1. The Hydrogen Fuel Quality Issue: The Vision of a Fuel Supplier Françoise Barbier and Martine Carré Air Liquide Research & Development NHA Conference – 5 May 2010

2. 2 Outline Company overview Fuel quality issues Hydrogen production and supply Analytical methods capabilities Hydrogen quality and cost Summary

3. 3 Air Liquide overview The world leader in gases for industry, health & the environment Total revenue 2009 : €12 billion Over 1 million customers in 75 countries 42300 employees A strategy built around 5 growth drivers Energy Environment Emerging economies Health High-Tech 36% of Air Liquide’s revenue derived from gas applications designed to preserve life and protect the environment 60% of Air Liquide’s R&D budget devoted to developing technologies for sustainable development

4. 4 More than 40 years of experience with hydrogen for industrial and space applications More than 200 H 2 production units Broad range of H 2 distribution modes pipelines, trucks, cylinders Active since 2000 in Hydrogen Energy on the full supply chain from production to fuel cell Research & Development High technologies H 2 fueling stations Fuel cells through Deployments Worldwide large-scale projects Air Liquide: A global player in the Hydrogen Energy business

5. 5 Paving the way with early markets … … to be ready for 2015 Hychain utility vehicle powered by Axane fuel cell Airport loader powered by Axane fuel cell Remote site: Bouygues Telecom antenna Axane portable fuel cell Hychain fuel cell cargo bike Air Liquide H 2 refueling station for a fleet of busses in the city of Whistler

6. 6 Supplying H 2 at refueling stations US Delaware, 350 barCanada Kapuskasing, 700 bar Canada Whistler 2010, 700 bar Japan Kawasaki, 350 bar

7. 7 H 2 fuel quality specifications (ISO/TS 14687-2) International work (ISO TC 197/WG 12) is in progress to specify the quality of hydrogen for utilization in PEM fuel cell road vehicle systems still in discussion

8. 8 Defining H 2 fuel quality standard Impurities versus fuel cell performance degradation Trade-off between H 2 purity and H 2 supply cost Cost for production and delivery Cost for quality assurance including impurities analysis Analytical methods to be applied and their capabilities (quantification limits) Factors affecting the threshold limits of impurities

9. 9 The quality of hydrogen is known to affect the operation of fuel cells Different behavior depending on impurities Need to classify “negative” impurities: “critical” or “significant” Effects of H 2 impurities on operation of fuel cells Effect of COEffect of H 2 S PEM fuel cell performance decreases rapidly with the increase of CO or H 2 S concentrations introduced into hydrogen

10. 10 Diverse H 2 sourcing Different production pathways and feedstocks The future standard must reflect this diversity Fossil fuels: the current route Steam methane reforming Partial oxydation / autothermal reforming of hydrocarbons Coal gasification Water and electricity: pathway towards renewable fuel Low temperature electrolysis High temperature electrolysis Renewable sources: technologies being developed Bio-derived liquids reforming Biogas reforming Biomass gasification Biological processes) Photo(electro)catalysis Solar thermochemical cycles

11. 11 Traditional H 2 production & purification techniques Hydrocarbon source SMR POX ATR H2 + CO Syngas PSA Membrane Cryogenic Purification H2 Production SMR = Steam Methane Reformer POX = Partial Oxidation ATR = Autothermal Reformer PSA = Pressure Swing Adsorption

12. 12 Description of H 2 purification with PSA Based on adsorbent technology Adsorb different gas impurities depending on the affinity Multiple adsorbents: silica, alumina, molecular sieves, activated carbons Better quality of H 2 is produced compared to other purifications process Between 99% to 99.99% The PSA is very effective for removing H 2 S, NH 3, CO, CO 2, CH 4 but it has relatively more difficulty retaining inert gases

13. 13 General PSA relationship PSA Unit size H 2 recovery H 2 Cost H 2 Product purity - PSA inlet H 2 Product purity – PSA outlet Changing SMR and PSA operating conditions in existing plants to meet ISO specifications significant effect on the H 2 cost Plant design dedicated to H 2 fuel quality H 2 cost may be slightly affected by the ISO specifications

14. 14 Gas in tube trailer & cylinder Liquid in cryogenic truck Gas in pipeline ProductionPurificationCompressionLiquefaction Delivery Dispenser H2 gas production center The hydrogen chain Existing hydrogen infrastructure

15. 15 Impurities in the hydrogen chain Commercial hydrocarbon feedstock H 2 S, MeSH, EtSH, oxygenates (CH 3 OH…), N 2, higher hydrocarbons, alkenes, alkynes … SMR operating conditions CO, CO 2, CH 4, NH 3... Subsequent purification process PSA can reduce impurity concentration at very low levels Delivery modes Pipelines: chemical industry grades Tube trailers: various grades Cylinders: various and special grades case-by-case Cryogenic truck: specifications > 99.999% Purity of gaseous H 2 from cryogenic methods is extremely high Relative amount of impurities in H 2 is dependent on the infrastructure diversity:

16. 16 Commercial hydrogen impurities No grade for hydrogen as a fuel H2 gradeMinimum assay purity Total max impurity level ISO TS 14687-2 fuel specification fuel specification 99.99 % N40 100 ppm Compressed, semiconductor CGA (L) 99.999 % N50 10 ppm Compressed, for analysis CGA (F) 99.995 % N45 50 ppm Compressed, for analysis Europe 99.999 % N50 10 ppm Compressed, high industrial grade, Europe 99.995 % N45 50 ppm Compressed, industrial grade, Europe 99.9 % N30 1000 ppm

17. 17 Quality control for H 2 as a fuel Customers are requesting analysis of H 2 according to the specifications defined in the ISO standard: Which analytical protocol can be applied ? Is it possible (or practical) for all the species in the ISO specification ?

18. 18 Which analytical protocol can be applied ? Make difference between Analytical methods for demonstrating compliance to specifications which can be done off-line in laboratories after sampling of H2 and Analytical method for continuous control of species done on-line in plants Various options 1. on-line analysis of all the species in the ISO specifications 2. on-line analysis of “canary” species 3. batch analysis of all the species in the ISO specifications

19. 19 Analytical protocol relationship Technical capability Guarantee for customer Cost 1. On-line analysis of all species ☹☺ ✰✰✰ 2. On-line analysis “canary” species ☹☺ ✰✰ 3. Off-line analysis by batch analysis ☺☹ ✰  Not enough available analytical methods  Which “canary” species to choose ?  High cost due to number of impurities to control and low level (ppb)

20. 20 Example: On-line analysis by FTIR method Typical data from Fourier Transform Infra-Red (FTIR) analyzer

21. 21 Example: Off-line analysis by GC method Typical data from Gas Chromatograph (GC)

22. 22 Traceability in H 2 impurities analysis For the development and validation of newly developed analytical methods: Strong needs for standard and/or reference gas mixture to control the accuracy of the measurement Strong needs for Round Robin Test for validation of selected analytical methods and getting statistically reasonable numbers of Limit of Detection and Limit of Quantification

23. 23 H 2 quality assurance procedure Continuous on-line monitoring of all impurity species with one-by-one identification Very expensive Cannot be routinely applied On-line analysis “canary” species (+ batch analysis of other species) Need to identify a canary constituent: CO suggested Reasonable cost if assumption of CO detection proves that all other impurity levels will be known Off-line analysis by batch analysis Spot analysis Have representative sampling Various solutions more or less complex and financially viable Work in progress with ISO TC 197 WG 12 members

24. 24 Addressing hydrogen quality and cost Identify the impurities and the contents that have a real detrimental impact on operation of PEM fuel cells (“right” set of H 2 specifications) Define what type of analysis is needed to meet the specification (“right” analysis) Costs need to be considered broadly Consider impact on possibility to use existing sources Implementation of additional measures and purification on existing plants is costly and not always feasible Loss of hydrogen (= loss of efficiency and capacity) Need for a cost-benefit analysis (“right” balance between cost and impact on fuel cell)

25. 25 Summary H 2 quality specifications must be practical, sustainable and cost effective to implement Difficulties still exist for defining the quality specification of the ISO standard Analytical methods are not qualified at worldwide level All international key actors for ISO standardization are required for consensus The target is moving: evolution of fuel cell requirements with the development of new materials

26. 26 Thank you for your attention francoise.barbier@airliquide.com