Solar Hydrogen from Thermochemical Water-Splitting: The HYDROSOL process and beyond

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HYDROSOL-II Solar Hydrogen from Thermochemical Water-Splitting: The HYDROSOL process and beyond Athanasios G. Konstandopoulos Coordinator Aerosol and Particle Technology Laboratory (APTL) CPERI/CERTH, Thessaloniki, Greece

Renewable Hydrogen Pathways

Consortium APTL/CERTH/CPERI - Aerosol & Particle Technology Laboratory (Coordinator) DLR - Deutsches Zentrum für Luft- und Raumfahrt JOHNSON MATTHEY STOBBE TECHNICAL CERAMICS CIEMAT - Centro de Investigaciones Energéticas, MedioAmbientales Y Tecnológicas DURATION: 01/11/05-31/10/09; Total cost: 4.297.400 ; EU funding: 2.182.700

The HYDROSOL Concept Solar Hydrogen production via a two-step water splitting process, performed on monolithic honeycomb reactors, capable of developing high temperatures under concentrated solar irradiance and coated with active redox materials capable of water-splitting and regeneration, so that complete operation (water-splitting and redox material regeneration) is achieved in a closed solar reactor. M O H O M O H Reduced state x Oxidized state x 1 + 2 x + (Exothermic) 2 Oxidized state M O M O + O (Endothermic) 1 x 1 2 2 Reduced state

The HYDROSOL Concept Renewable energy sources and raw materials Zero greenhouse gas emissions Long-term potential Descartes Prize (Mar. 7, 2007) IPHE Inaugural Technical Achievement Award (Jun. 13, 2006) 100 Global Ecotech Award-EXPO Japan (Sept. 1, 2005)

The HYDROSOL Concept 800 C 1200 C

The HYDROSOL Concept Basic Features Use of solar radiation absorbing ceramic honeycomb structures Synthesis of active water-splitting redox nanomaterials with non-conventional techniques Fixing/coating of the redox materials on the channels of the honeycomb Advantages No circulation of (hot) solid reactants Product separation straightforward No problems with the recovery of high temperature heat

Project Goals The aim of HYDROSOL-II is to design and build a solar Hydrogen pilot plant (100 kw th ) based on thermochemical water-splitting, carried out on monolithic ceramic honeycombs coated with active redox materials. Set the stage for further scale-up of the HYDROSOL technology and its effective coupling with solar thermal concentration systems, in order to exploit and demonstrate all potential advantages.

Key project activities Optimisation of metal oxide/ceramic support assembly (enhancement to achieve long-term multi-cyclic solar operation with high efficiency) Design of the 100kW th solar pilot plant (geometry and size of pilot plant modular absorber/reactor; adaptation of the heliostat field of Plataforma Solar de Almería to the specific thermo-chemical process and alternating heat flux requirements Manufacture of the integrated pilot-scale solar reactor system Test operation of pilot plant for continuous Hydrogen production Evaluation of technical and economic potential

Hydrosol technology scale-up Hydrosol-II 2008: World s largest STC H 2 reactor (100 kw) 2005: Continuous STC Η 2 production PSA solar tower Hydrosol-I 2004: First solar thermochemical (STC) Η 2 production DLR solar furnace

Materials Development Water-splitting on redox coated honeycombs 50-cycles of solar water-splitting Field evaluation of coated monoliths 18 Redox material coated SiSiC honeycombs m dot,h2 in 10-5 g/s 16 14 12 10 8 6 4 1. day 2. day 3. day 4. day 5. day Hydrogen Yield 2 0 0 5 10 15 20 25 30 35 40 Time in h SEM analysis for the investigation of the quality of coating and the effect of solar water splitting Key milestone

Solar reactor development Design of the reactor Reactor integration with heliostat field Thermo-structural modeling of the reactor

Solar reactor control Process flowsheet Reactor temperature control Power East (23.04.2009) 70 Power Simulated Power Measured 60 50 40 30 20 10 0 Power [kw] 10:15:00 10:30:00 10:45:00 11:00:00 11:15:00 11:30:00 11:45:00 12:00:00 12:15:00 12:30:00 12:45:00 13:00:00 13:15:00 13:30:00 13:45:00 14:00:00 14:15:00 14:30:00 14:45:00 15:00:00 Time

SSPS Tower of Plataforma Solar Almeria, Spain HYDROSOL-ΙΙ Reactor

9 8 7 6 5 4 3 2 1 0 Hydrogen production in the Hydrosol II Reactor c(h2 ) [%] 10:14:25:00 10:32:44:07 10:41:52:96 10:51:02:50 11:00:11:62 11:09:20:68 11:18:29:71 11:27:39:00 11:36:48:32 11:46:05:43 11:56:01:18 12:05:54:21 12:15:39:75 10:23:35:20 12:25:34:45 12:35:25:87 12:45:16:01 12:55:09:93 13:05:27:85 13:15:38:89 13:25:49:78 13:36:25:34 13:46:39:26 13:57:08:35 14:07:44:28 14:17:45:50 14:28:13:50 14:38:43:34 14:48:38:73 14:59:09:28 15:09:48:46 15:20:15:14 15:30:54:76 15:41:34:09 15:52:11:10 16:02:50:15 16:13:29:14 16:23:59:71 16:34:38:90 16:45:13:87 16:54:56:40

Summary Optimization of the coating material and method Investigation of the operational parameters that affect H 2 production (amount of O 2 during regeneration, increase of splitting temperature etc). The HYDROSOL II reactor concept was scaled up from the solar furnace to a 100 kw pilot plant on the tower of the PSA A control system guarantees stable working conditions, proven by thermal and hydrogen production tests

Challenges & Opportunities: Fuels from CO 2 and solar H 2 Η 2 Η 2 Ο Cycle Η 2 Ο Η 2 + ½ Ο 2 C + O 2 CO 2 2 Cycle CO 4Η 2 + CO 2 CΗ 4 +2H 2 O 3Η 2 + CO 2 CΗ 3 ΟΗ+ H 2 O Η 2 Ο CO 2 From sequestration

Tomorrow s Solar Thermochemical Plant Production of Solar Fuels (renewable H 2 and CH 4 / CH 3 OH), Recycling of CO 2, Production of Electricity and Desalinated H 2 O H 2 O Captured CO 2 H 2 CH 4, CH 3 OH Heat Electricity Sea water Desalinated H 2 O A. G. Konstandopoulos. No reproduction without permission. Contact agk@cperi.certh.gr

A Renewable Future for Europe Mare Nostrum (Reloaded) Solar thermal HYDROSOL Photovoltaic Wind Hydroelectric Biomass Geothermal dapted from DESERTEC White Paper (2007)

Thank you for your attention! www.hydrosol-project.org