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Trans. Indian Inst. Met. Vol.57, No. 3, June 2004, pp. 277-281

TP 1893

CORROSION BEHAVIOUR OF PIPELINE STEEL IN CO 2 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 (30-120 o C) on the corrosion behavior of low carbon pipeline steels in the CO 2 saturated solutions in the closed autoclave system has been studied. At lower temperatures, the surface films have an open porous structure and hence the FeCO 3 film formed dissolved continuously in the CO 2 saturated solution. Between 60 to 90 o C, the FeCO 3 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 90 o C, a dense protective FeCO 3 film is formed and the corrosion rate decreases significantly at 120 o C.

1. INTRODUCTION

Dissolved CO 2 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 CO 2 corrosion process such as pH, temperature, pressure and surface films. 1 Present study focuses on the role of CO 2 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 CO 2 environment. Typical laboratory tests carried out continuously for 48 hours under static condition in CO 2 containing solution at pH 4.5 and 5.8. The formation of surface films, mainly of FeCO 3 , and their influence on the corrosion rate has significant role in the CO 2 aqueous solutions. 2,3 Iron carbonate (FeCO 3 ) formation is temperature dependent and important in the formation of protective layers over the metal surface. 2,4

1.1 Theoretical Background of CO 2 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+CO 2 +H 2 O = FeCO 3 + H 2 (1)

The electrochemical reactions are often accompanied by the formation of films of solid FeCO 3 (and/or Fe 3 O 4 ), 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:

(2)

It is believed that the presence of CO 2 increases the rate of corrosion of mild steel in aqueous solution by increasing the rate of the hydrogen reaction. The presence of H 2 CO 3 enables hydrogen evolution at a higher rate even at pH greater than 5. 5 Thus at a given pH as the partial pressure of CO 2 increases the solubility of CO 2 in the solution increases leading

Fe = Fe 2+ + 2e -

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

suspension of the sample inside of an autoclave of Fig. 1 : Corrosion rate of API

Fig. 1 :

Corrosion rate of API grade steels at 30 o C

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 120 o C) 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

The temperature was raised to the testing condition then Fig. 2 : Corrosion rate of API

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

Fig. 2 : Corrosion rate of API grade steels at 60 o C F i g

Fig. 3 :

Corrosion rate of API grade steels at 90 o C

g r a d e s t e e l s a t 9 0 o

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

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DAS AND KHANNA : CORROSION BEHAVIOUR OF PIPELINE STEEL IN CO 2 ENVIRONMENT

Table 1

CHEMICAL COMPOSITION OF THE ALLOYS USED (IN WT%)

GRADE

C

Mn

Si

S

P

Cr

Mo

API X-52

0.20

1.23

0.47

0.12

0.17

0.065

-

API X-56

0.16

1.19

0.19

0.22

0.29

0.047

-

L-80

0.22

1.38

0.22

0.21

0.28

0.013

-

API X-60

0.10

0.74

0.014

0.20

0.26

0.067

0.06

CO 2 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.

at different temperatures are shown in Figs. 1 to 4. Fig. 5 : ESEM micrographs showing

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

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

At low temperature, corrosion rate of samples slowly increases due to continuous dissolution of Fe 2+ ion in the solution as a result of formation of porous FeCO 3 , which is not protective in nature, however as the temperature increases from 30 to 60 o C, the FeCO 3 film becomes less porous, more adherent to the metal surface and protective in nature and hence the corrosion rate decreases. Beyond 60 o C, the corrosion rate increases and it is higher at 90 0 C due to accumulation of more porous inner FeCO 3 film on the metal surface which initiates formation of cracks and finally spallation of FeCO 3 film. The corrosion rates of all the samples are higher at 90 o C as shown in Fig.3. In all the cases, corrosion rate of the pipeline steel increases as the partial pressure of CO 2 increases due to local depletion of HCO 3 - , which is favoring the cathodic reaction. Crolet and co-workers 6 have reported that FeCO 3 can precipitate on the steel surface with higher rate of dissolution of Fe 2+ ion and the additional HCO 3 - anions produced

by the cathodic reduction of CO 2 It has been also reported that FeCO 3 precipitation is temperature dependent and for its precipitation super saturation with the Fe 2+ ion is required which is 5-10 times higher than the thermodynamically calculated values of solubility. 7-9 The surface morphology of API X-

52 and API X-56 as shown in Fig. 5 indicates

cracking and spallation of FeCO 3 film at 90 o C and

300 PSI. However, at 120 o C and 300 PSI, the FeCO 3

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 90 o C 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 FeCO 3, Fe 3 O 4 , and Fe 2 O 3

of FeCO 3 , Fe 3 O 4 , and Fe 2 O 3 Fig. 6

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

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DAS AND KHANNA : CORROSION BEHAVIOUR OF PIPELINE STEEL IN CO 2 ENVIRONMENT

BEHAVIOUR OF PIPELINE STEEL IN CO 2 ENVIRONMENT Fig.7 : XRD Patterns of all the four

Fig.7 :

XRD Patterns of all the four samples exposed at 120 o C and 300 PSI

4.

CONCLUSIONS

1. At lower temperature the FeCO 3 film gets dissolved continuously and hence the corrosion rate somewhat increases but at higher temperature the dense protective layer of FeCO 3 film formed on the metal surface which is adherent and more protective in nature.

2. The Corrosion behaviour of line pipe steel is related to the formation of FeCO 3 , which is a corrosion product in CO 2 environment.

3. At high temperature a solid protective film of FeCO 3 formed on the metal surface, which acts as a corrosion barrier against corrosion.

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.

2. C. de Waard, Lotz U, and Milliams D E, Predictive model for CO 2 corrosion engineering in wet natural gas pipelines. Corrosion 47 (1991) pp. 976–985.

3. C. de Waard and Lotz U, Prediction of CO 2 corrosion of carbon steel in the Oil and Gas Industry, Institute of Materials Publisher, UK (1994) pp. 30–49.

4. Palacios C A, and Shadley J R, Characteristics of corrosion scales on steel in a CO 2 -saturated NaCl brine. Corrosion 47 (1991) pp. 122–127.

5. C. de Waard and Milliams D E, Carbonic acid corrosion of steel. Corrosion 31 (1975) pp. 177–181.

6. Nesic S, Thevenot N, Crolet J L, and Drazic D M,

Electrochemical properties of iron dissolution in the presence of CO 2 Corrosion’96 NACE, USA, paper 3,

1996.

7. Ogundele G I, and White W E, Some observations on corrosion of carbon steel in aqueous environments containing carbon dioxide. Corrosion 42 (1986), pp.

71–78.

8. Videm K, and Dugstad A, Corrosion of carbon steel in an aqueous carbon dioxide environment. Part 2. Film formation. Mats. Perf. 28 (1989), pp. 46–50.

9. Johnson M L, and Tomson M B, Ferrous carbonate precipitation kinetics and its impact CO 2 corrosion, Corrosion’91, NACE, USA, paper 268 1991.

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