Applied Catalysis, 58 (1990) 199-208 199

Elsevier Science Publishers B.V., Amsterdam - - Printed in The Netherlands

Studies of Molybdena-Alumina Catalysts

XVII. Sulfided Catalysts Exposed to Air

F.E. MASSOTH*, C.-S. KIM and JIAN-W. CUIa

Department of Fuels Engineering, University of Utah, Salt Lake City, Utah 84112 (U.S.A.)
(Received 1 May 1989, revised manuscript received 17 October 1989)

ABSTRACT

Catalysts containing various levels of Mo supported on gamma-alumina were activated by: ( 1 )

sulfiding at 400 ° C; or (2) sulfiding in steps to 400 ° C; or (3) sulfiding in steps to 400 ° C, followed
by cooling to room temperature, exposing to air, and finally resulfiding at 400 ° C. The latter cat-
alysts exhibited significantly lower NO chemisorption, but only slightly lower hydrodesulfuriza-
tion activity as compared to the former catalysts. We propose that oxygen adsorbed during air
exposure is not completely removed during resulfiding, leading to more active reaction centers but
less of them. We further propose that the more active center consists of an oxygen anion adjacent
to a vacancy site, instead of the regular sulfide center of a sulfide anion and a vacancy site. Step-
sulfided catalysts not exposed to air also displayed higher intrinsic activities, which was attributed
to incomplete sulfiding.

INTRODUCTION

Nitric oxide chemisorption has been used to characterize sulfided Mo/A1203

and CoMo/A1203 catalysts [1-7]. Quantitative measurements of NO on sul-
tided Mo/A1203 catalysts have been shown to correlate well with thiophene
hydrodesulfurization (HDS) activity [1,6]. In the latter studies, the catalysts
were all sulfided in the same prescribed manner. In the course of investigating
the effect of different sulfiding schedules, we have encountered an interesting
phenomenon which points to different sites for sulfided catalysts which have
been exposed to air prior to resulfiding.

EXPERIMENTAL

Catalysts containing various levels of molybdenum were prepared by incip-

ient wetness impregnation of a Ketjen 001-1.5 alumina (196 m2/g), sieved to

aVisiting scholar, Research Institute of Petroleum Processing, Beijing, P.R.C.

0166-9834/90/$03.50 © 1990 Elsevier Science Publishers B.V.

200

20-40 mesh, with ammonium paramolybdate, followed by either oven drying

at 110 ° C for 6 h or oven drying followed by calcination at 500 ° C for 16 h. Three
sulfiding procedures were used: (a) Standard-Sulfiding (Std-Sulf) - the cat-
alyst was heated in helium at 400 oC for 1 h, followed by flowing 10% H2S/H2
for 2 h and then helium for 2 h; (b) Step-In-Sulfiding (Step-In) - the catalyst
was heated to 100°C in helium, then subjected to a flow of H2S/H2 for 1/2 h
at 50°C step intervals to 400°C, 1/2 h at 400°C, and finally a 15 min helium
purge at 400 ° C. In these two sulfiding procedures, the catalysts were sulfided
in situ in the chemisorption apparatus or the reactor. (c) Step-Ex-Sulfiding
(Step-Ex) - the same procedure as for (b) above was performed in a separate
U-tube reactor, after which the catalyst was cooled to room temperature in
helium and stored in a closed bottle. The latter catalysts were then subse-
quently weighed in air prior to introduction into the chemisorption apparatus
or reactor, followed by heating in helium to 400°C and 1/2 h resulfiding at
400 ° C. This exposure to air proved to be critical in the subsequent evaluations.
Chemisorption of NO was measured on the sulfided catalysts by a pulse
technique [6]. Briefly this consisted of lowering the temperature of the cata-
lyst after sulfiding to 0°C in a stream of purified helium (Hydrox, Model 8301 ),
after which known pulses of pure NO were introduced until no further adsorp-
tion was detected by a thermal conductivity cell. Correction for support con-
tribution was made from NO chemisorption measurements on the support sim-
ilarly sulfided and corrected for MoS2 coverage as determined by carbon dioxide
measurements on the sulfided support and catalysts [8].
Temperature-programmed desorption (TPD) experiments of adsorbed NO
were carried out by a linear heating rate (10 ° C/min) in helium, monitoring
the effluent stream by thermal conductivity. A companion series was per-
formed elsewherea, where the effluent was monitored by mass spectrometry.
In the latter, NO was flowed over the sulfided catalyst at 35°C for 15 min,
followed by an argon purge for 1.2 h before starting the TPD.
Catalyst HDS activities were determined in a fixed-bed reactor at 350°C
and atmospheric pressure with a mixture of thiophene (0 ° C)/H2 (60 cm3/
min) and 10% H2S/H2 (20 cm3/min). The extra hydrogen sulfide was added
to maintain an essentially constant hydrogen sulfide inhibition in order that
pseudo-first order rate constant could be calculated [9]. First-order rate con-
stants were determined from conversion obtained after 18 h on stream.

RESULTS

Net NO chemisorption (corrected for support contribution) per molybde-

num as a function of the molybdenum content is given in Fig. 1A. The data
show that the Step-Ex sulfided catalysts adsorbed appreciably less NO than

aPerformed by P. Blom at Tops~e Laboratories, Denmark.

 201

0.4
)<-- X - - > ( ~

0.2
Z

0 I I I
20

10

I I I

0 I0 20
% Mo

Fig. 1. (A) Chemisorption of NO per Mo (mmol/mmol) and (B) HDS pseudo first-order rate
constant kT per Mo (cma/g min mmol) vs.% Mo loading. Symbols: (©) Std-Sulf; (D) Step-In;
(I) Step-Ex; (X) ref. 6.

the Std-Sulf catalysts. No essential difference in results was obtained for the
calcined and oven-dried catalysts. The data for the Std-Sulf catalysts agreed
well with previous data on catalysts sulfided in an identical way [6]. In order
to determine whether the step-sulfiding procedure or the catalyst exposure to
air (during weighing and charging to the adsorption apparatus) was respon-
sible for the lower NO uptake of the Step-Ex catalysts, the step-sulfiding was
done in-situ (Step-In catalyst). The NO adsorption was again lower, but not
as low as the Step-Ex catalysts (Fig. 1A ). Thus, both in-situ step-sulfiding and
air exposure contribute to lower NO adsorption.
Catalyst HDS activities (in terms of rate constant, kw/Mo) as a function of
molybdenum loading are given in Fig. lB. The Step-Ex catalysts show some-
what lower activities than the respective Std-Sulf catalysts, while the Step-In
catalysts are in between.
In order to determine whether the time of exposure to air affected the NO
adsorption after resulfiding, samples of 7.7% Mo catalysts which had been step
202

sulfided were exposed to laboratory air for extended times. After resulfiding
(Step-Ex procedure), the data of Table 1 were obtained. It can be seen that
continued exposure to air resulted in lower NO uptakes. The last entry shows
that resulting for two hours instead of the usual one-half hour had little effect
on NO adsorption.
The general similarity of the shapes of the curves of Figs. 1A and B suggests
a relationship between NO chemisorption and HDS activity. Fig. 2 displays
such a relationship in terms of kw/NO versus Mo loading. The kw/NO ratio
can be considered an intrinsic activity similar to a turnover frequency. The
remarkable feature of Fig. 2 is essential invariance in kw/NO with molybde-
num loading for all the catalysts. This suggests that the nature of the sites for
NO adsorption and HDS activity does not change with molybdenum content,
only their number decreases. The variation in the Step-Ex catalyst data is most
likely due to different times of exposure of the catalysts to air (see later).
Unfortunately, NO chemisorption measurements could not be made on cat-

TABLE 1

NO chemisorption on Step-Ex catalysts exposed to air for extended times

Resulfiding time Exposure to air NO adsorption

(h) (month) (mmol/g)

0.5 1 0.098
0.5 7 0.088
0.5 16 0.081
2.0 16 0.071

200

mr - lm---m--m

o
Z
)-- I00
[]

© ©

0 I I !

0 5 I0 15 20

%Mo

Fig. 2. Intrinsic HDS activity, kT/NO, vs. % Mo loading. Symbols as in Fig. 1.

 203

alysts after reaction with thiophene because of exposure to air during transfer
of the catalyst to the pulse reactor, invalidating the NO measurements. Since
HDS conversions were taken after 18 h on stream (to obtain line out), the
effect of this long exposure time in the presence of H2S/H2 at 350 °C on NO
adsorption was checked by measuring NO adsorption after 18 h under reaction
conditions (but without thiophene). The results showed little difference in NO
adsorption, viz. 4% and 14% lower for Std-Sulf and Step-Ex catalysts,
respectively.
Fig. 3 displays the relationship between kw/NO and NO/Mo. The Std-Sulf
catalysts all have the same intrinsic activity, independent of the NO/Mo ratio.
A similar situation approximately obtains for the Step catalysts, the In-Step
catalysts being closer to the Std-Sulf catalysts than to the Ex-Step catalysts.
Thus, within each catalyst series, the same intrinsic site activity prevails, but
this activity is different for each series. The high kw/NO, together with the low
NO/Mo for the Step-Ex catalysts, suggests that fewer but more active sites are
present as compared with the Std-Sulf catalysts.
In order to determine whether the two different sites can be distinguished,
temperature-programmeddesorption (TPD) experiments of adsorbed NO were
performed. Fig. 4 shows spectra for a reduced catalyst, a Step-Ex catalyst, and
a Std-Sulf catalyst. Also, TPD was carried out on a sample of MoS2 prepared
to give a reasonably high surface area [8]. All catalysts showed desorption
peaks below 100 ° C due to weakly adsorbed NO. However, the reduced catalyst
and the Step-Ex catalyst exhibited a characteristic peak at 119 oC, while the
MoS2 and Std-Sulf catalyst showed a characteristic peak at 141 ° C. This indi-

200

0
Z
I00
F-

%Mo = 18.2148 11.5 7.7

I I I
0 0.2 0.4

NO/Mo

Fig. 3. Intrinsic HDS activity, kw/NO as a function of NO/Mo. Symbols as in Fig. 1. ([~) 7.7,
( ~ ) 11.3, (A) 14.8, (V) 18.2% Mo.
204

>~

0 200 400

Temperature, eC

Fig. 4. Temperature-programmed desorption of adsorbed NO in helium (a) Mo/A1203 catalyst

reduced in hydrogen at 400°C for 2 h; (b) Step-Ex catalyst; (c) MoS2; (d) Std-Sulf catalyst; (e)
second NO adsorption-TPD of catalyst (d).

cates that the Step-Ex catalyst displays desorption characteristics of the re-
duced catalyst, while the Std-Sulf catalyst resembles that of MoS2.
Fig. 5 displays the results of similar TPD experiments in which the effluent
stream was monitored by mass spectrometry. Again a significant difference in
the NO desorption pattern is seen between the Std-Sulf and the Step-Ex cat-
alysts, the former showing evidence of two peaks, while the latter showing a
single broad peak. In particular, the high-temperature peak for the Std-Sulf
catalyst occurs at a higher temperature, in agreement with the previous TPD
results. Also, N20 was observed in the Std-Sulfpattern, which was not detected
in the Step-Ex pattern. (The apparently low responses of N20 compared to
the data of Jung et al. [ 1 ] may be due to a low sensitivity setting as the relative
intensities of the different species were not quantitative). It is also noted that
 205

/so,
N20~ ..."'"" "........
, j
1 I

i b
c

fNO

j
• . . . . o.

I I I
100 300 500
Temperature, =C

Fig. 5. Mass spectrometic analyses of TPD of adsorbed NO. (A) Std-Sulf catalyst; (B) Step-Ex
catalyst.

some SO2 was generated at high temperature, presumably from reaction of

some oxygen (from NO decompositionto N20 ) with catalyst sulfur. The lower
SO2 peak for the Step-Ex catalyst is in line with its lower NO adsorption.

DISCUSSION

Each series of catalysts show a decrease in NO/Mo with increasing molyb-

denum content, indicative of increasing MoS2 slab size, as NO adsorption has
been shown to be related to relative slab size for standard sulfided catalysts
[3,5 ]. A similar decline in HDS activity with molybdenum loading is also con-
sistent with increasing lateral slab size, as HDS catalytic activity has been
associated with edge sites [10,11]. Furthermore, the invariance in intrinsic
activity (Fig. 2) with molybdenum content indicates that the activity of the
sites for these catalysts are independent of their lateral size.
The relatively low NO chemisorption of the Step-Ex catalysts cannot be due
to larger lateral slab sizes due to sintering of MoS2 because their activities are
not proportionally lowered, i.e. intrinsic activity is not in line with that ex-
pected if the same site activity prevailed as for the Std-Sulf or Step-In cata-
206

lysts. Recent studies have shown that larger slab sizes exhibit the same kT/NO
values [ 12 ].
On air exposure of the sulfided catalysts, oxygen is adsorbed [13-15]. To
explain the lower NO chemisorption, it is proposed that during resulfiding for
1/2 h at 400 ° C, not all of the adsorbed oxygen is removed. The residual oxygen
can produce a more active type of site. For example, Massoth and Kibby [16],
earlier proposed a combination of a vacancy and an oxide ion to be a more
active HDS site than a vacancy and a sulfide ion. Also, deBeer et al. [17]
reported that a sulfided Mo/A1203 catalyst exposed to air had significantly
enhanced initial HDS activity as compared with the in-situ sulfided catalyst.
On this basis, the intrinsic activity of the sites for the Step-Ex catalysts would
be considerably higher than for the Std-Sulf or Step-In catalysts, as found in
Fig. 3. Conceptually, the two types of active sites may be visualized as follows:

0 S Fl 0

Mo / Mo /
(S) (0)

where [] is an anion vacancy. Anion vacancies are believed to be sites for NO

adsorption and HDS activity [18].
A possible reaction scheme leading to Type-O sites is schematically envi-
sioned as follows:

0
/
S [] [] S S 0 0 S--O
\ / \/ \/
Mo Mo ~ Mo Mo

He/& -S02

s\ /s o\ [] s\ / o o\
[]

Mo Mo ~" &O0"C Mo Mo

This accounts both for the formation of Type-O sites and decrease in the total
number of vacancies. Microbalance measurements [13] have shown a slow,
continued oxygen uptake after a rapid adsorption. The slow uptake is evidently
due to adsorption on sulfur as formation of S-O bonds have been found by
XPS [ 19,20 ] on sulfided catalysts exposed to air. Upon exposure of a sulfided
CoMo/Al203 catalyst to air, Parham and Merrill [21], based on extended X-
ray absorption fine structure analysis, suggested an isomorphic substitution
into the MoS2 structure. During heating in helium, evolution of S02 was ob-
served in the mass spectrometry experiments, as was also previously reported
 207

[22]. The oxygen associated with a vacancy is apparently difficult to remove

by sulfiding, as prereduced catalysts were found to sulfide less than oxide cat-
alysts [23].
Although not as marked as the Step-Ex catalysts, the Step-In catalysts also
exhibit a higher intrinsic activity than the Std-Sulf catalysts (Fig. 2). This
suggests that in-situ presulfiding may not be as effective as standard sulfiding
in removing all the oxygen associated with the molybdenum, leading to some
residual oxygen sites.
Although infrared spectra of NO adsorbed show nearly no difference be-
tween sulfided and reduced catalysts [24], our TPD data show differences in
desorption profiles for these catalysts (Fig. 4A vs. 4B). Infrared studies have
shown that NO adsorbs in a dimer or nitrosyl form on sulfided catalysts [2].
Shuxian et al. [25 ] have reported decomposition of NO on bulk MoS2 to occur
below room temperature, with retension of atomic oxygen. The decomposition
of (NO)2 dimer to N20 during TPD also results in some oxygen being left on
the adsorption site. This is evident from spectrum e of Fig. 4, in which NO was
readsorbed after TPD of the Std-Sulf catalyst, whence the 141°C peak was
considerably depressed, while the weaker low-temperature peaks (presumably
due to weakly chemisorbed NO) were unaffected. Additional evidence that
residual oxygen blocks NO adsorption sites comes from NO measurements
before an after TPD, viz., before 0.29, after 0.11 mmol/g.

CONCLUSIONS

Presulfided catalysts exposed to air and then resulfided, exhibit different

properties from in-situ sulfided catalysts. We propose that some of the ad-
sorbed oxygen is not removed by resulfiding, leading to more reactive centers
but less of them. We propose that the more active center consists of an oxygen
anion adjacent to a vacancy site, in contrast to the regular sulfide center of an
sulfur anion and a vacancy site. Step-sulfided catalysts not exposed to air also
exhibit higher intrinsic activities, which is attributed to incomplete sulfiding.
These results show that good correlations between HDS activity and NO
chemisorption cannot be expected for catalyst which are sulfided by different
procedures.

ACKNOWLEDGEMENT

Support of this work by the Office of Basic Sciences of the Department of

Energy is grateful acknowledged.
208

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