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Chevron
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chromium oxides of stainless steel 304 has also been match the environment of production wells could help in
reported.10 Divalent cations found in the sea (i.e. cost minimisation.
calcium and magnesium) can reduce the corrosion rate In this work, carbon steel (L80) and stainless steel
by forming a protective film layer of calcium and/or (13Cr) were used for the study of corrosion in natural
magnesium carbonate on the metal surface via calcar- gas production in the Gulf of Thailand. Conditions
eous film formation (a form of inhibition) may be corresponding to the gas field were simulated and
disrupted by dissolution in carbon dioxide. The effect of factors of temperature, PCO2 , chloride concentration
CaCl2 in simulated seawater on carbon steel corrosion in and mercury concentration were investigated. The
stagnant and flowing conditions of a 46%NaCl solution experiments were carried out using the potentiodynamic
saturated with CO2 at 57uC has been reported.11 polarisation technique.
Mercury exists in reservoirs in many forms, e.g. as
organic mercury and as inorganic mercury. The total Experimental
concentration of mercury in the Gulf of Thailand is 3 Materials and chemicals
6 ppm. On a global scale, the implications of the effects The stainless steel was 13% chromium, AISI 420 type
of mercury were not reported until 1973, when a (13Cr) and the carbon steel type was API 5CT L80
catastrophic failure of aluminum heat exchangers (L80). Produced water was simulated using analytical
occurred at the Skikda liquefied natural gas plant in grade reagents, sodium chloride (NaCl, 99?0% purity),
Algeria and in the gas gathering system of the Groninger sodium bicarbonate (NaHCO3, 99?7% purity), potas-
field in The Nertherlands.12 However, studies about the sium chloride (KCl, 99?8% purity), anhydrous calcium
effect of dissolved mercury on the corrosion behavior of chloride (CaCl2, 95?0% purity) and magnesium chloride
metallic materials in a reservoir environment seem to be (MgCl2.6H2O, 99?0% purity). All chemicals were sup-
very limited in the literature. plied by Labscan Asia. The solution was first deoxyge-
A possible mechanism for corrosion caused by the nated by nitrogen purging for 1 h and then saturated
presence of metallic mercury involves elemental mercury with carbon dioxide. Hydrochloric acid and sodium
amalgamating with the surface of a metal (e.g. for al- hydroxide were used to adjust the pH of the solution.
uminium). In this case, the protective passive film cannot be Ethyl alcohol was used as a cleaning agent for the
formed and the aluminium corrodes at an exceptionally electrodes.
high rate. Many metals form amalgams with mercury with
the notable exception of iron. However, where mercury
Procedure
may be deposited from solution, a local galvanic cell will Simulated produced water (SPW) was prepared based on
operate with the less noble metal (e.g. iron) corroding the composition provided by Chevron Thailand Explora-
preferentially.13 tion and Production Ltd (Table 1). The effect of tempera-
In the presence of CO2 or H2S, the corrosion products ture was determined in the range of 3060uC in a water
on ferrous alloys are metal carbonates or sulphides, bath, while the simulated produced water was saturated
correspondingly. Although the concentration of mercury with CO2. In order to illustrate the effect of carbon dioxide,
in the natural gas is very low, its effect is cumulative, and nitrogen was used to adjust the carbon dioxide partial
it is likely to gradually increase in concentration on the pressure. The effect of chloride was studied by varying the
chloride concentration using sodium chloride in the range
metal surface.14 Other mercury species are also present in
of 0?13?5 wt-%. The initial solution pH of the SPW was
natural gas. This mercury(II), is a powerful oxidising
adjusted using hydrochloric acid and sodium hydroxide
agent [standard potential50?788 V(SHE), compared to
solutions before saturation with CO2. The effect of mercury
hydrogen], and will act as a cathodic reactant and, as a
was studied by adding trace amounts of Hg(II) from 0 to
consequence, elemental mercury will be deposited with
12 ppm at various temperatures and CO2 pressures, as
increased corrosion of the substrate.
summarised in Table 1.
The selection of materials used as production tubing
emphasises mechanical properties and corrosion resistance. Potentiodynamic polarisation technique
Carbon steel is mostly used due to its cost, availability and The experiments for this study were carried out using a
strength. However, in some conditions where carbon steel is conventional three-electrode system connected to an
not durable enough, stainless steel is more attractive, as it Autolab PGSTAT20 potentiostat. Platinum was used as
provides better corrosion resistance.15 Chromium present a counter electrode. The reference electrode was a
in the steel forming a passive chromium oxide layer acts as saturated calomel electrode which was connected to the
a barrier in preventing corrosion when encountering an system using a Luggin capillary. Therefore, all potentials
aggressive media. Generally, stainless steel is much more reported in this work are based on the potential of a
expensive than carbon steel. Instead of the unnecessary use saturated calomel electrode (SCE). L80 and 13%Cr
of stainless steel for the entire design, smart design and coupons or working electrodes were polished with 1200
selection of appropriate types of steels for the tubing to grit silicon carbide paper and cleaned with ethyl alcohol in
1 Polarisation curves of 13Cr in simulated produced 2 Polarisation curves of L80 in SPW saturated with CO2
water (SPW) saturated with CO2 at 3060uC at 3060uC
Table 2 Corrosion parameters of 13Cr and L80 in SPW saturated with CO2 at different temperatures
Table 3 Corrosion parameters of 13Cr and L80 in SPW saturated with CO2 at 60uC in different chloride concentrations
Effect of carbon dioxide partial pressure at PCO2 equal to 0?5 and 1 atm respectively. It can be
Carbon dioxide is the key factor for corrosion in natural clearly seen that the corrosion rate of L80 was much
gas production. These experiments were carried out in higher than the corrosion rate of 13Cr. A corrosion rate
SPW at a constant temperature of 60uC with various of 3?861021 g cm22/year was obtained from the solu-
partial pressures of CO2: 0, 0?5, and 1 atm. An increase tion saturated with CO2. Without CO2, the corrosion
in corrosion potential was observed in 13Cr from rate of L80 is about one order of magnitude lower, as
20?878 to 20?725 to 20?678 V as the partial pressure can be seen in Table 4. The oxide of L80 was able to
of the carbon dioxide was increased from 0 to 0?5 to react with the dissolved carbon dioxide to produce
1?0 atm, as shown in Fig. 5 and Table 4. Additionally, ferrous carbonate and a dissolved complex of iron,
the pitting potential in the carbon dioxide saturated FeCO3 2{
2 , which accelerated the dissolution of the iron
solution was significantly decreased, which confirmed element.5
the effect of carbon dioxide on increasing the possibility
of pitting corrosion on the stainless steel. For L80, the Effect of mercury
polarisation curves in Fig. 6 show a large increase in the Mercury(II) and temperature
cathodic current density. The corrosion potential was The polarisation curves of 13Cr in various concentra-
20?873 V in the absence of CO2 and increased to tions of Hg(II) in SPW are shown in Figs. 7 and 8. There
20?751 and 20?735 V as the carbon dioxide partial was no significant difference in the cathodic part. The
pressure was 0?5 and 1?0 atm respectively. The signifi- anodic polarisation curves show a decrease in the
cant increase in corrosion potential may come from the current density in the passive region with increasing
additional cathodic reaction, i.e. carbonic acid reduction potential. At extremely low concentrations of Hg(II),
and hydrogen evolution. e.g. 3 ppm, the observed passive current density was
The corrosion rate of 13Cr was slightly affected by the lower than that observed from the 6 and 12 ppm curves.
carbon dioxide partial pressure. The corrosion rate of The current densities in the passive region also became
13Cr was 1?361022 g cm22/year in the absence of CO2 noisy during polarisation. This suggests that mercury, or
and increased to 2?061022 and 2?861022 g cm22/year Hg(II), influences the passive layer and the pitting
Table 4 Corrosion parameters of 13Cr and L80 in SPW saturated at 60uC with different CO2 partial pressures
Material CO2 partial pressure, atm Ecorr, V icorr, mA cm22 Epit, V Corrosion rate, g cm22/year
7 Polarisation curves of 13Cr in SPW with 012 ppm 9 Polarisation curves of L80 in SPW with 012 ppm Hg(II)
Hg(II) and saturated with of CO2 at 30uC and saturated with CO2 at 30uC
8 Polarisation curves of 13Cr in SPW with 012 ppm 10 Polarisation curves of L80 in SPW with 012 ppm
Hg(II) and saturated with CO2 at 60uC Hg(II) and saturated with CO2 at 60uC
behaviour of 13Cr during anodic polarisation. Since the Table 5; therefore, the uniform corrosion rate of 13Cr is
standard potentials of Hg(II) is 0?788 V(SHE), it would nearly constant and does not depend on the concentra-
be expected to be reduced at all potentials during the tion of Hg(II) in the range of 012 ppm.
potentiodynamic polarisation experiment. Thus, ele- The change of temperature from 30 to 60uC did not
mental mercury is expected to be present during both alter much the corrosion behaviour in the anodic part of
cathodic and anodic polarisation of the substrate. It was 13Cr. However, as can be seen in Table 5, the corrosion
found that the pitting potentials of 13Cr at the various rate has doubled as the temperature increased from 30 to
Hg(II) concentrations were slightly shifted to a more 60uC.
noble value and the passive currents were slightly lower. For L80, the addition of small amounts of Hg(II) (0
This may lead to an important role of elemental mercury 12 ppm) at 30uC (Fig. 9) and 60uC (Fig. 10) resulted in a
during the passivation of 13Cr and suggests that the slight shift in corrosion potential to a more noble value.
passive films with codeposition of mercury are more The shift of corrosion potential is probably because of
resistant. However, for long term corrosion of the metal the stronger oxidising power of the solution, i.e. due to
substrates in a mercury containing environment, the the presence of Hg(II). The current densities in the
corrosion behaviour is expected to be different. In this anodic part slightly increased with increasing concentra-
case, elemental mercury can be formed and plated on the tion of Hg(II). As can be seen in Table 6, the corrosion
surface resulting in a local galvanic effect.13 Hence, since current densities from L80 in SPW in the presence of
elemental mercury is more noble than typical carbon Hg(II) were lower than that obtained from the SPW.
and stainless steels, the site covered by mercury will be The corrosion current density or corrosion rate of L80 in
the cathode, while the remainder will be the anode. The SPW at 60uC was y4?5 times higher than that at 30uC.
galvanic corrosion promoted in such an environment
will lead to a higher localized corrosion rate. Mercury(II) and PCO2
The corrosion current densities of all curves at 30uC In the presence of 3 ppm Hg(II) at 60uC with varying
were nearly the same at 1?361023 mA cm22, as listed in partial pressures of CO2, the polarisation curves of 13Cr
Table 5 Corrosion parameters of 13Cr in SPW saturated with CO2 at different Hg(II) concentrations
Temperature, uC [Hg(II)], ppm Ecorr, V icorr, mA cm22 Epit, V Corrosion rate, g cm22/year
11 Polarisation curves of 13Cr in SPW at 60uC and 12 Polarisation curves of L80 in SPW at 60uC and 3 ppm
3 ppm Hg(II) with varying CO2 partial pressures Hg(II) with varying CO2 partial pressures
(Fig. 11) and the corresponding parameters (Table 7) and L80 in various conditions of SPW, including the
indicate that the corrosion current density or corrosion effect of dissolved mercury. The following can be
rate was slightly increased, while the pitting potential of concluded from this work:
13Cr was almost constant at between 0?060 and 0?089 V 1. The corrosion rate of 13Cr is slightly increased by
with partial pressure of CO2 from 0?5 to 1?0 atm. One the carbon dioxide partial pressure. The pitting potential
point that should be made is that a significant decrease is lower in the presence of carbon dioxide.
in current density in the passive region was not 2. A small amount of Hg(II) lowers the current
observed, as seen earlier in the absence of CO2. density in the passive region and increases the pitting
Figure 12 is the polarisation curves of L80 at 60uC potential of 13Cr.
and 3 ppm Hg(II) with varying CO2 partial pressures. 3. The corrosion rate of L80 is decreased with the
The corrosion potential of the L80 in the presence of addition of a small amount of Hg(II).
3 ppm Hg(II) was shifted from 20?810 to 20?740 V as 4. Dissolved CO2 could be an important chemical
the CO2 partial pressure was increased from 0 to 1 atm species for helping Hg(II) to interact with the passive
(Table 7). A higher oxidising power of solution for L80 layer of the 13Cr.
was obtained in the presence of CO2. The corrosion 5. The 13Cr shows a lower uniform corrosion rate
current density was also increased in the presence of than the L80 in all conditions of simulated produced
CO2. water.
For the polarisation curve of L80 without CO2,
pseudopassivity was briefly observed from about 20?630 Acknowledgements
to 20?470 V with a rather high current density of
y2?061022 mA cm22. This effect seems to exist with The authors would like to thank Chevron Thailand
the higher partial pressure of CO2, but the occurrence Exploration and Production for the research funds.
took place at much higher potential and yield to a much Many thanks are extended to the Chevron staff
higher current density. Because of this high current members who were involved in the research project,
density, it is, therefore, not a true passivation. especially at the Process, Analytical and Catalysis
Department, Chevron Energy Technology Company,
Houston, TX, USA, and Mr T. Sasichay and his
Conclusions colleagues from Chevron Thailand Exploration and
The potentiodynamic polarisation technique was Production for their kind coordination. Also, thank is
employed to investigate the corrosion behavior of 13Cr extended to Mr R. White for revision of English.
Table 6 Corrosion parameters of L80 in SPW saturated with CO2 at different Hg(II) concentrations
Temperature, uC [Hg(II)], ppm Ecorr, V icorr, mA cm22 Epit, V Corrosion rate, g cm22/year
Table 7 Corrosion parameters of 13Cr and L80 in SPW with varying CO2 partial pressures at 3 ppm Hg(II) and 60uC
Material CO2 partial pressure, atm Ecorr, V icorr, mA cm22 Epit, V Corrosion rate, g cm22/year