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Applied: Simulation of The Catalytic Partial Oxidation of Methane To Synthesis Gas
Applied: Simulation of The Catalytic Partial Oxidation of Methane To Synthesis Gas
ID CATALYSIS
A: GENERAL
ELSEVIER Applied Catalysis A: General 138 (1996) 245-264
Abstract
The modeling and simulation of reactors for the catalytic partial oxidation of natural gas to
synthesis gas is complex and requires detailed kinetics if it is to be representative and reliable.
Adiabatic fixed bed reactors with a catalytic combustion zone fed with m e t h a n e / o x y g e n or
m e t h a n e / a i r mixtures were simulated based upon the kinetics of total combustion, steam
reforming and water-gas shift on a Ni catalyst. The steam reforming reactions and water-gas shift
reaction are parallel or more or less consecutive to the total combustion, depending upon the
degree of reduction of the catalyst, which is determined by the temperature and the gas phase
composition. The calculation of the net rates of coke formation was included in the simulation.
The influence of carbon dioxide and steam was also investigated.
I. Introduction
In recent years, natural gas has received increased attention as a feedstock for
the chemical industry.
The first step in natural gas conversion is often the production of synthesis
gas (CO + H2). The synthesis gas can then be used for the production of
methanol, for oxo-synthesis and Fischer-Tropsch synthesis. After removal of
CO it also provides the hydrogen for ammonia synthesis and hydrogenations.
Syngas is mainly produced by steam reforming in large, gas fired furnaces,
containing a large number of parallel reactor tubes. The CO content of the
synthesis gas obtained by steam reforming is too low for methanol synthesis, for
* Corresponding author. Tel. ( + 32) 92644516, fax. ( + 32) 92644999, e-mail gf@elptrs3.rug.ac.be.
2. Rate equations
CH4
-3 H2 +3 H2 + 4 H2 -4 H2
H20 + H2
CO ~ ~ CO 2
+ H20 - H2
III
248 A.M. De Groote. G.F. Froment/Applied Catalysis A: General 138 (1996) 245-264
The overall reaction scheme includes the CO 2 reforming (2') and WGS
reaction (4) as well as the steam reforming reactions (2) and (3). Indeed, CO 2
reforming is a linear combination of reactions (II) and (III) of the above scheme.
The corresponding rate equations are given in Table 1.
Another problem encountered in the simulation of the catalytic partial oxida-
tion of methane is the degree of reduction of the Ni catalyst required for the
steam reforming. In this process, the catalyst is operating in the reduced state, at
least as soon as hydrogen is formed. It is not clear whether or not a partially
reduced catalyst is active for steam reforming; if so then to a lesser degree. Will
steam reforming only occur in the catalytic partial oxidation process after all the
oxygen has been used? In other words: is steam reforming completely or
partially consecutive or completely parallel to the catalytic total combustion of
natural gas? According to Dissanayake et al. [14], three different zones exist in a
reactor for the catalytic partial oxidation of methane over a Ni/AI203 catalyst.
In the first zone, there is a NiA1204 phase with moderate activity for the total
combustion to CO 2 and H20. In the second zone, the catalyst consists of NiO
and Al203 and shows high activity for the total combustion. Finally, in the last
zone, metallic Ni is present and CO and H 2 are produced. These observations
would mean that steam reforming is consecutive to complete combustion, so that
the state of reduction of the catalyst has to be incorporated in the kinetic model.
This has been accounted for in the present simulations by multiplying the rate of
Table 1
Kinetic equations
Reaction Kinetic equation
k.[C.,][O2] k~[CH,][O2]-~
(l) = +
r~ (l+r'[C"4]+K2[O:]): 1+r,[C.,]+X2[O2]
(2) r2
( l + K c o P c o + K n ~ p " 2+Kcg4pc" +K,2oPn20/PH2) 2
(3) r3
(1 + KcoPc 0 + Kn2Pn 2 + Ken,Pen ,+ K n 2 0 P n 2 0 / p , 2 ) 2
k4/Pn2( PcoPn:o - P"2 Pc02/K4)
(4) r4
(1 + KcoPc 0 + K n : p . : + Kcn4Pc.4 + K.20prl20/p.~) 2
k6 Pco - k7Pc02/Pco
(5)
rs ( 1 + goPco 2 / P c o )
3 1
k8 Pc.4/P~2 - kgP~2
(6)
r~ (I+K"~P"~) ~
kto PH20 / P~l:
(7) r7
(l + krt2PH2 + Kwpn20/Pn2) 2
(8) rs = f(Po:)
A.M. De Groote, G.F. Froment // Applied Catalysis A: General 138 (1996) 245-264 249
T, (K) (%)
1800 100
1600 red
8O
1400
6O
1200
40
1000
20
8O0
60O 0
o o.~ 1 1.s 2 2.5
z (m)
Fig. 1. Reduction profile of the catalyst for a simulation using the VDR-model.
the steam reforming reactions and the WGS reaction with a reduction factor,
which is a power function of the fractional oxygen conversion. The power in
this reduction factor (Xo2)~2 was determined by trial and error with respect to
the maximum temperature in the partial oxidation of a C H 4 / O 2 feed. The same
reduction factor is used for feeds containing CO 2 and H20, since, no informa-
tion regarding the maximum temperature was available for those cases. An
example of the reduction profile of the catalyst is shown in Fig. 1 for a feed
consisting of C H 4 and O 2 only. It is clear from the figure that the catalyst is
completely reduced as soon as all oxygen is consumed.
In previous work, the C-formation zones were based upon thermodynamic
calculations. Wagner and Froment [15] predicted the zones in which C-forma-
tion is possible through methane cracking and through the Boudouard reaction
by means of experimentally determined 'threshold constants'. To go beyond this
and to predict the amounts of carbon that can be formed on the catalyst, requires
kinetic equations. These were also derived by Wagner and Froment [16] from
experiments in a differentially operated electrobalance reactor.
For the Boudouard reaction (5), methane cracking (6) and carbon gasification
by steam (7), the reaction rates determined by Wagner and Froment [16] are
applied. The rate equations are presented in Table 1.
3. R e a c t o r m o d e l
dxo 2 Pb~
d'---~ = "----6-(2rllrl
E + r/8r8)
02
d Xco Pb 0
d z = F, 0 (T/2r2 - 7/4r4 - 2r/sr5 + r / 7 r 7 )
CH4
d Xco2 Pb 0
d------~ = ----6--(~11rl
F + "r/3r3 Jr "r/4r4 at- "r/5r5 + "08r8)
CH4
Energy equation:
8
dr Pb E rliri(- AH)i
dz u s pgCp i= 1
Pressure drop equation:
dpt fpg u 2
dz dp
Table 2
Comparison of the simulation results with the industrially observed values for an autothermal reformer
Industrial VDR-model BV-model
Feed 1: CH4, 02, H 2 0
F°H4 ( N m 3 / h ) 3483 3483 3483
02/CH 4 0.598 0.598 0.598
H 20/CH 4 1.4 1.4 1.4
pt° (bar) 25 25 25
Tmax (K) 1444 1210
Product yields
Yo2 0 0.00026 0
YCHa 0.008 0.0055 0.010
YH~ 0.456 0.458 0.456
YCO 0.160 0.156 0.153
YCO2 0.07 0.06 0.068
YH20 0.306 0.318 0.312
Outlet conditions
Tout (K) 1223 1247 1210
FH 2 ( N m 3 / h ) 6976 6925 6872
Fco ( N m 3 / h ) 2444 2355 2307
252 A.M. De Groote, G.F. Froment/Applied Catalysis A: General 138 (1996) 245-264
Table 3
Simulation results for the catalytic partial oxidation of methane with oxygen using the VDR-model. Influence
of the addition of steam and CO 2 to the feed mixture
Feed 1 2 3 4
XcH, (%) 97.61 98.37 92.85 93.01
go2 (%) 99.81 100 99.30 100
x co (%) 67.31 80.97 73.28 92.96
Xco 2 (%) 27.38 5.25 16.28 - 5.19
Tmax (K) 1444 1782 1305 1540
ax max (m) 1.3963 0.5224 1.7731 0.7344
Tout (K) 1247 1412 1159 1274
P~out (bar) 25.1 40 25.221 25.112 25.207
H 2//CO 2.9407 2.0825 2.3513 1.6030
Fco ( N m a / h ) 2355 2829 2576 3254
Fn 2 (Nm 3 / h ) 6925 5891 6057 5216
C-bal. 97.07 87.85 97.81 95.55
Table 4
Simulation results for the catalytic partial oxidation of methane with oxygen using the BV-model. Influence of
the addition of steam and CO 2 to the feed mixture
Feed 1 2 3 4
Xcn, (%) 95.51 97.24 91.84 96.29
Xo2 (%) I00 100 99.87 100
Xco (%) 65.94 86.90 74.55 95.03
Xco 2 (%) 29.51 4.76 17.22 - 6.57
Tmax (K) 1210 1393 1153 1319
aXmax (m) 5.9335 1.2747 6 1.9228
Tout (K) 1210 1393 1153 1318
Pt,out (bar) 24.992 25.106 24.908 25.077
H 2//CO 2.9793 1.9714 2.3240 1.6300
Fco (Nm3//h) 2307 3036 2609 3326
Fn 2 ( N m 3 / h ) 6872 5985 6064 5422
C-bal. 99.94 94.42 99.95 93.35
A.M. De Groote, G.F. Froment /Applied Catalysis A: General 138 (1996) 245-264 253
Table 5
Reaction dimensions and feed conditions
Feed 1 2 3 4 5
Ft° ( N m 3 / h ) 10490.40 5583.78 11661.36 6215.76 6184.26
pt° (bar) 25.331 25.331 25.331 25.331 25.331
T O (K) 808 808 808 808 808
02/CH 4 0.598 0.598 0.598 0.598 0.598
H 20/CH 4 1.4 0.0 1.4 0.0 0.0
yO~ 0.19945 0.37419 0.17950 0.33676 0.33680
Y~n 4 0.33352 0.62571 0.30017 0.56314 0.56320
y° 2 0.00010 0.00010 0.00010 0.00010 0.10000
Y~o2 0 0 0.10000 0.100130 0
yO 20 0.46693 0 0.42023 0 0
d r (m) 1.20 1.20 1.20 1.20 1.20
l(m) 3 or 6 3 or 6 3 or6 3 or6 3
dp (m) 0.0050 0.0050 0.0050 0.0050 0.0050
maximum temperature, which is much higher when total combustion and steam
reforming occur consecutively.
T, (K)
1600
1400 2
f : _,
1200 3
1000 t
6oo i i i i i
0 1 2 3 4 5
z (m)
Fig, 2. Temperature profiles through the catalyst bed for the partial oxidation of methane with oxygen at 25
bar. BV-model. Influence of the addition of steam and carbon dioxide to the feed.
T s (K)
2000
Feed:
IBO0 1: CH 4, 0 2, H20
2: CH 4, 02
3: CH 4, 0 2, H20, C02
1800
02, C02
I I ,-c_,..
1400
12O0
'%
1000
.oo
z (rn)
Fig. 3. Temperature profiles through the catalyst bed for the partial oxidation of methane with oxygen at 25
bar. VDR-model. Influence of the addition of steam and carbon dioxide to the feed.
A.M. De Groote, G.F. Froment /Applied Catalysis A: General 138 (1996) 245-264 255
rc (mol/kgca t s)
0.03
Feed:
12: CH 4, 0 2
1
4: CH 4, 0 2 , CO 2
0.02
0.01
\
0 i r
r c (mol/kgcat s)
0.04
2 Feed:
1:
2:
CH 4, 0 2 , H20
CH 4, 02
02j
0.03
3: CH 4, 02 , H20, C
4: CH 4, 0 2 , CO 2
0.02
0.01
0 i i i i
r 2 i~rno.-=
IIItn
cat s)
2
Feed:
1: CH4, 0 2 , H20
1.5 2: CH 4, 02
3: CH 4, 0 2 , H20, CO2
4: CH 4, 0 2 . CO 2
0.5
-0.5
0,5 1 1.5 2 2.5
z (m)
Fig. 6. Effective rate of carbon monoxide production by steam reforming through the catalyst bed for the
partial oxidation of methane with oxygen at 25 bar. VDR-model. Influence of the addition of s e a m and carbon
dioxide to the feed.
When steam is added to the feed, steam reforming starts sooner in the reactor
(Fig. 6), so that the maximum temperature is lower. This leads in turn to lower
reforming rates (Fig. 6) and lower combustion rates (Fig. 7), since, both the
temperature and the partial pressure of methane are lower. Because of the
presence of steam in the feed, the equilibrium in the WGS reaction (Fig. 8)
r I (mol/kgcat s)
0.5
Feed:
1: CH 4, 0 2 , HzO
0.4 2: CH 4, 02
3: CH 4, 0 2 , H20, CO2
4: CH 4, 0 2 , CO 2
0.3
CH4 + 2 0 2 ~ C O 2+ 2H20
4
0.2
0.1 1
r4 (mol/kgcat s)
0.2
0.1
1
. _ _
0
3
-0.1
CO + H2 0 ~ C O 2 + H2
-0.2
Feed:
-0.3
1: CH 4, 02 , H 2 0
2: CH 4, 02
-0.4 3: CH 4 , 0 2 , H20, CO2
4: CH 4, 02, CO2
2 4
-0.5
0.5 1 1.5 2 2.5
Z (m)
Fig. 8. Effective rate of the water-gas shift reaction through the catalyst bed for the partial oxidation of
methane with oxygen at 25 bar. VDR-model. Influence of the addition of steam and carbon dioxide to the feed.
Xco=(%)
30
Feed: ~ 1
1: CH 4, 0 2 , H 2 0
2: CH 4, 0 z
20 3: CH 4, 0 2 , H20, CO2
4: CH 4, 0 2 , CO 2
2
0
4
-10 ~
0.5 1 1.5 2 2.5 3
Z (m)
Fig. 9. Conversion of methane to carbon dioxide through the catalyst bed for the partial oxidation of methane
with oxygen at 25 bar. VDR-model. Influence of the addition of steam and carbon dioxide to the feed.
258 A.M. De Groote, G.F. Froment /Applied Catalysis A: General 138 (1996) 245-264
When the feed does not contain any steam, a peak is observed in the
conversion to CO 2 (Fig. 9, curves 2 and 4). The rising part of the peak results
from the higher effective combustion rate due to the higher temperature and the
lower effective reforming rates resulting from the lower partial pressure of
steam. The decreasing part of the peak can be explained by the WGS reaction.
Indeed, when a considerable amount of CO 2 is formed, the equilibrium of the
reaction shifts towards H 2° and CO. This in turn leads to a higher conversion to
CO and to a syngas with lower H 2 / C O product ratio (Table 3).
The effective net coking rate predicted by the BV-model and by the VDR-
model is presented in Figs. 4 and 5. A peak is observed in the net coking rate
near the reactor inlet. This is due to the endothermic methane cracking and also
explains the small temperature decrease in Figs. 2 and 3. Although the reactor
inlet temperature is relatively low and methane cracking is enhanced at high
temperatures, the reaction still proceeds because of the high partial pressure of
methane. It is also clear from Fig. 5 (curves 1 and 3) that for feeds containing
steam there is almost no coke deposition. In the literature, it is found that
addition of CO 2 to the partial oxidation feed decreases the amount of carbon
deposited on the catalyst surface, because of the equilibrium in the Boudouard
reaction. Checking the carbon balances in Table 4 for simulations using the
BV-model shows that the opposite would be true. When the total combustion
reaction and the reforming reactions are considered in series (VDR-model), on
the other hand, addition of carbon dioxide to the feed decreases the amount of
carbon considerably (Table 3, feed 2 and 4), although the zone of the catalyst
bed covered with coke is slightly larger (Fig. 5, curves 2 and 4). The methane
r (mol/kgcat s)
0.3
A: 2 CO --~C + CO2 B Feed 2: CH4, 02
B: CH4 "--~'C + 2 H2 I
0.2
C:C+ H20"-~CO+ H2
0.1 1D:C+O2--~CO2 /
-o.1 ~ A
-0.2 I I
Fig. 10. Effective rate of the coking reactions for feed 2 through the first part of the catalyst bed for the partial
oxidation of methane with oxygen at 25 bar. VDR-model. Influence of the addition of steam and carbon
dioxide to the feed.
A.M. De Groote, G.F. Froment / Applied Catalysis A: General 138 (1996) 245-264 259
(mol/kg cat s)
0.03
A: 2 CO --~-C + CO 2
B:CH 4 - - ~ C + 2 H 2
0.02 C: C + H20 --=-CO + H 2
D : C + O2 - - ~ CO 2
Feed 4: CH 4, 02, CO 2
B
0.01
-0.01
-0.02
o o12 o:, o16 0:8
z (m)
Fig. ] 1. Effective rate of the coking reactions for feed 4 through the first part of the catalyst bed for the partial
oxidation of methane with oxygen at 25 bar. VDR-model. Influence of the addition of steam and carbon
dioxide to the feed.
cracking is slower because of the lower temperature, but the reverse Boudouard
reaction is slower too, so that the zone of the reactor in which coke is deposited
is extended. This follows from Figs. 10 and 11, in which the effective rates of
the individual coking and gasification reactions are shown for feed 2 and 4, in
(mol/kgca t s)
0.04
I
Reaction Feed:
0.03 I A: 2 CO--="C + CO 2 2: CH 4, O z
~B: CH 4 --P-C + 2 H 2 4: CH 4, 0 2 , CO 2
0.02
0.01 ~ ~ 2B
4B
o
4A
-o.o12
-o,o2
0 0.2 0.4 0.6 0.8
z (m)
Fig. 12. Effective rate of the coking reactions through the first part of the catalyst bed for the partial oxidation
of methane with oxygen at 25 bar. BV-model. Influence of the addition of steam and carbon dioxide to the
feed.
260 A.M. De Groote, G.F. Froment / A p p l i e d Catalysis A: General 138 (1996)245-264
Table 6
Simulation results for the catalytic partial oxidation of methane with oxygen using the VDR-model. Influence
of the addition of hydrogen to the feed mixture
Feed 2 5
pt° (bar) 25.33125 25.33125
XcH, (%) 98.37 95.61
Xo2 (%) 100 100
Xco (%) 80.97 84.36
Xco2 (%) 5.25 5.03
Tmax (K) 1782 1776
aXmax (m) 0.5224 0.3397
Tout (K) 1412 1361
Pt.out (bar) 25.221 25.265
H2/CO 2.0825 2.1787
Fco (Nm3/h) 2829 2938
Fn 2 (Nm 3/h) 5891 6401
C-bal. 87.85 93.78
that part of the reactor in which net coke formation is observed. For parallel
combustion and reforming reactions, the reverse Boudouard reaction is much
slower when CO 2 is present in the feed mixture (Fig. 12), so that the net coking
rate is increased.
r C ( m o l / k g c a t s)
o.05
Feed: 2
2: CH 4 , 0 2 5
0.04 5: CH 4 , O 2, H
2
0.03
0.02
0.01
o .J,
o o'., o.2 ;.3 0'.4 o.5 0 .s
z (m)
Fig. 13. Effective net coking rate through the first part of the catalyst bed for the partial oxidation of methane
with oxygen at 25 bar. VDR-model. Influence of the addition of hydrogen to the feed.
r ( m o l / k g c a t s)
0.3
A: 2 C O ~ , C + CO 2 tSB / 2B
B: CH 4 C + 2 H2 / [
o.
Ol / /
-o.1 2: CH 4, 0 2
5: CH 4 , 0 2 , H 2 5A 2A
-0.2
o o., o.2 o12 oi, o15 06
Z (m)
Fig. 14. Effective rate of the individual coking and gasification reactions for feeds 2 and 5 through the first
part of the catalyst bed for the partial oxidation of methane with oxygen at 25 bar. VDR-model. Influence of
the addition of hydrogen to the feed.
262 A.M. De Groote, G.F. Froment /Applied Catalysis A: General 138 (1996) 245-264
Table 7
Simulation results for the catalytic partial oxidation of methane with air using the VDR-model
Feed A B
pt° (bar) 25.33125 61.423
XcH, (%) 98.17 89.09
Xo2 (%) 100 100
Xco (%) 70.05 72.77
Xco~ (%) 7.67 8.00
Tmax (K) 1292 1461
aXmax (m) 5.0017 1.4116
Tout (K) 1291 1286
Pt.out (bar) 24.553 61.096
Hz/CO 2.3150 2.0255
Fco (Nm3/h) 2440 2535
FH 2 (Nm3/h) 5648 5134
C-bal. 79.55 91.68
5. Conclusions
From the simulations, it appears that the temperatures during the catalytic
partial oxidation of methane to synthesis gas are within acceptable bounds when
A.M. De Groote, G.F. Froment /Applied Catalysis A: General 138 (1996) 245-264 263
air is used or when steam or carbon dioxide are added to the feed. In the
catalytic partial oxidation of methane with oxygen, a maximum temperature of
about 1500°C was predicted by the VDR-model. This peak temperature is
detrimental for the Ni catalyst, because of plastification.
When steam is added, the amount of coke becomes negligible. CO 2 also
reduces the amount of carbon formation, but increases the area in which coke is
deposited. Adding H 2 to the feed is not an efficient way of reducing coke
formation.
In the catalytic partial oxidation of methane with air instead of oxygen, the
maximum temperatures are considerably lower and less coke is formed. The
separation of N 2 from the synthesis gas is a drawback of this mode of operation.
6. Symbols
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