INTERCOMPANY MEMORANDUM

CAL CHEM CORPORATION

To: CHE Juniors Date: Winter Quarter
File: CHE 333
From: CHE faculty
Laboratory Managers
Subject: a! Se"aratio# Membra#e E$"erime#t
http://www.e!al.co/en/ebranes/nitrogen/in!e".asp
Fi%ure &' Hollow#fiber o!ule use! for air separation.
$as separation with polyer ebrane is becoing an iportant coponent of separation technology
%
.
E"aples of coonly use! ebrane separations are enrichent of nitrogen fro air& hy!rogen
separation in aonia plants an! refineries& reo'al of carbon !io"i!e fro natural gas& an! reo'al of
'olatile organic copoun!s fro i"tures with light gases. $as separation ebranes are often
pac(age! in hollow fiber o!ules !epicte! in )igure %. *s air flows un!er pressure into the o!ule
through the bores of the hollow fiber& soe of the air gases pereate through the wall of the fibers into
the shell of the hollow fiber. +he gas in the shell si!e of the fibers lea'es the o!ule as the pereate
strea. ,ince o"ygen& water& an! carbon !io"i!e are ore pereable than nitrogen an! argon& the gas in
the fiber bore is enriche! as it o'es fro the fee! to the resi!ue en! of the o!ule.
t
N
O 2
N
N 2
x , P
y , p 1 - y
1 - x
P > p
P P
O 2 N 2
>
Fi%ure (' ,cheatic of a ebrane with thic(ness t use! to separate -
.
fro /
.
.
+he flu" N
-.
of o"ygen across the ebrane shown in )igure . is gi'en as
N
-.
0
t
-.
P
1xP yp2 1%2
where
-.
P
is the pereance of the ebrane to o"ygen& x is the ole fraction of o"ygen on the
upstrea& or high pressure P& si!e of the ebrane& an! y is the ole fraction of o"ygen on the
!ownstrea& or low pressure p& si!e of the ebrane. +he ratio of pereance to ebrane thic(ness is
calle! the pereability
. O
P
of the ebrane to o"ygen. +he pereability can be 'iewe! as a ass
transfer coefficient that connects the flu" with the !ri'ing force for transport& which is the partial
pressure !ifference between the upstrea an! !ownstrea si!es of the ebrane.
We now nee! to consi!er the fact that as the fee! gas tra'els through the hollow fibers& its coposition
changes as selecti'e pereation !epletes the ore pereable coponents fro the fee! gas i"ture.
)igure 3 illustrates the i!eal countercurrent flow pattern for the binary i"ture of o"ygen an! nitrogen
o'ing through the fiber o!ule.
P e r m e a t e
y , n = n
P P F

F e e d
x , n
F F
x n x n + d ( x n )
d A
P
p
d ( y n )
y
i
R e t e n t a t e
x , n
R R
Fi%ure )' 3!eal countercurrent flow pattern through the separator.
+he total ole an! -
.
species balances aroun! the separator are
.
n
)
0 n
4
5 n
6
1.2
x
)
n
)
0 x
4
n
4
5 y
6
n
6
132
where n
)
& n
4
& an! n
6
are the olar flow rates of the fee!& retentate& an! pereate streas&
respecti'ely& an! x
)
& x
4
& an! x
6
are the fee!& retentate& an! pereate -
.
ole fraction&
respecti'ely. +he olar flu" of o"ygen through a !ifferential area dA in the ebrane is gi'en
by e7uation 1%2 or by
N
-.
0
dA
xn d 2 1
0
t
-.
P
1xP yp2 0 Q
-.
1xP yp2
+herefore d1xn2 0 Q
-.
1xP yp2dA = d1yn2 182
+he abo'e e7uation is 9ust the -
.
species balance aroun! the !ifferential 'olue eleent in the
ebrane. +he re!uction in the -
.
olar flow rate d1xn2 of the retentate strea pro'i!es the
sae -
.
olar flow rate d1yn2 through the ebrane. P an! p are the a'erage retentate an!
pereate si!e pressures& respecti'ely. ,iilar species balance for nitrogen aroun! the !ifferential
'olue eleent in the ebrane yiel!s
d:1%x2n; 0 Q
/.
:1%x2P 1%y2p2;dA 1<2
=i'i!ing e7uation 182 by e7uation 1<2& we obtain
; 2 % :1
2 1
n x d
xn d

0
.
.
>
>
N
O
Q
Q
p y P x
yp xP
2 % 1 2 % 1

1?2
+he ratio
; 2 % :1
2 1
n x d
xn d

is 9ust the olar flow rate of o"ygen o'er that of nitrogen in the
pereate strea& therefore it is e7ual to the ratio of the ole fraction of o"ygen o'er that of
nitrogen
y
y
%
as shown scheatically in )igure 8. Let
@
0
.
.
>
>
N
O
Q
Q
& e7uation 1?2 becoes
y
y
%
0
@
p y P x
yp xP
2 % 1 2 % 1

1A2
P e r m e a t e
y , n = n
P P F

F e e d
x , n
F F
x n x n + d ( x n )
d ( y n )
y
i
R e t e n t a t e
x , n
R R
P
p
Fi%ure *' Molar flow rate ratio is e7ual to ole fraction ratio.
+he separation factor
@
is assue! to be constant. +he pereate coposition at the cappe! en!
of the hollow fibers is obtaine! fro e7uation 1A2 by replacing y with y
i
an! x with x
4
.
i
i
y
y
%
0
@
p y P x
p y P x
i R
i R
2 % 1 2 % 1

1A2
When the change in fee! ole fraction of o"ygen is less than <BC& the !ri'ing force for !iffusion
across the ebrane& 0 xP yp& is assue! to be a linear function of the change in the olar
flow on the fee! si!e of the ebrane
d1xn2 0
F R
F R
xn xn

2 1 2 1
d 1D2
)ro the species balance aroun! the separator x
)
n
)
0 x
4
n
4
5 y
6
n
6
1xn2
4
1xn2
)
0 1yn2
6
1E2
Cobine e7uations. 1D2 an! 1E2 with e7uation 182 d1xn2 0 Q
-.
1xP yp2dA& we obtain
y
6
n
6

F R
d

0 Q
-.
dA
,eparate the 'ariables an! integrate
y
6
n
6

R
F
d
0 Q
-.
1
4

)
2

m
A
dA
B
y
6
n
6

F
R
ln

0 Q
-.
1
4

)
2A

y
6
n
6
0 Q
-.

l
A

1%B2
where the log ean a'erage
l
is !efine! as

l
0
F
R
F R

ln
0 1xP yp2
l
0
F
R
F R
yp xP
yp xP
yp xP yp xP
2 1
2 1
ln
2 1 2 1

1%%2
E7uation 1%B2 e"presses the olar flow rate y
6
n
6
of o"ygen as a function of the pereance Q
-.
or ass transfer coefficient& area of ebrane A

for ass transfer& an! an a'erage !ri'ing force

l
across the ebrane. ,iilarly& the olar flow rate of nitrogen in the pereate strea can
be foun!
1%y
6
2n
P
0 Q
/.
:1%x2P 1%y2p2;
l
A

1%.2
+he o"ygen species balance& x
)
n
)
0 x
4
1

n
)
n
6
2 5 y
6
n
6
& can be written in !iensionless for
using the !efinition of the cut 0 n
6
/n
)
&
x
)
0 x
4
1

% 2 5 y
6
1%32
,iilarly& e7uations 1A2& 1%B2& an! 1%.2 in !iensionless fors are
i
i
y
y
%
0
@
2 % 1 2 % 1
i R
i R
y r x
y r x

1%82
y
6
n
6
F
R
n
n
.
>
%
N
Q
0
F
R
n
n
.
>
%
N
Q
Q
-.

l
A

y
6
p A Q
n
m N
R
.
>
F
P
n
n
0

F
P
n
n
%
.
.
>
>
N
O
Q
Q
1xr y2
l
y
6
K
4
0 1% 2
@
1xr y2
l
1%<2
where 1xr y2
l
is !efine! by E7. 1%%2
1%y
6
2 K
4
0 1% 2:1%x2r 1%y22;
l
1%?2
where :1%x2r 1%y22;
l
is !efine! by E7. 1%%2 with "Fs an! yFs
replace! by 1%#"2Fs an! 1%#y2Fs
where r 0 P/p an! K
4
0
p A Q
n
m N
R
.
>
+he algebraic o!el e7uations 1%3#%?2 represent a syste with four e7uations in eight 'ariables:
x
)
& x
4
& y
6
& r& y
i
& &
@
& an! K
4
. +he syste can be sol'e! with easure! 'alues of x
)
& x
4
& y
6
& an! r&
lea'ing y
i
& &
@
& an! K
4
as un(nowns in the solution.
+he algebraic e7uations 1%32 through 1%?2 can be sol'e! by the following iterati'e etho! using
EGCEL. 3agine that if you coul! cobine e7uations 1%3#%?2 by eliinating &
@
& an! K
4&
then
you woul! ha'e one e7uation an! one un(nown y
i.
Hecause of the non#linear nature of these
e7uations& you cannot cobine the algebraically an! you ha'e to sol'e for y
i
by trial#an! error.
+he following is a proce!ure that you can use.

,tep 1%2 Calculate using E7uation 1%32 fro easure! 'alues of x
)
& x
4
an!

y
6
,tep1.2 $uess a 'alue for y
i
. Choose a 'alue for y
i
such that

x
R
P > y
i
p or y
i
I

x
R
P/

p to ensure
that the log ean !ri'ing force !efine! by e7uation1%%2 is 'ali!.
,tep 132 Calculate using E7uation 1%82
,tep 182 Calculate K
4
using E7uation 1%<2
,tep 1<2 Calculate the Left Han! ,i!e 1LH,2 an! 4ight Han! ,i!e 14H,2 of E7uation 1%?2.
,tep 1?2 Jse ,-LKE4 in EGCEL to fin! the 'alue of y
i
such that the absolute 'alue of
14H,#LH,2 e7uals Lero.
+he algebraic e7uations 1%32 an! 1%?2 can also be sol'e! by /ewtonFs etho! presente! in
*ppen!i" *
E$"erime#tal Proce+ure
Copresse! air at about %%B psig is supplie! to the ebrane o!ule through an air regulator.
+he supplie! air pressure can be controlle! by turning the (nob on top of the regulator. +he
o"ygen concentration is easure! by a portable o"ygen analyLer o!el $64#3B. Mou can
calibrate the o"ygen analyLer by turn it on while in the abient air an! set the o"ygen
concentration to .%.B C.
*!9ust the inlet pressure of the ebrane o!ule to 3B psig. 4ea! the flow rate on the pereate
si!e of the ebrane an! set the sae flow rate for the retentate. 4ecor! the o"ygen
concentrations on both si!es of the ebrane when the syste reaches stea!y state. +he
pereate pressure p is assue! to be the abient pressure an! the retentate pressure P is the
a'erage of the fee! an! retentate pressures as easure! by the pressure gages.
Measure the o"ygen concentrations an! the retentate pressures again at the retentate flow rates of
twice an! four ties the pereate flow rate. 4epeat the proce!ure at 8B& <B& ?B& AB& an! DB psig.
A#al,!i!
%. 6lot the e"periental separation factor
@
as a function of r 1= P/p2 an! !iscuss the results.
.. Copare calculate! cut with e"periental 10 n
6
/n
)
2 an! plot the e"periental an!
calculate! cut 10 n
6
/n
)
2 as a function of r an! !iscuss the results.
3. 3f you are using the /ewtonFs etho!& present one iteration at 3B psig an! 0 B.< using the
guesse! 'alues y
i
0 B..& 0 B.<&
@
0 ?& an! K
4
0 .. Clearly in!icate how you e'aluate the
Jacobian atri".
8. E"plain the !ifference in the !iffusion rates of gases through the ebrane.
Re-ere#ce!
%. Co(er& =. +.& 6rabha(ar& 4.& )reean& N+ools for +eaching $as ,eparation Jsing 6olyers&N
Chemical Engineering Educatin& ).& Winter .BB.& ?B
.. =a'is& 4. *.& ,an!all& -. C.& O* ,iple *nalysis for $as ,eparation Mebrane E"perients&N
Chemical Engineering Educatin& ).& Winter .BB.& A8
3. Welty& J. 4.& Wic(s& C. E.& Wilson& /. E.& an! 4orrer& $. L.& )un!aentals of Moentu&
Heat an! Mass +ransfer& John Wiley an! ,on& 1.BB%2