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ADSORPTION AND IONIC

EXCHANGE
BY:
ALVIS REY C. AYSON
REYMARK D. VILLAR
MA.ARILELA MAE V. RIMBAO
Adsorption and Ionic
Exchange
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 solid’s
surface or to a reaction with the solid.
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.
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 considered
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.
Equilibrium Process
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
solute–adsorbent systems.
FIGURE 22.1
Types of adsorption isotherms.
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:
The adsorption rate of A is expressed by the equation:

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:

The adsorption equilibrium constant can be defined as:

Obtaining:
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:

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):

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, m1A 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:
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:
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 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:
If the equivalent fractions of A in the liquid and resin phases are defined as:
Process Kinetics
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 fluid–solid interphase in which the concentration is Ci. The
mass flux is given by the equation:

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
3. Adsorption stage: For the simpler case, expressed before, it
can be stated that:

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.
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 resin’s 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 A is
bound to the resin while such a way that B passes to the fluid phase.
4. Diffusion of ion B through the pores of the resin until reaching the
resin’s 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:
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. The most common ways
of operation are single stage or contact and multistage,
which can be repeated single contact or countercurrent
multiple stage.
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 slight variation between the
inlet and outlet, so they are considered constant.
which, in the m–C 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 m–C 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).
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).
 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 m–C 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.
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 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.
In the m–C 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).
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.

where v is the fluid’s circulation linear velocity, A is the transversal


section of the column, 𝜀 is the porosity of the solid in the column, and aS
is the specific surface of the solid bed, while N is the flux of the
transferred solute, its value being:
FIGURE 22.6
Moving-bed column.
In this equation, kF is the mass transfer constant and Ci is the
concentration of the solute at the fluid–solid 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:

Generally, the integral does not have an analytical solution and should be
solved by numerical or graphical methods.