Investigation of Ni/ZrO2 catalysts for the hydrodeoxygenation of microalgae oil

139 Pages·2017·5.27 MB·English

by  Sebastian Foraita

TECHNISCHE UNIVERSITÄT MÜNCHEN
Department Chemie
Lehrstuhl für Technische Chemie II

Investigation of Ni/ZrO catalysts for the
2
hydrodeoxygenation of microalgae oil

Sebastian Dieter Foraita

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

Doktors der Naturwissenschaften (Dr. rer. nat.)

genehmigten Dissertation.

Vorsitzender: Univ.-Prof. Dr.-Ing. Kai-Olaf Hinrichsen
Prüfer der Dissertation:
1. Univ.-Prof. Dr. Johannes A. Lercher
2. Univ.-Prof. Dr. Thomas Brück

Die Dissertation wurde am 13.02.2017 bei der Technischen Universität München einge-
reicht und durch die Fakultät für Chemie am 13.03.2017 angenommen.

„Mit meinem Gott überspringe ich Mauern.“ Psalm 18,30

Acknowledgment
It has been a long way and a hard piece of work. There are many people, who supported me
all the way or significant parts of it and contributed to this thesis. I am deeply grateful and
want to particularly thank them, here.
First of all I want to express my sincere gratitude to Johannes (Prof. Dr. Johannes A. Lercher)
giving me an opportunity with this interesting topic in your high level and famous catalysis
group. Thank you for teaching me well and your critical guidance with your broad
knowledge in catalysis and science. I enjoyed the international style and experience of your
group.
I thank Prof. Dr. Thomas Brück as my second examinor and project leader of the Algen-
FlugKraft project supported by Bavarian Ministry of Economic Affairs and Media, Energy
and Technology (“Bayerisches Staatsministerium für Wirtschaft und Medien, Energie und
Technologie”) and Bavarian State Ministry of Education, Science and the Arts (“Bayerisches
Staatsministerium für Bildung und Kultus, Wissenschaft und Kunst”).
I want to thank Chen, Eszter and Yue for their co-supervision as responsible subgroup lead-
ers. Thank you for the help in planning experiments, discussing results and shaping paper
manuscripts and presentations.
Many and special thank deserve to Gary (Prof. Gary Haller) for our fruitful collaboration,
discussions, your patience and the additional guidance. I appreciate your advice a lot.
I am grateful to Don (Donald M. Camaioni) and John L. Fulton from Pacific Northwest
National Laboratory (PNNL) for co-supervision, EXAFS-lessons, scientific discussions,
good collaboration, overwhelming hospitality and the great time at the Advanced Photon
Source in Argonne, IL and the PNNL in Richland, WA.
I appreciate the feedback and support of Andy, Oliver, Maricruz, Erika and André in daily
lab situations and especially in our group’s seminars.
I want to thank Dipl.-Min. Katia Rodewald for teaching me how to operate the High Reso-
lution SEM and sharing her extensive experience with me and Dr. Gabriele Raudaschl-
Sieber for solid state 29Si-NMR measurements.

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Nothing would work without Xaver – I appreciate your help and the support of Martin and
Andreas. My work would not have been possible without Steffi, Uli, Bettina and Karen man-
aging everything from the administrative side.
Many special thanks deserve to my dear office colleagues Xianyong, Eva, Tobias, Stanislav,
Jeongnam, Marco, Yang Song, Takaaki and Christoph for the good atmosphere and being
the first place to go for scientific discussions and other problems. I keep my former col-
leagues Christian, Sebastian G., Sebastian M., Navneet, Lisl, Max, Jenny, Daniela, Jiayue,
Claudia, Robin, Stefan, Anastasia, Bo, Baoxiang, Monica, Steffi, Linus and Sonja in good
memory for their support and the good collaboration especially in the beginning. Addition-
ally, I thank the remaining members of TC II Ferdinand, Martina, Andreas, Kai, Daniel,
Peter, Moritz, Sylvia, Manuel, Edith, Yu, Matthias, Udishnu and Yuanshuai for working
with you. I thank Zizwe, Aleksei and Pinghong from PNNL for our fruitful cooperation as
well.
I thank my former classmates David, Markus, Julia, Sabrina, Sabine and Alex for the inter-
disciplinary discussions and support.
Thanks to my interested, motivated, skilled and hardworking students Sebastian E., Tommy,
Thomas, Christian, Zhe Liang, Lorenz, Patrick, Christoph, Julia, Johannes, My, Ferdinand,
Sebastian H., Janosch and Matthew I did not have to do all the work on my own. I benefited
a lot from teaching you and I like to see that you are carrying on so well.

Last but not least, I want to thank my family for their support, open ear and refocusing to the
important things especially during the toughest times.

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Symbols and Abbreviations
AAS Atomic absorption spectroscopy
BAS Brønsted acid site
BET Brunauer-Emmett-Teller
CN Coordination number
Conv. Conversion
CRF Common reporting format
c-ZrO cubic-ZrO
2 2
D Dispersion
d Diameter of particle from element A
A
DFT Density functional theory
EDX Energy dispersive X-ray (spectroscopy)
Eq. Equation
EU European Union
EXAFS Extended X-ray absorption fine structure
FAME Fatty acid methyl ester
FID Flame ionization detector
FT Fourier transformation
GC Gas chromatography
GHG Green house gas
HDN Hydrodenitrogenation

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HDO Hydrodeoxygenation
HDS Hydrodesulfurization
HR-SEM High resolution scanning electron microscopy
ICP-OES Inductively Coupled Plasma Optical Emission Spectrometry
IR (spectroscopy) Infrared spectroscopy
K Reaction equilibrium constant
k Reaction rate constant
LAS Lewis acid site
LULUCF Land use, land-use change and forestry
MS Mass spectrometry
m-ZrO monoclinic-ZrO
2 2
NERD Non-esterified renewable diesel
p Pressure
R Radial distance in EXAFS
S Selectivity
S Specific surface area, derived from BET-model
BET
SEM Scanning electron microscopy
T Temperature
TEM Transmission electron microscopy
TMS Tetramethylsilan
TOF Turnover frequency
TPD Temperature programmed desorption (of NH or CO )
3 2

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TPIE Temperature programmed isotope exchange
TPR Temperature programmed reaction (commonly also used as
Temperature programmed reduction)
t-ZrO tetragonal-ZrO
2 2
UN United Nations
wt% Weight percent
X Conversion
XANES X-ray absorption near edge structure
XAS X-ray absorption spectroscopy
XRD X-ray diffraction
Y Yield

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Physical units
°C Degree Celsius/centigrade
A Ampere
Å Ångstrom (= 10-10 m)
a Year (lat. annum)
bar Bar (= 105 Pa = 1 kg·m-1·s-2)
cm-1 Reciprocal centimeter (= 1.99·10-23 J)
eV Electron volt (= 1.6·10-19 J)
g Gram
h Hour
Hz Hertz (= s-1)
J Joule (= 1 N·m)
L Liter
m Meter
min Minute
mol Mole
rpm Rounds per minute (= min-1)
t Metric ton (= 1000 kg)
T Tesla
V Volt

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