Transformation of biogenic carbohydrates into levulinic acid and further hydrogenation using supported nanoparticle catalysts synthesized by chemical fluid deposition [Elektronische Ressource] / Kai Yan

Zzhang

Informations

• Publié par: rheinisch-westfalischen_technischen_hochschule_-rwth-_aachen
• Publié le: 01 janvier 2011
• Nombre de lectures: 29
• Langue: English
• Poids de l'ouvrage: 15 Mo

Extrait

Transformation of Biogenic Carbohydrates
into Levulinic Acid and further Hydrogenation
using Supported Nanoparticle Catalysts
Synthesized by Chemical Fluid Deposition

Von der Fakultät für Mathematik, Informatik und Naturwissenschaften
der RWTH Aachen University zur Erlangung des akademischen Grades
eines Doktors der Naturwissenschaften genehmigte Dissertation
vorgelegt von

M. Sc. Kai Yan
Aus Anhui / PR China




Berichter: Universitätsprofessor Dr. Walter Leitner
Universitätsprofessor Dr. Jürgen Klankermayer


Tag der mündlichen Prüfung: 28. November 2011



Diese Dissertation ist auf den Internetseiten der Hochschulbibliothek online
verfügbar.















Die vorliegende Arbeit wurde in der Zeit von Oktober 2008 bis November 2011 am
Max-Planck-Institut für Kohlenforschung in Mülheim an der Ruhr unter der Leitung
von Herrn Prof. Dr. Walter Leitner angefertigt.




Referent: Prof. Dr. Walter Leitner
Koreferent: Prof. Dr. Jürgen Klankermayer









Acknowledgments

Firstly and foremost, I would like to thank my supervisors and mentors,
Prof. Dr. Walter Leitner and Dr. Nils Theyssen, for giving me the opportunity to carry
out this interesting and challenging scientific work. Especially for Dr. Theyssen, I am
deeply grateful for his immense support and guidance throughout the entire PhD
thesis. Through his superb leadership he gave me the maximum freedom and great
opportunity for personal development. He is also a good model young researcher for
me. His passion is always unlimited and makes most things perfectly. I would also
like to thank Prof. Dr. Walter Leitner for his fruitful support and agreeing to be my
first referee in the examination board.

Many thanks to Professor Leitner and Dr. Theyssen for the wholehearted introduction
into the world of sustainable biofuel-production and for trusting me fully by the given
freedom. Our exiting team work at the beginning of my thesis has developed into a
sincere friendship, which I cherish and am very proud of.

During my PhD thesis, I was very fortunate to work at the Max-Planck-Institute (MPI)
für Kohlenforschung in Mülheim an der Ruhr. My deep gratitude and respect goes to
the co-worker and the technical staff of the MPI in Mülheim. In particular, I would
like to thank Dr. R. Weiß and especially Mr. F. Qin for a close and highly fruitful
collaboration. During my PhD study, nearly all catalysts were prepared and provided
by them.

Besides, the following coworkers are highly acknowledged for their continuous
support in analyzing my samples:
• C. Heigen (GC),
• H. Hinrichs and A. Deege (HPLC),
• Dr. C. Weidenthaler (XRD and XPS),
• S. Palm (EDX),
• Dr. W. Schmidt (BET),
• H. Bongard (SEM) and
• A. Dreier and B. Spliethoff (TEM). I would like to thank all members of the Dr. Theyssen Group not only for the highly
professional team work I experienced there, but also for the great time during social
activities. I will never forget our daily breakfast meetings, the famous Christmas
parties, birthday celebrations and the group trips.

Finally, I would like to express my sincere thanks to my great parents, brother, sister
and my girlfriend, for their unlimited support and unconditional love. I love all of you!



































Content
CHAPTER 1 – INTRODUCTION........................................................................................................1
1.1 THESIS OUTLINE.............................................................................................................................1
1.2 FUEL GENERATION AND CHEMICALS PRODUCTION DERIVED FROM BIOMASS ..................................3
1.3 DEFINITION, COMPOSITION AND UTILIZATION OF BIOMASS.............................................................4
1.3.1 Definition and composition of biomass ..................................................................................4
1.3.2 Technological description of biomass utilization ...................................................................9
1.3.3 Utilization of biomass in TMFB Project...............................................................................11
1.4 CONVERSION OF BIOMASS TO LEVULINIC ACID .............................................................................13
1.4.1 Methods and catalytic system ...............................................................................................13
1.4.2 Mechanistic aspects of the formation of levulinic acid.........................................................21
1.5 POTENTIAL APPLICATIONS OF LA AND ITS DERIVATIVES..............................................................23
1.5.1 Building blocks derived from levulinic acid .........................................................................23
1.5.2 Economical and ecological considerations ..........................................................................23
1.6 CONVERSION OF BIOMASS-DERIVED MONOMERS TO Γ-VALERLACTONE........................................25
1.6.1 Properties of γ-valerolactone ...............................................................................................25
1.6.2 Catalytic system for production of γ-valerolactone..............................................................27
1.6.3 Mechanistic asepcts for formation of γ-valerolactone..........................................................29
1.7 POTENTIAL DERIVATIVES FROM Γ-VALEROLACTONE ....................................................................30
1.8 PREPARATION OF NANO-CATALYST BY CHEMICAL FLUID DEPOSITION..........................................32
1.8.1 Supercritical fluids ...............................................................................................................32
1.8.2 Preparation of nanostructured catalysts using chemical fluid deposition............................35
1.9 DESCRIPTION AND ACKNOWLEDGEMENT OF THE INTERDISCIPLINARY COLLABORATION ..............39
1.10 REFERENCES ..............................................................................................................................40
CHAPTER 2 EXPERIMENTAL SECTION .....................................................................................47
2.1 CHEMICALS ..................................................................................................................................47
2.2 SBA-15 AND ALSBA-15 SYNTHESIS............................................................................................47
2.2.1 Preparation of SBA-15 .........................................................................................................47
2.2.2 Preparation of AlSBA-15......................................................................................................48
2.3 MCM-41, ALMCM-41 AND ZRMCM-41 SYNTHESIS ..................................................................48
2.3.1 MCM-41 synthesis ................................................................................................................48
2.3.2 AlMCM-41 synthesis.............................................................................................................49
2.3.3 ZrMCM-41 synthesis ............................................................................................................49
2.4 HY SYNTHESIS..............................................................................................................................49
2.5 SYNTHESIS OF (CYCLOPENTADIENYL) ALLYL-PALLADIUM (II) .....................................................49
2.6 SYNTHESIS OF PD NANOPARTICLE BY A MODIFIED CHEMICAL FLUID DEPOSITION.........................51
2.7 HOMO- AND BIMETALLIC CATALYSTS SYNTHESIS BY CHEMICAL FLUID DEPOSITION.....................51 2.8 SELECTIVE DEHYDRATION OF D-FRUCTOSE AND D-GLUCOSE.......................................................53
2.8.1 Dehydration procedure.........................................................................................................53
2.8.2 Sample analysis by HPLC ....................................................................................................54
2.9 DEHYDRATION OF HMF ...............................................................................................................61
2.10 HYDROGENATION OF LEVULINIC ACID INTO Γ-VALEROLACTONE................................................61
2.11 STATISTICAL ANALYSIS BY DESIGN EXPERT..............................................................................62
2.12 PROVING ETHYL LEVULINATE FORMATION.................................................................................62
2.13 FORMIC ACID AS A SUBSTRATE...................................................................................................63
2.14 CATALYST RECYCLING.............................................