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P267 Applied Production Technology Corrosion Engineering

Tony Cole EPT-DW Completions and Multi-lateral Technology Team RTS Rijswijk +31 (0)70 311 3049

Completions and Multi-lateral Team

 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

s.l.fisher@siep.shell.com m.anderson@siep.shell.com m.e.amory@siep.shell.com g.mulder@siep.shell.com m.bayfield@siep.shell.com t.cole@siep.shell.com w.r.moore@siep.shell.com

Multi-lateral wells
multiple reservoirs single reservoirs

Completions and Multi-lateral Team


 Advanced completion design
 ML well technology
 Casing exiting using milling/explosives  Novel multi-lateral junction designs

 Expandable systems, monobore completions, slim wells

 Materials selection/new materials/preparation of standards


 Materials advice  Testing procedures/Industry Standards

 New coiled tubing technology


 Amorphous bonding  Use of CRAs with orbital TIG

 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

Applicable specifications Non-NACE*

 API 5CT / ISO 11960  API 6A / ISO10423  API 17D  ISO 13680

(under rev.)

Steel pipes for casing and tubing of wells


Wellhead and christmas tree equipment Sub-sea wellhead and christmas tree equipment CRA tubes for use as casing and tubing

*NACE

= National Association of Corrosion Engineers

Applicable specifications NACE

 MR0175  RP0475  MR0176  TM0177  RP0273  RP0291  RP0186

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

General Corrosion Principles

 Electrochemical in nature
 Involves the transfer of electrons  Requires electron path and ionic path

 Requires two half reactions


 Production of electrons  Allows consumption of electrons Fe + H +e Fe
2+

+2e H

General Corrosion Principles

 Must consider two aspects


 Thermodynamics - Willingness to corrode
Measured using potential difference (Voltage)

 Kinetics - Rate of corrosion


Indicated by electrical current flow Increases with concentration/temp./fluid velocity

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

 They do not say anything about the kinetics, or rate, of corrosion

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

High impedance voltmeter

Types of corrosion

Unusual types of corrosion


 Ring-worm corrosion
 Localized corrosion around box end

 Wireline attack (also in coated tubing)


 Internal scratches along the tubular corrode rapidly

 Caliper track corrosion


 Similar to wireline attack, but caused by the feelers of the caliper tools

 Sucker rod failure


 Often caused by pitting, then fatigue

 Tong damage
 May lead to localised corrosion

Wireline damage - WI well ExPro

What makes Wells special...


 Geometry
 There are usually concentric strings of casing  Direct corrosion monitoring is difficult, preferably nonintrusive (or its usually high cost)  To a certain extent the annulus environment can be controlled

 Completions designs are determined by:


 tubing size required for flow performance  mechanical integrity (principally tension, burst and collapse)  Life expectancy (typically the time to a workover, usu. 10 years)

 Tubing, casing and jewelry to consider  Acidisation for stimulation may be a factor

Potential corrosion sites in a well...

Internal casing corrosion

 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

Factors influencing corrosion


 Aggressive species
 Water plus
 O2  CO2  H2S  Cl-

 Others
 Pressure  Temperature  Flow rate  pH  Bicarbonate  Bacteria  Galvanic couples  Differential concentration  Dew point  Inhibitor  Coating/lining

Corrosion rates - Species dependency

O2 is about 80 times more corrosive than CO2 and 400 times more corrosive than H2S

Common corrosion reactions


 Sweet corrosion
CO2+ Fe + H2O FeCO3 + H2

 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+

The types of corrosion caused

Sweet



Sour


General corrosion
(calculate using model. Shell uses Hydrocor which has been provided)

Pitting  Leaks  Grooves Scaling

Hydrogen induced cracks  Sulphide stress cracking (esp. < 80 C)  Blistering




The types of corrosion caused

Chloride  Pitting  Stress corrosion cracking of corrosion resistant alloys


(esp. above 80 C)

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

Mitigation methods: Operations

 Remove the corrosive species


 Downhole dehydration?  Injection of chemicals to prevent or remove H2S

 Inhibit
 Continuous  Batch

 Cathodic protection (for casing)


 Impressed (continuous or pulsed for casing protection)  Sacrificial

Inhibitor application: Batch


 Tubing displacement and Squeeze treatments
 Inhibitor flowed through tubing  For displacement the tubular is filled and the well shut-in. With squeeze the inhibitor is injected through the tubular into the reservoir  Typically shut-in for a day  Inhibitor residuals monitored at wellhead  Another treatment is necessary when ppm falls below a pre-determined level  May require one treatment every 3 or 4 months  Squeeze protects below the packer

Inhibitor application Batch


 Weighted inhibitors
 Intended to fall to rat hole and slowly release

 Encapsulation
 Inhibitors encapsulated in polymer gel are introduced into the well, either in a basket or in the rat hole.

Inhibitor application Continuous


 Continuous
 Through the production annulus  Into the casing through a valve positioned in a side pocket  Its possible to inject into a specific region of the string  Can simply fill the annulus with inhibitor and inject through a gas lift valve, but this lacks control.  Doesnt protect below the packer

Casing cathodic protection


 Usually requires quite large currents  Is difficult to directly measure the affect of applying current
 Often attenuation calculations are used to give a comfortable feeling  Casing pressure surveys may be used to measure success, provided enough baseline data exists  Remote well-head measurements are often used

 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

E lg i for cathodic protection - Equipment

 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.

E lg i for cathodic protection Results


 Results look similar to lab tests on small coupons  The change in gradient as the Tafel portion of the slope is reached gives an indication of current  However it is only an indication and should be supported by other techniques to provide greater confidence

Monitoring and measuring

 Split into two categories


 Intrusive
 Those which require production to stop

 Non-intrusive
 Can be done without interrupting flow

Monitoring and measuring

         

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..)

Monitoring and measuring: Intrusive

    

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)

 Inspection of recovered tubing  Pressure testing

Kinley Mechanical Caliper tool (www.kinley.com)


Other similar tools available eg. www.read-well.co.uk/mfctool.htm - electronic version www.mws.no/mws.nsf/pages/FrameSet3

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

Kinley caliper - Fingers

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.

Kapuni Caliper corrosion.

Kapuni Caliper Corrosion

Ultrasonic corrosion inspection tool (Schlumberger)


http://www.connect.slb.com
Features: Rotating pulse-echo transducer gives 360 coverage. High-resolution focused transducer quantifies even small defects on both internal and external casing surfaces. Precise first echo time gives accurate and detailed internal radius measurement. Second echo time gives casing thickness. Internal and external surface echo amplitudes give a qualitative visual image of casing condition. Well-site presentation is corrected for tool ex-centralization effects. Detailed examination of both inner and outer casing surfaces, ranging in diameter from 4 1/2 to 13 3/8 in. Multi-finger calipers can examine only the internal surface and may even damage the casing. Flux leakage instruments presently offer limited accuracy and coverage. Good resolution of the UCI tool is due to the very high transducer frequency of 2 MHz. The signal is, however, attenuated by the bore-hole fluid, and for best results brine, oil or very light muds should be used (no solids). Logging rate is 425 to 3000 ft/hr depending on sampling rate. Not much use if solids are present in the fluids (noise!)

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.

Casing potential profile - Equipment


 A casing potential profile is a measurement of the difference in potential between two points inside the casing not a measure of the casing to soil potential which is indicative of the likelihood of corrosion.  Typically the contacts are 3 to 10 metres apart with wires brought up to surface and connected across a voltmeter  The tool is moved along the inside of the casing with potential difference measurements taken as needed.

Casing potential profile - Results


 It is usual to run the tool without CP to get baseline data and then with CP.  A positive shift indicates current flow up the casing  In the example on the left the entire casing appears to be receiving current  Note that the tool does not indicate the casing to soil potential and therefore does not provide direct information about external corrosion.

Corrosion monitoring - Application limits

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

Downhole corrosion monitoring

Monitoring and measuring: Non-intrusive

     

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)

 Inhibitors  A combination of these methods

the damage they cause.


 Sweet corrosion
 Pitting
 At best - pin hole leaks

 Sour corrosion
 Hydrogen induced cracking
 Sulphide stress cracking  Step-wise cracking  Blistering  Hydrogen assisted ductile failure

 Deep grooves along wetted areas of gas lines


 May lead to rupture

 Often accompanied by severe scaling

 FeS dust can also block gas line filters

 Susceptibility increases with;


 Increasing pp(CO )  Increasing velocity  Increasing Temperature  Presence of particulates
2

 Susceptibility increases with;


 Increasing pp(H S)  Increasing hardness/strength  Decreasing pH/Temperature  Increasing stress (residual or applied)
2

Mid-wall cracking caused by H2S

.and how to prevent it


 Sweet corrosion
 Dehydration  Corrosion resistant material
 13 Cr or better  Non-metallic

 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.)

 Coat/line (ie. Isolate from environment)  Remove hydrogen sulphide


 Use NACE criteria (see next slide)

Factors influencing the choice of materials


 Mechanical properties required
 Dimensions and strength of material governed by well characteristics  Corrosion allowances are not normally used

 Require lowest life cycle costs (often emphasise is on capex)


 Corrosion which may cause sudden failure (eg. SCC, SSC) must be designed out  Cost of failure (eg. offshore v onshore)

 Worst case composition, pressure, temperature and flow velocity of fluids


 Differences between tubing/casing/wellhead  Internal and external

 Confidence in ability to operate within boundary conditions


 How accurate is the well data (esp. during the engineering phase)  Can inhibition continuity be guaranteed  Will water break through occur, will H S levels increase with age
2

NACE MR 0175-97 Criteria for Sour Service

API 5CT Compositions

Corrosion and API5CT/ISO 11960


 For sweet service, where calculated CO2 corrosion rates are high L80 type 13 Cr should be the minimum grade specified. If H2S is also present the synergistic effect can require a higher alloy.  Consult NACE MR 0175 for temperature limitations on the use of carbon steel materials in sour environments.  At low temperatures the relatively high strength materials C90 and T95 may be used in sour environments because they are tested for resistance against SSC during the manufacturing procedure. Specify NACE type D testing.

API 5CT and SSC


Paragraph 6.2.12 of 5CT - Refers to SSC

Effect of temperature on CO2 corrosion

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.

Manufacturers selection guide

Based on NACE, with additional data to allow selection of CRAs.

Manufacturers materials selection guideline

NAM Materials Selection Guide

NB. Should be used in conjunction with the .DOC guideline document .

Draft Shell Oil Guidelines

See the .xls spreadsheet CRA from Shell Oil. Bear in mind that this is a guide only and that the recommendations are incomplete.

Relative costs of common OCTG materials


(carbon steel = 1).

GRE 13% Chrome Super 13% Chrome 22% Chrome 25% Chrome Incoloy 825/Sanicro 28 Inconel 625/C276

2.5 3.5 7 9.5 10 20 40

Tests for materials selection

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)

For stress corrosion cracking use ripple testing

You now know:


 Types of corrosion and how to prevent them  Data required to select an appropriate corrosion mitigation technique  Some fundamental corrosion knowledge to allow you to challenge corrosion decision in an intelligent way.

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.

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