From DuraDemo to MARANDA project- use of industrial site for hydrogen fuelcell durability testing

October 9th 2017, Kivimiehentie 3 Espoo,Finland

Jari Ihonen, VTT

210.10.2017

Contents

§ PEMFC durability testing results from Durademo project

§ The possible use of by-product hydrogen from sodiumchlorate production as vehicle fuel

§ PEMFC durability testing in MARANDA project and how itwill help for accepting by-product hydrogen as vehicle fuelin fuel cell electric vehicles (FCEV)

310.10.2017

DURADEMO PROJECT 2012-2015

410.10.2017

Motivation for the DuraDemo project§ In 2012-2013 TEKES FC programme supported industry

project Demo 2013

§ Durability demonstration of PEMFC technology was andstill is important for working machine industry

§ In Finnish sodium chlorate and chlor-alkali industry needfor large PEMFC systems for the use of by-producthydrogen – near term market

§ VTT had sufficient knowledge to demonstrate PEMFCsystems using by-product hydrogen from e.g. sodiumchlorate industry

NaCl + 3 H2O –> 2 NaClO3 + 3 H2 (and O2 + Cl2)2 H2O + 2 NaCl –> 2 NaOH + H2 + Cl2

510.10.2017

DuraDemo project phases and industry participation

§ Initially 2-year (1.1.2012-31.3.2014)TEKES funded project supportingDemo2013§ Initial total budget 1,5 M€§ 10% industry§ 70% Tekes§ 20% VTT

§ Extension of the project duration andbudget (up to 1.66 M€ ) in September2014§ Only WP1 work (demo) was continued

§ Extension of the project duration until theend of 2015 (accepted in May 2015)

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The durability testing site at Kemira sodiumchlorate factory Sastamala, Finland

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Results from Durademo project - overview

Jari Ihonen; Pauli Koski; Valtteri Pulkkinen; Timo Keränen; Henri Karimäki; Sonja Auvinen; Kaj Nikiforow; Mikko Kotisaari; Heidi Tuiskula; Jaana Viitakangas. Operational experiences ofPEMFC pilot plant using low grade hydrogen from sodium chlorate production process International Journal of Hydrogen energy. in press (Available online 8 October 2017)

• 5 stages of operation during 21 months

• Initial start-up was difficult due to watercondensation when stack were cold

• Remote start-up required a lot of extra work

• The main reliability issue was hydrogen supplyside components leading long down-time

• System control and system safety featureworked without any problems

810.10.2017

Results from Durademo project– performance fluctuation

• Hydrogen supply pressuretriggered most of the shut-downs (>100)

• Slow fluctuation ofperformance could belinked to H2 quality• Operation T <60° C

• Longest continuousoperation was over 700hours

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Durability testing results from Durademo project

• Degradation rate was2-3 mvolts / h for 10-150 A range

• At higher currentdensities the rate washigher

• Degradation rate wassimilar to the literatureresults with higherquality hydrogen

• Extrapolated lifetime> 20000 h, when 20%voltage degradation asend-of-life criteria

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By-product hydrogen production in Finlandand globally

§ Largest by-products sites now in Finland:§ Kemira Chemicals, Äetsä, Kuusankoski,

Joutseno§ Total > 18 000 ton/a (> 0,6 TWh)§ Significant increase of H2 from

Joutseno in 2018§ Eka Chemicals (Akzo Nobel), Oulu about

2000 ton/a§ 10000 ton/a would fuel 1000-2000 city buses

§ Globally§ By product H2 from chlorine production is

about 1 600 000 ton/a§ By product H2 from sodium chlorate

production is about 220 000 ton/a

Enough for 5-10 million fuelcell electric vehicles!

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The quality of by-product hydrogen from sodiumchlorate production

§ According to thesis ofBraxenholm by-producthydrogen from sodiumchlorate production can not beused as FCEV fuel as it doesnot fulfil ISO 14687-2:2012requirements

§ Is this true?

§ What can be done to makethis hydrogen suitable asFCEV fuel?

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A typical sodium chlorate hydrogen purification system*

* Braxenholm, D. By-Product Hydrogen to Fuel Cell Vehicleshttp://publications.lib.chalmers.se/records/fulltext/237961/237961.pdf

Reaction: NaCl + 3 H2O –> 2 NaClO3 + 3 H2 (and O2 + Cl2)

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In DuraDemo and HyCoRA projects the quality ofhydrogen in Sastamala has been measured

[27] Braxenholm, D. By-Product Hydrogen to Fuel Cell Vehicleshttp://publications.lib.chalmers.se/records/fulltext/237961/237961.pdf

ISO 14687-2:2012Requirements

> 99.97 vol-%

< 100 vol-ppm< 0.004 vol-ppm< 0.05 vol-ppm< 5 vol-ppm< 0.2 vol-ppm

< 2 vol-ppm< 5 vol-ppm< 100 vol-ppm

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CO measurements in HyCoRA project (5 weeks)

ISO 14687-2limit 200 ppb

Exceeded frequently,even if average COlevel was <100 ppb

HyCoRA – Deliverable 6.7 final report

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CO2 measurements in HyCoRA project (5 weeks)

ISO 14687-2 limit 2 ppm exceeded all the time

HyCoRA – Deliverable 6.7 final report

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Some conclusions

§ According to measurements hydrogen sodium chlorate productionfrom does not fulfil ISO 14687-2:2012 or ISO 14687-3:2014§ CO2 level is the main issue (as for H2 from chlor-alkali*)§ CO level is within limits most of the time§ N2, O2 and HCl level have not been measured

§ According to DuraDemo results hydrogen is pure enough that itdoes not cause additional degradation§ Indirect evidence for low HCl level

§ Options for getting this H2 available for FCEV fuel§ Additional purification – can be expensive§ Change CO2 limit in ISO 14687-2:2012 – will take 2-4 years§ Use H2 only in bus fleets – no issues if H2 quality measured

* http://hycora.eu/workshops/30092014/HyCoRa_Workshop_2014-09-30-SINTEF_v2.pdf

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MARANDA durability testing timeline

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Some goals of durability testing in MARANDA project

§ Validate the system performance on a powertrain testbench and in a target marine vessel for a period ofminimum 6 months (4380 hours)

§ Fuel cell stack life should exceed 15,000 hours§ Same power – 10% lower stack voltage

§ Monitor quality of by-product hydrogen, including allrelevant impurities in ISO 14687-2:2012 standard

1910.10.2017

WP7FC System integration to

containers with fuel storage

T7.1Designing and

building adurability test

bench

T7.2Designing andintegration of

fuel cell systemsinto containersfor the target

vessel

T7.3Safety

assessments ofthe fuel cellsystems and

hydrogen

T7.4Initial testing of

the fuel cellsystems and

hydrogenstorage solution

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Task 7.1 Designing and building a durability test bench

DesignPhase

SystemIntegration

InitialTesting at

VTT

Durabilitytest inÄetsä

D7.1 (M8)Oct 2017

MS3 (M13)Mar 2018

D7.4 (M12)Feb 2018

MS2 (M9)Nov 2017

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Task 7.1 Designing and building a durability test bench

§ Integration and containerization

§ Fuel Cell Power Module (SH)§ Power Electronics (ABB)§ Higher-level control system (VTT)

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Hydrogen gas purity control in MARANDA projectduring durability testing

§ Continuously: CO, CO2, CH4, N2, O2 and H2O§ Methods: GC-FID with methaniser (CO, CO2, CH4) and TCD for

N2 and O2§ Valve flushing in GC with Ar/He to enable ppm level O2

measurements§ H2O measurement with humidity sensor (?)

§ A measurement campaign (few weeks to few months): HCl§ Instrument to be selected

§ Filtering and collection of particles

2310.10.2017

Acknowledgements

§ DuraDemo project work was carried out under the Fuel Cells research program of TEKES, theFinnish Funding Agency for Technology, within a jointly funded project involving VTT TechnicalResearch Centre of Finland Ltd and Finnish industry partners Kemira Chemicals Oy, CargotecFinland Oy, Konecranes Plc, Leppäkosken sähkö Oy, ABB Oy, Woikoski Oy, MSc Electronics Oy,Wärtsilä Finland Oy and Fuel Cell Finland industry grouping, a part of Teknologiateollisuus Ry.

§ MARANDA project has received funding from the Fuel Cells and Hydrogen 2 Joint Undertakingunder grant agreement No 735717. This Joint Undertaking receives support from the EuropeanUnion’s Horizon 2020 research and innovation programme and Hydrogen Europe and N.ERGHY

§ HyCoRA project: The research leading to these results has received funding from the EuropeanUnion's Seventh Framework Programme(FP7/2007 2013)for the Fuel Cells and Hydrogen JointTechnology Initiative under grant agreement n°621223