SUMMARY OF WORK WP5.2 METHANATION AND OTHER SYNTHESIS ROUTES

SUMMARY OF WORK WP5.2 METHANATION AND OTHER SYNTHESIS ROUTES Final researcher s seminar Francisco Vidal Vázquez (Paco)

CONTENTS Methanation Methanol synthesis Durability of catalysts CO production from CO 2 by rwgs CO 2 to higher value chemicals and products (next presentation)

CO 2 METHANATION

Experimental work: Study conventional process. Tasks Study and kinetic modeling experiments of particulate catalyst tubular HEX reactor. Development of coated catalyst. Optimization of coated catalyst. Kinetic modeling experiments of optimized coated catalyst. Reactor modeling work: Thermodynamically constrained model based on experimental results of HEX tubular reactor with particulate catalyst. Kinetic model for coated catalyst. Heat exchanger reactor with coated catalyst simulation.

CO 2 methanation: Study of conv. process Experiments: Quartz tubular reactor using commercial catalyst at different feed flowrates and pressures. Results: Reaction oversoot even for high flowrates and small catalyst bed. Main challenge are heat transfer and heat management in the reactor.

CO 2 methanation: Kinetic model developed Experiments: Kinetic modeling experiments with the tubular heat exchange reactor using commercial particulate catalyst. Results: using HEX tubular reactor Thermodynamically constrained model for CO 2 methanation (published). Figure: Scheme and picture of HEX tubular reactor

CO 2 methanation: Kinetic model developed using HEX tubular reactor

CO 2 methanation: Development of coated Experiments: catalyst Catalyst screening of different Ni-Alumina catalysts. Results: Suitable coated catalysts for CO 2 methanation over 300 C. Results published in Master s thesis (URL: https://aaltodoc.aalto.fi/handle/123456789/15564) Figure: Experimental set up for catalyst screening Figure: Pictures of tubular reactors with internally coated catalyst

CO 2 methanation: Development of coated Experiments: catalyst Catalyst screening for Ni-Hydrotalcite coated catalyst Results: Up to 6 times higher activity compared to Ni-Alumina coated catalysts. Suitable Ni-Hydrotalcite coated catalysts for low temperature CO 2 methanation 250-300 C. Results published in Master s thesis (URL: https://aaltodoc.aalto.fi/handle/123456789/27024) Figure: Experimental set up for catalyst screening

CO 2 methanation: Kinetic and reactor Experiments: modeling for coated catalyst Kinetic experiments for Ni-Hydrotalcite coated catalyst in tubular reactor cooled by thermal oil in a continuous stirred tank reactor. Results: Kinetic model for Ni-Hydrotalcite coated catalyst. 1D and 2D-axial symmetry reactor models. Results published in Master s thesis (URL: ask Pasi Vainikka) Velocity profiles for catalytically coated helicoidal tubular reactor Picture of tubular reactors with internally coated catalyst Picture of experimental set up with stirred autoclave

CO 2 METHANOL SYNTHESIS

Experimental work: Tasks Study of process with commercial catalyst. Screening of new formulation catalysts. Modeling and techno-economic analysis: Assessment of kinetic models in literature by Aspen Plus. Techno-economic analysis of the Power-to-Methanol and Methanol-to-Power cases.

Experiments: CO 2 methanol synthesis: Catalyst screening of ca. 20 catalyst in a continuously stirred autoclave. Collaboration with University of Porto for catalyst development. Results: Commercial catalysts performed as good as best performing develop catalysts. Top coating improved performance in all catalysts. Results published in Master s thesis (URL: https://aaltodoc.aalto.fi/handle/123456789/19938). FEUP Continuous stirred autoclave used in the experiments Performance comparison of the different catalysts

Techno-economic analysis PEM-EC/FC METHANOL REFORMING METHANOL SYNTHESIS Methanol URL:https://www.researchgate.net/publication/312553503_Closing_energy_cycle_Power-to-Methanol_and_Methanol-to-Power

CATALYST DURABILITY TESTS FOR CO 2 HYDROGENATION

Effect of impurities on CO 2 hydrogenation Experiments: Effect of H 2 S and MEA on methanation, methanol synthesis and Fischer-Tropsch synthesis (FT) catalysts. Results: Effect of MEA: Methanation and FT catalyst lost activity. Methanol synthesis catalyst changed selectivity (more CH 4 formation). Effect of H 2 S: Methanation and FT catalyst lost activity. Methanol synthesis resistant to H 2 S (30 and 60 ppm). Results published in Master s thesis (URL: https://aaltodoc.aalto.fi/handle/123456789/23622). Picture of experimental set up

CO PRODUCTION FROM CO 2 BY REVERSE WATER GAS SHIFT

Collaboration between VTT and IMVT (KIT) Direct collaboration with Institute of Microprocessing Engineering (IMVT-KIT and INERATEC GmbH for the Power-to-X case. Research exchange of Francisco Vidal at KIT (Germany) during Jan-July 2016 for jointly development of bench-scale rwgs reactor for CO production for Fischer-Tropsch synthesis (Power-to-Liquid case). Topic:

- Özgül, Agbaba Sener - Fanni Henriksson - Ajenthan Mylvaganam - And other collaborators Acknowledgements

TECHNOLOGY FOR BUSINESS NEO-CARBON ENERGY project is one of the Tekes strategic research openings and the project is carried out in cooperation with Technical Research Centre of Finland VTT Ltd, Lappeenranta University of Technology LUT and University of Turku, Finland Futures Research Centre FFRC. http://www.neocarbonenergy.fi/