Scaled up production of ceramic membranes for oxyfuel capture Marie-Laure Fontaine (SINTEF), Christelle Denonville (SINTEF), Adam Stevenson (Saint Gobain CREE), Christian His (Saint Gobain CREE), Emmanuel Mercier (Saint Gobain CREE), Caroline Tardivat (Saint Gobain CREE), Marijke Jacobs (VITO), Frans Snijkers (VITO), Falk Schulze-Küppers (FZJ), Wilhelm Meulenberg (FZJ), Wen Xing (SINTEF), Zuoan Li (SINTEF) Jonathan Polfus (SINTEF), Ove Paulsen (SINTEF), Paul Inge Dahl (SINTEF), Partow Henriksen (SINTEF), Rune Bredesen (SINTEF)
Efficient Tubular Membranes for Oxy-Combustion • EU FP7 (2011-2016): Demonstration project • Coordinator: RISOE DTU (DK) • Partners: Air Liquide (FR), INABENZA (SP), Saint-Gobain Cree (FR), FZJ (DE), VITO (BE), SINTEF (NO), IKTS (DE)
CaTi 0.85- x Fe 0.15 Mn x O 3- δ , x = 0.0-0.4 • Low creep rate • Low cost • Stable in large oxygen partial pressure gradient and in CO 2 atmosphere • No phase transition from RT→ sintering T • Fairly good sinterability (1300°C – 1400°C) • TEC about 13. 10 ‐6 K ‐1 (RT – 900 °C) 3
Scaling up CaTi 1-x Fe x O 3- d asymmetric membrane Quality control parameters : Step 3: 70 cm ++ • Thickness, • Porosity, • Powder +Tubular supports • Straightness, roundness, • Leak tightness at RT 50 microns • Thin film membranes • Flux data Step 2: 25cm < L ≤ 50cm • Porous catalytic layers • Powder production • Sealing Step 1: Length ≤ 25cm • Tubular supports • • Powder production Thin film membranes Infrastructure up- • Tubular supports • Porous catalytic layers grade (coating • Thin film membranes tools, furnaces, • mixers …) • Porous catalytic layers Sealing 4 • Sealing (several partners)
Production line Calendaring Sintering Sealing of caps Slurries and Pre- Powder Dip- Extrusion Sintering pastes annealing production coating of supports preparation (100 kg++) Clean room Clean room class 7 class 7 45 cm Up to 1 m long 5
SG1 SG1 Scaling up of membranes SG2 SG2 4.0 SG11 SG11 3.5 Small layer HT21 Log Differential Intrusion (mL/g) 3.0 2.5 25cm < L ≤ 50cm 2.0 1.5 1.0 0.5 0.0 0.1 1 10 100 Pore size Diameter (um) Samples Open porosity (%) SG1 45.2 SG011 40.8 HT21 40.0 HT31 40.2 Expected porosity versus volume 6 of pore former: 45%
X-ray computational tomography Porosity and tortuosity Porosity in central volume: 45 % Tortuosity: 1.7 Pore size distribution Average size: 7.5 µm St. deviation: 2.8 µm A 753*753*1411 µm 3 (800x800x1500 pixels) volume 7
Dr. Falk Schulze-Küppers Sealing : glass ceramic Stability of seal tested in operation for 6 months at ambient pressure Leak rate: 6.10 -4 mbar.l/s TEC transfer CTF Steel CTF Seal 8 Leak rate: 1.10 -7 mbar.l/s 50 microns 100 microns
Flux measurements for the first scaling up Adjustment of procedures for heat treatment and coating for long membranes improve flux * Reference case for transfer: 45 microns thick CTF membranes 9
Scaling up at SG membranes: 70 cm ≤ Membrane 100 microns 100 microns • Thickness of the dense CTF layer: ca. 45 microns from top to bottom • Thickness of porous support: ca. 0.9 mm 10
Scaling up at SG membranes: 70 cm ≤ OTM Gradient Air/Vacuum: Leak rate: 0.24 ml/min i.e. ca 1% leak rate for a flux of 0.1 ml/min.cm 2 Bubble test at 0.5 bar over pressure: no leak 11
Activation layer by spray-coating Jacobs M. et al, Journal of Membrane Science 477 (2015) 58-64 10 microns 50 microns 7-8 µm CTF coating on short membrane 6-9 µm CTF coating on 70cm long membrane 30 cm • Air and Ar flow of 50 ml/min • Effective membrane surface areas: 9-10 cm 2 12
Testing of 70 cm membrane Furnace Sweep gas supply; there is a similar inside feed gas supply tube Cooling system Base 13 Probostat TM
Flux as function of T and pO 2 T=1000°C, inner sweep Ar (400 mL/min), feed (600 mL/min) T=950°C, inner sweep Ar (400 mL/min), feed (600 mL/min) 0.8 T=900°C, inner sweep Ar (400 mL/min), feed (400 mL/min) T=850°C, outer sweep Ar (500 mL/min), feed (400 mL/min) T=850°C, inner sweep Ar (200 mL/min), feed (400 mL/min) 0.7 T=800°C, inner sweep Ar (200 mL/min), feed (200 mL/min) 0.6 2 ) J (O 2 ) (mL/min cm 0.5 0.4 0.3 oxygen purity above 99% 0.2 0.1 0.0 0.0 0.2 0.4 0.6 0.8 1.0 pO 2 (atm) 14
Summary • Manufacturing protocol for CTF based tubular asymmetric membranes developed • Protocol transfer from SINTEF to SG CREE achieved • Further scaling-up of membranes to 70 cm by SG achieved • Scaling-up of activation layer at VITO achieved • Protocol transfer from SINTEF to FZJ on sealing technology achieved 15
Acknowledgements This work has been supported by the EC within the 7th framework programme under grant agreement no. FP7-ENERGY-268165 16
HETMOC • Line 1: Air/vacuum stability • Line 2: CO 2 , steam stability 17
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