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Maritime: Update on Hydrogen as Cargo

Dr. Chris LaFleur, PEHydrogen Safety Codes & Standards Program ManagerSandia National LaboratoriesMarine Chemists Association SeminarJuly 19, 2017

SAND2017-7842 PE

International Maritime Organization: Hazardous Goods

• Sub-Committee on Carriage of Cargoes and Containers (CCC), under the Maritime Safety ad Marine Environment Protection Committees, covers:

– Effective implementation of codes and standards dealing with cargo operations, including packaged dangerous goods, solid bulk cargoes, bulk gas cargoes, and containers;

– Evaluation of safety and pollution hazards of packaged dangerous goods, solid bulk cargoes and gas cargoes;

– Survey and certification of ships carrying hazardous cargoes; – Enhancement of the safety, security culture and environmental consciousness in

all cargo and container operations; and – cooperation with other relevant UN bodies, IGOs and NGOs

• Relevant sections– Fuel – IGF Code – International Code of Safety for Ships using Gases or other

Low-flashpoint Fuels (Mandatory under SOLAS)– Cargo – IGC Code - International Code of the Construction and Equipment of

Ships Carrying Liquefied Gases in Bulk

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IGF 2016 – amended to include LNG

• IGF aims to minimize the risk to the ship, its crew and the environment• IGF contains mandatory provisions for the arrangement, installation, control

and monitoring of machinery, equipment and systems using low-flashpoint fuels, focusing initially on LNG

• IGF Code will not apply to ships subject to the IGC Code for gaseous fuels • Other fuels, such as hydrogen, will be added when developed by IMO

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IGC - International Code for the Construction and Equipment of Ships carrying Liquefied Gases in Bulk

• IGC provide an international standard for the safe carriage for bulk liquefied gases and other the substances by prescribing the design and construction standards of ships and the equipment they should carry so as to minimize the risk to the ship, to its crew and to the environment

• IGC applies to ships regardless of their size, including those of less than 500 gross tonnage engaged in carriage of liquefied gases having a vapor pressure exceeding 2.8 bar absolute (50.6 psi) at a temperature of 37.8°C (100°F)

• Developed specific requirements for carriage of liquefied hydrogen in bulk in 2016

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Hydrogen vs. Hydrocarbon Hydrogen exhibits different physical behaviors than hydrocarbon fuels• Diffusion characteristics (Diffuses 3x faster than hydrocarbons in air)• Non-ideal gas behavior at high pressures or low temperatures• Highly buoyant• Very low ignition energy (an order of magnitude lower than

hydrocarbons: 0.017 mJ vs 0.8 mJ gasoline and 0.3 mJ methane)• Broad flammability range (4% - 75% in air)• Hydrogen diffusion causes embrittlement in many metals• Lower radiative heat flux • Higher heat of combustion• More rapid generation of overpressures (and higher peak pressures)

due to fast flame speed

LH2 vs LNG

LH2 LNGTemperature 20K (-423 F) 112K (-258 F)

Can condense air (O2 and N2)

Will not condense air (N2: 77K, O2: 90 K)

Liquid Density ~ 70 kg/m3 (4.4 lb/ft3) 423 kg/m3 (Vapor Density at boiling point

1.2 kg/m3 1.81 kg/m3

Vapor Density at 293K 0.08 kg/m3 0.67 kg/m3Temperature at Buoyancy 22K (-420 F) 170K (-153 F)Flammability Range 4 to 75 mole % 5 to 15 mole %

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Objective:• The primary objective of the low-temperature H2 delivery

system is to study flow and flame characteristics that result from cryogenic hydrogen jets.

Cold Hydrogen Behavior Experiments for Model Development/Validation

Winters, SAND Report 2009-0035Winters & Houf, IJHE, 2011Houf & Winters, IJHE, 2013

Multi-phase behavior is important—particularly for high-humidity conditions

ADREA-HF CFD Simulations Giannissi et al, ICHS, 2013

Liquid and vapor phases have different velocities due to density differences —slip models have captured these effects in CFD simulations.

Substantial differences in model results suggest 2-phase effects cannot be neglected for LH2 releases

HSL Measurements: Sample probesHooker et al, ICHS, 2011

data

model with different solid and gas velocities

models with same solid and gas velocities

Turbulent Combustion Lab - Releasing Ultra-cold Hydrogen in the Laboratory

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¾ Accurate control/measurement of boundary conditions

Schlieren Imaging and Laser Spark Applied to Ignite Ultra-cold Releases

¾ Multiple diagnostics are used to precisely characterize releases10

Temperature Profile of Hydrogen Releases

11 ¾ Experimental challenges include avoidance of freezing air and hydrogen

The first study looked at the ignition distance using a laser spark to ignite the flows

¾ Entrained moisture (and possibly air) condenses in the cold flow

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P = 1 bar, T = 290 K, distance = 85 mm P = 1 bar, T = 37 K, distance = 325 mm

The maximum ignition distance scales with the effective diameter

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¾ for a given mass flow, ignition of cold H2 occurs much further from the release point¾ temperature affects ignition distance much more than pressure¾ a maximum ignition height is achieved at a lower mass flow rate of hydrogen for the

colder jets¾ Maximum ignition distance linearly varies as a function of effective diameter (same

as room temperature releases)

𝑅𝑅 = 𝑂𝑂𝑅𝑅 � 𝐼𝐼 � 𝑆𝑆𝑡𝑡 + 𝑆𝑆𝐵𝐵 � 𝑝𝑝𝐹𝐹 + 𝐵𝐵𝐺𝐺

R: Raw imageBG: Background luminositypF: Laser power fluctuationOR: Camera/lens optical responseSB: Background scatterSt: Laser sheet profile variationI: Corrected intensity

𝜒𝜒𝐻𝐻𝐻 𝜒𝜒𝐻𝐻𝐻

Mole Fraction 𝜒𝜒𝐻𝐻𝐻 ∝ 𝐼𝐼

Instantaneous Mean

Planar laser Rayleigh scattering has historically been used to measure concentration fields in the lab

Icing observed at the nozzle during cryogenic H2release, and cold jet condenses moisture

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(air, moisture?)icing around liq. H2 jet column

Array of thermocouples measuringthe plume temperature

¾ Challenging to provide sufficiently dried air while maintaining experimental integrity

• Goal: Use QRA tools and methods to revise bulk liquid hydrogen system separation distances in NFPA 55/NFPA 2

• Progress:– Using planar Raman imaging to measure

concentration of cryogenic releases of 2 and 4 bar hydrogen at 64K

– Validating testing is ongoing– Multi-Party CRADA with Bki and Fire

Protection Research Foundation has allowed industry to provide matching funds in support of LH2 model validation experimentation efforts

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LH2 Informing Science-based Code Revisions

Validated LH2 release model will be used to risk-inform the revised LH2 bulk separation

Planning Underway for Full Scale Release Experiments

Large scale releases will be used to study other phenomena needed for high-priority scenarios• Thermal test complex at Sandia Albuquerque

– Flame cell• Up to 3m diameter pool• 50 ft. tall indoor cell• Well characterized

ambient conditions– Humidity– Water-cooled walls

– Crosswind test facility• Dispersion in controlled crosswind• Single-direction flow• Well-characterized ambient conditions

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IMO LH2 Safety Workshop Fall 2016• Lead by Japanese delegation• Key perspective given on impetus for adding LH2 to IFC Code

– Fukishima cut ~27% of Japan’s energy supply– Victoria Australia as the worlds 2nd largest brown coal deposit located in

close proximity to a world class CO2 storage resource – Australia has pilot, demonstration and commercial carbon capture &

storage (CCS) projects– Low energy density and typically high

moisture content, brown coal is inefficient to transport and is not tradedextensively on the world market compared with higher coal grades.It is often burned in power stations near the mines. ~6% hydrogen

What is driving LH2 as cargo?*The following slides are from the Japanese presentation at the LH2 Workshop

Liquefied hydrogen shipping is critical to the success of the Hydrogen Energy Supply Chain project

Timeline

Pilot Project

Issues with Interim Guidance on LH2 as Cargo

• No consensus on:– Vent size design– Tank insulation requirements– Ability to vent GH2 in emergency (preference to capture or burn off

vented hydrogen)– Hydrogen detection methods – Extent of electrical classified areas

• Strong resistance to approving the Interim Guidance due to the outstanding issues

In Plenary Session

• Proposal was made to restrict the scope of the Interim Guidance to the Japanese/Australia pilot ship only

• Key point of agreement– Lessons learned from pilot would feed back into the LH2 Cargo

requirements– More time for all parties to study the key issues– Uncertainty around LH2 properties, behavior and hazards guided all

stakeholders to a risk averse position

In the Working Group

• Efficient progress was made on all issues because the requirements only apply to the pilot ship

• Approved document contained in Working Group Report (CCC3-WP-4_final with changes.docx)

• Default stance on sticky issues was that the Guidance says “X must be considered” without actually telling what the requirements are

Questions – follow up

• Can low concentrations of H2 cause embrittlement in steel tanks?– Embrittlement requires both H2 and stress. Ferritic materials do show

degradation at low concentrations, but are designed to have low stresses to account for this and are often used for H2 storage. Austenitic stainless steels typically withstand much higher H2 concentrations before degradation occurs. Additionally, other gases (O2, CO) can out-compete H2 at surface. Bottom line, depends on specific material and system design. (see notes for more details)

• Will standard detonation and flame arrestors work on a hydrogen flame/detonable mass?– Flame arrestors are designed for specific IEC and NEC flammable gas

groups as well as specific piping configurations. Hydrogen is classified as IEC group IIC and NEC group B and arrestors designed for these groups will function with hydrogen when installed according to design specifications.

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Vapor Pressure Comparison LH2 vs LNG

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Questions

Dr. Chris LaFleur, PEFire Protection EngineerSandia National LaboratoriesRisk & Reliability Department 8851PO Box 5800, MS 0748Albuquerque NM 87185Office: (505) 844-5425Mobile: (505) 977-8460aclafle@sandia.gov

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