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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.
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)
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.
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
For liquids: larger pores, much slower rate of adsorption than for gases.
Equipment
a. Fixed bed
Adsorption of solvent vapours (Fig. 1)
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.
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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
If the adsorption isotherm is favourable the desorption is similar to the adsorption with
unfavourable isotherm.
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.
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.
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)
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