mechanistic prediction models
TRANSCRIPT
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Mechanistic prediction models
Mechanistic Prediction Models Of CO 2 Corrosion
Introduction
In order to assess and predict corrosion in oil and gas production, it is necessary to
define the chemistry contained in the oil and gas environment in line with mechanism of
the corrosion reactions. Sometime, the corrosion reactions on the steel surface attack at
the different ways which may lead to misinterpretation. Many variations of damages
due to corrosion indicate how corrosion mechanism happens in multi chemical
reactions. Corrosion attacking pipeline material forms various model damages such as:
pitting, cracking and scale detachment (spalling). Thus, prediction
corrosion mechanism is a significant importance tool to enhance the understanding of
corrosion behavior. The main concepts of mechanistic models are the interrelation of
chemical reactions or physical changes of state. The corrosion model is developed by
using information about standard state properties of all species of interest with a
formulation for the Gibbs energy. The thermodynamics model is used to predict the
concentration and activities of both ionic and molecular species in the systems.
Factors Influencing CO2 Corrosion
a. pH
Normally, the higher pH, the lower is the corrosion rate. The pH is influenced bychanging the H+ ions concentration, temperature, pressure, and ionic strength. The
effects of the dissolved iron bicarbonate will also increase pH . The increase of pH
causes film thickening and film becoming more dense and protective. Dependency of
pH to the temperature and pressure is expressed in the following expression:
b. Temperature
The temperature influences the conditions of protective iron carbonate layers. At
temperature below 60oC, Hydrogen evolution acts a rate determinating step and
carbonate scale does not form well. Carbonate scale governs corrosion rate at the range
temperature of 60 - 100oC when protective films is formed. Such temperature is called
as scaling temperature which is formulated as:
Tscale= 2400/(6.7+0.6Log(fCO2)) ..(2)
The effect of temperature of the diffusion coefficient is given by:
c. The effect Of CO2 Partial Pressure
In the case of no protective film, an increase in CO2 partial pressure, corrosion rate will
increase. The higher the partial pressure of CO2, the higher is CO32- ions concentrationwill have higher supersaturation (at the high pH) results in increasing of corrosion rate.
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In the case of non-ideal gas, the total pressure must be corrected with CO2 fugacity
which is formulated as:
CO2=a.pCO2. (4)
Where a is the fugacity coefficient
d Effects Of Flow
Flow induced corrosion is due to combination effects of mechanical and
electrochemical forces. The flow results in thinner boundary layer which allows
dissolved oxygen in water to corrode the surface more quickly. Higher flow will also
increase the wall stress that can cause localized corrosion and surface damage.
e Effects Of Acetic Acid (HAc)
The presence of HAc can change the mechanism of the anodic dissolution of iron
through competitive adsorption of acetate ions, CH3COO- (or Ac-) and HCO-3. The
fact that carbonic acid (H2CO3) is not fully dissociated in the solution, it provides a
reservoir of H+ ions which contribute the additional cathodic reactions. The increase of
corrosion rates is also attributed to the forming of thinner iron carbonate films since the
formation of iron acetate.
d. Effects Of Fe2+ Concentration
The effects of Fe2+ ions on corrosion rate are influenced by their ability to form iron
carbonate. It has been commonly accepted that solid iron carbonate scale precipitates onthe steel surface when the concentrations of Fe2+ and CO3 2- ions in the CO2 water
solution exceed the solubility limit. Protective scale will not form when scaling
tendency very low although Fe2+ have achieved a saturation value. In this condition,
the iron carbonate film is porous and non protective which does not have effects in
reducing corrosion rate.
Corrosion Rate Calculation
The mathematical model of corrosion occurring at the metal surface can be expressed in
the several equations from Equation 5 to Equation 8. These corrosion mechanisms are
based on several assumptions which can be described as follows: convective diffusion(Eq. 5), molecular diffusion (Eq. 6) and diffusion via solid film (Eq. 7). Corrosion
mechanism which happens in solutions as a combination of mix gases can be expressed
as:
Convective diffusion reactions through the mass transfer boundary layer.
Molecular diffusion through the liquid in the porous outer scale:
There is always a very this film and dense film at the metal surface acting as a surface
barrier. Using an assumption that outward diffusion of Fe2+ is neglected and the filmcontinuously grows through a cyclic process, the outer scale of film is controlled by
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mass transfer reaction. Then, solid state diffusion through the inner film can be
formulated as:
By eliminating the unknown interfacial concentration co and ci, from equations, the
following equation is obtained for the corrosion rate of steel due to mixed species will
become:
In case when inner solid film does not form, Equation 7 can be neglected. Thus,
Equation 8 will become:
Where:
Km is mass transfer coefficient of species I (m/s)
is bulk concentration of species i (mol/m3)
is the interfacial concentration of species i at outer scale/solution interface (mol/m3)
is diffusion coefficient for dissolved species i (m2/s)
is outer scale porosity
is tortuosity factor
is interfacial concentration of species i
is the thickness of outer film sacle
A is Arhrhenius constants
Tk is temperature (Kelvin)
cs is surface temperature
The total corrosion rate equals to the sum of the corrosion caused by each species.
Based on the description of the CO2 corrosion process, a schematic of the CO2
corrosion process is shown in Figure 1 below.
Scale Properties
The corrosion process happens via a direct heterogeneous solid state reaction at the steel
surface which acts as a solid state diffusion barrier. The amount of scale retained on the
metal surface depend on time, hydrodynamic stresses, chemical reaction, precipitation
rate, change of mass scale removal of the outer scale. Empirically, competition growth
between scale formation and scale damage is formulated:
This equation is used to calculate the changes of the scale, thus the change in mass of
the outer scale can be calculated.
Experiment Setup
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Electrodes
A three-electrode set-up was used in all electrochemical experiments. A rotating
cylinder electrode with a speed control unit was used as the working electrode. A
platinum or graphite was used as a counter electrode. Glass cell was fitted with graphite
electrodes as auxiliaries electrode and a Ag/AgCl as a reference electrode.
Specimen preparation
The working electrodes were carbon steels which have chemical compositions as can be
seen in Table 1. It was used a cylinder rod of 1.2 cm2 in diameter and 1 cm thickness.
Before immersion, the specimen surfaces were polished successively with 240, 400 and
600 grit SiC paper, rinsed with alcohol, and degreased using acetone. Some of the
experiments were repeated in order to obtain the reproducible results.
Cell Solutions
The schematic of the experimental setup are shown in Figure 2. The experiments were
performed both in flow and stagnant solutions condition. The total pressure was 1 bar,
the glass cell was filled with 1 liter of distilled water and 3% wt NaCl which was stirred
with magnetic stirrer. Then, CO2 gas was bubbled through the cell (at least one hour
prior to experiments) in order to saturate and de-aerate the solution. Temperature was
set using a hot plate. After the solution was prepared, the pH was measured to reach the
pH set by using NaHCO3 as buffer solutions.
Simulation of flow condition test was conducted using rotating cylinder electrode
(RCE). A cylindrical working electrode was screwed onto an electrode holder at thecenter of the cell for rotating in the RCE. The Linear Polarization Resistance (LPR)
technique was used to measure the polarization resistance, Rp, and the corrosion rate.
The procedure is similar to that described in ASTM G 5-94 - Standard Reference Test
Method for Making Potentiostatic and Potentiodynamic Polarization Measurements.
Results And Discussions
Effects Of Temperature And pH On Corrosion Rate
The effects of increasing temperature on the corrosion rate in solutions containing 3%
sodium chloride and different pH is shown in Figure 3. The model prediction was
assumed that there was no inner solid film formation. The barrier film was due to only
outer porous film. The results were shown that both of the experimental and predictions
results presented an increased of the corrosion rate. Comparison of those two results,
there were clearly a good agreement. The effect of temperature increased corrosion rate
fast at the pH 3.8. While, at the pH 6, the corrosion rate increased slowly. The corrosion
rate was not reduced significantly, at pH 6, which reflects a relatively porous, detached
and un-protective of scale. It may relate to the fast formation of the scale. All the results
were also revealed that at the range temperature of 50oC to 60oC, corrosion rate started
to decrease that associated to the scaling temperature. This showed that electrochemical
reactions and mass transfer also increased with temperature.
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Effects Of Acetic Acid And Rotation Rate On Corrosion Rate
The mechanistic calculation of effect of acetic acid concentration on the corrosion rate
in solutions containing 3% sodium chloride and CO2 gas is shown in Figure 4.a. It was
an evident that the corrosion rate calculated using mechanistic corrosion formula was
not in good agreement with the experiments. The data from the calculation showed thatwhen HAc was present, corrosion rate was consistently increased as HAc was increased.
But, from the experiments results, effects of HAc in increasing corrosion rate happen
only until concentration less than 200 ppm. At the HAc concentration more than 200
ppm, the corrosion rate was decreased.
The effect of rotating rate in 3% sodium chloride solutions at pH of 3.8 and at 22C is
shown in Figure 4.b. An increase in rotating rate up to 6000 rpm results an increase of
corrosion rate. These data were obtained both from experiments and calculation results.
Effects of flow in changing corrosion rate are caused by the changes of mass transfer
boundary layer that have a prime role in corrosion behavior.
Conclusion
The mechanistic prediction models of CO2 corrosion have shown a satisfied model in
calculating corrosion rate, predicting corrosion mechanism and simulating the growth of
corrosion products. Using this prediction, the parameters influencing corrosion such as:
rate of controlling step corrosion reaction, rate of ions dissolution in the solution can
easily be observed and analyzing. Through studying CO2 corrosion mechanism, it can
be concluded that CO2 corrosion produce a very thin films (1-5 m). The film
properties such as: porosity, contour surface appearance and quality of the film change
with time and influenced by solution compositions. The decrease of corrosion rate in thehigher of pH is controlled by the film formation. The other factors affecting corrosion
rate are the scale formation rate and the scale damage rate. The scale formation rate
includes both the corrosion rate and precipitation rate have also role in corrosion
mechanisms.
Acknowledgments
The authors are thankful to Universiti Teknologi PETRONAS for providing grant and
facilities for the research.
References
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