Engineering Conferences International ECI Digital Archives BioEnergy IV: Innovations in Biomass Conversion for Heat, Power, Fuels and Chemicals Proceedings Spring 6-11-2013 Clean hydrogen rich gas from catalytic steam gasification of biomass Sergio Rapagna Faculty of Biosciences, Technology Agro-food and Environmental Technology, University of Teramo Annalisa D'Orazio Faculty of Biosciences, Technology Agro-food and Environmental Technology, University of Teramo Katia Galluci Department of Industrial Engineering, Information and Economy, University of L Aquila Manuela Di Marcello Faculty of Biosciences, Technology Agro-food and Environmental Technology, University of Teramo Manfred Nacken Pall Filtersystems GmbH Werk Schumacher See next page for additional authors Follow this and additional works at: http://dc.engconfintl.org/bioenergy_iv Part of the Chemical Engineering Commons Recommended Citation Sergio Rapagna, Annalisa D'Orazio, Katia Galluci, Manuela Di Marcello, Manfred Nacken, Steffen Heidenreich, and Pier Foscolo, "Clean hydrogen rich gas from catalytic steam gasification of biomass" in "BioEnergy IV: Innovations in Biomass Conversion for Heat, Power, Fuels and Chemicals", Manuel Garcia-Perez,Washington State University, USA Dietrich Meier, Thünen Institute of Wood Research, Germany Raffaella Ocone, Heriot-Watt University, United Kingdom Paul de Wild, Biomass & Energy Efficiency, ECN, The Netherlands Eds, ECI Symposium Series, (2013). http://dc.engconfintl.org/bioenergy_iv/20 This Conference Proceeding is brought to you for free and open access by the Proceedings at ECI Digital Archives. It has been accepted for inclusion in BioEnergy IV: Innovations in Biomass Conversion for Heat, Power, Fuels and Chemicals by an authorized administrator of ECI Digital Archives. For more information, please contact franco@bepress.com.
Authors Sergio Rapagna, Annalisa D'Orazio, Katia Galluci, Manuela Di Marcello, Manfred Nacken, Steffen Heidenreich, and Pier Foscolo This conference proceeding is available at ECI Digital Archives: http://dc.engconfintl.org/bioenergy_iv/20
CLEAN HYDROGEN RICH GAS FROM CATALYTIC STEAM GASIFICATION OF BIOMASS Sergio Rapagnà, Annalisa D Orazio, 1 Katia Gallucci, Manuela Di Marcello, 2 Manfred Nacken, 2 Steffen Heidenreich and 1 Pier Ugo Foscolo Faculty of Biosciences, Technology Agro-food and Environmental Technology, University of Teramo, Via Carlo R. Lerici 1, 64023 Mosciano Sant Angelo, Teramo, Italy 1 Department of Industrial Engineering, Information and Economy, University of L Aquila, Via Campo di Pile, Zona industriale di Pile 67100 L Aquila, Italy 2 Pall Filtersystems GmbH Werk Schumacher Zur Flügelau 70, 74564 Crailsheim, Germany
Introduction Biomass gasification is a thermo-chemical conversion process which produces a fuel gas rich in hydrogen and carbon monoxide, with a significant content of methane and carbon dioxide. Steam is also present in the producer gas, in addition to organic (tar) and inorganic (H 2 S, HCl, NH 3, alkali metals) impurities, and particulate. + heat + steam Biomass particles Gas + hydrocarbons H 2, CO, CO 2, CH 4, C n H m Gas cleaning is normally done by filtration and scrubbing of the producer gas, to drastically reduce particulate and tar content.
To increase the efficiency of the utilization of thermal and chemical energy of the producer gas, hot gas cleaning and conditioning systems (abatement of particulate content and tar conversion at a temperature close to the gasification temperature) should be developed and implemented through a compact design and reliable and simple-to-operate equipment. Process simplification and intensification could play a very important role to a real breakthrough in the utilization of biomass in general, and specifically of gasification plants. Catalytic filter candles have been proposed as an alternative, very promising technology to be coupled to biomass gasification processes (UNIQUE and UNIfHY Projects).
Experimental apparatus DP1 DP1 DP1 T5 The organic component (tar) in the condensate samples was determined by Total Organic Carbon (TOC) analysis Gas Gasmete r T2 T3 Pump T4 H 2 CO, CO 2 CH 4 H 2 S NH 3 Ciller Gas Analysers Air N 2 T1 Heater Water Ciller Pump Tar fraction sampled in 2- propanol, according to the Technical Specification CEN/TS 15439 The composition of the tar fraction was determined by GCMS or HPLC/UV
Fluidized bed gasifier 870 mm + Catalytic filter candle 260 mm
Candle Outer diameter= 60 mm Inner diameter= 40 mm Total length 450 mm Filtering length 400 mm
Process conditions Biomass feed rate = (8 10) g/min Steam flow rate = (7.7 9.5) g/min Steam/biomass dry = (0.9 1.11) Bed temperature = (800 815) C Reactor outlet temperature = (760 800) C Olivine d m = 350micron Biomass d m = 1100micron Biomass properties Dry matter = 92.3% Ash= 1.1% Volatile matter= 71.9 Fixed carbon= 19.5
Filter Candles N260912,1 : Al 2 O 3 based hot filter candle of new improved candle support type (UHT) and with an Al 2 O 3 outer membrane. N051112,1 : Al 2 O 3 based hot filter candle of new improved candle support type (UHT) and with an Al 2 O 3 outer membrane. C280912,1 : catalytically activated Al 2 O 3 filter candle of new improved candle support type (UHT) with an Al 2 O 3 outer membrane. MgO- NiO catalytic layer system was applied. C181212,1 : catalytically activated Al 2 O 3 filter candle of new improved candle support type (UHT) with an Al 2 O 3 outer membrane and with integrated catalytic ceramic foam. MgO-NiO catalytic layer system was appliedon the catalytic filter candle support; a MgO- Al 2 O 3 -NiO based catalytic layer system was applied on the integrated catalytic ceramic foam.
Tests Test code 0101 0102 0103 0104 0105 0106 0107 0108 0109 0110 0111 0112 0113 Candle C1/NC C1/NC C3/C C3/C C3/C C3/C C3/C C4/CF C4/CF C4/CF C4/CF C4/CF C4/CF Test number I I I II III IV V I II III IV V VI Biomass feed rate, [g/min] 8,1 8,1 8,1 8,1 8,1 10 10 10 10 10 10 10 10 Steam/biomass dry 1,11 1,15 1,13 1,19 1,18 1,03 1 0,94 0,94 0,95 1,08 1,12 1,10 Total gasification time [min] 247 313 210 420 420 183 180 190 240 111 180 300 239 Legend C1/NC C1/NC C3/C C4/CF Candle N260912,1 N051112,1 C280912,1 C181212,1 Type No catalytic No catalytic Catalytic Layer Catalytic + catalytic foam
No-catalytic Candle N260912,1 / N051112,1 : Al 2 O 3 based hot filter candle of new improved candle support type (UHT) and with an Al 2 O 3 outer membrane Test 0101 0102 Candle C1/NC C1/NC Bed state USED FRESH Bed using-time >10:00:00 0 Biomass feed rate, g/min 8.1 8.1 Steam/biomass dry 1.11 1.15 Condensate [g/min] 6.09 6.49 Water conversion % 29 25.2 Gas yield, Nm 3 /kgdaf 1.76 1.41 Tar content, g/nm 3, by TOC 0.049 0.651 Tar content, g/nm 3 by GCMS 5.958 ------ H 2 free) 55 51.5 60 50 40 30 20 10 USED FRESH CO 2 free) 22,5 25 CO free) 20 18 CH 4 free) 2,5 5,5 0 H2 CO2 CO CH4
No catalytic Candle 1 st Test - Ni % N260912,1 / N051112,1 : Al 2 O 3 based hot filter candle of new improved candle support type (UHT) and with an Al 2 O 3 outer membrane Biomass composition X-Ray Fluorescence Measured - w% K 4,03 Si 1,64 mg / Kg_dry K 5237,9 Ni 16,7 Olivine composition w% SiO2 42 NiO 0,3 Ni 0,11 (expected < 0,03)
Catalytic Candle C280912,1 : catalytically activated Al 2 O 3 filter candle of new improved candle support type (UHT) with an Al 2 O 3 outer membrane. MgO-NiO catalytic layer system was applied. Test 0106 0107 Candle C3/C C3/C Bed state USED FRESH Bed using-time 23:30:00 0 60 Catalytic Candle Biomass feed rate, g/min 10 10 Steam/biomass dry 1.03 1 Condensate [g/min] 6 6.36 Water conversion % 36.8 31 Gas yield, Nm 3 /kgdaf 1.63 1.48 Tar content, g/nm 3 by TOC 0.022 0.120 Tar content, g/nm 3 by GCMS 1.071 2.545 H 2 free) 54 52 CO 2 free) 22 24 50 40 30 20 10 0 H2 CO2 CO CH4 USED FRESH CO free) 19 18 CH 4 free) 5 6
Catalytic Candle + catalytic foam C181212,1 : catalytically activated Al 2 O 3 filter candle of new improved candle support type (UHT) with an Al 2 O 3 outer membrane and with integrated catalytic ceramic foam. MgO-NiO catalytic layer system was appliedon the catalytic filter candle support; a MgO-Al 2 O 3 -NiO based catalytic layer system was applied on the integrated catalytic ceramic foam Test 0108 0112 Candle C4/CF C4/Cf Bed state USED FRESH Bed using-time 31:16:00 0 Biomass feed rate, g/min 10 10 Steam/biomass dry 1.12 0.94 Condensate [g/min] 6.1 5.64 Water conversion % 41 33.5 Gas yield, Nm 3 /kgdaf 1.84 1.48 Tar content, g/nm 3 by TOC 0.010 0.062 Tar content, g/nm 3 by GCMS 1.311 0.142 60 50 40 30 20 Catalytic Candle + Catalytic Foam USED FRESH H 2 free) 55.5 51 10 CO 2 free) 20 22 0 H2 CO2 CO CH4 CO free) 21.5 22 CH 4 free) 3 5
TAR abatement (GCMS) GCMS- measurement on catalytic candle with catalytic foam (C181212,1) : BED USED FRESH 0.8 COMPOUNDS TAR content [g/nm 3 ] TAR content [g/nm 3 ] ACENAPTHYLENE 0.004 0.010 FLUORENE 0.002 0.006 PHENANTRENE 0.006 0.023 ANTHRACENE 0.006 0.004 PYRENE 0.000 0.003 PHENOL 0.000 0.000 NAPTHALENE 0.037 0.466 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0.0 0.03 0.02 0.02 0.01 0.01 0.00 FRESH USED STYRENE 0.000 0.045 XYLENE 0.000 0.040 TOLUENE 0.087 0.714 TOTAL 0.142 1.311
Pressure drop through the filter, cm of H 2 O % by volume n N 2 free Gas composition and pressure drop for the catalytic candle with catalytic foam with used olivine 60 H 2 50 40 30 CO 20 CO 2 10 CH 4 0 0 60 120 180 240 300 360 420 480 540 600 time, min 100 80 60 40 20 0 0 60 120 180 240 300 360 420 480 540 600 time, min
Candles performance comparison Candle None C1/NC C1/NC C3/C C3/C C4/CF C4/CF Bed state best - value USED * FRESH USED FRESH USED FRESH Gas yeld [Nm 3 (dry N 2 free)/kg daf] 1 1.76* 1.41 1.63 1.48 1.84 1.48 H 2 [%vol (dry gas, N 2 free)] CH 4 [%vol (dry gas, N 2 free)] 39 55* 51.5 54 52 55.5 51 10 2.5* 5.5 5 6 3 5 Water conversion [%] 16 29* 25.2 36.8 31 41 33.5 TAR content g/nm 3 by TOC 3.7 0.049* 0.651 0.022 0.12 0.01 0.062 TAR content g/nm 3 by HPLC/UV or GCMS 7 (HPLC/UV) 5.958 (GCMS) ------- 1.071 (GCMS) 2.545 (GCMS) 0.14 (GCMS) 1.31 (GCMS) *Ni contamination
Conclusions The innovative concept of integrating a catalytic hot gas filter in the freeboard of a fluidized bed gasifier has been tested. This promising technology results in greatly increased gas and hydrogen yields, as the same time giving rise to significant power plant simplification and intensification The best results, in respect to the gasification without candle, show: Hydrogen content increases more than 40% Methane content decreases more than 70% Gas yield increases more than 80% Water conversion increases more than 2 times TAR content decreases more than 1 order
hot water clean hydrogen rich gas biomas steam exhaust gases exhaust gas steam air air Tank you for your attention.