Cap 22 Absorption and Ionic Exchange

TX69299 ch01 frame.
book Page 823 Wednesday, September 4, 2002 2:13 PM
22
Adsorption and Ionic Exchange
22.1 Introduction
Adsorption and ionic exchange are mass transfer unit operations in which
a solute contained in a fluid phase is transferred to the solid phase due to
retention on the solids surface or to a reaction with the solid.
22.1.1
Adsorption
The solute retained in adsorption processes is called adsorbate, whereas the

solid on which it is retained is called adsorbent. Solids with a large contact
surface are used as adsorbents and are generally porous. Activated carbon
is widely used as adsorbent, although there are synthetic polymers called
molecular sieves also used for adsorption processes.
The force with which the solute is retained can be of three types: electric,
Van der Waals forces, and chemical. Electric forces are due to attractions
between a solute with a certain charge and points of the adsorbent with an
opposite charge. The adsorption is called physical when the forces are of
Van der Waals type, and adsorption is usually reversible. However, adsorption can be due to a chemical reaction between the solute and the adsorbent
a chemisorption. While in the physical adsorption the solute can be retained
on any point of the surface of the adsorbent, in chemisorption the adsorbent
presents active points on which the adsorbate is retained.
Adsorption is used in many cases of purification of fluids containing
contaminants that give them unpleasant flavors or aromas. Limonene is a
compound that confers bitter flavor to orange juice, and it can be eliminated
by adsorption on polymers. In the same way, melanins and melanoidins,
formed by enzymatic and nonenzymatic browning, can be eliminated by
adsorption on activated carbon.
22.1.2
Ionic Exchange
Ionic exchange consists of replacing ions of a solution with others contained

in a solid, which is called exchange resin. The ionic exchange can be consid823
2003 by CRC Press LLC
TX69299 ch01 frame.book Page 824 Wednesday, September 4, 2002 2:13 PM
824
Unit Operations in Food Engineering
ered a chemical adsorption, where ion exchange occurs at defined points of

the resin. The mathematical treatment for calculation of exchange columns
is similar to that for adsorption. Depending on the type of ions that they can
exchange, resins can be anionic or cationic. One of the most important
applications of ion exchange is desalination and conditioning of water.
22.2 Equilibrium Process

22.2.1
Adsorption Equilibrium
When a solid adsorbent and a fluid containing a solute come into contact,
the system evolves in such a way that the solute is transferred to the surface
of the solid and retained there. This process continues until reaching a
dynamic equilibrium between both phases. At that moment, the fluid phase
has a concentration of solute C, while in the solid phase the amount of solute
per unit mass is m. The values of C and m at equilibrium depend on temperature, and the function that gives the variation of the amount of solute
retained by the adsorbent (m) with the concentration of solute in the fluid
phase (C) is called adsorption isotherm. This type of isotherm can have
different forms. Figure 22.1 shows the typical isotherms that can be presented
in different types of soluteadsorbent systems.
m
g adsorbed / g solid
Irreversible
O
O
FIGURE 22.1
Types of adsorption isotherms.
Linear
g dissolved / 1C solution
825
The theoretical obtainment of the adsorption isotherms can be based on

kinetic or thermodynamic considerations, the former more intuitive. Also, it
depends on considering whether the solute is retained by the adsorbent in
one or in various molecular layers.
One intuitive and simple case is adsorption of one adsorbate on one molecular layer. Thus, if it is supposed that solute A in the fluid phase is adsorbed
by solid S, according to the kinetic mechanism:
K
1
S A
A( F ) + S
K2
The adsorption rate of A is expressed by the equation:
rA = k1 CA m0 mA k2 mA
(22.1)
where:
rA = adsorption rate of A
CA = concentration of A in the fluid phase
m0 = maximum concentration of A retained by the adsorbent
mA = concentration of A retained by the adsorbent
At the adsorption equilibrium, rA = 0, hence:
k1 CA m0 mA = k2 mA
The adsorption equilibrium constant can be defined as:
K=
k1
mA
=
k2 CA m0 mA
(22.2)
Obtaining:
mA
K CA
=
m0 1 + K CA
(22.3)
This equation is called isotherm of Langmuir, and experimental data of

many different systems fit well. However, another equation frequently used
is the isotherm of Freundlich, which is an empirical equation of the form:
mA = K(CA )n
(22.4)
826
where K and n are parameters, the values of which are a function of the type
of adsorbate-adsorbent system and of temperature. The determination of
these parameters should be made experimentally.
Another isotherm is that of Brunauer, Emmett, and Teller (BET), used for
adsorption of one solute on multilayers (Brunauer et al., 1938; Emmett and
de Witt, 1941):
mA =
BCA mA1
C
CAS CA 1 B 1 AS
CA
(22.5)
where mA is the amount of adsorbed solute per unit mass of adsorbent for
the concentration CA, CAS is the saturation concentration of the solute, mA1 is
the amount of solute adsorbed per unit of adsorbent that forms a monolayer
on the surface of the solid, and B is a constant representing the interaction
energy with the surface.
For solutes contained in a gas phase, the BET isotherm for n layers can be
expressed according to the equation:
mA
Bx 1 (n + 1) x n + nx n +1
=
m0 1 x 1 + (B 1) x b X n +1
(22.6)
where:
x=
PA
partial pressure of A
=
PA0 vapor pressure of pure A
When the number of layers n = 1, it is obtained that:

mA
Bx
=
m0 1 x
(22.7)
which coincides with the isotherm of Langmuir.

If the number of layers is high, the BET isotherm is transformed into:
mA
Bx
=
m0
1 x 1 + (B 1) x
)(
For low values of x, the last equation is transformed as:

mA
Bx
=
m0 1 + (B 1) x

22.2.2
827
Ionic Exchange Equilibrium
If a fluid that contains an anion An+ with charge n+ is available and comes
into contact with a resin that can exchange a cation Bn+ with the same charge
as A, it can be considered that the following cationic exchange reaction is
complied with:
K
1
Bn + + R A
An+ + R B
K
2
The disappearing rate of the cation An+ is:
( r ) = k C
A
CR B k2 CB CR A
When equilibrium is reached, the disappearing rate of A is null, so the

following is complied with:
K=
k1 CBCR A
=
k2 CA CR B
Substitution in the last equation allows expression of the disappearing rate

of A as a function of the equilibrium constant K.
The concentration in the liquid phase of the ions involved in the ionic
exchange is usually expressed in equivalents/liter of solution; while in the
solid phase, the concentration is expressed in equivalents of ions per unit
mass of resin. In this way, if CA0 is the initial concentration of A in the solution
and CA is the concentration of A at a determined instant, and if CB is the
concentration of ions B that have been exchanged for A, then it is complied
that CB = CA0 CA. For the resin, EA are the equivalents of A per unit mass of
dry resin and EM is the maximum capacity of the resin, expressed as equivalents of A per unit mass of dry resin that it can exchange with ions A. The
concentration of B in the resin is:
EB = EM EA
Therefore, at equilibrium, it is complied that:
(C
K=
0
A
CA EA
CA EM EA
(22.8)
If the equivalent fractions of A in the liquid and resin phases are defined as:
828
liquid phase:
Y=
CA
CA0
resin phase:
X=
EA
EM
the equilibrium constant is expressed as:
K=
(1 Y ) X
Y (1 X )
(22.9)
This equilibrium constant is called the separation factor.
22.3 Process Kinetics

22.3.1
Adsorption Kinetics
In every adsorption process, three solute transfer stages can be considered:

1. External transfer: The solute at the fluid phase with a concentration
C is transferred to the fluidsolid interphase in which the concentration is Ci. The mass flux is given by the equation:
N = k F C Ci
(22.10)
where kF is the mass transfer coefficient in the external phase.

2. Diffusion inside the solid: The mass flux on the wall of the solid
for a spherical solid particle with radius ri is expressed as:
N = De
CS
r
(22.11)
where CS is the concentration of solute in the solid and De is the

effective diffusivity of the solute.
3. Adsorption stage: For the simpler case, expressed before, it can be
stated that:
r = k1 CS m0 mS k2 mS
829
and at equilibrium:
mS
K CS
=
m0 1 + K CS
Generally, the first of these stages controls the process, so it can logically
be assumed that equilibrium is reached during the adsorption stage. Therefore, if the mass transfer stage controls the process, it is complied that Ci =
CS, and its value is constant along the whole solid.
22.3.2
Ionic Exchange Kinetics
As they occur in physical adsorption processes, different stages of mass

transfer can be considered during ionic exchange:
1. External mass transfer of ion A from the solution to the resins
surface
2. Diffusion of ion A through the pores of the resin until reaching the
exchange points
3. Ionic exchange reaction in which ion A is exchanged by ion B in
such a way that A is bound to the resin while B passes to the fluid
phase
4. Diffusion of ion B through the pores of the resin until reaching the
resins surface
5. External mass transfer of B from the surface of the resin to the
solution
The slowest stage is the one that controls the ionic exchange process.
Generally, the diffusion stages or the external mass transfer stages control
the global process:
( r) = k A CA CAi = k B CBi CB
where the superscript i indicates interface concentrations, and it is complied

that CAi is in equilibrium with C Bi .
22.4 Operation by Stages

As in other mass transfer unit operations, adsorption and ionic exchange
processes can operate in stages, in batch as well as in continuous operations.
830
The most common ways of operation are single stage or contact and multistage, which can be repeated single contact or countercurrent multiple stage.
22.4.1
Single Simple Contact
This is the simple method of operation. As shown in Figure 22.2a, a fluid
stream containing the solute and the solid stream are contacted in one stage.
The solute passes to the solid stream, thereby decreasing its concentration
in the fluid phase. It is assumed that the fluid and solid that leave the stage
are in equilibrium; this means that an ideal stage is supposed.
The mass flows of the fluid and solid streams are F and S, respectively.
Also, C and m are the concentrations in the fluid and solid streams, respectively. Generally, the mass flows of the fluid and solid streams present a
a)
S
mE
F
CE
CS
S
mS
b)
m
Isotherm
mS
(C E , m E )
CS
FIGURE 22.2
Single contact: (a) operation sketch; (b) operation in the equilibrium diagram.
831
slight variation between the inlet and outlet, so they are considered constant.
When performing a solute balance in the system it is complied that:
) (
F CE CS = S mS mE
where the subscript E means inlet and S means outlet. Rearranging:

mS =
F
F
CS + mE + CE
S
S
(22.12)
which, in the mC diagram, is the equation of a straight line with slope F/S.
Therefore, if the conditions of the inlet streams are known, the concentrations
of the streams that leave the stage can be determined in the mC diagram
(Figure 22.2b). For this reason, a straight line with slope F/S is traced from
the point that represents the inlet streams (CE,mE), and the concentrations of
the outlet streams (CS,mS) are obtained where the straight line crosses the
equilibrium curve (adsorption isotherm).
For a batch operation, it is convenient to use total amounts and concentrations:
V CI CF = S mF mI
(22.13)
where V is the total volume of the fluid and S is the total amount of solid,
while the subscripts I and F denote initial and final concentration, respectively.
22.4.2
Repeated Simple Contact
This is a multistage operation in which the fluid phase that leaves a stage is
fed to the following stage (Figure 22.3a). It is considered that all the stages
present an ideal behavior, so the concentrations of the fluid and solid streams
that leave any stage are in equilibrium. Generally, the solid fed to each stage
contains no solute; therefore, mE = 0. In addition, the amount of solid used
in each stage is the same (S1 = S2 = = SN = S).
When performing a solute balance around any stage i:
) (
F Ci 1 Ci = S mi mE
Rearranging the equation:
F
F
mi = Ci + mE + Ci 1
S
S
(22.14)
832

a)
S1
F1
F2
2
C1
CE
S1
b)
SN
mE
S2
mE
m1
S2
mE
FN
....
N
CN
C2
SN
m2
mN
m
Isotherm
Slope
CN
C1
C0
= -
F/S
FIGURE 22.3
Repeated simple contact: (a) sketch of the operation; (b) operation in the equilibrium diagram.
If it is desired to determine the concentrations of the streams that leave

each stage, one should operate as follows. The point that represents the inlet
streams (mE,C0) is represented in the mC diagram. A straight line with slope
F/S is traced from this point. The point where this straight line crosses the
equilibrium curve determines the concentrations m1 and C1. A straight line
with the same slope is traced from the point (C1,mE); the point where it crosses
the equilibrium curve determines the composition C2 and m2 of the streams
that leave the second stage. The process continues until N, which allows one
to obtain the concentration of solute CN in the fluid phase (Figure 22.3b).
When the final concentration of the fluid phase is known and it is desired
to determine the number of stages required, the way to operate is similar.
The graphical process begins at point (C0,mE), and straight lines with slope
F/S will be traced as described previously until exceeding the final concentration CN. The number of straight lines of slope F/S traced is exactly
the number of stages N needed to decrease the solute content in the fluid
stream from C0 to CN.
22.4.3
Countercurrent Multiple Contact
N stages are used in this type of operation, and the fluid and solid streams
circulate in opposite directions. The outlet stream of each stage is fed to the
833
a)
F
C0
F
CN
C2
C1
1
2
m2
m1
b)
....
S
m N+1
mN
m
Isotherm
m1
Operating
straight line
m N+1
CN
C0
FIGURE 22.4
Countercurrent multiple contact.
following one. The fluid stream enters the system by the first stage, while
the solid stream is introduced in the last stage (Figure 22.4). As in the other
cases, it is supposed that the stages are ideal and that equilibrium is reached
in each one.
The following equation is obtained from the global balance:
) (
F C0 CN = S m1 mN + 1
In the mC diagram, this is the equation of a straight line with slope F/S
that passes through the points (C0,m1) and (CN,mN+1), called the operating
straight line. The number of stages required to decrease the concentration
in the fluid phase from C0 to CN+1 is obtained by plotting steps between the
operating line and the equilibrium curve (Figure 22.4).
The maximum fluid flow to treat per unit of solid is obtained by drawing
the straight line that passes through the point (CN,mN+1) and the point on the
equilibrium curve with abscissa C0. This line has a slope equal to (F/S)MAX
(Figure 22.5a). It can occur that, when tracing the straight line with maximum
slope, it crosses the equilibrium curve. In this case, the tangent to the curve
should be traced and its slope is given by the relationship (F/S)MAX (Fig. 25.5b).
834

a)
m
Isotherm
(F/S)
max
m N+1
C0
CN
b)
m
Isotherm
(F/S) max
m N+1
C0
CN
FIGURE 22.5
Countercurrent multiple stage. Conditions of maximum treatment flow: (a) convex isotherm;
(b) concave isotherm.
22.5 Movable-Bed Columns

In certain cases, the adsorption or ionic exchange stage consists of a cylindrical column in which the fluid and solid phases are fed under countercurrent (Figure 22.6). It is assumed that the solid moves along the column under
plug flow.
A solute balance around a differential section of height dz yields:
v A C = v A C + dC + N A dz 1 aS
where v is the fluids circulation linear velocity, A is the transversal section
of the column, is the porosity of the solid in the column, and aS is the
835
C1
m-dm
C- dC
dz
C0
FIGURE 22.6
Moving-bed column.
specific surface of the solid bed, while N is the flux of the transferred solute,
its value being:
N = k F C Ci
In this equation, kF is the mass transfer constant and Ci is the concentration

of the solute at the fluidsolid interphase. The calculation of Ci can be difficult, so it is convenient to express this transfer as a function of the concentration of the fluid Ce, which is in equilibrium with the concentration of the
solid:
N = k F C Ce
Therefore, when substituting this expression in the solutes balance, the

height of the column can be obtained if the resulting equation is integrated:
z
v
z = dz =
k F aS 1
C0
C1
dC
C Ce
(22.15)
836
Generally, the integral does not have an analytical solution and should be
solved by numerical or graphical methods.
22.6 Fixed-Bed Columns

Fixed-bed columns are the most used equipment for adsorption and ionic
exchange processes. The adsorbent solid or exchange resin is contained in
the column, and the fluid that contains the solute to retain or exchange is
circulated through the column (Figure 22.7).
C0
C-dC
A
dz
FIGURE 22.7
Fixed-bed column.
If a solute balance is performed at a column differential of height dz, it is

observed that the inlet term is equal to the outlet term plus the part accumulated in the liquid retained in the porous fraction of dz and that accumulated in the solid:
v A C = v A C dC +
d
A dz C + 1 A dz P m
dt
In this equation, v is the fluids circulation linear velocity, A is the transversal section of the column, is the porosity of the solid bed, C is the
concentration of solute in the fluid phase, m is the concentration of solute
in the solid phase, and P is the density of the adsorbent particles or exchange
resins.
When developing the accumulation term, and rearranging all the terms,
the last equation can be expressed as:
dC dC 1 dm
dz
dt
P dt
(22.16)
This is a basic equation that allows calculation of the height of the column,
although the solution method varies according to the operation conditions.
Three methods to calculate the height of solid particle beds are presented
next.

22.6.1
837
Fixed-Bed Columns with Phase Equilibrium
To solve Equation 22.16, it will be assumed that the equation does not control
the mass transfer stage and also that the fluid and solid phases are in
equilibrium. The rate at which a point with constant concentration moves
along the column can be obtained from this equation:
dz
v
=
dt
1
dm
1 + P dC
(22.17)
where the relationship dm/dC is the slope of the equilibrium curve.

If it is considered that a volume V of a fluid that passes at a rate v through
a column with transversal section A has been treated in a time t, it is complied
that: V = A v t.
For constant concentration, integration of Equation 22.17 allows calculation of the height of the solid bed contained in the column:
z=
vt
V
=
1
1
dm
dm
P
A1 +
1 + P dC
dC
(22.18)
Sometimes it is desired to know the amount of solid that should be charged

to the column to carry out the operation or the amount of fluid that can be
treated per kg of solid contained in the column. If V is the amount of fluid
to treat and S is the amount of solid in the column, it is complied that:
V
Avt
1
1 dm
+
=
=
S z A 1 P
1 P dt
22.6.2
(22.19)
Rosens Deductive Method
This is another method that allows solution of problems related to solute

adsorption by fixed beds of adsorbent. It is assumed that resistance to mass
transfer occurs inside the adsorbent.
When performing a solute balance for the whole column, it is supposed
that all the solute that enters is accumulated on the surface of the solid. The
solutes inlet and accumulation terms are:
Inlet:
N A z aS = k F C Ce A z aS
838
Accumulation:
d
m A z 1
dt
= A z 1 dm
p
dt
The following expression is obtained when equaling and rearranging the

inlet and accumulation terms:
) (
k F aS
dm
=
C Ce
dt
1 p
(22.20)
where Ce is the concentration of the fluid phase in equilibrium with the

concentration in the solid phase m and is obtained from the equilibrium
curve.
In the case that the isotherm is linear, m = KaC, the equation has an
analytical solution (Rosen, 1952; 1954). Thus, the concentration of the fluid
stream that leaves the column is calculated by the expression:

3

1
1
C = C0 1 + erf 2
1 + S
2
2

(22.21)
where erf is the error function of Gauss, while the parameters , , and are:
Time parameter:
Length parameter:
Resistance parameter:
8 De
z
1
2
v
dP
(22.22)
12 De Ka (1 ) z
v dP2 p
(22.23)
2De K a
dp k F
(22.24)
where De is the effective diffusivity, Ka is the slope of the equilibrium line,

kF is the mass transfer, dP is the diameter of the particles in the bed, v is the
linear circulation velocity of the fluid, and z is the height of the column.
22.6.3
The Exchange Zone Method
The exchange zone is defined as the part of the bed of solids where the mass
exchange is produced. When a fluid stream contains a solute with a concen 2003 by CRC Press LLC

a)
839
b)
F
C
C0
ZC
ZC
F
C0
FIGURE 22.8
Exchange zone and concentration profile of the fluid stream in this zone.
tration C0 and is introduced in a column with an adsorbent bed or exchange

resin, the solute passes to the solid phase and the fluid stream leaves the
column free from this solute. The upper layers of solid will fill first, and a
concentration profile of the fluid phase is created in the column as shown
in Figure 22.8. It can be observed that when the first layer of adsorbent is
full, there is a layer at certain height zC that still has not retained or exchanged
solute, and the fluid is free from solute. The height zC is called height of the
exchange zone. The time required to form this exchange zone is the formation
time tF .
Once the zone is formed with the corresponding concentration profile, the
concentration front crosses the whole column until it reaches the outlet,
which occurs when this front has crossed the total column height zT. The
breakpoint is defined as the instant in which the fluid stream leaving the
column starts leaving solute, although in practice it is considered that this
point is reached when the concentration of the fluid stream is 5% of the inlet
stream concentration. At the instant when the breakpoint is reached, the
volume of fluid treated is VR, while the elapsed time is the breakpoint time
tR . When the fluid stream that leaves the column has the same concentration
as the inlet stream, the solid is completely full and the saturation point is
reached, although in practice it is considered that this point has been reached
when the concentration of the fluid at the columns outlet is 95% of the inlet
concentration. At the saturation point, a volume of fluid VT has been treated
in a total time tT .
Figure 22.9 is obtained by plotting the concentration of solute in the fluid
stream against the volume of fluid treated. It is easy to deduce that the
volume treated to form the exchange zone is the difference between the
840
C0
SATURATION
MR
MC
BREAKPOINT
VR
VT
FIGURE 22.9
Volume of fluid treated under breakpoint and saturation conditions.
volume treated to reach the saturation point and that required to reach the
breakpoint: VC = VT VR.
The amounts of solute retained or exchanged by the solid at different
operation points can also be obtained. The amount of solute retained or
exchanged by the solid bed to form the exchange zone is defined as MC,
while MR is the solute retained or exchanged by the solid until the breakpoint:
MR = VR C0. In this equation, C0 is the concentration of solute in the fluid
stream at the columns inlet. In adsorption processes these amounts are
expressed in grams or moles of solute, while in ionic exchange processes
they are given in equivalents of solute.
Time tF has been previously defined as the time needed to develop the
exchange zone; however, definitions of new parameters are required. Thus,
the time needed by the exchange zone to cross its own height zC is defined
as the relationship between the volume of fluid to form the exchange zone
and the circulation volumetric flow rate of the fluid stream:
tC =
VC VC
=
q
vA
(22.25)
where v is the linear velocity and A is the transversal section of the column.
In the same way, the total time required to reach the saturation point is
given by the relationship between the total volume treated and the volumetric flow rate:
tT =
VT VT
=
q
vA
(22.26)
The rate with which the exchange zone moves is:

v=
zT
tT tF
(22.27)
841
It is easy to deduce from all these definitions the relationship between the
total height of the bed and the height of the exchange zone:
zT
tT tF
zC = tC v = tC
(22.28)
On the other hand, the relationship between the total time and the time
required by the exchange zone to cross its own height is obtained by combining the last equations:
tT = tC
VT
VC
(22.29)
The amount of solutes retained or exchanged from the breakpoint to the

saturation point is obtained by integrating the variation of the concentration
in this range:
VT
MC =
(C C) dV
(22.30)
VR
It is easy to observe that the maximum amount of solute that can be

retained or exchanged in this zone is:
(M )
C MAX
= C0 VT VR = C0 VC
A new parameter i is defined as a fraction of the exchange zone with

capacity for retaining or exchanging:
VT
(C C) dV
VT
MC
i=
=
MC MAX
( )
VR
VC C0
=1
C dV
VR
VC C0
(22.31)
The formation time of the exchange zone and the time required by the
exchange zone to cross its own height can be related according to the equation:
tF = 1 i tC
(22.32)
The concentration profile of the exchange zone is different according to

the value of the parameter i (Figure 22.10). In the case when i = 0.5, it is said
that the breakthrough curve is symmetrical, complying that tF = 0.5 tC.
842
C0
C0
C0
i 0
a)
i = 0.5
i1
ZC
ZC
b)
c)
ZC
FIGURE 22.10
Concentration profile (breakthrough curve) of the exchange zone as a function of the value of i.
F
C2
S
m2
SATURATION
C + dC
m + dm
N
BREAKPOINT
F
C1
S
m1
FIGURE 22.11
Conditions of the exchange zone.
22.6.3.1
Calculation of Height of Exchange Zone

in an Adsorption Column
The calculation of the height of the exchange zone is made assuming that
this zone is similar to a countercurrent unit of infinite height that operates
under stationary conditions. Therefore, it is considered that, in this zone, the
conditions represented in Figure 22.11 are given, where a fluid stream F with
a solute concentration C0 is fed by the top of the column, while a stream S
of the adsorbent solid with a concentration m1 is fed by the bottom of the
column. The fluid that leaves the column has a solute concentration equal
to C1, while the solute content of solid stream is m1.
843
Since the columns height is infinite, the saturation conditions will be given
in zone 2 while the breakpoint conditions are in section 1. Therefore it is
complied that C1 = 0 and m2 = mMAX, where mMAX is the maximum concentration of solute that the solid can adsorb.
When performing a solute balance between the bottom of the column and
any column section, it is obtained that:
) (
F C C1 = S m m1
(22.33)
But C1 = 0 and if, in addition, the adsorbent solid is free from solute when
it enters into the column, m1 = 0. Hence:
F C = Sm
If the solute balance is made for a dz of column, then:
F dC = k F C Ce aS A dz
This equation allows calculation of the height of the exchange zone. If it
is integrated with the boundary conditions marked in Figure 22.11:
F A
zC =
k F aS
C2
dC
C C
C1
(22.34)
e
This equation is generally solved by graphical or numerical integration.

When the equilibrium isotherm is linear (m = KaC), the equilibrium concentration Ce is:
Ce =
m
FC
=
Ka S Ka
Substitution into Equation 22.34 yields an expression easy to integrate, in

which the height of the exchange zone is:
zC =
C
F A
ln 2
K k F aS C1
(22.35)
where C1 and C2 are the concentrations of the fluid phase at the breakpoint
and saturation point, respectively, while K is a parameter defined as:
K = 1
F
SK a
844
If it is considered that the following is complied at the breakpoint and

saturation point:
C1 = 0.05 C0 and C2 = 0.95 C0
then Equation 22.35 is transformed into:
zC =
( )
F A
ln 19
K k F aS
(22.36)
22.6.3.2
Calculation of Height of Exchange Zone in an Ionic

Exchange Column
The way to operate is similar to the case of the adsorption column. From
the solute balance between the bottom of the column and any column section,
it is obtained that:
) (
F C C1 = S m m1
(22.33)
The equivalent fractions in the fluid phase (Y) and the resin (X) can be
defined as:
Y=
X=
C
C0
m
mMAX
In this equation the concentration C of the fluid phase is expressed as

equivalents of solute per liter and the concentration in the resin m is
expressed as equivalents of solute per kg of resin. Also, mMAX is the maximum
retention capacity of the resin. The equation of the solute balance is:
F C0 Y Y1 = SmMAX X X1
(22.37)
which is the so-called operating line in the equilibrium diagram.

If the balance is performed between the bottom and the top of the column,
this equation is transformed into:
F C0 Y2 Y1 = SmMAX X2 X1
(22.38)
Since sections 1 and 2 of the column correspond to the breakpoint and

saturation point, respectively, it should be complied that:

Breakpoint:
Saturation point:
845
X1 = 0
X2 = 1
Y1 = 0
Y2 = 1
Combination of Equations 22.37 and 22.38 yields that the operating line
(Equation 22.33) is a straight line with slope 1 and ordinate to the origin 0;
this means Y = X.
When performing a solute balance around a dz of the column, it is obtained
that:
F C0 Y = k F C0 Y Ye aS A dz
This equation allows calculation of the height of the exchange zone:
F A
zC =
k F aS
Y2
dY
Y Y
(22.39)
Y1
In this case, this equation has an analytical solution, since from the operating line (Y = X) and the definition of the separation factor (Equation 22.9),
a relationship between Ye and Y is obtained:
Ye =
Y
K 1Y +Y
(22.40)
Substitution in Equation 22.39 allows one to obtain the height of the

exchange zone by integration as:
zC =
Y
1 Y2
F A
K ln 2 ln
k F aS K 1
Y1
1 Y1
(22.41)
Since in the exchange zone it is complied that the equivalent fractions of

the fluid phase Y1 and Y2 correspond to the breakpoint and saturation point
(Y1 = 0.05 and Y2 = 0.95), then the height of the exchange zone can be
calculated using the following equation:
zC =
( F A) (K + 1) ln (19)
k a ( K 1)
F
(22.42)
Besides this method, the height of the exchange zone can also be calculated
using the equation of Wilke:
846

zC = b v0.51
(22.43)
where v is the linear velocity expressed in cm/s, and b is a parameter that

depends on the type of transfer. In case of an exchange of ions Ca2+ and Mg2+
by Na+ ions, the value of this constant is 37.4.
The height of the exchange zone can also be calculated by experimentation.
For this reason, different experiments are performed with different bed
heights zT, and the volume of fluid VT required to fill the column is determined; then, the height of the column zT is plotted against VT. Data are fitted
to a straight line, and the value of the ordinate to the origin is the height zC
of the exchange zone.
Problems
22.1
One of the causes of deterioration of clarified juices of fruits is nonenzymatic
browning due to the formation of melanoidins that can be eliminated from
the juice by adsorption on activated carbon. The degree of nonenzymatic
browning of a juice can be evaluated by measuring its absorbance at a
wavelength of 420 nm (A420). In an experimental series at the laboratory,
different amounts of activated carbon (particles of 1 mm of mean diameter)
are mixed with loads of 10 Brix juice, whose A420 is 0.646, until reaching
equilibrium. Data obtained are given in the following table:
A420
b
0.646
0
0.532
0.01
0.491
0.02
0.385
0.06
0.288
0.12
0.180
0.26
in which A420 is expressed as absorbance/kg of solution, while b is the kg of

carbon/kg of solution. Determine: (a) data of the equilibrium isotherm as a
table; (b) the number of stages required, operating under repeated single
contact, if it is desired to decrease the A420 of the juice down to a value of
0.200, using in each stage 0.025 kg of carbon per each kg of 10Brix juice;
and (c) the flow of carbon that should be fed to a countercurrent movingbed column with a juice flow of 1000 kg/h, if it operates with a carbon flow
that is double the minimum, and it is desired to obtain juice with an A420
value not higher than 0.2.
(a) The equilibrium data are obtained from the problem statement, since the
concentration of melanoidins in the liquid phase is given by the absorbance
at A420. A measure of the melanoidins adsorbed by the carbon is given by
the difference between the initial absorbance of the juice and the absorbance
that it has at a determined instant. For this reason, the melanoidin concentration in the liquid and solid phases is:

absorbance
C = A
kg juice
Liquid phase:
m=
Solid phase:
847
A0 A melanoidines adsorbed
kg carbon
b
Hence, the data of the equilibrium isotherm are:

absorbance
C
kg juice
0.532
0.491
0.385
0.288
0.180
melan. adsorb.
m
kg carbon
11.4
7.75
4.35
2.98
1.79
(b) When performing a solute balance for the first stage, in which it is
supposed that the carbon that enters has no solute, it is obtained that:
L
L
m1 = C1 + C0
S
S
This equation indicates that, when a straight line with slope (L/S) is
traced in the equilibrium diagram from the point with abscissa C0, the values
of C1 and m1 are obtained from the equilibrium curve.
The slope of this straight line can be easily obtained from the data in the
problem statement:
( )
L S = 1 0.025 = 40 kg juice kg carbon
Once C1 has been obtained, a straight line with the same slope as before
is drawn from this abscissa, which allows one to obtain the values of C2 and
m2 on the equilibrium curve (Fig. 22.P1a). The process is repeated until
exceeding the value of Cn = 0.2. Table 22.P1 presents the values obtained for
the outlet streams of each stage.
TABLE 22.P1
Concentrations in the Stages
Stage
absorbance
C
kg juice
melan. adsorb.
m
kg carbon
1
2
3
4
5
0.470
0.365
0.285
0.225
0.180
7.1
4.0
2.9
2.2
1.8
848
a)
m
()
10
L
S max
m1
5
- L = - 40
S
1
2
5
0
0
0.1
0.2
0.3
0.4
c1
0.5
0.6
0.7
b)
S
L
c2
m2
L
c1
S
m1
FIGURE 22.P1
(a) Graphical calculation of the stages and maximum slope; (b) movable column.
849
Since Cn = 0.2, five stages will be required.

(c) For the column that works with a moving bed, solute balance between
the top of the column and any section yields:
m = m2 +
L
C C2
S
It is assumed that the carbon entering the column is free from the solute
(m2 = 0) and that the concentration of the liquid stream that leaves the column
is C2 = 0.2. Therefore, substitution of data yields the following operation line:
m=
L
C 0.2
S
The maximum slope for this straight line is obtained for C = C1 in the
equilibrium curve. However, this is not possible since the straight line that
joins point 2 with the point at the equilibrium isotherm for C = C1 will cross
the curve. The value of (L/S)MAX is obtained by tracing a straight line tangent
to the equilibrium curve from point 2, in such way that its value is:
L
= 25.11 kg juice kg carbon

S MAX
Since the juice stream that circulates by the column is L = 1000 kg, the
minimum amount of carbon is SMIN = 39.82 kg carbon. Since the amount of
carbon required is double the minimum:
S = 2 SMIN = 79.64 kg carbon
22.2
An industry that processes navel oranges obtains juice that contains 110 ppm
of limonene that gives it a bitter taste. With the objective of eliminating the
bitter taste from the juice, a 100 kg/h juice stream is fed to a cylindrical
column (0.15 m2 of cross section) that contains a synthetic molecular sieve
that adsorbs limonene. The adsorbent solid has a density of 950 kg/m3 of
packing, with a volumetric transfer coefficient equal to 1.5 102 h1, and
maximum retention capacity of 10 mg of limonene per kg of adsorbent. The
density of the juice can be considered 1000 kg/m3. The adsorption isotherm
in the concentration range at which the column operates is linear and
expressed by the equation: m = 0.12 C, where C is the limonene content in
the juice in mg/kg, while m is the concentration in the solid expressed in
mg/kg of adsorbent. It can be assumed that the breakthrough curve is
symmetrical. Calculate: (a) the height of the exchange zone; and (b) if 25 min
are required for limonene in the juice stream to begin leaving the column,
calculate the height that the adsorbent bed should have.
850
S
2
C2
m2
Saturation
m + dm
C + dc
dz
Breakpoint
1
L
C1
m1
FIGURE 22.P2
Conditions of an exchange zone.
(a) The exchange zone behaves as a moving bed column with infinite height,
so the saturation conditions are given on the columns top, while breakpoint
conditions are on the bottom: m1 = 0 and C1 = 0. From the global balance of
solute, it is obtained that S = L C2/m2. If the balance is performed between
section 1 and any section: S = L C/m. Since the adsorption isotherm is linear
(m = K Ce), it is possible to obtain a relationship between the equilibrium
concentration and the composition of juice by combining the last equations:
Ce =
m2
C
K C2
The height of the exchange zone is obtained from the expression:

L A
zC =
K L aS
C2
C1
C
K C2
dC
L A
=
ln 2
C Ce K L aS KC2 m2
C1
851
From data in the statement:

C0 = 110 mg limonene/kg juice
C1 = 0.05 C0 = 5.5 mg limonene/kg juice
C2 = 0.95 C0 = 104.5 mg limonene/kg juice
m2 = m0 = 10 mg limonene/kg adsorbent
Therefore:
zC =
(0.12)(104.5) ln 0.95
)( ) (0.12)(104.5) (10) 0.05
100 kg h
1000 0.15 150
)(
ZC = 0.0646 m
(b) The volume of the exchange zone is Vc = zC A = 0.00969 m3. The amount
of limonene that enters the column with the juice stream is:
( )( )
w C0 = 100 110 = 1100 mg limonene h

The breakpoint is reached when limonene begins to be present in the
stream leaving the column, which occurs at 25 min (tR = 25 min). The amount
of limonene that entered during 25 min has been retained in the adsorbent
in the column. If V is the volume occupied by the adsorbent in the whole
column, the volume of saturated adsorbent is (V VC). Therefore, the following is complied at the breakpoint:
w C0 tR = V VC a m0 + VC a m0 i
Substituting data:
(100)(110)(25 60) = (V 0.00969)(950)(10) + (0.00969)(950)(10)(0.5)

Thus, the volume that the adsorbent occupies in the column is obtained:
V = 0.468 m 3
The height of the adsorbent is z = V/A = 3.12 m.
22.3
In a stage of a certain food process, 8000 kg/h of water with a magnesium
salts content of 40 meq/kg are treated in an ionic exchange cylindrical
column. The exchange capacity of the resin is 15 eq/kg, with a separation
852
factor of 50 and an apparent density of 550 kg/m3. The column has a 30 cm

diameter and contains 110 kg of resin. From previous experiments, it has
been obtained that the mass transfer coefficient is KL aS = 2.5 106 l/(h.m3).
If it is a fixed-bed column and the breakthrough curve is symmetric, determine: (a) height of the exchange zone; (b) the breakpoint and saturation
times; and (c) the magnesium salts content after 75 min of operation.
If it is supposed that the density of the liquid stream is 1000 kg/m3, then
the volumetric flow rate is q = 8 m3/h.
The mass transfer coefficient is expressed in proper units to facilitate later
calculations:
K L aS = 2.5 106 l h m 3 = 2500 h 1

(a) The height of the exchange zone is calculated by Equation 22.42:
zC =
q A K+1
ln 19
K L aS K 1
The volume of the exchange zone can be obtained from the previous
equation:
VC = zC A =
( 8)
50 + 1
3
ln 19 = 0.00981 m
2500 50 1
which corresponds to an exchange zone height equal to zC = 0.139 m.

The volume occupied by the resin is the total of the column:
VRESIN =
25 kg
= 0.04546 m 3
550 kg m 3
and a total column height equal to z = 0.643 m.

(b) The breakpoint time is produced when salts begin to exit with the liquid
stream leaving the column. At the saturation volume, no more ions can be
exchanged. Also, the exchange zone will have half of its exchange capacity.
Saturation volume:
VS = V VC = 0.03565 m 3
The amount of ions that entered during the breakpoint time have been
retained in the volume of saturated resin and in the exchange zone, complying with the following:
w C0 tR = VS a EM + VC a EM i 320 eq Mg2+ h tR
)( )( )
)( )( )( )
= 0.03565 550 15 eq Mg2+ + 0.00981 550 15 0.5 eq Mg2+

853
Thus, the breakpoint time is:

tR = 1.046 h = 63 minutes
At saturation time, the resin of the column would be saturated; also, it has
passed the exchange zone:
w C0 tR = VRESIN a EM + VC a EM i 320 eq Mg2+ h tS
)( )( )
)( )( )( )
= 0.04546 550 15 eqMg2+ + 0.00981 550 15 0.5 eqMg2+

Hence, the saturation time is:
tS = 1.298 h = 78 minutes
(c) Concentration after 75 min in the water stream leaving the column is
obtained by linear interpolation between the breakpoint and saturation
times:
t t
C = C0 1 S
= 32 meq kg
tS tR

Cap 22 Absorption and Ionic Exchange

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TX69299 ch01 frame.

book Page 823 Wednesday, September 4, 2002 2:13 PM

The solute retained in adsorption processes is called adsorbate, whereas the

Ionic exchange consists of replacing ions of a solution with others contained

TX69299 ch01 frame.book Page 824 Wednesday, September 4, 2002 2:13 PM

Unit Operations in Food Engineering

ered a chemical adsorption, where ion exchange occurs at defined points of

22.2 Equilibrium Process

2003 by CRC Press LLC

TX69299 ch01 frame.book Page 825 Wednesday, September 4, 2002 2:13 PM

Adsorption and Ionic Exchange

The theoretical obtainment of the adsorption isotherms can be based on

This equation is called isotherm of Langmuir, and experimental data of

2003 by CRC Press LLC

TX69299 ch01 frame.book Page 826 Wednesday, September 4, 2002 2:13 PM

Unit Operations in Food Engineering

When the number of layers n = 1, it is obtained that:

which coincides with the isotherm of Langmuir.

For low values of x, the last equation is transformed as:

2003 by CRC Press LLC

TX69299 ch01 frame.book Page 827 Wednesday, September 4, 2002 2:13 PM

Adsorption and Ionic Exchange

Ionic Exchange Equilibrium

The disappearing rate of the cation An+ is:

When equilibrium is reached, the disappearing rate of A is null, so the

Substitution in the last equation allows expression of the disappearing rate

2003 by CRC Press LLC

TX69299 ch01 frame.book Page 828 Wednesday, September 4, 2002 2:13 PM

Unit Operations in Food Engineering

the equilibrium constant is expressed as:

This equilibrium constant is called the separation factor.

22.3 Process Kinetics

In every adsorption process, three solute transfer stages can be considered:

where kF is the mass transfer coefficient in the external phase.

where CS is the concentration of solute in the solid and De is the

2003 by CRC Press LLC

TX69299 ch01 frame.book Page 829 Wednesday, September 4, 2002 2:13 PM

Adsorption and Ionic Exchange

Ionic Exchange Kinetics

As they occur in physical adsorption processes, different stages of mass

where the superscript i indicates interface concentrations, and it is complied

22.4 Operation by Stages

2003 by CRC Press LLC

TX69299 ch01 frame.book Page 830 Wednesday, September 4, 2002 2:13 PM

Unit Operations in Food Engineering

2003 by CRC Press LLC

TX69299 ch01 frame.book Page 831 Wednesday, September 4, 2002 2:13 PM

Adsorption and Ionic Exchange

where the subscript E means inlet and S means outlet. Rearranging:

Repeated Simple Contact

Rearranging the equation:

2003 by CRC Press LLC

TX69299 ch01 frame.book Page 832 Wednesday, September 4, 2002 2:13 PM

Unit Operations in Food Engineering

If it is desired to determine the concentrations of the streams that leave

Countercurrent Multiple Contact

2003 by CRC Press LLC

TX69299 ch01 frame.book Page 833 Wednesday, September 4, 2002 2:13 PM

Adsorption and Ionic Exchange

2003 by CRC Press LLC

TX69299 ch01 frame.book Page 834 Wednesday, September 4, 2002 2:13 PM

Unit Operations in Food Engineering

22.5 Movable-Bed Columns

2003 by CRC Press LLC