02555E02

2 General revision CESCOR STIN CORM 15.06.
95
REV. DESCRIPTION COMP. VERIF. APPR. DATE
Il presente documento RISERVATO ed di propriet dell'AGIP. Esso non sar mostrato a Terzi n sar utilizzato per scopi diversi da quelli per i quali stato inviato.
This document is CONFIDENTIAL and the sole property of AGIP. It shall neither be shown to third parties nor used for purposes other than those for which it has been sent.
DESIGN CRITERIA
INTERNAL CORROSION
CORROSION PARAMETERS AND CLASSIFICATION OF THE
FLUIDS
02555.VAR.COR.PRG
Rev. 2
June 1995
02555.VAR.COR.PRG
Rev.2 June 1995
Sheet 2
FOREWORD
Rev. 2 No. Sheets 47
June 1995
The type of document has been changed from GENERAL SPECIFICATION
to DESIGN CRITERIA.
The Normative References chapter has been revised and updated.
It has been deeply revised the paragraphs concerning the corrosion parameters
and the corrosion forms; corrosion evaluation criteria have also been updated.
With respect to the previous revision, it has been completely eliminated the
classification by corrosion environments. In this revision, fluids are defined
only in terms of type of fluid and corrosivity class.
A detailed list of definition has been introduced.
Definition of sour conditions in accordance to EFC - European Federation of
Corrosion, has been introduced.

02555.VAR.COR.PRG
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Sheet 3
CONTENTS
1 GENERAL
1.1 Scope
1.2 Normative references
1.2.1 European normative references
1.2.2 Normative references of ISO, IEC and national organizations
1.2.3 Normative references of other organizations
1.3 Definitions
1.4 Abbreviations and conversion factors
2 FLUID TYPES AND CORROSIVITY CLASSES
2.1 Fluid types
2.1.1 Liquid hydrocarbons and multiphase
2.1.2 Gas and gas condensate
2.1.3 Glycol
2.1.4 Waters
2.2 Corrosivity classes
3 CORROSION PARAMETERS
3.1 Foreword
3.2 Temperature
3.3 Pressure
3.4 Water content
3.5 Gas Oil Ratio
3.6 Hydrodynamic conditions
3.7 CO
2
molar fraction
3.8 H
2
S molar fraction
3.9 API Grade
3.10 Water chemical analysis
3.11 Sulphates-reducing bacteria
3.12 Sand and suspended solids
4 CORROSIVITY CLASSES
4.1 Liquid hydrocarbons and multiphase systems (I.L.)
4.1.1 Corrosion parameters
4.1.2 Corrosivity classes
4.2 Gas hydrocarbons and gas with condensates
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4.3 Glycol
4.4 Waters
5 CORROSION FORMS
5.1 General
5.1.1 Foreword
5.1.2 Materials
5.1.3 Corrosion morphologies
5.2 Water wetting conditions
5.2.1 Liquid and multiphase systems
5.2.2 Gas and gas with condensates system
5.3 O
2
corrosion
5.4 H
2
S corrosion
5.5 Elemental sulphur corrosion
5.6 CO
2
corrosion
5.6.1 Effects of chemical species in solution
5.6.2 De Waard and Milliams model.
5.6.3 Top of line corrosion
5.6.4 Prediction rules for CO
2
corrosion (Crolet Model)
5.6.5 Corrosion products
5.7 Galvanic corrosion
5.8 Pitting and crevice
5.8.1 Susceptible materials
5.8.2 Initiation conditions
5.9 Stress Corrosion Cracking (SCC)
5.9.1 Chlorides stress corrosion cracking
5.9.2 Polythionic Acids Stress Corrosion Cracking
5.10 Sulphide Stress Cracking (SSC)
5.10.1 Sour service conditions according to NACE
5.10.2 Sour service conditions according to EFC
5.11 Stepwise Cracking
5.11.1 Limits for initiation
5.12 Erosion corrosion
5.13 Sand erosion
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Sheet 5
1 GENERAL
1.1 Scope
Scope of this document is provide criteria to classify, from the corrosion
viewpoint, the main fluids encountered in plants for oil and gas production.
The plants covered in this document are those ones from well head, excluded,
to the delivery of treated gas and stabilised oil. Refining plants are outside the
scope of this document.
For each type of fluid the parameters are indicated to be gathered to allow the
corrosion experts to assess the corrosivity and to select materials and corrosion
control methods.
The most common corrosion forms in oil and gas industry are reviewed and
proved criteria for corrosion prediction are indicated.
This document does not cover the corrosivity of the external environment
which the plant components are in contact with, as soil, sea water; also non
metallic materials such as elastomeric, ceramic, composites are not dealt with.
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1.2 Normative references
1.2.1 European normative references
No European normatives exist on the argument of this specification.
1.2.2 Normative references of ISO, IEC and national organizations
ISO 8044 Basic Terms and Definitions on Corrosion.
1.2.3 Normative references of other organizations
EFC O&G 93-1 Guidelines on Material Requirements for Carbon
and Low Alloy Steels for H
2
S Containing Oil and
Gasfield Service
NACE MR0175 Sulphide Stress Cracking Metallic Material for
Oil Field Equipment
NACE TM0284 Evaluation of Pipeline Steels for Resistance to
Stepwise Cracking
API RP-14E Design and Installation of Offshore Production
Platform Piping System
ASTM 287-92 Standard Test Method for API Gravity of Crude
Petroleum and Petroleum Products (Hydrometer
Method)
ASTM G 78-46 Standard Test Method for Pitting and Crevice
Corrosion Resistance of Stainless Steels and
Related Alloys by the Use of Ferric Chloride
Solutions
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1.3 Definitions
Chloride Stress Corrosion Cracking - CSCC
Formation of cracks caused by stress corrosion in a water- and chloride ions-
containing environments (NACE MR0175).
Corrosion
Physicochemical interaction between a metal and its environment that results in
changes in the properties of the metal and which may often lead to impairment
of the function of the metal, the environment, or the technical system, of which
these form a part (ISO 8044).
Corrosion product
Substance formed as a result of corrosion (ISO 8044).
Corrosion rate
Corrosion effect on a metal per unit of time.
Corrosion resistance
Ability of a metal to withstand corrosion in a given corrosion system (ISO
8044).
Corrosion system
System consisting of one or more metals and all parts of the environment which
influence corrosion (ISO 8044).
Corrosive agent
Substance which when in contact with a given metal will react with it (ISO
8044).
Corrosive environment
Environment that contains one or more corrosive agent (ISO 8044).
Corrosivity
Ability of an environment to cause corrosion in a given corrosion system (ISO
8044).
Corrosivity class
In the present document, it is an attribute conventionally assigned to each type
of fluid in order to point out the most significant corrosivity features. For the
fluid designed: liquid hydrocarbons and multiphase (I.L.), gas and gas with
condensates hydrocarbon (I.G.) and glycol (G.), the corrosivity class is defined
on the base of CO
2
and H
2
S partial pressures as follows:
N. non containing CO
2
and H
2
S
C. containing CO
2
S. containing H
2
S
CS. containing CO
2
e H
2
S
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Crevice Corrosion
Corrosion associated with, and taking place in, or immediately around, a
narrow aperture or clearance (ISO 8044).
Dew point temperature
It is the temperature, below which liquid condensation starts from gas phase at
a given pressure. On the state diagram condensation conditions are indicated by
the dew point curve. In particular the water dew point refers to condensation
conditions of water from gas.
Fugacity
It is thermodynamic function, in pressure units, that, when used in a
thermodynamic equation of an ideal gas in substitution of pressure, allows to
apply the same function to a non-ideal gas.
Hydrocarbon
Gas: a mixture of hydrocarbons with 1 to 4 carbon atoms at a temperature
above the critical temperature. Gas can be in form of dry gas or gas with
condensates depending on thermodynamic conditions.
Liquid: a mixture of hydrocarbons whose temperature is below the critical
temperature of the particular system of natural hydrocarbons that the mixture
contains; in the mixture the liquid phase, always present, can be combined
with a gas phase or an aqueous phase or both; in this cases the system is
called multiphase.
Hydrogen embrittlement
A process resulting in a decrease of the toughness or ductility of a metal due to
absorption of hydrogen. (ISO 8044).
Hydrogen Induced Cracking - HIC
A type of "stepwise cracking" in steels for pipes, or laminated products; cracks
on the same plane have the tendency to join with cracks in near levels forming
steps through the metallic wall, reducing its mechanical resistance.
Ionic strength
The ionic strength of a solution, , is defined as
=
1
2
C Z
i
i
2
where C
i
is the concentration of i
-th
ion with Z
i
charge.
Microbial Corrosion
Corrosion associated with the action of micro-organism present in the corrosion
system (ISO 8044).
Molar fraction
Measurement of the concentration of a chemical species expressed as ratio
between the number of moles of the given chemical species and the total
number of moles.
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Oil
In the present specification the terms oil and crude are considered synonymous
to indicate liquid hydrocarbons.
Passivity (passive state)
State of a corrosion system characterised by a reduced corrosion rate of a metal
as a consequence of the formation of corrosion products on its surface.
Pitting Corrosion
Corrosion resulting in pits, i.e. cavities extending from the surface into the
metal (ISO 8044).
Predicted corrosion rate
It is the corrosion rate, usually expressed quantitatively (in mm/y) and/or
qualitatively, determined: (a) after the corrosion study, applying all the
available knowledge and tools; (b) through laboratory tests, simulating the real
conditions; (c) on the base of field corrosion monitoring data applicable to the
case under study. The following categories are recommended to express in a
qualitative way the penetration rate for general corrosion forms: negligible,
low, moderate, severe, very severe.
Reservoir
Dry gas: reservoir whose temperature is above the cricondetermical
temperature of the particular system of natural hydrocarbons that it contains.
The cricondetermical temperature is the highest temperature at which the
coexistence between liquid and gas phase is still possible.
Gas with condensates: reservoir whose temperature is between critical and
cricondetermical temperatures of the particular system of natural
hydrocarbons that it contains. The condensation of the liquid phase from gas
takes place by reverse condensation, that is the phenomenon by which
decreasing the pressure below the dew point, there is initially an increase of
the liquid phase percentage and eventually a partial or total ri-evaporation of
the latter.
Crude oil: reservoir whose temperature is below the critical temperature of
the particular system of hydrocarbons that in contains.
Residual corrosion rate
It is the corrosion rate after treatments with corrosion inhibitors.
Sour conditions
Conditions, usually with H
2
S presence, that cause Sulphide Stress Cracking
occurrence in susceptible materials. The definition is according to NACE
MR0175 or EFC O&G 93-1.
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Specific gravity
It is the ratio between the weight of a given volume of liquid and the weight of
the same volume of water; for a gas it is the ratio between the weight of a given
volume of gas and the weight of the same volume of dry air in the same
standard conditions.
Stepwise Cracking - SWC
Formation of cracks, even in absence of mechanical solicitations, as a
consequence of diffusion of atomic hydrogen, produced in the cathodic reaction
in H
2
S containing environments, and the successive recombination to molecular
hydrogen inside the metallic lattice near microcracks, inclusions or defects.
Stepwise Cracking includes: Stress Oriented Hydrogen Induced Cracking,
Blistering, Hydrogen Induced Cracking.
Stress Corrosion Cracking - SCC
A process resulting from the combined action of corrosion and tension
mechanical solicitations due to residual or applied stresses; it causes the
formation of surface stress corrosion cracks; cracks are usually perpendicular to
the stress direction.
Sulphide Stress Cracking - SSC
Formation of cracks caused by stress corrosion, with a significant contribution
of H
2
S as a corroding agent.
Type of fluid
In the present document the following types of fluid are considered: liquid
hydrocarbons (I.L.); gas and gas with condensates hydrocarbons (I.G.); glycol
(G.); sea water (A.M.); fresh water (A.D.); brackish water (A.S.); formation
water (A.F.).
Wettability
Tendency of a fluid to disperse or to adhere to a solid surface in presence of
another insoluble liquid. Wettability is a measure of the preference of corrosion
products or metallic surfaces for water or oil.
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1.4 Abbreviations and conversion factors
Table 1.1 shows the corrosivity parameters mentioned in this document with
their abbreviations and measure units. Table 1.2 shows the main conversion
factors.
Tab. 1.1 - Corrosion parameters, abbreviations, and units.
PARAMETER Abbreviation Unit
operating pressure P MPa
operating temperature T C
minimum temperature T
min
C
maximum temperature T
max
C
H
2
S molar fraction yH
2
S mole/mole%
CO
2
molar fraction yCO
2
mole/mole%
H
2
S partial pressure pH
2
S MPa
CO
2
partial pressure pCO
2
MPa
water cut percentage WCUT m/m %
water oil ratio percentage WOR m/m %
gas oil ratio GOR Nm/m
API grade API (-)
total salinity in the water phase TDS g.l
-1
water chemical analysis
chlorides concentration
Cl
-
mg
.
l
-1
(ppm)
bicarbonates concentration
HCO
3
-
mg
.
l
-1
(ppm)
acetates concentration
HAC mg
.
l
-1
(ppm)
sulphates concentration
SO
4
--
mg
.
l
-1
(ppm)
sodium concentration
Na
+
mg
.
l
-1
(ppm)
potassium concentration
K
+
mg
.
l
-1
(ppm)
magnesium concentration
Mg
2+
mg
.
l
-1
(ppm)
calcium concentration
Ca
2+
mg
.
l
-1
(ppm)
iron concentration
Fe
2+
mg
.
l
-1
(ppm)
oxygen in aqueous phase cO
2
mg
.
l
-1
(ppm) or ppb
water pH in situ pH
in-situ
(-)
water pH in air pH
in-air
(-)
elemental sulphur S yes/no
mercury Hg yes/no
average flow rate v m/s
applied load
MPa
yield strength
YS
MPa
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Tab. 1.2 - Conversion factors
PARAMETER from to multiplying
factor
concentrations:
bicarbonates mg
.
l
-1
(ppm) meq
.
l
-1
0.016
acetates mg
.
l
-1
(ppm) meq
.
l
-1
0.017
sulphates mg
.
l
-1
(ppm) meq
.
l
-1
0.021
sodium mg
.
l
-1
(ppm) meq
.
l
-1
0.043
potassium mg
.
l
-1
(ppm) meq
.
l
-1
0.026
magnesium mg
.
l
-1
(ppm) meq
.
l
-1
0.083
calcium mg
.
l
-1
(ppm) meq
.
l
-1
0.050
iron mg
.
l
-1
(ppm) meq
.
l
-1
0.036
chlorides mg
.
l
-1
(ppm) meq
.
l
-1
0.029
pressure psi MPa 0.006895
pressure bar MPa 0.1
temperature
o
F
o
C (F-32)/1,8
volume barrel (US) m
3
0.1589
gas/liquid ratio ft
3
/barrel Nm
3
/m
3
0.178
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2 FLUID TYPES AND CORROSIVITY CLASSES
2.1 Fluid types
The following types of fluids are considered in this specification:
fluid types abbreviation
liquid hydrocarbons and multiphase systems I.L.
gas and gas with condensates I.G.
glycol G.
sea water A.M.
fresh waters A.D.
brackish waters A.S.
formation waters A.F.
The above listed types of fluids do not obviously cover the whole range of the
fluids met in oil and gas production plants, but only the main categories.
Particularly, all the fluids for decarbonation and desulphuration treatment are
excluded, as well as all chemical additives (corrosion inhibitors, fluidizers,
etc.).
2.1.1 Liquid hydrocarbons and multiphase
These fluids include oil, alone or in combination with gas phase and water
phase.
2.1.2 Gas and gas condensate
These fluids include gas, alone or in combination with condensates or water.
Reference is particularly made to fluids coming from dry gas and gas
condensate reservoirs.
2.1.3 Glycol
Reference is made to pure glycol, water and glycol mixtures, in gas dehydration
units and injected to prevent hydrate formation in gas lines.
2.1.4 Waters
They include all types of industrial water met in oil and gas production, and in
particular: fresh, brackish, formation and sea waters.
Fresh waters are usually shallow waters (from rivers or lakes) or waters from
shallow formations. Drinkable waters are characterised by a salinity below 1.5
g/l.
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Sea water has a salinity of 35 g/l, but locally can assume very different values.
Formation waters (brines) produced along oil and gas, are characterised by high
salinity. Sometimes they require to be re-injected into the formation, often after
an adequate corrosion control treatment.
The following criteria are used to define the different kinds of waters:
Fresh waters - A.D.
shallow waters
TDS < 2.0 g/l
Brackish waters - A.S.
shallow waters
TDS > 2.0 g/l
Sea waters - A.M.
TDS 35 g/l
Formation waters - A.F.
reservoir waters (deep formations)
TDS > 2.0 g/l
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Sheet 15
2.2 Corrosivity classes
For each type of fluid, the following corrosivity classes are identified:
type class properties
I.L. I.L.N. non containing CO
2
or H
2
S
I.L.C. containing CO
2
I.L.S. containing H
2
S
I.L.CS. containing CO
2
and H
2
S
I.G. I.G.N. non containing CO
2
or H
2
S
I.G.C. containing CO
2
I.G.S. containing H
2
S
I.G.CS. containing CO
2
and H
2
S
G. G.N. non containing CO
2
or H
2
S
G.C. containing CO
2
G.S. containing H
2
S
G.CS. containing CO
2
and H
2
S
For waters in general (A.), the following corrosivity classes are defined:
type class properties
A. deaerated non containing O
2
aerated containing O
2
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3 CORROSION PARAMETERS
3.1 Foreword
Corrosivity assessment of the fluids is carried out considering a set of corrosion
parameters regarding the fluid itself and the operating conditions.
3.2 Temperature
Temperature has a complex effect on corrosion rate, increasing or decreasing
the aggressiveness of a fluid in different ways; the following effects are
mentioned:
increase of the kinetics of corrosion reactions as the temperature rises;
inhibition, as temperature rises, of the susceptibility to hydrogen
embrittlement in presence of H
2
S;
formation of protective corrosion products (for example FeS, FeCO
3
or
CaCO
3
) at high temperatures.

Operating temperature values, T, shall be collected, as well as maximum fluid
temperature, T
max
, and minimum temperature that the system or the examined
component can reach, also considering temperature of external environment.
Minimum temperature, T
min
, can be a key factor in selecting the proper
materials because of its effects on the resistance to brittle fracture.
3.3 Pressure
Partial pressure of gas corroding agents in water phase, as CO
2
, H
2
S, O
2
depends on total pressure P.
3.4 Water content
Water content in production fluids is a key factor in determining the actual
water wetting conditions on metallic walls. It can be expressed as:
water cut percentage, WCUT, in m/m %, that is water volume on total
volume of liquid phases,
water oil ratio percentage, WOR, in m/m %, that is water volume on total
volume of hydrocarbons in liquid phase
In liquid hydrocarbons and in multiphase systems water is present as formation
water; in gas systems water can be present as condensation water or formation
water dragged from the reservoir. In the latter case water has a high salinity.
Water is always associated to gas from reservoir.
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Conservatively, a gas whose temperature is at least 10

C above its dew point
temperature, is considered non corrosive because of the absence of liquid water
phase.
3.5 Gas Oil Ratio
Gas Oil Ratio, GOR, is referred to the standard conditions (1 bar - 0.1 MPa and
25C) and it is expressed as Nm (gas)/m(oil).
Systems with high GOR show a high turbulence with probable contact between
the gas and the water phases with metallic walls.
3.6 Hydrodynamic conditions
For monophase fluids, gas or liquids, flowing in a pipe, the average flow rate
can be defined as ratio between flow and cross section of the pipe.
In multiphase systems, it is useful to define the surface flow rate as the velocity
that each phase would have if it flew alone through the entire section of the
tube. Surface velocity in multiphase systems, through horizontal or vertical
pipes, allows to determine the type of flow pattern.
Hydrodynamic conditions affects corrosion in the following modes:
effects on phase transportation: high turbulence conditions, particularly in
correspondence of geometrical discontinuities (for instance protuberant
weld head), cause local water separation; on the other hand, stagnating
conditions or low flow rates promote water separation from oil;
effects on transport phenomena in solution: turbulence affects mass
transport of corrosion reactions reagents and products;
decrease in corrosion inhibitor efficiency in high flow rate conditions;
mechanical effects in removing protective deposits (corrosion products or
scales) on metallic surfaces;
mechanical abrasion effects on metallic walls in sand or solid particles
containing fluids.
The mentioned effects need, in the most complex cases, an evaluation to be
carried out by both corrosion and hydrodynamics experts.
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3.7 CO
2
molar fraction
To evaluate the CO
2
corrosion, and to calculate the partial pressure, CO
2
content in the gas phase expressed as molar fraction, yCO
2
.
The CO
2
content in the gas phase can also be approximately expressed as
weight percent.
The CO
2
partial pressure, pCO
2
, is calculated as:
pCO
2
= P yCO
2
For higher pressures, roughly above 100 bar (10 MPa), the fugacity, f, is used
to calculate partial pressure:
pCO
2
= f yCO
2
3.8 H
2
S molar fraction
The H
2
S content is expressed as molar fraction in the gas. In ideal gas, molar
fraction and volume percentage are the same.
As in CO
2
case, H
2
S molar fraction is used to estimate the H
2
S partial pressure
as:
pH
2
S = P yH
2
S
For higher pressures, roughly above 100 bar (10 MPa), the fugacity, f, is used
to calculate partial pressure:
pH
2
S

= f yH
2
S
3.9 API Grade
API grade, or API gravity, is a measure for fluid density (oil, water, natural gas)
(ASTM D 287-92). It is calculated with the following expression:
= API
141, 5
131, 5
with:
= specific gravity at 15 C.
Water has an API grade 10, as raw oil's, while crude oil has values ranging
from 6 (very heavy) to 60 (very light). Usually oils range from 25 to 35
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API grade. Oils are considered light when they have API grade values between
35 and 45, and heavy when API grade is below 25.
3.10 Water chemical analysis
To correctly evaluate corrosivity, a complete chemical analysis of the water
phase is required. Along the analysis all information regarding sampling
procedures shall be retained.
Some chemical composition parameters have primary importance and are
reviewed here below.
Total salinity
It is the solid residue after boiling, expressed in g/l.
High salinity, especially in presence of oxygen, enhances localised corrosion
forms, promoting separation between anodic and cathodic areas, and galvanic
coupling effects.
pH
pH has a significant effect on water corrosivity, through the hydrogen evolution
reaction; precipitation equilibria of protective scales also depend on pH.
In aqueous phase associated with hydrocarbon production pH, is determined by
the solubility equilibria of acid gas as CO
2
and H
2
S (and the following
dissociation and reaction equilibria). pH measurements at operating conditions,
called pH in situ, pH
in-situ
, have intrinsic difficulties. To obviate to this problem
some software programs based on temperature, pressure and water composition
are available to calculate the pH in situ (for instance CORMED program
developed by ELF).
Acid environments (pH < 6) are more corrosive than neutral pH (from 6 to 8) or
alkaline (pH > 8) ones. Alkaline fluids with pH above 11-12 are not considered
corrosive for carbon steel.
Chlorides
Chlorides concentration affects localised corrosion forms, mainly through the
depassivation effect caused by chloride ions, especially with stainless steels.
Oxygen
Oxygen is dissolved in waters contacting with the atmosphere. It is absent in
reservoir fluids. Whenever oxygen is afterwards introduced into the fluid, i.e.
by contact with the atmosphere or through faulty seals or because it is
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Sheet 20
contained in additives, its effect on corrosivity shall be carefully evaluated. In
H
2
S containing fluids, oxygen may cause H
2
S oxidation to elemental sulphur,
tiosulphates etc., thus producing an aqueous phase acidification.
Organic acids
Organic acids (formic HCOOH, and acetic CH
3
COOH) are often present in
production fluids containing CO
2
. Their presence shall be considered in water
pH calculations.
Elemental sulphur
Elemental sulphur, that can be found in some reservoir, often in combination
with H
2
S, is a strong oxidant and it is extremely aggressive also for corrosion
resistant alloys.
3.11 Sulphates-reducing bacteria
Sulphates-reducing bacteria (SRB) grow in anaerobic conditions in presence of
sulphates ions, that are reduced to sulphides. The microbial corrosive attack is
characterised by formation of black deposits of sulphides-containing corrosion
products on the metal.
Bacteria are present in soil, natural waters and mud; they are not normally
found in hydrocarbon reservoirs, unless they are introduced there, for example,
during drilling or through water injection systems.
3.12 Sand and suspended solids
The presence of sand and suspended solids in the fluid causes erosion of
metallic surface, at a rate that depends on flow rate and density of the fluid and
on quantity, density and morphology of the solids present in the fluid.
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Sheet 21
4 CORROSIVITY CLASSES
4.1 Liquid hydrocarbons and multiphase systems (I.L.)
Liquid hydrocarbons and multiphase systems are classified according to the
following corrosion parameters:
CO
2
partial pressure;
H
2
S partial pressure;
maximum and minimum operating temperature;
water cut percentage or water oil ratio percentage;
gas oil ratio;
total salinity and/or chloride content of the aqueous phase;
average flow rate;
elemental sulphur;
oxygen;
sand.;
water chemical analysis;
water pH-in-situ;
water pH-in-air;
API grade;
sulphates reducing bacteria;
flow pattern.
Liquid hydrocarbons and multiphase systems are classified according the
following criteria:
Non containing CO
2
and H
2
S, I.L.N.
pCO
2
< 0.001 bar (0.0001 MPa), and
pH
2
S < 0.0035 bar (0.00035 MPa).
containing CO
2
I.L.C.
pCO
2
> 0.001 bar, and
pH
2
S < 0.0035 bar.
containing H
2
S I.L.S.
pCO
2
< 0.001 bar, and
pH
2
S > 0.0035 bar.
containing CO
2
and H
2
S I.L.CS.
pCO
2
> 0.001 bar, and
pH
2
S > 0.0035 bar.
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4.2 Gas hydrocarbons and gas with condensates
Gas hydrocarbons and gas with condensates are classified according to the
following parameters:
CO
2
partial pressure;
H
2
S partial pressure;
maximum and minimum operating temperature;
water cut percentage or water oil ratio percentage;
total salinity and/or chloride content of the aqueous phase;
elemental sulphur;
average flow rate of the fluids;
oxygen;
sand and suspended solids;
water chemical analysis;
water pH-in-situ;
water pH-in-air;
sand;
flow rate;
sulphates reducing bacteria.
Gas hydrocarbons and gas with condensates are classified according the
following criteria:
Non containing CO
2
and H
2
S, I.G.N.
pCO
2
< 0.001 and
pH
2
S < 0.0035
containing CO
2
I.G.C.
pCO
2
> 0.001 and
pH
2
S < 0.0035
containing H
2
S I.G.S.
pCO
2
< 0.001 and
pH
2
S > 0.0035
containing CO
2
and H
2
S I.G.CS.
pCO
2
> 0.001 and
pH
2
S > 0.0035
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Sheet 23
4.3 Glycol
Glycol are classified according to the following corrosion parameters:
water percentage;
operating temperature;
CO
2
partial pressure;
H
2
S partial pressure;
dissolved oxygen;
water salinity;
sand and suspended solids;
pH.
The eventual presence of oxygen, i.e. from contact between glycol and
atmosphere, with water presence in glycol, causes a high corrosivity, even
when there is no CO
2
or H
2
S.
Similarly to gas hydrocarbons, liquids and multiphase systems, glycol are
classified according the following criteria:
Non containing CO
2
and H
2
S G.N.
pCO
2
< 0.001 and
pH
2
S < 0.0035
containing CO
2
G.C.
pCO
2
> 0.001 and
pH
2
S < 0.0035
containing H
2
S G.S.
pCO
2
> 0.001 and
pH
2
S < 0.0035
containing CO
2
and H
2
S G.CS.
pCO
2
> 0.001 and
pH
2
S > 0.0035
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Sheet 24
4.4 Waters
Waters are classified according to the following corrosion parameters:
dissolved oxygen;
pH;
H
2
S content;
operating temperature;
total salinity aqueous phase;
sulphates reducing bacteria;
hydrodynamic conditions;
chemical analysis;
conductivity.
Waters are classified according to the following corrosivity classes
deaerated waters
cO
2
<0.010 mg.l
-1
(10 ppb)
deaerated waters
cO
2
<0.010 mg.l
-1
(10 ppb)
The following conditions are individuated for waters:
waters with low pH: 3 < pH < 6
waters with high pH: pH > 6
H
2
S containing waters; H
2
S < 1 mg.l
-1
(1 ppm)
H
2
S non containing waters; H
2
S < 1 mg.l
-1
(1 ppm)
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Sheet 25
5 CORROSION FORMS
5.1 General
5.1.1 Foreword
In this section the most common corrosion forms occurring in oil and gas
production are reviewed.
For each corrosion form, the relevant definitions are reported and the criteria to
predict corrosivity are illustrated.
5.1.2 Materials
The main metallic materials families utilised in oil industry are the following:
carbon steels
low alloy steels
stainless steels
ferritic
martensitic
austenitic
ferritic-austenitic (duplex)
nickel alloys
cobalt alloys
titanium and titanium alloys.
Stainless steels, nickel and cobalt alloys and titanium are generally defined
CRA, which stands for corrosion resistant alloys.
5.1.3 Corrosion morphologies
Corrosion forms can be divided into the following fundamental types,
according to the morphology of the attack:
general corrosion: it occurs on the whole surface of the metal in contact with
the environment; it can be uniform, with a generalised and regular loss of metal
on the exposed surface, or non uniform, with corrosion penetration varying
from area to area.
localised corrosion: it happens in a limited portion of surface in contact with the
environment. The morphology of localised corrosion changes considerably,
depending on material and environment. The entity of the damage does not
depend on the total quantity of oxidised metal.
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The following classes can be used for to express the penetration rate of general
corrosion forms:
negligible <50 m/y
low 50-100 m/y
moderate 100-500 m/y
severe 500-1000 m/y
very severe >1000 m/y
5.2 Water wetting conditions
Below 400 C corrosion can occur:
in presence of liquid water and
if water is, even only temporarily, in direct contact with the metallic
surface;
those conditions define the water wetting of the metallic surfaces.
Water stabilises ionic species in solution that participate, as reagents, products
or intermediates, in the electrochemical corrosion reaction, and it activates local
micro cells on metallic surfaces. In particular situations, other solvents such as
methanol, can acquit a similar function, even if with different effectiveness.
5.2.1 Liquid and multiphase systems
In multiphase systems corrosion is directly proportional to the fraction of time
the metal is microscopically wetted by the aqueous phase. In multiphase
systems, water separation and transportation of the aqueous phase in contact
with the metallic wall (wetting), depend on:
nature of the phases and repartition;
phases composition;
hydrodynamics;
geometry.
The content of formation water in crude oil is quite variable. When water
fraction is very low, below a few percents, the metallic walls are always oil-
wetted; when water is the pre-eminent phase, water wetting conditions prevail;
when water concentration is intermediate, there is an intermittent water wetting.
Local water wetting conditions can occur in presence of geometrical
discontinuities, which cause turbulence and water separation from the oil phase,
even if water content is quite low. Significant cases are extruding weld beads or
valves. In stagnant conditions, as in tanks or in horizontal pipes in laminar
regimen, where water phase spontaneously separates on the lower part of the
pipe or at the tank bottom, even a low percentage of water is enough to produce
water wetting conditions.
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5.2.2 Gas and gas with condensates system
In gas and gas with condensates reservoirs, gas is saturated with water, in
equilibrium with the liquid water in the reservoir. During production, the gas
expands and cools: when it reaches the water dew point, water starts to
condensate from gas; gasoline, when present, can condensate before or after
water condensation.
Without reliable information on the presence of water or on condensation
conditions, it is convenient to assume that an aqueous phase is always present
in contact with the metallic surface. On the contrary if operating temperature is
at least 10 C above the water dew point temperature, the presence of liquid
water can be excluded.
Beyond condensation water, also formation water, mechanically dragged by the
gas can be produced. In case of condensation water, salinity is very low, while
in formation waters it can be quite high; usually the most common situation is
an intermediate one, with a water composition diluted in comparison to
formation water, due to condensation water.
Water is conventionally assumed to be a formation water when the ionic
strength is higher than 0.5.
Water, depending on hydrodynamic conditions, can be present as small drops
dispersed in the gas or as a liquid film that wets the walls while flowing,
dragged by the gas. The thickness of the liquid film is tens or hundreds of
micron class, and decreases as the quantity of liquid produced decreases and as
the gas flow rate increases. Corrosion rate presumably increases as the
thickness of the liquid film and its flow rate increase.
The liquid film can be constituted by water, hydrocarbons or a mixture of both.
In the last case, water wetting depends on the quantity of the produced water,
and, in particular, by the water fraction in the liquid.
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5.3 O
2
corrosion
Oxygen corrosion of carbon and low alloy steels occurs in aerated
environments as general corrosion. Corrosion rate is directly proportional to the
amount of oxygen available at the metal solution interface, i.e. the oxygen flux.
This depends on:
1. environmental conditions:
- oxygen concentration;
- hydrodynamic conditions:
- temperature.
2. the steel surface conditions.
In stagnant aerated water and at room temperature, corrosion rate, expressed in
m/y, is about 20 times the oxygen concentration expressed in ppm.
In non-stagnant conditions this value shall be multiplied by a factor
approximately equal to the square root of the flow rate (in m/s) for laminar
flow, and equal to the flow rate (in m/s) for turbulent flow.
In aerated waters with flow rate above 1 m/s and temperature above 30C, the
following equation can be applied to predict corrosion rate of carbon and low
alloy steels:
v
corr
= 0.020 cO
2
2
(T-30)/30
v
n
where:
v
corr
corrosion rate, m/y
cO
2
oxygen concentration, ppb
v flow rate, m/s (it is assumed to be v=1 if v<1)
T temperature, C
n 0.5 for laminar flow and 1 for turbulent flow.
In deaerated waters, with oxygen concentration below 10 ppb, the following
formula has been proposed by Oldfield et al. to predict oxygen corrosion rate in
steel pipes:
v
corr
= 5.29 cO
2
(v
7
/d)
1/8
exp
(T/42.6)
where:
v'
corr
corrosion rate, m/y
cO
2
oxygen concentration, ppb
v flow rate, m/s
T temperature, C
d internal diameter of the pipe, m.
The predicted values v
corr
, represent the maximum corrosion rates occurring on
steel surface in absence of any protective products. The actual corrosion rate,
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Sheet 29
after formation of partially protective scales, is approximately an order of
magnitude lower.
5.4 H
2
S corrosion
H
2
S promotes localised corrosion forms on carbon and low alloy steels.
The maximum corrosivity occurs when the content of H
2
S in solution is
between 100 and 1000 ppm, approximately corresponding to 0.02-0.2 bar
(0.002-0.02 MPa). At 60C, the penetration rate can be as high as 1 mm/y; at
higher temperatures corrosion rate decreases, but the risk of localised corrosion
increases.
Localised corrosion is enhanced by the galvanic coupling effect between steel
and iron sulphide corrosion products: iron sulphide, in fact, is an electronic
conductor and it behaves cathodically with respect to steel.
5.5 Elemental sulphur corrosion
Elemental sulphur is present in a few reservoirs, often combined with H
2
S.
Sulphur is a strong oxidant: at a low temperature (<120C), elemental sulphur
reacts with carbon or low alloys steels, or with their oxides, to form sulphides.
At normal temperature, in presence of chlorides, general corrosion rate is very
severe, even above 20 mm/y. As temperature increases, corrosion rate grows,
but not by orders of magnitude. At temperatures above 120C corrosivity grows
in relation to H
2
S, sulphuric acid (4S+4H
2
O=3H
2
S+H
2
SO
4
) and polysulphanes
(H
2
S
x
) formation. Above 150 C there is a decrease of the corrosion due to
partially protective scales; however corrosion rate remains very high (8-10
mm/y a 180C).
Corrosion rate increases sensibly in presence of salts like NaCl and Na
2
SO
4
and
it is substantially independent from presence of H
2
S.
CRA in presence of elemental sulphur are susceptible to localised attacks. Low
nickel austenitic stainless steels (AISI 304) and austenitic-ferritic stainless
steels are particularly sensible to elemental sulphur presence, with corrosion
rates as high as those ones observed on carbon steels and low alloy steels.
Corrosion resistance to elemental sulphur increases in high alloyed material:
nickel, chromium and molybdenum have a beneficial effect; high nickel
austenitic stainless steels, nickel alloys and cobalt alloys can be susceptible to
localised attack, as pitting, crevice or stress corrosion cracking, in particular
above 150C and in presence of chloride ions.
Nickel-chromium-molybdenum alloys with Ni>50%, Mo>12% and Cr>15%
are resistant to elemental sulphur corrosion.
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5.6 CO
2
corrosion
CO
2
is one of the main corroding agents in oil and gas production.
CO
2
corrosion occurs with quite different morphologies, often designed with
specific terms as: mesa corrosion, pitting corrosion, ring worm corrosion.
Prediction of CO
2
corrosion is based on the following parameters:
CO
2
partial pressure;
water phase composition;
pH;
temperature;
hydrodynamic conditions
presence of H
2
S.
5.6.1 Effects of chemical species in solution
Chemical composition of the water phase in contact with steel, has a great
influence on CO
2
corrosion rate, especially through the modification of local
pH (pH
in-situ
); corrosion rate, in fact, is negligible, or low, when pH
in-situ
is above
5.5-5.6.
The effect of the main chemical species that influence the phenomenon are
briefly reviewed here below.
Bicarbonates. In waters with high alkalinity (HCO
3
-
= 30150 meq/l), corrosion
rate is low or moderate. Also the Ca
2+
/HCO
3
-
ratio affects the water
aggressiveness: in alkaline waters, with HCO
3
-
>>Ca
2+
, corrosion rate is low or
moderate as above said; when Ca
2+
/ HCO
3
-
is high (>1000 meq/meq), pH is
low, but corrosion results uniform, since separation of anodic and cathodic
areas cannot occur. Furthermore, when the content of Ca
2+
ions in solution is
high, precipitation of a protective layer of CaCO
3
can occur in relation to local
pH conditions.
Acetates. Several reservoir fluids contain volatile organic acids, in particular
acetic acid (CH
3
COOH). With the term acetates, the sum of all organic acid
in solution, expressed as meq/l, is normally intended; when bicarbonates are
determined through titration, a part of acetates is expressed as bicarbonates.
According to some authors, CO
2
corrosion depends on the acetate concentration
in solution; in particular CO
2
corrosion is predicted to be low when the acetates
content is low (<1 meq/l).
Presence of acetates affects the equilibria that determine the pH
in-situ
; moreover
acetates are strong complexant and, from this viewpoint, they could be an
obstacle to the formation of protective corrosion products.
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Fe
2+
ions. The contamination of Fe
2+
ions, coming for instance from steel
corrosion, causes an increase of pH (compared with the pH determined by CO
2
dissolution alone) due to the formation of FeCO
3
and Fe
3
O
4
. Corrosion
products, through the modification of pH, affect corrosion rate, with a decrease
effect.
Variation of pH, when Fe
2+
saturation conditions are reached, is between 0.5
and 1.6. The saturation pH for FeCO
3
and Fe
3
O
4
can be calculated as a function
of temperature and CO
2
partial pressure data.
H
2
S. Presence of H
2
S in solution, even in very small quantities, highly modifies
the chemistry of the solution and the corrosion behaviour of steels. The
formation of a protective film of iron sulphide, FeS, passivates the steel thus
reducing its corrosion rate. However the risk of localised corrosion (pitting ) is
higher: iron sulphide, in fact, is an electronic conductor and causes an increase
of free corrosion potential.
5.6.2 De Waard and Milliams model.
Base equation. In presence of water with a very low salt content (i.e.
condensation water) CO
2
corrosion rate can be calculated with the De Waard
and Milliams base equation.
Log v
T
Log pCO
corr
( ) . . ( ) = + 5 8
1710
0 67
2
where:
v
corr
corrosion rate in mm/y;
T temperature in K;
pCO
2
CO
2
partial pressure in bar;
Log logarithms are decimal.
At high pressure, approximately above 100 bar (10 MPa), the ideal gas model
is not applicable and fugacity shall be used instead of pressure in calculating
the CO
2
partial pressure.
Fugacity is calculated from pressure through the fugacity coefficient a:
f = a P
The values of corrosion rate predicted by the base equation are often much
higher than the corrosion rates actually observed. For this reason, some
correction factors have been introduced to take into account of specific effects
on corrosion rate.
Formation of protective corrosion products . Above a certain temperature,
named scaling temperature (T
scale
), the actual corrosion rate is lower then
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Sheet 32
predicted by the base equation due to formation of protective corrosion
products effects, provided that hydrodynamic conditions do not cause their
removal.
The scale temperature, T
scale
, is given by the following equations:
Tscale K
Log fCO
( )
. . ( )
=
+
2400
6 7 0 6 2
and the correspondent multiplying factor, F
scale
, is:
Log F
T
Log fCO scale ( ) . ( ) . =
2400
0 6 6 7 2

The new corrosion rate, v
corr ,
is:
v
corr
= v
corr
F
scale
Fe
2+
and pH effect. As previously seen, in absence of other buffering chemical
species, contamination of the solution with Fe
2+
ions causes, at constant
temperature and CO
2
partial pressure, a reduction of corrosion rate, connected
to a local pH variation.
When the scaling factor, F
scale
, is not applicable to modify (i.e. reduce) the
corrosion rate calculated by the base equation (T < T
scale
or F
scale
= 1), the pH
effect is considered as shown here below.
The saturation pH, pH
sat
, for Fe
3
O
4
and FeCO
3
, is calculated with the following
equations:
pH
T
Log fCO sat = + 136
1307
017 2 . . ( )
corresponding to the formation of Fe
3
O
4
, and:
pH Log fCO sat = 54 0 66 2 . . ( )
corresponding to the formation of FeCO
3
.
The corrosion product with the lowest saturation pH is the most stable and that
one with the highest probability of formation.
The following parameter is then defined:
pH = pH
sat
- pH
in-situ
and the correction factor F
pH
is calculated through the following procedure:
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Sheet 33
if: pH
sat
pH
in-situ
:
Log F pH pH pH sat insitu ( ) . ( ) = 032
if: pH
sat
< pH
in-situ
Log F pH pH pH insitu sat ( ) . ( )
.6
= 013
1
In fluids containing CO
2
and small quantities of H
2
S, the following expression
has been proposed for F
pH
:
F
pH
= 1 -0.34 pH
The new corrosion rate, V
corr
, corrected for pH is then calculated as:
V
corr
= V
corr
F
pH
Effect of glycol. In presence of glycol and in oxygen free environments, a
significant reduction of corrosion rate is observed, as a consequence of an
inhibition effect.
The relevant correction factor for the corrosion rate calculated from the base
equation A.1. is given by the following formula:
Log F A Log W
glyc
( ) ( ( %) ) = 2
where:
W% is the weight percentage of water in the glycol;
A is a constant which depend on type of glycol; it is
normally
assumed A=1,6.
The correction is applicable for a water content above 10% in weight; the
corrected corrosion rate, V
corr
, is given by:
V
corr
= V
corr
F
glyc
5.6.3 Top of line corrosion
It can occur in pipes where the gas phase flows over a liquid water vein. On the
upper side, condensing water is saturated by CO
2
eventually present: corrosion
rate in this situation, where the efficiency of corrosion inhibitor may result
limited, depends on the rate of water condensation from gas.
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If the fluid flow in the conduct is slug type, the passage of liquid slugs modifies
favourably the pH of water (removing or diluting the condensation water film)
and eventually filming the metallic wall with liquid hydrocarbons.
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5.6.4 Prediction rules for CO
2
corrosion (Crolet Model)
A completely different approach to predict the corrosivity of CO
2
containing
fluids has been proposed by Crolet for corrosion in oil and gas wells. The
predictive model is part of a software program, named CORMED, (by the
same author) for the calculation of in-situ pH.
Prediction of corrosivity is expressed using the following classes of corrosion-
risk:
very low;
medium;
high.
No corrosion rate values are associated to such classes, but reference is made to
an approximate operating life, which is considered acceptable, equal to 8-10
years.
The rules to predict the risk of CO
2
corrosion consider the following
parameters:
type of produced water, formation or condensation;
CO
2
partial pressure;
in-situ pH;
potential corrosivity (PC): it is a parameter which can be calculated with
CORMED program; alternatively, corrosion rate calculated with the base
equation of De Waard and Milliams model can be used;
in situ acetic acid content;
Ca
2+
/HCO
3
-
ratio.
The prediction rules are reported here below.
Condensation water
corrosion risk is very low if:
pCO
2
< 0.05 bar (0.005 MPa) or
PC < 0.2 mm/y or
pCO
2
< 0.2 bar (0.002 MPa) and in situ acetic acid < 0.1 meq/l
corrosion risk is medium if:
0.2 < pCO
2
< 5 bar (0.02<pCO
2
<0.5 MPa) and in situ acetic acid< 0.1 meq/l
in every other condition the corrosion risk is high
formation water
corrosion risk is very low if:
pCO
2
< 0.05 bar (0.005 MPa) or
PC < 0.2 mm/y or
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Sheet 36
in situ pH > 5.6 or
0.05 < pCO
2
< 10 bar (0.005<pCO
2
<1 MPa) and in situ acetic acid < 0.5
meq/l
corrosion risk is medium if:
PC < 1 mm/y
in situ acetic acid < 0.1 meq/l
Ca
2+
/HCO
3
-
< 1000
in every other condition the corrosion risk is high.
5.6.5 Corrosion products
Prediction of corrosion products on steel in CO
2
containing fluids may prove
useful for predicting the morphology of the corrosion attack. The following
criteria are applicable:
T<60C and pCO
2
< 5 bar (0.5 MPa): formation occurs of amorphous FeCO
3
with scarce adherence;
60<T<100: formation of a protective layer of FeCO
3
occurs;
T>100: the layer increases considerably its protectiveness and formation of
Fe
3
O
4
occurs.
The protective effect of corrosion products is strictly related to hydrodynamic
conditions.
5.7 Galvanic corrosion
Galvanic corrosion occurs when metallic materials with different nobility -
different electrochemical potential - are in electrical contact and exposed to an
aggressive environment. On less noble metal - the one with the most negative
potential - accelerated anodic corrosion processes take place, while the more
noble metal becomes a cathode, without corroding.
The presence of galvanic coupling gives place to an increase in corrosion rate
or to localised corrosion only if the environment is corrosive and with sufficient
electric conductivity. Corrosion rate of the less noble metal of the couple results
higher compared to the one exhibited by the same metal if uncoupled; the
intensification factor depends on the ratio between the two metal surfaces.
Depending on the configuration of the aqueous phase, if it is present as a layer
or as a bulk, the coupling is possible between anodic and cathodic areas
geometrically separated: the higher are the water phase conductivity and the
available cross section of the flux tubes, the higher is the distance between
electrically coupled areas.
Galvanic contact effects can also occur between metal and scales, fragments or
corrosion products with electronic conductivity It is the case, for instance, of
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magnetite scales or of iron sulphide corrosion products, both showing a
cathodic behaviour with respect to carbon or low alloy steel.
Severe situations of galvanic contact can be observed in salt waters, with high
conductivity and aerated, as for instance sea water.
Negative effects can be observed also on the more noble metal. This is the case
of coupling between CRA (stainless steel or nickel alloy) with carbon or low
alloy steel in deaerated environments, where the main cathodic reaction is
hydrogen evolution: hydrogen embrittlement is possible on the more noble
metal if it is susceptible; low temperatures and presence of H
2
S promote these
situations.
The following table summarises the different situations.
environment (T) galvanic coupling effects
carbon steel - anode
E
corr
less noble
CRA - cathode
E
corr
more noble
low temperature
(< 60 C)
general corrosion
pitting and crevice
hydrogen
embrittlement
medium-high
temperature
(> 60 C)
general corrosion
pitting and crevice
stress corrosion
cathodic protection
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5.8 Pitting and crevice
Pitting and crevice are localised corrosion forms typical of metals showing an
active-passive behaviour, characterised by formation of a galvanic macro-cell
between a passive area of the metal, where the cathodic process takes place,
and an active one, where anodic dissolution occurs.
The surface fraction interested is always very low, compared to the total
exposed area.
In pitting corrosion, the anodic area is the bottom of the pit, while in crevice
corrosion it is the shielded metal surface within the crevice.
5.8.1 Susceptible materials
The susceptible materials are those ones that normally operate in passive
conditions; in particular:
stainless steels;
nickel alloys;
copper alloys;
titanium alloys (crevice corrosion).
To express comparatively the pitting resistance of nickel alloys and of stainless
steels, in particular the austenitic and austenitic-ferritic types, specific indexes
have been proposed, based on alloy composition.
The index named P.R.E. (Pitting Resistance Equivalent) is calculated according
to the chemical composition, and in particular to the content of Cr, Mo and N,
as:
P.R.E. = Cr% + 3.3 Mo% + 16N%
Another formula has also been proposed which takes into account of the
presence of tungsten in the alloy:
P.R.E. = Cr% + 3.3 (Mo% + 0.5W%) + 16N%
For crevice corrosion, the following index, named Critical Crevice Index,
C.C.I., has been proposed:
C.C.I. = Cr% + 4.1Mo% +27N%
The pitting and crevice indexes are often utilised as absolute values, but the
most appropriate use is as ranking parameters of different materials.
Another evaluation parameter is the critical pitting temperature (C.P.T.)
experimentally determined by immersion tests in FeCl
3
(see ASTM G48-76) or
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Rev.2 June 1995
Sheet 39
by electrochemical methods. A good relationship between C.P.T. and P.R.E.
has been found for austenitic and austenitic-ferritic stainless steels.
In the same way, critical crevice temperature (C.C.T.) is determined for crevice
corrosion.
5.8.2 Initiation conditions
Initiation of pitting and crevice corrosion occurs in presence of chloride ions in
solution. 200 ppm is the threshold for chloride ions concentration to avoid risks
of pitting or crevice initiation of austenitic stainless steels (types AISI 304 and
316).
Availability of a cathodic process, i.e. oxygen reduction; hydrogen evolution;
elemental sulphur reduction, is needed for propagation to occur.
Hydrodynamic conditions have a great influence on pitting initiation: AISI 316
stainless steel, for instance, is resistant to pitting corrosion in sea water
provided that flow rate is above 1.5 m/s, while in stagnating conditions pitting
corrosion occurs.
Temperature has a strong influence too: tendency to pitting and crevice
increases as temperature increases.
02555.VAR.COR.PRG
Rev.2 June 1995
Sheet 40
5.9 Stress Corrosion Cracking (SCC)
In addition to stress corrosion in presence of H
2
S (SSC), the following types of
stress corrosion cracking can take place in oil and gas production plants:
SCC of stainless steels in chloride containing environments;
SCC in presence of polythionic acids.
5.9.1 Chlorides stress corrosion cracking
It concerns mainly the austenitic stainless steels of the 300 series (i.e. AISI 304
and 316), austenitic-ferritic stainless steels are also susceptible, while nickel
alloys are practically immune.
Austenitic stainless steels. SCC in austenitic stainless steels type AISI 304 and
316 is observed in the following conditions:
T > 60
o
C;
Cl
-
>10 ppm;
applied or residual stress state, > 150 MPa ( > 30%
YS
).
With respect to temperature and chloride concentration, which are the most
influencing parameters, the following limits can be assumed for stainless steels
type AISI 304 or 316:
T < 50
o
C Cl
-
concentration without limits
50 < T <100
o
C Cl
-
< 100 ppm
100 < T < 150
o
C Cl
-
< 30 ppm
T > 150
o
C Cl
-
< 10 ppm
However, the indicated limits for Cl
-
concentration have to be used very
carefully, because of unexpected local concentration phenomena. practically,
the use of austenitic stainless steels is recommended only for temperature below
50
o
C.
Austenitic stainless steels characterised by a higher nickel content (above 15%)
show a resistance to SCC which increases as the content of alloying elements
increases.
Other influencing parameters are:
content of dissolved oxygen in solution: it reduces the time to failure;
pH: low pHs reduce the time to failure (it shall be mentioned that below pH
2 general corrosion prevails and the conditions for SCC, that is coexistence
of active and passive surfaces, vanish);
stress state: high applied or residual loads determine a reduction of the time
to failure;
cold-working: it has a beneficial effect until a certain degree of cold working
has been reached (around 20%), after which the susceptibility to SCC
increases sensibly;
02555.VAR.COR.PRG
Rev.2 June 1995
Sheet 41
alloying elements: the nickel content (above 10%) has a beneficial effect;
other beneficial elements are: silicon (the effect is quite evident above 2%)
and carbon (above 0.10%); the harmful elements are: phosphorus and
nitrogen, which that have a synergetic negative effect; their content shall be
limited: P < 0.005% and N < 0.02%;
welds are preferential sites for SCC initiation because of residual stress
conditions and because of their own criticality.
Ferritic and martensitic stainless steels . Stainless steels with ferritic or
martensitic microstructure are less susceptible to stress corrosion, although not
immune, because of the low nickel content (Ni < 1%). The low nickel content,
in fact, leads to a lower stability of the passive film and promotes uniform
corrosion.
Austenitic-ferritic (duplex) stainless steels . Biphasic austenite-ferrite stainless
steels offer higher resistance to SCC, compared to ferritic and austenitic types.
The optimum resistance conditions are obtained when the two phases are
present in balanced quantities an for the highest nickel contents.
Nickel alloys. Nickel alloys are quite resistant to chloride stress corrosion;
alloys with nickel contents above 45% are practically immune.
5.9.2 Polythionic Acids Stress Corrosion Cracking
In correspondence to the periodical shut down of the plants, because of
entrance of air and humidity, polythionic acids (H
2
S
x
O
6
with x = 3, 4 or 5) can
form by oxidation of iron sulphide:
8FeS + 11O
2
+ 2H
2
O = 4Fe
2
O
3
+ 2H
2
S
4
O
6
Polythionic acids stress corrosion has been found mostly in refinery plants, and
particularly in desulphuration units. Austenitic stainless steels, especially if
sensitised, are quite susceptible. Failure occurs by crack formation, mostly
intergranular; transgranular cracks may be present, caused by chlorides.
Austenitic-ferritic stainless steels are more resistant than austenitic types; nickel
alloys (800 and 600 series) do not seem to be prone to the phenomenon.
Prevention is based on operation control in correspondence to the plant shut
downs, for instance foreseeing nitrogen conditioning of the equipment to
prevent sulphide oxidation.
Recommended materials are stabilised stainless steels (AISI 321 and 347) and
weld stabilisation heat treatments (900
o
C for at least 20 minutes).
02555.VAR.COR.PRG
Rev.2 June 1995
Sheet 42
5.10 Sulphide Stress Cracking (SSC)
Sulphide Stress Cracking (SSC) occurs on susceptible materials when specific
environmental conditions are met, characterised by presence of H
2
S and
mechanical stresses, applied or residual.
In oil and gas production, sour service are defined those conditions that give
place to SSC on susceptible materials, in particular carbon or low alloy steels.
In sour service conditions SSC resistant materials shall be selected.
5.10.1 Sour service conditions according to NACE
With reference to the NACE MR0175 Standard, sour conditions are defined as
follows:
gas systems (see also fig. 1)
P > 5 bar (0.5 MPa) and
pH
2
S > 0.0035 bar (0.005 MPa)
multiphase systems (see also fig. 2)
P > 20 bar (2 MPa) and pH
2
S > 0.0035 bar (0.00035 MPa)
5 < P < 20 bar (0.5<P<2 MPa) and pH
2
S > 0.65 bar (0.065 MPa)
P < 5 bar (0.5 MPa) and yH
2
S > 0.15
02555.VAR.COR.PRG
Rev.2 June 1995
Sheet 43
1
10
100
1000
0.0001 0.001 0.01 0.1 1 10
H2S molar fraction (yH2 S) in gas fase (%)
T
o
t
a
l

P
r
e
s
s
u
r
e

(
b
a
r
)
Sour Service
Fig. 1. - Sour service conditions for gas systems according to NACE.
1
10
100
1000
0.0001 0.001 0.01 0.1 1 10 100
H2S molar fraction (yH2 S) in gas fase (%)
T
o
t
a
l

p
r
e
s
s
u
r
e

(
b
a
r
)
Sour Service
Fig. 2. - Sour service conditions for multiphase systems according to NACE.
02555.VAR.COR.PRG
Rev.2 June 1995
Sheet 44
5.10.2 Sour service conditions according to EFC
Definition of sour service conditions according to EFC takes into account also
the in-situ pH of the water phase; in-situ pH values can be calculated using
algorithms, nomograms or software programs, based on chemical analysis of
the aqueous solution.
According to EFC, the following fields are defined (see also fig. 3):
sour conditions
pH 3.5
pH
2
S < 0.011 bar (0.0010.1 MPa) and pH 5.5 + log pH
2
S (bar)
pH
2
S > 1 bar (0.1 MPa) and pH 5.5
sour / non-sour transition zone
pH
2
S = 0.0010.01 bar (0.00010.001 MPa) and 3.5 < pH 5.5 + log pH
2
S
(bar)
pH
2
S > 1 bar (0.1 MPa) and pH = 5.5 6.5
Conditions outside these ones are defined non-sour and also susceptible
materials can be used.
In sour service conditions, materials resistant to SSC shall be used.
Sour / non sour transition conditions are considered as sour.
2.5
3.5
4.5
5.5
6.5
7.5
0.0001 0.001 0.01 0.1 1 10
Hydrogen Sulphide Partial Pressure (pH2S - bar)
S
o
l
u
t
i
o
n

p
H
"Non Sour Service"
Transition Region
Sour Service
Fig. 3. - Sour service conditions according to EFC
02555.VAR.COR.PRG
Rev.2 June 1995
Sheet 45
5.11 Stepwise Cracking
The term Stepwise Cracking refers to metal damages which occur as surface
blistering or as formation of internal stepwise microcracks, even in absence of
mechanical solicitations. Other terms are often used, as Stress Oriented
Hydrogen Induced Cracking, Blistering, Hydrogen Induced Cracking to
describe the same phenomenon.
Formation of microcracks or blisters is caused by atomic hydrogen produced on
the corroding metal surface which, in presence of H
2
S, diffuses into the metal
lattice. The atomic hydrogen eventually gathers in correspondence of inclusions
or segregation bands of the microstructure and recombines to molecular
hydrogen, producing a very high internal pressures and the mentioned metal
damages.
Materials susceptible to Stepwise Cracking are carbon and low alloy steels
produced by lamination and containing inclusions, and in particular C-Mn
steels with manganese sulphide inclusions, MnS type II.
5.11.1 Limits for initiation
The following limits are applicable for stepwise cracking initiation:
pH
2
S > 0.1 bar (0.01 MPa);
T < 80C;
pH
in-situ
< 6.

In case of fluids containing both CO
2
and H
2
S, the following limits applies (see
also fig. 4):
pH
2
S > 0.1 bar (0.01 MPa) if pCO
2
< 0.5 bar;
pH
2
S > 0.1107-0.0214pCO2 (bar) if 0.5 < pCO
2
< 5 bar;
pH
2
S > 0.0035 bar (0.00035 MPa) if pCO
2
> 5 bar.
02555.VAR.COR.PRG
Rev.2 June 1995
Sheet 46
0.0001
0.001
0.01
0.1
1
0.01 0.1 1 10
CO2 partial pressure (bar)
H
2
S

p
a
r
t
i
a
l

p
r
e
s
s
u
r
e

(
b
a
r
)
"Stepwise Cracking"
(T < 80C - pH < 6)
Fig. 4 - Limits for initiation of Stepwise Cracking.
02555.VAR.COR.PRG
Rev.2 June 1995
Sheet 47
5.12 Erosion corrosion
It is a corrosion form where there is the concurrence of electrochemical
corrosion with mechanical removal of the corrosion products caused by the
high flow rate.
It occurs on all the metallic materials. Whenever the aggressiveness conditions
are particularly severe it becomes necessary to make use of hard coatings with
high corrosion resistance, such as stellites or ceramics.
In absence of solid particles, corrosion-erosion initiates if the fluid velocity is
above a critical value. In API RP-14E the following formula is given for the
calculation of critical rate v
c
:
v
C
c
m
=
where:
v
c
= erosion critical velocity
C = erosion constant

m
= fluid density at operating conditions
The erosion constant can take different values depending on the material
(carbon steel or CRA), the type of service (continuous or intermittent) and the
inhibitor injection.
In the S.I. system, the units for the C constant are (kg/ms
2
)
1/2
, while in the
American system units are (lb/fts
2
)
1/2
; the conversion factor from the American
system to S.I. is 1.22.
The following values for the C constant, expressed here in the S.I. units, are
recommended:
C = 122 carbon steel, corrosive fluids, continuous service;
C = 152 carbon steel, corrosive fluids, intermittent s ervice;
C = 183-244 carbon steel, non corrosive fluids, continuous service;
C = 305 carbon steel, non corrosive fluids, intermittent service;
C = 183-244 carbon steel, corrosive fluids, continuous service,
continuous corrosion inhibitors injection;
C = 305 carbon steel, corrosive fluids, intermittent service,
continuous corrosion inhibitors injection;
C = 183-244 CRA alloys, continuous service;
C = 305 CRA alloys, intermittent service.
02555.VAR.COR.PRG
Rev.2 June 1995
Sheet 48
5.13 Sand erosion
The API formula for predicting corrosion-erosion rate shown in previous
paragraph is not applicable when sand or solid particle are present in the fluid.
Sand erosion rate is related to the following parameters:
content of solid particles in the fluid;
flow rate;
fluid density;
fluid viscosity;
density of solid particles;
dimension of solid particles;
morphology of solid particles;
dimensions and geometry of the metallic component.
The calculation of sand erosion rate can be estimated by the use of algorithms
based on the influence parameters previously seen.
According to a model proposed by Erosion Corrosion Research Centre of the
Tulsa University, the ratio between mass of metal lost by erosion and the mass
of the solid particles produced, defined as base erosion rate, ER
b
(kg
m
/kg
p
), is
given by the following formula:
ER
b
= 1.73 10
-7
VL
1.623
where:
VL = impingement rate of particles; it depends on system geometry, on fluid
and particles density, and on flow rate; it is expressed as m/s.
kg
m
= eroded mass of metal, in kg.
kg
p
= mass of sand produced, in kg.
The calculated value for ER
b
shall be further corrected by multiplying factors to
take into account of the other parameters reported above.
To carry out the calculation procedure a software program, E/CRC Software
Version 1.0, prepared by Erosion/Corrosion Research Centre, is available.

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2 General revision CESCOR STIN CORM 15.06.

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