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O r d e r N u m b e r 902 2 2 3 7
M echanism s of CO2 corrosion related to velocity in two-phase

flow system s
Palacios, Carlos Alberto, Ph.D.

The University of Tulsa, 1990
Copyright 1990 b y Palacios, Carlos A lb erto. A ll rights reserved.
UMI
300 N. Zeeb Rd.
Ann Arbor, MI 48106
T H E U N I V E R S I T Y OF T U L S A
THE GRADUATE SCHOOL
MECHANISMS OF C 0 2 CORROSION RELATED TO

VELOCITY IN TWO-PHASE FLOW SYSTEMS
by
Carles Alberto Palacios Tenreiro
A dissertation submitted in partial fulfillment of
the requirements for the degree of Doctor of Philosophy
in the Discipline of Mechanical Engineering
The Graduate School
The University of Tulsa
1990
THE U N I V E R S I T Y OF TULSA
THE GRADUATE SCHOOL
MECHANISMS OF C 02 CORROSION RELATED TO

VELOCITY IN TWO-PHASE FLOW SYSTEMS
A DISSERTATION
APPROVED FOR THE DISCIPLINE OF
MECHANICAL ENGINEERING
By Dissertation Committee
j Chairperson
ABSTRACT
Palacios, Carlos Alberto (Doctor of Philosophy in Mechanical Engineering)
Mechanisms of CO2 Corrosion Related to Velocity in Two-Phase Flow Systems.
(229 pp. - Chapter VH)
Directed by Dr. John R. Shadley, Associate Professor of Mechanical Engineering, The

University of Tulsa.
(347 words)
This dissertation presents a study on carbon dioxide corrosion at CO2 pressure
of 150 psig and temperature of 160F. Steel corroding in certain CO 2 environments forms
a corrosion product layer (iron carbonate, FeCOg) that can dramatically retard the corro
sion rate. Factors affecting the protectiveness of this scale include the metal microstruc
ture and electrolyte chemistry. Factors affecting the formation and/or removal of this scale
are electrolyte pH, CO 2 partial pressure, temperature, flow conditions, and the presence of
solid particles in the flow. Both protectiveness and formation are examined in this disser
tation by means of experiments performed in an autoclave. Models for FeCOg formation
and removal are presented. Formation and adherence of the scale depend on the micro
structure of the steel specimens. Removal of scales were studied by means of an erosion
apparatus and a two-phase flow loop. The erosion apparatus was designed to shoot slugs
of liquid (with or without solid particles entrained) at iron carbonate layers formed on steel
specimens. Liquid impingement erosion did not damage the FeCOg scale for the condi
tions tested. On the other hand, solid particle erosion caused damage to the scale after only
a few impacts. The two-phase flow loop test facility for studying effects of flow vc ocity
was designed to produce two-phase flow conditions with superficial gas velocities up to
iii
130 ft/sec and superficial liquid velocities up to 8 ft/sec. A test cell for the flow loop was
designed to allow for electrochemical measurements of corrosion rate using removable
pipe spools. Performance testing of the flow loop facility verified that it can produce the
desired two-phase flow regimes such as stratified, slug, froth, and mist flows. In tests
performed in the flow loop, iron carbonate was formed only for low velocity single phase
flows in which the pH was allowed to increase to 5.5. Corrosion rates after scale forma
tion decreased by an order of magnitude. No iron carbonate scale was formed in tests
involving higher single phase flow velocities or two-phase flow velocities. Corrosion rates
in these tests were independent of whether pH was maintained constant at 3.4, or allowed
to increase to about 5.5.
ACKNOWLEDGEMENTS
The author expresses his sincerest gratitude to Dr. John R. Shadley for his
friendship, understanding, guidance, words of advice, patience and dedication through the
course of my career and preparation of this dissertation. He sets an excellent example and
has encouraged me in this work and will encourage me in my work in the years to come. I
will never forget you Dr. Shadley. You will always have my devoted friendship. Thank
you for everything!
Special thanks are extended to Dr. Edmund F. Rybicki for serving in my
committee and for his words of advice throughout the preparation of this dissertation and
my studies.
I am also specially thankful and honored to have had Dr. Sergio Kapusta, Dr.
Shoham Ovadia, and Dr. Robert Howard as part of my dissertation committee. Thank you
very much for all your comments and feedback.
I would like to give thanks to the professors o f the Mechanical Engineering
Department who had something to do with my education. They helped shape my knowl
edge and prepared me to go out and confront the engineering world. I hope to do as good
of a job teaching others, what they so carefully taught me.
Special thanks to the University of Tulsa graduate school for their financial
support and the Erosion/Corrosion Research Center and companies that sponsor it for
supporting this research.
The financial assistance provided by CORPOVEN S.A., an oil company from
Venezuela, is greatly appreciated.
I am indebted to Tommie Sue Hampton for her wonderful help in putting to
gether this dissertation and for her friendship. Thank you for all those extra hours that you
spent so that this dissertation would look as nice as it does. Thanks are also extended to
Deloris, the Mechanical Engineering Secretary.
I would like to recognize all my peers for their friendship, their comments and
their company throughout my research. Wes, Chuck, Elie, Mike, Roy (thanks for your
corrections), David, Chris, Dan, John, los Poquioma, my sister and others (too many to
mention here), your friendship will always be remembered. I want to thank you for the
good memories and the good times.
Finally, I would like to thank Ed Bowers, the Erosion/Corrosion technician, for
his comments and work which were always of great value.
DEDICATION
To my beloved wife Maru for her love, understanding, patience, and for
couraging me to pursue my Ph.D.; I love you with all my soul. Te Adoro.
To my two wonderful children Carlos Alberto and Carlota Elisabeth.
and to you mother; whom, despite all this time, I still miss.
vii
TABLE OF CONTENTS
PAGE
APPROVAL PAGE.......................................................................................................... ii
ABSTRACT..................................................................................................................... iii
ACKNOWLEDGEMENTS............................................................................................. v
DEDICATION.................................................................................................................. vii
TABLE OF CONTENTS................................................................................................. viii
LIST OF FIGURES.......................................................................................................... xii
LIST OF TABLES............................................................................................................ xix
CHAPTER I INTRODUCTION.............................................................................. 1
Research Objectives.................................................................. 5
CHAPTER H BACKGROUND................................................... 7
CARBON DIOXIDE PROPERTIES............................................. 7
Physical Properties.................................................................... 7
Chemical Properties.................................................................. 7
CARBON DIOXIDE CORROSION............................................ 10
Corrosion Mechanism.............................................................. 10
The Interface Mechanism................................................... 14
The Interphase Mechanism................................................ 15
C O j Corrosion Rate................................................................. 16
Metallurgy................................................................................. 31
pH and C 0 2 ............................................................................. 32
Bicarbonate Effects................................................................... 34
Experimental Equipment......................................................... 35
viii
PAGE
Velocity E ffects.................................................................... 42
BASICS OF ELECTROCHEMISTRY..................................... 52
Nemst Equation.................................................................... 54
Pourbaix Diagrams................................................................ 55
Electrochemical Measurements........................................... 57
Polarization...................................................................... 57
Activation Polarization............................................... 58
Linear Polarization...................................................... 61
Concentration Polarization......................................... 62
CHAPTER HI FORMATION AND STRUCTURE OF IRON CARBONATE
SCALES........................................................................................... 63
Structure of Iron Carbonate Scales....................................... 63
Discussion of Preliminary Results................................... 67
Tests at Low Temperatures............................................. 75
Summary.......................................................................... 77
Observations....................... 82
Specimen Metallurgy............................................................ 91
Iron Dissolution................................................... 99
Iron Dissolution at Constant p H ...................................... 104
Dissolution of Iron Carbonate................................................ 108
CHAPTER IV EROSION OF IRON CARBONATE SCALES............................. 116
Description of Erosion Apparatus......................................... 116
Main Features.................................................................... 118
Major Components............................................................ 118
Liquid Impingement T ests.................................................... 119
API N-80 Steel Specimen............................................... 119
ix
PAGE
A IS I1018 CR Specimen.................................................. 122
Solid Particle Im pingem ent.................................................. 130
Summary................................................................................. 135
CHAPTER V EXPERIMENTAL APPARATUS.................................................. 143
Carbon Dioxide Loop............................................................ 143
Two-Phase Flows.............................................................. 143
Loop Capabilities.............................................................. 144
Equipment.......................................................................... 146
Instrumentation................................................................ 149
Data Acquisition System.................................................. 149
CO2 Loop Operation........................................................ 150
Test Cell D e sig n .............................................................. 151
Calibration T ests.............................................................. 158
CHAPTER VI VELOCITY EFFECTS ON C 0 2 CORROSION........................... 172
Tests in the C 0 2 L o o p .......................................................... 172
Single Phase F lo w s.......................................................... 173
Two-Phase Flows.............................................................. 182
Summary................................................................................. 198
Effect of pH and Velocity................................................ 198
Effect of Local Turbulence.............................................. 201
Evaluation of Correlations................................................ 206
CHAPTER VH CONCLUSIONS AND RECOMMENDATIONS......................... 211
Conclusions............................................................................. 211
Autoclave Experiments.................................................... 211
Liquid Impingement Erosion............................................ 212
PAGE
Solid Particle Impingement Erosion............................... 212
CC>2 Loop Experiments.................................................... 213

Recommendations................................................................ 215
REFERENCES ............................................................................................................ 216
APPENDIX A ................................................................................................................ 219
APPENDIX B ................................................................................................................ 226
xi
LIST OF FIGURES
PAGE
Figure I-1. Flowchart of the CO? Corrosion Studies of the Erosion/
Corrosion Research Center.................................................................. 4
Figure II-l. Carbon Dioxide Phase D ia g ra m ........................................................ 9
Figure EI-2. Overview of the CO2 Corrosion M echanism s................................. 17
Figure H-3. Influence of CO2 Pressure and Temperature on Corrosion Rate

of Carbon Steel..................................................................................... 18
Figure H-4. Nomograph of de Waard and Milliams Correlation........................ 20
Figure n-5. Corrosion Rate vs. CO2 Partial Pressure for Five Different
A uthors................................................................................................. 21
Figure II-6 . COPRA Correlation for Uninhibited Tubing..................................... 23
Figure H-7. COPRA Correlation for Inhibited Tubing......................................... 24
Figure n - 8 . Isocorrosion Lines from Coupons in a Continuous Inhibition CO2

Flood System ....................................................................................... 26
Figure H-9. Effect of Gas-Solution Condition on Corrosion Rate in Loop

Tester "A." CO2 Partial Pressure, 100 kPa; Temperature, 60C;
Velocity, 2.5 m / s ................................................................................. 27
Figure II-10. Effect of Temperature on Corrosion Rate in Autoclave. CO?

Partial Pressure, 3 MPa; Room Temperature; 2.5 m/s Velocity
S tirring...................... 28
Figure H-11. Effect of CO? Partial Pressure in Autoclave and in the Loop
Tester "A"............................................................................................. 29
Figure II-12. Effect of Temperature on Corrosion Rate in Loop Tester "B,"

CO? Partial Pressure 3.0 MPa, Room Temperature, How
Velocity 7.0 m /s................................................................................... 30
Figure n-13. Effect of Temperature on pH at 1 Bar CO ?....................................... 33
Figure D-14. Variations of the pH of a 0.5 M NaCl Solution:

a) with Its Bicarbonate Content under 0.1 MPa of Pure CO?; and
b) with 10 meq Bicarbonate and Variable Pressure of Pure C O ? .... 36
Figure H-15. How Loop Used by Eriksrud.............................................................. 37
xii
PAGE
Figure 11-16. Corrosion of A IS I1018 CR in Autoclave Test................................... 39
Figure 11-17. Schematic of the Autoclave System................................................... 40
Figure II-18. Schematic of Flow Loop "A"............................................................. 41
Figure II-19. Schematic of Flow Loop "B"............................................................. 43
Figure H-20. Velocity Profile of the S lu g............................................................... 45
Figure H-21. Velocity Profile of the Him at Bottom of the Pipe............................ 46
Figure 11-22. Wall Shear Stress in Slug How........................................................... 47
Figure H-23. Schematic Representation of Main Results Obtained by

Reference [10]....................................................................................... 48
Figure n-24. Effect of How Velocity on C 0 2 Corrosion in Loop "A".

C 0 2 pp= 100kPa,T = 60C.............................................................. 50
Figure n-25. Effect of How Velocity on C 0 2 Corrosion in Loop "B".

CO2 pp = 3.0 MPa, T = Room............................................................ 51
Figure H-26. Corrosion Cell Showing the Reactions............................................... 53
Figure 11-27. Pourbaix Diagram for the Iron-C0 2 -H20 System, at 100C and
100psiCO2 p p ..................................................................................... 56
Figure 11-28. Polarization D iagram ......................................................................... 60
Figure EH-1 Micrograph of Siderite Crystals Scattered on the Surface of an

API N-80 Steel Specimen.................................................................... 68
Figure m -2. Photograph of the API N-80 Steel Specimens Used for the First
Three Experiments............................................................................... 70
Figure m -3. Micrograph of an Iron Carbonate Scale on the Surface of an API

N-80 Steel Specimen............................................................................. 71
Figure EH-4. Micrograph of an Iron Carbonate Scale on the Surface of an API

N-80 Steel Specimen.......................................................................... 72
Figure m -5. X-Ray Diffraction Analysis on an API N-80 Steel Specimen to

Identify a Uniform Siderite Scale........................................................ 73
Figure m - 6 . X-Ray Diffraction Analysis of an API N-80 Specimen Identifying

a Siderite Scale and Some Iron Presence............................................ 76
Figure m -7. Micrograph of a Non-Uniform Siderite Scale on an API N-80 Steel

Specimen............................................................................................... 78
PAGE
Figure m - 8 . X-Ray Diffraction of a Siderite Scale on the Surface on an AISI
1018 CR Steel Specimen...................................................................... 79
Figure m -9. Micrograph of a Siderite Scale on a 1018 CR Steel Specimen 80
Figure IE-10. Micrograph of a Siderite Scale on a 1018 CR Steel Specimen 81
Figure m-11. Micrograph of a "Thin" Iron Carbonate Scale on a 1018 CR Steel

Specimen......................................... 83
Figure Id -12. Micrograph of a "Thick" Scale on an N-80 Q&T Steel Specimen.. . 84
Figure m-13. Micrograph of the Two Types of Scales on an N-80 Q&T Steel
Specimen. "A" Top Scale, "B" Primary Scale, and "C" P o res 86
Figure m-14. Micrograph Showing the Cross-Sectional Area of a 1018 CR Steel

Specimen with the Primary Scale on the Left and the Secondary
Scale to the R ight................................................................................. 88
Figure HI-15. Micrograph of a FeCOg Scale Showing How the Secondary Scale
Is Delaminated from the Primary Scale.............................................. 89
Figure ID-16. Micrograph of a FeCOg Scale Showing How the Secondary Scale
Ruptured from the Primary Scale........................................................ 90
Figure m-17. Micrograph Showing the Microstructure of API N-80 Q&T Steel
Specimen............................................................................................... 92
Figure m-18. Micrograph Showing the Microstructure of API N-80 Normalized

Steel Specimen..................................................................................... 93
Figure HI-19. Micrograph Showing the Microstructure of AISI 1018 CR

Steel Specimen..................................................................................... 94
Figure HI-20. Micrograph Shewing the Cross-Sectional Area of an N-80

Normalized Steel Specimen with a FeCOj Scale............................... 95
Figure HI-21. Micrograph of a Cross-Sectional Area of an N-80 Q&T Steel

Specimen with a FeCOj Scale............................................................ 96
Figure HI-22. Mechanism of FeCOj Formation on an N-80 Normalized Steel

Specimen................................................................................................ 97
Figure HI-23. Dissolution of Iron for 4% Brine Only for Three Tests
at Same Conditions............................................................................... 101
Figure HI-24. Dissolution of Iron in a 4% Brine Plus 2 g/1 of NaHCOj Solution

for Two Tests at Same Conditions...................................................... 102
Figure HI-25. Dissolution of Iron in 4% Brine Plus 4 g/1 of NaHCOj Solution 103
xiv
PAGE
Figure IH-26. Maximum Dissolved Iron (Fe++) Concentration vs. Initial
Concentration of NaHCOj in mg/1...................................................... 105
Figure HI-27. Iron Dissolution in 1,400 ml of 4% Brine Using Crolets Recipe.. . 107
Figure 111-28. Dissolution of Iron Carbonate in 4% Brine Crolets Recipe.............. 110
Figure HI-29. Iron and Iron Carbonate Dissolution................................................... I l l
Figure IH-30. Siderite Composition Diagram........................................................... 113
Figure ffl-31. Dissolution of Iron Carbonate Scale from a Stainless Steel

Specimen................................................................................................ 115
Figure IV-1 Photograph of the Erosion Apparatus for the Iron Carbonate
Studies.................................................................................................... 117
Figure IV-2. Micrograph of a Siderite Scale on N-80 Steel Showing the

Reference H ole..................................................................................... 120
Figure IV-3. Micrograph of the Siderite Scale on N-80 Steel after Exposed to
Additional 300,000 Cycles of Liquid Impingement at 160 ft/sec 121
Figure IV-4 Micrograph of a Siderite Scale on a 1018 CR Steel Specimen 123
Figure IV-5 Micrograph of a Siderite Scale on a 1018 CR Steel Specimen

Showing the Reference Hole and a Crack, in a Direction
Radially from the Hole......................................................................... 124
Figure IV-6 Micrograph of the Damage that Occurred on the Area around the
Hole after 2,000 Cycles of Exposure to Liquid Impingement at 160
ft/sec...................................................................................................... 125
Figure IV-7. Micrograph of the Siderite Scale around the Reference Hole
Showing How the Scale Has Been Removed after Exposed to
Liquid Impingement............................................................................. 126
Figure IV -8 Model for Liquid Impingement on a Metal Surface.......................... 128
Figure IV-9 Geometry of a Sudden Expansion........................................................ 129
Figure IV-10 Particle Size Distribution of Glass Beads........................................... 131
Figure IV-11 FeCOj Scale Damage after It Was Exposed to .2% Solid Particle
Concentration Impingement; after 100 Liquid/Solid Impacts, 160
ft/sec...................................................................................................... 132
Figure IV-12 Velocity of Liquid/Solid Jet vs. Number o f Impacts to Initiate

Damage.................................................................................................. 134
Figure IV-13 Schematic of FeCOg Scale on Steel................................................... 138
xv
PAGE
Figure IV-14 Mechanism of FeCQj Scale Damage................................................... 139
Figure IV-15 Pit Growth Mechanism Underneath a Protective Coating.................. 141

Figure IV-16 Proposed Mechanism for FeCOg Scale Removal................................ 142
Figure V-1 Flow Regimes - Madhane Correlation Showing the Loop

Capability....................................... 145
Figure V-2 Schematic of the CO2 Loop................................................................. 147
Figure V-3 Photograph of the CO2 Loop Showing the Test Section and
Potentiostat........................................................................................... 152
Figure V-4 Photograph of the COb Loop Showing the Main Separator(Left),
Receiver Tank (Right), and Mixing Tank (Lower Left)..................... 153
Figure V-5 Photograph of the CO2 Loop Showing from Left to Right:Cooler
Heat Exchanger, Heater Heat Exchanger, Secondary Separator,
and Condenser Heat Exchanger.......................................................... 154
Figure V -6 Photograph of the Compressors........................................................... 155
Figure V-7 Schematic of the Mass-Transfer Process............................................ 157
Figure V -8 Schematic of the Test C ell................................................................... 159
Figure V-9 Test Cell without 'Dummy Pipe" Showing the Electrodes............... 160
Figure V-10 Test Cell with "Dummy Pipe" and Electrodes.................................... 161
Figure V -11 Test Cell in the CO2 Loop, Horizontal Section.................................. 162
Figure V-12 Schematic of the Test Section............................................................... 163
Figure V-13 Iron Concentration as a Function of Tim e.......................................... 164
Figure V -14 a) O 2 and pH as Function of Time for Calibration Test #3

b) O 2 and pH as Function of Time for Calibration Test #4............ 166
Figure V-15 Temperature Variation for Calibration Tests...................................... 167
Figure V-16 Variation of pH as a Function of Dissolved Iron................................ 168
Figure V-17 Photograph of Stratified Flow............................................................... 169
Figure V-18 Photograph of Annular Mist Flow ....................................................... 170
Figure VI-1 Corrosion Rates for Single Phase Flow Tests, with Vsj = 1ft/sec
and pH Constant at 3.4......................................................................... 177
xvi
PAGE
Figure VI-2 Corrosion Rates for Single Phase Flow Tests, with Vsi = 8 ft/sec
and pH Constant at 3.4........................................................................ 178
Figure VI-3 Variation of Ferrous Ion Concentration for Single Phase Flow
Tests Having pH Constant at 3 .4 ........................................................ 180
Figure VI-4 Corrosion Rate for Single Phase Flow Tests with Vsi = 1.2,2 and
8 ft/sec and Variable pH ...................................................................... 181
Figure VI-5 Corrosion Rate and pH for Single Phase Fiow Test with Vsl = 1.2
fit/sec..................................................................................................... 183
Figure VI-6 Corrosion Rate and pH for Single Phase Flow Test with Vm = 2
ft/sec..................................................................................................... 184
Figure VI-7 Corrosion Rate for Single Phase Flow Test with Vsi = 8 ft/sec
and pH ....................................................................................... 185
Figure VI-8 Corrosion Rate vs. pH for Single Phase Flow Tests with Vsi = 1.2,
2 and 8 ft/sec......................................................................................... 186
Figure VI-9 Variation of Ferrous Ion Concentration for Single Phase Row
Tests with a Vsj = 1.2,2 and 8 ft sec at Variable p H ........................ 187
Figure VI-10 Corrosion Rate for Two-Phase Row Test v'si= I ft/sec, V s2 = 1
ft/sec, and pH = 3.4................................................................. ............ 188
Figure VI-11 Ferrous Ion Concentration for a Two-Phase R ow Test Having V~i =
1 ft/sec and VSg = 1 ft/sec.................................................................... 190
Figure VI-12 Corrosion Rate for Two-Phase Row Test Vsi = 1 ft/sec,Vse = 60
ft/sec, and pH = 3.4..................................... . 7 .......................7?......... 191
Figure VI-13 Variation of Ferrous Ion Concentration for Two-Phase Row Tests
Having Vsj = 1 ft/sec, VSg = 60 ft/sec, and pH = 3.4......................... 192
Figure VI-14 Corrosion Rates for a Two-Phase Row Test Vsi = 8 ft/sec, Vs = 6
ft/sec, and pH = 3.4..................................................................... ? . . . . 193
Figure VI-15 Corrosion Rate for a Two-Phase Row Test with Vsj = 8 ft/sec,
VSg = 6 ft/sec, and pH Constant at 3.4................................................ 195
Figure VI-16 Variation of Iron Concentration for Two-Phase Row Tests at V sj =

1 ft/sec, VSg = 60 ft/sec, and Constant pH = 3.4................................. 197
Figure VI-17 Corrosion Rate for Two-Phase Row Tests with Vsi = 8 ft/sec, Vsg
= 6 ft/sec, Vsj = 2 ft/sec, VSg = 2 ft/sec, and Variable p H . 199
Figure VI-18 Corrosion Rates for Two Tests Having the Same Two-phase Row
Condition but Different p H ................................................................. 200
xvii
PAGE
Figure VI-19 Corrosion Rates for Two Tests Having the Same Single Phase
Flow Conditions but Different p H ...................................................... 202
Figure VI-20 Corrosion Rates for Single Phase Flow V-j = 8 ft/sec
and Two-phase Flow Vsj = 8 ft/sec, and VSg = 6 ft/sec..................... 203
Figure VI-21 Corrosion Rates for 5 Tests Having Different Flow and
pH Conditions...................................................................................... 204
Figure VI-22. Photograph of "Dummy Pipe" Showing Corrosion Damage 207
Figure VI-23. Photograph of "Dummy Pipe" Showing Corroded Area.

The Dark Line Shows the Borderline.................................................. 208
xviii
LIST OF TABLES
PAGE
Table III-1 Chemical Analysis of API N-80 Q&T Steel......................................... 64
Table m -2 Chemical Analysis of API N-80 Normalized Steel.............................. 65
Table HI-3 Specification of AISI 1018 CR Steel................................................... 66
Table IH-4 Chemical Analysis of Tulsa Tap W ater............................................... 69
Table m -5 High Intensity Peaks for Iron Carbonate (FeCOg).............................. 74
Table HI-6 High Intensity Peaks for Iron (Fe)....................................................... 74
Table 1H-7 Conditions for Formation of FeCOj..................................................... 85
Table HI-8 Characteristics o f FeCOg...................................................................... 98
Table 1H-9 Aqueous Chemistry Conditions U sed.................................................. 100
Table HI-10 Testing Conditions as Described by C rolet........................................ 106
Table HI-11 Summary of Tests in the Autoclave for 1,400 ml of Solution 109
Table IV-1 Number of Impacts to Initiate Damage of FeCOo Scale on AISI

1018 CR Steel........................................................ 133
Table IV-2 Number of Impacts to Initiate Damage o f FeCO-j Scale on API

N-80 Steel.............................................................. 133
Table VI-1 Test Conditions for CO2 Loop............................................................. 174
Table VI-2 Example of How the Data Is Tabulated............................................... 175
Table VI-3 Summary of Corrosion Rates for Loop Tests...................................... 205
Table VI-4 Validity Limits Established by Investigators of

de Waard and Milliams Equation........................................................ 210
xix
CHAPTER I
INTRODUCTION
Velocity enhanced corrosion problems in oil and gas production equipment are
common. These often occur when producing fluids are accompanied by carbon dioxide
(sweet corrosion) and/or hydrogen sulfide (sour corrosion). In recent years the presence of
carbon dioxide in the produced fluid is encountered more frequently due to the use of
enhanced oil recovery techniques involving CO2 injection into reservoirs and also due to
the occurrence of sweet gas production from deeper wells.
Carbon dioxide dissolves in the presence of a water phase framing a weak acid
(carbonic acid) which ionizes to a degree, thus reducing the pH and corroding carbon steel
pipes. As the carbon steel corrodes, the steel forms a corrosion product scale (ferrous
carbonate) which is believed to provide a degree o f protection of the steel from further
corrosion. The protectiveness of the scale depends on environmental factors and character
istics of steel. Environmental factors are those factors that define the medium of the
corroding steel; such as, temperature, carbon dioxide partial pressure, solution chemistry,
fluid velocity, single-phase or multi-phase flows, pipe geometry, and solution pH. Steel
characteristics include chemical composition and heat treatment, which determine the
microstructure of the steeL
Velocity enhanced carbon dioxide corrosion occurs by accelerating the process
of dissolution of a protective film; such as, the corrosion product scale, or by erosion of the
film by the mechanical forces impressed on the film by the moving fluid, or by increasing
the transport of carbonic acid to the metal surface, or by a combination of any or all three.
Once the protective film has been removed, the protectiveness of the scale is lost, and the
steel pipe again corrodes freely. Scale growth and scale removal affect the rate at which
2
the steel conodes. This type of corrosion is more severe and most frequently seen in two-
phase or multi-phase flow systems. Near the pipe wall, in single-phase flows, the velocity
of the fluid component normal to the pipe wall is zero or very close to zero; therefore the
dissolution process and/or the transport of carbonic acid to the pipe wall and/or erosion is a
slow process controlled by diffusion. On the other hand, in two or multi-phase flows, the
liquid phase, in the form of slugs or small drops, can be impulsively directed towards
metal surfaces creating high dissolution and transport rates and high local mechanical
forces.
Velocity induced carbon dioxide corrosion is known to have caused problems
to the oil and gas industry. Downhole tubing, valves, and various surface equipment are
affected by this type of corrosion. Techniques to control CO2 corrosion include applica
tion of plastic coating, the use of inhibitors and corrosion resistant alloys, and/or control
ling production velocities.
Some field and laboratory data suggest the existence of a velocity below which
the material removal (mass transport) rates are low and above which the material removal
(mass transport) rates grow rapidly with increasing velocity. This velocity has been called
the "critical," "threshold," "breakaway" or "erosional" velocity. For this reason, producers
limit production velocities to values below a "critical velocity." This limiting velocity
value varies from company to company. Very few guidelines exist on limiting the produc
tion velocities, especially in corrosive mediums such as carbon dioxide and water. One of
the guidelines used to limit production velocities is based on the American Petroleum Insti
tute recommended practice RP 14E [1] shown below:
Where Ve is the erosional critical velocity, C is a constant and ^ is the density
of the flowing medium. Values of C of 100 for continuous service and 125 for intermittent
service are recommended when P has units of pound-mass per cubic foot, Ve has units of
3
feet per second, and C has units of y l b m / ft sec2. Equation 1-1 does not account for
solids; such as, sand, the amount o f condensate, temperature, pressure, amount of corrosive
agents in the flow, or whether an inhibitor is used or not. Therefore, there is interest
among the oil and gas producers to generalize this equation to account for these factors.
To accomplish the task of understanding and generalising the RP14E equation,
the Erosion/Corrosion Research Center (ECRC) at the University of Tulsa was formed.
Among the objectives of the ECRC is the better understanding carbon dioxide corrosion.
To study carbon dioxide corrosion, a flow loop has been built and an autoclave
has been used. The Carbon Dioxide Loop has been designed and built to study the effects
of velocity on carbon dioxide corrosion. The autoclave has been used to help understand
the formation of the corrosion scale, its protectiveness, and also to study the characteristics
of the corroding steel. To measure corrosion rates a special test cell was designed to
accommodate electrochemical techniques.
As mentioned before, the general and end objective of the ECRC is to improve
corrosion design guidelines where flow velocities are a controlling factor. The general
objectives in the area of CO 2 corrosion can be presented in the form of a flowchart as
shown in Figure 1-1. In this figure two main areas of study can be appreciated: the theoret
ical and the experimental. These two main areas are subdivided into more specific areas of
study, and it is within these subdivisions that the objectives of this dissertation are found.
Both the general goals of the ECRC and the specific objectives of this dissertation concern
velocity guidelines for CO 2 corrosion.
CO2 CO RROSIO N
S T U D IE S
THEORETICAL EXPERIMENTAL
STUDIES STUDIES
Literature Computer Autoclave Erosion

Review Mode! Apparatus
FeCQ 3
CO2 CO RROSIO N
G U ID E L IN E S
Figure 1-1. Flowchart o f the CO ^ Corrosion Studies

of the Erosion/Corrosion Research Center.
5
Research Objectives
The specific objectives of tins research are:
1 Design and construct a system that will produce the desired two-phase flow
conditions with controlled parameters; such as, pressure, temperature, pH, and flow veloci
ties.
2.- Design and construct a test cell that allows for electrochemical measure
ments to monitor the corrosion rates.
3.- Study characteristics o f the formation of the corrosion scale in an auto
clave. Identify parameters; such as, aqueous chemistry, protectiveness, crystal size, scale
thickness, and effects of the steel composition and microstructure.
4.- Study characteristics of the corrosion rates of bare metal in a carbon diox
ide environment in the CO2 Loop exposed to single and two-phase flows at constant and
variable pH.
5.- Establish guidelines and norms for performing tests in the CO 2 Loop.
6 .- Study characteristics of the corrosion rates on bare metal in a carbon diox
ide environment in the CX>2 Loop exposed to single and two-phase flows at constant and
variable pH.
It is important to point out that very little information exists in the literature
about research on velocity effects on carbon dioxide corrosion in two-phase flow systems
with controlled parameters and where flow velocities vary from a few feet per second up to
150 feet per second. Therefore, it is intended that this research will result in the develop
ment of new and useful techniques for studying problems involving velocity influences on
carbon dioxide corrosion. It is also expected that the work presented in this dissertation
will represent a step towards understanding and improving the current guidelines for
6
controlling production velocities and establish a procedure for performing tests in single
and two-phase flows in the CO2 Loop.

The format of this dissertation follows closely the flow presented in the flow
chart in Figure 1-1. First a literature review is presented to familiarize the reader with
terminology, correlations, testing procedures, and testing apparatuses used to date to study
CO2 corrosion problems. Then, parameters influencing the characteristics of iron carbon
ate scale are studied in an autoclave, followed by a study of the erosion of iron carbonate
scales. These two areas of study helped set guidelines for performing tests in the CO 2
Loop.
A full description of the CO2 Loop is presented along with calibration tests.
The section following the description of the loop presents results of the tests performed at
different single and two-phase flow velocities, at constant and variable pH.
CHAPTER H
BACKGROUND
CARBON DIOXIDE PROPERTIES

Before going into depth in describing different aspects of carbon dioxide corro
sion, some properties of carbon dioxide [2 ] are described below.
Physical Properties
At standard temperature and pressure, CO 2 is a gas. It is odorless and color
less, not flammable, with density 1.5 times that of air. It will not support combustion nor
sustain life. As a gas, CO2 is readily expandable and is soluble in various liquids. CO2 as
a treating fluid, when it is pumped into a well, becomes at some point a gas. When the
well is reopened to flow, the gas expands as the pressure decreases. The expansion of the
gas lightens the hydrostatic pressure of the well bore fluids, allowing the well to flow. The
gas lift characteristic of CO 2 is accomplished by the portion of the gas not soluble. The
solubility of CO 2 is very dependent on pressure and to some extent on the fluid present.
The solubility in brine is less than that in pure water. At high pressures all the CO 2 may
be soluble in the liquid, which means that higher and higher concentrations of the gas must
be pumped to receive any gas lift effect
CO2 may exist simultaneously as a liquid, a solid, and a gas at its triple point,
-69C and 60.43 psig. Figure II-1 shows the phase diagram for CO2 .
Chemical Properties
The chemical properties of CO 2 are revealed by the characteristic ways in
which it undergoes chemical reactions. It is usually referred to as an inert gas since it does
not easily react with other gases in the atmosphere. But it does react when in solution,
8
with plants, metals, and at elevated temperatures with many other molecules in all forms.
The most important reaction of CO2 for purposes of the oil and gas industry is
that which occurs when C O j is mixed with w ater H 2 O + CO2 = H2 CO3 which is carbon
ic acid. This is a weak acid and in water dissociates to form ions H 3 0 + and HCO 3 '
These ions eventually reach an equilibrium with the undissociated form. The concentra
tion of H 3 <D+ ions present determines the pH. CO 2 is corrosive because it forms a weak
acid (H2 CO 3 ) when mixed with water.
5,000 - SOLID
LIQUID
2,000
1,000
o>
M VAPOR
CL
500
iLi
CE
ZD
CO
CO 200
Ui
o:
CL
100
50
C02 LOOP
CONDITIONS
- 1 2 0 -1 0 0 -6 0 -2 0 0 20 60 100 120
TEMPERATURE (C)
Figure II-1. Carbon Dioxide Phase Diagram [2].
10
CARBON DIOXIDE CORROSION
This section presents a summary o f some selected papers dealing with CO 2
corrosion in the oil and gas industry.
It has been experienced that failures due to CO2 corrosion are among the most
severe in the oil and gas industry. It has not been until recently that this type of corrosion
has received special attention. Among investigators there seems to be disagreement on the
exact mechanism by which CO2 corrosion occurs; although all agree that a formation of a
protective scale of iron carbonate occurs, creating a protective barrier between the corro
sion medium and the bare metal surface. The effectiveness of this scale depends on its
morphology, scale thickness, and permeability. Also, it has been found by many investiga
tors that the reduction of hydrogen at the cathode in solutions containing CO2 is different
from that occurring in strong acids such as H Q . For the case of strong acid solutions, the
diffusion of protons from the bulk is the rate controlling reaction.
Corrosion Mechanism
Many authors believe that the reduction of hydrogen at the cathode in solutions
containing CO2 is different from that occurring in strong acid solutions. For example, for
the case of a strong acid solution, the diffusion o f protons from the bulk is the rate control
ling reaction. The hydrogen evolution in solutions that contains CO 2 can occur by two
different mechanisms. Schmitt [3] describes these mechanisms as follows:
1. Hydrogen evolves electrochemically at the cathode by the reduction of
hydrogen ions that are present in the solution coming from the dissociation of carbonic
acid, then this hydrogen diffuses to the metal surface.
C0 2sol + H2 <-----> H2C3 so l n_1
H2C03sol + H20 < - - > H3Oso1+ + HC03so1- n2
H 3 +sol <---- > H 3 +* n-3
11
H 3 0 +* + e- <-----> Had + H 2 0 * n-4
where, means near the phase boundary, and "ad" means adsorbed.
2. Schmitt [3] showed experimentally that the hydrogen formation occurs
according to the following sequence of reactions:
C0 2 sol <_ > c o 2 ad n '5
C 2 a d + H2 <--- > H2c o 3ad n 6
H2C 0 3ad + e~ <-----> Had + HC 0 3ad" n '7
H 3 0"*"* + e <----- > + H20 * II-8
or by the following sequence of reactions:
C0 2 sol <_ > C 2 ad n '9
C0 2ad + H2 <--- > H2C 0 3ad n ' 10
h 2 c o 3+ h 2o < > h 3 o +* + h c o 3- n -i i
H 3 0 +* + e - <------ > H ^ + H 2 0 * H-12
According to Schmitt [3], the difference between the reactions described in 1
and 2 above is that in 2, the hydration of C 0 2 occurs at metal interface (equation II- 6 ),
while for the reaction in 1, the hydration of C 0 2 occurs in the bulk solution (equation II-
1). He also argues that the C 0 2 will adsorb on the iron surface and the adsorption is
accomplished by an interaction with the iron-hydrogen bonds forming COOH at the metal
surface. Then, the hydration of COOH produces carbonic acid. This carbonic acid can be
reduced to give adsorbed hydrogen atoms and bicarbonate, or it can be dissociated to
produce hydrogen ions near the phase boundary. These hydrogen ions are later reduced to
form hydrogen gas.
12
As discussed by Hausler [4], during the corrosion of a metal in a C 0 2 saturated
solution, two mass transfer gradients develop: one in which the iron ions Fe++ diffuse
away from the metal surface; the other is towards the surface to where pH increases, pH
being a function of the carbonic acid H 2 CO3 , bicarbonate ions H C 03, and carbonate ions
CC>3 =. Then at some point in the interphase, the iron carbonate precipitates forming a
scale. The morphology of this scale depends on where and for what conditions the precipi
tation occurs. Two possibilities are described in this paper:
1.- Topochemical Scale Growth: This mechanism appears in the presence of
high alkalinity. The scales formed are usually dense and protective. And parabolic corro
sion rates will be observed until the iron starts diffusing into the bulk of the solution at a
rate that matches the corrosion rate. This behavior is observed in autoclaves because the
solution saturates with iron carbonate. Then:
Corrosion rate = P/8 = Iron removal rate II-13
where: P = scale permeability.
5 = scale thickness.
2.- Precipitation Nearer the Surface:
a) If saturation concentration is near the surface, then the van der Waals Force
may attract the iron carbonate (FeCOj) particles back to the surface. Then these particles
may attract each other and form a scale, decreasing the corrosion rate.
b) If particles are precipitated away from the surface, Brownian motion would
carry these particles into the bulk solution, and no passivation would occur.
The chemistry of the CO 2 corrosion mechanism as described by Hausler [5] in
another paper, is as follows:
C 0 2 + H20 <- > H 2 C 0 3 <--> H+ + HCO 3 - H-14
13
In this equation, the hydrolysis (formation of H 2 CO3 ) and dissociation (forma
tion of H+ + HCO 3 ') are very fast at high temperatures; therefore, the corrosion rate is
determined by die C 0 2 concentration rather titan pH. There are two dissociation constants
associated with equation 11-14. These dissociation constants are:
[H+] [HCO3-] [H+] [HCO3 I

Ki = K l* = ------------------ II-15a,b
[h 2c o 3]
where K j = 6.38 x 10^ and K j* = 3.76 x 10 at C 0 2 partial pressure = 14.7 psia and
temperature = 27C. At these conditions, water contains 3.5 x 10 "^ mol/1 of dissolved
C 0 2. The overall C 0 2 corrosion reaction in the presence o f iron is as follows:
Fe + 2H2 C 0 3 <- > Fe++ + 2H C 03' + H 2 11-16
The H 2 CC>3 dissociates and forms H 2 + 2 HCO 3 '. A consequence of this reac
tion is the build up of HCO 3 " in the solution leading to an increase in pH, where:
pH = log [HCO3 '] - log [C0 2 pp] - log K j n - 17
where: C O ^ p = C 0 2 partial pressure.
This means that ongoing corrosion will increase the pH of the solution unless it
is renewed or FeC 0 3 (iron carbonate, ferrous carbonate, siderite) starts to precipitate as
shown in the following equation:
Fe++ + 2 HCO 3 ' -> FeCOs + H20 + C 0 2 H-18
The formation of FeC0 3 can cause complete passivation. Such complete passi
vation was observed by Jasinski [6 ]. The structure of this passivation scale depends on the
solubility of the product and the ability o f the scale to adhere to the steel surface. The
alkalinity of the water influences the amount o f ferrous ions in solution by establishing the
amount of carbonate ions required to precipitate FeCC^.
14
The formation of a passivation scale leads to two different corrosion mecha
nisms as described in reference [5]. They are: an Interface Corrosion Mechanism at the
bare metal surface and an Interphase Corrosion Mechanism where the corroding surface is
covered by a corrosion product layer. Localized corrosion occurs in the transition zone
between the two mechanisms.
The Interface Mechanism
When a clean specimen is immersed in a solution containing CO2 and water at
a temperature higher than room temperature, the surface of the specimen becomes dark
after some time. This state was identified by Jasinski [6 ] "as an accumulation of FegC
(Iron Carbide) which is insoluble and does not corrode." This carbide forms on the surface
of the specimen as porous layers composed o f carbide platelets or needles. Whether it
forms platelets or needles depends on the type of steel [7]. The carbide layer plays an
important role in the formation of an FeCC>3 sca^e 01 a agnetite scale. FegC forms easily
even at high velocities because of the high pH generated near the surface as a result of a
high corrosion rate.
The corrosion kinetics c f this interface mechanism as described by Hausler [5]
are as follows:
* At temperatures below 30C the hydrolysis of CO2 to form carbonic acid is
rate determining.
* At temperatures above 40C the diffusion of H 2 CO3 to the corroding sur
face becomes the rate limiting step.
* At temperatures below 30C, CO2 corrosion is very much independent of
flow rate, except at very low velocities, when diffusion rate is slower than the hydrolysis of
co2.
Below 30C the corrosion rate increases with increasing temperature and CO2
partial pressure. As temperature increases, the corrosion rate (hydrolysis rate) eventually
becomes equal to the CO2 diffusion rate.
15
The Interphase Mechanism
This mechanism concerns the formation of FeCC>3 or magnetite (Fe 3 0 4 )
scales. Once the corrosion layer begins to build on the metal surface, the corrosion kinet
ics change. The rate determining step becomes the mass and/or charge transfer across the
solid interface. The corrosion rate is then determined by:
Corrosion Rate = P x l / 8 II-19
where P is the scale permeability as defined by Hausler [5] and 5 the thickness of the scale.
In an unsteady state, 5 is a function of time:
d(8)
= F^ (corrosion rate) - F 2 (dissolution rate) 11-20
dt
where F j and F2 are functions describing the corrosion rate and the dissolution
rate as a function of time, respectively.
The dissolution rate is the rate at which the scale is removed. When the dissolu
tion rate equals the corrosion rate, we have the steady state case. The dissolution rate of
FeC 0 3 is not easily calculated and is inversely proportional to some function of the ion
concentration in the solution. Therefore, it is flow dependent as long as the solution is not
saturated with FeCC^.
According to Hausler, permeability does not control corrosion rate by itself,
since it acts in conjunction with the thickness of the scale. Increasing temperature, pH, and
sodium bicarbonate (NaHCC>3 ) content increases the film formation rate (also observed by
Jasinski [6 ]), but they affect permeability as well since the permeability decreases with
increasing temperature and pH and also is affected by the brine components; such as, Al,
Hg ions, and silicates. The fact that corrosion rate decreases as temperature increases in
flowing CO2 systems is due to chemical factors [5], since as temperature increases (for
temperature greater than 250F) the metal surface becomes more covered with magnetite
16
(instead of FeCOg). This magnetite scale is very protective. The reaction of the forma tion
of the magnetite scale is as follows:
3Fe + 4 H 2 O -----> Fe 3 C>4 +4H 2 11-21
3Fe(OH)2 > Fe30 4 + H2 + 2H20 11-22
The protectiveness of the F ejC ^ scale is affected by the presence of chlorides
at high temperature, while the FeCOj scale is not.
Figure II-2 shows an overview o f the CO 2 corrosion mechanisms just de
scribed.
CO2 Corrosion Rate
The corrosion rate of bare steel was found to obey the relationship developed
by de Waaid and Milliams [8]. This relation is as follows:
log v = 1/2 A log (CO2 PP) + B H-23
where:
A = 1.3, from Figure II-3. This value of A gives the best fit for all the data
obtained.
B = constant introducing corrections for temperature,
v = corrosion rate in mpy (mils per year).
CO2 PP = partial pressure of CO 2 1 psig.
C02 CORROSION MECHANISM
IN T E R F A C E C O N T R O I.I.E D INTERPIIASE CONTROLLED
RATE DETERMINING STEP CONTROLLING PARAMETERS RATE DETERMINING STEP CONTROUJNG PARAMETERS
T <M"C MASS or CHARGE TRANSFER

h y d r o g e n e v o l u t io n P C O , ,T , ( PII) ACROSS SOLID ENTER PHASE
METAU.URGY
fi, THICKNESS OP SCALS
HYDROLYSIS OF COj M effect uf FLOW
STKADYSTATB CORK. RATE D1SSOL. RATE
COj . HjO lI2CO}
T> 3'C q isiou / tio m o fjo u d A***2) ,
PCO} ,T ,
Boixmss
SOLUBILITY OP SCALE
METALLURGY
pH , T ,u lts ,
DIFFUSION OF COj TO (pin,luiu),
FCiTAL SURFACE
P, K RM EABIUTY OP SCALE
T ,aiU(Hct l ,S l0 2tAlY3ctc.)
i& H GROWTH RATE OP FILM

NON-STEADY STATE v ,p H pH COj , T
METALLURGY
IF FILMS FORM THEY ARE THIN FORMATION OF SOLID
AND NOT VERY PROTECTIVE INTElPtLUl
Pc3C, F(Mfc C)C03 FILMS ARK VERY PROTECTIVE
F ^C O j, F304
TRANSITION OCCURS IN TEMPERATURE REGION

OF 40 - I20C DEPENDING ON REMOVAL OR
GROWTH MECHANISM OF SCALE, MAIN PARAMETERS
ARE FLOW RATE OR SHEAR STRESS
SUMMARY AND OVERVIEW OF THE C 0 2 CORROSION MECHANISM.
Figure H-2. Overview of CO 2 Corrosion Mechanisms [5].
10
8
o 60C , POLISHED
6
25C , POLISHED
a 15C, GRIT- BLASTED
E
E
Ll T
5
az
o
rk
cn 2
tr
8 0.1
8
6
4 -
0.01 J I i i i n I
0.01 2 4 6 8 0 .1 2 4 6 8
C02 PARTIAL PRESSURE, BAR
Figure H-3. Influence of CO2 Pressure and Temperature

on Corrosion Rate of Carbon Steel [8 ].
19
Craig [9] writes the de Waard and Milliams equation as follows:
log r = 8.78 - 2.320 - 5.55 x 10' 3 T + 0.67 log PCO? 11-24

T + 273
where:
r = corrosion rate, mpy (mils per year)
T = temperature, C
P(X >2 = partial pressure of CO2 , psi
From this equation, a nomograph can be constructed, and it is shown in Figure
H-4. For example, assuming the CO2 partial pressure of 1.5 psi at a temperature of 7C,
the corrosion rate would be 4 mpy. If the CO2 partial pressure is 100 psi and the tempera
ture is 45C, the corrosion rate is about 400 mpy.
The use of the de W aard and Milliams equation (11-23) has received much
attention since it has been the only correlation available to calculate corrosion rates as a
function of CO 2 partial pressure. Many authors have established their own validity limits
for the use of this equation. For example, Schmitt [3] established its limits at CO2 partial
pressure below 2 bar and temperatures up to 60C (140F). He argues that at higher pres
sures and temperatures the experimental conosion rates are generally lower than calculated
from the de Waard and Milliams equation. Eriksrud [10] established the limits at a CO2
partial pressure of 1 bar and up to 20C. On the other hand, Ikeda [11] established the
limits at a CO 2 partial pressure of 2 bar and a temperature up to 60C.
As pointed out by Burke [12], many of the variations of the de Waard and
Millians equation may be due to the experimental conditions; such as, surface preparation,
metal surface to volume ratios, etc. Figure II-5 shows the result obtained by five different
authors. Below 2 bar and 60C the data is consistent The variation lies on the intercept
not on the slope of the lines.
8020
CORROSION CO2 PARTIAL

RATE, mpy PRESSURE, psi
TEMPERATURE C
Figure H-4. Nomograph of de Waard and Milliams Correlation [8 ].
SATOH MURATA
dWAARD 3 MILLIAMS *MASAMURA
IKEDA
100
100*C#
60C L00P_ *"60C
2.5 m/s '
E AUTOCLAVE..
2 .5 m /s..-'
10 r 60* C
Lul
LOOP AUTOCLAVE
<E
(C
o
tn
in 1 .0 r
LOOP 100C
o AUTOCLAVE
cr * 2 0 0 #C
a:
o |_60* AUTOCLAVE
o
AUTOCLAVE 1 m/s
0.1 -u . i i n m l '<! 1 1 1 " " ll i - 1. U l-LUl I I m i
0.01 0.1 1.0 10 100 1000
C 0 2 ATM
Figure H-5. Corrosion Rate vs. CO2 Partial Pressure for Five
Different Authors [11].
22
Gatzke [13] defined a correlation called COPRA (Corrosion Rate - Production
Rate) for determining average corrosion rates. The COPRA correlation is defined as fol
lows:
Average Corrosion Rate (mpy) = KG x QHjO 11-25
where:
QH2 O = the water production rate in BPMMCF of gas (Barrels of water
Produced per Million Cubic Feet of gas).
Average Corrosion Rate = corrosion rate determined by iron counts.
K = the proportionality factor is a function of the gas production rate:
log K = log Ch + K x log Qgas n-26
where:
Qgas = gas production rate in MMSCFD (Million Standard Cubic Feet/Day)
K and Cjj = are constants determined empirically and depend on the
chemistry of the system.
For gas flow rates above 4 MMSCFD:
log KG = log Ch* + K x Qgas H-27
The COPRA correlation allows for the comparison of corrosionrates before
and after chemical treatment of a well. It helps in determining which inhibitor to use in a
certain well and helps in the prediction of the life span of tubulars. Figure 11-6 shows a
typical COPRA correlation for uninhibited tubing corrosion. KG for this case = mpy/bbl
H2 O per MMSCF of gas. Figure II-7 shows a typical COPRA correlation for coupons in a
continuous injection inhibition system. From this Figure, the following equation can be
written:
0.6
0 .4
0.2
a 0.1
* 0 .0 8
0 .0 6
/ INHIBITED
0 .0 4
0.02
GAS PRODUCTION
0.01
0.1 0.2 0 .4 0 .6 0.81
MMcf/D
Figure IE-6. COPRA Correlation for Uninhibited Tubing [13].
COPRA CORRELATION
5 _ AVERAGE OF ALL COUPON
CORROSION RATES
INHIBITOR CONCENTRATION ,f /
2 _ 2 5 0 - 3 5 0 PPM /
/
WATER PRODUCTION /
4 5 0 0 -1 0 0 B8L/MMCF / /
1CT2 - 1 5 0 -4 5 0 BBL/D / I
C02 PARTIAL PRESSURE / INHIBITOR C
5 - 1 5 0 -6 0 0 PSI / 3 0 0 ppm
7
/'
2 /
o /
10*3 - I /
5 - /
/ INHIBITOR B
2 /
10'4 - J
5
/
2 l 1 1 1 1 1 1
0 .0 2 0 .0 5 0.1 0 .2 0 .5 1 2 5
GAS PRODUCTION RATE, MMCFD
Figure H-7. COPRA Correlation for Inhibited Tubing [13].
25
mpy = 0.00189 x Qgas x QH20 11-28
Using this equation, isocorrosion lines can be calculated for particular field
conditions; Figure IE-8 shows these isocorrosion lines.
Also in [13] a correlation is given to calculate average tubing corrosion rates

from iron counts. This equation, given below, assumes uniform corrosion throughout the
inside of the pipe.
(Cpe) (Qgas) (Qh 2C>)

Average Tubing Corrosion Rate (mpy) = " n-29
(0.082) (L) (ID)
where:
L = tubing length (feet).
ID = tubing inside diameter (inches).
Qgas = gas flow (MMSCFD).
QH20 = produced water (BPMMCF of gas, Barrels of Water per Million
Cubic Feet of produced gas).
Cpe = Iron counts in ppm.
Ikeda [ 11 ] performed experiments on three kinds of apparatus described later in
the experimental equipment section. He shows the behavior o f the corrosion rate as a
function of steel composition, temperature, and testing apparatus. The results from these
tests are described in the following figures. Figure II-9 shows the effect of the solution on
the corrosion rate for three different steels. Figure 11-10 shows the effect of temperature on
corrosion rate for tests performed in an autoclave. Figure 11-11 shows the effect of C 0 2
partial pressure for tests performed in an autoclave and in Loop Tester "A." Figure 11-12
shows the effect of temperature in the Loop Tester "B." These figures summarize the work
done by reference [ 11 ].
ISO-CORROSION LINES FROM COUPONS IN C 02 FLOOD
INHIBITOR B, 3 0 0 ppm
0 .5 1 2 4 mpy
WELL
3 5 -7
WELL
3 6 -3
10 20 50 100 200 500 1000

QH 2 o b b l /D
Figure n - 8 . Isocorrosion Lines from Coupons in a Continuous

Inhibition C O j Flood System [13].
27
2 Cr
500
CORROSION RATE (mpy)

E

Ui
5
ir
z
o
CO
o
cr
cr
o
o
0 -
COg-synthetic C02*pure Ar- synthetic

sea water water sea water
(pH 5.3 ) (pH 5 .4 ) (pH 5 .3 )
Figure II-9. Effect of Gas-Solution Condition on Corrosion Rate in Loop

Tester "A." CO2 Partial Pressure = lOOkPa; Temperature,
60C; Velocity, 2.5 m/s [11].
TEMPERATURE (F)
70
2500
60 C -steel
2Cr
5Cr
50 9Cr-lMo 2000

13Cr
25C r-6N i-3M o
40
1500
O 30
co
1000
20
o
500
A - -
100 200 300

TEMPERATURE (C)
Figure n-10. Effect of Temperature on Corrosion Rate in Autoclave.

CX>2 Partial Pressure, 3 MPa; Room Temperature;
2.5 m/s Velocity Stirring [11].
1 1 ' ' ------
3 (100C(212F))
50 7 (L 00P 60C ) /%
(140F) / S 1000
/ (AUTOCLAVE)
500
10

E ^ (60C(140F))
J 5
uj (60C) 100
5 (1 4 0 F L /
50
o \+ s
o 1 * C -steel
g o e e C -steel
g - 5r a 13% C r-steel
10
(AUTOCLAVE 100C) 5
(212F)
0.1 A -----------A
I I I I____
0 .0 5 0.1 0 .5 1.0 2 .0 3 .0
PARTIAL PRESSURE OF C02 (MPa)
Figure n-11. Effect of CO2 Partial Pressure in Autoclave

and in the Loop Tester "A" [11].
TEMPERATURE (F)
200 300 400
T T T
C -steel
v lC r -0 .5 Mo
50 A 2Cr 2000
9C r-lM o
13Cr
25C r-6N i-3M o
s 40

E 1500
E
Ui
5 30
tz
z
o 1000
CO
o
jg 20
o
o
500
10
j.
100 150 200
TEMPERATURE (C)
Figure II-12. Effect of Temperature on Corrosion Rate in Loop Tester "B,"

CO2 Partial Pressure 3.0 MPa, Room Temperature,
Flow Velocity 7.0 m/s [11].
31
Metallurgy
Carbon steels when exposed to CO2 corrosion environments are not directly
affected by the chloride content of the solution but by the specific composition of steel.
Hausler [5] mentions that the effect of metallurgy plays an important role in the
interphase controlled mechanism. There is a difference in the morphology of the corrosion
product on different metallurgy. For example in A IS I1020 CR, which consists of a fer-
rite-pearlite grain structure, the ferrite dissolves very fast while leaving behind pearlite
platelets. These platelets may influence the anchoring of carbonate crystals on the metal
surface. Also, the platelets may roughen the surface of the specimen creating high local
turbulence (if specimen is in a flowing system) increasing corrosion rates. Low carbon
steels such as AISI 1020 CR and API (American Petroleum Institute) specifications J-55
and C-75 show large area mesa corrosion in the laboratory and in the field.
On the other hand, metals such as API N-80 and P-105 type quenched and
tempered (Q&T) with carbide structures that look like needles sticking out (bainite) may
offer better anchorage for the scale. This is because for this case instead of mesa attack,
pitting was observed [4]. According to this author [4], the carbide structure is then a
controlling factor on the morphology of the FeC0 3 scale when the metal is exposed to
flowing conditions.
Craig [14] mentions in his paper that the formation of cementite is commonly
referred to as "metal dusting" when the environment is carbon monoxide and hydrocarbon.
When the environment contains carbon dioxide, the formation of cementite is termed
"breakaway oxidation," but both terms are used interchangeably. For Craigs case, the
formation of FejC was favored over other corrosion products such as FeCOj. The main
purpose of his paper was to show that F ejC can be produced as a corrosion product.
32
pH an d C O ;
The effect of temperature on pH at C 0 2 partial pressure of 1 bar was studied by

de Waard and Milliams [8 ]; they gave an empirical equation which is shown below:
pH(PCC>2 = 1 bar) = 4.17 x 1 0 '3 T(C) + 3.71 11-30
This equation plotted in Figure 11-13.
Bonis [15] presents an equation describing pH as a function o f C 0 2 partial
pressure in a NaCl (0.5 M) solution. This equation is as follows:
pH = 4.1 - 1/2 logPC0 2 (bars) @ 80C 11-31
Eriksrud [10] presented an equation for pH while it was being monitored in the
flow loop. This equation is as follows:
pH = - 0.5 log PCCtybars) - 0.5 log K / b 11-32
where:
K = the dissociation constant for carbonic acid.
b = the Henrys law constant, constant for their experimental conditions.
Murata [16] presents an equation for pH which was obtained using conductivity
data:
pH = 2.98 + 3.49 x 103 T - (0.19 + 9.78 x 10 r 4) logPC0 2 11-33
where:
T = temperature (C)
PC 0 2 = C 0 2 partial pressure (bars)
This equation is valid for temperatures between 20C and 80C.
33
4.1
4 .0
3.9
X
Q.
3.8
3.7
0 10 20 30 40 50 60 70 80
TEMPERATURE C
Figure 11-13. Effect of Temperature on pH at 1 Bar CO 2 $]
34
Bicarbonate Effects
Jasiiiski [6 ] studied corrosion rates as a function of temperature and CO2 partial
pressures. He waited until the specimens were passivated. By doing so, the specimen
would be covered by a corrosion layer. The adherence of this corrosion layer to the steel
surface depends on many factors; such as, CO 2 partial pressure, temperature, and ions in
solution. He found that at 0.83 MPa CO 2 partial pressure and at room temperature, in a
solution of plain tap water the corrosion layer formed on the surface of the metal specimen
was Fe3 C (cementite). This iron carbide product acts as a protective layer from the corro
sive medium while at the same time it may increase corrosion of the metal within the metal
surface by galvanic coupling, the metal being the anode and FegC the cathode. The poten
tial between the FejC and the iron is 30 mV cathodically at 70F.
At a temperature of 95C and the same partial pressure in plain tap water Jasin-
ski found a combination of FegC and FeC O j. His experiments were performed in an
autoclave with different solutions, temperatures, and CO 2 partial pressures. He found that
the corrosion rates after a period of 72 hours were higher for pure tap water than for a
solution of 4% NaCl and a solution of 14 ppt (parts per thousand) of NaHC0 3 for both
conditions, room temperature, and 95C at the same CO2 partial pressure of 0.83 MPa.
The corrosion rates were low est when the solution contained 14 ppt of
NaHC0 3 at a temperature of 95C. same 0.83 MPa 0 3 2 partial pressure. For this case the
corrosion rate decreased after 72 hours to 0.5 mpy, while for the case of 4% NaCl, it
decreased to 50 mpy and to 280 mpy for pure tap water, at the same conditions. This
implies, that as time increased, a protective corrosion layer was being formed; and, it
seems that the protectiveness of this scale was increased when the 14 ppt NaHCC>3 solu
tion was used. This corrosion layer prevented the corrodant from acting further on the
metal surface, thus decreasing the corrosion rate. This corrosion layer was identified as
FeC0 3 , iron carbonate scale. From these experiments it seems that the presence of bicar
bonate ions and the temperature influence the corrosion rates through the formation of a
35
protective layer of FeC 0 3 , which reduces the corrosion rates by about three orders of
magnitude (from 280 mpy for plain water to 0.5 mpy for a solution of 14 ppt of NaHCOj)
for a temperature of 95C, and by about one order of magnitude (from 120 mpy for plain
water to 12 mpy for a solution of 14 ppt of NaHCOj) for room temperature.
The effects of bicarbonated solutions were also studied by Crolet [17]. He
added different amounts of bicarbonate to a 0.5 M NaCl solution under a CO 2 partial
pressure of 0.1 MPa. Some results from this study are presented in Figure 11-14.
Experimental Equipment
The experimental apparatus used by Eriksrud [10] was a flow loop. The super
ficial liquid velocity (Vsj) could be varied from 0 to 10 m/sec, and the superficial gas
velocity (VSg) from 0 to 17 m/sec. But most of their tests were performed using Vsj up to
1 m/sec and VSg up to 3.3 m/sec. To observe the flow, they used borosilicate glass as the
material for the test section. The CO2 partial pressure used was up to 2 bars, and tempera
tures were up to 60C. The two-phase flow consists of 4% NaCl and CO2 . They were
able to produce stratified, elongated, and slug flows. Their main interest was in the slug
flow regime. They also introduced an oil phase to study the observations discussed by
many authors: that the oil phase in pipelines helps form a more protective corrosion film
on the steel, organic compounds in oil dissolve in water and act as inhibitors, and that
water may be emulsified by oil/water/gas mixtures making corrosion rates lower than for a
pure water phase. Figure 11-15 shows a schematic of the flow loop used by this author.
H ausler [4] mentions that the factor controlling the corrosion is the scale
permeability. On die other hand, Hausler suggests that in flowing systems, the factor con
trolling the corrosion is the dissolution rate of iron carbonate, which in turn is mass trans
fer controlled and affected by the parameters influencing the iron carbonate solubility.
X
a.
0.1 1 0 0 m q 0.1 M Pa
Figure 11-14. Variations o f the pH of a 0.5 M NaCl Solution:

a) with Its Bicarbonate Content under 0.1 MPa of
Pure CO 2 ; and b) with 10 meq Bicarbonate and
Variable Pressure of Pure CO2 [17].
ho
T2
BYPASS W
L 'a \ I fa LIQUID
L = 0 l -b
- = = = = =
02
= = * _
id
1 P5
Tl
_2 .
\ CORROSION PROBES
GAS
Figure 11-15. Flow Loop Used by Eriksrud [10].
38
The experiments performed by Hausler [4] in autoclaves were done using three
electrodes. The configurations of these electrodes were linear and triangular. The linear
configuration was preferred because the triangular one introduced a much higher IR drop
error. The working electrodes were made of AISI 1018 CR steel. The electrodes were
sandblasted and cleaned with acetone. After the autoclaves were assembled, the solution
was purged with N 2 for deaeration. The CO2 pressure was adjusted prior to heating up.
At the end of the experiment, the specimens were cleaned with acetone, weighed and the
scale removed in an inhibited acid (HC1) at 75 C to observe its dissolution. Then the elec
trodes were weighed again to determine the amount of scale build up. Figure 11-16 shows
the corrosion of the AISI 1018 CR steel in an autoclave. The high peaks represent the high
corrosion rates during heat up; then, the corrosion rate decreased.
The main purpose of the Hausler [4] experiments was to study the kinetics of
CO2 corrosion at various temperatures (6 0 ,9 0 ,120C) and pressures (100 and 150 psi). It
was determined that not much variation in corrosion rate existed at these two pressures.
The solution was NaCl and 3,300 ppm of bicarbonate. During the heat up, the corrosion
rate was high, but once the desired temperature was reached the corrosion rate decreased.
Hausler reasoned that this decrease in corrosion rate was due to a protective iron carbonate
scale being formed.
According to Hausler [4], the saturation of the solution by FeC 0 3 occurred
between 1/2 to 4 hours after heat up started. The time required depended on the final
temperature of testing. Even after saturation of the solution by FeCC>3 , the corrosion rate
increased further, maybe due to a tendency of FeCC>3 to supersaturate the solution.
Iron carbonate has an inverse temperature solubility characteristic in NaCl and
water solutions, and passivation of carbon steel is fast as temperature increases, as can be
observed in Figure II-16.
Ikeda [11] tested steels with various compositions of chromium. He used three
types of apparatus to perform his tests. Most of the time they used an autoclave system as
CORROSION OF 1018 STEEL IN CO2
5 5 0 0 ppm Cl
0 . 0 5 5 mKOH
100 psi CO2 TEMP #C
60
19 0
NEW SCALE FOR
> 120
_ START - INDICATE APPROX.
HEATING TIME FOR SOLUTION
SATURATION WITH
FeCOg
mpy
ROOM TEMP.
TIME, hrs
Figure D-16. Coirosion of AISI 1018 CR in an Autoclave Test [4].
40
STIRRER^ j - i
I THERMO
COUPLE^
--------
HEATER-"-
co2 n2
Figure 11-17. Schematic o f the Autoclave System [11].
TEST PIECE HOLDER
(Pi PE)
r
PUMP
TEST PIECE HOLDER
(COUPON)
Figure 11-18. Schematic of Flow Loop "A" [11].
42
shown in Figure 11-17 or Flow Loop "A" as shown in Figure 11-18. The autoclave was
used for high temperature and pressure tests; i.e., 104 - 480F and 430 psia, respectively,
and at a velocity of 2.5 m/s stirred. Flow Loop "A" was used for a pressure of 14.7 psia
and a temperature up to 60C at flow velocities up to 2.5 m/s. A second loop, Flow Loop
"B," was used to detennine the effects of flow velocity at pressures up to 3 MPa (430 psia),
temperatures from 100 to 200C, and flow velocities up to 7 m/s. This flow loop is shown
in Figure 11-19.
The use of Loop "A" gave an advantage with respect to the other two systems
because of the high ratio of volume to specimen area, and therefore the total amount of
dissolved FeCOj in solution would be higher than for the other two test systems. This
condition simulated more closely the actual field conditions, in which there is plenty of
formation water.
Velocity Effects
Jasinski [6 ] performed his experiments in an autoclave at 300 RPM. The veloc
ities for autoclave systems are produced due to the action of an internal stirrer. The hydro-
dynamic characteristics of autoclave systems are different from those of flowing systems.
Eriksrud [10] performed experiments in a flowing system able to handle two-
phase flows. Using 4% NaCl and CO2 , the pH hardly varied due to flow rate. Polarization
curves at low velocities were equal to polarization curves at stagnant and slightly stirred
conditions. The experiments were performed to study the influence of liquid and gas flows
on the protective layer formed in formation waters. She formed the protective scale out
side the loop, then introduced them into the loop, where they were subjected to the differ
ent flow conditions. While forming this scale the corrosion rate was being monitored. The
period required for scale formation varied between 4 to 72 hours. Eriksrud believed the
action of the shear stresses on this layer caused a mechanical fatigue action on i t Based on
this theory she designed two types of experiments to determine the instantaneous wall
shear stresses exerted by the fluid on the metal surface.
AUTOCLAVE HEATING
ELEMENT
PVHI
o TEST SPECIMEN
FLOW
METER DRAIN
VALVE
Figure H-19. Schematic of Flow Loop "B" [11].
44
1) Using a laser Doppler velocimeter (LDV) in combination with optical

probes she recorded velocity profiles in the bottom of the pipe in slug flow. Then, the wall
shear stresses were calculated from this velocity profile.
2) Also, she used flush-mounted hot film probes to measure directly the wall
shear stresses.
Figures H-20,11-21, and 11-22 show the type of results obtained by experiments
1) and 2) above. Figure H-20 and 11-21 show the velocity profile in the bottom of the pipe
in the slug and in the film of the slug flow. Figure 11-22 shows the wall shear stress in a
slug flow.
Figure 11-23 shows the typical corrosion rate (in terms of icorr) results obtained
by Eriksrud. Portion "A" shows the corrosion rate as the protective scale is being formed
outside the flow loop. During time period "B, only liquid flow was applied (Vsj = 1
m/sec). As it can be seen, the corrosion rate (icorr) remained low. Then over period "C"
gas was introduced producing slug flow conditions. The corrosion rate remained low for
about an hour, then a drastic increase in corrosion rate was observed. In "D," the gas flow
is stopped ana only liquid is circulated. At this point, the corrosion rate decreases again
due to the formation of a protective layer.
This author gives three theories by which the scale is removed from the metal
surface:
1) The removal of the protective layer is due to the fatigue action of the slug
flow on the surface. The presence of gas was necessary for the removal of the corrosion
layer to occur.
2) The removal of the protective layer could have been a chemical transforma
tion of the layer. This is due to the argument that the layer was formed outside the loop;
therefore, once in the loop there was no longer an equilibrium between the scale and the
medium.
0 6 12 13
iw A L L DISTANCE FROM WALL, mm
Figure H-20. Velocity Profile of the Slug [10].
5.0
A A A A A A
3 .0
E
>
0.0
24
DISTANCE FROM THE WALL, mm
WALL
Figure 11-21. Velocity Profile of the Film at Bottom of the Pipe [10].
CM SLUG A
E f il m
z
Figure 11-22. Wall Shear Stress in Slug Flow [10].
48
W
W

g
FILMING
LIQUID FLOW
SLUG FLOW
LIQUID FLOW
STAGNANT
TIME
Figure H-23. Schematic Representation of the Main Results

Obtained by Reference [10].
49
3) The layer broke down electrochemically when the polarization potential
became too positive.
Ikeda [11], as mentioned, had two flow loops, "A" and "B" described previous
ly in the experimental equipment section. He found a critical velocity of 0.32 m/sec.
Below this velocity the rate-determining step for CO 2 corrosion was found to be mass
transfer. Above this velocity he determined the reaction process to be independent of
diffusion. Also, 0.32 m/sec was independent o f the chromium content of the steel. For
their conditions (described in the experimental equipment section) and a velocity of 0.03
m/sec, turbulent flow was estimated from a Reynolds number based on an equivalent
diameter of 6.11 cm, a density of 1.03 gr/cm^, and a viscosity of 5.1 x 10"^ gr/cm-sec.
There was no evidence of FeCOj scale formation but only small traces of Fe 3 C. Figures
H-24 and 11-25 show the corrosion rate as a function of velocity for both Loops "A" and
"B," respectively.
Dunlop [18] presented a critical velocity defined as follows:
Critical Velocity = Y U 11-34
where:
^ = produced fluid density in kg/m^ OT lb/ft^
K = 7.6 for velocity in m/s and ^ inkg/m^
K = 100 for velocity in ft/s and ^ in lb/ft^
In this case, "Critical Velocity" is defined as that velocity at which the mass
transfer exceeds the kinetics of the formation of FeCC^.
50
O 0.22C
a 0.23C
0.24C
CORROSION RATE (mm/y)

0.08C-1.2Cr -0.5M o
0 .0 5 C - 2Cr
500
6 ^
1 L J L
10
VELOCITY (m/s)
Figure H-24. Effect of Flow Velocity on CO2 Corrosion in

Loop "A." CO2 pp = 100 kPa, T = 60C [11].
50 2000


5 40
E 1500
E
us C -steel
5 30 v 1C r-0.5M o
<r a 2Cr
z
o 9Cr-1M o
CO
1000
o 13 Cr
E 2 0 2 5 C r-6 N i-3 M o
O
o
500
10
__
------- ~Yr
T ------------------- -
1
____ _____________ i l l 1
7 15
VELOCITY (m /s)
Figure 11-25. Effect of Flow Velocity on CO 2 Corrosion

in Loop "B." CO2 PP = 3.0 MPa, T = Room [11].
52
BASICS OF ELECTROCHEMISTRY
Electrochemistry is the study of the conversion of electric energy into chemical
energy or vice versa. Electrons flowing through a wire constitute an electric current.
Likewise, ions flowing through a solution constitute an electric current. When corrosion is
taking place, the decomposition of iron occuis in the form of iron ions (Fe++). For every
iron ion going into solution, two electrons are produced. Iron goes into solution from the
anodes; thus these reactions are called anodic reactions. The electrons produced by the
corrosion of iron move through the metal or any metallic connection. The places the elec
trons transfer to are called cathodes. Thus, reactions occurring at the cathode are called ca-
thodic reactions. At the cathode, in deaerated acid solutions, the electrons combine with
hydrogen ions to form hydrogen gas; when oxygen is present, the electrons combine with
oxygen and hydrogen ions to produce water. In the case o f oxygenated basic or neutral
solutions, the electrons combine with oxygen and water to form hydroxyl ions (OH').
Figure 11-26 shows a schematic of this process. This figure represents a corrosion cell. As
can be observed from the figure, the reactions occurring in the corrosion cell produce a
flow of electrons. Therefore corrosion is merely an electrochemical process.

In an electrochemical or corrosion cell, four things happen simultaneously:
1) An oxidation (anodic) reaction occurs at the surface of the anode.
2) A reduction (cathodic) reaction occurs at the surface of the cathode.
3) Electrons flow through a metallic path to the cathode.
4) Ions flow in the electrolyte.
If one of these four reactions is prevented, then corrosion will not occur.
A general anodic reaction can be shown with the following equation of the
corrosion of metal (M) into a metal ion and free electrons:
M > Mn+ + n e' H-35
ELECTROLYTE
2e
* + Cf
Fe++
Cf
ANODE CATHODE
Figure H-26. Corrosion Cell Showing the Reactions.
In oxygen free acids, the controlling cathodic reaction is shown in the equation
below:
2H+ + 2e ' ---- > H 2 (g) H-36
When a metal is exposed to a corrosive medium, both reduction and oxidation
reactions occur on its surface. The metal functions as both the anode and the cathode.
These areas are present in the metal in areas of, for example, contact between cold worked
metal and annealed metal, phase change boundaries, grain boundaries in contact with
grain, metal imperfections, etc.
N em st Equation
The Nemst equation is an equation which expresses the relationship between
the potential of corrosion cells and the activities of the species that undergo reactions in the
cell. This equation permits the calculation o f cell potentials at a non-standard state.
Standard potentials are those potentials measured with respect to the hydrogen electrode at
standard conditions (25, 1 atm). The Nemst equation is expressed as follows:
2.303 (R) (T)

E = E ---------------------x log Q H-37
nF
where:
E = Potential at non-standard state.
E = Standard potential
R = gas constant, 8.314 KJ/Kg mole K
T = temperature, K
F = Faradays constant, 96,493 coulombs/mol e '
n = number of electrons transferred in the reaction
Q = the reaction quotient
For example, in a chemical reaction as follows:
aA + bB <-----> cC + dD E-38
[C]c [D]d
Q = - r n -39
[A]a [B]b
In equation 11-39, the quantities inside the brackets are the concentrations or
activities of the species. At equilibrium E = 0 and the reaction quotient, Q, becomes the
equilibrium constant, K. Substituting for R, and T = 298K, the equation n-39 becomes:
0.059
E = x log K H-40
n
Pourbaix Diagrams
Pourbaix diagrams are diagrams o f pH versus electrochemical potential (see
Figure n-27 [19]). These diagrams make it possible to compare metals and give an idea of
the description of the elements involved in the reactions; i.e., corrosion. Also, they help in
the prediction of the spontaneous direction of a reaction, the estimation of the composition
of corrosion products, and in the prediction of environmental changes that will prevent or
reduce corrosion attack. Pourbaix diagrams represent equilibrium and should never be
used to predict velocity of a reaction. These diagrams are obtained using Nemst equation.
Figure 11-27 shows the Pourbaix diagram for the iron-carbon dioxide-water
system. The horizontal lines of this figure represent an equilibrium that is independent of
potential, a non-redox equilibrium but pH dependent The vertical lines represent redox
equilibrium, that is, independent of pH but dependent on potential. The diagonal lines
represent equilibrium that is dependent on both pH and potential.
100C
0.8
0.6
0 .4
>
lii
m
-J
<
h-
Z
FeOH (aq)
- 0.6
Fe(C05 ) U)
- 0.8
0 2 4 6 8 10 12 14
pH
Figure 11-27. Pourbaix Diagram for the Iron-CC^-I^O

System, at 100C and 100 psig CO2 pp [19].
Electrochemical Measurements
Methods to measure corrosion rate include weight loss, ultrasonic thickness
measurements, electrochemical methods, and others [20,21], The methods utilized in this
work are electrochemical and weight loss methods.
Modem electrochemical methods are based on Faradays law:
"The quantity of substances undergoing change at each electrode during elec
trolysis is directly proportional to the quantity of electricity that passed through the electro
lytic cell [22]." In other words, the amount o f current produced in an electrochemical cell
is proportional to the electrochemical reactions occurring in the cell. Corrosion is an elec
trochemical process; therefore, by measuring the current when corrosion is taking place,
corrosion rates can be estimated.
Electrochemical measurements deal with the production and interpretation of

polarization diagrams (plots of potential vs. current density) and can lead to information on
corrosion rates, pitting tendencies, passivity and Ouier important information.
As has already been mentioned, when a metal is exposed to a corrosive medi
um, both reduction and oxidation reactions occur on its surface. When the metal is in an
electrolytic solution and not connected to any instrument, the metal acquires a potential.
This potential is referenced to a reference electrode and is referred to as the corrosion
potential or open circuit potential Ecorr or rest potential E j ^ . A metal at Ecorr has both
local anodic and cathodic reactions occurring on its surface and no net current flows to or
from the metal.
Polarization
If a potential is externally applied to the metal, then it is forced to assume a
potential other than Ecorr and the metal is said to be polarized. When this external poten
tial is applied, there is a net current flow from the metal that can be measured. As this
externally applied potential gets more positive than Eco rr an anodic current predominates
over the cathodic current. At this point, the electrode being polarized is said to be anodical-
ly polarized. When this potential is increased in the negative direction, below Ecorr the
opposite happens. This process is referred to as cathodic polarization.
Polarization diagrams o f corroding metals are graphs o f applied potential
versus log current or log current density or just current density (as for the case of linear
polarization). To perform electrochemical polarization measurements, a set of electrodes
and a potentiostat are used. The set of electrodes is comprised of a working electrode, a
counter or auxiliary electrode, and a reference electrode. The working electrode is made, of
the material under study (API N-80, for this work). The reference electrode, as the name
suggests, is the electrode used as the potential reference. The counter electrode is the elec
trode where cathodic reactions occur when anodic polarization is being performed. In this
work, the reference electrode is made of cast iron and the counter electrode of stainless
steel.
A potentiostat is a device that maintains the desired potential difference be
tween the reference and the working electrode by continuously controlling the current
between the working and the counter electrode.
Activation Polarization
Activation polarization is an electrochemical reaction that is controlled by the
reaction sequence at the metal-electrolyte interface. For example, the rate at which hydro
gen ions are reduced to hydrogen gas depends on factors such as how fast the electrons
transfer to the metal surface to combine with the hydrogen ions (H+). It is an electrochem
ical phenomenon controlled the way the reactions occur at the metal-electrolyte interface.
Activation polarization is usually the controlling factor during corrosion in strong acids.
For activation polarization the relation between the overvoltage and the reac
tion rate is given by the following equation [23]:
= p l o g ( i / i 0) H-41
Where Y j is the overpotential or overvoltage, which is the applied potential
above or below the open circuit potential (E - Ecorr), and p is the Tafel slope. Whether the
value p is positive or negative depends on the direction of the overpotential. The Tafel
slopes are calculated from the linear regions of the polarization diagra m s. The measured
current is i, and i0 is the current flowing in the metal at Ec o rr This current, iQ, also re
ferred to as the corrosion current, ico rr cannot be measured directly, and it is proportional
to the corrosion rate. Although iQcannot be measured direcdy, it can be estimated with the
aid o f polarization diagrams. This current is estimated from the point of intersection
between the anodic Tafel slope Pa and the cathodic Tafel slope Pc. Figure 11-28 shows a
typical polarization diagram, showing the Tafel slopes and estimation of icorr The equa
tion governing the curved lines in Figure 11-28 is as follows:
iappl = icorr (exp[-pc( ^ )] + exp[+Pa ( T ])]} II-42
where:
Iappi = applied current
ic o rr = conosion current
*Y| = overpotential (E - Ecoir)
Pa = anodic Tafel constant = 2.3 RT/anF
Pc = cathodic Tafel constant = - 2.3 RT/(1 - a)nF
a = transfer coefficient
R, T, F, and n were defined previously for equation 11-37; a is called the trans
fer coefficient, it varies between 0 and 1, often close to 0.5. Equation 11-42 is a form of the
Tafel equation and referred to as the Butler-Volmer equation.
I L
lu
_ o
appl
corr
log i
Figure 11-28. Polarization Diagram.
Linear Polarization
If the potentials are applied to within 10 mV of Ecorr in the positive or negative
directions, the applied current density can be approximated by a linear function of the elec
trode potential. The slope of this curve is the polarization resistance AE / Aiappl. If a metal
is very corrosion resistant to a certain environment, when linear polarization is performed,
the slope of this curve would be a large value, representing the resistance of the metal to
this corrosion environment The polarization resistance leads to an estimate of icoir which
in turns leads to an estimate of the corrosion rate. If the overpotential Y j is less than 10
mV, the Butler-Volmer equation 11-42 reduces to the following equation:
AE Pa 0c
H-43
Aiappl 2.3 (icorr) (Pa + Pc)
This equation relates the slope, AE / Aiappj, to the kinetic parameters of the
corroding system. Once this slope has been estimated, corrosion rates can be calculated
using the following equation:
C.R. = [0.13 (icorr) (E.W.)] / ^ n-44
where:
C.R. = Corrosion Rate in mils per year (mpy)
^ = metal density (g/cm^)
ic o rr = corrosin current ( jiA/cm^)

E.W. = equivalent chemical weight, which is the atomic weight of the corrod
ing species divided by the number of electrons transferred. For iron,
the number of electrons transferred is 2 (F e > Fe2+ + 2e).
Concentration Polarization
Concentration polarization refers to an electrochemical process that is rate
controlled by the concentration changes in the solution adjacent to the metal surface. This
usually happens when a metal is corroding rapidly. Then the region very close to the metal
surface will become depleted of hydrogen ions because they are being consumed by the
cathodic reaction. The reaction then is controlled by the diffusion rate of the hydrogen
ions to the metal surface.
Concentration polarization is usually the controlling factor during corrosion in
dilute acids, aerated water, and salt solutions. It is also called diffusion polarization. Ac
cording to Ficks law, the flux o f the substance to the electrode is proportional to the
concentration gradient. Where D is the proportionality constant and is called the diffusion
coefficient Combining Ficks law with Faradays law, we have:
i = - nFD (cQ - c) / 8 11-45
where:
cQ = concentration in the bulk solution.
c = concentration at the metal surface.
D = diffusion coefficient of the corroding species.
F = Faradays constant
n = number of electrons transferred in the reaction.
5 = Nemst diffusion boundary layer, assuming a linear concentration gradient
i = diffusion current density.
CHAPTER HI
FORMATION AND STRUCTURE OF IRON CARBONATE SCALES
Structure of Iron Carbonate Scales

The puipose of the tests made in the autoclave was to study the structure of iron
carbonate scales formed on steel specimens at different test conditions (pressures, tempera
ture, and aqueous chemistries). These tests also helped to identify some initial guidelines
for testing in the CO2 Loop. Specimens having an iron carbonate scale were also trans
ferred to an erosion apparatus similar to that designed by Camacho [24] and subjected to
different impingement loadings involving a liquid and solid particles entrained in a liquid.
The subject of erosion of iron carbonate scales will be discussed in Chapter IV.
Tests in the autoclave have been performed using API N-80 and 1018 CR steel
specimens. Some API N-80 steel specimens had a quenched and tempered (Q&T) micro-
structure and some had a normalized microstructure. The A IS I1018 CR specimens had a
normalized microstructure. Figures 111-17, III-18 and 111-19 show micrographs of the
microstructures of these three types of steel. Tables HI-1, IH-2 and IH-3 show the chemical
compositions of these three types of steel.
Scales have been formed at various temperatures and CO 2 partial pressures.
The morphology of the scales formed on these three kinds of steels has been studied and a
discussion of the findings is presented later in this chapter.
The initial puipose of these tests was to obtain experience in forming and iden
tifying iron carbonate scales using X-ray diffraction, an optical microscope, and a Scan
ning Electron Microscope (SEM). Additional objectives were to evaluate the mechanical
strength properties of these scales under erosion loadings discussed in Chapter IV.
63
TABLE HI-1
Chemical Analysis of API N-80 O&T Steel
c,% .29
Si, % .34
Mn, % 1.48
P,% 0.012
S,% 0.014
Ni, % 0.08
Cr, % 0.24
Mo, % 0.09
Cu, % <0.01
Al, % 0.04
Ti, % <0.01
TABLE m-2
Chemical Analysis of API N-80 Normalized Steel
c,% .33
Si, % .41
Mn, % 1.59
P,% 0.016
S,% 0.017
Ni, % 0.09
Cr, % 0.58
Mo, % 0.24
Cu, % 0.01
Al, % 0.04
Ti, % 0.01
TABLE m -3
Specification of A IS I1018 CR Steel
C,% 0.15/0.20
Si,%
Mn, % 0.60/0/90
P,% 0.040
S,% 0.05
Ni, %
Cr, %
Mo, %
Cu, %
Al,%
Ti, %
67
Discussion of Preliminary Results

Observations made during the preliminary tests to make iron carbonate are
discussed here. Figure IH-1 shows an SEM photograph of iron carbonate crystals scattered
on the surface of an API N-80 Q&T specimen. The conditions for these first tests were
those used by Arismendi [25] which were: a CO2 partial pressure of 800 psi, a temperature
of 200F, a stirring speed of 250 - 300 rpm, a solution of 1,600 ml of 4% NaCl in deaerat
ed water for 96 hours. The water used for this and the subsequent tests is City of Tulsa tap
water. The composition of the water is shown in Table HI-4. This test was done using six
specimens similar to the one shown in Figure HI-2. As can be observed from Figure IH-1,
the FeCC>3 crystals are scattered on the surface of the specimen and do not form a uniform
scale. This type of surface was also observed by Jasinski [6 ] at (0.83 MPa) 120 psi CCb,
200F in water after 4 hours of exposure.
To form a more uniform iron carbonate scale, a greater concentration of ferrous
ions were needed in solution [26]. Therefore larger coupons were used for the subsequent
tests. Three coupons of API N-80 Q&T steel and three coupons of A IS I1018 CR steel
were used under the same conditions as before but at 600 psi CO 2 partial pressure. The six
coupons provided enough ferrous ions to form a uniform scale on both steel types. Figures
m -3 and III-4 show SEM photographs of FeC0 3 scale on an N-80 specimen. As can be
seen from these photographs, the scale formed is very uniform and the crystals are densely
packed. These scales are very similar to those described by Jasinski [6 ]. The scales on the
specimens were identified as siderite (FeCC^) by the use of X-ray diffraction. Figure El-5
shows the X-ray diffraction pattern for this case. The peaks correspond to the angles iden
tifying siderite, as shown by Table El-5. Table IE -6 shows the angles at which iron oc
curs. Contrary to the method used by Jasinski [6 ], in which he scraped the FeC 0 3 off the
metal surface, the X-ray diffraction was done directly on the specimen with the scale
present. By performing the X-ray diffraction directly on the specimen, the presence of iron
can be detected on the surface of the specimen if the scale is not uniform and dense. This
Figure HI-1. Micrograph of Siderite Crystals Scattered
on the Surface of an API N-80 Steel Specimen
at 167X Magnification.
TABLE m-4
Chemical Analysis of Tulsa Tap Water
pecies Concentration
(mg/1)
Ca 36.2
Mg 1.57
Si 3.70
Mn <0.005
Na 6.21
Ba 0.062
Fe <0.010
F 0.89
N 2.3
CaC0 3 80
cr 9.7
so4= 8.3
h c o 3- 80
pH =7.8
70
Figure ffl-2. Photograph of the API N-80 Steel Specimens

Used for the First Three Experiments.
Figure ffl-3. Micrograph of an Iron Carbonate Scale on the
Surface o f an API N-80 Steel Specimen
Figure m -4. Micrograph o f an Iron Carbonate Scale on
the Surface of an API N-80 Steel
Figure HI-5. X-Ray Diffraction Analysis on an API N-80 Steel
Specimen to Identify a Uniform Siderite Scale.
TABLE m-5
High Intensity Peaks for Iron Carbonate (FeCCty
d, Angstrom 2.79 1.73 1.96 3.59 2.13 2.341
Wi 100 45 30 25 25 20
2 0 , Degrees 32.05 52.87 46.28 24.77 42.39 38.42
TABLE m-6
High Intensity Peaks for Iron (Fe)
d, Angstrom 2.03 1.17 1.43
Wi 100 30 20
2 0 , Degrees 44.6 82.35 65.2
75
type of X-ray diffraction pattern is shown in Figure HI-6 . The iron peak occurs at 4 4 .7 as
shown in Table HI-6 , with as much or higher intensity as the one shown for FeCOj at
45.9. (The angles shown on Tables m -5 and IE -6 may not correspond exacdy to those of
the X-ray sweep, because of a calibration offset in the instrument. Calibration errors were
observed using a sample of silicon as a reference.)
Subsequent tests were made at lower pressures and temperatures. The objec
tive was to simulate the CO2 Loop conditions. Therefore, tests were made at 185F and
150 psig CC>2 partial pressure. But unfortunately, no iron carbonate was identified.
A m ixed solution o f 4% NaCl and 14,000 ppm o f sodium bicarbonate

(NaHCOg) was used following the Jasinski [6 ] recipe at the same temperature and pressure
cited above. For this case, an FeCO j scale was formed on both types of steels. Further
observation of this scale showed that the scale formed on the N-80 steel specimen was less
dense than that formed on the A IS I1018 CR steel specimen. X-ray diffraction detected
some iron on the API N-80 QcLT steel specimen.
Also, by analysis under an optical microscope (64X) the FeCOj scale looked
thicker on the 1018 CR steel than the N-80 Q&T. This finding is contrary to what Aris-
mendi [25] found.
Tests at Low Temperatures

The viewing sections on the test section of the CO 2 Loop are made of clear
polysulfone. The viewing sections on another test loop [27] have been proven to be very
useful when identifying the flow regimes. Therefore, it is desired that this feature be re
tained for the CO 2 Loop. However, there is a temperature limitation on the polysulfone
material of about 160F at a pressure of about 150 psig.
A series of tests were conducted at a temperature of 155F and 120 psig CO2
partial pressure in a solution of 1,600 ml of 4% NaCl in deaerated water. At these condi
tions, FeCQ 3 along with some Fe was identified by the X-ray diffraction on an N-80 Q&T
wmwmmr**
i ;.i u/i/n i 11
*> : 'M
Figure m-6. X-Ray Diffraction Analysis of an API N-80

Specimen Identifying a Siderite Scale and
Some Iron Presence.
77
specimen. Figure HI-6 shows the X-ray diffraction pattern for this case. As can be seen
from this figure, the peak occurs at an angle of 44.6, one of the angles corresponds to the
presence of iron as shown in Table HI-6 . The other angles correspond to the presence of
FeCOg (siderite), as shown by Table HI-5. Under the SEM the scale formed on this N-80
steel specimen did not look like the scale as identified earlier (i.e., Figure m-4) in which
iron carbonate crystals easily could be identified. Figure HI-7 shows a photograph of a
type of iron carbonate scale which is not uniform nor dense, and crystals could not be
identified. On the other hand, the X-ray diffraction on the 1018 CR steel specimen showed
no peaks at the angles indicating iron but only those indicating siderite (see Figure ni-8).
This means that the scale formed on the 1018 CR was more dense, as shown in Figure HI-9
and Figure HI-10.
Summary
Iron carbonate scales were formed in the autoclave. This scale has been identi
fied by means of X-ray diffraction, the use of an SEM and an optical microscope.
It seems that the characteristics o f the scale formed depend not only on the
temperature, CO2 partial pressure, and aqueous chemistry, but on the metallurgy or chemi
cal composition of the steel. On the 1018 CR, an FeCOg scale was formed 100% of the
time; while for some conditions tested, the scale was not formed on the N-80 Q&T speci
men. The formation of iron carbonate scale on the N-80 Q&T steel specimens is very
dependent on test conditions, while for 1018 CR steel specimens it is not.
Figure HI-7. Micrograph of a Non-Uniform Siderite
Scale on an API N-80 Steel Specimen
at 1,030X Magnification.
Figure HI-8. X-Ray Diffraction of a Siderite Scale on
the Surface on an A IS I1018 CR Steel Specimen.
Figure HI-9. Micrograph o f a Siderite Scale on a 1018 CR
Steel Specimen at 620X Magnification.
Figure HI-10. Micrograph of a Siderite Scale on a 1018 CR
Steel Specimen at S20X Magnification.
82
Observations
It has been experienced that when no iron peaks are shown in the X-ray sweep,
the iron carbonate scale formed on the specimen surface is a thick one with a secondary
scale on top of the scale first formed. For the X-ray diffraction conditions used in this
study, it appears that the penetration depth o f the X-ray beam is at least 30 Jim. This
means that when no iron is shown in the sweep, the scale should be expected to be at least
30 Jim thick. By observing a cross-sectional area of a specimen with iron carbonate scale
under the microscope, the thickness of the scale could be estimated. Thickness estimates
made this way indicate, that when no iron peaks are present in the X-ray diffraction analy
sis, the scale is at least 30 pm thick. X-ray diffraction is made directly on the specimen
surface. By this procedure, when the scale is thin, the presence of iron is detected in the
X-ray sweep. For example, Figure HI-11 shows a micrograph of a "thin" iron carbonate
scale, and the X-ray diffraction shows an iron peak in the X-ray sweep, Figure n i- 6 . On
the other hand, Figure HI-12 shows a micrograph of a "thick" scale, and the X-ray diffrac
tion shows no iron peaks present in the X-ray sweep, (Figure IE-5).
With the use o f an optical microscope one is able to view a cross section of a
specimen. This allows a characterization of the thickness of the scale and observations of
how the scale is formed within the metal and the microstructure of the specimens used.
Examination of the specimens showed that whenever a "thick" scale was ob
tained it was due to this recrystallization o f iron carbonate. Recrystallization of iron
carbonate occurs when the solution reaches saturation by FeCOj; at this point there is a
precipitation of iron carbonate on to any surface in contact with the solution, including the
metal specimen already containing an iron carbonate scale. When this secondary scale was
formed, an iron peak was not detected in the X-ray sweep. For all the specimens subjected
to the conditions of Table HI-7, the type of scale formed was a thick one with the two
different kinds of iron carbonate layers. From Figure HI-13 it can be observed that the iron
METAL
Figure HI-11. Micrograph of a "Thin" Iron Carbonate Scale

on a 1018 CR Steel Specimen, 900X Magnification.
Figure m-12. Micrograph of a "Thick" Scale on an N-80
Q&T Steel Specimen, 900X Magnification.
TABLE m-7
Conditions for Formation of FeCOg
TEMP (F) PRESSURE (psig) SOLUTION TIME
160 150 4% NaCl + 2 g/1 NaHC0 3 72 Hrs.
in Deaerated Water
Figure m-13. Micrograph of the Two Types of Scales on an
N-80 Q&T Steel Specimen. "A" Top Scale,
"B" Primary Scale, and "C" Pores, 1000X Magnification.
87
carbonate crystals of the primary scale are larger than those of the secondary one. The
primary scale does not completely cover the metal surface leaving some porous areas or
areas of bare metal in between the FeCOj crystals (see "B" in Figure HI-13). On the other
hand, the secondary scale is densely packed forming a uniform scale throughout the
specimen surface (see "A" in Figure IH-13). But for some specimens the bond between the
secondary scale and the primary one is not as strong as the bonding between the primary
scale and the metal surface. This was observed by scratching one of the specimens with a
knife blade. The secondary scale was easily removed from the primary one, but the pri
mary scale stayed bonded to the metal surface. The primary scale is not so easily removed
from the metal surface as the secondary scale is removed from primary scale. Figure HI-
14 shows a cross-sectional view of the scale remaining after it was scratched (to the left of
"C") compared to the unscratched one with the secondary layer still attached (to the right
of "C").
For some other cases, it appears that the secondary scale can delaminate from
the primary one. Evidence of this fact can be seen in Figure HI-15, where there is a divid
ing line "A" between the two scales. For other cases, the specimens came out of the auto
clave with the secondary scale broken in some places. One possible explanation for this
delamination is that perhaps some o f the solution was trapped inside the pores of the
primary scale. When the secondary scale precipitated on top of the primary one, it covered
the whole specimen including the solution in the pores. When the autoclave was de
pressurized, the dissolved CO2 trapped in the pores of the primary scale came out of solu
tion and expanded, breaking the secondary scale and exposing the primary one (see Figure
HI-16). If the recrystallization phenomenon is one that may be occurring in oil and gas
wells, then any changes in the flow that cause pressures changes may result in the phe
nomenon described above. The primary scale is porous, and once it is exposed through the
secondary scale to the flow, the bare metal at the root of the pores is once again in contact
88
SECONDARY
P R IM A R Y
METAL
Figure HI-14. Micrograph Showing the Cross-Sectional

Area of a 1018 CR Steel Specimen with the
Primary Scale on the Left and the Secondary
Scale to the Right, 900X Magnification.
METAL
Figure m-15. Micrograph of a FeCC>3 Scale Showing

How the Secondary Scale Is Delaminated
from the Primary Scale, 900X Magnification.
Reproduced with permission of the copyright owner. Further reproduction prohibited without permission
Figure m-16. Micrograph of a FeCOg Scale Showing
How the Secondary Scale Ruptured from
the Primary Scale, 63SX Magnification.
91
with the corroding medium. On the other hand, the secondary scale is very compact, but it
can be easily debonded from the primary scale by the phenomenon described above.
Specimen Metallurgy
It has been experienced that the "primary" iron carbonate scales formed on the
N-80 and A IS I1018 CR normalized specimens are thicker and more tenacious than those
formed on the N-80 Q&T ones. The "secondary" scale has the same characteristics for
both cases. Figures ID-17 and ID-18 show the microstructures of N-80 Q&T and normal
ized, respectively. Figure ID-19 shows the microstructure of AISI 1018 CR normalized
specimen. Figure 111-20 shows a cross section o f a FeCOg scale formed on an N-80
normalized specimen. For this case the thickness of the primary FeC O j scale is more
uniform over the specimen surface. Also the FeC 0 3 crystals are larger on the normalized
specimen than for the case of N-80 Q&T specimens. Figure ID-21 shows a cross section
of a FeCOg scale formed on an N-80 Q&T specimen. The crystals for this case are smaller
and the thickness of the scale varies from point to point This variation in thickness of the
scales for the two types of N-80 specimens has been observed for many specimens.
Hausler [4] suggests that the variation of the scales is due to the metallurgy of the steels.
For a normalized steel, the pearlite phase is at low concentration. The ferrite corrodes
while the pearlite forms carbide platelets which may help anchor the iron carbonate crys
tals to the surface. This process is depicted in Figure ID-22 where the ferrite is corroded
away leaving behind the pearlite phases as shown. The flow of liquid perpendicular to
these pearlites create some kind of stagnant conditions making the crystals of FeC 0 3
larger than if no stagnation was present which is the case for the N-80 and 1018 CR
normalized steels. The stagnant condition may create a higher local iron concentration
allowing the crystals to grow larger.
The conditions used to form iron carbonate scales have been identified and are
described in Table ID-7. Characteristics of the iron carbonate scale are summarized in
Table ID-8.
Figure ffl-17. Micrograph Showing the Microstructure of
API N-80 Q&T Steel Specimen, 900X Magnification
Etched with Nital.
Figure HI-18. Micrograph Showing the Microstructure of API N-80
Normalized Steel Specimen, 900X Magnification
Etched with NitaL
Reproduced with permission o f the copyright owner. Further reproduction prohibited without permission.
Figure 0 -1 9 . Micrograph Showing die Microstructure of
AISI 1018 CR Steel Specimen, 900X Magnification
Etched with NitaL
METAL
Figure HI-20. Micrograph Showing the Cross-Sectional Area

of an N-80 Normalized Steel Specimen with a
FeCC>3 Scale, 900X Magnification.
METAL
Figure HI-21. Micrograph of a Cross-Sectional Area of an

N-80 Q&T Steel Specimen with a FeCO-i Scale,
900X Magnification.
97
STEPL Metal is exposed to

corroding medium.
Ferrite corrodes leaving

Pearlite plateletes.
FeCOj crystals grow

between platelets forming
an adherent scale.
Figure HI-22. Mechanism o f FeCOg Formation

on an N-80 Normalized Steel Specimen.
TABLE m-8
Characteristics of FeCOg
- compact
- debonds easy
recrystallized - small crystals
scale (secondary) - non-porous
- protective
- brown color
- non-compact
- porous
non-recrystallized - larger crystals
scale (primary) - non-protective
- well adhered
- black color
99
Iron Dissolution
The specimens used for this series o f tests were API N-80 steel with a
quenched and tempered microstructure. The aqueous chemistry used was 4% brine with
varying amounts of sodium bicarbonate. Table HI-9 describes the three different aqueous
chemistries used. The partial pressure of CO2 and temperature were 150 psi and 160F,
respectively, at a stirring speed of 250 rpm. From these tests, it was found that the maxi
mum amount of soluble iron found in the solution depends on the amount of sodium bicar
bonate added to the solution.
Figures 111-23,111-24, and HI-25 show the amount o f iron in solution as a
function of time. From these figures it can be seen that the amount of iron reached a cer
tain maximum concentration value, which may be higher or lower depending on the origi
nal pH of the solution. After this maximum value of iron concentration had been attained,
and after some time has passed, the amount of soluble iron decreased by about 300 ppm.
One interesting observation made from these figures is that after the iron concentration had
reached its maximum value, the concentration decreased for all cases by about 300 ppm,
after which the specimens were found to have an FeCOj scale. Since one purpose of these
tests was to form iron carbonate scales on specimens to test the scale erosion resistance,
once this decrease had been observed, the specimens usually were taken out of the auto
clave. Identification of the scale was made by the use of X-ray diffraction techniques.
When the specimens were left for longer periods o f time after the 300 ppm
decrease in dissolved iron and after FeC0 3 had precipitated, it appeared that a steady state
condition (equilibrium) was achieved. For Figure HI-23, for example, this equilibrium
condition was reached at a dissolved iron value of 700 ppm. One interpretation of Figure
m -23 is that before the FeCOg precipitates, the solution oversaturates in iron by as much
as 300 ppm above the equilibrium value.
TABLE m -9
Aqueous Chemistry Conditions Used
1.400 ml of 4% Brine
1.400 ml of 4% Brine + 2 g/1 of NaHCOj

1.400 ml of 4 % Brine + 4 g/1 of NaHCOj
1 lO O
1000
I f\ I
Cppm)
900 TEST '
800 i TE%/ \ s j X
700
IRON
600
500
DI SSOLVED
400 Temp 160 F
300
CQ2pp = 150 p sig
200
lOO
-10 10 20 30 40 50 60 70 80 90 100
TIME
Figure m-23. Dissolution of Iron for 4% Brine Only

for Three Tests at Same Conditions.
900
800 .09 Q
\T E S T D
Cppm5
TEST E
700
600
IRON
500 * b - O
400
DI SS OLVED
300
200
100
O 10 20 30 40 50 60 70 80 90
TIME (H ours)
Figure IH-24. Dissolution of Iron in a 4% Brine

Plus 2 g/1 of NaHCOg Solution
for Two Tests at Same Conditions.
500
co2=150Psi
<ppm>
400 T = 160F e e
300
IRON
200
DI SSOLVED
1 00
10 20 30 40 50
TIME
Figure m-25. Dissolution of Iron in 4% Brine

Plus 4 g/1 of NaHC0 3 Solution.
104
It is interesting to see that for each case shown in Figures IH-23, HI-24 and HI-
25, the maximum amount of dissolved iron concentration depends on the presence and
amount of NaHC03. For example, for Figure HI-23 the maximum value of dissolved iron
was 1000 ppm, while for Figure HI-24 it was 400 ppm. Figure HE-26 shows the maximum
amount of dissolved iron concentration as a function of added NaHC03.
It has been found that after this 300 ppm drop in dissolved iron concentration,
FeC 03 scale is formed on the specimen surface. The presence of sodium bicarbonate
(NaHCC>3 ) means that carbonate ions ( C O ^ are present. From these tests it appears that
the more carbonate ions in solution the less the amount of dissolved iron before formation
ofF eC 03 scales. The amount of dissolved iron in solution appears to be inversely related
to the amount of carbonate ions in solution.
It is also interesting to see that for Figures HI-23 to HI-25 the maximum dis
solved iron values, 1000, 800 and 400 ppm, reach a plateau. The concentration is main
tained at this maximum for some period of time ranging from 10 to 30 hrs. And after this
time has passed, FeC 03 forms.
The next section discusses dissolution of iron when the pH is held constant at
3.4, the value of pH corresponding to a solution of 4% brine, a CO2 partial pressure of 150
psi, and a temperature of 160F.
Iron Dissolution at Constant pH
Crolet [28] describes a computer program that allows for the optimization of
the test medium by stabilizing the pH and maintaining, at the same time, a metal/solution
interface sim ilar to those obtained under natural conditions. For our conditions, the opti
mized testing procedure is summarized in Table HI-10 [28].
Figure HI-27 shows the result from a test conducted under these conditions. As
can be seen from the figure, the soluble iron in solution reached a maximum value of 5000
ppm. For this case, the pH was maintained constant at 3.4 and no sodium bicarbonate was
introduced into the system. This case is analogous to that of Figure HI-23, except that in
105
FERROUS ION CONCENTRATION

NaCl PLUS ADDED NaHCOS
1.1
1
CONCENTRATION
(T hauaanda)
O.S
0.7
0.0
IRON
0.4
0 2 4
NaHCOS in irt% /\
Figure HI-26. Maximum Dissolved Iron (Fe"1-^) Concentration

vs. Initial Concentration of NaHCOg in mg/1.
TABLE m-10
Testing Conditions as Described by Crolet T281
1) Prepare the base solution

2) Add 1.149 g/1 of sodium acetate
per every 100 ppm of expected iron
in solution.
3) Acidize with strong acid to pH = 3.4
4) Deaerate
5) Apply pressure and temperature
5500
5000
4500
(ppm)
4000
3500
IRON
3000
2500
DI SSOLVED
2000
CC>2 = 150 psig
1500
T = 160F
1000
500
15 30 45 SO 75 90 105 120 135 150 165

TIME (H ours)
Figure HI-27. Iron Dissolution in 1,400 ml of 4% Brine

Using Crolets Recipe.
108
this case the pH was held constant For this case the maximum amount of dissolved iron
measured was 5000 ppm. After the test period, the specimens were taken out of the auto
clave and an iron carbonate scale was observed.
For this case, it is assumed that a decrease in dissolved iron also occurred to
precipitate the iron carbonate. But it was not detected because of the way the dissolved
iron measurements were made. These measurements were performed by using colometric
kits, and, when iron is found in such large amounts, changes as small as 300 ppm are
impossible to detect.
Table HI-11 summarizes the results of the four types of tests performed in the
autoclave.
Dissolution of Iron Carbonate
Corrosion rates that occur after an iron carbonate scale has been formed are
much different from the corrosion rates that occur when no scale is present. To fully
understand the mechanism of CO2 corrosion, studies on dissolution rates of iron carbonate
are important. Therefore, some experiments were performed to determine the role of
FeCOj dissolution in the erosion-corrosion process.
A piece of siderite (FeCOg) rock was immersed in the autoclave in 1,400 ml of
4% NaCl solution at a pressure and temperature of 150 psig and 160F and at a rotating
shaft speed of 250 rpm. Dissolution of the siderite was determined by measuring the solu
ble iron in a 4% brine solution and in a solution using Crolets [28] recipe.
Results from this experiment are displayed in Figure HI-28. As can be seen
from the figure, the siderite rock released up to 80 ppm of iron in a solution of 4% brine.
On the other hand it released up to 200 ppm in a solution using Crolets recipe. Figure IH-
29 shows the dissolution rate for iron carbonate as well as the dissolution rate for iron. As
can be observed from the figure, the amount of iron (Fe^+) released to the solution is
higher for the iron than for the iron carbonate rock. This suggests that when iron carbonate
is formed on a steel surface, the rate of iron release to the solution could decrease to that of
TABLE m-11
Summary of Tests in the Autoclave for 1,400 ml of Solution.
Solution Maximum Dissolved

Composition. Iron (ppm)
4% NaCl 1000
4% NaCl 800
2 g/1 NaHC03
4% NaCl 400
4 g/1 NaHC03
4% NaCl 5000
Crolets recipe
C 0 2 = 150 psig - T = 160F
250 l i , r i " i i i i
CROLET'S RECIPE
Cppm)
200
150
IRON
DISSOLVED
100
50 4X BRINE ONLY
0
O 20 40 SO 80 100 120 140 ISO 180
TIME (H ours)
Figure m-28. Dissolution of Iron Carbonate in 4% Brine,

Crolets Recipe.
CC>2 = 150 psig T = 160F
55Q Q
5000
E 4500
4000
3500
3000
C ro le t's Recipe
2500
2000
4% B rine Sol
1500
1000
500
-20 o 20 40 60 80 100 120 140 160 ISO

T IM E (H o u rs )
Figure HI-29. Iron and Iron Carbonate Dissolution.
112
the iron carbonate. If the amount of dissolved iron in solution is a form of determining
corrosion rates, then corrosion rates of steel specimen may decrease to those of the iron
carbonate. Because the formation of a secondary scale (recrystallization) has been ob

served, this suggests that even after the formation of the primary scale, corrosion (iron
dissolution) takes place, in which case, the controlling mechanism of CO2 corrosion would
be the dissolution rate of the scale and corrosion through pores in the scale. This suggests
a model explaining an important mechanism in the corrosion process in systems containing
CO2 . In this model, the iron under the scale corrodes and diffuses out through pores of the
scale. Loss of iron at the base of the scale may weaken the bond between the base metal
and the scale causing the iron carbonate crystals to detach from the base ...etal. These
crystals may then be carried into the main flow by convection-mass-transfer. This model
is presented and described in detail in Chapter IV.
The experiment done to study the dissolution of iron carbonate was performed
as described above, using a siderite rock. Siderite occurs naturally in nature. But this does
not imply that the rock is 100% pure FeCOg. From the composition diagram of siderite
[29], it can be seen that it can coexist with Mg and Mn (see Figure EI-30). As siderite is
being formed, if these additional components are present, they will coexist with it. This
means that within the same siderite molecule, one or two atoms of Mn may occupy an
atomic site. Kow many Mn atoms will occupy an atomic site depends on the amount of
Mn present in the environment when FeCO j forms. Take for instance point "X" in Figure
m-30. In the Mg-Mn-Fe system FeCOg could be found up to 80%, with 10% MnCOj and
10% MgCC>3 . In the Mn-Fe system (zero Mg), as much as 90% FeCOj can be found with
10% MnCOg. These additional components in the siderite may play a role in its dissolu
tion. The siderite rock may therefore have a different dissolution rate than that of an iron
carbonate scale. An experiment was done in which an iron carbonate scale was precipitated
onto a stainless steel specimen.
Figure EI-30. Siderite Composition Diagram.
114
Once the scale was formed, the specimen was taken out of the autoclave. The
stainless steel specimen with the FeCOj scale was then immersed in the autoclave with a
new solution batch. The iron carbonate scale dissolved without corrosion taking place.
This dissolution process simulates conditions in which an iron carbonate scale precipitates
on a steel surface and then dissolves. Figure DI-31 shows the result of this experiment. As
can be seen from the figure, the dissolution for this case gave only 100 ppm of dissolved
iron in solution, a smaller quantity than for the previous cases in which the siderite rock
was used.
One interesting observation from this experiment is that the iron carbonate
scale adheres much better to the stainless steel specimen than it did to API N-80 or AISI
1018 specimens. The reason this point is raised is because FeC O j deposition onto a
corroding specimen may be completely different from that deposition occurring onto a
noncorroding one. For a corroding specimen, reactions may be occurring at the interface
between the scale and the metal surface that affect the bonding characteristics of the scale.
Adherence of this scale is another parameter that should be taken into account when deal
ing with C O j corrosion.
In steels, Mn is added as an alloying element to improve strength and notch
toughness. In the case of some API N-80 specimens used, Mn was found in amounts of
1.66%. In the case of the AISI 1018 CR specimens, Mn was found from 0.6-0.9%. These
results suggest that in future studies it may be useful to examine whether the presence of
Mn may play a significant role in the dissolution characteristics of iron carbonate.
C 0 2 = 150psig - T = 160F
250
<ppnO
200
S id a n its Rock
150
IRON
1 00 GB-
DISSOLVED
50 FaC03 on S ta in le s s S te e l
10 0 10 20 30 40 50 60 70 80 90 100
T IM E (H o u rs )
Figure m -3 1. Dissolution of Iron Carbonate Scale from

a Stainless Steel Specimen.
CHAPTER IV
EROSION OF IRON CARBONATE SCALES
An iron carbonate scale was formed on API N-80 and AISI 1018 CR steel
specimens, and they were both tested on the Erosion Apparatus. Conditions at which these
scales were formed were those shown in Table IH-1. X-ray diffraction of the scale showed
that no iron was present on the surface; therefore, the scale was assumed to be dense. The
purpose of this study was to investigate the erosion resistance of iron carbonate scales
when subjected to the mechanical forces of liquid and solid particle impingement. The
liquid used for this series of tests was a light jet turbine oil. The objective of using this
liquid is to study the response of iron carbonate scales to mechanical loadings only, factor
ing out the corrosion component of erosion-corrosion. This oil was also used as the trans
port medium for the particles when solid particle impingement tests were performed. The
particles were suspended in the medium by constantly stirring the solution.
Description of Erosion Apparatus

The Erosion Apparatus has been built to study the erosion resistance on the
FeCOj scales formed at different conditions and subjected to liquid slugs impinging at dif
ferent velocities and angles. Also, the erosion effects of solid particle concentrations in the
liquid. Figure IV-1 shows a photograph of the apparatus. The design of this apparatus was
taken after Camacho [24]; for detail information the reader is referred to this reference.
116
Figure IV-1. Photograph of the Erosion Apparatus for the
Iron Carbonate Studies.
118
Main Features
The main features of the Erosion Apparatus are described below:
It is capable of shooting liquid jets and liquid jets containing solid parti
cles at a target specimen.
It is capable of producing a wide range of velocities, from 50 ft/sec up
to 200 ft/sec.
The velocity of the liquid-solid jet can be measured with the aid of two
photocells.
The specimen can be accommodated at different angles of impinge
m ent
When using solid particles, the particles are maintained in suspension
by a stirrer inside a tank containing the liquid.
Major Components
The main components of the Erosion Apparatus are:
A high pressure, low volume air driven reciprocating pump. This type
of pump has a small piston area and stroke to provide a very small volume
of slurry at high pressure per stroke. This allows each stroke to provide a
single liquid or slurry jet of discrete size at high enough pressures as to
accelerate it to the desired velocities.
A nozzle to accelerate the jet to high velocities. Different nozzles of
different sizes can be placed to achieve the desired velocity conditions.
A receiver tank that provides a reservoir of compressed air for the
pump, since during a pump stroke a very high flow rate of air is required
for a short time.
Two photoelectric transducers to measure the velocity of the jet. The
velocity is determined by measuring the time of flight of the liquid jet
between these two cells, which are located at a known distance apart.
119
Speed control valves to control the pump stroke rate.
A reservoir that collects the liquid and the solid particles after the jet
has hit the target.
The Erosion Apparatus is also equipped with a 16 gallon tank that
contains the liquid or the liquid with solid particles. The tank has a stirrer
that maintains the solid particles in suspension in the liquid.
Liquid Impingement Tests

API N-80 Steel Specimen
This specimen was placed in the Erosion Apparatus and subjected to liquid
impingement at 50 ft/sec at an angle normal to the impinging jet for more than one million
cycles. After the test and analysis o f the specimen it was concluded that even after this
many cycles no mass loss was detected. Looking at the surface of the specimen under an
optical microscope (64X) and the SEM (Scanning Electron Microscope), no damage to the
FeCOj scaled was observed, except in an area adjacent to the reference hole, discussed
below.
To insure that SEM photographs were taken around the same area of the
specimen every time, a very small hole was pierced in the center of the specimen as a
reference point. By doing so, the FeCOj scale broke in the hole, see Figure IV-2. After
exposing the specimen to 1,000 impacts at 50 fi/sec, damage could be observed in the area
adjacent to the pierced hole. This amount of damage was not increased by further expo
sure of the specimen to the 500,000 impacts at 50 ft/sec mentioned above.
The impingement velocity was then increased to 160 ft/sec, and the same
specimen exposed to this velocity. At this velocity, some damage, on an area away from
the reference hole, started to appear. This damage could not be detected by weight loss
measurements but was detected under the SEM. Figure IV-3 shows how the FeCOg scale
was damaged after the specimen had been exposed to additional 300,000 cycles at an
impingement velocity of 160 ft/sec.
Figure IV-2. Micrograph o f a Siderite Scale on N-80 Steel
Showing the Reference Hole. 75X Magnification.
Figure IV-3. Micrograph o f the Siderite Scale on N-80 Steel
after Exposed to Additional 300,000 Cycles of
of Liquid Impingement at 160 ft/sec 470X
Magnification.
122
A ISI 1018 CR Specimen
An iron carbonate scale was formed on an AISI 1018 CR specimen under the
following conditions: 100 psig COj partial pressure, 160F, in a solution of 3% NaCl plus
0.84 ppm of NaHCOj diluted in deaerated water. The scale was identified by X-ray dif
fraction to be siderite; Figure IV-4 shows a SEM photograph of this scale.
This specimen was then exposed, in the Erosion Apparatus, to a velocity of 160
ft/sec. A reference hole was also pierced on this specimen as shown in Figure IV-5. It was
observed, as for the case of the API N-80 steel specimen, that some damage occurred to
the area adjacent to the reference hole after only few thousand cycles, see Figure IV-6 and
IV-7. The specimen was then observed after 200,000 cycles, 400,000 cycles, and
1,000,000 cycles; and no further damage was observed or measured by weight loss meth
ods. These same observations were made on another 1018 CR specimen.
For both types of specimens (N-80 and 1018 CR), the impingement angle was
either 60 or 90, and velocities were 60 ft/sec, 150 ft/sec and 250 ft/sec. The impinge
ment angle for this case is defined as the angle formed between the liquid slug and the
specimen, being 90 normal impingement The number of cycles or impingements was in
some cases up to 1,500,000 impacts. To achieve 1,000,000 impacts, the Erosion Appara
tus was kept running for about 3 to 4 days.
For the 1018 CR specimens, no damage was observed after 1,000,000 impacts.
For N-80 specimens, scale damage was observed in an area other than near the reference
hole in only one case. This might have been due to the fact that the scale was formed on a
steel specimen having a quenched and tempered microstructure. It was discussed in Chap
ter IE that iron carbonate scale on this type o f microstructure was not as well adhered to
the metal matrix as for the 1018 CR specimens with a normalized microstructure.
Figure IV-4. Micrograph of a Siderite Scale on a 1018 CR
Steel Specimen. 520X Magnification.
Figure IV-5. Micrograph of the Siderite Scale on the 1018 CR
Steel Specimen Showing the Reference Hole and a
Crack, in a Direction Radially from the Hole.
95X Magnification.
M ETAt
Figure IV-6. Micrograph o f the Damage that Occurred on the

Area around the Hole after 2,000 Cycles of Exposure
to Liquid Impingement at 160 ft/sec.
S9X Magnification.
126
METAL
Figure IV-7. Micrograph of die Siderite Scale around

the Reference Hole Showing How the Scale
Has Been Removed after Exposed to Liquid
Impingement 600X Magnification.
127
Based on observations made after this series of tests, it was concluded that the
mechanical action of the liquid impingement did not cause the removal of well formed and
well adhered iron carbonate scales. This does not necessarily mean that Kqm'd impinge
ment cannot cause damage at all to carbon steel. From calibration tests performed in the
CO2 loop, it was found that corrosion rates can be as high as 2,0 0 0 mpy for specimens
located at the impingement points of capped tees. This can be explained as follows; con
sider a liquid drop traveling in the gas phase in a CO2 environment. The drop impinging
against the metal surface or FeCC>3 scale may have a pH (pH^) due to the carbonic acid
less than the pH near the metal surface (pHw) (see Figure IV-7). The pHw may be higher
than pH}, because corrosion reactions have been taking place at the liquid-metal interface
that raised the pH near the wall with respect to the pH in the bulk flow. Recall from
Chapter n, where it was mentioned that for every iron ion going into solution, two ions of
carbonate are formed; these carbonate ions increase the pH locally. The drop containing
H 2 CO 3 hits the metal surface with pH^. At that moment, the pH at the metal-drop inter
face equals pHjj, and the iron dissolution rate temporarily increases. But in production
situations there are millions of drops hitting the metal. Under these circumstances, the
wall may be exposed to the bulk conditions nearly continuously, and significant corrosion
damage may result If impingement points at the wall are exposed to the bulk conditions
nearly continuously, a mass-transfer boundary layer may never form, and higher corrosion
rates may occur.
The mechanism in Figure IV-8 may explain why, in the regions of direct im
pingement damage due to erosion-corrosion is very likely to occur. Bussman [31] found
that shear stresses for pipe fitting geometries, i.e., expansions, contractions, are very high
at points of direct impingement ("Reattachment Point"), see Figure IV-9.
128
Tilt 1
WA L L
TIME 2
PIPE
Mass |
transfer
Boundary
Layer
TIME 3
Figure IV-8. Model for liq u id Impingement on a Metal Surface.
REATTACHMENT POINT
RECIRCULATION
REGION
W ALL
r -k /
s e p a r a t io n
DIVIDING
STREAMLINE
AXIS O F SYMMETRY
Figure IV-9. Geometry of a Sudden Expansion [31].

(By Permission o f Author.)
130
Solid Particle Impingement

After finding that liquid impingement tests were not capable of damaging the
iron carbonate scales, it was decided to examine the erosion resistance of the scales to solid
particle impingement. For the solid particles, glass beads of known size and shape were
selected. They are the same type of particles used for the bare metal erosion studies [32].
The sizes of the glass beads used are defined by the distribution shown in Figure IV-10.
For the first set of tests, a specimen with iron carbonate scale was positioned in
the Erosion Apparatus for normal impingement. The specimen was impinged at a velocity
of 160 ft/sec with a solid particle concentration of 0.2% by weight. And at this velocity it
was found that the scale was damaged after just 100 shots. Figure IV -11 shows the area of
the specimen where the scale was removed. Then the impingement velocity was reduced
in increments of 20 ft/sec down to 60 ft/sec. Table IV -1 summarizes the observations

marie after the 1018 CR specimen had been exposed to these different velocities, and Table
IV-2 shows damage after specimens have been exposed to these velocities for N-80 steel
specimens. Figure IV -12 shows a plot of velocity versus the number of impacts required
to damage the iron carbonate scale for two tests. As can be seen from this figure, the lower
the velocity the more impacts required to cause damage to the scale. For these preliminary
tests, damage is defined as deterioration of the scale which is observed with the aid of an
optical microscope having a magnification of 100X.
PARTICLE SIZE DISTRIBUTION
ISC 0S BEKS

59
10
0 rja n K /A A \ Y '* r r -jr * j/7
> * -7 4 74 C B -S 53-44 44-37 37>
R K fiE S E Q K K K )
s#1 E 3 s W #2
Figure IV-10. Particle Size Distribution of Glass Beads [32].
Figure IV-11. FeCOj Scale Damage after It Was
Exposed to .2% Solid Particle
Concentration Impingement; after
100 Liquid/Solid Impacts, 160 ft/sec.
TABLE IV-1
Number of Impacts to Initiate Damage of FeCOg Scale on
A IS I1018 CR Steel
Velocity # Impacts to Initiate Damage

(ft/sec) Test A TestB
160 9 0 -1 0 0 190-210
140 200 - 300 200 - 260
120 600 - 700 700-800
100 1,400 - 1,500 1,700 - 2,000
80 9,000-10,000 10,000 -12,000
60 45,000 - 50,000
TABLE IV-2
Number of Impacts to Initiate Damage o f FeCCh Scale on
API N-80 Steel
Velocity # Impacts to Initiate Damage

(ft/sec)
160 90-110
140 150-200
120 550-600
100 1,400-1,500
80 8,000-9,000
50000
DAMAGE
F q C0 3 on 1018CR s te o l o ld to s t
40000
INITIATE
30000
20000
TO
F q C0 3 on 1018CR s ta el
IMPACTS
10000 F q C0 3 on N8 0 sto o l
50 60 70 80 90 100 110 120 130 140 150 160 170

VELOCITY C ft/s a o )
Figure IV-12. Velocity of Liquid/Solid Jet vs.

Number of Impacts to Initiate Damage.
135
Summary
Observations of the iron carbonate scales show that this scale is extremely brit
tle. But when strong bonding exists between the scale and the metal, erosion damage due
to liquid impingement will not occur on the scale. If the bonding is weak, the FeC0 3 scale
can be easily removed by the impingement action of the liquid even at a velocity of 50
ft/sec.
After observations were made on the N-80 steel specimen, it could be noticed
that some scale was actually removed from the surface of the specimen after 300,000
cycles at a velocity of 160 ft/sec in an area other than around the reference hole. At a
velocity of 50 ft/sec no damage, besides that on the area adjacent to the reference hole,
could be observed.
Observations of the iron carbonate scale on the A IS I1018 CR specimens show
that damage was done only to that area adjacent to the reference hole, and no further
damage was observed on the rest of the specimen, even after being exposed to 1,000,000
cycles at 160 ft/sec.
The fact that the N-80 specimens were damaged in an area other than the one
surrounding the reference hole raises the following argument: As discussed in Chapter III,
the success rate of creating iron carbonate scales on the N-80 steel specimens with
quenched and tempered microstructure was low, and the scale on this type of specimen
was not tightly adhered to the metal surface, making it susceptible to liquid impingement
damage.
On the other hand, the fact that for both steels the FeC 0 3 scale eroded easily
from the area surrounding the reference hole raises the following arguments: Piercing the
reference hole in the center of the specimen created micro-cracks on the FeC 0 3 scale.
Then the impinging action of the liquid on the surface caused these micro-cracks to inter
connect and caused the material to break o u t The existence of these micro-cracks can be
verified by Figure IV-5. This figure shows a micro-crack on the FeC 0 3 scale. This
136
photograph was taken just after the hole was made on the surface, previous to being ex
posed to the impingement forces.
The liquid impinging on the FeCOg scale does not cause further damage other
than that occurring in the area surrounding the reference hole.
What initiates the removal of iron carbonate scales from metal surfaces is the
impingement o f a solid particle against the scale. The panicle damages the scale and
causes micro-cracks. Then the parameter controlling the removal of iron carbonate scales
is the characteristic of the solid produced. It was found by Camacho [24] that a 50 |xm size
solid particle in the flow can cause erosion damage on a bare metal surface. This size
particle could easily damage an iron carbonate scale.
The only way liquid impingement can mechanically damage a scale is if the
scale is already predamaged with micro-cracks or delamination.
Erosion damage by solid particle impingement was found on the FeCC^ scale.
It has been found from the solid particle testing that solid particles do cause damage to the
scale. In fact, damage was observed at 160 ft/sec after only 100 impacts. Whereas no
damage occurred with liquid impingement at 250 ft/sec in up to one million impacts.
Particles do play an important role in the removal of iron carbonate scales. Solid particle
erosion damage is also probably related to particle concentration and size, and velocity and
angle of impingement as observed in bare metal erosion studies. Preliminary observations
from these tests suggest that damage to the iron carbonate scale should be expected to
occur sooner than damage to bare metal.
Since liquid impingement does not mechanically damage a well formed FeCOg
scale, this mechanism can be discarded as a possible controlling mechanism of scale
removal. But there are other mechanisms that may cause the damage to the scale. Two of
those mechanisms are solid particle impingement and dissolution of the scale. A third
mechanism is one proposed in this chapter and it is discussed later.
137
Dissolution of the FeCOg scale is another competing mechanism for scale
removal. In this mechanism, as velocity increases, iron carbonate in the fluid stream
adjacent to the iron carbonate already adhered to the metal is convected away into the main
stream. This creates a concentration gradient which causes the scale to dissolve. Dissolu
tion of the scale causes the metal to be exposed to the fluid medium. If the fluid medium is
corrosive, it then causes further corrosion of the metal. Then the controlling parameter of
the removal o f iron carbonate scales is convective-mass-transfer-controlled [33]. But it
appears that the dissolution of the iron carbonate in CO2 containing environments is a slow
process. It is much slower than the dissolution of iron under the same conditions. If the
dissolution process is a slow one, then it may not play an important role in the removal of
iron carbonate scale because other competing processes are occurring faster. Autoclave
studies done on a piece of siderite (FeCOj) showed that this dissolution process was much
slower than expected. This test was done by using a piece of siderite of known weight
introduced in the autoclave and exposed to the same conditions the scale was formed on to
the metal specimens (see Table III-7L After 72 hours, the siderite piece was weighed
again and found that no mass was lost. For the conditions of Table II-4, the dissolution
process is a very slow one.
A third mechanism is proposed. This mechanism is similar to the mechanism
studied by Luis Sanchez-Caldera [34] for the erosion-corrosion of magnetite. Assuming
the dissolution of the iron carbonate is indeed a slow process, the flowing media contains
no solid particles, and that we have an iron carbonate scale on the inside surface of a pipe
exposed to flowing conditions. Once the FeC 0 3 scale is formed it protects the metal
surface that is directly underneath the scale, see Figure IV-13. But as mentioned before,
this scale is porous, leaving areas of bare metal directly exposed to the corroding medium.
The metal exposed to the corroding medium starts to corrode, see Figure IV-14. These
pores may act as anodic sites in the corrosion process ("Type II scale" [11]) creating pits
which tend to grow underneath the iron carbonate (FeCOg) crystal adjacent to the pit. The
FLO W
^ T T T > o . n m r r r
-unprotected
METAL
protected
Figure IV-13. Schematic of FeCOj Scale on Steel.
FLOW
P IT S
METAL
Figure IV-14. Mechanism o f FeCOj Scale Damage.
copyright owner. Further reproduction prohibited without permission.

Reproduced w ith permission
140
process in which pits grow underneath the adjacent iron carbonate crystals can be visual
ized by comparing it to a corrosion process happening underneath a protective coating (see
Figure IV-15). As the pits grow, the base of the FeCOg crystals adjacent to this pit weak
ens. Then the action of the flow (i.e., shear stresses, turbulent kinetic energy carried by
eddies acting on the already weakened scale) causes this scale to finally debond or break
loose.
Then the flow removes the crystal into the main flowstream by a convection-
mass-transfer process. Once these crystals are removed from the vicinity of the pit, more
metal is then exposed to the corroding medium. The flowing condition helps diffuse some
of the iron ions from the pit into the main flow. So, the higher the velocity, the harder for
the iron ions to reach a local saturation because some of this iron is convected away to the
main flow. Figure IV- 16 depicts and su m m arizes this proposed mechanism. If the dissolu
tion of iron carbonate were an important process, then the mechanism described above in
addition to the dissolution process could cause damage to the metal at a much faster rate.
COAT
METAL
Figure IV-15. Pit Growth Mechanism Underneath

a Protective Coating.
STEP L FeCOj scale precipitates on
PORE to the metal surface leaving
porous areas.
M PIT
E STEPH. Pits grow underneath crystals
T weakening its base.
A
L Shear stresses, turbulent kinetic
energy help debond the ctystai.
STEP IV. Crystal goes into main stream by

a convection-mass-transfer mechanism.
Figure IV-16. Proposed Mechanism for FeCOg Scale Removal.
CHAPTER V
EXPERIMENTAL APPARATUS
To study velocity effects on carbon dioxide corrosion, a two-phase flow loop
was constructed. This loop is called the CO2 Loop. The medium circulated by the Carbon
Dioxide Loop consists of a liquid phase composed of 3% NaCl in deaerated distilled water
and a gas phase of CO2 . The loop has been designed to produce two-phase flow condi
tions at different gas-liquid ratios.
Carbon Dioxide L o o p
Two-Phase Flows
In the oil and gas industry, the type of flow most frequently found in flow lines
and well tubing is two or multiphase flows involving gas (CO2 , H 2 S, etc.), oil, water, and
sand in various mixes. Ellison [35] found that the erosional velocity was affected by flow
patterns in multiphase flow.
Definitions of variables used describing two-phase flows are given below [36]:
Superficial Gas Velocity (vSg): Is the velocity the gas phase would exhibit if it flowed
through the total cross section of the pipe alone.
Superficial L iquid Velocity (vS|): Is the velocity the liquid phase would exhibit if it
flowed through the total cross section of the pipe alone.
Whenever two fluids with different physical properties flow together in a pipe,
there is a wide range of patterns that can form. Flow pattern refers to the distribution of
each phase in the pipe relative to the other phase. Govier and Aziz [37] present a series of
flow patterns for horizontal and vertical flows of water and air. In horizontal flows, for
143
144
instance, the annular mist flow pattern can occur for vSg of about 100 ft/sec and for vsj
from 0.1 to 1 ft/sec. If vSg is sufficiently decreased, slug flow may occur.
Loop Capabilities
The CO2 Loop is designed to produce two-phase flow conditions at different
gas and liquid ratios. The flow patterns produced are stratified, annular, slug, chum, and
froth flow. The capability of the C O j Loop in relation to flow conditions is shown in
Figure V -l. This figure shows a flow regime map in horizontal flows [38], In this figure,
the different flow patterns that form as functions of superficial gas and liquid velocities are
indicated.
The loop is capable of producing superficial liquid velocities up to 6 ft/sec and
superficial gas velocities up to 150 ft/sec. The combination of these velocities will pro
duce the different flow patterns encountered in the oil field pipelines; i.e., stratified, slug,
and annular mist flow, as shown in Figure V -l. The maximum design working pressure is
150 psig at a temperature of 160F. Higher temperatures can be achieved by decreasing
the working pressure. The test section of the CO 2 Loop is designed to accommodate a
variety of geometries; i.e., elbows, tees, reducers, expansions, collars, etc. For the first
series of tests, the test section will consist of three straight sections, a horizontal, vertical
and horizontal, coupled together by elbows, and a section containing three capped tees.
Also, as with the other test loop of the ECRC [27], viewing sections are ahead of each
elbow. These clear viewing sections allow identification of the flow regime. The test
section is equipped with instrumentation that allows for continuous monitoring of parame
ters such as pH, temperature, pressure, and superficial gas and liquid velocities. These
parameters are monitored with transducers through an Analog/Digital-Digital/Analog
board and a computer.
145
f V / T I C 02 LOOP CAPABILITY
---------- ACTUAL CAPABILITY
DESIGN CAPABILITY
20.0
DISPERSED FLOW

Li-
-I
so B U B B L E ,///
>v ELONGATED /
>
SLUG,
BUBBLE FLOW
h- 'FLOW
o 1.0
UJ ANNULAR,
> ANNULAR
g MIST FLOW
ZD
a
_j
_j
<
o
it STRATIFIED FLOW
er
u
a.
ZD
CO
0.01
0.1 1.0 10.0 100.0 50 0 .0
SUPERFICIAL GAS VELOCITY, VSG, FT/SEC
Figure V -l. Flow Regimes - Madhane Correlation Showing

Loop Capability [38].
146
Equipment
The equipment of the CO2 Loop consists of:
"T h e M ain S ep arato r" ( Item # 6, Figure V-2) is designed to hold a 25
gallon sump. It separates the gas from the liquid using a 10 inch diameter by 6 inch thick
mist eliminator. This separator is made o f 316L stainless steel. It is equipped with two
external band heaters to maintain the operational temperature. It is also equipped with a
low liquid level shut down.
"A Secondary Separator (Item # 8, Figure V-2). The main function of this
separator is to separate from the gas any liquid after it has been condensed in one of the
heat exchangers. This separator is also made of 316L stainless steel. The main and sec
ondary separators and the receiver tank have been designed and built by the Erosion/
Corrosion Research Center. The secondary separator is equipped with an automatic air
actuated "dump system." This "dump system" injects back into the main separator the
condensed water that has been trapped, when it reaches a certain level, allowing tests to be
performed for long periods of time without adding make-up water. This pneumatic "dump
system" consists of a floater located inside the separator; when the liquid in this separator
reaches the floater, it automatically opens a valve at the same time it activates the injection
pump.
"T he Condenser Heat Exchanger" (Item # 7, Figure V-2). The function of
this heat exchanger is to condense the liquid that may still be entrained in the gas stream,
to insure that dry CO2 gas enters the compressors. This condensate is then separated by
the secondary separator. The CO 2 gas flows in the tube side of the heat exchanger. These
tubes are made of titanium. The gas entrance and exit cap sections of the heat exchanger
are made of carbon steel clad with 316L stainless steel. The shell, where the cooling water
circulates, is made of carbon steel. Tulsa city water is used as the cooling water in this
heat exchanger. It was designed to cool the CO2 entering at a temperature of 170F down
to 90F assuming summer conditions. (Tulsa city water temperature in summer is 80F.)
147
PSDH
ORAIN
CHECK VALVE
PUM P
1.- Compressors 2.- Cooler Heat Exchanger

3.-Receiver Tank 4.- Gas Flow Meters
5.- Mixing Tee 6.- Main Separator
7.- Condenser 8.- Secondary Separator
9.-Heater lO.-Main Pump
11.-Liquid Flow Meters 12.-Mixing Tank
13.-By-pass Valve 14.-By-pass Filter
15.-C02 Dryer 16.-pH and Temp Probe
17.-CO2 Injection Point
Figure V-2. Schematic of the CO2 Loop.
148
"Heater Heat Exchanger" (Item # 9, Figure V-2). Its function is to increase

the temperature of the CO2 before it enters the compressors for further insurance that the
gas is dry when entering the compressors. This is a counter flow heat exchanger, in which
the gas flows in the shell side o f the heat exchanger, made of carbon steel. The hot water
comes from the "cooler" heat exchanger. The water flows in a fin tube made of aluminum.
The heater was designed to increase the temperature of the CO 2 gas from 70F to 100F.
"Compressors." (Item # 1, Figure V-2). Two compressors, the hearts of the

CO2 Loop, are connected in parallel to provide the gas volumetric flow rate when operat
ing at high velocities. These compressors are each driven by 15 HP electric motors. With
this size motors the compressors are designed to provide gas at velocities up to 150 ft/sec.
"The Cooler Heat Exchanger" (Item # 2, Figure V-2). W ith this heat
exchanger, the temperature of the CO2 gas entering the test section is controlled. This is a
shell and tube type heat exchanger. The CO2 , coming from the compressors, flows in the
shell side made of carbon steel. The cooling water flows in the tube side; tubes are made
of copper. This heat exchanger is designed to cool the CO 2 gas from 250F to 140F. The
water (hot water) coming out of this heat exchanger is used in the "heater" heat exchanger
to heat the CO2 before it enters the compressors.
"The Receiver Tank" (Item # 3, Figure V-2). The main function of this
component is to reduce compressor pulsations and to provide a large reservoir of gas; so
that when operating at high velocities, the gas flow is continuous. This tank is made of
carbon steel, and it has a capacity of 60 gallons.
"T he Main Circulating Pump" (Item # 10, Figure V-2) has a capacity of 16
GPM at a total dynamic head of 115 feet, driven by a 5 HP electric motor. This pump will
recirculate the liquid phase from the main separator back into the test section.
"The Test Section" is made of 1 inch diameter 316L stainless steel. Its total
length is about 30 feet. It has been provided with viewing sections near every test port for
identifying the flow regimes.
149
Instrum entation
The CO 2 Loop is designed for "semi-automated" operation; i.e., the loop will
have instruments monitoring the important parameters that will allow for long, unattended
running periods. For example, instruments will monitor the liquid level in the separators,
pump performance (temperature, vibration, pressure, etc.), compressor performance
(temperature, suction and discharge pressures, vibration, oil pressure, etc.). All these
parameters are connected to an automatic shutdown circuit, recording rime and cause of
shut down. The pH and oxygen level are monitored continuously with in-line type probes.
The deaeration process is described in detail in reference [27].
For tests in which it is desired to maintain the pH constant, a pH control system
is installed to the loop. This system consists on a pH probe, controller, a pump, and a tank
containing a deaerated solution of HC1. This system maintains the pH constant to a desired
value to within plus or minus 0.04.
Pressure and temperature gages are placed throughout the loop to monitor its
operational conditions, i.e., temperature gages at inlet and outlet of every heat exchanger.
Data Acquisition System

The data acquisition system consists of a computer, a METRABYTE analog
to digital-digital to analog (A/D-D/A) converter board, a configuration patch panel, condi
tioning electronics and transducers. This modem data acquisition facility allows for stand
ardization of experimental regimens and eliminates the error associated with manual data
acquisition.
Gas and liquid turbine flow meters are utilized to measure the superficial gas
and liquid flow rates, which then are converted to the respective superficial velocities.
There are two Pt-RTD temperature transducers. One at the test section (T2)
and the other located before the gas turbine meter (Tl). Two strain gage pressure trans
ducers are placed in the loop. One before the gas turbine flow meter (PI), measuring the
gas pressure as it enters the test section; and the other one at the test section (P2). Using
150
these pressures and temperature, and the volumetric flow rate of the gas and liquid flow
meters, the superficial gas and liquid velocities at the test section are calculated.
The software used by the data acquisition system uses METRABYTE soft
ware to drive the A/D-D/A board. A program was developed [38] using this software.
This program also calculates the superficial gas and liquid velocities.
CO; L o o p Operation
Following the schematic of the CC>2 Loop shown in Figure V-2, a description
of the operation of the loop is given: The Compressors (1) discharge the gas at 160 psig
pressure and 250F temperature. After the discharge, the gas is cooled to the desired
temperature through the Cooler Heat Exchanger (2). The gas then goes to the Receiver
Tank (3), then passes through the gas turbine flow meter (4), where flow rates are meas
ured, and enters the test section through the mixing tee (5). A by-pass loop controlled by a
manual globe valve (13) controls the volume of gas entering the test section.
In the mixing tee, the gas mixes with the liquid. A 3% brine solution, serving as
the electrolyte, is prepared externally to the loop in the liquid tank (12). Then it is pumped
into the Main Separator sump (6) where it is deaerated using a vacuum pump. During a
test, the brine is pumped into the test section by the Main Circulating Pump (10) through a
liquid turbine flow meter (11), to measure flow rates, and into the mixing tee (5).
Downstream of the mixing tee is the first horizontal straight segment of the test
section where the gas and the liquid mix and reach the desired velocity. Ahead of each test
cell and throughout the test section are pressure and temperature transducers as well as
gages. Upstream of each test cell there are also clear segments for viewing the flow mix
ture.
When the flow exits the test section it enters the Main Separator (6) where the
liquid and gas phases are separated. The liquid recirculates through the Main Circulating
Pump (10) and the gas flows to the Condenser Heat Exchanger (7) where it is cooled and
entrained water condenses out. The condensed water flows with the gas through the
151
Secondary Separator (8) where the water is separated out. The gas continues flowing
through the Heater Heat Exchanger (9) where it is heated before it enters the compressors
(1). The Secondary Separator (8) is equipped with an automatic, pneumatic rinmp control
system, which injects the condensed water into the Main Separator. In this way, water
entrained in the CO 2 gas is collected and replenished, allowing for long periods of opera
tion.
The C O j Loop is equipped with an automatic pH control system, that injects an
acid solution into the test solution through (port "E") the Main Separator (6). The pH and
temperature compensation probes (16) are located between the Main Separator (6) and the
Main Circulating Pump (10). The pH probe is calibrated before every test
A heater, to maintain the temperature o f the liquid, is provided in the Main

Separator (6).
At the pump discharge, a full-flow strainer and a partial flow filter are provided
in the liquid side of the loop to remove the large and small particles from circulation.
Figures V-3 to V-5 show photographs of the CO2 Loop. Figure V-6 shows a
photograph of the compressors.
Test Cell Design

In single pass CO2 containing flowing systems, the pH and the iron content of
the solution remain constant due to the fact of the continuous replenishment of new solu
tion. But still in these systems iron carbonate scale can be formed. This may be due to the
fact that close to die pipe wall the concentration of iron is higher than that of the bulk flow.
A mass-transfer boundary layer (MTBL) is present within the viscous sublayer (in turbu
lent flows). Within this mass-transfer boundary layer the iron concentration and carbonate
ions may be present in sufficient amounts to form the iron carbonate scale. The amount of
iron and carbonates in the solution contained within the mass-transfer boundary layer close
to the pipe wall depends on the velocity of the bulk flow. The lower the flow velocity, the
larger the thickness of the mass-transfer boundary layer (5C), the higher the iron and
Figure V-3. Photograph of the CO2 Loop Showing the
Test Section and PotentiostaL
Figure V-4. Photograph o f the CO 2 Loop Showing
the Main Separator (Left), Receiver Tank
(Right), and Mixing Tank (Lower Left).
Figure V-5. Photograph of the CO 2 Loop Showing
from Left to Right: Cooler Heat Exchanger,
Heater Heat Exchanger, Secondary Separator,
and Condenser Heat Exchanger.
Figure V-6. Photograph of the Compressors.
156
carbonate concentrations close to the wall, and the higher the possibilities of precipitation
of an FeCOg scale. Formation o f the FeCOj scale leads to lower rates o f dissolution of
iron from the pipe wall. This process is possible provided that mass-transfer is the mecha
nism controlling the corrosion rate. The lower the velocity, the lower the corrosion rate.
Or, in the case that the iron carbonate is already formed, the lower the flow velocity, the
lower the dissolution rate of the scale. On the other hand, as the velocity increases, 8 C
decreases, the iron and/or the carbonate ions are convected away into the bulk flow more
rapidly thereby decreasing their concentration close to the pipe wall. As mentioned before,
the presence of the carbonate ions are associated with a pH which is higher than if carbon
ates were not present The opposite could also be happening. Instead of Fe++ and CC>3 =
ions being convected away as velocity increases, H 2 CO3 present in the bulk flow may be
convected more rapidly to the pipe wall, leading to higher rates of iron dissolution. Figure
V-7 shows a series of actions explaining this mass transfer process.
A new test cell has been designed to allow for studying the mass transfer proc
esses (the Mass-Transfer Test Cell, MTTC) in corrosion and to allow for the use of weight
loss measurements and electrochemical techniques to determine corrosion rates as a func
tion of velocity. This cell has a removable piece o f pipe (a dummy pipe) made of the
material of interest, which is located just upstream of the working electrode. If the pipe is
of carbon steel, as it corrodes it will provide a concentration gradient of iron throughout
the length of this pipe ( a mass-transfer boundary layer will develop) and at the surface of
the working electrode which is placed at the downstream end of the dummy pipe. This
concentration profile is contained within the mass-transfer boundary layer.
The idea of the MTTC is to permit correlation o f the iron concentration gradi
ent with current density, for the conditions of the CO2 Loop. Once concentration gradients
are known, they can be applied to mass-transfer models, and corrosion rates can be esti
mated. These correlations may have the same form as the one presented by Ross and
Jones [40], Equation V -l.
FEARTIE W
ALL BULKFLOY
pH. C03 pH*
HGO3
/U s;ss/;s/ 7/ / / / s / s / / ; ; /; 7777777777-77/r>
777777777771
VI
tfH a, cd,
>7777)7/77/z . /7 / 7 - 7 / // y/ & / / / / / / \
VadCITY V
77/777777777r7 7 /7 /7 A r/7 7777777? 7777777/7777777/7777771
V2 H
jC
D,, ft* ft* f t* f t* CDs
\ 4 ^ /. A A '
c2
^77^7777 7/ /a 777777vJj) 7JV777#77 7777-^ 7 7 M7. //7 J //7 J
VELOCITYV,
V >V
2 1
^C2 < 8C
Figure V-7. Schematic of the Mass-Transfer Process.
158
i = K (AC) z F V-l
where:
i = anodic current density, mA/cm^
K = mass transfer coefficient, g-mole/[(sec cm^)(g-mole/cm^)]
AC = concentration gradient of mass-transfer boundary layer, g/cm^
z = number of electrons exchanged, g.equiv/mole
F = Faraday constant = 96,500 coulomb/g. equiv
Figure V-8 shows a schematic of the test cell. Appendix B contains specifica
tions for the test cell as well as for the electrodes. Figures V-9 and V-10 show photographs
of the test cell. And Figure V-l 1 shows the test cell installed in the loop.
An important feature o f this test cell is that it affords flexibility in the types of
test that can be performed. Test cells are installed in the test section following a viewing
section, which allows for verification of the flow regimes. They are located in the horizon
tal and vertical sections of the test section. The test section also has three capped tees, in
which specimens can be installed to study liquid impingement in the corrosive medium of
the loop. Corrosion rates of the specimens from the tees can be estimated with weight loss
measures and compared to the corrosion rates of the specimens located in the test cell.
Figure V-12 shows a schematic of the test section.
Calibration Tests
Calibration tests on the CO 2 Loop have been performed. The purpose of these
tests is to observe the functioning o f the loop over long periods of time to verify that each
piece of equipment functions according to their design. Parameters such as pH, tempera
ture, pressure, iron counts, oxygen, and velocities were monitored for periods of one week
of non-stop operations. For these tests, the loop was operated in the annular-mist flow
regime.
Figure V -l3 shows the iron concentration as a function of time. This figure
shows how the iron increases up to a maximum value of 100 ppm for calibration test #3
159
STADiESS
oum y PIPE STELPIPE
STAIM.E3S
STEEL PIPE
Figure V-8. Schematic of the Test Ceil.
Figure V-9. Test Cell without "Dummy Pipe" Showing the Electrodes.
Figure V-10. Test Cell with "Dummy Pipe" and Electrodes.
Figure V -l 1. Test Cell in the CO2 Loop, Horizontal Section.
163
TEST 7'
CELL VIEWING s
, SECTION
VIEWING
SECTION 2.5'
TEST CELL
VIEWING SECTION
LIQUID VIEWING SECTION
8.5
V
SEPARATOR
TEST PORTS FOR 1,2 8 3
LIQUID IMPINGEMENT TESTS
Figure V-12. Schematic of the Test Section.
250
C ol lb . to s t #3
<ppm>
200
__ C a l i b . to s t #4
I
ISO /
IRON
/
I
100
DISSOLVED
SO
0
O 20 40 60 80 100 1 2 0 1 4 0 1 6 0 1 8 0 2 0 0 2 2 0 240 260
TIME (H o u r 's)
Figure V-13. Iron Concentration as a Function of Time.
165
and 200 ppm for calibration test #4. For both cases, the flow regime was annular mist
flow; although for calibration test #4, the gas-liquid-ratio (GLR) was slighdy greater than
for test #3. Figure V- 14a shows how oxygen content and pH of the test section varied with
time during the test period for calibration test #3. The oxygen content in the solution
decreased with time until reaching a constant value of 10 ppb. Figure V-14b shows how
oxygen and pH varied for calibration test #4. Figure V-15 shows how temperature varied
with time for both calibration tests. As can be seen, temperature fluctuated between 135-
160F for test #3 while for calibration test #4 the temperature remained somewhat con
stant. After this test, the loop was thermally insulated, and subsequent tests showed the
temperature remained constant at 160F without regulation of the test room temperature.
Figure V -l6 shows the pH variation as a function of the dissolved iron concen
tration for calibration test #4. The figure shows how pH increases with the amount of iron
in solution.
From this series of calibration tests, it was also found that the loop achieved
superficial gas velocities up to about 130 ft/sec and superficial liquid velocities up to 8
ft/sec. With these velocities, still the different flow patterns can be obtained, as shown in
Figure V -l. Figures V-17 and V-18 show photographs of two of the flow patterns pro
duced in the CO2 Loop.
The main purpose o f components such as the condenser and the heater heat
exchangers was to insure the CO2 gas was dry when entering the compressors, in order to
minimize the corrosion of the compressors. To insure the gas was dry when entering the
compressors, corrosion coupons are installed at the inlet of the compressors. These cou
pons are checked periodically. It has been determined from analysis of these coupons that
no corrosion is taking place, which implies the heater and condenser heat exchangers are
performing as they were designed.
As observed in Figures V-14a and V-14b, the dissolved oxygen fluctuated from
test to test, due to the oxygen content of the CC>2- To remove the oxygen from the CO2 , a
166
C02 Loop C alibration Test H 3

4. a 10
4. 7 io o
XI
4. 6 Q. 90
0.
4. 5
80
4. 4 Z
UJ 70
4. 3
u
X
>
X 60
Q. 4. 2 Q
50
4. 1 Ul
> 40
4 _l
a
(/) 30
3. 9 (/)
3. 8 20 OXYGEN
3. 7 10 O'OOOO OOOQ
TIME
5 70
4. 8
JD 60
CL
4. 6 CL
4. 4 50
Z
4. 2 tu
u
w
40
X 4 X
a. o
30
3. 8 D
Li
3. 6
>
J 20
O OXYGEN
3. 4 w
w
lO
3. 2
3 O
0 30 60 90 120 150 180 210 240
TIME (H o u r s)
Figure V-14. a) O 2 and pH as Function of Time for Calibration Test #3.

b) O 2 and pH as Function of Time for Calibration Test #4.
170
160
F5
150
(Dag.
140
130
120
TEMPERATURE
1 10
C alib ration to s t #4
100
90 C alib ration te s t #3
80
70
30 60 90 120 150 180 210 240 270
TIME (H ours)
Figure V-15. Temperature Variation for Calibration Tests.
5
8
C alib ration t e s t #4
3. 6
3. 2
3
0 20 40 60 30 I OO 1 2 0 140 160 180 200 220
D IS S O L V E D IR O N CppirO
Figure V-16. Variation of pH as a Function of Dissolved Iron.
Figure V-17. Photograph o f Stratified Flow.
Figure V -18. Photograph of Annular M ist Flow.
171
deaeration system was designed. This system consists of a canister containing copper
turnings heated to 400F. The C O j gas is passed through this system before it is injected
in the loop. Subsequent tests showed the oxygen level to start up at 5-10 ppb, then de
creased to zero for an entire test period (1 to 3 weeks).
CHAPTER VI
VELOCITY EFFECTS ON C 02 CORROSION
This chapter presents information on a number of tests performed in the C 0 2
Loop system o f the ECRC. These tests were performed at different single and two-phase
flow velocities. The pH was held constant at 3.4 for one set of tests; for another set of tests
the pH was allowed to drift Figures presenting the resuits are followed by a discussion.
These results are grouped into two categories: single-phase flow tests and two-phase flow
tests. The raw data is tabulated and included in Appendix A.
As shown in Figure 1-1, this chapter falls into the category of experimental
studies under the C 0 2 Loop section. This chapter represents an important pan of this
dissertation because it is in this chapter that the effects of flow velocity on C 0 2 corrosion
at a C 0 2 pressure of 150 psig and a temperature of 160F are presented.
Tests in the C 02 L oop

To monitor corrosion rates, electrochemical measurements are performed with
the aid of a software controlled potentiostat. Corrosion rates are calculated using polariza
tion resistance methods, in this way, the slope of the polarization curve is calculated. Then
icorr can be estimated by means of Equation 11-43. Finally Equation 11-44 gives the corro
sion rates in m ils per year. The Tafel slopes values used were Pa = Pc = 120 mV/decade.
Substituting these values in Equation 11-43 and Equation n-44 gives Equation VI-1 for the
corrosion rate of steel.
C.R. = 23,674 x 1 / Q VI-1
172
where:
C.R. = corrosion rate (mils per year)
2 = slope of the linear polarization curve ( AE/Aiappj in mV/|iA, polarization

resistance)
For the tests performed in the loop, the working electrodes were API N-80
grade steel with a quenched and tempered microstructure as shown in Figure 111-17 and
chemical composition shown in Table HI-1, reference electrodes were cast iron and coun
ter electrodes were stainless steel, Appendix B shows a schematic of the electrodes as well
as the chemical composition of the "dummy pipe." Electrodes are located 180 opposite
each other as shown in Figures V-8 to V -l 1. Electrodes are electrically isolated from the
stainless steel test cells by an epoxy coat and shrink tubing on the sides of the electrodes
and tied against a rubber washer. The dummy pipe is also epoxy coated on the outside
surface. Hence, only the surfaces of the pipe and electrodes facing the flow are exposed to
the corroding medium of the CO2 Loop.
To facilitate the interpretation of some graphs, Table V I-1 presents the test
numbers and the conditions at which these tests were performed.
Single Phase Flows

Before describing the test results from the Loop, it is important to describe
some o f the terms used in producing the graphs. Table VI-2 shows an example of how the
data is tabulated. Time is that time in hours when a measurement is made. The terms
H.T., H.B., V.N., and V.S. are designations that describe the position of the electrodes in
the test section. For example H.B. stands for the electrode located in the Horizontal sec
tion of the test section at the Bottom (6:00 oclock position), see Figure V-7; V.S. denotes
the electrodes located in the test cell located in the Vertical section o f the test section
facing South.
Figures showing results show the corrosion rates measured for each set of elec
trodes plus an average line. This average line is found by taking the average over the four
TABLE VI-1
Tests Conditions for COn Loop
T est# v sl V PH
v sg
(ft/sec) (fit/sec)
09 1 0 3.4
10 8.5 0 3.4
11 1 1 3.4
12 1 60 3.4
13 1 60 3.4
14 8 6 3.4
16 8 6 3.4
17 8 6 variable
18 1.2 0 variable
21 8 6 variable
25 2 0 variable
26 8 0 variable
27 2 2 variable
TABLE VI-2
Example of How the Data Is Tabulated
TEST #21 pH = VARIABLE
TWO-PHASE Vsl - 8 ft/sec

Vsg 6 ft/sec
TIME HTOP HBOT VN0R VSOU ROW AVERA

0 769 1024 1168 1353 1078.5
4 1012 1204 1294 1421 1232.75
18. 1 655 397 612 960
24.2 1416 895 1351 1587 1312.25
42.2 1245 874 1489 1578 1296.5
47.5 1293 998 1536 1578 1351.25
55.4 1873 1332 1480 1392 1519.25
71.1 1378 1080 1375 1404 1309.25
92.9 1198 1248 1418 1468 1333
100 1050 1191 1315 1405 1240.25
114.8 1127 1213 1324 1380 1261
129.3 1011 1142 1243 1315 1177.75
143.5 985 1125 1200 1260 1142.5
187 909 1081 1106 1153 1062.25
202.2 891 992 1053 1166 1025.5
217.9 861 953 959 962 933.75
253.8 782 826 804
283.1 861 805 894 1014 893.5
318 864 789 865 927 861.25
319.9 847 749 820 953 842.25
COLUMN
AVERAGE 1051.35 995.9 1184.315 1277.684 1140.881
WEIGHT
LOSS 1296 905 1462 1488
176
sets of electrodes (row average in Table VI-2). Sometimes one or more electrodes are left
out of the average. For example, when measuring corrosion rates in stratified flow, the
corrosion rate from the electrode located at the horizontal top (H.T.) of the test section will
be left out of the average since the flow past this electrode is much different from the flow
past the other three electrodes.
In the figures presented in this chapter, above the figures, some numbers are
shown. These numbers represent the average corrosion rates as measured by weight loss
techniques at the end of the tests. They are presented in the figures as references.
Figure VI-1 shows the corrosion rate for a test having superficial liquid veloci
ties of 1 ft/sec; the pH was kept constant at 3.4. For this case, the average corrosion rate
shown is over three electrodes instead of four. The data from the H.T. electrode was not
included because of the wide spread in corrosion rate. At this low velocity, gas bubbles
develop. These bubbles ride on the top of the flow, causing the electrodes to be wetted for
some measurements and dry for other. This causes the electrochemical measurements to
fluctuate. For this case, the corrosion rates varied from 50 mpy to 3,000 mpy. The bub
bles present in this case may have also contributed to the low corrosion rates for this elec
trode as measured by weight loss techniques, which was 269 mpy. For the other three
electrodes, electrochemical corrosion rates agree with the weight loss measurements
averaged over these three electrodes, about 1,400 mpy.

Figure VI-2 shows corrosion rates for a test with superficial liquid velocity of 8
ft/sec at constant pH of 3.4. The average corrosion rate for this case is averaged over the
four electrodes. The spread in the data for this case as compared to the previous case is
less because no gas bubbles formed. It can be seen that a corrosion rate of 1,200 mpy
characterizes this system. This corrosion rate, measured electrochemically, agrees well
with the corrosion rates calculated from weight loss measurements, which were also
around 1,200 -1,300 mpy. At these higher liquid velocities the system seems to behave
well electrochemically because the flow is continuous, without the formation of gas bub-
TEST 09
WEIGHT LOSS
H.T. = 230 mpy
H.B. = 1,392 mpy
V.N. = 1,348 mpy
V.S. = 1,244 mpy
SINGLE PHASE - Vsi = 1 ft/s e c

TEST 0 9 3 .4
2
1.9
1.5
1.7
1.5
1.5
CORROSION RATE (m py)
1 .4
1.3
1 .2
(Thouaanda)
1.1
1 -
0 .9 -
0 .5 -
0 .7 -
0 .5 -
0 .5 -
0 .4 -
0 .3 -
0.2 -
0.1 -
o -in.
o 20 40 60 so 100
TIME (hr*)
H.T. + H .5. 4 V.N. A V.S. AVERAGE
Figure VI-1. Corrosion Rates for Single Phase Flow Tests with
Vsi = 1 ft/sec and pH Constant at 3.4.
178
TEST 10
WEIGHT LOSS
H.T. = 1,225 mpy
H.B. = 1,256 mpy
V.N. = 1,196 mpy
V.S. = 1,287 mpy
SINGLE PHASE - Vsl = 8 f t / s e c

TEST 10
2
1 .0
1 .8
1 .7
1 .8
1.S
1 .4
1 .3
1.2
(Thouaanda)
1 .1
1
0.0
0.8
0 .7
0.8
0 .3
0 .4
0 .3
0.2
0.1
0
0 20 40 60 80 100 120
TIME (hr)
H.T. + H.B. 4 V.N. A V.S. AVERAGE
Figure VI-2. Corrosion Rates for Single Phase Flow Tests with
Vsi = 8 ft/sec and pH Constant at 3.4.
179
bles which may interfere with the measurements. This continuity also occurs for the
bottom electrode (H.B.) and the two vertical electrodes V.N. and V.S. even if the flow
velocity is as low as 1 ft/sec. These three electrodes see a more continuous liquid phase
than the H.T. one. Comparing tests of Figures VI-1 and VI-2, they both have similar
corrosion rates. It appears that velocity did not have a significant influence on the corro
sion rates for single-phase flows for these conditions; i.e., CO 2 pp = 150 psig, T = 160F.
Figure VI-3 shows the variation of ferrous ion concentration for both tests.
Figure VI-4 shows the average corrosion rates for three tests having superficial
liquid velocities of 1.2 ft/sec, 2 ft/sec and 8 ft/sec, respectively. For these cases the pH was
not kept constant; it was permitted to increase as the corrosion progressed. The figure
shows how corrosion rates decrease with time for two of these cases; while, it remained
constant for another. From the figure, it can be seen that the corrosion rate for the test of
Vsj =1.2 ft/sec starts high, at about 1,800 mpy, and gradually decreases to about 800 mpy
and then it decreased rapidly to 500 mpy after adding sodium bicarbonate (NaHCOg). A
decrease in corrosion rate was also observed for the case of Vsj = 2 ft/sec; in which the
corrosion rate decreased from about 2,300 mpy to about 200 mpy, an order of magnitude
difference. This difference of about 1,300 mpy for the former case and about 2,100 mpy
for the latter from the original corrosion rates was not observed for tests in which the pH
was held constant at 3.4. An even more important observation is that for these two cases
an FeCC>3 (iron carbonate) scale was detected on the surface of the electrodes at the end of
the test. FeCC>3 scale was not observed for the case where the pH was held constant nor
for the case of Vsj = 8 ft/sec in which the pH was allowed to increase. For the 1.2 ft/sec
velocity test, the decrease in corrosion rate observed, and perhaps the formation of the
FeC0 3 scale, occurred after adding sodium bicarbonate to the test solution. A 2 g/1 solu
tion of sodium bicarbonate was added to the test solution in the loop in sufficient quantity
to increase the pH to 5.5. The addition of sodium bicarbonate to this test was done, be
cause it has been experienced in the autoclave that the iron carbonate forms after the pH
FERROUS IRON CONCENTRATION
CONSTANT pH - 3 .4
BOO
400
(p p m )
300
IKON
DISSOLVES
200
100
0
0 20 40 80 80 100 120
TIME (h r* )
VM 1 tt/mma + Vd - 8 f t/M O
Figure VI-3. Variation of Ferrous Ion Concentration for Single Phase

Flow Tests Having pH Constant at 3.4.
TEST 25 TEST 26
WEIGHT LOSS WEIGHT LOSS
H.T. = 1,468 mpy H.T. = 1,903 mpy
H.B. = 1,066 mpy H.B. = 2,016 mpy
V.N. = 1,036 mpy V.N. = 1,662 mpy
V.S. = 1,151 mpy V.S. = 1,609 mpy
SINGLE PHASE FLOW - pH = VARIABLE

TESTS 1 8 . 2 5 . 2 8
(m p y )
RAT*
200
TUIE (h ra )
Val - 1 .2 n/mmm + Val - 2 f t / a
Val 8 f t /a a o
Figure VI-4. Corrosion Rate for Single Phase Flow Tests with
Vsj = 1.2,2 and 8 ft/sec and Variable pH.
182
has reached a value greater than 5.3. After the addition o f NaHCOj there was a rapid
decrease in corrosion rate as well as an increase of pH as shown in Figure VI-5. After a

while, the test was terminated by a leak in the pump seal. Then the specimens were
examined under X-ray diffraction, which identified the presence of an iron carbonate seals.
This scale was very porous and thin. In the case for which the velocity was 8 ft/sec, no
FeCOg scale was formed and corrosion rates decreased only slightly, remaining nearly
constant at about 1,200 mpy, as measured electrochemically. Formation of an FeCO j
scale was also found for the 2 ft/sec case. In this case the scale formed naturally without
the addition of sodium bicarbonate. The corrosion rates for this case dropped by one order
of magnitude, from about 2,000 mpy at the beginning of the test to about 200 mpy at the
end. Figure VI-6 shows the decrease in corrosion rate as pH increased. This figure shows
that there is a rapid decrease in corrosion rates as compared to Figure VI-5.
Figure VI-7 shows that for the test having single-phase velocity of 8 ft/sec, the
corrosion rates stayed constant throughout the test period, even though pH increased. For
this case, the increase in pH did not affect the corrosion rates. Figure VI-8 shows more
clearly how corrosion rate changes as pH increases for the single-phase velocity tests.
Figure VI-9 shows the variation of ferrous ion concentration as a function of time for the
single-phase velocity tests.
Two-Phase Flows
Figure VI-10 shows a plot of corrosion rates for a test performed at a superfi
cial liquid velocity of 1 ft/sec and a superficial gas velocity of about 1 ft/sec. The flow
pattern identified for this condition was a slug flow for the horizontal section of the test
section (H.T. and H.B) and chum flow for the vertical section of the test section (V.N. and
V.S.). The pH for this case was kept constant at 3.4 by adding HC1. Corrosion rates for
the H.T. electrode varied from 200 to 2,000 mpy. This was due to the presence of the gas
bubble riding on the top of the flow, interfering with the electrochemical measurements.
Therefore, for this case, the average corrosion rate was taken over three electrodes only.
CORROSION RATE AND pH
vi - 1.2 n/i - pH
2 .1
2
(mpy)
RATE
1
-8
0.6
-6
-4
-2
0
0 20 40 0 0 100 120 140 160 180 200
TIME (hra)
V*J - 1.2 ft/M S + pH
Figure VI-5. Corrosion Rate and pH for Single Phase Flow Test
with Vsi = 1.2 ft/sec.
v*i
2
(mpy)
CORROSION RATE
O.S
-6
0.4. -4
0
0 20 40 O so 100
TIME (hra)
Vat - 2 f t / m + pH
F ig u re VI-6. Corrosion Rate and pH for Single Phase Flow Test

with Vsi = 2 ft/sec.
Vl I ft/M Q pH
2.S
2
(mpy)
ION RATE
1
-8
0.0 -6
-4
-2
0
0 20 40 SO SO 100 120 140 ISO ISO
TUIC ( h n )
VM m S n/mmm + pH
Figure VI-7. Corrosion Rate for Single Phase Flow Test with
Vsi = 8 ft/sec and pH.
VARIABLE pH
2.6
2 .4 -
23. -
2 -
1.5 -
1.6 -
1 .4 -
1.2 -
1 -
0.6 -
0.6 -
0 .4 -
03 -
0 -- 1 I 1 1 1 r
S .4 S3 43 4 .6 B 8 .4 B.6
pH
Y1 - 13 ft /a a a Vi - 2 ft/'aao
Val - 8 f t / n o
Figure VI-8. Corrosion Rate vs. pH for Single Phase Flow Tests
with Vsl = 1.2,2 and 8 ft/sec.
187
SINGLE PHASE FLOW - pH = VARIABLE

FERROUS CONCENTRATION
00
BOO
(p p m )
400
IRON
300
DISSOLVED
200
100
0 20 40 0 0 100 120 140 ISO 200

TIME ( h ra )
Val - 1 .2 ft/'aao -l- Val - 2 ft /a o o
o Val - n / a a a
Figure VI-9. Variation of Ferrous Ion Concentration for Single Phase Flow Tests
with a Vsi = 1.2,2 and 8 ft/sec at Variable pH.
188
TEST 11
WEIGHT LOSS
H.T. = 1,172 mpy
H.B. = 1,597 mpy
V.N. = 1,345 mpy
V.S. = 1,331 mpy
2 PHASE Vsl = 1 f t / s e c , Vsg = 1 f t / s e c

TEST 11 - pH = 3.4.
3 .2
2.8
2.6
2 .4
(Thouaanda)
1.8
1 .4
1.2
0.8
0.6
0 .4
0.2 -j |
0 20 40 80 80 100
TIME (hra)
a H.T. + H .8. V.N. A V.S. AVERAOE
Figure VI-10. Corrosion Rate for Two-Phase Flow Test

Vsl = 1 ft/sec, Vsg = 1 ft/sec, and pH = 3.4.
189
The average corrosion rate for this case is at around 1,400 mpy which compares closely to
the average corrosion rate measured by weight loss methods of 1,425 mpy. Figure VI-11
shows variation of ferrous ion concentration with time for this two-phase flow test
Figure V I-12 shows corrosion rates for two tests having a superficial liquid
velocity o f 1 ft/sec and superficial gas velocity of 60 ft/sec. The pH was kept constant at
3.4. The corrosion rates from weight loss measurements for test 12 shown in the figure are
much higher than those measured electrochemically. Electrochemically measured corro
sion rates averaged about 400 mpy, while weight loss values were about 1,600 mpy. The
difference between the electrochemical measurements and the weight loss measurements
may be due to higher gas velocities. These higher gas velocities decrease the thickness of
the liquid film on the inner pipe wall which may introduce a high IR drop in the electro
chemical measurements. IR drop is a voltage error in electrochemical measurements due
to the resistance of the electrolyte solution between the working and reference electrode.
The corrosion rates shown in Figure VI-12 for test 13 are lower than the corro
sion rates shown for test 12 by a factor of 1/2. The flow conditions were exactly the same
for both tests. Again for test 13 the corrosion rates measured electrochemically were much
lower than for the ones measured by weight loss. By examining the electrodes after the
test it was found that the test 13 specimens had a scale. The scale was not FeCOj. This
scale was dark and soft and appeared similar to dry mud flakes. In this test, oil was dis
covered to have leaked past the compressor seals. This oil mixed with the test solution of
the loop. It is possible that the oil may have affected test 13 as well as a later test. Figure
VI-13 shows the variation of ferrous ion concentration for the tests of Figure VI-12. From
Figure VI-13, it can be seen that the amount of dissolved iron in the solution for test 12 is
about two times as much as for test 13, where oil was present
Figure VI-14 shows the corrosion rates for a test with a superficial gas velocity
of 6 ft/sec, superficial liquid velocity of 8 ft/sec and a constant pH of 3.4. In this Figure,
the average corrosion rate is computed over three electrodes (H.T., V.N., V.S.). In this
190

Val 1 f t /a a o , Vag m 1 ft/a a o p H aS .4
SOS
400
300
WON
DISSOLVED
200
100
0
0 20 40 SO SO 100 120
TIME (lira)
Figure VI-11. Ferrous Ion Concentration for a Two-Phase Flow Test

Having Vsj = 1 ft/sec and VSg = 1 ft/sec.
191
TEST 12 TEST 13
WEIGHT LOSS WEIGHT LOSS
H.T. = 1,732 mpy H.T. = 475 mpy
H.B. = 1,283 mpy H.B. = 942 mpy
V.S. = 1,915 mpy V.N. = 388 mpy
V.S. = 1,167 mpy
CORROSION RATE - pH = 3 . 4
Val m 1 f t /a a o . Vag - f 0 ff/a a o
2.*
2 .4 -
22 -
2 -
-
13 -
1 .4 -
13 -
1 -
03 -
03 -
0 .4 - h
-B -
03 -T

0 1------------r I ~I-------- 1 -I
0 20 40 80 80 100
TIME (hr*)
n TEST 12 + TEST IS
Figure VI-12. Corrosion Rate for Two-Phase Flow Test

Vsi = 1 ft/sec, VSg = 60 ft/sec, and pH = 3.4.
192

Val at 1 f t / n o . V ag m > 0 f f / a M
too
S00
(p p m )
400
IRON
300
DISSOLVED
200
100
0
0 20 40 tO 80 100
TIME (h ra )
TEST 1 2 + TEST I S
Figure VI-13. Variation of Ferrous Ion Concentration for Two-Phase Flow Tests
Having Vsl = 1 ft/sec, Vsg = 60 ft/sec, and pH = 3.4.
TEST 14
WEIGHT LOSS
H.T. = 1,436 mpy
H.B. = 181 mpy
V.N. = 1,446 mpy
V.S. = 1,587 mpy
2 PHASE V s l= 8 f t /s e c , V s g = 6 f t /s e c
TEST 14 pH = 3.4.
2
1 .9
1.8
1 .7
1.8
1 .5
(m py)
1 .4
1 .3
1.2
(T houaanda)
1.1
CORROSION RATE
1
0 .9
0.8
0 .7
0.6
0 .5
0 .4
0 .3
0.2
0 .1
0
0 20 40 80 80 100
TIME (hr*)
O H.T. + H.B. O V.N. 4 V.S. AVERAGE
Figure VI-14. Corrosion Rates for a Two-Phase Flow Test

Vsi = 8 ft/sec, Vsg = 6 ft/sec, and pH = 3.4.
test, the corrosion rate started high and decreased gradually to a corrosion rate of about 700
mpy. The corrosion rates for the H.B. electrode started at about 950 mpy and decreased to
an average of about 160 mpy. The electrochemically measured corrosion rate for this elec
trode, 160 mpy, agrees well with the corrosion rate measured by weight loss, of 181 mpy.
The reason for the behavior of this electrode is unknown. No FeC0 3 scale was found on
this electrode. The corrosion rates on the other three electrodes measured by weight loss
measurements were about 1,500 mpy. On the other hand, the average corrosion rate
measured electrochemically for the other three electrodes were about 800 mpy. This dif
ference may again be due to the flow pattern introducing an IR drop as for the case of
= 60 ft/sec.
For Figure VI-15, the flow conditions were two-phase flows with Vsj = 8 ft/sec
and VSg = 6 ft/sec. The average corrosion rate was computed over two of the electrodes,
the H.B. and the V.S. Those two were the only electrodes in this test for which electro
chemical measurements were taken. The reason for doing this, was to determine if making
electrochemical measurements changed the surfaces of the electrodes compared to surfaces
of electrodes that were not disturbed by electrochemical measurements [41]. But no visi
ble difference was observed in the condition of the surfaces of these electrodes as com
pared to electrodes for which electrochemical measurements were made. And no differ
ence in corrosion rate by weight loss measurements was observed. Weight loss measure
ments for electrodes where electrochemical measurements were performed had corrosion
rates of about 2,000 mpy as compared to about 1,900 mpy for electrodes where no meas
urements were performed. No iron carbonate scale was formed on any of the specimens.
Corrosion rates as measured by weight loss methods for test 12 of Figure VI-12
are higher than those measured electrochemically. Corrosion rates measured electrochemi
cally show a difference of about 1,000 mpy with respect to weight loss measurements. The
presence of large amount of gas and small amount of liquid (high GLR) in the flow have
affected the electrochemical measurements by reasons explained before.
195
TEST 16
WEIGHT LOSS
H.T. = 1,914 mpy
H.B. = 2,053 mpy
V.N. = 1,940 mpy
V.S. = 1,991 mpy
2 PHASE V s l= 8 f t / s e c , V s g = 6 f t / s e c
t e st is pH ** 3 .4
1.t -
1 .8 -
1 .7 -
1 .6
1 .3 -if
1 .4 -
1 .3 -
1.2
(ThousaiKla)
0.8 -
0.8 -
0 .7 -
0.6 -
0 .3 -
0 .4 -
0 .3 -
0.2 -
0.1 -
0 20 40 60 80 100 120
TIME (hra)
n H.6. + V.S. AVERAGE
Figure VI-15. Corrosion Rate for a Two-Phase Row Test with

Vsi = 8 ft/sec, VSg = 6 ft/sec, and pH Constant at 3.4.
196
On the other hand, for test having lower GLR the difference between electro
chemically measured and weight loss corrosion rates is smaller.
Figure VI-16 shows the amount and variation of ferrous ion in the CO2 Loop
versus rime for the two-phase flow tests mentioned above. The testing conditions for these
two tests were Vsj = 8 ft/sec and VSg = 6 ft/sec. From the figure it can be seen that there is
a difference of about one order of magnitude in the concentration of ferrous ion. This
difference may again be caused by the oil leaked from the compressor seals detected in test
13 of Figure VI-13. On the other hand, the corrosion rates are different only by about 800
mpy, measured electrochemically as well as by weight loss. The lower concentration of
ferrous ion belongs to the test with lower corrosion rates. After tests 13 and 14, the com
pressor seals were fixed and the presence of oil in the test solution in the loop was elimi
nated for subsequent tests.
Figure VI-17 shows corrosion rates for three two-phase flow tests in which the
pH was permitted to drift as corrosion occurred. Test 17 and 21 were performed both at
the same conditions; i.e., V$i = 8 ft/sec and VSg = 6 ft/sec. The conditions for test 27 were
Vsi = 2 ft/sec and V Sg = 2 ft/sec. For tests 17 and 21 the average corrosion rates were
performed overall four electrodes, while for test 27 only three electrodes were included in
the average. For this last case one of the electrodes (V.S.) was excluded from the electro
chemical measurements for the same reason as for test of Figure VI-15, i.e., test 16. After
analyzing the electrodes and comparing them one to another, no difference was observed
between the electrodes that underwent electrochemical measurements and the one that did
not. It turned out that the corrosion rate as determined by weight loss methods was highest
for the undisturbed electrode as compared to the other three. The corrosion rate of test 21
shows a low corrosion rate value after about 20 hours of operation, this value was low
because the temperature of the system dropped to 130F due to a malfunction, which was
fixed thereafter.
197
FERROUS ION CONCENTRATION - pH = 3 .4

Val - f t / . a o , Yap - f t/a a o
2.S
2
1.S
(ppm)
1 .4
o.
0 .4
0
0 20 40 0 0 100 120 140
TIME ( h r a )
TEST 1 4 + TEST 1 0
Figure VI-16. Variation of Iron Concentration for Two-Phase Flow Tests

at Vsl = 1 ft/sec, Vsg = 60 fi/sec, and Constant pH = 3.4.
For the case of test 17, in Figure VI-17, the corrosion rates started high at a
value o f 2,201 mpy and slowly decreased to a characteristic value o f about 1,300 for an
approximate decrease o f 700 mpy. Comparing this characteristic value to the corrosion
rates using weight loss methods (2,000 mpy), there is a difference of about 700 mpy. Test
conditions of test 21 were the same as those for tests 17, except that the test period for this
case was longer. Comparing these two tests, it can be seen that the corrosion rates for both
tests are about the same 1,300 mpy up to 164 hours. After this period, corrosion rates for
test 21 start decreasing to about 800 mpy. The characteristic corrosion rates from weight
loss measurements for test 21 are about 1,200 mpy which are about the same as the elec
trochemically determined ones, of about 1,200 mpy also. On the other hand, test 27
showed lower corrosion rates than for the two previous cases. The characteristic corrosion
rates from electrochemical measurements are about 1,100 mpy while for weight loss
methods are about 1,500 mpy.
Summary
The following observations refer to corrosion testing in the CO2 Loop at a
temperature of 160F and a CO2 partial pressure of 150 psig.
Effect of pH and Velocity

The corrosion rates (from both weight loss and electrochemistry) for the two-
phase flow tests in which the pH drifted are similar to the corrosion rates in which the pH
was held constant at 3.4. For instance, characteristic corrosion rates (electrochemically)
for test 16 in Figure VI-15 (pH = 3.4) were about 1,300 mpy which is about the same as
for test 17 in Figure VI-17 (pH = variable), see Figure VI-18. Therefore, for two-phase
flow conditions, corrosion rates were independent of pH.
The same observation can be made for the single-phase flow tests in which
the Vsi was 8 ft/sec. At this high liquid velocity, pH did not seem to be a factor in corro
sion rates either. Where pH was held constant in one test and allowed to increase in the
199
TEST 17 TEST 21 TEST 27

WEIGHT LOSS WEIGHT LOSS WEIGHT LOSS
H.T. = 1,931 mpy H.T. = 1,296 mpy H.T. = 1,609 mpy
H.B. = 1,710 mpy H.B. = 905 mpy H.B. = 1,386 mpy
V.N. = 2,014 mpy V.N. = 1,462 mpy V.N. = 1,522 mpy
V.S. = 2,586 mpy V.S. = 1,488 mpy V.S. = 1.654 mpy
CORROSION RATE - TWO-PHASE FLOWS

TESTS 1 7 . 2 1 . 2 7 - pH - VARIABLE
(m py)
(T hauaonda)
RATE
CORROSION
400
TIME (h r* )
Vb1b | ip a ,V s g - fp a V a l f p a . V a p - t fpa
O V a l 2 f p * .V e fl 2 f p a
Figure VI-17. Corrosion Rate for Two-Phase Flow Tests with

Vsi - 8 ft/sec, VSg = 6 ft/sec,
Vsi = 2 ft/sec, VSg = 2 ft/sec,
and Variable pH.
200
TW O -P H A S E F L O W S FROTH FLOW
TEST 1. 1 7 Vsl - 8 fp s , Vsg - C fp s
2.8
2 .4
2.2
1 .8
1 .8
(Thousand*)
1 .4
1.2
0.8
0 .8
0 .4 -
0.2 -
0 20 40 SO 80 100 120 140 180

TIME (hrs)
D pH - VARIABLE + pH - S .4
Figure VI-18. Corrosion Rates for Two Tests Having the Same
Two-phase Flow Condition but Different pH.
201
other, characteristic corrosion rates o f 1,200 to 1,300 mpy were found for both tests, see
Figure VI-19. Figure VI-20 shows corrosion rates for single-phase and two-phase flow
tests with both constant and variable pH. As shown in this figure, corrosion rates are about
the same for both 8 ft/sec single-phase flows and two-phase flows tests, and independent of
pH.
For low velocity single-phase tests, pH was a factor in determining the corro
sion rates. For constant pH, corrosion rates were high at around 1,300 mpy. For pH varia
ble corrosion rates decrease to about 200 mpy and a FeCOj scale was formed, see Figure
VI-6.
It is important to point out that corrosion rates were nearly independent of the
pH of the solution for all flow conditions except the lower single-phase flow velocities.
For all cases involving a high degree o f mixing and turbulence (high velocity single-phase
flow and two-phase flows), the corrosion rates were in the range 1,200 to 1,500 mpy and
appeared to be independent of pH and flow velocity.
Figure VI-21 shows the average corrosion rates for five tests at different flow
conditions and pH. From the figure it can be seen that for the pressure (CO2 PP = 150 psig)
temperature (160F) and flow conditions (high velocity single-phase flow and two-phase
flow) at which these tests were performed, the flow velocity and flow conditions (single or
two phase) did not play a significant role on the corrosion rates.
A summary of corrosion rates for all tests performed at CO2 PP of 150 psig
and temperature of 160F is presented in Table VI-3
Effect of Local Turbulence
Even for the case in which FeC0 3 was naturally formed in the loop, VS1 = 2
ft/sec, it can be seen how the local turbulence affected corrosion in some areas. Chapter V
described in detail the design of the test cell used for these tests. In the test cells a piece of
pipe, called "dummy pipe," is placed in the cell as depicted in Figure V-10. Once this pipe
SINGLE PHASE FLOW - Vsl = 8 fp s
TEST O*. 2 pH - 3 .4 AND VARIABLE
2.B
2 .4
2.2
2
1 .8
1 .6
(ThouMnda)
1 .4
1 .2
0.8
0 .6
0 .4
0
0 20 40 0 80 100 120 140 180 180
TtME (hr*)
pH at 3 .4 + pH m VARIABLE
Figure VI-19. Corrosion Rates for Two Tests Having the Same
Single Phase Flow Conditions but Different pH.
203
SINGLE PHASE AND 2 -P H A S E FLOWS

TEST 1 0 . 1 . 1 7 . 2 8
2.8
(m p y )
(T h o u sa n d s)
CORROSION RATE
180
TIME ( h r s )
O Vs< 8 f p s + Vsl - f p s
O V ils M p ti V tg s lf p * A V s la S f p a . V i g M f p *
Figure VI-20. Corrosion Rates for Single Phase Flow Vsj = 8 ft/sec
and Two-phase Flow Vsj = 8 ft/sec, and VSg = 6 ft/sec.
204
SINGLE PHASE AND 2 -P H A S E FLOWS

TEST 1 0 . 1 1 . 17. 2 * . 2 7
2 .4
2.2
(mpy)
1 .8
CORROSION RATE
0.8
0.8
0 20 40 80 80 100 120 180 200
TIME (hra)
Val m a fpa + V slB lfp a , Vfl1 tp > Vl8 fp , V ag~8fp a .
A Vsl 8 fp a X V 0 -2 fp ^ V at2fpa
Figure VI-21. Corrosion Rates for 5 Tests Having Different

R ow and pH Conditions.
TABLE VI-3
Summary o f Corrosion Rates for Loop Tests
T est# Vsl Vsg pH Corrosion Rate (mt

(ft/sec) (ft/sec) W. L * Elec.
09 1 0 3.4 1,400 1,400

10 8.5 0 3.4 1,200 1,400
11 1 1 3.4 1,300 1,400
12 1 60 3.4 1,600 400
13 (oil) 1 60 3.4 700 2 00
14 (oil) 8 6 3.4 1,400 1,100
16 8 6 3.4 1,700 1,200
17 8 6 variable 2 ,0 0 0 1,400
IS 1.2 0 variable 1,000
21 8 6 variable 1,300 1,200
25(FeC03) 2 0 variable 1,000 2 00
26 8 0 variable 1,400
27 2 2 variable 1,500 1,100
* Corrosion rates measured by weight loss methods.

** Characteristic Corrosion rate, calculated from electrochemical measurements
Characteristic Corrosion Rate is the corrosion rate that best describe the corrosion
behavior of the system throughout the test period.
206
is in place, there is a small gap present between the "dummy pipe" and the stainless steel
cell. This gap induces turbulence. Where the turbulence is induced, an iron carbonate
scale never forms and therefore corrosion damage to the pipe is w orst Figures VI-22 and
VI-23 show how the "dummy pipe" corroded down stream o f this gap. Only this area
experienced severe corrosion, while corrosion in the rest of this pipe is much less. This
type of phenomenon was observed most frequently during single-phase flows at low veloc
ities (2 ft/sec) and variable pH.
On the other hand, for cases o f constant pH having low or high velocity
single-phase flows or two-phase flows, and for variable pH having high velocity single
phase or two-phase flows, the corrosion of this "dummy pipe" was uniform throughout the
surface exposed to the flow.
For the cases in which oil was present (two-phase flows) in the test solution,
a sim ilar effect as die one in Figure VI-23 was experienced instead o f uniform corrosion,
as for the two-phase flow tests. The dark line shown in the figure was drawn in it to show
and separate the two different corrosion areas.
The effect of gaps inducing turbulence have been studied in detail by Bussman
[31]. In his work he examined the effects of depth-to-length ratios of these gaps. He found
that downstream o f these gaps high turbulent intensity levels are created increasing the
mass transport away from the pipe wall or increasing the mass transport of the bulk flow
towards the pipe wall.
Evaluation of Correlations
Chapter II presented information on some of the correlations used to predict
corrosion rates in CO2 containing environments. Among those, perhaps the most widely
known is the de Waard and Milliams correlation:
log r = 8.78 - 2.320 - 5.55 x 10' 3 T + 0.67 log PC 0 2 11-24

T + 273
FLOW
Figure VI-22. Photograph of "Dummy Pipe" Showing Corrosion Damage.
208
FLOW
Figure VI-23. Photograph o f "Dummy Pipe" Showing Corroded Area.

The Dark Line Shows die Borderline.
209
This correlation was the first one to be published to predict corrosion rates in
CC>2 environments. It has received a lot o f attention and criticism from investigators.
Many investigators have established their own validity limits to this correlation. Often the
correlation has been accused o f over predicting corrosion rates. Table VI-4 presents condi
tions for which the de Waard and Milliams correlation has been found by some investiga
tors to be valid.
Using the de Waard and Milliams equation with the temperature and pressure
conditions m a in ta in e d in the C O 2 Loop tests, a corrosion rate of 12S8 mpy is predicted.
This agrees very well with the corrosion rates measured for high velocity single-phase
flows and for two-phase flows.

It was found in this investigation that among available correlations for predict
ing CO 2 corrosion, the de Waard and Milliams correlation best describes corrosion rates
measured in the CO 2 Loop for high single-phase flow velocities or two-phase flows.
TABLE VI-4
Validity Limits Established by Investigators

of
de Waard and Milliams Equation
Author CO2 pp Temperature

(bars) (C)
Schmitt [3] 2 60
Eriksrud [10] 1 20
Ikeda [ 11 ] 2 60
Murata [16] 70 60
Palacios [*] 11 75
* Present work. Valid for high single-phase flow velocities

(8 ft/sec) and two-phase flows where VS<Tup to 130 ft/sec
Vgj up to 8 ft/sec.
CHAPTER VH
CONCLUSIONS AND RECOMMENDATIONS
Conclusions
Autoclave Experiments
Experiments performed in the autoclave helped to identify characteristics of
iron carbonate scales related to the corrosion protection that the scale can provide. These
studies showed that iron carbonate scales are very brittle and, under some conditions, can
be removed easily from metal surfaces.
Adherence of the scale to the metal as well as thickness of the scale depend
on the microstructure of the metal specimen. It was determined that for the cases in which
the metal specimen had a normalized microstructure (1018 CR and API N-80 Normalized)
the iron carbonate scale was better adhered and for some cases was thicker than for speci
mens having a quenched and tempered microstructure. Moreover, the crystals forming the
scale on normalized steel specimens were found to be more densely packed than those for
quenched and tempered specimens. The success rate in forming iron carbonate scales on
specimens was greater on normalized steel than quenched and tempered steel.
The mechanism of FeCX>3 formation on a normalized specimen depends on
the pearlite matrix left behind. As the iron corrodes away, there is a pearlite matrix left
behind. Cavities in this matrix allow an increase in the local concentration of ferrous ions
in the cavities. Local flow stagnation and the higher local Fe^+ concentrations in cavities
allow the formation of an iron carbonate scale within the cavities of the pearlite matrix. At
the same time, the pearlite matrix helps anchor the scale. This mechanism explains why
211
212
adherence, formation success rate, and liquid impingement resistance are better for the
normalized steel than for steel having a quenched and tempered microstructure.
Autoclave studies o f the aqueous chemistry effects on FeCOg formation
showed that the initial pH of the solution affects the maximum amount of ferrous ion that
will be dissolved in solution. Initial pH was changed by adding different concentrations of
sodium bicarbonate.
The dissolved iron reached a maximum amount, a plateau. After some time
at this plateau, the dissolved iron concentration decreased by about 300 ppm. After this
decrease had occurred, the experiments were terminated and iron carbonate scale was
found on the specimens. The pH value related to this maximum amount of iron was
determined to be about 5.3.
Liquid Impineement Erosion

Scales tested on the erosion apparatus, subjected to liquid impingement,
showed that scales formed on normalized steel specimens were much more erosion resist
ant than scales formed on quenched and tempered specimens. No damage was observed
on the scale formed on 1018 CR specimens after exposure of 1,000,000 impingements
cycles for velocities up to 250 fit/sec.
Solid Particle Impingement Erosion

Solid particle impingement caused damage to all types ofFeCOg scales. For
impingement velocities ranging from 100 -160 ft/sec, few impacts were required to initiate
damage. For velocities lower than 100 ft/sec, the number o f impacts to cause damage
increased by about one order of magnitude. A graph of the test results suggests that the
number of impacts required to initiate damage of the scale decreased very rapidly with
increasing impact velocity at velocities below 100 ft/sec.
213
CO 3 L oop E xperim ents
A flow loop was designed and constructed for producing single and two-
phase flow velocities to study effects of velocity on CO2 corrosion. Performance tests
showed that the CO2 Loop produces superficial liquid velocities up to 8 ft/sec and superfi
cial gas velocities up to 130 fi/sec. Combinations of these velocities produced the different
flow regimes encountered in oil and gas production; i.e., stratified, slug, froth, mist flow,
etc. These tests also showed that the major pieces of equipment performed as designed.
For example, equipment such as condenser, secondary separator and heater were designed
to protect the compressor from corrosion due to wet CO2 . Coupons to monitor corrosion,
placed in the inlet line of the compressors, have shown no weight loss or corrosion damage
after one year o f loop operation. It is concluded that equipment designed to protect the
compressors is working as intended.
Viewing sections in the loop proved to be helpful when operating the loop
because they allow visual confirmation of the flow regime. The CO2 Loop has transducers
and control systems that monitor and control the important loop parameters and allow for
long duration tests. The data acquisition hardware and custom-designed software have
proved satisfactory for taking, storing, and analyzing data. The use of the computer con
trolled potentiostat makes electrochemical measurements easy to perform and insures
u n ifo rm ity in the procedure.
Test cells were designed and constructed for making electrochemical meas
urements. Electrodes were flush-mounted at the inner pipe wall of the tests cells to mini
mize flow disturbances.
Corrosion rates at constant pH were independent of the flow velocity and
independent of whether die flow is single-phase flow or two-phase flows. Corrosion rates
were in general in the 1,200 -1,400 mpy range for all flow velocities, single-phase or two-
phase, no FeCOj scale was formed, and corrosion rates were fairly constant throughout the
test period.
214
Corrosion rates for high velocity single-phase flows and two-phase flows did
not depend on the flow condition, even when the pH was allowed to increase.
Corrosion rates were independent of pH for high velocity single-phase flows
and for all two-phase flow conditions.
Corrosion rates for all conditions, except low velocity single-phase flows in
which iron carbonate was formed, were predictable by the de Waard and Milliams correla
tion for CO2 corrosion. The de Waard and Milliams correlation described, better than any
other available correlation, the CO2 corrosion rates measured in the CO 2 Loop.
For low velocity single-phase flow tests in which pH was allowed to in
crease, corrosion rates decreased to about 800 mpy for one case and 2 0 0 mpy for another.
For these cases, iron carbonate scale was found on the surfaces o f the steel. After an
FeCOg scale was formed, corrosion rates decreased by about as much as 500 -1 0 0 0 mpy
for one case and about one order of magnitude for another.
For low velocity single-phase flows having variable pH, areas o f severe
corrosion were observed due to the presence of high local turbulence.
The presence of a hydrocarbon phase caused a significant reduction in the
corrosion rates.
215
Recommendations
It was discovered while running this series of tests that the presence of lubri
cation oil leaking past the compressor seals may have had significant influence on the
corrosion rates observed in two of the tests. Therefore, tests should be performed investi
gating the effect of the presence of a hydrocarbon phase in the electrolyte. Initial tests
should be performed in the autoclave using a kerosene, monitoring the pH continuously.
Corrosion rates should be calculated using weight loss methods.
A series of tests similar to the tests presented here should be performed to
study the influence of flow velocity in CO2 corrosion at a temperature of 200F. FeCOj
scales should form more readily at this temperature than at the 160F temperature exam
ined in this work.
Corrosion rates should be monitored for cases where FeC 0 3 has formed to
characterize the magnitude of the corrosion rates under these conditions. An iron carbon
ate scale can be formed on the surface of the loop electrodes in the autoclave while moni
toring the pH at which formation occurs. The electrodes can then be transferred to the
loop for monitoring corrosion rates in single and two-phase flow conditions at different
velocities. In this way the magnitude of corrosion rates after a scale is formed could be
examined, and the influence of single and two-phase flow velocities on the removal of
FeC0 3 scales could be studied.
REFERENCES
[ 1] American Petroleum Institute Recommended Practice 14E (API RP14E), Recom

mended Practice for Design and Installation of Offshore Production Platform Piping
Systems, API Specifications R P 14, December 1981, p. 22.
[ 2] Saylors, S. E., Basile, P. F., "CCh: Properties and Handling with Safety Considera
tions," Southwestern Petroleum Short Course, 1985.
I 3] Schmitt, G., "Fundamental Aspects of CO2 Corrosion," Advances in COo Corro

sion. Vol. 1, NACE, Houston, Texas, 1984.
[ 4] Hausler, R. H., "The Mechanism o f CO2 Corrosion o f Steels in Hot, Deep Gas
Wells," Advances in CO3 Corrosion, Vol. 1, NACE, Houston, Texas, 1984.
[ 5] Hausler, R. HL, and Stegman, D. W "CO2 Corrosion and its Prevention by Chemi
cal Inhibition in Oil and Gas Production," Corrosion 8 8 , Paper No. 363, NACE,
Houston, Texas, 1984.
[ 6] Jasinski, R., "Corrosion of N80-Type Steel by CD-y/Water Mixtures," Corrosion.

Vol. 43, No. 4, pp. 214-218, April 1987.
[ 7] Crolet, J. L., Private Communication, May 1988.
[ 8] de Waard, C., and Milliams, D. E., "Carbonic Acid Corrosion of Steel," Corrosion.
Vol. 31, No. 5, pp. 177 - 181, May 1975.
[ 9] Craig, B. D., Practical Oil-Field Metallurgy, PennWell Books, Tulsa, Oklahoma,

1984.
[10] Eriksrud, E., and Sontvedt, T., "Effect of Flow on CO2 Corrosion Rates in Real and
Synthetic Formation Waters," Advances in COo Corrosion. Vol. 1, NAC*!, Houston,
Texas, 1984.
[11] Ikeda, A., Ueda, M., and Mukai, S., "CO? Behavior o f Carbon and Cr Steels,"
Advances in CO? Corrosion. Vol. 1, NACE, Houston, Texas, 1984.
[12] Burke, P. A., "Synopsis: Recent Progress in the Understanding of C0 2 Corrosion,"

Advances in COo Corrosion, Vol. 1, NACE, Houston, Texas, 1984.
[13] Gatzke, L. K., and Hausler, R. H., "A Novel Correlation of Tubing Corrosion Rates
in Deep, Hot Gas Wells with Water and Gas Production Rates," Advances in CO?
Corrosion, Vol. 1, NACE, Houston, Texas, 1984.
[14] Craig, B. D., "The Occurrence of Cementite as a Corrosion Product at Low Temper
atures 50 C (120F) in a Gas Environment," M aterials Performance. NACE,
February 1977.
216
[15] Bonis, M , and Crolet J., Metaux Corrosion Industrie. Nov - Dec, p. 361,1981.
[16] Murata, T., Sato. E., and Matsuhashi, R., "Factors Controlling Corrosion of Steels in
CQo Saturated Environments, Advances in CO> Corrosion. Vol. 1, NACE, Hous
ton, 1984.
[17] Crolet, J. L., and Bonis, M. R., "pH Measurements in Aqueous CO 2 Solutions
Under High Pressure and Temperature," Corrosion. Vol. 39, No. 2, Feb. 1983.
[18] Dunlop, A. K., Hassell, H. L., and Rhodes, P. R., "Fundamental Considerations in
Sweet Gas Well Corrosion," Advances in CQo Corrosion. NACE, Houston, Texas,
1984.
[19] Kapusta, S., Private Communication, Shell Research and Development Center,
Houston, Texas, May 1989.
[20] Fontana, M. G., Corrosion Engineering, 3rd Edition, McGraw-Hill, 1986.
[21] Uligh, H. H., and Revie, R. H., Corrosion and Corrosion Control: An Introduction
to Corrosion Science and Engineering, 3rd Edition, John Wiley and Son, 1985.
[22] Bailar Jr., J. C., Moeller, T., et al., Chemistry 2nc* Ed., Academic Press, Orlando,
Florida, 1984.
[23] Tafel, J. Z , For Phvsiki Chemie 641-712,1905.
[24] Camacho, R. A., "The Design, Construction, and Testing of a Liquid Jet Impinge
ment Apparatus and the Evaluation o f Metal Surfaces Eroded by Liquid Jet Im
pingement" Master of Science Thesis, The University of Tulsa, 1988.
[25] Arismendi, Felix, "The Erosion Response of an Iron Carbonate Corrosion Scale to
Impulsively Applied Hydrostatic Pressures," Master o f Science Thesis, The Univer
sity of Tulsa, 1985.
[26] Oney, C. Private Communication, Oxy U.S A ., Tulsa, Oklahoma, March 1988.
[27] Palacios, C. A., "The Design, Construction and Testing of an Experimental Facility
to Study Effects of Flow Velocity on Erosion-Corrosion in Oil and Gas Production
Equipment" Master of Science Thesis, The University of Tulsa, 1987.
[28] Crolet J. L., and Bonis, M , "An Optimized Procedure for Corrosion Testing under
CO2 and H2 S Gas Pressure," private communication, 1988.
[29] C rolet J. L, Private Communication, Elf Aquitaine, 1989.
[30] Reeder, R. J., Editor, Reviews in Mineralogy. Vol. 11, Carbonates: Mineralogy and
Chemistry, Mineralogical Society of America, Bookcrafters, Inc., Michigan, 1983.
[31] Bussman, W. R., "Computational Modeling of Single-Phase Flow Through Pipeline

Fittings with Application to Erosion-Coirosion Damage," Master of Science Thesis,
The University of Tulsa, 1988.
218
[32] Mutsakis, E. G., "An Experimental Investigation o f the Erosion o f an API N80
Grade Steel by Solid Particle Impingement," Master o f Science Thesis, The Univer
sity of Tulsa, 1989.
[33] Ellison, B. T., and Wen, C. J., "Hydrodynamic Effects on Corrosion," Tutorial
Lectures in Electrochemical Engineering and Technology, AIChE Symposium
Series, No. 204, Vol. 77, pp. 161-169,1981.
[34] Sanchez-Caldera, L. E., "The Mechanism of Corrosion-Erosion in Steam Extraction

Lines of Power Stations," P hD . Dissertation, Massachusetts Institute of Technolo
gy, 1984.
[35] Ellison, B. T., "Corrosion-Erosion in Multiphase Systems," 70th AIChE Annual

Meeting, Paper No. 35C, 1977.
[36] Beggs D., and Brill, J. Two-Phase Flow in Pipes. 6 th Edition, The University of
Tulsa, Dec. 1988.
[37] Govier, G. W., and Aziz, K., The Flow o f Complex Mixtures in Pipes. Van Nos
trand Reinhold Co., New Yoric, 1972.
[38] Madhane, J. M., Gregory, G. A., and Aziz, K., "Some Design Considerations for
Two-Phase Flow in Pipes," presented at 25th Annual Tech. Mtg. of Petroleum
Society o f CIM, Calgary, May 7-10,1974, Paper No. 374020.
[39] Hansen, B., Software Development, Erosion/Corrosion Research Center, The

University of Tulsa, 1988.
[40] Ross, T. K., and Jones, D. H., "Corrosion Inhibition in Moving Media," Journal of
Applied Chemistry. No. 12, July 1962.
[41] Videm, K., and Dugstad, A., "Film Covered Corrosion, Film Breakdown and Pitting
Attack of Carbon Steels in Aqueous CO2 Environments," Paper #186, Corrosion 88 ,
S t Louis, Missouri, March 21-25,1988.
APPENDIX A
RAW DATA
219
CORROSION RATES (mpy)
TEST # 0 9 PH - 3.4
SINGLE PHASE Ve 1 * 1 ft/sec
TIME HTOP HBOT VNOR VSOU ROW AVERA
0 12.71 1913 1994 1856 1921

2 17.13 1550 1612 1513 1558.333
7 36.49 1353 2440 1461 1751.333
18 75 1248 1883 1518 1549.666
31 985 1506 1461 1247 1404.666
44 1740 1057 1042 1132 1077
49 1826 1105 1121 1212 1146
54 2344 1874 1281 1269 1474.666
66 2723 1883 1354 1237 1491.333
75.5 482 1584 1289 1291 1388
80.5 2994 1565 1578 1248 1463.666
COLUMN
AVERAGE 1204.02 1312.545 1550.454 1362.181 1475.060
WEIGHT
LOSS 269 L490 1453 1244
TEST #10 pH * 3.4
SINGLE-PHASE Vsl * 8.0 ft/sec
3 1305.2 1850 1577.6

21.6 1190.6 1010.6 1250.8 1301.8 1188.45
27.6 1394 1330.9 1065.5 1338.2 1282.15
38.1 1063 1022.6 1023 1181 1072.4
45.1 1168.2 1129.37 1122.43 1217.06 1159.265
64.1 1181.68 1155.8 1259.4 1177.5 1193.595
98.4 1188.5 1128.58 1546.8 1293.05 1289.232
110.4 1178.5 1319.6 1527.36 1334.7 1340.04
COLUMN
AVERAGE 1208.71 1243.431 1256.47 1263.33 1262.841
WEIGHT
LOSS 1225 1256 1196 1286
TEST #11 pH > 3.4
V s 1 * 1 ft/6ec
TWO-PHASE Vsg = 1 ft/sec
0 165.55 .'453.3 1631.5 1493.6 1526.133

9.5 195.45 3101.5 1279.1 985 1786.533
15.2 585.37 2122.3 1286.4 1222.8 1543.833
20.7 380.86 2039.47 1257.2 1013.4 1436.69
32.5 562.6 1862.98 1341.65 1235.7 1480.11
38.5 507.93 1600 1209 1172.6 1327.2
43.8 807.7 1727.9 1167.1 1145.4 1346.8
56.1 799 1632.95 1166.9 1159.2 1319.683
62. 3 976.24 2636.6 1051.8 1107.2 1598.533
79.2 1814 1527 1042 1026.6 1198.533
82.7 1362 1640.6 1018.67 991 1216.756
COLUMN
AVERAGE 741.5181 1940.418 1222.847 1141.136 1434.800
WEIGHT
LOSS 1172 1597 1348 1331
TEST # 1 2 pH = 3.4
TWO-PHASE Vsl 1 ft/sec

Vsg = 60 ft/sec
TIME HTOP HBOT VNOR VSOU ROW a v e r ;
0 267.1 641.05 452.31 453.4866

16.3 242.4 612.05 398.55 417.6666
41.2 241.1 500.5 534 357.07 408.1675
52.2 253.5 483.14 400.6 349.5 371.665
63.6 261.4 468.14 407.75 348.8 371.5225
74.2 267.44 445. 6 347.89 322.71 345.91
86.4 235.09 453.26 322.93 302.5 328.445
COLUMN
AVERAGE 294.6716 600.6233 503.2925 421.9066 449.4805
WEIGHT
LOSS 1732 1283.65 1915.4
TEST * 13 pH * 3.4
TWO-PHASE Vsl - 1 ft/sec

Vsg 60 ft/sec
TIME HTOP HBOT VNOR VSOU ROW AVER/
0 179.4 417.75 179.14 336.13 278.105

. 6.6 167.4 493.5 181 365.5 301.85
24.2 84 350.67 89.1 253.4 194.2925
31.6 69.7 329.4 80.27 225.08 176.1125
56.2 63.2 279.07 136.37 189.15 166.9475
74.8 55.6 255.65 48.5 163.42 130.7925
COLUMN
AVERAGE 123.8599 425.2079 119.0633 255.4466 208.0166
WEIGHT
LOSS 475 942 388 1167 743
TEST #16 pH 3.4
TWO-PHASE Vsl * 8 ft/sec

Vsg * 6 ft/sec
TIME HTOP HBOT VNOR VSOU TOTAL AVE
0 7261 1526 1393 1610 1568

9.6 1500 1360 1430
21.3 1440 994 1217
45.2 1296 970 1133
51.8 1502 1042 1272
76.7 1184 1140 1162
97 1392 821 1106.5
COLUMN
AVERAGE 1405.714 1133.857 1269.785
WEIGHT
LOSS 945 2053 1940 1991 1732.25
TEST # 17 pH * VARIABLE
TWO-PHASE Vsl 8 ft/sec

Vsg 6 ft/aec
0 1607 2067 2287 2845 2201.5

17 1241 1352 1104 2944 1660.25
41.5 996 1253 1096 1835 1295
54.7 1376 1620 1289 1558 1460.75
65.1 1286 1516 1289 1367 1364.5
80.6 921 1100 952 1258 1057.75
94.8 1244 1500 1325 1454 1380.75
117.8 1122 1553 1368 1422 1366.25
142 979 1428 1285 1305 1249.25
163.9 990 1392 1270 1246 1224.5
COLUMN
AVERAGE 1176.2 1478.1 1326.5 1723.4 1426.05
WEIGHT
LOSS 1931 1710 2014 2586 2060.25
TEST #18 pH = VARIABLE
SINGLE PHASE Vsl 1.2 ft/sec

0 0 1419 1568 2246 1744.333
14.4 0 1173 1223 1208 1201.333
38 0 999 1518 1133 1216.666
63.1 0 948 1038 750 912
110.4 0 832 938 811 860.3333
134.2 0 797 832 758 795.6666
159. 2 731 958 728 805.6666
166 614 677 572 621
173 593 494 543.5
COLUMN
AVERAGE 900.6666 1027.333 1025.75 966.7222
WEIGHT NON - AVAILABLE

LOSS
TEST #21 pH b VARIABLE
TWO-PHASE Vsl = S ft/sec

Vsg 6 ft/sec
0 769 1024 1168 1353 1078.5

4 1012 1204 1294 1421 1232.75
18.1 655 397 612 960
24.2 1416 895 1351 1587 1312.25
42.2 1245 874 1489 1578 1296.5
47.5 1293 998 1536 1578 1351.25
55.4 1873 1332 1480 1392 1519.25
71.1 1378 1080 1375 1404 1309.25
92.9 1198 1248 1418 1468 1333
100 1050 1191 1315 1405 1240.25
114.8 1127 1213 1324 1380 1261
129.3 1011 1142 1243 1315 1177.75
143.5 985 1125 1200 1260 1142.5
187 909 1081 1106 1153 1062.25
202.2 891 992 1053 1166 1025.5
217.9 861 953 959 962 933.75
253.8 782 826 804
283.1 861 805 894 1014 893.5
318 864 789 865 927 861.25
319.9 847 749 820 953 842.25
COLUMN
AVERAGE 1051.35 995.9 1184.315 1277.684 1140.881
WEIGHT
LOSS 1296 905 1462 1488
TEST it 25 12/05/89
pH - VARIABLE Vsl 2 fps Vsg 0 fps
HBOT VNOR VSOU ROW AVERA

TIME HTOP
2044 2930 1624 2280.5
0 2524
1493.5
2.5 1516 1566 1450 1442
1273 1193 1211 1223.75
20.6 121 o 764.5
47 572 87 3 792 821
510 446 430 454.75
64 433
527 368 320 294 377.25
72 225
89 336 205 197 162
COLUMN
1018 977 1046.857 854.8571 974.1785
AVERAGE
WEIGHT
LOSS 1468 1066 1030 1151
TEST # 27 12/12/89
pH VARIABLE Vsl 2 fps Vsg 2 fps
TIME HTOP HBOT VNOR VSOU ROW AVERAGE

0 841 1177 1149 1064 1057.75
6.25 1121 1453 1494 1312 1345
28.8 1028 1185 1384 1199
52.7 1085 1319 1168 1190.666
76.7 820 1279 1335 1144.666
120 739 1138 1069 982
191.7 745 1101 970 938.6666
COLUMN
AVERAGE 911.2857 1236 1224.142 1188 1122.535
WEIGHT
LOSS 1609 1386 1522 1654
TEST # 26 12/12/89
pH - VARIABLE Vsl 8 fps Vsg 0 fps
0 1356 1214 1457 1555 1395.5

16 1300 1366 1152 1191 1252.25
40 1378 1382 1113 1145 1254.5
67.6 1365 1498 1171 1162 1299
112 1163 1135 1177 1223 1174.5
135.8 1181 1181 1152 1303 1204.25
142 1258 1461 1291 1362 1343
160 1165 1291 1143 1120 1179.75
COLUMN
AVERAGE 1270.75 1316 1207 1257.625 1262.843
WEIGHT
LOSS NOT - AVAILABLE
APPENDIX B
TEST CELL AND ELECTRODE DIMENSIONS
AND
CHEMICAL COM POSITION OF TH E "DUMMY PIPE*
226
227
m
n
o
05
oo
(C
III
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(A
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o
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Reproduced with permission o f the copyright owner. Further reproduction prohibited without permission.
STEEL SPECIMEN
N 8 0 - STEEL 0 .2 in. DRILL 8 TAP
ROD, 0.158 in. DIA. APPROX.
0.312 in. DIA.

1.5 in.
WORKING ELECTRODE
REFERENCE AND COUNTER ELECTRODE
to
to
00
TABLE B -l
Specification o f "Dummy Pipe" (A I S I 1012 or 1015 SteeD
c,% 0.15
A
Si,% U .U/
Mn, % 0.59
P ,% 0.013
S ,% 0.28
N i, % 0.09
Cr, % 0.02
Mo, % 0.02
Cu, % 0.02
A l, % 0.06
Ti, % 0.01

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M echanism s of CO2 corrosion related to velocity in two-phase

Palacios, Carlos Alberto, Ph.D.

Copyright 1990 b y Palacios, Carlos A lb erto. A ll rights reserved.

THE GRADUATE SCHOOL

MECHANISMS OF C 0 2 CORROSION RELATED TO

A dissertation submitted in partial fulfillment of

the requirements for the degree of Doctor of Philosophy

in the Discipline of Mechanical Engineering

The Graduate School

The University of Tulsa

THE GRADUATE SCHOOL

MECHANISMS OF C 02 CORROSION RELATED TO

APPROVED FOR THE DISCIPLINE OF

Palacios, Carlos Alberto (Doctor of Philosophy in Mechanical Engineering)

Mechanisms of CO2 Corrosion Related to Velocity in Two-Phase Flow Systems.

(229 pp. - Chapter VH)

Directed by Dr. John R. Shadley, Associate Professor of Mechanical Engineering, The

This dissertation presents a study on carbon dioxide corrosion at CO2 pressure

tation by means of experiments performed in an autoclave. Models for FeCOg formation

designed to allow for electrochemical measurements of corrosion rate using removable

to increase to about 5.5.

Special thanks are extended to Dr. Edmund F. Rybicki for serving in my

very much for all your comments and feedback.

I would like to give thanks to the professors o f the Mechanical Engineering

of a job teaching others, what they so carefully taught me.

supporting this research.

The financial assistance provided by CORPOVEN S.A., an oil company from

Venezuela, is greatly appreciated.

good memories and the good times.

Finally, I would like to thank Ed Bowers, the Erosion/Corrosion technician, for

his comments and work which were always of great value.

couraging me to pursue my Ph.D.; I love you with all my soul. Te Adoro.

To my two wonderful children Carlos Alberto and Carlota Elisabeth.

TABLE OF CONTENTS................................................................................................. viii

LIST OF FIGURES.......................................................................................................... xii

LIST OF TABLES............................................................................................................ xix

CARBON DIOXIDE PROPERTIES............................................. 7

CARBON DIOXIDE CORROSION............................................ 10

The Interface Mechanism................................................... 14

The Interphase Mechanism................................................ 15

Structure of Iron Carbonate Scales....................................... 63

Discussion of Preliminary Results................................... 67

Tests at Low Temperatures............................................. 75

Iron Dissolution at Constant p H ...................................... 104

Dissolution of Iron Carbonate................................................ 108

CHAPTER IV EROSION OF IRON CARBONATE SCALES............................. 116

Description of Erosion Apparatus......................................... 116

Main Features.................................................................... 118

Major Components............................................................ 118

Liquid Impingement T ests.................................................... 119

API N-80 Steel Specimen............................................... 119

CHAPTER V EXPERIMENTAL APPARATUS.................................................. 143

Carbon Dioxide Loop............................................................ 143

Two-Phase Flows.............................................................. 143

Loop Capabilities.............................................................. 144

Data Acquisition System.................................................. 149