BOOK OF ABSTRACTS

27 – 29 May 2019
Festung Marienberg, Würzburg/Germany

Jahrestreffen Reaktionstechnik 2019

gemeinsam mit der
Fachgruppe Mehrphasenströmungen
Annual Meeting on Reaction Engineering 2019
in cooperation with the subject divison
Multiphase Flows
www.processnet.org/REAKT2019
 Abstracts of
Plenary Lectures
 Energetic efficiency of drop breakup and mass transfer
accompanied by chemical reactions in liquid-liquid systems

Jerzy Bałdyga, Magdalena Jasińska, Michał Kotowicz and Grzegorz Tyl

Warsaw University of Technology, Warsaw/Poland;

In this work we consider energetic efficiency of the dispersion/mixing

processes depicting this fraction of the rate of energy dissipation that is used directly
to perform processes of drop breakup and mass transfer in two-phase, liquid-liquid
systems. Experiments to be interpreted using this concept are carried out in the high-
shear rotor-stator mixers: Silverson 088/150 MS in-line mixer, the T 50 Ultra-Turrax®
- IKA rotor-stator mixer and the batch reactor of diameter 12cm, equipped with the
Silverson rotor-stator mixer. Applied experimental method is based on determination of
the product distribution of the complex chemical test reactions, which enables to
characterise energetic efficiency of the overall process of dispersion and mass
transfer. To do this one needs to construct the calibration curve representing the
theoretical dependence of the product distribution on k L a or the related rate of energy
dissipation. When the drop size distribution is measured as well, one can determine
separately efficiency of drop breakup. Results of this procedure show how the mode
of operation (inline or batch), screen geometry and rotor speed affect energetic
efficiency of dispersion processes.
Performing of the above mentioned procedure generates some problems and
questions that will be considered as well:.
1. Problem of development and choice of test reactions.
2. Problem of mass transfer coefficient for different viscosity of the continuous
and dispersed phase.
3. Choice of the drop breakage model.
4. Application of bivariate population balances to follow simultaneously drop
breakage and mass transfer; examples and methods of solution.
5. Effects of fluid flow structure; interpretation based on the structure of the
rotation and deformation tensors.
6. Relation between efficiency of mixing observed in the single phase systems
and the two-phase systems.
 Solid oxide steam-CO 2 co-electrolysis.

From theoretical analysis to the cell design aspects

R. Kodýma, P. Vágnera, M. Paidara, D. Niakolasb, S. Neophytidesb, K. Bouzeka

a
University of Chemistry and Technology, Prague, Czech Republic; bFORTH/ICE-HT,
Patras, Greece

Clime changes connected with an increased CO 2 concentration in the atmosphere

have provoked important political decision to reduce emissions of this greenhouse
gas substantially within the next decades. This decision is, at the same time,
motivated by the decreased dependence on the fossil fuels connected with important
political and ecological aspects. Targets set by the decarbonisation policy and
extensive utilization of the renewable sources of energy raises, however, important
technological challenges. To the most important ones belongs stabilization of the
distribution grid and utilization of intermittently excessive energy. So-called
Power-to-X technologies represent one of the possible approaches. Solid oxide
steam electrolysis and steam-CO 2 co-electrolysis (SOSCE), i.e. topic of this
presentation, represent one important part of this approach.
SOSCE represents a complex technology possessing still numerous challenges
including its fundamental understanding, construction materials, cell design and its
subsequent operation. The target of this contribution is to document above points on
the example of a single electrolysis cell. The problem is handled in several
consecutive steps. The initial one is represented by the thermodynamic analysis of
the problem and definition of thermodynamically safe domains of operation. In the
next step, kinetic parameters of the main processes occurring in the cell are
characterised. This includes both chemical and electrochemical reactions. The
results obtained represent fundamental base for prediction of the cell behaviour
under various conditions, its scale-up and simulation of its dynamic behaviour under
various configurations and operation protocols.

Acknowledgement
This project has received funding from the Fuel Cells and Hydrogen 2 Joint
Undertaking under grant agreement No (671481). This Joint Undertaking receives
support from the European Union’s Horizon 2020 research and innovation
programme, Hydrogen Europe and Hydrogen Europe research.
 Micro- and Macrokinetics in Electrochemical Cells
Ulrike Krewer, Institute of Energy and Process Systems Engineering, Technische
Universität Braunschweig, Braunschweig/Germany

Electrochemical cells, such as fuel cells, batteries and electrolysers are essential
components of future sustainable energy systems. Furthermore, the power-to-
chemicals concept promises to generate not only fuel, such as H 2 , but also base
chemicals from water, air and electricity from renewables. A bewildering range of cell
chemistries exists, with many of these showing high thermodynamic efficiencies. Still,
only few so far succeeded to enter mass market. This may be attributed to a high
demand for expensive cell materials, which scales linearily with power, and to
performance losses due to reaction kinetic issues at the electrodes.
Qualitative and especially quantitative understanding of the reactions at the electrode
surface is an important key to improving cell performance and durability, and to
identify optimal material and operating conditions. Furthermore, technical electrodes
are three-dimensional porous structures containing two or three different phases with
irregular distribution of reactants, electrolyte and electrode material. As reaction only
occurs where these phases meet, transport processes may often limit local activity
and, thus, productivity. As a result, knowledge-driven design and improvement of
performance of electrochemical cells requires in-depth knowledge on a cell's
microkinetics as well as macrokinetics, and sophisticated methods to analyse and
identify them.
Focus of this talk is on electrochemical reaction kinetics and to elucidate the interplay
of reaction rate, current, voltage and transport, i.e. micro- and macrokinetics, for a
wide range of electrochemical cells. Besides complex multistep reactions, the role of
adsorbates, local operating conditions, side reactions and surface changes of
electrodes will be discussed. Further, the effect of transport phenomena and the
distribution of properties and uncertainties is illustrated. Examples cover established
technologies like Li ion batteries and more complex electrodes of next generation
cells, like metal air batteries, alkaline cells, microbial cells and Li sulfur batteries. The
combination of mechanistic modelling, dynamic electrochemical and further operando
or ex-situ measurements is shown to yield not only a better quantitative and
qualitative understanding of electrode performance, but to be the base for a
knowledge-driven, model-based electrode and cell development.
 Contribution of reaction engineering to the long-term reduction

of CO 2 -emissions by process innovation

Dr. K. Ehrhardt, Dr. A. Bode, Dr. F. Scheiff, D. Flick,

BASF SE, Ludwigshafen, Germany

The climate treaty signed at Paris in 2015 and its target to keep global warming
below 2°C will require massive reduction of greenhouse gas emissions and will have
a deep impact on the chemical industry. The target described in the Roadmap of the
European Union [1] is a reduction by 80 – 95% until 2050 compared to 1990. And the
industrial sector including the chemical industry must reduce emissions by 50% until
2030 compared to 1990 or by 22% compared to 2014 [2]. So, utilization of renewable
energy, renewable and recycled raw materials, avoidance of CO2 emission and
recovery of waste heat etc. will become very important. In parallel, the interrelation-
ship of feedstock prices might change too. E.g. less refineries will foreseeably be
needed in an e-mobile environment if cars no longer use gasoline or diesel.

Such a fundamental change of boundary conditions for the chemical industry could
change the raw material base, the chemical Verbund structure (interconnection of
chemical plants), logistics and so on. Therefore, new chemical processes need to be
developed, and existing ones need to be modified. Unfortunately, such developments
must deal with high uncertainties, as legislation will develop over time, likewise
customer needs will change, and long-term forecasting of prices is always difficult.
However, the transition must be initiated now due to the very long timescales of R&D
and investments, especially for the currently most CO2-intensive technologies in the
petrochemical sector.

Reactions engineering plays an important role during the development of new

processes. This role, its contributions and the interrelationship between reaction
engineering and other disciplines will be exemplified using the publicly funded project
FfPaG (solid and fluid products from gas), as it covers all aspects of process
development. Furthermore, challenges linked to the raw material change mentioned
above become obvious. The FfPaG project was a joint effort of eight partners (BASF
SE, BASF New Business GmbH, hte GmbH, Linde AG, thyssenkrupp Steel AG
(tkSE), thyssenkrupp Industrial Solution (tk-IS), VDEh-Betriebsforschungsinstitut
GmbH (BFI) and Technische Universität Dortmund) and it was supported by the
BMBF (federal ministry of education and research, Germany). [3]

Target of the project was the development of a pilot scale plant concept for the
pyrolysis of natural gas to hydrogen and solid carbon, the catalytic activation of CO2
with hydrogen by reverse water gas shift and the formulation of carbon as high-priced
raw material to substitute coke and the like. The 10 work packages comprised kinetic
studies, investigation of energy integration, development of reactor concepts,
conceptual design of pilot facilities, testing of carbon applications and the economic
assessment.

The results of the project were, first, that reverse water gas shift was is not
economical for the considered boundary conditions of typical industrial sites. Second,
methane pyrolysis is technically highly demanding but a promising technology for low
CO2 hydrogen production [4]. Therefore, the latter technology will be developed
further in a project, which was applied for recently.

[1] European Commission, The roadmap for transforming the EU into a competitive,
low-carbon economy by 2050
[2] Klimaschutzplan 2050, Klimaschutzpolitische Grundsätze und Ziele der
Bundesregierung
[3] BASF SE, hte GmbH, VdEh Betriebsforschungsinstitut, Linde AG, thyssenkrupp
Industrial Solutions AG, thyssenkrupp Steel Europe AG, Technische Unversität
Dortmund (2017): Feste und fluide Produkte aus Gas – FfPaG,
Förderkennzeichen: 033RC1301 A-G Schlussbericht an das Bundesministerium
für Bildung und Forschung (BMBF)
[4] Bode A.: New process for clean hydrogen, BASF R&D press conference,
10.01.2019, Ludwigshafen am Rhein, Germany (presentation)
Lecture abstracts
Monday, 27 May 2019
Heterogeneously catalysed gas-liquid reaction in a novel gas-liquid-
liquid slug flow capillary reactor

D. Hellmann, TU Dortmund; D. W. Agar, TU

Two different reactor concepts are presently available for implementing

heterogeneously catalysed gas-liquid reactions in microchannels: the catalytically
coated wall reactor and a miniaturised version of the classical trickle-bed reactor.
Both strategies have pros and cons. The micro-fixed-bed suffers from the high
pressure drop due to the small catalyst particle size (<100 µm) within the capillary
and the non-uniform residence time distribution, which impairs reactor performance
for consecutive reactions. The coated wall reactor overcomes these drawbacks, but
offers only a limited catalyst area surface per volume, necessitating the application of
very active catalyst systems. In both cases catalyst installation and removal can
present a challenge.
The suspension reactor described here attempts to resolve these shortcomings by
suspending ultra-fine catalyst particles directly in a second immiscible liquid phase.
Good accessibility of the catalyst is guaranteed by the Taylor vortices within the slugs
and the catalyst can subsequently easily be separated off by decantation. To
demonstrate the utility of this approach, such a reactor is compared to the existing
alternative concepts with respect to its residence time distribution, pressure drop and
accessible catalyst surface.
Methods
The flow pattern for the gas-liquid-liquid suspension flow reactor is illustrated in Fig.
1. The dispersed liquid phase (blue) is used as a support medium for the catalyst
particles. The techniques for generating such uniform flow patterns and the
introduction of catalyst suspension into the capillary will be presented in detail. The
specific catalytic surface available in each of the three concepts has been evaluated.
The pressure drop in the capillary was measured at two points 1 m apart and
compared with literature values for a micro-fixed-bed reactor. The residence time
distribution was determined with two optical detectors 0.33 m apart using crystal
violet as tracer and the results were benchmarked against literature data for a micro-
fixed-bed

Fig 1: Flow pattern for three phase slug flow. Red: first liquid phase, Blue: second liquid phase two
containing suspended catalyst particles White: gas phase

Results and Discussion

Fig.2 shows the catalytic surface area available per meter of reactor length for a
capillary of 1 mm inner diameter for the different reactors.
50000
40000 Coated wall
Specific surface
area m2 m-3
30000 Fixed bed
20000 1 w% suspension

10000 2 w% suspension

Fig. 2 Comparison of catalytic surfaces for a coated wall, a solid foam, a fixed bed with 100 µm
particles and 1 and 2 wt% catalyst suspension with 1 µm particle size. Particle size for the micro-fixed-
bed is taken from [1].

The suspension reactor can attain values comparable to those in the micro-fixed bed
due to the small catalyst particle size and offers much greater catalyst surfaces than
the catalytically coated wall concept.
As expected, the comparison of the measured pressure drops reveals that the three
fluid phase system exhibits similar behaviour to gas-liquid flow in the catalytically
coated wall reactor, while the micro-fixed- bed pressure drop is a factor of 22 higher
(Fig.3)

1,2
Pressure drop bar m-1

1
Fixed bed
0,8
Gas liquid liquid slug flow
0,6
Gas liquid slug flow
0,4
0,2
0

Fig. 3: Pressure drop for micro-fixed-bed with 100 µm particles [2], gas-liquid-liquid and gas-liquid flow
for 0,045 m/s overall velocity and 1,75 mm inner diameter. The pressure drop for the multiphase flow
is calculated based on the experimental results for 1 mm inner diameter capillaries to be consistent
with the micro-fixed-bed data.

The comparison of the residence time distributions is depicted in Fig. 4 and indicates
a superior narrower distribution for the suspension reactor as opposed to the micro-
fixed-bed. It is assumed that the residence time distribution for the catalytically
coated wall reactor is equivalent to that of the three fluid phase system, since back-
mixing can only occur via the thin organic film on the capillary surface, which is
similar in both instances.
 8

6
Gas-Liquid-

E (Θ) -
4 liquid slug flow
2 Fixed bed

0
0 0,5 1 1,5 2
Θ-

Fig. 4: Measured residence time distributions for a three fluid phase flow and a micro-fixed-bed [1].

Conclusion
The gas-liquid-liquid catalyst suspension reactor concept provides tighter residence
time distributions and lower pressure drop than micro-fixed-beds, whilst offering
higher catalytic surface areas than the coated wall reactor. Under certain
circumstances, with ultra-fine particles one can even exceed the surface area of a
micro-fixed-bed reactor. The suspension reactor can thus be particularly
advantageous for reaction networks where a very narrow residence time distribution
is important and catalyst loadings need not be too high. The suspension reactor is
expected to exhibit slightly lower mass transfer rates than the other concepts and
may thus be limited to slightly slower reactions. Nevertheless, this new concept
appears eminently feasible and should be considered as a viable alternative for
heterogeneously catalysed gas-liquid reactions in fine chemical syntheses using
microreactors.
References
[1] Serres, N., Scheich, D., Vidal, V., Philippe R., 2018. Liquid residence time
distribution of multiphase horizontal flow in packed bed milli-channel: Spherical
beads versus open cell solid foams. Chem. Eng. Sci. 190, 149-163.
[2] Knobloch, C., Güttel, R., Turek, T., 2013. Holdup and Pressure Drop in Micro
Packed-Bed Reactors for Fischer-Tropsch Synthesis. Chem. Ing. T. 85, 455-460.
Investigation of gas-liquid reaction kinetics in homogeneous phase
at the example of the oxidation of toluene
S. Gast, U. Tuttlies, U. Nieken
University of Stuttgart, Institute of Chemical Process Engineering, Stuttgart

Gas-liquid reactors are used in the chemical industry for a wide variety of reactions,
such as oxidations or dehydrogenations of organic liquids. The main reactor type for
these processes is the bubble column, a reactor where gas is dispersed in the liquid
phase.
Although the construction of bubble columns can be very simple, the underlying pro-
cesses are quite complex. In particular, the strong interactions between mass
transport, hydrodynamics and chemical reactions in gas-liquid reactors are still an
open problem. Since these effects have a large impact on product conversion, selec-
tivity, and performance [1] it is of critical importance to understand each of these pro-
cesses in detail. Due to the interaction of these processes, each process must be
studied independently in order to understand its contribution to the whole. Therefore,
the following project is focusing on the independent measurement of the reaction ki-
netics of a gas-liquid reaction system without the constraints of mass transport and
hydrodynamics. Further, the influence of the flow conditions around a bubble on
chemical reaction and product selectivities is investigated.
Our approach is to determine the single-phase kinetics for a gas-liquid reaction only
in the liquid phase, thus providing kinetic parameters for further usage in computa-
tional fluid dynamics (CFD) models without the influence of other parameters like
mass transfer, surface tension or bubble wakes.
Within the presented work a new reactor concept has been developed in order to de-
termine the liquid phase kinetics of toluene oxidation in homogeneous liquid phase.
The setup consists of a heated reactor and an external loop, which is cooled down to
room temperature. In order to decouple the mass transfer and the reaction, oxygen is
added and solved in the liquid phase within the chilled external loop. To avoid multi-
ple coexisting phases, experiments are performed at an elevated pressure. A further
advantage of a single-phase reaction is the minimization of the risk of explosion due
to the absence of an explosive gas phase in oxidizing reactions of organic liquids.
One major task turned out to be the PhCH2OH
O2 O2 + PhCH2OOH
measurement of the liquid oxygen 2 5 4 H2O + PhCH2OOH

concentration within the reactor. It was 1 2

PhCH3 PhCH2OOH PhCOH
solved by continuously discharging a O2 H2O
O2
5 3

small amount of reaction mixture, fol-

PhCOOH H2O
lowed by degasification and a thermo-
6

dynamic flash calculation[2].

Fig. 1: Reaction network of the oxidation of toluene based
Using the described system, experi- on [3] [4].

ments with controlled reaction conditions were conducted. The presentation will detail
the experimental proof-of-concept and will show that by extending the concentration
analysis for peroxides and including peroxides and its contribution to (intermediate)
reactions to the reaction network (see Fig. 1) it is possible to describe measured da-
ta. We will show that the obtained kinetic model fits well to experiments with e.g. dif-
ferent O 2 -concentrations (example in Fig. 2).
The reaction kinetics was further used for theoretical studies, which will show the cor-
relation between flow conditions (e.g. wakes behind bubbles), the reaction network
and the resulting product spectrum in order to show the connection between the time
scales of mixing and chemical reac-
tion.

The authors gratefully acknowledge

the financial support from the DFG pri-
ority program SPP1740, project
Ni 932/9-2.
[1] A. A. Koynov and J. G. Khinast,
Chem. Eng. Technol., vol. 29, no. 1, pp.
13–23, 2006.
[2] S. Gast et al., Chem. Eng.
Technol., vol. 40, no. 8, 2017.
[3] I. Hermans et al., J. Mol. Catal. A
Chem., vol. 251, no. 1–2, pp. 221–228,
2006.
[4] J. A. A. Hoorn et al., Inst. Chem.
Fig. 2: Comparison of experimental data and kinetic simu- Eng., no. February, pp. 187–195, 2005.
-3
lations in mol m .
 Oxidation von Cumol in Blasensäulen – Leistungseintrag für die
Modellierung der Fluiddynamik
Manfred Weber, INEOS Phenol GmbH, Gladbeck/Germany
Vortrag ProcessNet Fachgruppe Mehrphasenströmungen 27. – 29. Mai 2019

Im Phenol-Prozess wird Cumol mit Luftsauerstoff zu Cumolhydroperoxid (CHP)

oxidiert. Das CHP wird dann in der sogenannten Spaltung in Phenol und Aceton
umgewandelt. Anschließend erfolgt die Aufarbeitung in der Destillation. Mit diesem
Verfahren, auch Hock-Prozess genannt, werden weltweit mehr als 98% des
gesamten Phenols hergestellt.

Für die Oxidation von Cumol werden Blasensäulen mit Durchmessern von mehreren
Metern eingesetzt bei Temperaturen um 100°C, Drücken von mehreren bar und
Gasleerohrgeschwindigkeiten von wenigen cm/s. Für die Modellierung ist neben der
Kenntnis der Reaktionskinetik und der Stoffübertragung die korrekte Beschreibung
der Fluiddynamik mit Fokus auf die Durchmischung der flüssigen Phase essentiell.
Die Rückvermischung der flüssigen Phase kann über das axiale Dispersionsmodell
beschrieben werden. Das Scale-up des axialen Dispersionskoeffizienten D ax auf
große Blasensäulen ist aber nach wie vor mit Ungenauigkeiten behaftet.

Eigene Messungen /1/ an Reaktoren

im Produktionsmaßstab zeigen, dass T, p
mit bekannten Korrelationen aus der
Literatur Abweichungen um den
Faktor 10 möglich sind. Im Vortrag Gasvolumen
-strom
wird dem nachgegangen. Basis für VG (m3/s)
h (m)

die Bewertung der fluiddynamischen bei T, p

Grenzfälle „homogen aufsteigender Flüssigkeits-

Blasenschwarm“ und „turbulente dichte ρL
(kg/m3)
Flüssigkeitswirbel“ ist dabei die durch
das aufsteigende Gas eingebrachte Gas
Leistung P = ρ · g · h · V [W] /2/. (Luft)
L G

/1/ J.-B. Große Daldrup, Mf. Weber, M. Grünewald, N. Abel, L. Schlusemann

„Modellgestützte Beschreibung von Blasensäulen“, Vortrag auf der ProcessNet Jahrestagung
der FG Fluiddynamik und Trenntechnik 2013
/2/ P. B. Whally, J. F. Davidson, “Liquid Circulation in Bubble Columns”
Instn. Chem. Engrs. Symp. Ser. No. 38, J5, London 1974
Modeling and simulation studies on the design and dimensioning of
bubble column reactors
I. Rieth, M. Grünewald
Ruhr Universität Bochum, Bochum/Deutschland
The challenge of modeling gas-liquid reactors in industrial scale is the mathematical
description of the ongoing closely linked single phenomena inside the reactor. A
typical industrial gas-liquid reactor is the bubble column used for example for
chemical synthesis, fermentation and as a chemical absorption apparatus. On the
one hand, bubble columns provide the advantage of a simple construction. On the
other hand, the occurring hydrodynamics are very complex. More specifically, the
resulting hydrodynamics are linked with mass and heat transfer as well as reaction
phenomena.
In the literature, different modeling approaches are described. The main approaches
are dispersion models, CFD models and compartment models. Simple approaches
like dispersion models have the advantage of describing the above-mentioned linked
phenomena. However, the complex hydrodynamics of bubble columns cannot be
radially resolved with this approach. In contrast, complex approaches like CFD
models allow a detailed modeling of hydrodynamic behaviour whereby the integration
of single phenomena requires sophisticated modeling tools and increased
computational performance.
As a compromise between Shortcut and numerical modeling, compartment modeling
of bubble column reactors offers the opportunity to integrate the above-mentioned
single phenomena while enabling a radial distribution with acceptable computing
effort.
Goal of our research carried out during the last years has been to describe a
technical as well as an industrial bubble column with radial distribution utilising a
validated compartment model. Hence methods for generating correlations and
parameters for the used model were developed, including compartment geometry,
radial dispersion and mass transfer coefficients.
In our presentation, we will give a closer look to the effect of radial distribution and
reaction kinetics on modeling of bubble columns. Therefore, the cumene oxidation as
a typical industrial process, will be modeled with a compartment and a dispersion
model. The simulation results will be compared regarding the influence of radial
resolution. Examining the effect of reaction kinetics of cumene oxidation on reactor
dimensioning using both model approaches is another object of our presentation.
Consequently, different kinetic descriptions as well as inaccuracy of experimentally
determined kinetic constants, which are published in literature, will be studied.
Moreover, in order to further classify compartment models in this context, an
overview of approaches for modeling of bubble columns will be given.
 A Control strategy for production of biologics – From risk
assessment to process validation

T. Wucherpfennig, Biopharma Process Development, Germany, Boehringer

Ingelheim Pharma GmbH & Co. KG, Biberach an der Riss, Germany

The demand for complex therapeutic proteins and antibodies for treatment of various
diseases has increased continuously in the last decades, prompting the continuous
development of new processes. The development and production of drugs is a
heavily regulated environment, with severe constraints on development and later on
production. In comparison to other biotech industries the possibility for process
optimization during the life cycle of an active ingredient is very limited.
For the commercialization of a biopharmaceutical production process a
comprehensive late stage development concept is required comprising: development
of a robust and economical process, scale up to full scale facility, comprehensive risk
assessment which triggers process characterization studies including scale down
model establishment—these results are transferred into the control strategy and
enable process performance qualification runs (PPQ) and finally the implementation
of a well-controlled and robust commercial process.
The process knowledge gained during development and clinical manufacturing runs
is compiled and utilized in a series of risk assessments to help define the process
characterization study plan.
The presentation summarizes the requirements and challenges for the risk
assessment, establishment of scale down model and extensive process
characterization.
Lecture abstracts
Tuesday, 28 May 2019
 Dynamic Modeling of reversible solid oxide cells (rSOCs)

Lukas Wehrlea, Yuqing Wanga,b, Aayan Banerjeea,c, Nigel Brandonc, Olaf

Deutschmanna
a
Institute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of
Technology
b
National Key Laboratory on Electromechanical Dynamic Control, Beijing Institute of
Technology, China
c
Department of Earth Science and Engineering, Imperial College London, South
Kensington Campus, UK

Introduction
The envisioned transition to a decentralized power supply based on renewable
energy sources (RES) depends on energy storage systems, which can assist in
matching the demand and varying supply associated with RES. In this regard,
reversible oxide cells (rSOCs) are among the most sophisticated and most promising
developments. The rSOC combines both fuel cell (SOFC) and electrolysis (SOEC)
modes in one single device, and is therefore capable of both supplying electrical
energy and storing energy in form of fuel in attached tanks. In order to achieve a
leveled power supply, this mode switching will have to occur quite frequently in real
world applications. Thereby, potentially severe challenges arise such as cyclic effects
on long-term durability and degradation processes as well as thermal management
[1]. In this study, the characteristics of the mode switch are investigated by applying a
dynamic 3-D stack model.

Model Description
The model utilized is based on a hierarchical approach comprising several length
scales. It encompasses the physico-chemical processes on the molecular level as
well as a 2-D or 3-D modeling methodology for planar single cells and stacks [2].
Heterogeneous reactions occurring at the interface between the Ni particles in the
fuel electrode and the gas phase are modeled via a 42-step elementary reaction
mechanism [3]. Modified expressions of the Butler-Volmer (B-V) equation derived
from multi-step charge-transfer mechanisms for each current pathway are used [4].
The electrochemical model was calibrated and validated in both SOFC and SOEC
modes against experimental data measured by Ebbesen et al. [5]. Stack simulations
were carried out based on the anode-supported F-type design cell of the
Forschungszentrum Jülich [6].

Results
Step voltage changes were imposed to detail the dynamic behavior of a 50-cell rSOC
stack running either on H2O/H2- or on H2/CO/H2O/CO2-mixtures during a mode
switch from SOEC to SOFC mode. The simulations revealed that the current density
and species mole fractions firstly undergo instantaneous changes following the
voltage perturbation, whereas the continuous temperature response approaches its
steady-state much more slowly due to the intrinsic thermal resistivity of the stack.
Furthermore, it could be shown that the temperature evolution after a mode switch
leads to pronounced thermal stresses during dynamic operation. In this regard, a 3-D
model is required to capture the transient behavior of the temperature distribution
within the stack during the mode switch. This is of vital importance to provide an
informative basis for control strategies. Thus, several options for temperature control
management were investigated in detail. The simulation results demonstrated that
enhancing the air ratio is a powerful tool to lower temperature variations during both
dynamic and steady-state operation. Furthermore, a gradual voltage change can be
applied to perform a mode switch in a more controlled manner to minimize thermal
stress.

References
[1] P. Kazempoor, R. J. Braun, Int. J. Hydrogen Energy 2014, 39 (11), 5955-5971.
[2] A. Banerjee, Y. Wang, J. Diercks, O. Deutschmann, Appl. Energy 2018, 230, 996-1013.
[3] L. Maier, B. Schädel, K. H. Delgado, S. Tischer, O. Deutschmann, Top. Catal. 2011, 54, 845-858.
[4] H. Zhu, R. J. Kee, V. M. Janardhanan, O. Deutschmann, D. G. Goodwin, J. Electrochem. Soc.
2005, 152 (12), A2427-2440.
[5] S. D. Ebbesen, C. Graves, M. Mogensen, Int. J. Green Energy 2009, 6 (6), 646-660.
[6] L. Blum, H.-P. Buchkremer, S. Gross, A. Gubner, L. G. J. de Haart, H. Nabielek, W. J. Quadakkers,
U. Reisgen, M. J. Smith, R. Steinberger-Wilckens, R. W. Steinbrech, F. Tietz, I. C. Vinke, Fuel Cells
07 2007, 7 (3), 204-210.
 Comparison of µ-PIV flow pattern measurements and CFD
simulation of high-pressure homogenizer orifices

Peter Walzel*, Ariane Bisten†, Gerhard Schaldach*, Felix Johannes Preiss†, Heike
Petra Karbstein†

*Department of Biochemical and Chemical Engineering, TU Dortmund University,

44227 Dortmund, Germany
†
Institute of Process Engineering in Life Sciences Chair of Food Process
Engineering, Karlsruhe Institute of Technology, 76131 Karlsruhe, Germany

Emulsions have a wide scope of applications. They can be found in the cosmetic,
chemical, pharmaceutical, and food industry. Emulsion properties, such as stability,
rheological behavior, and color depend on the droplet size and droplet size
distribution (DSD) of the emulsion. High-pressure homogenization (HPH) is mostly
used to produce emulsions with droplets smaller than one micrometer. During this
process, an emulsion premix with larger droplets is pumped with a pressure of
several hundred bar through a disruption unit. In this unit, the characteristic
dimension through which the product flows, is significantly reduced. This results in a
drastic increase in flow velocity. Thereby, droplets are exposed stresses resulting
from laminar, turbulent and cavitating flow patterns, which cause droplet breakup.
Nonetheless, the influence of geometrical or process parameters on resulting droplet
sizes is still focus of ongoing research. Therefore, the design of a HPH process,
which should result in a specific droplet size, is still mostly based on process
functions [1] and empirical knowledge [2].

This investigation focuses on the influence of the geometry of the disruption unit, and
the process parameters on the local flow pattern and resulting stresses. Previous
experimental works have demonstrated that even small changes in the geometry of
the disruption unit result in significant changes on the DSD [3]. In addition, CFD
simulations have shown that the elongation rate in front of the smallest cross section
depends on the geometry of the disruption unit [4]. These higher elongation rates
may be responsible for smaller droplets, as they induce elongation into extremely thin
filaments (hypothesis of this work). However, due to the very small dimensions of the
disruption unit, CFD results (already presented in this ProcessNet section) could not
be corroborated up to now. Micro particle image velocimetry (µ-PIV) proposes a
promising approach to verify these results. It is a non-intrusive measurement method,
which allows an inside view on local HPH process conditions.

In this work, a micro particle image velocimetry setup was used to obtain velocity
profiles in two optical accessible orifices with varied inlet geometry. The obtained
averaged two-dimensional velocity profiles were used to calculate local shear and
elongation stresses in the laminar inlet of the orifices. Furthermore, three-dimensional
CFD simulations were carried out and the obtained results were compared with the
µ-PIV flow patterns.

References
[1] Schuchmann, H. P., Advances in Hydrodynamic Pressure Processing for
Enhancing Emulsification and Dispersion, in: Knoerzer, K., Juliano, P., Smithers,
G. (Eds.), Innovative Food Processing Technologies : Extraction, Separation,
Component Modification and Process Intensification, 1st Ed., Woodhead
Publishing, 2016, pp. 387–412.
[2] Floury, J., Desrumaux, A., Lardières, J., Effect of high-pressure homogenization
on droplet size distributions and rheological properties of model oil-in-water
emulsions. Innovative Food Science & Emerging Technologies 2000, 1, 127–134.
[3] Ramamurthi, K., Nandakumar, K., Characteristics of flow through small sharp-
edged cylindrical orifices. Flow Measurement and Instrumentation 1999, 10, 133–
143.
[4] Nagel, W. E., Kröner, D. B., Resch, M. M., Kissling, K. et al. (Eds.), Numerical
Investigation on the Deformation of Droplets in High-Pressure Homogenizers:
High Performance Computing in Science and Engineering '10, Berlin, Heidelberg,
Springer Berlin Heidelberg, 2011.
Peter Ehrhard, Ina Dittmar, Christian Heckmann,
Strömungsmechanik, Bio- und Chemieingenieurwesen
TU Dortmund

Zur flüssig/flüssig Pfropfenströmung und zum Stofftransport im Mikrokapillarreaktor

Der Stofftransport in mehrphasigen Strömungen hat viele Anwendung im Chemieingenieurwesen,

etwa in Reaktoren oder bei der Extraktion. Bei flüssig/flüssig Systemen tritt hierbei die Besonderheit
zutage, dass für den Stofftransport über die Grenzfläche die Eigenschaften beider Flüssigkeiten eine
vergleichbare Rolle spielen, d.h. es liegt ein sog. konjugiertes Problem vor.
In den vorliegenden Untersuchungen wird ein Extraktionsprozess in einem Mikrokapillarreaktor
numerisch simuliert und die Ergebnisse werden mit integralen Ergebnissen aus Experimenten
validiert. Ein Mikrokapillarreaktor besteht aus einem Pfropfenerzeuger, einer gerade Kapillare für eine
ausreichende Verweilzeit, und einem Phasentrenner. Das Simulationsmodell berechnet zunächst
mithilfe der Einfeldformulierung und der modifizierten „level-set“-Methode für eine periodische
Elementarzelle in der Kapillare das Strömungsfeld in beiden Phasen sowie die freie Grenzfläche.
Hierfür wird an der Grenzfläche eine definierte Verschmierung der „level-set“-Funktion über wenige
Knoten notwendig, damit der Gradient der „level-set“-Funktion numerisch handhabbar werden.
Eine Berechnung des Stofftransports über eine solche unscharfen Grenzfläche würde aufgrund der
dünnen Konzentrationsgrenzschichten sehr ungenau und schwierig. Deshalb wird die (stationäre)
Grenzfläche exportiert und jeweils ein hochauflösendes Gitter auf beiden Seiten der Grenzfläche in
beiden Flüssigkeiten arrangiert. Somit entsteht eine scharfe Grenzfläche und explizite
Übergangsbedingungen koppeln die Felder auf beiden Seiten der Grenzfläche. So wird eine
hochgenaue numerische Berechnung der Hydrodynamik und des Stofftransorts in beiden
Flüssigkeiten möglich.
 Spray Characteristics of the SpraySyn-nozzle

Malte F.B. Stodt a, b, Lizoel Buss a, Johannes Kiefer b, Udo Fritsching a, c

a
Leibniz-Institut für Werkstofforientierte Technologien – IWT, Badgasteiner Straße 3, 28359 Bremen,
Germany
b
Technische Thermodynamik, Universität Bremen, Badgasteiner Straße 1, 28359 Bremen, Germany
c
Mechanische Verfahrenstechnik, Universität Bremen, Bibliothekstraße 1, 28359 Bremen, Germany
Kontaktdaten Autor: Tel: +49 (0)421 218-51280; E-mail: m.stodt@iwt.uni-bremen.de

Atomization and spray characteristics of a twin-fluid nozzle

The flame spray pyrolysis (FSP) process is a powerful technique for the synthesis of
functional metal and metalloxide nanoparticles from a broad spectrum of available
precursor. Control of particle synthesis in the process is of great importance, as small
deviations of the processing conditions may have a huge impact on the quality and
properties of the nanoparticles. Most recent studies on FSP are focused on gas
phase reaction and particle formation without taking the antecedent spray formation
into account. In the present study, the atomization characteristics, both under burning
and non-burning conditions, are investigated experimentally and numerically using
the twin-fluid nozzle of the SpraySyn-burner (SPP 1980). In order to characterize the
spray formation of this twin-fluid nozzle, the variation of the relevant spray
parameters such as gas to liquid mass ratio (GLR) and equivalence ratio (EQR) is
studied.

Figure 1: Sketch of the experimental setup of the SpraySyn-burner and the PDA optics for droplet size and
velocity measurements.
For this purpose, the breakup and droplet dynamics are investigated using High
speed camera (HSC) imaging, laser sheet Mie-scattering (LSMS) and phase Doppler
anemometry (PDA) along the axial center line. Fig. 1 illustrates the PDA setup and
shows some example results.
Computational fluid dynamics (CFD) are utilized to obtain further information about
droplet trajectories, velocities, lifetime, and the evolution of the mean droplet
diameter along the axial center line of the flame spray. A two-dimensional (2D)
axisymmetric domain with 0.5 m height and 0.075 m width (radius of the domain) are
meshed with a computational grid of ~280.000 hexahedral cells. The discrete phase
is modelled using an Euler-Lagrange approach (two-way coupling) under steady-
state and compressible flow conditions. The turbulence scales are represented using
Reynolds-averaged Navier-Stokes (RANS) equations calculating the turbulence
viscosity by the shear stress transport (SST) k-ω model. The combustion reactions
are assumed to be mixing limited and are described using the eddy dissipation
concept (EDC) model.
It is found that the mean droplet diameter for the burning and non-burning spray were
in the same size range (~15 μm > dp > ~ 25 μm). The droplets in the flame spray
reached significantly higher mean velocities (up ≈ 120 m s-1) compared to the non-
burning spray (up ≈ 70 m s-1). Furthermore, a Stokes-number analysis allowed the
estimation of gas flow velocities from experimental PDA-data that were consistent
with results of the numerical simulations.

The financial support of this project through the German Research Foundation (DFG)
within the priority program SPP 1980 “SpraySyn” is gratefully acknowledged.
 Continuous multiphase flow: Heterogeneously catalysed reactions
combined with liquid-liquid extraction
Annika Grafschafter, Matthäus Siebenhofer, Graz University of Technology,
Graz/Austria

The economic isolation of constituents from dilute aqueous effluents, as can arise in
downstream processing of the biobased industry, may be achieved by the
combination of reactive separations (e.g. esterification) with liquid-liquid extraction.
By simultaneous extraction of the target product with a suitable solvent, conversion
can be enhanced. Slow chemical reactions, such as esterification reactions, require
catalytic acceleration. For continuous operation, heterogeneous catalysts are very
suitable since it is simple to separate them from the reaction broth. Heterogeneously
catalysed reactions combined with liquid-liquid extraction require adequate apparatus
design. Although different equipment is available on the market, equipment design
and optimization is still a challenge, especially when targeting continuous multiphase
flow. The Taylor-Couette Disc Contactor (TCDC) [1], a hybrid of the Rotating Disc
Contactor (RDC) and the Taylor-Couette Reactor (TCR) satisfies the requirements
for intensive continuous multiphase operation. The design of internals provides
flexible operation under harsh operation conditions. The design is similar to the RDC,
but with increased shaft diameter and without stator rings whereby dead zones for
accumulation of solid catalysts can be avoided. At convenient operation conditions,
the shaft and rotor discs of the TCDC induce banded flow pattern, providing
appropriate mixing of the liquid phases and the solid phase and sufficient residence
time for the solid catalysts.
Continuous liquid-liquid-solid flow has been implemented in the TCDC and the
hydrodynamic characteristics have been investigated in detail. ShellSol-T was used
as solvent phase, deionized water as continuous phase and Amberlyst15® as solid
phase. To gain data about the hydraulic performance the effect of hydraulic load, rate
of rotation and mass load of the catalyst were investigated. Beyond a critical
rotational speed, the vorticity of the continuous phase overcomes sedimentation
force of the dispersed phase and the solid phase and procure intensive phase
contact. The solid phase is dragged by the toroidal vortexes and even in the
presence of the dispersed phase, the catalyst particles remain within the single
compartment for reasonable
nable re
residence
iden e time. Due to the hydrophilic
h drophilic
drophili propertie
properties of the
catalyst,
atal t, it remains
remain dispersed
di persed in the aqueous
aqueou phase
pha e and can
an easily be separated at
the bottom of the column by sedimentation. The e
experimental
perimental inve
investigation
tigation of the
residence
re iden e time distribution
di tribution ffor liquid-liquid flow suggests the tank--in-series (CSTR)
model for rea
reactor
tor design [2]. The
T modeling of three-phase
pha e flow with chemical
hemi al
conversion
on er ion iis ob
obvious
iou via reactor-extractor
rea tor e tra tor cascade
a ade of CSTRs since the solid
particles
parti le are mainl
mainly collected
ollected in the lower p
part
art of one compartment,
ompartment, a
as shown
hown in
Figure 1. The e
experimental
perimental results confirm
firm appli
applicability
abilit of the multiphase
multipha e reactor
TCDC for intensifying heterogeneou
heterogeneously
l catalysed
atal ed reactions
rea tion such
u h a
uch as e
esterification
terifi ation
combined with liquid-liquid
liquid extraction.
extra tion.

t: Single compartment
Figure 1. Left: ompartment of the TCDC in multipha
multiphase
e operation mode with solid
olid parti
particles
le
mainly di
mainl dispersed
per ed in the lower toroidal vortex.
orte . Right: S
Schematic
hemati drawing of the process
pro
procee modelling setup
etup
with the produ
productt C being in
instantaneou
tantaneously
l extracted
e tra ted from the aqueou
aqueous p
phase
ha e by liquid
liquid-liquid extraction
with an appropriate solvent

[1] E. Aksamija, Ph.D. Thesis,

The i 2015.
[2] A. Graf
Grafschafter,
hafter, E. Ak
Aksamija,
amija, M. Siebenhofer, Chem. Eng. Technol.
Te hnol. 2016, 39
(11), DOI: 10.1002/ceat.201600191
 Displacement of adhering liquid droplets by air flow in a
channel-flow and a flat plate boundary layer flow configuration
B. Barwari1*, S. Burgmann1, N. Janssen1, M. Rohde1, U. Janoske1
1
Chair of Fluid Mechanics, Bergische Universität Wuppertal
Gaußstraße 20, 42119 Wuppertal, Germany
*barwari@uni-wuppertal.de

Droplets adhering to surfaces appear in a variety of technical applications. Often

there is an air flow over these surfaces, so that the droplet experiences a shear flow.
If the surface forces at the contact line are overcome by the external force from the
air flow, i.e. when a specific critical velocity of the air flow is exceeded, the droplet
becomes unstable, may detach and move over the surface. The time at which the
droplet begins to move is referred to as the state of droplet detachment. Apart from
that, in literature there are various interpretations for the definition of droplet
detachment, e.g. by using the point at which the advancing and receding contact
lines are moved for the first time [1] or with the same velocity [2]. However, the
process of droplet detachment is strongly affected by the air flow boundary
conditions. For instance, various velocity-ramp-function can be set such as applying
constant air velocity [3] or increasing flow over time [4]. In addition, the velocity profile
and the type of e.g. turbulence seems to affect the results as literature suggests for
flat plate boundary layer flow [5] or channel-flow [6]. Hence, the specific critical
conditions for a droplet detachment are not completely understood. In our latest work
[7], in a first step a robust definition for the beginning of the droplet movement has
been defined. In this work we focus on the boundary conditions.

The effect of the velocity-ramp-function (stepwise increasing air velocity) is

investigated in order to determine temporal effects on droplet detachment.
Furthermore, the influence of the boundary layer thickness is analyzed to elucidate
the fundamental parameters for determining the onset of droplet movement. Hence,
the experimental investigation deals with adhering liquid droplets on PMMA in a
shear flow for two configurations: in a rectangular cross-section Plexiglas-channel
(22x22 mm²) and in a wind tunnel (0.8x1.2 m²). The volume flow rate of the air flow is
adjusted by a mass flow controller for the Plexiglas-channel and by a fan for the wind
tunnel. The velocity profile measurements were carried out with a constant-
temperature anemometer using a hot-film-boundary layer probe. The position of the
droplet contour is measured with a high-speed camera using shadowgraph
technique. The comparison of the experimental data for both setups shows that only
the local velocity of the shear flow profile at the maximum height of the droplet is
decisive for the droplet detachment. The results indicate that the critical velocity for
the droplet detachment depends on time, i.e. velocity-ramp-function. The longer an
air flow velocity level is kept constant, the lower the critical velocities are. In addition,
if the jump of the velocity rate increases, i.e. the impulse rises through the higher
velocity jump, the critical velocity continues to decrease.

References

[1] C. Lv, et al., Sliding of water droplets on microstructured hydrophobic

surfaces, Langmuir 26 (11) (2010) 8704-8708 (DOI: 10.1021/la9044495).
[2] T. Maurer, Experimentelle und numerische Untersuchung der
Tropfenbewegung unter Einfluss von äußeren Kräften, Shaker, 2017 (ISBN: 978-3-
8440-5135-3).
[3] E. C. Kumbur, K. V. Sharp, M. M. Mench, Liquid droplet behavior and
instability in a polymer electrolyte fuel cell flow channel, Journal of Power Sources
161 (2006) 333-345 (DOI: 10.1016/j.jpowsour.2006.04.093).
[4] A. J. B. Milne, A. Amirfazli, Drop shedding by shear flow for hydrophilic to
superhydrophobic surfaces, Langmuir 25 (24) (2009) 14155-14164 (DOI:
10.1016/j.jcis.2006.04.021).
[5] S. C. Fu, et al., Detachment of droplets in a fully developed turbulent channel
flow, Aerosol Science and Technology 48 (9) (2014) 916-923 (DOI:
10.1080/02786826.2014.938801).
[6] J. Fan, M.C.T. Wilson, N. Kapur, Displacement of liquid droplets on a surface
by a shearing air flow, Journal of Colloid and Interface Science 356 (2011) 286-292.
(DOI: 10.1016/j.jcis.2010.12.087).
[7] B. Barwari, et al., Untersuchung der Dynamik von Tropfen in einem
Rechteckkanal unter Einfluss von Anströmung und Vibration, ProcessNet -
Jahrestreffen Bremen (2018), Bremen, Germany, Mar. 6 - Mar. 9.
 Multidimensional separation by magnetic-seeded filtration:
Modelling and experiment

Frank Rhein, Hermann Nirschl, Karlsruhe Institute of Technology,

Karlsruhe/Deutschland
The process commonly referred to as magnetic-seeded filtration [1] aims to separate
fine paramagnetic particles by agglomerating them with magnetic particles followed
by a HGMS (high-gradient-magnetic-separation) step. While many authors focus on
the HGMS part, this work takes a closer look at the first step: The hetero-
agglomeration of ferro- and paramagnetic particles.
When talking about particle agglomeration there are two crucial aspects that always
have to be taken into account: The pair potential between two particles as well as the
hydrodynamic conditions in which the agglomeration process takes place. The former
point is commonly described by the DLVO theory which considers the (repulsive)
electrostatic as well as the (attractive) van-der-Waals interactions. These potentials
however are often not sufficient to describe certain phenomena. In these cases, the
so-called non-DLVO forces come into play: Most notably and relevant for this work
are the magnetic as well as the surface related hydrophobic interactions. The
(ambitious) aim of this work is to not only characterize the agglomeration step with
regard to various potential related parameters, but to also shed light on possible
repercussions of these forces on the hydrodynamic conditions. When regarding a
suspension containing ferro- as well as paramagnetic particles under the influence of
a magnetic field one can observe a rapid agglomeration of ferromagnetic particles
due to the dominating magnetic force. One of the questions motivating this work is
whether this dominant homo-agglomeration process will have a positive, negative or
completely indifferent effect on the overall hetero-agglomeration rate. Preceding
studies [2] came to the conclusion that there might be an inclusion effect of
paramagnetic particles which to this point has not been accounted for. When
describing a hetero-agglomeration process, a thorough and simultaneous evaluation
of multiple parameters is crucial and cannot be simplified to e.g. only particle size or
surface properties. A different level of detail is necessary and thus the prefix
multidimensional is added in the title.
In the experimental part of this work a profound parameter study of the hetero-
agglomeration process is conducted. Additionally, a model calculation in the form of a
population balan
balance
e may reveal - upon comparison
ompari on with the e
experimental
perimental re
results
ult - if
there are still
till effects
effe t present that have
ha e not yet
et been accounted
a ounted for. If accepted,
a epted, thi
this
presentation
pre entation may
ma give
gi e new in
insights
ight in the intere
interesting
ting and complex
omple
omplex pro
processes
e e at wor
work
in hetero-agglomeration.

1. Ying, T.Y., S. Yiacoumi, and C. Tsouris,

T ouri , High-gradient
gradient magnetically
magneti all seeded
eeded
filtration. Chemi
Chemical
al Engineering S
Science,
ien e, 2000. 55(6):
(6): p. 1101-1113.
1101
2. Forster,
For ter, E., et al., Hetero Agglomeration ProProcesses
e e in a High-Gradient
High
Magnetic Filter Design. Chemi
Magneti Chemical
al Engineering & TeTechnology,
hnology, 2016. 39(3): p.
477-483.
 Analyse der Beschichtung freifallender Partikel
L. Pasternak und M. Sommerfeld
Otto-von-Guericke-Universität Magdeburg, Institut für Verfahrenstechnik, Germany,
D-39106 Magdeburg, Deutschland, email: lars.pasternak@ovgu.de

Aufgrund der Bedeutung von Beschichtungsprozessen in der Verfahrenstechnik,

wurde eine Versuchsanlage entwickelt, an der Tropfen-Partikel Kollisionen im
Labormaßstab untersucht werden können. Dabei werden mit Hilfe zweier
Hochgeschwindigkeitskameras, die freifallenden Partikel bis zur Kollision mit den
Tropfen verfolgt und das Kollisionsergebnis, sowie Größe und Geschwindigkeit des
Partikels und der Tropfen vor und nach der Kollision, bestimmt (Abb. 1). Da sich im
industriellen Beschichtungsprozess die Partikel frei bewegen und eine eigene
Geschwindigkeit aufweisen, werden die Partikel im freien Fall durch Schwerkraft
beschleunigt und ihre Bahn durch eine Führung kontrolliert. Aufgrund der kurzen
Dauer der Kollision und der limitierten Aufnahmezeit der Kameras, erfolgt eine
Triggerung der Kameras durch die fallenden Tropfen. Dies geschieht mittels einer
Lichtschranke, welche kurz vor dem Kollisionspunkt montiert ist und bei Passieren
der Partikel automatisch die Aufnahme startet.

Abb. 1 Kollisionssequenz eines 1.1 mm Polystyrol Partikels mit zwei deponierenden

300 µm Wassertropfen, Δt =266 µs, Tropfenabstand = 13x Tropfendurchmesser

Da der Tropfengenerator eine kontinuierliche Tropfenkette erzeugt, kollidieren meist

mehrere Tropfen mit einem Partikel. Da dies auch im realen Beschichtungsprozess
stattfindet, wird nur darauf geachtet, dass der Abstand zwischen den Einzeltropfen
groß genug für eine einzelne Kollisionsauswertung ist. Durch die Auswertung der
Tropfen Volumina vor und nach der Kollision beim Breakup soll zudem die
Beschichtungseffizienz mit untersucht werden. Dabei werden Größenverhältnisse
zwischen 0.3 - 0.8, unterschiedliche Partikelmaterialen und Flüssigkeiten untersucht.
In Anlehnung an die Arbeit von Mundo et al. [1] werden Tropfen-Partikel
Kollisionsergebnisse oft in Oh – Re Diagrammen dargestellt. Da die vorhandenen
Daten keine erkennbare Trennung zwischen Deposition, Breakup und Splashing in
diesem aufweisen, werden die Ergebnisse im B – We Diagramm, entsprechend
Ashgriz,N.; Poo,J.Y. [2], dargestellt.

1
0,8
0,6
Deposition
B [-]

0,4
0,2 Breakup

0 Rebounce
0 20 40 60 80 100
We [-]

Abb. 2 B - We Diagramm; 1.1 mm Polystyrol Partikel - 300 µm Wassertropfen

Entsprechend Tropfen-Tropfen Kollisionen kann eine klare Trennung zwischen den

einzelnen Kollisionsereignissen identifiziert werden, siehe Abb. 2.

Literatur
[1] Mundo, Chr., Sommerfeld, M., Tropea, C.: Droplet-wall collisions: experimental
studies of the deformation and breakup process. Int. J. Multiphase Flow 21 (1995)
151-173.
[2] Ashgriz, N.; Poo, J.Y.:”Coalescence and separation in binary collisions of liquid
drops”, 1990, Journal of Fluid Mechanics 221, pp. 183-204.
 Euler-Lagrange/DEM Model for the Simulation of Carbonate-
Looping Process
F. Alobaid, J. May, A. Stroh, A. Daikeler, J. Ströhle, B. Epple, Technische Universität
Darmstadt

In the last ten years, considerable experimental research has been carried out on
calcium carbonate-looping (CCL) with respect to process design and development.
By contrast, few numerical works that are mostly based on one-dimensional or
equilibrium-state are available. For a precise description of these processes, more
sophisticated approaches are, however, required.
In this work, a three-dimensional transient CFD-DEM model has been developed for
the simulation of the calcium carbonate-looping process at MWth scale. Sets of
experimental data obtained from a 1 MW th pilot plant and a downscaled 3D-cold flow
model are applied for model validation. For the numerical simulations of CCL, the
ANSYS-FLUENT software is used, combined with in-house codes (User-Defined-
Functions) for the modeling of EMMS drag model and thermochemical reactions.
Here, kinetic models for the homogenous and heterogeneous reactions as well as
the associated heat and mass transfer between gas and solid phase are considered.
The numerical results are in good agreement with the measurements and suggest
that the solid velocity, the solid fraction, the pressure drop and the temperature along
the reactors, the concentrations of gaseous and solid substances at the outlet of
reactors can be predicted with good accuracy. The validated models are of relevance
for further development of DEM model, feasibility and scale-up studies of CCL
processes.

Figure 1 Comparison of simulation and measurement

 CFD characterization of an improved design of downer reactor for
particle rounding

Juan S. Gomez Bonilla, Zhaochen Jiang, Andreas Bück, Jochen Schmidt, Wolfgang
Peukert, Institute of Particle Technology (LFG), Friedrich-Alexander-Universität
Erlangen-Nürnberg, Cauerstraße 4, D-91058 Erlangen

Selective laser sintering (SLS) of polymers is a powder-based technique, which

allows the series production of 3D functional parts by sintering consecutive layers of
powder with a laser from a CAD geometry without the need for tools or molds. About
95% of the SLS powder market is made up by polyamides, which limits the field of
application of this technique in the industry. Hence, current challenges lie mainly in
the development of new engineering-grade powders, which enhance the efficiency of
the process, and simultaneously customize the properties of the final parts. Common
techniques for the production of polymer powders for SLS involve the comminution of
polymers, which allows to tailor the particle size. However, the comminution of
polymers often results in powders made of irregular shaped particles with a low bulk
density and a bad flow behaviour, which cannot be processed efficiently in SLS
machines. With the aim of improve the flow behaviour of grinded powders, a thermal
process for particle shape modification was developed. This process consists in the
rounding of irregular polymer particles in a downer reactor. This rounding process
has been applied successfully for the rounding of grinded particles of polystyrene
(PS), polybutylene terephthalate (PBT), and PBT/glass composite particles.
Nevertheless, the main drawback of this process is the low yield achieved due to
particle build-up at the reactor walls due tribo-electrification of the particles and the
flow regime in the downer.

In this contribution, an improved design of rounding reactor in terms of the flow

regime is presented. Whit this aim, a CFD-DPM (Disperse phase model) aided
systematic characterization of the fluid dynamics in the current downer was
performed. Based on the results of the simulations an improved design is proposed.
The performance of both designs is also assessed experimentally including the
comparison of yields and particle size distribution of the rounded particles obtained
by both designs.
 CATALYST PERFORMANCE STUDIES FOR THE DIRECT DME
SYNTHESIS FROM VARIABLE CO/CO2/H2 FEEDS

Stefan Wilda, Nirvana Delgado Otalvaroa, David Guseb, Karla Herrera Delgadoa,
Matthias Kindb, Stephan Pittera, Sabrina Polierera and Jörg Sauera Institute for
Catalysis Research and Technology (IKFT) a, Institute of Thermal Process
Engineering (TVT) b, Karlsruhe Institute of Technology (KIT) D-76131
Karlsruhe/Germany

An increasing demand for clean fuels calls for technologically advanced solutions to
maximize the productivity and selectivity of renewable energy sources. One
promising approach is the “Power to Fuels” (PtF) concept. In particular, dimethyl
ether (DME) as chemical energy carrier is a promising candidate that can be
produced directly from CO/CO2/H2 gas streams derived from a variety of feedstocks
and renewable energy sources1.

Within this study, the direct DME synthesis is investigated in a fixed-bed reactor
aiming at dynamic processing with variable feed compositions. For initial methanol
formation, a Cu/ZnO/ZrO2 (CZZ) catalyst prepared at IKFT, and a ferrierite-type
zeolite (FER) for methanol dehydration to DME is used. Experiments have been
carried out under following reaction conditions: 483-523 K; 50 bar; gas hourly space
velocity (GHSV) between 18.000 and 42.000 mlN/(g*h); initial CO2/(CO2+CO) inlet-
ratio between 0 and 1.

The investigated catalyst showed a stable performance over 400 hours time on
stream. Figure 1 (left) shows that the CZZ catalyst enables up to 76 % higher DME
productivity compared to a commercial Cu/ZnO/Al2O3 (CZA) reference catalyst. DME
productivity can be even increased at 503 K by raising CO2 content in the feed. At
higher reaction temperature, the thermodynamic equilibrium becomes more
noticeable, reflected by lower DME productivity for CO2-rich feed composition. More
CO2 in the feed generally favors water formation by reverse water-gas shift reaction,
what also leads to a reduction of DME productivity2. By varying the CO2/(CO2+CO)
inlet-ratio the product selectivity changes and DME selectivity reaches a maximum of
95 % at a CO2/(CO2+CO) inlet-ratio of 0.47 (Figure 1 right).
 Figure 1: DME productivity (left) using CZZ (black) and commercial CZA (red) catalyst, each with FER-type
zeolite, Selectivity of CZZ/FER (right)

Both catalyst systems were subjected to an extensive kinetic study in which

temperature, GHSV and feed composition were varied.
References:
1
Niethammer, B., et al., Alternative Liquid Fuels from Renewable Resources. Chemie Ingenieur
Technik, 2018. 90(1-2): p. 99-112.
2
Catizzone, E., et al., CO2 Recycling to Dimethyl Ether: State-of-the-Art and Perspectives. Molecules,
2018. 23(1). 31
Forced Periodic Operation: Effect of shapes for two simultaneously
imposed modulations

M. Felischak1, D. Nikolic2, M. Petkovska2, C. Hamel1,3, A. Seidel-Morgenstern1,4

1
Otto-von-Guericke University Magdeburg, 39106 Magdeburg, Germany; 2University
of Belgrade, Serbia; 3Anhalt University of Applied Sciences, Köthen, Germany; 4Max
Planck Institute for Dynamics of Complex Technical Systems, Magdeburg, Germany.
Corresponding author: matthias.felischak@ovgu.de

Introduction
The classical design of continuous chemical reactors exploits steady-state operation,
which is optimized and maintained by appropriate control systems. Nevertheless, it is
well-known that the reactor performance can be enhanced by applying periodic
regimes, like forced modulations of input parameters [1,2].
The identification and evaluation of suitable periodic operation conditions is
challenging. One approach that can be used is based on nonlinear frequency
response (NFR) analysis [3]. The focus of this work is the experimental analysis of
shapes for two simultaneously imposed modulations (sinusoidal and square) in
comparison to results predicted by the NFR method. The acetic anhydride hydrolysis
was studied in an adiabatic CSTR exploiting a periodic operation mode, which was
found to be superior to the corresponding steady-state operation.

Theoretical Method
The Nonlinear Frequency Response (NFR) method is fast and easy to apply
analytical method, capable of predicting the performance of forced periodically
operated chemical reactors. Frequency response functions (FRF) of a weakly
nonlinear system, in addition to the basic harmonic, contain a non-periodic (DC) term
and an infinite sequence of higher harmonics [3]. The DC component of the output is
directly linked to the average performance of the periodically operated reactor. The
sign and value of the DC component define whether, and to which extent, the
periodic operation leads to process improvement. Using the NFR method, this DC
component can be approximated. For the case of multiple input variables modulated
simultaneously the optimal phase difference between the modulated inputs can be
directly determined [4,5]. The original method was developed for sinusoidal forcing
functions. However, it can be extended to any shape of periodic input, such as simple
square-waves (see Figure 1a) [6].
 a) b) T T κ Conductivity
meter

Overflow

T
T P2
P1 P1
P1
T T

AA
Thermostat 2 Anhydride
H2O H2 O Thermostat 1 H2O Product
T2 TRef
TRef T1 P
Balance

Figure 1: a) Comparison of yields for sinusoidal and square wave functions with optimal phase difference; b)
Experimental setup for simultaneously modulating various inlet parameters.

Experimental Study
Based on theoretically developed FRFs for an adiabatic CSTR [5], the NFR analysis
was performed for a model reaction, namely the acetic anhydride hydrolysis. Periodic
operation around a steady-state were analyzed and compared to the optimal steady-
state operation. Acetic acid yield was used for comparison, since it can be monitored
easily using conductivity measurements. To verify the theoretical predictions of the
NFR method, an experimental setup has been build (Figure 1b), which is capable to
implement and control the input parameter modulation (frequency, amplitude and
phase difference) for single or simultaneous modulation of the available parameters
(flowrate, feed composition, inlet temperature).

Results
Preliminary experiments evaluated that the forced periodic operation is possible and
reliable for both single and simultaneous modulations. The experimental
investigations confirmed the predictions of NFR analysis, simultaneously modulating
the inlet concentration and flowrate imposing a sinusoidal function. For properly
chosen phase differences, it was possible to obtain beneficial reactor operation.
Based on the evaluation of general inlet function shapes, in addition to harmonic
inlets, also square waves were implemented. The application of the latter is even
more promising, because the nonlinearities are more pronounced. Predicted mean
reactor performance improvements are experimentally validated to evaluate the
potential of both the concept and the NFR method as a predictive tool.

[1] J.E. Bailey, Chem. Eng. Communications 1 (1973) 111-124.

[2] P.L. Silveston, R.R. Hudgins (Editors), Periodic operation of chemical reactors, Elsevier, Oxford, 2013
[3] M. Petkovska , A. Seidel-Morgenstern, Evaluation of Periodic Processes. In: [2], Chapter 14, 387-413.
[4] M. Petkovska, D. Nikolic, A. Seidel-Morgenstern Israel Journal of Chemistry 58 (2018) 663-681.
[5] D. Nikolić, M. Felischak, A. Seidel-Morgenstern, M. Petkovska Chem. Eng. & Technology 39 (2016) 2126-2134.
[6] D. Nikolic, M. Petkovska Chemie Ingenieur Technik 88 (2016) 1715-1722
 Analysis of a cyclically operated semi-batch reactor for the
hydroformylation of long-chain olefins in a continuous production
process under uncertain feed composition

Karsten H. G. Rätze, Otto von Guericke University, Magdeburg;

Kai Sundmacher, Max Planck Institute for Dynamics of Complex Technical Systems,
Otto von Guericke University, Magdeburg

The transition to renewable feedstocks in chemicals production is a challenging task

due to fluctuating compositions of the substrate mixture. State-of-the-art chemical
production plants are not designed for frequent changes in the feedstock quality,
which may lead to degradation of process performance and product quality. To
circumvent this drawback, new processes with advanced control capabilities are
necessary to increase process flexibility.

In a recent contribution, the integration of a repeatedly operated semi-batch reactor

(RSBR) in a continuous production process for the hydroformylation of 1-dodecene
was proposed (Kaiser et al. 2017), which allowed for the adjustment of process
parameters in response to the substrate composition for each batch. In contrast to a
more traditional process arrangement (Jokiel et al. 2018), the full potential of the
setup may be leveraged for a greater operating window at the cost of a more
complex process operation. To evaluate the potential of a quasi-continuous
production process, a detailed, dynamic process model for the aforementioned
example reaction was proposed and compared to experimental results (Rätze et al.
2018; Jokiel et al. 2018) confirming a significant increase in process performance
with respect to selectivity and conversion in comparison to a state-of-the-art process.
However, the potential increase in process performance due to the flexibility of the
RSBR-setup requires further investigation.

In this contribution, the performance of a conventional continuous process and a

RSBR-setup for the hydroformylation of 1-dodecene are compared while considering
a fluctuating ratio of 1-dodecene and dodecene isomers in the substrate feed. For the
RSBR-process, the dynamic process model introduced in (Rätze et al. 2018) is
utilized with a total residence time of 210 min. Using the same constraints for the
continuous
ontinuou pro
process,
e , the helically
helicall coiled
oiled tubular reactor
rea tor (HCTR)
(HCTR) model from Jokiel
o iel et
al. (2018) is employed.

In Figure 1, the
selectivity- conversion
behavior is shown for
both processes.
Through its ability to
incorporate optimal
control trajectories
for the synthesis
gas composition
and to adjust Figure 1:: Selectivity
Selectivit toward
towards the linear aldeh
aldehyde
de tride
tridecanal
anal (nC13al) and
the batch
time for each conversion of 1--dodecene (nC12en) of the (RSBR+CSTR) and continuous batch, the
(HCTR+CSTR) process
pro e setup
etup for flu
fluctuating
tu substrate feed ratios. The start-
RSBR up of the RSBR-setup
RSBR is shown. For the HCTR-setup, steady-state
process is
able to simulations
imulation were performed with varying
ar ing n/iso-ratios
n/i o of the feedstock. outperform
the HCTR with re
respect
pe t to conversion
con
on er ion and selectivity
ele ti it de
despite
pite additional preparation
time and the ne
necessity
e it of up-
up and downstream buffer tanks.

References

Jokiel, M., Kaiser, N. M., Kováts, P., et al. (2018). Heli

Helically
all Coiled Segmented Flow Tubular Rea
Reactor
tor for the Hydroformylation
H droform lation of
Long-Chain
Chain Olefin
Olefins in a Thermomorphi
Thermomorphic Multipha
MultiphaseeSSystem.
tem. Chemical
Chemi al Engineering Journal.
ournal. DOI: 10.1016/j.cej.2018.09.221.
10.1016/j. ej.2018.09.221.

Kaiser, N. M., Jokiel, M., McBride, K., Fla

Flas ig, R. J.,
Flassig, ., and Sundma
Sundmacher,her, K. (2017). Optimal Reactor
Rea tor Design
De ign via
ia Flux
Flu Profile
Analysis
Anal i for an Integrated HHydroformylation
droformylation
droform lation Pro
Process.
e . Indu
Industrial
trial & Engineering Chemi
Chemistry
tr Re
Research
ear h 56(40): 11507
11507–11518.

Jokiel,
o iel, M., Rätze,
Rät e, K. H. G., Kaiser,
Kai er, N. M., et al. (20
(2018). Miniplant Scale Evaluation of a Semibatch-Continuou
Continuous Tandem Reactor
Rea tor
System for the Hydroformylation of Long--Chain
Chain Olefin
Olefins.. Indu
Industrial
trial & Engineering Chemi
Chemistry
tr Re
Research
earch Resubmitted
Re ubmitted 15.11.2018.

Rät e, K. H. G., Jokiel,

Rätze, o iel, M., Kaiser,
Kai er, N. M., and Sundma
Sundmacher,
her, K. (2018). Cyclic Operation of a Semi-Batch
Batch Reactor
Rea tor for the
Hydroformylation of Long-Chain
Chain Olefin
Olefins and Integration in a Continuou
Continuous Produ
Production
tion Pro
Process.
e . Chemi
Chemical
al Engineering Journal.
ournal.
DOI: 10.1016/j.cej.2018.11.151.
Machine learning approaches for the prediction of oxygen evolution
catalysts.
Stefan Palkovits,
Institute for Technical and Macromolecular Chemistry, RWTH Aachen University

The predictions of catalysts that enable a specific reaction is still in most cases a
problem that is not solved until today. Very often more traditional approaches are
used in chemistry where a small amount of catalysts is first synthesized, then tested
and then modified according to the observations made during the testing procedure
and the subsequent analytics of the catalyst.

Especially in the 1990'ies some efforts existed to speed up the synthesis and testing
procedures in heterogeneous catalysis [1, 2] by suitable protocols and the use of
high-throughput reactors. This ultimately led to the idea to predict solid catalysts
based on suitable descriptors [3]. These kinds
of predictions were not continued in the next
years, methods like the high-throughput testing
of large catalyst libraries remained, but the
evaluation of performance criteria is most of
the time in the hands of skilled experts.

In parallel, but a completely different field, the

development of new search algorithms used
for example for picture search and
classification machine learning methods and
artificial intelligence evolved with the growing
of the internet and the availability of huge data
Figure 1: Structure of one used machine
sets. Companies like Google or Facebook learning model.
drive these developments actively as they are
at the heart of their business model.

But can artificial intelligence also be used in chemistry? There are well performing
examples where machine learning is used in computational chemistry to speed-up
some parts of the time-consuming calculations [4]. Also, especially in the field of
organic synthesis critical voices exist who prefer chemical expert knowledge over
machine learning approaches [5].

But is there a chance to bring

together the world of artificial
intelligence and combinatorial
heterogenous catalysis? In this work
we present how predictions can be
made for water oxidation catalysts
based on machine learning
approaches (Figure 1).
Figure 2: Prediction of a published data set for an
artificial neural network.
To do so published data sets with
about 6.000 samples of Ni/Fe/Co/Ce catalysts in varying compositions were used to
train different machine learning algorithms (e.g. Artificial Neural Networks).
Depending on the respective method a decent prediction precision can be achieved
not only for the train and test fractions of the data set (Figure 2) but also for
completely different prepared solids from own work on water splitting. The
performance of the materials predicted by the used models, also shows that simpler
linear machine learning methods exhibit a similar performance compared to more
complicated ones.

References

[1] S. M. Senkan, Nature (1998), 394, 350.

[2] S. Olejnik (Palkovits), C. Baltes, M. Muhler, F. Schüth, Journal of Combinatorial
Chemistry (2008) 10 (3), 387-390
[3] C. Klanner, D. Farrusseng, L. Baumes, M. Lengliz, C. Mirodatos, F. Schüth, Angew. Chem.
(2004) 116, 5461-5463
[4] F. Brockherde, L. Vogt, L. Li, M. E. Tuckerman, K. Burke, K.-R. Müller, Nature
Communications (2017) 8, 872
[5] B. Maryasin, P. Marquetand, N. Maulide, Angew. Chem. Int. Ed. (2018) 57 (24), 6978-6980
 Novel flexible electrochemical microreactor and its application to
Kolbe electrolysis and Cation Pool / Flow method

Athanassios Ziogas1, Christian

Chri tian Hofmann1, Sebastian Baranyai1,2, Patrick Löb1,
Gunther Kolb1; 1 Fraunhofer Institute
In titute for Mi
Microengineering
roengineering and Microsystems
Micro tem IMM,
Mainz, Germany; 2 Ho
Hoch
Hochschule
h hule Kon
Konstanz
tan Te
Technik,
hni , Wirt
Wirtschaft
haft und Gestaltung,
Ge taltung
Konstanz, Germany

Currently a renaissance of ele

electrochemistry
tro hemi tr for the synthesis
nthe i of organi
organic compounds
has started.. It iis dri
driven
en by the search for „green“ synthesis routes, by the emergence
of no
novel
el synthesis
nthe i strategie
trategies and also by the ambition for a direct
dire t utilization of
sustainable (e e ) electric energy.[1] Therefore,, organi
(excess) organic electrochemistry
electrochemi tr is now
considered as future emerging technology for the environment-friendl
friendly produ
production
tion of
chemical
hemi al compounds.
ompound . Neverthele
Nevertheless,, there are still
till challenges
hallenge and problem
problems lin
linked
ed to
electrosynthesis
ele tro nthe i and there is al
also
o a need for fle
flexible
ible reactor oncepts.[2]
rea tor concepts.
Electrochemical
Ele tro hemi al microreactor
mi roreactors - characterized by small electrode distances
distan e and great
surface-to-volume-ratios - contribute to solve these issues. Ba
Based
ed on itits long tra
track in
developing and realizing electrochemical
electro hemi al mi rorea tor [3], Fraunhofer IMM developed
microreactors
an inno
innovative
ati e reactor
rea tor concept
on ept addre
addressing
ing e
especially
pe iall the a
aspects
pe
pects
t of modularity,
flexibility,
fle ibilit , high pre
pressure
ure operation and accessibility
a e ibilit to produ
production
tion scale.

Fig. 1:
Single reactor
rea tor plate with mi
micro-
ro
structured
tru tured electrode (Pt coated)
oated) and
integrated heat exchanger (left).
Assembled
A embled flexible ele
electrochemical
tro hemi al
microreactor with four reactor
rea tor plates
plate
(right).

This new reactor (see Fig. 1) has a plate stack design as basis for a flexible
fle ible rea
reactor
tor
concept. The plates host the structured
tru tured ele
electrodes
trode typically
t pi all on both sides
ide and are
equipped with an integrated heat exchanger. A combination
ination of additi e
additive
manufacturing
manufa turing to realize
reali e the ba
base
e plate
plates with their complex
omple fluid stru
structures,
ture , surface
urfa e
coating
oating (e.g. with PTFE) of the plates
plate for ele
electric
tri insulation,
in ulation, milling to create
reate the micro
channels
hannel on the plates surface
surfa e and electroplating to depositit different electrode
ele trode
materials are used to realize the versatile electrochemical microreactor. The basic
reactor plates are characterized as follows:
 Electrode outer dimension: 100 mm x 118 mm
 Active electrode surface per structured plate side: 53.6 cm2 provided via 67
micro channels (dimensions: width 800 μm, depth 100 μm and length 100 mm)
 Channel volume per structured plate side amounts to 0.5 cm3
The reactor is designed for operation up to 200 °C and up to 100 bar for electrolyte
flow rates up to 100 mL min-1. The reactor concept allows a multitude of optional
operation conditions:
 Operation of 1 to 9 electrode assembly units in the overall reactor housing
 Operation of the electrode assemblies as mono or bipolar cells
 Operation of the electrode assemblies as undivided or divided cell
 Parallel, serial or mixed operation of the electrode assemblies. Therewith,
numbering-up and scale-up possibilities are also provided.
The design, different possible operation conditions and underlying COMSOL
simulations regarding fluid flow distribution and heat exchange will be presented.
Furthermore, recent results of applying this novel reactor concept to two different
chemistries will be reported. Former results regarding the Kolbe electrolysis in
context of producing fuels from fatty acids [4] could be further improved with the new
reactor concept. E.g. for the asymmetric continuous Kolbe electrolysis at current
densities of 1.7 kA*m-2 and residence time of 0.1 s the Faraday efficiency could be
increased further to 91%. The yield was quantitative with a selectivity towards 97% of
n-alkanes. As second application, the Cation Pool / Flow method as modern organic
synthesis approach will be presented.

[1] A. Wiebe et al., Angew. Chem. 130 (2018) 2-30.

[2] M. Yan et al., Angew. Chem. Int. Ed. 56 (2017) 2-9.
[3] A. Ziogas et al., J. Appl. Electrochem. 39 (12) (2009) 2297-2313.
[4] A. Ziogas et al., WO 2016/70075 A1.
 Optimizing Gas Diffusion Electrodes for High-Rate CO2/H2O Co-
Electrolysis towards Formic Acid / Formate

A. Löwe1, D. Kopljar2, F. Bienen2, N. Wagner2, E. Klemm1

1
: University of Stuttgart - Germany,
2
: German Aerospace Center, Stuttgart - Germany

Electrochemical low-temperature conversion of CO2 is a promising way to reduce

GHG emissions and to valorize CO2 as a carbon-source to produce basic chemicals
and/or to store excess electricity from renewable resources. In contrast to CO and
CH4, aqueous formic acid or formate solutions offer advantages regarding handling,
storage, toxicity and safety. In terms of its use as chemical formic acid/formate may
serve as a key precursor for the decentralized production of synthesis gas, as it can
be decomposed to hydrogen or carbon monoxide. Other than that, formatotrophic
bacteria can utilize it as substrate to produce higher hydrocarbons like isobutene or
propane.[1] Regarding the energetic use, two major pathways are under
consideration. Either via the direct utilization in Direct Formate or Formic Acid Fuel
Cells (DFFC or DFAFC), or by upstream hydrogen production from dehydrogenation
and subsequent use in a H2-fuel cell.

CO2 + H2O + 2e-  HCOO- + OH- φ0 = -0.665 V (vs. SHE, pH=10)

Alkaline CO2 reduction provides one big benefit; it helps to suppress the parasitic
water reduction to hydrogen. However, this comes with the downside of producing
formate instead of formic acid and the coupled production of bicarbonate as another
CO2 molecule can react with the produced hydroxide ion. To solve for this problem
bipolar membrane electrodialysis may be a reasonable solution, which can yield a
product stream of pure formic acid, assuming no conducting salts other than formate
and bicarbonate were used in electrolysis.
One of the biggest problems to overcome in electrochemical CO2 reduction reaction
(CO2RR) are the typically very low reaction rates (current densities) achievable due
to the low solubility of CO2 in aqueous solutions. Recently we demonstrated SnOx-
loaded Gas Diffusion Electrodes (GDE) to be a key factor to solve this issue.[2-4]
These electrodes provide a large internal surface area and combine an
advantageous pore structure with high hydrophobicity. However, so far only the
electrodes properties (carbon structure, electrode wetting and catalyst dispersion)
were optimized. We now demonstrate that process conditions like temperature,
electrolyte composition and a controlled start-up phase are as well of upmost
importance. The results shown in figure 1 demonstrate the influence of these
parameters. In short, an optimum temperature exists, which results from slow intrinsic
reaction kinetics and little mass transport coefficients at lower temperatures and
decreasing CO2 solubility at higher temperatures. Optimizing the used electrolyte by
avoiding gas formation and carefully starting-up the GDE helps to further raise the
performance up to 1200 mA cm-2.

Figure 1: Left side: Average FE of CO2RR towards formate and hydrogen. CO

selectivity is not shown but ranges between 6 % and 11 %. Right side: Comparison
of our optimized GDE with literature values. Literature (black), recent own
publications [2,3] (red) and unpublished results (blue). a) Temperature optimization. b)
Optimized electrolyte and controlled electrode start-up.

[1] www.eforfuel.eu
[2] D. Kopljar, N. Wagner, E. Klemm, Chem. Eng. Technol., 39 (11), 2016, p. 2042-
2050.
[3] D. Kopljar, A. Inan, P. Vindayer, N. Wagner, E. Klemm, J. Appl. Electrochem., 44
(10), 2014, p. 1107-1116
[4] D. Kopljar, A. Inan, P. Vindayer, R. Scholz, N. Frangos, N. Wagner, E. Klemm,
Chem. Ing. Techn., 87 (6), 2015, p. 855-859
The authors would like to thank the German BMWi (Bundesministerium für Wirtschaft
und Energie - support code: 03ET1037B) for the financial support.
 Experimental and Model-Based Characterization of Gas-Diffusion
Electrodes for Oxygen Reduction

T. Turek, TU Clausthal; U. Krewer, TU Braunschweig; I. Manke, M. Paulisch,

Helmholtz-Zentrum Berlin; P. Kunz, U. Nieken, Universität Stuttgart; C. Roth, FU
Berlin; W. Schuhmann, Ruhr-Universität Bochum; T. Vidaković-Koch, Max-Planck-
Institut für Dynamik komplexer technischer Systeme Magdeburg

Introduction
In gas diffusion electrodes (GDE), electrocatalysts are in contact with gas and
electrolyte ensuring a large active three-phase boundary. GDE are used for important
technical applications in energy transformation and chemical synthesis such as fuel
cells and modern electrolysis processes. Silver-based GDE have been
commercialized for a new energy-efficient chlor-alkali process [1] and are presently
also under investigation for CO2 electrolysis yielding CO and H2 [2]. Within the DFG
Research Unit 2397 “Multi-scale analysis of complex three-phase systems” the
interplay of reaction and transport processes in silver-based GDE during oxygen
reduction in alkaline electrolyte is being studied with a variety of modern methods.
From a reaction engineering point of view, a physico-chemically based description of
this type of GDE is especially demanding. This is because the distribution of liquid
electrolyte and gases in the pore system is unknown and might be influenced not
only by the hydrophilic/hydrophobic surface properties of the GDE, but also by the
local reaction conditions, i.e. temperature, concentrations, and potential. This
contribution describes the present status achieved in the Research Unit with
emphasis on the following topics:
 Analysis of the local distribution of pore sizes and surface properties in GDE.
 In situ analysis of electrolyte distribution and local measurement of activities.
 Development of mathematical models for description of overvoltage during
steady-state and transient operation.

Results
GDE with different properties are prepared from Ag powders and PTFE suspensions
via spraying on nickel nets as current collectors. Electrodes with low overvoltage
during oxygen reduction at typical chlor-alkali conditions (80 °C, 30 wt.% NaOH)
contain 2 – 5 wt.% PTFE and have average pore sizes of 1 – 3 μm. We believe that
GDE
E with e
even
en lower PTFE content
ontent suffer
uffer from ele
electrolyte
trol te flooding wherea
whereas higher
PTFE contents
ontent lead to in
insufficient
insuffi
uffi ient liquid penetration. Figure 1 (left) shows
show
how the result
re ult
of a tomographi
tomographic anal
analysis
i revealing
re ealing intimate contact
onta t between silver
il er ele
electrocatalyst
tro atal t
and PTFE binder. The intru
intrusion
ion of liquid ele
electrolyte
trol te in the pores
pore iis mathemati
mathematically
all
modelled (Fig. 1 middle) while first
f results of in situ measurements
ea urements of a working
wor ing GDE
depicted in Fig. 1 (right) provide
pro ide insight
in ight into the electrolyte transport under reaction
conditions.

Fig. 1. Di
Distribution
tribution of Ag (grey) and PTFE (green) in a GDE (left), simulated
imulated intrusion of ele
electrolyte
trol te in
pore structure
tru ture (middle), mea
measured
ured liquid distribution
di tribution in wor
working
ing GDE (right).

i en the complexity
Given omple it of the three
three-dimensional
dimen ional GDE structure
tru ture and the e
extremely
tremel large
tomographic data sets,
tomographi ets, the structure
tru ture is
i represented
repre ented by
b virtual but realistic
reali ti
microstructures through stochastic
stocha ti modeling [3]. The mea
measurements
urements of the electrolyte
ele trol te
distribution
n are supported
upported by
b calculations
al ulation of the contact angles
ngles during fluid-solid
interactions in the GDE [4]. Ele
Electrode
trode structure
tru ture and ele
electrolyte
trol te distribution
di tribution are finally
finall
used
u ed together with the oxygen
o gen redu
reduction
tion kinetics
ineti to develop
de elop a mathemati
mathematical
al model for
the de
description
ription of the o
overvoltage.
er oltage. In contrast
ontra t to earlier a
assumptions
umptions
umption that only the low
oxygen solubility
olubilit and diffusivity
diffusi it limits the a
achievable
hie able GDE performan
performance
e at higher
current densities [5],, recent findings
finding indicate
indi ate that local changes a ti it of OH-
hange in the activity
ions and H2O must be also taken into account [6].

References
[1] I. Moussallem, J.. Jörissen, U. Kunz, S. Pinnow, T.. Ture Turek,, J.. Appl. Electrochem.
Ele tro hem. 38
(2008) 1177–1194
[2] T. Haa
Haas,, R. Krau
Krause, e, R. Weber, M. Demler, G. S Schmid,
hmid, Nature Catalysis
Catal i 1 (2018) 32–
32
39
[3] M. Neumann, M. O Osenberg,
enberg, A. Hilger, D. Franzen,
Fran en, T. Turek,
Ture , I. Man
Manke,e, V. S
Schmidt,
hmidt,
Comp. Mater. S Sci.i. 156 (2019) 325–331
325
[4] P. Kun
Kunz,, S. M. Hassanizadeh, U. Nieken,
Nie en, Tran
Transp.p. Porou
Porous Med. 122 (2018) 253–277
253
[5] S. Pinnow, N. Chavan, T. Turek,
Ture , J.. Appl. Ele
Electrochem.
tro hem. 41 (2011) 1053–1064
1053
[6] A. Botz, J. Clausmeyer, D. Öhl, T. Tarnev, D. Franzen, T. Turek, W. Schuhmann,
Angew. Chem. Int. Ed. 57 (2018) 12285–12289
Lecture abstracts
Wednesday, 29 May 2019
Liquid core waveguide membrane microreactor in situ studies of V-
substitution in heteropoly acid catalysts in biomass oxidation
Sebastian Ponce1, Jakob
a ob Albert2, Alfons Drochner1, Bastian B.
B.J.M. Et old 1, 1Ernst-
.M. Etzold*
Berl-Institute
In titute for Te
Technical
hnical
hni al and Ma
Macromolecular
romole ular Chemi
Chemistry,
tr , Te
Technis
hnische
hni he Universität
Uni er ität
Darmstadt,
tadt, 64287 Darmstadt, Germany;
German Lehr
Lehrstuhl
tuhl für Chemi
Chemische
he Reaktionstechnik,
Rea tion te hni ,
Universität
Uni er ität Erlangen-Nürnberg,
Erlangen Nürnberg, 91058 Erlangen, Germany.
German

The partial oxidation

idation of bioma
biomass b
by mole
molecular
ular o
oxygen
gen into valuable
aluable energy
energ carrier
arrier
molecules,
mole ule , platform chemical
hemicals,, and bio
bio-based
ba ed produ
products
t iis an important alternative
alternati e to
avoid fossil based CO2 emissions
emis ion [1]. In this sense, the
euuse
e of heteropolyacid
heteropol a id (HPA
(HPA-
n) (Hx[PVnMozO40]) ha
has emerged a
as a promi
promising
ing catalysts
atal ts
t for the selectively
ele ti el
transformation
tran formation of biomass into formic
formi acid
a id and CO2, a
as re
recently
ently demonstrated
demon trated b
by
Albert et al. in the so-called
alled OxFA
O FA pro
process
e [2]. While high V-substitution
ubstitution is
i known
nown to
positively
po iti el influence
influen e the rea
reaction
tion o
overall
erall a
activity,
ti it , e
experimental
perimental obser
observations
ob er ation ha
have
e
shown
hown a contrasting
ontra ting beha
behavior.
ior. Therefore, further studies
tudie how V-substitution
V
influences
influen e the redox
redo cycle
ycle are ne
necessary.
e ar . HPA
HPA-n
n catalysts
atal t present characteristic
hara teri ti
UV/Vis ab
UV/Vi absorption
orption spectra
pectra
pe tra in their oxidized
o idi ed and reduced
redu ed forms.
form . Thus,
Thu , redu
reduction
tion and
reoxidation rates under anaerobi
anaerobic and aerobi
aerobic conditions
ondition could
ould be studied.
tudied. Re
Recently,
entl ,
we reported a liquid core
ore wa
waveguide
eguide membrane microreactor
mi rorea tor (LCWM), based
ba ed on a
Teflon AF tube (Fig. 1), which
whi h allow
allows in situ UV/Vi
UV/Vis spectra
pe tra of liquid phases
pha e while
complete
omplete ga
gas/liquid
/liquid saturat
aturation is achieved [3].. In thi
this study,
tud , the novel concept
on ept of a
LCWM mi
microreactor
rorea tor iis u
used
ed to carry
arr out spectroscopic
pe tro opi studies
tudie of the redox
redo kinetics
ineti of
different HPA-n
n catalysts
atal ts during the OxFA
O FA process.
pro e .

Figure 1: SScheme
heme of LCWM setup. etup -- Teflon AF tube, -- Optical fiber, LS: light
source, FC: fluidic cells, P: pre
pressure
ure sensor,
en or, T: temperature control,
ontrol, HW: heating
wire, BPR: ba
backpressure
pre ure regulator,
regulat SP: spectrometer, V: valve.
Results
While high V-substituted (HPA-5) catalysts showed the fastest reduction kinetics, no
direct linear correlation of the substitution degree to the reduction kinetics was
obtained. Combining the kinetic results with cyclovoltammetry (Fig. 2 left) and EPR
characterization indicates, that two competing active sites influence the reduction
kinetics. On the one hand, dissolved (VO2+), and on the other hand the
heteropolyanion itself. While the activity of the heteropolyanions as active site itself
seem to slow down with higher V-substitution degree, the amount of highly active
(VO2+) dissolved increases with higher substitution. The detrimental effect of V-
substitution on activity and number of active sites explains the observed reduction
activity trend as also selectivity patterns reported in literature [1]. Moreover, for
reoxidation experiments, the degree of V-substitution played again a determinant
role. HPA-5 complexes showed the highest initial reoxidation rates even at mild
temperature conditions, while for mono-and non-substituted catalysts reoxidation was
attained only at higher temperatures (at T> 100 oC) (Fig. 2 right). All in all, this study
shows, that the recently introduced LCWM microreactor concept suits very well for
fast and reliable in situ UV/Vis kinetic studies on gas-liquid systems.

0.25
0,5
40 - 80 oC
HPA-1
0.20 HPA-5
0,0
kred / min-1

0.15
ln(kox)

-0,5 HPA-0
HPA-0 HPA-5
0.10 HPA-2
-1,0
0.05
HPA-1
120 - 150 oC HPA-2
-1,5
0.00
-470 -460 -450 -440 -430 0,0024 0,00280 0,00315
-1
Potential / mV 1/T / K

Figure 2: Left: Correlation between reduction rate constants and reduction potential
of the HPA-n catalysts, and right: Arrhenius plot of the reoxidation of HPA-n
catalysts.
References
[1] J. Albert, Selective oxidation of lignocellulosic biomass to formic acid and high-grade cellulose using tailor-
made polyoxometalate catalysts, Faraday discussions 202 (2017) 99-109.
[2] J. Albert, R. Wölfel, A. Bösmann, P. Wasserscheid, Selective oxidation of complex, water-insoluble biomass
to formic acid using additives as reaction accelerators, Energy & Environmental Science 5 (2012) 7956-7962.
[3] S. Ponce, H. Christians, A. Drochner, B.J.M. Etzold, An Optical Microreactor Enabling In Situ Spectroscopy
Combined with Fast Gas-Liquid Mass Transfer, Chemie Ingenieur Technik 90 (2018) 1855-1863.
 Digital Development and Application of 3D-printed Reactionware and
Reactors for Emulsion Copolymerizations
Sven Bettermann, Hans-Ulrich Moritz, Werner Pauer
Institute for Technical and Macromolecular Chemistry, University of Hamburg,
Bundesstraße 45, 20146 Hamburg, Germany
The design and construction of individualized, configurable devices for the exploration of
chemical processes can strongly profit from current innovative 3D printing techniques.[1]
We demonstrate the application of 3D-printed tubular reactors for the accelerated devel-
opment of continuous emulsion copolymerizations (EPs) as well as 3D-printed
reactionware for batch reactors based on the combination of CAD modeling and CFD
simulation.
A tubular bended reactor was 3D-printed from polylactic acid by fused deposition model-
ing (FDM) as a sophisticated concept to gain easy access to continuous reactors. The
device features a short and narrow residence time distribution, dead volumes below
5 vol% and air-cooling. We show its integration into a modular reaction system, a prod-
uct change in one run and how innovative thermal imaging was used as an online moni-
toring tool.[2] The digital characterization by CFD simulation in combination with CAD
fabrication led to a lean development method of the reactor resulting in detailed flow vis-
ualizations and the incorporation of temperature sensors as well as 3D-printed sampling
points along the device. Thus, processes were investigated along the reactor to enable
detailed temperature, conversion and particle size developments.
Furthermore, we present a flexible scale-manufacturing concept of customizable 3D-
printed stirrers for the investigation, optimization and scale-up processes of batch EPs.
Diverse and cost-effective polyamide stirrers were 3D-printed by FDM and initially used
in a reaction calorimeter to investigate their suitability and performance. The results en-
couraged the design of adjusted stirrers for applications in scale-up processes in a 10 L
reactor. This approach enables easy access to further optimized stirrers with respect to
special mixing demands or mass and heat transfer requirements as well as tailor-made
implementation to already existing plant systems.

[1] C. Parra-Cabrera, C. Achille, S. Kuhn, R. Ameloot, Chem. Soc. Rev. 2018, 47, 209–230. S.
[2] Bettermann, B. Schroeter, H.-U. Moritz, W. Pauer, M. Fassbender, G. A. Luinstra,
Chem. Eng. J. 2018, 338, 311–322.
 Investigating Ethylene Epoxidation under Industrial Conditions
in a Compact Profile Reactor

Viktor Berg1, Oliver Korup1,3

1
, Michael Geske2, Michael Schmidt3, Frank
Fran Ro ow i2,4,
Rosowski
Raimund Horn1,3
1) Hamburg University
i er it of Technolog
Technology,Germany;
, 2) BasCat-BASF UniCat Joint Lab, TU Berlin/Germany;
Berlin
3) Rea
Reacnostics
no ti GmbH, Hamburg/German
Hamburg/Germany 4) BASF SE, Ludwigshafen, Germany

The operando anal

analysis
i of catalytic
catal ti reactions
rea tion is becoming more and more important.
important
Reactors,
Rea tor , enabling the spatiall
spatially re
resolved
ol ed detection
dete tion of temperatures
temperatures and gas
ga pha
phase
e
compositions,
ompo ition , were constructed
onstructed for catalyst samples of a few gram,
ram, often supported
e.g. on monoliths [1]. We present
pre ent a new and versatile Compa
Compactt Profile Reactor
Rea tor (CPR)
for full
fully automated measurement of concentration
on entration and tem
temperature
perature profiles
profile through
particulate catalyst samples
amples of less
le than one gram, at temperatures up to 550 °C and
pressures up to 20 bar. Axial
xial temperature gradients
gradient in the reactor are minimal and
radial concentration
on entration and temperature gradient
gradients are negligible. This allows
mechanistic
me hani ti and kinetic
inetic studie
studies on small amounts of catalyst typically
typicall obtained in
laboratory synthesis
laborator nthe i but at indu
industrially
triall rele
relevant
ant temperature and pres
pre
pressure
ure conditions.
ondition .
We demon
demonstrate
trate the performan
performance
e of the CPR for the selective
ele ti e o
oxidation
idation of eth
ethylene
lene
to ethylene oxide (EO) on an
a alumina supported
upported silver
il er catalyst
atal t at 16 bar pressure.
pre ure.

Figure 1: Picture of used Compact Profile Reactor

A glass tube with 6 mm OD and 4 mm ID wa

was filled with split
plit particle
particles of an Ag/-
Al2O3 catalyst (pro
(provided
ided by BASF) and mounted in the Compact Profile Reactor
Rea tor
(Fig.1) for profile measurements.
measurement The principle is described in patent application
appli ation
PCT/EP2017/070633 [2]. Ga
Gas samples
ample have
ha e been taken
ta en along the axial direction of
the rea
reactor
tor via
ia a steel
teel capillar
capillary (Ø 0.7 mm) whi
which
h had a laser drilled orifice
orifi e of
approximately 50 µm in its wall.
wall A K-type
t pe thermo
thermocouple
ouple was
wa situated
ituated in the capillary
apillar
tip-aligned at the orifice. The reaction
rea tion wa
was conducted
ondu ted at 16 bar gauge pressure and a
gas phase composition
ompo ition of C2H4/O2/CO2/H2O, 35/7/1/0.15 vol-%.
%. 1,2 – dichloroethane
(mixed in methane) was added to the
the feed to promote the catalyst
atalyst towards
toward higher
ethylene
eth lene o
oxide
ide selectivity.
ele tivity. Nitrogen wa
was ta
taken
en a
as inert
nert to balance the feed gas
ga
composition and 2.5 vol-%
% of methane
m as internal standard. In order to analyze
anal e the
gas composition
ga ompo ition an Agilent GC 7890 was used. Concentration
on entration and temperature
profiles were mea ured at a GHSV of 4750 h-1 with a catalyst
measured atal t sieve
ieve fraction
fra tion of 200 –
400 µm and a bed length of 37 mm.

-1
Figure 2: Molar flow and Temperature Profiles at GHSV of 4750h

In Figure 2 the mea

measured
ured molar flow rate
rates are shown.
hown. The
These
e profiles are well suitable
uitable
to study
tud the epoxidation
epo idation rea
reaction
tion under indu
industrial
trial conditions
ondition
onditions and to get more
information about the kinetic
kineti
ineti parameter
parameters b
by fitting the profiles
profile e.g. to a p
pseudo
eudo
homogeneous model. It can be seen
een that the eth
ethylene
lene oxide production rate
decreases
de rea e with the bed length and ceases at about 21 mm while CO2 is formed
throughout the entire bed. This
Thi non
non-monotonic
monotoni behavior
beha ior of the EO formation could
ould be
explained
e plained b
by surface
urfa e blocking
blo ing of selective
ele ti e EO sites
ite bby a product,
produ t, e.g. CO2, or a
potential change
hange of catalyst
atalystt structure.
atal tru ture. This
Thi is
i currently
urrentl under in
investigation
e tigation b
by
conducting
ondu ting spatially
patiall re
resolved
olved spectroscopy.
pe tro op

References

[1] Anal
Analyst,
t, 2010, 135, 2260
2260-2272; [2] Te
Technische
hni he Universität
Uni er ität Hamburg
Hamburg-Harburg. 2018.
APPLICATION PROFILE REACTOR FOR OPERANDO MEASUREMENTS. Inventor:
In entor:
Raimund Horn, Oli
Oliver
er Korup. Filling Date: 14.08.2
14.08.2017,
017, EN, PCT/EP2017/070633
 Spatial characterization of heterogeneously catalyzed gas phase
reactions via operando NMR imaging methods
Harm Riddera, Mojtaba Mirdrikvandb, Mehrdad Sadeghia, Jürgen Ulptsa,
Wolfgang Dreherb, Jorg Thöminga
a
University of Bremen, Faculty of Production Engineering, Chemical Process
Engineering, 28359 Bremen, Germany
b
University of Bremen, Faculty of Chemistry, in vivo MR group, 28359 Bremen,
Germany
For optimizing heterogeneously catalyzed gas phase reactions it is crucial to gain
insight into local heat, mass, and momentum transport phenomena inside the
catalyst bed. For such investigations, a great variety of measurement techniques
have been developed, often using invasive or integral methods which reduce the
potentially available spatial resolution. Many non-invasive techniques, however,
suffer from reduced applicability due to the opaque structure of solid catalyst
supports.

We present studies on operando nuclear magnetic resonance (NMR) based imaging

methods, which allow minimal-invasive mapping of concentration, temperature, and
velocity within solid monolithic sponges and packed beds. To achieve this, a lab-
scale fixed-bed glass reactor was designed and horizontally inserted into a 7 Tesla
NMR tomograph. The measurements were performed using the hydrogenation of
ethylene as a case study reaction.

The measured process parameters (such as temperature, gas phase concentrations

and yield) were compared to simultaneously performed mass-spectrometric
measurements and predictive 1D pseudo-homogeneous calculations of the process.
Both were in remarkable agreement with the NMR results and underline the
applicability of the measured values (Figure 1). Further, we were able to measure
gas flow velocities in monolithic catalyst supports. At present, operando
measurements in catalytic sponges resemble very well the results of CFD flow
simulations (Figure 2).
In our previous work, temperature measurements with NMR were limited to an upper
temperature of 160 °C. In order to exceed the current limit, a new NMR measurement
approach has been applied. Whereas the former method depends
depend on the MR
spectrum of liquid ethylene glycol (MRSI), the new method measures the
temperature dependent self-diffusion
self coefficient, which is no longer bound to
ethylene glycol (DW-MRI). Comparisons between two approaches are in reasonable
agreement, validating the new measurement technique for further use. Furthermore,
a new reactor concept is under way, aiming to perform heterogeneously
heterogeneou l catalyzed
gas phase reactions at temperatures
temperat of up to 250 °C and a pressure of 30 bar inside
the 7 Tesla NMR tomograph.
tomograph The up-to-date finding and first results of this concept
will be part of this pre
presentation.
entation.
a c)
c)
a c

b)

Fig. 1. Operando NMR measurements

mea urement of the hydrogenation of ethylene to ethane: 2D
concentration maps obtained via spectroscopic imaging, MRSI (a), product-rea
reactant
tant ratio profiles
along the monolithic sponge in comparison with a predictive simulation and a result of integral
measurements using process mass spectrometry (pMS) at the outlet of the reactor (b), and
temperature profiles in compari
omparison
on with a predictive simulation; error bars result from deviations
between the ethylene glycol spectra
spe tra used for temperature determination (c).. (Ulpts et al. 2018,
Catalysis Today. doi.org/10.1016/j.cattod.2017.05.009)
doi.org/10.1016/j. attod.2017.05.009)
Fig. 2. Operando NMR measurements and simulation of laminar flow in an empty reactor tube.
 Experimental and numerical investigation of reactive species
transport around a small rising bubble
Andre Weiner, TU Darmstadt, Germany; Jens Timmermann, Sasol GmbH, Germany;
Chiara Pesci, TU Darmstadt, Germany; Marko Hoffmann, TU Hamburg, Germany;
Michael Schlüter, TU Hamburg, Germany; Dieter Bothe, TU Darmstadt, Germany;
We present experimental and numerical investigations of small oxygen bubbles
which are released into a measurement cell filled with tap water. The oxygen
dissolves and reacts with sulfite to sulfate. Laser-induced fluorescence was used to
visualize the oxygen concentration in the bubble wake from which the global mass
transfer coefficient could be calculated. The ruthenium-based fluorescent dye
seemed to be surface active, such that the rise velocity was reduced by up to 50 %
compared to the experiment without fluorescent dye and a recirculation zone formed
in the bubble wake. To access the local mass transfer at the interface, we performed
complementary numerical simulations. Since the fluorescence tracer was essential
for the experimental method, the effect of surface contamination was also considered
in the simulation. Rise velocity and mass transfer coefficient agree within a few
percents between experiment, simulation and literature results. Because the
fluorescence tracer is frequently used in mass transfer experiments, we discuss its
potential surface activity.

Fig. 2: Flow around a rising bubble with

Fig. 1: Oxygen concentration in the
clean (left) and contaminated interface
bubble wake – experiment (left) and
(right).
simulation (right).

Acknowledgement
The authors gratefully acknowledge the financial support provided by the German
Research Foundation within the Priority Program Reactive Bubbly Flows, SPP 1740
(SCHL 617/12-1 and BO 1879/13-2). We would also like to thank Prof. S. Schindler,
Prof. S. Herres-Pawlis and Dr. habil. R. Miller for fruitful discussions. Numerical
simulations were performed on the Lichtenberg high performance computer of the TU
Darmstadt.
References
[1] A. Weiner, D. Bothe: Advanced subgrid-scale modeling for convection-dominated
species transport at fluid interfaces with application to mass transfer from rising
bubbles. Journal of Computational Physics, vol. 347, pp. 261-289, 2017.
[2] C. Pesci, A. Weiner, H. Marschall, D. Bothe: Computational analysis of single
rising bubbles influenced by soluble surfactant. Journal of Fluid Mechanics, vol. 856,
pp. 709-763, 2018.
[3] A. Weiner, J. Timmermann, C. Pesci, J. Grewe, M. Hoffmann, M. Schlüter, D.
Bothe: Experimental and numerical investigation of reactive species transport around
a small rising bubble. Under review.
 Correlation of Process Conditions and Polymer Properties in
Continuous Solution Polymerization

Julia Eigenseer, Mohammad Al-Haj Ali, Noureddine Ajellal, Markus Busch;

TU Darmstadt, Ernst-Berl-Institut für Technische und Makromolekulare Chemie,

Darmstadt/Germany;

markus.busch@pre.tu-darmstadt.de

Polyethylene is one of the most important polymers with around one third of the
allover turnover in Europe. Main reason for this demand is the high versatility with a
broad range of possible properties. [1] Its physical specifics and processability
strongly depend on the respective polymeric microstructure. As polyethylene only
consists of hydrocarbons, the microstructure is given by short-chain branches (SCBs)
and long-chain branches (LCBs). HDPE (High Density Polyethylene) shows nearly
no SCB’s or LCB’s, LLDPE (Linear Low Density Polyethylene) has only short-chain
branches, while LDPE (Low Density Polyethylene) contains all sorts of branches.
HDPE as well as LLDPE can be produced in solution using catalysts at moderate
pressure (10-200 bar) and temperature (70-300°C) conditions. [2] The shift in
properties from hard and brittle HDPE to flexible LLDPE is achieved by adding α-
olefins as co-monomer during the LLDPE synthesis. Each time the co-monomer is
added to the backbone an SCB is formed, which results in a lower crystallinity,
density and melting temperature of the produced polymer. By the amount and length
of the short chain-branches as well as the molecular weight of the polymer the
macroscopic properties of the polymer can be adjusted very precisely.
The homo-polymerization of ethene using metallocenes and cocatalysts is a known
and very active system in polyolefin polymerization. Regarding co-polymerization
batch and semi-batch investigations were already performed. [3] In this work a new
fully continuous mini-plant was assembled with the possibility to feed up to three
different monomers at any desired ratio to the stirred autoclave reactor. As a special
aspect also hydrogen can be fed continuously to the reactor as a chain transfer agent
(CTA). By this, the possibility is given to produce co- and ter-polymers with different
lengths and amounts of short-chain branches at a desired molecular weight. Using
different analytical methods like IR, LS, DSC and NMR different samples of HDPE
and LLDPE were characterized and compared on the micro- and macromolecular
scale to investigate the impact of the short-chain branches and molecular weight
separately.
By this, characteristics of the product and the polymerization process not accessible
under batch or semi-batch conditions can be investigated and correlated now.

Acknowledgement: Borealis AG

References:
1
PlasticsEurope, Annual Review 2017-2018.
2
Soares, J.B.P.; McKenna T.F.L., Polyolefin Reaction Engineering 2012, Wiley-VCH.
3
Mehdiabadi, S; Soares, J.B.P.; Bilbao, D.; Brinen, J. Macromolecules 2003, 46,
1312-1324.
 Numerical Parameter Study on Single Pellet String Reactors
– a Reactor Concept for Heterogeneous Catalysis

Johanna Fernengel1,2, Leslie Bolton3, Olaf Hinrichsen1,2

1
Technical University of Munich, Department of Chemistry, Garching, Germany
2
Technical University of Munich, Catalysis Research Center, Garching, Germany
3
BP, Sunbury-on-Thames, UK

In order to develop new heterogeneous catalyst systems as well as to optimise

existing units there is the need for testing the performance of commercial catalysts at
industrial process conditions but preferably at smaller scale [1]. When maintaining
the size of the catalyst particles, conventional design criteria for catalytic testing
result in long packed bed reactors [2] with tube diameters much larger than the
catalyst pellet size [3]. These criteria lead to relatively large and costly reactors which
require substantial gas flow rates and may pose a significant level of hazard.
On the contrary, a reactor concept where pellets are packed into tubes of only slightly
larger diameter was named Single Pellet String Reactor (SPSR) by Scott et al. in
1974 [4] who already describe the similarity of the reactor’s flow behaviour to
conventional packed beds. But are SPSRs suitable for kinetic experiments and
industrial catalyst performance testing? Recent publications [5-7] demonstrate a
renewed interest in this reactor concept, including its use for catalyst testing.
Here, an attempt is made to systematically characterise SPSRs of spherical, non-
porous particles in cylindrical confining walls using computational fluid dynamics. A
parameter study on the reactor geometry is conducted whilst keeping the space time
constant, where residence time behaviour as well as the conversion of an isothermal,
irreversible hypothetical first order gas phase reaction at the pellet surface are
evaluated and compared to corresponding plug flow results. The applicability of
common design criteria for conventional fixed-bed reactors to SPSR is discussed
before deriving a design criterion for which SPSRs show a behaviour close to ideal
plug flow.
Overall bed conversion
on er ion re
results
ult of various
ariou
simulated SPSR
PSR scenarios
enarios are compared in
Fig. 1, where the ba
base
e case corresponds
orre pond to a
reactor with 20 catalytic
atalytic particles
parti le of
diameter and a cylinder-to-parti
particle-diameter
le ratio
of . A reactor with similar geometry,
except that the pellets
ellets are stacked along the
tube a
axis
i on top of each other
other, yields a slightly
larger conversion. Bed conversion
con er ion is
i also
al o
increased
in rea ed with the scale
ale of the rea
reactor,
tor, with
decreasing cylinder-to-parti
particle
le diameter ratio
and with an increasing number of particles.

Similar trends were obtained regarding the flow Figure 1:: Con
Conversion
ersion re
results
ult for SPSR
scenarios; dashed line indicating 5 %
behaviour
beha iour in the laminar regime using
u ing a non-
non deviation
de iation to ideal PFR beha
behaviour.
iour.
diffusive
diffu i e numerical
numeri al tracer
tra er to e
evaluate
aluate the corresponding
orre ponding RTDs.
RTD . The SPSRs
considered are in the range of the a
axial
ial dispersion
di per ion criterion
riterion by
b Gierman [[2] and
clearly violate the criterion for radial dispersion by Chu and Ng [3].
A novel de
design
ign criterion
riterion relating the de
deviation
iation to plug flow conversion
conver
on er ion to reactor
geometry, flow velocity
elocity and
diffusion
diffu ion coefficient
oeffi ient is
i proposed as
a
indicated in Fig. 2.
Conversion results deviating less
le
than 5 % from ideal plug flow can
an
readily be achieved with SPSRs,
making
ma ing them particularly
parti ularly well
suited
uited to te
testing
ting commercial
ommercial full-
size catalyst pellets.

Figure 2: Trend analysis showing

howing deviation
de iation
References to PFR conversion
on er ion based on number of
[1] H. Heinemann, Catal. Today 1994,
1994 22, 281-293. particles, cylinder-to-parti
particle
le diameter ratio
[2] H. Gierman, Appl. Catal. 1988,
1988 43, 277-286. and Péclet number .
[3] C.F. Chu, K.M. Ng, AIChE J. 1989,
1989 35, 148-158.
[4] D.S.
S. S
Scott,
ott, W. Lee, J.. Papa, Chem. Eng. S
Sci.i. 1974, 29, 2155-2167.
[5] R. Moonen, J. Alles, E.-J.J. Ras, C. Harvey,
Har e , J.. A. Moulijn,
Moulijn Chem. Eng. Technol. 2017, 40, 2025-
2034.
[6] A. Müller, J. Kanz, S. Haase, K. Becker, H.-M. Vorbrodt, Chem. Eng. Process. 2017, 113, 2-13.
[7] A. Klyushina, K. Pacultová, L. Obalová, React. Kinet., Mech. Catal. 2015, 115, 651-662.

Acknowledgements
The authors acknowledge the financial support from the twelve companies in the Eurokin consortium
(http://www.eurokin.org): Albemarle, Aramco Overseas, BP, DSM, Eni, Evonik Industries, IFP
Energies nouvelles, Johnson Matthey, Lhoist, Linde, Sabic and Shell. The authors are grateful to the
members of Eurokin for permission to present this work.
 Measurement of MNIC and DNIC in a free rising bubble

K. Haase, C.J. Kähler, Universität der Bundeswehr, München Germany;

In order to better understand how the mass transfer scales with the flow state the
transported species need to be visualized and quantified. To achieve the
visualization of the mass transfer through the bubble surface into the liquid, a
specially manufactured reaction system was used, provided by Prof. Klüfers from
LMU Munich in Germany. This utilizes a Fe²Cl/NO system to induce a reaction when
the oxygen gas diffuses out of the bubble. The carrier substance for the oxygen was
nitrogen, which is why nitrogen monoxide bubbles (NO-bubbles) were use. The
resulting chemical HNEt3[FeCl2NO] is called MNIC since one (M = mono) NO is
bound to the complex. This can then further react with a second NO molecule to the
so called DNIC (D = double). With these two species the transport and the selectivity
can be visualized. The two substances absorb differently at two distinct wavelengths.
MNIC has its absorption peak at around 590 nm while DNIC absorbs at 690 nm. In
this abstract the first experiments with this system will be presented and shown on a
simple free rising bubble.

Experimental setup
To measure simultaneously both products a two camera setup was chosen. Both
cameras were looking through a beams splitter to get the same field of view. To
separate the two products MNIC and DNIC on each camera a filter was mounted to
separate the two wavelengths (case a) ). The illumination was done with a white
backlight. Several individual bubbles were released in the channel and recorded. In
addition two other chemical systems were used that only produce either MNIC (case
b) ) or DNIC (case d) ).

Results
In the Fig. 1 an example recording is shown that depicts the image in both cameras.
a) b) c)

Fig. 1 Example recordings from reaction where a) both the MMIN + DNIC b) only
MNIC and c) only DNIC is produced. Top row shows the image from the camera that
had a 590 bandwidth filter mounted and the second row from the camera with a 695
long pass filter. In the third row a special comparison of the images is shown. The
outlines of both cameras are overlayed. In the fourth row the intensity ratios between
the two cameras are shown.

If both images are overlap no special difference can be seen between the two
images. Since most likely both products are produced simultaneously, both products
appear to be in the same areas. If one takes a look at the different intensity values
one can compare the ratio between MNIC and DNIC for the different cases b) and c).
As can be seen in the last row of Fig. 1 the intensity ratio in for the DNIC case is
different from the one in the MNIC case. With that the case in which both reactions
taking place can be studied further. With this experiment it was shown that the mass
transport through a bubbles interface can be visualized and further studied.
 Lagrangian Coherent Structures to Understand Dynamics in
Multiphase Flows with Chemical Reactions
A. v. Kameke, S. Rüttinger, S. Kastens, M. Hoffmann, M. Schlüter

Institute of Multiphase Flows,

Hamburg University of Technology, Hamburg
alexandra.vonkameke@tuhh.de

Reactive bubbly flows are essential for many chemical industrial applications e.g.
hydrogenation, oxidation and chlorination reactions in bubble column and loop
reactors. The efficiency of these reactors is mostly described by the yield and
selectivity of the products and side products, which can be measured and estimated
globally by various methods [1]. However to achieve more reliable estimations it has
to betaken into account that yield and selectivity depend sensitively on the coupling
of the fluidic and microscopic transport processes and the reaction kinetics [2]. To
study the dependency between local hydrodynamics, mass transfer and a chemical
reaction at a single gas bubble we use Taylor bubbles which are a helpful
simplification. This enables us to obtain quasi steady conditions with well-defined and
reproducible flow structures. It also allows us to adjust the hydrodynamics in the
bubble wake by changing the hydraulic diameter of the capillary and accordingly the
Reynolds number of the flow. Taylor bubbles are elongated gas bubbles in channels,
where the gas volume is forced into a bullet shape by the channel geometry and the
continuous liquid which wets the glass wall. The rising velocity of Taylor bubbles is
independent of the bubble volume and can be predicted by the dimensionless Eötvös
number of the fluidic system [3]. In order to analyze the hydrodynamics in our reactor
we calculate the Lagrangian coherent structures (LCS) and the finite-time Lyapunov
exponent fields (FTLE-fields) from the measured two-dimensional velocity and
concentration fields (PIV-LIF). LCS are defined to be the most repelling, attracting or
shearing material lines of the tracer field in finite time [4]. Here we focus on the so
called hyperbolic LCS which correspond to the most attracting and repelling material
lines. The LCS give us new insights into the flow topology for the finite time .
Imagine an artificial tracer released at some point in the fluid inside or outside the red
repelling LCS in Fig. 1. After a time the tracers released inside the red LCS will still
largely remain in the vortical structures close to the bubble bottom while tracers
released below the red LCS will have been flushed away rapidly. This affects the
local residence times of the chemical molecules dramatically. Especially the
dissolved gas is thus highly dependent on the local hydrodynamics and thus prone to
chemical reactions with longer timescales. This fact can have undesired effects on
overall yield and selectivity of the targeted reaction. We find that the local residence
times vary strongly for different Reynolds numbers of the flow. We show that these
local effects of mixing intensity and residence times should be taken into account for
the design and operation of bubbly flows in multiphase reactors. These local effects
on residence behavior analyzed by LCS might also play a role in other multiphase
and chemical reactors where wake flow is the main cause for mixing.

Fig. 1. LCS calculated from the velocity fields

derived from Particle Image Velocimetry (PIV)
data for a pipe channel diameter of D = 7mm. The
mean free velocity (sufficiently ahead of the
bubble) is 22 mm/s. The red lines denote the
repelling- and the blue lines the attracting LCS.
On the right side below the bubble a combination
of the forward and the backward FTLE-field is
shown in the background. The liquid is an
aqueous solution of fluorescein sodium salt which
shows a decrease in fluorescence intensity for
higher amounts of dissolved carbon dioxide gas
released from the bubble. This decrease is
visualized using Laser Induced Fluorescence
(LIF) [1].

[1] S. Kastens, J. Timmermann, F. Strassl, R. F. Rampmaier, A. Hoffmann, S.

Herres-Pawlis and M. Schlüter, Chem. Eng. Technol., 2017, 40, 14941501.
DOI:10.1002/ceat.201700047.
[2] J. Baldyga, J. R. Bourne: Turbulent Mixing and Chemical Reactions, John Wiley
and Sons Ltd., Chichester, UK. 1999.
[3] K. Hayashi, R. Kurimoto, A. Tomiyama, Int. J. Multiphase Flow, 2011, 37, 241-
251, DOI:10.1016/j.ijmultiphaseflow.2010.10.008.
[4] K. Onu and F. Huhn and G. Haller, J. Comput. Sci., 7 (2015), pp. 26-36,
DOI:10.1016/j.jocs.2014.12.002.
 Magnetic Resonance Imaging: Spatially resolved experimental
analyses of mass transfer on Taylor bubbles by means of NMR

Philip Kemper1, Wolfgang Dreher2, Ekkehard Küstermann2, Jorg Thöming1

1
University of Bremen, Faculty of Production Engineering, Chemical Process
Engineering, Bremen, Germany
2
University of Bremen, Faculty of Chemistry, in-vivo MR group, Bremen, Germany

Gas-Liquid reactions play an important role in industrial processes. They are used in
a wide area of applications ranging from large-scale chemical reactions involving
bubble columns to small-scale synthesis of fine chemicals based on single bubble
reactions. A great deal of interest (and focus of the DFG Priority Program SPP 1740
„Reactive Bubbly Flows“) is to understand the chemical processes inside the tail of
the bubble because of its huge influence on the selectivity and yield of chemical
reactions.

Magnetic Resonance Tomography (MRI) continuously gains popularity in the field of

engineering. Various experiments have been carried over the last decades,
investigating catalytic gas phase reactions, flow velocities inside porous media and
catalytic beds as well as droplet dynamics.

In this study, MRI is used as a non-invasive tool to spatially resolve the processes
inside the tail of the bubbles. In order to obtain highly resolved spatial data of the
area behind the bubble we use a Bruker BioSpec 70/20 USR 7T tomograph with a
horizontal bore (Figure 1 (a)). Therefore a NMR compatible setup has been
constructed which allows the continuous observation of a single bubble under flow
conditions (Figure 1 (b)). A buoyancy driven Taylor bubble rising inside a glass
capillary is held in place by means of a counter flow. Thus, longer acquisition times of
different NMR sequences (usually in the range of 0,1 – 10 s) can be achieved.

First measurements with phantoms containing water were carried out to see how the
whole setup, including the self-made coil, performs inside the tomograph (Figure 1
(c)). Rapid prototyping technologies such as 3d printing were then used to further
improve the setup.

Our next step is to perform first measurements under real flow conditions. Therefore,
a NMR compatible reaction system is provided (cooperation SPP 1740, RWTH
Aachen). It consists of a Cu (I) complex, dissolved in acetonitrile which reacts with
oxygen to a Cu (II) complex. As this reaction takes place, the NMR can detect a
difference in relaxation times between the diamagnetic Cu (I) and the paramagnetic
Cu (II). Thus, making it possible to determine the concentration of both copper
complexes inside the tail of the bubble it becomes possible to draw conclusions on
how the hydrodynamics influence selectivity and yield.
NMR-based methods have the potential to be utilized for operando studies of
transport phenomena within the tail of the bubble to obtain concentration maps
during reactions.
Figure 1: NMR tomographraph Bruker BioSpec
BioSpe 70/20 USR (a (a) for performing mea
measurement
urements,, in whi
which h the NMR
compatible setup (b)) with a gla
glasss capillar
capillary
apillar for bubble creation,
reation, surrounded
urrounded bby the mea
measurement
urement coil,
oil is inserted.
Firstt measurements
Fir mea urement were performed u using
ing water filled phantoms
phan of square capillaries (c).
 Experimentelle Untersuchung dreidimensionaler disperser
Zweiphasenströmungen
Martin Neumann1, Uwe Hampel1,2
1
Professur für Bildgebende Messverfahren für die Energie- und Verfahrenstechnik,
Technische Universität Dresden, 01062 Dresden, Deutschland.
2
Institut für Fluiddynamik, Helmholtz-Zentrum Dresden - Rossendorf,
Bautzner Landstraße 400, 01328 Dresden, Deutschland.

Kurzfassung
In vielen industriellen Prozessen und Apparaten treten Mehrphasenströmungen auf.
Dies sind häufig Flüssigkeits-Gas-Strömungen, beispielsweise in der
Kraftwerkstechnik, in Wärmetauschern, chemischen Reaktoren und Trennapparaten
oder in Ölfördersystemen. Ein großes Ziel ist die Berechnung solcher Strömungen
mittels computergestützter Simulationswerkzeuge (CFD-Codes) zur Unterstützung
der Auslegung, zur Optimierung, aber auch zur Sicherheitsbewertung. Die komplexe
Physik von Zweiphasenströmungen erschwert dieses Vorhaben im Vergleich zu
einphasigen Strömungen erheblich. Grund dafür ist die Komplexität der
Transportprozesse über stark verformbare und sich verändernde
Phasengrenzflächen in mehreren Zeit- und Längenskalen. Zudem werden durch
anlagentechnische Komponenten, wie beispielsweise Krümmer, Ventile, T-Stücke
oder querschnittsverändernde Einbauten, ausgeprägte dreidimensionale
Strömungsfelder erzeugt, welche von aktuellen CFD-Codes nur sehr stark
eingeschränkt berechnet werden können.
Der Beitrag beschäftigt sich mit der experimentellen Untersuchung von generischen
dreidimensionalen Zweiphasenströmungen. Mit Hilfe neuartiger experimenteller
Methoden wurde eine Datenbasis für die nachhaltige Validierung und
Weiterentwicklung von CFD-Codes, speziell für dreidimensionale Strömungseffekte,
generiert.
Gegenstand der Untersuchungen war die vertikal aufwärtsgerichtete Blasenströmung
in einer DN50 Rohrleitung mit einer Länge von 5000 mm. Zwei verschiedene
Strömungshindernisse erzeugen dreidimensionale Strömungsphänomene für ein
breites Spektrum von möglichen Lehrrohrströmungsgeschwindigkeiten. Für die
Studien wurden, neben konventioneller Messtechnik für die Erfassung von
Massenströmen, Drücken und Temperaturen, speziell entwickelte Messsysteme des
Helmholtz-Zentrum Dresden – Rossendorf eingesetzt. Dabei handelt es sich zum
einen um das ultraschnelle Röntgentomographiesystem ROFEX zur Bestimmung der
Gasphasenhydrodynamik und zum anderen um neuartige thermische Anemometer
Sonden zur Bestimmung der Flüssigphasengeschwindigkeit. Die Kombination dieser
Messverfahren ermöglicht die simultane Bestimmung der zeitlich und räumlich
hochaufgelösten Gasphasendynamik, sowie lokalen zeitlich hochaufgelösten
Flüssigphasengeschwindigkeiten.
 Mass transfer at rising single bubbles in reacting iron ligand
systems

David
Da id Merker,
Mer er Lutz Böhm and Matthias Kraume

Technische
Te hni he Universität
Uni er ität Berlin, Chair of Chemi
Chemical
al and Pro
Process
e Engineering, Berlin,
Germany

Gas-liquid
liquid rea
reactions
tion still
till pose a major challenge
hallenge in the calculation
al ulation and de
design
ign of
suitable
uitable apparatu
apparatus.. For thi
this rea
reason,
on, the DFG Priority
Priorit Program 1740 "Reactive
" Bubbly
Flows" focuses on the in
inve
investigation
e tigation of ga
gas/liquid
/liquid rea
reactions
tion on different scales.
ale . It
promotes the close
promote lo e cooperation of chemists,
hemi t , simulation
imulation groups and process
pro e
engineers.. Thi
engineer This subproject
ubprojectt deal
ubproje deals with single
ingle bubble
bubbles to reduce
redu e the complexity
omple it and
enable experiments with high spatial and temporal resolution.

Experimental setup
The setup built in thi
this project can be seen in Figure 1. It consists
on i ts of a 2 m long glass
tube, in whi
which
h a single
ingle bubble can
an ri
rise
e freely through a stagnant fluid. The
temperature iis controlled
ontrolled with an acrylic glass jacket that also provides
pro ide a b
better
optical access. The bubble
ubble is tracked with two high-speed cameras,
ameras, which
whi h are moved
along with the ri
rising
ing bubble. It iis po
possible
ible to perform e
experiments
periments under a protective
prote ti e
atmosphere.

Figure 1:: E
Experimental
perimental setup:
etup: schemati
schematic
hemati sketch
et h (left), single
ingle bubble
bubbles ri
rise
e in a temperature
temperature-controlled
glass tube (h = 2m) ob
observed
er ed with high-speed
high peed cameras;
amera ; Cross
Cro section
e tion of the system (right)
Apart from the solution
olution of carbon dioxide (CO2) in water/NaOHaq, experiments
e periment with
different iron complexes rea
reacting
ting with NO a
as the ga
gas pha
phase
e were carried
arried out
out. The
choice of ligand influences the reaction
rea tion rate of the system.
tem.
Figure 2 shows a nitric oxide
o ide (NO) bubble in an iron sulfate edta solution
olution
(FeII(edta)aq). The produ
productt iis colored
olored and can
an be detected
dete ted in the wake
wa e of the bubble.
The two image
images were taken at the same
ame time by the two cameras
ameras with an offset of
90°. The
he size,
i e, shape
hape and 3D rising path can be resolved with a high temporal and
spatial resolution.

II
Figure 2: nitric oxide (NO) bubble in Fe (edta)aq with a concentration
on entration of 75 mmol/l, view from the two
cameras at the same time

It iis po
possible
ible to mea
measure
ure the volume
olume change
hange and thus
thu evaluate the mass
ma tran
transfer of a
bubble depending on the contact
onta t time. Due to the detailed measurements,
mea urement ,
enhancement fa
factors
tor can
an be mea
measured
ured depending on the educt
edu t concentrat
concentration.
on entrat

Acknowledgements

The author
authors gratefull
gratefully a
acknowledge
nowledge the finan
financial
ial support
upport provided
pro ided by
b the German
Research
Re ear h Foundation within the Priorit
Priority Program ‘‘Rea
‘‘Reactive
ti e Bubbly
Bubbl Flows’’,
Flow ’’, SPP
1740.
Does the wake structure in bubbly flows affect yield and selectivity
of a competitive consecutive reaction? – A Taylor-Bubble study
S. Rüttinger, S. Kastens, M. Hoffmann, A. v. Kameke, M. Schlüter

Institute of Multiphase Flows,

Hamburg University of Technology, Hamburg
sophie.ruettinger@tuhh.de

Fast gas-liquid reactions are often performed in bubbly flows to provide an intensive
mixing with high heat and mass transfer performance. In such flows, the gaseous
reactants have to be transferred across the interface, through the hydrodynamic
boundary layer into the liquid bulk phase that is dominated by bubble wakes and
other turbulent structures. The pathway of reactants and its residence time within the
boundary layer and the bubble wake is strongly dominated by the bubble shape and
velocity. Common theories like the penetration theory or the two-layer theory are
underlying strong assumptions and their application to reactive bubbly flows is
therefore questionable.
Within the DFG priority program 1740 “Reactive Bubbly Flows” new chemical
systems have been developed to study the influence of such transport phenomena
on yield and selectivity of fast competitive consecutive reactions in detail.
Furthermore with a new experimental set up it is possible, to adjust the timescales of
mass transfer and mixing in a well-defined way. Background illumination with a
sequentially pulsed laser-LED panel and high-speed imaging allows the detection of
the concentration distribution of products and byproducts independently (UV-VIS
Imaging). The Taylor-Bubble setup has been designed with a well-defined gas
atmosphere and organic solvents to be used in a fume hood. Therefore an
application to industrial systems should be possible.
In this presentation the latest results of the product and byproduct distribution of a
competitive consecutive reaction in a Taylor-Bubble flow under different flow
conditions will be shown. Furthermore a new mathematical method to acknowledge
the flow trajectories and local residence times of reactants and products will be
presented. With the new methods, a deep insight into the interplay of mass transfer,
mixing and reaction becomes possible and should help in future to design more
efficient gas-liquid processes with higher yield and selectivity.
Figure 1: Oxygen Taylor-Bubble reacting in a Cu(btmgp)I – acetonitrile solution

Kastens, S.; Timmermann, J.; Strassl, F.; Rampmaier, R. F.; Hoffmann, A.; Herres-Pawlis, S.; Schlüter, M.: Test
system for the investigation of reactive Taylor bubbles. Chem. Eng. Tech., 2017, 40(8), pp. 1494-1501, DOI:
10.1002/ceat.201700047.
Paul, M.; Strassl, F.; Hoffmann, A.; Hoffmann, M.; Schlüter, M.; Herres-Pawlis, S.: Reaction systems for bubbly
flows, European Journal of Inorganic Chemistry, 2018, issue 20-21, pp. 2101-2124, DOI: 10.1002/ejic.201800146.
 Untersuchungen der hydromechanischen Beanspruchung von
Partikeln in gerührten Reaktoren
C. Bliatsiou, R. Panckow, P. Waldherr, L. Böhm, M. Kraume
Fachgebiet Verfahrenstechnik, Technische Universität Berlin, Deutschland
FH 6-1, Fraunhoferstraße 33-36, 10587 Berlin, Deutschland

Die hydrodynamische Beanspruchung von Partikeln in Reaktoren ist für viele

verfahrenstechnische Prozesse von entscheidender Bedeutung. Die
Partikelzerströrung kann entweder erwünscht, z.B. in Dispergiervorgängen von
(Flüssig/flüssig-) oder (Gas/flüssig-) Zweiphasensystemen, oder nachteilig, z.B. in
Kristallisations- oder Bio-Prozessen, sein. Im Rahmen des DFG
Schwerpunktprogramms ‚SPP1934 DiSPBiotech‘ wird die Untersuchung der
hydromechanischen Beanspruchung auf Bioagglomerate betrachtet. Die
Quantifizierung der hydromechanischen Beanspruchung ist durch die Nutzung von
zwei-phasigen Flüssig/flüssig- und Fest/flüssig-Stoffsystemen, vereinfacht.
Als Modellsysteme wurden in dieser Arbeit sowohl Dispersionen von Silikonöltropfen
in newtonchen (H2O) und nicht-newtonschen (Xanthan Lsg.) kontinuierlichen Phasen
als auch eine Suspension von Ton/Polymer-Flocken eingesetzt.
Die Partikelbeanspruchung wurde durch Messungen der Tropfenzerkleinerung in
einem Rührkessel im Labormaßstab quantifiziert. 15 unterschiedliche Rührorgane
wurden verwendet. Neben den typisch benutzten Rührer (Scheiben-,
Schrägblattrührer, Propeller) wurden neue Rührergeometrien getestet (Abbildung 1).
Der von jedem Rührer verursachte Partikelbruch wurde inline im Rührreaktor mit
einer Endoskopmesstechnik gemessen. Die Interpretation der Ergebnisse erfolgt
mittels fluiddynamsichen Untersuchungen mit Particle Image Velocimetry.

Abb. 1. Neuartige Rührorgane, die im Rahmen des
SPP 1934 DiSPBiotech untersucht wurden (Patent
pending EvoLogics GmbH).
Danksagung
Die Autoren danken der Deutschen
Forschungsgemeinschaft für die finanzielle
Unterstützung im Rahmen des SPP 1934
DiSPBiotech und der EvoLogics GmbH für die
Entwicklung der Rührorgane.
Poster Abstracts
Multiphase Flows
 Hybrid field-flow fractionation using acoustic resonance in an
electrostatic precipitator

Krischan Sandmann1, Udo Fritsching1,2

1
Leibniz-Institute for Materials Engineering - IWT, Bremen, Germany
2
Particles and Process Engineering, University of Bremen, Germany

The selective classification of particles on hand of different properties and property

functions (as for instance shape, size, surface roughness, …) is a core task in
particles and process engineering. Minor differences in the property distributions
require high standards with respect to the separation processes used. Applying Multi-
Field-Flow Fractionation (M-FFF) is one approach to overcome this issue.

The Multi-FFF separation approach is based on the idea that particles, guided and
manipulated according to their multidimensional distributed properties, can be
separated directly from the aerosol into different fractions. Therefore, several
potential fields can be applied. In this thesis the focus is set on the particle behavior
in a combination of an ultrasonic resonant acoustic field (AF) and an electrostatic
field (EF).

In a first step, a proof of principle is performed using the analytical description of a

nonideal resonant ultrasonic wave and numerically solve for the induced particle
trajectories for different sized particles.

The results illustrate the size sensitive fractionation of the particles in the ultrasonic
resonant acoustic field. The smaller particles accumulate at sound velocity nodes the
lager particles move to sound velocity lobes. Previous investigations assuming model
and boundary conditions as: 1-dimensional flow field, spherical particles, Schiller &
Naumann drag, homogenous density etc. have been extended to a more complex
structure using openFoam.

On the simulation side, the key functions are implemented in individual stages. First
the description of a standing sound wave in the simulation environment, then the
integration of particle tracking and thereafter the superposition of an electric field.
The resulting 3-dimensional, compressible, Euler-Lagrangian setup is then compared
and benchmarked by controlled experiments in a M-FFF test rig.
The project may ultimately lead to the development of a highly specific and
continuously operated separation process capable of separating particle collectives
according to multi-dimensionally distributed target values. For example, due to size,
shape, density and particle distribution – depending on field settings – in
agglomerates. The convertibility into the industrial scale should also be considered.

The financial support of the German Research Foundation (DFG) within the priority
program SPP 2045 "MehrDimPart" is gratefully acknowledged.
 Investigations on selectivity of gas-liquid reactions in capillaries
J. Grühn, N. Kockmann
Laboratory of Equipment Design, TU Dortmund University, Germany

Gas-liquid reactions are of great importance in the chemical industry and subject of
current research since they are often limited by mass transfer or show low selectivity
[1]. Krieger et al. investigated the consecutive oxidation of leuco-indigo carmine with
a colorimetric technique to visualize local gas-liquid mass transfer in capillary plug
flow [2]. The two changes of color during this oxidation are advantageous for
investigations on selectivity. Furthermore, studies on flow behavior have shown three
relevant flow regimes depending on different operating conditions [2]. Since the
selectivity in bio-catalytic reaction systems is an important field in research as well,
investigations of bio-catalytic parallel reactions were performed. Different suitable
reaction systems, including reaction systems from the DFG-SPP1740 “Reactive
Bubbly Flows”, were tested and an optical measuring method was established. The
experiments were performed in a flow regime, which is dominated by Taylor vortices
of two-phase flow in capillaries. According to the approach of Krieger et al. the
experimental setup consists of a straight capillary with 1.6 mm inner diameter.
Building on this, investigations on gas-liquid reactions in coiled capillaries and coiled
flow inverters (CFI) follow. In comparing the experimental results of the consecutive
oxidation with the bio-catalytic parallel reaction and other reaction systems, a deeper
understanding of selectivity of gas-liquid reactions is developed.

[1] P.V. Danckwerts, Gas-liquid reactions, McGraw-Hill, New York, 1970

[2] W. Krieger, J. Lamsfuß, W. Zhang, N. Kockmann, Chem. Eng. Technol. 2017,

40 (11), 2134-2143.
 Modellierung und Simulation des Stressverweilzeitverhaltens an
flüssig/flüssig Phasengrenzen in mikroporösen Strukturen
Tobias Wollborn1, Laura Luhede1, Udo Fritsching1,2
1
Leibniz-Institut für Werkstofforientierte Technologien - IWT, Bremen, Deutschland;
2
Particles and Process Engineering, Universität Bremen, Deutschland

Die Erzeugung und Formulierung von Emulsionen erfolgt z.B. in der

Lebensmitteltechnologie oder der pharmazeutischen Industrie. Qualitativ hochwertige
Emulsionen weisen eine feine und eng verteilte Tropfengrößenverteilung auf. Der
Membranemulgierprozess besitzt hierbei den Vorteil, die Tropfengröße gezielt anhand
der Porengeometrie der Membran einstellen zu können. Gleichzeitig handelt es sich um
einen beanspruchungsarmen Prozess, sodass schersensitive Medien (z.B. biologische
Systeme) Anwendung finden können. Während das Emulgierverhalten hinsichtlich der
relevanten Prozessparameter bereits hinreichend untersucht wurde, sind die
Mechanismen der Tropfendeformation und des Tropfenaufbruchs innerhalb der
verzweigten porösen Struktur noch unzureichend geklärt. Die Beanspruchungen (Scher-
und Dehnstress) an der Grenzfläche sind direkt von der Porengeometrie abhängig und
bestimmen das Deformations- und Aufbruchverhalten. Zudem können Scher- und
Dehneffekte an der Grenzfläche das Verhalten adsorbierter Strukturen (z.B.
Emulgatoren) beeinflussen und Schädigungen herbeiführen, beziehungsweise die
Adsorptions-/Desorptionsvorgänge an der Phasengrenze während des Prozesses
beeinflussen. Dies kann die Qualität des Endprodukts beeinflussen.
Die Bestimmung von Tropfendeformation und -aufbruch und die dabei wirkenden
Verteilungen von Scher- und Dehnstress an der Phasengrenzfläche findet auf Basis
des OpenFOAM interFoam Solvers statt. Das Stressverweilzeitverhalten an der
Tropfengrenzfläche wird beschrieben und lokale sowie integrale Aussagen über die
Beanspruchung getroffen. Für grundlegende Aussagen über die Beziehung von
Grenzflächenstress zur Tropfendeformation wurden zunächst idealisierte
Porenstrukturen (Verjüngung, Blende) betrachtet. Anschließend wurde der
Untersuchungsrahmen auf reale Porenstrukturen erweitert. Dabei wurden
Parametervariationen der Kapillarzahl, des Tropfendurchmessers und des Kontakt-
winkels durchgeführt.
Dieses Projekt wird durch das DFG SPP 1934 „DiSPBiotech“ am Leibniz-IWT Bremen
und die MIMENIMA Graduate School an der Universität Bremen gefördert.
 Influence of the micro structure onto the multiphase flow of
hydrocarbons in horizontal tubes
Simon Fries, Andrea Luke
University of Kassel, Technical Thermodynamics, Kassel, Germany

Gas-liquid flows of saturated fluids are crucial in many technical applications.

Although many experimental and numerical investigations are conducted in the
literature, the physical phenomena of multiphase flow of these fluids is still not
entirely understood. Therefore many components in process engineering cannot be
designed precisely. Recent investigations do not consider the influence of the wall
surface microstructure, although the significance of the influence onto single phase
transport phenomena is already known.

The institute of Technical Thermodynamics of the University of Kassel operates a

newly designed test facility, where the transport processes of single and multiphase
flow of saturated hydrocarbons are investigated along the vapor pressure curve. At
first, the influence of the wall surface structure on single phase transport processes is
quantified. In addition, gas-liquid flows of the same hydrocarbons are investigated by
changing the saturation pressure, the mass flow rate and the vapor quality. Drawn
copper as well as drawn mild steel are used as tubes materials. The surface
structures of both tubes vary, although manufactured by the same method.

The mean surface roughness of the drawn steel tube is six times as high as the
roughness of the copper tube. As presumed, the pressure drop of single phase flow
increases up to 30% in the mild steel tube compared to the copper tube. However, in
multiphase flow no increase in pressure loss with the same experimental setup is
observed. This phenomenon can be explained by the occurring boundary layer in the
respective flow pattern in tubes.
 Centrifugal
entrifugal pumps as extractors
P. Schmitt and H.-J. Bart
TU Kai
Kaiserslautern,
er lautern, Chair of Separation S
Science
ien e and Technolog
Technology
67663 Kaiserslautern
Radial centrifugal
entrifugal pumps are the working horse in industry and can be found in
numerous installations. The use
u e in liquid two-phase flows a
as mixing unit is
i rare and
besides
be ide the primary
primar pumping effe
effect,
t additional di
dispersing
per ing and coalescing
oalescing phenomena
of the droplets can
n be observed [1].
A te
testt ben
bench
h was constructed
con tru ted in order to analyze the dispersing
di per ing and
coalescing effects
t of centrifugal
entrifugal pump
pumps for different geometrie
geometries and different modes
mode
of operation. The heart of the system
tem iis a tran
transparent
parent centrifugal
entrifugal pump that allows
allow
optical analysis within the impeller
impelle region and the pump housing.. Parameters
Parameter such
u haas
the pump speed, flow
low rate, pha
phase
e ratio of an organi
organic to an aqueous
aqueou pha
phase
e can
an be
varied
aried in addition to geometri
geometric parameter
parameters of the test pump.. Pump performance
performan e data
can be determined during operation.
Results
Re ult on the di
dispersion
disper
per ion effe
effectt of centrifugal
entrifugal pumps
pump using
u ing a standard
tandard
chemical pump for various paraffin oil-water systems are shown.
hown. High
High-speed images
of the impeller region during operation
operation enable the anal
analysis
i of drop breakage
brea age and
coalescence depending on the mode of operation. Droplet size
ize distributions
di tribution vary
radially in the impeller region.
region. On thi
this ba
basis,
i , flow regime
regimes are to be evaluated
e aluated whi
which
h
have a predominant coales
oalescing
ing or di
dispersing
per ing effe
effect.
t. The performance
performan e data and
dispersion
di per ion characteristics
hara teri tics in the impeller region are u
used
ed to validate
alidate CFD simulations
coupled with droplet population balances
balan e in order to re
resolve
ol e local
lo al phenomena and to
provide
pro ide a ba
basis
i for flow optimization.
optimi ation.

Fig 1: Detailed view:: tran

transparent
parent centrifugal pump (left: camera,.
amera,. middle pump, right: white LED screen)
reen)

[1] M. Weber, Chara

Characterization
terization of Liquid-Liquid
Liquid Liquid Mi
Mixing
ing Intensities
Inten itie in Static Mixer
Mixers,, Turbulent Pipe
Flow and Centrifugal Pumps, in: Proc.
Pro . of ISEC 2014, pp. 577–582.
577
 Cutting of rising bubbles by a wire without contact

M. Börnhorst1, T. Homan2, P. Rohlfs1, N. Deen2, O. Deutschmann1,3, M. Wörner3

1
Multiphase and Reactive Flows Group, Department of Mechanical Engineering,
Eindhoven University of Technology, Eindhoven, Netherlands
2
Institute for Chemical Technology and Polymer Chemistry, Karlsruhe Institute of
Technology, Karlsruhe, Germany
3
Institute of Catalysis Research and Technology, Karlsruhe Institute of Technology,
Karlsruhe, Germany

Bubble columns are widely used multiphase reactors for industrial applications.
Conversion of bubble columns mainly relies on heat and mass transfer between the
phases, which are dependent on the effective transfer area and residence time.
Often structured packings or wire-meshes are used as reactor internals to reduce
bubble size by cutting the bubbles. This enhances efficiency by both increasing the
interfacial area and reducing the bubble rise velocity, extending contact time. The
wire mesh may further serve as support for a catalytic coating [1], which may modify
the wettability. Previous studies investigated the interaction of a single bubble with a
solid wire for a wide range of parameters like bubble size and velocity [2, 3] but did
not address the influence of wire wettability. Recent numerical simulations indicate
that the latter may affect the bubble-wire interaction especially under hydrophobic
conditions [4]. However, these simulations have not been validated by experiments
so far and the exact physical mechanisms governing the bubble-wire interaction are
still largely unknown.

In this work, the effect of wettability on the bubble cutting process is investigated by
bubble cutting experiments using cylindrical wires made of different material (glass
with and without hydrophobic coating, stainless steel, teflon). An air bubble is
generated at the bottom of a container filled with a high viscosity liquid (90 w%
glycerol-water mixture). Besides the wire wettability (contact angle 40 – 150°) and
wire diameter (3 – 5 mm), the bubble size (50 – 1000 µl) and thus the bubble rise
velocity is varied. The rising bubble and its interaction with the horizontal
wire/cylinder is captured by high-speed imaging using backlight illumination.
Subsequent image processing delivers the sizes of mother and daughter bubbles
and potential satellite bubbles are tracked in time. Additional information such as the
thickness of the liquid film and the length of the gas thread connecting the two
daughter bubbles is obtained.

Results show that for all experiments in the studied viscosity regime there is no
actual contact between bubble and wire. A uniform liquid film forms during bubble-
wire interaction as shown in Figure 1. In contrast to numerical predictions [4],
wettability does not influence the bubble cutting process in the measured parameter
range. The thickness of the evolving liquid film increases with bubble volume and is
largely independent from wire diameter and material. Only the behavior of a central
satellite bubble which may form during the cutting of very large bubbles via the
breakup of the thinning gas thread is observed to depend on the wire wettability.

Figure 1: The mother bubble is cut by the horizontal wire into two equally
sized daughter bubbles. A liquid layer between wire and bubble inhibits
the influence of wire material properties on bubble-wire interaction.

References
[1] Höller, V., Radevik, K., Kiwi-Minsker, L., Renken, A. Bubble Columns Staged with
Structured Fibrous Catalytic Layers:  Residence Time Distribution and Mass
Transfer. Ind. Eng. Chem. Res., Vol. 40, pp. 1575 – 11579 (2001)
[2] Baltussen, M.W., Segers, Q.I.E., Kuipers, J.A.M., Deen, N.G. Cutting bubbles
with a single wire. Chem. Eng. Sci., Vol. 157, pp. 138 – 146 (2017)
[3] Segers, Q.I.E., Cutting Bubbles using Wire-Mesh Structures - Direct Numerical
Simulations, PhD thesis, Eindhoven University of Technology, 2015
[4] Cai, X., Wörner, M., Marschall, H., Deutschmann, O. Numerical study on the
wettability dependent interaction of a rising bubble with a periodic open cellular
structure. Catalysis Today, Vol. 273, pp. 151 – 160 (2016)
 Measurement of bubble size
si e in a vertical pipe using Wire-Mesh
Wire
Sensor and optical probe

C. Theßeling, P. Biessey,
Bie e , M. Grünewald, Ruhr Uni
Universität
er ität Bochum,
Bo hum,
Bochum/Germany
In the chemical
hemi al industry
indu tr
try bubble columns
olumn are widely
widel used
u ed as
a multipha
multiphase
e contactors
onta tor
and rea
reactors
tor for the operation of ga
gas-liquid
liquid rea
reactions
tion such
u h as oxidations and
hydrogenations. Despite
pite their simple
imple construction
on tru tion complex
omple fluid dynami
dynamic phenomena
occur
o ur in bubble columns
olumns ma
olumn making
ing an a
accurate
urate prediction
predi tion of h
hydrodynamics
hydrod
drod nami or
extrapolation from technical
al to industrial
indu trial scale
ale still
till difficult.
diffi ult. Up to now, the design
de ign of
bubble columns
olumn still
till relies
relie on empiri
empirical
al rule
rules and correlations
orrelation which
whi h are often ba
based
ed
on mea
measurements
urement of integral values
alue such
u haas the o
overall
erall ga
gas hold-up.
hold up.

The de
development
elopment and improvement of m
measurement
ea urement techniques
te hniques in the la
lastt de
decades,
ade
however, allow for a more detailed observation
ob er ation of hydrodynamic
h drod namic parameters
parameter such
u h as
a
local
lo al phase
pha e distribution
di tribution or bubble size.
i e. In the in
investigation
e tigation of bubble columns
olumn a
precise
pre i e acquisition
a qui ition of the pre
prevalent
alent bubble size
i e is
i eessential
ential since
in
ince
e the bubble size
i e
determines the interfacial
al area of a specific
pe ifi reaction
rea tion and therefore has
ha a strong
trong
influence on the performance
mance of bubble column
olumn rea
reactors.
tor

In this work, the signal and accuracy

a ura of the wire-mesh
sensor technology [1] for the measurement
mea urement of single bubble
sizes is investigated. Based on the measurement
mea urement of the
electrical conductivity, wire mesh
me h sensors
en or provide
pro ide cross-
ro
sectional images of the local
lo al phase distribution. Two
perpendicular
perpendi ular plane
planes of electrode wires
wire with a small
mall axial
a ial
distance to each other build a matrix
matri of crossing
ro ing points,
point , in Figure 1: Rising
Ri ing air bubble
(db = 2.7 mm) hitting an
which the conductivity of the fluid is measured. Further electrode wire of the wire-
wire
mesh sensor
analysis
anal i of the image data results
re ult in the measurement
mea urement of
individual bubble size.

The e
experimental
perimental setup
etup con
consists
on i t of a cylindrical
lindri al gla
glass column
olumn (inner diameter
di = 0.15 m) with deionized water as
a the liquid pha
phase
e an
and air as the gas phase. The
applied wire-mesh
me h sensor
ensor has
ha a lateral distance of 4.8 mm and an axial
a ial di
distance
tan e of
3 mm between the wires.. Single bubbles
bubble with defined gas volume
lume are generated via
ia
syringes, resulting in bubble sizes
i e ranging from 2 mm to 12 mm. In addition to the
wire-mesh sensor, the passage of the rising bubble through the electrode grid is
recorded with a camera system. This allows for a determination of the local bubble
position within the mesh grid during the passage.

Our contribution will focus on the influencing parameters that are induced by single
rising bubbles to a wire mesh sensor. Furthermore, the comparison between
measured bubble size by wire mesh sensor and reference bubble size will be
presented. Based on this discussion, the applicability of wire mesh sensors for the
characterization of gas liquid flow behavior will be evaluated.

[1] H. – M. Prasser et al., Flow Measurement and Instrumentation, 1998, 9, 111-119

The motion of non-spherical particles in a pseudo-2D fluidized bed:
PTV measurement and CFD-DEM simulation

Zhaochen Jiang, Institute of Particle Technology (LFG), FAU Erlangen-Nuremberg,

Erlangen, Germany

Andreas Bück, Institute of Particle Technology (LFG), FAU Erlangen-Nuremberg,

Erlangen, Germany

Evangelos Tsotsas, Thermal Process Engineering, Otto-von-Guericke University

Magdeburg, Magdeburg, Germany

Non-spherical particles are commonly encountered in industrial applications, for

instance, tablet coating in Wurster fluidized bed. Knowledge about the influence of
particle shape on particle motion is essential for process design and optimization. In
this work, a new particle tracking velocimetry method was developed to measure
translational and rotational motion of non-spherical (tablet) particles in a pseudo-2D
fluidized bed. The watershed transform was used to separate slight overlaps of
particles. Single particle calibration including both, area and aspect ratio, was
conducted to identify the orientation based on digital image analysis. The novel
methodology was verified by synthetic images generated from corresponding CFD-
DEM simulations using superquadric particles, as shown in Figure 1. In addition,
simulation results were compared with measurement data.

Figure 1: Particle tracking velocimetry (PTV) for tablets

 Continuous Flow Production of the Bio Fuel Butyltetrahydrofuran
from Lignocellulose-Derived Furfuralacetone

Marc Strohmann, Andreas Vorholt and Walter Leitner, Max Planck Institute for
Chemical Energy Conversion, Mülheim a. d. Ruhr

The utilization of lignocellulosic biomass as feedstock for fuels and chemicals has
been an ongoing field of research in the last decades. Furfuralacetone (FFA), the
aldol condensation product of furfural and acetone, is a promising precursor for
diesel fuels. A lot of work focused on the complete deoxygenation of FFA to form
hydrocarbon fuels. However, fewer investigations dealt with the selective
transformation of FFA towards oxygen containing products such as 1-Octanol or 2-
Butyltetrahydrofuran (BTHF). Additionally, only discontinuous procedures towards 1-
Octanol or BTHF have been reported so far.[1,2] In this study, the first example of a
continuous flow production of BTHF from FFA is presented.

The transformation consist of two consecutive catalytic reactions for which

commercial catalysts are applied. First, FFA is hydrogenated to 4-(tetrahydrofuran-2-
yl)butan-2-ol (THFA) over Ru/C. The resulting THFA is hydrodeoxygenated to BTHF,
in the second step, catalyzed by a combination of Ru/C and an acidic ion exchange
resin. The separation of the two reactions is necessary, in order to avoid
polymerization of FFA under acidic conditions. A continuous flow process is finally
realized in a custom-built miniplant, which is equipped with two consecutive tubular
reactors.

The first reaction step gives the fully hydrogenated product THFA with selectivity up
to 97% and an open chain diol as main side product. In comparison to batch
hydrogenations, the use of a continuous flow reactor leads to a higher productivity
and provides an easy catalyst separation. The further conversion of THFA to BTHF in
continuous flow is possible with a selectivity of over 70% so far. However, batch
experiments showed a selectivity towards BTHF of up to 94%. Side products are the
BTHF isomer 2-Propyltetrahydrofuran and the linear 1-Octanol.
Long-term experiments of the FFA hydrogenation revealed that the Ru/C catalyst
deactivates rapidly under certain conditions. Therefore, the catalyst was analyzed
before and after the reaction with different microscopic and spectroscopic methods,
in order to understand the nature of the deactivation.

[1] J. Julis, W. Leitner, Angew. Chem. Int. Ed. 2012, 51, 8615-8619.
[2] K. L. Luska, J. Julis, E. Stavitski, D. N. Zakharov, A. Adams, W. Leitner, Chem.
Sci. 2014, 5, 4895-4905.
 Experimental Flow Structure Analysis in a 1 MWth Fluidized Bed
Pilot Plant

Alexander Daikeler, Jochen Ströhle, Bernd Epple

Institute for Energy Systems & Technology, Technische Universität Darmstadt, 64287
Darmstadt, Germany

Abstract
Gas-solid fluidized beds are used for various different processes, like fluid catalytic
cracking, combustion of solid fuels and newly developed carbon capture processes
such as carbonate and chemical looping. Gas-solid fluidized beds have been
extensively studied over the past decades. Knowledge of the hydrodynamic behavior
of fluidized beds is of key interest since the internal distribution and movement of
solid and gas phase has a strong influence on reactor performance. Furthermore, the
increasing power and applicability of 3-D CFD models requires careful comparison of
the simulation results with experimental measurements. Due to the demanding
conditions in a high temperature CFB reactor, only few locally resolved
measurements of particle concentrations and velocities have been published so far.
A water-cooled capacitance probe measurement system has been developed in
order to conduct inbed flow pattern measurements within the two circulating fluidized
bed (CFB) reactors of the Institute’s 1 MW th pilot plant. The refractory lined pilot plant
consists of two coupled fluidized bed reactors with inner diameters of 600 and 400
mm and heights of 9 and 12 m respectively. Several processes like carbonate
looping, chemical looping, gasification and fluidized bed combustion are investigated
at this test rig.
This contribution presents new measurement results of the 1 MWth pilot plant and of
the scaled cold flow model. Special attention is paid to the investigation of particle
cluster structures, which has not been done before. Particle clusters are loosely
bound particle agglomerates, which have a strong influence on the overall
hydrodynamic behavior of fluidized beds. Based on analysis of the measurement
signals for specific pre-defined criteria, several cluster characteristics like cluster
length, cluster appearance frequency, cluster velocity etc. can be identified. Cluster
characteristics of cold flow model experiments are compared with measurements in
real hot conditions of the 1 MW th pilot plant.
 Investigation of upstream and downstream flow conditions in a
swirling inline fluid separator – experiments with a wire-mesh
sensor and CFD studies
B. Sahovic1*, E. Schleicher1, U. Hampel 1,2
1
Helmholtz-Zentrum Dresden - Rossendorf, Institute of Fluid Dynamics, Dresden,
Germany
2
Technische Universität Dresden, AREVA Endowed Chair of Imaging Techniques in
Energy and Process Engineering, Dresden, Germany

Gas-liquid separation is an important process for multiphase flow in the oil, natural
gas and chemical industry. These industries have been developing separation
systems and each time with a little improvement regards to efficiency. The
fundamental principal of working is dividing different phases in fluid mixture based on
their density. Initial experiments were needed to further develop an efficient
separation system. Our particular objective was the analysis of the correlation of
upstream flow patterns with the shape of the swirling gas cores downstream the swirl.
We used the wire-mesh sensor to study the flow conditions upstream a swirling
device, which is used in the oil and gas industry as a separator. Wire-mesh sensors
have been developed to measure gas-liquid distributions in two-phase flows at high
speed. In a wire-mesh sensor, a wire electrode grid is formed in the flow cross-
section by wires running in two planes of a small axial distance. Its functional
principle is based on the measurement of either electrical conductivity (conductivity
wire-mesh sensor) or relative permittivity (capacitance wire-mesh sensor) in the
electrode crossings. Repeated scanning gives high speed sequences of cross-
sectional phase indicator distributions. The flow pattern and especially its transition
have an impact on the shape and interface stability of the swirling gas core
downstream. Hence the wire-mesh data can be used as a predictor for expected
hollow vortex variations and can be used for automatic control of the swirling device.
To assess the relationship between wire-mesh data and vortex shape we used a
high-speed camera to record downstream behaviour. Digital image processing
techniques like edge-based segmentation have been used to quantify geometry
characteristics of the produced gas core and estimate its stability (figure 1). As
automatic control requires a good process model we intend to use an original
computational fluid dynamics (CFD) coupling a Volume-of-Fluid (VoF) method for
interface resolution and an Immersed Boundary Method (IBM) for the separator
description (figure 2). For that we performed first CFD studies which give key
indications of required model improvements and future numerical research work.

a) original image b) mask c) binarized gas core

Figure 1: Steps in image processing

Figure 2: Streamlines of single phase flow through the separator

 Separation efficiency and design optimization of continuous
gravity settlers

E. Charlafti1, J. Steinhoff2, D. Leleu3, L. Reinecke4,

A. Pfennig3, H. -J. Bart2, M. Kraume1
1
TU Berlin, Berlin, Germany, 2TU Kaiserslautern, Kaiserslautern, Germany
3
Université de Liège, Liège, Belgium, 4Franken Filtertechnik KG, Hürth, Germany

The separation of liquid/liquid dispersions through gravity settlers is a

fundamental and widely implemented process, thanks to its simplicity and its cost
and energy efficiency. The joint research project ERICAA (‘Energy and resources
saving through innovative and CFD-based design of liquid/liquid gravity separators’)
aims to optimize design standards for gravity settlers used in industrial liquid/liquid
separation applications. This collaboration is funded by BMWi as part of the “Wanted
Technologies” initiative.
For the purposes of the experimental investigation, three identical continuous
mixer-settler setups were constructed and are operated in parallel in three different
locations in Germany. They all consist of a standard DN150 settler without internals,
through which liquid/liquid dispersions of paraffin oil and water separate. By directing
the aqueous and organic phases towards two secondary DN100 gravity settlers with
built-in coalescers, phases are purified before recirculation and the total separation
efficiency is determined. Droplet sizes of the dispersed phase are measured both at
the inlet and the outlet of the DN150 settler, thus allowing the calculation of
separation factors for droplet size classes of various flow conditions. To better
observe swarm sedimentation and coalescence phenomena, batch settling
experiments are conducted in a bypass parallel to the inlet of the continuous
separator and the results are modelled after Henschke’s approach [1].
CFD simulations of the DN150 gravity settler are performed with the goals of
ultimately predicting the separation efficiency of the continuous process in a more
cost-sustainable way and of generating additional information about parameters
which are not easily measurable, such as the velocity fields and the evolution of the
average droplet sizes inside the separation vessel. Multiphase flow models are
coupled with population balance equations and a novel coalescence model is
implemented. The results of the CFD simulations are compared to the experimental
results and their validation is discussed.

______________________
[1] Henschke, M., Holger Schlieper, L., Pfennig A., 2001. Determination of a coalescence parameter from batch – settling
experiments. Chemical Engineering Journal 85, 369-378
 Influence of microbubble aeration on hydrodynamics and mass
transfer in a 3 L Stirred Tank Reactor

Simon Matthes1, Sven Kastens

Ka ten 1, Benjamin Thomas2, Daniel Ohde2,
Paul Bubenheim2, Andreas
Andrea Lie e2, Koichi Terasaka3, Mi
Liese Michael S hlüter1
hael Schlüter
1: Institute of Multipha
Multiphase
e Flows,
Flow , Hamburg University
Uni er it of Te
Technolog
hnolog
hnology,, German
Germany
2: In
Institute
titute of Technical
Te hni al Bio
Biocatalysis,
atal i , Hamburg Uni
University
er it of Te
Technolog
hnology,
hnolog , Germany
German
3: Department of Applied Chemi
Chemistry,
tr , Keio Uni
University,
er it , Japan
apan

Many chemical
Man hemi al and biocatalytic
biocatal ti reactions
rea tion are consuming
on uming gaseous
gaseou species
pe ie lilike
e
oxygen,
o gen, pro
provided
ided by
b the ma
mass tran
transfer
fer across
a ro interfa
interfaces
e of multiphase
multipha e contact
onta t
apparatuses. In large-scale
scale
ale pro
processes
e e the gas
ga is
i often supplied
upplied to the liquid bulk
bul
phase
pha e b
by bubble aeration. E
Especially
pe iall for bio
biocatalytic
atal ti rea
reactions
tions
tion the ma
macroscopic
ro
aeration can
an lead to redu
reduced
ed en
enzyme
me a
activity
ti it bby foaming and indu
induced
ed shear
hear for
forces.
e .
For fast chemical rea
reactions
tions in multipha
tion multiphase
e flow
flows,, the ma
mass tran
transfer
fer limitation iis often
the bottlene
bottleneck for a pro
process
e optimi
optimization.
ation. Con
Considering
idering bubbles
bubble with diameter
diameters le
less
than 100 μm, large volume
olume-specific
pe ifi interfa
interfacial
ial areas
area a and therefore high ma
mass
transfer rates βLa of the ga
gaseou
gaseous
eou rea
reactant
tant on itits wa
way to the bul
bulk phase
pha e are offered. In
addition the high Laplace pressure
pre ure at that size
i e is leading to an acceleration of the
mass transfer. Compared to large-scale
large ale bubble aeration, the potential of using
u ing
bubbles with diameters smaller
maller than 100 μm iis le
less e
explored
plored so
o far. At that point this
thi
projectt starts
proje tart in
investigating
e tigating the aeration with fine bubble
bubbles,, due to the rising
ri ing demand in
process
pro e engineering for aeration with high ma
mass transfer
tran fer performance,
performan e, low pre
pressure
ure
drop, low shear stress
e and the avoidance
a oidan e of foaming.

Figure 1: Compari
Comparison
on between conventional aeration and fine bubble aer
aeration
ation in bio
biocatalytic
atalytic processes
pro e e in a STR
STR.
Furthermore, the rise velocity of a bubble decreases with decreasing bubble diameter
leading to higher residence time and low induced shear stress. To determine the
potential of fine bubbles for biocatalytic processes, the promising properties of fine
bubble aeration compared to conventional aeration (as shown in figure 1) is under
investigation in close collaboration with the Institute of Technical Biocatalysis (ITB) at
the Hamburg University of Technology and Prof. Koichi Terasaka from Keio
University, Japan.

Experimental approach
To quantify the influence of fine bubble aeration on the hydrodynamics and the mass
transfer, measurements of the bubble size distribution and the mass transfer rates
from oxygen into the liquid phase are executed in a 3 L stirred tank reactor. The
effect of different stirring speeds and gas flow rates are determined for the reference
system deionized water/ air and the two aqueous solutions of glucose (133 mmol/ L)
and rhododendrol (10 mmol/ L) as bioactalytic model systems which are also aerated
with air. All investigations took place in a turbulent state at stirrer speeds of 400, 600
and 800 rpm and gas flow rates from 25 mL/ min up to 100 mL/ min. Different fine
bubble generators working under the principle of the pressurized dissolution method
and membranes of pore sizes from 0.5 µm up to 2 µm are used for the aeration.
Their performance and influence on the systems are characterized and compared.

Figure 2: Visualization and detection of microbubbles via SOPAT-VI Pl (left) and mass transfer rates for
different gas flow rates for a sinterstone producing microbubbles with a pore size of 0.5 µm (right).

Acknowledgement
The authors gratefully acknowledge the financial support provided by the Deutsche
Forschungsgemeinschaft (DFG) within the project (SCHL-617_LI-899).
 Qualification of a photometer probe for local concentration
measurement in dense bubbly flows

Uwe Hampel1,2, Holger Kryk2, Ragna Kipping1

1
Technische Universität Dresden, Chair of Imaging Techniques in Energy and
Process Engineering, 01062 Dresden, Germany
2
Helmholtz-Zentrum Dresden - Rossendorf, Institute of Fluid Dynamics, Bautzner
Landstraße 400, 01328 Dresden, Germany

Motivation
Topics of current research activities within the DFG priority program SPP 1740
“Reactive Bubbly Flows” are studies on local mass transfer and reaction processes in
order to gain a deeper understanding about the coupling of hydrodynamics, mass
transfer and reaction kinetics in reactive bubbly flows as well as its influence on yield
and selectivity in case of complex chemical reactions. Precondition for experimental
investigations is the availability of sensors for local concentration measurements of
components in the liquid phase. Due to limitations of currently available non-invasive
measuring techniques, local concentration measurements in dense bubbly flows at
technical scale pose technological challenges. Therefore, a minimal-invasive
photometer probe have been qualified to measure concentrations of intermediates
and products within the liquid phase of dense bubbly flows with high temporal and
spatial resolution.

Sensor design
To ensure a minimal-invasive design of the photometer probe, a modular measuring
system was used where light emitters, detectors and further electronic components
are integrated in a remote unit. The light is guided between the electronics unit and
the probe as well as insight the probe using optical fibers. To deflect the light beams
at the tip of the probe, micro prisms are used. Thus, a forked probe with two legs of a
diameter of only 1 mm and a distance of 3 mm was realized allowing for photometric
concentration measurements in the UV/Vis range within a volume of approx. 3 mm³.
The sensor is prepared for simultaneous measurements at three different
wavelengths using three LEDs and three detectors with upstream optical filters (two
are currently in use). In such way, it is possible to distinguish between two liquid
components and the gaseous phase (bubbles) allowing for high measuring
frequencies of up to 5 kHz.

Calibration and test

The sensor was qualified to measure the concentration of the liquid product complex
[Fe(II)(EDTA)-NO]2- at 435 nm during the reaction of [Fe(II)(EDTA)]2- with NO in a
bubble column. By calibration using [Fe(II)(EDTA)-NO]2- solutions of defined
concentrations, a linear dependency between concentration and extinction according
to Lambert-Beer law was found for product concentrations of up to 7 mmol/L.
Furthermore, a lower measuring limit of approx. 0.01 mmol/L was proven. By
simultaneous transmission measurements at 780 nm (reference wavelength), it was
clearly possible to distinguish between local concentration peaks in the liquid phase
and the presence of a gaseous phase. In such way, concentration gradients in the
wake of single bubbles as well as bubble swarms could be detected.

Outlook
It is planned to use the third wavelength in order to measure the concentration of a
second liquid component (e.g. intermediate product) simultaneously. Thus, the
sensor is going to be capable to monitor reactions that are more complex.
Furthermore, simultaneous measurements of bubble swarm dynamics using our fast
electron beam X-ray tomograph ROFEX and of local concentrations using the
photometer probe are intended to elucidate the interplay between hydrodynamics,
mass transfer and chemical conversion.

This work was supported by the German Research Foundation (DFG), reactive
bubbly flows (SPP 1740).
 A generalised bouncing boundary line for the modelling of droplets
collision outcomes

Maohong Sui, Martin Sommerfeld, Lars Pasternak

Multiphase Flow Systems, Institute for Process Engineering, Otto-von-Guericke-

University Magdeburg; Zeppelinstraße 1, D-06130 Halle (Saale), Germany
E-mail: Maohong.sui@ovgu.de

Spraying systems are of great important in a range of different technical and industrial
applications. Depending on the operational conditions and the spray structure the
produced droplet size spectrum may be largely affected by collisions between droplets.
For a numerical prediction of spraying processes by the Euler/Lagrange approach,
therefore reliable models are required for predicting the collision outcome. This is mainly
done using so-called collision maps demarking the different outcome scenarios by
appropriate boundary lines (i.e. bouncing, separation and coalescence). These
boundary lines should be reasonably general including all relevant influential effects,
such as impact conditions, droplet size ratio and liquid properties.

Therefore, a variety of detailed experimental studies on the collision of higher viscous

pure liquids and solution droplets were used for developing a model for the boundary
line between coalescence and stretching separation. However, the boundary line for
bouncing, mostly used in numerical studies so far, was derived based on experiments
with ethanol droplets (Estrade et al.[1]), and completely neglects viscous dissipation.
Therefore, the deviations for predicting the region of bouncing are quiet large for liquids
with high viscosity or different properties.

In this work, a new, more general correlation for the bouncing boundary was derived,
which however includes new assumption and definitions. The new boundary line is
based on the studies of Estrade et al. [1] and Hu et al. [2]. The original model already
includes a shape parameter ∅ which actually also should dependent in the impact
parameter B, reflecting the deformation during the collision process. Moreover, an
additional parameter β was included reflecting the degree of dissipation or the energy
conversion during collision. Both parameters could be linearly correlated with the impact
parameter B. The included slope and initial values could be very well correlated with the
Ohnesorge number and approximated by third order polynomials which fitted the
available experimental results, separately for pure fluids and solution droplets. The new
bouncing boundary line has been has been developed based on experimental result by
Kuschel and Sommerfeld [3], [4] and Pasternak and Sommerfeld [5]. Consequently, the
boundary line for bouncing is predicted more accurately and the trends with changing
liquid viscosity and droplet size ratio are very well captured.

Keywords: Droplet collision, collision map, bouncing boundary, viscosity effects, energy
dissipation
References

[1] J.-P. Estrade, H. Carentz, G. Lavergne, and Y. Biscos, “Experimental investigation of

dynamic binary collision of ethanol droplets – a model for droplet coalescence and
bouncing,” Int. J. Heat Fluid Flow, vol. 20, no. 5, pp. 486–491, Oct. 1999.
[2] C. Hu, S. Xia, C. Li, and G. Wu, “Three-dimensional numerical investigation and
modeling of binary alumina droplet collisions,” Int. J. Heat Mass Transf., vol. 113, pp.
569–588, Oct. 2017.
[3] M. Kuschel and M. Sommerfeld, “Investigation of droplet collisions for solutions with
different solids content,” Exp. Fluids, vol. 54, no. 2, Feb. 2013.
[4] M. Sommerfeld and M. Kuschel, “Modelling droplet collision outcomes for different
substances and viscosities,” Exp. Fluids, vol. 57, no. 12, Dec. 2016.
[5] L. Pasternak and M. Sommerfeld, “Experimental investigation of size effects in
colliding droplet,” in Ilass Europe. 28th european conference on Liquid Atomization
and Spray Systems, 2017, pp. 710–715.
 Experimental investigation of the multiphase flow in oil injected
multiphase twin screw pumps

Marian Lottis, Mohammad Deeb, Andrea Luke

University of Kassel, department of Technical Thermodynamics, Kassel, Germany

Twin screw pumps are used to transport liquid-gas mixtures in process technology,
since they are suitable for multi component and multiphase mixtures with high gas
fraction. Additionally, they are suitable for the conveyance for saturated liquids and
they are not sensible towards phase change. Thus, phase change phenomena as
condensation or evaporation has not to be avoided and new and more efficient
processes may be developed. Nevertheless, a new cooling concept has to be
developed for conveying mixtures with high gas content. An idea is, to inject the
liquid process fluid into the chambers of the pump. Such a method has a positive
influence on the cooling effect on the one hand side and on the other hand side this
method contributes to a better sealing of the gaps, hence increasing the volume flow.
Since the fluid is saturated, various sorption effects need to be taken into account,
especially within the narrow gaps.

In the first step, a transparent test rig simulating one chamber of the
pump/compressor with external fluid injection is designed and taken into operation to
investigate the effect of the injection into the chamber of a twin screw pump. The test
rig allows an optical pre analysis regarding the fluid dynamics in the gaps by varying
different parameters (direction of injection, number and type of injection nozzles, fluid
properties and sorption effects). In this work, the experimental setup and the first
experimental results from the rig are presented. The second step is to realize the
experiments in a test rig in an industrial scale with the real pump / compressor. The
rise of the temperature with the pressure by the conveyance of the multiphase
mixture is discussed in detail.
 Effect of Surfactants on the Flow Patterns of Horizontal Tube
Bundles with a Falling Film

Federico Lonardi1, Michael Olbricht2, Andrea Luke1

1
University of Kassel, Department of Technical Thermodynamics, Kassel, Germany
2
ARVOS GmbH, Schmidtsche Schack, Kassel, Germany

Absorption chillers can provide a cooling supply with negligible electrical power
consumption compared to traditional vapor compression chillers, since they are
driven by low-temperature waste heat. Nevertheless, their large size and high costs
make them not yet competitive and, thus, they have to be further optimized. The heat
exchangers of an absorption chiller with the working pair water/aqueous LiBr are
usually designed as horizontal tube bundles with a falling film because of the low
pressure of the refrigerant (water). In order to increase the heat and mass transfer of
the absorber, which has been widely recognized as the limiting component of such
chillers, small quantities of alcoholic surfactants are added to the aqueous lithium
bromide solution. As a consequence, its surface tension is reduced and the
wettability is increased, thus promoting an enhanced heat and mass transfer in the
absorber.
Recently it has been shown that these surfactants are not only present in the liquid
phase, but also in the vapor phase due to their volatility and the low pressure of the
chiller. Thus, they are also expected to reduce the surface tension of the aqueous
LiBr solution in the generator and of water in the condenser and evaporator. Hence,
a change in the flow pattern of the falling film in all components, which influences the
heat transfer as well, is also predicted.

The aim of this work is to investigate the influence of two different alcoholic
surfactants on the flow regimes of tube bundles with a falling film. The flow patterns
measured in an experimental setup of an absorption chiller in absence of surfactants
are compared with the ones available in the literature. The surface tension of water
and aqueous lithium bromide solution with different concentrations of 1-octanol and
2-ethylhexanol is measured at low pressure in a saturated atmosphere. Its influence
on the Galileo-Number and on the flow patterns in the absorber, generator,
condenser and evaporator is then discussed quantitatively.
 Modeling of transport of rheological complex multiphase fluids in
porous membranes
A. Schulz, U. Fritsching, Universität Bremen, Bremen/Germany

In our project we analyse the relevant interactions in the membrane emulsification

process by means of experiments and Lattice Boltzmann simulation methods. A
liquid/liquid mixture is dispersed through a porous media forming shear sensitive
emulsions. In order to produce stable Newtonian and non-Newtonian emulsions
surface active components are added to the system. The surfactants and the
behaviour of non-Newtonian liquids change the topology, resulting in different
filament breakage and coalescence behaviour of the dispersed phase. This leads to
drop sizes, that are smaller than the pore diameter of the porous membrane. In order
to model the dynamics of the liquid/liquid system numerical simulations on shear
thinning and viscoelastic droplets are carried out. The deformation and drop break-up
behaviour in porous media are investigated. Building up on this, we investigate the
role of surfactants and non-Newtonian liquids in the multiphase flow through porous
model structures like capillaries. Further, we use CT scans of porous membranes to
get realistic geometries to simulate the membrane emulsification process. NMR
velocity field measurements are used to validate the flow field of the liquids.
 Breakup Behavior of a Capillary Bridge on a Hydrophobic Stripe
Separating two Hydrophilic Stripes

M. Hartmann1, M. Fricke2, D. Bothe2, S. Hardt1

1
Institute for Nano- and Microfluidics, TU Darmstadt, Germany,
2
Mathematical Modeling and Analysis, TU Darmstadt, Germany.

The breakup dynamics of a capillary bridge on a hydrophobic area between two liquid
filaments occupying two parallel hydrophilic stripes is studied experimentally and
numerically with the Volume-of-Fluid (VOF) method.

Glass substrates with alternating covered and uncovered stripes of different widths and
width ratios are produced by common photolithography steps. The resulting substrates are
exposed to a silane atmosphere in a low pressure chemical vapor deposition process
leading to a silanization of the uncovered glass areas. After rinsing off the photoresist,
former uncovered stripes are more hydrophobic than former covered stripes. By using two
different silanes (1H,1H,2H,2H-Perfluorodecyltrichlorosilane and 3,3,3-
Trifluoropropyltrichlorosilane) the hydrophobicity can be chosen. Additionally, by
performing plasma treatment prior to photolithography, it is possible to influence the
hydrophilic contact angle. By doing so, chemically striped patterns with 4 different wetting
contrasts in total are produced.

Droplets of de-ionized water are placed on these substrates. Their volume decreases by
evaporation. This results in a droplet shaped as the letter “H” covering two hydrophilic
stripes separated by one hydrophobic stripe (see figure 1). The evolution of the capillary
bridge on the hydrophobic stripe is recorded using a high-speed camera mounted on a
bright-field microscope. Evaluation is performed by an inhouse software.

While the critical diameter dcrit,

i.e. the minimal width d of the
capillary bridge where the
droplet becomes unstable,
primarily depends on the ratio
between the width of the
hydrophobic and the hydrophilic
stripes, the results of the
Figure 1: Sketch of an evaporating droplet on a
experiments show that the time
derivative d’(t) first chemically striped patterned surface from below decreases
at a certain time t before the critical diameter dcrit
after dcrit has been reached.
Surprisingly, the breakup dynamics is a function of the contact angle contrast and mainly
depends on the wetting behavior of water on the hydrophilic stripe. For further
characterization of the breakup process, numerical simulations are performed.

The Volume-of-Fluid method is particularly well-suited to handle topological changes in

two-phase flow problems. It is based on the idea that the fluid-fluid interface can be
reconstructed from the volume fraction of the fluid phase in each computational cell. In the
present method, the interface is reconstructed as piecewise linear. Moreover, the VOF
method ensures exact conservation of the fluid volume in the discrete problem. To
incorporate the effect of contact angle hysteresis, we use the method proposed by Fang
and co-authors. The idea is to alter the geometrical reconstruction method such that the
contact line stays pinned for contact angles in the hysteresis interval.
In the hydrophobic region, we use the method proposed by Afkhami and Bussmann to
enforce the dynamic contact angle. To validate the numerical method, we compare the
rupture dynamics of the liquid bridge with the experimental data.

Acknowledgements
We kindly acknowledge the financial support by the German Research Foundation (DFG)
within the Collaborative Research Center 1194 Interaction of Transport and Wetting
Processes, Projects A02b and B01.
 Challenges in the design and scale up of multiphase reactors
– report on the Campus Multiphase Reactors –

Marcus Grünewald, Ruhr-Universität Bochum, 44801 Bochum

Michael Schlüter, Technische Universität Hamburg, 21073 Hamburg

The German research network „Campus Multiphase Reactors” (Campus

Mehrphasenreaktoren) under the roof of the ProcessNET has been initiated following
up the “Campus Bubble Columns” to transfer the methods, tools and results from
Bubble Column Reactors to all kind of multiphase apparatuses. One remaining goal
is the applicability of all methods and tools from laboratory conditions to industrial
conditions building a bridge between academia and production. In 2018 the main
challenges in the design and scale up of multiphase reactors have been identified in
workshops with representatives from industry, universities and research centers. First
research initiatives have been created and will continue in 2019 with bilateral pro-
jects, applications and programs.

In this lecture the identified challenges will be presented and discussed. Furthermore
it will be shown, which tools and methods are already available to solve future prob-
lems and how the next challenges of the design and scale up of multiphase reactors
will be addressed.
 Characterization of the gas input during Aqueous Two-Phase
Flotation (ATPF) for enzyme purification

Lucas Jakob, Hermann Nirschl, Karlsruher Institut für Technologie,

Karlsruhe/Germany

Motivation and Challenges

The purification of industrial enzymes from complex biosuspensions represents a
major challenge for the bioprocess. Many separation steps are necessary to capture
the target protein from the fermentation broth and to increase the purity up to the final
product. During downstream processing, various processes are used, such as
centrifugation, filtration, precipitation, extraction or chromatography, so that losses
and energy costs of the individual steps sum up and the purification costs for
enzymes usually represent more than 50% of the production costs (Chmiel, 2011).
In protein extraction from complex biosuspensions, Aqueous Two-Phase Systems
(ATPS) ensure mild conditions and high selectivity against the target protein. ATPS
are formed when a polymer or a lower alcohol is dissolved in water with another
polymer or salt above the critical concentrations (mixing gap). During extraction,
impurities (cells, cell debris, media components, ...) remain in the heavy lower phase
while the target protein diffuses into the upper, lighter phase. The yield is often
satisfactory only after several extraction stages and using large quantities of
extraction phase, since the diffusive mass transfer is low. The flotation of enzymes in
Aqueous Two-Phase Systems (Aqueous Two-Phase Flotation, ATPF) combines the
selectivity of the extraction with the high mass transfer of the flotation. By introducing
gas bubbles into the Two-Phase System, proteins with their hydrophobic part attach
themselves to the gas-liquid interface and are transported to the upper phase after
the bubbles have risen (see Fig.1). This allows to perfom "Capture" and "Clean" in
one step. The ATPF was described for the first time in 2009 (Bi, Li and Dong, 2009)
and promises to be an efficient alternative to conventional purification processes of
biotechnological products by eliminating several separation steps warranting mild
conditions.
 Atmosphere

Polymer or
Top Phase
Alcohol

Polymer or FA Diffusion
Salt
rising Bottom
Bubbles Phase

Fig. 1 A) Flotation in an Aqueous Two-Phase B) Schematic illustration of the mass transfer

System (ATPF) during the ATPF

Research Approach and Results

Within the research project, ATPF will be fundamentally investigated for its
application potential for the purification of industrial enzymes. First, the relevant
chemical parameters for ATPF will be identified and suitable Two-Phase Systems will
be found. Subsequently, the purification of different industrial model enzymes (e.g.
amylases, proteases and lipases) will be investigated and mass transfer
characterized. The yield of ATPF will be increased by process optimization. The
influence of flotation parameters (e.g. type of gas input, bubble size and residence
time) will be investigated. The aim is to find an ideal operating window for the gas
flotation which guarantees a maximum flotation rate but prevents mixing of the
aqueous phases due to turbulence.
In this talk the project concept and the first results will be presented. These include
the bubble characterization during gas introduction via porous media (e.g. sintered
plastic membranes and metal mesh), as well as the influence of the gas introduction
on the flow conditions within the two-phase system.

Literature
Bi, P., Li, D. and Dong, H. (2009) ‘A novel technique for the separation and
concentration of penicillin G from fermentation broth: Aqueous two-phase flotation’,
Separation and Purification Technology. Elsevier, 69(2), pp. 205–209. doi:
10.1016/J.SEPPUR.2009.07.019.
Chmiel, H. (ed.) (2011) Bioprozesstechnik. Heidelberg: Spektrum Akademischer
Verlag. doi: 10.1007/978-3-8274-2477-8.
 3D-Konzentrations-Bestimmungen in Blasensäulen mittels

UV/Vis-Tomographie

Jajnabalkya Guhathakurta1, Rinke Günter2, Manfred Kraut2, Sven Simon1,

1
Institute für Parallele and Verteilte Systeme (IPVS), Universitätsstr. 38, 70569
Stuttgart; 2 Institute for Micro Process Engineering (IMVT), Karlsruher Institut für
Technologie, Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen

Einführung

Blasensäulen spielen in der chemischen Industrie für zweiphasige Systeme eine

entscheidende Rolle und sind vor allem für Reaktionen wie Oxidation, Hydrierung,
Alkylierung etc. relevant. Eine realistische Beschreibung und Vorhersage der
Reaktionskinetik und des Stofftransfers ist jedoch nach wie vor ein wesentlicher
Problem in industriell relevanten reaktiven Blasensäulen. Darüber hinaus ist eine
ortsaufgelöste Konzentrationsmessung aufgrund der schnellen Reaktionen und der
schwierigen Zugänglichkeit des Aufbaus problematisch. Ziel dieser Arbeit ist die
Entwicklung einer räumlich und zeitlich aufgelösten 3D-Konzentrationsmesstechnik
in reaktiven Blasensäulen mittels UV/Vis-Computertomographie.

Eine weitere wichtige Herausforderung für Chemie- und Verfahrensingenieure ist die
Bestimmung der Selektivität in einem Zweiphasenreaktionssystem. Dies ist ein
vorrangiges Entwicklungsziel des vorgeschlagenen Messystems. Das System
verwendet mehrere Wellenlängen und schnell schaltende Lichtquellen, um
gleichzeitig und getrennt die Konzentration beider Produkte in einer konkurrierenden
aufeinanderfolgenden Reaktion zu messen und daraus die Selektivität der Reaktion
abzuleiten.

Experimenteller Aufbau

Das entwickelte UV/Vis-Computertomographie-System nimmt die

Absorptionsprojektionen aus verschiedenen Winkeln um die Blasensäule herum auf
(blauer Kreis in Abb. 1 Mitte). Diese gerichtete Absorptionsprojektionen werden dann
in einen iterativen Rekonstruktionsalgorithmus eingespeist, um ein 2D-
Konzentrationsfeld senkrecht zur Strömungsrichtung zu erhalten. Obwohl die
Technik für das Fe(edta)NO-System entwickelt wurde, kann sie auf jedes chemische
System angewendet werden, das einen unterschiedlichen Peak für Produkte im
Absorptionsspektrum
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Abb. 1. (links) UV/Vis-Spektrum

Spektrum für Fe(EDTA)NO-System[1],
Fe(EDTA)NO System[1], (mittlerer) Querschnitt der
Blasensäule mit 75mm Durchmesser und achteckigem Brechungsindex-Anpassungsmantel
Brechungsindex Anpassungsmantel
mit Richtungsvorsprüngen, (rechts) tatsächliche Blasensäule

Ergebnisse
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Abb. 2. (links) Zeemax-Strahlenverfolgungssimulation für jede Projektion, (Mitte)
Rekonstruiertes Konzentrationsfeld auf Simulationsdaten in Blasensäulen.
 Nozzle tip wetting during coaxial atomization in the context of
nanoparticle spray flame synthesis

Malte Bieber, Manuel A. Reddemann, Reinhold Kneer,

RWTH Aachen University, Germany

Introduction
Nanoparticle synthesis based on spray flame pyrolysis offers high potential to design
nanoparticles with unique properties. Therein, the influence of the atomization
process the resulting particle output is not yet fully understood but offers a high
potential, as it determines the initial droplet size and velocity distribution, i.e. the initial
conditions for development of flame shape and temperature field. Aimed
manipulation of atomization towards optimized initial conditions can be achieved by
variation of nozzle geometry, injection parameter or fluid properties. The resulting
effects of these changes on atomization, spray and flame formation and finally on
particle properties is not yet fully understood and requires a profound understanding
of the early process chain. The standardized SpraySyn burner is utilized, that
represents a key component in the DFG priority program SPP1980 and offers a well-
defined burner geometry based on the coaxial atomization principle. The burner is
embedded in a semi-closed combustion chamber that enables full visual access.
Towards understanding of the entire process chain, high-speed shadowgraphy
measurements are conducted directly at nozzle exit for investigation of primary
breakup under hot conditions.

Results
In Figure 1 left, exemplary microscopic high speed images of the primary breakup
directly at nozzle exit are shown for pure Ethanol. For a better interpretation of jet
diameter and position, a scaled schematic drawing of the nozzle geometry is added
at the bottom of each image (white scetch). Analysis of corresponding high-speed
videos indicate, that the radial position of the main jet axis and jet diameter at nozzle
outlet are not constant over time, but are subject to an oscillating behavior as
indicated in exemplary microscopic images (3-6). In image 5, the jet is well centered
relative to the needle axis and the jet diameter is close to the inner needle diameter.
In image 6, the jet exits equally centered but shows an additional spreading on the
flat top of the needle tip and therefore an increased diameter. Consequently, the jet
diameter is changing over time. In both images, the expanding gas phase interacts
with the liquid phase by means of pushing it back towards the center. Without
dispersion gas, the liquid phase spreads over the entire nozzle tip, including the
annular gap for dispersion gas, until it reaches a force equilibrium of capillary force
driven spreading and surface tension induced contraction force. Therefore, the
position of the phase boundary r(t) during atomization reflects a power equilibrium of
capillary force driven spreading, contracting surface tension and gas pressure.

Figure 1: Left, microscopic high speed images at nozzle exit of the ignited Ethanol spray flame. Right, measured jet diameter
oscillations at nozzle exit and oscillation of jet center position over time combined with corresponding Fast Fourier transform
of the signal for determination of prominent oscillation frequencies.

In lateral direction, a second oscillation of the jet can be observed as shown in

images 3 and 4. Lateral oscillation in 2d-images are either a side shift of the jet or
caused by a circumferential jet movement. Further downstream, high-speed video
data indicates that the droplets follow a swirling movement of the gas phase, caused
by a tangential velocity component. This swirl and tangential velocity share of the gas
phase appears to be present from nozzle exit. Consequently the tangential velocity
share is caused by internal nozzle flow. In numerical analysis of diameter and jet axis
position, two main frequencies of described jet movements have been identified to
~100 Hz for jet diameter oscillation and ~900 Hz for side shift frequency of the jet
center and thus for the presumably circumferetial movement of the jet center.
Conclusion
Conducted microscopic high-speed imaging of primary atomization at nozzle exit
revealed two oscillating liquid jet movements that represent initial conditions for
primary atomization and consequently spray formation. Capillary force driven surface
wetting causes the liquid jet to spread directly at nozzle exit until it interacts with the
gas phase. As a result, the liquid jet diameter and the jet axis position relative to the
needle axis are oscillating over time directly at nozzle exit. In order to further
understand the physics behind present force equilibrium, further investigations are
required with varying gas mass flow and fluid properties, e.g. viscosity and surface
tension and resulting influence on absolute values (Dmin/max) and relevant
frequencies.
 A thorough analysis of the dispersion of glycerol in dimethyl
carbonate with video microscopy
Jesús Esteban1, Halina Murasiewicz2
1
Max-Planck-Institut für Chemische Energiekonversion, Abteilung Molekulare
Katalyse. Mülheim an der Ruhr/Germany
2
Faculty of Chemical Technology and Engineering, West Pomeranian University of
Technology, Szczecin/Poland

Motivation
The valorization of glycerol has gained attention in the past years. One of the most
relevant products derived thereof is glycerol carbonate, which stems from the
transesterification of glycerol (Gly) with dimethyl carbonate (DMC), which is used in
large excess [1]. Gly and DMC show limited miscibility at the early stages of the
reaction and then a transition to a single liquid phase occurs as the concentration of
the products glycerol carbonate and methanol increases [2]. This study focuses on
the analysis of the dispersion of Gly in different volumetric excesses of DMC and
temperatures, both relevant to the eventual chemical reaction that would occur
adding a catalyst. The aim is to understand the droplet size distribution (DSD) as well
as the coalescence and breakage behaviour of the dispersed glycerol upon stirring
given the fact that basic catalysts needed for the reaction dissolve in this phase [3].

Methods
The dispersion in a tank stirred with a Rushton turbine was recorded ex-situ by video
microscopy and the images acquired were analyzed using a plugin developed for the
ImageJ program (1.52e release). An example of an image is given in Fig. 1.

Fig. 1. Image of Gly dispersed in DMC at ϕd=0.15,T= 333.15 K and N=300 rpm before (left) and after processing (right).

Results
From the DSDs obtained from the experiments, the Sauter mean diameter (d32) was
calculated as characteristic drop size. Temperature affected mainly the change of
viscosity, whereas not so much the interfacial tension. At the lowest viscosities, the
d32 observed were much smaller, as shown in Fig. 2. The effect of an increased
impeller speed is a reduced droplet size as a consequence of a greater energy input
that promotes breakage of the droplets. Finally, d32 increased with the holdup, being
this phenomenon more pronounced at low impeller speeds because as this variable
increases, the breakage zone is enlarged while a volume of the coalescence region
is reduced; however, the latter variable is not as influential on drop size as viscosity.
Operating at 500 rpm at the highest temperature (lower viscosity) and a holdup of
0.08 (i.e., molar ratio DMC:Gly=10:1) is most appropriate to generate the smaller
droplets and thus a higher interfacial area, which is beneficial for enhanced mass
transfer in the eventual chemical reaction between Gly and DMC.

Fig. 2. Effect of temperature at N=300 rpm (left) as well as stirring rate and holdup of dispersed phase (right) on d32.

d32 was correlated as a function of the Weber number considering an additional term
Vi for viscous forces given the nature of Gly, which cause cohesive stress, as shown
in eq.1 [4]. Also, d32 was correlated successfully with available theoretical models
based on energy dissipation rate (eq.2). Both fittings can be observed in Fig. 3.

. .
(eq.1)
= (1 + )
!
, = ̅ . (eq.2)

Fig. 3. Correlation of d32 with respect to the Weber number (left) and energy dissipation rate (right).

References:
[1] M.O. Sonnati et al. Green Chem. 15 (2013) 283-306. [2] J. Esteban et al., Chem.
Eng. Res. Des. 92 (2014) 2797-2805. [3] J. Esteban et al., Chem. Eng. J. 260 (2015)
434-443. [4] C.Y. Wang and R.V. Calabrese, AlChE J. 32 (1986) 667-676.
Poster Abstracts
Electrochemical Reaction
Engineering
 Improved Operating Parameters for
Hydrogen Peroxide Generating Gas Diffusion Electrodes
T. Muddemann, Institute of Chemical and Electrochemical Process Engineering,
Clausthal-Zellerfeld, Germany; D. Haupt, CUTEC Research Center for Environmental
Technologies, Clausthal-Zellerfeld, Germany; M. Sievers, CUTEC Research Center
for Environmental Technologies, Clausthal-Zellerfeld, Germany; U. Kunz, Institute of
Chemical and Electrochemical Process Engineering, Clausthal-Zellerfeld, Germany

Due to increasing water scarcity and stringent environmental regulations for dealing
with production residues, the re-use of process waters is getting continuously more
relevant as a solution for industrial growth in spite of water scarcity. For such
applications, electrochemical treatment methods beside others have moved into
focus of research and development.

An innovative concept for removing trace elements is a combination of a boron-

doped diamond electrode and a gas diffusion electrode (GDE) for generating highly
oxidative species at both electrodes simultaneously. Such a system is not
commercially available yet, and the absence of efficient hydrogen peroxide GDEs
(H2O2-GDE) working at high current densities is one of the reasons.
High yields H2O2 are crucial for efficient water purification, but also for decentralized
and demand-oriented production of H2O2 solutions through renewable electricity at
best.
Next to the technical design of H2O2-forming GDEs, the process conditions
significantly determine the H2O2 yield and are focused by this contribution.

System, functionality and outlook

To optimize the cathodes performance, the impact of diverse process parameters
were investigated and evaluated regarding the H2O2 yield.
For the evaluation, a divided system (100 cm2 active area) with an oxygen-forming
anode and a H2O2-GDE (Vulcan XC72 carbon black and PTFE on gold-plated nickel
wire cloth) were constructed and operated (figure 1). A continuous dosing and
overflow operation enable stationary steady-states for evaluation of cathodic
performances by mass balances.
This study proceeds our previously published article (Muddemann et al. 2018),
2018
investigating the influen
influence
e of ele
electrolyte
trol te temperature, electrolyte
ele trolyte
trol te volume
olume flow and
current
urrent den
density
it in the alkaline environment.
en ironment.
Therefore, the present parameter variation
ariation examines the influence of electrolyte
temperature in the full pH range, which is de
decisive
i i e for the design of wastewater
specific processes.. In addition, the influence
influen e of water load independent operating
parameters are in
investigated
e tigated, especially the influence of gaseous volume flow, gas
differential pressure, o
oxygen
ygen concentration
on entratio and current density.
Selected Results
The results reveal current
urrent yields
ield greater 90 % (1.6 wt%) at defined process
conditions with a current
urrent den it of ≥ 0.5 kA/m2. In addition, considerable voltage
density oltage
savings of greater 70 mV are a
achieved
hie ed in particular
parti ular by
b selecting
ele ting the right differential
pressure
re and o
oxygen
gen volume flow rate. This will further in
increase
rease the application
potential of ele
electrochemical
tro hemical processes
pro e e babased
ed on H2O2-producing
producing GDEs through
lower operating costs.

Fig.1: Schematic of the operated

perated electr
electrolysis
l sis wit
with aimed reactions aand material flows.
fl ws

References
Muddemann, Thorben; Kun
Kunz,, Ulrich;
Ulri h; Haupt, Denni
Dennis René; Sie
Sievers,
er
ers,, Mi
Michael
hael (2018):
Optimized
Optimi ed Process
Pro e Conditions
Condition for Hydrogen
H drogen Peroxide
Pero ide Generating Gas Diffusion
Diffu ion
Electrodes. In: ECS Trans. 86 (4), S. 41–53.
53. DOI: 10.1149/08604.0041ecst.
10.1149/08604.0041e t.
 A Simulative Approach for Linking Electrode and Electrolyte
Properties to Supercapacitor Performance

Konrad Krois1, Lucas Hüfner1, Jan Gläsel1, Bastian Etzold1,

1
Technische Universität Darmstadt, Darmstadt Deutschland

Supercapacitors are energy storage devices with the distinct advantage of a high
power density as well as high cycle stability, robustness and the use of non-critical
materials. Current applications leverage mainly the high power density, though in
future non-mobile storage devices also the aspect of the robustness and employed
materials could show great benefit in the case when lower charging/discharging time
constants are acceptable. In this sense optimizing the electrode design for higher
energy densities, while potentially comprising power density is of interest. This can
be achieved on the hand by the development of new high performance active
materials.[1, 2] On the other hand increasing the share of active material to inactive
overhead (current collectors, packaging, and separator) is a possibility. In this study,
a simulative approach based on the porous electrode theory and the groundwork of
Liu, et al. [3] and Kroupa, et al. [4] is employed to study the complex interplay of
mass transfer, electric losses, double layer capacitance for different electrode
thicknesses, electrode and electrolyte conductivities and charging/discharging time
constants.

Methods
A 1D chemical reaction engineering simulation was employed to study the interplay
of material properties, electrode thickness and time constant for charging/discharging
on the achievable capacitance and overall voltage efficiency. The
pseudohomogeneous model accounts for electric losses in the liquid and solid
phase, for mass transfer within the open porosity of the electrode (but not within
particle grains) and for the storage mechanism through a Guoy-Chapman-Stern
mechanism. Within the simulation cyclic voltammetry (CV), galvanostatic cycling
(GC) as also electrochemical impedance spectroscopy (EIS) experiment could be
realized. With this, the dependency of achievable maximum capacitance as also
voltage efficiency on various properties could be deduced and allows obtaining a full
picture of suitable electrode designs based on the energy storage scenario.
Results
The simulation allowed to calculate properly the response of supercapacitors for CV,
GC and EIS experiments. While simulations of the CV experiment could cover the full
range of charging/discarging time constants, it is rather time consuming. EIS
simulations allowed to obtain the response for relatively low time constants and GC
for relatively high time constants, both in a fast manner.
Varying in the layer thickness from 50 µm to 1 mm and the time constant from 10 to
10000 s revealed, the strong dependency of the optimal electrode thickness from the
charging/discharging time constant. From this an achievable capacitance and voltage
efficiency could be deduced. For energy storage scenarios with time constants in the
range of seconds, approx. sub 100 µm layers are optimal, which reflect current
application of supercapacitors. Interestingly, when increasing the time constant to
hours, approx. sub mm layers are attractive (Fig. 1 a). The simulation revealed that
increasing electrode or electrolyte conductivities in parallel is needed to leverage
high capacitance for 1 mm thick layers. (Fig. 1b)
The example shows nicely how the simulation can be employed to obtain an integral
picture and identify bottlenecks in the electrode design.
a) b)
60000 60000
= 0.0521 S m-1,
CIdeal  = 0.077 S m-1
Ceff for: = 0.1 S m-1,
 = 10 s  = 0.766 S m-1
40000  = 1000 s 40000 = 0.0521 S m-1,
 = 10000 s  = 0.766 S m-1
= 0.1 S m-1,
C/F
C/ F

 = 0.077 S m-1

20000 20000

0 0
0 250 500 750 1000 0 250 500 750 1000

Le / µm Le / µm

Figure 1 a) Maximum Capacitance as line, effective capacitance at different time constants for optimized solid
electrode and ionic conductivities in bars, as well as. b) Comparison between optimized and standard values for
the conductivities at a time constant of τ = 1000 s.

[1] M. Zeiger, T. Ariyanto, B. Krüner, S. Fleischmann, N. J. Peter, B. J. Etzold, V. Presser, Journal

of Materials Chemistry A, 2016.
[2] T. Ariyanto, B. Dyatkin, G.-R. Zhang, A. Kern, Y. Gogotsi, B. J. M. Etzold, Microporous and
Mesoporous Materials, 2015, 218, 130-136. DOI:
http://dx.doi.org/10.1016/j.micromeso.2015.07.007
[3] P. Liu, M. Verbrugge, S. Soukiazian, Journal of Power Sources, 2006, 156 (2), 712-718.
[4] M. Kroupa, G. J. Offer, J. Kosek, Journal of The Electrochemical Society, 2016, 163 (10),
A2475-A2487.
 Assessing catalytic activity of oxygen reduction catalysts at high
current densities

Nicolai Schmitt, Gui-Rong Zhang, Bastian J.M. Etzold

Technische Universität Darmstadt, Ernst-Berl-Institute for Technical Chemistry and

Macromolecular Science, Alarich-Weiss-Straße 8, 64287 Darmstadt

Background
Proton exchange membrane fuel cells (PEMFCs) are predicted to have a great
application potential in future clean energy scenario, but so far cost intensive
platinum-based electrocatalysts with insufficient durability and unsatisfactory oxygen
reduction reaction (ORR) kinetics represent major obstacles for a widespread use of
the technique.[1] In academic research promising catalyst concepts have been
developed. During this development the assessment of the ORR activity is commonly
based on thin-film rotating disk electrode (RDE) techniques. While these half-cell set-
ups allow to study the ORR kinetics at defined potential control and without influence
of the corresponding anode reaction, the activity can only be assessed at low current
densities and not at the operational point of the fuel cell application.[2] In contrary,
single cell tests are close to technical conditions but less defined and the resulting
performance is influenced by several factors and not only the catalytic activity. To
overcome these drawbacks of both systems, in this study the applicability of a half-
cell based on a gas diffusion electrode (GDE) for assessing catalytic activity at high
current densities is studied and compared to classical RDE testing.
Experimental
Half-cell GDE experiments were carried out at ambient temperature in a
commercially available test cell (Flexcell, Gaskatel) with a non-woven carbon paper
(Sigracet 39 BC) as gas diffusion layer (GDL). Catalyst coated GDEs were prepared
by drop casting a specific amount of Pt/C catalyst (HiSPEC-3000, 20 wt.-%, Johnson
Matthey) suspension onto the microporous layer (MPL) side of the GDL. For
determination of the electrochemically active surface area (ECSA) of the catalyst,
cyclic voltammogramms (CVs) were recorded while purging the GDE from the
backside with N2. Linear sweep voltammogramms (LSVs) in oxygen atmosphere
were recorded for determination of ORR specific activity (SA). All potentials in this
work are referred to the RHE scale. HClO4 solutions with different concentrations
ranging from 0.1 to 4 M were used as electrolyte in GDE measurements to assess
the optimum electrolyte concentration.
Results
Catalytic activity assessed in GDE measurements is strongly influenced by the
electrolyte concentration. At low overpotentials, HClO4 concentrations from 0.5 to 4 M
result in similar ORR activity (SA at 0.90 V = 0.25-0.32 mA cm-2Pt), while 0.1 M HClO4
results in lower SA of 0.10 mA cm-2Pt. At higher overpotentials the influence of HClO4
concentration becomes more and more evident (e.g., SA at 0.65 V: 4.00 mA cm-2Pt
for 0.1 M, 20.49 for 0.5 M, 24.05 for 1 M, 36.99 for 2 M and 31.19 for 4 M). A
concentration of 2 M is found as optimum that fulfills the requirement of non-limiting
H+ transport while minimizing the effect of electrolyte impurities, which reduce Pt
activity. The effect of HClO4 concentration on ECSA is less pronounced and values
between 21.0 and 27.4 m2 g-1Pt were determined, which are significantly lower than
those obtained using RDE (91.4 m2 g-1Pt), indicating a low catalyst utilization due to
non-optimized catalyst coating on the GDL. ORR activity obtained from RDE at low
overpotentials is in the same range as for GDE measurements (SA at 0.90 V = 0.40
mA cm-2Pt). However, in contrast to RDE, no diffusion limited current plateau is
observed in GDE measurements and fuel cell relevant current densities up to
~1 A cm-2geo could be achieved.
These results reveal inherent advantages of GDE measurements over the RDE
technique and highlight key challenges in the application of GDEs.
Cat.
Layer GDL
A) B)
0

-200 0
geo
Current / mA cm-2

-5
O2
-400 -10
H+
-15
-20
-600 0.8 0.9 1.0

-800 RDE
GDE
Gas
Electrolyte -1000
Phase 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Potential vs. RHE / V
MPL
Figure 1: A) Schematic illustration of the half-cell GDE setup for assessing ORR activity. B) ORR polarization
-1
curves recorded using RDE in O2 sat. 0.1 M HClO4 at 1600 rpm and GDE in 2 M HClO4. Sweep rate = 20 mV s ;
-2
Catalyst loading = 20 µgPt cm .
[1] C. Cui, L. Gan, H.-H. Li, S.-H. Yu, M. Heggen and P. Strasser, Nano letters 2012,
12, 5885-5889.
[2] P. Strasser, M. Gliech, S. Kuehl and T. J. C. S. R. Moeller, 2018, 47, 715-735.
 Robot assisted ultrasonic spray coating as key towards high
current density fuel cell MEA for catalyst testing

Katharina Jeschonek, TU Darmstadt, Darmstadt/Germany;

Gui-Rong Zhang, TU Darmstadt, Darmstadt/Germany, Bastian JM Etzold,
TU Darmstadt, Darmstadt/Germany

The membrane electrode assembly (MEA) is a key component of low temperature

polymer electrolyte fuel cells and consists of the anode and cathode catalyst layers,
gas diffusion layers and the membrane. The fuel cell performance especially at
technically interesting high current densities is controlled by the complex interplay of
mass transfer and reaction within the MEA.[1] E.g. for the cathode side gaseous
oxygen and liquid water needs to be transported within the pores/voids, as also
protons within the polymer electrolyte and electrons within the solid carbon. Due to
this complex interplay, assessing catalyst performance at high current densities is
often influenced more by the mass transfer phenomena, despite the catalyst activity.
As key step to be able to evaluate catalyst activities at high current densities, the
catalyst layer can be seen and several preparation methods are known (decal,
spraying, painting, …).[2]
Within this study we aim to prepare highly reproducible MEAs allowing to obtain high
current densities, by combining:
 an ultrasonic spray nozzle increasing homogeneity of the catalyst layer,
 a syringe pump for defined slurry dosage and
 an automated CNC robot for homogenous and reproducible spraying.

Experimental
As catalyst a commercial 20% Platinum on Carbon (HiSPEC 3000, Alfa Aesar) was
used for the cathode and anode side. 5 cm2 MEAs were prepared using Nafion
NR211 membranes (Ion Power, NafionTM Store) and 39BC GDLs (Sigracet®). A
slurry was made with catalyst, ultrapure water, isopropyl alcohol and 20 wt% of
Nafion ionomer solution (Sigma-Aldrich). The loading of Ionomer was kept at 30 wt%
(I/C ratio of 0.54). The prepared catalyst ink is sprayed for 20 minutes with a dosing
rate of 60 μl min-1. Additionally, a manual air-brush spraying, commonly employed in
laboratories, was used to prepare reference catalyst layers. The catalyst layers were
directly sprayed on membranes
membrane (3-layer CCM) and the
he final MEA obtained by
b in situ
itu
hot pressing at 80°C and 1 bar. Single cell performance was obtained using
u ing a baltic
Fuel cell
ell system
tem qCF FC25/FC50 type bi-polar
polar plate, constant
on tant MEA fi
fixation
ation pre
pressure
ure
of 1 bar and a fuel cell
ell test
te t station
tation (S
(Scribner
ribner Associates
A o iate 850e system).
system)
tem) The cell was
analyzed
anal ed at ambient pressure and the temperature wa
was adju
adjusted
ted to 80°C, the gases
were set at 80°C (RH 100) and a fixed flow rate of 0.2 L min-1 H2 /O2.

Results and discussion

Despite
De pite employing
emplo ing the same
ame catalyst,
atal t, both spraying
pra ing pro
processes
e
esses
e re
reveal
eal strongly
trongl
different performances
e at high current
urrent den
densities. ies of 900 mW cm-
itie . High power densities
2
and current
rent den itie close to 3000 mA cm-2 are a
densities achievable
hie able with the ultra
ultrasonic
oni and
automated spaying
pa ing process,
pro e , while the manual spraying
pra ing re
results
ults
ult in strongly
strongl
trongl reduced
redu ed
power densities of 500 mW cm-2. Scanning
anning ele
electron
tron mi
microscope
ro cope shows that the
spraying technique shows
hows a strong
trong impact
impa t on the catalyst
atal t layer morpholog
morphology an a
more homogenou
homogenous la
layer
er for the ultra
ultrasonic
oni te
technique.
hnique In conclusion
on lusion it can
an be seen,
een,
that the catalyst
atal t la
layer
er fabri
fabrication
ation te
technique
hnique ha
has a huge influence
influen e on the resulting
re ulting
catalyst
atal t performance
performan e at hi
high
gh current
urrent densities.
den itie . It was
wa further shown that the
combination
ombination of ultra
ultrasonic
onic spra
oni spraying
pra ing with automation gives
gi e ri
rise
e to assess
a e catalyst
atal t
performance
performan e at high current
urrent densities.
den itie .

iR-corrected
iR- orre ted Potential Power Density

1.0 1000
iR-Corrected Potential / V

Power Density / mW/cm2

0.8 800

0.6 600

0.4 400

0.2 200

0 0
0 750 1500 2250 3000

Current density / mA/ m2geo

mA/cm

Figure 1: Scheme illustrating left the fuel cell

ell performance at different spray levels, Airbrush (blue) with Pt loading
2 2
0.27 mg/cm and modified spray
pray sy tem with ultrasonic
system ultra oni (orange) and a Pt loading of 0.17 mg/cm . Test
conditions: 80°C cell at ambient pressure,
pressure H2/O2 80°C (RH100), 0.2L/min flow and right SEM characterization
hara teri ation of
both.

References
[1] J.. Huang, Z. Li, J. Zhang, Frontiers in Energy 2017, 11, 334-364.
364.
[2] V. Mehta, J. S. Cooper, Journal of Power Sources 2003, 114, 32-53.
 Electrochemical and spectroscopic investigations on
heteropolyacids as homogeneous catalysts

Jakob Albert1*, Daniela Lüders1, Matthias Mendt2, Michael Mozer1 and Dorothea
Voß1
1 Lehrstuhl für Chemische Reaktionstechnik, Friedrich-Alexander-Universität
Erlangen-Nürnberg, Egerlandstr. 3, 91058 Erlangen, Germany; *jakob.albert@fau.de
2 Felix-Bloch-Institut für Festkörperphysik, Universität Leipzig, Linnéstraße 5,
04103 Leipzig, Germany

Our contribution investigates the formation of various catalytically active vanadium

species for different glucose transformation reactions. Therefore, we have
synthesized a series of different heteropolyacids of the general type H3+n [PVnMo12-
nO40] (n=0-6) and applied them in homogeneous glucose transformation reactions in
aqueous media.
51
By applying both V-NMR (nuclear magnetic resonance) and continuous wave EPR
(electron paramagnetic resonance) spectroscopy, we were able to identify the
different vanadium species that catalyse glucose transformation to several organic
acids in aqueous solution depending on the reaction atmosphere and type of
vanadium precursor.
The higher V-substitute complexes (n= 2-6) showed far better activities than the
lower V-substituted complexes (n= 0-1). To explain this trend, the best system, HPA-
5, was compared to the lowest V-substituted system of good activity, HPA-2, using
different optical and electrochemical methods.
As the most important result of the spectroelectrochemical investigations the
formation of the pervanadyl species was only discernable for the higher V-substituted
species HPA-5 under oxidative conditions. According to our mechanistic
interpretation this species is responsible for the observed enhanced catalytic activity.
Moreover, our results suggest that substituted V5+ species are the predominantly
catalytic active species in the production of formic acid.
Using anaerobic conditions (20 bar nitrogen atmosphere), we could show that
different vanadium species are formed depending on the nature of the precursor.
Hereby, paramagnetic acid-bound vanadyl species formed from the VOSO4 and
NH4VO3 as well as the HPA-5 precursor seem to be predominantly responsible for
lactic acid formation from glucose under anaerobic conditions.
As such, we have shed new light onto the mechanism of the POM catalysed
oxidation of biomass and have linked different catalytic activities to the vanadium
content in catalytic POM complexes.

References:
1 J. Albert, D. Lüders, A. Bösmann, D. M. Guldi, P. Wasserscheid, “Spectroscopic and
electrochemical characterization of heteropoly acids for their optimized application in
selective biomass oxidation to formic acid”, Green Chemistry, 2014, 16 (1), 226-237.
2. J. Albert, M. Mendt, M. Mozer, D. Voß, “Investigations on the role of vanadium in
homogeneous biomass transformation reactions using NMR and EPR spectroscopy”,
Applied Catalysis A: General, 2018, 570, 262-270.
 Development of Gas Diffusion Electrodes for the non-aqueous
Electrochemical CO2 Reduction to Oxalic Acid

M. König1,2, D. Pant2, E. Klemm1

1
University of Stuttgart – Stuttgart, Germany,
2
Flemish Institute for Technological Research (VITO) – Mol, Belgium

Introduction
The electrochemical CO2 reduction is increasingly getting attention as a means to
store energy chemically (e.g. through methane, formate) and to produce value-added
chemicals (e.g. CO, methanol, oxalic acid) from CO2 waste streams. One challenge
in the electrochemical reduction of carbon dioxide is the relatively low solubility of
CO2 in water of c≈33 mmol·L-1. The low local concentration of CO2 reduces the
achievable current densities of the reaction due to a mass transfer limitation using
conventional electrodes. Once the limiting current density ilimit is exceeded, the
observed side reaction is the water reduction in aqueous electrolytes (hydrogen
evolution reaction, HER). Several possibilities have been proposed to increase ilimit.
This includes the electrochemical reduction at high pressures, the use of alternative
solvents and the application of gas diffusion electrodes (GDEs). GDEs are highly
porous three-dimensional electrodes, in which a three-phase boundary, consisting of
the solid electrode (catalyst and support), the liquid electrolyte and a gas phase, is
formed during the electrochemical reaction [1]. As opposed to submerged electrodes,
porous gas diffusion electrodes (GDEs) allow for the formation of the interfacial area
between liquid and gas within the material of the electrode and thus can largely
reduce mass transfer limitations and enhance the corresponding current densities [2].
While GDEs are already commercially applied (PEM fuel cells, chloralkali process)
and are commonly applied in the electrochemical CO2 reduction in aqueous
media [3], there is still need for research exploring applications in non-aqueous
solvents.

Electrochemical CO2 reduction in non-aqueous media

While water is a favorable reaction medium in many aspects, the use of organic
solvents has several advantages. With the application of organic solvents, the
solubility of CO2 can be increased drastically (ca. 5-fold for methanol, 10-fold for
acetonitrile). In addition, the production of alternative, value-added reduction
products such as oxalic acid (compare figure 1) are possible. In aprotic solvents, a
direct C-C coupling through the dimerization of CO2 radical anions are accessible [4].
Many organic solvents are less susceptible to a cathodic reduction compared to
water, which provides a larger potential window while avoiding the, in aqueous
electrolytes competing, HER.

Figure 1: Proposed reaction mechanism for the formation of oxalate in aprotic solvents [4].

Challenges for the application of GDEs in non-aqueous media

- Investigation into the effect of different organic solvents on the catalyst activity,
product selectivity.
- Screening of organic solvents based on their conductivity, CO2 solubility,
toxicity, viscosity.
- Adjustment of wetting properties of GDEs (hydrophobicity, wettability, porosity)
for specific solvent requirements to ensure a stable three-phase boundary
during the reaction to facilitate an ideal mass transport for carbon dioxide.
- Development of a compatible anode oxidation reaction.

Sources:
[1] Y. Alvarez-Gallego et al., “Development of gas diffusion electrodes for cogeneration of
chemicals and electricity,” Electrochim. Acta, vol. 82, pp. 415–426, 2012.
[2] D. Kopljar, A. Inan, P. Vindayer, N. Wagner, and E. Klemm, “Electrochemical
reduction of CO2 to formate at high current density using gas diffusion electrodes,” J.
Appl. Electrochem., vol. 44, no. 10, pp. 1107–1116, 2014.
[3] S. Bajracharya, K. Vanbroekhoven, C. J. N. Buisman, D. Pant, and D. P. B. T. B. Strik,
“Application of gas diffusion biocathode in microbial electrosynthesis from carbon
dioxide,” Environ. Sci. Pollut. Res., vol. 23, no. 22, pp. 22292–22308, 2016.
[4] V. U. Kaiser and E. Heitz, “Zum Mechanismus der elektrochemischen Dimerisierung
von CO2 zur Oxalsaeure,” Berichte der Bunsen-Gesellschaft, vol. 77, no. 10/11, pp.
818–823, 1973.
Silver-based gas diffusion electrodes for oxygen reduction reaction
in alkaline electrolyte: Influence of PTFE content on pore system
and electrochemical performance

David Franzen, TU Clausthal, Barbara Ellendorff, TU Clausthal, Melanie C. Paulisch,

Helmholtz-Zentrum Berlin, Ingo Manke, Helmholtz-Zentrum Berlin,
Thomas Turek, TU Clausthal
Introduction
Gas diffusion electrodes (GDE) are an essential part of various electrochemical
processes. Particularly noteworthy are energy conversion systems such as fuel cells
or electrolysis processes, e.g. chlor-alkali electrolysis. In many cases the GDE is the
limiting component and thus the biggest cost factor. In order to optimize GDE, a
general understanding of the complex overall system including the transport and
reaction processes is necessary in order to maximize the electrocatalyst utilization.

Gas diffusion electrodes are complex functional materials with a wide range of
requirements. Within the GDE, a three-phase interface must be formed at which
gaseous and liquid reactants are electrochemically converted on a solid catalyst. This
requires a complex pore structure with hydrophilic and hydrophobic areas in order to
achieve the best possible wetting with the electrolyte, but at the same time to prevent
complete flooding of the electrode.

Setup and Results

In the present work silver-based GDE are produced by means of a spray process [1]
and characterized by physical and electrochemical methods. Systematic variation of
the PTFE content influences the pore system of the produced electrodes. The
resulting pore system is analyzed using various measuring methods, such as
capillary flow porometry, helium pycnometry and BET surface area measurements.
The obtained results are supported by imaging procedures, such as FIB/SEM and the
resulting reconstruction analysis. All techniques combined offer a clear view of the
inside of the electrodes and show the influence of the PTFE content on the physical
properties.

The electrochemical performance is determined under stationary conditions in half

cell experiments using linear sweep voltammetry. Particular importance is set on the
determination of the electrochemical kinetics and signs of transport limitation.
 10 -1
9 PTFE -0.9
content
8 -0.8
2%
Diff. pore flow / %

7 8% -0.7
6 10 % -0.6

η/V
5 -0.5
4 -0.4
PTFE
3 -0.3 content
2 -0.2 2%
8%
1 -0.1 10%
0 0
0.05 0.1 0.2 0.5 1 2 5 0 1 2 3 4 5 6
Pore diameter / µm current density / kA m-2

Fig. 1: Examples of capillary flow pore size distribution (left) and polarization curves
(right) due to varied PTFE content.
Selected electrodes are also examined in a specially designed half-cell under various
pressure conditions to determine effects of different electrolyte intrusions.

The presented contribution shows how physical measurement methods characterize

the inner pore structure of GDE and represents the relation between the inner
structure and the resulting electrochemical performance.

[1] I. Moussallem, S. Pinnow, N. Wagner et al. (2012) Development of high-

performance silver-based gas-diffusion electrodes for chlor-alkali electrolysis
with oxygen depolarized cathodes. Chemical Engineering and Processing:
Process Intensification 52: 125–131. doi: 10.1016/j.cep.2011.11.003
 eForFuel – Acidic CO2-Electrolysis to Formic Acid for Microbial
Conversion

M. Stoll, A. Löwe, E. Klemm, University of Stuttgart, Germany

Introduction
Reducing CO2 electrochemically with high faraday efficiencies and current densities
towards formate/formic acid is possible when using gas diffusion electrodes (GDEs)
[1-3]
with highly dispersed and active Sn-particles as catalyst . Usually, the electrolysis
is operated in aqueous and alkaline electrolytes, leading to the formation of formate
salts. However, the market for formate is rather small, which is why formate is usually
considered as energy storage chemical. Due to this fact, the European funded
project eForFuel aims to switch the typical operation conditions to acidic pH-values
[4]
and produce formic acid . Ultimately, we want to couple CO2-electrolysis with
fermentation of formic acid by formatotrophic bacteria. During the fermentation
process both formate and protons are consumed equally, thereby the production of
undissociated formic acid is essential. The target products of the fermentation are
propane and isobutene, which can be used as fuels, contributing to a fossil-free and
instead CO2-based economy (see figure 1) [5].

Figure 1: eForFuel strategy for the production of fuels from H2O, CO2 and electricity.

Challenges for acidic electrolysis

In principle cathodic CO2 reduction combined with anodic water splitting is a proton-
balanced process:
Cathode: CO2 + H+ + 2 e- → HCOOH E0 = - 0.08 V (vs. SHE) at pH = 0
Anode H2O → 2 H+ + ½ O2 + 2 e- E0 = 1.23 V (vs. SHE) at pH = 0
Instead, a pH drop on the cathode and a pH rise on the anode side is observed
during electrolysis. The underlying problem here is that high concentrations of
potassium salts are used as conductive salts. Due to 10 to 100 times higher
concentrations and larger ionic radii, the transfer of potassium cations is actually
preferred to the proton transfer through the ion exchange membrane, which
separates cathode and anode. We want to solve this problem by adapting our
electrolyzer design and testing different types of separators like diaphragms, bipolar
membranes or membrane-electrode-assemblies.
When coupling electrolysis with fermentation it will be necessary to use non-toxic
electrolytes. Sulfates or phosphates will be tolerable for the microbes. Nevertheless
the salt load should be reduced as much as possible, to not add additional stress on
the cells. To encounter the lower conductivity of sulfates and phosphates the reactor
geometry will be optimized to reduce ohmic losses throughout the cell.
According to Hori the formation of the radical anion CO2 species has such a negative
potential that the reduction step is not pH-dependent, while the standard potential of
the hydrogen evolution reaction, the most prevalent side reaction, is getting less
[6]
negative with falling pH according to the Nernst-equation . Nevertheless, we
believe that by finely tuning the pH-range of the process we can achieve high
selectivities while still maintaining acceptable current densities.

The authors would like to thank the European Union for the funding from the Horizon
2020 research and innovation programme under grant agreement No 763911.

Literature:
[1] D. Kopljar, N. Wagner, E. Klemm, Chem. Eng. Technol., 39 (11), 2016, p. 2042-
2050.
[2] D. Kopljar, A. Inan, P. Vindayer, N. Wagner, E. Klemm, J. Appl. Electrochem., 44
(10), 2014, p. 1107-1116
[3] D. Kopljar, A. Inan, P. Vindayer, R. Scholz, N. Frangos, N. Wagner, E. Klemm,
Chem. Ing. Techn., 87 (6), 2015, p. 855-859
[4] eforfuel.eu
[5] O. Yishai, S. N Lindner, J. G. de la Cruz, H. Tenenboim, A. Bar-Even, Curr. Opin.
Chem. Biol., 2016, 35: 1-9
[6] Hori Y. (2008) In: Vayenas C.G., White R.E., Gamboa-Aldeco M.E. (eds) Modern
Aspects of Electrochemistry. vol 42. Springer, New York, NY
 Molecular Electroreduction of CO2 to Formate

P. Rößner, E. Klemm,

University of Stuttgart, Institute of Chemical Technology, Stuttgart/Germany

Introduction - Why are chemical energy storage solutions important?

Storing energy is one of great technological challenges of the future. An increasing
share of renewable energies and a strong development of the mobility sector towards
electrification means that storage capacities have to keep up with the demand.
Power-to-X processes are a key technology to store electricity and have experienced
great development over the last years. Here we present a Power-to-Chemical
process with formate as target molecule. Formate is the salt of formic acid which is
formed under the given basic pH conditions, it is non-toxic and can be easily stored
as aqueous solution. The feedstock CO2 is used as a C1 building block and
advantageously combined to serve as a vector to store the hydrogen that the CO2
reacts with towards formate as well as the electric energy that drives the chemical
reaction. Subsequent decomposition of formate allows for recovery of the stored
energy via hydrogen fuel cell or the formate is used to drive a direct formate fuel cell.
The technology could be used to stabilize the grid by balancing the demand and
production of energy market participants, e.g. by buffering peak inputs from
renewables or shave peak demand of industrial participants. A flexible storage
solution would be applicable in distributed off-grid systems as well as in stationary
systems within the energy-, home storage-, mobility- and (chemical-) industry-sector.
With formate as energy vector these applications/sectors could be
coupled/connected by transporting the formate in already existing infrastructure due
to its liquid nature.

How can we store energy in Formate?

The most common approach is the use of metal particles as catalyst which, mostly
Sn, to reduce CO2 electrochemically. The catalyst allows for high current densities
[1]
and faradaic efficiencies but due to the relatively high overpotential the energy
efficiency of the overall process is limited (below 50%). This could be improved by
applying highly active and selective metal complexes. The well defined structures
and properties of homogeneous catalysts allow for targeted optimization of the metal-
ligand en
ensemble
emble toward
towards a specific
spe
pe ifi rea
reaction
tion that re
result
ult in a lower overpotential
o erpotential of the
CO2 reduction reaction
on and hen
hence
e a better energ
energy efficiency
effi ien of the pro
process.
e . Howe
However
er
the u
use
e of homogeneou
homogeneous catalysts
catal
atal t in the ele
electrochemical
tro hemi al reduction
redu tion of CO2 is little
[2]
known
nown and the re
research
ear h is only
onl at the beginning . The system
tem has to be balanced
balan ed
and optimi
optimized
ed between all rea
reaction
tion partner
partners,, the catalyst,
atal t, the substrate
ubstrate CO2 and the
productt formate to work
produ wor properl
properly..

Figure 1 Process flow scheme of a Micro Flow

Figure 1 shows
how the Electrochemi
Ele trochemical
hemealofCell
flow scheme a (MFEC)
Mi ro for
Micro ele
electroreduction
Flow troredu
Ele trotionhemi
of CO2al
Electrochemical
hemical . Cell comprising
ompri ing all
[3]
key
e feature
features of the system
stem, whi
which
h iis ba
based
ed on preliminary
preliminar experiment
experiments . Future
challenges
hallenge in
include,
lude, amongst others,
other , the ele
electrochemical
tro hemi al rea
reaction
tion engineering of the
process
pro e and in a ne
nextt step
tep the immobilization
immobili ation of the catalyst.
atal t.
In the pre
presented
ented proje
projectt a steep
teep learning curve
ur e is
i expected
e pe ted and important knowledge
nowledge
will be gained whether mole
molecular
ular catalysts
atal t are a viable
iable option to impro
improve
e future
energy storage
energ torage te
technologies.
hnologies.

[1] D. Kopljar, N. Wagner,, E. Klemm, Chem. Eng. Technol., 39 (11), 2016,

2016 p. 2042-2050
[2] R. Fran
Francke,
e, B. Schille,
S hille, M. Roemelt, Chemical Reviews, 2018
[3] S.-F.
F. H
Hsu,
u, S. Rommel, P. E
Eversfield,
er field, K. Muller, E. Klemm, W. R. Thiel, B. Plietker,
Pliet er,
Angew. Chem. Int.,, 53, 2014, p. 7074-7078
 Feasibility of demand response in the chemical industry on the
example of electrochemical synthesis of Adiponitrile

N. Milojević, M. Neumann, R. Schomäcker

Technische Universität Berlin,
Department of Chemistry, Strasse des 17. Juni 124, D-10623 Berlin

Abstract
In the field of power generation, the aim is to increase the part of renewable energy.
This also brings an increase of fluctuations in power supply, which leads to a higher
need of adaptability, meaning more flexibility in production and consumption of
electricity. Load changes in energy-intensive industries like chemical industry would
be a way to provide this. In the joint project ChemEFlex the feasibility of demand
response in Chlor-Alkali-Electrolysis (CAE) as well as in other electrochemical
processes of the chemical industry is analysed. In this work, to find a process other
then CAE, suitable operating parameters and their tolerable limits for electrochemical
processes were evaluated. From a preliminary selection of piloted and/or
[1]
commercialised processes , the electrohydrodimerization of Acrylonitrile (ACN) to
Adiponitrile (ADN) was considered most suitable.

+ 2 e- + ACN CN + 2 H+ CN
CN CN NC NC
ACN ADN
Dimerization

Fig. 1: Electrohydrodimerization of Acrylonitrile to Adiponitrile.

Adiponitrile is an intermediate in the production of Nylon. Worldwide the production

rate of ADN is around 1.31 Mio. t/a, of which 300.000 t are made through cathodic
hydrodimerization. This makes the so called Monsanto-Process the most important
electroorganical synthesis. An advantage of this process is, that it is not in need of a
membrane, which makes it very attractive for demand response because this
bottleneck in flexibility options has not to be considered.
 [2]
An experimental plant was built in laboratory scale to test the application of
demand-side management in Adiponitrile synthesis. The changes in the selected
parameters like aging oft the electrodes, product quality etc. are documented and
evaluated while three temporal flexibility profiles (load changes in hours, days or
weeks) are applied. With this knowledge the potential for flexibility in the
electrochemical hydrodimerization of Acrylonitrile can be determined.

Experimental section

Experiments were carried out in a Microflowcell by ElectroCell AB (Sweden) with Cd

foil on steel plate as cathode and a low carbon steel anode, arranged in a plate-and-
frame-manner with polypropylene frames and epdm-gaskets. The experiments were
performed at 55°C temperature. The aqueous electrolyte is in an emulsion system
with the organic reactant Acrylonitrile. The mixing is provided through static mixers
before entering the electrolysis cell plus turbulent flow rates in the cell. To analyse
the conversion of Acrylonitrile to Adiponitrile and other possible byproducts samples
of the emulsion were taken after leaving the Microflowcell. Without mixing the
emulsion turned into a two-phase system, so that the organic phase could easily be
separated and analysed by gaschromatography.

References
[1] C. A. C. Sequeira, D. M. F. Santos, J. Braz. Chem. Soc. 20, 3 (2009) 387–406.
[2] K. Scott, B. Hayati, Chem. Eng. Sci. 45, 8 (1990) 2341–2347.
Poster Abstracts
In-Situ Monitoring
 Model-based Scale-up Predictions:
From Micro- to Millireactors using Inline FT-IR Measurements

V. Fath1,2, S. Szmais3, P. Lau3, P. Weller4, N. Kockmann1, T. Röder2

1
Department of Biochemical and Chemical Engineering, Equipment Design/TU
Dortmund University, Dortmund/Germany;
2
Institute of Chemical Process Engineering/Mannheim University of Applied
Sciences, Mannheim/Germany;
3
Merck KGaA, Darmstadt/Germany;
4
Institute of Instrumental Analytics and Bioanalysis/Mannheim University of Applied
Sciences, Mannheim/Germany;

Scale-up predictions from lab to pilot or production scale are important but not trivial.
A model-based approach relating to previous lab experiments can overcome the
necessity of time-consuming measurements on pilot or production scale with better
understanding of the chemical process. Experiments on laboratory scale can usually
be carried out under nearly ideal conditions, especially when using micro-structured
devices with rapid mixing and excellent temperature control. Particularly in the case
of fast and exothermic reactions, the transfer to larger equipment scale requires good
knowledge of the kinetic model and reactor characteristics.

In this work, complete process development for a highly exothermic organometallic

model reaction is presented. Kinetic studies on lab-scale provide the basis for a
systematic scale-up approach. In preliminary experiments, the industry-relevant
synthesis of a lithiated intermediate through the deprotonation of a CH-acidic
hydrocarbon compound is carried out in a coiled capillary stainless steel
microreactor, aiming to receive reliable kinetic data. The lab-scale reactor
characteristics justify the assumption of an ideal, nearly isothermal plug flow reactor
behavior (high Bodenstein numbers, negligible hot spot generation at the entrance of
the reactor). Therefore, it can be ensured that the kinetic parameters are obtained
independent of complex physical processes such as formation of hot spots and back-
mixing.
An in-situ reaction monitoring through inline FT-IR spectroscopy is used within the
microreactor setup, since analysis of highly reactive, not isolable lithiated
components is highly challenging. Based on turnover-residence time curves at
different reaction temperatures, an appropriate kinetic model could be found,
illuminating the reaction mechanism.

In a following step, the scale-up from the microreactor (inner diameter 0.5 mm) to a
milli-scale pilot reactor (inner diameter of 2 mm) by increasing the channel diameter
and the flow rates is investigated. Now, the efficiency in heat transfer and the
formation of hot spots have to be considered. Moreover, the mixing performance and
the residence time distribution are strongly influenced. Ideal conditions can no longer
be assumed. Therefore, a model based prediction of the mixing dependence, a
possible hot spot generation and the residence time distribution become essential.

A complete process development for the transfer of an organometallic model reaction

from lab to pilot scale is finally carried out on the basis of the detailed understanding
of the reactor characteristics including heat and mass balances and kinetic studies.
 Non-invasive sensors and analysis techniques for two-phase flow
in capillaries
W. Krieger1, L. Kaiser1, M. Hörbelt1, A.C. Kufner1, C. Tewes1, J. Muckermann1,
G. Wiese2, S. zur Horst-Meyer2, N. Kockmann1
1
Laboratory of Equipment Design, TU Dortmund University, Germany
2
SONOTEC Ultraschallsensorik GmbH, Germany

Implementation of sensors and measurement techniques in microreactors is a

challenging task since disturbances of flow lead to deviations in the desired flow
behavior. Particularly in two phase flow, the sensitivity towards flow disturbances
increases considerably. Crystallization and gas-liquid reactions are examples of
important two-phase flow systems in process engineering that are investigated in
micro-scale equipment. In order to transfer these processes to larger scales non-
invasive online measurement techniques are required for i) responsive process
control and ii) fundamental understanding of underlying phenomena. In this work, a
responsive and non-invasive ultrasonic sensor is utilized in order to monitor a
crystallization process by measuring the weight fraction in the outlet. Its accuracy and
applicability for crystallization are discussed and evaluated. A colorimetric technique
is applied to investigate gas-liquid Taylor flow in coiled capillaries on a fundamental
level by resolving local concentration profiles.

In present research Taylor flow is often utilized in coiled capillaries although the
occurring flow phenomena are not fully understood. The superposition of
characteristic Taylor and Dean vortices leads to a complex flow behavior that is
visualized and evaluated with the colorimetric technique. This technique is based on
image processing and the consecutive oxidation of leuco-indigo carmine [1], which
undergoes two distinct color changes enabling the analysis of local mass transfer
and selectivity. By employing open-source hardware the temporal resolution is
increased and the entire life time of a slug can be analyzed providing meaningful
data for the development of models and numerical simulations. Overall, this work
introduces non-invasive measurement techniques for process control and contributes
to the fundamental understanding of gas-liquid Taylor flow in coiled capillaries, which
are important aspects for the transfer of micro process engineering into industry.
[1] W. Krieger, J. Lamsfuß, W. Zhang, N. Kockmann, Chem. Eng. Technol. 2017,
40 (11), 2134-2143.
 Vergleich zwischen einem wellendurchmischten und einem
gerührten Bioreaktor hinsichtlich der Partikelbeanspruchung in
einem Flüssig/flüssig-Modellstoffsystem

Robert P. Panckow1, Chrysoula Bliatsiou1, Lutz Böhm1, Matthias Kraume1

1
Technische Universität Berlin, FG Verfahrenstechnik, Berlin, Deutschland

Durch die hohen mechanischen Energieeinträge zum Erzielen eines schnellen

Wärme- und Stoffaustauschs kann eine vorliegende Dispersphase geschädigt
werden, wobei bioverfahrenstechnisch Zellen und Zellagglomerate von Interesse
sind. Diese fluidmechanische Partikelbeanspruchung wird in dieser Studie anhand
eines Modellstoffsystems mit flüssiger Dispersphase [1] charakterisiert.

Experimenteller Aufbau und Methodik

Die Untersuchungen wurden vergleichend in einem wellendurchmischten Single-Use
Bioreaktor (CELL-tainer® 20L, Fa. Celltainer Biotech BV) und in einem DN160
Rührkessel mit Klöpperboden durchgeführt, siehe Abb. 1.

Abb. 1: Bewegungsform CELL-tainer® 20L (links), Aufzeichnung der Tropfengrößen (Mitte), DN160
Rührkessel mit Klöpperboden (rechts)

Durch Variation von Arbeitsvolumen V, Rotationsfrequenz k und Anstellwinkel φ

(CELL-tainer) sowie von Rührorgan und dessen Drehfrequenz n (Rührkessel)
wurden mittels fotooptischer Partikelmesstechnik der SOPAT GmbH [2] die
Partikelgrößen der Dispersphase in-situ aufgezeichnet, siehe Abb. 1 (Mitte). Die
Vermessung der zweidimensionalen Rohbilddaten durch automatisierte Bildanalyse,
gestützt durch neuronale Netze, lieferte die Tropfengrößenverteilung. Deren zeitliche
Zerstörungskinetik für verschiedene Betriebspunkte beider Reaktoren generiert neue
Erkenntnisse zur Übertragbarkeit der beiden Reaktortypen.

Literatur
[1] Wollny S, Sperling R, (2007). Partikelbeanspruchung in gerührten Behältern. Chem. Ing.
Tech. 79 (3) 199–208
[2] Maaß et al. (2012). Automated Drop Detection Using Image Analysis for Online Particle
Size Monitoring in Multiphase Systems. Comput. Chem. Eng. 45 27–37.
 In situ studies on the preparation, stability and application of well-
defined isolated Co nanoparticles supported on exfoliated graphite

Moritz Wolf, Nico Fischer, Michael Claeys, Catalysis Institute and DST-NRF Centre
of Excellence in Catalysis c*change, University of Cape Town, South Africa

For a long time, most support materials have been regarded as inert. The potential
presence of metal-support interaction anchoring metallic nanoparticles on common
metal oxide carriers such as Al2O3 or SiO2 was established in literature in the 1980s
[1]. More recently, such metal oxide carriers have been shown to exhibit a strong
effect on the catalytic behaviour of supported metallic nanoparticles [2]. In contrast to
metal oxides, pristine carbon (unless functionalised) does not exhibit significant
stabilisation of nanoparticles in heterogeneous catalysts. This inert character makes
pristine carbon the carrier of choice for fundamental studies on relatively isolated
nanoparticles, but the limited thermal stability typically results in sintering during
activation.
Herein, pristine graphite powder has been exfoliated via ultrasonication in 1-methyl-
2-pyrrolidinone [3] yielding exfoliated graphite (EG). This inert support material was
utilised in a comparative in situ XRD study on the size-dependent reduction
behaviour of cobalt oxide in H2. At first, EG was decorated with separately
synthesised, well-defined Co3O4 nanoparticles in the range of 3-8 nm [4]. However,
sintering of a significant fraction of nanoparticles was identified for a Co loading of 5
wt.% in all catalysts during reduction to CoO and, more pronounced, in the second
reduction step to fcc-Co. Even though sintering induced a widening of the initially
narrow size distribution, a mild size-dependent reduction behaviour was identified. In
a second reduction series, synchrotron radiation-based in situ XRD and in situ
magnetometry revealed the absence of sintering in 1 wt.% Co/EG model catalysts
demonstrating the successful preparation of well-defined metallic Co nanoparticles
on an inert support.
The newly developed model catalyst was then applied in a fundamental study on the
H2O-induced deactivation behaviour of Co-based Fischer-Tropsch (FT) catalysts. A 1
wt.% Co/EG catalyst with well-defined nanoparticles (average size: 6 nm) was
reduced in H2 and exposed to simulated high conversion FT environment with
incrementally increasing partial pressures of H2O in an in situ magnetometer. H2O is
a main product of the FT synthesis and generally accepted to induce deactivation of
nano-sized supported Co catalysts
catal t [[5,6]. An inter-connection
onne tion between hydrothermal
h drothermal
sintering
intering and o
oxidation
idation of C
Co
o nanoparti
nanoparticles
le to cobalt
obalt oxide
o ide has been h
hypothesised
pothe i ed
[6]. In our study, utilisation
ation of a carbonaceous
arbona eou support
upport allow
allows for the iisolation
olation of said
aid
oxidation
o idation pro
process
e pre
preventing
enting an underlying
underl ing formation of cobalt-support
obalt support compounds.
ompound .
A rapid o
oxidation
idation of the cobal
cobaltt pha
phase
e was
wa observed
ob er ed under simulated high FT
conversion
on er ion le
levels.
el . Surprisingly,
Surprisingl , the oxidised
o idi ed cobalt
obalt re-reduced
re redu ed due to an in
increase
rea e in
the crystallite size via hydrothermal sintering
intering in its oxidised phase.
phase Capturing this
inter-connection
onne tion between water-induced
water indu ed o
oxidation
idation and subsequent
ub equent re
re-reduction of
the sintered crystallites in situ repre
represents
ent a fir
firstt in re
research
ear h on deactivation
deacti ation of cobalt-
obalt
based FT catalysts. Further, the re-reduction of sintered
intered nanoparticles
nanoparticle once again
exhibits the identified size--dependent stability of Co again
againstt oxidation to cobalt(II)
obalt(II)
oxide [7,8].

Figure 1 Magnetisation, corresponding

corre ponding to the amount of metallic
metalli fcc-Co
f Co with an initial average
a erage
size
i e of 6 nm (top), relative to the magnetisation after reduction and weight fraction
fra tion of
material di
displaying
playing remnant magnetisation
magneti ation ((crystallites
r tallite larger than critical
riti al diameter for
superparamagneti
uperparamagnetism; m; bottom) of the Co/C model catalyst
atal t o
over
er time on stream
tream during
simulated
imulated high F Fischer-Tropsch conversion.
on er ion. Inserts
In ert show
how schemati
schematics of supported
upported
particles
parti le (grey: cobalt, red: oxygen,
o gen, blablack:: exfoliated
e foliated graphite support):
upport a) after
reduction,
redu tion, b) surface
surfa e modified during Fischer-Tropsch
F synthe i at moderate
synthesis
conversion
on er ion levels
levels, c) oxidised, d) sintered and re-reduced.

References
[1] S.
S.J.. Tau
Tauster,
ter, S.C. Fung, R.T.K. Baker,
Ba er, J.A.
.A. Horsley,
Hor le , Science 21 (1981) 1121.
[2] S. Lögdberg, M. Boutonnet, et int.,
int E.A. Blekkan, Appl. Catal. A Gen. 393 (2011) 109.
[3] Y. Hernandez, V. Nicolosi, et int.,
int J.N. Coleman, Nat. Nanotechnol. 3 (2008) 563.
[4] M. Wolf, N. Fischer, M. Claeys, Mater. Chem. Phys. 213 (2018) 305.
[5] M. Wolf, B.K. Mutuma, N.J. Coville, N. Fischer, M. Claeys, ACS Catal. 8 (2018) 3985.
[6] M. Sadeqzadeh, J. Hong, et int., A.Y. Khodakov, Ind. Eng. Chem. Res. 51 (2012) 11955.
[7] E. van Steen, M. Claeys, et int., J.L. Visagie, J. Phys. Chem. B. 109 (2005) 3575.
[8] M. Wolf, H. Kotzé, N. Fischer, M. Claeys, Faraday Discuss. 197 (2017) 243.
Poster Abstracts
Kinetics
 Investigation of gas transport through PECVD-SiO2 protection
layers
F. Knaus1, F. Utzmann1,2, P. Michaelis1, F. Eder2, A. Drochner1, B. J. M. Etzold1
1
Technische Universität Darmstadt, Ernst-Berl-Institut für Technische und
Makromolekulare Chemie, Alarich-Weiss-Straße 8, 64287 Darmstadt, Germany
2
Siemens AG; Corporate Technology, Research in Energy and Electronics, Polymers
(CT REE MDM POL-DE), Günther-Scharowsky-Str. 1, 91058 Erlangen, Germany

Motivation
Circuit paths, (solder) connections and electronic components of printed circuit board
assemblies (PCBAs) are sensitive to the corrosive influences of harsh environmental
conditions. Especially to ensure functionality in an ambience of damp heat and
corrosive gases (e.g. in industrial atmosphere) PCBAs need to be protected by a
coating. Silica-based films deposited by low-pressure plasma polymerization are
studied as alternative to common solvent-based polymer varnishing. For a better
fundamental based understanding how the synthesis conditions influence the
protective properties of PECVD-SiO2 layers, the gas transport through these films is
studied.

Investigation of gas transport through protection films

The investigation of the gas transport through silica-based plasma polymers is
realized by a modified W ICKE-KALLENBACH-cell1. Challenge is the high accuracy
needed as naturally only a minimal gas transport takes place through these
protective coatings. Thus, a high surface area between the separated chambers as
also minimal dead volume needs to be realized. To be able to study the nanoscale
films, these were further deposited on polymer films as substrate. An online QMS is
used for analytics, that allows to determine low diffusion fluxes through the specific
design of the measuring cell (Fig. 1B).
A) B) A A+B

B B+A

Figure 1: A) Schematic of a W ICKE-K

- ALLENBACH-experiment for thin film prote
protection
tion layers.
layers B) CAD model of the
used measuring cell.

Results
First,
ir t, the ga
gas tran
transport
port through commercially
ommer iall aavailable
ailable pol
polymer
mer foils as
a substrate
ub trate was
wa
investigated.. Mo
Mostt suitable
uitable for the measurements
mea urement is
i a di
di-acetate foil with a diffusion
flux of = 10-5 mol m-2 s-1
-
(for = 30 µm). Moreo
Moreover,
er, the inversel
inversely proportional
behavior
beha ior of la
layer
er thickness
thi ness and diffu
diffusion
ion flu
flux (according
(a ording to FICK’s first law) was
verified by using di-acetate
acetate
a etate foil
foils with different la
layer
er thickne
thicknesses.
thi ne e . Different
measurements
mea urement of coated
oated film
films show
how a dependen
dependency of depo
deposition
ition time and diffusion
diffu ion
flux, what shows
how the potential of the setup
etup to e
examine
amine different PEC
PECVD coatings. The
lowest currently
ntl detected
dete ted diffu
diffusion
ion flu
flux is = 3·10-6 mol m-2 s-1.
These permeabilit
permeability measurement
measurements offer the opportunit
opportunity to check
heck the quality
qualit of the
investigated
n e tigated thin film material.

References
(1) Wi
Wicke,
e, E.; Kallenbach,
Kallenba h, R. Die Oberflä
Oberflächendiffusion
hendiffu ion von
on Kohlendio
Kohlendioxyd
d in a
aktiven
ti e
Kohlen. Kolloid-Zeitschrift 1941,
1941 97, 135–151.
 Kinetics of the reductive amination of long chain olefins
in different solvent systems
S. Kirschtowski1, C. Kadar2, A. Seidel-Morgenstern1,3, C. Hamel4
1
Otto von Guericke University, Institute of Process Engineering, Magdeburg, Germany
2
Nuremberg Institute of Technology, Faculty of applied Chemistry, Nuremberg, Germany
3
Max Planck Institute for Dynamics of Complex Technical Systems, Magdeburg, Germany
4
Anhalt University of Applied Sciences, Processing Engineering, Köthen, Germany

Introduction
The hydroaminomethylation (HAM) tandem reaction, which couples hydroformylation
and reductive amination, offers a direct and efficient pathway to various pharmaceu-
ticals, natural products, agrochemicals and fine chemicals [1]. The Collaborative Re-
search Center “InPROMPT - Transregio 63” funded by the German Research Foun-
dation investigates the HAM as an attractive of a complex homogeneously catalysed
tandem reaction. To require detailed knowledge regarding the overall reaction the
sub-network of the reductive amination (RA) step is analysed separately.
To recover the expensive Rh-catalysts from the homogeneous reaction solution
thermomorphic solvent systems (TMS) are applied. In TMS the separation between
products and catalysts is realized exploiting temperature dependent miscibility gaps
in mixture of solvents of different polarity [2]. Rational process development and op-
timization require detailed quantitative knowledge regarding the reaction rates. We
will report on results investigating the reaction kinetics for converting the model sub-
strate 1-undecanale in a homogeneous solvent and in a suitable TMS.

Experimental
RA experiments were conducted in a high-pressure batch reactor system equipped
with a gas supplying system and pressure and temperature controllers. The homo-
geneous solvent system considered of the reactants undecanale and diethylamine
(cundecanal = 0,18 mol/L, nDEA:nundecanal=4:1) and isopropanol (with 1 wt-% dodecane as
internal standard). The TMS is constituted of undecanale, dimethylformamide (DMF)
and dodecane (wDMF : wdodecane = 50 : 50, cundecanal = 0,19 mol/L). The catalyst was
formed from the pre-catalyst Rh(1)(acac)(COD) and the ligand triphenylphosphine
(nRh:nLig:nundecanal= 1:2:1000). Kinetic experiments were carried out in the temperature
and H2 pressure ranges between 85°C…115°C and 10 bar…30 bar, respectively.
Results and discussion
Based on the experimental results a reaction network for the reductive amination of a
long chain aldehyde could be described with four groups of compounds: the interme-
diate n-enamine, the desired product n-amine and the side products n-alcohol and n-
aldols (Figure 1). [Rh]
H2

Figure 1: Main and side products of the rhodium-catalysed reductive amination of a linear aldehyde.

Concerning the RA performed in isopropanol significant conversion X of the reactant

1-undecanale and a relative high yield Y with respect to the n-amine were observed
after 120 minutes (Xundecanale = 91 %, Yamine = 69 %, Figure 2a). The RA carried out in
the TMS revealed a different behaviour. For the same reaction conditions and after
the same reaction time the reactant conversion is significantly lower (XUndecanale = 64
%) and the yield is Yamine = 27 %. In this case the hydrogenation of the enamine to
the amine is clearly inhibited, which is currently quantified in more detail in order to
provide a corresponding kinetic model for the TMS system.

a) b)
Figure 2: Reductive amination of 1-undecanale at T = 100 °C and pH2 = 30 bar.
a) In isopropanol, b) In the TMS (DMF:dodecane = 50 : 50)

References
[1] P. Eilbracht, L. Bärfacker, C. Buss, C. Hollmann et al. Chem. Rev. 1999, 99(11), 3329-3366
[2] T. Gaide, A. Jörke, K.E. Schlipköter et al., Appl. Catal. A, 2017, 532, 50-56
 Activity based kinetic modeling of solvent effects for the
hydroformylation of 1-dodecene
M. Gerlach1, F. Huxoll2, A. Seidel-Morgenstern1,3, C. Hamel1,4, G. Sadowski2
1
Otto von Guericke University, Institute of Process Engineering, Magdeburg, DE
2
Technical University Dortmund, Laboratory of Thermodynamics, Dortmund, DE
3
Max Planck Institute for Dynamics of Complex Technical Systems, Magdeburg, DE
4
Anhalt University of Applied Sciences, Process Engineering, Köthen, DE

Introduction
The Collaborative Research Center Transregio 63 of the DFG studies the concept of
thermomorphic multi-component solvent systems (TMS systems) for the
Rh/BIPHEPHOS-catalyzed hydroformylation of long chain olefins. For a TMS system
consisting of N,N-dimethylformamide (DMF), decane and a terminal long chain olefin,
the reaction kinetics were investigated in detail [1,2]. By changing the DMF/decane
composition, the effect of solvents on the chemical equilibrium of the
hydroformylation was successfully quantified using a thermodynamic consistent
description [3]. In this contribution, solvent effects on the reaction kinetics of the
hydroformylation are studied theoretically and experimentally using mechanistic and
thermodynamic consistent, activity based kinetic models.

Activity based kinetic modeling

In order to consider non-idealities caused by interactions between the components in
a hydroformylation system, the PC-SAFT equation of state was applied, which
quantifies residual Helmholtz energies. It describes systems very comprehensively
and all thermodynamic properties can be derived as for example the state variables
(T,p…) or activity coefficients .
At first a mechanistic kinetic model for the hydroformylation of 1-dodecene was
parameterized for a TMS system with a fixed composition (Eq. 1). The simple
concentration based approach includes the solvent dependent kinetic parameters
, and .

∙ − ∙ ∙ ∙
∙ !" # $
= ∙ '(),(') +
(1)
1+ ∙ #
+ ∙ #
∙ $
In order to explain the effect of the solvent on the hydroformylation kinetics
alternatively an activity based approach was used, replacing the concentrations of
the substrates 1-olefin, H2 and CO by thermodynamic activities (Eq. 2).
"),
∙ − ∙ ∙, !" ∙, #
∙ ,$
")
= "), "),
∙ '(),(') +
(2)
1+ ∙, #
+ ∙, #
∙ ,$

"), "),
Applying Eq. 2, intrinsic solvent independent kinetic parameters , and
"),
could be calculated and used to predict the hydroformylation of 1-dodecene in
TMS systems with varying composition of DMF and decane considering the
thermodynamic activities. Corresponding simulation results could be successfully
validated in kinetic experiments.

Literature
[1] Hentschel, B.; Kiedorf, G.; Gerlach, M.; Hamel, C.; Seidel-Morgenstern, A.;
Freund, H.; Sundmacher, K.; Ind. Eng. Chem. Res., 2015, 54, 1755-1765.
[2] Jörke, A.; Gaide, T.; Behr, A.; Vorholt, A.; Seidel-Morgenstern, A.; Hamel, C.;
Chem. Eng. J., 2017, 313, 382-397.
[3] Lemberg, M.; Sadowski, G.; Gerlach, M.; Kohls, E.; Stein, M.; Hamel, C.;
Seidel-Morgenstern, A., AIChE J., 2017, 63(10), 4576-4585.
 Kinetic investigation of polyurethane rubber formation from CO2-
containing polyols

Georg A. Buchner1, Maik Rudolph1, Jochen Norwig2, Vol er Marker2, Christoph

Volker
Gürtler2, Reinhard Schomäcker1

1 Te
Technische
hni he Universität
Uni er ität Berlin, Department of Chemistry,
Chemi tr , Straße des
de 17. Juni
uni 124,
D-10623 Berlin, Germany

2 Co
Covestro
e tro Deutschland
Deut hland AG, Catal
Catalysis
i and Te
Technology
hnolog In
Incubation,
ubation, Kaiser-Wilhelm-
Allee 60, 51373 Leverkusen

A CO2 utilization te
technology
hnology developed
de eloped in the re
recent
ent years
ear enables the produ
production
tion of
polyether-based polyols with carbon dioxide covalently
o alentl bound in the pol
polymer
mer
backbone
ba bone a
as carbonate
arbonate unit
units.. Moreo
Moreover,
er, it iis possible
po ible to add functionalit
fun
functionality
tionalit to these
polyols b
by copolymerizing
opol merizing double bond moieties such as maleicc anhydride [1-3].
Long-chain polyols with suitable double bond content
ontent can
an be pro
processed
e ed with
diisocyanates to form a polyurethane rubber which
whi h can
an be pro
processed
essed and vulcanized
((crosslinked)
ro lin ed) lilike
e conventional
on entional synthetic rubber
rubbers to obtain elastomers
elastomer as shown in
Figure 1.

Figure 1: Ela
Elastomer
tomer production
production from pol
polyols
ol based
ba ed on propylene
prop lene oxide
o ide (PO) and
including
in luding carbon
arbon dioxide
dio ide (CO2) and a double bond moiety (e.g. maleic
malei anh
anhydride,
dride,
MA), block flow diagram
Polyol and pol
polyurethane
urethane ha
have
e in the meantime been produced
produ ed at technical scale.
While polyol synthesis (1) run
runs in a sufficiently
uffi ientl uniform and well characterized
hara teri ed
process, the rubber formation (2) re
reveals
eal some
ome characteristics,
hara teri ti , which indi
indicate
ate a more
detailed in
investigation
e tigation of kineti
kinetics
ineti and thermod
thermodynamics
nami in order to allow for rea
reactor
tor
simulation
imulation and preparation of scalable process concepts [4].
]. For this
thi rea
reaction,
tion,
thermal analysis offers a good choice
hoi e for simple
imple and quick
qui kinetic
ineti in
inetic inve
investigation
e tigation [5-7].
[
In thi
this study,
tud , the kinetic
inetic beha
ineti behavior
ior of different reaction
rea tion systems
tems
tem is
i examined
e amined using
u ing
temperature programmed differential scanning calorimetry (DSC) measurements.
The thermal conversion over time and temperature is calculated as respective
fractions of the total reaction heat released [8]. Multiple measurements are
simultaneously fit with simple power law models and Arrhenius equation to yield a
kinetic description comprising the parameters pre-exponential factor, activation
energy and overall reaction order. Activation energies between 40 (with catalyst) and
90 kJ/mol (without catalyst) are obtained and lie within the expected range for
urethane reactions. An overall reaction order of approximately 1 is obtained for most
systems suggesting a strong influence of the polymer chain’s mobility on the reaction
rate. For toluene diisocyanate, two reaction rates are observed due to the different
steric situations of the isocyanate groups. At room temperature, the reaction rate of
the isocyanate group in para position is over one order of magnitude higher than the
reaction rate of the isocyanate group in ortho position [9]. Isocyanate conversion is
verified by IR spectroscopy. Alcohol and urethane groups can not be quantified via IR
due to insufficient signals resulting from very low concentrations. For the same
reason, potential side reactions cannot be observed by means of IR spectroscopy.
The two-parameter Schulz-Flory (SF) equation gives a good description of the
molecular weight distribution of resulting polyurethanes [10,11]. Deviations result
from the polyol’s polydispersity and different reactivities of the reactive groups during
the reaction.
We gratefully acknowledge the financial support by the European Institute of
Innovation and Technology (EIT) and the German Federal Ministry of Education and
Research (BMBF).
[1] J. Langanke et al., Green Chem., 16, 1865-1870, 2014 [2] T.E. Müller, EP
2604642 A1, 2011/2013 [3] C. Gürtler, Plenary Lecture LT1, International Conference
on Carbon Dioxide Utilisation, 12th Sept, Sheffield UK, 2016 [4] EIT “CroCO2PETs”
project description, http://enco2re.climate-kic.org/projects/croco2pets/ [2017-11-28]
[5] Journal of Thermal Analysis and Calorimetry, Vol. 83, 2, 355–359, 2006 [6] S.
Vyazovkin, Int. Journal of Chemical Kinetics. 28. 95 – 101, 1996 [7] P. Hugo, Chemie
Ingenieur Technik, 65, 1497 – 1500, 1993 [8] G. Höhne et al., Differential Scanning
Calorimetry, 2. Ed., pp. 115–146, Springer, 2003 [9] M.F. Sonnenschein,
Polyurethanes, pp. 105–126, Wiley Inc, 2014 [10] P.J. Flory, J. Am. Chem. Soc., 58,
1936 [11] Macromol. Theory Simul., 24, 500–512, 2015
 Kinetic investigations on olefin interconversion and hydrogen
transfer reactions over an H-ZSM-5
5 catalyst
Felix Warnecke1, Lin Lin2, Stéphane Haag2, Hann jörg Freund1
Hannsjörg
1
Friedrich-Alexander-Uni
Universität
er ität Erlangen
Erlangen-Nürnberg,
Nürnberg, Lehr
Lehrstuhl
tuhl für Chemische
Chemi he
Reaktion te hni , Erlangen, Germany
Reaktionstechnik, German
2
AIR LIQUIDE For
Forschung
hung und Entwi
Entwicklung
lung GmbH, Fran
Frankfurt
furt Re
Research
earch
ear h & Technology
Te hnolog
Center, Frankfurt
Fran furt am Main, German
Germany
The inter
interconversion
on er ion rea
reactions
reaction
tion of olefin
olefins on zeolite
eolite catalysts
atal t are important in man
many
petrochemical
petro hemi al processes
pro e es such as, e.g., catalytic
atal ti naphtha cracking
racking or methanol
downstream
down tream processes
pro e e for the produ
production
tion of light olefin
olefins such
u h as
a the MTO or MTP
processes [1, 2].. Due to the complexity
omple it of the reaction
rea tion mechani
me hani m and a high
mechanism
number of in
involved
ol ed component
omponents it still
omponent till remain
remains challenging
hallenging to e
establish
tablish
tabli h reliable kinetic
ineti
models suitable
model uitable for process design,
de ign, particularly
parti ularl in terms
term of applicabilit
applicability for rea
reactor
tor
optimization purposes.

Figure 1:: Rea

Reaction
tion scheme
heme for olefin inter
interconversion
on er ion and hydrogen transfer reactions

This wor
Thi work aim
aims at kinetic
ineti modeling based
ba ed on extensive
e ten i e own e
experimental
perimental
measurement
mea urement data. We propose
propo e a novel
no el reaction
rea tion network scheme (Fehler!
Verweisquelle konnte nicht gefunden werden.)
werden. for the inter
interconversion
onversion reactions
rea tion of
the olefin
olefins in
including
luding cracking,
ra ing, oligomeri
oligomerization
ation and di
disproportionation
proportionation reactions.
rea tion .
Additionally, a reaction
ion kinetic
kineti model for the formation of side
ide products
produ t ha
has been
developed based on a new mechanism to precisely describe the hydrogen transfer
reactions.

Figure 2: Kinetic setup

Reaction kinetics of C2 to C7 olefin cracking over a commercial H-ZSM-5 catalyst

were studied in detail using a Berty-type reactor. Figure shows the experimental
setup used for the kinetic measurements. To investigate the behavior of olefins,
dosing of pure (individual) olefins as well as different olefin mixtures was performed
over a wide range of conversion. The reaction mechanism of olefin cracking was
systematically analyzed to identify the best suitable model, taking into account both,
the reaction network and the reaction kinetic model approach. The numerical
regression of the kinetic parameters was carried out using state-of-the-art solvers.
The formation of side products was analyzed in detail using a custom-made gas
chromatograph which was capable of separating and analyzing more than 100
hydrocarbon species (Figure 1). Based on this high degree of information for the
product distribution, a novel reaction mechanism for modeling the hydrogen transfer
reactions is proposed in this work. Considered side products include paraffins,
naphthenes, cycloolefins and BTX aromatics.
1. Liu, D., et al., Inter-conversion of light olefins on ZSM-5 in catalytic naphtha cracking
condition. Catalysis Today, 2014. 226: p. 52-66.
2. Huang, X., D. Aihemaitijiang, and W.-D. Xiao, Reaction pathway and kinetics of C3–C7 olefin
transformation over high-silicon HZSM-5 zeolite at 400–490°C. Chemical Engineering Journal,
2015. 280: p. 222-232.
 Modelling of enzymatic reaction kinetics in multiphase systems

S.Rusli, J. Grabowski, M.Kraume, TU Berlin, Germany

The enzymatic hydrolysis reaction with lipase enzyme holds a promising industrial
application as alternative to the saponification processes, including the production of
biodiesel. Lipase enzymes (EC. 3.1.3.) has a unique properties to adsorbed on water
– oil interfaces, to access to both substrates, triglyceride (TG) in the oil phase and
water (W) in the aqueous phase. Therefore, the kinetics of such reaction follows the
heterogenous reaction kinetics as it is dependent on the availability of surface area
between the oil and water phase.

Experimental data
Experiments were conducted in an emulsion reactor, with sunflower oil as source for
triglycerides. A stirred tank reactor was used to create the emulsion, equipped with
an endoscope to analyze the drop sizes. As the stirring rate increases, the drops
become smaller, and surface area becomes larger. The tendency such shown in the
following graph was observed.

This graph shows two distinct kinetics. At low stirring rate, surface area determines
the reaction rate. It increases with increasing surface area, until all enzyme
molecules are adsorbed. After which, the reaction rate is only dependent on the
enzyme concentration, as normal enzymatic reaction kinetics would predict.
Modelling approach
To model such kinetics,
ineti s,, modifi
modification
ation of the Mi
Michaelis
haeli Menten Kinet
Kinetics is needed to
include
in lude the limitation of surface area
area.

The fir
firstt step
tep of the rea
reaction
tion me
mechanism
hani m is
i the adsorption
ad orption of enzyme
en me molecules
mole ule to
w/o interface. Thi
This allow
allows the limitation of adsorbed
ad orbed enzyme
en me in the emulsion.
emul ion. The
adsorption
ad orption and desorption
de orption constants ( , ) were fitted against experimental data
with pendant drop measurements,
measurement , where the surface
urfa e area ( ) can
an be hold constant.
on tant.
Ping-Pong Bi-Bi
Bi approa
approach
h wa
was u
used
ed to describe
de ribe the rea
reaction
tion with two substrates
ub trate (TG
and W). The main reaction steps
p are describe
de ribe with 8 constants
( , , , , , , , ), which
whi h are fitted again
againstt e
experimental
perimental data in the emulsion
reactor
rea tor with high stirring
tirring rate to e
exclude
lude the surface
urfa e area limitation. B
By modelling the
different rea
reaction
tion steps,
tep , it is po
possible
ible to appl
apply the model with different lipase
lipa e enzymes
en me
with different specificity
pe ifi it toward
towards the substrate
ub trate (TG/DG/MG), as
a the formation of the
intermediate products Di- and Mono-
Mono Gl
Glycerides
eride are also
al o predi
predicted.
ted. Furthermore, the
model is also aimed to include
include the influen
influence
e of Glycerol
Gl erol (Gly)
(Gl ) as side produ
product,
t as
productt inhibition was
produ wa observed in the e
experiments.
periment .
The model iis validated
alidated with e
experimental
perimental data for both limiting and non
non-limiting
surface area, at different enzyme
enz me concentration,
on entration water-oil ratio, glycerol concentration
on entration
and with different oils.
 Reaction kinetics of Ni/MgO catalyzed CO2 methanation

Astrid Loder, Susanne Lux, Georg Baldauf-Sommerbauer, Matthäus Siebenhofer,

Graz University of Technology, Graz/Austria

A reduction of CO2 emissions can be achieved through methanation of carbon

dioxide rich offgas (e.g. from calcining carbonates). A bifunctional Ni/MgO catalyst
was prepared and investigated in terms of its activity and reaction kinetics. Nickel
provides the catalyst’s adsorbent capacity for hydrogen, and it is highly selective to
methane. MgO activates carbon dioxide and reduces catalyst deactivation. The
Ni/MgO catalyst is a highly active, cheap, easy to synthesize and robust catalyst for
the methanation of carbon dioxide.
Ni/MgO catalysts were compared for different nickel loads between 11-27%wt. The
process parameters temperature and gas flow rate were analyzed for their effect on
methane selectivity and CO2 conversion.
High nickel load leads to higher methane selectivity and higher carbon dioxide
conversion. At 27% nickel load and 598 K the equilibrium CO2 conversion was
reached.
The reaction rate of the carbon dioxide methanation was modelled with a Langmuir-
Hinshelwood based approach. Temperature dependency was included. The
activation energies are the same for all tested Ni/MgO catalysts. The values suggest
a reaction limited regime. The frequency factors can be described by a linear
equation for different nickel loads.
 A Case Study for Mechanistic Kinetic Modelling of Biocatalytic

Reactions: Formation of Galacto-Oligosaccharides

I. Mueller 1, K. Kowalski 1, S. Kirschtowski 2, A. Seidel-Morgenstern 2, C. Hamel 1,2

1
Anhalt University of Applied Sciences, Koethen (Anhalt), Germany
2
Otto von Guericke University, Magdeburg, Germany

Introduction
Galacto-oligosaccharides (GOS) are classified as prebiotics, defined as a non-
digestible food ingredient which selectively stimulate the beneficial bacterial flora of
the large intestines [1]. In particular, a great interest exists in utilization of galacto-
oligosaccharides (GOS) as health-promoting food supplement e. g. for infant
formulas as well as special nutrition requirement for care-dependent people.
Furthermore, GOS provide/possess excellent techno-functional properties [2] which
makes it attractive for a broad spectrum of end-use applications.

Enyzmatic Synthesis of Galacto-Oligosaccharides

GOS is a natural part of the human breast milk. In contrast, bovine milk contains
GOS as minor component only. Thus, a promising approach for GOS formation is
provided by the enzymatic catalysis of the GOS synthesis from bovine lactose using
β-galactosidase. Currently, lactose is a low cost side and waste product [3]. The
enzyme based synthesis is characterized by a reaction mechanism called
transgalactosylation and stands in a competing relation to a hydrolysis reaction (see
fig.1). The equilibrium limited GOS formation process can be strongly influenced by
the choice of the enzyme/catalyst origin in return.

Figure 1: Simplistic mechanism of the GOS formation from lactose

Network Elucidation and Mechanistic Kinetic Modelling
In literature, the GOS formation is mostly described with simple Michaelis Menten
kinetics [4,5]. Mechanistic kinetic models instead, are often used in chemical reaction
engineering but are not well established in enzyme catalyzed reactions yet and will
be presented in this contribution.
The reaction mechanism was investigated for the GOS formation from lactose as
substrate with the enzyme -galactosidase from B. circulans. Systematic experiments
were conducted to identify optimal operating parameters with respect to ph value,
temperature and the substrate-enzyme-concentration-ratio. Based on the experi-
mental data the reaction network was elucidated and a catalytic cycle postulated
(fig.2). This contribution applies an optimized Christiansen approach by coupling mul-
tiple cylces with loop coefficients [6] as well as with the inclusion of inhibitory effects.
Based on the developed catalytic cycle, reversible mechanistic kinetic models were
derived. For model reduction and parameterization a sensitivity analysis was per-
formed with detailed kinetic studies. The reduced and parameterized mechanistic
models allowed a good model based description in a broad range of operating condi-
tion, which will be evaluated by experimental data and discussed for validity.

Figure 2: Catalytic cycle for

mechanistic modelling of
the GOS formation kinetics
with inclusion of inhibition
effects

This study is ment to implement the general mechanistic approach as an example for
biocatalytic processes presented by the GOS formation. Furthermore, the kinetic
models and parameters generate a foundation for an apparatus-based and model-
based optimization of bioreactors and process intensification.
References
[1] M. Roberfroid, et al., British Journal of Nutrition, 104 (2010) S1-S63.
[2] D.P. Torres, et al., Comprehensive Reviews in Food Science and Food Safety, 9 (2010) 438-454.
[3] M.G. Gänzle, et al., International Dairy Journal, 18 (2008) 685-694.
[4] T. Palai, et al., Materials Today: Proceedings, 3 (2016) 3568-3586.
[5] C.S. Kim, et al., Biochemical and biophysical research communications, 316 (2004) 738-743.
[6] F.G. Helfferich, The Journal of Physical Chemistry, 93 (1989) 6676-6681.
 Kinetic Modeling and Optimization of Photocatalytic Reactions

Julia Patzsch, DECHEMA-Forschungsinstitut, Frankfurt/Germany; Fabian Guba, Ulm

University, Ulm/Germany; Dirk Ziegenbalg, Ulm University, Ulm/Germany; Jonathan
Z. Bloh, DECHEMA-Forschungsinstitut, Frankfurt/Germany

Photocatalytic reactions present a very appealing alternative to many conventional

processes as they can be performed under very mild conditions and without the need
for dangerous high-energy reagents. Moreover, the potential use of electricity from
renewable sources to power the lamps can make these reactions carbon neutral and
sustainable.
However, industrial implementation of these reactions has up to now been hindered
by the requirements for expensive and specialized equipment as well as little
knowledge of the underlying reaction mechanisms and kinetics and how to optimize
them.[1] While on the former issue, new approaches using photomicroreactors or
internal illumination offer interesting solutions,[2,3] kinetic analysis and optimization
are still very challenging. This is mainly due to the fact that the local light intensity
and with it the catalyst activity varies dramatically over the reaction volume, making
complex numerical simulations mandatory.
Herein, we present a simplified approach to model the kinetics of heterogeneous
photocatalytic reactions that is applicable to many reactor geometries.[4,5] This
approach uses explicit equations and therefore does not require numerical methods,
making kinetic analysis and optimization much easier and faster. This model is
subsequently evaluated for two exemplary reactions: the photocatalytic reduction of
nitrobenzene in ethanol and the degradation of methylene blue in water.
The photocatalytic reduction of nitroarenes presents an interesting alternative to
hydrogenation for the preparation of aromatic amines, which are very important
intermediates for the chemical industry.[6] Moreover, if a primary alcohol is used as
the electron donor, the reaction proceeds to form imines and condensated ring
systems such as quinolines. This gives direct access to these functionalized
compounds from the nitroarene in an one-pot reaction.[6] The reaction therefore
presents a very good example of efficient photocatalytic synthesis, combining three
separate reactions: reduction, oxidation and condensation. However, there is little
information about the kinetics and photonic efficiency of the overall reaction.
On the other hand, heterogeneous photocatalysis can be applied for the degradation
of unwanted pollutants in wastewater. Due to the ease of monitoring its degradation
through optical spectroscopy, methylene blue is often used as a representative
prototype substance to judge the photocatalyst's efficacy in mineralizing waterborne
pollutants.
For these two reactions, we present a detailed study of kinetics under different
reaction conditions such as illumination intensities, catalyst loadings and
temperature. The results show that our newly developed model is applicable and can
be used to optimize the reaction both with respect to productivity and efficiency.

References
[1] F. Guba, Ü. Tastan, K. Gugeler, M. Buntrock, T. Rommel, D. Ziegenbalg, Chem Ing. Tech.
2018, accepted, doi: 10.1002/cite.201800035.
[2] D. Ziegenbalg, B. Wriedt, G. Kreisel, D. Kralisch, Chem. Eng. Technol. 2016, 39, 123–134.
[3] B. O. Burek, A. Sutor, D. W. Bahnemann, J. Z. Bloh, Catal. Sci. Technol. 2017, 7, 4977–4983.
[4] J. Z. Bloh, Front. Chem. 2018, submitted.
[5] B. O. Burek, D. W. Bahnemann, J. Z. Bloh, ACS Catal. 2019, 9, 25-37.
[6] Y. Shiraishi, Y. Togawa, D. Tsukamoto, S. Tanaka, T. Hirai, ACS Catal. 2012, 2, 2475–2481.
[7] A. Hakki, R. Dillert, D.W. Bahnemann, ACS Catal. 2013, 3, 565–572.
 Influence of thermophysical properties of the saturated liquid and
the heating surface on the heat transfer in boiling

Niklas Buchholz, Andrea Luke

Universität Kassel, Fachgebiet Technische Thermodynamik, Kurt-Wolters-Str. 3, 34125, Kassel,

Deutschland
ttk@uni-kassel.de

Abstract

The thermophysical properties of the boiling liquid and those of the material of the
heater surface are one of the main influence parameters in evaporators. They are not
considered in typical correlation of the design of industrial apparatus. However, new
prediction methods for heat and mass transfer in boiling are required in future to
replace the empirical correlation used until now, since they are inaccurate in many
cases.

Characteristic features of the heating surface and the bubble formation considering
the thermophysical properties shall be introduced into the calculation methods for the
heat transfer in boiling. New developments in computer calculations and in
measurement techniques support these efforts. Obviously, very accurate heat
transfer measurements are not sufficient without the study of the roughness and of
the bubble formation with the same accuracy in order to develop a correlation
describing the phenomena of boiling. Little progress has been made so far in the
development of theoretically based predictive methods, especially for heat transfer
conditions relevant in practice, because less quantitative information exists on the
microstructure, especially of the topography, of the heated surfaces and on bubble
formation than on heat transfer.

In this context, the heat transfer for different hydrocarbons boiling on the outside of a
horizontal tubes with defined surface properties will be presented and compared to
correlations and to data from literature. A new correlation will be developed based on
the wetting conditions of the micro structured surface, because the microscopic
structure with all its peaks and cavities influences directly the wetting condition of the
heated surface by the fluid and therefore the bubble formation and the heat transfer.
The results show a better coincidence with measured data in literature than the
conventional calculation methods for the design of evaporators.
Poster Abstracts
Heterogeneous Catalysis
 Simulation of the transient CO2 methanation – Are steady-state
kinetics sufficient?
Bjarne Kreitz, Jan Martin, Steffen Flaischlen, Gregor D. Wehinger, Thomas Turek
Institute of Chemical and Electrochemical Process Engineering, Clausthal University
of Technology, Leibnizstr. 17, 38678 Clausthal-Zellerfeld, Germany

Heterogeneously catalyzed processes are usually operated in steady state. The

coupling of these processes to renewable energy sources, such as the methanation
of CO2 in the Power-to-Gas process, may require a dynamic operation of the reactor.
Reaction kinetics resulting from steady-state measurements, mostly in the form of
Langmuir-Hinshelwood-Hougen-Watson approaches, are typically used for the
reactor design or the investigation of suitable operating conditions. The simulation of
the periodic operation of a methanation reactor based on steady-state kinetics
predicted dramatic effects of the inlet composition on temperature profile and outlet
composition [1]. However, the underlying description of the reaction rate is a strong
simplification of the actual processes on the catalyst surface. A detailed description
of the transient and steady-state operation can be achieved by microkinetic models
[2]. But microkinetics are rarely applicable for simulation and design on the reactor
scale. Therefore, the development of a dynamic kinetic model for the methanation of
CO2 over a Ni catalyst that allows a thorough description of transient phenomena
without calculating each elementary step, is the aim of this study.

In order to develop a proper kinetic approach, measurements with a Ni catalyst in a

Berty reactor are carried out. At temperatures of 200 - 400°C and pressures up to 30
bar, this reactor can be regarded as an ideally mixed continuous stirred tank reactor
(CSTR). Through online analysis of the gas composition with a mass spectrometer,
both stationary and dynamic measurements can be performed with high temporal
resolution. For the investigation of the dynamic behavior of the methanation reaction,
concentration pulses and steps are applied to the system. The high frequency of the
step changes also allows for a periodic modulation of the system. During the dynamic
catalyst operation, storage effects of adsorbed educts and intermediate products
become visible. Additionally, the storage capacity is studied via the adsorption of CO2
and H2 at reaction temperatures by volumetric and dynamic adsorption methods,
which allows the determination of adsorption isotherms and adsorption kinetics.
Based on the experiments, approaches for the reaction kinetics (steady-state,
dynamic) are developed. These are used in a model of the Berty reactor to explore
the limits of steady-state kinetics and the applicability of simplified dynamic kinetics.
The Berty reactor is modelled as a CSTR taking the catalyst as a separate solid
phase into account.

Figure 1 (a) Periodic composition modulation between H2 and CO2 with a cycle time of 60 s and a cycle split ratio
of 0.5 over a Ni catalyst in a Berty reactor showing experiments (dots) and simulations with steady-state reaction
kinetics (solid). (b) Experimental (dots) and simulation (solid) results when the Berty-reactor is flushed with He for
10 min between a change from CO2 to H2. The zoom is located at the step change of H2. Conditions: 20 wt.-%
Ni/Al2O3, 0.5 g, 250 °C, 2 bar, 200 mLN/min.

The diagram shows the transient operation of a Ni/Al2O3 catalyst in (a) bang-bang
operation switching between the pure reactants and (b) with a flush of He between
the step changes. The periodic operation can be described with relatively good
accuracy by using a published steady-state reaction kinetics [3]. However, when the
reactor is flushed with inert gas, the remaining CO2 is removed from the gas phase.
Switching to H2 then leads to desorption of adsorbed CO2 and methane formation
sets in. This simple experiment nicely illustrates the failure of the steady-state
reaction kinetics. Since H2 and CO2 do not simultaneously occur in the reactor, the
calculated reaction rate is always zero. The observed methane formation reveals that
significant quantities of CO2 and/or carbon containing intermediates are adsorbed on
the catalyst surface, which is also evidenced by the adsorption measurements.

References
[1] Kreitz, B., Wehinger, G.D., Turek, T. Chem. Eng. Sci., 2018. DOI: 10.1016/j.ces.2018.09.053
[2] Seidel, C., Jörke, A., Vollbrecht, B., Seidel-Morgenstern, A., Kienle, A. Chem. Eng. Sci., 2018,
175, 130–138. DOI: 10.1016/j.ces.2017.09.043
[3] Koschany, F., Schlereth, D., Hinrichsen, O. Appl. Catal., B, 2016, 181, 504–516. DOI:
10.1016/j.apcatb.2015.07.026
 Aromatization
romati ation of bio-derivable
bio isobutyraldehyde
e over HZSM-5
HZSM
zeolite
eolite catalysts in a continuous fixed bed reactor

Jeff
eff Deischter,
Deis hter Kai Schute, Regina Palkovits
Institut
In titut für Technische
Te hni he und Ma
Makromolekulare
romole ulare Chemie, RWTH Aachen University,
Uni er it ,
Aachen

Aromatic h
hydrocarbons
dro arbon such
u haas ben
benzene,
ene, toluene, eth
ethylbenzene
lben ene and xylene
lene isomers
i omer
(which
(whi h are referred to a
as BTX) pla
play a very
er important role for the petrochemical
petro hemi al and
fine chemical industry. Currentl
Currently,, BTX is
i mainly
mainl obtained from catalyti
catalytic
atal ti cracking
ra ing and
catalytic reforming
ming pro esses of petroleum.[1] Renewable and sustainable
processes ustainable alternatives
alternati e
for accessing Bio-BTX,
BTX, however,
howe er, remain challenging.
hallenging. In connection
onnection with the world-
world
wide search for bio-derivable
derivable fossil
fo il energ
energy carriers,
arrier oxygen-containing
ontaining hydrocarbons
h dro arbon
e.g. a
acetone
etone or iisobutanol,
obutanol, whi
which
h are a
accessible
e ible via bioma
biomasss fermentation, have
been considered
on idered for the production aromati .[2] Besides the more common
produ tion of aromatics. ommon
candidates such as ketones
etones and alcohols,
al ohol , also aldehydes like iisobutyraldeh
obutyraldehyde
de (IBA)
are promi
promising
ing starting
tarting material
materials.. Their produ
production
tion fulfill
fulfills the criteria of sustainable
u tainable
chemistry as they can
an be readily
read obtained either from glu
glucose
ose in a bio-catalytic
bio
pathway or by the
he dire
directt photo
photosynthetic
ntheti recycling
re ling of carbon ide [3] Herein, we
arbon dioxide.
dio
dioxide
report on a novel
no el heterogeneou
heterogeneously
l catalyzed
atal ed aromatization pro e
process of
isobutyraldehyde o
over
er HZSM
HZSM-5
5 zeolites
eolite in a continuous
ontinuou fixed bed rea
reactor
tor
(Figure 1).[4,5]

Figure 1: Continuous gas-pha

phase
pha e aromati
aromatization
ation process
pro e of isobutyraldeh
i obut raldehyde
raldeh de to aromati
aromatic
hydrocarbons.
The effect of catalyst properties, in particular the Si/Al ratio of the zeolite material, as
well as the reaction parameters weight hourly space velocity (WHSV) and
temperature were carefully studied. The utilized zeolite catalysts were characterized
using XRD, NH3-TPD, N2-physisorption, and ICP-OES. Moreover, long term stability
and successful catalyst recycling through in situ calcination were also demonstrated
as similar results over several reaction cycles were achieved.

References
[1] G. Ertl, H. Knözinger, F. Schüth, J. Weitkamp, Handbook of Heterogeneous
Catalysis. 2nd Edition, Wiley-VCH.
[2] S. Setiadi, N. M. Slamet, Int. J. Eng. Technol 2011, 11, 72-79.
[3] S. Atsumi, W. Higashide, J. C. Liao, Nat. Biotechnol. 2009, 27, 1177.
[4] J. Deischter, K. Schute, R. Palkovits, DE Patent Application Pending, No. 10
2018 114 979.4 2018.
[5] J. Deischter, K. Schute, R. Palkovits, under preparation
 Suppression of Carbon Formation during CO2 Hydrogenation
by Fe@SiO2 Core-Shell Catalysts
Johann Kirchnera, Christian Zambrzyckib, Zeynep Baysala,
Sven Kuretia, Robert Güttelb
a
Institute of Energy Process Engineering and Chemical Engineering,
TU Bergakademie Freiberg, 09599 Freiberg, Germany
b
Institute of Chemical Engineering, Ulm University, 89081 Ulm, Germany

The rapid growth of global energy consumption leading to increased emission of the
greenhouse gas CO2 substantially concerns modern civilization. Many efforts were
made using CO2 as abundant and inexpensive feedstock in the synthesis of chemi-
cals and fuels. In this respect, hydrogenation of CO2 towards hydrocarbons over Fe
based catalysts is a possible route [1].
For the unambiguous identification of the catalytic activity, Fe based core-shell model
catalysts were prepared with desired properties, e.g. core size and shell thickness.
The synthesis of these core-shell structures was performed using a modified water-
in-oil microemulsion system. The method yields FexOy@SiO2 core-shell particles with
core sizes < 10 nm and total particle sizes < 30 nm, which is in agreement with litera-
ture [2]. The total Fe amount (8 - 42 wt.%) and the size of the metal oxide core (3.5 -
8 nm) are controlled by adjusting the synthesis parameters. It is well known that Fe
based catalysts undergo complex structural changes under synthesis gas conditions,
e.g. phase transformations, deposition of different carbon species and morphological
changes [3]. Therefore, physical-chemical properties of the core-shell material were
57
thoroughly investigated by X-ray diffraction, Fe Moessbauer spectroscopy, N2
physisorption and transmission electron spectroscopy. Catalytic CO2 hydrogenation
performance after H2 activation was evaluated between 300 and 550°C and pres-
sures up to 8 bar, while using a catalyst mass up to 0.5 g (125 - 250 µm).
The catalytic CO2 hydrogenation activity, expressed in terms of CH4 formation rate
per Fe amount of core-shell catalysts, is comparable to bare iron oxide catalysts (Fig.
1, left). Different stages concerning time-dependent performance behavior as well as
structural transformations were found. While initial activity is mainly determined by
the degree of reduction of the core-shell catalysts achieved upon H2 activation, CH4
formation for increasing time on stream is associated with carburization of the cata-
lysts. In this context, pronounced carburization is related to larger Fe core particles
as revealed by detailed characterization of the spent samples (Fig. 1, right).

Fig. 1. CH4 formation rate during CO2 hydrogenation at 400°C and 1 bar for core-shell catalysts with
different Fe loadings and 6 nm core size (left). Temperature programmed hydrogenation after reaction
of core-shell catalyst with 15 wt.% Fe and different core sizes (right).

In conclusion, Fe based core-shell materials were prepared as suitable catalysts for

CO2 hydrogenation, exhibiting similar methane formation rates compared to bare iron
catalysts (derived from -Fe2O3 after reduction). The influence of specific material
properties, e.g. shell thickness and core size, on structural changes, carburization
behavior and catalytic activity was studied. It was found that carburization of the cata-
lysts under methanation conditions is more pronounced for large Fe core particles,
even though coking is suppressed. Finally, a clear relation between CH4 formation
rate, carburization and the material structure was observed.

References
[1] J. Kirchner, J.K. Anolleck, H. Lösch, S. Kureti, Appl. Catal. B Environ. 223 (2018) 47.
[2] S. Takenaka, H. Umebayashi, E. Tanabe, H. Matsune, M. Kishida, J. Catal. 245 (2007) 392.
[3] C.H. Bartholomew, Appl. Catal. A 212 (2001) 17.
 Hierarchical Open Cellular Raney® Copper Foams for CO
Hydrogenation to Methanol
Christina Heßelmann, Jakob Albert, Peter Wasserscheid
Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Lehrstuhl für Chemische
Reaktionstechnik (CRT), Egerlandstr. 3, 91058 Erlangen, Germany

We present a novel manufacturing technique for synthesizing hierarchical open

foams made from Raney® copper. Unlike existing techniques, where an additional
support structure is coated, we form the structure from copper directly.

Raney® type catalyst are bulk catalysts, which are known for their high
hydrogenation activity by relatively low production costs[1]. Usually they are used as
fine dispersed powders in liquid phase hydrogenation reactions. Based on the arising
pressure drop, Raney® catalyst have to be shaped when using in fixed-bed reactors.
Copper-based structures are a promising catalytic system for the methanol synthesis
due to the availability, high catalytic activity and good thermal conductivity. Therefore
we used the methanol synthesis as case study to test the produced Raney®
structures. The resulting open cellular foams have interesting properties compared to
classical fixed-bed reactors in terms of mass and heat transfer. Different design
parameters in the manufacturing process allow a tight control of the catalyst density
and the pressure drop in the reactor [2].
Based on high temperatures during the manufacturing process, open cellular foams
could not synthesize so far directly out of the catalytic active material. State-of-the-art
is to functionalize an open cellular ceramic or metal foam by coating with the catalytic
active material[3]. This procedure involves several process steps, like multiple
coating, calcination and catalytic activation. Our novel approach is to facilitate the
catalyst preparation based on the principal of Raney®.

Therefore, an open-cellular copper-aluminum foam is synthesized by the replication

technique[4], where sodium chloride serves as space-holder (s. Figure 1). Liquid
copper-aluminum melt is pressed in a well-defined sodium chloride packing.
Afterwards, the sodium chloride is leached out with water to receive a copper
aluminum
inum metal foam. For catalytic
catal
atal ti activation
a ti ation the aluminum is
i leached
lea hed selectively
ele ti el in
a la
lastt step
tep to generate a catal
catalytic
atal ti aactive
ti e nanoporou
nanoporous Raney®
Rane ® copper
opper foam.

Figure 1: Con
Concept
ept of hierar
hierarchical
hierarchi
hi al open cellular
ellular Rane
Raney®
® copper
opper foams
foam

Firstt e
Fir experiments
periment showed
howed promi
promising
ing re
results
ult in synthesizing
nthe i ing catal
catalytically
atal ti all aactive
ti e
Raney®
Rane ® copper
opper foam
foams.. In thi
this study,
tud , we focused
fo u ed on the aluminum lea
leaching
hing with
sodium hydroxide to generate a stable
table and a
active
ti e foam. The hierar
hierarchical
hi al Rane
Raney®
®
copper foams were tested
sted in the gas-phase
ga pha e CO hydrogenation
h drogenation to methanol. In
addition to the catalytic
atal ti investigation
investigations,
in e tigation , different anal
analytical
ti al te
techniques
hnique
hniques ha
have
e been u
used
ed
to characterize
hara teri e the Raney® copper foams.
foam .

References

[1] A. Wolf, T. Turek, and L. Mleczko,

Mle o, "Stru
"Structured
tured Raney Ni
Nickel
el Catal
Catalysts
t
for Liquid-Phase
Pha e Hydrogenation,"
H drogenation," Chemi
Chemical
al Engineering & Te
Technology,
hnolog , vol.
ol.
39, no. 10, pp. 1933--1938, 2016.
[2] C. Bu
Busse,
e, H. Freund, and W. S
Schwieger,
hwieger, "Intensification
"Inten ifi ation of heat tran
transfer
fer in
catalytic
atal ti reactors
rea tors by additi
additively
el manufactured
manufa tured periodi
periodic open cellular structures
tru ture
(POCS)," Chemical Engineering and Processing
Pro e ing - Pro
Process
ess Intensification,
Inten ifi ation, vol.
ol.
124, pp. 199-214,
214, 2018/02/01/ 2018.
[3] A. Reit
Reitzmann,
mann, F. C. Patcas,
Pat a , and B. Krau
Kraushaar-Czarnetzki
haar C arnetzki, "Keramische
Schwämme – Anwendung
Anwendungspotenzial
poten ial monolithischer
monolithi her Netz
Net tru turen al
Netzstrukturen als
katalytische
atal ti he Pa
Packungen"
kungen"
ungen" Chemie Ingenieur Te
Technik,
hni , vol.
ol. 78, no. 7, pp. 885
885-
898, 2006.
[4] Y. Conde et al., "Repli
"Replication
ation Pro
Processing
e ing of Highl
Highly Porous
Porou Material
Materials,"
,"
Advanced Engineering
ng Materials,
Material , vol.
ol. 8, no. 9, pp. 795
795-803,
803, 2006.
 From Carboxylic Acids to sustainable Polymers: Novel Catalytic
Processes for the Valori
Valorization
ation of Biomass

M.O. Haus,, Y. Louven and R. Palkovits,

Pal o it RWTH Aachen, Aachen/DE

Subtopics: Heterogeneous Catalysis, Processes

Figure 1: Two po
possible
ible routes to a
access
e N-vinyl-2-pyrrolidone
p rrolidone and comparable
omparable monomer
monomers starting
tarting
from biomass-derived
deri ed platform chemi
chemicals;
al ; special
pe ial focus
fo u in this
thi contribution
ontribution is laid on the upper
alternative,
alternati e, thu
thus a
avoiding
oiding the hazard of high-pressure
high pre ure acetylene
a et lene chemistry
hemi tr in a green pro
process.
e .

To date, the la
lack of efficient conversion
on er ion strategies
trategie for bio
bio-based
ba ed platform chemicals,
hemi al ,
such
u h as
a succinic,
u ini , ita
itaconic
onic and le
oni levulinic
ulini acid,
a id, hampers
hamper the ne
necessary
e
essary
ar replacement
repla ement of
fossilil re
fo resources
our e aas feed
feedstock
feedstoc
to of the chemical
hemi al indu
industries.
trie . This
Thi is
i mo
mostly
tl due to the
inapplicability
nappli abilit of traditional catalytic
catal ti routes
route – established in oil-chemi
chemicals
al pro
processing
e ing
– to the upgrading of oxygen-rich,
oxygen biomass-derived moieties.[1] In this context,
strategies
trategie for the introdu
introduction
tion of nitrogen fun
functionalities
tionalitie are especiall
especially
e pe iall sought-after.
ought
Consequently,
Con equentl , the manufacture
manufa ture of p
pyrrolidones
rrolidone from carboxylic
arbo ylic
li aacids
id ha
has been
described
de ribed in several
e eral arti
articles,
le , dealing mo
mostly
tl with the produ
production
tion of pharmaceutical
pharma euti al
intermediates from ea
intermediate easily
ily redu
reducible
ible le
levulinic
ulini a id.[2]
acid.
In contrast,
ontra t, our re
research
earch focuses
fo u e on the conversion
on er ion of succinic
u inic and itaconic
ita oni aacid
id
towards N-vinyl-2-pyrrolidone
p rrolidone (NVP), the monomer of pol
polyvinylpyrrolidone
in lpyrrolidone. Due to its
favorable properties, the latter ha
has a plethora of appli
applications
ation in the food, cosmetic
o meti
and pharma
pharmaceutical
euti al industrie
industries.. A
As a consequence,
on equen e, the steadily
teadil growing NVP mar
market,
et
which leaves room for new producers and production strategies,[3] lends economic
merit to our envisioned, green valorization chain.

While we are also working on the production of N-unsubstituted pyrrolidones, which

may be fed into the classical Reppe vinylation,[4] the current contribution focuses on
an alternative pathway to NVP via N-(hydroxyethyl)pyrrolidones (HEP). The latter,
which are obtained through the reductive amidation of carboxylic acids with
monoethanolamine, are easily dehydrated, thus avoiding the difficult handling of
pressurized acetylene.[5] With succinic acid as the model compound, an extensive
screening of catalysts and process conditions for the reductive amidation will be
shown. As a consequence, the production of HEP in high yields with subsequent
purification can be realized under optimized conditions. Finally, the dehydration of
HEP is achieved over mild solid acids in a continuous gas phase reactor. Optimized
acid properties and process conditions are implemented to avoid cleavage of the
hydroxyethyl substituent. Purification by distillation ultimately yields the desired
monomer, thus completing a process chain characterized by efficient catalytic
conversions and simple purification operations.

Acknowledgements
We thank the German Federal Ministry of Education and Research (BMBF) for funding of the project
Bio-PVP (FKZ 031B0487A) in the framework “Neue Produkte für die Bioökonomie”. Furthermore, the
Chemical Industry Fund (FCI) is gratefully acknowledged for its support through a PhD scholarship to
Mr. Haus.

Literature
[1] T. A. Werpy, J. E. Holladay, J. F. White, Top Value Added Chemicals From Biomass. I.
Results of Screening for Potential Candidates from Sugars and Synthesis Gas, 2004.
[2] X.-L. Du, L. He, S. Zhao, Y.-M. Liu, Y. Cao, H.-Y. He, K.-N. Fan, Angew. Chem. 2011, 123,
7961.
[3] Grand View Research Inc., Polyvinylpyrrolidone (PVP) Market Worth $2.75 Billion by 2024,
PR Newswire 2016. Visited 15.10.2017.
[4] Y. Louven, K. Schute, R. Palkovits, ChemCatChem (accepted) [DOI: 1002/cctc.201801751].
[5] a) Y. Shimasaki, H. Yano, K. Ariyoshi und H. Kambe, Journal of Molecular Catalysis A:
Chemical 2005, 239, 125–129. b) Y. Shimasaki and H. Yano, Nippon Shokubai Co., Process for
production of tertiary n-alkenyl carboxylic acid amide, EP 0701998 B1 1998.

Image Sources
[1] Imbedded images designed by Cornecoba and Freepik - Freepik.com
 Experimental Investigation of the Unsteady-State Operated co-
Methanation of CO/CO2 mixtures using Ni/Al2O3 Catalysts
D. Meyer1, J.Schumacher1, J. Friedland1, R. Güttel1
1
Institute of Chemical Engineering, Ulm University

Typically, chemical processes are operated in steady-state mode. The operating

parameters are kept constant to achieve an optimum yield, a constant product quality
and to minimize the effort for process control. However, for utilization of renewable
resources it could be beneficial to operate chemical reactors dynamically, due to
fluctuating inlet streams, being the Power-to-Methane (PtM) process a current
example. An interesting carbon source for the PtM process are industrial exhaust
gases, such as coke oven gas, which consist of a mixture of CO and CO2 [1] leading
to a co-methanation reaction mechanism. For the steady-state case the co-
methanation mechanism is widely investigated, especially the inhibiting effect of CO
[2]. However, for the unsteady-state case only little is known on the influence of CO,
even though a profound understanding of the dynamic methanation of CO/CO2
mixtures is essential for the implementation of the co-methanation in a sustainable
energy scenario based on renewables.

In this contribution, we present experimental results on the effect of CO for CO2

methanation using Ni-based catalysts. The experiments are carried out under
isothermal and stoichiometric conditions with a differential reactor design. The inlet
composition is step-changed periodically with variation in frequency. In order to
address fluctuations expected in realistic environments a rather broad range of period
durations is studied by variation of the CO fraction at different reaction temperatures.
An internal standard is used to determine the inherent dynamic system behavior,
according to Friedland [3]. The results in the unsteady-state case are compared with
the steady-state case based on the reaction rate of methane and the conversion of
the carbon source.

Exemplarily, the effect of CO is shown by a periodic exchange of CO and CO2 in

Figure 1 for a period of 120 s. The results reveal the inhibiting effect of CO at the
catalyst surface, which is evident due to the observed maximum in the methane and
H2O concentration, when the partial pressure of CO decreases and consequently the
surface concentration of CO. The opposite effect occurs as the CO concentration
increases in the gas phase and thus at the active surface. The methane
concentration drops to a minimum, accordingly.

Figure 1: Average response curves of the reactants individual normalized ion current on a periodic exchange of
CO with CO2 (period duration 120 s, T = 553 K, p = 2 bar); H2 is in a stoichiometric ratio to the carbon source and
40 mol-% Ar are used.

In summary, the influence of CO on the unsteady-state co-methanation is studied by

analyzing the system response of the reactants with respect to an internal standard.
The obtained conversion and reaction rates under dynamic conditions are compared
with the steady-state case. The results give a valuable insight of the poisoning effect
of CO in unsteady-state co-methanation and lead to conclusion about the tolerant
operation windows for dynamic feed operation.

[1] M.A. Schöß, A. Redenius, T. Turek, R. Güttel, Chemie Ingenieur Technik 86 (2014) 734–739.
[2] G.D. Weatherbee, C.H. Bartholomew, J. Catal. 77 (1982) 460–472.
[3] J. Friedland, Charakterisierung eines instationären Reaktionssystems mittels Pulsreaktion am
Beispiel der CO-Methanisierung, Dissertation, TU Clausthal, 2018.
 Cobalt-Based
Based Core-Shell
Core Shell Catalysts for COx Hydrogenation:
Investigation of Stability under Reaction Conditions
A. Straß-Eifert,
Straß C. Zambrzycki and R. Güttel
Institute of Chemical
Chemi al Engineering
Engineering, Ulm University, D-89069
89069 Ulm
In term
terms of energ
energy re
revolution
olution the Fischer-Tropsch
Trop h (FT) Synthesis
S nthe i has
ha gained more and more
attention in scientific
ientifi research
re earch, since it offers a CO2-neutral
neutral wa
way for the production
produ tion of high
quality fuels
qualit fuel from alternative resour
resources.
e Here, the conversion
on er ion of syngas
ngas (CO and H2) derived
from biomass at ele
elevated
ated temperature and pre
pressure
ure using
u ing for example
e ample Co
Co-based catalysts
leads to produ
lead production
tion of long-chain
long hydrocarbons, like paraffins and olefins
olefin as well as
oxygenates and the co-product
product water [1].
[ Additionally, novel core-shell
hell material
materials are under
investigation
in e tigation offering many advantages,
ad antage such as stabilizing
tabili ing metal nanoparti
nanoparticles
le from
sintering
intering and the po
possibility
ibility to tailor the combination
ibilit ombination of physical
ph i al and chemi
chemical
hemi al fun
functionalities
tionalitie
on the nanoscale [2].
]. Therefore, Kruse et al. [3] combined a cobalt core
ore and a zeolitic shell
(e. g. ZSM5)) to lin
link both Fischer-Tropsch
Fischer Trop h (FT) and hydrocracking
h dro ra ing (HP) a
activity
ti it within one
single
ingle nanoparti
nanoparticle.
le. The gained re
results
ult re
revealed
ealed a better re
resistance
i tance
tan e against
again t catalyst
atal t
deactivation
dea ti ation as
a well a
as a narrowed product
produ t distribution.
di tributi
However, there are further investigations
inve tigation necessary to understand
er tand morphology
morpholog and structural
tru tural
changes
hange during redu
reduction,
tion, catalyst
catal
atal t activation
a ti ation and reaction
rea tion to de
design
ign the optimal FT catalyst,
atal t,
being stable
table in the h
hydrothermal
drothermal en
environment
ironment and able to control
ontrol the FT produ
productt di
distribution.
tribution.
Therefore, we investigate these zeolite encapsulated cobalt catalyst materials
material before and
after FT synthesis
nthe i using
u ing transmi
transmission
tran mi ion ele
electron
tron mi
microscopy
ro op (TEM), detecting
dete ting a change
hange of the
structure of the cobalt
obalt particles lo
located
ated at the external surface of the zeolite
eolite crystals.
r tal In order
to o
overcome
er ome di
disadvantages
ad antages of these
the e ex
e situ
itu measurements en
environmental
ironmental TEM (ETEM)
experiments
e periment were performed under synthesis
nthe i gas
ga atmosphere
atmo phere and elevated
ele ated temperature.
Two different cobalt
obalt species
pecies with different stability
tabilit behavior depending on the chemical
hemi al
surrounding are ob
observed
er ed in terms
term of metal particle
p sintering up to 700°C.
In addition, the degree of cobalt
obalt parti
particle
le encapsulation
en ap ulation in the zeolite
eolite crystal
rystal
r tal was
wa investigated
by cutting slices of the composite
omposite material using
u ing the fo
focused
u ed
ion beam (FIB) method (Fig. 1), since the location of the
cobalt parti
particles
le inside
in ide and/or outside
out ide the zeolite
eolite matrix
matri
considerably
on iderabl affe
affects
t the resulting FT product
produ t distribution,
di tribution, as
a
recently pointed out by Carvalho
rvalho et al. [4].
[4 For improving the
encapsulation
en ap ulation degree the bottom-up synthesis route
developed by Kruse et al. [3]] was
wa modified as shown in Fig.

2. For this purpose Co3O4 nanoparticles

nanoparti le are synthesized
nthe i ed and Figure 1:: TEM image of a foil of
Co3O4@HZSM5
@HZS prepared via FIB
subsequently
ub equentl covered
o ered b
by a non-porous
non silica shell yielding Co3O4@SiO2. In an additional
step the core-shell
hell particle
particles
parti le were covered
o ered b
by a porou
porous silica
ili a shell
hell yielding
ielding
Co3O4@SiO2@mSiO2. Finally, the double la
layer
er silica
ili a shell
hell is
i transformed
tran formed into zeolite
eolite ZSM5
through h
hydrothermal
drothermal (HT) [3] or steam-assisted
team a i ted (SAC) [5] treatment, after the addition of an
aluminum source.

Figure 2: Modified synthesis

nthe i strategy nthe i of Co3O4@HZSM5
trategy for the bottom up synthesis ZSM5 particles
particle via
ia h
hydrothermal
drothermal or
steam-assisted crystallization.

The results reveal successful

u essful conversion to zeolitic material dete
detected
ted by x-ray diffraction
(XRD) and N2-physisorption
h i orption data
data, as well as a higher degree of en
encapsulation
apsulation of the cobalt
obalt
oxide particles in
inside
ide the zeolite
eolite crystals
r tal byb scanning
anning ele
electron
tron microscopy
mi
microscop
ro op with energy
energ
dispersive x-ray
ra spectroscopy
pe tro copy (SEM-EDX).
(SEM Catalytic testing under CO and CO2 methanation
conditions were performed
ormed confirming
onfirming the activity
a ti it of the improved
impro ed material
materials..

References
[1]] R. Güttel, T. Ture
Turek,, Energy Technolog
Technology 2016, 4, 44.
[2] Q. Sun, X.-Q.
Q. Zhang, Y. Wang, A.-H.
A. H. Lu, Chine
Chinese
e Journal
ournal of Catalysis
Catal i 2015, 36, 683.
[3]] N. Kru
Kruse,
e, A. G. Ma
Machoke,
ho e, W. Schwieger,
S hwieger, R. Güttel, ChemCatChem 2015, 7, 1018.
[4]] A. Car
Carvalho,
alho, M. Marino
Marinova,
a, N. Batalha, N. R. Marcilio,
Mar ilio, A. Y. Khod
Khodakov,
a o , V. V. Ordom
Ordomsky,, Catal
Catalysis
i
Science
S ien e & Te
Technology
hnolog 2017, 7, 5019.
[5] A. G. Ma
Machoke,
ho e, A. M. Beltrán, A. Ina
Inayat,
at, B. Winter, T. Wei
Weissenberger,
enberger, N. Kruse,
Kruse
Kru e R. Güttel, E.
Spiecker,
Spie er, W. S
Schwieger,
hwieger, Advanced
Advan ed Materials
Material 2015, 27, 1066.
Conditioning of coke oven gas: catalytic conversion of oxygen
traces on platinum catalyst
T. Wiesmann1*, H. Lohmann1, S. Kaluza1,2
1
Fraunhofer Institute for Environmental, Safety, and Energy Technology UMSICHT, Oberhausen/Germany
2
Hochschule Düsseldorf - University of Applied Sciences, Düsseldorf/Germany

Motivation
The steelmaking industry is the largest energy consuming manufacturing sector in
the world and is responsible for 5-7 % of anthropogenic CO2 emissions [1, 2]. In the
processes of steel production, large quantities of process gases are generated. The
process gas with the second largest share in the steel making process is coke oven
gas. With a volumetric hydrogen fraction over 60 %, coke oven gas is regarded a po-
tential source for synthesis gas based processes instead of the conventional energet-
ic utilization [1, 2]. However, the gas mixture requires extensive gas purification in
order to be used for downstream catalytic processes. A reasonable option is the sep-
aration of hydrogen by pressure swing adsorption [3]. As even traces of oxygen re-
duces the efficiency of the adsorption process and moreover, could lead to the for-
mation of explosive gas mixtures its removal is of major importance [4, 5]. In this con-
text, our public funded research project aims on the investigation of noble and non-
noble metal-based catalysts for the catalytic conversion of oxygen traces in complex
gas mixtures.

Experimental
The test system used for the catalytic tests comprised seven pure gas components
and one test gas. An evaporator allow the addition of water to the gas mixture. The
reactor has an diameter of 1 inch and a length of 500 mm. In a first approach, a cata-
lyst based on platinum supported on alumina spheres with a diameter of 3 mm was
applied. At a space velocity (GHSV) of 10000 h-1, the temperature was varied be-
tween 50 °C and 500 °C. The gas matrix consisted of the main gas components of
coke oven gas (H2 60 vol-%, CH4 24 vol-%, CO 5 vol-%, CO2 2 vol-%, O2 0,5-1 vol-
%, taces of H2S) [6].

Results
Due to the complex gas matrix of the coke oven gas, an analysis of the individual
reaction paths in the first step is not feasible. Therefore, the complexity was de-
creased by successively applying only the single main gas components together with
oxygen at in
increasing
rea ing temperature.
temperature As expected, the
he highe
highestt conversion
conver ion of oxygen
was achieved with h
hydroge
drogen already below 60 °C in the reaction gas. Nevertheless, it
is important to know the reaction
rea tion path and the temperature at which methane and
carbon
arbon mono
monoxide
ide are reacted
reacted. The activation energy for the o
oxidation
idation of methane and
carbon
arbon mono
monoxide
ide is
i higher compared to hydrogen. This higher energy
energ could
ould be pr
pro-
vide by the
he e
exothermic
othermi energ
energy of the h
hydrogen conversion. Following
ollowing the investiga-
in e tig
tion of the indi
individual
idual main ga
gas components
omponent with oxygen, the main gas
ga components
omponent
were te
tested
ted together with different feasible rea
reaction
tion inhibiting component
omponents.. While the
influence
influen e of carbon
arbon dioxide wa
was relatively low, the addition of carbon monoxide
mono ide at
temperatures below 100 °C led to a drastic decrease of conversion.
on ersion. This decrease is
attributable to the ad
adsorption
orption of carbon
arbon mon
monoxide
o ide on the catalyst
atalyst surface.
urfa e An en-
hancement of the temperature led to an increased desorption rate of carbon
arbon mono
monox-
ide from the catalyst
atal t surface
urface and thus, to an increased oxygen conver
onversion.
ion

Our re
recent
ent studies
tudie fo
focus
us on different compositions of the main gas components
component in a
temperature range between 150 and 250 °C. Furthermore, the gas complexity
omple it will
increase by adding water vapor and further relevant components such as
a H2S.

Acknowledgments
The work is performed in collaboration with our partner
partners from the research project
Carbon2Chem® supported
upported b
by the German Federal Ministry
Mini tr of Edu
Education
ation and Re-
R
search.

References
[1] J.. M. Bermúdez,
Bermúde , B. Fidalgo, A. Arenilla
Arenillas,, J.. A. Menénde
Menéndez,, Fuel 2010, 89 (10), 2897 – 2902.
DOI: 10.1016/j.fuel.2010.01.014.
[2] Y. Kim, E. Worrell, Energ
Energy Policy 2002, 30 (10), 827 – 838. DOI: 10.1016/S0301-4215(01)00130
4215(01)00130-6.
[3] J. Shen, Z.-z. Wang, H.-w.
w. Yang, R.-s.
R. Yao, Energy Fuels 2007, 21 (6), 3588 – 3592. DOI: 10.1021/ef700217j.
[4] T. Wiesmann,
mann, C. Hamel, S. Kaluza, Chemie Ingenieur Technik 2018, 90 (10), 1446 – 1452.
DOI: 10.1002/cite.201800022.
[5] W. Leitma
Leitmayr,
r, P. Leitgeb, U. Wenning, T. Keller, EP 1 967 491 A2, 2008.
[6] J. M. Bermúdez, N. Ferrera-Lorenzo, S. Luque, A. Arenillas, J. A. Menéndez, Fuel Processing Technology 2013, 115,
215 – 221. DOI: 10.1016/j.fuproc.2013.06.006.
A study on the dehydrogenation of loaded liquid organic hydrogen
carriers (LOHC) with heterogeneous catalysts

X. Chen, R. Palkovits, J. Artz, RWTH Aachen, Aachen/D

Hydrogen is gaining importance as an energy vector and CO2-free hydrogen

production followed by the application in the mobility sector and chemical industry are
desired. A new concept is to store hydrogen in so called Liquid Organic Hydrogen
Carriers (LOHC) and release it as soon as needed. For this a catalytic hydrogenation
of a hydrogen-lean organic compound is performed, receiving a LOHC. The
hydrogen-rich compound can then be stored without energy losses and transported
over long distances using common transport logistics and infrastructure for liquid
fuels such as pipelines, ships or trucks.
In this work supported metal catalysts were investigated and optimized for the
dehydrogenation step within the LOHC system perhydro
dibenzyltoluene/dibenzyltoluene (H18-DBT/H0-DBT). The catalysts’ choice was
subject to a systematical screening process. Based on the current benchmark Pt/γ-
Al2O3, the active species (metal) and the support were kept constant, respectively,
while the other compound was changed in order to elucidate the individual
contributions on the resulting dehydrogenation activity. Among the oxidic supports
(γ-Al2O3, α-Al2O3, TiO2, ZrO2, CeO2, SiO2) that were impregnated with Pt, Pt/TiO2
(0.5 wt% Pt) based on TiO2 anatase resulted in the highest degree of
dehydrogenation (ca. 88 %). This is even higher than the degree of dehydrogenation
of ca. 70 % achieved with Pt/γ-Al2O3 (0.5 wt% Pt) under comparable reaction
conditions. Therefore, further studies focused on the optimization and comparison of
the two catalysts Pt/γ-Al2O3 and Pt/TiO2 were undertaken.
Selective poisoning by introducing 0.1 wt% sulfur[1] to Pt/γ-Al2O3 and Pt/TiO2
with a Pt-loading of 0.3 wt% respectively, resulted in an enhanced performance of
the catalysts in dehydrogenation reactions. While the degree of dehydrogenation
enhanced from 89 to 90%, for the sulfated Pt/γ-Al2O3 catalysts compared to a rise
from 85 to 90% after 1.5 h reaction time in case of sulfated Pt/TiO2. Kinetic studies of
these two Pt/TiO2 catalysts are performed and the dehydrogenation at different
temperatures between 270 °C and 320 °C are being compared.
 Besides selective poisoning, the electronic properties of Pt can be modified by
introducing a second metal species, which can have an influence on the H2
adsorption behavior[2]. In order to simplify the comparison of the same active species
on different supports and therefore to unify the metal particles size, supported Pt-
nanoparticles (Pt-NPs) and bimetallic Pt/Co- and Pt/Ni-nanoparticles on γ-Al2O3 were
synthesized for the dehydrogenation of H18-DBT. The received catalysts possess a
very high dispersion of platinum particles (PDI ~ 0.1) with a particle size of 2-3 nm.
The Pt-(NPs)/γ-Al2O3 with 0.3 wt% metal loading resulted in lower degrees of
dehydrogenation compared to the benchmark Pt/γ-Al2O3 and the synthesis and
workup procedure are being optimized to achieve comparable results. The bimetallic
Pt/Co-NPs on γ-Al2O3 (0.3 wt% Pt and 1 wt% Co) on the other hand resulted in a
degree of dehydrogenation of 90% after a reaction time of 1.5 h. This promising
catalyst will be characterized in further studies.

Acknowledgment
The authors gratefully acknowledge funding by the German Federal Ministry of
Education and Research (BMBF) within the Kopernikus Project P2X: Flexible use of
renewable resources – exploration, validation and implementation of ‘Power-to-X’
concepts.

References
[1] F. Alhumaidan, D. Cresswell, A. Garforth, Energy Fuels, 2011, 25(10), 4217-4234.
[2] J.R. Kitchin, J.K. Nørskov, M.A. Barteau, J.G. Chen, The American Physical
Society, 2004, 93 (15).
 Reaction kinetic modeling of the direct synthesis of dimethylether
from CO2-rich synthesis gas, model-based reactor optimization and
experimental validation
N. Delgado Otalvaroa, M. Kaisera, K. Herrera Delgadob, S. Wildb, J. Sauerb, H. Freunda
a
Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Erlangen/Germany
b
Karlsruhe Institute of Technology (KIT), Karlsruhe/Germany

Introduction
Predictive models are essential in chemical reaction engineering for process design,
process optimization and scale-up. In this work, model-based optimization was
applied to the direct synthesis of dimethylether (DME). The direct synthesis combines
methanol synthesis from syngas and its succeeding dehydration to DME in a single
step. This route is believed to be an effective pathway for the production of one of the
most promising fossil fuel alternatives for diesel engines1.

Experimental Investigations, Modeling & Optimization

To perform model-based optimization, resilient reaction kinetic models are essential.
Accordingly, kinetic measurements were carried out in a fixed-bed reactor using a
mechanical mixture 1:1 of a commercial CZA catalyst for methanol synthesis and γ-
Al2O3 for selective methanol dehydration to DME at different space-times,
temperatures and feed compositions. A reaction kinetic approach from open
literature2 was modified and parametrized using a non-linear regression method
implemented in Matlab. In the further course, this model was applied within a
dynamic optimization scheme based on Freund et.al.3 in order to improve the
laboratory scale reactor performance. For this aim, a predictive model consisting of
balance equations, kinetic approaches and thermodynamic considerations was
developed, implemented and utilized for the maximization of the single-pass
conversion of COx based on an exemplary feed composition. The considered
optimization variables were the total gas flow, temperature and composition of the
mixed catalytic bed.

Results and Discussion

A major achievement is the reaction kinetic model itself. Based on an existing
approach4, it was developed to exhibit increased numerical stability, adapted to fulfill
the requirement
requirements of the optimi
optimization
ation routine, and parametrized
parametri ed to fit the experimental
e perimental
data consisting
on i ting of 240 experiments.
experiment . The goodness of fit of this model is
i illu
illustrated
trated b
by
means of parity plots (Fig. 1). The enhancement of the COx-conversion
onversion achieved by
optimization is outlined
ined in the state
tate space
pa e diagram (Fig
(Fig. 2) where the COx-conversion
is plotted against the temperature for a reference and an optimized
ized catalytic bed
composition. Compared to reference
referen e conditions
ondition (1), the
he conversion
conver ion could be
improved
impro ed b
by appr. 20% at the calculated optimal conditions (2) reaching almost the
thermodynamic
thermod nami equilibrium. The
he optimi
optimization
ation results
re ult obtained numerically
numeri all were
validated e
experimentally
perimentally whereby the enhan
enhancement
ement of the single-pass
single COx-
conversion and the DME-yield
yield could be demonstrated.

Conclusions
A rea
reaction
tion kinetic
ineti model with a broad validity
alidit range suitable
uitable for optimi
optimization
ation purpo
purposes
e
was developed and parametrized.
parametri ed. An optimi
optimization
ation problem aimed towards the
maximization
ma imi ation of the single
ingle-pass COx-conversion by selecting
ele ting optimal values
alue for
temperature, total gas flow and the catalytic
atal ti bed composition
ompo ition was
wa solved.
ol ed The
performance
performan e enhancement
enhan ement wa
was demonstrated experimentally closing
clo ing the loop
between kinetic in
investigation
e tigations,, optimi
optimization
ation via
ia rigorou
rigorous mathematical modeling and
experimental validation.

Figure
Figure 1. Parity 2.for
Plots State
tate
CO,space diagram
CO2, DME and H2
Total
otal
Temp.: 220-260 °C,ga
gas flow:
.: 500.2
Pres.:
Pre SLPM,
bar, Feed Feed
gas gas comp.:
ga comp.:
omp.:
yCO: 4-15 %, yyCO2
CO :: 1-3
yCO2%,
: yTotal
: 16gas
H2otal % :flow:
ga 2.8 % : 48.4SLPM
0.2
0.2-0.7 %

References
1
H.G. Roh and C.S. Lee and S. Chang. Fuel Propertie
Properties and Emi
Emission
ion Chara
Characteristics
teri ti of Dimethyl
Dim Ether in a
Diesel Engine. In Lo
Locomotives
omoti e and Rail Road Tran
Transportation.
portation Springer, Singapore, pp. 113-128,
113 2017
2
W. Lu, L. Teng, and W. Xiao. Simulation and experiment
e periment study
tud of dimeth
dimethyll ether synthesis
nthesis from syngas
nga in a
fluidized-bed reactor. Chem. Eng. Sci,
Sci 59 (22-23):5455-5464, 2004.
3
H. Freund, A. Pe
Peschel,
hel, K. Sundmacher, Model
Model-based
ba ed rea
reactor
tor de
design
ign ba
based
ed on the optimal reaction
rea tion route, Chem.-
Ing.-Tech. 83 (4)420–426, 2011
 Catalysts for the conversion of dimethyl ether to low-aromatic
gasoline

Benjamin Niethammer, Ulrich Arnold, Jörg Sauer

Karlsruhe Institute of Technology (KIT), Institute of Catalysis Research and

Technology (IKFT)

Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany

Abstract:
The production of fuels from renewable feedstocks can help to reduce CO2 emissions
in the transport sector and to achieve the current climate targets. Several strategies,
such as the Dimethylether-To-Gasoline (DTG) process, have been developed and
feasibility has been demonstrated on industrial scale. The DTG approach employs
zeolite catalysts for the production of gasoline fractions from dimethyl ether (DME)
with relatively high contents of aromatic compounds in the final product. These
products can be used as anti-knock additives for gasoline, due to their high octane
numbers, without increasing the oxygen content and lowering the heating value.
However, aromatics are known to be precursors of soot formation in the engine
combustion chamber. Besides the reduction of greenhouse gases, improving the air
quality, especially in densely populated areas, is currently a major topic. In addition to
improved exhaust aftertreatment systems, changes of the fuel composition can
contribute to a reduction in harmful particulate emissions. One approach for this
purpose is to reduce the aromatics content in gasoline.
Zeolites that differ in their morphology from the standard ZSM-5 type can change the
product spectrum of the DTG reaction. Within this work, different zeolite types are
tested in a newly constructed continuously operated laboratory plant. The catalysts
are assessed and compared regarding their selectivity to non-aromatic C5+
compounds. The main focus is on increasing the content of highly branched alkanes
in the boiling range of gasoline with high octane numbers. A remaining challenge is
the rapid deactivation of the catalysts. Strategies for catalyst modification with the
objective of improved long-term stability are currently investigated and will be
presented and discussed.
Regeneration of supported catalytically active liquid metal solutions
(SCALMS) for propane dehydrogenation

Moritz Wolf, Narayanan Raman, Nicola Taccardi, Marco Haumann, Lehrstuhl für
Chemische Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg
(FAU), Erlangen, Germany; Peter Wasserscheid, Lehrstuhl für Chemische
Reaktionstechnik, Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU),
Erlangen, Helmholtz-Institut Erlangen-Nürnberg für Erneuerbare Energien (IEK-11),
Forschungszentrum Jülich, Germany

Supported catalytically active liquid metal solutions (SCALMS) offer the potential for
new and unusual catalytic reactivity in alkane dehydrogenation. SCALMS are
composed of catalytically active liquid alloy droplets on a porous support [1]. In
contrast to conventional supported liquid phase catalysis, the catalytic reaction in
SCALMS occurs only at the highly dynamic liquid metal/gas interface, as the liquid
metal does not provide any relevant reactant solubility. Recently, we reported the use
of Ga-rich Ga/Pd mixtures (atomic Ga/Pd ratio >10) on porous glass in the highly
endothermal n-butane dehydrogenation [1]. The liquid nature of the supported alloy
droplet under the reaction conditions was confirmed through a combination of XRD,
SEM, XPS, and ab initio dynamics calculations. Most remarkably, these SCALMS
materials outperform commercial dehydrogenation catalysts (Pt/Al2O3, Cr2O3/Al2O3)
without any material or process optimisation. The most remarkable finding, however,
is that coking, the typical deactivation mechanism for this type of high temperature
hydrocarbon chemistry under reductive conditions [2-4], is largely suppressed with
SCALMS systems. As explanation for this unexpected behaviour molecular dynamics
calculations suggest that the topmost layer of the Ga-rich Ga/Pd alloy is depleted in
Pd, but the layer directly underneath is enriched [1].

In our current study, the scope of SCALMS was extended to Al2O3 supported Ga-rich
Ga/Rh catalysts for propane dehydrogenation. The unique properties of the SCALMS
approach resulted in a remarkable activity and selectivity towards propene, which is
in contrast to literature reporting a poor performance of Rh based catalysts in alkane
dehydrogenation [5,6]. Once again, the formation of carbon was limited by the highly
dynamic liquid/gas interface of the supported liquid alloy. Nevertheless, observed
deactivation may be related to the formation of coke. Hence, spent catalysts were
regenerated via
ia temperature programmed o
oxidation
idation (TPO) in 21% O2/He. The TPO
was monitored by
wa b means
mean of thermogra
thermogravimetry
imetr in a XEMIS sorption
orption analyser
anal er (Hiden
IIsochema)
o hema) equipped with a ma
mass spectrometer
pe trometer (MS) to identif
identify different ttypes
pe of
carbonaceous
arbona eou species.
pe ie . Furthermore, performan
performance
e data during dehydrogenation
deh drogenation are
compared
mpared to the amount of formed coke.
o e. In addition, in situ
itu deh
dehydrogenation-
drogenation
regeneration cycles were conducted
condu ted allowing for dire
directt monitoring of the formation of
coke
o e while deactivation
dea ti ation can be validated
alidated u
using
ing the MS
MS.. La
Lastly,
tly, the kinetic
ineti of coke
o e
oxidation by O2 during catalyst
catal
atal t regeneration ha
has been anal
analysed
ed by
b iisoconversional
o on er ional
methods pro
providing
iding insight
in ight into the rea
reactivity
ti it of the formed coke.
o e

Figure 1 Compari on of various

Comparison variou conversion
on er ion levels
le el of coke
o e (α
( i) in the Arrhenius
Arrheniu plot according
a ording to
the iisoconversional
o on ersional method by Starink [7] during temperature programmed oxidation
o idation in
21% O2/He at different heating rates
rate (β
( i) for a spent
pent Ga/Rh SCALMS catalyst
atal t applied
in propane dehydrogenation.

References
[1] N. Ta
Taccardi,
ardi, M. Grabau, J.. Debu
Debuschewitz,
hewit , M. Distaso,
Di ta o, M. Brandl, R. Ho
Hock,, F. Maier, C. Papp, J..
Erhard, C. Nei
Neiss,, W. Peu
Peukert,
ert, A. Görling, H.P. Steinrück,
Steinrü , P. Wasserscheid, Nat. Chem.
Chem 9 (2017) 862.
[2] J.R. Rostrup-Nielsen, J.. Catal
Catal. 85, (1984) 31.
[3] V.L.
L. Ku
Kuznetsov,
net o , A.N. UUsol’tseva,
ol’tseva, Y.V. Butenko,
Buten o, Kin. Catal. 44 (2003) 726.
[4] J.J.H.B. Sattler, J. Ruiz-Martine
Martinez,, E. Santillan-Jimenez,
Santillan B.M. Weckhuysen, Chem. Rev. 114 (2014)
10613.
[5] D.E. Resasco, G.L. Haller, J. Phys.
Ph . Chem.
Chem 88 (1984) 4552.
[6] F. Sol
Solymosi,
mo i, P. Tomal
Tomalcsov,
ov, K. Kedves,
Ked e , J. Catal. 216 (2003) 377.
[7] M.J. Starink, Thermo
Thermochimhim Acta 404 (2003) 163.
 Aerosol synthesis of metal catalyst particles with tunable pore
sizes, defined metal crystallite sizes and different loadings.

A. Martinez Arias, A.P. Weber, Institute of Particle Technology / TU Clausthal

Abstract

Due to their unique properties, porous particles with well-defined pore structures are
of interest for many applications including as catalysts support for metallic active
components. The efficiency of the final catalyst strongly depends on the properties of
the support such as pore size as well as of the metal nanoparticles such as crystallite
size and metal loading, herein for the production of the desired catalyst particles,
these parameters needs to be defined.
The aim of this contribution is to introduce a “one-step” aerosol synthesis
method for porous catalyst particles with SiO2 as a support and different metals like
cobalt oxide and nickel oxide with tunable pore size and defined metal crystallite size.
Furthermore, a model of the mechanics representing the growth of the metal particles
inside this SiO2 matrix will be outlined as a function of calcination time and
temperature, metal loading, and surface area.
For the production of these catalyst particles, the metal component was
directly dissolved as nitrate into the silica suspension and spray-dried. The metal
particles were formed directly during the drying and calcination process within the
porous silica matrix.
In this one-step aerosol synthesis of porous catalyst particles the metal
crystallite size can be controlled through the calcination parameters (duration and
temperature). The pore size can be adjusted in broader steps by varying the primary
particles size of the support, and in smaller steps by changing the pH of the final
suspension before the spray drying.
The advantage of this method is the formation of catalyst particles with independently
adjustable pore size, crystallite particle size and metal loading. Moreover, this
aerosol synthesis method is a flexible process that can be extended for the
preparation of catalyst containing different supports and metals for several
applications.
 Selective Oxidation of n-Butane to Maleic Anhydride: Kinetic
Investigation in a Milli-structured Reactor

Mauritio Müller1, Gerhard Mestl2, Thomas Turek1,

1
Institute of Chemical and Electrochemical Process Engineering, Clausthal University
of Technology, Germany
2
Clariant Produkte Deutschland GmbH, Bruckmühl, Germany

The selective oxidation of n-butane to maleic anhydride (MA) is one important

example of highly exothermic processes, which are typically carried out in salt bath
cooled multi-tubular fixed bed reactors. Due to limited heat removal, the process is
accompanied by the occurrence of hot spots up to 70 K above the temperature of the
surrounding salt [1]. In order to prevent the reactor from thermal runaway, the n-
butane concentration in industrial reactors is restricted to values below 2 %.
As could be demonstrated in previous work [2], it is possible to carry out the selective
oxidation of n-butane under well-defined nearly isothermal conditions using a milli-
structured fixed bed reactor. While modelling this reactor it was found, that none of
the published kinetics can satisfactorily reproduce the experiments. In particular, the
published kinetics cannot describe the formation of the by-products like acetic and
acrylic acid. Therefore, the objective of the current work is to determine the kinetics of
the process, including the formation of by-products under well-defined conditions.

To investigate the kinetics, experiments were carried out in an improved version of a

previously described [2] salt bath cooled milli-structured fixed bed reactor of
44x72x1.65 mm. The experiments were conducted under industry-near conditions,
namely 380 to 440 °C and 0.9 to 2.1 % n-nutane in air. For a more detailed
investigation of the undesired decomposition reaction of MA, some experiments were
carried out under co-feeding of MA using a two-step saturator. Additionally, to obtain
a better description of the influence of water on the reaction kinetics, some
experiments were performed under dosing of up to 4% water(vapor) to the feed.
In order to avoid disadvantageous effects of mass transfer resistances, the
experiments were carried out under higher flow rates (3900 to 4800 Nm³/(m³h) than
used for industrial reactors and with fine particles obtained from milling industrial
catalysts.
The effluent ga
gases
e were analyzed
anal ed by
b an online ga
gas chromatograph
hromatograph for butane, MA
and organi
organic side
ide products like
li acetic acid
id and a pro
process
e gagas analyzer
analy er for butane,
CO, CO2 and O2. For determining the kinetic
ineti parameters,
parameter , the reactor was
wa de
described
ribed
by a detailed heterogeneou
b heterogeneous rea
reactor
tor model in gPROMS. Thi
This model wa
was u
used
ed to fit
the e
experimental
perimental data u
using
ing the parameter e
estimation
timation tool of gPROMS.

In the e
experiments,
periment , no differen
differences
e between catalysts
atal t of different parti
particle
le sizes could
be ob
observed,
er ed, so
o that ma
mass tran
transfer
fer can
an be regarded a
as sufficiently
uffi ientl
iently good for reliable
kinetic
ineti eexperiments.
periment . The ob
observed
er ed hot spots
pot are below 5 K and can
an be well
described by the model. Therefore,
Therefore the error through the non-isothermal
isothermal behavior
beha ior of
the rea
reactor
tor should
hould be small.
mall.

From a comparison
ompari on of the different kinetic
ineti approa
approaches
he published
publi hed in the literature ((e.g.
Eley-Rideal, Langmuir-Hinshelwood
Hinshelwood,, and Mar
Mars van
an Krevelen
Kre elen model
models) it could be
shown, that an Eley-Rideal
Rideal approa
approach
h lilike
e de
described
ribed by
b Lesser
Le er et al. [3] is the best
one to fit the e
experimental
perimental data. A
According
ording to thi
this kinetic
ineti model, the reaction
rea tion iis
inhibited by n-butane
utane and water. In contrast to literature, the measured selectivities
e of
acetic and acrylic acid
id are in the range of up to 3.8 and 3.2 % (Figure 1) and
therefore are considered
on idered in the kinetics.
ineti . To account for these side products,
produ t , the
reaction
rea tion network
networ was
wa expanded lilike
e shown
hown in figure 2.

Figure 1. Measured selectivity

ele ti it to MA, CO, CO2, Acetic Figure 2. Reaction Network (MA: maleic
malei anh
anhydride,
dride,
Acid
A id and Acrylic
A r li Acid
A id as
a a function
fun tion of the conversion
on er ion AcA:
A A: a
acetic
eti aacid,
id, A
AcrA:
rA: acrylic
acr li Acid)
A id)

[1] G. Me
Mestl,
tl, D. Le
Lesser,
er, T. Ture
Turek,, Top. Catal. 59 (2016) 1533-1544
[2] S. Hofmann, T. Turek, Chem. Eng. Technol. 40 (2017) 2008-2015
[3] D. Le
Lesser,
er, G. Mestl,
Me tl, T. Ture
Turek,, Chem. Eng. Sci.
S i. 172 (2017) 559-570
559
Poster Abstracts
New Reactor Concepts
 Modelling of Integrated Membrane Reactors for the Selective
Dehydrogenation of Propane
A. Brune, Otto von Guericke University, Process Engineering, Magdeburg, Germany,
A. Seidel-Morgenstern, Otto von Guericke University, Magdeburg, Germany,
C. Hamel, Otto von Guericke University, Process Engineering, Magdeburg, Germany
and Anhalt University of Applied Sciences, Engineering, Köthen, Germany

Propene is one of the key building blocks in petrochemical industry. Traditional routes
for propene production are refining and steam cracking processes. Since the
feedstock for cracking shifts to light olefins, on-purpose production of propene
attracts significant attention [1].

A highly selective already industrially established reaction for propene production is

the thermal dehydrogenation of propane (TDH). Several processes are commercially
available (CATOFIN®/STAR®/Oleflex® process). A major drawback is the rapid coking
of the catalysts applied, that makes regeneration necessary. Catalyst regeneration
can be realized periodically or continuously [2]. An alternative reaction for the
production of propene is oxidative dehydrogenation (ODH) of propane. Since O2 is
involved undesired total and partial oxidations are hard to prevent. Integrated
membrane reactor concepts can help to reduce the disadvantages of both process
concepts (TDH and ODH) by combining them in one apparatus. The main idea is
illustrated in Figure 1.

Figure 1: Example for an integrated membrane reactor concept with operando regeneration by flow reversal.

Different integrated reactor setups have been evaluated in preliminary studies. For
both TDH and ODH a VOx catalyst (Al2O3 support) was used [3]. Improved
performance with respect to the overall yield of propene was observed.

To evaluate the full potential of the suggested new concepts a sound knowledge of
all chemical and thermodynamic processes occurring in the reactor is needed. This
includes predominantly the reaction kinetics as well as deactivation and regeneration
kinetics. For modelling the process, mass and heat transfer problems have to be
accounted as well.

Long time PFTR experiments (>24h) have been conducted to determine kinetic
parameters of the underlying reaction network, including deactivation kinetics. The
following parameter range was covered: Tdeact = 350°C – 550°C, cC3H8,in = 0% - 5%,
cO2,in = 0% - 1%. Reactivation has been studied with thermogravimetric
measurements at different temperatures and oxygen concentrations (NETZSCH STA
449F5, cO2,in = 0% - 20%, Treact = 350°C – 550°C). A broad range of different process
conditions was covered to establish a robust kinetic model. Results of 1-D
simulations of a PFTR and a membrane reactors have been acquired exploiting

MATLAB. An example is given is given in Figure 2.

Figure 2: Simulation of a membrane reactor in MATLAB (WHSV = 400, xO2,in,MB = 1%, xC3H8,in = 1%, TS/SS = 1/8)

To analyze the more sophisticated membrane reactor concepts in more detail radial
gradients have to be considered as well. To study this, corresponding solutions were
generated using COMSOL Multiphysics® [4] (Fig. 3). Thus, it was possible to
evaluate and compare different reactor concepts with respect to their overall
performance. The integrated reactor concepts offer promising results and motivate

TODH,max=799 K
Porous membrane wall

ODH
TDH

TTDH,max=783 K steel tube

further experimental investigations in a pilot scale.

®
Figure 3: Simulation of a membrane reactor using COMSOL Multiphysics [4] (W/F = 100 (kg s)/m³, C3H8,in = 1 %,
O2/C3H8,in = 2, Tin = 430 °C).
References
[1] V. Blay, B. Louis, R. Miravalles, T. Yokoi, K. A. Peccatiello, M. Clough, B. Yilmaz, ACS Catal.
2017, 7 (10), 6542 – 6566. DOI: 10.1021/acscatal.7b02011.
[2] P. Eisele, R. Killpack, in Ullmann's encyclopedia of industrial chemistry, Vol. 82, Wiley.
Chichester 2010.
[3] C. Hamel, T. Wolff, P. Subramaniam, A. Seidel-Morgenstern, Ind. Eng. Chem. Res. 2011, 50
(23), 12895 – 12903. DOI: 10.1021/ie2001692.
®
[4] COMSOL Multiphysics 5.3a, Chemical Engineering Module, https://www.comsol.com/
 Benefits of Actinometry for Systematic Photoreactor Development
B. Wriedt, M. Sender, F. Huber,
Huber S. Rau, D. Ziegenbalg, Ulm University,
Univer it Germany.

In the course
our e of the growing intere
interestt in photo
photochemical
hemi al synthe
ynthesis
nthe i route
routes,, the
increasing
in rea ing research
re ear h effort ha
has led to a huge di
diversity
er it of photoreactor
reactor geometries
geometrie and
operation conditions. [1-3] In many
man of these
the studies,
tudie , the main focus is on the general
feasibility
ilit of photo
photochemical
hemical reactions.
rea tion . Howe
However,
er, the development
de elopment of general de
design
ign
and appli
application
ation rule
rules to optimi
optimize
e process
pro e concepts
on ept require
requires more specific
pe ifi and
sophisticated measure-ment
ment tool
tools to pro
provide
ide accurate
a urate and reliable experimental
e perimental data
of further measures.
The efficiency of photochemical
photochemi al reactors
rea tor iis quite important a
as it comes
come to appli
application
ation
on a larger scale.
ale. It is
i essential to e
evaluate
aluate and compare
ompare the efficiency
efficien of the setup
as a whole. As the geometri
geometrical
al arrangement of the different component
omponent within the
omponents
irradiated space (e.g. the light source
our e and size
i e of the rea
reaction
tion chamber)
hamber) plays a
significant role, it iis too simple to consider
on ider onl
only the installed
in talled component
components on their
own.
An ambitious effort to gain holistic
holi ti insight iis to close
lo e the photon balan
balance
e of the whole
reactor setup. Sin
Since
e the rea
reaction
tion rate of photoreactions
photorea tion is
i usually
u uall limited b
by the
absorbed
ab orbed photon flux,
flu , accurate
a urate mea
measurement
urement method
methods need to be established.
e tabli hed. For
this, a self-validating procedure of actinometry and radiometry was
wa de
developed
eloped to
accurately determine the amount of photon
photons per time interval initiating the
photoreaction.
This
Thi pre
presentation
entation focuses
fo u e on
actinometry. By this method, the
t
amount of photons being actually
absorbed within the reactor
rea tor can be
measured
mea ured spectrally
pectrally re
resolved
ol ed in
the rele
relevant
ant wavelength range (see
Fig. 1). Opti
Optical
al effects
effe t such
u h a
as
reflec-tion, scatter
scattering and
transmission are intrinsically
accounted. With this information,
reactor geometries and materials
Figure 1: Absorption
A s r ti spectr
spectra off s me material and improve-ments
some improve can
actinometers. be evaluated and their influence
influen e
meaningfully quantified.
meaningfull
Additionally,, a further application
Additionall appli ation of a
actinometry
tinometr is
i the transfer
tran fer from a low
low-scale batch
experiment to a continuously
inuously operated process.
pro e . SSystematic
temati reactor development
de elopment and
improvement
impro ement can
an benefit signifi
significantly
ignifi antl if supported
upported by
b actinometry.
a tinometr
tinometry.. Thi
This can
an be ea
easily
il
realized
reali ed due to the relatively simple
imple handling and the well-known
well nown properties
propertie of the
actinometric reaction.

Figure 2: Example for an Ru-based

Ru ba ed photo
photocatalyst
atal t (left). The process
pro ess was
wa tran
transferred
ferred
from a bat
batch
h fla
flask (middle) to a continuously
ontinuou l operated photo mi
microrea
roreactor
rorea tor (right).

This approach will be exemplarily

exemplaril demonstrated
demon trated on photocatalytic water-splitting
water with
[4]
a Ru-based mole
molecular
ular catal
catalyst. The oxygen-sensitive
en iti e product require
requires an inert
atmosphere, hence optimizing the external photonic efficiency by use of the actual
a tual
chemical system is not only very resource and time consuming but also
al o prone to
errors. To ta
tackle
le the
these
e issues,
issue a recycle-reactor has been e
extensivel
tensively evaluated by
actinometry prior to conducting
onducting the reaction of interest in thi
this reactor.
reactor The gained
results
re ult could
ould successfully
u e full
fully be used
u ed to transfer
tran fer the reaction
rea tion from a S
Schlenk-flask
Schlen
hlen to the
recycle-reactor,
rea tor, yielding
ielding better rea
reaction
tion control,
ontrol, the possibility
po ibility
ibilit to in
install
tall online
analytics
anal ti and in
insights
ight on possible
pos ible scale-up
ale strategies.

References
[1]] Ziegenbalg, D.; Krei
Kreisel,
el, G.; Weiß, D.; Krali
Kralisch,
h, D.: OLEDs
OLED as
a prospective
pro pe ti e light sour
sources
our e for
microstructured photoreactors, Photochemical
Photo hemi al & Photobiological
Photobiologi al Sciences,
S ien e 2014,, 13, 1005–1015.
[2]] Lé
Lévesque,
e que, F.; Seeberger, P. H.: Highly
Highl Efficient
Effi ient Continuous
Continuou Flow Rea
Reaction
tion Using Singlet O
Oxygen
gen
as a "Green"Reagent, Organi
Organic Letter
Letters, 2011, 13/19, 5008–5011.
[3]] Vin
Vincze,
e, L.; Kemp, T. J.;
.; Unwin, P. R.: Flow a
actinometry
tinometr in a thin film rea
reactor:
tor:
modeling and measurements, Journal of Photochemistry and Photobiology, A: Chemistry, 1999, 123.
[4] Mengele, A. K.; Seibold, G.M.; Eikmanns, B.J.; Rau, S.: Coupling Molecular Photocatalysis to
Enzymatic Conversion, ChemCatChem Catalysis, 2017, 9, 4369-4376.
Optimal “Egg-Yolk” Catalyst Particle Design for Thermal Sensitivity
Reduction of Industrial Scale Fixed-Bed CO2 Methanation Reactors

Ronny Tobias Zimmermann, M.Sc.1, Jens Bremer, M.Sc.2,

Prof. Dr.-Ing. Kai Sundmacher1,2
1
Otto-von-Guericke Universität, Universitätsplatz 2, 39106 Magdeburg, Germany
2
Max-Planck-Institut für Dynamik komplexer technischer Systeme,
Sandtorstraße 1, 39106 Magdeburg, Germany

Power-to-Methane processes enable efficient surplus electricity storage harvested

from volatile energy sources (e.g. wind, solar). In order to avoid the integration of
large gas buffer tanks, a flexible operation of commonly used fixed-bed methanation
reactors is favorable. According to the availability of surplus energy, these reactors
need to operate in a broad load range. However, this further amplifies the importance
of heat management, as the high exothermicity of the methanation reaction is a
challenge even at steady-state operation. Much research has been dedicated to this
purpose, focusing mainly on the manipulation of reactor scale variables. The
influence of catalyst particles has not been studied in depth so far.
To fill this knowledge gap, simulation studies were performed by employing a
heterogeneous reactor model. Suitable degrees of freedom on the particle scale
have been identified, which can be used to improve the performance of the
methanation reactor for flexible operation. Subsequently, the carbon dioxide
conversion of the reactor was rigorously optimized with different catalyst particle
concepts subject to the particle activity, permeability and heat conductivity. The
optimized concepts were then further evaluated via sensitivity analyzes regarding
coolant temperature, reactor inlet flow rate and reactor pressure. Additionally,
dynamic simulation studies were performed, in order to identify the influence of the
catalyst particle design on the dynamic reactor behavior.
The results show that reactors filled with optimized “egg-yolk” catalyst particles
exhibit a reduced thermal sensitivity due to a damped ignition (Figure 1).
Furthermore, these particles offer a more flexible reactor operation under different
reactor loads and a beneficial dynamic behavior.
Figure 1: Comparison of the ignition curves of a catalytic fixed-bed tubular reactor filled with optimized homogeneous
particles and optimized “egg-yolk” particles.
 Reactor concept for scale-up of hazardous flow chemistry

Marlies Moser, Esteban Maria Rosasco, Alain Georg, Fluitec mixing + reaction
solutions AG, Seuzachstrasse 40, 8413 Neftenbach, Switzerland

Flow Chemistry at production and pilot scale presents new challenges to plant
manufacturers. Scale-up of highly exothermic and fast reactions requires reliable
safety measures. This poster shows a reactor concept with safety elements for
hazardous reactions including technical and electronic solutions to prevent an
excessive temperature and pressure.
The DN50 reference pilot plant for 2500 – 4300 t y-1 consists of two dosing systems,
a tubular reactor containing static mixer heat exchangers [1], the safety purge system
and a quench tank (Figure 1). Its underlying concept merges directives and
standards of four fields: mechanical engineering (PED 2014/68/EU, MD 2006/42/EC,
ATEX 2014/34/EU), chemical engineering (thermal safety concepts from F. Stoessel
[2]), electrical engineering and safety (functional safety SIL according to EN 61511).

Figure 1: Reference pilot plant (2500 – 4300 t y-1) containing two dosing systems,
DN50 mixer heat exchanger and the safety purge system with quench tank.
With this plant, three protection goals are met: dosing, inadmissible temperature and
pressure. The devices are monitored by multiple mass flow meters, axial temperature
sensors along the reactor, SIL approved temperature sensors and pressure sensors.
In the case of a failure, the SIL approved safety purge system will empty out the
reactor within a few seconds and direct the media to the quench tank, where it will be
immediately inertised. It was developed as an event preventing safety device.
Besides this also damage limiting devices were installed such as rupture discs and a
safety valve.
This concept together with the scalable bundle mixer heat exchanger provides a way
to tackle the scale-up problem of highly exothermic reactions in tubular reactors. The
reactor and programming of the control system needs to be adjusted according to the
characteristic temperature levels of the desired and decomposition reaction.

[1] A. Georg, M. B. Däscher, Chem. Ing. Tech. 2005, 77 (6), 681–693. DOI:
10.1002/cite.200407095.
[2] F. Stoessel, Thermal Safety of Chemical Processes: Risk Assessment and
Process Design, John Wiley & Sons, Weinheim 2008.
 New reactor concept for continuous milli-reactors
milli reactors

Marlies Moser, Esteban Maria Rosasco, Alain Guy Georg, Fluitec mixing
mi ing + rea
reaction
tion
solutions AG, Seuzachstrasse
Seu a h tra e 40, 8413 Neftenba
Neftenbach,
h, Switzerland

Based
Ba ed on the safety
afet concept
concepts
on ept for bat
batch
h pro
processes,
e e , a new safet
safety
afet concept
on ept for
continuous milli-reactors
rea tor
tors wa
was de
developed.
eloped. The new concept
on ept can
an be used
u ed for tube and
loop rea
reactors
tor aas well a
as for combinations
ombination of tube and loop reactors.
reactor
rea tor . The reactor
rea tor
concepts are in
increasingly
rea ingl
ingly being implemented with a new design
de ign of stati
static
tati mi
mixer
er heat
exchangers [1]. The new method covers
o er all current
urrent European standards
tandard and
regulations and merges the four different field
fields:: me
mechanical
hani al engineering (PED
2014/68/EU, MD 2006/42/EC,
2006/42/EC ATEX 2014/34/EU),
), chemical
hemi al engineering (thermal
safety concepts from F. Stoessel
Stoe el [2]),
), ele
electrical
tri al engineering and safet
safety (fun
(functional
tional
safety SIL according to EN 61511).
61511 The reactor concept consists
onsists of the following
parts (Figure 1):

Thermal
Safety
risk
objectives
analysis

Proof of
calculation safety
classes
Registration
1-5

Number of
protection
levels 2 - 3

Figure 1: S
Schematically
hemati all illustrated method of the reactor design.

The functional safety SIL is based

ba ed on the pro
proven
en model of protection la
layer.
er. The proof
of calculation
al ulation ha
has been certified by
b the swiss
wi safety
afet center.
enter.
The re
result
ult iis a no
novel
el design of continuous
ontinuou milli
milli-reactor that allows to carry
arr out high
highly
exothermic
e othermi rea
reactions
tion with a signifi
significantly
ignifi antl lower amount of solvent.
ol ent. In a referen
reference
e plant
(Figure 2),, solvents
ol ent can
an even
e en be completely
ompletel eliminated, re
resulting
ulting in considerable
on iderable
energy savings.
Figure 2: Reference plant DN50, annual capacity from 2500 to 4300 t y-1, L x W x H,
6 m x 2 m x 2.5 m.

[1] A. Georg, M. B. Däscher, Chem. Ing. Tech. 2005, 77 (6), 681–693. DOI:
10.1002/cite.200407095.
[2] F. Stoessel, Thermal Safety of Chemical Processes: Risk Assessment and
Process Design, John Wiley & Sons, Weinheim 2008.
Development of reactors for the plasma-catalytic removal of oxygen
traces in steel mill gases

T. Nitsche*, C. Unger‡, M. Budt‡, W: Althaus ‡,.

*: Fraunhofer UMSICHT, Osterfelder Straße 3, 46047 Oberhausen, tim.nitsche@umsicht.fraunhofer.de
‡: Fraunhofer UMSICHT, Osterfelder Straße 3, 46047 Oberhausen

Motivation
The required process temperature of industrial chemical conversions can be reduced
by using catalysts. Opportunities for further improvement of the reaction are the ex-
ternal excitation of reactants or active centers of the catalyst, which allows even fur-
ther reduction of the reaction temperature in certain reaction setups. Microwaves,
UV-radiation and plasma are known technologies for external excitation. The poten-
tial of non-thermal plasma in combination with a catalyst is already intensively inves-
tigated for removal of trace components such as volatile organic compounds (VOC)
in air [1] and NOx in diesel exhaust gases [2]. Within the research project Car-
bon2Chem® the potential of plasma-catalysis shall be investigated for the treatment
of off-gases from steel production. general feasibility of the process with respect to
industrial scalability of plasma-catalytic reactor systems must be proven. The focus of
the plasma-catalytic conversion in this project lies in the conversion of oxygen traces
in steel mill gases.

Experimental
A test rig for the plasma catalytic conversion has been designed and assembled. The
test system provides gas mixtures for typical steel mill gas compositions (possible
main components: H2, CH4, CO2, CO, N2; minor components: O2). Additionally, an
evaporator allows the feed-in of water vapor from liquid water to the gas mixture. The
presented plasma reactor in Figure 1 is based on the packed-bed-DBD design [3–5].
 Figure 1: plasma catalytic reactor setup (packed bed DBD)

The reactor allows conversions in the residence time range of 1-2 s (= GHSV of 3600
– 1800 h-1). The discharge gap of the DBD is varied from 2-4 mm. Furthermore, other
reactor setups are in development (a surface-DBD-setup is tested at Ruhr-University
Bochum and the design of a corona discharge reactor and further volume-reactor-
DBD concept is under development at Fraunhofer UMSICHT). The reaction products
are analyzed by IR-spectroscopy, a thermal conductivity detector (TCD), paramag-
netic and electrochemical sensors.

Results

The combination of non-thermal plasma with catalyst allows the conversion of oxy-
gen traces in hydrogen rich (20 – 60 vol%) gas mixtures similar to coke oven gas
mixtures. The investigated DeOxo-catalyst shows complete conversion of O2 traces
with hydrogen in the investigated GHSV range, but the catalyst is deactivated by CO.
Non-thermal plasma allows partial O2 conversion in presence of CO. Placement of
catalyst granules in the discharge zone (in-plasma-catalysis) allows improvement of
the oxygen conversion compared to the non-thermal plasma treatment. While the
principle feasibility has been clearly demonstrated, the conversion rate has to be fur-
ther optimized by geometrical adaption of the reactor setups to establish a homoge-
neous and better controllable plasma treatment. Afterwards the next scale-up step
towards a pilot installation using real process gas streams can be taken.
Detailed results will be presented at the congress.

Acknowledgments
The work is performed in collaboration with our partners in the research project Car-
bon2Chem® supported by the German Federal Ministry of Education and Research.

References
[1] Vandenbroucke AM, Morent R, Geyter N de, Leys C. Non-thermal plasmas for
non-catalytic and catalytic VOC abatement. J. Hazard. Mater. 2011;195:30–54.
[2] Bhattacharyya A, Rajanikanth BS. Discharge plasma combined with bauxite res-
idue for biodiesel exhaust cleaning: A case study on NOx removal. IEEE Trans.
Plasma Sci. 2015;43(6):1974–82.
[3] Y. Zeng, X. Tu. Plasma-Catalytic CO2 Hydrogenation at Low Temperatures.
IEEE Transactions on Plasma Science 2016;44(4):405–11.
[4] Gómez-Ramírez A, M. Montoro-Damas A, Rodríguez MA, R. González-Elipe A,
Cotrino J. Improving the pollutant removal efficiency of packed-bed plasma reac-
tors incorporating ferroelectric components. Chem. Eng. J. 2017;314:311–9.
[5] Khalifeh O, Taghvaei H, Mosallanejad A, Rahimpour MR, Shariati A. Extra pure
hydrogen production through methane decomposition using nanosecond pulsed
plasma and Pt–Re catalyst. Chemical Engineering Journal 2016;294:132–45.
 Bridging the gap by printing a gap:

Metallic porous-dense composites by selective laser melting

D. Xie, E. Hansjosten, M. Hofheinz, M. Klumpp, R. Dittmeyer

1
Institute for Micro Process Engineering,
2
Institute for Catalysis Research and Technology,
Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen/Germany;

Introduction
For small-scale application, modular microstructured chemical reactor systems are
very promising for the intensification of chemical processes by the high ratio of
surface area to reactor volume allowing to e.g. efficiently remove the heat of reaction.
Further, by using advanced fabrication methods, additional functionalities can be
implemented. One example is the combination of methane steam reforming with
separation of the hydrogen generated via a selective palladium membrane allowing to
shift the thermodynamic equilibrium and to generate hydrogen of highest purity.[1] To
support the thin membrane, porous metallic structures are to be incorporated in the
microstructured reactor. However, the combination of porous (membrane support)
and dense (reactor body) structures requires several additional fabrication steps such
as laser welding. A promising approach to simplify the production process is using
3D printing of metals to additively manufacture the reaction module with integrated
porous structures. 3D-printing also allows for more complex geometries for further
miniaturization as well as for customization adopted to the needs of the given
application. Nowadays, there are several powder bed based methods commercially
available to 3D-print porous metallic structure (e.g. binder jetting[2]) as well as several
techniques for 3D-printing of dense metallic structure (e.g. selective laser melting,[3]
selective electron beam melting[4]). However, to the best of our knowledge, there is
no systematic study on the combination of porous and dense parts within one single
3D-printed structure. In this contribution, we present our first results in combining
different 3D-printing parameters for realizing porous-dense composite structures
using selective laser melting. The relations between the different printing parameters
and the properties of the resulting test specimen (porous array within dense frame)
help understanding the additive manufacturing of such composite structures with
potential application in e.g. membrane and phase separation processes.
Experimental and Results
Selective laser melting (SLM125
(SLM by ReaLizer GmbH,, see
ee Fig. 1
1) was used for
printing the test specimen based on metallic powder (316L
316L stainles
tainless steel,
teel particle
size 5-30 μm). A
As depicted in Fig.
Fig 2, several printing parameters have
ha e been varied
systematically in order to achieve
achie e porous
porou structures
tru ture with pore size well below 150µm
and optimized surface roughness
roughne within a dense frame. In particular, the
t influence of
e.g. hatch distance / orientation,
orientation and laser point distance applied in the 3D-printing
3D
process were studied. SEM and optical profilometry were u
used
ed to characterize the
surface morphology of the samples (Fig. 3). It could,, for in
instance,
tance, been shown that
with de
decreasing
rea ing hat
hatch
h di
distance,
distan
tan e, the surface
urfa e roughness
roughne and the appearan
appearance
e of large
defect holes increase.

Based on the relation

relations found, iin this study composite structures with combined dense
and porous arrays with optimized
optimi ed pore size
i e and surface were achieved.
achie ed Ongoing
research is focusing on the permeabilit
permeability of the composite
ompo ite structure
tructures in order to
quantify the characteristics
quantif hara teri tics of the porous
porou arrays.
arra .

[1] T. Böltken et al. (2014). International Journal of Hydrogen Energy, 39(31), 18058-18068.
18058
[2] B. Verlee et al. (2012). Powder Metallurgy,
Metallurg , 55(4), 260-267.
[3] E. Louvis et al. (2011). Journal
ournal of Material
Materials Pro
Processing
e ing Te
Technology,
hnolog , 211(2), 275-284.
275
[4] C. Körner (2016), International Materials
Material Reviews
Re iew 61(5), 361-377.
 Design Concepts for Increasing the Photonic Efficiency in
Photomicroreactors
Maximilian Sender, Benjamin Wriedt and Dirk Ziegenbalg, Ulm University, Germany;

In times when ecological aspects widely affect science and economy, the
development of new photochemical synthesis routes grows unabated. The increasing
research effort in the investigation of photochemical reactions has led to a huge
[1-4]
diversity of reactor geometries and operation conditions. Furthermore, modern
UV-LEDs begin to become widely used in lab-scale photoreactors because of their
beneficial photons per cost ratio. This fact itself could be considered as a gain in
efficiency, however, in many published studies, the focus is on the general feasibility
of the photochemical reaction, whereas the focus of our work is the development of
general design and application rules to optimize process concepts. This requires
more specific and sophisticated measurement tools to provide accurate and reliable
experimental data of further measures.
For this sake, it is essential to evaluate and compare the photochemical setups as a
whole. Considering only the installed components (e.g. the light source and size of
the reaction chamber) on their own is too simple, because the geometrical
arrangement of the different components within the irradiated space plays a
significant role.
An ambitious effort is to close the photon balance of a whole reactor setup. For this,
the research group developed a method for an accurate measurement of the amount
of photons per time interval by chemical actinometry and radiometry. These two
methods can be validated against each other. In addition, the radiometric method is
also capable to detect the amount of photons at a specific location in the
photoreactor. This is realized by a calibrated spectrometer, scanning the radiation
field of the setup. For this, the spectrometer is moved by a custom-made system (see
Fig. 1).
Within our studies, two reasons for the loss of photons in photochemical setups were
identified. One of them is the mismatch of the illuminated area and the area where
radiation can be absorbed by the reaction inside the photoreactor. The second one is
the fact that radiation gets lost by scattering and diffraction every time it crosses a
phase boundary.
An approach to tackle these two issues
i ue b by an ad
advanced
an ed reactor concept
on ept will be
presented in this work. B
By adapting the radiation field of the light source,
our e the
mismatch
t h between illuminated area and reaction
rea tion area is minimized. This is done by
the use of lenses or mirrors,
mirrors, fo
focusing
u ing the emitted light. In order to minimize
minimi e the pha
phase
e
and material tran
transitions
itions on the light path, one concept
on ept is
i to integrate light emitting
diodes into the reactor
diode rea tor wall. The rea
reactor
tor wall material of choice
hoi e is silicone.
sili one. B
By FDM
3D-printing,
rinting, CAD de
designed
igned mold
molds can
an be produ
produced
ed rapidly.
rapidl . The reactor
rea tor then can
an be
produced
produ ed b
by mold casting
a ting with tran
transparent
paren silicone, light
ight sources
ources can
an be alread
already
included during the casting
asting process.
pro e . BBy thi
this,, not onl
only more efficient reactors
rea tor can
an be
produced, they can also be easily in
investigated
e tigated b
by the radiometric scanning de
device
i e of
the research group. This was
wa done for differ
different rea
reactor
tor geometries, reactor
rea tor material
and the efficiency improvements
improvement were e
evaluated
aluated and their influen
influence
e meaningfull
meaningfully
quantified.

Figure 1: Schematic drawing of the constructed

on tru ted cube,
ube, the arrangement of the reactor
rea tor
and the mea
measuring
uring de
device
i e (left). Rendered CAD pi
picture
ture of the belt driven
dri en slid
lid (right).

References
[1] Aillet, T.; Loubiere, K.; Dechy--Cabaret,
Cabaret, O.; Prat, L.: A
Accurate
urate Measurements
Mea urements of the Photon Flux
Flu
Received
Re ei ed In
Inside
ide Two Contiuous Flow Microphotoreactors
Mi rophotorea tor by
b Actinometry,
A tinomet International Journal
ournal of
Chemical Reactor Engineering, 2014,
2014 12, 1–13.
[2] Ziegenbalg, D.; Krei
Kreisel,
el, G.; Weiß, D.; Krali
Kralisch,
h, D.: OLED
OLEDs a
as pro
prospective
pe ti e light sources
sour
our e for
microstructured photoreactors, Photochemical
Photo hemi al & Photobiological
Photobiologi al Sciences,
S ien e 2014,, 13, 1005–1015.
[3] Lé
Lévesque,
e que, F.; Seeberger, P. H.: Highl
Highly Efficient
Effi ient Continuou
Continuous Flow Rea
Reaction
tion Using
U ing Singlet Oxygen
O gen
as a "Green"Reagent, Organi
Organic Letter
Letters, 2011, 13/19, 5008–5011.
[4] Vin
Vincze,
e, L.; Kemp, T. J.;
.; Unwin, P. R.: Flow a
actinometry
tinometr in a thin film rea
reactor:
tor:
modeling and measurements, Journal of Photochemistry and Photobiology, A: Chemistry, 1999, 123.
 Novel approaches in rapid prototyping for the development of
reactors for photocatalytic applications

Fabian Guba, Ulm University/Germany, Dirk Ziegenbalg, Ulm University/Germany

The new relevance of photochemical reactors

The benefits of photochemistry for synthetic chemistry are well known for many
decades. High selectivities and a prevention of harsh, high temperatures are just one
of these features. Nevertheless, in chemical industry photoreactions and
photoreactors lead a shadowy existence. However, thanks to the invention of UV light
emitting diodes (UV-LEDs), revealing multiple game-changing features such as a
compact design and quasi-monochromatic emission characteristics, new
perspectives are opened.[1]

In this contribution, these features are combined with another exciting technology,
Fused Filament Fabrication (FFF) 3D-printing, to investigate new reactor designs for
photochemical reactions. By application of a rapid prototyping workflow, that includes
the use of a feedback cycle between developed prototypes, a consistent adaption of
the reactor geometry is targeted.[2]

Photocatalytic reactions and Rapid Prototyping

In photochemistry, the use of semiconductors such as TiO2 as photocatalyst can

open the way to completely new synthetic routes.[3,4] One outstanding example for
such a reaction is the one-pot photocatalytic synthesis of quinoline from nitroarenes.
However, this reaction raises special demands to the reactor as well as to the rapid
prototyping approach. The reactor has to handle high catalyst loadings and has to be
manufactured from a chemical resistant material.

In this contribution three reactor types for the photocatalytic synthesis of quinoline are
presented including a batch and a flowthrough reactor prototype as well as a reactor
concept with immobilized photocatalyst (Figure 1). All reactors were fabricated from
chemical resistant polypropylene.

Aiming for an adequate suspension quality and photon input, multiple stirrer designs
and installations such as baffles were tested in the batch reactor. To evaluate the
impact of these modifications, an experimental protocol including actinometry
measurements, mixing experiments and photocatalytic test reactions was developed.
The flowthrough reactor was designed in a modular diffuser/nozzle design comprising
a composable top and bottom part. This feature allowed easy modifications of the
inner reactor geometry, which enabled detailed investigations of the effect of
extended shadowed zones on the photocatalytic reaction. To support these trails
additionally, computational fluid dynamics calculations were conducted to identify
beneficial fluid guidance. Tedious catalyst removal represents one major drawback
for photocatalytic reactions that are conducted in suspensions. To circumvent this
point, a manufacturing procedure is presented that allows catalyst insertion into the
printing material leading to photoactive printed reactor models.

Advantages and challenges of the reactor prototypes are presented in this study. In
this context perspectives of rapid prototyping for the development of photoreactors
will be discussed.

Figure 1: Photo batch reactor setup (left) and a flowthrough reactor prototype.

[1] J.Wan-Kuen, Ind. Eng. Chem. Res. 53 (6), S. 2073–2084.

[2] F.Guba, U. Tastan, K. Gugeler, M. Buntrock, T. Rommel, D. Ziegenbalg, Chemie
Ingenieur Technik, accepted, to be published
[3] H. Kisch, Angew. Chem. (Int. Ed.), 2013, 52, 812–47.
[4] M. Cherevatskaya & B. König, Russ. Chem. Rev., 2014, 83, 183–195.
 Dehydrogenation of LOHC in a reactive plate heat exchanger

Thomas Solymosi, Patrick Preuster, Peter Wasserscheid

Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU),

Institute of Chemical Reaction Engineering

Hydrogen is a key player in the process of developing an energy storage concept

without carbon dioxide emission. The storage of hydrogen in Liquid Organic
Hydrogen Carriers (LOHCs) is a strategy that benefits in many ways: the liquid is not
flammable, the volumetric energy density is comparable to liquefied hydrogen but the
LOHC needs no permanent cooling and can be transported and stored using existing
fuel facilities. [1] Dibenzyltoluene (DBT) is a LOHC that can be loaded with hydrogen
exothermically at 150-250 °C and 30-100 bar. The endothermic dehydrogenation is
carried out under pressure of 1-5 bar and temperatures up to 310 °C as shown in
scheme 1.

Pt on Al2O3
+ 9 H2
Ru on Al2O3

ΔHR = 65

Scheme 1: Dehydrogenation of H18-DBT and hydrogenation of DBT after [2]

The common catalyst for the dehydrogenation is a Platinum on γ-Al2O3 spherical

eggshell catalyst, which is used in a tubular fixed bed reactor. Especially in the first
part of the reaction zone, the endothermicity causes a radial temperature gradient
that leads to a lower catalyst utilization.
The reactor concept of a reactive plate heat exchanger helps to reach a more
homogenious temperature profile. For this concept metal sheets need to be coated
on one side with a catalytically active layer, which withstands mechanical and
thermal stress and reaches similar productivities as the commonly used catalyst.
This work deals with different methods to prepare a catalyst coating on small metal
plates and possible approaches to arising challenges. It compares different coating
techniques of the catalyst support as dipcoating and electrophoretic deposition,
different metals for the primary support, as shown on the left in graphic 1, a variation
of the Pt-nanoparticle
nanoparti le size
ize and a variation
ariation of the post
po t heat treatment of the prepared
catalyst plates.
Due to the large amount of e
experiments
periment to be carried
arried out, a screening
reening rea
reactor
tor for
twelve
twel e plates
plate was
wa designed
de igned and built to be able to monitor twel
twelve
e samples
sample
ample in parallel,
as shown on the right in graphic
graphi 1. Ea
Each
h chamber
hamber is
i connected
onne ted to a ga
gas inlet for
inertization,
inerti ation, catalyst
atal t release
relea e and sample
ample ta
taking
ing and a reflu
reflux cooling
ooling ssystem
tem a
as a ga
gas
outlet. Additionall
Additionally,, the reactor consists
on i t of a heated gla
glass top part, so
o the LOHC

vapor will not condensate

onden ate and block
blo the view
iew into the rea
reactor
tor chamber
hambers..

Once, the
he preparation method iis optimi
optimized
ed regarding mechanical
me hanical
hani al stability
tabilit of the
coating
oating and produ
productivity
ti ity of the catalyst,
atal t, it is
i scaled
aled up to manufacture heat exchanger
e hanger
plates.. A reactive
plate rea ti e plate heat e
exchanger
hanger will be built and compared
ompared to other
dehydrogenation setups
ups in terms
up term of performance
performan e by
b reactor
rea tor weight, re
response
pon e time to
changes
hange in power demand, manufacturing
manufa turing costs
o t and scalability.
alabilit .

References
[1]] Brü
Brückner
ner N, Obesser
Obe ser K, Bö
Bösmann
mann A, Tei
Teichmann
hmann D, Arlt W, Dungs
Dung J,, et al.,
Graphic 1: Variation of the primar
primary support
upport metal and it
its influen
influence
e on the wet impregnation (left), side-cut
ide CAD
Evaluation
E aluation of Indu
Industrially
model of the screening
trially Applied
reening reactor
rea tor for the deh
Heat-Transfer Fluids as Liquid Organic
dehydrogenation
drogenation (right)
Organi HHydrogen
drogen
Carrier S
Systems.
tem . ChemSusChem. 2014;7:229-35.
2014;7:229
[2]] P. Preu
Preuster,
ter, C. Papp, P. Wa
Wasserscheid,
er heid, Liquid Organic
Organi Hydrogen
H drogen Carrier
Carriers
(LOHCs):
(LOHC ): Toward a Hydrogen-free
Hydrogen free H
Hydrogen
drogen Economy,
E onom , Account
Accounts of Chemi
Chemical
al
Research, 2017; 50(1), 74-85.
85.
 Scale-up of a Heterogeneous Reactive Extraction with Structured
Packing from Laboratory-Scale to a Pilot-Plant

F. Schwering, U. Hoffmann and U.Kunz

Institute of Chemical and Electrochemical Process Engineering, TU Clausthal

Secondary butyl alcohol (SBA) can be synthesized in a multiphase reaction by the

hydration of butene. An acid ion-exchange resin with an average diameter of 0.6 mm
catalyzes the reaction. The catalyst is hydrophilic, and the reaction takes place inside
the aqueous phase. This means that only the dissolved butene reacts to SBA. Since
the solubility of butene in water is very poor, a second fluid phase, an organic butene
phase is needed to achieve high production rates for SBA. Since SBA dissolves
better in the organic than the aqueous phase, the product is extracted into the
organic phase simultaneously. This process is called heterogeneous reactive
extraction and leads to the benefit that the reaction equilibrium will not be achieved.
This heads for higher production rates since the reaction rates stays on a high level.
In the industry, the synthesis is a bottom-up co-current process, where the organic
phase is dispersed in the aqueous phase.
However, because of the small size of the catalyst it is not possible for the bubbles of
organic phase to pass the fixed bed properly. This leads to a malfunction of the
process. The organic phase formats a slug under the fixed bed and the pressure
drop increases. At one point, it is so high that the jammed butene releases through
channels through the whole bed, which are closing afterwards and the process starts
again from the beginning. [1]
This means that only a small part of the catalyst is used. Furthermore, this
malfunction promotes the subsequent reaction of SBA to the corresponding ether,
because a huge amount of organic phase is in contact with the catalyst. Therefore
Pfeuffer et al [2] developed a new arrangement of the catalyst inside the reactor.
They filled the catalyst into catalytic packing for reactive extraction.
Experiments in a laboratory column showed that the utilization of the catalyst inside
the structured packing is much better than the fixed bed. This effect also
overcompensates the disadvantage of a smaller amount of catalyst in structured
packing with respect to a fixed bed. For this reason, the process will be tested in a
given pilot plant. To get an idea of the operating conditions a scale up was made with
an adjusted packing model of Hoffmann et al. [3]. Fluid dynamic data was given by
Celik [4]. For calculations of the expected production rate the data from the
laboratory experiments and the micro kinetics of Pfeuffer [1] with a new adjustment
were used.
The results show a dramatically change of the mass flux ratio of the reactants with
respect to the current process and an increase of the production rate.

[1] B. Pfeuffer, Process Intensification by Heterogeneous Reactive Extraction,

Dissertation, TU Clausthal 2011.
[2] B. Pfeuffer, U. Kunz, U. Hoffmann, T. Turek, D. Hoell, Catalysis Today 2009,
147, S357-S361. DOI: 10.1016/j.cattod.2009.07.052.
[3] A. Hoffmann, C. Noeres, A. Górak, Chemical Engineering and Processing:
Process Intensification 2004, 43 (3), 383 – 395. DOI: 10.1016/S0255-
2701(03)00121-1.
[4] Y. C. Celik, Fluiddynamische Untersuchungen zur reaktiven Extraktion an
strukturierten Packungen, Diplomarbeit, TU Clausthal 2009.
 Plasma driven fluidized bed reactor concept to reduce metal
powders with oxidized surfaces
M. Bierwirth1, M. Seipenbusch2, A.P. Weber1,
1
Institute of Particle Technology / TU Clausthal, 2ParteQ GmbH

Abstract
The processes of the metal industry are always performed in the presence of oxygen,
naturally in an ambient atmosphere. Therefore, a permanent oxidation of the metallic
surface is occurring, which, dependent on the process and material, leads to oxide
layers of different thickness. Besides the positive effect of corrosion protection, the
oxide layers are mainly an interfering factor in the manufacturing processes.
Therefore, the goal of this work is to present a setup to reduce metal powder in a
fluidized bed reactor. A dielectric barrier discharge (DBD) reactor is used to generate
the active species, which are needed to deoxidize the metal powder.
The process works in an ambient environment. For reducing the metal powder, it is
essential to remove trace oxygen from the system. The goal is to reach an oxygen
partial pressure equivalent to an extremely high vacuum (XHV). The process gas is
doped with silane at very low percentages. The extreme reactivity of silane at room
temperature enables it to react with the trace oxygen and water, thereby producing
hydrogen and silicon dioxide. Only a low doping of silane is needed to reach XHV-
equivalent oxygen partial pressures.
Hydrogen is added to the system through the DBD reactor, where the plasma
generates the reactive species, which enables a reduction of the metal powder. The
short lifetime of these reactive species, introduces a design problem dealing with the
integration of the DBD reactor with the fluidized bed reactor (FBR).
Therefore, results of a miniature fluidized bed reactor are presented. In this reactor
design, the plasma is positioned at the bottom of the fluidized bed to allow the whole
fluidization gas to pass through the plasma.
In a FBR, the residence time required to reduce the batch is easily adjustable, so as
to reach the desired degree of reduction. When the batch is reduced, the gas velocity
is increased, which elutriates the powder into a cyclone, where the powder is
separated into a gas tight container.
Power-to-Gas: CO2 Methanation concepts for SNG production at the
Engler-Bunte-Institut
M. Held, S. Sauerschell, D. Schollenberger, S. Bajohr, T. Kolb,
Engler-Bunte-Institut, Karlsruhe Institute of Technology (KIT)

Power-to-Gas approaches comprise different activities to store electric power in form of

gaseous energy carriers like H2 or CH4. In this context, the synthesis of CH4 used as SNG
(substitute natural gas) with H2 from surplus electric energy and a suitable carbon source
shows several benefits. CH4 is a clean energy carrier of great importance in industry, energy
and transportation sectors. Furthermore, the existing natural gas infrastructure provides huge
storage capacities and a well-established network for distribution and utilization.
Most reactors commonly used for SNG production with electrolytically produced hydrogen
are multi-stage fixed-bed reactor types. The main issue with these reactors is efficient heat
control, since the methanation reaction is highly exothermic. At the Engler-Bunte-Institut
research focuses on methanation in slurry bubble column reactors as well as in honeycomb
reactors to evaluate alternative reactor concepts offering various benefits.

Methanation in a slurry bubble column reactor

The slurry bubble column reactor is characterized by the three phases involved in the
reaction: The reactor volume is filled with a suspension of solid catalyst and an inert heat
transfer liquid; gas flow of educts fluidizes the catalyst. Introducing a heat transfer liquid
facilitates exact temperature control inside the reactor. Further, the reaction system features
high robustness towards dynamic changes e.g. in reactor gas load. This is especially
beneficial in the context of renewable energies where changes in electric power are common
due to the inevitable environmental influences.

Methanation in a honeycomb reactor

A honeycomb reactor features specific metallic installments used to control the temperature
inside the reactor. These metallic structures possess high thermal conductivity, which allow
the efficient removal of reaction heat. The good heat control enables operation of the reactor
system at optimized trajectories of reaction rate. Research topics concerning honeycomb
reactors are experimental characterization of heat transfer and reaction kinetics as well as
CFD calculations for reactor design.
The contribution to the conference will give an overview of the research activities at the
Engler-Bunte-Institut in developing both methanation technologies. Furthermore, it will
compare the technologies and identify viable boundary conditions for their application.
Methanol synthesis in fixed-bed and slurry bubble column reactors

Rafael Becka; Siegfried Bajohr; Thomas Kolb, Engler-Bunte-Institut,

Fuel Technology, KIT, Karlsruhe/Germany
Florian Nestler; Max Hadrich; Ouda M. Salem; Achim Schaadt,
Fraunhofer Institute for Solar Energy Systems ISE, Freiburg/Germany

Methanol synthesis based on synthesis gas obtained from renewable sources and/or
industrial off-gases can provide a sustainable solution for energy and carbon storage.
Methanol can be used as fuel or as a key intermediate for the chemical industry. The
utilization of renewable feedstocks for methanol synthesis leads to two major
challenges namely: (1) the fluctuation of available hydrogen depending on natural
resources like wind and sun radiation and (2) the significantly higher concentrations
of CO2 in the synthesis gas compared with conventional methanol synthesis. Two
reactor concepts are considered promising to meet these requirements: the state-of-
the-art two phase isothermal fixed bed reactor and three phase slurry bubble column
reactor.

The slurry bubble column reactor is in focus of the research activities at the Engler-
Bunte-Institute at KIT. In this reactor concept, catalyst is suspended in a heat transfer
fluid capable of efficiently removing the heat produced by the exothermal methanol
synthesis reaction. It therefore allows perfect control of isothermal reaction
conditions. As the high heat capacity of the heat transfer fluid stabilizes the thermal
behavior of the reactor, the slurry bubble column reactor is a promising concept for
methanol synthesis with fluctuating feed from renewable sources.

The dynamic behavior of the isothermal steam raising reactor is investigated at

Fraunhofer Institute for Solar Energy Systems ISE in Freiburg. In this reactor
concept, the heat of reaction is removed by boiling water evaporating on the shell
side of the catalyst-filled reactor tubes. In contrast to other fixed-bed converters such
as the adiabatic quench bed reactor or the isothermal gas cooled reactor, the steam
raising reactor is more robust against fluctuating process conditions. However,
operation and design of load flexible fixed bed converters is still a topic of research,
as deactivation of the catalyst can be accelerated by high hot-spot temperatures
and/or high water contents inside the reactor. A dynamic simulation has been
implemented in order to describe the practical limitations of the dynamic load
changes inside this reactor.

The slurry bubble column reactor and the isothermal fixed bed reactor will be
compared by their technological potentials in terms of process dynamics, catalyst
lifetime and space-time yield. This is done by a case study performed for both reactor
setups with benchmark feed parameters and reaction conditions, delivering specific
design data for the converters. The lab setups for experimental validation of the
simulations will be introduced, and an outlook for the planned experimental
campaigns will be presented.
Poster Abstracts
Modelling and Simulation
 Dynamic operation strategies for alkaline water electrolyzers
powered by renewable energies

Jörn Brauns, Thomas Turek

Institute of Chemical and Electrochemical Process Engineering, Clausthal University

of Technology, 38678 Clausthal-Zellerfeld, Germany

To utilize higher amounts of fluctuating and intermittent renewable energies, flexible

storage solutions have to be developed. As a solution, hydrogen can be stored in
underground caverns. For large-scale hydrogen production, alkaline water
electrolysis is a promising technology. Unfortunately, these electrolyzers are mainly
operated under stationary conditions and problems with fluctuating energy profiles
might occur. One important problem is related to higher gas impurities at low current
densities during phases with low availability of renewable energies. Since hydrogen
and oxygen form explosive mixtures between around 4 vol.-% and 96 vol.-% of the
foreign gas, water electrolyzers must be shut down for safety reasons when a gas
impurity of 2 vol.-% (50 % of lower explosion limit) is reached [1]. To enhance the
part load range of alkaline water electrolyzers, dynamic operation strategies can be
used. By separating the anodic and cathodic electrolyte cycle (Fig. 1), the hydrogen
content in the anodic oxygen can be lowered significantly.

Fig. 1: Hydrogen content in anodic oxygen during switching between flow modes at
5 bar, 60 °C, 0.35 L min-1 and 30 wt.-% KOH.
The electrolyte volume flow rates are further suitable variables to affect the gas purity
in dynamic operation. Furthermore, temperature and pressure can be also adjusted,
although the system needs some time to respond to those changes [1, 2]. It should
be also kept in mind that the overall cell voltage must be as low as possible since a
high efficiency is necessary for economic operation. Therefore, the separation of both
electrolyte cycles is only possible for limited time since the electrolyte concentration
will drift away from the optimum, resulting in lower conductivity.

For the evaluation of possible dynamic operation strategies, a mathematical model is

used which extends an existing approach by implementing dynamic balance
equations and pressure effects [3]. In addition to simulations with a constant current,
fluctuating energy profiles will be regarded as well.

References

[1] P. Haug, M. Koj, T. Turek, Influence of process conditions on gas purity in alkaline
water electrolysis, Int. J. Hydrogen Energy. 42 (2017) 9406–9418.
doi:10.1016/j.ijhydene.2016.12.111.

[2] P. Trinke, P. Haug, J. Brauns, B. Bensmann, R. Hanke-Rauschenbach, T. Turek,

Hydrogen Crossover in PEM and Alkaline Water Electrolysis: Mechanisms, Direct
Comparison and Mitigation Strategies, J. Electrochem. Soc. 165 (2018) F502–F513.
doi:10.1149/2.0541807jes.

[3] P. Haug, B. Kreitz, M. Koj, T. Turek, Process modelling of an alkaline water

electrolyzer, Int. J. Hydrogen Energy. 42 (2017) 15689–15707.
doi:10.1016/j.ijhydene.2017.05.031.
 Limiting Processes in Oxygen Depolarized Cathodes: A Dynamic
Model-Based Analysis
Maximilian Röhe, Fabian Kubannek, Ulrike Krewer;
Institute of Energy and Process Systems Engineering, TU Braunschweig, Germany
Phone: 0531 391 3038, E-Mail: m.roehe@tu-braunschweig.de

Silver based oxygen depolarized cathodes are of high interest for alkaline fuel cells,
metal-air batteries or advanced chlor-alkaline electrolysis processes. [1] Due to the
fast reaction rate of the oxygen reduction reaction at silver catalysts in alkaline media
and the low oxygen solubility, a tailored design of the gas diffusion electrode is
needed to enlarge the three-phase-boundary and to minimize diffusion limitation.
In this contribution, the first one-dimensional dynamic three-phase model for
analyzing the oxygen reduction reaction in porous silver-based oxygen depolarized
cathodes is presented and it is used for a systematic macroscopic evaluation of the
interaction of electrochemical reaction and mass transport processes. In the model,
the electrode behavior is described by Tafel-Equation, Stefan-flow in the gaseous
phase and Maxwell-Stefan-diffusion in the liquid phase, oxygen dissolution following
Henry’s law and water evaporation following Raoul’s law. [1] Further, due to the high
ionic concentration, the activities of the different species are taken into account. [2]
With the model, we were able to reveal essential new insights into limiting processes.
In particular, the slow mass transport of water or hydroxide ions in the liquid phase
was identified as the overall performance restricting factor. As a negative result of the
slow mass transport, an enrichment of the hydroxide ions close to the gas-liquid
interface causes a shift of the phase equilibrium, which diminishes the oxygen
solubility further and leads to a total depletion of oxygen and finally to the limiting
current density.
Stationary simulation results give insight into the local concentrations and partial
pressure profiles of the different species and reveal a stiff gradient of oxygen in the
liquid phase (see Fig. 2 a) and the enrichment of ions. Dynamic simulations with
potential steps (see Fig. 2 b) are used to identify the different time constants and to
separate overlapping processes. Dynamics of current and local oxygen availability is
strongly impacted by the slow mass transport of hydroxide ions. Thus, future studies
should target to tackle this limiting process to improve the electrodes.
 a) b)

Fig. 2: a) Oxygen concentration dependent on the current density and the diffusion
length in the flooded agglomerates under steady state conditions. b) Dynamic
simulation of potential steps and the according current density

[1] Pinnow, S., Chavan, N., & Turek, T. (2011). Thin-film flooded agglomerate model
for silver-based oxygen depolarized cathodes. In Journal of Applied Electrochemistry,
Vol. 41, pp. 1053–1064.
[2] J. Balej, Activity coefficients of aqueous solutions of NaOH and KOH in wide
concentration and temperature ranges. Collect. Czech. Chem. Commun., vol. 61, pp.
1549–1562, 1996.
 A dual-grid method for dense gas-solid flow using CFD-DEM

Daniel Hirche1,2, Olaf Hinrichsen1,2

1
Technical University of Munich, Department of Chemistry, Lichtenbergstr. 4, 85748
Garching near Munich, Germany
2
Technical University of Munich, Catalysis Research Center, Ernst-Otto-Fischer-Str.
1, 85748 Garching near Munich, Germany

Simulations of chemical reactors using computational fluid dynamics (CFD) has

become more popular over the last years. Dense gas-solid flow simulations can be
achieved through several methods. The most common simulation approaches
comprise the Eulerian-Eulerian, Eulerian-Lagrangian model and the Direct Numerical
Simulation. With the Eulerian-Lagrangian approach the fluid phase is modeled in a
Eulerian way, while the particles are tracked individually with the equations of
Newton’s Second Law of Motion. This approach consists of several sub-models, e.g.,
Discrete Element Model [1], often called CFD-DEM on which the will be on in this
work. The coupling between the fluid and solid phase is done with the calculation of
cell averaged forces between the fluid and particles. Important parameters
influencing these forces are for example the solid phase fraction and the solid phase
velocity. Particles which volumes are overlapping multiple cells are troublesome for
the calculation of cell averaged values [2], as for example the solid phase fraction is
calculated by dividing the total volume of all particles in a cell by the volume of the
cell. Most approaches use the center point of a particle to determine if a particle is
within a certain cell. At the worst, a maximum volume fraction of the particle of 87.5
% is outside of the cell but still accounted for the calculation of the cell-averaged solid
volume fraction. To minimize the magnitude of error for this issue, the cell-to-particle
volume ratio has to be great. In the literature a value of at least two is suggested [3].
The cell size can be scaled up to overcome this problem with the disadvantage of
inaccuracies regarding the fluid flow. Also, simulations of smaller particles are
preferable according to this, but as a result the number of total particles often
increases as well as the computational time.
Figure 1: Schematic overview of dual-grid method for gas-solid flow simulations: a finer grid
for the fluid phase (left) and a coarser grid for the solid phase (right).

A dual-grid method for CFD-DEM simulations was developed to overcome the

problem of grid resolution for the fluid and solid phase. With this method the fluid
phase and the solid phase are calculated on separate computational grids (cf. Figure
1). The grid for the fluid phase consists of a finer grid to resolve the flow structure.
The grid for the solid phase is a coarser one. CFD-DEM simulations require a coarser
grid to model the particulate phase with a high accuracy. Parameters which are
necessary for the calculation of closure terms, e.g., momentum exchange or cell-
averaged volume fraction of the solid phase, are mapped between those grids in a
separate inner loop of the time-step until convergence is reached for each transient
time-step. CFD-DEM simulations with the dual-grid method were performed with lab-
scale geometries found in literature. The grid sizes were varied for the fluid and the
solid phase. All simulation results performed with the dual-grid model are compared
to conventional CFD-DEM solvers. Furthermore, the simulation times for all cases
are evaluated to determine the computational efficiency of the dual-grid method
compared to the conventional solvers.

References

[1] P. A. Cundall and O. D. L. Strack, Géotechnique, (1979), 29, 47–65.

[2] D. Hirche et al., Chem. Eng. J. (in press).

[3] Z. Zhou et al., J. Fluid Mech. (2010), 661, 482-510.

In Operando Adjustable Mass Transport and Flow Characteristics in
Additively Manufactured Periodic Open Cellular Structures

Sebastian Trunk, Giang Do, Wilhelm S

Schwieger,
hwieger, Hannsjörg
Hann jörg Freund
Lehrstuhl für Chemische
Chemi he Reaktionstechnik
Rea tion te hni
Friedrich-Alexander--Universität Erlangen-Nürnberg,
Nürnberg, Erlangen,
Erlangen Germany

In conventional
on entional randomly pa
packed
ed bed reactors,, the flow and mass
ma tran
transport
port
characteristics
hara teri ti are predefined by
b the particle
parti le diameter and the tube diameter.
Structured reactors offer the opportunity
opp to tailor ma
mass transport and flow field
according
a ording to the needs of the reaction system. Howe
However,
er, once
on e the design
de ign iis fi
fixed
ed
they still
the till la
lack fle
flexibility
ibilit and the possibility
po ibilit to precisely adjust and optimize
optimi e the flow
field. One option to enable a highly flexible in operando tuning of the flow field and
the mass transport characteri
haracteristics
ti in chemical
hemi al rea
reactors
tor without changing
hanging the system’s
tem’
periphery is to operate the reactor
rea tor with so-called interpenetrating
interpenetratin Periodic Open
Cellular Structures (interPOCS)
(interPOC as catalyst support structures [1]. By inserting one
POCS ba
based
ed on a diamond unit cell
ell in
into the cavities
a itie of a second diamond cell
ell
structure
tru ture (“loose”
(“loo e” structure),
tru ture), an interwo
interwoven
en and movable
mo able structure
tru ture is formed (Figure
1), whi
which
h can
an be built via
ia additive
additi e manufacturing
manufa turing (e.g. selective
elective
ele ti e ele
electron
tron beam
melting, SEBM).

Figure 1 : CAD sketch

et h of the diamond cell interPOCS; blue: fix structure, orange:: loose
loo e structure
tru ture

These structures offer all the benefits

benefit known from POCS such
u h as,
as e.g., good heat
management and low pressure drop [2, 3], and additionall
additionally provide
pro ide the opportunity of
flow and mixing adju
adjustments
tments by
b shifting
hifting the position of the “loose” structure.
stru ture
Based on detailed computational
omputational fluid d
dynamics
nami (CFD) simulations
imulations
imulation uusing
ing the open
source toolbox OpenFOAM [4] with an additional in-house particle-tra
tracking
ing algorithm
implementation we systemati
stematically
all investigate
in e tigate the local
lo al and
and global flow and mass
ma
transport characteristics within the interPOCS in dependen
dependency of the po
positioning
itioning of the
loose structure. The highly adju
adjustable
table structure
tru ture allow
allows for a broad variation of mixing
mi ing
characteristics and enables
enable ma
mass tran
transport
port optimi
optimization
ation for a given
gi en system.
tem.
Moreover,
Moreo er, it represents
repre ents a completel
completely new appli
application
ation of additive
dditively manufactured
catalyst
atal t support
upport structures
tru tures for highly flexible in operando tuning of flow field and
mass transport characteristic
hara teristics (see Figure 2).
a) b)

Figure 2:
2 a) Axial velocity and b) Longitudinal dispersion
of interPOCS in dependency
dependen of the relative position of the loo
loose
e structure
tructure

References
[1] Do, G; Stiegler, T; Fiegl, M; Adler, L; Körner, C; Bö
Bösmann,
mann, A; Freund, H; Schwieger,
S hwieger, W;
Wasserscheid,
Wa er heid, P. (2017): “Ele
“Electrophoretic
trophoreti Deposition
Depo ition of Boehmite on Additively
Additi
Additivel
el Manufactured,
Manufa tured,
Interpenetrating Periodic
riodic Open Cellular Stru
riodi Structures
ture for Catalytic
Catal ti Applications”,
Appli ations”,
ation ”, Industrial &
Engineering Chemi
Chemistrytr Research
Resear h 45, S. 13402–13410.
[2] Inayat,
Ina at, A; Klumpp, M; Lämmermann, M; Freund, H; S Schwieger,
hwieger, W. (2016): “De
“Development
elopment of a
new pre
pressure
ure drop correlation
orrelation for open
open-cell
ell foams
foam based
ba ed completely
ompletel on theoreti
theoretical
al ground
grounds-
Taking
Ta ing into account
a ount strut
trut shape and geometri
geometric tortuo
tortuosity”,
it ”, Chemi
Chemical
al Engineering Journal,
ournal S. 704–
719.
[3] Busse,
Bu e, C; Freund, H; Schwieger,
S hwieger, W. (2018): “Inten
“Intensification
ifi ation of heat tran
transfer
fer in catalytic
atal ti reactors
rea tor
by additively
b additi el manufa
manufactured
tured periodic
periodi open cellular
ellular structures
tru ture (POCS)”, Chemical Engineering and
Processing - Pro
Process
e Intensifi
Intensification,
ation S. 199–214.
[4] Weller, H.G; Tabor, G; Jasak,
a a , H; Fureby,
Fureb , C. (1998): “A ten
tensorial
orial approa
approach
h to computational
omputational
continuum mechanics
ni using object-oriented
obje t techniques”, Computer
Computers in Physic
Physics 6, S. 620.
 Stochastic Modeling of the Molecular Weight Distribution by
Conceiving a Virtual GPC

Paul Peikert, Markus Busch*

TU-Darmstadt, Ernst-Berl-Institut für Technische und Makromolekulare Chemie,
D-64287 Darmstadt, Germany
*markus.busch@pre.tu-darmstadt.de

While reaction engineering of low-molecular weight compounds mainly focuses on

equilibria, conversion and selectivities, product properties of polymers as well as the
associated area of application are additionally influenced by the molecular weight
distribution as well as the branching structure. Consequently, polymer reaction
engineering is employed in order to produce macromolecules tailor-made for its
application. Polyethylene (PE) exhibits a simple polyolefine structure and serves as
excellent example. With a worldwide production of more than 90 million tons per year
PE represents the most commonly produced plastic material1 and can be divided
into three different types with regard to its branching structure: high-density (HDPE),
linear low-density (LLDPE) and low-density polyethylene (LDPE). While HDPE and
LLDPE are produced catalytically, the LDPE-process is based on high-pressures up
to 3000 bar and high temperatures up to 300 °C.2

As a result, a product with unique properties resulting from its microstructure

exhibiting randomly distributed long- (LCB) and short-chain branches (SCB) is
obtained. While SCBs mainly affect density and crystallinity, LCBs are crucial for the
viscoelastic behavior and processability of the product. Therefore, depending on the
microstructure LDPE can be employed as packaging material for food or
pharmaceuticals as well as in terms of co-polymers for encapsulating material in the
photovoltaic industry or insulation for high-voltages lines.

Due to its extraordinary process conditions, an experimental sensitivity analysis

regarding reaction conditions proved to be time and cost intensive. In order to obtain
a product tailor-made for its application simulation-aided product design is frequently
applied.

In this contribution, a coupled deterministic and stochastic hybrid approach is applied

in order to capture the exact position of long- and short-chain branches. The stored
data is afterwards employed to calculate the radius of gyration in dependence on the
chain length. Thereby, a newly developed and validated self-avoiding random walker
enables the prediction of the macromolecular dimension in dependence on the
process conditions at the plant.

Furthermore, on basis of the determined chain-length dependent radius of gyration of

an ensemble of macromolecules a virtual gel permeation chromatography (GPC) is
developed in order to calculate the molecular weight distribution. Common modelling
approaches assume a separation of polymer chains with regard to its molecular
weight. However, a GPC experimentally separates macromolecules on basis of its
hydrodynamic volume which can be quantified by the radius of gyration. Therefore, a
deviation of the molecular weight distribution between these approaches and the
product obtained from the plant is inevitable. Modelling the GPC by virtually
separating the polymer chains exposes that deviation.

Thus, with this contribution it is possible to establish a more detailed view on the
process-structure-property relationship for the high-pressure ethene polymerization.
In dependence of the chosen process conditions it is possible to predict the structure
of an ensemble of macromolecules as well as the radius of gyration of an ensemble
of individual macromolecules. Via the hydrodynamic volume of the stored individual
macromolecules the molecular weight distribution can be calculated virtually resulting
in a more realistic description of the separation process during gel permeation
chromatography.

References
[1] PlasticsEurope, 2016, Plastics - the Facts 2016: An analysis of European plastics
production, demand and waste data.

[2] G. Luft, Chemie in unserer Zeit, 2000, 34(3), 190-199.

[3] T. Herrmann, PhD-Thesis, TU-Darmstadt, 2011.

Acknowledgement:
Lyondell Basell Polyolefine GmbH
 Influence of Catalyst Bed Packing Density and Gas Velocity
Distribution on the Performance of Multi-Tubular Fixed Bed
Reactors

A. Kubicka, Clausthal University of Technology, Clausthal-Zellerfeld/DE;

G. Mestl, Clariant, Bruckmühl/DE; T. Turek, Clausthal University of Technology,

Clausthal-Zellerfeld/DE

One of the most important reactor types for the large-scale synthesis of chemicals is
the fixed bed reactor variations of which are frequently observed throughout the
chemical industry. If the occurring reaction releases high amounts of energy, the
configuration of choice is often a multi-tubular arrangement due to its excellent heat
dissipation properties and cooling capabilities. The fixed bed inside this reactor is
realized by filling the individual reactor tubes with catalyst pellets [1].
In state-of-the-art simulations of multi-tubular reactors, the packing density of the
catalyst pellets is assumed to be constant across all reactor tubes in order to simplify
the simulation and shorten the computational time. In reality, however, the packing
density is not uniform. Instead there exists a random distribution of catalyst porosity
which is dictated by the duration and type of process used to fill the tubes with
catalyst. In order to minimize the effects of such a distribution on the overall
conversion, selectivity and yield, its standard deviation is kept small. Tubes that
deviate too far from the porosity limits, which are assessed through pressure drop
measurements, are refilled until the arbitrarily set limit is met. Such a process is
costly and can lead, depending on the width of the desired distribution and the
precision of the packing process, to long reactor downtime.
Even though so much effort is put into keeping the porosity distribution as narrow as
possible, only little is known about the actual impact of a non-uniformly packed
catalyst bed on the overall performance of the reactor. It has likewise only
sporadically been analyzed whether the distribution can be used to optimize the
performance of the reactor further or if even thermal runaway may occur.
In our study we investigated all these points and determined the reactor performance
as a function of various operating parameters such as volumetric flow of the feed,
variation in catalyst packing density and operating modes of the cooling system.
The partial oxidation of n-butane to maleic anhydride [2] was used as an exemplary
reaction to investigate the interrelations between different values of bed porosity, the
resulting reactor performance and also the safety aspects concerning thermal
runaway of the reactor (see Figure). If the modification ofy the bed porosity
distribution is used in the right way and not arbitrarily, it can be a tool to change and
optimise reactor performance and also to enhance process safety.
a) b)

Conversion Reactor standard deviation

εc
Selectivity 24
0.9 Yield 14
1000
8
Conversion, Selectivity, Yield / -

0.8
800

Number of tubes / -
0.7

600
0.6

0.5 400

0.4
200

0.3
0
0.4 0.5 0.6 0.7 0.8 0.9 0.48 0.50 0.52 0.54 0.56 0.58 0.60 0.62 0.64
Bed porosity / - Bed porosity / -

Diagram a) of the Figure shows the influence of bed porosity on conversion,

selectivity and yield during the partial oxidation of n-butane in a fixed bed reactor at a
gas hourly space velocity (GHSV) of 1600 1/h. It can be seen that the maximum yield
would be obtained at a bed porosity of about 0.65 whereas the actual catalyst
packings have porosities around 0.56 (diagram b)). This right hand figure shows
randomized porosity normal distributions of the packing with different standard
deviations but identical mean values. The red line indicates the critical porosity εc
below which thermal runaway of the individual tubes would occur.

References:
[1] G. Eigenberger and W. Ruppel, “Catalytic Fixed-Bed Reactors,” Ullmann’s
Encycl. Ind. Chem., 2012.
[2] D. Lesser, G. Mestl, and T. Turek, “Modeling the dynamic behavior of industrial
fixed bed reactors for the manufacture of maleic anhydride,” Chem. Eng. Sci.,
vol. 172, pp. 559–570, 2017.
 Numerical characterization of open-cell ceramic foams

G. Ganzer, W. Beckert, Ch. Freytag, A. Füssel, J. Schöne

Fraunhofer IKTS, 01277 Dresden, Germany

Open-cell ceramic foams have unique properties like light weight, low pressure drops
and high specific surface areas. They can be used for heterogeneous catalytic
conversion (porous burners) or volumetric solar receivers. Their geometrical and
morphological parameters (porosity, pore size, strut thickness …) have a huge
influence on the transport properties which can be determined by experiments,
correlations or numerical simulation.
In this study a 3D CFD analysis of open-cell ceramic foams is presented. Different
foam geometries are synthetically generated with GeoDict (Math2Market GmbH), a
commercial material simulator. Mesh generation is based on the exported voxel
geometry in an efficient way for up to 15 Mio. computational cells. The CFD analysis
is performed in ANSYS Fluent using periodic conditions for a representative
elementary volume. The model solves the mass, momentum and energy balance
equations. The permeability, effective thermal conductivity and volumetric heat
transfer coefficients are calculated and compared with published correlations
showing good agreement.

Figure 1: Contour plot of gas velocity for an open-cell ceramic foam (left) and
contour plot of gas temperature (right)
 Synthetic packed beds for CFD-simulations:
imulations:
Rigid body
b vs. soft body approach
Steffen Flaischlen1,2, Prof. Dr.-Ing. Gregor D. Wehinger1,2,
1
Institute of Chemical
cal and Electrochemical
Ele tro hemi al Pro
Process
e Engineering, Clausthal
Clau thal
University
Uni er it of Technology,
Te hnolog , Clausthal-Zellerfeld,
Zellerfeld, Germany
German
2
Research
Re ear h Center Energ
Energy Storage Te
Technologies
hnologie (EST), Clausthal
Clau thal University
Uni er it of
Technology, Goslar, Germany
Introduction
For fixed-bed rea
reactors
tor with a small
mall tube-to-particle-diameter
tube diameter ratio, the
t local bed
structure has a large influence
luence on the local
lo al tran
transport
port phenomena. In order to describe
de ribe
these effects in detail, CFD simulations with a three-dimensional resolution of every
particle are used [1].. In this
thi work, we loo
looked
ed critically
riti all at two common
commonly applied
methods for synthetic
method ntheti fixe
fixed-bed generation,, i.e. the rigid body and the soft
oft bod
body
approach, respectively.

Methods
The commonly u
used
ed Di
Discrete
rete Element Method (DEM) iis a soft
oft body
bod approa
approach,
h, where
the contact
onta t for
forces
e are formulated based
ba ed on a single sphere.
phere. For description
de ription of
deformation, o
overlaps
erlap between the parti
particles
le are allowed. Complex pa
particle shapes
are approximated
ro imated with a specifi
specific number of merged spheres
pher (composite
omposite particle).
parti le

Fig. 1:: Compari

Comparisonon between DEM and Bullet Ph Physics.
i . In the DEM the appro
approximation
imation of particles
parti le in pa
packing
ing
generation iis leading to overlaps
o erlap between the parti
particles.
le .

A challenge
hallenge of this
thi method iis shown
hown in Fig. 1, were the transformation
tran formation of parti
particles
le
used
u ed for the filling process
pro e
ess into the CFD geometr
geometry lead
leads to o
overlaps.
erlap
erlaps..
Additionally, the simulation time for the bed generation scales with the number of
spheres. As an alternative, Ref. [2] used the video-animation program Blender, which
contains an own physical library (Bullet Physics)[3]. The objects are simplified as rigid
bodies, were no deformation occurs. Since the contact forces are surface-based in
this approach, the CAD surface can be used directy for collision detection. Packed
beds with different pellet shapes were generated with the two methods and were
compared with experimental data in terms of porosity, velocity and particle alignment.

Results
The comparison in Fig. 2 (a) shows packed beds of cylinder pellets for both methods.
The bed height for DEM is slightly lower than the height of the Blender bed because
of the overlaps. This is also seen in the radial porosity profile in Fig. 2 (b), which
shows lower values. The bed structure affects directly the velocity profile, cf. Fig. 2
(c).

Fig. 2: a) Comparison of synthetic fixed beds from Blender and DEM. (b) Radial porosity. (c) Specific velocity.
Experimental data taken from [3].

With these results Blender seems to be a true alternative for non-spherical particles.
In addition, it shows a low simulation time and large agreement between
experimental and synthetic bed structures.

References
[1] Wehinger, G. D., Eppinger, T., & Kraume, M. (2015). Chem. Ing. Tech., 87(6), 734-745.
[2] Boccardo, G., Augier, F., Haroun, Y., Ferre, D., & Marchisio, D. L. (2015). Chem. Eng. J., 279,
809-820.
[3] https://pybullet.org
[4] Giese, M., Rottschäfer, K., & Vortmeyer, D. (1998). AIChE J., 44(2), 484-490
 Dynamic CO2 Methanation in a Wall-Cooled Fixed Bed Reactor:
Comparative Evaluation of Reactor Models

Konrad L. Fischer, Moritz R. Langer, Hannsjörg Freund

Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU),

Lehrstuhl für Chemische Reaktionstechnik, Erlangen, Germany

The methanation of carbon oxides has gained a renewed interest as a possible

power- to-gas process for energy storage. The volatile nature of renewable energy
sources leads to an unsteady production of hydrogen by electrolysis of water.
Expensive hydrogen storage facilities can be avoided by a dynamic operation of the
methanation reactor with fluctuating inlet conditions. A review of recent simulation
and optimization studies regarding the unsteady-state methanation reveals that there
is no clear consensus in the used dynamic reactor model formulations1-4.
In order to support further modeling works, this study focuses on the comparison of
four different dynamic reactor models of varying complexity regarding dimensionality
and phase treatment in order to reveal the most decisive influences on the model
predictions. The basis of the comparison is a fixed-bed reactor with active wall-
cooling and high conversion.
Regarding the dynamic behavior, the reactor response of both positive and negative
step changes of the inlet molar flow rate is investigated. An increase of the flow rate
causes lower temperature profiles within the reactor as well as a reduced conversion,
which is shown for a one dimensional pseudo-homogenous reactor model in Figure
1. However, the reduction of the flow rate can cause a severe stress for the reactor
due to reduced convective heat transport and increased transport resistances. The
result is an increased temperature profile which can lead to an unstable operation
point or even a reactor runaway. The same dynamic scenario is examined for each of
the studied reactor models. The results indicate considerable discrepancies of the
predicted response for different reactor models, which are currently evaluated in
detail and will be presented in this work.
Figure 1: Hot spot temperature and carbon dioxide conversion progress as result of a
step change in the inlet molar flow rate. A new steady state is reached after 114s.

References
[1] Bremer, J., Rätze, K. H. & Sundmacher, K. (2017). CO2 methanation: Optimal
start‐up control of a fixed‐bed reactor for power‐to‐gas applications. AIChE
Journal.
[2] Kreitz, B., Wehinger, G. D. & Turek, T. (2018). Dynamic simulation of the CO2
methanation in a micro-structured fixed-bed reactor. Chemical Engineering
Science.
[3] Matthischke, S., Roensch, S. & Güttel, R. (2018). Start-up Time and Load Range
for the Methanation of Carbon Dioxide in a Fixed-Bed Recycle Reactor. Industrial
& Engineering Chemistry Research.
[4] Try, R., Bengaouer, A., Baurens, P. & Jallut, C. (2017). Dynamic modeling and
simulations of the behavior of a fixed‐bed reactor‐exchanger used for CO2
methanation. AIChE Journal.
 Compartmentalization of a Hybrid-Stochastical
Hybrid Stochastical LDPE Model to
Describe Mixing Effects on the Polymeric Microstructure

Oliver Salman, Markus Busch*

TU Darmstadt, Ernst-Berl
Berl-Institute für Te
Technische
hni he und Makromolekulare
Ma romolekulare Chemie,
D-64287 Darmstadt, Germany
*mar
*markus.busch@pre.tu-darmstadt.de

Due to its unique properties,

properties low-density
den it pol
polyethylene
eth lene is
i one of the mo
mostt important
thermoplastics with a market share
hare of more than 17
17%.[1] The
These
e properties
propertie re
result
ult from
its typical mole
molecular
ular microstructure
microstru ture when LDPE is produced at process
proces conditions up
to 300 °C and 3500 bar in a free radical polymerization. Besides
Beside the process
conditions,
ondition , the rea
reactor
tor type affects the mi
microstructure
ro tru ture and with this the propertie
properties of
the resulting polymer. While tubular reactors
rea tor are mo
mostt commonly
ommonly used
u ed because of
their higher produ
productivities
ti ities due to better temperature handling, autoclave
auto la e produ
products
t
enables important applications
enable application aas extrusion
e tru ion coating
oating due to its
it tree like
li e branching
structure with a wider molecular
mole ular weight di
distribution.
tribution To predict the molecular
mole ular
microstructure
mi ro tru ture of LDPE produ
produced
ed in auto
autoclave
la e reactors,
rea tor , a h
hybrid
brid numeri
numerical-
al
stochastical model is developed considering
on idering mi
mixing
ing effects
effe t besides
beside the kinetic
ineti
network and heat balance.

Figure 1:: Scheme of the implemented segmentation in the kinetic model.

Describing mixing effects in the autoclave process is relevant, because of very fast
reaction rates in the free radical polymerization. This leads to high temperature
sensitivities, where concentration and temperature gradients can affect the resulting
polymer structure. To consider mixing effects for the free radical polymerization of
ethylene in an autoclave reactor, a compartmentalization approach, based on the
work of G. Wells, is used.[2] Therefore, each reactor zone is divided in multiple
segments where the segments are described by the mass and heat balance of a
continuous stirred-tank reactor. Figure 1 shows the conjunction of the segments in
the kinetic model. The mixing of the main reaction mass with the injection plume is
implemented by intermediate streams, connecting the main segment individually with
the plume segments. In order to describe the infiltration of the injection plume into the
main reaction mass, the segment size is increasing from the supply point and the
flow rates from the main reaction mass into the segments is correlated to the
individual segment volumes to describe the eroding injection plume.

The developed model gives an insight of the influence of mixing and how the use of
different initiators affects the temperature profile and concentration gradients inside
the autoclave reactor. The Monte Carlo algorithm enables the possibility to
investigate effects of mixing on the molecular microstructure and gives detailed
information about the origin and distribution of branches.

Literature:
[1] Plasctis – the Facts 2017, PlasticsEurope 2017

[2] G. Wells, H. Ray, Macromolecular Materials and Engineering, 290(4):319–346, 2005

Acknowledgement:
SCG plc.
 Equilibrium Modelling Insights to Process Tolerance and
Operational Capabilities of Plasma Gasification in Waste to Value
Concepts

Maximilian Hungsberg1, Christian Dreiser2, Stefan Brand2, Alfons Drochner1,

Bastian JM Etzold1
1
Technische Universität Darmstadt, Darmstadt/Germany;
2
CLARIANT, Group Process Technology, Frankfurt/Germany

Introduction
Regarding a sustainable development, the realization of concepts like Circular
Economy calls for processes capable to connect the ends of a linear (take-make-use-
dispose) economy [1]. Through the closing of this cycle, variations in feed stream
composition is more likely. In consequence, the demand rises for tolerant processes,
capable to handle these variations also to enable waste-to-value concepts. In
addition, the further development of renewable energies and the associated
fluctuating energy supply results in a rising need for highly flexible electricity based
processes.[2,3] A promising technology which can contribute to these three
demands, 1) the development of closed material cycles by utilizing waste as
alternative feedstock, 2) increased tolerance towards feed and power fluctuations
and 3) the use of renewable energy, is plasma gasification.
Results
To study the capability of plasma gasification in waste-to-value concepts, a non-
stoichiometric equilibrium model was employed. As feedstocks, representing low to
highly functionalized materials, coal (CH0.6O0.02), lignin (CH1.1O0.4), and
cellulose (CH1.65O0.8) were chosen. Furthermore, the addition of oxygen, hydrogen
and steam as gasification agents and also pre-drying of the feedstock was studied.
The changed composition, resulting after these steps, is named operational
composition and is represented by overall O:C- and H:C-ratios. For these
compositional variations and temperatures from 800 to 1800 K the equilibrium
product gas composition is calculated. In difference to waste to energy concepts, not
the caloric value of the product stream, but the achievable total amount of syngas
(H2+CO), the syngas ratio (H2/CO) and also the amount of solid carbon formed is in
focus. Solid carbon not only represents unused feedstock, but high carbon contents
give also rise to difficulties
ies in the handling of the gasification process and product gas
purification. It can
an be obser
observed
ob er ed that for temperature
temperatures abo
above
e 1400 K a plateau is
reached,
rea hed, where variations
ariations in temperature onl
only slightly
lightl affect
affe t the molar amount of
syngas and the syngas
ngas ratio, which
whi h iis an important prerequisite for a tolerant
process. If a certain
ertain product gas
ga composition
ompo ition iis needed,, the present model can
an be
used
u ed to determine, within given
gi en thermod
thermodynamic
nami limitation
limitations,, the optimal route to the
target specification. Limitation
Limitations ari
arise
e for e
example
ample from the aimed synga
syngas
nga ratio and a
high amounts of total syngas
yngas produ
produced
ed combined with a low amount of solid
olid carbon.
arbon
By defining criteria for these properties,
propertie , van Krevelen plots are employed
emplo ed to identif
identify
the proper O:C- and H:C-ratio
ratio by
b adding borderlines
rderline for ea
each
h criterion, as shown in
Figure 1. The area
rea defined by
b overlaying
o erla ing all borderlines
borderline of all property
propert criteria,
riteria gives
the operational window of the process, represented
by the white area of Figure 1.
b 1 The O:C- and H:C-ratio
of the operational compositi
omposition needs to be within this
area in order to achieve
ieve the aimed product
produ t
specification. The proper addition of gasification
ga ifi ation
agents or a necessary pre--drying of the feedstock to
achieve
a hie e such
u h an operational composition,
ompo ition, can
an be
derived
deri ed from the van
an Krevelen plot. In Figure 1, this is

exemplarily illu
illustrated
trated for moist, ash-free Lignin. Figure 1:: van Krevelen
Kre elen plot with
overlaying
o erla ing borderlines
borderline for the aimed
Thereby, it was demonstrated how a similar
imilar produ
productt product gas gives the proper area of
the operational composition
ompo ition (white).
spectrum
pe trum can
an result
re ult through the fle
flexible
ible use
u e of Lignin (af) is the moist,moi t, a
ash-free
h
feedstock
feed to composition.
compo The arrows
gasification agents, independent of the employed
emplo ed represent
repre ent possible shifts
hift b
by adding the
labelled ga
gasification
ification agent.
feedstock
feed to compositions.
ompo itions. Thus,
Thu , process
pro e toleran
tolerance
e
against feed variations is feasible.
fea ible
Conclusion
Consequently,
Con equentl , the combination
ombination of high temperature
temperatures of pla
plasma
ma gasification
ga
gasifi
ifi ation and the
use
u e of gasification
ga ifi ation agents, gi
gives
e ri
rise
e to a pro
process
e being highly tolerant to various or
fluctuating feedstocks – a key
ke
e element for the implementation of closed
lo ed material
cycles.
References
1 Lieder, M.; Ra
Rashid,
hid, A., J. Clean Prod. 2016, 115, 36–51
2 Ausfelder, F.; Beilmann, C.; Bertau, M.; Bräuninger, S.; Heinzel, A.; Hoer, R.;
Koch, W.; Mahlendorf, F.; Metzelthin, A.; Peuckert, M. et al., Chemie Ingenieur
Technik 2015, 87, 17–89
3 Moseley, P. T.; Garche, J. Electrochemical Energy Storage for Renewable
Sources and Grid Balancing; Elsevier Science: Burlington, 2014.
Evaluating New Multi-Phase Reactors - a Detailed CFD-based Model
Andrea Rathgeb, Benedikt Weber, Andreas Jupke
RWTH Aachen University - Fluid Process Engineering (AVT.FVT), Aachen, Germany

The development of an efficient integrated reaction-separation device requires

detailed knowledge of the complex interactions between mass transfer, reaction
kinetics and fluid dynamics. The goal of the presented work is to meet the need for
new detailed multi-scale reactor models1 for liquid-liquid reaction-separation systems.
The applicability of the developed model is shown by the evaluation of reactor
concepts for the reaction system of fructose to 5-hydroxymethylfurfural (5-HMF). This
system benefits from an in situ product removal into a disperse phase that
suppresses the formation of undesired by-products2.
While coupling of chemical reactions and multi-phase flow is crucial to liquid-liquid
reaction engineering, incorporating multi-scale models and nonlinear chemical
reactions in a CFD code leads to a steep increase in computational time3. In the
presented approach, this problem is addressed by using the 3D flow profile of the
continuous phase obtained from a CFD simulation for the calculation of convection
across the boundaries of defined compartments. Simultaneously, a droplet
population balance equation (PBE) is solved for the disperse phase, as a state of the
art method for the simulation of extraction columns4,5. Detailed models for
coalescence4, breakage6 and droplet sedimentation7 describe droplet behavior. For
the system of 5-HMF, experimentally determined continuous phase reaction kinetics8
are calculated for each compartment, followed by mass transfer of the product over
the disperse phase interface. Thus, the device’s flow profile translates to space-
dependent residence times and a concentration profile along the reaction path.
For the investigated integrated reaction-separation system, two different continuous
reactor concepts in counter- and co-current flow, namely a Kühni-column and a plug-
flow reactor, have been evaluated and compared. For both reactors a concentration
profile evolves over the column height, resulting in local reaction rates. The Kühni-
column reactor suffers from high axial dispersion reducing yield. In the plug-flow
reactor, however, lower energy dissipation reduces breakage, which leads to less
interfacial area lowering mass transfer efficiency. Additionally, in counter-current
mode, a back extraction occurs, where saturated disperse phase is in contact with
the fresh continuous phase.
In conclusion, a detailed compartment model, which combines flow-profile, droplet
population effects and system kinetics, enables investigation of the intricate
interactions of fluid dynamics, mass transfer and reaction for the selected
geometries. Thereby, the influence of fluid dynamics and energy dissipation is
evaluated and shown to be an important factor in the choice of a reaction device for
the synthesis of 5-HMF. A versatile reactor model has been established, which can
easily be extended to further reaction kinetics or device geometries.

References
(1) Duduković, M. P.; Mills, P. L. (2015): Scale-up and multiphase reaction
engineering. Current Opinion in Chemical Engineering 9, pp. 49–58.

(2) Blumenthal, L. C.; Jens, C. M.; Ulbrich, J.; Schwering, F.; Langrehr, V.; Turek, T.;
Kunz, U.; Leonhard, K.; Palkovits, R. (2016): Systematic Identification of Solvents
Optimal for the Extraction of 5-Hydroxymethylfurfural from Aqueous Reactive
Solutions. ACS Sustainable Chem. Eng. 4 (1), pp. 228–235.

(3) Rigopoulos, S.; Jones, A. (2003): A hybrid CFD—reaction engineering

framework for multiphase reactor modelling. Basic concept and application to bubble
column reactors. Chemical Engineering Science 58 (14), pp. 3077–3089.

(4) Henschke, M. (2004): Auslegung pulsierter Siebboden-Extraktionskolonnen.

Aachen: Shaker (Berichte aus der Verfahrenstechnik).

(5) Attarakih, M.; Al-Zyod, S.; Abu-Khader, M.; Bart, H. J. (2012): PPBLAB: A New
Multivariate Population Balance Environment for Particulate System Modelling and
Simulation. Procedia Engineering 42, pp. 1445–1462.

(6) Luo, H.; Svendsen, H. F. (1996): Theoretical model for drop and bubble breakup
in turbulent dispersions. AIChE J. 42 (5), pp. 1225–1233.

(7) Garthe, D. (2006): Fluiddynamics and Mass Transfer of Single Particles and
Swarms of Particles in Extraction Columns. Dissertation. München.

(8) Aigner, M.; Roth, D., Rußkamp, J., Jupke, A. (2018): Model-Based Equipment
Design for the Biphasic Production of 5-Hydroxymethylfurfural. AIChE Annual
Meeting
 Modelling and Simulation of Porous Catalyst Pellets for Unsteady-
State Methanation: Comparison of Diffusion Models

J. Schumacher1, D. Meyer1, J. Friedland1, R. Güttel1

1
Institute of Chemical Engineering, Ulm University

The methanation process is a promising part of a sustainable energy supply and

storage. Since the energy production from renewable sources is fluctuating, the
methanation reactor has to work under unsteady-state conditions as well, depending
on the upstream storage capacities [1]. One of the main challenges arising from this
situation is the dynamic behavior of the porous catalyst pellets used for methanation,
where heat and mass transfer occur simultaneously with the chemical reaction.
Dynamically changing spatial profiles of temperature and concentrations develop,
which are coupled non-linearly. Since the measurement of those profiles, especially
under operando-conditions is very challenging [2], modelling and simulation provides
a powerful tool for analyzing the occurring dynamic processes.
This work puts emphasis on the comparison of different diffusion models under
isothermal and unsteady-state methanation conditions as a basis for reliable
simulation results. The compared diffusion models comprise, but are not limited to,
the models by Fick and Wilke-Bosanquet as well as the dusty-gas model [3]. The
models are evaluated based on accuracy and numerical effort. Due to a lack of
experimental data for validation the dusty-gas-model is assumed as the most
accurate model, since it is the most complex one and thus probably considers all
relevant effects on diffusion. Thus, the alternative (and simpler) models are
compared to the results of the dusty-gas model as benchmark.
The model equations for the unsteady-state reaction-diffusion problem are
implemented to Aspen Custom Modeler for simulation. The diffusion models in
accordance to Solsvik et al. [4] are used, while the reaction kinetics are taken from
Xu and Froment [5]. For simulation typical methanation conditions are chosen with
respect to temperature, pressure and reactant composition. The catalyst pellet is
assumed to be isothermal. The effects on reactor scale are neglected, as well as
external heat and mass transfer resistances, in order to isolate the diffusion effects.
After the decision for a suitable diffusion model the unsteady-state profiles for the
start-up process of the methanation reaction are calculated.
As example figure 1 shows the simulated steady-state profile of the methane molar
fraction in the well-known methane steam reforming process for different diffusion
models, which are validated with data from Solsvik et al. [4] for the same reaction.
Obviously, the Wilke-Bosanquet approach is a suitable simplification of the dusty-gas
model, whereas Fick’s law results in significant deviation, which is in agreement with

1.00
Fick's law
Wilke-Bosanquet
Dimensionless Concentration

dusty gas
0.95

0.90

0.85

0.80
0.0 0.2 0.4 0.6 0.8 1.0
Dimensionless Pellet Radius

literature [4].
Figure 1: Simulated steady-state mole fraction profile of methane inside a porous catalyst pellet for the steam
methane reforming process with different diffusion models.

Since the methanation represents the reverse reaction of methane steam reforming,
the observed differences are transferable. However, under dynamic start-up
conditions, an even more pronounced effect of the chosen diffusion model on the
temporal-spatial profiles can be observed.

[1] J. Lefebvre, M. Götz, S. Bajohr, R. Reimert, T. Kolb, Fuel Process. Technol. 132 (2015) 83–90.
[2] T. Titze, C. Chmelik, J. Kullmann, L. Prager, E. Miersemann, R. Gläser, D. Enke, J. Weitkamp, J.
Kärger, Angew. Chem. 127 (2015) 5148–5153.
[3] R. Krishna, J.A. Wesselingh, Chem. Eng Sci. 52 (1997) 861–911.
[4] J. Solsvik, S. Tangen, H.A. Jakobsen, Ind. Eng. Chem. Res. 51 (2012) 8222–8236.
[5] J. Xu, G.F. Froment, AIChE Journal 35 (1989) 88–96.
 Process Design for the Production of Oxymethylene Ether via
Adsorption on Hypercrosslinked Polymers
Christian Henning Gierlich, Irina Delidovich, Regina Palkovits, Rheinisch-
Westfälische Technische Hochschule Aachen, 52074 Aachen
The recent discussion on banning diesel vehicles in German cities highlights the
demand for low NOx and soot exhaust emissions significantly.1-2 Without
modifications of the vehicle hardware, emissions can be reduced by blending the fuel
with oxymethylene ethers (OME).3 Optimal blending can be achieved with a mixture
of diesel and OME3-5. In the conventional OME production, trioxane is used for the
oligomerisation of dimethoxymethane (methylal).4 On the one hand this reaction
pathway is completely water-free on the other hand the production of trioxane is
rather cost and energy intensive. Therefore, the preferred reaction is based on
methanol and para-formaldehyde (FA).
In the present study we produce OME from methanol and FA (Figure 1). During the
reaction of methanol and FA water is generated as co-product. Hence, the water
removal from the product mixture is a crucial step for an effective oligomerisation.
Firstly, the reaction is heterogeneously catalyzed within the reactor (Figure 1).
Subsequently, the reaction mixture is separated via distillation, directly recycling
OME6 into the reactor. The head of column 1 containing OME1-5, methanol and water
is fed into column 2 separating OME3-5 in the bottom stream. OME1-2, water and
methanol is separated over the head of the column. Since water and OME2 have very
similar characteristics, such as evaporation temperature and polarity, separation via
distillation is not feasible. The design of alternative processes for water and OME2
separation has become the focus of attention.
 Water Waste
OME1-2

Methanol
OME1-5
Adsorber
Reactor

FA OME6+
OME3-5

Figure 1: Process flow sheet for the production of OME3-5 starting from methanol and para-formaldehyde
(FA) and including two distillation columns and an adsorber for the separation of OME fractions and
water as well as a recycling stream.

Adsorption of OME on Hypercrosslinked Polymers

A highly promising approach for the water removal from OME product mixtures is the
adsorption of OMEs on different materials e.g. activated carbon or hypercrosslinked
polymers (HCP). In preliminary material screenings, HCPs showed the highest
performance for the adsorption of OMEs. Ensuing studies focused on restructuring
the powdery HCPs to reduce the pressure drop in a continuous adsorption set-up.

Figure 2: Restructured hypercrosslinked polymers.

A method was established for the restructuring of HCPs while keeping the high
surface area intact. First tests in the continuous set-up showed the same
performance for the restructured HCPs compared to the powdery parent material. In
addition, desorption was investigated using ethanol as desorption agent and varying
the temperature. Further investigations will be focused on the restructuring of
different HCPs to improve the adsorption capacity.

Acknowledgement
The research leading to this contribution was funded by the German Federal Ministry
of Education and Research (BMBF) under grant number 03SFK2A. The responsibility
for the content lies with the authors.

1. H, T.; Cw, L., Performances, Emissions and Soot Properties from a Diesel-Biodiesel-
Ethanol Blend Fuelled Engine. Advances in Automobile Engineering 2016, 01 (S1).
2. Barba, C.; Dyckmans, J.; Förster, J.; Schnekenburger, T., Natural gas-Diesel dual fuel
for commercial vehicle engines. In Internationaler Motorenkongress 2017: Mit Konferenzen
Nfz-Motorentechnologie und Neue Kraftstoffe, Liebl, J.; Beidl, C., Eds. Springer Fachmedien
Wiesbaden: Wiesbaden, 2017; pp 391-407.
3. Omari, A.; Heuser, B.; Pischinger, S., Potential of oxymethylenether-diesel blends for
ultra-low emission engines. Fuel 2017, 209 (Supplement C), 232-237.
4. Oestreich, D.; Lautenschütz, L.; Arnold, U.; Sauer, J., Reaction kinetics and
equilibrium parameters for the production of oxymethylene dimethyl ethers (OME) from
methanol and formaldehyde. Chem. Eng. Sci. 2017, 163, 92-104.
 Model-based determination of axial dispersion coefficients for
liquid-liquid multiphase reactors

Daniel Roth, Julia Rußkamp, Maximilian Aigner, Andreas Jupke

RWTH Aachen University - Fluid Process Engineering (AVT.FVT), Aachen,
Germany

Countercurrent liquid-liquid reactors are a promising concept for process

intensification in yield limited biomass reactions. We recently exemplified this for the
biphasic production of 5-HMF from fructose in a tubular reactor. To design this
reactor we developed a one-dimensional rate model, calculating a dynamic
concentration profile over the reactor height1. The formation of HMF is obtained by a
kinetic model and the in situ extraction of HMF is calculated by a mass transfer
model. Axial mass transfer is retrieved by convection in both phases based on single
droplet sedimentation and the consideration of swarm effects. As of yet, it is
assumed that the two phases in the reactor behave like a plug flow. However, it is
known that in countercurrent columns this assumption is too simplified2. Hence, we
want to extend our model by considering back mixing in both phases to determine
the influence on the reactor performance.
To account for this back mixing we use the most prominent approach by
Danckwerts3, which requires an axial dispersion coefficient. This coefficient is usually
obtained by time-consuming experiments or correlations valid only for specific
geometries and operating conditions4.
In this work, we derive the axial dispersion coefficient based on detailed flow
simulations for the continuous phase and the disperse phase. This approach enables
a fast evaluation of the back mixing in the liquid-liquid reactor, which reduces the
experimental effort drastically.
To evaluate the continuous phase’s flow behavior 3-D CFD simulations are carried
out using an Euler-Euler approach5,6. In order to investigate the effects of the
disperse phase on the continuous phase we assume the disperse phase as
monodisperse droplets. By the in silico injection of a tracer in the continuous phase
an axial dispersion coefficient can be determined. To evaluate the disperse phase we
used a 1-D population balance model7. This 1-D population balance model considers
the different sedimentation velocity of droplets in a polydispersion. Furthermore,
droplet coalescence and breakage are considered in the model. The predictive
determination of the axial dispersion coefficient allows us to investigate different flow
profiles efficiently. By merging those results with our one-dimensional reactor model,
we obtain optimal operating conditions for the countercurrent liquid-liquid reactor.

References
(1) Aigner, M.; Roth, D., Rußkamp, J., Jupke, A., Model-Based Equipment Design for the
Biphasic Production of 5-Hydroxymethylfurfural, AIChE Annual Meeting, 2018, ISBN: 978-0-
8169-1108-0
(2) Garthe, D., Fluiddynamics and Mass Transfer of Single Particles and Swarms of
Particles in Extraction Columns, Dissertation, München, 2006
(3) Danckwerts, P.V., Continuous flow systems, Chem. Eng. Sci., 1953, 2, 1-13
(4) Charton, S.; Duhamet, J.; Borda, G.; Ode, D.; Axial dispersion in pulsed disk and
doughnut columns: A unified law, Chem. Eng. Sci., 2012, 75, 468-477
(5) Yadav, R.L.; Patwardhan, A. W.; CFD modeling of sieve and pulsed-sieve plate
extraction columns, Chem. Eng. Res. Des., 2009, 87, 25-35
(6) Hlawitschka, Computational Fluid Dynamics Aided Design of Stirred Liquid-Liquid
Extraction Columns, Disseration, 2013
(7) Henschke, Auslegung pulsierter Siebboden-Extraktionskolonnen, Habilitation, 2004
 Modeling Rheological Properties of HDPE and LLDPE

Maria Dernbach, Markus Busch*

TU Darmstadt, Ernst-Berl-Institut für Technische und Makromolekulare Chemie,
D-64287 Darmstadt, Germany
*markus.busch@pre.tu-darmstadt.de

Polyethylene (PE) is of great importance within the chemical industry with its large
share of the overall global plastic material demand. The division of PE in different
types is done using its density that are given by variations of the micro-structure. In
particular, the degree and length of branching of the backbone influences the density
and mechanical properties. The branching of the polymer is determined by the
chosen process and synthesis method.

High-density polyethylene (HDPE) is produced using a catalytic system, mainly a

heterogeneous Ziegler-Natta or homogeneous metallocene catalyst, at temperatures
up to 300 °C and pressures up to 200 bar. This leads to the characteristic structure of
linear chains with almost no branching. The polymerization is typically performed by
gas-phase, slurry or solution processes. The same procedure is used for the
production of linear low-density polyethylene (LLDPE) with the only difference of
adding -olefins as comonomers. By insertion of an -olefin short-chain branches
(SCB) in the respective length to the comonomer is introduced in the polymer
backbone and by this the characteristic structure of LLDPE results. Low-density
polyethylene (LDPE) is mainly produced under high pressures up to 3000 bar by free
radical polymerization initiated by various peroxides or oxygen. This polymerization
results in the typical structure of the polymer with long-chain branches (LCB) and
SCBs.1 The properties of PE can further be influenced by comonomers. The
application range of PE is broad due to widely varying properties. Common
applications are foils, films, containers, pipes and isolation.

For further processing of the thermoplastic, the rheological melt properties of the
polymers are particularly interesting due to its influence on the necessary processing
parameters. The rheological properties can be used to describe the flow behavior of
the polymer melts.2 Knowledge of the flow behavior supports the design and
parameter selection for extrusion and injection molding. Another common example is
the film blowing process where the linear and non-linear rheological properties of the
polymer melts are important for operation parameters and product properties.

The use of modeling in addition to experiments is advantageous due to a possible

reduction of experimental expense, time, and costs. Therefore, a predictive model is
required.

In this work, a modeling approach to obtain rheological properties of HDPE and

LLDPE from the kinetics of the metallocene-catalyzed homo- and co-polymerization
of ethylene is developed. First, a deterministic kinetic model for the metallocene-
catalyzed homopolymerization of ethylene,2 using the software Predici by CiT, is
validated with experiments performed in a continuous lab-scale stirred tank reactor.
The considered system exists of the monomer ethylene, the precursor rac-
dimethylsilylbis(indenyl)hafnium dimethyl, the activator tetrakis(penta-fluorophenyl)
borate, the scavenger trioctylaluminium, and the solvent toluene. For the
deterministic metallocene-catalyzed LLDPE model, the HDPE model is extended by
including the comonomer to the reaction network. The kinetic model of HDPE and
LLDPE are coupled with a Monte-Carlo (MC) algorithm to obtain the polymeric
microstructure. The generated topological information can be used as input for the
branch-on-branch (BOB) model to compute the linear and non-linear rheological
properties.3 By using this approach, a simulation-based study of the linear and non-
linear rheological melt properties of HDPE and LLDPE in comparison to LDPE4 is
performed and the influence on the linear and non-linear rheological melt properties
of low LCB contents inside HDPE is investigated.

References
[1] J. L. White, D. D. Choi, Polyolefins – Processing, Structure Development, and
Properties, Carl Hanser Verlag, München, 2005.
[2] S. Mehdiabadi, J. B. P. Soares, D. Bilbao, J. L. Brinen, Macromol. React. Eng., 5,
418-430, 2011.
[3] D. J. Read, Journal of Polymer Science, Part B: Polymer Physics, 53, 123-141,
2015.
[4] K. Pflug, Dissertation: Linking Reaction Conditions with Polymer Properties for the
LDPE Process, TU Darmstadt, 2018.
 Entropic Analysis in Tubular Reactor Design

Marcílio Silva, Willy Araújo, David Rosa, João Manzi,

Federal University of Campina Grande, Aprígio Veloso 882, Campina Grande,

Paraíba, Brazil

Abstract

The classical design of reactors uses the kinetic concepts applied to the mass and
energy balances to determine the various steady states [1,2]. Therefore, no
information is given about which of these is the best [3]. The use of the second law of
thermodynamics can provide the minimal irreversibilities conditions, which works as
the target. The use of the entropy concept provides information about the optimal
thermodynamic point of operation [4]. These ideas have been applied to a tubular
reactor study case, such case is presented in [2].
The set of equations presented by [5] is used to obtain the optimal point, found from
a trade-off between the entropy production and the entropic costs, which is directly
involved in separation, treatment, reuse, and disposal expenses.
The new approach proposed in this paper is used to optimize the design of a tubular
reactor resulting in a 6% decreasing from the classical one. Analyzing the area under
the incomes and cost curves, it is found a 96% increase in the net profit. It can be
directly related with less undesired products along the reactor. The analyzes are
made on the basis of standardized indexes both for the production of entropy and for
cost. It should be noted that the specification of monetary values for costs is
unnecessary, since such values are strongly dependent on each process.
Figure 1 summarizes the results obtained by comparing the classical and the
proposed methodology, which offers a smaller reactor in terms of length, with more
tubes and less catalyst mass to same production with higher net profit. The
intersection point represents the maximum profitability.
 Balances:
 Mass
Balances:  Energy
 Entropy
Steady-State 1
Steady-State 2 0.05

0.045

M 0.04

0.035

0.03

Steady-State optimal 0.025

0.02

M 0.015

0.01

0.005

Steady-State n 0
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18
Catalyst Mass (1000kg)

REFERENCES

[1] H. S. Fogler, Elements of Chemical Reaction Engineering, 5th Ed., Prentice

Hall, New Jersey, p 992, 2016.
[2] W. L. Luyben, Chemical Reactor Design and Control, 1st Ed., John Wiley &
Sons, Hoboken, New Jersey, p 419, 2007.
[3] H. Bispo, N. Silva, R. Brito, J. Manzi, Energy Conversion and Management,
vol 76, pp 26 – 31,2013.
[4] J. Manzi, R. Vianna, H. Bispo, Chemical Engineering and Processing: Process
Intensification, vol 48, pp 470 – 475, 2009.
[5] D. Rosa, P. Goes, J. Manzi, Proc. of ESCAPE 2018 - 28th European
Symposium on Computer Aided Process Engineering, Graz, Austria, pp 507 – 512,
2018.
 Modeling the effect of exothermic reactions on conjugate heat
transfer in open-cell foams through uniform heat sources using CFD

Christoph Sinn, Georg Pesch, Jorg Thöming, University of Bremen, Chemical Process
Engineering, Bremen, Germany

Lars Kiewidt, Wageningen University & Research, Biobased Chemistry & Technology,
Wageningen, The Netherlands

Abstract

Open-cell foams, often referred to as solid sponges, are subject of great interest in the
field of chemical and process engineering because they combine a low pressure loss
with a large specific surface area and good heat transport properties due to the
continuous solid phase. This combination makes them a highly attractive option for
monolithic catalyst supports. A crucial step in the design of catalyst supports is the
prediction of temperature fields and the identification of hot spots to avoid increased
catalyst deactivation.

Even though the potential of open-cell foams to reduce hot spots has been reported, the
coupled solid and fluid temperature fields in solid sponges during exothermal reactions
have not been described thoroughly yet. The experimental full-field mapping through
infrared thermography (IRT) or magnetic resonance imaging (MRI) have limitations in
terms of material (opacity) and flowrates and are complex to perform. Computational
fluid dynamics (CFD) deliver a high resolution and already proved to be a valuable tool
for investigating conjugate heat transfer in solid sponges. Despite their advantages,
CFD simulations of heterogeneous catalytic reactions in open-cell foams require a high
modelling effort as well as high computational cost because of the non-linearity and high
degree of coupling of the transport equations.

Therefore, we propose to perform µCT-based conjugate heat transfer simulations of real

open-cell foams with artificial heat production in the solid domain. The implemented
heat sources mimic the heat of reaction
rea tion during an exothermal chemical
chemi al reaction,
rea tion, and
allow to

Fig. 1: Temperature field of the alumina foam with 50 W heat Fig. 2: Ma

Maximum
imum temperature increase of alumina for different heat
source and air (500 K; 0.1 m s-1) flowing from left to right. sources
our e plotted again
againstt the superficial
uperficial velocity
elo it vs.

study the effe

effectt of heat production
produ tion on heat transfer and the coupled solid and fluid
temperature fields.

Here, we simulated
imulated the solid and fluid temperature fields
field in a cylindrical
lindrical 10 ppi open-cell
foam (25 mm o.d. x 24 mm) in a tube for different solid
olid materials, fluid velocities,
elo itie , and
intensities
inten itie of the inserted
in erted heat sources.
our e . The intensity
inten it of the heat sources
sour e was adjusted
to repre
represent
ent the ttypical
pi al heat production
produ tion in CO2 methanation. The results
re ult indicate
significant
ignifi ant temperature increa
increases
e per applied heat source in the alumina foam of up to
1.8 K W -1 (see Figs.. 1 and 2).
2 Similar trends
trend could
ould be reported for other material
materials with
different thermal conductivitie
onductivities such as s-Sic and mullite (thermal conductivities
co range
from 3 to 50 W m-1 K-1). Further
urther, a comparison of the simulated
imulated temperature field
fields and
the temperature field calculated
cal ulated with a pseudo-homogeneous
homogeneous model showed
discrepancies
di repan ie in the temperature field up to 43 K.

The results thus demonstrate

demon trate that the solid
olid temperature iis significantl
ignificantly
ignifi antl higher than the
fluid temperature and highly non-uniform for relevant material
materials and pro
process
e conditions
ondition
in heterogeneou
heterogeneous catalysis.
atalysis. The developed
de eloped relation
relationship
hip between temperature increase,
in rea e,
fluid velocity,
t , material, and inten
intensity
it of the heat source,
our e, however,
howe er, enables
enable the e
estimation
timation
of the maximal
ma imal temperature in the open-cell
open foam and provides
pro ides guidance
guidan e under which
whi h
conditions pseudo-homogeneou
homogeneous models
model are applicable.
appli able Further anal
analysis
i of the coupled
oupled
solid and fluid temperature fields will provide valuable insight into the combination of
heat transport and heat transfer for the development of heterogeneous reactor models
for open-cell foam.
 CFD Simulation of Spray Formation Combining the Volume of Fluid
(VOF) and the Discrete Phase Model (DPM)
J. Kolliyil1, G. Schaldach1, D. Pieloth 1,2, M. Thommes1
1
Laboratory of Solids Process Engineering, Technische Universität Dortmund, Germany
2
Hochschule Anhalt, Köthen, Deutschland, Germany

Purpose
The transformation of bulk liquid into sprays using nozzles/atomizers in a gaseous
atmosphere is of importance to a broad range of practical processes (e.g., Spray drying,
fuel injection for combustion). These processes, however, have specific spray
requirements; traditionally, these requirements are met by first designing nozzle heads
and then characterizing the spray via experiments. Computational Fluid Dynamics (CFD)
provides an alternative to this approach by simulating sprays from different nozzle
designs. VOF and DPM are popular multiphase models to simulate droplets and sprays.
However, VOF simulations of sprays demand huge computational efforts and are prone
to numerical diffusion; whereas DPM is less resource intensive but provide no
information about the propagation of the liquid interface. ANSYS® 19 contains a new
hybrid model called “VOF-to-DPM” which shifts small VOF lumps to DPM, hence
reducing computational effort while still providing valuable information. This work aims to
test this hybrid model.

Methods
Experiments with a pneumatic atomizer for a range of gas to liquid mass flow ratios
(GLR) were conducted at the Laboratory of Solids Processing at TU Dortmund.
Simulations using the hybrid model were performed in ANSYS® 19 for the atomizer on a
Linux HPC cluster.
 Results and Conclusion

Experiment
Simulation

Fig 1: Image of simulated spray Fig 2: Comparison of particle size distribution

formation from pneumatic obtained from simulation and experiment
atomizer at GLR = 1

Figure 1 shows the numerical

simulation of the disintegration of the liquid at the tip of the nebulizer by the concentric
high-speed gas flow. The primary formed ligaments tracked as Eulerian (VOF) phase and
can be distinguished by the highly resolved numerical grit. In the second step, the
droplets converted into Lagrangian mass points and colored by their diameter. The
measured and simulated volume based drop size distributions at an axial distance of 30
mm are shown in figure 2. Comparing the results from the new hybrid model with the
experimental data, this technique seems an appropriate tool for the prediction of the
performance of a pneumatic nebulizer.
Due to the separation of the droplet formation process and the tracking of the resulting
droplets, the application of CFD for the simulation of the nebulization process with its high
CPU requirement becomes practicable.
However, different atomizer types need to be tested for complete validation of the hybrid
model.
 Full-field assessment of gaseous flow within open-cell foams:
comparison of µCT based CFD simulations and magnetic
resonance velocimetry results

Mehrdad Sadeghi1, Mojtaba Mirdrikvand2, Georg Pesch1, Wolfgang Dreher2, Jorg

Thöming1
1
University of Bremen, Faculty of Production Engineering, Chemical Process
Engineering, Bremen, Germany
2
University of Bremen, Faculty of Chemistry, in-vivo MR group, Bremen, Germany

Open-cell foams, which are also known as solid sponges, enjoy beneficial
morphological properties such as a low pressure drop, a high thermal conductivity
and an excellent soli-gas heat and mass transfer which make them a good choice as
monolithic catalyst supports. Computational fluid dynamics (CFD) simulations have
been employed as a cost-effective and reliable numerical tool for the study of
transport phenomena through catalytic sponges; however, their irregular and
complex geometries demands high computational effort. Nevertheless, the
complexity of the geometry is a major cause for the good performance of the solid
sponge. It significantly controls flow pattern and the sponge’s heat and mass transfer
characteristics. Apart from detailed experimental studies, this fact requires in-depth
numerical studies which spatially resolve transport phenomena in the sponge locally.
As opposed to studies focusing on representative volume elements or simplifications
this demands a model of the fully-resolved geometry of the sponges to allow tuning
of the structural features of catalytic sponges for better performance. In this study, we
simulated the entire fully-resolved geometry of sponges which were obtained from
micro computer tomography (µCT) imaging of real samples. Subsequently, CFD
results were validated by experimental velocimetry measurements. Magnetic
resonance velocimetry (MRV) is a non-invasive method which has been applied for
measurement of flow within solid sponges. MRV is based on nuclear magnetic
resonance (NMR) and operates in common magnetic resonance imaging devices for
clinical imaging. NMR-based methods have the potential to be utilized for in-situ and
operando studies of transport phenomena within catalytic sponges such as flow
mapping, temperature field measurements, and to obtain concentration maps during
reactions. By our comparison, we are able to strengthen the reliability of both
methods. On the one hand, NMR-based techniques provide the opportunity to
validate CFD simulations which could be used later as a less expensive tool for
deducing design rules for the catalytic sponges. On the other, NMR mapping of
concentration, velocity, and temperature in the gas phase is a rather novel technique
which is not universally validated. Obtaining similar results with both methods
improves the reliability of either method.
In this study, incompressible gaseous fluid flow within cylindrical (25 × 68 mm) 20
PPI Al2O3 open cell foams is investigated numerically and experimentally. A gas flow
of Methane at different flow rates of 0.5, 1 and 1.5 l/min was examined. Due to
hardships in generating the computational network (mesh), a majority of µCT-based
numerical simulations utilized representative elementary volume (REV) of sponges
containing a few pores only. In this study, CFD simulations are based on the real,
large segments of sponges. This allows us to measure the differences between CFD
simulations and full-field MRV measurements. The computational cell size and MRV
voxels are 0.1 and 0.8 mm, respectively. To compare CFD and MRV results, average
axial velocity profiles within sponges were compared together. The results showed
remarkable agreement with an accuracy of ±10% (see Figure 1). This justifies the
use of CFD of large sponge segments as an adequate and reliable tool for the study
of gaseous flow within porous structures. The quantitative agreement between CFD
and MRV results amplifies the reliability of CFD simulations and underpins the
capability of NMR based measurements for in-situ temperature and concentration
measurements. Especially, motivate us for the next full-field numerical and NMR-
based experimental studies of heat transfer and chemical reactions within catalytic
sponges.
 Fig1. Obtained average axial velocity profile within Al2O3 sponge from CFD
simulations and MRV measurements for different flow rates of: 0.5, 1 and 1.5 l/min
 Simulation der CO2 Verteilung im durchströmten Photobioreaktor
basierend auf Lattice-Boltzmann Methoden
Albert Mink, Hermann Nirschl, Mathias J. Krause
Karlsruher Institut für Technologie, Karlsruhe, Deutschland

Abstrakt
Mit Photobioreaktoren (PBR) kann in großen Mengen CO2 neutrale Biomasse für
Kraftstoffe oder für die Futterindustrie gewonnen werden, aber auch qualitativ sehr
anspruchsvolle Feinchemikalien wie ungesättigte Fettsäuren und Carotinoide. Zur
Minimierung des relativen Energieeintrags ist es gängige Praxis die Durchmischung
zu reduzieren. Dieses Vorgehen ist zweischneidig, läuft man doch Gefahr das
Algenwachstum durch Unterversorgung von CO2 wissentlich zu beschränken.
Ein aussichtreicher Ansatz zum rentablen und wirtschaftlichen PBR sind daher
präzise Vorhersagen des Strömungsfeldes und die Analysen des Gastransports. In
diesem Beitrag wird die Simulation eines Schwamm-artigen PBR präsentiert und die
CO2 Versorgung der Algen diskutiert. Das zugrunde liegende numerische Verfahren
basiert auf den Lattice-Boltzmann Methoden, deren Stärken in der Gittergenerierung
und parallelen Effizienz auf Hochleistungsrechnern liegen [1,2].

References
[1] R. Trunk, T. Henn, W. Dörfler, H. Nirschl, M.J. Krause Inertial dilute particulate
fluid flow simulations with an Euler–Euler lattice Boltzmann method Journal of
Computational Science, 2016
[2] OpenLB, www.openlb.net.
 Multi-Objective Reactor Design Under Uncertainty

Johannes Maußner, Hannsjörg Freund

Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU),

Lehrstuhl für Chemische Reaktionstechnik, Erlangen, Germany

Model-based reactor design proved to be a reliable tool for the design of resource
and energy efficient chemical reactors [1]. The adequacy and the accuracy of the
utilized models (e.g. reaction kinetics, heat and mass transport kinetics) is crucial for
the success of this design approach. However, the model coefficients (e.g. activation
energies) are typically determined from experimental data and are thus subject to
uncertainty. Moreover, also the feed composition can be subject to uncertainty, e.g.,
when the utilized raw materials are based on renewable resources with a high
regional and/or seasonal variability [2]. The consideration of parametric uncertainty
for chemical reactor design is thus an important research area in chemical reaction
engineering. Additionally, the design objectives for chemical reactors are almost
always conflicting in nature. For example, typically a high conversion of the educts is
desired to reduce recycle streams but at the same time also a high product selectivity
is important to reduce byproducts. When multiple competing objectives have to be
considered, the design task revolves around finding optimal compromise solutions.
This leads to the research field of multi-objective optimization.

In the present work, we propose an efficient reactor design strategy to tackle the
combined challenges of parametric uncertainty and multi-objective optimization. The
approach combines the normal boundary intersection [3] with a monomial cubature
rule [4] to efficiently determine robust compromise solutions. The cubature rule is
used to approximate the first two statistical moments of the objectives and of all
critical constraints. The approximation of the statistical moments is thereby
performed offline, i.e., separate from the optimization problem. This leads to an
iterative approach with improved computational performance. The proposed
approach is illustrated and compared to an existing approach from literature by
studying the production of lysine in a semi-batch reactor [5].
The results show that the proposed approach is considerably faster compared to the
existing approach when a large number of uncertain parameters has to be
considered. The advantage of the approach proposed in the present work thus is
particularly relevant and important for the application to complex reactor design tasks
such as, e.g., the design of polymerization reactors or multi-phase reactors.

References
[1] Peschel, A., Freund, H., Sundmacher, K. (2010). Methodology for the design of
optimal chemical reactors based on the concept of elementary process functions.
Industrial & Engineering Chemistry Research.
[2] Wachsen, O., Bacher, V., Geisbauer, A., Appel, J., Niebuhr, V., Lade, O. (2015).
Anforderungen der zukunftsorientierten Spezialchemie an die angewandte
Reaktionstechnik. Chemie Ingenieur Technik.
[3] Das, I., Dennis, J. E. (1998). A new method for generating the Pareto surface in
nonlinear multicriteria optimization problems. SIAM Journal on Optimization.
[4] Cools, R., Rabinowitz, P. (1993). Monomial cubature rules since “Stroud”: A
compilation. Journal of Computational and Applied Mathematics.
[5] Nimmegeers, P., Vallerio, M., Telen, D., Van Impe, J., Logist, F. (2018).
Interactive Multi‐objective Dynamic Optimization of Bioreactors under Parametric
Uncertainty. Chemie Ingenieur Technik.
 On Pore-Scale Simulations of Reactive Transport for Complex
Reaction Networks

Torben Prill, Fraunhofer ITWM, Kaiserslautern; Oleg Iliev, Fraunhofer ITWM,

Kaiserslautern

Introduction

Reactive flows in porous media are important processes in many industrial and
environmental applications. The reactive transport in porous media is influenced by
the interplay between convection, diffusion and reaction, coupled with the
heterogeneity of the pore space (e.g., pore size distribution and connectivity) and
chemical heterogeneity. Further complications arise when many species are
involved, mobile or immobile connected by a complex reaction network with non-
linear rate functions. On this poster, we present a new simulation method for pore-
scale simulations when many species and reactions are involved.

Pore-Scale Simulation
For the pore-scale simulations Fraunhofer ITWM has developed PoreChem, a
software package dedicated to the simulation of reactive flow on the pore-scale. It
enables the simulation of reactive flows in resolved porous media in a reasonable
time. The software can compute the flow of a fluid in the pore space, as well as the
diffusive and advective transport of a solute species. Reactions can then be
simulated occurring not only in the fluid volume but also on the surface of the porous
medium.

The flow is computed by solving the Navier-Stokes-Brinkman system of equations

with a finite volume discretization on a regular voxel grid. Transport and reactions are
simulated by solving the reaction-diffusion-advection equation with the same
discretization. For the reactions, different reaction kinetics can be taken into account.
The fast voxel based solver enables calculations directly on µCT-Images. Transient
phenomena can be simulated, as well as steady states ones.
Results
To demonstrate the simulation method, we will show results of simulations of pore-
scale processes in catalytic filters and porous reactors. We will show how the
simulations can be performed on images based on micro-CT data and synthetically
generated random porous media, to predict conversion efficiencies. Also, we will
show how these simulations can be used in multiscale modeling by computing
macroscopic effective dispersion coefficients and reactions rates.
 Model-Based Reactor Design using a Modular Optimization
Framework

Markus Kaiser, Hannsjörg Freund

Lehrstuhl für Chemische Reaktionstechnik
Friedrich-Alexander-Universität Erlangen-Nürnberg, Erlangen

The multi-level reactor design method (MLRD) is based on the concept of the
elementary process functions (EPF) stating a flux based description of chemical
processes [1,2,3]. By means of MLRD, innovative reactors are developed
independently of known or existing apparatuses by application of three levels. The
reaction system for which a reactor is to be designed, is first modeled within a fluid
element, which is then optimized on its way through the - as yet unknown - reactor
with respect to the reaction conditions. On the first and second MLRD level, the
reactor is thus abstracted as a state space in which the best route to achieve a
specific objective function must be found. In this regard, the difference between the
first two levels is the way fluxes across the fluid element boundary (outer flows) are
considered. These are initially unrestricted, so that any state within the fluid element
can be set as desired (level 1). However, in the further course, these fluxes are
subject to physical and / or process-related restrictions, which thus also limit the
range of adjustable states (level 2). Finally, the last MLRD level addresses the
approximation of the optimal route by means of a technical implementation, which is
tailored to the course of the route (level 3). While the complexity of the mathematical
model increases in the course of the MLRD method, specific information is derived
on each MLRD level that determines what to do next.
The present work considers the second level of the MLRD method, only. Outer flows
are described by kinetic approaches whose kinetic factors and driving forces in turn
depend on different models or correlations (e.g., heat transport model, pressure drop
correlation, etc.). Additionally, in the case of a heterogeneously catalyzed gas phase
reaction, the reaction flux in the fluid element interior can be influenced by transport
processes within the catalyst. Then, in order to describe the reaction flux properly, a
catalyst model must be solved in addition to the fluid element [4]. Also, the fluxes
within the catalyst can be described by different models and correlations (e.g.,
diffusion model, etc.).
The combination of different models and correlations to describe the reaction system
is referred to as model configuration here. The resulting variety of model
configurations that depict the same physical system leads to different optimal routes
in state space and thus also to different reactor concepts. In order to quantify this
uncertainty, three heat transport models, pressure drop correlations, and diffusion
models are examined in this contribution. For that, a pseudo-heterogeneous model
structure was implemented, in which the aforementioned model components can be
incorporated as independent modules [4]. This kind of modular structure requires a
strict separation of the module equations and the balance equations, as well as the
partial reformulation of these equations to avoid numerical problems during
optimization. Using this model framework, the aforementioned modules are then
permuted and examined in the optimization of an example reaction system. This
results in 27 configurations that were used to maximize the carbon conversion during
methanol synthesis while maintaining a minimum space-time yield considering the
catalyst diameter as a degree of freedom while meeting a maximum allowable
pressure drop. In addition to its technical relevance, this optimization task sets the
interaction of the modules examined here under maximum load. Thereby, the
optimization result is forced to be non-trivial. While nearly identical conversion is
achieved for all model configurations, the operating conditions required to achieve
this conversion and the distribution of different catalyst sizes along the reactor to be
used are very different. This analysis can thus be understood as the sensitivity of the
model-based reactor concept with regard to the model configuration.

Literatur
[1] Freund, H., Sundmacher, K. (2008). Chemical Engineering and Processing: Process
Intensification 47, 2051-2060
[2] Freund, H., Peschel, A., Sundmacher, K. (2010). Chemie Ingenieur Technik 83, 420-426
[3] Peschel, A., et al. (2012). Chemical Engineering Journal 207-208, 656-674.
[4] Kaiser, M., Freund, H. (2019). Chemical Engineering Science, in press
Poster Abstracts
Processes
 APPtec - a new generation of spray pyrolysis technology to
produce advanced powder materials
Dr. Thomas Jähnert, Glatt Ingenieurtechnik GmbH, Weimar/Germany; Dr. Michael
Jacob, Glatt Ingenieurtechnik GmbH, Weimar/Germany

INTRODUCTION
The worldwide increasing demands on the functionality and service life of
components, devices and appliances lead to constantly new challenges in material
development across the entire value-added chain and reliably generating particles
with unique functionalities is an arduous task. Because of that many producers tend
to standardize to increase profit margins. The APPtec from Glatt attempts to fill the
void for a reliable technology to create unique and more reactive materials. Greater
functionality and extraordinary performance can be realized with high-performance
powders generated by APPtec.

RESULTS AND DISCUSSION

APPtec stands as synonym for Advanced Powder Process technology and allows
controlling the product properties of new types of powders, impacting or changing the
particle structure, composition or surface properties. The thermodynamic conditions
of our technology are exceptional and perfect to create highly functional inorganic
pigments catalyst and ceramic materials.
A pulsating stream of hot gas is the core of
the technology (Figure 1). This pulsating hot
gas stream brings turbulences into the

Fig. 1: Representation of the pulsation reaction chamber and these lead to new and
in the reaction chamber. exciting product properties. Through the
turbulences the heat transfer between gas stream and reactant is five to ten times
higher than in a conventional spray pyrolysis. It also leads to a very homogeneous
temperature across the reaction chamber and practically gets rid of the retention time
gradient, leading to very homogeneous powders. The specially designed combustion
chamber produces a strictly pulsating stream of hot gas, whose amplitude,
temperature and pulsation-frequency can be freely adjusted to tailor the products
properties and functions to the customers’ wishes.
Adjusting the temperature is one factor used to tailor the materials properties. If the
aim is to coat a substrate the possibilities can include the calcination and possible
oxidation of the coating material, but at lower temperatures it is also possible to coat
with metal salts or even organic materials like polymers.
Other process parameters are frequency and amplitude. The frequency and
amplitude describe how often and how strong the stream of hot gas pulses. Adjusting
these to higher values increases the heat transfer even more. This can be used to
decrease the retention times or give the option for phase transitions or calcination-
reactions to occur at lower temperatures. The amplitude and frequency can be
adjusted separately from one another.
APPtec is a versatile technology that can
not only produce simple metal oxides, but
also mixed oxides, doped oxides and
coated particles (Figure 2). In addition to Fig. 2: Functionalization of powder
particles with APPtec.
that it can also be used under inert or
reducing conditions, expanding the applications significantly. The pore size is also
freely adjustable and particle sizes from nano to micro can be achieved. Nearly all
raw materials can be used, ranging from solutions and suspensions to powders. A
big advantage of the APPtec for catalysts comes also from its ability to generate
particles with amorphous morphologies and large specific surface areas. Pigments
can be generated as well as coated with a protecting or functional layers and ceramic
materials can be formed with complex stoichiometries or crystal structures.

CONCLUSION
The exceptional thermodynamic conditions of APPtec create advanced powder
properties and allow the exact configuration of particles with combinations of
properties or the addition of new functions and surface properties.
Inorganic powders produced with APPtec are highly uniform and reactive. Surface
areas are larger than with comparable technologies. There are almost no limitations
regarding raw materials, which allows for a wide variety of raw materials to adjust the
products´ properties.
APPtec is the leading technology to produce highly functionalized and unique
specialty inorganic powder materials.
Continuous heterogeneous di-N-Alkylation of 1H-benzimidazole in a
fixed bed reactor

Tobias Sauk, Laurids Henke, Chunyu Xiao, Stephan Scholl, TU Braunschweig,

Institute for Chemical and Thermal Process Engineering and Research Center for
Pharmaceutical Engineering, Braunschweig/Germany

In recent years, both imidazol and benzimidazole derivatives have gained interest
due to their capability to form stable carbenes [1]. The resulting N-
heterocyclic carbenes (NHC) became widely used as ligands in the synthesis of
organometallic complexes (M-NHC) [2]. These diazoles can be considered as
scaffold chemicals for e.g. M-NHC synthesis which themselves act as catalysts but
also active pharmaceutical ingredients (API) [3, 4]. Heterogeneous di-N-alkylation of
diazoles by alkyl halides can suffer from long reaction times. By performing the
reaction in continuous flow, the synthesis of the resulting diazolium salts can benefit
from process intensification resulting in reduced reaction times and low holdup, thus
enabling fast and versatile on-demand production. In this contribution, an approach
for the continuous, heterogeneous di-N-alkylation of diazoles is presented.

Figure 1: Reaction scheme of the N-alkylation of 1H-benzimidazole in acetonitrile (ACN).

The exemplary synthesis (see Fig. 1) is performed in presence of the alkyl halide
methylene iodide and a solid base to form a diazolium salt derived from 1H-
benzimidazole: 1,3-dimethyl-1H-benzoimidazol-3-ium iodide (DMeBI). The synthesis is
realized in an electrically heated, pressurized fixed bed reactor (L = 250 mm,
ID = 8 mm) in combination with a subsequent electrically heated coil reactor (L = 5 m,
ID= 1 mm), a back-pressure regulator (7 bar) as well as two pumps, valves and a
mixer to direct and combine the reagent solutions as well as the cleaning solvent. In
order to achieve total conversion of the reagents in the first reaction step, a basic
reagent or catalyst is required. The second reaction step is independent of the basic
component. The synthesis is performed regarding the influence of temperature,
volume flow and therefore residence time, type of basic reagent/catalyst (K2CO3,
zeolites, metal oxides, activated carbon, ion exchange resins) and packing (packing
density, surface area, stability) as well as ratio of the reagents. The focus is to
achieve full and fast conversion to
the desired product, whereas 70°C

Mole fractionDMeBI [%]

100
avoidance of decomposition of the 100°C
80
130°C
alkylating agent at high 60 150°C
temperatures and utilization of an 40
effective yet low cost catalyst has 20
to be taken into account. Results 0
0 10 20 30 40 50 60
indicate increased conversion Fixed bed residence time [min]
Figure 2: Influence of residence time and temperature on the
rates at elevated temperatures continuous synthesis in the fixed bed reactor.
above the boiling point at atmospheric pressure of acetonitrile (approx. 82 °C) but
also an upper temperature limit as indicated by a lower total conversion and strong
yellow coloring of the product solution at 150 °C (see Fig. 2). Different basic catalysts
show slightly better or worse conversion rates in comparison to the basic reagent
K2CO3 and simultaneously
100% increase impurities indicated by a
Mole fractionDMeBI [%]

80% yellow coloring of the reaction

60% solution (see Fig. 3). In case of
K2CO3
Act. carbon (RST) activated carbon, the conversion
40%
Act. carbon (ROY)
20% CaO rate surpasses that in presence of
Zeolite (KX)
0% K2CO3. It is worthwhile noting, that
0 50 100 150 200
Time [min] the basic character in combination
Figure 3: Effect of different catalysts on the synthesis of DMeBI
in a batch process at 70°C. with a high surface area of
activated carbon due to its porosity is accountable for the increased conversion rates
towards the intermediate and subsequently to the product whereas the used K2CO3
is a non-porous reagent with a lower surface area. In general, the feasibility of the
heterogeneous N-alkylation of diazoles in continuous flow in a fixed bed reactor has
been shown while also comparing a cost efficient and abundant basic reagent and a
selection of basic catalysts. The results can be transferred to the synthesis of other
diazolium salts derived from various derivatives of 1H-imidazole and 1H-
benzimidazol.

References
[1] Arduengo, A. J., et al. J. Am. Chem. Soc. DOI=10.1021/ja00001a054.
[2] Crudden, C. M., et al. Coordination Chemistry Reviews. DOI=10.1016/j.ccr.2004.05.013.
[3] Frémont, P. de, et al. Coordination Chemistry Reviews. DOI=10.1016/j.ccr.2008.05.018.
[4] Oehninger, L., et al. Chemistry (Weinheim an der Bergstrasse, Germany).
DOI=10.1002/chem.201302819.
 Design and optimization of a continuous Krapcho dealkoxy-
carbonylation process within the scope of Paullone synthesis

M. C. Rehbein1,3, J. Wolters1, L. Priess1, C. Kunick2,3, S. Scholl1,3

1
Institute for Chemical and Thermal Process Engineering, TU Braunschweig, Germany
2
Institute for Medicinal and Pharmaceutical Chemistry, TU Braunschweig, Germany
3
Center for Pharmaceutical Engineering Research (PVZ), TU Braunschweig, Germany

Protein kinase inhibitors and

polar aprotic
anti-cancer agents from the solvent
class of paullones [1,2] and ΔT

closely related substances [3]

have gained increased attention Figure 1: Krapcho dealkoxycarbonylation reaction for the synthesis of 3,4-
dihydro-1H-1-benzazepine-2,5-dione (DHBD)
during the last two decades.
The synthesis of the aforementioned compounds requires the scaffold 3,4-dihydro-
1H-1-benzazepine-2,5-dione (DHBD) or its derivatives. DHBD is derived via Krapcho
dealkoxycarbonylation [4] of ethyl 5-hydroxy-2-oxo-2,3-dihydro-1H-1-benzazepine-4-
carboxylate (R). According to Figure 1, a typical lab synthesis of DHBD proceeds in
high-boiling polar aprotic solvents like DMSO with water as co-reactant under neutral
conditions at temperatures of about 150 °C. The conventional lab synthesis under
ambient pressure is limited in terms of solvent choice and reaction temperature,
resulting in reaction times of several hours [5].
In this contribution, a continuous flow process for the synthesis of DHBD under
increased pressure and temperature is designed and the flow reaction is
characterized with regards to reaction temperature, ratio of reactant to added water
and choice of solvent. The general aim was to intensify the reaction and maximize
reactant solubility, in order to increase
1
space-time-yield (STY) and therefore extrapolation
of the model

design a more efficient reaction 0,8

Conversion of R / -

compared to the batch process. 0,6

For reactor design, a first order kinetic 0,4

batch - 135 °C
batch - 145 °C
batch - 160 °C
model was employed, based on data conti. - 145 °C
conti. - 160 °C
0,2 conti. - 170 °C
determined via in-situ ATR-FTIR in conti. - 185 °C
conti. - 200 °C
0
batch [6]. Reactor length and therefore 10 100 1000 10000
Reaction or residence time /model
s
residence time was adjusted so that the conversion

model predicted conversions between 0.2 and 1, dependent on flow rate and
Figure 2 Conversion for various temperatures in batch and
continuous reactors, lines: first order kinetic model; parameters:
DMSO, cR = 5 mg/mL
temperature. A tubular stainless steel flow reactor with dimensions L x di = 2,500 x 1
mm was utilized. A back pressure regulator at the reactor outlet prevented boiling up
to 200 °C also for low boiling solvents.
Initial characterization proves that reactant conversion in DMSO is well described by
the model and extrapolation to higher temperatures nicely predicts results from the
continuous reactor (Figure 2). Reaction temperature has a significant influence on
reaction rate. Compared to the reaction in batch and as predicted, reaction time for
complete conversion could be significantly reduced in the flow reactor at 200 °C [7].
The amount of water added has only a minor effect on reaction rate. When reactant
concentration is high however, rates are slowed down, if no water is added.
Screening different solvents revealed that the reaction proceeds very well and
without unwanted byproducts in polar aprotic, but to no significant extend in polar
protic solvents like ethanol. For aprotic polar solvents, reaction rate constants
seemingly depend on the polarity of the solvent used. Highest reaction rates were
determined in DMSO, DMF and DMAc.
20
To identify the optimum solvent, measured reaction
STY / mg mL-1 min-1

15
kinetic and solubility data were incorporated in a
theoretical assessment of STY (Figure 3). In 10

general, DMSO, DMF and DMAc are superior to 5

other aprotic polar solvents in terms of STY, 0

especially because of their higher reactant Figure 3: Calculated STY in different solvents
and comparison to batch in DMSO
solubility. Comparing the batch and continuous
reaction process, the possibility to operate the continuous reactor at higher
temperatures with vastly improved rates results in a significantly higher STY. Since
most Krapcho dealkoxycarbonylation reactions suffer from relatively long reaction
times, the adaptation of the presented flow methodology might significantly
accelerate a number of those transformations and increase reaction efficiency.

References
[1] N. Tolle, C. Kunick, Curr. Top. Med. Chem. 11 (2011) 1320–1332.
[2] C. Schultz, et al., J. Med. Chem. 42 (1999) 2909–2919.
[3] H. Falke, et al., Journal of medicinal chemistry 58 (2015) 3131–3143.
[4] A. P. Krapcho, et al., Tetrahedron Letters 8 (1967) 215–217.
[5] C. Kunick, Arch. Pharm. Pharm. Med. Chem. 324 (1991) 579–581.
[6] M. C. Rehbein, et al., Eur. J. Pharm. Biopharm. 126 (2018) 95–100.
[7] M. C. Rehbein, et al., J. Flow. Chem. (2018) (submitted).
Solvent Regeneration via Transesterification in Reactive Distillation

Andreas Toth, Susanne Lux, Daniela Painer, Matthäus Siebenhofer

Graz University of Technology, Institute of Chemical Engineering and Environmental

Technology, NAWI Graz, Graz/Austria

Introduction
Holistic utilization of biomass feedstock is currently one of the most challenging tasks
in biorefinery affairs with exploitation of (hydroxy-) carboxylic acids from aqueous
effluents playing a major role. Chemical conversion of carboxylic acids with 1-octanol
in a biphasic, emulsified system was proven applicable for providing economical,
feasible solutions for acid isolation from dilute effluents. [1] To enable implementation
of this concept in a continuous process, solvent regeneration and product isolation
need to be investigated.

Methodology
Regenerating the solvent (1-octanol diluted in n-undecane) may be achieved by
transesterification of the octyl esters with the low molecular weight alcohol methanol.
Transesterification grants two benefits: firstly, the reactant for the esterification step
(1-octanol) is a reaction product of transesterification. Secondly, the low molecular
weight esters enable simple distillative separation from the reaction broth due to their
lower boiling point. Esterification is accelerated with the catalyst 4-dodecyl-
benzenesulfonic acid (4DBSA). According to Hagen et al. [2], the catalyst used in
the esterification step (4-dodecylbenzenesulfonic acid) is also a highly potent catalyst
for transesterification. The proof of concept for transesterification/distillation was
performed in batch reactive distillation. A mixture of 1-octanol, n-undecane, octyl
acetate and 4DBSA from single step extraction was transesterified with methanol.

Results and Conclusion

Methyl acetate yields above 63% confirm the proposed concept for product isolation.
Solvent regeneration is proven by a very low amount of volatile residues in the
bottom product of the batch reactive distillation of 0.3 wt%.

References
[1] A. Toth, S. Lux, D. Painer, M. Siebenhofer, React. Chem. Eng. 2018, 3, 905-911. DOI:
10.1039/C8RE00194D.
[2] J. Hagen, D. Henke, Chemie Ing. Tech. 2009, 81 (9), 1429–1438. DOI: 10.1002/cite.200800186.
 Coupled
oupled extraction and partial synthesis for the production of an
antimalarial: Solvent
Solvent and acid dependences
dependence

Susann Triemer,, Ma
Max Plan
Planck
Planc In
Institute
titute for D
Dynamics
nami of Comple
Complex Technical
Te
Techni
hni al S
Systems,
tem ,
Magdeburg/Germany;
Kerry Gilmore, Ma
Max Planck Institute
In titute of Colloid
Colloids and Interfa
Interfaces,
e , Potsdam/German
Potsdam/Germany;;
Andreas Seidel-Morgen
Morgenstern,
tern, Max Planck Institute for D
Dynamics
namics of Complex
Comple
Techni al S
Technical Systems,
tem , Magdeburg/German
Magdeburg/Germany

In the millennium de
development
elopment goals
goal of the United Nations,
Nation the combat
ombat again
againstt
malaria was stated as a major task.
ta . In
Increasing
rea ing the a
availability
ailabilit and redu
reducing
ing the cost
o t
of artemisinin-based
ba ed treatments
treatment - currently the mo
mostt a
active
ti e medication
medications again
againstt the
disease - are important steps
step to a
achieve
hie e that goal. Although an industrial
indu trial pro
process
e
based
ba ed on biotechnological
biote hnologi
hnological
al and chemical
hemi al conversion
on er ion is
i already
alread implemented,
artemisinin
artemi inin iis still
till mainly produced
produ ed by
b extraction
e tra tion of the plant Artemisia annua,
annua where
it iis formed a
as secondary
e ondary metabolite. The low content
ontent of the API in the dried matter
(max. 1.4 wt-%) and the long cultivation
ulti ation time of the plant caused
au ed in recent
re ent years
ear high
prices a
as well a
as strong
trong price fluctuation.
flu tuation.
One approa
approach
h to ma
make
e artemi
artemisinin-based
inin ba ed medi
medications
ation more widely available
a ailable iis to
increase
in rea e the yield
ield of artemisinin
artemi inin obtained from e
extracti
traction
tra ti by utilizing
dihydroartemisinic
dih droartemi ini aacid
id (DHAA) - a precursor to artemisinin.. DHAA is
i traditionally a
co-extracted waste product of the process.
pro e It can
an be converted
on erted to artemi
artemisinin
inin via
ia a
photooxidation
photoo idation and subsequent
ubsequent acid-catalyzed
a id reaction sequence [1].
[1] To initiate the
photooxidation, a photoactive
photoactive compound
ompound iis required whi
which
h transfers absorbed
ab orbed light
energy to triplet o
oxygen
gen forming singlet
inglet oxygen.
o gen. Recently, we
e demonstrated
demon trate that

Figure 1:: Schematic representation of the process for continuous artemisinin production starting from
the plant Artemisia annua.
chlorophyll, a second byproduct of the extraction, can be utilized to initiate the
photooxidation making the addition of other, often toxic photosensitizers
unnecessary [2]. Thus, artemisinin can be synthesized out of crude extract of A.
annua – which contains both the reactant and the photosensitizer – by treating it just
with oxygen, visible light, and acid (figure 1).
To carry out the overall process to artemisinin efficiently, the conditions for both the
extraction and the partial synthesis need to be attuned and optimized regarding
operation costs, sustainability, and intrinsic process safety. In this respect the most
important operation parameters are the solvent chosen for extraction and partial
synthesis as well as the acid used in the acid-catalyzed reaction sequence.
The extraction is investigated by contacting ground leaves of. A. annua with different
solvents (e.g. toluene, ethanol and butanol) in batch mode. The obtained extract is
pumped in a mini-channel tubular reactor, contacted with oxygen in a T-mixer, and
illuminated by a high-intensity LED lamp. The small dimensions of the reactor ensure
high mass transfer rates and strong illumination of the whole reactant solution. The
acid-catalyzed step is either initiated by trifluoroacetic acid added to the feed solution
or by solid acid present in a fixed-bed reactor. Different heterogeneous Lewis and
Brønstedt acids were investigated. The operation conditions were optimized.
The results show that sufficient amounts of chlorophyll for the photooxidation can be
obtained with all tested solvents leading to more flexibility with respect to the solvent
selection. The application of solid acids in the partial synthesis was found to be a
beneficial alternative to homogenous acids yielding good selectivity of artemisinin
and enabling easy separation and re-use.

References:

1. Kopetzki, D., F. Levesque, and P.H. Seeberger, A continuous-flow process for

the synthesis of artemisinin. Chemistry-a European Journal, 2013. 19(17): p.
5450-6.
2. Triemer, S., K. Gilmore, G.T. Vu, P.H. Seeberger, and A. Seidel-Morgenstern,
Literally Green Chemical Synthesis of Artemisinin from Plant Extracts.
Angewandte Chemie - International Edition, 2018. 57(19): p. 5525-5528.
 Model-based
based performance analysis
analysis and optimi
optimization
ation approach
of an industrial methacrylic acid reactor

T. Bürger
Bürg and B. Kraushaar-Czarnetzki,
Institute
In titute of Chemical
Chemi al Proces
Process
Pro e Engineering (CVT), Karl
Karlsruhe
ruhe Institute
In titute of Te
Technology,
hnolog ,
KIT Campus
Campu South, 76131 Karlsruhe/Germany

Motivation
Methacrylic
Metha r li acid
a id (MAA) iis an important intermediate of the chemical
hemical
hemi al industry
indu tr which
whi h is
i
used
u ed especially
e pe iall in form of its
it al
alkyll e
esters
ter for the produ
production
tion of pol
polymer
polymers
mer and pla
plastics.
ti .
Mostt synthesis
Mo nthe i routes
route to MAA in
include
lude a
as the la
lastt step
tep the partial oxidation
o idation of
methacrolein
metha rolein (MA) o
over
er heteropol
heteropoly a
acid
id (HPA) catalysts
atal t which
whi h is
i carried
arried out in cooled
ooled
multitubular rea
reactors
tor due to itits high rea
reaction
tion heat. Especially
E pe iall Keggin type
t pe Mo/V/P/Cs
Mo/V/P/C
based
ba ed HPA are suitable
uitable catal
catalysts
t showing
howing both good a
activity
ti it and selectivity
sele ti it toward
MAA, though al
also
o a relati
relatively
el low stability
tabilit due to irreversible
irre er ible deactivation
dea ti ation leading to a
catalyst
atal t lifetime of a couple
ouple of month
months.. Hen
Hence,
e, it is
i of parti
particular
ular intere
interestt to study
tud an
industrial
indu trial MAA reactor
rea tor by numeri
numerical
al simulation
imulation searching
ear hing for levers to optimize
optimi e the
current
urrent rea
reactor
tor performance.

Model Development
In order to obtain a referen
reference
e basis
ba i for the subsequent
ub equent model cal
calculations,
al ulation , the
characteristic
hara teri ti dimensions
dimen ion
ions and operating conditions
ondition of an industrial
indu trial MAA rea
reactor
tor were
chosen on the ba
basis
i of a patent search.
ear h. Afterward
Afterwards,, a kinetic
ineti model wa
was de
developed
eloped
using
u ing experimental
e perimental data of a pilot
pilot-scale
ale tubular multi
multisampling
ampling reactor which
whi h were
acquired
a quired to study
tud the performan
performance
e of an indu
industrial
trial HPA catalyst.
atal t. Empiri
Empirical
al e
estimation
timation
criteria were applied to determine the ne
necessary
e ar level
le el of detail of the reactor
rea tor model to
be de
developed
eloped leading to a pseudo-homogeneous
pseudo two-dimensional
dimen ional reactor
rea tor model with
negligible a
axial
ial dispersion of heat and
mass whi
ma which
h was then validated
alidated by
b
recalculating
re al ulating comparati
omparative
e e
examples in
the sighted patents.

Figure 1: Sketch of the industrial

indu trial MAA reactor.
rea tor.
Results
Results of the performance analysis of the industrial MAA reactor are shown in Fig. 2,
representing our reference case. Contrary to our expectations, the mean temperature
of the gas phase is nearly constant at a certain point of the catalyst bed and thus no
pronounced hot spot behavior is observable. Along the catalyst bed the maximum
temperature of the gas phase is about 300 °C occurring at an axial position of 1,6 m
at the reaction tube center. The conversion of MA and the yield of MAA are 66 % and
56 % at the end of the catalyst bed, thus specifying the current reactor performance.

320 100 100 300

TG
TS
300 80 80 298

YMAA,MA / %
280 60 60 296
XMA / %

TG / °C
T / °C

260 40 40 294

240 XMA 20 20 292

YMAA,MA
220 0 0 290
0 1 2 3 4 0 2 4 6 8 10 12
z/m r / mm
Figure 2: The mean temperature of the gas phase TG and the temperature of the molten salt TS along
a single tube of the industrial MAA reactor together with the associated profiles of both the conversion
of MA XMA and the yield of MAA YMAA,MA (left) and the temperature of the gas phase TG as a function of
the reaction tube radius r at the axial position of 1,6 m (right).

Based on these results, a case study was carried out in which the dimensions and
operating conditions of the industrial MAA reactor were varied, thus looking for ways
to increase the current yield of MAA. An improvement of the temperature distribution
is not really required since there is no pronounced hot spot behavior observable.
However, it specifies the current deactivation rate which is strongly influenced by the
reaction temperature. Hence, account was taken of the fact that the temperature of
the gas phase along the catalyst bed should not exceed the limit value of 300 °C in
order to prevent a potentially faster deactivation of the HPA catalyst in question. The
case study revealed some optimization potential leading to an increase of the yield of
MAA of up to 15 % compared to our reference case. The knowledge gained was then
used to develop an improved reactor design with regard to the yield of MAA which
will be discussed in more detail in the presentation.
Reactive separations for downstream processing in the biorefinery
Daniela Painer, Susanne Lux, Matthäus Siebenhofer, Graz University of Technology,
Graz/Austria

The shift from fossil to biobased resources is inevitable, due to limited fossil
resources and due to the global environmental impact of fossil resources based
greenhouse gas emissions. To be able to satisfy the market needs via biobased
resources complete utilisation of biomass is essential must. Also byproducts and
waste need to be valorised. One of the largest player in the biorefinery business, the
pulping industry, still mainly focuses on the main product cellulose fibres, while the
byproducts e.g. lignins, carboxylic acids and hydroxycarboxylic acids are just
considered for energy production. For isolation of low value products from
multicomponent mixtures, like carboxylic acids from black liquor condensate,
downstream processing needs to be highly intensified to obtain economic
competitiveness.
State of the art of carboxylic acid recovery from aqueous feed is reactive extraction
with the drawback of difficult and energy consuming solvent regeneration. Therefore
reactive distillation was investigated for solvent regeneration. Esterification of acids
with methanol provides simple reaction product removal from reaction broths by
reactive distillation due to a significant change of constituent properties by making
use of elevated temperature in the reboiler. Enhancing the reaction rate through
admixture of the homogeneous catalyst 4-dodecylbenzenesulfonic acid (4-DBSA) is
necessary for high conversion. In batch reactive distillation, yields of methyl formate
and methyl acetate in the distillate of 100 % and 92 %, respectively, were obtained.
In addition to its catalytic activity, 4-DBSA is preferably present in the solvent phase,
marginally influencing the extraction performance. Therefore, catalyst separation
from the solvent is not required. It is feasible to recirculate the catalyst in the solvent
phase.
To offer flexible process implementation, performance of the heterogeneous catalyst
Amberlite®IR-120 was investigated Amberlite®IR-120 was able to achieve similar
methyl ester yields with slightly higher reaction rates compared to homogeneous
catalysis. Heterogeneous catalysis neither influences extraction efficiency nor
requires complex catalyst recovery.
Poster Abstracts
Miscellaneous
 Additive manufacturing and hydrodynamic characteristics of
3D structured monoliths with hierarchical porosity
Sebastian Hock, Marcus Rose, Ernst-Berl-Institut für Technische und
Makromolekulare Chemie, TU Darmstadt, Germany.

3D printing has gained enormous interest over the past few years in both industry
and science. Especially for the production of monolithic catalyst this technology
provides new innovative opportunities to produce complex 3D structures in
comparison to conventional methods.[1] In relation to traditional packed beds or
monoliths with one dimensional channels more complex structures offer advantages
for heat and mass transport, pressure drop and scale up.[2] The optimization of these
parameters is an important challenge in catalysis and reaction engineering and often
requires complex setups, high costs and time effort. For this reason the utilization of
computational fluid dynamics (CFD) is beneficial. The combination of computer-aided
manufacturing technologies with simulation and data processing methods results in a
new research field with great potential. In industry it could not only result in improved
reactors or structured catalysts but even change the way of designing and
manufacturing functional objects.[3]
In our work, we designed and 3D printed cylindrical monoliths with differently
structured pore channels. The hydrodynamic characteristics of four selected
structures were experimentally investigated by measuring the residence time
distribution and the pressure drop. Complementary, a CFD simulation of the
monoliths’ hydrodynamic behaviour was carried out and compared to the
experimental results that showed a good agreement.[4]
Another aspect is the creation of monoliths with hierarchical porosity, i.e.,
integrating high surface areas on/in the pore walls of macroporous structures,
especially motivated by the integration of catalytic active materials. In this context,
polymer composite filaments containing zeolites as well as porous polymer particles
were prepared by melt extrusion and subsequently printed into 3D structured
monoliths. Printing by melt extrusion was possible up to a filler content of 50 wt-%
zeolite and 40 wt-% porous polymer. Thereby, specific BET surface areas of the
monoliths of up to 171 m2 ∙g-1 were achieved. Printable filaments with intrinsic
microporosity in combination with additive manufacturing provide the basis for the
production of functional and complex structured monolithic catalysts and adsorbents.
References
[1] A. Ambrosi, M. Pumera, Chem. Soc. Rev.2016, 45, 2740-2755.
[2] T. Zhou, C.‐J. Liu, Adv. Funct. Mater. 2017, 27, 1701134.
[3] C. Parra-Cabrera, C. Achille, S. Kuhn, R. Ameloot, Chem. Soc. Rev. 2018, 47, 209-230.
[4] S.Hock, M. Rose, manuscript in preparation.
 Development of Ceramic Composites for Electrically Heated
Catalytic Converters

V. Schallharta, H. Bertholdb, T. Endlichb, H. Gottschalkb, L. Möltnera,

I. Worschischekb, E. Klemmc,
a
MCI Management Center Innsbruck, Innsbruck/Austria, bCoorsTek Advanced
Materials Lauf GmbH, Lauf a. d. Pegnitz/Germany, cInstitute of Chemical
Technology, University of Stuttgart, Stuttgart/Germany

The rate of a heterogeneous catalytic process is strongly dependent on the

simultaneously occurring heat and mass transfer. In particular, an adequate
catalyst’s temperature during transient operating conditions can represent a major
challenge. For instance, the implemented catalytic converters in a vehicle’s exhaust
gas system require a so-called light-off temperature of approximately 473 K for an
effective conversion of emissions [1].

The goal of this study is to develop conductive ceramic composite materials to

directly heat catalytic converters and thus considerably decrease the catalysts’ light-
off period. An automotive catalyst commonly consists of a ceramic carrier material
coated with a highly porous washcoat including the catalytic active component.
Cordierite is a widespread support material due to its excellent material properties
and cost-effectiveness [2]. The insulating cordierite is in this study combined with
different (semi-)conducting materials and the resulting material properties are
investigated.

The fabrication of electrically conductive ceramic composite materials is greatly

influenced by the fraction of conductive material within the insulating cordierite. The
share of conductive fillers must be above a critical threshold for the formation of an
interconnected network structure in the ceramic matrix. In the case of a binary
system consisting of an insulator and a conductor, the electrical properties drastically
change from insulating to conducting above this percolation threshold, whereby the
conductivity of the composite material is in the same range as that of the conductive
filler [3]. For a more effective influence on the conductivity of the composite materials,
ternary mixtures were fabricated by combining the cordierite ceramic with a metallic
and a semi-conducting compound. Furthermore, the ability of a metal to wet the
ceramic surface is rather poor but mitigated with the additional semiconducting
compound [4], which is crucial for the formation of an interconnected network.

This approach allowed the fabrication of several conductive composite materials,

which could enable the direct heating of catalytic converters. Figure 1 reveals the
heat-up behavior from 303 K to 473 K at 32 V and an average current of 1.2 A for a
cylindrically shaped composite sample (L = 8 cm, D = 1 cm, m = 15 g). The
experimentally displayed temperature indicates the center point of the sample and is
compared to a 1D-simulation, whereby the temperature-dependent specific ohmic
resistance of the sample was previously determined by a four-wire ohms
measurement.

Figure 1: Empirically and numerically determined temperature progression for a cylindrical composite
operated with 32 V and an average current of 1.2 A

Challenges for the application of the developed composite materials as catalyst

support are the mechanical stability and particularly the oxidation stability of the
materials at high temperatures. In a next step, the materials are thus artificially aged
at different temperatures under atmospheric conditions and the change in
conductivity is determined. In addition, a simulation model is developed to calculate
the material properties of the composites and to consequently enable the
optimization or design of composite materials for a specific application.
[1] Laible, T.; et al.; “Light-off/out-Unterstützung beim Katalysator von Dieselmotoren.”
Motortechnische Zeitschrift 11, 2015, ISSN 0024-8525 10824.
[2] Radwan, N.; et.al.; “Cordierite as catalyst support for cobalt and manganese oxides in oxidation-
reduction reactions.” Applied Catalysis A: General (274) 87-99, 2004.
[3] Seung H.; et.al.; “The effect of polymer particle size on three-dimensional percolation in core-shell
networks of PMMA/MWCNTs nanocomposites: Properties and mathematical percolation model.”
Composites Science and Technology (165), 2018.
[4] Nascimento, R.; et.al.; “Review Article: recent advances in metal-ceramic brazing.” Ceramica
49(312), 2003.
 Ultra-low temperature methanol reforming using immobilized
Ru-Pincer complexes

Christian Schwarz, Marco Haumann, Friedrich-Alexander-Universität Erlangen-

Nürnberg (FAU), Chemische Reaktionstechnik (CRT), Egerlandstr. 3, 91058
Erlangen, Germany

Recently, a range of noble-metal and base-metal complexes has been successfully

employed for the homogeneously catalyzed dehydrogenation of methanol.[1] Hereby,
one of the most active systems, working at extremely low temperatures below
100 °C, is catalyzed by an aliphatic Ru-pincer complex under highly basic
conditions.[2] As depicted in Scheme 1, the complete aqueous phase reforming
(APR) process leads to the consecutive formation of formaldehyde, formic acid and
carbon dioxide and the concomitant release of one hydrogen molecule during each
step. Under basic reaction conditions, the CO2 is initially captured as carbonate. The
dehydrogenation of formate to CO2 was determined to be the rate-determining step
since it accumulated during the reaction.[3]

Scheme 1: Overview of possible reaction intermediates in methanol dehydrogenation.

One attractive feature of these low temperature MeOH reforming catalysts is the
drastically reduced formation of CO, a potential fuel cell poison. However, in order to
design potential processes based on such attractive catalysts, continuous operation
must be ensured. Liquid-phase operation is not feasible, since the high amount of
formed carbonates and the corrosive nature of the KOH constitute major obstacles.

Based on Supported Ionic Liquid Phase (SILP) technology we envisioned a similar

approach for the immobilization of the methanol dehydrogenation catalyst.[4]
Preliminary studies showed that a dispersed thin film of KOH on the inner surface of
highly porous solid materials simultaneously facilitates the immobilization of the
Ru-complex and acts as a basic additive. Under reaction conditions the latter
described catalyst forms a liquid layer inside the pore system of the support material
and therefore can be described as a SLP (Supported Liquid Phase) catalyst. These
materials can be handled like classical heterogeneous catalysts and are highly
attractive for large-scale continuous applications

Figure 1: Schematic illustration of SLP technology for continuous vapor-phase applications.

In this work, we present our immobilization studies using commercially available

Ru-Pincer catalysts for vapor-phase applications. Additionally we plan to show first
results of the coupling of our continuous methanol reformer to a High-Temperature
PEM Fuel Cell. It is anticipated that such a technology would allow decentralized
hydrogen storage and release for a variety of future applications.

References

1. a) Alberico, E., et al., Selective hydrogen production from methanol with a defined iron pincer
catalyst under mild conditions. Angew Chem Int Ed Engl, 2013. 52(52): p. 14162-6; b)
Bielinski, E.A., et al., Base-Free Methanol Dehydrogenation Using a Pincer-Supported Iron
Compound and Lewis Acid Co-catalyst. ACS Catalysis, 2015. 5(4): p. 2404-2415; c) Campos,
J., et al., Methanol dehydrogenation by iridium N-heterocyclic carbene complexes. Inorg
Chem, 2015. 54(11): p. 5079-84; d) Hu, P., et al., Reusable Homogeneous Catalytic System
for Hydrogen Production from Methanol and Water. ACS Catalysis, 2014. 4(8): p. 2649-2652;
e) Rodriguez-Lugo, R.E., et al., A homogeneous transition metal complex for clean hydrogen
production from methanol-water mixtures. Nat Chem, 2013. 5(4): p. 342-7.
2. Nielsen, M., et al., Low-temperature aqueous-phase methanol dehydrogenation to hydrogen
and carbon dioxide. Nature, 2013. 495(7439): p. 85-9.
3. Strobel, V., et al., Shining light on low-temperature methanol aqueous-phase reforming using
homogeneous Ru-pincer complexes – operando Raman-GC studies. React. Chem. Eng.,
2017. 2(3): p. 390-396.
4. Riisager, A., et al., Supported Ionic Liquid Phase (SILP) catalysis: An innovative concept for
homogeneous catalysis in continuous fixed-bed reactors. European Journal of Inorganic
Chemistry, 2006. 2006(4): p. 695-706.
 Investigation of polymer depositions during the synthesis
in a heat exchanger

A. Hohlen, W. Augustin and S. Scholl, Technische Universität Braunschweig,

Institute for Chemical and Thermal Process Engineering, Braunschweig/ Germany

During the synthesis and processing of polymers, a significant amount of polymer

may be deposited on the heat transfer surfaces. These deposits, also named fouling,
form an additional heat conducting resistance and reduce the efficiency of the heat
exchanger. This increases the required heat transfer area for a given production
capacity as well as energy demand and thus ultimately increases CO2 emission. In
addition, deposited fouling layers can come off again from the reactor walls and thus
deteriorate product quality. Until now, a lack of understanding of the reaction-side
formation of polymer fouling during continuous polymerization prevents from the
development of possible strategies to reduce fouling.
In order to obtain basic information about polymerization fouling, the deposition
behavior of a polymer dispersion on a heat transfer surface was investigated during
the synthesis of this polymer. The influence of different operating parameters was
investigated in order to identify possible fouling reducing factors. Especially surface

Figure 1: Flow chart of the experimental setup

temperature and surface properties were varied.

. A bench scale unit was operated and the deposition behavior of a polymer during its
synthesis was investigated by varying different parameters in a defined way. The test
unit is run in a loop and essentially consists of a double-walled reaction vessel and a
flow channel, as shown in Figure 1. The reaction vessel serves as storage vessel in
which the reactants are mixed and preheated while the flow channel represents the
heat-transferring surface for the fouling investigations. The initiator is added previous
to the inlet of the flow channel, so that the reaction takes place inside the flow
channel. The deposition was quantified by the mass based fouling resistance, the
height of the fouling layer and optically by the surface coverage using a digital
microscopy.
First investigations have shown that the type of substrate used has a significant
influence on fouling. For this purpose, the fouling layers on a technically smooth
surface, an electropolished surface and a surface coated with diamond-like
carbon (DLC) were compared. It was found that both the deposited fouling mass and
the layer height were reduced by modifying the surface. The same effects have
already been observed in previous investigations with a polymer suspension that has
already reacted [1]. Furthermore, the influence of the surface temperature was
investigated. A particularly influence is exerted by the direction of the heat flow, i.e.
whether the surface is heated or cooled. While only a very thin film of a few
micrometers is deposited on the surface on cooled surfaces, a relatively thick fouling
layer with crater-shaped elevations is formed on the heated surface. To receive more
detailed information about the polymeric composition of the deposit, the structure of
the deposit material as well as the molecular weight were measured via gel
permeation chromatography (GPC) and nuclear magnetic-spectroscopy (NMR).

[1] Gottschalk, N., Kuschnerow, J. C., Föste, H., Augustin, W., Scholl, S.:
Experimentelle Untersuchung zur Foulingneigung einer Polymerdispersion auf
modifizierten Oberflächen, Chem. Tech. 87 (2015), pp. 600-608