Analytical methods for hydrogen fuel QC Thomas Bacquart, Sam Bartlett, Abigail S.O. Morris, Nick Allen, Arul Murugan

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1 Analytical methods for hydrogen fuel QC Thomas Bacquart, Sam Bartlett, Abigail S.O. Morris, Nick Allen, Arul Murugan 06-07/06/2017, HYCORA workshop (Trondheim)Laboratory

2 NPL s Gas Metrology Group Analytical techniques Standardisation Projects Future work

3 Analytical techniques

4 Hydrogen Component Amount fraction range (μmol/mol) Component Amount fraction range (μmol/mol) Water 5 Carbon monoxide 0.2 Total hydrocarbons 2 Total sulphur compounds Oxygen 5 Formaldehyde 0.01 Helium 300 Formic acid 0.2 Nitrogen 100 Ammonia 0.1 Argon 100 Total halogenated compounds Carbon dioxide ISO

5 Dew point analyser Electrostatic capacity moisture meter Vibrating quartz analyser FTIR Galvanic cell analyser GC-FID with methaniser GC-FID GC-TCD GC-MS GC-PDHID GC-SCD GC-FPD GC-ECD GC-ELCD Combustion ion chromatography Adsorptiuon Ion chromatography Gravimetry CRDS OFCEAS GC-AED Techniques overview Water Total hydrocarbons Oxygen Helium Nitrogen Argon Carbon dioxide Carbon monoxide Total sulphur Formaldehyde Formic acid Ammonia Total halogenated Particle concentration New methods: quantum laser, SIFT-MS, IMS??? : pre-concentration used; not all sulphur compounds

6 Which analytical methods? Techniques Methods performance vs ISO and customer requirements Stability of the analytes Which standards? Method validation?

7 Hydrogen NPL s capabilities cavity ringdown spectroscopy Water Quartz crystal microbalance Gas chromatography with thermal conductivity detector Helium Ammonia UV-visible spectroscopy Thermo-desorption - Gas chromatography with mass spectrometer detector Organo-halogenated compounds (excluding HCl and Cl2) Formic acid Oxygen Nitrogen Argon Sulphur Compounds Formaldehyde Carbon dioxide Hydrocarbons Carbon monoxide Methane Gas chromatography with methaniser and flame ionisation detector Fourier Transform Infra-Red spectroscopy Gas chromatography with helium discharge ionisation detector Methane Carbon monoxide Carbon dioxide Gas chromatography with sulphur chemiluminescence detector

8 NPL analytical capabilities Impurity ISO (µmol/mol) Analytical Method Detection Limit (µmol/mol) Required amount of gas [L] Water 5 Quartz crystal microbalance CRDS L L Total Hydrocarbons 2 GC-Methaniser-FID L Oxygen 5 GC-PDHID L Helium 300 GC-TCD 10 2 L Argon Nitrogen 100 GC-PDHID Carbon Dioxide 2 GC-Methaniser-FID L Carbon Monoxide 0.2 GC-Methaniser-FID L Total sulphur compounds GC-SCD (s/n) (s Ls ) Formaldehyde 0.01 GC-Methaniser-FID L Formic Acid 0.2 FTIR L Ammonia 0.1 Total halogenated compounds (only organic halogenated compounds, excluding HCl and Cl2) GC-MS UV-visible spectroscopy L 1 L 2 L 15 L 0.05 TD-GC-MS L

9 NPL analytical capabilities Impurity ISO (µmol/mol) Analytical Method Detection Limit (µmol/mol) Required amount of gas [L] Water 5 Quartz crystal microbalance CRDS L L Total Hydrocarbons 2 GC-Methaniser-FID L Oxygen 5 GC-PDHID L Helium 300 GC-TCD 10 2 L Argon Nitrogen 100 GC-PDHID Carbon Dioxide 2 GC-Methaniser-FID L Carbon Monoxide 0.2 GC-Methaniser-FID L Total sulphur compounds GC-SCD (s/n) (s Ls ) Formaldehyde 0.01 GC-Methaniser-FID L Formic Acid 0.2 FTIR L Ammonia 0.1 Total halogenated compounds (only organic halogenated compounds, excluding HCl and Cl2) GC-MS UV-visible spectroscopy L 1 L 2 L 15 L 0.05 TD-GC-MS L Need clarification from laboratories and standardisation body

Formaldehyde T=0 days Formaldehyde Dimethoxy methane What

10 Stability of chemical compounds in H 2 Onsite versus offsite Example: CH 2 O stability over time at 10 µmol/mol Formaldehyde T=0 days Formaldehyde Dimethoxy methane What happens for 10 nmol/mol in sampling container T=40 days Methanol

11 Stability of chemical compounds in hydrogen Onsite versus offsite Study/comparison required for: Sulphur compounds Water Formaldehyde Ammonia Halogenated Oxygen? Development of trapping techniques: Thermo-desorption Impingers/bubbling Filters Development and validation of online analyser

12 Calibration Gas standards Impurity ISO (µmol/mol) Gas standards (µmol/mol) Water Total Hydrocarbons List of compounds available upon request) Oxygen Helium Argon Nitrogen Carbon Dioxide Carbon Monoxide Formic Acid Total sulphur compounds (List of compounds available upon request) Formaldehyde (unstable) Ammonia Total halogenated compounds (only organic halogenated compounds, excluding HCl and Cl2) Dilution system Validation at low level Uncertainty

13 Calibration - Gas standard mixture Hydrogen PRGM mixture permanent gas: Amount fraction [µmol/mol] Matrix N 2 O 2 CO CO 2 CH 4 C 2 H 6 Mix Mix Mix Mix Mix Sulphur compounds: Compounds: H 2 S, carbonyl sulphide (OCS), carbon disulphide (CS2), 2-methyl-2-propanethiol (TBM), tetrahydrothiophene (THT) Range: µmol/mol Halogenated compounds: Compounds: dichloromethane, chloroform and chlorobenzene Range: µmol/mol Under development: HCl and C 4 Cl 4 F 6

14 Trueness / inter-comparison / Benchmarking Analyte Sample ID Lab 1 Average and expanded uncertainty [µmol/mol] Lab 2 Average and expanded uncertainty [µmol/mol] O 2 Hycora S ± 0.10 N 2 Hycora S8 97 ± 6 75 Ar Hycora S ± 0.10 Analyte Sample ID Lab 1 Average and expanded uncertainty [µmol/mol] Decision making Lab 2 Average and expanded uncertainty [µmol/mol] CH 2 Cl 2 Hycora S ± C 4 Cl 4 F 6 Hycora S < O 2 Hycora S ± 0.7 N 2 Hycora S ± Ar Hycora S ± 0.20 Need for quality assurance / Method validation

15 Standardisation

16 Analytical methods and quality control requirements Choice of the calibrants (concentration, matrix, traceability) Method validation / performance Selectivity, limit of detection (LOD) and limit of quantification (LOQ), working range, trueness, precision, measurement uncertainty, ruggedness Method fit for purpose LOQ + u LOQ < threshold value < highest value of working range / 2 trueness, precision, uncertainty: uncertainty < 20% at threshold value Working document - ISO WD20187

17 Analytical methods and quality control requirements Choice of the calibrants (concentration, matrix, traceability) Analytical methods / international Method validation / performance standards Selectivity, limit of detection (LOD) and limit of quantification (LOQ), working range, trueness, precision, measurement uncertainty, ruggedness Really suitable for hydrogen purity Method fit for analysis purposeaccording to ISO 14687? LOQ + u LOQ < threshold value < highest value of working range / 2 trueness, precision, uncertainty: uncertainty < 20% at threshold value Working document - ISO WD20187

18 Inter-comparison - Euramet st inter-comparison for Hydrogen purity Validation of laboratory measurement: Test method Calibrant Staff CO and H 2 S chosen for study Industrial laboratories and NMI s

19 Projects

20 EMPIR Metrology for Hydrogen Vehicles ( ) Supported by 45 stakeholders including: Flow metering Quality assurance 20 project partners: Quality control Sampling Creating impact

EMPIR Hydrogen (2016-2019) NPL s hydrogen purity

degradation testing rig What levels of impurities

21 EMPIR Hydrogen ( ) NPL s hydrogen purity laboratory NPL s high accuracy fuel cell degradation testing rig What levels of impurities are in hydrogen from SMR, electrolysis and chlor-alkali? RISK What levels of impurities in hydrogen damage the fuel cell? NH3 and halogenated compounds IMPACT Prioritisation matrix to help quality control standards and hydrogen purity requirements (i.e. ISO 14687)

EMPIR Hydrogen (2016-2019) Total = analytical challenges Real understanding of process impurities Total compounds?

22 EMPIR Hydrogen ( ) Total = analytical challenges Real understanding of process impurities Total compounds? New methods under development Sulphur compounds speciation Cryofocussing GC-SCD Hydrocarbons speciation GC/FID (C1-C5) and TD/GC/FID-MS for C5 Evidences for the revision of ISO HCl traceable results at nmol/mol level by CRDS

23 Future work

24 NPL future work NPL s hydrogen impurity enrichment device Method development Gas analysis / Method development Novel instrumentation H2 gas sampling device Impurities in hydrogen Fuel cell degradation

$Hydrogen Component Amount fraction range (μmol/mol) Component Amount fraction range (μmol/mol) Water 5 Carbon monoxide 0.$ 2 Nitrogen 100 Ammonia 0.1 Argon 100 Total halogenated compounds Carbon dioxide 2 - - 0.

2 Nitrogen 100 Ammonia 0.1 Argon 100 Total halogenated compounds Carbon dioxide 2 - - 0.

25 Hydrogen Component Amount fraction range (μmol/mol) Component Amount fraction range (μmol/mol) Water 5 Carbon monoxide 0.2 Total hydrocarbons 2 Total sulphur compounds Oxygen 5 Formaldehyde 0.01 Helium 300 Formic acid 0.2 Nitrogen 100 Ammonia 0.1 Argon 100 Total halogenated compounds Carbon dioxide ISO Services offered: - Hydrogen purity analysis against ISO (UKAS testing) - Hydrogen mixtures containing low level impurities - Validation of online purity analysers

Dr Thomas Bacquart thomas.bacquart@npl.co.

26 Dr Thomas Bacquart The National Physical Laboratory is operated by NPL Management Ltd, a whollyowned company of the Department for Business, Energy and Industrial Strategy BEIS).

Monomer Analysis. Analysis by Gas Chromatography WASSON - ECE INSTRUMENTATION. Engineered Solutions, Guaranteed Results.

Monomer Analysis. Analysis by Gas Chromatography WASSON - ECE INSTRUMENTATION. Engineered Solutions, Guaranteed Results. Monomer Analysis Analysis by Gas Chromatography Engineered Solutions, Guaranteed Results. WASSON - ECE INSTRUMENTATION Polymer Grade Monomer Analysis Monomer Analysis Impurities in feedstocks can adversely