Gaseous Hydrogen Fuel Quality Testing Project of the California Department of Food and Agriculture – Division. of Measurement Standards. Special Funding Provided by the California Energy Commission Contract 600-09-015 Presentation Prepared By: John Mough, Ron Nies, Kevin Schnepp, Pamela Fitch
Gaseous Hydrogen Fuel Quality Testing • California Department of Food and Agriculture – Division of Measurement Standards • Reasons/justification for analytical evaluation. • Fuel-cell grade hydrogen as a transportation fuel. • Presentation of analytical approaches for testing • Results and on-going method development. • Future Considerations and Collaborations.
Gaseous Hydrogen Fuel Quality TestingCalifornia Department of Food and Agriculture Division of Measurement Standards Mission: We, as an important member of the California Department of Food and Agriculture, serve the people of California by aggressively preserving and defending the measurement standards essential in providing the citizens a basis of value comparison and fair competition in the marketplace. Website: http://www.cdfa.ca.gov/dms/
Gaseous Hydrogen Fuel Quality TestingCalifornia Energy MandatesThe California Energy Commission Project • Under California’s Business and Professions Code, the Division of Measurement Standards of the Department of Food and Agriculture is responsible for the enforcement of quality standards for transportation fuels, including hydrogen, throughout California. • Motor fuels produced and offered for sale in California are sampled and tested in the Division’s laboratories to verify that they meet the quality, performance, and drivability standards established in state law, Senate Bill 76 (Stats 2005, Chapter 91) defined hydrogen as a motor vehicle fuel in BPC Division, Chapter 14, Section 13401. This legislation made the DMS responsible for enforcing quality standards for hydrogen fuel in California.
Gaseous Hydrogen Fuel Quality TestingCalifornia Energy MandatesThe California Energy Commission Project • Assembly Bill 118 (Núñez, Chapter 750, Statutes of 2007), created the Alternative and Renewable Fuel and Vehicle Technology Program (ARFVT Program). • The statute, subsequently amended by AB 109 (Núñez) Chapter 313, Statutes of 2008), authorizes the California Energy Commission to develop and deploy alternative and renewable fuels and advanced transportation technologies to help achieve the state’s climate change, clean air, and energy strategies. • The California Air Resources Board has established the Advanced Clean Car Program, which includes regulations to increase the number of zero emissions vehicles on California’s highways. Specifically, hydrogen fuel cell vehicles are expected to be introduced for sale in California in 2015.
Gaseous Hydrogen Fuel Quality TestingThe California Energy Commission Project • The work outlined in this presentation was undertaken by DMS as a step in the development of test methods to be adopted by ASTM International. The project was funded by the Energy Commission under Contract 600-09-015 with CDFA DMS. The project involved several steps: • a survey of available test methods for the required analytes in hydrogen • a selection of the most promising of the available methods for evaluation • the purchase and installation of the equipment required to carry out the selected methods • the evaluation of the selected test methods • (continued)
Gaseous Hydrogen Fuel Quality TestingThe California Energy Commission Project (cont.) • Project Steps continued: • the identification of gaps in analytical capability exposed in testing • the development of recommendations for future work to address these gaps • the presentation of results and recommendations to the CEC, ASTM and other stakeholders • The end goal of this work is the development of robust analytical methods to detect and quantify impurities in hydrogen fuel as outlined in SAE J2719. Studies include the separation, identification, and quantification of analytes above, at, and below the proposed reporting limits.
Gaseous Hydrogen Fuel Quality Testing • The goal of the survey of existing test methods was to identify a minimum number of methods that address all the analytes and: • Have sufficient sensitivity. • Are rapid. • Use readily available and affordable laboratory equipment and apparatus. • Do not require exceptional expertise to perform. • To the extent possible, provide secondary methods for confirmation of findings. • These goals were formulated to provide gas suppliers and station operators with analytical methods that are fast, inexpensive and reliable; to ensure that their hydrogen fuel meets the specifications of J2719.
Gaseous Hydrogen Fuel Quality TestingList of Analytical Instruments • Fourier Transform Infra-Red (FTIR) detector with thermally controlled gas cell and LN2 cooled MCT detector. • A gas chromatograph (GC) instrument equipped with flame ionization detector (FID), thermal conductivity detector (TCD), and a pulse-discharge helium ionization detector (PDHID). • A gas chromatography with mass detector (GC-MS) coupled with an electron capture detector (ECD) and pulse flame photometric detector (PFPD). • Two cavity ring-down spectroscopic instruments (CRDS) with detectors for water, ammonia, and formaldeyde. • An ion chromatograph with a conductivity detector (IC/CD).
Gaseous Hydrogen Fuel Quality TestingExperimental Results The GC equipped with FID, TCD, and PDHID has been evaluated for determination of Argon (Ar)*, Nitrogen (N2), Oxygen (O2)*, Helium, total hydrocarbons (THC), carbon monoxide (CO)**, carbon dioxide (CO2), and Methane (CH4). Instrument detection limits were determined in accordance with procedures outlined in US EPA 40 CFR 401.13 subsection 136 Appendix B. Analyte Carrier GasDetector Ar, N2, O2 Helium PDHID THC, CO2, CO, Methane Helium FID Helium Argon TCD
Gaseous Hydrogen Fuel Quality TestingExperimental Results The instrument method detection limits (MDL) by GC PDHID, FID, and TCD following this procedure are shown in the following table: MDL: GC System 2 Detection Limits Analyte R2 MDL J2719 Limits Ar 0.9916 11.079 ppm 100 ppm N2 0.9650 11.080 ppm 100 ppm Methane 0.9996 0.0439 ppm 2 ppm CO2 0.9927 0.2341 ppm 2 ppm THC 0.9999 0.0122 ppm 2 ppm CO n/a indeterminate 0.2 ppm * O2 n/a indeterminate 5 ppm* Helium 0.9982 25.00 ppm 300 ppm
Gaseous Hydrogen Fuel Quality TestingExperimental Results GC with PDHID, FID, and TCD
Gaseous Hydrogen Fuel Quality TestingExperimental Results The FTIR was considered for the analysis of Water, Methane, Carbon Monoxide, Carbon Dioxide, Formaldehyde, Formic acid, and Ammonia. It is equipped with a LN2 MCT-A detector, 10 m gas cell, purged optical bench, and heated sample introduction lines. Optical resolution was set at 0.25 cm-1, and 128 scans from 4000-650 cm-1 Multi point calibrations and MDL studies were performed, with the following results:
Gaseous Hydrogen Fuel Quality TestingExperimental Results FTIR Calibration and Detection Limits (all units in ppm v/v) Analyte R2 MDL J2719 Limits CO 0.99975 0.020 0.2 CO2 0.99994 0.011 2 Methane 0.99991 0.044 2 Water 0.99664 5.33 5 NH3 0.99914 0.138 0.1 CH2O2 Not analyzed / determined 0.2 CH2O Not analyzed / determined 0.01
Gaseous Hydrogen Fuel Quality TestingExperimental Results IC/CD Ion Chromatography: An Ion chromatograph was set-up in accordance with ASTM D7550. Ammonia analysis by IC/CD was promising as the detection limits were remarkable low and separation from other ionic species was good. Multi point initial calibrations were performed, with an analytical range from 0.77 ng/ml to 38.3 ng/ml. IDL study using this calibration gave an IDL of 0. 76 ng/ml
Gaseous Hydrogen Fuel Quality TestingExperimental Results IC/CD The challenge we faced was an inability to generate consistency and repeatability into the transfer of ammonia gas into the aqueous medium for IC/CD analysis. Laboratory results yielded 65% – 85% conversion of ammonia gas to ammonium ion. The next slide illustrates a chromatogram of an ion standard diluted to 0.766 ppb ammonium ion as nitrate salt in de-ionized water.
Gaseous Hydrogen Fuel Quality TestingExperimental Results CRDS Inconsistent results from ammonia trapping experiments prompted research into alternative methods for analysis of ammonia in hydrogen. FTIR work was revealing challenges detecting and quantifying ammonia in a hydrogen matrix with other analytes present. Cavity ring-down spectroscopy instruments were evaluated as an alternative approach for ammonia analysis. Recent improvements have produced instruments capable of detecting ammonia over the analytical range required to address the contaminant limits outlined in SAE J2719 for fuel cell grade hydrogen.
Gaseous Hydrogen Fuel Quality TestingExperimental Results GC/MS GC/MS A gas chromatograph with a mass selective detector was used for the quantitation and speciation of halogenated organic compounds. A combination of EPA method TO-15 and EPA 8260c were used.
Gaseous Hydrogen Fuel Quality TestingExperimental Results GC/MS GC/MS Calibration and Detection Limits (all units in ppm v/v) Analyte R2 MDL J2719 Limits Total Halogenates In progress 0.05 Although still in progress, typical single analyte MDLs using EPA TO-15 are on the order of 0.0003 to 0.001 ppm
Gaseous Hydrogen Fuel Quality TestingSample Testing Process Diagram
Gaseous Hydrogen Fuel Quality TestingFuture Strategy and Considerations • Evaluation and identification of methods for determination of formaldehyde and formic acid. • Complete Oxygen analysis by GC/ECD • Complete CRDS analysis for ammonia and formaldehyde. Oxygen by CRDS is also an option. • Establish working groups for various test methods. • Evaluation of new technologies as they become available.
Gaseous Hydrogen Fuel Quality TestingCommentary and Suggestions • Important Feedback from Audience
Gaseous Hydrogen Fuel Quality TestingACKNOWLEDGEMENTS California Department of Food and Agriculture California Energy Commission Kristin Macey Tobias Muench R. Allan Morrison Jean Baronas Kevin Batchelor Jim McKinney Steven Cook Pat Perez Roger Macey Randy Roes John Butler Toyota Motor Corporation California Fuel Cell Partnership Jackie Birdsall Jennifer Hamilton Catherine Dunwoody California State University, Los Angeles David Blekhman I-CONNECT Chris Petty California Air Resources Board Lotus Consulting Michael Kashuba Randy Cook Gerhard Achtelik Edward Cook Bruker Daltonics, Inc. ASTM D03 Committee Ed Nygren
California Department of Food and Agriculture Division of Measurement Standards Personnel Contact Information Pamela Fitch 916-229-3058 firstname.lastname@example.org John Mough 916-229-3054 email@example.com Ron Nies 916-229-3030 firstname.lastname@example.org Kevin Schnepp 916-229-3458 email@example.com