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 Testing
California 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 Testing
California Energy Mandates
The 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 Testing
California Energy Mandates
The 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 Testing
The 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 Testing
The 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 Testing
List 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 Testing
Analyte-Detector Matrix
Analytical Options Evaluated
Detectors
MethanizerFID
GCECD
GCPDHID
GCPFPD
GCTCD
GCMS
FTIR
X
X
X
X
X
IC
Analyte
Water
Hydrocarbons
X
X
Oxygen
X
Helium
X
X
X
X
Nitrogen
Argon
Carbon Dioxide
Carbon Monoxide
X
X
X
Sulfur compounds
Formaldehyde
X
Formic acid
Ammonia
Halogenates
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Gaseous Hydrogen Fuel Quality Testing
Experimental 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 Gas
Detector
Ar, N2, O2
Helium
PDHID
THC, CO2, CO, Methane
Helium
FID
Helium
Argon
TCD
Gaseous Hydrogen Fuel Quality Testing
Experimental 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
Ar
N2
Methane
CO2
THC
CO
O2
Helium
R2
0.9916
0.9650
0.9996
0.9927
0.9999
n/a
n/a
0.9982
MDL
11.079 ppm
11.080 ppm
0.0439 ppm
0.2341 ppm
0.0122 ppm
indeterminate
indeterminate
25.00 ppm
J2719 Limits
100 ppm
100 ppm
2 ppm
2 ppm
2 ppm
0.2 ppm *
5 ppm *
300 ppm
Gaseous Hydrogen Fuel Quality Testing
Experimental Results
GC with PDHID, FID, and TCD
Gaseous Hydrogen Fuel Quality Testing
Experimental 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 Testing
Experimental Results
FTIR Calibration and Detection Limits (all units in ppm v/v)
Analyte
CO
CO2
Methane
Water
NH3
CH2O2
CH2O
R2
MDL
J2719 Limits
0.99975
0.020
0.99994
0.011
0.99991
0.044
0.99664
5.33
0.99914
0.138
Not analyzed / determined
Not analyzed / determined
0.2
2
2
5
0.1
0.2
0.01
Gaseous Hydrogen Fuel Quality Testing
Experimental Results
FTIR
Gaseous Hydrogen Fuel Quality Testing
Experimental 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 Testing
Experimental 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 Testing
Experimental Results IC/CD
Gaseous Hydrogen Fuel Quality Testing
Experimental Results IC/CD
Gaseous Hydrogen Fuel Quality Testing
Experimental 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 Testing
Experimental Results CRDS
Gaseous Hydrogen Fuel Quality Testing
Experimental 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 Testing
Experimental Results GC/MS
GC/MS Calibration and Detection Limits (all units in ppm v/v)
Analyte
Total Halogenates
R2
MDL
In progress
J2719 Limits
0.05
Although still in progress, typical single analyte MDLs using EPA TO15 are on the order of 0.0003 to 0.001 ppm
Gaseous Hydrogen Fuel Quality Testing
Experimental Results GC/MS
Gaseous Hydrogen Fuel Quality Testing
Sample Testing Process Diagram
Sample Arrival
Log-In Assign Analysis
0.5 hour
FTIR Analysis
Instrument is prepped
ahead of sample
1.0 hour
CRDS Analysis
Instrument prep concurrent
with FTIR analysis
1.0 hour
GC Analysis
Instrument prep concurrent
with previous analysis
1.5 hours
GC/MS
Instrument prep concurrent
with previous analysis
2.0 hours
Review Results
Results Reviewed and
signed off. Generate report
1.5 hours
Gaseous Hydrogen Fuel Quality Testing
Future 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 Testing
Commentary and Suggestions

Important Feedback from Audience
Gaseous Hydrogen Fuel Quality Testing
ACKNOWLEDGEMENTS
California Department of Food and Agriculture
Kristin Macey
R. Allan Morrison
Kevin Batchelor
Steven Cook
Roger Macey
Toyota Motor Corporation
Jackie Birdsall
California State University, Los Angeles
David Blekhman
California Air Resources Board
Michael Kashuba
Gerhard Achtelik
Bruker Daltonics, Inc.
Ed Nygren
California Energy Commission
Tobias Muench
Jean Baronas
Jim McKinney
Pat Perez
Randy Roes
John Butler
California Fuel Cell Partnership
Jennifer Hamilton
Catherine Dunwoody
I-CONNECT
Chris Petty
Lotus Consulting
Randy Cook
Edward Cook
ASTM D03 Committee
California Department of Food and Agriculture
Division of Measurement Standards
Personnel Contact Information
Pamela Fitch
916-229-3058
pamela.fitch@cdfa.ca.gov
John Mough
916-229-3054
john.mough@cdfa.ca.gov
Ron Nies
916-229-3030
ron.nies@cdfa.ca.gov
Kevin Schnepp
916-229-3458
kevin.schnepp@cdfa.ca.gov