Catalytic conversion of alkylaromatics to aromatic nitriles

162 Pages·2017·10.42 MB·English

Catalytic conversion of alkylaromatics to aromatic nitriles
Citation for published version (APA):
Stobbelaar, P. J. (2000). Catalytic conversion of alkylaromatics to aromatic nitriles. [Phd Thesis 1 (Research
TU/e / Graduation TU/e), Chemical Engineering and Chemistry]. Technische Universiteit Eindhoven.
https://doi.org/10.6100/IR538872
DOI:
10.6100/IR538872
Document status and date:
Published: 01/01/2000
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ter verkrijging van de graad van doctor aan de
Technische Universiteit Eindhoven, op gezag van de
Rector Magnificus, prof.dr. M. Rem, voor een
commissie aangewezen door het College voor
Promoties in het openbaar te verdedigen op
dinsdag 28 november 2000 om 16.00 uur

door

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geboren te Driebergen-Rijsenburg
Dit proefschrift is goedgekeurd door de promotoren:

prof.dr. R.A. van Santen
en
prof.dr. B.K. Hodnett

CIP-DATA LIBRARY TECHNISCHE UNIVERSITEIT EINDHOVEN

Stobbelaar, Pieter J.

Catalytic conversion of alkylaromatics to aromatic nitriles / by
Pieter J. Stobbelaar. - Eindhoven : Technische Universiteit Eindhoven,
2000. - Proefschrift. - ISBN 90-386-2612-6
NUGI 813
Trefwoorden: katalytische oxidatie ; ammoxidatie / heterogene katalyse ;
zeolieten / overgangsmetaalverbindingen ; molybdeenverbindingen
Subject headings: catalytic oxidation ; ammoxidation / heterogeneous
catalysis ; zeolites / transition metal compounds ; molybdenum
compounds

The work described in this thesis has been carried out at the Schuit Institute
of Catalysis (part of NIOK: the Netherlands School for Catalysis
Research), Laboratory of Inorganic Chemistry and Catalysis, Eindhoven
University of Technology, The Netherlands. Financial support has been
supplied by the European Community under the Industrial & Materials
Technologies Programme (Brite-EuRam III).

Printed at Universiteitsdrukkerij, Eindhoven University of Technology.

Contents

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Abstract 1
1. Aromatic nitriles: Production and applications 1
1.1 Ammoxidation reactions 1
1.2 (Potential) Applications of nitriles 3
1.3 Aromatic nitriles as intermediates in selective oxidation reactions 5
2. Scope of research 7
References 9

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Abstract 11
1. Main reaction steps during toluene ammoxidation 11
2. Toluene activation 12
2.1 Hydrocarbon rupture 12
2.2 Effect of substituents on the aromatic ring 13
2.3 Effect of the catalyst basicity on the ammoxidation of 15
alkylaromatics
2.4 Nature of aromatic reaction intermediate 18
3. Ammonia activation 23
4. Catalyst reoxidation 27
5. Toluene ammoxidation reaction schemes 29
5.1 The propylene ammoxidation mechanism 29
5.2 The ammoxidation of toluene 32
6. Conclusions 35
References 36

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Abstract 41
1. Introduction 41
2. Experimental methods 43
2.1 Catalyst preparation and characterization 43
2.2 Catalyst testing 45
3. Results and discussion 46
3.1 Catalyst screening 46
3.2 Catalyst deactivation 50
3.2.1 Performance of ion-exchanged catalysts 52
Contents
3.2.2 Performance of catalysts prepared by CVD of metal carbonyls 52
3.2.3 Performance of NaY based impregnated catalysts 53
3.2.4 Performance of γ-alumina supported catalysts 55
3.3 Benzonitrile selectivity 57
3.4 Temperature influence 60
3.5 Nitroxidation of toluene 61
4. Conclusions 64
References 64

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Abstract 67
1. Introduction 67
2. Materials and methods 71
2.1 Catalyst preparation 71
2.2 Catalyst characterization 72
2.2.1 Determination of the catalyst composition 72
2.2.2 X-Ray Photoelectron Spectroscopy 73
2.2.3 Transmission Electron Microscopy 73
2.2.4 Temperature Programmed Oxidative Decarbonylation 73
2.3 Catalytic tests 74
2.3.1 2-Methyl-3-butyn-2-ol decomposition 74
2.3.2 Toluene ammoxidation 74
3. Results and discussion 75
3.1 Thermal activation of intra-zeolite Mo(CO) 75
6
3.2 XPS analysis of Mo(CO) /NaY and MoO /NaY 80
6 x
3.3 Dispersion of molybdenum oxide clusters in NaY 84
3.4 Mo(CO) interaction with the faujasite lattice 87
6
3.5 Introduction of other transition metal carbonyls by CVD 92
3.5.1 Introduction of V(CO) into NaY 92
6
3.5.2 Introduction of Mn (CO) into NaY 94
2 10
3.5.3 Introduction of Co(NO)(CO) into NaY 96
3
3.6 Catalytic activity in the ammoxidation of toluene 97
3.7 The effect of the Lewis acidity and basicity on the ammoxidation 99
of toluene over MoO /Y
x
4. Conclusions 100
References 101
Contents

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Abstract 105
1. Introduction 105
1.1 Preparation methods of supported Mo catalysts 106
1.2 Notation of different Mo species 107
1.3 Molybdate surface species 108
1.4 Characterization of Mo surface species 110
1.5 Molybdate and Mo oxide reduction 112
2. Materials and methods 114
2.1 Catalyst preparation 114
2.2 Catalyst characterization 114
2.2.1 Diffuse reflection UV-Vis spectroscopy 114
2.2.2 Temperature Programmed Reduction 115
2.2.3 Raman Spectroscopy 115
2.2.4 Transmission Electron Microscopy 115
2.2.5 X-Ray Diffraction 116
2.2.6 X-Ray Photoelectron Spectroscopy 116
2.2.7 Hydrogen–deuterium exchange reactions 116
2.3 Ammoxidation of toluene 117
3. Results and discussion 117
3.1 Addition of a second metal to Mo/Al 117
3.2 Variation of the molybdenum oxide loading 120
3.3 DR-UVVis Spectroscopy 121
3.4 Reduction of Mo/Al catalysts 124
3.5 Hydrogen-deuterium exchange over Mo/Al catalysts 126
3.6 Transmission Electron Microscopy on Mo/Al samples 131
3.7 In situ treatment of Mo/Al 131
4. Conclusions 137
References 138

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Chapter 1
Nitrile formation and conversion reactions

Abstract
The background of the research project is described. Ammoxidation of
alkylaromatics is a simple gas-phase reaction that yields aromatic nitriles.
These nitriles have versatile applications, mainly as raw material in the
polymer industry. Additionally, alkylaromate ammoxidation can be applied
in the production of selective oxidation products since nitriles can be
converted by hydrolysis and hydrogenation reactions towards acids,
aldehydes, amines and amides. This two-step approach cleanly yields the
oxygenate without production of harmful side products. The project focuses
on the ammoxidation of toluene. For this reaction the development of new
faujasite-based catalysts was performed. Additionally, a comparison with
more conventional γ-alumina supported molybdenum oxide catalysts has
been made.

1. Aromatic nitriles: Production and applications
1.1 Ammoxidation reactions
Aromatic nitriles can be formed by reacting an aromatic hydrocarbon with
ammonia and oxygen. The simplest example is benzonitrile production
from toluene, as shown in Equation 1.1.
CH + NH + 3/2 O CN + 3 H O (1.1)
3 3 2 2
The reaction of a reducible hydrocarbon with ammonia and oxygen are
referred to as ammoxidation reactions. Alkenes, alkanes and aromatics are
used most often in ammoxidation reactions. The catalysts that are active in
ammoxidation reactions consist mainly of mixed oxides containing
variable-valence transition metals.

For the ammoxidation of propylene bismuth-molybdate based systems are
applied industrially on a large scale [1]. The ammoxidation of propylene is
well developed and is commercially applied by Sohio since the early sixties
1