ISO 14687-2:2012

INTERNATIONAL ISO
STANDARD 14687-2
First edition
2012-12-01
Hydrogen fuel — Product
specification —
Part 2:
Proton exchange membrane (PEM)
fuel cell applications for road vehicles
Carburant hydrogène — Spécification de produit —
Partie 2: Applications des piles à combustible à membrane à échange
de protons (MEP) pour les véhicules routiers
Reference number
ISO 14687-2:2012(E)
©
ISO 2012

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ISO 14687-2:2012(E)

COPYRIGHT PROTECTED DOCUMENT
© ISO 2012
All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized in any form or by any
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Published in Switzerland
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ISO 14687-2:2012(E)

Contents Page
Foreword .iv
Introduction .v
1 Scope . 1
2  Normative references . 1
3  Terms and definitions . 1
4  Requirements . 2
4.1 Classification . 2
4.2 Applications . 2
4.3 Limiting characteristics . 3
5  Hydrogen fuel qualification test . 3
5.1 General requirements . 3
5.2 Report results . 4
6  Sampling . 4
6.1 Sample size . 4
6.2 Gaseous hydrogen . 4
6.3 Particulates in gaseous hydrogen . 4
6.4 Liquid hydrogen . 4
7  Analytical methods. 4
7.1 General . 4
7.2 Parameters of analysis. 5
7.3 Water content . 5
7.4 Total hydrocarbon content . 5
7.5 Oxygen content . 5
7.6 Helium content. 6
7.7 Argon and nitrogen contents . 6
7.8 Carbon dioxide content. 6
7.9 Carbon monoxide content . 6
7.10 Total sulfur content . 6
7.11 Formaldehyde content . 6
7.12 Formic acid content . 7
7.13 Ammonia content . 7
7.14 Total halogenated compounds content . 7
7.15 Particulates concentration . 7
8  Detection limit and determination limit . 7
9  Quality assurance . 8
9.1 On-site fuel supply . 8
9.2 Off-site fuel supply . 8
10  Safety . 8
Annex A (informative) Rationale for the selection of hydrogen contaminants .9
Annex B (informative) Suggested analytical and sampling methods with detection and
determination limits .11
Annex C (informative) One common practice of quality assurance for hydrogen production
processes that utilize reforming processes associated with pressure swing adsorption
(PSA) purification .13
Bibliography .15
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ISO 14687-2:2012(E)

Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards
bodies (ISO member bodies). The work of preparing International Standards is normally carried out
through ISO technical committees. Each member body interested in a subject for which a technical
committee has been established has the right to be represented on that committee. International
organizations, governmental and non-governmental, in liaison with ISO, also take part in the work.
ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of
electrotechnical standardization.
International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.
The main task of technical committees is to prepare International Standards. Draft International
Standards adopted by the technical committees are circulated to the member bodies for voting.
Publication as an International Standard requires approval by at least 75 % of the member bodies
casting a vote.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. ISO shall not be held responsible for identifying any or all such patent rights.
ISO 14687-2 was prepared by Technical Committee ISO/TC 197, Hydrogen technologies.
This first edition of ISO 14687-2 cancels and replaces the first edition of ISO/TS 14687-2:2008.
ISO 14687 consists of the following parts, under the general title Hydrogen fuel — Product specification:
— Part 1: All applications except proton exchange membrane (PEM) fuel cell for road vehicles
— Part 2: Proton exchange membrane (PEM) fuel cell applications for road vehicles
— Part 3: Proton exchange membrane (PEM) fuel cell applications for stationary appliances
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ISO 14687-2:2012(E)

Introduction
This part of ISO 14687 specifies two grades of hydrogen fuel, “Type I, grade D” and ― Type II, grade D.
These grades are intended to apply to the interim stage of proton exchange membrane (PEM) fuel cells
for road vehicles (FCV) on a limited production scale.
It is also noted that this part of ISO 14687 has been prepared based on the research and development
focusing on the following items:
— PEM catalyst and fuel cell components tolerance to hydrogen fuel contaminants;
— effects/mechanisms of contaminants on fuel cell systems and components;
— contaminant measurement techniques for laboratory, production, and in-field operations;
— onboard hydrogen storage technology;
— vehicle demonstration results.
Since the FCV and related technology are developing rapidly, this part of ISO 14687 needs to be
revised according to technological progress as necessary. Technical Committee ISO/TC 197, Hydrogen
Technologies, will monitor this technology trend.
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INTERNATIONAL STANDARD  ISO 14687-2:2012(E)
Hydrogen fuel — Product specification —
Part 2:
Proton exchange membrane (PEM) fuel cell applications
for road vehicles
1 Scope
This part of ISO 14687 specifies the quality characteristics of hydrogen fuel in order to ensure uniformity
of the hydrogen product as dispensed for utilization in proton exchange membrane (PEM) fuel cell road
vehicle systems.
2  Normative references
The following documents, in whole or in part, are normatively referenced in this document and are
indispensable for its application. For dated references, only the edition cited applies. For undated
references, the latest edition of the referenced document (including any amendments) applies.
ISO 6145 (all parts), Gas analysis — Preparation of calibration gas mixtures using dynamic volumetric methods
ISO 14687-1, Hydrogen fuel — Product specification — Part 1: All applications except proton exchange
membrane (PEM) fuel cell for road vehicles
3  Terms and definitions
For the purposes of this document, the terms and definitions given in ISO 14687-1 and the following apply.
3.1
constituent
component (or compound) found within a hydrogen fuel mixture
3.2
contaminant
impurity that adversely affects the components within the fuel cell system or the hydrogen storage system
NOTE An adverse effect can be reversible or irreversible.
3.3
detection limit
lowest quantity of a substance that can be distinguished from the absence of that substance with a
stated confidence limit
3.4
determination limit
lowest quantity which can be measured at a given acceptable level of uncertainty
3.5
fuel cell system
power system used for the generation of electricity on a fuel cell vehicle, typically containing the following
subsystems: fuel cell stack, air processing, fuel processing, thermal management and water management
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ISO 14687-2:2012(E)

3.6
hydrogen fuel index
fraction or percentage of a fuel mixture that is hydrogen
3.7
irreversible effect
effect, which results in a permanent degradation of the fuel cell power system performance that cannot
be restored by practical changes of operational conditions and/or gas composition
3.8
on-site fuel supply
hydrogen fuel supplying system with a hydrogen production system in the same site
3.9
off-site fuel supply
hydrogen fuel supplying system without a hydrogen production system in the same site, receiving
hydrogen fuel which is produced out of the site
3.10
particulate
solid or aerosol particle that can be entrained somewhere in the delivery, storage, or transfer of the
hydrogen fuel
3.11
reversible effect
effect, which results in a temporary degradation of the fuel cell power system performance that can be
restored by practical changes of operational conditions and/or gas composition
4  Requirements
4.1  Classification
Hydrogen fuel for PEM fuel cell applications for road vehicles shall be classified according to the following
types and grade designations:
a) Type I (grade D):     Gaseous hydrogen
b) Type II (grade D):    Liquid hydrogen
4.2  Applications
The following information characterizes representative applications of each type and grade of hydrogen
fuel. It is noted that suppliers commonly transport hydrogen of a higher quality than some users may require.
Type I (grade D)      Gaseous hydrogen fuel for PEM fuel cell road vehicle systems
Type II (grade D)     Liquid hydrogen fuel for PEM fuel cell road vehicle systems
NOTE 1 Type I, grade A, B, C, Type II, grade C and Type III, which are applicable for all applications except PEM
fuel cells applications, are defined in ISO 14687-1.
NOTE 2 There is no equivalent grade A and B for Type II fuels.
NOTE 3 Hydrogen fuel specifications applicable to PEM fuel cell applications for stationary appliances are
addressed in ISO 14687-3.
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ISO 14687-2:2012(E)

4.3  Limiting characteristics
The fuel quality requirements at the dispenser nozzle applicable to the aforementioned grades of hydrogen
fuel for PEM fuel cells in road vehicles shall meet the requirements of Table 1. The fuel specifications are
not process or feed stock specific. Non-listed contaminants have no guarantee of being benign.
NOTE Annex A provides the rationale for the selection of the impurities specified in Table 1.
Table 1 — Directory of limiting characteristics
Type I, Type II
Characteristics
(assay)
Grade D
a
Hydrogen fuel index (minimum mole fraction) 99,97 %
Total non-hydrogen gases 300 μmol/mol
Maximum concentration of individual contaminants
Water (H O) 5 μmol/mol
2
b
Total hydrocarbons (Methane basis) 2 μmol/mol
Oxygen (O ) 5 μmol/mol
2
Helium (He) 300 μmol/mol
b
Total Nitrogen (N ) and Argon (Ar) 100 μmol/mol
2
Carbon dioxide (CO ) 2 μmol/mol
2
Carbon monoxide (CO) 0,2 μmol/mol
c
Total sulfur compounds 0,004 μmol/mol
(H S basis)
2
Formaldehyde (HCHO) 0,01 μmol/mol
Formic acid (HCOOH) 0,2 μmol/mol
Ammonia (NH ) 0,1 μmol/mol
3
d
Total halogenated compounds 0,05 μmol/mol
(Halogenate ion basis)
Maximum particulates concentration 1 mg/kg
For the constituents that are additive, such as total hydrocarbons and total sulfur compounds, the sum of the constituents
are to be less than or equal to the acceptable limit.
a
The hydrogen fuel index is determined by subtracting the “total non-hydrogen gases” in this table, expressed in mole
percent, from 100 mole percent.
b
Total hydrocarbons include oxygenated organic species. Total hydrocarbons shall be measured on a carbon basis
(μmolC/mol). Total hydrocarbons may exceed 2 μmol/mol due only to the presence of methane, in which case the summation
of methane, nitrogen and argon shall not exceed 100 μmol/mol.
c
As a minimum, total sulphur compounds include H S, COS, CS and mercaptans, which are typically found in natural gas.
2 2
d
Total halogenated compounds include, for example, hydrogen bromide (HBr), hydrogen chloride (HCl), chlorine (Cl2),
and organic halides (R-X).
5  Hydrogen fuel qualification test
5.1  General requirements
Quality verification requirements for the qualification tests shall be performed at the dispenser
nozzle under applicable standardized sampling and analytical methods where available. Alternatively,
the quality verification requirements may be performed at other locations or under other methods
acceptable to the supplier and the customer.
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ISO 14687-2:2012(E)

5.2 Report results
The detection and determination limits for analytical methods and instruments used shall be reported
along with the results of each test as well as the employed analytical method, the employed sampling
method and the amount of sample gas.
6  Sampling
6.1  Sample size
The quantity of hydrogen in a single sample container should be sufficient to perform the analyses for
the limiting characteristics specified in Table 1. If a single sample does not contain a sufficient quantity
of hydrogen to perform all of the analyses required to assess the quality level, additional samples from
the same lot shall be taken under similar conditions.
6.2  Gaseous hydrogen
Gaseous hydrogen samples shall be representative of the dispensed hydrogen. The sampling location
shall be in accordance with 5.1.
A sample from the dispenser nozzle shall be withdrawn through a suitable connection that does not
contaminate the sample or compromise safety. Attention shall be paid to ensure that the sampled
hydrogen is not contaminated with residual gases inside the sample container by repeated purge cycles.
A validated sampling method should be used (see Annex B for guidance).
Clause 9 provides guidance relative to managing hazards associated with withdrawing samples from
the high pressure hydrogen system.
6.3  Particulates in gaseous hydrogen
Particulates in hydrogen should be sampled from a dispenser nozzle. Samples shall be collected in a
manner that does not compromise safety. Appropriate measures should be taken for the sample gas not
to be contaminated by particulates coming from the connection device and/or the ambient air. When
using a filter, samples should be collected if possible under the same conditions (pressure and flow rate)
as employed in the actual refuelling operation. To avoid trapping particles or contaminating the sample,
no regulator should be used between the dispenser nozzle and the particulate filter.
6.4  Liquid hydrogen
Vaporized liquid samples shall be representative of the liquid hydrogen supply. Samples shall be obtained
in a manner that does not compromise safety. For example, one of the following procedures can be used
to obtain samples:
a) vaporizing, in the sampling line, liquid hydrogen from the supply container;
b) flowing liquid hydrogen from the supply container into or through a suitable container in which a
representative sample is collected and then vaporized.
7  Analytical methods
7.1  General
The analytical methods suitable for measuring characteristics listed in Table 1 are described below.
Other analytical methods are acceptable if their performances, including safety of use are equivalent to
those of the methods listed below.
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7.2  Parameters of analysis
The parameters for analytical techniques contained in this clause are
a) mole fraction, expressed as a percentage (%),
b) number of micromoles per mole (μmol/mol), and
c) number of milligrams per kilogram of hydrogen (mg/kg) (particulate concentration only).
The determination limits for the analytical methods listed should be less than or equal to the limiting
characteristics of hydrogen for all constituents listed in Table 1.
If calibration gas standards which contain the applicable gaseous components at applicable
concentrations and standardized dilution procedures are used to calibrate the analytical instruments
used to determine the limiting characteristics of hydrogen, calibration gas mixtures shall be prepared
in accordance with ISO 6145.
The calibration of measuring equipment should be traceable to a primary standard.
Analytical equipment shall be operated in accordance with the manufacturer’s instructions and validated.
7.3  Water content
The water content can be determined using one of the following instruments:
a) an electrostatic capacity type moisture meter;
b) a fourier transform infrared spectrometer (FTIR) with suitable cell path length, scan wavelength
and detector;
c) a gas chromatograph-mass spectrometer (GC-MS) and jet pulse injection;
d) a vibrating quartz analyser.
Alternatively, water content may be determined with a dew point analyser in which the temperature of
a viewed surface is measured at the time moisture first begins to form.
7.4  Total hydrocarbon content
The total (volatile) hydrocarbon content (as methane) can be determined using one of the following
instruments:
a) a gas chromatograph with a flame ionization detector (GC/FID);
b) a flame ionization detector (FID) based total hydrocarbon analyser;
c) a fourier transform infrared spectrometer (FTIR) with suitable cell path length, scan wavelength
and detectorp;
d) a gas chromatograph-mass spectrometer (GC-MS) with a concentrating device.
7.5 Oxygen content
The oxygen content can be determined using one of the following instruments:
a) a galvanic cell type oxygen analyser;
b) a gas chromatograph-mass spectrometer (GC-MS) and jet pulse injection;
c) a gas chromatograph with thermal conductivity detector (GC/TCD).
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7.6  Helium content
The helium content in hydrogen can be determined using a gas chromatograph with thermal conductivity
detector (GC/TCD) or a gas chromatograph-mass spectrometer (GC-MS).
7.7  Argon and nitrogen contents
The argon and nitrogen contents can be determined using one of the following instruments:
a) a gas chromatograph with thermal conductivity detector (GC/TCD) or a gas chromatograph with a
pulsed discharge helium ionization detector (GC/PDHID);
b) a gas chromatograph-mass spectrometer (GC-MS) and jet pulse injection.
7.8  Carbon dioxide content
The carbon dioxide content can be determined using one of the following instruments:
a) a gas chromatograph-mass spectrometer (GC-MS) and jet pulse injection;
b) a gas chromatograph equipped with a catalytic methanizer and a flame ionization detector (GC/FID
with methanizer);
c) a gas chromatograph with a pulsed discharge helium ionization detector (GC/PDHID);
d) a fourier transform infrared spectrometer(FTIR) with suitable cell path length, scan wavelength
and detector.
7.9  Carbon monoxide content
The carbon monoxide content can be determined using one of the following instruments:
a) a gas chromatograph equipped with a catalytic methanizer and a flame ionization detector (GC/FID
with methanizer);
b) a gas chromatograph with a pulsed discharge helium ionization detector (GC/PDHID);
c) a fourier transform infrared spectrometer (FTIR) with suitable cell path length, scan wavelength
and detector.
7.10 Total sulfur content
The content of inorganic and organic sulfur compounds shall be determined using a gas chromatograph
(GC) and a chemiluminescence detector with concentration device.
Alternatively, the total sulfur content may be determined using the following procedure. An oxy-
hydrogen flame, whose sulfur contents have been removed completely by absorption or by other
suitable method, may be used to burn the sample at a high temperature. The combustion products are
absorbed in hydrogen peroxide/water to oxidize the sulfur to sulfuric acid, after which the content is
determined and calculated as sulfur dioxide. The sulfur content analysis can be conducted with an ion
chromatograph (IC), capable of separating and detecting the desired component. Appropriate impurity-
concentrating techniques may be used to attain the sensitivity.
7.11 Formaldehyde content
The formaldehyde content can be determined using one of the following instruments:
a) a gas chromatograph with a flame ionization detector (GC/FID);
b) a gas chromatograph with a pulsed discharge helium ionization detector (GC/PDHID);
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ISO 14687-2:2012(E)

c) a fourier transform infrared spectrometer (FTIR) with suitable cell path length, scan wavelength
and detector;
d) a gas chromatograph-mass spectrometer (GC-MS) with concentration device.
Alternatively, the formaldehyde content may be determined using the following procedure. The
formaldehyde is absorbed in a 2,4-Dinitrophenylhydrazine (DNPH) cartridge by flowing the sampled
hydrogen through the cartridge and then extracted from the cartridge with solvent. The extraction
liquid can be analysed with a high-performance liquid chromatography (HPLC) technique, capable of
separating and detecting the desired component. Appropriate impurity-concentrating techniques may
be used to attain the sensitivity.
7.12 Formic acid content
The formic acid content can be determined using one of the following instruments:
a) a fourier transform infrared spectrometer (FTIR) with suitable cell path length, scan wavelength
and detector;
b) a gas chromatograph-mass spectrometer (GC-MS) with concentration device.
Alternatively, the formic acid content may be determined using the following procedure. The formic acid
is absorbed in an appropriate solution in a series of impingers by flowing the sampled hydrogen through
the impingers. The absorbing solution can be analysed with an ion chromatograph (IC).
7.13 Ammonia content
The ammonia content can be determined using a fourier transform infrared spectrometer (FTIR) with
suitable cell path length, scan wavelength and detector. Alternatively, the ammonia content may be
determined using the following procedure. The ammonia is absorbed in an appropriate solution and
determined with an ion chromatograph (IC).
7.14 Total halogenated compounds content
The total halogenated compounds can be determined using the one of the following instruments:
a) a gas chromatograph equipped with an electron capture detection (GC/ELCD) with concentration
device for HBr, HCl, and Cl ;
2
b) a gas chromatograph-mass spectrometer (GC-MS) with concentration device for organic halides;
c) an ion chromatograph (IC) with a concentrator.
Alternatively, the halogenated compounds may be determined using the following procedure. The
total halogenated compounds are absorbed in an appropriate solution and determined with ion
chromatograph (IC).
7.15 Particulates concentration
The concentration of
...