Fuel 82 (2003) 581–586

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Support effect of Co/Al2O3 catalysts for Fischer –Tropsch synthesisq

Junling Zhang, Jiangang Chen, Jie Ren, Yongwang Li, Yuhan Sun*
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, P.O. Box 165, Taiyuan 030001,
People’s Republic of China
Received 6 August 2001; accepted 4 October 2002; available online 28 October 2002

Abstract
Cobalt supported on different g-alumina carries prepared by incipient wetness impregnation are used to investigate the effect of support on
the performance of cobalt catalysts for Fischer – Tropsch synthesis (FTS). It is found that the acidity of support has a great influence on the
interaction between metallic cobalt and support and then the reducibility of cobalt. The support with low acidity leads to the higher active
FTS catalysts. Furthermore, the high reducibility and more bridged type CO which is favored by g-alumina with low acidity appears to be
responsible for high Cþ
5 hydrocarbon selectivity and low methane selectivity.
q 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Fischer–Tropsch synthesis; Support; Cobalt/alumina; Characterization; Syngas

1. Introduction It is well known that metal oxides – metal oxides and

metal – metal oxides interactions play an important role in
The Fischer – Tropsch synthesis (FTS) is one of major the chemistry of alumina-supported cobalt catalysts, and the
routes for converting coal-based and/or natural gas-derived extent of such interaction is affected by metal loading,
syngas into environmentally sound production of chemicals preparation, pretreatment, and support properties. A specific
and fuels [1]. Cobalt has been one of the most commonly feature of alumina-supported cobalt catalysts is their
used metals for Fischer –Tropsch catalysts since the 1930s incomplete reduction and the possibility of cobalt ion
due to its high activity. It has recently stimulated renewed insertion in the aluminum oxides lattice to form spinel
interest in the development of cobalt FTS catalysts when the structures [8 –11], resulting in their low reducibility and
plant was built in Malaysia making use of shell’s SMDS catalytic activity. In other words, the catalytic performance
process, a novel technique of gas utilization. of alumina-supported cobalt depends upon the support
For supported cobalt catalysts, both texture and surface properties and the nature of the surface species formed after
properties of support have a great influence on the the catalyst preparation [12 – 17].
dispersion and reducibility of cobalt [2 – 4]. Lapszewicz Hercules and Chin [12] reported that the percentage of
[4] observed that the pore size of silica determined the cobalt ions inserting into the support lattice increased as the
dispersion of cobalt and product selectivity but did not metal loading decreased or the calcination temperature
modify site-time yield (TOF). Different from silica, metal increased. Dimitrova and Mehandjiev [2] found that there
oxides such as ZrO2 and TiO2 tend to have a strong was an impregnation solution concentration at which a
interaction with the cobalt metal. Electrons can transfer specific surface area maximum of active oxide was formed.
from the partially reduced TiOx or ZrOx to the metallic Bechara et al. [13] pointed out that the cobalt loading and
surface and the migration and covering of partially reduced the porosity of supports modified the reducibility and the
titania and zirconia species onto the surface of metal catalytic properties. In addition, Fan et al. [18] reported that
particles can suppress the activity during the course of high the metal dispersion increased as the support pore size
temperature reduction and reaction [5 –7]. increased for Rh/Al2O3 catalysts. However, a few literatures
reported the influence of support features (such as the
* Corresponding author. Tel.: þ86-351-4130-327; fax: þ 86-351-4041-
153.
texture and surface acidity of the same kind of support) on
E-mail address: [email protected] (Y. Sun). the dispersion and reducibility of cobalt and the catalytic
q
Published first on the web via Fuelfirst.com_http://www.fuelfirst.com performance. In the present work, the properties of alumina
0016-2361/03/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 6 - 2 3 6 1 ( 0 2 ) 0 0 3 3 1 - 9
582 J. Zhang et al. / Fuel 82 (2003) 581–586

support and cobalt catalysts were characterized to highlight 723 K for 1 h to remove H2, and then maintained at 298 K
the relationships between the support properties and the for O2 adsorption.
catalytic performance. The total uptakes of H2 were determined by Micro-
meritics Autochem 2950 with TCD. The samples (0.2 g)
were reduced under H2 at 673 K for 6 h and then purged
2. Experimentals with Ar at 673 K for 2 h. H2 was pulsed to the reduced
catalyst at 373 K to determine the uptakes of adsorbed H2.
The dispersion of catalyst was calculated based on the total
2.1. Catalyst preparation
uptakes and reducibility from oxygen titration.
DRIFTS spectra were recorded with the Nicolet Magna
In order to investigate the support effect, three commer-
550 spectrometer using a resolution of 8 cm21. The
cial g-Al2O3 (denoted as A-F, A-R, and A-L) were used as
catalysts were pretreated in hydrogen for 6 h at 673 K
the support for FTS catalysts. All of them were pretreated at
before in situ FTIR. Then the temperature of the sample fell
773 K in air for 2 h. In addition, sample A-W was prepared
to 298 K and gas CO was adsorbed. After saturation, the
by hydrothermally treating A-R in the presence of distilled
sample was purged with Ar until there was no carbon
water at 773 K for 2 h for the comparison. Co/Al2O3
monoxide gas.
catalysts with 12 wt% metallic cobalt were prepared by
incipient wetness impregnation method using cobalt nitrate
2.3. Catalyst testing
as the precursor and calcined at 673 K for 6 h, thereafter
named as CA-F, CA-R, CA-L and CA-W.
Catalysts were evaluated at 2 MPa, 493 K, and 500 h21
with the H2/CO ratio of 2 in a fixed-bed reactor of i.d.
2.2. Catalyst characterization 10 mm. The catalysts (5 ml) were reduced in a flowing H2 at
673 K for 6 h prior to reaction. The catalyst was cooled to
The textural properties of support was measured with lower than 350 K before switching to syngas. Steady state
Micromeritics ASAP-2000. NH3-TPD were carried out in a was reached after 12 h in all cases. Then liquid products
flow apparatus. The sample (0.1 g) was treated at 873 K in were collected in a cold trap and wax was collected in a heat
Ar for 30 min. After cooling to 373 K, the sample was trap. The gas effluents were analyzed by use of Carbosieve-
saturated with ammonia. After this purging treatment, the packed column with TCD. The gas hydrocarbons were
sample was heated to 903 K at a rate of 10 K/min in a argon analyzed through Porapack-Q column with FID. Oil and
flow of 50 ml/min. The effluent gas was monitored by TCD wax were analyzed OV-101 columns with FID.
and adsorbed into 0.01 mol/l HCl solution. The total amount
of acidity was calculated by re-titration of 0.01 mol/l NaOH
solution to excessive HCl solution. 3. Results
Pyridine FTIR spectra were recorded in Shimadzu FT25
spectrometer. The samples were pressed into self-support- 3.1. Characteristics of support
ing discs, placed in an IR cell, and treated under vacuum at
673 K for 2 h. After cooling down to 298 K, the samples The data in Table 1 and Fig. 1 indicate the difference in
were exposed to pyridine for 0.5 min. Then, IR spectra were textural characteristics of the supports. The sample A-F has
recorded after evacuation for 1 h at different temperatures.
XRD was recorded in Rigaku D/max-gA using Cu target
Table 1
with Ni filtration. The patterns were obtained with the X- The physico-chemical properties of g-Al2O3 supports
ray gun operated at 50 kV and 30 mA, using a scan rate
0.28/min (2u ). Support Source Surface Average Average pore Total
area pore size volume aciditya
XPS was obtained in PHI5300 electron spectrometer 2 3
(m /g) (nm) (cm /g) (mmol/g)
fitted with an Al Ka source. The binding energies of O1s,
Al2p and Co2p were referenced to the C1s band at A-F Fushun Third 256 9.6 0.4 0.25
284.6 eV. Petroleum Firm
TPR were carried out in a U-tube quartz reactor with 5% A-L Lanzhou 235 8.5 0.5 0.45
H2/Ar as the reductive gas. The samples (0.1 g) were Petroleum
Factory
initially flushed with Ar at 393 K to remove water and then A-R Institute of 167 19.0 0.8 0.41
reduced in the 5% H2/Ar mixture of 40 ml/min ramping at Commodity
10 K/min. The effluent gas was monitored by a TCD. Chemistry
The reducibility of catalyst was calculated based on the A-W A-R hydrother- 153 18.7 0.7 0.31
weight gain after re-oxidation of reduced sample at 673 K mally treated
at 773 K
for 6 h on a Cahn TG-151 analyzer. The catalyst (0.2 g) was
a
firstly reduced at 673 K, further purged with a flow of Ar at Measured by acid– base titration.
 J. Zhang et al. / Fuel 82 (2003) 581–586 583

Fig. 1. The pore size distributions of supports.

Fig. 3. Pyridine infrared spectrascopy of alumina supports.

the similar textural structure to A-L, but it shows a lower to weak acid-sites are predominant on the surface of
acidity than A-L. Furthermore, the sample A-F shows the alumina. The total amounts of acid decrease in the order: A-
bimodal pore distributions which appears the pore volume L . A-R . A-W . A-F.
maxima at 3 and 8.5 nm, and the sample A-L are typical of
monomodal material with the pore volume maximum at 3.2. State of oxidic cobalt phases
8 nm. However, the samples A-R and A-W exhibit almost
the same surface area and the pore size distributions. The The characteristic peaks of the Co3O4 spinel phase are
pores with the size of 11 nm make up most of the pore illustrated by XRD. The data in Table 2 indicates that the
volume of A-R and A-W. catalysts except for the catalyst CA-F with higher dispersion
Pyridine-FTIR indicates that the adsorption peaks at ca. give the similar particle size of cobalt oxides.
1620, 1613, 1593, 1577, 1490, and 1450 cm21 are observed For cobalt in an oxidic state, XPS indicates that Co2p3/2
on alumina after evacuation at 298 and 473 K, respectively in Co3O4 has lower binding energy than that in CoAl2O4,
(Fig. 2). Except for the peak at 1593 cm21, which is assigned and the Co2p3/2 binding energies of the catalysts reflect the
to pyridine bonded to the OH groups on the alumina surface total values for that of both Co3O4 and of surface phase [7].
and weakens with increasing the evacuation temperature to In the present case, the binding energies of Co2p3/2 for CA-
473 K, others are attributed to pyridine adsorbed on the R and CA-L match neither with that of Co3O4, nor of CoO,
Lewis acid sites. The band intensities of supports A-L and A- while the binding energy of Co2p3/2 for CA-F and CA-W is
R are stronger than those of A-F and A-W. the same as that of bulk Co3O4 (Table 3). Thus, it is possible
NH3-TPD of Al2O3 support shows two desorbed peaks in that the cobalt in CA-R and CA-L has a stronger interaction
Fig. 3. Obviously, the low temperature peaks corresponding with alumina than that in CA-F and CA-W. In addition, the
bulk Co/Al atom ratio is greatly higher than surface atom
ratio for all the catalysts. This implies the low dispersion or
the aggregation state of cobalt on the surface of these
catalysts. The surface Co/Al ratio decreases as the sequence:
CA-F . CA-W . CA-R . CA-L, which well agrees with
that of XRD.

3.3. Characteristics of reduced catalysts

The Co/Al2O3 catalysts were investigated using tem-

perature-programmed reduction. It was found that the
shoulder peak appears at ca. 540 K for these catalysts,
which is assigned to the reduction of residued cobalt nitrate,
as proposed in literature [8]. Another two reduction peaks
are also observed for all catalysts. According to the
literature [3,8,12], the low temperature peak at ca. 633 K
is assigned to the reduction of bulk Co3O4 and the high
Fig. 2. NH3-TPD profiles of different supports. temperature peak above 700 K may be caused by the surface
584 J. Zhang et al. / Fuel 82 (2003) 581–586

Table 2
The properties of Co/g-Al2O3 catalysts

Catalyst Average Co3O4 particle Reduction degree by Reduction degree by Total H2 uptake Dispersion
size by XRD (nm) TPR 373 –1000 K (%) O2 titration (%) (mmol g21) (%)

CA-F 10 49 46 74 16
CA-L 15 28 21 33 12
CA-R 14 39 33 42 13
CA-W 16 44 40 52 13

irreducible species. A quantitative analysis of these peaks activity increases as follows: CA-L , CA-R , CA-
shows that the reduction degree of CA-F is the largest W , CA-F. Methane selectivity decreases and Cþ 5 selectiv-
among these catalysts (Table 2). ity increases for cobalt supported upon A-F compared to
Furthermore, the reduction degree of CA-F, CA-R, CA- that supported on A-W, A-L and A-R. It seems that CA-F
L, and CA-W in Table 2 are 49, 33, 21, and 40% from and CA-W produce more diesel and wax fractions. CO2
oxygen titration, respectively. The amount of hydrogen selectivity keeps rather a low level for all cases. Further-
from H2 chemisorption decreases as follows: CA-F . CA- more, CO2 selectivity seems to be linked with the unreduced
W . CA-R . CA-L. But it is not observed that there is a surface compounds (CoAl2O4-like phase which are inactive
distinct difference in the dispersion of these catalysts except for FTS but active for the water –gas shift reaction [21]).
for the reduced CA-F catalyst. This suggests that the The turnover frequency (TOF) remained constant and does
increment of active-site numbers of H atoms is not from the not depend on the dispersion and the supports (Table 4).
dispersions but from their different reducibilities. This implies that the overall rate is only determined by the
In situ DRIFTS were used to investigate support effect on number of reduced cobalt atoms and that reaction is a
the adsorption properties of the reduced catalysts using CO structure insensitive reaction. This observation is in good
as a probe molecular (Fig. 4). Carbon monoxide adsorbed on agreement with what reported by Iglesia et al. [24].
the reduced catalysts at 298 K led to an IR spectrum with the
feature bands at 2060, 2044, 2032, 1990, 1937, 1897, 1867,
1816, 1648, 1524, 1436, 1395, and 1376 cm21. Generally, 4. Discussion
the bands above 2000 cm21 are assigned to the linear-type
CO adsorbed onto metallic cobalt [19,20]. The lower bands The important features of support for FTS reaction
at 1990, 1937, 1897, 1867 and 1816 cm21 are attributed to include the texture and surface properties. Data in Table 1
the bridged-mode CO. The vibrational bands corresponding clearly indicate that supports A-F and A-L have the similar
to bicarbonate and carbonate species are also observed at textural features but exhibit the different acidity. The
1648, 1524, 1436, 1395 and 1376 cm21, but the intensities hydrothermal treatment of support A-R at 773 K hardly
of these species adsorbed on different catalysts vary. The change its texture but decreases the acidity.
intensities of bridged-type CO are weaker for CA-L and All other catalysts show the similar dispersion except for
CA-R than those of CA-F and CA-W, but CA-R shows the CA-F (Table 2). It seems that the high Co dispersion CA-F
strongest intensity of linear-type CO among these catalysts. results from the higher surface area of support. But the large
surface area of support does not always lead to the high
3.4. Catalytic activity and selectivity

The Fischer –Tropsch activity and selectivity of alumina-

supported cobalt catalysts are listed in Table 4. Catalytic

Table 3
Co2p3/2 electronic binding energy and surface and bulk Co/Al ratios

Catalyst Binding energy Surface atom ratio Bulk atom ratio

Co2p (eV) Co2p/Al2p3/2 Co2p/Al2p3/2

CA-F 780.1 0.029 0.118

CA-L 780.4 0.016 0.118
CA-R 780.7 0.019 0.118
CA-W 780.1 0.021 0.118
CoO 781.1
Co3O4 780.1
Fig. 4. IR spectra of CO adsorbed onto different Co/Al2O3 catalysts.
 J. Zhang et al. / Fuel 82 (2003) 581–586 585

Table 4
The catalytic performance of Co/g-Al2O3 catalysts in the FTS

Catalyst CO conversion (%) Reaction rate (mmol g21 s21) CO2 selectivity (%) Hydrocarbon distribution (%) a TOF ( £ 100 s21)

C1 C2 –C4 C5 –C11 C12 –C18 Cþ

18

CA-F 61.1 19.2 0.6 14.7 7.1 33.1 21.8 23.3 0.85 13.0
CA-L 33.1 6.2 3.2 32.0 16.2 31.3 11.8 8.7 0.77 9.4
CA-R 55.5 11.2 1.5 30.3 15.1 33.8 12.9 7.9 0.79 13.3
CA-W 57.3 14.6 1.8 23.1 19.9 24.7 20.9 11.4 0.81 14.0

Reaction conditions: 493 K, 2 MPa, GHSV ¼ 500 h21, CO=H2 ¼ 1=2:

dispersion of metal, such as cobalt supported on A-L with monoxide, but cobalt catalysts supported on high acidity
the high surface area which does not lead to the high alumina suppress the reduction of catalysts and led to the
dispersion. van Steen et al. [23] found that the silanol groups linear-type CO. It seems that the dispersion of catalyst has
could form these bands with the water ligands of the cobalt hardly any influence on the adsorption of CO. The bridged-
complex and then led to an enhanced possibility for the type bands of CA-L and CA-R are much weaker than those
formation of the precursor of surface cobalt silicate. of CA-W. Simultaneously, the above facts also suggests that
The interaction between cobalt and hydroxide groups on the uptakes of CO are not suitable to calculate the dispersion
the alumina support should be similar to that during the of metal cobalt due to the uncertainty of the CO/Cos
preparing process of Co/SiO2 catalyst. Hence, it is deduced stoichiometry for Co/Al2O3 catalyst.
out that the surface acidity of support plays an important Data in Tables 2 and 4 clarified the relationship between
role in the cobalt dispersion, and probably the low acidity of the reducibility, dispersion and the overall rate of catalyst.
support A-F is the main cause for the high Co dispersion on The high dispersion and reducibility of CA-F can lead to the
the CA-F catalyst. Furthermore, when such alumina with high overall activity. But the lower activity of CA-L seems
stronger acidity is used as support, the formation of surface not to result from its dispersion but lower reducibility.
cobalt aluminate is enhanced, possibly resulting from more Furthermore, the overall rate of catalyst seems to be
separated hydroxides of alumina. As a result, the reduction associated with the change in the adsorption mode of CO.
process of Co/Al2O3 is suppressed and the extent of Generally, it has been pointed out that the bridged-type CO
reduction decreases. This is supported by the results is more active than the linear-type CO [22], due to CO in
of TPR and O2 titration, indicating that the reduction degree bridged-mode which is easily cleaved to surface carbon and
of CA-F is the highest and that of CA-L is the lowest. oxygen. However, the TOF keeps constant for these
The BE value for Co2p3/2 in Co3O4 is lower than that in catalysts. This implies that the reaction here is a structure
CoAl2O4. Ishihara et al. [25] reported that the support insensitive reaction and the apparent rate is determined by
acidity determined the extent of electron withdrawal or the number of active sites and CO adsorption mode.
donation from the support used, which brought about a Support effects on the product selectivity are more
change in the electron density of active metal. The Co2p3/2 complicated than on the activity. Iglesia et al. reported [21]
BE values for CA-L and CA-R are an intermediate between that the Cþ
5 hydrocarbons selectivity depends on the particle
that of Co3O4 and of CoO, suggesting that the Co2p3/2 BE size, the crystal composition of cobalt, and the support of
values is an outcome co-contributed by that of Co3O4 and of metal oxides. Lapidus et al. [26] investigated the support
CoO on the surface of catalysts. It is likely that cobalt in and pretreatment effects on reaction activity and selectivity
CA-L and CA-R has a stronger interaction with alumina of cobalt supported on SiO2 and Al2O3. Their results
than that in CA-F and CA-W. In addition, the bulk Co/Al revealed that the existence of CoAl2O4 suppressed the
atom ratio is much higher than the surface atom ratio for all growth of carbon chain and Co3O4 improved the chain
catalysts. This implies the low dispersion or the aggregation growing probability. They also pointed out that the bridged-
state of cobalt on the surface of catalysts, especially for type form adsorbed on the stronger sites favored the
CA-R and CA-L. dissociation of CO and chain growing of –CH2 – fragments.
CO adsorption shows many peaks in FTIR spectra. As for Sharma et al. [27] observed that the selectivity of Cþ5 liquid
CA-F and CA-W catalysts, the bridged-type bands of CO hydrocarbons increased for the modified Co/SiO2 –Al2O3
are major; however, the linear-type CO becomes the main catalysts. They attributed the enhanced selectivity to a
species in the reduced CA-L and CA-R. The change in decrease in the surface area, and the loss of oxygen from
adsorption mode may be associated with the reducibility of SiO2 sites, thereby, creating reactive centers on the catalyst
catalyst. Cobalt catalysts supported on alumina with low surface in the form of intermediate cobalt silicate. Here,
acidity can lead to the higher reducibility, and then favor to XPS and TPR exhibit that there are more difficult reduced
produce the stronger bands of bridged-type CO and more surface species for CA-L and CA-R, whereas more Co3O4
active sites for the adsorption of hydrogen and carbon species for CA-W and CA-F. FTIR spectra show that
586 J. Zhang et al. / Fuel 82 (2003) 581–586

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