IBP1089_19

CORROSION CHARACTERISTICS OF API 5L X65

STEEL IN HYDROUS ETHANOL FUEL
Célia A. L. dos Santos, Neusvaldo L. de Almeida1, Lorena
C. de O. Tiroel2, Vinícius de A. Jorge2, Élcio C. de
Oliveira2,3
Copyright 2019, Brazilian Petroleum, Gas and Biofuels Institute - IBP
This Technical Paper was prepared for presentation at the Rio Pipeline Conference and Exhibition 2019, held
between 03 and 05 of September, in Rio de Janeiro. This Technical Paper was selected for presentation by the
Technical Committee of the event according to the information contained in the final paper submitted by the
author(s). The organizers are not supposed to translate or correct the submitted papers. 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 and Exhibition 2019.

Abstract

There are some works in literature about ethanol fuel corrosiveness. They had already shown
anhydrous ethanol is weakly aggressive and some compounds like water, chloride ions and
acetic acid increased the ethanol fuel aggressiveness to carbon steel alloys. In this work,
hydrous ethanol fuel (7 % m/m) and carbon steel API 5L X65 were studied by stagnant
immersion tests and optical and electron microscopy. It was observed a general corrosion
during the first 24 h of exposure. After 48 h, it was possible to verify a few localized stains
and after 120 h, the stains became pits. After 720 h of exposure, the reddish color pits were
intensified but no new pits have arisen. The observed pits were larger in diameter than in
depth. This behavior favors the hydrous ethanol pipelines integrity because the depth of the
pits will not grow quickly which can decrease the risk of pipeline perforation. Although the
pits do not represent an imminent risk to the pipeline, care should be taken with long
interruption periods of the hydrous ethanol flow so that there is no nucleation or pitting
growth.
Keywords: Corrosion. Hydrous Ethanol Fuel. API 5L X65 Steel; Stagnant Immersion Tests.

1. Introduction

The Brazilian drive force to produce ethanol fuel was the petroleum crisis in 1970.
Nowadays, the most important aspect is that ethanol fuel is a clear energy and does not affect
the warming global because the CO2 production balance is positive to carbon fixation
(Wyman and Hinman, 1990).
Brazil has been developing a wide expertise with production, storage and distribution
of anhydrous and hydrous ethanol fuels since 1970. Anhydrous is mixed to gasoline and the
hydrous is marketed directly to the final consumer (Belicanta et al., 2016 e SANTOS et al.,
2018).
Anhydrous and hydrous ethanol fuels are storage on tanks and they are transported by
road, railroad and pipelines, the latter cannot be exclusive for ethanol fuel (Belicanta et al.,
2016).
______________________________
Instituto de Pesquisas Tecnológicas do Estado de São Paulo S. A. – IPT
2
PETROBRAS TRANSPORTE S. A. – TRANSPETRO
3
Postgraduate Programme in Metrology, Pontifical Catholic University of Rio de Janeiro
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Tanks and pipelines are generally built by carbon steel and the pipelines are built by a
specific kind of carbon steel, the API 5L grades (Soeiro Jr et al., 2013).
According to Moreira et al., the anhydrous ethanol fuel was not aggressive to API 5L
X46 and to API 5L X70 in both stagnant and non-stagnant conditions. The hydrous ethanol
was aggressive to API 5L X46 and to API 5L X70 in stagnant condition and nonaggressive in
non-stagnant condition (Moreira et al., 2010).
In the 1970s and 1980s Brazilian researches institutions became involved in
investigating the corrosiveness of hydrous ethanol and in one of these studies, Uller et al,
showed that carbon steel 1020 specimens have a low velocity corrosive process when
immersed in hydrous ethanol. in non-aerated conditions (Uller et al, 1981)
The aim of this work is to verify the behavior of hydrous ethanol fuel (7 % m/m)
related to carbon steel API 5L X65 during stagnant immersion tests and analyze the carbon
steel surfaces after the immersion tests by optical and electron microscopy to observe what
kind of corrosion can occur.

2. Experimental Procedure

Specimens of API 5L X65 and glass made immersion bottles were used during the
immersion tests. The test times were 24, 48, 120, 240, 360, 480, 600 and 720 hours. Dried
synthetic air passed through traps containing blue silica gel to absorb possible traces of
moisture before the specimens were introduced in the vials of immersion experiments, Figure
1.

Figure 1. Bottle of immersion with support screws for attachment of three specimens

The commercial hydrous was collected in “Terminal REPLAN” in September of 2018.

The API 5L X65 specimens were obtained from a pipeline by cutting and machining. The
specimens were initially identified by alphanumeric types, degreased with acetone, blasted
with glass bead until they reach the surface roughness Ry of 20 m to 25 m, followed by
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ultrasonic cleaning bath with anhydrous ethanol PA and drying under hot air flow. After
preparation of the surfaces, the specimens were kept 24 h in a desiccator for the subsequent
assembly of the immersion tests. The specimens shown about 23.0 cm2 and they were
weighed before and after the immersion tests in an analytical balance with a precision to
0.0001 g. Three API 5L X65 specimens were fixed by a bracket and screws made of Teflon®
according to Figure 1.
After the positioning of the specimens on the glass immersion bottles, they were
closed and purged with dried synthetic air. The ethanol was transferred to the immersion
bottle after being purged with dried synthetic air under the pressure of the same gas.
The API 5L X65 specimens were cleaned according to ASTM G1-2017 standard
(ASTM G1, 2017). After that, they were weighed and the corrosion rates were determined
according to ASTM G31-12a (ASTM G31, 2012). The surfaces of the specimens after the
tests were observed by a Confocal Microscope Zeiss and a Scanning Electronic Microscope
FEI-FEG Quanta 400, scanning electronic microscopy (SEM).

3. Results

Table 1 and Figure 2 present the API 5L X65 corrosion rates, the standard deviations
and the relative standard deviations obtained from the immersion tests in hydrous ethanol
fuel.

Table 1. API 5l X65 corrosion rate in hydrous ethanol fuel

Hydrous ethanol fuel – Corrosion rate
Standard deviation Relative standard
Immersion time (h) Average (mm/year)
(mm/year) deviation (%)
24 15.57 x 10-3 4.7 x 10-4 3.0
48 20.15 x 10-3 1.0 x 10-4 0.49
120 6.15 x 10-3 3.4 x 10-4 5.4
240 2.98 x 10-3 0.9 x 10-4 3.0
360 1.51 x 10-3 0.4 x 10-4 2.7
480 1.16 x 10-3 0.1 x 10-4 0.70
600 1.72 x 10-3 0.1 x 10-4 0.002
720 1.19 x 10-3 0.6 x 10-4 5.4

The corrosion rates had decreased over time, and they stabilized from 360 h of
immersion when the pits intensified. The tested period which showed the highest corrosion
rate was the first 48 h of immersion, Table 1.
It was observed a generalized corrosion in 24 h of immersion, Table 2. The rates
decreased with the increase of the hours probably due to the protective layer oxide formation
that was broken giving rise to pits formation. The corrosion rates became small with pits
formation and because of that it was verified a small loss of mass, Table 1.
As additional information, the hydrous ethanol fuel keeps colorless at the end of the
immersion tests.
The images of the specimens after the immersion tests with comments are presented in
Table 2.

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Table 2. Specimens’ images after immersion tests

Time (h) Specimen Comment

Without
24
stains

A few
48 corrosion
spots

A few
120 corrosion
spots

A few
240 corrosion
spots

Corrosion
360
spots

Corrosion
480
spots

Many
600 corrosion
spots

Corrosion
720 spots and
stain

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Hydrous ethanol fuel

0.035

0.030
Corrosion rate (mm/ano)

0.025

0.020

0.015

0.010

0.005

0.000
0 100 200 300 400 500 600 700 800 900

Time (h)

Figure 2. API 5l X65 corrosion rates in hydrous ethanol fuel

The biggest corrosion rate was 0.020 mm/year for 48 h of immersion, Figure 2. This
corrosion rate value is considered low corrosion according to PETROBRAS N-2785
standards:
 Low: < 0.025 mm/year.
 Moderate: from 0.025 mm/year to 0.125 mm/year.
 Severe: > 0.125 mm/year.

The width and depth measures of the pits were measured by Confocal Microscope.
These values are presented in Table 3 and the profiles are presented in Table 4.

Table 3. Width and depth values of the pits observed on API 5l X65 specimens after
immersion tests in hydrous ethanol fuel
Time (h) Specimen Pit width (m) Pit depth (m)
240 CP10 94.4 19.7
CP13 97.0 20.9
360
CP15 144.4 33.6
CP16 102.2 29.0
480
CP18 143.5 43.2
CP19 150.0 38.6
600 CP20 143.5 32.9
CP21 179.2 29.9

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The width of the pits values was from 3 to 6 times greater than the depth values, Table
3.

Table 4. Profile of the pits observed on API 5l X65 specimens after immersion tests in
hydrous ethanol fuel
Specimen /
Profile (µm)
Time (h)

CP10/240

CP13/360

CP15/360

CP16/480

CP18/480

CP19/600

CP20/600

CP21/600

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Table 4 shows the pits formed on the API 5L steel in hydrous ethanol had the width
greater than the depth and there was no evidence of pointed shapes pit.

(a) (b)

Figure 3. 3D images from pits obtained by Confocal Microscope (a) Specimen 18/480 h (b)
Specimen 20/600 h

(a) (b)

Figure 4. SEM images from pits (a) Specimen 18/480 h (b) Specimen 20/600 h

The images from Figure 3 and 4 show aggregate pits formation for 480 h and 600 h of
immersion.
These aggregated pits could be related to the API 5L X65. According to Pereira et al.
(2016), API 5L grade steels have high sulfide inclusions which are cathodic in related to
matrix. The latter suffers corrosion, the sulfides detached themselves and pits are created. Due
to a high level of inclusions, the formed pits join and raise an alveolar corrosion.

4. Conclusion
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In API 5L X65 carbon steel specimens studied in stagnant immersion tests with
hydrous ethanol, a generalized corrosion process was observed in the first 24 hours of
exposure. After 48h of exposure there is a reduction in generalized corrosion rates. Localized
corrosion was observed after 48h of exposure and the pits, evaluated by focal microscopy,
showed the width dimension greater than the depth in a ratio of 3 to 6 times. No pits with
sharp formations were observed, but on the contrary the width / depth ratio of the pits tends to
increase with the exposure time suggesting that alveolar corrosion predominates in specimens
that are exposed to hydrous ethanol longer.

5. Acknowledgements

The authors thank the TRANSPETRO-Fipt for financial support for this work. The
authors thank Fabiano Raymundo dos Santos, Juliana Pereira Flor and Renata Angelon
Brunelli for their assistance during tests and characterization of specimens.

6. References

ASTM - American Society for Testing and Materials. ASTM G1-03 (2017): Standard
Practice for Preparing, Cleaning, and Evaluating Corrosion Test Specimens. West
Conshohocken:ASTM International, 2017.
ASTM - American Society for Testing and Materials. ASTM G31-12a (2012): Standard
Guide for Laboratory Immersion Corrosion Testing of Metals. West Conshohocken:ASTM
International, 2012.
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etílico hidratado. 1981. 8p Relatório. Fundação de Tecnologia Industrial, 1981
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