Pipeline Technology Conference 2021.

Berlin

Hydrogen Pipelines – Design and Materials Challenges and Mitigations

N. Gallon - ROSEN, Newcastle upon Tyne, United Kingdom

R.M.Andrews – ROSEN, Newcastle upon Tyne, United Kingdom
O.J.C. Huising – Gasunie, Groningen, Netherlands

Abstract

The issue of decarbonizing the energy system is one of the greatest challenges worldwide at
the moment. The transition towards a hydrogen driven economy is globally gathering pace,
and at a European level there are already several pilot projects to prove hydrogen
technologies and their economic applicability. There is clear evidence that hydrogen is
actively perceived from both industry and politics as being an important sustainable energy
source in the future.

A key enabler within the hydrogen energy transition is the ability to safely and economically
transport hydrogen. The use of pipelines is an obvious solution to this challenge, however
hydrogen induced degradation of materials is acknowledged as one of the key challenges for
the pipeline industry. There are thousands of kilometres of pipelines already transporting
hydrogen gas, however almost all of these have been designed, built and operated in
accordance with hydrogen specific codes. Re-purposing of existing natural gas pipelines will
therefore imply different challenges.

EPRG recognise that extensive research has already been performed into the effects of
hydrogen on materials. For example previous studies show that there are existing specific
combinations of susceptible material, hydrogen concentration and stress level, which can
lead to an accelerated fatigue crack growth rate. However this information has not to date
been combined into one comprehensive study summarising the effects of gaseous hydrogen
on pipeline materials.

This paper summarises the outcome of an EPRG sponsored literature study looking at the
effects of hydrogen on pipeline materials, and potential mitigation strategies.

The original literature study extended to over 100 pages. It is available for download on the
EPRG website. For reasons of conciseness this paper only includes the main conclusions and
a bibliography.

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Hydrogen and Steel

Hydrogen has been produced, transported and stored in steel for hundreds of years and there
are currently thousands of kilometres of hydrogen pipelines in service around the world (1).
These pipelines have, almost without exception been designed and built in accordance with
hydrogen-specific codes. These codes tend to be more prescriptive in terms of allowable
loading (both static and dynamic) than their natural gas equivalents and the pipelines tend to
be manufactured from lower strength steel, but their existence proves that it is possible to
transport gaseous hydrogen through pipelines.

Company km Miles

Air Liquide 1936 1203

Air Products 1140 708

Linde 244 152

Praxair 739 459

Others 483 300

World Total 4542 2823

Table 1 - Existing Hydrogen Pipelines by Company

Region km Miles

U.S. 2608 1621

Europe 1598 993

Rest of World 337 209

World total 4542 2823

Table 2 - Existing Hydrogen Pipelines by Region

Hydrogen Damage

The exact mechanism(s) of hydrogen damage are still the subject of much debate. It is
generally agreed that most damage mechanisms involve concentration of hydrogen at regions
of high stress in the metallic lattice (e.g. crack tips), and that this concentration is highest
where direct dissociation from gaseous external hydrogen can occur. This dissociation of
gaseous hydrogen leads directly to a various effects as discussed below.

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Figure 1 - Schematic Showing Possible Hydrogen Traps from Koyama et al (2).

Effects on Steel Properties

The principal effects of gaseous hydrogen are an increase in fatigue crack growth rate, a
decrease in fracture toughness and a decrease in ductility. The magnitudes of these effects
appear to vary according to different reports, this variation may be due to differences in
materials, hydrogen purity or testing methods. Strength may be reduced slightly, but this is
unproven.

Fatigue Crack Growth Rate

Fatigue crack growth rates (FCGR) increase even in very low concentrations of hydrogen, with
large increases being reported even in low partial pressures of hydrogen. Higher
concentrations of hydrogen lead to higher fatigue crack growth rates, although the magnitude
of these increases is dependent on multiple other factors.

• Compared to the crack growth rates in air, the acceleration in hydrogen depends
on the ΔK magnitude. The largest hydrogen effect is often found to occur in the
high ΔK regime.
• The degradation of crack growth resistance increases with increasing hydrogen
partial pressure. Crack growth acceleration can occur in hydrogen pressure as low
as 0.2 MPa.
• The acceleration in crack growth rates in hydrogen increases with decreasing
loading frequency.
• Although crack growth rates in hydrogen increase with increasing stress ratio R, as
in air, the acceleration is more evident at lower stress ratio.
• The effect of material strength on FCGR in hydrogen is not conclusive.
• Inhibitor additives such as O2 and CO are seen to drastically reduce the effects of
both hydrogen embrittlement (HE) and FCGR.

The most recent edition of ASME B31.12 (3) includes a formula for calculating FCGR based on
work by Drexler et al. (4) who derived an upper bound FCGR from work looking at X52 and

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X70 steels in 5.5 MPa gaseous hydrogen. The applicability of this for European pipeline
infrastructure has not yet been demonstrated.

Figure 2 is taken from Drexler, with the black line being the upper bound limit, the grey circles
being data in air and grey diamonds in hydrogen.

Figure 2 - FCGR of X52 and X70 Steels in Air and Hydrogen Gas – from Drexler et al.

Fracture Toughness

Most sources appear to agree on a significant reduction in fracture toughness when measured
as a stress intensity factor or CTOD, although there are large variations in the results reported
and Charpy results appear to be largely unaffected. The origin of these variations appears to
be related to various factors, including the hydrogen partial pressure, strain rate and steel
microstructure. Importantly a number of sources report fracture toughness values in
hydrogen of less than 50 ksi.in1/2 (55 MPa.m1/2). This value is referenced in ASME B31.12 as a
default minimum threshold for preventing hydrogen assisted cracking (time dependent crack
growth) for Option B designs, but the derivation of it is unclear. The toughness of material in
hydrogen is dependent on the pipeline material as well as the hydrogen concentration. This
has implications for the conversion of existing pipelines, however there is also reason to
believe that laboratory small scale tests are not entirely representative of full scale pipes, and
therefore may be unnecessarily conservative.

Given the complexity of this subject, some key papers are summarised below:

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Title Reference Summary Major Findings

Technical (5) Comprehensive 2012 Text concludes that “At a
Reference on summary of available constant pressure of 6.9
Hydrogen fracture toughness MPa, the fracture
Compatibility of data. Compilation of toughness is degraded
Materials – Plain various historic test by as much as 50% in
Carbon Ferritic results with different hydrogen gas”, various
Steels: C-Mn Alloys test protocols, data presented in tables
(Sandia Report) materials, hydrogen reflects degradation of
concentrations etc. between 13 and 69%,
reflecting the difficulties
in quantifying different
effects.
Integrity (6) 2009 summary of Cracks are identified as
Management for NATURALHY findings. the most critical defects
Pipelines No details given in the presence of
Transporting about test protocols hydrogen. Drop of 49%
Hydrogen – or materials (nominal in fracture toughness for
Natural Gas grade only). X52 (150 to 76 MPa.m1/2)
Mixtures (Muller- and 63% for X70 (120 to
Syring on behalf of MPa.m1/2) when
NATURALHY) comparing 60 bar
hydrogen to nitrogen.
The impact of pure
hydrogen on critical
initial crack depth is
significant (up to 62%
smaller for the examples
presented) but reduced
for smaller hydrogen
partial pressures.
Hydrogen Effect on (7) Summary of work Relatively small effect
Fatigue and performed during (<10%) of hydrogen on
Fracture of Pipe NATURALHY looking KI,i but larger (up to
Steels (Capelle et at electrolytically ~44%) effect on δi.
al., NATURALHY charged X52, X70 and Effect is reported to be
work) X100 material. higher for X52 than for
Compact Tension (CT) stronger steels. This is
tests performed, attributed to the fact
actual hydrogen that the X52 was 1960’s
concentration was construction with
not reported. Some presumably lower
fatigue tests also quality standards than
reported as part of modern steels, but no
this paper. details are given.
Sensitivity of (8) NATURALHY paper Time dependence of
pipelines with steel demonstrating the local hydrogen

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Title Reference Summary Major Findings

API X52 to importance of concentration and
hydrogen hydrogen “fracture toughness” is
embrittlement concentration (and measured and
(Capelle et al., hence time) on quantified. Up to ~65%
NATURALHY work) “fracture toughness”. reduction in total work
“Roman tile” of local fracture
electrolytically emanating from a notch.
charged tests used.
Full scale burst tests
also reported.
Influence of (9) Toughness measured Large decreases in δ for
hydrogen and as CTOD per ISO small additions of
oxygen impurity 12135:2002 (10) on hydrogen (0.85 bar).
content in a CT specimens of X70 Significant mitigating
natural gas / steels. Testing effects for small (100
hydrogen blend on performed in-situ ppm) additions of
the toughness of with various different oxygen. Different
an API X70 Steel – concentrations of fracture morphologies
Briottet et al. hydrogen and noted under nitrogen,
oxygen. hydrogen and with small
oxygen additions.
Effects of purity (11) Literature survey Decreases in both
and pressure on reporting various threshold stress intensity
the hydrogen publicly available test factor and fracture
embrittlement of data. Test data toughness with
steels and other reported for wedge increasing hydrogen
metallic materials opening load and pressure. Magnitude of
– Barthelemy compact tension the decrease depends on
specimens. various factors including
steel microstructure.
Full-scale burst test (12) Report into full scale Crack arrest occurred
of hydrogen gas burst test and small after a short propagation
X65 pipeline – scale hydrogen in the burst test.
Aihara et al. embrittlement / Simulations predicted
fracture mechanics the arrest distance to be
tests (3PB pre- shorter than for
charged specimens, J- methane gas, and no
integral resistance clear influence on the
curves constructed). slope of the dynamic J
Test was performed resistance curve of
on modern high- hydrogen.
toughness line pipe.
Durability of Steels (13) Extensive testing Fracture toughness
for Transmission performed on varying decreases with
Pipes with materials of different increasing hydrogen
grades and vintages partial pressure, but

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Title Reference Summary Major Findings

Hydrogen - using both gaseous amount of decrease is
NATURALHY hydrogen and relatively small and low
electrolytically levels of oxygen
charged samples, and additions counteract this
investigating the role effect. Up to 25% v/v
of oxygen. hydrogen the effect is
not considered
significant.
Table 3 - Summary of Hydrogen Fracture Toughness Sources

Strength and Ductility

Ductility (as measured by either reduction in area or elongation at rupture) appears to

decrease by 20-80% in hydrogen, with the magnitude of this decrease varying due to the
material and test method used. The effect on uniform elongation is less defined, and there
appears to be little or no effect on strength (either yield strength or tensile strength).

Hydrogen Cracking

There does not appear to be any risk of direct hydrogen cracking (HIC) under normal gaseous
transportation conditions, although there is a theoretical risk associated with hard spots or
welds. Most existing codes have severe restrictions on allowable hardness, the derivation of
these limits is unclear. It is probable that these limits are over-conservative, however work is
required to validate this hypothesis.

Code Material Maximum Permissible

Hardness
AIGA / EIGA Hydrogen Steels (Parent and Welds) 22 HRC / 250 HB / 248 HV
Pipeline Systems (14) Microalloyed Steels (Parent 95 HRB
and Welds)
ASME B31.12:2014 (15) PWHT Carbon Steel 200 HV
PWHT Alloy Steels Cr =< 2% 225 HV
PWHT Alloy Steels 2 ¼ % =< 241 HV
Cr =<10%
Production Testing 237 HB
ASME B31.12:2019 Carbon Steel 235 HV10
Alloy Steels Cr =< 2% 235 HV10
Alloy Steels 2 ¼ % < Cr =< 248 HV10
10%
Table 4 - Hardness Limitations in Hydrogen Pipeline Codes

Non-Carbon Steel Materials

Hydrogen appears generally compatible with most polymeric materials in natural gas service,
however permeation and hence leakage rates may increase. Hydrogen has differing effects

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on non-carbon steel metals, with austenitic materials generally being less affected and higher
hardness or martensitic materials being more prone to damage.

Surface Treatment

Surface coatings and the addition of some impurities (e.g. oxygen) to gaseous hydrogen have
both been shown to be effective in reducing the damage arising from hydrogen. A good
summary is given by Holbrook et al. (16). Unfortunately it is difficult to visualise how either of
these methods could be proven to be effective 100% of the time.

Maximum Allowable Hydrogen Content

There is no clear industry consensus regarding the maximum allowable hydrogen content in
existing natural gas transmission pipelines. Most guidelines refer to maximum levels of ~10-
20% volume, however some documents refer to up to 100% hydrogen and some sources show
an effect at <2% hydrogen. The existing codes already allow up to 100% hydrogen (although
they do not apply at <10% hydrogen), but are both high level and fairly restrictive in how
conversions can be managed. The principal limits appear to be fatigue loading and the
possibility of low toughness material or large pre-existing flaws in natural gas pipelines.

Publication Maximum Hydrogen Percentage Comments

European Commission JRC Final Up to 10% v/v 10% limit based on current
Report (17) consensus, some areas need
further investigation
HSE Report (18) Up to 20% v/v Vulnerable appliances to be
identified and modified for
hydrogen levels >10%
NREL Report (19) Up to 15% v/v Appears to be feasible with very
few modifications to existing
pipeline systems or end-use
appliances
CEN / ISO Draft Roadmap (20) Up to 100% v/v Allowable hydrogen content is
dependent on the partial H2
pressure and the fatigue load. If
fatigue cycling can be controlled,
“100% hydrogen gas up to the
design pressure can be
transported in existing natural gas
pipelines without affecting the
integrity of the pipeline during its
lifetime”
ASME B31.12 (3) Up to 100% v/v Guidelines for conversion of
pipelines to hydrogen service are
included in section PL-3.21
although these are relatively high
level and restrictive, and not
particularly useable for existing
gas pipelines.
AIGA / EIGA Guidelines (14) Up to 100% v/v Guidelines for conversion of
pipelines to hydrogen service are
included in Appendix H. These
have similar restrictions to ASME
B31.12.
Table 5 - Maximum Allowable Hydrogen Contents - Various Sources

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