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 Electricity (e-) Hydrogen (H2)
Hydrogen can be produced by
Water (H2O) Electrolyser Oxygen (O2)
- water electrolysis using electricity

- steam reforming of natural gas

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Natural Gas (CH4) Hydrogen (H2)

Steam (H2O) Reformer Carbon Dioxide (CO2)

Delivery by

- transportable containers
- trailers
- pipeline

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 Electrolysers:

- producing hydrogen and oxygen from water and (green) electricity

- for immediate or later use

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- most often used in industrial applications

- scalable size (0,1 to 20.000 m3/h)

- can be easily regulated from 0 to 100 %

- relatively short start up time (minutes)

- produce very pure hydrogen at elevated pressures (1 to 30 bar)

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 Reformers:

- producing hydrogen from natural gas, steam and heat.

- most often used in industrial applications

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- capacity ranges from a few hundred to more than 100 000 Nm3/h

- operated 24/7 at constant load

- relatively long start up time (days)

- emit CO2

- produced hydrogen is not very clean and at atmospheric pressure

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 In an electrolyser cell, electricity causes dissociation of water into hydrogen and oxygen
molecules. An electric current is passed between two electrodes separated by a conductive
electrolyte or “ion transport medium”, producing hydrogen at the negative electrode (cathode)
and oxygen at the positive electrode (anode).
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Two main technologies of electrolysers exist:

electrolysers based on the
- Alkaline electrolysis process and electrolysers based on the
- PEM (Proton Exchange Membrane) electrolysis process.

Their technical maturities, their operating temperatures and their electrolytes are different.

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 Alkaline electrolysis:

- most often used in industrial applications

- electrolyte is a potassium hydroxide solution (KOH)
- operating temperature ranges from 60 to 100°C
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- operating pressure ranges from 1 to 30 bar

- relatively bulky systems
- efficiency is around 65%.

Figure 128: Electrolyser developed by Norsk Hydro

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 PEM electrolysis:

- key component is the membrane (polymer) – electrode (catalyst) system

- anode: water is broken down in oxygen, electrons and protons
- protons: migrate through the membrane
- cathode: protons are reduced in hydrogen molecules
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- electrons: migrate via the external circuit to the cathode

- membrane: good chemical stability, mechanical resistance, protons conductivity, gas separation
- advantages of PEM electrolysers: load changes don’t have much influence on lifetime, high pressure
- disadvantage: high costs of the electrolyte and electro catalysts
- still at development stage

Figure 129: PEM electrolyser

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 Hazardous situations Prevention or mitigation
measures
Loss of segregation within system of H2 and O2 produced – Process reliability and detection
process pressure is an aggravating factor as this increases of O2 in H2
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amount of reactants in the system and burst pressure of

equipment
Formation of flammable mixture in container due to a H2 leak Permanent ventilation and H2
detection
Fire due to failure/overheating of high current electrical Electrical safety, fire detection
components
In case of liquid electrolyte: short circuit from electrolyte leaks Quality of assembly, periodic
inspection
In case of liquid electrolyte: corrosive electrolyte leaks Quality of assembly, periodic
inspection

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 ISO 22734-1:2008 Hydrogen generators using water electrolysis process
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Part 1: Industrial and commercial applications, Edition 1

ISO 22734-2 Hydrogen generators using water electrolysis process

Part 2: Residential applications, Edition 1

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 - 2% of hydrogen is added in the natural gas
- pre-heating to 350°C
- desulphurization
- process gas is mixed with steam
- pre-heating to about 500°C
- process gas flows through the reforming tubes filled with catalyst
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- Catalytic reactions produces syngas (H2, CO, CO2, H2O, CH4).

The reactions producing hydrogen are: CH4 + H2O → CO + 3H2

CO + H2O → CO2 + H2

- steam methane reforming reaction is very endothermic

- syngas has a temperature of 850°C
- then cooled down to about 350°C
- flows through a CO converter
- catalytic reaction produces H2 and CO2 from H2O and CO
- cooling down to 35°C
- condensation of remaining steam
- raw hydrogen concentration is more than 70% with some impurities (mostly CO2)
- removal of impurities in a purification unit

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 9
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4 8
3 5 7

2
6

Figure 131: Steam methane reforming

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 Units to be considered during safety assessment:

burner, its flame and the combustion quality, the reforming tubes and steam production unit.
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explosive atmosphere might be ignited by the burner

 increase of flame and gas temperature would damage materials of the reforming tubes.
 incomplete combustion of gases leads to formation of deposits in the exchangers

Main hazard for the reforming tubes is the formation of a leak on these tubes because
of an early ageing of the reforming tubes.

The main hazard for the steam production unit is an abnormal pressure increase.

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 ISO 16110-1:2007 Hydrogen generators using fuel processing technologies
Part 1: Safety, Edition 1

Applicable to stationary hydrogen generators intended for indoor and outdoor commercial,
industrial, light industrial and residential use with a capacity of less than 400 m3/h .
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Aims to cover all significant hazards, hazardous situations and events relevant to
hydrogen generators, with the exception of those associated with environmental compatibility
(installation conditions), when they are used as intended and under the conditions foreseen
by the manufacturer.

A list of significant hazards and hazardous situations dealt with in this part of ISO 16110
is found in Annex A.

This part of ISO 16110 is a product safety standard suitable for conformity assessment as
stated in IEC Guide 104, ISO/IEC Guide 51 and ISO/IEC Guide 7.

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 Hydrogen transport to / from refineries.

Compressed hydrogen transport in metallic pipelines.

Above-ground piping systems or
underground piping systems (open trench and/or cathodic protection).
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Material: stainless steel

Rotterdam Germany
Hydrogen Pipelines
Dordrecht
Marl
Rheinberg Dortmund
Netherlands
Zeebrugge Duisburg
Herne
Antwerp
Dunkerque Krefeld
Düsseldorf
Ghent Genk
Figure 132: Hydrogen
Lille
Brussels Geelen
Leverkussen pipeline network of
Mons Belgium Air Liquide in
Charleroi
Liège
12 networks worldwide Northern Europe
France F/Be/NL: 810 km (100 bar)
Maubeuge Germany : 240 km (200 bar)

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 Hazard Safety measures
Rupture of pipes and fittings because Hydrogen compatible materials should be chosen.
of hydrogen embrittlement
Corrosion for underground piping Piping must be externally coated to an approved specification, to protect against
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soil corrosion by cathodic protection.

Rupture of the pipe material due to Electrical continuity between underground hydrogen piping and above ground
lightning strikes or ground fault piping, or other metal structures, should be adhered.
conditions All above-ground pipelines shall have electrical continuity across all connections,
except insulating flanges, and shall be earthed at suitable intervals to protect
against the effects of lightning and static electricity
Rupture due to external forces Piping should not be exposed to external forces which can cause a failure or
dangerous situation. The main cause of pipe rupture is attack by external
operation (e.g. when a mechanical digger knocks on a pipe).
Hazards specific to underground It is preferable to have no flanged or other mechanical joints underground.
piping Only gaseous hydrogen pipes with welded joints may be buried.

Table 41: Safety measures for pipes

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Consumptions of up to a 200 Nm3/h:

CGH2 in transportable containers or trailers

Larger consumptions: hydrogen production at the site of use

Figure 133: Examples of compressed hydrogen tube trailers

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 In order to increase its density, hydrogen may be liquefied and transported by
liquid hydrogen tankers. However, storing liquid hydrogen over a long period
of time is challenging because of its rapid evaporation in case of parasitic heat input.
Tankers are insulated, and they may have large capacities exceeding 60 000L.
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Figure 134: Liquid hydrogen tanker

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 Safety devices of trailers or tankers:
 Safety relief valves and burst discs protect the vessels from an excessive pressure

Safety relief valves start to open at their set pressure.

They re-set when the pressure is at 90% of the set pressure.
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 burst discs are metal foil discs which are designed to rupture at a set
pressure. They do not re-set once they have burst.
 Emergency valves prevent any loss of hydrogen in case of pipes failures, or in case of an accident
during the trailer / tanker filling or discharge.
 Vacuum safety devices protect the outer jacket from bursting and / or the inner vessel from
collapsing in the case of a product leak into the vacuum interspace
 Anti tow-away devices to prevent the vehicle from moving when the cabin’s doors are open OR
when a product transfer and / or vent hose is connected to the road transport equipment pipework
coupling.

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 IGC Doc 81/06/E: Road Vehicle Emergency and Recovery, Revision of Doc 81/01,
European Industrial Gases Association AISBL

ISO 10961 specifies the requirements for the design, construction, testing and initial inspection
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of a transportable cylinder bundle.

Trailers EN 13807
This European Standard specifies the requirements for the design, manufacture, identification
and testing of a battery vehicle.

ADR:
Accord European Relatif au Transport International du Merchandis Dangereuses par Route
European Agreement concerning the International Carriage of Dangerous Goods by Road

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 Hydrogen installations usually

(i) store hydrogen delivered by road

(ii) distribute hydrogen to point of use

The storage function is typically performed in one of the following two ways:
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1.Even exchange of containers:

delivery and storage in transportable hydrogen containers

To ensure continuity of supply, two hydrogen containers are connected (Fig. 135)

2. Product transfer:

Hydrogen is transferred by pressure difference from the delivery trailer to a stationary hydrogen
storage tank (Fig. 136).

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Figure 135: Block diagram for hydrogen supply from two hydrogen trailers

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Figure 136: Flow diagram for gas transfer

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 Main risk:
tearing the high pressure flexible hoses by moving a container still connected to the
fixed installation.
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Preventive measures:

 Prevention of movement of trailers that are connected to the installation,

e.g. by locking the trailer’s brakes when the high pressure hose is connected to the trailer.

 Isolation valve on the trailer located on the forward side. In case of high pressure hose
rupture, the trailer can be safely isolated in order to prevent it from being emptied

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 H2 supply system Installation:
ISO/DIS 20100 clause 5.2 Gaseous hydrogen supply by tube trailers and Multi
Cylinder Packs (MCPs) and 14 Separation distances
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List of all the standards of TC 58 and TC 197 relative to vessels/tanks

ISO 15399: Gaseous hydrogen. Cylinders and tubes for stationary storage

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