Propane aromatization over gallium containing HZSM-5 zeolites

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Propane aromatization over gallium containing HZSM-5
zeolites
Citation for published version (APA):
Bayense, C. R. (1991). Propane aromatization over gallium containing HZSM-5 zeolites. [Phd Thesis 1
(Research TU/e / Graduation TU/e), Chemical Engineering and Chemistry]. Technische Universiteit Eindhoven.
https://doi.org/10.6100/IR357356
DOI:
10.6100/IR357356
Document status and date:
Published: 01/01/1991
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C.R. Baijense
PROPANE AROMATIZATION
OVER
GALLIUM CONTAINING
HZSM-5 ZEOLITES
PROEFSCHRIFr
ter verkrijging van de graad van doctor aan de
Technische Universiteit Eindhoven, op gezag van
de Rector Magnificus, prof.dr. J.H. van lint, voor
een commissie aangewezen door het College van
Dekanen in het openbaar te verdedigen op
dinsdag 24 september 1991 om 16.00 uur
door
CORNELIS ROELAND BADENSE
geboren te Gameren
Dit proefschrift is goedgekeurd door de promotoren:
Prof. dr. ir. J.H.C. van Hooff
en
Prof. dr. R.A. van Santen
Dr. ir. J.W. de Haan (co-promotor)
"Wat hebt gij, dat gij niet hebt ontvangen?"
(1 Kor. 4: 7b)
Voor mijn Moeder
AanJetty
The investigations described in this thesis were supported by het Netherlands
Organization of Scientific Research (NWO)
CONTENTS
CHAPTER 1: GENERAL INTRODUCTION 1
1.1 Hydrocarbon conversions over zeolites 1
1.2 Zeolites and related materials: definition and classification 3
1.3 Scope .of the thesis 6
1.4 References 7
CHAPTER 2: CATALYfIC PROPERTIES OF THE BIFUNCTIONAL
Pt-and Ga/HZSMS SYSTEM 9
2.1 General Introduction 9
2.2 Acid catalysis over zeolites 10
2.3 Paraffin aromatization over the bifunctional Pt/· or
Ga/H(Al)ZSMS system 13
2.4 The chemical and physical properties of gallium and galliumo:xide 14
2.5 References 19
CHAPTER 3: PREPARATION OF HZSMS ZEOLITES CONTAINING
GALLIUM 22
3.1 General Introduction 22
3.2 Preparation of isomorphously substituted H(Ga)ZSM5 zeolites 22
3.2 1. Preparation via the direct method 22
3.2.2 Preparation via trimethylgallium (TMG) decomposition 29
3.3 Preparation of Ga/H(Al)ZSMS zeolites 39
3.4 References 41
CHAPTER 4: APPLICATION OF GALLIUM CONTAINING HZSMS
ZEOLITES FOR PROPANE AROMATIZATION 43
4.1 General Introduction 43
42 The role of gallium in the separate reaction steps 43
4.3 Activity of framework gallium versus extra-framework gallium 52
4.4 Hz chemisorption on H(Ga)ZSMS zeolites and mechanism of molecular
hydrogen formation 56
4.5 References 59
CHAPTER 5: DEACTIVATION BEHAVIOUR OF Ga-CONTAINING
HZSMS ZEOLITES DURING PROPANE AROMATIZATION 62
5.1 Influence of the preparation method 62
5.2 The nature of the coke formed on HZSM5 zeolites as studied by Be MAS
n
N~
5.3 Structural changes in the catalyst induced by coking and regeneratio~ 80
5.4 The influence of Hz in the feed on the deactivation rate 83
5.5 Conversion of paraffin/olefin mixtures over H(Ga)ZSM5 87
5.6 References 91
CHAPTER 6: THE SELECTIVE INTRODUCTION OF EXTRA
FRAMEWORK GALLIUM IN H(AJ +Ga)ZSMS ZEOLITES 93
6.1 Introduction 93
6.2 Experimental 94
6.3 Results and Discussion 95
6.4 Conclusions 105
6.5 References 106
1
CHAPTER 7: APPLICATION OF 7 Ga MAS NMR ON H(Ga)ZSMS
GALWSILICATES 107
7.1 General Introduction 107
7 .2 Theoretical aspects of (MAS) NMR 108
7.3 Steaming of H(Ga)ZSM5 zeolites: determination of tetrahedrally and
octahedrally coordinated gallium 110
7.4 Factors affecting the shape of the 71Ga and 69Ga NMR lines 114
7.5 References 119
CHAPTER 8: QUANTITATIVE DETERMINATION OF GALLIUM IN
1
H(Ga)ZSMS ZEOLITES BY 7 Ga MAS NMR SPECTROSCOPY 121
8.1 General Introduction 121
8.2 Experimental 122
8.3 Results 125
8.4 Discussion 133
8.5 Conclusions 139
8.6 References 140
CHAPTER 9: THE USE OF ZINC CONTAINING HZSMS ZEOLITES
FOR THE AROMATIZATION OF PROPANE 142
9.1 General Introduction 142
92 Preparation of HZSM5 zeolites containing zinc 143
9.3 The preparation of Zn-Al-coprecipitate/H(Al)ZSM5 and its use for alkane
aromatization 149
9.4 Conclusions 157
9.5 References 157
CHAPTER 10: PREPARATION, CHARACTERIZATION AND
CATALYSIS OVER GAPS0-11 MOLECULAR SIEVES 159
10.1 General Introduction 158
10.2 Experimental 160
10.3 Results and Discussion 161
10.4 Conclusions 168
10.5 References 168
CHAPTER 11: CONCLUDING REMARKS 169
SUMARRY 174
SAMENVA1TING 176
DANKWOORD 179
LIST OF PUBLICATIONS 180
CURRICULUM VITAE 181
Nomenclature of the different Ga-containinii HZSMS zeolites
ISOMORPHOUSLY SUBSTITUTED ZEOLITES
General:
H(Al)ZSMS : ZSMS with framework aluminum
H(Ga)ZSMS : ZSMS with framework gallium
H(Al+Ga)ZSMS : ZSMS with framework aluminum and framework gallium
Detailed composition (all Al and Ga on framework positions):
Al-y : H(Al)ZSMS containing y framework-Al atoms/unit cell
Ga-x : H(Ga)ZSMS containing x framework-Ga atoms/unit cell
Al-y/Ga-x : H(Al + Ga)ZSMS containing x framework Ga and y
framework Al atoms/unit cell
SYSTEMS CONTAINING NON·FRAMEWORK. GALLIUM:
prepared by impregnation:
with galliumchloride: Al-y/Ga-x/IM/Cl
with galliumnitrate: Al-y/Ga-x/IM/NO)
prepared by ion-exchange: Al-y/Ga-x/IE
prepared by physical mixing with Ga203: Al-y /Ga-x/PM
where y = number of framework Al atoms/unit cell
x = number of extra-framework Ga atoms/unit cell