Lecture Water Quality Control and Design: Ion Exchange

Department of Chemical &
Environmental Engineering
ENVE 120, Fall 2013
Ion Exchange
Chapter 5
Mark Matsumoto
Chemical & Environmental Engineering
A213 Bourns Hall and 454 Chung Hall, x2-3197
mark.matsumoto@ucr.edu
Ion Exchange
Purpose Removal of _______________ from Solution
Water Treatment
__________
Demineralization (deionization)
Wastewater Treatment
________________________
Demineralization
Metal removal and recovery (industrial wastewater)
Remediation
___________________________________________________
Cations not mobile in soils
Ion Exchange
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Ca
2+
Ca
2+
Ca
2+
Na
+
Ca
2+
Ca
2+
Ca
2+
Mg
2+
Mg
2+
Mg
2+
Mg
2+
Mg
2+
Ca
2+
Ca
2+
Ca
2+
Ca
2+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+ Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Na
+
Ca
2+
Ca
2+
Ca
2+
Na
+
Ca
2+
Mg
2+
Mg
2+
Mg
2+
Mg
2+
Mg
2+
Ca
2+
Ca
2+
Ca
2+
Na
+
Na
+
Na
+
Na
+
Ion Exchange Material (Resins)
Ion exchange resins are __________ created by cross-linking hydrocarbon
chains. These resins are _________, inert and relatively rigid. Ionic functional
groups are attached to this framework.
Styrene
Divinyl-
benzene
Polystyrene chain
Divinylbenzene
crosslink
Ion Exchange Material (Resins)
Resin Types
Resins are classified based on the type of ________________ they contain and
their % of ________________.
Cationic exchangers
Strongly acidic functional groups derived from ______ acids e.g., R-SO
3
H
(sulfonic) work at a wide range of pH values.
Weakly acidic functional groups derived from _____ acids, e.g., R-COOH
(carboxylic) work at a narrow range of pH values.
Anionic exchangers
Strongly basic functional groups derived from ___________________________,
R-N-OH work at a wide range of pH values.
Weakly basic functional groups derived from ___________________________,
R-NH
3
OH or R-R-NH
2
OH work at a narrow range of pH values.
Ion Exchange Reactions
__________________ must be maintained in the bulk fluid
Two monovalent ions exchanged for one divalent ion
Generalized reactions:
nR
-
A
+
+ B
n+
R
n
-
B
n+
+ nA
+
nR
+
A
-
+B
n-
R
n
+
B
n-
+nA
-
(cationic)
(anionic)
where R = ionic group attached to a solid exchange resin
A = soluble functional group that can be exchanged with similar ion in the bulk water
Equilibrium Expression (Cationic)
In ion exchange, the equilibrium expression is termed the _________________
K, which varies with T, pH, ionic strength.
If the power term is ignored, then the equilibrium expression is termed the
________________ or selectivity quotient o
]
When o
]
> 1 B will be preferentially adsorbed over A. The higher o
]
is, the
greater the affinity or preference.
K
A
+
B
n+
=
R
n
-
B
n+
A
+ n
R
n
-
A
+ n
B
n+
= K
]
=
C
]
n
q
q
]
n
o
]
=
C
]
q
q
]
K
]
= o
]
q
n-1
Selectivity or Preference of Exchange
The selectivity or ______________________ varies with resin. However, the
selectivity preference depends on primarily two factors.
Valence or charge
Ions with _______ valence are preferred. Typical preferences:
Exceptions due occur:
Hydration radius
If ions have the same valence, ions with _________ hydration radii are preferred. The
percentage of cross-linking is interrelated since it affects pore size. Typical preferences based
on hydration radii:
Ib
4+
> Al
3+
> Co
2+
> No
+
P0
4
3-
> S0
4
2-
> Cl
-
S0
4
2-
> I
-
> N0
3
-
> Cr0
4
2-
> Br
-
Ag
+
> Cu
+
> K
+
> NE
4
+
> No
+
> E
+
> Ii
+
Pb
2+
> Eg
2+
> Co
2+
> Ni
2+
> CJ
2+
> Cu
2+
> Zn
2+
> Fc
2+
> Hg
2+
> Hn
2+
Fc
3+
> Al
3+
Caution: Selectivity coefficients
and preference series only apply
for low ionic strength waters,
typical of drinking water.
Selectivity Coefficients
Selectivity coefficients for ______________________ can be easily determined.
Example: Home water softener systems often use ion exchange resins that are
initially charged with Na
+
by using high concentrations of NaCl (brine).
However, as noted on the prior table, the selectivity coefficients are based on
having hydrogen ion as the initial ion on the resin. Using the values given in the
table, the selectivity coefficient between Na
+
and Ca
2+
can be determined for
the 4% cross-linked resin:
K
Nu
+
Cu
2+
=
K
H
+
Cu
2+
K
H
+
Nu
+
=
S.14
1.2u
= 2.62
Exchange Capacity Concepts
As noted before, a ______________ must be maintained. Thus, it is useful to
track ion concentrations in terms of ___________ rather than moles. This leads
to two definitions:
This latter term is also known as the ___________________.
During the exchange process, we want to know how much of the target ion for
removal is in the liquid and solid phases. Let be the fraction of A
+
in
solution compared to the total amount of ions in solution and let be the
fraction of A
+
on the resin compared to the total amount of exchangeable ions
on the resin:
q
1
=
C
1
=Total concentration of exchangeable ions in the liquid phase, eq/L
Total concentration of exchangeable sites on the resin, eq/L of bulk volume
X
A
+
RX
A
+
X
A
+ =
A
+
C
1
RX
A
+ =
RA
+
q
1
Equilibrium Expression (Cationic)
If the total exchange capacity of the ion exchange resin is defined as:
Then, the _____________ of counterion i at any time is:
q
=
C
q
1
C
+C
]
o
]
q
1
= q
+q
]
For divalent ions:
For now consider monovalent exchange between A and B. Recall:
Assuming that A and B are the only cations:
X
B
2+ =
B
2+
C
1
RX
B
2+ =
RB
2+
q
1
X
A
+ =
A
+
C
1

yielus
A
+
= C
1
X
A
+
X
B
+ =
B
+
C
1

yielus
B
+
= C
1
X
B
+
X
B
+ = 1 -X
A
+ B
+
= C
1
1 -X
A
+
R
-
B
+
+A
+
R
-
A
+
+ B
+
Using similar logic and analysis on the resin:
Substituting into the selectivity coefficient:
Rearranging:
RA
+
= q
1
X
A
+
RB
+
= q
1
X
B
+ = q
1
1 - X
A
+
K
B
+
A
+
=
R
n
-
A
+
B
+
R
n
-
B
+
A
+
=
q
1
X
A
+ C
1
1 -X
A
+
q
1
1 -X
A
+ C
1
X
A
+
=
X
A
+ 1 -X
A
+
X
A
+ 1 -X
A
+
X
A
+
1 - X
A
+
= K
B
+
A
+ X
A
+
1 - X
A
+
For a divalent exchange it can be shown that:
These ion exchange equations (monovalent, divalent) form the relationship for
the amount of target ion exchanged as a function of the amount in solution.
2R
-
B
+
+A
2+
R
-
A
2+
+ 2B
+
2R
-
B
+
+A
2+
R
-
A
2+
+ 2B
+
X
A
2+
1 -X
A
2+
2
= K
B
+
A
2+ X
A
2+
1 -X
A
2+
2

q
1
C
1
Example
Nitrate NO
3
-
is to be removed by ion exchange on a strong base anionic resin
initially charged with chloride Cl
-
. The resin has the following characteristics:
The influent has the following characteristics:
Determine how much water can be treated by an ion exchanger with 1 ft
3
of this
resin assuming rapid kinetics and equilibrium between the water and resin.
K
CI
-
N0
3
-
= 4
q
1
= 1.S
cq
L
Cl
-
= S
mcq
L
N0
3
-
= 1.S
mcq
L
Example
First, determine X
N0
3
at equilibrium with the influent relative to the influent
water composition.
Solving for X
N0
3
leads to X
N0
3
= u.67. This value is the maximum fraction of
resin sites that can be occupied by NO
3
-
for this water. When this fraction has
been reached the resin is exhausted.
The total amount of NO
3
-
that this resin can exchange is:
X
N0
3
-
1 -X
N0
3
-
= K
CI
-
N0
3
- X
N0
3
-
1 -X
N0
3
-
= 4
u.SS
1 -u.SS
= 2
X
N0
3
-
=
N0
3
-
N0
3
-
+Cl
-
=
1.S
1.S +S.u
= u.SS
q
N0
3
-
= q
1
X
N0
3
= 1.S
cq
L
u.67 = u.87
cq
L
Example
The volume of water that can be treated assuming a fully Cl
-
charged resin is:
Assuming rapid kinetics (narrow exchange zone), the effluent (exiting the
column) nitrate concentration will be near zero
I =
q
N0
3
-
C
N0
3
-
=
u.87
cq
L csn
1.S
mcq
L wutc
cq
1,000 mcq
= S8u
L wutc
L csn
I = S8u
L wutc
L csn
= S8u
guI wutc
guI csn
7.48
guI
]t
3
= 4,Suu
guI
]t
3
csn
Example 2
Calcium Ca
2+
is to be removed by ion exchange on a strong acid cationic resin
initially charged with chloride Na
+
. The resin has the following characteristics:
The influent has the following characteristics:
Determine how much water can be treated per L of ion exchange resin
assuming rapid kinetics and equilibrium between the water and resin.
o
Nu
+
Cu
2+
= 1.9
q
1
= 2.u
cq
L
No
+
= 2.6
mcq
L
Co
2+
= 1.4
mcq
L
Example 2
An alternative method to the previous method is to use the separation factor
and the relationship.
Recall that i represents the ion in solution that is to be removed and j is the ion
on the resin that will be exchanged. Thus,
Leading to:
q
=
C
q
1
C
+C
]
o
]
o
Cu
2+
Nu
+
= 1 o
Nu
+
Cu
2+
, =
1
1.9
= u.S26
q
Cu
2+ =
1.4
mcq
L
2.u
cq
L
1,uuu
mcq
cq
1.4
mcq
L
+ 2.6
mcq
I
u.S26
= 1,u1u
mcq
L
Example 2
The volume of water that can be treated assuming a fully Na
+
charged resin is:
Assuming rapid kinetics (narrow exchange zone), the effluent (exiting the
column) nitrate concentration will be near zero
I =
q
Cu
2+
C
Cu
2+
=
1,u1u
mcq
L csn
1.4
mcq
L wutc
= 72u
L wutc
L csn
Continuous-Flow Operation
____________ dominated process Transport of ions from bulk solution
to the ________ or film layer
Diffusion of ions through the film
layer
Diffusion of ions into the ______
where the exchange sites are
Exchange of ions via reversible
reaction
Diffusion of exchanged ions outward
through the ______
Diffusion of exchanged ions through
the film layer toward the film layer
Transport of ions from the film layer
into the bulk solution
Bulk solution
Film layer
Concentration
L
e
n
g
t
h

a
l
o
n
g

r
e
a
c
t
o
r
Concentration
L
e
n
g
t
h

a
l
o
n
g

r
e
a
c
t
o
r
Concentration
L
e
n
g
t
h

a
l
o
n
g

r
e
a
c
t
o
r
Service Cycle
Service: Normal operation
Backwash: Upflow flow to expand
bed by 50% to _________ and
remove any trapped particles
Regeneration: Regenerant solution
(concentrate) passed slowly through
the bed to ____________________
(follows principles of equilibrium)
Slow rinse: Clean water slowly
passed through bed to remove
________________
Fast rinse: Final rinse of the resin
Return to service
Regeneration
After all of the available exchange sites are utilized, the spent or _________
column must be regenerated.
As its name implies ion exchange is a reversible process that can be
accomplished by exposing the resin to an appropriate regeneration solution or
______________.
For home water softening system, resins are initially charged with Na
+
. After a
period of time, most of the exchange sites are filled with ____________ ions
and the softening process ceases.
To restore the softening capacity of the resins, the system must be regenerated
by soaking the resin in a solution containing a high concentration of ______.
Because of the high concentration of Na
+
in solution, Na
+
attachment to the
exchange sites are favored over the Ca
2+
and Mg
2+
ions. The Ca
2+
and Mg
2+
ions on the resin are released into the brine (salt) solution and Na
+
ions are
exchanged back onto the resin.
After regeneration, the brine solution is purged from the resin and the ion
exchange system is put back into service.
Example
A spent water softening column that primarily removes Ca
2+
is to be
regenerated in a batch mode back to the Na
+
form. A strong NaCl brine is
contacted with the exhausted resin to replace Ca
2+
with Na
+
. The composition
of the brine (regenerant) after equilibration with the exhausted resin is:
For this resin, the exchange capacity and selectivity coefficient are:
Note: Most of the Ca
2+
is from the spent column. Na
+
in the fresh brine was
slightly higher than 2 eq/L.
Determine the effectiveness of the regeneration. In other words, what is X
Cu
2+
after the regeneration is complete?
No
+
= 2
cq
L
46 gI
Co
2+
= u.2
cq
L
4 gI
q
1
= 2
cq
L
K
Nu
+
Cu
2+
= 4
Example
After equilibrium in the regenerant:
Solving for X
Cu
2+ using the quadratic formula:
The fraction of Na
+
on the regenerated resin is:
X
Cu
2+ =
u.2
mcq
L
2 +u.2
mcq
L
= u.u91
X
Cu
2+
1 - X
Cu
2+
2
= K
Nu
+
Cu
2+ X
Cu
2+
1 -X
Cu
2+
2

q
1
C
1
X
Cu
2+
1 - X
Cu
2+
2
= 4
u.u91
1 -u.u91
2

2
2.2
= u.4u
X
Cu
2+ = u.2S4
X
Nu
+ = 1 -X
Cu
2+ = u.766
Example
Only 76.5% regeneration can be accomplished with this regenerant because
even small amounts of Ca can have a significant effect because of the high
selectivity coefficient in favor of Ca. To get higher regeneration the NaCl
concentration must be higher or the total volume of regenerant must be greater
to dilute the Ca that comes off the exhausted column. Both options cost money
and there needs to be a tradeoff evaluated between higher column utilization
and more costly regeneration.
Design Considerations
Selection of resin: ________________ (meq/mL) less than total
capacity (see previous example)
_________________
Service flow rate (SFR) = Q/V
resin
Typical 200 to 1,000 m
3
/m
3
-d
Typical 8 to 40 BV/hr
Empty-bed contact time (EBCT) = V
resin
/Q
Typical 1.5 to 7.5 min
Surface loading rate (SLR) = Q/A
s
Typical 175 to 880 m/d (depending on headloss)
Limit headloss to <140 kPa (20 psi)
Water Softening: Typical Design Criteria
___________________: 400-800 m
3
/d m
2
of bed cross-sectional area
Backwash rate: Want __________ expansion of the resin bed. Rate is
dependent on density of the resin and temperature of the backwash
water.
Regeneration: For strong acid and strong base resins: 2 to 10%
solutions, weak acid and base resins: 1 to 5% solutions.
Water Softening: Typical Design Criteria
Regeneration:
Minimum contact time of ________
Flow rate of 60 -120 m
3
/d m
2
of cross sectional area
Quantity of resin depends on manufacturer specifications
Rinsing to remove excess regenerant:
___________ the bed volume (BV) of resin
Bed depth: Minimum of 0.9 m
Freeboard: Length of 50 to 75% of the bed depth

Lecture Water Quality Control and Design: Ion Exchange

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