Petroleum 6 (2020) 106–113

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Petroleum
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CO2 corrosion behaviors of 13Cr steel in the high-temperature steam T

environment
Guoqing Xiaoa,b,∗, SiZhou Tana, Zhiming Yub, Baojun Dongb, Yonggang Yic, Gang Tianc,
Huiyong Yuc, Shanzhi Shic
a
College of Chemical Engineering, Southwest Petroleum University, Chengdu, 610500, China
b
State Key Laboratory of Oil & Gas Reservoir Geology and Exploitation (Southwest Petroleum University), Chengdu, 610500, China
c
Research Institute of Engineering Technology, Xinjiang Oilfield Company, PetroChina, Karamay, 834000, China

ARTICLE INFO ABSTRACT

Keywords: The study aims to explore the corrosion behaviors of 13Cr steel in the high-temperature steam environment. The
CO2 auxiliary steam drive corrosion behaviors of 13Cr steel were tested in CO2 auxiliary steam drive environment simulated with the
Temperature HTHP autoclave. The corrosion morphology and product composition were explored by SEM, EDS, XRD and XPS.
Cl− concentration The exploration results showed the corrosion rate of 13Cr steel in the high-temperature steam environment was
Corrosion
less than 0.04 mm/a. The corrosion behaviors of 13Cr steel were mainly affected by temperature and chloride
13Cr steel
ion concentration. Temperature inhibited steam condensation and the compactness of Cr-rich layer. With the
increase in temperature, more droplets were adsorbed on the surface of 13Cr steel and the compactness of the Cr-
rich layer is worse. Chloride ions affects the activity of Fe atoms in the metal matrix. When chloride con-
centration increased, Fe2+ concentration in the solution and FeCO3 content in the rich-Cr layer were increased
and the rich-Cr layer became looser.

1. Introduction higher level of Cr should be adopted [6].

In previous studies on CO2 corrosion of 13Cr steel, only the water-
Industrial CO2 emissions largely lead to global warming. At present, phase environment was usually considered, but the effect of steam on
the main technology of emission reduction is CCUS (carbon capture, corrosion was seldom explored [7–9]. However, the injected medium is
utilization and storage). Currently, CCUS is mainly applied in CO2-EOR usually a mixture of steam and CO2. The steam is one of the important
drive recovery. CO2-EOR enhanced oil recovery technology not only factors affecting the corrosion behavior of the system. Therefore, if the
reduces CO2 emissions, but also increases the recovery rate of oil fields materials recommended in the wellbore specifications were adopted,
[1,2]. overestimated corrosion damage and high cost would be generated.
The viscosity of heavy oil in heavy oil reservoir formation can be 13Cr steel is widely used in oil and gas industry due to its good
decreased by injecting steam and a small quantity of CO2 into gas wells. corrosion resistance. The main factors influencing CO2 corrosion of
During steam injection, the wellbore temperature (160–220 °C) of gas 13Cr steel are temperature, CO2 partial pressure, velocity and Cl− ion
injection wells is high and injected CO2 cools the wellbore to generate concentration [10]. The corrosion behaviors of 13Cr steel were ex-
the water film on the inner wall of wellbore [3]. When steam injection tensively studied. Hua pointed that the general corrosion rate of 13Cr
stops, the temperature of wellbore gradually decreases and the water steel was less than 0.02 mm/a in water-saturated supercritical CO2
film is formed on the inner wall of wellbore. When CO2 is dissolved in environments with SO2/O2 [11]. However, the CO2 corrosion behaviors
water, carbonic acid is formed. Carbonic acid significantly increases the in the high-temperature steam environment were seldom explored
corrosion rate of tubing and casing steel and causes sweet corrosion [12,13].
[4,5]. The safe storage of CO2 problem in gas injection wells remains to The study aims to explore the corrosion behaviors of 13Cr steel in
be solved. According to the study results of the Kawasaki Heavy In- the high-temperature steam environment. The corrosion behaviors of
dustries and Sumitomo Metal Industries, when the temperature was 13Cr steel were tested in CO2 auxiliary steam drive environment si-
higher than 180 °C, stainless steel (22Cr and 25Cr steel) containing the mulated with the HTHP autoclave. In addition, the CO2 corrosion

Peer review under responsibility of Southwest Petroleum University.

∗
Corresponding author. College of Chemical Engineering, Southwest Petroleum University, Chengdu, 610500, China.
E-mail address: [email protected] (G. Xiao).

https://doi.org/10.1016/j.petlm.2019.12.001
Received 3 September 2019; Received in revised form 16 September 2019; Accepted 16 December 2019
2405-6561/ Copyright © 2020 Southwest Petroleum University. Production and hosting by Elsevier B. V. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/BY-NC-ND/4.0/).
G. Xiao, et al. Petroleum 6 (2020) 106–113

Table 1 Table 2
Chemical composition of 13Cr steel (wt.%). Test conditions.
Steel C Mn Cr Ni Cu P Si Fe Temperature (°C) CO2 Flow chloride Experimental Test
partial rate ion content medium time (h)
13Cr 0.22 0.75 13 0.5 0.25 0.02 1.00 Bal. pressure (m/s) (ppm)
(MPa)

160 2 – – deionized 72
mechanism in the high-temperature steam environment was discussed,
water
thus providing the basis for the application of 13Cr steel in gas injec- 180 2 – – – 72
tion. 200 2 – – – 72
220 2 – – – 72

2. Experiments 160 1 – – – 72
160 3 – – – 72
2.1. Materials and solutions 160 4 – – – 72

160 2 3 – – 72
The 13Cr steel was selected as the experimental material. The 160 2 4.5 – – 72
chemical composition of 13Cr steel specimen is listed in Table 1. Ac- 160 2 6 – – 72
cording to the ASTM standards, the testing specimens were machined
160 2 – 1000 ppm Formation 72
into a size of 30×15×3 mm. The surface of each specimen was po-
water
lished with 1200# silicon sandpaper to eliminate scratches. The po- 160 2 – 2000 ppm Formation 72
lished specimens were cleaned with anhydrous ethanol, degreased with water
acetone, finally dried in the air and stored in the desiccator for 2 h. The 160 2 – 3000 ppm Formation 72
weight of the specimen was taken using an analytical balance with the water

accuracy of 0.1 mg.

The experimental medium was deionized water. Before the experi-
removed according to ASTM Standard G1-03. Then the specimens were
ment, purified CO2 was bubbled into deionized water to purge oxygen
weighed on an electronic balance with the precision of 0.1 mg. The
for 12 h.
general corrosion rates were calculated with Eq. (1) [14].
m
2.2. Weight loss test v = 87600
A t (1)
The experiments were conducted in a self-machined HTHP auto- where v is corrosion rate (mm/a); m is the weight loss (g); is the
clave (Fig. 1). Firstly, 60 mL of deoxidized deionized water was added density of steel (g/cm3); A is the surface area (cm2); t is corrosion
into the autoclave. The specimens were hung on the specimen holders, time (h).
which were then placed above the liquid level. The autoclave was The other specimen was washed with deionized water, dehydrated
sealed and purged with CO2 for 2 h at a low flow rate. The experiment with alcohol, and dried in air. The surface morphology of the dried
temperature and flow rate were respectively set after oxygen removal. specimen was analyzed with SEM (JSM-7500F) and its chemical com-
When the experimental temperature raised to the required temperature, position of the corrosion scale was determined with XRD (XPert Pro
CO2 was purged into the autoclave by using a booster pump. The cor- MPD) and XPS (Phi-Quantera II).
rosion experiments were performed for 72 h.
After corrosion experiments, four parallel specimens were taken out 2.3. Testing scheme
from the autoclave. The three specimens were cleaned immediately by
deionized water followed with alcohol. The corrosion products were The main corrosion factors of injection wells were temperature, CO2

Fig. 1. Schematic diagram of dynamic HTHP autoclave.

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Fig. 2. Corrosion rates of 13Cr steel.

pressure, flow rate and chloride ion content. According to the statistical concentration was 3000 ppm, many corrosion products were observed
data of gas injection wells, the experimental scheme is listed in Table 2. on the specimen surface.
Fig. 6 was the SEM images (×10000) of 13Cr steel under different
3. Results flow rate. Corrosion scales were damaged. Cubic crystals occurred on
the specimen surface. EDS and XPS results indicated that the cubic
3.1. Weight loss corrosion rate crystals were FeCO3.

Fig. 2 shows the corrosion rates of 13Cr steel at various tempera-

tures. The corrosion rates of 13Cr steel were lower than 0.04 mm/a, 3.3. XRD analysis
indicating that 13Cr steel had the good corrosion resistance. Among all
the corrosion factors, temperature and Cl− content had a great influ- Fig. 7 shows the XRD results of steel. Only Fe peaks were detected.
ence on the corrosion of 13Cr steel (Fig. 2). Xu also pointed out that these base metal peaks were detected because
the layer formed on the steel surface was thin. Xu reported similar re-
3.2. SEM observation and EDS analysis sults that the corrosion scales of steel were thin in the high-temperature
steam environment [10].
Fig. 3 shows the SEM images (×100) of 13Cr steel at various tem-
peratures. From Fig. 3a–d, the corrosion of specimen was slight. The
circled corrosion products appeared on the surface of specimens. As the 3.4. XPS analysis
temperature increased, the corrosion products on the surface of speci-
mens increased. To further confirm the chemical composition of corrosion scales, the
Fig. 4 shows the SEM images (×10000) of 13Cr steel at various XPS test was conducted with the specimen. Fig. 8 shows the XPS result
temperatures. The corresponding EDS results are provided in Table 3. of 13Cr steel under conditions (160 °C and 2 MPa CO2). The O peaks at
From Fig. 4, the circular corrosion products were scattered on the 530.7 ev and 531.8 ev (Fig. 8a) were ascribed to O2− components. The
specimen surface. The compact and integrated corrosion scales covered O1s peak was related to the presence of FeCO3, Fe2O3, and Cr2O3 [15].
the specimen surface. The cubic corrosion products were existed on the The C peak at 289.6 ev corresponded to adventitious carbon (Fig. 8b). A
surface of specimen. The corrosion products mainly included FeCO3 and couple of Cr2p3/2 (577.3 ev) and Cr2p1/2 (587.1 ev) peaks were as-
Cr(OH)3, as indicated in the XPS analysis results in Fig. 8. The Cr cribed to Cr(OH)3 and Cr2O3 (Fig. 8c). A pair of Fe2p3/2 and Fe2p1/2
content of corrosion products was slightly higher than that in the metal peaks at 724.02 ev, 710.61 ev were observed (Fig. 8d). The XPS results
matrix. of 13Cr steel indicated that the main components of the passive film
Fig. 5 shows the SEM images (×100) of 13Cr steel under various were FeCO3, Fe2O3, Cr(OH)3, and Cr2O3.
chloride concentrations. The corrosion of specimens was slight. The
scratches on the specimen surface were obvious. When the chloride ion

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Fig. 3. SEM images (×100) of 13Cr steel at various temperatures. (a: 160 °C; b: 180 °C; c: 200 °C; d: 220 °C).

Fig. 4. SEM image (×10000) of 13Cr steel at various temperatures. (a: 160 °C; b: 180 °C; c: 200 °C; d: 220 °C).

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Table 3
EDS results of 13Cr Steel at different temperatures.
Temperatures Elements

Zones C O Si Cr Fe

160 °C 7.28 6.48 0.71 15.02 70.51

180 °C 4.72 3.06 0.61 14.16 72.88
200 °C Zone A 3.95 2.06 0.06 10.79 75.26
Zone B 3.95 2.06 0.06 15.21 73.26
220 °C 4.62 4.40 – 14.19 77.20

4. Discussions

4.1. Corrosion reactions of 13Cr steel

During the corrosion of 13Cr steel in a high-temperature steam

environment containing CO2, water was first absorbed on the steel
surface to form a thin water film.
CO2 is dissolved in water film to form H2CO3 (Eq. (2)). H2CO3 is
further decomposed to generate HCO3−, CO32− and H+. Cathodic re-
actions of the water film are provided as Eq. (3)- Eq. (5) [16,17]. Fig. 7. XRD spectra of corrosion films of 13Cr steel.

CO2 (g ) + H2 O H2 CO3 (2)

(9)) [18]:
2H2 CO3 + 2e 2HCO3 + H2 (3)
Cr 3 + + 3H2 O C r(OH )3 + 3H+ (8)
2HCO3 + 2e 2CO32 + H2 (4)
2Cr (OH )3 Cr2 O3 + 2H2 O (9)
2H+ + 2e H2 (5)
+
H ion is produced by the hydrolysis of Cr, thus reducing the pH
Anodic reactions involve the iron dissolution (Eq. (6) and Eq. (7)):
value of the solution and promoting the rapid dissolution of Fe2+. Lots
Fe F e2 + + 2e (6) of Fe2+ accumulates in the amorphous Cr(OH)3 layers. When the con-
tents of Fe2+ and CO32− are above the solubility of FeCO3, will FeCO3
Cr Cr 3 + + 2e (7)
precipitates on steel surface (Eq. (10)-Eq. (12)). According to Chen's
XPS results showed that the corrosion products were mainly FeCO3, report, when the Cr content in steel exceeded 3%, a Cr-rich layer was
Cr(OH)3, Fe2O3 and Cr2O3. The Ksp of Cr(OH)3 was much lower than formed on the surface of steel. The formation of Cr(OH)3 decreased the
that of FeCO3, so Cr(OH)3 rapidly reached the saturation state and pH value of the solution near the Cr-rich layer, further accelerating the
amorphous Cr(OH)3 was formed on the surface of substrate (Eq. (8)-Eq. dissolution of FeCO3.

Fig. 5. SEM images (×100) of 13Cr steel under different chloride concentrations. (a:1000 ppm; b: 2000 ppm; c: 2000 ppm).

Fig. 6. SEM images (×100) of 13Cr steel under different flow rate. (a: 3 m/s; b: 4.5 m/s; c: 6 m/s).

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Fig. 8. XPS of 13Cr steel after corrosion at 160 °C under 2 MPa CO2: (a) o, (b) C, (C) Cr, (d) Fe.

F e2 + + CO32 F eCO3 (10) 4.2. Influence of temperature

F e2 + + 2HCO3 F e(HCO3) 2 (11) When the steam was cooled, it was condensed on the specimen
surface. The specimens were corroded at the condensed area. With the
F e(HCO3) 2 F eCO3 + CO2 + H2 O (12)
temperature increase, corrosion products on the specimen increased,
FeCO3 was decomposed into FeO at high temperature (Eq. (13)). indicating that temperature affected the quantity of adsorbed water on
When the specimens were taken out from the autoclave, FeO were the specimen surface. Steam absorbed a lot of heat during the con-
oxidized in the air to form Fe2O3 (Eq. (14)). Cr2O3 was generated from densation process. The higher temperature resulted in more condensed
the dehydration of Cr(OH)3 (Eq. (15)). steam on the specimen surface.
Lin indicated that the formation of the Cr-rich layer was ascribed to
F eCO3 F eO + CO2 (13)
the competition between Cr(OH)3 and FeCO3. Fig. 9 shows the influ-
4F eO + O2 2F e2 O3 (14) ence of temperature on the corrosion of 13Cr steel. Temperature mainly
affected the ratio of Cr(OH)3 to FeCO3 in the Cr-rich layer. The solu-
2Cr (OH )3 Cr2 O3 + 2H2 O (15) bility of Cr(OH)3 (Ksp = 6.3 × 10−31) was far less than that of FeCO3

Fig. 9. Influence of temperature on the corrosion of 13Cr steel.

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Fig. 10. Schematic diagram of chloride ion activation mechanism.

(Ksp = 3.13 × 10−11). The content of Cr(OH)3 in the Cr-rich layer was Acknowledgements
much higher than that of FeCO3 at low temperature [19]. The Cr-rich
layer could prevent anions such as CO32− and HCO3− from penetrating The research was financially supported by the National Science and
through the Cr-rich layer to react with the matrix. The Cr-rich layer Technology Major Project of China (Grant No. 2016ZX05012-001).
could also inhibit the active dissolution of Fe [20]. The active dis-
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