NanoGLOWA post-combustion CO 2 capture membranes

Transcription

1 NanoGLOWA post-combustion CO 2 capture membranes Progress, performance and pilot testing at six industrial test sites Martijn Huibers, Ludwin Daal, Paul Raats (KEMA Netherlands) Post-Combustion Capture Conference 2011 (PCCC1) Abu Dhabi, May 17-19, 2011

2 Ambitious goal for materials project: from fundamental research to vast plants 2 µm R&D start: 10 cm 2 Final app: ~1-10 M m 2 Scale factor = ten billion x! 2

3 KEMA and R&D history Membranes for CO 2 capture / NanoGLOWA NanoGLOWA key membranes & facts DTM: Diffusion Transport Membrane tests KEMA flue gas simulator Ruthenberg power plant Borssele power plant Scholven power plant FSC: Fixed Site Carrier membrane tests ICHP dedicated test rig Borssele power plant Sines power plant Conclusions so far & outlook Contents Acknowledgement: All 26 NanoGLOWA project partners 3

4 KEMA: covering the energy value chain 4

5 Before CO 2 : water capture with membranes 400 MW coal-fired PP: Emits 150 m 3 / h H 2 O (l) Needs 30 m 3 / h H 2 O (l) 20% capture suffices Reheating of flue gas = 1% energy penalty Performance: 3-4 kg / m 2 h ~20 µs / cm 5000h (waste inc.) Now upscaling (CapWa) and commercialising (patented) Furnace ESP Flue gas Desulphurization Membranes 5

6 Membranes for CO 2 capture: essentials Feed Feed Feed Membrane Membrane Driving force c, P, T, E Driving force! Retentate Membrane unit Permeate Permeate Permeate Essence of a membrane: Selective transport of components through material Speed*: permeance Speed ratio: selectivity Driving force needed partial pressure, e.g.: Feed compression Permeate vacuum Sweep gas * In volume per time per pressure unit 6 6

7 Membranes for CC: appealing potential Post-combustion CO 2 -selective membrane advantages: No chemicals involved (also political / legal pro) No waste streams Continuous: no separate regeneration step Easily scalable (modular) Plug & play Note: absorber technology seems more mature, but: Membranes are large scale and commercial, e.g.: natural gas sweetening (gas separation) reverse osmosis (millions of m 2 ) Absorbers need post FGD SO 2 polishing NanoGLOWA membranes: aiming for no pretreatment 7

8 Location in power plant Scheme: flue gas flow of coal-fired power plant Capture location: best conditions ( clean, T, ) - NOx - SO 2 - particles 8

9 NanoGLOWA: key membranes and facts Objective: To develop optimal nanostructured membranes and installations for different applications in CO 2 capture from power plants Content Post and precombustion capture - CO 2 /N 2, CO 2 /H 2 5 membrane materials - polymer (3), ceramic and carbon 4 module types - fibers, spiral wound, tubular and flat sheet Process 5 development paths 6 universities 5 end users Budget 13 mio EUR 26 partners (KEMA co.) 14 countries Duration 5 years 1) IP: aimed at industrial breakthrough 1)

10 Diffusion Transport Membranes (DTM) univ. Twente Porous support fibre with selective coating Very high selectivities, lower permeabilities Glassy polymers provides selectivity Proven high durability, >5000h in flue gas Coating < 1µm possible, but difficult µm 1 µm

11 Fixed Site Carrier (FSC) membranes univ. Trondheim (NTNU) Composite fixed-site carrier-membrane µm-thin selective PVAm layer on PSf support Very high selectivities attainable Challenge: durability (amines) 11

12 NanoGLOWA membrane R&D progress Selectivity: up to 320 (CO 2 over N 2 ) Permeance: over 1 m 3 / m 2 h bar Durability: ppm SO 2 / NO x Energy penalty: -7.4 % pt. possible (Siemens, RWTH) 75% recovery, 97% purity, 200 bar Focus: consortium vote best performing ones chosen FSC membranes (NTNU) DTM: SPEEK - based membranes (Univ. Twente) Proceeding from labs to next phase: industrial testing (small and medium scale) 12

13 Factual overview: NanoGLOWA testing activities on three levels Laboratories Industrial: simulators Industrial: p. plants Gas supply CO 2 / N 2 / H 2 O + O 2 / SO 2 / NO X complete flue gases Feed flow << 1 m 3 /h 1-10 m 3 /h 5-50 m 3 /h Membrane area ~ 5 cm m m 2 Scale factor n = 1 n = 200 n = 2,000 Tests duration mins - hours up to 500 hours half a year year 13

14 Visual overview of testing phase DTM Time FSC KEMA I. Big lab scale ICHP Ruthenberg PP Borssele PP II. Power plant: durability Borssele PP Scholven PP III. Power plant: duration Sines PP After NanoGLOWA Commercial tests / app.? After NanoGLOWA 14

15 DTM Test module: hollow fibres Curtain prototype module Developed from scratch Outside-in Principle KEMA DTM I. Big lab scale 15

16 KEMA flue gas simulator exhaust A R T I F I C I A L F L U E G A S Gas burner DTM I. Big lab scale bypass valve FEED IN Flue gas sim Feed ~6,5 % CO 2 ~ m 3 /h Up to 100% RH no particles no SO 2 (optional) Heating wire Membrane module cooler drain feed out (module bypass) vacuum pump RETENTATE PERMEATE 16 valve

17 Ruthenberg power plant DTM II. PP durability Curtain module PES without selective coating Tested: module performance membrane durability Pressure drop: negligible (1-2 mbar) 17 Durability: satisfactory

18 Before Ruthenberg PP No visible damage No pressure drop increase Visually: slight fouling (ash) DTM II. PP durability After 18

19 Ruthenberg PP Commercial modules: uncoated PPO Inside out filters required Most effective separation, but filters and this module config pressure drop Permeance 0,04 m 3 /m 2 hbar Selectivity (dep. on T) CO 2 purity 30-60%, dep. on conditions to be optimised DTM II. PP durability 19

20 Borssele PP: updated module Performance and durability testing Moderate CO 2 purity Small leak occurred DTM II. PP durability 20

21 Borssele PP: updated module DTM II. PP durability Flue gas composition: 80% N 2, 14% CO 2, 6% O 2 Relative humidity: 100% Average SO 2 : 90 mg / m 3 Average NO x : 150 mg / m 3 Flue gas feed temp.: +/- 42 C Permeate vacuum: mbar 21

22 Scholven PP: starting next week 2 module types 3 weeks for each module 1w determine optimal process conditions 2w monitoring optimum Also much water captured; measure quality DTM III. PP duration 22

23 Test setup KEMA curtain shaped module Flue gas downstream FGD C, +3 hpa Trace heated - Temperature - Pressure Fan 30 m³/h Bypass p Membrane - Temperature - Pressure - Volumeflow - CO 2, SO 2, O 2 Flue gas back to the duct - Pressure - Volumeflow Micro GC (by KEMA) Condenser DTM III. PP duration 23

24 Test setup Parker membrane module - Temperature - Pressure Flue gas downstream FGD C, +3 hpa Trace heated m³/h Bypass p Filter - Temperature - Pressure Pump Bypass p Membrane - Temperature - Pressure - Volumeflow - CO 2, SO 2, O 2 Flue gas back to the duct - Pressure - Flowrate Condenser Micro GC (by KEMA) Fibers: 6000 Length: 0,58 m Membrane area: 5,8 m 2 DTM III. PP duration 24

25 FSC Upscaled perf. tests: artificial flue gas vent vent vent vent FR 1 MFC 1 PR 1 TR 1 HR 1 SO 2, NO analyser PR 2 TR 2 HR 2 BPV 7 6-port automatic valve GC 10 vent FR 2 2 MFC 2 6 drain 8 MFC 3 MFC 4 PR 3 TR 3 HR 3 drain 7 drain mix NO 3 4 N 2 + SO drain 9 1 drain Flue gas sim, from scratch 1-10 m 3 /h Well controllable, automated FSC I. Big lab scale C, 95% RH Feed 17% CO 2 SO 2 and NO x added 3 months continuous test 25

26 Upscaled perf. tests: ICHP test rig FSC I. Big lab scale 26

27 Upscaled perf. tests: results Membrane performance meets end user criteria proven operation in real / realistic flue gas Feed ~13-17% CO 2, ~95% RH 200 mg/m 3 SO 2 and NO x >75% performance over time (in fact stable at >80%) Selectivity / permeance good up to ~90% CO 2 purity Modest breakthrough achieved Research membranes: often high selectivity and/or permeance, but no durability, too complex, expensive NanoGLOWA: robust and high-performance membranes! FSC I. Big lab scale 27

28 Durability Borssele PP ICHP before and after comparison Result: identical (within normal fluctuations) Last indication of durability GO for duration test FSC II. PP durability 28

29 Duration Sines PP Test installation: membranes in module in test rig FDG bypass plus analytical equipment Boiler SCR ESP FGD FSC III. PP duration 29

30 Duration Sines PP Scale: m 3 /h flue gas Some m 2 of membrane area ± 6 months continuous testing Special interest: particles, durability, condensation Exploration of pretreatment options (optional!) Novel test rig design Novel flat sheet module design ESP ESP GGH FGD Startup: tomorrow! FSC III. PP duration 30

31 Conclusions so far NanoGLOWA membranes CO 2 -membranes evolving from labs to power plants! Significant R&D progress & experimental confirmation, e.g. Durability mg SO 2 / NO x! Selectivity up to 320 Permeance up to 1 m 3 / m 2 hbar Industrial tests at 6 sites 4 industrial tests carried out succesfully 2 pilot tests about to begin, expectations high Technology maturing rapidly Not commercial CCS today, but tomorrow? other industries / processes 31

32 Outlook NanoGLOWA membranes Completion of duration tests Durability data: 6 Scholven, 6 Sines Performance in time, e.g. purity & recovery Process / system experience: behavior at various settings Further explore optimal system layout tradeoff energy / recovery / purity / area / CAPEX Commercialisation steps Commercial designs (module, system, ) Scaleup (membranes, module, ) Partners / clients 32

33 Thanks for your attention For more information: Participate in NanoGLOWA s Workshop at ICOM 2011, July 24 th, Amsterdam ( martijn.huibers@kema.com / paul.raats@kema.com

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35 Two-stage system Example of a two-stage membrane system Compressor Retentate Expander To atmosphere Flue Gas Retentate 0.2 bar Vacuum pump P Permeate (40-60% CO 2 ) Compressor 1.0 bar 0.2 bar Vacuum pump P Permeate (95.5% CO 2 ) 130 bar To pipeline CO 2 Compressor Consensus: two stage minimum requirement to capture >95% purity CO 2 at recoveries of >90% 35

36 Novel membrane module and test rig FSC III. PP duration Moving into different project phase Selectivity, permeance, etc Purity, recovery, flow etc. 36

37 Some NanoGLOWA aims Energy < 2 GJ / ton Recovery > 60% CO 2 purity > 95% Selectivity > 150 Permeance > 1 m 3 / m 2 h bar Durability > 3 years 37