Analysis of Sulfides, Formaldehyde, and Organic Halides in High-Purity Hydrogen for Fuel Cell Vehicles

Importance of the topic

High-purity hydrogen is essential for reliable, long-lasting operation of proton exchange membrane fuel cells (PEMFCs). Even trace levels of sulfur compounds, formaldehyde, and organic halides can poison catalysts, degrade membranes, and reduce system efficiency. Regulatory standards such as ISO 14687, SAE J2719, and GB/T 37244 define maximum allowable levels for these impurities to guarantee performance and safety in fuel cell vehicles.

Objectives and study overview

This application note presents a streamlined analytical workflow to simultaneously quantify seven sulfides, formaldehyde, and eight organic halides in high-purity hydrogen. Key aims include:

• Developing a single GC-based platform with dual detection (SCD + MSD).
• Validating linearity, repeatability, accuracy, and detection limits across regulatory ranges.
• Demonstrating compliance with international fuel cell hydrogen quality standards.

Methodology and instrumentation

Hydrogen samples were collected in passivated cylinders and preconcentrated via a thermal desorption (TD) system. Desorbed analytes were separated on an Agilent J&W DB-Sulfur SCD column. A purged two-way splitter directed 75 % of the flow to a sulfur chemiluminescence detector (SCD) for sulfides and 25 % to a mass spectrometer detector (MSD) for formaldehyde and organic halides. Calibration relied on static dilution to generate multi-point standard curves over 0.1–400 nmol/mol.

Used instrumentation

• Agilent 8890 Gas Chromatograph
• Agilent 8355 Sulfur Chemiluminescence Detector (SCD)
• Agilent 5977 Mass Spectrometer Detector (MSD) in Scan/SIM modes
• Markes Multi-Gas CIA Advantage-xr Thermal Desorption System
• Agilent J&W DB-Sulfur SCD column (60 m × 0.32 mm, 4.2 μm)
• Purged two-way splitter with deactivated fused silica restrictors

Main results and discussion

Linear calibration through the origin afforded correlation coefficients ≥ 0.997 for all analytes. Repeatability (n=6) yielded area RSDs ≤ 3.4 % for sulfides and ≤ 7.9 % for organic halides. Accuracy across the calibration range remained within ± 30 % relative error, satisfying quality control criteria. Method detection limits (MDLs) were determined by seven replicate analyses at low levels (0.05–1 nmol/mol), resulting in MDLs < 0.01 nmol/mol for sulfides, 0.08 nmol/mol for formaldehyde, and ≤ 0.09 nmol/mol for organic halides. This performance surpasses the requirements of ISO 14687, SAE J2719, and GB/T 37244.

Benefits and practical applications

• Single-run analysis for multiple impurity classes reduces instrument time and sample handling.
• Sulfur-specific detection by SCD ensures high selectivity and sensitivity for sulfides.
• MSD with SIM and full scan enables precise quantification of formaldehyde and halides.
• Passivated flow path and purge protocols minimize sample adsorption and carryover.
• Compliance with global standards supports fuel cell vehicle quality assurance.

Future trends and potential applications

Advances may include on-line monitoring of hydrogen purity in refueling stations, integration of additional detectors for expanded impurity screening (e.g., ammonia, CO/CO2), and miniaturized GC systems for field deployment. Data fusion with diagnostic software could enable predictive maintenance of fuel cell stacks.

Conclusion

The Agilent 8890 GC combined with thermal desorption, dual detection by SCD and MSD, and rigorous calibration protocols delivers robust, sensitive analysis of sulfides, formaldehyde, and organic halides in high-purity hydrogen. This approach meets or exceeds international standards, offering a practical solution for fuel cell vehicle hydrogen quality control.

References

1. Xu C., Xu G. Analysis Technology of Trace Impurities in Hydrogen for Hydrogen Fuel Cell Vehicles. Chem. Ind. Eng. Prog. 2021, 40(2), 688–702.
2. Zhang Y., Wang Y. Development and Application of Overall Solution for Hydrogen Quality Analysis of Proton Exchange Membrane Fuel Cell Vehicles. Chin. J. Anal. Lab. 2021.
3. ISO 14687:2019. Hydrogen Fuel — Product Specification.
4. SAE J2719:2015. Hydrogen Fuel Quality for Fuel Cell Vehicles.
5. GB/T 37244:2018. Fuel Specification for Proton Exchange Membrane Fuel Cell Vehicles — Hydrogen.
6. GB/T 44243:2024. Determination of Sulfur-Containing Compounds, Formaldehyde, and Organic Halides in Hydrogen for Proton Exchange Membrane Fuel Cell Vehicles by Gas Chromatography.