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Supplement G15. CO2 Corrosion

Supplement G15. CO2 Corrosion

Scope
The scope of this Technical Supplement module is to develop a simple means by which carbonic
acid corrosion rates can be conservatively estimated in an upstream environment. The module is
predominantly based on the NORSOK Standard M-506 Rev 1, which account for the effect of the
CO2 partial pressure, temperature and the effect of fluid velocity. M-506 was specifically
developed to account for the fluids, pressures, and temperatures expected in oil and gas
production.
Description of Damage
Carbon Dioxide is a weakly acidic gas which is corrosive when dissolved in water becoming
carbonic acid (H2CO3). CO2 is commonly found in upstream sections before treatment. CO2
corrosion requires the presence of water in order to produce the Carbonic acid. The primary
variables, which influence CO2 corrosion rates, are the CO2 concentration, operating pressure,
operating temperature, application of inhibitors, flow rate, and presence of hydrocarbon fluids and
contaminants in the system.
Aqueous CO2 corrosion of carbon and low alloy steels is an electrochemical process involving the
anodic dissolution of iron and the cathodic evolution of hydrogen. The electrochemical reactions
are often accompanied by the formation of films of FeCO 3 (and/or Fe3O4) which can be protective
or non-protective depending on the conditions under which these are formed.
Basic Data
The data listed in Table 1 are required for the estimation of the CO 2 corrosion rate. Figure 1
illustrates the steps required to determine the corrosion rate. Entering only the data marked
required will result in a conservative calculated corrosion rate. As more optional data is entered,
the calculation of the corrosion rate is more refined. If precise data have not been measured, a
knowledgeable process specialist should be consulted.
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Table 2. Basic Data Required for Analysis

Basic Data
Temperature Required
Pressure Required
CO2 concentration (mole %)
Required
pCO2 Required, if CO2 concentration
is not given
Material of Construction Required
pH Required
Stream properties: bulk density, m,
viscosity, m, gas to liquid ratios
Required
For systems with liquids: Water Cut
Optional
For gas systems: Relative humidity,
RH or dew point temperature, Td
Optional
Glycol/Water mix - Optional
Inhibition efficiency - Optional
Comments
The corrosion phenomenon is highly temperature dependent. The
maximum temperature of the process is required. Temperatures above
140C (284F) are not considered in this module.
Total pressure of the system. The total pressure of the gas is a big
contributor in the corrosion rate up to about 250 psig.
Determine the CO2 partial pressure (pCO2) = (mol fraction of CO2 total
pressure) A max 580 Psi partial CO2 pressure is considered in this module.
CO2 partial pressure, which is converted to CO2 fugacity to account for
non-ideal behavior.
Determine the material of construction of equipment/piping. Stainless steels
and copper alloys are assumed to be resistant to CO2 corrosion
If known explicitly, the pH of the stream should be used. Otherwise
Equations 1, 2, or 3 can be used to estimate the pH based on the CO2
partial pressure, whether the water in the stream is Fe++ saturated or water
with salinity slightly larger than seawater.
This module gives some guidance with respect to typical values properties
expected in natural gas-oil mixtures (ie reservoir fluids). Estimation of
densities can be made on the basis of the oil density (API), gas oil ratio
(GOR) and pressure, P and temperature, T. For other streams, a process
engineer should assess these parameters.
Determine the percentage of water in the system. The default for this field
is 30%
Determine the dew point temperature, Td based on the water content.
Equation 4 is provided for guidance, but should not be assumed to be
accurate within 10F. If not provided the gas stream temperature is
assumed to below the dew point.
Water content of glycol/water mix in %weight (%water in the total
glycol/water mix). The default value would assume no glycol added in the
system.
Requires %efficiency of the inhibitor. No inhibitor injected as a default
value.

Calculation of the corrosion rate

The corrosion rate, CR is calculated as the product of two factors, the base corrosion rate, CRbase
and the effect the corrosion inhibitors, Finhib or glycol, Fglycol.
CR min Fglycol , Finhib CRbase ............................................................................5

The calculation of the base corrosion, CRbase is most complex; it depends on the temperature, the
partial pressure of CO2, the fluid flow velocity and the pH of the fluid. The following paragraphs
detail how these can be estimated for RBI purposes for some simple mixtures of crude oil, water,
and natural gas mixtures. In order to estimate corrosion rates for situations outside this simple
mixture, the analyst should refer to the NORSOK standard M-506. In cases where the equipment
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is not associated with upstream production, the analyst should also be prepared to adjust or
estimate corrosion rates for fluids that are not mixtures of crude, water and natural gas.
Primary screening criteria
CO2 must be present in the system
The material of construction must be carbon steel
There must be liquid water in the system. If it is a gas system the temperature must be below
the dew point for water to condense that is the relative humidity must be 100%.
Relative humidity
In order for corrosion to occur, there must be liquid water present in the line. In a system
transporting gas, liquid water exists only if the temperature is below the dew point and the relative
humidity in the stream is greater than 100%. When a mixture of water vapor and natural gas
behaves approximately as ideal gases, the relative humidity in a gas is 100% when the partial
pressure of the water vapor is equal to the saturation pressure. This result in the simplified
formula for the relative humidity,
xP / Psat T
RH ....................................................................................................6
0.622 x
where x = ratio of the mass of water to the mass of dry gas, or %w/(100%%w), where %w is the
percent water by weight in the stream. P is the pressure and Psat(T) is the saturation pressure for
water at temperature T, which can be obtained from steam tables. The 0.622 is the ratio of the
molecular weight of water (18) to the average molecular weight of air (29). Using Equation 7
and the steam tables, an approximate equation for the dew point temperature Td (F) as a function
of the pressure and P water content %w can be developed.
log10 Td 2.0866 0.2088 log10 % w / 100 0.2242 log10 P ..................................8

where P is the pressure in psia, %w is the percent water by weight in the stream (lbm/100lbm),
between 0 and 30.

Base Corrosion Rate

The base corrosion rate in mm/y is calculated from the following function,
0.146 0.0324 f CO 2
S
CRbase f T , pH f CO 2
0.62
................................................9
19
where f(T, pH) the temperature-pH function, tabulated in Table 3 as a function of the temperature,
T (C) and the pH. This tabulated function was calculated by combining M-506s temperature
and temperature dependent function pH function into a single quantity. The resulting function is
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also plotted as a surface plot in Figure 2. The analyst should note that these functions jump
sharply between 80C and 90C.
Note that the base corrosion rate given by Equation 10 is in mm/year. Multiply the result in mm/y
by 40.8 to get mpy.
The parameters, the CO2 fugacity fCO2 (bar), pH, and the shear stress from the flow S (Pa) needed
to calculate the basic corrosion rate are discussed in the following paragraphs.
Table 4. pH-temperature function
Temperature C
pH 20 30 40 50 60 70 80
3.5 6.00 8.52 10.98 11.92 12.83 13.42 13.93
4.0 5.45 7.77 10.06 10.96 11.86 12.01 12.12
4.5 4.90 7.02 9.13 10.01 10.89 10.60 10.31
5.0 3.72 5.16 6.49 6.86 7.18 6.58 6.01
5.5 2.55 3.40 4.08 4.10 4.05 3.61 3.20
6.0 1.55 2.00 2.30 2.20 2.03 1.86 1.70
6.5 0.72 0.91 1.02 0.94 0.84 0.87 0.90
Temperature C
pH 90 100 110 120 130 140 150
3.5 9.37 9.23 8.96 8.55 7.38 6.26 5.20
4.0 7.91 8.04 8.09 8.06 6.39 4.91 3.62
4.5 6.45 6.38 6.22 5.98 3.98 2.31 0.98
5.0 2.44 2.19 1.87 1.48 0.96 0.53 0.19
5.5 0.82 0.94 1.07 1.20 0.80 0.46 0.19
6.0 0.49 0.62 0.77 0.92 0.63 0.39 0.19
6.5 0.32 0.42 0.53 0.65 0.47 0.32 0.19
Notes:
C = 5(F-32)/9
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14.0

12.0

10.0

8.0
f (T,pH)
6.0

4.0

2.0

0.0
20
40
60
3.5 80
100
4.5 120
5.5 T (C)
pH 140
6.5

Figure 3. pH-temperature function

Fugacity
Fugacity has units of pressure. It is used in place of the pressure or partial pressure in
calculations concerning the equilibrium of real gas mixtures. When the fugacity is used in place of
the pressure, real gases can be modeled using the equations for ideal gases. M-506 uses the
following equation for modeling the fugacity, fCO2.
1.4
log10 f CO 2 log10 pCO 2 min 250, pCO 2 0.0031
T 273 ...............................11
log10 pCO 2 log10 a

where pCO2 is the CO2 partial pressure in bar, T is the temperature in C, and a is the fugacity
coefficient, the ratio between CO2 fugacity and the partial pressure, that is fCO2 = apCO2. Figure 4
shows the fugacity coefficient a plotted for a range of temperatures and pressures.
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Notes:
pCO2 (psi)
Chart is for fugacity coefficients for
0 500 1000 1500 2000 2500 3000 3500
mixtures of natural gas and CO2, with less
1.0 than 5mole % CO2.
Partial pressure is equal to the product of the
total pressure and the mole fraction of CO2
0.9
150C
302F
For partial pressures above 250 bar (3625
psi) use the fugacity coefficient for the
125C temperature of interest evaluated at pCO2 =
257F
0.8 250 bar the values on the right side of the
chart.
100C The values in the chart are identical to
212F
0.7 Equation 12.
75C
167F

0.6

50C
122F
25C
0.5 77F

0.4
0C
32F

0.3
0 50 100 150 200 250
PCO2 (bar)

Figure 5.Fugacity coefficients for CO2 in natural gas.

pH
For RBI purposes, the pH can be calculated using one of the following approximations. For
condensation,
pH 2.8686 0.7931log10 T 0.57 log10 pCO 2 ..............................................13
for Fe++ saturated water,
pH 2.5907 0.8668 log10 T 0.49 log10 pCO 2 ..............................................14
and for water with salinity slightly greater than seawater (salinity = 46 g/l),
pH 2.7137 0.8002 log10 T 0.57 log10 pCO 2 ..............................................15
where T is the temperature in F and pCO2 is the CO2 partial pressure in psi. These approximations
were developed from Monte Carlo simulations. These simulation studies used the equilibrium
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equations recommended and by M-506 to calculate the concentration of hydrogen cation and then
the pH for a wide range of temperatures, pressures, and CO2 mole fractions. Figure 6 shows that
the expressions developed are conservative compared to the values obtained from M-506.
Equations 16, 17, and 18 apply to water, seawater and Fe++ saturated water and do not account for
the buffering action of bicarbonate ions or for the increase acidity caused by salinity levels higher
than 45 g/l. In cases where these factors are significant, the analyst should consider using an
alternative analysis such as direct application of the provisions in M-506 for salinity and dissolved
bicarbonate.
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5.5 5.5

5.0 5.0

4.5 4.5

4.0 4.0

3.5 3.5

3.0 3.0

2.5 2.5
2.5 3.0 3.5 4.0 4.5 5.0 5.5 2.5 3.0 3.5 4.0 4.5 5.0 5.5

Norsok Norsok

CO2 in water. Equation 19 CO2 in Fe++ saturated water. Equation 20

Notes:
5.5
Charts are scatter plots for pHs calculated using the
M-506 software provided by NORSOK and the
5.0 approximate expressions Equations 21, 22, and 23.
Each chart contains 1000 simulated temperatures,
pressures, and CO2 pressures
4.5
Diagonal line represents the condition where the
approximate expression equals the pH calculated by
4.0 the M-506 software.
The charts demonstrate that the approximate
expressions are conservative. A majority of the
3.5
simulations fall below the lines indicating that the
approximate expression calculates a pH, which tends
3.0 to be lower than the M-506 software does for the
same conditions.
2.5
2.5 3.0 3.5 4.0 4.5 5.0 5.5
Norsok

Salinity = 45 g/l. Equation 24

Figure 7. Norsok vs Equations 25, 26 and 27 for approximating pH
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Flow velocity
M-506 uses the fluid flow shear stress to model the effect of flow velocity on the base corrosion
rate. M-506 recommends the following equation to calculate the stress, S in Pa,
m u m2
S f ...........................................................................................................28
2
where f is the friction factor, um is the mixture flow velocity in m/s, and m is the mixture mass
density in kg/m3. The friction coefficient is approximated for turbulent flow (Re > 2300) by,
e 10 6
0.33

f 0.0013751 20000 .................................................................29
D Re

where the e/D is the relative roughness, Re is the Reynolds Number of the mixture
D mum m D
Re ..............................................................................................30
m A m
where D is the diameter in m, and m is viscosity of the mixture, in Pas (0.001cP = Pas).
Equation 31 also shows that the Reynolds number can be calculated using the mass flux, m , the
cross sectional area, A. Figure 8 shows f as a function of Re assuming that the relative roughness
e/D is 0.0002. The shear stress need not exceed 150 Pa.

0.01

0.001
1.00E+04 1.00E+05 1.00E+06 1.00E+07 1.00E+08
Reynolds number, Re

Figure 9. Friction factor, f as a function of Re with e/D = 0.0002

M-506 gives some guidance on the calculation of the two-phase viscosity, m, density, m and fluid
velocity, um. These factors depend on the volumetric ratio of the liquid flow to the flow ,
sometimes called the liquid hold up, the amount of water in the liquid fraction (or water cut, ),
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the gas water and oil viscosities at the temperature and pressure. These calculations are complex
and go beyond the scope of an RBI study. If required, the analyst can refer to the
recommendations in NORSOK or use the software provided by NORSOK to perform the
calculations recommended in M-506 to approximate the two-phase flow characteristics. While M-
506 provides some guidelines for the calculation of bulk fluid properties, they do not explicitly
account for the solubility of natural gas in oil, which can also effect the all of these properties.
Several simulations using typical correlation used to approximate the properties typical reservoir
fluids mixtures of gas, crude oil and water resulted in the typical bulk properties tabulated in
Table 5 at 1000, 500, and 200 psi. Table 6 shows typical properties for natural gas with a gas
gravity of 0.8 (Air = 1). These figures indicate that for gas oil ratios (GOR) less than 2000 scf/stb
or 360 m3/m3, and at pressures higher than 500 psi, a viscosity value of 1.2 cP is a conservative
estimate of most light to medium crude oils. A value of 5 cP or greater is appropriate for heavier
products with GORs greater than 500 scf/stb or medium or light products with GORs less than
500 scf/stb. However, much higher viscosity values can be expected for heavy products with low
GORs < 100 scf/stb. For natural gas streams, the viscosity values less 0.03 cP the value
recommended by M-506 is conservative.
For the calculation, natural gas densities the real gas equation is appropriate,
P
g ....................................................................................32
0.46306 Z T 460

where g is the density in lb/ft3, T is the temperature in F, P is the pressure in psia, and Z is the
compressibility factor. Figure 10 shows the Z-factor as a function of both temperature and
pressure for a typical natural gas with a specific gravity of 0.8 (Air = 1).
The density of a mixture of gas and oil is more complex. At low pressures, the amount of gas in
solution is relatively small and the density of the liquid fraction is near it density at standard or
stock tank conditions. However, at higher pressures, the gas dissolves in the liquid, this reduces
the amount of free gas and changes the density and viscosity of the liquid fraction. For oil-gas
mixtures, the density of the mixture can be approximated in the following steps:
Calculate mass of one cubic foot of the liquid portion of the fluid at standard conditions,
141.5
M o 62.43 ....................................................................................33
131.5 API
Calculate the volume of this mass of material at the temperature, T (F) in the line
Vo 1 5.25 10 4 T 60 .................................................................................34

Calculate the mass of the gas associated with one cubic foot of liquid at standard conditions
M g 1.0877 10 2 GOR .....................................................................................35
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Calculate the volume of that mass of gas assuming the gas is insoluble in the liquid fraction,
with Z-factor evaluated at the pressure P (psi) and temperature, T (F) in the line
GOR 5.0368 10 3 Z P, T T 460
Vg ..........................................................36
P
Estimate the density of the mixture,
Mo Mg
m .......................................................................................................37
Vo V g

Figure 11 compares the above procedure to that accounts for volume changes in liquid fraction due
to solution gas. This chart was developed for temperatures between 90F and 150F, liquid
fraction densities of 20 API and 30 API and GORs between 200 and 2000 scf/stb. The chart
shows that the approximate procedure tends to under-predict the high densities as much as 25%,
when the GOR is high. Even so, these differences are small compared to the uncertainties
associated with the estimation of viscosity values and friction factors for two-phase flow.

1.8

1.6

1.4

60
1.2
100
150
1.0
200

0.8

0.6

0.4
0 2000 4000 6000 8000 10000
Pressure (psi)

Figure 12. Z-factor for natural gas with a gas gravity of 0.8 (Air =1)
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Table 7. Typical bulk densities and viscosity values for some

typical oil-gas mixtures.
Fluid Bubble point 3000 psi 1000 psi 500 psi 200 psi
API GOR pb m m m m m m m m m m
API scf/stb psi lbm/ft2 cP lbm/ft2 cP lbm/ft2 cP lbm/ft2 cP lbm/ft2 cP
20 100 731 55.5 22.1 - - - - 46.6 24.1 26.3 20.3
30 100 548 52.0 4.3 49.3 4.3 26.1 3.2
20 500 2781 50.8 5.2 - - 30.4 8.6 17.4 8.4 7.6 5.4
30 500 2085 47.6 1.6 - - 30.3 1.6 16.9 1.37 7.2 0.82
40 500 1564 44.8 0.79 - - 31.4 0.66 16.8 0.48 7.0 0.27
20 1000 4943 45.6 2.6 39.8 3.4 19.8 5.1 10.5 4.6 4.3 2.8
30 1000 3707 42.8 0.97 39.4 0.97 19.1 0.94 10.1 0.74 4.1 0.43
40 1000 2780 40.2 0.54 - - 18.8 0.36 9.7 0.26 3.9 0.14
20 1500 6921 41.5 1.7 33.6 2.6 15.3 3.6 7.9 3.2 3.2 1.9
30 1500 5190 38.9 0.72 32.3 0.71 14.7 0.66 7.5 0.51 3.0 0.29
40 1500 3892 36.6 0.43 32.1 0.37 14.2 0.25 7.2 0.18 2.9 0.10
30 2000 6590 35.9 0.58 28.4 0.56 12.3 0.51 6.2 0.39 2.5 0.22
Notes:

Unit conversions: cP = 0.001 Pas; lbm/ft 3 = 16.02 kg/m3; scf/stb = standard cubic foot per stock tank barrel, =
0.1781 m3/m3

All properties calculated at 130F.

10% water cut assumed. Gas gravity = 0.8 (Air = 1)

Values were calculated using correlation relations See The Properties of Petroleum Fluids 2nd ed., by W.D.
McCain, Jr.(Pennwell Books) or Applied Petroleum Reservoir Engineering, by B.C. Craft and M. Hawkins
(SPE)
Temperature Bubble point 3000 psi 1000 psi 500 psi 200 psi
pb m m m m m m m m m m
F psi lbm/ft2 cP lbm/ft2 cP lbm/ft2 cP lbm/ft2 cP lbm/ft2 cP
90 4773 39.6 0.97 35.0 1.0 16.8 1.1 8.4 0.94 3.4 0.58
150 5412 38.6 0.63 31.1 0.59 13.9 0.52 7.1 0.39 2.9 0.22
200 6010 37.8 0.47 28.0 0.39 12.1 0.29 6.3 0.21 2.5 0.11
Notes:

Standard oil density = 30 API

GOR = 1500 scf/stb

Table 8. Typical properties for natural gas.

Temperature
90 130 160
Pressure pb m pb m pb m
psi lbm/ft2 cP lbm/ft2 cP lbm/ft2 cP
200 0.84 0.012 0.77 0.012 0.73 0.012
500 2.25 0.014 2.04 0.013 1.91 0.013
1000 5.05 0.016 4.43 0.015 4.08 0.015
3000 16.3 0.033 14.3 0.028 13.0 0.026
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60

best estimate
50 = simplified

40

30
simplified = 75% of
best estimate
20

10
30 API
20 API
0
0 20 40 60
3
Best estimate density lbm/ft

Figure 13. Comparison of Equations 38 through 39 with a procedure that accounts for
volume change caused by solution gas
Adjustment for inhibitors or glycol
The addition of glycol reduces the CO2 corrosion rate. M-506 accounts for this by simply
reducing the corrosion rate by applying a factor of the form:
log10 Fglycol 1.6 log100 G 2 ......................................................................40

where G is the percent weight of glycol as a percent of water in the system. Fglycol is limited to a
minimum value of 0.008. Figure 14 shows the form of this expression. The base corrosion rate is
multiplied by the factor Fglycol to account for the corrosion reduction due to glycol.
For other types of corrosion inhibitors added to the stream, M-506 requires that its effectiveness
must be independently determined and used directly as a reduction factor, Finhib. If both glycol and
an inhibitor are used, the minimum of Finhib and Fglycol should be used.
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1.000

0.100

0.010

0.001
0 20 40 60 80 100
wt% glycol

Figure TM1.I 15. NORSOK M-506 recommended adjustment to corrosion rate for glycol
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Figure 16 Flow Chart

Start

Yes Is material
No Considered resistant
Carbon Steel or
<13% Cr? to CO2 corrosion

Are liquid Water Yes Fluid Yes No corrosion

Yes Content
HCs Velocity caused by CO2
present? <20% >1m/s

No No No

No Check dew
No liquid water
in stream point
T < Td?

Pressure
Temperature
Calculate Base Corrosion Rate CRbase
pH
Equation 2
Shear stress

Is there
glycol or CR = CRbase
inhibitor?

Yes
% weight glycol Calculate min(Fglycol, Finhib) CR = min(Fglycol, Finhib) CRbase