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Adsorption

(Lecture notes, Prof. Peter LANG, [1])

Definition: separation method: selective fixation of the components of a fluid phase (gaseous
or liquid mixtures) on the surface of a solid material. It is applied for
- purification (most often, to remove small amounts of pollutants) and
- bulk separation (separation of gas mixtures with considerable concentration of adsorbates.
Equilibrium between the fluid and solid phases. Separation occurs because of differences in
molecular weight, shape, or polarity.

Absorption: selective dissolution of the components of a gas mixture in a liquid. Equilibrium


between the gas and liquid phases.

The name of reverse the operation of both the adsorption and absorption is desorption!

Nomenclature:
- solute/adsorbate: component (to be) adsorbed
- adsorber: equipment (e.g. fixed bed column) where adsorption takes place
- adsorbent: solid material of porous structure with very high specific surface area (often 500
to 1000 m2/g)

The most frequent adsorbents:


-activated carbon
-zeolites (molecular sieves)
-silica gel
- activated alumina

Activated carbon:
Carbon produced from carbonaceous source materials like nutshells, wood, lignite, coal etc.
by one of the following processes:
1. Physical reactivation: by using one or a combination of the following processes:
o Carbonization: Pyrolysis at T= 600–900 °C, in absence of oxygen (usually in
inert atmosphere (argon or nitrogen))
o Activation/Oxidation: Raw material or carbonized material is exposed to
oxidizing atmospheres (CO, O2, or steam) at T above 250 °C, usually in the T
range of 600–1200 °C.
2. Chemical activation: The raw material is
a. impregnated with certain chemicals (acid, strong base, or a salt (H3PO4,
KOH, NaOH, ZnCl2)).
b. carbonized at lower T (450–900°C).
Chemical activation is preferred over physical one owing to the lower T and shorter
time needed for activating material.

Requirements for the adsorbents:


1. high selectivity (to enable sharp separations)
2. high capacity (to minimize the amount of adsorbent needed)
3. rapid sorption (good kinetic and transport properties)
4. chemical and thermal stability (including low solubility in the contacting fluid)
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5. hardness and mechanical strength (to prevent crushing and erosion)
6. ease of filling and emptying vessels
7. high resistance to fouling
8. no tendency to promote undesirable chemical reactions
9. capability of being regenerated
10. low cost

Applications:
I. From vapour/gas phase
a. Recovery of organic solvents (used in paints, printing inks etc.):
1. some of the solvent are collected in a condenser
2. adsorption in a bed of activated carbon
b. Removal of pollutants (H2S, CS2 and other odorous compounds).
-from air circulating in ventilation systems
-to prevent gasoline vapours from being vented to the air (canisters of carbon in the
cars)
c. Drying of gases: e.g. adsorbing of water on silica gel
d. Separations: O2/N2 on molecular sieves, pure H2 from synthesis gas,
normal paraffins/branched and aromatic ones

II. From liquid phase


a. Removal of
-organic components from drinking water and aqueous wastes
-colored impurities from sugar solutions
-water from organic liquids
b. Recovery of reaction products

For liquids: larger pores, much slower rate of adsorption than for gases.

Equipment
a. Fixed bed
Adsorption of solvent vapours (Fig. 1)

Fig. 1 Adsorption of solvent vapours in a fix bed system


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Downflow is preferred, upflow might fluidise the particles (attrition and loss of fines)
In one column adsorption in the other desorption (regeneration of adsorbent) takes place.

Regeneration is made with


-steam (if the solvent is not miscible with water) or
-hot inert gas
Steam
-condenses in the bed,
-raises T of the solid and
-provides energy for desorption.
The solvent is 1. condensed, 2. separated from the water, 3. sometimes dried before reuse.
After regeneration the bed may be cooled and dried with inert gas. If some water vapour can
be in the clean gas the evaporation of water remaining in the bed helps cool the bed during
absorption.

b. Gas drying equipment


Similar to the above equipment but instead of steam hot gases are used for regeneration.
The moist gas from the bed may be vented or water may be removed in a condenser then the
gas recycled to the bed through a heater.

c. Pressure swing adsorption (PSA)


Bulk separation process based on the differences in the equilibrium used for
-small scale air (O2/N2) separation plants on molecular sieves
-concentration of H2 in process streams.
Two beds of adsorbents: in one of them adsorption at high P while in the other regeneration at
P=1 atm. For the same concentration N2 is adsorbed 3-4 times more strongly than O2, nearly
pure O2 can be produced.

Remark: Air separation can be also performed based on the differences in adsorption kinetics
on other (carbon) molecular sieves with small pore mouths admitting O2 (smaller molecule)
better. The diffusivity of O2 is 100 times greater. Nearly pure N2 can be produced.

d. Adsorption from liquids


1. Tall fix carbon beds for removal of
- pollutants from aqueous wastes
-trace organics from municipal water supply.

2. Large stirred tank (of waste water) with powdered carbon:


Mechanical stirrers or air spargers keep the particles suspended.
With fine particles:
-the adsorption is more rapid than with granular carbon but
-larger equipment is needed to remove the spent carbon (by sedimentation or filtration)
The adsorption on powdered carbon can be combined with microbiological treatment in large
aerated tanks. The pollutants not biodegradable are adsorbed.
The price of powdered carbon is half that of granular one.

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Equilibria, adsorption isotherms
Isotherms: equil. relationship between the concentrations of the solute in the fluid and solid
phase at T=const.
Concentration units:
-Fluid phase (c): liquids e.g. mg/l, gases: mole percent/partial pressure/ppm
-Solid (W): e.g. g adsorbate/g adsorbent

Types of isotherms (c-W) (Fig. 2):

Fig. 2 Adsorption isotherms

a. favourable: at low c relatively high W


Langmuir: W=Wmax[Kc/(1+Kc)], where K is adsorption constant
Good estimation only for gases weakly adsorbed
b. Strongly favourable:
K is large and Kc>>1
Freundlich equation:W=bcm b and m are constants, m<1, for adsorption from liquids
c. linear:
if Kc<1 the isotherm nearly linear
d. irreversible:
High, constant W independently from c
e. Unfavourable: relatively low W

If the adsorption isotherm is favourable the desorption is similar to the adsorption with
unfavourable isotherm.

Different types of isotherms for adsorption of water from air (Fig. 3)

a. Silica gel: nearly linear until φ=50 %, then saturation. Higher ultimate capacity (cca.
0.42 g W/g dry solid) than that of the other two adsorbents.

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At high humidity capillary condensation in the small pores so the capacity depends not
only on the surface area but also on the volume of pores.
b. Molecular sieve (4 A): almost irreversible, W is held the most strongly, but smaller
volume of pores.
c. Alumina: lowest capacity

The isotherms fall on a single curve if they are taken in the function of φ, otherwise the
capacity decreases strongly with increasing T.

Fig. 3. Adsorption isotherms for water in air at 20 to 50 °C


(g adsorbed/g dry solid vs. relative humidity (φ))

Concentration profile in a fix bed adsorber


The concentration in both phases varies with both time and position in the bed: e.g. c=f(t,l)
1. At first mass transfer takes place near the inlet of the bed (Fig. 4, curve t1). The solid
contains no absorbate at the start the concentration in the fluid phase (c) drops
exponentially to zero before the end of the bed (l=L)
2. Later the solid is (nearly) saturated near the inlet, mass transfer takes place farther
from the inlet, the c-profile becomes S-shaped (curve t2).
The region where most of change of c (c/c0 between 0.95 and 0.05) occurs:
mass transfer (or active) zone.
3. With time the active zone moves toward the outlet (curves t3 and t4). The profiles t2,t3
and t4 have the same shape (self-sharpening) characteristic for systems with favourable
isotherms. (The profiles for systems with linear isotherms become broader with
distance because of axial dispersion.)

Similar profiles could be drawn for the solid phase. Instead of W the concentration in the fluid
phase in equilibrium with the solid is drawn (ceq, dashed line for t2). ceq is smaller than c, the
difference is the driving force which is large where the c-profile is steep.

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Breakthrough curve
Breakthrough curve: c/c0 for fluid leaving the bed vs. time. At t1, t2 and t3 c is practically zero.
At tb c reaches the max. permissible value (break (through) point, e.g. c/c0=0.05) and the feed
is diverted to another column. (The av. fraction of solute removed from the start to the break
point is 0.99 or higher.)
If adsorption is continued after tb c/c0 rises quickly to 0.5 then more and more slowly
approaches 1.0. The breakthrough curve is S-shaped and nearly symmetric. The area between
the line c/c0=1 and the curve is proportional to the amount of solute adsorbed.

Fig. 4. Concentration profiles (a) and breakthrough curve (b)

t* is the adsorption time for an ideal (vertical) breakthrough curve. For a symmetric curve at t*
c/c0=0.5.

Calculation of t*
The solute feed rate for unit cross section area from the superficial velocity (u0)

F=u0c0 (mol/m2s)

In ideal case all the solute fed until t* is adsorbed while in the solid W increased from W0 to
the saturation value Wsat.
u0c0t*=Lρ(Wsat-W0) (mol/m2)

or t*=Lρ(Wsat-W0)/ (u0c0)

where ρ is the bulk density of the bed.


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For fresh or completely regenerated (too costly!) adsorbent W0=0 .

The length of the active zone can be


-infinitesimal (ideal case),
-small: the breakthrough curve is steep (Fig. 5a), most of the capacity of the bed is utilized,
-large: the breakthrough curve is extended (Fig. 5b), less than half of the capacity of the bed is
utilized.

Fig. 5. Breakthrough curve for short (a) and long (b) active zone

Continuous Operation
In a fixed bed adsorber the active zone is often only a small fraction of the bed. Continuous
countercurrent flow of adsorbent and fluid means more efficient use of adsorbent.

- Two beds arranged vertically (Fig. 6a):, solids move from the top by gravity through the
desorber and the absorber. From the bottom they are carried to the top by pneumatic conveyor
or bucket elevator. The whole process (inlet and outlet concentrations, operating and
equilibrium line) is presented in Fig. 6b by assuming that the adsorption and desorption is
carried out at the same temperature.

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Fig. 6. Countercurrent adsorber
a. Scheme b. Presentation of the process in equilibrium diagram
-Simulated moving bed (Sorbex process, Fig. 7)
Tall column divided into 12 segments, each with flow distributor for addition or removal of
liquid. The inlet and exit points for the 4 streams are moved to the adjacent segments of the
bed with each new position of the rotary valve.
The effect is similar as for the countercurrent flow.

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Fig. 7. Scheme of the Sorbex process

In the case of separation of binary mixtures (A-B) the desorbent (D) has
-greater affinity for the solid than the component weakly bound but
-less affinity than the component more strongly bound

Literature:
[1] Mc Cabe W. L., J. C. Smith, P. Harriott:Unit Operations of Chemical Engineering, 7-th edition