UNIT-4

Corrosion prevention methods

Cathodic protection
 The philosophy of cathodic protection use is that organic coatings` application on
metallic structures is the main (leading) method of corrosion control, and cathodic
protection is a complement to protect the defects that are always exist or appear in
organic coatings during application and service.
 Electrochemical mechanism of corrosion of metals in solutions of electrolytes allows
the use of electric current and electric potential to protect metal surface from
corrosion.
 Therefore, cathodic protection works only in solutions of electrolytes and does not
work in media of high electrical resistivity which cannot conduct electrical current: in
natural gas, air, oil, and fuels.
 Two ways exist for cathodic polarization in practice: connection the main metal to be
protected (for example, iron) to less noble metal (aluminum, zinc, magnesium, or
their alloys), or connection to the negative pole of outer power supply (rectifier or
battery).
 The first method is based on sacrificial anodes use, because they are sacrificed being
dissolved as anode, and turn the metallic construction to cathode which does not
corrode. Sometimes this method of cathodic protection is called a passive one (there
is no relationship to passivity!), because we connect equipment to be protected to
sacrificial anode, and “forget” about corrosion for some period.
 The second method of cathodic protection is based on the connection to the negative
pole of the rectifier and use of impressed electric current. This method is called
sometimes an active method of cathodic protection.
 Cathodic protection is one of wide spread methods of corrosion control of
underground and submerged metallic structures and equipment.
 Cathodic protection works only on external surfaces that contact with the electrolyte
and it does not mean the media flowing or stored inside: gas, oil, fuel, or water.
 Many standards exist to implement cathodic protection, testing methods and
monitoring efficacy. High temperatures, destroyed coatings, shielding, microbial
attack, areas of pipes and tanks that are not in contact with the electrolyte and dry
soil are the conditions when cathodic protection is not effective or is working only a
part of time.
 Cathodic protection does not work for thermal insulating structures. It is important to
remember that cathodic protection is working when the following components exist:
an anode, a cathode, an electrolyte, and a complete electrical circuit.
 The absence of one of these components prevents the activity of the cathodic
protection. Sometimes people forget about it and try to use cathodic protection for
hot pipes when hot water evaporates and there is no electrolyte for the passage of
an electric current.
 American engineer Robert Kuhn was the first who used cathodic protection on
pipelines for transporting natural gas in the U.S. in 1928 and more widely in the
1930s. There are several methods to test the efficacy of cathodic protection. The
most common method is to check the electrical potential of the protected pipe.
  Its corrosion rate decreases to two orders of magnitude when electric potential
lower than -0.85 V with respect to a saturated copper/copper sulfate reference
electrode. Keep in mind that the corrosion rate of cathodically protected structure is
never zero but very low value and acceptable for safe use without corrosion risk.
 In the early years (1920-1950) of use of cathodic protection, it was generally
accepted that corrosion structures could be fully protected in soil and water. Then
cathodic protection was begun to use in combination with coatings.
 Cathodic protection is not an alternative to the protection by coatings of pipes and
tanks but an addition. Coatings allow to reduce electric current on several orders of
magnitude and to extend the service life of structures.
 It should be noted that cathodic protection can be used for the protection not only
carbon steel but also cast iron, ductile iron, stainless steel, brass, and aluminum.
Cathodic protection can cause the following problems :
a) Impressed current systems may cause stray current corrosion if
metallic constructions are in the region of cathodic protection activity and are not
connected to impressed current.
b) Coating debonding.
c) Hydrogen embrittlement (in the case of overprotection, less than –1 V
with respect to a saturated copper/ copper sulfate reference electrode and as a result
of water decomposition and hydrogen evolving).
d) Corrosion of aluminum (because hydroxyl ions forming during
cathodic protection are harmful to aluminum).
SACRIFICIAL ANODIC PROTECTION METHOD(Galvanic system)
 In this method, the metallic structure to be protected is made cathode by connection
it with more active metal (anodic metal). Hence, all the corrosion will concentrate
only on the active metal. The parent structure is thus protected.
 The more active metal so employed is called sacrificial anode. The corroded sacrificial
anode block is replaced by a fresh one.
 Metals commonly employed as sacrificial anodes are magnesium, zinc, aluminium
and their alloys.
 Magnesium has the most negative potential and can provide highest current output
and hence is widely used in high resistivity electrolytes like soil.
 Applications:
1. Protection as buried pipelines, underground cables from soil corrosion.
2. Protection from marine corrosion of cables, ship hulls, piers etc.
3. Insertion of magnesium sheets into the domestic water boilers to prevent the
formation of rust.
4. Calcium metal is employed to minimize engine corrosion.
  Advantages:
1. Low installation and operating cost.
2. Capacity to protect complex structures.
3. Applied to wide range of severe corrodents.

 Limitations:
1. High starting current is required.
2. Uncoated parts cannot be protected.
3. Limited driving potential, hence, not applicable for large objects.
Corrosion prevention coatings
 Use of any coating is based on the fact that metal must be isolated from the
aggressive environment.
 All coatings can be differentiated into three groups according to the nature of
basic material: organic, inorganic, and metallic.
 Organic coatings may be paints, polymeric materials, greases, and other
paraffinic mixtures.
 Inorganic coatings may be enamels, ceramics (among them cement), and
glasses.
 Metallic coatings are any metal or alloy.
 All three groups of these coatings are used for the protection of pipes, tanks,
pumps, columns, numerous structures and equipment in contact with natural
gas, atmosphere, water, soil, and different technological solutions.
 Natural gas systems are situated in different geographical areas.
 Therefore, it is important to create coating specifications that protect
structures and equipment under various conditions: resistant to gas, fuels,
water and aqueous solutions, atmosphere, soil, high temperature, and under
thermal insulation.
 There are several types of coatings that are used to prevent corrosion in
drilling and well completion equipment.
 These can be broadly classed as metallic coatings, inorganic coatings and
organic coatings. With all of these classes, the one feature that has a huge
role in the final success rate is the surface preparation.
 The surface needs to be clean and free of contaminants and exhibit the
proper surface profile for the specific coating being applied.
 Metallic coatings include
(1) hot-dip galvanizing,
(2) electroplating of nickel, chromium, copper, tin, and zinc,
(3) electroless nickel plating,
(4) high velocity (oxy-fuel) spray coatings—also known as HVOF,
(5) metallizing (arc or flame spraying),
(6) plasma (PVD) and ion implantation,
(7) chemical vapor deposition (CVD) coatings,
(8) cladding, and
(9) weld overlays.
 The major use of these metallic coatings is to prevent corrosion on carbon
and low alloy steels.
  There are applications of copper plating and hard surfacing for reasons other
than corrosion control. Inorganic coatings include
(1) surface conversions,
(2) inorganic zinc silicate,
(3) HVOF ceramic coatings, and
(4) flame and arc spray ceramic coatings.
 The common surface conversions are anodizing used on aluminum,
phosphating and oxidizing processes used on steels and chromate surface
conversions on steel.
 Organic coatings include
(1) epoxy paints,
(2) acrylic paints,
(3) polyurethane paints,
(4) organic zinc paints,
(5) phenolic coatings,
(6) epoxy-phenolic coatings,
(7) fluorocarbon based coatings,
(8) molybdenum disulfide coatings,
(9) and silicone paints and coatings.
 Generally, where the word paint appears in the above list, the coating consists
of at least two components, one a carrier and one the paint.
 In many cases, with two or more part products that are mixed, the paint
undergoes a chemical reaction causing or assisting in the curing and/or drying
cycles.
 The coatings listed above that do not list plant generally require a heat curing
cycle that sets the coating onto the substrate.
 Most of the common paint systems designed for marine and offshore oil and
gas drilling and surface well completion equipment will be coated successively
with two or more layers of paint to provide the desired corrosion protection.
One common three-coat system is described in Table 4.19.8.
Corrosion prevention inhibitors
 An inhibitor is a substance that slows or stops a chemical reaction. When an
inhibitor is present in sufficient enough quantity to slow a corrosion reaction,
the corrosion is prevented.
 The basic mechanisms by which inhibitors function are as follows :

1). They absorb onto the corroding material as a thin film.

2). They induce formation of a thick corrosion product, which forms a passive
layer.
3). They change the characteristics of the environment either by producing
protective particulates or by removing or inactivating an aggressive
constituent in the environments.
 As a type of material, the inhibitor may be an organic or an inorganic
compound. Inorganic inhibitors include chromates (CrO−24), silicates (SiO−23)
and phosphates (PO−24).
 The three basic types of inorganic inhibitors are anodic passivating inhibitors,
cathodic inhibitors and cathodic precipitators.
 There are also mixed inhibitors that suppress both anodic and cathodic
reactions.
 Anodic inhibitors suppress or prevent anodic reactions by assisting the natural
passivation of metal surfaces or by forming films/deposits that isolate the
metal from the environment.
 These anodic inhibitors are sometimes categorized by being either highly
oxidizing or by being much less oxidizing.
 Examples of the highly oxidizing anions include chromates, nitrites and
nitrates. Sodium nitrite and sodium chromate are two of the most effective;
their effect on the reduction-oxidation (redox) potentials are presented
below:
 2NO−2 + 6H+ + 4e− = N2O + 3H2O where E0 =+1.29V
 2CrO−24 +10H+ +6e− = Cr2O3 + 5H2O where E0 =1.33V
 The low oxidizing anodic inhibitors include phosphates, molybdates, and
tungstates.
 The low oxidizing anions require an external source of oxygen for passivation.
These low oxidizing anions are sometimes referred to as dangerous inhibitors
because they can actually cause pitting when present in low concentrations.
 Anodic inhibitors are also considered dangerous because cathodic reactions
may not be inhibited on unprotected areas .
 The cathodic inhibitors suppress the cathodic chemical reaction and these are
further sub grouped by the way in which the cathodic reaction is affected.
 The three basic types are cathodic poisons, cathodic precipitators and oxygen
scavengers. Of these, oxygen scavengers are the type that are used in drilling
and well completion operations.
 The oxygen scavenger works by combining with free oxygen, this inhibitor
type prevents cathodic depolarization.
 One common effective oxygen scavenger is sodium sulfite and the reaction to
scavenge oxygen is as follows:
2Na2SO4+O2 =2Na2SO4
 The organic type of inhibitors affect the entire surface of the metal by forming
films on the surface. The organic inhibitors are semi-polar in that the make-up
of the inhibitor includes a polar (conductive) and a non-polar (non-
conductive) component.
 The semi-polar nature renders one end of the molecule hydrophobic (water
repelling) and the other hydrophilic (water loving). These semi-polar
molecules bond or attach to the metal surface on the polar (conductive) end
of the chemical compound.
 A thin film only a few molecules thick is adsorbed according to the ionic
charge of the inhibitor molecule and the charge of the metal surface.
 These organic inhibitors can preferentially attach to either the cathode or the
anode of the system; these inhibitors are termed cationic inhibitors (positively
charged) and anionic inhibitors (negatively charged).
  Amines are examples of organic cationic inhibitors and sulfonates are examples of
organic anionic inhibitors. The bonding of these inhibitors is illustrated in Figure
below.

 One advantage of the organic inhibitors is that they are typically self-healing when the
inhibitor is present is sufficient concentration; if the film is damaged or removed through
flowing conditions, the film reforms.
 The factors that effect how well the inhibitor works includes:
1. Molecule size
2. Bond strength to the metal surface
3. Type and number of bonding atoms
4. Filming characteristics
 The value of the corrosion inhibitor is related to how much the corrosion rate is lowered
by use of the inhibitor.
 This can be calculated by the use of the following formula:
E=100(R0−Ri)/R0
where E= inhibitor efficiency
R0 = rate of corrosion without inhibitor
Ri = rate of corrosion with inhibitor
 These inhibitors are used and applied in a number of ways. First, an inhibitor can be used
directly on the metal requiring protection such as drill pipe. This is typically sprayed onto
the metal surface. Second, the inhibitor can be added to the environment such as
additions made to drilling fluids.
 When the inhibitor is added to the environment, it is either added continuously or by
batch. When added continuously, a small quantity is added to maintain a minimum
concentration in the environment.
 When added by batch, a much larger concentration is added at intervals that are
determined through monitoring. When inhibition is selected as the means by which
corrosion is prevented, the environment should be monitored to ensure a minimum
effectiveness of the inhibitor. This is true regardless of the addition method, continuous or
batch.

Types of corrosion inhibitors

 Inhibitors are classified based on their mechanism, chemical structure, chemical properties,
etc. Likewise, corrosion inhibitors were also classified based on how they control corrosion.
 Sometimes, corrosion inhibitor can form two-dimensional (2𝐷) or threedimensional (3𝐷)
protective layer. The difference in the dimensionality of the protective layer is one way by
which the inhibitor can be classified as either adsorption or film forming.

𝑝𝐻. However, the different authors agreed that none of these classifications is entirely
 Figure below shown typical corrosion inhibitor classifications which are in near neutral

satisfactory since they are not mutually exclusive, and some are more informative than
others.
 Organic or Inorganic inhibitors
 This classification is based on the chemical nature of the inhibitors. The inhibitive actions of
many compounds that are organic are similar to those that are inorganic.
 For example, the sodium salts of carboxylic acid (organic) are similar to the sodium salt of
phosphoric acid (inorganic).
 Organic inhibitors are film forming inhibitors which protect the metal by forming a
hydrophobic film on the metal surface.

𝐶12-𝐶18 with amine group on hydrophobic end and some other functional group on the
 Organic inhibitors which are used in oil and gas industry have hydrocarbon chains in range of

opposite end.
 The effectiveness of the inhibitor depends on the chemical composition, molecular
structure, and their affinities for the metal surface.

Oxidizing or Non-oxidizing Inhibitors

 The classification is based on their ability to passivate the metal surface. For non-oxidising
inhibitors like phosphate, tungstate, and molybdate, oxygen is always required for the
maintenance of the passive oxide film but this is not necessary for oxidising inhibitors such
as chromate, nitrite, and nitrate.
Safe or Dangerous Inhibitors
 This refers to the kind of corrosion that will occur if the available corrosion inhibitor
concentration is below the minimum or critical value.
 A safe inhibitor is when the available inhibitor is insufficient in the corrosive medium and
allows uniform corrosion to proceed at a rate that would be experienced if there were no
inhibitor presence.
 However, the insufficient inhibitor concentration would be ‘dangerous’ if it enhances
localised corrosion. The inhibitor is said to be ‘safe’ when the inhibitor concentration in the
corrosive medium is below the minimum or critical value.
 Anodic inhibitors could be categorised as ‘unsafe’ especially at lower concentrations while
cathodic inhibitors are referred to as ‘safe’ inhibitors because they still provide inhibition at
low concentration and their efficiency increases with increase concentration.
Precipitation Inhibitors
 These types of inhibitors are film-forming compounds that affect the metal surface by
blocking both the anodic and/or the cathodic sites thereby providing a protective film on the

The effectiveness of these inhibitors depends heavily on 𝑝𝐻 and a saturation index that also
surface.

depends on water composition and temperature.
Anodic or Cathodic Inhibitors
 This can be regarded as the most informative classification because it indicates which
electrode reactions the corrosion inhibitor interferes with to bring about the protection at
the metal surface.
 The classification is based on whether or not the inhibitor causes increased polarisation on

The anodic (passivating) inhibitors produce a large shift corrosion potential, 𝐸𝑐𝑜𝑟𝑟 in
the kinetics of the reactions involved in a corrosion process.


passive region with a decrease in corrosion current density, 𝑖𝑐𝑜𝑟𝑟.

positive direction to the corrosion potential ,thereby forcing the metallic surface into the

corrosion potential, 𝐸𝑐𝑜𝑟𝑟 to a more negative value or may selectively precipitate on the
 However, cathodic inhibitors will either slow down the cathodic reaction by shifting the

reducible species to the areas with corresponding decrease in 𝑖𝑐𝑜𝑟𝑟.

cathodic areas (electrode) thereby increase the surface impedance and limit the migration of

positive or negative) in 𝐸𝑐𝑜𝑟𝑟 with a decrease in 𝑖𝑐𝑜𝑟𝑟. Fouda et al also used anodic and
 Some corrosion inhibitors behave as mixed inhibitors when there is little change (either

cathodic Tafel slopes (𝛽𝑎, 𝛽𝑐) to explain the type of inhibitor used in their work. Increase in
only anodic (cathodic) Tafel slope indicates anodic (cathodic) inhibitor, and when there is
increase in both anodic and cathodic Tafel slopes is an indication of mixed inhibitor.
Volatile Corrosion Inhibitors

 Volatile corrosion inhibitors are also known as Vapour phase inhibitors (𝑉𝑃𝐼𝑠)
because the inhibitors would be transported to the corrosion sites in vapour phase.

to protect the 𝑇𝐿𝐶 there is a need to incorporate inhibitor that could vaporise from the
 Most of the inhibitor formulation is designed to stay in the liquid phase, and in order

aqueous phase at 𝐵𝑂𝐿 to the upper part of the pipe wall.

 As a result, 𝑉𝑃𝐼𝑠 are usually used as part of corrosion inhibitor formulations.
According to Oehler et al, most of the primary, secondary and tertiary volatile amines that

However, Anbarasi et al disclosed the use of 𝑉𝑃𝐼𝑠 such as cyclohexylamine, 𝑁,𝑁-

are presently use in the industry still remain as patents products.

dicyclohexylamine, and guanidine that provide some level of protection to 𝑇𝐿𝐶.



Inhibitor Application Methods

 There are two important properties to consider when selecting a corrosion inhibitor
application method. First is that the corrosion inhibitor initial concentration must be
sufficient to cover the entire exposed surface of the steel structure.
 The second property is that if portions of the corrosion inhibitor get stripped away, a
new film should form spontaneously. The common types of the corrosion inhibitor
application methods are batch, continuous, and squeeze treatments:
(a) Batch treatment: This can be further subdivided into standard batch, extended
batch, annular slug, tubing displacement, and between pigs batch.
 (b) Continuous treatment: This method is used on producing wells, injection wells,
pipelines, and flow lines. For continuous corrosion inhibitor treatment, Table 1.3 gives the
general criteria for selecting the treatment dosage.
(c) Squeeze treatment: Caution must be exercised when applying this method not to
damage or plug the formation.
Inhibitor Selection and injection
Brief discussions are made here of the different corrosion inhibitors employed in this
work to mitigate both the top and bottom of the line corrosion. These inhibitors were

carbon steel-𝐶𝑂2 corrosion or acidic environments such as 𝐻𝐶𝑙. The physical and
carefully chosen based on previous reports on open literatures of their inhibitive effects on

chemical properties of the different corrosion inhibitors selected for the work were
presented in Table

Methyl di ethanol amine (𝑴𝑫𝑬𝑨)

 Methyl di ethanol amine (𝑀𝐷𝐸𝐴) has always been a material choice as 𝑝𝐻

pipelines but recent researches confirmed the use or selection of 𝑀𝐷𝐸𝐴 for 𝐻2𝑆-
stabiliser to protect oil and gas pipelines. It has been successively applied to protect sweet

containing offshore fields in Persian Gulf, North Sea , and Oceania.

 𝑀𝐷𝐸𝐴 acts as corrosion inhibitor by raising the 𝑝𝐻 of the solution and helps to
increase the carbonate ion (𝐶𝑂3 2−) concentrations. The use of 𝑀𝐷𝐸𝐴 as 𝑝𝐻 stabiliser


di ethylene glycol for hydrate prevention. Generally, any base with high 𝑝𝐻 can be applied
could be dated back to 1972 when it was used in conjunction with mono ethylene glycol or

such as 𝑀𝐷𝐸𝐴 is a better choice because of the thermal stability of the amine.
to neutralise the dissolved carbon dioxide to generate carbonate ions but a tertiary amine

𝑀𝐷𝐸𝐴 can also be recycled in the 𝑀𝐸𝐺 loop to reduce the amount of
neutraliser needed in the flow process. It is important to note that 𝑀𝐷𝐸𝐴 is applicable as


However, the use of 𝑀𝐷𝐸𝐴 will result in flow challenges if the formation water is
inhibitor if the produced water that is formed only developed from condensation.

produced from wells because of its potential for scale formation. It has been reported that

calcite and barite, respectively in the presence of 𝑀𝐷𝐸𝐴.

formation waters usually contain calcium and barium ions, and could lead to formation of

Mono ethylene glycol (𝑴𝑬𝑮)

 Mono ethylene glycol (𝑀𝐸𝐺) is often referred to as hydrate preventer because of

its application to prevent formation of solid-gas hydrate in wet natural gas pipelines at low

It has been reported that 𝑀𝐸𝐺 could be used as inhibitor in 𝐶𝑂2 corrosion when
operating temperatures such as sealines.

the 𝐶𝑂2 partial pressure is very low. However, the use of corrosion control methods such as


application of 𝑝𝐻 stabilisation would be required at higher 𝐶𝑂2 partial pressure. 𝑀𝐸𝐺 is

Previous report has shown that glycol saturated with air at 5-20 oC could contain 𝑂2
expected to be properly de-aerated before injecting to the flowline.

concentration up to 4-5ppm in the glycol mixture which could eventually lead to higher
corrosion rate due to mass transfer of oxygen to the metal surface; which will result in an

The use of 𝑀𝐸𝐺 is cost effective because the rich 𝑀𝐸𝐺 which initially injected
oxygen reduction controlled reaction.


volatile salts) that precipitated in the formation water, and produced a lean 𝑀𝐸𝐺 which
into the flowline can undergo ‘reclamation’ which is a process of removing solids (non-

operated under vacuum (0.10 to 0.15 bar). 𝑀𝐸𝐺 is thereafter vaporised at lower
can be re-injected into the flowline. The reclamation is always carried out in a separator

temperature to avoid decomposition of the 𝑀𝐸𝐺 which could take place around 170-
195oC.

Dicyclohexylamine (𝐷𝐻𝐴) has been used to mitigate 𝐶𝑂2 corrosion as a volatile

Dicyclohexylamine (𝑫𝑯𝑨)

corrosion inhibitor (𝑉𝐶𝐼) where it was assumed that even a small concentration of 𝐷𝐻𝐴


the low solubility of 𝐷𝐻𝐴 in water, it has always been used in a mixture with oleylamine
in the vapour phase could provide sufficient inhibition at the upper wall of the pipe. Due to

(𝑂𝐴) because of its surfactant properties; which is added to 𝐷𝐻𝐴 to maximize the contact
surface area for effective inhibition on metal surface. The inhibition mechanism of 𝐷𝐻𝐴 is
attributed to the strong interactions between the 𝑁 atoms with unshared electron pair from
𝐷𝐻𝐴 and the negatively charged metal surface.

2-mercaptobenzimidazole (𝟐𝑴𝑩𝑰)
 2-mercaptobenzimidazole (2𝑀𝐵𝐼) is a heterocyclic compound which contains
nitrogen and sulphur atoms and have been used over the years to protect corrosion of
different materials such as stainless steel, mild steel, zinc, and copper.
 2𝑀𝐵𝐼 has been reported as a good inhibitor in acid media where acids such as
hydrochloride acid or sulphuric acid were used for acid pickling, industrial acid cleaning, acid
descaling and oil well acidizing.
 In all cases where 2𝑀𝐵𝐼 had been used as corrosion inhibitor, it has always behave
as mixed adsorption inhibitor. The protonated species would adsorb on the cathodic sites of

anodic sites through 𝑁 and 𝑆 atoms, heterocyclic and aromatic ring; which are electron
the metal to decrease hydrogen evolution reaction and at the same time adsorb at the

donating groups to act as barrier to ion migration to the metal surface.

 The study conducted by Moreira et al on benzimidazole confirmed that the inhibitive
effects of the molecules on metal surface is by adsorption of electron pairs isolated from
pyrrole nitrogen or parallel to the surface of the imidazole ring. However, there is no report
in open literature where 2𝑀𝐵𝐼 had been used in organic (acetic) acid environment

2-phenyl-2-imidazoline (𝟐𝑷𝑰)

series aluminium alloy such as 𝐴𝐴5052 in hydrochloric acid solution. Aluminium always has
 2-phenyl-2-imidazoline (2𝑃𝐼) has been reported as a good corrosion inhibitor of 500

good corrosion resistance but the presence of the alloying elements can leads to local
breakdown of passive films resulting in localised corrosion.
 There is no report in open literature where 2𝑃𝐼 has been used as a corrosion

media such as 𝐶𝑂2 environment and brine solution containing acetic acid.
inhibitor for other metals such as copper, and iron (carbon steel), and in other corrosive

2-amino-5-ethyl-1,3,4-thiodiazole (𝑨𝑬𝑻𝑫𝑨)

 2-amino-5-ethyl-1,3,4-thiodiazole (𝐴𝐸𝑇𝐷𝐴) is also a heterocyclic compound

Similar to the discussion on 2𝑀𝐵𝐼, organic compounds such as 𝐴𝐸𝑇𝐷𝐴 which contain
containing polar functional groups which are responsible for adsorption on a metal surface.

polar groups such as nitrogen, sulphur, and oxygen are effective as inhibitor for metals like

The interesting part of this present work is that 𝐴𝐸𝑇𝐷𝐴 has not been effectively
copper and iron in hydrochloric acid solution.

investigated on carbon steel in 𝐶𝑂2 brine solution with/without acetic acid. 𝐴𝐸𝑇𝐷𝐴 is


also a mixed inhibitor because it always affects the anodic and cathodic reactions; resulting

𝐴𝐸𝑇𝐷𝐴 molecules on metal surface increases with increasing concentrations to prevent

in low corrosion rate. Reports also confirmed that the inhibition efficiency and adsorption of

pitting corrosion.

Zinc Chloride (𝒁𝒏𝑪𝒍𝟐)

 Since the use of chromate and dichromate inhibitors have been discouraged because
of toxicity to the environment, and researchers have been opting for other environmental
friendly inorganic inhibitors which could be a good replacement for chromates.
 Zinc chloride has been one of the replacements for chromate. It is also an inorganic
inhibitor. It is believed that zinc chloride is a cathodic inhibitor which was by precipitation of
zinc hydroxide at cathodes.
 𝑍𝑛𝐶𝑙2 also has little effects on the solution 𝑝𝐻 and it is assumed to have
significant effects on the formation of iron carbonate if it is used in 𝐶𝑂2 environment.


However, it has not been used to protect oil and gas pipelines. It is incorporated with other
organic inhibitors as formulation in this study.

Commercial Inhibitor formulation (Defined as 𝑪𝑰-A)

A commercial corrosion inhibitor defined in this work as 𝐶𝐼-𝐴 was supplied by

𝑁𝐴𝐿𝐶𝑂 (an Ecolab company). The formulation comprises of 𝑁-benzyl-alkylpyridinium,


tall oil, diethylene triamine imidazoline, 2-mercaptoethyl alcohol, and a proprietary amine

The initial 𝑝𝐻 of the formulation is 9.75 which is high enough to act as 𝑝𝐻

compound.

stabiliser to encourage formation of iron carbonate in 𝐶𝑂2-brine solution. 𝐶𝐼-𝐴 is a



𝐶𝑂2/𝐻2𝑆 corrosion.
patented mixture that has been used previous by some pipeline operators to mitigate

effect of 𝐶𝐼-𝐴 is compared with other corrosion inhibitors in different corrosive media.
 Further details of the formulation cannot be provided in this report. The inhibitive

𝐶𝐼-𝐴 is a patent commercial corrosion inhibitor formulation that was supplied by

𝑁𝐴𝐿𝐶𝑂 Holding Company, and comprises of the following compounds:  𝑁-Benzyl-
alkylpyridinium  Tall oil, diethylene triamine imidazoline 2-mercaptoethyl alcohol 
Proprietary amine compound
Injectables:
 Injected Fluids (Drilling Fluids, Oxygen and Acids) Drilling fluids are comprised of
many potential constituents. The drilling fluid could be water based, oil based or synthetic
based.
 Brines are a form of water-based fluids. The fluids could have the pH adjusted to high
levels with the use of alkalis such as sodium and potassium hydroxide.
 The role of the drilling fluid on corrosion is related to many factors, including the pH,
the chloride content, and the oxygen content.
 Two of common failure modes in drill strings are fatigue and corrosion fatigue. An
example of a corrosion related affect is increasing chloride contents decrease the fatigue life
in drilling fluids. the corrosion fatigue tests conducted related chloride content to fatigue life
in different drilling fluids.
 The highest corrosion rates are found in corrosive systems in the presence of even
minute quantities of oxygen. Oxygen has anodic and cathodic effects in that it acts as a
cathodic depolarizer and an anodic polarizer. Oxygen accelerates corrosion due to other
corrodents such as CO2, H2S, salt solutions, and injected mineral acids.
 In drilling operations, the fluids used in drilling are exposed to air and this leads to
oxygen being dissolved in the drilling fluid. This dissolved oxygen with chlorides increases
corrosion .The effect of oxygen was found to be linear with the range and conditions but this
is not typical.
 Oxygen also decreases corrosion fatigue life. Corrosion fatigue tests have been
conducted demonstrating the relationship between oxygen content and fatigue life in drilling
muds.
 An additional problem exists when the injected oxygen containing fluid mixes with
production fluids that may contain acid gases. When H 2S is present, the oxygen could reduce
the hydrogen sulfide to elemental sulfur with potential drastically increased environment
severity. When combined with CO2 even at low parts per million (ppm) levels, the corrosion
rates increase dramatically.
 Acids can result in very rapid corrosion rates and the can render normally passive
materials active. When passive materials become active, there can be localized as well as
general corrosion.
 One risk in many downhole anaerobic conditions is that the active pits may not
repassivate when the acids are no longer in contact with the metal.
 Mineral acids are often injected to stimulate production by cleaning out formations.
These acids are typically hydrochloric acid or a mixture of hydrochloric and hydrofluoric
acids.
 These mineral acids are very corrosive at ambient temperatures and the increase in
temperature in downhole environments can render the acid attack even more aggressive.
The effect of temperature on corrosion rates was previously discussed .
 These acids are most often inhibited to prevent corrosion on tubing string but the
inhibitor used may not be effective in the specific downhole condition, not protective against
one of the materials of construction used or may cause corrosion.