Ion Exchange_F11

Ion Exchange (3rd DC 197; 4th DC 255)

Definition

- the reversible interchange of ions between a solid and a liquid phase in which
there is no permanent change in the structure of the solid.

Types of Ion Exchange Resins

1) Cation Resin remove cations

2) Anion Resin remove anions

Type Remove Example Regenerant

--------------------------------------------------------------------------------
Cation Resin
Strong Acid Salts of strong Ca2+ H2SO4
base, weak base NH4+ HCl
- Nonselective
.........................................................
Weak Acid Salts of strong Ca2+, Mg2+ H2SO4
base Na+ HCl
- Selective no NH4+
Type Remove Example Regnerant
--------------------------------------------------------------------------------
Anion Resin

Strong Base Salts of strong SO42-, Cl- NaOH

acids, weak acid HCO3-,
- non selective NO3-
...........................................................
Weak Base Salts of strong SO42- NaOH,
acid Cl- ,NO3-
- selective
-------------------------------------------------------------------------------

Applications of Ion Exchange Processes

a. Water Softning (Ca2+, Mg2+)

b. P-removal (PO43-)
c. N-removal (NH4+, NO3)
d. Demineralization (Ca2+, Mg2+, Fe3+, Mn2+, Na+)
e. Radionuclides removal (Sr-85, Cs-134, I-131)
 Ion Exchange_F11

Types of ion exchange material

a. Natural
b. Synthetic

Natural ion exchange material:

1) Zeolite
Naturally occurring clays, used for water softening to remove Ca2+ and Mg2+.
Na2SO4 + Al2(SO4)3 -----> precipitate ---------> Na2O Al2O3
heat

Ion exchange capacity of Zeolite:

20 kilograins of hardness as CaCO3

--------------------------------------------------
ft3 zeolite

Units: 1 grain / gal = 17.1 mg / L

20 kgr ft3 103 gr

--------- ------------ ---------- = 2673.8 gr/gal
ft3 7.48 gal kgr

2673.8 gr 17.1 mg/L

--------------- ---------------- = 45,722 mg/L
gal gr /gal

45722 mg kg 103 L
-------------- ----------- ---------- = 45.7 kg/m3
L 106 mg m3

2) Sulfonated coal

Synthetic (Commercial) ion exchange resin

Characteristics:
- cross linked polystyrene
- very rigid
- porous for good hydraulic characteristics
- higher exchange capacity
- high melting point
- require less regenerant (e.g., NaCl)
- more expensive ($)
 Ion Exchange_F11

Ion Exchange Equilibria

a. Ion exchange reaction:

HR + Na+ NaR + H+
where R = ion exchange resin
HR = Hydrogen resin (Strong acid resin)
NaR = Sodium resin

{NaR} {H+}
Keq = -------------------
{HR} {Na+}

where Keq = selectivity coefficient; { } = activity

b. Regeneration Reaction

NaR + H+ Cl
HR + Na+ Cl

Note:
Equilibrium:

aA + bB <===> cC + dD
c d
{C} {D}
K = ---------------
{A}a {B}b

Note:

- We want the selectivity coefficient to be large, but not too large. If it's too large, then
regeneration will be difficult.

Water Softning by Ion Exchange

1. General chemical reactions with zeolites

- Zeolites are used in the ion exchange process for water softening to adsorb calcium and magnesium. The calcium and
magnesium ions are exchanged for sodium ions.

(2Na)-Z + Ca2+
Ca-Z + 2 Na+

(2Na)-Z + Mg2+
Mg-Z + 2 Na+

Z = ion exchange resin such as zeolites

- Other ions may be substituted for calcium and magnesium in the reaction.
 Ion Exchange_F11

If calcium or magnesium is in the form of bicarbonate or sulfate, the equation may be

written in molecular form as:

(2Na)-Z + Ca(HCO3)2
Ca-Z + 2 Na(HCO3)

(2Na)-Z + Mg(HCO3)2
Mg-Z + 2 Na(HCO3)

(2Na)-Z + CaSO4
Ca-Z + Na2 SO4

(2Na)-Z + MgSO4
Mg-Z + Na2 SO4

Regeneration
After the zeolite bed is exhausted it may be regenerated with sodium chloride according
to the equation:

Ca-Z + 2NaCl
(2Na)-Z + Ca2+ + 2 Cl

Mg-Z + 2NaCl
(2Na)-Z + Mg2+ + 2 Cl

The ion-exchange material can now be used to remove more hardness.

Ca2+ and Mg2+ is a water stream that must be disposed of.

Advantages and Disadvantages (Water softening using Ion Exchange)

Advantages

1) Easy to operate
- Properly designed systems are relatively easy to operate

2) Near zero hardness

- Near zero hardness levels can be achieved in most cases

3) Regeneration with common salt

- Regeneration of ion resin with common salt can be readily accomplished

Disadvantages

1) No reduction of total solids or alkalinity

- Reduction in alkalinity or total solids cannot be achieved

2) Waste brine disposal problems

- Waste regenerant brine may cause disposal problems, if contaminated.

3) Health problem
- Relatively high sodium level in treated water may cause health problem.
 Ion Exchange_F11

General Rules

a. Effect of Charge on Exchange Potential

The higher the charge, the greater the attraction to the resin (easier to remove)
- but tough to get off removed ions during regeneration.

Higher affinity Lower affinity

Easier to remove Harder to remove
<----------------------------------------------------------------->
Examples:
PO43 SO42 Cl
4+ 3+ 2+
Th Fe Ca Na+
4+ 3+ 2+
Th Al Ca Na+

b. Effect of Hydrated Radius on Exchange Potential

Larger hydrated radius, easier to remove.

- The Extended Debye-Hckel Equation:

- The effective hydrated radius of the ion, a is the radius of the ion and its closely bound water
molecules.
- Large ions and less highly charged ions bind water less tightly and have smaller hydrated radii
than smaller, more highly charged ions.

c. High ion concentration

High ion concentration can reduces or reverse the effect of charge and the
effective hydrated radius of the ion
- This gives clues to the best flow scheme (including regeneration)

d. High temperature

- High temperature reduces the effect of atomic number

Notes:
1) Exchange potential may be approximated by their activity coefficients
2) Organic ions and metalic complexes (e.g., MnO3-) have very high exchange potentials
 Ion Exchange_F11

Breakthrough curve (continuous flow-through run)

rd th
- see Fig 3-21 (3 DC 199); Fig 4-23 (4 DC 256)

Water, Cin Influent

hardness

Hardness, mg/L as CaCO3

Exhausted
resin

Due to
saturation of ion
exchange
Fresh Effluent material
resin
hardness

Time, hr
Treated water Breakthrough time
Cout

Breakthrough time

time to breakthrough,
time to saturate (exhaust) the exchange resin
the length of time between regeneration cycle

Total Capacity of the resin

Breakthrough time = -----------------------------------------
Mass of ions removed / time

In the water softening problems, ions = hardness

Example 3-19 (3rd DC 199); Example 4-19 (4th DC 256)

A home water softener has 0.1 m3 of ion-exchange resin with an exchange
capacity of 57 kg /m3 (i.e., 57 kg of hardness as CaCO3 per m3 of resin volume). The
occupants use 2,000 L of water per day. The water contains 280 mg/L of hardness as
CaCO3 and it is desired to soften it to 85 mg/L as CaCO3.

In this example, it is assumed all (100%) hardness in the water which passes through
the ion exchange column is removed.

(1) How much water should be bypassed?

(2) What is the time between regeneration cycle Breakthrough time?
 Ion Exchange_F11

(Solution)

C = Concentration
Q, Cin Q = flow rate

Mass loading rate =

CQ
(Q-Qb), Cin

Qb
Cin

(Q-Qb), Ce

(Q-Qb), Ce~0
Qb,Cin

Q, Cp Q, Cp

1) Mass Balance:

Accum = Inputs Outputs + Reactions

Because there is no accumulation at the pipe joint and no reactions,

Inputs = Outputs

(Q - Qb) Ce + Qb Cin = QCp

If Ce = 0

Qb Cin = QCp

Qb Cp 85 mg/L
----- = ------ = -------------- = 0.30 (30% of total flow)
Q Cin 280 mg/L

Qb = 0.3 Q = (0.3)(2000 L/d) = 600 L/d

 Ion Exchange_F11

1) Loading Rate = (1- 0.3) Q Cin = 0.7 (2000 L/d) (280 mg/L)

= 392,000 mg/d

2)
Total Capacity of the resin
Break through time = -------------------------------------------
Mass of ions removed / time

(57 kg/m3)(0.1 m3)

= --------------------------------------- = 14.5 days
(392,000 mg/d)(10-6 kg/mg)

Note that it is assumed all (100%) hardness in the water which passes through the ion
exchange column is removed.
 Ion Exchange_F11
Example )
An ion exchange process is to be used to soften water with an analysis as shown in Table 1. A synthetic zeolite resin is to
be used with an exchange capacity of 20 Kilograins of hardness as CaCO3 per ft3 when regenerated at the rate of 15 lb of salt per
ft3. Flow rate is 300 gpm. Assume a final hardness level of 2 mg/L (as CaCO3) is required. (1 grain/gal = 17.1 mg/L)

Use the following design criteria:

a. The maximum loading rate < 5 gpm/ft3 of resin
b. The bed depth = 30 < 72 inches.

Assume a 24 hour regeneration cycle for each softner unit.

(Actual frequency of regeneration would depend upon operating conditions.)

Table 1. Water Analysis

===================================
Component Conc. (mg/L as CaCO3)
-------------------------------------------------------------
Calcium 85
Magnesium 26
Sodium 37
Chloride 10
Sulfate 60
Bicarbonate 78
-------------------------------------------------------------

1. Write general chemical reactions that occur in the

ion exchange process.
2. Calculate total hardness (mg/L as CaCO3)
3. Calculate hardness to be removed (grains/gal)
4. Calculate hardness to be removed (Kilograins/d)
5. Calculate total resin required (ft3)
6. Calculate the amount of salt required for regeneration.
7. Calculate the bed depth and shell diameter for
the ion exchange equipment.

Given:
a) use Zeolite (20 kgr/ft3 resin)
b) 15 lb NaCl/ft3 resin for regeneration/day
c) Q = 300 gpm
d) final hardness = 2 mg/L as CaCO3

1. Write general chemical reactions that occur in the

ion exchange process. ..... see above

2. Total Hardness = (Ca2+ + Mg2+) = 85 + 26

= 111 mg/L as CaCO3

3. Hardness to be removed
= (Initial Hardness) - (Final Hardness)
= 111 mg/L - 2 mg/L = 109 mg/L as CaCO3

1 grain/gal
= 109 mg/L (----------------) = 6.37 grains/gallon
17.1 mg/L

4.

Hardness 300 6.37 1440 2.752E6

removed gal grains min grains
-------------------- = -------- ----------- ---------- = ---------------
1 day (24 hrs) min gal day day

= 2752 Kilograins/day
 Ion Exchange_F11
5.

Total resin Hardness removed 2752 Kgr

required = ---------------------------- = ----------------- = 138 ft3
Exchange capacity 20 Kgr/ft3

6.Calculate the lbs of salt required per month for zeolite

regeneration.

15 lbs salt / d
Salt required = (138 ft3)(--------------------)
1 ft3 resin

= 2070 lbs salt/day = 62,100 lbs/month

7. Calculate the bed depth and shell diameter for

the ion exchange equipment.

For 2 units,
Actual design resin volume/unit = 138 ft3/2 units
= 69
ft3/unit
When one unit is in regeneration (flow rate through each unit at normal flow),

Maximum loading rate 300 gpm

------------------------------- = --------------- = 4.34 gpm/ft3/unit
unit 69 ft3/unit

(Criteria: <5 gpm/ft3)

Using a 60 inch (5 ft) diameter shell,

Surface area, A = r2 = 3.14 (2.5)2 ft2 = 19.6 ft2

V
Bed depth, H = ------
A

69 ft3
Bed depth = --------------- = 3.52 ft = 42 inches
19.6 ft2
(Criteria: 30 < 72 inches)

Flow rate through each unit at normal flow,

Normal loading rate 300 gpm / 2

---------------------------- = --------------------
unit 69 ft3/unit

= 2.2 gpm /ft3 /unit

(Criteria: <5 gpm / ft3)

Example
An ion exchange process is to be used to soften water at the rate of 500 gpm. A synthetic zeolite resin will be packed in
shells with diameter of 5 ft. The resin has an exchange capacity of 20 Kilograins of CaCO3 per ft3 when regenerated at the rate of
15 lb of salt per ft3. The raw water has total hardness of 100 mg/L as CaCO3. Assume this process can achieve 95% hardness
removal efficiency. 1 grain/gal = 17.1 mg/L.

Use the design criteria:

a. The maximum loading rate = 5 gpm/ft3 of resin
 Ion Exchange_F11
b. The bed depth = 30 < 72 inches.

a. Calculate the bed depth for the ion exchange equipment.

Total Hardness = 100 mg/L as CaCO3

Hardness to be removed = 100 mg/L - 5 mg/L

= 95 mg/L as CaCO3

1 grain/gal
= 95 mg/L (----------------) = 5.5556 grains/gallon
17.1 mg/L

Hardness removed 500 gal 5.5556 grains 1440 min

-------------------------- = ----------- --------------------- -------------
1 day (24 hrs) min gal day

4,000,000 grains
= -------------------------- = 4,000 Kirograins/day
day

Total resin 4000 Kgr

required = ------------------ = 200 ft3
20 Kgr/ft3

For 2 units,
Actual design resin volume/unit = 200 ft3/2 = 100 ft3/unit

When One unit is in regeneration (flow rate through eeach unit at normal flow),

Maximum loading rate 500 gpm

-------------------------------- = ------------------
unit 100 ft3/unit

= 5.0 gpm/ft3/unit OK

Using a 60 inch (5 ft) diameter shell,

Surface area = pi r2 = 3.14 (2.5)2 ft2 = 19.6 ft2

100 ft3
Bed depth = --------------- = 5.1 ft = 61 inches
19.6 ft2
(30 < 72 inches) OK

Flow rate through each unit at normal flow,

Normal loading rate 500 gpm/2

---------------------------- = ------------------- = 2.5 gpm/ft3/unit
unit 100 ft3/unit

OK
3. Calculate the lbs of salt required per day for zeolite regeneration assuming a 24 hour regeneration cycle for each softener unit.

For zeolite regeneration,

15 lbs salt
Salt required = (200 ft3)(---------------) = 3000 lbs salt/day
1 ft3 resin