Daftar Isi
Daftar Isi....................................................................................................... i
Daftar Tabel ............................................................................................... iv
Daftar Gambar ............................................................................................. v
Chapter 1: Nitriles formation and conversion reactions ............................. 1

Abstract ........................................................................................... 1
1. Aromatic nitriles: Produktion and applications........................... 1
1.1. Ammoxidation reactions ....................................................... 1
1.2. (Potensial) Applications of nitriles........................................ 1
1.3. Aromatic nitriles as intermediates in selective oxidation reactions 1
2. Scope of research ........................................................................ 1

References ....................................................................................... 1
Chapter 2: Toluene ammoxidation mechanism........................................... 1

Abstract ........................................................................................... 2
1. Main reaction step during ammoxidation ................................... 2
2. Toluene activation ....................................................................... 2
2.1. Hydrocarbon rupture ............................................................. 2
2.2. Effect of subtituents on the aromatic ring ............................. 2
2.3. Effect of the catalyst basicity on the ammoxidation of alkyarromatics ............................................................................................. 2
2.4. Nature of aromatic reaction intermediate .............................. 2
3. Ammonium activation ................................................................. 2
4. Catalyst reoxidation .................................................................... 3
5. Toluene ammoxidation reaction schemes ................................... 3
5.1. The propylene ammoxidation mechanism ............................ 3
5.2. The ammoxidation of toluene ............................................... 3
6. Conclusions ................................................................................. 3

References ....................................................................................... 3
Chapter 3: Screening of new toluene ammoxidation catalyst ..................... 3

Abstract ........................................................................................... 3
1. Introduction ................................................................................. 3
2. Experimental methods ................................................................. 4
2.1. Catalyst preparation and characterization ............................. 4
2.2. Catalyst testing ...................................................................... 4
3. Result and discussion .................................................................. 4
3.1. Catalyst screening ................................................................. 4
3.2. Catalyst deactivation ............................................................. 4
3.2.1. Performance of ion-exchanged catalyst ......................... 4
3.2.2. Performance of catalyst prepared by CVD of metal carbonyls 4
3.2.3. Performance of NaY based impregnated catalyst .......... 4
3.2.4. Performance of γ-alumina supported catalyst ................ 4
i

3.3. Benzonitrile selective ............................................................ 4
3.4. Temperature influence .......................................................... 4
4. Conclusions ................................................................................. 4

References ....................................................................................... 5
Chapter 4: Faujasite encaged metal oxide toluene ammoxidation catalyst prepared from metal carbonyl precursors ............................................................... 5

Abstract ........................................................................................... 5
1. Introduction ................................................................................. 5
2. Material and methods .................................................................. 5
2.1. Catalyst preparation .............................................................. 5
2.2. Catalyst characterization ....................................................... 5
2.2.1. Determination of the catalyst composition .................... 5
2.2.2. X-ray photoelectron spectroscopy.................................. 5
2.2.3. Transmission Electron Microscopy ............................... 5
2.2.4. Temperature Programmed Oxidative Decarbonylation . 5
2.3. Catalytic test .......................................................................... 5
2.3.1. 2-methyl-3butyn-2-ol decomposition............................. 5
2.3.2. Toluene ammoxidation................................................... 5
3. Result and discussion .................................................................. 6
3.1. Thermal activation of intra-zeolite Mo(CO)
6
........................ 6
3.2. XPS analysis of Mo(CO)
6
/NaY and Mo(CO) x
/NaY ............. 6
3.3. Dispersion of molybdenum oxide clusters in NaY ............... 6
3.4. Mo(CO)
6
interaction with the faujasite lattice ...................... 6
3.5. Introduction of other transition metal carbonyls by CVD .... 6
3.5.1. Intoduction of V(CO)
6
into NaY .................................... 6
3.5.2. Introduction of Mn
2
(CO)
10
into NaY ............................. 6
3.5.3. Introduction of Co(NO)(CO)
3
into NaY ........................ 6
3.6. Catalytic activity in the ammoxidation of toluene ................ 6
3.7. The effect of the lwis acidity and basicity on the ammoxidation of toluene over MoO
X
/Y ..................................................... 6
4. Conclusion .................................................................................. 6

References ....................................................................................... 7
Chapter 5: The effect molybdenum oxide reducibility on the ammoxidation of toluene......................................................................................... 7

Abstract ........................................................................................... 7
1. Introduction ................................................................................. 7
1.1. Preparation methods of supported Mo catalyst ..................... 7
1.2. Notation of different Mo species........................................... 7
1.3. Molybdate surface species .................................................... 7
1.4. Characterization of Mo surface species ................................ 7
1.5. Molybdate and Mo oxide reduction ...................................... 7
2. Material and methods .................................................................. 8
2.1. Catalyst preparation .............................................................. 8
2.2. Catalyst characterization ....................................................... 8
2.2.1. Diffuse reflection UV-Vis spectroscopy ........................ 8
2.2.2. Temperature Programmed Reduction ............................ 8
ii

2.2.3. Raman Spectroscopy ...................................................... 8
2.2.4. Tranmmision Electron Microscopy ............................... 8
2.2.5. X-ray Diffraction ............................................................ 8
2.2.6. X-ray Photoelectron Spectroscopy ................................. 8
2.2.7. Hydrogen-deuterium exchange reaction ........................ 8
2.3. Ammoxidation toluene .......................................................... 9
3. Results and discussion ................................................................ 9
3.1. Addition of a second metal to Mo/Al .................................... 9
3.2. Variation of the molybdenum oxide loading ........................ 9
3.3. DR-UVVis Spectroscopy ...................................................... 9
3.4. Reduction of Mo/Al catalyst ................................................. 9
3.5. Hydrogen-deuterium exchange over Mo/Al catalyst ............ 9
3.6. Transmission Electron Microscopy on Mo/Al samples ........ 9
3.7.
In situ treatment of Mo/Al..................................................... 9
4. Conclusions ................................................................................. 9

Reference......................................................................................... 9
Summary ..................................................................................................... 9
Samenvatting .............................................................................................. vi
Dankwoord ................................................................................................ vii
Curriculum Vitae ...................................................................................... viii
iii

Daftar Tabel
Tabel 1: Tabel kosong ............................................................................................ 2
Tabel 2: Tabel baru ................................................................................................ 4
Tabel 3: Tabel juga................................................................................................. 6
Tabel 4: Tabel keempat .......................................................................................... 7
Tabel 5: Aku tabel .................................................................................................. 8
iv

Daftar Gambar
gambar 1: dari si aneh ............................................................................................ 1
gambar 2: arale jorok ............................................................................................. 2
gambar 3: Chibi ...................................................................................................... 3
gambar 4: Lucu ya .................................................................................................. 5
gambar 5: Sailor moon ........................................................................................... 9
v

Chapter 1: Nitriles formation and conversion reactions

Abstract
1. Aromatic nitriles: Produktion and applications
1.1.
Ammoxidation reactions
The reaction of reducible hydrocarbon with ammonia and oxygen are reffered to as ammoxidation reactions. Alkenes, alkanes and aromatic ae used most often in ammoxidation reactions. The catalyst that are activate in ammoxidation reaction consist mainly of mixed oxides containing variablevalence transition metals.
1.2.
(Potensial) Applications of nitriles
1.3.
Aromatic nitriles as intermediates in selective oxidation reactions
2. Scope of research
The research in this thesis was aimed at the development of new, selective and clean processes for alkylaromatic side chain oxidation. A gas phase was chosen for the conversion of the alkylaromatic side chain oxidation, based on the poor opportunities for liquid-phase processes. Catalyst leaching complicates severely the possibilities of liquid-phase heterogeneously catalyzed processes.
Lihat gambar 1.
gambar 1: dari si aneh

References
Chapter 2: Toluene ammoxidation mechanism
1


Abstract
1. Main reaction step during ammoxidation
In Toluene ammoxidation reactions three important processes occur: toluene activation, during which the methyl group has to be dehydrogenated.
Ammonia activation, leading to formation of the nitrogen insertion species.
Reoxidation of the catalyst by consumption of gas-phase oxygen.
2. Toluene activation
The pathway of the hydrocarbon activation has been studied by several group, mostly by applying kinetic studies or spectroscopy. If nitriles productions occurs along the side chain three basic types of C-H activation must be
considered. Lihat Tabel 1.
Tabel 1: Tabel kosong
2.1.
Hydrocarbon rupture
2.2.
Effect of subtituents on the aromatic ring
2.3.
Effect of the catalyst basicity on the ammoxidation of alkyarromatics
2.4.
Nature of aromatic reaction intermediate
3. Ammonium activation
Ammonium plays multiple ole in the ammoxidation of toluene. It is the source of nitrogen atoms, it also reduces the catalyst and/or it is absorbed on the catalyst blocking sites that otherwise could have weakly bound oxygen, which
could lead to total oxidation. Lihat gambar 2
gambar 2: arale jorok
2

4. Catalyst reoxidation
With respect to the oxygen inserting species in the alkylaromatic
(amm)oxidation mechanism a Mars-Van Krevelen Mechanism is Originally accepted. The hydrocarbon is oxygenated by lattice oxygen.
5. Toluene ammoxidation reaction schemes
5.1.
The propylene ammoxidation mechanism
5.2.
The ammoxidation of toluene
6. Conclusions
Up to now, there is no general agreement in literature considering the exact reaction mechanism for ammoxidation of toluene. Many authors, though, agree on the presence of an oxygenated adsorbed organic intermediate as first
reaction step. Lihat gambar 3
gambar 3: Chibi

References
Chapter 3: Screening of new toluene ammoxidation catalyst

Abstract
1. Introduction
Aromatic nitriles are widely used as solvents in organic reactions. In addition the nitriles group can be easily converted by means of hydrogenation, hydrtions, or hydrolysis reactions to amines, amides, imines and other functional group. These functional group are found in many intermediates in polymer and pharmaceutical industry.
3

2. Experimental methods
2.1.
Catalyst preparation and characterization
2.2.
Catalyst testing
3. Result and discussion
It must be noted that the catalytic performance of supported vanadia catalyst generally strongly depends on the loading. Cavalli et al. found higher benzonitrile yields upon increase of the V for V/Ti. When the monolayer loading
was reached no further increase benzonitrile yield was observed. Lihat Tabel 2.
Tabel 2: Tabel baru
3.1.
Catalyst screening
3.2.
Catalyst deactivation
3.2.1.
Performance of ion-exchanged catalyst
3.2.2.
Performance of catalyst prepared by CVD of metal carbonyls
3.2.3.
Performance of NaY based impregnated catalyst
3.2.4.
Performance of γ -alumina supported catalyst
3.3.
Benzonitrile selective
3.4.
Temperature influence
4. Conclusions
The toluene ammoxidation can be catalyzed by the zeolitic and by γalumina supported metal oxide catalyst. Among the zeolite-based samples, both incipient wetness and VCD methods can be applied.
Although the benzonitrile can be greatly improved by using ion exchanged technique, the initial stability during time on steam is dramatically lowered for
Cu(ie,4.4)/NaY. Lihat
4

gambar 4: Lucu ya

References
Chapter 4: Faujasite encaged metal oxide toluene ammoxidation catalyst prepared from metal carbonyl precursors

Abstract
1. Introduction
The introduction of high valent metal ions inti zeolite via ion exchange is imposible, due to insufficient stabilization of highly charged cations inside the zeolite lattice. Application of conventional impregnation size techniques also is not preferable in most cases, because of the restricted size of zeolite pores.
2. Material and methods
2.1.
Catalyst preparation
2.2.
Catalyst characterization
2.2.1.
Determination of the catalyst composition
2.2.2.
X-ray photoelectron spectroscopy
2.2.3.
Transmission Electron Microscopy
2.2.4.
Temperature Programmed Oxidative Decarbonylation
2.3.
Catalytic test
2.3.1.
2-methyl-3butyn-2-ol decomposition
2.3.2.
Toluene ammoxidation
5

Tabel 3: Tabel juga
3. Result and discussion
The absence of a second CO desorption peak may be explain by the experimental conditions. In comparison with experiments using catalyst in the form of thin wafers we have used a relatively large a mount o catalyst. During the temperature programmed desorption the He flow becomes partly can be saturated with the desorbing CO.
3.1.
Thermal activation of intra-zeolite Mo(CO)
6
3.2.
XPS analysis of Mo(CO)
6
/NaY and Mo(CO) x
/NaY
3.3.
Dispersion of molybdenum oxide clusters in NaY
3.4.
Mo(CO)
6
interaction with the faujasite lattice
3.5.
Introduction of other transition metal carbonyls by CVD
3.5.1.
Intoduction of V(CO)
6
into NaY
TEM confirmed the expected low dispersion of vanadia clusters over the sample. EDX analysis showed that some sefments of the sample did contain only vanadium whereas other parts of the sample did not contain any vanadium at all.
3.5.2.
Introduction of Mn
2
(CO)
10
into NaY
3.5.3.
Introduction of Co(NO)(CO)
3
into NaY
3.6.
Catalytic activity in the ammoxidation of toluene
3.7.
The effect of the lwis acidity and basicity on the ammoxidation of toluene over MoO
X
/Y
4. Conclusion
Over Mn/NaY catalyst the ammoxidation of toluene was accompanied with strong deactivation. Lack of available oxygen seemed to govern the low benzonitrile selectivity. Toluene ammoxidation over Mo/NaY was influenced by
the acid/base properties of the catalyst. Lihat Tabel 4.
6

Tabel 4: Tabel keempat

References
Chapter 5: The effect molybdenum oxide reducibility on the ammoxidation of toluene

Abstract
1. Introduction
Supported molybdenum oxide catalyst have been described in the literature very frequently. Since Mo based catalyst formulations are applied in many type of catalytic reactions, such as selective (amm)oxidations, metathasis and hydrotreating, both the preparation and the surface properties of these catalyst have been intensively studied.
1.1.
Preparation methods of supported Mo catalyst
1.2.
Notation of different Mo species
1.3.
Molybdate surface species
1.4.
Characterization of Mo surface species
1.5.
Molybdate and Mo oxide reduction
Raman spectroscopy has been applied very frequently to study the Mo surface species, which are formed after calcinations of the impregnated catalyst.
As explained above, AHM impregnation followed by cacination can lead to different surface molybdate and molybdenum oxide species.
7

2. Material and methods
2.1.
Catalyst preparation
2.2.
Catalyst characterization
2.2.1.
Diffuse reflection UV-Vis spectroscopy
2.2.2.
Temperature Programmed Reduction
2.2.3.
Raman Spectroscopy
2.2.4.
Tranmmision Electron Microscopy
Lihat Tabel 5
Tabel 5: Aku tabel
2.2.5.
X-ray Diffraction
2.2.6.
X-ray Photoelectron Spectroscopy
2.2.7.
Hydrogen-deuterium exchange reaction
8

2.3.
Ammoxidation toluene
3. Results and discussion
3.1.
Addition of a second metal to Mo/Al
3.2.
Variation of the molybdenum oxide loading
3.3.
DR-UVVis Spectroscopy
3.4.
Reduction of Mo/Al catalyst
3.5.
Hydrogen-deuterium exchange over Mo/Al catalyst
3.6.
Transmission Electron Microscopy on Mo/Al samples
3.7.
In situ treatment of Mo/Al
The lower of Mo/Al samples tahat have a Mo loading below 10 wt% may explain the lower toluene ammoxidation. In situ Raman spectroscopy applied to examine the effect of thermal treatment using various gas flow on the chemisty
surface molybdates. Lihat gambar 5.
gambar 5: Sailor moon
4. Conclusions

Reference
Summary
Alkyaromatic oxidations is peformed nowadays as a liquid phase reactions, catalysed by metal oxide salt dissolved in the aciditic solution.
Although this processes yields high mounts of oxygenated, the reaction environment is highly demanding on both the equipment is expected to lead the more stringent legislation.
9

Samenvatting vi

Dankwoord vii

Curriculum Vitae viii