5

Key Parameters Affecting Corrosion

CO 2 corrosion is affected by a n u m b e r of factors i n c l u d i n g e n v i r o n m e n t a l ,

metallurgical and hydrodynamic parameters. These are described in this Section.

5.1. Water Wetting

For CO 2 corrosion to occur there must be water present and it must wet the steel
surface. The severity of CO 2corrosion attack is proportional to the time during which
the steel surface is wetted by the water phase. Consequently the water cut is an
important parameter. However, the influence of the water cut on the corrosion rate
cannot be separated from the flow velocity and the flow regime effects. In o i l / w a t e r
systems emulsions can form. If a water-in-oil emulsion is formed then the water
may be held in the emulsion and water wetting of the pipewall prevented or greatly
reduced leading to a consequential reduction in the rate of corrosion. If, on the other
hand, an oil-in-water emulsion is formed, then water wetting of the pipewall will
occur. The transition from a water-in-oil emulsion to an oil-in-water emulsion occurs
around 30 to 40 wt% water in oil and, in straight pipe with emulsified liquids, a clear
jump in the corrosion rate can be demonstrated [12]. This had lead to a rule-of-thumb
that corrosion is greatly reduced for water cuts below around 30 wt% water cut in a
crude oil line.
However, the 30 wt% rule-of-thumb is only valid if an emulsion is formed and no
water drops out along the line. This is a stringent criterion and is not usually met in
flowlines and export lines. Operators' experience in systems such as Forties is that
water drop out can occur at very low water cuts (ie less that 5 wt%) and that emulsions
cannot be relied on for corrosion control. Thus, the 30 wt% rule-of-thumb is not
normally recommended and analysis of corrosion risk should assume that water
drop-out will occur at some point in the line.
Principal factors influencing water wetting include:

• O i l / w a t e r ratio;
• Flow rate and regime;
• Surface condition (roughness, cleanliness);
• Water drop-out (low spots);
• Water shedding due to changing flow profile (bends, welds); and
• 3rd party entries (mixing effect).
10 CO2 Corrosion Control in Oil and Gas Production--Design Considerations

5.1.1. Water Characteristics

The water associated with oil and gas production arises from two principle sources:

As 'Condensed Water'; this water is formed by the condensation of water

vapour from the gas phase.

As 'Reservoir Water'; this is reservoir (or formation) brine entrained with the
main hydrocarbon well stream fluids.

Reservoir water contains a wide range of dissolved salts which can influence the
pH of the wet CO2-containing hydrocarbon system. Bicarbonates can be particularly
beneficial as they can usefully increase system pH rendering the CO2-bearing liquids
potentially less harmful.
Further information on water characteristics is given in EFC Publication Number 17.

5.1.2. Hydrocarbon Characteristics

Crude oils can successfully entrap water to form stable water-in-oil emulsions.
Significant levels of water can be effectively held up in this manner thereby preventing
the water from wetting and corroding the steel. Depending on the water content
and other variables an oil-in-water emulsion can form, resulting in water wetting
of the steel.
The ability of crude oils to form stable emulsions will depend on oil chemistry,
specific gravity, viscosity, velocity and system pressure, temperature and flow
conditions. In general it has been found that most crude oils can incorporate water
up to at about 20 vol.% as long as the liquid flow velocity is above a critical level [13].
For any particular pipe diameter the critical velocity for water uptake by flowing
crude oil can be predicted after the method proposed by Wicks and Fraser [14].
Typically this critical velocity is around 1 ms -1 for most crude oils or as low as 0.5
ms -1 in deviated wells where temperature has a major influence.
In practice the emulsion forming capability of the crude oils of interest should be
determined experimentally to establish the actual amount of water that can be held
in an oil-based emulsion.
Lighter hydrocarbon condensates (e.g. NGLs) do not hold up water as effectively
as crude oils. The emulsions that are formed are weak and can break down rapidly
resulting in water wetting.
The corrosion problems in the oil lines and deviated oil wells with stratified flow
regime are well established (water line corrosion). At velocities below the critical
velocity for water/oil separation, the flow regime is generally of the segregated type.
The steel surface is almost permanently wetted by the water phase even for the water
cuts as low as 1%. Corrosion products and other solid particles coming from the
reservoir accumulate in the water phase at the lower side of the line or tubing and
may erode the corrosion product scale on the steel.
Some field results show that the water/condensate or oil/water separation is
possible even in slug flow where the flowing gas pushes the separated condensate/
oil phase above the water phase [15]. The water phase may remain at low spots until
 Key ParametersAffecting Corrosion 11
its volume becomes large enough to disturb the gas flow. Consequently full water
wetting may occur even in slug flow and with very low water cuts.
For the design of new installations, the evaluation of the flow regime, based on
the estimated development of the production rates during the field life, is of a
paramount importance. Whatever the water cut is, the line or tubing diameter should
ideally be selected in order to prevent segregated flow.
It is also important to consider the impact of production/process chemical
treatments on crude oil emulsion stability. Emulsion breakers are often introduced
into production facilities to enhance water/oil separation. It is not unusual for these
to carry through with the separated liquid hydrocarbon stream if they are used in
excess. The carry through of such treatment chemicals to later parts of the plant will
influence the ability of the crude oil to entrain and retain water as a stable emulsion
through the production facilities.
The separation of water from crude oils (with or without added de-emulsifiers)
may occur even at very low water cuts (e.g. less than 5%) at low points in a
pipeline. Consequently, for pipeline corrosion control a regular pipeline pigging
campaign may be required to ensure that any separated water accumulations
are effectively removed, particularly as flow rates decrease towards the end of
the field life.

5.1.3. Top-of-the-Line Wetting

In gas/condensate pipelines the corrosion rate may vary between the top and the
bottom of the pipe. Under stratified flow regimes, the top-of-line (TOL) location in a
pipeline is not continually water wetted. However, there is always some condensation
of water on the inner pipe wall. If this water is rapidly saturated with corrosion
products, the pH in the water increases and causes the formation of fairly protective
corrosion product films on the steel surface which can reduce the corrosion rate. A
constant corrosion rate is obtained when the corrosion rate has been reduced so
much that it is balanced by the rate at which corrosion products are transported
away from the surface by the condensed water. (At high condensation rates the water
may be undersaturated and remain acidic and corrosive).
Experiments at IFE showed that the corrosion rate could be calculated when the
condensation rate and the solubility of iron carbonate in the condensed water are
known, and a simple model was developed [16]. At moderate condensing rates
(< 0.25 gm-2s -1) the corrosion rate will be less than 0.1 r a m / y e a r over a wide range of
CO 2 partial pressures (0-12 bars) and temperatures (20-100°C).
It is also possible to calculate the TOL corrosion rate using the Shell corrosion rate
prediction model as a condensation factor is included [3]. The factor Fcondis equal to
1 for high condensation rates (= 2.5 g m-2s -1) and is reduced to Fcond= 0.1 when the
condensation rate is less than 0.25 gm-2s -1. The factor is regarded as conservative.
Excessive corrosion rates can be mitigated by reducing the cooling rate of the
pipe wall and by avoiding cold spots. Under practical conditions, at low cooling and
condensing rates, it seems to be generally accepted that no serious corrosion problems
have been experienced in gas pipelines with CO 2 only, but that traces of H2S have
led to some attack in a few cases (in these cases the buffering by corrosion products
is lowered by the lower solubility of iron sulfides). Nevertheless, TOL corrosion can
12 CO2 Corrosion Control in Oil and Gas Production--Design Considerations

be difficult to control with a reasonable degree of certainty, since injected chemicals

can not in general be expected to be present in the condensing water.

5.2. Partial Pressure and Fugacity of CO 2

CO 2 corrosion results from the reaction of a steel surface with carbonic acid arising
from the solution of CO 2 in an aqueous phase m i.e. it is not a direct reaction with
gaseous CO 2. The concentration of CO 2 in the aqueous phase is directly related to
the partial pressure of CO 2 in the gas in equilibrium with the aqueous phase. Thus in
CO 2 corrosion, estimates of corrosion rate are based on the partial pressure of CO 2 in
the gas phase.
It should be noted that if there is no free gas present then the CO 2 content of the
water will be determined by the PCO2of the last gas phase in contact with the fluids
(e.g. the PCO2at the bubble point for well bore fluids; the PCO2in the low pressure
separator gas for fluids in an export pipeline).
Strictly, it is the thermodynamic activity of the CO 2 in the aqueous phase that will
be important in the corrosion reaction rather than its concentration per se. This activity
will vary with concentration depending on the chemical composition of the aqueous
phase. However, the activity of the CO 2 in the aqueous phase is directly linked to the
activity in the gas phase, known as the fugacity. The fugacity of a gas is effectively
the activity of the gas and for ideal gases, this is equal to the partial pressure.
However, with increasing pressure the non-ideality of the natural gas will play an
increasing role, and instead of the CO 2 partial pressure, the CO 2 fugacity fc02 should
be used with some models:

fco 2 = f'Pco2 (7)

where f is the fugacity coefficient. Figure 1 provides a conservative estimate for f.

The presence of other gases will generally further reduce the fugacity coefficient.
When necessary, the fugacity should certainly be taken into account in any predictive
model for system pressures exceeding 100 bar.
However, it is important to keep a consistent approach for both gas and water
phases. If there is insufficient information to establish the non-ideality in the aqueous
phase, then Pco2should be used in considering the gas phase. This is particularly
true for pH calculation.

5.3. Temperature

The corrosion of carbon and low alloy steels in a w e t C O 2 environment can lead to
iron carbonate as a reaction product. Although recent work suggests that an iron
carbide matrix may be first exposed on the surface of corroding steel, a carbonate
scale which may protect the underlying metal can often be formed [17]. The formation
and protectiveness of such a scale depends on a number of factors that are described
in Section 5.5.
 Key Parameters Affecting Corrosion 13

0.9

------..44o oC

0.8 120~
,

O
0.7
40 " ~ ~

U_
0.6

0.5

0.4
0 50 1O0 150 200

Total system pressure, bar

Fig. 1 Fugacity coefficient for CO 2 in methane for gas mixtures with less than 5 mole% CO 2 [4].

H o w e v e r , at h i g h e r t e m p e r a t u r e s (e.g. a r o u n d 80°C) the iron c a r b o n a t e

solubility is decreased to such an extent that scale formation is more likely. Under
laboratory conditions, rates of u n i f o r m corrosion are consistently reduced at
higher temperatures.
Some laboratory studies show that the initial rate of uniform corrosion increases
up to 70-90°C, probably due to the increase of mass transfer and charge transfer
rates [2,3]. Above these temperatures, the corrosion rate starts to decrease. This is
attributed to the formation of a more protective scale due to a decrease in the iron
carbonate solubility and also to the competition between the mass transfer and
corrosion rates. As a result, a diffusion process becomes the rate determining step
for the corrosion rate.
Field evidence for a m a x i m u m t e m p e r a t u r e for CO 2 corrosion has been found
in some wells. These case histories s h o w that in oil and gas wells m a x i m u m
corrosion takes place where the t e m p e r a t u r e is b e t w e e n about 60 and 100°C
[2,18,19] which m a y coincide with d e w point t e m p e r a t u r e in gas wells. In these
cases, below 60-70-°C, the corrosion rate increased with increasing t e m p e r a t u r e
and above 80-100°C the corrosion rate decreased with increasing temperature.
Conversely, very high corrosion rates have been observed up to 130°C at the top
of some gas wells exascerbated by high rates of water condensation.
14 CO2 Corrosion Control in Oil and Gas Production reDesign Considerations

5.4. p H

The pH value is an important parameter in corrosion of carbon and low alloy steels.
The pH affects both the electrochemical reactions and the precipitation of corrosion
products and other scales. Under certain production conditions the associated
aqueous phase can contain salts which will buffer the pH. This tends to decrease the
corrosion rate and lead to conditions under which the precipitation of a protective
film or scale is more likely.
For bare metal surfaces which are representative for worst case corrosion,
laboratory experiments indicate that a flow sensitive H + reduction dominates the
cathodic reaction at low pH (pH < 4.5) while the amount of dissolved CO 2 controls
the cathodic reaction rate at higher pH (pH > 5).
In addition to the effects on the cathodic and the anodic reaction rates, pH has a
dominant effect on the formation of corrosion films due to its effect on the solubility
of ferrous carbonate, as illustrated in Fig. 2. It is seen that the solubility of corrosion
products released during the corrosion process is reduced by just five times when
the pH is increased from 4 to 5 but by a hundred times with an increase from 5 to 6.
The lower solubility gives a much higher FeCO 3 supersaturation on the steel surface
and a subsequent acceleration in precipitation and deposition of iron carbonate scale
[17]. The likelihood of protective film formation is therefore increased significantly
when the pH is increased beyond 5 and this can explain w h y low corrosion rates
have been reported for many fields where the pH is in the range 5.5--6. However, the
solubility of FeCO 3 must not be confused with that of ferrous ions (Fe2+).

100

10-
(p
LI_

E
C)..
C~.
1 -
o~
o~
..O

cO 0.1 m
o
oQ)
Li.

0.01 -

0.001 I I
5 6

pH

Fig.2 Solubility of iron carbonate released during the corrosion process at 2 bar CO 2 partial
pressure and 40 °C [17].
 Key ParametersAffecting Corrosion 15

5.5. Carbonate Scale

Reliance on carbonate scales/film as described in section 5.3 to give continuous

protection is not totally warranted. In particular, in regions of high flow or at welds,
scale breakdown can lead to rapid rates of localised corrosion ('mesa attack').
Recent extensive work on the subject has shown that the corrosion process involves
the initial production of an iron carbide matrix on the surface of corroding steel.
Corrosion product film of FeCO 3 or Fe30 4 will then form as a scale on the surface
resulting in a reduction in the corrosion rate [20]. The formation and protectiveness
of such a scale depends on a number of factors such as the solubility of iron carbonate
(which will vary with pH and the presence of other salts), the rate of reaction of the
underlying steel and the surface condition (roughness/cleanliness/prior corrosion).
The scale [9] may be weakened by high chloride concentrations, by the presence
of organic acids or it can be eroded by high speed liquids. Practical velocities for
smooth flow in systems with single phase liquid flow are often too low to achieve
this; only the impact of high speed liquid droplets can damage the scale. The
occurrence of such a disturbed flow pattern in practical systems can be predicted
from the suggestion made by Smart [21] that the onset of erosion-corrosion is
coincident with the transition to the annular mist flow regime in multiphase flow.
With the superficial liquid velocities associated with wet gas transport, this transition
arises at superficial gas velocities between 15 and 20 ms -1. Above these velocities the
scale protectiveness may be impaired.
The effects of short term scaling will often make interpretation of short-term
laboratory experiments difficult and for this reason such data must be treated with
care m especially results that give unexpectedly low rates of corrosion.

5.6. The Effect of H2S

Leaving aside the cracking and corrosion problems associated with sour service,
H2S can have a beneficial effect on wet hydrocarbon CO 2 corrosion as sulfide scales
can give protection to the underlying steel. The effect is not quantified but it does
mean that facilities exposed to gas containing low levels of H2S may often corrode at
a lower rate than completely sweet systems in which the temperatures and CO 2
partial pressures are similar.
The acid formed by the dissolution of hydrogen sulfide is about 3 times weaker
than carbonic acid but H2S gas is about 3 times more soluble than CO 2 gas. As a
result, the contributions of CO 2 and H2S partial pressures to pH lowering are basically
similar. H2S may cause corrosion also in neutral solutions, with a uniform corrosion
rate which is generally very low [22]. Furthermore, H2S may play an important role
in the type and mechanical resistance of corrosion product films, increasing or
decreasing their strength.
Many papers have been published on the interaction of H2S with low carbon steels
under ambient conditions and the work relating to H2S corrosion problems in the oil
and gas industry is well documented. However, literature data on the interaction of
H2S and CO 2 is still limited. The nature of the interaction of H2S and CO 2 with carbon
16 CO2 Corrosion Control in Oil and Gas Production ~Design Considerations

steel is complex. From past experience corrosion product layers formed on mild steel
can be protective or can lead to rapid failure depending on the production conditions.
This is primarily because an iron sulfide (FeS) film will form if H2S is predominant
and iron carbonate (FeCO 3) will form if CO 2 is predominant in the gas.
The majority of the open literature does indicate that the CO 2 corrosion rate is
reduced in the presence of H2S at ambient temperatures. However, it must be
emphasised that H2S may also form non-protective layers [23], and that it catalyses
the anodic dissolution of bare steel [24]. There is a concern that steels may experience
some form of localised corrosion, but very little information is available.
Published laboratory work has not been conclusive, indicating that there is a need
to carry out further study in order to clarify the mechanism [25,26]. A recent failure
showed how the corrosion rate in the presence of a high concentration of H2S may
be higher than predicted using CO 2 corrosion prediction models [27]. However, in
spite of the work on H2S corrosion of steels, no equations or models are available to
predict corrosion as is the case for CO 2 corrosion of steels.
Cracking of metals in production environments containing H2S is a major risk.
Hydrogen sufide can cause cracking of carbon and low alloy steels within certain
conditions of H2S partial pressure, pH, temperature, stress level and steel metallurgy
and mechanical properties (e.g. hardness). The type of damage manifests itself in
the form of cracking such as sufide stress cracking (SSC), stepwise cracking and
other forms of damage which are discussed at greater length in EFC Publication No.
16.

5.7. Wax Effect

The presence of wax in main oil lines can influence C O 2 corrosion damage in two
ways; exacerbating the damage or retarding it, the effects depending on other
operational parameters such as temperature, flow, etc. and uniformity and the nature
of the wax layer.
Field experience in sweet oil lines in the USA, have shown that a layer of wax
(paraffin) deposited on a carbon steel surface can result in severe pitting of the steel
in anaerobic aqueous solutions of carbon dioxide [28]. Severe pitting occurred along
the bottom of the pipe. Pitting (small random pits) tended to concentrate at the start
of an uphill run where water could collect. Scale analysis showed the presence of
iron sulfide. This was attributed to the presence of bacteria. (The detection of sulfide
in a sweet oil line is not usual. In fact in the case of microbially assisted corrosion,
scale analyses often show 15-30% Fe x S.y ). Velocity was an apparent factor affecting
the location of pits; there being a decrease in the number of pits at flow velocities
above about 0.6 ms -1. (The principal practical observation was that conventional
commercial corrosion inhibitors were ineffective in controlling corrosion; the corrosion
control measure finally adopted for the gathering lines was to install pull-through
polyvinyl chloride liners). In this case the proposed corrosion mechanism is of
diffusion of carbon dioxide through the wax layer which is thought to provide a
large cathodic area that supports anodic dissolution of the steel at discontinuities of
the wax layer. The effect was reproduced in laboratory tests with paraffin coated
specimens exposed to CO 2 saturated water at atmospheric pressure and ambient
 Key ParametersAffecting Corrosion 17

temperature. Localised corrosion only took place where there was no wax deposit.
The areas covered with wax were protected from the CO 2 containing solution. The
difficulty in controlling this type of localised corrosion with commercial oilfield
inhibitors was demonstrated in these laboratory tests [28].
In contrast, field experience of a 20 in. (50.8 cm) oil line in Indonesia (about 20 km
length) showed almost nil corrosion rate during about 10 years service which was
attributed to a wax deposit on the pipe wall. The water cut was up to 50%. Internal
corrosion started when light hydrocarbon condensate produced from a gas field was
injected into the line. This dissolved the wax deposit exposing the steel surface, as
confirmed by internal inspection of a corroded pipe section.