INTRODUCTION to ION

EXCHANGE
Part 1

© 2002 Rohm and Haas Company Intro 1 / 1

ION EXCHANGE RESINS
 Introduction to Ion Exchange

 Structure and activity of resins

• Matrix
• Functional group
• Cross-linking
• Classification
 Ion exchange resin properties
• Capacity
• Particle size
• Moisture
 Ion exchange reactions
 Selectivity
 Column operation
• Mode of regeneration

© 2002 Rohm and Haas Company Intro 1 / 2

 Structure

 Structure of Ion Exchange Resins

• An ion exchanger consists of the polymer matrix and
the functional groups that interact with the ions

 Polymer matrix:
• Polystyrene (85% of all resins)
• Polyacrylate (10%)
• Phenol-formaldehyde

 Functional groups:
• Cation-exchange
• Anion-exchange
• Chelating groups

© 2002 Rohm and Haas Company Intro 1 / 3

 Polystyrene

H
CH
H
C

H C H
C C
C
H C CH
H
Simplified
Styrene monomer representation
of styrene

Linear polystyrene

© 2002 Rohm and Haas Company Intro 1 / 4

 Cross-Linking

Styrene Divinylbenzene
(DVB)

Cross-linked polystyrene
DVB links linear chains of polystyrene
to obtain 3-dimensional stability

© 2002 Rohm and Haas Company Intro 1 / 5

 Gel structure

Pores
 Cross_linking is evenly
distributed in the matrix
 Pseudo-crystalline structure
 Pores = mesh of the matrix
 Natural porosity
 Even pore size (a few Å)
 Gel resin is transparent

© 2002 Rohm and Haas Company Intro 1 / 6

 Macroporosity

 Artificial porosity is created

with a porogen or phase
extender
Macropore  The porogen doesn't
participate in the
Macropore polymerisation
 It just takes room in the
system
 It is washed away once the
Macropore polymerisation is complete
 It leaves voids in the
structure = macropores
 Macroporous resins are
opaque

© 2002 Rohm and Haas Company Intro 1 / 7

 Sulphonation

Non-reactive polystyrene

H2SO4

Sulphonated polystyrene
= strongly acidic cation exchange
resin (SAC)
SO3H SO3H SO3H SO3H

Sulphonic group Amberjet 1200 H, Amberlite IR120 H

© 2002 Rohm and Haas Company Intro 1 / 8

 Chloromethylation

Anion exchange resins :

Activation is a
2-step process

CH3- O - CH2Cl
Chloromethyl ether

Chloromethylated polystyrene
(not an ion exchanger !)

CH2Cl CH2Cl CH2Cl CH2Cl Cl is covalent, not ionic

© 2002 Rohm and Haas Company Intro 1 / 9

 Amination

This Cl is ionic

CH3
CH3 -
+ CH3 N Cl
CH3 +
CH2 N CH3
CH2Cl
CH3

Trimethyl amine Quaternary ammonium

= Strongly basic anion exchange

resin (SBA)
Called Type 1

Amberlite IRA 402 Cl, Amberjet 4200 Cl

© 2002 Rohm and Haas Company Intro 1 / 10

 Other amines

Dimethyl
CH3
CH3
ethanol CH3 N Dimethyl
amine CH2Cl H N
CH2 CH2 OH amine
CH3

CH3 -
Cl CH3
+
CH2 N CH3 CH2 N + H+ Cl-
CH3
CH2CH2OH

SBA type 2 WBA

Amberjet 4600 Cl Amberlite IRA96

© 2002 Rohm and Haas Company Intro 1 / 11

 Basicity

CH3 CH3
OH- OH- CH3
+ +
CH2 N CH3 CH2 N CH3 CH2 N
CH3
CH3 CH2 CH2 OH
SBA type 1 SBA type 2 WBA Resins shown
IRA402 IRA410 IRA96 in their
regenerated
form

Decreasing basicity
© 2002 Rohm and Haas Company Intro 1 / 12
 Weakly Acidic Resins

There are two routes to produce the acrylic matrix:

CH2 CH2 CH2

H CH2
 C CH CH CH

CN CN CN CN
Acrylonitrile

H CH2 CH2 CH2 CH2

 C CH CH CH

COOCH3 COOCH3 COOCH3 COOCH3

Methyl acrylate

Both are crosslinked, with DVB or other cross-linkers

© 2002 Rohm and Haas Company Intro 1 / 13

 Hydrolysis

CH2 CH2 CH2

CH CH CH H2SO4
CN CN CN CH2 CH2 CH2
CH CH CH
NaOH
COOH COOH COOH
CH2 CH2 CH2 Polycarboxylic acid
CH CH CH
=
COOCH3 COOCH3 COOCH3 Weakly acidic cation
exchange resin (WAC)

Amberlite IRC86

© 2002 Rohm and Haas Company Intro 1 / 14

 Summary

O CH3
_
R C H
+ WAC R CH2 N WBA
O CH3

Amberlite IRC86 Amberlite IRA96

CH3 -
Cl
+
R SO3- H+ SAC R CH2 N CH3 SBA
CH3

Amberjet 1200 H Amberjet 4200 Cl

© 2002 Rohm and Haas Company Intro 1 / 15

 Acrylic anion resins
Same
polymerisation
Polymerisation
as WAC !
H CH2 CH2 CH2 CH2
C CH CH CH

COOCH3 COOCH3 COOCH3 COOCH3

CH2
CH2
CH3 CH
+ CH3 OH
CH
+ NH2 CH2 CH2 CH2 N Amidation CH3
C
COCH3
CH3 NHCH2 CH2 CH2 N
O
O
Dimethylaminopropylamine CH3

WBA
Amberlite IRA67

© 2002 Rohm and Haas Company Intro 1 / 16

 Weak and strong acrylic resins

Quaternisation

CH2 CH2
CH CH CH3Cl CH CH
CH3 Cl-
C CH3 or (CH3)2SO4 C
O NHCH2CH2N O NHCH2CH2N+-CH3
CH3 CH3

WBA SBA

Amberlite IRA67 Amberlite IRA458 Cl

© 2002 Rohm and Haas Company Intro 1 / 17

 Secondary cross-linking

CH2 CH2 CH2 CH2

CH CH CH CH

CH2 +HCl
Cl CH2
H

CH CH
CH CH CH2 CH2
CH2 CH2

© 2002 Rohm and Haas Company Intro 1 / 18

 Tertiary cross-linking

CH2 CH2 CH2 CH2

CH CH CH CH

CH2 Cl
CH2
Cl-
CH3 N CH3 N+ CH3
CH3
CH2 CH2

CH CH CH
CH
CH2 CH2 CH2
CH2

© 2002 Rohm and Haas Company Intro 1 / 19

 Cross-linking and porosity

High
Operating capacity
Mobility of ions (kinetics)

Resistance to oxidation
Difference in ionic affinity

Low DVB High

© 2002 Rohm and Haas Company Intro 1 / 20

 Other types
of ion-exchange resin

 Thiol -SH

 Aminodiacetic acid -CH2N(CH2COOH)2

 Aminophosphonic acid -CH2NHCH2CH2PO3H

 N-Methylglucamine -CH2N-(CHOH)4CH2OH

CH3

© 2002 Rohm and Haas Company Intro 1 / 21

 Examples of special resins

CH2 CH2 CH2 COOH

O
SH CH2 N CH2 N
P
OH CH2 COOH
H OH

Thiol Aminophosphonic Aminodiacetic

Duolite GT73 Duolite C467 Amberlite IRC748

© 2002 Rohm and Haas Company Intro 1 / 22

 Properties: capacity

DEFINITIONS
Total capacity : quantity of active
groups = total quantity of
exchangeable ions

Operating capacity : quantity of ions

really exchanged
during one cycle

© 2002 Rohm and Haas Company Intro 1 / 23

 Properties : moisture holding

100
90
Moisture content % H2O

80
70
60
50
40
30
20
10
0
0 2 4 6 8 10 12 14 16 18 20
% cross-linking (DVB)

Gel type sulphonic polystyrene resins

© 2002 Rohm and Haas Company Intro 1 / 24

 Particle size of standard resins

Gaussian distribution
Number of beads
between sieves

0
< 315 315 400 500 630 800 1000 > 1250
- - - - - -
400 500 630 800 1000 1250
Particle size range in µm

© 2002 Rohm and Haas Company Intro 1 / 25

 Particle size definitions

Gaussian-logarithmic plot
99.9 % Volume passing through sieve

99

90

U.C.= d60 / d10

60
50
40 Mean Diameter (d50) On graph:
d10 = 0.48 mm
d50 = 0.74 mm
10 d60 = 0.78 mm
Effective size (d10) UC = 1.62

1
d10 d60
0.1
0.2 0.3 0.4 0.6 0.8 1.2 mm

© 2002 Rohm and Haas Company Intro 1 / 26

 SAC exchange

R - SO-3 H+ + NaCl R - SO-3 Na+ + HCl

2 R - SO-3 H+ + Ca(HCO3)2 (R - SO-3)2 Ca++ + H2CO3

2 R - SO-3 Na+ + CaCl2 (R - SO-3)2 Ca++ + 2 NaCl

(Softening)

© 2002 Rohm and Haas Company Intro 1 / 27

 WAC exchange

2 R - COOH + Ca(HCO3)2 (R - COO-)2 Ca++ + 2 H2CO3

CO2 + H2 O
R - COOH + CaCl2 No reaction !

R - COOH + NaHCO3 R - COO- Na+ + H2CO3

R - COOH + NaOH R - COO- Na+ + H2O

(Neutralisation : possible only with macroporous resins)

WAC resins (H+) work only with alkalinity

© 2002 Rohm and Haas Company Intro 1 / 28

 SBA exchange

Neutral salt
R - N+R’3 OH- + NaCl R - N+R’3 Cl- + NaOH

Strong acid
R - N+R’3 OH- + HCl R - N+R’3 Cl- + H2O Irreversible !

CO2 = weak acid

R - N+R’3 OH- + CO2 R - N+R’3 HCO-3

SiO2 = very weak acid

R - N+R’3 OH- + SiO2 R - N+R’3 HSiO-3

© 2002 Rohm and Haas Company Intro 1 / 29

 WBA exchange

Neutral salt
R - NR’2 + NaCl No reaction !

Strong acid
R - NR’2 + HCl R - N+HR’2 Cl- (or R - NR’2.HCl)
Only strong acids can be exchanged because the weak base needs a proton

CO2 = weak acid

R - NR’2 + CO2 No reaction except with acrylics

SiO2 = very weak acid

R - NR’2 + SiO2 No reaction

© 2002 Rohm and Haas Company Intro 1 / 30

 Selectivity

In general (dilute solutions)

Trivalent > Divalent > Monovalent ions

Sulphonic (SAC) resins Amberjet 1200

Ba > Pb > Sr > Ca > Ni > Cu > Mg
Ag >> Cs > K > NH4 > Na > H > Li

Quaternary Ammonium (SBA) Amberjet 4200

SO4 > CrO4 > NO3 > CH3COO > I > Br > Cl > F > OH

© 2002 Rohm and Haas Company Intro 1 / 31

 Selectivity scales SAC

Amberjet
1200

SAC resin, 8% DVB SAC resin, 8% DVB

Monovalent Selectivity Divalent Selectivity
H 1.0 Mn 2.3
Li 0.85 Mg 2.5
Na 1.5 Fe 2.6
NH4 1.9 Zn 2.7
K 2.5 Cu 2.9
Cs 2.7 Ca 3.9
Cu 5.3 Sr 4.9
Ag 7.6 Pb 7.5
Ba 8.7

© 2002 Rohm and Haas Company Intro 1 / 32

 Selectivity scales SBA

Quaternary ammonium resin

Ion Type 1 Amberjet Type 2 Amberjet
4200 4600
OH 1.0 1.0
F 1.6 0.3
HCO3 6.0 1.2
Cl 22 2.3
NO2 24 3
CN 28 3
NO3 65 8
HSO4 85 15
I 175 17
Benzenesulphonate 600 75

Note : this is only typical : Different SBA resins have different affinity scales

© 2002 Rohm and Haas Company Intro 1 / 33

 Selectivity cont.

Note on crosslinking
Resins with higher X-linking (higher DVB) have a higher
affinity scale
SAC % DVB Na/H affinity
4 1.3
8 1.5
12 1.7
16 1.9

Note for SBA resins

Different active groups may change the order of affinities
(e.g. Nitrate-specific resin)

© 2002 Rohm and Haas Company Intro 1 / 34

 Selectivity cont.

Carboxylic (WAC) resins

H >> Ca > Mg >> Na
IRC86
Note 1 : At pH < 5, WAC resins are in the -COOH form, very little dissociated.
They can be used only in neutral or alkaline solutions.
Note 2 : Ba and Sr are not well removed by a WAC resin

Weakly Basic resins (amines, usually tertiary)

IRA96 They remove only Strong Acids from solution, e.g. HCl, H2SO4. They can
operate only in acidic solutions.

Note on Acrylic WBA resins

IRA67 They remove also carbonic acid (CO2), to a great extent.

© 2002 Rohm and Haas Company Intro 1 / 35

 Column operation

Fluid to be treated
(Influent)

Total capacity
Resin bed
2.1 eq/l resin
1 Bed volume
(BV)

Treated fluid
(Effluent)
© 2002 Rohm and Haas Company Intro 1 / 36
 Operating capacity

Exhausted resin

Bed
Depth Reaction zone

0 100
Exhaustion, % Regenerated resin

© 2002 Rohm and Haas Company Intro 1 / 37

 Cycle end point

Operating capacity
1.3 eq/l resin
Exhausted resin

Reaction zone

0 100
Regenerated resin
Exhaustion, % Leakage

© 2002 Rohm and Haas Company Intro 1 / 38

 Co-flow regeneration

Regenerant Liquid to
be treated

Eluate
(spent regenerant) Leakage

© 2002 Rohm and Haas Company Intro 1 / 39

 Counter-flow regeneration

Liquid to
be treated

Eluate
(spent
regenerant)

Clean
polishing
zone

Regenerant

© 2002 Rohm and Haas Company Intro 1 / 40