MEMBRANE SEPARATION

PROCESSES

What is Membrane?
A membrane is defined as a thin layer of material which separates two liquid phases,
two gas phases, or a liquid - gas phase.

A selective barrier that permits the separation of certain species in a fluid.

Membrane Materials

Polymeric membranes
organic membranes e.g. synthetic polymers
Non-polymeric membranes

inorganic membranes e.g. metal, ceramic, carbon and zeolites

- liquid membranes e.g. thin oil film
Hybrid membranes

Mixed matrix membranes where both organic and inorganic components are used

Some Major Applications of Membrane Technology

1)

Microfiltration (MF)
removes particles (0.08-2 m) and operates within a range of 7-100 kPa.
separate microorganisms and suspended particles from process liquid.

2)

Ultrafiltration (UF)
removes particles (0.005-2 m) and operates within a range of 70-700kPa.
used to remove dissolved compounds with high molecular weight, such as proteins and
carbohydrates. Also, remove viruses and some endotoxins.

3)

Dialysis (D)
process of eliminating waste (diffusion) and unwanted water (ultrafiltration) from the
blood.

4)

Reverse Osmosis (RO)

RO is commonly used for the removal of dissolved constituents from wastewater and
seawater desalination.

Membrane Processes
The retentate (concentrate/residual) is part of
the feed that does not pass through the
membrane.
The permeate (filtrate/product) is that part of
the feed that does pass through the membrane.
The driving forces for transport across the
membrane is the chemical potential gradient
and the physical structure of the membrane.
Effectiveness of any membrane process is
described in term of the permeation rate (flux)
and selectivity.
The degree of membrane selectivity is depends
on the membrane pore size.

Liquid Permeation Membrane

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.
The equilibrium distribution coefficient K is defined as

c c
c
K'
c c
c
S

1 iS

2 iS

1i

2i

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

DAB
N A kc1 (c1 c1i )
(c1is c2is ) kc 2 (c2i c2 )
L

c1 = bulk liquid phase concentration of the diffusing solute A (kg mol A/m3)
c1i = concentration of A in the fluid just adjacent to the solid
c1is = concentration of A in the solid at the surface and is in equilibrium with c1i
kc1 and kc2 = mass transfer coefficients (m/s)

 Substituting c1is = Kc1i and c2is = Kc2i

N A kc1 (c1 c1i ) pM (c1i c2i ) kc 2 (c2i c2 )

DAB K '
pM
L

pM

= permeance in the solid (m/s)

= solid thickness, (m)

DAB

= diffusivity of A in solid (m2/s)

NA
NA
NA
c1 c1i
c1i c2i
c2 i c2
kc1
pM
kc 2
The overall flux equation:

c1 c2
NA
1
1
1

kc1 pM kc 2

Total resistance

Gas Permeation Membrane Process

In membrane process with two gas phases and a solid membrane, the equilibrium
relation between the solid and gas phases is given by

cs
c1is
c2is
S
H

22.414 p A p A1i p A 2i

H = equilibrium relation (kg mol/ m3.atm)

S = solubility of A (m3(STP)/atm.m3 solid)

The flux equations in each phase :

k c1
kc 2
PM
p A1 p A1i p A1i p A2i p A2i p A2
NA
RT
L
RT
Permeability PM DAB H

The overall flux equation:

DAB S kgmol

22.414 s m atm

p A1 p A 2
NA
1 / kc1 / RT 1 / PM / L 1 / kc 2 / RT

TYPES OF EQUIPMENT FOR GAS PERMEATION MEMBRANE PROCESS

Flat membranes
Mainly used in experiments to characterize the permeability of the membrane. The
modules are easy to fabricate. This type of membrane has very small membrane area per
unit separator volume.

Spiral-wound membranes
This configuration
increases markedly the
membrane area per unit separator volume up to 328
m2/ m3 and decreases the pressure drop.
The assembly consists of a sandwich of four sheets
wrapped around a central core of a perforated
collecting tube.
The feed gas enters at the left end of the shell, enters
the feed channel and flows through this channel in
the axial direction of the spiral to the right end of the
assembly.
Then, the exit residue gas leaves the shell at this
point.
The feed stream permeates perpendicularly through
the membrane.
This permeate then flows through the permeate
channel toward the perforated collecting tube.

Hollow-fibre membranes
The membranes are in the shape of very small diameter
hollow fibres.
The inside diameter of the fibres is in the range of 100 to
500 m and the outside 200 to 1000 m with the length
up to 3 to 5 m.
The module resembles a shell-and-tube heat exchanger.
Thousands of fine tubes are bound together at each end
into a tube sheet that is surrounded by a metal shell
having a diameter of 0.1 to 0.2 m.
The high pressure feed enters the shell side at one end
and leaves at the other end.
The hollow fibres are closed at one end of the tube
bundles.
The permeate gas inside the fibres flows counter-current
to the shell side flow and is collected in a chamber where
the open ends of the fibres terminate.
Then the permeate exits the device.

TYPES OF FLOW IN GAS PERMEATION

Figure (a), complete mixing is assumed for
the feed and the permeate chamber. Similar
to continuous-stirred tank, the reject
(residue) and the product (permeate)
compositions are equal to their respective
uniform compositions.
Figure (b), the feed stream is in plug flow
and the permeate flows in normal direction
away from the membrane without mixing.
The permeate concentration varies along
the membrane path.
Figure (c), both the feed stream and
permeate stream are in plug flow countercurrent to each other. The composition of
each stream varies along its flow path.
Figure (d), both the feed stream and
permeate stream are in plug flow co-current
to each other. The composition of each
stream varies along its flow path.

Ideal flow patterns in a membrane separator for gases:

(a) complete mixing; (b) cross-flow; (c) counter-current flow;
(d) co-current flow.

Example 13.2-1
A liquid containing dilute solute A at a concentration c1 = 3 x 10-2 kg mol/m3
is flowing rapidly past a membrane of thickness L = 3.0 x 10-5 m. The
distribution coefficient K = 1.5 and DAB = 7.0 x 10-11 m2/s in the membrane.
The solute diffuse through the membrane and its concentration on the other
side is c2 = 0.50 x 10-2 kg mol/m3. The mass transfer coefficient kc1 is large
and can be considered as infinite and kc2 = 2.02 x 10-5 m/s.
(a) Derive the equation to calculate the steady-state flux NA and make a
sketch.
(b) Calculate the flux and concentrations at the membrane interfaces.

Example 13.2-1 - SOLUTION

Part (a). Concentration profile on the left side is flat (kc1 = ). The concentration of c1i= c1. Hence,
1/kc1=0.

c1 c2
NA
10 1
1

kc1 pM kc 2

Part (b). To calculate the flux:

Calculate
flux

DAB K ' 7.0 10 11 (1.5)

6
pM

3
.
5

10
m/s
5
L
3 10
c1 c2
3 10 2 0.5 10 2
NA

1 / pm 1 / k c 2 1 / 3.5 10 6 1 / 2.02 10 5
7.458 10 -8 kg.mol/s.m 2
N A 7.458 10 -8 kc2 (c2 i c2 ) 2.02 10 5 (c2 i 0.5 10 2 )
c2 i 8.692 10 3 kg.mol/m3
c2 iS
c2 iS
K 1 .5

c2 i 8.692 10 3
'

Calculate
concentration,
c2is

c2 iS 1.304 10 2 kg.mol/m3

Example 13.2-2
Calculate the flux and the rate of removal of urea at steady state in g/h from blood in a
cellophane membrane dialyzer at 37oC. The membrane is 0.025 mm thick and has an
area of 2.0 m2. The mass transfer coefficient on the blood side is estimated as kc1 = 1.25 x
10-5 m/s and that on the aqueous side is 3.33 x 10-5 m/s. The permeance of the membrane
is 8.73 x 10-6 m/s. The concentration of urea in the blood is 0.02 g urea/100 mL and that
in the dialyzing fluid will be assumed as 0.
Example 13.2-2 - Solution
NA

c1 c2
1 / k c1 1 / p M 1 / k c 2

200 - 0
1/1.25 10 -5 1 / 8.73 10 6 1 / 3.33 10 5
8.91 10 - 4 g/s.m 2

For a time of 1 h and an area of 2.0 m 2

rate of romoval 8.91 10 - 4 (3600)(2.0)
6.42 g urea/h

17

Discuss the applications and the benefit (e.g. cost savings, enable
maximum product recovery, optimize economic efficiency and
sustainable environment) of membrane technology in:
PETROCHEMICAL INDUSTRIES
OIL AND GAS INDUSTRIES
FOOD INDUSTRIES
WASTEWATER TREATMENT
DESALINATION OF SEAWATER