CO Corrosion Rate Calculation Model: Norsok Standard
CO Corrosion Rate Calculation Model: Norsok Standard
CO Corrosion Rate Calculation Model: Norsok Standard
M-506
Rev. 1, June 1998
This NORSOK standard is developed by NTS with broad industry participation. Please note that
whilst every effort has been made to ensure the accuracy of this standard, neither OLF nor TBL or
any of their members will assume liability for any use thereof. NTS is responsible for the
administration and publication of this standard.
Telephone: + 47 22 59 67 00 Fax: + 47 22 59 67 29
Email: [email protected] Website: http://www.nts.no/norsok
Copyrights reserved
CO2 corrosion rate calculation model M-506
________________________________________________________ Rev. 1, June 1998
CONTENTS
FOREWORD 2
INTRODUCTION 2
1 SCOPE 3
2 NORMATIVE REFERENCES 3
3 DEFINITIONS AND ABBREVIATIONS 3
3.1 Definitions 3
3.2 Symbols 3
4 PRINCIPLES FOR USE OF THE COMPUTER PROGRAM 4
5 DESCRIPTION OF THE CO2 CORROSION RATE MODEL 5
5.1 General 5
5.2 The corrosion model 6
5.3 The effect of glycol and corrosion inhibitors 7
6 STRUCTURE OF THE COMPUTER PROGRAMME 8
7 INPUT PARAMETERS 8
7.1 Basic input parameters 8
7.2 Other input parameters 9
8 PREDICTION OF SOME OF THE INPUT PARAMETERS 11
8.1 Fugacity of CO2 11
8.2 pH 12
8.3 Humidity 14
8.4 Wall shear stress 15
9 INFORMATIVE REFERENCES 18
FOREWORD
NORSOK (The competitive standing of the Norwegian offshore sector) is the industry initiative to
add value, reduce cost and lead time and eliminate unnecessary activities in offshore field
developments and operations.
The NORSOK standards are developed by the Norwegian petroleum industry as a part of the
NORSOK initiative and supported by OLF (The Norwegian Oil Industry Association) and TBL
(Federation of Norwegian Engineering Industries). NORSOK standards are administered and issued
by NTS (Norwegian Technology Standards Institution).
The purpose of NORSOK standards is to contribute to meet the NORSOK goals, e.g. by replacing
individual oil company specifications and other industry guidelines and documents for use in
existing and future petroleum industry developments.
The NORSOK standards make extensive references to international standards. Where relevant, the
contents of a NORSOK standard will be used to provide input to the international standardisation
process. Subject to implementation into international standards, the NORSOK standard will be
withdrawn.
INTRODUCTION
1. The Clauses 4, 5, 6, 7 and 8 in this standard acts as the user manual for the computer program. A
description of the calculation model, the algorithms and the conditions for the corrosion rate
calculations are given. In additions, methods and algorithms for calculation of essential input
parameters to the corrosion rate calculations are given.
2. The computer program for corrosion rate calculations is available for downloading free of charge
from the NTS/NORSOK Internet website (http://www.nts.no/norsok) or it may be procured from
NTS, Oslo.
1 SCOPE
The scope of this standard is to present a method for calculation of corrosion rates in hydrocarbon
production and process systems where the corrosive agent is CO2.
The standard has primarily been developed for calculation of corrosion rates in topside piping
systems and vessels, but the program may also be used for calculation of corrosion rates in pipeline
systems and subsea production facilities.
2 NORMATIVE REFERENCES
The following standard includes provisions which, through reference in this text, constitute
provisions of this NORSOK standard. Latest issue of the reference shall be used unless otherwise
agreed. Other recognised standards may be used provided it can be shown that they meet or exceed
the requirements of the standard referenced below.
3.1 Definitions
Can Verbal form used for statements of possibility and capability, whether
material, physical or casual.
Informative references Shall mean informative in the application of NORSOK standards.
May Verbal form used to indicate a course of action permissible within the
limits of the standard.
Shall Verbal form used to indicate requirements strictly to be followed in order
to conform to the standard and from which no deviation is permitted,
unless accepted by all involved parties.
Should Verbal form used to indicate that among several possibilities one is
recommended as particularly suitable, without mentioning or excluding
others, or that a certain course of action is preferred but not necessarily
required.
3.2 Symbols
The corrosion rate equations included in this standard describe the calculation model which shall
apply, while the computer program itself is an optional aid which the users of the model may apply
such that they possess an efficient tool to conduct corrosion rate calculations and parameter studies.
This computer program is developed based on the corrosion rate model given as equations in this
standard.
The computer program is an aid in CO2 corrosion rate assessments, but the user of the computer
program is responsible for the results and the final material selections and piping and equipment
design. Therefore the user of the program must perform a critical evaluation of all results and the
applicability of these in each case. Corrosion rate calculation, is only one element in a material
selection process. Other essential factors are uncertainty in input data for corrosion rate calculations,
construction and commissioning conditions, consideration of normal and upset operating
conditions, actual corrosivity of produced fluids, scale, wax, inhibitor efficiency and geometry of
corrosion attacks. These and other factors may influence the actual corrosion rates considerably,
and be more important than any uncertainty in the corrosion rate calculations.
As the computer program is distributed electronically and may be used on computers and program
versions outside the control of NTS/NORSOK, users of the computer program are sole responsible
to verify that the computer calculations are in accordance with the equations in this standard.
This standard provides an introduction to the corrosion rate computer program. It also gives
limitations and requirements to input parameters and results. Instructions for running the program
are given in the help functions to the program.
The program covers only calculation of corrosion rates where CO2 is the corrosive agent. It does not
include additional effects of other constituents which may influence the corrosivity, e.g.
contamination’s of O2, H2S etc. If such constituents are present, which is common in e.g. produced
water systems, these effects must be evaluated separately.
Principles for materials selection is given in NORSOK standard M-001 “Material Selection”. The
requirements in NORSOK M-001 shall be used when generating input data and when interpreting
results from this CO2 corrosion rate calculation standard. It is important to note that this standard
and computer program may use or generate data which are outside the limits of NORSOK M-001.
One example is corrosion inhibitor efficiency, where NORSOK M-001 provides maximum
allowable values, while the computer program accepts all values from 0 to 100%. In case of
conflict, NORSOK M-001 shall apply when selecting materials.
5.1 General
The model is an empirical corrosion rate model for carbon steel in water containing CO2 at different
temperatures, pH's, CO2 fugacities and wall shear stresses. It is based on flow-loop experiments at
temperatures from 20-160°C. A large amount of data at various temperatures, CO2 fugacities, pH's
and wall shear stresses are used.
The main bulk of the flow loop tests used in developing the calculation model is taken from the
Kjeller Sweet Corrosion research program at Institute for Energy Technology in Norway. The main
principles for the testing is described in a paper by Dugstad et. al. /1/. Most of the data directly used
in the modelling work has been generated after this paper /1/ was presented.
5.2.1 General
The following general equation of the CO2 corrosion rate for carbon steel at each of the
temperatures (t); 20, 40, 60, 80, 90, 120 and 150°C is used:
The corrosion rate between temperatures where a constant Kt has been generated, is found by a
linear extrapolation between the calculated corrosion rate at the temperature above and below the
desired temperature. The constant Kt is given in the table below.
Temperature °C Kt
20 4,762
40 8,927
60 10,695
80 9,949
90 6,250
120 7,770
150 5,203
Temperatur pH f(pH)
e
The effect of glycol on the corrosion rate is calculated as a reduction factor /2/:
• Glycol reduction factor = 10 1,6 (log (100-wt%Glycol)-2) for less than 95 weight-% glycol.
• For > 95 weight-% glycol, the glycol reduction factor is set to 0,008.
The effect of corrosion inhibitors is entered directly as a reduction factor in the computer program.
When both addition of corrosion inhibitors and glycol is entered into the computer program, the one
effect giving the greatest corrosion rate reduction factor will be used for calculation of the resulting
corrosion rate, i.e. the two effects will not be combined.
The computer program has a main dialogue box, denoted as the “Main Menu”, where all corrosion
rate calculations can be performed. All input parameters can be entered into the program directly at
this stage for point calculations.
As options and support functions, it is possible to calculate several of the important parameters by
selecting optional dialogue boxes. Such options are:
• pH calculations
• shear stress calculations
• humidity calculations for gas systems (not an input parameter used in the calculations, but
essential in evaluating risk for corrosion in gas systems)
These program options are included in order to generate adequate input data for corrosion rate
prediction based on data normally presented in process flow diagrams and design basis documents.
The support program options are prepared to give adequate accuracy for corrosion rate calculations,
and shall not be used for other purposes, e.g. genuine process, scale or flow calculations.
In the clauses below, the input parameters and the corrosion rate calculation model are explained.
Additionally, the support functions for calculation of some of the input parameters are explained.
Other support functions, such as “Parameter study”, “Accumulated corrosion”, saving of data, print
of data etc. are not specifically explained in this standard, but are covered by the “Help” function
provided in the computer program.
7 INPUT PARAMETERS
The basic input parameters for the CO2 corrosion model for carbon steel are given in table 7.1. The
allowed units and ranges are also given.
To calculate the wall shear stress, the input parameters given in table 7.2, are as a minimum
required.
Table 7.2. Input parameters for simplified calculation of wall shear stress
For more accurate wall shear stress calculations, the input parameters given in table 7.3 should also
be used.
Table 7.3 - Input parameters for accurate calculation of wall shear stress.
To predict the pH in the condensed water or formation water, the parameters given in table 7.4 are
needed.
250(0,0031 - 1,4/T)
a = 10 for P > 250 bar
where T is the temperature in °K and P is the total pressure given in bar. The total pressure is set to
250 bar in the fugacity constant for all pressures above 250.
8.2 pH
The program contains a pH calculation module. The pH in both condensed water and formation
water can be calculated. Some essential general considerations relevant for pH assessment is given
below.
The reported pH in water analyses is usually measured after depressurisation and atmospheric
exposure of the sample. Such pH’s give no information about the in situ pH which is a requisite for
the corrosion rate evaluation. The in situ pH has to be determined by calculations which take into
-
account the three controlling buffer systems CO2 /HCO3 , H2S/HS- and CH3COOH/CH3COO-. The
buffer system CH3COOH/CH3COO- can be extended to include all the other organic acids that may
influence the pH determination as these acids have similar dissociation constants.
The bicarbonate concentration, which is used for pH calculation, is routinely determined by titration
and the reported value is set equal to the alkalinity. This is correct as long as the H2S concentration
is low and the system does not contain acetic acid. For waters containing significant amount of
organic acids, the reported bicarbonate concentration requires correction because organic acids
contributes to the measured value of total alkalinity. The correction will be 2/3 of the organic acid
concentration assuming that the end point pH of the titration is 4.3. Lower pH requires a higher
fraction. More details about the interpretation of the water analysis and the determination of pH can
be found in the EFC publication number 16 /3/.
8.2.2 Calculation of pH
The routine for calculation of pH is based on the following chemical reactions and equilibrium
constants:
C
CO
2
CO2 (g) = CO2 (aq) K =
H p
CO
2
C
H CO
2 3
CO2 (aq) + H2O = H2CO3 K =
0 C
CO
2
C − C +
HCO H
H2CO3 = H+ + HCO3- K = 3
1 C
H CO
2 3
C 2− C +
CO H
HCO3- = H+ + CO32- K = 3
2 C −
HCO
3
H2O = H+ + OH- K =C +
C −
W
H OH
The system has to be electro-neutral, which can be described by the following equation:
C +
+C + = C −
+ 2C 2−
+C −
+C −
Na H HCO CO OH Cl
3 3
It is assumed that bicarbonate is added as sodium bicarbonate (NaHCO3). It is also assumed that no
other salts than sodium bicarbonate and sodium chloride (NaCl) are present in the solution. These
salts will dissolve as follows:
NaCl = Na+ + Cl-
NaHCO3 = Na+ + HCO3-
Based on these assumptions, the amount of sodium bicarbonate equals the difference in the
concentrations of sodium and chloride as shown below. The mass balance for bicarbonate will
therefore be as follows:
C =C −C
0. Bicarb + −
Na Cl
By combining the equations for the equilibrium constants with the required electro-neutrality and
the mass balance for bicarbonate one get the following expression for the concentration of the
Hydrogen cation:
3 2
C + +C C + − (K K K p + K )C + − 2K K K K p =0
0 , Bicarb H 0 1 CO W H 0 1 2 CO
H H 2 H 2
The pH in a condensed water system saturated with iron carbonate can also be calculated. Based on
a similar deduction as above, the equation becomes:
2K 4
C
3 2
SP
+ C + C C + − ( KH K0 K1 pCO + KW )C + − 2KH K0 K1 K2 pCO = 0
K K K K p + + 0, Bicarb
H 0 1 2 CO2 H H H 2 H 2
K0 = 0,00258
The equilibrium constant for iron carbonate was taken from IUPAC /5/:
-(10,13 + 0,0182Tc)
KSP = 10 molar2 where Tc is the temperature in oC.
The rest of the equilibrium constants were given by Oddo and Tomson /6/:
−3 −6 2
− ( 2 ,27 + 5, 65 × 10 T − 8,06 × 10 T + 0,075 I )
14,5 f f
K = × 10 molar / bar
H 1,00258
−3 −6 2 −5 1/ 2
− ( 6,41 − 1,594 × 10 T + 8,52 × 10 T − 3,07 × 10 P − 0,4772 I + 0,1180 I )
f f
K = 387,6 × 10 molar
1
−3 −5 2 −5 1/ 2
− (10, 61− 4 ,97 × 10 T + 1,331 × 10 T − 2 , 624 × 10 P − 1,166 I + 0,3466 I )
f f
K = 10 molar
2
The equation for the equilibrium constant for the dissociation of water was based on data given by
Delahay/7/:
−5 2
− ( 29 ,3868 − 0,0737549 T + 7 ,47881x10 T )
2
K = 10 molar
w
T: Temperature in Kelvin.
8.3 Humidity
A prerequisite for corrosion to occur is that there is liquid water present in the system. In gas
systems, an essential assessment is to determine if the presence of condensed water is possible.
The program therefore includes a support function to calculate humidity in pure water /8/, i.e. in
systems without glycol.
The dew point temperature (Tdew) equals the temperature where the humidity is 100%.
Obstacles and other geometrical changes in the flow will give rise to higher shear stresses than
calculated by this program. Further, different flow regimes and geometrical obstacles may generate
shear stress fluctuations where the shear stress peaks may be considerably higher than the average
shear stress.
High shear stress may cause mesa attacks, with corrosion rates significantly higher than what is
estimated by this computer program.
It is not the objective of this computer program to cover all such eventualities, and the user of the
program must evaluate the flow effect in each system/part of a system based on expertise and
available experience and documentation.
The mean wall shear on the wall at medium to high superficial velocities of one or both of the liquid
and gas velocities:
S = 0,5 x ρm x f x um2 (Pa)
where the friction factor, f, can be expressed as:
µ
0,33
k 6
f = 0,001375 1 + 20000 + 10 m
D ρ u D
m m
ρm = ρL λ + ρG (1 - λ)
ρL = φ ρw + ρo (1 - λ)
ρG = 2,7 . 14,5 . 16,018 . P . specific gravity/(Z . (460 + Tf))
φ = water cut and Z = compressibility of the gas
um = uLs + uGs
The liquid is considered incompressible: uLs = QL / A
The gas superficial velocity is: uGs = (QG / A) Z (T/Tstd)
µm = µL x λ + µG (1 - λ)
QL
λ =
QL + QG
The effective viscosity of a kinetically stable oil/water mixture depends on the watercut /10/.
Preferably the maximum magnitude of viscosity and the corresponding watercut should be known.
The viscosity of the oil wet region, i.e. below the inversion point in a dispersed flow, can be
represented as:
2 ,5
φ
(Ns/m2 )
K
µ = µ + 0
L 0 1 φ
1 ,1 8 7 −
K
0
The value of K0 for the maximum relative viscosity µrelmax (relative to the oil) and corresponding
watercut at the inversion point, φc, is equal to :
φ
K = c
0 0 ,4
1
1 ,1 8 7
1 −
µ
rel m ax
If not known, data for a medium viscosity oil/water dispersion will be used. This dispersion
exhibits a maximum value of relative viscosity = 7,06 at a watercut of 0,5. The oil viscosity is
equal to 0,0011 Ns/m2 at 60°C and the water viscosity is equal to 0,00046 Ns/m2.
Above the inversion point, the viscosity of any dispersion is given as:
1− φ
2 ,5
+ K (Ns/m2 )
µ = µ w
1
L w
1− φ
1,1 8 7 −
K
w
Where:
1 − φ
K = c
w 0 ,4
R
1 ,1 8 7
1 −
µ
rel m ax
µ
R = water
µ
oil
The viscosity of water is as default given as function of temperature, Tc, given in oC /8/:
0 - 20 oC:
2
1301/ ( 998,333 + 8,1855( T − 20 ) + 0,00585( T − 20 ) ) − 1,30233 −3
µ = 10 ⋅ 10
c c
(Ns/m2 )
w
20 - 150 oC (the formula is strictly only valid up to 100 oC, but used up to 150 oC in this context):
2
(1,3272(20−T ) −0,001053(T −20) )/(T +105)
−3
µ = 1002
c c
, (10 ) 10 (Ns/m2 )
w
For the medium viscosity oil at 60oC , R is equal to 0,42.
9 INFORMATIVE REFERENCES
/1/ A. Dugstad, L. Lunde, K.Videm “Parametric study of CO2 corrosion of carbon steel” NACE-
Corrosion-94 paper No 14.
/2/ C. de Waard, U. Lotz, D.E.Milliams "Predictive model for CO2 Corrosion engineering in wet
natural gas pipelines", Corrosion December 1991 pp. 976
/3/ Guidelines on materials requirement for carbon and low alloy steels for H2S-containing
environments in oil and gas production, European Federation of corrosion publication number
16, the Institute of Materials, 1995
/4/ D. A. Palmer and R. V. Eldik, Chem. Rev., Vol. 83, p. 651, 1983.
/5/ IUPAC: Chemical Data Series No 21. Stability constants of Metal-Ion Complexes. Par A:
Inorganic ligands. Pergamon Press.
/6/ J. E. Oddo and M. B. Tomson, "Simplified Calculation of CaCO3 Saturation at High
Temperatures and Pressures in Brine Solutions". SPE of AIME, pp. 1583, 1982.
/7/ P. Delahay, “Implication of the Kinetics of Ionic Dissociation with regard to some
Electrochemical Process-application to Polarography.” I.Am.Chem.Sic, 74, 1952 pp 3497.
/8/ D. R. Lide, “CRC Handbook of Chemistry and Physics” 66th edition, CRC Press Inc. 1985-
1986
/9/ A. E. Dukler, M. Wicks III, R.G. Cleveland, Frictional pressure drop in two phase flow. An
approach through similarity analysis, A.I.Ch.E. Journal, Vol. 10, No 1, January 1964
/10/ H. Kvandal, T. Søntvedt, Frictional pressure loss for stable oil-water emulsions in pipeflow.
Symposium on two phase flow modelling and experimentation, Rome 1995.