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)

Noble Metals Supported on Mesoporous Materials MCM-41

Hydrodesulfurization Catalysts
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

Yasuharu Kanda and 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

Pt/MCM-41 catalysts showed high and stable catalytic activity for the hydrodesulfurization of
thiophene at 350ºC and the activities were higher than that of commercial catalyst
CoMo/Al2O3. Acidc property of support material MCM-41 and the spillover hydrogen formed
on Pt particle in Pt/MCM-41 catalysts play important roles for the hydrodesulfurization of
thiophene.

Keywords:Noble metal, mesoporous MCM-41,acidity control, thiophene hydrodesulfurization

1. Introduction
Fast growing of demand for transportation fuel that meet changing environmental regulation bring
challenge for production of clean petroleum feedstocks in the petroleum industry. The importance to
fulfill the growing transportation fuels demand that meet the environmental regulation, where petroleum
feedstocks should be clean and least polluting, is urged for regional and global environment protection. It
is stated in various countries that sulfur content for the diesel fuel would be lessen to 50 ppm level by
2005 as a goal. This goal is setted in order to limit the emission of the oxides of the sulfur (SOx) which
lead to acid rain, ozone depletion and smog. On the other hand, low-sulfur fuels would enable the
automobile manufacturers to implement their advanced low-sulfur sensitive technology that can reduce
further the emission of oxide and nitrogen particulate of fuel combustion.
One of the strategy for achieving above target of producing clean petroleum feedstocks, is by
developing new highly active hydrodesulfurization catalysts which is much more active than present
industrial hydrotreating catalysts. The authors has proposed that one potential concept to achieve the goal
is by employing the combination of acidic properties of support materials, such as mesoporous silicates
MCM-41 [1], FSM-16 [2], and SBA-15 [3], and supported metal active species as hydrodesulfurization
catalyst [4-6].
The authors have reported that noble metals supported on mesoporous silicates, especially
Pt/mesoporous silicates, showed high and stable activity in the hydrodesulfurization of thiophene. It was
proposed that the acid sites of support material mesoporous silicates playing important role for the
activation of thiophene, while hydrogen is activated on Pt particle to form spillover hydrogen that would
attacks the activated thiophene, in the tiophene hydrodesulfurization. Therefore, it is desirable to define
methodology to control the surface acidity of support material that would possibly improve further the
catalytic performance of the catalyst system.
In the present work, silicate and aluminosilicate MCM-41 (SiMCM-41, SiAlMCM-41) was
synthesized and applied as support material of noble metal catalysts for thiophene hydrodesulfurization.
We also studied the effect of application of SiMCM-41 modified with impregnation of Al2O3 and Al-sec-
butoxide as support material of Pt (Pt/Si(Al)MCM-41, Pt/Si(Al-OR)MCM-41) for thiophene
hydrodesulfurization, in order to develop highly active mesoporous material based hydrodesulfurization
catalyst.

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2. Experimental
Mesoporous silicate (SiMCM-41) MCM-41 was synthesized using DTABr, TPABr, CTAC surfactants
(Aldrich) with SiO2.Na2O as silica source. Acidic AlSiMCM-41, was synthesized by adding sodium
aluminate (NaAl2O4) during synthesisvwith Si/Al 5, 15, 30 to the gels mixture. Obtained hexagonal
structure of SiMCM-41 was further impregnated with Al aqueous solution or Al-sec-butoxide 1 wt% and
4 wt% metal loading to obtain Si(Al)MCM-41 and Si(Al-OR). All catalysts were calcinet at 500ºC for
4 hours in air and reduced at 450ºC for 1 hour prior to the reaction. Presulfiding treatment of the catalysts
was performed using 5% H2S-H2 gas mixture at 400ºC for 1 hour.
Hydrodesulfurization of thiophene was carried out at 350ºC under atmospheric pressure, employing
0.1 g amount of catalyst by use of a conventional fixed bed flow reactor. Thiophene was introduced into
the reactor by passing hydrogen (30 ml/min) through thiophene trap cooled at 0ºC. The reaction products
were analyzed by Shimadzu gas chromatograph equipped with SD-550 column.
Characterization of SiAlMCM-41 and surface modified SiMCM-41 was performed by employing
infrared spectroscopic measurement of pyridine adsorption using Jasco FT-IR spectrometer. Pyridine
adsorption was performed at 100ºC.

3. Results and Discussions

3.1. Catalytic Activities of Noble Metals Supported on MCM-41 in the Hydrodesulfurization of
Thiophene

The hydrodesulfurization of thiophene over various noble metals (Pt, Pd, Rh, Ru) supported on
mesoporous silicate MCM-41 catalysts at 350°C is shown in Figure 1. The catalytic activities of noble
metals/SiMCM-41 were observed vary remarkably for differend kind of noble metal supported on
SiMCM-41 and the catalytic activities after 2 hours reaction were revealed in the order as follow;
Pt/SiMCM-41 > Pd/SiMCM-41 > Rh/SiMCM-41 >> Ru/SiMCM-41. Moreover, Pt/SiMCM-41
and Pd/SiMCM-41 catalysts was revealed showing higher initial activities than that of commercial
catalyst CoMo/Al2O3. It was observed that the high activities of both catalysts were kept steady after
5 hours reaction.

100
5 wt% Pt/SiMCM-41
5 wt% Pd/SiMCM-41
80 5 wt% Rh/SiMCM-41
5 wt% Ru/SiMCM-41
Conversion (%)

CoMo/Al2O3
60

40

20

0
0 60 120 180 240 300
Time on S tream (min)

Figure 1 - Thiophene hydrosulfurization over noble metals supported on mesoporous silicate MCM-41
(SiMCM-41).
W/F = 37.9 g.h/mol, reaction temperature 350°C

Figure 2 shows the hydrodesulfurization of thiophene over various noble metals (Pt, Pd, Rh, Ru)
supported on mesoporous aluminosilicate MCM-41 (SiAlMCM-41, Si/Al=15) catalysts at 350°C. The
effect of application of acidic support to the catalytic activities of noble metals/MCM-41 were observed
vary remarkably for differend kind of noble metals. and the catalytic activities after 2 hours reaction were
revealed in the order as follow; Pt/SiAlMCM-41 > Pd/SiAlMCM-41 > Rh/SiAlMCM-41 >>
Ru/SiAlMCM-41. Moreover, Pt/SiAlMCM-41catalyst was revealed showing much higher activity than
that of commercial catalyst CoMo/Al2O3 at steady after 5 hours reaction. It was found that the application
of acidic support was very effective to improve the hydrodesulfurization of Pt based catalyst system.

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 100

80

Conversion (%)
60

40

5 wt% Pt/SiAlMCM-41
20 5 wt% Pd/SiAlMCM-41
5 wt% Rh/SiAlMCM-41
5 wt% Ru/SiAlMCM-41
CoMo/ALO
0
0 60 120 180 240 300
Time on S tream (min)

Figure 2 - Thiophene hydrosulfurization over noble metals supported on mesoporous aluminosilicate

MCM-41 (SiAlMCM-41, Si/Al=15).
W/F = 37.9 g.h/mol, reaction temperature 350°C

3.2. Catalytic Activities of Pt Supported on Acidic SiAlMCM-41 in the hydrodesulfurization of

thiophene

In order to study further the effect of support acidity to Pt/MCM-41 catalysts system we employing
several SiAlMCM-41 (Si/Al = 30, 15, 5) with different acidic properties in order to examine the effect
of support acidity properties toward the hydrodesulfurization performance of Pt/SiAlMCM-41 catalysts.
It is assume that the acidic properties of support material is in the order of Si/Al as follow :
Si/Al=30<15<5 as studied in the infrared spectroscopic measurement of pyridine adsorption.
Catalytic activities of Pt supported on various mesoporous aluminosilicate MCM-41 in the
hydrodesulfurization of thiophene is shown in Table 1. The activities were based on conversion after
2 hours reaction. As shown in the table, Pt/SiAlMCM-41 with Si/Al=15 showed the best thiophene
hydrodesulfurization activity which lead to the conclusion that medium acidity (Si/Al=15) of support
material would be most suitable for synthesizing highly active Pt/SiAlMCM-41 catalyst system for
thiophene hydrodesulfurization. Less (Si/Al=30) or high (Si/Al=5) acidic support material would lead to
the decrease of catalytic performance. It is assumed that proper acidic properties of support material
would improve the hydrogenation capability of the catalyst system that lead to higher thiophene
hydrodesulfurization catalytic performance, as higher saturated product of n-C4 observed as shown
in Table 1.

Table 1 – Thiophene Hydrodesulfurization over Pt supported on Acidic SiAlMCM-41

Composition (%)
Catalysts Conversion (%) C1-C3 n-C4 1-C4= t-2-C4= c-2-C4=

CoMo/ALO 46.4 0.6 17.5 17.6 36.3 28.0

5 wt% Pt/SiMCM-41 51.5 1.9 71.5 6.5 11.4 8.3

5 wt% Pt/SiAlMCM-41 (Si/Al=30) 62.8 0.5 78.8 5.5 8.7 6.5

5 wt% Pt/SiAlMCM-41 (Si/Al=15) 74.1 1.4 90.6 1.3 3.8 2.8
5 wt% Pt/SiAlMCM-41 (Si/Al = 5) 36.0 0.6 71.8 7.2 11.6 8.8

W/F = 37.9 g.h/mol, reaction temperature 350°C

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3.3. Catalytic Activities of Pt Supported on Surface Modified SiMCM-41 in the
hydrodesulfurization of thiophene

In previous study we have reported the application of SiMCM-41 modified with aqueous solution
Al2O3 as support material for Pt improved the catalytic performance of Pt/mesoporous silicate in the
hydrodesulfurization of thiophene. The improvement is concluded having related with the increase of
surface acidity of support material in the catalyst system. In this study we examine further the
modification of siliceous SiMCM-41 in order to improve the catalytic activity in thiophene
hydrodesulfurization. In the study, siliceous SiMCM-41 was modified with aqueous solution Al2O3 and
organic Al-sec-butoxide with Al metal loading 1 wt% and 4 wt% and the hydrodesulfurization
performance with Pt as supported metal was evaluated.
Catalytic activities of Pt supported on surface modified mesoporous silicate SiMCM-41 (Si(Al)MCM-
41, Si(AL-OR)MCM-41) in the hydrodesulfurization of thiophene is shown in Table 2. The activities
were based on conversion after 2 hours reaction. As shown in the table, the application of SiMCM-41
modified with both of Al2O3 and Al-sec-butoxide improve the catalytic performance in thiophene
hydrodesulfurization.
It was observed that for modification with aqueous solution Al2O3, the performance improvement is
better for lower Al metal loading. It was also observed, that higher saturated product n-C4 obtained at
lower Al metal loading, indicating better hydrogenation capability have some contribution for fine
activity of Pt/SiAl(1)MCM-41.
On the other hand, for modification with organic Al-sec-butoxide the improvement is better for higher
metal loading. It is interesting to note that lower saturated product n-C4 obtained for higher Al metal
loading. It is assumed that acidic properties of support material plays an important role for the catalytic
activity improvement.

Table 2 - Thiophene Hydrodesulfurization over Pt supported on Acidic SiAlMCM-41

Composition (%)
Catalysts Conversion (%) C1-C3 n-C4 1-C4= t-2-C4= c-2-C4=

CoMo/Al2O3 46.4 0.6 17.5 17.6 36.3 28.0

5 wt% Pt/SiMCM-41 51.5 1.9 71.5 6.5 11.4 8.3

5 wt% Pt/Al(1)SiMCM-41 64.4 0.6 86.9 2.2 5.9 4.3

5 wt% Pt/Al(4)SiMCM-41 62.8 1.0 82.9 4.6 6.6 5.0

5 wt% Pt/Al-OR(1)SiMCM-41 60.7 0.4 90.7 1.4 4.3 3.1

5 wt% Pt/Al-OR(4)SiMCM-41 65.0 0.8 84.4 4.4 5.9 4.5

W/F = 37.9 g.h/mol, reaction temperature 350°C

3.4. Surface Characterization of Supported Materials MCM-41

We have proposed in previous study that surface acidity of support material plays an important role for
high activity of Pt/mesoporous material catalyst system for thiophene hydrodesulfurization [6-8]. In order
to clarify the acidity properties of synthesized mesoporous aluminosilicate ant the effect of modification
of SiMCM-41 with Al2O3 and Al-sec-butoxide, we observed the infrared spectras of SiMCM-41,
SiAlMCM-41, surface modified SiMCM-41 in the pyridine adsorption.
Figure 3 shows infrared spectras of pyridine adsorbed on SiAlMCM-41. Pyridine was adsorbed at
100°C followed with evacuation at the same temperature. It was observed that SiMCM-41 shows weak
absorption of coordinated pyridine at Lewis acid site indicating the present of small amount of Lewis acid
sites. In the case of SiAlMCM-41 small absorption band based on Bronsted acid sites was observed
around 1550 cm-1.
Infrared spectras of pyridine adsorbed on SiMCM-41 modified with aqueous Al2O3 and organic
Al-sec-butoxide with metal loading 4 wt% is shown in Figure 4. It was observed that the modification of

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siliceous SiMCM-41 with Al impregnation resulting the appearance of pyridinium ion absorption band
around 1550cm -1. These results clarified that modification of siliceous SiMCM-41 with aqueous Al2O3
and organic Al-sec-butoxide might be a fine method for controlling surface acidity of silicate mesoporous
material, correlated with synthesizing highly active noble metal based hydrodesulfurization catalyst.

Si/Al = 5
0.1

Abs

Si/Al = 15

Si/Al = 30

SiMCM-41

1570 Wave Number [cm-1] 1400

Figure 3 – Infrared spectras of SiAlMCM-41 (Si/Al = 30, 15, 5) in the pyridine adsorption region.
Pyridine was adsorbed at 100°C.

c)

0.02
b)

Abs a)

1680 Wave Number [cm-1] 1380

Figure 4 - Infrared spectras of SiMCM-41 modified with Al2O3 and Al-sec-butoxide in the pyridine
adsorption region. A) SiMCM-41, b) SiAlOR(4)MCM-41, c) SiAl(4)MCM-41
Pyridine was adsorbed at 100°C.

Summary

It was found that the application of acidic support material in the Pt/MCM-41 would improve the
catalytic performance in thiophene hydrodesulfurization. Medium acidity is concluded the best condition
to synthesize highly active Pt/MCM-41 hydrodesulfurization catalyst. Some methods such as
modification of siliceous SiMCM-41 with Al2O3, Al-sec-butoxide was demonstrated as effective way to
control surface acidity of support material MCM-41 in order to synthesize highly active
hydrodesulfurization catalyst. Therefore, the control of surface acidity of support material mesoporous

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silicates is an important aspect for the synthesis of highly active hydrodesulfurization catalysts based on
noble metals and mesoporous materials.
Based on results in the study we popose a possible mechanism of thiophene hydrodesulfurization over
Pt/MCM-41 as shown in scheme 1. In the proposed mechanism, thiophene is activated on the acid site of
mesoporous silicates and hydrogen is activated on Pt to form spillover hydrogen. The spillover hydrogen
formed on Pt particle attacks the activated thiophene formed on the acid site of mesoporous silicates.

Scheme 1 – Hydrodesulfurization mechanism of thiophene over Pt/Mesoporous catalyst

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