Accepted Manuscript

Film former corrosion inhibitors for oil and gas pipelines - A technical review

M. Askari, M. Aliofkhazraei, S. Ghaffari, A. Hajizadeh

PII: S1875-5100(18)30336-6
DOI: 10.1016/j.jngse.2018.07.025
Reference: JNGSE 2670

To appear in: Journal of Natural Gas Science and Engineering

Received Date: 1 December 2017

Revised Date: 25 April 2018
Accepted Date: 24 July 2018

Please cite this article as: Askari, M., Aliofkhazraei, M., Ghaffari, S., Hajizadeh, A., Film Former
Corrosion Inhibitors for Oil and Gas Pipelines - A Technical Review, Journal of Natural Gas Science &
Engineering (2018), doi: 10.1016/j.jngse.2018.07.025.

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.
 ACCEPTED MANUSCRIPT
Film Former Corrosion Inhibitors for Oil and Gas Pipelines - A Technical

Review

M. Askari, M. Aliofkhazraei∗, S. Ghaffari, A. Hajizadeh

PT
Department of Materials Engineering, Tarbiat Modares University, Tehran, Iran, P.O. Box:

14115-143

RI
SC
Table of Contents
Abstract ............................................................................................................................... 1

U
1. Introduction ...................................................................................................................... 2
AN
2. Internal corrosion in oil and gas pipelines........................................................................... 4
2.1. Factors affecting the internal corrosion ........................................................................ 4
2.2. CO2 corrosion (sweet corrosion) ................................................................................... 5
M

2.3. H2S corrosion (sour corrosion) ..................................................................................... 7

3. Flow regime and its effect on the corrosion and inhibition ................................................... 8
D

4. Internal corrosion control methods in oil and gas pipelines ................................................. 9

TE

4.1. Material selection ........................................................................................................ 9

4.2. pH stabilization ..........................................................................................................11
4.3. Corrosion Inhibitor ....................................................................................................12
EP

5. Types, structure and classification of organic film former corrosion inhibitors ...................15
5.1. Imidazoline 18
C

5.2. Amidoamines..............................................................................................................27
AC

5.3. Aliphatic Amines ........................................................................................................30

5.4. Ethoxylated amines.....................................................................................................31
5.5. Quaternary ammonium compounds ............................................................................32
5.6. Sulfur compounds.......................................................................................................35
5.7. Polymeric inhibitors based on polyamine derivatives ...................................................36
6. Evaluation of the inhibition mechanisms by film former corrosion inhibitors......................40

∗
) Corresponding author: Tel.: +98-912-6905626, E-mail address: maliofkh@gmail.com, khazraei@modares.ac.ir

0
 ACCEPTED MANUSCRIPT
6.1. Electrochemical Impedance Spectroscopy (EIS) ...........................................................41
6.2. Electrochemical Noise Analysis (ENA) .........................................................................44
6.3. Harmonic Analysis (HA) .............................................................................................45
6.4. Thermogravimetric Analysis (TGA) ............................................................................45
6.5. Quartz Crystal Microbalance (QCM) ..........................................................................46
7. The selection process of corrosion inhibitors for oil and gas pipelines .................................46

PT
8. Conclusion .......................................................................................................................52
9. References........................................................................................................................53

RI
SC
Abstract

Pipelines play a significant role in production and transportation of oil and gas. The use of

U
film-former corrosion inhibitors is one of the most economical and reliable methods of
AN
controlling internal corrosion of sour oil, sweet oil and gas pipelines. In this paper, the

general mechanisms of internal corrosion in oil and gas pipelines, formulation and chemical
M

structure of film-forming organic corrosion inhibitors and their different types were reviewed.
D

The mechanisms of film formation of these corrosion inhibitors are also reviewed based on
TE

electrochemical techniques. In addition, the selection process of corrosion inhibitors for

pipelines is discussed.
EP

Keywords: Oil and gas pipelines; Organic corrosion inhibitors; Film forming inhibition
C

mechanism; Molecular structures; Inhibition efficiency.

AC

List of abbreviations

AFM: Atomic Force Microscopy

CAPEX: Capital Expenditure
CRA: Corrosion Resistant Alloy
EAC: Environmentally Assisted Cracking
EDS: Energy Dispersive Spectroscopy
EIS: Electrochemical Impedance Spectroscopy

1
 ACCEPTED MANUSCRIPT
EN: Electrochemical Noise
IE: Inhibition Efficiency
LPR: Linear Polarization Resistance
MEG: Monoethylene Glycol
NACE: National Association of Corrosion Engineers
OD: Outside Diameter
OPEX: Operational Expenditure
PDS: Potentiodynamic Scanning
QCM: Quartz Crystal Microbalance

PT
SEM: Scanning Electron Microscopy
SRB: Sulfate Reducing Bactria
TOLC: Top of Line Corrosion

RI
UT: Ultrasonic Test

SC
1. Introduction

Wet hydrocarbons make form a corrosive medium for pipelines [1]. The corrosivity of fluids

U
depends on various factors, including acid gases, pressure, temperature, bacteria, pH, fluid
AN
velocity and solids [2]. Depending on fluid corrosivity, internal corrosion rate of pipeline can

be high enough to consume 3-6 mm corrosion allowance within one year. Moreover,
M

localized corrosion and environmental assisted cracking mechanisms can impose serious
D

failures to pipelines if not properly mitigated. During the engineering stage and the material

selection phase for pipeline projects, based on corrosivity of fluid and CAPEX/OPEX
TE

balances, carbon steel or CRA (cladded or solid) can be chosen as the pipeline material.
EP

Since most of oil and gas pipelines are made of carbon steel, a corrosion control program is

required to ensure that the designed operation life is achieved [3-5].

C

Although, for corrosive media dependent on corrosion rate, usually the minimum allowed
AC

corrosion thickness is considered for pipelines, but chemical treatment is essential for

minimizing the risk of general and localized corrosion, and for responding to any

environmental variations. One of the most effective methods of corrosion prevention for oil

and gas pipelines is the chemical treatment by film-forming corrosion inhibitors. Most of the

corrosion inhibitors used in oil wells and pipelines are composed of nitrogen-containing

2
 ACCEPTED MANUSCRIPT
organic compounds. The structure of these corrosion inhibitors generally includes a long-

chain hydrocarbon structure (usually C18) [6-8].

Most of the effective corrosion inhibitors in the oil and gas industry are based on a long-chain

of aliphatic diamine or imidazoline with a long carbon chain. Different methods were

proposed for optimization of these components, and variations of their physical properties.

PT
For example, ethylene oxide reacts with these components in different percentages and

RI
produces various polyoxyethylene derivatives, which result in various degrees of distribution

in saline solution. In addition, many carboxylic acids derivatives are used for the production

SC
of amine salts and imidazoline [9, 10].

Corrosion inhibitors which generally used in the oil and gas industries in the manufacturing

sector are classified as follows:

U
AN
−Amides/Imidazoline
M

−Salts of nitrogen-containing molecules with carboxylic acids

−Nitrogen quaternary salts

D

−Amines, amides and polyoxyalkylized imidazoline

TE

−Heterocyclic compounds containing N, P, S and O [8, 11]

EP

This paper discusses all these categories of corrosion inhibitors by focusing on their specific

applications in oil and gas pipelines, both sour and sweet. Testing or application conditions,
C

test methods, the rate of injection and their corrosion inhibition efficiency were addressed and
AC

tabulated, which can serve as a master guide for those involved in pipeline corrosion

inhibitors. Pipelines with other purposes, such as water injections with the risk of oxygen

corrosion, are not discussed in this paper.

3
 ACCEPTED MANUSCRIPT
2. Internal corrosion in oil and gas pipelines

2.1. Factors affecting the internal corrosion

The main risks of internal corrosion in pipelines are classified in Table 1. Corrosion and fluid

type associated with influencing factors are also discussed.

PT
Table 1. The major risks of internal corrosion in oil and gas pipelines

RI
Active mechanisms of corrosion and their rate are dependent on the chemical composition of

SC
the fluid. Chemistry of water in oil and gas pipelines (condensate water and formation water)

is the main feature of the fluid’s corrosivity.

U
Hence, it is necessary to check the aqueous phase inside the pipeline before analyzing any
AN
other chemical compounds [12-14]. The main components of the chemical composition of
M

water on corrosion of CO2/H2S in the production and transportation of oil and gas pipelines

and water injection lines are presented in Table 1.

D

Measurement of fluid’s pH in un-pressurized samples should be taken precisely since CO2 is

TE

rapidly released from the un-pressurized solution and in this way, the measured pH does not

introduce the in-situ conditions of the fluid.

EP

Due to the presence of dissolved salts such as sodium chloride, barium sulfate, sodium sulfate
C

and calcium carbonate, the formation water of reservoir may lead to scaling in the pipeline.
AC

Injection of water into some reservoirs may cause the release of water from the formation and

souring. Mixing of chemical compounds and generation of H2S can cause scales in the

pipelines. Some of the fields also contain acetic acid, which increases the corrosion rate in the

systems containing CO2 [15].

4
 ACCEPTED MANUSCRIPT
2.2. CO2 corrosion (sweet corrosion)

Corrosion by CO2 is regarded as a common problem in the oil and gas production fields.

Despite the systematic efforts taken to analyze and extract the appropriate models for

prediction of this type of corrosion, it is still a phenomenon which not all of its aspects are

clear, and there is some uncertainty regarding the mechanism and effective parameters. In

PT
addition, the existing and exact information models do not include detailed about the

RI
environments with severe corrosivity [16-18]. CO2 corrosion problem is known for a long

time and many studies were done on this corrosion mechanism. Dry carbon dioxide is not

SC
corrosive at common temperatures of oil and gas systems, but when it dissolves in the

aqueous phase, cause to electrochemical reaction between the steel and media to be activated.

U
CO2 gas has a very high solubility in water and saline water, and its solubility in
AN
hydrocarbons is slightly higher. Hydrocarbon fluids are generally produced in contact with
M

the aqueous phase and in many cases, hydrocarbon reservoirs contain a significant amount of

CO2. As a result, CO2 dissolves in the aqueous phase of the hydrocarbon product and this
D

aqueous phase causes corrosion of carbon steel [19].

TE

Carbon dioxide corrosion mechanisms are complex. At first, CO2 gas dissolves in water to

produce bicarbonate ions, carbonic acid and hydrogen ions. All these components have the
EP

ability to migrate toward metal surfaces and contribute to the reduction reaction. Reactions
C

including bicarbonates lead to increased corrosion rates higher than what was expected from
AC

the amount of acidity. At temperatures lower than 60°C and pH values less than 4 corrosion

is controlled by the rate of production of iron ions with a surface covered by iron carbonate.

In many cases, the semi-protective film of iron carbonate is formed at temperatures higher

than 70°C, and the reaction is controlled cathodically, which leads to the decrease of

corrosion rate. This rate is also controlled by the partial pressure of CO2, temperature, pH

5
 ACCEPTED MANUSCRIPT
(controlled by the concentration of bicarbonate ions) and fluid conditions. The highest

corrosion rate has been reported at about 70°C [20, 21].

Some other different mechanisms have been proposed for this type of corrosion, and they all

include carbonic acid or bicarbonate ion formed by dissolution of CO2 in water. It causes

higher corrosion rates than what was expected from corrosion in strong acids in the same pH.

PT
CO2 dissolves in water and forms carbonic acid, which is weaker in comparison to mineral

RI
acids [22, 23].

The steps of carbonic acid reaction are as follows [20, 21, 23]:

SC
CO2(g)+H2O
CO2(dissolved) (1)

CO2(dissolved)+H2O H2CO3  H++HCO3- (2)

U
The mechanism introduced by De-Waard is also well known [24-26].
AN
H2CO3+e-
H+HCO3- (3)

Fe
Fe2++2e-
M

(4)

CO2+H2O+Fe  FeCO3+H2 (5)

D

In the case of corrosion mechanism of CO2, there is a debate as to when other dissolved
TE

components exist in the corrosion reaction. The corrosion rate is dependent on the partial

pressure of CO2 since this parameter determines the pH and concentration of dissolved
EP

solution components. In fact, the entire chain of electrochemical reactions is more

C

complicated than mentioned cases. Depending on which step controls the corrosion rate, the
AC

dependence of corrosion reactions to pH and dissolved CO2 will be different [22, 23].

Localized corrosion caused by CO2 (sweet corrosion) is a serious concern for oil and gas

pipelines. Depending on the stagnant/flowing condition and the velocity of the fluid, CO2

localized corrosion is divided into three groups including pitting, mesa attack and flow-

induced localized corrosion. Pitting occurs at a low velocity of the fluid and around the dew

point temperature range. Sensitivity to pitting is raised by increasing the temperature and

6
 ACCEPTED MANUSCRIPT
partial pressure of CO2 [21, 27, 28]. Mesa attack corrosion is a type of sweet corrosion which

occurs at low to average velocities of the fluid, where the iron carbonate film formed at these

conditions is unstable and unable tolerate the fluid regime [19]. Flow-induced localized

corrosion is formed in fluid velocities above the critical point starts from the pitting or mesa

attack sites and accelerates with the turbulence caused by cavities, bridges around the mesa

PT
sites and any projections in the path. The localized turbulence and stresses will generate

RI
during growth if the carbonate film can lead to the destruction and removal of protective

scales. Once deleted, high velocity of the fluid film does not allow the re-formation of the

SC
film [20, 21].

2.3. H2S corrosion (sour corrosion)

U
AN
Corrosion reactions of hydrogen sulfide, water and steel are very complex. H2S dissolves in
M

water to form a weak acid, which is then partially decomposed to form hydrogen and

bisulfate ions [29]. The low solubility of FeS leads to the development of corrosion products
D

to protect steel from corrosion, especially in high concentrations of H2S.

TE

Depending on the CO2/H2S ratio in the fluid inside the pipe, the corrosion mechanisms are

classified into the following three categories:

EP

- CO2/H2S <20: H2S corrosion is dominant.

C

- 20≤CO2 / H2S≤500: H2S and CO2 combined corrosion

AC

- CO2/H2S> 500: CO2 corrosion is dominant.

In general, high concentrations of hydrogen (higher than 200 ppm) in the aqueous phase at

high temperature produces a highly passive film. However, the iron sulfide conductor films

are effective cathodes and in many systems, breaking of the film can cause localized attack

due to the impossibility of re-formation of film on the surface of the anode pit. At

temperatures below 40°C and in presence of low H2S and CO2, films are often made of iron

7
 ACCEPTED MANUSCRIPT
sulfide deposits with very low adhesion at top of the gray iron carbonate layer, as the general

corrosion can be seen. The localized attack can be seen at the average level of H2S[30].

3. Flow regime and its effect on the corrosion and inhibition

There are 12 flow patterns in the oil-gas-water system, including bubble flow, intermittent

PT
flow, annular flow, stratified flow and several other regimes introduced by Sarica and Zhang

RI
[31]. Stratified flow is a regime where two distinct phases flow together, with the gas phase at

the top and the liquid fluids down at the bottom of the pipe. In low velocities of gas and

SC
liquid fluids, a flat interface is formed between them. By increasing the velocity of the gas,

some waves are formed on the surface of the liquid fluid, and by increasing the velocity of

U
the liquid fluid, slug flow is formed. Considering the velocity of the gas and liquid fluids and
AN
also the different densities of flow regimes, each type can be observed. Table 2 represents the
M

vertical location of water in three-phase systems.

D

Table 2. Water flow distribution in water-oil-gas flow

TE

The slug flow has four regions; leveled liquid film along with gas air pockets at the top,
EP

mixed region, slug’s body and slug-shaped tail. This flow is the most likely pattern in pipes
C

containing oil-water-gas which increases the corrosion and decreases the corrosion inhibitor
AC

performance[32]. Sun and Jepson [33] have shown that slug flow, due to high turbulence and

high tensile stress, may prevent any formation of the film while detaching the corrosion

products from the surface and increasing the corrosion rate. Therefore, awareness of time and

location of the occurrence of slug regime is of great importance.

Recent researches indicate a strong relationship between the corrosion rate and patterns of

flow in the pipeline in three-phase systems inside the pipelines [34, 35]. In these researches, a

8
 ACCEPTED MANUSCRIPT
constant factor known as Froude is defined. Froude number represents the amount of input

turbulence to the film placed on the surface of the slugs while passing over the liquid film. By

thinning the boundary layers and their eventual breakdown, corrosion rate was increased. It

was also observed that in the upward moving paths, Froude number has a higher value in

comparison to the downward paths in a fluid with the similar regime, which is due to the

PT
decrease of stopping the power of the gas bubbles by the liquid fluid due to the gravitational

RI
force.

Obviously, multi-phase flow models are highly dependent on the gas fluid velocity. Research

SC
has shown that higher velocity of the gas reduces the frequency of slug movement [36, 37], as

the reduction lowers corrosion rate. Decreasing water wettability can be another reason for

U
corrosion rate reduction by decreasing the sludge frequency.
AN
At the lower region of the pipe, where the pipe is in direct contact with water, there is the
M

possibility of corrosion especially in the saline water-oil solutions, and for decreasing the

corrosion rate caused by this phenomenon, the two fluids must be blended more [34, 38].
D
TE

4. Internal corrosion control methods in oil and gas pipelines

4.1. Material selection

EP

Different metallic and non-metallic facilities and equipment are used in oil and gas industry.
C

Although non-metallic materials have a remarkable and sometimes critical performance,

AC

more than 90 percent of the used components are metallic materials. However, in some key

parts, there is a significant tendency toward replacement with metallic materials.

In the oil and gas pipelines, depending on the corrosivity of the fluid, carbon steel or alloy

steels are used. Most of the oil and gas pipelines of carbon steel are manufactured in

accordance with API 5L standard or other similar standards. The most common grade of

carbon steel pipes is the API, X65, as their minimum nominal tensile strength is equal to 65

9
 ACCEPTED MANUSCRIPT
ksi. The higher grades such as X80 are also used in limited applications. Hydrogen cracking

caused by fluid, SRB-rich soils and cathodic protection are among the obvious characteristics

of X80 and a high-strength group of API 5L pipelines[12].

When the corrosivity of the fluid in the pipeline is very high and/or control of corrosion by

adding chemicals is not technically and operationally feasible, CRA can emerge as a viable

PT
choice. In this case, the pipes are in a solid form where the tube is completely made of CRA,

RI
or they are in clad form in which carbon steel pipes are internally cladded with the corrosion

resistant steel alloys.

SC
Common types of CRA alloys used in pipelines include 13Cr, 316L, 625 and 825 steel. For

example, in terms of design of "partial pressure of hydrogen sulfide gas equal to 1.6 bars, the

U
temperature of 86ᵒC, high chloride concentrations and pH less than 3.5", carbon steel with
AN
825 clad alloy is a proper choice. From a technical standpoint, the CRA clad pipes are
M

suitable for such working conditions.

The cost of 825 alloy is highly dependent on the market price of nickel, and usually has the
D

price 2.8 times of the carbon steel price (which is inhibited using pH stabilizers or corrosion
TE

inhibitors) and CAPEX and OPEX considerations. CAPEX difference between the choice of

CRA and carbon steel can be recovered in extended periods of time.

EP

The operational costs are considerable and it is clear that selecting the service of carbon steel,
C

leads to lower operational costs than the choice of CRA. The same comparison has been
AC

conducted using same diameter and length of pipes, one operated with CRA pipes and

another operated with carbon steel and corrosion inhibitors [39].

10
 ACCEPTED MANUSCRIPT
4.2. pH stabilization

Control of corrosion using pH stabilizers was studied in connection with industrial projects

during the recent years. The data was also analyzed along with operational feedback from

companies using this technique for corrosion control [40-42].

Corrosion control by pH stabilizers, for sweet wet gas system which does not produce water,

PT
is a viable option. In the sweet wet gas service, pH stabilizer is used once in the system

RI
(chemical recovery is not required). However, from an economic point of view, it is not as

attractive compared to the conventional corrosion inhibitors.

SC
pH stabilizers are suitable for the chemical recovery systems, where pH stabilizer chemicals

are recovered by hydrate inhibitor chemical compounds (such as MEG). Addition of a limited

U
amount of pH stabilizer is enough to compensate the amount of waste in the system. This
AN
method is technically justified in pipelines where pH stabilizer is in recovery mode and has a
M

very low operational cost in relation to the corrosion inhibitor systems. pH stabilizer

technique is not useful in pipelines containing formation water [43]. Control of corrosion by
D

pH stabilization in the sour service has not yet been technically proven.
TE

pH stabilization method is connected with the hydrate control mode. A selected option for

control of hydrate is the kinetic hydrate inhibitors (KHI), which may be required for six
EP

months of the year when the water temperature is lower than the hydrate formation
C

temperature. In the case of KHI injection, considering that its performance differs from the
AC

thermodynamic hydrate inhibitors such as MEG, it is not recycled and therefore will go out of

the system. In these conditions, corrosion control by the method of stabilizing the pH is not

possible, and corrosion inhibitor injection is the corrosion mitigation option. In comparison, it

can be stated that the use of the KHI system is better than the MEG system for lowering

capital expenditure (CAPEX) and reducing costs in a proper lifetime [39, 42].

11
 ACCEPTED MANUSCRIPT
The key element in stabilizing pH is to encourage the system to form a protective layer of

corrosion products on the surface (iron carbonate layer in sweet environments and iron

sulfide layer in sour environments). To ensure full protection, achieving a minimum target

pH is essential. There are two limitations for pH stabilization systems: 1-water chemical

composition (presence of the salts, which leads to the formation of salt scales) and 2-high

PT
acidity of the solution, which increases the injection rate of pH stabilizer chemical. Instead,

RI
the main advantages of this method include prevention of solid particles from forming, which

are formed as a product of corrosion inhibitor at the end of the pipeline. This method has less

SC
environmental effects than corrosion inhibitors technique [30, 43].

The basics of this method involve injecting an alkaline chemical such as Methyl Di Ethanol

U
Amine (MDEA), NaOH and KOH with a specific concentration for raising the pH of
AN
condensed water in the line. If pH increases to a certain level (target pH), internal corrosion
M

of carbon steel pipelines will be controlled and minimized. As mentioned earlier, injection of

an alkaline pH stabilizer is usually taken with a hydrate controller chemical compound

D

(usually from (HO-CH2-CH2-OH) (MEG)) which in this case is provided with the
TE

opportunity of recovery in the downstream, and the chemical components are recycled and

injected to the starting point of the pipeline. The role of MDEA(CH3-N-(CH2-CH2-OH)2 is

EP

the absorption of H+ and, thereby increasing the concentration of bicarbonate ions, which
C

contributes to the increasing of pH and reduction of fluid corrosivity accordingly [12, 41, 44].
AC

4.3. Corrosion Inhibitor

Use of corrosion inhibitors is the most common and widespread technique of controlling

internal corrosion in oil and gas pipelines, as injection is taken by very low dosage of

chemical in the range of 10 to 1000 parts per million (ppm) in case of the continuous

12
 ACCEPTED MANUSCRIPT
injection mode and 1 to 20 volume percent in batch treatment mode. The type and amount of

corrosion inhibitor is associated with the degree of corrosivity of fluid [45].

In this method, the aim is to reduce the corrosion rate to less than 0.1 mm per year. The

strategy of proper corrosion inhibitor selection requires a comprehensive test protocol that

covers a wide range of laboratory and field evaluations [12, 39].

PT
Possible internal corrosion risks for corrosion of carbon steel pipelines with corrosion

RI
inhibitors are summarized in Table 3.

SC
To further understand the corrosion issues and the possibility of using corrosion inhibitors,

some risks mentioned in Table 3 are described below in greater details.

U
AN
Table 3. Internal corrosion/erosion risk in sour gas pipelines
M

Acid refluxed from the wells after acidizing operation can directly destroy the protective iron
D

sulfide film. So, for evaluation of corrosion inhibitor, the chloride content (equal to the
TE

concentration in produced water) should be taken into consideration. In case of water

production from the reservoir, chloride concentration in the reservoir is predicted to be high
EP

which is then decreased during the service, and water becomes more condensed. In a
C

practical perspective, stricter corrosion control methods are required when the chloride
AC

concentration is above 1000 ppm. Corrosion control requirements related to acid flow back

varies depending on the type of formed water [39]. If only the condensed water is formed:

• Wells must be cleaned to reach pH≥4 and chloride content less than the designed

value. During the cleanup process, the fluid must not flow in pipelines.

• Corrosion control is stricter when the level of chloride is above 10000 ppm and

corrosion control is applicable such as what happens when the formation water exists.

13
 ACCEPTED MANUSCRIPT
• Below10000 ppm of chloride content, using the corrosion control methods is

dependent on what is applied for the condensed water.

If the condensed water and formation water have been formed:

• Wells should be cleaned to reach 4≥pH and chloride content less than the designed

value. During the cleaning, the fluid must not flow in pipelines.

PT
• Corrosion control method that is applicable to the formation water should be used.

RI
It is worth noting that even after the fluid reached the desired pH and chloride content, there

was the possibility of intermittent slug production in acid flow back. Hence, monitoring the

SC
pH value and chloride content is necessary. Based on experiences of Shell company, the

amount of chloride has a significant effect on the corrosion rate of the system, as it destroys

the protective film of iron sulfide [15, 39].

U
AN
The corrosion inhibitor is used to control the uniform corrosion. Sweet systems often suffer
M

from pitting attacks, especially in presences of organic acids. Sour systems also tend to have

localized pitting. A number of production fluids lead to the formation of scale or sludge
D

sediments, leading to the emergence of pitting or crevice. In these cases, corrosion control
TE

often requires a proper dosage of the corrosion inhibitor in combination with other

treatments such as scale inhibition and biocide treatment, in addition to the cleaning pigging
EP

of pipeline [46].
C

API RP 14E defines the maximum wear rate for gas and liquid flow based on fluid density
AC

[47]. However, a number of sweet systems, such as BP Prudhoe Bay fields, due to high

multiphase velocity or slug flow regime, have experienced Mesa attack corrosion which was

successfully controlled by applying design requirements, appropriate corrosion inhibitor and

proper monitoring [48]. Mesa attack corrosion is dependent on the structure of the corrosion

products, as well as fluid condition which leads to the breakdown of iron carbonate scales

through fatigue mechanism [48, 49]. Schmitt et al. [50] suggested that some of corrosion

14
 ACCEPTED MANUSCRIPT
inhibitor molecules not only provide protection, but also decrease the slug of fluid related to

the wall shear stress, and thus decrease the energy transfer process which leads to film

fatigue.

The use of corrosion inhibitors to control the environmental cracking (stress corrosion cracks

and sulfide stress cracks) has not been recommended. However, there are significant

PT
numbers of pipelines susceptible to hydrogen-induced damages (hydrogen-induced cracking

RI
and blistering) at sour service, but so far no problems were observed through the usage of

corrosion inhibitors during the operation. Risks related to the use of corrosion inhibitors on

SC
the hydrogen diffusion and sensitivity to hydrogen damage can be evaluated using full ring

test under simulated conditions [51]. Using corrosion inhibitors to reduce the damage of

U
hydrogen is a high-risk strategy, and it needs a well-organized management of corrosion
AN
monitoring and injection systems. It should be noted that this approach is in contrast with
M

NACE recommendations [52]. But it follows the principle that the crack is a function of

hydrogen diffusing into the steel microstructure. Diffusion and the concentration of
D

hydrogen in a metal can be controlled by the rate of corrosion/hydrogen production. For sour
TE

service cracking control, selection of crack resistant material in compliance with NACE

MR0175 is the only reliable option.

EP

From a corrosion management point of view, the corrosion mechanism which can lead to
C

destruction can be controlled if mitigation methods and procedures are well organized. The
AC

primary reason for many of damages related to corrosion is poor management and human

errors [39].

5. Types, structure and classification of organic film former corrosion inhibitors

The frequent question discussed in this case is that the film former corrosion inhibitors refer

to which group of corrosion inhibitors. Basically, most of the inhibitors used in oilfields are

15
 ACCEPTED MANUSCRIPT
film former types, as the films can be thin (single layer) or thick. Corrosion inhibition

mechanism can be as the formation of a protective layer, such as oily wetting film. The

following are some of the most common film-forming inhibitors [53]:

- Alkyl Morpholine

-Amide

PT
- Amide/Imidazoline

RI
- Amide/Imidazoline+ quarterly salts

- Amines

SC
- Amine Salts

- Ethoxylates

- Long-chain carboxylic acids

U
AN
- Multifunction polymers with low molecular weight
M

- Phosphonates and Phosphonate esters

- Salt of pyridine
D

- Quaternary ammonium salts

TE

- Sulfonates
EP

Much effort has been made to improve the efficiency and performance of film-forming
C

corrosion inhibitors in recent years, but there are still some ambiguities which need to be
AC

addressed. Due to the commercial and proprietary nature of most corrosion inhibitors,

manufacturers keep the chemical formulations confidential and therefore, articles and reports

presented in the recent two decades in the case of film-forming corrosion inhibitors are

limited.

Gregg et al. [54] discussed the philosophy and concepts of chemical formulae developed for

subsea pipeline corrosion inhibitors. Furthermore, Cassidy studied the design of acid

16
 ACCEPTED MANUSCRIPT
corrosion inhibitors [55]. Focus on providing proper corrosion inhibitors for the harsh

environments is the main area of research in the corrosion inhibitor technology. Jenkins [56]

stated that the performance of the most of bio-degradable inhibitors is generally limited to

temperatures less than 90ᵒC. Chemical industry seeks to develop corrosion inhibitors

applicable in corrosive environments at temperatures up to 120ᵒC under almost similar

PT
circumstances. Alink et al. [57] described the chemical composition and performance of

RI
corrosion inhibitors based on phosphate esters for oil and gas industries.

The published articles are mostly related to the field applications, including corrosion control

SC
program, design philosophies, programs of chemical management, corrosion monitoring and

injection and distribution of corrosion inhibitor in the line. Bonis et al. [58] have fully studied

U
most aspects of corrosion control using the corrosion inhibitors in pipelines. Chen et al. [59]
AN
used a flow loop to show that corrosion inhibitors based on imidazoline do not have a proper
M

performance for reducing the corrosion in a two-phase system (including salt water and

carbon dioxide gas) at high levels of shear stress.

D

Kolts et al. [60] have shown that the corrosion inhibitors can be affected by existence and
TE

flow of hydrocarbon liquids, and in order to select a proper corrosion inhibitor at the three-

phase condition, conducting the field tests at high and low velocities is essential.
EP

The corrosion rate in the presence of tested corrosion inhibitors is raised by increasing the
C

fluid velocity. Tajallipour et al. [61] have described that the corrosion inhibitors can decrease
AC

the surface tension force, and thus reducing the shear stress to improve corrosion inhibition.

Twelve o’clock corrosion control of pipe by means of corrosion inhibitors is studied

extensively in recent years, and challenges such as reaching the corrosion inhibitor to top of

the line, the effect of type of injection and flow regime were of great interest for the

researchers. Using the corrosion monitoring and measurement of residual corrosion inhibitor

has been discussed for evaluating the performance of corrosion inhibitors.

17
 ACCEPTED MANUSCRIPT
Film-forming amines, also known as fatty amines, are derivatives of fatty acids. These

components which have poor alkaline properties, have been neutralized due to the use of

organic acids in the formulation of the corrosion inhibitor or neutralized by the effect of acid

gasses of fluid which finally convert them to cationic components with positive charges.

Since the electron is released on cathode due to corrosion, these cationic components are

PT
linked to the cathode and form an oily layer on the surface of the metal which prevents the

RI
contact of acid gases, while releasing hydrogen on cathode [62].

Corrosion inhibitors have different functional groups that regularly have a polar head which

SC
includes fatty acids, amines, imidazoline, oxyalkylated amines and components like oxygen,

sulfur, or phosphorus and quaternary amine salts. Moreover, corrosion inhibitors which have

U
a long chain of hydrocarbon (normally C14-C18) adhere strongly to the surface.
AN
M

5.1. Imidazoline

Imidazolines are used extensively in the oil and gas industry, but their properties and
D

behavior are still not understood well. They are categorized as negatively charged cationic
TE

surfactants on imidazoline cores that do not change by the changing of pH, and therefore can

be readily adsorbed on the negatively charged metal surface [63]. To find out the exact
EP

mechanism of corrosion inhibition, determining which functional groups are attached to the
C

metal surface is essential.

AC

Imidazolines are organic compounds with two nitrogen atoms in heterocycle, and three

different proper bonding locations including pyridine-like nitrogen atoms of N3, pyrrole such

as N1 nitrogen atom and aromatic ring [64]. Some of the studies have provided the modeling

of the head and functional groups affiliated to adhesion of the corrosion inhibitor molecules

to the metal surface, while the hydrocarbon tail limits the migration of corrosive agents from

the solution bulk to the metal surface and form a monolayer.

18
 ACCEPTED MANUSCRIPT
It is generally believed that these types of corrosion inhibitors form a self-assembled layer

and protect the surface against the corrosion [65]. Self-assembled systems are a set of

regulated molecules that are formed simultaneously through surface adsorption of active

surfactant molecules on a solid surface as a result of the interaction between molecules,

molecule-substrate and molecule-solvent [66, 67]. Due to the surfactant properties of

PT
corrosion inhibitors, while dissolving in a solution, the free energy of the system is

RI
increased, resulting in an increase of the concentration of corrosion inhibitor at the interface

of the solution. Surfactant molecules are preferably located at the solution/air interface

SC
which leads to reduction of surface tension. Reduction of surface tension is continued until

increasing concentration of surfactant up to the critical micelle concentration (CMC). The

U
shape and the size of the micelles are defined by the nature of surfactant, temperature, pH,
AN
concentration and ionic strength of the solution. Full coverage of the surface by the film is
M

usually taken after saturation of surfactant molecules in the solution [68]. Researches have

shown that corrosion inhibitors with higher concentrations of CMC have more efficiency
D

compared to the corrosion inhibitors with lower concentrations of CMC [69].

TE

Imidazoline is one of the most effective film-forming combinations which is considered as a

starting point of formulations in many patents[70]. In natural conditions, they have low
EP

solubility in water. So in order to generate corrosion inhibitors, they are neutralized by

C

organic acids to increase their effectiveness and to get cationic properties[71]. Figure 1
AC

shows different molecules of imidazoline used in formulations of corrosion inhibitors.

Jevremovic et al. [72] have studied the corrosion inhibition effects of talloil

diethylenetriamine imidazoline (TOFA/DETA imidazoline) on carbon steel in 3 wt% NaCl

media, which was saturated with carbon dioxide at 20 and 70 °C and pH=5 in the presence of

70 ppmv of TOFA/DETA imidazoline corrosion inhibitors. The results indicated that at 20°C,

19
 ACCEPTED MANUSCRIPT
the corrosion rate was reduced with the addition of 70 ppmv of inhibitor from 1 mm/y (in the

case without corrosion inhibitor) to 0.1 mm/y. Furthermore, at 70 °C, the corrosion rate was

reduced with the addition of 70 ppmv of corrosion inhibitor from 4 mm/y (in the case without

corrosion inhibitor) to 0.2 mm/y.

In another study, Jevremovic et al. [73] studied the corrosion inhibition behavior of

PT
TOFA/DETA imidazoline on carbon steel in 3wt% NaCl media in CO2 saturated state

RI
through weight loss method. The surface of the test samples, in presence and absence of

corrosion inhibitors, was studied using atomic force microscopy (AFM). Their research

SC
focuses more on the kinetics and mechanism of adsorption of corrosion inhibitor (TOFA /

DETA imidazoline) on gold in a solution of 3%wt NaCl saturated by carbon dioxide.

U
Corrosion assessment test conditions are shown in Table 4.
AN
M

Table 4. Experimental conditions of corrosion assessment[73]

D

The molecular structure of TOFA/DETA imidazoline is shown in Figure 2. As can be seen,

TE

the structure is composed of a long-chain nitrogen surfactant, and its properties at the

interface of solution/air were evaluated by measuring the stress via drop count method.
EP

Further studies were undertaken by matching laboratory and analytical equations to describe
C

adsorption isotherm data and to determine the thermodynamic parameters. In order to

AC

determine the CMC for TOFA/DETA imidazoline corrosion inhibitor, surface tension was

measured in the range of concentration of 10-90 ppmv.

Based on the results of weight loss experiments with the addition of TOFA/DETA

imidazoline corrosion inhibitor, corrosion rate was significantly reduced while corrosion

inhibition efficiency was at 95%. Assessments carried out by AFM showed that the corrosion

inhibitor TOFA/DETA imidazoline had reduced the surface roughness, and as a result of the

20
 ACCEPTED MANUSCRIPT
formation of corrosion inhibitor film, it effectively protects the surface of plain carbon steel

against corrosion.

QCM measurements confirm that TOFA/DETA imidazoline corrosion inhibitor forms a self-

assembled monolayer on crystals coated with gold. Gold surfaces are known as models to

assess the adsorption of TOFA/DETA imidazoline corrosion inhibitor. It also has been

PT
proven that the uptake kinetics of self-assembly systems can be described by Langmuir

RI
adsorption isotherm [72, 73].

TOFA/DETA imidazoline corrosion inhibitors, through electrostatic interactions between the

SC
TOFA/DETA imidazoline head groups or active sites of gold surface, are adsorbed on the

gold hydrophilic surface having opposite charge which is accompanied by repelling of the

U
small molecules or ions, such as H2O and Cl- [74].
AN
Inhibition of H2S corrosion in the pipeline by hydroxyethyl imidazoline corrosion inhibitors
M

has been assessed using LPR, EIS and EN. Evaluations have been made with different

concentrations of corrosion inhibitors including 5, 10, 25, 50 and 100 ppm in 3%wt of NaCl
D

solution containing H2S. Based on these assessments, the most effective concentration of
TE

inhibitor was found to be 5 and 10 ppm, yet the corrosion inhibition performance was

lowered after 8 hours. In addition, EN results indicated that steel samples tested at a
EP

concentration of less than 10 ppm of corrosion inhibitor is highly susceptible to localized

C

corrosion due to the formation of porous film of corrosion inhibitor. At concentrations of 50

AC

or 100 ppm, steel is susceptible to a combination of general corrosion and localized

corrosion. In the existence of the corrosion inhibitor, the Hurst exponent was higher at time

periods of less than 8 hours, which indicates the short retaining time of corrosion inhibitor.

The obtained data were not applicable to any of the adsorption isotherm models which

represent the extreme weakness in adsorption of corrosion inhibitor on the metal surface [75].

21
 ACCEPTED MANUSCRIPT
The molecular structure of hydroxyethyl imidazoline is shown in Figure 3, where R is the

alkyl chain derivatives.

Diaz et al. [76] studied the control of H2S corrosion in high strength carbon steel pipeline

(API X120) with carboxyethyl-imidazoline corrosion inhibitor. Various electrochemical

PT
techniques such as polarization curves, LPR, EIS and EN methods were employed for this

RI
purpose. 3wt. % NaCl solution containing H2S was used with and without diesel. The tests

were conducted at a temperature of 50°C with different doses of corrosion inhibitor. To

SC
produce H2S, the reaction of sodium sulfide (Na2S) and acetic acid was applied. The overall

structure of carboxyethyl-imidazoline corrosion inhibitor is shown in Figure 4, where a

U
nitrogen-containing ring, saturated C-14 hydrophobic groups and dependent group and
AN
hydrophilic carboxyamido groups were linked to one of the nitrogen atoms. Pure 2-propanol
M

was used for diluting the corrosion inhibitor.

The aforementioned study showed that in the absence of diesel in the test solution, the best
D

corrosion control condition occurred at the 50 ppm dosage with an IE of 98%, as the
TE

efficiency tends to drop with time. This is due to the low residence time of the corrosion

inhibitor. In the solution of 3wt.% NaCl + diesel containing 50 ppm carboxyethyl-

EP

imidazoline corrosion inhibitors, three semicircles were observed in the Nyquist graph. The
C

semicircle of the high frequency was attributed to the charge transfer phenomenon from the
AC

metal surface to the solution while the second semicircle at middle frequencies was ascribed

to the development of oily phase films. Finally, the last semicircle at lower frequencies

indicated the formation of corrosion inhibitor films on the surface. It was observed that with

the addition of diesel, the rate of corrosion is lower than non-diesel conditions. Given that the

tested corrosion inhibitor was oil soluble, it would seem that diesel exhibited co-adsorption

effect, increasing the performance of corrosion inhibitor [76].

22
 ACCEPTED MANUSCRIPT
Ortega-Toledo et al. [77] thoroughly investigated carbon dioxide corrosion of API X120

pipeline using the optimized imidazoline corrosion inhibitor carried out under flow

conditions. A commercial carboxyethyl- imidazoline produced at Lakeland laboratories was

used in this study. This corrosion inhibitor was first dissolved in pure 2-propanol solution and

was used without any further additives. Corrosion inhibitor concentration, according to the

PT
manufacturer recommendations at a constant temperature of 50°C, was considered to be

8.1×10-5 M. The test solution was prepared with the addition of 3wt. % NaCl and purging the

RI
carbon dioxide gas, by de-aeration for 2 hours during continuous injection of bubbles. Two

SC
hours after the pre-corrosion of samples, the inhibitor was added to the solution containing

CO2 and measurements began after one hour.

U
According to polarization curves for solutions containing CO2 and without corrosion inhibitor
AN
in a state of static and rotating fluid (figure 5), an active behavior has been observed in the
M

anode that by increasing the applied potential, the current was also increased without

formation of the passive layer. The density of anode current remains constant, free of the
D

rotation velocity. In the other word, the cathodic branch shows a limiting current which is
TE

also increased by the increase of rpm, that is due to the CO2 hydration for the formation of

carbonic acid [77].

EP

Due to the de-aeration of the solution, reduction of H+ ions is the preferred cathodic reaction
C

which is produced through decomposition of carbonic acid.

AC

H2CO3H++HCO-3 (30)

HCO-3H++CO32- (31)

H++e-1/2H2 (32)

23
 ACCEPTED MANUSCRIPT
According to polarization curves, Ecorr becomes nobler and icorr is also raised along with

rotation speed, and after the speed of 500 rpm, it reaches an almost constant rate. In the

presence of corrosion inhibitors, when the polarization potential is close to relatively positive

values, except for 1000 and 2500 rpm rotational speed, a sudden increase in the content of

anodic branch is visible. This would represent a desorption process [78].

PT
Surface coverage of the adsorbed components with inhibition property (θ) usually decreases

RI
with increasing anodic potential. Increasing polarization potential increases the metal

dissolution, not only on surfaces without corrosion inhibiting components but also for the

SC
surfaces possessing corrosion inhibiting components, since the components become stable at

high potentials. This desorption process ends at the potentials closed to -530 mV/SCE at

U
speeds near 0, 250 and 500 rpm. But at 1000 or 2500 rpm speeds, this process is not present
AN
which indicates the film being unstable at these speeds. In all cases, limited anodic current
M

density is detected that can be due to the influence of the diffusion of electrolyte through the

film-forming corrosion inhibitor. In the cathodic branch, a limited cathode current density is
D

observed which is the result of the CO2 hydration. Table 5 shows the summary of the results.
TE

According to the table, by increasing the rotation speed, an approximate increase in

efficiency and percentage of coverage for corrosion inhibitors have been observed.
C EP

Table 5. Electrochemical parameters obtained from polarization curves[77]

AC

It was also shown that for the solution without corrosion inhibitors, the highest polarization

resistance (Rp) and thus the lowest rate of corrosion is achieved in static conditions. By

increasing rotation speed, the resistance is lowered which is due to the increase of mass

transfer. The lowest amount of Rp was always 2500 rpm during the test. Rp values decreased

with the time, and the amount was almost constant. In other words, for the solution

24
 ACCEPTED MANUSCRIPT
containing corrosion inhibitor, Rp was decreased in 250 rpm and reached its maximum value

(more than double) at 500 rpm. With further increase of rotation speed, a reduction was

observed in Rp that in the case of solution containing corrosion inhibitor solution, the

minimum corrosion rate happened at 500 rpm [78].

The general opinion is that the initial stage of the adsorption of organic corrosion inhibitors

PT
on the surface of a metal, is their replacement by water molecules adsorbed on the surface:

RI
Inhsol+xH2OadsInhads+xH2Osol (33)

Moreover, the corrosion inhibitors are combined with the freshly produced Fe++ ions and

SC
form inhibitor-metal complexes [79, 80]:

FeFe2++2e (34)

Fe2++ Inhads[Fe-Inh]2+ads
U (35)
AN
Depending on the rational solubility, the obtained complexes can either inhibit the additional
M

dissolution of metal or accelerate it. Carboxyethyl-imidazoline in low concentrations does not

possess the ability to form compact complexes, and the complex adsorbed in an acidic
D

solution is easily dissolved. However, at the relatively higher concentrations, enough

TE

molecules of carboxyethyl-imidazoline are provided to form a complex, and thus the

dissolution of the surface layer is reduced and corrosion inhibition is increased.

EP

In the flowing conditions, various effects of corrosion inhibitor’s function can be observed as
C

follows:
AC

1. Flow raises the mass transfer of corrosion inhibitor molecules and also increases the

presence of corrosion inhibitor on the metal surface, thus increasing the corrosion inhibitor’s

function.

2. The hydrodynamics cause increasing of mass transfer of iron ions (Fe2+) during the

dissolution of the metal in the electrolyte bulk, leading to a reduction in the presence of

25
 ACCEPTED MANUSCRIPT
2+
complexes of [Fe-Inh] on the electrode, and as a result, will have a negative effect on

corrosion inhibitor’s performance.

3. The high shear stress caused by high flow rate leads to disconnection of a film of [Fe-

Inh]2+ complex on the electrode’s surface, causing the loss of corrosion inhibitor’s

performance [81].

PT
Imidazolines are products of the reaction between diethylenetriamine (DETA) and fatty acids

RI
in two stages. The fatty acid reacts at the temperature of 160°C for one to two hours to

produce the amidoamines components. Heating the amidoamines at 240°C for 2 to 4 hours

SC
leads to conversion to imidazoline. Amidoamines of the reaction can be used as amine film

formers to fabricate a corrosion inhibitor, which is also cheaper than imidazoline. The fatty

U
acid used to amidoamines and imidazoline must contain at least twelve carbons, and
AN
preferably about eighteen carbons as longer fatty acids can also be used for this purpose.
M

Fatty acids derived from the hydrolysis of vegetable oils with eighteen carbons and at least

one double bond of oleic acid (an unsaturated bond), linoleic acid (two unsaturated bonds)
D

and Tall Oil Fatty Acid (TOFA) are among the best raw materials for this purpose [82-84].
TE

It should be noted that TOFA is a mixture of unsaturated fatty acids, including oleic and

linoleic acid, derived from purified side products of pulp and paper industries. Furthermore,
EP

saturated fatty acids derived from animal oils such as stearic acid are not suitable for the
C

aforementioned reaction, since the imidazoline obtained from saturated fatty acids is waxy
AC

and has low solubility which makes it difficult for formulation and application.

Imidazolines are usually made through condensation of carboxylic acid with 1,2- diamines by

prolonged heating at temperatures above 200°C under an acid catalyst, in the presence or

absence of solvent [85-88]. The latter process often leads to the formation of imidazoline in

low amount and purity. However, milder conditions for the synthesis of imidazoline from

alkanenitriles and DETA [89, 90] is to use S, CS2 [91], H2S [90] or cysteine as a catalyst.

26
 ACCEPTED MANUSCRIPT
For recent works, the imidazoline was made through heating of H2N (CH2CH2NH) n-H

(DETA, n = 2; TEPA, n=4) oligoamines and octadecanenitrile at 150°C by adding elemental

sulfur, which acts as a catalyst while the nitrile with DETA results in Imidazoline 1,

according to reaction with 1 and 0.5 equivalent to TEPA that result in 2 and 3 base-

imidazoline (figure 6). It was the first synthesis reported of heptadecyl-tailed bis-imidazoline

PT
from TEPA [85].

RI
5.2. Amidoamines

SC
Nowadays, the success of using organic nitrogenous base corrosion inhibitors such as

imidazoline, amides, amines and amidoamines and their salts, has been known in the

U
petroleum industry. Due to the different structures and the relevant properties, amidoamines
AN
are superior to alkylamines and their derivatives, as well as the imidazoline. Moreover, in
M

comparison to the alkyl amines, these materials have greater ability to receive more nitrogen,

higher cationic coverage, higher surface activity and higher capacity to neutralize most acids
D

[92].
TE

Simple amidoamines such as monoleyl or monopalmitylamide of EDA are used as anti-rust

additives in lube oils or electronic parts. Soya diamide of DETA can be used as ethoxylate
EP

anti-corrosive agent, although DPTA diamide is also recommended. Formulations containing

C

N-(dimethylaminopropyl) oleylamide and H3PO4 lead to an increase in corrosion resistance

AC

and lubrication of surface of the steel. Corrosion inhibition applications of monoamides such

as 1,3-propanediamine or DMAPA in oilfield equipment have been confirmed [92].

The reaction between of equal amounts of N-oleypropanediamine and maleic anhydride leads

to the production of a vigorous corrosion inhibitor. The exact nature of the component

remains unknown, although the imide should be considered as the main product with a

diamine-anhydride as a byproduct [92].

27
 ACCEPTED MANUSCRIPT
Oxidized microcrystalline wax, considered as an unusual source of acid, is introduced by

Witco Corporation. Condensation of this wax with TEPA produces an anticorrosion

emulsifier which can be formulated as standard amidoamines, such as stearic acid/DETA or

coconut fatty acid/TEPA. A protective coating containing a combination of zinc powder,

silicate and amidoamines are registered for iron metals. Terephthalic acid is a proper anti-

PT
corrosion film for steel. Tall oil fatty acid distillation pitch combined with DETA is

RI
formulated as an anti-corrosion layer. These paints containing chromium oxide, lead oxide

and zinc oxide form anti-corrosion components by adding thallium amidoamines [92].

SC
Desimone et al. [93] have investigated the corrosion inhibition efficiency of amidoamines

amphiphilic in CO2 saturated solutions. In this study, the corrosion inhibitor of N-[2-[(2-

U
aminoethyl)amino]ethyl]-9-octadecenamide (AAOA) was used. Its molecular structure is
AN
shown in Figure 7. Results of polarization and impedance curves revealed that in corrosion

inhibitor concentrations higher than 0.27×10-5M, the corrosion of carbon steel was reduced
M

due to the formation of film on the surface, while at concentrations less than this value, the
D

blocking surface sites of corrosion inhibitor results in the reduction of corrosion. Formation
TE

of the protective layer at higher concentrations is also proved by PM-IRRAS studies, which

have shown that the chemical adsorption of corrosion inhibitor on the metal surface occurs by
EP

forming a bond between the d orbital of iron and N and O atoms. The significant change in
C

Tafel slope and anodic current density in comparison with cathodic current density were
AC

observed, which can be attributed to the formation of the film [69]. Furthermore, in another

study conducted by this group, the effects of variation of temperature and concentration on

the corrosion inhibition of the component in the solution saturated by CO2 was also studied,

and it was indicated that the corrosion inhibition followed the Framkin adsorption

mechanism. At lower concentrations of corrosion inhibitor, inhibition efficiency was reduced

28
 ACCEPTED MANUSCRIPT
by raising the temperature, while at concentrations higher than 8.2 µmole/dm3, corrosion

inhibition efficiency was constant regardless of raising the temperature [93].

Figure 7. N-[2-[(2-aminoethyl)amino] ethyl]-9-octadecenamide [93]

PT
In another study, the corrosion inhibition interaction between the amidoimidazoline corrosion

RI
inhibitor and iodine ions on X52 steel was investigated. Studies have shown that the addition

of these corrosion inhibitors reduced the corrosion rate, as well as corrosion potential. But the

SC
addition of 2 gr/lit of KI further lowered the corrosion current density. According to

polarization curves, the highest interaction was related to the addition of 75 ppm of corrosion

U
inhibitor per liter of amido-imidazoline derivative (IM). Here, the addition of KI led to
AN
decrease of corrosion potential as well, which could be due to adsorption of iodine ions on
M

the surface of the steel. Therefore, it was discovered that addition of IM corrosion inhibitor

additives alone, in general, improves the corrosion inhibition efficiency, and with the addition
D

of iodine ions, it is improved even further due to the synergistic effect. The Gibbs free energy
TE

values of corrosion inhibitor molecules absorption on the surface of the metal determined that

absorption of IM to the metal surface had taken place chemically, and with the addition of
EP

iodine ions, the absorption becomes stable [74].

C

Since imidazoline production process is a two-step and complex procedure that requires high
AC

temperatures and pressures, the whole procedure would be expensive. Amidoamines are

cheaper and easy-to-reach. Amidoamines also contain unsaturated fatty acids as their chain

length is depended on the type of the oil, for instance, if the coconut oil is used, the number

of carbon atoms is 12 and the obtained amidoamine would not be a strong film-forming

agent. Whereas if the 18-carbon fatty acids were used, the resulting amidoamine would be

more effective in the case of formation of a film. It should be noted that neither imidazoline

29
 ACCEPTED MANUSCRIPT
nor amidoamine are effective in hindering the corrosion alone, but rather depend on the

pipeline condition and number of phases in the fluid and its chemical composition to other

components, these compositions can be formulated as the formed film become stable and in

addition to providing proper protective properties to the corrosion inhibitor.

PT
5.3. Aliphatic Amines

RI
In aliphatic amines, nitrogen is only directly connected to the hydrogen atoms and the alkyl

groups. The number of alkyl groups varies between one to three, and based on the number of

SC
attached alkyl groups, these amines are divided into primary amines, secondary amines and

tertiary amines. In the structure of these amines, no benzene or aromatic ring is attached to

U
the nitrogen atom. The alkalinity of these amines is more than ammonia and with the addition
AN
of the alkyl group, the alkalinity is increased further. Hence, the tertiary amines are more
M

alkaline in comparison to primary and secondary amines. The structures of these amines are

shown in Figure 8.
D
TE

In terms of chemical structure, aliphatic amines are simpler than amidoamines and

imidazoline, which contains hydrocarbon chains with 12 to 18 carbon atoms and an attached
EP

amino (NH2) agent. Because of the applications in different industries, using them as a film-
C

former is cheaper and more affordable than other compounds. One of the problems of
AC

aliphatic amines, especially the types containing 14 to 18 carbons, is that they are solid at

room temperature (melting point of 25 to 50 °C) with usually little solubility in organic

solvents, therefore their formulation for the synthesis of corrosion inhibitors is difficult. Of

course, 12-chains aliphatic amines derived from coconut oil have a lower melting point [94].

There are two ways of lowering the melting point of these compounds, including

methylation and ethoxylation. For example, while the melting point of dodecyl amine is

30
 ACCEPTED MANUSCRIPT
24°C, melting point of its methylized derivative (dimethylamine dodecyl) is -19°C.

Corrosion inhibition by aliphatic amines takes place by the following formula:

RNH3+(sol)<=> RNH2+H+<=>RNH2-Fe0 (40)

In which RNH2-Fe0 is an amine reagent that is chemically adsorbed. The chemical

absorption degree depends on the strength of amine-metal bands. A variety of aliphatic

PT
amines under ARMEEN brand are produced by AkzoNobel company. Moreover, in the

RI
patent of Nalco company, aliphatic amines are used as film-forming agents.

The high efficiency of protection in the presence of aliphatic amines may be related to the

SC
presence of nitrogen atoms in the amino (-NH2) functional group. Because of the high

electron density, the nitrogen atom in aliphatic amines acts as a reaction center. In the

U
presence of ethanolamine, relatively high corrosion inhibition was observed in hydrochloric
AN
acid. This behavior can be due to -OH group acting as an electron repellent and providing
M

high electron density for nitrogen, which leads to greater protection. Bond of Lewis acid-

base with corrosion inhibitor as electron donator and the metal surface as electron acceptor
D

plays an important role in the reduction of the corrosion rate.

TE

5.4. Ethoxylated amines

EP

The fourth group of film-forming amines is the ethoxylated amines, formed through the
C

reaction of aliphatic amines and ethylene oxide gas. Due to their good solubility in water,
AC

they play the role of the film-former and surfactant in the formulation of corrosion inhibitors.

Usually, these films are used as auxiliary film-formers and surfactants in conjunction with

other film-forming agents. Similar to other fatty amines, these compounds also have alkaline

properties and should be neutralized by the organic acids to reach their cationic state [84].

Aliphatic amines derived from animal fats such as tallow amine are a suitable material for

ethoxylation reaction. Tallow amine is an eighteen-carbon compound that is solid at ambient

31
 ACCEPTED MANUSCRIPT
temperature and is hardly soluble in organic solvents. Moreover, due to ethoxylation, it turns

to a liquid with high solubility in aqueous and organic solvents. The greater the degree of

ethoxylation, the more solubility of the component in water [95]. Tallow amine synthesis

reaction in ethoxylation process is shown in Figure 9.

PT
5.5. Quaternary ammonium compounds

RI
Commercial corrosion inhibitors are mostly organic compounds containing atoms of oxygen,

nitrogen, sulfur and phosphorus, in which corrosion inhibitor molecules in acidic

SC
environments are adsorbed on the metal surface. The surface inhibitor film separates the

metal from the environment. One of the members of the organic corrosion inhibitors is the

U
quaternary ammonium salts (QASs), that have found widespread applications in various
AN
industries due to their cost-effectiveness, are applied with the purpose of preventing the
M

corrosion of iron and steel in acidic environments [96-100].

Migahed et al. [101] have studied corrosion inhibition of three components of quaternary
D

ammonium compounds on steel X-70 in formation water solution containing sulfide. In this
TE

study, 3-Dimethylamino-1-propanol and sodium metal were mixed under nitrogen

atmosphere, and then the hydrochloric acid was added to the mixture in the presence of
EP

acetone. The reaction mixture was refluxed for 6 hours and was let to cool down. The
C

resulting product was crystallized twice from diethyl ether, and this derivative of dodecanoyl
AC

was considered as E11. In the next step, Butylamine, hexylamine and octylamine and

epichlorohydrin were refluxed separately in a round flask of 250 ml, and the reaction mixture

was let to cool down. The products obtained from dichloro alkylamines were named N4 for

the butyl derivative, N6 for the hexyl derivative and N8 for the octyl derivative. N, n-

Dimethylaminopropyl ester derived from saturated fatty acids (E11) was refluxed in the

presence of acetone with N4, N6 and N8, later cooled and evaporated in order to remove the

32
 ACCEPTED MANUSCRIPT
solvent. Then, the quaternary ammonium gemini cationic compounds were re-crystallized in

two stages and the final compound was labeled as E11N4, E11N6 and E11N8. In general,

quaternary ammonium gemini surfactant was found to be an eco-friendly and effective

corrosion inhibitor for carbon steel in the formation water holding sulfide ions in oil wells.

It was also discovered that IE in all corrosion inhibitors was raised by increasing the

PT
concentration, and the IE order is as: E11N8> E11N6> E11N4. The results of EIS showed that

RI
by raising the corrosion inhibitor dosage, Cdl values were reduced, while Rct and IE% were

increased. This is due to the increase in thickness of the protective film. In addition, it was

SC
found that the adsorption of these corrosion inhibitors on the surface of carbon steel followed

the Langmuir isotherm, and the adsorption-equivalent values indicated that the corrosion

U
inhibitor was effectively adsorbed on the surface. Furthermore, the process was a
AN
combination of physical and chemical adsorption type. Results of surface examination
M

including SEM and EDX, have determined that the corrosion inhibitor made a powerful

protective layer on the surface which isolated the metal surface from the corrosive media.
D

Moreover, the N-vanillyl-O2'-hydroxypropyl trimethylammonium chloride chitosan (VHTC)

TE

was used to evaluate the corrosion inhibition of Q235 steel. Q235 is a widely utilized steel

with a low resistance to chemical corrosion. Chitosan is a natural polymer product of chitin
EP

deacetylation, that due to its non-toxicity, biocompatibility and multi-functionality, has found
C

vast applications [102-104]. Type and adsorption behavior of corrosion inhibitors depends on
AC

their type and structure [105]. Furthermore, the presence of amino groups and multiple

hydroxyl groups in the structure of chitosan, which can interact with the metal surface and be

adsorbed on it, converts this chemical to a potential corrosion inhibitor for metals. In a study

conducted by Wang et al.[106], quaternary ammonium salt composed of vanillin chitosan

Schiff base, and its function as a corrosion inhibitor was investigated through weight loss and

electrochemical methods. In this study, 3-chloro-2-hydroxypropyl trimethylammonium

33
 ACCEPTED MANUSCRIPT
chloride (CHPTA) was obtained by mixing trimethylamine hydrochloride and

epichlorohydrin for 3 hours. First, chitosan soaked in a solution of methanol in the flask and

stirred, and then vanillin dissolved in methanol was introduced into the flask under

temperature during a specified time. Then, CHPTA was added to vanillin-chitosan Schiff-

base and isopropanol in proper temperature and duration. In Figure 10, the Q235 steel

PT
corrosion inhibition efficiency is shown in 1M solution of HCl by adding different

RI
concentrations of VHTC, the vanillin-chitosan Schiff-base, chitosan and imidazoline at 298K.

Corrosion inhibition efficiency is enhanced by increasing the concentration of corrosion

SC
inhibitor and its value is in this order: imidazoline>VHTC> Chitosan>vanillin-chitosan

Schiff-base. Results of potentiodynamic and electrochemical impedance studies have shown

U
that VHTC has a good performance as a corrosion inhibitor on Q235 steel in 1M HCl
AN
solution at 298K. Moreover, when the concentration of VHTC reaches 200 mg/lit, IE is at
M

90% [101].

Zhang et al. [107] have studied the synergistic effect of imidazoline-based dessummetric bis-
D

quaternary ammonium salts and thiourea for corrosion inhibition of CO2 corrosion at high
TE

temperatures. Imidazoline quaternary ammonium salts are already used extensively for CO2

corrosion control. An imidazoline-based dessummetric bis-quaternary ammonium salt (DBA)

EP

has been synthesized in the laboratory, and its eco-friendly properties and effectiveness in
C

CO2 corrosion control have been proven. DBA has been relatively effective under normal
AC

conditions, but at high temperatures, it is required to increase the dosage in order to retain its

protection ability [108, 109]. On the other hand, Thiourea (TU) is a corrosion inhibitor with

outstanding inhibition function, easy production and low price for metals. The disadvantage

of this corrosion inhibitor is its small concentration range for application in acidic

environments.

34
 ACCEPTED MANUSCRIPT
Quaternary ammonium compounds with the general formula of R4N+X, in which R may be

the same group or different groups of the alkyl or heterocycles with long chain (12 to 20

carbon atoms), X is a halide anion such as chloride and bromide anions. The nitrogen atom is

positively charged and four carbons are attached to it.

Quaternary ammonium salts are the main cationic surfactant groups with anti-corrosion and

PT
softening properties. Given that most solid and metal surfaces are normally negatively

RI
charged, these compounds have a strong tendency to attach to the surface of metals and

inhibit corrosion due to their positive charge.

SC
Considering that there is a large amount of H+ in sour environment, it could attack the

negatively charged metal surface and cause severe corrosion. Positively charged quaternary

U
ammonium compounds compete with H+ to be bound to the surface of the metal, and when
AN
they are attached to the metal surface, they inhibit the contact with corrosive materials by
M

forming an oily layer. Of course, all quaternary ammonium compounds are not suitable for

this purpose and must contain at least one aromatic ring to establish a strong bond with the
D

metal surface.
TE

Unlike fatty amines, quaternary ammonium compounds have cationic nature and do not need

to be neutralized by the acid. Due to their high water solubility, their film-forming
EP

capabilities are not as strong as imidazoline and polyamide amine, but they can also act as a
C

surfactant [92].
AC

5.6. Sulfur compounds

Some of the sulfur components have little individual effect in reduction of corrosion, but in

combination with the film-forming amines, they are capable of improving their efficiency.

Mercapto-acetic acid is one of these components which is used in the formulation of some of

the commercial products [62]. Chemical structure of mercapto-acetic acid is shown in Figure

35
 ACCEPTED MANUSCRIPT
11.

Efficacy of a number of thiourea derivatives in decreasing the sweet corrosion was patented.

The compound was obtained by condensation reaction of thiourea with diethylene triamine,

and since it has both nitrogen and sulfur in its structure, it forms a strong bond with the metal

surface capable of reducing corrosion substantially [110]. The process of production of

PT
corrosion inhibitor is conducted through the condensation reaction of thiourea with DETA at

RI
180°C in 5 hours, as shown in Figure 12.

It is worth noting that sulfur compounds are foul-smelling and more toxic than the film

SC
former amines.

5.7.
U
Polymeric inhibitors based on polyamine derivatives
AN
Long-chain polymers, particularly those derived from fatty acids, are typical examples of
M

film-forming corrosion inhibitors [111]. Various studies support the fact that amines have a

specific chain length. Hence, several patents described several derivatives of polyamines in
D

order to achieve adequate corrosion inhibition [112, 113]. Some molecular structures of
TE

polymeric film former corrosion inhibitors are shown in figure 13 [114].

These acids consist of substitute acrylic acids and additional unsaturated acids such as
EP

naphthylpropiolic, pentynoic, hexynoic, octynoic and linoleic acids. Particular polycarboxylic

C

acids may be used, although carbon chain length must be controlled for specific examples
AC

when freezing of products is not required.

Corrosion inhibitors, which are established from this matrix, can be obtained by the reaction

of a polyalkylen amine and unsaturated diol in the presence of a metal catalyst such as

Cu(C2H3O2)2, CuCl2, CoCl2, TiCl4 or SnCl2. Afterward, the organic acids are added to the

amine-diol product.

36
 ACCEPTED MANUSCRIPT
The film-former corrosion inhibitors can dissolve in hydrocarbon-based solvents and get

pumped into the well’s fluid or low dimension pipes directly and get released at the end of

the well, where the fluid pressure should be sufficient for carrying the materials in the tube.

In addition, this category of corrosion inhibitors still possesses high water dispersion [114].

Polyamines react with diones in order to synthesize water-soluble corrosion inhibitors

PT
suitable for brine hydrocarbon environments [115]. The reaction product consists of

RI
hemiaminals, aminals, enamines and imines composed of roughly 10 ppm to 70% of the

effective corrosion inhibitor. Imines and hemiaminals, in particular, are more effective than

SC
other groups. The effective concentration range is 10-250 ppm of process streams in the

continues operation exposure.

U
It is shown that the polymerization reaction product is able to react with hydrogen sulfide to
AN
form a derivative, which is effective in metal corrosion protection. Its applications are in the
M

areas of downhole pipes, subsurface water injection, pressure maintenance or disposal, and

drilling and flowing lines above ground. Corrosion inhibitors of this category can preferably
D

work in batch operation using dense film formulation achieved by using aromatic
TE

hydrocarbon solvents.

Surfactants may be added to improve the properties of film formation and dispersion. General
EP

corrosion tests using different cuts of water from the mixture of water-oil include Texaco
C

EDM lube oil fluids and saltwater containing 10% NaCl and 0.5% CaCl2. Among all the
AC

tested matrices, the 2,5-hexanedione component and mixture of 1,8-diaminoctaneand H2S

derivatives mixtures exhibited the best performance in the test environment at concentrations

lower than 10 ppm [114].

In order to improve the corrosion inhibition performance of polyamine or amino-containing

mercaptans or thiols, these agents can be associated via different ways to form a single

chemical structure. Thiols can react with unsaturated carboxylic acid, epichlorohydrin or

37
 ACCEPTED MANUSCRIPT
acrylonitrile derivatives to form thioester bonding. The formed molecules can result in

effective corrosion inhibition with polyamides. In other words, acidic derivatives can directly

react with polyamines in order to form the corrosion inhibitors [116]. Figure 14 displays a

number of representatives. For example, the reaction product of polyamine octyl thiol or

dodecylthiol, methyl methacrylate and diethylenetriamine for corrosion protection efficiency

PT
of 85-90% was tested in 2% NaCl brine solution saturated with CO2.

RI
An alternative sample is composed of decylthioacetic acid and aminoethylethanolamine. Not

only the aforementioned corrosion inhibitors are operative in the normal oil and gas wells

SC
applications, they can also be applied to other applications including enhanced oil recovery

by flotation wastewater consumption. Additionally, they are used for pickling of ferrous

U
metals which form a passive oxide layer. This formula is claimed to be effective for acidizing
AN
treatment of earth formation and deep wells.
M

A great deal of effort was dedicated to the production of corrosion inhibitors effective for

various types of saltwater and seawater with high levels of biodegradability. Corrosion
D

inhibitors of a quaternized oligomeric/polymeric compound with at least two units of

TE

alkoxylated amine and two or more anhydride units were recently introduced as alkoxylated

fatty amine which produces a dicarboxylic acid derivative as corrosion inhibitors for steel
EP

surfaces in oil and gas processes.

C

In recent studies, a new series of quaternary amines and alkoxylated amine with improved
AC

molecular weight and distributed molecular weight have been reported, which have a greater

absorption on metal surfaces and hydrophobic alkyl chain compared to commercial

monomeric corrosion inhibitors. The polymer structure shown in Figure 15 may differ in

alkyl chain length and position, the presence of ethyleneoxy and longer chain as well as the

type of the amines [117]. Surface tension analysis of polymers created the structures shown

in Figure 16 indicates a high surface activity and behavior of monomeric surfactant with

38
 ACCEPTED MANUSCRIPT
critical micelle concentration levels of 0.05-0.1 g/l. In case of compatibility, poly-CI Q and

AEF showed the highest tolerance for salt water, while Q had the lowest width of solubility.

Based on bubble test and rotating cylinder electrode (RCE), these structures and the polymers

labeled as A, Q, AEF and EQ have suitable corrosion inhibition properties [114].

Corrosion inhibitors for oil and gas can be made based on a silicon backbone with amine

PT
derivatives. Polyether silicone copolymer with amine moieties can be combined with water

RI
and carboxylate from the ether or a metal salt, and act as the corrosion inhibitor [118].

Carboxylate ions facilitate the delayed washing of filter cake dissolved in acid after

SC
hydrolysis to form carboxylic acids. Additionally, it can also react with amine groups of

silicon-based polymer to form ammonium ions, which are very well known for stable

U
absorption of corrosion inhibitor molecules on the metal surface.
AN
Based on the weight loss analysis, polymeric corrosion inhibitor can prevent the weight loss

less than 0.05 lb/ft2 at 200 oF and 500 psi for 24 hours. In addition, the produced corrosion
M

inhibitor is biocompatible.
D
TE

Some laboratory test results of corrosion inhibitors from different discussed categories have

been listed in table 6. This review table includes the generic types of organic film-forming
EP

corrosion inhibitors, tested material grade, the concentration of corrosion inhibitor, type of
C

experiments and test results. By considering the dosage of corrosion inhibitor and obtained
AC

efficiency for each type of film-forming corrosion inhibitor, a guideline for selection of

proper chemicals for the intended application is provided.

Table 6. Review table including the generic type of organic film former corrosion inhibitors,

tested material grade, the concentration of corrosion inhibitor, type of experiments and test

results

39
 ACCEPTED MANUSCRIPT

6. Evaluation of the inhibition mechanisms by film former corrosion inhibitors

There are various hypotheses and theories on the performance mechanisms of nitrogen-

containing compounds with long chains. One of the classical theories in the field is the

sandwich theory. In this theory, the lower part of the sandwich is the connection between the

PT
polar head of the molecule and the metal surface, and the protective function depends on the

RI
strength of this link.

The middle part of the sandwich is the non-polar end of the molecules, and the degree of

SC
protection participation in the sector is dependent on the covering or wetting level of the

surface by the molecules. The upper part of the protective sandwich is a hydrophobic layer of

U
oil or hydrocarbon that is attached to the tails and long carbon chain. This oil layer acts as an
AN
external protective film that, by coverage of the corrosion inhibitor film, acts as a barrier
M

against the penetration of iron ions from the metal surface to the electrolyte while also

decreasing the diffusion to the internal parts and corrosive factors [119]. Figure 17 shows the
D

schematic of the film.

TE

Imidazoline has numerous applications in CO2 corroded oil and gas pipelines.
EP

Electrochemical impedance spectroscopy (EIS) as a reliable technique for study on corrosion

C

inhibitors [120] was used to study the formation and destruction of imidazoline corrosion
AC

inhibitor film against CO2. The results of EIS are helpful in analyzing the corrosion

inhibition mechanism. The results indicated that the formed film was multi-layered, as the

internal layer was a combination of the base phase and the corrosion inhibitor, and the

external layers were comprised of the corrosion inhibitor molecules. The corrosion inhibitors

are injected into the oil and gas transfer pipelines in either continuous or batch form, as one

of these two methods is selected based on fixing the concentration of corrosion inhibitor to

40
 ACCEPTED MANUSCRIPT
oppose CO2 corrosion [121, 122]. EIS method has limitations in regards to the continuous

control of corrosion inhibitor film performance, since EIS measurements take approximately

1 hour which is a relatively long time, and thus is not suitable for usage in systems where the

parameters of corrosion, including potential, are continuously changed. For example, when

adding the corrosion inhibitor, the EIS test results are not accurate. Electrochemical noise

PT
analysis (ENA) has managed to overcome these limitations. ENA method is used to study

RI
the rate of corrosion and localized corrosion [123, 124].

Due to the existing complexities, in order to study the performance of the corrosion

SC
inhibitor, it is required to conduct an improved monitoring. Various methods have been

introduced in order to study the performance of the corrosion inhibitors such as weight loss

U
coupons and resistive probes and machine test, which can be used for determination of the
AN
film durability and adhesion. The durability and adhesion of the film on the surface are one
M

of the essential aspects of studying the corrosion inhibitor characteristics. Sufficient

concentration of the corrosion inhibitor on the surface is one of the important factors of
D

making more durable film on the surface [62].

TE

6.1. Electrochemical Impedance Spectroscopy (EIS)

EP

A multi-step test was conducted by Tan et al. [125] in order to study the film formation on
C

the surface in a solution containing 50 ppm of corrosion inhibitor (47 hours testing period).
AC

Later, in order to analyze the effects of the corrosion inhibitor film at very low

concentrations, the electrode was tested for 22h in a solution containing 5ppm of imidazoline

using EIS. In the next step, to evaluate how the surface inhibitor film will be destroyed, the

electrode was rapidly moved to a solution free of corrosion inhibitors, and EIS was conducted

on it (after 20 hours testing period). The electrode was stable in all steps. Finally, in order to

assess the shear stress effect on corrosion inhibitor films, the electrode was placed in a

41
 ACCEPTED MANUSCRIPT
solution under 1000rpm rotation with a sufficient concentration of corrosion inhibitor (for 85

hours testing period).

In the first stage for 42 hours, the size increase of half circles of Nyquist plots clearly

indicates changes in reaction mechanisms in the presence of corrosion inhibitors.

Furthermore, a new phase transition presented in bode plot shows the changes of electrodes

PT
surface structure proportional to the growth of the film. In bode plot, two peaks were

RI
observed which represent two original electrochemical kinetics. The smallest ring in the

Nyquist plot represents a corrosion stage corresponding to 1Hz in bode-phase plot [126]. This

SC
impression is confirmed by testing of weight coupons [125, 127]. Semi-circles with the

higher frequency generally indicate the presence of corrosion inhibitors, since the insulating

U
film generally has a higher time constant so that the phase degree transfers to higher
AN
frequencies. Fitting of the two mentioned graphs with the resistance model does not coincide
M

in an ideal manner, which is explained using pseudo inductance phenomenon [128-130]. The

high transmission phase angle in bode plot at higher frequencies is also indicative of a
D

multilayered surface film structure. Tan et al., [131] with the help of NLLS-fit 4-layered
TE

computer modeling, have identified four layers with different resistivity which shows the

difference in the density of layers. The first layer has the highest resistance while the lowest
EP

layer has the least resistance. The results show that the corrosion inhibitor film was formed
C

within the initial 8.5 hours. After 42 hours, the resistance of corrosion inhibitor layer was
AC

changed from 1119 ohms to 5246 ohms. These changes are shown in Figure 18. This chart

shows these changes in the first 8.5 hours. R1 (the resistance of the first layer) was increased,

followed by a rapid increase of Rt. These changes can be justified by the slow chemical

reaction on the electrode surface, which leads to the enhancement of film resistivity. In this

case, the time required to reach electrochemical equilibrium takes too long which shows that

surface chemical reactions or chemisorption occur more frequently than physical adsorption.

42
 ACCEPTED MANUSCRIPT
In the second step of the experiments, when the electrode remained in corrosion inhibitor

containing solution for 48h, and the concentration of corrosion inhibitor was lowered from

50 to 5 ppm, the destruction of the film was investigated and this condition was found to be

similar to the drop of corrosion inhibitor concentration with time in the pipeline.

The results of EIS studies were drawn in both Nyquist and Bode plots and, as expected, the

PT
total resistance of the film was suddenly dropped, as the main cause was the destruction of

RI
the corrosion inhibitor film through an unknown mechanism. But contrary to expectations,

the impedance of electrode was enhanced, which can be ascribed to the repairing of film

SC
layers. A similar experiment was carried out in the same solution but without corrosion

inhibitor and, similar changes were observed. This proves that the main structures of the

U
corrosion inhibitor film and the double layer was not changed, and it can be concluded that
AN
the corrosion inhibitor film did not follow the physical adsorption rules since it was mostly
M

absorbed in the chemical. CO2 corrosion products can also be placed in holes in the

corrosion inhibitors surface film and seal it. In the third step, which was mostly concerned
D

with studying the effect of shear stress on the film, the results of EIS studies were drawn in
TE

two Nyquist and Bode plots, as the continuous reduction in diameter in Nyquist and the

gradual disappearance at higher frequencies of a shift in phase degree represent the

EP

separation of the film by surface shear stress (Figure 19).

C

The performance of imidazoline based corrosion inhibitors on carbon steel was studied in
AC

large-scale turbulent flow in oil-sea water at a temperature of 90°C and pressure of 300psi

by EIS method. The results indicated that with the addition of corrosion inhibitors to the

solution, corrosion resistance was improved. It was also observed that the charge transfer

resistance and Warburg factor were increased progressively for up to 8 hours, as a result of

the condensation time and formation of surface film by the corrosion inhibitor. Furthermore,

it was shown that the charge transfer resistance and Warburg factor were not much different

43
 ACCEPTED MANUSCRIPT
in the presence of either 100 or 50 ppm, which indicated no difference of corrosion

resistance by increasing the excess amounts of the corrosion inhibitor [132].

6.2. Electrochemical Noise Analysis (ENA)

In the first step of the experiments, the working electrode was put in the mentioned solution

PT
for 45h containing 25ppm of corrosion inhibitor in order to study the formation of the

RI
corrosion inhibitor film. Afterward, it was placed in the inhibitor-free solution with a stirring

rate of 1000rpm to investigate the destruction of the film (about 20h). After inserting two

SC
electrodes exposed to a solution containing the test inhibitor and consistent implementation

of ENA test, 40mV increase at 1000s was observed. Using moving average removal method

U
in potential-time charts, real noise voltage was specified. Unlike several works [106, 133] no
AN
direct link was observed between the film formation and the rate of corrosion. There is a
M

stronger relationship between film formation type and fluctuations of noise current. It was

also observed that decreasing the noise current fluctuations occurred over time. Although
D

there is a relationship between noise current with the type of corrosion inhibitor film
TE

formation, no exact ratio exists between them. It is indicated that by using the rate of noise

voltage, standard deviation and standard deviation of the noise current, noise resistance can
EP

be determined and subsequently, the corrosion rate could be calculated [134, 135].
C

Tan et al. [125] have investigated the performance and the durability of the added corrosion
AC

inhibitor film in continuous form in order to evaluate the benefits and limitations of the EIS

procedure. In this study, impedance test was conducted on the corrosion inhibitor in different

stages, and results indicated that EIS was a time-consuming method, only applicable in the

electrochemically stable systems. As a result, it cannot be used in gradual film formation

processes as well as its failure. In the electrochemical noise analysis, the possibility of

continuous monitoring of corrosion process and thus, monitoring the corrosion inhibitor is

44
 ACCEPTED MANUSCRIPT
possible.

In another study by Tan et al. [136], type of the corrosion inhibitor film formation and

destruction were studied in an environment similar to the pipeline using ENA method. The

observations indicated that by the formation of the corrosion inhibitor film, the noise current

was dramatically decreased while its resistance was enhanced. The opposite trend also

PT
happened in its destruction. It is noted that the electrochemical noise analysis method is able

RI
to evaluate the performance capability of corrosion inhibitor film in real time, and has the

ability to record changes at any given moment. The test results showed good compliance

SC
with LPR.

6.3. Harmonic Analysis (HA)

U
AN
This method has a wider range of chemicals using non-linear analysis based on AC current
M

distortion and nonlinear reflected analysis in the frequency range. Thereby, the corrosion

rate can be obtained using Tafel test in both cathode and anode [137]. Harmonic analysis
D

method creates sinuous waves and then analyses the results with the help of filtering of the
TE

polarization data by DFT equation [138]. Suarez et al. [139] have dedicated a part of their

research to examination of the LPR test results with HA analysis, and have reported the
EP

compatibility of HA method. It should be noted that the corrosion rate of the survey with the
C

help of HR methods is half of that of the LPR method. Results have shown that interactions
AC

between the hydrocarbonic phases and corrosion inhibitor films improve the surface

adhesion and hydrophobic performance, similar to the conclusion obtained by using EIS

[140, 141].

6.4. Thermogravimetric Analysis (TGA)

TGA method requires continuous weighing of samples in special environments, as a

45
 ACCEPTED MANUSCRIPT
function of temperature or at a constant temperature. This method is widely used for

evaluation of oxidation and hot corrosion. This method was used to study the kinetics and

high-temperature oxidation mechanism of alloys. It has also been used in laboratory research

in order to study the corrosion kinetics of metallic nickel and cobalt-based alloys. The results

indicate the effects of alloy composition, corrosive salt composition, gas composition and

PT
temperature on the rate and the mechanism of corrosion [62].

RI
6.5. Quartz Crystal Microbalance (QCM)

SC
Initially, the QCM method was utilized to measure weight changes caused by thin film

deposition in vacuum systems. This method has the ability to measure weight in the scale of

U
nanograms and picograms. The design of this method is based on piezoelectric technology
AN
[123].
M

7. The selection process of corrosion inhibitors for oil and gas pipelines
D

One of the biggest challenges of the leading manufacturers of corrosion inhibitors is to

TE

perform the laboratory tests to reflect real field conditions to some extent. In general, a

suitable corrosion inhibitor should act in an effective way to protect pipelines from corrosion
EP

in a wide range of operating conditions such as fluid regimes, different ratios of oil to water,
C

diverse surface quality, etc. Therefore, designing a testing unit for field simulation in the
AC

laboratory is not quite feasible. Accordingly, to evaluate the corrosion inhibitor for field

applications, it is necessary to perform a series of laboratory tests where each one assesses

the specific performance of corrosion inhibitor. A typical development process for a

corrosion inhibitor evaluation in oil and gas industry is shown in Figure 20. This process has

been shown continually since the knowledge obtained in each stage of improving cycle of

corrosion inhibitor provides the information about the molecular structure for the synthesis

46
 ACCEPTED MANUSCRIPT
of corrosion inhibitor components.

Jorge et al. [142] have outlined environmental conditions and corrosion potential for

determination of essential tests for evaluation of corrosion inhibitors in pipelines. In this case,

the fluid in the pipe was considered a composition of the wet gas and crude oil. The wet gas

PT
pipeline is roughly designed for gas transfer, which contains condensed water and oil. The

RI
crude oil pipelines are also designed for oil transfer while still containing water and gas. The

chemical composition of water also changes from low salt content water to produced water

SC
with high amounts of salt. A complete and accurate assessment of corrosion inhibitor should

consider changes occurring during the production period. The tests carried out in the

U
laboratory for selection of the corrosion inhibitor include wheel, bubble, static, rotating disc
AN
electrode, rotating cylinder electrode, jet impingement and rotating cage tests taken at
M

elevated pressures. Moreover, field tests and monitoring are done by installing a loop to the

pipeline and using coupons, respectively.

D

Bubble Test: This test is generally known as a corrosion test in stirred movement. This is a
TE

very flexible laboratory test taken to study the corrosion rate and performance of the

corrosion inhibitor. Considering the laboratory errors, differences in bubbling speed have
EP

minimal impact on the corrosion rate.

C

Static Test: Static testing is used to evaluate the performance of corrosion inhibitor in
AC

absence of the flow. The corrosion rate is evaluated by using the measured weight loss or

electrochemical methods. Since these tests are measured in absence of the flow, they

represent a situation in which the pipe is not in service.

Rotating Disk Electrode (RDE): One of the problems in the test is concerning RDE-flow

with pipe flow, and the difference in the geometry of two systems. RDE flow is in the linear

range and does not cover the areas of transition and turbulent flows. The biggest problem

47
 ACCEPTED MANUSCRIPT
with this test is that its results cannot be generalized to the actual results since these results

belong to the linear flow. In general, the rate of corrosion in presence and absence of

corrosion inhibitors is increased by raising the velocity.

Rotating Cylinder Electrode (RCE): The test is compact, inexpensive and has high

controllability. This test can be used in a turbulent regime with a wide range of Reynolds

PT
number.

RI
JI: This method is widely used to study corrosion in high-velocity flows, and is a new way of

evaluating the performance of corrosion inhibitors. This method can design the turbulence in

SC
multiphase systems. Furthermore, the control of this test is very simple.

RC: This technique, which simulates the corrosion of pipeline at high temperature and

U
pressure, is one of the best methods of simulating pipeline corrosion in the laboratory. The
AN
flow pattern is determined qualitatively in this method. The corrosion rate and morphology of
M

pipes must be determined using a combination of gas, liquid and steel. Other factors are

temperature, pressure and flow.

D

Bubble and static tests are the laboratory methods, which have low compliance with the field
TE

results. Rotating cage is the best method for selection of corrosion inhibitors. Using this

method, larger and deeper holes can be detected in the system. Methods of jet impingement,
EP

RCE and RDE are also evaluated. These methods properly model the flow patterns inside the
C

tube well, but cannot evaluate the conditions such as coupons pitting corrosion in the bottom
AC

of the pipe [143-145].

Finally, one of the most important characteristics of laboratory tests is the capability to

evaluate the pitting corrosion [146, 147]. There are several problems with using the corrosion

inhibitors in gas pipelines. At first, they are only effective if the flow regime in the pipe and

the tube are the same. In other words, if they do not prove effective, another corrosion

inhibitor should be used. Moreover, phase distribution in the pipe must be considered to

48
 ACCEPTED MANUSCRIPT
choose a proper concentration of the corrosion inhibitor. Finally, it should be considered that

some of the pipelines operate at high velocities. As a result, the corrosion inhibitors are

confirmed only for severe shear conditions. There are two reasons for the ineffectiveness of

the corrosion inhibitor. First, the corrosion inhibitor passes into the dehydration system and

numerous lines operate in a wavy manner. As a result, a corrosion inhibitor is required which

PT
is soluble in water and able to protect the bottom of the pipeline. Oil and gas mix pipelines,

RI
for example, pipes with 30 to 40 percent of water and velocities higher than 1 to 1.5 meters

per second are not corroded. Most pipes are not under such circumstances, however. Use of

SC
corrosion inhibitors in most of the tubes has met with failure. First, most of the chemical

compounds are only effective when the system is clean and it is not yet known which

chemical composition should be used.

U
AN
The importance of cleanliness can be explained by the fact that corrosion compounds
M

inhibitors are film-forming. If there are sediments in the system, it means that there is a large

surface area that must be covered by corrosion inhibitor. As a result, a greater concentration
D

of corrosion inhibitor is required. Therefore, a higher concentration of corrosion inhibitor is

TE

required which raises the costs [148]. Oil and gas pipeline corrosion is strongly influenced by

fluid flow, transfer volume and fluid properties change over time. As a result, the nature of
EP

the corrosion and the need to prevent corrosion in the pipeline over time change with the
C

passage of time and change of location in the pipeline [33, 149]. Refined petroleum pipelines
AC

or products are generally not corrosive and do not need to be protected. Dehydrated gas is not

corrosive to steel tubes and does not need to be protected [150]. Tubes used for extraction

from seawater are normally protected by deoxygenation and addition of biocide. In three-

phase and crude oil pipelines, film-forming inhibitors are used. Several considerations should

be kept in mind in order to prevent corrosion. These considerations must be taken throughout

the design, engineering and manufacturing. Phases in the pipe may change with time,

49
 ACCEPTED MANUSCRIPT
including temperature, speed, composition and production of oil or gas, water components

and the percentage of the current regime, etc.

Furthermore, design manufacture and commissioning in deep waters are among the most

expensive items. Environmental concerns should also be taken into consideration when it

comes to the use of corrosion inhibitors.

PT
In case of pipelines used for prolonged times, the cost of using corrosion inhibitors is greater

RI
than the use of CRA. As a result, the use of CRA in short segments is of high importance,

particularly in corrosive environments. Briefly, for designing the corrosion inhibitor of

SC
pipelines, all phases in the pipeline must be investigated, including the highest and the lowest

rate of production, the highest and the lowest pressure, different flow regimes regarding the

U
lifetime and combination of products [53]. The results of studying inhibitors in an experiment
AN
cannot account for other projects since the tests have been taken under specific
M

circumstances. The use of corrosion inhibitors in the pipeline has three types of applications.

First: water and wet gas system without concentrated hydrocarbon, in these systems, the
D

corrosion inhibitor should act in a way that it can be used without the benefit of
TE

hydrocarbons. Second: water hydrocarbons systems with low velocity (either with or without

gas) with the classified flow condition. In this case, the corrosion inhibitor should adjust its
EP

condition to the aqueous phase. Research has proven that low solubility of hydrocarbons in
C

water can improve the performance of corrosion inhibitors. Third: water hydrocarbon systems
AC

with high turbulence in the pipelines with mixing flow conditions, for example in multiphase

pipelines [151].

Generally, in order to select the proper corrosion inhibitor, the following criteria shall be

considered and determined:

50
 ACCEPTED MANUSCRIPT
- A reliable model of the flow, temperature profiles along the pipeline, flow regime in

the case of constant flow, changes in the composition and phase behavior of large diameter

pipeline and distribution of corrosion inhibitor during batch pigging application .

- Detection of corrosion mechanism: corrosion location (top or bottom of the line) and

sweet and sour mechanisms.

PT
- Modeling of the corrosion using the proprietary corrosion models

RI
- Determination of laboratory testing program to evaluate the extent of corrosion

reduction

SC
- Field monitoring to determine the optimum corrosion inhibitor and the exact

U
inspection of pipelines AN
The existing water in the wet gas pipeline can form scales out of the corrosion products.

Therefore, it is essential to conduct a complete water analysis to select the best corrosion
M

inhibitor. This point is highly important when high volumes of water are produced.

In long pipelines, there is a significant difference between input and output pipeline
D

temperature. Pipeline temperature determines the formation of scales on the metal surface.
TE

Higher temperatures at the input can cause the formation of a stable film of corrosion
EP

products on the surface, while at lower temperatures; the formed film is less stable and has a

higher porosity. As a result, in order to investigate the use of the corrosion inhibitor, the
C

examinations should not only be limited to the input temperature, the lower temperatures at
AC

which film is not formed on the surface should also be examined.

The flow regime is dependent on the pipe diameter and loaded liquid. If the separated water

phase is at bottom of the pipeline, corrosion will occur in this section. In wet gas pipes, the

water condensed at the top of the pipe results in corrosion, since the corrosion inhibitor

cannot access these points.

51
 ACCEPTED MANUSCRIPT
In order to prevent top-of-the-line corrosion, the corrosion inhibitor should be moved to the

top of the pipeline, which depends on the velocity of the gas, liquid volume and the surface

tension of the liquid. As a result, the concentration of the corrosion inhibitor is dependent on

these factors. Deposition and scales are also effective in the performance of corrosion

inhibitors [152].

PT
RI
8. Conclusion and future remarks

This work reviewed different groups of film-forming corrosion inhibitors including amides/

SC
imidazolines; salts of nitrogen-containing molecules with carboxylic acids, quaternary salts

of nitrogen, amines, amides and poly oxyalkylated imidazoline, nitrogen heterocycles and

U
compounds containing P, S and O and polymer corrosion inhibitors.
AN
In case of the imidazoline inhibitors, due to the surfactant properties of the corrosion
M

inhibitors, the free energy of the system is increased while dissolving in a solution, resulting

in an increase of corrosion inhibitor concentration solution at the interface. Surfactant

D

molecules are preferably located at the interface of solution-air, which results in a reduction
TE

of surface tension. Loss of surface tension is continued until the increase of the surfactant

concentration up to the critical micelle concentration (CMC).

EP

At sufficient concentrations, carboxyethyl-imidazoline molecules form a complex and thus

C

reducing the dissolution of the surface layer, leading to an increase in corrosion inhibition
AC

ability.

Addition of amine corrosion inhibitor alone could reduce the corrosion rate, but more

efficiency could be obtained by addition of iodine ions due to the synergistic effects. The

values of Gibbs free energy of absorption of corrosion inhibitor molecules on metal surfaces

indicated that adsorption of amine corrosion inhibitors on the metal surface was

chemisorption, which is more stable with the addition of iodine ions.

52
 ACCEPTED MANUSCRIPT
The high efficiency of protection in the presence of aliphatic amines may be related to the

presence of nitrogen atoms in the amino functional group (-NH2). Nitrogen atoms in aliphatic

amines act as the reaction center due to their high electron density. However, in presence of

ethanolamine, relatively high corrosion inhibition was observed in hydrochloric acid. This

can be due to the behavior of -OH group as electron repellent which provides high nitrogen

PT
electron density, leading to better protection.

RI
Polymeric corrosion inhibitors have not been widely utilized like amine-based corrosion

inhibitors, yet some features, such as better film-forming properties due to macromolecule

SC
structures, make them attractive for corrosion control applications.

Development of corrosion inhibitors for harsh environmental conditions of oil and gas

U
applications including elevated temperatures, multi-phase fluids, high fluid velocity and shear
AN
stress, compatibility with other pipeline chemicals such as hydrate corrosion inhibitor, scale
M

corrosion inhibitors, are still areas of interest for future research. Encapsulation of corrosion

inhibitors for multiphase pipeline fluid is also remarked of future works. In this case
D

corrosion inhibitors can perform their role as smart protection. The formulating and
TE

evaluation of applicability and effectiveness of intelligent corrosion inhibitors for pipelines

and their release rate based on fluid conditions are recommended as future research .
EP

Concentrating on sour top of the line (Sour TOLC) corrosion inhibitors including their
C

synthesis, characterization, development of test setups and field performance is also

AC

recommended for future trends in film former corrosion inhibitor.

9. References

[1] S. Papavinasam, A. Doiron, T. Panneerselvam, R.W. Revie, Effect of Hydrocarbons on the Internal
Corrosion of Oil and Gas Pipelines, CORROSION, 63 (2007) 704-712.
[2] X.S. Huang, Y.M. Qi, C.F. Chen, H.B. Yu, G.W. Lu, Effect of environmental factors on corrosion
behaviour of l360QCS pipeline steel in H2S/CO2 environments, Corrosion Engineering Science and
Technology, 50 (2015) 169-177.

53
 ACCEPTED MANUSCRIPT
[3] R.T. Hill, F.A. Ramirez, B. Monty, G. Palanivel, Material selection assessment for topside process
equipment for production fluids with high CO2 content, in: NACE - International Corrosion
Conference Series, 2011.
[4] J.C. Price, Options in material, coating and chemical selection to mitigate failure in hydrocarbon
production, in: Proceedings of the International Offshore and Polar Engineering Conference, 2012,
pp. 413-419.
[5] B. Singh, T. Folk, P. Jukes, J. Garcia, W. Perich, D.V. Oostendorp, Engineering pragmatic solutions
for CO2 corrosion problems, in: NACE - International Corrosion Conference Series, 2007, pp.
073101-0731016.

PT
[6] Z. Ahmad, D. Macdonald, N. Fredj, Principles of Corrosion Engineering and Corrosion Control,
Butterworth-Heinemann, 2017.
[7] A. Bahadori, Corrosion and Materials Selection: A Guide for Chemical and Petroleum Industries,
2014.

RI
[8] M.A. Kelland, Production Chemicals for the Oil and Gas Industry, Second Edition, Taylor & Francis,
2014.
[9] Q. Haiyan, D. Jun, Study on synthesis and properties of a new imidazoline corrosion inhibitor, in:

SC
Advanced Materials Research, 2011, pp. 325-331.
[10] S. Schauhoff, New corrosion inhibitors for high temperature applications, Materials and
Corrosion, 51 (2000) 141-146.

U
[11] S. Papavinasam, Corrosion Control in the Oil and Gas Industry, Elsevier Science, 2013.
[12] B.K.T. Chevrot, Recommended practice for corrosion management of pipelines in oil and gas
AN
production and transportation (EFC 64), Institute of Materials, London, UK, 2012.
[13] M.E. Olvera-Martínez, J. Mendoza-Flores, J. Genesca, CO2 corrosion control in steel pipelines.
Influence of turbulent flow on the performance of corrosion inhibitors, Journal of Loss Prevention in
the Process Industries, 35 (2015) 19-28.
M

[14] S. Nesic, Effects of Multiphase Flow on Internal CO2 Corrosion of Mild Steel Pipelines, Energy &
Fuels, 26 (2012) 4098-4111.
[15] S. Papavinasam, Corrosion Control in the Oil and Gas Industry, 2013.
D

[16] S. Nešić, Key issues related to modelling of internal corrosion of oil and gas pipelines - A review,
Corrosion Science, 49 (2007) 4308-4338.
TE

[17] S. Nesic, M. Nordsveen, N. Maxwell, M. Vrhovac, Probabilistic modelling of CO2 corrosion

laboratory data using neural networks, Corrosion Science, 43 (2001) 1373-1392.
[18] A.R. V. Balostro, G. Gabetta, Comparison of models for CO2 corrosion prediction and their
application to field cases, Metallurgia Italiana 104 (2012) 37-43.
EP

[19] L.M.S. M.B. Kermani, CO2 Corrosion Control in Oil and Gas Production-Design Considerations,
Institute of Materials, London, UK, 1997.
[20] M.B. Kermani, A. Morshed, Carbon dioxide corrosion in oil and gas production - A compendium,
C

Corrosion, 59 (2003) 659-683.

[21] G. Schmitt, Fundamental aspects of CO<inf>2</inf> metal loss corrosion. Part II: Influence of
AC

different parameters on CO<inf>2</inf> corrosion mechanism, in: NACE - International Corrosion

Conference Series, 2015.
[22] R. Nyborg, Overview of CO2 Corrosion Models for Wells and Pipelines, in, NACE International,
2002.
[23] B.F.M. Pots, Mechanistic models for the prediction of CO{sub 2} corrosion rates under multi-
phase flow conditions, NACE International, Houston, TX (United States), United States, 1995.
[24] C. de Waard, U. Lotz, D.E. Milliams, Predictive Model for CO2 Corrosion Engineering in Wet
Natural Gas Pipelines, CORROSION, 47 (1991) 976-985.
[25] U.L. C. de Waard, Prediction of CO2 Corrosion in Carbon Steel, in: Corrosion, NACE
International, Houston, TX, 1993.

54
 ACCEPTED MANUSCRIPT
[26] K. George, S. Wang, S. Nesic, K. de Waard, Modeling of CO2 Corrosion of Mild Steel in the
Presence of High Partial Pressures of CO2 and Acetic Acid - Electrochemical Modeling and a
Modification to the de Waard Corrosion Model, in, NACE International, 2004.
[27] G. Schmitt, S. Feinen, Effect of Anions and Cations on the Pit Initiation in CO2 Corrosion of Iron
and Steel, in, NACE International, 2000.
[28] G. Schmitt, E. D., SEM/EDX Analysis of Corrosion Products for Investigations on Metallurgy and
Solution Effects in CO2 Corrosion, in: NACE - International Corrosion Conference Series, 1998.
[29] E. Brunner, W. Woll, Solubility of Sulfur in Hydrogen Sulfide and Sour Gases, (1980).
[30] J. Kvarekval, A. Dugstad, Corrosion Mitigation with pH Stabilization in Slightly Sour

PT
Gas/Condensate Pipelines, in, NACE International, 2006.
[31] Z.H. Sarica C, Development of next generation multiphase pipe flow prediction tools, The
University of Tulsa, (2008).
[32] K.E. Kee, M. Babic, S. Richter, L. Paolinelli, W. Li, S. Nesic, Flow Patterns and Water Wetting in

RI
Gas-Oil-Water Three-phase Flow – A Flow Loop Study, in: CORROSION 2015, NACE International,
Dallas, Texas, 2015.
[33] W.P.J. Sun. J-Y, Slug flow characterstics and their effect on corrosion rates in horizontal oil and

SC
gas pipelines, SPE, (1992).
[34] P. Jepson, National Science Foundation Industry/University Co-operative Research Centre for
Corrosion in Multiphase Systems, in, Ohio Univercity, 2000.

U
[35] T.J.a.W. Hill, D.G, Slug Flow: Occurrence, Consequences and Prediction paper, in: University of
Tulsa Centennial Petroleum Engineering Symposium, 1994.
AN
[36] J.W. Kang C, Gopal M, Effect of drag-reducing agent on slug characteristics in multiphase flow in
inclined pipes, J Energy Resour Technol, 121 (1999).
[37] L.D. Villarreal J, Fuentes C, Carbon-steel corrosion in multiphase slug flow and CO2, Corros Sci,
48 (2006).
M

[38] L.C. Cai JY, Tang XP, Ayello F, Richter S, Nesic S, Experimental study of water wetting in oil-water
two phase flow – horizontal flow of model oil, Chem Eng Sci, 73 (2012).
[39] I. Rippon, Corrosion Management for an Offshore Sour Gas Pipeline System, in, NACE
D

International, 2005.
[40] A. Dugstad, P.-E. Dronen, Efficient Corrosion Control of Gas Condensate Pipelines by pH -
TE

Stabilization, in, NACE International, 1999.

[41] A. Dugstad, M. Seiersten, pH-stabilisation, a Reliable Method for Corrosion Control of Wet Gas
Pipelines, in, Society of Petroleum Engineers, 2004.
[42] A. Dugstad, M. Seiersten, R. Nyborg, Flow Assurance of pH Stabilized Wet Gas Pipelines, in,
EP

NACE International, 2003.

[43] A.M.K. Halvorsen, T.R. Andersen, PH Stabilization for Internal Corrosion Protection of Pipeline
Carrying Wet Gas With CO2 and Acetic Acid, in, NACE International, 2003.
C

[44] S. Olsen, A.M.K. Halvorsen, Corrosion Control by pH Stabilization, in, NACE International, 2015.
[45] H.W. Palmer J. W., Dawson J.L., The use of corrosion inhibitors in oil and gas production, first
AC

edition ed., Maney piublishing, 2004.

[46] S. Papavinasam, Corrosion Inhibitors, in: Uhlig's Corrosion Handbook, John Wiley & Sons, Inc.,
2011, pp. 1021-1032.
[47] API, Recommended practice for design and installation of offshore productionpipeing systems,
in, API, 1991.
[48] G.B. Schmitt, Christoph; Mueller, Michael; Siegmund, Gerit, A Probabilistic Model for Flow
Induced Localized Corrosion, in, NACE International, 2000.
[49] G. Schmitt, C. Bosch, M. Mueller, H. Bauer, Modeling the Drag Reducing Effect of CO2 Corrosion
Inhibitors, in, NACE International, 2002.
[50] G. Schmitt, P. Plagemann, K. Moeller, C. Bosch, Local Wall Shear Stress Gradients in the Slug
Flow Regime - Effects of Hydrocarbon and Corrosion Inhibitor, in, NACE International, 2002.

55
 ACCEPTED MANUSCRIPT
[51] A test method to determine the susceptibility to cracking of linepipe steels in sour service', in:
Off-Shore Technology Report 95 635, 1996.
[52] NACE MR0175/ISO 15156-2,Petroleum and natural gas industries – materials for use in H2S
containing environments in oil and gas production – Part 2: Cracking-resistant carbon and low alloy
steel, and the use of cast iron, in, NACE International, NACE MR0175/ISO 15156-2, 2015.
[53] M. Achour, J. Kolts, Corrosion Control by Inhibition Part I: Corrosion Control by Film Forming
Inhibitors, in, NACE International, 2015.
[54] M. Gregg, S. Ramachandran, Review of Corrosion Inhibitor Developments and Testing for
Offshore Oil and Gas Production Systems, in, NACE International, 2004.

PT
[55] J. Cassidy, Design and Investigation of a North Sea Acid Corrosion Inhibition System, in, NACE
International, 2006.
[56] A. Jenkins, Performance of High-Temperature, Biodegradable Corrosion Inhibitors, in, NACE
International, 2011.

RI
[57] B.A. Alink, B. Outlaw, V. Jovancicevic, S. Ramachandran, S. Campbell, Mechanism of CO2
Corrosion Inhibition by Phosphate Esters, in, NACE International, 1999.
[58] M.R. Bonis, J.L. Crolet, An Inhibition Policy Based on Laboratory and Field Experience, in, NACE

SC
International, 1998.
[59] J.W. Chen Y, EIS measurement for corrosion monitoring under multiphase flow conditions,
Electrochim Acta, 44 (1999).

U
[60] E.B. Juri Kolts, Flow Effects in Corrosion Inhibitor Selection, in: Corrosion, NACE International,
Houston, TX., 1995.
AN
[61] N. Tajallipour, Z. Zhu, P.J. Teevens, The Effect of Slug Liquid Front On Inhibitor Effectiveness In
Petroleum Pipelines, in, NACE International, 2011.
[62] V.S. Sastri, Corrosion Inhibitors: Principles and Applications, John Wiley and Sons, 1998.
[63] D. Bajpai, V.K. Tyagi, Fatty Imidazolines: Chemistry, Synthesis, Properties and Their Industrial
M

Applications, Journal of Oleo Science, 55 (2006) 319-329.

[64] G. Bereket, C. Öğretir, A. Yurt, Quantum mechanical calculations on some 4-methyl-5-
substituted imidazole derivatives as acidic corrosion inhibitor for zinc, Journal of Molecular
D

Structure: THEOCHEM, 571 (2001) 139-145.

[65] K. Bílková, E. Gulbrandsen, Kinetic and mechanistic study of CO2 corrosion inhibition by cetyl
TE

trimethyl ammonium bromide, Electrochimica Acta, 53 (2008) 5423-5433.

[66] A. de Oliveira Wanderley Neto, E.F. Moura, H.S. Júnior, T.N.d.C. Dantas, A.A.D. Neto, A. Gurgel,
Preparation and application of self-assembled systems containing dodecylammonium bromide and
chloride as corrosion inhibitors of carbon-steel, Colloids and Surfaces A: Physicochemical and
EP

Engineering Aspects, 398 (2012) 76-83.

[67] A. Ulman, Formation and Structure of Self-Assembled Monolayers, Chemical Reviews, 96 (1996)
1533-1554.
C

[68] F. Schreiber, Structure and growth of self-assembling monolayers, Progress in Surface Science,
65 (2000) 151-257.
AC

[69] V. Jovancicevic, S. Ramachandran, P. Prince, Inhibition of Carbon Dioxide Corrosion of Mild Steel
by Imidazolines and Their Precursors, CORROSION, 55 (1999) 449-455.
[70] X. Guan, Y. Hu, Imidazoline derivatives: a patent review (2006 – present), Expert Opinion on
Therapeutic Patents, 22 (2012) 1353-1365.
[71] R.G. Bistline, J.W. Hampson, W.M. LinField, Synthesis and properties of fatty imidazolines and
their N-(2-aminoethyl) derivatives, J Amer Oil Chem Soc, 60 (1983) 823-828.
[72] I. Jevremović, M. Singer, M. Achour, D. Blumer, T. Baugh, V. Misković-Stanković, S. Nes̆ić, A
Novel Method to Mitigate the Top-of-the-Line Corrosion in Wet Gas Pipelines by Corrosion Inhibitor
within a Foam Matrix, CORROSION, 69 (2012) 186-192.
[73] I. Jevremović, M. Singer, S. Nešić, V. Mišković-Stanković, Inhibition properties of self-assembled
corrosion inhibitor talloil diethylenetriamine imidazoline for mild steel corrosion in chloride solution
saturated with carbon dioxide, Corrosion Science, 77 (2013) 265-272.

56
 ACCEPTED MANUSCRIPT
[74] M. Heydari, M. Javidi, Corrosion inhibition and adsorption behaviour of an amido-imidazoline
derivative on API 5L X52 steel in CO2-saturated solution and synergistic effect of iodide ions,
Corrosion Science, 61 (2012) 148-155.
[75] M.A. Lucio-Garcia, J.G. Gonzalez-Rodriguez, A. Martinez-Villafañe, G. Dominguez-Patiño, M.A.
Neri-Flores, J.G. Chacon-Nava, A study of hydroxyethyl imidazoline as H2S corrosion inhibitor using
electrochemical noise and electrochemical impedance spectroscopy, Journal of Applied
Electrochemistry, 40 (2010) 393-399.
[76] E.F. Diaz, J.G. Gonzalez-Rodriguez, A. Martinez-Villafañe, C. Gaona-Tiburcio, H2S corrosion
inhibition of an ultra high strength pipeline by carboxyethyl-imidazoline, Journal of Applied

PT
Electrochemistry, 40 (2010) 1633-1640.
[77] D.M. Ortega-Toledo, J.G. Gonzalez-Rodriguez, M. Casales, L. Martinez, A. Martinez-Villafañe,
Co2 corrosion inhibition of X-120 pipeline steel by a modified imidazoline under flow conditions,
Corrosion Science, 53 (2011) 3780-3787.

RI
[78] T. Hong, Y.H. Sun, W.P. Jepson, Study on corrosion inhibitor in large pipelines under multiphase
flow using EIS, Corrosion Science, 44 (2002) 101-112.
[79] X. Jiang, Y.G. Zheng, W. Ke, Effect of flow velocity and entrained sand on inhibition

SC
performances of two inhibitors for CO2 corrosion of N80 steel in 3% NaCl solution, Corrosion
Science, 47 (2005) 2636-2658.
[80] E.E. Oguzie, Y. Li, F.H. Wang, Corrosion inhibition and adsorption behavior of methionine on

U
mild steel in sulfuric acid and synergistic effect of iodide ion, Journal of Colloid and Interface Science,
310 (2007) 90-98.
AN
[81] V. Branzoi, F. Branzoi, M. Baibarac, The inhibition of the corrosion of Armco iron in HCl solutions
in the presence of surfactants of the type of N-alkyl quaternary ammonium salts, Materials
Chemistry and Physics, 65 (2000) 288-297.
[82] G.R. Meyerm, Imidazoline corrosion inhibitors, in: U. Patent (Ed.), USA, 2006.
M

[83] D. Leinweber, M. Feustel, Corrosion inhibitors containing cationic surfactants, in, Google
Patents, 2009.
[84] J.A. Dougherty, B.T. Outlaw, B.A.O. Alink, Corrosion inhibition by ethoxylated fatty amine salts
D

of maleated unsaturated acids, in, Google Patents, 1996.

[85] M.W.S. Jawich, G.A. Oweimreen, S.A. Ali, Heptadecyl-tailed mono- and bis-imidazolines: A study
TE

of the newly synthesized compounds on the inhibition of mild steel corrosion in a carbon dioxide-
saturated saline medium, Corrosion Science, 65 (2012) 104-112.
[86] K.D.C. Oppenlaender, K.D.C. Stork, K.D.C. Barthold, Inhibitors against the corrosion of hydrogen
sulphide and carbon dioxide in water-in-oil emulsions, in, Google Patents, 1984.
EP

[87] A.N. Acharya, J.M. Ostresh, R.A. Houghten, A Novel Approach for Solid-Phase Synthesis of
Substituted Imidazolines and Bis-Imidazolines, The Journal of Organic Chemistry, 66 (2001) 8673-
8676.
C

[88] Y. Duda, R. Govea-Rueda, M. Galicia, H.I. Beltrán, L.S. Zamudio-Rivera, Corrosion Inhibitors: 
Design, Performance, and Computer Simulations, The Journal of Physical Chemistry B, 109 (2005)
AC

22674-22684.
[89] I.A.-A. Mohammadpoor-Baltork, M., Microwave-Assisted Facile and Convenient Synthesis of
Imidazolines
Bulletin of the Korean Chemical Society, 24 (2003) 1354-1356.
[90] T.J. Doyle, J. Haseltine, Synthesis, structure, and NMR characterization of a novel [3.3]
metacyclophane, Journal of Heterocyclic Chemistry, 31 (1994) 1417-1420.
[91] A. Marxer, Imidazole urea and amido compounds, in, Google Patents, 1983.
[92] J.M. Richmond, Cationic Surfactants Organic Chemistry, in: Surfactant Science Series Vol34,
Marcel Dekker Inc., New York And Basel, 1990, pp. 73-75.
[93] M.P. Desimone, G. Gordillo, S.N. Simison, The effect of temperature and concentration on the
corrosion inhibition mechanism of an amphiphilic amido-amine in CO2 saturated solution, Corrosion
Science, 53 (2011) 4033-4043.

57
 ACCEPTED MANUSCRIPT
[94] S.R. M., Aliphatic hydrocarbon amine corrosion inhibitors, in: U. Patent (Ed.), USA, 1968.
[95] M. Abdallah, Ethoxylated fatty alcohols as corrosion inhibitors for dissolution of zinc in
hydrochloric acid, Corrosion Science, 45 (2003) 2705-2716.
[96] M.M. Osam, Omar, A.M.A., Al-Sabagh, A.M., Corrosion inhibition of benzyl triethanol
ammonium chloride and its ethoxylate on steel in sulphuric acid solution, Materials Chemistry and
Physics, 50 (1997) 271-274.
[97] A.A.A. Saleh.M.M, Effects of structure of the ionic head of cationic surfactant on its inhibition of
acid corrosion of mild steel
Journal of Applied Electrochemistry, 36 (2006) 899-905.

PT
[98] Z.H. Niu.L, Wei.F, Wu.S, Cao.X, Liu.P, Corrosion inhibition of iron in acidic solutions by alkyl
quaternary ammonium halides: Correlation between inhibition efficiency and molecular structure,
Applied Surface Science, 252 (2005) 1634-1642.

RI
[99] M.S. Mohnan.S, Kalaiselvi.N, Palaniappan.R, Venkatachari.G, Palaniswamy.N, Raghavan.M, Role
of quaternary ammonium compounds and ATMP on biocidal effect and corrosion inhibition of mild
steel and copper,, Corrosion Reviews, 23 (2005) 425-444.

SC
[100] D.P. Schweinsberg, V. Ashworth, The inhibition of the corrosion of pure iron in 0.5 M sulphuric
acid by n-alkyl quaternary ammonium iodides, Corrosion Science, 28 (1988) 539-545.
[101] M.A. Migahed, M.M. Shaban, A.A. Fadda, T.A. Ali, N.A. Negm, Synthesis of some quaternary
ammonium gemini surfactants and evaluation of their performance as corrosion inhibitors for

U
carbon steel in oil well formation water containing sulfide ions, RSC Advances, 5 (2015) 104480-
104492.
AN
[102] S. Nofrizal, A.A. Rahim, B. Saad, P. Bothi Raja, A.M. Shah, S. Yahya, Elucidation of the Corrosion
Inhibition of Mild Steel in 1.0 M HCl by Catechin Monomers from Commercial Green Tea Extracts,
Metallurgical and Materials Transactions A, 43 (2012) 1382-1393.
M

[103] M.M. Balakrishnan B, Umashankar PR, Jayakrishnan A, Evaluation of an in situ forming

hydrogel wound dressing based on oxidized alginate and gelatin, Biomaterials, 26 (2005) 6335-6342.
[104] Y. Yan, W. Li, L. Cai, B. Hou, Electrochemical and quantum chemical study of purines as
corrosion inhibitors for mild steel in 1 M HCl solution, Electrochimica Acta, 53 (2008) 5953-5960.
D

[105] J. Sinko, Challenges of chromate inhibitor pigments replacement in organic coatings, Progress
in Organic Coatings, 42 (2001) 267-282.
TE

[106] Q. Wang, J. Zhang, D. Shi, M. Du, Synthesis, Characterization and Inhibition Performance of
Vanillin-Modified Chitosan Quaternary Ammonium Salts for Q235 Steel Corrosion in HCl Solution,
Journal of Surfactants and Detergents, 18 (2015) 825-835.
EP

[107] J. Zhang, X. Sun, Y. Ren, M. Du, The Synergistic Effect Between Imidazoline-Based Dissymmetric
bis-Quaternary Ammonium Salts and Thiourea Against CO2 Corrosion at High Temperature, Journal
of Surfactants and Detergents, 18 (2015) 981-987.
[108] J. Zhang, L. Niu, F. Zhu, C. Li, M. Du, Theoretical and Experimental Studies for Corrosion
C

Inhibition Performance of Q235 Steel by Imidazoline Inhibitors against CO2 Corrosion, Journal of
Surfactants and Detergents, 16 (2013) 947-956.
AC

[109] J. Zhang, D. Shi, X. Gong, F. Zhu, M. Du, Inhibition Performance of Novel Dissymmetric
Bisquaternary Ammonium Salt with an Imidazoline Ring and an Ester Group, Journal of Surfactants
and Detergents, 16 (2013) 515-522.
[110] I. Singh, Inhibition of Steel Corrosion by Thiourea Derivatives, (1993).
[111] W.F.G. J.C.M. Blair, Processes for preventing corrosion and corrosion inhibitors, in, 2015.
[112] J.O.L. Riggs, Process of Reacting Equimolar Amounts of a Monounsaturated Diol, a Polyalkylene
Polyamine, and a Monocarboxylic Acid and Product, in, 1966.
[113] R. Hausler, Alkylene Polyamine Polymeric Reaction Product Corrosion Inhibitor, in, 1974.
[114] B.D.B. Tiu, R.C. Advincula, Polymeric corrosion inhibitors for the oil and gas industry: Design
principles and mechanism, Reactive and Functional Polymers, 95 (2015) 25-45.
[115] U.A. M.J. Incorvia, Reaction Product of Hydrogen Sulfide With the Reaction Product of a Dione
and a Primary Polyamine, in, 1987.

58
 ACCEPTED MANUSCRIPT
[116] D.R. N.E.S. Thompson, B.A.O. Alink, B.T. Outlaw,, Process of Corrosion Inhibi- tion Using
Compounds Containing Sulfur and Amino Groups, in, 1987.
[117] A.Z. P.-E. Hellberg, P, olymeric corrosion inhibitors — a new class of
versatile oilfield formulation bases,, in: International Petroleum Technology Confer- ence, 2014.
[118] A.K. G. Misra, Treatment Fluid Containing a Corrosion Inhibitor Polymer of a Carbohydrate and
Quaternary Amine, in, 2014.
[119] J.I. Bregman, Corrosion inhibitors, Macmillan, 1963.
[120] A. Fateh, M. Aliofkhazraei, A.R. Rezvanian, Review of corrosive environments for copper and its
corrosion inhibitors, Arabian Journal of Chemistry, (2017).

PT
[121] S.webster, Corrosion Inhibitor Selection for Oil field Pipelines, NACE, corrosion 93 (1993).
[122] A.Nestle, Corrosion Inhibitors in Petroleum Production Primary Recovery, NACE, Corrosion
Inhibitors (1973).

RI
[123] P. Marcus, F.B. Mansfeld, Analytical Methods In Corrosion Science and Engineering, CRC Press,
2005.
[124] Y.M. Tan, R.W. Revie, Heterogeneous Electrode Processes and Localized Corrosion, Wiley,

SC
2012.
[125] S.B.a.B.K. Y. J. TAN, . Elsevier,, AN INVESTIGATION OF THE FORMATION AND DESTRUCTION OF
CORROSION INHIBITOR FILMS USING ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY (EIS), 38
(1996) 16.

U
[126] D. C. Silverman, (1990) 7.
[127] S.B.a.B.K. Y. J. Tan, An Experimental Comparison of Corrosion Rate Measurement Techniques:
AN
Weight-loss measurement, Linear Polarization, Electrochemical Impedance Spectroscopy and
Electrochemical Noise Analysis,. Corrosion and Prevention, 1995. 95.
[128] W.J.L.a.F. Mansfeid, Corros Sci, 21 (1981).
M

[129] M.K.a.H.T. I. Epelboin, J. Appl, Elecfrochem., 2 (1972) 71.

[130] D.C. Silverman, Corrosion, 45 (1989).
[131] Y.J. Tan, S. Bailey, B. Kinsella, An investigation of the formation and destruction of corrosion
inhibitor films using electrochemical impedance spectroscopy (EIS), Corrosion Science, 38 (1996)
D

1545-1561.
[132] A. Nestle, Corrosion inhibitors in petroleum production primary recovery, NACE Publication,
TE

(1973).
[133] M.C. Villamizar W, Chow H,, CORROSION, (2008).
[134] C. H. Tsai and F. Mansfeld, Corrosion
EP

9(1993).
[135] H. Hilliard, . NACE, Use of inhibitors For Downhole Corrosion Control In Gus Wells, CO2
Corrosion in Oil and Gas Production, (1978).
C

[136] Y.J. Tan, B. Kinsella, S. Bailey, Monitoring batch treatment inhibitor performance continuously
using electrochemical noise analysis, British Corrosion Journal, 32 (1997) 212-216.
AC

[137] W.F.B. R. W. Bosch, Instantaneous Corrosion Rate Measurement with Small-Amplitude

Potential Intermodulation Techniques, CORROSION SCIENCE, 43 (1996).
[138] W.A.S. Sutham Srilomsak, Steven M. Pilgrim, Francis A. Williams Jr., , Harmonic Analysis of
Polarization Hysteresis of Aged PZTs, Journal of the American Ceramic Society, 88 (2005) 5.
[139] J.M.M. W. Villamizar-Sua´rez , A. Martı´nez-Villafan˜e , J. G. Chacon-Nava,, Evaluation of
corrosion inhibitors performance using real-time monitoring methods. , Appl Electrochem, 41
(2011).
[140] L.M. Rodríguez-Valdez, W. Villamisar, M. Casales, J.G. González-Rodriguez, A. Martínez-
Villafañe, L. Martinez, D. Glossman-Mitnik, Computational simulations of the molecular structure
and corrosion properties of amidoethyl, aminoethyl and hydroxyethyl imidazolines inhibitors,
Corrosion Science, 48 (2006) 4053-4064.

59
 ACCEPTED MANUSCRIPT
[141] W. Villamizar, M. Casales, J.G. Gonzalez-Rodriguez, L. Martinez, CO2 corrosion inhibition by
hydroxyethyl, aminoethyl, and amidoethyl imidazolines in water–oil mixtures, Journal of Solid State
Electrochemistry, 11 (2007) 619-629.
[142] J.L. Pacheco, T.G. Martin, J. Regina, P.I. Abrams, S.R. Hickman, L.D. Talley, Corrosion Inhibitor
Qualification Testing For Subsea Wet Gas Pipelines, in, NACE International, 2008.
[143] R. Baboian, Corrosion Tests and Standards: Application and Interpretation, American Society
for Testing & Materials, 2005.
[144] R.W. Revie, Uhlig's Corrosion Handbook, Wiley, 2005.
[145] V.S. Sastri, Green Corrosion Inhibitors: Theory and Practice, Wiley, 2011.

PT
[146] S. Papavinasam, R.W. Revie, M. Attard, A. Demoz, K. Michaelian, J.C. Donini, H. Sun, Inhibitor
Selection for Internal Corrosion Control of Pipelines: Comparison of Rates of General Corrosion and
Pitting Corrosion Under Gassy-Oil Pipeline Conditions in the Laboratory and in the Field, in, NACE
International, 2000.

RI
[147] S. Papavinasam, R.W. Revie, M. Attard, K. Michaelian, H. Sun, A. Demoz, J.C. Donini, Inhibitor
Selection for Internal Corrosion Control of Pipelines: 1. Laboratory Methodologies, in, NACE
International, 1999.

SC
[148] M.J.J. Simon-Thomas, Corrosion Inhibitor Selection - Feedback From the Field, in, NACE
International, 2000.
[149] M. Calvarano, D. Condanni, B. Bazzoni, "Corrosion Intelligence": An Application To Oil And Gas

U
Pipelines, in: Corrosion97, NACE International, New Orleans, Louisiana, 1997.
[150] L. Garverick, Corrosion in the petrochemical industry, ASM International, 1994.
AN
[151] H. De Reus, M.J.J.S. Thomas, Corrosion Inhibitor Selection and Field Verification in Oil and Gas
Production, in, NACE International, 2002.
[152] J.L. Pacheco, F.C. Ibrahim, R.J. Franco, Testing Requirements Of Corrosion Inhibitor
Qualification For Pipeline Applications, in, NACE International, 2010.
M
D
TE
C EP
AC

60
 ACCEPTED MANUSCRIPT

Highlights

1- Pipeline corrosion mechanisms and mitigation methods have been reviewed.

2- Film former corrosion inhibitors including molecular structure are well

classified.

PT
3- Various experiments case studies have been reflected.

4- Corrosion inhibition mechanisms by film forming are discussed.

RI
5- A guide for selection of pipeline inhibitors has been provided.

U SC
AN
M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT

List of tables
Table 1. The major risk of internal corrosion in oil and gas pipelines
Corrosion type Fluid of pipeline Major affective factors

PT
Microbiologically influenced Oil and produced/ injection water Sulphate, nutrients,
corrosion (MIC) bacteria type, pH, flow

RI
rate, salinity, temperature

SC
CO2 corrosion Oil, gas and water/gas injection Pressure and temperature,
acid gas content, in-situ pH,

U
flow regime, water cut

AN
H2S + CO2 corrosion Oil, gas and water/gas injection Pressure and temperature,
acid gas content, in-situ

M
pH, flow regime, water
cut, acid gas ratio,
microbial activities

D
Top-of-line corrosion Stratified wet gas temperature, organic acid

TE
(TOLC) content, water
condensation rate
EP
Oxygen corrosion and other Water injection O2 content, temperature and
oxidants flow rate, residual chlorine
C

Under-deposit corrosion Oil and produced/ water injection Solids, scales, flow rate
AC

Preferential weld corrosion Oil, gas and PW/PG injection Weldment metallurgy, flow
regime, type inhibitor, water
salinity
 ACCEPTED MANUSCRIPT

Table 2. Water flow distribution in water-oil-gas flow

Flow pattern Water distribution of water and its

PT
location

RI
Stratified (ST) Separated, bottom

Elongated bubble(EB) Separated, bottom

SC
Slug (SL) Dispersed/separated, mostly bottom

U
Wavy annular (WA) Dispersed, mostly circumferential

AN
Annular- mist (AM) Dispersed, mostly circumferential

M
D
TE
C EP
AC
 ACCEPTED MANUSCRIPT

Table 3. Internal corrosion/erosion risk in sour gas pipelines

Failure modes General corrosion mechanism/location focus for
corrosion

PT
General corrosion, CO2 in flowing conditions (for CO2/H2S ratios ≥
internal 20)
Flow back of acid returns that have not been

RI
neutralized (can also lead to localized corrosion)
Localized H2S/CO2 in stagnant/low flow conditions H2S

SC
corrosion, internal in flowing and stagnant conditions (for
CO2/H2S ratios ≤500)
Presence of elemental sulphur

U
AN
Under deposit corrosion
Flow back of acid returns that have not been
neutralized (can also lead to general corrosion)

M
Flow back of completion fluids
Oxygen entry – leading to direct corrosion,

D
formation of elemental sulphur, removal of

TE
protective scales. Oxygen may enter directly or
through injection of oxygenated fluids (e.g.
MeOH)
EP
Bacteria
Erosion by fluid Focused on bends, tees, downstream of reducers
C

stream at high and control valves, vessel inlet and outlet nozzles
velocity
AC

Erosion by Focused on bends, tees, downstream of reducers and

entrained sand control valves, vessel inlet and outlet nozzles
 ACCEPTED MANUSCRIPT

Table 4. Experimental conditions of corrosion assessment [73]

Parameters Conditions

PT
Total pressure (bar) 1

RI
Test solution 3 wt.% NaCl
3
Solution volume, dm 1.8

SC
Corrosion inhibitor TOFA/DETA imidazoline
Inhibitor concentration (ppmv) 0, 70

U
Liquid temperature (oC) 20, 70

AN
pH 5

M
Measurements Weight loss

D
TE
C EP
AC
 ACCEPTED MANUSCRIPT

PT
RI
SC
Table 5. Electrochemical parameters obtained from polarization curves [77]

Carboxyethyl-imidazoline concentration 0 rpm 250 rpm 500 rpm 1000 rpm 2500 rpm

U
(mol/l)

AN
0 Ecorr (mVSCE) -700 -668 -686 -670 -647

M
icorr (mA/cm2) 0.15 0.30 0.35 0.40 0.60
8.1 x 10-5 Ecorr (mVSCE) -640 -627 -610 -590 -610

D
icorr (mA/cm2) 0.07 0.08 0.1 0.12 0.11
η (%) 53.3 73.3 71.4 70 81.6

TE
C EP
AC
 ACCEPTED MANUSCRIPT

Table 6. Review table includes the generic type of organic film former corrosion inhibitors, tested material grade, concentration of
inhibitor, type of experiments and test results
Inhibitor Medium Material Inhibitor Concentration Test Inhibition efficiency (IE) Testing References

PT
condition techniques
TOFA/DETA imidazoline 3 wt.% NaCl Mild steel 70 ppmv T=20 oC,70 90% LPR
o
+CO2 C EIS
[72]
pH=5 PDS

RI
TOFA/DETA imidazoline 3 wt.% NaCl API X65 70 ppmv T=20 oC,70 95% WL
o
+CO2 C QCM
[73]

SC
pH=5 AFM

Hydroxyethyl imidazoline 3 wt.% NaCl Mild steel 5, 10, 25, 50, and 100 T=50 oC 95% for 5 and 10 ppm LPR
+H2S ppm inhibitor EIS
[75]
EN

U
Carboxyethyl-imidazoline 3 wt.% NaCl API X120 5, 10, 25, 50, and 100 T=50 oC 98% for 50 ppm inhibitor PDS

AN
+H2S ppm LPR
with/without 10% EIS [76]
diesel EN

M
Carboxyethyl-imidazoline 3 wt.% NaCl API X120 8.1 x 10-5 mol/l T=50 oC @ 0 rpm: 53.3 PDS
+CO2 pH=5 @ 250 rpm: 73.3 LPR
stirring @ 500 rpm: 71.4 EIS
conditions: @ 1000 rpm: 70 EN [77]

D
0, 250, 500, @ 2500rpm: 81.6
1000 and

TE
2500 rpm
Diethylenetetramine- derived 0.5 M NaCl +CO2 Mild steel 100 ppm T=40 oC 84% PDS
imidazoline pH= 5-5.5 LPR [66]

Tetraethylenepentamine-derived 0.5 M NaCl +CO2 Mild steel 100 ppm T=40 oC 95% PDS
EP
imidazoline pH= 5-5.5 LPR [67]

Bis-imidazoline 0.5 M NaCl +CO2 Mild steel 100 ppm T=40 oC 96% PDS
pH= 5-5.5 LPR [96]
C

N-[2-[(2-aminoethyl)amino] ethyl]-9- 5% NaCl +CO2 Mild steel 0.07,0.14,0.27,0.82, 1.36, T=25 oC 28%, 45%, 65%, PDS
AC

octadecenamide (AAOA) 2.72, 4.08,5.44 90%,98%,99%,99%,99% EIS

[99]
(x10 -5 mol dm-3) for specified dosages PM-IRRAS
respectively
Amido-imidazoline 5% NaCl +CO2 API X52 25, 50,75,100 and 150 mg/l T=25 oC 68.8%, 76.7%, 91.2%, PDS
pH= 4 91.8%, 95% EIS [98]

Vanillin-Modified Chitosan HCl Solution Q235 200 mg/L T=25 oC 90% WL

Quaternary Ammonium Salts [119]
 ACCEPTED MANUSCRIPT

Amphiphilic amido-amine 5% NaCl +CO2 Mild steel (0.27, T=25 oC 65%, 90%, 98%, 99%, 99%, EIS
AISI 1018 0.87,1.36,2.72,4.08,5.4 low speed 99% PDS
[107]
)×10−5 M. magnetic PM-IRRAS
stirring
pentabenzyldiethylenetriamine 1 L diesel oil, Mild steel 50-1000 ppm T=25 oC 75-90% PDS
kerosene and LPR

PT
petrol+100 H2S- [111]
saturated water+20
mL HCl(30%)
carboxylic acid+ polyamine(H2N(-R- kerosene/5% NaCl Mild steel 10 ppm T=160 oF 99% Wheel test

RI
NH)xH) (1:1) + CO2 [121]
carboxylic acid+ polyamine(H2N(-R- Oil/water: 40/160 10 ppm T=160 oF 80% Wheel test
NH)xH) Oil/water: 10/190 88%
[103]

SC
Both aturated with
H2S
polyester aliphatic amine Formation water API X60 40–200 T=21 oC 86–96% WL
(Cl-: 120-150 ppm) pH=5.7 PDS [124]

U
Methylamine 1M H2SO4 Mild steel 1x10 -4 M T=30 oC 12.61 WL
1x10 -3 M 18.62 PDS [115]
1x10 -2 M 35.82 EIS

AN
Methylamine 1M H2SO4 Mild steel 1x10 -4 M T=30 oC 82.09 WL
+1 x 10-4 M KI 1x10 -3 M 89.74 PDS [136]
1x10 -2 M 94.69 EIS
WL

M
Surface tension
Carbon pH=5.7
Polyester aliphatic amine Formation water 40-200 ppm 86-96 measurements [119]
steel T = 298 K
OCP

D
PDS
Gravimetric and
T= 278-308
aliphatic amines HCl (2M) Mild Steel 10-1-10-6 M 85-95 Polarization [120]

TE
K
Techniques
WL
Carbon PDS
Aliphatic amines + iodide ions H2SO4 (1M) 10-100 (*10-4) mol.L-1 ---- 88-94 [121]
Steel LP
EP
EIS
HCl T=303-323 WL
Aliphatic amines Zinc 5-25 mM 39-98 [122]
(0.025 N and 0.01 N) K PDS
C

Aliphatic amines HCl Aluminum ---- ----- 85-90 WL [123]

WL
SS SX pH=3.5-4
AC

Aliphatic amines Citric Acid 100-700ppm 95 PDS [124]

316 T=298
EIS
NaCl + CO2+H2S 90 (in presence of H2S & EIS
salts of higher oxyethylated amines St3 Steel 25-100 mg.l-1 ---- [125]
HCl+ CO2+H2S CO2) PDS
Carbon WL
Emulgin HCl+ CO2+H2S 0.078-0.625 nMol.L-1 ------ 97 (In presence of H2S) [126]
Steel PDS
 ACCEPTED MANUSCRIPT

Caption of figures:

Figure 1. Different molecules of imidazoline

Figure 2. Molecular structure of TOFA/DETA imidazoline
Figure 3. The general structure of the hydroxyethyl imidazoline corrosion inhibitor
molecule [75]

PT
Figure 4. The overall structure of the corrosion inhibitors molecule of
carboxyethyl- imidazoline [76]

RI
Figure 5. Effect of rotation on the polarization curves [77]
Figure 6. Synthesis of imidazolines [85]

SC
Figure 7. N-[2-[(2-aminoethyl)amino] ethyl]-9-octadecenamide [93]
Figure 8. The structure of aliphatic amines and ammonia

U
Figure 9. Tallow amine synthesis by ethoxylation
AN
Figure 10. Comparison of the corrosion inhibition efficiency of VHTC,
vanillin-chitosan Schiff-base and Chitosan and imidazoline at a temperature of
298 K [101]
M

Figure 11. Chemical structure of mercapto acetic acid

Figure 12. Production of corrosion inhibitor by condensation reaction of
D

thiourea with DETA

TE

Figure 13. The composition of a film former corrosion inhibitor (A)

unsaturated diol (B) polyalkylene amine and (C) carboxylic acid [114]
Figure 14. The structure of the polyaralkylamine as corrosion inhibitors (A)
EP

Rs can be hydrogens or structure (B) [114]

Figure 15. A new class of polyamine and polyquaternary amine corrosion
C

inhibitors [114]
AC

Figure 16. Oligomeric model structure

Figure 17. Schematic figure of the film formed by corrosion inhibitor
Figure 18. The relationship between the layers’ resistance and the primary
layer resistance R1 during inhibitor film formation [130]
Figure 19. Breakdown of the corrosion inhibitor film formed on the
electrode while spinning at1000 rpm in corrosion inhibitor-free solution [130]
Figure 20. Test development process for evaluation of corrosion inhibitors

1
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC
 ACCEPTED MANUSCRIPT

PT
RI
U SC
AN
M
D
TE
EP
C
AC