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HyCoRA Recent development on hydrogen impurity analysis Thomas Bacquart 2 nd OEM Workshop 9 th October 2015 1 NPL Management Ltd - Internal New developments on hydrogen impurities New capability at NPL Perspective for the NPL

  1. HyCoRA Recent development on hydrogen impurity analysis Thomas Bacquart 2 nd OEM Workshop – 9 th October 2015 1 NPL Management Ltd - Internal

  2. � New developments on hydrogen impurities � New capability at NPL � Perspective for the NPL enrichment device 2

  3. Hydrogen Analysis at NPL Quartz crystal cavity ringdown Gas chromatography with thermal microbalance spectroscopy conductivity detector Helium Water Validation ongoing Formaldehyde under validation Under development… Hydrocarbons Formaldehyde Carbon dioxide Formic acid Gas chromatography with mass Methane Gas chromatography with spectrometer detector Ammonia methaniser and flame Carbon monoxide (or cavity ringdown spectroscopy) ionisation detector Sulphur Oxygen Compounds Nitrogen Argon Gas chromatography with sulphur Gas chromatography with helium chemiluminescence detector discharge ionisation detector 3 UKAS accredited ISO 17025

  4. New development on hydrogen impurities Reactive gases Reactive gases • Water (5 µmol/mol) • Total hydrocarbons (2 µmol/mol) • Oxygen (5 µmol/mol) • Carbon dioxide (2 µmol/mol) • Formic acid (0.2 µmol/mol) • Carbon monoxide (0.2 µmol/mol) • Ammonia (0.1 µmol/mol) • Total halogenated compounds (0.05 µmol/mol) • Formaldehyde (0.01 µmol/mol) • Total sulphur compounds (0.004 µmol/mol) ISO 14687-2:2012 Inert gases Inert gases Hydrogen fuel – Product specification – Part 2: Proton exchange membrane (PEM) fuel cell applications for road • Helium (300 µmol/mol) vehicles • Nitrogen (100 µmol/mol) • Argon (100 µmol/mol) Non-gases Non-gases • Particulates (1 mg/kg) 4

  5. Water analysis Water is added to the gas cylinder using a syringe and loop Pure water Evacuated transfer loop 10 L cylinder Syringe Pure H 2 5 Gravimetric addition

  6. Water analysis Primary reference materials for water content in hydrogen A501 A504 11.18 ppm 2.125 ppm 1919 H2O in H2 H2O in H2 50.13 ppm H2O in H2 7.74 % (QCM) < 0.2 % (CRDS) 0.52 % (CRDS) 8.87 % (QCM) 1918 1953 NG591 10.24 ppm 2.042 ppm 51.37 ppm H2O in H2 H2O in H2 H2O in H2 1530 A465 A458 4.99 ppm 19.53 ppm 100.36 ppm H2O in H2 H2O in H2 Pure water H2O in H2 1.41 % (QCM) 0.56 % (QCM) 1.28 % (QCM) 0.87 % (CRDS) 3.82 % (CRDS) 1857 A459 1867 20.06 ppm 100.19 ppm 4.99 ppm H2O in H2 H2O in H2 H2O in H2 6

  7. Water analysis – Linearity – QCM Acceptable linearity from 5-100 ppm water in H 2 Repeatability of slope: ± 30 % (day to day effect on instrument sensitivity) Repeatability of analysis: < 1 % Intermediate precision: study ongoing Trueness: comparison with primary method (Dew point) 7

  8. Water analysis – Linearity – CRDS 20000 Water concentration measured by 18000 y = 898.77x - 535.73 R² = 0.9983 16000 14000 CRDS [ppb] 12000 10000 8000 6000 4000 2000 0 0 5 10 15 20 25 Water concentration [µmol/mol] Good linearity from 2-20 ppm water in H 2 Repeatability of slope: ± 5 % Repeatability of analysis: < 2 % Intermediate precision: study ongoing Trueness: comparison with primary method (Dew point) 8

  9. Water analysis – Trueness assessment Comparability of matrix N 2 and H 2 Compare our mixtures against dynamic standards and instruments against primary standard method: H 2 controlled Dew point atmosphere analysis Certify N 2 controlled (primary method) atmosphere Certification Comparability of matrix N 2 and H 2 (correction factor between the matrix) 9 Standard 5 - 20 ppm H2O in N 2 H2O in H 2

  10. Water analysis - Summary � CRDS � QCM Linear 2-20 ppm Linear: 5-100 ppm Repeatable Repeatable Low day-to-day effect Significant day-to-day effect Trueness ongoing Trueness ongoing Not accredited ISO17025 at Method accredited ISO17025 at NPL NPL Method extensively validated by end of October 2015 10

  11. Formaldehyde analysis NPL capability: GC-PDHID: under development Methaniser GC-FID: method not fully validated (theoretical LOD ~ 10 ppb) GC-MS with pre-concentration : validated by another NPL team (LOD < 10 ppb) FTIR: only qualitative, identification 11

  12. Formaldehyde analysis Produce and validate formaldehyde standards at 2 ppm and 10 ppm in hydrogen matrix - Pure formaldehyde is not stable (100% formaldehyde cannot be purchased easily) - Formaldehyde gas standards can be derived from trioxane - System is built for producing standards in nitrogen - Two gas mixtures containing 2 ppm and 10 ppm of formaldehyde in hydrogen have been prepared 12

  13. Formaldehyde analysis - 1 st observation 2 ppm Formaldehyde in hydrogen FTIR 2 ppm Formaldehyde in H 2 Methanol! Dimethoxymethane GC-MS (p re-concentration) 0 ppm 3 0 Time [months] 13

  14. Formaldehyde analysis - 1 st observation 2 ppm Formaldehyde in hydrogen 2 ppm Formaldehyde in H 2 How fast formaldehyde degrades in cylinder???? 0 ppm 3 0 Time [months] 14

  15. Formaldehyde analysis – Stability study New standards: Agreement 10 ppm formaldehyde in H 2 ± 15 % 10 ppm formaldehyde in H 2 Degradation monitoring: FTIR, GC-MS, methaniser GC-FID Formaldehyde T=0 days Formaldehyde Dimethoxy methane Methanol Slow degradation 15 T=40 days (loss of 10 – 20 % within 2 months)

  16. Formaldehyde analysis - Summary � Analysis of formaldehyde in hydrogen - Several methods under development/validation - Gas standard for Formaldehyde in H 2 � Stability of formaldehyde in hydrogen - 2 ppm formaldehyde in H 2 � 0 % after 3 months - 10 ppm formaldehyde in H 2 � stable after 1 month - Study ongoing until complete degradation 16

  17. Halogenated compounds in hydrogen � Analysis of 3 freons gases (CHClF 2 , CCl 2 F 2 , C 2 H 2 F 4 ) in N 2 using ThermoDesorption GC-MS (TD-GC-MS) hydrogen Chromosorb sorbent tube 15 min at 30 ml/min 50 ppb CHClF 2 TD-GC-MS 50 ppb CCl 2 F 2 50 ppb C 2 H 2 F 4 Matrix: N 2 Gravimetrically prepared 17

  18. Halogenated compounds in hydrogen � Analysis of 3 freons gases (CHClF 2 , CCl 2 F 2 , C 2 H 2 F 4 ) in N 2 using ThermoDesorption GC-MS (TD-GC-MS) CHClF 2 C 2 H 2 F 4 Thermal desorption CCl 2 F 2 TD-GC-MS 18 Chromatogram

  19. Halogenated compounds in hydrogen � Capability to analyse halogenated compounds at low concentration in gas � Preparation of standard of halogenated compounds in hydrogen � to be evaluated - Purchasing pure compounds - Oxy-flame mixture - Stability � Improvement of procedure � Funding required! 19

  20. � New developments on hydrogen impurities � New capability at NPL � Perspective NPL enrichment device 20

  21. Characterisation of palladium-based membranes for hydrogen purification SAES H 2 S and CO membranes adsorption Feedback of results New membranes Testing Helium permeation chamber tests NPL gas testing Evacuation Evacuation testing rig SAES testing NPL Pressure rig Pressure testing characterisation AIM OF PROJECT New and improved methods for characterising palladium- Microscopy FIB-SEM XPS based membranes Adsorbed Adsorbed layer Micro crack 3D layer Stress/ Impurities on Amount of 2D profiling Roughness thickness identification profiling damage surface adsorption (e.g. 21 monolayer) monolayer)

  22. Characterisation of palladium-based membranes for hydrogen purification Project outcomes New membrane Improved characterisation New projects membranes techniques Improved New testing facilities Development of membranes for available to end hydrogen impurity users hydrogen purifiers enrichment device 22

  23. � New developments on hydrogen impurities � New capability at NPL � Perspective NPL enrichment device 23

  24. Perspective NPL enrichment device � Private partner needed for the commercialisation of the device 24

  25. Conclusion � New development on hydrogen impurities - Water analysis almost extensively validated and traceable to SI - Formaldehyde in Hydrogen: 1 month stability ensured - Halogenated analysis: - Organo-halogenated compounds analysed by TD-GC-MS - Investment needed to continue further � New capability at NPL New service: Characterisation of palladium-based membranes for hydrogen purification � Perspective NPL enrichment device - Private laboratory partner needed to commercialise the device 25

  26. Progress in other projects… � Report of analysis for impurities in hydrogen under UKAS ISO17025 accreditation in process � New development ongoing for ammonia, formaldehyde (GC-MS), formic acid and formaldehyde (GC-PDHID) new binary standards in hydrogen in preparation � Participation in project proposal EMPIR co- normative call – Project proposal called Hydrogen 26

  27. Acknowledgement Hydrogen Quality control Innovate UK Gas and Particulate Metrology group Humidity group 27

  28. Thanks, Questions? 28 NPL Management Ltd - Internal

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