NPTEL

Novel Separation Processes

Module :
5
Gas separation

Dr. Sirshendu De
Professor, Department of Chemical Engineering
Indian Institute of Technology, Kharagpur
e-mail: sde@che.iitkgp.ernet.in

Keywords:
Separation processes, membranes, electric field assisted separation, liquid
membrane, cloud point extraction, electrophoretic separation, supercritical fluid
extraction

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Novel Separation Processes

Gas Separation
In case of gas separation by membranes, high pressure feed gas is supplied to one

side of the membrane and permeate comes out normal to the membrane to the low

pressure side. Due of high diffusivity in gases, concentration gradient in the gas phase

normal to the membrane surface is small. So, gas film resistance is neglected compared to

membrane resistance. This means concentration in gas phase in a direction normal to

membrane is uniform whether gas stream flows parallel to the surface or not.

There are various types of gas separation processes depending upon the flow

characterizations. Since the permeate comes normal to the flow direction of the feed, this

is known as simple cross flow (Fig. 5.1a). If there is complete mixing of the feed and

permeate by an external agent (stirrer or mixer), then the configuration is complete

mixing (Fig. 5.1b). If feed and permeate are in the same direction, then the flow is

cocurrent flow (Fig. 5.1c). If they are in opposite direction, then it is counter current flow

(Fig. 5.1d).

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Novel Separation Processes

Permeate

Reject
Feed
Fig. 5.1a: Cross Flow

Permeat

Feed Reject

Fig. 5.1b: Complete Mixing

Permeate

Feed Reject
Fig. 5.1c:Co-current

Permeate
PF

PFR
Feed Reject

Fig. 5.1d: Counter current

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Novel Separation Processes

In the following section, the working principles and calculations involved in complete

mixing mode are considered. This case is like a continuous stirred tank reactor (CSTR).

The assumptions involved are:

(i) Isothermal condition.

(ii) Negligible pressure drop in feed and permeate side.

(iii) Permeability of each component is constant.

qp = θqf

Pl, yp
Low pressure

High pressure side Ph, x0 q0 =(1-θ)qf

Feed qf, xf

Fig. 5.2: Schematic of a complete mixing configuration with the process conditions

In the above figure, q f is total feed flow rate (in m3 /s) ; q0is outlet reject flow (m3 /s) ;

qp
q p is outlet permeate flow (m3 /s) ; θ is fraction of feed permeate = .
qf

Overall material balance yields the following relation.

q f = q0 + q p (5.1)

Rate of diffusion/ permeation of species A (in a binary mixture of A and B) is given as,

q A q p y p ⎛ PA' ⎞
= = ⎜ ⎟ ( Ph x0 − Pl y p ) (5.2)
Am Am ⎝ t ⎠

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Novel Separation Processes

⎛ cm3 .cm ⎞
where, PA' is permeability of A in membrane ⎜ 2 ⎟ ; q A is the flow rate of A in
⎝ s.cm .cmHg ⎠

permeate; Am is the membrane area; t is the membrane thickness; Ph is feed side total

pressure (cm.Hg); x0 is mole fraction of A in reject; x f is mole fraction of A in feed;

y p is mole fraction of A in permeate; Ph x0 is partial pressure of A in reject gas phase.

Rate of permeation of species B is given as,

qB q p (1 − y p ) PB' ⎡
= = Ph (1 − x0 ) − Pl (1 − y p ) ⎤⎦ (5.3)
Am Am t ⎣

Where, PB' is permeability of B. Dividing Eq.(5.2) by (5.3), the following expression is

obtained.

⎡ ⎛ Pl ⎞ ⎤
α ∗ ⎢ x0 − ⎜
⎟ yp ⎥
yp ⎣ ⎝ Ph ⎠ ⎦
= (5.4)
1− yp ⎛P⎞
(1 − x0 ) − ⎜ l ⎟ (1 − y p )
⎝ Ph ⎠

PA'
Where, α = '∗

PB

Overall component balance for A:

An overall balance of component A results into the following equation.

q f x f = q0 x0 + q p y p (5.5)

Rearrangement of above equation results,

q0 x0 q p y p
xf = + (5.6)
qf qf

qp q0
Defining, =θ; and = 1 − θ , the above equation is written as,
qf qf

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Novel Separation Processes

x f = (1 − θ ) x0 + θ y p (5.7)

The above equation is re-organized to estimate the feed mole fraction or that in the

permeate.

x f −θ yp x f − x0 (1 − θ )
x0 = or yp = (5.8)
1−θ θ

But, q p = θ q f and the membrane area can be estimated as follows.

qp yp ⎛ P' ⎞
= ⎜ A ⎟ ( Ph x0 − Pl y p )
Am ⎝ t ⎠

θ q f yp
Am = (5.9)
⎛P ⎞'

⎜ ⎟ ( Ph x0 − Pl y p )
A

⎝ t ⎠

For design purposes:

Pl
There are 7 variables, namely, x f , x0 , y p ,θ , α ∗ , , Am . 4 of them are generally
Ph

independent.

Pl
Case 1: x f , x0 , α ∗ , are given and y p , θ , Am need to be determined.
Ph

From Eq. (5.3),

⎛ P⎞
y p = y p ⎜ x0 , α ∗ , l ⎟ (5.10)
⎝ Ph ⎠

It is a quadratic equation. We can solve for yp. θ is calculated from Eq. (5.8)

x f −θ yp
x0 =
1−θ

Am can be calculated from Eq. (5.9).

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Novel Separation Processes

Pl
Case 2: x f , θ , α ∗ , are given and y p , x0 , Am to be calculated
Ph

Minimum concentration of Reject Stream:

If all the feed is permeated, then θ=1 and feed composition xf = yp

For all values of θ <1, yp > xf

Substitute, xf = yp in Eq. (5.3).

x0m = Minimum rejection component for a given xf

⎡ ⎛P⎞ ⎤
( )
x f ⎢1 + α ∗ − 1 ⎜ l ⎟ (1 − x f ) ⎥
⎝ Ph ⎠
= ⎣ ⎦ (5.11)
α (1 − x f ) + x f
∗

So, a feed component xf cannot be stripped lower than x0m even with an infinitely large

membrane area for a completely mixed system. To do this cascade may be used.

Cross Flow model for gas Permeation:

Permeat
qp = θqf

Low
Pl y, dq pressure

q, x q – dq
qf, xf Ph x -dx
Reject
Feed in high
x0, q0 = (1-θ)qf
pressure dAm
Plug Flow

Fig. 5.3: Schematic of a cross flow model

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Novel Separation Processes

Longitudinal velocity in high pressure or reject stream is high. So that gas is in plug flow

and flows parallel to membrane. Low pressure side, permeate stream is almost pulled into

vacuum. So, flow is essentially perpendicular to membrane. No mixing is assumed. So

that composition varies as length. Over a different membrane area dAm at any point, local

permeation rates are presented below.

Component A balance:

PA'
− ydq = [ Ph x − Pl y ] dAm (5.12)
t

Component B balance:

PB'
− (1 − y ) dq = ⎡ Ph (1 − x ) − Pl (1 − y ) ⎤⎦ dAm (5.13)
t ⎣

dq = total flow rate perpendicular to dAm. Dividing Eq.(5.12) by (5.13),

⎡ ⎛ Pl ⎞ ⎤
α ∗ ⎢x − ⎜ ⎟ y⎥
y ⎣ ⎝ Ph ⎠ ⎦
= (5.14)
1− y ⎛P⎞
(1 − x ) − ⎜ l ⎟ (1 − y )
⎝ Ph ⎠

Permeate composition y as a function of reject composition x at a point along the length.

Analytical solution:

The design equation is presented below:

R
⎛ E⎞
( ∗
)
1 − θ (1 − x ) ⎜ u f − D ⎟
=
S
⎛ uf −α∗ + F ⎞ ⎛ uf − F ⎞
T

⎜⎜ ⎟⎟ ⎜ (5.15)
(1 − x f ) ⎜⎜ u − E ⎟⎟ ⎝ u − α ∗
+ F ⎠ ⎝ u−F ⎠
⎟
⎝ D ⎠

q x
Where, θ ∗ = 1 − , i= ; u = − Di + D 2i 2 + 2 Ei + F 2 ;
qf 1− x

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Novel Separation Processes

(
⎡ 1 − α ∗ Pl) ⎤ α∗ ⎡ P ⎤
D = 0.5 ⎢
⎢⎣ Ph
+α∗⎥;
⎥⎦
E=
2
− DF ; ( )
F = −0.5 ⎢ 1 − α ∗ l − 1⎥
Ph ⎦
⎣

1 α ∗ ( D − 1) + F 1
R= ; S= ; T=
2D −1 ⎛α∗ ⎞ E
( 2 D − 1) ⎜ −F⎟ 1− D −
F
⎝ 2 ⎠

xf
uf =value of u at i = i f = .
1− xf

Composition of exit:

At exit, x=x0, θ* = θ (cut ratio) = fraction of feed permeated.

yp= mole fraction at the exit of permeate is estimated by overall material balance

Membrane area required,

tq f
if
(1 − θ ) (1 − x )
∗

Am =
Ph PB' ∫ ⎡ 1 P⎛ 1 ⎞⎤
di (5.16)
i0
( fi − i ) ⎢ − l ⎜ ⎟⎥
⎣1 + i Ph ⎝ 1 + fi ⎠⎦

Where, fi = ( Di − F ) + D 2i 2 + 2 Ei + F 2 and t = thickness of membrane and

PB’ = membrane permeability of species B

Counter-current gas Separation:

q’f, yp yi = 0

qf, xf q0, x0

Fig. 5.4: Schematic of a counter current flow model

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Novel Separation Processes

q’, y yi = 0

q, x q0, x0

Am Am = 0

Fig. 5.5: Schematic of balance over a small element

The schematic of the counter current flow model is presented in Fig. 6.4 and the small

element is shown in Fig. 5.5.

Overall material balance:

Total material in = Total material out

q = q0 + q ' (5.17)

Overall A balance:

Total A in = Total A out

qx = q0 x0 + q ' y (5.18)

Species A balance over a differential element,

d (qx) = d (q ' y ) (5.19)

dq, y

q, x (q - dq)
dAm
(x - dx)

In the above differential volume, species A balance provides,

qx = ( q − dq )( x − dx ) + ydq

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Novel Separation Processes

ydq = d ( qx ) (5.20)

Local flux of A across the membrane is presented,

PA'
− ydq = [ Ph x − Pl y ] dAm (5.21)
t

For species B, the following balance equation is provided:

PB'
− (1 − y ) dq = ⎡ Ph (1 − x ) − Pl (1 − y ) ⎤⎦ dAm (5.22)
t ⎣

Combining Eqs. (5.21) and (5.22), the following expression is obtained.

⎛P ⎞
x −⎜ l ⎟y
y ⎛P ⎞ '
⎝ Ph ⎠
=⎜ ⎟ A
(5.23)
1− y ⎝ P ⎠ '
⎛P ⎞
(1 − x ) − ⎜ l
B
⎟ (1 − y )
⎝ Ph ⎠

Eliminate q ' by using equations (5.17) and (5.18),

qx = q0 x0 + ( q − q0 ) y (5.24)

The above equation can be rearranged as

q0 = q
( x − y) (5.25)
( x0 − y )
Bu using this equation substitute q in equation (5.21) then we get,

⎡ ( x − y) ⎤
d ⎢ q0 0 ⎥
⎣ ( x − y ) ⎦ PA'
−y = [ Ph x − Pl y ]
dAm t

⎡x − y⎤
d⎢ 0
x − y ⎥⎦ PA'
− yq0 ⎣ = [ Ph x − Pl y ]
dAm t

By derivating this equation and by rearranging it finally we get it as,

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Novel Separation Processes

⎡ dy dx ⎤ PA'
q0 y ⎢( x − x0 ) + ( x0 − y ) ⎥ = ( x − y )( xPh − yPl ) (5.26)
⎣ dAm dAm ⎦ t

From Eq. (5.23),

y x − ry
= α∗ (5.27)
1− y (1 − x ) − r (1 − y )
Pl
Where, r = . The above equation is simplified as,
Ph

y (1 − x) − r ( y − y 2 ) = α ∗ (1 − y )( x − ry ) (5.28)

Differentiate the above equation with respect to Am,

dy ⎡ y + α ∗ (1 − y ) ⎤ dx
=⎢ ⎥
dAm ⎣ (1 − x) − r (1 − 2 y ) + α (1 − y )r + α ( x − ry ) ⎦ dAm
∗ ∗

dx
=β (5.29)
dAm

The above equation is rearranged as,

⎛ PA' ⎞
⎜ ⎟ ( x − y )( xPh − yPl )
dx
= ⎝ t ⎠ (5.30)
dAm q0 y ⎡⎣( x0 − x ) − β ( x, y )( x0 − y ) ⎤⎦

dy
Similarly, the expression of can be derived.
dAm

Overall Material Balance provides,

q f = q0 + q 'p = q0 + θ q f

q0 = (1 − θ ) q f (5.31)

Overall ‘A’ balance results,

q f x f = q0 x0 + q 'p y p

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Novel Separation Processes

x f − (1 − θ ) x0
yp = (5.32)
θ

For a value of given θ, then

(i) Guess x0

(ii) Solve for yp from equation (5.32)

(iii) Check value of yp for solving ordinary differential equations.

(iv) Iterate.

Solved Problems

1) A membrane is used to separate a gaseous mixture A and B whose feed rate is

q f = 104 cm3 ( STP ) / s and feed composition of A, xf =0.5; The desired composition of

the reject is x0 = 0.25. The membrane thickness, t = 3*10-3 cm; Ph= feed side pressure =

80 cm Hg and Pl = permeate side pressure = 20 cm Hg. The permeabilities are,

cm3 ( STP ).cm

p = 60 ×10
'
A
−10
2
and pB' = 6 ×10−10 of above units. Assuming complete
s.cm .cmHg

mixing model, calculate permeate concentration, yp, fraction permeated θ and membrane

area (Am) required?

Solution:
x f , x0 , α * , Pl / Ph are given

y p , θ , Am are to be determined

−b + b 2 − 4ac
From Eq.(), yp =
2a
Where,
Ph P
a = 1 − α *; b = (1 − x0 ) − 1 + α * h x0 + α *
Pl Pl

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Ph
c = −α * x0
Pl

p A' 60 ×10−10
α* = = = 10
pB' 6 ×10−10

a = 1 − α * = 1 − 10 = −9
Ph P
b= (1 − x0 ) − 1 + α * h x0 + α *
Pl Pl
80 80
= (1 − 0.25) − 1 + 10 × × 0.25 + 10
20 20
= 22
Ph ⎛ 80 ⎞
c = −α * x0 = −10 ⎜ ⎟ ( 0.25 ) = −10
Pl ⎝ 20 ⎠

−b + b 2 − 4ac
yp = = 0.604
2a
x f −θ yp
x0 =
1−θ
0.5 − θ × 0.604
0.25 =
1−θ
θ = 0.706
θ q f yp 0.706 × 104 × 0.604
Am = =
( p / t)(P x
'
− Pl y p ) ⎛ 60 × 10−10 ⎞
−3 ⎟ (
A h 0
⎜ 80 × 0.25 − 20 × 0.604 )
⎝ 3.0 × 10 ⎠
Am = 2.7 × 108 cm 2

2) It is desired to find the membrane area required to separate air using a membrane 3*10-3

cm3 ( STP ).cm

cm thickness with oxygen permeability p A' = 300 ×10−10 and α * = 10 for
s.cm 2 .cmHg

permeability ratio of oxygen to nitrogen. Feed rate, q f = 2 × 106 cm3 ( STP) / s and fraction

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Novel Separation Processes

cut θ = 0.20; Ph=200 cm Hg and Pl = 20 cm Hg. Assume, complete mixing model,

calculate permeate composition, reject composition and membrane area?

Solution:
xf = 0.21 (mole fraction of oxygen in air)
Pl Pl P P
a1 = θ + − θ − α *θ − α * l + α * l θ
Ph Ph Ph Ph
20 20 20 20
= 0.2 + − × 0.2 − 10 × 0.2 − 10 × + 10 × × 0.2
200 200 200 200
= 0.2 + 0.1 − 0.02 − 2 − 1 + 0.2
= −2.52
Pl Pl P P
b1 = 1 − θ − x f − + θ + α *θ + α * l − α * l θ + α * x f
Ph Ph Ph Ph
20 20 20 20
= 1 − 0.2 − 0.21 − + × 0.2 + 10 × 0.2 + 10 × − 10 × × 0.2 + 10 × 0.21
200 200 200 200
= 1 − 0.2 − 0.21 − 0.1 + 0.02 + 2 + 1 − 0.2 + 2.1
= 5.41
c1 = −α * x f = −10 × 0.21 = −2.1

−b + b 2 − 4ac −5.41 + 5.41 − 4 × 2.52 × ( −2.1)

2

yp = =
2a 2 × ( −2.52 )

= 0.509
x f −θ yp 0.21 − 0.2 × 0.509
x0 = = = 0.135
1−θ 1 − 0.2
θ q f yp
Am =
( p / t)(P x
'
A h 0 − Pl y p )

0.2 × 2 ×106 × 0.509

=
⎛ 300 × 10−10 ⎞
⎜ −3 ⎟ ( 200 × 0.135 − 20 × 0.509 )
⎝ 3 × 10 ⎠
= 1.21× 109 cm 2

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References:

1. C. J. Geankoplis, Transport Processes and Unit Operations, Prentice Hall of India,

New Delhi,1997.

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