DOI 10.

1007/s11237-016-9459-5
Theoretical and Experimental Chemistry, Vol. 52, No. 2, May, 2016 (Russian Original Vol. 52, No. 2, March-April, 2016)

EFFECT OF Co, Ce, AND La OXIDES AS MODIFYING ADDITIVES ON

THE ACTIVITY OF AN NiO/g-Al2O3 CATALYST IN THE OXIDATION
OF METHANE TO GIVE SYNTHESIS GAS

K. Dossumov,1 G. Ye. Yergazieva,2 L. K. Myltykbaieva,2 and N. A. Asanov2 UDC 542.943;547.211

A study was carried out on the effect of Co, Ce, and La oxides as modifying additives on the activity of an
NiO/g-Al2O3 catalyst in the partial oxidation of methane. The introduction of cerium and lanthanum oxides
enhances the resistance of the catalyst to coking. The increase in the activity of the lanthanum-modified catalyst is
related to a lower temperature required for its reduction and increased dispersion of the metallic nickel particles.

Key words: methane, oxidation, synthesis gas, nickel catalyst, modifying additives, cobalt oxide, cerium oxide,
lanthanum oxide.

The present major area of research on methane transformation concerns oxidation to give synthesis gas. Hydrogen is a
component of synthesis gas and used in a number of large-scale industrial chemical reactions. In addition, hydrogen may be
used in the future as an alternative motor fuel [1-3]. The steam reforming methane conversion is the only industrial
heterogeneous catalytic process for the production of synthesis gas. Disadvantages of this method include large energy
expenditures and the use of expensive catalysts with high nickel content up to 30 mass % [4, 5]. An alternative to this process
might be the partial oxidation of methane in the presence of oxygen. The major reason holding back the practical application of
such a process is the lack of inexpensive, selective, and stable catalysts resistant to coking. Thus, there is now considerable
work on the search for coking-resistant catalysts for the selective oxidation of methane [6-9].
In the present work, we studied the effect of Co, Ce, and La oxides as modifying additives on the activity and selectivity
of an NiO/g-Al2O3 catalyst in the partial oxidation of methane to give synthesis gas.

EXPERIMENTAL

The catalysts were prepared by the combined capillary (incipient wetness) impregnation of the support using solutions
of nickel nitrate salts (Ni(NO3)2·6H2O) and modifying additives (La(NO3)3·6H2O, Ce(NO3)2·6H2O, and Co(NO3)2·6H2O),

________
1
Center of Physical and Chemical Methods of Investigation and Analysis of the al-Farabi Kazakh National University, Tolebi
Street, 96A, Almaty 050012, Republic of Kazakhstan.
2
Institute of Combustion Problems, Bogenbai Batyr Street, 172, Almaty 050012, Republic of Kazakhstan. E-mail:
ergazieva_g@mail.ru.
___________________________________________________________________________________________________
Translated from Teoreticheskaya i Éksperimental’naya Khimiya, Vol. 52, No. 2, pp. 117-120, March-April, 2016.
Original article submitted February 15, 2016.

0040-5760/16/5202-0119 ©2016 Springer Science+Business Media New York 119

 TABLE 1. Effect of Modifying Additives on the Activity of an NiO/g-Al2O3 Catalyst in the Partial
Oxidation of Methane at 750 °C (CH4 : O2 = 2 : 1, W = 1000 h–1)

Catalyst content, mass % Methane conversion, % Selectivity rel. to H2, % Selectivity rel. to CO2, %

3% NiÎ/g-Al2O3 94 47 40
3% NiÎ + 2% ÑîÎ/g-Al2O3 90 49 42
3% NiÎ + 2% ÑåÎ2/g-Al2O3 90 51 41
3% NiÎ + 2% La2Î3/g-Al2O3 95 52 44

subsequent drying at 300 °C for 2 h and roasting at 500 °C for 3 h. The catalysts were subjected to prior reduction in a hydrogen
stream at 400 °C for 1 h.
The testing of the catalytic activity characterized by methane conversion, was carried out in a PKU-1 automatic flow
system containing a block for preparation of the initial gas mixture, a quartz catalytic reactor, and a gas chromatograph. The
samples were tested in the range 600-850 °C with methane volumetric flow rate 500-4500 h–1 at atmospheric pressure. The
catalyst sample was placed in a 25-cm-long quartz tube reactor with 9 mm internal diameter. The initial reagents (methane and
O2) and reaction products (CO, H2, and CO2) were analyzed on a Khromos-1000 chromatograph equipped with a thermal
conduction detector. The argon gas carrier flow rate was 20 mL/min. H2, N2, and O2 were determined by using a 2-m column
packed with CaA phase (d = 3 mm, T = 350 °C), while CO, CO2, and methane were determined on an activated carbon column
at T = 250 °C with H2 as the gas carrier (flow rate 20 mL/min).
The prepared catalysts were characterized by scanning electron microscopy (SEM) on a Quanta 200 3D instrument,
X-ray diffraction (XRD) on a Bruker AXS instrument, and temperature-programmed hydrogen reduction (TPHR) using a
USGA-101 universal adsorption gas analyzer.

RESULTS AND DISCUSSION

Table 1 shows the effect of Co, Ce, and La oxides as modifying additives on the activity of an NiO/g-Al2O3 catalyst in
the partial oxidation of methane with optimal catalyst compositions, CH4 : O2 = 2 : 1, T = 750 °C, and W = 1000 h–1.
The introduction of cobalt oxide and cerium oxide into the NiO/g-Al2O3 catalyst leads to a slight drop in methane
conversion along with an increase in the selectivity for formation of the desired products: hydrogen from 47% to 51% and
carbon monoxide from 40% to 42%. The introduction of lanthanum oxide into the nickel catalyst gives 95% methane
conversion, 52% selectivity relative to hydrogen and 44% relative to carbon monoxide. Carbon dioxide and water are formed in
addition to CO and H2 on all the catalysts.
After testing in the partial oxidation of methane for 30 h, the catalysts were studied by scanning electron microscopy.
Figure 1 shows that catalysis of the oxidation of methane on the NiO/g-Al2O3 surface proceeds with the formation of carbon
fibers. The SEM data showed that the cobalt oxide-modified sample also undergoes coking. Modification of NiO/g-Al2O3 with
cerium oxide or lanthanum oxide leads to enhanced dispersion of the catalyst. No coke formation was observed on the surface
of the nickel-lanthanum and nickel-cerium catalysts (Fig. 1a). The intensity of the metallic nickel reflection is enhanced by
introduction of the modifying additives (Fig. 1b). The greatest Ni0 reflection is observed for the sample modified with
lanthanum oxide.
The prepared samples were studied by TPHR since catalyst activation requires reduction with the formation of metallic
Ni0 particles which are active in the oxidation reaction.

120
 a

Fig. 1. SEM photographs (a) and X-ray diffraction patterns (b) of

catalysts: 1) 3% NiO/g-Al2O3, 2) 3% NiO + 2% CoO/g-Al2O3,
3) 3% NiO + 2% CeO2/g-Al2O3, 4) 3% NiO + 2% La2O3/g-Al2O3.

The TPHR spectrum of the NiO/g-Al2O3 catalyst (Fig. 2) shows a peak with maximum at 814 °C with a shoulder at
625 °C. This shoulder may be assigned to highly-dispersed amorphous NiO [10]. The peak at 814 °C is assigned to nickel
aluminate and the amount of adsorbed hydrogen A = 159 mmol/g. The shape of the TPHR spectrum is altered upon the
introduction of lanthanum oxide. Peaks arise at 251, 357, 446, and 750 °C and the amount of adsorbed hydrogen is diminished
(A = 82 mmol/g). The low-temperature peak at 251 °C may correspond to reduction of the Ni2+ ion to Ni0. Thus,
Garrido Pedrosa et al. [11] observed peaks at 238 and 507 °C and attributed these two peaks to the reduction of Ni2+ cations to
Ni0 stabilized on different support particles (HY). The peak at 357 °C may be caused by reduction of the nickel ion to
lanthanum nickelate. According to de Lima et al. [12], the NiO/MgO-La2O3 catalyst shows a peak at 350 °C, which they
attributed to the reduction of Ni3+ ions to Ni2+ ions in La2Ni2O5. According to Pengpanich et al. [13], the hydrogen adsorption
range at 400-750 °C with maxima at 446 and 750 °C corresponds to the reduction of Ni2+ ions (in dispersed nickel oxide)
characterized, respectively by weak and strong metal-support interactions.
Analysis of the results of our study of these catalysts by XRD, TPHR, and SEM showed that the introduction of La2O3
into the NiO/g-Al2O3 catalyst leads to the formation of La-Ni compounds, enhanced particle dispersion, and a greater fraction
of Ni2+ ions reduced in the low-temperature region. Modification of the nickel catalyst by lanthanum oxide prevents surface
coking and enhances the selectivity for formation of the desired products (CO and H2). Under the experimental conditions with
CH4 : O2 = 2 : 1, T = 750 °C, and W = 1000 h–1, methane conversion on the catalyst with 3% NiO and 2% La2O3/g-Al2O3 is 95%
and the selectivity relative to carbon monoxide and hydrogen is 44 and 52%, respectively.
Thus, we propose an efficient catalyst with 3% NiO + 2% La2O3/g-Al2O3 for the partial oxidation of methane to give
synthesis gas. A complex investigation using XRD, SEM, and TPHR showed that modification of NiO/g-Al2O3 by lanthanum

121
 Fig. 2. TPHR curves for catalysts 3% NiO/g-Al2O3, A = 159 mmol/g (a)
and 3% NiO + 2% La2O3/g-Al2O3, A = 82 mmol/g (b).

oxide yields a catalyst resistant to coking. Modification with La2O3 gives new phases, enhanced dispersion of the catalyst, and a
lower temperature for the reduction of nickel oxide. This catalyst does not lose its activity after use over 250 h under the
laboratory conditions (CH4 : O2 = 2 : 1, T = 750 °C, and W = 1000 h–1).
This catalyst will be tested in a pilot plant under real conditions for the production of synthesis gas from methane.

This work was carried out with a grant from the Ministry of Education and Science of the Republic of Kazakhstan. The
authors express their gratitude to Professor H. Kurokawa and E.Tulebayev for assistance in the physicochemical investigation
of these samples.

REFERENCES

1. M. Dixit, A. Menon, R. Baruah, et al., React. Kinet. Mech. Cat., 115, 611-624 (2015).
2. B. Valle, B. Aramburu, A. Remiro, et al., Appl. Catal. B, 147, 402-410 (2014).
3. Y. Benguerba, L. Dehimi, M. Virginie, et al., React. Kinet. Mech. Cat., 114, 109-119 (2015).
4. Y. Zeng, H. Ma, H. Zhang, and W. Ying, Int. J. Chem., Nucl., Mater., Metallurg. Eng., 8, 624-628 (2014).
5. Y. Wang, J. Peng, Ch. Zhou, et al., Int. J. Hydrogen Energy, 39, 778-787 (2014).
6. K. Dossumov, G. E. Yergazyieva, L. K. Myltykbayeva, et al., Coke Chemistry, 58, No. 5, 178-183 (2015).
7. T. P. Maniecki, K. Bawolak, P. Mierczyski, et al., Kinet. Catal., 52, 711-715 (2011).
8. H.-T.Wang, Z.-H. Li, and S.-X. Tian, React. Kinet. Catal. Lett., 83, 245-252 (2004).
9. T. N. Gartman, F. S. Sovetin, E. A. Borovkova, et al., Petrol. Chem., 55, 455-461 (2015).
10. C. Campos, P. Osorio-Vargas, N. Flores-Gonzales, et al., Catal. Lett., 146, 433-441 (2016).
11. A. M. Garrido Pedrosa, M. J. B. Souza, D. M. A. Melo, et al., J. Thermal Anal. Calorim., 79, 439-443 (2005).
12. S. M. de Lima, M. A. Pena, L. G. Fierro, et al., Catal. Lett., 124, 195-203 (2008).
13. S. Pengpanich, V. Meeyoo, and T. Rirksomboon, Catal. Today, 93-95, 95-105 (2004).

122