Production and stability of low amount fraction of formaldehyde in hydrogen gas standards

Bacquart, Thomas; Perkins, Mark J.; Ferracci, Valerio; Martin, Nicholas A.; Resner, Kate; Ward, M. K.; Cassidy, Nathan; Hook, Joshua B.; Brewer, Paul J.; Irvine, John T. S.; Connor, Paul A.; Murugan, Arul

doi:10.1016/j.ijhydene.2018.02.026

Cited by 17 publications

(6 citation statements)

References 32 publications

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“…The stability of the HCOOH in hydrogen was studied with FTIR by NPL and with PD-HID and electrophoresis by VTT before and after fuel cell measurements. The stability of HCHO in H 2 at NPL has been reported by Bacquart et al 38 The online gas sampling was conducted with a gas chromatograph for CO, CO 2 and CH 4 during all measurements. The gas chromatograph was equipped with a packed Carboxen-1000 column (45/60 mesh, 2 m × 1/8") and a FID with a methanizer built in-house.…”

Section: Methodsmentioning

confidence: 95%

Study of Formaldehyde and Formic Acid Contamination Effect on PEMFC

Viitakangas

Ihonen

Koski

et al. 2018

J. Electrochem. Soc.

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The contamination effect of formaldehyde (HCHO) and formic acid (HCOOH) was studied using state-of-the-art automotive PEMFC stacks and with high fuel utilization and automotive-type operation with hydrogen recirculation. The results, measured at current density of 0.6 A/cm 2 , show that the contamination effect of formaldehyde was observable when the concentration was 2 ppm, 200 times higher than the current limit in the ISO 14687-2:2012 standard. The effect of formaldehyde was less than 10% compared to 2 ppm of CO in the same operating conditions. Moreover, the contamination effect of formic acid was barely measurable at 2 ppm, corresponding to a concentration 100 times the limit of the ISO standard. Thus, the limits of HCHO and HCOOH in the current ISO standard seem to be too strict.

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Section: Methodsmentioning

confidence: 95%

Study of Formaldehyde and Formic Acid Contamination Effect on PEMFC

Viitakangas

Ihonen

Koski

et al. 2018

J. Electrochem. Soc.

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“…A previous study [28] has showed how formaldehyde is unstable in a hydrogen matrix, so reaction (1) could potentially represent the first step of the degradation of formic acid into secondary products once formaldehyde is formed, as indicated by Equation (4):…”

Section: Thermodynamic Calculationsmentioning

confidence: 99%

Formic Acid in Hydrogen: Is It Stable in a Gas Container?

et al. 2023

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Formic acid is an intermediate of the steam methane reforming process for hydrogen production. According to International Standard ISO 14687, the amount fraction level of formic acid present in the hydrogen supplied to fuel cell electric vehicles must not exceed 200 nmol.mol−1. The development of formic acid standards in hydrogen is crucial to validate the analytical results and ensure measurement reliability for the fuel cell electric vehicles industry. NPL demonstrated that these standards can be gravimetrically prepared and validated at 4 to 100 µmol.mol−1, with a shelf-life of 1 year (stability uncertainty < 7%; k = 2). Stability was not affected over 1 year or by low temperature or pressure. At sub-µmol.mol−1 level, formic acid amount fraction was found to decrease due to adsorption on the gas cylinder surface; however, it is possible to certify the formic acid amount fraction after a period of 20 days and ensure the certified value validity for 1 year with an uncertainty below 7% (k = 1) confirmed by thermodynamic investigation. This study demonstrated that formic acid in hydrogen gas reference materials can be prepared with reasonable uncertainty (>7%, k = 1) and shelf life (>1 year). Potential applications include the calibration of analysers and for studying the impact of formic acid on future application with relevant traceability and accuracy.

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“…Requirements for grade D hydrogen in ISO 14687 [21] include specifications for maximum levels of carbon dioxide, nitrogen, argon, sulfurcontaining species (see section 8.2), halides (see sections 8.8 and 8.10), carbon monoxide (see section 8.4), formic acid (see section 8.12) and formaldehyde (see section 8.11). An assessment of the likelihood of finding these impurities has been made in hydrogen from various sources [57]. Also a review of available methods for hydrogen purity assessments has been made [58].…”

Section: Hydrogenmentioning

confidence: 99%

“…The sensitivity of the CRDS method fulfils therefore criteria set in [21] and [133]. Static formaldehyde in hydrogen gas standards are highly unstable due to degradation of formaldehyde into methanol and dimethoxymethane [57]. Dynamic preparation of formaldehyde standards is therefore the method of choice to prepare calibration gas mixtures of formaldehyde in hydrogen.…”

Section: Formaldehydementioning

confidence: 99%

Advances in metrology for energy-containing gases and emerging demands

Veen¹,

Nieuwenkamp²,

Zalewska³

et al. 2020

Metrologia

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Metrological services from National Metrology Institutes related to energy gases have been supported by the programme of key comparisons of the Gas Analysis Working Group of the Consultative Committee for Amount of Substance: Metrology in Chemistry and Biology since its conception in 1993. Most of the key comparisons have been performed on natural gas composition measurement, which is key to the calculation of natural gas properties, thereby facilitating fiscal metering and the trade in natural gas. In the recent years, non-conventional energy gases and natural gas substitutes, such as refinery gas and biogas have been addressed. The paper gives an overview over the achievements in this area from the first key comparison (CCQM-K1) onward and outlines the current challenges to the metrological community. The ongoing energy transition towards renewable energy gases is at the centre of these challenges. The associated emerging challenges primarily concern the measurement of the concentrations of impurities, such as silicon in biomethane and upgraded biogas, carbon monoxide in hydrogen, and many others. The paper presents the first results of the development of measurement standards and methods for impurities in biogas, biomethane and hydrogen and the implications for the programme of key comparisons.

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Production and stability of low amount fraction of formaldehyde in hydrogen gas standards

Cited by 17 publications

References 32 publications

Study of Formaldehyde and Formic Acid Contamination Effect on PEMFC

Study of Formaldehyde and Formic Acid Contamination Effect on PEMFC

Formic Acid in Hydrogen: Is It Stable in a Gas Container?

Advances in metrology for energy-containing gases and emerging demands

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