Overview of activities in CASTOR, ENCAP, CATO and Dynamis at TNO

Transcription

1 Overview of activities in CASTOR, ENCAP, CATO and Dynamis at TNO TNO Science & Industry Department of separation technology Internet:

2 Overview Post-combustion related activities: MGA Developments in CASTOR/CATO Post combustion CO 2 capture in EU-Dynamis Caprice Construction of hybrid-pilot in CATO Chemical Looping Combustion related activities: Development of fixed bed CLC reactors in ENCAP and CATO

3 CASTOR CO 2 CApture and STORage CASTOR Main activities CO 2 -storage, verification and monitoring (TNO NITG) Esbjerg pilot plant experimental program (TNO I&T) System modelling and economic optimalisation (TNO I&T) Development of MGA for absorption/desorption (TNO I&T) Membrane selection (absorption/desorption) MGA contactor development (absorption/desorption) Basic design of absorption MGA installation

4 Principle CO 2 Membrane Gas Absorption CO 2, present in the flue gas, is selectively absorbed into a proprietary absorption liquid through a porous membrane

5 Advantages CO 2 MGA High selectivity Compact equipment Independent flow control No entrainment, flooding, channelling, foaming Not influenced by tilt Low liquid pumping power Flexibility in scale-up

6 Future - Membrane Gas Absorption/Desorption Flue gas out CO 2 storage Flue gas in

7 MGA process development Breakthrough pressures of membranes with absorption liquids Liquid site mass transfer (with spacer) 1 1 Oxygen desorption tests kl = + Membrane characterisation Kov kgas k SO 2 experiments km and kg 1 membrane + k 1 liquid Bulk of Gas Gas boundary layer Microporous membrane Liquid boundary layer Bulk of liquid CCO 2 (g) CCO m2 (g) CCO m1 (g) CCO m2 (l) CCO 2 (l) 1/k g 1/k m 1/mEk l

8 Liquid-side mass transfer of membrane channel (kl) Oxygen-setup

9 Liquid-side mass transfer of membrane channel (kl) 8,00E-06 Mass transfer coefficient (m/s) 7,00E-06 6,00E-06 5,00E-06 4,00E-06 3,00E-06 kact ktheor 2,00E Liquid flow rate (l/min)

10 Gas and membrane mass transfer resistance SO 2 -setup N 2 cylinder SO 2 Analyser MFC2 MFC1 SO 2 cylinder E-1 Membrane module TI-1 PI-1 PI-2 TI-2 P-5 Gas Side Cold Trap TI-3 PI-3 Liquid Side PI-4 TI-4 SO 2 Analyser I-11 1M KOH

11 SO 2 -experiments Overall mass transfer coefficient SO 2 reaction with KOH very rapid mk L E CO2 >>k m, k g 1 K ov = 1 k g + 1 k m 1 K o v = α g 1 Re β + 1 k m 1/K ov 1 / αg 1/k m 1/Re β

12 Membrane desorption set-up at TNO

13 Membrane desorption Membrane testing at various temperatures and pressures Membrane desorption process development AL=0.24 AL=0.24 H2O CO 2 Flux vs Liquid side pressure (T= 120ºC, P=0.15 bar) J CO2 (g/m 2. m in) Liquid pre ssure (bara)

14 Membrane absorption set-up at TNO

15 Preliminary results of membrane absorption/desorption 5.0E-03 Mass Transfer Coefficients for varing Absorption Liquids 4.5E E E-03 ko v [m/s] 3.0E E E E E E E+00 Solve nt A CORAL MEA - Fresh NB_8 Solve nt C Solve nt B MEA - Reg.

16 Membrane contactor development Boundary conditions and choices for a membrane contactor Module channel wide Module channel length Module total height Module gas channel height Module liquid channel height Number of gas channels 322 Number of liquid channels 322 Number of baffles liquid side Gas speed Liquid speed Gas side pressure drop Liquid side pressure drop Membrane area per feed gas 1.0 meter 3.0 meter Approx. 1 meter Weight module filled (approx.) 2500 kg 2.0 mm (spacer filled) 1.0 mm (spacer filled) 5 x (approach counter current) 2.0 m/s m/s 3 4 kpa CO 2 capture ratio 90 % kpa CO 2 content in flue gas 5 25 % Flue gas mass flow single channel Total module gas side mass flow Total module liquid side mass flow Weight module empty (approx.) Approx. 0.5 m 2 per m 3 /hour kg/h (at 2 m/s gas speed) Around 6000 kg/h (at 2 m/s) kg/h (at 2 m/s) (depending on CO 2 inlet conc.) 1400 kg (incl. heavy support mounting)

17 Power plant Results CASTOR conventional absorber and MGA Gas fired combined cycle [393 MW e ] Conventional column Gas fired combined cycle [393 MW e ] MGA Bituminous coal fired power plant [600 MW e ] conventional column Bituminous coal fired power plant [600 MW e ] conventional column CO 2 product capacity ton CO 2 /hr Equipment Parameter Absorber column Columns Dimension Φ 10.7m x 29.5m Φ 11.4m x 17.0m Φ 10.9m x 28.1m Φ 11.2m x 16.0m Packing 1605 m E 6 m E 5 m 2 Radial flow profile with flat sheet contactor Based on in-house measured data with Coral liquids Conclusions: Significant lower footprint possible (drive for improved liquids)

18 Large scale flat sheet modules by Keppel Seghers and TNO

19 DYNAMIS Towards hydrogen production with CO 2 management Program The EU HYPOGEN initiative for hydrogen economy Started march 2006 To asses the options for full scale HYPOGEN Power Plant Full scale pilot to be build by industry post-2008 Full production HYPOGEN Power Plant to go on stream by 2012 Boundary conditions Combined cycle power generation 400 MWe (approx. 700 MW) Hydrogen production MW (flexible 0-100% hydrogen????) Hydrogen spec s according EU hydrogen infrastructure (2010) 90% CO 2 capture CO 2 capture cost of per tonne CO 2

20 DYNAMIS Post-combustion CO 2 capture options researched by TNO Coal gasification with post-combustion CO2 capture split stream amine scrubbing of H 2 producing WGS reactor H 2 Off-gas PSA Water gas shift CO 2 H 2 Pressurised Amine scrubber H 2 (minor N 2 ) Steam or water Coal COAL Oxidizer gasification 90% O 2, 10% N 2 Syngas AIR Off-gas Syngas turbine combined cycle (state of the art) Flue gas recycle (HP-Steam) Flue Gas 15% CO 2 15 Rich Amine Lean Amine Postcombustion Capture CO 2 Exhaust

21 CAPRICE CO 2 capture using Amine Processes: International Cooperation and Exchange o o o o STREP currently under negotiation with EC Cooperation between CASTOR-partners and consortium around International Test Centre on CO 2 capture (University of Regina, Canada) Extending research efforts to other CSLF countries (China, Russia, Brasil) Partnership EU - linked: TNO, NTNU, Stuttgart University, IFP, Elsam, E2, E.ON- UK, TIPS, Tsinghua University Canada - linked: Energy Inet, ITC, Un. of Regina, Alberta Research Council, Unifacs

22 Caprice Project activities: 1. Benchmarking and validation of amine processes 2. Membrane contactor validation studies 3. Development of tools for integration Budget: Total 1.1 MEuro EC-contribution: 0.38 MEuro Equal effort by EU and CDN partnership Key deliverables: Input to CSLF Action plan for further post-combustion R,D&D on global scale

23 Construction of hybrid-pilot in CATO Dutch post-combustion CO 2 capture pilot plant (250 kg/h) Budget around K 1000 Start construction expected third quarter of 2006, finished second quarter 2007 Location? (planned at a coal-fired power plant) First operation with conventional columns but with CORAL liquids Pilot to be upgraded with membrane contactors for SO 2 and CO 2 removal.

24 Chemical Looping Combustion (CLC) in ENCAP and CATO Important features of CLC Air and fuel are only contacted via an oxygen carrier (a metal/metal oxide, e.g. Ni/NiO, Fe/Fe 2 O 3 ) No NOx formation (absence of flame) No dilution of CO 2 with N 2 no energy penalty for separation Air MeO CO 2, H 2 O I II N 2 Me Fuel I: 4 Me + 2 O 2 4 MeO ( H < 0) II: 4 MeO + CH 4 4 Me + CO H 2 O ( H > 0)

25 Chemical Looping Combustion (CLC) in ENCAP and CATO CLC has in theory high potential for Zero Emission Power Production: Theoretical high thermal efficiency Low CO 2 separation cost Fluidising Circulating Bed technology close to current standard Current development status of CLC: Only applicable for gaseous/liquid fuels No integration with gas turbine Risk of particle carry-over Limited intermediate temperature stability High particle cost (environmental concerns) CLC is more expensive then post-combustion CO 2 capture

26 Chemical Looping Combustion (CLC) in ENCAP and CATO New developments on CLC: Integration of CLC-reactor with Combined Cycle Power Plant Reactor concept for CLC: N 2 /O 2 N 2 /O 2 CO 2 /H 2 O CO 2 /H 2 O air CH 4 air CH 4 Recirculation or stationary solids?

27 Chemical Looping Combustion (CLC) in ENCAP and CATO Fixed bed diffusive reactor

28 Chemical Looping Combustion (CLC) in ENCAP and CATO Results of modelling work The formation of a reaction front in the packed bed around an active membrane based on diffusion

29 Chemical Looping Combustion (CLC) in ENCAP and CATO Future work on CLC Further development of fixed bed CLC reactors integrated with combined cycle power plant Development of new temperature stable intermediates Modelling of complete process Testing of pilot installation

30 Conclusions TNO focuses on CO 2 post-combustion capture! 1. Most developed CO 2 capture technology 2. High potential for further improvement Development of improved liquids Process integration and novel processes steps Optimized and new contactors Process modelling and economic optimisation Future development includes fixed bed CLC processes!