Hydrogenation of tetralin over oxide supported Pt and Pt-Pd catalysts [Elektronische Ressource] / Benjamin Fonfé

B9542

Informations

• Publié par: technische_universitat_munchen
• Publié le: 01 janvier 2008
• Nombre de lectures: 17
• Langue: English
• Poids de l'ouvrage: 7 Mo

Extrait

TECHNISCHE UNIVERSITÄT MÜNCHEN
Lehrstuhl für Technische Chemie II


Hydrogenation of tetralin over oxide supported Pt and
Pt-Pd catalysts

Benjamin Fonfé

Vollständiger Abdruck der von der Fakultät für Chemie der Technischen
Universität München zur Erlangung des akademischen Grades eines

Doktors der Naturwissenschaften

genehmigten Dissertation.


Vorsitzender: Univ.-Prof. Dr. Kai-Olaf Hinrichsen

Prüfer der Dissertation:
1. Univ.-Prof. Dr. Johannes A. Lercher
2. Univ.-Prof. Dr. Klaus Köhler



Die Dissertation wurde am 27.08.2008 bei der Technischen Universität München
eingereicht und durch die Fakultät für Chemie am 17.11.2008 angenommen.

Acknowledgements

During the last four years working at TC 2 I have met many interesting people from all over
the world. Although I cannot acknowledge everyone here in person I would like to thank all
of you as every single person has contributed in some way on my climb to the top of the
mountain called PhD thesis.
Johannes, thank you for having given me the opportunity to experience science in an
ambitious and challenging, but also pleasant environment. I was always pleased to get your
opinion on the deeper understanding of catalysis and on the question how to combine data sets
to a fascinating story. It was fun to walk with you through Amsterdam discussing about sulfur
tolerance and stroopwafels. Moreover I greatly appreciate that you provided me the contacts
to Enrique Iglesia and Katia Fajerwerg during my undergraduate studies. Besides Garching,
Berkeley and Paris were the most interesting periods of my life. There, I did not only get
perfect scientific access to catalysis and an insight into the American and French culture. I
also made a lot of friends worldwide, who still play an important role in my life today.
Rob van Veen was the most friendly project partner I could imagine. Thanks for the
productive discussions and the generous financial support of Shell R.T.C. Amsterdam.
Florencia, you are a special person for me and I will never forget your Argentinean temper.
Thank you for your guidance during the first year. We were a really cool team!
Although the EXAFS trips to Hamburg were very exhausting it was always a special
atmosphere at Hasylab and a lot fun to work in the team during day and night. Thank you
Andy for introducing me into the topic and helping me in the particle modeling.
Thanks Marianne for showing me the art of taking TEM pictures in focus. Thanks Xaver and
Andreas for all your help in building the set-up and solving technical problems whenever it
was necessary. Martin, thank you for the BET and AAS measurements.
Many students did a great job and contributed to the present work. I would like to point out
especially Yanzhe and Mahdi, who spent a lot of time operating the trickle bed reactor set-up
and analyzing the data. Thank you!
Virginia and Ella, thanks for your deep friendship! I could not imagine better office mates and
I hope that we will keep close contact in the future even when separated by the Atlantic
Ocean.
Finally, I would like to mention my family and friends for invaluable support. Thank you
forever for your love and all the things you did for me!
Contents
Chapter 1
General introduction
1 Background and motivation ........................................................................................ 2
1.1 Growing diesel fuel demand worldwide ............................................................. 2
1.2 Pollution caused by diesel engines and their effects ........................................... 4
1.3 Reduction of diesel engine emissions ................................................................. 6
1.4 Diesel fuel properties and their effect on emissions............................................ 8
1.4.1 Physical properties ...................................................................................... 8
1.4.2 Cetane number............................................................................................. 9
1.4.3 Sulfur compounds ..................................................................................... 10
1.4.4 Aromatic compounds ................................................................................ 10
1.5 Legislation for diesel fuel composition............................................................. 12
2 Ultra clean diesel fuel production by catalytic hydrotreating ................................... 12
2.1 Hydrodesulfurization (HDS) ............................................................................. 13
2.2 Hydrodenitrogenation (HDN) ........................................................................... 15
2.3 Hydrodearomatization (HDA)........................................................................... 17
2.4 Industrial process options for deep hydrotreatment .......................................... 20
2.5 Catalysts and nature of catalytic sites for deep hydrodearomatization ............. 22
2.5.1 Role of the acidity for the activity and sulfur resistance of noble metals . 23
2.5.2 Active phase and sulfur tolerance of bimetallic Pt-Pd catalysts ............... 24
3 Scope of the thesis..................................................................................................... 26
4 References ................................................................................................................. 28
Chapter 2
Characterization of ASA-supported platinum and platinum-palladium catalysts
27by Al (3Q) MAS NMR, IR, TEM, EXAFS and XANES
1 Introduction ............................................................................................................... 34
2 Experimental ............................................................................................................. 36
I2.1 Preparation and chemical composition of oxide supported Pt and Pt-Pd-
catalysts ......................................................................................................................... 36
2.2 Atomic absorption spectroscopy ....................................................................... 36
2.3 Specific surface area and porosity..................................................................... 36
2.4 Nuclear magnetic resonance spectroscopy........................................................ 37
2.5 Infrared spectroscopy ........................................................................................ 37
2.5.1 Pyridine adsorption ................................................................................... 37
2.5.2 CO adsorption ........................................................................................... 38
2.6 Transmission electron microscopy (TEM)........................................................ 39
2.7 Extended X-ray absorption fine structure ......................................................... 39
3 Results ....................................................................................................................... 41
3.1 Chemical composition and textural properties of the oxide supported Pt and Pt-
Pd catalysts.................................................................................................................... 41
3.2 Characterization of the aluminum species......................................................... 42
3.3 Acidic properties of the noble metal catalysts .................................................. 46
3.4 Characterization of the noble metal nanoclusters.............................................. 49
3.4.1 Platinum particles...................................................................................... 49
3.4.2 Bimetallic platinum-palladium particles ................................................... 59
4 Discussion ................................................................................................................. 72
4.1 Domains in amorphous silica alumina and their implications on the acid site
distribution .................................................................................................................... 72
4.2 Characterization of the Pt phase in the ASA supported platinum catalysts ...... 75
4.3 Alloy formation in the oxide supported bimetallic Pt-Pd phase ....................... 77
5 Conclusions ............................................................................................................... 80
6 References ................................................................................................................. 81
Chapter 3
Hydrogenation of tetralin by silica-alumina supported Pt catalysts I -Mechanistic
aspects in the presence of sulfur and nitrogen containing poisons
1 Introduction ............................................................................................................... 86
2 Experimental ............................................................................................................. 87
2.1 Catalytic measurements..................................................................................... 87
2.2 Characterization of the spent catalyst samples.................................................. 90
II3 Results ................................