Separation Processes

Laboratory

Membranes –
Lecture 01 and 02
Dr. Viola Becattini
Separation Processes Laboratory
Rate Controlled Separations
28.10.2021 – 04.11.2021
Outline – Lecture 28.10.2021

1. Basics, definitions, and module design

2. Simple well-mixed module

3. Solution-diffusion model

4. Reverse osmosis

5. Gas permeation

6. Recap

Separation Processes Laboratory 28.10.21 2

Outline – Lecture 28.10.2021

1. Basics, definitions, and module design

2. Simple well-mixed module

3. Solution-diffusion model

4. Reverse osmosis

5. Gas permeation

6. Recap

Separation Processes Laboratory 28.10.21 3

Membranes: Basics
FEED RETENTATE

Driving
MEMBRANE force

SWEEP PERMEATE
(optional)

• A membrane is an interfacial structure that restricts the movement of some species while allowing
other species to permeate through (if there is a driving force, e.g., gradient of pressure,
concentration, or chemical potential).

• Membranes are used in a wide range of applications, because:

1. Allow controlling carefully the permeation rate of a chemical species
2. Are inherently low-energy consumers (if pressure-energy is available)
3. Have simple design and no moving parts

Separation Processes Laboratory 28.10.21 4

Membranes: Definitions
FEED RETENTATE

Driving
MEMBRANE force

SWEEP PERMEATE
(optional)

• Feed: stream entering the membrane separation module.

• Permeate: stream that is separated from the feed and therefore crosses the membrane barrier.
• Permeate flux: term describing the rate at which a product passes through a membrane. Flux is
specific to the membrane, the application, the operating conditions, and usually varies in time.
• Retentate: amount of the feed stream that is not separated.
• Permeability: coefficient linking the flux to the driving force (and to the membrane thickness).
• Selectivity: ratio of permeability coefficients of two species (grater or equal to 1).
• Sweep: (optional) stream entering the membrane on the permeate side and conveying the permeate.

Separation Processes Laboratory 28.10.21 5

Membranes: Basic Requirements

• High permeability for the component to be separated (smaller area for given permeate flow)

• High selectivity toward the component to be separated in relation to other components (higher
purity)

• Low effective thickness of the active portion of the membrane (to ensure a high permeation and
low cost)

• Good mechanical strength to support the physical structure

• High membrane stability in real working conditions (e.g., humidity)

• Uniformity-freedom from pinholes or other defects

Separation Processes Laboratory 28.10.21 6

Membrane Separation Processes

• Microfiltration (MF): Filtration of micron particulates from liquid and gases à Pressure gradient
E.g., Sterilization of drugs, clarification and biological stabilization of beverages, purification of antibiotics

• Ultrafiltration (UF): Removal of macromolecules and colloids from liquids à Pressure gradient
E.g., Pre-concentration of milk before making cheese, clarification of fruit juice, recovery of vaccines and antibiotics from
fermentation broth

• Reverse Osmosis (RO): Removal of all material from water or other solvents à Pressure gradient
E.g., Desalinization of brackish water, treatment of wastewater to remove a wide variety of impurities, treatment of surface and
ground water, removal of alcohol from beer and wine

• Gas Separation (GS): Selective separation of mixtures of gases and vapors à Pressure gradient
E.g., Separation of CO2 or H2 from methane and other hydrocarbons, adjustment of the H2/CO ration in synthesis gas, separation of
air into nitrogen and oxygen enriched streams, recovery of helium, recovery of methane from biogas

• Pervaporation (PV): Separation of mixtures of miscible liquids à Concentration gradient

E.g., Dehydration of ethanol-water azeotrope, removal of water from organic solvents, removal of organics from water

• Electric Dialysis (ED): Selective transport of only ionic species à Electrical potential gradient
E.g., Production of table salt from seawater, demineralization of cheese whey, production of ultrapure water for semiconductor
industry

Separation Processes Laboratory 28.10.21 7

Membrane Separation Processes
Types of membrane processes, the particle size typically removed by the membrane, and the driving force of the processes

Separation Processes Laboratory H. K. Shon et al., Nanofiltration for water and wastewater treatment – a mini review, Drink. Water Eng. Sci., 2013 28.10.21 8
Membrane classification: Structure and separation principles

Synthetic membranes can be classified based on their (i) structure and separation principles, (ii) morphology, (iii)
membrane material.

Structure and separation principles:

Porous (mean pore size diameter 5000-1 nm): induce

separation by discriminating between particle size; the
selectivity is mainly determined by the pore size in relation
to the size of the particles to be separated, with the
membrane material having only a small effect on the
separation.

Nonporous (mean pore size diameter less than 1nm): able to separate molecules of approximately the same size from
each other; separation takes place through differences in solubility and/or in diffusivity; intrinsic properties of the
polymeric material determine the extent of selectivity and permeability.

Carrier membranes (charged or with special chemical affinity): transport solely determined by very specific carrier
molecule, which allows achieving extremely high selectivity; similar functionality to cell membrane.

Mulder, Basic Principles of Membrane Technology, 1996.

Separation Processes Laboratory 28.10.21 9

Membrane classification: Morphology
Schematic representation of membrane cross-sections.
• Isotropic (“symmetric”) membranes have a uniform
composition and structure throughout:
- They can be porous or dense
- Resistance to mass transfer determined by the total
membrane thickness (generally between 10 and 200 µm)
- A decrease in membrane thickness results in in an
increased permeation rate
• Anisotropic membranes ( “asymmetric”): thin, selective top
layer (or skin, 0.1-0.5 µm) supported on a much thicker,
highly permeable and porous sublayer
- They combine the high selectivity of a dense membrane
with the high permeation rate of a very thin membrane
- Resistance to mass transfer determined largely or
completely by the thin top layer
• Composite membranes: top layer and sublayer can be
optimized independently; generally, the support layer is
already an asymmetric membrane on which a thin dense
layer is deposited.

Mulder, Basic Principles of Membrane Technology, 1996.

Separation Processes Laboratory 28.10.21 10

 Membrane classification: Anisotropic membranes

ß Functionality à • The discovery and development of

anisotropic membranes (for reverse
osmosis seawater desalination, by
ß Support à Loeb and Sourirajan, 1963) was a
mechanical strength critical breakthrough in membrane
technology

Ø The cross-sectional microstructures

of an anisotropic membrane: (a) the
general view, (b) top layer, (c) top
layer and porous sublayer, (d) the
porous sublayer.

Chen, L. et al., (2018). Asymmetric membrane structure: An efficient approach to enhance hydrogen separation performance. Separation and Purification Technology, 207, 363-369.

Separation Processes Laboratory 28.10.21 11

Membrane materials: Synthetic membranes
Organic Inorganic

Polymer Ceramic Metallic Carbon

membranes membranes membranes membranes
(cellulose, PTFE, (metal oxide, metal (palladium and (graphene, CNTs,
PVDF, PP) carbide, zeolite) palladium alloys) coal)

• Rigid in glassy
form or flexible • Chemically and thermally stable, mechanically robust,
in rubbery state operational under harsh feed conditions
• Cost-effective,
good selectivity, • Withstand harsh chemical cleaning, ability to be sterilized and
autoclaved, high temperature (up to 500°C) and water
easy
processability resistance, well-defined and stable pore structure, high
• Fouling, chemical stability, long life time
chemically non
resistant, limited • Fragile, rigid
operating T & P,
short life time

Kayvani Fard, A. et al., (2018). Inorganic membranes: Preparation and application for water treatment and desalination. Materials, 11(1), 74.

Separation Processes Laboratory 28.10.21 12

Membrane modules
• Module: smallest unit into which the membrane area is packed à Several module configurations available
• System: arrangement of a number of single modules
Module
Feed Retentate

Permeate

• Flat configuration
i. Plate-and-frame modules
ii. Spiral-wound modules Choice of module depends on:
- Economic considerations
- Separation problem
- Ease of cleaning, maintenance, operation
• Tubular configuration - Compactness of the system
i. Tubular modules (D>10.0 mm) - Scale and possibility of membrane replacement
ii. Capillary modules (D: 0.5-10.0 mm)
iii. Hollow-fiber modules (D<0.5 mm)

Separation Processes Laboratory 28.10.21 13

 Plate-and-frame modules

• Similar to laboratory configuration

• Sets of two membranes are placed in a sandwich-like
fashion with their feed sides facing each other
• Packing density: 100-400 m2/m3

Mulder, Basic Principles of Membrane Technology, 1996.

Separation Processes Laboratory 28.10.21 14

Spiral-wound modules

• Plate-and-frame system wrapped around a central collection

pipe
• Fairly low manufacturing costs
• High surface to volume ratio (packing density: 300-1000
m2/m3)
• Modules can be easily connected in series inside a tubular
pressure vessel
• The feed flows axial through the cylindrical module parallel
along the central pipe whereas the permeate flows radially
toward the central pipe

Separation Processes Laboratory 28.10.21 15

Spiral-wound modules

Separation Processes Laboratory 28.10.21 16

Tubular modules

Permeate
Membrane
• The feed always flows through the
Feed Stream/Retentate center of the tubes while the permeate
Feed flows through the porous supporting
tube into the module housing
Stream
• Not self-supporting
• High cost (low surface / volume ratio)
Retentate
• Packing density: less than 300 m2/m3
• Turbulent flow à good resistance to
fouling
• Ceramic membranes mostly assembled
in these modules
Permeate

https://synderfiltration.com/learning-center/articles/module-configurations-process/tubular-membranes/

Separation Processes Laboratory 28.10.21 17

Hollow-fiber module

Porous, dense and double layer hollow fibers.

• The feed solution can enter inside the fiber («inside-out») or on the outside
(«outside-in»)
• Highest packing density: up to 30’000 m2/m3
• Used when the feed stream is relatively clean, e.g., gas separation or
pervaporation

Separation Processes Laboratory 28.10.21 18

Membrane processes: Advantages and challenges

ü Appreciable energy savings with respect to x Fouling: (ir)reversible deposition of material

alternative separations (ambient in the membrane causing a decrease in flux
temperature) over time

ü Easy to operate and control x Withstanding high pressure differences with

limited membrane thickness
ü Compact system
x Increasing selectivity for specific applications
ü High flexibility in designing the systems
x Uniformity of pore sizes
ü Lower capital cost than alternatives
x Temperature stability

Separation Processes Laboratory 28.10.21 19

Outline – Lecture 28.10.2021

1. Basics, definitions, and module design

2. Simple well-mixed module

3. Solution-diffusion model

4. Reverse osmosis

5. Gas permeation

6. Recap

Separation Processes Laboratory 28.10.21 20

Simple well-mixed membrane module
Assumptions
• No chemical reactions

∞
• No pressure drop
• Well-mixed in both sides

∞
Nomenclature
• n:̇ molar flow rate
z • yi: molar fraction of species i
• L: length of the membrane module

Control volume Total mass balance :

Single species mass balance :

Separation Processes Laboratory 28.10.21 21

Simple well-mixed membrane module
Assumptions
• No chemical reactions

∞
• No pressure drop
• Well-mixed in both sides

J
∞
Nomenclature
• n:̇ molar flow rate
• yi: molar fraction of species i
• L: length of the membrane module

Control volume Total mass balance :

• J is the total molar flux of permeating species:
• A is the membrane section area where mass transfer occurs

Single species mass balance :

Separation Processes Laboratory 28.10.21 22

Simple well-mixed membrane module

Overall driving force producing movement of a permeant is the gradient in its chemical potential:
𝑑𝜇!
𝐽! = −𝐿!
𝑑𝑥
"#!
Where is the gradient in chemical potential of component i and 𝐿! is a coefficient of proportionality.
"$

Ø Main assumption governing transport though membrane: The chemical potential of the feed or
permeate fluids are in equilibrium with the adjacent membrane surfaces à Continuous gradient in
chemical potential from one side of the membrane to the other*
High pR Low pP
(Retentate) (Permeate)
Membrane
Ø Two models based on the way
𝜇! the chemical potential gradient
in the membrane phase is
expressed

*Therefore, rate of absorption and desorption at

the membrane interface are much higher that the
rate of diffusion through the membrane
x Wijmans, Johannes G., and Richard W. Baker. "The solution-diffusion
model: a review." Journal of membrane science 107.1-2 (1995): 1-21.
Separation Processes Laboratory δ 28.10.21 23
Outline – Lecture 28.10.2021

1. Basics, definitions, and module design

2. Simple well-mixed module

3. Solution-diffusion model

4. Reverse osmosis

5. Gas permeation

6. Recap

Separation Processes Laboratory 28.10.21 24

 Models for permeating processes

Pore-flow model Solution-diffusion model

Permeants are separated by a pressure-driven convective Permeants first dissolve in the membrane matrix and then
flow through tiny membrane pores diffuse through the membrane under a concentration gradient
Ø Separation achieved because one of the permeants is Ø Separation achieved because of differences in the
excluded from some of the pores in the membrane solubility of each permeants into the membrane material
through which other permeants move and their diffusivity through the membrane
Ø It assumes that the chemical potential gradient across the Ø It assumes that the chemical potential gradient across the
membrane is expressed solely as a pressure gradient membrane is expressed solely as a concentration gradient
Ø Widely accepted model for transport in reverse osmosis,
gas permeation, and pervaporation
Separation Processes Laboratory 28.10.21 25
Solution-diffusion model
High pR Low pP
(Retentate) (Permeate)
Membrane
Assumptions
𝜇!
• Isothermal process
• Constant pressure within the membrane, equal to
pF=pR
the retentate pressure (high pressure value)
• Components dissolved in dense membranes act as wi,R pP
if they were a liquid wi,P
x
δ

Assuming the validity of Fick’s Law within the membrane:

Integration over the

membrane thickness

where Di is the diffusion coefficient, and wi is the molar fraction of species i

dissolved in the membrane at the retentate (wi,R) or permeate interface (wi,P)

Separation Processes Laboratory 28.10.21 26

Solution-diffusion model
Since dissolved components in dense membranes act as if they were liquid, the fugacity of species i inside of
the membranes is given by:

Where:
• is the pure liquid fugacity of species i
• is the Poynting factor of species i à pressure inside the membrane is
constant and equal to pR
• is the vapor pressure of species i
By replacing wi,R and wi,P in the expression of the permeation flux using the definitions of the fugacities, one
can obtain the final expression of the solution-diffusion model :

Ø Apply the iso-fugacity equilibrium condition at the fluid/membrane interface to obtain the permeating flux of
species i as a function of the retentate and permeate concentrations
Separation Processes Laboratory 28.10.21 27
 Solution-diffusion model: iso-fugacity equilibrium condition

à Thermodynamic equilibrium: iso-fugacity of component i

at the membrane/fluid interface

High pR Low pP High pR Low pP High pR Low pP

(Retentate) (Permeate) (Retentate) (Permeate) (Retentate) (Permeate)
Membrane Membrane Membrane

Liquid Liquid Gas Gas Liquid Gas

(+) (() (,) (() (+) (()
𝑓!,& 𝑓!,& 𝑓!,& 𝑓!,& 𝑓!,& 𝑓!,&
(() (+) (() (,) (() (,)
𝑓!,* 𝑓!,* 𝑓!,* 𝑓!,* 𝑓!,* 𝑓!,*
pF=pR
pP pP pP
x x x
δ δ δ

• Liquid-liquid separation • Gas-Gas separation • Liquid-Gas separation

à Reverse osmosis à Gas permeation à Pervaporation

Separation Processes Laboratory 28.10.21 28

Outline – Lecture 28.10.2021

1. Basics, definitions, and module design

2. Simple well-mixed module

3. Solution-diffusion model

4. Reverse osmosis

5. Gas permeation

6. Recap

Separation Processes Laboratory 28.10.21 29

Reverse osmosis
Osmosis (reverse or normal) refers to the use of a permselective membrane (membrane that is freely
permeable to water but much less permeable to salt) to separate a salt solution from pure water.

Solution-diffusion model:

Fugacities of the liquids at the membrane interface and local equilibrium condition: High pR Low pP
(Retentate) (Permeate)
Membrane

Liquid Liquid
(+) (()
𝑓!,& 𝑓!,&
(() (+)
𝑓!,* 𝑓!,*
pF=pR
pP
x
δ

Separation Processes Laboratory 28.10.21 30

Reverse osmosis
The equation is simplified by assuming that the ratio between the activity coefficients is the same at the
retentate or at the permeate side:

: Sorption coefficient of species i in the membrane

: Diffusion coefficient of species i in the membrane

: permeability of species i in the membrane (extent at which a species dissolves

and diffuses through a membrane)

: permeance of species i in the membrane

𝑣1! (𝑝& − 𝑝* )
𝐽! = 𝑃! 𝑦!,& − 𝑦!,* exp(− )
𝑅𝑇

Separation Processes Laboratory 28.10.21 31

 Reverse osmosis: Water desalination
At t=0s, we have side (1) that has salt water and side (2) that has only
water. If both p1 and p2 are atmospheric pressure, then we have :

p1 p2

The osmotic pressure Δπ is the pressure difference necessary to

t = 0s
Δπ have a null water flux through the membrane, due to the
concentration differences in the two sides of the membrane :
t = ∞s

Salt + H2O H2O

(1) (2)
Jw
For dilute systems (𝑦-,. ≈ 1), a linear approximation can
be used for the logarithm:
!"
Δ𝜋 = $# (1 − 𝑦%,' )
!

Separation Processes Laboratory 28.10.21 32

 Reverse osmosis: Water desalination

𝑄- 𝑣1- ∆𝑝
p1 p2 𝐽- = 𝑦 − 𝑦-,. exp(− ) with ∆𝑝 = (𝑝/ − 𝑝. )
𝛿 -,/ 𝑅𝑇

• p1 – p2 < Δπ : Normal osmosis, water flows from the pure water

Δp>Δπ side to the sea-water side

• p1 – p2 = Δπ : Osmotic equilibrium, no flux since the osmotic

pressure is counterbalanced by the pressure difference

Salt + H2O H2O • p1 – p2 > Δπ : Reverse osmosis, water flows from the sea water
(1) (2) side to the pure water side : water desalination
Jw

Separation Processes Laboratory 28.10.21 33

Outline – Lecture 28.10.2021

1. Basics, definitions, and module design

2. Simple well-mixed module

3. Solution-diffusion model

4. Reverse osmosis

5. Gas permeation

6. Recap

Separation Processes Laboratory 28.10.21 34

Gas permeation
Gas permeation corresponds to the separation of gases. Typically, a high pressure gas mixture at pR is
fed to one side of the membrane while the permeate is removed on the other side at a lower pressure pP
High pR Low pP
(Retentate) (Permeate) Solution-diffusion model:
Membrane

Gas Gas
(,) (()
𝑓!,& 𝑓!,&
(()
Fugacities of the gases at the membrane interface and local equilibrium condition:
(,)
𝑓!,* 𝑓!,*

pP
x (,) P
𝐾!,&
δ

: sorption coefficient of species i in the membrane

: diffusion coefficient of species i in the membrane permeability of species i
in the membrane
Separation Processes Laboratory 28.10.21 35
Gas permeation
Assuming the equality of sorption coefficients respectively on the retentate and permeate sides, and
considering that the Poynting correction factor is close to 1 for systems at relatively low pressure:

Where ; : Permeance of species i in the membrane

Selectivity: Pressure ratio:

Permeate concentrations from the permeating fluxes :

For a binary mixture (A+B), the equation becomes quadratic with respect to y1,P and can be solved:

Separation Processes Laboratory 28.10.21 36

Gas permeation: Binary mixture

∞ Assumptions
• No chemical reactions
• No pressure drop
∞ • Well-mixed on both sides

For a binary mixture A-B, we do not write the subscripts for the compounds anymore, but consider that
yA,P=yP and yA,R=yR. The complete model equations are :

Known parameters (3) :

Unknown parameters (8) :

Equations (6) 2 degrees of freedom

Separation Processes Laboratory 28.10.21 37

Gas permeation: Binary mixture and design considerations
We define characteristic dimensionless parameters for a membrane separation:

Selectivity: Pressure ratio: Stage cut:

Recovery: Purity:

Given the operating conditions (pressures, retentate stream properties, flow patterns), the membrane
technology (permeability, selectivity, thickness) and the upstream conditions (feed stream properties),
the process performance (recovery, purity and required membrane area) can be calculated.
Two degrees of freedom: in the design of a membrane
process, two parameters can be fixed (e.g., Re and Pu)
For the simple well-mixed module:

Separation Processes Laboratory 28.10.21 38

Gas permeation: Binary mixture and design considerations

Let : Selectivity limited region

Pressure ratio limited region

(φ >> α) selectivity limited (α >> φ) pressure-ratio limited

Separation Processes Laboratory 28.10.21 39

Gas permeation: Binary mixture and design considerations
Polymeric membrane materials: Selectivity and permeability have a pareto-optimum, obtained from
empirical observations

For materials close to the Robenson Upper Bound, it is not possible to increase simultaneously the
selectivity and the permeance à Trade-off between increasing the purity or the stage-cut

Separation Processes Laboratory Robenson, L. M., The Upper Bound Revisited, 2008. 28.10.21 40
Gas permeation: Binary mixture and design considerations
The recovery and purity maps on the A – β shows
the limitations of a one stage membrane process :

• Recovery and purity behave oppositely with

respect to changes in membrane area. The
recovery increases while the purity decreases
as the area increases, due to the permeation of
the least permeant component along the module
à High purity is only achievable at low recovery
rate (possibly not economical)

• An increase in selectivity (decrease in

permeability) leads to an increase in purity
(decrease in recovery).

• For large selectivity and pressure ratio, the

permeate purity is almost independent from the
membrane area

Separation Processes Laboratory 28.10.21 41

Outline – Lecture 28.10.2021

1. Basics, definitions, and module design

2. Simple well-mixed module

3. Solution-diffusion model

4. Reverse osmosis

5. Gas permeation

6. Recap

Separation Processes Laboratory 28.10.21 42

Solution-diffusion model: General approach - Summary
High pR Low pP
a. Apply Fick’s law within the membrane: (Retentate) (Permeate)

𝐷! With wi being the molar fraction of species i

Membrane
𝐽! = 𝑐 (𝑤!,& − 𝑤!,* )
𝛿 dissolved in the membrane
(0) (()
𝑓!,& 𝑓!,&
b. Replace wi,R and wi,P in the expression of the permeation flux Ji using the definitions of
(&) (&)
the fugacities inside the membrane 𝑓",$ and 𝑓",( (() (0)
𝑓!,* 𝑓!,*
c. The chemical potential of the retentate and permeate fluids (f) are in equilibrium pF=pR
with the adjacent membrane surfaces à apply iso-fugacity equilibrium condition pP
x
(0) (() (0) (()
𝑓!,& = 𝑓!,& and 𝑓!,* = 𝑓!,* δ
d. The fugacity in the fluid and membrane phases can be equated using the appropriate expressions for the gas and
liquid fugacity (for the retentate and permeate sides):
(0) (() (+) 1 + 𝑣1! (𝑝& − 𝑝!1 )
𝑓!,& = 𝑓!,& = 𝑓!,& = 𝑝! (𝑇)𝑦!,& 𝛾!,& exp( ) For liquid
𝑅𝑇
(0) (() (,)
𝑓!,& = 𝑓!,& = 𝑓!,& = 𝑝& 𝑦!,& 𝜙!,& For gas
()) ())
d. Plug-in the fugacity definitions for the fluid on the retentate and permeate sides (𝑓",$ and 𝑓",( ) in the permeation flux
expression Ji , which can be expressed as function of the concentration of species i in the retentate and permeate
(𝑦",$ and 𝑦",( )
Separation Processes Laboratory 28.10.21 43
Outline – Lecture 04.11.2021

• Recap

• Pervaporation

• Membrane modules:

- Challenges for membrane commercial application

- Limits of a single-stage membrane process

- Multi-stage cascade processes

• Graphene membranes (Dr. Karl-Philipp Schlichting)

• Summary: Main concepts for binary systems (not on slides)

Separation Processes Laboratory 04.11.21 44

Pressure drop in a hollow fibre module

Hagen-Poiseuille pressure drop in a laminar flow

inside of a tube of internal radius r

Inside of the hollow fibre, in the retentate side, the

derivation is straightforward :

McKeen, L. W., Permeability properties of plastics and elastomers, 2016.

Sekino, Masaaki. "Study of an analytical model for hollow fiber reverse

osmosis module systems." Desalination 100.1-3 (1995): 85-97.
Hanbury, W. T., et al. "Pressure drops along the bores of hollow fibre
membranes—their measurement, prediction and effect on fibre bundle
performance." Desalination 38 (1981): 301-318.
Separation Processes Laboratory 04.11.21
Pressure drop in a hollow fibre module

For the permeate side, one has to define a hydraulic

diameter since the shape is not tubular.
Assumption: square pitch mode arrangement of the
hollow fibres inside of the module

We define the packing ratio ϕ of the module, ranging

between 45% and 60% in commercial modules :

cross-section

The hydraulic diameter for the permeate side is

defined such that the red surface is worth :

Eventually, one finds the hydraulic diameter :

Separation Processes Laboratory 04.11.21

Pressure drop in a hollow fibre module

Hagen-Poiseuille pressure drop in a laminar flow

with a hydraulic radius rh

cross-section Outside of the hollow fibre, in the permeate side, the

pressure drop is :

Separation Processes Laboratory 04.11.21

Solution-diffusion model: General approach - Summary
High pR Low pP
a. Apply Fick’s law within the membrane: (Retentate) (Permeate)

𝐷! With wi being the molar fraction of species i

Membrane
𝐽! = 𝑐 (𝑤!,& − 𝑤!,* )
𝛿 dissolved in the membrane
(0) (()
𝑓!,& 𝑓!,&
b. Replace wi,R and wi,P in the expression of the permeation flux Ji using the definitions of
(&) (&)
the fugacities inside the membrane 𝑓",$ and 𝑓",( (() (0)
𝑓!,* 𝑓!,*
c. The chemical potential of the retentate and permeate fluids (f) are in equilibrium pF=pR
with the adjacent membrane surfaces à apply iso-fugacity equilibrium condition pP
x
(0) (() (0) (()
𝑓!,& = 𝑓!,& and 𝑓!,* = 𝑓!,* δ
d. The fugacity in the fluid and membrane phases can be equated using the appropriate expressions for the gas and
liquid fugacity (for the retentate and permeate sides):
(0) (() (+) 1 + 𝑣1! (𝑝& − 𝑝!1 )
𝑓!,& = 𝑓!,& = 𝑓!,& = 𝑝! (𝑇)𝑦!,& 𝛾!,& exp( ) For liquid
𝑅𝑇
(0) (() (,)
𝑓!,& = 𝑓!,& = 𝑓!,& = 𝑝& 𝑦!,& 𝜙!,& For gas
()) ())
d. Plug-in the fugacity definitions for the fluid on the retentate and permeate sides (𝑓",$ and 𝑓",( ) in the permeation flux
expression Ji , which can be expressed as function of the concentration of species i in the retentate and permeate
(𝑦",$ and 𝑦",( )
Separation Processes Laboratory 04.11.21 48
Pervaporation
An intermediate separation process between gas separation and reverse osmosis processes: the
retentate is in liquid phase and the permeate is in gas phase. The feed pressure is sufficient to
maintain liquid state on the retentate side even as the composition is changing. The permeate pressure is
fixed to a value below the saturation pressure of the permeating mixture, often applying vacuum.
The isothermal assumption will be assumed for simplicity, but in reality an energy balance equation should
be coupled with material balances to account for the heat of vaporization.
High pR Low pP
(Retentate) (Permeate)
Membrane
Solution-diffusion model:
Liquid Gas
(+) (()
𝑓!,& 𝑓!,&
(() (,)
𝑓!,* 𝑓!,* Fugacities of the gases at the membrane interface and local
equilibrium condition:
pP
x
δ
Ø Local equilibrium at interfaces
Ø No mass transfer resistance in the
retentate and permeate streams
Separation Processes Laboratory 04.11.21 49
Pervaporation
The solution-diffusion model equation for pervaporation becomes:

: gas sorption coefficient of species i in the membrane

: liquid sorption coefficient of species i in the membrane
: diffusion coefficient of species i in the membrane

: Henry’s constant solubility for species i (liquid-vapor equilibrium property)

: gas permeability of species i in the membrane

Considering that the Poynting correction factor is close to 1 for systems at relatively low pressure,
we have:

Separation Processes Laboratory 04.11.21 50

Pervaporation: Separation Factor

We can define the vapor pressures of the liquid retentate (pi,R) and of the permeate (pi,P) :

The separation factor indicates how well was the component i separated compared to component j.
To note that we have :
In pervaporation, the separation
factor is a product of two terms: One
represents the contribution of
relative volatility, and the other the
contribution of the membrane.

Now we have three factors: the

contribution of relative volatility, the
selectivity of the membrane and the
vapor pressures of feed and
permeate (operating parameters).
Separation Processes Laboratory 04.11.21 51
Separation Factor: Limiting Scenarios

1. High selectivity scenario α >> (pR/pP) : 3. Low pressure ratio, low selectivity:
Species i is preferred and dilute :

All these effects are dominated by the

fact that α is not constant, but usually
a strong function of yR:
α = α (yR)
2. High pressure ratio scenario (pR/pP) >> α: Hence it is possible to have both
α>>(pR/pP) and (pR/pP)>>α for the
same membrane and ratio pR/pP,
simply by varying yR.

Separation Processes Laboratory 04.11.21 52

Design considerations for pervaporation processes

• The minor component should permeate

(always favorable in membrane separation)
• To benefit from high selectivities, one should start from highly concentrated feeds
(hence hybrid processes are favorable, e.g. distillation + membrane separation)
• Working at elevated temperatures facilitates the process
(the latent heat of vaporization has to be provided with the feed)
• The pressure ratio is usually increased by applying vacuum on the permeate side
(e.g. by cooling condensation of the permeate stream)
• Mass transfer resistance through the surface boundary layer has to be considered
(especially if high purity of the retentate stream is desired)

Separation Processes Laboratory 04.11.21 53

Comparison of osmosis, gas permeation and pervaporation

Solution-diffusion model equations

pP,sat

Separation Processes Laboratory 04.11.21 54

Comparison of osmosis, gas permeation and pervaporation

Separation Processes Laboratory 04.11.21 55

Outline – Lecture 04.11.2021

• Recap

• Pervaporation

• Membrane modules:

- Challenges for membrane commercial application

- Limits of a single-stage membrane process

- Multi-stage cascade processes

• Graphene membranes (Dr. Karl-Philipp Schlichting)

• Summary: Main concepts for binary systems (not on slides)

Separation Processes Laboratory 04.11.21 56

 Challenges for membrane commercial application

Commercial Membrane Process

Produce a selective, high flux, thin and defect free

Material science
membrane

Key Assemble membranes into compact, high surface

Manufacture
area, economical membrane modules
Challenges

Develop an energetically and economically optimised

Process Design
and reliable process

Separation Processes Laboratory 04.11.21 57

One stage process : limitations

Robenson, L. M., The Upper Bound Revisited, 2008.

Close to the Upper Bound, it is not possible to For a given membrane material, further
increase simultaneously the membrane increasing the pressure ratio becomes
selectivity and permeability uneffective due to the selectivity-limited region
=> Limitation due to membranes properties => Limitation due to the permeation physics

58
Separation Processes Laboratory 04.11.21
One stage process : limitations

The recovery and purity maps show the limitations

of a one stage membrane process :

• Recovery and purity behave oppositely against

the membrane area
• => High permeate purity is only achievable at
low recovery rate, which is not economical

• An increase in selectivity (decrease in

permeability) leads to an increase in purity
(decrease in recovery).

Separation Processes Laboratory 04.11.21

Multi-stage cascade membrane processes
The separation of a volatile organic compound (VOC, e.g. ethane, butane, methanol,…) from a nitrogen
feed gas is studied. The permeances of the membranes are calculated with the Robenson’s Upper Bound.

The one-stage system does not provide

the desired separation. The VOC purity
(4.1%) and the recovery (90%) are too low.

This two-stage system is used to decrease

the VOC concentration at the outlet. The
recovery is now of 99%, but the VOC purity
is still low.

Rule of thumb : Area required to remove first 90% of the VOC = Area required to remove last 9% of the VOC

Separation Processes Laboratory 04.11.21

Multi-stage cascade membrane processes
The separation of a volatile organic compound (VOC, e.g. ethane, butane, methanol,…) from a nitrogen
feed gas is studied. The permeances of the membranes are calculated with the Robenson’s Upper Bound.

The one-stage system does not provide

the desired separation. The VOC purity
(4.1%) and the recovery (90%) are too low.

This two-stage system is used to increase

the purity of the product. The final permeate
has been enriched twice to achieve a 20.8%
VOC purity, but the recovery is still 90%.

Separation Processes Laboratory 04.11.21

Assignment 06
The exercise will study the limitations of single stage membrane processes by solving the equations of the
simple well-mixed module.
• Overall balance equations.
𝒏𝒑̇ + 𝒏𝒓̇ = 𝒏𝒇̇
𝒏𝒑̇ 𝒚𝜶,𝒑 + 𝒏𝒓̇ 𝒚𝜶,𝒓 = 𝒏𝒇̇ 𝒚𝜶,𝒇
• Membrane flow balance equations.
𝒏𝒑̇ 𝒚𝜶,𝒑 = 𝑱𝜶 𝑨

𝒏𝒑̇ 𝟏 −̇ 𝒚𝜶,𝒑 = 𝑱𝜷 𝑨
• Flux equations for the solution-diffusion model.
𝑱𝜶 = 𝑷𝜶 𝒑𝒇 𝒚𝜶,𝒓 − 𝒑 𝒚𝜶,𝒑

𝑱𝜷 = 𝑷𝜷 𝒑𝒇 𝟏 − 𝒚𝜶,𝒓 − 𝒑 𝟏 − 𝒚𝜶,𝒑
a. Implement a MATLAB function that:
o Takes as input: 𝒏𝒇̇ , 𝒚𝜶,𝒇 , 𝒑𝒇 , 𝑷𝜶 , 𝑷𝜷 , 𝑨, 𝒑 Code will be available on Monday
morning for those who did not manage
o Computes the component α purity (Pu) and recovery (Re)

̇ 𝐦𝐨𝐥
b. Let 𝒏𝒇 = 𝟏 [ 𝐬 ], 𝒚𝜶,𝒇 = 𝟎. 𝟏𝟐 − , 𝒑𝒇 = 𝟐𝐞𝟓 𝐏𝐚 , 𝑷𝜶 = 𝟏𝟎𝟎𝟎 𝐆𝐏𝐔 , 𝑷𝜷 =
𝐦𝐨𝐥 Study the one-stage membrane process
𝟐𝟎 [𝐆𝐏𝐔] where 𝟏 𝐆𝐏𝐔 = 𝟑. 𝟑𝟓𝐞-𝟏𝟎 [𝐦𝟐 𝐬 𝐏𝐚]. The membrane permeances on post-combustion carbon capture
correspond to state-of-the-art polymer membranes for CO2/N2 separation.

Separation Processes Laboratory 04.11.21

Outline – Lecture 04.11.2021

• Recap

• Pervaporation

• Membrane modules:

- Challenges for membrane commercial application

- Limits of a single-stage membrane process

- Multi-stage cascade processes

• Graphene membranes (Dr. Karl-Philipp Schlichting)

• Summary: Main concepts for binary systems (not on slides)

Separation Processes Laboratory 04.11.21 63

Outline – Lecture 04.11.2021

• Recap

• Pervaporation

• Membrane modules:

- Challenges for membrane commercial application

- Limits of a single-stage membrane process

- Multi-stage cascade processes

• Graphene membranes (Dr. Karl-Philipp Schlichting)

• Summary: Main concepts for binary systems (not on slides)

Separation Processes Laboratory 04.11.21 64