Energy-to-Chemicals: Methanation and other synthesis routes. Researchers seminar Francisco Vidal, Dr. Pekka Simell, Dr. Matti Reinikainen VTT Technical Research Centre of Finland
Content of the presentation Power-to-Liquids Fischer-Tropsch synthesis Methanol synthesis Mixed alcohols synthesis Hydrodeoxigenation HDO and hydrogenation of bio-oil SPERA-hydrogen process Power-to-Gas Production of ammonia DME synthesis Methanation Experimental work: Conventional process Intensified process 10/02/2016 2
Power-to-Liquids 3
Fischer-Tropsch synthesis H 2 + CO + (CO 2 )--> Wide range of product Reaction conditions (Co-catalyst): Temp: 200-230 C Pressure: 20-30bar Heavier products Reaction conditions (Fe-catalyst): Temp: 250-350 C. Pressure: 5-20 bar. Lighter products Multiphase reaction (Gas-Liquid-Solid) Highly exothermic (deltah = -180 kj/mol) Mass transfer limitations. At VTT: - Extensive experience in FT-synthesis with Fe and Co catalysts. (Matti Reinikainen) - VTT has patents on Co and Fe catalysts. Specially important to control the reaction temperature and heat management 10/02/2016 4
Methanol synthesis + 2. = 90.7 +3 +. = 40.9 Reaction conditions: Temp: 250-280 C Pressure 50-100 bar Cu/Zn-based catalyst Several step and recycling in the process At VTT: - Literature survey on methanol synthesis in 90 s (Pekka Simell). - Reforming of methanol. (Francisco Vidal). - Experimental work in CO2 methanol synthesis. (Matti Reinikainen) Specially important to control the reaction temperature and heat management Methanol can be converted to gasoline ExxonMobil MTG process 10/02/2016 5
Mixed alcohols synthesis H 2 + CO --> Mixed Alcohols + H 2 O Reaction conditions: Temp: 250-450 C Pressure 80-200 bar Rh-based catalysts, Cu-based catalysts, and Mo-based catalysts. Exothermic process. Product distribution depending on the catalyst composition. Adaptable to different product distribution. Difficult to have high selectivity to certain products (except methanol) Non-commercial process. At VTT: - Experimental work on Co/Mo-catalyst. (Matti Reinikainen) 10/02/2016 6
Hydrodeoxigenation (HDO) and hydrogenation of bio-oils H 2 + Pyrolisis Oil (unstable) --> Pyrolisis Oil (stable) + H 2 O High oxygen content in bio-oil which need to be removed. HDO and hydrogenation are highly exothermic reactions. High pressure and low temperature (150-350 C and 100-150 bar). Difficult to get high selectivity and yield. Large amount of hydrogen is required. At VTT: - Experimental work in pilot plant Bioruuki. (Christian Lindfords and Matti Reinikainen) in cooperation with National Renewable Energy Laboratory NREL, USA. 10/02/2016 7
SPERA-hydrogen process Hydrogenation of toluene, widely used technology. Dehydrogenation of methylcyclohexane (MCH) developed by Chiyoda. Highly exothermic/endothermic process Main disadvantage of the H2 storage system. 10/02/2016 8
Power-to-Gas
Ammonia synthesis +3 2 = 92 / Reaction conditions: Temp: 300-500 C Very high pressure 150-300 bar Very demanding process. Techno-economically feasible at large scales. Well known process. At VTT: - Work done for KEMIRA ammonia plant in the early 90 s for syngas production (peat gasification and gas cleaning) 10/02/2016 10
Dimethyl ether (DME) synthesis + + 2 + = / = 21.5 / Dehydratation of methanol Low exothermic reaction. Low pressure process. Acidic catalysts ( -Alumina). DME is considered as chemical platform for production of other chemicals Haldor Topsoe has one step process to DME from syngas (TIGAS-process, either to DME or gasoline, 40 bar 250-300 C) 10/02/2016 11
Methanation +3 + +4 + 2 = 206.1 = 165.0 Highly exothermic Decrease in total moles Reactions favoured by low temperature and high pressures Important to control the reaction temperature and heat management Reaction conditions: Temp: 250-700 C Pressure = 5-50 bar Fixed bed Ni-based catalyst Figure: Specht M. et al. 2010 - VTT has made techno-economic assessment in VETAANI project (Ilkka Hannula). - Extensive knowledge in reforming of methane (Catalysis and Synfuels team). 10/02/2016 12
TREMP process (Haldor Topsøe) Adiabatic reactors in series. Reaction conditions: Temp: 250-700 C. Max. Pressure: 30 bar. Designed for production of SNG and superheated steam (540 C and 140 bar) from CO+H2 feed. It can be easily adapted to different feed compositions (Syngas, Biogas+H2, Gasification gas + H2 ). Designed for large scale plants. 10/02/2016 13
Heat exchanger plate reactor (ETOGAS) One heat exchanger reactor. Reaction conditions: Temp: 250-550 C. Max. Pressure: 15-20 bar. Designed for production of SNG and process steam (280 C and 40 bar) from Biogas+H2 feed. It can be also adapted to different feed compositions (Syngas, Biogas+H2, Gasification gas + H2 ). Designed for small-scale modular plants of 1,2 MWe, around 60-70 Nm3/hr of SNG production. 10/02/2016 14
Experimental work in methanation Two research paths: Adiabatic process (Haldor Topsoe TREMP process) Several stages reactor with recirculation. Heat exchanger intensified reactor (ETOGAS one stage reactor) One stage intensified reactor cooled by high pressure water/steam (either packed-bed or coated catalysts). 10/02/2016 15
Experimental work for adiabatic process Objective: assess the effect of the different factors in the convetional process and test the commercially available catalysts. Test of the process with commercial catalysts. Different gas feed compositions. Different gas recirculation in the first stage. Different GHSV. Different H2/CO2 ratios. Different pressures (H2-CO2)/(CO2+CO)ratio Pressure (bar) GHSV (1st step) Recirculation (at the 1st step) Different catalysts Different feed 2.8 1 10000 0Reformax Pure feed (H2 and CO2) 3 5 15000 0.25METH-135 (High nickel load) Biomass gasification (CO and low CH4) 3.2 20 20000 0.5METH-150 (Ru-based) Biogas (no CO and high CH4) 10/02/2016 16
Conclusions Provide useful information for the WP4 in the modelling of the different chemical process and in particular for the methanation process. Provide basic design data for companies developing small-scale processes applying intensified reactors. VTT with its expertise in the field of fuel conversion is ready and capable to go to bench/pilot/demo scale. 10/02/2016 17
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