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- Adsorption
- Adsorption
- Adsorption
- Adsorption
- Sample Problem #3
- Langmuir Adsorption Isotherm
- Adsorption Engineering, Suzuki (1990)
- Adsorption
- Adsorption Isotherm Of Acetic Acid Solutions On Activated Carbon
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- 5. Adsorption Column Design
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- Ruthven-Adsorption
- Adsorption — from theory to practice
- Solid-Liquid Extraction (Leaching)
- Sample Problem #6
- Adsorption
- Rr312301 Mass Transfer and Separation

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Caparanga

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.

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

chemical reaction

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

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.

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)

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

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

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 generally decreases with increasing temperature.

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.

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.

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.

Name of isotherm Equation Comment

Not common, but can be

C

Adsorption Alvin R. Caparanga

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.

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

J9.7 Modes of Operation

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

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

c* c

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

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

M2 M2

q1 q2

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

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.

G

Adsorption Alvin R. Caparanga

S S S S

S c1 c2 cN-1 cN

c0

MN+1

q1 q2 q3 qN qN+1

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).

cn-1 cn

Stage n

qn qn+1

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

S

where A = , a quantity analogous to absorption factor; hence, it will also be referred to

MK

as ‘absorption’ factor for adsorption..

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

becomes

H

Adsorption Alvin R. Caparanga

or

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

A ( 1_ A n )

2 3 n

A + A + A + ... + A = (J9-17)

1_ A

_

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.

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.

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

N

cN

qN+1 q2 q1

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.

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.

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

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

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

Mass transfer

zone

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

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

As the

G.4.1 Breakthrough Concentration Curve

G.4.2 Capacity and Scale-Up Design

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

C. Stripping, which sets up a contaminant lean (low partial pressure) condition that results to

its diffusion from solid to sweep gas

J9.9 Applications

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

M

Adsorption Alvin R. Caparanga

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

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