Corrosion Introduction
Corrosion Introduction
Corrosion Introduction
Corrosion Basics
General corrosion theory Corrosion examples
Specialty Problems
CO2 and H2S O2 in sea water injection Acid Treatment Packer Fluids
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Corrosion Control
Recognition of Corrosion Causes of Corrosion Corrosion Prevention
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Other Factors
pH Chlorides (influences corrosion inhibitor solubility) Temperature (Increase usually increases corrosion) Pressures (CO2 and H2S more soluble in H20) Velocity - important in stripping films, even for sweet systems Wear/Abrasion (accelerates corrosion) Solids strips film and erodes metal
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Chemical Corrosion
H2S
weak acid, source of H+ very corrosive, especially at low pressure different regions of corrosion w/temp.
CO2
weak acid, (must hydrate to become acid) leads to pitting damage
Strong acids - HCl, HCl/HF, acetic, formic Brines - chlorides and zinc are worst
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Corrosion Recognition
Failures have many causes and appearances
abrasion (rod wear on tubing, etc.) erosion(solids, droplets, mists) wear chemical (oxidizing, acids, acid gases, chlorides, etc) galvanic coupling (electromotive series) metal alteration
chemical physical
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Schlumberger O.F.R.
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Steel loss at the Anode weight loss and pitting are simply illustrations of iron going into solution.
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The size and number of the crystals present in metals are a function of the cooling process (quenching). George E. King, Engineering
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Corrosion Types
Galvanic a potential difference between dissimilar metals in contact
creates a current flow. This may also occur in some metals at the grain boundaries.
Pitting Extremely localized attack that results in holes in the metal. Stress Corrosion Occurs in metal that is subject to both stress and
a corrosive environment. May start at a stress riser like a wrench mark or packer slip mark.
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Corrosion Types
Erosion Corrosion Passage of fluid at high velocity may remove
the thin, protective oxide film that protects exposed metal surface.
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Partial pressure is the mole fraction of the specific gas times the total pressure.
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The corrosion rate of CO2 is a function of partial pressure, temperature, chloride presence of water and the type of material.
Corrosion rate in MPY mills per year is a standard method of expression, but not a good way to express corrosion where pitting is the major failure.
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Cost factors between the tubulars is about 2x to 4x for Chrome-13 over low alloy steel and about 8x to 10x for duplex (nickel replacing the iron).
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H2S corrosion
Several forms Results in some form of iron sulfide Most FeSx only very slowly acid soluble in thicker deposits
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H2S corrosion is minimized by sweetening the gas (knocking the H2S out or raising pH.
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5.5
0.03bara
pH 4.5
FURTHER ASSESSMENT REQUIRED
3.5
UNACCEPTABLE
0.001
0.01
1.0
Domain Diagram For The Sulphide Stress Cracking Limits Of 95ksi Super 13Cr Alloys In High Chloride (120,000 ppm Cl-) Waters
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Gas, water and sand flowed from the tubing bore to the annulus, resulting in significant erosion of both the tubing and casing. Tubing replaced with CR13 95ksi 13/5/2, casing repaired with an expandable solid casing patch.
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Crevice Corrosion
The physical nature of the crevice formed by the tubing to coupling metal-to-metal seal may produce a low pH aggressive environment that is different from the bulk solution chemistry hence a material that looks fine when tested as a flat strip of metal can fail when the test sample (or actual tubing) includes a tight crevice. This damage can be very rapid in water injection wells, wells that produce some brine or in wells where there is water alternating gas (WAG) sequencing causing failure at the metal-to-metal seals in a matter of months.
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Crevice Corrosion
Note the seal crevice corrosion this caused a leak to the annulus.
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Crevice Corrosion
There have been three notable instances of this occurring in 13Cr seawater injection systems in the North Sea a Statoil well after 9 months, Gyda where they claimed O2 levels were kept to <20 ppb, at Machar (part of ETAP) where O2 levels were controlled to 50 ppb or lower (Super 13Cr).
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Crevice Corrosion
Note the pit that started the washout seal crevice corrosion.
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O2 Corrosion
There is no corrosion mechanism more damaging on a concentration basis than oxygen small amounts of oxygen, water and chlorides can ruin a chrome tubing completion in a few months. Injection wells are the most severely affected minimise oxygen and dont use chrome pipe in injectors.
O2 CO2 H2S
0 0
20 ppb O2 limit for seawater in carbon steel injection tubulars. 13Cr is CO2 resistant but very susceptible to pitting corrosion in aerated brines. 5 ppb O2 is suggested as a limit, but even these levels have not been confirmed.
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A split in the side of 5-1/2 casing. Cause was unknown mechanical damage (thinning by drill string abrasion) was suspected.
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Abrasion by solids, gas bubbles or liquid droplets may significantly increase corrosion by continuously removing the protective oxide or other films that cover the surface following the initial chemical reaction.
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Most graphs do not show the effect of too low a velocity on the corrosion rate. When the surface is not swept clean, biofilms can develop or the surface liquid layer may saturate with CO2 or other gas, increasing corrosion.
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Maximum Velocities
Conditions Tubing Pressure 1000 psi 5000 psi ________ _______ Wet, non corrosive gas 85 fps 75 fps Wet, corrosive gas 50 fps 40 fps Wet,corros. & abrasive 30 fps 25 fps
There may be minimum velocities needed to prevent biofilms or other static fluid problems.
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Note the effect of increasing flowing fluid density on corrosion rate. Also presence of solids in the flowing fluids very significantly lowers the maximum permissible flow rate.
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Critical or maximum velocities for flow using the API RP 14E equation. The variable is the C factor for short lived projects, this factor may be 200 or more. It may also rise when CRA pipe is used.
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Corrosion increases after water cut reaches 10 to 20%. The cause is removal of the protective oil film. In the third phase, the pipe is completely water coated and corrosion rate becomes more constant.
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A rise in chlorides is usually accompanied by a drop in pH. Iron content often reflects corrosion in the system, but is also a reflection ofGeorge low pH. E. King, Engineering 3/14/2009 47
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Effect of pitting on penetration rate Low mpy (mils per year) readings can mask pit development that leads to leaks.
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Welds
The heating that occurs during the welding process will cause the weld metal and the heat affected zone around the weld to be physically different from the surrounding, original metal. An anode is created by this difference.
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Pitting in the heat affected zone around a weld. May be an example of galvanic corrosion.
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4.
CO2 injection wells have special metallurgy requirements. Designs should minimize un-swept or static areas. Corrosion may occur preferentially downstream of the coupling.
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Biological Corrosion
Anaerobic
SRBs - sours the well/reservoir Iron Fixers - slime and sludge Slime Formers - formation damage
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Bacterial deposits on injection tubing. Pitting under the bacterial colony can be severe.
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Generates high H2S concentration in small area worst where velocity < 3-1/2 fps
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Location Relative Cost Wytch Farm, UK 1 S.N.Sea, Trinidad 3 Rhum, Tuscaloosa 5 Miller, T. Horse 8-10 Miller, Congo - Liners 12-15 Middle East (825) 20 Gulf Of Mexico (G3) >20
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Bacterial Corrosion
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Severe CO2 corrosion probably along a low side/trapped volume of water that is saturated with CO2.
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very
CO2 corrosion
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George E. King, Engineering Co2 corrosion in box, just past gap in coupling. 3/14/2009 GEKEngineering.com
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George E.trenches King, Engineering Parted coupling CO2 corrosion note and pits. GEKEngineering.com
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Galled Threads physical damage. Galvanic corrosion would have metal loss specific to one George E. King, Engineering member 3/14/2009 of the coupling. 75 GEKEngineering.com
CT Corrosion Problems
cyclic imersion increases corrosion flow assisted corrosion abrasion assisted corrosion (fines) abrasion damage (> 50 micron) storage may be worst problem area salt fluids increase Cl- corrosion stressed locations see accelerated corrosion marks, welds, HAZ are problem areas
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Chrome pipe after acidizing with the proper inhibitor and a inhibitor intensifier. Source
Khalefa Esaklul
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Chrome pipe after acidizing with marginal inhibitor. Source Khalefa Esaklul
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pump
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Inhibitor Mixing
What will work? Air sparging or rolling the tank with gas paddle mixing that creates a vortex vigorous rolling
mixer
Effect of oxygen in acid oxygen increases corrosion oxygen saturation in acid is 7 parts per billion effect is limited
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Electrochemical
Galvanic - two dissimilar metals - couplings, centralizers, pumps, packers, profiles usually severe metal loss on one metal near contact point. May see galvanic loss on a single metal with current. Crevice Corrosion - localized, forced penetration, oxygen and chloride major factors Stray Current Corrosion - extraneous AC or DC current in earth. Point of arrival is cathode departure point is anode.
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Sacrificial anode (magnesium) from an offshore platform. This was a round bar stock anode.
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Controlling Corrosion
1. Maintain high pH 2. Control gas breakout 3. Use passive metals 4. Remove Oxygen 5. Control velocities 6. Lower chlorides 7. Bacteria control 8. Acid/brine use considerations and alternatives 9. Liquid removal 10. Inhibitor injection 11. coatings
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Corrosion Films
First products of corrosion films may form a tight, barrier film and reduce corrosion.
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Chromium
Increasing Cr content of the alloy increases the Cr content (and film resistivity) of corrosion layer. Above 10% Cr in alloy, composition of layer is constant. Why use more???? - chemical resistance. For 13% and 22% Chrome tubulars, critical erosion velocities are twice carbon steels in CO2.
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Crack in the casing immediately below the wellhead. Probably due to a minor defect in the tubular and perhaps compounded by wellhead stress.
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This is the starting point but what caused the break? Clues are found in the well environment, the history and the area surrounding the break.
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