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
