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

k.polak-krasna@bath.ac.uk

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).