Applied Surface Science Advances 6 (2021) 100128

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Applied Surface Science Advances

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Downhole corrosion inhibitors for oil and gas production – a review

M. Askari, M. Aliofkhazraei *, R. Jafari, P. Hamghalam, A. Hajizadeh
Department of Materials Engineering, Tarbiat Modares University, P.O. Box: 14115-143, Tehran, Iran

A R T I C L E I N F O A B S T R A C T

Keywords: This review article provides structured guidelines on the selection of corrosion inhibitors for broad applications
Corrosion inhibitor in downhole for oil and gas wells. It aims to address the shortage in the relevant academic research area and
Downhole corrosion industrial applications. In this regard, the historical and latest research findings regarding these chemicals are
Oil and gas production
assessed. Moreover, it highlights the areas which can be further explored to respond to industrial requirements.
Acidizing
This review, in particular, describes the corrosion mechanisms in the downhole tubing and the influential factors
such as the partial pressure of CO2 and H2S, temperature, water content, fluid regime, etc. Furthermore, it
elucidates the corrosion control methods, including material selection, internal lining, and the application of
corrosion inhibitors. The main focus is dedicated to the different types of downhole corrosion inhibitors.
Therefore, a holistic review of downhole corrosion inhibition has been discussed, such as the type of chemicals
and their application, through a novel and comprehensive classification of the inhibitors. Finally, the injection
methods of corrosion inhibitors in the downhole application are evaluated, and implications in introducing novel
corrosion inhibitors are explored.

1. Introduction independently focusing on a specific element or component [11, 12].

Tubings and casings play an essential role in the production of oil and
gas. Sustainable production from a reservoir is highly dependent on the
integrity of these downhole strings. One of the significant threats to any
well’s integrity (based on NORSOK D-010 and ISO 16530 standards [1,
2]) is corrosion, which can lead to production shut-down, explosion, and
high-risk incidents, as well as the high cost for the wells’ workover in
case of lack of proper identification, control, and monitoring of corro­
sion [3, 4]. Indeed, due to the importance and the sensitivity of wells as
the heart of hydrocarbon production upstream, any loss or stop of pro­
duction will directly affect the downstream processes. Meanwhile, in­
dustrial accidents, as well as human and environmental disasters, have
been reported as a result of tube corrosion and poor performance of
tubing, further emphasizing the importance of this issue.
Some reports have been published to address corrosion phenomena
in downhole tubing and accessories. Massive failure studies have also
been done to understand the root causes of downhole corrosion failures
[5-10]. Since materials degradation for metallic components of wells can
occur in different sides of production tubing (internal and external) and
depends on the different well intervention activities from completion,
acidizing, and production, many publications are available discussing
corrosion and its control in downhole. Still, they mostly are
In this review paper, based on both our academic and industrial
experiences [13-16], it was determined that there is a clear gap in an
integrated approach to review the downhole corrosion inhibition pro­
cesses within the whole oil and gas well life. Furthermore, with a novel
and comprehensive approach, we have focused on the chemical inhi­
bition of carbon steel casing and tubing in different media, including
completion fluid, acidizing and stimulation fluid, and the production
stream. This approach covers the whole asset life and all possible con­
ditions. In each part, the latest advancements of corrosion inhibitors and
their inhibition mechanism have been reviewed from the scientific point
of view. Also, their injection, application, and testing have been dis­
cussed from the operational and industrial viewpoint. This review also
bridges the research findings and the application of downhole corrosion
inhibitors. To provide a better understanding of the objectives, for the
initial parts of this review, corrosion mechanisms and different mitiga­
tion methods have been briefly discussed.
The main parameters that influence the selection of downhole
corrosion control measures include the corrosivity and content of CO2
and H2S. Operating conditions of the reservoir in terms of temperature
and pressure, the amount of formation water production, the water-to-
gas and condensate-to-gas ratios, the depth of the well are also impor­
tant. The condition of the well in terms of the onshore or the offshore

* Corresponding author.
E-mail addresses: maliofkh@gmail.com, khazraei@modares.ac.ir (M. Aliofkhazraei).

https://doi.org/10.1016/j.apsadv.2021.100128
Received 31 January 2021; Received in revised form 16 May 2021; Accepted 18 June 2021
Available online 27 June 2021
2666-5239/© 2021 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
M. Askari et al.
location, well design and completion procedure, the side effect of
chemical injection on the downstream process, and the possibility of
downhole corrosion monitoring and economic issues must also be
considered [17-21]. Concerning all these factors, there are three
methods of controlling corrosion in downhole coiled tubing, including
the selection of corrosion-resistant alloys (CRA), implementing internal
coatings, and injecting downhole corrosion inhibitors. Among these
three methods, practical experience has shown that the highest reli­
ability in production and continuous operation is obtained through CRA
alloys, where the operating costs throughout the operation are mini­
mized. However, if the analysis and the balancing of CAPEX and OPEX
indicate that the decision to use carbon steel tubing is viable to control
the tubing corrosion against well fluid and maximize the workover and
re-tubing periods, using one of the methods of chemical treatment or
internal coating is inevitable [22, 23].
Annual corrosion cost in the upstream oil and gas industry is esti­
mated at around 1.3 billion USD, and about 33% of this expense (around
463 million USD) is associated with downhole corrosion and material
challenges [24, 25]. Different corrosion mitigation methods have
diverse cost impacts during the life cycle of the oil and gas well, where
integrity and safety are two main aspects that shall be maintained for the
entire duration. The life cycle cost analysis has shown an interesting
trend that helps in decision-making for downhole tubing materials based
on the selection of the tubing grade with or without corrosion inhibitor.
If the final selection is the carbon steel tubing with corrosion inhibitor
injection, operating expenditures (OPEX) during the design life will be
highly dependent on the corrosion inhibitor chemical cost and perfor­
mance. Especially for harsh downhole conditions and high tempera­
tures, the effectiveness, film persistency, and thermal stability will be a
serious challenge. Fig. 1 shows an estimation of cost versus time com­
parison of different scenarios of tubing materials selection and corrosion
control.
Based on Fig. 1, except for the CRA option, the cost of corrosion
mitigation is increasing for other mitigation methods, which are due to
OPEX costs during the life cycle of the wells. For the CRA case, with a
high value of CAPEX at the project development phase, the cost of
corrosion will be fixed for the design life period. Alternatively, if the
carbon steel has been selected, costly workovers and well interventions
can incrementally increase the operational costs. Besides, in this trend,
the condition of the well, type of production fluid (oil or gas), and
location (offshore or onshore) should be considered. Thereby, the ma­
terial selection scenarios and life cycle cost analysis can be widely
different in each of them.
Considering the different processes of the completion and operation
of wells, three different approaches can be adopted regarding the
downhole chemical treatment:
Fig. 1. Typical life cycle cost (LCC) comparison for downhole corrosion control methods.
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Applied Surface Science Advances 6 (2021) 100128
1- The corrosion inhibitors that are injected into the wells to protect the
carbon steel tubes’ internal walls for various API 5CT grades.
2- The corrosion inhibitors that are injected into the tubing during the
well acidizing stage to stimulate or clean the wells. Throughout this
procedure, the HCl or HF acids (depending on reservoir character­
istics) are exposed to tubing. The corrosion risk is extremely high,
which implies that controlling this corrosivity involves selecting an
appropriate corrosion inhibitor.
3- The annular space between the production tubing and its outer
casing is filled with oil-based or water-based fluid during the well
completion stage to provide a suitable hydrostatic pressure. In the
case of using a water-based fluid with heavy brine, the corrosion of
the external surface of the tubing and internal wall of the casing will
be problematic, especially when there is the possibility of leakage of
reservoir fluid into the annular space; The developed corrosion in­
hibitors for corrosion control in this environment are considered in
this paper.
2. Corrosion mechanisms in the casing and tubing
In the absence of water, oil is not corrosive to steel components
typically used in oil and gas production. Therefore, when small water
droplets are surrounded by oil and an emulsion is created, corrosion is
not the primary concern. However, oil wells are faced with various
amounts of formation water, leading to corrosion in the presence of
oxygen and other reducing agents. In the presence of CO2 gas, sweet
corrosion occurs, which is the most common problem caused by hy­
drocarbon fluids, which creates a mass loss. Naturally, oxygen in the gas
form does not exist in oilfield reservoirs. Still, during some operations
such as gas or water injection and the brine handling, there is the pos­
sibility of oxygen ingress to hydrocarbon phase in downhole conditions
and impose server attack to exposed metallic materials. Also, for oil well
with sucker rod and some of the low-pressure gas wells, in case of
improper inert gas blanketing, the leakage of air and oxygen into wells
can be a risk [26].
In the design of many wells, the possibility of sour corrosion due to
H2S is also considered, although this type of corrosion is not always
obvious [26, 27]. Generally, the corrosive conditions in the well depend
on various parameters, including the partial pressure of CO2, the partial
pressure of H2S, fluid temperature, water salinity, water cut, flow
regime, pH, organic acids, and presence of elemental sulfur [27]. Among
these parameters, the partial pressure of acidic gasses, namely CO2 and
H2S, plays a decisive role in the well’s fluid corrosion. The formation of
sulfide and carbonate films under different temperature conditions can
have either destructive or protective effects [28].
Downhole corrosion becomes more complicated in the presence of
corrosion products such as FeCO3 and FeS. In sweet systems, the
M. Askari et al.
formation of FeCO3 creates a semi-protective layer on the metal sur­
faces. The operating temperatures govern the formation and
morphology of this carbonate corrosion product layer. This layer
thickness is associated with the pressure changes over the depth of the
well. In the case of sweet downhole corrosion, by increasing temperature
and pressure, the magnitude of deposition is increased, which leads to an
increase in corrosion rate and solubility of CO2 during flow back [29].
In contrast, extensive studies on the behavior of carbonate film have
shown that the formed layers act as a barrier against the diffusion of
anionic components involved in the electrochemical reactions, and as
the reaction progresses and the layer becomes thicker, the oxidation of
the steel substrate is reduced.
In the presence of H2S, all corrosion rate calculations by CO2 models
will change. Since the FeS inner layers have higher adhesion and pro­
tection than the carbonate layer, the corrosion rate is expected to be
slower than the condition in the presence of pure CO2.
The graph in Fig. 2 is proposed to improve the de Waard-Milliams
corrosion models [30-32] by Pots et al. [33]. This graph illustrates
which corrosion mechanisms and models will be dominant based on CO2
and H2S downhole partial pressure. In the case of the simultaneous
presence of both acid gasses, there is a possibility in which the iron
sulfide layer locally covers the surface, and as a result of the galvanic
corrosion between the covered and bare areas, pitting corrosion domi­
nance the degradation processes. This condition is more probable if the
pCO2/pH2S area ratio is between 20 and 500.
Another critical factor affecting downhole corrosion is the water
wetting effect. Understanding water behavior is vital to determine
which part of the well production is more susceptible to water wetting
and the subsequent risks of corrosion. Above the dew point and at the
height of tubing above which water condensation occurs, the inner layer
becomes wet and susceptible to electrochemical reactions. Besides dew
point, the other factors influential on the water wetting include the gas-
water ratio (GWR), condensate-gas ratio (CGR), and condensate film-
forming properties.
Considering the effects of chloride on downhole corrosion, Liu et al.
[34] studied the effect of chloride concentration on CO2 corrosion of
N80 carbon steel through immersion and electrochemical tests simu­
lating well conditions. SEM observations and XRD analysis concluded
Fig. 2. Corrosion regimes in the presence of H2S and CO2.
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that chloride ions could result in the destruction of the protective
corrosion product layer, and change its morphological characteristics.
However, chloride ions do not change the chemical composition of
corrosion product layers. Under constant temperature and partial pres­
sure, increasing the chloride ion concentration increases the CO2
corrosion damage.
2.1. Flow regime interactions with corrosion in production wells
The fluid flow regime is one of the parameters which has a great
effect on the corrosion rate. The type of flow regime affects thickness
and the velocity of the water layer on the tubing wall and defines the
shear stress and mass transfer towards the metal surface [35]. Changes
of route, curve and projections alter the mass transfer coefficient, and in
multiphase fluids, can alter the corrosion mechanisms. Erosion is also
possible due to fluid flow containing impurities and salts, which can
even influence electrochemical aspects [36-38].
Downhole corrosion is generally associated with wear-related issues.
The fluid regime significantly influences downhole corrosion by
considering water chemistry. Fig. 3 presents the typical downhole flow
patterns and their erosive effects [39]. The concept of "slip and holdup"
is mostly used to measure the corrosion of the two-phase gas corrosion,
which describes the slip of the lighter phase with less density (gas phase)
in the presence of the heavier phase (water). The volume fraction ratio
of the heavier phase to the lighter phase in a low-velocity flow de­
termines the accumulated water within the well, leading to corrosion.
In cases where the high-velocity fluids (annular or mist flow) with
water in the gas phase or a high volume of water in the form of bands
(slug flow or bubble) are accumulated, the well fluid can be character­
ized by the concept of "slip and holdup." During the lifetime of the well,
it is expected that the reservoir pressure and the rate of gas production
will decline. In this case, within the gas and condensate wells, fluids
accumulate during the production stage [40]. Fig. 4 presents the fluid
regimes by reducing the gas flow velocity in a vertical gas/liquid well
[41].
In the bubble regime, the liquid phase is continuous, and the bubbles
are dispersed throughout it. The slug flow condition happens when the
bubble size equals the tubing size, with small bubbles appearing
M. Askari et al.
Fig. 3. General schematic of downhole fluid patterns.
between the bigger bubbles. In the annular regime, the liquid phase fluid
flows in the film mode on the tube wall, and gas flows in the middle.
Usually, small droplets of the liquid enter the gas, and at high velocities,
the gas bubbles also enter the liquid film. Sometimes, due to large
droplets accumulating in relatively high mass flux, the wispy annular
mode occurs [42]. Gas wells usually corrode in the reflux area (the area
between the bottom of the well and the wellhead where condensation
occurs). As the gas rises through the well, the temperature is reduced
due to its expansion; and it is condensed when it reaches the dew point.
3. Corrosion control methods inside the well
Despite the significance of industrial corrosion mitigation strategies
developed in the past few decades, the applicable corrosion control plan
should be selected carefully following the numerous, affecting factors.
These parameters include the corrosion rate of the well, presence, and
concentration of sour hydrocarbon, operating conditions and variation
such as temperature and pressure along with the well depth, formation
water, fluid regimes, depth of the well, location of well as onshore or
offshore, human-crewed or crewless operation of offshore platforms, the
design life of the well, the well completion design and installation of
wellhead and downhole equipment, application feasibility of chemicals
and coatings, possible side effects on downstream processes and the
possibility of monitoring downhole corrosion, and finally economic is­
sues. There are three techniques to control corrosion in downhole tubing
in practice concerning all these factors, including the selection of
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Applied Surface Science Advances 6 (2021) 100128
corrosion resistance alloy, internal lining, and chemical treatment.
In corrosion studies, downhole, special attention should be placed on
pressure and temperature. Corrosion prediction models comprise the
effects of temperature and pressure in the corrosion evaluation while
involving gas composition, velocity, the chemical composition of the
brine, and the mechanical factors [43]. The temperature gradient along
the transmission path from the depth of the well to the wellhead has a
direct impact on the phase density, solubility, and stability of corrosion
products. Nevertheless, the pressure role is different; the total pressure
has no direct impact on corrosion. However, it should be noted that the
total pressure is proportional to the partial pressure of CO2 and H2S,
which has a major effect on corrosion [35].
Fig. 5 shows three scenarios for control corrosion of casing and
tubing in oil and gas production wells addressing produced fluid, acid
treatment, and completion fluids in the annular space between casing
and tubing. Gas and water injection wells are excluded.
3.1. Material selection and use of corrosion resistance alloys (CRA)
Under the circumstances where the fluid is highly corrosive so that
the use of carbon steel tubing in combination with other corrosion
control methods are ineffective in ensuring the integrity of the well, as
well as by taking OPEX, including the cost of chemicals, corrosion
monitoring, and workover and strings replacement costs, usage of car­
bon steel grades are not economically justified, and the use of tubing
with CRA grading will become the only reliable option. Such decisions
are based on field experience and evaluation of a specific alloy in a
specific medium and through simulations. The severity of the corrosion
attacks governs the use of CRA and its type. The use of CRA will lead to
an increase in the initial investment cost, while the use of carbon steel
can lead to higher operational costs. Therefore, during the design stage,
the balance between these two options concerning OPEX and CAPEX
should be considered. Based on this selection, various activities need to
be undertaken for each option, like monitoring and maintenance ac­
tivities [44, 45].
ISO 11960 introduces different grades and the relevant requirements
for various carbon steels used in the downhole casing and tubing [46].
Selecting each grade depends on the design of the well by considering
conditions such as well depth, temperature, and pressure. In the pres­
ence of CO2 and water and the corrosive reservoir fluid, the selection of
carbon steel grades requires corrosion control methods such as in­
hibitors or tubing lining. If the reservoir includes H2S, see ISO 15156 /
NACE MR0175, the standard proposes environmental restrictions for
each of the grades introduced in the ISO 11960 standard. [47].
ISO 15156 / NACE MR0175 Standards and ISO 13680 define CRA
alloys as “alloys that are resistant to uniform and localized corrosion in
oil and gas production environments, while carbon and low alloy steels
are not resistant in such environments” [48]. Accordingly, the ISO
13680 standard introduces various CRA alloys grades used in downhole
tubing and their manufacturing requirements. Nowadays, based on
numerous new wells conditions, there is a significant increase in the use
of CRAs, where corrosion inhibitors are ineffective [49].
Reservoir temperature rarely undergoes significant changes over the
well’s life, but the production rate is lowered with increasing lifetime.
Changes in temperature and pressure during the fluid upward move­
ment in the tubing alter the breakout location in oil wells and the
condensate formation location in gas wells. Corrosion problems are
mostly reported on these sites. Tubing replacement costs could be more
than a million dollars per well. Thus, many of the operators have
adopted the CRA alloys policy to avoid replacing tubing [44, 50].
The SCC behavior of an alloy should be carefully considered while
selecting a suitable alloy. When it comes to selecting materials, it should
be considered that the produced fluid and the future downhole opera­
tion such as acid treatment or temporary shut-in could have a significant
impact on the material resistance. Acid treatment in many CRA alloys
could lead to severe corrosion attacks even in the presence of inhibitors.
M. Askari et al. Applied Surface Science Advances 6 (2021) 100128

Fig. 4. Fluid regimes within the gas well tubing following the increase of fluids and the reduction of the speed and the rate of gas production.

Fig. 5. Downhole corrosion control techniques.

The applied CRA ranges from AISI 420 Stainless (13% chrome) have
been used in environments with CO2 to high nickel alloys such as Has­
telloy C-276 in wells with high H2S concentrations (sour environments)
and extremely high temperatures [32, 51-54]. Selecting the appropriate
CRA grade for the intended environmental conditions is based on lab­
oratory tests and field experiences. Fig. 6 illustrates an example of the
chart used to select a suitable family of CRA alloys relating to the partial
pressures of CO2 and H2S, chloride, sulfur, and downhole temperature.
3.2. Casing and tubing internal lining
The use of coating as tubing lining is also a practical option for
downhole corrosion control. Such coatings are required to be tested in
conditions that replicate operating conditions, such as high pressure,
high temperatures, wear and abrasion, hydrogen sulfide and carbon
dioxide, and all chemicals used in the completion and acidizing stages.
The use of epoxies, phenolics, nylons, novolacs, and several other

5
M. Askari et al.
Fig. 6. Chart of CRA selection based on partial pressures of CO2 and H2S, chloride, sulfur, and downhole temperature [55].
polymer-based coating families have been employed [56, 57]. As an
economical method of dealing with the downhole corrosive conditions,
glass-reinforced epoxies or fiberglass liners and composite liners are of
practical interest. Sharif, et al. [58] have analyzed the use of carbon steel
tubing with fiberglass (GRE) lining, addressed the corrosion records,
challenges related to the use of this method, and evaluated their per­
formance. With successful results of the field analyses by others, the use
of this strategy in oil production wells and water injection wells is
approved from the industrial standpoints [59-62].
Hsi, et al. [63] have evaluated the performance of tubing with
internally plastic coated (IPC) lining installed between 1980 and the
early 1990s in a study revolving around the downhole corrosion control
methods. Regular wireline operations, inspections, stimulations, and
acid treatment operations led to the destruction of the inner coating.
Therefore, the usage of the lining was not recommended in oil and gas
production wells. However, the low friction rate of these coatings and,
consequently, the increased production rate should not be ignored as a
particular advantage [44]. It should be noted that it has always been
attempted to improve the technology and reduce restrictions so that
through using more resistant composites and improving the design of
Fig. 7. downhole internal tubing coating with GRE [66].
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the connection. The application of this method has become common in
more difficult conditions, such as higher temperature and pressure by
increasing abrasion resistance and mechanical damage, as well as the
reduced risk of gas leakage and penetration. For instance, Lauer has
studied the recent developments in the abrasion resistance of internally
plastic coated (IPC) [64, 65].
Fig. 7 presents the assembly of tubing with GRE composite lining. As
can be seen, filling the space between the GRE inner tube and metal
tubing, the cement is injected to enhance the adhesion of the inner layer.
A corrosion barrier ring and flare are utilized to ensure the lack of
leakage of fluid inside tubing from the threaded connection and prevent
corrosion of the carbon steel tubing in the area without coating.
4. Chemical treatment and corrosion inhibitors for downhole
corrosion control
Corrosion inhibitors have been used in oil and gas wells since the
1930s. These days, corrosion inhibitors are well-known as the most
common method of corrosion control, particularly in wells made of
carbon steel components. Using chemical scavengers for oxygen and H2S
M. Askari et al.
removal is common in closed environments like casing/tubing annular
space. The inhibitors are used in batch-wise or continuous injection
programs, and the selection of either of these methods is based on the
type of system.
The type of well’s fluid has a vital role in determining the necessity,
type, and application method of inhibitors. Usually, the new oil wells
have a lower corrosion rate, and their corrosivity is increased over time
by increasing the flow of formation water. Therefore, a common
approach is to wait until the conditions become corrosive to the point
that demands corrosion inhibitor injection. This drawback of this
approach is that at the beginning of corrosion control, and after the
onset of corrosion, the corrosion products have accumulated, and a
rough compositionally heterogeneous surface topography has been
formed. Thus, mechanical or chemical cleaning is recommended before
the application of corrosion inhibitors. In gas wells, the corrosion
problem is a matter of concern from the beginning of production. As
discussed earlier, the gas product is not corrosive by nature.
Nevertheless, the condensed aqueous phase in the tube, which can
also cause the dissolution of the organic acids, is regarded as corrosive
media. Given that the phase volume is much smaller than the fluid
produced in the oil well, the use of inhibitors in these wells can be more
effective [50, 67]. Lower doses of corrosion inhibitors are needed to
protect the cleaner surfaces of the wells. Periodic cleaning results in
effective savings in the use of the inhibitors. Such actions in the case of
film former inhibitors mean that a higher dose of the inhibitor should be
injected after cleaning so that the surfaces are covered with the inhibitor
film once more [44].
Another method of corrosion control is changing the environment
and reducing the water corrosiveness for the metal used in the down­
hole. For this purpose, the use of scavengers and environmental agents
that adjust pH are common. Hydrogen sulfide and oxygen scavengers
remove the aggressive gasses from the environment, and pH agents
control corrosion by reducing the acidity of media. Since the oxygen
scavengers do not properly function in acid environments, they are
usually used along with a pH adjusting agent. Usual commercial oxygen
scavengers are sodium sulfite, ammonium bisulfite, and sulfur dioxide,
to name a few. Nitrites are also known as effective Hydrogen sulfide
scavengers in the production process [44].
Usually, corrosion inhibitors present poor results where an oil film
on the metal surface lacks [68]. However, this issue is resolvable
through the use of water-soluble inhibitors instead of oil-soluble ones.
Choosing the appropriate corrosion inhibitor in deep wells with high
temperatures with large amounts of corrosive gasses, such as sour gas
wells, requires extensive laboratory tests to assess the oil inhibiting
systems. While the continuous inhibitor injection process provides bet­
ter results, the inhibitor injection in most well environments is the batch
mode. Wells with high degrees of corrosion requires the injection of
inhibitors as daily batches [69]. Roughly 10 ppm inhibitor added to the
condensate phase can control corrosion, but the reasonable rate of liquid
production is not clear; therefore, using the rule of thumbs to approxi­
mate the injection rate is a common approach.
To maintain a successful corrosion control program, the following
objectives are to be fulfilled:
1 An effective corrosion inhibitor should be injected.
2 The inhibitor should be in contact with the metal surface.
3 A monitoring program should be organized to measure the effec­
tiveness and the longevity of the operation under operating
conditions.
Since this article has focused on the investigation of downhole
corrosion inhibitors, these chemicals will be studied in detail by classi­
fication into three categories, i.e., downhole injection to control internal
corrosion of production tubing, acidizing corrosion inhibitors, and the
application in the annular space between casing and tubing.
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Applied Surface Science Advances 6 (2021) 100128
4.1. Corrosion inhibitors for production fluid
Among the options for reducing corrosion damage to wells for the
one in the production stage, the use of inhibitors is a more cost-effective
solution than CRAs [70].
Corrosion inhibitors are the chemicals injected into the well in
various ways, such that they protect the tubing lining against internal
corrosion caused by produced fluid. It should be noted that some op­
erators, by selecting the appropriate type and dose of injected inhibitors
into the wells, further protect parts of the upstream facilities after the
wellhead.
There are various inhibitor formulations to be injected into the
produced fluid; however, all of these inhibitors are comprised of a
limited number of base molecules. Fatty acids and several nitrogen-
containing compounds are the main resources to form these chem­
icals. The most common organic inhibitors are fatty imidazolines, which
are made of fatty acids and polyethylene amines. These imidazoline-type
products are soluble in hydrocarbon or water-alcohol-based solutions.
Common reactions are salting with acetic acid or quaternization by alkyl
chloride [69]. Imidazoline with strong annular heterocyclic structures
has been widely used as an efficient corrosion inhibitor in oil and gas
fields, and its positive synergistic effect with scale inhibitors has been
studied, and a proper mixing ratio has been obtained [71].
The film-forming ability of the inhibitors of imidazoline and amino
imidazole inhibitors resulted from nitrogenous functional groups that
can stick to the metal surface by coordination bonding. The repulsion of
the hydrophobic branch prevents the movement of the corrosive sub­
stances toward the surface. Laboratory tests show that the C1018 carbon
steel’s polarization resistance is improved with the proper concentration
of the inhibitor, such that the corrosion current is reduced by more than
95% [72]. Similar trends were reported for imidazole derivatives such as
2-ethyl-4-methylimidazole and 1- benzyl imidazole. These inhibitors
showed 82% efficiency in 1 M HCl solution [73]
Among the inhibitors used in the oil and gas industry, the application
of organic film former surfactants -mainly cationic - is more developed
than the others. Film former amines have hydrophobic alkyl groups that
are connected to nitrogen or ammonium functional groups. Nitrogen-
containing groups are hydrophilic in nature, unlike alkyl groups, and
owing to their positive charge, they can attach to metals negatively
charged surface. The hydrophobic parts provide solubility in oil mole­
cules, and given these two cases, the formation of the barrier layer is
anticipated. The alkyl group has the main role in enhancing corrosion
mitigation efficiency. In other words, the longer alkyl tail results in
better inhibitor performance [74]. The use of inhibitors at high tem­
peratures is often associated with problems such as inefficiency or in­
hibitor decomposition, which usually increases the corrosion rate.
Therefore, the necessity of developing high-temperature and biode­
gradable inhibitors is paramount. Efforts made in this regard are
generally based on alkyl amine, imidazoline, and biopolymer groups
[75].
Inhibitors used today contain a more complex combination of char­
acteristics and are designed to meet the competitive requirements of the
industry. Some of these requirements are as follows.
- Pour point: since the inhibitors are usually stored, they need to
remain in liquid form at low temperatures. The pour point de­
termines the activity and solvent system of an inhibitor. The pour
point of − 30 ◦ C is appropriate. Based on the location, a pour point of
− 40 to − 45 ◦ C might be required.
- Solubility: the solubility/dispersion properties of an inhibitor are
determined by the inhibitor’s purpose. In practice, most inhibitors
are not fully dissolved in water or hydrocarbons, and the matter of
concern is their ability to disperse.
- Performance: the ultimate consumer of the corrosion inhibitor
product should carry out laboratory tests to evaluate the inhibitor’s
performance before purchase or usage in the well.
M. Askari et al.
- Emulsion tendency: the use of inhibitors should not cause secondary
problems. The batch injection method often leads to the formation of
hydrocarbons and water emulsions. In some cases, the emulsions
formed by batch injection have such a high viscosity that results in
the blockage of surface separation equipment in high concentrations
of the inhibitor. As a result, some inhibitors contain special formu­
lations to avoid emulsification. Only a small amount of chemicals
should be used to prevent the formation of brittle emulsions.
Table 1 includes molecular structures that are found in many com­
mercial inhibitors. The amines are often neutralized by an organic acid
or quaternized. Throughout the formulation of numerous inhibitors, the
selection of anionic acid or molecule plays a fundamental role in the
final performance of the product. Furthermore, a mixture of acids is used
to obtain the desired feature in some cases [69].
Corrosion inhibitors are being tested in the field along with scale
inhibitors. The stability of their molecules must be ensured in hot and
cold temperatures. The efficiency of scale inhibitors, such as phosphate
ester polymer compounds and vinyl sulfonate copolymer with imida­
zoline corrosion inhibitor, is higher than the sole use of inhibitors and
does not leave a reduced impact on the corrosion inhibition. As a
favorable instance, the addition of vinyl sulfonate (VS-Co) as a scale
inhibitor does not change the efficiency of corrosion inhibitors [76].
Many inhibitors are a mixture of imidazolines, quaternary ammo­
nium compounds, amides, phosphate ester compounds, and surfactants.
The amide-to-imidazoline ratio in the final compound impacts various
properties such as solubility. Once the inhibitor enters the well, the
different phases are separated. UV-Visible spectroscopy with portable
equipment is one of the chemical analysis solutions available in the field.
If higher accuracy is needed, more advanced techniques, such as fluo­
rescence spectroscopy, are employed. The problem of complex com­
pounds analysis is resolved by using separation methods such as
chromatography. Considering the aforementioned information,
employing these methods with other spectroscopy techniques such as
FTIR and mass spectrometry provides higher accuracy [77].
In a recent study, Wang et al. [78] have studied the capsules con­
taining corrosion inhibitors to control downhole tubing corrosion. In
this study, alginate gel capsules (Alg-Ca2+) were filled with corrosion
inhibitors and additives. The inhibitor release process, along with its
inhibition efficiency, was studied on steel P110 in 3.5 wt.% NaCl
aqueous solution. The results indicated that the synthetic capsules can
gradually release the corrosion inhibitor and effectively prevent tube
corrosion in oil wells. By adding the right amount of BaSO4 additive into
the capsule filled with inhibitor, flooding is facilitated, and the inhib­
iting process is improved. In the other hand by adjusting the weight of
BaSO4 in the capsule, immersion and submergence time of capsule
containing corrosion inhibitor down to annular space can be adjusted
and consequently exposure time for film formation/persistency and
finally inhibition performance can be controlled. The inhibitor mainly
used in this study was imidazolyl-quaternary-ammonium-salt (IQAS),
and its molecular structure is displayed in Fig. 8.
Experiments indicate that IQAS is released through the NaCl solution
in two phases: the release due to swelling and splintering. Once the
capsules were introduced into the solution, the solution penetrates the
capsules, and then the dry capsules swell within the first 4 h. IQAS is
dissolved in open cavities and easily leaves the capsule’s surface. In the
second phase, the mechanical properties of Alg-Ca2+capsules were
degraded, and they were splintered depending on the solution rheology,
acidity, and temperature. The released IQAS concentration progres­
sively increases with prolonged exposure time. Finally, the capsules
become fully splintered. Through the force of gravity, Alg-Ca+2 capsules
loaded with IQAS can reach the bottom of the well. Furthermore, with
the sinking of the Alg-Ca+2 capsules into the wells, IQAS can touch the
entire well-string surface. As a result, the tubes were protected from the
top to the bottom of the well.
In general, when carbon steel is immersed in a non-inhibiting solu­
8
Applied Surface Science Advances 6 (2021) 100128
tion, with the progress of corrosion, the concentration of Fe2+ increases
in the solution. The solubility product Ksp of the FeCO3 compound and a
supersaturation (Ss) can be calculated as follows:
[ ]
[Fe2+ ] × CO2−3
Ss = (1)
Ksp
When the product of [Fe2− ] × [CO2+ 3 ] exceeds the Ksp of the FeCO3
compound, Ss > 1, FeCO3 tends to deposit on the surface, leading to the
formation of a layer that protects the steel substrate from subsequent
corrosion reactions. This film is mostly composed of FeCO3, preventing
both the anodic and cathodic processes by blocking corrosion agents
from reaching the steel substrate. Besides, the protective effect and the
physical properties of the film are changed with environmental condi­
tions such as pH, temperature, and fluid velocity. In general, a dense,
protective film layer is obtained by increasing temperature, especially
over 90 ◦ C and static pH values. As time goes by, an external loose film
can be formed when FeCO3 continued to deposit. The black film formed
on the substrate is not dense and protective after immersion for 48 h
[78].
Zhang et al. [79] have performed rotating cage tests at a velocity of 4
m/s in the aqueous phase saturated with CO2 to evaluate corrosion in­
hibitors’ performance in supercritical CO2 systems. The experiments
were conducted on 38Mn6/C75 downhole tubing (in quenched and
tempered conditions) with martensite-bainite microstructure, an X65
pipeline (with ferrite-pearlite microstructure) as well as three
chrome-containing steels. In supercritical conditions, the highest
corrosion rate was observed at 80 ◦ C. The tested corrosion inhibitors
included two types of imidazoline based on oleic acid, hex­
adecenylsuccinic anhydride, and hexadecyltrimethylammonium (HTA)
bromide. Furthermore, the tested inhibitors have been effective for
chrome-nickel alloys, which displayed a similar performance to carbon
steel. It should be noted that significant cavitation is observed on
low-carbon steels in all tests (with and without corrosion inhibitors).
The minimum pitting density is observed in the presence of the HTA
bromide inhibitor. However, even in this inhibitor’s presence, the depth
of pits reached 30 µm after 96 h of testing.
Fatty acid triazoles have been studied for N80 downhole steels and
carbon steels [80]. Three synthetic fatty acid triazoles in HCl 15 wt.%
were studied based on weight loss and electrochemical methods. Elec­
trochemical polarization measurements showed that triazoles are
mixed-type inhibitors that impact both anodic and cathodic reactions.
Inhibition efficiency percent values (% IE) and the corrosion rate ob­
tained by the mass loss methods in different triazole fatty acid concen­
trations in HCl 15% were examined under boiling conditions at 105 ± 2
◦
C. Maximum IE% was achieved at 5000 ppm. All three inhibitors pre­
sent a suitable protection level at a concentration level of 5000 ppm.
Desirable corrosion inhibition behavior of triazoles is probably
related to the single pairs of electrons in atoms N and S and π electrons in
the heterocyclic ring. The proper adsorption of these compounds on the
surface leads to the high efficiency of inhibition. Also, the side in­
teractions of the long-chain hydrocarbons are bilateral and can lead to
compact inhibitor film formation due to its dense structural network.
The triazole with relatively moderate efficiency includes a double in­
ternal bond, which cafuses lower inhibition efficiency compared with
the triazole-3 π bond [80].
Studies on corrosion inhibitors for elevated temperature acids have
shown that corrosion inhibitors provide protection properties on their
own and are also highly effective in combination with other inhibitors
that usually contain an intensifier along with groups such as acetylenic
alcohols, derivatives of cinnamaldehyde, and organic nitrogen com­
pounds. The most common acid corrosion inhibitors include organic
nitrogen compounds such as amines, amides, heterocyclics, and qua­
ternary ammonium salts, intensifiers such as formic acid, iodides, and
acid-soluble salts of copper, bismuth, antimony, and mercury with
compound groups such as alpha hydroxy acetylene, alkenyl phenones
M. Askari et al. Applied Surface Science Advances 6 (2021) 100128

Table 1
Molecular structures of some commercial corrosion inhibitors in oil fields [26].
Compound chemical name Molecular structure

Imidazolines

Dimerized amido-amines

Oxyethylated primary amin

Alkyl pyridine

Quaternized amines

Dimer-trimer acids (C18 average)

Fatty acids

Naphthenic acids

esters of ethoxylated alcohol

Note: The letter R in this table denotes fatty acids derived from such oils as soya, coconut, tallow, and tall oil.

9
M. Askari et al.
Fig. 8. IQAS, R1, and R2 molecular structures of different hydrocarbon
chains [78].
and cinnamaldehyde derivatives [81].
Zeng et al. [82] have synthesized chitosan-g N-carbox­
ymethyl-2sulfo-4,5–2H imidazolinone (CSIDZ) with various attaching
polymers containing 2-bromoacetic acid, chitosan, 2-sulfo imidazoli­
none as raw materials. Antibacterial grafted polymer activities of a se­
ries of microorganisms were tested by the quantitative suspension
method. Yang Yong-Fei has also synthesized a corrosion inhibitor with
quinolone and benzyl and then mixed it with synergist agents to fabri­
cate ammonium nitrogen quaternary organic corrosion inhibitors [83].
The inhibition and the absorption behavior of 2-undecyl1-sodium
ethanoate-imidazoline salt (2M2) and thiourea (TU) were investigated
using electrochemical methods on N80 steel in 3 wt.% NaCl solution and
saturated with CO2. The results indicated that the corrosion inhibitor
compounds act as mixing inhibitors, and synergistic effects were
observed between TU and 2M2 [84]. Moreover, the synergistic effect of
TU and imidazoline was investigated. It has been shown that utilizing
5–5 mg/L of TU and imidazoline results in 95.1% inhibition efficiency.
In this study, the mechanism of a two-layer film was proposed in which
the TU adsorb on the surface of the steel, and then a film of imidazoline
forms on the top of that, thereby it manipulates the access of water to the
surface of the steel in CO2 saturated 3.5 wt.% NaCl [85].
As it was discussed, the functionality of corrosion inhibitors might be
influenced by fluid flow. CO2 corrosion inhibition of N80 steel is
analyzed by Liu et al. [86]. in single-phase liquid flow and two-phase
liquid/particle by 2-undecyl-1-hydroxyethyl imidazoline (HEI-11), and
2-undecyl-1-hydroxyethyl-1-hydroxyethyl quaternary imidazoline
(HQI-11). The results showed that the corrosion inhibition, in the
presence and absence of imidazolines, is greatly dependent on the flow
conditions as well as the existence of sand particles.
The high pressure of the fluid and the presence of solid particles can
cause erosion-corrosion conditions. The application of corrosion in­
hibitors can be effective for the inhibition of erosion-corrosion [87]. In
recent studies, the following chemical compounds have been evaluated
as corrosion inhibitors for oil and gas applications [88]:
- Monomeric amine surfactant − 1 (MAS-1): With the oxyethylene.
- Polymeric corrosion inhibitor-1 (PCI-1): formation over the MAS-1
agglomeration- polymerization process.
- Polymeric corrosion inhibitor-1 Quaternized (PCI-1Q): same as PCI-1
in which all nitrogens have quaternized with methyl chloride.
- Polymeric corrosion inhibitor-1 (PCI-2Q): formed based on three
types of monomers.
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Applied Surface Science Advances 6 (2021) 100128
- Oleic diamine + 1 EO (glycolic acid salt): an amine with a molecular
weight lower than 700, which exhibits an acceptable performance in
numerous tests in corrosion prevention.
The monomeric structure reduced the surface stress more than the
polymeric structure, which provides a more reliable barrier in reaching
the metal surface in corrosive environments. QCM results (through the
kinetics analysis of the formation of the film) indicated the subjected
inhibitors made the steel surface hydrophobic and were attributed to
this phenomenon; they improve corrosion protection for the surface. The
adsorbed layers provide a relatively good resistance to fluid flow,
especially at lower flow rates [88, 89].
For low-pressure gas wells, keeping the pressure at a constant level
and lowering the hydrostatic pressure at the bottom of the hole through
the formation of agents is an effective conventional method. However,
the continuous use of these agents may cause corrosion problems by
wakening the effects of corrosion inhibitors. Foaming agents such as
alkyl sulfonate (C), dioctyl sulfosuccinate, and ethoxylated nonylphenol
(H) provide anti-corrosion properties in lower temperature levels but are
highly corrosive above this temperature. The use of foaming agents with
corrosion inhibitors results in an acceptable corrosion behavior. How­
ever, the incompatibility between anionic foaming agents and cationic
corrosion inhibitors, which can lead to foam instability and a higher
corrosion rate, needs to be carefully considered beforehand [90].
One of the methods of dealing with corrosion is utilizing emulsions
for the inhibitor carriers to convey corrosion inhibitors into the tubing
space. This method has the advantage of long-lasting inhibition and thus
the reduced consumption of chemicals. When the fluid comes up, the
inhibitors are gradually released, and through being absorbed by the
wall, they prevent water and other corrosive fluids from accessing the
metal surface. For a better comparison of the effects of emulsion,
different doses of various inhibitors were injected. It was observed that
the amount of inhibitor that should be left to cover the surface of the
tube is lowered. On the other hand, these laboratory-scale experiments
have shown their effectiveness and require further field trials [91].
Keeping the corrosion inhibitor film’s consistency at high tempera­
tures within the well has been one of the major challenges of the
corrosion inhibitors [92]. The oil-soluble corrosion inhibitors are
developed for usage in high-temperature (HT) gas wells. Under harsh
laboratory conditions, this type of corrosion inhibitor’s efficiency in the
condition with high pressure and temperature, the presence of brine and
various salts, and the partial pressure of carbon dioxide and hydrogen
sulfide have been studied [93]. Inhibitors that function in such condi­
tions in most cases have alkyl groups with long alkyl trails that attach a
monolayer or bilayer film to the surface [94-96].
On the other hand, the methods of formulating organic molecules
with long trail alkyl in water-based products are also expanding [92,
97]. Yang et al. [98] have found that in several cases, the water-based
corrosion inhibitors exhibit better protection and longer inhibition life
than their oil-based counterparts. A new high
temperature/water-dispersible corrosion inhibitor is identified by
Ramachandran et al. [92], which has high-temperature stability and
corrosion control properties similar to a corrosion inhibitor soluble in
oil.
Besides providing better performance or corrosion control, water-
based corrosion inhibitors also have other benefits, including
improved resolution properties of water and higher flashpoints. Labo­
ratory evaluations using white light interferometry are performed on the
film thickness. In contrast, the film uniformity in the presence of the
water-based corrosion inhibitor is measured, and the information ob­
tained is compared with the field survey results. The results have indi­
cated that the film stability and thickness in corrosion inhibitors emitted
in water are greater than the oil-based corrosion inhibitor [92].
Imidazoline and quaternary amine compounds are the best corrosion
inhibitors in oil and gas production systems. These chemicals prevent
H2S and CO2 corrosion by forming imidazoline and quaternary amine
M. Askari et al.
film, which is absorbed slowly on the metal surface. In other words,
optimal chemical composition with high corrosion protection perfor­
mance and low emulsification tendency can be formulated by modifying
the ratio of quaternary amine to imidazoline [28].
In another study, the effect of inhibition behavior of -undecyl-1-
aminoethyl imidazoline (AEI-11) and 2-undecyl-1-aminoethyl-1-
hydroxyethyl quaternary imidazoline (AQI-11) is studied on the corro­
sion of CO2 in N80 steel in the single-phase liquid flow and two-phase
liquid/particle. Based on the assessments, it became clear that the
ability of AQI-11 in a fuzzy state is better than AEI-11 due to the mul­
ticentral absorption sites in its structure [99]. In a similar study, the use
of 2-mercaptopyrimidine has been reported as an inhibitor for steel
pipelines to prevent CO2 corrosion, which can be integrated into
downhole applications [100].
In 1969, the Shell Oil Company discovered the Thomasville field
about 15 miles south of Jackson, Mississippi. Each well is equipped with
string (tubing) circulation, does not have packers, and the casing of well
is a pressure string. From the beginning of production at Thomasville,
the oil and the inhibitor are circulated to prevent the deposition of sulfur
and corrosion. Despite the frequent injection of the inhibitor, severe
corrosion appeared in the tubing strings, leading to cavitation.
A successful continuous inhibitor system has several characteristics
linked together, including appropriate fuzzy behavior, consistent qual­
ity, handle, dehydration, low vapor pressure, the solubility of sulfur, and
corrosion inhibition [101]. The reason for the initial damages has been
ascribed to the evaporation of the mixture inhibitor-oil carrier under the
bottom, which led to severe corrosion to the depth of wells to the surface
where the inhibitor system condensation takes place. Above this point,
the corrosion was minimal. Regarding this issue, the corrosion problems
are studied in a fuzzy state to develop an oil carrier that is not evapo­
rated until 2000 PSIG at 204 ◦ C (400◦ F) in the presence of sour gas. The
annular deposition problem is examined in two aspects.
- In the field, the laboratory tools simulated the well conditions and
the statistic tests designed based on varying levels of temperature,
tar, oil, and suspended solids are implemented.
- In the research equipment. The laboratory tests to produce tar are
conducted on the controlled sources of nitrogen, sulfur, and oil to
determine the composition of the material, which leads to scale
formation.
The actual program designed for the field utilizes inhibitors that can
be dispersed in water due to its cheap price, ease of access, and lower
required volume for gas saturation.
Smith et al. [102] have published thirty years of experience in wells,
corrosion control mechanisms, and Big Escambia Creek (BEC). Con­
cerning his book, the gas/condensate field began production in 1974.
The produced gas contained 40% CO2 and 20% H2S, while the aqueous
phase possessed 200,000 ppm chloride. These conditions resulted in
severe corrosion, which encouraged further studies on corrosion and
corrosion control methods. Most wells had L80, C75, and N80 grades,
and numerous reports of damage were made on the wells with high
amounts of formation water. Recently, thiadiazole derivatives were
introduced as inhibitors to enhance the carbon steel corrosion resistance
downhole. The CO2-saturated formation water was used to simulate the
oilfield environment. It has been shown that even with the low amounts
of these derivatives, 0.005 mM, the inhibition efficiency of the%99.8
will be achieved. Interestingly, the contact angle of the surface after
immersion was 101◦ , while the parameter was only 26◦ for the bare
carbon steel, which shows the hydrophobic nature of the surface. This
intrinsic feature belongs mostly to the high adsorption of the inhibitor
on the surface [103].
A continuous corrosion inhibitor injection system is developed to
enhance the effectiveness of the process. First, a system of capillaries is
considered. However, the amount of inhibitor required for high volume
production wells and pressure drop is proportional to the capillary
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Applied Surface Science Advances 6 (2021) 100128
tubing length. For this reason, a continuous system is developed via the
injection of inhibitor fluid to the tubing through the casing annular
spaces. A pressure-controlled downhole injection valve, placed in a
mandrel, is located immediately above the packer to control the injec­
tion rate. Since the mandrel is not controlled with corrosion inhibitor, a
single joint of tubing made of 825 alloys is installed under the mandrel
[102].
Corrosion inhibitors with high dispersion capacity in water are
selected for the operations based on laboratory tests. These tests eval­
uated the performance and stability during the time of transfer in the
casing annular space. The inhibitor is mixed with fresh, deoxygenated
water in the wellhead and pumped into the annular well.
It has been concluded that during the years of production, downhole
corrosion in BEC reservoirs has shown phased reduction. Although the
reduced partial pressure of H2S has been effective in this regard, the
reduced dew point in the middle of the tubing string to the lower parts of
the well and lower is among the major causes of reduced corrosion. Also,
the presence of hydrocarbon has dissolved sulfur, which significantly
reduces corrosion. Table 2 shows examples of the corrosion inhibitors
examined for production fluid.
4.2. Corrosion inhibitors for acidizing
Acid treatment of the wells is one of the common methods used to
increase oil and gas production. Acidizing enhances the permeability of
formations and assists the flow of oil and gas into the well [106]. It is
also used in testing and the preparation of the wells, cleaning of the oil
and gas tubing, and water transmission lines to remove the salt deposits
from the inner surface of the metal [107]. Stimulating oil and gas wells
with concentrated HCl solution is essential for increasing production
and eliminating the formation damage [108]. The use of hydrochloric
acid takes priority over other inorganic acids in treatment operations, as
it forms the metallic chlorides, which are soluble in aqueous phases.
Formerly, other acids had been with no remarkable success in compar­
ison with hydrochloric acid. One major reason is that sulfate, nitrate,
and phosphate salts exhibit lower solubility than chloride salts [109].
Acids used in this process react with acid-sensitive materials in the
well as a result of their high chemical reactivity. This means that if the
acid is not hindered, it will be consumed before reaching an acceptable
penetration level in the formation. To reduce the reaction rate of these,
various techniques, such as aqueous acid emulsion in an oil-rich envi­
ronment or dissolving the acids in non-aqueous solutions, have been
proposed [110]. During the acid treatment operation, tubing near the
surface is exposed to low-temperature acids while the bottom of the
wells is in contact with hot acids. Moreover, the inner tube micro­
structure is heterogeneous even if the alloy with the same API degree is
used across the well [108]. Thus, there are corrosion complications is­
sues associated with the acid treatment process.
Using inhibitors is the most effective way of reducing corrosion
during the stimulation of the well [111]. In the absence of a corrosion
inhibitor, the general corrosion rate escalates exponentially by
increasing the acid concentration and temperature. This can be reduced
by adding the right concentration of corrosion inhibitors to protect the
metals in the well [112]. For oil well stimulations, typically, a batch of
corrosion inhibitors is added to the acid solutions. This one-time addi­
tion of the inhibitor’s required dose into the acid holder chamber
corrosion is the most affordable and practical corrosion control method.
Introducing a proper inhibitor can render the usage of simpler and
cheaper alloys possible, which can subsequently reduce the wells’ cost
during the initial investment compared to advanced CRA alloys [113].
Since the acid requires passage through the tubing before reaching
the formation, it needs to contain corrosion inhibitor content. These
inhibitors also need to be active for at least two hours since being
pumped to the formation. In some circumstances (e.g., when the acid is
used for fracturing), the inhibitor needs to protect for at least 24 h [108].
The maximum temperature limit also plays one of the most important
M. Askari et al. Applied Surface Science Advances 6 (2021) 100128

Table 2
Examples of corrosion inhibitors for production fluid based on the field or electrochemical tests.
Inhibitor Medium Material Inhibitorconcentration Test test/ IE(%)(orCR) References
methods treatmentconditions

2-undecyl-1-aminoethyl CO2-saturated 3% N80 100 ppm WL, LPR, RT, static conditions 90.8% [99]
imidazoline (AEI-11) NaCl PDS, EIS,
SEM
2-undecyl-1-aminoethyl CO2-saturated 3% N80 100 ppm WL, LPR, RT, Single phase flow 36.4% [99]
imidazoline (AEI-11) NaCl PDS, EIS, conditions
SEM
2-undecyl-1-aminoethyl CO2-saturated 3% N80 100 ppm WL, LPR, RT, Two-phase flow 19.6% [99]
imidazoline (AEI-11) NaCl PDS, EIS, conditions
SEM
2-undecyl-1-aminoethyl-1- CO2-saturated 3% N80 100 ppm WL, LPR, RT, static conditions 99.2% [99]
hydroxyethyl quaternary NaCl PDS, EIS,
imidazoline (AQI-11) SEM
2-undecyl-1-aminoethyl-1- CO2-saturated 3% N80 100 ppm WL, LPR, RT, Single phase flow 80.9% [99]
hydroxyethyl quaternary NaCl PDS, EIS, conditions
imidazoline (AQI-11) SEM
2-undecyl-1-aminoethyl-1- CO2-saturated 3% N80 100 ppm WL, LPR, RT, Two-phase flow 73.9% [99]
hydroxyethyl quaternary NaCl PDS, EIS, conditions
imidazoline (AQI-11) SEM
imidazolinyl-quaternary- CO2-saturated P110 - PDS, EIS, 70 ◦ C 86.7% after 48 hrs [78]
ammonium-salt (IQAS) 3.5% NaCl SEM, FTIR immersion
in capsule
3-undecane-4-aryl-5- 15%HCl N80 1000, 5000 ppm WL, PDS 107 ◦ C 42.31%, [80]
mercapto-1,2,4-triazole 60.2%
(triazole 1),
3(heptadeca-8-ene)- 15%HCl N80 1000, 5000 ppm WL, PDS 107 ◦ C 61.23%, [80]
4-aryl-5-mercapto-1,2,4- 90.53%
triazole (triazole 2),
3(deca-9-ene)− 4-aryl-5- 15%HCl 1000, 5000 ppm WL, PDS 107 ◦ C 51.42%, [80]
mercapto-1,2–4-triazole 96.2%
(triazole 3)
2-undecyl-1-hydroxyethyl CO2-saturated N80 100 ppm WL, LPR, RT 90.8% [86]
imidazoline (HEI-11) 3% NaCl PDS, EIS,
SEM
2-undecyl-1-hydroxyethyl- CO2-saturated N80 100 ppm WL, LPR, RT 99% [86]
1-hydroxyethyl 3% NaCl PDS, EIS,
quaternary imidazoline SEM
(HQI-11)
2-undecyl-1-sodium CO2-saturated N80 50, 400 pm LPR, PDS, 25 ◦ C, pH=4, 1 bar CO2 83.6%, 94% [84]
ethanoate-imidazoline 3% NaCl EIS pressure by LPR
salt (2M2)
Thiourea (TU) CO2-saturated N80 50, 100 pm LPR, PDS, 25 ◦ C, pH=4, 1 bar CO2 90.2%, 77.9% [84]
3% NaCl EIS pressure by LPR
2-undecyl-1-sodium CO2-saturated N80 20 (2M2)/ 100 (TU) pm LPR, PDS, 25 ◦ C, pH=4, 1 bar CO2 94.3% [84]
ethanoate-imidazoline 3% NaCl EIS pressure by PDS
salt (2M2) + Thiourea
(TU)

2-undecyl-1-sodium CO2-saturated N80 400 (2M2)/ 100 (TU) pm LPR, PDS, 25 ◦ C, pH=4, 1 bar CO2 97.2% [84]
ethanoate-imidazoline 3% NaCl EIS pressure by PDS
salt (2M2) + Thiourea
(TU)

Olefin with an imidazoline Field test: 35% H2S, MS – Field test 204 ◦ C, 19,000 psi CR=12–14 mpy [101]
ring 10% CO2, and 55% ,10,000 mg/l Cl−
CH4
Oil-soluble Field test: 19% H2S, L80, C75 – Field test 138 ◦ C, 7700 psi Successful [104]
42% CO2 and 23%
CH4 + 15% C2+

Imidazoline CO2-saturated N80 25,100,125 ppm WL, LPR, 25 ± 1 ◦ C 49%,84.2%,60.2% [105]

3% NaCl PDS, EIS by EIS

roles during the selection of an inhibitor, as several compounds are donor-type bond [115].
sensitive to decomposition at high temperatures, which results in the Three different mechanisms of absorption can be considered for
loss of their inhibitory effects [114]. Corrosion inhibitors are used in the organic inhibitors, including:
acid treatment of organic molecules and film-forming amines. These
inhibitors are mixed type, which influences both anodic and cathodic 1- π-bond orbital adsorption
branches of corrosion reaction. Their performance is dependent on their 2- Electrostatic adsorption
absorption ability on the metal or the oxide surface. Absorption happens 3- Chemisorption [116]
due to the polar and ionic nature of the molecular and organic compo­
nents that have formed a film via the van der Waals forces with a Following the absorption of the inhibitor molecules on the metal,
physisorption nature, and the film is stabilized by chemisorption and corrosion behavior is influenced by several aspects. Corrosion inhibitors

12
M. Askari et al.
can provide a physical barrier on the metal surface to prevent the
penetration of molecules and ions. It can also directly block the active
sites of anodic and cathodic reactions from interacting with corrosion
reaction intermediates absorbed on the surface. It also affects the elec­
trochemical reactions by altering the electric double layer formed at the
metal/solution interface. Iron oxide is harder than active iron, which is a
weak acid. Moreover, O and N are harder alkalies than S, P, and Se,
which are soft alkali. Hardness implies lower polarizability and higher
electronegativity. In general, the corroding metal surface is free of oxide,
allowing the inhibitor to resume its cathodic/anodic electrochemical
functions. Therefore, adsorption is the main stage of inhibition in acidic
solutions.
The adsorption process involves proton acceptors, electron accep­
tors, and combined molecules. The proton acceptors are a type of
organic molecules that are absorbed on the cathode sites. The group-
specific inhibitors are acidic environments that migrate to the cathode
and receive hydrogen ions or protons. Various common inhibitors in this
group are anilines, quinolines, urea, and aliphatic amines. Electron ac­
ceptors are active in anodic sites and are capable of capturing electrons.
Besides, the passivation inhibitors also fit in this category. Organic
peroxides, selenols, organic thiols, and inorganic nitrates and chromates
are some of the common inhibitors belonging to this category.
Mix inhibitors contain more than one functional group (e.g., NH2 and
SH) in their molecular structure. These inhibitors may have the
following properties:
1- The main structure that is common in both factorial groups.
2- A salt formed by proton or electron directed acceptor groups from
two separate molecules, such as benzene thiol and aniline.
3- A corrosion product with an organic structure capable of creating
organic ions in the acidic systems (pyridinium benzyl bromide).
As mentioned earlier, inhibitors mainly include quaternary salts,
acetylenic alcohols, surfactants, solvents, and impurities. Based on these
techniques, various analysis tools are needed to characterize these
compounds [117]. Acid corrosion inhibitors tend to have a relatively
complex nature and comprise amines, quaternary, various
nitrogen-containing heterogeneous rings, thiourea, and Mannich reac­
tion products, sulfonium salts, and acetylenic alcohols. They usually
contain surfactants to spread the corrosion inhibitor inside the acid and
solvents required for product formulation [118].
Surfactants are surface-active compounds and are referred to as the
compounds that improve the inhibitor’s emission in acid and emulsify it.
These compounds generally have good wetting for the metal surface
[119-121]. Indeed, the surfactants can sometimes have corrosion resis­
tance properties [122, 123], such as the ones commonly used in the
downhole oil and gas industry, including alkylphenol ethoxylates, e.g.
nonylphenol ethoxylate (NPE) [123-126]. The solvents are applied for
the purposes like reducing viscosity and ensuring the stability of the
product in different environments. The intensifiers are mainly added
along with the inhibitor to strengthen the impact of the organic in­
hibitors that are incapable of creating adequate protection for metal
[127]. Typical acid corrosion inhibitors require these compounds,
especially when used in strong acids, high temperatures, or prolonged
contact times. However, the major effective intensifiers have a high
degree of toxicity. For instance, copper and antimony salts can act
deadly at concentrations less than 10 ppm and intoxicate heavy metals.
Observations suggest a significant synergistic effect when multiple types
of intensifiers are used simultaneously. Therefore, using two or more
intensifiers with a low degree of toxicity can make their usage possible in
situations with serious environmental concerns. Formic acid and po­
tassium iodide are among the items for which the synergistic intensifier
effect is observed [127].
The maximum temperature limit is another critical criterion for
selecting an acidizing environment corrosion inhibitor, as several com­
pounds are sensitive to decomposition at high temperatures, resulting in
13
Applied Surface Science Advances 6 (2021) 100128
a loss of their inhibitory effects [114]. For an inhibitor to function
successfully, it should be dispersed in the solution for a certain time. The
effective distribution of the inhibitor in the acidic environment is of
great importance. The inhibitor should remain in the solution during the
field operation and maintain its performance when unforeseen delays
might occur [128].
In this study, it has been attempted to investigate cases of studies
where the inhibitory properties of compounds are used on common steel
in the oil wells and according to the well conditions.
The inhibitor molecular structure has a major impact on the inhibi­
tion performance of N-aryl pyrroles on steel corrosion in acidic solu­
tions. It is observed that pyrroles’ inhibition effect is largely a function of
the type and position of functional groups. The most effective identified
pyrrole is N-pyrrole bearing fluorine at the ortho position [129].
The n-dodecylpyridinium bromide (n-DDPB) and L-octyn-3–01 are
used as corrosion inhibitors for J55 alloy in the oil fields. Both inhibitors
are absorbed by the surface covered by water and lead to a lack of access
to water molecules. Studies have shown that pyridinium forms a weak
bond with the surface covered by chloride, sensitive to temperature and
hydrochloric acid concentration. This mechanism is complete in the case
of DDPB. However, in the case of Actonel, the molecules absorbed to
form the film undergo a chemical reaction. Therefore, Actonel is an
example of a secondary inhibitor. The resultant film has the thickness of
a few molecules and contains unreacted Actonel [108].
Inhibitor performance based on Imidazoline for the carbon steel in a
two-phase fluid loop system with oil-brine fluid at 90 ◦ C and pressure of
300 psi has been studied using the EIS technique. It was discovered that
the load transfer resistance emerges within the first 8 h, and then it
remains constant. It has been suggested that during the first 8 h, the
inhibitor film is compacted over time, then a stable film is obtained. The
improved inhibitory properties through the increase of the inhibitor
concentration from 50 ppm to 100 ppm were negligible [130].
It has been observed that the effectiveness of sodium N -Alkyl-
Phthalamates (Alkyl = nC6H13, n-C10H21, n-C14H29) as a corrosion in­
hibitor on steel SAE 1018 CS in 0.5 mol / L HCl, in addition to its con­
centration, depends on the length of the alkyl chain. By increasing the
two, this effectiveness is also improved. These inhibitors act as mix-type
inhibitors and have prevented oxidation by physical adsorption on iron
[131].
Hao et al. [132] have successfully synthesized 3- (4-Hydrox­
yphenylimino) Indolin − 2-one and analyzed its corrosion inhibition
properties for Q235A steel in hydrochloric acid solution. The inhibitory
efficiency of the compound was at 77.63% with hexamethylenetetra­
mine (HMTA) and reached up to 85.33% with 1,4-dihydroxy-2-butyne
(BOZ). Electrochemical tests show that the inhibitors are combined.
Quraishi et al. [133] have conducted numerous studies on the inhi­
bition impact of several compounds on the wells’ steels. In one study,
through the synthesis of dicinnamylidene acetone, disalicylidene
acetone, and divanillidene acetone as corrosion inhibitors on steel N-80
in15% HCl solution, it was discovered that these compounds act as
mixed-type corrosion inhibitors and that the former two compounds
have greater impacts at 105 ◦ C. All the compounds indicated better
effectiveness in the presence of a potassium intensifier. Three oxadia­
zoles components titled 2-undecane-5-Mercapto-1-Oxa-3,4-Diazole,
2-Heptadecene-5- Mercapto-1-Oxa-3,4-Diazole, and 2-Decene- 5-mer­
capto-1-oxa-3,4-diazole were also synthesized. It was observed that
2-undecane-5-mercapto-1-oxa-3,4-diazole acts as an inhibitor for steel
N-80 in 15% HCl solution with an efficiency of roughly 45%, while the
impact of the same compound with the same condition in the cold rolled
mild steel was about found to be 99% [134].
In another study, dianils were introduced as a successful corrosion
inhibitor. 2,4 didimethyl aminobenzyledene aminophenylene (DDAP),
2,4-dibenzyledene aminophenylene (DBAP), 2,4-divanilledene amino­
phenylene (DVAP), 2,4-disalicyledene aminophenylene (DSAP), and
2,4-dicinnamyledene aminophenylene (DCAP) were synthesized, and
their inhibitory effect in 15% HCl solution at 105 ◦ C was tested on cold-
M. Askari et al.
rolled mild steel, as well as DCAP on N-80 steel. In the case of N-80 steel,
it was discovered that this anode inhibitor possessed a higher efficiency
with increasing temperature from 28 to 105 ◦ C, and reaches 99% at the
concentration of 5000 mg/lit [135].
Three non-ionic complexes based on oleic acid monoamide surfac­
tants, named ET-5, ET-20, and ET-40 were analyzed to address their
inhibitory effects on steel corrosion in 1 M hydrochloric acid. Poten­
tiodynamic polarization curves indicated that the ET-5, ET-20, and ET-
40 acted as hybrid inhibitors and prevented the dissolution of the metal
in the anode and the reduction of hydrogen in the cathode. Electron
microscopy revealed that the inhibitor molecules had formed a strong
protective film on the steel surface [122].
The inhibitory effect of 1- (2-aminoethyl) − 2-oley limidazoline
(AEOI) and 1- (2-oleylamidoethyl) − 2-oleylimidazoline (OAEOI) eco-
friendly compounds are investigated as a corrosion inhibitor in 15%
HCl acid and at the temperature of 298 – 323 K on N80 steel. The OAEOI
compound exhibited a significantly higher inhibition than AEOI due to
the larger size and more active centers. Both of these inhibitors have
mixed functions and implement their inhibitory functions through
adsorption, as confirmed by SEM and Langmuir adsorption isotherm
observations. EIS observations were in agreement with these results
[136].
Menezes et al. [137] have examined halogenated salt (HS)-acetylenic
compound (AC) mixtures as corrosion inhibitors on CRAs of 13Cr and
22Cr stainless steel, ss well as N80 steel and P110 carbon steel in contact
with 15% HCl at 50 ◦ C, 80 ◦ C, and 100 ◦ C, and elucidated the effect of
these compounds. Both Halogenated salt (HS) and acetylenic compound
(AC) with a concentration of 1.5 wt.% demonstrated the best inhibitory
results. The use of these inhibitors renders the application of 13Cr, N80,
and P110 steels in wells at temperatures above 100 ◦ C possible.
In another study, the performance of ester and quaternary ammo­
nium combined with amine was evaluated in different concentrations at
room temperature. Five hours after the mass loss, the optimum con­
centrations of these compounds were compared. It can be seen that the
formula containing 5000 ppm amine, 3000 ppm ester, and 2000 ppm
quaternary ammonium bromide demonstrates the best performance in
terms of corrosion, where the efficiency of this compound is measured as
89% [138].
A synthetic inhibitor called 6-methyl-5- [m -Nitro Styryl] − 3-Mer­
capto-1,2,4-triazine was synthesized as a corrosion inhibitor for acid
treatment in 12% HCl and 50 ◦ C on mild carbon steel. The findings
indicated that the inhibitory impact of the tested chemical was on the
anodic and cathodic branches is the mix-type. 6-methyl-5- [m-nitro
styryl] − 3-mercapto-1,2,4-triazine absorption on the surface is
directly through donor-acceptor interaction between heterocyclic π
electrons and empty d orbitals in steel, or the electrostatic absorption
between the positively charged nitrogen atoms and negatively charged
metal surface. The results of EIS showed that with the addition of a
corrosion inhibitor, Cdl concentration tends to drop, while Rt and η% are
increased, and this behavior is a result of the increased thickness of the
electric double layer [139].
It has been reported that 3-phenyl-2-propyn-1-ol (PPO) reduces
corrosion of J55 steel in solutions in hydrochloric acid medium with
different conditions [140].
Many of the selected hydrazines and the fatty acid thio­
semicarbazides have been produced with 11, 12, and 18 carbon atoms to
inhibit N80 steel corrosion, and their corrosion protection properties
were studied in boiling hydrochloric acid solution using the mass loss
method [141]. It was demonstrated that all the tested compounds are
mix-type for mild and N80 steel at room temperature. Accordingly, the
effective corrosion inhibitors for acid treatment are suggested as acet­
ylene alcohols, alkylphenols, aldehydes, heterocyclics including nitro­
gen and quaternary salts, carbonyl and amine condensate products, and
inorganic compounds such as arsenic halides.
Three long-chain oxadiazole fatty acids, including 2-undecane-5-Mer­
capto-1-Oxa-3,4Diazole (UMOD), 2-Heptadecene-5-Mercapto-1-Oxa-3,4-
14
Applied Surface Science Advances 6 (2021) 100128
Diazole (HMOD), and (DMOD) 2-decene-5-mercapto-1-oxa3,4-diazole
have been developed by Quraishi [142]. They were evaluated as corro­
sion inhibitors for carbon steel in 15% HCl at 105±2 ◦ C using the mass
loss method. The inhibitory tests are carried out on N80 steel under the
same conditions as in HCl 15% containing 5000 ppm UMOD. The results
showed that oxadiazoles are good corrosion inhibitors, and UMOD was
introduced as the optimal corrosion inhibitor. This inhibitor demon­
strated 94% inhibition efficiency for N80 steel and 72% for mild steel. In
another study, Quraishi et al. [141] investigated the effect of three
corrosion inhibitors on steel corrosion (N80) in boiling 15% HCl solution
via mass loss [141]. The studied compounds included Dicinnamylidene
acetone (DCA), Disalicylidene acetone (DSA), and divanillidene acetone
(DVA). Two new organic inhibitors, including dibenzylidene acetone
(DBA) and Di-N-dimethylaminobenzylideneacetone (DDABA), were syn­
thesized, and their corrosion behavior was also evaluated on N80 and
mild steels in HCl by mass loss [143]. These compounds had inhibition
efficiencies of 94.4 and 56.5% for mild steel, while their inhibiting effi­
ciencies were 99.7% and 73.8% for N80 steel. The remarkable point is
that both compounds’ inhibition efficiency was increased as synergy by
increasing potassium iodide (KI) content.
Lopez et al. [144] reviewed the information available on the effects
of carbon steel microstructure and composition on the corrosion resis­
tance of CO2 environments. Chemical and microstructure compositions
are not independent variables, and similar microstructures can have a
different chemical composition and vice versa. De-adsorption behavior
of four inhibitors on N80 steel with and without carbonate film was
studied using polarization and electrochemical impedance spectroscopy
(EIS) [145]. In this study, it was found that the de-adsorption behavior
and absorption capacity were different for different inhibitors both with
and without the carbonate film. Moreover, the acid inhibitors and the
inhibitors of small molecular size show different inhibitory behavior
[146].
Jiang et al. [147] have studied the performance of corrosion in­
hibitors for the protection of N80 steel against CO2 corrosion in flowing
and static conditions. Carbon steel corrosion exposed to carbon dioxide
is a major problem for the production and transportation of oil and gas.
However, most of the inhibitors’ analysis is based on the test results in
stagnant or low flow rates (<1 m/s). This leads to the inhibitor’s un­
expected performance in practical situations since higher flow rates for
single-phase flows or lower flow rates for multi-phase flows (gas-liquid
flow or two-phase sand-containing liquid-solid flow) may remove the
inhibitor film, especially the absorption tenacity. Vishwanatham et al.
[148] studied the inhibitory behavior of Methoxy phenol (MPH) and
phenol (NPH) on N80 steel in 15% HCl solution in periods of exposure (6
to 24 h) and the temperature range of 30 to 110 ◦ C. NPH and MPH
displayed the maximum inhibition efficiency of 83% and 78% in 75 mM
inhibitory concentration in acid after 6 h at room temperature.
Two types of organic corrosion N,N′ -bis-(2- thionobenzothiazolin-3-yl-
methyl)-n-octadecylamine (BTBMOA) and N,N′ -bis-(2-thionobenzothiazolin-
3-yl-methyl)-n-dodecylamine (BTBMDA) were synthesized under microwave
irradiation by Junping et al. [149]. The results showed that both inhibitors
prevent N80 steel corrosion in the simulated solution. The inhibitory effects of
(TVE-3A, TVE-3B, and TVE-3C) containing formaldehyde and phenol or cresol
on N80 steel corrosion behavior is examined in a 15% HCl solution [150]. The
effect of temperature (30–115 ◦ C) and time intervals (6–24 h) on the corrosion
rate of steel in acid is investigated in the presence and absence of inhibitors.
TVE-3B demonstrated maximum inhibition of 68.6 at ambient temperature,
while TVE-3A and TVE-3C showed the maximum inhibition at 62.2 and
65.7%.
Khaled et al. [151] synthesized N- (5,6-diphenyl-4,5-dihydro- [1,2,4]
triazin- 3-yl) -guanidine (NTG) as a green inhibitor, and studied its
inhibitory function on carbon steel corrosion in 1 M HCl and 0.5 M
H2SO4. These studies showed that NTG is a good inhibitor in an acidic
environment with a high inhibition efficiency of 99% and 96% in 1 M
HCl and 0.5 M sulfuric acid. Jiancum et al. [152] studied the corrosion
inhibition of a ß-unsaturated carbonyl compound on N80 steel at high
M. Askari et al. Applied Surface Science Advances 6 (2021) 100128

temperatures and concentrated acidic environments and proved that
both cinnamaldehyde and benzalacetone have good anti-corrosion
properties and can reduce steel corrosion in acidic environments effec­
tively. Migahed et al. [139] elucidated the impact of new synthetic
compounds called 6-methyl-5- [m-nitro styryl] − 3-mercapto-1,2,
4-triazine as corrosion inhibitors for mild steel in a solution of 12% HCl
at 50 ◦ C using chemical and electrochemical methods. The results
revealed that the anode solubility of carbon steel was significantly
reduced. Table 3 presents examples of the corrosion inhibitors examined
for acidizing conditions.
4.3. Corrosion inhibitors used in the annulus space
In recent years, several reports of the fractures of corrosion-resistant
alloys in annular space have been made. Consequently, choosing the
packer or the completion fluid chemically compatible with the alloy is
important, and managing the damage has become a matter of concern
[158]. However, based on experience, the impact of the inhibitors on
lowering the rate of cracks stemming from corrosion and its conse­
quences is discussable [159, 160]
Studies show that the chrome-treated sodium lignosulfonate im­
proves corrosion resistance and stress by forming a protective film both
in the laboratory and functional conditions, commonly associated with
magnetite [161]. Factors such as the presence of thiocyanate ions,
oxidizing agents, acid gasses such as H2S and CO2, and particles such as
HCO−3 and CO2− 3 in the packer fluid can affect this type of corrosion
[162]. In the brine-making process, various salts, including KCl, NaCl,
CaCl2, CaBr2, and ZnBr2 are used separately or in combination. As the
complexity arises, corrosion problems will be more noted for the
available alloys and elastomers. For managing this situation, using
amine film-forming inhibitors or organic compounds with low molecu­
lar weight is widely popular [163].
Since chlorine is effective in the formation of SCC corrosion, the use
of chlorine-free brines and other halide compounds is limited to prevent
SCC [164]. Sodium bromide (NaBr) is among the alternative compounds
used along with the film-forming inhibitors and low molecular weight
organic compounds for controlling corrosion. However, the thermal
decomposition at high temperatures is associated with problems, such as
the formation of H2S, which worsens the conditions by reducing the
environment’s pH. The use of film-forming amines and mineral sulfur
compounds with low molecular weight in high temperatures has always
been problematic [43]. Moreover, adverse effects on the compounds
forming the tubes and the elastomers used in the well and the formations
of lumps have been reported [165]. Although several initiatives, such as
insulating packer fluids by polyamine-nanosilica dispersion in packer
fluid [166], the degradation of inhibitors at elevated temperature is still
challenging.
The use of buffers to control the pH is an affordable, easy, and
controllable way of solving this issue. Depending on the type of brine,
sodium hydroxide (NaOH), lime (CaO), and lime hydrate (Ca(OH)2) are
used to increase pH [167].
Thiocyanate salts, such as NH4SCN, KSCN, and NaSCN, are among
the inhibitors in packer fluid used first for brine. Under the high thermal
and pressure conditions, the well suffers from thermal decomposition,
and sulfur or H2S is produced. This process has occurred in ZnBr2 brine
at lower temperatures, and with increasing temperature and prolonged
times, it is intensified, which is followed by corrosion damage and
destruction in the wake of ZnS formation. Given the devastating effects
of thiocyanate thermal decomposition on SCC, the use of these inhibitors
in wells containing CaBr2 and NaBr where CRA alloys are used is not
recommended [168].
The use of nitrate methanol-water mixture (ANM) with low pH
proper calcareous and argillaceous as the completion fluid is due to the
high corrosion on carbon steel even at room temperatures, which

Table 3
Examples of corrosion inhibitors for acidizing conditions based on the field or electrochemical tests.
Inhibitor Medium Material Inhibitorconcentration Test test/ IE(%) References
methods treatmentconditions (orCR)

1-(1H-benzo[d]imidazole-2-yl)-N- 15%HCl N80 3.17 × 10− 3M PDS, EIS, 303 K 71.8% [153]
((furan-2-yl)methylene)− 2- SEM, AFM
phenylethanamine (BIFP)
1-(1H-benzo[d]imidazole-2-yl)-N- 15%HCl N80 31.71 × 10− 3M PDS, EIS, 303 K 97.5% [153]
((furan-2-yl)methylene)− 2- SEM, AFM
phenylethanamine (BIFP)
1-(1H-benzo[d]imidazole-2-yl)-N- 15%HCl N80 3.17 × 10− 3M PDS, EIS, 303 K 62.5% [153]
((furan-2-yl)methylene) SEM, AFM
methanamine (BIFM)
1-(1H-benzo[d]imidazole-2-yl)-N- 15%HCl N80 31.71 × 10− 3M PDS, EIS, 303 K 94.7% [153]
((furan-2-yl)methylene) SEM, AFM
methanamine (BIFM)
2-undecyl-1-ethylamino-1- 1.0 M H2SO4 N80 50, 150 ppm LPR, PDS, RT 63.4%, [154]
methylbenzyl quaternary EIS 95.5%
imidazoline (2UMQI)
2-undecyl-1-ethylamino-1- 1.0 M H2SO4 N80 50 ppm 2UMQI+ 5 mM LPR, PDS, RT 99.3% [154]
methylbenzyl quaternary KI EIS
imidazoline (2UMQI) and KI
YC-JTHSJ NaCl 50 mg/L + H2S J55 80 pm WL 25 ◦ C, pH=4, 1 bar CO2 87.04% [28]
200 mg/L + CO2 pressure
200 mg/L
Indole 1 mol/LHCl MS 2 mmol/L WL 25 ◦ C 92.5% [155]
1H-benzotriazole 1 mol/LHCl MS 2 mmol/L WL 25 ◦ C 87.1% [74]
1,3-Benzothiazole 1 mol/LHCl MS 2 mmol/L WL 25 ◦ C 85.7% [155]
4-Amino-5-mercapto-1,2,4-triazole 1 mol/LHCl MS 0.4 g/L Tafel 25 ◦ C 68.4% [156]
3-Phenyl-4-amino-5-mercapto-1,2,4- 1 mol/LHCl N80 0.4 g/L Tafel 25 ◦ C 88.8% [156]
triazole
Polyaspartate CO2 saturated mild 20 ppm LPR, RCE, 338 K 72% [157]
North Sea steel Bubble Test
brine
Alkyl CO2 saturated mild 20 ppm LPR, RCE, 338 K 83% [157]
PolyGlucoside North Sea steel Bubble Test

15
M. Askari et al.
requires inhibitors to reduce the corrosion rate to an acceptable indus­
trial level. It is expected that film-forming agents, including amine and
phosphate base inhibitors, are effective on the steel surface. The pre­
liminary results in the inhibitor study are achieved based on the com­
mercial inorganic anode inhibitor compounds based on nitrite-borate.
Inorganic inhibitors are practically the complex combinations of organic
and inorganic inhibitors formed on mixtures in which diammonium
hydrogen phosphate and ammonium hydrogen phosphate are the main
components. Commercial organic and inorganic inhibitors filtered
through a 45-micrometer filter reduce the corrosion rate by a significant
amount (over 95%) without affecting the permeability. However, based
on the potentiodynamic tests, these inhibitors lack high anode passiv­
ation ability, and there is a requirement to reach the protective outer
layer [169].
Another requirement is to reduce the adverse effects of oxygen levels
on corrosion [170]. For this purpose, oxygen scavengers effectively
mitigate the negative effects of the dissolved oxygen, such as extreme
degradation of polymer additives and incorporating the corrosion of
in-service metals [171]. These chemical materials are oxidized during
the reaction with oxygen, leaving no oxygen to cause further damage.
The problem with the majority of the oxygen scavengers is their insta­
bility and degradation at high temperatures, which creates destructive
compounds [172]. The described problems are among the causes that
necessitate the development and production of new oxygen scavengers.
Erythorbate mixture and alkylhydroxylamin compounds in the
packer fluid have demonstrated a synergistic effect of oxygen depriva­
tion and corrosion inhibition. The use of alkylhydroxylamins, such as
Isoprpylhydroxylamin, leads to the stability of erythorbate compounds
such as ammonium erythorbate, zinc erythorbate, and other formed
erythorbate compounds at higher temperatures (up to about 260 ◦ C)
[173]. The comparison between these new scavenger and erythorbate
compounds indicates the reduction of oxygen level at higher periods in a
range of brines such as NaCl, NaBr, CaCl2, and in both room and high
temperatures.
Recently, propargyl alcohol’s inhibitory effect as a metal corrosion
inhibitor in acid environments was studied on the stress corrosion of
13Cr steel in completion fluid CaCl2 saturated with CO2. Electro­
chemical experiments, including polarization and electrochemical noise
as well as the surface observations and analysis of compounds, indicated
the uniform pitting and corrosion control during PA polymerization and
reaction with corrosion products, consequently forming the film. It is
expected that by increasing the PA concentration, a thicker protective
layer would be formed. With increased PA concentrations, the anodic
reactions are prevented, and the potential shifts towards more anodic
Fig. 9. The surface characteristics of 13Cr steel in the packer fluid containing 0.2% acetic acid, a - without inhibitors b – 0.02% PA c – 0.1% PA D- 1% PA[174].
16
Applied Surface Science Advances 6 (2021) 100128
values. Thus, it can be deduced that PA counters corrosion in anodic
mode. Moreover, the electrochemical noise analyses and fracture sur­
face observations indicate that at low PA concentrations, the stress
corrosion and SCC are prevented at concentrations above 1% wt. The
effect of this issue is also true on the flow throughput of hydrogen [174].
Fig. 9 illustrates the performance of the mentioned inhibitor on 13Cr
steel.
Table 4 presents examples of the corrosion inhibitors examined for
annulus space purposes. These tests include laboratory tests and field
results. The applied materials generally embrace the steels and alloys
used in the manufacturing of tubing and casing. For each inhibitor, the
molecular structure (and sometimes brand), test environment, MIC,
evaluation, and testing techniques, and the results of performance
monitoring or corrosion protection data such as corrosion rate, are
provided.
5. A technical review on the methods of inhibitor injection
Different methods of injecting inhibitors in the wells have been
discussed [175, 176]. The oil-soluble inhibitors applied as a batch are
usually injected as "batch and fall" to provide the possibility of forming a
layer of protective film on the tubing.
At sites where the batch inhibitors are physically or chemically
absorbed on the downhole tubing, the erosion removes the physically
absorbed components while active compounds remain on the surface.
The applied inhibitors in a batch mode need to be reapplied within the
defined intervals since they increase erosion effects of removing the film
and the tendency to reform it. Water-soluble inhibitors are injected
continuously and protected by the formation and reformation of the film
and the tubing. However, the cost of installing and maintaining the
continuous injection facilities in the well’s lifetime could be problem­
atic. For downhole corrosion inhibitors, chemical injection methods
include continuous injection, batch injection, and squeezing [175-179].
5.1. Continuous injection
This injection method is carried out via injection through a spaghetti
tube and the annulus. It is widely used in multiphase wells with high
production rates, especially in systems with high water content where
the inhibitor is injected by a tube in the annular space between the
tubing and casing. In the continuous injection method through the
annular space, a precise formulation is required to avoid the phenom­
enon of flashing off at high temperatures at the bottom of the well. This
phenomenon converts the injected fluid into a sticky substance that
M. Askari et al. Applied Surface Science Advances 6 (2021) 100128

Table 4
Examples of annulus space inhibitors based on the field or electrochemical tests.
Inhibitor Medium Material Inhibitorconcentration Test methods test/treatmentconditions IE(%) References
(orCR)

NaSCN ZnBr2 Brines C4130 carbon 0.25% Immersion test, 436 K 93% [168]
steel SEM/EDS seven days expossure

KSCN ZnBr2 Brines C4130 carbon 0.25% Immersion test, 436 K 93% [168]
steel SEM/EDS seven days expossure

NH4SCN ZnBr2 Brines C4130 carbon 0.25% Immersion test, 436 K 93% [168]
steel SEM/EDS seven days exposure

buffer (NaOH, CaO, NaBr Brines HP1 13Cr 1 to 10 ppb buffer WL, C-ring 450 K 50% [167]
Ca(OH)2) under 90 to 100% addition under a 400 psig nitrogen+ 30
yield stress psig CO2
buffer (NaOH, CaO, NaBr Brines Q125 1 to 10 ppb buffer WL, C-ring 450 K 96.5% [167]
Ca(OH)2) under 90 to 100% addition under a 400 psig nitrogen+ 30
yield stress psig CO2

eventually leads to the clogging of the injection valve. Therefore, it is

essential to avoid this issue in the case of solvents with a high boiling
point, such as polyethylene glycol [176].

5.1.1. Continuous injection through the annulus

Due to the relatively simple implementation, continuous injection is
a technique that is commonly used in downhole injection. The disad­
vantages of this method are as follows:

1 Inhibitor slugging: the inhibitor flow in the tubing is not fixed, and
although the inhibitor injection in the surface in the annular space is
steady and continuous, this problem is intensified as reservoir pres­
sure is lowered and the reliability of the injection valves is reduced
due to their inertia.
2 Clogging of the valve: particles and solid objects such as sand, shells,
and corrosion products may block the injection valves. Solving this
problem may be complicated and expensive. In general, it is enough
to pull out the valve by the wireline, but in more extreme circum­
stances, it is necessary to pull out the tubing, which is followed by a
pause in production.
3 Large required quantities: to fill the annular space, often a large
amount of inhibitor is required.
4 Long stay: If the injection rate is too low, the inhibitor may remain in
the annular space for a long time, leading to the degradation of
inhibitory material and reduced efficiency, the formation of solid
mass, and clogging of the valve. The thermal stability test can reduce
this risk.
5 The risk of killing the well: At low-pressure wells, if the injection
valves are destroyed, the fluids will be pumped into the wells
through the annular space which will likely result in the death of the
well.

5.1.2. Continuous injection through spaghetti tubes

In this method, controlling the injection rate is easier (see Fig. 10),
and many of the problems related to the annular injection are resolved
[180, 181]. However, this method has other issues as described below:

- The risk of injection line damage during installation or operation.

- The cost of additional equipment such as a packer, equipment for
modifying the wellhead, injection tube, and injection site in the
tubing.
- The reduced effective size of tubing: If the injection spaghetti tube is
implemented inside the tubing, the tubing size will be reduced, and
in the case of tubing with lower diameters, this change could be
significant. Moreover, this tube can be damaged by sand.
- The difficulty of implementing this method in vertical wells.
Fig. 10. Injection inhibitor through the capillary tube.
5.2. Batch injection
This method can be utilized when the implementation of continuous
injection is difficult or not feasible from a technical and economic point
of view. The disadvantages of this are summarized below:
• Corrosion in the intervals between the injection operations.

17
M. Askari et al. Applied Surface Science Advances 6 (2021) 100128

• Suspension of production for several hours.
• Formation of a stable emulsion.
• Waste of large volumes of inhibitor during restarting production.
Batch injection using the inhibitor with a stable film is often used in
gas wells. Furthermore, this method is proposed for remote wells with no
power access and places where the conditions are not severe (e.g., the
corrosion rate is low). With deteriorating operating conditions, the
proposed method is changed from batch to continuous, or batch along
with continuous methods [182]. The batch injection method is imple­
mented in two ways:
5.2.1. Batch and fall
This method is successfully applied in gas wells with high corrosion
and with no fluid in the bottom of the well at the shut-in. In this method,
a certain amount of inhibitor combined with a diluted wetting agent is
pumped into the well. Within a few hours, the inhibitor on the tubing
wall moves down. One of the disadvantages of this method is the flow
back and the waste of large amounts of inhibitor during the reproduc­
tion. The formation of a sticky/stable emulsion at high pressure of gas
condensates. A brush-like commercial tool can improve the inhibitor
film and reduce the shut-in [183, 184].
5.2.2. Tubing displacement
This method is effective for oil wells. The inhibitor mixture is diluted
and transferred to the bottom of the well by the produced fluid, or the
nitrogen gas pumped into the well. Pumping rates will be selected to
optimize the formation of the inhibitor film [185].
After the inhibitor mixture reaches the bottom of the well, it is kept
there for several hours. As the well returns to production, a large volume
of the inhibitor is removed, resulting in the formation of stable emul­
sions unless the emulsion breaker component is added to the inhibitor.
Depending on the circumstances and the type of inhibitor, the operation
period might last from one week to several months.
5.2.3. Squeeze injection
In this method, the inhibitor solution is pumped into the well
through the tubing with pressure after closing the well. The aim is that
the inhibitor solution penetrates the pores of the formation. This method
can be used in wells with different completions. Injection periods
depend on the type of inhibitor, nature of the formation, and production
speed. The well is placed in the production circuit following the
injection. First, the concentration of the inhibitor is high in the gas, and
at the same time, the protective film is formed on the surface. After a
while, the inhibitor concentration is decreased; therefore the protective
film is strengthened and repaired [177, 181, 186].
For wells containing packers, the addition of the protective fluid in
the space between the tubing and casing protects both the inner casing
and the outer wall of the tubing. The protective fluid is applied in the
space along with the inhibitor.
Table 5 compares the different inhibitor injection methods from the
application, limitations, and disadvantages perspective [44].
6. Implications in developing new corrosion inhibitors
6.1. Tailoring the products to demands in oil well corrosion management
It is crystal clear that the development of new corrosion inhibitors for
oil and gas industry applications demands a comprehensive series of
considerations in the supply chain. There should be an integrated
connection in all stages, from the development of chemicals on a labo­
ratory scale to final use. Many research documents dealing with newly
developed inhibitors remained in the research stage due to limiting the
electrochemical lab-scale in a simplified environment. Due to the lack of
a comprehensive understanding and consensus of the mechanisms/role
of inhibitors, the prediction of a certain compound acting in a particular
situation is usually difficult, if not impossible [187]. Running laboratory
tests in the same operating conditions of the tube, i.e., at the same
temperature and pressure conditions using coupons made of the tubing
material, is essential for general insight. Practically, in laboratory
corrosion tests, autoclaves and glass equipment with special design are
used to simulate the conditions of the well during the acid treatment
[112]. In addition, numerous analytical and computational tools have
been developed [171, 188-190] that can be adopted for corrosion in­
hibitors application assessment, reducing the need or validating labo­
ratory tests. Thus, there should be a strong impetus to shift the
fundamental study to the experimental stage by facilitating the inter­
mediate level of semi-field tests. Industrial sectors barely trust a sheer
scientific report without compelling technical justifications. Having a
solid connection is required to transfer industrial demands to academic
sections and facilitate the evaluating research outcome under the
framework and standards of industries.

Table 5
Comparison of different inhibitor injection techniques [6].
Method (Frequency) Basic Description Applications Disadvantages Additional Comments

Batch and fall Shut-in, pump into tubing, allow Gas wells Cannot treat below Wells >1000 psi, rate of fall depends on
(monthly) to fall liquid level gas density

Tubing displacement Shut-in, pump full Use full volume diluted Over displacement Requires reservoir and
(quarterly) tubing displacement minus safety chemical or slug displaced with diesel, can damage formation subsurface evaluation to identify wells
factor crude oil, water, or nitrogen that can have displacement treatment

Squeeze (monthly or Similar to displacement, Chemical returns into the produced fluid High risk of formation Not normally
semiannually) chemicals forced into the from reservoir storage damage recommended due to risk of formation
reservoir damage

Gas lift (continuous) Pump small volume Gas-lift wells only

of the chemical into gas-lift gas at
wellhead continuously

Downhole injection Chemical injection Any new well that Plugging Injection valves
(continuous) lines chemical injection lines can have installed potential, initial adjusted to control injection rate
capital cost

Dump bail Use wireline bailer May needs several trips to deliver sufficient Mechanical risk Aluminum bailers do
to spot chemical to the location in inhibitor using concentrated products not hold much chemical volume
well

18
M. Askari et al.
6.2. The urge to develop and assess the green or eco-friendly corrosion
inhibitors
In recent years, efforts have been increased to apply green inhibitors
to industrial applications. Community expectations and regulations of
related institutions have led to the extensive investigation on the source
of green inhibitors, their performance, and the possibility of their
employing in industrials [191]. Paris commission as a trustee demands
three characteristics to be tested; Toxicity, biodegradation, and bio­
accumulation [192]. The green inhibitors considering mentioned pa­
rameters are including plant extracts [193], natural oils [194], ionic
liquids [195], drugs [196], amino acids [197], and natural polymers
[198].
Eco-friendly corrosion inhibitors have been utilized to manage
corrosion of the downhole tubing. Sunday Aribo et al. [199] utilized
Tridax procumbens and Chromolaena odorata extracts to protect the
super austenitic stainless steel in 1:1 4M HCl and CO2 saturated 3.5 %wt.
saline solution and obtained over 90% inhibition efficiency. Loto et al.
[200] reported the 80% inhibition efficiency for basil oil extract (CLB)
and atlas cedar oil extract (CLA) in HCl and H2SO4 medium. Recently,
employing rosemary and cinnamon cassia essential oil extracts resulted
in a 90% inhibition efficiency for the mild steel in a low concentration
HCl acidic medium [201]. The same inhibition efficiency was also re­
ported for the pipeline steel in the presence of Gum Arabic [202]
Vanillin modified chitosan was also utilized and showed 92% efficiency
in 15% HCl [203]. Furtado et al. [204] introduced Cashewnut shell
derived as a green inhibitor. The Cardanol residue along with Acetylenic
alcohol and Butylglycol had a synergistic effect and offered a remark­
ably inhibition efficiency of 99.47% in API P110 carbon steel in 15%
HCl.
The inhibition of two eco-friendly compounds known as 2-Amino-N-
octadecylacetamide (AOA) and 2-Amino-N-octadecyl-3- (4-hydrox­
yphenyl) propionamide (AOHP) is addressed on the API grade N80 steel
in 15% hydrochloric acid solution. Different concentrations of the syn­
thesized inhibitors are introduced into the test solution, and the inhib­
itor efficiency was determined with mass loss, potentiodynamic
polarization, and EIS. AOA and AOHP exhibited the best efficiency at a
concentration of 150 ppm, which was the highest concentration used in
the inhibition tests. This efficiency was reported as 90.04% and 94.97%
for AOA and AOHP weight reduction tests, respectively. AOHP has
better efficiency than AOA in all test categories due to the more
numerous active centers and larger AOHP molecules compared to the
AOA. Electrochemical tests and FTIR and SEM analyses indicated that
the inhibitors are hybrid, and the inhibition mechanism of these com­
pounds was governed by absorption on steel N80 alloy [205].
The effect of 2-(2-pyridyl) benzimidazole as a CO2 corrosion green
inhibitor was studied under turbulent hydrodynamics in a sweet envi­
ronment. The inhibitor showed 90% efficiency in the rotation of 2000
rpm [206]. They even reported at least 86% efficiency in 4000 rpm after
12hours. The efficiency was further enhanced by including thio­
barbituric acid and reached 95.6% after 12hours of immersion [207].
The mixture of zinc sulfate and calcium gluconate is among these
proposed compounds. Furthermore, in surveys about the synergistic
effect of aspartates and alkyl polyglucosides as effective and environ­
mentally friendly inhibitors, it has been made clear that an optimal
length of the alkyl chain is required for effectiveness in the formation of
corrosion protection film. These inhibitors show good compatibility
with the fluids and oil field equipment. However, to achieve better ef­
ficacy, higher amounts of these inhibitors are injected compared with
the conventional inhibitors [157].
Although high inhibition efficiency has been reported for several
components as reviewed, there is still not clear that, for instance, in
plant extracts, molecules hinder the corrosion and even from which
components they are formed. Moreover, toxicity, biodegradation, and
bioaccumulation should be considered as none of the studies typically
report the data on these parameters. Also, in a few papers, the process of
19
Applied Surface Science Advances 6 (2021) 100128
inhibitor extraction from its source has been reported clearly, which is
essential for evaluating the cost and difficulty of mass-producing these
inhibitors. Finally, there is still a need for more investigation with actual
downhole formulation and environment to ranking green inhibitors as
candidates to replacing current inhibitors.
7. Knowledge gap on downhole corrosion inhibitors for oil and
gas production
As the oil and gas wells go deeper and toward harsher conditions, the
corrosion challenges for downhole tubing and accessories are increased.
HTHP wells which refer to high/temperature and high-pressure reser­
voirs, demand a high level of knowledge to assess the corrosion behavior
and estimate the corrosion rate. This complexity is even greater in the
study and application of corrosion inhibitors. Since chemical testing in
the simulated conditions requires advanced devices and special vessels,
despite some publications in this area, there is still a significant gap of
knowledge about the type of corrosion inhibitors, mechanism of inhi­
bition, and their real effectiveness.
Moreover, other major influencing factors like gas velocity and high
H2S and CO2 level increase the severity of conditions and corrosivity of
the systems. Obot et al. [43] has identified the salient knowledge gap for
high-temperature sweet corrosion inhibitors. In the scope of downhole
corrosion inhibitors for the oil and gas industry, customized tests,
specialized formulations, and molecular modeling by chemical manu­
facturers are the main shortcomings for efficient corrosion inhibition in
such conditions. Limited information on downhole corrosion inhibitors
regarding pitting and localized corrosion protection in those above se­
vere susceptible conditions and their mechanisms of inhibitions render
chemical treatment less confident in such conditions.
In some of the cases addressed above, some laboratory tests and
research results might have been present. Still, due to lack of field data,
there is little to no reliability of the research results and the performance
of chemicals on the industrial scale. These can be considered as the
reasons that operators tend to select corrosion resistance alloys instead
of less confident chemical treatment by corrosion inhibitors.
In addition, most of the tests have been carried out in a solution
containing 3.5 wt% NaCl. In contrast, in many practical cases, the for­
mation water of the well may contain more than 20 wt% NaCl and a high
concentration of TDS, which greatly impacts the corrosion inhibitor film
performance.
8. Conclusions and recommendations
Maintenance of the equipment for sustainable production during the
life of the reservoir involves employing an effective corrosion control
method while considering the economic feasibility. The emphasis on this
point is a reason for the development of this review paper, in which the
corrosion inhibitors are considered as an efficient method of controlling
downhole corrosion. As the projected corrosion rate is too high, the
corrosion inhibitor will not be as effective in reducing the corrosion rate
of the carbon steels since even at the maximum protection efficiency, it
will remain high. Considering the point mentioned above, the use of
CRA tubes is the the most reliable way to prevent corrosion in highly
corrosive wells with high temperature, pressure, and depth provided
that the correct alloy is selected and the lack of sensitivity to stress
corrosion cracking is tested under laboratory conditions.
In the three structural levels of this work, different inhibitors are
studied from different points of view. The comparison of testing/oper­
ating conditions and obtained efficiencies can be effective in selecting
the inhibitory formulation or the groups of chemicals. The working and
study conditions were so extensive that there were overlaps in the
operating conditions in most oil and gas wells in the world. This study
can serve as a bridge between industry needs and research findings. In
the other hand, it has been tried to provide key guidelines for proper
selection and application of downhole corrosion inhibitors for the oil
M. Askari et al.
and gas industry. Meanwhile, a historical and latest research outcome is
reported so that researchers can find new lines to work based on the gaps
and necessities.
However, despite all the efforts made in the synthesis and formula­
tion of downhole inhibitors and optimization techniques of injection and
monitoring, it is observed that corrosion is still a great concern in
operating the wells with inhibitor injection, where extensive deterio­
ration is reported in such wells. For this reason, recommendations are
made for continued field surveys and studies by the downhole corrosion
inhibitor injection.
- Synthesis and design of the downhole encapsulated inhibitor injec­
tion, particularly in situations where there is no possibility of
injecting the inhibitor in the liquid phase.
- Field assessment of the encapsulated inhibitors based on monitoring
and inspection results.
- Analysis of the hydrodynamic effects of the fluid on the stability of
the inhibitor film in simulated wells.
- Examination of corrosion inhibitors for controlling stress corrosion
cracking.
- Analysis of the possibility of using corrosion inhibitors for control­
ling stress corrosion cracking caused by hydrogen.
Environmentally friendly inhibitors and their production in indus­
trial scales and novel application techniques are areas that are recom­
mendable to be involved in-depth. In this regard, encapsulation of the
inhibitors applies them in the annular space of the well to control casing
corrosion (in which inhibitor injection equipment is not seen).
Furthermore, the possibility of controlling the destructions with
cracking mechanisms is on this research group’s agenda, and they are
the prospect of the authors as the safe production of the wells operating
with such inhibitors.
Declaration of Competing Interests
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
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