Hot Gas Cleanup R&D at Forschungszentrum Karlsruhe

Transcription

1 Hot Gas Cleanup R&D at Forschungszentrum Karlsruhe H. Leibold; A. Hornung; H. Seifert Forschungszentrum Karlsruhe GmbH, Germany Thermal Treatment Division IEA Bioenergy Agreement: Task 33: Thermal Gasification of Biomass Dresden, Germany June 12-14,

2 Outline Introduction Activities of Basic research Particulates Gaseous Components/Technology development HT gas cleaning line at REGA gasifier HALOCLEAN rotary kiln with HGF Cooperations/Projects Summary 2

3 Waste to Energy and Products ENERGY W AS TE mixed solid industrial construction demolition PT 4 biomass PT 2 gas treatment particle technology incineration pyrolysis gasification PT 5 combination with power plant co-combustion combustion silicatic products PT 4 metals organic products halogens salts PRO DUC TS residues emissions syngas 3

4 Incineration Pyrolysis Gasification < 1400 C Aerosol Formation Analysis < 1300 C < 700 C HT Particle Removal Combined HT Particle Removal Tar Cracking Reforming < 400 C < 200 C Combined Particle Removal Catalysis, Sorption HEPA Filtration Aerosols Hg, VOC Abatement Flue Gas Pyrolysis Gas Syngas 4

5 HT Filter Candles 5

6 Comparative Adhesion Forces Particle Detachment Degree A D [-] Nanomembrane RH = 16 % I = 15 nn I = 80 nn Conventional Membrane RH = 16 % Conventional Membrane Nanomembrane 20 µm Centrifugal Force F [nn] C Adhesion force and interquartile range on nanomembrane 5 times lower than on conventional membrane 6

7 LISA Forschungszentrum Karlsruhe particle analysis FC FC recleaning air control unit recleaning air FC LPC EMS/ CNC control unit EMS dilution filter heating raw gas LPC M clean gas p Δp p M PC LPC EMS air FC spray type p dust feeder aerosol generation fast opening valve 7

8 Recleaning sticky particulates 100 grain diameter 20 nm grain diameter 300 nm mullite Cycletime[min] 10 LT tar catalyst 100 Wax: 1 µm 90 vf: 90 m/h Operation time [h] Yield [%] FeNiPt Ni Naphthalene: 6000 mg C/m³ Temperature [ C] 8

9 Screening of sorption materials for HCl und H 2 S Syngas composition H 2 O/HCl TIRC Gas Vol.% CO MFC H 2 MFC CO 2 MFC CO 35 H 2 30 N2 CH 4 H 2 S MFC MFC MFC S T 600 C CO 2 10 CH 4 3 H 2 O 15 Sorption layer TIRC S T 1000 C HCl 5000 ppmv Stack H 2 S 2 N 2 S Sorption reactor 9

10 Screening of sorption materials for HCl und H 2 S removal HCl sorbent H 2 S sorbent 2 sorbent beds K 2 CO 3 ZnTiO 3 t res [s] Trona Zn 2 TiO 4 1 / 2 s G-92 C G-72 D RGM 1 NiSAT-H RS T [ C] 300/350/400/450 CuO / ZnO RGM 3 α-fe CuMnO 3 c HCl 0 c HCl II c H2S 0 c H2Sl II 150 ppm 200 ppb 180 ppm 350 ppb CuTiO 3 Trona Trona CaCO 3 CaCO 3 T [ C] 750/800/850/900 10

11 Porous duct Safety filter Blower Filter element Recleaning valve pressure inside element CPP Recleaning intensity Pressurized increased Jet pipe gas Adaption to fine and sticky particulates Influence of dust loading minimized Energy conversion improved Pressure of recleaning gas decreased Cost benefit (mainly HTHP) Expansion induced cooling minimized Thermal load reduced Filter element Fail-safe system integrated pressure inside element Jet Pulse Self blockage of damaged filter element 11

12 Filtration of Eutectic NaCl/CaCl 2 Mixture 4,0 Pressure drop [kpa] 3,8 3,6 3,4 3,2 3,0 2,8 2,6 50 %w glass 33 %w NaCl 17 %w CaCl 2 c=10g/nm 3 T F = 525 ºC v F =85m/h t =60min cycl Jet pulse 0.6 MPa Torque [mnm] maximales maximum Drehmoment Torque Temperature [ C] 2,4 2,2 CCP 0.1 MPa 2, Time [h] 12

13 Pilot-scale Ceramic Hot Gas Filter at the PYDRA Facility 5 cluster à 3 candles; max. 550 C; recleaning gas N 2 Recleaning valves Hydraulic switches Safety filter Ceramic candles 13

14 Syngas Conditioning On short-term gas conditioning by state-of-the-art (Rectisol) HTHD gas conditioning for improved heat recovery and energetic optimisation HP Gasifier HTHP Syngas conditioning Synthesis FT, Methanol, DME bar,1200 C Lab scale: 60 bar, 500 C, PDU up to 40 bar, 350 C Expansion HT Syngas conditioning PDU plant: 800 C, REGA Lab scale: up to 1000 C Compression Cooling Syngas scrubbing Heating State of the art: -70 C RECTISOL up to 58/22 bar, PDU, Pilot 14

15 PDU Entrained flow gasifier REGA (60 kw therm,)

16 Basic HTHP syngas cleaning line at REGA PDU entrained flow sorbents H 2 S, HCl Gas analysis raw syngas synthesis gas from entrained flow gasifier I II ceramic filter fixed bed reactors catalyst guard bed filter/catalyst particulates alkalines H 2 S, HCl alkalines COS, NH 3 S, Cl, NH 3

17 Development of optimized HT syngas cleaning entrained flow sorbents H 2 S, HCl Gas analysis raw syngas from entrained flow gasifier syngas ceramic filter + catalyst layer guard bed filter/catalyst particulates NH 3 S, Cl, NH 3

18 HALOCLEAN Pyrolysis Facility HT-Filter Scrubber System Stack Electronic scrap Coconut shells Straw Condenser Haloclean Rotary kiln Coke Salts, Fly Ash Pyrolysis Oil Combustion Chamber Blower 18

19 Gas Filtration during Coconut Shell Pyrolysis 3 candles L: 0.5 m; Ø: 60 mm CPP recleaning N 2 Feed 9-42 (4 runs) T Pyrolysis T Filtration kg/h C C T Reclean 450 C P Reclean 0.5 bar N Reclean 4 ΔP 7-22 mbar

20 Cooperation U Karlsruhe EBI (Profs. Reimert, Schaub) U Karlsruhe IMVM (Prof. Kasper) U Karlsruhe ITTK (Prof. Schaber) Helmholtz- Gemeinschaft GFZ FilterGas TU Darmstadt ITMC (Prof. Vogel) U Kaiserslautern FB Chemie TC (Prof. Ernst) ITC -TAB Particle Technology Gas Conditioning Source Sewage gas Landfill gas Bio gas Biomass gasification Utilization lines ReGasNet Gas cleaning/- Utilization conditioning µturbine Gas turbine PEFC MCFC/SOFC Hydrogen 5.0 SNG G a s m o t o r Numerical Simulation Analysis Gasification Gas treatment Extraction washing Pyrolysis Slurry Syngas Pre treatment Gas Liquid Solid Upgrading Reforming Fertilizer Chemical products Formic/Acetic acid

21 U Karlsruhe EBI (Profs. Reimert, Schaub) U Karlsruhe IMVM (Prof. Kasper) TU Darmstadt ITMC (Prof. Vogel) U Karlsruhe ITTK (Prof. Schaber) Helmholtz- Gemeinschaft GFZ FilterGas U Kaiserslautern FB Chemie TC (Prof. Ernst) ITC -TAB Particle Technology Gas Conditioning

22 Cooperation U Karlsruhe EBI (Profs. Reimert, Schaub) U Karlsruhe IMVM (Prof. Kasper) U Karlsruhe ITTK (Prof. Schaber) Helmholtz- Gemeinschaft GFZ FilterGas TU Darmstadt ITMC (Prof. Vogel) U Kaiserslautern FB Chemie TC (Prof. Ernst) ITC -TAB Particle Technology Gas Conditioning Source Sewage gas Landfill gas Bio gas Biomass gasification Utilization lines ReGasNet Gas cleaning/- Utilization conditioning µturbine Gas turbine PEFC MCFC/SOFC Hydrogen 5.0 SNG G a s m o t o r Numerical Simulation Analysis Gasification Gas treatment Extraction washing Pyrolysis Slurry Syngas Pre treatment Gas Liquid Solid Upgrading Reforming Fertilizer Chemical products Formic/Acetic acid

23 CTCB Center of competence in thermal-chemical treatment of biomass Numerical Simulation Analysis Gasification Gas treatment Extraction washing Pre treatment Pyrolysis Liquid Gas Slurry Syngas Solid Upgrading Reforming Fertilizer Chemical products Formic/Acetic acid 23

24 Cooperation U Karlsruhe EBI (Profs. Reimert, Schaub) U Karlsruhe IMVM (Prof. Kasper) U Karlsruhe ITTK (Prof. Schaber) Helmholtz- Gemeinschaft GFZ FilterGas TU Darmstadt ITMC (Prof. Vogel) U Kaiserslautern FB Chemie TC (Prof. Ernst) ITC -TAB Particle Technology Gas Conditioning Source Sewage gas Landfill gas Bio gas Biomass gasification Utilization lines ReGasNet Gas cleaning/- Utilization conditioning µturbine Gas turbine PEFC MCFC/SOFC Hydrogen 5.0 SNG G a s m o t o r Numerical Simulation Analysis Gasification Gas treatment Extraction washing Pyrolysis Slurry Syngas Pre treatment Gas Liquid Solid Upgrading Reforming Fertilizer Chemical products Formic/Acetic acid

25 ReGasNet BMBF-Networks: Basic Research on Renewable Energies and Efficient Energy Conversion Utilization lines ReGasNet Source Sewage gas Landfill gas Bio gas Biomass gasification Gas cleaning/- conditioning Utilization µturbine Gas turbine PEFC MCFC/SOFC Hydrogen 5.0 SNG G a s m o t o r 25

26 Cooperation U Karlsruhe EBI (Profs. Reimert, Schaub) U Karlsruhe IMVM (Prof. Kasper) U Karlsruhe ITTK (Prof. Schaber) Helmholtz- Gemeinschaft GFZ FilterGas TU Darmstadt ITMC (Prof. Vogel) U Kaiserslautern FB Chemie TC (Prof. Ernst) ITC -TAB Particle Technology Gas Conditioning Source Sewage gas Landfill gas Bio gas Biomass gasification Utilization lines ReGasNet Gas cleaning/- Utilization conditioning µturbine Gas turbine PEFC MCFC/SOFC Hydrogen 5.0 SNG G a s m o t o r Numerical Simulation Analysis Gasification Gas treatment Extraction washing Pyrolysis Slurry Syngas Pre treatment Gas Liquid Solid Upgrading Reforming Fertilizer Chemical products Formic/Acetic acid

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28 Summary HT gas cleaning in thermal treatment of waste and biomass Basic research Particulates: Filtration of sticky and fine particles Gaseous: Sorption of HCl, H 2 S with alkali / earth alkali based sorbents up to 800 C LT catalysis of PAH at C Tar removal / reforming Components / systems Ceramic candle filters: Filter medium, recleaning, configuration Entrained flow sorption with natural sorbents Process / process integration HT syngas cleaning at 500 / 800 C bioliq process HT pyrolysis gas cleaning/conditioning HALOCLEAN process 28

29 Backup 29

30 Target concentration of Syngas pollutants SASOL Neby et al Vogel 2003 ECN 2003 CO 2 < 10 % n.s. < 5 Vol% < 5 Vol% Particulate n.s. < 0,1 ppm n.s. < 0,1 ppm HCN NH 3 < 20 ppb < 10 ppb < 10 ppm < 20 ppb < 1 ppm H 2 S COS < 10 ppb < 60 ppb < 10 ppb < 1ppm HCl < 10 ppb < 10 ppb < 10 ppb < 10 ppb Br, F n.s. n.s. < 10 ppb Alkalines < 10 ppb n.s. < 10 ppb < 10 ppb Tar n.s. n.s. below dew point below dew point n.s. not specified 30

31 Combination Filter - Catalysts Raw gas Clean gas KOMBINATION Raw gas Clean gas FILTER CATALYST 31

32 LARA Versuchsstand Teerkonversion/-partitionierung in Staubschichten V. V. V. V. Dosierung Modellteer A V. p A V. p V. p Teeranalyse Gasanalyse V. Modellstaub Dosierung V. V. V. V. Synthesegas Mischbehälter Gaswäsche Heizung Kühlung Spül-/Inertgas Isolierung Schnitt AA: Laboratory unit for Ash - Refractory Analysis

33 Coupled Pressure Pulse Recleaning Filtration Recleaning Blower Recleaning valve closed Blower Recleaning valve opened Porous duct Safety filter Porous duct Safety filter Filter element Filter element 33

34 HT Gas Cleaning Separation of fines particulates in HT processes Filtration of sticky particles pyrolysis and gasification of biomass Recleaning of HT gas filters Nanostructured highly porous filter membranes Catalytic coatings of filter materials and elements Tar conversion, reforming, NH 3 conversion 34

35 Recleaning intensity (Cluster 18 candles) Recleaning Pressure pressure [kpa] [kpa] Butterfly valve Butterfly valve Ø 250 mm Butterfly valve Ø 150 mm Slide valve Ø 150 mm Jet Pulse Jet Pulse Coax valve Coax-Valve Ø 50 mm 50 mm Venturi Venturi 0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 Loading Pressure [MPa] Recleaning pressure 35

36 Hot Gas Filter with Safety Function Recleaning valves Hydraulic switches Safety filter Ceramic candles 36

37 Entrained flow gasifier REGA (60 kw therm ) Primärluft Erdgas Brennstoff Inertgas Brenner + Pilotbrenner Synthesegas Rauchgas Analytik HT-Gasreinigung Vergasungszone Wasser Messebene Rauchgas Sekundärluft + Stützbrenner Nachverbrennungszone Steuerung, Messwert- Erfassung Elektroheizung Brennkammer Schlacke Rauchgaskühler Rauchgaswäscher

38 Compact HT Filter System with CPP Technology Filtration Recleaning 38

39 Fly ash from MSW Incineration 5 µm 5 µm 5 µm 200 C 300 C 550 C 1µm 1µm 1µm 39

40 Allothermal gasification of biomass with SOFC Fuel gas Anode rest gas Product gas MPA - Schunk IVD - Wünning FZK - Schumacher ZSW DLR FLOX Radiation burner Fluidized bed Gasification HT Gas cleaning Prereforming SOFC SOFC heat Off-gas Bio mass Current 40

41 HT Processes Waste treatment Residues Energy generation Chemicals processing Metallurgy Glass Mineral processing Process Temperature [ C] Pressure [bar] Incineration Soil decontamination Pyrolysis plastics < 1100 < Gasification biomass < 600 (1200) 1 (100) PFBC < IGCC < PCC < Catalytic cracking 300 bis 500 < 5 Calcination < Particle generation < 1200 < 5 Ore roasting < Smelting, casting < Glass smelting < 1200 Ceramics <