Effect of Temperature on the Corrosion Behaviours of L360QCS in the Environments Containing Elemental Sulphur and H₂S/CO₂
The effect of temperature on the corrosion behaviours of L360QCS in H₂S, CO₂ and elemental sulphur environments are investigated. The corrosion weight-loss rate, microscopy, chemical compositions and phase compositions of corrosion products are studied by means of the weight-loss analysis, SEM and X...
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Інститут металофізики ім. Г.В. Курдюмова НАН України
2012
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nasplib_isofts_kiev_ua-123456789-1677032025-02-09T16:00:32Z Effect of Temperature on the Corrosion Behaviours of L360QCS in the Environments Containing Elemental Sulphur and H₂S/CO₂ Влияние температуры на режимы коррозии L360QCS в средах, содержащих атомарную серу и H₂S/CO₂ Shuqi Zheng Chunyu Li Changfeng Chen Дефекты кристаллической решётки The effect of temperature on the corrosion behaviours of L360QCS in H₂S, CO₂ and elemental sulphur environments are investigated. The corrosion weight-loss rate, microscopy, chemical compositions and phase compositions of corrosion products are studied by means of the weight-loss analysis, SEM and XRD techniques. As shown, the corrosion rate increased greatly with an increase of the temperature, and the corrosion scale is dropped off easily because of the weak adhesion force between the matrix and the corrosion products. The composition and structure analysed by energy-dispersive x-ray spectroscopy (EDS) and XRD show that the corrosion product scales are composed of cubic FeS and little tetragonal FeS. Исследовано влияние температуры на режимы коррозии L360QCS в атмосферах H₂S, CO₂ и атомарной серы. Скорость коррозии, измеряемая по потере веса, микроскопия, химический и фазовый состав продуктов коррозии определялись анализом потери веса, СЭМ и рентгеноструктурным анализом (РСА). Показано, что скорость коррозии сильно возрастает с температурой, и коррозионная окалина легко отпадает благодаря слабой силе адгезии между матрицей и продуктами коррозии. Исследования состава и структуры методами рентгеноспектрального электронно-зондового микроанализа и РСА показали, что окалины продуктов реакции состоят из кубического FeS и небольшой части тетрагонального FeS. Досліджено вплив температури на режими корозії L360QCS в атмосфері H₂S, CO₂ та атомарної сірки. Швидкість корозії, яка вимірюється за втратами ваги, мікроскопія, хемічний та фазовий склад продуктів корозії визначалися аналізою втрати ваги, СЕМ та рентґеноструктурною аналізою (РСА). Показано, що швидкість корозії сильно збільшується з температурою, і корозійна жужелиця легко відпадає через слабку силу адгезії між матрицею та продуктами корозії. Дослідження складу та структури методами рентґеноспектральної електронно-зондової мікроаналізи та РСА показали, що жужелиці продуктів реакції складаються з кубічного FeS та незначної частки тетрагонального FeS. This study is funded by the National Nature Science Foundation of China (No. 50871122). 2012 Article Effect of Temperature on the Corrosion Behaviours of L360QCS in the Environments Containing Elemental Sulphur and H₂S/CO₂ / Shuqi Zheng, Chunyu Li, Changfeng Chen // Металлофизика и новейшие технологии. — 2012. — Т. 34, № 1. — С. 57-63. — Бібліогр.: 8 назв. — англ. 1024-1809 PACS numbers:61.72.Dd, 61.72.Ff,61.72.Hh,68.35.Np,68.37.Hk,81.65.Kn, 82.45.Bb https://nasplib.isofts.kiev.ua/handle/123456789/167703 en Металлофизика и новейшие технологии application/pdf Інститут металофізики ім. Г.В. Курдюмова НАН України |
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Дефекты кристаллической решётки Дефекты кристаллической решётки |
| spellingShingle |
Дефекты кристаллической решётки Дефекты кристаллической решётки Shuqi Zheng Chunyu Li Changfeng Chen Effect of Temperature on the Corrosion Behaviours of L360QCS in the Environments Containing Elemental Sulphur and H₂S/CO₂ Металлофизика и новейшие технологии |
| description |
The effect of temperature on the corrosion behaviours of L360QCS in H₂S, CO₂ and elemental sulphur environments are investigated. The corrosion weight-loss rate, microscopy, chemical compositions and phase compositions of corrosion products are studied by means of the weight-loss analysis, SEM and XRD techniques. As shown, the corrosion rate increased greatly with an increase of the temperature, and the corrosion scale is dropped off easily because of the weak adhesion force between the matrix and the corrosion products. The composition and structure analysed by energy-dispersive x-ray spectroscopy (EDS) and XRD show that the corrosion product scales are composed of cubic FeS and little tetragonal FeS. |
| format |
Article |
| author |
Shuqi Zheng Chunyu Li Changfeng Chen |
| author_facet |
Shuqi Zheng Chunyu Li Changfeng Chen |
| author_sort |
Shuqi Zheng |
| title |
Effect of Temperature on the Corrosion Behaviours of L360QCS in the Environments Containing Elemental Sulphur and H₂S/CO₂ |
| title_short |
Effect of Temperature on the Corrosion Behaviours of L360QCS in the Environments Containing Elemental Sulphur and H₂S/CO₂ |
| title_full |
Effect of Temperature on the Corrosion Behaviours of L360QCS in the Environments Containing Elemental Sulphur and H₂S/CO₂ |
| title_fullStr |
Effect of Temperature on the Corrosion Behaviours of L360QCS in the Environments Containing Elemental Sulphur and H₂S/CO₂ |
| title_full_unstemmed |
Effect of Temperature on the Corrosion Behaviours of L360QCS in the Environments Containing Elemental Sulphur and H₂S/CO₂ |
| title_sort |
effect of temperature on the corrosion behaviours of l360qcs in the environments containing elemental sulphur and h₂s/co₂ |
| publisher |
Інститут металофізики ім. Г.В. Курдюмова НАН України |
| publishDate |
2012 |
| topic_facet |
Дефекты кристаллической решётки |
| url |
https://nasplib.isofts.kiev.ua/handle/123456789/167703 |
| citation_txt |
Effect of Temperature on the Corrosion Behaviours of L360QCS in the Environments Containing Elemental Sulphur and H₂S/CO₂ / Shuqi Zheng, Chunyu Li, Changfeng Chen // Металлофизика и новейшие технологии. — 2012. — Т. 34, № 1. — С. 57-63. — Бібліогр.: 8 назв. — англ. |
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Металлофизика и новейшие технологии |
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57
PACS numbers:61.72.Dd, 61.72.Ff,61.72.Hh,68.35.Np,68.37.Hk,81.65.Kn, 82.45.Bb
Effect of Temperature on the Corrosion Behaviours of L360QCS
in the Environments Containing Elemental Sulphur and H2S/CO2
Shuqi Zheng, Chunyu Li, and Changfeng Chen
China University of Petroleum,
Department of Materials Science and Engineering,
102249 Beijing, China
The effect of temperature on the corrosion behaviours of L360QCS in H2S,
CO2 and elemental sulphur environments are investigated. The corrosion
weight-loss rate, microscopy, chemical compositions and phase compositions
of corrosion products are studied by means of the weight-loss analysis, SEM
and XRD techniques. As shown, the corrosion rate increased greatly with an
increase of the temperature, and the corrosion scale is dropped off easily be-
cause of the weak adhesion force between the matrix and the corrosion prod-
ucts. The composition and structure analysed by energy-dispersive x-ray
spectroscopy (EDS) and XRD show that the corrosion product scales are com-
posed of cubic FeS and little tetragonal FeS.
Досліджено вплив температури на режими корозії L360QCS в атмосфері
H2S, CO2 та атомарної сірки. Швидкість корозії, яка вимірюється за втра-
тами ваги, мікроскопія, хемічний та фазовий склад продуктів корозії ви-
значалися аналізою втрати ваги, СЕМ та рентґеноструктурною аналізою
(РСА). Показано, що швидкість корозії сильно збільшується з температу-
рою, і корозійна жужелиця легко відпадає через слабку силу адгезії між
матрицею та продуктами корозії. Дослідження складу та структури мето-
дами рентґеноспектральної електронно-зондової мікроаналізи та РСА по-
казали, що жужелиці продуктів реакції складаються з кубічного FeS та
незначної частки тетрагонального FeS.
Исследовано влияние температуры на режимы коррозии L360QCS в атмо-
сферах H2S, CO2 и атомарной серы. Скорость коррозии, измеряемая по по-
тере веса, микроскопия, химический и фазовый состав продуктов корро-
зии определялись анализом потери веса, СЭМ и рентгеноструктурным
анализом (РСА). Показано, что скорость коррозии сильно возрастает с
температурой, и коррозионная окалина легко отпадает благодаря слабой
силе адгезии между матрицей и продуктами коррозии. Исследования со-
става и структуры методами рентгеноспектрального электронно-зондово-
го микроанализа и РСА показали, что окалины продуктов реакции состо-
Металлофиз. новейшие технол. / Metallofiz. Noveishie Tekhnol.
2012, т. 34, № 1, сс. 57—63
Оттиски доступны непосредственно от издателя
Фотокопирование разрешено только
в соответствии с лицензией
© 2012 ИМФ (Институт металлофизики
им. Г. В. Курдюмова НАН Украины)
Напечатано в Украине.
58 Shuqi ZHENG, Chunyu LI, and Changfeng CHEN
ят из кубического FeS и небольшой части тетрагонального FeS.
Key words: elemental sulphur, corrosion, L360QCS, microstructure.
(Received July 9, 2011)
1. INTRODUCTION
More and more sour oil and gas fields containing higher partial pres-
sure H2S and CO2 are being exploited for sweet fields being depleted
and higher oil price. The pipeline used in the environments containing
high pressure H2S are often corroded, especially in the case of ele-
mental sulphur existence in the environment. The sulphur will be dis-
solved out in high H2S partial pressure environment as the solubility of
sulphur in solution decreases with the decrease of pressure and tem-
perature from bottom to top of oil or gas reservoir [1]. The corrosion
problem is the key point to the development of acid gas or oil fields in
the environment containing high H2S/CO2 pressure, elemental sul-
phur, and salinity brine.
A concern in the production and transportation sour oil and gas is
the corrosion caused by the acid gases CO2 and H2S. Many measure-
ments have been taken to mitigate H2S and CO2 corrosion, such as us-
ing corrosion inhibitor, stainless steel and resistant HIC pipeline [2—
5]. At present, carbon steel is in general more cost-effective for oil and
gas facilities and hence is the most widely used material option [1].
However, a few reports involve in the role of the temperature in the
corrosion of L360QCS in the environment of H2S/CO2 and salinity
brine as well as elemental sulphur existence.
L360QCS is one of the low alloy carbon steels, which are widely used
in the gathering system in oil or gas field containing H2S and CO2 gas-
es. Its service temperature is almost lower than 90°C, which is below
the sulphur melting point (112.8°C). Therefore, in a given paper, the
effect of temperature on the L360QCS corrosion was studied below
90°C.
2. EXPERIMENTAL
The test samples were cut from L360QCS pipeline steel. Their chemical
compositions (wt.%) are as follow: C–0.13, Si–0.4, Mn–1.5, P–
0.02, S–0.003, Cr–0.03, Mo–0.1, Ni–0.3, Ti–0.04, Fe–balance.
The metallographic structure of L360QCS is tempered sorbitol.
The test solution was prepared by simulating some oil gas field in
China. The total mineralization of the solution is 67900 mg/l, and the
mass concentration of cations is 2.61⋅104
mg/l, while the anionic mass
EFFECT OF TEMPERATURE ON THE CORROSION BEHAVIOURS OF L360QCS 59
concentration is 4.18⋅104
mg/l. The water type is CaCl2 with the
pH 7.97. The H2S and CO2 partial pressures are 1.5 MPa and 1.0 MPa,
respectively. The elemental sulphur was used at the ratio of 10 g per
litre solution to simulate the deposited environment. The corrosion be-
haviours of L360QCS at different temperatures were studied. The
simulation experiments were conducted during 72 hours at 30°C, 50°C
and 90°C.
Three standard corrosion coupons are cut from L360QCS pipeline.
Each coupon was polished to 800 grits abrasive paper. The samples
were carefully weighted after acetone washing. The corrosion progress
with no oxygen participation is run at the high temperature and high-
pressure reaction autoclave, in which a special holder fixes the sam-
ples.
After the experiment, the samples were taken out from the reaction
autoclave and cleaned with ethyl alcohol before drying. The corrosion
weight loss method is used to research the effect of temperature on the
corrosion behaviours of L360QCS in the environments containing ele-
mental sulphur and H2S/CO2, and SEM, EDS and XRD are used to ana-
lyse the corrosion production scales.
3. RESULT AND DISCUSSION
3.1. Effect of Temperature on the Corrosion Rate
Figure 1 shows the corrosion rate of L360QCS at different tempera-
tures. It was shown that the corrosion rate of L360QCS increased
quickly with the increase of test temperature. The rate is 14 mm/a at
30°C, it reaches 50.5 mm/a at 50°C, and the rate rushes to 120.9 mm/a
at 90°C. Therefore, in the wet H2S/CO2 environment with 10 g/l ele-
Fig. 1. The corrosion rates of L360QCS at different temperatures.
60 Shuqi ZHENG, Chunyu LI, and Changfeng CHEN
mental sulphur, the increase of temperature speeded up the corrosion
rate rapidly even at the temperature lower than sulphur melting point.
The accelerated corrosion rate was also certificated by means of elec-
trochemical method with the temperature increasing from 30°C to
80°C in sulphide corrosion environment [6]. The temperature raises
the slope coefficient of Tafel anticathode curve. Meanwhile, the cath-
ode reaction changed and the corrosion potential became more positive.
Therefore, the temperature improves both anode and cathode reac-
tions.
3.2. Effect of Temperature on Macromorphology
From the results above, we found that the temperature greatly affect-
ed the corrosion behaviours of carbon steel in the environment. Fig-
ure 2 shows the macromorphology of corrosion production of L360QCS
at different temperatures and Fig. 3 shows the macromorphology of
the matrix of homologous samples. It was shown that there was an ob-
vious change in the corrosion shape with the increase of the tempera-
ture, the sample shape can keep the pervious shape after the corrosion
at 30°C. However, it was far different from the basics shape after cor-
rosion at 90°C.
It was also found that the morphologies of corrosion products are
different at different temperatures. At the temperature of 30°C, the
scale of corrosion production is very thin but compact, and it is not
easy to exfoliate. There is lots of pitting on the surface of matrix, espe-
cially on the region around the edge of the sample. When it comes to
50°C, the scale becomes thicker, but much of the corrosion products
exfoliate from the matrix, the inner layer is much more looser and
thinner than those of at 30°C. The corrosion took on a uniform corro-
sion characteristics. When the temperature is raised to 90°C, the cor-
rosion reaction is much more acute, most of the corrosion products
dropped off from the sample. From the picture (c) in Fig. 2, we can see
that there is only about a half of the sample left for the heavy corro-
Fig. 2. The macromorphology of corrosion products of L360QCS formed at
different temperatures: 30°C (a), 50°C (b), 90°C (c).
EFFECT OF TEMPERATURE ON THE CORROSION BEHAVIOURS OF L360QCS 61
sion.
3.3. Effect of Temperature on Micromorphology and Composition
In order to study the effect of temperature on micromorphology and
composition of corrosion products of L360QCS, SEM and EDS were
used to investigate the corrosion products. The micromorphology of
the corrosion products on the surface of L360QCS formed at different
temperatures is shown in Fig. 4.
At 30°C, the corrosion production scales are very flat and adhere to
the matrix tightly. However, there are many irregular potholes in the
film. When it comes to 50°C, the corrosion product scale becomes
thicker, but the bond of the film is so weak that the part of corrosion
scale is dropped off. From Fig. 4, it was found that the corrosion scales
were composed of two layers. The outer layer can be easily torn off and
the inner one is too thin and loose to protect the matrix of the sample,
but the compositions are nearly the same. The outer layer is much more
compact and consisting of regular FeS crystals. When the temperature
reaches 90°C, the adhesive force between the corrosion production and
matrix turns weaker, so, almost all of the products are dropped off.
Fig. 3. The macromorphology of matrix after removing the corrosion products
L360QS formed at different temperatures: 30°C (a), 50°C (b), 90°C (c).
Fig. 4. The micromorphologies of corrosion products L360QS formed at dif-
ferent temperatures: 30°C (a), 50°C (b), 90°C (c).
62 Shuqi ZHENG, Chunyu LI, and Changfeng CHEN
3.4. Effect of Temperature on the Structure of the Corrosion Produc-
tion
The phase compositions of the corrosion production were analysed by
x-ray diffraction. The results of the x-ray diffraction are shown in
Fig. 5. The corrosion production of L360QCS pipeline are similar at
different temperatures, which are composed of cubic crystal structure
FeS and little square crystal structure FeS.
The corrosion of carbon steel in the environment of H2O/CO2 with-
out sulphur has been researched by G. Firro [7] and K. Masamura [8].
If
2 2CO H S
200P P < , the corrosion is mainly H2S attacked. FeS film will
be the first produced when the carbon steel is dipped into the corrosion
solution, which will prevent the formation of FeCO3 film. In our test,
2 2CO H S
1.0 1.5 0.67P P = = . Therefore, the corrosion reaction is mainly
H2S attacking especially in the environment containing sulphur depo-
sition. The results of our test confirmed the point and there is no FeCO3
in the production.
4. CONCLUSIONS
1. When the temperature is lower than sulphur melting point, the cor-
rosion rate of L360QCS increases linearly dependent on the tempera-
ture.
2. At a higher temperature, the corrosion scale turn thicker and the
adhesive force between the corrosion scale and metal matrix turns
weaker.
3. At low temperature, the corrosion type is mainly local corrosion,
when it comes to 50°C, the corrosion type becomes an uniform attack;
at higher temperature of 90°C there are many corrosion grooves on the
Fig. 5. XRD pattern of L360QCS after corrosion at different temperatures:
30°C (a), 50°C (b).
EFFECT OF TEMPERATURE ON THE CORROSION BEHAVIOURS OF L360QCS 63
sample surface.
4. The results of XRD show that the corrosion products are composed
of cubic FeS crystal and less tetragonal FeS crystal. Temperature has
little effect on the chemical composition of the corrosion production.
ACKNOWLEDGMENT
This study is funded by the National Nature Science Foundation of
China (No. 50871122).
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