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IBP1131_11

INTERNAL CORROSION OF STABILIZED CRUDE OIL API-


X100 STEEL PIPELINES
1 1 2
Farzad Mohammadi , Faysal Fayez Eliyan Eliyan , Zhenjin Zhu ,
2 1
Patrick J. Teevens and Akram Alfantazi

IBP1131_11
Copyright 2011, Brazilian Petroleum, Gas and Biofuels Institute - IBP
This Technical Paper was prepared for presentation at the Rio Pipeline Conference & Exposition 2011, held between September, 20-
22, 2011, in Rio de Janeiro. This Technical Paper was selected for presentation by the Technical Committee of the event. The
material as it is presented, does not necessarily represent Brazilian Petroleum, Gas and Biofuels Institute’ opinion or that of its
Members or Representatives. Authors consent to the publication of this Technical Paper in the Rio Pipeline Conference &
Exposition 2011.

Abstract
Carbon dioxide corrosion behavior of API-X100 steel pipeline in simulated stratified pipeline flow was investigated
experimentally. An autoclave system was used to simulate the service condition. Samples were mounted on an externally
controlled rotating shaft inside the autoclave. Emulsions with 1:1 and 1:9 diesel:water ratio were used at the temperature
of 100 ± 1 °C. In a solution with 1:9 diesel:water ratio, in the absence of carbon dioxide, the average corrosion rate of
the samples was calculated to be 12 mpy after the immersion time of 24 hours. When carbon dioxide was introduced to
the system at 50 psi, the corrosion rate of the samples under new conditions increased to 78 mpy after two days of
exposure but decreased to an almost constant amount of 10 mpy after 16 days. Potentiodynamic polarization and Open
Circuit Potential (OCP) experiments were performed at 40°C, 60°C, 80°C and 100°C while carbon dioxide was
continuously purged into the systems with 1:1 and 1:9 diesel:water ratios. Corrosion rates were measured and the results
were compared with the weight loss measurements obtained from the exposure experiments. Scanning Electron
Microscopy (SEM) micrographs of the corroded surfaces confirm the formation of scales on the surface which become
more compact as the exposure time increases. Performing Energy-dispersive X-ray spectroscopy (EDX) on the corroded
surfaces revealed that in the first few days of exposure, cubic shaped deposits are present in the scale that are rich in
manganese, however, as the experiment progresses the cubic deposits are disappeared and more uniform and compact
scales are observed in which alloying elements are uniformly distributed.

1. Introduction

Pipelines are important means of fuel transportation since high flow rates of hydrocarbons can be provided by
them over long distances. In order to obtain sustainable supplies, pipeline protection and maintenance strategies are
crucial. Over the long distances pipelines spread, the pipe material faces different and harsh environmental conditions
that impose difficulties on the protection. However, the internal environment the line pipe material is exposed to is also
extremely important. Although internal corrosion of oil and gas steel pipelines is often influenced by species other than
carbon dioxide, this type of corrosion is most frequently referred to as carbon dioxide corrosion (Nesic, 2007) . The
main reason is the large number of reported problems in pipeline materials caused by carbon dioxide corrosion. While
the presence of carbon dioxide increases the recovery by reducing oil viscosity, its dissolution in water cuts
accompanying the oil can result in carbon containing species, which promote the corrosion rate of line pipe materials
(Zeberg-mikkelsen et al., 2002). Aqueous carbon dioxide corrosion of line pipe materials is an electrochemical process
frequently observed in the oil and gas pipeline failures. This type of internal corrosion often results in the formation of
scales that depending on conditions and their degree of permeability and adherence may be either protective or non-
protective (Nazari et al., 2010; Videm et al., 1993). This type of corrosion is influenced by many factors some of which
are temperature and flow pattern (Davis et al., 1980; Lin et al., 2006). A frequently observed flow pattern in pipelines is
the stratified flow where an established separation of flow phases, liquids and associated gases, occurs during the
transportation of products. Stratified flow pattern is more noticeable at higher temperatures. As expected, when the
water to oil ratio increases, the associated corrosion problems increase and materials become more susceptible.
Formation of species such as carbonates and bicarbonates may affect both anodic and cathodic reaction rates and
consequently alter the corrosion rates (Ogundele et al., 1987; Ikeda et al., 1984).
______________________________
1
Dept. Mat. Eng., Univ. of British Columbia, 6350 Stores Road, Vancouver, BC V6T 1Z4, Canada
2
Broadsword Corrosion Engineering Ltd., 90 Commercial Drive, Calgary, AB, T3Z 2A7, Canada
Rio Pipeline Conference & Exposition

In order to minimize the risks and costs, to increase the efficiency and to prevent premature failures, industries need to
be able to control and predict the line pipe corrosion problems especially those associated with the presence of carbon
dioxide. A better understanding of the corrosion process and the relevant parameters is therefore necessary to achieve
such a goal. Correlating physical and chemical parameters contributing to the corrosion problem either at steel surface
or in the medium, is important for characterization of the problem. The constant request of industries for increased
production rates has led to using higher strength grades of steel pipelines, which accommodate higher operating
pressures without increasing the pipe wall thickness. API-X100 steel is a relatively new generation of High Strength
Low Alloy (HSLA) steels which is a possible candidate for many current and future applications. Alloying elements
such as V, Ti and Nb are added to the composition of this type of steel. These elements tend to combine with carbon
leaving Cr and Mo to form protective layers on the surface (Li et. Al., 1998; Alvez et al., 2002). Present work deals
with the corrosion behavior of API-X100 steel in the presence of carbon dioxide.

2. Experimental

20 mm x 15 mm x 3 mm samples were cut from an API-X100 steel pipeline. A 2 mm hole was drilled in the
center of each sample for installation on the sample holder. Before experiments, each sample was ground using 300-grit
silicon carbide sand paper. Samples were then degreased ultrasonically in acetone for 10 minutes. The chemical
composition of API-X100 steel was determined using Inductive Coupled Plasma (ICP) and carbon analysis. The
summarized composition analysis is available in Table 1.

Figura 1 Schematic representation of the autoclave test setup.

The sample holder was made cylindrically with a concentric hole in the middle with the same diameter as the
autoclave’s rotating shaft where the sample holder was mounted. Sixteen holes were drilled into the sidewall of the
sample holder with the same diameter as those that were drilled in the center of the samples. The sample holder and the
screws that were used to attach the samples to it were all made of Teflon. Figure 1 shows a schematic of the samples
installed on the sample holder, which is mounted on the rotating shaft of the autoclave.
In order to study the microstructure of the samples, epoxy mounted samples were ground using 1200-grit silicon carbide
sand paper. Samples were further polished with 6 and 1 μm diamond suspensions. The polished surface was then etched
using 2% nital solution (2 ml nitric acid + 98 ml ethyl alcohol), washed with alcohol and distilled water and dried in air
stream.

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The simulated test solution used in the experiments was an emulsion consisting of 1:1 and 1:9 commercial diesel fuel
and water ratios. The diesel fuel is a complex mixture of hydrocarbons consisting of paraffins, cycloparaffins, aromatic
and olefinic hydrocarbons. The physical and chemical properties of the diesel fuel are reported in Table 2 according to
Shell ©.

Table 1 The chemical composition of the working electrode.

Composition (wt. %)
C Mn Mo Ni Al Cu Ti Nb Cr V
0.1 1.67 0.21 0.1337 0.02 0.25 0.01 0.043 0.016 0.003

Corrosion experiments were performed in a high pressure/temperature titanium autoclave with a capacity of 1.8 L
(Figure 1). The autoclave is manufactured by Parr © and is controlled by a digital interface where readings of pressure,
temperature and rpm are provided. Operating temperature and pressure limits of the autoclave system are 250°C and
2000 psi, respectively.

Table 2 Physical and chemical properties of the diesel fuel.

Property Details
Initial Boiling Point 170 °C
Boiling Range 170 - 390 °C
Flash point Typical 63 °C
Lower / upper Flammability 1 - 6 %(V)
Auto-ignition temperature > 220 °C
Vapor pressure < 1 hPa at 20 °C
3
Density 0.84 g/cm at 15 °C
2
Kinematic viscosity 2 - 4.5 mm /s at 40 °C

Weight loss experiments were performed at absence and presence of 50 psi constant pressure of carbon dioxide. The
sample holder shaft was rotated at 50 rpm inside the autoclave throughout the experiments. Weight loss experiments
were performed at 100 °C. Experiment was interrupted at two days intervals and four samples were drawn from the
autoclave each time. Drawn samples were washed carefully, dried and then weighted precisely.
OCP and potentiodynamic polarization experiments were performed using an 800 ml standard three electrode Pyrex
electrochemical cell. Saturated Calomel Electrode (SCE) and graphite rod were used as reference and counter
electrodes, respectively. A Versastat 4 Parr potentiostat was used for performing electrochemical measurements.
Potentiodynamic polarization experiments were performed from – 0.25 VOCP to 1.6 VSCE with a controlled scan rate
of 0.16 mV/s. Electrochemical experiments were performed at 40°C, 60°C, 80°C and 100°C.

3. Results and discussion

The microstructural studies of the as received API-X100 steel samples were performed using optical
microscopy. As shown in Figure 2, a complex microstructure was observed for the samples. Ferrite and martensite are
observable phases where some bainite that has grown from the primary austenite grain boundaries and elongated during
the rolling process can also be found in the microstructure.
Results of the weight loss experiments are shown in Figure 3. As apparent, early in the experiments the corrosion rates
were more than 100 mpy for both ratios of diesel:water. These values are also much higher than that observed for the
condition where no carbon dioxide was present (the star on Figure 3). As the experiments progressed the corrosion rates
decreased at both diesel:water ratios, which indicate the gradual formation and deposition of corrosion products in the
form of a protective barrier layer on the surface. However, for all exposure periods the corrosion rates of the samples
exposed to the 1:9 diesel:water ratio solutions were higher than those of the samples exposed to the solutions with 1:1
diesel:water ratio.

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Figura 2 Optical microstructure of the as received API-X100 sample.

After nearly sixteen days of exposure the corrosion rates do not vary greatly yet the values for 1:9 diesel:water ratio are
still larger than those of 1:1. The fixed values obtained for corrosion rates after sixteen days indicate that the surface
layer has formed completely and provides consistent protection.

Figure 3 Corrosion rates measured through weight loss experiments.

The results of SEM observations are presented in Figures 4 and 5. Figure 4 shows the morphology of the scale that has
formed on the surface after two days of autoclave testing.

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Figura 4 X-ray maps for Mn from API X-100 steel after two days of corrosion in 1:9 diesel:water ratio and 50 psi
CO2 pressure.

On the top left of the Figure a lower magnification image is presented which reveals cubic deposits covering the entire
surface. X-ray maps of the deposits are also provided in Figure 4 at both low and high magnifications which indicate
that the deposits are rich in manganese.

Figure 5 API-X100 surface morphology at different exposure times at 1:9 diesel:water ratio.
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Figure 5 on the other hand, shows the evolution of the scale on the surface as the exposure time is increased. It can be
seen that the cubic deposits start to disappear after four days of exposure; however, the scale is not yet uniform. After
six days, the cubic deposits are completely disappeared yet the scale seems to be porous. Finally after ten days the
surface seems more compact and a more uniform scale with fewer grooves and pores can be observed which is expected
to provide better protection. The surface morphologies observed in Figure 5 are in good agreement with the weight loss
measurements presented in Figure 3 in that a lower corrosion rate is observed as the scale becomes more compact and
uniform. Formation of the scale on the surface affects the kinetics of anodic and cathodic reactions since the scale may
act as a barrier that the electroactive species have to pass through in order to get either oxidized or reduced. Formation
of the scales on the surface has been the subject of many studies. It has been reported that the following reactions are
frequently held responsible for FeCO3 formation in aqueous carbon dioxide solution (Ogundele et al., 1986):

2+ 2−
Fe + CO3 → FeCO3 (1)
2+ −
Fe + 2HCO3 → Fe(HCO3 )2 (2a)
Fe(HCO3 )2 → FeCO3 +CO2 + H2O (2b)

Open circuit potential (OCP) measurements of the systems at different diesel:water ratios and at different temperatures
are presented in Figure 6. Comparing the graphs presented in Figure 6 it is understood that the OCP values for the
samples in solutions with 1:1 diesel:water ratio is higher than those of 1:9 at temperatures below 80°C. This shows that
at these temperatures, the anodic reactions become harder to proceed or may be less probable as the amount of water in
the solution is decreased. When the amount of water present in the solution is increased the OCP values are lower and
the effect of temperature on them is not significant comparing to the 1:1 ratio. However, at the 1:1 ratio the minimum
OCP value is observed at 80°C indicating that the maximum corrosion rate may be observed at this temperature.

Figure 6 OCP measurements at 1:1 and 1:9 diesel:water ratios at different temperatures.

As mentioned earlier, the potentiodynamic polarization experiments were performed at temperatures ranging from 40°C
to 100°C. The results for 1:1 diesel:water ratio are presented in Figure7. As apparent, in the anodic region of these
curves the minimum current density is observed at 40°C. Increasing the temperature increases the current density in the
anodic region until 80°C is reached. A further increase in the temperature from 80°C to 100°C reduces the current
density in the anodic region.

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Figure 7 Potentiodynamic polarization of the samples at 1:1 diesel:water ratio at different temperatures.

Potentiodynamic polarization curves for the 1:9 diesel:water ratios at different temperatures are shown in Figure 8. A
similar behaviour to the 1:1 ratio is also observed in Figure 8. Increasing the temperature up to 80°C increases the
current density in the anodic region where a further increase to 100°C reduces the current density.

Figure 8 Potentiodynamic polarization of the samples at 1:9 diesel:water ratio at different temperatures.

Figure 9 is the overlay of the data in Figures 7 and 8. A comparison between the results shows the effect of diesel:water
ratio on the polarization curves. Interestingly, the curves of the 1:9 ratios stand on the right hand side of the curves for

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1:1 ratio at each temperature indicating a higher corrosion rate for the solutions with higher water content. This
observation is in good agreement with the results of weight loss measurement in Figure 3.

Figure 9 overlay of the Potentiodynamic polarization data for both 1:1 and 1:9 diesel:water ratio.

The method described in Figure 10 was employed to calculate the corrosion current densities, anodic and cathodic Tafel
slopes with minimum possible error. The Butler-Volmer equation was fitted to the experimental data within 20 mV of
the OCP using a computer program. The main advantage of using this method is that the human error is eliminated and
more accurate and reproducible results are obtained. The calculated corrosion current densities were used to calculate
the corrosion rates in different conditions using Faraday equation. The results are shown in Figure 10. As apparent, the
corrosion rate of the samples increases by increasing the temperature until a maximum is reached at 80°C. Further
increase in the temperature reduces the corrosion rates. This trend is observed for both ratios of diesel:water only the
rates are higher for the 1:9 diesel:water ratios.

Figure 10 Butler-Volmer equation fitted to the experimental data.


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The results are also in good agreement with weight loss measurements presented in Figure 3; however, the corrosion
rates presented in Figure 3 are higher due to the higher carbon dioxide pressure applied to the system. An increase in the
pressure of carbon dioxide results in higher concentrations of carbonic species and thus higher reaction rates according
to reactions 1 and 2.

Figure 11 Electrochemically measured corrosion rates as a function of temperature.

4. Conclusions

The deposits on the surface of API-X100 steel samples in solutions containing water and diesel at 100°C and
50 psi CO2 pressure form protective scales which over time reduce the corrosion rate of the samples. Surface
morphology of the samples indicates the evolution of consistent scales after 16 days of exposure. Decreasing the water
content of the test solution results in the reduction of the corrosion rate of the samples at all temperatures.
Electrochemical corrosion rate measurements reveal that increasing the temperature from 40°C to 80°C increases the
corrosion rate; however, a further increase to 100°C only reduces the corrosion rate of the samples.

5. Acknowledgement

The authors would like to thank Natural Sciences and Engineering Research Council of Canada (NSERC) and
Broadsword Corrosion Engineering ltd. for providing the financial and technical support to this research project.

6. References

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1980.
Ikeda, A., Ueda, M., Mukai, S. CO2 bevaviour of carbon and Cr steels, Advances in CO2 corrosion. Corrosion, NACE,
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Li, J., Meier, D. An AFM study of the properties of passive films on iron surface. J. electro analytical chemistry, v. 454,
p. 53-58, 1998.

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Lin, G., Zheng, M., Zhao, X. Effect of temperature and pressure on the morphology of carbon dioxide corrosion scales.
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chemistries on corrosion of an API-L80 steel. Corrosion, v. 43, n. 11, p. 665-673, 1987.
- -
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