Mitglied der Helmholtz-Gemeinschaft Oxygen Transport Membrane Modules for Oxyfuel Applications developed in GREEN-CC AMPEA Workshop Materials for membranes in energy applications: gas separation membranes, electrolysers and fuel cells SINTEF, Oslo, NO, Feb 7-8 th 2017 Stefan Baumann Forschungszentrum Jülich Institute of Energy and Climate Research IEK-1 52425 Jülich, Germany
Project facts and figures Graded Membranes for Energy Efficient New generation Carbon Capture Process WP1: Membrane - Materials - Support - Assembly - Modeling Coordinator: Dr. Wilhelm A. Meulenberg - Application - Stability Forschungszentrum - Slip stream in real PP Jülich - Modeling WP2: Catalyst - Materials WP3: Application oriented testing - Permeation WP4: Proof-of-concept - Module design - Membrane assembling - Test facilities design www.green-cc.eu - Module testing WP5: Process Engineering - Process Simulations - Scale up rules - Cost estimations Total Budget: 8.200.000 Funding: 5.400.000 Duration: 01.09.2013-31.08.2017 FP7 project no. 608524 2
Outline Graded Membranes for Energy Efficient New generation Carbon Capture Process Coordinator: Dr. Wilhelm A. Meulenberg Forschungszentrum Jülich WP5: Process Engineering - Process Simulations www.green-cc.eu - Scale up rules - Cost estimations Total Budget: 8.200.000 Funding: 5.400.000 Duration: 01.09.2013-31.08.2017 FP7 project no. 608524 3
4-end membranes for oxyfuel combustion in industrial applications retentate (depleted Air p O2, retentate ) feed (Air, p O2, feed ) O 2- e - j(o 2 ) sweep (O 2 -lean gas, p O2, sweep ) permeate (O 2 -rich gas, p O2, permeate ) Main target: Identifying the energetic and economic benefit of an OTM in all 3 process routes under consideration of realistic boundary conditions IGCC Oxyfuel Power Plant Oxyfuel Cement 4
Process conditions Oxyfuel process - 4-end integration Depleted air O 2 Hot flue gas cleaning Flue gas concentration component CO 850 C 2 H 2 O/CO 2 balance H 2 O 25 % O 2 3-5% SO 2 NO x 2000 ppm (no gas cleaning) CO 2 H 2 O 500 ppm (state-of-the-art HT-cleaning) Steam 50 ppm (state-of-the-art LT-cleaning) 140 ppm HCl 30 ppm Feed-air O 2 /H 2 O/CO 2 CO Others (incl. Ash) 10 ppm??? Water Fuel/Coal 5
Project facts and figures Graded Membranes for Energy Efficient New generation Carbon Capture Process Coordinator: Dr. Wilhelm A. Meulenberg Forschungszentrum Jülich WP4: Proof-of-concept - Module design - Membrane assembling - Test facilities design www.green-cc.eu - Module testing WP5: Process Engineering - Process Simulations - Scale up rules - Cost estimations Total Budget: 8.200.000 Funding: 5.400.000 Duration: 01.09.2013-31.08.2017 FP7 project no. 608524 6
Module design and operation Design and build of a proof- of-concept membrane module Planar stack with asymmetric membranes Effective area at least 300 cm 2 4-end operation Key issues/activities Mechanical stress analysis CFD simulation Joining techniques for ceramic-ceramic and ceramic-metal joints Design and build of a pilot loop for module testing Proof of performance (TRL 4) Operating temperature 750 900 C Leakage lower than 2% Long term tests (1000 h) in a synthetic flue gas stream 7
Outline WP1: Membrane - Materials - Support - Assembly - Modeling WP4: Proof-of-concept - Module design - Membrane assembling - Test facilities design - Module testing WP5: Process Engineering - Process Simulations - Scale up rules - Cost estimations 8
Oxygen Transport in Mixed Conductors Zone III Bulk diffusion j O 1 RT σ i σ e 2 = ln L 16 F² σ + σ i e p p ' O 2 '' O 2 I & VI II & IV III V Gastransport Surface Exchange Bulk Diffusion Gastransport in Support (1) Zone II & IV Zone V Surface exchange kinetics 1 RT σ i σ p e jo 2 = ln L + 2L 16 F² σ + σ p D k Gas transport in support c * L c = Characteristic Thickness TT,PP xx ii + xx ii pp pp gggggg = RRRR xx iijj jj xx jj jj ii gggggg PP gggggg DD iiii nn jj =1 i e ' O '' O 2 2 (2) ff RRRR iiii jj pp ii gggggg 1. Schulze-Küppers, Dissertation Ruhr-Universität Bochum (2010) 2. Bouwmeester et al. Fundamentals of Inorganic Membrane Science and Technology (1996) driving force molecular diffusion Knudsen-Diff. + viscos flow 9
Selected materials Single phase perovskites Dual phase composites Ionic conductor: Doped Ce 0.8 Gd ceria 0.2 O 2 stabilized zirconia La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (reference) Electronic conductor: Spinels FeCo 2 O 4 doped ZnO perovskites High performance Asymmetric membranes developed Good stability in CO 2 Limited stability in SO 2 10
Ce 0.8 Gd 0.2 O 2-δ - FeCo 2 O 4 TEM Analysis 3 phases identified: Ce-Gd-O Gd-Ce-Fe-Co-O Fe-Co-O is wrapped in porous O deficient Fe/Co-O phase (with preferential porosity) After optimized sintering cycle FeO y Ramasamy et al. J Amer Ceram Soc 99 (2016) 349-355 CoO y 11
60 wt% Ce 0.8 Gd 0.2 O 2-δ - 40 wt% FeCo 2 O 4 Temperature C 1050 1000 950 900 850 800 750 700 650-6.5 CGO-FCO CGO-FCO-LSCF-AB LSCF58 log permeance mol/(cm2 s) -7.0-7.5-8.0-8.5 E a (CGO-FCO)= 97 kj/mol E a (LSCF58) =138 kj/mol E a (CGO-FCO+LSCF-AB)= 66 kj/mol -9.0 0.8 0.9 1.0 1.1 j permeance = ln 1000/T (K -1 ) O2 p' p'' O2 O2 = 1 R σ it L 16 F² Ionic conductivity of CGO is rate limiting if surfaces are activated Ramasamy et al. J. Am. Ceram. Soc., 99 [1] 349 355 (2016) approximate composition of the perovskite phase is 15% Ce on A- site, 25% Co on B-site, i.e. Gd 0.85 Ce 0.15 Fe 0.75 Co 0.25 O 3 (GCFCO) Ramasamy et al. Ceram Sci Eng Proc, ICACC 2016, accepted manuscript 12
Electrical conductivity GCFCO is a pure electronic conductor contributing to ambipolar conductivity Electronic conductivity still dominant for 20 wt% spinel content Percolating network present in as low as 10 wt% of spinel content Ramasamy et al. Ceram Sci Eng Proc, ICACC 2016, accepted manuscript 13
Oxygen permeation rate CGO-FCO in wt % CGO-FCO in vol % 60:40 54:46 65:35 59:41 70:30 64.5:35.5 75:25 70:30 80:20 76:24 85:15 81.5:18.5 90:10 87.5:12.5 Maximum permeation rate achieved using 15 wt% spinel Ramasamy et al. to be submitted 14
Performance of selected OTM materials LSCF vs 85CGO-15FCO La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF) as reference material and ready for scale up Dual phase composites more stable, but less mature. Selection for scale up made for 85 wt% Ce 0.8 Gd 0.2 O 2-δ 15 wt% FeCo 2 O 4 (CGO-FCO) 15
Sequential Tape Casing Requirements for membranes according to transport Model: Thin, defect free membrane layer on a porous support Tape casting support (slurry obtaining pore former) Pre-sintering Support Screen printing on support Composite sintering Tape casting Membrane layer (slurry without pore former) Tape casting Support (slurry containing pore former) Co-firing Membrane layer + support Membrane layer porous support Tape casting + screen printing Polymer carrier Sequential tape casting 16
Membrane Development Ce 0.8 Gd 0.2 O 2-δ - FeCo 2 O 4 Activation layer: 6 µm Thickness ~ 1000 µm Surface exchange limited!!! Activation layer: 5 µm Membrane layer: 14 µm Support porosity: 41 % Thickness ~ 700 µm 17
Scale up of LSCF membranes Tape casting Tape casting/ lamination/ milling Tape casting 18
Scale up LSCF Component 7 x 10 cm 2 Masks for milling process tape casting in larger scale Closing of porous edges 19
Acknowledgement Thank You for Your attention FP7 project no. 608524 20