MEMBRANE

DR NONNI SORAYA SAMBUDI

 Learning Outcomes
At the end of this chapter, student is expected to be able to:

1) explain the theories involved in membrane process

2) describe different types of membrane mechanisms
3) describe the factors affecting the membrane performance
4) derive the steady state flux and understand the transport mechanism of liquid
permeation process
5) derive the steady state flux for gas permeation process
6) apply the theory of complete mixing model in solving problems related to gas
permeation
2
Lecture Learning
Outcomes
• By the end of this sub-topics,
you should be able to:
• explain the theories involved
in membrane process
• describe different types of
membrane mechanisms
• describe the factors affecting
the membrane performance

3
What is Membrane?
A membrane is defined as a thin layer of semipermeable material which partially
separates two phases and controls the movement of solutes across it in a specific
manner.
OR
A selective barrier that permits the separation of certain species in a fluid/gas by
combination of sieving and sorption diffusion mechanism.

4
APPLICATIONS

• Any
applications or
example of
membrane in
your daily life?

5
 EXAMPLE OF MEMBRANE APPLICATION

Kidney

6
ULTRAFILTRATION

7
 Membrane components
In membrane separation :
1) the two products are usually
miscible
2) the separating agent is a
semipermeable barrier

Feed - Stream that fed to the membrane

Retentate - Does not pass through the membrane

Permeate - Passes through the membrane

Sweep (Optional stream) – use to help remove the permeate

Solute - Component(s) of interest 8

Membrane Materials
 Polymeric membranes
 organic membranes e.g. sulfone
membrane, PVDF, polyamide, polystyrene To maintain
and Teflon performance and
 natural polymers- rubber, wool, cellulose selectivity
membrane MUST
 Non-polymeric membranes NOT
 inorganic membranes e.g. metal, ceramic,  Dissolve
carbon and zeolites
 liquid membranes e.g. thin oil film
 Disintegrate

 Hybrid membranes  Break

 or Mixed Matrix Membranes where both 9

organic and inorganic components are

used
9
How is Separation achieved?

Membrane selectively
Membrane retarding the
Feeding a miscible stream into passing (permeating) one of
passage of one or more
membrane separation system more components of a
other components
stream through it

DRIVING FORCE FOR MEMBRANE

Pressure, concentration, temperature, electrical potential.

10
 Mechanism for transport across membrane

Knudsen diffusion: Diffusion Solution diffusion: solution

Bulk flow :pore diameter is large through pores. Pressure on Sieving: pore size is of diffusion in which the solute of
compared to molecular diameter of both side of membrane is the the order of molecular interest will have to be absorb
solute, and pressure difference same. Separation occurs due size for some of the into the membrane, diffuse
exist across the membrane allowing to difference in concentration, component, resulting through the solid membrane
bulk flow to pass through the pores. partial pressure, fugacity, in sieving effect to the other side. Main
No separation occurs. activity coefficient or chemical transport mechanism in
potential. reverse osmosis, gas & liquid
11
permeation
 Mechanisms for GAS SEPARATION
Dense Membrane
Solution-diffusion model has postulated a three-step process for gas transport
through a dense membrane/polymer:

1) Dissolution of the gas into the high-pressure (or high chemical potential)
upstream face of the polymer,
2) Diffusion of the gas through the polymer, and
3) Desorption from the low-pressure (i.e., low chemical potential) downstream
face of the polymer
12
 Types of membrane
Flat sheet

• One of the earliest types of membrane

system
• Easy to fabricate and use
• Well defines membrane areas
• Very small membrane areas per unit
separate volume
• Relatively high cost
• Commonly use for experiment
purposes (to find the permeability
gases through the membrane)

13
Types of membrane
SPIRAL WOUND

 Configuration similar to flat membranes

 Increases membrane area per unit
separator volume up to 100 ft2/ft3
 Four sheets wrapped around a central core
of perforated collecting tube
 Top sheet has grid for feed channel
 Multi-envelope designs minimise the
pressure drop encountered by the
permeate travelling toward the central pipe
 Permeate flow perpendicular to the feed
flow towards the perforated collecting
tube
14
Types of membrane
HOLLOW FIBRE
• Range of inside diameter =
100-500 micronmeter
• Range of outside diameter =
200 – 1000 microns
• Resemble shell & tube HE
• Thousands of fine tubes
bound together resulting in
large membrane area per
unit volume
• Typically, high pressure feed
enters the shell side

15
Gas permeation modules
1. Gas diffusion in porous solid / membrane
• Microporous solid used to separate gas-gas mixture
• Rates of molecular diffusion depends on pore size and
molecular weight
2. Gas permeation in dense membrane
• Gaseous solute dissolve and diffuse through non-porous
membrane to the other gas phase.
Membrane Performance
Permeabilities of various gases in membranes, cm3 (STP). cm /cm2.s.cmHg
x 1010

Material Temp He H2 CH4 CO2 O2 N2

(oC)
Silicon rubber 25 300 550 800 2700 500 250
Natural rubber 25 31 49 30 131 24 8.1

Polycarbonate 25-30 15 12 - 5.6,10 - -

Nylon 66 25 1 - - 0.17 0.008 0.008
Silicon- 25 - 210 - 970 70 70
polycarbonate
Teflon 30 62 1.4 25

Ethyl cellulose 30 35.7 49.2 7.47 47.5 11.2 3.29

Polystyrene 30 40.8 56 2.72 23.3 7.47 2.55

(Geankoplis 4th Edition, Table 13.3.2 page 848

17
 Membrane Performance

1) PERMEATION FLUX
 volume flowing through the membrane per 2) PERMEABILITY COEFFICIENT (Pi)
unit area per unit time.  flux of species through the membrane per
 SI unit = [ m3/m2.s] unit driving force
 SI unit = Barrer
1 Barrer = 10-10 cm3.cm /cm2. s . cmHg at STP

larger pore size and more porous

Pi = K i Di (1)
Membrane
Type base on the pore size
and porosity
Flux
Ki is the sorption coefficient
small pore size and less porous Di is the permeate diffusion coefficient

Pressure

18
 Membrane Performance
3) PERMEANCE (PM) 4) MEMBRANE SELECTIVITY
 ratio of the permeability coefficient (αAB)
(Pi) to the membrane thickness (L).  Given by ratio of permeability
 Analogous to mass transfer
coefficient
PA
α AB =
PB
(3)
DAB K'
pM = (2) Replacing for PA and PB using [1], and re-arrange:

L K A DA
pM - permeance in the solid, (m/s) α AB = (4)
K B DB
L - solid thickness, (m)
DAB - diffusivity of A in solid (m2/s)
19
Membrane Performance
Exercise 1) Choose the best membrane material
to separate H2 from CH4, H2 and CO2 mixture.

Material Temp H2 CH4 CO2

(oC)
Silicon rubber 25 550 800 2700
Natural rubber 25 49 30 131

Ethyl cellulose 30 49.2 7.47 47.5

Polystyrene 30 56 2.72 23.3

(Geankoplis 4th Edition, Table 13.3.2

page 848

20
Membrane Performance

Exercise 2) Choose the best membrane material

to separate CO2 from CH4

Material Temp CH4 CO2

(oC)
Silicon rubber 25 800 2700
Natural rubber 25 30 131

Ethyl cellulose 30 7.47 47.5

Polystyrene 30 2.72 23.3

(Geankoplis 4th Edition, Table 13.3.2

page 848
21
Liquid permeation
process

22
 Series Resistance in Membrane
Processes
Dense
Solute diffuses Feed Permeate
membrane
through the
liquid film on L
c1 c1i Finally the solute passes
one side of the through the liquid film
kc1 c
membrane. 1iS on the other side of the
membrane
c2i
NA c2
c2iS
kc2
DAB

Solute passes ** indicator:

through the 1- bulk fluid
c - concentration (kg mol/m3) 2 – permeate
membrane
kc - mass transfer coefficient (m/s) i – adjacent to solid surface
iS- in the solid
NA - Flux through membrane (kg mol/m2.s)

Concentration profiles for membrane processes: two liquid films 23

 Dense Permeate
Feed
membrane
L
c1 c1i
kc c
c1is and c2is are unknown and
1
1iS
unmeasurable, thus how can we
solve this problem?
kc
NA c2
c2iS 2c2i
DAB
I II III

DAB = k c 2 ( c2 i − c2 ) (3)
N A = kc1 (c1 − c1i ) = (c1is − c2is )
L

I II III

Boundary Inside Boundary

layer at the Membrane layer at the
feed side permeate
side
DAB=Diffusivity of A, m2/s
L=thickness, m 24
 DAB
N A = kc1 (c1 − c1i ) = (c1is − c2is ) = kc 2 (c2i − c2 )
L
Derive the equation!
Discuss with your neighbor, given that:
Equilibrium distribution coefficient K’ and permeance are defined as

DAB K' c c c
pM = K '= = = S 1 iS 2 iS

L c c c L 1i 2i

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

pM - permeance in the solid (m/s)
L - solid thickness, (m)
DAB - diffusivity of A in solid (m2/s)
25
 N A = kc1( c1 − c1i ) = pM ( c1i − c2i ) = kc 2 ( c2i − c2 ) (4)

Dense
Feed Permeate
membrane

L
c1 c1i
𝑁𝑁𝐴𝐴
kc1 c
1iS
c1 − c1i = 𝑘𝑘𝑐𝑐𝑐
𝑁𝑁𝐴𝐴
c1i − c2i =
kc2 𝑝𝑝𝑀𝑀
NA
c2iS c2i
c2
c2 i − c2 = 𝑁𝑁𝐴𝐴
DAB
𝑘𝑘𝑐𝑐𝑐

26
 Series resistances in membrane
processes
Solving for the concentration difference

NA NA NA
c1 − c1i = c1i − c2i = c2 i − c2 = [6]
kc1 pM kc 2
Adding the equations:

c1 − c2 [7]
NA =
1 1 1
+ + Series
k c1 pM kc 2 resistances

flux is inversely
proportional to the
NA - flux (kg mol/s m2 ) resistance

27
 • How much has passed through the
membrane?
According to Fick’ Law,

Permeability
Flux = [Driving Force]
Membrane thickness
Steady state!

pressure gradient,
concentration gradient,
electrical force, etc.
28
 EXAMPLE 1: Liquid Permeation

A liquid containing dilute solute A at a concentration c1 = 3 x10-2 kgmol/m3 is

flowing rapidly past a membrane of thickness L = 3.0x10-5 m. The distribution
coefficient, K’ = 1.5 and DAB = 7.0x10-11 m2/s in the membrane. The solute
diffuses through the membrane and its concentration on the other side is c2 =
0.50 x 10-2 kgmol/m3. The mass transfer coefficient kc1 is large and can be
considered as infinite and kc2 = 2.02x10-5 m/s.
a) Derive the equation to calculate the steady state flux NA and make a
sketch.
b) Calculate the flux and the concentrations at the membrane interfaces.

29
 Dense
Feed Permeate
membrane
L
c1iS
Kc1=
c1 c1i

kc2
NA c2
c2iS c2i
DAB

Part (a). Since the flow is very rapid, no resistance flow at the feed side of the
membrane. The concentration of C1i=C1. Hence, 1/kcl=0. Equation [9] becomes,

c1 − c2
NA =
1 1 1
+ +
0 k c1 pM kc 2
30
 Transport-Liquid Permeation
Part (b)
D AB K ' 7.0 × 10 −11 (1.5) −6
pM = = −5
= 3 . 5 × 10 m/s
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 = 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
∴ c2 iS = 1.304 × 10 − 2 kg.mol/m3
31
 EXAMPLE 2

Calculate the flux and the rate of removal of urea at steady state in g/h from
blood in a cuprophane (cellophane) membrane dialyzer at 37°C. 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.

32
Solution
The concentration c1 = 0.02/100 = 2 × 10-4 g/mL = 200 g/m3

And c2 = 0

𝑐𝑐1 − 𝑐𝑐2
𝑁𝑁𝐴𝐴 =
1 1 1
+ +
𝑘𝑘𝑐𝑐𝑐 𝑝𝑝𝑀𝑀 𝑘𝑘𝑐𝑐𝑐
200 − 0
𝑁𝑁𝐴𝐴 =
1� + 1� + 1�
1.25 × 10 −5 8.73 × 10 −6 3.33 × 10−5
−4
𝑔𝑔 2
𝑁𝑁𝐴𝐴 = 8.91 × 10 . 𝑚𝑚
𝑠𝑠

For a time of 1 h and an area of 2 m2,

rate of removal = 8.91 × 10-4 (3600) (2) = 6.42 g urea/h

33
Gas permeation
process

34
 What are the mechanisms for GAS SEPARATION
in membrane?
Dense Membrane
Solution-diffusion model has postulated a three-step process for gas transport
through a dense membrane/polymer:

1) Dissolution of the gas into the high-pressure (or high chemical potential) upstream
face of the polymer,
2) Diffusion of the gas through the polymer, and
3) Desorption from the low-pressure (i.e., low chemical potential) downstream face
of the polymer 35
 Gas Permeation: Concentration profile
The flux through the membrane is given
PA1
PA1i L as:
kc1 kc1
c1iS
NA = ( p A1 − p A1i )
RT
NA
PA2i
DAB
c2iS
kc2 = (c1iS − c2iS )
PA2
L
Dense kc 2
Feed membrane Permeate
= ( p A 2i − p A 2 )
RT
P - partial pressure 1- bulk fluid
kc - mass transfer coefficient i- adj to solid
2 - permeate iS - in the solid surface
36
 Gas Permeation: Concentration profile
Converting from c to p using
PA1i L
PA1 Henry’s Law: H=S/22.414 = Cs/Cl
kc1
c1iS PM=DAB.S/22.414

N A = DAB (c1iS − c2iS ) S*=Solubilit

y @ STP
PA2i L
NA
c2iS
kc2 DAB  S 
PA2 =  ( p A1i − p A2i )
L  22.414 
Dense
membrane Permeate  PM 
Feed =  ( p A1i − p A 2i )
 L 
P - partial pressure 1- bulk fluid
permeability
kc - mass transfer coefficient i- adj to solid
2 - permeate iS - in the solid surface
37
 Is this equation
similar to liquid
permeation?

kc1
NA = ( p A1 − p A1i )
RT
 PM 
= ( p A1i − p A2i )
 L 
kc 2 Ideal Gas
=
RT
( p A 2i − p A 2 )
Law
38
 Gas Permeation Membrane
By eliminating the interfacial concentration, the flux
through the membrane is given as:

p A1 − p A 2
NA =
1 1 1
+ +
(kc1 / RT ) (PM / L ) (kc 2 / RT )
S = solubility of A in m3 (STP)/atm.m3
DAB = diffusivity of A in solid (m2/s)

39
Complete
mixing model

40
Complete mixing model
Vp = θ L f yp permeate

low pressure side pl , y p

reject
feed Low pressure side
Lf Lo = (1 − θ )L f
high pressure side ph , xo
xf xo

Units (of L & V) = cm3(STP)/s

Overall material balance: L f = Lo + V p 1
Complete mixing model – component
balance
Overall balance on component A:
L f x f = Lo xo + V p y p 2

 Divide eq. 2 by Lf , and rearrange to solve reject

composition:

x f −θ yp x f − xo (1 − θ )
xo = or y p = 3
(1 − θ ) θ

Cut or fraction of Vp
feed permeated: θ= Lf
Complete mixing model – component
balance
• Rate of diffusion (or permeation) of
component A The ratio of these
two equation will
4 give us a
relationship
Vp y p  P' A 
( ph xo − pl y p )
between
= concentration in
Am  t  the feed and
• Rate of diffusion (or permeation) of
permeate
component B

5
α* = P' A P'
V p (1 − y p )  P' B 
B

= ( ph (1 − xo ) − pl (1 − y p ))
Am  t 
Complete mixing model – membrane area for separation

• Substitute into eq. 4 and solving for the membrane

area, Am

Vp
θ= Lf

θL f y p
Am = 6
 P' A 
 ( ph xo − pl y p )
 t 
Complete mixing model – component
balance
• Dividing equations 4 and 5:

α* = P' A P'
B

α *  xo −  pl p  y p 
yp   h  7
=
1− yp (1 − xo ) −  pl p (1 − y p )
 h 
 y
Solve for ,pwe will get quadratic equation:

− b + b 2 − 4ac
yp = 8
2a

where,
a = 1− α *,
1 x0
b = −1 + α + +*
,
r r (α − 1)
*

− α * x0
c= , r = pl / ph
r
Gas
Permeation
– Complete
mixing
model
Hands on problem
solving
Case 1
• Xf, xo, α*, and pl/ph are given
• yp, θ, and Am are to be determined by solutions of the
equations

48
 Example 3 GIVEN:
yp =
− b + b 2 − 4ac
2a
A membrane is used to separate a gaseous
mixture of A and B. Feed flow rate is Lf = 1 x 104 where,
cm3(STP)/s and mole fraction of A in feed is xf = a = 1−α *,
0.5. The desired composition of the reject is xo = 1 x0 *
b = −1 + α * + + (α − 1),
r r
0.25. Assuming complete mixing model,
− α * x0
calculate: c= , r = pl / ph
r
(i) Permeate composition, yp and fraction
Membrane thickness, t = 2.54 x 10-3 cm
permeated, Pressure on the feed side, ph = 80 cm Hg
Pressure on permeate side is pl = 20 cm Hg
(ii) Membrane area required for the process,
Permeability: P’A = 50 x 10-10 cm3 (STP).cm/(s.cm2.cm
Am Hg)
P’B = 5 x 10-10 cm3 (STP).cm/(s. cm2.cm Hg) .
Substitute all values:

a = 1 − 10 = −9
1 0.25
b = −1 + 10 + + (10 − 1) = 22.0
0.25 0.25
− 10(0.25)
c= = −10
0.25
r = pl / ph = 0.25
− 22 + 22 2 − 4(−9)(−10)
yp = = 0.604
2(−9)

50
Using material balance equation: x f −θ yp
xo =
(1 − θ )
0.5 − θ (0.604)
0.25 =
(1 − θ )
θ = 0.706

Using equation for flux to solve for Area:

θL f y p
Am =
 P' A 
 ( ph xo − pl y p )
 t 
0.706(1×10 4 )(0.604)
=
 50 ×10 −10 
 (80(0.25) − 20(0.604) )
−3 
 2.54 ×10 
= 2.735 ×108 cm 2
51
 PROBLEM 1
AA
A polyamide spiral wound membrane is operating as figure and table below:

Parameter Value
Assume the complete mixing model Membrane thickness, t 2.53 × 10-5 m
Feed side pressure, Ph 400 cm Hg
is applied, Permeate side 20 cm Hg
i. The permeate composition, yp. pressure, Pl
Carbon dioxide 100 × 10-10
permeability, PCO2 cm3(STP).cm/(s.c
m2. cm Hg)
i. The fraction permeated, θ Natural gas 5 × 10-10
permeability, PNG cm3(STP).cm/(s.c
m2. cm Hg)
Mole fraction of CO2, xf 0.25
i. The membrane area, Am Flowrate, Lf 10,000 cm3
Reject, x 0.10
52
53
i. The permeate composition, yp.
100 × 10 −10
α* = = 20
5 × 10 −10
p 20
r= l = = 0.05
ph 400
a = 1 − α * = 1 − 10 = −19
1 x 1 0.10
b = −1 + α * + + o (α * −1) = −1 + ( 20) + + ( 20 − 1)
r r 0.05 0.05
= 19 + 20 + 38
= 77
− α * xo − 20(0.10)
c= = = −40
r 0.05

− b + b 2 − 4ac − 77 + (77) 2 − 4(−19)(−40)

yp = =
2a 2(−19)
− 77 + 5929 − 3040 This result shows that the permeate
= = 0.611
− 38 composition is richer with carbon dioxide
as compared with the feed composition. 54
•The fraction permeated, θ

𝑥𝑥𝑓𝑓 − 𝜃𝜃 𝑦𝑦𝑝𝑝
𝑥𝑥𝑜𝑜 =
1 − 𝜃𝜃
0.25 − 𝜃𝜃(0.611)
0.10 =
(1 − 𝜃𝜃)
∴ 0.1 + 0.1𝜃𝜃 = 0.25 − 0.611𝜃𝜃
∴ 0.711𝜃𝜃 = 0.15
∴ 𝜃𝜃 = 0.210

55
 •The membrane area, Am

𝜃𝜃𝐿𝐿𝑓𝑓 𝑦𝑦𝑝𝑝
𝐴𝐴𝑚𝑚 =
(𝑃𝑃′𝐴𝐴 /𝑡𝑡)(𝑝𝑝ℎ 𝑥𝑥𝑜𝑜 − 𝑝𝑝𝑙𝑙 𝑦𝑦𝑝𝑝 )
0.210(1 × 104 )(0.611)
=
(100 × 10−10 /2.53 × 10−5 )(200 × 0.10 − 20 × 0.611)
1.283 × 103 1.38 × 103 5 cm2
= = = 4.17 × 10
3.952 × 10−4 (7.78) 3.79 × 10−3

56
Case 2

• Xf, θ, α*, and pl/ph are given

• yp, xo, and Am are to be determined by solutions of the
equations
−𝑏𝑏1 + 𝑏𝑏12 −4𝑎𝑎1 𝑐𝑐1
• 𝑦𝑦𝑝𝑝 =
2𝑎𝑎1
Where,
𝑝𝑝𝑙𝑙 𝑝𝑝𝑙𝑙 ∗ ∗
𝑝𝑝𝑙𝑙 ∗
𝑝𝑝𝑙𝑙
𝑎𝑎1 = 𝜃𝜃 + − 𝜃𝜃 − 𝛼𝛼 𝜃𝜃 − 𝛼𝛼 + 𝛼𝛼 𝜃𝜃
𝑝𝑝ℎ 𝑝𝑝ℎ 𝑝𝑝ℎ 𝑝𝑝ℎ
𝑝𝑝𝑙𝑙 𝑝𝑝𝑙𝑙 ∗ ∗
𝑝𝑝𝑙𝑙 ∗
𝑝𝑝𝑙𝑙
𝑏𝑏1 = 1 − 𝜃𝜃 − 𝑥𝑥𝑓𝑓 − + 𝜃𝜃 + 𝛼𝛼 𝜃𝜃 + 𝛼𝛼 − 𝛼𝛼 𝜃𝜃 + 𝛼𝛼 ∗ 𝑥𝑥𝑓𝑓
𝑝𝑝ℎ 𝑝𝑝ℎ 𝑝𝑝ℎ 𝑝𝑝ℎ
𝑐𝑐1 = −𝛼𝛼 ∗ 𝑥𝑥𝑓𝑓

57
Example 4
• Membrane design for separation of air
It is desired to determine the membrane area needed to separate an air
stream using a membrane 1 mil thick with an oxygen permeability of P’A =
500 × 10-10 cm3 (STP).cm/(s.cm2.cmHg).
An α* = 10 for oxygen permeability divided by nitrogen permeability will be
used. The feed rate is Lf = 1 x 106 cm3 (STP)/s and the fraction cut θ = 0.20.
The pressures selected for use are ph = 190 cmHg and pl = 19 cmHg. Again,
assuming the complete-mixing model, calculate the permeate
composition, the reject composition, and the area. Feed composition, Xf =
0.209.

58
Solution
𝑝𝑝𝑙𝑙 𝑝𝑝𝑙𝑙 ∗
𝑝𝑝
∗ 𝑙𝑙
𝑝𝑝
∗ 𝑙𝑙
𝑎𝑎1 = 𝜃𝜃 + − 𝜃𝜃 − 𝛼𝛼 𝜃𝜃 − 𝛼𝛼 + 𝛼𝛼 𝜃𝜃
𝑝𝑝ℎ 𝑝𝑝ℎ 𝑝𝑝ℎ 𝑝𝑝ℎ
19 19 19 19
𝑎𝑎1 = 0.2 + − 0.2 − 10 0.2 − 10 + 10 0.2 = −2.52
190 190 190 190

𝑝𝑝𝑙𝑙 𝑝𝑝𝑙𝑙 𝑝𝑝𝑙𝑙 𝑝𝑝𝑙𝑙

𝑏𝑏1 = 1 − 𝜃𝜃 − 𝑥𝑥𝑓𝑓 − + 𝜃𝜃 + 𝛼𝛼 ∗ 𝜃𝜃 + 𝛼𝛼 ∗ − 𝛼𝛼 ∗ 𝜃𝜃 + 𝛼𝛼 ∗ 𝑥𝑥𝑓𝑓
𝑝𝑝ℎ 𝑝𝑝ℎ 𝑝𝑝ℎ 𝑝𝑝ℎ
𝑏𝑏1
19 19 19 19
= 1 − 0.2 − 0.209 − + 0.2 + 10 0.2 + 10 − 10 0.2
190 190 190 190
+ 10 0.209 = 5.401

𝑐𝑐1 = −𝛼𝛼 ∗ 𝑥𝑥𝑓𝑓 = -10(0.209) = -2.09

59
Solution
−𝑏𝑏1 + 𝑏𝑏12 − 4𝑎𝑎1 𝑐𝑐1 −5.401 + 5.401 2 − 4(−2.52)(−2.09)
𝑦𝑦𝑝𝑝 = = = 0.5067
2𝑎𝑎1 2(−2.52)

𝑥𝑥𝑓𝑓 − 𝜃𝜃 𝑦𝑦𝑝𝑝 0.209 − 0.2(0.5067)

𝑥𝑥𝑜𝑜 = = = 0.1346
1 − 𝜃𝜃 (1 − 0.2)

𝜃𝜃𝐿𝐿𝑓𝑓 𝑦𝑦𝑝𝑝
𝐴𝐴𝑚𝑚 =
(𝑃𝑃′𝐴𝐴 /𝑡𝑡)(𝑝𝑝ℎ 𝑥𝑥𝑜𝑜 − 𝑝𝑝𝑙𝑙 𝑦𝑦𝑝𝑝 )

0.2(1 × 106 )(0.5067)

𝐴𝐴𝑚𝑚 =
(500 × 10−10 ⁄2.54 × 10−3 )(190 × 0.1346 − 19 × 0.5067)
𝐴𝐴𝑚𝑚 = 3.228 × 108 𝑐𝑐𝑐𝑐2

60
Minimum concentration of reject stream
• The minimum reject composition xoM for a given xf value is:

∗ 𝑝𝑝𝑙𝑙
𝑥𝑥𝑓𝑓 1 + 𝛼𝛼 − 1 1 − 𝑥𝑥𝑓𝑓
𝑝𝑝ℎ
𝑥𝑥𝑜𝑜𝑜𝑜 =
𝛼𝛼 ∗ 1 − 𝑥𝑥𝑓𝑓 + 𝑥𝑥𝑓𝑓

61
Example 5
• Calculate the minimum reject concentration for Example 3 where
the feed concentration is xf = 0.50. Also, what is the effect of
raising the feed purity to xf = 0.65.

62
𝑥𝑥𝑓𝑓 = 0.5
𝑝𝑝𝑙𝑙
𝑥𝑥𝑓𝑓 1 + 𝛼𝛼 ∗ − 1 1 − 𝑥𝑥𝑓𝑓
𝑝𝑝ℎ
𝑥𝑥𝑜𝑜𝑜𝑜 =
𝛼𝛼 ∗ 1 − 𝑥𝑥𝑓𝑓 + 𝑥𝑥𝑓𝑓

20
0.5 1 + (10 − 1) (1 − 0.5)
80
𝑥𝑥𝑜𝑜𝑜𝑜 = = 0.1932
10 1 − 0.5 + 0.5

𝑥𝑥𝑓𝑓 = 0.65
20
0.65 1 + (10 − 1) (1 − 0.65)
80
𝑥𝑥𝑜𝑜𝑜𝑜 = = 0.278
10 1 − 0.65 + 0.65

63
 PROBLEM 2
Separation of air stream is using a membrane with an oxygen
permeability of P’A = 500 × 10-10 cm3 (STP).cm/(s.cm2.cmHg).

An α* = 10 for oxygen permeability divided by nitrogen

permeability will be used. The pressures selected for use are ph
= 190 cmHg and pl = 19 cmHg. Again, assuming the complete-
mixing model, make a plot of 𝑦𝑦𝑝𝑝 vs θ for θ = 0.25, 0.5, and 0.75.
Feed composition, Xf = 0.209.

64
Solution
𝑝𝑝𝑙𝑙 𝑝𝑝𝑙𝑙 𝑝𝑝𝑙𝑙 𝑝𝑝𝑙𝑙
𝑎𝑎1 = 𝜃𝜃 + − 𝜃𝜃 − 𝛼𝛼 ∗ 𝜃𝜃 − 𝛼𝛼 ∗ + 𝛼𝛼 ∗ 𝜃𝜃
𝑝𝑝ℎ 𝑝𝑝ℎ 𝑝𝑝ℎ 𝑝𝑝ℎ
𝑝𝑝𝑙𝑙 𝑝𝑝𝑙𝑙 𝑝𝑝𝑙𝑙 𝑝𝑝𝑙𝑙
𝑏𝑏1 = 1 − 𝜃𝜃 − 𝑥𝑥𝑓𝑓 − + 𝜃𝜃 + 𝛼𝛼 ∗ 𝜃𝜃 + 𝛼𝛼 ∗ − 𝛼𝛼 ∗ 𝜃𝜃 + 𝛼𝛼 ∗ 𝑥𝑥𝑓𝑓
𝑝𝑝ℎ 𝑝𝑝ℎ 𝑝𝑝ℎ 𝑝𝑝ℎ
𝑐𝑐1 = −𝛼𝛼 ∗ 𝑥𝑥𝑓𝑓

−𝑏𝑏1 + 𝑏𝑏12 − 4𝑎𝑎1 𝑐𝑐1

𝑦𝑦𝑝𝑝 =
2𝑎𝑎1

Variable Θ = 0.25 Θ = 0.5 Θ = 0.75

a1 -2.925 -4.95 -6.975
b1 5.806 7.831 9.856
c1 -2.09 -2.09 -2.09
yp 0.472398 0.339928 0.259831
65
 0,5

0,45

0,4

0,35

0,3
yp
0,25

0,2

0,15

0,1

0,05

0
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8

θ
66
Reverse osmosis

67
Reverse osmosis membrane processes

68
Osmotic pressure of solutions
• Van’t Hoff equation:
𝑛𝑛
𝜋𝜋 = 𝑅𝑅𝑅𝑅
𝑉𝑉𝑚𝑚
n = number of kg mol of solute
Vm = volume of pure solvent water in m3 associated with kg mol of
solute
R = gas law constant, 82.057 x 10-3 m3.atm/kg mol. K
T = temperature in K

69
Osmotic pressure of solutions
Example
• Calculate the osmotic pressure of a solution containing 0.10 g
mol NaCl/1000 g H2O at 25°C.
• Solution
ρ of water = 997 kg/m3.
N = 2 x 0.10 x 10-3 = 2 x 10-4 kg mol (NaCl gives 2 ions)
Vm = 1 kg/(997 kg/m3)
𝑛𝑛 2 × 10−4 82.057 × 10−3 298.15
𝜋𝜋 = 𝑅𝑅𝑅𝑅 = = 4.88 atm
𝑉𝑉𝑚𝑚 1/997

70
Osmotic pressure of solutions

71
Osmotic pressure of solutions

72
Flux equations for reverse osmosis
• Diffusion-type model

𝑃𝑃𝑤𝑤
𝑁𝑁𝑤𝑤 = ∆𝑃𝑃 − ∆𝜋𝜋 = 𝐴𝐴𝑤𝑤 ∆𝑃𝑃 − ∆𝜋𝜋
𝐿𝐿𝑚𝑚
𝑃𝑃𝑤𝑤
𝐴𝐴𝑤𝑤 =
𝐿𝐿𝑚𝑚
Nw = solvent (water) flux, kg/s.m2
Pw = solvent membrane permeability, kg solvents/s.m.atm
Lm = membrane thickness, m
Aw = solvent permeability constant, kg solvents/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 on product
solution), atm
73
Flux equations for reverse osmosis
𝐷𝐷𝑠𝑠 𝐾𝐾𝑠𝑠
𝑁𝑁𝑠𝑠 = 𝑐𝑐1 − 𝑐𝑐2 = 𝐴𝐴𝑠𝑠 𝑐𝑐1 − 𝑐𝑐2
𝐿𝐿𝑚𝑚
𝐷𝐷𝑠𝑠 𝐾𝐾𝑠𝑠
𝐴𝐴𝑠𝑠 =
𝐿𝐿𝑚𝑚
Ns = solute (salt) flux, kg solute/s.m2
Ds = diffusivity of solute in membrane, m2/s
Ks = cm/c (distribution coefficient), concentration of solute in
membrane/concentration of solute in solution
As = solute permeability constant, m/s
c1 = solute concentration in upstream/feed solution, kg solute/m3
c2 = solute concentration in downstream/product solution, kg
solute/m3
74
Flux equations for reverse osmosis
𝑁𝑁𝑤𝑤 𝑐𝑐2
𝑁𝑁𝑠𝑠 =
𝑐𝑐𝑤𝑤𝑤
cw2 = concentration of solvent in stream 2 (permeate), kg
solvent/m3. if stream 2 is dilute, cw2 is approximately the density of
the solvent.

75
Solute rejection of reverse osmosis
𝑐𝑐1 − 𝑐𝑐2 𝑐𝑐2
𝑅𝑅 = =1−
𝑐𝑐1 𝑐𝑐1

𝐵𝐵 ∆𝑃𝑃 − ∆𝜋𝜋
𝑅𝑅 =
1 + 𝐵𝐵 ∆𝑃𝑃 − ∆𝜋𝜋
B is in atm-1
𝑃𝑃𝑤𝑤 𝐴𝐴𝑤𝑤
𝐵𝐵 = =
𝐷𝐷𝑠𝑠 𝐾𝐾𝑠𝑠 𝑐𝑐𝑤𝑤𝑤 𝐴𝐴𝑠𝑠 𝑐𝑐𝑤𝑤𝑤

76
 Example 6
Experiments at 25°C were performed to determine the permeabilities of a cellulose acetate
membrane. The laboratory test section shown in below figure has membrane are A = 2 x 10-3
m2. The inlet feed solution concentration of NaCl is c1 = 10 kg NaCl/m3 solution (10 g NaCl/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 5514 kPa (54.42 atm) is
used.
Calculate the permeability constants of the membrane and the solute rejection R.

77
Solution
• Since c2 is very low (dilute solution), the value of cw2 can be
assumed as the density of water, cw2 = 997 kg solvent/m3. To
convert the product flow rate to water flux:
Nw = (1.92 x 10-8 m3/s) (997 kg solvent/m3) (1/2 x 10-3 m2)
= 9.57 x 10-3 kg solvents/s.m2
𝑁𝑁𝑤𝑤 𝑐𝑐2 9.57 × 10−3 0.39
𝑁𝑁𝑠𝑠 = =
𝑐𝑐𝑤𝑤𝑤 997
−6
NaCl 2
= 3.774 × 10 kg solute .m
s

78
 Calculation of osmotic pressure
• For c1, 10 kg NaCl is in 1004 kg solution/m3 (ρ1 = 1004).
• Then, 1004 – 10 = 994 kg H2O in 1 m3 solution.
• MW of NaCl = 58.45 g/gmol
10 kg × 1000 g/kg
• Hence, = 0.1721 g mol NaCl/kg H2O
994 kg H2O × 58.45 g/gmol
• Using table below, π1 = 7.8 atm

79
Calculation of osmotic pressure
• For product solution, 997 – 0.39 = 996.6 kg H2O
0.39 ×1000
• Hence, = 0.00670 g mol NaCl/kg H2O
996.6 ×58.45
• Using table below, π2 = 0.32 atm

• Δπ = π1 – π2 = 7.8 – 0.32 = 7.48 atm

80
Calculations of permeability constants
−3
𝑃𝑃𝑤𝑤 𝑃𝑃𝑤𝑤
𝑁𝑁𝑤𝑤 = 9.57 × 10 = ∆𝑃𝑃 − ∆𝜋𝜋 = 54.42 − 7.48
𝐿𝐿𝑚𝑚 𝐿𝐿𝑚𝑚
𝑃𝑃𝑤𝑤 9.57 × 10 −3 kg solvent
−4
= 𝐴𝐴𝑤𝑤 = = 2.039 × 10
𝐿𝐿𝑚𝑚 54.42 − 7.48 s.m2 .atm

−6
𝐷𝐷𝑠𝑠 𝐾𝐾𝑠𝑠 𝐷𝐷𝑠𝑠 𝐾𝐾𝑠𝑠
𝑁𝑁𝑠𝑠 = 3.774 × 10 = 𝑐𝑐1 − 𝑐𝑐2 = 10 − 0.39
𝐿𝐿𝑚𝑚 𝐿𝐿𝑚𝑚
𝐷𝐷𝑠𝑠 𝐾𝐾𝑠𝑠 3.774 × 10 −6
= 𝐴𝐴𝑠𝑠 = = 3.896 × 10−7 m/s
𝐿𝐿𝑚𝑚 10 − 0.39

81
Calculations of solute rejection
𝑐𝑐1 − 𝑐𝑐2 10 − 0.39
𝑅𝑅 = = = 0.961
𝑐𝑐1 10

𝐴𝐴𝑤𝑤 2.039 × 10−4 −1

𝐵𝐵 = = = 0.5249 atm
𝐴𝐴𝑠𝑠 𝑐𝑐𝑤𝑤𝑤 3.896 × 10−7 997

𝐵𝐵 ∆𝑃𝑃 − ∆𝜋𝜋 0.5249 54.42 − 7.48

𝑅𝑅 = = = 0.961
1 + 𝐵𝐵 ∆𝑃𝑃 − ∆𝜋𝜋 1 + 0.5249 54.42 − 7.48

82