Advances in Materials Research for CCT

Transcription

1 Advances in Materials Research for CCT Lorenz Singheiser JARA ENERGY Institute of Energy Research at Forschungszentrum Jülich GmbH CCT 2009 May Dresden 2. Juni 2009 Folie 1

2 ntent Materials and atings for advanced gas turbines Advanced steam turbines and boilers Membranes for new power plant processes 2 2. Juni 2009 Folie 2

3 Progress in Gas Turbine Development 1400 Film cooling Temperature [ºC] S-816 Firing temperature N 80 A M 252U500 IN738 U700 IN939 Single Crystal IN792 DS Year TBC Material Improvement 2000 Source V. Thien, Siemens PG Advances in oling, atings, and Structural Material technologies are prerequisites for advanced gas turbine engines 2. Juni 2009 Folie 4

4 CO 2 reduction by increased efficiency of combined cycle Power plants CO 2 - Reduction (%) GT 13E1 GT 13D2 GT 26 GT 13E2 Source : Alstom GT 13D GT 13B sis: Turbine with 880 C, 9,6 bar GT 13C Year of introduction Efficiency increase: less emissions & fossil fuel savings 2. Juni 2009 Folie 5

5 Materials Research for Gas Turbines - reliable thermal barrier coatings (TBCs) for combustors and front stage blading - new TBCs with higher temperature capability 1400 C - life prediction methodologies for TBC coated SX alloys as integral part of the design - austenitic rotors (also for steam turbines) Source: Siemens Journals Gas temperature target: > 1400 C se material life: h ating life: h Rotor life: h - fibre reinforced ceramics and intermetallics to ensure efficiencies > 65 % (2015) > 70 % (beyond 2020) 2. Juni 2009 Folie 6

6 Thermal rrier atings (TBCs) blades 1000 C 1200 C 1400 C Hot Gas Thermal rrier ating Bond at se Material vanes oling Gas Increase in efficiency: Higher hot gas temperature Reduced cooling 2. Juni 2009 Folie 7

7 Single gas turbine blade a turbine blade has. the power of 10 Porsche but the price of a blade - is only that of one Volkswagen Rabbit! V. Thien, Siemens Power Gen 8 2. Juni 2009 Folie 8

8 Process Technology and Diagnostics have to be improved APS HVOF - powder processing - industrial scale - plasma-spray facilities - sophisticated diagnostic systems VPS - instrumented burner rigs & TMF diagnostics Vaßen et al. 2. Juni 2009 Folie 9

9 Life modelling of high Thermal rrier atings Process modelling process understanding using diagnostics improved reproducibility microstructural design by modelling deformation rate [1/s] 1E C 1050 C 950 C 850 C 20 C 1E-5 1E-6 1E-7 1E-8 1E-9 1E-10 1E-3 1E-2 1E-1 1E+0 1E+1 1E+2 1E+3 time [h] life prediction modelling evaluate visco-plastic properties of TBC Bond ating TGO implementation into life model extend life model to 3 D implement crack growth extension to new TBC systems Beck, Steinbrech et al Juni 2009 Folie 11

10 New TBC Systems for > 65 % Efficiency offer highest potential for GTs > 1400 C 1100 C 1100 C La 2 Zr 2 O 7 YSZ 950 C > 1000 C YSZ MCrAlY bond coating new bond coatings current DS, SX alloys next gen. SX alloy 200 µm state of the art TBC system Temperature goal 2015 TBC system Vaßen, Quadakkers, et al. 2. Juni 2009 Folie 12

11 Sensor coatings Hot gas YSZ (APS) NiCrAlY (VPS) CMSX4 T[ C] Siemens Full exploitation of lifetime benefit at high temperatures by smart coatings providing: Light Phosphore A λ A λ B at 380 Celsius 6000 at 500 celsius 4000 at 600 Celsius Time / microseconds Protection of metallic components Online monitoring of critical temperature load Indication of degradation Phosphore B Standard coating Vaßen, et al. Doped layers Southside Thermal Sciences Limited 2. Juni 2009 Folie 14

12 Materials for boilers and steam turbines Materials key technolgy for η increase 2. Juni 2009 Folie 16 PAG

13 Materials are key technology to increase η Technology C, 275 bar η = 45 % ferritic martensitic steels (P92, VM 12) austenitics for super heaters Technology > C, 350 bar η > 50 % ferritic martensitic steels (P92, VM 12) Nickel alloys for super heaters, pipes and rotors Technology > C, 350 bar, η = 55 % advanced Ni alloys 2. Juni 2009 Folie 17

14 Maximum operation temperature for hours life 1Cr0.5Mo 13 CrMo Cr1Mo 9Cr1Mo 12Cr1MoV P91 E911 P92 AISI 316 AISI 321 AISI 347 IN CrMo 9 10 Low alloyed Cr- steels X10 CrMo 9 1 CrMo 9 1 X20 CrMoV P91 E911 P92 X3 CrNiMoN X10 CrNiTi 18 9 High alloyed Cr-steels X10 CrNiNb 18 9 Nickel base alloys > 750 C Laves reinforced ferritics austenitic steels Ennis 2. Juni 2009 Folie 18

15 Materials for boilers and steam turbines Ferritic- martensitic 9-12 % Cr- steels steam high steam oxidation rates < 12 %Cr decreasing creep strength > 10 %Cr air 600 C, 1000 h T- Capability < 600 C Oxyfuel atmosphere: internal carburization of 9 12 % Cr steels by non protective Fe 3 O 4 Oxyfuel environment: 550 C, 1000 h, 70 % CO 2 30 % H 2 O T- capability: approx. 500 C potential of 9-12 Cr- steels exhausted at 600 C no further research on these materials 2. Juni 2009 Folie 19

16 New Laves phase reinforced steels up to 650 C Laves phase 20 µm Advantages: 22 % Cr Laves reinforced 1000 h, 600 C, 70 % CO 2 30 % H 2 O higher creep strength corrosion resistant in steam no carburization in oxyfuel sulfidation resistant in syngas Juni 2009 Folie 21

17 Stability of Materials in oxyfuel slag deposits Thermodynamic Calculation Model with SimuSage Formation of alkali carbonates Low formation at < 700 C for λ >= 1 strong formation at <= 850 C for λ < 1 Weber, Müller et al Juni 2009 Folie 22

18 Nickel alloys > 700 C for power plants 700 C steam Alloy 617, 700 C 10 4 h steam corrosion resistance in: steam fireside & deposits conventional boilers oxyfuel processes advanced gasification. creep and TMF life prediction under dual atmosphere operation conditions (corrosion, H- embrittlement) PAG 2. Juni 2009 Folie 23

19 Microstructure determines manufacturing and long-term properties IN 617 Waspaloy IN C/5000h Heat treated carbide film γ η γ /γ Microstructure determines properties Seliga, Penkalla 2. Juni 2009 Folie 24

20 Forging of large rotor components from nickel base alloys INCONEL 617 INCONEL 706 WASPALOY Equivalent Stress (von Mises) in MPa 499,9 436,7 373,4 310,1 246,9 183,6 120,4 57,1 25,5 The higher the creep strength the higher forging forces!!!! Kopp et al. 2. Juni 2009 Folie 26

21 Materials for Boilers and steam turbines Till 2015 Reliable components from Ni- based alloys Life models for Ni- based components Potential of new ferritics for up to 650 validated Austenitics with higher T- capability Performance of materials in new power plant environments validated (oxyfuel, gasification) After 2015 New materials ready for long-term use Nickel base alloys beyond 760 available Erosion and corrosion resistant coatings for steam turbines 2. Juni 2009 Folie 27

22 Gas separation membranes in power plants Post combustion air fuel(fossil, biomass) CO 2 (90%N 2 /10%CO 2 ) N 2 /CO 2 Power plant separation N 2 fuel(fossil, biomass) Oxyfuel air O N 2 /O 2 2 Power plant separation N 2 CO 2 +H 2 O condensation CO 2 Pre fuel Power plant H 2 O (N 2 ), H 2 O combustion (fossil, biomass) H 2 CO H 2,CO 2 air O partial 2 N 2 /O 2 2 CO H 2 /CO 2 condensation separation oxidation shift (N 2 ) separation N 2 CO 2 + H 2 O 2. Juni 2009 Folie 28

23 New membrane compositions Oxygen vacancies in TiO 3 Development of new membrane materials with high permeability & selectivity long-term stability in power plant environments mechanical integrity under thermal & mechanical loads Jia and Urban, Science 303 (2004) O 16 Development of components and testing Manufacturing technologies for components (bulk and supported) brazing and sealing technologies k D component testing (permeability, chemical & mechanical integrity) development of life prediction methodologies O 18 Martin et al. 2. Juni 2009 Folie 29

24 Development of components and testing Powder processing & manufacturing components & upscaling 150 LSCV po 2 = bar po 2 = bar stress [MPa] air 0 0 0,05 0,1 0,15 0,2 strain [%] mechanical integrity & environmental stability permeability & selectivity 2. Juni 2009 Folie 30

25 Determination of Change of Oxygen- Non-Stoichiometry 2. Juni 2009 Folie 31

26 Stability Investigations of BSCF SEM picture and EDX spectra of 0,5 Sr 0,5 0,8 Fe 0,2 O 3-δ annealed at 800 C in air for 200h O Fe Sr Points 1 and 3 1 Fe C Sr Sr Fe Fe Full Scale 571 cts Cursor: (4 cts) kev O Point 2 2 C Full Scale 980 cts Cursor: (6 cts) kev SEM picture and EDX spectra of 0,5 Sr 0,5 0,8 Fe 0,2 O 3-δ annealed at 800 C in air+10% CO 2 for 200h CO 3, SrCO 3 Sr O Point µm C Sr Sr Full Scale 1565 cts Cursor: (36 cts) kev O Fe Sr Point 2 2 Fe Fe Sr Sr Fe Full Scale 137 cts Cursor: (3 cts) kev 2. Juni 2009 Folie 32

27 BSCF Results - Stiffness, Fracture Stress and Toughness Stiffness Fracture stress Toughness Normalised value Temperature / C 2. Juni 2009 Folie 33

28 Advanced Gasification RWE s IGGC CCS-Project Vision: High temperature gasification 2. Juni 2009 Folie 35

29 Materials for hydrogen rich gases Advanced gasification processes: chemical hot gas cleaning (filters) MCrAlY, H 2 / H 2 O blistering base materials & coatings stability in H 2 /H 2 O, H 2 S atmospheres H 2 - separating membranes Hydrogen embrittlement Subanovic, Quadakkers et al Juni 2009 Folie 36

30 Roadmap: Materials for Power plants 7000 x CO 2 -free Technologies Membrane Research LSCF 1 nm New membranes (b ) OXYCOAL- AC, 500 KW MEM-BRAIN I sic research sic Research Vattenfall Oxyfuel, 30 MW ADECOS mponent tests mponent MEM-BRAINdevelopment II mponent development components RWE- IGCC, 450 MW CCS Technology MEM-BRAIN Upscaling & Testing III Upscaling testing CO 2 free power plants η Technologies CC Irsching Siemens, η > 60 % DL TBC 700 C steam PP, > 500 MW EON, η > 50 % Juni 2009 Folie 38

31 Thank you for your attention RWE- Pre-combustion IGCC brown or hard coal 450 MW el demo plant start: 2014 storage of 2,3 Mio. t/a CO 2 costs: 1000 Mio. 2. Juni 2009 Folie 39