SPE 124733

Holistic Design of Cement Systems to Survive CO2 Environment

N. Moroni, Eni E&P Division, and A. Santra, K. Ravi, and W. Hunter, Halliburton

Copyright 2009, Society of Petroleum Engineers

This paper was prepared for presentation at the 2009 SPE Annual Technical Conference and Exhibition held in New Orleans, Louisiana, USA, 4–7 October 2009.

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
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Abstract
Cement systems that can survive in the CO2 environment are needed in various applications. Examples of these applications
include: 1) producers: CO2 in the reservoir is produced along with the hydrocarbons, 2) injectors: CO2 is injected for
sequestration and/or enhanced oil recovery, and 3) producers and injectors: produced CO2 can subsequently be injected for
the purpose of enhanced oil recovery/sequestration.
However, the carbonation of Portland cement is a well-documented, thermodynamically favorable process. When CO2 or
carbonic acid comes in contact with Portland cement, it initially reacts with it to form water-insoluble calcium carbonate.
Longer term, the presence of water dissolved with CO2 (or carbonic acid), if allowed to contact the cement sheath, can
dissolve the calcium carbonate to bi-carbonate, which then could be displaced if a flow channel were to be present or formed
during the life of the well. This can threaten long-term effective zonal isolation.
A dual level solution is required to effectively address this challenge. As a first level, the potential for CO2 to enter the
cemented annulus and contact the cement sheath is minimized, by placing the cement slurry in the entire annulus, reducing
the permeability and endowing the set sheath with the properties necessary to withstand the well events. The second level
involves reducing the amount of material in the set cement sheath that is reactive to CO2. This holistic approach has worked
well in practice. Both the physical and chemical integrity of the cement sheath is addressed using this approach.
Following the design logic described above, a cement system with improved resistance to CO2 environments was created
by 1) designing a reduced-permeability cement sheath to withstand well operations with low cement hydration volume
shrinkage and 2) optimizing the cement slurry formulation so that its hydration products have a lower amount of materials
that are reactive to CO2. This cement system was then tested in the laboratory under expected in situ conditions and
optimized for different well situations before placement in the field.
The cement systems have been successfully placed in anumber of wells and these wells are all operating as required with
no loss of zonal isolation reported. The design approach, laboratory test procedure and results from laboratory and field are
presented and discussed in this paper.

Introduction
Technologies associated with carbon capture and storage (CCS) are coming more and more to the forefront as the world
tackles long-term trends for increasing global energy demand coupled with the need to address the challenge of associated
CO2 emissions (Fig. 1). In addition, it has been estimated that 40% of the world’s remaining gas reserves contain more than
2% CO2.
In considering how to deal with CO2 emissions, the scale of the task ahead cannot be underestimated. Global CO2
emissions are projected to rise from less than 20 thousand million tons in 1980, to wells in excess of 30 thousand million tons
by the year 2030. CCS is one way in which it is hoped CO2 emissions to the atmosphere can be reduced. Currently four large-
scale CCS projects are operating around the world, each separating around 1 million tons of carbon dioxide per year from
produced natural gas: Sleipner and Snohvit in Norway, Weyburn in Canada (with the carbon dioxide sourced in the United
States), and In Salah in Algeria. In considering these numbers it is easy to see that as many as 10,000 Sleipner-sized projects
might be required by the year 2030 if CCS were the only method selected to reduce CO2 emissions to 1980 levels.
The wellbores that are used in CCS projects to convey the CO2 from surface to the selected storage reservoir, or in gas
production projects to convey the gas from reservoir to surface, are lined with steel casing and well cement. The purpose of
the well cement is to support and protect the steel casing from corrosion and to act as a barrier to the flow of any fluid in the
annular space between the casing and the rock formations penetrated. In considering the long-term integrity of the cement, it
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is well known that the potential exists for CO2 to degrade conventional Portland well cements. The ability to design well
cements that will survive in CO2 environments is therefore a key CCS technology.

Fig. 1—Projected world energy demand and CO2 emissions (Rising to the CO2 Challenge 2009).

This will require a dual-level solution, one in which the challenge is effectively addressed with a holistic approach. First
and foremost, it is necessary to successfully place the cement in slurry form such that it provides uniform annular coverage
across the chosen areas of the wellbore. The cement, once it transitions to solid form, must then exhibit low permeability and
be able to maintain integrity under the mechanical loads imposed upon it by well conditions both expected and unexpected.
Then, the second of the dual-levels involves endowing the set cement with resistance to attack by chemical reactions.
The results from using this dual-level technology in actual wellbores is highlighted in this paper.

The Necessity for a Holistic Approach

The main objective of a primary cement job is the provision of zonal isolation for the life of the well. This is important if
operators are to meet and exceed the environmental and economic performance goals for a project. Achieving zonal isolation
protects casing from corrosion, prevents sustained casing pressure, reduces premature water production, limits inter-zonal
communication and reduces the need for remedial work on a well. If a cement slurry is designed and delivered such that it is
placed in the designated section of the annulus and the set cement sheath maintains chemical, mechanical, and thermal
integrity during the life of the well, then this helps the asset team meet and exceed their performance targets.
The challenges faced in placing the cement slurry into a wellbore effectively are discussed in detail in other publications.
If the drilling fluid is not efficiently removed from the annulus, then this provides the pathway for produced and injected
fluids to enter the annulus. Figs 2a and 2b show examples where the drilling fluid has not been removed and the gelled mud
surrounding the set cement sheath is clearly unable to provide zonal isolation. As this material dehydrates over time, the
situation further deteriorates. Primary cement-job parameters such as casing stand-off, spacer and cement-slurry volume, flow
rate, rheology, and pipe rotation should all be optimized to achieve effective cement-slurry placement in the targeted annular
space (Moroni et al. 2009c). Computer software is available for workers to use during this optimization process. One new
type of software recently made the use of a specialized three dimensional (3D) computational fluid-dynamics simulator
available for the industry (AADE-08-DF-HO-08). A snapshot from the graphical user interface of this simulator is provided
in Fig. 2c. With this tool, the user can model and clearly assess the ability of one fluid to displace another from different
wellbore geometries under specific well conditions.
The importance of the set cement sheath properties that will allow it to withstand well operations and the cyclic loads to
which it is subjected is discussed in detail in other publications. The mechanical properties such as Young’s modulus, tensile
strength, and compressive strength determine the failure modes of the cement sheath and should be optimized to withstand
the cyclic loads during the life of the well. Figs. 3a and 3b show how a cement sheath could crack and de-bond when the
temperature and pressure change during well operations. If the cement were to fail in such a manner, then any micro fractures
or micro annuli that might develop in the cement sheath can act as potential flow paths for CO2 and other well fluids in the
annular space. If CO2 is allowed to flow in the annulus through such pathways, this will allow carbonation to progress more
rapidly through the cement column than if the cement sheath remained intact. Additionally, if the flow is associated with an
acidic solvent, such as carbonic acid, and is able to transport material, then it will erode any carbonated cement.
SPE 124733 3

To help workers minimize the possibility of potential flow paths for CO2 through and around the cement sheath in any
microfractures or microannuli that might be created if the cement sheath fails, FEA-based software packages are available to
determine the recommended mechanical properties and also importantly the shrinkage/expansion characteristics for the
cement to be able to withstand expected well events without failure.

Fig. 2a and 2b—slabs showing undisplaced mud channels.

Fig. 2c —Snapshot from graphical interface of 3D computational fluid dynamics simulator.

Fig. 3a and 3b—Crack formation and de-bonding in the cement sheath as a result of the temperature and pressure change during
well operations.
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Then, to maximize the ability of the sheath to maintain chemical and thermal integrity, it is necessary to:
• Reduce the amount of products that could react with produced and injected fluids such as CO2, H2S, and other
downhole fluids.
o Optimize a Portland-based cement slurry with selected components, or
o Use a cement system that does not chemically react with CO2, e.g.; calcium aluminate phosphate cement.
• Select components that are thermally stable at the downhole temperature and pressure.

The failure to deliver any one of these elements when delivering the primary cementation in a well constructed in a CO2
environment can mean that the integrity of the zonal isolation provided might be compromised at some point during the life
of the asset. For this reason, a holistic approach that incorporates all these elements must be followed.

Experimental
Slurry Preparation
Cement slurries for this study were prepared using standard API RP 10B [10]. The neat cement slurry was prepared using
Class G cement at 15.8-lbm/gal density, whereas, the cement sample-A was prepared with a CO2-resistant formulation.

Sample Curing
All the slurries were poured in cylinders that were 2.5 in. in length and 1 in. in diameter and cured in an autoclave filled with
water at 2,000 psi and 200°F for 15 days before CO2 treatment.

HPHT Static CO2 Treatment

All the cured samples were de-molded and subjected to treatment with supercritical CO2 using test cells made of hastelloy
(Fig. 4) at 2,000 psi CO2 pressure at 200°F. The samples were fully immersed in fresh water during testing. The test duration
was 15 days for one set of samples and 90 days for another set.

Fig. 4—Test cells used at 200°F and 2,000 psi CO2.

Dynamic CO2 Core Flow Test

A freshly cured sample in cylinders of 2 in. in length and 1 in. in diameter was subjected to a flow test using a typical
Hassler’s sleeve with an option of injecting two fluids.

Mechanical Properties Testing

Uni-axial and tri-axial stress-strain tests were performed on cylindrical samples to determine Young’s modulus, Poisson’s
ratio, friction angle, and plasticity parameters. Tests were performed according to ASTM D 3148–02 and D 2664–95a. Dual-
axial extensometers and a circumferential chain extensometer were used to measure strains on samples.
SPE 124733 5

Analytical Measurements
A Phillips X-Ray diffractometer TA instrument was used to carry out XRD and thermal gravimetric analysis (TGA).

Results and Discussion

Cement System A and a neat Portland cement were tested in this study. Cement System A is designed to decrease the
permeability and reduce the cement hydration products that could react with CO2. Details of the cement-CO2 reaction has
been recently discussed (Santra et al. 2009) and are described below:

Reactions
Portland cement mainly consists of tricalcium silicate (C3S) and dicalcium silicate (C2S). These react with water to form
calcium silicate hydrate (C-S-H) and Portlandite or calcium hydroxide [Ca(OH)2]. The CSH gives strength and set properties
to the cement sheath.

C3S + H2O = C-S-H + Ca(OH)2 (1a)

C2S + H2O = C-S-H + Ca(OH)2 (1b)

However, C-S-H and Ca(OH)2, when exposed to CO2, form precipitate of calcium carbonate (CaCO3).

C-S-H + CO2 = CaCO3 + SiO2 (gel) (2a)

Ca(OH)2 + CO2 = CaCO3 (2b)

Calcium carbonate alone cannot be a problem unless so much of it is formed that it could crack the cement sheath. It is
the dissolution of the calcium carbonate in the presence of carbonic acid (CO2 and water) that leads to the formation of
calcium bi-carbonate, which is soluble in water.

CO2 + H2O = H2CO3 ------------- (3)

CaCO3 + H2CO3 = Ca(HCO3)2 -------------- (4)

Hence it helps to reduce the amount of C-S-H and Ca(OH)2 formed in a set cement sheath so that less CO2 reactive
products are formed in the set cement sheath. This should be balanced with the need for strength requirement and other
properties of the cement slurry and the cement sheath.
Obviously, one definite way to eliminate the CO2-reactive products formed in the cement sheath is to use a non-Portland
cement. However, the results will show this is only necessary in the most severe conditions.
In addition to reducing the CO2 reactive products in the cement sheath, it is necessary to reduce the permeability of the
cement sheath and also design and deliver the cement slurry to withstand well operations. The details of designing and
delivering the cement slurry to withstand well operations are discussed in other publications (Moroni et al. 2009a and 2009b).
This study focuses mainly on the effect of CO2 on neat Portland and Cement System A.

Dynamic CO2 Flow Test

A dynamic flow test was conducted in the test device discussed earlier. Fig. 5 shows the flow obtained when nitrogen gas is
passed through the cement sheath formulated with Cement System A, at a differential pressure of 500 psi. The length of the
sample is 2 in. and the diameter is 1 in. The nitrogen flows through the sample at a rate of 3 SCCM (standard cubic
centimeter per minute). This translates to a permeability of about 0.026 millidarcies (mD) to the nitrogen gas. This is a low-
permeability cement sheath.
After establishing the flow with nitrogen, a moist CO2 gas is flowed through the sample at a differential pressure of 500
psi. Soon after the moist CO2 is passed through the sample there is no flow of CO2 detected from the other end. This means
that the permeability to the moist CO2 gas is zero or no flow through the sample could be established even at a differential
pressure as high as 500 psi.

TGA Analysis
The dynamic test shows that Cement System A did not let the moist CO2 flow through it. The cement sample was further
investigated. A TGA was performed and is shown in Figs. 6 and 7. For comparison, the TGA analysis of a neat Portland
cement was also conducted and shown in these figures. Fig. 6 shows the results of TGA on the hydrated cement samples
before exposing them to CO2. This figure shows that the amount of Portlandite and Ca(OH)2, formed during hydration of the
Cement System A is much less than what is formed during the hydration of the neat Portland cement. This is important
because as per the chemical reactions in Figs. 2a and 2b, these hydration products react with CO2 to form CaCO3.
Fig. 7 shows the TGA on the samples after they are exposed to supercritical CO2 using the test apparatus shown in Fig. 4
at 200°F, 2,000 psi, and 3 months. As can be seen in this figure, the amount of CaCO3 formed when Cement System A is
exposed to CO2 is about half of that is formed with neat Portland cement. This is because Cement System A contained a
6 SPE 124733

lower amount of products that could react with CO2 and form CaCO3. As per Figs. 3 and 4, CaCO3 has the potential to react
with water to form calcium-bi-carbonate, Ca(HCO3)2 which is soluble in water. The dynamic tests and the TGA tests validate
the hypothesis that it is important to reduce the amount of products that can react with CO2 to form CaCO3. The conversion to
bi-carbonate is the culprit as this provides an easy pathway for the carbonic acid to continuously invade the cement-sheath
matrix. This is confirmed from the Phenolphthalein test.

Fig. 5—Core flow test using Hassler’s sleeve.

Fig. 6—TGA spectra before CO2 treatment.

SPE 124733 7

Fig. 7—TGA spectra after CO2 treatment.

Conceptual Diagram
The results obtained above are pictorially depicted in the conceptual diagrams shown in Fig. 8. This figure shows what could
be happening to a neat Portland cement sheath and Cement System A when they are exposed to carbonic acid. After
hydration there are more products such as Ca(OH)2 in the neat cement sheath that could react with CO2 whereas Cement
System A has fewer products in the cement sheath that could be attacked by CO2. On exposure to carbonic acid, the products
in a neat cement sheath react with CO2 to form calcium carbonate, which subsequently forms calcium bi-carbonate and
dissolves. Because the neat cement sheath has more products which can react with carbonic acid, the latter can invade the
cement sheath matrix and result in a highly permeable cement sheath. In contrast, the Cement System A has fewer products
that could react with CO2 and hence the damage is limited.

Mechanical Properties
Table 1 shows the mechanical properties of neat Portland cement system and Cement System A before and after exposure to
CO2 for a period of three months at 200°F and 2,000 psi. The neat Portland cement shows a decreased in compressive and
tensile strength after exposure to carbonic acid. The possible reason is that when the neat Portland cement is exposed to CO2,
a considerable amount of CaCO3 is formed. This causes tremendous expansion-related stress in the cement sheath matrix and
in the process could crack the cement sheath matrix. These induced defects can be the reason behind decreased compressive
and tensile strength. Cement System A does not show any decrease in strength that was observed with the neat Portland
cement system. This could be a result of the lower amount of CaCO3 that is formed when Cement System A is exposed to
CO2.
8 SPE 124733

Fig. 8—Conceptual diagram of CO2-cement sheath interaction.

Holistic Placement of Cements with Improved CO2 Resistance—Field Experience

As previously mentioned, CO2 environments can be found in different types of wells that are used for a variety of
applications, not only CCS wells, although obviously more and more of these are expected as the world begins to tackle the
challenge of limiting CO2 emissions. The general approach described here has been successfully applied in a number of wells
around the world to deliver a CO2-resistant annular seal. Three representative examples will be highlighted.

High Pressure Wells with Associated CO2 Environment in Kazakhstan. The Kashagan field in Kazakhstan is a massive oil
and gas field, with a reservoir characterized by high pressure (~ 800 bars) and high concentrations of both H2S and CO2 in the
production flow stream. The approach detailed in this paper has been successfully employed on more than eleven wells
constructed in this field (Maroni 2009a) at the time of writing, with good results. The cements placed in the wells were
mechanically modified such that they would be expected to withstand the stresses imposed by predicted well operations.
They were also designed with reduced permeability and the set cement sheath had fewer components that could react with
CO2. In addition, the spacer and cement-slurry rheology were optimized and the surfactant concentration in the spacer was
optimized to promote effective hole cleaning and improved cement-sheath bonding. The annular seal in all of these wells is
reported to still be functioning well at this time.
SPE 124733 9

Table 1. Mechanical Properties After and Before CO2 Treatment

Neat Cement, Class G
Before CO2 Treatment After 3 Months CO2 Treatment
Compressive Strength, psi 8,654 6,285
Tensile Strength, psi 748 588
Young’s Modulus 1.6E+06 1.595E+06
Poisson’s Ratio 0.167 0.175
Density, lbm/gal 16.33 17.76
Sample A
Compressive Strength, psi 6,188 8,486
Tensile Strength, psi 677 770
Young’s Modulus 2.0E+06 1.65E+06
Poisson’s Ratio 0.191 0.161
Density, lbm/gal 16.26 16.91

Demonstration Power Plant CCS Project Environment in the U.S. In 2008, at a power plant located in Mississippi, two
9,500 ft demonstration wells were successfully cemented following this general holistic approach. Part of a U.S. government
Department of Energy (DOE) consortium project, one injection and one observation well were constructed at the power plant
site in question. The intention of the project was to document how the injection of CO2 can affect the targeted storage
reservoir there. To this end, after construction, 3,020 tons of CO2 was pumped into the injection well in the fall of 2008. The
project is currently being monitored via the observation well and a very comprehensive monitoring package featuring a large
variety of measurement techniques (Table 2). At the time that this paper was written, no problems had been reported with the
annular seal in these wells. The targeted saline formation being tested in this demonstration is the Lower Tuscaloosa
sandstone and is significant in that it is considered to be representative of the geology that could be used to store up to 50% of
the CO2 produced in the southeastern U.S. region during the next 100 years (14 to 54 thousand million tons).

Geothermal Energy Project with Associated CO2 Environment in the U.S.A. In Imperial Valley, California, a number of
geothermal plants in the Salton Sea Field which together produce enough electricity to power 100,000 homes. The flow
streams from the wells that power these plants feature high temperatures and also significant CO2 concentrations. Using the
general approach outlined in this paper, namely cement with enhanced mechanical properties (imparted by foaming the
material with nitrogen) and the minimum of CO2 reactive components, a successful annular seal was established in one of
these wells (Berard et al. 2009). At the time of writing this paper no problems have been reported with that annular seal.

Summary
In designing well cements for use in CO2 environments a holistic approach is required. Firstly, it is necessary to carefully
consider, plan and then execute the task of effectively displacing the drilling fluid from the annular space while avoiding
losses and well control issues and replacing this drilling fluid with cement in slurry form. The slurry thus placed also needs to
be designed such that is does not permit fluid or gas migration as it transitions from slurry to solid form.
Then, the set cement needs to be endowed with low permeability and mechanical properties that would be expected to
allow it to withstand predicted well events. Finally, the amount of hydration products that could react with CO2 needs to be
minimized. If this holistic approach is taken, then experience has indicated both in the laboratory and the field, that a more
reliable annular seal can be provided in wells in which CO2 is present.
10 SPE 124733

Table 2. Measurement Techniques in Use at USA CCS site where Wells Cemented Using Holistic Approach
(Southeast Regional Carbon Sequestration Partnership (SECARB) the Mississippi Test Site Field Test Fact Sheet)
SPE 124733 11

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