ADSORPTION

SYSTEM

Ayu Dahliyanti, M.Eng.

Chemical Process Equipment Design
ChE-Universitas Pertamina
2020
 Books and Grading
Reference Books are available @UP library
• McCabe, Smith, & Harriott, "Unit Operations of
Chemical Engineering." 7th Ed., McGraw-Hill. 2005
• Seader, Henley and Roper, “Separation Process
Principles”, 3rd Edition, John Wiley and Sons, Inc.,
2011
• Brownell.L.E. and Young.E.H., “Process Equipment
Design” 3rd edition, John Wiley & Sons, New York,
1959
• Wankat, "Separation Process Engineering Includes
Mass Transfer Analysis", 3rd Ed., Prentice Hall, 2011
• Perry’s Handbook Of Chemical Engineers
• Etc.

Grading:
UTS: 25%, UAS: 25%, Assignment: 25%, Quiz 25%
 Main Topics Objective
• Basic Principles • To explain the basic principles of
• Adsorbent Selection adsorption
• Adsorption Isotherms • To select a suitable adsorbent
• Adsorbent • To calculate adsorbent capacity,
Regeneration/Reactivation/Disposal adsorbent bed length/volume, and
cycle time.
• Adsorber Design

References:
• Gabelman, Alan. “Adsorption Basic”. AICHE, 2017.
• Chapter 15- Seader, Henley and Roper, “Separation Process Principles,” 3rd Edition, John Wiley and Sons, Inc., 2011
• Chapter 18 - Wankat, "Separation Process Engineering Includes Mass Transfer Analysis", 3rd Ed., Prentice Hall, 2011
• Chapter 25 - McCabe, Smith, & Harriott, "Unit Operations of Chemical Engineering." 7th Ed., McGraw-Hill. 2005
• U.S. Army Corps of Engineers, “Adsorption Design Guide,” 2001.
 Gas/liquid
(adsorbate)
accumulates on the
surface of a solid
Solid Adsorbent (adsorbent)
Adsorption
vs
Absorption
Interphase transfer;
gas to liquid
 Affinity of one or more components to collect on
Why the surface of a solid
adsorption
The affinity depends on:
can happen? • Molecular size
• Shape
• Polarity
• System temperature or pressure
 Properties Physical Chemical
Physical vs Bonding Weak, long range Van der Short, short range
Chemical Waals interaction ionic or covalent
bond
Adsorption Heat of Low (20-40 kJ/mol) High (>40 kJ/mol)
adsorption

Saturation Monolayer or multilayer Monolayer only

Nature Reversible (by changing T Mostly irreversible

or P)
 Commercial adsorbents are highly porous, with pore surface areas
ranging from 100 to 1200 m2/kg. Large surface area allows a high
Adsorbent adsorption capacity. Typically, 98% of the adsorption occurs in the
pores and only 2% on the external surface.
Selection
Adsorbent Selection: Activated Carbon
• Hydrophobic and versatile;
• Activated carbon can be made by roasting various organic material, followed by
activation process such as heat treatment at 1000oc or higher at oxidizing
atmosphere.
• Properties can be tailored by changing production variables.

Science Direct
Adsorbent Selection: Synthetic Zeolite Molecular Sieve
• General formula:
Mx/n[(AlO2)x(SiO2)y].zH2O
M is metal cation (Li, Na, K, Ca, etc.) with
valence n.
• Have uniform aperture (pore) size
• Adsorption selectivity determined by pore
size, while activity is related to the size of
the cavity.
mdpi.com
Type Pore Size Applications
(Angstrom)
3A 3 Dehydration of unsaturated hydrocarbon
streams; drying polar liquids such as
methanol and ethanol; Adsorption of
NH3 and H2O from a N2/H2 flow.
4A 4 Static dehydration in closed liquid or gas
systems, e.g., in packaging of drugs,
electric components and perishable
chemicals; Adsorbed species include SO2,
CO2, H2S, C2H4, C2H6, and C3H6.
5A 5 Removal of H2S, CO2 and mercaptans
from natural gas
13X 10 Commercial gas drying, air plantfeed
purification (simultaneous H2O and CO2
removal) and liquid hydrocarbon/natural
gas sweetening (H2S and mercaptan
removal).
 Silica gel
Adsorbent Selection: Silica gel and Activated Alumina

Properties Silica gel/powder Activated Alumina

Polarity Polar Polar

Surface 300 – 850 m2/g ~320 m2/g

Area
Application Removal of water Dessicant to dry
and other polar gases; removal of Activated Alumina
components from fluoride, arsenic, and
gas stream; selenium from
humidity control in drinking water
food products, etc.
 Four basic methods:
Selection of method depends on adsorbent and adsorbate characteristics
Adsorbent
(1) Contact with gas/liquid which contain little or no adsorbate
Regeneration • Eg. Activated carbon for air/wastewater purification→Using
N2/clean air/ clean water purging

(2) Using chemicals that has higher affinity for the adsorbate
• Eg. Activated carbon for sugar colorant removal → using
NaOH
• Zeolite for heavy metal removal → using HCl
(3) Increasing temperature (Thermal Swing Adsorption)
• Eg. Silica gel for gas dehydration → TSA to evaporate water

(4) Decreasing pressure (Pressure Swing Adsorption)

• Eg. Zeolite for high purity oxygen production → PSA to
release N2

Adsorption
Isotherms
Langmuir
Adsorbent consists of
individual adsorption sites
which capable of adsorbing
one layer of molecule each
Chemi/Physisorption
(single component)
• Equilibrium relationship between the mass of volume
adsorbed to the partial pressure or concentration of
adsorbate in the solution at constant temperature.
• To determine the adsorbent capacity
• Different system → different isotherm
• Which isotherm model to be used is determined by
matching experimental data
Brunauer-Emmet-Teller (BET) Freundlich
Adsorbent consists of individual Adsorbent consists of individual
adsorption sites which capable of adsorption sites with different
adsorbing more than one layer of adsorption potential
molecules
Chemi/Physisorption Multilayer Physisorption
 Langmuir • Gas system:
Isotherms

Linearized
form

• Liquid system:

Other form

To check if Langmuir model is valid for a certain
system: [p/q vs p] or [c/q vs. c] is plotted
Where:
qA : amount of species A adsorbed (kg/kg adsorbent or
mol/kg adsorbent)
PA : partial pressure of species A at equilibrium
(mmHg, kPa, etc.)
cA: liquid concentration at equilibrium (mol/m3 or
kg/m3)
KA : adsorption equilibrium constant
Langmuir
Isotherms
• Usually less material is adsorbed as the temperature increase
• At different temperature; adsorption equilibrium constant (KA)
often follows Arhennius form:

∆𝐻 1
Linearized form: ln 𝐾𝑎 = − + ln 𝐾𝐴𝑂
𝑅 𝑇
If the Arhennius form is followed, a plot of ln Ka vs. 1/T
will be a straight line with slope of - ∆H/R
Where:
KAO : initial value
∆H : heat of adsorption (eg. In J/kg for SI)
R : gas constant (respective unit)
T : absolute temperature (K or R)
Langmuir
Isotherms
How much Calgon PCB activated carbon is needed to reduce the
concentration of methane from 40% mol to 5% mol by adsorption at
373 K and 200 kPa?
 Freundlich
Freundlich isotherm is the most widely used, especially for data which do
Isotherms not fit Langmuir isotherm
• Gas system: • Liquid system:
1ൗ 1ൗ
𝑞𝐴 = 𝐾𝑃𝐴 𝑛 𝑞𝐴 = 𝐾𝐶𝐴 𝑛

Linearized log qA = (1/n) log PA +log k

form slope intercept

log qA = (1/n) log CA + log k

Where:
(q) qA : amount of species A adsorbed per amount of adsorbent;
[in other forms q = x/m]
PA : partial pressure of species A at equilibrium/
after adsorption is complete (mmHg, kPa, etc.)
cA: concentration of solute remaining in solution at equilibrium/
after adsorption is complete (mol/m3 or kg/m3)
K, n : equilibrium constants to be determined from experiment

K and n are temperature dependent constant. In general, K decreases and n

increases with increasing temperature, indicating less adsorption capacity
Freundlich
Isotherms
Freundlich
Isotherms
Freundlich Example. Adsorption of benzene onto activated carbon has been reported to obey
the following Freundlich isotherm equation, where c is in mg/L and q is in mg/g:
Isotherms
qbenz = 50.1 cbenz
0.533

A solution at 25oC containing 0.50 mg/L benzene is to be treated in a batch process to

reduce the concentration to 0.01 mg/L. Calculate the activated carbon requirement.
Assignment 1
Carbon dioxide (CO2) is a major greenhouse gases that is fueling global warming. It is
therefore essential to develop Carbon Capture and Sequestration (CCS) technologies to
cope with the global demand of CO2 reduction. Among them, adsorption is one of the most
promising options due to its low energy consumption, low equipment costs and ease of
application (Mandal and Bandyopadhay, 2006).

Review one reputable international scientific journal or patent discussing CO2 adsorption
and make an one/two page summary (A4 size) which contains:
1) Choice of adsorbent, synthesis method and its physical properties
2) Type of adsorption (chemical/ physical) and adsorption isotherm
3) Optimum operating conditions
4) Regeneration method
5) Breakthrough curve
Submit one paper to be checked by me tomorrow. If it’s OK-ed, submit the review next week.
Filename: NIM_NAME_PAPER REVIEW
 ADSORBER
DESIGN
• Most common type : packed
column
• Continuous operation
• Most large scale operations
employ three columns
installed in series so that the
equipment can still be
operated (online) while one of
the columns is being
regenerated
Adsorber
design
1 Choose Adsorbent
& Particle Size
• Choose the adsorbent based on
adsorbent-adsorbate
characteristics, cost, extent of
removal, regeneration, so on.
• Preffered particle size is the
smallest one which still has
tolerable pressure drop. Gas
adsorption > liquid adsorption
particle size because of higher
diffusion rate.
• Pressure drop → Ergun equation
2 Choose superficial velocity
or EBCT (empty bed
contact time)
3
Calculate Bed
diameter &
length
• Suitable velocity→ highest velocity • Longer bed (+) → more
which provides sufficient residence adsorbent → longer time
time, adequate bed utilization, and before regeneration → higher
acceptable pressure drop. bed utilization efficiency.
• Gas velocity > liquid velocity • Longer bed (-) → taller column
because of higher diffusion rate. → more expensive, higher
• Typical velocities are 0.15 - 0.6 m/s pressure drop.
for gases and 0.001 – 0.004 m/s for
liquids
• Typical EBCT from low ppm to ppb
levels is ±15 min; from medium
ppm to ppb is ± 30 min.
Adsorber
design
 Breakthrough LES

Curve
• An S-curve which shows the ratio of solute
concentration in the outlet to solute LUB
concentration in the inlet [C/C0] fluid as a
function of time [t]
• Breakthrough curve can be obtained from
pilot plant experiment or predicted using
kinetic model [Thomas, Yoon & Nelson, etc.]

Total bed length (LB):

t
tB te

Length of equilibrium section (LES)

Length of unused bed (LUB) • Breakthrough time (tB) → when solute is first detected in the outlet
• Exhaustion time (te) → when C =C0
• t* =(tB - te)/2
When breakthrough occurs, adsorbent must be regenerated
Adsorber
design
Pressure Swing • Basic principle: different adsorption capacities at
different pressure & constant temperatures.
Adsorption • Strongly adsorbed component → heavy
• Weakly adsorbed component → light
PSA (Skarstrom) cycle
• Similar method: vacuum swing cycle
• Applications: drying gases, H2 purification,
production of O2 from air.
Pressure Swing
Adsorption

From compressor

PSA Flowsheet for on-site air separation (production of N2/O2)

ADSORPTION
SELECTIVITY

Pressure
Swing
 Thermal Swing • Basic principle: different adsorption capacity at
different temperatures & constant pressure.
Adsorption • Used for the recovery or removal of adsorbates
which are strongly adsorbed.
• Disadvantage: required large amount of pure hot
regeneration gas → might be expensive.
TSA cycle

OMICS International