Solar Technologies redox cycles for hydrogen and syngas production Dr. Christian Sattler

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DLR.de Chart 1 Solar Technologies redox cycles for hydrogen and syngas production Dr. Christian Sattler Christian.sattler@dlr.de

DLR.de Chart 2 > R&D on CSP and Solar Chemistry > Sattler Japanese CSP Society > 11/12/2014 DLR German Aerospace Center Research Institution Space Agency Project Management Agency >8000 employees across 32 institutes and facilities at 16 sites. Offices in Brussels, Paris, Tokyo and Washington, Almería. Stade Hamburg Neustrelitz Bremen Trauen Braunschweig Berlin Goettingen Juelich Cologne Bonn Lampoldshausen Stuttgart Augsburg Oberpfaffenhofen Weilheim

DLR.de Chart 3 > R&D on CSP and Solar Chemistry > Sattler Japanese CSP Society > 11/12/2014 Institute of Solar Research Prof. Dr. Robert Pitz-Paal p 3 Evaluation Renewable Energies 26th January 2009

DLR.de Chart 4 Solar Pathways from Water or CO 2 to Fuels Carbon Monoxide

DLR.de Chart 5 Efficiency comparison for solar hydrogen production from water (Siegel et al., 2013)* Process T [ C] Solar plant Solarreceiver + power [MW th ] η T/C (HHV) η Optical η Receiver η Annual Efficiency Solar H 2 Elctrolysis (+solarthermal power) NA Actual Solar tower Molten Salt 700 30% 57% 83% 13% High temperature steam electrolysis 850 Future Solar tower Particle 700 45% 57% 76,2% 20% Hybrid Sulfurprocess 850 Future Solar tower Particle 700 50% 57% 76% 22% Hybrid Copper Chlorine-process 600 Future Solar tower Molten Salt 700 44% 57% 83% 21% Metaloxide two step Cycle 1800 Future Solar dish Particle Reactor < 1 52% 77% 62% 25% *N.P. Siegel, J.E. Miller, I. Ermanoski, R.B. Diver, E.B. Stechel, Ind. Eng.Chem. Res., 2013, 52, 3276-3286. 5

DLR.de Chart 6 Technical Optimization in all Dimensions necessary 10 4 10 2 m Solar Plant Site Solar field Simulation Environmental impact 10 2 10 1 m Receiver Design Simulation Construction Testing Next-Generation- Development 10 1 10-2 m Receivercomponents Materials Design Heat and Mass transport Simulation Testing and Develpment 10-2 10-8 m Reactive Systems Simulation Synthesis Chemical Charactristics Physical Characteristics

DLR.de Chart 7 Receiver - Concepts Challenges: Temperature Corrosion Abrasion Process operation Goals: Efficiency Durability Cost Solar heated Rotary Kiln, DLR Solar heated Cavity-Gas Receiver with porous Ceramic structur A. Steinfeld et al., ETH Zürich Solar heated Partikel-Receiver I. Ermanoski et al., Sandia Natl. Lab.

DLR.de Chart 8 2 Step Thermochemical Cycle for H 2 O or CO 2 Splitting Example: HYDROSOL concept 1. Water Splitting H H 900 C H 2 O + MO red MO ox + H 2 O 2. Regeneration MO ox MO red + ½ O 2 1300 C O O Net Reaction: H 2 O H 2 + ½ O 2

DLR.de Chart 9 Hydrosol technology scale up PSA solar tower 2008: Pilot reactor (100 kw) 2005: Continuous Η 2 production 2004: First solar thermochemical Η 2 production DLR Solar Furnace

DLR.de Chart 10 Solar fuels from thermochemical cycles- HYDROSOL 3D project- Main results Economic analysis of the demonstration plant Demonstration plant thermal energy input: 1 MW Cost calculation of the new designed reactor was carried out. Cost calculation of the overall process units was performed. More than half of process investment results from the solar system.

DLR.de Chart 11 Hydrosol Plant - Design for CRS tower PSA, Spain European FCH-JU project Partner: APTL (GR), HELPE (GR), CIEMAT (ES), HYGEAR (NL) 750 kw th demonstration of thermochemical water splitting Location: Plataforma Solar de Almería, Spain, 2015 Use of all heliostats Reactor located on the CRS tower Storage tanks and PSA on the ground

DLR.de Chart 12 HYDROSOL, HYDROSLOL 2, HYDROSOL-3D, HYDROSOL Plant APTL (GR), DLR (DE), CIEMAT (SP), StobbeTech (DK), Johnson Matthey (UK), HyGear (NL), HELPE (GR) 2002 Start HYDROSOL, EU FP5 2004 First solar hydrogen, DLR 2005 Quasi-continuous solar hydrogen, DLR 2008 HYDROSOL 2, EU FP6, 100 kw demonstration CRS Tower PSA, Spain 2013 HYDROSOL-3D, FCH JU, Design of a 1,5 MW demonstration plant ready 2014 HYDROSOL PLANT, FCH JU 2016 Operation of the 750 kw Demonstration plant, CRS Tower, PSA, Spain 2020 Pre-commercial plant

DLR.de Chart 13 H 2 O/CO 2 -Splitting Thermochemical Cycles Solar Production of Jet Fuel EU-FP7 Project SOLAR-JET (2011-2015) SOLAR-JET aims to ascertain the potential for producing jet fuel from concentrated sunlight, CO 2, and water. SOLAR-JET will optimize a two-step solar thermochemical cycle based on ceria redox reactions to produce synthesis gas (syngas) from CO 2 and water, achieving higher solar-to-fuel energy conversion efficiency over current bio and solar fuel processes. First jet fuel produced in Fischer-Tropsch (FT) unit from solar-produced syngas! Int. J. Heat & Fluid Flow 29, 315-326, 2008. Materials 5, 192-209, 2012. Partners: Bauhaus Luftfahrt (D), ETH (CH), DLR (D), SHELL (NL), ARTTIC (F) Funding: EC

DLR.de Chart 14 Solar Pathways from Water or CO 2 to Hydrogen Carbon Monoxide

Hybrid Sulfur Cycle (HyS, Westinghouse) O 2 Wasser H 2 Solar 800 1200 C Elektrolysis High temperature step Low temperature step

DLR.de Chart 16 Solar reactor for sulfuric acid decomposition H 2 SO 4 SO 3 + H 2 O 400 C 850 C 750 C 650 C SO 3 SO 2 + ½ O 2

DLR.de Chart 17 Implementation into a Solar Tower

DLR.de Chart 18 SOL2HY2 Solar To Hydrogen Hybrid Cycles https://sol2hy2.eurocoord.com FCH JU project on the solar driven Utilization of waste SO 2 from fossil sources for co-production of hydrogen and sulphuric acid Hybridization by usage of renewable energy for electrolysis Partners: EngineSoft (IT), Aalto University (FI), DLR (DE), ENEA (IT), Outotec (FI), Erbicol (CH), Oy Woikoski (FI) 100 kw demonstration plant on the solar tower in Jülich, Germany in 2015 Outotec TM Open Cycle (OOC) Utilization of waste SO 2 from fossil sources Co-production of hydrogen and sulphuric acid Hybridization by renewable energy for electrolysis

DLR.de Chart 19 Investments vs. revenues Reduction of initial investments Financing of HyS development by payback of OOC Increase of total revenues

DLR.de Chart 20 Next Step: Pre-commercial application Specific Solar Fuel Tower needed! CRS Tower PSA, Spain Solar Fuels Tower High concentration > 1000 Heliostats fit to receiver size Field control adapted to fuel production processes

DLR.de Chart 21 Thank you very much for your attention!

DLR.de Chart 22 Promising and well researched Thermochemical Cycles Steps Maximum Temperature ( C) LHV Efficiency (%) Sulphur Cycles Hybrid Sulphur (Westinghouse, ISPRA Mark 11) 2 900 (1150 without catalyst) Sulphur Iodine (General Atomics, ISPRA Mark 16) 3 900 (1150 without catalyst) Volatile Metal Oxide Cycles Zinc/Zinc Oxide 2 1800 45 Hybrid Cadmium 1600 42 Non-volatile Metal Oxide Cycles Iron Oxide 2 2200 42 Cerium Oxide 2 2000 68 Ferrites 2 1100 1800 43 Low-Temperature Cycles Hybrid Copper Chlorine 4 530 39 43 38