Chapter Eight- Membrane Separation…………………………………………Dr.

Farah Taliib Al-Sudani………1

Chapter Eight
Membrane Separation

8.1 Membrane Separation Processes

Membrane separations represent a new type of unit operation. In membrane

separation process, a feed consisting of a mixture of two or more components
is partially separated by means of a semi-permeable barrier which separates
components of a mixture or solution by selectively controlling their movement
from one side of the membrane to the other. In some cases, particles or
molecules of sizes larger than those of the pores of the membrane are excluded
right at the upstream side while in others, they move through the membranes
at differential rates depending upon their molecular weights or volumes so that
separation becomes possible.

8.2 Classification of membrane processes

In their early stage of development, membrane processes were classified as

follows:
(i) gaseous diffusion or effusion and permeation in separation of gases
(ii) dialysis and permeation in separation of liquids.

According to present practice, membrane processes are classified in terms of

different types of pressure driven membrane filtration as:

- microfiltration (MF) for separation of colloidal to micron particles and

microorganisms,
- ultrafiltration (UF) for separation of organics with molecular weight of
above 5000,
- nanofiltration (NF) for separation of divalent salts and organics while
permeating monovalent salts such as NaCl,
- reverse osmosis (RO) for very high degree of salt separation including NaCl
and soluble organics.

Reverse osmosis membranes are classified further into three categories:

Chapter Eight- Membrane Separation…………………………………………Dr.Farah Taliib Al-Sudani………2

- Sea water type membranes for 99.9% rejection of all salts even from 3 to 4%
salts with high osmotic pressures, and high separation of organics of low
molecular weight such as chlorobenzenes, etc., Brackish water type
membranes (low to moderate osmotic pressures, salt < 5000 ppm and high
separation of organics of low molecular weight); Ultra low pressure (Ozaki
and Li 2002) reverse osmosis (purification of water from low ppm to ppb
range).

8.3 GENERAL MEMBRANE EQUATION

It is not possible at present to provide an equation, or set of equations, that allows
the prediction from first principles of the membrane permeation rate and solute
rejection for a given real separation.
The general membrane equation is an attempt to state the factors which may be
important in determining the membrane permeation rate for pressure driven
processes.

……………………………..8.1

where J is the membrane flux*, expressed as volumetric rate per unit area, |ΔP| is the
pressure difference applied across the membrane, the transmembrane pressure, ΔΠ
is the difference in osmotic pressure across the membrane, Rm is the resistance of
the membrane, and Rc is the resistance of layers deposited on the membrane, the
Chapter Eight- Membrane Separation…………………………………………Dr.Farah Taliib Al-Sudani………3

filter cake and gel foulants. If the membrane is only exposed to pure solvent, say
water, then equation 8.1 reduces to
J =|ΔP|/R m µ……………………………8.2

For microfiltration and ultrafiltration membranes where solvent flow is most often
essentially laminar through an arrangement of tortuous channels, this is analogous
to the Carman–Kozeny equation. Knowledge of such water fluxes is useful for
characterising new membranes and also for assessing the effectiveness of membrane
cleaning procedures. In the processing of solutes, equation 8.1 shows that the
transmembrane pressure must exceed the osmotic pressure for flow to occur. It is
generally assumed that the osmotic pressure of most retained solutes is likely to be
negligible in the cases of microfiltration. The resistance R c is due to the formation
of a filter cake, the formation of a gel when the concentration of macromolecules at
the membrane surface exceeds their solubility giving rise to a precipitation, or due
to materials in the process feed that adsorb on the membrane surface producing an
additional barrier to solvent flow. The separation of a solute by a membrane gives
rise to an increased concentration of that solute at the membrane surface, an effect
known as concentration polarisation. This may be described in terms of an increase
in ΔΠ.

8.4.Membrane Processes

8.4.1. Separation of Liquids

Several processes have been developed for separation of liquids using both porous
and polymeric membranes. In dialysis, porous membranes are used and separation
generally depends on diffusivity difference between the solutes of different
molecular weights. In liquid-liquid extraction, which also employs porous
membranes, the raffinate and extract phases are separated by the membrane.
Differences in equilibrium solute distribution and diffusivity determine the extract
composition. In permeation of liquids, dense polymeric membranes are used for
separation of components of liquids.

8.4.1.1. Dialysis
In this case the small solutes in one liquid phase diffuse through a porous membrane
to the second liquid phase where the permeants are diluted by means of a so-called
sweeping solvent. The driving force is a concentration gradient so the flux rates are
low. If the boiling point of the permeants is much lower than that of the sweeping
Chapter Eight- Membrane Separation…………………………………………Dr.Farah Taliib Al-Sudani………4

liquid, the permeants can be separated by flashing from the sweeping liquid, the
dialysis process is called pertraction.

In practice dialysis is used to separate species that differ appreciably in size, which
have a large difference in diffusion rates.
Applications include recovery of sodium hydroxide in cellulose processing, recovery
of acids from metallurgical liquors, removal of products from a culture solution in
fermentation.

Pressure difference across the membrane being negligible, the flux of each
component is proportional to the concentration difference at the two ends of the
membrane, which acts as the driving force. Solutes of high molecular weight are
mostly retained by the feed solution because of their low diffusivities and the high
resistance encountered by them during diffusion through pores of almost their own
size. At equilibrium, the chemical potentials of the diffusing component on both
sides of the membrane are equal.

- Series resistances in membrane processes

In dialysis, the solute molecules must first be transported or diffuse through the
liquid film of the first liquid phase on one side of the solid membrane, through the
membrane itself, and then through the film of the second liquid phase. This is
shown in Figure 2, where c1 is the bulk liquid phase concentration of the diffusing
solute A in kg mol A/m3 , c1i is the concentration of A in the fluid just adjacent to
the solid, and c1iS is the concentration of A in the solid at the surface and is in
equilibrium with c1i .The mass transfer coefficients are k c1 and k c2 in m/s. The
equilibrium distribution coefficient K’ is defined as:

………….8.3
Chapter Eight- Membrane Separation…………………………………………Dr.Farah Taliib Al-Sudani………5

Figure1

The flux equations through each phase are all equal to each other at steady state:

……..8.4

Substituting Eq. (8.3) into Eq. (8.4),

……………………..8.5

…………8.6

where pM is the permeability in the solid in m/s, L is the thickness in m, and DAB
is the diffusivity of A in the solid in m2/s. Instead of determining DAB and K’ in two
separate experiments, it is more convenient to determine p M in one experiment.
The concentration differences can be obtained from Eq. (8.5):

………………8.6
Chapter Eight- Membrane Separation…………………………………………Dr.Farah Taliib Al-Sudani………6

By adding three equations, the internal concentrations drop out, the final equation
is

………8.7
The denominator can be considered as the inverse of overall mass transfer
coefficient. In some cases, the resistances in the two liquid films are quite small
compared to that of the membrane resistance, which controls the permeation rate.

2- Separation of Gases

Gaseous diffusion or effusion : When a gas mixture having two or more

components, is allowed to pass through a porous membrane from a zone of higher
pressure to that of lower pressure, the down-stream gas gets enriched in lower
molecular weight components since they diffuse at faster rates. This phenomenon is
known as gaseous diffusion or effusion. If the pores are much smaller than the mean
free path of the gas, then the gas diffuses independently by Kundsen diffusion.
Because of tortuous micropores within the membrane, the diffusivity of the gas gets
appreciably reduced.

Permeation of gases : Transport of gases through dense nonporous polymeric

membranes is known as permeation. Permeation occurs by the mechanism of
solution diffusion, which is more or less similar to that involved in structure
insensitive diffusion. The gas gets dissolved in the polymer at the high pressure side,
diffuses through the membrane and is released at the low pressure side. The rate of
mass transfer is a function of the concentration gradient within the membrane, which
in turn is proportional to the pressure gradient if solubility depends on pressure. If
the gas film resistance at the gas-polymer interface is neglected, then the partial
pressures of the diffusing components at the gas-polymer interface are same as those
in the bulk gas.

Similar equations to dialysis can be written for gas permeation. The equilibrium
relation between the solid and gas phases is given by

……..8.8
Chapter Eight- Membrane Separation…………………………………………Dr.Farah Taliib Al-Sudani………7

where S is the solubility of A in m3 (STP)/atm m3 solid, and H is the equilibrium

relation in kg mol/m3 atm. This is similar to Henry’s law. The flux equations in
each phase are as follows:

…….8.9

The permeability Pm in kg mol/s m atm is given by

…….……………8.10

Eliminating the interfacial concentrations as before,

…………8.11

Note that k G1= k c1 /RT. An example of gas permeation in

a membrane is use of a polymeric membrane as an is on one side of a thin

membrane and blood is on the other side. oxygenator for a heart-lung machine.
Pure O2 Oxygen diffuses through the membrane into the blood and CO2 diffuses
in a reverse direction into the gas stream.
Chapter Eight- Membrane Separation…………………………………………Dr.Farah Taliib Al-Sudani………8

If the gas film resistance at the gas-polymer interface is neglected, then the
partial pressures of the diffusing components at the gas-polymer interface are
same as those in the bulk gas.The flux for gas A is given by :-

………………………………………….…………………8.12

If the system obeys Henry’s law, then

where, HA = Henry’s law constant for A , From Eq. (8.12), we have

……………………….……………………………………………….8.13

(DA/HA) is the flux of component A per unit pressure gradient and is called
the permeability coefficient (qA). Since the actual membrane thickness is not
always known, it is customary to express flux per unit pressure difference,
which is called permeability (QA).

…………………8.14

The ratio of permeabilities for a binary mixture is known as membrane

selectivity and is denoted by a,

…………………………………………….8.15

High selectivity may be obtained either from a favourable diffusivity ratio or

from a large difference in solubilities. Diffusivities in membrane depend more
strongly on the size and shape of the molecules than gas-phase diffusivities do.
Gas solubilities also vary widely with the nature of the gas and the type of
Chapter Eight- Membrane Separation…………………………………………Dr.Farah Taliib Al-Sudani………9

polymer. For most gases, permeability increases with temperature since the
increase in diffusivity caused by temperature rise, outweighs any decrease in
solubility. The change in permeability may be correlated by Eq. (15.10):

………………………………….8.16

where, E is the activation energy.

Membrane selectivity usually decreases at elevated temperature. The operating
temperature should therefore be determined by striking a balance between high
flux and high selectivity. The compositions of the permeate and the residue
depend on feed composition, permeability's of the components present,
pressure difference across the membrane and the ratio of permeate to feed.
Equations have been developed (Fane et al. 1981) which show the effect of
these parameters on permeate composition and are useful in estimation of the
amount of permeate, its composition and the required membrane area.

3. Reverse Osmosis
In osmosis, miscible solutions of different compositions are separated by a
membrane, which allows the solvent but not the solutes to pass through its
pores. Thus, the spontaneous passage of a liquid from a dilute to a more
concentrated solution across an ideal semipermeable membrane takes place by
diffusion, where the activity of the solvent is relatively low. Osmotic transfer
of water occurs in many plants and animal cells. If an external force is executed
on the more concentrated solution, the equilibrium is disturbed and the activity
of the solvent at this end increases. As a result, the flow of solvent is reversed.
Thus, the process selectively restricts flow of solute while permitting flow of
solvent only.

The chemical potentials of the solvent on both sides of the membrane are
equal. The osmotic pressure depends on the property of the solution, but
not the membrane provided it is truly semipermeable. To reverse the
flow of water so that it flows from the salt solution to the fresh solvent,
the pressure is increased above the osmotic pressure on the solution side.
 Chapter Eight- Membrane Separation…………………………………………Dr.Farah Taliib Al-
Sudani………10

This phenomenon is known as reverse osmosis (RO), and depicted in Figure 2.

1. Osmotic pressure of solutions

Figure2
The osmotic pressure of a solution is proportional to the concentration of the solute and
temperature T. The relationship is similar to that for pressure of an ideal gas. For
example, for dilute water solutions,

…………………….8.17

where n is the number of kg mol of solute, V m the volume of pure solvent water in m3
associated with n kg mol of solute, R is the gas constant, and T is temperature in K. If a
solute exists as two or more ions in solution, n represents the total number of ions. For
more concentrated solutions, Eq. (1) is modified using an osmotic coefficient , which is
the ratio of the actual osmotic pressure  to the ideal  calculated from the equation.

3. Flux equations for reverse osmosis

There are two basic types of mass-transport mechanisms in membranes. In the first type,
using tight membranes, which are capable of retaining solutes of about 10 Ao in size or less,
diffusion-type transport mainly occurs. Both the solute and the solvent migrate by
molecular or Fickian diffusion in the polymer, driven by the concentration gradients set up
in the membrane by the applied pressure difference. In the second type, a sieve-type
mechanism occurs where the solvent moves through the micropores in viscous flow, and
 Chapter Eight- Membrane Separation…………………………………………Dr.Farah Taliib Al-
Sudani………11

the solute molecules small enough to pass through the pores are carried out by convection
with the solvent.

For diffusion-type membranes, the solvent and solute are given below: steady-state
equations governing the transport of
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Sudani………12

The chemical potentials of the solvent on both sides of the membrane are
equal. The osmotic pressure depends on the property of the solution, but
not the membrane provided it is truly semipermeable. To reverse the
 Chapter Eight- Membrane Separation…………………………………………Dr.Farah Taliib Al-
Sudani………13

flow of water so that it flows from the salt solution to the fresh solvent,
the pressure is increased above the osmotic pressure on the solution side

4. CROSS-FLOW MICROFILTRATION

The solids–liquid separation of slurries containing particles below 10 µm is difficult by

conventional filtration techniques. A conventional approach would be to use a slurry
thickener in which the formation of a filter cake is restricted and the product is discharged
continuously as a concentrated slurry. Such filters use filter cloths as the filtration
medium and are limited to concentrating particles above 5 µm in size.Dead end or frontal
membrane microfiltration, in which the particle containing fluid is pumped directly
through a polymeric membrane, is used for the industrial clarification and sterilisation of
liquids. Such a process allows the removal of particles down to 0.1 µm or less, but is only
suitable for feeds containing very low concentrations of particles as otherwise the
membrane becomes too rapidly clogged.

Ideally, cross-flow microfiltration would be the pressure-driven removal of the process

liquid through a porous medium without the deposition of particulate material. The flux
decrease occurring during cross-flow microfiltration shows that this is not the case. If the
decrease is due to particle deposition resulting from incomplete removal by the cross-
 Chapter Eight- Membrane Separation…………………………………………Dr.Farah Taliib Al-
Sudani………14

flow liquid, then a description analogous to that of generalised cake filtration theory , the
The general membrane equation become :

where Rc now represents the resistance of the cake, which if all filtered particles remain

in the cake, may be written as:

where r is the specific resistance of the deposit, V the total volume filtered, Vs the volume
of particles deposited, Cb the bulk concentration of particles in the feed (particle
volume/feed volume) and Am the membrane area. The specific resistance may theoretically
be related to the particle properties for spherical particles by the Carman relationship

where e is the void volume of the cake and ds the mean particle diameter. And combined
above equations:

Then Solution abone equation for V at constant pressure gives:

yielding a straight line on plotting t/V against V .

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Sudani………15
 Chapter Eight- Membrane Separation…………………………………………Dr.Farah Taliib Al-
Sudani………16

5. ULTRAFILTRATION

Ultrafiltration is one of the most widely used of the pressure-driven membrane separation
processes. The solutes retained or rejected by ultrafiltration membranes are those with
molecular weights of 103 or greater, depending mostly on the MWCO of the membrane
chosen. The process liquid, dissolved salts and low molecular weight organic molecules
(500–1000 kg/kmol) generally pass through the membrane. The pressure difference
applied across the membrane is usually in the range 0.1–0.7 MN/m 2 and membrane
permeation rates are typically 0.01–0.2 m3/m2 h. In industry, ultrafiltration is always
operated in the cross-flow mode.The separation of process liquid and solute that takes place
at the membrane during ultrafiltration gives rise to an increase in solute concentration close
to the membrane surface, as shown in Figure below. This is termed concentration
polarization and takes place within the boundary film generated by the applied cross-flow.
With a greater concentration at the membrane, there will be a tendency for solute to diffuse
back into the bulk feed according to Fick’s Law,. At steady state, the rate of back-diffusion
will be equal to the rate of removal of solute at the membrane, minus the rate of solute
leakage through the membrane:
Chapter Eight- Membrane Separation…………………………………………Dr.Farah Taliib Al-
Sudani………17
Chapter Eight- Membrane Separation…………………………………………Dr.Farah Taliib Al-
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