Ion Exchange (IEX) Process

with focus on organic matter removal

CHBE 373 October 28th , 2014

What are we studying today ?

IEX, an efficient process for water treatment
How does IEX work?
Fundamentals and applications
Operation and challenges
Lets do some calculations
Think-Pair-Share

Water analysis
What needs to be removed from water?

Organics

Inorganics

Taste & odor compounds

Synthetic organic chemicals
Pesticides, herbicides and etc.
Natural Organic Matter (NOM)

Hardness (Ca+2 , Mg+2)

Alkalinity (CO3-, HCO3-2)
Salts (Na+, K+, Cl-, NO3-)
Scale forming chemicals (SiO2)

ionic : + & - charge

nonionic: no charge !
3

Courtesy of Franois de Dardel, ([Link])

IEX Applications

Water Treatment (softening, NOM removal)

Food Industry (sugar extraction)

Chemical Industry (metal extraction)

Pharmaceutical Industry (drug purification)

Other Applications

[Link]

Mining
[Link]

Analytical chromatography

[Link]

How IEX works ?

Exchange of the ions on the resin structure with the ones
present in the solution
Courtesy of Franois de Dardel, ([Link])

Ca+2

Cation IEX
Ca+2 + 2 Na-R

NO3-

Counter ion
Ca-R2 + 2 Na+

Anion IEX
NO3- + Cl-R

NO3-R + Cl6

How IEX works ?

Cation +

Courtesy of Lewatit

Removal mechanisms:

Anion -

Ionic exchange of negatively charged NOM

Adsorption of NOM
Regeneration
resin

Adsorption

resin

Courtesy of ORICA

Important characteristics of resin

Functional group (strong or weak)
Backbone structure (acrylic or styrene)
Resin water content
Physical form (gel or macroporous)

Bead size
Treatment process
8

Resin Structure
Polystyrene

Polyacrylic
DVB

Gel

Macroporous

Courtesy of Franois de Dardel, ([Link])

Resin Types
Remove hardness/alkalinity and other cations
Weakly Acidic Cation Exchange Resins (-COOH)
Strongly Acidic Cation Exchange Resins (-HSO3- )
Remove anions (NO3-, SO4-2, HCO3-) and organics

organics are typically

negatively charged

Weakly Basic Anion Exchange Resins (-N(CH3)2)

Strongly Basic Anion Exchange resins (-N(CH3)3 OH)
o Type I (trimethyl amine)
o Type II (dimethyl ethanol amine)
10

Capacity
Exchange capacity (eq/L)
The number of ion exchange sites
Operating capacity (useful capacity)
The number of ion exchange sites where exchange has really
taken place during the loading run.

Operating capacity < Total capacity

11

Operating capacity depends on:

Concentration and type of ions to be adsorbed
Service flow rate
Temperature
Type, concentration and quantity of regenerant
Type of regeneration process (co-flow, reverse flow)

Bed depth (reverse flow regeneration only)

Particle size of the ion exchange resins

Performance data and computer programs

12

 The typical operating capacity of a weak base anion

exchange resin is 70 to 90 % of the total capacity.

The typical operating capacity of SAC and SBA resins is about

40 to 60 % of their total capacity.
Resin type

Total Capacity

Operating
Capacity

WAC

3.7- 4.5

1-3.5

SAC

1.7-2.2

0.6-1.7

WBA

1.1-1.7

0.8-1.3

SBA

0.9-1.4

0.4-0.9
Courtesy of Franois de Dardel, ([Link])

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Throughput
Volume produced until the cartridge has to be replaced

Salinity of the feed water

Volume of resin in the cartridge
Type of resin used
Quality and efficiency of the off-site regeneration process
Endpoint (conductivity at which the unit is considered
exhausted)
With good resins and good regeneration, the throughput can be
approximately calculated as:
Throughput [L] = 500 (Resin volume [L]) / (Salinity [meq/L])

14

Water Softening
Remove hardness mainly Ca+2 and Mg+2
Strongly acidic cation exchange resin in Na+ form
Applications

Domestic and industrial water boilers

Laundries, Dish washer
Soft drink plants
Treated water quality
Residual hardness < 0.02 meq/L (1 mg/L as CaCO3) with
reverse flow regeneration
Regeneration: brine (NaCl as a 10 % solution)
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Degasification
2 R-H + Ca (HCO3)2 R2-Ca+2 H+ + 2 HCO3H+ + HCO3CO2 + H2O
(CO2 solubility @ 25 : 1.5 g/L)

Reduce the ionic load thus regenerant

CO2 residual 10 mg/L

A Liquicel membrane degasifier

Courtesy of Franois de Dardel, ([Link])

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Degasifier

Courtesy of Franois de Dardel, ([Link])

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Degasifier
Atmospheric degasser (bicarbonate + CO2 < 0.6

meq/L)
Forced draft degasser
Thermal degasser, (O2-CO2)
Vacuum degasser, (1-5 kPa, O2-CO2)
Membrane degasser

Small size, for RO permeates with low pH and high

free CO2, small demineralization systems
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Water Dealkalization
Remove bicarbonate and temporary associated hardness
Weakly acidic cation exchange resin in H+ form
Applications

Beverages, Soft drink plants, municipal water

Treated water quality
Endpoint at 10 % of the raw water alkalinity
Contains CO2 which requires degasifier
Regeneration: Acid (preferably HCl at 5 % concentration)
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Water Demineralization
Remove all forms of ions from water CIX (H+) - AIX (OH-)
Treated water contains only traces of sodium and silica
Applications
Beverages, soft drink plants, municipal water
Treated water quality (lower than RO or Distillation)
Conductivity: 0.2 to 1 S/cm
Residual silica 5 to 50 g/L
Regeneration: strong acid and caustic soda
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Water Demineralization

Courtesy of Franois de Dardel, ([Link])

Water for high pressure boilers

Rinse water used in electronic devices
Water for batteries
Water for laboratories
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Natural Organic Matter (NOM)

Negatively charged molecules (OH-, COOH-)

Wide range of molecular sizes
Measured as Dissolved Organic Carbon (DOC), UV254
[Link]

22

Conventional Drinking Water Treatment

Plant
IEX
Clogging

IEX

IEX

Use of chemicals

Large footprint, Sludge

[Link]

IEX can positively improve the performance of

entire treatment as well as individual units
23

IEX as pre-treatment
Coagulation

can remove hardness, alkalinity, and organics (NOM)

if they can be removed prior to adding coagulant (less
coagulant will be needed)

Complimentary role
Lower coagulant dose
Lower pH adjustment
Better settling and dewatering characteristics of flocs

Disinfection-Oxidation
Lower chlorine dosage
DBPs precursor removal

Reduced fouling and plugging

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Configurations
SIX Process

Conventional Packed bed

MIEX Process
25

Operational aspect
Column Operation

Courtesy of Franois de Dardel, ([Link])

26

Operational aspect
Batch (well-mixed)

Courtesy of ORICA, [Link]

27

Regeneration

Courtesy of Franois de Dardel, ([Link])

28

Regeneration
Co-flow regeneration
Reverse exchange (displacement
of low affinity with high affinity
ions)
Requires large excess of solution
to fully regenerate
Leakage in the next run
Counter-flow regeneration
Higher reg. Efficiency, lower reg.
quantity
Lower elution leakage
Lower resin inventory
Improved water quality
Hard to keep the resin bed
consolidated
Resin mixing
Purity of the regenerant

Courtesy of Franois de Dardel, ([Link])

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Regenerant
NaCl (10% ) or NaOH (4%) for SBA
WBA, NaOH, NH3, bicarbonate
HCl for nitrate removal
De-alkalization WAC , HCl, H2SO4 (0.7%)
Demineralization (SAC)
o HCl (5%), efficient no precipitation
o H2SO4 (0.7-6%), cheaper and easier to store , less efficient,
potential for precipitation
o HNO3, exothermic reaction, dangerous, not recommended

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Brine reuse
Reduction of regenerant salt disposal and waste
requirements

Biological denitrification (sludge blanket reactors, 96%)

Sulphate reduction (62%)

GAC and or NF(contaminants ellimination)

Capacitive deionization (CDI)

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Column test : Breakthrough Curve

32

Batch test : Jar Test

33

Kinetics of NOM (DOC) removal

1

DOC/DOC0

0.8

Fast initial removal

0.6
0.4
Slow removal
0.2
Equilibrium

0
0

100

200
300
Time (min)

400

500

at equilibrium resin is exhausted

34

Bottle point experiments

1. Constant concentration Vary adsorbent
2. Constant adsorbent Vary concentration

A
B
C

Measure initial C
Mix solution and adsorbents continuously

Measure C vs. t till equilibrium

Equilibrium : no further change in C vs. t

Measure residual C i.e., Ceq

Construct q vs. Ceq for steps 1 and or 2

35

Kinetics of IEX
Liquid phase

Solid phase

m An+ +n Bm+ m An+ + n Bm+

qA

qB

K A B

n m
A
. B

n m
A
. B

cB
cA

KAB : equilibrium constant (Thermodynamic) , selectivity coefficient

36

Kinetics of IEX
, A : substance adsorbed (mg/g) at equilibrium (solid phase concentration)
m : resin mass (g)
V : solution volume (L)

(0 )
=

0 : initial concentration of substance in the solution (mg/L)

, c : equilibrium concentration of substance in the solution (mg/L)

@ Equilibrium & using [1]

qA
K A B
cA

cB

q
B

n
2

37

Kinetics of IEX
=

Q : total exchange capacity of the IEX resin (eq/L)

C : total ionic concentration in the solution (eq/L)
XA : fraction of A specie in solution
YA : fraction of A specie in solid phase, Note : =

, =

+ = 1 , + = 1

Considering above and eqn. [2]

Y
K A B A
X
A
YA

XA
A
B
YB
XB

1 X A

1Y
A

Q

C

mn
3

Separation factor: indicate ion

exchange preference
38

Kinetics of IEX
0.2
0.4
0.6
0.8

Fraction of A in solid phase , YA ,

Fraction of B in solid phase , YB ,

1
Fraction of A in liquid phase , XA ,

What does higher KAB mean ?

What does KAB=1 mean?
What does =1 mean?

Chen et al., 2006

39

Selectivity
Charge, hydrated radius, activity of functional group, ionic strength
Strongly acidic
Li+ < H+ < Na+ < NH4+ < K+ < Ag+< Mn2+ < Mg2+ < Cu2+ < Ni2+ < Ca2+< Pb2+ <Al3+
Weak-acid ion exchange resins adsorb hydrogen ions most strongly

Weakly basic
Ac < F < Cl < Br < I < NO3 < H2AsO3< H2PO4 < oxalate < HSO4 < OH
Strongly basic

F < OH < Ac < HCO3 < Cl < CN< Br < NO3 < ClO3 < HSO4< I
Chen et al., 2006

40

Clifford , 1999

41

IEX Calculations - Isotherms

Degree of ion uptake depends on chemical and physical properties of the resin and
the solution chemistry
Equilibrium (sorption isotherm)

What is an isotherm ?

Langmuir theoretical isotherm

qmax .[Link]
qe
1 [Link]
: substance adsorbed (mg/g) at equilibrium (solid phase concentration)
(0 )
=

m : resin mass (g)

V : solution volume (L)

0 : initial concentration of substance in the solution (mg/L)

: equilibrium concentration of substance in the solution (mg/L)
Langmuir constant (related to heat of adsorption)
: maximum sorption capacity
42

Linearized Langmuir equation

qe

qmax .[Link]
1 [Link]

1
1
1
1
=
+

1
.

43

Freundlich empirical isotherm

1

: ,
1
: , .

1
log = log + log

1
:

empirical equations fail to describe mechanism and also amount of the

ion released

44

Favorable : 1/n < 1

Linear : 1/n = 1

Unfavorable : 1/n > 1

C
45

Chemical Equivalence
An amount of material that will release or react with an Avogadro's number of
electrical charges (i.e., 1 mol) on molecules like OH-, H+ and or electrons.
The equivalent weight of an element is its gram atomic weight divided by its valence
Acid : the amount of the acid that donates one mole of H+ in reactions with bases
Base : the amount of the base that will react with one mole of H+

where n is the number of H+, OH- , # of valence

()
=

1 mol H3PO4 = 3 equivalents H3PO4

1 mol H3PO4 = 98 grams H3PO4 ; 1 equivalent H3PO4 = 32 grams H3PO4
1 eq H2SO4 = 49.04 g H2SO4
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Chemical Equivalence
Calculate the #eq of Ca(OH)2 in 6.32 g of Ca(OH)2

=
2

MW
2

74.09
2

= 37.05

Using the formula:

# . 2 =

2
6.32
=
= 0.171 .
2
37.05

Substances react with each other in stoichiometric, or chemically equivalent,

proportions

47

Think-pair-share
Blue baby syndrome
Strong base anion exchange is used to remove nitrate from the water with
following characteristics
ion

Conc. mg/L

ion

Conc. mg/L

Ca+2

30

Cl-

106.5

Mg+2

24.30

SO4-2

Na+

49.9

NO3-

150

Resin capacity = 2 eq/L

Selectivity for nitrate = 5

Maximum volume of water that can be treated if 15 L of resin is used?

48