BMBF, 2014, Chemical Processes and Use of CO2
BMBF, 2014, Chemical Processes and Use of CO2
BMBF, 2014, Chemical Processes and Use of CO2
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FORSCHUNG
BILDUNG
contents
Contents
Preface3
Dr. Georg Schtte, State Secretary at the Ministry of Education and Research
CONFERENCE KEYNOTES
Chemical Processes and Use of CO2 4
Lothar Mennicken Dr. sc., BMBF
Five Years down the Road Expectations and Results from the Industry Perspective6
Prof. Michael Rper
Gas Innovation for the Future Power to Gas8
Prof. Thomas Kolb, head of the DVGW Research Center at the University of Karlsruhe Engler Bunte Institute
Opportunities for Carbon Dioxide Utilization at Bayer10
Dr. Martina Peters, Bayer Technology Services GmbH
EUROPEAN ACTIVITIES
SCOT Smart Carbon Dioxide Transformation69
National Contact Point (NCP): the Horizon 2020 European Research and Innovation Framework Program
71
POSTERS
77
preface
Preface
Energiewende, climate protection
and resource efficiency all
together are major societal challenges, we have to face. One key
question in this regard is how
chemical processes and techniques can be modified so that
carbon dioxide emissions can be
reduced and the combustion waste product (CO2) can
become a feedstock for the chemical industry.
Against this background, the Federal Ministry of Education and Research (BMBF) and Siemens organized a
joint seminar on CO2 utilization potential at Petersberg/
Bonn in 2009. International and national representatives
from science and industry who attended the seminar
discussed the potential for protecting the climate
through CO2 mitigation and the use of CO2 as well as
where that potential can be realized and what the associated research needs are. Based on these results, that
same year BMBF announced the call for Technologies
for Sustainability and Climate Protection Chemical
Processes and Use of CO2 under the umbrella of the
FONA (Research for Sustainable Development) program. Since then, BMBF has provided approximately
100 million euros in funding for technologies such as
the use of carbon dioxide in basic chemicals, chemical
storage of renewable energy and industrial energy efficiency in processes, which have high emissions reduction potential. This makes Germany the world leader in
this innovative future technology. Private industry is
providing approximately 50 million euros in additional
funding for these research projects.
Collaboration between industry, SMEs and research
organizations on these projects promotes the development of young scientists and fully exploits the expertise of everyone involved.
conference keynotes
Researchers working in the chemical energy storage cluster are looking at technologies for chemical
storage of renewable energy. Two pathways, currently
under investigation, are the production of hydrogen
and methane (Power to Gas) as well as gasoline, diesel
and kerosene (Power to Fuel, Power to Liquid). (Excess)
electricity generated from renewable resources is used
for water electrolysis to gain hydrogen. In a subsequent
process, hydrogen is processed with CO2 to produce
methane or liquid fuel.
In the SEE Storage of Electrical Energy from Renewable Resources in the Natural Gas Grid project for example, researchers are looking at all of the steps in the
process sequence (electrolysis, methanation and conditioning to adjust the calorific value) used to produce
methane (synthetic natural gas). The consortium,
which is coordinated by the DVGW Research Center
at the University of Karlsruhe, at the Engler Bunte Institute, consists of eight partners from science and industry. EnBW Energie Baden-Wrttemberg, a potential
applicant, is evaluating the economic viability and is
looking at possible sites for demonstrators. An innovative technique for using highly efficient high-temperature steam electrolysis and renewable energy to convert CO2 and H2O into liquid fuel is being developed on
the Sunfire project. Eight partners are involved in this
project with sunfire GmbH acting as coordinator. The
primary objective is to eventually ramp up production
to pre-industrial scale. To promote development in
this field of technology, BMBF is currently funding six
consortium projects in this research program and two
projects in other research programs (Entrepreneurial
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10
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So where are we? If ways are found to use carbon dioxide as a feedstock in energy-efficient industrial applications, new sustainable chemical production processes
could be developed. This could reduce carbon resource
consumption and make a limited but very welcome
and economically attractive contribution to climate
protection. Direct CO2 emissions into the atmosphere
could be reduced and oil-based substances could be replaced with carbon dioxide. Bayer has developed some
initial examples of plastics production to the point
where an environmental and economic assessment can
be made, but a significant level of long-term research
will be needed for other reactions. There is no lack of
ideas.
11
12
COOMem
The goal of the COOMem subproject is to develop innovative composite carbon capture membranes. Membrane technologies are used in the iC4 cluster for gas
separation, e.g. to capture CO2 emissions from power
plants and CO2/CH4 gas mixtures from biogas plants.
The project team is conducting in-depth research on
the membrane materials, membrane production and
simulated system integration, and they are also carrying out an economic and environmental assessment of
the technology. The composite membranes consist of a
selective layer on a support membrane. Silicon elastomers with intrinsically high gas permeability are used
as the support material for the asymmetric hollow-fiber membranes.
Polyelectrolytes with high CO2 selectivity were chosen
as the base material for the selective separation layer.
Based on the development work done by the project
team, large scale production of asymmetrically micro-porous hollow-fiber membranes is now feasible,
and it is possible to make separation layers with CO2/
N2 selectivity of approximately 60.
AdCOO
The research team on the COOMeth subproject is
trying to derive economic value from CO2 by using
renewable hydrogen for methanation. The technology
is highly dependent on the availability of hydrogen and
CO2 at an affordable cost.
Existing post-combustion capture techniques based on
wet scrubbing with reactive amine reagents are very
expensive and not particularly efficient. A technical/
economic feasibility study is being carried out in the
AdCOO subproject to determine whether solid sorbents in combination with suitable process technology
can improve energy efficiency. Therefore, various solid
sorbents have been produced and characterized. Some
are made using different combinations of support materials impregnated with suitable receptor molecules
while others are non-impregnated sorbents which have
a defined pore structure such as zeolites and meso-porous silicas.
The acquired analytical data is used by the technology
partner Siemens Energy to assess the economic feasibility of alternative process technologies such as fixed
bed and fluidized bed reactors. The project team is also
looking at the suitability of various solid sorbent options under pre-combustion conditions for next-generation power station technologies.
As things stand now, the results indicate that under
fixed-bed based post-combustion capture conditions,
there are no substantial energy efficiency or economic advantages compared to advanced wet scrubbing
techniques. While solid sorbents do have the advantage
of greatly reduced heat capacity, lower heat transfer
means that compared to wet scrubbing, extraction of
absorption heat for the subsequent desorption stage
requires sophisticated and expensive heat exchanger
technology.
Project partners:
13
PhotoCOO
Researchers are investigating various aspects of photochemical CO2 reduction. Calculations based on quantum mechanics provide indications of possible reaction paths, activation energies and equilibrium states.
Experiments can then be set up to test the theoretical
models, initiating an iterative process. Initial results
based on this approach look promising. The team has
synthesized various rhenium and iridium complexes
which can be used to investigate the kinetics of selective CO2 reduction to CO. The researchers have gained
an in-depth insight into the electron transfer mechanism and the deactivation steps. They have developed
systems which are capable of making a large portion of
the sunlight spectrum available for the reduction process. Photochemical water splitting is an additional aspect which is being investigated using GaN/ZnO based
heterogeneous catalysts. Through selection of particle
composition and size along with suitable promoters
(Pt, Pd and Ag), the team is attempting to determine the
reaction kinetics and thermodynamics. Initial results
indicate that this approach is very promising. An Xe/Hg
lamp which simulates sunlight is being used to make
a detailed study of oxygen and hydrogen evolution.
There are strong indications that promoter cluster size
is crucial. With the aid of a DEMS (differential electrochemical mass spectrometer), the researchers are carrying out investigations on photoelectric CO2 reduction
to make various products such as formic acid, formaldehyde and methanol with the aid of decorated silicon
surfaces. Initial results indicate that covalent bonding
of organocatalysts on the silicon surface tends to increase the activity of CO2 reduction.
Contact:
Prof. Bernhard Rieger
Technische Universitt Mnchen
Wacker Lehrstuhl fr Makromolekulare Chemie
Lichtenbergstr. 4
85748 Garching
Tel.: +49 (0)89 289-13570
E-Mail: [email protected]
14
The goal of this consortium project is to develop technology to help manage the fluctuating supply of electricity from wind and solar power by storing energy as
SNG (Substitute Natural Gas). CO2 will act as the carbon
source..
Fig. 1: Process flow for production of SNG from excess electricity and CO2
Germany has an excellent natural gas storage and distribution infrastructure. The countrys pore and cavern
natural gas reservoirs have a working gas volume of
approximately 23 Giga m which is equivalent to about
250 TWhchem (the figure for pumped storage power stations is approx. 0.04 TWhel). Additional storage
facilities with a volume of 7 Gm are currently under
construction or at the planning stage. Leaving aside
the natural gas grid, storage capacity of at least 326
TWhchem will then be available, which is roughly seven
times the total amount of electricity generated from
wind power in 2012.
In the planned process (Figure 1) a PEM pressure electrolyser with highly dynamic responding behaviour
produces hydrogen, which is subsequently transformed
into CH4 utilising CO2:
CO2 + 4 H2 CH4 + 2 H2O (g)
Three-phase (slurry) reactors have advantages compared to the two-phase methanation which has been
the predominant pathway in the past. The reaction of
gaseous educts takes place at a solid catalyst, suspended
in a special heat transfer fluid (e.g. heat transfer oil or
15
Project partners:
Contact:
Dipl.-Ing. Dominic Buchholz
DVGW-Forschungsstelle am Engler-Bunte-Institut
des Karlsruher Instituts fr Technologie (KIT)
Bereich Gastechnologie
Engler-Bunte-Ring 1
76131 Karlsruhe
Tel.: +49 (0)721 608 426 93
Fax: +49 (0)721 964 02 13
E-Mail: [email protected]
16
High throughput synthesis and activity measurements using a rapid screening system integrated
into a synthesis robot
photocatalyst synthesis
investigate the photocatalytic water splitting mechanism in the presence of sacrificial agents. They were
able to identify the best catalysis to promote the formation of molecular hydrogen and molecular oxygen.
Time-resolved laser pulse photolysis studies enabled
the team for the first time to identify intermediary
oxygen radicals during water oxidation and study their
subsequent reaction kinetics in detail. They developed
a synthesis robot with integrated rapid screening system (photo reactor with a gas chromatograph attached)
for high throughput production and rapid testing of
photocatalysts. The team prepared and tested approximately 620 tantalate and niobate based samples using
a variety of synthesis techniques. The most promising
photocatalysis were optimised under for conditions
analogous to those in a production environment. The
researchers analyzed the influence which different
scalable production methods and parameters have on
the physical properties, and hence the hydrogen formation rate, of the photocatalysts. A number of different
co-catalysts were also tested. Successful test results for
hydrogen production using particulate systems and
electrodes were obtained with three different types of
reactors. The solar efficiency and economic viability of
various catalysts were evaluated. A solar concentrator
test bed (SoCRatus=Solar Concentrator with a Rectangular Flat Focus) was set up and a suspension reactor
with two separate reaction chambers along with the
appropriate instrumentation was placed into operation. For parallel testing, the suspension reactor was
mounted next to a photoelectrochemical cell in the
focal plane of the SoCRatus.
Hydrogen produced using renewable resources can
make a major contribution to climate protection in a
wide range of applications such as conversion of CO2
to hydrocarbons, fuel for domestic energy supply or
vehicle fuel cells. Compared to other known renewable-based techniques, solar chemical production of
hydrogen has the advantage of much simpler process
technology, because water is split in a single low-temperature reactor. This can be an advantage in distributed applications. Hydrogen for domestic heating
systems or fuel cells could be supplied under ideal
conditions with simplified infrastructure. Hydrogen
produced on a large scale at industrial solar parks could
17
Project partners:
Contact:
Dr. Sven Albrecht
H.C. Starck GmbH
Im Schleeke 78 - 91
38642 Goslar
Tel.: +49 (0)5321 751 3735
Fax: +49 (0)5321 751 6872
E-Mail: [email protected]
www.hcstarck.com
18
Fig. 1: Using hydrogen produced from renewable resources, CO2 can be converted to useful products in the chemical industry
(photo: Bayer)
19
Contact:
Dr. Stefanie Eiden
Bayer Technology Services GmbH
BTS-TD-UP-CC
Leverkusen, E 41
Tel.: +49 (0)214 30 22761
Fax: +49 (0)214 30 50262
E-Mail: [email protected]
20
Fig. 1: Steam electrolysis degradation at the start of the project (left) and one year later (right)
21
sunfire
Herstellung
von
SUNFIRE
PRODUCTION OF
FUEL
Kraftstoffen
aus
Co2
und
H2o
FROM CO AND H O
2
CH2
CH2
gasoline,
diesel,
kerosene,
Benzin,
diesel,
Kerosin,
Methangas
methane
gas
HGM
CO2 +H2O
Co2 +H2o
carbon
dioxide
Kohlenstoffdioxyd
Wasser
water
Contact:
Christian Olshausen
Sunfire GmbH
Gasanstaltstrae 2
01237 Dresden
Tel.: +49 (0)351 89 67 97 908
E-Mail: [email protected]
22
ENERGY-EFFICIENT PROCESSING
and BASF Personal Care & Nutrition). The researchers were also able to develop a range of membranes
with different cut-off values. Two module generations
were developed. Project partners carried out feasibility
studies on flat sheets and additionally spiral-wound
modules were also produced and made available to the
partners.
ENERGY-EFFICIENT PROCESSING
23
Fig. 2: Contribution of a spiral-wound module to the product carbon footprint broken down by
class.
Project partners:
Evonik Industries AG
Bayer Technology Services GmbH
BASF Personal Care and Nutrition GmbH
RWTH Aachen
Contact:
Dr. Daniela Kruse
Creavis Technologies & Innovation
Evonik Industries AG
Paul-Baumann-Strae 1
45772 Marl
24
ENERGY-EFFICIENT PROCESSING
The following are members of the consortium: software development - ifu Hamburg; scientific research
- the Institute for Industrial Ecology (INEC, Pforzheim
University) and the Chemical and Thermal Process Engineering Institute (ICTV, TU Braunschweig); chemical
industry - H.C. Starck GmbH and Sachtleben Chemie. Wacker Chemie, BASF SE and Worle-Chemie (a
mid-tier company) are also involved in the project as
associate members. Funding for the three-year project
is being provided by the Federal Ministry of Education
and Research (BMBF).
Project status
Last year, the project team achieved some important
conceptual and technical results. They developed a
methodology model for integrated resource efficiency
analysis which describes the interaction between the
different analytical methods used in the application.
While doing so, they defined the specific IT support
requirements and developed the initial prototypes.
Material flow modeling plays a key role as the unifying
overall model (Fig. 2). Complementary methodologies
ENERGY-EFFICIENT PROCESSING
25
P3: emissions
710304.6523437 kJ
1527354.652344 kJ
125700 kJ
P1: water return
8709114 kJ
T5:pump
1975309.339844 kJ
8395136.71875 kJ
1767804.6875 kJ
T1
P4: auxiliaries
Flow sheet
(ChemCAD)
T1: boiler
2289286.621094 kJ
8990754.911402 kJ
Interaction via
Interaction
transition scriptvia
transition script
26
ENERGY-EFFICIENT PROCESSING
Project partners:
Contact:
Nicolas Denz
ifu Hamburg GmbH
Max-Brauer-Allee 50
22765 Hamburg
Germany
Tel.: +49 (0)40 480009-0
E-Mail: [email protected]
ENERGY-EFFICIENT PROCESSING
27
28
ENERGY-EFFICIENT PROCESSING
Fig. 2: Increment factors for condensation of iso-propanol, n-pentane and isooctane in a finned tube made
of carbon steel and comparison to literature models ( LAPt, TU Mnchen)
ENERGY-EFFICIENT PROCESSING
29
have already been submitted to peer-reviewed professional journals for 2014. A special Chemie Ingenieur
Technik magazine supplement entitled Innovative
Equipment and System Design is planned for the
autumn of 2014 for whith the InnovA2 project will
contribute the bulk of the articles.
Project partners:
Contact:
Prof. Dr.-Ing. Stephan Scholl
Technische Universitt Braunschweig
Institut fr Chemische und Thermische
Verfahrenstechnik ICTV
Langer Kamp 7
38106 Braunschweig
Tel.: +49 (0)531 391 2780
Fax: +49 (0)531 391 2792
E-Mail: [email protected]
www.ictv.tu-bs.de
www.innova2.de
30
ENERGY-EFFICIENT PROCESSING
Researchers at universities in Darmstadt and ErlangenNuremberg are working closely with Evonik on 10 work
packages. The results of WP3 should give the researchers
a better understanding of how the different components
of a SILP catalyst influence the behavior of the catalyst
in continuous gas-phase hydroformylation. The results
so far clearly show that interaction between the precursor, ligand and ionic liquid (IL) in the substrates
pore network is highly complex. The complexation
behavior of the precursor and ligand as well as the
type of IL or substrate have a pivotal influence on the
activity, stability and selectivity of the catalysts. When
different ILs were used, a correlation was found to
exist between catalyst activity and the solubility of
1 Schnweiz et al. Ligand-modified rhodium catalysts on porous silica in continuous gas phase hydroformylation of short-chain alkenes catalytic reaction in
liquid supported aldol product, ChemCatChem 2013, 5(10), 2955296.
2 Franke et al. Accurate pre-calculation of limiting activity coefficients by COSMO-RS with molecular-class based parameterization, Fluid Phase Equilibria
2013, 340, 11-14.
3 Y. Hou; R. E. Baltus, Experimental Measurement of the Solubility and Diffusivity of CO2 in Room-Temperature Ionic Liquids Using a Transient Thin-LiquidFilm Method. Industrial & Engineering Chemistry Research 2007, 46, 24, 8166-8175.
ENERGY-EFFICIENT PROCESSING
31
Project partners:
Contact:
Evonik Industries AG
Friedrich-Alexander-Universitt Erlangen-Nrnberg
Technische Universitt Darmstadt
32
ENERGY-EFFICIENT PROCESSING
The measurement techniques have now been developed and thoroughly tested on the pilot reactor at
Evonik Industries (Fig. 2). The researchers are using the
results to identify, validate and enhance suitable calculation models. The experimental data and calculation
models are being archived in a web-accessible database.
Other project work packages will be looking at the potential for CO2 mitigation in an industrial process. The
ENERGY-EFFICIENT PROCESSING
33
Project partners:
Evonik Industries AG
BRUKER OPTIK GMBH
Eurotechnica GmbH
ILA Intelligent Laser Applications GmbH
PreSens Precision Sensing GmbH
Helmholtz-Zentrum Dresden-Rossendorf e.V.
Ruhr-Universitt Bochum
TU Hamburg-Harburg
Contact:
Dr. Marc Becker
Evonik Industries AG
Rellinghauser Str. 1-11
45128 Essen
Tel.:
+49 (0)2365 49-6737
E-Mail: [email protected]
34
ENERGY-EFFICIENT PROCESSING
Project status
The methods used to make the design calculations for
the hydraulic stages have progressed to the point where
an initial compressor stage consisting of an impeller
and diffuser has been evaluated in the simulator. Rotordynamic analysis has been performed for the shaft,
and the results obtained through iterative simulation
have been verified during trials. At speeds up to around
180,000 RPM, vibration resulting from the rotors rigid
and deformable body modes made it necessary to redesign the rotor and stator in the electric motor drive
unit. A drive unit with oil-lubricated rolling bearings
has run at speeds up to 170,000 RPM during trials. The
speed was kept below 180,000 RPM due to the characteristics of the rolling bearings. The compressor
will have gas bearings, so that aspect is of no practical
consequence. The fluid mechanics characteristics of
ENERGY-EFFICIENT PROCESSING
35
For society in general, development of a CO2 compressor which can help heat existing residential homes and
buildings at a relatively affordable cost and provide security of supply to meet the basic human need for heat
is a very significant step forward. Involvement by the
universities in Stuttgart, Kaiserslautern and Mannheim
in the project provides opportunities for students to
complete degree course requirements, which is another
important social contribution made by the project.
Project partners:
Contact:
KSB Aktiengesellschaft
Universitt Stuttgart
Hochschule Mannheim
Technische Universitt Kaiserslautern
36
ENERGY-EFFICIENT PROCESSING
The heat exchanger must meet very demanding requirements (pressure up to 6 bar, temperatures up to
90C, aggressive organic media such as toluene, hexane
and tetrahydrofuran). Researchers have invested two
years of intensive work studying the chemical, mechanical and thermal resistance of polymer materials.
Besides investigating the creep resistance of the film
under the specified operating conditions, they also
looked at how the foil behaves when exposed to vibration stress. Tests showed that film made of polytetrafluoroethylene and polyimide meets the resistance
requirements if it is properly supported. Heat transfer
performance was determined by experiment and numerical analysis. A simple model heat exchanger was
set up in the department to run experiments on different configurations (cross-flow, counter-flow, parallel
flow). Data collected during the experiments was used
to validate numerical models which were then used to
define the final geometry.
Because the film is highly susceptible to pressure deformation, FSI (fluid solid interaction) was used for numerical simulation of heat transfer. With this approach,
it is possible to model the geometric changes which
take place during ongoing operation and understand
the effect which these changes have on flow and heat
transfer.
Nine student papers were completed during the project
including 2 Bachelors theses and 2 Masters theses.
3 other students are currently working on papers.
A final dissertation is expected to be completed at the
beginning of 2015. Information on the economic findings from the project in material science, heat transfer
and fluid mechanics is being shared with the public at
conferences and congresses.
There is constant demand in the chemical industry for
small heat exchangers, many of which are used at test
ENERGY-EFFICIENT PROCESSING
37
centers. Polymer film heat exchangers have the advantage of lower CO2 consumption during equipment
manufacturing (up to 30 t CO2e/yr compared to glass
heat exchangers). Other advantages include lighter
weight and significantly lower material costs due to the
low thickness of the heat transfer surfaces. The new
technology can give manufacturers a competitive edge
and contribute to job security. The lower costs can also
help manufacturers reduce their equipment production
costs.
Project partners:
Contact:
Dmitrij Laaber
TU Kaiserslautern
Gottlieb-Daimler Strae
67663 Kaiserslautern
Tel.: +49 (0)631 205-2124
E-Mail: dmitrij.laaber[at]mv.uni-kl.de
38
ENERGY-EFFICIENT PROCESSING
Project status
The polymer matrix is made of rubbery, silicon-based
polymers which facilitate the transport of long-chain
hydrocarbons. In order to support solubility controlled
transport in the polymer matrix, modified hydrocarbon-selective activated charcoal is being developed on
the project as an active filler.
A number of factors influence the separation performance of the hybrid material. The materials must have
good compatibility to avoid non-selective defects at
the interfacial surface. The particles should also be well
distributed in the polymer matrix to derive maximum
benefit from the fillers properties. Determining the
ENERGY-EFFICIENT PROCESSING
39
Project partners:
Contact:
Dipl.-Ing. Torsten Brinkmann Ph. D.
Helmholtz-Zentrum Geesthacht Zentrum
fr Material- und Kstenforschung GmbH
Institut fr Polymerforschung
Max-Planck-Strae 1
21502 Geesthacht
Tel.: +49 (0)4152 87 2400
E-Mail: [email protected]
40
ENERGY-EFFICIENT PROCESSING
The STRUCTese energy management system developed by Bayer to facilitate continuous, sustained
maximization of energy efficiency forms the basis of
the project. In contrast to conventional energy management systems, STRUCTese not only reports and
tracks (specific) energy consumption over time, it also
compares specific primary energy consumption to various theoretical optima. The losses (actual vs. optimum)
caused by suboptimal equipment, partial load, the
product mix, external factors and suboptimal operation are presented in a clear and transparent manner.
Using this approach, energy efficiency becomes measurable. STRUCTese provides an optimization pathway
and removes the obstacles mentioned above.
Advanced development work is being done on the
project to transform the method into a standardized
energy efficiency management and benchmarking tool
which many companies can use for different process
scenarios. The method was implemented in a number
of real-world processes and enhanced so that it can
model a very broad spectrum of process scenarios, e.g.
parallel production lines, production of multiple products and batch-continuous transitions. The researchers
worked closely with universities to define the theoretical optima. They did this to ensure that the bench-
ENERGY-EFFICIENT PROCESSING
41
Project partners:
Contact:
Dr. Christian Drumm
Bayer Technology Services GmbH
Tel.: +49 (0)214 30 41978
E-Mail: [email protected]
42
ENERGY-EFFICIENT PROCESSING
ENERGY-EFFICIENT PROCESSING
43
Project partners:
Evonik Industries AG
Universitt Erlangen-Nrnberg
Universitt Duisburg-Essen
Contact:
Dr. Jens Busse
Paul-Baumann-Strae 1
45764 Marl
Tel.: +49 (0)2365 49-86509
E-Mail: [email protected]
44
ENERGY-EFFICIENT PROCESSING
Project status
The research team on the IL WIND project developed
halogen-free ionic liquids (ILs) with a target solubility
of 5 wt% in petroleum-based oil and evaluated their
thermal properties. COSMO-RS was used to help identify the required structural elements of the ILs. The
tribologic properties (friction and wear surfaces) of the
ILs in contact with 100Cr6 steel in air, argon and CO2
atmospheres were assessed and compared with standard oils. The corrosion behavior of the ILs was also
evaluated using six different metals and alloys.
The consortium partners took responsibility for different aspects of the overall development effort. The
University of Erlangen-Nrnberg provided basic scien-
The researchers conducted screening trials to demonstrate the tribologic suitability of the structures for subsequent rolling bearing trials. A basic test bed was set
up which uses IR spectroscopy for in situ investigation
of the damage mechanism.
ENERGY-EFFICIENT PROCESSING
45
The intention is to run field verification trials and continue development of the lubricant right up through
market introduction
The project outcome would of course not have been
possible without productive collaboration between
industry and the university. 10 Bachelors theses, 4
Masters theses and four doctoral dissertations were
completed during the project.
Project partners:
Merck KGaA
Schaeffler Technologies GmbH & Co. KG
Friedrich-Alexander-Universitt ErlangenNrnberg
Assoziierter Partner:
Senvion SE
Contact:
Prof. Dr. P. Wasserscheid
Friedrich-Alexander-Universitt Erlangen-Nrnberg
Lehrstuhl fr Chemische Reaktionstechnik
Egerlandstr. 3
91058 Erlangen
Tel.: +49 (0)9131 85-27420
Fax: +49 (0)9131 85-27421
E-Mail: [email protected]
46
ENERGY-EFFICIENT PROCESSING
Project partners:
Hochschule Aalen
Universitt Hamburg
J. Rettenmaier & Shne GmbH + Co KG
Bayer Technology Services GmbH
Contact:
Prof. Dr. Willi Kantlehner
Hochschule Aalen
Beethovenstr. 1
73430 Aalen
Tel.: +49 (0)7361 576-2152 oder (0)7366-6766
Fax: +49 (0)7361 576-2250
E-Mail: [email protected]
ENERGY-EFFICIENT PROCESSING
47
48
ENERGY-EFFICIENT PROCESSING
Institute for Technical Thermodynamics and Refrigeration (KIT) - see Fig. 1. A water ionic liquid material pairing is currently being evaluated on the system
under various operating conditions. The experimental
results are used to evaluate predictions generated by
a simulation program and interpret the differences.
New equipment design features with highly promising
operating characteristics have been built into the lab
system. A patent application is being prepared in partnership with API Schmidt-Bretten for the fluid distribution system of the new absorber.
In parallel, the suitability of a different absorber design
is under evaluation at BASF SE, and the suitability of
the new material pairing is also being assessed under
various operating conditions. The researchers have
identified additional heat sources and the company is
considering using the process at its integrated site in
Ludwigshafen as well as at other sites.
The ionic fluids can be regenerated and reused. Recycling would further reduce costs and enhance the
sustainability of the sorption system lifecycle. Manufacturers of sorption systems would not be the only
ones to benefit from the use of sorption technology to
recover waste heat. The technology could also create
new market opportunities for the recycling industry.
Given the magnitude of the potential opportunities,
demand for the materials would probably be measured
in tonnes.
Four Bachelors theses, two Masters theses and three
degree dissertations were completed during the course
of the project, and the research has generated greater
interest in this approach to energy recovery. A doctoral
dissertation on absorption heat transformation using
the water - ionic fluid material pairing is being written
this year. Information on the research results was
shared with the scientific community on posters and
during talks at various conferences.
The results achieved at KIT so far indicate that megawatt range absorption heat transformers using the
material pairings which are currently under investigation could be economically viable. Measurements and
initial estimates by BASF SE suggest that the economic
advantages are more likely to be significant if operating
conditions are favorable. As energy costs continue
to rise and CO2 emissions regulations become more
stringent, absorption loops and heat flow integration
could become more attractive. Initial estimates indicate
that annual savings by 2030 could be in the region of
500,000 t CO2e.
Project partners:
Contact:
Nina Merkel
Karlsruher Institut fr Technologie (KIT)
Institut fr Technische Thermodynamik und
Kltetechnik (ITTK)
Engler-Bunte-Ring 21
76131 Karlsruhe
Tel.: +49 (0)721 608 42733
E-Mail: [email protected]
ENERGY-EFFICIENT PROCESSING
49
New working fluid pairs based on ionic liquids are being developed for absorption heat pumps. By tailoring
suitable ternary working fluid pairings, it is possible to
enhance overall performance and create advantages
compared to conventional working fluid pairings.
Process engineering assessment and validation are carried out using pilot-scale heat pumps as well as commercially available heat pumps.
In order to develop a thermo-chemical heat storage
system with high energy storage density, the researchers are working to identify and evaluate suitable reac-
Project status
The project came to an end on October 31st, 2013. Two
different working fluid pairings were identified for use
in absorption heat pump systems. These pairings are
suitable for different temperature ranges. The systems
have been used successfully on a demonstration-scale
and in commercially available absorption heat pump
systems. Lifecycle analysis was carried out for production of an ionic liquid based working fluid pairing
which reduces resource and energy consumption compared to conventional working fluid pairings. Possible
storage materials were evaluated for use in chemical
heat storage systems, and lab-scale testing was carried
out on a material which the
researchers identified. They also
identified and tested various
reactor designs for a chemical
heat storage system. Important
knowledge was gained during
the project, which provides a
foundation for further development of full-scale chemical
heat storage systems. A carbon
footprint estimate derived from
the research results provides a basis for gauging the
possible reduction in CO2 emissions and resource
consumption.
50
ENERGY-EFFICIENT PROCESSING
and generate long-term growth in the country. Development of thermochemical heat storage systems is still
at an early stage and it is not yet possible to operate
an absorption heat pump and heat storage system in
combination at full scale. The work done during the
project did however demonstrate that this technology
could create opportunities to reduce CO2 emissions.
Close collaboration between university research organizations and industrial partners created opportunities
to align innovative research with application-related
needs. Young scientists involved in the project completed 4 doctoral dissertations and a number of Bachelors
and Masters theses.
Project partners:
Evonik Industries AG
Friedrich-Alexander-Universitt ErlangenNrnberg
Deutsches Zentrum fr Luft- und Raumfahrt e.V.
(DLR)
GasKlima GmbH
Contact:
Dr. Jens Busse
Senior Project Manager Sustainable Businesses - Upstream SolutionsCREAVIS Science to Business
Tel.: +49 2365 49-86509
Fax: +49 2365 49-8086509
E-Mail: [email protected]
CO2 UTILIZATION
51
Project partners:
Assoziierter Partner:
RWE Power AG
Contact:
Dr. Martina Peters
Bayer Technology Services GmbH
Tel.:
+49 (0)214 30 20063
E-Mail: [email protected]
Dr. Christoph Grtler
Bayer Material Science AG
Tel.:
+49 (0)214 30 21771
E-Mail: [email protected]
52
CO2 UTILIZATION
Project status
Since January 2011, researchers at the Catalysis Research Laboratory (CaRLa) which is supported by BASF,
hte AG (part of BASF), TUM in Munich and the University of Stuttgart have been working together on the
ACER project (Acrylates ex Renewables) to find ways of
using CO2 on an industrial scale for the production of
sodium acrylate. The process must be viable from both
CO2 UTILIZATION
53
an established process for making ethylene from renewable bioethanol already exists, complete changeover of acrylate synthesis to a renewable feedstock base
would be feasible. The bioethanol feedstock can contain two CO2 equivalents, so a maximum 7.3 million
tonnes of CO2 could be utilized along this value-add
pathway if total global demand for acrylic acid were
satisfied using this technology. In addition, migrating
synthesis from propylene to ethylene could substantially reduce material, energy and fossil-based feedstock consumption and drive down investment costs.
Information on the project is regularly shared with international opinion-making bodies from government
and industry.
Project partners:
Contact:
BASF SE
Universitt Stuttgart
Technische Universitt Mnchen
hte GmbH the high throughput experimentation
company
54
CO2 UTILIZATION
H2
The vision of the Valery project is to develop new feedstock sources for the chemical industry. The researchers are looking in particular at CO2 and alkanes as
alternative carbon sources for industrial-scale production of high value-add products. The specific objective
is to find an alternative process to replace conversion
of olefins and carbon monoxide (CO) into aldehydes by
hydroformylation. Carbon dioxide (CO2) will be substituted for toxic carbon monoxide, and energy-efficient
dehydrogenation of alkanes will provide the source of
olefins. The researchers have chosen synthesis of valeraldehyde from n-butane as an example.
CO2/H2
new ligand class has increased throughput and improved selectivity. In the case of energy-efficient dehydrogenation, selectivity performance was greatly improved. In addition, a suitable combination of two ionic
fluids and a substrate material was used to stabilize the
CO2 UTILIZATION
55
Project partners:
Evonik Industries AG
Universitt Bayreuth
Leibniz-Institut fr Katalyse e.V. an der Universitt
Rostock
Contact:
Dr. Daniela Kruse
Evonik Degussa GmbH
Creavis Technologies & Innovation
Tel.:
+49 (0)2365 49-9077
E-Mail: [email protected]
56
CO2 UTILIZATION
Fig. 1: Left: schematic diagram of the complete metal-sealed gas phase photo reactor with CF flanges (1), quartz window (2), VCR connections
(3), cooling jacket (4), sample compartment (5) and cooling circuit connections (6); right: photo of the actual reactor with valves and 200 W HgXe
lamp.
CO2 UTILIZATION
Formaldehyde was identified as one of the intermediates. Formation of CO could not be demonstrated using
the existing gas analysis technique. A methanizer is being added to the GC application. Deposition of gold on
57
Fig. 2: a) Time sequence for methane formation on TiOx/SBA-15 and Au/TiOx/SBA-15 in two successive CO2 reduction experiments, each with
7 hours exposure time, uncorrected values. The samples were not purified between successive experiments. No GC product gas analysis after
7 hours was performed for Au/TiOx/SBA-15 in the first experiment. b) Hydrocarbon concentrations in the product gas after 5 hr exposure time
in two successive CO2 reduction experiments. The hydrocarbon yields were corrected to make provision for possible contaminants which could
remain in the catalyst even after purification.
Contact:
Dr. Jennifer Strunk
Lehrstuhl fr Technische Chemie
Ruhr-Universitt Bochum
44801 Bochum
Tel.:
+49 (0)234 32-23566
E-Mail: [email protected]
www.techem.rub.de
58
CO2 UTILIZATION
Project status
The goal is to develop a fermentation process for biotechnology production of acetone using acetogenic
microorganisms along with carbon dioxide (CO2) as
the sole carbon building block. To the extent possible,
the CO2 should be supplied from industrial waste gas
streams and used to produce acetone which is an important base product in the chemical industry. Industrial waste gas streams which contain carbon monoxide
(CO) and hydrogen (H2) as well as CO2 are particularly
well suited for cost-effective, sustainable production of
acetone in a fermentation process. Microbiological production of acetone from CO2-laden waste gas streams
could be an economically viable and environmentally
friendly alternative to the petrochemical production
pathway.
The next step was to insert the genes needed for acetone production into the selected strains, creating new
recombinant strains capable of producing acetone
from CO2. C13-marked CO2 was used to ensure that
the acetone is actually produced from CO2 rather than
from other media constituents.
The next step in development of a production strain
was strain optimization to enhance acetone productivity. This work is currently still in progress and will
continue right through to the end of the project.
Work proceeded in parallel on development and optimization of the fermentation process. The researchers
CO2 UTILIZATION
59
Project partners:
Evonik Industries AG
Universitt Rostock
Universitt Ulm
Contact:
Dr. Jrg-Joachim Nitz
Paul-Baumann-Str. 1
D-45764 Marl
Tel.:
+49 (0)2365 49 4882
E-Mail: [email protected]
60
CO2 UTILIZATION
O
O
oder
R
R
TP1
CO2H
O
O
O
R
R
TP4
TP2
CO2
O
R
TP3
O
R
O
CO2H
Fig. 1. Utilization of CO2 through direct chemical fixation. See posters TP1: Hydroxy-Phosphoniumsalze Aktive Organokatalysatoren zur
Synthese zyklischer Carbonate, H. Bttner, T. Werner*, 08 April 2014, Knigswinter; TP2: Entwicklung neuer Katalysatorsysteme zur Synthese
von Polycarbonaten, A. Pommeres, W. Desens, T. Werner*, 08 April 2014, Knigswinter; TP3: Carboxylierung CH- acider Verbindungen mittels zwitterionischen Imidazoliumcarboxylaten, W. Desens, T. Werner*, 08 April 2014, Knigswinter.
The results so far from sub-project 1 look very promising. The catalyst used for synthesis of cyclic carbonates
has two different functionalities in the molecule. The
bi-functional organocatalysts are particularly active
and in contrast to their mono-functional equivalents
they are able to promote synthesis of cyclic carbonate
under very mild reaction conditions. Two classes of
bi-functional organocatalysts have been identified.
Lifecycle analysis using the most active catalyst was
carried out to assess the possible environmental impact
of glycerol carbonate methacrylate (GCMA) synthesis.
This product is of interest to industry because it is an
excellent polymer building block.[1]
[1] a) D.-W. Park, J.-Y. Moon, H.-J. Jang, K.-H. Kim, React. Kinet. Catal. Lett. 2001, 72, 8392; b) N. Kihara, T. Endo, Makromol. Chem. 1992, 193, 14811492.
[2] a) K. M. Doll, S. Z. Erhan, J. Agri. Food Chem. 2005, 53, 96089614; b) G. Rokicki, Prog. Polym. Sci. 2000, 25, 259342; c) J. Langanke, L. Greiner, W. Leitner,
Green Chem. 2013, 15, 11731182; d) B. Schffner (Evonik Industries AG) Presentation at 2nd International Scientific Forum on CO2 Chemistry and Biochemistry, Lyon, September 2728, 2012.
CO2 UTILIZATION
61
nearly the same in ten successive reactions. The heterogeneous catalysts are particularly well suited for transfer from batch reactors to a micro reactor.
Project partners:
Contact:
Leibniz-Institut fr Katalyse e. V.
an der Universitt Rostock
Bayer Technology Services GmbH
Creavis Technologies & Innovation
62
CO2 UTILIZATION
online Produktanalytik
(Selektivitt der Reaktion)
the investigations, the team is using additional complementary techniques, for example combining electrochemistry with online element analysis, to generate
more detailed data. Based on this new approach, the
researchers are trying to gain an in-depth understanding of electrochemical CO2 reduction and also oxygen
evolution which is the other half-reaction. They intend
to use the results to develop new active, stable, selective
catalysts.
Project Status
During the first two years of the project, the team
developed a new high-throughput catalyst screening
and online analysis setup (Fig. 1). The core element is
an electrochemical cell (Scanning Flow Cell) with flow
system and fully automatic positioning. The SFC can be
used to scan the surface of a sample and carry out local
2mm
elektrochemische Untersuchung
(Katalysatoraktivitt)
online-Elementanalytik
(Katalysatorstabilitt)
Fig. 1: Schematic representation of the new experimental setup using an electrochemical flow cell (top right) for high-throughput screening
(bottom
right)
with online electrolyte analysis (left).
Mittwoch,
5. coupled
Mrz 2014
CO2 UTILIZATION
63
Fig. 2: Top: Product analysis of hydrogen, methane, ethylene and methanol evolution during cyclic voltammograms at a copper electrode.
Bottom: Example of element analysis showing the dissolution behavior of a copper electrode
64
Future Potential
Given the initial starting point, this project is by necessity focused on basic research. As a result, it is not yet
possible to estimate the potential economic, environmental and societal effects of CO2 utilization based
on this technology. The technical developments and
results to date show the enormous benefits of this
CO2 UTILIZATION
Contact:
Dr. Karl J.J. Mayrhofer
Abteilung fr Grenzflchenchemie und
Oberflchentechnik,
Max-Planck-Institut fr Eisenforschung GmbH
Max-Planck-Strae 1
40237 Dsseldorf
Tel.:
+49 (0)211 6792-160
Fax:
+49 (0)211 6792-218
E-Mail: [email protected]
CO2 UTILIZATION
65
The technology protects and enhances the competitiveness of participating companies in the hydrogen
and syngas market. Plant construction, catalyst pro
duction and sales, engineering and scientific service
activities provide job security. The technique creates
the need for new types of systems and instrumentation.
The list includes reactors, temperature measurement,
infeed and discharge systems and carbon formulation
equipment, much of which will be developed by
mid-tier companies. Marketing on a broad scale can
be expected to create new market opportunities. From
the scientific perspective, utilization involves coke, iron
and steel, chemical engineering and process engineering and enhances interaction between these disciplines.
66
CO2 UTILIZATION
project work. In parallel, preliminary trials on hightemperature pyrolysis and heating systems are being
conducted to gain experience and provide a reliable set
of data for the pilot systems which are currently at the
planning stage or under construction. Initial pyrolysis
trials to produce samples in significant quantities are
planned for 2014. Development trials for CO2 activation catalysts are proceeding according to plan.
Project partners:
Contact:
Dr.-Ing. Andreas Bode
BASF New Business GmbH
4. Gartenweg Z025
67063 Ludwigshafen
CO2 UTILIZATION
67
Single-stage synthesis of DME from syngas is a markedly exothermic reaction. The research team is looking
at running the reaction in a slurry bubble column reactor which creates the option of isothermal operation.
A pilot system to explore that possibility as well was
started up in Q4/2013. Initial results indicate that this
process variant is feasible, but a final evaluation has not
yet been completed.
Basic mechanistic research is underway to determine
the best way of fabricating the multi-function catalyst
system. The options include a physical mixture of multiple catalysts and catalysts in which the various functions are atomically dispersed right next to each other.
Project status
Two catalyst formulations were identified during
high-throughput screening, and catalyst molds have
been fabricated. Since Q4/2013, the researchers have
been running long-term tests on a new tube reactor
test bed. Several hundred hours of testing have confirmed the screening results. In parallel with catalyst
screening, complete material and heat integrated
process simulations were run for the new process and
for current 2-stage state-of-the-art DME synthesis. The
catalyst design reflects the simulation results, particularly as they relate to the optimal temperature operating
window.
68
CO2 UTILIZATION
The CO2 footprint of the process could be further reduced by obtaining the energy needed for the process
from renewable sources. The process can be coupled to
biomass-based syngas production. Production of a CO/
H2 mixture through gasification is conceivable as well
as direct upgrading of biogas (CO2/CH4) in place of
biomass gasification, utilizing both C sources. Utilization
The project has provided a framework for three doctoral dissertations on process simulation, kinetics and
catalyst development at partner academic institutions.
One Masters Thesis has already been completed. A
number of students have supported or added to the
project with their scientific contributions.
Contact:
Dr. Ekkehard Schwab
Chemicals Research and Engineering
BASF SE
D-67056 Ludwigshafen/Rhein
E-Mail: [email protected]
Technische
Universitt
Mnchen
CO2 UTILIZATION
69
70
Contact:
Dr. Alexis Bazzanella
DECHEMA e.V.
Theodor-Heuss-Allee 25
60486 Frankfurt am Main
Tel.: +49 (0)69 7564-343
E-Mail: [email protected]
Dennis Krmer
DECHEMA e.V.
Tel.: +49 (0)69 7564-618
E-Mail: [email protected]
71
72
Place to contact:
Persons to contact:
www.nks-umwelt.de
73
Contact:
Freek Kapteijn
University of Technology Delft
Catalysis Engineering
Deutschland
Tel.:
+31 15 278 6725
E-Mail: [email protected]
74
EUROPEAN PROJECTS
EUROPEAN PROJECTS
75
Partner:
Projektkoordinator:
76
poster
77
Conclusion
Gleichrichter,
Hilfs-/ Sicherheitssysteme
Steuerungssystem & Automatisierung
ZnS, CdS buffers (CBD) and sputtered (Zn,Mg)O, i-ZnO, and ZnO:Al layers
I-V analysis under AM 1.5G and EQE without background illumination
Electron beam induced current measurements in junction configuration (J-EBIC)
Capacitance analysis (Cf and CV) at room temperature after 30 minutes of light soaking
The gain in jSC (350 - 550 nm) is accompanied by a reduced VOC for our ZnS cells.
J-EBIC Geometry
&
Komponentenauslegung
Study the carrier collection properties,
ZnS, CdS buffers (CBD) and sputtered (Zn,Mg)O, i-ZnO, and ZnO:Al layers
I-V analysis under AM 1.5G and EQE without background illumination
(350
- 550 nm) is accom The gain in jSCmit
Solar
Untersttzung
Simulationsdaten
CellBlockkonstruktion
Parametersund Komponentenauslegung
panied by a reduced VOC for our ZnS cells.
Validierung entwickelter Einzelmodelle mit Versuchsdaten
J-EBIC Geometry
Abbildung 1: Auslegung Systemumgebung mit IPSEpro
& Kurzblock-Realisierung
Study
the carrier collection properties,
space charge width and charge density
Zellrahmenkonzept
aus Zweistoffverbund
of the
ZnS and CdS devices
Alkalische
Elektrolyse
ZnS, AEL:
CdS buffers
(CBD)
and sputtered (Zn,Mg)O, i-ZnO, and ZnO:Al layers
I-V analysis under AM 1.5G and EQE without background illumination
Electron beam induced current measurements in junction configuration (J-EBIC)
Capacitance analysis (Cf and CV) at room temperature after 30 minutes of light soaking
Conclusion
Keine zustzlichen Einlegeteile
(integrierte Dichtungen, Membran und Elektrodenpackages)
Solar
Entwicklung
Elektrodenpackages The gain in jSC (350 - 550 nm) is accomCellinnovativer
Parameters
panied by a reduced VOC for our ZnS cells.
Aufbau und Qualifizierung des AEL-Druckelektrolyse-Kurzblocks
mit 300 kWel in Systemumgebung
Abbildung 2: Aufbau Modell
& the
Systemkomponenten
Study
carrier collection properties,
space
charge widthdes
andPrfstandes
charge density
Leistungsdaten
of the ZnS and CdS devices
Druck-Bereich: 6 25 bara
Conclusion
J-EBIC Geometry
Abbildung 3: Strmungsfhrung Stack (negativ)
ZnS, CdS buffers (CBD) and sputtered (Zn,Mg)O, i-ZnO, and ZnO:Al layers
I-V analysis under AM 1.5G and EQE without background illumination
Electron beam induced current measurements in junction configuration (J-EBIC)
Capacitance analysis (Cf and CV) at room temperature after 30 minutes of light soaking
Ausblick
J-EBIC Geometry
Abbildung 4: AEL-Prfsttand
bis 02 / 2015
bis 04 / 2015
DANKSAGUNG: Dieses Projekt wird finanziert mit Mitteln des Bundesministeriums fr Umwelt, Naturschutz, Bau und Reaktorsicherheit (BMUB) unter
dem
Frderkennzeichen 0325524A.
ZSW June 14
78
poster
Power-to-Gas - P2G
Renewable Energy Storage
Power-to-Gas Concept
Together with the Fraunhofer Institute for Wind Energy and Energy System
Technology (IWES) and the company ETOGAS, the Centre for Solar Energy
and Hydrogen Research (ZSW) has developed a new method for electricity
storage and to guarantee grid stability in electricity grids with a high
percentage of renewable power generation.
Electricity
grid
Gas distribution
system
Wind
CCPP /
B-CHP
Solar
POWER GENERATION
Biomass
Gas
underground
storage
ELECTRICITY STORAGE
Electrolysis /
H2 buffer
Biogas plant
with SNG
production
CO2
CO2 buffer
H2
H2
CH4
Methanation
CO2
Heat
BEV
H2
Electricity
Mobility
Plug-In HEV
SNG
FCEV
Plug-In HEV
CNG-V
CCPP: Combined
Cycle Power Plant;
B-CHP: Block-type
Combined Heat and
Power Station; BEV:
Battery Electric
Vehicle; FCEV: Fuel
Cell Electric Vehicle;
CNG-V: Compressed
Natural Gas Vehicle;
Plug-In HEV: Plug-In
Hybrid Electric
Vehicle
[TWh/a]
Natural
gas
Liquid
fuels
595
909
711
80
Average Power
[GW]
70
1002)
Storage capacity
[TWh]
0,043)
2174)
2505)
0,6
2000
3000
[h]
Commercialisation Plan
PILOT PLANT
Alpha Plant
25 kWel
2013
2012
Nov. 2009
DEMONSTRATION PLANT
Alpha-Plus
Plant
250 kWel
Beta Plant
6 MWel
2015
COMMERCIAL PRODUCT
Gamma Plant
poster
79
Das Entwicklungsprogramm
Kooperation
BASF - Linde - RWE Power
> BASF
Abtrenntechnologie OASE blue,
Waschmittelperformance
(Wirkungsgrad, Waschmittelstabilitt, Kosten)
Kondensat
Desorber
Feinwsche
Absorber
Rauchgas
Rauchgas
Kondensat
2010
2011
2012
2013
Phase II
2014
2015
2016
Phase III
Rauchgasteilstrom: 1.550
NaOHaq
Nm3/h
Waschmittel
Kondensat
Anlagenverfgbarkeit > 97 %
Optimierung, Langzeittest
Gesamtoptimum Emissionsminderung
Zwischenversuch (+ O2)
Wasserwsche
Trockenes Bett
Saure Wsche
Wasser,
Sure
Manahme
vor Absorber
Wasser
Ergebnisse
Regeneration
Energy [MJ/t
CO2]CO2]
Spezifischer
Energiebedarf
[MJ/t
Kondensator
Wasser
Phase I
CO2
WasserWsche
Zusatzwsche
Kraftwerk
> Linde
Engineering Abtrennungsanlage,
Komponenten
(Wirkungsgrad, Scale-Up, Kosten)
2009
Wasser
Engineering
Chemie
Optimierungsaufgaben
Waschmittelversuche
CO2-armes
Rauchgas Wasser
Additiv
Wasser
Absorber
Absorber
Absorber
Absorber
4000
3800
Rauchgas
Rauchgas
Rauchgas
Rauchgas
3600
3400
Optimum MEA
3200
3000
2800
2600
2400
Optimum
OptimumGUSTAV200
OASE blue
MEA
GUSTAV200
OASE blue
Parametervariationen:
> Waschwassertemperatur (40, 60C)
> Zwischenkhlertemperatur
> pH-Wert Saure Wsche
Circulation rate
Waschmittel-Umlaufrate
lange Kolonne
trockenes Bett
Absorber
Absorber
Aminkonzentration
> Waschmittel OASE blue ber einen Zeitraum von mehr als
26.000 Betriebsstunden getestet
Rauchgas
Rauchgas
1
11
13
15
17
19
21
23
25
27
Zeit [Tage]
Frderkennzeichen: 0327793A-I
CO2-Wsche
CO2
CO2-Verflssigungs-,
Aufbereitungs- und
Abfllstation
CO2
CO2
Direktanwendung
CO2
Chemie
CO2
chem. Energiespeicher
Verflssigung/Kompression
Projekt CO2RRECT
80
poster
CO2 im AUFWIND
Algen
Algen bilden eine noch weitgehend ungenutzte Quelle fr Treib- und Baustoffe oder Plattformchemikalien meist werden sie fr
Nahrungszustze, Pharmazie und Kosmetik eingesetzt. Sie haben weit hheres Potential zur Biomasseproduktion als
Landpflanzen, knnen auch hohe CO2-Konzentrationen sehr gut nutzen und ihr Anbau ist nicht auf Agrarflchen beschrnkt.
OptimAL: Erhhung der Lipidproduktion von einzelligen Grnalgen.
Methodischer Schwerpunkt ist die Stammentwicklung als Grundlage
fr neue Anwendungen, so werden Algen auf mgliche
Einsatzgebiete
gezchtet,
zum
Beispiel
bezglich
Ihres
Energiegehaltes, der Lichtausnutzung, der CO2-Fixierung oder
Temperaturtoleranz.
AUFWIND: Analysiert werden Algenproduktion, DownstreamProcessing, die Kraftstoffproduktion und Konversion sowie weitere
verwertbare Nebenprodukte (Kohlenhydrate, Proteine). Fokus liegt auf
der konomische und kologische Effizienz und ein Upscaling zum
wirtschaftlichen Groanlagenkonzept. Die Forschungsergebnisse
werden in eine LCA eingebettet.
Projekt: OptimALl
Projekt: AUFWIND
12 Partner aus
Industrie und
Forschung
Nhrstoffe, CO2
Algen-Suspension in
Schluchen
im Gewchshaus
Kontakt
Dr. Dominik Behrendt
IBG-2: Pflanzenwissenschaften
Institut fr Bio- und Geowissenschaften
Forschungszentrum Jlich GmbH
52425 Jlich
Algen-Suspension tropft
durch Netze in einer CO2angereicherten Atmosphre
Finanzierung
Algen-Suspension in
freihngenden
Schluchen
Partner
poster
81
B i o t e c h n o l o g i e 2 0 2 0 p l u s B a s i s t e c h n o l o g i e n f r e i n e n c h s t e G e n e r a t i o n b i o t e c h n o l o g i s c h e r Ve r f a h r e n
Background
The project is an interdisciplinary approach of wet lab experiments and computational modeling. The goal is to evaluate the capacity of bacterial enzymes for
utilizing CO2 as a feedstock for organic chemicals or fuels. Work packages of the participating partners include:
Biberach University of Applied Science
13C metabolomics for identifying CO2-fixing pathways
Isolation and kinetic characterization of CO2-fixing enzymes
in vitro (electrochemical) operation of enzyme cascades
The starting point: Systems Biology development of the purple bacterium Rhodospirillum rubrum for biotechnological applications
1, 2, 5 % CO2
Production of:
Porphyrins
Photodynamic Tumor Therapy
0 % CO2
Poly-b-hydroxyalkanoates
Biopolymers
Biohydrogen
Energy carrier
Carotenoids
Food supplement
Vitamins,
Coenzymes
Food industry
B12, Q10
10 % CO2
0 % CO2
Membrane proteins
Vaccines
2 % CO2
1 % CO2
Fructose
Succinate
Fructose/Succinate
Figure 2. Metabolic network of central carbon metabolism in purple nonsulfur bacteria, implemented in CellNetAnalyzer (1) .
pyruvate +Fdox
(K'eq = 0.018), DE0 -520 mV
Tab 1. Specific enzyme activity of pyruvate:ferredoxinoxidoreductase of anaerobically grown C. tepidum and R. rubrum
Strain
C. tepidum
C. tepidum + 50 mM acetate
R. rubrum
U/mg
0.101 0.015
0.039 0.007
0.0014 0.00033
f ocus.de
Figure 5: CO2 fixation by the reductive TCA cycle. E1: PFOR; E2:
pyruvate formate-lyase; E3: a-ketoglutarate synthase; E4: isocitrate
dehydrogenase; E5: pyruvate carboxylase
1) Hdicke, O., H. Grammel, and S. Klamt. 2011. Metabolic network modeling of redox balancing and biohydrogen production in purple nonsulfur bacteria. BMC Syst. Biol. 5:150.
2) Rudolf, C., and H. Grammel. 2012. Fructose metabolism of the purple non-sulfur bacterium Rhodospirillum rubrum: Effect of carbon dioxide on growth, and production of bacteriochlorophyll and organic acids. Enzyme Microb. Technol. 50:238-246.
3) Evans, M.C.W., Buchanan, B.B. and D. I. Arnon. 1966. A new ferredoxin-dependent carbon reduction cycle in a photosynthetic bacterium. Proc. Natl. Acad. Sci. USA 55, 928-934.
82
poster
CH CH O C O
CH CH O
R2
R1
R2
n R1
CO2
(pure polycarbonate: m = 0)
[ Catalyst ]
P,T
R2
O
C
O
Cyclisation
ryls
ente Ac
2 quval
R1
O
NH2
NH
NH2
vat
urederi
NH
NH
NH2
NH2
R1
NH
NH
NH2
NH2
NH2
NH2
NH2
NH2
NH2
(H2C)2
NH2
NH2
(H2C)4
NH2
(H2C)6
NH2
NH2
H2N
NH2
NH2
NH2
NH2
O
R2
NH
Fe(OAc)2
DMF
Pyridin
Fe
I2
Fe
Pyridin
66%
95%
+ CO2
Entrya) epoxide
Cat.
Catalyst (a)
co-Cat.
Cat. /
mol%
p/bar
T/C
Yield
1.0
50
80
nBu4NBr
0.2
35
80
37%
Fe(II)
O
Fe
N
O
O
O
N
1.0
50
80
91%
0.2
50
80
99%
0.1
35
80
69%
0.2
80
36%
O
Fe
O
O
N
Fe(II)
0.2
50
80
TBAB
0.2
50
80
75%
TBAB
1.0
50
80
94%
O
N
O
N
Fe
N
/bar
Yield b)
50
96
50
100
35
98
50
99
35
95
50
100
50
50
50
50
Ph
Ph
Ph
Ph
t-Bu
O
O
Cl
7
9
O
O
Bu
10
Ph
O
O
Cl
6
8
O
O
0.2
0.2
0.1
0.2
0.2
1.0
T
(C)
p
(bar)
80
100
80
80
80
80
50
50
50
50
50
2
t
(h)
PCHC
Carbonate
Linkageb
20
20
20
10
20
48
100%
99%
100%
100%
100%
99%
Yieldc
TON
Mnd
(g mol-1)
PDId
Tge
(C)
77%
76%
66%
46%
32%
29%
384
379
660
230
158
29
11 100
7 000
15 000
7 600
4 200
3 100
1.53
1.65
1.28
1.233
1.49
1.37
103.9
93.0
106.3
101.1
93.0
93.8
X ray structure:
(Lester(Cl)2N2O2)Zn(DMSO)
X ray structure:
[(Lnitrile(Me)2N2O2)Zn(DMSO]
monomeric unit
TBAB
Fe(III)
O
Ph
O
N
N
product
O
(b)
2 + DMAP
2 + TBAB
2 + TBAB
2 + TBAB
2 + TBABf
2 + TBAB
High activity in the formation of Cyclic Carbonates via the Cat/Co-Cat in one concept.
O
Catalysta
Entry
10
11
12
13
14
15
c(cat.)
(mol%)
O
N
C
O
I
O
O
O
Cat.
NH
+ CO2
NH2
NH2
NH2
NH2
NH2
O
O
NH2
NH2
R2
R1
NH2
R1
(1,3-dioxolan-2-one)
R2
R1
The ligands are formed by condensation of a diamine and ethyl 2-cyano-3-ethoxy-acrylate or diethylethoxymethylenemalonate in yields of up to 99%.
Synthesis adapted from E.G.
Jger et al., Z. anorg. Allg.
Chem. 1985, 525, 67.
Cyclic Carbonate
R1
aliphatic poly(ether-carbonate)
O
R1
Bu
O
O
O
t-Bu
O
O
O
O
O
+ CO2
Cat.
O
O
Y1
Y2
N
+
OAc
5 Y1, Y2 = H , 78%
6 Y1, Y2 = Cl , 78%
7 Y1 = H, Y2 = NO2 , 63%
8 Y1, Y2 = Me , 51%
Pyridine
NH2
NH2
Y1
O
NH
N
Y2
Cl
O
Triphenylphosphite
Y2
OH
2
Co
Y1
Y1
More details in Polyhedron, 2012, 48(1), 92-98 and Dalton Transactions, 2014, 43(8), 32853296
OAc
O
NH
N
+ MCl2-3
1 Y1, Y2 = H , 50%
2 Y1, Y2 = Cl , 62%
3 Y1 = H, Y2 = NO2 , 36%
4 Y1, Y2 = Me , 78%
Catalyst a
Br
N
N
20 Y1, Y2 = H , 56%
21 Y1, Y2 = Cl , 65%
22 Y1 = H, Y2 = NO2 , 62%
23 Y1, Y2 = Me , 74%
Cl
R
Product
Mn (g/mol)d Mw/Mn
Co/L(H)/OAc
9600
1.15
Co/L(Cl)/OAc
50
80
70
100-
7600
1.28
104
Co/L(NO2)/OAc
50
80
35
100
10100
1.27
106
Co/L(Me)/OAc
50
80
83
100
8600
1.27
105
+ CO2
p (bar)
35
T (C)
80
Yield
62
Co/L(Cl)/OAc
35
84
50
Co/L(NO2)/OAc
35
80
32
Co/L(Me)/OAc
35
80
70
P
(bar)
Cl
Catalyst
O
N
Conversionb
50
76
35
78
50
60
50
60
50
96
50
93
50
99
50
Tg (C)e
104
O
O
PC
O
C
Cl
Cl
O
O
Catalyst
Co/L(H)/OAc
N
N
Co
N
Yield CO3 b
%c
64
100-
Cat.
Co
Cat.
Br
PCHC
T
(C)
80
Y2
Y1
Cl
Cl
O
O
Epoxide a
p
(bar)
50
DMF
+ CO2
Cl
C
O
Cat.
DMF
Y2
+ CoBr2
+ CO2
O
O
O
O
O
O
O
O
Acknowledgement: This work was supported by the BMBF-Project Dream Reactions (Frderkennzeichen 01RC0901A) and the Helmholtz Research School Energy-Related Catalysis.
poster
83
84
poster
iC4 - PhotoCOO
Die vierte, weiter in die Zukunft blickende Sule des iC4-Projektclusters - PhotoCOO - untersucht die direkte,
photochemische Umsetzung von Kohlendioxid und Wasser zu Wertprodukten analog zur natrlichen Photosynthese.
Unter besten kologischen und auch vorteilhaften konomischen Bedingungen wrde vorab emittiertes CO2 - via
Adsorption oder membrangesttzter Trennverfahren (siehe die komplementren iC4-Teilprojekte AdCOO und
COOMem zum Stand der Optimierung der CO2-Abtrennung) - wieder dem Stoffkreislauf zugefhrt werden. Dies schtzt
die Umwelt und dient zudem zwei Wirtschaftssektoren Energie und Chemie - in perfekter Symbiose.
AK Rieger
Kontrollierte Si-Funktionalisierung:
Erhhung der elektrochemischen Reaktivitt
2000
*M*cm
1600
AG Krischer
Zweikerniger
Katalysator
1200
--- Einkerniger
Katalysator
800
400
0
450
470
490
510
530
550
/nm
Triplett-MLCT- Absorption :
(3MLCT)=474nm +506nm,
d(Ir)-*(tpy)
Elektrochemische Eigenschaften
C1
C2
-0.6
-0.8
-0.4
-0.6
C2
-2.0
C3
-2.5
-2.0
-1.5
A1
A2
0.0
-0.2
-1.0
-0.5
C1
-1.5
-1.0
0.0
0.5
+/0
45
0.6
-0.4
-0.6
C2
C1
-0.8
-1.0
-1.4
0.2
A2
0.0
-0.6
-2.0
-1.5
-1.0
C1
C2
-2.0
-1.5
-1.0
C3
-2.5
1.0
A1
0.4
-0.2
-0.4
-1.2
-0.5
relative irradiance/%
0.2
-0.4
Current [ mA/cm ]
0.4
-0.2
-0.5
0.0
-0.5
0.5
40
35
30
25
20
15
10
5
0
1.0
On-line Produktanalyse:
Optimierte DEMS-Zelle (Differentielle
elektrochemische Massensprektrometrie)
Bessere Verzahnung von Produktanalyse
und (photo-)elektrochemischem Experiment
50
A1
0.0
450
500
Decrease of
enthalpic barrier
from
9 to 25 kcalmol-1
with the aid of
water
2 H2O
650
700
750
800
Porse,
gasdurchlssige
PTFE-Membran
20
18
16
14
12
10
8
6
4
2
0
HPLC und
Referenzelektrode
y = 524,25x - 0,0825
0,01
0,02
c(TEOA)*l/mol
0,03
HCOO
formation
0 kcalmol-1 :
sum of reduced
(neutral)
reactants
F0/F1 - 1
600
/nm
AG Rsch
0 H2O
550
Emission: em =562nm
0,04
Beleuchtung
0.2
-0.2
i [mA/cm]
A1
A2
0.0
i [mA/cm]
Current [ mA/cm ]
0.2
DEMS
Probe
ElektrolytFluss
Potential hydrogenation
pathways from various
CO2/H configurations
21
PhotoCOO
14
12
2HCOO species
most stable isomer
2
0
H2O
-9
-9
AG Reuter
Ab initio Methodik fr
ladungsgetriebene Redoxreaktionen
O2
GaN:ZnO
Treibstoffe
Chemikalien
Wasserspaltung
Charakterisierung
Biomasse
H2O
H2 + O2/CO2
Wasserstoffdarstellung
CO2
CH4/CO
Katalyse
CO2-Reduktion
zu Treibstoffen
Synthese
ZnO
Ga2O3
(Ga(1-x) Znx)(N(1-x)Ox)
Co-Katalysator
Modifikation
Struktur-Aktivitts-Beziehungen
Photokatalytische
Produktbildungsraten
AG Heiz
poster
85
iC4
iC4 - AdCOO
Die Bedeutung von AdCOO im iC4 Verbund: Die Verfgbarkeit einer effizienten Abtrenntechnologie stellt die notwendige Voraussetzung dar, um
CO2 in ausreichender Reinheit der stofflichen Nutzung zuzufhren. Ziel ist sowohl die Entwicklung von neuartigen flssigen, sowie modifizierten
festen Sorbentien, welche im Vergleich zum Stand der Technik eine energieeffizientere Abtrennung von CO2 ermglichen sollen. Auf Basis der
bisherigen Ergebnislage und grundlegender thermodynamischer Betrachtungen erscheint eine Reduzierung des Energieaufwandes fr den
Regenerationsschritt auf 2 GJ/t CO2 bei Verwendung fester Sorbentien erreichbar, allerdings steigen auch die Ansprche an die Prozesstechnik.
In der Projektlaufzeit sollen die wesentlichen Grundlagen zur Auslegung eines Prozesskonzeptes fr eine anschlieende Pilotierungsphase
erarbeitet werden.
Langzeitziel: Die Minimierung des Wirkungsgradverlustes fr Kraftwerksprozesse mit CO2 Abscheidung bei gleichzeitiger Kostenreduktion.
AP1:Charakterisierunggeeigenter CO2 Fngermolekle
ErmittlungthermodynamischerundkinetischerDaten
BasisfrrationaleEntwicklungoptimierterCO2 Fnger
AP2:HerstellunggeeigneterTrgerpartikeldurchunterschiedlicheMethoden
derFormgebungauskostengnstigenRohstoffen
AP3:Coating vonTrgerpartikelnmitFngermoleklen zurHerstellung
funktionalisierter,festerCO2 Sorbentien
AP4:Computational ScreeningzurIdentifikationgeeigneterFngermolekle,
systematischesScreeningaufBasisvonKraftfeld undDichtefunktionaltheorie
AP5:Analytik:Charakterisierungderrelevantenthermodynamischenund
kinetischenMaterialparameter,PerformanceberVielfachzyklen
Postcombustion:
C+O2 /N2 CO2 /N2 ,Partialdruck CO2 ~100 150mbar
Precombustion:
WGShift
C+O2 /H2O Synthesegas CO/H2 CO2 /H2,Druck ~20 40bar
Analytik
AK Lercher
Hochdruck CO2 Adsorptionsanlage zur Simulation von
statischen Adsorptionsvorgngen bis 40 bar und max
350 C.
AdCOO
Die Abtrennung von CO2 mit aliphatischen Aminen wird als Benchmark
herangezogen, um in Kooperation mit Computational Screening geeignete
Fngermolekle zu bestimmen. In einem Reaktor knnen Ab- und Desorption flssiger Systeme untersucht, sowie deren pH - nderung verfolgt
werden. Zustzlich werden Polymersysteme entwickelt, die Nachteile der
aliphatischen Amine lsen sollen.
Computational Screening
Zielsetzung: Verstndnis der grundlegenden
Mechanismen und energetischen Beitrge bei
der Reaktion von CO2 und Fngermoleklen.
Berechnung von Reaktionskinetiken z.B. fr
die Bildung der Carbamat- / Hydrogencarbonat Spezies. Beispiel: Monoethanolamin
~2.3
AK Rieger
Computational Screening:
Voraussage und Design energetisch optimierter Fngermolekle ber Kraftfeld / DFT
Rechnungen
Beispiel: Guanidin
Carbamat
Bicarbonat
AK Reuter
Prozesskonzept
Eine zentrale Fragestellung des Projektes mit Auswirkungen auf die Entwicklung geeigneter
Adsorbentien bezieht sich auf die Suche nach einem entsprechenden Prozesskonzept, mit dem CO2 aus den Rauchgasen von
Kraftwerken effizient und nachhaltig abgetrennt werden kann. Aufbauend auf den Erfahrungen von Siemens bei der Entwicklung eines entsprechenden
Abtrennverfahrens auf Basis Flssig-Absorption (PostCap-Verfahren) konnten vielversprechende Konzepte identifiziert werden. Mit einem Apparate- und
Prozessdesign fr mgliche Full-Scale-Anlagen und basierend auf ersten Messdaten ausgewhlter Adsorbentien wurden Wirtschaftlichkeitsbetrachtungen fr
Festbett- sowie gestufte Wirbelschichtverfahren als beste Konzepte durchgefhrt. Es zeigt sich, dass die Verfahren deutlich verringerte Betriebskosten gegenber
den etablierten Aminwschen erreichen knnen insbesondere jedoch hinsichtlich der Kapitalkosten noch verbessert werden mssen. Die im Kraftwerk zu
realisierende Grenordnung der CO2-Abtrennung stellt eine besondere Herausforderung dar. Als besonders relevant fr die Wirtschaftlichkeit und somit bei der
zuknftigen Entwicklung fester Sorbentien besonders zu beachten erweist sich die Abfuhr groer Mengen an Adsorptionswrme oder der Preis des Adsorbens.
86
poster
iC4
iC4 - COOMem
Trennschicht
(TUM)
Membranherstellung &
Beschichtung (FhG IGB)
Grenzflche
(WACKER & TUM)
Siliconelastomere
Aufbau asymmetrisch porser Trgermembranen
Substanz
ZH
2.2
38.7
5a
5b
OCH3 / H
5c
OCH3 / OCH3
H/H
6b
6c
N2
2900
260
PVOH Membran
asymmetrisch
(best value)
2800
2700
7100
700
H/H
6a
CO2
Silikonvollfilm
S / S
Permeabilitt [Barrer]
OCH3 / H
OCH3 / OCH3
25 C
Selektivitt CO2/N2
15 C
25 C
CO2
N2
CO2
N2
[P66614][5a]
742
35.0
770
57.0
21.20
13.51
[P66614][5b]
430
28.5
463
35.0
15.09
13.23
[P66614][5c]
385
17.3
487
25.7
22.23
18.95
[P66614][6a]
282
6.50
303
12.2
43.38
24.85
[P66614][6b]
207
4.80
160
5.34
43.13
29.96
[P66614][6c]
199
2.94
347
11.3
67.69
30.71
Aktuellwird
wirdweiter
weiteran
ander
der
Aktuell
mechanischenund
undchemischen
chemischen
mechanischen
Stabilittder
derMaterialien
Materialiengearbeitet.
gearbeitet.
Stabilitt
AmFraunhofer
FraunhoferIGB
IGBwird
wirddas
dasMaterial
Material
Am
zurEntwicklung
Entwicklungvon
vonKompositKompositzur
Hohlfasermembranenverwendet.
verwendet.
Hohlfasermembranen
Eigenschaften
TPSE 100
NEU : SHPNM
Degradation
180
Schmelzpunkt
133
Schmilzt nicht !
Polymerisation
Reaktivextrusion
Polymerisation in Lsung
200
Membranperformance
Polyelektrolyt (TUM)
beschichteter
Silikonvollfilm
Asymmetrische TPSE
Membran
COOMem
COOMem
TPSE100 in iPrOH/NMP
Mw = 120000 g/mol
Prozessbedingungen
Feed/Permeat Druck [bara]
1.3 - 7
Temperatur [C]
25
Feedmenge [Nm3/h]
1-4
Feedgas
N2
Exp
Fit
Ausblick
Vermessung von Membranmodulen mit CO2 -selektiver Trennschicht
Bestimmung von Mischgaspermeanzen unter prozessrelevanten Bedingungen
REM-Aufnahmen einer
TPSE-Hohlfasermembran
poster
87
iC4
iC4
- COOMeth
Abstract:
Teilprojekt mit dem Ziel der Entwicklung von Katalysatoren zur effizienten und unstetigen Methanisierung von Kohlendioxid zur Speicherung
elektrischer berschussenergie. Auf Materialbasis der Clariant und Wacker Chemie AG wurden durch die TU Mnchen erste Katalysatoren
prpariert, untersucht und mit Nickel-basierten Benchmarks verglichen. Auf Basis von Literaturkinetiken wurden von der TUM bereits kinetische
Modelle implementiert, die eine Simulation der Reaktionsfhrung ermglichen. Bei MAN erfolgten erste Pilotversuche zur Bestimmung der
Aktivitt der Benchmarks. Von Linde und E.ON wurden die Rahmenbedingungen beleuchtet und verfahrenstechnische Simulationen zum
Verfahrenskonzept durchgefhrt.
Katalysatorentwicklung zur Methanisierung von Kohlendioxid mit dem Ziel zur
Speicherung elektrischer berschussenergie mit bestehender Infrastruktur:
Sabatier-Reaktion
CO2 + 4 H2 CH4 + 2 H2O RH0 = -253,15 kJ mol-1
Anforderungsprofil fr die Entwicklung:
VerwertungrealerKraftwerksabgase
Verunreinigungeninrealen Verbrennungsabgasen
vergiftungsresistenteKatalysatoren
unsteterAnfallvonberschussenergie
erfordernkurzfristigeAnpassungderBeladunganVerfgbarkeit derEnergie
lastwechselstabileKatalysatoren
gekhlteRohrbndelreaktoren
hoheExothermie derMethanisierung
ausWrmetnungderUmsetzung resultierendeBeanspruchungsowie
Gleichgewichtslimitierung
gekhlteRohrbndelreaktoren
DarstellungeinspeisefertigerGasqualitten
ohneAbtrennungvonEdukten,Nachverdichtung,
UmsetzungstchiometrischerMischungen
Katalysatorentwicklung
100%
80%
60%
40%
20%
Abgeschlossene Arbeiten
0%
unmodifiziert
modifiziert
Wacker
WACKER
HDK (SiO2)
Kommende Arbeiten
Vermessung weiterer, im Projektrahmen hergestellter Katalysatoren mit
anschlieender mikrokinetischer Modellierung.
Detaillierte Charakterisierung der Katalysatorsysteme im Hinblick auf
Struktur-Eigenschaftsbeziehungen
COOMeth
Verfahrenssimulation:
Gesamtkonzept
Energie- und Massenbilanz
Kostenabschtzung und
Dimensionierung
Blau: Methangehalt > 92%
Variation der GHSV
Das System zeichnet sich durch gute Beherrschung der Hotspot Entwicklung aus. Entsprechend der
Zielanwendung, der Speicherung von intermittierend verfgbarer berschuelektrizitt, wurde die GHSV
zur Simulation von Lastwechseln auf unterschiedlichen Zeitskalen variiiert sowie mehrere Start / Stop
Zyklen mit unterschiedlichen Stillstandszeiten durchgefhrt. Die unter diesen Bedingungen erhaltene
Produktgaszusammensetzung entspricht den Einspeisebedingungen der DVGW fr L- Gas-Netze.
Das Diagramm zeigt die Ergebnisse unter Verwendung eines Benchmark-Katalysators von Clariant.
Pilotversuche
Muster des von der TUM neu entwickelten Katalysators werden von Clariant und WACKER LINDE LE zur
Verfgung gestellt. In einer designierten Testanlage werden diese auf ihr Verhalten gegenber
Katalysatorgiften untersucht.
In Zusammenarbeit mit MAN Turbo und E.on erstellt LINDE LE ein Verfahrenskonzept, Energie und
Massenbilanzen. Anhand der von der TUM erstellten Kinetik erfolgt die Dimensionierung der Reaktoren
und anschlieend die Kostenabschtzung des gesamten Methanisierungsprozesses.
E.ON identifiziert Randparameter zur Auslegung der Methanisierung wie:
Die erforderlichen Gasbeschaffenheiten und -reinheiten zur Produkteeinspeisung ins Erdgasnetz.
Identifikation, Bewertung und Spezifikation von CO2-Quellen: Sowohl CO2-Mengen als auch deren
Reinheiten werden in erheblichem Umfang die Auslegung und damit die Kosten der CO2-Methanisierung
beeinflussen, bercksichtigt werden soll CO2 aus Kraftwerksabgasen und aus Biogasanlagen.
Des Weiteren wird E.ON eine techno-konomische Bewertung der Gesamtketten
durchfhren. Je nach Konzept wird die Methanisierung und Nutzung des Methans zu
unterschiedlichen Kosten und Erlsen fhren. Im Rahmen des Projektes sollen
daher entsprechende Anwendungsflle identifiziert und bewertet werden.
Verfahrenskonzept
88
poster
DVGW-Forschungsstelle
Engler-Bunte-Institut (KIT)
Engler-Bunte-Ring 1
76131 Karlsruhe
http://www.dvgw-ebi.de/
4 H2 + CO2
Konzept
Erneuerbare Energien
Elektrolyse
dynamisch
el. Energie
(fluktuierend)
Erdgasnetz
H2-Speicher
Chemische
In Deutschland sehr gut
Energietrger
H2
ausgebaut
Groe Speicherfhigkeit
in Poren- und Kavernenspeichern
H2O
O2
H2O
H2 + O2
Vergasung
Entschwefelung Biogas
CO/CO2-Quellen
Klein: Biogasanlage,
BHKW
Synthese: CH4 + KW
CO2 (CO)
Nutzung O2
Speicherbedarf / Wirkungsgrad
Quellen: www.bbfm.de,
http://www.repotec.at,
Badische Zeitung
Gro: Industrie,
Mittel: Vergasung,
Kraftwerke
BHKW, Heizwerke
Prognostizierter Speicherbedarf
schwankt von 0,1 bis 15 TWh fr 2020
In Poren- und Kavernenspeichern
knnen ca. 230 TWh gespeichert
werden (vgl. Pumpspeicherkraftwerke:
0,04 TWh)
Wirkungsgrad der Prozesskette Strom
Methan derzeit 55 - 65 %
Durch Kopplung mit anderen
Prozessen und Abwrmenutzung
knnen Wirkungsgrade erhht werden
1)
2)
3)
Arbeitspakete
AP1 Elektrolyse
Entwicklung eines PEMDruckelektrolyseurs
System- und Betriebsoptimierung fr eine
dynamische Betriebsweise
Teststand
Fluktuation
Windkraft
Leistungsgefhrt: 5 - 100 %
AP2
2-Phasen-Methanisierung
Frischgas:
a. 10 000 m/h (NTP) CO2
b. 40 000 m/h (NTP) H2
Prozessparameter:
a. P = 20 bar
b. Tein (R1, R2) = 220 C
c. Taus (R1) = 550 C
d. Taus (R2) = 240 C
Produktspezifikation:
98 %
a. CH4
b. CO2
<2%
<1%
c. H2
d. H2O
< 100 ppm
Betrieb der Anlage: autark
Khlwasser: 7,5 MW (T < 80 C)
Nutzwrme:
a. 12 MW (T > 220 C)
b. 9,2 MW (80 bis 180 C)
R2 = Reaktor 2
S2 = Molekularsieb
S1 = Wasserabscheider 1
S3 = Wasserabscheider 2
Fluktuation Photovoltaik
Temperatureffekt
AP4 Brennwertanpassung
Erzeugung von C2-C4 aus regenerativen Quellen
HS
Beispiel(kWh/m) Mischung (%)
H2
3,5
5
CH4
11,1
85,7
C2H6
19,5
9,3
C3H8
28,1
Randbedingungen
Festbettreaktor
T= 250-330C
p= 1 -2 MPa
H2/CO2, ein= 3-8
mod= 100-6000 kg s/m3
MischErdgas H
Stack current in A
AP5 Systemanalyse
Simulation einer Power to Gas-Anlage im
markt- und erzeugergefhrten Betrieb
marktgefhrt, zentral
Methanisierung im 3-Phasen-System
Gute Temperaturkontrolle, optimale Wrmeabfuhr,
vereinfachter Aufbau
erzeugergefhrt, dezentral
Randbedingungen
800 m H2-Speicher als Puffer
Elektrolyseur (10 MW) folgt eingespeistem Strom 1:1
Methanisierung (6 MW) folgt langsamer:
10 % Lastwechsel pro 10 min
40..100 % Last
11,5
AP6 Wirtschaftlichkeit
Abschtzung des Einflusses fluktuierender Energiebereitstellung
auf das Energiesystem Strom
Ermittlung der Residuallast
auf Basis der ErneuerbarenAusbauszenarien des
Netzentwicklungsplans
2013 mit Hilfe historischer
Stromnachfrage- und
Wetterdaten
Residuallast in GW
Stack voltage in V
3-Phasen-Methanisierung
R1 = Reaktor 1
3)
A 2023
Onshore 45,7 GW
Offshore 10,3 GW
PV
55,3 GW
B 2023
Onshore 49,3 GW
Offshore 14,1 GW
PV
61,3 GW
B 2033
Onshore 66,3 GW
Offshore 25,3 GW
PV
65,3 GW
C 2023
Onshore 86,0 GW
Offshore 17,8 GW
PV
55,6 GW
poster
89
4. BMBF-Statuskonferenz 08.04.2014
Werner Zinsser
Detlef Bahnemann
Irina Ivanova
Sven Albrecht
Dieter Ostermann
Durchgefhrte Arbeiten:
TEM an NaTaO3
Experimental shape
analysis for pure NaTaO3
nanoparticles: a) TEM
bright-field micrograph, b)
electron diffraction
pattern of circa 100 nm
circular area in a indexed
according to [010] zone
axis, c) STEM annular
dark-field micrograph with
normal distances of
polyhedron facets to
center of crystal, d)
reconstructed polyhedron
shape, e) relative
abundance of crystal
facets (same color index
applies for as in c). e)
Secondary electron closeup
30
100
25
90
80
20
70
15
60
10
50
40
Aufsteigende Wasserstoffblschen
aus NaTaO3-Suspension
Zusammenfassung:
Toolbox wurde entwickelt und wird fr weitere Entwicklung genutzt werden
Quanteneffizienzen verbessert, aber Ziel nicht erreicht; Stand der Wissenschaft aus der Literatur z.T. noch nicht nachvollziehbar
Solarer Konzentratorteststand am DLR liefert Wasserstoff, weitere Tests in Zusammenarbeit mit ODB und H.C. Starck werden
derzeit durchgefhrt
Bare
0,57 % La
0,83 % La
1,11 % La
30
H 2 ( mol/h)
Projektziele:
Entwicklung von Photokatalysatoren und Reaktortechnologien fr die solare Wasserspaltung
[email protected]
www.hcstarck.com
Christian Jung
Michael Wullenkord
t1/2 ( s)
Thomas Bredow
90
poster
Dynamische
H2O-Elektrolyse fr
H2 als chem. Energiespeicher
Lastregulierung
H2-Speicherkonzepte
Nutzung von
Stromspitzen fr
chemische
Prozesse
Reaktorentwicklung
Katalysatorentwicklung
Bewertung des
Gesamtprozesses
(konomisch,
kologisch)
Integration in
bestehende
Wertschpfungskette
Szenarien zur
Verfgbarkeit von
regenerativen
Energien
CO2
50
Austretender Molenbruch / %
Entwicklung flexibler
Prozesskonzepte
RWGS
CO2-Reforming
Ameisensuresynthese
Produktionskonzepte der
Zukunft
CH4
CO
H2
TOfen
Stabiler Ni/MgAlOx-Katalysator
40
30
600
20
400
10
0
800
50 mol% Ni
0
20
40
5 mol% Ni
60
80
Temperatur / C
Nutzung
regenerativer
Energien
CO2 als
chemischer
Rohstoff
Katalysatorentwicklung
Fr die Umsetzung von CO2 in der Trockenreformierung und der RWGS bei
Temperaturen ber 800 C wurden unterschiedliche Wege der
Katalysatoroptimierung verfolgt
An der TU Dresden wurde das Problem der lokalen Unterkhlung, dem
Auftreten sogenannter Coldspots, durch Entwicklung eines Siliziumcarbidbasierten Nickel-Katalysators begegnet.
Das Fritz-Haber-Institut Berlin hat zusammen mit dem Lehrstuhl fr
Technische Chemie an der Ruhr-Universitt Bochum bzgl.
Temperaturstabilitt auf Magnesium-Aluminium-Mischoxide gesetzt. Auch
hier wurde Nickel als aktive Katalysatorkomponente eingesetzt.
BMS und BTS hat einen Katalysator auf Perowskit-Basis entwickelt sowie
eine Katalysatorbeschichtungstechnologie fr die Heizwendeln.
In situ XRD-Untersuchungen zur Stabilitt erfolgten am LIKAT Rostock
200
100
Zeit / h
Reaktorentwicklung
Vom Heizkonzept bis zum Demonstrator unter Nutzung von berschussstrom fr
hohe Temperaturen ber 800C
ICVT und Uni Stuttgart: Funktionsprinzip des Reaktors dargestellt am Einzelrohr.
Notwendige Wrme durch diskrete O2-Einspeisung gewhrleistet. Erwrmung
direkt im Reaktionsraum und nicht ber Wand.
KIT: Entwicklung einer Mikrowellenbeheizung, die eine direkte Beheizung des
Katalysators ermglicht.
BTS: Elektrische direkte Beheizung des Reaktionsraums ber Heizwendeln.
INVITE: Auslegung und Betrieb einer Demonstrationsanlage zum Nachweis der
Machbarkeit der direkten elektrischen Beheizung gemss des Bayer-Konzepts.
Inbetriebnahme im Juni 2014: Betrieb von RWGS- und CO2-ReformingKampagnen
POX beheizter
keramischer
Gegenstromreaktor
Mikrowellenbeheizung
Elektrisch
beheizter
Monolithreaktor
Heizwendel
Monolith
Die Proton Exchange Membrane (PEM)Elektrolyse von Siemens ist in der Lage, auch
starke Lastschwankungen zu folgen, was im
Labormastab bereits in mehreren Tausend
Betriebsstunden gezeigt wurde. Am RWEStandort Niederauem bei Kln wurde ein
Elektrolysecontainer mit 100kW (300kW peak)
installiert und im Mrz 2013 in Betrieb
genommen. Dauer- und berlastbetrieb,
Dynamik
des
Lastwechsels
und
der
Wirkungsgrad der Anlage wurden untersucht
und bewertet. Mehr als 4 t H2 wurden erzeugt.
6 Heating
Elements
Ceramic
Insulation
Gas Sampling
Electrical
Connections
poster
91
Motivation
How to compare
storage systems with
non-equal products?
By environmental
impact reductions
Direct storage
product
Power
Power
Power
Conventional process
Mobility
Heat
1 MWh
Surplus
electricity
Hydrogen
H2
Power
H2
Methane
H2
Methanol
production6
Methanol
Chemical
Power
H2
Syngas
production7
Syngas
Chemical
Power
Electrolysis4
Environmental impact
of product from
storage system
Chemical
Methane
production5
Heat supply8
CO2 supply8
Mobility
Steam-Methane-Reforming
Fossil natural gas
Grid power
supply8
Mobility
Environmental impact
of product from
conventional process8
Combustion of fuel
Environmental impact
reduction
for storage systems
Conclusions
Environmental assessment:
Among Power-to-Fuel:
1. Power-to-Heat
2. Power-to-Mobility
Further Information
Andr Sternberg
vCard
3. Power-to-Power
4. Power-to-Fuel
Acknowledgements
This
work
References
1 P. Denholm and G. L. Kulcinski, Energy Conversion and Management, 2004, 45, 2153 2172.
2 M. Metz and C. Doetsch, Energy, 2012, 48, 369 374.
3 FIZ Karlsruhe GmBH, Electrical driven heat pumps, Technical report, 2013.
4 F. Schth, Chemie Ingenieur Technik, 2011, 83, 19841993.
5 B. Mller, K. Mller, D. Teichmann and W. Arlt, Chemie Ingenieur Technik, 2011, 83, 20022013.
6 L. K. Rihko-Struckmann et. al., Industrial & Engineering Chemistry Research, 2010, 49, 1107311078.
7 Project report CO2RRECT (ref. no. 33RC1006B)
8 PE INTERNATIONAL AG, GaBi 6, Software-System and Database for Life Cycle Engineering., 2013.
92
poster
Das BMBF-gefrderte Projekt Sunfire befasst sich mit Forschung zur Entwicklung einer
Versuchsbedingungen
Untersuchte Proben
Atmosphre
Wasserdampf
ausgesetzt, im uersten Fall Atmosphren aus reinem Sauerstoff (O2) oder aus reinem
Wasserdampf (H2O).
Grundmaterial
ITM
Beschichtung
RC LSM
RC MCF
RC LSM
RC MCF
RC LSM
RC MCF
RC LSM
RC MCF
Crofer 22 APU
Sauerstoff
ZielsetZung
ITM
Crofer 22 APU
Untersuchung des Korrosionsverhaltens ausgewhlter InterkonnektorBeschichtungen in O2 und in H2O bei 850 C und 30 bar
Schweinaht
1.000 h
x
Proben
x
x
x
x
x
Miniatur-Testautoklaven
aus Nicrofer 6025 HT
zugeschweit
Beitrag zum Verstndnis der Degradationsmechanismen und des Einflusses von Druck
Beurteilung der Korrosionsbestndigkeit bei den gegebenen systemspezifischen
Betriebsbedingungen
Material
Crofer 22 APU
ITM
Fe
Bal.
Bal.
Cr
22,0
26,0
Mn
0,42
Ti
0,08
Al
0,12
<0,03
Si
0,11
<0,03
Andere
La (0,08)
(Mo)x, (Ti)y, (Y)xy
Versuchsaufbau: Testautoklav im
geschlossenen Ofen mit Druck- und
Temperaturberwachung und
Wasser-Nachdosierung
e r g e b n i s s e Q u e r s c h l i f f e d e r s c h i c h t e n n a c h a u s l a g e r u n g i n r e i n e m o 2 u n d r e i n e m h 2o b e i 8 5 0 c u n d 3 0 b a r
RC-mCF + Crofer 22 APU
O2 1000 h
x2000
RC-mCF + ITm
O2 1000 h
RC-mCF + ITm
H2O 1000 h
RC-lSm + ITm
O2 1000 h
RC-lSm + ITm
H2O 300 h
Oberflche
RC-lSm + ITm
H2O 1000 h
Oberflche
x1000
e l e m e n ta n a ly s e m a p p i n g
Schicht
Sauerstoff 1000 h
RC-MCF
CoCr2O4/CoOCr2O3
RC-LSM
SrCrO4, La0,65Sr0,35MnO3
RC-MCF
Co, (FeO)0,099(MnO)0,901
RC-LSM
Sr0,1MnLa0,9O3
Wasserdampf 300 h
cr
Formel
Atmosphre
cr
Z u s a m m e n fa s s u n g
Die RC-MCF Schicht ist in reinem Sauerstoff in ihrer Zusammensetzung bestndig.
Chrom ist in gleichmig verteilter Konzentration in der Schicht zu finden.
In Wasserdampf tritt eine Reduktion der Schicht zu metallischem Kobalt auf und
mn
mn
fe
co
das Gefge wird grobkrnig. Dagegen ist in Wasserdampf kein Chrom in der
fe
Schicht zu sehen.
In beiden Fllen wchst auf dem Interkonnektor-Material unterhalb der
Beschichtung eine Cr2O3-Schicht auf, in Sauerstoff unterwachsen von MnCr2O4.
RC-LSM: in Sauerstoff bildet sich auf der Oberflche eine nicht
zusammenhngende Anhufung von SrCrO4. Das bedeutet, RC-LSM kann die
Abdampfung von Cr in Sauerstoff weniger unterbinden als RC-MCF.
cr
x2000
cr
mn
la
sr
mn
la
sr
poster
93
Flow sheet
(CHEMCAD)
T1
Interaction via
transition script
94
poster
Motivation
Reale Stoffsysteme
Laboranlagen
Groanlagen
Laborapparate
Modellsysteme
Groapparate
Reale Stoffsysteme
Technikumsapparate
A2 Thermoblech-Naturumlaufverdampfer
Wasser-Glycerin Gemisch
xH2O = 0,71 molH2O/molges
pBA = 200 mbar
TU Mnchen
Uni Paderborn
Uni Kassel
HSU Hamburg
Eintrittsgeschwindigkeit [m/s]
0,07
Laboranlagen
an Universitten
0,05
0,04
0,03
536
447
358
268
0,02
179
0,01
0
89
20
40
60
80
100
120
140
A5 Multistream-Kondensatoren
35
iso-Propanol
Werkstoff: VA-Stahl
p = 1,013 bar
1
16000
18000
20000
Reihe 1
Reihe 2
Reihe 3
22000
24000
26000
30
Reibungsdruckverlust pR,Kor
Steigerungsfaktor Nuelt
Wrmestromdichte q in W/m
[deg-engineering.de]
TU Braunschweig
Verbindende
Elemente
20
15
10
5
0
Stoffsysteme
- Reinstoffe
- Gemische
hs* = 117 %
hs* = 77 %
hs* = 33 %
0,2
14205
hs* = 100 %
hs* = 50 %
0,15
8523
0,1
5682
0,05
2841
0
0
10
15
20
25
10
15
20
25
30
35
Identifizierung und
Quantifizierung von
Verbesserungspotentialen
Bercksichtigung von
konom. und kolog.
Aspekten
Stand heute
11364
Chlorbenzol
H/dH = 85,7
AW/ASt = 343
ReEin [-]
0,25
Platteneintrittsgeschwindigkeit [m/s]
Charakteristische
geometrische
Parameter: dhydr, Aeff
Technikumsanlagen bei
Industrie-Partnern
Potentialabschtzung
[wieland.de]
Datenverdichtung
25
Linde AG
Versuchsdurchfhrung und
Auswertung
626
T = 7 K
T = 8 K
T = 10 K
T = 12.5 K
T = 15 K
T = 17.5 K
T = 20 K
0,06
A4 ThermoblechKondensatoren
715
Reein [-]
0,08
Strmungsrichtung
Ausgewhlte Ergebnisse
BTS GmbH
Projektpartner
poster
95
HY-SILP:
Ligands
Ionic liquids
Hydroformylation
Concept Supported
Ionic Liquid Phase
(SILP) catalyst
SILP catalyst
powder
SILP particle
Pore
structure
Technical equipment
Results I
IL film
Results II
High boiling side product fills pores of
the support material
Model for pore filling[5,6] in accordance
with start-up behavior of conversion tests
Conversion (related to all butenes) over time in continuous gas phase hydroformylation of
industrial C4 feedstock using Rh-BzP/SiO2 catalyst material. Parameter: mcat=12.0g,
mRh=0.2wt-%, L/Rh=10, T=100-120C, p=10bar, pbutenes=1.6bar (1.3bar), pbutanes=0.6bar
(0.5bar),pH2=pCO=3.9bar (4.1bar) before (and after) variation of syngas/butene ratio from 6 to 8
after 170 h on stream, residence time=48s (43s).
Homogenous solved
catalyst complex
96
poster
Multi-Phase
Arbeitspakete
1. Entwicklung geeigneter Messtechnik fr den Einsatz unter
industriellen Bedingungen
2. Aufbau von Versuchsanlagen zur Bestimmung kritischer
Messdaten
3. Validierung und Ableitung von Modellen zur Auslegung anhand
der Messdaten
1. Entwicklung Messtechnik
2. Versuchsanlagen
3. Modellbildung
Simulation von Einzelblasen und
Blasenschwrmen mit Hilfe von
Direkter Numerischer Simulation
(DNS)
Euler-Euler-Simulation einer
Technikumsblasensule DN160,
Geschwindigkeitsprofil der
Flssigphase
Vom HZDR entwickelter Gittersensor
zur Messung radialer Gasgehaltsprofile
radial distance
radial distance
Kompartment-Modellierung
Ausblick
Auswertung der Messdaten der
verschiedenen Versuchsreaktoren
Ableitung von verbesserten
Modellgleichungen fr die Nutzung in
1D/2D- sowie CFD-Modellen
bertragung auf technischen Prozess
und Ableitung von Optimierungspotenzialen
LCA und Bewertung des CO2Einsparpotenzials
poster
97
Projektinformationen
Budget:
BMBF Frderung:
Projektdauer:
Projektstart:
3,5 Jahre
01. Mai 2011
Funktionsweise Wrmepumpe
Bei ausschlielicher Frderung durch das BMBF ist auf allen visuellen Formen von Publizitts- und Informationsmanahmen das unten
stehende BMBF-Logo zu verwenden. Zustzlich sollte das Logo des Projekttrgers und Frderschwerpunkts mit angegeben sein. Wo
vorhanden, kann auerdem das eigene Projektlogo verwendet werden:
Logo des
Frderschwerpunkts
le aufnimmt (Qzu) und diese auf einem hheren Temperaturniveau einem Verbraucher zur Verfgung stellt (Qab).
Qab
Projektpartner
Forschung: Startup-Projekte
Traugott Ulrich
Gerd Janson
Wrmetauscher_1
Drossel
Verdichter
Wzu
Wrmetauscher_2
SAM
1
Qzu
Herausforderungen
Die miniaturisierte Bauweise der Maschine bringt neue aerodynamische, fertigungstechnische und konzeptionelle
Schwierigkeiten mit sich.
Hohe Drehzahl-Drehmoment-Niveaus verlangen die
Auslegung eines neuartigen Elektroantriebs.
Bedingt durch die lfreie Funktionsweise mssen bestehende
Lagerkonzepte weiterentwickelt werden.
Projektplan
98
poster
Motivation
Mixed-Matrix-Membranen (MMM)
Einsparung von Energie & Kosten durch Einsatz selektiverer MixedMatrix-Membranen (MMM)
Mgliche Anwendungsbereiche:
- Erdgaskonditionierung
- Lsungsmittelrckgewinnung
- Prozessgasaufbereitung (z.B. Fischer-Tropsch-Synthese)
Polymer / AKSuspension
Fertige MMM
nach Vernetzung
Beschichtungsrichtung
Automatisiertes
Filmziehgert
Sttzschicht
Polymer/
Aktivkohlesuspension
Selektivitt nC5H12/N2 []
Beschichtungsanlage
Experimentelle Ergebnisse
SelektivittnC4H10/CH4 []
35
pF =1040bar
=20C
yF,nC4H10 =0,030,05
pP =1bar
30
25
POMS
MilestoneMMM
MMMBatch1
MMMBatch2
20
15
0.20
100
pF =30bar
=20C
yF,nC5H12 =0,015
pP =1bar
50
0
10
MMM
POMS
20
Zeit [d]
1.6
1.4
1.2
=20C
1
0.0
0.1
0.2
0.3
POMSExperiment
15
40
AM
.
Q
.
P
10
0.4
Retentat
yF,n-C4H10 = 0,01
Kondensat
=20C
yF,nC4H10 =0,030,05
pP =1bar
20
40
60
Feeddruck [bar]
MMM
Einzelgas
n-C4H10
MMM
Gasgemisch
n-C4H10/CH4
POMS
Gasgemisch
n-C4H10/CH4
1%
6,4 %
3,7%
Gute bereinstimmung
zwischen Modell und
Experiment
PROJEKTKOORDINATION:
0.25
0.30
0.35
0.40
mittlere Fugazitt nC4H10 [bar]
POMSFreeVolumeModell
Zusammenfassung
15
POMSModell
20
Mittl. rel.
Abweichung
MMMModell
25
30
Feed
VF = 1000 Nm/h
pF = 30 bar
F = 20 C
yF,n-C4H10 = 0,05
MMMExperiment
Emergieverbrauch [kW]
Selektivitt nC4H10/CH4[]
Permeanz nC4H10
[Nm/(mhbar)]
1.8
PDMS
PDMS/AK
PDMS/Zeolith
17
Einsparpotential
.
30
19
150
Permeation Gasgemisch
21
0.20
200
35
2.2
pF =1030bar
=20C
yF,nC4H10 =0,020,04
pP =1bar
23
0.40
0.60
0.80
1.00
mittlereFugazitt nC4H10 [bar]
Mechanistische Modellierung
Permeation Einzelgas
25
Langzeitstabilitt
250
Filmapplikator
2.4
Selektivitt nC4H10/CH4 []
150
100
50
0
PDMS
POMS
MMM
POMS/AK
Ausblick
poster
99
Ziele
Methode
Projekt
Im Rahmen des Projektes wird die Methode zu einem standardisierten, unternehmens- und
prozessbergreifenden Managementund Benchmarking-System fr
Energieeffizienz
weiterentwickelt, das die effizientesten Technologien bercksichtigt, die Wissenschaft und Industrie
heute kennen. Dabei wird die Methode an Prozessen der industriellen Partnern aus der
chemischen Industrie und den Life Sciences validiert.
Ergebnisse
Utility
Systems
Heat
integration
Benzene
Insulation /
Illumination
730 kW
Chloroform
1. Jahr
2. Jahr
3. Jahr
Partner
Toluene
Oper.
Improvem. /
Automation
475 kW
Acetone
1 bar
Benzene
5.1 bar
1.8 bar
Feed
Number of Measures*
1 bar
Chloroform
Toluene
2.8 bar
Acetone
10 bar
Feed
200
180
160
140
120
100
80
60
40
20
0
Equipment /
Unit
Operation
100
poster
IL-WIND
FK: 01RC1009B
www.crt.cbi.uni-erlangen.de
Entwicklungsziel
Herstellung eines Schmiermittels basierend auf einer Ionischen Flssigkeit (IL), welche folgende Eigenschaften aufweist:
IL
IL
IL
IL
IL
IL
Gute Schmierleistung
IL
IL
IL
IL
IL
IL
IL
IL
IL
IL
IL
CO2-Reduktion
IL
IL
IL
Ammonium
IL
Sulfat
IL
Phosphat
IL
zur
der
Ergebnisse
Gute Schmierleistung
Vermeidet verfrhten Lagerausfall
IL
IL
Steuerung
IL
IL
Halogenfrei
IL
IL
IL
IL
CO2
T [C]
IL
IL
IL
von
IL
IL
Phosphinat
IL
Verwendung
IL
IL
IL
VI
VI
>>100
IL
IL
Sulfonat
VI <100
VI
< 100
IL
IL
Phosphonat
IL
R = Rest
IL
IL
IL
Imidazolium
llllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
IL
IL
Phosphonium
IL
IL
[mm2/s]
IL
IL
IL
IL
Projektpartner:
2. Fall: Wartungsfrei 90 %
poster
101
EinneuesVerfahrenzurGewinnungvonLignin,Celluloseund
Hemicellulose ausbiogenemMaterialmitHilfeneuartiger
ionischerFlssigkeiten
R.Janzon1,B.Saake1,K.Becker2 ,H.G.Brendle3,S.Saur4undW.Kantlehner4
1UniversittHamburg,Leuschnerstrae91b,D21031Hamburg
2
BayerTechnologyServicesGmbH,BTSTDDPDPS,GebudeB310,D51368Leverkusen
&ShneGmbH&Co.KG,Holzmhle1,D73494Rosenberg
HochschuleAalen,InstitutfrAngewandteForschung,Beethovenstr.1,D73430Aalen
Kontakt:[email protected]
3 J.Rettenmaier
Fazit
Einleitung
Ein neues energie und rohstoffeffizientes Aufschlussverfahren
ist in der Entwicklung, welches es ermglicht Faserstoffe (FS),
Lignin und Hemicellulosen zu gewinnen. Die Aufschlusslsung
besteht aus einer ionischen Flssigkeit (IL; Alkoxymethylen
Iminiumsalz) und einem organischen Lsungsmittel.
Fr
den
Labormastab
liegt
nach
eingehenden
Untersuchungen ein erprobtes Verfahrenskonzept vor. Darauf
basierend wurden die Aufschlussparameter Temperatur
(100160C), Zeit (45240 min) sowie die Konzentration der
IL (115% bzgl. Aufschlusslsung) fr den Aufschluss von
industriellen FichtenHackschnitzeln (HS) bei einem
Flottenverhltnis von 1:5,5 (HS:Aufschlusslsung) optimiert.
Die mittels des ILAufschlusses aus dem Rohstoff gewonnenen
Faserstoff, Lignin und Hemicellulosenproben zeigt Abb. 1.
Mittels des ILAufschlusses ist eine gute Fraktionierung der Cellulose und
Ligninanteile des Holzes mglich. Dies zeigen die FSAusbeute von 55%
sowie die LigninAusbeute von 26% in Kombination mit den hohen
Reinheitsgraden von 90% Glucose bzw. 86% Lignin der jeweiligen Fraktion
(Abb. 2).
Bei einer Polydispersitt von 4,1 weisen die ILLignine mit Werten unter
6.000 g/mol eine relativ geringe molare Masse auf (Abb. 3).
Nach 21 Tagen sind bei der Vergrung der HemicellulosenFraktion 277 mL
Methan/goTS entstanden und der oTSGehalt wurde von 5% auf unter 1%
abgesenkt (Abb. 4).
Verwertungspotentiale: Aufgrund der engen Faserlngenverteilung zeigen
die FS gute Filtrationseigenschaften. Fr die Lignine ist angesichts der
hohen Reinheit und der niedrigen MWWerte der Einsatz bei PFHarzen und
Polyurethanen denkbar. Auf Grundlage der Biogastests ist die anaerobe
Vergrung der HemicellulosenFraktion bzw. der Fllabwsser mglich.
Ergebnisse
Lignin [%]
Hemicellulosen [%]
Glucose [%]
FS-Ausbeute [%]
Lignin-Ausbeute [%]
Rohstoff:FichtenHS
50
60
Hemicellulosen
Lignin
(gelstinProzessabwssern)
Abb.1:Rohstoff(FichteHS)sowiemittelsdesILAufschlussesgewonneneFaserstoff,Lignin
undHemicellulosenFraktion
0,8
40
40
30
20
0
Faserstoff
60
80
Ausbeute [%]
Zusammensetzung [%]
100
FaserstoffFraktion
LigninFraktion
20
Abb.2:Zusammensetzung(rechteYAchse)undAusbeute(linkeYAchse)der
mittelsdesILAufschlussesgewonnenenFaserstoff undLigninfraktion
MW = 5.700 g/mol
MW /MN = 4,1
0,6
W(log M)
0,4
0,2
0,0
10x100
100x100
1x103
10x103
100x103
1x106
Das BMBFVerbundprojekt Ein neues Verfahren zur Gewinnung von Lignin, Cellulose und Hemicellulose aus biogenem Material mit Hilfe neuartiger ionischer
Flssigkeiten wurde durch den Projekttrger DLR gefrdert. Das vorliegende Poster wurde auf der 4. Statuskonferenz der BMBFFrdermanahme "Technologien fr
Nachhaltigkeit und Klimaschutz Chemische Prozesse und stoffliche Nutzung von CO2 am 08.04.2014 in Knigswinter vorgestellt.
102
poster
STOFFDATEN
VLE-Messungen ber FTIR-Spektroskopie
Temperaturstabilitt
t = 80C
Temperatur
der IL im AWT
TH: Wasserthermostat
GZ: Gleichgewichtszelle
CP: Kreislaufpumpe
D:
Demister
FTIR: Fourier Transform-Infrarot Spektrometer
Nach [1]
Anion entscheidend fr
Dampfdruckabsenkung
Unkritisch im AWT
SIMULATION
Annahmen fr die Simulation
Stationrer Prozess
tHeiz = 90C
tKhl = 25C
EXPERIMENTE
Apparatekonzepte der 4kW-Technikumsanlage
Desorption im gefluteten Shell & Plate Apparat
Ausblick
Dimensionierung der Apparatekonzepte fr Anlagen > 10 MW
Wirtschaftliche und kologische Gesamtbewertung
Fazit
Wasser ionische Flssigkeit ist ein mgliches Arbeitsstoffpaar fr
Absorptionskreislufe
1)
2)
3)
4)
poster
103
Motivation
Information/
Kommunikation Beleuchtung
2%
3%
31%
Mechanische
Energie 37%
Raumwrme
4%
2%
21%
Klima/Prozessklte
Warmwasser
Prozesswrme
Projektziel
Projektergebnisse
Gesamtsystem
Absorptionswrmepumpe
Wrmespeicher
Auslass
P-7
TIR
I-1
V-5
Wasserdampf
Messung
V-2
P-6
Taus
P-3
Paus
Reaktor
T
W-01
P-5
P-2
Thermostatbad
P-4
V-1
Tein
TIR
112
TIRCS
113
MFC
FIR
114
Pein
Druckhalter
Luft
312
111
FIR
I-5
2,5
2,2
2,0
1,8
1,6
1,4
1,2
1,0
0,8
0,6
0,4
0,2
0,0
2,0
1,5
1,0
0,5
0,0
LiBr *
IL 1
2.700
Wrmeleistung [kW]
COP [-]
IL 2
Thermostatbad
150
2.900
120
1.700
56
50
805
24
Gas
Steinkohle
Braunkohle
SIT
Sensible
Latent
Sorption
Chemisch
SIT
1st generation
Durch das Zusammenspiel von Wrmepumpe und Wrmespeicher kann bei der Bereitstellung von thermischer Energie ein erhebliches
CO2e-Reduktionspotential realisiert werden
Kontakt:
Projektpartner:
104
poster
Acrylate Formation from CO2 and Ethylene Mediated by NickelComplexes Mechanistic Studies
Philipp N. Plessow,a,b Andrey Y. Khalimon,b S. Chantal E. Stieber,b Nria Huguet,b Ivana Jevtovikj,b Miriam Bru,b Ronald
Lindner,b Michael Lejkowski,b Ansgar Schfer,a Michael Limbach,b,c* Peter Hofmannb,d*
aBASF SE, GVM/M, Ludwigshafen, Germany; bCaRLa, Heidelberg, Germany;
SE, GCS/C, Ludwigshafen, Germany; dRuprecht-Karls-Universitt Heidelberg, Organisch-Chemisches Institut, Heidelberg, Germany
cBASF
Introduction
Sodium Acrylate
Catalytic cycle
High Pressure
C2H4
tBu
P
P
tBu
outer sphere
t Bu
2
H2
P
Ni
P O
t Bu
2
P
Ni
H1 H2
P
t Bu
2
H1
O
t Bu
2
G = 82
Ni
tBu
P
Ni
P
t Bu
2
CO2
G = 110
H1
H2
CO2
tBu
ONa
TON = 10.2
tBu
BuOH
ONa
H1
P
Ni
P O
t Bu
2
CO2
G = 124
G: = 0
NHCP Ligands:
H2
G = 15
CO2
Ox idati ve Coupli ng
Ni
L
G:
Pt Bu2
Ni
t Bu
2
Ni
t Bu
2
G=1
t Bu
2
G = 73
O
+MeI
G = 131
Ni
t Bu
2
OMe
G = 73
t Bu
2
t Bu
2
Ni
Ni
CO2Na
Pt Bu2
15 kJ/mol
5 (-7) kJ/mol
P
Ni
P
t Bu
2
G = 22
CO2H
G = -4
CO2Na
t Bu
2
CO2Me
G = 21
OMe
Ni
G# ~ 104
G = 21
OMe
t Bu
2
t Bu
2
Ni
ClSiMe2t Bu
NR3
t Bu
2
P O
t Bu
2
O
t Bu
2
Ni
P
Ni
P
t Bu
2
O
OSiMe2t Bu
OSiMe2t Bu
t Bu
2
CO2Me
t Bu
2
1. MeOTf
2. NR3
G = -95
G = -4
N t Bu
OMe
t Bu
2
P
t Bu
2
CO2H
Ni
G = -22
P
t Bu
2
t Bu
2
+base
-Hbase+
-I-
+NaOMe
-HOMe
t Bu
2
G = -19
G: = 0
G = 138
G = 75
t Bu
2
Ni
O
Pt Bu2
G = 109
NaOtBu
OtBu
Ni
P O
tBu
2
t Bu
2
Ni
P O
tBu
2
ONa
inner sphere
t Bu
2
G = 66
G = 15
High Pressure
CO2
Ni
tBu
Ni
t Bu
2
Computational Details
All geometries were optimized at the BP86/def2-SV(P) level of theory. Gas-phase
free energies were obtained based on single-point energies at the RPA@PBE/def2QZVPP level of theory. Free energies in solution (THF) were obtained by adding
solvation free energies calculated with COSMO-RS, and the parameterization for
BP86/def-TZVP (reference state: T = 298.15 K; = 0.1). All calculations were
carried out with TURBOMOLE.
References
[1] Hoberg, H.; Peres, Y.; Krger, C.; Tsay, Y. H. Angew. Chem. Int. Ed. Engl. 1987, 26, 771.
[2] Lejkowski, M. L.; Lindner, R.; Kageyama, T.; Bdizs, G. .; Plessow, P. N.; Mller, I. B.; Schfer, A.; Rominger, F.;
Hofmann, P.; Futter, F.; Schunk, S. A.; Limbach, M. Chem. Eur. J. 2012, 18, 14017.
[3] Graham, D. C.; Mitchell, C.; Bruce, M. I.; Metha, G. F.; Bowie, J. H.; Buntine, M. A. Organometallics 2007, 26, 6784.
[4] Plessow, P. N.; Schfer, A.; Limbach, M.; Hofmann, P. Submitted.
[5] Bruckmeier, C.; Lehenmeier, M. W.; Reichardt, R.; Vagin, S.; Rieger, B.; Organometallics 2010, 29, 2199.
[6] Lee, S. Y. T.; Cokoja, M.; Drees, M.; Li, Y.; Mink, J.; Herrmann, W. A.; Kuehn, F. K. ChemSusChem 2011, 4, 1275.
[7] Plessow, P. N.; Weigel, L.; Lindner, R.; Schfer, A.; Rominger, F.; Limbach, M.; Hofmann, P. Organometallics 2013,
32, 3327.
Acknowledgements
The presenting authors work at CaRLa of Heidelberg University, which is co-financed by the University of Heidelberg,
the State of Baden-Wrttemberg and BASF SE. Support from these institutions and financial support from the BMBF
(Chemische Prozesse und stoffliche Nutzung von CO2 : Technologien fr Nachhaltigkeit und Klimaschutz, grant
01RC1015A) is gratefully acknowledged.
poster
105
Introduction
Sodium acrylate is an important basic chemical that serves as a
monomer for the synthesis of polyacrylates. Those are frequently
utilized as superabsorber polymers in many consumer products.
The current process utilized for the synthesis of acrylic acid is
based on the two-step oxidation of propylene.
The direct synthesis of acrylates from CO2 and alkenes is
considered to be a dream reaction. In spite of huge effort [1,2], this
dream has not come true until recently. [3]
Synthesis of Nickelalactones
Almost 40 years ago Hoberg observed that carbon dioxide and ethylene could undergo
oxidative coupling reaction to give nickelactones. [1]
L
L +
Ni(COD)2
CO2 +
15 bar
C2H4
30 bar
78 oC to 40 oC
90h, THF
L: DBU, Py
Ni
O
O
OH
O
We have systematically studied the influence of bidentate ligands on the Ni-catalyzed oxidative
coupling of ethylene with CO2.
C2H4 2 bar
Ni(COD)2
R2P
R2
P
Ni
P O
nR
2
CO2 6 bar
PR2
THF
1a - 6a
Entry
ligand
Yield 1a-6a
(%)
1b-6b
(%)
1c-6c
(%)
0
dppm
Ph
dppe
Ph
65
dppp
Ph
24
dt bpm
tBu
60
40
dt bpe
tBu
35
62
dt bpp
tBu
97
Ph
P Ph
tBu
P tBu
P Ph
Ph
dppp
P tBu
tBu
dtbpp
+
O
R2
P
Ni
P
R2
+
n
1b - 6b
R2 R2
P P
Ni
P P
R2 R2
1c - 6c
Bulky
residues
on
the
phosphorous (e.g. tBu) promote
the oxidative coupling and
prevent coordinative saturation
of the metal as non reactive
tetrakis phosphino complexes
(1c-6c).
Decomposition
Nickelalactone
pressure.
of
dtbpm
without
CO2
Ph
P Ph
tBu
P tBu
Ph
P Ph
tBu
P tBu
P Ph
Ph
P tBu
tBu
P Ph
Ph
P tBu
tBu
dppe
dtbpe
dppm
dtbpm
t Bu
2
Ni
P O
t Bu
2
Yield
P
P
t Bu
2
45 oC, PhCl
ONa
Ni
Yield
t Bu
2
5a
t Bu
2
ONa
Ni
t Bu
2
5d
Entry
Base
Time
Additives
Temperature
Yield (%)
NaOtBu
0.25
r.t
90
NaHMDS
0.25
r.t.
87
NaOMe
24
r.t.
50(70)
NaOH
24
70 oC
0 (70)
Na2CO3
72
70 oC
NBu4OMe
72
50 oC
NBu4OMe
72
NaBARF
50 oC
50
DBU
72
70 oC
DBU
72
NaBARF
70 oC
10
P1
72
50 oC
11
P1
72
NaBARF
50 oC
50
Catalytic Process
Strong bases irreversibly form half-esters with carbon dioxide. [4]
ROM
CO2
RO
.
In order to avoid this side reaction, the one-pot process was divided into
OM
two stages, varying the pressure of carbon dioxide.
Using this procedure a TON of 10.2 ! was obtained, proving the catalytic character of the reaction. [3]
Ni(dtbpe)(ethylene)
Ni(dtbpe)(nickelalactone)
References
[1] Hoberg, H.; Peres, Y.; Krger, C.; Tsay, Y.H. Angew. Chem. Int. Ed. 1987, 26, 771-773.
[2] Fischer, R.; Langer, J.; Malassa, A.; Walther, D.; Grls, H.; Vaughan, G. Chem. Commun. 2006, 23, 2510-2512.
[3] Lejkowski M.; Lindner, R.; Kageyama, T.; Bdizs, G.E.; Plessow, P.N.; Schfer, A.; Mller, I.B.; Rominger, F.; Hofmann, P.; Futter, C.; Schunk, S.A.; Limbach, M. Chem. Eur. J., 2012, 18, 14017-14025.
[4] Behrend, W.; Gattow, G.; Drger, M. Z. Anorg. Allg. Chem. 1973, 397, 237-246.
Acknowledgement
NH, IJ, CS, AK, MB, AG, PA, TK, and RL work at CaRLa of Heidelberg University, being co-financed by University of Heidelberg, the state of Baden-Wrttemberg and BASF SE. Support from these institutions and financial
support from the BMBF (Chemische Prozesse und stoffliche Nutzung von CO2 : Technologien fr Nachhaltigkeit und Klimaschutz, grant 01RC1015A) is gratefully acknowledged.
106
poster
Motivation
CO2-Emissions1)
3,000
2,500
2,000
Utilization of CO2
Energy efficient processes (e.g.
photocatalytic reactions) to avoid CO2Emissions
/mt
Butadiene
Isobutene
1,500
1,000
Butane
500
Year
1) Energy data - National and international development, Federal ministry of Economics and Technology, May 2013
Valery
1
Photocatalytic Dehydrogenation
200
Yield [%]
50
40
150
40.0
30
20
16.5
19.7
-21%
165
130
100
14.6
10
0
C12H26
Partners:
80
60
82
87
Literature4)
New system
0
T [C]
98
20
C8H18
90
40
50
9.4
100
total yield
[%]
Oxo yield
4) Tominaga et al. Chem. Lett. 1994
[%]
poster
107
- TECHNISCHE CHEMIE
PhotoKat
Entwicklung aktiver und selektiver heterogener
Photokatalysatoren fr die Reduktion von CO2 zu C1Basischemikalien
Jennifer Strunk
Ruhr-Universitt Bochum, 44801 Bochum
H
O
SiO2
H
O
Ti
or
TiO2
Si
SiO2
60
Sn(1.0)/TiO2
Sn(1.5)/TiO2
Ti/SBA-15
Au/Ti/SBA-15
self-trapped excitons
CH4-Ausbeute [ppm]
surface states
20
10
5h
1h
0h
7h
5h
1h
XPS
5 5
Relative
Intensitt
x 10
Rel. intensity
x 10
2000
1000
Ti0.3/SBA
Ti1.0/SBA
Ti2.0/SBA
Ti2.7/SBA
30
60
90
150
120
CO2
c)
1.5
a)
Yield
CH4 [nmol/h]
CH
[nmol/h]
4-Ausbeute
CO 2 [%]
3.0
b)
-2-2
1.0
1.5
4+
Sn 5p
Anti-bonding
(Sn 5s O 2p)* + Sn 5p
1.0
0.5
Wenig Ti-O-Si
Au/Ti/Zn/SBA-15
180
20
40
60
80
100
16
CO2-Reduktion
14
12
10
nur Ti
8
6
Zn
2+
0.0
200 250 300 350 400 450 500 550 600 650 700 750 800
Znacac/T03
T03
ZnCub/T03
Temperatur
temperature[K]
[K]
ZnO-Spezies
SiO2
Schematische Darstellung des Graftings von ZnO: Isolierte
Spezies oder sehr kleine Cluster werden aus Zn(acac)2 erhalten,
grere Agglomerate werden ber ein Zinkkuban eingebracht.
O 2pz
Bonding
(Sn 5s O 2p)
10
-2
Bindungsenergie / eV
18
d)
0.5
0.5
Methylenblauzersetzung
2+
Time[min]
[min]
Zeit
TPD
3.5
1.0
Sn 5s
12
Au/Ti/SBA-15
Viel Ti-O-Si
1.5
4.5
2.0
0.5
0.0
Sn(1.5)/TiO2
unbehandelt
Untreated
reduziert@250
Reduced@250
reduziert@350
Reduced@350
Au/Zn/Ti/SBA-15
2.0
0.0
5.5 x 10-3
e)
5.0
2.5
H2-Entwicklung (H2O:CH3OH)
Sn
nm
Sn / nm
2.5
Si
Si
1.0
Relative CPS
Zeit [min]
SiO2
Si
7h
Zeit
Au
HOMO
2+
0h
TiO2
1.5
550
4+
30
2.0
0.0
400
450
500
Wellenlnge
nm
Wavelength // nm
4000
H2-Konzentration [ppm]
350
evacuation
Evakuierung
Metallisches Gold
negativ
Sn(0.5)/TiO2
50
Titanreiche Schale
Ti
O
e-
D/D+
positiv
PL
Sn(0.3)/TiO2
Metallgedichteter Gasphasenphotoreaktor;
(1) CF Flansche, (2) Vakuumfenster, (3)
VCR-Anschlsse, (4) doppelwandiger
Mantel, (5) Gitter als Unterlage fr
Probengef, (6) Anschlsse fr
Khlkreislauf.
h+
h+
Sn(0.1)/TiO2
Si
Si
i
[1]
Schematische Darstellung der Synthese des isolierten Titanats ber Grafting von Ti(O Pr)4 auf SiO2 . Schematische Darstellung
der isolierten Titanatspezies
40
e-
A/A-
eVB
Ti
LUMO
e-
e-
eh+
1,0
11day
Tagafter
nachreduction
Reduktion
0,8
two
weeks nach
after reduction
2
Wochen
Reduktion
0,6
(C0-C)/C0
H H
O O
H
O
or
OiPr
LB
Sn/TiO2
Intensity // a.u.
Intensitt
a.u.
OiPr
OH
iPrO
OiPr
Ti
Ti
Ti
Kalzinierung:
O O O
O OiPr
O
Ti(OiPr)4
300 C; N2
Toluol, Ar
500 C; O2/N2
SiO2
SiO2
PrO
eh
-1
Titanat/SBA-15
E
h
-1
H22-Entwicklung
H
evolution rate // mmol
mmol hh
Molekulare Photokatalysatoren
(am Beispiel von Titanat auf SiO 2)
Halbleitermaterialien
0,4
Anatas
AnataseTiO
TiO
2 2
0,2
Sn(1.5)/TiO
Sn(1.5)/TiO22
Anatas
Anatse TiO
TiO22 red@250
red@250
TiO2 red@250
Sn(1.5)/
Sn(1.5)TiO
2
0,0
0,0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
Bestrahlungszeit
Irradiation time / /hh
Schlussfolgerungen
Isolierte Titanatspezies auf SBA-15 sind aktiv in der photokatalytischen
Reduktion von CO2 zu Methan, obwohl keine Adsorption von CO2 am
Titanat gefunden wurde (ohne Bestrahlung).
Photoabscheidung von Goldnanopartikeln erhht die Ausbeute an
photokatalytisch gebildetem Methan.
Whrend der Photoabscheidung von Gold sind die Titanatspezies
mobil, und sie bilden eine Schale um die Goldnanopartikel.
Grafting von ZnO ermglicht CO2-Adsorption, aber nur agglomerierte
ZnO-Spezies erhhen die Methanausbeute.
4+
Das Grafting von Sn verbessert die Trennung der durch Anregung
erzeugten Ladungstrger, beeinflusst aber nicht die Lichtabsorption.
4+
Isolierte Sn -Spezies beschleunigen H2-Entwicklung aus CH3OH:H2O;
synergetischer Effekt mit photoabgeschiedenem Rh wird beobachtet.
Sn2+ Lochfangzentren auf der TiO2-Oberflche erhhen die Aktivitt des
TiO2 in der Methylenblauzersetzung.
Literatur
[1] B. Mei, A. Becerikli, A. Pougin, D. Heeskens, I. Sinev, W. Grnert, M. Muhler, J. Strunk, J. Phys. Chem. C 2012, 116, 14318 (und Ref. darin).
[2] B. Mei, A. Pougin, J. Strunk, J. Catal. 2013, 306, 184.
[3] B. Mei, Ch. Wiktor, S. Turner, A. Pougin, G. van Tendeloo, R.A. Fischer, M. Muhler, J. Strunk, ACS Catal. 2013, 3, 3041.
[4] A. Pougin, B. Mei, M. Dilla, I. Sinev, J. Strunk, wird eingereicht bei J. Catal. 2014.
[5] S. Chu, A.E. Becerikli, B. Bartlewski, F.E. Oropeza, J. Strunk, wird eingereicht bei Int. J. Hydrdogen Energy 2014.
[6] F. E. Oropeza, B. Mei, I. Sinev, A.E. Becerikli, M. Muhler, J. Strunk, Applied Catalysis B: Environmental 2013, 140-141, 51 (und Ref. darin).
Finanzierung
Gefrdert vom Bundesministerium fr Bildung und
Forschung (BMBF) im Rahmen der Frdermanahme:
Technologien fr Nachhaltigkeit und Klimaschutz Chemische Prozesse und Stoffliche Nutzung von CO2
(033RC1007A, Nachwuchsgruppe PhotoKat)
108
poster
Introduction
Acetone is an important raw material in the chemical industry as a solvent and for the syntheses of various
products, e.g. poly(methyl methacrylate) (PMMA), also known as acrylic glass. Today, acetone still is mainly
produced from fossil resources. However, future challenges require alternative strategies enabling the
generation of chemicals and biofuels from renewable resources, such as the usage of a greenhouse gas,
carbon dioxide (CO2), as a substrate.
Working with many different homoacetogenic microorganisms makes it necessary to create a vector system that
can be adapted to a broad range of them. Therefore, we developed a novel modular vector system for
homoacetogenic and/or thermophilic microorganisms. This offers the opportunity of easy and fast analysis of
the best combinations of origins of replication (GP), promoters upstream of the acetone operon (P) and the
acetone operons (AO) themselves. Therefore, we used unique restriction sites in front of each module type, to
allow a free exchange with other modules of this type.
1.
2.
3.
4.
5.
3 CO2 + 8 H2
Resistance gene
Ori
(Gram-positive)
Promotor
(Resistance gene)
Ori
Promotor
(Gram-negative)
(acetone-operon)
Acetone + 5 H2O
H2
CO2
1.
2.
3.
4.
Plasmid
CO2 is a less expensive feedstock, available in great quantities, and does not interfere with food production,
as glucose and other sugars do. Thus, the aim of the project CO2-based fermentation of acetone (funded
by the German Federal Ministry of Education and Research (BMBF)) is the development of a fermentation
process in which acetogenic bacteria produce acetone by using CO2 as starting material.
CO2 fixation and acetone formation
with genetically modified
acetogenic bacteria strains
GPA
GPB
GPC
GPD
GPE
1.
2.
3.
4.
PA
PB
PC
PD
Acetoneoperon
AOA
AOB
AOC
AOD
Fig. 2: Modular vector system for homoacetogenic and/or thermophilic microorganisms. Each arrow
represents one exchangeable module type. The Gram-positive origin of replication is indicated in red, the
promoter for the acetone operon is indicated in dark blue and the acetone operon is indicated in light blue.
Acetogens and
the Wood-Ljungdahl pathway
Acetogenic bacteria (acetogens) are
anaerobes that use the WoodLjungdahl
pathway to (I) synthesize acetyl-CoA by the
reduction of CO2 or CO + H2 (II) conserve
energy and (III) assimilate CO2 for the
synthesis of cell carbon [1].
The Wood-Ljungdahl pathway (Fig. 1) is
found in a broad range of phylogenetic
classes. Until now, 22 genera are known for
harboring acetogens. [2, 3].
Thus, acetogens bear a great potential for the
autotrophic production of bulk chemicals and
the industrial interest has risen dramatically.
Although more than 100 acetogenic bacterial
species are isolated and described so far,
there is little knowledge about their
applicability as production strains. Therefore,
we screened different acetogenic strains,
enabling the application of a synthetic
industrial waste gas stream simulating a
potential future biotechnological application.
2,0
2,5
1,20
1,00
2,0
1,6
Acetone concentration
0,8
0,80
Acetone concentration
1,2
1,5
0,60
1,0
0,40
2
0,4
0,5
0,20
0,0
100
200
300
400
500
600
700
800
0,0
50
acetone
strainstrain
acetonemesophilic
thermophilic
100
150
200
250
300
0,00
acetone
acetonemesophilic strain
Fig. 3: Growth and acetone production of recombinant thermophilic and mesophilic autotrophic
recombinant acetogens with H2 + CO2 as substrate. (a) cultivated in flask (b) cultivated in 2 L
stirred tank reactors
poster
109
Introduction
Subject
The impact of CO2 emission on global warming and the various CO2 management
strategies are topic of current social, political as well as scientific discussions.[1]
With carbon capture and utilization (CCU) there is a reconsideration of the
frequently discussed carbon capture and storage (CCS) strategy, considering
CO2 rather as an economical and abundant raw material than as waste.[2]
Consequently, the conversion of the CO2 into value added products is widely
studied in current research.[3] One promising approach for the utilization of CO2 as
a chemical building block is the incorporation into novel polymeric materials. In
recent years significant progress has been made in the field of epoxide based
polymers.[4] In contrast the use of alternative comonomers such as formaldehyde
was more or less neglected and only a very few examples are known.[5] The
development of novel CO2 based materials remain a challenging and up-to-date
research objective. We focus on the organocatalyzed copolymerization of CO2
and formaldehyde employing paraformaldehyde as the premonomer.
Results
weight loss
CO2
C=O vibration
CH2O
OAc
Aim
carbonyl region
Oligomeric material
confirmed by GPC
Oligomeric material
confirmed by MALDI-TOF
The great advantages of this novel material are on the one hand the theoretically possible high CO2 incorporation of up to 60 wt%. On the other hand, formaldehyde
can be obtained from renewable resources. As a result the new polymer is 100% based on renewable ressources and the carbon footprint is expected to be
extraordinary low. Initial experiments led to novel oligomeric materials. Furthermore, the effects of the reaction parameters including reaction time, pressure and
temperature as well as the nature of the catalyst on the composition and molecular weight distribution were studied. So far the obtained copolymers were
characterized by GPC, TGA/MS and IR methods. The properties of the new materials are not fully explored yet, but are subject of current investigations.
References
[1] a) Positionspapier, Verwertung und Speicherung von CO2, Verband der Chemischen Industrie e.V. (VCI), Gesellschaft fr Chemische Technik und Biotechnologie
e.V. (DECHEMA), 2009. b) G. A. Olah, G. K. S. Prakash, A. Goeppert, J. Am. Chem. Soc. 2011, 133, 1288112898. [2] a) M. Peters, B. Khler, W. Kuckshinrichs, W.
Leitner, P. Markewitz, T. E. Mller, ChemSusChem 2011, 4, 12161240. b) A. J. Hunt, E. H. K. Sin, R. Marriott, J. H. Clark, ChemSusChem 2010, 3, 306322. [3] M.
Aresta, A. Dibenedetto, Dalton Trans. 2007, 29752992. [4] D. Darensbourg, S. J. Wilson, Green Chem. 2012, 14, 26652671. [5] R. K. Sharma, E. S. Olson, Abstr.
Pap. Am. Chem. Soc. 2000, 45, 676680
Leibniz-Institut
fr Katalyse e.V.
Leibniz-Institut fr Katalyse e.V.
(LIKAT
(LIKAT Rostock)
Rostock)
Albert-Einstein-Str. 2929
A a
Albert-Einstein-Str.
18059 Rostock
18059
Rostock
www.catalysis.de
[email protected]
110
poster
Carboxylation of Acetophenone
Imidazolium-2-carboxylates can be utilized as precursors for
ligands in metalorganic chemistry, whereas the captured carbon
dioxide is released. According to Tommasi et al. the sodium salt of
3-phenylpropionic acid was generated by dimethylimidazolium-2carboxylate starting from acetophenone.[8] As mentioned above we
are interested in setting up a catalytic cycle to apply imidazolium
Entry
NaX
Solvent
Bu
NaBF4
THF
Bu
NaBPh4
THF
Yield [%]
Bu
NaI
THF
Bu
NaBF4
CH3CN
Bu
NaI
CH3CN
Me
NaBF4
THF
Me
NaBPh4
THF
Me
NaBF4
CH3CN
Me
NaBPh4
CH3CN
Summary
Imidazolium-2-carboxylates were readily synthesized either by deprotonating the imidazolium salt and subsequent conversion with carbon dioxide
or by direct conversion with dimethylcarbonate. Unfortunately, the synthesis of the 3-phenylpropionate starting from acetophenone was not yet
accomplished by stoichiometric amounts of the imidazolium-2-carboxylates. The conversion of acetophenone to the desired product was
performed by a two-step synthesis in moderate yields. The conversion of the sodium salt to the corresponding methylester could be achieved in
moderate yields by applying Meerwein salt.
Leibniz-Institut
fr Katalyse e.V.
Leibniz-Institut fr Katalyse e.V.
(LIKAT
(LIKAT Rostock)
Rostock)
Albert-Einstein-Str. 2929
A a
Albert-Einstein-Str.
18059 Rostock
18059
ROSTOCK
www.catalysis.de
[email protected]
poster
Department of Interface
Chemistry and Surface
Engineering
Prof. Dr. M. Stratmann
111
Electrocatalysis Group
Dr. K.J.J. Mayrhofer
Motivation
Wind and solar renewable electricity surplus can be applied for conversion of carbon dioxide
into hydrocarbons by means of electrolysis. Generated hydrocarbons can be used as fuel or as
valuable feedstock for the chemical industry. In the most general case, main
electrochemical reactions will be cathodic CO2 reduction and
anodic water oxidation. Overall cell efficiency, thus, will
depend on the activity of electrocatalysts applied for both
reactions. Moreover, economic viability will be evaluated by
the original catalyst price and the cell operation time. The
latter parameter can be predicted by detailed stability
investigation part of which is shown in the current work.
1 Figure
caption
Dissolution of model nobleFig.
metal
catalysts
For all studied noble metals surface oxidation
and reduction results in dissolution;
PtX+
PtX+
PtX+
PtX+
PtX+
PtX+
PtX+
ICP-MS
NexION 300X
Time resolved dissolution profiles
with low detection limit by ICP-MS
(less than 10 ppt);
Ar
Ar
Automated
synchronization
of Silicon sealing
electrochemical
and
downstream
Working electrode 2mm
analytics datasets;
Schematic representation: a) ICP-MS; b)
CAD-model illustrating the experimental setup of
Local micro-electrochemistry on
the SFC2,3, including the electrodes, force sensor,
electrode areas below mm;
and indicating gas and electrolyte flow;
Max-Planck-Institut fr
Eisenforschung GmbH
Dsseldorf/Germany
Parallel
activity
determination
and
monitoring of degradation rate with respect to
material composition;4
and
parameter
References
[1] Topalov, A. A.; Katsounaros, I.; Meier, J. C.; Klemm, S. O.; Mayrhofer, K. J. J.; Rev. Sci.
Instrum. 82 (2011), art. no. 114103, doi:10.1063/1.3660814
[2] Klemm, S. O.; Topalov, A. A.; Laska, C. A.; Mayrhofer, K. J. J.; Electrochem. Commun. 13
(2011), 15331535, doi:10.1016/j.elecom.2011.10.017
[3] Cherevko, S.; Topalov, A. A.; Katsounaros, I.; Mayrhofer, K. J. J.; Electrochem. Commun.
28 (2013), 44-46, doi: 10.1016/j.elecom.2012.11.040
[4] Schuppert, A. K.; Topalov, A. A.; Savan, A.; Ludwig, A.; Mayrhofer, K. J. J.
ChemElectroChem Communications 1 (2013), 358361, doi:10.1002/celc.201300078
[5] Zeradjanin A.R.; Topalov A.A.; Van Oveermere Q.; Cherevko S.; Chen X.; Ventosa E.;
Schuhmann W.; Mayrhofer K.J.J.; RSC Adv. 4 (2014) 9579-9587, doi: 10.1039/c3ra45998e
The unique coupling of the mass spectrometry and electrochemistry has already proven to
be a powerful technique for the parallel investigation of stability and activity of single- and multicomponent systems. Fundamental issues of electrode material dissolution, both noble and nonnoble, can be addressed on a new level. The example of noble metals shows the sensitivity of
detecting dissolution of sub-monolayer amounts. Furthermore, the correlation between the
potential and dissolution profile for more complex systems like the gradient PtCu alloys provide a
closer look for instance into dealloying phenomena. Additionally, setup was shown to be useful
for the analysis of porous samples with industrial relevance.
Acknowledgement
We acknowledge the Bundesministerium fr Bildung und Forschung (Kz:033RC1101A) for
financial support.
112
poster
Department of Interface
Chemistry and Surface
Engineering
Prof. Dr. M. Stratmann
Electrocatalysis Group
Max-Planck-Institut fr
Eisenforschung GmbH
Dsseldorf/Germany
Introduction
The strategy for the efficient conversion of CO2 into useful products (methanol, methane) can have multilateral significance, but still represents a serious scientific and technical challenge. The
conversion of CO2 at the electrochemical interface has some distinct advantages: 1) operation at ambient conditions 2) flexible control of reaction rate by the electrode potential 3) rather straightforward
separation of the products. The priority task is to design catalytic materials (electrocatalysts) which will allow high rate of electrode reaction with acceptable selectivity and sufficient stability. After
coupling a scanning flow cell (SFC) to an inductively-coupled-plasma mass spectrometer (ICP-MS) for stability investigations, we now coupled a differential electrochemical mass spectrometer (DEMS)
to the SFC for studying selectivity. [1][2]
Alloys
are
promising
cathode
materials
to
overcome challenges.
Motivation
Operation
Conditions
Voltage/Current
Technique
Temperature
...
Electrode Material
Composition
Morphology
Roughness
...
SFC-DEMS
Electrolyte
pH
Ionic concentration
Impurities
...
valve
mass
spectrometer
pre-pump
Hydrogen evolution
Reproducibility
Acknowledgement
We acknowledge the Bundesministerium fr Bildung und Forschung
(Kz:033RC1101A) for financial support.
References
[1] Hori, Y., K. Kikuchi, et al. (1985). Chemistry Letters 14(11): 1695-1698.
[2] Hori, Y. (2008). Modern Aspects of Electrochemistry. C. Vayenas, R. White and M.
Gamboa-Aldeco, Springer New York. 42: 89-189.
[3] Klemm, S. O.; Topalov, A. A.; Laska, C. A.; Mayrhofer, K. J. J.; Electrochem. Commun. 13
(2011), 15331535, doi:10.1016/j.elecom.2011.10.017
[4] Topalov, A. A.; Katsounaros, I.; Meier, J. C.; Klemm, S. O.; Mayrhofer, K. J. J.; Rev. Sci.
Instrum. 82 (2011), art. no. 114103, doi:10.1063/1.3660814
[5] Schuppert, A. K.; Topalov, A. A.; Katsounaros, I.; Klemm, S. O.; Mayrhofer, K. J. J., J.
Electrochem. Soc. (in press) (2012), doi: 10.1149/2.009211jes
The successful coupling between Scanning Flow Cell and ICP-MS enabled us to investigate
the stability of some important electrode materials like ruthenium oxide. The microstructured
surfaces lower overpotentials and increase stability and are therefore an interesting candidate for
counter electrodes in CO2 reduction.
First measurements with the SFC coupled to the DEMS show characteristic behavior during
hydrogen evolution and CO2 reduction on copper electrodes. Further investigations will concern the
production of hydrocarbons and alcohols on various electrodes during electrolysis in an CO2
saturated electrolyte.
The focus will be set on Cu electrodes alloyed for
example with Ni, Co, Ag or Au.
Special alloy electrodes with a concentration
gradient will be used5
Alloys are prepared by Prof. Ludwig, RuhrUniversitt Bochum, Institute of Materials,
Faculty of Mechanical Engineering
poster
113
4. Statuskonferenz der BMBF-Frdermanahme "Technologien fr Nachhaltigkeit und Klimaschutz - Chemische Prozesse und stoffliche Nutzung von CO2"
08. April 2014, Steigenberger Grandhotel Petersberg, Knigswinter
3 Jahre
01.07.2013
9,2 Mio.
033RC1301
Gefrdert vom
Konzept FfPaG
BMBF Projekt
CO2
100 TNm3/h *
Zielsetzung
Energie
Pyrolyse
(CH4 2 H2 + C)
Formulierung
Erdgas
C-Produkte
Kohlenstoff
36 t/h *
Basischemikalien
Kraftstoffe
Kompetenzen im Konsortium
Chemische Industrie
Synthesegas
Wasserstoff
Stahlindustrie
Kokskohle Blend
Einblaskohle
300.000 t/a *
Hochofen
Herausforderungen
Pyrolyse
Hochtemperaturprozess
Energieeintrag
Wrmeintegration
Gasaufreinigung
Spezifikation Kohlenstoff
Feststoffhandling
Werkstoffe
CO2-Aktivierung
Aktivmassen
Stabilitt
Prozessfhrung
Wrmeintegration
Werkstoffe
CO2-Quelle
Branchenbergreifende Zusammenarbeit
Stahlindustrie
Quelle: TKSE
(http://www.de.stratus.com/Uber_Uns/Anwenderberichte/ThyssenKruppSteelAG)
Anlagenbau
Chemieindustrie
Gaseindustrie
Kokerei
114
poster
Motivation
Ziel des Projektes ist die Entwicklung eines einstufigen, heterogen
katalysierten Verfahrens zur Synthese von Dimethylether (DME).
Das Verfahren soll stofflich und energetisch in die vorgelagerte
Synthesegasstufe integriert sein und die stoffliche Nutzung von
CO2 ermglichen.
Integriertes Verfahrenskonzept
Katalysator-Screening
Stand der Technik: zweistufige DME Synthese ber die Zwischenstufe Methanol
Problem: starke Umsatzlimitierung durch
75
MeOH
das thermodynamische Gleichgewicht
Neues Verfahren: einstufige DME Synthe50
se erhht den Gleichgewichtsumsatz durch
56 %
die unmittelbare Folgereaktion zu DME
25
Benchmark: Vergleich beider Prozesse
auf einheitlicher Basis mit kommerziellen
p = 50 bar
und proprietren Prozesssimulatoren
0
200
250
300
Ergebnis: signifikante Verbesserung von
Temperatur in C
Kaltgaseffizienz und spezifischer CO2
Thermodynamischer Gleichgewichtsumsatz von Wasserstoff fr DME- und Methanolsynthese als Funktion der
Emissionen pro Tonne DME gegenber
Temperatur bei einem Druck von p = 50 bar. AusgangsStand der Technik
punkt sind jeweils stchiometrische Gemische; fr DME
100
Umsatz in %
DME
91 %
Reaktionsmechanismus
Differentialkreislaufreaktor
vom Typ Berty
Starke Durchmischung des
Reaktionsraums
Verhalten nahe dem Modell
des idealen Rhrkessels
Gradientenfreie Vermessung der Reaktionskinetik
Kinetik dient als Grundlage
fr die Reaktorauslegung
Novel
Concept
Differentialkreislaufreaktor vom
Typ Berty (Linde)
Reaktor und
Katalysatorkorb (Linde)
Zusammenfassung
Die durchgefhrten Prozesssimulationen zeigen im Vergleich
zum Stand der Technik eine signifikante Verbesserung der
Kaltgaseffizienz und der spezifischen CO2 Emissionen. Mehrere
hundert Katalysatoren fr die direkte DME Synthese wurden im
Hochdurchsatzverfahren analysiert. Besonders aktive und stabile
Formulierungen werden zur Bestimmung kinetischer Daten
fr die Reaktorauslegung verwendet. Das Langzeitverhalten
des Katalysators wird im Festbettreaktor als Formkrper und
im Slurry Verfahren als Dispersion unter industriell relevanten
Rahmenbedingungen untersucht.
DMEEXCO2
www.apt.mw.tum.de
www.chemieundco2.de
c APT 2014
www.apt.mw.tum.de