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Tony Cole EPT-DW Completions and Multi-lateral Technology Team RTS Rijswijk +31 (0)70 311 3049
Simon Fisher Mark Anderson Marc Amory Gerard Mulder Matt Bayfield Tony Cole Wes Moore
+31 70 311 3242 +31 70 311 6149 +31 70 311 3506 +31 70 311 6148 +31 70 311 6126 +31 70 311 3049 +31 70 311 3550
Multi-lateral wells
multiple reservoirs single reservoirs
ML database/newsletter/web site
Dissemination of latest completions technology http://swwrij.siep.shell.com/cc/dw/cmlt/home.htm
Useful URLs
CMLT Team http://swwrij.siep.shell.com/cc/dw/cmlt/ Corrosion engineering discussion site http://sww1.epglobal.shell.com/forums/aca-16/dispatch.cgi Well engineering discussion site http://sww1.epglobal.shell.com/forums/welleng/dispatch.cgi
Objectives
Introduction to:
The types of corrosion which may occur in downhole environments Methods to prevent corrosion Methods to find corrosion
Provide enough background knowledge to allow you to question Corrosion decisions in an intelligent way.
Contents
General Corrosion Principles Corrosion expected in Oil and Gas facilities Prevention Materials selection guidelines Monitoring and Measuring
API 5CT / ISO 11960 API 6A / ISO10423 API 17D ISO 13680
(under rev.)
*NACE
SSC resistant metallic materials for oilfield equipment Selection of metallic materials to be used in all phases of water handling for injection into oil-bearing formations Metallic materials for sucker rod pumps for corrosive oilfield environment Lab. Testing of metals for resistance to specific forms of environmental cracking in H2S environments. Handling and proper usage of inhibited oilfield acids Care, handling and installation of internally plastic-coated oilfield tubular goods Application of CP for external surfaces of steel well casings
Electrochemical cell
Electrochemical in nature
Involves the transfer of electrons Requires electron path and ionic path
+2e H
Thermodynamics
Pourbaix diagrams
For particular conditions these demonstrate the stability of metals They suggest different methods of mitigating corrosion
Lower potential Raise pH Raise potential
Galvanic Series
Electrochemical series indicates the relative thermodynamic stability of metals under standard conditions Galvanic series indicate relative stability of metals in real environments
Note that joining dissimilar metals may lead to rapid attack of the least noble one, however if there is no aggressive species corrosion will not take place. This forms the basis for sacrificial anode cathodic protection Galvanic attack may also happen if there are significant metallurgical differences in one piece of metal (eg. Heavy local cold working such as tong marks)
Kinetics
Evans diagram and related Potential/Current graphs
Illustrates the speed of a reaction Illustrates how exposure to different environments can create a galvanic cell Can be used to demonstrate how changes in the environment might affect the corrosion rate Can be determined for simulated conditions and used in the materials selection process Illustrates a way to measure corrosion instantaneously in the field
Electrochemical measurements
Electrochemical measurement, whether done in the lab or in the field, require three electrodes. A. Sample B. Reference C. Auxillary They are used to determine: a. corrosion rates b. current required for CP c. polarization behaviour
Ammeter
Types of corrosion
Tong damage
May lead to localised corrosion
Tubing, casing and jewelry to consider Acidisation for stimulation may be a factor
Internal casing corrosion can occur in the absence of a packer or if the packer fails. Water can condense at cool areas on the casing and H2S and/or CO2 can corrode the steel. The tubing wouldnt necessarily be corroded at the same area because fluid travelling along it may keep its temperature above the dew point
Others
Pressure Temperature Flow rate pH Bicarbonate Bacteria Galvanic couples Differential concentration Dew point Inhibitor Coating/lining
O2 is about 80 times more corrosive than CO2 and 400 times more corrosive than H2S
Sour corrosion
H2S + Fe FeS + H2
Half reactions
CO2+ H2O Fe 2H + CO3 Fe + 2e
2+ + 2-
Half reactions
H2S 2H + S
+ 2-
2H + 2e
H2
(disassociates in water)
Fe
Fe + 2e
2+
Sweet
Sour
General corrosion
(calculate using model. Shell uses Hydrocor which has been provided)
Mitigation methods
Engineer
Permanent solution particularly for corrosion which can cause rapid/sudden failure Increases CAPEX
Operate
Adds to OPEX Requires confidence in Operations and commitment
Inhibit
Continuous Batch
Encapsulation
Inhibitors encapsulated in polymer gel are introduced into the well, either in a basket or in the rat hole.
Can cause interference with flowlines, other wells or surface equipment. For this reason well-heads require good electrical insulation (also to prevent galvanic problems) Groups of wells are usually protected simultaneously To ensure CP to the bottom of the casing, current is sometimes pulsed
Well casings may need cathodic protection Obtaining E lg I data is an accepted method of determining current requirements. Instant off readings should be used The reference electrode should be remote from the well head Note the similarity between this set-up and that shown earlier regarding determination of corrosion rate and V-i graphs.
Non-intrusive
Can be done without interrupting flow
Downhole calipers, mechanical, magnetic, ultrasonic Video cameras Downhole CP logging tools Weight loss coupons Electrochemical techniques (LPR, EIS, potentiodynamic) Hydrogen probes Electrical resistance probes Field signature monitoring Intelligent pigging of pipelines Conventional non-destructive test techniques (UT etc..)
Downhole calipers: mechanical, magnetic, ultrasonic Video cameras Weight loss coupons/Electrical resistance probes Electrochemical techniques (LPR, EIS, potentiodynamic) Downhole CP monitoring using logging tools (casing
potential profile tool)
Trip Section
Drive Section
Feeler Section
Centralizer
Trip Section operates like a Tubing End Locator. Once the survey depth is reached, pick up, shear pin and begin survey.
Rotation of Drive Wheel is transmitted through a Transmission system which feeds the CHART past the recording Stylus .
Simultaneous, Continuous and Independent movement of each feeler is recorded on a CHART housed inside the Caliper .
Male Quick-Lok Connection on Top Three Centralizer Shoes one each 120O
The movement of the Feeler is transmitted through the Feeler Spring to the recording Stylus and this action is SCRIBED on the Chart for each of the Feelers. The recordings are wrapped around the outside of the Survey Chart.
Schlumberger UCI
The UCI takes 180 highly focused measurements during each revolution of the ultrasonic sensor. It has up to 5 rotations every inch of travel inside the casing and can measure pits and other anomalies down to diameters of approximately 8 mm on either the inside or outside surface.
A variety of monitoring devices can be inserted downhole. The amount of time between insertion and retrieval with useful information depends on the sensitivity of the probe
Wellhead and remote CP monitoring (external casing) Inspecting tubulars retrieved for some other purpose Iron, Mn or bacterial counts Inhibitor concentration monitoring Annulus pressure monitoring Monitoring of flowlines and/or other surface equipment using conventional methods to infer well conditions
Electrical resistance probes Electrochemistry UT etc..
Mitigation methods
Corrosion allowance Remove the corrosive species
Prevent ingress/gas blanket Scavenge Kill bacteria
Cathodic protection
Impressed (continuous or pulsed for casing protection) Sacrificial
Resistant materials
Solid corrosion resistant material CRA Clad CRA (low alloys to nickel alloys) Coatings/linings Composite materials (fibre reinforced plastics)
Sour corrosion
Hydrogen induced cracking
Sulphide stress cracking Step-wise cracking Blistering Hydrogen assisted ductile failure
Sour corrosion
Dehydration Resistant material
SSC NACE qualified materials
Bear in mind the potential for other kinds of failure
Use inhibitor
Prefer continuous application Batching is possible Require tests to determine most effective Need to ensure it gets to the correct location
Requires qualification; slow strain and ripple strain tests now used
Apply inhibitor
(As sweet, opposite)
Coat/line
Insert lining into new/existing line (particularly for water disposal) Coat with GRE/FBE/PE (sometimes used for down hole eqpt.)
Note: CO2 corrosion is flow sensitive, turbulence can remove the protective carbonate scale. Its not good practice to rely on high temperature alone to reduce corrosion to an acceptable level.
See the .xls spreadsheet CRA from Shell Oil. Bear in mind that this is a guide only and that the recommendations are incomplete.
GRE 13% Chrome Super 13% Chrome 22% Chrome 25% Chrome Incoloy 825/Sanicro 28 Inconel 625/C276
First phase
Expose in the (simulated) environment and determine weight loss, pit density/depth For SSC determine hardness
Second phase
Sulphide stress cracking Double cantilever beam testing to determine K1ssc (NACE type D
pass u33 MPam)
Glossary
AC Impedance spectroscopy- A technique used to measure corrosion rates over a short period of time (half an hour test). Also known as electrochemical impedance spectroscopy or EIS. Carbon dioxide corrosion - dissolved in water, carbon dioxide forms an acid which reacts to corrode steel and form a scale, the scale becomes protective at higher temperatures. Cathodic protection - A means of reducing or preventing corrosion by altering the electrical potential of the structure being protected so that it is thermodynamically stable. This can be achieved by either deliberately forming a galvanic cell with a more reactive material (eg. Zn, Mg or Al) or by applying an impressed current. When applying an impressed current it is important that the potential of the structure is controlled to prevent excessive production of hydrogen which may cause cracking. Differential concentration - corrosion cells may be set up because different potentials are caused when varying concentrations of aggressive species are present across a metal surface. One of the most common types of differential concentration cell is the differential aeration cell. where differences in oxygen concentration lead to higher corrosion rates where there is less oxygen (this is why corrosion is often found under washers and at crevices) Environmentally assisted failure - A general term used to describe failure mechanisms where the co-joint action of stress and corrosion caused by the environment results in an apparent loss of ductility. Eg. Hydrogen induced cracking, hydrogen assisted ductile failure, stress corrosion cracking, corrosion fatigue, hydrogen blistering, liquid metal embrittlement Erosion corrosion - Corrosion products may be removed by fast moving fluids or solids. Once removed the corrosion product re-forms and this repeated removal/reforming can lead to rapid failure. Often occurs in combination with carbon dioxide and hydrogen sulphide corrosion where a carbonate scale or sulphide film, which may otherwise protect against further corrosion, is removed. General Corrosion - Corrosion which occurs over a large surface area, as opposed to forming pits, cracks etc. In practice very few instances of corrosion are really general, most general corrosion starts life as discrete pits which then broaden and merge. Galvanic corrosion - When two metals which have adopted different natural potentials are electrically connected the voltage between them can accelerate corrosion of one and reduce it in the other. This is known as galvanic corrosion. High alloy valves connected to carbon steels pipe with a conductive fluid passing through may allow galvanic corrosion to take place.Under some circumstances, where a piece of corroded steel is connected to a clean piece of steel for example, the galvanic couple can cause rapid failure of the new piece of metal. Hydrogen induced cracking (HIC) - Cracks caused by the accumulation of hydrogen in metals. Hydrogen may result from reactions with hydrogen sulphide gas but may also be created by over enthusiastic application of a cathodic protection system. Hydrogen sulphide - A corrosive species which reacts to form FeS and hydrogen. Particularly nasty because it a. produces monotonic hydrogen and b. sulphur poisons the hydrogen re-combination reaction. This allows hydrogen to travel into the metal lattice where it can cause serious damage. In addition to general corrosion and pitting, dramatic failures can occur because hydrogen in lattice can cause blistering, cracks and significant reductions in ductility. In general, cracking becomes more of a problem as strength increases. However, if the temperature is high then hydrogen tends to diffuse more readily, it then doesnt accumulate and hydrogen damage is less likely to occur. In fact it is possible to bake outhydrogen and return affected materials to their original condition, but this isnt an option in a well! Intergranular corrosion - During heat treatment, manufacture or welding metallurgical changes can take place which cause grain boundaries to adopt a significantly different electrical potential to grains. This can lead to accelerated corrosion at the boundary and may lead to cracking.
Glossary (Cont.)
LME Liquid metal embrittlement - Liquid metal (eg mercury or other metals (eg. lead, aluminium, tin, zinc) at higher temperatures) wets the grain boundary of metal and causes grains to separate. Unusual in EP, although there have been instances where lubricants containing these metals have been used at high temperatures and LME has caused failure! Microbially induced corrosion - Degradation as the result of the metal reacting with products created by bacteria, particularly sulphate reducing bacteria (SRBs) which are found in anaerobic conditions. Typically at temperatures below 80 Celsius. NACE - National Association of Corrosion Engineers. A professional institute which has developed Recommended Practices, Materials Requirements and Test Methods in the field of corrosion. Now known as NACE International. Oxygen - A corrosive species which is not usually found downhole although it may be present (particularly in beam pumped wells) and may present in injection waters. Pitting - A form of localised corrosion in which the depth of metal removed from the surface is significantly greater than the width of the corroded area. Environments within pits can become extremely aggressive (pH 1or less in some stainless steels) and this can lead to rapid penetration of casing/tubing/vessels etc.. Because of the changes in local environment and geometry of the defect this type of corrosion can be particularly difficult to stop once it has started. Pits may also act as stress concentrators enhancing fatigue and/or hydrogen cracking. SCC Stress corrosion cracking - One of a number of failure modes resulting from the combined effects of tensile stress (applied or residual) and the environment. Often leads to catastrophic failure because the cracks are not easily detected. Occurs readily in metals and alloys which passivate in combination with a species which breaks down the passive layer. Combinations include Brass with Ammonia (the first to be discovered) and austenitic stainless steels with chlorides. May be intergranular or transgranular depending on the alloy/environment combination. Unlike hydrogen induced cracking, SCC is more severe at higher temperature and in stainless steel is rare below approx. 65 Celsius. SSC Sulphide stress cracking - A form of HIC which develops in sour service through the presence of hydrogen sulphide gas. A particular problem where operating conditions are below 60 Celsius and in high strength steels. Sour Service - See detailed definition in NACE MR0175. Note that it is the purchasers responsibility to ensure that materials are suitable for use in sour service, and that they are resistant to other forms of corrosion which may occur in the environment. Rigorous materials qualification through laboratory testing is often required. Weld decay - The rapid heating and cooling of stainless steels associated with welding can lead to the formation of chromium carbides in an area adjacent to the weld. This depletes the area of free chromium and prevents formation of a passive film allowing corrosion. This phenomena can be avoided by specifying very low carbon or stabilised steels.