Multicomponent Separations

Adsorption

1
Adsorption “clean” gas

Air+SO2

“dirty” gas

Adsorption is a process that occurs when a gas or liquid solute

accumulates on the surface of a solid (adsorbent), forming a molecular
or atomic film (adsorbate)

2
Introduction
 Adsorption is a process that occurs when a gas or liquid
solute accumulates on the surface of a solid (adsorbent),
forming a molecular or atomic film (adsorbate).
 In commercial processes, the adsorbent is usually in the
form of small particles in a fixed bed.
 The fluid is passed through the bed and 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 desorption occurs.
 The adsorbed material (adsorbate) is thus recovered and
the solid adsorbent is ready for another cycle of adsorption.

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Multi-Component Separations H83MCS
Multi-Component Separations H83MCS
Criteria for the Use of
Adsorption
Adsorption is an attractive alternative over distillation in the
following situations:
 Separability: key relative volatility < 1.5 (including
azeotropes).
 The product of interest is a high-boiler at low concentration
in the feed stream (< 20 wt%) .
 An undesirable high-boiler, present in low concentration
(only a few wt%) , must be removed from the feed stream.
 The boiling range of one set of components overlaps the
range of another set of components which must be purified.

Multi-Component Separations H83MCS

Criteria for the Use of
Adsorption
 Cryogenic conditions or high (> 523 K) temperatures are
required for distillation.
 Vacuum pressures (< 2 KPa) or high pressures (> 5 MPa)
are required for distillation.
 Undesirable side reactions occur during distillation.
 Throughputs are less than a few tons per day.
 Corrosion and precipitation is a problem.
 Explosive conditions are encountered in the column.

Multi-Component Separations H83MCS

Introduction
 Adsorbents are in the form of small pellets, beads or
granules ranging from about 0.1mm to 12mm size.
 A particle of adsorbents has a very porous structure with
many fine pores and pore volumes up to 50% of the total
particle volume.
 The rate of mass transfer of the adsorbate onto the
adsorbent (fixed-bed) is based on the diffusion of adsorbate
from the bulk solution through the stagnant film surrounding
the particle external surface (external film mass transfer).
 Once reaching the surface, adsorption occurs
instantaneously and equilibrium is established between the
adsorbate in the fluid and that on the adsorbent surface.

Multi-Component Separations H83MCS

Introduction
 The adsorbed material then diffuses into the pores and
finally the adsorbate is adsorbed on the pore’s surface.

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Multi-Component Separations H83MCS
Application
 Since ancient times, water tastes better when treated with
charred wood.
 Certain materials to remove colour from solutions in the
15th century.
 Bone char for decolourising sugar solutions in the late 18th
century.
 Wood charcoal for air purification in respirators in hospitals
in the mid-19th century.
 Large-scale, bulk gas adsorption processes in the early
1920s – the removal of alcohol and benzene from a gas
stream by Bayer AG in Germany, and the recovery of
ethane and higher hydrocarbons from natural gas by Union
Carbide in US.
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Application
 Today, adsorption to be the most widely used non vapor-
liquid technology for molecular separations in the
petroleum, natural gas, petrochemical and chemical
industries.
 Applications of liquid-phase adsorption include removal of
organic compounds from water or organic solutions,
colored impurities from organics and fermentation products
from fermentor effluents.
 Application of gas-phase adsorption include removal of
water from hydrocarbon gases, sulfur compounds from
natural gas, solvents from air and other gases, and odors
from air.

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Desorption / Regeneration
 Desorption is a phenomenon whereby a substance is
released from or through a surface
 By increasing the temperature of the adsorbent or
reducing an adsorbate’s partial pressure (or concentration
in a liquid), the adsorbate can be desorbed.
 Allows recovery of valuable adsorbates.
 Permits re-use of the adsorbent for further cycles.
 Sometimes, desorption is not practical, and the adsorbate
must be removed by thermal destruction or another
chemical reaction, or the adsorbent is simply discarded.

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Desorption / Regeneration
 To subject adsorbent to one set of conditions and then
another (eg. low temp followed by high temp), the
adsorbent has to move from one place to another.
 Must have two zones (or fixed beds), and the conditions
must be periodically changed in each zone.
 Such complexity leads to high costs; thus adsorption
processes are less common than they might otherwise be.

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Adsorbents
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
components.
2. Must show reversibility – so the adsorbate can be
recovered, and the adsorbent reused.

Multi-Component Separations H83MCS

Adsorbents
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.

 The selection of size and shape of adsorbent is influenced

by :
- minimization of mass transfer effects (so that
equilibrium is approached),
- minimization of pressure drop (to maximise flow-rates).
Pore sizes:
Macropores d>50 nm
Mesopores 2<d<50 nm
Micropores d<2 nm
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 Adsorbents
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.
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.

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Adsorbents
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 more polar solutes in aqueous
solutions.

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In ‘bulk separations’, the adsorbate concentration is greater than about 10
wt % in the feed.
In ‘purifications’, it is generally no more than a very few wt%.

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 Adsorbents
Estimated Annual Worldwide Sales
of Major Adsorbents in 1995

Adsorbent Sales
Activated carbon $380 million
Molecular sieve zeolites $100 million
Silica gel $27 million
Activated alumina $26 million

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 Adsorption is always
exothermic – why?
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
Multi-Component Separations H83MCS
 Adsorption Equilibrium
m

V, C0 V, C
T is constant

m3 kg/m3
kg/kg
V C0  C 
q
m
kg
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Adsorption Equilibrium
 When the equilibrium value, q is plotted against C, the
adsorption isotherm is obtained.

Multi-Component Separations H83MCS

Adsorption Equilibrium
 Adsorption Isotherm - Isothermal relationship for the
equilibrium, between the concentration (or partial pressure) of
adsorbate in the external fluid and the concentration of
adsorbate in the adsorbent.
 Isotherms are in semi-empirical form, where the constants of
standard equations are fitted to experimental data.
1) Henry’s Law
q  KC
- Where K is a constant determined experimentally, m3/kg
adsorbent.
- This linear isotherm is not common, but in dilute region it
can be used to approximate data of many systems.

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Adsorption Equilibrium
2) Freundlich Isotherm

1
q  KC n

- where K is Freundlich capacity parameter and 1/n is

Freundlich intensity parameter.
- This isotherm is empirical, often approximates data for
many physical adsorption systems and is particularly
useful for liquids.
- The K and n are constant and must be determined
experimentally based on a log-log plot of q versus C.
- The dimensions of K depend on the value of n.
Multi-Component Separations H83MCS
Adsorption Equilibrium
3) Langmuir Isotherm

qo C
q
K C

- where qo (kg adsorbate/kg solid) and K (kg/m3) are

empirical constant.
- The equation was derived assuming that there are only
a fixed number of active sites available for adsorption,
only a monolayer is formed, and the adsorption is
reversible and reaches an equilibrium condition.

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Types of adsorption
isotherms

•Type I: unimolecular adsorption and applies to microporous small pore sizes,

which are not significantly greater than the molecular diameter of the adsorbate.
•type II or III: wide range of pore sizes, monolayer to multilayer.
•type IV: multilayer adsorption followed by capillary condensation
•Type V: similar to type III isotherms at low relative pressure but has capillary
condensation at high relative pressure
•Type VI: stepped isotherm: materials with relatively strong fluid – surface
forces, usually when the temperature is near the melting point for the adsorbed
gas

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Typical gas sorption data
(for a mesoporous silica material)

700
Hysteresis
Volume adsorbed/(cc(STP)/g)

600 Type IV

500
400 Desorption

300
Ads.
200
100
0
0.0 0.2 0.4 0.6 0.8 1.0
Relative pressure

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Adsorption Equilibrium
Problem 1:
Batch tests were performed in the laboratory using solutions of phenol in water
and particles of granular activated carbon. The equilibrium data at room
temperature are shown in the table. Determine the isotherm that fits the data.
C q
(kg phenol/m3 solution) (kg phenol/kg carbon)
0.322 0.150
0.117 0.122
0.039 0.094
0.0061 0.059
0.0011 0.045

1 qo C
q
q  Kc q  KC n
K C

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Adsorption Equilibrium
Answer:

Henry’s Law: q  KC

1
q  KC n

Freundlich Isotherm:
Lnq   LnC   LnK 
1
n

q0C
q
K C
Langmuir Isotherm: 1 K1 1
  
q q0  C  q0

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Henry’s Law

Not adequate

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Freundlich Isotherm

Adequate

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Langmuir Isotherm

Not adequate

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Freundlich Isotherm

Ln(k) = -1.654 ==> K= 0.191

q  0.191C 0.2184

1/n = 0.2184 ==> n= 4.579

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Freundlich Isotherm

q  0.191C 0.2184

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 Batch Adsorption
Problem 2:
A wastewater solution having a volume of 1m3 contains 0.21 kg phenol/m3 of
solution. A total of 1.40 kg of fresh granular activated carbon is added to the solution,
which is then mixed thoroughly to reach equilibrium. Using the isotherm from problem
1, what are the final equilibrium values, and what percent of phenol is removed from
the wastewater?

C(kg/m3) 0.063
q(kg/kg) 0.105

Multi-Component Separations H83MCS

Multicomponent Adsorption
Equilibrium

 The Adsorption Equilibrium of Henry’s Law, Freundlich and

Langmuir isotherms are suitable for only single-solute
adsorption.
 When an adsorbent is mixed with a multicomponent
solution, adsorption of solute / adsorbate i in the presence
of other competing solutes occurs.
 Interaction between the solutes must be considered
 The equilibrium concentration of adsorbate i in the presence
of other competing organic solutes, ce,i expressed in term of
the solid phase loading of adsorbate, qi is expressed by the
Ideal Adsorbed Solution Theory (IAST).

Multi-Component Separations H83MCS

Multicomponent Adsorption
Equilibrium
 The IAST allows the single-solute behavior represented
by the Freundlich adsorption isotherm in predicting
multicomponent adsorption.
 The IAST is expressed as:
1
N
 1 
  qj
ni

qi  j 1 n j 
Ce ,i  N  1 
 qj 

Ki 
j 1  ni 
Ce, i = equilibrium concentration in multicomp. sys.
N = total number of solute
Ki = Freundlich capacity parameter
1/ni = Freundlich intensity parameter
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 Adsorption Cycles

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Basic Adsorption Cycles
 Extremely difficult to move adsorbents from one place to
another without damaging either particles or equipment.
 Most adsorption processes operate in semi-batch, where
adsorbent beds are periodically loaded and unloaded.
 Two or more beds, in parallel but out of phase, are operated
to achieve a pseudo steady-state operation.

Multi-Component Separations H83MCS

Basic Adsorption Cycles
 Three strategies to ‘load’ an adsorbate onto an adsorbent,
and then to desorb it are:

1. Temperature-Swing Adsorption (TSA), or thermal-swing

adsorption, by changing the temperature of the adsorbent.

2. Pressure-Swing Adsorption (PSA) in the gas phase (by

altering partial pressure of the adsorbate), and
Concentration-Swing Adsorption (CSA) in the liquid phase
(by altering adsorbate concentration).

3. Displacement-Purge Adsorption (DPA) (by adding/removing

a component that competitively adsorbs with the adsorbate,
used mostly in liquid separations.
Multi-Component Separations H83MCS
Basic Adsorption Cycles
 Heat effects can pose a major complication for many adsorption
processes.
 A significant amount of heat is released when materials adsorb, and a
significant amount of heat is required when they desorb.
 This heat tends to heat up the adsorbent and vessel, and the stream
leaving the bed.
 For bulk separation processes, a large fraction of the heat remains in
the bed to raise its temperature, and this will limit the maximum
adsorption.
 For purification processes, most of the heat departs with the stream
leaving the bed and the latter remains isothermal.
 The times required for an adsorbent to undergo a complete cycle – that
is, both adsorption and desorption or regeneration – varies markedly
with the type of cycle.
 Cycle times of PSA (few seconds to a few minutes) , TSA (hours)

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Temperature-Swing Adsorption (TSA)

T2>T1

Temperature-Swing Adsorption Cycle with Inert Purge

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Temperature-Swing Adsorption (TSA)

 A stream containing a small amount of an adsorbate at partial

pressure P1 is passed through the adsorbent bed at
temperature T1.
 The equilibrium ‘loading’ (adsorption) on the adsorbent is X1.
 After equilibrium between adsorbate in the feed and on the
adsorbent is reached, the bed temperature is raised to T2, and
more feed is passed through the bed.
 Desorption occurs, and a new equilibrium loading X2 is
established. The delta loading is then X1 – X2.
 Typical values are in excess of 1 kg per 100 kg of adsorbent.
 In place of introducing feed during desorption, a heated inert
stream (known as a purge) is also used.

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Temperature-Swing Adsorption (TSA)

Since TSA is generally used for purifications, the bed

operates at nearly isothermal conditions during the
adsorption step, and the heat of adsorption is removed by
the effluent stream.
During the regeneration step, the bed is heated, most
often directly by a hot gas or stream rather than indirectly
through the wall or via coils in the bed.
The heat both warms the bed and supplies the heat
necessary to desorb the adsorbate.
Note that a hot inert gas stream not only provides heat but
also dilutes the concentration of adsorbate in the fluid, and
thereby provides an additional incentive for desorption.

Multi-Component Separations H83MCS

Temperature-Swing Adsorption (TSA)

 In some cases the adsorbate can be condensed out of the

purge stream, and the remaining stream, which is much
lower in flow than the feed stream, can be recycled to the
feed stream going to another bed.
 In such a flowsheet, essentially all of the adsorbate can be
recovered.
 In other process variations, the adsorbate can be vented or
incinerated.
 At the end of the regeneration step, a cool gas stream is
usually fed for a short period to bring the bed back to the
adsorption temperature.
 TSA cycles can consume a substantial amount of energy
per unit of adsorbate.

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Pressure-Swing Adsorption (PSA)

P1>P2

Pressure-Swing Adsorption Cycle

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Pressure-Swing Adsorption (PSA)

 For bulk separation of gases, e.g. air separation to recover

oxygen or nitrogen, and hydrogen purification.
 For recovery of contaminants in vent streams.
 The feed step is operated at a relatively high pressure, and
the regeneration step at a lower pressure.
 A fraction of the adsorbate-free product is used to purge the
low-pressure bed.
 Regeneration step uses a total-pressure reduction and an
adsorbate-concentration reduction (inert-purge) to effect the
partial-pressure reduction that facilitates desorption.

Multi-Component Separations H83MCS

Pressure-Swing Adsorption (PSA)

 The time required to load, de-pressurise, regenerate, and

repressurise a bed is usually a few minutes.
 Although practical delta loadings are < 1 kg per 100 kg
adsorbent to minimise thermal gradient problems, the very
short cycle times make PSA cycle quite attractive for bulk-
gas separations.
 The use of part of the non-adsorbed product stream (rich in
the less adsorbed component) for purging greatly limits the
application of PSA.
 Only a fraction of the adsorbate-free stream is recovered.

Multi-Component Separations H83MCS

Pressure-Swing Adsorption (PSA)

 The adsorbate rich stream is contaminated with non-

adsorbate.
 Thus, PSA is limited to applications where only one pure
product is required.
 More complex flowsheets have been devised, with many
different types of gas exchanges between the beds, to
increase the percent recovery of non-adsorbed stream and
reduce the energy requirements for the process.
 Nevertheless, their increased complexity results in
inevitable investment penalty.

Multi-Component Separations H83MCS

Displacement-Purge Adsorption (DPA)

Displacement-Purge Adsorption (DPA) Processes

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Displacement-Purge Adsorption (DPA)
 Confined primarily to liquid-feed bulk separation.
 A gas/liquid that adsorbs about as strongly as the adsorbate
is used to remove the adsorbate.
 Desorption is thus facilitated both by adsorbate partial
pressure or concentration reduction in the fluid around the
particles, and by competitive adsorption of the displacement
medium.
 Since the displacement-purge fluid is actually adsorbed, it is
present when the adsorption part of the cycle begins and
therefore contaminates the less-adsorbed product.
 The displacement purge fluid must be recovered from both
streams.
 Process includes adsorption column with two distillation
columns. As such, cannot compete if distillation is a viable
option.
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Inert Purge Process

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Inert Purge Process
 Adsorbate is removed by passing a non-adsorbing inert gas
(with very little or no adsorbate) through the bed.
 Lower the partial pressure or concentration of the
adsorbate, to effect desorption.
 With enough purge gas, the adsorbate will be completely
removed, and the maximum delta loading will be X1.
 During subsequent adsorption, removal of adsorbate from
the feed would be until the adsorbent becomes nearly fully
loaded and breakthrough occurs.
 Usually limited to between 1 and a few kg adsorbate per
100 kg adsorbent.
 Cycle times are only a few minutes.

Multi-Component Separations H83MCS