Chemistry in Biomass Combustion ChemCom 2.0. Åbo Akademi University
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1 Chemistry in Biomass Combustion ChemCom 2.0 Åbo Akademi University
2 Project Introduction ( ) Mainly funded by Tekes Research Partners Åbo Akademi (co-ordinator) Helsinki University of Technology Tampere University of Technology VTT Industrial Partners Andritz Oy Metso Power Oy Oy Metsä-Botnia Ab Foster Wheeler Energia Oy UPM-Kymmene Oyj Clyde Bergemann GmbH International Paper Inc.
3 Research Structure (1/2) Workpackages (9/19) M1: Modelling and validation of recovery boiler measurements M2: Modelling and validation of BFB boiler measurements M3: Collection and improvement of thermodynamic data for trace element prediction in combustion and gasification systems Black Liquor Biomass Waste Oxyfuel conditions M4: Application specific model development for CFD I1: Update from the Nordic Graduate School of Biofuel Science and Technology Full-scale measurements Experiment Modelling and validation Information I2: Utilisation, developments and up-dating of the ÅA/PCCdatabases F1 F2 E1 E2 M1 E3 E4 M2 I1 I2 I3: Information on the progress of novel chemical recovery processes F3 E5 E6 M3 I3 I4: Oxy-fuel combustion in power boilers fired with solid fuels and fuel mixtures F4 M4 I4 I5 I5: National and international collaboration researcher and information exchange
4 Workpackages continue... Research Structure (2/2) F1: Full-scale measurements; technique development F2: Full-scale measurements in a recovery boiler: Pietarsaari, UPM-owner, Andritz built, February 2009 F3: Full-scale measurements in a bubbling FBC; Rauma, UPM-part owner, Metso built, October 2009 F4: Full scale measurements treatment of deposits; method development E1: High temperature laboratory reactors E2: Combustion and gasification analysis of black liquor E3:Combustion, oxyfuel, and gasification analysis of biofuels and fuel mixtures E4: Mineral matter and trace elements in biofuels and waste fuels E5: High temperature corrosion mechanisms in biomass cofiring, oxyfuel and black liquor combustion/gasification E6: Laser analytic diagnostics for biomass combustion F1 F2 F3 F4 E1 E2 E3 E4 E5 E6 M1 M2 M3 M4 I1 I2 I3 I4 I5 Workpackages and responsible research institute ÅA/PCC TKK TUT VTT
5 Rauman Voima Oy
6 Campaign program Day 1: Bark Day 2: Bark+Sludge Day 3: Bark+Sludge+REF
7 Measurement point overview Gas measurement Camera Deposit probe Suction pyrometer Laser
8 Bark+Sludge+REF
9 Reporting to industrial partners Twice a year technical meetings and steering board meetings Spring meeting Fall meeting 2-3 days with different topics each day (totally presentations) Solid fuels, modelling, corrosion, black liqour, etc. Usually about 20 participants from industry Totally about participants
10 on Power Production & Environment August 29 th - September 3 rd 2010 Lapland, Finland fuel.quality@abo.fi
11 Workpackages continue... Research Structure (2/2) F1: Full-scale measurements; technique development F2: Full-scale measurements in a recovery boiler: Pietarsaari, UPM-owner, Andritz built, February 2009 F3: Full-scale measurements in a bubbling FBC; Rauma, UPM-part owner, Metso built, October 2009 F4: Full scale measurements treatment of deposits; method development E1: High temperature laboratory reactors E2: Combustion and gasification analysis of black liquor E3:Combustion, oxyfuel, and gasification analysis of biofuels and fuel mixtures E4: Mineral matter and trace elements in biofuels and waste fuels E5: High temperature corrosion mechanisms in biomass cofiring, oxyfuel and black liquor combustion/gasification E6: Laser analytic diagnostics for biomass combustion F1 F2 F3 F4 E1 E2 E3 E4 E5 E6 M1 M2 M3 M4 I1 I2 I3 I4 I5 Workpackages and responsible research institute ÅA/PCC TKK TUT VTT
12 Reactions of pure chromium with different chlorides Juho Lehmusto V Liekkipäivä
13 The motives of the study Although high temperature chloride corrosion is a well-known phenomenon, reasons leading to it are still ambiguous. Detailed mechanisms may pave the road for better control of corrosion. Disagreements concerning the roles of different cations and chlorine.
14 Grabke et al., MPIE, Düsseldorf, Germany: Active oxidation. Molecular chlorine Doesn t explain the oxide breakdown. Svensson et al., HTCC, CUT, Gothenburg, Sweden: Two-stage reaction. 1) Oxide breakdown by potassium 2) Direct attack by KCl Shinata, MC, AU, Akita, Japan: Two-stage reaction. 1) Cl - acts as a catalyst 2) Chromate formation determines the magnitude.
15 Why chromium? The capability to form a thin, yet very dense oxide layer. Flue gases Superheater tube (alloyed steel) Cr 2 O 3 -layer
16 The effect of KCl Before After Cr-granule with one KCl crystal (0,6 mass-%): 10 Cmin -1 up to 400 C; 2 Cmin -1 up to 700 C; C. Mass growth: 7,1%.
17 Materials and Methods -DTA/TG- Gives a good general view about the possible reaction. Presents changes in mass and heat of reaction as a function of temperature and/or time.
18 Relative mass / % Temperature difference / o C Materials and Methods -DTA/TG- Sample is heated up under controlled conditions. Changes in mass are detected (TG) DTA TG 2,0 1,5 1,0 0,5 Other physical and chemical changes can also be detected (DTA) Exo Endo Temperature / o C 0,0-0,5
19 Test parameters Powder samples. Constant molar cation to chromium-ratio. 400 C, 500 C, 550 C and 600 C. Substance Melting point / C Cr 1890 CaCl 2 2H 2 O 772 (anhydr.) KCl 776 NaCl 801
20 Temperature / o C Heating profiles 20 Cmin -1 X C in N 2, X C in N 2, X C in synthetic air. 800 N 2 Synthetic air min 120 min 600 o C 550 o C 500 o C o C Time / min
21 Relative mass / % Chlorides at 550 C T 550 o C 110 Gas change Cr (dotted) Cr + KCl Cr + NaCl Cr + CaCl 2 *2H 2 O Time / min
22 Relative mass / % Chlorides at 600 C T Gas change 600 o C Cr (dotted) Cr + KCl Cr + NaCl Cr + CaCl 2 *2H 2 O Time / min
23 Oxide (Cr 2 O 3 ) formation 600 C Cr-powder C 1 μm 1 μm
24 Chromium with different 600 C Cr Cr + KCl 1 μm 1 μm Cr + NaCl 1 μm
25 Conclusions KCl and NaCl accelerate the corrosion reaction. NaCl and KCl corrosive already far below their melting points.
26 Thank You for Your attention! Lumaxart2d
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