TEKNOLOGI MEMBRAN

MATERI
 Introduction
 Membrane Transport Theory
 Membrane Materials & Properties
 MembraneModules
 Concentration Polarization
 Membrane Applications
OVERVIEW OF
TRANSPORT IN SOLIDS
Basic of Mass Transfer
Convection
 Movement of materials due to fluid flow,
e.g.
◦ Delivery of oxygen in the body fluid
Diffusion
 Transfer of material in a stagnant medium
due to concentration difference of solute
 Ficks Law of Diffusion
 Diffusion flux is proportional to
concentration gradient
c
c c2  c1 c1  Slope is
x

x x2  x1 c Flux J

c2
 The solute diffuses from a position
with a high concentration to another x1 x2
position with a low concentration; x
i.e. When concentration c1>c2, flux is
positive from x1 to x2

c
J  D
x
DIFFUSION IN SOLIDS
 Mass transfer in solid is quite important in
chemical processing : membrane separation
 Can be classified into two types :
◦ Diffusion that can be considered to follow
Fick’s law (not depend on the actual structure
of the solid
◦ Diffusion in porous solid where the actual
structure and void channels are important
DIFFUSION IN SOLIDS
 Diffusion occurs when the fluid or solute diffusing is actually
dissolved in the solid to form a more or less homogeneous
solution
 For binary solution, generally, the rate of diffusion :
Bulk flow Solid
dx A c A
N A  cDAB  (N A  NB )
dx c
cA1
NA
 The term of bulk flow is usually
small, since xA (cA/c) quite small
and if c is assumed constant, the cA2
flux is :
dc A x1 x2
N A   DAB
dx
c A1  c A 2
 For slab at steady state gives : N A  DAB
x2  x1
DIFFUSION IN SOLIDS
 The diffusion coefficient, DAB in the solid is not
dependent upon the pressure of gas or liquid on the
outside of the solid, however the solubility of gas is
directly proportional to partial pressure of gas, pA.
 The solubility of a solute gas (A) in a solid is usually
expressed as S in m3 solute(at STP of 0oC and 1 atm)
per m3 solid per atm partial pressure of (A)
 To convert the solubility (S) to cA concentrationin the
solid :
S p A kg mol A
cA 
22.414 m 3 solid
PERMEABILITY EQUATION FOR
DIFFUSION IN SOLIDS
 The diffusion coefficient, DAB in the solid can be
expressed as permeabilities, PM
 This can be related to Fick’s equation as follows
c A1  c A 2
N A  DAB
x2  x1
S p A1 S p A2
where : c A1  c A2 
22.414 22.414

DAB S p A1  p A2 PM p A1  p A2
thus NA  
22.414 x2  x1 22.414 x2  x1

m3 ( STP)
PM  DAB S Permeability
s m 2 C.S atm / m
Diffusivities and Permeabilities in Solids
Diffusion in Porous Solids
 In porous solids, pore or interconnected voids can be
affected the diffusion
 A cross section of a typical porous solid is shown as
follow


NA

z
z1 z2
Diffusion in Porous Solids
 If the voids are filled completly with liquid, the
concentration of solute at boudary 1 is cA1 and at poit 2
is cA2.
 The solute in diffusing through the liquid in the void
volume takes path which is unknown and greather than
(x2-x1) by a factor t, called tortuosity.
 For a dilute solution at steady state condition :

 .DAB (c A1  c A2 )
NA 
t ( x2  x1 )

 : is the open void fraction

t : is a factor tortuosity (a factor which corrects for the path)
Diffusion in Porous Solids
 For inert-type solid t can be vary from about 1.5 to 5

 The effective diffusivity is :

.D AB m2
D A,eff  ( )
t s

 Diffusion of gases in porous solids, if the pores are very

large so that diffusion occurs only by Fickian-type
diffusion :
 .DAB ( p A1  p A2 )
NA 
t .RT ( x2  x1 )
TRANSPORT THROUGH
MEMBRANES
TRANSPORT THROUGH
MEMBRANES
 The most important property of
membranes is their ability to control the
rate of permeation of different species.
 The two models used to describe the
mechanism of permeation are
◦ Solution-diffusion model
◦ Pore-flow model
Solution-diffusion model
 permeants dissolve in the
membrane material and
then diffuse through the
membrane down a
concentration gradient.
The permeants are
separated because of the
differences in the
solubilities of the materials
in the membrane and the
differences in the rates at
which the materials diffuse
through the membrane
Pore-flow model
 permeants are
transported by pressure-
driven convective flow
through tiny pores.
Separation occurs
because one of the
permeants is excluded
(filtered) from some of
the pores in the
membrane through
which other permeants
move.
Diffusion
 The basis of the solution-diffusion model, is the process by which
matter is transported from one part of a system to another by a
concentration gradient.
 The individual molecules in the membrane medium are in constant
random molecular motion. but in an isotropic medium, individual
molecules have no preferred direction of motion.
 if a concentration gradient of permeate molecules is formed in the
medium, simple statistics show that a net transport of matter will
occur from the high concentration to the low concentration
region.
Diffusion
 The concept of diffusion was first recognized by Fick theoretically
and experimentally.
 Fick formulated his results as the equation now called Fick’s law of
diffusion (1855),
dc A
J A   DA
dx
Conc. Gradient of A
Flux of A

Diffusion coefficient of A

 Diffusion is an inherently slow process. In practical diffusion-

controlled separation processes, useful fluxes across the membrane
are achieved by making the membranes very thin and creating large
concentration gradients in the membrane
 Diffusion
 The difference between the solution-diffusion and pore-flow
mechanisms lies in the relative size and permanence of the pores.
For membranes in which transport is best described by the
solution-diffusion model and Fick’s law, the free-volume elements
(pores) in the membrane are tiny spaces between polymer chains
caused by thermal motion of the polymer molecules. These volume
elements appear and disappear on about the same timescale as the
motions of the permeants traversing the membrane.

free-volume
elements

Micro solute
cavity
Pressure-driven convective flow
 Basis of the pore flow model, is most commonly used to describe
flow in a capillary or porous medium.
 The basic equation covering this type of transport is Darcy’s law,
which can be written as
dp
J A  K cA'

dx
Pressure gradient
Flux of A

coefficient reflecting the

nature of the medium

 Convective-pressure-driven membrane fluxes are high compared

with those obtained by simple diffusion
Pressure-driven convective flow
 For a membrane in which transport is best
described by a pore-flow model and Darcy’s
law, the free-volume elements (pores) are pore
relatively large and fixed, do not fluctuate in
position or volume on the timescale of
permeant motion, and are connected to one
another.
 The larger theindividual free volume elements
(pores), the more likely they are to be
present long enough to produce pore-flow
characteristics in the membrane.
 As a rough rule of thumb, the transition
between transient (solution-diffusion) and
permanent (pore-flow) pores is in the range
5–10 ˚A diameter.
HOW SEPARATION OCCURS

Difference in permeabilities through a

membrane :

 Difference in size,
 Affinity to the membrane,
 Charge, etc.
TRANSPORT THROUGH
MEMBRANES
 Driving force in a membrane process is
necessary to provide the motion of the
molecules.

 Membrane processes can be driven by :

 Pressure,
 Concentration,
 Electric field etc.
DRIVING FORCES

 Pressure difference,
 Concentration difference,
 Voltage difference, etc.
STRUCTURAL CLASSIFICATION
OF MEMBRANES
POROUS
 Hagen-Poisseuille Model
◦ molecules have a bulk motion due to the
pressure
 Knudsen Model
◦ diffusional motion of the molecules are
considered
◦ causes the selectivity
POROUS
 pore sizes should be as small as possible
to have the desired selectivity. However,
small pore size causes a big resistance to
permeate flow

How to Cope With This Problem?

ASYMMETRIC MEMBRANES
Composed of two membrane layers;
 thin layer
◦ small pore size
◦ determines the selectivity and the rate of the stream
 thick layer.
◦ supporting part
◦ it has no selectivity towards any of the mixture
component
◦ it has no resistence to the flow
NON-POROUS MEMBRANES
 There is a concept “permeability” considering solubility
and diffusivity
 Since the molecules pass through relatively small spaces,
interactions between the membrane material and the
passing molecule become important
 Permeability of the membrane to any of the mixture
component is proportional to the solubility of that
component in the membrane and the diffusivity of it
 There are also interacting systems in which high
concentrations favour the enlargement of the free
spaces in the membrane
 Permeability also depends on temperature, as
temperature increases permeability increases
TRANSPORT THROUGH
MEMBRANES

Membrane

High Low
Potential Potential
TRANSPORT THROUGH
MEMBRANES
 Flux of the molecules are proportional to the
driving force by a proportionality constant:

Fick’s Law :

dX
J  A
dx
TRANSPORT THROUGH
MEMBRANES
 Chemical Potential (Composite effect of
both the pressure and the chemical
activity gradient.):

  RT  ln a  V P
POROUS MEMBRANES
In Porous membranes, motion is assumed to
be through small pipes.

 Hagen-Poiseuille model
 Knudsen flow model (For gasses)
HAGEN-POISEUILLE MODEL

 Assuming all the pores have the same radius:

 r P 2
J
8t x
FLOW MODEL
Retentate

Membrane

Permeate

Feed
 NON-POROUS MEMBRANES
 In Non-Porous membranes, solubility diffusivity
model is used.

 Permeability = S x D

dC
J  D
dx
NON-POROUS MEMBRANES
 Solubility depends on the membrane
penetrant interaction

 Diffusivity depends on the geometry of

the penetrant molecule
Factors that Influence Diffusion Rates
 Distance
◦ The shorter the distance, the more quickly concentration gradients
are eliminated
◦ Few cells are father than 125 microns from a blood vessel
 Molecular Size
◦ Ions and small molecules diffuse more rapidly
 Temperature
◦ higher temp., faster motion of particles
 Steepness of concentrated gradient
◦ The larger the concentration gradient, the faster diffusion proceeds
 Membrane surface area
◦ The larger the area, the faster diffusion proceed
Estimation of Diffusion Coefficient
 The Stokes-Einstein equation is written as
T
D
6r
where k is Boltzman’s constant, T is absolute temperature, μ is the
viscosity of the solvent, and r is the radius of solute molecule.
 For a spherical molecule, the molecule mass is:
T  4
D ( 2 )1/ 3 where M  r 3 
3 6 M 3

 For proteins, ρ can be assumed to be constant.

T  1/ 3
DM 1/ 3  ( 2 )  constant, thus D  M 1/ 3
3 6
 Thus the diffusion coefficient of a solute in a liquid is approximately
inversely proportional to the cubic root of the molecular weight.
Effect of Membrane Permeability on Diffusion
Effect of Membrane Permeability on Diffusion and
Osmosis


 Partition Coefficient and Solubility
 When two materials or two Two phases in equilibrium
mixture of materials are
brought together, and yet they
interface
cannot be completely mixed to
become homogeneous, then
different phases coexist
 A solute that can be dissolved
in both phases eventually
reaches equilibrium in the two
phases
 The concentrations of the
solute in the two phases at H is the partition coefficient
equilibrium are related by a
partition coefficient
 Diffusion Across the Membrane
 Flux across the membrane is described by
Membrane

H is the partition coefficient

c1
Hc1
Permeability up
stream Hc2
c2
Concentration in the membrane is Down
hard to measure. The concentration stream
in the solutions C is often used. 
The concentration in the membrane
is calculated using the value of H.
THANK YOU FOR
LISTENING

QUESTIONS?