Adsorption

Department Editor: Kate Torzewski

NOMENCLATURE
uccessful adsorber design requires

S information about certain adsorbent

properties, including: adsorbent densi-
ties and void fractions; isotherms or other
βij =
1+
1 −ε
ε
1−ε
Aj
A
B
C
Henry’s law coefficient
empirical coefficient
Concentration (subscripts: 0, initial;
equilibrium data; and data on mass-transfer 1+ Ai (7) f, final; i, instantaneous)
kinetics and fixed-bed dynamics. Here, ε
dp particle diameter
these adsorbent properties are explained,
DAB adsorbate diffusivity in the liquid
along with corresponding equations. Kinetics Data
Deff effective diffusivity
Densities anD voiD Fractions Kinetics data describe the intraparticle F fractional conversion
mass-transfer resistance and control the i assigned to strongly adsorbed com-
Three densities are relevant: bulk, particle cycle time of a fixed-bed adsorption ponent
and solid. There are four pertinent void frac- process. Fast kinetics, or a high rate of j assigned to less strongly adsorbed
tions, three corresponding to the three den- diffusion, occur when the effluent concen- component
sities, and one representing the overall void tration remains level until the adsorbent is
jD Colburn-Chilton j-factor
fraction in the bed of adsorbent (e). These almost saturated, then rises sharply. Slow
kinetics, on the other hand, occur when the k fluid-to-particle mass transfer coeffi-
terms are related in the following way:
effluent concentration begins fluctuating cient
ρ B = (1 − ε B ) ρ P = (1 − ε B )(1 − ε P ) ρ S soon after adsorption starts. The effect of l particle radius (for a sphere or cyl-
slow diffusion can be overcome by add- inder), or half-thickness (for a rect-
( ) S angular solid)
ing adsorbent at the product end, or by
= 1−ε ρ (1)
increasing the cycle time. It is also possible L bed length
to use small particles. n* adsorbent loading
Bulk density is the mass of adsorbent in a
given volume. Particle density is the mass Intraparticle diffusion is characterized Re Reynolds number
of adsorbent per volume occupied by the by an effective diffusivity Deff, which equals Sc Schmidt number
particle. Solid density is the mass of the

adsorbent per volume occupied by the par-
ticle, but with the pores’ volume deducted.
equilibrium Data
Adsorption-equilibrium data are usually
gathered at a fixed temperature and plot-
ted or tabulated as isotherms: adsorbent
capacity (loading) versus fluid-phase
concentration (or partial pressure, for gases
and vapors). Below are three equilibrium
equations for isotherm data.
Henry’s Law:
n* = AC
Langmuir Isotherm:
AC
n* =
1 + BC
Freundlich Isotherm:
n* = AC B
Henry’s Law is the simplest isotherm,
while the Langmuir Isotherm takes surface
coverage into account, and the Freundlich
Isotherm is the result of fitting isotherm data
DABερ/τ. Dimensionless time is expressed
as Deff t/l 2, which allows the determination
of the fractional change (during adsorption
or regeneration), as shown below.
(8)
This equation shows that, when searching
for an effective adsorbent, it is usually safe
(2) to choose one having a large diffusivity, a
small diameter, or both.
FixeD-beD Dynamics
(3)
Interstitial mass transfer in fixed beds,
primarily fluid-to-particle transfer, can be
related to the fluid, adsorbent and system
properties via either of two equations,
depending on the value of the system’s
(4)
Reynolds number.
(9)
For 10<Re<2,500, use Equation (10),
t elapsed time
xi mole fraction in fluid phase
yi mole fraction in adsorbed phase
α selectivity, 1<α<infinity
β selectivity, 0<β<1
ε void fraction (subscripts: B, bulk; P,
particle; S, solid)
μ fluid viscosity
ρ fluid density (subscripts: B, bulk; P,
particle; S, solid)
τ tortuosity
υs superficial velocity
ψ particle shape factor
The particle shape factor, ψ, is 1.0 for
beads, 0.91 for pellets and 0.86 for flakes.
αi is the ratio of particle interfacial area to
volume, which equals 6(1 – ε)dP.
Another major factor in bed dynamics is
pressure drop. Most adsorbers are designed
to operate with relatively low pressure drop,
because large particles are used whenever
possible and the velocity is typically low,
to allow equilibration of the fluid with the
adsorbent. The pressure drop in a fixed bed
is represented by the Ergun Equation, below.
s B

to a linear equation on log-log coordinates. where Sc equals μ/ρDAB. ΔP ⎛ 1− ⎞ ⎛ ρυ 2

1− ε ⎞
εB
= ⎜ 150 + 175⎟ ⎜
⎠ ⎝ gc dp εB3 ⎟⎠
In situations that involve multiple adsor-
L ⎝
bate components in the feed, the concept j D = k υ s Sc0.667 = 1.17 Re−0.415
( ) Re
of selectivity comes into play. Selectivity, α (10) (12)
and β in the three equations below, is the
 References
ratio of the capacity of an adsorbent for For lower flowrates, corresponding to
1. Knaebel, K., The Basics of Adsorber Design,
one component to its capacity for another. values of a modified Reynolds number, Re’,
Chem. Eng., April 1999, pp. 92–101.
of below 50, use Equation (11).
yi y j 2. Knaebel, K., For Your Next Separation,
α ij = Consider Adsorption, Chem. Eng., November
xi x j (5) j = 0.91ψ Re'−0.51 (11) 1995, pp. 99–102.
3. Masel, R.I., “Principles of Adsorption and Reac-
α ij = Ai A j (6) (11a) tion on Solid Surfaces,” Wiley-Interscience,
New York, 1996.