SPE-182955-MS

The Impact of CO2 Injection for EOR & its Breakthrough on Corrosion and
Integrity of New and Existing Facilities

Abdulla Luqman and Ali Moosavi, ADCO

Copyright 2016, Society of Petroleum Engineers

This paper was prepared for presentation at the Abu Dhabi International Petroleum Exhibition & Conference held in Abu Dhabi, UAE, 7-10 November 2016.

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
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Abstract
Carbon Dioxide (CO2) Injections for Enhanced Oil Recovery (EOR) is used to increase the amount of
crude oil that can be extracted from reservoirs. The CO2 injected becomes miscible with the reservoir oil.
The resulting miscible fluid has the favorable properties of lower viscosity, enhanced mobility and lower
interfacial tension as compared to an oil reservoir without CO2. However, the produced oil through this
EOR contains greater amounts of CO2 and with the re-injection of produced CO2 this breakthrough will
increase over time.
This paper is based on Abu Dhabi Company for Onshore Petroleum Operations' (ADCO) experience
with regards to CO2 EOR studies on asset integrity, material selection and corrosion mitigation. It serves as
a guide to the main factors effecting CO2 corrosion, an assessment on what to look for in major equipment
and the recommended material of construction and corrosion mitigation / control methods.
Dry CO2 is not corrosive, however when dissolved in an aqueous phase it will produce carbonic acid
(H2CO3) which starts the corrosion process. Under ideal conditions Iron Carbonate (FeCO3) scales will form
which act as a protective layer preventing further corrosion. As the CO2 increases this will increase the
corrosion rate as no protective scale will be present.
Factors effecting CO2 corrosion and the FeCO3 protective scale are discussed; Water Wetting, Partial
Pressure, Temperature, pH, Flow Regime & Velocity and Effect of H2S. In addition, a corrosion assessment
highlighting areas of importance, material selection and mitigation methods is made on new and existing
facilities; CO2 Injection Systems, Downhole Equipment, New Oil Producers and Existing Facilities.
Lack of free water will prevent any CO2 corrosion from occurring. This is especially important in the
injection systems for transporting CO2 as, in the absence of free water, Carbon Steel can be used. Based
on ADCO's experience, downhole completion material of non-sour CO2 injector wells should be Super 13
Chromium and for Oil Producers Carbon Steel with Corrosion Inhibition with Nickel Alloy for the tubing
section under the packer.
For Oil Producers, this is subject to a case by case study. The use of Corrosion Resistant Alloys (CRA) or
going with Carbon Steel with Corrosion Inhibition is the main dilemma. This is dependent on the dominating
form of corrosion, formation of protective scales and the ability to maintain a stringent corrosion mitigation
and monitoring regime.
2 SPE-182955-MS

Finally, for existing equipment, evaluation of the current condition of the equipment is important. This
will guide the mitigations required. Some prevention methods include corrosion inhibition, neutralizing
acidity of service and material upgrade to CRA. Type of method used should be based on company
preference and life cycle cost analysis.
This paper serves as a guide to ADCO's experience for knowledge sharing and further development of
ideas and innovations.

Introduction
During primary production of wells, oil reservoirs may be under sufficient pressure to be able to push the
hydrocarbons onto the surface. As the fluids are produced the pressure will often decline and production
will falter. To be able to maintain the pressure to ensure production some artificial methods are used.
Enhanced Oil Recovery (EOR) is a technique used to increase the amount of crude oil that can be extracted
from an oil field. The injection of miscible gases to the reservoir causes a miscible displacement process;
maintaining reservoir pressure and improving oil displacement because the interfacial tension between oil
and water is reduced. This is done by removing the interface between the two interfacing fluids allowing
for total displacement efficiency.
Gases used included Carbon Dioxide (CO2), Natural Gas and Nitrogen (N2). The entity most commonly
used for miscible displacement is Carbon Dioxide as it reduces the oil viscosity, reduces the Greenhouse
Gas Emissions and is less expensive than liquefied petroleum gas. Oil displacement by Carbon Dioxide
relies heavily on the phase behavior of the mixtures of that gas and the crude.

Figure 1—Enhanced Oil Recovery with Carbon Dioxide Injection

CO2 EOR works most commonly by injecting CO2 into already developed oil fields where it mixes with
and "releases" the oil from the formation, thereby freeing it to move to production wells. CO2 that emerges
with the oil is separated in above-ground facilities and re-injected into the formation.
The secondary production of wells through EOR, contain additional traces of CO2. The impact of this
additional CO2 on the existing facilities will need to be studied to ensure the adequacy of the equipment.
Inadequacy of the current system to handle this change may require rerouting flow of the production to
other equipment able to handle the fluid, change in material for some equipment and change of the corrosion
mitigation philosophy.
This paper discusses some of the major factors in CO2 corrosion, the effects during CO2 breakthrough
and a guide to material selection and corrosion mitigation.
SPE-182955-MS 3

CO2 Corrosion
Injection of Carbon Dioxide (CO2) is a promising method for recovering large amounts of oil that cannot be
recovered by conventional technology. With benefits of injection of CO2 there are risks of internal corrosion.
Dry CO2 gas is not itself corrosive but is so when dissolved in an aqueous phase. Water is required for
corrosion to occur, dry carbon dioxide would be non-corrosive because CO2 relies on the formation of
carbonic acid, as shown below:

CO2 is extremely soluble in water & brine and it has even greater solubility in hydrocarbons. CO2
dissolves into the crude oil and follows through the production and transportation process. CO2 dissolves
in water and can react with iron in the carbon steel pipes. The overall reaction process is shown below:

Under ideal conditions, FeCO3 can create a protective layer and prevent further conversion of iron. This
protective layer would prevent the cathodic and anodic reactions shown below in Figure 2 to take place.

Figure 2—Electrochemical Cell for CO2 Corrosion on a Steel Surface

"Sweet" and "Sour" Corrosion Mechanisms

Corrosion primarily caused by dissolved carbon dioxide is commonly called "sweet" corrosion whereas
corrosion due to the combined presence of dissolved carbon dioxide and hydrogen sulphide is referred to as
"sour" corrosion. The generally accepted view of the effect of CO2/H2S ratio on the corrosion mechanism
is as follows:
a. For CO2/H2S ration < 20, the corrosion is fully governed by H2S. For Carbon Steels, the primary
corrosion product is a non-stoichiometric iron sulphide (FexSy), with varying protective properties
depending on its crystallographic structure.
b. For high CO2/H2S ratio, the corrosion rate is fully governed by CO2. The primary corrosion product
is iron carbonate (FeCO3). The limit ration is generally taken as 500 but depends on environmental
variables.
c. For intermediate rations, the corrosion regime is complex and difficult to anticipate.
4 SPE-182955-MS

The main features of sweet and sour corrosion are summarized in Table-1 below:

Table 1—Sweet & Sour Corrosion Highlights

CO2 (Sweet) (Ratio H2S (Sour) (Ration

Controlling Factor
CO2/H2S high) CO2/H2S<20)

Main Corrosion Product / Scale FeCO3 FexSy

Main Corrosion Damage Metal Loss Cracking

Typology of Metal Loss Corrosion Uniform in Principle Localized

Effect of Velocity on Corrosion Rate Increased Rate Uncertain

Effect of Chloride Content Neutral Increased Pitting Attack

Increased rate up to
Effect of Temperature Increased Pitting Attack
60°C, decreased above

Factors Effecting CO2 Corrosion

The severity of CO2 corrosion is dependent on many parameters. Some of the key parameters effecting CO2
corrosion are listed below:
– Water Wetting
– Partial Pressure of CO2
– Temperature
– pH
– Flow Velocity & Regime
– Effect of H2S

Water Wetting
For CO2 corrosion to occur there must be water present and it must wet the steel structure. When considering
two phase flow (oil & water), a pipeline is said to be water-wet when the contact angle between the interface
of the water and the pipe surface is less than 90°. This is the case in most crude oil pipelines.

Figure 3—Wettability of two phase oil water system, Water-Wet Case. (Crane, 2005)

At the extreme, an angle of 0° signifies the pipe is completely water wet. Wettability is dependent on
the fluid and its impurities. When a pipe wall is more water–wet, there is a larger area of contact with the
brine and the wall itself.
SPE-182955-MS 5

On the contrary, if the surface is oil-wet, then the oil will contact the walls of the pipe and reduce the
surface area for water contact. This is in direct relation to the area available for corrosion. The greater the
water wettability, the more likely corrosion is to occur.
In oil / water systems emulsions can form. If a water-in-oil emulsion is formed then water may be held
in emulsion and water wetting of steel surface prevented or greatly reduced, leading to a reduction in the
corrosion rate.
The transition from a water-in-oil emulsion to oil-in-water emulsion occurs around 30-40% water in oil
and a clear jump in corrosion rate can be demonstrated. This has led to a rule of thumb that corrosion is
greatly reduced for water cuts below 30%.
In addition, the influence of water cut on corrosion rate is linked to flow velocity and flow regime effects.

CO2 Partial Pressure

An increase in the partial pressure of CO2 leads to an increase in the corrosion rate. CO2 corrosion results
from reaction of steel surface with carbonic acid.
An increase in the partial pressure of CO2 would mean more carbonic acid could be formed with a greater
concentration of cathodic ions to carry out the reduction reaction, the corrosion rate would rise.
However, in favorable conditions where protective scales can form, the corrosion rate is reduced.
Increases in pressure increases the precipitation and formation of iron carbonate scales.
This is illustrated in the figure below, where corrosion rate rises sharply prior to scale formation and then
drops as scales form over time.

Figure 4—Predicted effect of CO2 partial pressure on the corrosion rate. (Lee, 2002)

Temperature
It is expected that the rate of a chemical reaction increases with temperature. Since more energy is available
at higher temperature, more iron can be oxidized because the activation energy barrier is easier to overcome.
For CO2 corrosion where water is a dependent factor there is an exception. At higher temperatures where
water is above the dew point, it does not condense. Without the presence of the condensed water, there is
a decrease in the rate of corrosion.
6 SPE-182955-MS

Also, with the formation of the protective iron carbonate scale, higher temperatures decrease the solubility
of this precipitate. Increasing likeliness of scale formation.
However, temperature effects are also linked with pH of the surrounding environment.
Figure below plots the effects of temperature alongside corrosion rates as a function of time (at pH of 6.6).

Figure 5—Predicted effect of temperature on the corrosion rate. (Lee, 2002)

pH
pH has a strong influence on the corrosion rate due to its effect on the cathodic reaction as well as its indirect
effect of forming protective scales.
It is seen that the solubility of corrosion products released is reduced by just five times when the pH is
increased from 4 to 5. When the pH is increased from 5 to 6, the solubility of corrosion products is increased
by a 100 times.
The indirect effect of pH is how it influences the rate of formation of scales. A high pH reduces the
solubility of the ions in water which leads to a high precipitation rate, thus reducing corrosivity.

Figure 6—Predicted effect of pH on the corrosion rate. (Lee, 2002)

SPE-182955-MS 7

Flow Regime & Velocity

The rate of corrosion in pipelines is dependent on the flow velocity and flow regime. The flow velocity and
regime namely affect the transport of ions and formation of protective scales.
The flowing velocity of the fluid affects corrosion in two ways, destruction of protective films and
reduction of ion concentration near the pipe wall. Flow regime of the fluid is very important as it largely
affects the formation of protective films.
When the flow is laminar, films can form without being stripped off. However, when flow regime
becomes transient or turbulent the protective film is removed and any further formation of a protective layer
is prevented. It is also noted that at high flow rates the film formed in the pits are not as effective at corrosion
prevention as the film is more porous and loose.

Figure 7—Left image is of Laminar (Smooth) Flow, Right image is of Turbulent (Disruptive) Flow.

Figure 8—Predicted effect of flow velocity on the corrosion rate. (Lee, 2002)

Effect of H2S
Leaving aside the cracking and corrosion problems associated with sour service, H2S can have a beneficial
effect on wet hydrocarbon CO2 corrosion as sulphide scales can give protection to the underlying steel.
The effect is not quantified but it does mean that facilities exposed to gas containing low levels of H2S
may often corrode at a lower rate than completely sweet systems.
8 SPE-182955-MS

Assessment Requirements
When dealing with CO2 corrosion it is necessary not to go with "best practices" or a standardized Material
Selection / Corrosion Mitigation system. Each case is very different to another and the input data required
to properly study and assess CO2 corrosion in EOR is vast. Also, existing equipment can be effected by
CO2 breakthrough and hence their impact needs to be evaluated as well. Below is a list of some of the data
that needs to be evaluated:

• Injected CO2 Composition

• Water Chemistry

• Injection Rate and Velocity of Injection

• Design and Operating Parameters

• Service Life

• Production Data & Anticipated Production Data

• Corrosion Simulation Software Inputs

• Inspection results on Existing Equipment

• Existing Equipment design details

Corrosion Assessment & Mitigation

CO2 Corrosion Assessment is extremely important. This will help in identifying the most cost-effective CO2
Corrosion Mitigation system. This may be in the following forms:

• Corrosion Allowance, is deliberately added wall thickness to compensate for accumulated

corrosion expected during the life time of equipment.
• Material Selection, whether the normal use of Carbon Steel can be tolerated or the use of Corrosion
Resistant Alloys (CRAs) are necessary to eliminate the threat of corrosion.
• Corrosion Inspection & Monitoring, this requires regular inspections on equipment wall thickness
and corrosion inhibition efficiency.
• CO2 Recovery Plant, is an option to eliminate excessive CO2 from breaking through onto existing
equipment.
This section will cover the main factors that will influence the corrosion mechanisms predicted and the
suggested preventative methods. This will cover the following above ground and sub-surface facilities:

• CO2 Injection System

• Downhole Equipment

• New Oil Producers

• Existing Equipment

CO2 Injection System

With regards to the Injection Systems, the main influencing factor would be the composition of the CO2
being injected. As stated earlier, no CO2 corrosion can occur if there is no free water present. Lack of water,
will lead to a less stringent material selection and simpler corrosion control. However, a mitigation plan
must be in place in case water ingress is allowed into this system. Therefore, it is imperative to ensure
SPE-182955-MS 9

that the amount of H2O present in the CO2 composition, under the subjective process and environmental
conditions, does not form free water. In addition, Water Analyzers would help at the source of the CO2. This
is intended to shut off the CO2 supply at the source if it exceeds the allowed water content, preventing the
formation of any free water which can lead to corrosion. Also, regular pigging and proper drying of the line
after a hydrotest would ensure no water settlement in the pipeline.
Also, for the pipelines transporting the CO2 for injection, they will need to be studied for Longitudinal
Ductile Fractures as this can occur in high pressure pipelines. A plan needs to be devised to make the line
fracture resistant. For CO2 pipelines, the pressure of the escaping CO2 at the crack tip is very high and is
sustained for a longer period of time due to the unusual phase behavior of CO2 when it depressurizes - when
contained, CO2 is a liquid but becomes a gas when released.

Figure 9—Phase Behavior of CO2 from a Pressure Enthalpy Diagram

Increasing wall thickness helps by reducing stress at the tip of the fracture, and increasing toughness
helps by enabling the steel to absorb more energy before it tears. Increasing wall thickness in this case to
prevent longitudinal ductile fractures in CO2 injection pipelines can be more economically viable because
it allows the operating pressure to be increased, reducing the number of pump stations and pipe diameter. A
ductile fracture control plan needs to be developed to determine the necessary wall thickness and toughness
required for the pipeline.
Other methods for controlling ductile fractures are the use of crack arrestors and controlling the
contaminants (through the use of filters) in the CO2 carried by the pipeline so that the pressure of the
decompressing CO2 at the crack tip is insufficient to cause a fracture to propagate.

Downhole Equipment
As part of one of the CO2 pilots conducted in ADCO, the oil producer was made of carbon steel with
corrosion inhibition above the packer. The downhole completion material of CO2 injector was Super 13 Cr.
Initial corrosion modelling predicted high corrosion rates in the producer tubing due to the carbonic acid
from the CO2. Corrosion logs carried out during the pilot period indicated active corrosion at the tubing
section below the packer.
Following the completion of the pilot the producer was retrieved and an investigation was conducted
which concluded that the corrosion was confined to the uninhibited tubing section in the reservoir zone.
10 SPE-182955-MS

The tubing section above the packer was in good condition due to the effective corrosion inhibition. CO2
Injector did not suffer any damage as it was made of Super 13 Cr.
Based on these findings it was recommended to replace the tubing section below the packer with CRA
such as Alloy 28 or 825 and continue with corrosion inhibition injection for the carbon steel section above
the packer of the oil producer.

New Oil Producers

For new oil producer pipelines, it is necessary to design for the practical worst case scenario. This includes
scenarios of differing possibilities; CO2 and H2S levels, water cut, temperature and pressure, bicarbonate
and flow velocity.
Dependent on the CO2/H2S ratio and the water cut, corrosion may be governed by sweet / sour corrosion.
Also, the H2S can have a mitigating effect on the CO2 corrosion at certain ratios with the formation of a
semi-protective sulfide film.
For new projects, flowlines and pipelines hold a major part of the total cost. So it is regarded as one
of the most important areas of corrosion prediction. The decision of going for Carbon Steel or CRA
material is of major importance. Corrosion Modelling Software are used to predict anticipated corrosion
rates for material selection. They identify the uninhibited and inhibited corrosion rates, give estimates for
the expected required corrosion allowance and define suitability of material to be selected.
However, with regards to CO2 Corrosion the prediction is very uncertain. There are several models
available in the market giving different results for the same input data. It is best to use a corrosion modelling
software tool that has more flexibility with regards to the data to be entered and has been proven in similar
service, as this will provide more reliable results.
Part of ADCO's current projects being constructed are two fields with CO2 Injection. The producers were
designed to be Carbon Steel with Alloy 825 Clad. This was due to predicted uninhibited corrosion rates
ranging from 1mm/year to over 15mm/year for various cases, depending on their water cut and H2S levels.
High amounts of Chloride prevented use of Stainless Steel. The inhibited corrosion rates were observed to
reach 1.5 mm/year for some cases which eliminated the use of carbon steel with inhibition alone.
For a recent pilot project under conceptual study, discussions were held with specialist consultants with
regards to the oil producers. Recent studies have shown that low concentrations of H2S can significantly
reduce the CO2 corrosion rates (Nesic, 2010). However there was a high variability in the H2S concentration
predicted in our projects. Corrosion rates predicted for flow lines indicated that controlling Carbon Steel
corrosion with inhibition at the highest expected CO2 concentration would be challenging if not enough H2S
is present. To facilitate the use of Carbon Steel with Inhibition the design life of the pipe would have to be
reduced from 30 to 10 years. Another option was use of CRA cladded lines based on a techno-economical
evaluation. Due to uncertainty in data no firm conclusion was made. This study was conducted using
a transient mechanistic model developed by the Ohio University Institute for Corrosion and Multiphase
Technology.

Existing Equipment
As CO2 is injected into the reservoirs, it will cause CO2 breakthrough amongst other nearby reservoirs
and enter into their production streams. Existing facilities were not initially designed to anticipate these
conditions and hence their impact needs to be further studied on a case by case basis. Also, gathering
facilities will see an increase in CO2 ratio in commingled fluids from oil producers.
For existing equipment, it is necessary to study what they were initially designed for. Also, it is a must
to evaluate the current condition of the equipment; i.e. remaining wall thickness. The new CO2 fueled
production will be diluted in the gathering systems and hence the corrosivity of the overall production will
decrease. It is necessary to evaluate the impact of the new CO2/H2S levels on the existing equipment.
SPE-182955-MS 11

The critical equipment in the gathering facilities are usually constructed from CRA. These will require
no additional protection from this new production. However, piping sections that cannot withstand this new
service may require corrosion inhibition and close monitoring. Based on life cycle cost analysis a better
decision can be made with regards to upgrading material to CRA and/or use of Corrosion Inhibition with
constant maintenance and monitoring.

Conclusion
For injection systems it is important to eliminate the possibility of free water formation. With no free water
present no corrosion can occur. Material selection is important due to the process conditions, for instance
the corrosive nature of CO2 when free water is present requires mitigation and design attention.
For production it is important to consider the partial pressure of both CO2 and H2S, as this will determine
the dominant form of corrosion. Based on this other factors can be influenced to give the desired outcome
with regards to the FeS/FeCO3 scale produced that would be protecting the steel structure.
Mitigation methods against CO2 corrosion are the introduction of inhibitors, neutralizing the acidity in the
service and upgrade of material to CRA when necessary. Inhibitors will need to be tested in the lab to ensure
that the desired effects are attainable in terms of effectiveness and availability of the inhibitor. Mitigation
methods should be based on company preferences, whether it is a pilot to be used for data gathering or a
full field facility that will need minimum down time. Selection of Material and Corrosion Mitigation to be
used should be based on a techno-economical evaluation.
Summary of ADCO's CO2 EOR Material of Construction is shown below:

Table 2—Summarized CO2 EOR Material Selection based on company experience

System Material of Construction

Carbon Steel with proper Toughness & Thickness as per Fracture Study.
CO2 Injector Pipeline
This is assuming that no free water will be formed.

CO2 Injector Well: Super 13 Cr

Downhole Material Producer Well: Carbon Steel with Corrosion Inhibition with Nickel Alloy
for Tubing Section under the packer

For Oil Producers it is difficult to determine what the best MOC for the
Oil Producers pipelines is. This is based on a case by case analysis whether Carbon Steel
with Inhibition might suffice or CRA Cladded Pipes will need to be used.

References
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Phase with Impurities. Presented at NACE International 2011. Paper 11377, 2011.
Crane, E. 2005. Wettability of Porous Rocks. Crain's Petrophysical Handbook.
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12 SPE-182955-MS

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