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
H2O
H2O
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
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!
M
M steam reforming -lug flo3 model
M includes 3aterBgas shift reaction and overall reaction
M
M this is an isothermal model 3ith no -ressure dro-N
M
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M 8:4 = :/4 OBP 84 = ?:/ r5n (
M 84 = :/4 OBP 84/ = :/ r5n /
M 8:4 = / :/4 OBP 84/ = 4 :/ r5n ?
M
M feed conditions
M a I 84
M 6 I :/4
M c I 84/
M d I :/
M e I :e
M f I 8:4
M
clear
figure(()
close
M
Fa0I0D Mmol;hr
F60I(0000D
Fc0I0D
Fd0I(00D
Fe0I0D
Ff0I(0000D
M
Ftot0IFa0=F60=Fc0=Fd0=Fe0=Ff0D
M
M -artial -ressures in atm
7tot0 I (D
7a0 I 7tot0QFa0;Ftot0D
760 I 7tot0QF60;Ftot0D
7c0 I 7tot0QFc0;Ftot0D
7d0 I 7tot0QFd0;Ftot0D
7e0 I 7tot0QFe0;Ftot0D
7f0 I 7tot0QFf0;Ftot0D
M
M tem-eratures in K
T0 I (000D
M
M set u- numerical model
d3I(eB(D
3(()I0D
M
Fa(()IFa0D
F6(()IF60D
Fc(()IFc0D
Fd(()IFd0D
Fe(()IFe0D
Ff(()IFf0D
M
7a(()I7a0D
76(()I760D
7c(()I7c0D
7d(()I7d0D
7e(()I7e0D
7f(()I7f0D
M
for iI(%?#/;d3=(D
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3(i=()I3(i)=d3D
M
K(Ie5-(?0!4/0B/"(01;T(i))D
K/Ie5-(B?!"$#=4(10;T(i))D
K?Ie5-(?4!/(#B?(/11;T(i))D
M
K8:4I1!1.eB4Qe5-(?#/#0;#!?(4;T(i))D
K84I#!/?eB.Qe5-("01.0;#!?(4;T(i))D
K:/I1!(/eB$Qe5-(#/$00;#!?(4;T(i))D
K:/4I(!""e.Qe5-(B##1#0;#!?(4;T(i))D
M
9in(I4!//4#e(.Qe5-(B/40(00;#!?(4;T(i))D
9in/I(!$..e1Qe5-(B1"(?0;#!?(4;T(i))D
9in?I(!0/0/e(.Qe5-(B/4?$00;#!?(4;T(i))D
M
2E*I(=K8:4Q7f(i)=K84Q7c(i)=K:/Q7d(i)=K:/4Q76(i);7d(i)D
r(I9in(;7d(i)R/!.;2E*R/Q(7f(i)Q76(i)B7d(i)R?Q7a(i);K()D
r/I9in/;7d(i);2E*R/Q(7a(i)Q76(i)B7d(i)Q7c(i);K/)D
r?I9in?;7d(i)R?!.;2E*R/Q(7f(i)Q76(i)R/B7d(i)R4Q7c(i);K?)D
M
Fa(i=()IFa(i)=(r(Br/)Qd3D
F6(i=()IF6(i)B(F60;Ff0)Q(r(=r/=/Qr?)Qd3D
Fc(i=()IFc(i)=(r/=r?)Qd3D
Fd(i=()IFd(i)=(?Qr(=r/=4Qr?)Qd3D
Fe(i=()IFe(i)D
Ff(i=()IFf(i)B(r(=r?)Qd3D
FtotIFa(i=()=F6(i=()=Fc(i=()=Fd(i=()=Fe(i=()=Ff(i=()D
M
7a(i=() I 7tot0QFa(i=();FtotD
76(i=() I 7tot0QF6(i=();FtotD
7c(i=() I 7tot0QFc(i=();FtotD
7d(i=() I 7tot0QFd(i=();FtotD
7e(i=() I 7tot0QFe(i=();FtotD
7f(i=() I 7tot0QFf(i=();FtotD
M
end
M
figure(()
-lot(3Fa)
hold on
-lot(3F6SrBBS)
-lot(3FcSgB!S)
-lot(3FdS9%S)
-lot(3FeScS)
-lot(3FfS6S)
5la6el(S8atalyst Geight gS)
yla6el(SMolar Flo3 Rate mol;hrS)
legend(S84SS:T/4SS84T/SS:T/SS:eSS8:T4S)
(
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2raft J!M! Keith 4cto6er (4 /00#
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2raft 7age # March /0 /00$
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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