Membrane Process

Prof. Chung-Hak Lee

School of Chemical and Biological Engineering
Seoul National University, Seoul, Korea

URL: http://wemt.snu.ac.kr

Membrane Process
References:
1)

Norman N. Li, A.G. Fane, W.S. Wisnton Ho, Takeshi Matsuura (2008),
Advanced Membrane Technology and Applications, John Wiley & Sons, Inc.

2) Cheryan, M. (1998), Ultrafiltration and Microfiltration Handbook,

Technomic Publishing Company, Inc.
3) Mulder,M. (1996), Basic Principles of Membrane Technology,
2nd Edition, Kluwer Academic Publishers.
4) Faisal I.Hai, Kazuo Yamamoto. Chung-Hak Lee (2014), Membrane
Biological Reactors, International Water Association.

Chapter 1
Introduction

Chapter 1-1. Definition of Membrane

1-2. Classification of Membrane Processes
1-3. Historical Development
1-4. Classification of Filter (Membrane)

1-1. Definition of Membrane separation Processes

WHAT IS A MEMBRANE?
i) A region of discontinuity interposed between two phases
Hwang & Kammermeyer (1975)
It can mean almost anything even air.

ii) A phase that acts as a barrier to prevent mass movement,

but allows restricted and/or regulated passage of one or more species.
Lakshminarayanaiah (1984)
Membrane can be gaseous, liquid, solid or combination
of these. better definition

Conventional vs.
- Conventional Filtration :

- Membrane Filtration

Membrane Filtration

Separation of solid, immiscible particles

from liquid or gaseous streams.

: Extends this application further, e.g.,

separation of dissolved solids in liquid streams
and separation of gas mixtures.

Chapter 1
Introduction

Chapter 1-1. Definition of Membrane

1-2. Classification of Membrane Processes
1-3. Historical Development
1-4. Classification of Filter (Membrane)

1-2. Classification of Membrane Processes

-The membrane has the ability to transport one component more readily
than other because of differences in physical and/or chemical properties
between the membrane and the permeating components.
- Transport through the membrane takes place as a result of a driving force
acting on the individual components in the feed.

Phenomenological Equations
-In many cases, the permeation rate through the membrane is
proportional to the driving force
J = - A dX/ dx
A : phenomenological coefficient
dX/dx : driving force (temp., pressure, concentration, etc.)
-Phenomenological equations cane also be used to describe
not only mass flux but heat flux, volume flux, momentum flux
and electrical flux.

Phenomenological Equations
J = - A dX/ dx
A : phenomenological coefficient
dX/dx : driving force (temp., pressure, concentration, etc.)
A = Diffusion coefficient
(mass flux, Ficks law))
= permeability coefficient (volume flux, Darcys law))
= thermal diffusivity
(heat flux,
Fouriers law)
= kinetic viscosity
(momentum flux, Newtons law)
= electrical conductivity (electrical flux, Ohms law)

Phenomenological Equations
J = - A dX/ dx
A : phenomenological coefficient
dX/dx : driving force
(temp., pressure, concentration, electrical potential, etc.)

- In using such equation, the transport process is considered as being

macroscopic and the membrane as a black box.
- For a pure component permeating through a membrane,
it is possible to employ linear relations to describe transport.
- However, two or more components permeate simultaneously,
such relations cannot be generally employed since coupling phenomena
may occur in the fluxes and forces.

Phases divided by membrane

Some Membrane Processes and Driving Forces

Chapter 1
Introduction

Chapter 1-1. Definition of Membrane

1-2. Classification of Membrane Processes
1-3. Historical Development
1-4. Classification of Filter (Membrane)

1-3. Historical Development of Membranes

Historical Development of Membranes

1748 : French, Abb Nollet
- Demonstrated semi-permeability for the first time
- He placed spirits of wine in a vessel, the mouth of which was
closed with an animal bladder and immersed in pure water.
Because it was more permeable to water than to wine, the bladder
swelled and sometimes even burst.
1855 : Fick
- He published his phenomenological laws of diffusion, which we
still use today as a first-order description of diffusion through
membrane.
- He prepared and studied some of the earliest artificial semi-permeable
membranes. (collodion ; ether-alcohol solution of cellulose nitrate)

Historical Development of Membranes

1861 : T. Graham
- Grahams law of diffusion in gases
- He made some of the first measurements of dialysis through
synthetic membranes.
- He discovered that rubber exhibits different permeabilities to
different gases.
Father : gas separations via membranes.

1860-1887 : Traube, Pfeffer, Vant Hoff

- They manufactured precipitated membrane.
- Osmotic pressure and diffusion phenomena were measured
quantitatively Vant Hoff equation.

Historical Development of Membranes

1907-1918 : Bech hold, Zsigmondy
- They developed methods for controlling the membrane pore size,
principally with collodion membrane

1911 : Donnan
- He studied the distribution of macromolecular and micromolecular
charged species across the semi-permeable membranes.
- Donnan Distribution Law still finds use in our understanding of
equilibrium phenomena in Donnan Dialysis and in coupled
transport
1930s : Teorell, Meyer, Sievers
-Theory of transport across neutral and fixed-charge membrane.
It formed the basis for our current understanding of both electrodialysis membranes and modern membrane electrodes.

Historical Development of Membranes

1927 : Satorius, Germany

- Membranes were manufactured commercially in small quantities.
1944 : Kolff
- He demonstrated Artificial Kidney as one of the first practical
applications of dialysis.
1951 : Goetz
- He imprinted grid lines on filters to facilitate bacteria counting.

Artificial Kidney

Dr. Kolff : Artificial Kidney

Historical Development of Membranes

1957 : United States Public Health Service (USPH)
- Officially adopted the membrane filtration procedure for drinking
water analysis.

Early 1950s : Samuel Yuster of U.C.L.A.

- He predicted that, based on Gibbs adsorption isotherm, it should
be possible to produce fresh water from brine. (Shortage of H2O in
California so came up with a desalination idea)

Samuel Yuster predicted that, based on Gibbs adsorption isotherm,

it should be possible to produce fresh water from brine.

Our species is the only creative species, and it

has only one creative instrument, the individual
mind and spirit of man. Nothing was ever created
by two men. There are no good collaborations,
whether in music, in art, in poetry, in
mathematics, in philosophy.
Once the miracle of creation has taken place, the
group can build and extend it, but the group
never invents anything. The preciousness lies in
the lonely mind of a man.
John Steinbeck, East of Eden, 1952

Gibbs Adsorption Isotherm

C2

)
S =
(
RT C 2

S = excess solute near the surface

C2 = concentration of solute
= surface tension
= surface area

) 0 ], there
- If a solute causes a decrease in surface tension [ (
C 2
will be adsorption on the surface.

) 0 ], the
- If a solute causes an increase in surface tension [ (
C 2
solute avoids the surface region.

S =

RT ln C 2
C2

=
(
)
RT C 2

a2 = 2C2
2 1 in dilute solution

Surface tension vs. concentration

(dyne/cm)
NaCl

73

C2H5OH

moles/L

Reverse Osmosis

- Unfortunately, most stuff we deal with, decrease surface tension.

- 2t ; need of appropriate size [2 x the thickness(t)] to get a water fall.

Birth of Asymmetric Membrane

1958-1960 : Sourirajan, Loeb
- They performed heat treatment (annealing) to expand the pores
and thus increase flux. But exactly the opposite happened :
heating contracted the pores.
So then they took commercially available UF Membrane and
performed the heat treatment 3rd row in Tab. 1.2
It caused the pores to shrink Better rejection
Asymmetry

higher flux

Historical Development of Membranes

Journal of membrane science, 339, 1-4, 2009

Seawater Desalination by Reverse Osmosis (RO)

International Market Trends

Total capacity of worldwide seawater desalination plants :
> 30 million tons/day
Total market growth rate : ~11%/year
(Sea Water Reverse Osmosis: ~17%/year)

Europe
Asia
Middle
East
(50%)

North America
Central
America

Africa
Australia

South America

= 1million m3/day (220MIGD)

Source: Wangnick (2004)

Chapter 1
Introduction

Chapter 1-1. Definition of Membrane

1-2. Classification of Membrane Processes
1-3. Historical Development
1-4. Classification of Filter (Membrane)

Depth filter vs. Screen filter

Depth Filter : - Filtration or particle removal occurs within the depths of the
filter material.
- A matrix of randomly oriented fibers or beads that are
bonded together to form a tortuous maze of flow channel.
- Removal mechanisms : interception, inertial impaction,
diffusion, etc.
Screen Filter : - Separation of particles by retaining them on its surface in
much the same manner as a sieve.
- Having a defined pore size. Membrane filters fall into this
category.

1- 5. Classification of Filter (Membrane)

FILTERS
Depth

Microporous

Isotropic

Screen
Asymmetric
(Skinned)

Anisotropic
Integrally
skinned

Nonintegrally
skinned

Depth Filter

Screen Filter

Advantages of screen filter

1) Grow-through of microorganisms is not as frequent a problem

2) Little danger of sloughing off (material migration)
3) Higher recovery of the retained material (microbial cell harvesting)
4) Little liquid hold-up
5) Pore size can be controlled.

Absolute vs. Nominal Rating

Microporous vs. Asymmetric

Microporous : - No skin.
- Absolute rating (retain all the particles larger than that rating)
Isotropic : pores of uniform size throughout the body of the membrane.
Anisotropic : pores change in size from one surface of the membrane
to the other.

Asymmetric : - A thin skin on the surface of membrane with supporting layer.

- Nominal rating (MWCO above which a certain percentage of
the solute will be retained by the membrane.
- Anisotropy and Asymmetry are (incorrectedly) used interchangeably.
Integrally skinned : homogeneous skin and support layers
Non-integrally Skinned: composite skin and support layers

MF membrane (Fluxxion,Eindhoven, Netherlands)

* http://www.fluxxion.com

MF membrane (Fluxxion,Eindhoven, Netherlands)

MF membrane (Isopore MINs Membrane, WEMT, SNU )