Oxidative dimerization of methane: Kinetics, mathematical modeling, and optimization with La/Ce catalysts

Article abstract of DOI:10.1134/S1070363209090333

Kinetic features of oxidative dimerization of methane to ethane and ethylene, catalyzed by a mixture of lanthanum and cerium oxides deposited onto a magnesium oxide support, were examined. A kinetic model was proposed, and the process optimization was performed for a plug-flow reactor in the quasi-homogeneous approximation.

Full text of DOI:10.1134/S1070363209090333

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 9, pp. 2016–2023. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © V.A. Makhlin, M.V. Podlesnaya, A.G. Dedov, A.S. Loktev, N.O. Tel’pukhovskaya, I.I. Moiseev, 2009, published in Rossiiskii
Khimicheskii Zhurnal, 2009, Vol. 52, No. 5, pp. 73–79.
NEW MATERIALS, PROCESSES,
AND TECHNOLOGIES
Oxidative Dimerization of Methane: Kinetics, Mathematical
Modeling, and Optimization with La/Ce Catalysts
V. A. Makhlina, M. V. Podlesnayaa, A. G. Dedovb,
A. S. Loktevb, N. O. Tel’pukhovskayab, and I. I. Moiseevb
a Karpov Scientific and Research Institute of Physical Chemistry,
ul. Vorontsovo Pole 10, Moscow, 105064 Russia
e-mail: podlesnaya@bk.ru
b Gubkin Russian State University of Oil and Gas, Moscow, Russia
Received July 20, 2008
Abstract—Kinetic features of oxidative dimerization of methane to ethane and ethylene, catalyzed by a
mixture of lanthanum and cerium oxides deposited onto a magnesium oxide support, were examined. A kinetic
model was proposed, and the process optimization was performed for a plug-flow reactor in the quasi-
homogeneous approximation.
DOI: 10.1134/S1070363209090333
The world’s oil-depletion problem makes natural
gas the focus of ever growing attention as an
alternative raw material for petrochemical production.
Conventionally, methane is converted to liquid
hydrocarbons via complex multistage processes. They
are run at high pressures and temperatures and entail
large capital investments.
[18], and cerium [19] oxides, were developed by
Atlantic Richfield Co. [13, 14] and Union Carbide
[16].
Oxidative dimerization of methane in the
continuous mode was for the first time carried out with
34% PbO/Al2O3 [20], 3–7% Li2O/MgO [21], and rare-
earth metal oxides [2] as catalysts. A fairly high yield
of C2 hydrocarbons, 19.6% at the selectivity of 50.3%,
was achieved with Li2O/MgO catalyst [21], and the
highest selectivity of 92.8–98.5%, with Sm2O3 at 700°С,
in which case the methane conversion was 1–5 % [22].
In this situation, a good practice will consist in
carrying out one-stage conversion of methane to
ethylene, in particular, oxidative dimerization of
methane at close to atmospheric pressures [1, 2].
The catalysts most active in oxidative dimerization
of methane can be divided into three main groups:
Reaction of Oxidative Dimerization of Methane
Considerable researchers’ interest in oxidative
dimerization of methane is indicated by a huge amount
of relevant publications (see, e.g. [1, 3–10]).
– oxides of d- and some p-element metals in
variable oxidation states, e.g., manganese and lead;
In one of the early studies on this subject, Keller
and Bhasin [11] described preparation of ethane and
ethylene from methane by alternately feeding methane
and air onto 5–10% variable-valence metal oxides
deposited on Al2O3. With MnO/Al2O3 and CdO/Al2O3
catalysts this afforded 10–11% conversion of methane
at 800°С with the selectivity of 40–45%. Similar
processes catalyzed by oxides capable for oxygen
accumulation, e.g., praseodymium [16, 17], terbium
– alkaline and alkali-earth metal oxides;
– rare-earth element oxides.
Also suitable are combinations of these catalysts, in
particular, on supports of different nature. For example,
products of oxidative dimerization of methane were
obtained in 25.8% yield with SrO/La2O3 catalyst at
800–850°С (selectivity 85.6%) [24], and in 19% yield,
with 50% SrF2/Sm2O3 catalyst at 800°С (methane
2016

OXIDATIVE DIMERIZATION OF METHANE
2017
conversion 34%) [25]. In the case of hydroxylapatite
the maximal yield of C2 hydrocarbons (ethylene, ethane)
was 22% at 750°С [24].
radicals quenching. Such design of the reactor allows
minimizing the contribution from gas-phase reactions.
The raw materials for the process were found in flow-
mixed oxygen and methane (99.999 vol % pure) and
methane (99.99 vol % pure, available from Moscow
Gas Processing Plant, Open Joint-Stock Company).
Bajus and Back [26] suggested active catalysts
based on WO3/ZrO2 superacids suitable as supports
onto which Eu or Ce, together with Li2CO3 or,
alternatively, Се or Mn, together with NaCl, were de-
posited by impregnation. The yield of C2 hydrocarbons
with the first type catalysts was 18%, and the catalysts
exhibited stable performance for over 100 h. The
second type catalysts provide a higher yield of
products but are rapidly deactivated.
The process was run under the following condi-
tions: atmospheric pressure; temperature 700–860°С;
methane:oxygen volume ratio 2–7; gas mixture supply
rate 1–15 l h–1. The reaction products were identified
by chromatomass spectrometry (an Automass-150
chromatomass spectrometer available from Delsi-
Nermag, France). Quantitative analysis was carried out
by gas-liquid chromatography. The components were
separated on three columns (2-m-long), packed with
poropack-Q, zeolite NaX, or alumogel modified with
sodium carbonate, respectively. A catharometer served
as detector, and helium, as carrier gas. The results are
summarized in Table 1.
For several years oxidative dimerization of methane
has been the focus of joint studies by Gubkin Russian
State University of Oil and Gas, Karpov Research
Physicochemical Institute, Federal State Unitary
Enterprise (NIFKhI), and Kurnakov Institute of
General and Inorganic Chemistry, Russian Academy
of Sciences. The process was catalyzed by rare-earth
element oxides synthesized, in particular, from
commercial nitrate solutions of rare-earth elements [2,
27–31]. Those studies showed that, by combining
lanthanum oxide with cerium oxide, of which the
former is catalytically more active in methane
dimerization, it is possible to achieve a synergistic
effect with respect to the yield of С2+ products
(ethylene, ethane, propylene, propane). It was also
shown that the catalyst comprised of a mixture of La
and Ce oxides (9:1 molar ratio), deposited onto molten
MgO (periclase), performs efficiently for over 100 h.
Development of the Kinetic Model of the Process
Table 1 suggests that, under the experimental
conditions, the conversion of reactants and selectivity
with respect to С2+ widely vary. Specifically, the
conversion changes from 1 to 35% and from 4 to 98%
for methane and oxygen, respectively, and selectivity,
from 30 to 70%. The data obtained were described by
the following system of stoichiometric equations:
4CH4 + O2 → 2C2H6 + 2H2O,
2C2H6 + O2 → 2C2H4 + 2H2O,
2CH4 + O2 → C2H4 + 2H2O,
C2H4 + 2O2 → 2CO + 2H2O,
C2H4 + 3O2 → 2CO2 + 2H2O,
CH4 + 2O2 → CO2 + 2H2O,
CO2 + H2 →← CO + H2O.
(1)
(2)
(3)
(4)
(5)
(6)
(7)
Today, there is good reason to be optimistic about
the prospects of ethylene preparation by oxidative
dimerization of methane. However, choosing the
optimal mode and implementation of the process
require the knowledge of the kinetic relationships for
this reaction.
According to this scheme, the kinetic model of the
process run in a flow reactor is represented by a system
of differential equations describing the rates of
consumption of reactants and formation of products in
reactions (1)–(7):
Kinetic Model of Oxidative Dimerization
of Methane
Experimental Technique
The kinetic examinations were carried out on a
laboratory setup comprising a flow reactor. The reactor
was designed as a 650×8 mm quartz tube supplied with
a mobile thermocouple for measuring the longitudinal
temperature profile. A La-Ce/MgO catalyst bed (particle
size 0.25–0.50 mm, weighed portion 0.1–0.5 g) was
placed into the temperature plateau zone of the reactor.
A quartz cotton bed at the reactor inlet, as well as
ahead of and after the catalyst bed, served for free
dy
CH4
= –4k1·p·CO – 2 k3·p·CO – k6·p·CO ,
2
2
2
dτ
= –k1·p·CO – k2·p2·CO ·CC2H6 – k3·p·CO
2
dy
O2
2
2
– 2k4·p2·CO ·CC2H4 – 3k5·p2·CO ·CC2H4 – 2k6·p·CO ,
2
2
2
dτ
dy
C2H4
= 2k2·p2·CO ·CC2H6 + k3·p·CO – k4·p2·CO ·CC2H4
2
2
2
dτ
– k5·p2·CO ·CC2H4,
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

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MAKHLIN et al.
Table 1. Results of kinetic examinations of oxidative dimerization of methane
Supplied, ml h–1
Obtained, ml h–1
C3H6 C3H8 CO2 CO
Exp.
no.
CH4/O2 t, °C
CH4
O2
N2
CH4
C2H4
C2H6
N2
O2
Н2
1
3.6
3.6
5.3
3.4
3.4
3.4
2.9
2.9
2.9
3
716
790
790
800
838
855
806
810
818
830
840
844
829
833
837
841
855
849
786
807
824
740
761
794
797
798
845
798
784
820
830
852
735
13577 3771
13427 3730
13244 2499
43
42
46
43
55
50
47
48
50
42
49
49
53
52
52
53
128
118
77
73
168
44
50
75
55
49
48
46
44
47
65
47
48
13352
12716
12689
7562
8673
7700
1992
1990
1947
1868
1822
1830
1987
1968
1958
2010
1343
1400
1519
1561
1521
1163
1172
1002
1030
1824
1699
3632
3673
3592
3590
3674
4373
4
24
19
36
154
181
33
29
43
71
71
81
59
64
66
71
81
86
41
59
61
4
33
148
136
117
227
213
30
28
30
29
28
28
31
31
31
31
39
31
44
51
39
10
11
11
11
23
21
51
27
48
48
56
12
43
42
46
43
55
50
47
48
50
42
49
49
53
52
52
53
128
118
77
73
168
44
50
75
55
49
48
46
44
47
65
47
48
0
0
0
2
8
14
2
2
3
4
4
4
3
3
3
3
5
4
2
3
3
0
0
1
1
2
2
0
0
1
2
3
0
0
4
4
2
10
9
1
1
1
1
1
1
1
1
1
1
1
1
3
2
2
0
0
0
0
1
0
0
0
1
1
1
0
91
237 118 3168 216
158 75 2115 163
60 3641 139
2
3
4
8242
2424
243 119 2095 178
433 185 1845 68
406 190 1535 170
5
10107 2973
6
9153
2325
2299
2328
2335
2310
2349
2379
2377
2367
2440
1951
2008
1995
2091
2029
1238
1256
1109
1162
2009
1957
3821
3776
3817
3828
4010
4436
2692
802
793
803
778
770
783
626
626
623
642
1027
956
688
721
700
344
349
326
342
457
445
554
547
553
555
581
870
7
123
115
135
171
75
71
88
81
423
451
370
269
74
71
75
78
86
90
76
77
77
80
58
58
72
65
59
26
27
27
29
42
49
45
39
49
50
64
15
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
3
165 110 219
171 115 178
3
3.8
3.8
3.8
3.8
1.9
2.1
2.9
2.9
2.9
3.6
3.6
3.4
3.4
4.4
4.4
6.9
6.9
6.9
6.9
6.9
5.1
113
118
113
119
294
312
241
270
253
36
87
89
90
95
56
47
50
25
40
11
14
12
23
23
32
11
8
220
213
203
193
29
29
83
19
39
274
286
259
163
273
144
408
433
338
323
246
784
5
38
12
16
21
46
15
4
46
52
65
86
46
33
25
29
56
2
59
14
15
21
4
60
79
31
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 9 2009

OXIDATIVE DIMERIZATION OF METHANE
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Table 1. (Contd.)
Supplied, ml h–1
CH4 O2 N2
Obtained, ml h–1
C3H6 C3H8 CO2 CO
Exp.
no.
CH4/O2 t, °C
CH4
4220
3640
3179
C2H4
3
C2H6
15
N2
47
46
51
O2
Н2
35
52
76
34
35
36
5.9
5.9
5.9
750
796
860
4297
3827
3597
728
649
610
47
46
51
1
0
5
0
0
1
33
63
5
727
573
306
16
38
16
45
76
49
105
dy
C2H6
= 2k1·p·CO – 2k2·p2·CO ·CC2H6,
This yielded the following data:
2
2
dτ
Аi
Ei/R
dy
k1
k2
k3
k4
k5
k6
k7
17.59
10.06
26.57
14.21
13.87
26.21
13.41
–11890
–9950
CO2
= 2k5·p2·CO ·CC2H4 + k6·p·CO – k7·p2·CO ·CH2
2
2
2
dτ
–20000
–2000
CCO·CH2O
1 –
,
×
K7·CCO2·CH2
–10050
–18870
–2000
dy
CO
= 2k4·p2·CC2H4·CO + 2k7·p2·CCO · CH
2
2
2
dτ
The average relative errors in description of the
output–input flux differences were estimated at 32.3,
24.4, 35.9, 49.5, 34.3, and 48.1 for СН4, О2, С2Н4,
С2Н6, СО2, and СО, respectively.
CCO·CH2O
1 –
,
×
K7·CCO2·CH2
dy
H2
CCO·CH2O
= –k7·p2·CCO2·CH
1 –
,
×
2
Mathematical Modeling and Theoretical
Optomization of the Process
dτ
K7·CCO2·CH2
dy
O2
= 2k1·p·CO + 2k2·p2·CO ·CC2H6 + 2k3·p·CO
2
In terms of the kinetic model developed, mathe-
matical modeling and theoretical optimization in the
quasihomogeneous approximation were carried out for
oxidative dimerization of methane in a plug-flow
reactor. The oxygen conversion and the ethane and
ethylene formation selectivity were examined in
relation to the conditional time of contact, temperature,
pressure, and volume ratio of reactants. The system of
differential equations of the kinetic model was solved
using the DLSODE program. It is conventionally
employed for finding solution to the Cauchy problem in
the case of integration of rigid systems of ordinary
differential equations by Gear’s method [33].
2
2
dτ
+ 2k4·p2·CO ·CC2H4 + 2k5·p2·CO ·CC2H4 + 2k6·p·CO
2
2
2
+ k7·p2·CCO ·CH
2
2
CCO·CH2O
1 –
,
×
K7·CCO2·CH2
where τ is the conditional contact time; yi = Wi/W0,
conditional proportion of ith component in the flux [W0
and Wi are the total flux at the reactor inlet and the flux
of ith component, ml h–1 g–1, respectively; р, total
pressure in the system, atm; Ci = yi/Σyi, mole fraction
of ith component in the system; kj, rate constant of jth
reaction; and K7, equilibrium constant of reversible
reaction (7)].
Oxygen Conversion in Relation to the Contact Time
of Reactants and Temperature
We determined the numerical values of the
Arrhenius parameters to be used for calculating the
reaction rate constants (ln ki = Ai + Ei/RT) in terms of
the kinetic model of the process. This was done by
minimizing the sum of squared deviations of the
experimental and calculated values of the output–input
flux differences in the reactor by the Davidon–
Fletcher–Powel method [32].
In commercial application, there will be the need in
methane recycling in the process. In this connection, it
seemed important to estimate the conditional time of
contact that affords high oxygen conversions. Figure 1
presents the plot of oxygen conversion vs. time of
contact at a constant volume ratio of reactants (3:1),
pressure of 0.1 MPa, and different temperatures. Deep
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MAKHLIN et al.
Contact time, s
Contact time, s
Fig. 3. Oxygen conversion vs. contact time of reactants at
different temperatures; p = 0.1 MPa, CH4:O2 = 6:1.
Fig. 1. Oxygen conversion vs. contact time of reactants at
different temperatures; p = 0.1 MPa, CH4:O2 = 3:1.
oxygen conversions (≥95%) are achieved at 700°С
within 0.9 s, and with temperature increasing to 1000°C
the contact time decreases to 0.009 s.
contact required for achievement of the same oxygen
conversion tends to decrease. For example, at the
pressure of 0.1 MPa and temperature of 700°C
exhaustive oxygen conversion is achieved within 0.9 s,
and at the pressure of 0.17 MPa and the same
temperature the time of contact is 0.5 s.
Oxygen Conversion in Relation to Pressure
Commercial application of the process will require
maintaining certain excessive pressure in the reactor.
Therefore, we examined the main parameters of the
process in relation to this pressure. Figure 2 presents
the plots of oxygen conversion vs. time of contact at
the pressure of 0.17 MPa. Comparison of Figs. 1 and 2
shows that, with increasing pressure, the time of
Oxygen Conversion in Relation to Reactant Ratio
Comparison of the plots of oxygen conversion vs.
time of contact at different temperatures and reactant
ratios of 3:1 (Fig. 1) and 6:1 (Fig. 3) suggests that,
with increasing CH4:O2 ratio, the time required for
exhaustive oxygen conversion tends to decrease. At
800°C and reactant ratio of 3:1 this time was estimated
at 0.25 s, and at the 6:1 ratio, at 0.18 s.
Reaction Selectivity in Relation to Oxygen Conversion
and Temperature
Figure 4а presents the plot of the reaction
selectivity with respect to ethane+ethylene vs. oxygen
conversion at different temperatures. It is seen that,
with increasing oxygen conversion, the selectivity of
the process tends to decrease, but the temperature
dependence exhibits a complex pattern. With increase-
ing temperature to 800°C the selectivity of the process
tends initially to decrease and subsequently, to increase.
To better understand the nature of this dependence, we
presented the modeled data on the selectivity–tem-
perature phase plane at three conversion levels, 20, 55,
and 95% (Fig. 4b). The resulting plots suggest that the
temperature dependence of the selectivity with respect
to ethane–ethylene mixture exhibits a pronounced
Contact time, s
Fig. 2. Oxygen conversion vs. contact time of reactants at
different temperatures; p = 17 MPa, CH4:O2 = 3:1.
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OXIDATIVE DIMERIZATION OF METHANE
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Temperature, °C
Oxygen conversion, %
Fig. 4. Process selectivity with respect to ethane-ethylene mixture vs. (a) oxygen conversion at different temperatures and
(b) temperature at different oxygen conversions; p = 0.1 MPa, CH4:O2 = 3:1.
minimum. For example, at 95% oxygen conversion the
minimal selectivity, 30.4%, is observed at 800°C. With
decreasing oxygen conversion the minimum is
smoothened.
temperature range examined, the selectivities exhibit
opposite trends, which is responsible for a minimum
observed in the plot of the total selectivity.
Reaction Selectivity in Relation to Pressure
and Reactant Ratio
To identify the factors responsible for such unusual
temperature dependence of the С2 product formation
selectivity, we plotted the temperature dependences of
the selectivity for each individual target product,
ethane and ethylene (Fig. 5). It is seen that, over the
Comparison of the temperature dependences of the
process selectivity with respect to ethane-ethylene
mixture (3:1 volume ratio of reactants) at different
pressures (see Figs. 4b and 6) shows that, with
Temperature, °C
Temperature, °C
Fig. 5. Process selectivity with respect to ethane and
ethylene vs. temperature at different oxygen conversions;
p = 0.1 MPa, CH4:O2 = 3:1.
Fig. 6. Temperature dependence of the reaction selectivity
with respect to ethane-ethylene mixture at different oxygen
conversions; p = 0.17 MPa.
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MAKHLIN et al.
Table 2. Results of theoretical optimization of oxidative dimerization of methane
Reaction selectivity, %, with respect to indicated
products
СН4:О2,
p, atm
t, °C
95% O2 conversion time, s
vol %
3:1
at С2Н4 + С2Н6, %
at С2Н4, %
700
800
0.9000
0.2500
0.0090
0.5000
0.0900
0.0035
0.6500
0.1800
0.0100
43.06
30.40
45.60
42.52
28.40
39.00
43.94
35.94
44.48
1.30
8.50
1.0
1000
700
35.26
0.77
1.7
1.0
3:1
6:1
800
5.24
1000
700
31.56
2.20
800
13.02
38.06
1000
increasing pressure, the selectivity of formation of the
ethane-ethylene mixture tends to slightly decrease.
(1) low-temperature area 700–750°C,
(2) high-temperature area 850–950°C.
With increasing volume ratio of reactants the
selectivity of the process tends to slightly increase: At
3:1 ratio the minimal selectivity is 30.4%, and at 6:1
ratio, 36.0 % (cf. Figs. 4b and 7).
The optimal pressure was estimated at 1.0–1.7 ata,
which is close to atmospheric pressure. Increase in
pressure is undesirable because this causes the
selectivity to decrease. The optimal volume ratio of
reactants СН4:О2 is within 3:1–6:1. Increase in the
ratio is beneficial for selectivity but increases the recycle
of methane. At the same time, the time of contact that
affords 95% oxygen conversion is 0.4–0.9 s in the low-
temperature area, and 0.02–0.125 s, in the high-
temperature area. This fact should also be taken into
account when choosing the best conditions, since the
time of contact decides the specific yield of the
catalyst, all other conditions being the same.
Theoretical optimization of oxidative dimerization
of methane (Table 2) revealed the parameter ranges
corresponding to the maximal selectivity of the process
with respect to С2 products:
ACKNOWLEDGMENTS
This study was financially supported by the
Program of Presidium of the Russian Academy of
Sciences no. 7 “Fundamental Problems of Power
Engineering” (Subprogram “Theoretical Principles of
the Technology of Motor Fuels and Basic Oil Products
from Non-Oil Raw Materials”), Russian Foundation
for Basic Research (project nos. 07-03-00533-а and
07-03-12039-ofi), and grant of the President of the
Russian Federation to support leading scientific
schools of the Russian Federation (Academician
I.I. Moiseev’s scientific school).
Temperature, °C
Fig. 7. Temperature dependence of the reaction selectivity
with respect to ethane–ethylene mixture at different oxygen
conversions; CH4:O2 = 6:1.
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OXIDATIVE DIMERIZATION OF METHANE
2023
17. US Patent 4727212.
18. US Patent 4499324.
19. Hinsen, W., Bytin, W., and Baerns, M., Abstracts of
Papers, Proc. VIII Int. Congr. on Catalysis, West Berlin,
1984, Basel: Weinheim, 1984, vol. 3, p. 581.
The authors are grateful to A.G. Zyskin, Cand. Sci.
(Phys.-Math.), for providing consultancy on the
calculations and for discussions on this study.
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