H2FC SUPERGEN Hub Research Forum 2016
1–2 September 2016, University of St-Andrews
V. Molkov, D. Makarov Hydrogen Safety Engineering and Research Centre, University of Ulster
Core research on hydrogen and fuel cell safety and EPSRC Challenge project
“Integrated safety strategies for onboard hydrogen storage systems”
Core research: Hydrogen and FC Safety
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.GB1602069.5 “Composite pressure vessel” (05.02.2016).
Research impact
Core research: Hydrogen and FC Safety
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
PhD project “Innovative solutions to reduce separation
distances in hydrogen systems” (Dr David Yates)
Core research: Hydrogen and FC Safety
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.
PhD project “Fire resistance of onboard high pressure
storage tanks for hydrogen-powered vehicles”
(Dr Sergii Kashkarov)
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
H2FC SUPERGEN Research Forum 2016
1st –2nd Sept 2016, University of St-Andrews
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
Previously reported results
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)
Summary
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
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)
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)
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
28.6 %
WP4 Testing of tanks with increased FRR
Further fire tests in cooperation with HSL:
o Agreed diffusive propane burner design following Global Technical Regulation (GTR) #13 requirements
T4.2: Fire tests
160
115
160
1650
1 3
5 6
8
2
4
7 9 115
WP4 Testing of tanks with increased FRR
Further fire tests in cooperation with HSL:
o Completed qualification mock fire testing
T4.2: Fire tests
0
200
400
600
800
1000
50 100 150 200 250 300
60 per. Mov. Avg. (Burner 4)
60 per. Mov. Avg. (Burner 5)
60 per. Mov. Avg. (Burner 6)
HRR=370 kW GTR#13 - OK
WP4 Testing of tanks with increased FRR
Experimental programme
T4.2: Fire tests
Test
No Tank condition
C3H8 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
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
WP6. Fire protocol, outreach programme
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
Adsorbent Polymer Liners in Type IV Hydrogen Storage Tanks
21 April, 2016
Dr Katarzyna Polak-Kraśna1
Dr S. Rochat2, L. Holyfield3, Dr R. Dawson2, Prof. A. Burrows2, Prof. C.R. Bowen1, Dr T.J.Mays3
University of Bath 1Department of Mechanical
Engineering 2Department of Chemistry
3Department of Chemical Engineering
— Solids – alternative to high pressure tanks and liquefied H2
— Mechanism of physisorption on the surface of materials – reversible H2 storage,
rapid adsorption and recovery
— Polymers of Intrinsic Microporosity – PIMs
Hydrogen storage in PIMs
(Jena, 2011)
Hydrogen Bridge 2016 UK-China, Hangzhou 21/04/2016
PIM-1’s exemplary molecular model (McKeown, 2006)
• accessible internal surface area in the range of 500-900 m2/g
• good mechanical properties
Syn
thes
is o
f PIM
-1
(Bud
d, 2
004)
PIM
-1 fi
lm
Hydrogen Bridge 2016 UK-China, Hangzhou 21/04/2016
CFRP Outer Casing
H2 impermeable liner
Bulk H2
H2 adsorbent
type IV hydrogen tank
PIM-1 composites for H2 storage liners
Polymer of Intrinsic Microporosity
- high surface area (900 m2/g)
- internal pores of 2 nm diameter
- soluble, forms films
- good mechanical properties
or
Metal Organic
Framework (MOF)
- powders with
huge surface
area (up to
5000 m2/g) Porous Aromatic
Framework (PAF)
lower pressure, improved safety, decreased
cost of hydrogen storage
N2 and H2 isotherms of PIM-1
Hydrogen Bridge 2016 UK-China, Hangzhou 21/04/2016
— N2 adsorption ( ) and desorption ( ), BET (Brunauer, Emmett and Teller theory) surface area 797 m2/g
— High hydrogen update but insufficient
— Fillers increasing surface area necessary
-2 0 2 4 6 8 10 12 14 16 18
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
1E-3 0.01 0.1 1 10 100
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
me / w
t%
Pressure / MPa
Adsorption
Desorption
me / w
t%
Pressure / MPa
H2 isotherms
Mechanical Testing
Hydrogen Bridge 2016 UK-China, Hangzhou 21/04/2016
0
0.05
0.1
0.15
0.2
0.25
0.3
1
10
100
1000
10000
-200 0 200 400
tan d
elta
[ ]
E', E
' [M
Pa
]
Temperature [˚C]
E'[MPa]
E"[MPa]
tan_delta []
Uniaxial static tensile testing • Thickness 43-143 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
Mechanical properties
sufficient for use in hydrogen
storage tank!
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 m2/g (insoluble powder)
— “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 m2/g
— Further properties to be investigated
Hydrogen Bridge 2016 UK-China, Hangzhou 21/04/2016
Can we improve PIM-1 to fulfil surface
area and H2 adsorption requirements?
Thank you for your attention!
Dr Rob Dawson
Hydrogen Bridge 2016 UK-China, Hangzhou 21/04/2016
Dr Katarzyna Polak-Kraśna @gwozdzie
Prof. Tim Mays https://youtu.be/quWalK0nH5s
Prof. Chris Bowen
@BowenNEMESIS Prof. Andy
Burrows
Leighton Holyfield Dr Sébastien Rochat @sebrochat
Dr Mi Tian @mitianzhang
WarwickFIRE
School of Engineering, University of Warwick
EPSRC Challenge Project “Integrated Safety Strategies for Onboard
Hydrogen Storage Systems”
Zaki Saldi, Jennifer Wen
Numerical models
• 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).
Mouritz et al (2009)
CFD
FE
Heat Flux
H2 cylinder, propane fire
• Type-4 composite cylinder
• Initial pressure 34.3 MPa.
• Propane flow rate 415-580 scfh.
• HRR ~ 370 kW.
• Rupture time 6 min 27 s, internal pressure at rupture = 357 bar.
Experiment: Zalosh R., and Weyandt N., Hydrogen Fuel Tank Fire Exposure Burst Test, SAE paper number 2005-01-1886, 2005.
H2 cylinder fire resistance
• 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;40:848–59 covering -2150C < T < 5000C 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.
Hu et al, IJHS, 2008
Failure time
Method Failure time [s] Remarks
Experiment 387 s Zalosh & Weyandt, 2005
Simulation, thermal, based on decomposition field
- 50% of CFRP fully decomposed in 600 s
Simulation, thermal, based on internal pressure & failure pressure in experiment
258 s, 597 s Emissivity = 0, 0.5
Simulation, thermo-mechanical, Tsai-Wu failure criteria
190 s Ply angles & number of layers unknown (used: angle = 0 deg, 6 layers).
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).