Ion Exchange Operations

Matt Roth
Content

• Performance Drivers
– Equilibrium
• Selectivity
• Equilibrium leakage
– Kinetics
• Performance Factors
– 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

A B
Potential Difference Equilibrium

5
Equilibrium Equation

K
R-X + O R-O + X

O [RO] [X]
K X = [RX] [O]

O
K 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

7
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) MARATHON A

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

8
Relative selectivity of common ions

Cation Exchanger Anion Exchanger

Inlet Inlet

Ca2+ SO42-

Mg2+ CO32-
Na+ Cl-, HSiO3-
H+ OH-

Outlet Outlet
 Example of equilibrium leakage

K
R-H + Na+ R-Na + H+

Na [R Na] [H+]
Observation:
Cond = 10 µS/cm
K H @ 1.7 = [RH] [Na+]
pH out of Cation unit = 2
Na Leakage = 0.92 ppm Na+
From dissociation [H+] = 10-2
[R Na]
Solve for
[RH]

0.7% Sites Na+ Form

10
Equilibrium calculations
-Predict leakage

Cond, µS/cm Na+ leakage % R-Na

10 920 ppb 0.7%
5 460 ppb 0.34%
2 185 ppb 0.14%
1 92 ppb 0.07%
0.5 44 ppb 0.03%
0.1 8 ppb 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

L In Ion Exchange
C
processes, overall
exchange kinetics is
R C* controlled by film
Solid
Bead diffusion

Stagnant
Film

C = Concentration of Ions in Bulk Liquid

C* = Concentration of Ions at Bead Surface
L = Film Thickness
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)

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

Treated fluid
(Effluent)
Operating capacity

Exhausted resin

Bed
Depth Reaction zone

0 100
Exhaustion, % Regenerated resin
Cycle end point

Operating
capacity
1.3 eq/l resin Exhausted resin

Reaction zone

0 100
Regenerated resin
Exhaustion, % Leakage
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 Operating capacity

available 60% of total
Co-flow regeneration

Regenerant Liquid to
be treated

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 Anions
Cations Anions
Ca 150 SO4 280
Mg 75 NO3 70 HCO3
Ca + Mg
Na 250 Cl 300
K 20 HCO3 545
Fe 0.5 SiO2 35
Total Total Cl + SO4
Na
Cations 496 Anions 1230
SiO2
Total Dissolved
Solids 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 Cl
Na Cl
Cl
Na
H OH

H H OH OH
(charges not shown)
Service cycle

• What happens in each bed?

Four Bed System

WAC  SAC  WBA  SBA

WAC SAC WBA SBA

30
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 > 0.2
ppm

SAC
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

CO2

WBA
 DI – Strong Base Anion

• Many choices

• Resin types • Selection criteria

• Type 1 vs. Type 2 • Temperature
• Acrylic vs. Styrenic • Organic loading
• Gel vs. Macroporous • Chemical efficiency
• UPS vs. Gaussian • Silica leakage
• High solids vs. Low solids • Silica load

CO2

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 120°F 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!

For more information please visit our web site or

contact your local Dow representative.
http://www.dowwaterandprocess.com/