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Ammoxidation Reactions 1 1.2 (Potential) Applications of Nitriles 3 1.3 Aromatic Nitriles As Intermediates in Selective Oxidation Reactions 5 2

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Ammoxidation Reactions 1 1.2 (Potential) Applications of Nitriles 3 1.3 Aromatic Nitriles As Intermediates in Selective Oxidation Reactions 5 2 Catalytic conversion of alkylaromatics to aromatic nitriles Citation for published version (APA): Stobbelaar, P. J. (2000). Catalytic conversion of alkylaromatics to aromatic nitriles. Technische Universiteit Eindhoven. https://doi.org/10.6100/IR538872 DOI: 10.6100/IR538872 Document status and date: Published: 01/01/2000 Document Version: Publisher’s PDF, also known as Version of Record (includes final page, issue and volume numbers) Please check the document version of this publication: • A submitted manuscript is the version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website. • The final author version and the galley proof are versions of the publication after peer review. • The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal. If the publication is distributed under the terms of Article 25fa of the Dutch Copyright Act, indicated by the “Taverne” license above, please follow below link for the End User Agreement: www.tue.nl/taverne Take down policy If you believe that this document breaches copyright please contact us at: [email protected] providing details and we will investigate your claim. Download date: 05. Oct. 2021 Catalytic Conversion of Alkylaromatics to Aromatic Nitriles Proefschrift 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 Pieter Johannes Stobbelaar 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 Chapter 1: Nitrile formation and conversion reactions 1 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 Chapter 2: Toluene ammoxidation mechanism 11 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 Chapter 3: Screening of new toluene ammoxidation catalysts 41 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 Chapter 4: Faujasite encaged metal oxide toluene ammoxidation catalysts 67 prepared from metal carbonyl precursors 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)6 75 3.2 XPS analysis of Mo(CO)6/NaY and MoOx/NaY 80 3.3 Dispersion of molybdenum oxide clusters in NaY 84 3.4 Mo(CO)6 interaction with the faujasite lattice 87 3.5 Introduction of other transition metal carbonyls by CVD 92 3.5.1 Introduction of V(CO)6 into NaY 92 3.5.2 Introduction of Mn2(CO)10 into NaY 94 3.5.3 Introduction of Co(NO)(CO)3 into NaY 96 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 MoOx/Y 4. Conclusions 100 References 101 Contents Chapter 5: The effect of molybdenum oxide reducibility on the ammoxidation of 105 toluene 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 Summary 143 Samenvatting 147 Dankwoord 151 Curriculum Vitae 153 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. CH3 + NH3 + 3/2 O2 CN + 3 H2O (1.1) 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 Chapter 1 [2]. The annual world production amounts to 4600 ktons [3]. Until recently the production of acrylonitrile from propane could only be performed at very high temperatures (750 – 1000 °C) [4]. In the late eighties propylene ammoxidation to acrylonitrile has been patented frequently, for example by BP America (previously SOHIO) [5]. Recently, a large variety of new catalysts have been developed for the ammoxidation of propane. Mostly vanadium antimony oxide [6] systems are reported, though also molybdenum based multi-component catalysts are frequently patented [7]. Pilot-plant studies have been performed already [8] and commercial production of acrylonitrile from propane was announced [9]. The feedstock price of propane is significantly lower than that of propylene, but the acrylonitrile yields are markedly lower because of the poor acrylonitrile selectivity [10,11]. This lower acrylonitrile yield per mole of feedstock delays commercial production of acrylonitrile from propane. To date acrylonitrile production from propane has not started yet [12].
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