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Applied Catalysis A: General 162 (1997) 235-238

Beneficial effects of cobalt addition to Ni-catalysts for

oxidative conversion of methane to syngas
V.R. C h o u d h a r y * , V.H. R a n e , A . M . R a j p u t
Chemical Engineering Division, National Chemical Laboratory, Pune-411 008, India

Received 9 July 1996; received in revised form 25 February 1997; accepted 26 February 1997

Abstract
Addition of cobalt to NiO/Yb203, NiO/ZrO2 and NiO/ThO2 catalysts causes a drastic reduction in the rate of carbon
formation and also results in a large decrease in the reaction start (or the catalyst activation) temperature in the oxidative
conversion of methane to syngas. ,~f: 1997 Elsevier Science B.V.

Keywords: Methane-to-syngas conversion; CoO-NiO-Yb203; CoO-NiO-ZrO2; CoO-NiO-ThO2; Oxidative conversion of

methane

1. Introduction
Nickel catalysts have high activity and selectivity in
the reforming of hydrocarbons to syngas (i.e. CO and
H2) and also have low cost [1-3]. Hence, these catalysts are commonly used in the syngas production
processes. These catalysts are, however, also known
for whiskar type carbon deposition on them in the
hydrocarbon reforming processes, creating technical
problems [ 1,2]. The coke deposition on nickel is much
faster than that on noble metals [4]. In our earlier
studies [5,6], NiO/Yb203 catalyst showed high
activity and selectivity but showed fast carbon
formation in the oxidative conversion of methane
to syngas at extremely low contact time. Our
preliminary studies on this reaction over NiO/ZrO2
and NiO/ThO2 catalysts also indicated that these two

*Corresponding author.
0926-860X/97/$17.00 ,~ 1997 Elsevier Science B.V. All rights reserved.
P I I S 0 9 2 6 - 8 6 0 X ( 9 7 ) 0 0 1 0 1-4

catalysts are highly active and selective but carbon

deposition on them is very fast. In this communication, we show that, because of the addition of cobalt to
NiO/Yb203, NiO/ZrO2 and NiO/ThO2 catalysts, the
rate of carbon deposition on these catalysts in the
oxidative conversion of methane to syngas is drastically reduced and also the reaction over these catalysts
starts (i.e. the catalyst is activated) at lower temperature.

2. Experimental
The NiO/Yb203, NiO/CoO/Yb203, NiO/ZrO2,
NiO/CoO/ZrO2, NiO/ThO2 and NiO/CoO/ThO2 catalysts (Table 1) were prepared by thoroughly mixing
finely ground nickel nitrate with or without cobalt
nitrate and Yb203 (Aldrich), zirconyl nitrate or thorium nitrate in required proportions with deionized
water to form a thick paste, drying and decomposing

236

V.R. Choudhary et al./Applied Catalysis A: General 162 (1997) 235-238

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V.R. Choudhary et al./Applied Catalysis A: General 162 (1997) 235-238

in air at 600C for 4 h and powdering, pressing

binder-free, crushing to 22-30 mesh size particles
and calcining at 900C for 6 h in static air. The
catalytic reaction was carried out at atmospheric
pressure in a continuous microreactor (i.d. 4 mm)
made up of quartz placed with 20 mg catalyst, using
a mixture of pure methane and oxygen as a feed with a
CH4/O2 mole ratio of 2.0 at a total space velocity
(measured at STP) of 5.2x 105 cm3/g per hour, as a
function of time-on-stream. The reaction temperature
was measured by a Chromel-Alumel thermocouple
located in the catalyst bed. The water from the reaction
products was separated by condensing at 0C. The
feed and products were analyzed by an on-line
GC using Spherocarb column. The reaction start
temperature, T~ (i.e. the temperature at which the
catalyst is activated by its reduction), was determined
by noting the temperature at which the reaction
was initiated, indicated by a sudden increase in the
catalyst temperature by a few degrees and also an
increase in the reactor outlet gas flow rate, forming
reaction products (confirmed by analysis), when the
catalyst temperature was increased slowly (5C/min).
After measuring T~, the time-on-stream activity
experiments on the catalyst were carried out under
steady-state conditions. The carbon deposited on
the catalysts was determined by its complete and
instantaneous oxidation by flash combustion using
Carlo Erba Analyzer Model EA 1108. The resulting
combustion gases were passed through a reduction
furnace and detected by gas chromatograph with
thermal conductivity detector (TCD) using PoropakQ column.

237

the Ni-catalysts was increased continuously with the

time-on-stream but the activity and selectivity of all
the catalysts were not affected at all due to the carbon
deposition. This is consistent with our earlier observations [5,6] and also with the formation of whiskar
carbon [1,2].
The higher pressure drop across the reactor for the
catalysts containing nickel alone (i.e. without cobalt)
is resulted from the formation of filamental (whiskar)
carbon on the catalysts, leading to the plugging of the
catalyst bed. The carbon formation can be due to the
Boudouard reaction (2CO---C+CO2), methane
decomposition (CH4-C+2H2) and the heterogeneous
water gas reaction ( C O + H 2 - C + H 2 0 ) , occurring
simultaneously. The observed drastic reduction in
the rate of carbon formation due to the addition of
cobalt to the Ni-catalysts may be attributed to their
reduced catalytic activity for the carbon forming
reactions and/or to their increased activity for oxidation of the carbon formed. Further study is necessary
to know the real cause.
The Ni and Co oxides in the catalysts are first
reduced to metallic form in the initial reaction and
then act as catalyst in the oxidative conversion of
methane to syngas [5,6]. The observed decrease in the
reaction start temperature is mostly because of reduction of the catalysts at lower temperatures due to the
addition of cobalt to them. It may be noted that the
reaction start temperature for CoO/Yb203 (T,:420C)
and CoO/ThO2 (Ts=410C) catalysts is much lower
than that for the NiO/Yb203 (~=545C) and NiO/
ThO2 (Ts=475C) catalysts, respectively.

4. Conclusions
3. Results and discussion
A comparison of the results (Table 1) on the Nicatalysts with and without cobalt for the oxidative
conversion of methane to syngas shows the following
two important beneficial effects of cobalt addition to
the Ni-catalysts on their performance. First, the carbon
deposition on all the three Ni-catalysts is reduced
drastically and second, the reaction start (or the activation) temperature for the catalyst is decreased
appreciably. The activity and selectivity of the Nicatalysts is, however, decreased to a small extent due
to the addition of cobalt to them. The pressure drop for

The results lead to the following important conclusions of practical importance. The carbon formation
on the Ni-catalysts which show high activity and
selectivity in the oxidative conversion of methane to
syngas is fast; its order for the catalysts is NiO/
ThO2>>NiO/ZrO2>NiO/Yb203. However, the addition of cobalt to these catalysts results in a drastic
reduction in the carbon formation, thus increasing
their stability and also causes a large decrease in their
reaction start temperature, making the catalyst activation easier (i.e. at lower temperature) in the catalytic
process.

238

V.R. Choudha~ et al./Applied Catalysis A: General 162 (1997) 235-238

Acknowledgements
V.H. R a n e is g r a t e f u l to the C o u n c i l o f Scientific
a n d I n d u s t r i a l R e s e a r c h , N e w Delhi, for the a w a r d o f a
P o o l Officership.

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