Chemical removal of carbonate scale in

pipes from oil and gas production

ABSTRACT
Scale deposition and corrosion are the two costliest problems in the oil
industries.During the inspection and maintenance carried out in onshore wells in
oil and gas production, the presence of adherent scales inside the pipes was
revealed. The oil, natural gas and formation water produced in these onshore oil
wells come from reservoir rocks rich in minerals such as calcite (CaCO3) and/or
dolomite (CaCO3.MgCO3).The formation waters of these wells contain sufficient
2+ 2+ -
levels of Ca , Mg and HCO3 ions to generate carbonate scale, causing
restrictions on the flow of oil and gas production. To return to the initial conditions
of oil production, it is necessary to remove the internal carbonate scales with
hydrochloric acid injection and to prevent internal corrosion of carbon steel pipes,
it is essential to add the corrosion inhibitor to the acid solution.The present study
evaluates the dissolution of carbonate scale and the corrosion resistance of
carbon steel using gravimetric (mass loss) and electrochemical (polarization)
tests. Studies were completed withand without the addition of 250, 500 and 1,000
mg/L propargyl alcohol in HCl solutions with concentrations of 10 wt. % and 15%
wt. % at temperatures of 25, 40 and 60 °C. Chemical analyses have revealed
that carbonate scales are predominantly composed of 83 % calcite, 2 %
dolomite, 2 % kaolinite and the rest is made up of iron oxides and hydroxides.
The hydrochloric acid solution with 10 wt. % and 15 wt. % has become an
excellent removing agent with a yield of more than 98%. The results of mass loss
assays showed that the addition of propargyl alcohol in 10 wt. % and 15 wt. %
HCl provided excellent protection to the carbon steel with an efficiency superior
of 95 %.

Keywords:incrustation, corrosion, corrosion inhibitor, acidizing, calcium

carbonate.

INTRODUCTION

Inspection and maintenance of onshore well tubes in oil and gas production
revealed the presence of corrosion and adherent deposits on the inside of the
pipes. Corrosion and the formation of mineralized incrustation are the two most
costly problems in the petroleum industries.
As shown in Figure 1, inorganic depositions cause a significant reduction in well
productivity and the injection of hydrochloric acid (HCl) into the oil well, called
acidification or acid stimulation, requires the addition of corrosion inhibitors to
prevent or avoid the corrosive process represented by the acidic medium.
The probability of the occurrence of mineralized scale inside the oil production
tubing and in the equipment associated (pumps, valves, fittings, flanges, etc.)
with the production of oil, directly or indirectly, is due to the physicochemical
characteristics of formation water, the oil/water ratios of each well, petroleum
properties, geology of the rocks and the variations in temperature, pressure and
hydrodynamic conditions from one’s own well [1,2].

Fig.1. Carbonate scale in oil tubing

The chemical composition and concentration of the constituents of the formation

water and consequently the water produced during extraction depend on
geological diversities of the reservoir rock and the petroleum and gas
characteristics. Formation water consists of a saline solution that can reach
values of 10-30% wt. % of soluble salts.
-
Generally, soluble salts contain high amount of chloride ions (Cl ) and smaller
2- 2-
amounts of sulfate ions (SO4 ), carbonate ions (CO3 ) and bicarbonate ions
- + +
(HCO3 ). The most common cations are sodium (Na ), potassium (K ), calcium
2+ 2+ 2+ 2+
(Ca ) magnesium (Mg ), strontium (Sr ) and barium (Ba ). The sediments
consist of microscopic particles such as clays, silica sand, silicates, iron sulfides,
and iron oxides. In addition, these may also contain small amounts of organic
acids and oily substances [1-5].
The carbonate scale, object of this study, that can occur in pipes and oil
production equipment are due, among others, of the following specific
parameters:

 The reservoir rock must be rich in minerals such as calcite (CaCO3) and/or
dolomite (CaCO3.MgCO3);

2
 2+ 2+ -
 The formation water must contain Ca , Mg and HCO3 ions in sufficient
concentrations to enable fouling;
 The occurrence of CO2 increases the possibility of these deposits [6-8].

Consequently, by associating these assumptions with the increase in

temperature, the abrupt reductions in pressure and the favorable hydrodynamic
conditions of the formation water, it is valid to admit the following reactions to
evidence the formation of carbonate scales:
2+ -
Ca + 2HCO3 → Ca(HCO3)2

Ca(HCO3)2 → CaCO3 + CO2 + H2O

Generally, these carbonate scales, which most often aggregate silica (SiO2) and
ferric oxide (Fe2O3), are adherent, hard and considerably reduce the productivity
of the oil well, forcing acid interventions, called acidification. This acidification of
carbonate rocks is a common practice to reduce formation damage near the oil
well. In this process, an acidic solution is injected to dissolve some of the rock,
creating conductive channels called wormholes [9,10].

In this process, an acidic solution is injected to dissolve some of the rock (with a
pressure lower than the reservoir rock turnover pressure) creating conductive
channels called wormholes. These wormholes facilitate the flow of hydrocarbons
to the wellbore as shown in the hydrochloric acid injection scheme with the
addition of a corrosion inhibitor shown in Figure 2 below.

Historically, the literature reports that since the 1930s, cases of acidification for
the removal of carbonate scale have been reported using mixtures of
hydrochloric acid (HCl) and hydrofluoric acid (HF) and using corrosion inhibitor
formulations to prevent strong acid attack on carbon steel pipes [2, 9,10]

It is important to note that certain factors such as the flow of the acid solution, the
concentration, the physicochemical characteristics, the additives added, the
pumping pressures and the dissolution rate of the rock are essential to obtain a
successful acidification process.

3
Fig.2. Hydrochloric acid injection scheme for removal of carbonate scale

The dissolution and formation of soluble salts of carbonate scales containing

silica (SiO2) and ferric oxide as impurities using mixtures of hydrochloric acid and
hydrofluoric acid can be evidenced by the following reactions:

CaCO3 + 2 HCl→ CaCl2 + CO2 + H2O

Fe2O3 + 6 HCl→ 2 FeCl3 + 3 H2O

SiO2 + 4 HF→ SiF4 + 2 H2O

The specialized literature informs that the acidification of the conventional matrix
acidizing of carbonate reservoirs uses hydrochloric acid, however, several
studies have shown acidification results with other acids, special additives or
mixtures with hydrofluoric acid and hydrochloric acid itself. Organic acids that are
used in the acidifications of carbonate reservoirs include formic acid, acetic acid,
citric acid, lactic acid and methanesulfonic acid (MSA). The experimental results
of the action of these organic acids on carbonate reservoirs or in the dissolution
of carbonate scales aim to evaluate the optimal injection rates, the
physicochemical properties and the development of new correlated research [11-
13].

Considering that carbonate scales are firmly adherent to the internal surface of
carbon steel pipes and as previously shown, hydrochloric acid is used in their
removal. It is evident that when dissolving the carbonate scale, hydrochloric acid
vigorously attacks the carbon steel, requiring the addition of corrosion inhibitors.

4
Corrosion inhibitors are substances or mixtures of substances that, when added
to the corrosive medium, in appropriate concentrations, can avoid, prevent or
prevent the development of corrosion reactions, whether in the gaseous,
aqueous or oily phases. The protection efficiency offered by inhibitors depends
on the metals and alloys, as well as the severity of the medium. The mechanism
of action of corrosion inhibitors is based on the formation of a barrier or film on
the surface of the metal, which prevents or slows down corrosion reactions,
and/or on the alteration of the corrosive medium, making it less aggressive. The
performance of commercially formulated corrosion inhibitors for the protection of
carbon steel in acidic solutions is more efficient than the chemical substance
itself. However, to evaluate the corrosion efficiency, it is important to note that the
performance depends on several factors such as: concentration, molecular
weight of the substance, temperature, pressure, velocity of the fluid, levels of
contaminants, etc[14,16].

Adsorption inhibitors of organic origin, according to data in the literature, are

preferentially used in processes in acidic media, such as the stimulation of oil
wells. Therefore, acetylene alcohol (2-propin-1-ol or propargyl alcohol) will be the
focus of the present study because it has great potential for inhibition of carbon
steel in acidic medium, according to bibliographic references [14-20].

The present work aims to investigate the scale formation that occurred in a
petroleum production tube, to propose a process to remove this scale using
hydrochloric acid (HCl) and to preserve the surface of the carbon steel pipe using
a propargyl alcohol-based corrosion inhibitor.

2. MATERIAL AND METHODS

2.1 Chemical analyses of carbonate scale

To identify the constituents of the scale presented in Figure 1, six samples were
removed: two close to the surface of the carbon steel, two in the central part and
two in the peripheral part. Crystalline chemical species were determined by X-ray
diffraction (XRD) with a D8-Bruker diffractometer (Kα X-ray tube), Ni-filter, 0.02,
0.2 s step and position-sensitive detector.

The analysis of the elements was done by X-ray fluorescence spectrometry

2- -
(XRF), and the concentrations of carbonate (CO3 ), chloride (Cl ) and sulfate
2-
(SO4 ) were determined by volumetric methods.

2.2Dissolution of carbonate scale

In the evaluation of the dissolution, ten samples of the scale were removed, each
weighing approximately 1 g. The samples were crushed, homogenized and the
resulting finer powder,thatpassed through an US sieve 80 mesh, was used in
three samples for the test.

The test consists of placing the 1g samples in a glass bottle and adding 200 mL
of 10 wt. % and 15 wt. % hydrochloric acid (HCl). The testing time was 90 min

5
and the temperature was maintained at 60°C. The corrosive solution was
agitated with a magnetic bar. It was then filtered and rinsed using deionized
water on a preweighed filter paper. Since the solutions were to pass through the
filter paper, a vacuum pump was used to create suction pressure in the conical
flask collecting the filtrate shown in Figure 3 below.

After filtration, the sample residue collected on the filter paper was placed in the
oven for 1 hour at 120°C. Finally, after cooling to room temperature, the final
mass (W2) was determined. To calculate the acid solubility percentage, the
following formula was used:

W1 − W2
% A. S. = × 100,
W1

Where:

A.S.= acid solubility, %; W1 = initial weight and W2 = final sample weight

The 10 wt. % and 15 wt. % hydrochloric acid solution used in the tests was
prepared using 37 wt. % concentrated high pure hydrochloric acid.

Fig.3. Filtration of dissolution of carbonate scale

2.3 Gravimetric test (mass loss) of coupons of carbon steel

The material evaluated in this study was a carbon steel AISI 1020 (0.21 %
carbon, 0.33 % Mn, 0.35 % Si, 0.011 % S, and 0.009 % P, with the reminder
consisting of iron) used in the confection of the coupons. The coupons used in
the gravimetric tests (weight loss) had the following dimensions: 45 mm x20 mm
x 2 mm.
The metal surfaces were prepared with sandpaper, ranging from grade 100 to
grade 600. After using sandpaper, the surfaces were cleaned with acetone and

6
ethanol and dried with hot air. The weights of the test coupons were recorded, up
to fourth decimal places, using a digital electronic balance.
The test is made by placing the coupon of carbon steel in a 200 mL plastic bottle
and adding 150 mL of the solution of 10 wt. % and 15 wt. % of HCl and additions
of250 mg/L, 500 mg/L and 1000 mg/L of propargyl alcohol (2-propyn-1-ol) as
corrosion inhibitor. Figure 4 shows a plastic bottle used in the immersion test.
For the thermostatic bath, temperatures were set at 25 °C, 45 °C and 60 °C with
an accuracy of 0.1 °C. The times of exposure to the corrosive medium are set at
1 h and 2 h.
Upon completion of the test the system shuts down and the coupons are quickly
removed from the corrosive medium, then washed with water, alcohol and dried
with hot air. The coupons are then weighed again to the nearest 0.0001 g.
The 10 wt. % and 15 wt. % hydrochloric acid solution used in the tests was
prepared using 37 wt. % concentrated high pure hydrochloric acid. The propargyl
alcohol (2-propin-1-ol) added to the hydrochloric acid solution has 99.5 % purity.

Fig.4.Immersion mass loss test of carbon steel specimens in hydrochloric

acid solution

The corrosion rate (CR) and the efficiency of each corrosion inhibitor (% E) were
defined by the following expressions:

Wo − Wf
R= = mg/cm . h
S ×t
Wa − Wi
%E= × 100
Wa

Where:

Corrosion Rate = CR ;
Corrosion Inhibitor Efficiency = E % ;
Wo and Wf are, respectively, the initial mass and the final mass of the coupon;
Wa and Wi are the weight loss in the absence and presence of inhibitor;

7
 2
S = area (cm );
t = exposure time, h.

2.4 Electrochemical test

In the preparation of the coupons for the polarization measurements, the carbon
steel samples were cut in order to obtain an electrode surface of 0.25 cm2. The
specimen was then embedded in polyester resin and sanded on a polishing
machine using 100 to 1200 grade sandpaper, as shown in Figure 5.After this
procedure, the samples were washedand passed through ultrasonic cleaning
equipment for 5 min, in order to remove residues that may have aggregated
during sanding.

Fig 5. Electrochemical coupons

At this point, the samples were inserted into aconventional polarization cell with a
volume of 200 mL,consisting of a working electrode, a platinum
counterelectrodeand a saturated calomel reference electrode(SCE), as shown in
Figure 6.

Fig. 6: Conventional polarization cell: 1) working electrode (carbon steel

coupon); 2) a platinum counter electrode; 3) saturated calomel reference
electrode (SCE),

All experiments were performed under atmospheric condition without stirring. The
polarization curves were recorded using a TypeIII Autolab potentiostat by varying
the potentials insteps of 60 mV/min over a range of -300 to +300 mVwith respect
to an open circuit potential. The corrosive medium used was a solution of 10 wt.

8
% and 15 wt. % of high purity HCl while the concentration of the corrosion
inhibitor, propargyl alcohol (2-Propyn-ol-1), was fixed to 250, 500 and 1,000
mg/L. Before each experiment, the electrode wasallowed to corrode freely and its
open circuitpotential (OCP) was recorded as a function of time up to 1 h [20,21].

3. RESULTS AND DISCUSSION

3.1 Chemical analyses of carbonate scale

The chemical analysis by x-ray fluorescence of the elements presented in Table

1 refers to the average of the six samples removed from the carbonate scale
adhering to the inner part of the pipe.

Table 1. Chemical analysis by x-ray fluorescence of the elements of

carbonate scale
Determined elements Weight %
Calcium 33.40
Iron 6.20
Silicon 1.60
Magnesium 0.28
Aluminum 0.30
Sodium 0.70
Chlorine 0.80
Sulfur 0.30

X-ray diffraction analysis shows that the crystalline phase present and dominant
in the samples is calcite (CaCO3), while in the form of small amounts dolomite
(CaCO3.MgCO3) and clay containing silicon and sodium appear. Clay is identified
by X-ray diffraction as kaolinite with the following formula:Al2Si2O5(OH)4.

No crystalline forms were detected referring to the total iron contents present in
the incrustation. Thus, it can be considered that the iron content is represented
by amorphous forms of iron oxide or hydroxide (FeO, Fe(OH)2, Fe(OH)3, FeCO3,
2-
Fe2O3 or FeOOH). The presence of sulfide (S ) was not identified by wet
chemical analysis, which means no iron sulfide (FeS) in the samples. Although it
has not been detected by the XRD it is very likely that there are significant
amounts of Fe3C residues from carbon steel pipes.

Small amounts of chlorides were detected by wet chemical analysis, which may
indicate small amounts of sodium chloride (NaCl) in the scale.

As previously noted, carbonate scale has occurred in onshore oil well tubes, that
operated in reservoir rock rich in minerals such as calcite (CaCO3) and dolomite
2+ 2+ -
(CaCO3.MgCO3), where the formation water contains Ca , Mg and HCO3
contents that enable scale and in addition, the natural gas produced was rich in
CO2.

9
Figures 1 and 7A show that the carbonate scale is formed by several overlapping
layers, with little adhesion between them, have flaws and fissures, are rough and
relatively porous. Figure 7B, below, represents a detail of a section of the
carbonate scale using a microscope with polarized light, with 50 X magnification
to indicate a continuous calcite (CaCO3) layer, with small fissures, associated
with ferric oxide layers.

Fig.7. A: Appearance of the inlay layers; B: Detail of the carbonate scale

using polarized light microscopy, 50 X.

Based on the chemical analysis, it can be estimated that the carbonate scale is
predominantly made up of 83 % calcite (CaCO3), 2 % dolomite (CaCO3.MgCO3),
2 % kaolinite and the rest is made up of iron oxides and hydroxides.

The formation of calcite and dolomite in the internal scale of the tubes can be
2+ 2+
clarified by the presence of Ca ions and Mg ions in the formation water based
on the following reactions:
2+ -
Ca + 2HCO3 → Ca(HCO3)2

Ca(HCO3)2 → CaCO3 + CO2 + H2O

2+ 2+ 2-
Ca + Mg +2 CO3 → CaCO3.MgCO3

Iron compounds can be attributed to the corrosive action of formation water on

carbon steel as the reactions show:
2+
Anodic reaction: Fe – 2e → Fe
-
Cathodic reaction: 2 H2O + 2 e → 2 OH + H2
2+ -
Fe + 2OH → Fe(OH)2

Fe(OH)2 + ½ O2 + H2O → 2 Fe(OH)3

Fe(OH)3 → FeOOH+ H2O

10
3.2 Results of carbonate scale dissolution test

Table 2 shows the results of scale removal efficiency test using 200 mL of a 10
wt. % and 15 wt. % HCl solutions at a temperature of 60°C for 90 minutes.

Table 2. Results of scale removal efficiency

Scale removal efficiency, %

Samples 10 wt. % HCl 15 wt. % HCl
A 98.5 99.5
B 98.1 98.8
C 98.2 98.5

Hydrochloric acid when reacting with scale may result in the following reactions:
CaCO3 + 2 HCl→ CaCl2 + CO2 + H2O

CaCO3.MgCO3+ 4 HCl→ CaCl2 + MgCl2 + 2 CO2 + 2 H2O

Fe2O3 + 6 HCl→ 2 FeCl3 + 3 H2O

This test showed the good performance of hydrochloric acid solutions in the
dissolution of carbonate scale in accordance with the referenced literature
[12,23].

3.3 Gravimetric test (mass loss) results

The gravimetric test results and the efficiency of corrosion inhibitor results of the
addition of 250, 500 and 1000 mg/L of propargyl alcohol (corrosion inhibitor) in
the acid solution containing 10 and 15 wt. % HCl, at temperatures of 25 °C, 45 °C
and 60 °C are presented in Table 3 to 6 and Figures 8and9, refer to the average
of three steel carbon coupons.
2
Table 3. Mass loss (mg/cm ) of carbon steel coupons in 10 wt. % HCl with
and without corrosion inhibitor (propargyl alcohol)
2
Corrosion Mass loss (mg/cm ), 10 wt. % HCl
Inhibitor, 25ºC 45ºC 60ºC
mg/L 1h 2h 1h 2h 1h 2h
0 0.39 0.93 4.20 17.35 12.26 39.10
250 0 0 0.19 0.38 0.34 0.86
500 0 0 0.15 0.24 0.22 0.68
1000 0 0 0.10 0.19 0.19 0.30

11
 Table 4. Efficiency of corrosion inhibitor (propargyl alcohol)
in 10 wt. % HClof carbon steel coupons
Corrosion Corrosion inhibitor efficiency, %
Inhibitor, 25ºC 45ºC 60ºC
mg/L 1h 2h 1h 2h 1h 2h
250 100 100 95.5 97.8 97.2 97.8
500 100 100 96.4 98.6 98.2 98.2
1000 100 100 97.6 98.9 98.4 99.2

2
Figure 8 . Mass loss (mg/cm ) of carbon steel coupons in 10 wt. % HCl with
and without corrosion inhibitor (propargyl alcohol)
2
Table 5. Mass loss (mg/cm ) of carbon steel coupons in 15 wt. % HCl with
and without corrosion inhibitor (propargyl alcohol)
2
Corrosion Mass loss (mg/cm ), 15 wt. % HCl
Inhibitor, 25ºC 45ºC 60ºC
mg/L 1h 2h 1h 2h 1h 2h
0 1.52 5.30 12.55 22.50 35.49 54.30
250 0 0.16 0.32 0.70 0.58 1.82
500 0 0.13 0.28 0.48 0.37 1.44
1000 0 0.10 0.19 0.27 0.29 0.48

12
 Table 6. Efficiency of corrosion inhibitor (propargyl alcohol)
in 15 wt. % HClof carbon steel coupons
Corrosion Corrosion inhibitor efficiency, %
Inhibitor, 25ºC 45ºC 60ºC
mg/L 1h 2h 1h 2h 1h 2h
250 100 97.0 97.4 96.9 98.3 96.6
500 100 97.5 97.7 97.8 98.9 97.3
1000 100 98.1 98.5 98.8 99.2 99.1

2
Figure 9 . Mass loss (mg/cm ) of carbon steel coupons in 15 wt. % HCl with
and without corrosion inhibitor (propargyl alcohol)
The results of mass loss assays showed that the addition of propargyl alcohol (2-
propyn-1-ol) in 10 wt. % and 15 wt. % HCl provided excellent protection to the
carbon steel with an efficiency superior of 95 %.

3.4 Electrochemical test

Polarization curves for carbon steel in 10 wt. % and 15 wt. % HCl solutions in the
absence and presence of corrosion inhibitor - propargyl alcohol (250, 500 and
1,000 mg/L) performed under atmospheric condition and without stirring are
shown in Figures 10 and 11.
Values for the polarization resistance (Rp), potential (Ecorr)and corrosion current
density (Icorr) were obtained byextrapolating the Tafel slope of the referenced
polarization curves,and are shown in Table7 and 8 [24, 25].

13
Figure 10. Polarization curves of the carbon steel in 10 wt. % HCl with
absence and presence of propargyl alcohol (250, 500 and 1,000 mg/L)
performed under atmospheric condition and without stirring

Figure 11. Polarization curves of the carbon steel in 15wt. % HCl with
absence and presence of propargyl alcohol (250, 500 and 1,000 mg/L)
performed under atmospheric condition and without stirring

14
Table 7 – Results of current density (Icorr), potential (Ecorr), polarization
resistance (Rp) and corrosion inhibitor efficiency referring to the
polarization curve performed at 10 wt. % HCl with additions of propargyl
alcohol
Corrosion Current density, Potential Polarization Corrosion
2
Inhibitor, (Icorr), A/cm (Ecorr), V resistance inhibitor
2
mg/L (Rp),.cm efficiency, %
-2
0 1.66 x 10 - 0.424 108.2 --------
-5
250 6.05 x 10 - 0.450 10,030 99.63
-5
500 4.18 x 10 - 0.429 11,836 99.75
-5
1000 3.67 x 10 - 0.410 14,516 99.80

Table 8 – Results of current density (Icorr), potential (Ecorr), polarization

resistance (Rp) and corrosion inhibitor efficiency referring to the
polarization curve performed at 15wt. % HCl with additions of propargyl
alcohol
Corrosion Current density, Potential Polarization Corrosion
2
Inhibitor, (Icorr), A/cm (Ecorr), V resistance inhibitor
2
mg/L (Rp),.cm efficiency, %
-2
0 2.48 x 10 - 0.418 54.8 --------
-4
250 1.26 x 10 - 0.420 7,375 99.45
-5
500 7.53 x 10 - 0.427 8,628 99.69
-6
1000 4,45 x 10 - 0.417 11,241 99.82

Through the curves in Figures 10 and 11 and the results presented in Tables 9
and 10, it is possible to verify that with the increase in the concentration of the
inhibitor the current density of the system (Icorr) decreases.
According to Elachouri et al.[26] for an corrosion inhibitor to be considered
efficient, it is necessary that the electrical current that runs through a given
system must be significantly reduced. This is because the inhibitor molecules
form a barrier of resistance to the passage of current, preventing corrosion from
occurring on the metal surface.
Another parameter to look out for is the polarization resistance (Rp). Through the
Rp value it is possible to verify whether there has been an increase or a decrease
in the corrosiveness of the medium.According to Tables 7 and 8, there is an
increase in Rp and, therefore, an increase in protection efficiency [ 27].

3.5 Proposal for carbonate scale dissolution mechanism and corrosion

protection with corrosion inhibitor

Based on the tests carried out, supported by the bibliographic references and
with the didactic vision, a mechanism is proposed in Figure 12 to explain the

15
dissolution of carbonate scale and the protection exerted by propargyl alcohol as
a corrosion inhibitor.

Figure 9 – Proposal of a diagram of carbonate scale dissolution and the

action of propargyl alcohol in an acid medium

As previously reported, hydrochloric acid removes carbonate scale and exposes

the surface of carbon steel to the acidic medium with hydrogen evolution and
2+
formation of Fe ions according to the reactions:
2+
Anodic reaction: Fe – 2e → Fe
+
Cathodic reaction: 2 H + 2 e → H2

The addition of propargyl alcohol to hydrochloric acid can lead to a partial or total
+
reaction even with the H ions dissociated in acid solution, having spontaneously
captured the positive charges by the inhibitory molecules, a process called
"protonation [28].
+
Thus there is an intense competition between the H ions and protonated
inhibitor molecules (propargyl alcohol) moving into areas where they accumulate
+
cathode electrons. Even considering that the ionic mobility of H ions is superior
(minor ion) to protonated inhibitor molecules, stable adsorption of the inhibitor
occurs on the metal surface, thus preventing the formation of atomic hydrogen
(H) and the release of molecular hydrogen (H2) and consequently the release of
2+
Fe ions [1,2].

It is important to report there are theories that point out that the good adsorption
capacity of propargyl alcohol molecules by carbon steel is linked to their π-
electrons, which interact with metal surfaces and, consequently, form triple

16
bonds, HC≡C-CH-OH [1, 29]. Other theories show that the propargyl alcohol
molecules polymerize on the substrate and form a film and/or an adsorbed
coating preventing the corrosive action of the acidic medium [1, 30, 31].
For safety, it is important to report that all laboratory experiments were carried
out in a fume hood with good exhaustion of gases.
Propargyl alcohol or 2-propyn-1-ol (CASRN 107-19-7) is also pretty dangerous
product to man and the environment. This product causes burns to tissues, skin,
eyes, mouth and by aspiration can injure, nose, larynx, esophagus and stomach.
It is selective toxic to the contamination of liver and kidneys [32, 33].

4. CONCLUSION

The chemical removal of carbonate scale in oil production pipes and anti-
corrosion protection using corrosion inhibitors (propargyl alcohol) was studied on
the basis of laboratory tests and references. The following conclusions may be
drawn:

 Based on the chemical analysis, it can be estimated that the carbonate scale
is predominantly made up of 83 % calcite (CaCO3), 2 % dolomite
(CaCO3.MgCO3), 2 % kaolinite(Al2Si2O5(OH)4) and the rest is made up of iron
oxides and hydroxides;

 The hydrochloric acid solution with 10 wt. % and 15 wt. % has become an
excellent removing agent with a yield of more than 98%;

 The results of mass loss assays showed that the addition of propargyl alcohol
(2-propyn-1-ol) in 10 wt. % and 15 wt. % HCl provided excellent protection to
the carbon steel with an efficiency superior of 95 %;

 The polarization curves at room temperature also attest to the excellent

efficiency of propargyl alcohol (99%) in acidic medium.

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