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



Lining Xu* University of Science and Technology Beijing, Beijing, China

Wenliang Zhang University of Science and Technology Beijing, Beijing, China China Petroleum and Chemical Corporation(SINOPEC) Beijing, China

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

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

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

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

ABSTRACT CO2 corrosion is frequently encountered in oil and gas industry. The search for new sources of oil and gas has pushed the operational activities to harsher environment and this requires new tubing and pipeline materials which can endure tough circumstances. Low alloy steel containing Chromium, which fills the gap between carbon steels and corrosion resistant alloys in terms of cost and corrosion resistance, has aroused significant interest from steel enterprises and scholars. At present, these studies mainly focus on 3%-5%Cr steel, and little study concerns the 2%Cr steel, which is more economic and weldable. In this paper, novel Cr2MoNbTi steel was developed and the microstructure and mechanical properties were studied. Corrosion behavior of the Cr2MoNbTi steel immersed in the CO2-containing solutions, which corresponded to the environment of bottom-of-line corrosion (BLC), was studied using high temperature-high pressure autoclave. In addition, dynamic high temperature-high pressure condensation autoclave was employed to simulate the top-of-line corrosion (TLC) environment and the corrosion behavior of the Cr2MoNbTi steel under wet gas environment was investigated. The composition and morphology of the corrosion scale were characterized by energy dispersive spectroscopy and scanning electron microscopy analyses. The results show that the Cr2MoNbTi steel exhibited uniform corrosion and presented good resistance to CO2 corrosion compared with X65 pipeline steel.

Keywords: Pipeline steel, CO2 corrosion, Low alloy steel containing Chromium, Top-of-line corrosion

INTRODUCTION The carbon dioxide (CO2) corrosion of carbon steel pipelines is one of the most serious problems in the oil and gas industry (1, 2, 3 and 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). 3%Cr steel have shown good CO2 corrosion resistance with relative low cost, and it is successfully applied as casing pipe. Even so, for transportation line pipe, not only good CO2 corrosion resistance but also good mechanical property and weldability is needed. Low alloy steel containing Cr has larger difference with carbon steel in weldability. The addition of Cr increases the hardness of weld joint and induces crack after welding, which may increase the risk of damage in use. In addition, the coarse grains will occur and the toughness will decline in heat affect zone (HAZ), which is due to the welding heat cycle. This can also cause the cracking of the welded joint. The results of Kermani et al(2) in the welding ability for low alloy steel containing Cr showed that, the measured hardness is lower than the predicted value, but still higher than the

*CorrespondingAuthor: Lining Xu E-mail address:

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requirements for sour environment. Muraki(6) investigated the welding of 3%Cr steel using argon tungsten-arc welding (TIG) and high frequency electric resistance welding (ERW) and obtained HAZ with good toughness based on appropriate contents of C, Si, Mn, Nb and Ti alloying elements. In addition, similar to Cr in the steel substrate can influence weldability of pipeline steel, Cr in weld metal will also change the microstructure and mechanical properties of the welding joint. Therefore, if it can be guaranteed that low alloy steel with reduced Cr content have good corrosion resistance in CO2 environment, the mechanical properties and the welding performance of low alloy steel will be significantly improved. In this paper, Cr2MoNbTi pipeline steel by adding 2%Cr element was investigated after forging and hot rolling process. Besides microstructure and mechanical properties test, the corrosion performance under CO2 corrosion environment was studied.

cooling temperature were kept 50 and 10, respectively. Test duration was 120h. The gas flow rate was 1.72m/s, controlled by the rotation of the sample holder. The CO2 partial pressure is 0.8MPa. Prior to both tests, the samples were subsequently ground with 300, 600, 800 and 1200 grit silicon carbide papers and then cleaned with distilled water, degreased in acetone. Test solution was made from analytical grade reagents and deionized water (18 Mcm in resistivity) to simulate the formation water in oil field. The ion concentrations (g/L) were: Na+ 19.935, K+ 0.14467, Ca2+ 0.142, Mg2+ 0.086, Cl- 30.00, SO42- 1.334, CO320.111, and HCO3- 0.500. The surface and cross sectional morphologies of corrosion scales were characterized by scanning electron microscopy (LEO-1450). Corrosion products on the corroded samples were analyzed by using X-ray diffraction (CuK, =0.154nm, Rigaku). Energy dispersive X-ray spectroscopy (Kevex Super Dry) was employed for the composition analysis of the corrosion scales.

EXPERIMENTAL The chemical composition (wt.%) of Cr2MoNbTi steel is: 0.05C, 0.14Si, 0.53Mn, 2.09Cr, 0.22Mo, 0.041Nb, 0.025Ti and Fe balance. And that of 3%Cr steel is: 0.07C, 0.20Si, 0.55Mn, 2.99Cr, 0.15Mo, 0.03Nb, 0.02Ti and Fe balance. Steel ingots were reheated and forged into 80 mm80 mm230 mm slabs for controlled rolling. The slabs were heated up to 1200 and maintained for 1 hour and then rolled at above 1000 for 2 passes to a thickness of 34 mm followed by 3 rolling passes between 920 and 820. The final thickness of the plate was about 12 mm. The plates after rolling went through water curtain cooling and the cooling rate was 15 - 20/s. Simulating bottom-of-line corrosion (BLC) tests were performed in flow condition in a 4L autoclave under high temperature and high pressure. The arc-shaped samples were vertically installed in the fixture which was driven to rotate by a motor, and then immersed in the formation water. The solution was initially purged with N2 for at least 8 hours, and then CO2 was introduced by bubbling for at least 4 hours to the autoclave before heating. The CO2 partial pressure and the temperature were 0.8 MPa and 80, respectively. The tests were kept running for 517 hours. Simulating top-of-line corrosion (TLC) tests were performed in a high temperature-high pressure condensation autoclave, as shown in Fig. 1. It was specially designed to provoke water condensation on the surface of the samples, which were placed in a holder above the solution surface and covered with a thin film of water condensed from the water vapor contained in the gas phase. The temperature of the gas phase in the autoclave was controlled by a heating system, simulating the wet gas temperature in pipelines. Another side of the samples was cooled by an external cooling system, simulating the lower temperature of the pipe wall. The gas temperature and the

Figure 1. The schematic of the condensation autoclave simulating top-of-line corrosion

RESULTS AND DISCUSSION The microstructure of Cr2MoNbTi steel (Fig.2a), shows a mixture of acicular ferrite and a small amount of ferrite. In contrast, the microstructure of carbon steel X65 consists of ferrite with a small amount of pearlite. The results of tensile test are shown in Table 1. Adding 2%Cr into the ordinary carbon steel and reducing the content of C and Mn inhibit the growth of austenitic grain in high-temperature region and improve the stability of austenite. Then after proper rough and fine rolling process, austenitic grains will be fully flattened, which provides more nucleation site for the ferrite transformation and increases the driving force of transformation. Subsequently, by cooling in an appropriate speed, a mixed microstructure composed of acicular ferrite and a small amount of polygonal ferrite can be obtained, which indicated a good combination of strength and toughness.

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steel improved the localized corrosion resistance simultaneously reduced the corrosion rate.
(a) (b)


Figure 2. Microstructure of Cr2MoNbTi (a) and X65 (b) Table 1 Mechanical properties of the Cr2MoNbTi steel 0.2 /MPa 545.1 UTS/MPa 0.2 / UTS 0.723 Elongation /% Figure 4. Microscopic morphology of corrosion scales on X65 (a) and Cr2MoNbTi (b) steels (80, 0.8 MPa, 517h) The composition of amorphous scale was measured by using EDS (energy dispersive spectrum) analysis and the result is shown in Fig.5. As exhibited in the Figure, Cr was enriched in the amorphous scale. Thus, the improved corrosion performance was attributed to the formation of a Cr enriched amorphous layer, which is in accordance with many literatures(9, 10 and 11).



Where 0.2 is the 0.2% yield strength and UTS is ultimate tensile strength. Cr2MoNbTi steel and X65 steel were exposed to the CO2 containing formation water at 80 for 517h, and the macroscopic morphology of both steels after the removal of corrosion scales are shown in Fig.3. X65 steel suffered severe localized corrosion, with deep pits on the surface, and the deepest pit reached three millimeters. In contrast, Cr2MoNbTi steel presented general corrosion morphology, indicating that chromium addition in carbon steel improved the localized corrosion resistance. The average corrosion rate of X65 and Cr2MoNbTi steel measured by weight loss method under 80 0.8 MPa were 9.83 mm/y and 1.50mm/y respectively. As the immersion test is simulating bottom-of-line corrosion (BLC), combining the corrosion rate and localized corrosion resistance, Cr2MoNbTi steel possesses better BLC performance than X65 steel. The corrosion rate of 3%Cr steel at the same test condition was 1.37mm/y, indicating that the reduction of Cr content from 3% to 2% can guarantee good corrosion performance.
(a) (b)

Figure 5. EDS analysis results of Cr2MoNbTi steel corrosion scales (BLC environment) Figure 6 shows the macroscopic morphology of Cr2MoNbTi steel under top of line corrosion environment. The sample surface is completely covered by a layer of continuous and compact scales. After the removal of corrosion scale, general corrosion morphology can be seen without pits on the surface. The average corrosion rate is 0.306 mm/y.
(a) (b)

Figure 3. Macroscopic morphology of X65 (a) and Cr2MoNbTi (b) after the removal of corrosion scales (BLC, 80, 0.8 MPa, 517h) The microscopic morphology of corrosion scales on Cr2MoNbTi steel and X65 steel are shown in Fig.4, The scales of X65 steel shows crystal pilling morphology, while that of Cr2MoNbTi steel is amorphous. The mud cracking morphology of Cr2MoNbTi steel was due to dehydration(7, 8), and the scale was continuous and tough when immersed in the solution. It is deduced that the amorphous corrosion scales of Cr2MoNbTi

Figure 6. Macroscopic morphology of Cr2MoNbTi steel with scale(a) and after the removal of corrosion scale(b) Figure 7 shows the surface and cross-section microscopic morphology of the corrosion scale on Cr2MoNbTi steel under CO2 top of line corrosion environment. In Fig.7 (a), the

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corrosion scale is compact with an amorphous morphology, and FeCO3 corrosion product in form of crystals can also be observed spreading upon the amorphous scale. In Fig.7 (b), it can be found that the interface between the corrosion scale and steel substrate is smooth without apparent pits. The thickness of the corrosion scale is about 100m. The composition of corrosion scale was measured by using EDS analysis and the results are shown in Fig.8. 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. As exhibited in the figures, Cr, Fe and O elements are the primary elements and the 42.3% Cr content is much higher than that in the steel substrate, which indicates the Cr enrichment in the corrosion scale. The right image of Fig.8, which is the Cr distribution in the corrosion scale at the same location of Fig.7 (b), shows obvious enrichment of Cr with uniform distribution.
(a) (b)

Cr(OH)3 in the corrosion product film increases and results in the Cr enrichment shown in Fig.7. Moreover, because Cr(OH)3 usually appears as amorphous state(13), the corrosion scale on Cr2MoNbTi steel presents amorphous morphology. Cr enriched amorphous scale benefits the improvement of corrosion resistance of the steel, especially for the localized corrosion. Since there is few hole or interstice induced by grain boundary, the scale with good compactness will inhibit the ion transfer between the solution and the steel substrate(13), which will result in the decrease of corrosion rate. Also the better bonding capacity of the scale with steel substrate will additionally enhance the corrosion resistance.

CONCLUSION Novel Cr2MoNbTi steel with a microstructure of acicular ferrite and a small amount of polygonal ferrite and well-matched strength and toughness has been obtained by adding 2% Cr, reducing C and Mn content properly based on the composition of traditional pipeline steel and controlling cooling of rolling process. The localized CO2 corrosion of Cr2MoNbTi steel can be obviously inhibited. A layer of amorphous corrosion scale with Cr enrichment is formed on the steel surface and has a good protection effect on the steel. ACKNOWLEDGMENTS The project is supported by National S&T Major Project of China (Grant No. 2011ZX05056). REFERENCES Put references here. [1] Farelas, F., Galicia, M., Brown, B., et al., 2010, Evolution of dissolution process at the interface of carbon steel corroding in a CO2 environment studied by EIS, Corros Sci Vol.52, pp. 509517. [2] Kermani, M. B., Morshed, A., 2003, Carbon dioxide

Figure 7. SEM image of the top of line corrosion scale on Cr2MoNbTi steel surface (a) and in cross-section (b)

Figure 8. EDS analysis results of Cr2MoNbTi steel corrosion scales and the EDS image of Cr distribution in the corrosion scale at the same location of Fig.7 (b) Previous researches(12-13) showed the electrochemical reaction of steel containing Cr in CO2 corrosion environment mainly occurs as follows:

corrosion in oil and gas production a compendium, 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

Fe Fe 2 2e 2H 2e H 2

(1) (2)

2H 2 CO3 2e H 2 2HCO3
Fe2 CO3 FeCO3

(3) (4) (5)

Cr 3 3H 2 O Cr(OH) 3 3H

FeCO3 can dissolve in the week acid solution saturated with CO2, while Cr(OH)3 is more stable. Therefore, the content of

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media in the presence of Hac, Electrochim Acta, Vol. 54, pp. 73387344. [6] Muraki T, Nose K, Asahi H. 2003, Developmen of 3% chromium linepipe steel, Corrosion/03. Houston: NACE, paper No. 03117. [7] Sun J B, Liu W, 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(1), pp. 84 [8] Lu X H, Zhao G X, Zhang J B, et al. 2009, Corrosion behavior of low Cr steel at the simulated H2S/CO2 Environment, J Mater Eng, Vol.10, pp. 20 [9] Carvalho DS, Joia CJB, Mattos OR. 2005, Corrosion rate of iron and iron-chromium alloys in CO2 medium. Corros Sci, Vol. 47, pp. 2974-2986. [10] Kermani MB, Gonzales JC, Turconi GL, et al. 2004,

In-field corrosion performance of 3%Cr steels in sweet and sour downhole production and water injection. Corrosion/04, Houston: NACE, Paper NO. 04111. [11] Pigliacampo L, Gonzales JC, Turconi GL, et al. 2006, Window of application and operational track record of low carbon 3Cr steel tubular. Corrosion/06, Houston: NACE. Paper NO. 06133. [12] Chen C F, Lu M X, Zhao G X, et al. 2003, Characteristics of CO2 corrosion scales on 1%Cr- containing N80steel, J Chin Soc Corros Port, Vol. 23(6), pp. 330 [13] Chen, C. F., Lu, M. X., and Sun, D. B., et al., 2005, Effect of chromium on the pitting resistance of oil tube steel in carbon dioxide corrosion system, Corrosion 61, Vol. 6, pp. 594.

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