Engineering Failure Analysis 118 (2020) 104892

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Engineering Failure Analysis

journal homepage: www.elsevier.com/locate/engfailanal

Study on corrosion mechanism and its influencing factors of a short

T
distance intermittent crude oil transmission and distribution
pipeline
Qi Wanga,b, , Muyang Aia, Wen Shia, Yunrong Lyub, Wei Yuc
⁎

a
Petroleum Engineering College of Southwest Petroleum University, No. 8 Xindu Avenue, Chengdu City, Sichuan Province 610500, China
b
Guangdong University of Petrochemical Technology, Maoming City, Guangdong Province 525000, China
c
Dept. of Chemistry and Materials Engineering, University of Auckland, Private Bag 92019, Auckland 1142, New Zealand

ARTICLE INFO ABSTRACT

Keywords: Based on the characteristics of short transmission and distribution distance, large fluctuation
Refinery angle and intermittent operation, the corrosion of pipelines of crude oil storage and transpor-
Corrosion of oil pipelines tation unit transporting crude oil to refinery processing units in refineries is unique. In this paper,
Sulfate reducing bacteria corrosion field data collection, fluid simulation analysis and coupon simulation experiments were carried
The flow rate
out to study the corrosion of oil pipelines. It was found that sulfate reducing bacteria (SRB)
Inhibitor
corrosion induced by scaling on the surface of the pipeline was the main mechanism leading to
the continuous corrosion perforation of the pipeline, and its induced tendency was related to the
chemical composition of the bottom water of the tank and the oil flow rate. Furthermore, if the
water had a strong tendency to scale, increasing the oil flow rate would increase the tendency of
SRB. The inhibitor was not suitable for controlling the corrosion of this type of pipeline, since it
only increased the scaling tendency and the risk of SRB would increase.

1. Introduction

Corrosion has always been one of the most important problems affecting the safety of equipment in the oil and gas industry, and
its induced failures account for about 25% of the total all equipment failures [1]. Therefore, corrosion management has become very
important for major oil and gas companies, and corresponding management standards [2,3] have been issued successively.
Even the International Organization for Standardization (ISO) has launched corresponding international standards [4]. In all
kinds of corrosion, microbial induced corrosion (MIC) will rapidly speed up the corrosion rate of equipment and facilities, resulting in
equipment failure and product loss [5], so MIC has become a focus of the oil and gas industry. In relevant studies, it has been pointed
out that MIC is mainly caused by bacteria, archaea, fungi and other anaerobic microorganisms [6], and that sediment is an important
inducement. Therefore, prediction of solid particle deposition, including wax deposition and sand deposition [7], has become an
important management measure for effective MIC prevention. In this aspect, most research has mainly focused on the study of sand
particle deposition law in long-distance pipelines. Ko t et al. [8] studied a single particle law in fluid. Danielson et al. [9] focused on
sand transport modeling in multiphase pipelines. Horender et al. [10] investigaged fluid-particle correlated motion and turbulent
energy transfer in a two-dimensional particle-laden flow. Capecelatro et al. [11] focused on turbulent liquid solid slurries in

Corresponding author.
⁎

E-mail addresses: 13790914645@163.com (Q. Wang), 653176137@qq.com (M. Ai), 672391197@qq.com (W. Shi), lyclyr@yeah.net (Y. Lyu),
w.yu@auckland.ac.nz (W. Yu).

https://doi.org/10.1016/j.engfailanal.2020.104892
Received 3 May 2020; Received in revised form 4 September 2020; Accepted 5 September 2020
Available online 11 September 2020
1350-6307/ © 2020 Elsevier Ltd. All rights reserved.
Q. Wang, et al. Engineering Failure Analysis 118 (2020) 104892

horizontal pipes. Hahsemi et al. [12] concluded laws about solid velocity and concentration fluctuations. Dabirian et al. [13] in-
dicated solid-particles flow regimes in water stratified flow in a horizontal pipeline. These methods were used to predict the critical
velocity, minimum deposition rate and initial deposition location [14,15]. But these methods are not usually suitable for the crude oil
transmission pipeline in the storage system of the refinery which often has a complex layout, large altitude fluctuations, large inclined
angles and short pipe segments, mixed crude oil transportation, frequent intermittent operation and so on, unlike long-distance
pipelines with simple operation conditions such as small inclined angles, single crude oil and long-distance continuous transporta-
tion. Thus, the validity and adaptability of these existing prediction models based on long-distance pipelines need to be verified for
use on shorter pipelines in a refinery’s storage system.
The use of an inhibitor has always been a simple, economic and effective method to control corrosion in crude oil transmission
pipelines [16,17]. However, there are many factors affecting the corrosion control effects of an inhibitor, including temperature,
inhibitor concentration, carrier flow rate, water content ratio [18], Chemical Compatibility in Corrosion Inhibitor [19], inhibitor type
[20], etc., in which the flow rate has a greater impact on the efficiency of inhibitor film-forming, and the factors affecting the
corrosion is relatively complex, including flow state [21], inhibitor film-forming [22], corrosion mechanism [23], and so it is gen-
erally believed that the static evaluation results of corrosion inhibitors cannot truly reflect their actual effect under the flowing state.
For a pipeline system with variable flowing state, like in an oil refinery storage system, it is more important to study the actual effect
of an inhibitor on the corrosion and its mechanism, so as to put forward a reasonable corrosion control strategy. This paper researches
the corrosion problem of a short-distance intermittent crude oil transmission pipeline in the crude oil storage and transportation unit
in a refinery. Based on typical failure cases, the corrosion mechanism, influencing factors and their action mechanisms are de-
termined through the field data collection, fluid simulation analysis and coupon simulation experiments, so as to formulate targeted
corrosion management and control methods.

2. Failure case

The crude oil transmission pipeline in a petrochemical company has a nominal diameter of Φ 630 mm, a nominal wall thickness of
10.7 mm, and a length of about 2000 m; it is made from Q235 carbon steel. The transmission medium in the pipeline is crude oil from
tanks, with an operating temperature of 45–55 °C. Due to crude oil processing needs, the crude oil is transported intermittently, with
a nominal flow rate of 1 m/s in the normal transportation stage. During the shutdown, crude oil is not transported to tanks but stays
in the pipeline. Since 2012, there have been many corrosion leaks in the pipeline, and especially so after 2015, when there were five
consecutive perforation leaks in about 3 years, all of which were related to the internal corrosion of the pipeline (see Table 1).
The corrosion morphology of the corrosion perforation is shown in Fig. 1. The corrosion defect is some elliptical regular holes of
about 5–10 mm, surrounded by oil sludge and dirt, and the pipe wall thickness around the holes is basically free of corrosion
thinning.

3. Failure mechanism analysis method based on leakage risk identification of each single corrosion mechanism

According to the corrosion morphology shown in Fig. 1, the corrosion mechanism inducing corrosion leakage is likely to be
corrosion under scale (CUS). However, failure samples of the corrosion leakage locations have not been completely preserved during
the previous repair and replacement of the pipeline (only some image information has been preserved) and so it is impossible to
directly analyze the failure mechanism of this earlier corrosion and its influencing factors. Therefore, the risk identification method of
a single corrosion mechanism is adopted to eliminate, one by one, the corrosion mechanisms that are inconsistent with the actual
corrosion risk, so as to find the most likely corrosion failure mechanism. The risk identification method adopted in this paper is that
recommended by API 581 [24]. The risk calculation results of the API 581 method are highly related to the type and corrosion rate of
corrosion defects; i.e. as long as there are obvious differences in the type and corrosion rate of corrosion defects between the
corrosion mechanisms, the risk level must be different. Therefore, by comparing the calculated risk with the actual risk of leakage, the
corrosion mechanism that is most likely to lead to pipeline leakage can be identified, as well as the types of corrosion defects and their
corrosion.
When the element S and organic acid in crude oil are lower than 204 °C, they are not corrosive [24]. Therefore, the corrosive
medium in the leaking crude oil pipeline mainly comes from the bottom drain water in the tank. The chemical test and analysis
results of the bottom water medium of each tank related to the pipeline are shown in Table 2.
From Table 2, due to the presence of dissolved oxygen, NH4+, sulfide, Cl−, etc., the carbon steel water corrosion may be induced

Table 1
Leakage statistical information of crude oil pipeline.
Order Pipe No. Leakage date Leakage location Corrosion type Remarks

1 L115 2012.02.08 G107 south side Perforation (internal corrosion) Perforated

2 L115 2015.01.14 G107 south side Perforation (internal corrosion) Perforated
3 L115 2015.09.13 G105 west side Perforation (internal corrosion) Perforated
4 L115 2015.12.03 Intersection of Beihengwu and Dongyou Road Perforation (internal corrosion) Perforated
5 L115 2017.11.17 G111 southeast side up turn Perforation (internal corrosion) Perforated
6 L115 2018.01.15 G111Southeast tee downstream 5° horizontal pipe Perforation (internal and external corrosion) Perforated

2
Q. Wang, et al. Engineering Failure Analysis 118 (2020) 104892

Fig. 1. Corrosion defects in the leakage part of the crude oil pipeline.

Table 2
Chemical compositions testing results of bottom water.
Testing items unit Crude oil tank 112 Crude oil tank 113 Waste oil tank 104 Waste oil tank 107 Waste oil tank 108

pH 7.08 7.01 6.52 6.97 6.71

Dissolved oxygen (mg/L) 0.02 0.26 0.14 0.02 0.45
Ca2+ (mg/L) 1802.45 1460.31 191.93 200.27 116.83
Mg2+ (mg/L) 612.67 809.07 224.47 432.66 91.37
NH4+ (mg/L) 76.29 62.65 81.43 99.83 48.04
Cl− (mg/L) 29,430 22,910 1898.53 1893.2 1080.98
HCO3− (mg/L) 0 0 0 0 0
SO42− (mg/L) 11.54 9.54 4.54 51.36 3.91
Sulfide (mg/L) 7.0 7.5 7.0 7.6 8.9
Hardness (N/mm2) 2415.12 2269.38 416.4 632.93 208.2

according to API 581. Furthermore, the high concentrations of Ca2+ and Mg2+ ions and the hardness above 200 °C are all causes of
the corrosion under scale (CUS). So, two potential corrosion mechanisms have been identified that could be causing the continuous
leakages of the pipeline.
According to the statistical data in Table 1, five consecutive perforation leaks have occurred in the pipeline in recent three years,
so the leakage rate is ＞ 3.06 × 10−2. According to API 581, the failure probability level is 5, and the consequence level of crude oil
leakage is 2. The real risk level is shown in Fig. 2(a), and the risk level is medium high.
According to the prediction model of alkaline water corrosion of carbon steel in API 581, the corrosion rate (CR) of the five
corrosive media in Table 2 is between 0.14 and 0.2 mm/y [25], so the failure probability level is level 2, and the final risk level falls in
the area shown in Fig. 2(b), which is low risk. There are at least two orders of magnitude differences in failure rate and risk level
compared with the risk shown in Fig. 2(a). Therefore, from the perspective of safety risk, it is unlikely that an alkaline acid water
corrosion mechanism is leading to continuous leakage of the pipeline, and so CUS needs to be investigated further.
Table 2 shows that the medium contains oxygen, Cl−, SO42− and other substances so there may be the three potential CUS
mechanisms: an oxygen concentration mechanism, a Cl occluded battery mechanism, and/or a microbial induced corrosion me-
chanism. The average corrosion rate of these mechanisms is 0.85~2.25 mm/y, so the failure probability level is 5, and the final risk
level falls in the area shown in Fig. 2(c). This is medium high risk – the same risk level as the real risk shown in Fig. 2(a). Therefore,
compared with the corrosion mechanism of alkaline acid water, CUS is more likely to be the main corrosion mechanism inducing
continuous leakage of the pipeline.
Given that CUS is likely to be the dominant corrosion mechanism, leakage risk now needs to be examined. CUS is different from

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Q. Wang, et al. Engineering Failure Analysis 118 (2020) 104892

16
1

16

(a) Real corrosion risk (b) Alkaline acid water (c) CUS
Fig. 2. Comparison of actual risk and potential risk levels of various corrosion mechanisms of the pipeline.

general uniform corrosion as it is considered to be a sensitive corrosion mechanism under certain conditions, namely when deposited
scale is produced from fluid in the pipeline. Aiming at this necessary condition, the Reiner Scaling index (RSI) is adopted (as
recommended by API 581), which comprehensively considers the influences of various factors, such as total solid solution, Ca2+
hardness, total alkalinity, temperature, etc. in the medium to determine the tendency of metal pipeline surface scaling. The formulae
for the Reiner Scaling index are shown in Eqs. (1) and (2).
RSI = 2PHs PH (1)

PHs = (9.3 + C1 + C2) (C3 + C4 ) (2)

where RSI is the Renner index; PHS is the calculated saturated pH value of water; PH is the measured pH value of water; C1 is the total
solid solution influence coefficient; C2 is the temperature influence coefficient; C3 is the total hardness influence coefficient; and C4 is
the total alkalinity of methyl orange.
The corresponding relationship between RSI and scaling tendency of a metal surface is shown in Table 3.
According to Eqs. (1) and (2) and Table 2, the calculated RSI of five media water are shown in Table 4, as are their corresponding
scaling tendencies according to Table 3.
From the calculation results in Table 4, almost all the media have an obvious scaling tendency. The exception is waste oil 108, but
even that medium is close to the equilibrium state, which means that it is easily affected by external interference factors and the
scaling tendency could easily change from no scaling to scaling tendency. In addition, the RSI indicates that waste oil 108 not only
has no scaling tendency, but also has potential for severe corrosion, which is in accordance with the corrosion rate and risk predicting
results of alkaline water corrosion.
To sum up, the corrosiveness of the water in the pipeline is very weak, meaning that the probability that it is water causing the
frequent pipeline leakages is very low. However, the scaling tendency of the media samples from the pipeline is relatively severe,
meaning it is much more likely that the pipeline leakages are being caused by CUS, which has a very high CR and leakage risk.

4. Failure root cause analysis method based on simulation experiment

Although the potential corrosion mechanism that is most likely to lead to pipeline leakage can be screened out by risk identi-
fication and corrosion mechanism analysis, the root cause of pipeline failure cannot be accurately determined. Therefore, a com-
prehensive method is adopted to accurately identify the corrosion mechanism and its influencing factors leading to pipeline failure.
The method involves collecting field corrosion state information, simulation modeling analysis and CUS simulating experiments, so as
to identify quantitatively the root cause of pipeline failure and hence guide radical corrosion control and maintenance.

4.1. Verification on alkaline water corrosion impacts

To further confirm the impact of alkaline water corrosion, a comprehensive method is applied to accurately locate the local

Table 3
Corresponding relationship between RSI and scaling tendency
on a metal surface in API 581.
RSI Scaling tendency

<4 severe scaling

5–6 slight scaling
6–6.5 balance
6.5–7 no scaling
>8 no scaling and severe corrosion

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Q. Wang, et al. Engineering Failure Analysis 118 (2020) 104892

Table 4
RSI of each medium and scaling tendency of metal surface.
Tank media RSI Scaling tendency

Waste oil 108 7.09 no scaling

Crude oil 113 3.99 severe scaling
Crude oil 112 3.92 severe scaling
Waste oil 104 6.08 balanced
Waste oil 107 4.83 scaling

corrosion defects combined with quantitative wall thickness revision along the 1500-m pipeline with perforation. The location points
are shown with circle marks in Fig. 3 and the detection strategy is shown in Fig. 4.
In the strategy, the possible areas with local corrosion can be quickly located by ultrasonic guided wave (GW), and the exact
location of the local corrosion defects can be further confirmed by magneto-resistive wall measurement (MWM) array C-scan method,
so as to distinguish between the local corrosion and non-corrosion areas. Finally, the ultrasonic testing (UT) thickness reading data at
the thinnest defects is applied to more accurately revise the wall thickness all over the pipeline to describe the actual corrosion
conditions distribution.
After all the measurements in Fig. 4 were taken, only one local thinning area was found. The C–scan result of this local thinning
area is shown with a rectangular frame in Fig. 5.
The local corrosion area is large in Fig. 5 and the edge shape of the corrosion defect is irregular – characteristics which are both
obviously different from the corrosion morphology characteristics of CUS. The thickness at the thinnest part of the wall is 9.8 mm,
which when compared with the original wall thickness of 10.7 mm, is only a slight change. Combined with all the other inspection
results, these measurements indicate that the local thinning shown in Fig. 5 is caused by fluid erosion, not by CUS. The other parts are
uniform corrosion problems, and their measurement results are shown in Table 5.
From the data in Table 5, the maximum thinning area of the wall occurs at the bottom of the pipeline and is mainly concentrated
between the 5 and 7 o’clock areas. The maximum reduction in thickness is 0.6 mm, and the corresponding maximum CR is 0.06 mm/
y. As the water content of the medium is far less than 5% (at 0.05%), a dilute phase model (DPM) is more suitable to simulate the flow
state of the medium in the pipeline. Furthermore, considering that the slight corrosion of the metal has indicated that water has had a
wetting effect on the metal surface, it is assumed that the dilute phase particles have the property of adsorbing on the metal surface in
DPM. The distribution of dilute phase water is shown in Fig. 6 at different flow velocities.
From Fig. 6, the magnified pipe in the red area rotates 90° outwards. When the flow velocity is lower than 1.5 m/s, the dilute
phase water can gradually settle onto the bottom of the pipeline. Even when the flow rate is increased to 4.5 m/s, there is still obvious
concentrated water phase settlement in the local area of the pipeline bottom, mainly in the 5–7 o’clock area which is basically
coincident with the general thinning area at the bottom of the pipeline (see Table 5). Considering the actual flow rate of the pipeline
is only 0.98 m/s, it can be recognized that it is the low flow velocity inside the pipeline that causes the deposition and precipitation of
dilute phase water at the bottom of the pipeline. However, according to the thickness testing data of the pipeline and chemical
analysis data of the water, due to the weak corrosiveness of the water, the CR of water is very slow and so its leakage risk is low. These
findings agree with the judgement in Section 3 that water cannot be the key corrosion mechanism causing the continuous corrosion
leakage.

Fig. 3. Location distribution of pipeline measuring points.

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Q. Wang, et al. Engineering Failure Analysis 118 (2020) 104892

Start

Guide wave(GW)
inspection

No echo signals during ±10m

Y
GW-locate the around the GW belt
high risk area
N

General thinning Locating the high risk area with

in inspected defects in axial ±20cm and
±10m pipe circumferential ±7.5° around the echo

MWM Array C C scanning the

Scan-accurately high risk area
locate the most
dangerous
corrosion defects Real corrosive defects
existed

N Y

UT thickness UT testing UT thickness reading

reading-accurately along the at the thinnest defect
quantify the circumferential from C scan
thickness direction of GW belt

Revise the thickness Revise the thickness of all

during ±10m area the defects during ±10m
beside the GW belt area beside the GW belt
Revise thickness
distribution over
all pipeline
corrosion conditions
distribution allover
pipeline

Fig. 4. Data acquisition and implementation process for all-over pipeline corrosion conditions distribution.

Fig. 5. C-scan results of local corrosion caused by fluid erosion.

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Q. Wang, et al. Engineering Failure Analysis 118 (2020) 104892

Table 5
UT testing results along the circumferential pipe.
Circumferential location Wall thickness (mm) Thickness reading range

12 o’clock area 10.7–10.8 ± 45°

3 o’clock area 10.4–10.5 ± 45°
6 o’clock area 10.1–10.3 ± 45°
9 o’clock area 10.4–10.5 ± 45°

v = 1.0m/s v = 1.5m/s

v = 2.5m/s v = 4.5m/s
Fig. 6. Distribution of dilute phase water at different flow velocities.

4.2. Verification on corrosion under scale (CUS)

According to the measured data in Table 5 and the simulation results in Fig. 6, the dilute phase water in the pipeline can settle and
gather at the bottom of the pipeline, but it can only cause general corrosion with slow CR at the bottom of the pipeline, and it cannot
be proved that the continuous perforation of the pipeline is related to CUS. Therefore, a coupon experiment is used to observe and
verify the scaling of the water medium and CUS morphology. In order to visually compare the difference between CUS and the
general corrosion, the coupons are divided into a blank group and CUS group in the waste oil 108 water without scaling tendency,
and a small amount of imidazoline is added to the water of the CUS group to increase the scaling tendency. The experimental
conditions are shown in Table 6, and the concentration of imidazoline (C12H42N2O) in the water of the CUS group is 100 mg/L.
The surface condition of the coupons after 360 h’ continuous corrosion test is shown in Fig. 7. There is only a slice of red corrosion
product on the surface of the blank group coupons and there is no scaling, while there are many areas of agglomerated surface scaling
on the surface of the CUS coupons. Two kinds of products or scales were scraped from the surface of the coupons for EDS analysis, and
the results are shown in Table 8. The products or scaling is iron oxidate composed of FeCO3, FeO, Fe2O3, etc. As the data in Table 2
showed that there was no iron ion in the experimental water, it is concluded that the scaling on the CUS coupons mainly comes from

Table 6
Testing conditions of corrosion coupon.
Blank group CUS group

Test temperature (°C) 50 50

Fluid speed (m/s) 1 1
Experimental medium Waste oil 108 water Waste oil 108 water + imidazoline
Experiment time (h) 360 360

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blank group CUS group

Fig. 7. Comparison of scale on the surface of hanging plate between blank group and corrosion group under scale.

Table 7
Chemical composition of Q235 coupons (mass fraction, %).
Element C Si Mn P S Ni Cr Cu

Mass fraction 0.17~0.23 0.17~0.37 0.35~0.65 ≤0.035 ≤0.035 ≤0.30 ≤0.25 ≤0.25

Table 8
EDS analysis results of surface corrosion products or scaling in the blank and CUS groups.
Elements Blank group (wt %) Blank group (atom %) CUS group (wt %) CUS group (atom %)

C 5.00 11.93 2.88 6.93

O 30.88 55.26 32.80 59.22
Al 0.83 0.88 0.57 0.61
Si 0.90 0.92 0.59 0.61
Cl — — 0.15 0.12
Ca 0.15 0.11 0.14 0.10
Mn — — 0.29 0.15
Fe 57.12 29.29 60.99 31.55
Cu 1.52 0.68 0.93 0.42
Zn 1.13 0.49 0.66 0.29
Tb 2.47 0.48 — —
Total 100.00 100.00

corrosion products containing Fe. Furthermore, the corrosion morphology of the coupons in the blank group (see Fig. 7) and the
composition of the corrosion products (see Table 8) further confirm that only alkaline water corrosion will occur in the pipeline under
a non-scaling condition, and its corrosion is slight enough not to induce frequent corrosion leakage.
After acetone degreasing, anhydrous ethanol dehydration and ultrasonic cleaning of the scale on the surface of the coupons, the
surfaces of the coupons from the blank group and the CUS group are dark brown, as shown in Fig. 8. Through SEM scanning, as shown
in Fig. 9, the surface is covered with a layer of non-metallic dense products with few local holes. The dense products are composed of
some iron oxide, such as Fe2O3, FeO and so on, according to the EDS data shown in Fig. 10, while only the element Fe is at the hole of
the covering products, as shown in Fig. 11. The EDS and SEM results from Figs. 9–11 show that the blank coupons have oxidized
corrosion to form a relatively dense corrosion product layer of Fe2O3 with few local holes on the metal surface.
The corrosion morphology of the coupons in the CUS group is obviously different from the blank group. The non-scaling area

Fig. 8. The macro-morphology of the coupons surface after cleaning.

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Q. Wang, et al. Engineering Failure Analysis 118 (2020) 104892

1 50X 2 150X
Fig. 9. Surface morphology of the blank group after cleaning.

Fig. 10. EDS results of dense non-metallic products.

Fig. 11. EDS results of the holes in the dense non-metallic products.

maintains a metallic luster, while the surface under the scaling is a black corrosion pit, and the SEM indicates that there are no
covering products on the non-scaling area, while the surface of the pit is covered with a loose non-metallic products, as shown in
Fig. 12.
From Fig. 13, it can be determined that almost no corrosion occurs in the non-scaling area because the EDS results indicate the
only element on the non-scaling surface is Fe. As shown in Fig. 14, through the EDS results, the non-metallic products at the pit area

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Q. Wang, et al. Engineering Failure Analysis 118 (2020) 104892

1 Metallic luster area 50X 2 corrosion pit area 150X

Fig. 12. SEM surface morphology of the CUS pit.

Fig. 13. EDS results of the non-scaling surface.

Fig. 14. EDS results of non-metal products on the surface of the pit.

contain not only elements Fe and O, but also the element S, with a mass percentage of 3.79%. By comparing the data in Tables 2 and
7, it can be seen that the S content in the products at the pit is far greater than that of the metal material itself and the total S content
in the aqueous solution; thus, the S content in the products can only come from the corrosion reaction products. The EDS results of the
non-metallic products are shown in Table 9 from different points at the pit area. The data shows that the non-metallic products
usually contain Fe and O, and the S content is more than 3% at those points having the element, which is greater than the S content in
the metal and water. Therefore, it is further confirmed that the S mainly comes from the corrosion reaction process, not the metal or
water. It is well known that the principal characteristic of SRB corrosion is the production of a high concentration of the element S

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Q. Wang, et al. Engineering Failure Analysis 118 (2020) 104892

Table 9
EDS results of non-metal products on the surface of the pit.
Points Fe (%) O (%) S (%)

(wt %) (atom%) (wt %) (atom%) (wt %) (atom %)

1 74.36 47.29 21.85 48.51 3.79 4.20

2 54.63 25.65 45.37 74.35 0 0
3 53.27 25.28 43.47 72.02 3.26 2.70
4 65.61 36.67 30.55 59.60 3.83 3.73
5 62.41 33.51 33.36 62.53 4.23 3.96
6 66.98 36.75 33.02 63.25 0 0
7 40.49 16.31 59.51 83.69 0 0

during the corrosion process. The electrochemical equations are shown in Eqs. (3)–(5). Among them, FeSx indicates that the black
non-metallic products under the scale may come from the sulfide during the SRB corrosion process. Furthermore, the EDS results at
the cracks of the black non-metallic products, as shown in Fig. 15, reveal only Fe (see Fig. 15). Based on all the EDS results, it can be
found that Cl− is contained in the scaling covering the surface of the CUS coupons, but there is no Cl− in either the corrosion
products or the cracks under the scaling. Therefore, it can be inferred that Cl− has not joined the CUS process, and so the occluded
cell effect can be eliminated. Besides, the very low concentration of Cl− under the scaling, helpful for the survival of microorganisms,
will induce the SRB corrosion together with the SO42− in the water. And during the SRB corrosion, the cracks in the corrosion product
film provide the necessary entrance to reach the metal surface under the film, making the corrosion process from Eqs. (3) to (5)
happen continuously, and then causing a severe CR. In addition, because SRB bacteria are anaerobic bacteria, when the water
solution under the scaling contains a high concentration of dissolved oxygen, it is difficult for SRB corrosion to occur. Indeed, SRB
corrosion won‘t occur until the dissolved oxygen is exhausted to form an anaerobic environment. Hence, the first step in the corrosion
process is oxygen corrosion under the scaling, caused by the oxygen concentration effect. An anaerobic environment is rapidly formed
because the nearly closed scaling means the oxygen is not easily replaced. Oxygen corrosion is why a layer of Fe oxide is formed on
the pit under the scaling, as can be seen in some points in Table 9 that contain Fe oxide but not S.

Fe 2e + Fe 2 + (3)

xSO42 + 8xH+ + 8e Sx2 + 4xH2 O (4)

Sx2 + Fe 2 + FeSx (5)

Table 10 compares the CR of the blank group and the CUS group.
From the data in Table 10, the maximum CR of the CUS group is close to 1000 times that of the blank group, reaching 5.597 mm/
y. With this CR, a pipeline with wall thickness 10.7 mm will have perforated to leak within 2 years, which is very close to the leakage
frequency calculated in Table 1. The CR data and calculations are further evidence that the major corrosion mechanism inducing
pipeline leakage is SRB corrosion under the scaling.

Fig. 15. EDS results at cracks of non-metallic products on a pit.

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Q. Wang, et al. Engineering Failure Analysis 118 (2020) 104892

Table 10
Comparison of CR between the blank group and the CUS group.
Coupon Group CR measuring method Measurement result Maximum corrosion rate (mm/y)

Blank group Weightlessness 0.4143(g) 0.0032

CUS group Maximum pit depth 0.23(mm) 5.597

5. Discussion of the impacting factors causing corrosion perforation of a short distance intermittent operational crude oil
pipeline

5.1. Impact of solution environment

Regardless of the field inspection measured data or the coupons experimental data, the CR of the CUS is always more than 100
times higher than that of general corrosion. The abnormally severe CR is caused by the following two reasons. Firstly, under the non-
scaling conditions, the electrochemical corrosion of the water is very weak, as shown in Table 2 and Table 4, and the dissolved
oxygen in the water inhibits the growth of SRB so that biological corrosion is also controlled. But under the scaling, which is a
relatively closed environment, whether the corrosion is initially oxidation corrosion and then SRB corrosion or the entire corrosion
process is only SRB corrosion, an out-of-control and continuously accelerating corrosion process develops. Secondly, there is suffi-
cient oxygen in the water to make the metal surface form a dense Fe2O3 corrosion product film, as shown in Fig. 10 and Fig. 9(1).
Even though few defects existed in the corrosion product film, its small circular hole, as shown in Fig. 9(2) and Fig. 11, affected the
integrity of the dense product film, reducing its ability to effectively control the CR. As for under the scaling, this is a closed corrosion
environment because the internal oxygen cannot be supplemented and SRB produce a strong acid environment, as shown in Eq. (4).
Hence, it is difficult to form a complete oxide corrosion product film. Meanwhile, the obvious network cracking defects, as shown in
Fig. 14 and Fig. 15, are formed to reach the metal surface directly. Therefore, the corrosion product film under the scaling cannot
effectively protect the metal from a greatly accelerating CR. Therefore, the corrosion product film under the scaling cannot effectively
protect the metal to greatly accelerate the CR. To sum up, once the surface scaling has been formed, the CUS will go on sponta-
neously, and during the CUS, the anaerobic growth of SRB plays a dominant role. Thus, controlling the scaling on the metal surface
and the amount of SRB in the water can be an effective measurement to control the risk of CUS.
According to the RSI Eqs. (1) and (2), Ca2+, Mg2+, total alkalinity of methyl orange and pH are all important factors affecting
scaling of water. Of these, Ca2+ and Mg2+ represent scaling tendency due to hardness, while total alkalinity of methyl orange
represents the potential scaling tendency due to HCO3− transforming to CO32−, and pH reflects the scaling tendency induced by
OH−. The total influence of all the above factors on scaling tendency can be calculated by the RSI.
In addition, Cl− has some influence on the stability of the scaling tendency. When Cl− concentration increases, the concentration
of dissolved oxygen will decrease which has the effect of increasing pH. The accompanying reduction in oxidation corrosion in the
water will reduce not only the CR of oxidation corrosion, but also decrease the scaling tendency caused by the pH values. Moreover,
Cl−is a bacteriostatic agent. Some studies have shown that a high concentration of Cl− can inhibit bacterial reproduction, thus
inhibiting the occurrence of microbial corrosion. In terms of SRB corrosion, the reproduction of other anaerobic bacteria can also
inhibit the growth of SRB, thus inhibiting SRB corrosion. For example, nitrate-reducing bacteria, which are also anaerobic bacteria,
can compete with SRB for carbon in organic matter, thus inhibiting the growth of SRB. Besides, nitrate-reducing bacteria only take
organic matter as the oxidation object, rather than oxidizing the metal, and so are often used as a SRB inhibitor and biological H2S
scavenger in oil fields.
In addition to the above factors, the comparative experiment in this paper also reflects the effect of a corrosion inhibitor in the oil
pipeline. Inhibitors usually utilize the lone pair electrons of N, O, Cl and the large π bond electrons of heterocyclic molecules to form
a coordination bond with the empty orbital in the 3d orbit of the Fe element. The anti π orbital (π*) on the heterocyclic molecule can
also form a back bond after receiving electrons from the 3d orbit of Fe element at same time. In this way, the chemical adsorption of
inhibitors on the metal surface [26] can be realized to form a hydrophobic film to prevent the corrosive medium from contacting the
metal. This kind of chemical adsorption has both positive and negative effects on pipeline corrosion at the same time. The positive
effect is that the inhibitor can form a film to prevent pipeline water corrosion, while the negative effect is that the inhibitor can also
promote the deposition and scaling of Fe oxides or hydroxides to induce CUS. This is mainly due to the fact that Fe2+ and Fe3+ in the
oxides or hydroxides also have empty orbits and electrons in their 3d orbits and form a stable adsorption with the inhibitor molecules
[27], thus promoting the nucleation and growth of scaling compounds. In addition, two other kinds of inhibitors, quaternary am-
monium salt (QAS)(C27H42ClNO2) and benzotriazole (BT) (C6H5N3), were used to replace imidazoline (ID) in the coupons experiment
under the same conditions. The experimental results are shown in Fig. 16. It is clear in this figure that the scaling of QAS and BT is
significantly more serious than that of ID shown in Fig. 7.
From the molecular structure model shown in Fig. 17, QAS and BT have larger π bond (heterocycle) and coordination elements
(N, O, Cl, etc.) than ID, so it is easier to adsorb the Fe oxide or hydroxide in the water, accelerating the scaling nucleation and growth
rate to cause higher coverage of scaling on a metal surface. Therefore, these chemical adsorption inhibitors may be not suitable for
anti-corrosion because the inhibitor can obviously increase the risk of CUS in a medium with possible slight scaling tendency.

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Q. Wang, et al. Engineering Failure Analysis 118 (2020) 104892

Fig. 16. Scaling on the surface of quaternary ammonium salt and benzotriazole coupons.

(a) Oil soluble ID (b) QAS (c) BT

Fig. 17. Molecular structure model of the three kinds of inhibitors.

5.2. Impact of fluid velocity

The flow velocity has a dual effect on the corrosion process. Firstly, turbulent kinetic energy will increase as flow velocity
increases, thus increasing the convective mass transfer efficiency on the metal surface. Secondly, an increase in flow velocity can
increase the shear force and decrease the stability of the attachment on the surface. For the common corrosion process, turbulent
kinetic energy increases the diffusion rate of both the corrosive agent from the medium to the metal surface and the corrosion
products from the metal surface to the medium, while shear stress destroys the corrosion product film on the metal surface to expose
the metal to the corrosion agent. Therefore, flow velocity can make the CR increase significantly during common corrosion. However,
turbulent kinetic energy and shear force have opposite effects for the inhibitor-added corrosion process. Turbulent kinetic energy
increases the adsorption rate of inhibitor molecules on the metal surface, so as to increase the inhibition rate and reduce the CR, while
shear force reduces the adsorption force to destroy the film-forming process of the inhibitor, and so increases the CR [28,29].
In general, with the flow velocities increasing, especially the increase of shear force on the metal surface, although the final
inhibition rate increases, it takes longer for the inhibition rate to initially become stable. This is because while a large amount of
inhibitor molecules rapidly adsorb on the metal surface at the beginning due to stronger turbulent kinetic energy, at the same time,
some inhibitor molecules with weak adsorption force are rapidly separated from the metal surface due to the stronger shear force.
Although, under the action of turbulent kinetic energy, other inhibitor molecules are rapidly supplemented to fill all the empty
locations on the newly exposed metal surface, these processes cause the inhibition rate to have a large continuous fluctuation until
the inhibitor forms a stable protective film. This occurs when the adsorption force of inhibitor molecules is greater than the fluid
shear force on the metal surface. Furthermore, during the gradually reducing fluctuation process, the faster the flow velocity, the
higher the surface shear force, and so the greater the fluctuation amplitude.
Therefore, it can be inferred that in the liquid, the lone pair electrons of N and O in the inhibitor droplet can form a coordination
bond and a back bond with the 3d orbit of Fe ion to adsorb Fe (OH)2 or Fe(OH)3 on the surface of the droplet, and accelerate the
nucleation and growth of scaling around the inhibitor droplet. In addition, the faster the flow velocity, the faster the thermal motion
of the inhibitor droplet, which means the inhibitor droplet can absorb more Fe(OH)2 or Fe(OH)3 from the surroundings to form a
small number of larger scaling particles during the same time period. Thus, it is inferred that a large number of smaller scaling
particles can be formed around the inhibitor droplets when in static fluid. To prove this inference, anther contrast coupons ex-
periment was done under the same experimental conditions and water as those in Table 6 but with static fluid. The experimental
results show a large number of smaller loose scaling particles attaching all over the CUS coupons under static fluid while a small
number of larger scaling particles are agglomerated and highly concentrated around just a few location of the surface of the CUS
coupon under the flowing fluid (see Fig. 18). Thus, the experimental data all agree with the inference on how flow velocity influences

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Q. Wang, et al. Engineering Failure Analysis 118 (2020) 104892

Static 4 Flowin 2

Fig. 18. Scaling of CUS coupons in static fluid and flowing fluid.

scaling.
The corrosion data of the blank group and the CUS group are shown in Table 11, Fig. 19 and Fig. 20 under the static fluid and
flowing fluid experimental conditions. These data enable us to observe the influence of flow velocity on corrosion.
From Fig. 19 and Table 11, the CR in the flowing fluid (sample 1) is significantly higher (about four times) than the CR in the
static fluid (sample 3) under non-inhibiting condition. This experimental data verify the previous inference that the turbulent kinetic
energy and shear force of fluid can increase the CR. Table 11 compares the experimental data of the blank group with that of the CUS
group in static fluid (samples 3 and 4, respectively), and shows that the inhibitor hardly plays any role – the CR of the two groups are
almost equal to each other and and both are general corrosion, not CUS The ineffectiveness of the inhibitor is due to the lack of
turbulent kinetic energy in static fluid, meaning there is insufficient diffusion power to the inhibitor molecules. Although the CR of
the CUS group is slightly higher than that of the blank group, this is likely due to the influence of uniform loose smaller scaling
particles on the coupon. However, as seen in Fig. 20, severe CUS occurred on the coupons with inhibitors added under flowing fluid
conditions, but there was almost no corrosion in the non-scaling areas. From the experimental data, two key points can be concluded:
(1) after the inhibitor is added, flow velocity can reduce general corrosion, but, conversely, (2) severe CUS can be induced, hence
increasing the corrosion risk dramatically, due to flow velocity increasing the scaling tendency and scaling rate.

6. Conclusions

Based on the case of the failure of a short-distance intermittent crude oil transmission and distribution pipeline, combined with
the field measured data and simulation experimental data, the following conclusions can be drawn for the corrosion and leakage of
this type of pipeline:

1) It is difficult to avoid water precipitation in flowing crude oil. The corrosivity of precipitated water is related to dissolved oxygen,
Cl− concentration and RSI, and the CR is positively related to flow velocity. Therefore, if there is no scaling deposition, the CR
under static fluid is far lower than that under flowing fluid.
2) In general, the scaling tendency of precipitated water is greater than the corrosion tendency in the pipeline, so the dominant
corrosion mechanism causing pipeline leakage accidents is CUS, especially SRB corrosion. The CR of this mechanism is 2 to 3

Table 11
Mass loss of blank and CUS coupons under static fluid and flowing fluid.
Sample No. 1 2 3 4

Group Blank CUS Blank CUS

Rotational speed (n/min) 198 198 0 0
Dose content (ppm) 0 100 0 100
Mass before testing (g) 25.5317 25.5269 26.1536 26.1394
Mass after testing (g) 25.1174 25.2204 26.0573 26.0421
Mass loss (g) 0.4143 0.3065 0.0963 0.0972

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Q. Wang, et al. Engineering Failure Analysis 118 (2020) 104892

Static Flowing
3 1

Fig. 19. Corrosion of blank coupons in static fluid and flowing fluid.

Fig. 20. Corrosion of CUS group coupons under static fluid and flowing fluid.

orders of magnitude higher than that of general corrosion under the same conditions, and it is a classic local corrosion with higher
leakage risk.
3) Chemical adsorption inhibitors are often used in long-distance transmission and distribution pipelines. However, in short-distance
transmission and distribution pipelines, because of the more frequent and complex change of flow velocity and flow regime, CUS
can actually be easily induced by chemical adsorption inhibitors. Thus, chemical adsorption inhibitors are not suitable to use as an
anti-corrosion mechanism in these pipelines.

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Q. Wang, et al. Engineering Failure Analysis 118 (2020) 104892

Funding

Guangdong Science and Technology Department (CN) grant number: 2018s001.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to
influence the work reported in this paper.

References

[1] M.B. Kermani, D. Harrop, The impact of corrosion on oil and gas industry, SPE Prod. Facil. 11 (3) (1996) 186–192.
[2] C. Limited, Review of Corrosion Management for Offffshore Oil and Gas Processing, HSE Books, Manchester, 2001.
[3] A. Morshed, An Introduction to Asset Corrosion Management in the Upstream Offshore Industry, NACE International, Houston, TX, 2011.
[4] ISO-51000: Risk Management. International Standards Organization, Geneva, Switzerland. 2009.
[5] A.M. Olszewski, Avoidable MIC-related failures, J. Fail. Anal. Prev. 7 (4) (2007) 239–246.
[6] M. Taleb-Berrouane, F. Khan, K. Hawboldt, Richard Eckert and Torben Lund Skovhus. Model for microbiologically influenced corrosion potential assessment for
the oil and gas industry, Corros. Eng. Sci. Technol. 53 (5) (2018) 378–392.
[7] D. Dall'Acqua, M. Benucci, F. Corvaro, M. Leporini, R.C. Grifoni, A. Del Monaco, B. Marchetti, Experimental results of pipeline dewatering through surfactant
injection, J. Pet. Sci. Eng. 159 (2017) 542–552.
[8] T. Ko, N. Patankar, D. Joseph, Lift-off of a Single Particle in an Oldroyd-b Fluid, University of Minnesota Computer Institute, Minneapolis, USA, 2001.
[9] Danielson TJ. Sand transport modeling in multiphase pipelines, Proceeding of Offshore Technology Conference, April 30-May 3, Houston, Texas, USA. 2007.
http//dx.doi.org/10.4043/18691-MS.
[10] S. Horender, Y. Hardalupas, Fluid-particle correlated motion and turbulent energy transfer in a two-dimensional particle-laden flow, Chem. Eng. Sci. 65 (2010)
5075–5091.
[11] J. Capecelatro, O. Desjardins, Eulerian-Lagrangian modeling of turbulent liquid solid slurries in horizontal pipes, Int. J. Multiphase Flows. 55 (2013) 64–79.
[12] S.A. Hahsemi, A. Sadighian, S.I.A. Shah, R.A. Sanders, Solid velocity and concentration fluctuations in highly concentrated liquid-solid (slurry) pipe flows, Int. J.
Multiphase Flows. 66 (2014) 46–61.
[13] R. Dabirian, R. Mohan, O. Shoham, G. Kouba, Solid-particles flow regimes in air/water stratified flow in a horizontal pipeline, Oil Gas Facilities. 5 (06) (2016)
1–14.
[14] J.A.R. Boulanger, Y. Wong, Sand suspension deposition in horizontal low concentration pipe flows, Granular Matter. 18 (2016) 15–24, https://doi.org/10.1007/
s10035-016-0616-2.
[15] K.W. Choong, L.P. Wen, L.L. Tiong, F. Anosike, M.A. Shoushtari, M.M. Saaid, A comparative study on sand transport modeling for horizontal multiphase pipeline,
Res. J. Appl. Sci. Eng. Technol. 7 (6) (2014) 1017–1024.
[16] M. Achour, J. Kolts, Corrosion control by inhibition Part i: corrosion control by film forming inhibitors, in: Corrosion 2015. NACE International, 2015, pp. 5475.
[17] F. Matjaž, J. Jennifer, Application of corrosion inhibitors for steels in acidic media for the oil and gas industry: a review, Corros. Sci. 86 (3) (2014) 17–41.
[18] Zhang Yinlong, Researches on pipeline corrosion and inhibitor evaluation in turpan-hami oil field, in: Cheng Du: Southwest Petroleum University, 2014.
[19] Y. Xiong, C. Li, S. Desai, et al., The importance of chemical compatibility in corrosion inhibitor performance, International Petroleum Technology Conference,
2015, p. 18435.
[20] Zhou Yongqiang, Application researches on imidazoline Co2 inhibitor in oil well, China Petroleum University, (East China), Qing Dao, 2014.
[21] A. Kaul, Study of slug flow characteristics and performance of corrosion inhibitors in multiphase flow in horizontal oil and gas pipelines, Ohio University,
Athene, 1996.
[22] W.A.N.G. Hongbin, The study of corrosion product and inhibitor films in multiphase flow, Ohio University, Athene, 2001.
[23] Y.U.E. Chen, Inhibition mechanisms of corrosion inhibitors in multiphase flow conditions using electrochemical techniques, Ohio University, Athene, 2000.
[24] API, API RP 581-2016 Risk-based inspection methodology, API, 2016.
[25] DNV-GL, DNV-GL RP G101-2010 Risk-based inspection of offshore topsides static mechanical equipment, DNV-GL, 2010.
[26] K. Suzuki, The study of inhibitor for sour gas service, NACE Corrosion. 7 (1982) 384–389.
[27] S. Ramachandran, et al., Molecular modeling of the inhibition of mild steel CO2 corrosion by imidazolines, NACE Corrosion. 17 (1998).
[28] Xu Ya-zhou, Liu Jian-guo, Li Zi-li, Research progress on corrosion inhibition of inhibitor in flow conditions, Equip. Environ. Eng. 14 (12) (2017) 19–23.
[29] Wang Bei, et al., Research on the impacts of wall shear stress on adsorption and desorption of corrosion inhibitors, Corros. Prot. 39 (supplement 1) (2018) 45–50.

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