1. Hervé Barthélémy Hydrogen storage - Industrial Prospectives INTERNATIONAL CONFERENCE ON HYDROGEN SAFETY ICHS 2011 September 12-14, 2011 San Francisco, California - USA

2. The world leader in gases for industry, health and the environment Hydrogen at Air Liquide H 2 Production Secondary Distribution LargeDistributionLargeDistribution Markets Markets Safety/Standards/Regulations Air Liquide is present worldwide on all segments of the Hydrogen Energy supply chain Space propulsion PEM Fuel Cells Refuelling stations Innovative gas storage & Packaging Trucks, trailors SMR, Electrolysis purification, liquefaction > 200 plants Hundred of thousands of 200 bar cylinders > 1000 trucks Cryogenic tank > 1700 km Pipelines

3. The world leader in gases for industry, health and the environment 3 I. COMPRESSED HYDROGEN STORAGE CASE STUDIES AND APPLICATIONS: HYDROGEN STORAGE AND INDUSTRIAL PROSPECTIVE II. CRYOGENIC VESSELS FOR THE STORAGE OF LIQUID HYDROGEN

4. The world leader in gases for industry, health and the environment 4 1. INTRODUCTION AND DIFFERENT TYPES 2. SOME HISTORY 3. DESIGN AND MANUFACTURING 4. SUITABLE MATERIALS FOR PRESSURE VESSELS I. COMPRESSED HYDROGEN STORAGE 5. NEW TRENDS DUE TO HYDROGEN ENERGY 6. CONCLUSION

5. The world leader in gases for industry, health and the environment 5 1. INTRODUCTION AND DIFFERENT TYPES OF PRESSURE VESSELS Type I : pressure vessel made of metal Type II :pressure vessel made of a thick metallic liner hoop wrapped with a fiber resin composite Type III :pressure vessel made of a metallic liner fully-wrapped with a fiber-resin composite Type IV :pressure vessel made of polymeric liner fully-wrapped with a fiber-resin composite

6. The world leader in gases for industry, health and the environment 6 4 pressure vessels types 1. INTRODUCTION AND DIFFERENT TYPES OF PRESSURE VESSELS

7. The world leader in gases for industry, health and the environment 7 Different types of pressure vessels Type I cylinderType II vessel Type III or IV vessel Toroid composite vessel 1. INTRODUCTION AND DIFFERENT TYPES OF PRESSURE VESSELS

8. The world leader in gases for industry, health and the environment 8 Gas transport - 1857 2. SOME HISTORY

9. The world leader in gases for industry, health and the environment 9 2. SOME HISTORY

10. The world leader in gases for industry, health and the environment 10  The experimentation of composite vessels started in the 50s  Composite vessels were introduced for space and military applications 2. SOME HISTORY

11. The world leader in gases for industry, health and the environment 11 3. DESIGN AND MANUFACTURING  Metallic vessels and composite vessels are very different : The metal is isotropic, the composite is anisotropic The failure modes are different The ageing is different

12. The world leader in gases for industry, health and the environment 12 3. DESIGN AND MANUFACTURING Main strains considered for the metallic pressure vessels design (type I and metallic liner)

13. The world leader in gases for industry, health and the environment 13 3. DESIGN AND MANUFACTURING Multi-layered element and vessel meshes example

14. The world leader in gases for industry, health and the environment 14 3. DESIGN AND MANUFACTURING  Type I : From plates From billets From tubes 3 different manufacturing processes

15. The world leader in gases for industry, health and the environment 15 3. DESIGN AND MANUFACTURING Principle of metallic tank manufacturing processes (1 : from plates / 2 : from billets / 3 : from tubes

16. The world leader in gases for industry, health and the environment 16 3. DESIGN AND MANUFACTURING From the polymer or the monomers by the rotomolding process From tubes : polymeric tubes (made by extrusion blow moding)  Polymers liners :

17. The world leader in gases for industry, health and the environment 17 3. DESIGN AND MANUFACTURING Winding machine and the 3 winding possibilities CNRS-LMARC-Besançon-France

18. The world leader in gases for industry, health and the environment 18 4. SUITABLE MATERIALS FOR HYDROGEN HIGH PRESSURE VESSELS  Risk of hydrogen embrittlement : Environment Material Design and surface conditions

19. The world leader in gases for industry, health and the environment 19 Steels acceptable for hydrogen pressure storage (ISO 11114-1) Type of steelNote Normalized and carbon steels Stainless steels Quenched and tempered steels Embrittlement to be assessed if (C + Mn/6) high Some of them can be sensitive to embrittlement (ex. : 304) More used (ex. : 34CrMo4) ; Embrittlement to be assessed if Rm > 950 Mpa. 4. SUITABLE STEELS

20. The world leader in gases for industry, health and the environment 20 Disk testing method – Rupture cell for embedded disk-specimen 1.Upper flange 2.Bolt Hole 3.High-strength steel ring 4.Disk 5.O-ring seal 6.Lower flange 7.Gas inlet 4. TEST METHODS

21. The world leader in gases for industry, health and the environment 21 Example of a disk rupture test curve 4. TEST METHODS

22. The world leader in gases for industry, health and the environment 22 1)The influence of the different parameters shall be addressed. 2)To safely use materials in presence of hydrogen, an internal specification shall cover the following : The « scope », i.e. the hydrogen pressure, the temperature and the hydrogen purity The material, i.e. the mechanical properties, chemical composition and heat treatment The stress level of the equipment The surface defects and quality of finishing And the welding procedure, if any 4. H 2 EMBRITTLEMENT - RECOMMENDATION

23. The world leader in gases for industry, health and the environment 23  Permeation rate through the polymeric liner : Permeation is specific of type IV vessels. It is the result of the H 2 gas dissolution and diffusion in the polymer matrix H 2 is a small molecule, and thus the permeation is enhanced. This leads to the development of special polymers Polyethylene and polyamide are the most used liners for type IV tanks 4. COMPOSITE CYLINDERS – SUITABLE MATERIALS One phenomena to avoid is the blistering of liner collaps

24. The world leader in gases for industry, health and the environment 24  No specific issue with aluminium alloys (except if presence of mercury or water) 4. COMPOSITE CYLINDERS – SUITABLE MATERIALS

25. The world leader in gases for industry, health and the environment 25 Range of fiber mechanical properties Fiber category Glass Amarid Carbon ~ 70 - 90 Tensile modulus (GPa) Tensile strength (MPa) Elongation (%) ~ 40 - 200 ~ 230 - 600 ~ 3300 - 4800 ~ 3500 ~ 3500 - 6500 ~ 5 ~ 1 - 9 ~ 0,7 – 2,2 4. COMPOSITE CYLINDERS – SUITABLE MATERIALS

26. The world leader in gases for industry, health and the environment 26 4. MATERIALS SUITABLE FOR HYDROGEN HIGH PRESSURE VESSELS Hydrogen requires special attention for the choice of : For type IV, permeation measurement is required (e.g. specified rate < 1 cm 3 /l/h). Material test generally requested to check “H 2 embrittlement” the polymer (type IV tanks) the steel (types I, II and III tanks)

27. The world leader in gases for industry, health and the environment 27 Cm and Cv as a function of the pressure (types III and IV) Cm : weight performance : mass of H 2 stored divided by the mass of the vessel (% wt) Cv : volume performance : mass of H 2 stored divided by the external volume of the vessel (g/l) 5.NEW TRENDS DUE TO HYDROGEN ENERGY

28. The world leader in gases for industry, health and the environment 28 6.COMPRESSED GAS STORAGE - CONCLUSION Main features for H 2 pressure vessel types in 2006 Type I Type II Type III Type IV Technology mature Cost performance Weight performance ++ Pressure limited to 300 bar (  density : –) + Pressure not limited (  density : +) For P < 350 bar; (700 bar under development ) For P < 350 bar; (700 bar under development ) ++ + – – + + – 0

29. The world leader in gases for industry, health and the environment 29 1. INTRODUCTION (COMPARISON OF EFFICIENCY/GROWS STORAGE) 2. DIFFERENT TYPES OF CRYOGENIC VESSELS 3. REDUCING THE WALL THICKNESS OF THE VESSELS II. CRYOGENIC VESSELS FOR THE STORAGE OF LIQUID HYDROGEN 4. TRANSPORT OF LIQUID HYDROGEN 5. MATERIAL ISSUES

30. The world leader in gases for industry, health and the environment 30 1. INTRODUCTION (COMPARISON OF EFFICIENCY/GROWS STORAGE)  Cryogenic vessels have been commonly used for more than 40 years for the storage and transportation of industrial and medical gases. The advantage of storing gases in such form is obvious: in a volume of 1 litre of liquid, about 800 litres of gas can be stored. This represents a clear advantage compared to the transportation of such gases in compressed form, which is done today at pressures of 200-300 bar (less gas per volume unit) and require thick walls (and heavy vessels) to resist the high pressure.

31. The world leader in gases for industry, health and the environment 31 1. INTRODUCTION (COMPARISON OF EFFICIENCY/GROWS STORAGE)  The disadvantage is, of course, that the gases need to be refrigerated down to very low temperatures to be in liquid form, especially for liquid hydrogen. The temperature gas/liquid equilibrium for different gases under a pressure of one atmosphere are given below. For gases being stored at such low temperatures, it is necessary to use high efficiency (vacuum) insulated vessels.

32. The world leader in gases for industry, health and the environment 32 1. INTRODUCTION (COMPARISON OF EFFICIENCY/GROWS STORAGE) Gases KrO2O2 ArAirN2N2 NeH2H2 He Boiling temperature - 153- 183- 186- 191- 196- 246- 253- 269 BOILING TEMPERATURES (°C) AT ATMOSPHERIC PRESSURE OF DIFFERENT GASES

33. The world leader in gases for industry, health and the environment 33  Cryogenic vessels used for gases requiring low temperature for liquefaction are normally vacuum insulated and composed of an inner pressure vessel and an external protective jacket. To reduce the thermal conductivity of the space between the inner vessel and the outer jacket, perlite (powder structure) or super insulation (wrapping with layers of aluminium film) are used. 2. DIFFERENT TYPES OF CRYOGENIC VESSELS

34. The world leader in gases for industry, health and the environment 34 2. DIFFERENT TYPES OF CRYOGENIC VESSELS SCHEMATIC SHOWING THE MAIN COMPONENTS OF A CRYOGENIC VESSEL

35. The world leader in gases for industry, health and the environment 35  For gases such as carbon dioxide or nitrous dioxide, due to the relatively high liquefaction temperature, non-vacuum insulated vessels are used. The insulation of the vessels normally consists of a thick layer of polyurethane 2. DIFFERENT TYPES OF CRYOGENIC VESSELS  Some cryogenic vessels are used for the storage of gases at the production site, others at the end-user site.

36. The world leader in gases for industry, health and the environment 36  Some cryogenic vessels are used for the transportation of gases. The most common are cryogenic trailers used to refill the stationary vessels at end-user sites. Large containers are also trans­ported by road, railroad or sea. All these types of vessels are called “large trans­portable cryogenic vessels” 2. DIFFERENT TYPES OF CRYOGENIC VESSELS

37. The world leader in gases for industry, health and the environment 37  Some other small cryogenic vessels (less than 1 000 litres water capacity) are also filled and transported by companies involved in the supply of industrial or medical gases to the end users  A large number of cryogenic vessels are being used around the world 2. DIFFERENT TYPES OF CRYOGENIC VESSELS

38. The world leader in gases for industry, health and the environment 38 2. DIFFERENT TYPES OF CRYOGENIC VESSELS CRYOGENIC TRAILER

39. The world leader in gases for industry, health and the environment 39 2. DIFFERENT TYPES OF CRYOGENIC VESSELS NUMBER OF DIFFERENT TYPES OF VESSELS BEING USE IN THE WORLD Type of vessels Units Vacuum insulatedNon vacuum insulated Static vessels2 00040 00050 00020020 000 Small transportable vessels (no more than 1000 L) 3 000100 000250 000--- Large transportable vessels 2005 000 401 000

40. The world leader in gases for industry, health and the environment 40 3. REDUCING THE WALL THICKNESS OF THE VESSELS  Modern methods “cold stretching” or “use of cold properties” are still not fully accepted in North America and Japan. These modern methods of designing and manufacturing stationary cryogenic vessels considerably reduce the wall thickness of the vessels. This method of reducing the price of cryogenic vessels by limiting the quantity of expensive materials used (such as stainless steel) is now widely used in Europe

41. The world leader in gases for industry, health and the environment 41 3. REDUCING THE WALL THICKNESS OF THE VESSELS  The principle and detail information on the cold stretching method is given in paper “An overview of RCS for hydrogen pressure vessels”  All efforts were made to produce efficient ISO standards for stationary cryogenic vessels in an expedient manner. ISO 21009-2, Cryogenic vessels – Static vacuum insulated vessels – Part 2: Operational requirements, is already available, while ISO 2 1009-1, Cryogenic vessels – Static vacuum-insulated vessels completed and waiting to be issued in the coming months

42. The world leader in gases for industry, health and the environment 42 4. TRANSPORT OF LIQUID HYDROGEN  In order to reduce the volume required to store a useful amount of hydrogen - particularly for vehicles - liquefaction may be employed. Since hydrogen does not liquefy until it reaches - 253° C (20 degrees above absolute zero), the process is both time consuming and energy intensive demanding. Up to 40 % of the energy content in the hydrogen can be lost (in comparison with 10 % energy loss with compressed hydrogen).

43. The world leader in gases for industry, health and the environment 43  The advantage of liquid hydrogen is its high energy/mass ratio, three times that of gasoline. It is the most energy dense fuel in use (excluding nuclear reactions fuels), which is why it is employed in all space programmes. However, energy/volume ratio remains low (X time less than gasoline). Liquid hydrogen it is difficult to store over a long period (product loss by vaporisation), and the insulated tank required may be large and bulky. 4. TRANSPORT OF LIQUID HYDROGEN

44. The world leader in gases for industry, health and the environment 44  At room temperature, INFLUENCE OF TEMPERATURE - PRINCIPLE 5. MATERIAL ISSUES – HYDROGEN EMBRITTLEMENT

45. The world leader in gases for industry, health and the environment 45  HE effect is normally attained at ambient temperatures and can often be neglected for temperatures above + 100°C. In the case of unstable austenitic stainless steels commonly used for cryogenic vessels, the maximum HE effect is attained at - 100°C, but can be neglected for temperatures below - 150°C 5. MATERIAL ISSUES – HYDROGEN EMBRITTLEMENT

46. The world leader in gases for industry, health and the environment 46 INFLUENCE OF TEMPERATURE FOR SOME STAINLESS STEELS 5. MATERIAL ISSUES – HYDROGEN EMBRITTLEMENT

47. The world leader in gases for industry, health and the environment 47 5. MATERIAL ISSUES – COMPATIBILITY OF METALS AND ALLOYS WITH LOW TEMPERATURE  Main materials employed: POSSIBILITY OF USING STEEL FOR THE DIFFERENT CRYOGENIC GASES

48. The world leader in gases for industry, health and the environment 48 5. MATERIAL ISSUES – COMPATIBILITY OF METALS AND ALLOYS WITH LOW TEMPERATURE  The use of metal at low temperatures entails special problems which must be resolved. Consideration must be given, in particular, to changes in mechanical characteristics, expansion and contractions phenomena and the thermal conduction of the various materials. However, the most important matter to be considered is certainly that of brittleness, which can affect certain metallic items of equipment when they are used at cryogenic temperature

49. The world leader in gases for industry, health and the environment 49 5. MATERIAL ISSUES – COMPATIBILITY OF METALS AND ALLOYS WITH LOW TEMPERATURE  In what follows, we shall only deal ferritic steels, stainless steels and aluminium alloys, which are the main materials used at low temperatures

50. The world leader in gases for industry, health and the environment 50 5. MATERIAL ISSUES – COMPATIBILITY OF METALS AND ALLOYS WITH LOW TEMPERATURE CHARPY TEST

51. The world leader in gases for industry, health and the environment 51 5. MATERIAL ISSUES – COMPATIBILITY OF METALS AND ALLOYS WITH LOW TEMPERATURE CHARPY TEST AT LIQUID HELIUM TEMPERATURE – TEMPERATURE VERSUS TIME