Chemistry in Biomass Combustion (ChemCom) Åbo Akademi together with Helsinki University of Technology Tampere University of Technology Umeå University with support of Tekes and industrial partners Andritz Oy Foster Wheeler Energia Oy International Paper Inc. Kvaerner Power Oy Oy Metsä-Botnia Ab Vattenfall Utveckling AB Presented at the 2nd FFRC Liekki-day, Turku, 24.1.06 Past – Present - Future - Since 1988 successful national research programs: • Long-term oriented research • Close collaboration between universities • Close cooperation with industrial partners Excellent experiences and results - Presently no national research program in combustion ChemCom Chemistry in Biomass Combustion (ChemCom) Fundamental Research on Chemistry in Biomass Combustion Project Steering Group Experiment Project Coordination (ÅA) Modelling Information Åbo Akademi Process Chemistry Centre Åbo Akademi Process Chemistry Centre Combustion and Materials Chemistry • Mikko Hupa • Christian Mueller • Bengt-Johan Skrifvars • Rainer Backman • Anders Brink • Edgardo Coda Zabetta • Mikael Forssén • Jukka Konttinen • Patrik Yrjas • Maria Zevenhoven Prof. Mikko Hupa Combustion Chemistry Materials Chemistry • Daniel Lindberg • Mischa Theis • Johan Werkelin • Vesna Barisic • Markus Engblom • Mikaela Westén-Karlsson • Tor Laurén HELSINKI UNIVERSITY OF TECHNOLOGY Laboratory of Energy Engineering and Environmental Protection • Carl-Johan Fogelholm • Mika Järvinen • Ari Kankkunen • Pasi Miikkulainen Tampere University of Technology Applied Optics Group • Rolf Hernberg • Jorma Keskinen • Toni Laurila • Albert Manninen Energy Technology and Thermal Process Chemistry • Rainer Backman • Dan Boström • Mathias Råberg • Anders Larsson Energy Technology and Thermal Process Chemistry • Umeå University ChemCom Mission To develop improved understanding of chemical aspects in biofuel combustion – this way paving the road for development of future fuel conversion technologies Research Areas in ChemCom Biomass Black Liquor Waste Characterisation & Conversion Inorganic Material Furnace Processes Experiment Modelling Gas Phase & Emissions Bed Processes Information ChemCom – Research Structure Biomass Black Liquor Waste Experiment E1 Modelling Information E2 M1 E3 E4 E5 E6 E7 E8 I1 I2 I3 I4 M2 M3 Research Topics – Solid Fuels Biomass/Waste • Ash Particles stickiness & deposition aerosols & heavy metals • Fuel particles conversion rates release • Fuel-N NOx formation tendencies • Ash-forming matter release & particle formation • Trace elements release & particle formation Inorganic Matter Behaviour Characterisation & Conversion Researchers – Solid Fuels Biomass/Waste ÅA Bengt-Johan Skrifvars Rainer Backman Patrik Yrjas Mischa Theis Micaela Westén-Karlsson Tor Laurén Inorganic Matter Behavior ÅA Mikael Forssén Jukka Konttinen Rainer Backman Johan Werkelin Edgardo Coda Zabetta Maria Zevenhoven Characterisation & Conversion TUT Rolf Hernberg Jorma Keskinen Toni Laurila Albert Manninen ÅA fuel-, char- and ash databases Fractionation database Fuel analysis data; proximate and ultimate analyses, selective leaching analyses for ash forming matter & trace elements Deposit database Data from full-scale deposit measurement campaigns since 1996; process data (fuel, char. temperatures, boiler type, boiler load, etc.) deposit growth, deposit analyses. Black liquor database Combustion experiments in single droplet reactors; pulping process type, standard liquor analyses, conversion time, swelling, formation of NO, SO2, CO2, and CO, pyrolysis and char yield Nitrogen database Data from novel combustion experiments in a small-scale FBC; distribution of fuel-N between reactive and non-reactive (N2) volatile components and char-nitrogen. Mineral Matter and Trace Elements Characteristics of ash particles and their formation with special focus on trace elements. - selective leaching in combination with ion chromatography - continued evaluation of the stepwise leaching technique - tests on fuels and partly oxidized chars combined with SEM/EDX. To give a deeper understanding of mineral matter & trace element release/behavior for better predictions and better model input values Chemical Fractionation /J. Werkelin, PhD work 2003-2006/ Metals in wood /J. Werkelin, PhD work 2003-2006/ Co-combustion & Ash Behavior Characteristic differences for fuel mixtures deposit formation vs erosion - Lab-scale studies of deposition and erosion tendencies 1) various fuels with strongly differing ash characteristics 2) taylor-made model substances - Full-scale verification measurements of fly ash behavior with in-situ, on-line fly ash measurement equipment To get validation data of deposition vs erosion submodel developed to be done in M1. Deposition rate [mg/(g cm 2 )] Ash deposition behavior of biofuel blends 90 80 70 60 50 40 30 20 10 0 negative interaction n io t c a ter n i o n positive interaction 0 20 40 60 "Dirty Fuel" [mass %] 80 100 /M. Theis, PhD work 2003-2006/ Deposit Sampling Sample feeder 500 g/40 min Gas burner 1000 ºC The EFR (University of Toronto) Particles < 1mm Furnace 1000 ºC Probe 550 ºC 9m 2 Deposition (g/m h) Deposition Results Peat/Straw Mixtures 160 140 120 100 80 60 40 20 0 Rest P2O5 Cl SO3 K2O Na2O MgO CaO Cr2O3 Fe2O3 Al2O3 SiO2 0 10 20 30 40 50 60 70 80 90 100 Straw fraction (wt-%) /M. Theis, PhD work 2003-2006/ Biofuel ash chemistry predictor Fuel sample 1 Stepwise leaching, SEM Fuel sample 2 Stepwise leaching, SEM Fuel sample 3 Stepwise leaching, SEM Equilibrium Composition + CFD Chemical equilibrium calculation 45% Plywood + 55% Bark, “reactive flyash” 1.4 liquid solid 1.2 amount g/100g 1.0 Na2 SO4 Na2 CO3 K2 SO4 K2 CO3 NaCl 0.8 KCl Na, K)2 (CO3 , SO4 , Cl2 ) Mg(SiO4 ) 0.5 MgO 0.6 Ca(SiO4 ) 0.5 0.4 CaCO3 0.2 CaO 0.0 400 500 /Backman, Zevenhoven 2002/ 600 700 800 900 Temperature °C 1000 1100 1200 Biofuel ash chemistry predictor Fly ash particle ”hit map” : Extreme fouling : High fouling : Fouling : Low fouling : No fouling /C. Mueller: “Wilhelm Jost” prize 2004/ Ash behaviour predictor – CFD - situation today sh a ly f ve Ac i t ac NH 4 e R O+ H2 Fuels Stepwise leaching, SEM Inert flyash, Cleaning effect Bot Bed tom a beh sh, a vi our In-situ diagnostics of combustion chemistry To explore the possibilities of developing Laser Photoacoustic Analysis LPA as a research tool for determining the composition of aerosols in combustion: - Analytical modelling of the photoacoustic response of aerosol particles - Experimental study of the photoacoustic response of aerosol particles containing trace elements To develop methods able to determine quantitative trace element species selective analysis results /Rolf Hernberg, Jorma Keskinen/ Manganese (Mn) chemistry in biomass utilisation Manganese (Mn) is one of the “dirty dozen” although important in wood (found in the same order of magnitude as Fe and Al) - To follow up the role of Mn in the trace element emission legislation and to review and report valuable information on environmental effects of Mn. - To summarize the Mn chemistry at combustion and gasification conditions Summary will focus on the chemical form of Mn in the fuel, Distribution between coarse-, fine ash fractions, and gas phase. - To determine how Mn reacts with bed materials in FBCs The experimental methods used in this study are: - Chemical analysis and chemical fractionation - Thermal analysis - Molecular Beam Mass Spectrometry (MBMS) - SEM/EDS analysis EU directive on incineration of waste containing fuels Sb + As + Cr + Co + Cu + Mn + Ni + Pb + V 0.5 mg/m3n* (twice a year) Cd +Tl 0.05 mg/m3n* (twice a year) Hg 0.05 mg/m3n* (twice a year) *6 % O2, dry gases 0.5 mg/m3n* in flue gases ≈ 3 – 4 ppm (mg/kg) in dry wood Metals in 37 wood species 1% 1 ppm P Mn Ni As Hg 0.0000001 0.000001 100 % B Cu Pb Cr Zn K Al Mg Fe C Na Mo Cd Se 0.00001 0.0001 0.001 0.01 Concentration (mass fraction) 0.1 1 Manganese in wood, Werkelin 2002 2500 Bark trunk 2000 Twigs max 1500 Average 1000 min 500 Tree species Birch Spruce Aspen Pine Birch Spruce Aspen Pine Birch Spruce Aspen Pine Birch Spruce Aspen 0 Pine mg Mn/kg dry wood Trunk wood Bark branches