SPE 134473

CO
2
-Induced Changes in Oilwell Cements Under Downhole Conditions:
First Experimental Results
Andr GARNIER
1
; Jean-Benot LAUDET
1
, Nadine NEUVILLE
2
, Yvi LE GUEN
2
, Dominique FOURMAINTRAUX
3
,
Noureddine RAFAI
4
, Nicolas BURLION
5
, Jian-Fu SHAO
5

1:
TOTAL - Centre Scientifique et Technique Jean Feger, avenue Larribau, 64000 Pau (France)
2:
OXAND SA - 49 avenue Franklin Roosevelt, 77210 Avon (France)
3:
DFi Ingnierie - 11 bis rue du Glazen Kervarlay, 56680 Plouhinec (France)
4:
LERM - 23 rue de la Madeleine, BP 60 136 - 13631 Arles Cedex (France)
5:
LML - UMR CNRS 8107, PolytechLille, Universit Lille1, Cit Scientifique, 59650 Villeneuve dAscq, France (France)



Copyright 2010, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Annual Technical Conference and Exhibition held in Florence, Italy, 1922 September 2010.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been reviewed
by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its officers, or
members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is
restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.


Abstract

One of the major technological issues for CO
2
injection (for EOR, CCS, etc.) is the long-term behavior of cement-based materials
used to ensure the overall sealing performance of the storage wells. When water is present, the CO
2
after injection can react
chemically with the cement (i.e. carbonation).
How do the CO
2
-enriched formation fluids changes the cements chemistry and properties? Could the sealing efficiency of the
wells be affected by these changes?

The objectives of our experimental program are to assess the kinetics and phenomenology of the changes that occur in different
class-G Portland cements exposed to CO
2
-enriched aqueous fluids at 8 MPa and two different temperatures.

The experimental program presented in this paper consists of: a first carbonation test (Test # 1) using neat G cement, at a
temperature of 90C (194 F) and a pressure (supercritical CO
2
above water) of 8 MPa (1160 psi); a second carbonation test (Test
# 2) using G cement with silica flour (to prevent strength retrogression), at a temperature of 140C (284F) and at the same CO
2

pressure of 8Mpa. Finally, coupled chemo-mechanical tests (dynamic tests) are underway on similar class-G cement and similar
CO
2
-rich water.

All the samples were prepared according to ISO/API specifications. The experimental set-up simulates downhole static
conditions: the samples were immersed in water in a cell thermally regulated and pressurized by CO
2
. Cement samples were
exposed to CO
2
-saturated water for various lengths of time (from one week to 3 months) and were characterized using advanced
methods for chemical and mineralogical analysis (X-ray tomography, SEM, XRD, TGA-TDA) and mechanical testing.

The main preliminary results show a reactive front (characterized by carbonation) progressing from the fluid-sample interface
towards the sample centre. The carbonation front moves faster during Test 2 (at higher temperature) than during Test 1 (at lower
temperature). SEM images of Test 2 also show a thin layer of dissolved carbonate at the samples surface. The carbonated cement
areas exhibit increased density and greater compressive strength.

The results of coupled chemo-mechanical tests with injection of CO
2
-enriched water in samples under deviatoric stress show that
the CO
2
flow rate in the cement rapidly decreases, finally resulting in carbonation clogging of the cement sample. These results
seem consistent with reported field observations.

2 SPE 134473
Introduction

When CO
2
is injected into a well, for various purposes (EOR: Enhanced Oil Recovery, CCS: Carbon Capture & Sequestration,
etc.) [Noik et al., 1998] the wells integrity becomes a major concern due to the acidic environment CO
2
creates when in contact
with water.
Well cementing is devoted to providing long-term zonal isolation and offering protection to the casing supporting the wellbore.
Long-term durability of the cement-based materials is therefore of paramount importance in this operation to guarantee the
tightness of these wells. The cement sheath has to ensure containment of the injected CO
2
in a specific geological layer (e.g.
depleted reservoir) without any leakage of CO
2
outside that selected layer.
Cement can be damaged by aggressive environments: (i) failure under mechanical stresses that can induce cracks (ii) chemical
degradation in acidic environments that can alter cement properties.
The available papers and discussions in conferences show that many experimental set-ups have been developed to increase
understanding of the behavior of oilwell cements under severe conditions, with respect to chemical attack by CO
2
. The main
results return contradictory feedback about the CO
2
reaction with cement [Mulders, 2007]. So Total decided to launch a research
program directed at characterizing the long-term behavior of Portland cement in a CO
2
environment. Portland cement (class G or
H) was selected as it has been the cement most commonly used by the Oil & Gas industry in well construction for decades. The
ongoing research program is focused on two objectives: (i) to assess the risk of injecting CO
2
in fields connected to old wells
cemented with Portland cement, and (ii) to evaluate the relevance for the industry today of using Portland cement as the base
component of most composite cements when drilling new wells in fields where CO
2
is already present.

Strategy

The experimental program is devoted to oilwell cement behavior at high temperature and pressure conditions with the aim of
improving knowledge concerning its long-term behavior in the presence of acid gases, and in terms of phenomenology, reaction
kinetics and evolution of the cements properties. The strategy implemented includes different sets of experimental tests (Table 1)
and numerical modeling.
The experimental tests and lab characterization methods have to be suitable to qualify the long-term zonal isolation of cement
sheaths in downhole conditions in the presence of CO
2
, including time effects (long-term and accelerated tests).
Tests with samples cured for a short period ( 1 week) refer to wells drilled in a formation already containing CO
2
, other tests with
samples cured for several months represent cement sheaths exposed to CO
2
after a long period of time.

This paper focuses on static and dynamic tests, which are the most advanced ones.

What kind of test? Why? Which characterization?
- Neat class-G cement curing (> 1 month)
- Class G + silica flour: short- ( 1 week)
and long-time curing (> 1 month)
Ensure reproducibility, quality control
(homogeneity)
Assess the impact of the curing time on
initial cement properties
Slurry: rheology, stability
Hardened material: X-Ray tomography
Static carbonation tests Assess phenomenology and the kinetics
of damaging processes

Damaging front progression; X-ray
tomography
Chemical evolution (sample and leachants)
Mechanical properties (micro-hardness,
triaxial test, UCS)
Transport properties (Porosity, Permeability)
Dynamic tests (coupled chemo-mechanical
test, CO
2
-rich aqueous fluids flux in cement
samples under triaxial stresses)
Assess mechanical and transport
properties
Mechanical properties: evolution of
deformation with time (creep test: time-
dependent behavior )
Transport properties : flowrate, permeability)
Characterization tests on completely
carbonated cement samples [Ollivier, 1997]
[Fernndez Bertos et al. 2004], and
completely lixiviated samples
Assess the mechanical and transport
properties of completely carbonated
cement samples and completely lixiviated
samples
Chemistry: chemical analyses, mineralogy,
SEM
Mechanics: triaxial tests, time dependent
creep tests
Table 1: Experimental strategy of the research program Ongoing lab experiments


Material and Method used for Static Tests

Material: sample preparation and control

Portland cement was prepared with the usual additives (we used Schlumberger: D153 antisettling, D604AM dispersant, D47
defoamer) according to ISO/API specification and hardened in cylindrical molds (diameter = 20 mm, height = 240 mm) in
SPE 134473 3
curing chambers using lime-saturated water. The first material used is neat class-G cement; the second is class-G cement with
addition of silica flour (35% bwoc). Adding silica flour produces secondary hydrates by pozzolanic reaction with the lime resulting
from primary hydration (SiO2+Ca(OH)2CSH), thereby avoiding strength retrogression during the hardening period due to
C
2
SH formation at 140C [Hewlett, 1991] [Taylor, 1997] [Meller et al., 2005].

A carefully followed QA/QC program requires that, before being molded, samples should display neither free water nor
sedimentation nor visible heterogeneity by X-ray tomography (e.g. air bubbles) so that all samples are homogeneous and similar.

The cement slurries were cured for more than 28 days under different conditions: the neat class-G cement at 90C and at
atmospheric pressure (for carbonation test at 90C); the class G + silica flour cement at 140C and 20.7 MPa (3000 psi) for the
first 10 days, then at 90C and at atmospheric pressure (for the carbonation test at 140C).
The curing conditions used for the class-G + silica flour cement represent a cement sheath rapidly exposed to CO
2
after well
drilling. Other tests are under way with cement cured for several months to represent a cement sheath exposed to CO
2
after a long
period of time.

After the curing periods, the cement samples were controlled by X-ray tomography to avoid any visible heterogeneities within the
bulk of the cement (as shown in Figure 1 for 2 samples of class G + silica flour cement). X-ray tomography images are used as
reference to assess the impact of test conditions during the tests.

Neat class-G cement samples have a porosity of about 30% and contain mainly amorphous phases (associated with calcium silicate
hydrates, or C-S-H, 67% wt.), portlandite ( 17% wt.) and katoite ( 8% wt.).
Samples of class-G cement with silica flour have a porosity of 28% and contain mainly C-S-H ( 67% wt.), quartz ( 10% wt.) and
katoite ( 7% wt.).

In order to obtain a 1-D progression of the reaction front during the carbonation tests, the cylindrical surface of the samples was
protected by PEEK (polyetheretherketone).


Method: Experimental Setup

Batch experiments were carried out in steel reactors under static conditions. Two sets of experiments (test#1, test#2) were
performed with supercritical CO
2
pressurized at 8 MPa (1160 psi). One type of cement was used for each temperature:
Test #1: neat class-G cement at 90C (194 F);
Test #2: class-G cement with 35% bwoc silica flour at 140C (284F).

The experimental setup is the same for static tests #1 and #2. Cement samples were cut after the curing period (diameter = 20 mm,
height = 40mm) and positioned 4 by 4 on a 3-tier sample-holder (12 samples in each cell, Figure 2). The sample-holder is placed in
a glass beaker filled with distilled water at 90C (about 350 ml) and the glass beaker is placed in the cell preheated at 90C.
Throughout the entire experiment, the samples are fully immersed in and covered by the water (Figure 2) which is in contact with
the CO
2
at 8 MPa. They are exposed for only a few seconds to air when removed from the cells and placed in storage flask for
characterization.

The cell is closed and CO
2
is injected into it, regulated at the selected temperatures: 90C or 140C. In order to avoid
thermal/mechanical stress within the samples while pressure and temperature increase, CO
2
pressure is increased gradually and
regularly from 0.1 MPa to 8 MPa at a rate of 0.2 MPa / minute (about 15 psi/min). Temperature is raised from 90C to 140C for
test #2 at a rate of 2C / minute (no temperature increase for test #1).

The injected CO
2
dissolves in the water until equilibrium is reached. The CO
2
concentration in aqueous solution can be estimated
from literature: CO
2
solubility in pure water is about 0.7 mol.kg
-1
H
2
O at 90C (Test #1) and about 0.6 mol.kg
-1
H
2
O at 140C
(Test #2) (Figure 3, Span et al. 1997).

The CO
2
-saturated aqueous solution thus formed reacts with the cement samples. Due to the dissolution of CO
2
in the water and
the chemical reactions with the samples, the CO
2
pressure has to be regularly adjusted during both tests to maintain it at 8 MPa.
Throughout the tests, CO
2
pressure (see Figure 4) and temperature are recorded. No variation in temperature was observed during
exposure of the samples to CO
2
.

At different points in time during the tests, two cement samples are removed from the cell: for test #1 (neat G cement at 90C)
after 7, 36, 65 and 90 days and for test #2 (G cement with 35% silica flour at 140C) after 4, 12, 21, 31, 55 and 88 days. To prevent
any mechanical damage to the samples due to depressurization, pressure and temperature are slowly decreased before opening the
4 SPE 134473
cells. Then, the two samples are weighed (for the mass measurements, samples are swabbed beforehand in a paper towel in order
to remove the excess water), and characterized by X-Ray tomography and complete chemical analysis.

At the end of each carbonation period in both tests, the fluid in the glass beaker is collected for chemical analyses, and replaced by
fresh distilled water at 90C to ensure that the aggressiveness of the solutions is kept high throughout the duration of the tests.


Results

Test #1 CO
2
test at 90C and 8 MPa with neat class G cement

This test is still running. Only the mass evolution and X-Ray tomography results are available for the period up to 65 days of
testing. The chemical and mineralogical analyses are ongoing.

X-ray tomography and mass variation increase

Figure 5 shows X-ray density in planar sections crossing the centre of each sample at different times. After 7, 36 and 65 days, only
two zones with different X-ray density are visible in the samples: the initial (un-reacted) cement and the modified (reacted)
cement. The modified material has a greater X-ray density than the initial cement. The increase in sample mass with time is
consistent with the increase in X-ray density, and maximum mass increase is 6% after 65 days of exposure. The lateral protection
(PEEK) is partly effective at 90C, even though zones of reacted cement are visible at the side of the samples.

Kinetics of the reaction fronts progress

Figure 6 shows the position of the carbonation front in the samples at different times during the test (measured from X-ray
tomography images, on the basis of visual contrasts in gray levels). The reaction front progresses linearly with the square root of
time for the first 65 days of test #1. The average thickness of the reacted zone is about 4 mm after 65 days of testing. This
corresponds to an average kinetics of the reaction front of about 9.3 mm.yr
-1/2
.


Chemical analyses of the leachant

Calcium and silicon released in the CO
2
-rich solution by each cement sample are respectively 28 and 29 mg after 65 days (Figure
7). Calcium is usually the most soluble ion during cement degradation processes; considering an initial CaO content in the material
of about 50%, the cement samples lose about 0.5% of calcium after 65 days of testing, which is low compared to other degradation
processes in natural fluids [Neuville, 2008], or pure water ([Kamali et al. (2008) showed that the leached calcium after the same
experimentation time is by two orders of magnitude higher in the presence of pure water). This result indicates that the main
cement degradation process involved in this test is not calcium leaching, but internal calcium carbonate precipitation, namely
carbonation.

Test #2 CO
2
test at 140C and 8 MPa with class-G cement + 35% bwoc. of silica flour

X-ray tomography and SEM observations

X-ray tomography images (Figure 5) show progression of a carbonation front from the outer surfaces to the centre of the samples
over the course of the test. The outer ring (i.e. the reacted zone) is characterized by an increase in x-ray density. Only one front is
observed, separating two zones of cement with different X-ray densities. At the end of the experiment, after 88 days, the entire
sample has reacted. No fracture is visible in the samples during the test.

Alteration is observed on the samples cut from the lateral surfaces, whereas unidirectional attack was expected; this was due to the
PEEK ribbons ineffective protection.

Additional analyses of the X-ray tomography data highlight the initial observations. Figure 8 shows cumulated frequencies of X-
ray densities respectively in the initial and reacted cement samples after different exposure times. The proportion of higher X-ray
density values (from 1650 to 1850) increases with time of exposure, reflecting the densification of the samples.

Mass measurements on carbonated samples are consistent with these results: the maximum mass increase is about 14% after 88
days of exposure.

SPE 134473 5
SEM observations by BSE (Back Scattered Electrons) images (Figure 9) show the presence of three different zones in the samples:
an inner zone of initial cement, then a carbonated zone, and finally a thin zone characterized by higher-porosity material close to
the sample surface. These layers are too thin to be seen by X-ray tomography.


Kinetics of the carbonation fronts progress

In the same way as for Test #1, X-ray density images were used to locate the position of the carbonation front in the samples at
different points in time during the test (Figure 10). The thickness of the reacted cement increases linearly with time: the kinetics of
the carbonation process is about 0.2 mm.d
-1
(i.e. 73 mm.year
-1
) for the 88 days of test #2.


Chemical analyses of the leachant and mineralogical analyses of the carbonated cement samples

Mineralogical analyses of the carbonated cement samples

In order to assess the evolution of carbonate content, thermogravimetric analyses (TGA) were performed on an initial sample
(sample before test #2) and on the carbonated samples removed from the cell after different lengths of time. Each analysis was
carried out on powders (about 100 mg) sampled every 2 mm from the surface to the core of each sample. Analysis conditions were
as follows: temperature increase from 20 to 1000C in increments of 10C/min. Nitrogen was flowed into the chamber (flow rate
=60 ml/ min) to avoid additional cement carbonation during the analyses.
The results indicate that the initial sample contains no calcium carbonate (CaCO
3
), while the most carbonated samples (i.e.
obtained at the end of the test after 88 days) contain from 30 wt% (in the centre of the samples) to 55 wt% (in the outer part of the
samples) of calcium carbonate (Figure 11), mainly aragonite and calcite.

The presence of neo-formed calcium carbonate results from the reaction between CO
2
and cement hydrates. This explains the
increased mass of the samples and the greater X-ray density values observed in their outer part.

Chemical analyses of the leachant

The cumulated masses of calcium and silicon released into the solution by each cement sample after 88 days of testing (Figure 12)
are respectively 460 and 167 mg. Considering that their initial CaO content is around 39%, the cement samples lose about 8.8% of
calcium after 88 days of testing.
This result shows that the process of cement carbonation is brought about mainly by internal carbonate precipitation as observed
during test #1. The more porous outer layer, visible only in the SEM images of Figure 9, may explain the greater calcium
quantities in the leachant compared to the test at 90C.


Chemo-Mechanical Tests (dynamic test)

Cement that is set in a well can be exposed to a number of mechanical and chemical stresses. To reproduce these conditions,
specific dynamic tests were performed to simultaneously apply chemical and mechanical stresses on a sample. Their objective is to
assess the impact of these stresses on the transport and mechanical properties of class-G Portland cement at selected downhole
conditions and in the presence of CO
2
. Some tests are still running.

The dynamic tests were performed on similar class-G cement samples at 90C. For all the experiments, neutral water (lime-
saturated water) was injected initially into the samples, followed by different fluids: CO
2
-saturated water or supercritical CO
2
.

The dynamic test (Figure 13) with CO
2
-saturated water was conducted for 12 days with a hydrostatic stress phase followed by a
deviatoric stress phase. Initial conditions were: injection pressure pi = 2.5 MPa; confining stress 3= 3 MPa; axial stress 1= 3.5
MPa during hydrostatic phase and 6 MPa during deviatoric phase (deviatoric stress 1 - 3 = 3 MPa).

Figure 14 shows the evolution of the parameters during the dynamic test, the samples axial deformation (1) and the total volume
of CO
2
-rich water injected.

It appears from the main results that adding CO
2
to the water injected throughout the mechanically stressed cement has no
significant impact on deformation of the cement (no change in the strain rate is observed). Simply, compaction was observed, as
expected due to the increase in deviatoric stress. No change in the cements mechanical properties was measured during CO
2
-rich
water injection. The permeability (K) measured during the hydrostatic phase (lasting 4 days) is 1.9x10
-3
mDarcy, and decreases
during the deviatoric phase to 1.6 x10
-3
mDarcy (Figure 14). After 10 days of the experiment, at the beginning of CO
2
-rich water
6 SPE 134473
injection, the flow rate decreases and permeability can no longer be measured. The decrease in permeability, and ultimate clogging
of the sample, is explained by the reaction of a thin layer of cement where the CO
2
-rich water is injected, whereas most of the
sample is not impacted by the injected fluid.

Mineralogical and microstructural analyses show that, for the sample area directly exposed to injection of the aggressive fluid, the
thickness of the carbonated material is very low: 300m, measured with a phenolphthalein test (Figure 15) (during the static test at
90C, the carbonated cement thickness is about 1.2 mm after 12 days, Figure 6).


Discussion on main results

For both static tests, CO2(g) dissolves in water according to: CO
2
(g)+2OH
-
(aq) CO
3
2-
(aq)+H
2
O. Contact of CO
2
-rich water with
cement modifies the equilibrium between cement hydrates and the pore solution [Adenot, 1992]. This induces dissolution of the
hydrate phases followed by internal precipitation of calcium carbonates. This process is known as carbonation.

For the cement used in test #1 (Portland cement), the carbonation mainly involves reactions with portlandite, followed by the
precipitation of calcium carbonate according to the reaction 1 below:

Ca(OH)
2
(s)+ CO
3
2-
(aq) CaCO
3
(s)+H2O(aq). Equation 1

During test #1 the kinetics of carbonation was observed to be proportional to the square root of time, which implies that cement
carbonation in this case is governed by diffusion processes [Adenot, 1992] [Duguid, 2006].

For the Portland cement with the addition of 35% bwoc silica flour (test #2), the reacted zone resulted from the reactions between
CO
2(aq)
and Calcium Silicate Hydrates, also named C-S-H (portlandite (Ca(OH)
2
) is absent in this material), according to reaction 2
[Thiery, 2005]:

C
x
-S
y
-H
z
+ xH
2
CO
3
xCaCO
3
+ ySiO
2
.tH
2
O + (x-t+z)H
2
O Equation 2

This is consistent with the TGA which showed the presence of calcium carbonate (CaCO
3
) in the outer part of the cement samples.
X-Ray tomography results showed that the kinetics of carbonation is proportional with time throughout the duration of the
experiment; it can therefore be limited by chemical reaction kinetics.
The carbonated front moves faster (and deeper) at 140C than at 90C. As the connected porosity exhibits a similar value for both
materials (about 30%), and the CO
2
solubility is similar in pure water at 90C and 140C (Figure 3), the difference may stem from
the mineralogical nature of the hydrates that react with the dissolved CO
2
, their proportion and microstructural assemblage [Rafai,
1992] (e.g. no portlandite in the cement used for test #2 with silica flour and 140C).

Shen et al., 1989 showed that for neat class-G cement, Ca(OH)
2
is carbonated into CaCO
3
, leading to an increase of the solid
matrix volume (because the molar volume of Ca(OH)
2
is lower than CaCO
3
). Consequently, the CaCO
3
formed from Ca(OH)
2
can
appreciably reduce the cements porosity and permeability by volume expansion (and ultimately limits the carbonation process).
Conversely, the reaction of C
x
S
y
H
z
(or C-S-H) with CO
2
results in a highly polymerized silica gel associated with a reduction of
solid matrix volume despite precipitation of calcium carbonate (that has a lower molar volume than C-S-H). The conclusions of
Shen et al., 1989 may explain the differences observed between the two carbonation tests presented in this paper: precipitation of
calcium carbonate in the neat class-G Portland cement (test #1) induces a drastic decrease in the transport processes of the
chemical species, while with class-G Portland cement with silica flour (test #2), the precipitation of calcium carbonate does not
affect the transport processes, allowing continuous carbonation of the samples.

The results of the coupled chemo-mechanical (dynamic) test are consistent with observations made by Carey et al., 2007 who
showed that in situ cement sheath samples were not altered by CO
2
attack after 30 years of CO
2
injection. The steep decrease of
cement permeability still provides protection against significant movement of CO
2
through the cement matrix.

Conclusions and Prospects


The static carbonation tests on neat class-G cement at 90C and class G with silica flour at 140C resulted in partial or total
carbonation of the samples (for the experimental conditions described in this paper). Class-G oilwell cement is thus reactive when
exposed to carbonic acid under downhole conditions. However, the behavior is different for each material: the carbonation front
progression is controlled by diffusion for neat class-G cement (the front evolves linearly with the square root of time), while it is
limited by reaction kinetics for class G + silica flour cement (the carbonation front evolves linearly with time).

SPE 134473 7
In addition to the static tests assessing the phenomenology and the kinetics of carbonation, dynamic tests were performed to assess
the evolution of the mechanical and transport properties of oilwell cements in selected downhole conditions in the presence of
CO
2
. The results of the first tests (still running) show that the cement sheath is not mechanically damaged and is still able to fulfill
its main function of ensuring the confinement of CO
2
in the target reservoir (by improving its transport properties).

From the preliminary results, the cement matrix reaction in CO
2
environments does not appear to be the driving phenomenon for
loss of well integrity; mechanically induced damage to the cement sheaths (hydro frac, micro-annulus, etc.) may give greater cause
for concern.


References


Adenot, F. Concrete durability: characterization and modelling of the chemical and physical processes of cement degradation.
Thse de Doctorat de lUniversit dOrlans, 1992 (in French).

Benge, G. Improving wellbore seal integrity in CO
2
wells. SPE/IADC 119267, 2009.

Carey, J.W., Wigand, M., Chipera, S.J., Wolde Gabriel, G., Pawar, R., Lichtner, P.C., Wehner, S.C., Raines, M.A., Guthrie Jr.,
G.D. Analysis and performance of oil well cement with 30 years of CO2 exposure from the SACROC Unit, West Texas, USA.
international journal of greenhouse gas control, 2007.

Duguid, A., The effect of carbonic acid on well cements, PhD Thesis of the faculty of Princeton University 2006.

Fernndez Bertos, M., Simons, S.J.R., Hills, C.D., Carey. P.J. A review of accelerated carbonation technology in the treatment of
cement-based materials and sequestration of CO2, Journal of Hazardous Materials, 2004.

Hewlett, P. Leas chemistry of cement and concrete. Fourth Edition, edited by Peter C. Hewlett, ARNOLD publishers, 1991.

Kamali, S., Moranville, M., Leclercq, S., Material and environmental parameter effects on the leaching of cement pastes:
Experiments and modeling, Cement and Concrete Research, 38, 2008

Meller, N., Hall, Ch., Phipps, J.S. A new phase diagram for the CaOAl2O3SiO2H2O hydroceramic system at 200C. Materials
Research Bulletin, 40, 2005.

Mulders Frans. Analysis of abandoned well integrity at a potential CO2 storage site. 3rd Well Bore Integrity Network Meeting,
Santa Fe, USA, 2007.

Neuville, N. Study and modeling of physico-chemical degradation of oil wells cementing materials, PhD thesis, Ecole des Mines
de Paris France, 2008 (in French).

Nok, Ch., Rivereau, A., Vernet, Ch., Novel cements materials for high-pressure/high-temperature wells, SPE 50589 SPE
European Petroleum Conference held in The Hague, The Netherlands, 1998.

Ollivier, J.P. Minutes of technical days AFPC-AFREM durabilit des btons Required methods for the measurements of
parameters associated to durability, Toulouse, France, 1997 (in french).

Rafai, N., Letolle, R., Blanc, P., Gegout, P., Revertegat, E. Carbonation-decarbonation of concretes studies by the way of carbon
and oxygen stable isotopes. Cement and Concrete Reseach, vol.22, 1992.

Shen. J.C., Pye, D.S. Effects of CO2 Attack on Cement in High-Temperature Applications. SPE/IADC 18618, 1989.

Span, R., and Wagner, W.. A new equation of state for carbon dioxide covering the fluid region from the triple-point temperature
to 1100 K at pressures up to 800 MPa. J. Phys. Chem. Ref. Data., 25, 1996.

Taylor H.F.W., Cement Chemistry, 2nd edition, edited by Thomas Telford, 1997.

8 SPE 134473
FIGURES:




Figure 1: Examples of RX density images for 2 cement samples used for the test #2 (class G + silica flour), after curing
period


Figure 2: Schematic of a cell used for experiments



Glass beaker
Tube
Samples
Distilled water
Heating resistance regulation at
90C or 140C
Supercritical CO
2
at 90C or
140C and 80 bar
Gas
injection Gas exit
3-tier sample-holder
Hounsfield scale: 1100 2600
20mm*40mm
SPE 134473 9
C
O
2
s
o
l
u
b
i
l
i
t
y
(
m
o
l
.
k
g

1
H
2
O
)
Temperature (C)
Test2
Test1

Figure 3: CO
2
solubility in pure water under various temperature and pressure conditions (Span et al. 1997)



Figure 4 : Pressure monitoring for the test #1 (black line) test #2 (grey line)

10 SPE 134473


Figure 5 : Sagittal sections obtained by RX tomography on samples taken at different times in the test #1 (top) and test #2
(bottom). The gray scale (Hounsfield scale) represents RX density scale

0
1
2
3
4
5
0 2 4 6 8 10
D
e
g
r
a
d
e
d

t
h
i
c
k
n
e
s
s

(
m
m
)
Timeofexperiment(day)

Figure 6: Thickness of carbonated cement as a function of square root of time (test #1: 90C)





Before test

7 days

36 days 65 days

Hounsfield scale: 1100 2600
Test #1
(90C)
Test #2
(140C)
Before test

4 days
21 days 31 days

88 days
SPE 134473 11
0
5
10
15
20
25
30
35
0 10 20 30 40 50 60 70
C
u
m
u
l
a
t
e
d

q
u
a
n
t
i
t
y

o
f

i
o
n
s

i
n

s
o
l
u
t
i
o
n

(
m
g

f
o
r

e
a
c
h

s
a
m
p
l
e
)
Timeofexperiment(day)
Calcium Silicon

Figure 7: Total quantity of calcium and silicon in solution in the leachant (test #1: 90C)


0
10
20
30
40
50
60
70
80
90
100
1600 1700 1800 1900 2000 2100 2200
C
u
m
u
l
a
t
e
d

f
r
e
q
u
e
n
c
y

(
%
)
RXdensity
4days 12days 88days Initialmaterial


Figure 8: Cumulated frequencies of RX density in the initial and the carbonated cement samples (test #2: 140C)

12 SPE 134473
4days
12days
31days
Carbonatedfront
Higher porous
zone
A
g
r
e
s
s
i
v
e

f
l
u
i
d

Figure 9: SEM image (BSE) of carbonated cement samples after 4, 12 and 31 days of test #2 (140C)



0
5
10
15
20
25
0 20 40 60 80 100
D
e
g
r
a
d
e
d

t
h
i
c
k
n
e
s
s

(
m
m
)
Timeofexperiment(day)

Figure 10: Thickness of carbonated cement as a function of time (test #2: 140C)




1 mm
SPE 134473 13
0
10
20
30
40
50
60
0 1 2 3 4 5 6 7 8 9 10
C
a
C
O
3

c
o
n
t
e
n
t

(
%

w
t
.
)
Materialdepth(mm)
Referencesample 4days
12days 21days
55days 88days

Figure 11: CaCO
3
content (% wt.) in the initial (reference) sample and in the carbonated cement after different lengths
of time (test #2: 140C)




0
50
100
150
200
250
300
350
400
450
0 20 40 60 80 100
C
u
m
u
l
a
t
e
d

q
u
a
n
t
i
t
y

o
f

i
o
n
s

i
n

s
o
l
u
t
i
o
n

(
m
g

f
o
r

e
a
c
h

s
a
m
p
l
e
)
Timeofexperiment(day)
Calcium Silicon


Figure 12: Quantity of calcium and silicon in solution in the leachant (test #2: 140C)






14 SPE 134473
Confining stress
Fluids :unreactive water,CO
2
rich fluid
Axialstress
Piston
Cement
sample
T = 90C
S3
S1

Figure 13: Schematic of the dynamic chemo-mechanical test




Limesaturated water CO
2
rich water

Figure 14: Evolution of parameters and sample response through to clogging: 1 and 3 stresses, injection pressure (pi),
axial deformation (1) and injected volume

SPE 134473 15

Figure 15: Photograph of cement sample after the chemo-mechanical test