Proceedings of the 2012 9th International Pipeline Conference IPC2012 September 24-28, 2012, Calgary, Alberta, Canada

IPC2012-90676
COMPARE THE CORROSION OF 3%Cr STEEL WITH X65 PIPELINE STEEL IN SUBSEA CO2 TOP-OF-LINE CORROSION ENVIRONMENT
Yunan Zhang University of Science and Technology Beijing, Beijing, China Lining Xu* University of Science and Technology Beijing, Beijing, China

Wei Chang
CNOOC Research Institute, Beijing, China

Minxu Lu University of Science and Technology Beijing, Beijing, China

Lei Zhang University of Science and Technology Beijing, Beijing, China

Shaoqiang Guo University of Science and Technology Beijing, Beijing, China

ABSTRACT CO2 Top-of-Line Corrosion (TLC) of carbon steel pipelines is a serious problem for subsea wet gas pipelines. A series of experiments were carried out in the high-pressure high-temperature condensation autoclave, in order to simulate the corrosion environment of TLC. The purpose of this paper was to compare the corrosion resistance of 3%Cr steel with API X65 pipeline steel in CO2 TLC environment. The composition and morphology of the corrosion scale were characterized by energy dispersive X-ray spectroscopy and scanning electron microscopy analyses. The results indicate that 3%Cr pipeline steel shows relative good resistance to CO2 TLC, with slight pitting at static condition, however, X65 suffers severe mesa corrosion. The analysis of composition and morphology revealed that the amorphous corrosion scales was formed on the surface of 3%Cr steel. The localized corrosion of 3%Cr steel may be related to the uneven filling of Cr compound under static condition. KeywordsWet gas, 3%Cr steel, X65 steel, CO2 corrosion, Cr enrichment

INTRODUCTION The carbon dioxide (CO2) corrosion of carbon steel pipelines are one of the most serious problems in the oil and gas industry(1,2 and 3), and CO2 Top-of-Line Corrosion (TLC) of carbon steel pipelines is a serious problem for subsea wet gas pipelines. This type of corrosion phenomena happens when vapor condenses due to a change in temperature between the gas flowing inside of the pipe and the pipe wall(4). Because of their low cost, carbon steels are widely used as construction materials for pipelines, but carbon steels are susceptible to the CO2 corrosion, causing the failure of pipelines(5).

In recent years, several researchers found that adding Cr element into steels could improve their CO2 corrosion resistance, by changing the structure, compactness and chemical composition of corrosion products(6, 7 and 8). For their superior CO2 corrosion resistance and relatively low cost, the new generation of low Cr (3 to 5%) bearing steels seems to be a good choice to meet the demand of mitigating CO2 TLC. Many scholars focus on the corrosion behavior and mechanism of 3%Cr steel when the samples immersed in the CO2-containing solutions. Hu, et al(9) had reported the difference between 3%Cr steel and X65 steel in corrosion resistance under solution immersion condition. The results showed the corrosion resistance of 3%Cr steel was superior to API X65 steel, and an amorphous scale was formed on the surface of 3%Cr steel due to the Cr element enrichment. Xu, et al(10) reported that the corrosion products on 3% had two-layer structure. They found the inner layer was denser and stable resulting from Cr enriching, and outer layer was composed of crystalline FeCO3. The data of extensive laboratory assessment and field experience have confirmed that low Cr bearing steels have an improved corrosion performance when immersed in CO2 containing solution, however, the corrosion resistance of 3%Cr steel on wet CO2 gas corrosion has not been clarified. In the paper, the corrosion test of 3%Cr steel and API X65 pipeline steel were investigated on wet gas CO2 corrosion. A series of experiments were carried out in the high-pressure high-temperature condensation autoclave under static condition, in order to simulate the corrosion environment of wet gas subsea pipelines. EXPERIMENTAL 1.1Material and solution The chemical composition of the steel used in this work was shown in Table 1. The arc shaped samples of 1/8 circle(108mm

*Corresponding Author: Lining Xu E-mail address: xulining@ustb.edu.cn

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of diameter and 11mm width) were polished using 360 and 800 grit emery papers, cleaned with distilled water, degreased in acetone, and then weighted using four digital balance. The ion concentrations of the corrosive solution simulating the formation water of a gas field were shown in Table 2. Table 1. Chemical composition of the steel tested (wt,%) Materials C Si Mn Cr Mo Fe 3Cr 0.05 0.18 0.58 2.90 0.19 Balance API X65 0.04 0.20 1.50 0.50 0.50 Balance Table 2. Ion concentration of test solution(mg/L) K+ Na+ Ca2+ Mg2+ ClSO42- CO32194.9 356.9 511.5 49.2 1631.9 115.2 46.8

NO316.7

1.2 Experimental methods Corrosion tests were performed in a dynamic high temperature-high pressure condensation autoclave, as shown in Fig.1. The samples were installed in a holder above the solution surface and covered with a layer of thin film of water condensed from the water vapor contained in the gas phase. A heating system was used to control the temperature of the gas phase in the autoclave for simulating the wet gas temperature in the pipelines. And an external cooling system was used to cool another side of the simples for simulating the lower temperature of the pipe wall. The solution was deoxygenated by purging N2 for 8h, and then CO2 was introduced into the autoclave gradually and continuously bubbled for 2h. In this experiment, the temperature of the gas phase and cooling were kept 80 and 27, respectively. The test duration was 696h. The CO2 partial pressure was 1.5MPa, and the experiment was carried out under the static conditions.

RESULTS AND DISCUSSION 2.1 Macroscopic morphology of X65 and 3%Cr steel in CO2 TLC environment Figure 2a shows the macroscopic morphology of corrosion scales formed on X65 pipeline steel, and it was loose and porous. After the corrosion scales were removed, severe mesa corrosion was observed on the surface of X65 pipeline steel (Fig.2b). Besides, as exhibited in the Fig.2, the position of localized damage on corrosion scales corresponded with the position of mesa corrosion after the removal of corrosion scales. Fig.2c shows the macroscopic morphology of corrosion scales on the surface of 3%Cr steel, and it was compact and tough when the samples immersed in the wet CO2 gas environment under high temperature-high pressure environment, and the mud cracking morphology was due to dehydration after the samples removed from the autoclave(11). After removing the corrosion scales, slight pitting corrosion was observed on the surface of 3%Cr steel(Fig.2d), and severe mesa corrosion occurred on the surface of X65(Fig.2b). The depth of the deepest pit on 3%Cr steel was 0.16mm, and the biggest altitude difference of mesa corrosion on X65 was 0.34mm. Fig. 2e exhibited the average corrosion rates of X65 steel and 3%Cr steel by weight loss measurement, and the result indicated that the corrosion rate of X65 was five times higher than 3%Cr steel in CO2 TLC environment. Thus, adding 3 wt% Cr into carbon steel, the corrosion rate decreased greatly and the morphology changed. This was in good agreement with the result of Xies research in Ref. (4). The morphology of X65 was mesa corrosion and that of 3%Cr steel was general corrosion. And, the corrosion rates of 3%Cr steel and X65 steel were 0.41mm/a and 2.88mm/a respectively. It should be noted that the corrosion rate in Xies research was under flow condition, while that in this paper was under static condition. It seems that localized corrosion prone to occur under static condition for 3%Cr steel.
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Figure 1. The schematic of the experimental setup 1.3 Morphology observation and composition analysis The surface and cross-sectional morphologies of corrosion scales were characterized by scanning electron microscopy (LEO-1450). Energy dispersive X-ray spectroscopy (Kevex SuperDry) was employed to analyze the composition of the corrosion scales.

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(c)
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Corrosion rate (mm/a)
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Figure 3. Surface morphologies of the corrosion scales of API X65 and 3%Cr steel: (a) and (b) X65; (c) and (d) 3%Cr
3%Cr

Figure 2. The surface morphologies of X65 and 3%Cr after corrosion (a)and(b)X65,(c)and (d)3%Cr and (e) the average corrosion rate of X65 and 3%Cr 2.2 Microscopic morphology of corrosion scales of X65 and 3%Cr steel Figure 3 shows the surface morphologies of the corrosion scales on X65 and 3%Cr steel in CO2 TLC environment. The microscopic morphology of corrosion scales on X65 pipeline steel was observed in Fig.3(a) and (b). The corrosion scales presented typical crystalline morphology, and it was loose and porous. The crystalline FeCO3 scale had many holes and gaps, through which the corrosive ions can easily penetrate, and the localized corrosion of X65 pipeline steel was very severe. Fig.3(c) and (d) showed the SEM images of the corrosion scales formed on 3%Cr steel. The two SEM images all indicated that amorphous corrosion scales formed on the surface of the 3%Cr steel. The corrosion scales presented compact and continuous characteristic, and the cracks existed in the scales were resulted from the dehydration. The chemical composition (wt%) of corrosion scales measured by EDS is listed in Table 3. The ratio of Cr(wt%)/Fe(wt%)of corrosion scales was 2.13, which meant that highly Cr enrichment in the corrosion scales. Due to the Cr enrichment, the corrosion scales changed from porous crystalline morphology to compact amorphous morphology, and greatly reduced the porosity. (b) (a)

Table 3 EDS results of the corrosion scales of X65 and 3%Cr (wt,%) Materials Fe Cr O Si Mn Mo C* API X65 61.61 35.35 0.53 1.81 0.72 / 3Cr 17.25 36.76 42.73 0.74 2.52 / * To enhance the conductivity of the corrosion scale for SEM analysis, some carbon powder was sprayed on the surface of the scale, so the content of carbon was inaccurate and thus neglected. 2.3 Cross-section analysis of corrosion scales of X65 and 3%Cr steel Figure 4 shows the corresponding cross-sectional morphology of X65 pipeline steel. As exhibited in Fig.4a, the corrosion scales of X65 at the scales/substrate interface were loose and mainly composed of small FeCO3 particles .However the outer layer of corrosion scales was compact FeCO3 layer. Figure 5 shows the corresponding cross-sectional morphology of 3%Cr steel in CO2 TLC environment, it is clear that the scales at the interface were more compact than that of X65, which may be why 3%Cr steel possessed better corrosion resistance than X65. According to the result of EDS analysis, the inner layer of 3%Cr steel was mainly composed of FeCO3, and the outer layer was Cr-enriching layer. However, it is unclear how these scales were formed on the surface of 3%Cr steel at the scales/substrate interface. To answer this question we studied the characteristic of corrosion scales by back-scattered image(Fig.5d). It was speculated that the FeCO3 were formed at the scales/substrate interface at the beginning. Then, some holes in FeCO3 layer were filled by Cr compound, forming more compact Cr-rich layer (outer layer). Thus, the outer layer of corrosion scales presented the characteristic of Cr-enriching. Meanwhile, the initiation and development of pitting corrosion may be related to the uneven Cr enrichment. For static condition in CO2 TLC environment, the filling of pores in the FeCO3 layer by Cr compound may not be uniform. On the unfilled area, the corrosive anions can easily reach the substrate and caused the pitting corrosion locally on the substrate. As shown in Fig.5d, in the outer layer there was little Cr on the top part of that picture (the mark in red was not obvious). And the depth of corrosion in that area was higher than other areas. Therefore, the localized corrosion may correspond to the uneven filling of FeCO3 layer by Cr

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compound. Besides, compared Fig.4 and Fig.5, the corrosion scales of 3%Cr steel was thinner than that of X65. (b) (a)

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Red-Cr Green-Fe

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(c) (d) Red-O Green-Fe

Figure 5. Cross-section micrographs of corrosion scales of 3%Cr steel: (a) the cross-section micrographs; (b) the distribution of chromium element; (c) the distribution of iron element; (d) the distribution of chromium element and iron element We study the formation of pit on 3%Cr steel, and Fig.6 shows a shallow pit on the surface of 3%Cr steel. It is clear that the corrosion scales above the pit did not fall off, which is much different from X65 steel. For carbon steels, localized corrosion was usually caused by the locally falling of corrosion scales, just as Fig.2a and Fig.2b show. As there were corrosion scales on the pitting area and non-pitting area, it is guessed that the protectiveness of corrosion scales on the pitting area was weaker than other areas. According to Fig.5d, the difference of protection may derive from the uneven filling of FeCO3 layer by Cr compound, and the local area filled by Cr compound was more tough and compact. In other words, the filling of Cr compound was not uniform in the scales, causing the protectiveness of scales were not better than other areas and a small pit formed. Thusslight pitting corrosion occurred on 3%Cr steel under static condition. And it is guessed that if the environment tends to restrain the uneven filling process, the localized corrosion may be mitigated. Fortunately, it was reported in Ref.(4) that uniform corrosion occurred under flow condition, with other test parameters the same as this paper. As flow can accelerate mass transfer and consequently restrain the uneven filling of corrosion scales, it can be deduced that the localized corrosion of 3%Cr steel may have a close link with the uneven filling. And this will be investaged thoroughly in our further study.

Figure 4. Cross-section micrographs of corrosion scales of X65 pipeline steel: (a) the cross-section micrographs; (b) the distribution of oxygen element; (c) the distribution of iron element; (d) the distribution of oxygen element and iron element (a) (b)

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Figure 6. Cross-section micrograph of corrosion scales on 3%Cr steel CONCLUSIONS In CO2 TLC environment, 3%Cr steel suffered slight pitting and presented relative good resistance to CO2 TLC compared with X65 pipeline steel. The corrosion rate of X65 pipeline steel was five times higher than 3%Cr steel. The corrosion scales of 3%Cr steel were characterized by the amorphous Cr-enriching scales. The pitting corrosion may be related to the local difference of Cr enrichment in the corrosion scale.

ACKNOWLEDGMENTS The project is supported by National S&T Major Project of China (Grant No. 2011ZX05056).

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Corrosion, Vol. 59, pp. 659683. [3] Ezuber, H. M., 2009, Influence of temperature and thiosulfate on the corrosion behavior of steel in chloride solutions saturated in CO2, Mater Des, Vol. 30, pp. 34203427. [4] Xie, Y., Xu, L. N., and Gao, C. L., et al., 2012, Corrosion behavior of novel 3%Cr pipeline steel in CO2 Top-of-Line Corrosion environment, Materials and Design, Vol. 36, pp. 54-57. [5] Amri, J., Gulbrandsen, E., and Nogueira, R. P., 2009, Pit growth and stifling on carbon steel in CO2-containing media in the presence of Hac, Electrochim Acta, Vol. 54, pp. 73387344. [6] Takabe, H., and Ueda, M., 2001, The formation behavior of corrosion protective films of low Cr bearing steels in CO2 environments, Corrosion/01. Houston: NACE, paper NO. 01066 [7] Chen, C. F., Zhao, G. X., and Yan, M. L., et al., 2002, Characteristics of CO2 Corrosion scales on Cr-Containing N80 steel, Journal of Chinese Society for Corrosion and Protection, Vol. 22, pp. 335-338. [8] Chen, C. F., Lu, M. X., and Zhao, G. X., et al., 2002, Characteristics of CO2 corrosion scales on 1%Cr-containing N80 steel, Journal of Chinese Society for Corrosion and Protection, Vol. 23, pp. 330-334. [9] Hu L. H., Zhang L., and Chang W., et al., 2011, Compared the corrosion resistance of 3%Cr steel with API X65 pipeline steel in CO2 corrosion environment, Corrosion/11. Houston: NACE, paper NO.11073. [10] Xu, L. N., Chen, T. H., and Chang, W., 2012, Effect of temperature on CO2 corrosion production scales on 3%Cr pipeline steel, Journal of University of Science and Technology Beijing, Vol. 34, pp. 149-156. [11] Sun, J. B., Liu, W., and Chang, W., et al., 2009, Characteristics and formation mechanism of corrosion scales on low-chromium X65 steels in CO2 environment, Acta. Metall. Sin, Vol. 45, pp. 84-90.

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