Ion Exchange Operations

Matt Roth

Content

Performance Drivers

Performance Factors

Equilibrium
Selectivity
Equilibrium leakage
Kinetics
Operating capacity
Cycle end point
Reaction zone
Flow distribution
Regeneration

Plant Operation

Feed water
Demineralization service cycle: WAC, SAC, WBA, SBA
Throughput; water quality
Regeneration: backwash, chemical injection, displacement, fast rinse

Equilibrium and Kinetics

-Controlling principles and performance

Performance drivers content

Equilibrium
Selectivity
Equilibrium leakage

Kinetics

Equilibrium as a Driving Force

B
Equilibrium

A
Potential Difference

Equilibrium Equation
K

R-X + O
[RO]
O
K X = [RX]

R-O + X
[X]
[O]

O
is Selectivity Coefficient
X

Describes the relative affinity (equilibrium) of an IER for two different ions

Selectivity

Relative preference for one ion over a different ion

Typically cations vs. H+ and anions vs. OH-

Divalent ions more selectively held than monovalent

Highest selectivity ion loads at the top of the bed
Least selective ion leaks first and indicates exhaustion
Sodium typically leaks first for cations
Silica typically leaks first for anions

Selectivity

In general (dilute solutions)

Trivalent+++ > Divalent++ > Monovalent+ ions

Sulfonic (SAC) resins

MARATHON C

Ba > Pb > Sr > Ca > Ni > Cu > Mg

Ag >> Cs > K > NH4 > Na > H > Li

Quaternary Ammonium (SBA)

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

MARATHON A

Relative selectivity of common ions

Cation Exchanger

Anion Exchanger

Inlet

Inlet

Ca2+

SO42-

Mg2+

CO32-

Na+

Cl-, HSiO3-

H+

OHOutlet

Outlet

Example of equilibrium leakage

K
R-H + Na+
Observation:
Cond = 10 S/cm

R-Na + H+

[R Na] [H+]
Na
K H @ 1.7 = [RH] [Na+]
pH out of Cation unit = 2

Na Leakage = 0.92 ppm Na+

From dissociation [H+] = 10-2
Solve for

[R Na]
[RH]

0.7% Sites Na+ Form

10

Equilibrium calculations
-Predict leakage

Cond, S/cm
10
5
2
1
0.5
0.1

Na+ leakage
920 ppb
460 ppb
185 ppb
92 ppb
44 ppb
8 ppb

% R-Na
0.7%
0.34%
0.14%
0.07%
0.03%
0.006%

Ion Exchange Kinetics

Rate at which ion moves to the resin surface and is
removed
In ion exchange film diffusion is the rate limiting step
Surface fouling slows down removal of ions.

Single Bead Kinetic Model

Bulk Liquid Flow

R
Solid
Bead

C
C*

Stagnant
Film
C = Concentration of Ions in Bulk Liquid
C* = Concentration of Ions at Bead Surface
L = Film Thickness

In Ion Exchange
processes, overall
exchange kinetics is
controlled by film
diffusion

What is controlling performance?

Equilibrium Controlled
Baseline Leakage determined by residual impurities at the outlet of the
column. (what is left on the resin after regeneration)
Regeneration efficiency-controlled by equlibrium

Kinetic Controlled
Mass transfer zone width
Time to breakthrough and shape of the curve
SO4 leakage at ppb levels anion surface fouling

Ion exchange resin breakthrough curve

Influent [O]

Concentration
of O

Baseline
Leakage of O
Zero

Time

IX Vessel Performance Factors

Performance factors content

Operating capacity
Cycle end point

Reaction zone
Flow distribution
Regeneration

Column operation
Fluid to be treated
(Influent)

Resin bed
1 Bed volume
(BV)

Total capacity
2.1 eq/l resin

Treated fluid
(Effluent)

Operating capacity

Exhausted resin

Bed
Depth
0

Reaction zone

100

Exhaustion, %

Regenerated resin

Cycle end point

Operating
capacity
1.3 eq/l resin

Exhausted resin

Reaction zone
0
100
Exhaustion, %

Leakage

Regenerated resin

Flow distribution in service vessels is

critical

21

Flow Distribution
Effect in Service
Widen mass transfer zone
Reduces throughput
Could increase leakage

Effect in Regeneration
Reduces throughput
Increase leakage
Increases rinse time
Chemical hideout

Operating capacity- After 1st Cycle

Begin

End

Exhausted resin

Reaction
zone
Not all total capacity
available

Operating capacity
60% of total

Co-flow regeneration
Liquid to
be treated

Regenerant

Eluate
(spent regenerant)

Leakage

Counter-flow regeneration
Liquid to
be treated

Eluate
(spent
regenerant)

Clean
polishing
zone

Regenerant

Plant operation

Feed Water
-TDS
Total Dissolved Solids (TDS)

Amount of saltsin the water: NaCl, Na2SO4 CaCl2, etc.

Feed Water Analysis, ppm as Ion

Cations
Ca
Mg
Na
K
Fe
Total
Cations

Anions
150
75
250
20
0.5
496

Total Dissolved
Solids

SO4
NO3
Cl
HCO3
SiO2
Total
Anions

280
70
300
545
35

Cations

Anions

Ca + Mg

HCO3

Na

Cl + SO4

1230

SiO2

1726

TDS is the load on the ion exchange Resin

Feed Water
-Other contaminants
Organics measured as TOC
Oil/hydrocarbons
Surfactants
Natural Organics

Oxidants
Chlorine
Chloramines

Particulate matter
TSS Dirt, Fe, flocculent, etc.
Turbidity

Not part of the load, but have an impact on performance

Demineralisation

Trying to remove all ionic contaminates

Cation resin removes cations from the water
Anion resin removes anions from the water
You have created new water molecules

Na

Na

Cl
Cl
Cl

Na

OH

H
H

H OH

OH
(charges not shown)

Service cycle
What happens in each bed?
Four Bed System
WAC SAC WBA SBA

WAC

SAC

WBA

30

SBA

DI Weak Acid Cation

Removes hardness associated with alkalinity
2R-H + Ca2+(HCO3)2 R2-Ca2+ + 2CO2 + 2H2O
Very efficient regeneration
1.05 to 1.15 eq of acid per eq of operating capacity
Use Rule of thumb
Total hardness >50% of total cations, Alkalinity/hardness ratio ~1

WAC

DI Strong Acid Cation

Most common is 8% DVB
Best balance of total capacity and regeneration efficiency

Uniform particle size (UPS) resins needed for reverse flow systems;
also preferred for Co-flow systems
Need less fines
Improved rinse with UPS

Higher DVB resins used when oxidant concentration is high

ppm

SAC

> 0.2

DI Weak Base Anion

Removes only strong acids
R-N: + H+Cl- R-N: HCl

Very efficient regeneration

1.20 to 1.30 eq of NaOH per equivalent of operating capacity

Use Rule of thumb

Total FMA >50% of total anions
High organics protect SBA

WBA

CO2

DI Strong Base Anion

Many choices

Resin types
Type 1 vs. Type 2
Acrylic vs. Styrenic
Gel vs. Macroporous
UPS vs. Gaussian
High solids vs. Low solids

CO2

Selection criteria
Temperature
Organic loading
Chemical efficiency
Silica leakage
Silica load

SBA

Throughput/Run Time
Feed water can vary greatly
Throughput/run time varies with amount of contaminants in
water
Higher load, lower throughput
Lower load, higher throughput
Flow distribution problems
Resin degradation
Excess loading of other contaminants
Fe
NOM

Water Quality
Measured by instrumentation and testing
Instruments need routine calibration
Testing very important to ensure water quality measured by
instruments

Boiler reliability and Process reliability dependent on

effluent water quality

Regeneration Steps
Backwash
Chemical Injection
Acid and Caustic

Chemical Displacement
Also called slow rinse

Fast Rinse

Backwash

Necessary on every regeneration for Co-flow Cation

and Anion Systems
Must remove particulate matter and Fe from cation
Must remove anion fines from anion
Counter-flow systems only backwashed when necessary

Poor backwash can create pressure drop and flow

distribution problems
Lower throughput/shorter runs
Lower water quality

Backwash

Extreme care must be taken to prevent loss of resin;

ESPECIALLY anion resin
Expand bed to 1 to 1.5 feet below the outlet
Ideally 80% expansion, minimum 60%

Backwash time starts when bed is fully expanded

Minimum of 20 minutes
Water temperature affects expansion!

Backwash

Chemical Injection
-Critical parameters

Quantity of Acid or Caustic

Concentration of Acid and Caustic
Temperature of Caustic
Flow Rate of Acid and Caustic
Contact Time

Chemical Injection
-Quantity of Acid or Caustic

Must use correct amount of chemical

Need mass action to drive equilibrium
Direct effect on throughput/run time
Direct effect on leakage in co-flow vessels

Chemical Injection
-Concentration of Acid and Caustic
As with quantity of chemical, concentration is critical
for mass action
Weak Acid Cation < 0.7% H2SO4
Critical to prevent CaSO4 precipitation

All other resins typical is 4-8%

Below 4% effectiveness decreases
Above 8% high potential for resin breakage

Chemical Injection
-Resin breakage
Resin shrink and swell as they change forms
Osmotic stress on the resin is very strong
Shrink/swell too fast causes beads to break

WBA are particularly susceptible

Regenerate very easily, shrink very fast

Macroporous to increase strength, but still not enough
Least physically stable resin in the system
Backwash critically important for good WBA performance

Chemical Injection
-Temperature of caustic
For more efficient SiO2 removal and prevention of SiO2
precipitation
Typical temperature 120F for co-flow systems
Hot water alone can remove SiO2 from the anion

Chemical Injection
-Flow rate
For cation, flow rate critical to keep
precipitation from occurring inside bed.
For all other resins, typical flow rate
0.25 1 gpm/ft3 (2-8 BV/hr)
Too low flow rate results in poor
distribution of chemical throughout the
bed.
Too fast flow rate results in inefficient
regeneration and waste of chemical

Chemical Injection
-Contact time
Given quantity, concentration, and flow rate, contact time
is set
Needs to be >20 minutes
Balanced to maximize effectiveness, minimize waste,
and minimize precipitation.

Chemical Displacement

Continuation of chemical injection

Must be done at same flow rate as chemical injection
Completes regeneration
Rinses out bulk of chemical
If fast rinse is started too quickly, fast rinse time may
be extended due to mixing in vessel.

Fast Rinse
Typically performed at service flow rate
Rinse to final conductivity and SiO2 requirements
Can be extended for many reasons

Resin degradation
NOM loading on anion resin
Fe loading on cation resin
Poor flow distribution

Thank You!

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