H.M. Abd El-Lateef et al / Chemistry Journal (2012), Vol. 02, Issue 02, pp.

52-63 ISSN 2049-954X

Review Article

Corrosion Protection of Steel Pipelines Against CO2

Corrosion-A Review
Hany Mohamed Abd El-Lateef 1, 2, Vagif Maharram Abbasov2, Leylufer Imran Aliyeva2 and Teyyub Allahverdi Ismayilov2
1
Mamedaliev Institute of Petrochemical Processes, National Academy of Sciences of Azerbaijan,Baku, Azerbaijan
2
Chemistry Department, Faculty of Science, Sohag University, 82524 Sohag, Egypt
*E-Mail: Hany_shubra@yahoo.co.uk

Abstract
One of the serious problems of oil extracting industry is the corrosion process. The successful application of carbon steels
in oil and gas pipelines and production tubular in Carbon Dioxide (CO2) containing environments depends mainly on either
the formation of protective corrosion product film or the use of corrosion inhibitors. The mechanism of corrosion of carbon
steel in media containing CO2 is complex, and in dependence on the prevailing conditions it may lead to general or local
corrosion and corrosion cracking. The inhibition mechanism is attributed to the strong adsorption ability of the selected
inhibitors on steel surface, forming a good protective layer, which isolates the surface from the aggressive environment.
The current state of research in corrosion protection of steel pipelines against CO2 corrosion is surveyed. The review covers
CO2 corrosion and its inhibition. The influence of inhibitors molecular structure on corrosion layers in CO2 corrosion is
discussed.

Keywords: CO2 Corrosion, Inhibition, Pipelines, Steel Inhibitors, Carbon Dioxide

1. Introduction

Pipelines play an extremely important role through the
world as a means of transporting gases and liquids over
long distances from their sources to ultimate consumers.
So that corrosion problems exist in the oil industry at every
stage of production from initial extraction to refining and
storage prior to use requiring the application of corrosion
inhibitors (Migahed, 2005).
Oilfield corrosion manifests itself in several forms, among
which CO2 corrosion (sweet corrosion) and hydrogen
sulfide (H2S) corrosion (sour corrosion) in the produced
fluids and corrosion by oxygen dissolved in water injection
are by far the most prevalent forms of attack found in oil
and gas production (Villamizar et al, 2007).
Corrosion of carbon steel is a significant problem in the oil
& gas production and transportation systems, which causes
significant economic loss (Song et al, 2004). As a result of
corrosion, rupture of the pipe wall frequently causes failure
of petroleum and gas pipelines. The breakdowns are
followed by large losses of the products, environmental
pollution and ecological disasters (Mikhailovskii et al,
1997). The majority of oil and gas pipelines failures result
from CO2 corrosion of carbon and low alloy steels (Lopez
et al, 2003). It occurs at all stages of production from
downhole to surface equipment and processing facilities
(Fu el al, 1993). The mechanism of carbon dioxide
corrosion is a complicated process that is influenced by
many factors and conditions (i.e. temperature, pH, partial
pressure of CO2, etc.) (Kermani and Morshed, 2003).
These range from corrosion pipeline and composition of
the solution to other environmental factors (Videm and
Dugstad, 1989). However, significant progress has been
achieved in understanding the mechanism of CO2
corrosion in the oil and gas industry (Kermani and
Morshed, 2003), but an understanding of its inhibition
mechanism and the kinetics of the inhibition process
necessary to quantify formulations that will provide a
desirable level of protection, remains incomplete.

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 H.M. Abd El-Lateef et al / Chemistry Journal (2012), Vol. 02, Issue 02, pp. 52-63
The use of chemical inhibitors has been acknowledged as
one, and a very practical and most economical, method of
combating CO2 corrosion (Ramachandran & Jovancicevic,
1999 and Durnie et al, 1999). The inhibiting molecule
retards the rate of corrosion by acting at the metal –
corrosive medium interface.
The following topics will be covered in the text below:
• CO2 Corrosion
• Effect of Corrosion Inhibition
• Inhibition of Carbon-Dioxide Corrosion
2. The Background
2.1. CO2 Corrosion
CO2 corrosion is one of the most studied forms of
corrosion in oil and gas industry. This is generally because
of the crude oil and natural gas from the oil reservoir / gas
well usually contains some level of CO2. The major
concern with CO2 corrosion in oil and gas industry is that
CO2 corrosion can cause failure on the equipment
especially the main downhole tubing and transmission
pipelines and thus can disrupt the oil/gas production.
CO2 corrosion was reported as early as 1940 (Ikeda et al,
1983). The enhanced corrosion rate of oil tube steels under
conditions in which carbon dioxide is present has been a
serious problem in the oil industry for many years.
Corrosion under these conditions occurs generally in
oxygen-free environment. The type of CO2 corrosion
varies according to the precise environmental conditions
(Crolet, 1994). In general, the reactions involved in the
CO2 corrosion of carbon steel in typical anaerobic aqueous
solution are (De Waard et al, 1975 and Dayalan et al,
1995):
Fe 2 + + CO 32 − → FeCO 3 ………………......(1)
H 2CO3 + 2e − ↔ H + + 2 HCO3− ……………….(2)
2 HCO3− + 2e − ↔ 2CO2− + H + ………………...(3)
2+ −
Fe → Fe + 2e …………………………….…..(4)
2HCO3− + Fe2+ → Fe( HCO3 ) 2 →
……………...…(5a)
Fe( HCO3 )2 → FeCO3 + CO2 + H 2O ………....(5b)
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Fe 2 + + CO32 − → FeCO 3 ………………………..(6)
During the process of CO2 corrosion, the corrosion
products such as FeCO3 and Fe(HCO3)2 build up over
time, partially passivating the corroding steel surface due
to their limited solubility. The works of Hausler and
Stegmann (1998) and Dugstad (1992) revealed that the
corrosion film influenced significantly on the corrosion
rate of carbon steel, which may also, influenced the
efficacy of the corrosion control practice by altering the
chemical nature of the steel surface. Obviously, it is
significant to understand the microstructure and the
characteristics of the surface film induced from carbon
dioxide corrosion under precise conditions in order to
achieve better protection of oil tube steels.
2.2. Effect of Corrosion Inhibition
The two most common sources of corrosion inhibition
need to be considered:
a) Inhibition by components present in the crude oil
b) Inhibition by addition of corrosion inhibitors
2.2.1. Corrosion Inhibition by Crude Oil
It has been known for a while that CO2 corrosion rates
seen in the field, in the presence of crude oil are much
lower than those obtained in laboratory conditions where
crude oil was not used or synthetic crude oil was used. One
can identify two main effects of crude oil on the CO2
corrosion rate. The first is a wettability effect and relates to
a hydrodynamic condition where crude oil entrains the
water and prevents it from wetting the steel surface
(continuously or intermittently). Cai et al (2003) discussed
this effect and its modeling in detail. The second effect is
corrosion inhibition by certain components of the crude
oil, which reach the steel surface either by direct contact or
by first partitioning into the water phase. Little is known
about the nature and the effectiveness of these
components, which inhibit corrosion. In a recent detailed
study on the subject, Hernandez et al (2003) declared that
the degree of inhibition was quantitatively related to the
chemical composition of the crude oil and specifically to
the concentration of saturates, aromatics, resins,
asphaltenes, nitrogen and sulphur (Nesˇic, 2007).
Research studies performed with different Venezuelan
crude oils, have shown the capability of some oils to
inhibit significantly the uniform corrosion rates as well as
the hydrogen permeation and sulfide stress cracking
susceptibility in the presence of CO2 and /or H2S. For
example, a reduction of over an order of magnitude in
corrosion rate was found with the addition of only 1% of
crude oil, in laboratory experiments at 72 psi CO2 and
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80°C. It was determined that protective corrosion
properties of the evaluated crude oils were related to the
adsorption of organic compounds, which modify the
morphology, composition, and compaction grade of
corrosion products. In addition, it was noticed that the
presence of some sulfur in chemical analyses performed on
the corroded coupons evaluated at those conditions
(Mendez et al, 2001).
The inhibiting effect of several crude oils on corrosion was
studied at different crude oil /water ratios. A statistical
analysis showed an important difference between
paraffinic and asphaltenic crude oils from the mechanistic
point of view, with new findings on the variables that
mostly influence the corrosion inhibiting mechanism
(Hernandez et al, 2002).
2.2.2. Corrosion Inhibitors
Most corrosion inhibitors used in oilfields are organic
compounds, containing nitrogen or sulfur functionalities.
They belong to the surfactant category of molecules
(surface-active agents), which preferentially adsorb onto
any surface or interface in a system and alter the surface
and interfacial free energies, even at low concentration
(Hernandez et al, 2003). The surface-active properties
come from their amphipathic, lipid like, molecular
structure, which contains a polar head group having strong
attraction to water, referred to as a hydrophilic head and a
non-polar hydrocarbon chain having little attraction to
water, called a hydrophobic tail.
The way organic corrosion inhibitors inhibiting CO2
corrosion of carbon steel is related to their surface active
properties can be described in three parts i.e. 1) adsorption
onto the steel surface (diffusion or protective layer), 2)
changing the wettability of the steel surface (so it is not
wetted with water), 3) accumulation at the oil-water
interfaces (changing the oil-water interfacial tension and
making it easier for the oil to entrain the water).
It is accepted that organic corrosion inhibitors adsorb onto
the steel surface to inhibit corrosion processes. The types
of adsorption can be distinguished by the mechanisms:
physical (electrostatic) adsorption involves an electrostatic
attractive force between ionic charges on inhibitor
molecules and electric charged steel surface;
chemisorption results from sharing free electron pairs or
charge transfer to form strong chemical bonds between
nonionic inhibitor molecules and steel (Papavinasam et al,
2007). The examples of ionic type and nonionic type
inhibitors are quaternary ammonium chloride, RN
(CH3)3+Cl- (Rosen, 2004) and imidazoline, R1N(CH2)2NR2
(Gusmano et al, 2006).
Independent on the adsorption mechanisms, the attractions
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or chemical bonds are between the hydrophilic head of
inhibitor molecule and the steel surface. In a layer of
adsorbed inhibitor molecules, the hydrophobic tail on the
inhibitor molecules face toward the bulk solution and have
a strong tendency for self-assembly to form a hydrophobic
barrier for corrosive water (Ramachandran et al, 1996). It
is believed that by forming the hydrophobic barrier,
surfactants can alter the surface wettability of carbon steel.
The wettability of a steel surface in oil-water two-phase
system, involves the interaction between oil-water, oil-
steel and water-steel interfacial tension. Since liquid-steel
interfacial tension is not easy to measure directly, the
contact angle of a liquid droplet on steel surface has been
used to indicate surface wettability (Rosen, 2004). The
force balance of three interfacial tensions acting on the
droplet is shown in Equation 7, called Young’s equation.
An angle of 90° or greater indicates that the surface is
hydrophobic and an angle less than 90° indicates that the
surface is hydrophilic (Dobbs, 1999).
σ oil − water cos α = σ water − steel − σ oil − steel …………(7)
Schmitt et al, (1998) and Li et al, (2008) conducted contact
angle measurements by placing oil and water droplets on
carbon steel specimens in a high pressure test apparatus.
The tests were performed on temperature between 75 and
80 °C and under a pressure of 5 bar CO2. The testing fluids
are different crude oils, a synthetic oil and brine with
surfactants (inhibitors and deemulsifiers) added into the
system. The contact angle measurements were made on the
clean surface and pre-corroded (6, 24, 48 and 72 hours)
surface. It was found that clean carbon steel surface and
pre-corroded surface covered with FeCO3 scale both show
hydrophilic wetting property. The addition of quaternary
ammonium inhibitor under FeCO3 scale formation
conditions, results in a hydrophilic surface, however fatty
amine and imidazoline-based inhibitors produce a
hydrophobic surface.
Foss et al (2008) investigated the effect of corrosion
inhibitors on the wettability of the steel surface covered by
FeCO3 protective scale. The wettability tests were
conducted with contact angle measurements in refined oil-
brine system. The authors found that oleic imidazoline and
phosphate ester promote oil wetting for clean steel surface
and FeCO3 covered steel surface. The initially oil wetted
steel surface becomes water wetted with the addition of
cetyltrimethylammonium bromide (ionic surfactant). The
corrosion tests on a stationary electrode in a 3-liters glass
cell showed that the inhibition performances of oleic
imidazoline and phosphate ester were greatly enhanced
after a direct contact of the test electrode to the oil phase.
Without a direct contact (i.e. the test electrode is wetted by
the brine phase), the presence of an oil phase on the top of
brine phase can also improve the inhibition performances
of two inhibitors. The authors assumed that the structure of
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adsorbed inhibitor molecules layer was altered by the
dissolved hydrocarbon in brine (micro-liter solubility) to
have better protectiveness.
It is a well-known fact that corrosion inhibitors partition
between the oil and water phases. The concentrations of
inhibitor in oil and water depend on the solubility of
specific inhibitor. Some inhibitor molecules are also
present at the oil-water interface, with their hydrophilic
heads facing to water and hydrophobic tails orienting to
oil. This behavior minimizes the contact area of oil-water
two-phase, which results in a reduction of oil-water
interfacial tension. The oil-water interfacial tension has a
significant effect on the water entrainment in oil-water
two-phase flow. With increasing surfactant concentration
in a media, at one point, called Critical Micelle
Concentration (CMC), colloidal-sized clusters (micelles)
of surfactant molecules form (Carlota et al, 2005). A
reduction break point of oil-water interfacial tension up to
the CMC can be found for some corrosion inhibitors.
Micelle formation of corrosion inhibitors in oil-water two-
phase flow promotes oil-in-water or water-in-oil emulsion,
which is the stable dispersion of one liquid phase in
another immiscible liquid phase.
Moon et al (2002) measured the changes of a model oil-
brine interfacial tension with five different corrosion
inhibitors with a tensiometer. A great reduction of oil-
water interfacial tension was found for even a low
concentration of inhibitor. Above the CMC point the
interfacial tension becomes stable and full dispersion
begins to form. The emulsion stability tests were
performed by mixing and separating oil and water in
sampling tubes. It was found that inhibitors enhance
stability of oil-water emulsions due to a lower interfacial
tension. A dramatic increase of oil-water interface area
during emulsion formation can trap appreciable amounts of
inhibitor molecules. The authors claimed that loss of
inhibitor at the oil-water emulsion interface can cause
corrosion inhibition failure. Knag et al (2006) reported
similar findings.
McMahon (1991) studied adsorption, interfacial
phenomenon and wettability by testing sodium
alkylethoxyphosphate (water-soluble), oleic imidazoline
and oleic amide (oil soluble) corrosion inhibitors. All the
tested inhibitors have a significant affinity for the oil-brine
interface. The reductions of interfacial tension measured
by a Wilhelmy plate exist up to the CMC points. The
author conducted adsorption tests by using iron powder.
The adsorption of inhibitors from either the oil or the brine
phase was proved fast enough to form a molecule
monolayer fitting a Langmuir isotherm. The corrosion
inhibition was proportional to the measured surface
coverage. The contact angle measurements of oil-in-water
and water-in-oil indicated that the surface became
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ISSN 2049-954X
hydrophobic and oil wetting is enhanced after inhibitor
adsorption.
2.2.3. The Influence of Inhibitors Molecular Structure
on Corrosion Layers in CO2 Corrosion
When the environment becomes highly aggressive or the
scales formed on the steel are non-protective, corrosion
inhibitors are added to the produced fluids in order to
reduce corrosion failures. The most widely used inhibitors
in the petroleum industry are nitrogen containing
compounds such as amines, amides, qua-ternary
ammonium salts and specially imidazolines and their
derivatives. They usually adsorb to the metallic surface
and can act by blocking the active sites or generating a
physical barrier to reduce the transport of corrosive species
to the metal surface. Despite their extensive use, their
mechanism of action is generally unknown (López et al,
2005).
Studies conducted by Rosenfeld et al (1982) established
that inhibitors are incorporated to the corrosion product
layer and form a protective barrier between the base
material and the corrosive media.
SEM results presented by French et al (1989) showed that
the inhibitors use to modify the structure of the corrosion
product layer. They suggested that the structure of the
inhibitor must be the appropriate one in order to interact
with the corrosion products, resulting in a selective
behaviour by which they can be effective on iron
carbonates or sulfides, but not effective on oxides.
Regarding the microstructure of the material, Oblonsky et
al (1995) studied the adsorption of
octadecyldimethylbenzylammonium chloride (ODBAC) to
carbon steel with two different heat treatments. They found
that ODBAC physisorbs strongly to the Ferritic–Perlitic
(F/P) microstructure and weakly to the martensitic
microstructure. They attributed the differences to the
persistency of the passive films on the two microstructures,
with the more stable passive film on the martensitic steel
preventing optimal adsorption of the inhibitor.
The molecular structure of commonly used imidazolines
and their derivatives have a significant role in their
performance as corrosion inhibitors in chloride media
containing CO2, although the information available is not
conclusive. The molecular structure of imidazolines can be
divided in to three different sub-structures: a nitrogen-
containing five-membered ring, a long hydrocarbon chain
(R1) and a pendant side chain with an active functional
group (R2) (Figure 1). The functional groups in R1 and R2
can be variable (Xiuyu et al, 2006).
According to Jovancicevic and Ramachandran (1999), the
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length of the hydrocarbon chain R1 has a key role in the
inhibitive behaviour of the imidazolines. Other authors,
however, consider that this is not a critical factor regarding
the inhibitory properties of the compound [Ramachandran
et al, 1996 and Cruz et al, 2001).
Figure 1. Scheme of a Typical Imidazoline Molecule
Even though it has great importance in field applications,
the interaction between the molecular structure of the
inhibitors and the microstructure of carbon steels in their
performance is barely considered. Bearing in mind that
imidazoline derivatives are widely used as inhibitors in the
oil and gas industry it is, however, important to have a
better understanding of the morphological and
compositional properties of the corrosion layers that are
formed during their usage in order to have a better
comprehension of their inhibition mechanism.
2.3. Inhibition of Carbon-Dioxide Corrosion
CO2 corrosion is a broad term that includes different types
of corrosive failures; seen at pH = 2-10, within a broad
range of temperatures in one-phase media, two-phase
(hydrocarbon-electrolyte) media, and three-phase
(hydrocarbon-electrolyte-vapour-gas phase) media; include
general corrosion; local corrosion, (in the form of pitting
& which takes place both in the absence of carbonate-
oxide deposits on the surface of the metal and under a
layer of such deposits) corrosion-erosion; and a special
type of failure – chalky fracture (Akhmadeeva
and Zagidullin, 2008). The latter type of failure is a
characteristic of CO2-corrosion exclusively. The main
factors that influence the rate and intensity of corrosion
processes and, ultimately, the type of corrosive failure,
which occurs, are the temperature and pH of the medium
and the partial pressure of the CO2. Temperature is the
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ISSN 2049-954X
most important factor. The rate of corrosion of steel below
60 °C in solutions that do not contain O2, is controlled by
the kinetics of the evolution of H2, which is in turn
determined by the homogeneous and /or heterogeneous
formation of H2CO3. Within the temperature range 60-100
°C, corrosion rate is controlled by the stage in which the
layers of siderite undergo chemical dissolution and become
permeable. Since the solubility of the corrosion, products
and the protective properties of the deposits depend on the
pH. This means, pH of the media largely determines the
rate of corrosion i.e. a decrease in pH leads to an increase
in corrosion rate. This relationship, however, is
ambiguous because experience shows that the probability
of local modes of fracture occurring under a layer of
deposits is very high in carbonic-acid media at pH > 7
(Moiseeva et al, 2001).
One of the important criteria during the creation of
multifunctional inhibitors is their chemical structure e.g.
for the creation of a inhibitor, it is important for its
molecule to have diphilic structure-containing a
hydrophilic functional group and a hydrophobic long chain
radical in the molecule (Abdullayeva et al, 2011). In this
case, hydrophilic functional group of molecule will
influence into the different biochemical processes, running
in the bacteria cells, causing their destruction and
perishing. Hydrophobic radical, on the other hand,
promotes inhibiting effect on the border of metal-
electrolyte.
The range of methods available for combatting CO2
corrosion is fairly broad. It is important to choose the
optimum method, which depends mostly on the corrosion
conditions and the mechanism of the corrosion process.
One of the most efficient and economical methods of
dealing with CO2 corrosion is the use of inhibitors.
The corrosion of steel in aqueous media that contain
dissolved carbon dioxide is an electrochemical process. As
is known (Moiseeva and Rashevskaya, 2001), CO2 acts in
two ways – it increases the amount of hydrogen formed on
the cathode and forms the carbonate-oxide films on the
surface of the metal. We can proceed on this basis to find
the most efficient ways of preventing CO2 corrosion. The
first approach involves using any available means to make
the cathodic process efficiently inhibitive, while the
second approach entails the formation of protective
carbonate oxide films or deposits. To realize the second
approach, it is necessary to regulate the pH of the medium
and temperature by physical and chemical methods. The
cathodic process can be slowed down effectively by using
three types of inhibitors:
Inhibitors that can displace depolarizers (HCO3-
ions and H2CO3 and CO2·H2O molecules) from
the surface of the metal.
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Inhibitors, which can form films of the mixed
type, those are impermeable to depolarizers.
Inhibitors that can form bonds with depolarizers
(HCO3- ions and H2CO3 and CO2 ·H2O
molecules).
To varying degrees, inhibitors of all three types can also
prevent the occurrence of the anodic process. However,
inhibition of the cathodic reaction will predominate.
In the first case, the most promising reagents will be
organic substances that are close in chemical structure to
carbonate ions i.e. carboxyl or carbonyl groups. Carbonic
acids, ketones, and esters should be effective inhibitors of
CO2 (when the dimensions of the molecules and their
concentrations in the solution are optimal). Substances that
contain these compounds however, are almost never used
as inhibitors. The domestic oil and gas industry has made
wider use of organic high-molecular weight compounds,
which contain nitrogen: amines, amides, and imidazoles,
nitrogen-bearing heterocyclic compounds, quaternary
ammonium bases and their salts. All of these compounds
efficiently inhibit mainly the anodic process (Rozenfel’d,
1977). The oil and gas industry continues its traditional use
of nitrogen-bearing inhibitors despite the numerous
instances of equipment having failed due to corrosion in
media that contain CO2 and have only small or negligible
amounts of hydrogen sulfide. These inhibitors efficiently
prevent CO2 corrosion only when the concentration of
hydrogen sulfide is substantial (Rozenfel’d, 1977). Thus,
one of the most effective methods of combatting CO2
corrosion has not been put into practice.
One group of inhibitors that is currently in wide use
consists of organic substances or compounds that contain
two or more heterocyclic atoms. Such atoms create (or
help to create) a film on the surface of the metal during
adhesion, and the film are impermeable to molecules and
ions of depolarizers. It is a known fact that inhibitors,
which simultaneously contain nitrogen, sulfur, and
phosphorus, as well as nitrogen and oxygen or sulfur and
phosphorus, can be introduced into oxide-carbonate films
on metal and in the process form mixed films, which are
impermeable to depolarizers (Lahogny-Sarc, 1985).
Two approaches could be taken in forming protective
carbonate-oxide films by regulating the pH and
temperature of the medium. In practice, pH is controlled
by the method of neutralization- with the use of reagents
that shift the pH to the alkaline region (pH = 8-10). This
helps to form a protective layer of siderite on the surface of
the metal. Regulating the temperature regime by means of
chemical reagents is possible theoretically but is difficult
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ISSN 2049-954X
in practice (Moiseeva and Rashevskaya, 2001). Thus, the
type of inhibitor of CO2 corrosion should be chosen based
on the pH and temperature, as well as the initial condition
of the metal surface (the type of film and /or deposits on
the surface of the metal being protected).
The addition of corrosion inhibitors is a standard practice
in oil and gas production systems to control the internal
corrosion of carbon steel structures. Nitrogen based
organic inhibitors, such as imidazolines or their salts, have
been successfully used in these applications even without
an understanding the inhibition mechanism (Jovancicevic,
1999). The corrosion inhibition of organic compounds is
related to their adsorption properties. Adsorption depends
on the nature and state of the metal surface, on the type of
corrosive environment, and on the chemical structure of
the inhibitor (Bentiss, 1999). Studies report that the
adsorption of the organic inhibitors mainly depends on
some physico-chemical properties of the molecule, (related
to its functional groups) to the possible steric effects and to
the electronic density of donor atoms. Adsorption is also
suppose to depend on the possible interaction of the π
orbitals of the inhibitor with the d-orbitals of the surface
atoms,-induces greater adsorption of the inhibitor
molecules onto the surface of metal which leads to the
formation of a corrosion protection film (Bentiss et al,
2001).
Kuznetsov and Ibatullin (2002) studied the inhibitive
effects of aliphatic carboxylic acids on steel corrosion in
the liquid and vapour phases of carbonate media. The
outcome of their study showed that the acids become more
effective with an increase in their hydrophobicity and can
inhibit both the cathodic and anodic processes on steel
because of their high adsorbabilities. Lauric acid has
declared to be the most effective inhibitor of carbon
dioxide corrosion among the carboxylic acids studied.
Although its molecule includes a relatively long alkyl
fragment (C11H23), this acid is rather volatile. Caprylic
acid, in a concentration of 3.7 m mol/L, inhibits steel
dissolution in the temperature range from 30 to 100 °C and
increases the apparent energy of corrosion activation.
According to Kuznetsov and Ibatullin (2002), films
containing fatty carboxylic acids with C10 to C12, cause the
best adhesion to the steel. It remains, however, unclear that
what is the role of the chemical structure of a carboxylic
acid itself and as an option less hydrophobic i.e. relatively
water-soluble, homologs can be used to protect steel from
carbon dioxide corrosion. This question becomes
increasingly topical since hydrophobicity, which often
enhances the protective effect of chemical compounds, can
make them environmentally dangerous. For example,
hydrophobic substances with log P> 3 tend to accumulate
in living organisms and hence their presence in water, even
in low concentrations, is ecologically unsafe (Frenier,
2000).
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Demand for environmentally safe inhibitors of CO2
induced steel corrosion stimulated a search for new classes
of organic compounds capable of functioning in this way.
It turned out that some carboxylic acid anhydrides can both
effectively inhibit corrosion and firmly chemisorb at the
steel surface from carbonate solutions (Frenier, 2000).
According to Schmitt et al (1993), this is due to the
formation of a salt like product of an inhibitor with Fe2+
and its inclusion into a protective carbonate film.
The inhibition activity of 2-mercaptopyrimidine, 2-
mercapto-4-methylpyrimidine hydrochloride, 2-mercapto-
4,6-dimethylpyrimidine and its hydrochloride upon CO2
corrosion of iron has been studied in a wide range of
concentrations at 40-90 °C using electrochemical and
mass-spectrometry methods. High activity has been found
for all compounds (IE % = 80-99%) at very
low concentrations (0.02–5 mg/L). Adsorption of inhibitor
by metal not only blocks its surface but changes the
reaction mechanism as well. Charge transfer is the limiting
stage of both cathode and anode reactions (Reznik et al,
2008).
Ortega-Sotelo et al (2001) studied CO2 corrosion inhibition
of X-70 pipeline steel by carboxyamido by using
electrochemical techniques. Good inhibition properties of
carboxyamido imidazoline in salt water saturated with
CO2, which increased with its concentration, reaching the
highest corrosion protection with 8.1×10-5 mol L-1. Lower
or higher carboxyamido imidazoline concentrations than
8.1×10-5 mol-1, increases the corrosion rate because the
surface area covered by the inhibitor decreases. A
mechanism, of charge transfer mechanism has been used,
to explain the inhibitor desorption for concentration higher
than the most efficient one. Carboxyamido imidazoline
was a kind of anodic inhibitor.
Farelas and Ramire (2010) studied the CO2 corrosion
inhibition, of carbon steels, through Bis-imidazoline and
Imidazoline Compounds. They found that 1-(2-
aminoethyl)-2(heptadec-8-enyl)-bis-imidazoline forms a
compact inhibitor layer and therefore the corrosion
protection was enhanced. The molecular structure of this
inhibitor allows the usage of lower concentration (10 ppm)
without loss of efficiency.
Okafor et al (2009) studied the corrosion inhibition of mild
steel by ethylamino imidazoline derivative in CO2
saturated solution. The findings of their study was that the
presence of the inhibitor has greatly increased the
corrosion potential (vs. Saturated Calomel Electrode
(SCE) to a more positive region and the shifts are
dependent on the inhibitor concentration. The large shift in
the corrosion potential (vs. SCE) indicates that the
inhibition for this system is probably due to the active sites
blocking effect (Okafor et al, 2009). Secondly, the anodic
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ISSN 2049-954X
reaction is slightly accelerated (above 0.5 V) by the
presence of the inhibitor. This effect, however, may be due
to the large change of the corrosion potential (vs. SCE) by
the inhibitor. Lastly, a pronounced effect is exerted on the
cathodic process. The limiting current for hydrogen
evolution is greatly reduced, indicating that the inhibition
is confined to the hindering of the hydrogen reduction
reaction. At pH 4 or below, direct reduction of H+ ions i.e.
2H++2e-↔H2 is important particularly at lower partial
pressure of CO2 and hindering this reduction process
greatly inhibits the rate of the corrosion reaction. In
addition, the corrosion current density is reduced to lower
values. Moreover, the current density decreased with
increasing concentration of the inhibiting molecules -
indicating an inhibiting effect. The polarization curves
indicate (Figure 2) that the corrosion process in the
presence of the inhibitor is under cathodic control. It
should be noted that the parameters (pH 4, 25 °C and 30
minutes) were chosen to yield conditions where corrosion
product film formation is unlikely or very slow.
The kinetics of the inhibition of CO2 corrosion on high
purity iron electrodes by cetyl trimethyl ammonium
bromide, were investigated in order to elucidate the
mechanism of inhibition. The inhibition was found to be a
combination of two processes. First a rapid process (order
of minutes) connected to diffusion limited adsorption of
the inhibitor, resulting in the inhibition of the anodic part
reaction and a second slower process (order of hours)
leading to a reduction in the corrosion rate through the
inhibition of the cathodic part reaction (Bílková and
Gulbrandsen, 2008).
In oil and gas industry, majority of modern corrosion
inhibitors use nitrogen-containing compounds. Various
amines (primary, secondary and tertiary both aliphatic and
heterocyclic) from pyridines and imidazoline class, their
salts, amine alcohols and triazines are applied as corrosion
inhibitors (Abbsov et al, 2010). These reagents are
practically feasible in application, stable and possess high
degree of protection in corrosive mediums. However,
under modern conditions the further improvement of their
operational characteristics, expansion of functionalities
and assortment is necessary that requires, in first place,
research of perspective kinds of raw materials. Use of
organic acids of various structure is expedient, (from oil
and oil fractions), the synthetic greasy acids etc.
Synthesis of N-derivatives oleic and isomer mono
carboxylic acids and their anticorrosive ability in corrosive
mediums containing CO2 was studding by Abdullayeva et
al (2011). Their results by using Linear Polarization
Resistance bubble tests (Figure 3) shows that 10 ppm dose
is all highly effective with corrosion rates of less than 0.1
mm/yr. This was achieved in the case of inhibitor AI after
200 minutes and for inhibitor AII decreases the corrosion
58
 H.M. Abd El-Lateef et al / Chemistry Journal (2012), Vol. 02, Issue 02, pp. 52-63 ISSN 2049-954X

rate till 0.9 mm/yr after 80 minutes. They also found that, 3. Conclusions
these inhibitors decreases the anodic and cathodic
reactions, act as an inhibitor of mixed type of the steel The following conclusions were drawn from this review:
electrode (Abbasov et al, 2005).

Figure 2. Polarization Curves for N80 Carbon Steel in CO2-Saturated 3% NaCl Solution Containing 2-Undecyl-1-Ethylamino Imidazoline at
25 °C and at pH 4 After 30 Minutes of Immersion (Okafor et al, 2009)

Corrosion inhibitor was obtained on the base of olefins,
extracted from light oil fractions. It has been extracted
amino alcohols with two hydroxyl groups from olefin
fraction at 160-180°C. Water-soluble corrosion inhibitor
on the on the basis of active substance has been prepared
which composes 5% of dosed inhibitor. Created inhibitor
(T-1) has demonstrated high inhibition property and low
corrosion rate. Reagent has been studied as corrosion
inhibitor with the methods of Linear Polarisation
Resistance (Figure 3) and Total Metal Loss. Influence of
potassium salts, of nitro derivative of high α-olefins in 1%
NaCl solution saturated with CO2 on steel corrosion, was
study by Abbsov et al (2010) (Figure 4). Potassium
nitronated, based on C8 olefin and propylene tetramer
protects from corrosion, showed the following protective
efficiency from corrosion.
1. Potassium nitronated (C12)-98.52%.
1. Carbon Dioxide corrosion is one the most studied
form of corrosion in oil and gas industry. This is
generally because of the crude oil and natural gas,
from the oil reservoir/gas well, usually contains
some level of CO2.
2. CO2 acts in two ways - it increases the amount of
hydrogen formed on the cathode and it forms
carbonate-oxide films on the surface of the metal.
3. The inhibitor for CO2 corrosion should be chosen
on the basis of the pH and temperature, as well as
the initial condition of the metal surface (the type
of film and/or deposits on the surface of the metal
being protected).
4. Most corrosion inhibitors used in oilfields are
organic compounds, containing nitrogen or sulfur
functionalities.

2. Potassium nitronated (C14)-97.78%. 5. The percentage inhibition efficiency (η %) of the

inhibitors increases by increasing inhibitor
3. Potassium nitronated (C16-18)-99.74%. molecule size.

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 H.M. Abd El-Lateef et al / Chemistry Journal (2012), Vol. 02, Issue 02, pp. 52-63 ISSN 2049-954X

3.5

3.0
Blank
AI
2.5 AII
(mm/Year)

2.0
Rate (mm/Year)

1.5
Corrosion Rate

1.0
Corrosion

0.5

0.0

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0

Time (Hour)
Figure 3. Aqueous Linear Polarization Resistance Bubble Test in Field Brine, 0.9 Bar CO2, at 50 °C (Abdullayeva et al, 2011)

3.0
Potassium nitronated (C14)
Potassium nitronated (C12)
2.5 Potassium nitronated (C16-18)

2.0

1.5

1.0

0.5

0.0
0 2 4 6 8 10 12 14 16 18 20

Time (Hour)

Figure 4. Effect of Potassium Salts of Nitro Derivative of High α-olefins (50 ppm) on the Kinetics Corrosion of Steel in 1% NaCl Solutions
Saturated with CO2 (Abbasov et al, 2010)

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 H.M. Abd El-Lateef et al / Chemistry Journal (2012), Vol. 02, Issue 02, pp. 52-63
6. The results indicated that the inhibitor molecules
formed a good protective film on the steel
surface.
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