Paper No.

11327 2011

EFFECTS OF TEMPERATURE ON CO2 TOP OF LINE CORROSION OF PIPELINE

STEEL

Yingfeng Chen, Lei Zhang, Huimin Qin, Lining Xu, Minxu Lu

Corrosion and Protection Center, Key Laboratory for Environmental Fracture (MOE),
University of Science and Technology Beijing, Beijing 100083, People’s Republic of China

ABSTRACT

The influence of the temperature of wet gas and the state of the thin liquid film on Top Of Line (TOL)
CO2 corrosion of X65 pipeline steel was studied in a high pressure, high temperature autoclave
designed to simulating water condensation in wet gas pipeline environment. The corrosion rate
increased with the wet gas temperature. The temperature of wet gas and the outside environment
temperature affected the thickness of the condensate film, the condensation rate, and the film
temperature. When the temperature of wet gas or condensed water film is relatively low, the
corrosion is mainly controlled by the electrochemical reaction with low corrosion rate. When the
temperature is increased, the corrosion rate becomes higher due to the increase of film thickness
and condensation rate. However, when the temperature of wet gas is higher, corrosion product scale
can precipitate and deposit, protecting the metal surface.

Keywords: Top of Line Corrosion, CO2 corrosion, Condensation rate, Temperature

INTRODUCTION

CO2 corrosion has been wildly studied and a lot of attention has been focused on top of line corrosion
in pipelines transporting wet gas in recent years [1-8]. CO2 corrosion can be obviously influenced by
factors such as partial pressure, temperature, pH, flow rate. The protection of CO2 corrosion product
scale has been suggested as one of the most important factors, based on the experiments
immersing steel samples in solution to simulate the corrosion process. However, there is some
difference between immersed in solution and exposed to wet gas or covered with condensed water.
In order to investigate the detail of corrosion behavior, an autoclave with a sample cooling system
was used to simulate the condensed water film on the samples under certain temperature range and
a high CO2 pressure.

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 EXPERIMENTAL PROCEDURE

The test specimens were machined out of X65 pipeline steel. All specimens were polished
mechanically through a series of silicon carbide papers up to 800 grit, washed by water and
degreased by acetone. The experimental corrosion equipment was a high temperature and high
pressure autoclave equipped to simulate condensing conditions. The chemical composition of the
solution is shown in Table 1. In the autoclave, the specimens were placed above the solution surface
and covered with a layer of thin film electrolyte condensed from the water vapour contained in the
gas phase. The temperature of the gas phase in autoclave was controlled by the heating system to
simulate a wet gas temperature in the pipeline. The temperature difference between the gas phase
and specimen surface was controlled by the cooling system located on the other side of the
specimen, which simulated a lower temperature on the pipeline wall. This set up caused a liquid film
to condense on the wall and thus a wet gas corrosion environment was simulated. Measurement of
the temperature difference could also be carried out through the adjustment of the gas temperature
in the autoclave and the cooling system. In this paper, a 40~80oC gas temperature range and 0~30oC
cooling temperature condition were set. High purity nitrogen was purged through the solution into the
autoclave for over 24 hours after which the specimens were installed. Next the solution was heated
up to test temperature and then CO2 was injected until the pre-established pressure was reached.
The CO2 partial pressure was 0.4MPa. The experiment time was 6 days. The gas flow rate was 2m/s,
controlled by the rotation of the specimen holder. Figure 1 shows schematics of the experimental
setup. The specimens were dehydrated with alcohol after the experiment and the corrosion rate was
measured using the weight loss (WL) method. Analysis of the corrosion products was performed
using Scanning Electron Microscopy (SEM) and X-Ray diffraction patterns (XRD).

RESULTS AND DISCUSSIONS

The general corrosion rate of X65 steel immersed in solution at 60oC and 0.4MPa CO2 partial
pressure is about 1.12mm/yr. Under the wet gas situation with the same temperature and pressure,
the corrosion rate of X65 steel covered with a condensate film is about 0.44mm/yr. Despite the same
corrosion reactions under these two situations, the mass transport process of reactants and the
charge transfer process of ions are different. Since the condensed water film formed upon the steel
surface is very thin, the mass transport might be the controlling factor. The higher electric resistivity
of the condensate film will also reduce the charge transfer rate. The morphologies of the corrosion
scales formed under these situations are shown in Figure 2. The close piled FeCO3 grains induce a
good protective ability. However, the corrosion scale formed under wet gas situation is more porous
and consist of smaller grains. The difference can be attributed to both the lower corrosion rate and
the limited growth process of corrosion product.

In order to find out the influence of temperature on the corrosion induced by condensate film under
wet gas situations, experiments were carried out under various gas temperatures (Tgas) and
temperature difference (ΔTgas-wall) between the gas and outside surface of pipeline wall. Figure 3
shows the influence of ΔTgas-wall on corrosion rate of X65 steels under wet gas situation with CO2
partial pressure of 0.4MPa and simulated gas flow rate 2m/s. At the same ΔTgas-wall, the corrosion rate
increases with Tgas elevation at the range of 40 to 80 oC. Since there is a condensate film between
gas and steel surface, the influence of gas temperature was achieved through its effects on the
characteristics and temperature of the condensate film.

2
Figure 3 also shows that the increase of ΔTgas-wall increases the corrosion rate. Actually, more
important parameters were influenced by Tgas and ΔTgas-wall, such as the condensate film thickness
(δfilm), the condensation rate (m) and the temperature of condensate film Tfilm.

The δfilm can be estimated using various Tgas and ΔTgas-wall. At the Tgas range of 40 to 60oC, corrosion
rate will increase with the thickening of δfilm. For this case, the mass transport process might become
the key factor and control the corrosion rate. However, at the Tgas of 80oC, since the formation of
corrosion scale might become easier under these situations. The effect of δfilm was not obvious,
which indicated that the key corrosion factor changed.

Under the flow wet gas condition, continuous evaporation and condensation take place in the liquid
film. The mass refresh controlled by the condensation rate will influence the corrosion process.
According to previous research works [8], the condensation occurred on the wall surface at the initial
stage, and then on the phase interface between gas and liquid film.

A mechanistic model [9] is applied for the prediction of the condensation rate during Top-of-the-Line
Corrosion (TLC). This model solves the hydrodynamics of the condensed liquid and the heat and
mass transfer in the gas phase to predict the condensation rate in a horizontal pipeline in the
presence of a non-condensable gas. Firstly, an initial value of the temperature Ti0 at the gas-liquid
interface is guessed with the corresponding mass fraction of water vapor at the interface calculated
according to Peng-Robinson’s equation of state. And then, based on the mass and heat transfer
balance, the initial value of the heat transfer in the condensed liquid film is determined. Using the
approach proposed by Gunaltun [1], the heat transfer from the liquid film to the pipe wall, and the heat
transfer from the inner pipe wall to the outside environment are taken into account. Finally, by
introducing the counter-balance equation of the heat transfer, a new value of the interfacial
temperature Ti is obtained. The procedure is repeated until the point of convergence of the interfacial
temperature Ti. Once the interfacial temperature Ti has converged, the condensation rate m can
finally be calculated.

When δfilm is small, it can be assumed temperatures of the liquid film Tfilm and the interface between
gas and liquid film Tinterface is approximately equal to each other. Then m can be estimated. Figure 4
shows the relationship between corrosion rate and condensate rate. For most of the data points, the
corrosion rate increases with an increase of the condensation rate. At the range of relatively low
temperature, the mass transport process might be accelerated by increasing the condensation rate.
However, at higher temperature, the influence of condensate rate becomes nonlinear due to the
influence of Tinterface and the corrosion scale formation.

Figure 5 shows the influence of Tfilm on the corrosion rate. The corrosion rate increases with Tfilm at
the range of 20 to 60oC. It can be suggested that Tfilm might act as one of the most direct factors
during top of line corrosion. The corrosion reaction and the formation of corrosion scale are
influenced by Tfilm. Figure 6 shows the morphology of CO2 corrosion product scale formed at different
Tfilm. At a low Tfilm, a loose corrosion scale formed on the steel surface due to the low corrosion
reaction rate. With Tfilm increasing, the corrosion scale becomes more compact with coarser grains.
When Tfilm reached 70oC, a dense and protective corrosion scale can be found, which indicates that
the corrosion rate will not increase.

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 CONCLUSIONS

An autoclave with condensation simulation capabilities was employed to investigate CO2 top of line
corrosion. Based on the experiments performed under various wet gas temperatures and
temperature differences between gas and pipe wall, the corrosion rate of X65 under wet gas
situations was tested. At the range of 40 to 80oC, the corrosion rate increased with gas temperature
elevation. At relatively low gas temperature range, the corrosion rate is influenced by the
condensation rate and the actual temperature of the condensate film. At higher temperature, the
corrosion scale formation becomes the key factor and control the corrosion process.

ACKNOWLEGMENT
This work is supported by National Natural Science Foundation of China (Grant No. 50701007).

REFERENCES
1. Gunaltun Y, Larrey D. Correlation of cases of line corrosion with calculated water
condensation rates. Corrosion/00[C], paper no.00071
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Corrosion/00, paper no.00072
3. Vitse F, Alam K, Gunaltun Y, et al. Semi-empirical model for prediction of the Top-Of-the-Line
corrosion risk, Crorrosion/02, paper no.02245
4. Dugstad A, Lunde L. Parametric study of CO2 corrosion of carbon steel[A]. Corrosion/94. paper
no.94014.
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Corrosion/2004, paper no.04626
6. Vitse F, Nesic S, Gunaltun Y, et al. Mechanistic model for the prediction of top-of-the line
corrosion risk. Corrosion/03, paper no.03633
7. Nyborg R, Dugstad A. Top of Line Corrosion and Water Condensation Rates in Wet Gas
Pipelines. Corrosion/07, paper no.07555
8. Zhang Z, Hinkson D, Singer M, Wang H, Nesic S. A Mechanistic Model of Top-of-the-line
corrosion. Corrosion, 2007, (11): 1052-1062
9. Vitse F. PhD Thesis. “Experimental and theoretical study of the phenomena of corrosion by
carbon dioxide under dewing conditions at the top of a horizontal pipeline in the presence of a
non-condensable gas.” America: Ohio University, 2002.

Table 1 Chemistry composition of simulated brine（g/L）

ions Cl- Na+ Ca2+ K+ HCO3- Mg2+ SO42-
content 32.92 23 0.88 12.18 0.6 1.05 3.23

4
 Figure 1. Schematics of the experimental setup

a b

Figure 2. SEM images of the corrosion scale morphology formed on X65 samples immersed in
solution and under wet gas condition. (a: solution, b: wet gas)

0.9

0.8

0.7
corrosion rate, mm/yr

0.6

0.5

0.4
o
Tgas=40 C
o
0.3 Tgas=60 C
o
Tgas=80 C
0.2
10 20 30 40 50 60
o
Δ T, C

Figure 3. The relationship between gas temperature and corrosion rate.

5
 0.9

0.8

0.7

corrosion rate, mm/yr

0.6

0.5

0.4

0.3

0.2
0 5 10 15 20 25 30 35
-2 -1
condensation rate, g m s

Figure 4. The relationship between condensate rate and corrosion rate.

0.9

0.8

0.7
corrosion rate, mm/yr

0.6

0.5

0.4

0.3

0.2
20 30 40 50 60 70
o
Tfilm, C

Figure 5. The effect of the condensate film temperature on corrosion rate.

a b

c d

Figure 6. SEM images of the corrosion scale morphology formed on X65 under wet gas conditions.
(a: Tfilm=33oC, b: Tfilm=45oC, c: Tfilm=55oC, d: Tfilm=75oC)