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CE4020 Advanced Mass Transfer
By Dr Zhentao Wu
Email: z.wu7@aston.ac.uk
Office: MB 110 F
Tel: 0121 204 3353

Chemical Engineering and Applied Chemistry

College of Engineering and Physical Sciences

2020-2021
CE4020 Advanced Mass Transfer

Module aims:

 To introduce key concepts and principles of advanced mass transfer in

Adsorption and Membrane Separation, and advance such knowledge
towards appraising a variety of applications of the two separation technologies.

 From a mass transfer point of view, training module students to identify key
engineering design steps to improve Adsorption and Membrane Separation
processes, and appraise/predict advantages and limitations under a variety of
circumstances.
CE4020 Advanced Mass Transfer

Learning Outcomes

On completion of the module students will be able to:

 Comprehend major principles, theories and mechanisms of Adsorption and

Membrane Separation, and conclude the nature and categorisation of mass
transfer processes involved.

 Analyse key roles of mass transfer in Adsorption and Membrane Separation,

and based on this identity the controlling/limiting step of each separation
process.

 Propose effective measures to improve/intensify mass transfer for more

efficient Adsorption and Membrane Separation, and appraise
advantages/limitations of such measures under different circumstances.
CE4020 Advanced Mass Transfer

 Methods of delivery & learning hours

Delivery type Quantity Length of hours Student hours

Lecture and tutorial 12 24 76

- Live-sessions for lectures

- Pre-recorded materials for question practices, which will be put
in BB Collaborate, together with recording of live-sessions.

 Assessment
- BB test, 100% (2.5 hour, open book)

 Reference books

1. Seader et.al. “Separation Process Principles”, edition 2 or 3. Wiley.

2. Coulson & Richardson’s Chemical Engineering, volume 2
 CE4020 Advanced Mass Transfer

Background information: Separation technology

Can see how mature

technology is They are different

“into” “onto”

Maturity of separation technologies

(William Koros, adapted from Humphrey, J. L. and Keller, G. E., II, 1997, Separation Process Technology,
McGraw-Hill.)
CE4020 Advanced Mass Transfer

Background information: Separation technology & process

Adsorption 5 lectures + 1 tutorial

• Adsorbents: highly porous materials
• Adsorption equilibrium
• Adsorption kinetics and transport
• Adsorption column design
• The opposite process of Adsorption

Membrane 5 lectures +1 tutorial

• Membranes: Macro- & micro-structure, material, performance
• Membrane modules: module design and flow patterns
• Transport in membranes: restricted diffusion, solution diffusion
• Technologies: filtration, gas separation, reverse osmosis
Adsorption technology

 Lecture 1
• Adsorption technology
• Adsorbents: porous materials
• Adsorption equilibrium
• Use of adsorption equilibrium

Liquid Gas
https://youtu.be/PDeLzq3WNfY https://youtu.be/BAfoMXruUHA

Inside a column
https://www.youtube.com/watch?v=YVZ_rizK1FI
Adsorption technology
Adsorption technologies are technologies that separate a substance (adsorbate) from one
fluid phase out by accumulating the substance on the surface of a solid phase (adsorbent).
Adsorbate: atoms, ions or molecules from a gas or liquid; Adsorbent: Solid powdered materials

Example in everyday life - purification

Industry example - separation

www.psanitrogengasgenerator.com/

PSA Oxygen Gas Generators

Adsorption technology
• Adsorbents: porous materials

Examples of
commercial
adsorbents
Adsorption technology

• High selectivity for “sharp” separations What we want

from adsorption
• High capacity for a low amount of adsorbent technology
• Favourable kinetic for rapid sorption
• Chemical and thermal stability
• Great mechanical properties
• High resistance to fouling for long lifetime
• Capability of being regenerated
• Low cost
• ……
Adsorption technology
• Adsorbents: porous materials – what are they in common ?

• Pore size & surface area

• Pore size distribution

• Porosity

• Density

This is why aerogel is extremely light, with 90 to 99.8% porosity

 Adsorption technology
• Adsorbents: porous materials – what are they in common ?
Particle density • Pore volume
Pore size (differs from material density) • Material

20-70%

< 15 nm

Porosity Surface area

(differs from geometric surface area)

Human hair ranges from around 20 to 200 microns in width

Adsorption technology
• Adsorbents: porous materials How to obtain these details?
1. Pore size /diameter (IUPAC)
- Micropore < 2nm (molecular sieves)
- Mesopore 2 - 50 nm
- Macropore > 50 nm ume
re vol
e po
lativ
Cumu
2. Pore volume
trib ution
re size dis
Po
3. Pore size distribution

4. Porosity/void fraction (between 0 and 1)

- Pore volume / total volume of a solid

5. Surface area / volume ratio

6. Surface area
- Geometric surface area (determined by particle size)
- Specific surface area (rely on internal pore structures)

BET analysis based on BET equation

 Adsorption technology
• Adsorption mechanisms - depending on the forces between fluid molecules and
solid surface

– Physical adsorption (vander Waals adsorption)

• Mono-molecular layer
• Multi-molecular layers
• Capillary condensation (hysteresis)
• Pore volume  capacity
– Chemisorption (activated adsorption)
• Chemical bonds between adsorbent and adsorbate
• Typically monolayer

• Difference between chemisorption and physical adsorption

Criterion Physical adsorption Chemisorption

Forces Vander Waals Chemical bond
This means? Enthalpy 8-20 kJ/mol 40-800 kJ/mol
Temperature low high
Layers Mono- & multi- Normally mono-
Adsorption technology

• Equilibrium considerations
– Dynamic equilibrium established for solute distribution
between the fluid and solid surface, in terms of
• Partial pressure (gas) or Concentration (liquid)
• Solute loading on the adsorbent (mass, moles per unit
mass of adsorbent)
– Lack of theory on fluid-solid adsorption equilibria, different
from vapour-liquid and liquid-liquid counterparts
– Measure  adsorption isotherms

Brunauer’s five types of adsorption isotherms (Pure Gas)

Adsorption technology

• Equilibrium considerations
Adsorption technology

• Adsorption isotherms
o Limit to the completion of a single monolayer adsorbate at
the adsorbent surface
o Microporous solids (< 2nm), pore size not much larger than
the molecular diameter of the adsorbate
o Complete filling of the narrow pores corresponds to the
completion of a molecular monolayer.
o Quick growth in quantity at a low pressure
o Slower growth in quantity of adsorbate at increasing
pressures, until nearly flat
Both Type I and II are desirable isotherms,
exhibiting strong adsorption and good adsorption
at low pressures

o A wider pore size distribution

o Monolayer formed on all surface pores (point B)
o Followed by indefinite multi-layer formation in bigger
pores
Adsorption technology
• Adsorption isotherms

Desorption
Desorption

Adsorption
Adsorption

o Monolayer “missing” o A variation of Type II o A variation of Type III

o Low adsorption except at o With finite multi-layer o Hysteresis occurs
high pressure o Monolayer completes at o With capillary
o Not desirable point B condensations
o Rare cases o Hysteresis occurs

• Use of adsorption isotherms

– Selection of adsorbent or even the adsorption process as a unit operation
– Type I, II or IV can be used for separation purpose (monolayer at low pressures)
– Type III or V are not economical for separation
 Adsorption technology
Adsorption isotherms for pure propane vapour at 298-303K (commercial adsorbents)

• Varied adsorption capacity (material,

pore structures)
• Type I adsorption isotherms (within the
testing conditions)
• Quick growth in adsorption quantity at
low pressures

Effects of temperature and pressure (Adsorption-equilibrium of NH 3 on charcoal)

• Type I adsorption isotherms
• Higher temperature  lower adsorption
(exothermic process / intensified molecule
movements)

• At low adsorption range (<25 cm3/g) in

25 this figure, isotherms are almost linear,
called linear isotherm (similar to
Henry’s law)
Also indicate the “temperature window” for adsorption-desportion cycles
Adsorption technology
• Linear isotherm (similar to the form of Henry’s law)
equilibrium loading or amount of a empirical, temperature-dependent
given specie adsorbed / unit mass of constant for the component
adsorbent

Loading
𝑞=𝑘𝑝 Partial pressure of the species

Loading
P
Loading

T P

T T
P

• Heat of adsorption ()
𝑑 ln 𝑝 − ∆ 𝑯 𝒂𝒅𝒔
=
𝑑 log 𝑝 − ∆ 𝑯 𝒂𝒅𝒔 Log p
or =
𝑑𝑇 𝑅𝑇2 𝑑 (1 / 𝑇 ) 2.303 𝑅𝑇

decreases from initial 7300 cal/mol at Initial for monolayer formation is

10cm3/g, to 6100 cal/mol at 100 cm 3/g higher than the following successive
layers
− 𝐸𝑎 / ( 𝑅𝑇 ) 1/T
Arrhenius equation 𝑘= 𝐴 𝑒
Adsorption technology
• Freundlich isotherm
𝑞=𝑘 𝑝
1 /𝑛
𝑘= 𝑓 ( 𝑇 ) 𝑛= 𝑓 ( 𝑇 ) between 1∧5

• Langmuir isotherm – restricted to Type I isotherms & monolayer

Assuming surface of the pores of the adsorbent be homogeneous ( is constant), with
negligible interaction forces between adsorbed molecules.
If is the fraction of surface covered by adsorbed molecules, is thus the fraction of bare surface,
the net rate of adsorption is the difference between the rate of adsorption on the bare surface
and the rate of desorption on the converted surface

𝑑𝑞 / 𝑑𝑡 =𝑘𝑎 𝑝 ( 1 − 𝜃 ) − 𝑘𝑑 𝜃 Maximum load corresponding

to complete surface coverage
At equilibrium ,
𝐾𝑝 𝑘𝑎
𝜃=
𝑞
𝜃= 𝐾= 𝑞𝑚
1+ 𝐾𝑝 𝑘𝑑

At low pressures, , linear isotherm

𝐾 𝑝 𝑞𝑚 At intermediate pressures, is non-linear against pressures
𝑞=
1+ 𝐾𝑝 At high pressures,

More complicated isotherms for gas mixtures and liquids

Example – adsorption isotherm

1 m
Exercise I
A gas mixture from a chemical process contains benzene. The gas mixture flows into a
buffer tank, and needs to be treated by activated carbon (until the benzene concentration
is lower than ), before being vented into atmosphere. It takes 2 h to fill the buffer tank,
with the flow rate of the gas mixture of , at C and . The partial pressure of benzene
inside the gas mixture is approximately .

Gas Buffer
Adsorber Venting
mixture tank

Q1: Estimate the minimum quantity of activated carbon (in kg) required to treat the gas mixture,
using the isotherm data below.

Q2: Assuming an ideal fixed bed adsorber, while using 2 times the minimum of activated carbon for a
cycle time of 2 hours (i.e. regenerating the adsorbent when re-filling the buffer tank). If the adsorbent
bed is 1 m in depth, and bulk density of the adsorbent is , in a vertically oriented cylindrical vessel,
calculate the adsorber diameter

Q3: During the regeneration, superheated steam at 1.4 bar and C is used to recover benzene.
Calculate the quantity of benzene (in vapour) from the adsorber when the partial pressure of benzene
in the exist steam is less than 10 mmHg
 Exercise I

L/kg
(0 C, 1 atm )
Exercise I – Answer for Q1

at C 2h
¿ 5 𝑚𝑔/𝑚3
Gas Buffer
Adsorber Venting
mixture tank
benzene

Q1: Estimate the minimum quantity of activated carbon (in kg) required to treat the
gas mixture, using the isotherm data below.

The total mole of benzene 0.113 × 2× 3600 ×0.06 ×1000

¿ mol
in the buffer tank 0.082× ( 273+ 30 )

Partial pressure of benzene log ( 760 × 0.06 ) =1.66 Check equilibrium data
in log form, mmHg

This is PV = nRT so n = PV/RT so the volume is the flowrate

(0.113m/s) multiplied by the time it flowed for which is 2hours (times
by 3600 to change to seconds) then times by 1000 to convert m^3 to
litres then multiply by the pressure (0.06atm). Divide this by R (0.082)
multiplied by the temperature in kelvin (273 +30). This gives
1964.7mol.
Next we need the partial pressure of benzene. It is given as 0.06atm
but this is not the units for the diagram, we need to convert it to
mmHg so to do this you do the log of 0.06 times 760 = 1.66
 Exercise I – Answer for Q1

L/kg
(0 C, 1 atm )

110 L/kg

𝟏 . 𝟔𝟔
So use the value of 1.66 at a temperature of 30 degrees
Celsius to get this value from the graph. This means the
loading is 110 litres benzene per kg of activated carbon
under standard conditions.
Exercise I – Answer for Q1

at C 2h
¿ 5 𝑚𝑔/𝑚3
Gas Buffer
Adsorber Venting So at equilib
mixture tank have 110L/k
benzene
convert litres
pv=nrt so n =
The total amount of 0.113 × 2× 3600 ×0.06 ×1000 The pressur
¿ mol
benzene in the buffer tank 0.082× ( 273+ 30 ) equilibrium i
just V/RT = 4
Partial pressure of benzene
So, if we hav
log ( 760 × 0.06 ) =1.66 Check equilibrium data
1964.7mols
in log form
benzene and
Equilibrium benzene per kg ¿
110 of benzene p
of adsorbent
110 L/kg
0.082 × 273 ¿ 4.9 mol / kg adsorbent, t
of kg of abso
Minimum quantity of 1964.7 Do you agree with
¿ =401 kg required is 1
adsorbent reuqired 4.9 such a calculation?
= 401kg.
Temperature of the adsorber is not specified, which can be higher or lower than C, is thus
not considered for the above calculation. If we assume the isothermal operation of adsorber
at C, how to revise the above calculation ?
 Exercise I - Answer to Q2

Q2: Assuming an ideal fixed bed adsorber, while using 2 times the minimum of activated carbon
for a cycle time of 2 hours (i.e. regenerating the adsorbent when re-filling the buffer tank). If the
adsorbent bed is 1 m in depth, and bulk density of the adsorbent is , in a vertically oriented
cylindrical vessel, calculate the adsorber diameter
Gas Buffer
adsorber Venting
mixture tank

2 times the minimum of

activated carbon
kg So it says using 2
times the minimum
802 activated caron which
Volume of the adsorbent ¿ m3
450 is 401kg so 2x401kg =
802kg. It tells you bulk

adsorber diameter ¿
√ 1.78 × 4
1 ×3.14
m
density is 450kg/m^3
so the volume is
802kg/450kg/m^3=
1.78m^3. Then area =
(Pi d^2)/4 rearrange
for diameter.
Exercise I - Answer to Q3
Q3: During the regeneration, superheated steam at 1.4 bar and C is used to recover
benzene. Calculate the quantity of benzene (in vapour) from the adsorber when the
partial pressure of benzene in the exist steam is less than 10 mmHg

¿ 10 𝑚𝑚 𝐻𝑔
Gas Buffer
adsorber Venting
mixture tank

Superheat steam

Under ideal situations, we can assume that the vented stream (re-generation)
is in equilibrium with the benzene loading inside the adsorber

Partial pressure of can use this

¿ log ⁡(10)=1 Check equilibrium data
benzene assumption so
then use this
equation to get th
value of 1.
 Exercise I – Answer for Q3

L/kg
(0 C, 1 atm )

15 L/kg

𝟏
From the graph get a
value of 15L/kg
Exercise I - Answer to Q3
Q3: During the regeneration, superheated steam at 1.4 bar and C is used to recover
benzene. Calculate the quantity of benzene (in vapour) from the adsorber when the Again
partial pressure of benzene in the exist steam is less than 10 mmHg conv
pv=n
¿ 10 𝑚𝑚 𝐻𝑔 equil
Gas Buffer
adsorber Venting and i
mixture tank
from
Superheat steam R is c
and T
Under ideal situations, we can assume that the vented stream (re-generation) multi
is in equilibrium with the benzene loading inside the adsorber
to ge
Partial pressure of its ow
¿ log ⁡(10)=1 Check equilibrium data
benzene
Benz
Mole of benzene left 15 is 19
¿ ×802 mol 1427
inside the adsorber 0.082 ×273
conv
Benzene recovered ¿ 1964.7 − 537.4=1427.3 𝑚𝑜𝑙=1427.3 × 78=111.3𝑘𝑔 by M
111.3
In Q1, if we assume the isothermal operation of adsorber at C, how to revise the calculation to
Q1? And how it will affect the answers to Q2 and Q3?