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Adsorption Alvin R.

Caparanga

PIChE Handbook Mapua Institute of Technology


J9 ADSORPTION

J9.1 Introduction

Sorption is a general term for any process in which a component (or components) of one
phase, usually a gas or a liquid mixture, transfers to another phase, where the migrating
component is accumulated. This is particular for situations in which the second phase is solid.
Both adsorption and absorption are sorption processes.

In adsorption, a component or components (atoms, molecules or ions) are extracted from the
fluid phase (gas or liquid mixture) and are concentrated on the surface of the solid phase. A
component, therefore, can be separated from a mixture if it selectively adsorbs onto a solid
surface. For most applications, only one component is usually separated from the fluid phase -
such adsorption can occur in either a gas-solid or liquid-solid system. The component that
concentrates (adsorbed) on the surface of the solid is called the adsorbate. The solid, which is
the separating agent, is called the adsorbent.

Most adsorbents are porous materials. Common examples are silica gel, alumina, zeolite,
charcoal, activated carbon, synthetic resins and some types of adsorbing clay minerals. In so
many cases of adsorption on these materials, the adsorbate is held strongly enough on the
walls of the pores or at specific sites inside the particle to allow (nearly) complete removal of
that component from the fluid. Because these materials are selective to some specific atoms,
ions or molecules, there is usually very little adsorption of other components.

J9.2 Driving Forces in Adsorption

A. Hydrophilic and hydrophobic character in an aqueous solution

B. Specific affinity of the solute for the solid adsorbent via van der Waals forces attraction or
chemical reaction

J9.3 Types of Adsorption

.A. Physical adsorption

Characterized by a relatively low energy of adsorption as a result of van der Waals forces of
attraction, this adsorption type is predominant at low temperatures. The adsorbate is not fixed
to a specific site; it is free to undergo translational movement within the interface.

B. Chemical adsorption

A
Adsorption Alvin R. Caparanga

PIChE Handbook Mapua Institute of Technology

Also referred to as chemisorption or activated adsorption, chemical adsorption, having high


energy of adsorption, is favored at higher temperature. Equilibrium is attained faster in
chemisorption.

C. Exchange adsorption

With the charge of the ions being the determining factor, ions of one component concentrate
on a surface as a result of electrostatic attraction
The adsorbate reacts with the adsorbent. Chemisorption, having a high energy of adsorption,
normally proceed rapidly at elevated temperatures.

J9.4 Mechanism of Adsorption

The mechanism of adsorption of solute from solution by porous adsorbents can be


summarized as follows:

1. Transport of adsorbate from the bulk phase through the surface film to the exterior of the
adsorbent (rate-determining step for continuous-flow systems)
2. Sorption by the porous adsorbent
3. Adsorption of the solute on the interior surfaces bounding the pore and capillary spaces of
the adsorbent (rate-determining step for agitated batch systems)

J9.5 Factors That Influence Adsorption

A. Surface area

The extent of adsorption is proportional to surface area (portion of the total area that is
available for adsorption).

B. Nature of adsorbate

1. Adsorption of solute is inversely proportional to its solubility in the solvent.

Lundelius’ Rule: The greater the solubility, the stronger is the solute-solvent bond and the
smaller is the extent of adsorption.

Traube’s Rule: In general, the solubility of any organic compound in water decreases with
increasing chain length, because the compound becomes more hydrocarbon-like as the
number of carbon atoms increases.

2. Molecular sizes

B
Adsorption Alvin R. Caparanga

PIChE Handbook Mapua Institute of Technology


Adsorption generally proceeds at faster rate if adsorbate molecules are small and the process
is controlled by intraparticle transport. This argument applies to a given class of compound.

3. Ionic charge

Adsorption is at its minimum for the charged species and at maximum for the neutral species
as long as the compounds are structurally simple. The effect of ionisation becomes less
important as the compounds become more complex.

4. pH

Hydrogen and hydroxide ions are adsorbed quite strongly; therefore, the adsorption of other
ions is influenced by the pH of the mixture.

5. Temperature

Adsorption, particularly physical adsorption, is normally exothermic; thus, the extent of


adsorption generally decreases with increasing temperature.

6. Presence of other solutes

Other solutes that may be present in the solution may compete with the desired solute for the
available surface area. Therefore, relative adsorptive affinities and relative concentrations of
the solutes are a factor.

7. Nature of the Adsorbent

An adsorbent’s performance is generally better if its specific surface area available for
adsorption is large and the general physico-chemical characteristics of the solid adsorbent
complement the corresponding properties of the adsorbate.

J9.6 Adsorption Equilibria and Isotherms

At equilibrium, there is a defined distribution of solute between the fluid and solid surface.
The distribution ratio may be a function of the concentration of the solute, the concentration
and nature of competing solutes, etc. The dynamic phase equilibrium that is established for
the distribution of solute between the fluid and the solid surface is somewhat similar to the
equilibrium solubility of gas in a liquid. These equilibrium relations are called isotherms.

Some of the common isotherms are summarized in Table J9-1.

Table J9-1 Common adsorption isotherms


Name of isotherm Equation Comment
Not common, but can be

C
Adsorption Alvin R. Caparanga

PIChE Handbook Mapua Institute of Technology


Linear q = Kc (J9-1) applied to approximate
data for dilute systems
Empirical; Can be used to
Freundlich q = Kc n (J9-2) approximate data for
many physical adsorption
systems, particularly
liquids
qoc
Langmuir q= (J9-3) Has a theoretical basis
K+c

When n = 1 in equation J9-2, the equation is reduced the Henry’s-law type equation (equation
J9-1).

Favorable isotherms permit higher loading (amount of adsorbate per unit mass of adsorbent)
at lower solution concentrations. On the other hand, isotherms, which start out flat are
unfavourable.; they only work well at high concentrations of solute.

The Langmuir isotherm (equation J9-3) was derived considering the following assumptions:
(a) The energies of adsorption on the surface are uniform.
(b) Adsorption is reversible and maximum adsorption, which occurs at equilibrium,
corresponds saturated monolayer of solute molecules on the adsorbent surface
such that the energy of adsorption is constant.
(c) There is no transmigration of adsorbate in the plane of the surface.

Another important equilibrium relation is the Brunauer-Emmet-Teller (BET) isotherm, which


has 5 forms (or types). This isotherm is based on the following assumptions:
(a) The energies of adsorption on the surface are uniform.
(b) A number of layers of adsorbate molecules form at the surface, where each layer is
described by the Langmuir isotherm.
(c) A given layer does not need to be completely formed before subsequent layers are
formed such that the equilibrium condition will involve several types of surfaces.

Given the q (solute loading on the adsorbent) versus c (concentration of solute in the fluid)
data at equilibrium, the temperature-dependent constants K and n of equation J9-2 can be
evaluated graphically from a ln q vs ln c plot, with slope equal to n and intercept equal to ln
K. On the other hand, the constants qo and K can be evaluated from equation J9-3 by plotting
1/q against 1/c, with slope as K/qo and intercept as 1/qo.

The solute loading on the solid adsorbent is usually expressed as mass, or moles, or volume of
adsorbate per unit mass or per unit BET surface area of adsorbent. On the other hand
concentration of solute in the fluid is usually in terms of partial pressure if the fluid is a gas; in
the case liquid, the concentration may be in terms of moles, or mass, or volume per unit
volume of the mixture.

D
Adsorption Alvin R. Caparanga

PIChE Handbook Mapua Institute of Technology


J9.7 Modes of Operation

A. Batch or Single-Stage Adsorption

Usually done with fresh (solute-free) adsorbent, batch adsorption is often used in small-scale
operations. Similar to other separation processes, an equilibrium relation (appropriate
isotherm) is required in addition to material balance (the equation of the operating line if to be
solved graphically). Based on Figure J9-1, the material (solute) balance, which represents the
operating line, for single-stage batch adsorption process for a binary mixture (liquid) is:
_
S(c _ c*) = M (q * q ) (J9-4)
o o

The material balance equation, J9-4, also applies to (equilibrium) single-stage continuous
adsorption.

Adsorbent
M kg adsorbent
Feed solution qo kg adsorbate/kg adsorbent
S kg solution
co kg solute/kg solution

Lean solution
S kg solution
Spent adsorbent c* kg solute/kg solution
M kg adsorbent
q* kg adsorbate/kg adsorbent

Figure J9-1 Batch or single-stage adsorption

Solving simultaneously equation J9-4 and the applicable isotherm equation, one can
determine the equilibrium values of q and c. Since in most cases, either the Langmuir or
Freundlich isotherm applies, either being non-linear, it is suggested that q and c be solved
graphically, with the intersection of the curves of the isotherm and material balance (equation
J9-4) as the coordinates of equilibrium values q* and c*. From these values the extent of
separation can be determined.

Operating line
q
Equilibrium curve
(isotherm)
q*
E
Adsorption Alvin R. Caparanga

PIChE Handbook Mapua Institute of Technology

c* c

Figure J9-2 Graphical solution to batch (single-stage) adsorption

Over small concentration ranges in dilute solution, however, the Freundlich isotherm (J9-2)
usually applies. If process starts with an adsorbent initially free of adsorbate (q0 = 0), then

c 0 _ c* M
= (J9-5)
K (c * ) n S

At different values of n, the solutions of J9-5 are given in Figure J9-3.

operating lines (slope: -M/S)

c0 n<1
equilibrium curves / isotherms
n =1

c* n>1

q
Figure J9-3 Single-stage adsorption at different values of n in Freundlich isotherm
B. Two-Stage Cross-Current Adsorption

In practice and for economic reasons, split-feed treatment is normally used; it uses smaller
batches of adsorbent rather than one large batch. However, two stages are generally optimal;
otherwise, additional filtration auxiliaries would eliminate any economic gain.

M1 M2
qo qo

Feed solution
S kg solution
co kg solute/kg solution c1 c2
Stage 1 Stage 2
F
Adsorption Alvin R. Caparanga

PIChE Handbook Mapua Institute of Technology

M2 M2
q1 q2

Figure 9-4 Two-stage cross-current adsorption

On the assumption that the amount of solution is practically constant (S ≈ S1 ≈ S2) like in
usual cases, the material balances are as follows.
_ _
For stage 1: S(c 0 c 1 ) = M 1 (q 1 q0 ) (J9-6)
_ _
For stage 2: S(c1 c 2 ) = M 2 (q 2 q0 ) (J9-7)

If fresh adsorbent is used in each stage (q0 = 0) and equilibrium is of the Freundlich type, then
equations J9-6 and J9-7, respectively, become

M 1 c o _ c1
= (J9-8)
S Kc1n
M 2 c1 _ c 2
= (J9-9)
S Kc n2

The total amount of adsorbent used is

M 1 + M 2 c o _ c1 c1 _ c 2
= + (J9-10)
S Kc1n Kcn2

At specified extent of separation or c2, the minimum total adsorbent can be obtained by setting
d M1 + M 2
the derivative to zero. Considering that K, n, c0 and c2 are constants, then
dc 1 S
equation J9-10 becomes

c1n _
c0
n =1_ n (J9-11)
c n2 c1

from which c1 at minimum total adsorbent can be evaluated. This c1 is then used to evaluate
the minimum total adsorbent using equation J9-10.

C. Multistage Countercurrent Adsorption

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Adsorption Alvin R. Caparanga

PIChE Handbook Mapua Institute of Technology

S S S S
S c1 c2 cN-1 cN
c0

Stage 1 Stage 2 Stage N


MN+1
q1 q2 q3 qN qN+1

Figure J9-5 Multistage countercurrent adsorption

1. Determination of Number of Stages Using Kremser Equation

The Kremser-type equation as used in other stage processes (gas absorption, extraction and
distillation) may also be applied to evaluate the number of equilibrium stages in
countercurrent adsorption provided that the following conditions are satisfied: (a) equilibrium
relation is of the Freundlich-type with n = 1 (or linear isotherm, equation J9-1); (b) flow rate
of solution is practically constant (S = S0 = S1 = S2 = … = SN); and, (c) adsorbent flow rate is
constant (M = M1 = M2 = … = MN+1).

Balance around any stage n:

cn-1 cn

Stage n

qn qn+1

M (qn – qn+1) = S (cn-1 – cn) (J9-12)

Substituting equation J9-1 into the preceding equation and rearranging yields:

cn+1 = cn – Acn-1 + Acn (J9-13)

S
where A = , a quantity analogous to absorption factor; hence, it will also be referred to
MK
as ‘absorption’ factor for adsorption..

For stage 1, using n = 1, equation J9-13 becomes

c2 = c1 – Ac0 + Ac1 = c1 (1 + A) – Ac0 (J9-14)

For stage 2, using n = 2, and eliminating c 2 from the resulting equation, equation J9-13
becomes

c3 = c1 (1 + A + A2) – c0 (A + A2) (J9-15)

H
Adsorption Alvin R. Caparanga

PIChE Handbook Mapua Institute of Technology

These equations can be generalized for the nth stage to yield

cn+1 = c1 (1 + A + A2 + … + An) – c0 (A + A2 + … + An) (J9-16a)


or
cn+1 = c1 + (c1 – c0) ( A + A2 + … + An) (J9-16b)

The terms in the parenthesis represent a sum of a geometric series:


A ( 1_ A n )
2 3 n
A + A + A + ... + A = (J9-17)
1_ A

Therefore, for stage N, equation J9-16 becomes


_
A(1_ A N 1 )
( _
c N = c1 + c1 c 0 ) (J9-18)
1_ A

This is a form of the Kremser equation for multistage countercurrent adsorption, which is
applicable as long as the previously mentioned conditions are satisfied.

Normally, q1 is known; therefore, the corresponding value of c1 can be estimated from


equation J9-1. Given the number of stages, the exit concentration of the solution from the last
stage can be estimated. Also, if desired extent of separation or c N is known, the number of
stages required to effect the separation can be calculated.

2. Determination of Number of Stages by Graphical Method

In case when the isotherm that describes the equilibrium is not linear, a graphical method
similar to McCabe-Thiele is applicable. Equilibrium isotherm can be that of Freundlich (with
the parameter n ≠ 1) or Langmuir type. Considering figure J9-5 to represent a multistage
countercurrent system and the assumptions b and c in the preceding section, the following
figure (J9-10) illustrates the procedure for determining the number of stages by graphical
method:

c0

1
c1

I
Adsorption Alvin R. Caparanga

PIChE Handbook Mapua Institute of Technology

N
cN

qN+1 q2 q1

Figure J9-6 Graphical solution for multistage countercurrent adsorption

D. Fixed-Bed Adsorption Columns

The Freundlich and Langmuir isotherms are applicable to batch adsorption systems where
sufficient time is provided to allow equilibrium between solute in the solution and the
adsorbate to occur. Many applications use a fixed-bed approach where the fluid stream flows
through a stationary mass of adsorbent. During the flow through the fixed-bed of adsorbent,
the solute components of the solution come into contact with active surface sites and are
retained on the surface of adsorbing media.

1. Design Parameters

In the design of these fixed bed adsorbers two significant parameters – minimum contact time
and the life of the bed – are required.

Minimum contact time

The minimum contact time is determined through a series of kinetic tests in which a known
mass of adsorbent is exposed to a solution of known solute concentration for specific amounts
of time. At the end of each time increment, the concentration of the solute in the solution is
measured; these values are plotted against time. The time at which the curve begins to flatten
is the minimum contact time required to attain pseudo-equilibrium. Separation or removal of
solute from the solution may still continue past this minimum time; however, longer contact
times in general are not economically efficient because the size of the fixed-bed adsorber will
need to be much greater for minimal additional removal.

Service life of the bed

The service life of the bed can be determined using the bed-depth-service-time (BDST)
model. The model is based on the Bohart and Adams quasi-chemical rate law, using the
following assumptions: (a) equilibrium is not instantaneous; and, (b) the rate of sorption is
proportional to the fraction of sorption capacity still remaining on the adsorbent. The
linearized BDST equation is

N0 1 C0 _ Cb
tb = D_ ln (J9-19)
1000 ενC 0 kC 0 Cb

J
Adsorption Alvin R. Caparanga

PIChE Handbook Mapua Institute of Technology


where tb = time until breakthrough (min)
C0 = initial concentration of solute (mg/L)
Cb = breakthrough concentration of solute (mg/L)
ν = fluid velocity or loading rate (m/min)
ε = porosity of the bed
k = quasi-chemical rate constant from Bohart and Adams theory (L/mg-sec)
N0 = capacity of the adsorbent for each solute in a multi-component solution
(mg/m3 of adsorbent bed)
D = depth of the adsorbent bed

2. Breakthrough Concentration Curve

The amount of material adsorbed within the fixed bed depends time of contact and position.
For example: as fluid enters the bed, it comes in contact with the first few layers of adsorbent
to a certain position. Instantaneously, solute adsorbs, filling up some of the available surfaces
or sites. After some time, the adsorbent near the entrance is saturated and the fluid penetrates
further into the bed before all solute is removed. The active region, therefore, shifts through
the bed progressively (see Figure J9-7).

Initially, the fluid emerging from the exit of the bed will have no solute remaining and this
will continue at least until the bulk of the bed becomes saturated. At the point when the bed is
almost saturated with the solute, little amount of solute starts to emerge with the fluid exiting.
When the concentration of the fluid leaving the bed spikes as unadsorbed solute, a break
point occurs. At this point the bed is already ineffective. See Figure J9-8. The corresponding
concentration at the break point is called the breakpoint or breakthrough concentration (cb).
This concentration corresponds to the maximum amount of acceptable solute lost and is
normally set at values ranging from 0.01 to 0.05co.

Figure J9-7 Concentration profiles at various positions and times in a fixed bed

K
Adsorption Alvin R. Caparanga

PIChE Handbook Mapua Institute of Technology

Mass transfer
zone

Figure J9-8a Breakthrough


concentration curve in the solution at the outlet of
bed

Mass transfer
zone
1
C/Co

0.5

break point, cb

time, t

L
Adsorption Alvin R. Caparanga

PIChE Handbook Mapua Institute of Technology


Figure J9-8b Breakthrough concentration curve in the solution at the outlet of bed

As the

G.4 Fixed-Bed Adsorption Columns


G.4.1 Breakthrough Concentration Curve
G.4.2 Capacity and Scale-Up Design

J9.8 Regeneration and Adsorption Cycles

Adsorption cycles are classified according to the method of regeneration. Most systems use a
combination of the following:

A. Temperature swing, which is used to regenerate bed by raising the vapor pressure of
contaminant by preheating sweep gas

B. Pressure swing, which vaporizes contaminant by pressure reduction

C. Stripping, which sets up a contaminant lean (low partial pressure) condition that results to
its diffusion from solid to sweep gas

D. Removal of contaminant to a sweep liquid

J9.9 Applications

Table J9-2 lists some of the applications of adsorption as a separation process.

Table J9-2 Some applications of adsorption


Liquid-Solid Systems Gas-Solid Systems
• Removal of organic components • Drying of gases by adsorbing the
from drinking water or aqueous water on silica gel or alumina
waste • Separation of oxygen and nitrogen
• Removal of colored impurities on molecular sieves
from sugar solution and vegetable • Removal of CO2 from natural gas
oils • Removal of H2S, CS2 and other
• Removal of water from organic odorous compounds from air
liquids circulating in ventilation systems
• Recovery of reaction products that • Separation of normal paraffins

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Adsorption Alvin R. Caparanga

PIChE Handbook Mapua Institute of Technology


are not easily separated by from branched paraffins or
distillation or crystallization aromatics
• Removal of sulfur compounds
from organic solutions
• Removal of heavy metals from
wastewater using biosorbents