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Analysis of internal corrosion in subsea oil
Article in Case Studies in Engineering Failure Analysis · January 2013
DOI: 10.1016/j.csefa.2013.12.003





2 authors:
Mochammad Noer Ilman

Kusmono Kusmono

Gadjah Mada University

Gadjah Mada University




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Title: Analysis of internal corrosion in subsea oil pipeline
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:+62 274 521673. E-mail address : Introduction Pipeline plays an important role in oil and gas industries.Ilman).N. Gadjah Mada University Jl. Crude oil. Flow pattern. Pipeline is commonly made of carbon steels due ∗ Corresponding Author. metallurgical examinations using light optical microscopy in combination with scanning electron microscopy (SEM) equipped with energy dispersive X-ray (EDX) analysis and corrosion test using a three-electrode potential (M. Flow-induced corrosion. The failure mechanism is discussed Ac ce p with specific attentions are paid to fluid flow rate and chloride-containing water phase. chemical and mechanical M characterizations. Page 1 of 18 . Up to now pipeline is perhaps the most economical and efficient means of large scale fluid transportation for crude oil and natural gas compared to rail.2. Results of this d investigation suggest that the cause of failure is electrochemical corrosion combined with te mechanical process known as flow-induced corrosion. Grafika No. Yogyakarta 55281. truck and tanker transportation in term of the flexibility of routes and large quantities to be moved on. The present investigation aims to analyze the main cause of failure by conducting standard failure analysis methods including visual examination. 1. Tel.N. Indonesia cr Abstract us Failure of a subsea crude oil API 5L X52 steel pipeline which led to oil leakage has been reported to occur after 27 years in service. fax: +62 274 521673. Some leaks were found to form at the bottom of the horizontal API 5L X52 steel pipeline near an elbow section which connected the pipeline an to a riser. Keywords : Subsea pipeline.Analysis of internal corrosion in subsea oil pipeline M. Ilman∗. Kusmono ip t Department of Mechanical and Industrial Engineering.

During operation.5 inch API 5L X-52 1.345 bwpd (barrel water per day) and 0. 28. Specification and Operating Data Value Pipe inner diameter Length Wall thickness Material Design pressure Test pressure Operating pressure Operating temperature Production (crude oil+water+gas) 16 inch 10. Ac ce p Some oil leaks were observed at the bottom of the horizontal pipeline just before the flow entered the elbow section.441 mmscf gas per day 2 Page 2 of 18 .677 ft 0. The crude oil then flowed out d the pipeline directly into a long radius elbow section which turned the crude oil flow [Figure 1 to appear here] te vertically allowing the flow to pass through a riser for further processing in platform. oil leaks have been reported to occur at a horizontal crude oil subsea pipeline an after 27 years in service. A schematic diagram of the crude oil flow and the actual picture of the failed crude oil pipeline under investigation are shown in Fig. i. Normally. carbon steels have good mechanical properties. as an oil well ages. some reasons. the production of oil starts to decline whereas water and gas flow rates tend to increase. Details of the failed pipeline and its operating data are as follows.576 bopd (barrel oil per day). No other areas of damage were identified during inspection.e. crude M oil was pumped from subsea wells into the horizontal pipeline.225 psi 170 psi (incoming) and 130 psi (outcoming) 152 F (incoming) 2. Therefore.480 psi 2. H2S and chlorine compounds which are dissolved in the fluids can accelerate corrosion process inside the pipeline[2-3]. cr the impact of changes in fluid composition on a pipeline should be anticipated during us maintenance program.1. ip t The presence of high corrosive agents such as CO2 . low cost and wider availability despite their corrosion resistance is relatively low [1].

[Table 1 to appear here] Fig. These leaks were nucleated locally at the bottom of pipeline (6 o’clock position) in the form of teardrop-shaped pits or cr grooves which elongated parallel to the fluid flow direction. Nb and V with impurities of P and S. this preliminary analysis needs to be verified by more detailed an characterizations as shown later. Mn. Of note is that elements such as Nb and V are normally added to steels as grain refiners during thermomechanical control process (TMCP).2. The main alloying elements specified by API 5L X52 are C.3 shows an optical photomicrograph of the pipeline under study. the ip t leaks were mainly observed at the inner surface of the pipeline. Analysis of crude oil pipeline material te Characterizations of the pipeline material were conducted using chemical composition analysis. However. M [Figure 2 to appear here] d 2. microstructural examination and mechanical property tests including tensile test and Ac ce p hardness measurement.2 shows visual examination results of leaks found in the pipeline. As is seen.2. it can be seen that the pipeline composition fulfills that specified by API 5L X52. It can be seen that microstructure of the pipeline is composed of ferrite and pearlite as commonly seen in low 3 Page 3 of 18 . Visual examination Fig.1. Referring to Table 1. This type of failure leads to us hypothesis that the leaks are resulted from combined effect of electrochemical corrosion and fluid flow. Table 1 shows chemical composition results obtained using emission spectrometer with the corresponding composition specified according to API 5L X52. Analytical Techniques 2.

[Table 3 to appear here] 2.3 Analysis of water phase present in crude oil Ac ce p Chemical composition of the water phase present in the crude oil was determined by atomic adsorption method with the results are given in Table 3. Water was identified to have pH of 8.8 MPa respectively and these data fulfil the minimum stresses specified by API 5L X52 standard.5 and 486. Fractography and chemical analysis of inner-side corrosion deposits Fig. bicarbonate (HCO3-) and sulphate (SO42-) where chloride (Cl-) has been known as aggressive ion. it is concluded that the pipeline material is closely match to API 5L X52 carbon steel.4 shows a surface profile taken from longitudinal section of the teardrop-shaped pits. Based on the surface profile. [Figure 3 to appear here] cr Results of tensile and hardness tests are shown in Table 2.carbon steels. the hardness value of the an pipeline does not exceed the maximum hardness specified by API 5L X52 standard. d [Table 2 to appear here] te 2. Again. The yield and ultimate us stresses of the pipeline are 381. The main ions detected were chloride (Cl-).5 or basic condition.4. it seemed that the crude oil flow produced undercutting in 4 Page 4 of 18 . Such microstructure can give high strength in steels via grain refinement according to Hall-Petch relationship and good impact toughness to meet stringent ip t requirements of pipeline material. These fine grained ferrite and pearlite are elongated along rolling direction known as texture. microstructural examination and mechanical property M tests. Based on the results of chemical composition.

SO42is anionic sulfur species in which S is fully oxidized state with the oxidation number of +6 and it is relatively unreactive.d). O.5a. It can be seen that the region marked A cr in Fig. Si and S (Fig. probably in the form of hydrous ferrous oxide Fe2O3. Of note is that C present in corrosion products probably comes from hydrocarbon and/or bicarbonate (HCO3-) whereas Cl is resulted from chloride ions (Cl-) dissolved in water.nH2O or ferrous hydroxide FeO(OH)2. Cl with low levels of Na. Region marked B in Fig.5a is the inner layer of corrosion product where this layer is directly in contact with the us steel pipeline surface. At outer deposit. The presence of S in corrosion deposits is likely associated with SO42. [Figure 4 to appear here] ip t Results of SEM microanalysis on the corroded surface near corrosion pits are shown in Fig.5c. this deposit te consists of mainly Fe and O (Fig.4.e.the downstream direction probably due to the presence of turbulence. C. EDX-microanalysis taken from this region reveals elements such as Fe.5c.5].d.5a with the EDX-spectra are shown in Fig.5a seems to be intermediate layer and it is composed of mainly Fe and O M with a considerable amount of S as shown in Fig.5d). Sulfate. These various corrosion products are consistent with the works reported by some researchers [4.5b) to outer deposits (Fig. The interpretated turbulent eddy is indicated by an arrow in Fig. oxygen easily comes into contact with the deposit and as expected.5b. i. Ac ce p It seems that the chemistry of oxides change from metal-rich to oxygen-rich as the distance moves from metal-oxide interface (Fig.5b) suggesting that this inner layer is in the an form of FeOCl as a result of chloride attack on hydrated passive film (FeOOH). the region marked d C in Fig.c. [Figure 5 to appear here] 5 Page 5 of 18 .in the water. Mg.

taken from Tafel plot.00327 (in mpy) (1) (in mm/year) (2) where D : density (g/cm3). In engineering practice. can be determined.129 ai i(EW ) = 0.62 μA/cm2 or equivalent to 8.6 shows polarization diagram (Tafel plot) for the pipeline from which the corrosion an rate. corrosion rate (r) expressed in the form of penetration per unit time (mpy and M mm/year) is commonly used and the corrosion rate can be calculated by substituting icorr . The equivalent weight (EW) in Eqs. Corrosion rate and passivity of the steel pipeline Corrosion rate of the steel pipeline was measured using a three-electrode cell with ip t saturated calomel electrode (SCE) as the reference electrode.129 nD D te r = 0. given in steady state current density icorr (μA/cm2).2.5.5 (basic) whereas H2S was not us detected.00327 nD D Ac ce p r = 0. i : current density (μA/cm2).616 mpy (0. This water was cr chemically identified to have 7183 ppm chloride with pH of 8. to the following equations [6] : d or ai i(EW) = 0.2184 mm/year) suggesting that the pipeline material has a good corrosion resistance. (1) and (2) can be determined by : EW = (NEQ )-1 (3) ⎛f n ⎞ N EQ = ∑⎜⎜ i i ⎟⎟ ⎝ ai ⎠ (4) where f is mass fraction of element in alloys. the corrosion rate of the steel pipeline is 18. the water phase extracted from crude oil was used as the electrolyte. a : atomic massa (g/mole). As it is demonstrated. Results of corrosion rate calculation are given in Table 4. Of note is that the corrosion rate measured in the laboratory test would 6 Page 6 of 18 . Fig. To simulate actual corrosion process. n : valency.

This type of corrosion could be d linked to aggressive agents such as chloride which destroy the passive film locally and te catalyze the liberation of Fe3+ according to [8]: Ac ce p FeOOH (hydrated passive film) + Cl. However. water and gas phases in horizontal pipeline. Fe + H2O + ½ O2 → Fe(OH)2 (passive film) (5) M Breakdown of passivity starts to occur at the potential of -175 mV SCE or higher suggesting that the steel pipeline has susceptibility to pitting corrosion. the surface of corrosion specimen was polished with no fluid flow during the test and test temperature was lower than the actual operating temperature.→ FeOCl + OHFeOCl + H2O → Fe3+ + Cl. from the ip t view point of passivity behavior. the polarization test may give useful information on activepassive behaviour of steel pipeline in aqueous environment.7]. it can be seen that at the potential range of -700 to -175 mV SCE. an the pipeline exhibits passivity presumably due to the formation of passive film [6. Due to density difference between liquids (crude oil and water) and gas. Flow pattern analysis The analysis of flow pattern in the present investigation is based on multiphase flow consisting of crude oil. us cr [Figure 6 to appear here] [Table 4 to appear here] Referring to Fig. different flow patterns or flow regimes can 7 Page 7 of 18 .6. 2.6.5b suggests that the mechanism in which chloride ions destroy passive film is operative.not be the same as that obtained from on-site observation due to the facts that in the laboratory test.+ 2OH- (6) (7) The presence of Cl in corrosion product as shown in EDX-spectra in Fig.

Ql and Qg are liquid and gas volumetric flow rates respectively and Af is pipeline flow cross- an sectional area. Disscussion Based on visual analysis.occur when liquids and gas flow simultaneously inside the pipeline. Such corrosion initially produces brittle scales or rusts on the pipe surface exposed to the fluid.7. it can be seen that Usl and Usg are relatively low and based on gas- te liquid flow regime curve for horizontal pipeline [9]. it can be seen that the leaks are in the form of teardrop shaped pits or grooves at the bottom of the pipeline (6 o’clock position) where water layers preferentially form. By using flow rate data in section 1 above and converting the data into SI unit. the flow pattern is expected to take place in the form of stratified flow where the gas and liquid completely segregate from each other Ac ce p as shown in Fig. In such a case as this. 3. water preferentially forms at the bottom of the pipeline allowing the pipe surface to come into contact with water phase. The absence of scales or deposits around the grooves suggest that the pipeline is locally attacked by flow-induced corrosion. These scales act as barrier between the metal surface and the fluid so that further corrosion penetration is inhibited. the flow regimes can be determined using Eqs. (8) and (9) as follows : M [Table 5 to appear here] [Figure 7 to appear here] d Referring to Table 5. 8 Page 8 of 18 . Flow parameters in the forms of superficial liquid and gas velocities can be determined using the equations [9]: (8) Qg (9) Af cr U sg = Ql Af ip t U sl = us where Usl and Usg are superficial liquid velocity and superficial gas velocity respectively.

ip t Failure mechanism of the horizontal subsea pipeline due to flow-induced corrosion is described in Fig. oxygen present in the water subsequently consumes the electrons from anode according to the following reaction.→ 2OH- (11) The addition of the two half-reactions leads to the overall reactions as follow : Fe + H2O + ½ O2 → Fe(OH)2 (12) The corrosion product of ferrous hydroxide [Fe(OH)2] forms a diffusion-barrier layer around the pit mouth through which oxygen must diffuse. The steel surface will act as anode and it dissociates as positively charged ions leaving Ac ce p electrons behind. Once the protective film is destroyed. As the crude oil flows through the elbow section. the pipeline surface is exposed to water te [Figure 8 to appear here] d and oxidation-reduction reactions are expected to occur. Fe → Fe2+ + 2e- (10) In neutral and basic condition. At the outer surface of the Fe(OH)2 layer. the flow pattern is cr expected to take place in the form of stratified flow where the gas and liquid completely us segregate from each other and the water layer is present at the bottom of the oil pipeline. the flow must turn resulting in impacts on the an regions near the bend pipeline wall. the eddy current and possibly entrainment of sand in the pipeline have a potency to destroy the M protective film. the fluid flow causes the erosion process and the scales or corrosion products are periodically scoured from the exposed surface hence increasing corrosion rate along the flow direction.Subsequently. This impact combined with chloride in the crude oil. According to the flow analysis as previously discussed. H2O + ½ O2 + 2e.8. 9 Page 9 of 18 .

2b. As a result. Such corrosion attack changes from pinhole shape. in accord with 2Fe(OH)2 + H2O + ½ O2 → 2Fe(OH)3 (13) ip t Ferric hydroxide [Fe(OH)3] appears to be reddish-brown in color as shown in Fig. It seems that the Fe(OH)2 or Fe(OH)3 deposits resulted from corrosion reaction are then cr scoured from the exposed surface by the fluid flow hence increasing corrosion rate along the us flow direction. te 2. M 4. Acknowledgement The authors would like to acknowledge CNOOC SES Ltd and Gadjah Mada University. give inhibitor injection into an oil pipeline fluid stream. Flow induced corrosion seems to be the main cause of leakages that occur locally at d the horizontal subsea pipeline near an elbow section. 10 Page 10 of 18 . The damage prevention options are suggested : first. Combined effect of pitting corrosion and erosive flow increases corrosion rate along Ac ce p the flow direction resulting in teardrop-shaped pits. 3. Conclusions and Recommendations an typical of purely corrosive attack to become teardrop-shaped pits or grooves.access to dissolved oxygen is easy leading to the formation of ferric hydroxide. Indonesia for their cooperation. the corrosion rate at the spread of corrosion downstream is higher than that of penetration and sideways. 1. prevent water separation by increasing oil flow sufficiently so that the pipeline surfaces are maintained oil wetted and secondly.

King RA. Rodriguez J. Offshore pipelines. Chacko J. Eng Fail Anal 2007. Burlington : Gulf Professional Publishing.263:567-571. Ac ce p [9] Guo B. Gonzalez R. [2] Rodriguez MALH. Al-Yousef FK. 2005. Failure analysis of a crude oil pipeline. Corrosion and corrosion control. Unzueta AP.2004. Analysis of corroded elbow section of carbon steel piping system of oil-gas separator vessel.14:978-994.1:6-14.139:239-244. 11 Page 11 of 18 . Principles and prevention of corrosion. d [7] Uhlig HH. Song S. Wear 2007. Corrosion products formed on mild steel samples submerged in various aqueous solution. Ghalambor A. NewYork:Parkins ed.1982. cr Corrosive wear failure analysis in a natural gas pipeline. Oklahoma : PennWell. Vorster SW. [4] Azevedo CRF.References [1] Tawancy HM. Solis RDM. te Sons. Delgado DM. Hyperfine Interact 2002. Applied Science. Al-Hadhrami LM.1996. Subsea pipeline engineering. Revie RW. New York:Prentice-Hall Inc.1995. us [3] Palmer AC. Corrosion processes. Case Studies in Engineering ip t Failure Analysis 2013. an [5] Waanders FB. M [6] Jones DA. New York:John Willey & [8] Jones DA.

(a) A schematic diagram of subsea pipeline-riser configuration. Fig. Table 5.2.5. Table 2. Table 4. List of Tables te d Fig.7.1.(d) EDX. us Fig. Microstructure of the pipeline under investigation. an Fig. Fig. (b) Magnified area outlined by square in (a).spectra taken from regions marked A.4. Chemical compositions of pipelines under study (wt%).8.(c). Corrosion rates of pipelines under study. cr Fig. Surface profile of the pipeline along the flow direction.C respectively in (a). (b) A view of the failed subsea pipeline. M Fig. Proposed mechanism of flow induced corrosion in oil pipelines. Ac ce p Table 1.3. Table 3.6. 12 Page 12 of 18 . Mechanical properties of pipelines under study.B.List of Figures ip t Fig. Chemical composition of water. Calculation results of Usl and Usg with expected flow pattern. Tafel plot for the pipeline in the water phase extracted from the crude oil. (a) Leaks found at the inner surface of pipeline at 6 o’clock position. (b).(a) Corrosion products at the region near leaks. Gas-liquid flow regimes in horizontal pipelines.

2. (b) A view of the failed subsea pipeline. Fig. 1.ip t cr us an Ac ce p te d M Fig. 13 Page 13 of 18 . (a) Leaks found at the inner surface of pipeline at 6 o’clock position. (b) Magnified area outlined by square in (a). (a) A schematic diagram of subsea pipeline-riser configuration.

Fig. Surface profile of the pipeline along the flow direction.4. Microstructure of the pipeline under investigation. 14 Page 14 of 18 .ip t cr us an M Ac ce p te d Fig.3.

spectra taken from regions marked A.6.B. Fig.(c).(d) EDX.C respectively in (a).ip t cr us an M d Ac ce p te Fig. Tafel plot for the pipeline in the water phase extracted from the crude oil. (b). 15 Page 15 of 18 .5.(a) Corrosion products at the region near leaks.

05 Max Al 0.05 V 0.045 - Ti 0.8 455 min Unit ppm ppm ppm Hardness (VHN) 162.007 - Mo 0.5 358 min Table 3.066 - Cr 0. Proposed mechanism of flow induced corrosion in oil pipelines.042 0.5 7183 324 279 16 Page 16 of 18 .25 Max Si 0.133 - Table 2.608 1. Mechanical properties of pipelines under study Material Pipeline API 5L X52 Yield Stress (MPa) 381. te d Fig.024 0.04 Nb 0.35 Max P 0.M an us cr ip t Fig.022 0. MATERIAL C 0. Gas-liquid flow regimes in horizontal pipelines.8.094 0.07 Ni 0.04 Max Ac ce p Pipeline API 5L X52 S 0.010 0.166 0. Chemical composition of water Parameter pH Chloride (Cl-) Sulphate (SO42-) Bicarbonate (HCO3-) Ultimate Stress (MPa) 486. Table 1.262 0.062 - Cu 0. Chemical compositions of pipelines under study (wt%).29 Max Mn 0.3 230 max Value 8.7.

Table 4.2184 Liquid flow rate (Ql) (m3/s) Gas flow rate (Qg) (m3/s) Liquid velocity (Usl) (m/s) Gas velocity (Usg) 4.55 7. Corrosion rates of pipelines under study Material icorr (μA/cm2) NEQ EW D (g/cm3) Corrosion rate mpy mm/year Pipeline 18. Calculation results of Usl and Usg with expected flow pattern. 0.616 ip t cr Table 5.2675 Flow Pattern Stratified flow Ac ce p te d M an us (m/s) 17 Page 17 of 18 .7918 x 10-3 0.68 8.0420 1.03630 27.1445 0.62 0.

The corrosion rate could be reduced by controlling flow patterns. Ac ce p te d M an us cr ip t • • • 18 Page 18 of 18 . The presence of chloride ions in the water phase promotes flow-induced corrosion.Highlight : Oil leakages of corroded subsea pipeline occurred after 27 years in service.