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Water Management Group 1

ION EXCHANGE
Introduction
Ion Exchange Resins
Cation Exchange
Anion Exchange
Dealkalizers
Demineralizers
Troubleshooting

Water Management Group 2


ION EXCHANGE
Removes dissolved solids
(also removes suspended solids)

Accomplished by passing
water through a column of
plastic bead called ion
exchange resin contained in
a vessel

Water Management Group 3


ION EXCHANGE RESINS

TYPES
Functionality
Material
Structure

Water Management Group 4


RESIN TYPES
FUNCTIONALITY
Cation Exchangers
Strong Acid Cation (SAC)
Weak Acid Cation (WAC)
Anion Exchangers
Strong Base Anion (SBA)
Weak Base Anion (WBA)

Water Management Group 5


CATION EXCHANGE RESIN
Strong Acid Cation (SAC)
Hydrogen or sodium form
Sodium form removes hardness (Ca/Mg) only
Hydrogen form removes nearly all cations
Functional group: sulfonic acid group - HSO3

Weak Acid Cations (WAC)


Removes only hardness associated with alkalinity
More efficient regeneration than SAC
Functional group: carboxylic group - COOH

Water Management Group 6


SAC

SO3-

Water Management Group 7


ANION EXCHANGE RESINS
Strong Base Anion Resin (SBA)
Removes all anions & CO2
Less efficient regeneration than WBA
Functional group: quaternary ammonium
group
Type I RN(CH3)3
Greater stability
Type II RN(CH3)2C2H5OH
Greater capacity

Water Management Group 8


ANION RESINS

Weak Base Anion Resin (WBA)


Removes only SO4, Cl, NO3, PO4 (strong acids)
More efficient regeneration
Better at releasing organics (elution) upon
regeneration
Used ahead of SBA to protect from fouling
Functional groups: amine groups R-NH2
Acts as an acid sponge

Water Management Group 9


Cation Exchange

Water Management Group 10


Cation Exchange
Reactions
Processes
Sodium Exchangers
Hydrogen Exchangers
Capacity Calculation
Leakage Estimates
Regeneration

Water Management Group 11


Demineralization Process

Similarities to Softener
Uses the same Resin (H form)
Has the same operating steps
Differences from Softener
Regenerant
Leakage
Paired with:
Anion Resin ==>Demineralizer

Water Management Group 12


Cation Exchange Reactions
Deminerlization Process
Raw Water Cation Resin Cation Water
Cations Anions Cations Anions
Ca++ HCO3- H2CO3
Mg++ R_H +
SO4= H+ SO4=
Na+ Cl- Cl-
1 equivalent 1 equvalent
1 ppm as CaCO3 1 ppm as CaCO3
20 mg Ca++ 1 mg H+
12 mg Mg++ 1 mg H+
23 mg Na+ 1 mg H+
GENERAL SELECTIVITY:
Fe 3+> AL 3+ > Ba 2 + >Sr 2+ > Cu 2+> Fe 2+>Ca 2 + > Mg 2+ > K +> NH4+> Na + > H+

Water Management Group 13


Cation Exchange Reactions
Demineralization Process
Raw Water Cation Water
Cation Resin
Cations Anions Cations Anions
Ca++ HCO3- H2CO3
R_H +
Mg++ SO4= H + SO4=
Na+ Cl- Cl-

Alkalinity Carbonic Acid

TMA FMA
Theoretical Mineral Acidity Free Mineral Acidity

Water Management Group 14


FMA
FMA is Free Mineral Acidity, or the
concentration of strong acid anions
present in a water sample. Always
expressed as CaCO3

Generally the FMA in a water sample is


composed of hydrochloric and sulfuric
acids.

Water Management Group 15


Leakage

Water Management Group 16


Strong Acid Cation
Free Mineral Acidity FMA
Effluent Profile

End of Rinse

End of Run

M3 Processed
Water Management Group 17
Strong Acid Cation
Free Mineral Acidity FMA
Effluent Profile

End of Rinse

Theoretical Mineral Acidity

End of Run

M3 Processed
Water Management Group 18
Strong Acid Cation
Free Mineral Acidity FMA
Effluent Profile

End of Rinse

Theoretical Mineral Acidity

Difference between actual


and theoretical mineral acidity
End of Run
is due to sodium leakage

M3 Processed
Water Management Group 19
Sodium Leakage
Leakage depends on:
Total Dissolved Solids
% Sodium of Total Cations
% Alkalinity of Total Anions
Regenerant Level
Resin Bed Depth

Water Management Group 20


Increasing Leakage

g e
ka
ea
L
Na
i ng
as
c re
In

Na, % of Total Cations

Total Dissolved Solids

Water Management Group 21


Decreasing Leakage
De
cr
ea
si
ng
Na
Le
ak
ag
e

Alkalinity % of Total Cations

Regenerant Dosage, Kg/m3 resin

Water Management Group 22


Calculate Na Leakage

Information Required
Acid Dosage (Kg/M3 resin)
% M-Alkalinity of Total Cations
% Na of Total Cations
Resin Bed Depth

Water Management Group 23


Backwash (10-15 minutes)
"Dirty" Water to Sewer
Service Flow

50% Exhausted
Bed Resin
Expansion

Water

Water Management Group 25


Regeneration Mode

Co-current (Co-flow)
regenerant flow in the same flow
direction as service flow
Counter-current (Reverse Flow)
regenerant flow in the opposite
direction as service flow

Water Management Group 26


Acid Injection Cycle (25-30 minutes)
Cond 4 - 5% HCl

Dilution Water

Acid
Conc. "plug flow"
SAC
HCl
Acid Pump
or
Eductor

Counter-Current Sample Drain


Water Management Group 27
NaOH Injection Cycle (30-50 minutes)
Cond 4 - 5% NaOH

Demin Water 45 C

Steam

NaOH
"plug flow"
50% SBA
NaOH
NaOH Pump
or
Eductor

Sample Drain
Water Management Group 28
Displacement Cycle (25- 40 minutes)
Slow Rinse: 1.0 - 1.5 bed volumes
Duration 20-30 minutes
(Displacement) Optimizes acid usage.
Minimize leakage

Dilution Water

Conc.
HCL "plug flow"
HCl

Sample Drain
Water Management Group 29
Fast Rinse Cycle - Cation (15-30 minutes)

Filtered Water Flow = Service Flow Rate

Dilution Water

Rinse out
Acid

SAC
Conc.
HCl
Acid Pump
or
Eductor

Sample Drain
Water Management Group 30
Fast Rinse Cycle - Anion (20 -60 minutes)
Decationized water
from Degas or SAC Flow = Service Flow Rate

Demin Water

Steam
Rinse out
NaOH
SBA
50%
NaOH < 10 us/cm
Cond
NaOH Pump
or
Eductor

Sample Drain
Water Management Group 31
Acid Regeneration - H2SO4

H+
SO4= SO4=
H+
H+
H +

SO3-

SO 3
- Ca++

Water Management Group 32


Total Capacity vs Operating Capacity
Ion exchange is a relatively inefficient process
With most strong acid or strong base resins
more than 60% of the total capacity is seldom
used
Example: SBA Type 1 resin (IRA-402) total
capacity is 60 Kg CaCO3/M3. At 60 Kg NaOH/M3
regeneration dosage, the operating capacity is
23 Kg CaCO3/M3
Doubling the NaOH dosage increases operating
capacity to 31 Kg/CaCO3/M3 (only a 35%
increase)

Water Management Group 33


H2SO4 vs. HCl
Commercially available
HCl @ 30-33%
H2SO4 @98%
$/Kg about the same
Usage cost higher for HCl as acid dosage is
based on Kg acid@100%/M3 resin
At equal acid dosage, HCl yields higher resin
exchange capacity (about 15-25%) and lower
Na leakage
Equivalent to CaCO3
HCl =1.37 (MW = 36.5)
H2SO4 = 1.02 (MW = 98.1)

No CaSO4 precipitation concern with HCl

Water Management Group 34


Exhausted Resin

Ca++ Mg++ ++
Ca
Mg++
Ca++
Ca++ Na+
Mg++
Mg ++
Ca++
Ca++ Ca++
Ca ++ Ca ++
Mg ++

Na + Mg++
Mg ++
Ca++
Ca++ Ca++
Mg++

Water Management Group 35


Step-wise H2SO4 Regeneration
2 & 4% H2SO4
On-Line Conductivity
Service Flow
Eductor
X M3/Hr
2X M3/Hr

Demin Water
Spent Acid

Acid "plug flow"

Conc.
To Degas
H2SO4
& Anion

Acid Injection Sample Drain


Pump
Water Management Group 36
Cation Operation
DISPLACEMENT: Acid out should be 0% at the end
of the slow rinse (conductivity)
Slow Rinse
1 - 2 bed volumes

Fast Rinse: Gets quality in line before the


service step begins, or before
the anion regeneration begins

Usually a timed step

May monitor conductivity, FMA


or Na+

Water Management Group 37


Regeneration Mode
Co-current
(Co-flow)
versus
Counter-Current
(Reverse Flow)

Water Management Group 38


At exhaustion - Profile

Strong
Acid Cation CALCIUM
Exchanger
MAGNESIUM
RESIN
BED
POTASSIUM Service
Flow
SODIUM

HYDROGEN

Water Management Group 39


Co-Current Regeneration

Strong
Acid
Cation HYDROGEN
Exchanger RESIN
BED

CALCIUM
MAGNESIUM Acid
POTASSIUM Flow
SODIUM

Water Management Group 40


Counter-Current : Regeneration

CALCIUM
Acid
Fow
STRONG ACID MAGNESIUM
CATION EXCHANGER
POTASSIUM
SODIUM

Polishing HYDROGEN
Zone

Water Management Group 41


Counter Current Regeneration
Applied to cation units typically but
can be used on Anion as well

Yields low Na leakage for cation and


low SiO2 leakage for Anion

Improves regeneration efficiency

Reduces rinse water requirement -


less waste water

Water Management Group 42


Counter-current Regeneration
To achieve lowest Na or SiO2 leakage with
counter-current regeneration, the resin bed
profile should not be disturbed
Full backwash and upflow regenerant can turn
the resin bed over and will increase the leakage
Sub-surface backwash and block water flow can
be used to overcome the problem
When full backwash is implemented, double
regeneration is required in order to restore the
polishing zone

Water Management Group 43