Journal of Catalysis 215 (2003) 66–77

www.elsevier.com/locate/jcat

Effect of zirconia-modified alumina on the properties

of Co/γ -Al2O3 catalysts
Bunjerd Jongsomjit,1 Joongjai Panpranot,1 and James G. Goodwin Jr. ∗
Department of Chemical Engineering, Clemson University, Clemson, SC 29634, USA
Received 15 April 2002; revised 4 November 2002; accepted 7 November 2002

Abstract
Zr promotion has been shown to improve the activity of Co/SiO2 and Co/Al2 O3 Fischer–Tropsch synthesis (FTS) catalysts. However,
little is known about how it works. The focus of this study was to investigate the impact of Zr modification of alumina used to support
Co catalysts. Zr was first impregnated into alumina to produce Zr-modified alumina supports containing 2–11 wt% of ZrO2 in the final
catalyst. Co catalysts having 20 wt% Co were then prepared from these supports by incipient wetness. It was found that Zr modification
had a significant impact on the catalyst properties: FTS rate per gram of catalyst increased significantly (> 65% at steady state) with
Zr modification and Co reducibility, especially during standard reduction, also increased. H2 chemisorption, however, was found to be
essentially constant with Zr modification. The impact of Zr modification is likely due to stabilization of the alumina support, prevention or
blockage of Co surface “aluminate” formation, and an increase in Co reducibility to the active catalytic metallic phase. SSITKA results for
CO hydrogenation showed an increase in the number of active surface intermediates (NM ) with Zr modification while the intrinsic activity
(1/τM ) remained constant, confirming that the major impact of Zr was in increasing the concentration of active Co surface sites. Because
of the inconsistency of the turnover frequency calculated based on H2 chemisorption with the 1/τM results, it is suggested that the standard
adsorption conditions usually used for Co may not be adequate for modified Co catalysts such as the ones studied here.
 2003 Elsevier Science (USA). All rights reserved.

Keywords: Zr modification; Co FTS catalysts; CO hydrogenation; Co-support compound formation

1. Introduction It has been shown that cobalt-support compound forma-

tion (Co-SCF) in cobalt-based catalysts, especially those
To increase catalyst activity, many promoters such as Ru used in Fischer–Tropsch synthesis (FTS), can occur during
[1–3], Zr [4,5], La [6], Rh [7–9], B [10], and Pt [11] have pretreatment and/or under reaction conditions [21–34]. This
been investigated for Co catalysts. It has been proposed that irreversible Co-SCF causes a decrease in the overall cata-
a variety of these promoters can increase the reducibility lyst activity due to the loss of active Co metal available for
of Co, preserve the activity by preventing the formation catalyzing the reaction.
of coke, exhibit cluster and ligand effects, act as a source A number of FTS patents by Shell [35,36] have involved
of hydrogen spillover, and enhance the dispersion. The Zr promotion of Co/SiO2 . Ali et al. [4] investigated Zr pro-
use of additives to specifically modify the metal–support motion of Co/SiO2 catalysts for FTS and found that Zr is
interaction has also been investigated. It has been found that basically a rate promoter. Rohr et al. [5] investigated the ef-
metal dispersion, chemical state, as well as catalyst activity fect of adding Zr to an alumina support for Co FTS catalysts.
are affected by changing the interaction between the metal They found that, at 5 bar and a H2 : CO ratio of 9 : 1, Zr-
catalytic phase and the support as a result of modification modified alumina-supported Co exhibited an increase in the
using B, Ge, Ga, and Zn [10,12–20]. activity and selectivity to C5+ hydrocarbons. Steady-state
isotopic transient kinetic analysis (SSITKA) showed that the
* Corresponding author.
intrinsic activity of Co/Al2 O3 was not greatly affected by
E-mail address: [email protected] (J.G. Goodwin Jr.).
Zr modification [5]. Although Zr modification appears to in-
1 Department of Chemical Engineering, Chulalongkorn University, crease the rate of FTS on Co catalysts [4,5], no studies have
Phyathai Road, Bangkok 10330, Thailand. specifically addressed how Zr promotes the reaction. Under-
0021-9517/03/$ – see front matter  2003 Elsevier Science (USA). All rights reserved.
doi:10.1016/S0021-9517(02)00102-1
 B. Jongsomjit et al. / Journal of Catalysis 215 (2003) 66–77 67

standing how Zr modifies catalyst properties could lead to Table 1

the design of more robust and active Co catalysts. Catalyst compositions
This investigation focused on studying the impact of Zr Catalyst samples Compositions (wt%)
modification of Co/γ -Al2 O3 catalysts. A series of Co/γ - Co ZrO2 γ -Al2 O3
Al2 O3 –Zr catalysts were prepared with a range of Zr Co/Al 20 0 80
concentrations. Since the presence of water vapor during Co/Al–Zr-02 20 2.2 77.8
reduction is known to increase Co–aluminate formation, Co/Al–Zr-05 20 5.4 74.6
the impact of Zr loading on the reducibility of Co in the Co/Al–Zr-11 20 10.8 69.2
absence and presence of water vapor was investigated. The
effect on the reaction rate and product distribution during (ii) Standard reduction of the calcined catalysts at 350 ◦ C
FTS was also measured. SSITKA of CO hydrogenation was using a high space velocity (16,000 h−1 ) of H2 fol-
performed to obtain a better understanding of the effect of Zr lowed by passivation with an O2 /He (5.20% of O2 )
modification on the intrinsic activity and surface coverage of mixture at room temperature for 2 h;
reaction intermediates. (iii) Standard reduction of the calcined catalysts at 350 ◦ C
using a high space velocity (16,000 h−1 ) of a mixture
of H2 and 3 vol% water vapor followed by passivation
2. Experimental with an O2 /He (5.20% of O2 ) mixture at room temper-
ature for 2 h.
2.1. Materials
The nomenclature used for samples in this study is the
2.1.1. Co/γ -Al2 O3 following:
The Co/γ -Al2 O3 catalyst was prepared by the incipient Co/Al–Zr-n-i,
wetness impregnation of γ -Al2 O3 . The support precursor
(Al2 O3 , Vista B) was first calcined at 500 ◦ C for 10 h before where n refers to wt% ZrO2 in the support; i = C refers to
impregnation to put it in the form of γ -Al2 O3 having a the calcined catalyst samples; i = RP refers to the reduced
specific surface area of 209 m2 /g and average particle size of and passivated catalyst samples; i = RW P refers to the
ca. 60 µm. Cobalt nitrate [Co(NO3 )2 · 6H2 O] was dissolved samples reduced in the presence of 3 vol% water vapor and
in deionized water and impregnated into the support using then passivated.
incipient wetness to give a final catalyst with 20 wt% cobalt. The catalyst compositions are shown in Table 1.
The catalyst was dried at 110 ◦ C for 12 h and calcined in
air at 300 ◦ C for 2 h following a ramp to temperature at 2.3. Catalyst characterization
1 ◦ C/min.
2.3.1. X-ray powder diffraction (XRD)
XRD was performed to determine the bulk crystalline
2.1.2. Co/γ -Al2 O3 –Zr
phases of the catalysts following different pretreatment con-
The Zr-modified alumina-supported Co catalysts (Co/γ -
ditions. X-ray powder diffraction patterns of samples were
Al2 O3 –Zr) were prepared by the sequential impregnation
collected using a Scintag XDS-2000 X-ray diffractometer
method. The same support (γ -Al2 O3 ) as mentioned above
with monochromatized Cu-Kα radiation (λ = 1.54439 Å).
was used. First, Zr was impregnated into the support using
The spectra were scanned at a rate of 2.4◦ /min from 2θ = 20
a solution of zirconium(IV) n-propoxide (70 wt% in n-
to 80◦ .
propanol, Alfa Aesar) to produce Zr-modified alumina
supports having 2, 5, and 11 wt% of ZrO2 . Second, the Zr- 2.3.2. Raman spectroscopy
modified supports were calcined at 350 ◦ C for 2 h (ramp rate The Raman spectra of the samples were collected by
1 ◦ C/min) prior to impregnation of cobalt. projecting a continuous wave laser of helium–neon (He–Ne)
Cobalt nitrate was used to impregnate the Zr-modified red (632.816 nm) through the samples exposed to air at room
supports to produce calcined catalysts with 20 wt% cobalt temperature. A scanning range between 100 and 1000 cm−1
using the same procedure as given in the previous section. with a resolution of 2 cm−1 was applied. The data were
analyzed using Renishaw WiRE (Windows-based Raman
2.2. Catalyst pretreatment and nomenclature Environment) software, which allowed Raman spectra to
be captured, calibrated, and analyzed using system 2000
Standard reduction was carried out at 350 ◦ C for 10 h in functionality via the Galactic GRAMS interface with global
flowing hydrogen after ramping to temperature at 1 ◦ C/min imaging capacity.
to reduce the Co to its active state for reaction. The catalysts
were characterized following these three pretreatments: 2.3.3. SEM and EDX
SEM and EDX were performed to study the morpholo-
(i) The original calcination step; gies of the catalyst samples and their elemental distributions,
68 B. Jongsomjit et al. / Journal of Catalysis 215 (2003) 66–77

respectively. A Hitachi S3500N SEM was used in the back- 2.5. Steady-state isotopic transient kinetic analysis
scattering electron (BSE) mode at 15 kV with a working dis- (SSITKA)
tance (the distance between a sample and the electron beam)
of 15 mm. After the SEM micrographs were taken, EDX SSITKA was performed using a differential fixed-bed
was performed to determine the elemental concentration on glass microreactor. Hydrogenation of CO was carried out
the catalyst surface (using INCA software). at 220 ◦ C and 1.8 atm. A flow rate of H2 /CO/He =
20/2/8 cc/min was used. A relatively high H2 /CO ratio
of 10 was used to minimize deactivation due to carbon
2.3.4. Hydrogen chemisorption deposition during reaction. Thermocouples at the top and at
Static H2 chemisorption on the re-reduced cobalt cata- the bottom of the catalyst bed assured precise temperature
lyst samples at 100 ◦ C was performed using the method control during pretreatment and reaction. Typically, 15 mg
described by Reuel and Bartholomew [37] and was used of a calcined catalyst sample was re-reduced in situ in
to determine the number of reduced cobalt metal surface flowing H2 (30 cc/min) at 350 ◦ C for 10 h prior to the
atoms. This is usually related to the overall activity of the reaction. As the reaction began, reactor effluent samples
catalyst during FTS. Chemisorption was conducted in a Mi- were taken at 1-h intervals and analyzed by on-line GC.
cromeritics ASAP 2010 and analyzed using ASAP 2010C Generally, steady state was reached after 5 h in all cases.
V3.00 software. Prior to H2 chemisorption, the reduced and During steady state, transients of methane and CO were
passivated catalyst samples were evacuated to 10−6 mm Hg obtained by switching the inlet flow of 12 CO/Ar to 13 CO
at 100 ◦ C for 15 min, reduced in flowing H2 (50 cc/min) without disturbing the stability of the reaction. A trace (5%)
at 100 ◦ C for 15 min, reduced at 350 ◦ C in flowing H2 for of Ar in the 12 CO was used to account for the gas-phase
10 h, and then evacuated at 350 ◦ C for 90 min to desorb any holdup of the system. The decay or increase of isotopically
hydrogen. marked species was monitored by an on-line Leybold-
Inficon Auditor-2 quadruple mass spectrometer. Average
2.3.5. Temperature-programmed reduction (TPR) surface residence times for the carbon in CH4 and CO
were calculated from these transient studies. The number of
TPR was performed to determine the reducibility and
surface intermediates which gave rise to CH4 and the amount
reduction behavior of the catalyst samples. TPR was carried
of reversibly chemisorbed CO were also calculated.
out in an Altamira AMI-1 system using 50 mg of catalyst
and a temperature ramp from 30 to 800 ◦ C at 5 ◦ C/min.
The reduction gas was 5% H2 in Ar. A cold trap (−70 ◦ C)
3. Results
was placed before the detector to remove water produced
during the reaction. A thermal conductivity detector (TCD)
3.1. X-ray diffraction
was used to determine the amount of hydrogen consumed.
The hydrogen consumption was calibrated using TPR of XRD patterns for the calcined Co catalysts (with and
silver oxide (Ag2 O) at the same conditions. The reduced without Zr modification) and Co3 O4 (spinel) are shown in
and passivated catalyst samples were re-calcined in situ at Fig. 1. They had identical XRD patterns. The diffraction
300 ◦ C for 2 h before TPR was performed. peaks at 31.3◦ , 36.8◦, 45◦ , 55◦ , 59.4◦ , and 65.4◦ are those
of Co3 O4 . Peaks for γ -Al2 O3 were also evident. No peaks
2.4. Reaction of ZrO2 or any other Zr compound, however, were detected.
This indicates that Zr was present in a highly dispersed
form [4]. It will be assumed from this point on in the
FTS was carried out under differential reaction conditions paper that Zr was in the form of ZrO2 . After reduction
(< 5% conversion) at 220 ◦ C and 1 atm total pressure. and passivation, only XRD peaks of CoO (at 37◦ , 42.6◦,
A flow rate of H2 /CO/Ar = 60/30/10 cc/min in a fixed- and 61.8◦ ) and γ -Al2 O3 were evident. No Co metal peaks
bed reactor under differential reaction conditions was used. were seen due to its high dispersion and their overlap with
Thermocouples at the top and the bottom of the catalyst bed those for γ -Al2 O3 . No XRD peaks of CoAl2 O4 (spinel) [38]
ensured precise temperature control during pretreatment and could be detected either for any of the catalyst samples.
reaction. Typically, 0.2 g of the pretreated catalyst sample Recalcination of the reduced catalysts caused the cobalt to
was re-reduced in situ in flowing H2 (50 cc/min) at 350 ◦ C revert back to Co3 O4 .
for 10 h prior to FTS. To avoid exotherms and hot spots
that lead to rapid catalyst deactivation, the reaction was 3.2. Raman spectroscopy
initiated in a controlled manner by gradually increasing the
reactant concentrations over a period of 2 h. After the start- Raman spectra for the calcined catalyst samples and
up, samples were taken in 3-h intervals and analyzed by on- Co3 O4 are shown in Fig. 2. After calcination, Raman bands
line gas chromatography. Steady state was reached after 24 h at 198, 480, 519, 619, and 690 cm−1 were observed for
in all cases. all calcined catalyst samples. These can be best assigned to
 B. Jongsomjit et al. / Journal of Catalysis 215 (2003) 66–77 69

Fig. 1. XRD patterns of Co3 O4 and the calcined Co catalysts.

Fig. 3. Raman spectra of CoO, Co3 O4 , CoAl2 O4 (spinel), and the reduced
and passivated catalysts.

Fig. 2. Raman spectra of Co3 O4 and the calcined catalysts.

Co3 O4 . The Raman spectrum for γ -Al2 O3 was essentially

flat. The Raman band (at 642 cm−1 ) for ZrO2 [39] was not
seen for any of the catalyst samples. Raman spectra of the
reduced and passivated catalyst samples are shown in Fig. 3.
Raman bands for all reduced and passivated catalyst samples
with Zr modification were identical, but different from
those for the reduced and passivated Co catalyst without
Zr modification (Co/Al-RP). Only two very broad Raman Fig. 4. Raman spectra of CoO, Co3 O4 , CoAl2 O4 (spinel), and the reduced
bands at ca. 690 and, especially, 560 cm−1 were detected for (with 3% H2 O vapor added) and passivated catalysts. The spectrum for
Co/Al-RP and this has been correlated to the formation of a Co/Al–Zr-05-RP is included for reference.
70 B. Jongsomjit et al. / Journal of Catalysis 215 (2003) 66–77

highly dispersed Co “aluminate” phase [38]. Similar results, 3.3. SEM and EDX
except stronger bands, can be observed for the Co/Al sample
reduced with 3 vol% added water vapor (RW P samples) The typical external particle/granule morphologies of
as shown in Fig. 4. Strong Raman bands at 690, 480, and the calcined catalyst samples are shown in Fig. 5. In all
198 cm−1 were observed for the reduced and passivated the Co catalyst micrographs, the white or light spots on the
catalyst samples with Zr modification (RP and RW P, Figs. 3 external surfaces represent high concentrations of Co and
and 4). These bands can best be assigned to Co3 O4 , present its compounds and the gray areas represent the alumina or
on the Co surface after the samples were passivated and Zr-modified alumina support with no/minimal Co present.
exposed to air, rather than CoO (detected in the bulk by There was no significant change in morphology between
XRD) since Raman is more of a surface technique. There the alumina and Zr-modified alumina supports. However, it
was also little evidence of much formation of the highly can be seen in Fig. 5 that Co on the Zr-modified alumina
dispersed Co “aluminate” phase [38] for the Zr-modified supports was better distributed (i.e., had smaller SEM–
catalysts. No peaks for CoAl2 O4 (spinel) were detected in visible Co patches/particles that were more scattered) than
any of the samples. on the unmodified alumina support.

Fig. 5. SEM micrographs of catalyst granules.

 B. Jongsomjit et al. / Journal of Catalysis 215 (2003) 66–77 71

Fig. 6. SEM micrograph and EDX mapping of a calcined Al–Zr-11-C support granule (cross section).

EDX gave useful information about the elemental dis- at 300 ◦ C (Fig. 8). There were two major peaks for Co/Al-
tribution on the cross-sectioned calcined catalyst granules, C located at ca. 350 ◦ C and between 400 and 700 ◦ C
i.e., in the catalyst granule interiors. Figure 6 shows the typ- (maximum at 600 ◦ C). These peaks have been related to
ical elemental distribution for a cross section of a granule of the following reduction steps: Co3 O4 → CoO and CoO →
Zr-modified alumina support. EDX mapping indicated that Co metal (ca. 350 ◦ C), and CoX OY –Al2 O3 → Co metal
all elements in the modified support were well distributed (between 400 and 700 ◦ C), respectively [3,11,38,40,41].
throughout the catalyst granules. This was also true for the There were also three major peaks for the Co catalysts
catalyst after Co loading, as shown in Fig. 7. with Zr modification located at 320–350 ◦ C and between 500
and 800 ◦ C (maximum at ca. 700 ◦ C). It would appear that
3.4. Temperature-programmed reduction (TPR) the broad peak with its maximum ca. 600 ◦ C was shifted
about 100 ◦ C higher with Zr modification. This indicates
To eliminate residual Co(NO3 )2 and its impact on the that Zr modification caused changes in reduction behavior
TPR spectra and the calculation of reducibility [38], all TPR of the Co catalysts. There was an apparent decrease in both
results are reported after initial reduction and re-calcination peak locations for the Zr-modified catalysts with Zr loading.
72 B. Jongsomjit et al. / Journal of Catalysis 215 (2003) 66–77

Fig. 7. SEM micrograph and EDX mapping of a Co/Al–Zr-11-C catalyst granule (cross section).

The TPR profile for the Zr-modified support [11 wt% ZrO2 – reduction peak to higher temperature, there was no evidence
Al2 O3 (without Co)] showed no reduction peak. Thus, the for any additional consumption of H2 . Thus, it is concluded
support would appear not to have been reducible during that, during TPR, activation of H2 by reduced Pt or Co was
TPR. However, one might ask what is the possibility that not sufficient to cause any significant reduction of ZrO2 .
Co impregnated into the Zr-modified supports can activate Figure 9 shows TPR profiles of the Co/Al and Co/Al–
hydrogen to partially reduce ZrO2 as a result of spillover. If Zr-05 catalysts after reduction with and without added water
that happened, any additional H2 consumed by ZrO2 would vapor. These catalysts had been re-calcined prior to TPR.
lead to an overestimation of Co reducibility. To answer this The two-peak reduction TPR profiles were observed for
question, TPR of alumina and modified supports containing the RW PC samples. However, water vapor present during
5 wt% Pt were studied. All the PtO2 on alumina was standard reduction resulted in a shift of the second TPR
reducible at temperatures 30–400 ◦ C (maximum at 200 ◦ C). reduction peak to even higher temperature for both the
While the addition of Zr resulted in a shift of the second unmodified and Zr-modified catalysts.
 B. Jongsomjit et al. / Journal of Catalysis 215 (2003) 66–77 73

3.5. H2 chemisorption

H2 chemisorption results are shown in Table 2. The

overall dispersion of reduced Co in the catalyst samples
based on the H2 chemisorption results is also given. The
Co metal dispersions of the catalysts ranged between 3.5
and 3.8%. The results indicate that the amount of adsorbed
H2 was not dramatically changed with Zr modification,
although there was perhaps a slight increase. The Zr-
modified support [11 wt% ZrO2 /γ -Al2 O3 (without Co)] was
inactive for H2 chemisorption.

3.6. Reaction rate

FTS was performed to determine the overall activity and

product distribution of the Co catalysts with and without Zr
modification. The results are shown in Table 3 and Fig. 10.
It can be seen that the presence of ZrO2 (2–11 wt%) as a
Fig. 8. TPR profiles of the reduced and recalcined catalysts. support modifier increased significantly both the initial and
the steady-state FTS rates, > 115% and > 65%, respec-
tively. TOF based on H2 chemisorption also increased by
approximately 50–100% with Zr modification due to the in-
crease in rate, since the amount of H2 adsorbed was essen-
tially constant. Considering the product distribution, it can
be observed that the addition of the Zr modifier resulted in a
slight increase in the Anderson–Schulz–Flory (ASF) chain-
growth probability (α). The hydrocarbons formed were pri-
marily straight chain alkanes, typical for Co FTS catalysts
at these conditions. As also seen in Table 3, it appears that
the amount of carbon deposited on the catalysts during FTS
for 24 h (a primary cause of Co deactivation during FTS)
decreased with Zr modification. The reaction rates on the
unmodified and Zr-modified catalysts after various pretreat-
ments are shown in Table 4. It is obvious that the rate on
the initially reduced samples (−R) was higher that than on
the reduced and passivated samples (−RPR and −RW PR,
re-reduced prior to FTS). Moreover, the rate on the reduced
and passivated samples decreased with the addition of wa-
ter vapor during standard reduction (again re-reduced prior
to FTS), although less so on the Zr-modified catalyst.

3.7. SSITKA
Fig. 9. TPR profiles of recalcined Co/Al and Co/Al–Zr-05 catalysts after
reduction with and without added water vapor.
Steady-state isotopic transient kinetic analysis was used
to determine in situ surface reaction parameters. SSITKA
enables one to calculate the surface concentration of reac-
tion intermediates and pseudo-first-order rate constant (kp )
The reducibilities of Co/γ -Al2 O3 and Co on Zr-modified [2,6,42]. During steady-state reaction, the surface residence
γ -Al2 O3 after various pretreatments are shown in Table 2. times (τ ) for CO and CH4 were determined by integrating
While the reducibilities during TPR to 800 ◦ C are interest- the areas between the transient curves for Ar and labeled
ing, the amount of reduction during TPR from 30 to 400 ◦ C CO or CH4 , respectively. The pseudo-first-order rate con-
is more important since it is related to the reducibilities of stant (kp ), a measure of intrinsic site activity for methana-
these Co catalysts during standard reduction at 350 ◦ C [23]. tion, was calculated by taking the inverse of the residence
It can be seen that the reducibility of alumina-supported Co time of CH4 . The method used to calculate these parameters
increased significantly with Zr modification. is described extensively by Shannon and Goodwin [42].
74 B. Jongsomjit et al. / Journal of Catalysis 215 (2003) 66–77

Table 2
Reducibility and H2 chemisorption results
Catalyst Zr/Co Reducibilitya,b,c Chemisorption
samples atom (30–800 ◦ C) (30–400 ◦ C)d Total H2 % Co
ratio chemisorptione dispersionf
C RPC RW PC C RPC RW PC
(µmol of H2 /g cat)
Co/Al 0 80 58 50 29 17 14 59 3.5
Co/Al–Zr-02 0.05 81 64 – 60 38 – 59 3.5
Co/Al–Zr-05 0.13 90 67 58 63 37 18 64 3.8
Co/Al–Zr-11 0.26 98 65 – 62 39 – 64 3.8
Al–Zr-11 NA 0 0 0 0 0 0 0 0
a The RP and RW P samples were re-calcined at 300 ◦ C in air for 2 h before TPR measurement.
b The reducibility was based on a calibration with Ag2 O (100% reducibility).
c Error = ±5% of measurement of reducibility, as determined directly.
d The reducibility during TPR between 30 and 400 ◦ C is related to the reducibility of the catalysts during standard reduction [23].
e Error = ±5% of measurement of H2 chemisorption, as determined directly.
f %Co dispersion (%) = [2 × (total H2 chemisorption/g cat)/(no. of µmol of Co total/g cat)] × 100%.

Table 5 shows the SSITKA results for Co catalysts achieved during TPR from 30 to 400 ◦ C (related to the
with and without Zr modification. The surface reaction reducibility during standard reduction at 350 ◦ C for alumina-
residence time for the CH4 intermediates (τ M ) remained supported Co catalysts [23]) increased more significantly
unchanged with Zr modification. Thus, there was no change with Zr modification, although the amount of Zr added did
in the intrinsic activity (1/τ M ) of the methane-producing not seem to have a great impact.
sites. This indicates that the mean activity of the sites It is known from our previous work [38] that a high partial
producing methane was not affected by Zr modification. pressure of water vapor during reduction results in a lower
The surface residence time for CO (τ CO ) was also found
reducibility for an unpromoted Co catalyst. Water present in
to show no significant difference. The surface abundance
the H2 reduction gas (such as naturally occurs as a byproduct
of intermediates leading to the formation of methane (N M ),
of metal catalyst reduction) decreases the reducibility of
however, was almost twice as much upon Zr modification.
The surface coverages for methane intermediates (θ M ) were Co catalysts due to the formation of nonreducible (at
found to be low (< 0.2), as is typical, but this was somewhat temperatures
900 ◦ C) Co “aluminate” [23,38], as is
higher with Zr modification. apparent in Table 2 for the unpromoted Co catalyst. This was
also true for the Zr-modified catalysts. The reducibility (30–
400 ◦ C) of Co/Al–Zr-05-RPC decreased from 37 to 18%
4. Discussion (Table 2) when water was added during standard reduction
(RW PC sample). However, it is obvious that the reducibility
It is obvious that Zr modification resulted in significant was still higher than that of unpromoted Co catalyst reduced
differences in the properties of alumina-supported Co. It also in the presence of water vapor (Co/Al-RW PC sample).
was found that the reducibility for TPR from 30 to 800 ◦ C In addition, as seen in Figs. 3 and 4, there was no Raman
(Table 2) increased somewhat with Zr modification (ZrO2 = evidence for the formation of Co “aluminate” for the
2–11 wt%). However, and more importantly, the reducibility Zr-modified catalysts. This suggests that Zr modification

Table 3
FTS reaction rate and product distribution
Catalyst Rate of CO TOFH c × 103 (s−1 ) Product distribution (wt%) Carbon
samples conversiona,b Initial SS C1 C2 –C4 C5 –C12 C13+ α content
(µmol/g cat/s) (wt%)d
Initial SS
Co/Al-R 3.0 2.2 25 19 14.2 48.0 35.9 1.9 0.63 0.42
Co/Al–Zr-02-R 6.5 3.6 55 31 11.0 42.5 42.5 4.0 0.66 –
Co/Al–Zr-05-R 7.5 3.6 59 28 11.3 43.1 41.9 3.7 0.66 0.14
Co/Al–Zr-11-R 6.5 3.8 51 30 11.1 42.7 42.3 3.9 0.68 –
a FTS was carried out at 220 ◦ C, 1 atm, and H /CO ratio = 2 (H /CO/Ar = 60/30/10 cc/min). Catalyst samples were reduced (R) after pretreatments
2 2
prior to the reaction.
b Error ± 5%, as determined directly.
c Based on total H chemisorption.
2
d Carbon content on the used catalyst samples after FTS for 24 h was analyzed using combustion/colometric titration by Galbraith Laboratories, Inc.
 B. Jongsomjit et al. / Journal of Catalysis 215 (2003) 66–77 75

Table 4
Effect of pretreatment on reaction rate during FTS
Catalyst samples Rate of CO conversiona,b
(µmol/g cat/s)
Initial Steady state
Co/Al-R 3.0 2.2
Co/Al-RPR 2.6 1.4
Co/Al-RW PR 2.2 0.6
Co/Al–Zr05-R 7.5 3.6
Co/Al–Zr05-RPR 6.5 2.2
Co/Al–Zr05-RW PR 5.0 1.8
a FTS was carried out at 220 ◦ C, 1 atm, and H /CO ratio = 2 (H /CO/
2 2
Ar = 60/30/10 cc/min). Catalyst samples were reduced after pretreatments
prior to the reaction.
b Error ± 5%, as determined directly.

As reported by Rohr et al. [5], reducibilities of Co/γ -

Al2 O3 during TPR to 900 ◦ C were not changed with
Zr modification. Our measurements of reducibility were
lower than those of Rohr et al., and we found that during
TPR to 800 ◦ C our Zr-modified catalysts exhibited slightly
higher reducibilities than the unmodified one. The difference
between our results and those of Rohr et al. was probably
due to the fact that we eliminated the contribution from
Fig. 10. Reaction rate vs TOS.
residual Co nitrate and TPR was performed to 800 ◦ C.
Probably because of the former, we were better able to detect
decreased the impact of water vapor during reduction, important reducibility differences upon Zr modification.
possibly by partially blocking Co “aluminate” formation. In the present study, dramatic changes in the characteris-
In general, most authors have reported reducibilities dur- tics of the Raman bands for the reduced and passivated cata-
ing TPR of Co catalysts in the calcined form. For catalysts lyst samples with Zr modification were observed. Basically,
prepared with Co nitrate, TPR measurement of reducibilities the Co “aluminate” bands were no longer present upon Zr
of catalysts initially only calcined can result in an overesti- modification. Only Raman bands for Co3 O4 at 690, 480, and
mation of the amount of Co reduced due to the consump- 198 cm−1 were evident on the reduced and passivated Zr-
tion of H2 by Co nitrate [3,38]. To eliminate this error, the modified samples (Fig. 3). Similar results were also found
residual nitrate has to be removed either by prolonging the even when water vapor was added during standard reduc-
initial calcination period from 2 to 14 h [3] or by reduc- tion, as shown in Fig. 4. This suggests that Zr modification
tion at 350 ◦ C followed by re-calcination prior to TPR mea- decreases the amount of Co “aluminate” formed, even in the
surement. After the elimination of the Co nitrate peak at ca. presence of water vapor. It should be noted, however, that
200 ◦ C [3,38], only two reduction peaks remain [3,38]. This XRD did not detect any differences upon Zr modification.
is the reason why reducibilities of the reduced, passivated, The XRD results were typical for reduced Co/γ -Al2 O3 cat-
and recalcined samples are reported in this paper (Figs. 8 alysts [3,23,38]. The Co “aluminate” formed has been con-
and 9) as they provide more accurate values of reducibility. cluded to be too dispersed to be detected by XRD [38].

Table 5
SSITKA results for CO hydrogenation (H2 /CO = 10, T = 220 ◦ C, and P = 1.8 atm)
Catalyst CO Rate of CO Rate of CH4 τ CO a N CO b τ Mc N Md θ Me kp f TOFH g
samples conversion conversion formation (s) (µmol/g cat) (s) (µmol/g cat) (s−1 ) (s−1 )
(%) (µmol/g cat/s) (µmol/g cat/s)
Co/Al 3.6 2.9 2.6 1.0 39 3.6 10 0.08 0.28 0.02
Co/Al–Zr11 7.0 5.5 4.9 1.0 41 3.5 17 0.13 0.28 0.04
a τ CO = surface residence time of reversibly adsorbed CO. Standard deviation = ±0.2 s.
b NCO = surface concentration of reversibly adsorbed CO. Standard deviation = ±2 µmol/g cat.
c τM = surface residence time of methane intermediates. Standard deviation = ±0.2 s.
d NM = surface concentration of methane intermediates. Standard deviation = ±2 µmol/g cat.
e θM = surface coverage of carbonaceous methane intermediates = NM /(total adsorbed H).
f kp = 1/τM , pseudo-first-order rate constant.
g TOF based on total H2 chemisorption.
76 B. Jongsomjit et al. / Journal of Catalysis 215 (2003) 66–77

One of the most critical parameters determining the cat- The conditions used, while appropriate for most Co cata-
alytic activity of Co FTS catalysts, besides Co reducibil- lysts, may not be appropriate for these Zr-modified ones.
ity, is H2 chemisorption. However, it was found that the
H2 chemisorption on the reduced Co catalysts was not dra-
matically affected by Zr modification; there was only a 5. Conclusions
slight increase in the amount of H2 chemisorption (Table 2).
Characterization of Co catalysts after FTS using hydrogen Zr modification of the alumina support had a significant
chemisorption is problematic since carbon deposited dur- impact on the properties of Co/γ -Al2 O3 catalysts. The
ing FTS can interact with the hydrogen as well as cause overall catalytic activity during FTS increased significantly
spillover. (> 65%) upon Zr modification. SSITKA showed that the
During FTS, the reaction rate declined on the average number of active reaction intermediates (NM ) increased
ca. 50% during time-on-stream to steady state (Fig. 10). with Zr modification while the intrinsic activity (1/τ M )
This is typical for supported Co catalysts and is usually due remained constant. Most of this increase appears to have
to carbon deposition (see Table 3) that blocks the active been due to an increase in reducibility during standard
sites. The initial activity of such catalysts can be usually reduction. The increase in reducibility appeared to have been
largely recovered by extensive treatment with hydrogen or caused by a decrease in the amount of Co-SCF, as seen
calcination/reduction. by Raman spectroscopy. Zr modification may have caused
(i) a stabilization of the alumina support by blocking its
Considering the unpromoted Co catalyst, its TOF was
defect sites, thus blocking Co “aluminate” formation, and/or
ca. 2 × 10−2 s−1 —typical for Co catalysts under these
(ii) a minimization of the impact of water vapor in modifying
conditions. Due to the large increases in FTS rate without
the surface properties of alumina, thereby decreasing the
any changes in H2 chemisorption, the calculated TOFs at
ease of Co reaction with the alumina. Thus, in summary,
steady-state based on H2 chemisorption were found to be
Zr modification increased Co reducibility and, probably, the
larger by a factor of 2 with Zr modification. Since TOF
number of exposed Co sites active for CO hydrogenation.
is basically related to the intrinsic activity by definition,
Considering the variation in TOFH but the lack of variation
it might appear that Zr modification caused an increase in in 1/τ M (a measure of intrinsic activity), it is likely that
the intrinsic activity for alumina-supported Co catalysts. TOFH is in error due to errors in measuring accurately by
However, this conclusion is rendered doubtful based on the H2 chemisorption the number of reduced Co surface atoms.
SSITKA results. The standard H2 chemisorption procedure of Reuel and
Our SSITKA results confirm those of Rohr et al. [5] that Bartholomew [37] typically used by us and others, thus, may
the intrinsic activity is not affected by Zr modification, as not be suitable for these Zr-modified Co catalysts.
indicated by the constant values of the intrinsic pseudo-first-
order activity (kp = 1/τM ). The SSITKA results show that
there was an increase in the number of active reaction inter- Acknowledgments
mediates (NM ) with Zr modification. Thus, the higher activ-
ity of the Co catalysts with Zr modification was due either to The authors would like to thank the Royal Thai Govern-
a greater concentration of active sites or a higher occupancy ment for financial support of B.J., Energy International, Inc.,
of the sites during reaction. It is known that the number of for providing the catalysts used in this study, and the Center
active intermediates on the Co surface obtained by SSITKA for Advanced Engineering Fibers and Films (CAEFF) for
during CO hydrogenation is only a small fraction (θ < 0.2) the Raman spectrometer used in this study.
of the number of Co metal surface atoms measured by H2
chemisorption [2]. It should also be noted that the number
of reaction intermediates is a better measure of the true num- References
ber of active CO hydrogenation sites than is the number of
reduced Co surface atoms obtained by H2 chemisorption. [1] E. Iglesia, S.L. Soled, F.A. Fiato, J. Catal. 137 (1992) 212.
[2] A.R. Belambe, R. Oukaci, J.G. Goodwin Jr., J. Catal. 166 (1997) 8.
Without any change in intrinsic activity, it is unlikely that [3] A. Kogelbauer, J.G. Goodwin Jr., R. Oukaci, J. Catal. 160 (1996) 125.
an increase in surface coverage (θ ) alone can explain the [4] S. Ali, B. Chen, J.G. Goodwin Jr., J. Catal. 157 (1995) 35.
rate change, suggesting an increase in the number of active [5] F. Rohr, O.A. Lindvag, A. Holmen, E.A. Blekkan, Catal. Today 58
Co sites. Clearly, the reducibility of Co/γ -Al2 O3 was in- (2000) 247.
[6] G.J. Haddad, B. Chen, J.G. Goodwin Jr., J. Catal. 160 (1996) 43.
creased by Zr modification, and it might be expected that [7] V.H.F.J. Blik, D.C. Köningsberger, R. Prins, J. Catal. 97 (1986) 210.
H2 chemisorption would also increase significantly. Given [8] J.H.A. Martens, V.H.F.J. Blik, R. Prins, J. Catal. 97 (1986) 200.
the consistency of the site activity (1/τ M ), it is possible that [9] V.H.F.J. Blik, R. Prins, J. Catal. 97 (1986) 188.
TOFH is in error (or at least variable) due to an incom- [10] M.A. Stranick, Houalla, D.M. Hercules, J. Catal. 104 (1987) 396.
[11] D. Schanke, S. Vada, E.A. Blekkan, A.M. Hilmen, A. Hoff, A. Hol-
plete chemisorption of H2 . The standard conditions for H2 men, J. Catal. 156 (1995) 85.
chemisorption on Co have been chosen to maximize acti- [12] A. Lycourghiotis, C. Defosse, F. Delannay, J. Lemaitre, B. Delmon,
vated chemisorption while minimizing hydrogen spillover. J. Chem. Soc. Faraday Trans. 76 (1980) 1677.
 B. Jongsomjit et al. / Journal of Catalysis 215 (2003) 66–77 77

[13] M. Houalla, J. Lemaitre, B. Delmon, J. Chem. Soc. Faraday Trans. 78 [28] J.M. Jablonski, M. Wolcyrz, L. Krajczyk, J. Catal. 173 (1998) 530.
(1982) 1389. [29] B. Ernst, A. Bensaddik, L. Hilaire, P. Chaumette, A. Kiennemann,
[14] M. Houalla, F. Delannay, B. Delmon, J. Phys. Chem. 85 (1981) 1704. Catal. Today 39 (1998) 329.
[15] A. Cimino, M. Logcono, M. Schiavello, J. Phys. Chem. 79 (1975) 243. [30] H. Ming, B.G. Baker, Appl. Catal. A 123 (1995) 23.
[16] M. Lo Jacono, M. Schiavello, V.H.J. DeBeer, G. Minelli, J. Phys. [31] D. Schanke, A.M. Hilmen, E. Bergene, K. Kinnari, E. Rytter, E.
Chem. 81 (1977) 1583. Adnanes, A. Holmen, Energy Fuels 10 (4) (1996) 867.
[17] G. Muralidhar, F.E. Massoth, J. Shabtai, J. Catal. 85 (1984) 44. [32] R.L. Chin, D.M. Hercules, J. Phys. Chem. 86 (1982) 360.
[18] F.E. Massoth, G. Muralidhar, J. Shabtai, J. Catal. 85 (1984) 53. [33] L.B. Backman, A. Rautiainen, A.O.I. Krause, M. Lindblad, Catal.
[19] R.L. Chin, D.M. Hercules, J. Catal. 74 (1982) 121.
Today 43 (1998) 11.
[20] B.K. Sharma, M.P. Sharma, S.K. Roy, S. Kumar, S.B. Tendulkar, S.S.
[34] R.B. Greegor, F.W. Lytle, R.L. Chin, D.M. Hercules, J. Phys. Chem. 85
Tembe, B.D. Kulkarni, Fuel 77 (15) (1998) 1763.
(1981) 1232.
[21] A. Kogelbauer, J.C. Weber, J.G. Goodwin Jr., Catal. Lett. 34 (1995)
[35] M.F. Post, S.T.B. Sie, European Patent Application, 0167,215 A2,
259.
[22] D. Schanke, A.M. Hilmen, E. Bergene, K. Kinnari, E. Rytter, E. Ad- 1985.
nanes, A. Holmen, Catal. Lett. 34 (1995) 269. [36] A. Hoek, A.H. Joustra, J.K. Minderhould, M.F. Post, UK Patent
[23] Y. Zhang, D. Wei, S. Hammache, J.G. Goodwin Jr., J. Catal. 188 Application, GB 2,125,062 A, 1983.
(1999) 218. [37] R.C. Reuel, C.H. Bartholomew, J. Catal. 85 (1984) 63.
[24] R. Riva, H. Miessner, R. Vitali, G.D. Piero, Appl. Catal. A 196 (2000) [38] B. Jongsomjit, J. Panpranot, J.G. Goodwin Jr., J. Catal. 204 (2001)
111. 98.
[25] R. Bechara, D. Balloy, J.Y. Dauphin, J. Grimblot, Chem. Mater. 11 [39] Z. Liu, L. Dong, W. Ji, Y. Chen, J. Chem. Soc. Faraday Trans. 94 (8)
(1999) 1703. (1998) 1137.
[26] M. Kraum, M. Baerns, Appl. Catal. A 186 (1999) 189. [40] P. Arnoldy, J.A. Moulijn, J. Catal. 93 (1985) 38.
[27] B. Ernst, S. Libs, P. Chaumette, A. Kiennemann, Appl. Catal. A 186 [41] A.M. Hilmen, D. Schanke, A. Holmen, Catal. Lett. 38 (1996) 143.
(1999) 145. [42] S.L. Shannon, J.G. Goodwin Jr., Chem. Rev. 95 (1995) 677.