Materials for CO2 capture and storage

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 .

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).

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.

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)

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.

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).

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.

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.

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;

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

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

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.

Resume : Presentation of the pilot arc process for waste treatment

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.

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

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.