CACHE Modules on Energy in the Curriculum

Fuel Cells
Module Title: Simulation of a Methane Steam Reforming Reactor
Module Author: Jason Keith
Author Affiliation: Michigan Technological University
Course: Kinetics and Reaction Engineering
Text Reference: Fogler (4
th
edition) Sections 4!" 4!# 4!$
Literature References% J! &u and '! Froment AIChE J. 35 ## (($#$) J! &u and '!
Froment AIChE J. 35 $" (($#$) F! )! *! Fernandes and )! +! Soares ,at! )m! )--l!
Res! 3!3" (.. (/001)!
Conce#ts% 2evelo- a numerical model to -redict the conversion and hydrogen yield
3ithin a steam reforming reactor!
$ro%lem Moti&ation:
Fuel cells are a -romising alternative energy conversion technology! 4ne ty-e of fuel cell
a -roton e5change mem6rane fuel cell (7EMF8) reacts hydrogen 3ith o5ygen to -roduce
electricity (Figure ()! Fundamental to a hydrogen economy -o3ered 6y fuel cells is the
generation of high -urity hydrogen!
8onsider the schematic of a com-ressed hydrogen tan9 (/000 -si regulated to (0 -si)
feeding a -roton e5change mem6rane fuel cell as seen in Figure / 6elo3! The focus of
this module is hydrogen generation 6y steam reforming of methane to fill the com-ressed
tan9!

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:
/
tan9
Fuel 8ell
8om-uter
(Electric
,oad)
:
/
out
)ir in
)ir ; :
/
4 out
Figure /! 2iagram for fueling a la-to-!
7ressure
regulator
:
/
feed line
H
2
H
2
H
2
H
2
H
2
O
2
O
2
H
+
e
-
e
-
Anode
Electrolyte
Cathode
O
2
H
2
O
H
2
O
O
2
H
+
H
+
H
+
H
2
H
2
H
2
H
2
H
2
O
H
2
O
Figure (! Reactions in the 7EMF8
'ac(ground
*atural gas has 6een -ro-osed as a source of hydrogen for fuel cell vehicle a--lications
6ecause of the e5isting infrastructure! <n a -rocess 9no3n as steam reforming natural gas
and steam are reacted into mostly car6on mono5ide and hydrogen 3ith some car6on
dio5ide also -roduced! There can also 6e e5cess 3ater in the reformate stream!
The steam reforming reaction is given as%
8:4 = :/4 > ? :/ = 84 (()
<n the steam reformer the 3ater gas shift reaction also ta9es -lace as%
84 = :/4 > :/ = 84/ (/)
)dding together the steam reforming and 3ater gas shift reactions gives the overall
reaction%
8:4 = / :/4 > 4 :/ = 84/ (?)
The e@uili6rium constants can 6e e5-ressed in terms of -artial -ressures (in atm) and
tem-erature in degrees Kelvin as AJ! R! Rostru-B*ielsen and K! )as6ergB7etersen CSteam
Reforming )TR 7artial 45idationD 8atalysts and Reaction EngineeringE 8h! (4 of
Handbook of Fuel Cells: Fundamentals, Technology, and Applications Fol ?! G!
Fielstich )! ,amm :! )! 'asteiger eds! Giley /00?H! The su6scri-t on the follo3ing
e@uili6rium constants refers to the e@uation num6er given a6ove%
) ; /"(01 4/ ! ?0 e5-(
/ 4
?
/
(
T


!
" H CH
C" H
= =
(4)
) ; 4(10 "$# ! ? e5-(
/
/ /
/
T


!
" H C"
C" H
+ = =
(.)
) ; ?(/11 /(# ! ?4 e5-(
/
/ 4
/
4
/
?
T


!
" H CH
C" H
= =
(1)
<n the reactor methane (8:4) and 3ater (:/4) are fed as reactants and car6on dio5ide
(84/) car6on mono5ide (84) and hydrogen (:/) are -roduced over a nic9el catalyst on
an alumina su--ort!
<n la6oratory e5-eriments a nonreacting inert gas such as helium (:e) may also 6e
-resent! <n the most general form the governing conservation e@uations for each of these
s-ecies is given 6elo3 3here
i
F
denotes the molar flo3 rate of s-ecies i in mol;h #
denotes the catalyst 3eight in g and $i denotes the reaction rate of e@uation i in units of
mol;(gBh)%
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) (
? (
4
$ $
d#
dF
CH
+ = 3ith
0
4 4
) 0 (
CH CH
F # F = = (")
) / (
? / (
/
$ $ $
d#
dF
" H
+ + = 3ith
0
/ /
) 0 (
" H " H
F # F = = (#)
) 4 ? (
? / (
/
$ $ $
d#
dF
H
+ + = 3ith
0
/ /
) 0 (
H H
F # F = = ($)
) (
/ (
$ $
d#
dF
C"
= 3ith
0
) 0 (
C" C"
F # F = = ((0)
) (
? /
/
$ $
d#
dF
C"
+ = 3ith
0
/ /
) 0 (
C" C"
F # F = = ((()
0 =
d#
dF
He
3ith
0
) 0 (
He He
F # F = = ((/)
The reaction rates are given 6y%
/
(
?
/
/ 4
. ! /
/
(
(
%E&
!

k
$
C" H
" H CH
H

=
((?)
/
/
/ /
/
/
/
/
%E&
!

k
$
C" H
" H C"
H

=
((4)
/
?
/
4
/ /
/ 4
. ! ?
/
?
?
%E&
!

k
$
C" H
" H CH
H

=
((.)
/
/ /
/ / 4 4
(
H
" H " H
H H C" C" CH CH

!
! ! ! %E& + + + + =
((1)
Furthermore the coefficients in E@uations (?B(1 are given 6y the )rrhenius relationshi-s
as%
) ; /40(00 e5-( (0 // ! 4
(.
(
$T k = ((")
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) ; 1"(?0 e5-( (0 $1 ! (
1
/
$T k = ((#)
) ; /4?$00 e5-( (0 0/ ! (
(.
?
$T k = (($)
) ; ?#/#0 e5-( (0 1. ! 1
4
4
$T !
CH

=
(/0)
) ; ##1#0 e5-( (0 "" ! (
.
/
$T !
" H
=
(/()
) ; #/$00 e5-( (0 (/ ! 1
$
/
$T !
H

= (//)
) ; "01.0 e5-( (0 /? ! #
.
$T !
C"

= (/?)
*ote that in the a6ove e5-ressions $ I #!?(4 J;(molBK) is the gas constant!
The reaction stoichiometry suggests that the num6er of moles 3ill increase 3ith the
distance do3n the reactor! Thus for a negligi6le -ressure dro- in the reactor the gas
e5-ands 6y increasing the volumetric flo3 rate! The -artial -ressure of a chemical s-ecies
is calculated from the total -ressure and the num6er of moles of that s-ecies!
tot
i
i
F
F
=
(/4)
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2raft J!M! Keith 4cto6er (4 /00#
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Exam#le $ro%lem )tatement: 8onsider a feed of (0000 mol;h 8:4 (0000 mol;h :/4
and (00 mol;h :/ to a steam reforming reactor that o-erates at (000 K and a ( atm feed
-ressure! 2etermine the molar flo3 rates of 8:4 :/4 84/ 84 and :/ as a function of
catalyst 3eight u- to ?#/ g! )lso determine the overall methane conversion!
Exam#le $ro%lem )olution:
'tep () ) numerical model can 6e made to simulate E@uations " J (/ 3ith the coefficients
determined in e@uations 4 J 1 and (? J /?! Using a sim-le Euler discretiKation of the
e@uations 3e have%
) (
? ( 4 ( 4
$ $ # F F
i CH i CH
+ =
+ (/.)
) / (
? / ( 4 / ( /
$ $ $ # F F
i " H i " H
+ + =
+ (/1)
) 4 ? (
? / ( / ( /
$ $ $ # F F
i H i H
+ + + =
+ (/")
) (
/ ( (
$ $ # F F
i C" i C"
+ =
+ (/#)
) (
/ / / ( /
$ $ # F F
i C" i C"
+ + =
+ (/$)
i He i He
F F
(
=
+
(?0)
su6Lect to the initial conditions
(0000
0 / 0 4
= =
" H CH
F F
mol;h and
(00
0 /
=
H
F
mol;h!
The other chemicals have Kero initial molar flo3s%
0
0 0 0 /
= = =
He C" C"
F F F
mol;h!
These e@uations can 6e solved iteratively until the end of the reactor is reached! The
-rocedure is as follo3s%
() 8alculate the rate constants k( k/ k? !8:4 !:/4 !84 !:/ and use them to
com-ute the reaction rates $( $/ $? at the feed conditions (location 0 total
catalyst 3eight # I 0)!
/) 8alculate chemical flo3 rates (location ( catalyst 3eight I #) using E@uations
/. J ?0!
?) 8alculate the total and -artial -ressures using E@uation /4!
4) 8alculate the rate constants k( k/ k? !8:4 !:/4 !84 !:/ and use them to
com-ute the reaction rates $( $/ $? at the feed conditions (location ( total
catalyst 3eight # I #)!
.) Re-eat ste-s /B4 as you -rogress do3n the length of the reactor!
The system is simulated using a ste- siKe of # I 0!( g! For more detail -lease see the
M)T,)+ code at the end of the e5am-le -ro6lem solution! ) -lot of the s-ecies molar
flo3 rates as a function of catalyst 3eight is sho3n in Figure ? 6elo3! There are some
o6servations to 6e made from this -lot! First of all as there is no helium -resent in the
feed the molar flo3 rate is Kero every3here in the reactor! Secondly 6oth the 84 and
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8:4 are sho3n as solid lines! The molar flo3 rate of 8:4 decreases 3ith catalyst 3eight
3hile the molar flo3 rate of 84 increases 3ith catalyst 3eight! Ge also note that if #
I0!0( g the results are nearly identical!
Figure ?! S-ecies molar flo3 rates as a function of catalyst 3eight!

'tep *) The e5it 8:4 molar flo3 rate is a6out /400 mol;h! This corres-onds to a 8:4
conversion of%
M "1
(0000
/400 (0000
0 4
4 0 4
=

=
CH
e+it CH CH
F
F F
,
(/()
)ummary: )fter a @uic9 change in the first g of catalyst (see the :/4 molar flo3 rate)
there is a slo3 a--roach to3ards e@uili6rium in the reactor!
Matla% Code% Follo3ing is the Matla6 code for this e5am-le -ro6lem!
%
% steam reforming plug fow model
% includes water-gas shift reaction and overall reaction
%
% this is an isothermal model with no pressure drop!
%
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% CH4 + H2O <- CO + !H2 r"n #
% CO + H2O <- CO2 + H2 r"n 2
% CH4 + 2 H2O <- CO2 + 4 H2 r"n !
%
% feed conditions
% a $ CO
% % $ H2O
% c $ CO2
% d $ H2
% e $ He
% f $ CH4
%
clear
&gure'#(
close
%
)a*$*+ %mol,hr
)%*$#****+
)c*$*+
)d*$#**+
)e*$*+
)f*$#****+
%
)tot*$)a*+)%*+)c*+)d*+)e*+)f*+
%
% partial pressures in atm
-tot* $ #+
-a* $ -tot*.)a*,)tot*+
-%* $ -tot*.)%*,)tot*+
-c* $ -tot*.)c*,)tot*+
-d* $ -tot*.)d*,)tot*+
-e* $ -tot*.)e*,)tot*+
-f* $ -tot*.)f*,)tot*+
%
% temperatures in /
0* $ #***+
%
% set up numerical model
dw$#e-#+
w'#($*+
%
)a'#($)a*+
)%'#($)%*+
)c'#($)c*+
)d'#($)d*+
)e'#($)e*+
)f'#($)f*+
%
-a'#($-a*+
-%'#($-%*+
-c'#($-c*+
-d'#($-d*+
-e'#($-e*+
-f'#($-f*+
%
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2raft J!M! Keith 4cto6er (4 /00#
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for i$#1!22,dw+#+
w'i+#($w'i(+dw+
%
/#$e"p'!*342*-24#*5,0'i((+
/2$e"p'-!3462+4#5*,0'i((+
/!$e"p'!432#2-!#255,0'i((+
%
/CH4$5357e-4.e"p'!222*,23!#4,0'i((+
/CO$232!e-7.e"p'4*57*,23!#4,0'i((+
/H2$53#2e-6.e"p'226**,23!#4,0'i((+
/H2O$#344e7.e"p'-2252*,23!#4,0'i((+
%
8in#$432242e#7.e"p'-24*#**,23!#4,0'i((+
8in2$#3677e5.e"p'-54#!*,23!#4,0'i((+
8in!$#3*2*2e#7.e"p'-24!6**,23!#4,0'i((+
%
9:;$#+/CH4.-f'i(+/CO.-c'i(+/H2.-d'i(+/H2O.-%'i(,-d'i(+
r#$8in#,-d'i(<237,9:;<2.'-f'i(.-%'i(--d'i(<!.-a'i(,/#(+
r2$8in2,-d'i(,9:;<2.'-a'i(.-%'i(--d'i(.-c'i(,/2(+
r!$8in!,-d'i(<!37,9:;<2.'-f'i(.-%'i(<2--d'i(<4.-c'i(,/!(+
%
)a'i+#($)a'i(+'r#-r2(.dw+
)%'i+#($)%'i(-')%*,)f*(.'r#+r2+2.r!(.dw+
)c'i+#($)c'i(+'r2+r!(.dw+
)d'i+#($)d'i(+'!.r#+r2+4.r!(.dw+
)e'i+#($)e'i(+
)f'i+#($)f'i(-'r#+r!(.dw+
)tot$)a'i+#(+)%'i+#(+)c'i+#(+)d'i+#(+)e'i+#(+)f'i+#(+
%
-a'i+#( $ -tot*.)a'i+#(,)tot+
-%'i+#( $ -tot*.)%'i+#(,)tot+
-c'i+#( $ -tot*.)c'i+#(,)tot+
-d'i+#( $ -tot*.)d'i+#(,)tot+
-e'i+#( $ -tot*.)e'i+#(,)tot+
-f'i+#( $ -tot*.)f'i+#(,)tot+
%
end
%
&gure'#(
plot'w=)a(
hold on
plot'w=)%=>r-->(
plot'w=)c=>g-3>(
plot'w=)d=>81>(
plot'w=)e=>c>(
plot'w=)f=>%>(
"la%el'>Catal?st @eight= g>(
?la%el'>Aolar )low Bate mol,hr>(
legend'>CO>=>HC2O>=>COC2>=>HC2>=>He>=>CHC4>(
(
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2raft J!M! Keith 4cto6er (4 /00#
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Home $ro%lem )tatement: 8onsider a feed of (0000 mol;h 8:4 and (00 mol;h :/ to a
steam reforming reactor that o-erates at $00 K and a / atm feed -ressure!
a" 2etermine the molar flo3 rates of 8:4 :/4 84/ 84 and :/ as a function of catalyst
3eight u- to ?#/ g for :/4 feed flo3 rates of /0000 mol;h ?0000 mol;h 40000 mol!h!
For each 3ater molar flo3 feed rate determine the methane conversion and the e5it
hydrogen molar flo3 rate!
%" <f the 3ater feed flo3 rate is /0000 mol;h determine the 6est choice for reactor
-ressure and tem-erature to give a minimum of $0M methane conversion!

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2raft J!M! Keith 4cto6er (4 /00#
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