Abstract:
A successful worldwide implementation of Carbon Capture, Utilisation and
Storage largely relies on the establishment of a safe and reliable CO₂
transmission network. CO₂ shipping hereby represents a promising transport
option, characterised by a high degree of flexibility in sink-source matching. This
study addressed some key knowledge gaps that currently pose a limitation on
large-scale commercialisation of this technology by providing information on
operational and maintenance challenges in the chain.
Firstly, an extensive review of technological advancements and future projections
in large scale CO₂ shipping drew the attention to the fact that key technical
challenges still need to be addressed in both pipeline and sea vessel systems in
order to establish a worldwide network of CO₂ transport infrastructure. In
particular, significant dearth concerns the adoption of appropriate safety
protocols during accidental scenarios and selection of suitable materials to
ensure integrity of transport infrastructure throughout real operations.
Thus, an experimental lab scale rig was built and commissioned, capable of
handling refrigerated carbon dioxide batches (up to 2.25 L) at conditions typical
of sea vessel transport (~0.7 - 2.7 MPa, 223 - 259 K); the facility was designed
to permit investigation of accidental leakage behaviour and to determine the
qualification assessment of elastomer materials exposed under real shipping
conditions.
A technical qualification of elastomer materials for CO₂ transport systems was
then performed with the aim of assessing their suitability in the intended systems
and propensity for degradation. Such elastomers are used as seals in pressure-
relief valves, providing elastomer-to-metal shutoff and eliminating leakage around
stem during relief mode. Samples previously tested under pipeline conditions (9.5
MPa, 318 K) at exposure times of 50 – 400 h were characterised for a visual
inspection, mechanical and thermo-analytical properties. Based on the suitable
performance of the elastomers under such pipeline conditions, Ethylene
Propylene Diene Monomer was selected for testing under operations typical of
CO₂ shipping; constrained (25% compression) samples thereby underwent 20 –
100 CO₂ loading and offloading cycles at average decompression rates of 1.6
MPa/min; tested materials were then qualified through the aforementioned
characterisation methodology, demonstrating a satisfactory resistance to rapid
gas decompression and mechanical stability.
A detailed experimental campaign was considered to assess the accidental
leakage behaviour of CO₂ under shipping conditions; the main risks associated
with CO₂ are asphyxiation due to displacement of oxygen to critically low levels,
and exposure to concentrations of 15% or above in air are deemed life threating
due to toxicological impacts on humans. The study highlighted that selection of
initial fluid conditions significantly affects the propensity for solid formation in the
vessel and blockages in the pipe section, thus resulting in significantly diverse
leakage behaviours. Low-pressure decompression tests (0.7 – 0.94 MPa)
resulted in the highest amount of inventory solidification (36 – 39 wt%) while high-
pressure decompression scenarios (1.8 – 2.65 MPa) demonstrated the lowest
(17 – 22 wt%).
Lastly, a real-scale investigation on liquid CO₂ discharge from the coupler of an
emergency release system was undertaken in order to scrutinise the applicability
of such spillage containment measure to CO₂ shipping operations. The study
focused on two refrigerated states, namely low- (0.87 – 0.94 MPa, 227 – 231 K)
and medium-pressure conditions (1.62 – 1.65 MPa, 239 – 240 K) typical of
shipping transport; findings demonstrated the presence of an abrupt outflow
behaviour, characterised by full inventory discharge form the coupler in less than
1 s and achievement of peak depressurisation rates of 6 MPa/s. Moreover, the
discharge behaviour showed considerable variations in relation to the selected
initial conditions.