Dissertations

University of Joensuu
Department of Chemistry
40/1999

Mika Suvanto

Hydrotreating Catalysts Based

on Tungsten Hexacarbonyl:
Controlled Preparation,
Characterisation and Activity in
Thiophene Hydrosulphurisation
CO
CO
CO
CO W CO

n CO

CO

Preparation

+
H2 S

Catalysis

Surface

Characterisation
Modelling

Hydrotreating Catalysts Based on Tungsten

Hexacarbonyl: Controlled Preparation,
Characterisation and Activity in Thiophene
Hydrodesulphurisation

Mika Suvanto

Department of Chemistry
University of Joensuu
Finland

Joensuu 1999

Mika Suvanto
Department of Chemistry, University of Joensuu
P.O. Box 111, FIN-80101 Joensuu, Finland

Supervisor
Prof. Tapani Pakkanen, University of Joensuu

Referees
Prof. Jouni Pursiainen, University of Oulu
Dr. Jari Kiviaho, VTT

Opponent
Prof. Risto Laitinen, University of Oulu

To be presented with the permission of the Faculty of Science of the University of

Joensuu for public criticism in the auditorium K1, Yliopistokatu 7, Joensuu on June
11th, 1999, at 12 o`clock noon.

Copyright 1999 Mika Suvanto

ISSN 1456-3975
ISBN 951-708-770-5

Joensuun yliopistopaino
Joensuu 1999

ABSTRACT
Hydrotreating catalysts based on tungsten oxide and supported on alumina are usually
prepared from hexavalent salts of tungsten by a liquid phase method such as
impregnation. A particular disadvantage of these traditional tungsten oxide catalyst is
that they are relatively difficult to reduce or to activate by sulphurisation at moderate
temperature. Thus, the development of a new preparation process for low valent
tungsten catalysts that can be activated without harsh reduction treatment would be
advantageous.
This thesis describes a novel route for the preparation of alumina supported tungsten
and tungsten cobalt hydrotreating catalysts. Zerovalent carbonyl precursor based
catalysts were prepared by controlled and gradual gas phase adsorption in a fluidised
bed reactor. The preparation process was monitored by diffuse reflectance Fourier
transform IR (DRIFT) and temperature programmed methods (TPR, TPO, PCO and
NH3-TPD). Interaction energies of tungsten hexacarbonyl with the various surface sites
of alumina were estimated by DFT calculations. The catalytic activity of the catalysts
was tested in thiophene hydrodesulphurisation (HDS) in a custom built batch reactor.
Catalytically relevant metal loadings with linear growth were achieved by applying the
pulse technique in catalyst preparation. The formation of unwelcome oxide-type
surface structures during preparation was observed to depend on the gas atmosphere
and temperatures applied. A partial decarbonylation introduced between the deposition
pulses hindered the formation of these oxidised species. Promising activities were
achieved, especially with bimetallic CoW/Al2O3 catalysts, where the existence of a
synergetic phase was suggested. The measurements of activity and reduction indicated
that use of the new method of preparation, together with zerovalent precursors, leads to
adsorbed surface species that are more easily activated by sulphur and more easily
reduced than traditional tungsten oxide catalysts.

LIST OF ORIGINAL PUBLICATIONS

This dissertation is a summary of publications I-III and submitted manuscripts IV-V.

Suvanto M. and Pakkanen T.A., Tungsten Hexacarbonyl on Alumina:

Controlled Deposition from Gas Phase, Appl. Catal. A, 166 (1998) 105.

II

Suvanto M. and Pakkanen T.A., Deposition of Tungsten Hexacarbonyl on

Alumina: A Diffuse Reflectance Infrared Fourier Transform Spectroscopy
Study, J. Mol. Catal. A: Chem., 138 (1999) 211.

III

Suvanto M., Rty J. and Pakkanen T.A., Catalytic Activity of Carbonyl

Precursor Based W/Al2O3 and CoW/Al2O3 Catalysts in Hydrodesulfurization
of Thiophene, Appl. Catal. A, 181 (1999) 189.

IV

Suvanto M., Rty J. and Pakkanen T.A., Temperature Programmed Studies on

Carbonyl Precursor Based W/Al2O3 and CoW/Al2O3 Catalysts, submitted.
(accepted 5 August, Catal.Lett., 62 (1999) 21.)

Myllyoja S., Suvanto M., Kurhinen M., Hirva P. and Pakkanen T.A.,
Interaction of M(CO)6 (M=Cr, Mo, W) with Surface Sites of Al2O3: A
Theoretical Study, submitted. (accepted 28 July, Surf. Sci., 441 (1999) 454.)

CONTENTS
Abstract
List of original publications
Contents
Abbreviations

3
4
5
6

1. INTRODUCTION
1.1. Hydrodesulphurisation and hydrotreating catalysts
1.2. Tungsten based catalysts
1.3. Aims of the study

7
7
8
9

2. CATALYST PREPARATION BY GAS PHASE ADSORPTION

2.1. General
2.2. Deposition of tungsten hexacarbonyl on alumina

9
9
10

3. CHARACTERISATION OF CATALYSTS AND CATALYST

PRECURSORS
3.1. Characterisation of alumina adsorbed W(CO)6 by Fourier transform
infrared spectroscopy
3.2. Modelling of tungsten carbonyl species on surface sites of alumina
3.3. Characterisation by temperature programmed methods
3.3.1. Temperature programmed reduction
3.3.2. Temperature programmed oxidation and oxygen pulse
chemisorption
3.3.3. Temperature programmed desorption of ammonia

14
14
18
20
20
23
26

4. HYDRODESULPHURISATION ACTIVITY OF W/Al2O3 AND

CoW/Al2O3 CATALYSTS
4.1. Reactor arrangement
4.2. Results of hydrodesuphurisation tests

27
27
28

5. CONCLUSIONS

30

Acknowledgements
References

32
33

ABBREVIATIONS
ALCVD
ALE
CVD
DFT
DRIFT
EDXRF
ESR
HDN
HDO
HDS
IR
NH3-TPD
PCO
TPD
TPO
TPR

atomic layer chemical vapour deposition

atomic layer epitaxy
chemical vapour deposition
density functional theory
diffuse reflectance infrared Fourier transform
energy dispersive X-ray fluorescence
electron spin resonance
hydrodenitrogenation
hydrodeoxygenation
hydrodesulphurisation
infrared
temperature programmed desorption of ammonia
oxygen pulse chemisorption
temperature programmed decomposition
temperature programmed oxidation
temperature programmed reduction

1. INTRODUCTION
1.1. HYDRODESULPHURISATION AND HYDROTREATING
CATALYSTS
Hydrodesulphurisation (HDS) is a process employed to remove sulphur from
petroleum and other fossil fuel feedstocks through reaction with hydrogen.1,2,3 In this
reaction the C-S bond breaks and the liberated sulphur is fixed as H2S. A general
reaction pathway for the HDS of thiophene is represented in Scheme 1.
S

n H2

catalyst

+ H2S

[1]

The hydrodesulphurisation reaction is of critical importance in petroleum refining

because the various sulphur compounds of fossil materials such as thiols, sulphides,
thiophenes and benzothiophenes affect the quality of products. Considering the current
world petroleum production of several tens of million barrels per day,
hydrodesulphurisation is probably one of the largest volume industrial applications of
transition metal catalysis. Corresponding reductive treatments have been developed for
the removal of nitrogen (HDN), oxygen (HDO) and metals from oil fractions and they,
along with hydrodesulphurisation, are collectively referred to as hydrotreating
processes. The upgrading of crude oil and coal derived liquids is of considerable
environmental importance. Any decrease in the amounts of sulphur and nitrogen
oxides in combustion gas will contribute to the diminishing of acid rain. Besides the
environmental aspects, most oil refining catalysts, such as noble metal and zeolite, can
not tolerate sulphur compounds, which means that sulphur must be removed from oil
fractions before further processing of oil products.1,2,3
The first hydrotreating catalysts, unsupported metal sulphides used to liquefy coal,
were developed in the 1920s. However, it took several decades before their structure
and catalytical action were reasonably understood. During the 1970s it was discovered
that the active metal, usually molybdenum, formed small disulphide particles, which
were located in the pores of the alumina support. A fair understanding of the structure
and role of the promoter metal was not established until the 1980s.1,3
Modern hydrotreating catalysts are based on molybdenum oxide supported on alumina
and promoted by cobalt or less often tungsten promoted by nickel. The activation of
oxide-form catalyst is usually carried out by H2S/H2 treatment. The structure of the
catalytically most active site in the sulphided catalyst has been widely studied and the
existence of the so-called CoMoS phase is generally accepted.1,4,5 The structure of this
synergetic phase is based on MoS2 microcrystals interacting in basal or edge
orientation with the alumina surface.1,4 Several models have been proposed for the
attachment of the promoter metal to MoS2 and the location at edge positions has been

regarded as providing the most active structure.1 Besides these two active metals,
hydrotreating catalysts may contain other elements, such as phosphorus, boron,
fluorine and chlorine, to modify the structural and mechanical properties of the
catalyst.3

1.2. TUNGSTEN BASED CATALYSTS

The chemical properties of tungsten are similar to those of molybdenum and the
formation of a corresponding active transition metal phase for the hydrotreating
process (WS2) has been observed.3,6-12 Tungsten catalysts are less studied and applied
in industry than the corresponding molybdenum based hydrotreating catalysts,
however. In part this is due to the higher cost of tungsten than molybdenum. During
the present decade, the need for more effective and environmentally benign catalysts
has increased the number of studies devoted to the structure and catalytic action of
tungsten based hydrotreating catalysts. The tungsten oxide based hydrotreating
catalysts are commonly promoted by nickel,6-9,13-23 while the use of other promoters,
such as cobalt, has been less thoroughly studied.24-29
Tungsten oxide based catalysts supported on alumina are commonly prepared by a
liquid phase method such as impregnation. Depending on the starting material,
typically ammonium tungstate ((NH4)6H2W12O40), and on the conditions of preparation,
a variety of oxide phases and dispersion of metal can be achieved. The preparation
process itself is simple and the metal content can be increased to a moderately high
level.30 However, because the solvent may interfere in liquid phase methods, the
formation of adsorbed tungsten structures is difficult to precisely control. A second
unfavourable feature of supported tungsten catalysts prepared by impregnation
methods is that the oxide structures that are formed are more difficult to reduce11-13,31-36
and sulphurise6-8,11,12 at moderate temperatures than are their bulk oxides. This
difficulty, which undoubtedly has dampened industrial interest in them, has been
attributed to the strong interactions between the adsorbed tungsten species and the
oxide support.7,11-13,31,32,36
An alternative approach, to avoid the problems associated with oxide based catalysts, is
to change the starting material of the catalyst preparation to zero valent complex of
tungsten, such as tungsten hexacarbonyl. The use of tungsten hexacarbonyl, which also
is a volatile complex, has the added advantage of allowing a gas phase preparation
method and avoidance of the solvent effect. The benefits of the zerovalent precursor
are easily lost, however, as a consequence of oxidative surface reactions.37-40 Strict
control of the preparation process is thus an essential requirement.
Several studies concerning the surface chemistry and catalytic activity of alumina
adsorbed W(CO)6 have been reported.37-47 The main purpose of these earlier studies
was to clarify the formation of subcarbonylic species during decarbonylation. The
catalytic activity of alumina-supported tungsten carbonyl has also been studied. Whilst

tungsten hexacarbonyl based catalysts have been tested in olefin disproportionation,48

metathesis,41,49 alkene hydrogenation50 and Fisher-Tropsch synthesis,51 there is no
indication of its use in hydrotreating processes such as hydrodesulphurisation. In the
earlier studies, impregnation and various gas phase methods, such as adsorption in a
vacuum cell and dry mixing, were utilised to adsorb W(CO)6 on alumina. The problem
with these two methods is that neither is easily controlled. In addition, the achieved
metal contents have been fairly low.

1.3. AIMS OF THE STUDY

The principal aim of this study was to develop a carbonyl precursor based controlled
route to increase tungsten content on the alumina surface and to find a better way to
produce active hydrodesulphurisation catalysts. Gas phase adsorption in a fluidised bed
reactor was applied in catalyst preparation. The gradual deposition process and the
surface species that formed were characterised by diffuse reflectance infrared Fourier
transform (DRIFT) spectroscopy. Modelling techniques were applied as a means of
clarifying the first interactions of the carbonyl complex with different surface sites of
alumina. In addition, the surface properties of prepared W/Al2O3 and CoW/Al2O3
catalysts were studied by several temperature programmed methods including TPD,
TPR, TPO, PCO and NH3-TPD. Hydrotreating activity of the carbonyl precursor based
catalysts was evaluated in thiophene hydrodesulphurisation in a custom developed
batch reactor.

2. CATALYST PREPARATION BY GAS PHASE

ADSORPTION
2.1. GENERAL
A chemical method where deposition takes place by adsorption or reaction from the
gas phase is generally referred to as chemical vapour deposition (CVD).52 The system,
originally developed for the growing of thin films, has been extended to provide a
potential route to prepare structurally well-defined porous catalytic surfaces. According
to the starting material and deposition conditions, the CVD techniques can be further
divided into several sub and special modes. In view of its interest as a method of
catalyst preparation, Atomic layer epitaxy (ALE or ALCVD) deserves mention in this
context.52-55 In the ALCVD method, each deposition pulse results in surface saturation
and the growth is controlled not by the dose of reactant but by the surface itself. A
primary demand for any gas solid based method of preparation is the existence of
suitable starting material which can be vaporised at moderate temperature.
In methods where each deposition pulse does not lead to complete surface saturation,

10

ensuring the homogeneity of the preparation process becomes a challenging task. In

contrast to the ALCVD process, where the use of a static bed always leads to good
homogeneity, in sub-saturation processes a uniform metal loading is not so easily
produced. One approach to the problem is to employ a fluidised bed system. The
advantages of the fluidised bed system are the acceleration of temperature and mass
flow and effective mixing. Gradients do not easily occur and the reacting surface areas
between adsorbate and support can be optimised.56 In practice, this means that
fluidisation during deposition offers homogeneous reaction conditions for all surface
particles and the gaseous precursor can more effectively enter the pores.

2.2. DEPOSITION OF TUNGSTEN HEXACARBONYL ON ALUMINAI

Three methods of preparation were tested as a means to controlling the surface
processes and growth of tungsten content on alumina. The primary aim here was to
find a route for the preparation of a low valent and well dispersed tungsten catalyst. All
depositions mentioned in this section were made on -alumina (Aldrich, 150 mesh, 155
m2/g) pre-treated at 500C under vacuum. After partial dehydroxylation, all handling
of the support material was done in a nitrogen glove box without exposure to air or
moisture.
4

Tungsten [wt%]

3.5
3
2.5

90C

80C

1.5
1
0.5
0
5

10

15

20

decarb.

Deposition time [h]

Figure 1. Tungsten content on alumina as a function of deposition time and two

sublimation temperatures, 80 and 90C (temperature of reactant vessel). Temperature
of the fluidised bed reactor was 100C in both cases.
In the first method, adsorption was allowed to take place over an extended period of
continuous deposition. Figure 1 presents the amount of tungsten loading (determined
with an energy dispersive X-ray fluorescence spectrometer, EDXRF) as a function of
deposition time and two different sublimation temperatures. As the figure shows, the

11

tungsten loading increased most effectively during the first few hours at both
temperatures and during the remainder of the reaction time there was only a slight
increase in metal content. The results indicate that the equilibrium level was achieved
or was very close to being achieved.
The clear difference in the amounts of tungsten deposited at 80 and 90C almost
vanishes after decarbonylation treatment at 350C. This kind of smoothing can be
attributed to the loss of weakly interacting tungsten complexes, which as would be
expected are present in higher proportion at 90C. The final tungsten content after 20h
was ~1.7 wt% at lower sublimation temperature and ~2.0 wt% at higher temperature.
These continuous deposition experiments show that steric hindrance begins to appear
on the surface during longer reaction time. The carbonyl ligands of supported tungsten
complexes make it difficult for new gaseous substrate to find a suitable site for
adsorption. To avoid these steric effects during the preparation process and further to
increase the metal loading, a pulse technique was tested as the second method.
The results of the pulse method, which involved successive deposition and
decarbonylation cycles, are displayed in Figure 2. As can be seen, a linear dependence
between the tungsten loading and the number of preparation pulses was achieved at
both 80 and 90C. The influence of dosage, which mostly depends on the sublimation
temperature, is observed more clearly than in the continuous deposition experiments.
7

Tungsten [wt%]

6
5
4

90C

80C
2
1
0
1

Number of preparation pulses

Figure 2. Tungsten content on alumina after successive deposition-decarbonylation

cycles at two sublimation temperatures, 80 and 90C (temperature of the reactant
vessel). Temperature of the fluidised bed reactor was 100C in both cases.
These pulse experiments clearly show that gas phase based preparation will provide
higher tungsten loading if at least part of the carbonyl ligands are removed before the

12

next pulse. Five pulses at 80C yielded ~4.5 wt% tungsten loading, and at higher
deposition temperature the concentration was ~5.8 wt%. Although the saturation level
was not achieved, the tungsten loadings were considerably higher than the values
reported in the literature (typically 1 wt% or less).37-39,42,43,45 Although the results
indicate uniform adsorption and good control of the preparation process, it should be
noted that the formation of multilayer structures is not excluded.
At higher temperatures, alumina supported carbonyl complex decomposes, and
reaction easily occurs between zero valent adsorbate and surface hydroxyl groups.40
As a consequence of this redox reaction (the mechanism is described in detail in the
literature40), the metal is oxidised and the benefit of low valent starting material is lost.
A removal of the first three carbonyls from adsorbed tungsten hexacarbonyl reportedly
can be achieved with no or only slight oxidation.38,39 According to TPD (temperature
programmed decomposition) studies, the partially decarbonylated W(CO)3 level can be
achieved by heating the sample at 200C.38,III With further heating, the metal starts to
lose the remaining ligands and becomes oxidised.
In the third method tested, partial decarbonylation was applied between the deposition
pulses. The aim of this third method was to prevent oxidisation during the preparation
without losing the benefits of the pulse technique. The effect of two different
decarbonylation treatments is depicted in Figure 3. Except for the differences in
decarbonylation, the preparation conditions were identical. The A columns describe an
experiment in which most of the carbonyl ligands were removed at higher
temperatures, and the B columns an experiment in which the decarbonylation was
reduced to W(CO)3 level in an attempt to avoid oxidation.
6

Tungsten [wt%]

5
4

2
1
0
1

Number of preparation pulses

Figure 3. Tungsten content on alumina after successive deposition decarbonylation

cycles. A) total decarbonylation between pulses at 350C and B) partial
decarbonylation between pulses at 200C. All sublimations were made at 90C.

13

Judging from the columns, growth is linear for the partially decarbonylated systems as
well. As can be seen, the three carbonyls left on the supported complex make the
binding of new adsorbate more difficult than on the surface that is virtually free of
carbonyl ligand. Although the steric hindrance is not strong enough to prevent a
controlled increase in the tungsten loading, the rate of growth decreases to almost one
half of what it was when all carbonyls were removed.
Five cycles carried out with the method of partial decarbonylation yielded ~3.1 wt%
tungsten loading. No attempt was made to maximise the content. After the final
deposition pulse, the remaining carbonyl ligands were removed at higher temperature.
The effect of oxidative surface reaction was minimised also during this final stage by
carrying out the decarbonylation under reducing atmosphere.
Besides allowing oxidation to be avoided, the method of partial decarbonylation can be
exploited to produce better dispersion, since the three remaining carbonyls of the
tungsten complex can be assumed to keep most of the tungsten atoms molecularly
dispersed.38 Moreover, the avoidance of higher temperatures during successive pulses
minimises the effect of agglomeration.
All these findings show that the targeted tungsten level and growth rate can be
achieved by varying the method and temperature of preparation. It may be added that
also the surface area and pore structure of the alumina support have a clear effect on
the amount of adsorbed tungsten.III The homogeneous reaction conditions in the
fluidised bed reactor combined with a controlled gradual preparation process, ensure
that the energetically most favourable surface sites will be occupied first. A partial
decarbonylation between the pulses could prove to be of some value in the preparation
of low valent tungsten catalyst with good dispersion.
Moderate-to-low cobalt loading on bimetallic tungsten cobalt catalysts and pure cobalt
samples was achieved by deposition of dicobalt octacarbonyl. In the case of
CoW/Al2O3 catalysts, all tungsten deposition cycles were made before the addition of
cobalt. To avoid oxidation, carbonyl ligands of the adsorbed cobalt compound were
removed under reducing hydrogen atmosphere.III,IV

14

3. CHARACTERISATION OF CATALYSTS AND

CATALYST PRECURSORSII,III,IV,V
3.1. CHARACTERISATION OF ALUMINA ADSORBED W(CO)6 BY
FOURIER TRANSFORM INFRARED SPECTROSCOPYI,II,III
Infrared spectroscopy (IR) is a widely used technique for study of the attachment of
transition metal complexes to a surface. Diffuse reflectance infrared Fourier transform
spectroscopy (DRIFT), a special mode of infrared spectroscopy, has proved to be
particularly useful for catalyst samples in powder form.57-59 One of the main
advantages of DRIFT is that sample preparation, which too often results in irreversible
changes in the surface properties, can be avoided.
DRIFT offer two advantages in the study of powdered alumina adsorbed transition
metal carbonyl based catalysts: carbonyl ligands have a characteristic C-O stretching
frequency region around 2200-1600 cm-1 which can be used to follow the formation of
subspecies and their interaction with different surface sites40-44,46,60 and analysis of the
O-H stretching region below 4000 cm-1 of partially dehydroxylated alumina can
provide information about the reactions between adsorbate and surface hydroxyl
groups.61-63
The primary objective of the DRIFT measurements of tungsten hexacarbonyl on
alumina was to achieve good control of the preparation. A second objective was to
discover possible new assignments for the adsorbed surface species. All measurements
were made under inert atmosphere in a nitrogen glove box. The background spectrum
of pure alumina (Aldrich, 150 mesh, 155 m2/g) was subtracted from all spectra except
in the hydroxyl region. The interpretation of the spectra is only qualitative.
Spectrum a in Figure 4 shows the carbonyl stretching region after a typical deposition
pulse. After decarbonylation at 350C under nitrogen (spectrum b), most of the
carbonyl ligands have been removed and only a few weak bands remain. This indicates
that the steric crowding due to carbonyl ligands has been minimised before the new
deposition pulse.
The intensities of the weak bands at 2008 and 1982 cm-1 in spectrum b increased
sharply when the sample was exposed to air during decarbonylation (spectrum c). The
shape and location of these two bands resemble closely the shape and location in
spectra presented for adsorbed rhenium and chromium oxide on alumina.64 Thus, the
weak bands observed at 2008 and 1982 cm-1 in spectrum b (and at 2005 and 1984 cm-1
in spectrum c) may be attributed to the formation of oxidised tungsten species. These
findings indicate, in agreement with the literature,38,39 that treatment at higher
temperature leads to the formation of oxidised tungsten species even under nitrogen
atmosphere.

15

As can be seen in spectrum b (and c) in Figure 4, thermal treatment under nitrogen

leads to the formation of new bands between 1700 and 1200 cm-1. These bands can be
assumed to be due to moderately stable carbonate and formate surface species formed
in reaction of released CO and CO2 with the surface. The bands are identified on the
basis of IR assignments given in the literature;65-71 the bands at 1591, 1394 and 1375
cm-1 indicate the presence of formate species on the surface, whereas the bands at
wavenumbers 1620 and 1478 cm -1 can be assigned to the formation of bicarbonates.
a

2008
b

Reflectance

2086
1982
2070
2005

1591
1478 1375

1984
1394
1620

2400

2200

2000 1800

1600

1400

-1

Wavenumbers [cm ]

Figure 4. Carbonyl region of W(CO)6 supported on -alumina pre-treated at 500C (a)

after deposition at 80C for 5h under N2, (b) after decarbonylation at 350C for 6h
under N2 and (c) after decarbonylation at 350C for 6 h under N2 with slight air
exposure.

The method of partial decarbonylation was applied as a means of preventing oxidation

of the catalyst during treatment at higher temperature. As seen in previous deposition
experiments, the remaining carbonyls did not, however, prevent linear growth of the
tungsten loading. The effect of different decarbonylation conditions can be studied by
inspection of the spectra a-f in Figure 5. When decarbonylation was adjusted to
W(CO)3 level, by heating the sample at 200C, several signals were left in the carbonyl
region (spectra b and c).
As a means of keeping the adsorbed tungsten complex in low oxidation state during the
final decarbonylation step, the sample was treated under reducing atmosphere. Spectra
d-f depict the changes in the carbonyl region as a function of increasing temperature
under hydrogen flow. Comparison of the shapes of spectra 4b and 5d (same

16

decarbonylation temperature but different fluidisation gas) around 2000 cm-1 reveals a
clear dependence on the treatment atmosphere. Evidently, similar oxide structures were
formed under nitrogen (spectrum 4b) as under slight air exposure (spectrum 4c), but
this was not the case for hydrogen atmosphere (spectrum 5d). In addition, and in
agreement with the literature,69 the unfavourable formation of carbonaceous species
was suppressed when treatment at higher temperatures was made under hydrogen.
f
1590
2100

1394

1540

Reflectance

c
b

a
2010 1867
1971
1915

2400 2200 2000 1800 1600 1400

Wavenumbers [cm-1]

Figure 5. W(CO)6 supported on -alumina pre-treated at 500C (a) after deposition at

90C/5h/N2, and after stepwise decarbonylation (b) at 200C/5h/N2, (c) at
200C/10h/N2, (d) at 350C/5h/H2, (e) at 400C/5h/H2 and (f) at 450C/5h/H2.

Earlier IR studies have demonstrated the formation of various tungsten subcarbonyl

species on alumina.42,43,44 Furthermore, the interaction of tungsten hexacarbonyl with
three kinds of Lewis acid sites, differing in geometry and acid strength, has been
shown.46 However, the interaction of tungsten subcarbonyl species with these various
cationic sites has not been reported, even though such attachment is known for the
corresponding molybdenum and chromium analogues.46,72
Earlier IR studies typically have been carried out in a special vacuum cell where
control of the preparation was not optimised and the achieved tungsten loading was
low.41-44,46 The characterisation of the carbonyl stretching region in our study, where
higher tungsten loading was achieved under more controlled deposition conditions,

17

provides new information on alumina adsorbed tungsten carbonyl.

The spectra in Figure 5 show the formation of several bands in the carbonyl stretching
region during decarbonylation treatment. Interpretation of these spectra, together with
the IR assignments given in the literature for adsorbed carbonyl compounds,46,72
suggests that the W(CO)3 species that was formed interacts with the surface not only
via W to three surface oxo groups but also via one carbonyl ligand to a Lewis acid site.
The band at 2100 cm-1 can be assigned to the terminal CO ligand of the W(CO)3
complex interacting with the most acidic, a defective site. The bands at wavenumber
2010 and 1915 cm-1 may be due to the two terminal carbonyl ligands of the complex
that is interacting with a tetrahedral site (the next acidic site). The bands at 1971 and
1876 cm-1 are accordingly ascribed to terminal ligands of the tricarbonyl species
interacting with the weakest octahedral site. The bands for oxygen bonded CO on
different sites are poorly resolved because they begin to overlap with the bands due to
carbonaceous species.
Similar interactions can be proposed for adsorbed tungsten pentacarbonyl. The
shoulder at 2086 and the band at 2070 cm-1 in spectrum 4a may be attributed to the
highest A1 modes of the pentacarbonyl species interacting with tetrahedral and
octahedral Lewis acid sites. The resolving of other bands due to this species (A1, E and
the band for interacting CO) is made difficult by the many superimposed structures.

Reflectance

e
d
c
b
3782

3754
3728 3675

3800

3600

3400

Wavenumbers [cm-1]

Figure 6. Hydroxyl region of -alumina (a) after pre-treatment at 500C, and after (b)
one, (c) two, (d) three, (e) four and (f) five successive preparation cycles comprising
deposition at 90C for 2h and decarbonylation at 350C for 6h. The final tungsten
content was ~5.8 wt% and the experiment was made under N2.

18

The hydroxyl groups remaining on partially dehydroxylated alumina play an important

role in the surface reactions and some changes are also expected in the OH stretching
region, varying with the degree of tungsten coverage. In previous IR studies, the OH
region has been reported to remain unmodified despite tungsten hexacarbonyl
adsorption.42,46 However, the spectra presented in Figure 6 indicate that when the
tungsten loading is increased gradually, in a controlled manner, the region of isolated
hydroxyl groups begins to change shape. The most basic hydroxyls at higher
wavenumbers (3782 cm-1) are most reactive in chemisorption, whereas the acidic OH
(3675 cm-1) groups take part only in physisorption.

3.2. MODELLING OF TUNGSTEN CARBONYL SPECIES ON

SURFACE SITES OF ALUMINAV
Although the adsorption of tungsten hexacarbonyl on alumina has been widely studied
by experimental methods, such as IR,41-44,46 TPDE37-39 and ESR45, there are no
references to theoretical studies. Computational methods nevertheless can be expected
to provide information useful to obtaining a better understanding of surface phenomena
at the atomic level. Accordingly, the initial interactions of tungsten hexacarbonyl with
the different surface sites of alumina were studied by non-local DFT method.

W
C O
Al

model O1

model T1

Al

O C

C O

Al
O

model O2

model T2

model O3

model T3

Figure 7. Surface models for tungsten carbonyl complexes interacting with different
octahedral and tetrahedral surface sites of alumina.

19

Because of its acid base character, the alumina surface provides various routes of
attachment for adsorbed tungsten carbonyl compound. Both ligand and metal centred
interactions are known.60 Figure 7 shows three kinds of interaction for tungsten
carbonyls with the surface sites of alumina. Octahedral and tetrahedral Lewis acid sites
were considered as active sites for hexacarbonyl complex interacting via one of its CO
ligands (models O1 and T1). This kind of surface complex can be taken as an example
of a ligand centred interaction, which takes place during the first step of the surface
reaction. A cleavage of one CO ligand from the carbonyl complex leads to interaction
with Lewis base sites. In the metal centred interactions, the carbonyl compound binds
directly via the metal atom to an O- site of alumina (models O2 and T2). For
comparison the interaction energies were also calculated for tungsten pentacarbonyl
interacting with neutralised Lewis base sites (models O3 and T3).
Calculated interaction energies for the models are summarised in Table 1. The results
show that the interaction is stronger with Lewis base sites (Al-O-) than Lewis acid sites
(Al3+). Neutralisation of Lewis base sites (Al-O) weakened the interaction of tungsten
complex with the surface. A comparison of the interaction energies for different
coordinations of aluminium reveals that on both Lewis base sites (anionic and
neutralised) the interaction is more effective when oxygen is coordinated to octahedral
Al. On cationic Lewis acid sites, in contrast, tungsten hexacarbonyl interacts more
strongly with tetrahedral Al3+ than the corresponding octahedral site. This is in
agreement with the reported stronger acceptor character (Lewis acidity) of the Al3+tet
sites.46

Table 1. Interaction energies of tungsten carbonyls on octahedral and tetrahedral sites

of alumina.
Surface site
Al3+oct
Al3+tet
Aloct-OAltet-OAloct-O
Altet-O

Complex
W(CO)6
W(CO)6
W(CO)5
W(CO)5
W(CO)5
W(CO)5

Model
O1
T1
O2
T2
O3
T3

E/kJ/mol-1
-4
-63
-352
-302
-242
-186

Table 2 presents the optimised bond lengths of the different models. The results
demonstrate that, on the Lewis acid site, the oxygenaluminium distances are clearly
shorter with tetrahedral aluminium than octahedral aluminium, as would indeed be
expected. In interaction with the cationic surface sites, the C-O bond of the interacting
ligands becomes slightly elongated, whereas the C-W bond is slightly shortened with
respect to the non-interacting CO ligands.
Surface Al-O bond lengths were also optimised without adsorbate and with hydrogen.
For the charged Lewis base site, aluminium-oxygen distances were 1.764 and 1.664

20

for the octahedral and tetrahedral coordinated sites, respectively. The corresponding
bond lengths for neutralised sites were 1.697 and 1.636 . An optimisation of the Al-O
lengths with hydrogen attached (Al-OH) generated values of 1.814 for octahedral
sites and 1.725 for tetrahedral sites. The results in Table 2 show that attachment of
W(CO)5 on Lewis base sites (charged and neutralised) does not markedly affect the AlO bond lengths. The replacement of hydrogen by carbonyl complex shortened the Al-O
bond distances noticeably, however.

Table 2. Optimised bond lengths for interactions of tungsten carbonyl on octahedral

and tetrahedral sites on alumina.
Surface site

Complex

Model

Al3+oct
Al3+tet
Aloct-OAltet-OAloct-O
Altet-O

W(CO)5
W(CO)5
W(CO)6
W(CO)6
W(CO)6
W(CO)6

O1
T1
O2
T2
O3
T3

r(Al-O)
[]
2.276
1.951
1.778
1.666
1.694
1.630

r(O-C)
[]
1.157
1.171
-

r(C-W)
[]
2.066
2.098
-

r(O-W)
[]
2.122
2.141
2.154
2.198

3.3. CHARACTERISATION BY TEMPERATURE PROGRAMMED

METHODSIII,IV
Temperature programmed methods such as TPR, TPD and TPO allow effective study
of the properties and reactivities of heterogeneous catalysts. In these experiments,
surface interactions between the solid catalyst and its gaseous environment are
continuously monitored through analysis of the gas phase composition as a function of
increasing temperature.73,74 One of the main advantages of the temperature
programmed methods is the simplicity of experiments. Furthermore, on a qualitative
basis the interpretation of the results is straightforward. Optimisation of the parameters
is usually a complicated task, however.

3.3.1. TEMPERATURE PROGRAMMED REDUCTIONIII

Temperature programmed reduction experiments were performed to determine the H2
consumption of the various tungsten catalysts. The observed H2 consumptions and
temperature maxima of reduction may be further related to hydroprocessing activity.
TPR results for catalysts and cobalt samples supported on two types of alumina
(Aldrich, 150 mesh, 155 m2/g and Akzo, 75-60 mesh, 195m2/g) are summarised in
Table 3.
As Table 3 indicates, and as would be expected, H2 consumption (ml/g sample)

21

increased with metal loading on both supports. The addition of Co promoter increased
H2 uptake, and bimetallic CoW/Al2O3 catalysts Cat 3 and Cat 6 exhibited the highest
values of H2 consumption. The CoW/Al2O3 catalysts also most clearly revealed the
effect of the support. Even though the tungsten loading was lower in catalyst Cat 3, this
catalyst took up more H2 (ml/g sample) than catalyst Cat 6 supported on other alumina.
Comparison of non-promoted tungsten catalysts reveals a similar trend.

Table 3. TPR results for tungsten based catalyst and Co/Al2O3 samples.
Catalyst
designation
Cat 1
Cat 2
Cat 3
Cat 4
Cat 5
Cat 6
Co sample
Co sample

Catalyst
metal
W
W
CoW
W
W
CoW
Co
Co

Al2O3
support
Akzo
Akzo
Akzo
Aldrich
Aldrich
Aldrich
Akzo
Aldrich

Metal content [wt%]

W
Co
2.2
4.8
4.8
0.3
1.9
6.1
6.1
0.3
0.3
0.3

H2 uptake
[ml/g sample]
0.123
0.213
0.302
0.082
0.227
0.232
0.403
0.408

H2/metal
molar ratio
0.041
0.033
0.039
0.032
0.028
0.024
0.996
1.009

The last column in Table 3 shows for both series of catalysts that the amount of
reducible surface species decreases as a function of tungsten loading. Unfortunately,
this may indicate a loss of dispersion at higher substrate concentration. The addition of
promoter raised the H2 uptake per metal in the case catalyst Cat 3, but no such trend
was evident for catalyst Cat 6. The unexpectedly high H2/metal molar ratio for the
cobalt samples suggests that alumina adsorbed cobalt is easier to reduce than alumina
adsorbed tungsten. The low cobalt loading leads to better dispersion on the surface,
however, which also may affect the results.
TPR profiles of the W/Al2O3 and CoW/Al2O3 catalysts are presented in Figure 8. The
patterns for tungsten catalysts Cat 1 and Cat 4 indicate a similar reduction behaviour
on the two supports at low tungsten loading; both of catalysts produces weak maxima
at 280C and 425C. However, when the metal loading is increased, new tungsten
phases form and the effect of the support becomes apparent. The catalyst Cat 2 shows a
broad downward peak at about 375C and a smaller maximum at 175C. The TPR
pattern for catalyst Cat 2 differs clearly from that for catalyst Cat 5, which has a single
maximum at 375C.
The TPR profiles of the bimetallic catalysts are noticeably different from those of the
pure tungsten and cobalt systems. Both cobalt samples show one relatively strong
reduction maximum at lower reduction temperature and two smaller peaks above this.
However, none of these cobalt or the above-mentioned tungsten based peaks is present
in the TPR pattern of the bimetallic CoW/Al2O3 catalysts. Moreover, the moderate-tohigh H2 uptake of the pure cobalt samples decreased sharply in the case of the

22

TCD Signal

bimetallic systems. These findings indicate that the reduction behaviour of alumina
adsorbed CoW/Al2O3 catalyst is unlike that of the monometallic systems and suggest
the formation of synergetic bimetallic phase.

CoW/Al2O3 (Akzo)
Cat 3

CoW/Al2O3 (Aldrich)
Cat 6

W/Al2O3 (Akzo)
Cat 2

W/Al2O3 (Aldrich)
Cat 5

W/Al2O3 (Akzo)
Cat 1

W/Al2O3 (Aldrich)
Cat 4

Co/Al2O3 (Akzo)

100 200 300 400 500

Co/Al2O3 (Aldrich)

100 200 300 400 500

Temperature [C]

Figure 8. TPR profiles of alumina adsorbed W and CoW catalyst and Co samples.

The TPR profile of CoW/Al2O3 catalyst Cat 3 showed a strong upward peak centred at
350C and a downward maximum at about 250C. The latter suggests the presence of
another reducible site at lower temperature region. No such low temperature reduction
peak was observed for the bimetallic catalyst Cat 6, however. The results for catalysts
Cat 3 and Cat 6, together with the values of H2 uptake presented in Table 3, indicate
that the reducibility of catalyst Cat 3 is better in the temperature region investigated,
and, that being the case, higher hydrotreating activity would be expected.
Studies of conventional tungsten catalysts have demonstrated the formation of various
tungsten oxide surface structures, which typically are not reducible under
800C.13,33,34,36,75 Carbonyl precursor based catalysts, in contrast, exhibit reduction
peaks in a region several hundred degrees lower. Evidently, the surface structures of
these catalyst systems are different. As well as the starting material, also the

23

preparation process that is utilised affects the surface species. In this respect, the
gradual and controlled deposition in gas phase, where oxidation during preparation
steps can be avoided, is advantageous for the production of more easily reducible
tungsten particles.

3.3.2. TEMPERATURE PROGRAMMED OXIDATION AND OXYGEN

PULSE CHEMISORPTIONIV
Temperature programmed oxidation experiments were performed to study reactivities
of the prepared catalysts in oxygen treatments as a function of metal loading. Figure 9
depicts the temperature programmed oxidation profiles of two W/Al2O3 catalysts with
different tungsten loadings. The TPO profile of the alumina supported cobalt sample is
included in to allow study of the behaviour of the promoter metal. The effect of
tungsten loading is clearly seen. At low tungsten loading (1.1 wt%) oxidation did not
take place until about 400C, but at higher tungsten loading (5.5 wt%) the beginning of
the O2 uptake was shifted to lower temperature region (260C).
260C

TCD Signal

390C

W-1.1 wt%
W-5.5 wt%
Co-0.3 wt%
0

100

200

300

400

500

Temperature [C]

Figure 9. TPO profiles of alumina adsorbed tungsten and cobalt samples.

This variation in the onset of oxidation suggests that, in the case of low tungsten
loading where particles are well dispersed, the interaction between the metal and
surface is so strong that higher temperature is required for oxidation to occur. When
tungsten concentration is increased, surface interactions diminish as new interactions
begin to appear between adjacent adsorbed tungsten particles. Weaker surface
interaction is reflected in the earlier O2 uptake in the TPO profile in Figure 9.
According to the literature, two oxidation steps would be expected for nitrate based
cobalt sample in temperature region examined.76 However, the TPO pattern shows only
one broad peak, centred at 490C. The absence of other oxidation peak, which one

24

might expect to see in much lower temperature region, must mean that in the case of
the carbonyl based cobalt sample the first oxidation step occurred immediately the
oxidizing gas mixture was passed over the sample, during the initial stabilisation
period before detection was initiated. Partial oxidation during decarbonylation may
also be relevant. Partial oxidation would similarly lead to a situation where the first
oxidation step was not detected. In any event, in an attempt to minimise the effect of
oxidation during the preparation, the carbonyl ligands were eliminated at higher
temperature under reducing environment (hydrogen flow).III
Even though, strightly speaking, oxygen pulse chemisorption is not a temperature
programmed method, the PCO results are considered here because they can usefully be
related to the TPO studies. In a dynamic pulse chemisorption technique, a known
quantity of reactive gas is injected into the carrier stream. When the gas passes through
the sample adsorption occurs and the amount of consumed active gas is monitored. The
surface is considered to be saturated when the amount of adsorption is the same during
two successive pulses.77
Oxygen pulse chemisorption results for the alumina adsorbed CoW catalysts at 250
and 500C are set out in Table 4. As can be seen, O2 consumption was clearly higher at
250C than at 500C. Even though the TPO experiments suggested that the O2 uptake
was more efficient at about 400C, the pulse chemisorption measurements, where O2
exposure was made during a longer period at constant temperature, showed O2 uptake
to be higher in the lower temperature region. Evidently, at higher temperature the
oxygen adsorption is hindered by the excess energy of the system. Furthermore, the
stability of the adsorbed oxygen begins to diminish at higher temperature, further
increasing the desorption.
Table 4. Results of O2 pulse chemisorption experiments for bimetallic CoW/Al2O3
catalyst at 250 and 500C.
Sample
CoW/Al2O3
CoW/Al2O3

Metal content [wt%]

W
Co
5.5
0.3
5.5
0.3

Oxidation temperature
[C]
250
500

O2 uptake
[ml/g sample]
1.917
1.358

Oxygen pulse chemisorption provides an effective way to study the effect of

decarbonylation conditions on surface species. Table 5 summarises the results of PCO
measurements where the remaining carbonyl ligands of the W(CO)3/Al2O3 samples
were removed under argon or hydrogen flow before the oxidative treatment. For
comparison, the table includes an results for the experiment where PCO study was
made directly, without complete decarbonylation treatment.
Inspection of the results reveals that the amount of oxygen consumed closely depends
on the decarbonylation conditions. The first sample was treated under inert Ar gas at
relative high temperature, and can be assumed to be oxidised before pulse

25

chemisorption treatment. This finding is in good agreement with the above described
IR studies, where complete decarbonylation under inert gas was found to lead to the
formation of tungsten oxide species on alumina.II
Table 5. Effect of decarbonylation conditions on the oxidation of W species formed on
alumina.
Sample
W [4.7 wt%]

Complete decarbonylation
treatment
[gas/temperature]
W(CO)3/Al2O3
Ar/500C
W(CO)3/Al2O3
-a
W(CO)3/Al2O3
H2/450C
a
not completely decarbonylated

O2 consumption
[ml/g sample]
0.26
1.16
1.38

When PCO measurement of the tricarbonyl sample was made directly, without pretreatment, the O2 uptake was considerably higher. According to the literature, the
supported carbonyl compound may form W(CO)2O2 and W(CO)2(O2)2 complexes
when reacting with oxygen.78 Thus the growth in O2 consumption in this case may in
part be related to the formation of these oxidised carbonyl complexes. The bottom row
in Table 5 shows the effect of hydrogen treatment. The five-fold difference in the O2
consumption between the samples treated under argon and hydrogen is too great to be
due to 50C temperature difference. Evidently, when complete decarbonylation (the
final step of preparation) is carried out under reducing atmosphere instead of argon or
nitrogen, the oxidative surface reaction is prevented or at least minimised.
Table 6 shows the results of oxygen pulse chemisorption experiments carried out on
alumina adsorbed W, Co and CoW samples at 250C. The O2 uptake (ml/g sample)
increased with tungsten loading, as would be expected. Bimetallic CoW/Al2O3 catalyst
showed the highest O2 consumption (1.917 ml/g sample), and the value was higher
than the sum of the values of the corresponding monometallic samples. Evidently the
surface structure of the bimetallic system differs from that of the mixture of pure
components and a bimetallic phase has been formed.
Table 6. Results of O2 pulse chemisorption experiments for alumina supported W, Co
and CoW samples at 250C.
Sample

O2 consumption
O2 content
[ml/g sample]
[*10-2 mmol]
Co-0.3
0.345
1.54
W-1.1
0.099
0.44
W-3.4
0.634
2.84
W-5.5
1.429
6.37
CoW-0.3/5.5
1.917
8.55
The metal contents of sample are indicated as W-1.1 etc.

Metal content
[*10-2 mmol]
5.09
5.98
18.5
29.9
35.0

O2/metal
molar ratio
0.30
0.07
0.15
0.21
0.24

26

Comparison of O2/metal molar ratios (last column in Table 6) shows that the
proportion of surface species reactive toward oxygen treatment increases with metal
loading. Evidently, larger surface particles begin to form, and this leads to a situation
where some of the interactions with the surface are replaced by interactions with
adjacent tungsten atoms. The diminishing of the strong surface effect on the outermost
parts of larger tungsten species is then seen as a higher reactivity toward oxygen
treatment. At low metal loadings, well-dispersed tungsten particles were surrounded by
many surface hydroxyls and oxo groups, making them inactive toward oxygen, in
agreement with TPO experiments.

3.3.3. TEMPERATURE PROGRAMMED DESORPTION OF

AMMONIAIV
Because of its small size and strong basicity, ammonia is a suitable probe molecule for
the detection of almost all the acidic sites on porous material.79-82 Even though
ammonia can interact with the surface in several ways, which makes it difficult to
resolve the distribution and number of different acidic sites, the approach provides an
effective tool for comparing the overall acidity of different supported catalysts.
The change in total acidity with metal loading is depicted in Figure 10. As can be seen,
the amount of desorbed NH3 was lowest for the sample (W-1.1) with low tungsten
loading and the total acidity of this sample was clearly lower than that of the pure
support. The result can be attributed to the disappearance of the most acidic sites
present on alumina before the deposition.

[mol/g sample]

Total acidity

750
725
700
675

716
704
682

650
625

674

667

W-3.4

W-5.5

625

600
575
Alumina
support

W-1.1

Co-0.3

CoW0.3/5.5

Figure 10. Total acidity of alumina and alumina supported W, Co and CoW samples.
The metal contents of samples are indicated as W-1.1 etc.

27

When tungsten loading was increased, the formation of new acidic sites of medium
strength led to an increase in total acidity. However, the results presented in Figure 10
show that even though the acidity increased with metal loading, the acidity of the
sample with highest tungsten concentration was still less than that of the pure support.
In conventional tungsten catalysts the formation of tungsten oxide surface species
reportedly increases the acidity over that of pure alumina, even at low metal loading.83
Our recent finding that surface acidity decreases at the beginning of tungsten
deposition suggests that the surface species that are formed are different in the
conventional and the present tungsten systems. This also suggested that the
unfavourable formation of tungsten oxide species might be reduced by utilising
zerovalent tungsten hexacarbonyl and controlled gas phase preparation.
The ammonia desorption results for the cobalt sample show that even moderate low
cobalt loading is sufficient to increase the total acidity of the Co/Al2O3 system.
Addition of the same amount of cobalt (0.3 wt%) to the W/Al2O3 sample (W-5.5)
produced a similar effect. Furthermore, the increase in acidity due to promoter was
more pronounced for tungsten sample than for pure support. This suggests that the
tungsten particles already present on the alumina support affect the adsorption and
reactivity of cobalt.

4. HYDRODESULPHURISATION ACTIVITY OF
W/Al2O3 AND CoW/Al2O3 CATALYSTSIII
4.1. REACTOR ARRANGEMENT
The hydrotreating activity of the W/Al2O3 and CoW/Al2O3 catalysts was determined in
thiophene hydrodesulphurisation (HDS) reaction. The HDS activities were evaluated in
a specially developed and constructed batch reactor system. The reactor arrangement is
illustrated in Figure 11. The system operates in gas phase only. Avoidance of the liquid
phase simplifies the arrangement for catalyst screening and there are no uncertainties
associated with the analysis of the two phases. The reactor system is easy to construct
and the amounts of poisonous reactants can be limited to moderate-to-low level. The
system is suitable for preliminary screening of new catalyst candidates, especially
when the operating temperature region is known.

28

To vacuum pump
To flue
Cold trap

a
NaOH bubblers
a

Pressure relief
valve

a
d
Batch reactor

d
N2

Oven

Temperature Magnetic stirrer

controller

Rotaflo flask
for thiophene

a. Needle valve
b. Ball valve (3-way)
c. Ball valve (2-way)
d. Check valve

H2

H2S/H2

Figure 11. Batch reactor system for thiophene HDS reaction.

4.2. RESULTS OF HYDRODESULPHURISATION TESTS

A commercial hydrodesulphurisation catalyst (CoMo/Al2O3) was used as reference
catalyst. For evaluation of the catalysts the amount of metal was adjusted to the same
level: 0.25g (0.026-0.095 mmol) for the prepared tungsten based catalysts and 0.055g
(0.094 mmol) for the commercial catalyst. The results of the HDS tests are summarised
in Table 7 (for designation of the catalysts see Table 3 in Section 3.3.1).
Table 7. Hydrodesulphurisation activity of the catalystsa.
Catalyst
Al2O3
Metal content [wt%]
Conversion of
Conversion/metal
designation
support
W/Mo
Co
thiophene [%]
[mol/mol]b
Cat 1
Akzo
2.2
48.7
41.2
Cat 2
Akzo
4.8
61.2
23.7
Cat 3
Akzo
4.8
0.3
82.7
26.8
Cat 4
Aldrich
1.9
40.7
39.9
Cat 5
Aldrich
6.1
55.9
17.0
Cat 6
Aldrich
6.1
0.3
67.5
17.9
Commercial
10.0
3.9
76.3
20.6
a
b
The reaction time was 2 h at 370C in all experiments. Calculated by dividing the amount of
converted thiophene by total amount of catalyst metal.

29

As can be seen, thiophene conversion increased with tungsten loading in both the
catalysts supported on Akzo and those supported on Aldrich alumina. The addition of a
small amount of cobalt as promoter increased the conversion further; bimetallic
CoW/Al2O3 catalyst Cat 3 showed the highest activity (82.7%), on a par with
commercial CoMo catalyst (76.3%). The conversion value observed for the other
CoW/Al2O3 catalyst Cat 6 (67.5%) was also at promising level.
The effect of the alumina support on the activity is clearly seen with the tungsten
catalysts Cat 2 and Cat 5: even though the metal loading of catalyst Cat 2 was lower, it
provided higher conversion. The addition of a small amount of cobalt to these catalysts
(to give Cat 3 and Cat 6) increased the difference in activity further.
The last column in Table 7 shows the calculated conversion/metal molar ratios.
Comparison of the results shows that the portion of active metal particles was higher
for the CoW/Al2O3 catalyst Cat 3 than the commercial reference catalyst. This was also
true for the tungsten catalyst with low metal loading. The difference demonstrates the
advantage of our preparation process; the formation of active sites is more efficient in
gas phase adsorption, as a consequence of either better dispersion or more effective
surface controlled occupation of the catalytically active sites (the most active sites are
occupied first), or both. Also in our case, however, the amount of reactive surface sites
seems to decrease as a function of metal loading. This is in good agreement with the
above-mentioned TPR and TPO/PCO studies, which indicated that the unfavourable
loss of dispersion begins to appear on the surface with increase in the tungsten
loading.III,IV
Comparison of the HDS activity and hydrogen treatment results reveals a evident
correlation between hydrotreating activity and H2 consumption. The TPR studies
(Section 3.3.1) show for the most active bimetallic CoW/Al2O3 catalyst, Cat 3, the
highest H2 uptake value and two reduction peaks below 370C (activation and reaction
temperature in HDS). The CoW/Al2O3 catalyst Cat 6 supported on a different alumina
shows only one reduction maximum and the total H2 uptake is clearly less than that of
catalyst Cat 3. The activities and H2 uptakes of the non-promoted catalysts show a
similar trend accordingly: The more active the catalyst, the more effective the H2
uptake at the applied activation and reaction temperatures.
The observed correlation between the HDS activity and the reducibility of the catalysts
is related to the number of surface species that can be activated by sulphurisation
(treatment under H2/H2S at elevated temperature). Estimaties of the degree of
sulphidation showed that for the CoW/Al2O3 catalyst Cat 3 the sulphur/metal molar
ratio is 1.85. That is, there are almost two sulphur atom per metal. Thus, if the active
tungsten phase on the surface is considered to be WS2, the achieved sulphidation level
for the most active tungsten based catalyst is good.III
Comparison of hydrotreating activity and acidity suggests that some relationship may
exist between these two properties as well. NH3-TPD measurements showed the acidity

30

to be highest for the corresponding bimetallic CoW/Al2O3 catalyst that in HDS tests
gave the best conversion. The increase in the hydrotreating activity with acidity is in
agreement with results reported in the literature for oxide based tungsten catalyst.13,17,25

Table 8. Product distributions obtained in HDS with selected catalysts.

Cat 1
Products [mol %]
Ethylene
Ethane
Acetylene
Propene
Propane
Isobutane
1-Butene
n-Butane
trans-2-Butene
Ethyl acetylene
Thiophene

Catalyst designation
Cat 2 Cat 3
Cat 4

0.2
1.1
0.3
0.6
0.2
4.7
33.7
10.3
7.2
41.6

1.0
2.3
0.3
2.6
2.0
1.8
52.2
4.0
2.7
31.1

0.7
1.4
0.2
1.9
2.1
1.0
75.6
2.6
1.7
12.9

0.5
1.1
6.3
1.8
3.4
4.6
3.9
18.6
7.3
4.8
47.9

Cat 5

Cat 6

Commercial

0.5
0.8
1.8
0.9
1.5
3.1
46.2
5.6
4.2
35.3

0.2
0.5
0.2
0.8
0.3
2.5
60.1
6.0
4.0
25.5

0.2
0.2
0.4
0.4
0.1
80.1
0.2
0.5
17.7

The product distribution of the catalysts is summarised in Table 8. As can be seen, nbutane was the main product in all experiments and, in general, the portion of other
products (cracked, branched, olefinic hydrocarbons) was minor. The ratio of n-butane
to other products increased with conversion, within both series of prepared catalysts.
Even though the selectivity to n-butane was not as good for the prepared catalysts as
for the commercial catalyst, the results for the most active CoW/Al2O3 catalyst can be
considered very promising.

5. CONCLUSIONS
Gradual gas phase adsorption of tungsten hexacarbonyl in a fluidised bed reactor was
found to be an effective system for producing alumina supported tungsten complexes
in a controlled way. The targeted tungsten level and growth rate were achieved by
varying the methods and temperatures of the preparation. Linear growth of the tungsten
loading was achieved by pulse technique, and a catalytically useful tungsten
concentration was produced. Characterisation of the catalysts by DRIFT, PCO and
NH3-TPD showed that undesirable formation of oxidised tungsten species can be
avoided in the partial decarbonylation method, when complete removal of the carbonyl
ligands is made in a final step under reducing atmosphere.
DRIFT measurements showed that when higher tungsten concentration is achieved in a
controlled preparation process, new assignments can be proposed for the adsorbed

31

surface species. Interaction of tungsten penta- and tricarbonyl species with various
cationic sites is suggested. Increase in the tungsten loading also changes the shape of
the hydroxyl region, where the most significant changes are associated with the most
basic hydroxyl groups. Theoretical studies of the first interaction steps on the alumina
surface supported the conclusion that the interaction of tungsten hexacarbonyl with the
Lewis acid site is moderate-to-weak. The attachment to the Lewis base site, which took
place with loss of one carbonyl ligand from the complex, led to the higher interaction
energy.
Temperature programmed studies showed clear changes in the reactivities of the
catalysts toward hydrogen and oxygen treatment as a function of metal loading.
Furthermore, the acidity of the surface systems changed when the tungsten
concentration was increased. Besides the changes in surface structures, there was an
unfavourable loss of dispersion at higher tungsten loadings. The results of TPR, PCO
and NH3-TPD experiments on the bimetallic CoW/Al2O3 catalysts suggested the
formation of a synergetic phase. Moreover, TPR patterns showed the reduction peaks
of the carbonyl precursor based tungsten catalysts to lie several hundred degrees lower
temperature than those of the traditional oxide-form tungsten catalysts, indicating
better activation capability.
The new method of preparation that was applied is a promising one for producing
alumina supported tungsten based catalysts for hydrodesulphurisation. The catalysts
containing cobalt as promoter were as active as the commercial CoMo hydrotreating
catalyst. The high concentration of active surface particles demonstrates the benefits of
using a zero valent starting material and gas phase preparation method. The overall
results are an encouragement to primary aim, which was to produce a tungsten based
hydrodesulphurisation catalyst, that is easily reduced and sulphurised at moderate
temperature.

32

ACKNOWLEDGEMENTS
The present work was carried out in the Department of Chemistry, University of
Joensuu, during the years 1994-1999.
I am deeply grateful to my supervisor, Professor Tapani Pakkanen, for providing me
with the opportunity to work in the field of transition metal and catalyst chemistry and
for his encouragement and wise guidance.
Sincerest thanks are extended to colleagues, co-workers and the whole staff at the
Department of Chemistry, University of Joensuu, both for their valuable assistance and
for creating a stimulating working atmosphere.
I wish to thank Dr. Kathleen Ahonen for revision of the language of this manuscript.
Most importantly, heartfelt thanks are owed to my dear wife Sari for her support and
patience and to son Jere, our lively two-year-old. Theirs was a valuable role, to
sometimes divert my thoughts away from the laboratory.
Financial support from the Technology Development Centre of Finland and the New
Hydrogen Transfer Catalysts Project is gratefully acknowledged.

Joensuu, May 1999

Mika Suvanto

33

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Earlier Dissertations from the Department of Chemistry, University of Joensuu

1/1985

2/1987

3/1987

4/1987

5/1987
6/1988

7/1989
8/1990
9/1991

10/1992
11/1992
12/1992
13/1992
14/1992
15/1993

16/1994
17/1994

VAINIOTALO Pirjo: Studies on pyrolytic and mass spectrometric decompositions of some

bicyclic alcohols and acetates (Annales Academiae Scientiarum Fennicae Series A. II. Chemica
no. 204).
PURSIAINEN Jouni: Studies on mixed-metal clusters containing cobalt, ruthenium and rhodium
and on the catalytic reactivity of homogeneous ruthenium-rhodium and ruthenium-cobalt systems
(Annales Academiae Scientiarum Fennicae Series A. II. Chemica no. 209).
VAINIOTALO Anto: Studies on complexation of dioxouranium(VI) with some 1- and 2monoximes of sulphonated 1,2-naphthoquinones (Annales Academiae Scientiarum Fennicae
Series A. II. Chemica no. 210).
VENLINEN Tapani: Heteronuclear cluster compounds of iron, ruthenium and osmium.
Characterization and catalytic application. (Annales Academiae Scientiarum Fennicae Series A.
II. Chemica no. 211)
HNNINEN Kari: Phenolic acids in humus chemistry (Annales Academiae Scientiarum
Fennicae Series A. II. Chemica no. 213).
NEVALAINEN Vesa: Systematic retrosynthetic analysis applied in the preparation of antifungal
5,6-dihydro-1,4-oxathlines and 5,6-dihydro-1,4-dithiines. The merits of manual and computerassisted synthetic analyses and evaluation of synthetic pathways verified by experiments
(Annales Academiae Scientiarum Fennicae Series A. II. Chemica no. 219).
HIETANIEMI Lauri: Studies on -blockers. Synthesis, analysis and inversion of enantiomers
thereof.
ROUVINEN Juha: Three-dimensional structure and function of cellobiohydrolase II (Annales
Academiae Scientiarum Fennicae Series A. II. Chemica no. 230).
BJRKROTH Jussi-Pekka: Evaluation of structure-activity relationships in drug design and an
application to bisphosphonates (Annales Academiae Scientiarum Fennicae Series A. II. Chemica
no. 236).
ALVILA Leila: Hydroformylation of C3-C7 olefins with group 8-9 metal carbonyl and chloride
derived catalysts (Annales Academiae Scientiarum Fennicae Series A. II. Chemica no. 237).
ROSSI Sirpa: Organochalcogenide ligands in clusters of ruthenium, cobalt and rhodium (Annales
Academiae Scientiarum Fennicae Series A. II. Chemica no. 238).
HIRVA Pipsa: Theoretical studies on the adsorption interactions on inorganic surfaces (Annales
Academiae Scientiarum Fennicae Series A. II. Chemica no. 239).
VEPSLINEN Jouko: Preparation of novel halomethylenebisphosphonate partial esters as
drugs (Annales Academiae Scientiarum Fennicae Series A. II. Chemica no. 240).
LINDBLAD Marina: Cluster models for chemisorption on nonmetallic surfaces (Annales
Academiae Scientiarum Fennicae Series A. II. Chemica no. 243).
IISKOLA Eero: Studies on the chemistry of donors in heterogenous TiCl4/MgCl2-supported
catalysts and stereoselective polymerization of propene (Annales Academiae Scientiarum
Fennicae Series A. II. Chemica no. 250).
HOFFRN Anna-Marja: Computer-aided protein modelling: Applications to antibody and
enzyme engineering (VTT Publications no. 185).
KAUPPINEN Matti: Determination of arsenic, gold, osmium, rhodium and ruthenium in aqueous
or in organic solutions by plasma atomic emission or atomic absorption methods (Annales
Academiae Scientiarum Fennicae Series A. II. Chemica no. 259).

18/1994 PERKYL Mikael: Ab initio quantum mechanical studies on bioreceptor-ligand systems. The
model assembly approach (Annales Academiae Scientiarum Fennicae Series A. II. Chemica no.
260).
19/1994 TRRNEN Anneli: Two major endo-1,4--xylanases from Trichoderma reesei (Annales
Academiae Scientiarum Fennicae Series A. II. Chemica no. 261).
20/1995 HAUKKA Matti: Ruthenium monobipyridines derived from Ru3(CO)12, [Ru(CO)3Cl2]2 and 2,2'bipyridine. Applications to heterogeneous 1-hexene hydroformulation and use as model
compounds for intermediates and active catalysts in water gas shift reaction and reduction of
CO2.
21/1995 HUKKA Terttu: Interaction of hydrogen, halogens, hydrogen halides and Cxy radicals on the
(100) surfaces of diamond and germanium.
22/1995 PERNIEMI Sirpa: Preconcentration of phosphorus, chromium, arsenic, selenium, mercury and
gold onto activated charcoal before determination by energy dispersive X-ray fluorescence
spectrometry.
23/1995 MUILU Juha: Use of translational properties in ab initio electronic structure studies. ZnS clusters
and crystallites.
24/1995 PARTANEN Tuula: Mass spectrometric studies of cyclic diols, amino alcohols, amino acids and
their heterocyclic derivatives. Stereochemical effects in the electron ionization, chemical
ionization and collision-induced dissociation mass spectra.
25/1995 RSNEN Jari: Interaction of monoanionic phosphonates and phosphinates, their sulfur
analogues and dianionic bisphosphonates with dicationic calcium and magnesium ions.
26/1995 KAKKONEN Heikki: Stabilization of tetrahedral mixed metal clusters of ruthenium, rhodium
and cobalt with phosphine ligands.
27/1996 KIVIAHO Jari: Fischer-Tropsch synthesis catalysed by cobalt-rhodium and cobalt-ruthenium
carbonyl clusters on silica (VTT Publications no. 290).
28/1996 PAKARINEN Jaana: Mass spectrometric and ab initio molecular orbital calculation studies of
hydroxyacetone, 2-methoxyethanol and methyl propionate.
29/1996 PUHAKKA, Eini: Ab initio studies on the heterogeneous Ziegler-Natta catalyst system.
30/1997 LAHTELA-KAKKONEN Maija: Theoretical studies on lubricants: Molecular and dynamics
modeling of branched alkanes.
31/1997 RSNEN Tiina: Substitution reactions of clusters of ruthenium, cobalt and rhodium with
heteroatom containing ligand.
32/1997 KALLINEN Kauko: Reactivity studies of derivatives of [Ru3(CO)12], [H4Ru4(CO)12] and
[Rh6(CO)16] Clusters.
33/1998 HRKNEN Aapo: Synthesis and characterization of derivatives of tetranuclear mixed-metal
clusters of ruthenium and iridium.
34/1998 HOMANEN Pertti: Catalyst precursors for the water-gas shift reaction: Synthesis and characteri
zation of modified ruthenium mono(2,2'-bipyridine) complexes.
35/1998 TYNJL Pekka: Modification of the shape selective properties of microporous zeolites.
36/1998 JOUTSINIEMI Karoliina: Mass spectrometric studies on differently substituted mono- and
multi-ring N,N, N,O and N,S heterocycles.
37/1998 AULASKARI Paula: Preparation of histamine analogues with potential pharmaceutical activity.
38/1998 TIMONEN Juha: High field NMR studies of solids and surfaces.
39/1999 TIMONEN Sari: Novel metallocene-type transition metal catalysts for ethylene polymerization.