Tests for Appropriate Class Determination (18.1)
Criticality: Medium
Progress: Addressed, Not Adequately
Score: 12
DOT Relevance: §173 Subpart D
Description of Key Area
DOT hazardous materials regulations for transportation are based
on the performance of the material when subjected to various tests. The
definitions and requirements classification and packing group assignments are
found in 49 CFR 173 of the hazardous materials regulations, specifically §173.50 through §173.156. The classification and
packing group assignment are, for the most part, based on tests found in the UN
Manual of Tests and Criteria and are essentially “open air” tests. Testing of
this type for the determination of the potential hazards associated with a
metal hydride-based hydrogen storage system may not be appropriate.
There are two broad types of metal hydride hydrogen storage
systems that are being developed and need to be considered, rechargeable and
non-rechargeable systems; where rechargeable systems contain a reversible metal
hydride are refilled by applying hydrogen to the system and non-rechargeable
systems are refilled by removing the spent hydrogen-depleted material and
replacing it with fresh hydrogen-containing material.
For non-rechargeable systems, the current material testing for
determination of hazard class and division may satisfactory address the actual
hazards presented by the hydrogen storage system. The systems may contain a
mixture of hazardous materials, such as a liquid phase that may or may not
contain a solid phase in slurry and possibly gaseous hydrogen. Each of the
various materials could be tested by the appropriate test methods and the
hazard class/division determined; the overall system classification and
division set according to 49 CFR 173.2a for mixtures and materials having more
than one hazard.
Rechargeable metal hydride systems will normally contain gaseous
hydrogen and a solid phase. While it might seem logical to classify them as a
mixture of hazardous materials: gaseous hydrogen (a 2.1 flammable gas) and a
solid material, which might be non-hazardous, a 4.1 flammable solid, a 4.2
self-heating solid or a 4.3 water reactive solid, this approach might not
represent the actual hazard represented by the overall hydrogen storage system.
The independent, separate hazards testing of the solid materials in the absence
of hydrogen gas does not accurately represent the state of the materials in a
hydrogen storage system in the presence of hydrogen gas. When charged with
hydrogen, the hydrogen is bonded to the solid phase, forming a distinctly
different chemical species. Reversible hydrogen storage materials, by design,
decompose under the operational conditions of the storage system to release
gaseous hydrogen. This process is normally endothermic, requiring an input of
heat, thus the materials cool upon hydrogen desorption. Also the hydrogen gas
might provide a barrier, slowing the diffusion of oxygen-containing air to the
material. Therefore the reactivity of the solid material in the presence of
hydrogen gas will be different than the combustion or oxygen reactivity of the
solid material at ambient temperature when in the totally desorbed state in the
absence of air. An extreme example of the difference between the hydrided and
non-hydrided state could be shown with titanium, which forms a stable hydride,
decomposing to release hydrogen only at high (600°C (1112°F)) temperatures. Dry
titanium powder (UN 2546) is a 4.2 self-heating solid assigned to packing group
I or II (i.e., either pyrophoric or at least produces moderate heat on air
exposure); whereas titanium hydride (UN 1871) is a moderate (packing group II)
4.1 flammable solid.
Additionally hydrogen storage systems that utilize metal hydrides
are more complex than simple storage containers. For example two engineered
features that these systems will likely contain for proper and optimal
operation include a manner to transfer heat between the contained solid phase
and an external heat sink and a method of preventing the solid phase from being
redistributed within the container. This second feature is to prevent
compaction of the solid which could over-stress the container. These engineered
features may mitigate potential hazards in case of an accident by minimizing
release of material or restricting the ability of air to diffuse to the solid
phase. Therefore again the hazard presented by the total system may not be
appropriately represented by the individual, open air material tests.
Discussion of Criticality
This item has been assigned a criticality of medium for several
reasons. Currently hydrogen storage systems where the hydrogen is absorbed in a
metal hydride are allowed for transport under special permits. The UN has
approved a listing in the dangerous goods table, UN 3468, and the US DOT issued
NA 9279, both of which classifies these systems as 2.1 flammable gas systems.
With review and approval of individual systems and manufacturers, potential
risks associated with these systems are minimized.
Low power fuel cell systems for portable power applications are
entering the commercial marketplace. Today the volumes are relative low with
few manufacturers. However it is expected that these applications will be the
first to achieve mass market status, with more products, manufacturers, and
higher volumes expected within the next few years.
Before packing instructions are put into regulations and some of
the materials currently under investigation are introduced into commercial
systems, it is recommended that a revised method to determine the true
potential hazards presented total system be considered.
Discussion of Progress
In the last several years, the US DOT issued hazardous materials
table listing NA 9279, Hydrogen absorbed
in metal hydride and the UN SCETDG approved entry UN 3468, Hydrogen in a metal hydride storage system
to the List of Dangerous Goods. Both of these listings assign a hazard
classification to the systems of 2.1 flammable gas. Currently these
identifications can only be used with approval from the OHMS after review and
approval of the packaging. No packaging instructions have been adopted in
either the US
regulations or the international Model Regulations. The OHMS has issued several
special permits for metal hydride hydrogen storage systems. All of the systems
that allow recharging use NA 9279 and/or UN 3468 with a 2.1 flammable gas
classification.
Progress on developing consensus standards that might be used as
packaging instructions include:
- The
ISO technical committee for hydrogen technologies (TC 197) has a working group
drafting a standard for transportable reversible metal hydride hydrogen storage
systems (document 16111). This document is currently in the approval stage as a
committee draft (“CD”) for advancement to the draft international standard
stage (“DIS”). In parallel to the CD approval, the document is being considered
for publication as a technical specification; this will allow publishing of a
consensus document at an earlier date than is possible with the International
Standard. Once the international standard is approved, the technical
specification will be withdrawn.
- CGA
has also considered developing a standard for portable metal hydride hydrogen
storage systems. The current status of this effort is not known at this time.
- Once
approved and published, either the ISO or CGA document might be used as the
basis for packaging instructions for NA 9279 or UN 3468. However it is expected
that neither will explicitly address the hazardous classification of the
materials or system.
Proposals have been submitted to ICAO and the UN SCETDG for
approval of metal hydride hydrogen storage systems of limited size being
transported aboard aircraft, both cargo and passenger, including within the
passenger cabin. ICAO has approved part of the request to allow transport
aboard cargo aircraft. These proposals have included introducing system level
tests of the systems and/or reference to ISO 16111 to approve packaging.
ASME's Boiler and Pressure Vessel project team on hydrogen tanks
is addressing metal hydride vessel design in a code case to Section VIII-1.
Recommendations
Currently metal hydride hydrogen storage systems can be
transported upon review and approval by the OHMS of the packaging. NA 9279 and UN
3468 are available for use as identifications, both with a hazard
classification of 2.1 flammable gas. This classification ignores any hazard
that might be presented by the solid phase material and/or combination of
hydrogen gas with the solid phase material.
Due to the nature of reversible metal hydride hydrogen storage
systems, it is recommended that they be considered as articles and system level
tests be developed that could predict the potential hazards associated with the
total systems under simulated real-life conditions. An example of the testing
that could be performed is catastrophic penetrations under several states of
charge. This test could include a measurement of the energy that is released
and that used to determine restrictions on mode and quantities for
transportation. This would not penalize manufacturers that use a material that
might appear to be more hazardous according to current test methods but mitigates
risk with system design.
While there is a lot of information available about the
traditional intermetallic metal hydrides, there is not a lot of public
information available about total system performance and their hazards in
accident scenarios. Also there are many materials under development that might
have very different properties, and thus hazards. By developing system level
tests to determine potential hazards, new materials and new designs will be
able to be introduced and appropriately classified without the risk of
misclassified.
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