Core research on hydrogen and fuel cell safety and EPSRC Challenge project Integrated safety strategies for onboard hydrogen storage systems

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1 H2FC SUPERGEN Hub Research Forum September 2016, University of St-Andrews Core research on hydrogen and fuel cell safety and EPSRC Challenge project Integrated safety strategies for onboard hydrogen storage systems V. Molkov, D. Makarov Hydrogen Safety Engineering and Research Centre, University of Ulster

2 Core research: Hydrogen and FC Safety Research impact Core safety research addressed: - Reduction of hazard distances, and - Fire resistance of tanks for CGH2 storage. A model of the load bearing ability of a composite tank under thermal and pressure loads is developed, including tank failure criterion in a fire. The validated model has served as a contemporary tool for the SUPERGEN Challenge project (EP/K021109/1) to study thermal protection of tanks by intumescent paint. A new technology for explosion-free hydrogen tank is proposed. Patent Application No.GB Composite pressure vessel ( ).

3 Core research: Hydrogen and FC Safety PhD project Innovative solutions to reduce separation distances in hydrogen systems (Dr David Yates) Addressed knowledge gaps: Reduction of hazard distance for pressure relief devices (PRD). CFD model is validated using data on plane nozzles. Hazard distances for fan nozzles (compared to round and plane), variable aperture PRD are investigated numerically. Wind effects on under-expanded hydrogen jet fires in ambient co-, counter-, and cross- flow are studied. Numerical results compared against experimental data by Kalghatgi (1983). PhD candidate had a successful viva 13 April 2016

4 Core research: Hydrogen and FC Safety PhD project Fire resistance of onboard high pressure storage tanks for hydrogen-powered vehicles (Dr Sergii Kashkarov) Addressed knowledge gaps: The original analytical model for assessment of blast wave decay after storage tank rupture in a fire (both stand-alone and under-vehicle) is developed. The model is validated against tests performed in USA, engineering nomograms are created. The conjugate heat transfer CFD model of fire resistance of storage tank in a fire is developed. The parametric study demonstrated the effect of heat release rate in a fire, burner design, and composite vessel failure criterion on the fire resistance rating. PhD candidate had a successful viva 14 June 2016.

5 H2FC SUPERGEN Research Forum st 2nd Sept 2016, University of St-Andrews H2FC SUPERGEN Challenge project Integrated safety strategies for onboard hydrogen storage systems (No. EP/K021109/1) D. Makarov, V. Molkov, Y. Kim, S. Kashkarov, V. Shentsov Hydrogen Safety Engineering and Research Centre, University of Ulster

6 Challenge project overview Participants University of Ulster (Dr D Makarov, Prof V. Molkov) University of Bath (Prof T. Mays) University of Warwick (Prof J. Wen) Aim Develop novel safety strategies and engineering solutions for onboard storage of hydrogen Objectives Conduct parametric studies of tank performance in fires to optimize its fire resistance Test Type 4 tanks, demonstrate performance of proposed solutions to increase fire resistance Improve bonfire and TPRD test protocols, including input of fire loading; Perform economic analysis and evaluate reduction in risk of HFC vehicles with longer fire resistance

7 Previously reported results Summary Completed bonfire experimental programme using KIT premixed burner (6 fire tests, bare and thermally protected) o Achieved FRR of intumescent paint protected Type 4 tank 1h 50m - beyond longest experimentally recorded car fire duration 1h 40m o Experimentally confirmed fire resistance rating (FRR) dependence on fire heat release rate (HRR) CFD model for analysis of load bearing ability of intumescent paint protected tank was developed and used to backup experimental studies Started material testing programme (carbon fibre, intumescent paint)

8 WP3 Fire resistance prediction tools (UU) T3.1: Fire resistance models CFD model with structural tank failure criterion update: o Validation against premixed burner experiment (KIT, 2015) Heat release rate 165 kw Heat release rate 79 kw

9 WP3 Fire resistance prediction tools (UU) T3.1: Fire resistance models CFD model with structural tank failure criterion update: o Validation against diffusive burner experiment (Weyandt, 2005)

10 Type 4 tanks fire resistance summary Fire resistance rating vs heat release rate Experimental and simulation data on fire resistance rating (FRR) of unprotected Type 4 cylinders vs bonfire heat release rate (HRR)

11 28.6 % Type 4 tanks fire resistance summary Fire resistance rating vs burner type CFD experiments: diffusive burner (Ulster design) and premixed burner (KIT), HRR=165 kw Premixed burner, KIT Diffusive burner, HSL

12 WP4 Testing of tanks with increased FRR T4.2: Fire tests Further fire tests in cooperation with HSL: o Agreed diffusive propane burner design following Global Technical Regulation (GTR) #13 requirements

13 WP4 Testing of tanks with increased FRR T4.2: Fire tests Further fire tests in cooperation with HSL: o Completed qualification mock fire testing HRR=370 kw GTR#13 - OK 60 per. Mov. Avg. (Burner 4) 60 per. Mov. Avg. (Burner 5) 60 per. Mov. Avg. (Burner 6)

14 WP4 Testing of tanks with increased FRR T4.2: Fire tests Experimental programme Test No Tank condition C 3 H 8 mass flow rate HRR 1 Bare tank 10.8 g/s 500 kw 2 Protected tank, intumescent paint (7 mm) 7.9 g/s 370 kw 3 Protected tank, intumescent paint (3 mm) 7.9 g/s 370 kw

15 WP6. Fire protocol, outreach programme International conference Hydrogen Bridge UK-China 2016: Safety of high pressure hydrogen storage (21-22 April 2016, Hangzhou, China) o 2 days event, 15 speakers, in cooperation with project partner Zhejiang University (Hangzhou) The team continues engagement within o International Association for Hydrogen Safety o ISO TC197 Hydrogen Technologies o IEA Hydrogen Implementation Agreement Task 37 Hydrogen Safety

16 Current progress summary Further update and development of CFD model to predict load bearing ability of thermally and pressure loaded Type 4 tanks The updated model was successfully validated against available experimental data Leak-no-burst (explosion free) technology was proposed based on analysis of experimental data and simulation results Experimental fire programme to be continued in cooperation with HSL The team successfully engaging with ISO TC197 Hydrogen Technologies, IEA HIA Task 37 group, IA HySafe, WP GTR#13

17 21 April, 2016 Adsorbent Polymer Liners in Type IV Hydrogen Storage Tanks Dr Katarzyna Polak-Kraśna 1 Dr S. Rochat 2, L. Holyfield 3, Dr R. Dawson 2, Prof. A. Burrows 2, Prof. C.R. Bowen 1, Dr T.J.Mays 3 University of Bath 1 Department of Mechanical Engineering 2 Department of Chemistry 3 Department of Chemical Engineering

18 Synthesis of PIM-1 (Budd, 2004) PIM-1 film Hydrogen storage in PIMs Solids alternative to high pressure tanks and liquefied H 2 Mechanism of physisorption on the surface of materials reversible H 2 storage, rapid adsorption and recovery (Jena, 2011) Polymers of Intrinsic Microporosity PIMs accessible internal surface area in the range of m 2 /g good mechanical properties PIM-1 s exemplary molecular model (McKeown, 2006) Hydrogen Bridge 2016 UK-China, Hangzhou 21/04/2016

19 PIM-1 composites for H2 storage liners Metal Organic Framework (MOF) or Porous Aromatic Framework (PAF) - powders with huge surface area (up to 5000 m 2 /g) Polymer of Intrinsic Microporosity - high surface area (900 m 2 /g) - internal pores of 2 nm diameter - soluble, forms films - good mechanical properties type IV hydrogen tank CFRP Outer Casing lower pressure, improved safety, decreased cost of hydrogen storage H 2 impermeable liner Bulk H 2 H 2 adsorbent Hydrogen Bridge 2016 UK-China, Hangzhou 21/04/2016

20 m e / wt% m e / wt% N 2 and H 2 isotherms of PIM-1 N 2 adsorption ( ) and desorption ( ), BET (Brunauer, Emmett and Teller theory) surface area 797 m 2 /g High hydrogen update but insufficient Fillers increasing surface area necessary 1.8 H 2 isotherms Adsorption Desorption E Pressure / MPa Pressure / MPa Hydrogen Bridge 2016 UK-China, Hangzhou 21/04/2016

21 E', E' [MPa] tan delta [ ] Mechanical Testing Uniaxial static tensile testing Thickness μm Average tensile stress 31 MPa Ultimate strain 4.4 % Average Young s modulus = 1.26 GPa Yielding stress 11 MPa Dynamic Mechanical Thermal Analysis No glass transition, decomposition at 350 Average storage modulus 970 ± 240 MPa High E, low E, low tan delta => sample almost purely elastic E' [MPa] E" [MPa] Mechanical properties sufficient for use in hydrogen storage tank! tan_del ta [] Temperature [ C] 0 Hydrogen Bridge 2016 UK-China, Hangzhou 21/04/2016

22 Composites PIM-1 has good mechanical and thermal properties but insufficient surface area PAF-1 is a porous aromatic framework with surface areas up to 5000 m 2 /g (insoluble powder) Can we improve PIM-1 to fulfil surface area and H 2 adsorption requirements? Doping PIM-1 films with high-surface area PAF-1 significantly increases the surface area Current best: 23 wt% PAF-1 gives a film with BET SA of 1241 m 2 /g Further properties to be investigated Hydrogen Bridge 2016 UK-China, Hangzhou 21/04/2016

23 Thank you for your attention! Dr Katarzyna Dr Sébastien Leighton Holyfield Dr Rob Dawson Dr Mi Prof. Andy Burrows Prof. Chris Prof. Tim Mays Hydrogen Bridge 2016 UK-China, Hangzhou 21/04/2016

24 EPSRC Challenge Project Integrated Safety Strategies for Onboard Hydrogen Storage Systems Zaki Saldi, Jennifer Wen WarwickFIRE School of Engineering, University of Warwick

25 Numerical models CFD Heat Flux FE Mouritz et al (2009) Computational Fluid Dynamics for fire (firefoam) Finite Element simulation for cylinder thermo-mechanics (heat transfer, decomposition, degradation). (Elmer) One-way coupling through heat flux from fire (CFD) to cylinder (FE).

26 H 2 cylinder, propane fire Experiment: Zalosh R., and Weyandt N., Hydrogen Fuel Tank Fire Exposure Burst Test, SAE paper number , Type-4 composite cylinder Initial pressure 34.3 MPa. Propane flow rate scfh. HRR ~ 370 kw. Rupture time 6 min 27 s, internal pressure at rupture = 357 bar.

27 H 2 cylinder fire resistance Hu et al, IJHS, 2008 Fire resistance (initial estimate) based on internal pressure (function of temperature). (Deming WE, Shupe LE. Some physical properties of compressed gases, III. Hydrogen. Phys Rev 1932;40: covering C < T < C and p up to 1200 atm). Internal pressure at failure time in experiment (Zalosh, 2005): 357 bar. Predicted fire resistance: 597 s (9 mins 57 s) (with radiative heat loss, emissivity = 0.5), 258 s (4 mins 18 s) (emissivity = 0), Zalosh experiment: 6 mins 27 s.

28 Failure time Method Failure time [s] Remarks Experiment 387 s Zalosh & Weyandt, 2005 Simulation, thermal, based on decomposition field Simulation, thermal, based on internal pressure & failure pressure in experiment Simulation, thermo-mechanical, Tsai-Wu failure criteria - 50% of CFRP fully decomposed in 600 s 258 s, 597 s Emissivity = 0, s Ply angles & number of layers unknown (used: angle = 0 deg, 6 layers).

29 Summary LES simulation of fire using FireFOAM. One way coupling between CFD (fire) & FE (cylinder) through mean heat flux predicted by CFD. Around 50% of tank CFRP decomposed after 600 s. Reduction in load bearing capability of cylinder when heated in fire demonstrated (increase in number of failed elements in thermomechanical simulation) Type-4 cylinder in propane fire (hydrogen tank fire exposure burst test, Zalosh & Weyandt, 2005): Failure time predicted using internal pressure = 258 s & 597 s (emissivity = 0, 0.5). Failure time based on thermomechanical simulation & failure analysis = 190 s. (Burst experiment = 387 s). Validation needed. More info needed on unknowns (ply angles & number of layers). Future works: non-zero ply angles, other failure criterion (e.g. Hanshin).