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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
Ionic Exchange
824
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
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)
(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
(22.7)
)(
827
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
( r ) = k C
A
CR B k2 CB CR A
k1 CBCR A
=
k2 CA CR B
(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
K=
(1 Y ) X
Y (1 X )
(22.9)
Adsorption Kinetics
N = k F C Ci
(22.10)
CS
r
(22.11)
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
( r) = k A CA CAi = k B CBi CB
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
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
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
F
F
mi = Ci + mE + Ci 1
S
S
(22.14)
832
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.
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
(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.
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
N = k F C Ce
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.
C0
C-dC
A
dz
FIGURE 22.7
Fixed-bed column.
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.
837
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)
vt
V
=
1
1
dm
dm
P
A1 +
1 + P dC
dC
(22.18)
22.6.2
(22.19)
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
) (
k F aS
dm
=
C Ce
dt
1 p
(22.20)
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)
22.6.3
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
839
b)
F
C
C0
ZC
ZC
F
C0
FIGURE 22.8
Exchange zone and concentration profile of the fluid stream in this zone.
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)
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)
MC =
(C C) dV
(22.30)
VR
(M )
C MAX
= C0 VT VR = C0 VC
(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)
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
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
m
FC
=
Ka S Ka
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
( )
F A
ln 19
K k F aS
(22.36)
22.6.3.2
) (
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
F C0 Y Y1 = SmMAX X X1
(22.37)
F C0 Y2 Y1 = SmMAX X2 X1
(22.38)
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)
zC =
Y
1 Y2
F A
K ln 2 ln
k F aS K 1
Y1
1 Y1
(22.41)
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
(22.43)
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
kg juice
Liquid phase:
m=
Solid phase:
847
A0 A melanoidines adsorbed
kg carbon
b
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:
( )
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
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.
2003 by CRC Press LLC
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
C2
C1
C
K C2
dC
L A
=
ln 2
C Ce K L aS KC2 m2
C1
851
(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 tR = V VC a m0 + VC a m0 i
Substituting data:
852
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
25 kg
= 0.04546 m 3
550 kg m 3
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
)( )( )
)( )( )( )
853
)( )( )
)( )( )( )
t t
C = C0 1 S
= 32 meq kg
tS tR