RICH, 1963

9.1 Mechanism of IE
 Can be classed as a unit operation
 Involves ionic concentrations & chemical equilibria
  unit proses
IE
 The displacement of ions of given species from
insoluble exchange materials
 By ions of different species
 When solutions of the latter are brought into contact
with the exchange materials
General equilibria
 B1+ + R-B2+  B2+ + R-B1+ (9-1)
 A1-+ R+A2-  A2- + R+A1+- (9-2)

Where:
 B1+ , B2+ = cations of two different species
 A1-, A2- = anions of two different species
 R-,+ R+= cationic & anionic exchange materials
tratio
 The exchange behaves as a chemically reversible
interaction between:
 A fixed, ionized exchange site on the exchange
material , and
 Ions in solution
The equilibrium expression:

 K = an equilibrium constant = equilibrium selectivity

coefficient
 Once K > 1:
 Exchange process involve a favorable equilibrium
 Eq 9-2: the exchange material will preferentially
take up cations of B1+
 If a solution contains:
 Concentration of B1+ = B3+
 Is contacted with exchange material R- B2+
 The species of cation having K > exchange material 
will be preferentially picked up over the other species
Relative order in displacing
 Table 9-1: the realtive order in which ion generally
displace other ions held by an exchange material.
 Ion species appearing low in the series are displaced
from the exchange material by species listed higher in
the series.
 Ex: solution: K+
 Exchange material Na+
 Na+ is lower in the order than K+  Na+ is replaced by
K+
 Displacement is a function of concentration (or
activity in the case of concentrated solution)
Materials for IE
 Originally, alumino silicates:zeolites
 Natural
 Synthetic
 Displaced now by:
 Synthetic resins
 Sulfonated carbonaceous compounds i.e. coal
 Synthetic resins  popular  will be used in all
new applications in the future.
Synthetic resins
 Most are polymeric containing ion active groups, i.e:
 SO3H-
 NH4+
 Physical form: Spherical
 Size: 16-30 mesh
 Average diameter: 0.5 – 0.75 mm
Capacity of IE materials
Can be expressed in a number of ways.
In WTP CaCO3 kilograins/ft3  water softening
Applications are now wider than water softening
 gram equivalent or millequivalents/volume
Capacity of IE materials vary with:
 The nature and
 The concentration of ions in the solution
 The concentration of regenerating solution
Ultimate capacity
The application of IE materials is economical only if
the materials are regenerated
9-2 IE in Water Treatment
 Application of IE:
 To concentrate valuable ionized materials from
dilute solutions
 For selective fractionation of certain ionized solutes
in solution
 To remove the objectionable ions from water used
for domestic & industrial purposes  widest
application
Removal of hardness
 Removal of hardness ions Ca++ & Mg++ only
  exchange materials operate on a sodium ion cycle
  exchange Na+ for Ca++ & Mg++
 The equilibrium equation for the removal of calcium:
Ca++ + R-2(Na+)2  2 Na+ + R-2Ca++ (9-4)
Regeneration
 Once the exchange material is “spent” ( equilibrium is
reached)  the exchange material in the form of R-
Ca++ is regenerated to R-2(Na+)2  reused
 By contacting the exchange material with a solution of
sodium ions
 Since the K in (9-4) = large values  at equilibrium 
 almost all the exchange material is in the R-Ca++
form
 solutions with high concentrations of Na+ are
required for regeneration
Regeneration
 Is accomplished normally using solutions of 5-10%
NaCl
 Table 9-2: approximate exchange capacity of several IE
materials with regeneration requirements
 Sea water & water from brine wells occasionally are
used for this.
 H/e the effect of less concentrated solutions on
exchange capacity is illustrated in Fig. 9-1.
Demineralization
 Total removal of all ions
 By contacting the water being treated with:
 Cationic
 Anionic exchange materials
Cationic exchange materials
 Operate on a hydrogen cycle
 Are regenerated with acid
 Ex. The equilibrium equation for the removal of
sodium ions
Na+ + R-H+  H+ + R-Na+ (9-5)
Anionic exchange materials
 Operate on a hydroxyl cycle
 Regenerant: a strong base
 Ex. The equilibrium equation for the removal of sulfate
ions
SO4-2 + R++(OH-)2 2OH- + R++SO4-2 (9-6)
The hydrogen & hydroxyl ions combine in conformance
with the equilibrium expression for water (Fig. 7-2) 
effecting an almost complete deionization.
Demineralization
 Using:
 Mixed beds  sometimes
 Separate units  more often
IE materials in WTP
 Limited to waters containing little turbidity
 Turbidity
  coat the surfaces of IE materialreducing:
 The exchange capacity
 Regeneration efficiencies
 Similar results occurred once feerous ions are
oxidized by DO & precipitate out as ferric
hydroxide
9-3 Design of fixed-bed exchangers
 Usage of IE:
 Continuous contacting & regenerating
concurrently
 Intermittent  for regeneration  most applied
 Consisting a strongly ionized IE material with a
favorable equilibrium
Design of fixed-bed exchangers
 Once a solution of ions passes through a fixed bed of
IE material the concentration of ions is reduced to
zero as the solution contacts successive portions of the
bed.
 Fig. 9-2: the location of a hypothetical gradient in a
fixed bed at different intervals of time.
 Such a gradient is located initially at the top of the bed
 travels downward through the bed as the top layers
of The IE material became spent.
Design of fixed-bed exchangers
 At t
  the gradient is located entirely within the bed
  none of the ionic species being removed escapes
in the effluent
 By t2
  the gradient has receded to a point where the
ions begin to appear in the effluent
 At t3
  the gradient has almost passed through the bed
  the concentration of ions is ≈ feed concentration
Design of fixed-bed exchangers
 The gradient delineates a moving zone  all the ions
are removed from the solution
 But, an exchange zone  the concentration of the ions
being removed is reduced from 95 to 5% of feed C.
Design of fixed-bed exchangers
 Constant:
 The height of the exchange zone
 The rate at which it moves through the bed
 Height & rate will vary with:
 Feed rate
 Feed C
 Exchange capacity
 Dimension of the bed
Breakthrough curve
 Fig. 9-3: determination of the height of the exchange
zone from an analysis of a breakthrough curve
 a breakthrough curve
 constructed from data obtained in the lab
 the effluent C of the ion being removed vs the vol of
effluent
 Effect of flow rate
 Points of breakthrough at C eff = 5% off C feed (C0)
 Points of exhaustion at C eff = 95% off C feed (C0)
Quantity of ion removed
 Height of the exchange zone remains constant
 The exchange zone will descend through the bed in a
distance = its height during the time it takes for a
volume of effluent (=VE) to pass through the bed
 The quantity of ions removed from the volume VE of
solution as it passes through the exchange zone must =
the quantity retained in the zone
Quantity of ion removed
 VE C0 = ZS (Q +ε C0) ---(9-7)
 VE = effluent volume collected between the point of
breakthrough & exhaustion, cm3
 C0 = initial solution concentration of ions being removed,
gme/cm3 of solution
 Z = height of exchange zone, cm
 S = cross-sectional area of the bed, cm2
 Q = exchange capacity of the bed material, gme/cm3 of
exchange material
 ε = bed porosity = ratio of volume of voids to the total
volume
Height of exchange zone
 (9-8)

 Z = transfer unit method

capacity
 Once breakthrough occurs:
 the IE bed is divided into 2 regions:
1. The exchange zone at the bottom of the bed
2. The remainder of the bed on top
 The capacity of the exchange zone at breakthrough
 only 50% utilized (the average of 5 & 95%)
 The rest of the bed  completely exhausted
 a balance struck between:
 The total capacity required and
 The feed ion content of the bed at breakthrough
Bed depth
 Capacity required =
 Feed ion content of exchange zone + Feed ion content
of remainder of the bed
 C = 0.5 S Z Q + S (L – Z) Q (9-9)
 L = 0.5 Z + (C/SQ) (9-10)
To calculate L
 Z (height of exchange zone) is a function of Vs
(superficial velocity)
Vs = Flow rate/S
Steps:
• Define required volume of exchange material (V)
• Assume cross –sectional area, S
• Calculate Vs
• Determine Z:
1. Lab
2. Transfer unit method
• Calculate L