ChE 3211: Mass Transfer II

Adsorption

by
Rashidunnby Ratul
Department of Chemical Engineering, KUET
Reference Books 2

 Transport Processes and Separation Process by Christie Geankoplis 3rd

Edition
What is Adsorption? 3

 Adsorption is the adhesion of atoms, ions or molecules from a gas, liquid or

dissolved solid to a surface.

 This process creates a film of the adsorbate on the surface of the adsorbent.

 Adsorption is very different from distillation, absorption, and extraction. Two phases
in contact are solid/fluid.

 Molecules distribute themselves between two phases by diffusing from the bulk of
the fluid to the surface of the solid, i.e. walls of the pores and inside the particle and
by getting adsorbed

 Unsteady process
Adsorption Mechanism 4

Solute  adsorbate
Solid  adsorbent
Commercial Adsorption Process 5
 In commercial adsorption processes, one or more
components of a gas or liquid stream are adsorbed on
the surface of a solid adsorbent and a separation is
accomplished.

 In this processes, the adsorbent is usually in the form

of small particles in a fixed bed.

 The fluid is passed through the bed and the solid

particles adsorb components from the fluid.

 When the bed is almost saturated, the flow in this bed

is stopped and the bed is regenerated thermally or by
other methods so that desorption occurs. The adsorbed
material (adsorbate) is thereby recovered and the solid
adsorbent is ready for another cycle of adsorption.
Adsorption is an Exothermic Process 6

 ΔH of adsorption is always negative.

 A+S → A-S
 Spontaneous process → ΔG<0
 When an adsorbate is adsorbed on a solid surface, its movement is restricted leading
to a decrease in the entropy of the adsorbate → ΔS<0

 ΔG = ΔH - TΔS
→ ΔH = ΔG + TΔS <0
 Hence, adsorption is always exothermic.

 What is the effect of temperature?

→ Usually, as temperature increases the amount adsorbed decreases
Adsorption vs Absorption 7
Adsorption vs Absorption(cont’d) 8
Types of Adsorption 9

 Physical adsorption: Atoms of solid surface have a residue of molecular force

called van der Waals forces. This kind of adsorption can be easily reversed

 Chemical adsorption: Chemical interaction occurs between the adsorbate and

adsorbent, i.e. exchange of ions, electrons, radicals etc. Regeneration may be a
problem

 Most commercial adsorbents rely on physical adsorption; while catalysis relies on

chemisorption.
Comparison 10
Advantages and Disadvantages of Adsorption 11

 Separation of components having similar volatilities. Example: separation of n

and iso paraffin
 Capability to remove gaseous and vapor contaminants from the process
stream to extremely low levels

 Limited capacity: useful for dilute solutions

 Solids are difficult to handle
 Property varies
 Regeneration can be energy intensive
Applications of Adsorption 12

 Water adsorption: Adsorption of water is of great importance in many fields

including but not limited to chemical engineering, materials science, and catalysis. It
is also called surface hydration. Surface hydration is important in understanding
interface properties, chemical reaction pathways, and catalytic performance in a wide
range of chemical systems.
 Polymer adsorption: Adsorption on polymers is useful in many ways such as in the
development of non-stick coating and biomedical devices etc.
 Gas masks: Gas masks are used in coal mines to adsorb poisonous gases. They
are based on the adsorption principle and work by purifying the air for breathing.
 Silica gels: Silica gels are used to adsorb moisture and thus, reduce humidity. They
are commonly put with newly made products, especially shoes, handbags,
pharmaceutical drugs etc.
 Separation of noble gases: Noble gases can be separated using charcoal as an
adsorbent
Applications of Adsorption (cont’d) 13

 Adsorption chillers: Adsorption chillers combine adsorbents with refrigerants and

use heat to provide a cooling effect.
 Adsorption in viruses: Getting adsorbed on a bacteria (as a bacteriophage) is the
first step in the viral life cycle.
 Chromatographic analysis: Chromatography is based on the adsorption process.
The running solvent (mobile phase) when run through a stationary phase, it desorbs
the adsorbed mixture substances and the separation (purpose of chromatography)
occurs. For example, paper chromatography, thin layer chromatography (TLC), etc.
 Purification of water: When alum stone is added to water, impurities get adsorbed
on the alum surface and the water gets purified.
 Ion exchange method: The ion exchange method is used to remove the hardness
of water. During ion exchange, the calcium and magnesium ions are adsorbed on the
surface of ion exchange resins, thus purifying water.
Selection of Adsorbents 14

 Requires 3 important features to be effective:

1. Must selectively concentrate one or more components from a fluid. This can be done
in one of three ways:
(i) Selective binding of one or more components onto the surface.
(ii) Selective geometric exclusion of certain components (molecular sieving).
(iii) Selective differences in intra-particle diffusion rates of molecular components.

2. Must show reversibility- so the adsorbate can be recovered and the adsorbent
reused.

3. Should have as high as possible a delta loading the change in weight of adsorbate
per unit weight of adsorbent between adsorbing and desorbing steps.
Types of Adsorbents 15
 Activated Carbon:
✓ Microcrystalline material made by thermal decomposition of wood, vegetable shells,
coal, etc.
✓ Surface areas from 300 - 2500 m2/g.
✓ Average pore diameter of 10 to 60 Å.
✓ Organics are generally adsorbed by activated carbon.

 Molecular Sieve Zeolites:

✓ Porous crystalline aluminosilicates, forming an open crystal lattice containing
precisely uniform pores.
✓ Used for drying, separation of hydrocarbons, mixtures, etc.

 Silica Gel:
✓ Made by acid treatment of sodium silicate solution and then dried.
✓ Surface area of 600 - 800 m2/g.
✓ Average pore diameters of 20 - 50 Å.
✓ To dehydrate gases and liquids, and to fractionate hydrocarbons.
Types of Adsorbents (cont’d) 16

 Activated Alumina:
✓ To prepare this material, hydrated aluminium oxide is activated by heating to dry off
the water.
✓ It is used mainly to dry gases and liquids.
✓ Surface areas 200 - 500 m2/g; Average pore diameters of 20 - 140 Å.

 Synthetic Polymers or Resins:

✓ Made by polymerizing two major types of monomers. Those made from aromatics
such as styrene and divinylbenzene are used to adsorb nonpolar organics from aqueous
solutions.
✓ Those made from acrylic esters are usable with polar solutes in more aqueous
solutions.
Adsorbents Market Size 17
Adsorption Equilibrium 18

 Adsorption equilibrium is the state in which the rate of adsorption of molecules

onto a surface equals the rate of desorption from that surface. At this point, the
concentration of adsorbate on the adsorbent remains constant over time.

 The concentration in the solid phase is expressed as q, kg adsorbate (solute)/kg

adsorbent (solid),

 and in the fluid phase (gas or liquid) as c, kg adsorbate/m3 fluid.

Adsorption Equilibrium (cont’d) 19
 Adsorption Isotherm describes the equilibrium of the adsorption of a material
at a surface at constant temperature.
 Isotherms are generally in semi-empirical form, where the constants of
standard equations are fitted to experimental data.
Adsorption Equilibrium (cont’d) 20

 Henry’s Law
q = KC
 where K is a constant determined experimentally, m3/kg adsorbent.
 This linear isotherm is not common, but in the dilute region it can be used to
approximate data for many systems.

 Freundlich isotherm
q = KCn

 where K is Freundlich capacity parameter and n is Freundlich intensity

parameter.
 This isotherm is empirical, often approximates data for adsorption systems and
is particularly useful for liquids.
 K and n must be determined experimentally.
 If a log–log plot is made for q versus c, the slope is the dimensionless exponent
n.
 The intercept gives the value of K.
Adsorption Equilibrium (cont’d) 21

 Langmuir isotherm
𝐪𝐪𝐨𝐨 𝐂𝐂
q=
𝐊𝐊 + 𝐂𝐂

 where qo is kg adsorbate/kg solid and K is kg/m3.

 Assumptions:
 Only a fixed number of active sites available for adsorption.
 Only a monolayer is formed.
 That the adsorption is reversible and reaches an equilibrium condition.
 By plotting 1/q versus 1/c, the slope is K/qo and the intercept is 1/qo.
Mathematical Problem 22
Problem 1:
Mathematical Problem (cont’d) 23
Solution: Henry’s Law:

Not Good enough

Mathematical Problem (cont’d) 24
Langmuir Isotherm:

Not Good enough

Mathematical Problem (cont’d) 25
Freundlich Isotherm:

Good enough
Mathematical Problem 26
Problem 2:

Adsorption
Mathematical Problem (cont’d) 27
Solution:
Batch Adsorption 28

 Batch adsorption is often used to adsorb solutes from liquid solutions when the
quantities treated are in small amounts, as in the pharmaceutical or other industries.

 As with many other processes, an equilibrium relation such as the Freundlich or

Langmuir isotherm and a material balance are needed.

 The initial feed concentration is cF and the final equilibrium concentration is c. Also,
the initial concentration of the solute adsorbed on the solid is qF and the final
equilibrium value is q. The material balance on the adsorbate is,

 where M is the amount of adsorbent, kg; and S is the volume of feed solution, m3.

 When the variable q in the equation is plotted versus c, the result is a straight line. If
the equilibrium isotherm is also plotted on the same graph, the intersection of both
lines gives the final equilibrium values of q and c.
Mathematical Problem 29
Problem 3:
Mathematical Problem (cont’d) 30
Solution:  The given values are cF = 0.21 kg phenol/m3, S = 1.0 m3, M = 1.40 kg carbon, and
qF is assumed as zero.
0(1.40) + 0.21(1.0) = q(1.40) + c(1.0)

 At the intersection, q = 0.106 kg

phenol/kg carbon and c = 0.062
kg phenol/m3.

 . The percent of phenol extracted is,

Design of Fixed Bed Adsorption Column 31

 A widely used method for adsorption of solutes from liquid or gases employs a fixed
bed of granular particles.

 The fluid to be treated is usually passed down through the packed bed at a constant
flow rate.

 The concentrations of the solute in the fluid phase and of the solid adsorbent phase
change with time and with position in the fixed bed as adsorption proceeds.

 At the inlet to the bed, the solid is assumed to contain no solute at the start of the
process. As the fluid first comes in contact with the inlet of the bed, most of the mass
transfer and adsorption takes place here.

 As the fluid passes through the bed, the concentration in this fluid drops very rapidly
with distance in the bed and reaches zero well before the end of the bed is reached.
 Design of Fixed Bed Adsorption Column 32
 The fluid concentration co is the feed concentration and c is the fluid concentration at a
point in the bed.

Figure: Concentration profiles for adsorption in a fixed bed: (a) profiles at various positions and times in the bed
Design of Fixed Bed Adsorption Column 33

 After a short time, the solid near the entrance to the tower is almost saturated, and
most of the mass transfer and adsorption now takes place at a point slightly farther
from the inlet.

 At a later time t2, the profile or mass transfer zone where most of the concentration
change takes place has moved farther down the bed.

 The solid at the entrance would be nearly saturated, and this concentration would
remain almost constant down to the mass-transfer zone, where it would drop off
rapidly to almost zero.

 The dashed line for time t3 shows the concentration in the fluid phase in equilibrium
with the solid. The difference in concentrations is the driving force for mass transfer.
 Breakthrough Curves 34

Figure: Concentration profiles for adsorption in a fixed bed: (a) profiles at various positions and times in the bed
(b) breakthrough concentration profile in the fluid at the outlet of the bed.
Breakthrough Curves 35
 As seen in Concentration profile(a), the major part of the adsorption at any time takes
place in a relatively narrow adsorption or mass-transfer zone. As the solution
continues to flow, this mass-transfer zone, which is S-shaped, moves down the
column.

 This outlet concentration remains near zero until the mass-transfer zone starts to
reach the tower outlet at time t4. Then, the outlet concentration starts to rise and at t5
the outlet concentration has risen to cb, which is called the break point.

 After the break-point time is reached, the concentration c rises very rapidly up to
point cd, which is the end of the breakthrough curve, where the bed is judged
ineffective.

 The break-point concentration represents the maximum that can be discarded and is
often taken as 0.01 to 0.05 for cb/co. The value cd/co is taken as the point where cd is
approximately equal to co.
Capacity of Column 36
 The mass-transfer-zone width and shape depend on the adsorption isotherm, flow
rate, mass-transfer rate to the particles, and diffusion in the pores. The total shaded
area represents the total or stoichiometric capacity of the bed as follows:

 where tt is the time equivalent to the total or stoichiometric capacity.

Capacity of Column (cont’d) 37
 The usable capacity of the bed up to the break-point time tb is the crosshatched area:

 where tu is the time equivalent to the usable capacity or the time at which the effluent
concentration reaches its maximum permissible level.

 The value of tu is usually very close to that of tb. The ratio tu/tt is the fraction of the
total bed capacity or length utilized up to the break point Hence, for a total bed length
of HT m, HB is the length of bed used up to the break point.
Capacity of Column (cont’d) 38

 The length of unused bed HUNB in m is then the unused fraction times the total
length:

 The HUNB represents the mass-transfer section or zone. The value of HB is directly
proportional to tb. Then, the length HUNB of the mass-transfer section is simply added
to the length HB needed to obtain the total length, HT:
Mathematical Problem 39
Problem 4:
A waste stream of alcohol vapor in air from a process was adsorbed by activated carbon
particles in a packed bed having a diameter of 4 cm and length of 14 cm containing 79.2 g of
carbon. The inlet gas stream having a concentration co of 600 ppm and a density of 0.00115
g/cm3 entered the bed at a flow rate of 754 cm3/s. Data in the Table give the concentrations of
the breakthrough curve. The break-point concentration is set at c/co = 0.01.
a. Determine the break-point time, the fraction of total capacity used up to the break point, and
the length of the unused bed. Also, determine the saturation loading capacity of the carbon.
b. If the break-point time required for a new column is 6.0 h, what is the new total length of the
column required?
 Mathematical Problem (cont’d) 40
Solution:
For c/co = 0.01, the break-point time is tb = 3.65 h from the graph. The value of td is approximately
6.95 h. Numerically or graphically integrating, the areas are A1 = 3.65 h and A2 = 1.51 h. Then, the
time equivalent to the total or stoichiometric capacity of the bed is,
 Mathematical Problem (cont’d) 41
Solution:
Hence, the fraction of total capacity used up to the break point is tu/tt = 3.65/5.16 = 0.707. The
length of the used bed is HB = 0.707(14) = 9.9 cm. The length of the unused bed,

We determine the saturation capacity of the carbon,

 Mathematical Problem (cont’d) 42
Solution:
For part (b), for a new tb of 6.0 h, the new HB is obtained simply from the ratio of the break-point
times multiplied by the old HB,

The fraction of the new bed used up to the break point is now 16.3/20.4, or 0.799.
Adsorption Cycle 43
 Large-scale adsorption processes can be divided into two broad classes:

 Cyclic batch system, in which the adsorption fixed bed is alternately saturated and
then regenerated in a cyclic manner.
 Continuous flow system which involves a continuous flow of adsorbent counter
current to a flow of feed.

 There are four basic methods in common use for the cyclic batch adsorption system
using fixed beds.

 After a bed has completed the adsorption cycle, the flow is switched to the second
newly regenerated bed for adsorption. The first bed is then regenerated by any of the
following methods.
Temperature-swing cycle 44

 This is also called the thermal-swing cycle.

 The spent adsorption bed is regenerated by heating it with embedded stream coils or
with a hot purge gas stream to remove the adsorbate.

 Finally, the bed must be cooled so that it can be used for adsorption in the next
cycle.

 The time for regeneration is generally a few hours or more.

Pressure-swing cycle 45

 In this use the bed is desorbed by reducing the pressure at essentially constant
temperature and then purging the bed at this low pressure with a small fraction of the
product stream.

 This process for gases uses a very short cycle time for regeneration compared to
that for the temperature swing cycle.
Inert-purge gas stripping cycle 46

 In this cycle the adsorbate is removed be passing nonadsorbing or inert gas through
the bed.

 This lowers the partial pressure or concentration around the particles and desorption
occurs.

 Regeneration cycle times are usually only a few minutes.

Displacement-purge cycle 47

 The pressure and temperature are kept essentially, constant as in purge-gas

stripping, but a gas or liquid is used that is adsorbed more strongly than the
adsorbate and displaces the adsorbate.

 Cycle times are usually only a few minutes.

 Steam stripping is often used in regeneration of solvent recovery systems using

activated carbon adsorbent.

 This can be considered as a combination of the temperature-swing cycle and the

displacement-purge cycle.
Practice Problems 48

Transport Processes and Separation Process by Christie Geankoplis 3rd Edition

Chapter 12: Problems
12.1-1, 12.2-1, 12.3-1, 12.3-2
Thank You