SHR Chapter 15

Adsorption
A very brief primer

Example: Dehumidification

Adsorption cycle:
water adsorbs onto
adsorbent (activated carbon)
adsorbent acts like a
sponge with an absorbent
front that saturates the bed
stop before breakthrough
when the bed is saturated
Pressure-swing
adsorption

Regeneration cycle:
cycle onto fresh bed for
adsorption
blow-down (drop pressure)
to regenerate.

SHR 15.1.1

Adsorbents
Activated Carbon
often made from biomass oxidation (char)
Molecular sieve carbon
very small pore size
Air separation

activated
carbon

N2: 3.0 x 4.1, O2: 2.8 x 4.0, O2 preferentially adsorbs

cryogenic distillation is another common technique...

Molecular sieve zeolites

uniform pore size
aluminosilicate minerals:
Zeolite 3A: K12[(AlO2)12(SiO2)12], dp=3
Zeolite 13X: Na86[(AlO2)86(SiO2)86], dp=10

Also commonly used as catalysts

Non-clumping cat litter
Air separation
Silica gel
affinity for polar compounds
in lots of items you buy (silica pouches) to reduce humidity
3

zeolite
ZSM-5

SHR 15.1.1, Table 15.2

Properties of Adsorbents
Key quantity: specific area, Sg
(surface area per unit mass).
activated
carbon

Specific
pore
volume:

p
porosity
Vp =
=
p
density

H2O Capacity
p
at 25C and
Sg
(g/cm3) (m2/g) 4.6 mmHg, wt
% (dry basis)

Adsorbent

Nature

dp
()

Activated
Alumina

Hydrophilic,
amorphous

1075

0.5

1.25

320

Silica gel
(small pore)

amorphous

2226

0.47

1.09

750850

11

1000.71
150

0.62

300350

Silica gel
(large pore)
Activated Carbon
(small pore)

Hydrophobic,
amorphous

Activated Carbon
(large pore)
Molecular-sieve
carbon
Molecular-sieve
zeolites

Hydrophobic,
nonpolar

1025

0.40.6

0.5-0.9

4001200

>30

0.6-0.8

200600

2-10

0.98

4001200

1.4

600700

20-25

Polar-hydrophilic,
0.23-10
crystaline
0.5

Area of a football field = 5,350 m2.

4

Equilibrium
No good theory exists for getting K-values for adsorption.
each adsorbate-absorbent pair needs to be treated individually - typically
using experiments.

Equilibrium is a function of:

concentration (liquids) or partial pressure (gases)
solute loading on the absorbent (moles adsorbate per unit mass of
adsorbent)

SHR 15.2.1

Isotherms - Pure Gases

Typically, data are taken over a range of adsorbate concentrations at
constant temperature to obtain an adsorption isotherm

NH3 on charcoal
6

Isotherm Models - Pure Gases

q - equilibrium loading (volume adsorbed per unit mass of adsorbent)
Linear isotherm
(empirical model)
Freundlich isotherm
(empirical model)

q = kp
1/n

q = kp

Henrys law - applicable

for low loadings.
k, n are empirical
parameters to fit data.

Assume adsorption/desorption is a first-order process:

dq
Kp
q
At equilibrium, dq/dt = 0 so =

= ka p(1 ) kd
1 + Kp
qm
dt
fraction of occupied sites
maximum loading (complete surface coverage)
adsorption rate constant
desorption rate constant
ka/kd (reaction equilibrium constant)

Kqm p
Langmuir isotherm q =
1 + Kp

K, qm are unknown
parameters.

140

120

q (cm3/g)

qm
ka
kd
K

data
Freundlich
Langmuir

100

80

SHR Example 15.4

60

Note: for liquids, concentrations rather

than pressures are commonly used.

40
0

200

400

600
p (psia)

800

1000

1200

Other ways of looking at equilibrium

Isobars

Isosteres

Isotherms

(constant amount adsorbed)

Effect of Adsorbent
Pure propane vapor

Typically, experiments are required for each adsorbent/solute pair

9

Regeneration
Pressure-swing absorption

Temperature-swing absorption

10

SHR 15.3.1

Analysis of Packed Bed

Adsorbers

Convection-Dispersion Model
Mole balance
in bulk phase

@cf
@cf
@J
+u
+
=
@t
@z
@z
Time-rate of
change of cf
at a point in
space.

Convection:
velocity
pushing cf
around.

Diffusion
of cf.

b @
cb
b @t

Decrease in cf due to
adsorption to solid.

cf - concentration of solute in fluid

c b - average adsorbed concentration
per unit mass
b - void fraction (bounded [0,1])
us - superficial velocity, us = bu
u - intersticial velocity
J - Diffusive flux

Ideal Breakthrough
Breakthrough time: when the solvent comes out the back of the bed
If adsorption is immediate and complete, then the breakthrough time can be
determined by the loading, flow rate of solute, and mass of sorbent.
1.
2.
3.

Ideal
1
Ideal
Actual

c f /cF

0.8

QF - Feed volumetric flow rate

cF - solute concentration in feed
tideal - ideal breakthrough time
Lideal - ideal breakthrough length
cb* - loading in equilibrium with cF
A
- cross-sectional area of bed
b - void fraction (bounded [0,1])

0.6
0.4
0.2
0

0.2

0.4

0.6

0.8

Negligible mass transfer resistance (external

and internal)
Ideal plug flow in the bed
Adsorption isotherm applies throughout,
local equilibrium is achieved instantaneously.

QF cF tideal =

cb A(1

b )Lideal

More Realistic Breakthrough

@cf
@cf
@J
+u
+
=
@t
@z
@z

Rp
kc,tot
cF
p*
kc
De
ka
kd
Kd

b @
cb
b @t

Approximate solution
(see SHR 15.3 for some assumptions):

p
cf
1 + erf

cF
3kc,tot z
=
Rp u

b
b

1
1
+ p + p
8
8

3kc,tot
=
t
Rp

1
Ideal
Actual

c f /cF

0.8

kc,tot

0.6

z
u

1
=
p (1 + Kd )

1
Rp
3
=
+
+
kc
5p De
Rp ka p
bulk
resistance

0.4
0.2
0

0.2

0.4

0.6

0.8

- radius of particle
- mass transfer coefficient
- feed concentration of solute
- pore volume fraction accessible to solute
- fluid phase mass transfer coefficient
- effective solute diffusivity in the pore
- kinetic-adsorption rate constant
- kinetic desorption rate constant
- ka/kd (adsorption/desorption equilibrium
constant)

internal
diffusion
resistance

Kd
1 + Kd

kinetic sorption resistance

Chromatography
Feed in a pulse (sample) of
material.
Sample constituents have
different affinities for the
solute.
As the fresh fluid follows
the sample, the adsorbed
species are flushed out.
Different elution times for
the various constituents allow
separation.