WHAT IS A MEMBRANE?

• Membranes are materials which

have voids in them, letting
some molecules (or particles)
pass more conveniently than
some other molecules.
• A semi-permeable membrane
is a VERY THIN film that
allows some types of matter to
pass through while leaving
others behind

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The concentrate,
the retained matter Basics
The filtrate,
the liquid passing
through the membrane

Transmembrane pressure
•Pressure gradient between the upstream (retentate side) and downstream (permeate
side)

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 HOW SEPARATION OCCURS
Difference in permeabilities through a membrane:
– Difference in pore size,
– Charge

DRIVING FORCES
• Pressure difference,
• Concentration difference,

ADVANTAGES DISADVANTAGES
•Continuous separation •Fouling
•Low energy requirement •Service periods
•Meet various separation demands

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Membrane material
•Membranes may be composed of natural (e.g modified
natural cellulose polymers ) or synthetic polymers (plastic
materials) or inorganic ceramic materials
Membrane filtration applications
1. Reverse osmosis (RO)
2. Nanofiltration (NF)
3. Ultrafiltration (UF)
4. Microfiltration (MF)

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5
MICROFILTRATION
Is a filtration process which removes contaminants from a fluid
(liquid & gas) by passage through a microporous membrane
operated at low pressure differences used to filter particles.

wide array of applications:

sterile water for
pharmaceutical industry
food & beverages
chemical industry
microelectronics industry
fermentation
laboratory/analytical uses
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ULTRAFILTRATION
Is a variety of membrane filtration in
which hydrostatic pressure forces a
liquid against a semi permeable
membrane.

Suspended solids and solutes of high

molecular weight are retained, while
water and low molecular weight solutes
pass through the membrane.

This separation process is used in industry

and research for purifying and
concentrating macromolecular, especially
protein solutions.

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ULTRAFILTRATION

has smaller pores than microfiltration membranes

driving force → pressure differential (2-10 bars to 25-30
bars).
used to separate species with pore sizes 10-1000 Å.
Usually assymmetric membrane.

Assymmetric - membrane in which the pore

size and structure vary from one side of the
membrane to the other of the membrane

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ULTRAFILTRATION
• wide range of applications :
– Oil emulsion waste treatment
– Treatment of whey in dairy industries
– Concentration of biological macromolecules
– Electrocoat paint recovery
– Concentration of textile sizing
– Concentration of heat sensitive proteins for food additives

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NANOFILTRATION
Relatively recent membrane
filtration process used most
often with low total dissolved
solids water such as surface
water and fresh groundwater,
with the purpose of softening
(polyvalent cation removal) and
removal of disinfection by-
product precursors such as
natural organic matter and
synthetic organic matter.

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NANOFILTRATION
Range between UF and RO membranes
The mass transfer mechanism is diffusion.
For small molecules from the solution.
cellulosic acetate and aromatic polyamide type
membranes (salt rejections; 95% for divalent salts to 40%
for monovalent salts)
can typically operate at higher recoveries; conserving
total water usage due to a lower concentrate stream flow
rate.
Typical applications:
–desalination of food, dairy and beverage products or
byproducts.
–partial desalination of whey(is a remaining liquid after
milk has curdled and strained).
–desalination of dyes and optical brighteners.
–color reduction or manipulation of food products.
–concentration of food, dairy and beverage products or
byproducts. 11
–fermentation byproduct concentration.
Membrane Configurations / modules
This refers to the packing of the membrane in the module
so that it can be installed in the system.

Common configurations include:

•Plate and frame
•Tubular
•Spirally wound
•Hollow fine fiber

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Flat membranes

Used directly.
In some cases modules are stacked together like a multilayer sandwich
or plate-and-frame filter press
Three basic structures are commonly used for membranes
1 homogeneous (no significant variation in pore diameter from the
filtering surface to the other side)
2 asymmetric (has a thin layer next to the filtering surface that has
varying structure)
3 composite (constructed from different types of materials)

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Plate and frame design

Membrane sandwiched between membrane support

plates which are arranged in stacks
Typically polymers (e.g polyethersulfone) with
polypropylene or polyolefin support.

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Spiral wound membranes

Constructed from flat sheet membranes separated by spacer

screens
Consists of a sandwich of four sheets wrapped around a
central core of a perforated collecting tube
The four sheets consist of a
1. top sheet of an open separator grid for feed channel
2. a membrane
3. a porous felt backing for the permeate channel
4. another membrane
The feed solution is fed into one end of the module and
flows through the separator screens along the surface of the
membranes
The retentate is collected in the other end of the module
The permeate spirals radially inward, eventually to be
collected through a central tube
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Spiral-wound elements and assembly
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spiral-wound membrane - cross section

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3. Hollow-fiber membranes
The membranes are in the shape of
very-small-diameter hollow fibers
Typically, the high-pressure feed
enters the shell side at one end and
leaves at the other end
The hollow fibers are closed at one
end of the tube bundles
Hollow-fiber separator assembly.
The permeate solution inside the
fibers flows countercurrent to the
shell-side flow and is collected in a
chamber where the open ends of the
fibers terminate
Then the permeate exits the device

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Comparison of membrane module

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Comparison of membrane module

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 Liquid Permeation Membrane Processes
(Dialysis)
Liquid Resistances in Membrane Processes

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 Liquid Resistances in Membrane Processes

= equilibrium distribution
coefficient

pM is the permeance in m/s

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 Liquid Resistances in Membrane Processes

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 Example 13.2-1 Solution

CHET306 Module IV Membrane Separation

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Processes
 Example 13.2-1 Soln. Contd.

CHET306 Module IV Membrane Separation

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Processes
 Dialysis Processes

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Hemodialysis:
http://en.wikipedia.org/wiki/File:Hemodial
ysis-en.svg

CHET306 Module IV Membrane Separation

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Processes
 Hemodialysis in Artificial Kidney
Solutes: urea, uric acid, creatinine, phosphates, Cl
Membrane: cellophane 0.025 mm (25 µm) thick
Solutes diffuse across the membrane to the dialyzing
aqueous solution.
Solute fluxes (low flux rates compared to RO & UF) depends
on the concentration gradient in the membrane

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 Hollow Fiber Artificial Kidney

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 Gas Permeation Membrane Processes

= [(DAB S/L(22.414))] (pA1i - pA2i)

Permeability PM given previously by equation 6.5-9.

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Gas Permeation Membrane Processes
Permeability PM is given in kg mol units by dividing equation 6.5-9 by
22.414 m3/kg mol (Eq. 13.3-5).
Then the flux NA through the membrane, given by Eq.13.3-3, becomes Eq.(13.3-
6).
Eliminating interfacial concentrations as before, Eq. (13.3-7) can be deduced:

PM /L in kmol/s m2 atm
Application:
The use of polymeric membrane as an oxygenator for a heart-lung machine to
oxygenate blood . Pure O2 gas on one side and blood is on the other side of a
membrane. O2 diffuses through membrane into blood and CO2 diffuses in reverse
direction into the gas stream.

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 Membrane Blood Oxygenator

Lung surface area= 80

m2 , Thickness = 1 µm

CHET306 Module IV Membrane Separation

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Processes
 Introduction to types of flow in Gas
Permeation
• Types of Flow and Diffusion Gradients:
• Due to high diffusivity in gases, concentration gradient in the gas
phase is small as compared to membrane resistance, gas film
resistance is neglected compared to membrane resistance.
• There are various types of gas separation processes depending upon
the flow characterizations.
1. If there is complete mixing of the feed and permeate by an external
agent (stirrer or mixer), then the configuration is complete mixing
(Fig. 13.3-4a).
2. Since the permeate comes normal to the flow direction of the feed,
this is known as simple cross flow (Fig. 13.3-4b).
3. If they are in opposite direction, then it is counter current flow (Fig.
13.3-4c).
4. If feed and permeate are in the same direction, then the flow is
concurrent flow (Fig.13.3-4d).

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 Ideal Flow Patterns in a Membrane Separator for
Gases

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 Complete mixing model for gas
separation by membranes

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Processes
 Complete mixing model for gas
separation by membranes

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 Complete mixing model for gas
separation by membranes

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 Complete mixing model for gas
separation by membranes

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 Complete mixing model for gas
separation by membranes

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continue

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43
Minimum concentration of Reject Stream

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OSMOSIS
Water flows from a dilute solution
through a semipermeable membrane
(water permeation only) to a higher
concentrated solution
Rise in volume to equilibrate the pressure
(osmotic pressure)
REVERSE OSMOSIS
If a pressure greater than the
osmotic pressure is applied to the
high concentration the direction of
water flow through the membrane
can be reversed.
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REVERSE OSMOSIS
• only remove some suspended materials larger than 1 micron
• the process eliminates the dissolved solids, bacteria, viruses and
other germs contained in the water
• only water molecules are allowed to pass by applying very high
pressure. 25- 70 bar

extensive applications:
– Prepare pure water from dilute aqueous solutions
– Purify organic solvent
– potable water from sea or brackish water
– Ultra pure water for food processing and electronic industries
– water for chemical, pulp & paper industry

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 Flux Equation for Reverse Osmosis
1. Osmotic pressure of solutions
Experimental data shows that the osmotic pressure π of a solution is
proportional to the concentration of the solute and the temperature T
Van’t Hoff originally showed that the relationship is similar to that for
pressure of an ideal gas
For example, for dilute water solutions,
n: number of kg mol of solute,
n Vm: volume of pure solvent water in m3
= RT (1) associated with n kg mol of solute,
Vm R: gas law constant 82.057 x 10-3 m3·atm/kg mol·K,
T: 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 the osmotic
coefficient Φ, which is the ratio of the actual osmotic pressure π to the ideal
π calculated from the equation 47
Example 13.9-1
Calculate the osmotic pressure of a solution containing 0.10 g mol NaCl/1000
g H20 at 25°C.
Solution:
The density of water = 997.0 kg/m3 and then, n = 2 x 0.10 x 10-3 =
2.00 x 10-4 kg mol (NaCl gives two ions). Also, the volume of the
pure solvent water Vm = 1.00 kg/(997.0 kg/m3). Substituting into
Eq. (1),

n 2.00 10 4 (82.057 10 3 )(298.15)

= RT = = 4.88atm
Vm 1.00 / 997.0

This compares with the experimental value in Table 13.9-1 of 4.56 atm.

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 Example 13.9-1
TABLE 13.9-1. Osmotic Pressure of Various Aqueous
Solutions at 25°C

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 Flux Equation for Reverse Osmosis
2. Diffusion-type models
For the diffusion of the solvent through the membrane,

Pw
Nw = ( P ) = Aw ( P )
Lm
Pw
Aw =
Lm

Nw is the solvent (water) flux in kg/s·m2;

Pw the solvent membrane permeability, kg solvent/s·m·atm;
Lm the membrane thickness, m;
Aw the solvent permeability constant, kg solvent/s·m2·atm;
ΔP = P1 - P2 (hydrostatic pressure difference with P1 pressure exerted on
feed and P2 on product solution), atm;
Δπ = π1 - π2 (osmotic pressure of feed solution - osmotic pressure of product
solution), atm.
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 Flux Equation for Reverse Osmosis
For the diffusion of the solute through a membrane, an approximation for
the flux of the solute is
Ds K s
Ns = (c1 c2 ) = As (c1 c2 )
Lm
Ds K s
As =
Lm

Ns is the solute (salt) flux in kg solute/s·m2;

Ds the diffusivity of solute in membrane, m2/s;
Ks = cm/c (distribution coefficient), concentration of solute in
membrane/concentration of solute in solution;
As is the solute permeability constant, m/s;
c1 the solute concentration in the feed (concentrate) solution, kg solute/m3;
c2 the solute concentration in the product (permeate) solution, kg solute/m3.
The distribution coefficient Ks is approximately constant over the
membrane.
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 Flux Equation for Reverse Osmosis
Solute mass balance around the membrane gives:

N w c2
Ns =
cw2

Where cw2 is the concentration of the solvent in the products, kg solvent/m3.

If the products solution is dilute, cw2 is approximately the density of the
solvent.
In reverse osmosis, the solute rejection R is defined as the ratio
concentration difference across the membrane divided by the bulk
concentration on the feed (fraction of solute remaining in the feed)
c1 c2 c
R= =1 2
c1 c1 52
 The solute rejection R can be expressed as :

B( P )
R=
1+ ( P )

where B composes of various physical properties and is in atm-1

Pw Aw
B= =
Ds K s cw2 As cw2

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Example 13.9-2
Experiments at 25°C were performed to determine the permeabilities of
a cellulose acetate membrane. The laboratory test section shown in Fig.3
has membrane area A = 2.00 x 10-3 m2. The inlet feed solution
concentration of NaCl is c1 = 10.0kg NaCl/m3 solution (10.0 g NaCI/L, ρ1
= 1004 kg solution/m3). The water recovery is assumed low so that the
concentration c1 in the entering feed solution flowing past the membrane
and the concentration of the exit feed solution are essentially equal. The
product solution contains c2 = 0.39 kg NaCl/m3 solution (ρ2 = 997 kg
solution/m3) and its measured flow rate is 1.92 x 10-8 m3 solution/s. A
pressure differential of 5514 kPa (54.42 atm) is used.

Calculate the permeability constants of the membrane and

the solute rejection R.

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FIGURE 3. Process flow diagram of experimental reverse-osmosis laboratory unit.

Solution:

Since c2 is very low (dilute solution), the value of c2 can be approximated

as the density of water , or cw2 = 997 kg solvent/m3.

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To convert the product flow rate to water flux, Nw, using an area of
2.00 x 10-3 m2, we can calculate the flux of water (solvent)

N w = (1.92 10 8 m 3 /s)(997kg solvent/m 3 )(1/ 2.00 10 3 m 2 )

N w = 9.57 10 3 kg solvent/s ×m 2
Using the mass balance around the membrane, the solute flux can
be calculated as:
N w c2 (9.57 10 3 )(0.39)
Ns = =
cw2 997
N s = 3.477 10 6 kg solute NaCl/s ×m 2

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 To determine the osmotic pressures from Table 13.9-1, the concentrations
are calculated as follows:
For c1, 10 kg NaCl is in1004 kg solution/m3
Hence, 1004 – 10 = 994 kg water in 1 m3 solution. And the molecular weight
of NaCl = 58.45,
(10)(1000)
= 0.1721gmol NaC1/kg H2O.
(994)(58.45)
From Table 13.9-1, π1 = 7.80 atm.

For the product solution, 997 - 0.39 = 996.6 kg water in 1 m3 solution .

(0.39)(1000)
= 0.00670 gmol NaCl/kg H2O
(996.6)(58.45)

From Table 13.9-1, π2 = 0.32 atm.

Then, Δπ = π1 - π2 =7.80 - 0.32 = 7.48 atm and ΔP = 54.42 atm.

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 The solvent permeability constant
Pw
Nw = ( P )
Lm
Pw
9.57 ´10 3 = (54.42 7.48)
. Lm
Pw
Recall Þ = Aw Þ Aw = 2.039 ´10 4 kg solvent/ s. m 2 atm
Lm

The solute permeability constant

Ds K s
Ns = (c1 c2 )
Lm
Ds K s
3.477 10 6 = (10.00 0.39)
Lm
Ds K s
Recall = AS AS = 3.896 10 7m/s
Lm

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 Solute rejection R

c1 c2 10.00 0.39
R= = = 0.961
c1 10.00

Or
Pw / Lm 2.039 ´10 4 1
B= = = 0.5249 atm
(Ds K s / Lm )cw2 (3.896 ´10 7 )997
B( P ) 0.5249(54.42 7.48)
R= = = 0.961
1+ B( P ) 1+ 0.5249(54.42 7.48)

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