LAAN-A-LM-E048

Application
Gas Chromatography

News Trace Impurity Analysis of Hydrogen Fuel in Fuel

Cell Vehicle-Related Fields

No. G283
With the development of fuel cell technology for n High-Sensitivity Analysis of Carbon Monoxide
electricity generation using hydrogen (H) as fuel, Using the Rt-Msieve 5A Column
attention is turning to household fuel cell systems and Molecular sieve 5A columns offer good separation of
fuel cell vehicles. However, one of the problems air components and carbon monoxide, and area
associated with fuel cells in their current state is the suitable type of column for the analysis of carbon
presence of carbon monoxide (CO) in the hydrogen fuel monoxide.
used in the fuel cells. Carbon monoxide adversely First, a standard gas was diluted with hydrogen to
affects the performance of the catalyst used in the adjust the concentration of each component (excluding
battery. This phenomenon is referred to as "catalyst air components) to about 0.2 ppm, and measurement
poisoning," and therefore necessitates the use of high- of the gas was then conducted using the Rt-Msieve 5A
purity hydrogen fuel. The international standard column.
(ISO 14687-2) pertaining to hydrogen fuel for fuel cell The chromatogram is shown in Fig. 1, and the analytical
vehicles, which went into effect in 2012, specifies that, conditions are shown in Table 1. The lower limit of
in addition to a maximum concentration of 0.2 ppm detection (S/N=3) of carbon monoxide was then
c a r b o n m o n o x i d e i n t h e h y d ro g e n , m a x i m u m calculated as 0.032 ppm.
concentrations are also specified for oxygen (O) and
carbon dioxide (CO2) as well as hydrocarbons. In the
past, analysis of impurities in hydrogen conventionally
required a complex system including multiple detectors
and columns, which from the standpoint of cost and
Table 1 Analytical Conditions for Trace Impurities in Hydrogen
maintenance, posed a significant hurdle. (Rt-Msieve 5A column)
The barrier discharge ionization detector (BID) is a new,
universal detector that can detect almost all Model : Tracera (GC-2010 Plus + BID-2010 Plus)
Column : RESTEK Rt-Msieve 5A (30 m × 0.53 mm I.D., df = 50 μm)
components, except helium (He, used as the plasma with Particle Trap 2.5 m
gas) and neon (Ne), with higher sensitivity than that Column Temp. : 35 ˚C (2.5 min) → 20 ˚C/min → 250 ˚C → 15 ˚C/min
→ 270 ˚C (3.42 min)
obtained using TCD and FID detectors. This Application Inj. Mode : Split 1:7
News introduces an example of high-sensitivity analysis Carrier Gas Controller : Constant linear velocity mode (He)
of carbon monoxide in hydrogen and simultaneous Linear Velocity : 45 cm/sec
Det. Temp. : 280 ˚C
analysis of impurities in hydrogen using the Tracera Discharge Gas : 50 mL/min (He)
high-sensitivity gas chromatograph equipped with a BID Inj. Volume : 3 mL
detector.

H2 O2 N2

S/N
Methane (CH4) 38
CH4
Carbon monoxide (CO) 19
CO
Ethane (C2H6) 74

Ar 4.5 5.0 5.5 6.5 7.0 7.5

C2H6
CH4 CO

2.5 5.0 7.5 10.0 min

O2: Approx. 100 ppm, N2: Approx. 340 ppm, Other Components: Approx. 0.2 ppm

Fig. 1 Chromatogram of Trace Impurities in Hydrogen (Rt-Msieve 5A Column)

Application No. G283
News

n Simultaneous Analysis of Impurities in component concentrations (other than air components)

Hydrogen Using the Micropacked ST Column to about 0.2 ppm, and this gas was analyzed using the
As carbon dioxide does not elute with the Rt-Msieve 5A Micropacked ST column.
column, a different system is required for analysis when The resultant chromatogram is shown in Fig. 2, and the
carbon dioxide is among the target substances. The analytical conditions are shown in Table 2. The lower
Micropacked ST column supports separation of limit of detection of carbon monoxide was calculated as
inorganic gasses, including carbon dioxide and lower 0.078 ppm (S/N=3). Though not as good as those
hydrocarbons, making it suitable for simultaneous obtained with the Rt-Msieve 5A column, the results
analysis of impurities in hydrogen gas. include detection of the maximum concentration
A standard gas was diluted with hydrogen to adjust the stipulated by ISO 14687-2.

H2 N2
S/N
Carbon monoxide (CO) 7.7
N2 Methane (CH4) 27
C2H6
Carbon dioxide (CO2) 42
CO
O2 Nitrous oxide (N2O) 21
CH4 CO2 C2H4
N2O C2H2
Acetylene (C2H2) 8.3
Ethylene (C2H4) 31
Ethane (C2H6) 42
2.0 3.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0

CO CH4 N2O C2H2 C2H4 C2H6

CO2

1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0 12.0 min

O2: Approx. 25 ppm, N2: Approx. 160 ppm, CO2: Approx. 0.44 ppm, Other Components: Approx. 0.2 ppm

Fig. 2 Chromatogram of Simultaneous Analysis of Impurities in Hydrogen (Micropacked ST Column)

Table 2 Analytical Conditions for Simultaneous Analysis of In this analysis, the MGS-2010 gas sampler was used
Impurities in Hydrogen (Micropacked ST Column) for the introduction of gas into the instrument; the
Model : Tracera (GC-2010 Plus + BID-2010 Plus) column was connected using the SPLITTER-INJ (P/N:
Column : Micropacked ST (2 m × 1 mm I.D.) 221-76252-41).
Column Temp. : 35 ˚C (2.5 min) → 20 ˚C/min → 250 ˚C → 15 ˚C/min
→ 265 ˚C (3 min) The MGS-2010 is a manual gas sampler for the Tracera
Inj. Mode : Split 1:4 (GC-2010 Plus). A purge mechanism is included to
Carrier Gas Controller : Pressure mode (He) reduce the leakage of peripheral air into the system.
Pressure Program : 226.8 kPa (2.5 min) - 15 kPa/min - 400 kPa (3.2 min)
Det. Temp. : 280 ˚C The SPLITTER-INJ refers to a special injection unit that
Discharge Gas : 50 mL/min (He) permits split injection of the sample without requiring
Inj. Volume : 3 mL
that it pass through the standard split/splitless injection
unit.
Using the MGS-2010 for sample gas injection together
with the SPLITTER-INJ unit, it is possible to
quantitatively analyze trace level air components,
including Oxygen (O 2), Nitrogen (N 2), etc., with high
accuracy.

Valve Unit Manual Flow Controller for Purge

Fig. 3 MGS-2010 Gas Sampler

First Edition: May. 2015

For Research Use Only. Not for use in diagnostic procedures.

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