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~ APE PLD I

CATALYSIS
A: GENERAL

ELSEVIER

Applied Catalysis A: General 138 (1996) 245-264

Simulation of the catalytic partial oxidation of methane to synthesis gas


A n n M. D e Groote, Gilbert F. Froment *
Laboratorium voor Petrochemische Techniek, Universiteit Gent, Krijgslaan 281, B-9000 Ghent, Belgium

Received 1 June 1995; revised 16 October 1995; accepted 20 October 1995

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.
Keywords: Oxidation (partial); Synthesis gas production; Methane

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. 0926-860X/96/$15.00 1996 Elsevier Science B.V. All rights reserved SSDI 0 9 2 6 - 8 6 0 X ( 9 5 ) 0 0 2 9 9 - 5

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A.M. De Groote, G.F. Froment /Applied Catalysis A: General 138 (1996) 245-264

which a ratio H 2 / ( C O + CO 2) of 2 is required. To achieve the desired H 2 / C O ratio, recycling CO 2 is necessary. This may cause carbon deposition and deactivation of the catalyst. An alternative technique for producing syngas with the desired C O / H 2 ratio is partial oxidation with oxygen or air. For the non-catalytic production of synthesis gas by partial oxidation of hydrocarbons, two industrial processes are in use: the Texaco process, developed in 1954 for the production of syngas from natural gas and heavy hydrocarbons, and the Shell gasification process, developed in 1956. Non-catalytic partial oxidation is well suited for the production of syngas for ammonia production. The CO is then converted in a catalytic shift reactor to CO 2, which is removed by means of absorption and reaction. One of the advantages of partial oxidation, catalytic or not, over steam reforming is the possibility of operating at high pressure and much higher temperatures. Indeed, the overall exothermicity of the process permits adiabatic operation, in refractory lined vessels, thus avoiding metallurgical problems. The partial oxidation can also be carried out on a bifunctional combustion/steam reforming catalyst. In that case, the gas is fed at a much lower temperature and pure oxygen can be used. This process combines the exothermic combustion of a fraction of the natural gas: CH 4 + 202 ~--- CO 2 + 2H20 with the endothermic steam reforming reactions: CH 4 + H 2 0 ~ CO + 3H 2 CH 4 + 2 H 2 0 ~ C O 2 -1- 4H 2 the accompanying water-gas shift: CO + H 2 0 #
C O 2 "]- H 2

(1)

(2) (3)

(4)

and the CO2-reforming reaction: CH 4 + CO 2 # 2CO + 2H 2 (2')

to achieve a syngas with the desired composition [1-3] [4-9]. Care has to be taken to avoid carbon deposition according to the Boudouard reaction [5]: 2CO .~ C + CO 2 and to methane cracking: CH 4 ~ C + 2 H 2 A fraction of the carbon can be gasified by steam or oxygen: C+H20
~- C O + H 2

(5)
(6)

C + 02 ~ CO 2

(7) (8)

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247

The H 2 / C O ratio of the process gas can be adjusted by controlling the O 2 / C H 4 ratio of the feed. Feeding only 02 and CH 4 leads to a syngas with low H 2 / C O ratio, but coke deposition is difficult to avoid. Air can be used instead, but the separation of N 2 from the synthesis gas is not easy. Air is required when the syngas is intended for ammonia synthesis. The present paper deals with the simulation of the catalytic partial oxidation of methane on a Ni catalyst by means of oxygen (or air) sometimes mixed with steam (in case of autothermal reforming), hydrogen a n d / o r carbon dioxide.

2. Rate equations
In the modeling of the partial oxidation of methane to syngas on a Ni catalyst, it is necessary to combine a reaction mechanism for the combustion (1) with a reaction mechanism for the reforming reactions [(2), (3) and (2')], WGS reaction (4) and coking and gasification reactions [(5)-(8)]. Kinetic equations for some of the steps of the catalytic partial oxidation process were reported by Hickmann and Schmidt [I0], but for Pt and Rh catalysts, not for a Ni catalyst. Trimm and Lam [11] have published a kinetic equation for the complete combustion of methane to CO 2 and H 2 0 on a Pt/A1203 catalyst, under the assumption that the rate determining step is the surface reaction between adsorbed methane and both diatomically adsorbed oxygen and oxygen from the gas phase. The equation is given in Table 1. Xu and Froment [12,13] described the steam reforming of methane on a Ni/MgOA1203 catalyst by the following reactions:
CH4

+ H20 -3 H2

- H20

-2

H20

+ 2 H 20
-4 H2

+3 H2

+ 4 H2

H20 CO

+ H2

~
+ H20 - H2

CO 2

III

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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 oxidation 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

(l) (2) (3)


(4)

k.[C.,][O2] k~[CH,][O2]-~ + r~ (l+r'[C"4]+K2[O:]): 1+r,[C.,]+X2[O2]


=
r2

( l + K c o P c o + K n ~ p " 2+Kcg4pc" +K,2oPn20/PH2) 2


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)
r4

(5) (6) (7) (8)

rs

(1 + KcoPc 0 + K n : p . : + Kcn4Pc.4 + K.20prl20/p.~) 2 k6 Pco - k7Pc02/Pco ( 1 + goPco 2 / P c o )


3 1

r~
r7

k8 Pc.4/P~2 - kgP~2 (I+K"~P"~) ~ kto PH20 / P~l:

(l + krt2PH2 + Kwpn20/Pn2) 2 rs = f(Po:)

A.M. De Groote, G.F. Froment // Applied Catalysis A: General 138 (1996) 245-264

249

T, (K)
1800

(%)
100

1600 1400

red
8O

6O

1200
40

1000
20

8O0

60O

o.~

1.s
z (m)

2.5

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 information 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-formation 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

For the simulation of the partial oxidation of methane to synthesis gas on a Ni catalyst, a one dimensional heterogeneous model is used [17]. Since, the reactor

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is adiabatic, concentration and temperature gradients only occur in the axial direction. The only transport mechanism operating in axial direction is the overall flow itself and this is considered to be of the plug flow type. Intraparticle diffusion limitations are expressed here for the sake of brevity in terms of effectiveness factors. Thus, the simulation of the partial oxidation reaction is based on the following set of differential equations: Continuity equations: d XCH~ Pb ff2 d----~ = ~ ( 7 / l r l F
CH 4

d- 172r 2 + "q3r3 + Y/6r6)

dxo 2 Pb~ d'---~ = "----6-(2rllrl + r/8r8) E


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 + "r/3r3 Jr "r/4r4 at- "r/5r5 + "08r8) F


CH4

Energy equation:
8

dr dz

Pb E rliri(- AH)i u s pgCp i= 1

Pressure drop equation:

dpt dz

fpg u 2 dp

4. Simulation of an adiabatic fixed bed reactor

In an industrial autothermal reformer, operating at 25 bar, with a feed consisting of methane, steam and oxygen, H 2 0 / C H 4 ratios of 2 are common. Ratios as low as 1.4 have been applied, thereby decreasing the H 2 / C O product ratio from 3.27 to 2.80. The O 2 / C H 4 molar feed ratio is 0.598 and the reactor outlet temperature amounts to 950C. Based on this case, simulations were performed for an adiabatic fixed bed reactor. The effectiveness factors used in these simulations were obtained from the integration of the second order differential equations describing the evolution of the various species inside the Ni catalyst pellet. To avoid having to integrate the continuity equations inside the pellets in each increment used in the integration of the fluid field equations,

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251

an average value based upon a number of off-line pellet simulations was selected for the various effectiveness factors. The values of the effectiveness factors are: "O~= "02 = "O,s= "O4= 0.05 0.07 0.06 0.70 for for for for the total combustion of CH 4 to CO 2 and H 20 CO production by steam reforming CO 2 production by steam reforming the WGS-reaction

The rates of carbon formation and gasification are also affected by the concentration profiles resulting from the four main reactions and this is also accounted for by the use of appropriate averaged effectiveness factors: "O5= "O6= r/7 = "O8= 0.05 0.05 0.05 0.05 for for for for the Boudouard reaction methane cracking C-gasification by steam C-gasification by oxygen.

Notice the very low values of these "O's, except that for the WGS reaction ([12,13]).

4.1. Discussion of simulation results


An industrial autothermal reformer for syngas production is simulated using two models for the state of the Ni catalyst. In the first the catalyst has a varying

Table 2 Comparison of the simulation results with the industrially observed values for an autothermal reformer Industrial Feed 1: CH4, 02, H 2 0 FH4 ( N m 3 / h ) 02/CH 4 H 20/CH 4 pt (bar) Tmax (K) Product yields Yo2 YCHa YH~ YCO YCO2 YH20 Outlet conditions Tout (K) FH 2 ( N m 3 / h ) Fco ( N m 3 / h ) 3483 0.598 1.4 25 VDR-model 3483 0.598 1.4 25 1444 BV-model 3483 0.598 1.4 25 1210

0 0.008 0.456 0.160 0.07 0.306

0.00026 0.0055 0.458 0.156 0.06 0.318

0 0.010 0.456 0.153 0.068 0.312

1223 6976 2444

1247 6925 2355

1210 6872 2307

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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 XcH, (%) go2 (%) x co (%) Xco 2 (%) Tmax (K) ax max (m) Tout (K) P~out (bar) H 2//CO Fco ( N m a / h ) Fn 2 (Nm 3 / h ) C-bal. 1 97.61 99.81 67.31 27.38 1444 1.3963 1247 25.1 40 2.9407 2355 6925 97.07 2 98.37 100 80.97 5.25 1782 0.5224 1412 25.221 2.0825 2829 5891 87.85 3 92.85 99.30 73.28 16.28 1305 1.7731 1159 25.112 2.3513 2576 6057 97.81 4 93.01 100 92.96 - 5.19 1540 0.7344 1274 25.207 1.6030 3254 5216 95.55

degree of reduction (VDR-model) and the steam reforming is mainly consecutive to the catalytic combustion. In the second model the catalyst is bivalent (BV-model) and the catalytic combustion and steam reforming operate purely in parallel. The simulation results are compared with the industrial values in Table 2, for an inlet temperature of 808 K. It is clear from Table 2 that the results at the exit are in reasonable agreement with those measured in industry. This indicates at least that the equilibrium values calculated in the simulation program are correct. Intermediate values, however, are also important, e.g., the maximum temperature, so as to garantee that the Ni catalyst is not damaged by excessive temperatures. It also follows from Table 2 that the main difference between the simulations with the BV-model and the VDR-model lies in the

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 Xcn, (%) Xo2 (%) Xco (%) Xco 2 (%) Tmax (K) aXmax (m) Tout (K) Pt,out (bar) H 2//CO Fco (Nm3//h) Fn 2 ( N m 3 / h ) C-bal. 1 95.51 I00 65.94 29.51 1210 5.9335 1210 24.992 2.9793 2307 6872 99.94 2 97.24 100 86.90 4.76 1393 1.2747 1393 25.106 1.9714 3036 5985 94.42 3 91.84 99.87 74.55 17.22 1153 6 1153 24.908 2.3240 2609 6064 99.95 4 96.29 100 95.03 - 6.57 1319 1.9228 1318 25.077 1.6300 3326 5422 93.35

A.M. De Groote, G.F. Froment /Applied Catalysis A: General 138 (1996) 245-264
Table 5 Reaction dimensions and feed conditions Feed Ft ( N m 3 / h ) pt (bar) T O (K) 02/CH 4 H 20/CH 4 yO~ Y~n 4 y 2 Y~o2 yO 20 d r (m) l(m) dp (m) 1 10490.40 25.331 808 0.598 1.4 0.19945 0.33352 0.00010 0 0.46693 1.20 3 or 6 0.0050 2 5583.78 25.331 808 0.598 0.0 0.37419 0.62571 0.00010 0 0 1.20 3 or 6 0.0050 3 11661.36 25.331 808 0.598 1.4 0.17950 0.30017 0.00010 0.10000 0.42023 1.20 3 or6 0.0050 4 6215.76 25.331 808 0.598 0.0 0.33676 0.56314 0.00010 0.100130 0 1.20 3 or6 0.0050 5 6184.26 25.331 808 0.598 0.0 0.33680 0.56320 0.10000 0 0 1.20 3 0.0050

253

maximum temperature, which is much higher when total combustion and steam reforming occur consecutively.

4.1.1. Influence of carbon dioxide and steam in the feed mixture The influence of CO 2 and H 2 in the feed mixture is investigated at 25 bar and constant FH,, using the BV-model and the VDR-model. The results are listed in Tables 3 and 4. Table 5 gives the composition of the corresponding feeds, feed 1-4, and the reactor dimensions. Since, the partial pressure of hydrogen is a multiplying factor in the denominator of the kinetic expressions for the steam reforming reactions, 0.01% H 2 is added to the feed mixture in all simulations, to avoid infinite reaction rates at the inlet. A reactor length of 3 m is used in the simulations with the VDR-model and of 6 m in the simulations with the BV-model. It is clear from the Tables that addition of CO 2 and H 2 0 to the feed is mainly reflected in the H 2 / C O product ratio. Adding CO 2 to the feed decreases the conversion of methane, but increases the conversion towards CO, thus leading to a syngas with lower H 2 / C O ratio. On the other hand, the H 2 / C O ratio in the effluent becomes higher when steam is added. By adding carbon dioxide or steam to the C H 4 / O 2 mixture, a syngas with the desired H 2 / C O ratio can be produced. A given H J C O ratio in the effluent can also be obtained by changing the C H 4 / O 2 feed ratio. The low carbon balances result either from a high rate of carbon deposition or from its insufficient gasification. The main difference between the BV-model and the VDR-model lies in the shape of the temperature profiles, shown in Figs. 2 and 3. Because of the partially consecutive character of total combustion and reforming reactions, the temperature profile predicted by the VDR-model shows a peak. The top of this peak corresponds to the take off of the endothermic reforming reactions. Since

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A.M. De Groote, G.F. Froment/Applied Catalysis A: General 138 (1996) 245-264

T, (K) 1600

1400

f
1200 1000 t

_,
3

800 6oo 0
i i i

41CH 4. Oa: CO 2' C02


i i

3 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.

all reactions occur simultaneously in the BV-model, a plateau is observed in the predicted temperature profile, instead of a peak. This difference between the temperature profiles is also reflected in the net coking rate, shown in Figs. 4 and 5, as will be discussed later in this section.

T s (K)
2000

IBO0

1800

I I

,-c_,..

Feed: 1: CH 4, 0 2, H20 2: CH 4, 02 3: CH 4, 0 2, H20, C02 02, C02

1400

12O0

1000

.oo

'%
0.5 1 1.5 2 2.5

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
rc

255

(mol/kgca t s)
0.03

12: CH 4, 0 2 4: CH 4, 0 2 , CO 2 0.02

Feed:

0.01

\
i r

0 0

0.2

0.4

0.6

0.8

z (m)
Fig. 4. Effective net coking rate 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.

Adding CO 2 and/or H 2 0 to the feed mixture shifts the temperature peak further downstream in the reactor and lowers the maximum temperature. The temperature peak also becomes broader. Indeed, the simulations are performed for constant methane flow rate and constant pressure, so that addition of CO 2 and H 2 0 also increases the total flow rate.

r c (mol/kgcat s)
0.04

2
0.03

Feed:
1: 2: 3: 4:

CH 4, 0 2 , H20 CH 4, 02 CH 4, 02 , H20, C CH 4, 0 2 , CO 2

02j

0.02

0.01

0 0

i 0.2

i 0.4

0.6

0.8

z (m)
Fig. 5. 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 steam and carbon dioxide to the feed.

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IIItn r2i ~rno.-= cat s)

2
Feed: 1.5

1: 2: 3: 4:

CH4, CH 4, CH 4, CH 4,

0 2 , H20 02 0 2 , H20, CO2 0 2 . CO 2

CH4 + H20 --=~CO + 3 H2 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:

0.4

1: 2: 3: 4:

CH 4, CH 4, CH 4, CH 4,

0 2 , HzO 02 0 2 , H20, CO2 0 2 , CO 2

0.3 CH4 + 2 0 2 ~ C O 0.2


4

2+ 2H20

0.1

0.5

1.5 Z (m)

2.5

Fig. 7. Effective total combustion rate of methane to carbon dioxide and steam 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

257

r4 (mol/kgcat s)
0.2

0.1

1
. _ _

3
-0.1

CO + H2 0 ~ C O
-0.2

2 + H2

Feed:
-0.3 -0.4

1: 2: 3: 4: 2
0.5

CH 4, 02 , H 2 0 CH 4, 02 CH 4 , 0 2 , H20, CO2 CH 4, 02, CO2


2 2.5

-0.5

4
1 1.5

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.

shifts towards CO 2 and H 2. This explains the higher conversion to CO 2 (Table 3) and the higher H 2 / C O product ratio. When both CO 2 and steam are added to the feed, the effective reaction rate, i.e., the rate including diffusion limitations of the WGS is first positive, exhibits a dip and then becomes positive again (Fig. 8, curve 3). This also explains the small discontinuity in curve 3 in Fig. 9.

Xco=(%) 30

Feed:
20 1: 2: 3: 4: CH 4, 0 2 , H 2 0 CH 4, 0 z CH 4, 0 2 , H20, CO2 CH 4, 0 2 , CO 2

2 0

4 -10 ~

0.5

1.5 Z (m)

2.5

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.

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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 VDRmodel 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/kgca s) t 0.3 A: 2 CO --~C + CO2 B: CH4 "--~'C + 2 H2 C:C+ H20"-~CO+ H2 0.2 0.1 1D:C+O2--~CO2

Feed 2: CH4, 02

/
A

-o.1 -0.2 0
I

~
I

0.2

0.4
z (m)

0.6

08

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
(mol/kg cat s) 0.03 A: 2 CO --~-C + CO 2 B:CH 4 - - ~ C + 2 H 2 C: C + H20 --=-CO + H 2 D : C + O2 - - ~ CO 2

259

0.02

Feed 4: CH 4, 02, CO 2 B
0.01

-0.01

-0.02

o12

o:,
z (m)

o16

0:8

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

0.03

Reaction I A: 2 CO--="C + CO 2 ~B: CH 4 --P-C + 2 H 2

0.02

I
2B

Feed: 2: CH 4, O z 4: CH 4, 0 2 , CO 2

0.01

4B

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.

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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 pt (bar) XcH, (%) Xo2 (%) Xco (%) Xco2 (%) Tma (K) x aXmax (m) Tout (K) Pt.out (bar) H2/CO Fco (Nm3/h) Fn 2 (Nm 3/h) C-bal. 2 25.33125 98.37 100 80.97 5.25 1782 0.5224 1412 25.221 2.0825 2829 5891 87.85 5 25.33125 95.61 100 84.36 5.03 1776 0.3397 1361 25.265 2.1787 2938 6401 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.

4.1.2. Influence of H 2 in the feed In the catalytic partial oxidation of methane to synthesis gas on a Ni catalyst in a fixed bed reactor, carbon is mainly deposited by methane cracking. Therefore, a simulation is performed considering a catalyst with varying reduction state (VDR-model), whereby 10% hydrogen is added to the C H 4 / O 2 feed mixture. The reactor dimensions and feed conditions are listed in Table 5. The results are compared with those obtained for a CH 4 / 0 2 feed mixture in Table 6. When hydrogen is present in the feed mixture, the percentage carbon deficiency is lowered by about 6%, but the conversion of CH 4 is about 3% lower, too. For the C H a / O 2 / H 2 feed mixture, the maximum temperature in the catalyst bed is slightly lower. In the presence of hydrogen, there is no temperature decrease near the reactor inlet and the temperature peak is shifted upstream. This can be explained by referring to Fig. 13, which presents the effective net coking rate in the first part of the reactor and to Fig. 14, which shows the rates of the individual coking and gasification reactions. It is clear from Figs. 13 and 14 that when hydrogen is added to the feed mixture there is no carbon formation due to the endothermic methane cracking near the reactor inlet. Because of this there is no temperature decrease and the combustion reaction starts further upstream in the reactor. The fraction of the catalyst bed covered with carbon is significantly smaller for a feed mixture containing hydrogen, but the net coking rate is higher than for a hydrogen-lean feed, so that this part of the catalyst bed is subject to

A.M. De Groote, G.F. Froment / Applied Catalysis A: General 138 (1996) 245-264 r C ( m o l / k g c a t s)
o.05

261

Feed: 0.04

2: CH 4 , 0 2

5
2

5: CH 4 , O 2, H

0.03

0.02

0.01

o'.,

.J,

o.2

;.3
z (m)

0'.4

o.5

0 .s

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.

severe deactivation. It may be concluded that adding hydrogen to the feed mixture only prevents methane cracking in the first part of the reactor and is not efficient for avoiding carbon deposition.

( m o l / k g c a t s)
0.3

A: 2 C O ~ , C + CO 2 B: CH 4 C + 2 H2

tSB
/

/ 2B
[

o. Ol
-o.1
-0.2

/
2: CH 4, 0 2 5: CH 4 , 0 2 , H 2

5A

2A

o.,

o.2

o12
Z (m)

oi,

o15

06

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 pt (bar) XcH, (%) Xo2 (%) Xco (%) Xco~ (%) Tma (K) x aXmax (m) Tout (K) Pt.out (bar) Hz/CO Fco (Nm3/h) FH 2 (Nm3/h) C-bal. A 25.33125 98.17 100 70.05 7.67 1292 5.0017 1291 24.553 2.3150 2440 5648 79.55 B 61.423 89.09 100 72.77 8.00 1461 1.4116 1286 61.096 2.0255 2535 5134 91.68

4.1.3. Methane-air mixtures Because of the high temperatures encountered in the partial oxidation of methane with oxygen only, some simulations were performed, using the VDRmodel, for a C H a / a i r mixture. In the first simulation, the inlet flow rate of methane, FOR,, the total pressure and the O2//CH 4 feed ratio are kept constant. The reactor length has been increased to 6 m. The results are given in Table 7 (feed A). The maximum temperature in the reactor is considerably lower and is acceptable. The temperature peak is shifted further downstream in the reactor, because of the dilution. The conversion of 0 2 and C H 4 and the conversion to CO are much lower. Indeed, the effective combustion rate and the effective rates of the reforming reactions are significantly slower, because of the lower temperature and partial pressures of methane and oxygen. It should also be noted that the amount of deposited carbon is much higher compared to the corresponding case with oxygen only (feed 2, Table 3). A second simulation was performed, whereby the partial pressures of the components in the feed were set equal to the ones in the corresponding case for catalytic partial oxidation with oxygen only (Table 3, Feed 2). This is done by increasing the total pressure to 61.4 bar. The results are shown in Table 7 (Feed B). The above conclusions are confirmed, except that the amount of carbon deposited on the catalyst is lower when air is used instead of oxygen. The maximum temperature can rise to 1200C for feed mixtures without steam and carbon dioxide, which is within the acceptable range for the Ni catalyst.

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 1500C 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
mol-% of component A (%). axial position where the maximum temperature occurs (m). a x max specific heat of fluid ( k J / k g K). Cp particle diameter (mp). dp reactor diameter (m). dr friction factor in Fanning equation. f F , Ft total molar feed rate (kmol/h). FA 0 molar feed rate of reactant A (kmol/h). flow rate of component A (Nm3/h). FA total molar flow rate ( k m o l / m ~ s). Ft adsorption constant of species A. KA reaction rate constant. ki adsorption and equilibrium constants. Ki length of reactor (m). l partial pressure of component A (bar). PA P t ' pO total pressure (bar). reaction rate of total combustion (kmol/kgca t s). rI rate of the steam reforming reaction (kmol/kgca t s). /'2 rate of CO 2 production by steam reforming (kmol/kgca t s). /'3 rate of WGS reaction (kmol/kgca t s). r4 rate of Boudouard reaction ( k m o l / k g ~ t s). r5 rate of methane cracking (kmol/kg~a t s). /'6 rate of carbon gasification by steam (kmol/kgc~ t s). /'7 rate of carbon gasification by oxygen (kmol/kgca t s). /'8 temperature (K). T maximum temperature (K). Tmax outlet temperature (K). Tout superficial velocity ( m 3 / m 2 s). g r Us [A]

264 XCH 4
XCO 2

A.M. De Groote, G.F. Froment / A p p l i e d Catalysis A: General 138 (1996) 245-264

XO 2

yO
YA
Z

conversion of methane (%). conversion of methane to CO 2 (%). conversion of oxygen (%). mol fraction of species A in the feed. mol fraction of species A. axial position (mr).

6.1. Greek symbols


r/1 r/2 7/3 r/4 r/5 r/6 r/7 r/s Pb Pg 0 effectiveness factor for total combustion. effectiveness factor for the steam reforming reaction. effectiveness factor for the CO 2 production by steam reforming. effectiveness factor for the WGS reaction. effectiveness factor for Boudouard reaction. effectiveness factor for methane cracking. effectiveness factor for carbon gasification by steam. effectiveness factor for carbon gasification by oxygen. catalyst bulk density (kg cat/m3r). gas density (kg/m3r). cross section of reactor (m2).

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