Kinetics of AlH 3 decomposition and subsequent Al oxidation / Hydrogen Jetfires Eisenreich N., Keßler A., Deimling, L. Energetic Systems, ES Fraunhofer ICT IA Hysafe Research Priorities Workshop BAM, Berlin, Germany 16./17.10.2012
ON THE KINETICS OF ALH3 DECOMPOSITION AND THE SUBSEQUENT AL OXIDATION Hydrogen storage: High pressure tanks 350 700 bar or higher in composites, mechanical stability Liquid hydrogen tanks: boil-off, cooling/isolation, safety Solid hydrides Heavy metals: low gravimetric storage Light metals: adsorption in nano structures Light metals: chem. bonded hydrides
Hydrogen Storage Systems - General Surve 18% AlH3 as model substance for storage of hydrogene hydride 17% 16% 15% 14% 13% 12% L H2 (cryo.) Amorphous light metal powders are about 5% 11% 10% AlH3 9% 8% 7% MgH2 LiNH2 MOF N 6% MgTiH2 5% 4% 3% 2% 1% comp. H2 (700 bar) 0% 1970 1975 1980 1985 1990 1995 2000 2005 20 Year
α-alh 3 polyhedra as cubes, cubic octahedron and hexagonal prisms For comparison: Alex: electro-exploded Al surface 12.28 m 2 /g Resulting Al is not passivated!!! On dehydrogenation => nano-porous Al structures emerge with surface 15 to 20 m 2 /g from AlH3 of 0.69 m 2 /g surface area
ON THE KINETICS OF ALH3 DECOMPOSITION AND THE SUBSEQUENT AL OXIDATION Risks arising from dehydrogenated hydrides * : The solids are highly porous or nano-structured to expose high surface areas to easy hydrogen access but also to easy air access on accidents. The metals => pure state, highly sensitive to oxidation if contact to air. The temperatures are elevated on operation in relation to oxidation reactions of metals, even they are considered moderate. In addition gaseous hydrogen is present Passivation reactions: thin protecting oxide layers (for Al ~ 2 4 nm) => 10-30% of metals might be oxidised at high reaction rates: Thermal explosion of container and the subsequent distribution Explosion of released metal of nano-size in air Even a Deflagration Detonation Transfer might be possible if well distributed nano-particles in air ignite. Investigation of this effect in more detail!!!
Al from dehydrogented AlH 3 behaves like Al nano or ultra-fine particles weight 1.5 1.4 1.3 1.2 1.1 1.0 0.9 400 600 800 1000 1200 temperature K TG-curve heated (2 K/min) in an inert Ar-atmosphere till 480K initiating dehydrogenation, then cooled down to 50 K with air entrainment causing passivation and subsequent heating to 1300 K (5 K/min) with two steps of oxidation at 850 K and 1100 K
Modelling the reactions => kinetics for simulation of thermal explosions 1.6 TG 2, 5, 10K/min Methods of Thermal DSC 2, 10 K/min Analysis: DSC, TG, X-Ray 50 40 weight 1.4 1.2 1.0 400 600 800 1000 1200 temperature K Dehydrogenation of formation of Al 2 O 3 2-4nm passivation layer chemical controlled 10 nm thick particle oxidation diffusion controlled particle oxidation weight 30 20 10 0 300 400 500 600 700 800 900 temperature K Dehydrogenation of formation of Al 2 O 3 2-4 nm passivation layer chemical Controlled 10 nm thick particle oxidation
rel. crystal size 0.30 0.25 0.20 0.15 0.10 0.05 0.00 430 440 450 460 470 480 490 temperature K Crystal growths estimated from weight increase on passivation depending on the heating rate 2, 5, 10 and 20 K/min At higher temperatures of dehydrogenation, less surface area is available for passivation and therefore for the oxidation reaction, which might lead to hazardous thermal explosion Results of kinetic parameters discussion of kinetic compensations effect in the paper Method: evaluated Dehydrogenation Dehydrogenation simultaneously TG-DSC TG-DSC (fitted n) Oxidation TG- DSC Activation energy [J] 115031 117770 83077 Pre-expon. Log Z 11.04 11.37 7.62 Avrami-Erofeev order n 3 2.58 3
Research needs oxidation of metal hydrides is strongly exothermal May lead to thermal explosion Experimental investigation needed for accident scenarios Tank rupture Dispersion of hydrides as particle cloud additional presence of gasuous hydrogen
Hydrogen Jet Fires Dominating risks of hydrogen jet fires beneath pressure effects are emerging from: Direct contact of the flame and its reacting species Dispersion of hot gases Radiation (for remote distances) Therefore the presented work fokuses on time resolved investigation of Explosive Volume Ignition behaviour Pressure wave propagation & speed Flame lengths & velocities
Introduction Evaluation of joint experiments at HSL (Buxton, UK) in 2008 under the work programme of HySafe HSL provided within HYPER Project: Test facilitiy for Hydrogen Jetfires and Ignition Pressure measurements Video analysis Fraunhofer ICT applied: Spectroscopic & Imaging Techniques
SKETCH OF THE EXPERIMENTAL SETUP
TEST PARAMETERS The campaign consists of 23 jet experiments Tank Volume Initial tank pressure Nozzle diameters Initial mass flow Ignition Point Ignition delay 100l (2x50l) 20 MPa 1.5 / 3.2 / 6.35 / 10 mm 40 / 160 / 450 / 670 g/s 160 / 220 / 250 / 300 / 400 cm behind orifice various
Background Oriented Schlieren Results are: Explosive Volume (before ignition) Flame speed / Flame dimensions Pressure wave speed & shape
Velocitiy of cold gas flow 0 0.02 hyper15.cin (Row 193...449) 0.04 0.06 Time [s] 0.08 0.1 0.12 0.14 Centerline of each frame 0.16 0 50 100 150 200 Path [cm] 250 300 350 400 50 hyper15.cin (Row 193...449) 300 gas flow propagation 45 40 250 Speed of flow Speed of pressure / shock waves can be evaluated using the same method Speed [m/s] 35 30 25 20 15 10 5 200 150 100 50 Path [cm] 0 0.02 0.04 0.06 0.08 0.1 Time [s] 0.12 0.14 0.16 0
Infrared Imaging Experiment HYPER 12, Filter 4, calibrated 10mm Orifice, 670g/s Initial flow
Data Analysis / Results Hyper15_4.ptw (X 0...319 / Y 0...189) 400 300 200 Sum up all pictures Path [cm] 100 0-100 -200-300 0 200 400 600 800 Path [cm] 1,000 1,200 Overall Radiation of the flame Seperately in four Spektral Ranges: 1.5-2.5 / 3.0-3.9 / 3.0-5.0 / 4.1-5.3μm
Data Analysis / Results Centerline of each frame Averaging 10 rows Time [s] Hyper12_4.ptw (Row 96...105) 0.6 0.8 1 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 2.8 3 3.2 3.4 3.6 3.8 4 4.2 0 200 400 600 800 1,000 1,200 Path [cm] HYPER12 1,5mm / 40g/s Time [s] Hyper15_4.ptw (Row 96...105) 0.6 0.8 1 1.2 1.4 1.6 1.8 2 2.2 2.4 2.6 2.8 3 3.2 3.4 3.6 3.8 4 4.2 0 200 400 600 800 1,000 1,200 Path [cm] HYPER15 10mm / 670g/s Flame length development
Data Analysis / Results: Flame Propagation Map Hyper04_4.ptw Path [cm] 180 160 140 120 100 80 60 40 20 0-20 -40-60 -80-100 -120-140 -160-180 Example for Flame Propagation Map Experiment HYPER4 3.2mm Orifice 160g/s Initial gas flow All regions of highest radiation gradient stacked, Ignition on top -50 0 50 100 150 200 250 300 Path [cm] 350 400 450 500 550 600
Averaged flame lengths vs. orifice diameter Shortly after Ignition after 4-6 Seconds Proportional increase of flame length with orifice diameter for smaller diameters Large scatter of ±1m in flame length
Averaged apparent flame velocities upstream (Start) downstream downstream averaged
CONCLUSION Image analysis techniques enable a detailed visualisation of hydrogen jets and jet flames Flame velocities after ignition exceed more than 100m/s, 2 of 23 reached 400m/s Low Ignition probability <-> increased probability for late ignition even for a stable free jet