International Journal of Greenhouse Gas Control 114 (2022) 103601

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International Journal of Greenhouse Gas Control

journal homepage: www.elsevier.com/locate/ijggc

Materials challenges with CO2 transport and injection for carbon capture
and storage
J. Sonke a, *, W.M. Bos b, S.J. Paterson c
a
Shell Global Solutions International B.V., Amsterdam, the Netherlands
b
Shell India Markets Pvt. Ltd
c
Arbeadie Consultants, Banchory, Scotland UK

A R T I C L E I N F O A B S T R A C T

Keywords: Carbon Capture and Storage (CCS) is a key technology to mitigate emissions from large-scale fossil fuel use. CCS
Materials Selection primarily involves capturing the CO2 arising from energy-related and industrial sources, treating of the CO2 to
Carbon Capture and Storage remove impurities, and injecting it in a storage site to ensure long-term isolation from the atmosphere. The
Impurities
specific difference in relation to experience with relatively pure CO2 injection is caused by the impurity of the
CO2 transport
Dense phase CO2
CCS CO2 which will be dictated by the CO2 source and the capture technology employed.
Corrosion The aim of this work is to identify an approach to materials selection and corrosion control that can address
the specific requirements of a CCS project. Depending on the phase envelope and CO2 composition, separate
liquid phases may be formed. It has been identified that these phases can comprise of water (causing CO2
corrosion) or reaction products including strong acids and elemental sulphur.
The type of liquids formed and shifts in the phase envelope can significantly influence materials integrity due
to corrosion, and impact the flexibility and degradation of polymers. For this reason, it is recommended to start
each project with the identification of the CO2 specification and operating scenarios, including upsets that might
occur during the service life. Other concerns include the impact of low temperature scenarios, and the possible
presence of O2 and a high salinity brine on materials used in wells.

1. Introduction and background to the CCS process 1.1. CO2 source

A substantial amount of the world’s rising energy demand is forecast Removing impurities down to very low concentrations may create a
to still be met by fossil fuels over the next decade (IPCC, 2005). Carbon significant energy requirement and cost penalty (Barker et al., 2017).
Capture and Storage (CCS) is a key available technology to mitigate Consequently, CO2 captured from power generation and industrial
emissions from large-scale fossil fuel use. Therefore, developing and sources for CCS is likely to contain many impurities. For CCS projects the
commercialising this technology is essential to help reduce the impact threats related to the purity of the CO2, can be classified by the gas
on climate change (Barker et al., 2017; Bertels, 2015). CCS primarily source as:
involves capturing the CO2 arising from energy-related and industrial
sources, treating of the CO2 to remove impurities, and compressing, • Relatively clean CO2 gas. There is a lot of experience with CO2 gas
transporting and injecting it in a storage site to ensure long-term isola­ injection used for EOR (Enhanced Oil Recovery). This is a relatively
tion from the atmosphere (Paul, 2010; Gasda et al., 2004). clean CO2 source and experience has shown that there are few
In using fossil fuels to generate power, the purity of CO2 emissions is operational problems provided the fluid is kept relatively pure and
not an important parameter and as a result the quality of CO2 for CCS the water content is controlled (Barker et al., 2017; Paul et al., 2012;
transport and injection will be predominantly dictated by the CO2 cap­ Dugstad and Halseid, 2011; DRET 2009).
ture technology employed at the plant with secondary consideration of • Impure CO2 gas. For CCS the source of CO2 can originate from
the pipeline and storage limitations. combustion or from a range of industrial sources. The impurities
include those present in the gas source (e.g. H2O, NOx, SOx, O2) as

* Corresponding author.
E-mail address: [email protected] (J. Sonke).

https://doi.org/10.1016/j.ijggc.2022.103601
Received 1 June 2021; Received in revised form 6 December 2021; Accepted 3 February 2022
Available online 11 February 2022
1750-5836/Crown Copyright © 2022 Published by Elsevier Ltd. All rights reserved.
J. Sonke et al. International Journal of Greenhouse Gas Control 114 (2022) 103601

well as those present from the cleaning process (e.g. glycol, amines) et al., 2014).
or other project specific impurities (e.g. methanol, HCN, etc.). Im­
purities can have a significant impact on the corrosivity of the CO2. 1.4. Injection

1.2. Processing Injection of CO2 via a well into an underground storage provides
specific challenges that are somewhat different to typical oil and gas
To capture CO2 a range of processes are available. These all have production wells. The flow is in the opposite direction, and the CO2
their benefits and drawbacks and a project will usually select a process stream often includes oxygen as an impurity. Temperatures can be much
that best fits their needs. The processes largely involve amine type sol­ lower especially for upset conditions where a drop in pressure causes
vent treatment often in combination with glycol treatment. The mate­ Joule-Thompson cooling.
rials selection for CO2 processing equipment should be based on an IOW The low temperature exposure requires low temperature toughness
(Integrity Operating Window) approach to define the operational limits and creates additional requirements for selected materials. The oxygen
for a given material. present in CO2 requires consideration when a reservoir is selected that
The regeneration of contaminated solvents may require elevated contains a high saline aquifer that can come in contact with the mate­
temperatures which can cause degradation of the solvent to form rials used at the bottom of the well. Presence of O2, with saline water at
organic acids and sometimes reducing environments that can be corro­ an elevated (downhole) temperature may require highly resistant alloys
sive to some corrosion resistant alloys. The material of choice is with specific qualification, unless a suitable well design solution is used
invariably carbon steel but if this is not suitable then materials upgrades (e.g. installing a barrier valve downhole to prevent flowback). Other
typically include AISI 316, 22 Cr duplex or 6 Mo stainless steels. The impurities from the captured CO2, (such as SOx, NOx, H2S, etc.) are also
materials selection will depend on the specific process and requires a introduced into the injection well, and their potential effects should not
detailed evaluation of the options, possibly including some qualification be ignored.
testing. This approach is familiar within the industry and will not be
covered in detail here (Fig. 1). 1.5. Equipment

1.3. Transport In addition to the main materials of construction for each section of
the CCS process, there are components like valves, pumps, seals, con­
Materials selection of transport pipelines (or vessel transport) typi­ nectors and other specific equipment which require due consideration in
cally involves understanding of the behaviour of the CO2. The gas for the overall materials selection. Operating with a CO2 specification that
transport is normally compressed to a pressure where the CO2 becomes a can cause acid formation may pose a specific threat for vessels and
liquid / dense phase (refer Fig. 2), and this creates some specific chal­ separators where flow is stagnant, which may trigger precipitation of
lenges which are covered below. Since transport pipelines can be many these acids. Some designs may pose a specific risk of galvanic couples
kilometres in length, the ability to use carbon steel can be a make or between different metal grades (causing galvanic corrosion), and the
break for a project. Understanding the phase behaviour and the impact presence of crevices between pipe connections can introduce crevice
of the CO2 composition including its impurities has proven to be corrosion. Moreover, the selection of non-metallic materials (especially
essential in identifying the potential threats of corrosion or other forms elastomeric seals) introduce their own specific challenges, and these will
of degradation. be covered later in this paper.
For transport via pipelines ISO Standard 27913 (ISO 27913 2016)
has been developed to provide some initial guidance, as well as ISO 2. Materials challenges
17349 (ISO 17349 2016) for offshore handling of CO2 streams at high
pressure. In developing a generic materials selection and corrosion control
For several projects ship transport of CO2 has been proposed and it is strategy the following two options exist:
worth mentioning that the threats outlined in the section on corrosion
can also be expected with ship transport (Tjelta et al., 2021). A possible 1 Threats that can be controlled (using barriers) and/or detected
additional issue with ship transport is the required cryo-compressed within a timely manner and can be tolerated with the application of a
conditions that can create temperatures down to − 30 ◦ C. These tem­ proper control strategy.
peratures are below the Tg (glass transition temperature) of a wide range 2 Threats that can lead to rapid failure that cannot be controlled or
of polymeric materials and selection requires detailed attention (Abas (timely) detected and require selection of resistant materials.

Fig. 1. Diagram showing an example of the CCS process: Modified from Shell.com (Shell.com 2016).

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J. Sonke et al. International Journal of Greenhouse Gas Control 114 (2022) 103601

Fig. 2. Phase diagram for CO2 with 0.1 mole% H2O, graph was generated with proprietary software (ST Flash).

Degradation mechanisms that can be controlled typically include pipeline, a modified Battelle Two Curve model (BTCM) as outlined in
corrosion and in this case particularly CO2 corrosion. ISO 27913 (ISO 2021) can be used. Key parameters include: purity of
In this section the threats that can potentially lead to catastrophic CO2, temperature, pressure, diameter, thickness and material strength.
failure and require to be designed out via selection of resistant materials Supplementary to the BTCM approach more accurate predictions of
are briefly reviewed. pipeline steel resistance to running fracture can be obtained from
coupled fluid-structure finite element calculations which can be used to
2.1. Low temperature define the requirements for a Fit For Service (FFS) assessment.

A cause of concern for a CCS project is the risk of low temperature 2.3. Hydrogen and H2S cracking
fracture that can lead to sudden and catastrophic failures. Any assess­
ment should include upset conditions, like start up – shut down and Hydrogen cracking can occur when atomic hydrogen (e.g. formed by
blow-down scenarios, where the effect of pressure drop can cause an anodic corrosion reaction or from welding) is adsorbed and diffuses
(Joule-Thompson) cooling and very low temperatures, with potential into the metal. The presence of atomic hydrogen in the lattice structure
tempertures down to -80 ◦ C (refer Fig. 2). Low temperature embrittle­ can cause embrittlement of the metal with the potential for catastrophic
ment of metallic materials is a well known threat in pressurised systems cracking.
(Bilio et al., 2009; Benac et al., 2016; ISO 17349 5 June 2007; API If molecular hydrogen is present it needs dissociate to be adsorbed
579/ASME FFS) and is also a critical factor for CCS projects. The phase into the metal. This is unlikely to occur at the low temperatures asso­
transition in a CCS project can cause severe sub-cooling and stretch the ciated with CCS and even the upper limit of the H2 concentrations
material toughness limits. When selecting a material, the toughness at potentially encountered in CCS are expected to have minimal impact on
the lowest possible design temperature needs to be included as part of the material fracture toughness.
the design criteria. When H2S is present in the fluid and corrosion occurs the H2S poisons
(impedes) the formation of H2 gas at the surface and more atomic
hydrogen is adsorbed by the metal. There are a variety of hydrogen
2.2. Running fracture
cracking mechanisms such as hydrogen embrittlement and sulphide
stress cracking (SSC) but these failure modes are relatively well under­
Another catastrophic risk is running ductile fracture in pipelines. The
stood and the limits for materials are defined in industry guidance (e.g.
physical properties of supercritical CO2 make CCS pipelines more sus­
ISO 15156 (ISO 2021)). This allows selection and/or treatment of
ceptible, especially for pipelines operating below 150 bar (Bilio et al.,
appropriate materials to avoid hydrogen related cracking mechanisms.
2009; DNV 2010; Andrew Cosham, 2008). The speed of a ductile frac­
Nevertheless, some differences for establishing sour resistant re­
ture is a function of the resistance of the steel to fracture and the force
quirements that require consideration with dense phase CO2 exposures
trying to fracture it (i.e. the pipeline internal pressure). If a leak occurs
include:
and vapour starts to form, the decompression speed of the CO2 stream
drops significantly (DNV 2010). However, during evaporation of liquid
- Water presence typically occurs at lower pressures (e.g. when mov­
CO2 (at the phase boundary liquid/gas) the pressure remains constant
ing towards the gas phase).
(plateau), whilst the CO2 decompression wave speed reduces, and the
fracture will not be arrested.
To determine the risk from this type of fracture in a CO2 transport

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J. Sonke et al. International Journal of Greenhouse Gas Control 114 (2022) 103601

- At high pressure the fugacity concept seems to be different for liquid/ addition to SO2 and NO2 other impurities might also have an effect on
dense phase and partitioning of H2S form CO2 to water seem more the cracking mechanisms and including a wider range of impurities may
critical in comparison with hydrocarbons. be relevant to project specific testing and validation.
- The pH of any water that drops out is typically around 3 and is lower
than the focussed pH range in ISO 15156. 3. Corrosion

2.4. Stress corrosion cracking The presence of impurities in the CO2 phase can impact corrosion
and these will be discussed in detail in this section.
Stress corrosion cracking (SCC) can occur as a consequence of the
local breakdown of a passive layer typically present with corrosion 3.1. CO2 corrosion
resistant alloys. SCC failure mechanisms are reasonably well under­
stood, but the specific conditions in a CCS project may create unusual When water is dissolved in the dense phase the water will not cause
circumstances that need further assessment and testing. The effective­ corrosion (Morland et al., 2017). However, when a separate phase of
ness of the passivation of a material is a key parameter and can be used water condenses or drops out at the metal substrate CO2 corrosion be­
as a measure (e.g. depassivation potential) of sensitivity to SCC. Typical comes a threat. From Fig. 3 it can be observed that the solubility of water
drivers for SCC are the presence of O2, chlorides, H2S, and higher tem­ depends on pressure and temperature. A step change in behaviour can be
peratures such as may be encountered in a well environment. This may seen corresponding to the point where CO2 becomes liquid and water is
create conditions for SCC in some CRA well tubulars, e.g. if high chloride much more soluble. This also implies that operational changes in pres­
containing water flow back occurs. In these circumstances it is important sure and temperature can cause water to drop out and the complete
to consult with sub-surface specialists to ensure that realistic factors are spectrum of operating conditions needs to be considered including
included in any assessment. possible upsets in order to ensure effective dewpoint control. In the KDC
A specific SCC mechanism that has been reported for carbon and low- JIP projects (Dugstad et al., 2015; Svenningsen et al., 2019) it has also
alloy (high strength) steels exposed to environments containing CO2 and been observed that when water drops out, re-dissolving the water can
CO is CO–CO2 SCC (Sandana et al., 2021; Chambers et al., 2010). If take much longer compared with exposures of dry gas.
sufficient water is present CO acts as an incomplete barrier for CO2 The CO2 dissolves in the water to form carbonic acid resulting in an
corrosion and may leave a small fraction of steel exposed. In such lo­ increase in corrosion. The main drivers for high corrosion rates are
cations local anodic attack can lead to cracking when high service stress partial pressure CO2 (pCO2), temperature, flow rate, and water chem­
or localized stresses are present. The mechanism is influenced by stress, istry. This corrosion mechanism has been widely studied and is well
the presence of water, oxygen and CO activity, and some limits have understood. Prediction models exist that can be reliably used for gas
been identified (Sandana et al., 2021; Chambers et al., 2010). Overall, operations (B.H. Morland et al., 2021; de Waard and Milliams, 1975;
this form of SCC typically occurs under a very limited set of conditions, Bonis and Crolet, 1989; de Waard et al., 1995; Gray et al., 1989; Pots,
when the rate of local anodic dissolution is less than the rate of SCC 1995; Zhang et al., 1997; Nesic et al., 1996; NORSOK 2021; Nyborg,
crack growth, otherwise corrosion would act as a crack blunting 2002).
mechanism. For dense phase CO2 a correlation model has been developed because
The effects of SO2 (Zeng and Li, 2020) and NO2 are thought to in­ at higher partial pressures, the dependence of corrosion rates on pCO2 is
fluence susceptibility to SCC as well. Beside a potentially direct effect in smaller than normally predicted. The current dense phase CO2 correla­
initiating SCC, the impact of their reaction products on local pH (see tion is based on the “De Waard-Milliams Nomogram” (de Waard et al.,
next section) can also be expected to contribute to the mechanism. In 1991), but uses a lower factor (0.27 instead of 0.67). It has been shown

Fig. 3. Water solubility limits (ppmv) in CO2 as a function of CO2 pressure at several temperatures, data were calculated using OLI (B.H. Morland et al., 2021).

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J. Sonke et al. International Journal of Greenhouse Gas Control 114 (2022) 103601

that the use of this factor results in a better fit between field/laboratory 3.2.1. Impurities affecting CO2 corrosion
data and model calculations. Since this approach is based on merely Impurities that potentially can trigger drop out of water but take no
"data fitting" and the Nomogram, it also has some drawbacks, such as no further part in the corrosion process, or produce a positive effect on CO2
influence of flow velocity. This may impact corrosion rates which can be corrosion, include chemicals typically used in the gas processing treat­
significantly lower with reducing velocity or higher with increasing ment (e.g. glycols [MEG/DEG/TEG] and alcohols such as methanol).
velocities. It would be beneficial to develop this model further and to The impact of glycols and methanol on normal CO2 corrosion are well
link it to more mechanistic CO2 corrosion models that are available. known and factors are usually applied to reduce the corrosion rate a
However, as will be discussed, the incorporation of the effects of im­ result of the presence of these components (de Waard et al., 1991). These
purities is likely to have an even greater impact and require inclusion in impurities typically have a more critical limit for operating in gas phase
a more robust prediction model. and transient conditions compared to dense/liquid phase because of the
Table 1 shows corrosion predictions using the dense phase CO2 lower solubility.
correlations. The predicted CO2 corrosion rates have less dependence on Another impurity that can be present due to carryover are amine type
pressure compared to a conventional CO2 corrosion prediction model. molecules (e.g. MEA/MDEA) (Barker et al., 2017; Zheng et al., 2018).
However, corrosion rates at high CO2 pressure are still high and corro­ The effects of amines have not been studied extensively, but data that
sion control is typically based on dewpoint/water specification control exist indicate that the impact with even small amounts of amine type
to avoid drop out/condensation. Conventional protection using corro­ molecules can cause a significant reduction of the average CO2 corrosion
sion inhibition is not commonly used because it is less effective in dense rate compared to no amines being present (Ayello et al., 2010; Thodla
phase CO2 due to the solubility of the chemicals in CO2 and the criti­ et al., 2009; Kanimozhi et al., 2014; Xiang et al., 2018). However, the
cality of distribution to the metal surface. Nevertheless, this potential data indicate that the reduction does not always give full mitigation and
corrosion mitigation option is worth further investigation. observations of localised corrosion have been identified as well. This
localised corrosion may have been caused by a second type of impurity
3.2. Effect of impurities (e.g. formation of acids) and it is not certain whether full miti­
gation/inhibition by amine type molecules is indeed possible. The use of
The effect of impurities on corrosion can be classified as follows: film forming corrosion inhibitors typically used for oil and gas rely on
the presence of hydrocarbons which are absent in CCS streams, and the
1 Impurities initiate a shift in the tendency of water to precipitate, thus degreasing effect of CO2 will also have a negative impact. Nevertheless,
creating conditions for CO2 corrosion. This was originally assumed to deployment of corrosion inhibitors may be successful (Jackson et al.,
be the predominant impact and was the focus of much research, but 2019) for specific circumstances. The distribution of the inhibitor mol­
other effects have since been identified and the focus of latest ecules where water drops out has been identified as crucial and further
research has shifted to reaction components (Dugstad et al., 2013), analysis needs to be done.
which should not be neglected.
2 Impurities react with other components creating new impurities that 3.2.2. Reaction products of impurities causing corrosion
might cause strong acids and elemental sulphur to drop out pro­ Continued research has shown that there are also liquids dropping
ducing a more severe type of corrosion. It has been observed that out of the dense phase which are reaction products formed by the
dense phase CO2, containing water, O2, SO2, NO2 and H2S can form presence of a combination of impurities. The reaction products that were
highly corrosive liquid phases containing sulphuric acid, nitric acid found include strong acids (HNO3 and H2SO4) and elemental sulphur
and elemental sulphur (Morland et al., 2017; Dugstad et al., 2015; (Morland et al., 2017; B.H. Morland et al., 2021; Dugstad et al., 2013;
Svenningsen et al., 2019; B.H. Morland et al., 2021; Dugstad et al., Dugstad, Halseid and Morland, 2014; Halseid et al., 2014; Bonis, 2011;
2013; Dugstad, Halseid and Morland, 2014; Halseid et al., 2014; Bonis, 2012; Morland and Dugstad, 2016; Morland et al., 2018; B.H.
Bonis, 2011; Bonis, 2012; Morland and Dugstad, 2016; Morland Morland et al., 2019; B.H. Morland et al., 2019; B.H. Morland et al.,
et al., 2018; B.H. Morland et al., 2019; B.H. Morland et al., 2019; B. 2021; Svenningsen and Morland, 2021; Ruhl and Kranzmann, 2013;
H. Morland et al., 2021; Svenningsen and Morland, 2021; Ruhl and Yevtushenko et al., 2014; Zheng et al., 2018; Ayello et al., 2010).
Kranzmann, 2013; Yevtushenko et al., 2014; Zheng et al., 2018; In the IFE KDC JIPs (Dugstad et al., 2015; Svenningsen et al., 2019)
Ayello et al., 2010). the relevant impurities were identified as well as the critical limits that
impact the formation of these highly corrosive reaction products. The
For a robust corrosion analysis, it is essential to know which impu­ identified impurities include H2O, O2, NO2, SO2, and H2S. The research
rities might be present and what the potential limits are. At the same has been focussed on identification of operating limits that prevent drop
time it is important to understand the process conditions and operating out of these acids, and also the solubility limits of the acids that are
envelope (including upsets) in the system to be able to estimate the formed. A summary of some of the results is presented in Table 2 (B.H.
potential risk of drop out of the impurities including water, and the Morland et al., 2021).
likely composition of the dropped out liquids. These impurity limits have only been verified for 100 bar and 25 ◦ C
(typical CO2 transport pipeline conditions). It is likely the limits will be
different for other temperatures and pressures. It should also be noted
that the observed corrosion rates reported in Table 2 are not likely to be
Table 1
representative of field conditions. Much higher corrosion rates can occur
Corrosion predictions for CO2 corrosion using the dense phase CO2 correlation
with the predicted corrosion rates using the Shell conventional CO2 corrosion
(Bonis, 2011; Bonis, 2012) in the field because of the larger volumes and
model, (2017 update of the LCR+ model (Pots, 1995; Pots et al., 2002)) shown in effects of flow (including replenishment of corrodents), and accumula­
italics and between brackets (). tion of liquids at low points. Short-term upsets might cause corrosion
effects over the longer term. It is recommended that safe operating limits
Hydrocor 2021 – Dense Phase CO2 correlation at a flow velocity of 1 m s¡1
and a pipe diameter of 0.1 m are identified for a project that avoid the drop out of acids and elemental
sulphur.
CO2 pressure 50 ◦ C 20 ◦ C 0 ◦C
[bar] [mm y¡1] [mm y¡1] [mm y¡1]
It has also been identified (B.H. Morland et al., 2021) that the
10 14 (20) 4 (4.5) 1.7 (3.4) presence and oxidation of NO2 drives other reactions including the
25 13 (35) 5 (6.5) 2 (5) formation of H2SO4 which is less soluble. Therefore the NO2 and O2
50 10 (50) 6 (8) 2 (6.5) limits are also relevant for assessing the risk of formation of H2SO4. NO2
100 8 (70) 7 (10) 2.5 (8)
is a strong oxidizing agent and drives most reactions. Its complete

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Table 2
Overview of several impurity concentrations for CO2 transport evaluated based on experimental testing at 25 ◦ C and 100 bar. (B.H. Morland et al., 2021).
No. Validated impurity content (ppmv) Remark

H2O SO2 O2 H2S NO2

1 2500* Negligible corrosion with under-saturated water. *

2 2500* 80** 240** Slight corrosion for water > 1600 ppmv. *
3 200 1000 100 Slight corrosion.
4 250 70** Significant corrosion with 630 ppmv water.
5 100 35 60 35 Visual observations indicated no corrosion or chemical reactions.
(300) (100) (350) (100) (Nonreactive experiment, but no visual conformation.)
6 50 35 80 30 Visual conformation and nonreactive experiment.
7 200 20 20 20 10 Formation of H2SO4 and HNO3 if (SO2+H2S) > 60 ppmv.
*
Precipitation of liquid water must be avoided. The water solubility varies with temperature and pressure. Check the temperature and pressure profile for the
transportation system to identify the point with lowest solubility.
**
These impurities might be increased, since it was the water concentration that was controlled/ramped up until corrosion occurred.

removal would make room for higher limits of other impurities like SO2, have a low solubility in CO2 (see Fig. 4) and are unlikely to be retained in
H2S and O2. This example shows the relevance of considering the wider solution for all operating scenarios, it is recommended to maintain a CO2
spectrum of impurities for identification of safe operating limits and CO2 specification with concentrations below the identified thresholds for
specification. their formation (B.H. Morland et al., 2021).
Additionally, the solubility limits of H2SO4 and HNO3 have been
determined (Fig. 4). It can be observed that the solubility limits are 3.2.3. Impurities with unknown impact
affected by pressure and temperature. This emphasises the need to In addition to the above-mentioned impurities, there is a much wider
consider the wider operating envelope in a project and include upset and range of potential impurities which have not yet been analysed with
transient conditions since these may initiate liquid drop out. respect to their effect on corrosivity. Further research is needed into
From the solubility graphs it can also be deduced that the risk of potential impurities in CCS systems such as organic acids, amines, ke­
liquid drop out significantly increases with pressure reduction, espe­ tones, ethers, sulphur containing species, etc., in their pure form and as
cially moving from the liquid to the gas phase. This highlights the need combinations, to ensure that there are no surprises as CCS is increasingly
in a CCS project to assess the risk of impurities, such as acids, dropping deployed.
out should upsets with a pressure drop occur, or under specific process
conditions where pressure is reduced, e.g. separators and vessels, etc. (B. 4. Corrosion resistant alloys (CRAs)
H. Morland et al., 2021).
In addition to understanding the solubility of the identified corrosive Another possible consequence of the presence of water in CCS sys­
phases, the threshold at which they are formed also needs to be tems is that under specific conditions it can lead to the breakdown of
considered. The reactivity of NO2 and O2 is high even at low concen­ passivity of low grade CRA materials such as 13Cr martensitic stainless
trations, and therefore the concentration of potentially formed HNO3 steel which is often used for the injection tubing in wells. The elevated
should be maintained below its solubility limit (see Fig. 4). The reac­ CO2 pressure can lower the pH of condensing water to create a condition
tivity of SO2 (H2S typically reacts by first forming SO2) is much lower where de-passivation can occur. De-passivation can cause localised
and formation of H2SO4 or elemental sulphur is not triggered below a corrosion and even pose a risk for cracking. If these conditions only
specific threshold (B.H. Morland et al., 2021; B.H. Morland et al., 2019; happen during upsets or specific operating scenarios, the damage caused
Svenningsen and Morland, 2021). Since the H2SO4 or elemental sulphur by de-passivation of a CRA is typically harder to detect and control than

Fig. 4. Comparison of calculated and experimental solubilities of sulphuric acid (solid lines, solid symbols) and nitric acid (dashed lines, hollow symbols) in CO2. The
lines show the OLI MSE model calculations whereas the symbols denote the experimental data. (B.H. Morland et al., 2019; B.H. Morland et al., 2021).

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Fig. 5. CRA materials with their depassivation limits in this case the depassivation pH of various stainless steels in NaCl 2 M (71 g/l Cl− ) de-aerated and acidified
with HCl at 23 ◦ C [based on (Stainless Steel and Corrosion 2010) ].

uniform corrosion of carbon steel, which could also be considered for projects, the main concern with suitability of non-metallics relates to
such applications. It is recommended to select a CRA material for con­ specific components such as O-rings, gaskets, valve seats, and liners that
ditions where de-passivation does not occur under any operating are widely used in CCS systems. The suitability of polymers and elas­
scenario. tomers for exposure to CO2 and impurities in dense phase CO2 service
The parameters that trigger de-passivation include: pH (de-passiv­ needs to be considered and various failure modes of polymeric materials
ation pH, Fig. 5), chloride content (initiates breakdown of passivity), have been identified:
temperature and presence of oxygen (which is often present as a im­
purity in CO2). Fig. 5 shows typical values of de-passivation pH for 5.1. CO2 absorption resulting in swelling
various stainless steels. For tubulars at the bottom of injection wells in a
reservoir with high salinity, selection of high grade CRAs may be Dense phase CO2 can behave as an efficient solvent and it can
required. penetrate and saturate certain non-metallic materials. Most polymers
Contrary to oil and gas applications (Craig and Smith, 2011) CCS are chemically resistant to CO2 and the interaction is mainly physical.
conditions often include the presence of small amounts of oxygen, which The actual amount of absorbed CO2 will depend on the polymer type and
can have a significant impact on SCC, especially with well completion grade, the exposure temperature, the pressure and the duration of
materials where there is a potential brine flow back scenario. At the exposure. Significant amounts of CO2 absorption will result in swelling
elevated temperatures with high chloride concentrations of such a sce­ of the polymer, causing a reduction of (desirable) properties such as
nario, the presence of oxygen could lead to chloride SCC. strength, stiffness and resistance to permeation. Excessive swelling is
often accompanied by extraction (leaching out) of components from the
5. Non-metallics / polymers polymer (Paul et al., 2012; Energy Institute, 2010; IEAGHG, 2010; Dosi
et al., 2010; Ansaloni et al., 2020).
Apart from flexible composite pipes which may be applied in CCS The Hildebrand and Hansen solubility parameters enable prediction

Fig. 6. Solubility parameters for liquid CO2 and some polymers at room temperature gathered from various sources (temperature is expected to significantly affect
these parameters). Modified from Ansaloni et al. (Ansaloni et al., 2020).

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J. Sonke et al. International Journal of Greenhouse Gas Control 114 (2022) 103601

of the degree of interaction between polymers and solvents (ISO 17349 Table 3
2016; Huizinga et al., 2013; Halma, 2012; Hildebrand and Scott, 1950; An exemplary chemical resistance list for polymer materials, modified from
Hildebrand, 1962; Hildebrand et al., 1970; Hansen, 2004; Barton, 1991; Ansaloni et al. (Ansaloni et al., 2020) and Hofland deltaflex (www.hdrt.nl).
Hansen, 2007). The approach used with the Hildebrand solubility
parameter proved to be a good first step for systems governed by co­
valent, or dispersive, interactions and can be used to identify the effect
of CO2 exposure on a polymer. Fig. 6 illustrates the potential for inter­
action between CO2 and elastomers thus indicating the potential for
absorption of CO2, which can impact the rapid gas decompression
sensitivity.

5.2. Rapid gas decompression (RGD)

High levels of CO2 absorption in a polymer can cause considerable

damage, if there is an uncontrolled reduction of the system pressure.
This phenomenon is known as rapid gas decompression (RGD). RGD
damage is caused by (dense) gases which have been absorbed into a
polymer under high pressure quickly expanding when the external
environment is rapidly depressurised. If the expanding gas cannot
diffuse out of the polymer fast enough, local expansion of the gas leads to
supersaturation, bubble nucleation, bubble expansion and blistering or
tearing of the polymer. RGD damage can occur after a single depres­
surisation event, although cumulative cyclic degradation due to several
less severe decompression events could also occur. Since elastomers
typically have a high free volume, they are especially sensitive to RGD
damage compared to other polymers (Dosi et al., 2010; Ansaloni et al.,
2020; Huizinga et al., 2013). Selection of seal materials is typically
product specific and it is not recommended to select on generic material
D1329 - 16 2016; ASTM D2137 - 11 A 2018) that are widely used in the
type. Suppliers of seals should provide qualification data in pure CO2 or
oil and gas industry.
test the performance and incorporate evaluation of rapid decompression
as outlined in several standards (ISO 2011; NORSOK 2014). Time for
6. Discussion
decompression should follow a realistic scenario for depressurising.
Also, a limit should be identified for operation (e.g. 1.7 bar/min) to
This paper is intended to generate greater awareness of potential
ensure seal materials can meet the required performance. This is a
materials issues and provide guidance for materials selection in CCS
critical parameter and it is recommended to test based upon a realistic
projects. It identifies an approach for materials selection and corrosion
scenario. For generic type materials for seals (pre-selection), data indi­
control that can address the specific requirements of a CCS project.
cate better results for EPDM in relation to RGD compared to others such
Depending on the phase envelope, shifts in the envelope, and CO2
as FKM (Ansaloni et al., 2020).
composition, separate liquid phases may be formed. These phases can
comprise of water (causing CO2 corrosion) and/or reaction products
5.3. Low temperature flexibility
including strong acids and elemental sulphur, which can significantly
influence integrity due to corrosion of metallic materials and degrada­
Elastomers lose flexibility at low temperatures resulting in reduced
tion of polymers. Identification of the CO2 specification and all oper­
or failed sealing (Huizinga et al., 2013). Polymers used in sealing ap­
ating scenarios, including upsets that might exist during service are key
plications (mainly elastomers) are usually operated above the glass
success factors for a CCS project. Other concerns include low tempera­
transition temperature Tg. However, Joule-Thompson cooling as a result
ture scenarios, and materials used in wells.
of high-rate depressurising (e.g. due to blow-down) may result in tem­
Various materials and corrosion challenges have been identified:
peratures well below the Tg and impact the elasticity of elastomers
causing loss of sealing.
- Water precipitation occurs at much lower water content when im­
purities are present, creating a corrosive phase.
5.4. Chemical resistance
- Dense phase CO2, containing water, O2, SO2, NO2 and H2S may form
elemental sulphur together with a highly corrosive liquid phase
In addition to physical interaction there is also the potential of
containing sulphuric and nitric acid.
chemical interaction with specific impurities. For evaluation of the
- Very little is known about the impact of dense phase CO2 with im­
chemical resistance of non-metallic materials a significant amount of
purities on polymers.
data can be obtained from vendors and suppliers of these type of ma­
- Cost-effective selection of CRA’s and elastomers for CO2 capture
terials. If not, the suitability of a material can be confirmed by testing
plants.
which typically includes an exposure period of the material submersed
- Low-temperature toughness of well tubing and pipelines trans­
in the chemical at relevant temperatures, followed by an evaluation of
porting impure CO2.
physical properties such as swell (uptake), tensile strength and elonga­
- Materials selection for CO2 injection wells related to de-passivation
tion (E-modulus).
of CRA’s particularly in a high salinity reservoir with O2 contami­
An example of an overview of chemical resistance for some polymers
nation of the CO2.
at ambient temperatures is presented in Table 3, an arbitrary list
modified from Ansaloni et al. (Ansaloni et al., 2020) and Hofland del­
The materials selection for CCS should be based on the following
taflex (www.hdrt.nl).
philosophy:
For the selection of polymer materials for CCS, guidance can be
obtained from standards (ISO 2009; ISO 2011; NORSOK 2014; ASTM

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J. Sonke et al. International Journal of Greenhouse Gas Control 114 (2022) 103601

Fig. 7. Schematic overview of the materials selection and integrity management process.

- Degradation threats that can be detected and controlled (using bar­ A Identification of the operating envelope, including an optimal CO2
riers) in a timely manner may be permitted provided there is an specification, pressure temperature and flow analysis and a review of
effective control strategy. potential upset / transient conditions.
- Threats that can lead to rapid failure and cannot be readily detected B Execution of a Failure Mode and Effect Analysis (FMEA), details from
or controlled require selection of resistant materials. this paper can be used as input.
C Execution of a risk/ feasibility analysis to ensure an optimal mate­
The following approach to materials selection for CCS is recom­ rials selection is made. This may be an iterative exercise involving
mended based on the information presented in this paper: changes to the operating envelope to arrive at the basis for an
optimal materials selection.
1 Start each project with identification of the applicable CO2 compo­ D Selection of materials and definition of corrosion control
sition including impurity limits and all operating scenarios (pressure, requirements.
temperature, flow) that might exist during service. E Operate and Maintain the facilities with continuous control of the
2 Validate these conditions against their potential for causing water impurity limits of the CO2 specification, process conditions as well as
drop out/condensation and include the effect of specific impurities active corrosion management /asset integrity.
that might trigger liquid water formation (e.g. alcohols, glycols, F If one of the parameters indicates an excursion or significant change
amines). (in specification or unforeseen degradation) a Management of
3 Validate these conditions against their potential for causing forma­ Change (MOC) exercise may be required including a review of all the
tion and drop out of acids or elemental sulphur and assess the impact relevant design and operational details, perhaps leading to a change
on corrosivity. in the operating envelope.
a Include effects of impurities like O2, SO2, NO2, H2S against spec­
ified limits and translated to actual service conditions. To close knowledge gaps identified in this paper, further research is
b Include the impact of upset conditions, blow-down, and potential required to identify the effects of a wider range of impurities, CO2 phase
excursions of CO2 specification and the potential for drop out and behaviour, and understanding of materials performance under specific
accumulation of corrosive liquids. CCS conditions.
4 Exclude the potential for uncontrollable failure mechanisms such as
cracking, running ductile fracture, and low temperature embrittle­ 7. Summary
ment by selecting resistant materials to avoid these threats.
5 Ensure sufficient data are available to assess the potential rate of The following have been identified as key factors for materials se­
degradation to allow implementation of a robust control strategy if lection in a CCS project:
feasible.
6 Include validation of specific parts of the design (seals, valves, sep­ • Materials need to be selected such that any degradation occurs in a
arators etc.) with respect to the use of materials that are compatible controllable and detectable way, and rapid degradation mechanisms
with CO2 and impurities over the range of operating conditions. are avoided.
7 Ensure implementation with continuous control of the above • The operating envelope, including potential upsets (in particular
mentioned critical parameters. pressure reduction) that might trigger drop out of water and other
corrosive liquids or cause temperature drops, needs to be defined.
An illustration of a typical process for materials selection and • The CO2 specification including the range of limits for impurities
integrity management is provided in Fig. 7. The proposed process should needs to be identified.
include:

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J. Sonke et al. International Journal of Greenhouse Gas Control 114 (2022) 103601

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