Conversion of glycerol to the valuable intermediates acrolein and allyl alcohol in the presence of heterogeneous catalysts [Elektronische Ressource] / vorgelegt von Arda Ülgen

Arda Ülgen

Informations

• Publié par: rheinisch-westfalischen_technischen_hochschule_-rwth-_aachen
• Publié le: 01 janvier 2009
• Nombre de lectures: 26
• Langue: English
• Poids de l'ouvrage: 1 Mo

Extrait

Conversion of glycerol to the valuable
intermediates acrolein and allyl alcohol in
the presence of heterogeneous catalysts

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

Diplom-Chemiker
Arda Ülgen
aus Istanbul

Berichter: Universitätsprofessor Dr. Wolfgang F. Hölderich sprofessor Dr. Manfred Martin
Tag der mündlichen Prüfung: 14.09.2009

Diese Dissertation ist auf den Internetseiten der Hochschulbibliothek online verfügbar.

For my beloved father Dr. Remzi Ülgen













This work was carried out between September 2005 and July 2008 at the Chair for
Chemical Technology and Heterogeneous Catalysis at the RWTH Aachen University.
Parts of this thesis have been published or submitted for publication.
I would like to express my sincere thanks to Prof. Dr. Hölderich for providing the
interesting topic, outstandingly good working conditions, for his advice, inspiration
and for the freedom of research which I always appreciated.
Prof. Dr. Martin, I thank for his kind assumption of the co-reference.
I would like to thank to the company Arkema S.A. for its financial support. The fruitful
discussions with Dr. Kervennal, Dr. Dubois, Dr. Devaux, Dr. Teissier, Dr. Linemann,
Ms. Serreau, Dr. Fauconet, Dr. Tretjak and Dr. Haller from Arkema S.A. were always
encouraging me throughout my studies.
Special thanks to Dr. Sabater, for the engineering support, constant help and
advices. I also like to thank to Mr. Vaessen and Ms. Biener, for the catalyst
characterization measurements.
I owe many thanks to the research students, Mr. Schill, Mr. Sopgwi and Ms. Tulimat,
for their energetic engagement.
I would like to thank all technicians, all my friends with whom I have shared the
laboratory for their help and support.
I am very grateful to my family, especially to my father who gave me continuous
support and encouragement during my studies.
Table of contents
A INTRODUCTION................................................................................................. 1
1 Scope of the work ............................................................................................ 1
2 The motivation 2
B BASIC KNOWLEDGE ......................................................................................... 6
1 Green chemistry and heterogeneous catalysis ................................................ 6
2 Relevant compounds ..................................................................................... 10
2.1 Glycerol .................................................................................................. 10
2.2 Acrolein................................................................................................... 18
2.3 Ally alcohol ............................................................................................. 23
3 Heterogeneous catalysts used in this work.................................................... 26
4 Brief information about techniques and reactors used in the work................. 30
C STATE OF THE ART......................................................................................... 33
D RESULTS AND DISCUSSION .......................................................................... 36
1 Zirconia based catalysts ................................................................................ 36
1.1 Tungstated zirconia 37
1.1.1 Commercial catalysts ...................................................................... 37
1.1.1.1 Preliminary experiments .............................................................. 38
1.1.1.2 Studies on the catalyst properties and its effect on the reaction.. 45
1.1.2 Self made WO /ZrO catalysts......................................................... 53 3 2
1.2 Heteropolytungstate on zirconia ............................................................. 55
1.3 Sulfated zirconia ..................................................................................... 56
1.4 A global view on acidity and basicity for zirconia catalysts ..................... 58
1.5 Cerium oxide on zirconia ........................................................................ 63
1.6 Reaction route studies with tungstated zirconia catalysts....................... 65
1.6.1 Statistical studies............................................................................. 65
1.6.2 Products applied as main reactants................................................. 69
1.6.3 Summary: The reaction route of glycerol dehydration ..................... 72
1.6.4 Formation of propionaldehyde......................................................... 74
1.6.5 Formation of acetaldehyde .............................................................. 77
1.6.6 The formation of acetol.................................................................... 78
1.6.7 Formation of other products............................................................. 78
2 Titania based catalysts .................................................................................. 79
2.1 Titania carriers without loading ............................................................... 80
I Table of contents
2.2 Influence of WO amount on Hombikat Typ II based catalysts ............... 82 3
2.3 Influence of temperature over 17,8 wt. % WO /TiO (Hombifine N)........ 86 3 2
2.4 Variation of titania carriers and influence of oxygen ............................... 87
2.5 Influence of calcination temperature....................................................... 91
2.6 Comparison of P-WO and WO ............................................................. 92 3 3
2.7 Comparison of different catalysts in the long term runs .......................... 93
2.8 Multi-component catalysts ...................................................................... 96
3 Studies for the production of allyl alcohol 99
E SUMMARY AND OUTLOOK ............................................................................101
F EXPERIMENTAL PART ...................................................................................105
1 Chemicals .....................................................................................................105
2 Catalyst preparation......................................................................................105
3 Reactor set-up and catalyst screening..........................................................106
4 Analysis ........................................................................................................109
4.1 Catalyst characterization .......................................................................109
4.1.1 Qualitative product analysis............................................................109
4.1.2 Quantitative product analysis..........................................................110
G APPENDIX .......................................................................................................122
1 Catalyst numbers..........................................................................................122
2 Experiment parameters.................................................................................123
3 Detailed experimental results........................................................................126
H REFERENCES.................................................................................................131



II Table of abbreviations
Å Angstrom
Acr Acrolein
Al. Alc. Allyl alcohol
BET Brunauer, Emmett and Teller
Calc. Calcined, calcination
CAS Chemical abstracts service
Cat. Catalyst
et al. et alii
Me Methyl
MeOH Methanol
Exp. Experiment
FID Flame ionization detector
Gly Glycerol
h Hour
Het. Heterogeneous
i.e. id est
ICP Inductive couple plasma
Min. Minimum, minute
mt Metric tons
mln Milliliter under normal conditions
N/A Not available
p Page
PSD50 Particle size distribution, 50 %
S Selectivity
scCO Super critical carbon dioxide 2
T Temperature
TCD Thermal conductivity detector
TPD programmed desorption
wt. % Weight percent
X Conversion
Y Yield

III Introduction
A INTRODUCTION
1 Scope of the work
The aim of the present work is the investigation of heterogeneously catalyzed
continuous conversion of glycerol out of the biodiesel production to the valuable
intermediates acrolein and allyl alcohol in the gas phase. In the case of acrolein, the
reaction is basically the elimination of two molecules of water from glycerol thus can
be also referred as dehydration.

Figure 1: The investigated reaction; dehydration of glycerol to acrolein.
In the case of allyl alcohol, the stoichiometric equation is given in figure 2.

Figure 2: The investigated reaction; dehydration of glycerol to allyl alcohol.
The development of suitable catalysts, screening of these catalysts under different
experimental conditions, as well as inve