Trans. Indian Inst. Met. Vol.57, No. 3, June 2004, pp.

277-281

TP 1893

CORROSION BEHAVIOUR OF PIPELINE STEEL IN CO2 ENVIRONMENT

G.S. Das and A.S. Khanna
Corrosion Science and Engineering, Indian Institute of Technology, Bombay, Mumbai-400076 E-mail : gsdas@met.iitb.ac.in (Received 5 October 2003 ; in revised form 7 April 2004)

ABSTRACT
The influence of temperature (30-120oC) on the corrosion behavior of low carbon pipeline steels in the CO2 saturated solutions in the closed autoclave system has been studied. At lower temperatures, the surface films have an open porous structure and hence the FeCO3 film formed dissolved continuously in the CO2 saturated solution. Between 60 to 90oC, the FeCO3 film accumulated more in the outer part, which is more porous, less dense and nonprotective in nature and hence the corrosion rates of samples increase with temperature. Incontrast, above 90oC, a dense protective FeCO3 film is formed and the corrosion rate decreases significantly at 120oC.

1. INTRODUCTION
Dissolved CO2 in water or aqueous solution causes severe corrosion of pipeline steel and process equipments used in the extraction, production and transportation of oil and gas in the petroleum industry. Many variables are associated with the CO2 corrosion process such as pH, temperature, pressure and surface films.1 Present study focuses on the role of CO2 in both anodic and cathodic reaction for the pipeline steels. Significant work has been reported in this direction by de Waard and Milliams.1,2 However, very few studies have been carried out on the long term corrosion behaviour of pipeline steel in CO2 environment. Typical laboratory tests carried out continuously for 48 hours under static condition in CO2 containing solution at pH 4.5 and 5.8. The formation of surface films, mainly of FeCO3, and their influence on the corrosion rate has significant role in the CO2 aqueous solutions.2,3 Iron carbonate (FeCO3) formation is temperature dependent and important in the formation of protective layers over the metal surface.2,4

1.1 Theoretical Background of CO2 Corrosion Aqueous CO 2 corrosion of carbon steel is an electrochemical process involving the anodic and cathodic evolution of hydrogen.4 The overall reaction is: Fe+CO2+H2O = FeCO3 + H2 (1)

The electrochemical reactions are often accompanied by the formation of films of solid FeCO3 (and/or Fe3O4), which can be protective or non protective depending on the condition under which they are formed. One of the most important individual reaction is the anodic dissolution of iron: Fe = Fe2+ + 2e(2)

It is believed that the presence of CO2 increases the rate of corrosion of mild steel in aqueous solution by increasing the rate of the hydrogen reaction. The presence of H2CO3 enables hydrogen evolution at a higher rate even at pH greater than 5.5 Thus at a given pH as the partial pressure of CO2 increases the solubility of CO2 in the solution increases leading

TRANS. INDIAN INST. MET., VOL. 57, NO. 3, JUNE 2004

to a higher corrosion rate than would be found in a solution of a strong acid.6

2. EXPERIMENTAL METHODS
The materials used for the experiment were supplied by ONGC Panvel and Juhu Helibase (Pipeline Group) Bombay, India. The chemical composition of alloys, as obtained by inductively coupled plasma and atomic emission spectroscopy (ICP-AES) technique, are shown in Table 1. The as received materials were cut into the rectangular specimens of dimension 15X12X3.5 mm and 12X10X2 mm with a hole of 1.5 mm diameter drilled near the top edge of each sample to facilitate suspension of the sample inside of an autoclave of

the capacity of 2.2 liters. All faces of the samples were initially coarse ground on SiC belt grinder machine then consequently machine polished in the successive grades of emery papers up to 600 grit. The polished samples were washed and subsequently cleaned in acetone. Experiments were carried out at four temperatures (30, 60, 90 and 120oC) and at pressures ranging from 50 to 300 PSI under static condition in a multiphase dynamic loop machine. Initial weight of the samples were measured and then kept inside of the autoclave for 48 hours continuous test. Initially the vessel was deaerated by using a vacuum pump and purging argon continuously for 1-2 hour for removing the oxygen impurity. Then deaerated solution was poured into the vessel. The temperature was raised to the testing condition then

Fig. 1 : Corrosion rate of API grade steels at 30oC

Fig. 2 : Corrosion rate of API grade steels at 60oC

Fig. 3 : Corrosion rate of API grade steels at 90oC

Fig. 4 : Corrosion rate of API grade steels at 120oC

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DAS AND KHANNA : CORROSION BEHAVIOUR OF PIPELINE STEEL IN CO2 ENVIRONMENT

Table 1
CHEMICAL COMPOSITION OF THE ALLOYS USED (IN WT%)

GRADE API X-52 API X-56 L-80 API X-60

C 0.20 0.16 0.22 0.10

Mn 1.23 1.19 1.38 0.74

Si 0.47 0.19 0.22 0.014

S 0.12 0.22 0.21 0.20

P 0.17 0.29 0.28 0.26

Cr 0.065 0.047 0.013 0.067

Mo 0.06

CO2 and argon were charged to maintain the pressure and observed from the digital display unit (DDU). Each experiment was conducted using the same procedures for a total period of 48 hours continuously with four samples and corrosion rates were measured in mils per year (mpy). In order to analyze corrosion products X-ray diffraction (XRD) and environmental

scanning electron microscope (ESEM) were used in this study.

3. RESULTS AND DISCUSSION

Corrosion rates of samples as a function of pressure at different temperatures are shown in Figs. 1 to 4.

Fig. 5 : ESEM micrographs showing surface morphology of (a) API X-52, (b) API X-56 exposed at 90oC and 300 PSI and (c) API X-52 and (d) API X-56 exposed at 120oC and 300 PSI

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At low temperature, corrosion rate of samples slowly increases due to continuous dissolution of Fe2+ ion in the solution as a result of formation of porous FeCO3, which is not protective in nature, however as the temperature increases from 30 to 60oC, the FeCO3 film becomes less porous, more adherent to the metal surface and protective in nature and hence the corrosion rate decreases. Beyond 60oC, the corrosion rate increases and it is higher at 90 0C due to accumulation of more porous inner FeCO3 film on the metal surface which initiates formation of cracks and finally spallation of FeCO3 film. The corrosion rates of all the samples are higher at 90oC as shown in Fig.3. In all the cases, corrosion rate of the pipeline steel increases as the partial pressure of CO2 increases due to local depletion of HCO3-, which is favoring the cathodic reaction. Crolet and co-workers6 have reported that FeCO3 can precipitate on the steel surface with higher rate of dissolution of Fe2+ ion and the additional HCO3- anions produced

by the cathodic reduction of CO2 It has been also reported that FeCO3 precipitation is temperature dependent and for its precipitation super saturation with the Fe2+ ion is required which is 5-10 times higher than the thermodynamically calculated values of solubility.7-9 The surface morphology of API X52 and API X-56 as shown in Fig. 5 indicates cracking and spallation of FeCO3 film at 90oC and 300 PSI. However, at 120oC and 300 PSI, the FeCO3 film is showing protective nature and good adherence on the metal surface as shown in Fig. 6. Similarly API X-60 and L-80 grade steels at 90oC and 300 PSI indicate crack formation and less adherence of the protective film with the base metal and thus corrosion rates are higher, but at higher temperature the oxide layer is more protective in nature and adheres on the metal surface with exception of L-80 grade steel. The phases formed on the metal surface were obtained by XRD analysis as shown in Fig.7 indicates the formation of FeCO3, Fe3O4, and Fe2O3

Fig. 6 : ESEM micrographs showing surface morphology of (a) API X-60 (b) L-80 exposed at 90oC and 300 PSI and (c) API X-60 and (d) L-80 exposed at 120oC and 300 PSI

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DAS AND KHANNA : CORROSION BEHAVIOUR OF PIPELINE STEEL IN CO2 ENVIRONMENT

Fig.7 : XRD Patterns of all the four samples exposed at 120oC and 300 PSI

4. CONCLUSIONS
1. At lower temperature the FeCO3 film gets dissolved continuously and hence the corrosion rate somewhat increases but at higher temperature the dense protective layer of FeCO3 film formed on the metal surface which is adherent and more protective in nature. The Corrosion behaviour of line pipe steel is related to the formation of FeCO3, which is a corrosion product in CO2 environment. At high temperature a solid protective film of FeCO3 formed on the metal surface, which acts as a corrosion barrier against corrosion.

3.

C. de Waard and Lotz U, Prediction of CO2 corrosion of carbon steel in the Oil and Gas Industry, Institute of Materials Publisher, UK (1994) pp. 3049. Palacios C A, and Shadley J R, Characteristics of corrosion scales on steel in a CO2-saturated NaCl brine. Corrosion 47 (1991) pp. 122127. C. de Waard and Milliams D E, Carbonic acid corrosion of steel. Corrosion 31 (1975) pp. 177181. Nesic S, Thevenot N, Crolet J L, and Drazic D M, Electrochemical properties of iron dissolution in the presence of CO2 Corrosion96 NACE, USA, paper 3, 1996. Ogundele G I, and White W E, Some observations on corrosion of carbon steel in aqueous environments containing carbon dioxide. Corrosion 42 (1986), pp. 7178. Videm K, and Dugstad A, Corrosion of carbon steel in an aqueous carbon dioxide environment. Part 2. Film formation. Mats. Perf. 28 (1989), pp. 4650. Johnson M L, and Tomson M B, Ferrous carbonate precipitation kinetics and its impact CO2 corrosion, Corrosion91, NACE, USA, paper 268 1991.

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REFERENCES
1. C. de Waard, and Milliams D E, Prediction of carbonic acid in natural gas pipelines, First International Conference on the Internal and External Protection of Pipes paper F-1, University of Durham, September 1975. C. de Waard, Lotz U, and Milliams D E, Predictive model for CO2 corrosion engineering in wet natural gas pipelines. Corrosion 47 (1991) pp. 976985.

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