Preprints202202 0319 v1
Preprints202202 0319 v1
Preprints202202 0319 v1
v1
Article
a Tubular Goods Research Institute, China National Petroleum Corporation, State Key Laboratory for Perfor-
mance and Structure Safety of Petroleum Tubular Goods and Equipment Materials, Shaanxi Xi’an 710065,
China;
b. Department of Applied Chemistry, School of Science, Northwestern Polytechnical University, Xi'an 710072,
China;
Abstract:The three-phase separator was perforated after four years’ service. The perforation posi-
tion is at the bottom of the vessel under the baffle plate in an oil transfer station. In order to find out
the causes of corrosion and perforation of the vessel, it was investigated by chemical analysis using
a direct-reading spectrometer, microstructure examined by optical microscope(OM), and lab simu-
lated corrosion experiments by electrochemical workstation, and the corrosion products examined
with scanning electron microscopy(SEM), energy dispersive spectrometer(EDS) in this paper. The
analyses indicated that the coating at the base of the pressure vessel failed and this led to the direct
exposure of the carbon steel plate to the corrosive medium. The reason for the corrosion and perfo-
ration is that base material in the concealed place of the vessel contacts with the medium directly
and corrodes due to coating failure. If the vessel carbon steel connects with the baffle plate stainless
steel to form a hetero-metallic couple in the corrosive medium, the vessel inner wall’s corrosion will
be further accelerated.
1. Introduction
Oil is a kind of non-renewable resources, it exploited out from the deep stratum of
earth will inevitably carries out some formation water and associated gas. Three-phase
separator is used for separating the produced wellhead fluids into gas, oil and water by
their density difference. Because of the existence of CO2 and H2S acidic gas media in the
gaseous products, highly mineralized produced water, especially the chloride ion. After
four years’ service, a three-phase separator’s bottom was perforated. A 30×50 mm perfo-
ration was found in the bottom plate, and the thickness of the plate near the perforation
position is seriously reduced, as shown in Fig. 1. There are two three-phase separators in
the oil transfer station. The crude oil separated from the separators is heated by the heat-
ing furnace and then pumped to the combined station. The oil transfer station is the main
block of the joint station, producing 900 t/d of oil. The produced water is about 300m3/d
and is injected back in stratum.
Baffle plate
The plate of the vessel is made of Q245R carbon steel with a thickness of 12 mm.
Samples were taken from the etched and perforated bottom plate of the vessel as shown
in Fig. 2(a), marked as hole A. The baffle plates made by 316L stainless steel with a thick-
ness of 0.5 mm as shown in Fig. 2(b).
(a) (b)
Hole A
50 mm Baffle plate
Figure 2. Failure samples of three-phase separator. (a) The perforated bottom plate of the vessel; (b)
The 316L stainless steel baffle plates.
Metal made equipment were corroded by hydrogen sulfide has been investigated in
some of the literatures[1-3], other researchers also studied the vessels and pipe chloride-
induced corrosion[4] and stress assisted corrosion[5-7]. Although, many scholars studied
the three-phase separator were about the designation through computational fluid dy-
namics[8-11], simulate the internal flow field of the three-phase separator[12] and detec-
tion technology[13]. However, the corrosion of a three-phase separator is rarely been stud-
ied. In this paper, we studied a three-phase separator perforation in the bottom of the
vessel, which corroded by the medium environment containing hydrogen sulfide, carbon
dioxide, oxygen, and chloride ions [14-17].
The objective of this work is to find out the causes of corrosion and perforation of the
vessel, the physical and chemical properties and corrosion resistance of the samples were
tested comprehensively. According to the test results, combined with the field service con-
ditions for comprehensive analysis, finally find out the cause of failure and put forward
suggestions.
2. Experimental
In order to find out the corrosion cause of the three-phase separator, a series of ex-
periments were carried out. According to GB/T 4336-2016 standard[18], the chemical com-
position samples were taken from the perforated vessel bottom plate was analysis by
ARL4460 photoelectric direct reading spectrometer. The perforated vessel bottom plate
Preprints (www.preprints.org) | NOT PEER-REVIEWED | Posted: 25 February 2022 doi:10.20944/preprints202202.0319.v1
sample was cut and prepared for the metallurgical examination. The MeEF4M metallo-
graphic microscope and image analysis system were used to observe the microstructure
and grain size of the perforated vessel bottom plate.
To study the corrosion mechanism of the sample in service-environment, the high-
temperature high-pressure autoclave was utilized to simulate the corrosion behavior of
the of failure vessel samples in the laboratory[19] as shown in Fig. 3. The specific ion con-
centration is shown in Table 1. The simulated solution was prepared by using deionized
water and pure grade chemical reagents (Na2SO4, NaHCO3, NaCl, CaCl2, KCl, MgCl2, and
SrCl2) to prepare the simulated solution. The pH value of the simulated solution was fitted
by using dilute hydrochloric acid or sodium hydroxide solution. The exact simulation test
parameters are given in Table 2.
Corrosion simulation test samples were taken from the vessel bottom plate, with
sampling specifications of 50 mm×10 mm×3 mm. As the baffle plate is relatively thin, the
hanging specimens were taken from the baffle plate with a length of 50 mm and a width
of 10 mm, so the two kind of samples’ area are almost the same. Use tin-welded and cop-
per wire to connect the different material hanging specimen, and the welding end is sealed
with silica gel.
The electrochemical workstation was used to test the open-circuit potential (OCP) of
the Q245R carbon steel sample, 316L stainless steel sample, and Q245R carbon steel and
316L stainless steel coupling sample were tested at 40℃ and saturated carbon dioxide
Preprints (www.preprints.org) | NOT PEER-REVIEWED | Posted: 25 February 2022 doi:10.20944/preprints202202.0319.v1
respectively. Besides, the dynamic potential polarization curves of Q245R carbon steel
sample and 316L stainless steel sample were tested either. The potential scanning param-
eters of OCP are given in Table 3.
Finally, the samples near the perforation site of the bottom plate were analyzed by
TESCAN VEGA3 XMU scanning electron microscope (SEM) energy dispersive spectrom-
eter (EDS).
Element C Si Mn P S Cr Mo Ni Nb V Ti Cu Al
GB 713-2014 ≤0.20 ≤0.35 0.50~0.10 ≤0.03 ≤0.01 ≤0.03 ≤0.03 ≤0.08 ≤0.05 ≤0.05 ≤0.03 ≤0.03 ≥0.02
Measured 0.13 0.21 0.53 0.015 <0.008 <0.1 <0.03 0.011 <0.02 <0.1 <0.015 <0.02 0.03
corrosion perforation
Figure 4. (a) Metallographic structure of the base material; (b) Metallographic structure around the
corrosion perforation.
after film removal is shown in Fig. 6. According to the corrosion degree specified in NACE
RP-0775-2005[21], the test results are classified as severe corrosion (>0.25mm/a).
(a) (b)
Figure 5. The macroscopic morphology of the sample before film removal (a) Carbon steel connected
to the stainless steel; (b) Carbon steel.
(a) (b)
Figure 6. The macroscopic morphology of the sample after film removal (a) Carbon steel connected
to the stainless steel; (b) Carbon steel.
The OCP of Q245R carbon steel is negative 240 mV compared with that of 316L stain-
less steel as shown in Fig. 7, and the corrosion potential of Q245R carbon steel is also sig-
nificantly lower than that of 316L stainless steel as shown in Fig. 7. Therefore, when they
are coupled, the Q245R carbon steel is the anode, the positive potential shift, the anode
reaction rate increases, the cathode reaction is inhibited. 316L stainless steel is the cathode,
the negative potential shift, the cathode reaction rate increases, the anode reaction is in-
hibited. On the other hand, the corrosion current of Q245R carbon steel is 1.48×10-4 A/cm2,
much greater than the corrosion current of 316L stainless steel. Therefore, the coupling
potential of Q245R carbon steel and 316L stainless steel is only slightly positive than that
of Q245R carbon steel. However, according to the polarization curve, the current of Q245R
carbon steel increases rapidly with the positive shift of the potential, so the coupling cur-
rent will greatly increase, the anode of Q245R carbon steel is significantly promoted, that
is, the corrosion accelerates.
(a) (b)
Figure 9. (a) SEM image near the perforated hole A; (b) Corrosion products in the pitting pits.
Other micro corrosion perforations were found besides the hole A in Fig. 2, one of
those SEM image as shown in Fig. 10(a), the micro corrosion perforation is elliptic, with a
diameter of 1.7 mm. The microstructure of corrosion products near the micro corrosion
perforation as shown in Fig. 10(b), and the corrosion products are abundant.
(a) (b)
1.7mm
Figure 10. (a) SEM image of the micro corrosion perforation; (b) The microstructure of corrosion
products near the micro corrosion perforation.
EDS was performed to analyze the distal and proximal ends of the micro corrosion
perforation in Fig. 10(a). The specific inspection locations are showed in Fig. 11, and the
detection results are presented in Table 6. According to the test results, the Cl and S ele-
ment content of Spectrum 2 were higher than Spectrum 1, indicating that the chloride ion
and Sulfur plays an important role in the formation of corrosion perforation.
Preprints (www.preprints.org) | NOT PEER-REVIEWED | Posted: 25 February 2022 doi:10.20944/preprints202202.0319.v1
Spectrum 1
Spectrum 2
Spectrum 2
Spectrum 1
Table 6. Energy dispersive spectrometer (EDS) analysis of corrosion perforation result (wt.%).
Element C O Al S Cl Ca Fe Tb Total
Spectrum 1 8.72 32.00 / / 0.41 1.06 54.66 3.16 100.00
Spectrum 2 9.16 29.80 0.41 0.45 0.81 0.61 58.76 / 100.00
During the four years of service, the sacrificial anode of the three-phase separator
was replaced twice in the process of maintenance, and the perforation occurred at the
bottom of the vessel under the baffle plate, which is a hidden place and not easy to find.
The enormous consumption of sacrificial anode indicates that the coating has fallen off or
the inner wall of the vessel has been directly contacted with the medium. When the sacri-
ficial anode is exhausted, the vessel inner wall which protected by the sacrificial anode
will be failed. Combining with the above test results, it is shown that serious corrosion
will occur on the inner plate of the vessel when the substrate contacts with the medium
directly, the Q245R carbon steel and baffle plate 316L stainless steel coupled form galvanic
corrosion[22-24], the corrosion will accelerate significantly.
Acknowledgement:This work has been supported by Tubular Goods Research Institute, China
National Petroleum Corporation, State Key Laboratory for Performance and Structure Safety of
Petroleum Tubular Goods and Equipment Materials.
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