 (Type 1)
R = CH2-CH2-OH (Type 2)
R = 0 (WBA)

CH2N+(CH3)2R ClStrong Base Anion Resin

2. Resins : matrix
Gel
Po r es

Cross-linking is evenly
distributed in the matrix

Pseudo-crystalline structure

Pores = mesh of the matrix

Natural porosity

Even pore size (a few )

Gel resin is transparent

2. Resins : matrix
Macroporosity

Artificial porosity is created with

a porogen or phase extender

The porogen doesn't participate

in the polymerisation

It just takes room in the system

It is washed away once the

polymerisation is complete

It leaves voids in the structure =

macropores

Macroporous resins are opaque

Macropore
Macropore

Macropore

2. Resin: Functionality
a lot of choice..
Cation Exchange Resins
Weak Acid
Strong Acid
Anion Exchange Resins
Weak base
Strong Base
Type 1
Type 2
Acrylic
special chemical groups

2.Resins: functionality
Cation Exchange Resin
Strong Acid Cation (SAC)
Exchange Resin

SO3-

H+

Weak Acid Cation

Exchange Resin

O
H+

C
O-

SO3-

Removes all cations

High operating capacity

High chemical efficiency

Removes hardness
in ratio to alkalinity

2.Resins: Functionality
Anion Exchange Resin Weak Base (WBA)

CH3

N:

HCl

Removes Free Mineral Acids Only:

HCl, H2SO4, HNO3, etc.

CH3
High Operating Capacity smaller vessels
High Regeneration Efficiency less chemicals
Good for organics removal less fouling

2.Resins: Functionality
Anion Exchange Resin Strong Base
Type 1 Anion
Exchange Resin

Type 2 Anion
Exchange Resin

CH3

CH3
OH-

N+ CH3

N+ CH3

OH-

CH2 CH2 OH

CH3
High Chemical Stability
High Silica Removal

High Operating Capacity/regeneration

Lower Silica Removal than Type 1!
Sensitive to temperature

Removes all anions

2.Resins: functionality
acrylic anion
CH2
CH

CH

C
O

CH2

Quaternisation

CH3
NHCH2CH2N

CH3Cl
or (CH3)2SO4
O

CH

CH

CH3 ClNHCH2CH2N+-CH3

CH3

WBA
Amberlite IRA67

CH3

SBA
Amberlite IRA458 Cl

2.Manufacturing steps

Cation

CO-POLYMERIZATION

Anion

DRYING
SIEVING
SULFONATION
HYDRATION

CHLOROMETHYLATION
AMINATION
WASHING
DEWATERING
PACKAGING

2.Stirred reactor
MONOMERS
STYRENE
DIVINYLBENZENE
CATALYSTS
(POROGENIC CHEM.)

CONTROL
TEMPERATURE

STIRRING
SUSPENSION MEDIUM
WATER + STABILISER

HEATING

2. DOW uniform resin JETTING

Copolymer exit

Suspension solution
Monomer feed

Orifice plate
Chamber

Piston
Motor

2. Resins: Particle size distribution

Conventional (Gaussian) resins typically 0.3-1.2 mm

bead size range.
UPS resins typically ~0.6 mm (600 m).
Information source: DOWEX Ion Exchange Resins, The Advantages
of Uniform Particle Sized Ion Exchange Resins, March 2006
Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow

2. Resins: Particle size

uniformity
Uniformity Coefficient (UC)

screen size passing 90%

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

Volume Percent

90%

90%
40%

200

400

Volume Percent

40%

600

800

1000

1200

Bead Size, microns

UC = 1010 m / 650 m = 1.6

1400

200

400

600

800

1000

Bead Size, microns

UC = 580 m / 540 m = 1.07

1200

1400

2. Resins: Particle size

Vol. (%)

A = Effective Size = 90% volume of beads retained

B = Harmonic mean diameter= 50% volume of beads passed

B
0

Bead diameter
50%
90%

3. The System
Application (softening, demin, polishing,
boron, nitrate, scavenging, etc)
Vessels + operational logic
Distribution system
Piping + valves
Regeneration station + chemical storage
Waste discharge / Neutralization facilities
Feed water and product water distribution
PLC control system

4. Ion exchange reactions

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+

H+
Na+
Cation
resin
bead

H+
H+
Na+

H+

H+

4. Ion exchange reactions

selectivity
Resin selectivity creates
chromatographic exhaustion:
loosely held ions travel
quickly
tightly held ions travel
2+
Ca
slowly
moving ionic wave fronts Mg2+
are established
Na+

H+

4. Ion exchange reactions

Selectivity
Selectivity Increases with Charge
Al3+ > Ca2+ > Na+
SO42- > Cl
Selectivity Increases with Atomic Number
Ca2+ > Mg2+
Br- > Cl- > F-

4. Ion exchange reactions

Cationic selectivity
ION VALENCE

DEGREE OF CROSS-LINKAGE
4% DVB
8% DVB
16% DVB

MONOVALENT IONS
H
Li
Na
NH4
K
Cs
Ag

1.0
0.90
1.3
1.6
1.75
2.0
6.0

1.0
0.85
1.5
1.95
2.5
2.7
7.6

1.0
0.7
1.9
2.5
3.3
3.4
17.0

DIVALENT IONS
Mn
Mg
Zn
Cu
Ca
Pb
Ba

2.2
2.4
2.6
2.7
3.4
5.4
6.15

2.35
2.5
2.7
2.9
3.9
7.5
8.7

2.7
2.8
3.0
3.6
5.8
14.5
16.5

KHNa > 1 means that the affinity for Na is higher than that for H

4. Ion exchange reactions

Selectivity

ANION RESINS SELECTIVITY COEFFICIENT

TYPE 1

TYPE 2

OH

1.0

1.0

FLUORIDE
ACETATE
BICARBONATE
CHLORIDE
BISULFITE
NITRATE
CITRATE

1.6
3.2
6.0
22
27
65
220

0.3
0.5
1.2
2.3
3
8
23

4. Ion exchange reactions

Weak acid cations
Neutralize bases:

R-H + Na+OH R-Na+ + H2O

High capacity for alkaline earth metals associated with alkalinity:

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

Limited capacity for the alkali metals with alkalinity:

2R-H + Na+2CO3 2R-Na+ + CO2 + H2O

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

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

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

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

WACs is responsible for capacity & efficiency

4. Ion exchange reactions

Weak acid cation

Feed water ions:

Na+
K+
RFR
Mg2+
Ca2+
ClSO42NO3- of
HCO
End
3
regeneration
HSiO
3

pH = 7

Outlet ions:
Na+
K+
ClSO42NO3-

Ca2+
2H+

In service

CO2
HSiO3pH ~ 5

4. Ion exchange reactions

Strong acid cations

Splits salts/neutralize bases:

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

2R-H + Ca2+(HCO3)2 R2-Ca2+ + 2CO2 + 2H2O
In the neutral (sodium) form, they can be used for softening:

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

SACs is responsible for water quality

4. Ion exchange reactions

Inlet ions:
Na+
K+
(Leakage)
ClSO42NO3CO2
-)
(HCO
End3of
regeneration
HSiO
3

Strong acid cation

Outlet ions:
Na+ leakage
H+

RFR
Na+

ClSO42NO3-

H+

In service

CO2
HSiO3-

= pH

4. 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

WBA is responsible for capacity & efficiency

4. Ion exchange reactions

Inlet ions:
Na+ leakage
H+
ClSO42NO3-

Weak base anion

RFR
Outlet ions:

Cl-

Na+ leakage

OH-

CO2
HSiO3-

CO2
HSiO3-

End of
regeneration

In service

4. 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

SBA is responsible for water quality

4. Ion exchange reactions

Strong base anion

Inlet ions:
Na+ leakage
CO2
HSiO3-

RFR
HSiO3-

Outlet ions:

OHNa+ leakage
OHEnd of
regeneration

In service

= pH

4. Ion exchange reactions

Change of resin volume change in ionic
form
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%

5. Ion exchange process

Batch process

Fresh bed

exhaustion

regeneration

exhaustion

Common regenerants:
HCl / H2SO4
NaCl
NaOH
NaCl

=
=
=
=

Cation resin
Cation softening
Anion resin
Anion organic scavenger

5. Ion exchange process

Production = loading of ions
Start

End

Regenerated
resin

Exhausted resin

Reaction zone

Total capacity
100%

Conductivity
Leakage

Operating capacity
75% of total

5. Ion exchange process

Regeneration = taking ions off the resin
Eluate

(spent
regenerant)

Before
regeneration

Regenerant
(upflow)

Reverse flow
regeneration

Feed water

After
regeneration

UPCORE
Amberpack

Clean
polishing
zone

5. Ion exchange process

Regeneration = taking ions off the resin
Regenerant
(downflow)

Feed water

Co flow regeneration

Before
regeneration

After
regeneration

Eluate

(spent regenerant)

Residual
close to
column
outlet

5. Ion exchange process

Na Na
Na
Na

CFR
Na
H
H

Na
H
H H
Na

End of
regeneration

InHservice

Na H

Co-flow regeneration:
H
The badly regenerated bottom layers cause ionic leakage

5. Ion exchange process

Quality during production
Conductivity profile
60

50

40

30

20

10

0
0

20

40

60
co-flow

80
counter flow

100

120

5. Ion exchange process

Regeneration brings quality and quantity
1.
2.
3.
4.
5.
6.

Amount of chemicals per liter resin (g/l)

Temperature of the regeneration (anion)
Contact time
Concentration of the injected chemicals
Bed Lift
Displacement of chemicals

Amount of regenerant : Quantity

The regeneration method : Quality

5. Ion exchange process

Equivalent per liter
Ion Exchange Process All parameters are calculated as charge
100 mgCa2+/liter = 100 / (40/2) (atomic mass / valence) = 5 meq/l
1 liter cation resin (H) = 1000 meq OperatingCapacity
1000 meq OC / 5 = 200 liter of water to treat until exhaustion
110% stoichiometry of HCl to regenerate:
1,1 * 1000 = 1100 meq HCl * 0,0365 = 40 gram 100% HCl / liter resin

5. Ion exchange process

Generating eq/l capacity with regeneration

TVC
OC

160% (log scale)

The amount of chemicals per volume of resin makes a certain amount of the
total volume capacity available (as equivalents per liter) = operating
capacity. For that you need 1 eq HCl for 1 eq cations + excess as
stoichiometry to the ionic load.

5. Ion exchange process

Typicals on capacity
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
1.5
1
0.5
0

Weak
cation

Strong
cation

Weak
anion

Strong
anion
type 1

Strong
anion
type 2

Additional support
More information is available on the web:

http://www.dowwaterandprocess.com/
- Product info
- Technical information
- Operational data like Tech Facts
- Troubleshooting guidance
- Literature
- The Answer center

Design and evalaution software : IXCalc / CADIX

introduction

6.Safety and Awareness

6.Safety and Awareness

Resins are active chemical products.
Concentrated chemicals are used in the process
Resin spill on the floor is dangerous
Sample connections and measurement connections
can be filled with chemicals
Chemicals do not always have odor or color
Be alert and protect yourself.

Thank
You