SEMINAR NASIONAL TEKNIK KIMIA INDONESIA 2003 ISBN 979-97893-0-3

Yogyakarta, 16-17 September 2003

bersamaan dengan Seminar Nasional
Soehadi Reksowardojo 2003 (ITB) dan Fundamental & Aplikasi Teknik Kimia 2003 (ITS)

Activity Enhancement of AgHZSM-5 Zeolites by Sulfiding with

Hydrogen Sulfide in Pentane and Butane Conversion
Lebong Andalaluna
Deputy for Information, Energy, Material and Environmental Technology,
Agency for Assessment and Application of Technology (BPPT)
Jl. M.H. Thamrin 8 Bldg II Fl. 21, Jakarta 10340
Telp/Fax. (021)3169094/3169095; e-mail : andalaluna@yahoo.com

Masatoshi Sugioka
Department of Applied Chemistry, Muroran Institute of Technology,
27 – 1 Mizumoto-cho, Muroran-shi 050-8585, Japan
e-mail : msugioka@mmm.muroran-it.ac.jp

Abstrak

Activity enhancement of Ag ion-exchanged HZSM-5 zeolite (AgHZSM-5) in the sulfiding with

hydrogen sulfide was studied using acid-catalysed reactions, butenes (1-butene, cis-2-butene)
isomerization, light alkanes (n-pentane, n-butane) conversion and deuterium exchange reaction.
Remarkable enhanced activities for the reactions which are higher than those of HZSM-5 were
obtained in the sulfiding of AgHZSM-5 zeolite at 300ºC. The high enhanced activities was
concluded due to the formation of new strong Brönsted acid sites involving the electron
abstraction effect of silver-sulfide species formed in the sulfiding with hydrogen sufide.

Keywords: AgHZSM-5, Sulfiding, Activity Enhancement

1. Introduction
Hydrogen sulfide is widely considered as poisonous material in the heteregoneous catalytic systems.
Adsorption of sulfur of hydrogen sulfide on the active site will decrease the activity of the catalysts. On
the other hand, there were cases in which hydrogen sulfide promoting the catalysis in the heterogenous
catalytic systems. The authors have been conducting a series studies on the enhancement effect of
hydrogen sulfide over Ag ion-exchanged zeolites (AgNa-zeolites, AgH-zeolites) and mesoporous silicate
material (MeFSM-16) in the acid-catalysed reactions involving the generation of Brönsted acid sites
through the sulfiding [1-6].
In the previous study, the authors reported the enhancement effect of hydrogen sulfide over silver ion-
exchanged proton zeolites (AgH-zeolites) for acid catalyzed reactions [3]. In current work the
enhancement effect of hydrogen sulfide over AgHZSM-5 zeolite and the aspect of activity enhancement
mechanism was studied. The activity enhancement of AgHZSM-5 zeolite was examined by employing
butenes (1-butene, cis-2-butene) isomerization and light alkane (n-pentane, n-butane) conversion as
model reactions.
Infrared spectroscopic studies of hydrogen sulfide and pyridine adsorption on AgHZSM-5 zeolite as
well as deuterium exchange over HZSM-5 and sulfided AgHZSM-5 zeolites were performed in order to
clarify the activity enhancement mechanism of AgHZSM-5 zeolite in the sulfiding with hydrogen sulfide.

2. Experimental
TOSOH Co. HSZ-820NAA NaZSM-5 was used as starting zeolites. HZSM-5 were prepared using 0.1
mol/l HCl aqueous solution. AgHZSM-5 was prepared by ion exchange of HZSM-5 using 0.1 mol/l
aqueous solution of AgNO3. All samples were dried at 110ºC overnight after filtration and calcined in air
at 500ºC for 4 hours. 1-butene and cis-2-butene isomerizations; n-pentane and n-butane conversions were
performed by use of a conventional closed circulating reactor at 0ºC, 75ºC, 220ºC and 200ºC,
respectively. Catalysts were evacuated at 500ºC for 2 hours prior to the reaction and sulfided with 40

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Torr of hydrogen sulfide at 300ºC for one hour followed with 0.5 hour evacuation at the same
temperature. The reaction products were analysed by gas chromatography equipped with propylene
carbonate column.
Infrared spectroscopic measurements were performed by Jasco FT-IR 230S using an in-situ cell.
Samples were evacuated at 500ºC for 2 hours prior to the measurement. Hydrogen sulfide adsorption was
performed by introducing 40 Torr of hydrogen sulfide into the cell at r.t. for one hour followed with 0.5
hour subsequent evacuation at r.t., 100ºC, 200ºC and 300ºC. Pyridine adsorption was performed by
introducing 10 Torr of pyridine into the cell at 150ºC for 0.5 hour followed with 0.5 hour subsequent
evacuation at the same temperature. Deuterium exchange was performed by introducing 100 Torr of
deuterium at 200ºC for 10 hours and the spectras were recorded after 1 hour evacuation at the same
temperature.

3. Results and Discussions

3.1. Activity Enhancement of AgHZSM-5 Zeolite over Butenes Isomerization
The activity enhancement of AgHZSM-5 zeolite in the sulfiding with hydrogen sulfide and the product
selectivity for the isomerization of 1-butene and cis-2-butene is shown in Figure 1. As shown in the figure,
it was revealed that AgHZSM-5 zeolite showed lower activities of the isomerizations than those of its
parent HZSM-5 zeolite which is correlated with the decrease of acid sites of HZSM-5 by Ag ion-
exchange. However, remarkable high enhanced activities were obtained after sulfiding of AgHZSM-5
with hydrogen sulfide and it was revealed that the enhanced activities of AgHZSM-5 were higher than
those of its parent HZSM-5.
It is generally known that for 1-butene isomerization proceed over Brönsted acid sites the product
selectivity (cis/trans ratio) is close to one. On the other hand, selectivity of product in the isomerization
of cis-2-butene (trans/1 ratio) might indicate some aspect of acidity of Brönsted acid sites of the catalysts
[7]. In other word, higher trans/1 ratio is obtained for higher acidity of Brönsted acid sites. On the other
hand, butenes isomerization proceed in stereoselective way over microporous solid acid catalysts such as
zeolite [8]. In 1-butene isomerization, formation of trans-2-butene is favored for the smaller pore size
pertaining to its steric hindrance than that of cis-2-butene. As the result, lower cis/trans ratio is obtained
for zeolite with smaller pore aperture.
As shown in Figure 1, it was observed that sulfided AgHZSM-5 zeolite showed lower cis/trans ratio
than that of HZSM-5. The decrease of selectivity in sulfided AgHZSM-5 zeolite is assumed due to the
increase of stereo-selectivity of zeolite aperture as the result of formation of silver sulfide species in
the sulfiding with hydrogen sulfide. Moreover, it was observed that sulfided AgHZSM-5 showed higher
trans/1 ratio of cis-2-butene isomerization than HZSM-5. It has been assumed that the decrease of

HZSM -5 HZSM-5
AgHZSM -5 Sulfided AgHZSM-5
Sulfided AgHZSM -5 6
30
5
25
Product Selectivity
Activity (%/g.min)

4
20
3
15

10 2

5 1

0 0
1-butene cis-2-butene 1-butene cis-2-butene
isomerization isomerization (cis/trans ratio) (trans/1 ratio)

Figure 1 - The activity enhancement of AgHZSM-5 zeolite by sulfiding with hydrogen sulfide and
product selectivity in butenes isomerizations.
Catalyst wt. : 0.05g (1-butene) and 0.035g (cis-2-butene), sulfiding temperature : 300ºC, reaction
temperature : 0ºC (1-butene) and 75ºC (cis-2-butene).

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product selectivity in 1-butene isomerization is due to narrowing of zeolite aperture as the result of
formation silver sulfide species inside zeolite pore. In the case of cis-2-butene as reactant, formation of
trans-2-butene is favored for smaller pore aperture as the result of higher diffusion rate of trans-2-butene
than 1-butene inside the pore due to smaller permanent dipole moment of trans-2-butene, and trans/1
ratio is expected to increase [8].
It is difficult to define the effect of pore size reduction of sulfided AgHZSM-5 zeolite to trans/1 ratio.
However, it might be possible to assume that the effect of pore size reduction is somewhat small as just
slight decrease of cis/trans ratio was observed over sulfided AgHZSM-5 compare to that of HZSM-5.
There is indication that in term of acidity, sulfided AgHZSM-5 might be better than HZSM-5 as
indicated by higher trans/1 ratio of sulfided AgHZSM-5.

3.2. Activity Enhancement of AgHZSM-5 Zeolite in Light Alkanes Conversion

Straight light alkane conversion is generally known require strong Brönsted acid sites to proceed.
In present study n-pentane and n-butane conversions were employed in order to examine further, the
reactivity of active sites formed over sulfided AgHZSM-5 zeolite. Skeletal isomerization of n-pentane
proceed via a protonated cyclopropane intermediate (cyclopropyl like structure) avoiding the energically
prohibitive stage of primary carbenium ion through a monomolecular mechanism [9]. In the case of
n-butane, opening of the protonated methylcyclopropane ring to a carbocation with iso-C4 structure
occurred via hydride and alkyl shift to form primary carbenium ion and the isomerization would proceed
through bimolecular mechanism [10].
Figure 2 shows the activity enhancement and product selectivity of AgHZSM-5 zeolite in the sulfiding
with hydrogen sulfide for the conversion of n-pentane. As shown in the figure, AgHZSM-5 showed no
activity of n-pentane conversion indicating that most of strong Bronsted acid sites were ion-exchanged
with Ag ion. Induction period was observed over HZSM-5 but not in the case of sulfided AgHZSM-5. It
was revealed that sulfided AgHZSM-5 showed remarkable high enhanced activities for the conversion
which is higher than that of HZSM-5.
HZSM-5
AgHZSM-5 HZSM-5
Sulfided AgHZSM-5 Sulfided AgHZSM-5
50
40

40
Conversion (%)

30
Composition (%)

30

20 20

10
10

0
0 60 120 180 240 300 0
Reaction Time (min) C3 i-C4 n-C4 i-C5
Figure 2 - Activity enhancement and product composition of AgHZSM-5 zeolite in the sulfiding with
hydrogen sulfide for n-pentane conversion.
Catalyst wt. : 0.1 g, sulfiding temperature : 300ºC, reaction temperature : 220ºC

Almost the same composition of product was observed over both of sulfided AgHZSM-5 and
HZSM-5. These results showed the same conversion pathway of n-pentane over sulfided AgHZSM-5 and
HZSM-5 zeolites. Moreover, it was observed that sulfided AgHZSM-5 showed lower branch i-butane and
higher straight-chain n-butane in product composition compare with those of HZSM-5. These results are
assumed due to narrowing of pore aperture of sulfided AgHZSM-5 zeolite as implied from cis/trans ratio
results in 1-butene isomerization.
The activity enhancement and product composition of AgHZSM-5 zeolite by sulfiding with hydrogen
sulfide in the conversion of n-butane is shown in Figure 3. As shown in the figure, induction period was
observed over HZSM-5 and sulfided AgHZSM-5 zeolites. The induction period was temperature
dependence that is shorter for higher temperature. Sulfided AgHZSM-5 was revealed showed remarkable
high enhanced activities in the conversion of n-butane which are remarkably higher than that of HZSM-5,

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 HZSM-5 HZSM-5
Sulfided AgHZSM-5 Sulfided AgHZSM-5
70
20
60
Conversion (%)

Composition (%)
15 50
40
10
30
5 20
10
0
0
0 240 480 720
C3 i-C4 i-C5 n-C5
Reaction Time (min)
Figure 3 - Activity enhancement and product composition of AgHZSM-5 zeolite by sulfiding with
hydrogen sulfide in n-butane conversion.
Catalyst wt : 0.1 g, sulfiding temperature : 300ºC, reaction temperature : 200ºC.

as well as in n-pentane conversion.

Almost the same composition of product was observed over sulfided AgHZSM-5 and HZSM-5. It
was observed that sulfided AgHZSM-5 showed lower isomerization product (i-butane) and higher
cracking product (C3, C5) in product composition compare with those of HZSM-5 which is assumed due
to narrowing of pore aperture of sulfided AgHZSM-5 zeolite.
It was revealed that the reactivity of HZSM-5 and sulfided AgHZSM-5 in n-pentane, n-butane
conversion was in the order of sulfided AgHZSM-5>HZSM-5. This order is in good agreement with the
observation of trans/1 ratio of cis-2-butene isomerization. Therefore, it might be possible to assume that
remarkable high enhanced activities of sulfided AgHZSM-5 in light alkane conversion might be due to
higher acidity of Brönsted acid sites of sulfided AgHZSM-5 than those of HZSM-5.
It was observed that the length of induction period of HZSM-5 and sulfided AgHZSM-5 zeolites in
n-butane conversion is in the order of HZSM-5>sulfided AgHZSM-5. It is interesting that the order is in
the reverse order to reactivity in paraffin conversion and trans/1 ratio of cis-2-butene isomerization.
Therefore, it seems possible to assume that length of induction period in the reaction may correlated with
some chemical aspect of Brönsted acid sites acidity of the catalyst surface.

3.3. Infrared Spectroscopy Study on the Sulfiding of AgHZSM-5 with Hydrogen Sulfide
In order to gain understanding on the mechanism aspect of activity enhancement of AgHZSM-5
zeolite in the sulfiding with hydrogen sulfide, infrared spectroscopic studies on the adsorption of
hydrogen sulfide and pyridine over AgHZSM-5 zeolite as well as deuterium exchange reaction were
performed. Figure 4 shows infrared spectras of AgHZSM-5 zeolite in the hydroxyl and thiol region of
hydrogen sulfide adsorption study. Small hydroxyl absorption bands were observed over AgHZSM-5

Figure 4 - Infrared spectroscopy of AgHZSM-5 in the adsorption of hydrogen sulfide.

a) AgHZSM-5 evacuated at 500ºC for 2 hours.
b) After H2S adsorption and evacuation at r.t.
c) ~ e) After subsequent evacuation at 100ºC, 200ºC, 300ºC.

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zeolite around 3615 cm-1 before hydrogen sulfide adsorption, indicating that most of Brönsted acid sites
of HZSM-5 were exchanged with Ag ion.
Adsorption of hydrogen sulfide at r.t. resulted the appearance of thiol absorption bands around
2558 cm-1 and new hydroxyl bands around 3605 cm-1. These results showed that hydrogen sulfide is
adsorbed dissociatively on Ag ion to form Brönsted acid sites at r.t. The hydroxyl group absorption bands
were observed increased and shifted to higher wave number along with the increase of evacuation
temperature while thiol absorption bands were decreased into broad peaks at 200ºC. The hydroxyl
absorption bands were observed being maximum after evacuation at 200ºC. These results showed that
further dissociation of adsorbed hydrogen sulfide at higher temperature correlated with breakage of
hydrogen-bond with surface hydroxyl groups. It was observed after subsequent evacuation to 300ºC that
new hydroxyl absorption bands were generated at 3610 cm-1 over sulfided AgHZSM-5.
Infrared spectras of ZSM-5 zeolites in the pyridine adsorption are shown in Figure 5. It was observed
that the sulfiding of AgHZSM-5 resulted in decreasing of absorption band correlated to pyridine
coordinated on silver ion at 1450 cm-1, as most of Ag ion transformed into silver sulfide species, and
regeneration of pyridinium absorption band at 1543 cm-1. It is interesting to note that acidic hydroxyl
group absorption band of sulfided AgHZSM-5 was observed at lower wave number and having higher
intensity than that of HZSM-5. These results might implied that the Brönsted acid sites formed over
sulfided AgHZSM-5 has better acidity than HZSM-5 zeolite.

Figure 5 – Infrared spectras of ZSM-5 zeolites in the pyridine adsorption.

a) HZSM-5 evacuated at 500ºC for 2 hours.
b) AgHZSM-5 evacuated at 500ºC for 2 hours.
c) AgHZSM-5, sulfided at 300ºC after evacuation.

Further study regarding the reactivity of Brönsted acid sites generated in the sulfiding with hydrogen
sulfide was performed by performing deuterium exchange reaction. Infrared spectras of ZSM-5 zeolites
over deuterium exchange reaction in OD region is shown in Figure 6. As shown in the figure, OD
absorption bands were observed at 2663 cm-1 and 2662 cm-1 for HZSM-5 and sulfided AgHZSM-5,
respectively.

Figure 6 - Infrared spectras of ZSM-5 zeolites in OD-region. a) HZSM-5, b) sulfided AgHZSM-5.

Sulfiding temperature : 300ºC, D2 treatment : 100 Torr D2 at 200ºC for 10 hours followed with 1 hour
evacuation at the same temperature.
It was revealed that OD absorption band of sulfided AgHZSM-5 was observed at lower wave number

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than HZSM-5 as well as OH absorption band. Moreover, sulfided AgHZSM-5 was observed having
higher intensity of OD absorption band than HZSM-5, indicating higher reactivity of sulfided AgHZSM-5.
Based on these results, it is concluded that higher enhanced activity of sulfided AgHZSM-5 than
sulfided HZSM-5 might be due to higher acidity of newly formed Brönsted acid sites of sulfided
AgHZSM-5.

3.4. Mechanism of AgHZSM-5 Zeolite Activity Enhancement

Based on the results obtained in this study, we propose a possible mechanism of activity enhancement
in the sulfiding of AgHZSM-5 zeolite as shown in Scheme 1. Most of the proton of HZSM-5 is
exchanged with silver ion to form AgHZSM-5. Sulfiding of AgHZSM-5 with hydrogen sulfide resulted
the formation of silver-sulfide cluster which might be electronegatively charged ([AgSy]-) and the
generation of Brönsted acid sites. The electron abstraction effect of this silver sulfide cluster would
increase the acidity of generated Brönsted acid sites and as a result, sulfided AgHZSM-5 zeolites showed
higher catalytic activity than HZSM-5.

Scheme 1 - Activity enhancement mechanism of AgHZSM-5 in the sulfiding with hydrogen sulfide.

Conclusion
It was revealed that the catalytic activities of AgHZSM-5 zeolite for acid-catalysed reactions (butenes
isomerization, alkanes conversion) were enhanced remarkably by sulfiding with hydrogen sulfide and the
enhanced activities were remarkably higher than those of HZSM-5. By sulfiding AgHZSM-5 with
hydrogen sulfide, new Brönsted acid sites were generated and the acidity of new Brönsted acid sites
might be increased by electron abstraction effect of silver sulfide cluster which is assumed to be
electronegatively charged.

References
1. Masatoshi Sugioka, (1993), “Activity Enhancement of Metal Ion Containing Catalysts by Sulfiding
with Hydrogen Sulfide”, Critical Reviews in Surface Chemistry, 3(2), p. 101-129
2. L. Andalaluna and M. Sugioka, (1996), “Activity Enhancement of Silver Ion-Exchanged Zeolites
(AgNa-zeolites) by Sulfiding with Hydrogen Sulfide”, Proceeding Regional Symposium Chemical
Engineering 1996, 3-10-1
3. M. Sugioka and L. Andalaluna, (1996), “Activity Enhancement of H-zeolites by Ag Ion-Exchange
and Sulfiding with Hydrogen Sulfide”, Studies in Surface Science and Catalysis Vol. 105, p. 1995
4. L. Andalaluna and M. Sugioka, (2001), “Acticity Enhancement of Silver Ion-exchanged Sodium
Zeolites (AgNa-zeolites) by Sulfiding with Hydrogen Sulfide”, Proceeding Regional Symposium
Chemical Engineering 2001, CR17-1
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Sulfiding with Hydrogen Sulfide”, Proceeding 4th Quality in Research Seminar, IV-1-2-1
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FSM-16 by Metal Ion-exchange and Sulfiding with Hydrogen Sulfide”, Studies in Surface Science
and Catalysis Vol. 129, p. 823-828
7. T. Okuhara and M. Misono, (1983), “Test Reaction : 1-Butene Isomerization”, Shokubai (Catalyst
and Catalysis) Vol. 25(4), p. 279-283
8. M. Richter, H.-L. Zubowa, E. Schreier, B. Parlitz and J. Richter-Mendau, (1994), “Double Bond
Isomerization of n-butenes over Silicon Modified Aluminophosphate Molecular Sieve Catalysts”,
Zeolites Vol. 14, p. 414-426
9. H. Liu, G. D. Lei, and W. M. H. Sachtler, (1996), “Alkane Isomerization over Solid Acid Catalysts
Effect of One-Dimensional Micropores”, Applied Catalysis A Vol. 137, 167-177
10. R. A. Asuquo, G. Eder-Mirth, and J. A. Lercher, (1995), “n-Butane Isomerization over Acidic
Mordenite”, Journal of Catalysis Vol. 155, 376-382

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