Ion Exchange Technology

Dr Liu Yu

1
What is an ion exchange?

Ions in solution are preferentially exchanged over

ions on solid medium

Ion A in solution + ion B-solid → ion B in solution + ion A-solid

ion exchange
A+ (l) + +B (s) B+ (l) + +A (s)

Solid
So d medium
ed u iss ccalled
ed ion
o eexchange
c ge resin
es

2
Applications
pp of Ion Exchange
g in Water Treatment

Ion exchange is applicable for the removal of soluble ions

from water:

• Water softening
• Demineralization
• Desalting
• Ammonia removal
• Removal of heavy metals
• Radioactive waste treatment

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Questions in mind:

1. Can ion exchange be applied for

desalting seawater?

2. Can ion exchanged be regarded as a special

case of adsorption in general?

4
Physical description of a resin

•. Ion exchange resins are formed in the shape of very

small beads, called resin beads, with an average
diameter of about 0.05 mm

•. Wet resin has the appearance of damp, transparent,

amber sand and is insoluble in water, acids, and
bases

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USfilter
6
 Resin beads

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Source: en.wikipedia
 Resin types
Two major types of ion exchange resins:

Type 1: Cation resins for exchanging positive ions

e.g. Ca2+, Mg2+, Fe2+, Mn2+ and so on

Type 2: Anion resins for exchanging negative ions

e.g. SO42-,CO32- ,NO3- and so on

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 Resins

Cation exchangers Anion exchangers

• Strong acid cation exchangers • Strong base anion exchangers

R SO3H
R-SO R NH3OH
R-NH

• Weak acid cation exchangers • Weak base anion exchangers

R-COOH R-NH2

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Example 1:

Strong acid cation exchange

RSO3H + Na+ ↔ RSO3Na + H+

2RSO3Na + Ca2+ ↔ (RSO3)2Ca + 2Na+

To remove Ca2+
W k acid
Weak id cation
ti exchange
h
RCOOH + Na+ ↔ RCOONa + H+

2RCOONa + Ca2+ ↔ (RCOO)2Ca + 2Na+

To remove Ca2+
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Example 2:

Strong base anion exchange

RR3’NOH + Cl- ↔ RR3’NCl + OH-

To remove chlorine
Weak base anion exchange

2RNH3Cl + SO42- ↔ ((RNH3)2SO4 + 2Cl-

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What is physical structure of resin?

Solid backbone + Ion active functional group

Immobile portion Exchangeable ion

R-SO3H

All resins have these three components!

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 Ion Exchange Chemistry

In theory, ion exchange is a pure chemical reaction

Reactions are stoichiometric and reversible, and in that way

they are similar to other solution phase reactions

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Example:

1. Ion exchange reaction in solution phase:

NiSO4 + Ca(OH)2 = Ni(OH)2 + CaSO4

The nickel ions are exchanged for the calcium ions

in solution-solution phase

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2. Ion exchange reaction on resin:

2(R-SO3H) + NiSO4 = (R-SO3)2Ni + H2SO4

solid liquid solid liquid

• Two resin sites are needed for nickel ions with a plus 2 valence
•.
(Ni2+)
●. Solution-solid phase reaction

How many resin sites are required for ferric ions?

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Question 1:
Q

What is the major difference between ion exchange

in solution and on resin?

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Question 2:
Is ion exchange reaction is reversible?

nR-H + Mn+ ↔ RnM + nH+

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 Th ion
The i exchange
h reaction
ti isi reversible
ibl

The degree the reaction proceeds to the right will

depend on the resins preference or selectivity

How to describe the selectivity of a resin for a specific ion?

18
The selectivityy coefficient ((K):
)

A+ + B+ = R
R-A
R B+ + A+
R-B

concentrat ion of B + in re sin concentrat ion of A + in solution

K= ×
concnetrat ion of A + in re sin concentrat ion of B + in solution

Concentration of R − B + Concentration of A +
K= ×
Concentration of R − A + Concentration of B

Equilibrium constant of ion exchange reaction!

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What is physical meanings of K?

K reflects the relative distribution of the ions

The greater the selectivity coefficient,

the greater the preference for the ion exchanger

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Factors affecting K:

The selectivity coefficient increases with:

•. Ionic valence

•. Inverse of hydrated ionic radius

•. Degree
D off polarization
l i ti

•. Inversely
y with degree
g of complexation
p in solution

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Cationic Preference Series:

Ba2+ > Pb2+ > Sr2+ > Ca2+ > Ni2+ > Cd2+ > Cu2+ > Co2+ > Zn2+ >
Mg2+ > Ag+ > Cs+ > K+ > NH4+ > H+

Wh no Na
Why N +?
Anionic Preference Series:

SO42- > I- > NO3- > HCrO4- > Br- > Cl- > OH-

Still remember the farmer’s q

question about nitrate?

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 Mechanisms of ion exchange

Step 1:Ion movement from bulk to the surface or pores of resin

•. Movement of the ions from bulk of solution

•. Diffusion of the ions through the laminar film
•. Diffusion
iff i off the ions
i through the pores

Laminar film

Ion

resin

Bulk solution 23
Step 2:Ion exchange

resin resin

Exchangeable ion on resin, such as H+, Na+ or OH- etc

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Step3: Movement of exchanged ion from resin to bulk

•. Diffusion of the exchanged ions outward

•.. Diffusion of the exchanged ions through laminar layer
•. Movement of exchanged ion into bulk of solution

Laminar film

resin

Bulk solution

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Ion
o eexchange
c ge capacity
c p c y

The total capacity of an ion exchange resin is defined as

the total number of chemical equivalents available for
exchange per some unit weight or unit volume of resin

ii.e.
e the amount of ions that a given amount of resin is
capable of removing

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Unitt o
U of ion
o exchange
e c a ge capac
capacity
ty

The capacity may be expressed in terms of

- milliequivalents
illi i l t per dry
d gram off resin
i or

- millequivalents per mL or L of resin

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Example:

A raw water is polluted by some undesired metals:

Copper: 2 mg/L
Zinc: 1 mg/L
Nickel: 1.5 mg/L

The flow rate is 0.5 m3/min. Design a cation exchange system operating
16 h/day to remove the metals. The operating capacity of
cation resin is 1
1.5
5 equivalent/L (dry vol)
vol).
(Zn=65; Cu=64; Ni=59)

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●. The cations to be removed:

Cu 2/32 = 0.06 meq/L

Zn 1/32.5 = 0.03 meq/L

q

Ni 1.5/29.5 = 0.05 meq/L

●. The total daily equivalent to be removed:

(Cu+Zn+Ni)×(500 L/min)×(16×60 min/day)

= (0.14×10
(0 14×10-3 eq/L)×(192000 L/day)

= 67 eq/day

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●. The resin required:
q

Cations to be removed 67 eq / day

= ≈ 45 L / day
exchange capacity 1.5 eq / L

How to use this figure in design?

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Question:
Why anion resin has a smaller exchange capacity than cation resin?
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 Cation resin Anion resin

D it off wett resin

Density i ((g/ml)
/ l) 1 27
1.27 1 10
1.10

Bulk density of loaded bed (including voids) 0.80 0.62

(g/ml))
(g

The anion resin is less dense than the cation resin

Thus, it has a smaller exchange capacity for a given

volume

Question:
How this affects the design of ion exchanger?
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Implication:

A larger volume (mass) is needed for anion resins than for

the cation resins to obtain equal total exchange capabilities

Small bed volume Large bed volume

Vc < Va

Cation Anion

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 Active or exchange zone

Exhausted

t1

t2
A ti zone
Active t3

fresh

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Estimate of active zone:
⎧ ⎛C + C n ⎞⎫
2 ⎨( Vx − Vb )C o − ∑ ( Vn +1 − Vn )⎜ n +1 ⎟⎬
⎝ ⎠⎭
δ= ⎩
2
⎛X⎞
A sρp ⎜ ⎟
⎝ M ⎠ ult

δ: length of active zone

Vx: total volume of water treated at complete exhaustion of bed
Vb: volume of water treated at breakthrough
Co: influent concentration to δ
Vn+1: total volume treated at time tn+1
Vn: total volume treated at time tn
Cn+1: concentration of solute at effluent of δ at time tn+1
Cn: concentration of solute at effluent of δ at time tn
As: superficial area of ion exchanger bed
ρp: packed density of ion exchange materials
(X/M)utl: maximum exchange capacity

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R
Remarks:
k

●. The length of active zone is dependent on the flow rate

●. The faster the rate of application, the longer the length of

active zone

●. The slower the rate of application, the shorter the length

off active
ti zone

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Breakthrough
When all exchangeable sites of resin are saturated, no ions can
be further removed, the resin bed is broken through
Na+ Na+ Ca2+

fresh

used

Fresh resin bed

Ca2+ Ca2+ Ca2+
with R-Na+

Active resin with R-Na Resin with R2Ca 37

Engineering breakthrough point:

To ensure a water quality required, ion exchanger must be regenerated

before theoretical breakthrough point

Ce

Ce=Ci

Ce=C
Ca
V

Vbt at which resin bed should be regenerated

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 Monitoring of the Performance of Ion Exchanger

1. Why needs to monitor the performance?

The ion exchange process is reversible

If too much solution is passed through the ion exchanger

The capacity of the resin has been exceeded

The exchange may reverse

Ions previously removed will be returned to the solution at the effluent

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Remark:

It is necessary to

periodically monitor the performance of the ion exchanger

and

either replace or regenerate the resin when indicated

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 2. How to monitor the performance?

Ion exchanger performance is measured by comparing

•. solution concentration or
•. conductivity or
•. radioactivity at the influent and effluent

The parameter measured depends upon the purpose of ion exchanger

•. Removal of heavy metals → Solution concentration

•. Desalination → Conductivity
•. Removal of radioactive ions → Radioactivity
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 Regeneration of a resin
1. General rule:

When?

When the allowable effluent concentration is reached, the

resin must be regenerated

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How?

●. Cation resin is regenerated by acid

●. Anion resin is regenerated by base

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2. Regeneration Chemistry

For Ca removal: 2R-Na + Ca2+ → R2Ca + 2Na+

For a cation system

Spent resin is converted first to the hydrogen form, R-H

R2Ca + 2HCl → 2R-H + CaCl2

Why?
then to the sodium form, R-Na

R-H + NaCl → R-Na + HCl

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Recall: Cationic Preference Series:

Ba2+ > Pb2+ > Sr2+ > Ca2+ > Ni2+ > Cd2+ > Cu2+ > Co2+ > Zn2+ >
Mg2+ > Ag+ > Cs+ > K+ > NH4+ > H+

Question:
Why cation resin can be regenerated by acid?

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Basic regeneration steps:

The column is backwashed to remove suspended solids

The resin bed is brought in contact with the regenerant

solution
l i

A slow and fast water rinse remove any residual regenerant

The column is returned to service

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 Inf

Solids Acid elutes NaCl elutes Slow/fast water rinse

Saturated
Exchangeable

Backwash Eluate Eluate Residuals

Eff

Saturated resin → R-H R-H → R-Na

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 Fixed-Bed Ion Exchanger
Almost all ion exchangers are designed as a fixed-bed system

Supporting layer 48
Remco Engineering
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 Main applications of ion exchange technology

●. Water softening for Ca2+ and Mg2+ removal

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 ●. Demineralization or desalination of water

To remove cation
and anion

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 Some configurations of ion exchanger

Configuration 1: To remove purely anions or cations of interest

Raw water Raw water

anion cation

Retention elements or other suitable devices in the bottom have

openings smaller than the diameter of the resin beads
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Configuration 2: To remove mixed anions and cations

Option-1: Separate Two-stage ion exchanger

Raw water

cation anion

Deionized water

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Option-2: Layered-bed ion exchanger

cation
anion

anion
cation

Question:
Th
These ttwo llayered
d iion exchangers,
h which
hi h one iis reasonable
bl
54
 anion
Packed density:
cation > anion
cation

•. The specific volume ratio of cation to anion depending on their

specific gravities

•. The ratio is normally 2 parts cation resin to 3 parts anion resin

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Option-3: Mixed-bed ion exchanger
The resin itself is a uniform mixture of cation and anion resins

cation

anion

Question:
Which flow pattern is a reasonable and why?
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Preferred flow pattern:

If the flow was reversed: bottom to top !

The lighter anion resin would gradually rise up to

th top
the t

Stratification process

resulting in a layer of anion resin on top of

the cation resin

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Mixed-bed ion exchanger over layered-bed ion exchanger

For fixed amounts of anion and cation resins, the efficiency

f removall off impurities
for i iti isi greater
t ini a mixed-bed
i d b d than
th a
layered arrangement

WHY?

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Main reason:

For layered resins there may be large pH gradients within

the column of resin

Why this hinders ion exchange?

59
Be aware that

Ion exchanger
g can not function as a filter

The resin column will filter some undissolved material,

but the efficiency for filtration is significantly less than that

for removal by ion exchange.

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Cost of commercially
y available resins for reference

R i
Resin C t (US$/ft3)
Cost
Strong acid cation 70-120
W k acid
Weak id cation
ti 150 200
150-200
Strong base anion 180-250
W kb
Weak base anion
i 180 200
180-200
Chelating cation 330-600

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Design consideration of ion exchange process

● To select a proper resin for specific use: selectivity coefficient

● To determine exchange capacity

● To determine mass and volume of resin required

● To determine the numbers of exchangers: even numbers

● To select regenerant

● To design the configuration of ion exchanger:

column-type fixed bed in water supply industry

● Pipeline and valves arrangement

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The resin column must:

→ contain and support the ion exchange resin

→ uniformly distribute the service and regeneration

flow through
g the resin bed

→ provide space to fluidize the resin during backwash

→ include the piping, valves, and instruments needed

to regulate
• flow
fl off feed
f d
• regenerant and backwash solutions

63