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

Formaldehyde is an intermediate of the steam methane reforming process for hydrogen production. According to International Standard ISO 14687-2 the amount fraction level of formaldehyde present in hydrogen supplied to fuel cell electric vehicles (FCEV) must not exceed 10 nmol mol^?1. The development of formaldehyde standards in hydrogen is crucial to validate the analytical results and ensure measurement reliability for the FCEV industry. NPL demonstrated that these standards can be gravimetrically prepared and validated at 10 μmol mol^?1 with a shelf-life of 8 weeks (stability uncertainty <10%; k = 1), but that formaldehyde degrades into methanol and dimethoxymethane, as measured by FTIR, GC-MS and SIFT-MS. The degradation kinetics is more rapid than predicted by thermodynamics, this may be due to the internal gas cylinder surface acting as a catalyst. The identification of by-products (methanol and dimethoxymethane) requires further investigation to establish any potential undesirable impacts to the FCEV.     

Hydrogen quality sampling at the hydrogen refuelling station – lessons learnt on sampling at the production and at the nozzle

Fuel cell electric vehicles and hydrogen refuelling infrastructure are developing quickly in Europe, the USA and Asia. Hydrogen quality for transport applications requires compliance with ISO 14687-2: 2012 and EN 17124:2018 - this needs representative sampling, at the hydrogen production process and at hydrogen dispenser nozzle (which typically fill vehicles to a Nominal Working Pressure of either 35 or 70 MPa). The low thresholds in ISO 14687-2 for oxygen and water can be exceeded if the sampling procedure fails to purge the system sufficiently, which would lead to false results (60% in this study). Purging requirements to remove water were studied using a low pressure sampling rig. For hydrogen dispenser sampling using the Linde H2 Qualitizer (suitable for dispensing pressures up to 70 MPa), purging number and the effect of the initial fill level of a vehicle compressed hydrogen storage system were investigated experimentally to avoid hydrogen quality violation due to oxygen false positive. The study procedure reduces from 60% to 0% hydrogen quality violation. The next challenges highlighted are safe purging and reliable sampling of reactive contaminants in gas cylinders.     

Probability of occurrence of ISO 14687-2 contaminants in hydrogen: Principles and examples from steam methane reforming and electrolysis (water and chlor-alkali) production processes model

According to European Directive 2014/94/EU, hydrogen providers have the responsibility to prove that their hydrogen is of suitable quality for fuel cell vehicles. Contaminants may originate from hydrogen production, transportation, refuelling station or maintenance operation. This study investigated the probability of presence of the 13 gaseous contaminants (ISO 14687-2) in hydrogen on 3 production processes: steam methane reforming (SMR) process with pressure swing adsorption (PSA), chlor-alkali membrane electrolysis process and water proton exchange membrane electrolysis process with temperature swing adsorption. The rationale behind the probability of contaminant presence according to process knowledge and existing barriers is highlighted. No contaminant was identified as possible or frequent for the three production processes except oxygen (frequent for chlor-alkali membrane process), carbon monoxide (frequent) and nitrogen (possible) for SMR with PSA. Based on it, a hydrogen quality assurance plan following ISO 19880-8 can be devised to support hydrogen providers in monitoring the relevant contaminants.     

Purity of hydrogen released from the Liquid Organic Hydrogen Carrier compound perhydro dibenzyltoluene by catalytic dehydrogenation

While Liquid Organic Hydrogen Carrier (LOHC) systems offer a very promising way of infrastructure-compatible storage and transport of hydrogen, the hydrogen quality released from charged LOHC compounds by catalytic dehydrogenation has been a surprisingly rarely discussed topic to date. This contribution deals, therefore, with a detailed analysis of the hydrogen purity released from the hydrogen-rich Liquid Organic Hydrogen Carrier compound perhydro dibenzyltoluene (H18-DBT). We demonstrate, that high purity hydrogen (>99.999%) with carbon monoxide levels below 0.2 ppmv can be obtained from the dehydrogenation of H18-DBT if the applied H18-DBT had been carefully pre-dried and pre-purified prior to the dehydrogenation experiment. Indeed, the largest part of relevant impurities to comply with the hydrogen quality standard for fuel cells in road vehicles (ISO 14687-2) was found to originate from water and oxygenate impurities present in the applied, technical LOHC qualities.     

Challenges in hydrogen fuel sampling due to contaminant behaviour in different gas cylinders

Increasing deployment of fuel cell electric vehicles (FCEVs) has led to implementation of hydrogen quality regulations (ISO 14687:2019) to prevent FCEV loss of performance. Hydrogen refuelling stations operators must be able to send representative samples of hydrogen fuel for analysis. Stability of contaminants in sampling vessels needs to be known at ISO 14687:2019 thresholds. A 4-month stability study was carried out on mixtures of ISO 14687 contaminants at amount fractions close to the thresholds in two types of sampling cylinders (SPECTRA-SEAL® and SGS? aluminium cylinders). SPECTRA-SEAL® cylinder allowed representative sampling of CO, CO₂, CH₄, C₂H₆, N₂, Ar, He, Cl₂CH₂, H₂O, O₂, CH₂O₂ in hydrogen fuel for 2 months. SGS? cylinder allowed representative sampling of CO, CO₂, CH4, C₂H₆, N₂, Ar, He, Cl₂CH₂, H₂O, O₂, H₂S for 4 months. Further work is needed to allow representative sampling of ammonia and formaldehyde.     

Preparation of gas standards for quality assurance of hydrogen fuel

This study has developed traceable standards for evaluating impurities in hydrogen fuel according to ISO 14687. Impurities in raw H₂, including sub μmol/mol levels of CO, CO₂, and CH₄, were analyzed using multiple detectors while avoiding contamination. The gravimetric standards prepared included mixtures of the following nominal concentrations: 1, 2, 3–5, 8–11, 17–23, and 47–65 μmol/mol for CO₂, CH₄ and CO, O₂, N₂, Ar, and He, respectively. The expanded uncertainty ranges were 0.8% for Ar, N₂, and He, 1% for CH₄ and CO, and 2% for CO₂ and O₂. These standards were stable, while that for CO varied by only 0.5% during a time span of three years. The prepared standards are useful for evaluating the compliance of H₂ fuel in service stations with ISO 14687 quality requirements.     

An experimental overview of the effects of hydrogen impurities on polymer electrolyte membrane fuel cell performance

Hydrogen quality is critical for increasing the reliability, stability, and durability of polymer electrolyte (PEM) fuel cells. In this work, several hydrogen impurities have been studied to understand their effects on PEM fuel cell performance at various operating concentrations. Our studies have shown that the following impurities suggested by industry stakeholders do not result in substantial fuel cell degradation when they are the sole impurity in hydrogen: 5 ppm formaldehyde, 2 ppm formic acid, 19 ppm chloromethane, 30 ppm acetaldehyde, 5% ethylene, 20 ppm toluene, and 10 ppm benzene. In addition, a specific mixture of impurities called the “specification concentration level cocktail” consisting of 0.2 ppm carbon monoxide, 4 ppb hydrogen sulphide, 0.2 ppm formic acid, 2 ppm benzene, and 0.1 ppm ammonia in hydrogen, also does not show significant effects on cell performance. In comparison, when a cocktail having five times the specification concentration is introduced into the cell, significant performance loss is evident.     

Photocatalytic hydrogen generation over alkaline-earth titanates in the presence of electron donors

The efficiency of alkaline-earth titanate-based compounds (Ca, Sr, Ba) for catalysts in photocatalytic hydrogen generation has been investigated. In this report, we have shown that the addition of organic donors (such as formic acid, acetic acid, methanol, 2-propanol and formaldehyde) enhanced the efficiency of the studied process. The systematic study has shown that the most efficient organic donor in regards to its hydrogen generation efficiency is formic acid. Of the catalysts explored, the highest photocatalytic activity was shown by SrTiO₃:TiO₂. Additionally, the effects of photocatalyst quantity and formic acid concentration on hydrogen evolution have been investigated.     

Development of a cross-contamination-free hydrogen sampling methodology and analysis of contaminants for hydrogen refueling stations

Hydrogen used in proton exchange membrane-based fuel cell applications is subject to very high quality requirements. While the influences of contaminations in hydrogen on long-term stability have been intensively studied, the purity of hydrogen for mobile applications provided at hydrogen refueling stations (HRS) is rarely analyzed. Hence, in this study, we present sampling of hydrogen at HRS with a specially designed mobile tank for up to 70 MPa. These samples are precisely analyzed with a sophisticated ion molecule reaction mass spectrometer (IMR-MS), able to determine concentrations of contaminants down to the ppb-level. Sampling and analysis of hydrogen at an HRS supplied by electrolysis revealed a high purity, but likewise considerable contaminations above the threshold of the international standard ISO 14687:2019. In this study, a state-of-the-art analysis coupled with a developed methodology for fuel cell electric vehicle-independent sampling of hydrogen with a mobile tank system is demonstrated and applied for comprehensive studies of hydrogen purity.     

Investigation of the interaction between intermediates from gasification of biomass in supercritical water: Formaldehyde/formic acid mixtures

Supercritical water gasification (SCWG) is a promising technology for converting wet biomass and waste into renewable energy. While the fundamental mechanism involved in SCWG of biomass is not completely understood, especially hydrogen (H₂) production produced from the interaction among key intermediates. In the present study, formaldehyde mixed with formic acid as model intermediates were tested in a batch reactor at 400 °C and 25 MPa for 30 min. The gas and liquid phases were collected and analyzed to determine a possible mechanism for H₂ production. Results clearly showed that both gasification efficiency (GE) and hydrogen efficiency (HE) increased with addition of formic acid, and the maximum H₂ yield reached 17.92 mol/kg with a relative formic acid content of 66.67% in the mixtures. The total organic carbon removal rate and formaldehyde conversion rate also increased to 67.33% and 89.81% respectively. The reaction pathways for H₂ formation form mixtures was proposed and evaluated, formic acid promoted self-decomposition of formaldehyde to generate H₂, and induced a radical reaction of generated methanol to produce more H₂.     

Nano-Cu catalyze hydrogen production from formaldehyde solution at room temperature

In this paper, high efficient production of CO-free hydrogen from formaldehyde (HCHO) aqueous solution catalyzed by various nano-metal catalysts was reported. It was found that nano-metal catalyst could catalyze formaldehyde into hydrogen and formic acid under room temperature and atmospheric pressure. Among Pt, Au, Ni, and Cu nano-metal particles, nano-Cu catalyst exhibited the highest activity and the long-term stability. The temperature seems influence the reaction significantly. For example, when the temperature was increased from 0 to 60 °C, the rate of hydrogen production increases from 2.34 to 140 mL min⁻¹ g⁻¹ catalyst over nano-Cu catalyst. Hydrogen was produced via the formic acid intermediate. When NaOH concentration was high, Cannizzaro reaction occurred, which resulted in the retardation of hydrogen generation at high concentration of NaOH and HCHO.     

Energy efficient hydrogen drying and purification for fuel cell vehicles

High-purity standards are required for hydrogen used in fuel cell vehicles. The relative abundance of contaminants is highly influenced by the production pathway. Hydrogen obtained from water electrolysis presents three main pollutants: Nitrogen, Oxygen and Water. Herein, the engineering and implementation of removal techniques in a commercial 50 kW alkaline electrolyzer are reported. The full system was characterized with various analytical techniques including gas chromatography and mass spectrometry. A reduction of contaminant levels compatible with ISO 14687:2019 standard was achieved. From cold start, 100 min of operation are required to reach the desired nitrogen levels. Oxygen was removed in one step with a catalytic converter. Drying of hydrogen was achieved by using an innovative vacuum assisted pressure swing adsorption system. Sub-ppm levels of water are obtained with a power consumption of only 0.5 kWh/kg H₂ and 98.4% of product recovery.     

Highly purified hydrogen production from ammonia for PEM fuel cell

Liquid ammonia is an attractive hydrogen carrier because of high storage capacity. According to ISO14687-2, an acceptable ammonia concentration in hydrogen for polymer electrolyte membrane (PEM) fuel cell vehicles is 0.1 ppm. When ammonia is used as the hydrogen carrier, about 1000 ppm of ammonia included in gas generated by ammonia decomposition at 773–823 K and 0.1 MPa has to be reduced to less than 0.1 ppm. Although several types of ammonia absorption materials are investigated as ammonia remover, the target value cannot be achieved by static adsorption methods. However, we have succeeded in that the ammonia concentration is reduced down to 0.01–0.02 ppm by using Li-exchange X-type zeolite (Li-X) as the absorbent and dynamic adsorption methods. Furthermore, Li-X is simply recycled by heating at 673 K. Therefore, Li-X is a durable and recyclable ammonia removal material for the highly purified hydrogen production from ammonia for PEM fuel cells.     

Co/multi-walled carbon nanotubes as highly efficient catalytic nanoreactor for hydrogen production from formic acid

Formic acid is well-recognized as safe and convenient hydrogen carrier. Development of active and cost-effective catalysts for formic acid to hydrogen conversion is important problem of hydrogen energy field. Herein, we report on new Co catalysts supported on oxidized multi-walled carbon nanotubes (MWCNTs), which demonstrate high efficiency in the gas-phase formic acid decomposition affording molecular hydrogen. Various parameters of the catalysts, Co loading, MWCNTs structure, and nanotubes treatment conditions, have been investigated in terms of their influence on the catalytic properties. The catalysts morphology has been characterized with a set of physicochemical methods. It is found that the catalytic activity of Co particles depends on their electronic state and location on the support. Co species located inside the MWCNTs channels are less active than Co species stabilized on the outer surface. An increase in the content of Co nanoparticles on the MWCNT outer surface leads to a higher catalytic activity.     

Development of a hydrogen impurity analyzer based on mobile-gas chromatography for online hydrogen fuel monitoring

Hydrogen is an excellent alternative energy source, particularly for vehicles. Despite the expansion of a considerable number of infrastructures, such as hydrogen refueling stations, there is a lack of efficient inspection methods for monitoring the hydrogen fuel quality. In this study, a hydrogen impurity analyzer (HIA) based on mobile gas chromatography with a thermal conductivity detector is developed and evaluated for the quality assurance of hydrogen fuel. Accordingly, O₂, N₂, and Ar which help in monitoring air leaks at hydrogen refueling stations, and CH₄, which can also be detected by HIA, are selected as target impurities. The HIA reached limits of detection of 2.93, 0.72, 0.84, and 1.54 μmol/mol for O₂, Ar, N₂, and CH₄, respectively. Moreover, the ISO 14687 requirements are satisfied with respective HIA expanded uncertainties of 2.6, 8.7, 8.2, and 9.4% (coverage factor k = 2). The developed system is ISO-compliant and offers enhanced mobility for online inspections.     

Hydrogen production from formic acid in fluidized bed made out of Ni-cenosphere catalyst

This research presents a method of hydrogen production from formic acid with the use of fluidized bed technology. The core-shell catalyst was developed by applying the Ni layer on cenospheres via a technique of gaseous deposition. The efficiency of the decomposition of formic acid was tested continuously in the range of 200–500 °C. An analytical method, based on infrared spectroscopy, allowing the continuous monitoring of the concentration of products in the gas phase has been developed. A 67% yield of hydrogen was achieved at 233 °C. The proposed solution in a fluidized bed has been compared with other methods of obtaining hydrogen from formic acid. The most important advantages of the proposed solutions are on-demand hydrogen generation; the use of an energy carrier that can be obtained from biomass or CO₂; simplicity of the process including easy control of the process temperature; repeatability; ease of scaling the fluidized process; the possibility of continuous monitoring of the products of the process; high efficiency of hydrogen generation per unit volume of the reactor.     

Accurate quantification of ultra-trace sulfur compounds in hydrogen by integrating fill-less trap pre-concentration with gas chromatograph and sulfur chemiluminescence detector

Accurate quantification of ultra-trace impurities in hydrogen, e.g., <0.004 μmol·mol^?1 for total sulfur compounds as specified in ISO 14687-2019, is of paramount importance to ensure the quality of hydrogen for fuel cell vehicles. Here, we developed a novel fill-less trap pre-concentration inlet system integrated with GC-SCD for measuring ultra-trace sulfides in hydrogen. This analytical system can achieve an optimum method detection limit range of 0.002–0.004 nmol mol^?1 (ppb(v)) for sulfides by trapping 400 mL hydrogen sample. The modified fill-less trap inlet system can avoid the deviation of desorption efficiency from adsorbents and shows a wide linearity range of up to 150 ppb(v) in 400 mL that is one order of magnitude higher than existing packing pre-concentration. Response sensitivity biases from the calibration pattern of constant volumes exhibit better sensitivity with deviation of up to ～10% smaller than constant concentrations at 0.1–10.0 ppb(v). The stability of sulfides in hydrogen at 0.1–4.0 ppb(v) stored in Silonite? canisters are firstly investigated. Poor stability is observed for H₂S and EtSH of which each about 30% loss after 3 days storage, indicating that the hydrogen sample stored in Silonite? containers should be analyzed within 4 days. Therefore, the developed analytical system with appropriate calibration pattern is well suitable for the accurate quantification of trace sulfides in hydrogen sampling from refueling station and production processing.     

Comparison of NFPA and ISO approaches for evaluating separation distances

The development of a set of safety codes and standards for hydrogen facilities is necessary to ensure they are designed and operated safely. To help ensure that a hydrogen facility meets an acceptable level of risk, code and standard development organizations (SDOs) are utilizing risk-informed concepts in developing hydrogen codes and standards. Two SDOs, the National Fire Protection Association (NFPA) and the International Organization for Standardization (ISO) through its Technical Committee (TC) 197 on hydrogen technologies have been developing standards for gaseous hydrogen facilities that specify the facilities have certain safety features, use equipment made of material suitable for a hydrogen environment, and have specified separation distances. Under Department of Energy funding, Sandia National Laboratories (SNL) has been supporting efforts by both of these SDOs to develop the separation distances included in their respective standards. Important goals in these efforts are to use a defensible, science-based approach to establish these requirements and to the extent possible, harmonize the requirements. International harmonization of regulations, codes and standards is critical for enabling global market penetration of hydrogen and fuel cell technologies.     

Direct high-purity hydrogen production from ammonia by using a membrane reactor combining V-10mol%Fe hydrogen permeable alloy membrane with Ru/Cs2O/Pr6O11 ammonia decomposition catalyst

The hydrogen production capabilities of the membrane reactor combining V-10 mol%Fe hydrogen permeable alloy membrane with Ru/Cs₂O/Pr₆O₁₁ ammonia decomposition catalyst are studied. The ammonia conversion is improved by 1.7 times compared to the Ru/Cs₂O/Pr₆O₁₁ catalyst alone by removing the produced hydrogen through the V-10mol%Fe alloy membrane during the ammonia decomposition. 79% of the hydrogen atoms contained in the ammonia gas are extracted directly as high-purity hydrogen gas. Both the Ru/Cs₂O/Pr₆O₁₁ catalyst and the V-10 mol% Fe alloy membrane are highly durable, and the initial performance of the hydrogen separation rate lasts for more than 3000 h. The produced hydrogen gas conforms to ISO 14687–2:2019 Grade D for fuel cell vehicles because the ammonia and nitrogen concentrations are less than 0.1 ppm and 100 ppm, respectively.     

Assessment of hydrogen quality dispensed for hydrogen refuelling stations in Europe

The fuel quality of hydrogen dispensed from 10 refuelling stations in Europe was assessed. Representative sampling was conducted from the nozzle by use of a sampling adapter allowing to bleed sample gas in parallel while refuelling an FCEV. Samples were split off and distributed to four laboratories for analysis in accordance with ISO 14687 and SAE J2719. The results indicated some inconsistencies between the laboratories but were still conclusive. The fuel quality was generally good. Elevated nitrogen concentrations were detected in two samples but not in violation with the new 300 μmol/mol tolerance limit. Four samples showed water concentrations higher than the 5 μmol/mol tolerance limit estimated by at least one laboratory. The results were ambiguous: none of the four samples showed all laboratories in agreement with the violation. One laboratory reported an elevated oxygen concentration that was not corroborated by the other two laboratories and thus considered an outlier.