Solar thermochemical H 2 O and CO 2 splitting
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1 Porous Ceramics for CSP Applications SUPSI, Solar thermochemical H O and C splitting utilizing a reticulated porous ceria redox system Philipp Furler Daniel Marxer Jonathan Scheffe Aldo Steinfeld 11 MW-electric/ 55 MW-thermal 0 MW-electric/ 100 MW-thermal H O Solar Reactor C Fuels
2 H O CO Thermolysis H + ½ O CO + ½ O Equilibrium Mole Fraction [kj/mol] H G TS H p = 1 bar H O H O H OH Temperature [K] Temperature [K] Solar Thermochemical Splitting of H O and C Concentrated Solar Energy MO ox 1 st step: Solar Reduction MO MO O ox red MO red H O/C red red nd step: Oxidation MO H OMO H ox MO CO MO CO ox H /CO recycle MO ox To Liquid Fuels
3 Solar Thermochemical Splitting of H O and C Concentrated Solar Energy Ce 1 st step: Solar Reduction CeO CeO O CeO H O/C nd step: Oxidation CeO H O CeO H CeO CO CeO CO H /CO recycle Ce To Liquid Fuels Solar Thermochemical Splitting of H O and C Panlener, J Physics Chem. Solids 36: 113-, Concentrated Solar Energy 1773 K 1573 K 1373 K 1173 K 1073 K Ce 1 st step: Solar Reduction CeO CeO O H O/C nd step: Oxidation CeO H O CeO H CeO CO CeO CO H /CO recycle Ce To Liquid Fuels Energy & Fuels 6, , 01.
4 Solar Reactor Technology CeO CeO HCeO O CeO O H CeO CO CeO CO Concentrated Solar Radiation Quartz Window Porous Ce CPC Al O 3 insulation Inconel Wall 1500 C 900 C H CO Syngas (H, CO) Science 330, , 010. Experimental Setup
5 Energy Conversion Efficiency solar-to-fuel heating value of fuel produced solar energy input + energy for inert gas recycling solar-to-fuel, average H rfueldt P dt E r dt solar inert inert solar-to-fuel, peak H r solar oxygen P E r inert inert Δ 0 Solar Experimental Results Ce bricks porosity = 76 % SSA =.7 m g -1 Reduction Oxidation Power Input: kw 1.4 kw Gas Flow: l min -1 Ar 9 l min -1 H O/C Ceria Structure: Porous monolithic bricks Total Mass: 35 g C -splitting H O-splitting solar-to-fuel, average 04.% solar-to-fuel, peak 0.8% for CO-splitting 0. 7 % for H O-splitting Science 330, , 010.
6 Simultaneous H O/C -Splitting H O:C = 5.7 Ce felt porosity = 96 % SSA = 6.0 m g -1 Reduction Oxidation Power Input: 3.6 kw 0.8 kw Gas Flows: Ar: l min -1 C : l min -1 H O:.15 l min -1 Ceria Structure: Felt; total mass: 17 g : Fuel = 0.5 ± 0.05 No hydrocarbons No C depositions Total selectivity Energy & Env. Science 5, , 01. Simultaneous H O/C -Splitting Ce felt porosity = 96 % SSA = 6.0 m g -1 Reduction Oxidation Power Input: 3.6 kw 0.7 kw Gas Flows: Ar: l min -1 C : 0.33 l min -1 H O:.0 l min -1 H O:C = 6.7 Ceria Structure: Felt, Total Mass: 17 g Energy & Env. Science 5, , 01.
7 Simultaneous H O/C -Splitting Ce felt porosity = 96 % SSA = 6.0 m g -1 Reduction Oxidation Power Input: 3.6 kw 0.8 kw Gas Flows: Ar: l/min C : l/min H O: l/min Ceria Felt; total mass: 17 g structure: Energy & Env. Science 5, , 01. C -Splitting Ce RPC Reduction Oxidation Power Input: 3.8 kw 0 kw Gas Flow: l min -1 Ar.5 l min -1 C Ceria Structure: RPC; total mass: 1416 g porosity = 88 % SSA = 1.45*10-4 m /g 0.6 reduction oxidation Rate [ml min -1 g -1 Ce ] T Ceria :.3 ml g -1 CO: 4.7 ml g l 6.61 l Time [min] Temperature [ C] : CO = 0.5 ± 0.1 No hydrocarbons No C depositions Total selectivity solar-to-fuel, average 1.73% solar-to-fuel, peak 353. % Energy & Fuels 6, , 01
![min -1 ] 00 500 400 300 00 100 Oxidation: CO evolution evolution Ce felt evolution Ce RPC - - - Heating Rate CeO felt - - - Heating Rate CeO RPC ----- O](/docs-images/96/128195871/images/8-2.jpg "evolution CeO felt ----- O evolution CeO RPC CO Felt : 0.49 l CO RPC : 8.")
8 Ce felt C -Splitting Ce RPC Reduction Oxidation Power Input: 3.6 kw 0.7 kw Gas Flow: l min -1 Ar 3 l min -1 C Ceria Structure: RPC & Felt x μm x μm SSA = 6.00 m /g SSA = 1.45*10-4 m /g Rate [ml min -1 ] Reduction: evolution Felt : 0.4 l RPC : 4.00 l evolution Ce felt evolution Ce RPC Heating Rate CeO felt Heating Rate CeO RPC O evolution CeO felt O evolution CeO RPC Rate [ml min -1 ] Oxidation: CO evolution evolution Ce felt evolution Ce RPC Heating Rate CeO felt Heating Rate CeO RPC O evolution CeO felt O evolution CeO RPC CO Felt : 0.49 l CO RPC : 8.7 l Time [min] Time [min] Energy & Fuels 6, , 01 C -Splitting Ce RPC Reduction Oxidation Power Input: 3.6 kw 0.7 kw Gas Flow: l min -1 Ar 3 l min -1 C Ceria Structure: RPC δ measured thermodynamic equilibrium Energy & Fuels 6, , 01
9 average pore diameter =.54 mm total porosity = 9% specific surface = 11 mm -1 Effective heat/mass transport properties: thermal conductivity heat transfer coefficient permeability extinction coefficient scattering phase function Reticulate Porous Ceramic (RPC) 10 mm J. Heat Transfer 13, 03305, 010. Materials, 5, 19-09, 01. I s Radiative properties of RPC di 4 I I s b I di ds 4 i 0 Change of attenuation augmentation augmentation radiation by by by intensity absorption+scattering internal emission incoming scattering Pore-level radiation Idealized continuous participating media β ASME J. Heat Transfer 13, , 010.
10 I s I s I Radiative properties of RPC di 4 I I s b I di ds 4 i 0 Change of attenuation augmentation augmentation radiation by by by intensity absorption+scattering internal emission incoming scattering exp - s cm MC ray tracing ASME J. Heat Transfer 13, , 010. Fluid transport properties across RPC Int. J. Heat & Fluid Flow 9, , 008. Materials 5, 19-09, 01.
11 Fluid transport properties across RPC p ud F u K pd c0 c1re u D D K F m m Int. J. Heat & Fluid Flow 9, , 008. Materials 5, 19-09, 01. Heat transfer transport across RPC h sf zz '' qdasf z T lm A sf Nu Re Pr Int. J. Heat & Fluid Flow 9, , 008. Materials 5, 19-09, 01.
12 Pore-scale modeling (work in progress) conduction convection radiation chemistry Concentrated Solar Radiation Solar Thermochemical Splitting of H O and C Concentrated Solar Energy MO ox 1 st step: Solar Reduction MO MO O ox red MO red H O/C recycle red red nd step: Oxidation MO H OMO H ox MO CO MO CO MO ox ox H /CO To Liquid Fuels
13 ADSORPTION C Capture from Air ambient air C -depleted air pure C DESORPTION H O and C mass balance Temp-Vacuum-Swing Amine-functionalized silica gel 5 C, 1 bar 90 C, 150 mbar RH = 50% Environmental Science & Tech. 46, , 01. Closing the Materials Cycle Solar Energy Concentrated Solar Energy atmospheric air adsorption desorption C H O H O reduction oxidation syngas catalytic conversion C -depleted air liquid fuels for transportation H O C ambient air + liquid hydrocarbons
14
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