Materials Science, Vol. 45, No.

1, 2009

BRIEF COMMUNICATIONS

EVALUATION OF THE EFFICIENCY OF CORROSION INHIBITORS FOR PIPE STEELS IN HYDROGEN-SULFIDE-CONTAINING MEDIA
R. M. Yurkevych
UDC 620.194

About one third of newly explored gas fields in the Ukraine contain at most 1 vol.% of hydrogen sulfide. For gas fields with relatively low contents of hydrogen sulfide, the application of materials with elevated resistance to hydrogen-sulfide stress-corrosion cracking (HSSC) and hydrogen-induced cracking leads to unreasonably high costs spent for the equipment of gas fields. At the same time, the application of insufficiently resistant materials may lead to failures of the equipment with unpredictable consequences [13]. Thus, it is most reasonable to use steels with relatively low resistance to HSSC in combination with inhibitors. For the protection against hydrogen-sulfide corrosion, it is proposed to use various domestic and foreign inhibitors [46]. They decrease the rate of general corrosion but not always serve as reliable protectors of steel against stress-corrosion cracking. Until recently, the gas-processing equipment of the Lokachyn Gas Field has been protected against possible corrosion failures by the Naftokhim-3 corrosion inhibitor produced by the Galychyna Enterprise (Drohobych) or by the DODICOR inhibitor (Germany) with similar properties [7]. At that time, the Naftokhim-8 inhibitor was not commercially produced. Its testing was originated in June 2005, parallel with testing of the Naftokhim-3 and DODICOR inhibitors. In view of these facts, the development of highly efficient commercially available domestic inhibitors and the analysis of their protective action under the conditions close to operating is a quite urgent problem. Materials and Methods of Investigations The influence of the Naftokhim-8, Naftokhim-3, and DODICOR inhibitors on the retardation of the general corrosion of 20 pipe steel and steel of the hardness group K (Table 1) were studied gravimetrically according to to the degree of protection Z and the coefficient of corrosion inhibition (principal criteria of the efficiency of inhibitors) in a NACE solution (5% aqueous solution of NaCl + 0.5% CH3 COOH saturated with H2 S; pH 34; 23 3C) [8]. The mechanism of protective action of the Naftokhim-8 and DODICOR inhibitors was studied by the electrochemical method based on measuring the stationary potential (for 24 h) and recording polarization curves on specimens of low-alloy K steel in the NACE solution. The working area of each specimen was 1 cm2 . The electrochemical characteristics were measured with a P-5827M potentiostat in the potentiodynamic mode. The rate of changes in the potential was equal to 1.67 mV / sec. As a reference electrode, we used a saturated silversilver-chloride electrode ( = 0.2 V) connected with the investigated electrode by using a bridge and a Lugin capillary.
Karpenko Physicomechanical Institute, Ukrainian National Academy of Sciences, Lviv, Ukraine; e-mail: iurkevych@ipm.lviv.ua. Translated from Fizyko-Khimichna Mekhanika Materialiv, Vol. 45, No. 1, pp. 117119, JanuaryFebruary, 2009. Original article submitted August 18, 2008. 132 1068820X/09/45010132 2009 Springer Science+Business Media, Inc.

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(a)

(b)

Fig. 1. Degree of protection (a) and the coefficient of corrosion inhibition (b) of the hydrogen-sulfide corrosion of K steel by the Naftokhim-8 (1), Naftokhim-3 (2), and DODICOR (3) inhibitors.

Table 1. Chemical Compositions and Mechanical Characteristics of K Steel and 20 Steel 0.2 S
0.02 0.02

Contents of elements, % Steel C

K 20 0.3 0.17

u MPa

Mn
0.8 0.35

Si
0.17 0.17

Cr
0.25

Ni
0.25

P
0.013 0.04

other
0.25 Cu 542 175

987 350

Results and Their Analysis It was established that the degrees of protection ( Z ) of the Naftokhim-8, Naftokhim-3, and DODICOR inhibitors are equal to 92, 86, and 80%, respectively. At the same time, the coefficients of inhibition of hydrogen-sulfide corrosion in the NACE medium ( ) are equal to 13, 7, and 5, respectively (Fig. 1). The visual inspection of the samples of 20 and K steels after testing in the hydrogen-sulfide-containing medium with Naftokhim-8 inhibitor proves its efficiency even after three months of holding. The surface of the samples was clean and without pittings (Fig. 2). The high efficiency of the Naftokhim-8 inhibitor is also confirmed by the data of electrochemical measurements (Fig.3). As a result of adding 50 mg / liter of the Naftokhim-8 and DODICOR inhibitors in the NACE medium, the corrosion potential shifts in the negative direction by 20 and 10 mV, respectively (Table 2). The corrosion current density for K steel becomes 8 and 4 times lower and the degrees of corrosion protection Z computed in the electrochemical investigations are equal to 89 and 76% for the Naftokhim-8 and DODICOR inhibitors, respectively, which agrees with the data obtained by the gravimetric method (Fig. 1). As a result of adsorption of the inhibitors on the surface of K steel, the Tafel slopes of the cathodic and anodic polarization curves increase. Under the action of the inhibitors, the rate of cathodic reaction becomes two times lower and the rate of the anodic reaction decreases by a factor of 1.7, which means that the analyzed inhibitors are of mixed action.

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R. M. YURKEVYCH

Fig. 2. Surfaces of 20 steel (1, 1 ) and K steel (2, 2 ) after testing for three months in NACE solutions: (1, 2) without inhibitors, (1,
2 ) in the presence of the Naftokhim-8 inhibitor.

Table 2. Electrochemical Characteristics of K steel in NACE Hydrogen Sulfide Solution without and with the Naftokhim-8 and DODICOR Inhibitors icor , A / m2
0.97 0.23 0.11

Inhibitors
DODICOR Naftokhim-8

C, mg / liter
50 50

Ecor , V
0.63 0.62 0.61

bc , V
0.038 0.055 0.078

ba , V
0.030 0.050 0.060

Thus, the best protective properties among three investigated inhibitors are exhibited by the Naftokhim-8 inhibitor produced from domestic raw materials and, thus, characterized by serious cost advantages.

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Fig. 3. Polarization curves of K steel: (1) NACE solution, (2) Naftokhim-8 inhibitor, (3) DODICOR inhibitor. CONCLUSIONS On the basis of the analysis of polarization curves, it is shown that the Naftokhim-8 and DODICOR are inhibitors of mixed action. It is also demonstrated that the Naftokhim-8 inhibitor exhibits the best protective properties in hydrogen-sulfide-containing media. REFERENCES
1. L. S. Saakyan, F. P. Efremov, and I. A. Sobolev, Enhancement of the Corrosion Resistance of Oil-Field Equipment [in Russian], Nedra, Moscow (1988). 2. O. I. Radkevych and V. I. Pokhmurskyi, Influence of hydrogen sulfide on the serviceability of materials of gas-field equipment, Fiz.-Khim. Mekh. Mater., 37, No. 2, 157173 (2001). 3. I. Ya. Sokol, E. A. Ulyanin, . G. Feldgandler, et al., Structure and Corrosion of Metals and Alloys: An Atlas [in Russian], Metallurgiya, Moscow (1989). 4. I. L. Rozenfeld, Corrosion Inhibitors [in Russian], Khimiya, Moscow (1977). 5. R. S. Karimov, V. M. Zhovnirchuk, and Yu. I. Babei, Corrosion Protection of the Udmurtneft Oil-Field Equipment [in Russian], Karpenko Physicomechanical Institute, Ukrainian National Academy of Sciences, Lvov (1985). 6. O. I. Radkevych, I. M. Dominyuk, and A. I. Tsynman, Influence of inhibitors on the corrosion-mechanical fracture of steels in hydrogen-sulfide media, Fiz.-Khim. Mekh. Mater., 38, No. 1, 101104 (2002). 7. V. P. Voitsitskyi (editor), Project of Exploitation of the Lokachyn Gas Field: Report of the Ukrainian Oil and Gas Academy [in Ukrainian], Lviv (1994). 8. NACE Standard MR-0175-96. Standard Material Requirements for Sulfide Stress Cracking Resistance of Metallic Materials for Oil-Field Equipment, National Association of Corrosion Engineers (NACE), Houston (1996).