Sie sind auf Seite 1von 8

IPTC 13785

Corrosion Modeling Within an Integrated Corrosion Prediction Approach


Wei Sun, Kevin Geurts, Dylan Pugh, ExxonMobil Upstream Research Company
Jorge Pacheco, Craig Monahan, ExxonMobil Development Company
Robert Franco, David Norman, ExxonMobil Production Company

Copyright 2009, International Petroleum Technology Conference


This paper was prepared for presentation at the International Petroleum Technology Conference held in Doha, Qatar, 79 December 2009.
This paper was selected for presentation by an IPTC Programme Committee following review of information contained in an abstract submitted by the author(s). Contents of the paper, as
presented, have not been reviewed by the International Petroleum Technology Conference and are subject to correction by the author(s). The material, as presented, does not necessarily
reflect any position of the International Petroleum Technology Conference, its officers, or members. Papers presented at IPTC are subject to publication review by Sponsor Society Committees
of IPTC. Electronic reproduction, distribution, or storage of any part of this paper for commercial purposes without the written consent of the International Petroleum Technology Conference is
prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of
where and by whom the paper was presented. Write Librarian, IPTC, P.O. Box 833836, Richardson, TX 75083-3836, U.S.A., fax +1-972-952-9435.

Abstract
This paper describes an integrated approach, based on corrosion modeling and laboratory testing, to
optimize the use of carbon steel in corrosive service for applications such as downhole tubulars, pipelines, and
facilities. This approach presents economic advantages, such as reducing the use of expensive corrosion resistant
alloys, while ensuring the operational integrity of equipment and facilities. A key part of this integrated approach is
to apply reliable corrosion models underpinned with laboratory data. To be most effective, the models should
account for the relevant chemistry and physics of the corrosion process, including the effects of detailed water
chemistry, liquid hydrocarbons, and the degree of protection from iron carbonate or iron sulfide scales. Ideally,
models should account for variations in conditions and flow characteristics along the length of a wellbore or
pipeline. Case studies are presented that demonstrate how corrosion modeling in conjunction with laboratory
testing may be used to the selection of validate carbon steel for challenging applications.

Introduction
Although high cost corrosion resistance alloys (CRAs) were developed to resist internal corrosion, carbon
steel is still the most cost effective material used in oil and gas production. It is very important to develop an
integrated corrosion prediction approach for optimizing the use of carbon steel in corrosive service while ensuring
the operational integrity of equipment and facilities.
Both corrosion models and laboratory testing are frequently used in this industry to make lifetime predictions of
facilities using carbon steel and further to make decisions on materials selection. Corrosion models, including
empirical, semi-empirical, and mechanistic ones, have been developed over the past several decades to predict
corrosion of carbon steel1-6. These corrosion models can provide engineers quick and economical corrosion
predictions. Most of the models were validated by laboratory data and/or field data. Empirical and semi-empirical
models usually provide reasonable predictions inside of their validation range but poor predictions outside of their
range. Mechanistic models generally can extrapolate to conditions outside of their validation range and remain
accurate to a certain degree. Consequently, one should always understand the validation range and limitations of
the models to apply these correctly. Moreover, although part of corrosion mechanisms are well understood in lab
investigations, due to the complexity in production operations, it is still challenging to apply lab short-term testing
results and corrosion models to predict corrosion of facilities for twenty to thirty years of service. An integrated
approach was therefore developed by ExxonMobil1 to apply a reliable corrosion model in conjunction with
laboratory testing for predicting corrosion in oil and gas production.

ExxonMobil herein refers to capabilities within ExxonMobil Development Co., ExxonMobil Upstream Reseach Co.
and ExxonMobil Production Co.

IPTC 13785

This paper describes ExxonMobil's corrosion prediction model and the application of this model as part of an
integrated corrosion prediction approach.

Model Overview
ExxonMobil's corrosion prediction model is one of the key components of ExxonMobil's integrated
approach for corrosion prediction. This integrated approach enables the optimal use of carbon steel in corrosive
service for downhole, pipeline, and facilities applications. This integrated approach is increasingly important, due
to increasing production from corrosive resources, such as highly sour gas fields, and the need to effectively
manage the integrity of existing resources. The software implementation of ExxonMobil's corrosion prediction
model, CorrCast, provides a window based, user-friendly tool for performing corrosion rate predictions in sweet
(CO2) and sour (H2S) services. Furthermore, CorrCast serves as a platform for delivering new corrosion prediction
capabilities, such as wet gas top-of-line corrosion prediction, to ExxonMobil operating companies.

Model Description
CorrCast is based on a mechanistic corrosion model that accounts for the relevant chemistry and physics
of the corrosion process in a mixed aqueous-liquid hydrocarbon environment, which is depicted schematically in
Figure 1. The model has a number of advanced capabilities including:

Predicting corrosion in sweet (CO2) and sour (CO2 + H2S) conditions


Predicting formation and protectiveness of corrosion scales (FeCO3 or FeS)
Accounting for detailed water chemistry, including salts and organic acids
Accounting for liquid hydrocarbon effects
Predicting changes in corrosion over the length of a pipeline / flowline
Predicting corrosion in a simulated autoclave test
Accounting for corrosion inhibitor efficiency

The model has been validated against a wide range of field and laboratory data.

Figure 1. Schematic depicting the features of the corrosion model


CorrCast predicts corrosion rates by modeling the chemistry and physics of the corrosion process, including CO2
and H2S solubility in the aqueous phase, solution equilibrium reactions, electrochemical reactions, mass transfer to
and from the steel surface, scale formation, and inhibition. The calculation methodology is illustrated in Figure 2.
The model requires users to input test / field conditions, gas composition, water analysis, flow parameters, and
hydrocarbon properties. Water chemistry and electrochemistry models are then applied to calculate an unscaled
corrosion rate. The effects of iron carbonate and iron sulfide scales are modeled by first calculating scale
protectiveness factors, which are then applied to the unscaled corrosion rate. The inhibitive or antagonistic effects
of liquid hydrocarbons are also modeled and incorporated as a multiplicative factor, similar to the approach taken

IPTC 13785

for an injected corrosion inhibitor. A sensitivity tool is included in the software implementation to test the variation
of results with changes to selected input parameters.
Corrosion rates can be predicted in CorrCast at selected points in pipes for field application or for a metal coupon
in a test condition-controlled vessel for laboratory application. Rates can also be predicted as a function of length
along a pipeline for field application, and as a function of time for a metal coupon in an autoclave for laboratory
application. A detailed description of the model and calculation methodology is described below.

Iterative calculation (pipe evolution and autoclave)


Conditions
(temperature, pressure)
Scale effects
(scale type and
protectiveness)

Electrochemistry
model
(unscaled rate)

Water chemistry
model

Gas composition
(pCO2, pH2S)

Scaled
corrosion rate

Water analysis
(salts, organic acids)
Input
Flow parameters
(pipe geometry,
velocity)

Mass transfer effects


Calculated
value

Hydrocarbon
properties
(water cut, inhibitive)

Hydrocarbon effects

Figure 2. Schematic depicting the calculation methodology of CorrCast

Water chemistry
The water chemistry model requires test/field conditions (temperature, pressure), gas composition (%H2S / PH2S,
and %CO2 / PCO2), and water analysis (salt concentrations, organic acids' concentrations, bicarbonate
concentration) as input parameters. Gas solubility is modeled using Henry's Law for CO2 and H2S. Fugacity
coefficients are estimated for CO2 and H2S to adjust for real gas pressure using the Peng-Robinson equation of
state.
The water chemistry model includes equilibrium reactions for: carbonic acid dissociation, hydrogen sulfide
dissociation, weak acid (HA) dissociation, and water dissociation. Salinity is represented by the ionic strength.
Equilibrium constants are taken from the literature and vary with temperature and salinity. pH and all the species
concentrations are computed from the water chemistry model and used as inputs for the electrochemistry model
which calculates the unscaled corrosion rate.

Electrochemistry model
+

CorrCast models the corrosion current by assuming direct attack by H , H2CO3 HCO3 , and HA at the surface of the
metal. The electrochemical reactions include the cathodic and anodic reactions listed below:
-

2H2CO3 + 2e = H2 + 2HCO3
2HCO3- + 2e- = H2 +2CO32+
2H + 2e = H2
2HA+2e = H2 + 2A2+
Fe = Fe + 2e

(1)
(2)
(3)
(4)
(5)

The corrosion current is equal to the anodic current which is equal to the sum of the cathodic currents:

icorr = iFe 2 + = iH+ + iH 2 CO3 + iHCO + iHA


3

(6)

IPTC 13785

The unscaled corrosion rate is therefore calculated using the following equation.

CR =
where

icorrMFe
= 1.155icorr
FenF

(7)

icorr is in A/m2, MFe is the molecular weight of iron in g/mol, Fe is the density of iron in kg/m3, n is number

of moles of electrons used in reducing or oxidizing a given species, F is the Faradays constant, and CR is in
mm/s, which can be conveniently converted to mm/y.
When H2S is present in the water solution, it is assumed that the adsorption of sulphur on iron affects the potential.
This effect varies with coverage and is fit by a Langmuir isotherm.

Mass transfer effect


Mass transfer allows the movement of solution species from the bulk fluid to a near-surface region, and vice versa.
Mass transfer in the model is described via Fick's First Law. Mass transfer "in" is equal to mass transfer "out",
making allowances for net flow. Hydrodynamic models are applied to calculate shear stresses and mass transfer
coefficients for both pipe and autoclave simulations. There are no local concentration surpluses. Electric field
effects are assumed to be dominated by hydrodynamics. Adsorption and desorption are neglected as a
conservative assumption.

Scaling methodology
In CO2 and CO2/H2S corrosion environments, corrosion products such as iron carbonate (FeCO3) and iron sulfide
(FexS), can form and decrease the corrosion rate of carbon steel. Scale formation is therefore one of the key
factors affecting corrosion rate. CorrCast applies scaling factors for quantifying the effects of scale on corrosion at
the conditions of interest.

CR scaled = CR unscaled SFFeCO3

or

FeS

(8)

where CR scaled is the scaled corrosion rate, CR unscaled is the unscaled corrosion rate, and SFFeCO
3

or FeS

is the

scaling factor for FeCO3 or FeS, which is a function of temperature, pH, and local supersaturation.

Hydrocarbon liquids
CorrCast includes the effects of hydrocarbon liquids (crude oil or condensate) on corrosion in two ways. First, it
uses a viscosity based drainage model to estimate how much the liquid hydrocarbon contacts the metal surface
versus the aqueous phase. This is a function of the water cut and the relative viscosities of the water and liquid
hydrocarbon phases. If no data exists on inhibitive or corrosive properties of the liquid hydrocarbon, it is assumed
to be corrosion neutral (simply reduces corrosion by displacing the aqueous phase). Second, it can account for
inhibitive or corrosive properties of the liquid hydrocarbon using the empirical equation below

CR = CR actual

a
1
W

b+

(9)

where a and b are constants, and W and H are water and hydrocarbon volumes respectively. This equation can
account for species in the liquid hydrocarbon that partition into the water that further inhibit or accelerate corrosion.
The empirical constants a and b can only be obtained for a particular hydrocarbon from experimental data.
Therefore, laboratory tests are required to establish how field hydrocarbons, if present, may affect the corrosion
rate.

IPTC 13785

Validation Range
Validation ranges of key parameters in CorrCast are given below:

Temperature: 39-316F (4-158C)


CO2 partial pressure: up to 648 psia (44 atm)
H2S partial pressure: up to 100 psia (6.8 atm)
Equivalent salt concentration: up to 32 wt%
Water cut: 3-100%

Obtaining Flow Parameters from a Flow Simulator


The current version of CorrCast can import hydraulic results from a flow simulator, such as OLGA, PipePhase, or
Prosper. Predicted values for fluid velocity, temperature, pressure, gas composition, water cut, viscosity, flow
regime, and liquid holdup along the pipe or tubing are imported. CorrCast predicts the corrosion rate beginning at
the entrance to the pipe, and proceeding to the exit, taking account along the way of changes in the fluid properties
and hydraulic variables, as well as changes in iron concentration, pH, and scale formation.

Laboratory Testing Methodology


Corrosion models are not ordinarily used alone to determine corrosion rates, especially if the conditions
are near the validation and/or validity limits of the model.7 Instead, confirmatory laboratory corrosion tests
frequently accompany or follow the modeling. Specialized laboratory test apparatuses, such as large-volume highpressure, high-temperature autoclave test cells and/or a large-diameter sour multiphase flow loop, are often
necessary to ensure proper replication of field conditions in the laboratory. In the course of corrosion research, the
ExxonMobil Materials and Corrosion Laboratory (M&CL) has been designed and constructed specifically for this
purpose. The M&CL includes a state-of-the art building control system to ensure optimal safety and environmental
performance, while also supporting the experimental facilities.
Figure 3 shows a photograph of a corrosion autoclave in the M&CL and includes a schematic depiction of the
autoclave internals. These autoclaves can deliver shear stresses to the coupons up to 90 Pa at temperatures as
high as 230oC (450oF) and a total pressure up to 34.5 MPa (5,000 psi).
Thermocouple

Gas
Impeller for
water/hydrocarbon
mixing

Test Material

Liquid

Baffles for
vortex
prevention

Impeller for
shear stress
production

Figure 3: Autoclaves at ExxonMobil's Materials and Corrosion Laboratory are specially designed to
replicate field conditions, including fluid chemistry and mass transfer
A large-diameter, multiphase flow loop can simulate flow regimes that are not attainable in a stirred autoclave,
primarily slug flow and flow with large upsets. Figure 4 is a photograph of the 102-mm (4-in) diameter multiphase,
Hastelloy C276 sour flow loop at the M&CL. This 30-m (100-ft) long flow loop pumps liquid and gas separately

IPTC 13785

and provides the ability to replicate all production flow regimes at inclinations between 0o and 90o. The maximum
gas and liquid velocities are ~9 m/s (30 f/s) and ~4 m/s (13 f/s) respectively. Liquid temperatures can be varied
from 5oC (40oF) to 120oC (250oF) with a maximum total pressure of 6.9 MPa (1,000 psi) and a maximum H2S
partial pressure of 0.2 MPa (30 psi). Both coupons and electrochemical probes can be used in the flow loop, which
provides the ability to remove coupons under pressure. Results can be extrapolated to other pipe sizes by
ensuring equivalent mass transfer between the flow loop and the service line based on the aforementioned
mechanistic relations.

Figure 4: 102-mm (4-in.) multiphase sour flow loop used for corrosion testing at the materials and
corrosion laboratory

Case Studies
Case 1
In this example, carbon steel was evaluated to determine its applicability for tubing in a new well at a
mature field. The well would initially be used as an appraisal well, producing oil for approximately three months,
and it would then be switched to a water injector for the remainder of its life. At this field, 13 Cr is used for tubing in
production wells to mitigate CO2 corrosion and carbon steel is used for tubing in water injection wells. If carbon
steel was not feasible in this case, 25 Cr Super Duplex would be required since 13 Cr is susceptible to pitting in
water injection service where there may be upsets in oxygen control. Reservoir and subsurface engineers
provided the design conditions during the initial production phase, including hydrocarbon liquid, hydrocarbon gas,
and formation water analyses for the reservoir (key component bicarbonate 160 ppm), expected range of
temperatures (55oC to 85oC) and pressures along the wellbore (PCO2 < 58 kPa, no H2S), and estimates of the flow
velocities (~1 m/s) and water cut (~10%).
Corrosion modeling was performed with a widely-used empirical model and CorrCast based on the expected upper
bound of CO2, the supplied formation water chemistry, and the range of temperatures expected along the wellbore.
The empirical model predicted general corrosion rates up to 6.9 mm/y (270 mpy). This model did not, however,
account for any beneficial effects from the formation of an iron carbonate scale or from the oil. This prediction
indicates that up to 1.7 mm of wall loss could occur during the three month production period, which corresponds
to more than 10% of the tubing thickness. In contrast, CorrCast, which includes the effect of a protective iron
carbonate scale, predicted general corrosion rates up to 0.5 mm/y (20 mpy) for 100% water cut. Corresponding
unscaled corrosion rate predictions were up to 8.0 mm/y (315 mpy), which agrees well with the empirical model,
but such high corrosion rates are unlikely because conditions should be favorable for the formation of an iron
carbonate scale. With the addition of oil (10% water cut), CorrCast predicted general corrosion rates of <0.1 mm/y
(<4 mpy). These predictions indicate that there will be less than 0.2 mm of wall loss during the three month
production period and that the prediction from the empirical model represents a conservative upper bound.
This example demonstrates how the advanced capabilities of the model enabled it to reduce the conservatism built
into the empirical model and provide a more realistic corrosion prediction. Based on this analysis, carbon steel

IPTC 13785

was used for the tubing in this well. Since the model was inside its validation range no laboratory testing was
conducted.

Case 2
In this example, inhibited carbon steel was evaluated for a wet gas flowline in highly corrosive service. The
o
flowline would transport full wellstream fluids with a CO2 partial pressure of 1,800 kPa at a temperature of ~30 C.
The reservoir is predicted to sour over time, giving rise to small amounts of H2S (up to ~0.7 kPa). Reservoir and
facilities engineers provided detailed conditions including gas and water analyses, flow rates, and temperature.
Corrosion modeling was conducted with CorrCast to confirm the need for inhibition and to compare against
uninhibited corrosion tests conducted at M&CL during the corrosion inhibitor qualification program. For the initial
conditions (sweet), CorrCast predicted general corrosion rates of 1.6-3.8 mm/y (64-155 mpy), which confirmed the
need for inhibition. A range of corrosion rates was reported because a poorly protective iron carbonate scale was
predicted to form (1.6 mm/y corresponds to the scaled rate, 3.8 mm/y corresponds to the unscaled rate). For the
end of life conditions (sour), CorrCast predicted a general corrosion rate of 0.2 mm/y (8 mpy). The reduction in
corrosion rate versus the initial conditions was due to the formation of a protective iron sulfide scale. CorrCast
predictions agreed well with uninhibited corrosion tests conducted on X52 and X65 pipeline steels. For the initial
conditions (sweet), the measured corrosion rates of the X52 and X65 coupons were 3.9 mm/y (154 mpy) and
1.4 mm/y (54 mpy), respectively. These rates agree well with the range predicted by CorrCast, and the measured
difference in rates between the two steels was attributed to differences in microstructure affecting the formation of
the iron carbonate scale. For the end of life conditions (sour), the measured corrosion rates of both steels was
0.2 mm/y, which agrees with the CorrCast prediction. Additional corrosion tests were conducted with inhibitor, and
the measured corrosion rates were 0.01 mm/y (0.4 mpy), which confirmed the inhibitor would mitigate corrosion at
the dosage tested.
This example demonstrates how an integrated approach of modeling and testing supported the use of inhibited
carbon steel for a challenging application. It also shows the ability of the model to predict the impact of corrosion
scales in both sweet and sour conditions. Based on the modeling and corrosion inhibitor qualification testing,
inhibited carbon steel was selected for the flowline.

Conclusions
This paper provides an overview of ExxonMobil's corrosion prediction model and its implementation in the
CorrCast software. It describes how to apply the model in conjunction with laboratory testing to evaluate the use of
carbon steel in oil and gas production environments. An integrated approach to corrosion modeling and laboratory
testing is important to ensure long-term reliability of carbon steel production equipment with minimal life-cycle cost.

Acknowledgement
The authors would like to acknowledge R. V. Reddy from ExxonMobil Upstream Research Company, and
J. C. Bondos and J. L. Nelson from ExxonMobil Production Company for early-stage corrosion model
development.

References
1. C. de Waard, D. E. Milliams, "Prediction of Carbonic Acid Corrosion in Natural Gas Pipelines", First
International Conference on the Internal and External Protection of Pipes, Paper F1, Cranfield, UK: BHRA
Fluid Engineering, 1975.
2. C. de Waard, U. Lotz, D. E. Milliams, "Predictive Model for CO2 Corrosion Engineering in Wet Natural Gas
Pipelines", Corrosion, Vol. 47, No. 12, p. 976, 1991.
3. C. de Waard and U. Lotz, Prediction of Corrosion of Carbon Steel, Corrosion/93, paper no. 69, Houston, TX:
NACE International, 1993.

IPTC 13785

4. CO2 Corrosion Rate Calculation Model, NORSOK standard No. M-506, http://www.nts.no/norsok, Oslo:
Norwegian Technology Standards Institution, 1998.
5. E. Dayalan, G. Vani, J. R. Shadley, S. A. Shirazi, and E. F. Rybicki, Modeling CO2 corrosion of carbon steels in
pipe flow, Corrosion/95, paper no. 118, Houston, TX: NACE International, 1995.
6. S. Nesic, J. Postlethwaite and S. Olsen, An electrochemical model for prediction of CO2 corrosion,
Corrosion/95, paper no. 131, Houston, TX: NACE International, 1995.
7. J. C. Bondos, R. V. Reddy, D. V. Pugh, D. A. Norman, J. L. Pacheco, and J. L. Nelson, Accurate corrosion
prediction through an integrated approach, SPE Production & Operations, SPE 111430, May 2007.