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Corrosion Prediction with

Cassandra


S/UTG/013/03


Adam Petersen
Richard Chapman
Bill Hedges















Upstream Technology Group, Sunbury
01/03/03 GQS






In Greek Mythology Cassandra was the daughter of
Priam and Hecuba. She was endowed with the gift of
prophecy but fated never to be believed. She is regarded
as the prophet of disaster..especially when
disregarded.





UTG Indexing Sheet
BRANCH REPORT NO. JOB NO.
U T G S / U T G / 0 1 3 / 0 3 1 1 9 0 1 5 2

AUTHOR TELEPHONE LOCATION DATE
Adam Petersen
Richard Chapman
Bill Hedges
+ 44 1932 775912
+ 44 1932 775944
+ 1 868 623 2862 x5042
B H Sunbury
B H Sunbury
POS Trinidad
01/03/03

MAIN TITLE
Corrosion Prediction with Cassandra



SUB TITLE




CLIENT PRINCIPAL RECIPIENT COMMISSIONED BY
Cassandra User Group






PLEASE TICK

SECURITY CLASSIFICATION X
UNCLASSIFIED

CONFIDENTIAL

TQA COMPLETED X
YES

NO

KEYWORDS
Cassandra, CO
2
, Corrosion, Rate, Prediction.



ACKNOWLEDGEMENT RECORD
PAGE
FOR EXTERNAL CLIENT LISTING DISTRIBUTION
OVERLEAF

ABSTRACT

PREPARED BY:


Adam Petersen




APPROVED BY:


Bill Hedges



.
AUTHORISED FOR ISSUE BY:


Don Harrop





ISSUE DATE: 01/03/03

The information contained in this document is the property of bp Exploration. Due
acknowledgement should be made if it is desired to refer to this information in publications
or discussions with third parties.







DISTRIBUTION LIST




COPIES

NAME
Electronic BDM/UTG Library
Electronic Issued with Cassandra installer to user group
















Contents
1. Introduction ........................................................................................................................................... 5
2. Simple Predictions using the Provided Spreadsheet .............................................................................. 5
a. Basic Corrosion Rate Prediction........................................................................................................ 5
b. Flow Sensitive Corrosion Rate Prediction......................................................................................... 6
3. Programming Your Own Spreadsheets.................................................................................................. 6
4. Corrosion Modelling.............................................................................................................................. 6
a. The 93 model (Flow Insensitive) ..................................................................................................... 7
b. The95 model (Flow-Sensitive)......................................................................................................... 7
c. Arguments (Inputs)............................................................................................................................ 8
i. Compulsory Arguments ................................................................................................................ 8
! Unit Code .................................................................................................................................. 8
! Temperature and Pressure ......................................................................................................... 8
! CO
2
Content .............................................................................................................................. 8
! pH Models................................................................................................................................. 9
! Liquid Velocity ......................................................................................................................... 9
! Hydraulic Diameter................................................................................................................... 9
ii. Optional Inputs............................................................................................................................ 10
! Scaling Temperature ............................................................................................................... 10
! H
2
S Content............................................................................................................................. 11
! Glycol Content ........................................................................................................................ 11
! Water chemistry ...................................................................................................................... 11
! Acetates................................................................................................................................... 11
d. Properties Available from CASS_RATE ........................................................................................ 12
i. Corrosion Rates ........................................................................................................................... 12
ii. Correction Factors ....................................................................................................................... 12
! pH Correction Factors ............................................................................................................. 12
! Fugacity Correction Factor...................................................................................................... 13
3

! Glycol Correction Factor......................................................................................................... 13
! Scaling Correction Factor ....................................................................................................... 13
! Overall Correction Factor ....................................................................................................... 14
iii. Other Properties ...................................................................................................................... 14
! Partial Pressures and Fugacity................................................................................................. 14
! Scaling Temperature ............................................................................................................... 14
! pH............................................................................................................................................ 14
5. Flow Modelling ................................................................................................................................... 14
a. Fluid Property Prediction ................................................................................................................ 14
b. Hydraulics and Flow Regime Prediction......................................................................................... 15
c. Arguments ....................................................................................................................................... 15
i. Compulsory Inputs ...................................................................................................................... 16
! Temperature and Pressure ....................................................................................................... 16
! Fluid Flow Rates and Properties ............................................................................................. 16
! Pipe Information...................................................................................................................... 16
ii. Optional Inputs............................................................................................................................ 16
! Gas Composition..................................................................................................................... 16
d. Properties Available from CASS_FLOW....................................................................................... 16
! Property Codes used in CASS_RATE .................................................................................... 16
6. Limitations........................................................................................................................................... 17
7. References ........................................................................................................................................... 17
8. Appendix ............................................................................................................................................. 18
a. History of Cassandra ....................................................................................................................... 18
i. BP Cassandra 98 ........................................................................................................................ 18
ii. Cassandra 2001 ........................................................................................................................... 19
iii. Cassandra ................................................................................................................................ 19
b. Property Codes for CASS_RATE ................................................................................................... 20
c. Property Codes for CASS_FLOW.................................................................................................. 21

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S/UTG/013/03


1. I ntroduction
This report accompanies the latest version of BPs corrosion prediction model Cassandra, which is based on
the CO
2
corrosion models published by de Waard et al [1-3]. Included with the corrosion prediction function
CASS_RATE are a number of pH prediction models (one of which is the BP-developed BPpH) and a
multiphase flow prediction function CASS_FLOW. CASS_FLOW is built from fluid property predictions
and two hydraulic flow models for horizontal and vertical flow, the BP GRE Mechanistic model (see section
5.b for description) and the BP coded Ansari [4] model.
The document Corrosion Prediction Modelling [5] described and included instruction for use of the first
version of Cassandra. This document is based on the original release but has been brought up to date to
reflect the differences in the latest release of the program. Corrosion Prediction Modelling also contains
advice on how a predictive model can be used for design purposes and describes topics including the
probabilistic approach to corrosion prediction modelling, inhibitor availabilities and corrosion risk, subjects
that are not covered here. Therefore, this report should be viewed as a supplement to the original document.
Further details relating to the history of the Cassandra program can be found in appendix a.
A second, extensive source of information for this report is the help file that comes as part of the installer for
Cassandra.
This latest release of the Cassandra software contains the same corrosion model as earlier releases, but in
response to requests from BP Corrosion Engineers for increased flexibility, the interface between the user
and the program has been significantly altered. The excel format allows the engineer to configure
calculations in a way that is most appropriate for the individuals needs. Intermediate properties can also be
interrogated enabling results to be sense-checked.
Thus the intent of this latest version of Cassandra is that the user will build their own spreadsheets to meet
their specific needs. However, the installer does include a simple spreadsheet that enables the most basic of
corrosion predictions for those who only want a quick indication of the likely corrosion rate.
2. Simple Predictions using the Provided Spreadsheet
A spreadsheet is supplied with the Cassandra installer that contains two of the simplest forms of the corrosion
prediction tool to enable quick predictions of corrosion rates.
a. Basic Corrosion Rate Prediction
The most simple corrosion prediction model within Cassandra is the so-called '93 model. It is based on
experimental results from stirred autoclave tests and consequently does not take the effects of flow on
corrosion into account.
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S/UTG/013/03
A simple version of the '93 model has been set-up; it requires input of temperature, pressure and acid gas
content along with the water chemistry. If these values are entered (cells G11 to G28), the predicted
corrosion rate will be displayed in cell G30.
If Status:OK is not displayed below the corrosion rate an error has occurred, details of which can be found in
the Cassandra help file under Error Messages in Cassandra.
b. Flow Sensitive Corrosion Rate Prediction
Another corrosion model within Cassandra, known as the '95 model, is based on data from flow loop tests
and is sensitive to flow effects. The most basic form of this model is included in the example spreadsheet.
The 95 model requires all of the entries that are needed for the 93 model (cells G11 to G28) in addition to
the flow parameters of liquid velocity and hydraulic diameter (cells K30 and K31). The predicted corrosion
rate will be displayed in cell K33.
In a similar manner to the 93 model Status:OK should be displayed below the corrosion rate, if this is not
returned the error messages section within the help file should be consulted. The flow sensitive model is not
valid for all flowing conditions, and if the '95 corrosion rate is less than the '93, it should be ignored.
3. Programming Your Own Spreadsheets
The spreadsheet that comes with the Cassandra installer allows prediction of corrosion rates for simple
examples only; there are many other features within the program, for example, the effects of glycol, or the
option of over-riding the internally predicted scaling temperature. To access the full potential of Cassandra in
terms of technical features, as well as flexibility, users must build their own spreadsheets. A reasonable
knowledge of MS Excel is required for this, but adequate guidance can be located in the Getting Started
section of the help file, and in MS Excel help under Array formulas and About cell and range references.
The excel program will run more slowly when the number of calculations increases, but this will rarely cause
concern because the number of calculations at which this effect becomes significant is in the order of
hundreds.
The Cassandra program consists of four functions; CASS_RATE for corrosion prediction and pH calculation;
CASS_FLOW for fluid property prediction and multiphase flow modelling; the other two functions
CASS_VERS and CASS_DLLV return information regarding the version of the program components, which
can be useful information when dealing with other Cassandra users.
4. Corrosion Modelling
CASS_RATE is the main function of Cassandra, designed to predict the pH and return corrosion rates
according to the de Waard models, or BPs interpretation of them, called the BP models in subsequent text.
The models are based on two papers reported at NACE corrosion conferences and have come to be known by
the years in which they were reported, i.e. 93 and 95 [2,3].
There are slight differences between the de Waard and BP models. For example they treat fugacity
differently; in the original de Waard models the partial pressure of CO
2
is used although the use of fugacity is
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S/UTG/013/03
discussed and recommended to account for the non-ideal behaviour of the gas. De Waard et al developed a
correction factor to accommodate non-ideal gas but were not consistent in its use and their equations alternate
between the use of partial pressure and fugacity. The BP models uses the fugacity in the original equations
and no fugacity correction factor is applied (see equations 4.1, 4.3 & 4.4 below). There are other differences
between the de Waard and BP models that are described below, but because the models are fundamentally
similar they should predict similar results.
The recommended pH and corrosion prediction models are obviously the BP versions, but the others can be
consulted for sense checking of results and may be useful when dealing with engineers from other
companies.
a. The 93 model (Flow I nsensitive)
The 93 models use an equation based on equation 4.1 to first calculate an uncorrected corrosion rate. This
corrosion rate is then adjusted by multiplication with correction factors due to the effects of the water pH, gas
fugacity, scaling temperature and amount of glycol. These correction factors are discussed in the outputs
section below.
) (fCO log 0.67
273 T
1710
- 5.8 = V log
2 10 cor 10
"
"
(4.1)
where T is the temperature in C, fCO
2
is the fugacity of carbon dioxide in bar, and V
cor
is the corrosion rate
in mm/y.
The data on which the model is based is from gently stirred, autoclave or cell experiments, which although
valuable does not accurately replicate pipeline conditions. Thus the 93 model is often referred to as a low
flow rate model.
b. The95 model (Flow-Sensitive)
The 95 model is based on experimental data from pipe flow and more accurately represents conditions in a
flowline or well. It calculates a corrosion rate in mm/y, V
cor
, by combining the contribution of the kinetics of
the corrosion reaction, V
r
, with the contribution from the flow dependent mass transfer of dissolved CO
2
, V
m
,
in the manner described by the following equations:
m r cor
V V V
#
"
#
$
#
(4.2)
where,
act 2 10 r 10
34pH 0 fCO log 41 0 T 0013 0
273 T
1119
23 6 = V log % & ' ( % " % "
"
& %
(4.3)
and,
' % $
2
0.2
0.8
m
(fCO
d
U
45 2 V (4.4)
where:
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S/UTG/013/03
T is the temperature in degrees Celsius.
fCO
2
is the fugacity of carbon dioxide in bara.
pH
act
is the actual pH.
U is the liquid velocity in ms
-1
.
d is the hydraulic diameter in metres.
c. Arguments (I nputs)
The inputs to the Cassandra functions are known in MS Excel as arguments and are described by both terms
in accompanying documents. Some of the arguments for the CASS_RATE function are compulsory, such as
the temperature and pressure, whereas others are not part of the main equation and not essential for predicting
a corrosion rate, for example, the water chemistry is not required if the pH is already known and entered
manually.
All of the arguments are highlighted in bold text and described below:
i. Compulsory Arguments
Unit Code !
!
!
The first argument requested by the function is the Unit Code and has the options C and F, these specify
whether the arguments and results will be expressed in C/bara/m or F/psia/ft respectively.
The program must also be instructed which outputs are required. This is done by specifying Property Codes
entered as an array of text. Typically these will be set to return corrosion rates, and an overall status indicator,
but a range of other quantities may also be returned. All of the property codes are listed with their
descriptions in the appendix b.
Temperature and Pressure
The Local Temp and Total Pressure for the point of interest in the system need to be entered in units of
C/bara or F/psia, depending on the selection of the unit code. The pressure itself is not used in the
prediction, but is used in combination with the gas composition to determine the concentration of dissolved
gases. If the pressure is greater than the bubble point of the fluid, the bubble point pressure should be entered
instead of the total pressure.
CO
2
Content
As stated above, the molar/volume percentage of carbon dioxide from the separated gas (Percent CO2) is
used to determine the concentration of the dissolved gas in the water phase. Therefore, even if there is no gas
present at the particular point, the CO
2
content of the gas phase that the liquid was last in contact with should
be used.
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pH Models !
A number of different pH prediction models are available within Cassandra. A code identifying which model
is required must be specified via the pH Model call. There are four options:
1. BP - the BPpH model calculates the pH with the individual ion
concentrations and balances the charge by adding either sodium or
chloride ions. There is an option to treat any acetate as either the sodium
salt or the acid (discussed below).
2. DW - the de Waard and Milliams model calculates the pH of salt-free water
containing dissolved CO
2
; it is calculated with the following equation
and is valid for temperatures between 10 and 80C [3].
(4.5) ) (fCO log 0.5 - T 0.000384 + 3.82 = ) pH(CO
2 10 2
3. OT - the Oddo and Tomson model is based on equation 4.6 and is valid for
temperatures up to 200C and pressures up to 1200 bara. The equation
does not give accurate results if [HCO
3
-
] is below 50 mg/l [6].
*
+
,
-
.
/
*
+
,
-
.
/
"
"
*
*
+
,
-
-
.
/
0
&
58500
TDS
0.193 +
58500
TDS
0.477 -
14.5)... * (P 0.0000307 - 32) 9/5 * (T 8 0.00000045 +
32)... 9/5 * (T 0.00405 + 8.68 +
61000 * 14.5 * fCO2
[HCO
log = pH
1/2
2
3
10
(4.6)
where the T is in C and P is in bara.
4. MANUAL - for direct entry of the pH into the Ph Manual argument if it has been
determined or measured elsewhere. If any of the other pH models are
selected any entry in the Ph Manual argument is ignored.
Depending on the selection for the pH model, other inputs may become compulsory, for example, the ion
definitions and concentrations when the BP pH model is selected.
Liquid Velocity !
!
The Liquid Velocity is compulsory for flow sensitive corrosion rate predictions using either of the de Waard
or BP 95 models, but is not required for the basic 93 models. It should be stressed that the actual liquid
velocity in either ms
-1
or fts
-1
is required, not the superficial velocity. The data from which the model was
built lies between 1.5 and 13 ms
-1
. When the model is used outside of this range the results should be used
with caution.
The value can either be entered directly if calculated with a different with a multiphase prediction package, or
calculated with the Cassandra multiphase flow model, CASS_FLOW.
Hydraulic Diameter
Another required argument for the flow sensitive models is the Hydraulic Diameter in units of either m or
ft, dependent on the unit code entry. In a similar manner to the liquid velocity, a value can be entered directly
or calculated with CASS_FLOW.
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S/UTG/013/03
ii. Optional I nputs
Scaling Temperature !
The corrosion reaction produces products, such as Fe
2+
ions, which can precipitate from solution onto the
metal surface to form scale. This formation of scale is dependent on several factors and is important as it may
provide some corrosion protection. Temperature is the most important factor in determining if a protective
scale is formed or not is. As the temperature increases the formation of a protective scale becomes favourable
and the de Waard models introduced the concept of a Scaling Temperature, which is the temperature at
which a protective film will form. The Scaling Temperature can be entered manually or calculated.
If a value for the Scaling Temp is not entered, the program automatically predicts a value using equation 4.7
[3],
123 "
" 44 % 5 6.7 ) log(fCO
2400
= T
2
s
(4.7)
where T
s
is the scaling temperature in C.
There is an opportunity to over-ride the internally calculated scaling temperature by manually entering a
value in the Scaling Temp argument.
Warning if the CASS_RATE function is directed to a blank cell, MS Excel assumes that a scaling
temperature of zero has been entered and a very low and incorrect corrosion rate will be returned.

Figure 4.1 Variation of corrosion rate with temperature. The figure depicts the
conflicting trends from experimental data used by de Waard and results from IFE.
The BP approach in light of this data lies between the two experimental data sets.
The treatment of the variation in corrosion rate above the scaling temperature is an area where the de Waard
and BP models differ. These different approaches are shown in Figure 4.1 along with the trend of data from
IFE, Norway. The two sets of experimental data, one used in developing the de Waard model and the second
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S/UTG/013/03
from IFE, indicate opposing trends, the de Waard approach indicates that the corrosion rate will fall whilst
IFE data suggest that the corrosion rate will continue to rise, albeit at a lower rate. In light of this conflicting
data and with the aim of being neither too conservative nor optimistic, the BP model assumes the corrosion
rate remains constant once the scaling temperature is exceeded. Cassandra achieves this by internally
performing the calculation at the scaling temperature for any case where it is exceeded by the actual
temperature.
H
2
S Content !
!
!
!
In a similar manner to the CO
2
content the molar/volume percentage of hydrogen sulphide in the gas phase
(Percent H2S) is used along with the total pressure to determine the amount of hydrogen sulphide in
solution. If there is no H
2
S present the argument can be left undefined. It should be noted that Cassandra
only takes into account the effect that H
2
S has on the pH of the solution and does not account for any changes
in the corrosion mechanism (i.e. sour corrosion).
Glycol Content
When glycol is present in the process stream it inhibits the corrosion reaction. This inhibition is accounted for
with a correction factor that requires entry of the percentage by weight of glycol in the aqueous phase
(Percent Glycol). The inhibitive effect is much smaller than that of specifically designed chemical corrosion
inhibitors, such that when both are present the effect of the corrosion inhibitor dominates the effect of glycol
and in these cases it should be assumed that the glycol content is zero.
Water chemistry
When either the BP or Oddo and Tomson pH models have been selected the water chemistry becomes
compulsory for pH prediction. The water chemistry requires two entries, firstly an array of text
corresponding to the Ions:
For the Oddo and Tomson model specification of bicarbonate concentration and total dissolved solids in
terms of the ions; Na, K, Ca, Mg, Sr, Ba, Fe, Cl, SO
4
, Ac (for acetate) are required.
The BP model allows a wider range of ions to be included; Mn, Al, Si, B, F, Li, Br, Zn, Cd, Pb, Cu, PO
4
, NO
3

and also permits all ions to be specified by name, e.g. Sodium, (ions cannot be specified by name for the
Oddo and Tomson model).
The entry for the ions must be consistent with the specification of Concentrations, entered as a numerical
array in the units of mg/l.
The BP pH prediction program also has a dependency on the Water Gravity, if the value is unknown the
argument can be left blank and the program will assume that the gravity is equal to that of pure water.
Acetates
The effect of acetates on the corrosion process can be two-fold; acetates cannot only affect the pH of the
solution, but possibly more importantly, the acetate species in solution can enhance the CO
2
corrosion
reaction. Research into the corrosion reaction enhancement is ongoing and in the future an enhancement
factor for acetates may be introduced into the Cassandra program. Early results have shown that acetate
concentrations of only 100 mg/L can have the effect of tripling the corrosion rate.
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In terms of the effect of acetate on the pH, the BP pH model provides an option of assuming that the acetates
were added in the form of acetic acid or the sodium acetate salt. The preference of these two options can be
specified through the Acetates as acid argument, which can be defined either as TRUE or FALSE. In the
cases where the acetate is treated as an acid, the pH will be lower and subsequently the predicted corrosion
rate will be higher. The default and recommended selection is FALSE unless there is data to suggest
otherwise (e.g. the measured pH of a de-gassed brine sample).
d. Properties Available from CASS_RATE
The flexibility in Cassandra enables a number of properties to be displayed to the user. These can be used to
determine the factors that are affecting the corrosion process, examine intermediate properties for quality
assurance purposes, etc. The user defines which properties are returned by entering the property codes,
written in bold type in the text below, into the CASS_RATE function (a full list is included in appendix b).
i. Corrosion Rates
It is recommended that the corrosion rates used for prediction are the BP versions, which are returned using
the codes BP93 and BP95 for the 93 and 95 models respectively. The codes DW93 and DW95 will return
predicted corrosion rates according to the original de Waard models. There are two other codes, VBP and
VDW, these return the largest of the 93 and 95 corrosion rates for the BP or de Waard assumptions.
ii. Correction Factors
Correction factors are used in the 93 corrosion models to adjust a corrosion rate that is derived using
equation 4.1 for the effects of pH, fugacity, glycol and scaling. The property codes for correction factors are
denoted by the first two characters CF, the third and fourth characters correspond to the property, for
example FU for fugacity, and the final character identifies whether the factor is used in the de Waard or BP
models (D or B respectively).
pH Correction Factors !
Equation 4.5 can be used to predict the pH of water containing dissolved CO
2.
, if the water contains dissolved
ions the actual pH of the water may differ significantly from this value. To accommodate for this effect the
original de Waard model uses the following correlation to calculate the correction factor CFPHD [1]:
pH pH for
pH (pH 0.32 = CFPHD log
act sat
act sat 10
6
' &
(4.8)
pH pH for
pH - (pH 0.13 - = CFPHD log
act sat
sat act 10
7
'
8 % #
(4.9)
where pH
act
is the actual pH of the brine, i.e. that pH calculated using the model selected with the pH model
argument or the pH entered manually. The value can be recalled by requesting the property code PHACT.
pH
sat
is the pH at which the brine becomes saturated with Fe
2+
, its value recalled with PHSAT (equation
4.10).
) (fCO log 0.66 - 5.4 = pH
2 10 sat
(4.10)
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The pH correction factor used in the BP model (CFPHB) is calculated slightly differently because it is felt
that pH
sat
is difficult to define especially when supersaturation occurs (the condition where dissolved Fe
2+

concentrations can exceed the theoretical saturation values by orders of magnitude, making the probability of
a fixed saturation pH unlikely). The BP method avoids this issue by using the BP pH model (that does
include the effects of ions) for PHACT and the pH of a salt free solution of CO
2
, PHDW (equation 4.5)
instead of PHSAT. This approach has the advantage that it is well defined and is valid over a wide range of
conditions.
Fugacity Correction Factor !
The original de Waard model includes a dependency on the partial pressure of CO
2
, and corrects for the non-
ideal nature of CO
2
with the correction factor, CFFUD.
P
273 + T
1.4
- (0.0031 0.67 = CFFUD log
10
' (4.11)
where T is the temperature in C and P the pressure in bara.
The de Waard paper states that models must take account of the non-ideal nature, which the BP approach
does by using fugacity in the original equation, therefore, no correction is needed and the correction factor,
CFFUB, will equal unity.
Glycol Correction Factor !
!
A correction factor is used to account for the inhibitive effect of glycol on the corrosion reaction. The
correction factor is identical for both the BP and de Waard approaches, consequently CFGLB will equal
CFGLD:
2) - W (log A = CFGLD log
10 10
(4.12)
where A is a constant which varies according to the glycol (1.6 is recommended)
W is the water content (%) in the water / glycol mixture
Scaling Correction Factor
Figure 4.1 and accompanying text describes the different approaches to the behaviour of corrosion rate
increase with temperature above the scaling temperature. The de Waard method uses the following equation
to calculate a correction factor, CFSCD, which accounts for the protection provided scale that forms above
the scaling temperature.
*
*
+
,
-
-
.
/
123 "
scale
10
T
1
-
273 + T
1
2400 = CFSCD log (4.13)
where T>T
s
, otherwise CFSCD = 1
T
scale
is the scaling temperature in C (equation 4.7)
The BP approach assumes that the corrosion rate remains constant above the scaling temperature. Therefore
the correction factor for scaling, CFSCB, is not used and is set equal to one (=1.0).
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Overall Correction Factor !
!
!
!
The above correction factors are combined into a single factor, equal to the product of the individual factors.
These overall correction factors are calculated by Cassandra and can be returned with the property codes
CFDW and CFBP for the de Waard and BP methods respectively.
iii. Other Properties
As well as the correction factors described above, Cassandra can return other calculated properties that can
be valuable for the purpose of sense-checking results.
Partial Pressures and Fugacity
The partial pressures of the acid gases can be returned with PPCO2 and PPH2S, but due to the non-ideal
nature of the gases

the BP approach uses the fugacity of CO
2
instead of the partial pressure. There are two
codes that can be used to return the fugacity, FCO2A, returns the fugacity of CO
2
at the system pressure. In
cases where the system temperature is above the scaling temperature, the fugacity at the scaling temperature
is used in the calculations and can be recalled with FCO2U.
Scaling Temperature
There is uncertainty in the manner that the corrosion rate varies above the scaling temperature, in light of this
fact it may be important to determine how similar the scaling and system temperature are and the effects of
any assumptions. The scaling temperature that is internally calculated by the program using equation 4.7 is
returned with the code CSCAT. The scaling temperature used by the program in calculations can be returned
with ASCAT, and will only differ from the calculated scaling temperature if it has entered manually.
pH
The pH value used in the calculations can be returned with PHUSD.
5. Flow Modelling
The Cassandra flow modelling function, CASS_FLOW, can perform predictions of fluid properties and also
hydraulics and flow regime. Many different properties can be predicted by the complex function, but the
focus of this document is corrosion prediction and so a brief overview of the CASS_FLOW function is
described below with particular attention to the properties used to predict corrosion rates. If there is any
uncertainty or if further information is required about the CASS_FLOW function, the Multiphase Flow
Group in UTG Sunbury should be contacted for guidance.
a. Fluid Property Prediction
The CASS_FLOW function contains correlations for the prediction of black oil physical properties for
conditions of temperature and pressure that are typical of reservoir and well applications; 30 to 150 C and
70 to 550 bara. Some correlations apply to wider ranges, but these conditions can be considered
representative and when values lie outside these ranges any key physical properties must be sense-checked.
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The model requires both gas and oil to be present in the system, but unfortunately there is a limit on the
relative values and is only valid for gas to oil ratios (GOR) up to a maximum of about 2000 scf/stb. When the
GOR raises above this value the need for careful inspection of the derived properties increases. Any
additional gas produced by the system, such as gas lift or injected gas that has broken through the reservoir,
must be included.
If unusual fluids are being modelled then advice should be sought from the Multiphase Flow Group in UTG
Sunbury, as not only may the black oil fluid models not be applicable but also the flow correlations. It should
be noted that the black oil viscosity correlations will not predict emulsion behaviour and therefore care
should be taken if emulsions are suspected to exist or at values close to the inversion point for the fluid (if
known).
Specifically, the correlations included are:
! Glaso correlation for solution gas-oil ratio and oil formation volume factor
prediction [7].
! Lee for the prediction of gas viscosity [8].
! Beggs and Robinson for the prediction of liquid viscosity [9].
! Baker and Swerdloff and Hough et al for the prediction of surface tension [10,11].
b. Hydraulics and Flow Regime Prediction
The hydraulic model available within Cassandra 2002 for estimating liquid velocity and hydraulic diameter
relies on the fluid property predictions outlined above and an integrated model for the prediction of
multiphase flow characteristics for which there are two options: For inclinations greater than or equal to 20
the BP-coded Ansari model [4] for the vertical upflow hydraulics is used whilst for inclinations less than 20
the BP GRE mechanistic model for near-horizontal multiphase flowline hydraulics is employed. The GRE
model is a mechanistic pressure drop model for stratified flow (developed in the 1990s at Sunbury) that
reverts to Beggs and Brill pressure drop calculations if it determines the flow is not stratified [12].
The horizontal flow regime prediction is extremely sensitive to inclination. For slight inclinations where the
angle is less than about 1, the inclination needs to be specified to the nearest 0.1. Unfortunately, the models
are not designed for downflow conditions although in the absence of any other data the GRE model can be
used with caution to angles as steep as 20.
Great care should be taken with the flow regime predictions provided by the function. The empirical nature
of the function will specify a particular flow regime, but naturally the regime boundaries are not precise.
Therefore, it is recommended that sensitivities be run to establish whether the operating point of concern is
near a regime boundary, and if so both regimes should be considered and that which produces the most
conservative results assumed.
c. Arguments
Many of the arguments that are required for the CASS_FLOW function are also required for the
CASS_RATE function; both functions can be directed to the same cell to ensure consistency. Of the many
properties that are calculated by the function only two are used as inputs for the flow sensitive 95 corrosion
rate, the liquid velocity and hydraulic diameter.
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i. Compulsory I nputs
The fields that are required for the flow prediction function CASS_FLOW include the Unit Code and a set of
Property Codes corresponding to the relevant outputs that are required. A list of the property codes with
descriptions is included in appendix c.
Temperature and Pressure !
!
!
!
!
Similar to the CASS_RATE function the Local Temperature, and Total Pressure at the point of interest are
required.
Fluid Flow Rates and Properties
The Gas, Oil and Water Flow Rates in mmscf/d or mbd are required, as well as the Gas, Oil and Water
Gravities relative to air and water.
Pipe I nformation
Some information about the pipe itself must also be entered; the Internal Diameter of the tubing or flowline
must be entered in m or ft and the Roughness needs to be entered in the same units. A typical value for the
roughness of an internal pipe surface is 4.57 x 10
-5
metres. The Inclination of the pipe of flowline must be
entered in degrees from the horizontal to not only be used in the calculations, but also select the appropriate
multiphase model.
ii. Optional I nputs
Gas Composition
Part of the gas composition should be entered, if available. This includes not only the molar/volume
percentage of carbon dioxide and hydrogen sulphide, which are also used for the CASS_RATE function
(PercentCO2 and PercentH2S), but also nitrogen (PercentN2).
d. Properties Available from CASS_FLOW
There are over thirty different property codes that can be returned from the CASS_FLOW function, of which
only two are used for the corrosion rate prediction. The other properties are, in many cases, intermediates that
can be used to sense-check results. The total list of property codes with brief descriptions and units is shown
in the appendix c. The Multiphase Flow Group in UTG Sunbury should be contacted if further clarification or
guidance is required.
Property Codes used in CASS_RATE
The property codes used for predicting the corrosion rate are the liquid velocity, which has the code VLIQ
and units of ms
-1
or fts
-1
, and the hydraulic diameter, HDIAM, with units of either m or ft.

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6. Limitations
The Cassandra model is based on equations that have been developed over a number of years by de Waard et
al. [1-3]. These equations can be used to produce precise corrosion rates, but the results should not be
interpreted in this way. The corrosion mechanism is inherently complex and cannot be accurately predicted
(or indeed measured) under all circumstances. This should be kept in mind when using corrosion prediction
models for design.
Within Cassandra there are a number of different models and correlations, the validity of which have not
been assured over all conditions. The following table describes the limits of certain elements of the model.
Element Validity Range
de Waard pH calculation 10 to 80 C
Oddo and Tomson pH calculation Up to 200C and 1200 bar
Flow sensitive corrosion rate BP95 and DW95 Liquid velocities between 1.5 and 13 ms
-1
Fugacity of CO
2
0.3 to 0.65 bar
Fugacity look up tables Total pressures below 200 bar

Table 6.1 Validity ranges for some elements of the Cassandra Prediction Program
7. References
[1] C. de Waard, U. Lotz and D. E. Milliams, Corrosion 47, 12, (1991) p976
[2] C. de Waard, U. Lotz, Paper 69, Corrosion 93 (NACE International)
[3] C. de Waard, U. Lotz and A. Dugstad, Paper 128, Corrosion 95 (NACE International)
[4] A. M. Ansari et al. SPE Production and Facilities, SPE 20630 (1994) p143-165
[5] A. J. McMahon and D. M. E. Paisley, Sunbury Report No. ESR.96.ER.066, (1997)
[6] J.E. Oddo and M.B. Tomson, J. Petroleum Tech., 34 (1982) p1583-1590
[7] O. Glaso, J. Petroleum Tech., (1980) p785-795
[8] A. L. Lee, M. H. Gonzalez and B. E. Eakin, J. Petroleum Tech., (1966) p997-1002
[9] H. D. Beggs and J. R. Robinson, J. Petroleum Tech., (1975) p1140-1144
[10] Baker and Swerdloff, Oil and Gas Journ., (1956) p125
[11] Hough et al., Trans AIME, (1951) p57
[12] H.D. Beggs and J. P. Brill, J. Petroleum Tech., (1973) p607-617
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8. Appendix
a. History of Cassandra
The Cassandra Corrosion Prediction Tool is based on the equations developed by the Shell Oil Company.
The first equations were published by C. de Waard & D.E. Milliams in the mid 1970s with significant
additions in 1991, 1993 and 1995. These equations became known as the de Waard & Milliams equations
and were widely used in the Oil & Gas industry including BP.
With time many companies modified the equations to account for their own preferences and /or experiences,
which led to an inconsistent use of them. Moreover, the exact method of calculation was obscured by the use
of different practices and correction factors. This proved increasingly problematic for BP when dealing with
external engineering companies who often did the calculations for BP Projects.
Consequently, in 1997 BP Sunbury began a project to formalize the way the calculations were done and
provide transparency to them. An Excel based spreadsheet was built by Drew McMahon to generate the
corrosion rates using standardized inputs. In May 1998 this was released to both BP and its contractors
under the name of BP Cassandra 98 (the winning name suggested by David Ray in a competition). It was
released with a guidance document detailing the logic used together with advice on how to use the results
during the design phase of a project (see reference 5).
i. BP Cassandra 98
The model, together with the guidelines, superseded previous BP documents covering this topic. They
described BP's approach to Corrosion Prediction and its use during the design of pipelines and facilities.
Important features were:
1. A clear, transparent method for calculating corrosion rates.
2. The introduction of probabilistic modelling as an alternative to the traditional deterministic approach
(reflecting the reality that real systems experience a distribution of corrosion rates and not a single,
discrete rate).
3. A move away from the use of corrosion inhibitor efficiencies to the use of availabilities.
4. The introduction of Corrosion Risk Categories as a way of classifying systems.
The guidelines were divided into two sections; the first section introduced the new prediction spreadsheet
called Cassandra 98 as BP's implementation of the CO
2
prediction models published by de Waard et al. It
built on these models to include BP's experience of such systems. The spreadsheet was provided on a floppy
disc with the guidelines. The second section discussed how the prediction model should be used for design
purposes and introduced several improvements over previous guidelines.
The new material and concepts originated from many sources including the results of Joint Industry Projects,
in-house R&D and practical experience from both BP and other operators. To illustrate the points made,
examples were provided from many BP assets worldwide.


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ii. Cassandra 2001
The Cassandra 2001 worksheet was developed based on feedback from the users of the Cassandra 98
version and because Microsoft had changed the macro structures in the Excel program. It included updated
macros and components, which were compatible with Windows 2000 software (BP COE3).
In order to provide the required functionality for the new version it was necessary to write detailed macros,
which inevitably reduced the transparency of the calculations.
Cassandra 2001 was designed to be compatible with the Corrosion Prediction Modelling guidelines. Due to
the loss of transparency of some of the calculations the need for reference to the guidelines was very
important for users who wanted to understand how the calculations were made.
New Features introduced were:
1. Option to store brine chemistries
2. Option to predict corrosion rates over a range of one parameter (e.g. Temperature).
3. Incorporation of a multiphase model
iii. Cassandra
The latest Cassandra has been developed to increase the functionality further and to fix a serious error in the
multiphase program. The flexibility has been introduced by the use of array functions. It is targeted at
experienced corrosion engineers.
The date suffix has been omitted to avoid any confusion that an out of date version may be being used.
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b. Property Codes for CASS_RATE
Property
Code
Description Units
PPCO2 Partial pressure of CO2 bara or psia
PPH2S Partial pressure of H2S bara or psia
FCO2A Fugacity of CO2 (actual) bara or psia
ASCAT Accepted scaling temperature C or F
FCO2U Fugacity of CO2 (used) bara or psia
CSCAT Calculated scaling temperature C or F
PHACT pH (actual) None
PHUSD pH (used) None
PHSAT pH of saturated CO2 in water None
CFPHB pH correction factor (BP model) None
CFGLB Glycol correction factor (BP model) None
CFFUB Fugacity correction factor (BP model) None
CFSCB Scaling correction factor (BP model) None
CFBP BP total correction factor None
CFPHD pH correction factor (de Waard model) None
CFGLD Glycol correction factor (de Waard model) None
CFFUD Fugacity correction factor (de Waard model) None
CFSCD Scaling correction factor (de Waard model) None
CFDW de Waard total correction factor None
PHDW de Waard pH None
BP93 BP 93 model corrosion rate mm/y
BP95 BP 95 model corrosion rate (requires non-zero liquid velocity & hydraulic diameter) mm/y
VBP BP overall corrosion rate (requires non-zero liquid velocity & hydraulic diameter) mm/y
DW93 de Waard 93 corrosion rate mm/y
DW95 de Waard 95 corrosion rate (requires non-zero liquid velocity & hydraulic diameter) mm/y
VDW de Waard overall corrosion rate ( ) mm/y
STATS Return status and error flags None

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21

c. Property Codes for CASS_FLOW
Property Code Description Units
GOR Input GOR scf/stb
API API gravity of oil API
RS Solution gas-oil ratio scf/stb
BO Oil formation volume factor stb/rb
RSW Solution gas-water ratio scf/stbw
BW Water formation volume factor stbw/rb
VFW Volume fraction of water None
SGDG Specific gravity of dissolved gas (air=1) None
SGFG Specific gravity of free gas (air=1) None
ZFAC Compressibility factor of gas None
BG Ideal gas equation constant ft
3
/scf
QG In situ volume gas rate mmscf/d
QL In situ volume liquid rate stb/d
VSG Superficial gas rate ft/s
VSL Superficial liquid rate ft/s
ODENS Oil density lb/ft
3
WDENS Water density lb/ft
3
GDENS Gas density lb/ft
3
LDENS Liquid density lb/ft
3
GVIS Gas viscosity cP
LVIS Liquid viscosity cP
STEN Surface tension dyn/cm
HL Liquid holdup None
DONR Depth/radius None
DPDL Pressure gradient psi/ft
FRGR Frictional pressure gradient psi/ft
ELGR Elevational pressure gradient psi/ft
ACCGR Accelerational pressure gradient psi/ft
HLNS No-slip liquid holdup None
HDIAM Hydraulic diameter m or ft
VLIQ Liquid velocity m/s or ft/s
FPAT Flow pattern None
STATS Return status and error flags None

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