Adsorption
Department Editor: Kate Torzewski
S
uccessful adsorber design requires
information about certain adsorbent
properties, including: adsorbent densi-
ties and void fractions; isotherms or other
equilibrium data; and data on mass-transfer
kinetics and fixed-bed dynamics. Here,
these adsorbent properties are explained,
along with corresponding equations.
Densities and void Fractions
Three densities are relevant: bulk, particle
and solid. There are four pertinent void frac-
tions, three corresponding to the three den-
sities, and one representing the overall void
fraction in the bed of adsorbent (e). These
terms are related in the following way:
ρ B = (1 − ε B ) ρ P = (1 − ε B ) (1 − ε P ) ρ S
(
= 1 − ε ρ
)
S
Bulk density is the mass of adsorbent in a
given volume. Particle density is the mass
of adsorbent per volume occupied by the
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
to a linear equation on log-log coordinates.
In situations that involve multiple adsor-
bate components in the feed, the concept
of selectivity comes into play. Selectivity, α
and β in the three equations below, is the
ratio of the capacity of an adsorbent for
one component to its capacity for another.
yi y j
α ij =
 xi x j
α = A A
ij i j
1−ε
1+ Aj
ε B empirical coefficient
βij =
1−ε
 1+ Ai
ε
Kinetics Data
Kinetics data describe the intraparticle
mass-transfer resistance and control the
cycle time of a fixed-bed adsorption
process. Fast kinetics, or a high rate of
diffusion, occur when the effluent concen-
tration remains level until the adsorbent is
almost saturated, then rises sharply. Slow
kinetics, on the other hand, occur when the
effluent concentration begins fluctuating
soon after adsorption starts. The effect of
(1) slow diffusion can be overcome by add-
ing adsorbent at the product end, or by
increasing the cycle time. It is also possible
to use small particles.
Intraparticle diffusion is characterized
by an effective diffusivity Deff, which equals
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,
(4) depending on the value of the system’s
Reynolds number.
 (9)
For 10<Re<2,500, use Equation (10),
where Sc equals μ/ρDAB.
jD = ( k υs ) Sc0.667 = 1.17 Re−0.415
 (10)
For lower flowrates, corresponding to
values of a modified Reynolds number, Re’,
of below 50, use Equation (11).
(5) jD = 0.91ψ Re'−0.51

(6)
 New York, 1996.
NOMENCLATURE
A Henry’s law coefficient
C Concentration (subscripts: 0, initial;
(7) f, final; i, instantaneous)
dp particle diameter
DAB adsorbate diffusivity in the liquid
Deff effective diffusivity
F fractional conversion
i assigned to strongly adsorbed com-
ponent
j assigned to less strongly adsorbed
component
jD Colburn-Chilton j-factor
k fluid-to-particle mass transfer coeffi-
cient
l particle radius (for a sphere or cyl-
inder), or half-thickness (for a rect-
angular solid)
L bed length
n* adsorbent loading
Re Reynolds number
Sc Schmidt number
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.
ΔP ⎛ 1 − εB ⎞⎛ ρυ 2s 1 − ε B ⎞
= ⎜150 + 175⎟⎜⎜ ⎟
L ⎝ Re ⎠⎝ gc dp ε B3 ⎠⎟
 (12)
References
1. Knaebel, K., The Basics of Adsorber Design,
Chem. Eng., April 1999, pp. 92–101.
2. Knaebel, K., For Your Next Separation,
Consider Adsorption, Chem. Eng., November
(11) 1995, pp. 99–102.
3. Masel, R.I., “Principles of Adsorption and Reac-
(11a) tion on Solid Surfaces,” Wiley-Interscience,