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Production/Facilities
Integrated CO 2 -Corrosion and
Multiphase-Flow Model
Several prediction models for CO2 corro-
sion of carbon steel exist. Most of these
models are semiempirical or even fully
empirical. An integrated CO2-corrosion
and multiphase-flow model was built.
The overall model was extensively verified
and was able to perform reasonably well
in all cases. The multiphase-flow model
also was benchmarked against an estab-
lished commercial software package.
Introduction
Only a few, more recent, models use mecha-
nistic descriptions of the processes underly-
ing CO2 corrosion. A recent study of a rep-
resentative group of models concluded that
most of the models predict the “worst-case”
CO2-corrosion rate well, but predictions
vary widely for more-complex effects (e.g.,
protective films, water entrainment/wetting,
or H2S). The main reason for this spread lies
in the arbitrary nature of the empirical cor-
rection factors used to account for the vari-
ous complicating effects.
The full-length paper details a new CO2-
corrosion and multiphase-flow model that
takes into account the effect of most of the
important variables. Most of the model is
mechanistic in nature and fully transparent,
and it uses solid theoretical foundations.
Some aspects of the model that cover areas
in which insufficient knowledge exists (e.g.,
H2S effect) use a semiempirical approach.
Integrated Model
The integrated model comprises a corrosion
model and a multiphase-flow model. An
interface module enables the transfer of data
between the two.
Corrosion Model. The Nesic transient
mechanistic CO2-corrosion model is the
basis of the corrosion model. The corrosion
model comprises the following submodels.
Electrochemical Reactions at the Steel
Surface. Because the CO2-corrosion process
is electrochemical in nature, the corrosion
rate can be determined explicitly by calcu-
lating the rate of the underlying electro-
chemical reactions, such as iron oxidation
and hydrogen-ion reductions by carbonic
and acetic acid.
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Transport Processes in the Surface Film
and the Boundary Layer. In corrosion, cer-
tain species in the solution are “produced”
at the steel surface (e.g., Fe2+) while others
are depleted (e.g., H+). This process leads to
concentration gradients and diffusion of
these species toward and away from the sur-
face. However, the rate of the electrochemi-
cal reactions depends on the species con-
centrations at the steel surface. Therefore, a
two-way coupling exists between the elec-
trochemical processes at the metal surface
(corrosion) and transport processes in the
adjacent solution layer (i.e., diffusion in the
boundary layer). Flow (i.e., turbulent
eddies) can penetrate deep into the bound-
ary layer and enhance the rate of species
transport to and from the surface signifi-
cantly, hence leading to a higher corrosion
rate. Conversely, when protective films form
on the steel surface, they may slow the
species diffusion and can reduce the corro-
sion rate.
In a uniform-corrosion model, a 1D
species-transport domain is sufficient,
stretching from the steel surface through the
pores of a surface film and the mass-transfer
boundary layer, ending in the turbulent
bulk of the solution. The concentration of
each species is governed by a species-con-
servation (mass-balance) equation.
Chemical Reactions. A variety of chem-
ical reactions may accompany the corro-
sion process, some homogeneous (occur-
ring everywhere in the solution), others
heterogeneous (occurring only at the metal
surface). Hydration and dissociation are
typical homogeneous chemical reactions
accounted for in CO2 corrosion. Pre-
cipitation of iron carbonate is the only het-
erogeneous chemical reaction considered
in the current model. Most chemical reac-
tions are very fast compared to diffusion
and electrochemical reactions (all occur-
ring simultaneously in corrosion) and can
maintain chemical equilibrium throughout
the solution. Conversely, when some
chemical reactions proceed slowly, other
faster processes (such as electrochemical
reactions or diffusion) can lead to localized
nonequilibrium in the solution. Either way,
by affecting the surface concentrations of
This article, written by Technology Editor
Dennis Denney, contains highlights of
paper SPE 87555, “Integrated CO2-
Corrosion and Multiphase-Flow Model,”
by Srdjan Nesic, Shihuai Wang,
Jiyong Cai, and Ying Xiao, Inst. for
Corrosion and Multiphase Technology,
Ohio U., prepared for the 2004 SPE
International Symposium on Oilfield
Corrosion, Aberdeen, 28 May.
species, chemical reactions can signifi-
cantly alter the rate of electrochemical
processes at the steel surface and the rate of
corrosion. This alteration is particularly
evident when, because of high local con-
centrations of species, the solubility limit
is exceeded and precipitation of surface
films occurs.
Growth of Iron Carbonate Films. When
iron carbonate precipitates at the steel sur-
face, it can slow the corrosion process with
a diffusion barrier for the species involved
in the process or by blocking (covering) a
portion of the steel surface and preventing
the electrochemical reactions.
Iron carbonate film growth depends pri-
marily on the precipitation rate. As more
iron carbonate precipitates, the film can
grow in density as well as thickness.
However, the steel surface corrodes under
the film, continuously creating a void
between the film and the steel surface
(called film undermining). As soon as it is
created, the void begins filling up by the
ongoing precipitation. When the rate of
precipitation at the steel surface equals or
exceeds the rate of corrosion (film under-
mining), dense protective films form—
sometimes very thin, but still protective.
Conversely, when the corrosion process
undermines the newly formed film faster
than precipitation can fill the voids, a
porous and unprotective film forms that
can be very thick but unprotective.
In the current model, a mass-balance
equation for solid iron carbonate, which
includes the effect of undermining, can be
written and expressed in terms of volumet-
ric film porosity.
DECEMBER 2004
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H2S Traces. Modeling the effect of H2S on
CO2 corrosion is in its early stages because
not enough is known about the complex
interactions. Dissolved H2S is a mild acid
and, if present in high-enough concentra-
tions, must be treated as another cathodic
species, similarly to carbonic and acetic
acid. The presence of H2S can lead to the
formation of various forms of iron sulfide
films that can be very protective. In other
cases, they can lead to localized attack.
Finally, elemental sulfur often occurs in
conjunction with high H2S concentrations,
further complicating the situation.
At this point in time and for the purpos-
es of modeling, evidence about the effect of
very low H2S concentrations (traces of H2S)
on CO2 corrosion at low pH suggests that
precipitation of iron sulfides does not
occur. For concentrations of H2S less than
500 ppm in the gas phase and for pH<5,
many carefully controlled corrosion experi-
ments showed that at temperatures of 20 to
80°C, partial pressures of CO2 were 1 to
7 bar and velocities were stagnant to 3 m/s
in both single- and multiphase flow. All
data strongly suggest that the presence of
even very small amounts of H2S (10 ppm in
the gas phase) leads to rapid and significant
reduction in the CO2-corrosion rate. At
higher H2S concentrations, this trend is
arrested or even slightly reversed. The
effect seems to be universal and depends
only on the H2S concentration.
Steel Type. The corrosion rate on differ-
ent types of steel was modeled on the basis
of electrochemical behavior in CO2 solu-
tions. The primary focus was on low-carbon
(mild) steels and low-alloy steels typically
used for pipelines.
Polarization experiments indicated that,
on the surface of these steels, the cathodic
reactions proceeded similarly. However, the
corrosion rates were different and were
ascribed to the different anodic-dissolution
rates for different steel compositions and
microstructures. The experimental data
were used to model the electrochemical
parameters specific for each steel needed to
characterize its anodic behavior.
Inhibition. Two sources of corrosion inhi-
bition were considered in the model: inhibi-
tion by addition of corrosion inhibitors and
inhibition by components present in the
crude oil. Modeling the corrosion-inhibitor
effects was not straightforward. Approaches
in the literature vary from the use of simple
inhibitor factors and inhibition efficiencies
to the application of complicated molecular-
modeling techniques to describe inhibitor
interactions with the steel surface and iron
carbonate film. The approach used here
DECEMBER 2004
assumes that corrosion protection is
achieved by surface coverage (i.e., the
inhibitor adsorbs onto the steel surface and
prevents electrochemical reactions from
occurring on the underlying steel). The
degree of protection is assumed to be direct-
ly proportional to the fraction of the steel
surface covered by the inhibitor.
CO2-corrosion rates seen in the field,
when crude oil is present, are much lower
than those obtained in laboratory condi-
tions where crude oil is not used or so-
called “dead” or synthetic crude oil is used.
Two main effects of crude oil on the CO2-
corrosion rate can be identified. The first is
a wettability effect and relates to a hydrody-
namic condition in which crude oil entrains
the water and prevents it from wetting the
steel surface (continuously or intermittent-
ly). This effect was included in the model.
The second effect is corrosion inhibition
by certain components of the crude oil that
reach the steel surface either by direct con-
tact or by first partitioning into the water
phase. Little is known about the nature and
effectiveness of these components. A recent
study on the subject was used as a basis for
the model such that the degree of inhibition
was quantitatively related to the chemical
composition of the crude oil, primarily to
the concentration of saturates, aromatics,
resins, asphaltenes, nitrogen, and sulfur. In
this model, given a crude-oil composition,
the surface coverage by a crude-oil inhibitor
can be determined, leading to a reduction in
corrosion rate.
Localized Attack. The possibility of local-
ized attack was modeled by use of the Pots
modified 2D stochastic algorithm. The algo-
rithm uses a single input parameter, scaling
tendency, which is calculated by the mecha-
nistic model. When the mechanistic model
predicts no precipitation, the algorithm pre-
dicts uniformly distributed corrosion attack.
For high precipitation rates, the algorithm
predicts a uniformly protected surface.
When precipitation is set between the
extremes, the algorithm predicts a partially
protective film leading to localized corro-
sion attack.
Multiphase-Flow Model. Pipelines fre-
quently transport natural gas, water, and
crude oil simultaneously. Different flow pat-
terns can be found, most often being strati-
fied, slug, or annular flow. In the liquid
phase, water and oil can flow separated or
mixed, with either phase being the continu-
ous phase and the other being the dispersed
phase. Different flow patterns lead to a vari-
ety of steel-surface-wetting mechanisms,
which affect corrosion greatly.
To properly predict the corrosion rate in
pipelines, it is essential to understand the
flow pattern and associated flow properties
and to know which liquid is in contact with
the pipe wall. This multiphase-flow model
uses water entrainment, wetting prediction,
and flow-property calculation to determine
flow patterns.
Flow-Pattern Determination. The proce-
dure of flow-pattern determination includes
calculation of two main flow-pattern transi-
tion criteria: stratified-to-nonstratified and
slug-to-annular flow. A flow-regime map
then can be built, and a particular flow
regime can be identified for a given set of
input conditions.
Water Entrainment and Wetting Predic-
tion. In the three main flow regimes (strati-
fied, slug, and annular), the liquid layer
touches the pipe wall. The key question is:
which phase is continuous, and if it is the oil
phase, is all the water entrained? A criterion
for forming stable water-in-oil dispersed
flow was derived as the means of calculating
the critical velocity for water entrainment
within the liquid layer. Two main physical
properties, maximum droplet size related to
breakup and coalescence and critical droplet
size related to settling and separation, were
compared to deduce this criterion. The tran-
sition from stratified flow to stable water-in-
oil dispersion takes places when the oil-
phase turbulence is intense enough to keep
the water phase in droplets no larger than
the maximum diameter, which must be
smaller than that of the critical droplet size
that causes droplet separation.
Flow-Properties Calculation. If the water
phase is fully entrained by the flowing-oil
phase, there is no, or very little, corrosion risk.
However, if the water phase is not entirely
entrained and flows separated from the oil
phase, it is crucial for corrosion calculations
to predict the in-situ water cut, water velocity,
and water-film thickness. This condition
holds for all three main flow regimes consid-
ered here. The momentum and mass balances
are solved for the liquid layer to obtain the
superficial velocities of a pure-water layer,
oil/water mixed layer, and a pure-oil layer, as
well as the corresponding layer thicknesses.
After the film thicknesses are calculated, the
in-situ velocities of the three layers can be
obtained and the information communicated
to the corrosion model. JPT
For a limited time, the full-length paper
is available free to SPE members at
www.spe.org/jpt. The paper has not
been peer reviewed.
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