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Corrosion Inhibition of Tubing Steel during Acidization of Oil and Gas Wells

M. Yadav,1 Sumit Kumar,1 and P. N. Yadav2


1Department of Applied Chemistry, Indian School of Mines, Dhanbad 826004, India
2Department of Physics, Post Graduate College, Ghazipur 233001, India
Received 13 September 2012; Accepted 14 November 2012
Academic Editor: Jorge Ancheyta
Abstract
Acidization is an oil reservoir stimulation technique for increasing oil well productivity. Hydrochloric
acid is used in oil and gas production to stimulate the formation. The acid treatment occurs through N80
steel tubes. The process requires a high degree of corrosion inhibition of tubing material (N80 steel). In
the present investigation effect of synthesized amino acid compounds, namely, acetamidoleucine (AAL)
and benzamidoleucine (BAL) as corrosion inhibitors for N80 steel in 15% HCl solution was studied by
polarization, AC impedance (EIS), and weight loss measurements. It was found that both the inhibitors
were effective inhibitors and their inhibition efficiency was significantly increased with increasing
concentration of inhibitors. Polarization curves revealed that the studied inhibitors represent mixed type
inhibitors. AC impedance studies revealed that charge transfer resistance increases and double layer
capacitance decreases in presence of inhibitors. Adsorption of inhibitors at the surface of N80 steel was
found to obey Langmuir isotherm.

1. Introduction
Acidization of a petroleum oil well is one of the important stimulation techniques for enhancing oil
production. It is commonly brought about by forcing a solution of 15% to 28% hydrochloric acid into the
well through N80 tubing to open up near bore channels in the formation and hence to increase the flow of
oil. To reduce the aggressive attack of the acid on tubing and casing materials (N80 steel), inhibitors are
added to the acid solution during the acidifying process. The effective acidizing inhibitors that are usually
found in commercial formulations are acetylenic alcohols, alkenyl phenones, aromatic aldehydes,
nitrogen-containing heterocyclics, quaternary salts, and condensation products of carbonyls and amines
[16]. However, these inhibitors are effective only at high concentrations, and they are harmful to the
environment due to their toxicity, so it is important to search for new nontoxic and effective organic
corrosion inhibitors for N80 steel15%HCl system. In this regard, amino acids have a promising
alternative for the design of ecofriendly corrosion inhibitors [710] which satisfy the environmental
requirements.
In the present investigation acetamidoleucine (AAL) and benzamidoleucine (BAL) were synthesized, and
their corrosion inhibiting properties on N80 (oil-well tubular steel) steel was studied in 15%HCl by using
weight loss, polarization, and AC impedance techniques. Influence of temperature (from 298 to 333K) on
the inhibition behavior was studied. Both the activation and thermodynamic parameters governing the
corrosion process were calculated and discussed.

2. Material and Methods


2.1. Materials
The working electrode and specimens for weight loss experiments were prepared from N80 steel sheets
(supplied by ONGC) having the following percentage by weight (%wt) composition: C: 0.31, Mn: 0.92,
Si: 0.19, P: 0.01, S: 0.008, Cr: 0.20, and Fe: remainder.
2.2. Weight Measurements
The specimens for the weight loss experiments were of the size 3cm 3cm .1cm, and for
electrochemical studies the exposed surface area of the working electrode was 1cm2. For weight loss
experiments 300mL of 15%HCl (v/v) was taken in 500mL glass beakers. The inhibition efficiencies (IE)
were evaluated after a preoptimized time interval of 6h using 10, 20, 50, 100, and 150ppm by weight of
inhibitors. The specimens were removed from the electrolyte, washed thoroughly with distilled water,
dried, and weighed. The inhibition efficiencies (IE) were calculated using the following equation:

[
(

2.3. Adsorption Isotherms


The information about the electrochemical interaction of inhibitors with metal surface can be provided by
the nature of adsorption isotherm. Different adsorption isotherm such as Langmuir, Temkin, and Frumkin,
were tested graphically by ploting surface coverages ()and concentration of studied (AAL and BAL) on
N80 steel in HCl solution. The surface coverage was calculated using the following equation:
[

2.4. Electrochemical Polarization Studies


The electrochemical studies were performed in a three necked glass assembly containing 150mL of the
electrolyte with different concentrations of inhibitors (10, 50, and 150ppm by weight) dissolved in it. The
potentiodynamic polarization studies were carried out with N80 steel strips having an exposed area of
1cm2. A conventional three electrode cell consisting of N80 steel as working electrode, platinum as
counter electrode, and a saturated calomel electrode as reference electrode were used. Polarisation studies
were carried out using VoltaLab 10 electrochemical analyser, and data was analysed using Voltamaster
4.0 software. The potential sweep rate was 10mVs1. All experiments were performed at 27C in an
electronically controlled air thermostat. For calculating inhibition efficiency by electrochemical
polarization method, the following formula was used:
[

where is I0 corrosion current in absence of inhibitor, and is I


inhibitor.

Inhb

the corrosion current in presence of

2.5. AC Impedance Studies


AC impedance studies were carried out in a three electrode cell assembly using computer-controlled
VoltaLab 10 electrochemical analyzer, as well as N80 steel as the working electrode, platinum as counter
electrode, and saturated calomel as reference electrode. The data were analysed using Voltamaster 4.0
software. The electrochemical impedance spectra (EIS) were taken in the frequency range from 10kHz to
1mHz at the rest potential by applying 5mV sine wave AC voltage. The charge transfer resistance (Rct)
and double layer capacitance (Cdl) were determined from Nyquist plots. The inhibition efficiencies were
calculated from charge transfer resistance values by using the following formula:

)
(

3. Results
3.1. Weight-Loss Study
Weight-loss studies were performed in accordance with ASTM method. Test was conducted in 15%HCl
(v/v) solution for 6h at different temperatures (from 298 to 333K) containing different concentration of
inhibitors (10150ppm).

3.1.1. Effect of Concentration


The percentage inhibition efficiencies (%IEs) in presence of 10, 20, 50, 100, and 150ppm of AAL and
BAL have been evaluated by weight-loss technique at 25C, and the results are summarized in Table 1. It
is evident from these values that the inhibitor is significantly effective even at low concentrations like
10ppm and there is a linear increase in %IE in the whole range of concentrations studied. The corrosion
rate decreases with an increase in concentration of each inhibitor and reached the maximum value in the
range of 150ppm concentration (Figure 1).
Table 1: Corrosion inhibition of N80 steel in 15% HCl in presence and absence of inhibitors AAL and
BAL at different concentration.
Conc.(ppm)

AAL

BAL

CR (mpy)

%IE

CR (mpy) %IE

9.55

9.55

10

3.98

58.2

3.41

64.2

20

3.39

64.4

2.66

72.1

50

2.55

73.3

1.78

81.3

100

1.88

80.3

1.10

88.4

150

1.70

82.2

0.93

90.2

Figure 1: Variation of inhibition efficiency with concentration in presence of AAL and BAL.

3.1.2. Effect of Temperature


The effect of temperature on the performance of AAL and BAL as corrosion inhibitors for N80 steel in
15%HCl was investigated by weight loss measurements in the temperature range 298333K in absence
and presence of both the inhibitors at optimum concentration (150ppm) in a thermostat. The variation of
inhibition efficiency and corrosion rate with temperature are shown in Table 2. The observation depicts
that rate of corrosion increases with increase in temperature. This may be due to the fact that at higher
temperature the metal organic complex layer dissociates leaving a porous diffused film, which is
responsible for corrosion [12].

Table 2: Corrosion parameters in absence and in presence of AAL and BAL at different temperatures.
Temperature (K)

Blank AAL

BAL

CR (mpy)

IE%

CR (mpy)

IE%

298

9.55

1.70

303

12.09

2.63

78.2

1.79

85.1

313

19.27

4.87

74.7

4.21

78.1

323

30.42

10.51

65.4

9.01

70.3

333

48.94

20.09

58.9

18.31

62.5

82.2

CR (mpy)
0.93

IE%
90.2

Table 4: Electrochemical corrosion parameters in absence and in presence of AAL and BAL at different
concentration.
Inhibitors
from wt. loss

Conc of inhibitors (ppm)

Tafel slopes
( A/cm2)
(mV)
Ba (mVdec1) Bc (mVdec1)

Blank

109

153

471

468

AAL

10

113

162

193

460

59.0

58.2

50

118

170

108

462

77.0

73.3

150

121

178

74

478

84.1

82.2

BAL

10

116

171

172

476

63.3

50

119

180

84

480

82.1

81.3

150

125

187

35

484

92.5

90.2

64.2

%IE

%IE

Figure 7: Potentiodynamic polarization curves for N80 steel in 15%HCl in absence and in
presence of BAL.

CONCLUSIONS
A commercial imidazoline base corrosion inhibitor has been modified with coconut oil and its
corrosion inhibition performance for carbon steel in acidic solution. It was found with different
techniques that even with small concentrations such as 20 ppm the corrosion inhibition of the
commercial imidazoline based inhibitor are improved by the modification with vegetable oil.
This indicates that small doses of coconut modified imidazoline could be used as a corrosion
inhibitor. The p electrons of double bonds interacted with the d-orbitals of the atoms on the metal
surface, and the unshared electron pair containing nitrogen enhanced the adsorption of the
modified imidazoline on the metal surface, resulting in the formation of a relatively stable barrier
against corrosion