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Should supercritical CO2 pipelines comply with ANSI/ NACE MR0175/ISO

15156?

Article in Materials Performance · December 2014

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MATERIALS SELECTION & DESIGN
Should Supercritical CO2
Pipelines Comply With ANSI/
NACE MR0175/ISO 15156?
B. Craig, FNACE, Stress Engineering
Services, Denver, Colorado
2 DECEMBER 2014 MATERIALS PERFORMANCE
Recent developments associated with
carbon capture and storage have sig-
nificantly increased the use of carbon
steel pipelines for the transport of su-
percritical carbon dioxide (CO2). These
pipelines are not specifically covered
by ANSI/NACE MR0175/ISO 15156,
which applies to oil and gas produc-
tion; however, it is prudent to consider
the possible risks of sulfide stress
cracking and hydrogen-induced crack­
ing that can arise in the presence of a
I
liquid water phase.
In 2008, leaders of the Group of Eight
(G8), a forum of governments from eight
industrialized countries, committed to
broad deployment of carbon capture and
storage (CCS) by 2020 and recommended
the launch of 20 large-scale CCS demonstra-
tion projects by 2010. Since 2008, govern-
ments have committed $26 billion in
funding for large-scale demonstration CCS
projects. Although progress has been made
since 2008, the 2010 target was not achieved
for a variety of reasons. To date, there is no
international agreement on a global
response to climate change. A charge on
carbon emissions, and as-yet-to-be-deter-
mined revenue-generating uses for carbon
dioxide (CO2) will be required to make many
of these projects economical. Currently,
only enhanced oil recovery projects have
positive economics. Yet the continuing
drive for CCS, along with the positive
economics for enhanced oil recovery, have
significantly increased the number of
projects worldwide that have constructed
carbon steel (CS) pipelines for transport of
supercritical CO 2. The long, successful
history of utilizing bare CS pipelines for this
transport is simply due to the dehydration
of CO 2 to levels that do not permit a
separate liquid water phase to be present.
However, regardless of how well pipelines
are designed and operated, there is always
the potential for water to be present at
some time during the life of the pipeline.
This raises the question of whether sul-
fide stress cracking (SSC) and hydrogen-
induced cracking (HIC), as described by
NACE International Standard ANSI/NACE/
MR0175/ISO 15156,1 should be considered
in the design and construction of super-
critical CO2 pipelines. This is especially rel-
evant where the CO2 source is gas contain-
ing hydrogen sulfide (H2S) that is recycled
from gas plants.
Industry Standards
and Requirements
Even though supercritical CO2 pipelines
have been in service in the United States for
more than 35 years, there are few standards
that apply to their design and construction.
Supercritical CO 2 pipelines are designed
and constructed in accordance with ASME
B31.4,2 which specifically covers CO2 pipe-
lines; however, there is no mention of the
presence of H2S in the CO2 or any require-
ments to consider the potential for crack-
ing from H2S.
NACE INTERNATIONAL: VOL. 53, NO. 12
 DNV RP J202 3 states, “Pipelines with
fluids containing hydrogen sulfide shall be
evaluated for sour service according to ISO
15156.” Strictly speaking, ANSI/NACE
MR0175/ISO 15156 does not apply to super-
critical CO2 pipelines or facilities since that
standard is specific to oil and gas develop-
ment.

Operating and
Upset Conditions in
Supercritical CO2
Typical sources of CO2 for enhanced oil
recovery come from tail gas off of gas
plants, while CCS projects are largely
aimed at sources from coal-fired power
plants and cement plants. In some cases,
actual CO2 reservoirs are produced in loca-
tions such as Jackson Dome, Mississippi,
and the Four Corners area of Colorado. The
CO 2 can contain a variety of impurities
depending on their source, including meth-
ane (CH4), hydrogen gas (H2), nitrogen gas
(N2), H2S, nitrogen oxides (NOx), and sulfur
oxides (SOx).
The critical pressure for pure CO 2 is
1,088 psi (7.5 MPa) and the critical temper-
ature is 88 °F (31 °C). However, it is com-
mon for CO2 pipelines in the United States
to operate at 2,220 psi (15.3 MPa) and
~100 °F (38 °C).
The design and operation of supercriti-
cal CO2 pipelines requires consideration of
several important mechanisms beyond the
common hydraulic and mechanical proper-
ties. These are water content of the fluid
( from a corrosion and hydrate perspective)
and the risk of running ductile fractures.
While the latter factor is very important to
the design of supercritical CO2 pipelines, it
is not addressed in this article.
It is well known that supercritical CO2 is
not corrosive unless a free liquid water
phase is present in the pipeline. This can
occur for various reasons, such as hydrotest
water that remains in the pipeline and
upset of the dehydration system. Assuming
liquid water is present, there is a risk of
hydrate formation. While it is beyond the
scope of this article, it is important to con-
sider the likely phases present in CO2-rich
systems during operation and shut downs
FIGURE 1 Effect of temperature and CO2 pressure on pH of water in supercritical CO2.
to determine whether the systems would
contain free liquid water. For example, if
hydrates form in preference to liquid water,
then corrosion—and thus HIC—might not
be a significant problem. The phases that
will form under normal pipeline operating
conditions and for upsets can be modeled
using the CSMGem program.4 According to
Sloan,4 if the temperature of the CO2 pipe-
line is 6.5 °F lower than the temperature
calculated by CSMGem for hydrate forma-
tion (or even lower than 6.5 °F), it can be
assumed that hydrates form immediately. If
hydrates form but no liquid water is pres-
ent, then corrosion will not occur and HIC
is unlikely.
Once pipeline conditions are estab-
lished and water is not a normal constitu-
ent, the risk of HIC is limited by the fre-
quency and duration of upsets that produce
liquid water and the time-of-wetness on
the pipe walls. If possible, time-of-wetness
should be limited, since the long-term pres-
ence of water will cause corrosion and the
risk that hydrates will form, which could
hamper operations. It can only be specu-
lated that time-of-wetness is likely to be
restricted to a few days or even weeks, and
not months.
Risk of SSC and HIC in
Supercritical CO2
There are no studies or data regarding
the potential for HIC of line pipe or plate
steel when exposed to supercritical CO 2
that contains H 2S. It is uncertain at this
time whether HIC or SSC would even occur
under these conditions, and whether or not
the H 2S cracking thresholds used for gas
and oil service would be the same for
supercritical CO2.
Just as for corrosion in gaseous CO2, the
risk of HIC in supercritical CO2 will depend
on the presence of liquid water. The pH of
free water under supercritical CO2 condi-
tions can be quite low. Choi and Nes̆ić5 found
that the pH would be ~3.0 to 3.2 under
supercritical conditions. Figure 1 shows the
relationship between CO2 pressure, temper-
ature, and the resulting pH from their work.
These investigators found corrosion
rates of 18 to 20 mm/y (710 to 788 mpy) in
the liquid water phase. In the presence of
liquid water, SSC of steel pipelines is a risk

NACE INTERNATIONAL: VOL. 53, NO. 12 MATERIALS PERFORMANCE DECEMBER 2014 3

MATERIALS SELECTION & DESIGN
described by ANSI/NACE MR0175/ISO
15156. When H 2S is present in the CO 2
stream, the rapid, catastrophic nature of
SSC makes consideration essential during
supercritical CO2 pipeline design.
In contrast, HIC is often a much slower
and less catastrophic cracking mechanism,
which also requires some consideration.
McIntyre6 presented over 25 case histories
from the Middle East of HIC in pipelines
and piping covering years of service. He
reported HIC crack growth rates ranging
from 0.0 to 0.036 in/y (0.9 mm/y) with one
exception where failure occurred in 10 days
(~4 in/y [102 mm/y]). This premature fail-
ure was in the highest H2S partial pressure
(84 kPa) and lowest pH (3.7) of all the cases
reported.
In laboratory studies, the crack initia-
tion rate and growth rates are typically
much faster than in actual service for vari-
ous reasons, such as only one-sided charg-
ing in service compared to multisided
charging in laboratory specimens (NACE
standard test method TM0284).7 Also, com-
pared to small laboratory samples, there
are much larger volumes of metal in a pipe-
line where hydrogen can accumulate before
crack initiation. Gonzalez, et al.8 found a
crack growth rate of ~0.09 in/d (2.3 mm/d)
in test samples exposed to a solution satu-
rated with H2S. This rate was before crack
linkage, which is an important factor in the
risk of HIC. Many companies detect HIC
early in the process of crack advance but
prior to linkage and allow the pipeline or
vessel to operate under some limitations
until linkage occurs and the component
becomes unsafe to operate.
Cayard, et al.9 reported the crack length
ratio (% CLR) for two steels, from which the
crack growth rate can be approximated.
For four days of exposure (the required
time frame for HIC testing per NACE
TM0284), the crack growth rate was essen-
tially zero for one steel and 0.18 in/d (4.6
mm/d) for another. After 30 days the rates
were 0.05 and 0.07 in/d (1.3 and 1.8 mm/d),
respectively.
Thus, it can be seen that the crack
growth rate from HIC is quite variable and
with few exceptions, is relatively slow, espe-
4 DECEMBER 2014 MATERIALS PERFORMANCE
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cially when there is an incubation period of
hours or days before achieving sufficient
hydrogen absorption to initiate cracks.
Discussion and Conclusions
Although currently there are no regula-
tory requirements to design and construct
supercritical CO 2 pipelines to resist SSC
and HIC if they contain some H 2 S, it
appears prudent as a minimum safeguard
to mitigate the risk of SSC. However, the
risk of HIC is more difficult to assess in
these systems. The corrosion rate from
supercritical CO2 when a free water phase
is present can be faster than HIC crack
growth rates, and hydrates can form so
quickly that HIC is not likely. Moreover, if
the presence of a water phase is due to
short duration upsets, the dry supercritical
CO2 entering the pipeline can be expected
to remove any liquid water, thereby drying
the pipeline and eliminating the free water
phase necessary for HIC to proceed.
The frequency and duration of upsets
that permit water to be present in the pipe-
line must be considered in the decision to
require HIC resistance. At the expected low
pH of water in contact with supercritical
CO2, the hydrogen absorption and perme-
ation could be significant. (TM0284 tests in
Solution A represent a similar pH [~2.7];
however, the test solution only contains
H 2S—no CO 2.) While it is less aggressive
than H 2S in enhancing the absorption of
hydrogen in steels, CO 2 still contributes
hydrogen to the total amount diffusing into
the steel. In addition, since hydrogen is
trapped in pipeline steels with little egress
after the water is removed, periodic upsets
will cause hydrogen to accumulate at traps,
and potentially lead to HIC crack initiation
at a later time. Therefore, until hydrogen
permeation studies can be made using
supercritical CO2 with H2S and these results
are coupled with HIC tests in the same
environment, it is impossible to be confi-
dent that HIC is not a potential threat for
supercritical CO 2 pipelines. Until labora-
tory testing has been performed to estab-
lish the level of risk for HIC in supercritical
CO2, it is prudent to require these pipeline
steels to be HIC resistant.
References
1 ANSI/NACE MR0175/ISO 15156, “Petroleum
and natural gas industries—Materials for use
in H2S-containing environments in oil and
gas production” (Houston, TX: NACE Inter-
national, 2009).
2 ASME B31.4, “Pipeline Transportation Sys-
tems for Liquids and Slurries” (New York, NY:
ASME International, 2012).
3 DNV RP J202, “Design And Operation of CO2
Pipeline” (Høvik, Norway: DNV, 2010).
4 E. Dendy Sloan, C.A. Koh, Clathrate Hydrates
of Natural Gases, 3rd ed. (Boca Raton, FL:
CRC Press, 2008).
5 Y. Choi, S. Nes̆ić, “Corrosion Behavior of Car-
bon Steel in Supercritical CO2—Water Envi-
ronments,” CORROSION 2009, paper no.
09256 (Houston, TX: NACE, 2009).
6 D.R. McIntyre, “Step-Wise Cracking Growth
Rates from Service Incidents,” Proc. 8th Mid-
dle East Corrosion Conference, held May
18-20, 1998 (Houston, TX: NACE, 1998), pp.
594-604.
7 ANSI/NACE Standard Test Method TM0284-
2011, “Evaluation of Pipeline and Pressure
Vessel Steels for Resistance to Hydrogen-
Induced Cracking” (Houston, TX: NACE,
2011).
8 J. Gonzales R. Ramirez, J.M. Hallen, R.A. Guz-
man, “Hydrogen-Induced Crack Growth Rate
in Steel Plates Exposed to Sour Environ-
ments,” Corrosion 53 (1997): p. 935.
9 M. Cayard, C. Joia, P. Bezerra, F. Assuncao,
“Fracture Toughness and Mechanical Prop-
erties of C-Mn Steels Exposed To Wet H2S
Environments,” CORROSION/99, paper no.
384 (Houston, TX: NACE, 1999).
BRUCE CRAIG, FNACE, is the subject matter
expert at Stress Engineering Services, 13800
Westfair East Dr., Bldg. 3, Houston, TX 77041,
e-mail: bruce.craig@stress.com. He has been
involved with the evaluation of corrosive oil
and gas wells and the transportation of these
corrosive fluids for projects ranging from
Mobile Bay to the deep water Gulf of Mexico
and Asia and the Middle East for more than
30 years. In addition he has consulted on many
projects around the world, including modeling
corrosion from CO2 in wet gas flow lines and
pipelines. He has consulted on numerous CO2
pipelines used to transport supercritical CO 2
and is an expert in sulfide stress cracking. He
has a Ph.D. in metallurgical engineering and
has published more than 90 papers and seven
books. A member of NACE International for
30 years, Craig is a Senior Research Fellow at
the Institute for Corrosion and Multiphase
Flow, Ohio University.
NACE INTERNATIONAL: VOL. 53, NO. 12