Proceedings of the ASME 2012 31st International Conference on Ocean, Offshore and Arctic Engineering
OMAE2012
The Use of Flexible Pipe for CO2 Enhanced Oil Recovery Applications.
C Taravel-Condat
Technip
Le Trait, France
ABSTRACT
The use of CO2 rich gas mixtures as injection fluid is nowadays
considered in order to enhance the oil recovery process.
Flexible pipes, which have been used to transport oil and gas in
offshore applications for more than 35 years, are attractive
products for the transportations of such fluids. The CO2 content
encountered for these applications can be higher than 90%. This
value being superior to what is found in standard applications
(<15%), and CO2 being known to behave as a supercritical fluid
as soon as the temperature and the pressure are higher than
31.1°C, 72.8 atm, the compatibility of the pipe materials with
the CO2 rich gas mixture had to be verified.
This paper will present the qualification work carried out so far
on several thermoplastic materials used for flexible pipe
pressure sheathes and stainless steel carcasses. This
qualification work covers application as high as
90°C/600bar/100%CO2.
The formation of blisters (blistering) is known as a possible
degradation mode of thermoplastic materials when subjected to
rapid gas decompression. This phenomenon is directly linked to
the fluid solubility in the polymer. Different materials have been
tested for their ability to withstand rapid gas decompression in
CO2 rich gas mixtures.
Long time exposure tests have been carried out. The objectives
of these tests were to check the impact of CO2 on the physical,
mechanical and chemical properties of the polymer grades. A
special attention has been brought to the plasticizer effect of
CO2. The impact of supercritical CO2 on the hydrolysis
degradation mode has also been assessed.
July 1-6, 2012, Rio de Janeiro, Brazil
OMAE2012-83321
T Epsztein
Technip
Le Trait, France
Finally, CO2 being a small molecule, it will permeate through
the pressure sheath to reach the annulus. The metallic layers
which are constitutive of this annulus are potentially sensitive to
corrosion phenomenon in acidic conditions. A good knowledge
of the permeation properties of the polymer materials when
subjected to high pressure CO2 is necessary in order to assess
the severity of this annulus and to select the appropriate steel
grade. The results of such tests will also be presented.
NOMENCLATURE
SCCO2 = Supercritical CO2
SC: Supercritical
Tc: Critical temperature
Pc: Critical pressure
CIV: Corrected Inherent Viscosity
SCC: Stress Corrosion Cracking
INTRODUCTION
Flexible pipes have been used for the transportation of
crude oil, gas and water in offshore applications for more than
35 years. They have been also successfully qualified at Technip
for ultra deep water applications up to 3000 m water depth.
Recent oilfield developments in ultra deep water have
needed the use of gas injection lines with very high pressure of
CO2 (few hundred bar) in order to Enhance the Oil Recovery
Process (EOR). Also, for sustainable development, Capture and
Storage of CO2 (CCS) is more and more envisaged using
reinjection lines which also contain very high pressure of CO2.
In these conditions, the CO2 behaves as a supercritical fluid
(SCCO2). Compared to flexible pipes applications up to 2009,
where partial pressure of transported CO2 never exceeded 50
bar in the bore, these new conditions lead to the necessity to
qualify flexible pipe for these applications. Indeed, the flexible
pipe is a combination of polymers and steel layers some of them
1 Copyright © 2012 by ASME
being in direct contact with the transported fluid. In particular, it
is well know that SCCO2 can behave as a good solvent for
polymers and is often used in food and pharmaceutical
industries for extraction. Consequently, the exposition of our
different polymer sheaths with high pressure SCCO2 needed to
be study.
In addition to that, the presence of water in the transported
fluid in conjunction with a high pressure of CO2, will drastically
increases the acidity of the environment by lowering the pH of
the water down to pH 3. Steel carcass layer, which is made of
stainless steel strips may consequently suffer from SCC or
localized corrosion and more corrosion resistant materials may
be necessary to be used.
In a flexible pipe, even layers which are not in direct
contact with the transported fluid may be exposed to high
pressure of CO2: For instance, carbon steel wires which are
located in the annulus are concerned. Indeed, CO2 in the bore
diffuses through the pressure sheath into the annulus giving the
possibility to reach high partial pressure of CO2 (few tenths of
bars). The annulus environment is not necessarily in its
supercritical state but the partial pressure of CO2 may be
sufficiently high enough to give more aggressive environment
for corrosion or corrosion fatigue.
The carcass and the pressure sheath are the only two layers in
direct contact with the fluid transported in the bore.
Consequently, this paper will mainly discuss the effect of
supercritical CO2 on stainless steel constitutive of the carcass
and on the polymer materials that can be used as a pressure
sheath. A brief summary of previous work demonstrating the
suitability of the carbon steel wires in the annulus is also
presented.
Four families of polymer are currently used as pressure sheath
in flexible pipes: polyethylene (PE), crosslinked polyethylene
(XLPE), polyamide (PA) and polyvinylidene fluoride (PVDF).
One of the main parameter governing the choice of the polymer
material is the design temperature of the flexible pipe as
illustrated in Figure 2.

PRESENTATION OF FLEXIBLE PIPE

Figure 1 presents a standard flexible pipe made of the following

layers;
-The first layer is a carcass (1) made of stainless steel. This
layer provides resistance against the external pressure.
-The second layer is a leakproof continuous polymer layer
and is called the pressure sheath (2).
-The third layer sustains internal pressure thanks to a vault
wire (3) spiraled at short pitch.
-The armours (4) are made of one or two pairs of
helicoidally spiraled steel wires and are designed to ensure
tensile load resistance.
-The tightness of the annulus regarding external
environment is ensured thanks to an external sheath (5) made of
polymer.
-If necessary, the thermal performances of the flexible pipe
can be improved thanks to syntactic foam tapes (6).
(6)
(5)
(4)
(3)
(2)
(1)
Figure 2: Classification of Polymer Material Used as Pressure
Sheath in Flexible Pipes.
Another important factor that needs to be taken into account in
the choice of the polymer material is the nature of the
transported fluid. CO2 is a substance commonly found in
standard flexible pipe applications with content very often
inferior to 15%. The fact that this content can be as high as 90%
in EOR applications and that the fluid will consequently be in a
supercritical state needs to be considered when evaluating each
materials ability to be used for such applications.
A first part of this paper will be dedicated to the definition of
what is a supercritical fluid and to the introduction of the
fugacity parameter. For each material (polymer and steel) the
degradation mode that needs to be considered when dealing
with CO2 injection will be recalled. The testing methodology
associated to the degradation mode will be recalled along with
first test results.

Figure 1: Layers of a Typical Flexible Pipe.

2 Copyright © 2012 by ASME

SUPERCRITICAL FLUID DEFINITION
RELEVANCE OF FUGACITY PARAMETER
Supercritical (SC) state is the state in which is a substance when
a high pressure and a high temperature are applied. At a given
critical temperature (Tc) and a given critical pressure (Pc), it is
no longer possible to define a liquid/gas frontier. On the phase
diagram the point with coordinates (T c, Pc) is called the critical
point of the substance. The substance is then in a supercritical
AND
Figure 5 illustrates the difference between CO2 fugacity and
total pressure at 40°C. A significant deviation from ideal gas
behavior (which is characterized by equality between partial
pressure and fugacity) can be seen when entering the
supercritical domain (i.e. above 72.8atm).
1000

state when P>Pc and T>Tc.

A typical phase diagram is presented in Figure 3. CO2 is the

substance which is the most commonly used in its supercritical

PRESSURE (bar)
state. This is due to the position of CO2 critical point which is
100
very close to atmospheric conditions: Tc= 31.1°C, Pc=72.8atm.

SOLID SUPER CRITICAL

10
10 100 1000
LIQUID FUGACITY (bar)
PRESUURE

Critical Point

Figure 5: Variation of CO2 Fugacity as a Function of Pressure at

40°C
Triple Point

It must be noticed that even for standard applications, fugacity

GAS
can be used to quantify precisely the chemical activity of the
substance transported in the bore, for example in the realization
of permeation calculation to predict the flexible pipe annulus
TEMPERATURE composition. The fact that fugacity based annulus predictions
are in better agreement with measurements than prediction
Figure 3: Temperature – Pressure Phase Diagram based on partial pressure has been a major conclusion of a Joint
Industry Project called ‘Permeation, Corrosion and Corrosion
In practice, the supercritical state is often referred as a state of Fatigue [1].
intermediate properties between a gas and a liquid. This fact is
presented in table in Figure 4. The same way of thinking applies to pH calculations when
dealing with CO2 dissolved in an aqueous phase. As presented
Properties Liquid SuperCritical Gas in Figure 6, when dealing with CO2 pressure above 50 bar, the
Density g.cm -3 1 0.1 to 0.5 0.001 hypothesis of a linear relationship between CO2 partial pressure
Diffusivity cm 2 .s -1 0.00001 0.001 0.1 and CO2 concentration in water is no longer correct. Calculating
Viscosity Pa.s 0.001 0.00001 0.000001 CO2 concentration using CO2 fugacity as input parameter allows
taking into account for some of this non-linearity while
Figure 4: Fluids properties – Order of magnitude remaining conservative.

Most of the degradation modes that need to be taken into

account when verifying a material ability to work in contact
with CO2 in supercritical state are linked to CO2 chemical
activity (either directly or through a pH calculation). Partial
pressure is commonly used to quantify the chemical activity of a
substance in a gaseous phase. This use of partial pressure is
correct when dealing with a substance which behaves close to
an ideal gas. A more precise evaluation of this activity will be
achieved through fugacity when dealing with a substance in
supercritical state.

3 Copyright © 2012 by ASME

 5 Gas Number of Decompression
Temperature Total Pressure CO2 Fugacity
composition Pressure Rate
Carbon Dioxyde Concentration in Water

4.5 °C Cycles bar bar bar/min

Experimental data from RGD Test between 25
4 250 121
Hangx [2] at 50°C expressed XLPE n°1 and 70
3.5 in partial pressure RGD Test
250 121 70
XLPE n°2
80°C 100%mol CO2 20
3 RGD Test between 40
(mol/kg)

350 151
Experimental data from XLPE n°3 and 70
2.5 RGD Test
Hangx[2] at 50°C expressed in
350 151 70
fugacity XLPE n°4
2

1.5
Carbon Dioxyde concentration
1 used at 50°C in pH Figure 7: CO2 RGD Tests Performed on XLPE Without Observation
0.5
calculations as a function of of Blistering.
CO2 partial pressure
0
0 100 200 300
PRESSURE or FUGACITY (bar)

Figure 6: CO2 Concentration in Water as a Function of Pressure or
Fugacity at 50°C [2].
SUPERCRITICAL CO2 RAPID GAS DECOMPRESSION
TESTS
The thermoplastic polymers, to which belong all the materials
used as pressure sheath in flexible pipe, are known to present a
good resistance to Rapid Gas Decompression (RGD) events in
comparison with elastomeric materials for example.
However, as specified in API 17J [3], the resistance of each
material to such event needs to be verified. For standard
applications, this verification is performed by exposing the
material to a gas mixture composed in majority of CH4 by
performing pressure cycles between the test pressure and
atmospheric pressure. The decompression rate is 70bar/min.
The test is performed at a pressure and a temperature equal or
superior to the pressure and the temperature of the targeted
application. After a minimum number of 20 cycles, the samples
are examined. The acceptance criterion is that no blister or
slitting is observed at the end of the test.
LONG TIME SUPERCRITICAL CO2 EXPOSURE TESTS
In order to assess the impact of CO2 in its supercritical state on
the mechanical and chemical properties of thermoplastic
materials used as pressure sheath in flexible pipe, exposure tests
as long as 6 months have been performed on PVDF and PA
materials. The testing conditions for such exposure tests are
generally between 400 and 600bar. The temperature can be as
high as 90°C. The fluid is a CO2 rich gas mixture with CO2
content as high as 90%mol. Tested specimens have dimensions in
accordance with ASTM D638 type IV. Samples are placed in a
testing vessel are presented in Figure 8. As exposure test are
followed by mechanical characterisations, oxidation is a
concern. Before the start of the test and after each sampling, a
special attention is brought to the removal of oxygen in order to
avoid this phenomenon. Every month, five tensile test
specimens are taken out of the vessel in order to be tensile
tested at room temperature.

Considering the fact that CO2 injection applications will lead to

a significant change in the gas composition, (methane no longer
the main component to be considered), specific RGD tests have
been performed using CO2 rich gas mixture (≥90%molCO2) on
XLPE, PA and PVDF materials.

Figure 7 presents the RGD tests performed on XLPE with pure

CO2 and for which no blister has been observed. These results
show that at 80°C this material can sustain RGD events from
pressure as high as 350bar when tested with pure CO2. Figure 8: PVDF Samples Placed in a Vessel After CO2 Exposure
Test

Figure 9 and Figure 10 illustrates the impact of such exposure

on the mechanical performances of a low plasticized PVDF.
After 1 month, a decrease of the Young’s Modulus is observed.
Such behavior is typical of a softening of the material induced
by CO2 solubility in PVDF. CO2 acts as a plasticizer of the
material. The fact that the modulus is then constant during the

4 Copyright © 2012 by ASME

last five months is a confirmation that this initial change is not confirm that exposure to CO2 rich gas mixture does not lead to
linked to any chemical degradation of the PVDF thermoplastic. any chemical degradation of the PVDF material.
Such a conclusion is also supported by the results presented in
1.40
Figure 10: during the six months of exposure the elongation at
break remains at a level equivalent to what was measured on the 1.20
un-aged material, and in any case well above what is required
1.00
for a flexible pipe pressure sheath applications.
0.80
1200
0.60 Mw aged / Mw unaged
1000 0.40
Mn aged / Mn unaged
800 0.20

0.00
600

400 Young's Modulus

(Mpa)
200

Figure 11: Evolution of a Low Plasticized PVDF Weight-average

0
and Number-average Molecular Weight during CO2 Exposure Test.

Figure 9: Evolution of a Low Plasticized PVDF Young’s Modulus

during CO2 Exposure Test.

300

250

200

150

100 Elongation at
Break (%)
Figure 12: Comparison of a PVDF Molecular Weight Distribution
50 Unaged and after 4, 5 and 6 months of Exposure to CO2 rich gas
Mixture.
0

SUPERCRITICAL CO2 PERMEATION TESTS

Thanks to the polymer pressure sheath, there is no direct contact

Figure 10: Evolution of a Low Plasticized PVDF Elongation at
Break during CO2 Exposure Test.
In addition to the mechanical characterization, the chemical
properties of the exposed PVDF are assessed. After each
sampling, the molecular weight distribution of the PVDF is
compared with the molecular weight distribution of un-aged
PVDF. Both the number-average molecular weight Mn and the
weight-average molecular weight Mw are reported. As presented
in Figure 11 and Figure 12, no evolution of the molecular
weight is observed during six months of exposure. These results
between the fluid transported in the bore of the flexible pipe
and the steel layers sustaining internal pressure and axial
tension. However, over a long period of time, active
components such as water, carbon dioxide and hydrogen
sulfide, will permeate through the polymer pressure sheath. This
permeation phenomenon, which is mainly activated by
temperature and by each component chemical activity (quantify
through partial pressure or fugacity) [4], is taken into account in
the design of every flexible pipe thanks to a dedicated fluid
permeation model [5].

5 Copyright © 2012 by ASME

The quantity of CO2 that can permeate through a given pressure
sheath per unit of time can be calculated through the following
equation
With
the CO2 permeability coefficient of the material
constitutive of the pressure sheath
the thickness of the pressure sheath
the surface area of the sheath in contact with the fluid
the fugacity of CO2 in the transported fluid
This permeability coefficient is measured through the
realization of permeation tests which consist of applying a given
pressure of CO2 on one side of a sealed membrane of the
material you want to characterize and on measuring the amount
of CO2 that can be transported through the membrane. When
steady state is achieved, a constant flowrate of CO2 can be
measured. This flowrate is then divided by the active surface of
the membrane, divided by the fugacity of the gas upstream and
multiplied by its thickness to calculate the CO2 permeability
coefficient.
Figure 13 illustrates the result curve obtained during a
permeation test and giving the amount of gas permeating
through the membrane as a function of time.
Figure 13: Result curve of a permeation test.
For standard flexible pipe application, the CO2 permeability
coefficient is measured through permeation test performed with
a CO2 total pressure inferior to 50 bar.
Specific permeation tests have been performed on PA and
PVDF material at higher pressure of CO2 with the objective of
studying the effect of CO2 total pressure on the CO2
permeability coefficient. Figure 14 and Figure 15 present the
result of these tests. In both cases, the data presented have been
obtained considering CO2 fugacity as the governing parameter
for permeation.
In the case of the PA material (Figure 14), increasing the CO 2
pressure up to 500 bar appears to lower significantly the CO2
permeability coefficient. On the other hand, an increase of
pressure does not appear to modify significantly the permeation
properties on the low plasticized PVDF materials. Additional
tests under CO2 high pressure at higher temperature are
currently performed on this material to confirm this tendency.
K CO2 measured below 50bar
K CO2 measured at 80 bar
K CO2
K CO2 measured at 300bar
K CO2 measured at 500bar
TEMPERATURE
Figure 14: Effect of CO2 Pressure on CO2 Permeability in a Non
Plasticized PA Material
K CO2 measured below 50
bar
K C02
K CO2 measured between
200 and 400 bar
TEMPERATURE
Figure 15: Effect of CO2 Pressure on CO2 Permeability in a Low
Plasticized PVDF Material
One hypothesis that can be made to explain the decrease of
transport properties in the PA material is that a higher total
pressure induces a compressive stress on the material which
lowers the free volume known to play a significant role in the
permeation phenomenon occurring in thermoplastic materials.
As observed during long time CO2 exposure tests, PVDF
appears to have a higher affinity regarding CO2. One can think
6 Copyright © 2012 by ASME
that CO2 plasticizer effect can be responsible for an increase of
the permeation properties which counter-balances reduction of
free volume induced by compressive stress. These two opposite
effects would then be responsible for the apparent low impact of
CO2 total pressure on the permeation properties of PVDF.
1203 h and 2150 h. In addition to the CIV measurements,
volume and mass changes were measured on ASTM D638 Type
IV specimen. It is important to outline that the test solution was
thoroughly de-aerated in order to reach less than 5 ppb of
residual O2 in the water at the beginning of each period. This
strict de-aeration is necessary to reproduce flexible pipes
conditions in the bore and in order to avoid any oxidation of the
samples that could accelerate the ageing process.

HYDROLYSIS UNDER SUPERCRITICAL CO2

Rilsan® P40 is a polyamide 11 mainly used in flexible Test results

pipes for pressure sheath in direct contact with the transported
fluid. This semi-crystalline polymer can sustain high The mass and volume changes were as expected. Indeed, a
temperature applications up to 100°C but is however limited by mass loss of (-7,5% in average) and a volume loss of (-6% in
hydrolysis in presence of hot acid water. Hydrolysis in hot water average) were measured after 2150h of test, corresponding to
depends on the temperature and on the pH which itself depends the progressive loss of plasticizer during ageing at 120°C (see
on the fugacity of CO2 and on the water composition. Figure 16). The evolution of CIV versus ageing time is
During hydrolysis, modifications of the polyamide structure presented in the Figure 17. We observe a decrease of CIV from
occur: the polymer chains are cut leading to a decrease of the its initial value (non aged) to a ‘plateau’ at end of the test. CIV
molecular weight and inherent viscosity and to an increase of evolution obtained during this test has been compared to the
the cristallinity. Also, at its final stage, the material may become one obtained using our ageing model based on APITR2 at pH
brittle. During the work conducted in the 90’s in the frame of 3.19 and at pH 3 (see Figure 17). We can see that the model fits
the Rilsan User Group, a methodology was proposed to follow quite well the CIV measurements and is a little bit conservative.
the hydrolysis of PA 11 in hot acid waters [3, 6, 7]. The main In conclusion, this study showed that even during
conclusion of this work was that the hydrolysis can be followed hydrolysis test at very high pressure of CO2 during 3 months, in
by measuring the evolution versus time of the Corrected CO2 conditions giving a low pH of 3.19, Rilsan® P40 shows no
Inherent Viscosity (CIV) of the material. Acceptance criteria extra degradation compared to hydrolysis test in the same
were also defined for static and dynamic applications and a conditions using strong acid. This test also demonstrates that
kinetic model was proposed. our ageing model used today below pH 4 is applicable at high
To study the hydrolysis of PA 11, tests are generally pressure CO2 down to pH 3.
conducted in autoclaves in different conditions of pH and
temperature and for several durations. In Technip, numerous
tests were conducted to establish the kinetic model between pH
2 and pH 7. Most of the time, the acidification of the water
between pH 4 and pH 7 was obtained using CO2 in equilibrium
with the water. On the other hand, below pH 4, the pH was
obtained using strong acids like phosphonic or hydrochloric
acid; this type of acidizing being different of the acidification
cause in flexible pipes.
For this work relative to the qualification of PA 11 Rilsan
P40 for SCCO2 applications, we conducted a hydrolysis test at
low pH using a very high pressure CO2 in supercritical
conditions instead of strong acids.

Hydrolysis procedure in SCCO2 conditions

This test was conducted at 350 bar CO2 and 120°C, using
spring water whose composition is known. In such conditions,
the pH has been calculated to be 3.19 with CORMED 2 Figure 16: Rilsan® P40 specimen after 1203 hours of hydrolysis at
program and using CO2 fugacity (190 bar). The duration of the 120°C – 350 bar CO2 - pH 3.19 compared to a non aged specimen
test was 2150 hours (roughly 3 months). During the test, (‘control’)
samplings of specimen were done periodically in order to
follow the evolution of the Rilsan P40 properties with time. At
total, 6 samplings were done after 23 h, 88 h, 252 h, 653 h,

7 Copyright © 2012 by ASME

 to calculate the fugacities of CO2 and H2S during tests in
SCCO2 conditions.
First results obtained demonstrated that Duplex 2205,
CIV measured
experimentally after Superduplex 2507 and Alloy 31 are qualified in supercritical
ageing at pH 3.19
CO2 for conditions covering both gas injection and production
conditions of this project.
CIV from ageing model at
CIV

pH3.19 This testing programme is still on going. One objective for

the future is to extend this programme to other carcasses grades
like lean Duplex and Austenitic 316L, mainly for gas injection
applications where there is no chloride in water. In addition to
that, corrosion tests at higher temperature than 90°C will be
done for production conditions.
TIME
Carbon steel Wires
Figure 17: Evolution of the CIV of Rilsan® P40 during Hydrolysis
Carbon steel pressure and tensile armours are not in direct
test at 120°C – 350 bar CO2 - pH 3.19
contact with the transported fluid, because they are located in
the annulus space above the pressure sheath. However, it has
STEELS QUALIFICATION IN SUPERCRITICAL CO2
been described previously that wires can be in contact with
water, CO2 and H2S due to gas diffusion of some bore
Carcasses
components into the annulus. The corrosivity of the annulus
environment was strongly studied during the last 12th past years
Carcasses in flexible pipes are made of different stainless
[9]. It was shown that the annulus is much less corrosive than
steel grades: for instance, Ferritics F12T (UNS S40900),
expected due to the high confinement rate of the wires which
Austenitics 316L (UNS S31603), Lean Duplex 2304 (UNS
leads to an environment oversaturated with iron, with the
S32304) and Duplex 2205 (UNS S31803). Recently, higher
consequence of a high pH and low corrosion rate. Nevertheless,
corrosion resistant materials have been qualified [8]: Super-
all these studies were based on tests done in conditions were the
Duplex 2507 (UNS S32750) and Alloy 31 (UNS N08031).
partial pressure of CO2 rarely exceeded 2 or 3 bars. In SCCO2
The choice of the carcass grade for a flexible pipe depends
applications, partial pressures of CO2 could sometimes reach a
mainly on its mechanical resistance to sustain collapse pressure
few tenth of bar so that it was clear for us that our domain of
and on its resistance to corrosion toward transported fluid. The
test had to be extended.
corrosivity of the fluid depends on different parameters:
Different programmes started then. The study on corrosion
presence of liquid water, fugacity of CO2, presence of H2S, pH,
rates and evolution of pH under high pressure of CO2 is on
chloride content in water and temperature.
going. For corrosion fatigue, it has been necessary to built new
For applications containing high pressure of CO2 (> 50
tests benches able to reach high pressure. Two new laboratories
bar), we have seen that the pH of the fluid may reach low values
have been qualified. Today more than 20 corrosion fatigue
down to 3 which were not tested before 2009. For that reason, it
benches are able to work at high pressure CO2, some of them up
has been necessary to explore this new domain by conducting
to 50 bar. You will find in Figure 18 a photograph showing a
corrosion tests on different carcasses grades and to see how
corrosion fatigue bench in one of our qualified laboratory. For
much their domain of use can be extended at low pH. For a
CO2 conditions with some amount of H2S, it has been shown the
specific project, several tests were performed at high CO2
importance to renew continuously the gas during the test in
pressure between 100 and 400 bar up to 90°C. In a first phase,
order to guaranty a stable gas composition. Indeed, without gas
corrosion resistant alloys like Duplex 2205, SuperDuplex 2507
circulation, the H2S is consumed by the large amount of steel
and Alloy 31 were chosen. Conditions simulating both Gas
used to reproduce annulus conditions. The autoclaves built for
Injection conditions (CO2 pressure between 300 bar and 400
this programme allow the continuous gas renewal even at 50 bar
bar, no chloride, 90°C) and Production conditions (100 bar CO2
pressure. Corrosion fatigue tests at high pressure of CO2 are
partial pressure, presence of Chlorides 90°C) were investigated.
today on going. Results will be described later in another paper.
In all the tests, some amount of H2S was added. The test
procedure is presented in details in reference [8]. Compared to
the tests conducted classically, the main difficulty was to find
autoclaves able to conduct tests at very high pressure for gas
injection conditions. In addition to that, one difficulty was also
in some cases to reproduce the real fluid conditions in term of
fugacities of CO2 and H2S. A significant work was done to
qualify new laboratories and to put in place new methodologies

8 Copyright © 2012 by ASME


Figure 18: Corrosion Fatigue Facility for High Pressure
CONCLUSION
A qualification programme was launched in 2009 to qualify
flexible pipes for transportation of Supercritical CO2 fluids.
This program consists in testing polymers materials used as
pressure sheath and steels grades at very high pressure of CO2
(up to 600 bar). Different types of tests were conducted:
Exposure tests up to 6 month duration, RGD and Permeability
tests for polymers, Corrosion and Corrosion Fatigue for carcass
strips and armours wires. To perform this program, new
equipments were built, more laboratories were qualified and
also new methodologies were put in place.
Today, Technip can propose flexible pipes solutions for
SCCO2 applications for gas injection lines as well as production
line with high level of CO2. Some solutions are already
operating.
This programme is still going on with the aim to qualify
more materials in the future, more particularly new polymers
materials developed recently.
ACKNOWLEDGMENTS
The authors would like to acknowledge all the laboratories
which have participated to this study, including Flexifrance
PED laboratory for their help in the characterisation of the
materials after testing.
REFERENCES
[1] OTC 14065 – ‘Comparison of Models to Predict the
Annulus Conditions of Flexible Pipes’ – May 2002, Houston.
[2] S.J.T.Hangx – Behaviour of the CO2-H2O system and
preliminary mineralization model and experiments. PhD project
report supported by Shell International E&P.
http://science.uwaterloo.ca/
[3] – API17J Third Edition 2008‘Specification for Un-bonded
Flexible Pipe’ (ISO 13628–2: 2006)
[4] B.Flaconneche, M-H.Klopffer, J.Martin, C.Taravel
Condat, ‘High Pressure Permeation of Gases in Semicrystalline
Polymers: Measurements Method and Experimental Data’,
M.E.R.L 2001.
[5] C.Taravel Condat, M.Guichard, J.Martin, ‘MOLDITM: A
Fluid Permeation Model to Calculate the Annulus Composition
in Flexible Pipes: Validation with Medium Scale Tests, Full
Scale Tests and Field Cases’, OMAE 2003 Paper 37193
[6] – API Technical Report 17TR2: ‘The ageing of PA 11 in
flexible pipes’: First edition June 2003
[7] – J Jarrin, A Driancourt, R Brunet, B Pierre: ‘Durability
of Polyamide 11 for Offshore Flexible Pipe Applications:
Offshore Technology Conférence Proc: 5231, 1-9 1998
[8] – E Remita, D Marchand, C Taravel Condat :
Qualification and Industrialization of SuperDuplex and Alloy
31 carcasses for unbounded flexible pipes applications;
Conference Duplex Beaunes 2010.
[9] C. Taravel-Condat, N. Desamais, “Qualification of very
high strength carbon steel wires for use in flexible pipes with
presence of small amount of H2S”, Eurocorr 2006, Maastricht,
(2006).
9 Copyright © 2012 by ASME