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2015 Fall

Materials and devices for energy and environment applications

B

Materials for CO2 capture and storage

Advanced functional materials for CO2 capture and storages (CCS) exhibit great potential for the new solutions of “the Grand Challenges to World”, as it lies in the crossing point of climate change and energy shortage. The development of high efficiency, low-cost CCS materials and related techniques is the cornerstone towards the goal. There are a lot of efforts over the world to consider carbon dioxide not only as a waste from combustion processes influencing the climate changing, but as a useful source of carbon, to produce, e.g. synfuel, methane, or methanol. However, the first step in all these processes should be a capture of CO2 and for that some liquid, membrane or solid sorbent are necessary.

Scope:

The scope of the symposium includes the mechanism, fabrication and applications of functional materials applied for carbon dioxide capture and storage (CCS). The idea of CCS is as follows: when large production facilities such as coal plants and steel mills produce carbon dioxide, the CO2 gases are immediately separated from the other components in the flue gas. The CO2 gas is then compressed into a liquid and transported to its final destination via pipeline or a vehicle. The carbon dioxide has then to be injected into rock formations far beneath the surface for long term storage. Alternatively, carbon dioxide can be transferred into useful products e.g. via photocatalysis or photosynthesis.

Nowadays CCS technology exist, however the current costs level is the only constraint to capturing carbon dioxide. The novel highly efficient materials which will reduce CCS energy consumption and then the price of CO2 capture are required to alleviate this problem.

During the symposium the updated state of CCS technologies, the economical issues and CCS legislation worldwide will be discussed. The main focus of the symposium will be novel materials which are cheap, selective toward CO2 that can be used in energy efficient processes. Such materials are not only useful for CCS application but also for classical chemistry processes like syngas purification where amine technologies may become obsolete.

There will be presented working pilot CCS installations like one in power plant in Łaziska (Poland).

The challenges of CCS technology in the frame of European energetic security, environmental impact, enhancement of public and political awareness will be discussed.

Hot topics to be covered by the symposium:

 

  • Economic and legal issues of CO2 emission
  • Materials for CO2 capture and storage
  • Zeolites as adsorbents for CO2
  • Processes for CO2 capture and storage
  • Post combustion capture on solids in moving bed reactors
  • Capture of CO2 on porous rocks
  • Shale gas and CO2
  • New solvents for CO2 absorption
  • Catalysts for CO2 processing

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Session 1 : -
08:30
Authors : R. Martins
Affiliations : FCT/UNL, Portugal

Resume : General Introduction of Symposium B "Material for CO2 capture & storage"

B.1.1
09:00
Authors : Koji Hashimoto, Naokazu Kumagai*, Koichi Izumiya*, Hiroyuki Takano*, Hiroyuki Shinomiya*, Yusuke Sasaki*, Tetsuya Yoshida* and Zenta Kato
Affiliations : Tohoku Institute of Technology, Sendai, 982-8577 Japan *Hitachi Zosen Corporation, Kashiwa, 277-8515 Japan

Resume : An increase in the world energy consumption at the current rate will lead to complete exhaustion of world fossil fuels and uranium until the middle of this century. In order to avoid the crisis of no fuels and intolerable global warming, we have been proposing and studying ?global carbon dioxide recycling? since more than 2 decades ago. In global carbon dioxide recycling we supply remote intermittent renewable energy to the world in the form of methane via electrolytic hydrogen generation by using carbon dioxide as a feedstock. For realization of global carbon dioxide recycling, we needed to establish the technologies of electrolytic hydrogen generation and methane synthesis by the reaction of hydrogen with carbon dioxide captured from chimney. We created active cathodes for hydrogen production and anodes for oxygen formation without forming chlorine even in direct seawater electrolysis. However, because the energy efficiency of direct seawater electrolysis is not sufficiently high, for immediate industrialization we adopted alkali water electrolysis and created active cathode and anode by electrodeposition for alkali water electrolysis. We also created remarkably active catalyst with almost 100% selectivity of methane formation by the reaction of CO2 4H2 = CH4 2H2O from amorphous Ni-Zr alloys. Using the knowledge obtained from the study of catalyst formed from amorphous alloy precursors we established the mass production method of the catalysts. Based on the creation of key materials we constructed a prototype plant of global carbon dioxide recycling in 1995 and industrial scale plants in 2003, and joint R & D work for industrial applications is in progress since 2011 with Japanese and foreign companies. The establishment of renewable energy storage in the form of methane is the most effective support for German effort to realize the country to use electricity generated only from renewable energy by 2050.

B.1.2
09:30
Authors : Lucyna Więcław-Solny. Marek Ściązko. Stanisław Tokarski. Adam Tatarczuk. Marcin Stec. Aleksander Krótki. Andrzej Wilk.
Affiliations : Institute for Chemical Processing of Coal

Resume : The present document reports on advanced operation and presents general results achieved during the largest post-combustion carbon capture project in Poland, carried out at two Tauron’s objects. Institute for Chemical Processing of Coal in cooperation with TAURON Polska Energia S.A. and TAURON Wytwarzanie S.A. designed, erected and operated 1,2 CO2 TPD mobile pilot plant. The flow sheet modification and using AMP/PZ solvent, allowed reaching CO2 recovery about 90% with the energy demand about 3,3 MJ/kgCO2 during campaigns at the Jaworzno Power Plant in 2014. The measurements are compared with results of a 30%(wt) MEA aqueous solution achieved at the Łaziska Power Plant in 2013. Novel construction of the stripper was verified during the test campaigns. The reduction in the reboiler heat duty for modified process during presented trials ranges from 8 to 11 % with higher CO2 recovery from 8 to 12 %. Since 2013 the pilot plant has been operated for >1400 h and successfully demonstrated reliable operation allowing the removal of over 55 000 kg of CO2 from flue gases using amine scrubbing process. The tests provided valuable experimental evidence for flow sheet modification like heat-integrated stripper, described in the literature mainly through modelling. Acquired data and operational experience will allow CO2 capture units optimization and will be useful for scaling-up amine scrubbing CO2 capture plants.

B.1.3
10:00
Authors : Andy Booth
Affiliations : SINTEF Materials and Chemistry

Resume : Owing to their specific material properties, solid sorbents engineered at the nano-scale have been subject to increasing attention. Whilst bulk materials exhibiting nano-scale structures are less likely to find their way into the environment, nano-sized particulate materials (NMs) are known to be released at different stages of their life cycle (e.g. production, application and waste processing). Many NMs elicit negative impacts on a range of freshwater, marine and soil organisms. However, understanding NM environmental fate and behaviour is necessary to assess the potential for exposure and risk. A simple strategy for the assessment of NM fate and behaviour in freshwater environments, and how this can be used for selecting relevant species for further toxicity (hazard) evaluation towards risk assessment, is presented. Ten carbon nanotubes (CNTs) and 3 TiO2 NMs representing candidate solid nano-sorbent materials for potential application in CO2 capture technology were selected. Studies have been conducted to investigate how physicochemical properties influence NM dispersability (concentration) and dispersion stability in aqueous media relevant to freshwater environments. A standard method for the dispersion of NMs in aquatic media has been developed to permit reproducible and comparable conditions for different test materials. A basic strategy for using such environmental data in a 'Safe by Design' approach to material development and selection will also be outlined.

B.1.4
10:20
Authors : U. Narkiewicz, R.J. Wrobel, A. W. Morawski, B. Michalkiewicz
Affiliations : West Pomeranian University of Technology, Szczecin

Resume : A decrease of the carbon dioxide emission has recently became one of global challenges, because of the impact on climate changes. Fossil fuel power plants are the main source of anthropogenic CO2 emissions, however industrial production plants are also the important contributors. The existing processes used for post combustion CO2 capture are based mainly on absorption in liquids are expensive, inefficient and may have inherent environmental problems, then there is a need to develop new solutions. Solid sorbents can be used in such processes, instead of traditional liquids. In the lecture a review of solid sorbents will be presented, followed by a presentation of results obtained recently in our laboratory. Acknowledgement The studies presented in the lecture were performed within the framework of Project Contract No Pol-Nor/237761/98/2014 funded from the Polish-Norwegian Research Programme operated by the National Centre for Research and Development under the Norwegian Financial Mechanism 2009-2014

B.1.5
10:40 Coffee Break    
 
Session 2 : -
11:00
Authors : Marcin Broda, Agnieszka M. Kierzkowska, Andac Armutlulu, Christoph R. Müller
Affiliations : ETH Zürich

Resume : One option to mitigate climate change is CO2 capture and storage (CCS). Here, CO2 is captured from large point sources, e.g. power plants, compressed, transported and stored in suitable geological formations. However, the cost of CO2 capture using amine based scrubbing technologies are probably prohibitively expensive. Hence, there is an urgent need to develop more efficient and less costly CO2 capture technologies. An emerging CO2 capture technology is based on the carbonation and calcination of CaO and CaCO3, respectively, i.e. CaO + CO2 ↔ CaCO3. This CO2 capture technology is commonly referred to as calcium looping. Economic analyses show that such a process is economically attractive, in particular due to the higher operating temperatures and the use of relatively inexpensive, naturally occurring sorbents, e.g. limestone. However, limestone shows a rapid decrease in CO2 uptake with cycle number largely due to thermal sintering. However, the exact deactivation mechanism and the detailed carbonation mechanism are still largely unknown. In this presentation we introduce the current understanding of the carbonation and calcination reaction of CaO and CaCO3, respectively and describe our recent attempts to develop synthetic CaO-rich CO2 sorbents that surpass the CO2 uptake of limestone by a large extent.

B.2.1
11:20
Authors : Richard Blom
Affiliations : SINTEF

Resume : Processes that utilizes selective adsorption of CO2 onto the surface of high surface area powders has been suggested as a way to separate CO2 from flue gases having potentially much lower energy demand as compared to the present solvent based technologies. Traditional adsorbent materials such as Zeolites have high affinity towards CO2, but it also adsorbs trace amounts of water vapor that is normally present in flue gas. On the other hand, activated carbons (ACs) has less affinity towards water, but show very low adsorption capacity of CO2 at partial pressures typical for flue gases. Novel adsorbent materials such as metal-organic frameworks (MOFs) are much more versatile class of porous hybrid materials with significant possibility for tuning the adsorption properties through proper choice of inorganic and organic parts. Such materials couple the richness of organic substitution chemistry with the high number of inorganic metal and metal oxide cluster moieties available. MOFs can exhibit extreme surface areas which give high adsorption capacities, and, in principle, the selectivity can be tuned by choosing the right MOF composition. But is it so straightforward? In the present presentation, the status of MOF development will be discussed. In addition, the different low temperature separation process concepts suggested for the utilization of solid adsorbents will be discussed in light of the new adsorbent development. In the end the main challenges connected to the development of post-combustion adsorption processes will be addressed. The question then is; how can novel adsorbents boost these novel technologies, and what is needed to take out this potential? The questions will be discussed keeping a realistic view on the possibilities.

B.2.2
11:40
Authors : K. Glonek1, B. Ulejczyk2, K. Krawczyk2, U. Narkiewicz1, A. W. Morawski1, R. J. Wróbel1, B. Michalkiewicz1
Affiliations : 1West Pomeranian University of Technology, Institute of Chemical and Environment Engineering, ul. Pułaskiego 10, 70-322 Szczecin, Poland;2 Warsaw University of Technology, Faculty of Chemistry, ul. Noakowskiego 3, 00-664 Warsaw, Poland

Resume : Activated carbons were produced from coal (coal mine Wieczorek). The coal was mixed with KOH by the three different methods. Different amounts of KOH were used. The mixture was left for 3 h and then dried 19 h at 200oC. Then the carbonization was carried out at temperature range 650-850oC. The activating agent was removed by washing with water and HCl and water again. All the activated carbons were washed to pH=7. Textural properties of activated carbons were obtained based on the adsorption and desorption nitrogen at 77K. The specific surface areas of the activated carbon was calculated by the Brunauer-Emmett-Teller (BET) method. The volume of micropores was obtained by DFT method (density functional theory). Only micropore of diameter no higher than 2 nm were taken into consideration. Adsorption properties of activated carbons obtained were characterized by adsorption of CO2 at 0°C and pressure up to 1 bar. It was observed that the greater amount of KOH and the increase of the pyrolysis temperature increases the surface area and adsorption capacity of CO2. Activated carbons prepared from hard coal and KOH solution can be a very good CO2 adsorbents. Acknowledgement Project funded by the Norwegian funds. under the Polish-Norwegian Cooperation Research carried out by the National Centre for Research and Development. 2009-2014. No. Pol-Nor/237761/98/2014 .

B.2.3
 
Session 4 : -
12:00
Authors : Rafał J. Wróbel, Andżelika Gęsikiewicz, Michał Zgrzebnicki, Beata Michalkiewicz, Urszula Narkiewicz, Antoni W. Morawski
Affiliations : West Pomeranian University of Technology, Szczecin Inst. Chem. Env. Eng

Resume : The commercial activated carbons are relatively cheap sorbents for sequestration of CO2 from flue gases. However they are usually not shaped for CO2 adsorption capacity. In the course of communication the methods of treatments of commercial activated carbons will be presented which enables CO2 capacity enhancement. The probable mechanism of improvement will be discussed. Acknowledgement: The studies presented in the lecture were performed within the framework of Project Contract No Pol-Nor/237761/98/2014 funded from the Polish-Norwegian Research Programme operated by the National Centre for Research and Development under the Norwegian Financial Mechanism 2009-2014

B.4.1
12:20 Lunch    
 
Session 3 : -
14:00
Authors : Richard H. Heyn
Affiliations : SINTEF Materials and Chemistry

Resume : Research on carbon dioxide (CO2) utilization (CDU) has been gaining momentum over the past decade. While the motivation for this surge in interest may well be a response to the increasing levels of CO2 in the atmosphere and the need for mitigating CO2 emissions, the shear volumes of CO2 emitted and relatively modest contribution CDU can make toward mitigation of these emissions, at least in terms of chemical production volumes, strongly suggest that a more proper motivation is the development of CO2 as a sustainable C1 source for the chemical industry. Since CO2 is a thermodynamically and kinetically inert molecule, advances in catalysis and process engineering are necessary in order to overcome these barriers for the industrial implementation of CDU technologies. This talk will present some of the current options for the chemical utilization of CO2, specifically for the production of CO2-based polymers or CO2-derived monomers for polymerization. Our own research results as well as relevant literature examples will be highlighted. The focus will be on specific R&D challenges which need to be overcome, and how materials technology may be able to provide new opportunities for CDU.

B.3.1
14:25
Authors : Zhenshan Hou
Affiliations : Key Laboratory for Advanced Materials, Research Institute of Industrial Catalysis, East China University of Science and Technology, Shanghai, 200237, China

Resume : The use of carbon dioxide as a renewable and environmentally friendly source of carbon has attracted increasing attention. One of promising methodology in this area is the transformation of carbon dioxide into high value-added chemicals although a catalytic approach. In this presentation, I will summarize our group's recent work about CO2 utilization. In this aspect, I would like to introduce the peroxoniobates or supported ionic liquid catalyzed synthesis of cyclic carbonates from CO2 and epoxides, Mg-Al layered double hydroxide catalyzed the synthesis of disubstituted ureas from amines and CO2, and also Mn-doping CeO2 catalyzed the synthesis of aliphatic carbamate from CO2, amine and methanol.

B.3.2
14:50
Authors : Michał Zgrzebnicki, Rafał J. Wróbel, Andżelika Gęsikiewicz, Beata Michalkiewicz, Urszula Narkiewicz, Antoni W. Morawski
Affiliations : West Pomeranian University of Technology in Szczecin

Resume : It has been proven that some anthropogenic gases in the atmosphere, like CH4, chlorofluorocarbon (CFC or commonly known as freon) and CO2 have an influence on increasing each year average temperature – it is called the greenhouse effect. Due to increasing concentration of these gases in the air, new solid sorbents are being investigated, to reduce emissions, especially carbon dioxide emission, from industry, for instance power plants or chemical industry. Results will be presented for zeolites and activated carbons - for each virgin and modified materials. Zeolites , as sorbents for the purpose for CCS (Carbon Capture and Storage) Technology, were studied, especially their carbon dioxide sorption capacity. The data obtained by BET and thermogravimetry analysis indicated most quantities of adsorbed gas above 4 mmol/g and even several above 5 mmol/g. Modification was based on ionic exchange. Activated carbons, as sorbents, were on the other hand oxidized in the first step and in the next impregnated in solution of diethylenodiamine (DEA) or monoethanaloamine (MEA).

B.3.3
15:10
Authors : Brian Ray, Evangelos Papaioannou, Ian Metcalfe
Affiliations : Chemical Engineering and Advanced Materials, Newcastle University ; Chemical Engineering and Advanced Materials, Newcastle University ; Chemical Engineering and Advanced Materials, Newcastle University

Resume : Carbon dioxide membranes are a promising technology with applications from carbon dioxide capture to novel chemical synthesis methods. Dual phase membranes consisting of a molten salt held within a solid oxide porous support show permeation coupled with high selectivity, along with the ability to design membranes with large permeation areas and the inherent self-healing ability of the molten phase to fill cracks.[1] These membranes support a wide array of possible permeation pathways through tailoring the molten salt composition as well as the supporting oxide composition.[2] Ambipolar diffusion means that carbon dioxide can even be driven uphill with enough of a driving force in the second permeable species.[3] One recent mechanism that is promising is steam-assisted carbon dioxide permeation in a porous oxide support with molten eutectic alkali carbonates where steam is fed on the permeate side and carbon dioxide on the feed side.[4] Here, we investigate the proposed mechanism by looking at the permeation rate of carbon dioxide with steam on either the feed and/or permeate side coupled with the composition of the molten salt and support, in these different environments via TGA, Raman spectrometry, and XRD. [1] Wade, Lackner, West”, Solid State Ionics, 178, 1530-40, 2007 [2] Zhang, Papaioannou, Metcalfe, Energy Environ Sci, 8 1220-23, 2015 [3] Papaioannou, Qi, Metcalfe, J Mem Sci, 485, 87-93, 2015 [4] Xing, Peters, et.al., J Mem Sci, 482, 115-19, 2015

B.3.4
15:30 Coffee Break    
15:50
Authors : Alexandra Siklitckaya, Mateusz Wlazlo, Jacek A. Majewski
Affiliations : Faculty of Physics, University of Warsaw, ul. L. Pasteura 5, 02-093 Warszawa, Poland

Resume : Gas adsorption on organic substances is a subject of vivid interest in the field of carbon capture and storage (CCS). Shale formations are one of the prime candidates for carbon dioxide deposition because of potentially strong bonding, and carbon dioxide is thought to exhibit stronger adsorption to those structures than methane. Therefore, the process of CO2-CH4 exchange may enhance natural gas recovery from shales. We investigate adsorption processes of carbon dioxide and methane on hexagonal carbon systems modeled by graphene layers and the whole range of minerals such as CaCO3, CaO, MgO, kaolinite, and illite. Chemi- and physisorption energies are determined via density functional theory (DFT) plane-wave calculations. Car-Parrinello molecular dynamics (CPMD) simulations in the canonical (NTV) ensemble are employed to give insight into kinetics of adsorption in finite temperature. These calculations use norm-conserving and ultrasoft pseudopotentials and BLYP exchange-correlation functional with semi-empirical DFT-D2 dispersion correction to account for important van der Waals bonding. The performed calculations reveal interesting adsorption mechanisms. For example, it turns out that the CO2 molecule does not bind to the calcite surface at any temperatures, whereas we observe its chemisorption at the calcium oxide surface. The adsorption of CO2 and CH4 to graphene layer is stronger in the neighborhood of a defect then to carbon atoms in the pristine graphene.

B.2.4
16:10
Authors : Sanosh Kunjalukkal Padmanabhan1, Stefania De Santis2, Carlo Terreni2 , Notaro Maurizio3, Antonio Licciulli1
Affiliations : 1. Dipartimento di Ingegneria dell'Innovazione, Università del Salento,Lecce (Italy) 73100 2. INDUSTRIE BITOSSI S.p.A.,Divisione Ceramici Tecnici - Ricerca & Sviluppo Sovigliana VINCI (Italy) 50059 3. RSE SpA – Ricerca sul Sistema Energetico , Milano(Italy) 20134

Resume : Ceramic-supported amines CO2 adsorbents, are a promising class of adsorbents because they can be operated at low temperature (ambient to ∼120 °C) with high capture performance. The present work carried out to develop and demonstrate a novel type of solid sorbent based on ceramic supported amines with enhanced efficiency and functional characteristics. Alumino silicate monomodal ceramic spheres were prepared for by drip casting the slurry made with low cost smelter grade alumina and colloidal silica in the presence of Cetyl trimethylammonium bromide surfactant, (CTAB) and gelling agent sodium alginate to CaCl2 solution. The sorbent supports synthesized characterized by XRD, SEM, Hg porosimetry and N2 adsorption–desorption analysis. The supports show mesoporous structure with low density and high porosity values. These alumino silicate supports were properly impregnated with 36 wt% Diethanolamine (DEA) and tested for their CO2 adsorption and desorption properties in a fixed bed reactor at 40C. The alumino silicate with Si/Al ratio 5:1 shows maximum CO2 adsorption capacity of 40 mg/g. The absorption capability was confirmed after several cycles of testing.

B.4.2
16:30
Authors : Wen Xing1, Thijs Peters1, Marie-Laure Fontaine1, Rahul Anantharaman2, Anna Evans3, Truls Norby3, Rune Bredesen1
Affiliations : 1SINTEF Materials and Chemistry, NO-0314 Oslo Norway 2SINTEF Energy research, NO-7465 Trondheim Norway 3Department of Chemistry, University of Oslo, NO-0349 Oslo, Norway

Resume : One of the new possible approaches for reducing the cost of CO2 capture in the CCS chain is to utilize a membrane that can separate CO2 from pre- or post- combustion gases. Dual-phase CO2 separation membranes consisting of a molten carbonate phase in a solid matrix of an electron conducting metal or ion conducting ceramic, were found to be possible candidates in cost-effective CO2 capture and CO2 utilization technologies.Our recent work on modelling of a ~400 MW power plant integrated with such a dual-phase membrane for pre-combustion CO2 capture shows great potential with respect to the net electric efficiency as compared to the Selexol process with a comparable CO2 capture rate. The high temperature CO2 separation from pre- or post- combustion gas mixtures opens up for processes with an integrated CO2 conversion to useful chemicals.We have made dual-phase membranes with different solid matrix materials and suitable sealants to obtain different transport properties and up to 100% selectivity of CO2. CeO2-supported dual-phase membranes infiltrated with an eutectic mixture of Li2CO3 and K2CO3 were tested in our lab with respect to their CO2 separation performance and stability. The CO2 flux has been improved by optimization of the composition of the molten phase and the microstructure of the solid matrix under different operational conditions.

B.4.3
16:50
Authors : J. Młodzik, U. Narkiewicz, A. W. Morawski, R. J. Wróbel, B. Michalkiewicz
Affiliations : West Pomeranian University of Technology in Szczecin Institute of Inorganic Chemical Technology and Environmental Engineering

Resume : Activated Carbons (ACs) advantages are great surface area and well developed porous structure [1, 2, 3].According to our knowledge, it was used twice as carbon source for ACs [1, 3].Molasses based ACs arevery effective in CH4 capturing [1]. The aim of this research was to obtain ACs from molasses, with high surface area and well developed porous structure. Activation agent was solid KOH. Until this study H2SO4, and saturatedsolution of KOHwere used [1, 3]. Molasses, was mixed with solid KOHuntil homogeneous mass was obtained. Weight ratio, calculated for dry materials mass, was as follows (KOH/molasses): 0.4, 0.5, 0.8, 1, 1.2, 1.5. Mixturewas left for 3 hours at 25oC. Materials were dried for 12 hours at 200oC. After grounding, pyrolysis at different temperatures (600oC to 850oC) was performed, at constant flow (18 dm3/min) of N2. For materials with mass ratios other than 1:1 pyrolysis was performed at 750oC.Powder was washed with water until filtrate pH was neutral. Materials were soaked in HCl (0.1 mol/dm3) for 19 hours, and washed with water until pH of filtrate wasneutral. This method is a subject of polish pending patent no. P404248. Adsorption and desorption of nitrogen at -196oC was provided. Surface area (SBET) was calculated using BET equation. Micropore volume was calculated with DFT method. The highest SBET, and the highest pore volume were developed by sorbents observed in 750oC in mass ratio 1.5 (3000 m2/g). Adsorption of CO2 was performed at 0oC, 1bar. The highest uptake (5.47 mmol/g) was noticed for ACpyrolyzed at 750oC, KOH/molasses=1. Molasses is effective carbon source. Obtained ACs have high surface area, and well developed porous structure. Acknowledgment: Project funded by the Norwegian funds. under the Polish-Norwegian Cooperation Research carried out by the National Centre for Research and Development 2009-2014. nr Pol-Nor/237761/98/2014. Reference [1] J. Sreńscek-Nazzal, W. Kamińska, B. Michalkiewicz, Z. C. Koren, Industrial Crops and Products 47 (2013) 153– 159 [2] Ioannidou, O., Zabaniotou, A., 2007. Agricultural residues as precursors for activated carbon production – a review. Renew. Sustain. Energ. Rev. 11, 1966–2005. [3] Legrouri, K., Khouya, E., Ezzine, M., Hannache, H., Denoyel, R., Pallier, R., Naslain, R., 2005. Production of activated carbon from a new precursor molasses by activation with sulphuric acid. J. Hazard. Mater. B 118, 259–263 University Press, (2005)

B.4.4
17:10
Authors : Guohua Liu and Kaiying Wang
Affiliations : Department of Micro and Nano Systems Technology, Buskerud-Vestfold University College, Horten, 3184, Norway

Resume : Due to current energy and environmental challenges, TiO2 nanotubes (TNTs) are being promoted as functional material for energy and environmental applications. However, the nature of as-prepared TNTs adhered on opaque Ti foil restricts their feasibility for the intention applications such as tube filling, flow-through redox reactions. The TNT membranes with free-standing and flow-through morphology present even more interesting performance than that of nanotube layer on Ti foils. The advantages of TNT membranes lie on their optimized microstructure, direct electrons transferring, stability of mechanical vibrations and they can be integrated or attached on any foreign substrates. In this work, a handy experimental procedure was reported to fabricate free-standing crystalline TNT membranes. The ordered TNT arrays are firstly fabricated under optimized parameters, after an annealing and followed by a second (detachment) anodization step, free-standing crystalline TNT membranes are detached from the substrate without any cracks. We systematically investigated the effects of voltage on the detachment process of free-standing crystalline TNT membranes. It demonstrated that the membrane detached at low voltage preserves its nanotube morphology and the bottom of tubes are closed, while through-hole membrane with fast detachment can be obtained at a high detachment voltage. This method provides a reliable technique for fabricating free-standing TNT membranes without the needs for any complicated processes or dangerous chemicals, and all the resulting membranes feature high-quality surfaces. This approach opens new prospects for application in chemical treatment of CO2. Future perspective of our work will be focus on design of cascade-heterogeneously membrane catalysts to enhance light absorption and realize long lifetime of separated charge states for solar fuels.

B.B.1
17:10
Authors : Carlos A. Grande, Hanne Kvamsdal, Giorgia Mondino, Richard Blom
Affiliations : SINTEF

Resume : The use of solid adsorbents is an alternative approach which may alleviate many of the problems connected to the liquid absorption processes. On a solid adsorbent the adsorption sites are spatially separated on a carrier, thus avoiding possible chemical degradation through site interaction. The number of adsorption sites is in most cases dependent on the surface area of the carrier, and often a linear relationship exists between the adsorption capacity of an adsorbent and its specific surface area. In addition, a good solid adsorbent will be chemically and physically stable at the operating conditions giving negligible loss of volatiles and good recyclability. For post-combustion CO2 capture, both pressure swing adsorption (PSA or VSA) and temperature swing adsorption (TSA) processes have been suggested. However, for post-combustion CO2 capture in a natural gas fired power plant (NGCC) context, where the partial pressure of CO2 is small (typically around 4 vol%), regeneration with temperature swing may be more appropriate. In a TSA process, adsorption takes place at the lower temperature of the process. When the adsorbent is saturated, it is heated to the desorption temperature, releasing CO2 as shown in Figure 1. The amount of CO2 released depends on the adsorbent employed and on the regeneration temperature. The adsorbents to be used in a TSA process for CCS should have a strong affinity (steep adsorption isotherms) to CO2 at low partial pressures. The main advantage of this process is the utilization of heat as the energy input of the process. Main disadvantage is related to the productivity of such units since temperature changes (heating and cooling) in large fixed-bed columns can take several hours. However, it has been previously shown that fast-cycle thermal swing processes result in lower energetic demand. With the proper conditions for adsorption and regeneration, it is possible to envisage a process that can remove CO2 from flue gas stream and in a separate step, desorb it for further storage. For conventional fixed bed adsorption processes based on either pressure swing or temperature swing mechanisms one would expect a potentially high pressure drop over the adsorbent bed in addition to the slow heat transfer. The moving bed temperature swing adsorption (MBTSA) concept is one way to overcome the pressure drop challenge. Recently a MBTSA process has been suggested in which hot flue gas was used to indirectly heat the adsorbent during regeneration. Indirect heating was necessary since Zeolite 5A, having high water affinity, was used as adsorbent. However, considering the adsorbent development during the last years, other adsorbents should also be taken into consideration. Also SRI has reported results from the development of MBTSA process development using direct heating with steam during regeneration with activated carbon based adsorbents. The aim of the present paper is to discuss the feasibility of a MBTSA process in a NGCC context. Firstly, the possible design of such a reactor will be discussed. Secondly, some considerations concerning the choice of adsorbent will be done. And, finally, based on the chosen design, the adsorbent properties, and a number of more or less well funded estimated of the heat transfer parameters in the system, the energy penalty for CO2 capture by a MBTSA process has been derived. The results give direction to the research to be done for further development of the MBTSA concept.

B.B.3
17:10
Authors : Andy Booth, Berit Glomstad, Florian Zindler, Lisbet St?en, Dag Altin
Affiliations : SINTEF Materials & Chemistry, NTNU, NTNU, SINTEF Materials & Chemistry, BioTrix

Resume : In the present study, the influence of phenanthrene adsorption to aqueous dispersions of 5 different CNTs containing dissolved natural organic matter (NOM) was investigated on the bioavailability and subsequent ecotoxicity of dissolved phenanthrene to standard freshwater test species. The study employed the microalga Pseudokirchneriella subcapitata and the cladoceran water flea Daphnia magna which represent two different trophic levels. In addition, the direct ecotoxicity of the CNT suite was investigated with both species at environmentally realistic dispersion concentrations. A significant change in phenanthrene toxicity to P. subcapitata was only seen in the presence of one type of CNT (SWCNT) when considering total phenanthrene concentration in the system. However, based on the measured concentrations of phenanthrene in the water phase, an increase in toxicity in the presence of CNTs was observed relative to phenanthrene only. This indicates that not only the phenanthrene remaining in the water, but also the phenanthrene adsorbed to CNTs, is available to the algae. In the case of D. magna, adsorption to CNTs reduces overall bioavailability of phenanthrene for some CNT types. However, a significant proportion of adsorbed phenanthrene remains bioavailable. Microscopy images show significant ingestion of CNTs by D. magna, which may offer an alternative route for phenanthrene uptake and toxicity.

B.B.4
17:10
Authors : Andy Booth, Berit Glomstad
Affiliations : SINTEF Materials & Chemistry, NTNU

Resume : Knowledge of CNT fate in aqueous environments provides important information regarding their possible environmental impacts. The dispersion stability of carbon nanotubes (CNTs) in aqueous media and their interaction with dissolved polycyclic aromatic hydrocarbons (PAHs) was investigated. Five different CNTs, including one single walled carbon nanotube (SWCNT), two multi walled carbon nanotubes (MWCNT-2 and MWCNT-3) and two functionalised MWCNTs (MWCNT-OH and MWCNT-COOH) were dispersed in two types of media; moderately hard reconstituted water (MHRW) and OECD algae growth media (TG 201). Stock solutions (100 mg/L) were prepared by adding CNTs to appropriate media containing Suwannee River natural organic matter (SR-NOM; 20 mg/L) and sonicated. The dispersion stability and settling of the CNTs in the two media was determined both in the absence and presence of SR-NOM (20 mg/L) by measuring the concentration of CNTs in the water phase over a period of 14 days (UV-vis, 800 nm). The results indicate that the fate of the CNTs in the environment might vary substantially both with CNT properties and the concentration of NOM. The adsorption of phenanthrene to the five types of CNTs was also investigated. The CNTs were dispersed in synthetic freshwater (MHRW) containing SR-NOM as described above. Specific surface area and surface chemistry of the CNTs appear to influence their adsorption of organic pollutants such as phenanthrene.

B.B.5
17:10
Authors : Bronisław Psiuk, Jacek Podw?rny, J?zef Wojsa, Anna Gerle, Jacek Szade
Affiliations : Institute of Ceramics and Building Materials, Refractory Materials Division in Gliwice; University of Silesia, Institute of Physics in Katowice

Resume : Chemical-looping combustion (CLC) is an attractive process in CO2 capture, especially when solid oxygen carriers are used in it. The main requirements for oxygen-transporting materials include appropriate oxidation (in air) and reduction (in the presence of fuel) ability. In the paper a conceptual proposition for CLC-related processes with the application of solid oxygen carriers oxidized in both air and CO2 atmosphere has been presented. SrTiO3 doped by Cr (STO:Cr) and a mixture of TiO2- and Ni-based compounds (TiO2-Ni) were investigated as oxygen transporting materials. The experiment methodology was based on thermogravimetric, diffraction and spectroscopic studies. Thermogravimetric (TGA) and Powder Diffraction (XRD) measurements were provided in-situ during a few cycles in a reducing (Ar 3%H2) and oxidizing environment. Moreover, the STO:Cr powders were characterized ex-situ by the X-ray Photoelectron Spectroscopy (XPS) method. It was found that in tested conditions the cyclic process of the investigated powders? oxidation and reduction is possible.

B.B.6
17:10
Authors : E. Piróg, J. Kapica-Kozar, R. J. Wrobel, B. Michalkiewicz, U. Narkiewicz, A. W. Morawski
Affiliations : West Pomeranian University of Technology in Szczecin

Resume : The advanced technique for the removal of CO2 is the chemical adsorption of CO2 on solid sorbents. Over the past decades, TiO2 materials with low cost, non toxicity, strong oxidizing power and high resistance to chemical or photo-induced corrosion, solar cells/batteries, electroluminescent and sensor have been widely investigated. Wet-impregnation is the most commonly used method in the preparation of amine-impregnation adsorbents. TiO2nanorods materials with different pore size were prepared and employed as support materials for impregnation with TEPA (tetraethylenepentamine). The properties of the obtained adsorbents were characterized and their CO2 adsorption performance was studied.CO2 adsorption/desorption measurements for sample at 30 C were carried using Netzsch STA 449 C thermobalance on the basis of the weight gain and loss during the sorption and desorption process. The sample was first heated from 30 oC to 100 oC at a rate of 5 o/min under a pure N2 (99.995 %) flow with a flow rate 30 cm3/min, and was kept at 100 oC for 60 min to remove any possible moisture from the sample. Then, the sample was cooled down to the desired temperature (30 oC) and kept at this temperature for 60 min. The sorption was started by switching from N2 to pure CO2 at the same flow rate and hold at the sorption temperature for 120 min for carbon dioxide adsorption. After the sorption, the temperature was increased to 100 oC, and the gas flow was switched from CO2 to N2 for desorption. The adsorption/desorptionprocedure was conducted for three cycles to test stability and adsorptive repeatability of the material modified with TEPA solution. The BET specific surface area measurements of the materials were carried out based on N2 adsorption isotherms at 77 K using Quadrasorb SI analyser (Quantachrome Instrumental).

B.B.7
17:10
Authors : E. Piróg, J. Kapica-Kozar, R. J. Wróbel, B. Michalkiewicz, U. Narkiewicz, A. W. Morawski
Affiliations : West Pomeranian University of Technology in Szczecin

Resume : Recently, extensive researches have been conducted on the synthesis, characterization and applications of TiO2nanorods because of their novel properties, such as unique shape and large specific surface area.Titaniananorods were prepared by a hydrothermal reaction in concentrated NaOH or KOH aqueous solution. Typically, 5g of commercial TiO2(GrupaAzotyZakładyChemicznePolice S.A., Poland) was added into a 150 mL Teflon-linead stainless steel autoclave, and filled with 80 mL 10 mol/L NaOH or KOH solution. Then the autoclave was maintained at 140 °C under autogenous pressure for 24 h and cooled to room temperature naturally. The resulting products were washed with distilled water till neutral. Then the samples were washed in a pH=1 solution adjusted by HCl for 24 h. and washed with distilled water to pH=7. Finally, the white products were annealed at 350 °C for 2 h in air. CO2 adsorption/desorption measurements for sample at 30 C were carried using Netzsch STA 449 C thermobalance on the basis of the weight gain and loss during the sorption and desorption process. The sample was first heated from 30 oC to 100 oC at a rate of 5 o/min under a pure N2 (99.995 %) flow with a flow rate 30 cm3/min, and was kept at 100 oC for 60 min to remove any possible moisture from the sample. Then, the sample was cooled down to the desired temperature (30 oC) and kept at this temperature for 60 min. The sorption was started by switching from N2 to pure CO2 at the same flow rate and hold at the sorption temperature for 120 min for carbon dioxide adsorption. After the sorption, the temperature was increased to 100 oC, and the gas flow was switched from CO2 to N2 for desorption. The adsorption/desorptionprocedure was conducted for three cycles to test stability and adsorptive repeatability of the nanorodsmaterials.

B.B.8
17:10
Authors : Kamila Maj, Ireneusz Kocemba
Affiliations : Insitute of General and Ecological Chemistry, Lodz University of Technology, 116 Zeromskiego St. 90-924 Lodz, Poland

Resume : Since the beginning of industrial revolution, the concentration of CO2 in the atmosphere has increased significantly. The emission of anthropogenic carbon dioxide has become a important issue. It is a cause of global warming and climatic changes. Therefore it is very important to develop materials and processes that can efficiently and economically capture and storage a carbon dioxide for a long time. A few methods of CO2 separation and capture are known: - physical and chemical adsorptions, - low-temperature distillation, - gas separation using membranes, - mineralization. We report on carbon nanostructures (CNs) for adsorption of CO2 and CO. CNs are obtained by direct methane decomposition over a nanocrystalline ferric catalyst with or without cobalt addition at 700oC. A sample of commercial active carbon was tested too. CNs were characterized by XRD, TG-DTA-MS and SEM/EDS which confirmed the formation of graphite nanostructures with different geometric shapes. Adsorption of CO2 and CO was carried out in a quartz reactor. The sample in the reactor was saturated by carbon monoxide or dioxide at room temperature at atmospheric pressure. Subsequently, the emitted volumes of gases during heating were measured. CNs obtained on the nanocystalline ferric catalyst with cobalt addition is a more efficient adsorber than carbon obtained on the catalyst without the cobalt addition and than commercial active carbon.

B.B.9
17:10
Authors : Olga Sneka-Płatek, Marcin Jędrzejczyk, Jacek Grams, Agnieszka Ruppert
Affiliations : Institute of General and Ecological Chemistry, Faculty of Chemistry Lodz University of Technology, Żeromskiego 116, 90-924 Łódź, Poland

Resume : The current energy crisis requires a search that will allow alternative sources of energy to be designed and optimized. One approach relies on the usage of catalytic decomposition of formic acid(FA) to generate hydrogen. Besides hydrogen in this reaction the carbon dioxide is formed as well. Competing process, which may also occur, isthe dehydratation of FAto CO and H2O.The aim of this work was to study Ru catalysts prepared by different methods towards selective decomposition of formic acid. The effect of reduction temperature of catalysts was examined to determine their influence on FA conversion and CO2 and H2yield.Preparation of catalysts (5% Ru by weight on titanium oxide (IV)) was performed using three different Ru precursors: ruthenium (III) acetylacetonate, ruthenium (III) nitrosyl nitrate and ruthenium (III) chloride hydrate.The reaction products were determined using high performance liquid chromatography (HPLC) and gas chromatography (GC). Physicochemical properties of the catalysts were examined by X-ray diffraction (XRD), transmission electron microscopy (TEM), temperature programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS), and BET for surface area measurements. The study by the temperature-programmed reduction showed that the type of precursor used in the catalyst preparation affects the type and potency of metal – support interaction. The highest activity and high selectivity towards H2 was observed for 5%Ru/TiO2 catalyst reduced at 100°C and synthetized from Ru(acac)3. References [1] A. M. Ruppert, K. Weinberg, R. Palkovits; Angew. Chem. Int. Ed. 51 (2012) 2564 – 2601 [2] G. Fiorentino, M. Ripa, S. Mellino, S. Fahd, S. UlgiatiJournal of Cleaner Production 2014, 66, 174-187; [3]. S. G. Wettstein, D. M. Alonso, E. I. Gürbüz, J. A. DumesicCurrent Opinion in Chemical Engineering 2012, 1, 218-224;

B.B.10
18:00 Best Student Presentation Awards Ceremony and Reception (Main Hall)    
Start atSubject View AllNum.
09:00 Plenary Session - Main Hall    
12:30 Lunch break    
 
Session 5 : -
14:00
Authors : Wojciech Gac
Affiliations : Maria Curie-Sklodowska University Faculty of Chemistry Department of Chemical Technology

Resume : Many efforts have been done for development of carbon capture and storage technologies in the last decades. Carbon capture and utilisation of CO2 into valuable chemicals and energy is perceived as an alternative route, and may bring more positive environmental, economic and social effects. CO2 has been widely used in various areas of modern industry, e.g. for urea production, welding, foaming, water treatment, food production. However more widespread utilisation of CO2 needs development of new integrated technologies, based on new catalysts, membranes, reactor concepts, heat exchangers, energy storage systems, etc. Physicochemical, engineering and economic aspects of the transformation of CO2 into new products and energy have been analysed in the present study. The attention has been mainly focused on the hydrogenation processes. Particular case studies, such as methanol and fuel production, and biogas valorisation have been discussed.

B.5.1
14:25
Authors : M. M. BETTAHAR
Affiliations : Institut Jean Barriol, SRSMC, UMR CNRS 7565, Faculté des Sciences et de la Technologie, Université de Lorraine, Boulevard des Aiguillettes, BP 7036, 54506 Vandœuvre Cedex, France

Resume : The utilization of CO2 as a raw material in the synthesis of chemicals and liquid energy carriers offers a way to mitigate the increasing CO2 [1]. A key product in chemical feedstock is methanol. Since decades up to 50 million tons of methanol are consumed for the fabrication e. g. of plastics, paints, organic solvents and clean fuels for fuel cells or combustion engines. Best catalysts for methanol synthesis by CO2 hydrogenation are copper based materials and the challenge is the selectivity of the reaction since CO is formed as a by-product [264]. The understanding of the chemical surface processes and solid catalysts properties is a requisite for optimizing the yield of the reaction. This talk deals with the kinetics and surface species involved in the formation of methanol from CO2 + H2 as well as changes in the solid state of the catalyst during the reaction. [1] Mette Mikkelsen, Mikkel Jørgensen and Frederik C. Krebs, Energy Environ. Sci., 2010, 3, 43–81 [2] Sahki, Rachid; Benlounes, Ouarda; Cherifi, Ouiza; Thouvenot, Rene; Bettahar, Mohammed M.; Hocine, Smain. React. Kinet. Mechanisms Catal. 2011, 103, 391-403. [3] Le Peltier, F.;Chaumette, P.; Saussey, J.; Bettahar, M. M.; Lavalley, J. C. J. Molec. Catal. A: Chemical 1997, 122, 131-139. [4] Le Peltier, F.; Chaumette, P.; Saussey, J.; Bettahar, M. M.; Lavalley, J. C. J. Molec. Catal. A: Chemical 1998, 132, 91-100.

B.5.2
14:50
Authors : L. Bedel
Affiliations : CEA-Liten, France

Resume : Presentation of CEOPS project and its last results. More information on www.ceops-project.eu

B.5.3
15:10
Authors : J.R. Morante
Affiliations : IREC, Spain

Resume : Presentation of the photocatalysis process for CO2 reduction developed by IREC in the frame of the CEOPS project. More information under www.ceops-project.eu

B.5.4
15:30
Authors : I. Graça, A. Westermann, M.C. Bacariza S. Bebiano, J.M. Lopes, C. Henriques
Affiliations : CATHPRO (Catalysis and Catalytic Process), CQE - Centro de Química Estrutural, Instituto Superior Técnico, University of Lisbon.

Resume : The development of a Ni/zeolite based catalyst, active and selective for the methanation reaction of CO2, under conventional heating conditions, is presented. Catalysts containing Ni and Ce supported on a HNaUSY zeolite were tested for the CO2 hydrogenation into methane. The results pointed out that, when prepared by impregnation, Ni-zeolite catalysts present very interesting levels of activity and selectivity for this reaction because of the easier reducibility of the NiO species, compared to the ion-exchanged Ni species. In fact, it was observed that the higher the Ni content on the catalysts, the better their performances, due to the greater amount of Ni0 species after reduction. The Ce addition to the Ni zeolites is also responsible for a further improvement of the catalysts activity and selectivity, which could be attributed to the presence of CeO2 that promotes the CO2 conversion into CO. Therefore, the final catalyst properties result from a synergetic effect between the metal active sites and the promoter. Furthermore, all these catalysts revealed a good stability when submitted to 10 h of reaction at 400 °C, with no sintering detected. Performed catalysts optimization includes topics as metal contents, Si/Al ratio, drying conditions before calcination and pre-reduction temperature. An operando IR study on Ni/USY catalysts, allows to verify that, in absence of hydrogen, CO2 is almost not adsorbed over acidic zeolite, but formates and carbonyls were detected in presence of hydrogen, suggesting that CO2 hydrogenation mechanism does not probably pass through the carbonate formation as intermediate. In fact carbonates formed on NiO seem to be spectator species, as they not react with H2. CO2 seems rather proceed through formate dissociation onto Ni0 particles leading, at lower temperatures, to the formation of adsorbed CO and in a minor way to methane. The simultaneous measurements of both adsorbed and gaseous species seems to confirm previous conclusions in the literature, indicating that the CO dissociation/hydrogenation is the rate-determining step for CO2 methanation. In addition, methane formation seems also to be controlled by the relative concentration of adsorbed species.

B.5.5
15:50 Coffee Break    
 
Session 6 : -
16:10
Authors : Magadalena Nizio1,2, Abdulkader Albarazi1, Simeon Cavadias1, Jacques Amouroux1,3, Maria Elena Galvez2, Patrick Da Costa2.
Affiliations : 1Institut de Recherche de Chimie Paris, CNRS - Chimie ParisTech, 11 rue Pierre et Marie Curie, 75005, Paris, France. 2Institut Jean Le Rond d’Alembert, UPMC Sorbonne Universites, CNRS UMR 7190, 2 Pl. de la gare de Ceinture, 78210 Saint-Cyr-L’Ecole, France. 3Université Pierre et Marie Curie Paris VI, 4 Place Jussieu, 75005, Paris, France.

Resume : The limited resources of oil and natural gas, together with the increasing energy demand, forces us to seek for each time more efficient and cleaner energy production alternatives. Hydrogen has been recently considered as promising energy carrier. However, there are several inherent problems to the utilization of H2, from its transportation to its distribution. Transformation of the H2 molecule by fixing into a carbon-containing compound, i.e. CH4, will offer the possibility of using the conventional transportation network. This process, generally called methanation, represents moreover a feasible approach contributing to the reduction of the emissions of CO2 to our atmosphere, through a closed carbon cycle involving the valorization of CO2, i.e. from capture. However, below a temperature of 250°C conversion becomes practically 0 %, whereas at higher temperatures (>300ºC), the co-existence of secondary reactions favors the formation of CO + H2. This is the reason why new catalyst and process conditions are continuously being investigated in order to maximize selectivity to methane at low reaction temperatures and at atmospheric pressure. Ceria-zirconia oxides have been recently considered as promising catalyst support in the preparation of active and selective catalytic systems for CO2 methanation. Ocampo et al. [1] evaluated CO2 methanation activity of Ni-ceria-zirconia for the first time and revealed that Ni-ceria-zirconia exhibited excellent catalytic activity and stability during 150 h on stream. Such high performances were due to the high oxygen storage capacity of ceria-zirconia oxides and the highly disperse nickel. Using ceria-zirconia based catalysts combination with Dielectric Barrier Discharge plasmas (DBD) can enhance the activation of the methanation reaction at low temperatures, overcoming the drawbacks of conventional operation. Moreover, DBD catalytic reactors require very low consumption of electricity power, less than 12 kJ/mole of CH4 and, at the same time, they meet all the requirements for large volume methane production [2]. Several Ni-containing catalysts were prepared using various ceria-zirconia oxides as support, with different Ce/Zr ratio. Catalysts were prepared using Ni loads between 5 and 15%, following a conventional impregnation route. Their activity towards methanation in the presence and in the absence of a DBD plasma was tested in a fixed bed reactor (20,000 h-1 GHSV). High voltage plasma 10-15 kV was used in the experiments at temperatures from 100 to 420°C. Under adiabatic conditions and at low temperatures (within the range of 140-160ºC), 100% selectivity to methane was achieved, in the presence of a gas mixture containing 20% of CO2 and 80% of H2. Total conversion of CO2 was 80%. The combination of nickel and ceria/zirconia was found to play a vital role in the catalytic behavior. Under conventional methanation conditions, i.e. in the absence of plasma, the same conversion and selectivity are only achievable at much higher temperatures, 80% conversion and selectivity at 300ºC. Plasma-activated catalysis allows the production of synthetic methane at low temperatures (<150°C) and at atmospheric pressure. Ni supported on ceria-zirconia mixtures exhibited enhanced catalytic activity, both in absence and in presence of a DBD plasma. REFERENCES [1] M. Ocampo, B. Louis, A.C. Roger, Appl. Catal. A. 369 (2009) 90-96. [2] Patent: J. Amouroux, S. Cavadias, M. Nizio, S. Ognier, T. Andreu, J. R. Morante, C. M. F. de B. Henriques, J. M. Lopes, M. F. Ribeiro, M. del C. Bacariza, I. Graça: Process for the carbon dioxide reduction to methane by DBD plasma activated catalyst. UPMC Paris VI, IREC, Univ. de Lisboa, Univ. de Barcelona, 28 Janvier 2015, P201530109. Submited.

B.6.1
16:30
Authors : V. Popov
Affiliations : Institute for Eletrophysics and Electric Power, RAS, Russia

Resume : Presentation of the pilot arc process for waste treatment

B.6.2
16:50
Authors : Vincent Thoreton(a), Mehdi Pishahang(b), Yngve Larring(b), Tommy Mokkelbost(c), Kjell Wiik(a)
Affiliations : (a) Dept. of Materials Science and Engineering, NTNU, Trondheim, Norway; (b) Dept. of Energy Conversion and Materials, SINTEF Materials and Chemistry, Oslo; (c) SINTEF Materials and Chemistry, Trondheim, Norway

Resume : Aiming for a technology with high efficiency and low cost for carbon capture, chemical looping combustion (CLC) shows a promising potential. It allows the inherent separation of CO2 during the fuel combustion which happens in a nitrogen free reactor thanks to the direct reaction of the fuel with oxygen released from a solid oxygen carrier material (OCM). The development of suitable OCM is a challenge. In circulating fluidized bed (CFB) CLC, OCM must keep a high oxygen capacity, high redox kinetics with both air and fuel and good mechanical properties. Furthermore it should be low cost and have a low toxicity. Lately, a significant interest has been shown to mixed OCM, especially to materials derived from the calcium manganite CaMnO3-δ perovskite. In the frame of BIGCCS, CaMn0.875.x-yFexTiyO3-δ OCM were produced from industrial chemicals by spray granulation which is an easily up-scalable process. OCM chemical composition of CaMn0.875.xFexTi0.125O3-δ was investigated for optimization of the spontaneous release of oxygen by the OCM (CLOU effect). The latter were measured using cyclic thermogravimetric measurements (TG) under redox atmospheres, simulating the conditions during CLC operation. It was shown that iron substitution improves the redox kinetics. The mechanical properties of OCM were also investigated at low and high temperature.

B.6.3
17:10
Authors : Olga Sneka-Płatek, Marcin Jędrzejczyk, Joanna Michalak, Jacek Grams, Agnieszka Ruppert
Affiliations : Institute of General and Ecological Chemistry, Faculty of Chemistry Lodz University of Technology, Żeromskiego 116, 90-924 Łódź, Poland

Resume : The decomposition of formic acid – a promising hydrogen storage material – has been mostly characterized by two reaction pathways: dehydrogenation to form H2 and CO2, and dehydration yielding H2O and CO. Our aim was to design active and selective catalysts for the former path so that, besides hydrogen, carbon dioxide ready for sequestration could be produced, which is the desired case for industry. Formic acid decomposition was performed in liquid phase in a batch reactor under autogenic pressure at 190°C. In our work we focused on Pd-Ag catalysts. Several factors were investigated, like different catalysts compositions (1-5% Me=Pd, Ag) and various synthesis methods (coimpregnation vs. subsequent impregnation).Physicochemical properties of the catalysts were examined by X-ray diffraction (XRD), transmission electron microscopy (TEM), temperature programmed reduction (TPR), X-Ray Photoelectron Spectroscopy (XPS), and BET surface area was measured as well. Our results confirmed that FA decomposition depends on the type of used catalyst.The bimetallic systems based on Ag and Pd showed much higher selectivity and activity towards hydrogen than their monometallic counterparts. The highest activity in FA decomposition was observed for 4%Ag-1%Pd/C prepared by co-impregnation (45% of H2; 47% of CO2). References [1] A. M. Ruppert, K. Weinberg, R. Palkovits; Angew. Chem. Int. Ed. 51 (2012) 2564 – 2601 [2] I. T. Horvath, H. Mehdi, V. Fábos, L. Boda, L. T. Mika, Green Chem. 10 (2008) 238-242 [3] M. Ojeda, E. Iglesia, Angew. Chem. 121 (2009) 4894 –4897

B.6.4
17:30
Authors : Dogukan H. Apaydin, Eric D. Glowacki, Engelbert Portenkirchner, N. Serdar Sariciftci
Affiliations : Linz Institute for Organic Solar Cells (LIOS), Institute of Physical Chemistry, Johannes Kepler University Linz, Austria

Resume : A key step for both sequestration and utilization of anthropogenic carbon dioxide which is a major issue we face today, is controlled capture, storage and release of CO2. Here we report an efficient way of controlled capture and release of carbon dioxide using nature inspired, cheap, abundant and non-toxic pigments namely, Quinacridone and Indigo. Electrochemically reduced electrodes having a structure of ITO/Pigment (~100nm) are capable of forming a Pigment·carbonate salt in an organic electrolyte environment saturated with CO2. Captured CO2 can be released by electrochemical oxidation as well as heating. The amount of captured CO2 was quantified by FT-IR spectroscopy. The uptake efficiency, which is described by the amount of captured CO2 in mmol per gram of capturing agent, was found as 4.6 mmol/g [1]. This value is among the highest reported uptake efficiency for electrochemical CO2 capture. One of the greatest advantages of this process is to have operating conditions at room temperature which might lead to future energy-efficient applications. For comparison, the state-of-the-art aqueous amine industrial capture process has an uptake efficiency of ~8 mmol/g Reference: [1] D. H. Apaydin, E. D. Głowacki, E. Portenkirchner, N. S. Sariciftci Angew.Chem.Int.Ed. 53 (2014) 6819

B.6.5
17:50
Authors : S. Messias(1), Margarida Sousa(1), A. S. R. Machado(1)*, T. R. C. Fernandes(1),T. Pardal(1),C.M. Rangel(2), D. Nunes(3), R. Martins(3), Zeljko Petrovsky(3) and Manuel Nunes-da-Ponte(3)
Affiliations : (1) Omnidea, Lda., Travessa António Gedeão. No. 9, 3510-017 Viseu, Portugal (2) Laboratório Nacional de Energia e Geologia, Estrada do Paço do Lumiar, 22, 1649-038 Lisboa, Portugal, (3) Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa, 2829-519 Caparica, Portugal *ana.machado@omnidea.net

Resume : To reach the target of 40% reduction of green- house-gas emissions (GHG) in 2030 compared to 1990 levels requires a wide portfolio of technologies ready to be deployed at an industrial level. Room temperature ionic liquids- based technologies are very promising and can contribute to this goal, still intense research is necessary to develop them to the industrial level. These technologies can be envisaged both as a process for carbon dioxide capture and as a reaction medium for CO2 transformation and valorisation. This presentation will address the potential contributions of ionic liquids from CO2 captureand storageto CO2 conversion in ionic liquid media. A comparison between these technologies and commercial deployed technologies will be carried out. In particular, results obtained in the conversion of CO2 into fuels by electrochemical reduction of CO2 using ionic-liquid based electrolyteswill be reported.The determinant role of the coupling of advanced catalytic cathodes/ionic liquid based electrolyte in the performance of the electrochemical system will be analysed. KEYWORDS: Carbon dioxide; ionic liquids; electrochemical reduction; catalysis.

B.6.6

Symposium organizers
Jacques AMOUROUXEcole Nationale Supérieure de Chimie (ENSCP)

11 rue Pierre et Marie Curie Université Pierre et Marie Curie Paris France

+ 33 6 7821 5886
jacquesamouroux@gmail.com
Richard BLOMSINTEF

P.O. Box 124 Blindern 0314 Oslo Norway

+4790622647
richard.blom@sintef.no
Kaiying WANGBuskerud and Vestfold University College

Raveien 215 Horten 3184 Norway

+47 3303 7721
Kaiying.Wang@hbv.no
Rafal J. WROBELWest Pomeranian University of Technology

Pulaskiego 10 70-322 Szczecin Poland

+48-914494730
rwrobel@zut.edu.pl