1. 1 Recent Research and Development on Unintended Releases of Hydrogen William Houf, Greg Evans, Robert Schefer, Jeff LaChance Sandia National Laboratories 2nd International Conference on Hydrogen Safety San Sebastian, Spain September 11-13, 2007 This presentation does not contain any proprietary, confidential, or otherwise restricted information

2. 2 Objectives Development of new hydrogen codes and standards needs a traceable technical basis: –characterize small-scale gaseous leaks, determine barrier wall effectiveness –perform physical and numerical experiments to quantify fluid mechanics, combustion, heat transfer, cloud dispersion behavior –develop validated engineering models and CFD models for consequence analysis –use quantitative risk assessment for risk-informed decision making and identification of risk mitigation strategies Provide advocacy and technical support for the codes and standards change process: –consequence and risk: ICC and NFPA –international engagement: HYPER (EU 6 th Framework Program), Installation Permitting Guidance for Hydrogen and Fuel Cell Stationary Applications

3. 3 We have completed experiments and analysis on large-scale high momentum leaks. Nighttime photograph of 413 bar (6000 psig) large-scale H 2 jet-flame test (d j = 5.08mm, L vis = 10.6 m) from Sandia/SRI tests. 11.3 m H 2 jet-flame radiation model verified at source pressures of 172 bar (2500 psig), 413 bar (6000 psig) Unignited jet concentration decay model verified against natural gas data (source pressure 3.5 - 76 bar) and compressible Navier-Stokes simulations for H 2 (206 bar, (3000 psig)) Experiments and safety distance modeling results published in peer-reviewed papers (1) Houf and Schefer, “Predicting Radiative Heat Fluxes and Flammability Envelopes from Unintended Releases of Hydrogen,” Int. Jour. of Hydrogen Energy, Vol. 32, Jan. 2007. (2) Schefer, Houf, San Marchi, Chernicoff, and Englom, “Characterization of Leaks from Compressed Hydrogen Dispensing Systems and Related Components,” Int. Jour. of Hydrogen Energy, Vol. 31, Aug. 2006. (3) Molina, Schefer, and Houf, “Radiative Fraction and Optical Thickness in Large-Scale Hydrogen Jet Flames,” Proceedings of the Combustion Institute, April, 2006. (4) Houf and Schefer, “Rad. Heat Flux & Flam. Env. Pred. from Unintended Rel. of H2,” Proc. 13 th Int. Heat Tran. Conf., Aug., 2006. (5) Schefer, Houf, Williams, Bourne, and Colton, “Characterization of High-Pressure, Under-Expanded Hydrogen-Jet Flames,” In Press, Int. Jour. of Hydrogen Energy, 2007. (6) Houf and Schefer, “Predicting Radiative Heat Fluxes and Flammability Envelopes from Unintended Releases of Hydrogen,” 16th NHA Meeting, Washington, DC, March 2005. (6) Schefer, R. W., Houf, W. G., Bourne, B. and Colton, J., “Turbulent Hydrogen-Jet Flame Characterization”, Int. Jour. of Hydrogen Energy, 2005. (7) Schefer, R. W., Houf, W. G., Bourne, B. and Colton, J., “Experimental Measurements to Characterize the Thermal and Radiation Properties of an Open-flame Hydrogen Plume”, 15 th NHA Meeting, April 26-30, 2004, Los Angeles, CA. (8) Schefer, “Combustion Basics,” in National Fire Protection Association (NFPA) Guide to Gas Safety, 2004.

4. 4 We have completed a study of the hydrogen small/slow leak regime. Goal - Provide technical information on small/slow leaks from hydrogen-based systems Slow leaks may occur from Low pressure electrolyzers Leaky fittings or O-rings with large amounts of pressure drop Vents from buildings or storage facilities containing hydrogen Previous work focused on the high-momentum leak regime where the effects of buoyancy on the flow were small In the slow leak regime both momentum and buoyant forces are important Buoyant forces affect the trajectory and rate of entrainment Significant curvature can occur in jet trajectory Concentration decay and the distance to mean lower ignition limit The ratio of momentum to buoyant forces for the leak can be characterized by the exit densimetric Froude number F den = U exit /(gD(rho amb - rho exit )/rho exit ) 1/2 Approach Experimentally characterize slow leaks (leak size and geometry) Develop validated engineering models Use engineering models to generate safety information Safety distance to (mean) lower concentration ignition limit Flowrate = 20 scfm, Hole Dia. = 9.44 mm Exit Mach Number = 0.1 (Unchoked Flow) F den = 117 *Photograph from: Dr. Michael Swain, (Univ. of Miami) Fuel Cell Summit Meeting June 17, 2004 Jet Flame from an Ignited H 2 Slow Leak*

5. 5 Rayleigh scattering system CCD camera laser sheet Rayleigh scattering is used to map concentration contours of small/slow leaks. Experimentally measured centerline concentration decay rates in vertical buoyant jets Instantaneous H 2 mole fraction images in unignited vertical jet Instantaneous H 2 mole fraction images in unignited horizontal jet g g 5% m.f. 4% m.f. 10% m.f. 20% m.f. 6.67% m.f. 6

6. 6 Mole Fraction 0.2 0.4 0.6 0.8 H 2 jet at Re=2,384; Fr = 268 H 2 flammability limits: LFL 4.0%; RFL 75% CH 4 flammability limits: LFL 5.2%; RFL 15% CH 4 jet at Re=6,813; Fr = 478 Ignitable gas envelope is significantly larger in H 2 jets than CH 4 jets. Comparison of ignitable gas envelopes for hydrogen and methane jets.

7. 7 Buoyancy effects are characterized by Froude number. Horizontal H 2 Jet (d j =1.9 mm) Time-averaged H 2 mole fraction distributions. Froude number is a measure of strength of momentum force relative to the buoyant force Increased upward jet curvature is due to increased buoyancy at lower Froude numbers. Fr=99 Fr=152 Fr=268 Fr=152 Fr=99 Mole Fraction 0.2 0.4 0.6 0.8

8. 8 We have developed an engineering model for the buoyant jet from an unignited small/slow hydrogen leak. Profiles of jet velocity and scalars assumed Gaussian in zone of established flow (for example) UU g Jet Axis   S  0 Z X r Discharge Point of Leak Engineering model for buoyant jet from hydrogen slow leak Jet trajectory H 2 concentration decay along jet trajectory Distance to lower flammability limit (LFL) Based on integral jet model in streamline coordinates Continuity Horizontal Momentum Vertical Momentum Concentration Trajectory Simulation executes in a few seconds on a workstation compared to several hours for Navier-Stokes calculations of the same problem

9. 9 Comparison of model with data from the Sandia slow-leak experiments for buoyant H 2 plumes The engineering model has been validated against data for buoyant slow leaks. Comparison of model and data for concentration decay of vertical buoyant He plume The buoyantly- driven flow model : uses a different entrainment law than our momentum jet model integrates along the stream line to capture plume trajectory Z/D HeH2H2 Lower Froude number leaks are more buoyant Buoyancy increases entrainment rate causing faster concentration decay New entrainment law adds buoyancy-induced entrainment to momentum induced entrainment Simulations

10. 10 Risk-Informed decision making should be used for separation distances. Current code separation distances are not reflective of future fueling station operations (e.g., 70 MPa) Facility parameters (e.g., operating pressure and volume) should be used to delineate separation distances Consequence-based separation distances (i.e., single event) can be large depending on pressure, leak size, and consequence parameter QRA insights are being considered by NFPA-2 to help establish meaningful separation distances and other code requirements Leak Diameter (mm) Consequence Parameter

11. 11 We are studying barriers as a mitigation strategy to reduce safety distances. Characterize H 2 transport and mixing near barrier walls through combined experiment and modeling Identify conditions leading to deflagration or detonation residence time and ignition timing magnitude of over-pressure and duration Develop correlations for wall heights dependency and wall- standoff distances Combine data and analysis with quantitative risk assessment for barrier configuration guidance Goal: determine if barriers are an effective jet mitigation technique since mixtures of H 2 and air can ignite and potentially generate large overpressures. Collaborating with the HYPER project in Europe. H2H2 (a) (b) (c) Unignited H 2 Jets Mixing Axial Distance Pressure Deflagration to detonation Over-pressure from ignition of premixed hydrogen / air Over-pressure characterization

12. 12 Characterize stabilization of H 2 jet flame on and behind barrier Characterize thermal/structural integrity of barriers Use CFD modeling and validation for H 2 jet flames to minimize the number of tests Develop correlations for wall height dependencies and wall stand-off distances Combine data and analysis with quantitative risk assessment for barrier configuration guidance We have initiated the barrier work by verifying the ability of our in house Navier-Stokes code (Fuego) to compute hydrogen jet flames and unignited jet concentration H2H2 (a) (b) (c) Stabilized flame Radiometers H 2 Jet Flames The behavior of H 2 jet flames near barrier walls is also an issue of importance. Barlow flame A (ref. Combustion and Flame, v. 117, pp. 4-31, 1999)

13. 13 We are performing Navier-Stokes calculations of hydrogen jet flames and jet flames on barriers. Fuego 3-D Navier-Stokes Simulation of H 2 Jet Flame Wall Impingement Sandia/SRI H 2 Jet Flame Wall Impingement Test (2500 psi) Simulations Sandia/SRI H 2 jet flame wall impingement tests Applied Mach disk model to 6000 psi jet at 100 s when stagnation pressure was 1505 psig 8 ft by 8 ft barrier with nozzle (dia. = 5.018 mm) 4 ft from wall (20.3 cm thick) on center Computed Mach disk diameter = 61.9 mm Simulated 1/2 domain (10 6 elements) 1st order upwind with std k-  or RNG k-  Radiation loss and heat fluxes predicted with discrete ordinates participating media model New barrier tests being performed at SRI Test site with pre-test CFD predictions

14. 14 We are investigating many different barrier jet flame impingement scenarios and barrier geometries with modeling and full-scale experiments. Different Leak Scenarios Vertical Wall - 90 deg impingement Vertical Wall - +45deg impingement Vertical Wall - Jet centerline aligned with top of wall 60 o Side View Top View Source pressure Leak to barrier spacing Leak trajectory Leak location Barrier geometry 3 Wall Configuration (135 o between walls) 60 o Tilted Wall Different Barrier Geometries

15. 15 Barriers can reduce the exposure from jet flame radiation heat flux as well as reduce jet flame impingement hazard. H 2 Jet Flame Impinging on Barrier H 2 Free Jet Flame d d No barrier (vertical jet flame) With barrier Barrier deflects horizontal issuing jet flame vertically The flame extends above the barrier Radiation at a distance (d) behind the barrier from the deflected flame is less than that from a free vertical jet flame with no barrier

16. 16 Full-scale jet flame impingement experiments provide valuable insight on barrier behavior as well as modeling validation data. Tests performed at SRI Corral Hollow test site Jet Centerline Aligned with Center of Barrier Jet Centerline Aligned with Top of Barrier Pressure (psig) Time (msec) Instrumentation Layout Overpressure from Ignition In front of barrier Behind barrier 2.4m x 2.4m wall with jet centered Time to ignition - 135 msec

17. 17 Summary Completed engineering model for buoyant plumes and reported at 2007 NHA meeting and SAE World Congress - Paper submitted to IJHE and in review QRA is being used to make risk-informed decisions regarding set- backs as part of the NFPA-2 activity Sandia staff are participating with the technical committee QRA incorporates Sandia hydrogen release engineering models QRA methodology is vetted through international risk experts as part of our involvement in IEA Hydrogen Safety Task 19 Barrier walls are being characterized as a jet mitigation strategy for set back reduction Partnership with SRI (testing) and HYPER (analysis) CFD best-practices working group

18. 18 Recent Publications 1.Houf and Schefer, “Small-Scale Unitended Releases of Hydrogen”, 2007 NHA Conference, San Antonio, TX, March 19-22, 2007. 2.Houf and Schefer, “Investigation of Small-Scale Unintended Releases of Hydrogen”, SAE World Congress, Detroit, MI, April 16-19, 2007, (invited paper). 3.LaChance, "Risk-Informed Separation Distances for Hydrogen Refueling Stations“, 2007 NHA Conference, San Antonio, TX, March 19-22, 2007. 4.Schefer and Houf, “Investigation of small-scale unintended releases of hydrogen: momentum-dominated regime”, submitted to International Journal of Hydrogen Energy. 5.Houf, Evans, and Schefer, “Analysis of Jet Flames and Unignited Jets from Unintended Releases of Hydrogen,” 2nd International Conference on Hydrogen Safety, San Sebastian, Spain, September 11-13, 2007. 6.LaChance, “Quantitative Risk Assessment, Safety Studies and Risk Mitigation,” 2nd International Conference on Hydrogen Safety, San Sebastian, Spain, September 11-13, 2007.