Chemical and Petroleum Engineering, Vol. 40, Nos.

1–2, 2004

MATERIALS SCIENCE AND CORROSION PROTECTION

CHEMICAL, HYDRODYNAMIC, AND METALLURGICAL

FACTORS IN WEST SIBERIAN OIL PIPELINE
CORROSION FAILURE

V. V. Zav’yalov1 and L. S. Moiseeva2

Various factors control the rate and character of the corrosion in pipelines handling three-phase gas–liquid mixtures,
of which the main ones are hydrodynamic, chemical, and metallurgical. The first two have been examined in the main detail.
The first incorporates the effect on the corrosion from the speed of the gas–liquid mixture GLM and the structure of it, while
the second represents the effects of the medium, including the tendency to produce solid deposits.
The structural forms of the GLM are usually considered relative to a gas–liquid system, but for the oil industry, it is
equally important to consider how the oil and water in a pipeline move one relative to another. When they move together, the
flow speed and water content control whether one gets an emulsion of the type of water in oil or of oil in water, and also the
stratification, when the oil and water move as separate phases.
One emulsion structure gives way to the other in the phase-inversion range for the water content of 55–65%, while
the stratification can occur at any water content and is considered to be of the main hazard as regards corrosion. A condition
for the stratified form of GLM to give way to an emulsion structure is related to increase in the flow speed. However, while
that can lead to complete inhibition of the corrosion at low and medium water contents, at high contents (80–99%) it increas-
es the corrosion rate, as is confirmed by accidents on petroleum pipelines, in particular at the Samotlor deposit. When oil con-
taining much water flows with a gas content of 70–80%, the flow speed may attain 2–5 m/sec, while the corrosion rate is 4–12
mm/yr. Reducing the flow speed to 0.1–1.0 m/sec and the flow gas content to 20–40% reduces the corrosion rate by more than
an order of magnitude, so it is necessary to minimize the speed of the gas–liquid flow when there is a high water content.
The effects on the corrosion rate from the composition are not so obvious. The stratal waters at Samotlor deposit
are of chloride-calcium type on Sulin’s classification, with salinity 10–30 g/liter and with a high tendency to deposit car-
bonate materials (CaCO3). The main component governing the corrosiveness of the stratal waters is the dissolved carbon
dioxide, whose mass concentration in Samotlor water samples varies from 10 to 250 mg/liter, while the molar concentra-
tion in the associated petroleum gas ranges from 0.16 to 1.00 mol/liter in accordance with the stratum. The mass concen-
tration of another corrosive component (hydrogen sulfide) is much less and constitutes not more than 5 mg/liter (average
1 mg/liter). The mass concentration of hydrogen sulfide in the petroleum gas is at the level of 5 mg/m3, but in some bore-
holes it attains 100 mg/m3. When one converts the mass and molar concentrations of carbon dioxide and hydrogen sulfide
to partial pressures by means of the Henry constants, one gets that the figure for carbon dioxide is 0.12 atm, as against
0.00024 atm for hydrogen sulfide.
With ratios of the partial pressures of carbon dioxide and hydrogen sulfide over 200, tube steels are corroded main-
ly by the carbonic acid mechanism [1]. That ratio is 250–500 at Samotlor, which confirms that the corrosion mechanism is

1
Nizhnevartovsk Oil Production Research Institute Limited.
2
LUKOIL Research Center.

Translated from Khimicheskoe i Neftegazovoe Mashinostroenie, No. 1, pp. 31–34, January, 2004.

0009-2355/04/0102-0045 ©2004 Plenum Publishing Corporation 45

mainly carbonic acid. The corrosion rate is then directly proportional to the carbon dioxide concentration and can be calcu-
lated from the De Waard–Milliams equation:

log K = 6.467 − 1710 /(273 + t ) + 0.67 log pCO ,

2

where K is the corrosion rate in mm/yr; t the temperature of the GLM in °C; and pCO2 is the carbon dioxide partial pressure in atm.
The corrosion rates given by that formula for the Samotlor strata are 0.2–0.4 mm/yr, but in practice corrosion fail-
ure in pipelines occurs at rates of 4–12 mm/yr, which in some cases attain 18 mm/yr (groove corrosion). The difference
between the actual and calculated rates occurs because that equation applies for uniform corrosion in the absence of deposits
on the surfaces, whereas the internal surface of a pipeline at West Siberian deposits is almost always coated with a layer of
sediment. That layer contains iron carbonate FeCO3 or siderite, which is a product from carbonic acid corrosion, and calci-
um carbonate CaCO3, which is due to carbonic acid instability. As a trace component there may be iron sulfide FeS, which
is mainly of biogenic origin. In nearly all cases, the compositions of these coatings are of sandwich type, i.e., include all the
above compounds in various ratios. In the region directly adjoining the surface of the pipeline, the deposit consists of FeCO3.
The high local corrosion rates in the presence of these deposits are due to macroscopic galvanic pairs, which include small
anodic zones and extended cathodic ones [2]. Their formation is mostly unpredictable, which hinders forecasting of local
damage for steel pipelines. As there is no direct contact between the stratal water and the pipeline surface when these deposits
are present, the corrosion damage rate in a petroleum pipeline is almost independent of the stratal water composition but is
determined by the stability and permeability of these deposits.
Only ten years ago there were few or no data on the effects of the metallurgical factor on the corrosion, by which
one means the composition and structure of the steel and the tube manufacturing technology. However, in the mid-1990s,
there was some reconsideration of the metallurgical factor in corrosion, which was due in part to the persistent increase in the
number of corrosion failures and the shortening of the periods of fault-free operation in new pipelines (up to the first failure).
In particular, at the Samotlor deposit it was 1–3 years.
Beginning in the 1960s, oil deposits in West Siberia were fitted with general-purpose steel tubes, whose production
was governed by GOST 8731-87, 8732-78, and 20295-85. Those regulatory documents lay down that tube quality is evalu-
ated from the composition and mechanical properties of the steel, in particular the impact toughness, which characterizes the
cold brittleness. It is necessary to consider the latter for tubes to be used in the climatic conditions of the Far North, where
the design temperature at which the pipe should not show brittle failure is –40°C.
The corrosion resistance is not considered in the currently applicable standards. It is therefore necessary to estimate
the effects of the metallurgical factor on the corrosion resistance for the conditions of West Siberia. We have examined the
microstructure on steel specimens cut from damaged parts of a pipeline and determined the granularity and banding scores
as well as the contents of nonmetallic inclusions in accordance with GOST 5639-82, 5640-68, and 1778-70.
The general corrosion rates were determined by few-cycle voltametry with a PI 50-1 potentiostat, with the electrode
supplied with triangular pulses of amplitude 5–20 mV relative to the corrosion potential [2]. The working medium was a car-
bonic acid model for the Samotlor stratal water with concentrations of the components as follows: NaCl 17.00 g/liter, CaCl2
0.14, and KHCO3 0.64. To remove the oxygen and keep the pH at the 6.2–6.6 level, we used a mixture of nitrogen and car-
bon dioxide. The partial pressure of the carbon dioxide in the mixture was 0.01 MPa. The temperature during the experiment
was maintained at 40 ± 2°C, with the solution stirred by a magnetic stirrer.
A galvanostatic method [3] was used to evaluate the tendency of the tube steels to local corrosion: polarization in a
boride buffer solution at pH 8.5 with recording of the potential change. Potential-time plots were used. At +1.2 ± 0.2 V, the
steel was considered as resistant, while with a potential of +0.1 ± 0.1 V, it was considered as unstable against local corrosion.
We determined the microstructure on specimens 10 × 10 × 7 mm, which were first etched in a 5% alcoholic solu-
tion of nitric acid for 20 min. They were then washed initially with tap water and then with distilled water, followed by dry-
ing and polishing. The microstructure was examined with a Meophot-30 optical microscope at a magnification of 100. We
evaluated the grain size, ferrite-pearlite banding, and level of nonmetallic inclusions by comparison with standard scales in
accordance with GOST 5639-82, 5640-68, and 1778-70.

46
 Fig. 1. Scheme for damaged part of pipe (a), with microstructure (b and c) and corrosion damage
to the surface (d and e), ×200 (b and c), ×400 (d), ×320 (e).

The composition of the steel was determined with a Perkin–Elmer atomic absorption spectrophotometer.
These tests on specimens cut from damaged parts of a pipeline showed that general-purpose tubes were supplied
without heat treatment. There was a high point score for banding in the pearlite phase (4–5 points on GOST 5640-68), and
the grain size was large (5 points on GOST 5639-82), and there were high levels of nonmetallic inclusions (sulfides, oxides,
and oxysulfides in accordance with GOST 1778-70). The most extensive damage due to groove corrosion and pitting occurred
for pipes made of steels with high manganese contents: 17G7S and the modifications of it 10G2 and 09G2S.
We examined one of the damaged parts of a pipeline consisting of tubes of different types: electrically welded ones
made by the Khartsyz plant and unwelded products from a Czech factory (in Khomutov), which showed that the first tube
was subject to groove corrosion at 8.7 mm/yr, while the second showed uniform corrosion at 0.7 mm/yr. Chemical analysis
showed that the two tubes were made of 17G1S steel.
Figure 1 shows the damaged part of the pipe of diameter 530 × 7 mm cut from an oil collector at 7 months after the
start of use. The microstructure in the steel forming the electrically welded tube had prominent banding in the pearlite phase
(4 points) on GOST 5640-68), which is to be considered as inhomogeneity in the steel structure (Fig. 1b) and is typical of

47
 Fig. 2. Cross section of specimen (a), tube surface outside groove (b), bottom of groove (c),
and microstructure of steel (d), ×100.

Fig. 3. Galvanostatic curves for tube steels at 40°C with N2 flowing into and a current
density of 3·10–4 A/cm2: 1) 06Kh1; 2) St 20S; 3) St 20; 4) 09G2S; τ experiment time.

electrically welded tubes made of 17G1S steel manufactured by controlled rolling. It has been found that pipes with that
structure in the steel have a high tendency to hydrogen cracking [4].
The microstructure of the steel in the unseamed tube had a platy arrangement for the pearlite phase (Fig. 1c), which
is characteristic of tubes made by hot rolling.
The corrosion damage to the tube surfaces is due to preferential dissolution of the pearlite phase along the rolling
lines (Fig. 1d and e). In the seamless tube, the corrosion at the surface was also due to dissolution of the pearlite component,
but the pearlite grains were more evenly distributed, so the corrosion did not propagate deep into the metal.
Figure 2 shows the corrosion damage to a seamless tube of diameter 219 × 18 mm made of 09G2S steel. The cor-
rosion rate attained 18 mm/yr. The groove was formed with the continuous removal of the protective deposit layer from the
surface due to the erosion by the flow containing solid particles, which favored the formation of galvanic pairs between the
exposed alloy and the rest of the surface of the tube coated with protective deposits [5].

48
 TABLE 1

Steel Maker Regulation document Uniform corrosion rate in mm/yr

17G1S ChTPZ GOST 20295-85 0.78

17G1S VMZ GOST 20295-85 1.65
09G2S Czech (Khomutov) GOST 8731-87 1.18
20 VTZ GOST 8732-78 0.80
20DS SinTZ TU 14-161-148-94 0.43
20S SevTZ TU 14-162-14-96 0.49
20A (22A) TMZ TU 14-157-42-96 0.38
20V VTZ TU 14-3-1971-97 0.44
06Kh1 VTZ TU 14-3-1972-97 0.41
08KhMChA SevTZ TU 14-162-11-95 0.48

The banding in the pearlite phase (4 points on GOST 5640-68) indicates that the hot-rolled pipe had not been sub-
ject to additional heat treatment. There were also nonmetallic inclusions consisting of calcium aluminate and mixed sulfides,
which are active [6] in producing local pitting foci where the corrosion rates exceed 10 mm/yr.
These results led to changes in tube manufacture at various Russian plants: Chelyabinsk (ChTPZ), Sinar (SinTZ),
Sever (SevTZ), Volga (VTZ), Vyksun (VMZ), and Taganrog (TMZ), which contained parts for heat treatment. In particular,
techniques were used such as microalloying with vanadium, niobium, titanium, and aluminum, and restricting the manganese
content to 1%. A key part of the technology is special heat treatment: quenching with double tempering, which provided a
finely divided ferrite-pearlite structure with carbides of rounded form [7] (granularity 9–12 points). This allowed a start to be
made on producing pipes from steel 20 and from low-alloy steels 06Kh1 and 08KhMChA with higher toughness and corro-
sion resistance.
Comparative tests showed that the rates of uniform corrosion for steels 20DS, 20S, 20V, 06Kh1, and 08KhMChA
are low and similar one to another (Table 1). The minimum corrosion rate as determined by the electrochemical method
occurred for steel 20A (22A). Steels 17G1S and 09G2S are considerably inferior as regards corrosion resistance in stratal
water saturated with carbon dioxide. Steel specimens of the same grade 17G1S but made by different producers differed con-
siderably in corrosion resistance.
Figure 3 shows galvanostatic curves for tube steel specimens made in accordance with various standards and tech-
nical conditions. The potentials E in galvanostatic polarization for steels 09G2S and 20, which had not been heat treated,
ranged from +0.1 to –0.1 V, while for steels 20S and 06Kh1 they were respectively +1.10 and +1.25 V, which indicates high-
er resistance to local corrosion in the latter. The galvanostatic polarization potentials for steels 20DS, 20A, and 20V (not
shown in Fig. 3) were in the range from +1.10 to +1.25 V, i.e., between the steady potentials for 20S and 06Kh1.
These results led to recommendations on altered technology for making tubes for oil use. Industrial tests on pipes
made by the altered technologies were carried out at Samotlor deposit between 1997 and 2001 and showed that their work-
ing reliability was increased relative to ordinary tubes, but it remains an open question at present what is the guaranteed peri-
od of fault-free operation.
Steels 17G1S and 09G2S have less corrosion resistance in West Siberian oilfield carbon dioxide media than do steels
20A (22A) and 20V. Therefore, the latter are preferable for use at West Siberian deposits.
These tests on various grades of steel and industrial tests over many years on steel pipes have provided technologies
for increasing the corrosion resistance in oilfield media in West Siberia:
• microalloying with V, Ni, Ti, Al, and Mn;
• reducing the Mn content to 1% in melting the steel; and
• heat treatment: quenching with double tempering.

49
REFERENCES

1. L. S. Saakiyan and A. P. Efremov, Protecting Petroleum Field Equipment from Corrosion [in Russian], Nedra,
Moscow (1982).
2. A. N. Markin, E. M. Gutman, I. S. Sivokon’, and L. P. Ermakova, “Small-amplitude cyclic voltametry of corrosion
inhibitors,” Zashch. Met., 27, No. 3, 368–371 (1991).
3. I. I. Reformatskaya, V. V. Zav’yalov, A. N. Podobaev, et al., “Effects of structural and phase inhomogeneities in car-
bon steels and low-alloy tube steels on the development of local corrosion,” Zashch. Met., 35, No. 5, 472–480
(1999).
4. N. A. Gafarov, A. A. Goncharov, and V. M. Kushnarenko, Equipment Corrosion and Protection at Petroleum
Deposits Containing Hydrogen Sulfide [in Russian], Nedra, Moscow (1998).
5. V. V. Zav’yalov, “Features of corrosion failure in pipelines at West Siberian deposits,” Zashch. Met., 39, No. 2, 1–5
(2003).
6. I. G. Rodionova, V. I. Stolyarov, O. N. Baklanova, et al., “Ways of improving the corrosion resistance of tubes made
of carbon steel and low-alloy steels,” in: Innovations in Making Pipes for the Oil and Gas Industry by Reference to
the Tube Metallurgical Company [in Russian], Volzhskii (2001).
7. T. V. Tetyueva, “Basic principles in devising technology for making tubes resistant to corrosion,” in: Making Pipes
for Oil Use with Elevated Working Reliability: Conference Proceedings [in Russian], Volzhskii (1997).

50