petroEDGE Corrosion Management for Oil & Gas Production a 27" to 30" April 2009 Kuala Lumpur Malaysia www petroedgeasia.netpetroEDGE we aslaDGE CORROSION MANAGEMENT FOR OIL & GAS PRODUCTION Kuala Lompur, Malaysia Dear learners, (On behalf of PetrOEDGE, welcome to “Corrsion Management for Oi & Gas Production’. This workshop il be delivered through a senes of lectures and interactive sessions. 19 order to maximize your leering in this traning course, please do bring-up your indvidval {questions to the expert trainer caring the terectve sessions scheduled through-out the ‘course, ease do take full advantage ofthis qpperunty ta also shere views with you? incusty peers attending this training course to ealure more insights on tis Subject matter ‘Should you require further clanfleation about this training couse, please do not hestate to aparoach ou PetrotOGE representative who wil be avaliable to desist you atte Feaistration desk. Alternatively, you may contact me directly at +65 67470775 or emall me 2 malinaasiaedae.net ‘Thank you for your participation at the workshop. Yours sincerely, Malina Raman PetrDEDGE (division of ASiaEDGE Pte Ltd) asiaEDGE t:Roraon Row #3.20 B07. Po Bak Farkas frane Bure Sopapaeis ears Seney igen SS 728, Gceancraie! Forsescrarersr Str iae lye Pen ns Sor, Mayen Ena onder ebate wenseandnerst wn zlowane ntpetroEDGE CORROSION MANAGEMENT FOR OIL & GAS PRODUCTION Kuala Lumpur, Malaysia Copyright {Ail material contained in these training notes is the copyright of Dr Chris Googan, the Facilitator of this workshop. [No part of these notes may be reproduced, stored in 2 retrieval system, or transmitted, in any form or by any means, electronic ar otherwise without the prior permission of the trainer's company, petroEDGE [Adivision of AsiaEDGE Pte Ltd The Course Organiser Info@asiaedae.netpetroEDGE petroEDGE Personnel at your service... Dear learners, (On behalf of petroEDGE, we always believe tat customers support and suggestions are Important to our business. ‘Should you have any suggestions to improve on our workshop or ideas on new topes for ext year, please do nat hesitate to contact any of our personne! below. Introducing petroEGE team members, they ar: Malina Raman Latifah Abdutah Strategic Lanning & Development Director | Head of alr (Publ Programmes) slaEDGE Pte Ua asiazDGe Pte Ltd Bio: +65 6747 0775 Dro: +65 erat 9749 Kt Mobile: $60 17 2263637 Mobites #05 9747 2320 mall lotfah@ecaedge.net Fazilah Abdul Hamat Corporate Telesales Executive Seintoge pte Ltd Bib: 265 6733 3009 mall feridaheasiaedge.net “Thank you for your participation atthe workshap, and we look forward to meeting you again In our future sessions.petroEDGE CORROSION MANAGEMENT FOR OIL & GAS ee PRODUCTION ‘ala Lumpur, Malaysia ABOUT YOUR WORKSHOP LEADER Dr Chris Googan is nice imenatinal Acree Carson Spec wn more thn 30 ‘ars operane aetured in oer 40 coutnan gers cores: mutes, cated ptt, bretcive costing bts and mortar. Me eretence Tas been prorat ne Ietecarton prcion mes, Oa har abo cried eu projets fang, chemi 8 [recs he fas pba and pesaed per on carn fo erode preteen, {Saunas ot caroson manogamers. Hoss covet UK Ofsore Suva Cems and 9 tow Socty areata Ect nse We ls cpl crags to reba of Coreen = ecg curse "Cosen mangenert nO and Gas ROG; peered say cnn th See ‘Traang related experience: 156+ reset: prepa and presrad exprencad sed waning ness wise Grreanaion engontng tps corosen inf and gas sic, cahoge potecon, catrax nhiton ane tasting, aroson of conte rerecemert a chemical Gear, lars vue: ABBAOFED (AE) ADNOL Aiko, Wa rer ee Rect oye agree, Konak Rerum Comorian, Gel (00, Exeraton (Asay “Thames Wher pe, Errermant Agen), Teeral (Kazaa), Dyn Old Cems (UK), Irtratoral Energy Fosdia (Ub),Sit OF Conga Ub, niu of Caran (A) fer Bown Rat Neth dre, 55 (pra), CO (Qa, nesey (UN), Bs Se, Marston O UK Lee, GEC O ah Gas (UN), ‘Vet ey Cots Lite, Das Reser CAME, Set EE ect acta Pret Epo? The flowing recent projects caida on ete bas, reed under headings: Coren Manager Netra Ctnose Petron and Cag fits he mutascpnary range of cares epee ard Pe ‘ocr once OTE aOR Ti Ok Pease aoa eT Medes consontngne recor trteSawater_| meng nevaaee etme orion rm and Ara 20 oh oa) ening ri twine hgses Sh S07 nce fr neta area 07 Kati rou Lied for OF Eon nanogmor sre rhea Sea Ovcgment | kent cg snare 09 8 ssomet |e ver ove Uma So Rw Da (OTR Grenier topos ancy Naat, | Pep Dae come are sy Cesk [Sots cone ad ar engarng 200s et OCT - ‘ron manent sey sen and pein | hn nes Pervert Chm fessor Samia) Caesn mente ten cine ct) os Noble egy (Un) ie = 5 Gass and Gs Enc OSE ‘estan corensmpmet emeamert tr ountwon | Arma cotenon natant nested 28s ope Ty ra Gie Seek ones Tay oar Rear emai, RO emene of bygeany patrn ‘Steg erie a kia PerCORROSION MANAGEMENT IN PETROLEUM PRODUCTION 27 - 30 April 2009 Concorde Hotel Kuala Lumpur Presented by Dr Chris Googan Anticorrosion Engineering Limited 4 Langley Drive Bayston Hill Shrewsbury ‘SY3 OPR. www anticorr.com,10 "1 12 Contents Introduction to Corrosion Forms of Corrosion Corrosion by Produced Fluids Microbiologically Influenced Corrosion Corrosion Under Insulation Corrosion Engineering Overview Materials Selection Cathodic Protection Protective Coatings Corrosion Inhibition Corrosion Monitoring Introduction to RBIINTRODUCTION TO CORROSION Definition Corrosion i the passage of @ meta into the chemically cémbined state. Cause Corrosion is = natural phenomenon govemed by the wel-established laws of thermodynamics. It completes the natural cycle begun when the metal was ‘exacted from its ore. ‘THE CORROSION CYCLE metal Extraction Corrosion — concen — —) at tm te Hoar Rap et ean eet, Survey of a UK indsty m ce 7 Percentage of GNP 11998: US Survey: corrosion costs 3.1% ofthe GNP sem [—] (1998-2000) own woe [———] kK offshore petroleum industry | oa pesseton [———————} Data from DT! study © Antconosin Erinerng Limes Hy uk Lumpur 2-9 2008INTRODUCTION TO CORROSION ‘The Rusting of ron the best known example of eorresion (Chemical action We + 20 +O > 2Fe(OHs iron water oxygen ferrous hydroxide Fe(Ok} reacts further to form rust Electrochemical Mechanism the metal Fe > Fe 4 20 © increase in valency > oxidation (chemical term) © lossofelections > anodic process ‘electrochemical term) ‘= the environment 2HO0 + O, + de > 40H" © decrease in valency > reduction (chemical term) © eonsumption of electrons -> cathodic process (electrochemical term) ‘Some Terminology ‘anodic reactions occur at anodes, or anodic sites, on the surface cathodic reactions occur at cathodes, of cathodic sites, on the surface negatively charged ions (anions: Cr, OF, SO,*...) are attracted to arades postively charged ions (cations: Na“, H’, Fo...) are attracted to cathodes © Anerotion Engineering Unt 1 ua Lumpur 290 2008INTRODUCTION TO CORROSION Corrosion in Acids commonly encountered example of corrosion ‘Chemical resection Fe + 2HoL > Foch + He iron acid ferous chloride hydrogen gas Electrochemical Mechanism + the metal Fe > ore +e + the environment 2HoI > om + 2or 2H > He ‘The Corrosion Cell ‘environment Fe 10 +0, Fete «© Ancorosin Erinerng Lied + ala umpur27-20 Ae 2088INTRODUCTION TO CORROSION What do we need for corrasion to occur? 1. metal capable of undergoing an anodic reaction * all tals can 2. an environment containing a corrodant (cathodic reactant) capable of ‘oxigizing the metal to a chemically combined state ‘= notall environments can 3. an environment that is electrochemically conducting * liquid water Environments that can (and cannot) give corrosion Corrodant Example Wetal ‘Sieel_[ Copper [Gold Gasolved oxygen | Seawater | eorodes [corrades | mmune ‘mineral acid Hel corodes |immune | immune oxidizing acid HNO; corrodes |carrodes | immune strong oxidizing acid] HOUHNOs | comrades | corrodes | corrodes Potemtiat Equilibrium ‘ Antcorson Ergeerng Utes a la Lumpur 2790 Ag 2008INTRODUCTION TO CORROSION ‘Some Standard Equilibrium Potentials Au 5 Aut + oe E a1s0v O24 2H.0 +40 = 40H EB 23v cu cut + 2e & 404v PH + 2 =H & 000v Fo Fo® + 26 & o4av (poten tered the Standard Hyrogen elect) Theory For corrosion to occur there must be a viable cathodic process available with an ‘equilbxium potential more positive than the equilbrium potential of the metal Hence: ‘+ ron corrodes in mineral acids or oxygenated waters ‘copper corrodes in oxygenated waters, but notin mineral acids ‘© gald does not corrode in either mineral acids or oxygenated waters, Practice Knowledge of equibrium potentials tells us whether or not a metal can corrode in a given environment. It does not tell us how fast. Most engineering structures and equipment is made of steel or other ferrous based alleys; 80 corrosion must be considered to be inevitable when they encounter any ‘environment containing moisture. Water ‘Often there is litle or no corrosion inthe absence of quid water. Gh gas (<125 0) | HClgas (<2506) | Crude Hydrocarbon (containing CO2) ary | _ carbon steel ‘carbon steal ‘carbon steel wet anim rickel alloy inhibitors oF corrosion resistant alloy © Anicersion Erlang Lmtes +s asta Lumpur 290A 2000INTRODUCTION TO CORROSION Factors Affecting Corrosion pt (acisty/alkainity ‘+ lower pH (usually) results in accelerated corrosion ‘+ some metals are amphoteric (they dissolve in alkalie environments) ‘©. examples: zine, aluminium ‘© for ste}, the corrosion rate is a minimum in weakly alkaline solutions (due to the formation of partially protective surface fis). allions influence corrosion allons add tothe conductivity of the solution ons which form insoluble compounds with the metal can lead to protective fim formation; but this. can promote pitting atack. ‘© exampies: COs", OH and S* (on steel) halides (particularly Cr) can be aggressive to passive films: S04" is also aggressive to passive fms only oxidizing (cathodic) ions actualy cause corrosion uid Eiow ‘= complex interaction with corosion processes ‘+ itcorrosion rate is determined by the flux of cathodic reactants (e.g. dissolved ‘oxygen) then increased flow will stimulate corrosion ‘© example: carbon steel in seawater conversely passive metals benefit rom some degree of flow © example: stainless steels perform well in flowing environments but are at risk under stagnant conditions ‘+ very high flow rates may give rise to erosionicortosion problems (passive and ‘non-passive metals) Temperature ‘+ most chemical reactions (Including corrosion) go faster asthe temperature increases. ‘ut, higher temperatures may reduce corrosion rates: ‘S elevation above the dew-point © disengaging dissolved zathocic gases ‘©. formation of insoluble, protective carbonate scales (© Artcanosion Engrg Lt +e Kala Lumpur 270 Ape 2000INTRODUCTION TO CORROSION Corrosion is not a property. Itis a process metal Jenvironment circumstance Corrosion engineering options to consider tesiantatey > tonetalion >) ¢ coating > a) Environment (Cchemical treatment >> iH |Crcumstance | (C clectrochemical >) © Antconoin Erinetng Ltd “7 ea Lumpur 2790 Ao 2000FORMS OF CORROSION Overview |We have looked at two forms of corrosion: rusting and dissolution in acids. But ‘corrosion occurs in numerous forms; not all of which are immediately recognizable a8 corrosion. =< om al c——S> core] [nowy tien] [mec a influenced | | crevice fatigue eae |e eee | ace eae ls = 4 Uniform Corrosion General Examples ‘+ rusting of iron and stee! ‘© dissolution in aids ‘+ atmospheric corosion of zinc (galvanizing) Most straightforward form of corrosion to deal with corrosion allowance inhibitors coatings ceathodie protection (combinations ofthe above) ‘© coro Engaaing Linas et uta Lumpur 2-30 Ap 208FORMS OF CORROSION Corrosion allowance: ea ehness or The wall thickness for pressure retention (x a safety factor is sometimes referred to 8 the minimurm allowable wall thickness (MAWT) Passivity Passive films are very thin corrosion product films (usualy oxides) that form very rapidly and then effectively prevent further attack 25 potienad meta surface (optically Hat) roughness 25010 Examples: ‘+ iron-chromium alloys (the stainiess steo!s) ‘+ aluminium and its alloys titanium = ickel alloys ‘Note: Providing the passive flm is undamaged (or, i its damaged, the condtions favour rapid film repair corrosion rates wil be very low indoed. However, if the fim is damaged, and the environment does not favour rapid film repair, then localized corrosion can occur (see notes on pitting and crevice corrosion). ‘© AnteareeanEnaoting Ltd 22 eta Lumpur 27:90 Ap 208FORMS OF CORROSION Localized Corrosion (Non-Mechanical) Bimetaic Corrosion (also commonly referred to as galvanic corrosion) Relative potentials in seawater: platinum 90t6 vo graphite ‘tanta “stalnieas ste! (pagive) kel passive) onel onze ‘copper brass Smal active) aa) ‘stainieas stot (active) 5, eobon seat ‘aluminium Example steel nt copper seawater Fem FepRem Fe 2040, 0+ ttt et eee ( Anicension Engnenng ied a3 da Lumpur 27:9 Ag 2008FORMS OF CORROSION ‘Bimetalic(Qalvani) corrosion ~ factors sensitive to + environment compostion (cathadic reactants} * environment conductivity + fuid flow relative area ratios ‘© small cathode : large anade - safe © large cathode : small nade > unsafe Bimetalic (galvanic design rules) ‘+ (possible) design using one metal ty to use metals close together in the galvanic series * consider isolating the mwa metals + make the anode camponent of thicker section > coat the cathode do NOT coat the anode * consider cathodic protection (important: just because there are two different metals does not necessarily mean that there wl be a bimetalic corrosion problem) revi jon Crevices can be formed between: ‘+ two similar metals, or ‘+ two dissimilar metals (may alsoaltematively produce bimetallic corrosion) ‘+ ametal and a non-metal (eg. a metal and a polymeric gasket) itis predominanty a problem of the passive metals For crevice corrosion to occur the crevice must be tight (¢.9. an interference fi), The following sequence may then occur: + (iiialy) corrosion occurs inside and outside the crevice ‘+ oxygen becomes depleted within the crevice '+ lateral variation in oxygen concentration gives rse © a potential diference between the inside and the outside ofthe crevice (also referred to as a differential aeration ce). ‘a corrosion cell develops with the crevice area being the anode Chloride (anions) diffuse under the electrical gradient into the crevice (anode) longer term: hydrolysis within the cravice = low pH conditions low pH and high [Cr] > depassivation and rapid corrosion within the crevice @ AniconotonEagnesting Ut ae et Lumpar 27.90 Apa 2008FORMS OF CORROSION Crevice corrosion factors ‘+ occurs only under immersed conditions ‘+ resistance depends on alloy composition © sek increases as: © [Ci] increases © temperature increases © pH decreases iting Ideally, whenever a passive fim is damage it repaisitsel: 1 Passive im nact es 2 Paasve tim damoged 3 Repassivation ee However, it aggressive anions are present then pitting may initiate 1 Passive tlm damaged 2 Pitintation M6 xc > Mey otabe) — © Arcorosen Engineering Lined 25 uta Lumps 27-90 Apt 000FORMS OF CORROSION it propagation - can become autocataytc: Examples of pting ‘+ (some) stainless steels in seawater ‘+ aluminium alloys in marine environments Pitting is exacerbated by: + increased concentration of aggressive ions + oxidizing agents * elevated temperatures + stagnant conditions + horizontal {upward facing) eurtaces (see notes on materials selection for information on the pitting of stainless steels) © dtcorsin Engng Leon a6 nla Lumpur 27.90 Ap 2000FORMS OF CORROSION lntearanular corrosion Example: stainless stee! (with corect heat treatment) Microscopic view of grain boundary region: Elemental analysis along dotted a, Example: Stainloss steel (heat treated at 550 - 800 0) (Cr depleted zone chromium carbides mm | fame . active ute | eal uur 27.30 Apa 208 ‘© aniconsienErgoering tos 27FORMS OF CORROSION Intergranular corrosion (cont) + problem © grain boundary region becomes less corrosion resistant © galvanic cell established ‘grain boundary > anode + grairinterior > cathode + example © stainless steels ‘© igh strength aluminium alloys + remedy © heat treatment > re-homagenize © modiy alloy formulation. For stainless steels > * "low carbon versions: + TiorNb stablized se hing (de-alloyin The selective dissolution of one element from an alloy mati examples ‘+ Fe trom grey cast ron (graphitic attack) ‘= Zn rom brasses (dezincfication) ‘+ Alfrom aluminium bronzes (de-aluminiication) Potentially serious Efocts are often dificult to see withthe naked eye {Not common in hyérocarbon production) Deposit Corrosion ‘© analogous to crevice corrosion ‘lateral variation in solution compostion between: ‘© under-deposit > oxygen depleted > anodic ©. deposit free > oxygen access > cathodic ‘+ metal loss occurs under deposit ‘+ problems usually involve passive metals (+ chloride) ‘+ note: in hydrocarbon production systems deposits can favour microbialy Influenced corrosion (MIC) ~ (see later notes) ( Arcorosin Engng Unto a8 la Lompur 730 Apt 2008FORMS OF CORROSION Localised Corrosion (Mechanical) ress Corosion Cracking specific tensile corrosive environment i) stress corrosion cracking ‘Stress corrosion cracking characteristics + sess © tensile (applied or residual) © 2mgl, T > 80.0) ‘+ duplex stainless steels in (some) HeSICT containing olf sds ** carbon steels in carbonate/bicarbonate mixtures (buried pipelines) ‘thers: ‘eric steels in NaOH solutions copper allays in ammoniacal solutions titanium alloys in ethanolnydrochloric acid mixtures nickel in fused caustic soda ‘carbon steel in hot nitrate solutions sensitive to stress level + environment (including concentration effects) ‘+ metallurgical condition + temperature The cracks are rarely visible (0 the naked eye prior to ‘allure; (require NOT techniques e.g. dye pene!ran}) ‘counter-measures: + eliminate stress ‘0 anneal (lowers residual stress) ‘© taconosin Engen intos 2-10 ula Lumpur 27-90 Ag 2008FORMS OF CORROSION © thicker section/lower applied load (reduce applied stress) © shot peening (surface stresses -> compressive) + oF eliminate corrosion ‘© material selection © cathodic protection (Gonosion Fatigue ‘Mon-specitic. cyclic corrosive oo ‘environment ‘coresion fatigue Fatigue Corrosion fatigue 'S-N Curves for Carbon Stee! © Ardcoroson Engng Lene a ala ump 27.30 Aye 2008FORMS OF CORROSION low frequency cycles are more damaging (per cycle) Cracks often itiate at corosion pits ‘not highly spect to metallenviranment (unike SCO) fatigue affects all metals, fatigue is accelerated by corrosion Ezosion Corrosion + piging standards (API APP14E, BSBO10) give guidelines for erosion: Ve = mp where Ve = erosional velocity (ns) m= emptrcal constant (122) B= fluid density (kgim’) ‘+ guidelines are useful as a "First Pass"; but a more considered analysis may ‘be required ‘high fu vetacty aiscupts passive fl often associate with ‘©. change of flow direct © onset of turbulence ‘+ depends on: (© degree of turbulence © presence of entrained solids © design Cavitation ‘+ sudden pressure drop in fuis © local fuid pressure <'iquid vapour pressure © > cloud of vapour bubbles * fluid pressure then re-established ‘©. vapour bubbles collapse ‘© implosion > percussive attack on surface © disruption of passive fm = damage: ‘© mechanical and © chemical (corosion) + Occurrence: pumps, piping, diesel engine cylinder ners + Remedies ‘©. design (pressure regime) © materials hard alloys, or + elastomeric linings ‘© setconoion Engng Litas a ea Lonpar 2730 Ao 2008FORMS OF CORROSION tina Corrosion features (© two metals sip relative to one another ina caccosive environment © (Similar to erosion corrosion) © protective flm removed mechanically © cortosive environment attacks freshly exposed surface © allack often exacerbated Dy abrasive nature of removed corrosion product + example ‘© wife rope in a marine environment ( Artconostn Engng Lined a8 usa Lumpar 27-20 ser 2008CORROSION IN PRODUCED FLUIDS INTRODUCTION “The inienal corrosion of hydrocarbon production pipelines, pipework and equipment Is due tothe presence of liquid water in the product stream, No water = No corrosion Water (as quia or vapour is produced from all hydrocarbon reservolrs. ‘The corrosvity ofthe water depends on: ‘composition: ‘dissolved geses (principally CO, and H,S) 3 cathodic reactants + dissolved saits > may modily corrosion behaviour ** presence of tresting chemicals > may inhbit (or accelerate) corrosion ‘sircumstances: + pressure: ‘+ temperature (and heat vanster) ‘flow (static, turbulent, muti-phase) In this module we wil look at: the properties of pure water Its role as a solvent the effect of dissolved CO, on corrosion the effect of H,S, both on corrosion and on cerrosion-related cracking WATER Pure Water ‘Tne properties of water are dominated by hydrogen bonding. For example, without hhyérogen bonding we would expect water tobe a low boiling poirt gas. =) qh ST wo i, vane ? vg Zo] us ctr Wag © Antoonosin Engng Linas ae la Lumpur 27 90 Apt 208CORROSION IN PRODUCED FLUIDS Pure water dissociates (slighty) to form hydrogen ions (H") and hydroxyl ions (OH). Ho = + oH + pH = 4ogulH] + pH of pure wateris 7 oH] =107gionst == 10% © [OH]=107 gions! = 4.7 x 10% gt © HO « 99.9998% + pH< 7 acid, pH>7 > alkaline Water as a Solvent Water is an extremely effective solvent, it comes into contact with: ‘+ atmospheric gases sali, rocks organic matter ‘+ industrial processes and pollutants: 28 a result natural water contains both dissolved and suspended solids Typical Waters Conductivity is related tothe concentration of dissolved ions: Log Resistivity (ohm.m) 2 3 4 5 6 Log Total Dissolved Solids (mgt) ( Aniconosin Enea Limtas a2 ala Limp 27-20 pt 2008CORROSION IN PRODUCED FLUIDS Constituents of Oilfield Brines Cations calcium ‘+ major component (up to 30.000 mgf) + precipitates with HCOs", CO,* and SO,* > scales andior suspended solids magnesium * typically lower concenttation than Ca (c<0.1 x (Ca) ‘+ MgCOsis mach more soluble than CaCOs + MgO: may be incorporated in CaCOs scales. sodium ‘© present at high concentration (thousands of mg) * does net form insoluble products barium ‘produces extremely insoluble scale with sulphate (BaSO,) ‘+ BaSO, scales are very dtfcut to remove + high Ba waters are usually low in $Oy" (and vice-versa) soxtam Goes an nse suphats (1504) + Sete aly one neoported BeSOuszaos 1 Siiodt ome may dave tom the omaton andor coneion othe production equpnat may be soluble: ferrous (Fe*) or insoluble: ferric (Fe*) tral be prosontssuopandod eal tones) Seposied ds can prove on onion conduct MC Anions chloride ‘+ major constituent (often > 100 000 mgf}) ‘+ not involved in deposition pracesses ‘+ nota cathodic reactant, but may promote localized attack on passive metals ‘+ may promote pitting of carbon steel otnerwise protected by a sulphide scale bicarbonste/carbonate **brines usually contain only HCO + small rise in pH can: 2 > COs © > insoluble sats with Ca ‘+ carbonate scales easily removed: acid or mechanical cleaning ‘sulphate “© hieorosionErgnocing Utes 3-3 aula Lump 27-90 Ag 2000CORROSION IN PRODUCED FLUIDS ‘readily forms insoluble salts with Cat*, Ba”, $2 ‘salts dificult to remove (chemically or mechanically) + S0.*is metabolized by suiphate reducing bacteria > risk of MIC Gases carbon dioxide (C02) ‘= may encourage scaling in high Ca®* waters ‘+ may reduce pH enough to: © prevent scaling © increase corrosion hydrogen suiohide (HS) *issolves to produce an acid solution + may produce protective sulphide films + > sour problems + may indicate MIC oxygen ‘+ not normally present in reservoir fuids ‘+ may be introduced into injection waters °°. @.9, due to defective seals on the suction side of the injection pumps ‘+ may be introduced wih treating chemicals © @4. dissolved in methanol ‘+ > greatly increases the corrosion rate of carbon steels Others + Heavy metals: ‘©. Vanadium: (present in some crude ols) > gives high temperature certosion problems when burnt as heavy fuel oll ‘© Mercury: (present as vapour in some gas fields) > may become liquid as gas is cooled (cryogenic plant) avoid aluminium perceived issue of high temperature embritlement of Ni alloys ‘© anteoroson Engng Lned a4 ts Lumpur 27-20 Ap 208CORROSION IN PRODUCED FLUIDS ‘SWEET CORROSION (ALSO CALLED “CARBONIC ACID" CORROSION) ‘An environment is classified as sweet fit contains CO» {out not H.S). ‘Typical example of sweet corrosion: (Only takes place in the presence of quid water; COs dissolves, lowers the pH and produces acid attack. CO, + HO > HCO. (carbonic aia) H:005 > H+ HOO; Heoy > H+ coe Rate of corrosion increases wit ‘+ temperature + C0; partial pressure + fluid turbulence Cathodle Reactions HCO. + 2) > COs +H 2H + 2 > He “The dominant cathodic process is the reduction of carbonic acid. At any given pH carbonic acid is more corrosive than hydrochloric acid. ‘Snell started conducting work on COs corrosion rates in the 1970's. Laboratory ‘experiments showed that corrosion rate increased with: + COs partial pressure + temperature Alarge number of corrosion rate tests were carried out at diferent levels of CO; and temperatures. Data were then examined to produce an empirical relationship. Results fst published in 1975, ‘© Ancanoson Engineering Lites a8 al Lumpur 27-20 2008CORROSION IN PRODUCED FLUIDS de Waard and Miltams Algorithm’ logR == «SB - 1710 + 0.87l0g(Poce) as where: corrosion rate of sige! (mmiyear) temperature (Kk) Partial pressure COr (bar) ‘mal tration CO; x Poyawm total system pressure (bar) ‘The algorithm has been widely used to decide whether: ‘+ carbon stee! can be used fr facilities construction and, iit ean, then + whether additional cerrsion control is required ‘The algorithen is generally regarded as giving @ worst case prediction. Subsequent ‘work by (mainly by Shell) accounts forthe moderating effect of + elevated pressure and temperature ‘+ the presence of other fluids (e.g. hydrocarbon iquids, treating chemicals) * pH Elevated Pressure ‘To account for the nor-ideal behaviour of natural gas the fugacly teoe should be used! fone aPeoe where ais the fugacity coeticiant (a < 1), Values of « are unlikely to be known for the gas mixture. As an approximation, the ‘multiplier Faysam Can be applied tothe consion tate R calculated by the algorithm, log Fayaum = 0.67(0.0031 = 1.4/7)Paytan levated Temperature ‘Above the scaling temperature (Tiexe) an FeCOs or FesOs corrosion product forms ‘28 apratectve film (providing the fui flow is <20 m/s and non-turbulent) Teste 2a BT + 0.8709 Toce Taps Toe log Frese 2400 - 0.6 logP coe - 6.7 oe 7G. de Waar U- Lo, U and DE Milams Conosion a7 376 (1201) © Aaicoroson Engineering Limi a6 at Lumpur 27-90 At 2008CORROSION IN PRODUCED FLUIDS Fae can then be applied to R to correct for the beneficial effect of the corrosion product. (i Toyam < Tze then Faye = 1) Presence of Oi Simplistic guideline Water Cut | Flow Vetocily | Free Waier any <1 mis Yes 50% >is No [-s0%-40% [1.5 ms No 30% - 40% 1=1.5mis Unlikely [7 340% [any Yes ‘+ Ifo free water then no corrosion (F=0) ‘+ Be aware (current corrosion rato models for multiphase fluids are less clear cut about whether or not iquid water will separate). It depends on the water- entraining capacity of the crude, which varies from reservoir to reservoir. Gondensates ‘+ law molecular weight gas condensates have litle inhibitve effect on CO, corrosien Ir hemicals ‘+ methanol (hydrate suppressant) > mild inhibitor ‘+ monethiylene glycol (MEG) (hydrate suppressant) > mild inhibitor ‘triethylene glycol (TEG) (used in dehydration) > mild inhibitor {glycols also reduce the dewpcint temperature ofthe gas) oH + the ofiginal Shell laboratory work was carried out in unbuffered NaCl solution. ‘= found to give reliable results for condensed watar in gas systems. ‘+ less reliable for produced waters: ‘2 some fluids contain ow melacular weight organic acids (lower pH) 5 bicarbonates provide buffering + algorithm modified to account for: ‘© measured pH (it available) © pH calculated from produced water chemist. Amicon Engeting Ute a7 la Lompi 2790 Apt 2008CORROSION IN PRODUCED FLUIDS ‘The Effect of Flow ‘The original Shell experiments were conducted in static test cells (with stived liquids) ‘988: porrants cared out fow Hoe at ete for Erno (FE) (Gee. Data analysed nthe form ofa “parallel resistance" mode Wer = M+ AN whore: Ver * — comosion rate v ‘maximum possible corosion rate (nfritly fast mass transfer) Ne = highest possible mass transfer rate. Effect of Fluid Velocity on CO2 Corrosion Ey as | ew 8 (1999) ° de 8 M(1998) 0 Corrosion rate (mmiy) 100 ‘Fluid Flow Fate (ms) 0. de Waard U. Lotz, and A, Dugstad Paper 128 CORROSIONS © Anconosion Erginerhg Unto ae ala Lumpur 27-90 Agr 2008CORROSION IN PRODUCED FLUIDS CO; Corrosion Rate Prediction Software Available (Excei ® spreadsheets) + Hydrocor Shel) ‘© Available under licence trom Shell Global Solutions © contains options to model the corrosion rate vsing different madels: ‘© doWaard, Miliams & Lotz algorithm best fits to JFE flow data + limiting corrosion rete (LCR) model - this is a means of deriving corrosion rates from electro-cherical principles © permits rate caldulation in the presence of H,S (less sound theory, Possitly more consarvative) © also includes the effect af elemental sulphur. (Predicted carbon steel corrosion rates in the presence of water + elemental sulphur are likely to be 80 high as only to be of academic interest) + Cassandra (BP) ‘© proprietary to BP but (early versione) disseminated more widely than Hydrocor © sirilar to Mycrocor (based on IFE flow data) (© no HeS or suighur assessment = NORSOK M506: ‘© available by download from NORSOK web-site © based on YFE flaw data ‘© no HS or sulphur assessment + ECE ‘© lence avallable from lntetech Limited (Chester UK) © models the eect of HS © contains a materials selection module Warning: De not over-interpret the models’ results: ‘+ Corrosion rate data presented to 4/- 0.01 mmiyaar ‘© Accuracy: probably no betta than +100 to -25% in the best ot cases! The role of the madels is to decide whether carbon steel can be used for a given application; for which the models’ ballpark results must be interpreted with “engineering judgement ‘Top-of-Line (TOL) Corrosion This isan area of potential concern in multiphase lines with stratified flow. Corosion inhibitors ae expected to work inthe liquid water phase al the bottom of tre tne: but are not expected reach the top ofthe line where condensation will be occurring ‘The models are less certain in dealing wth TOL corrosion: ‘+ Eally models simply estimated TOL rates as the BOL rate dhided by a (conservative) factor ‘@Anicoreton Engrs Linted a8 ai Lumpur 27-0 eseCORROSION IN PRODUCED FLUIDS + More recent modes assume tims of iron-saturated water, which promote ‘scaling and attenuated corrosion rates. ‘+ In practice TOL corrosion is rarely @ problom unless there is very rapid Cooling of the line (Le. high rates of water condensation) For example in a land-based pipeline ata river crossing HYDROGEN SULPHIDE HS Uke CO, HeS dissolves in water to form.an acid gas. Hence it provides a cathodic process that supports the anodic dissolution ofthe steel We need to consider: ‘+ The role HeS plays in the corrosion of steel ‘+The eracking problems in can give rse to under some circumstances (see below C0, and H:S Corrosion Even where crude hydrocarbons contain H:S, they invariably also contain COs in greater quantities. Accordingly, we do not consider H,$ corrosion as such. Rather Wwe examine how HeS modifies the GO: corrosion Viewed simplstcally, HsS tends to act as an inhibitor of COs corrosion. Conosionmode | 00s zed COWS Hs cons ato >e00 2500 <0 Doman cle eco, FeSO, Fs ronoloey gonerals | generals locaized | localized Cores ae cee moat | FEwOTeTTAN CO, | mel wit owe roscton vie | peat ‘An additional corrosion mitigation benefit of HpS, not reflected in the models, isthe fact that sulphide fms favour ol-wetting ‘Arico Eginoaing Unie a0 ut Lp 27-20 Ap 2008CORROSION IN PRODUCED FLUIDS ‘Sour Systems. "Note: the term “sour” fang out of fashion. tis now more normal to describe systems as "H,S-containing’ A system may be classiied as sourit it contains: © water ‘+ HS (ahove certain levels) ‘Definitions of a sour system AUNACE MR0175 Materials Requirements ~ Sulfide Stress Cracking Resistant Metalic ‘Materials for Oilfield Equipment ‘Souraas Pry > 0.4 Mpa (65 psia) hes) > 0.003 MPa (0.05 psia) Iroll Pay) > 1.8 MPa (285 psia) [HS] > 15 mob (gas phase] Pres) > 0.07 MPa (10 psia) GOR > 5000 SCFibbI (890 Sm*im®) os (IG j son 1 verso on i, ‘Sour I He tee sur (M0175 has been froquenty revised and updated since It was frst issued in 1975. Itis now issued as ISO 15156 ~ see below) ‘© satconosn Engen Lites on etme 27-20 Ap 208CORROSION IN PRODUCED FLUIDS ror ion of (EFC) Publ. No, 16 (1985) Guidelines on materials Requirements for Carton and Low Alloy ‘Steels for HeS-Containing Environments in Oil and Gas ‘production Publ. No. 17 (1996) Corrosion Resistant Alloys for Oil and Gas Production: Guidance on General Requirements and Test methods for HS Service, Define sourin terms of Pres and pH and also identifies an intermediate zone (2) and cance tocn 8) wetsour asl drogen Supise Prt Pressure) Pars of these EFC documents are also included in ISO 15156 (see below) aso 15156 Petroleum and Natura Gas Industries ~ Materials for use in HpS-containing ‘environments in oll and gas production Part 1 General principles for selection of cracking-resistant materials PPart 2 Cracking resistant carbon and low alloy steels and cast rons. art 3 Cracking resistant CRAS (corrosion resistant alloys) and other alloys (May be regarded as & combination of MRO175 & EFC documents, and supersedes both) Does not give an absolute definition of sour service. Rather, HeS-containing environments have to be evaluated on the basis of Pras, pH, ‘emperature and chiorde content. icone Engineering Ltd a une Lumpur 2-90 Ap 2008CORROSION IN PRODUCED FLUIDS (Cracking in H,S-Containing Environments ‘The Etlect of Sour Consitions on. ted Hdror Overall cathodic reaction in acid 2H (aqueous) + 20 => He (gas) a Reaction (1) proceeds via a series of sequential steps on the metal surtace: Ht (aqueous) > HY (adsorbed) (ia) Hi (adsorbed) + & > He (adsorbed) (1) 2H+ (adsorbed) > He (gas) (te) (where He is atomic hydrogen) Sulphide is a cathodie poison, It inhibits reaction (16) — atomic bydrogen recombination undischarged atomic hydrogen accumulates on the surface hydrogen atoms are small enough tofitint interstices in the metal latice ‘some atomic hydrogen diffuses into the metal this can cause hycrogen damage faeces SOHC) (Gaon blisters cracking cracking ‘e Anicenosen Ergun Lintod a19 usa Lumpur 27-9 Ap 2009CORROSION IN PRODUCED FLUIDS ‘The effect ofthe hydrogen depends on whetrer: ‘+ (combines to form molecular hydrogen gas (Hz) o> increase in volume © > pressure effects ‘+ remains as atomic hydrogen H+ ‘© > embritlement eects ‘+ Heand He exon a combined effect ‘© > stress atientated hydrogen induced cracking (SOHIC) yamane due {0 molecular hydrogen “The combination of H+ 16 fore He occurs at an internal surface: voids + laminations * inclusions + micro-eracks ‘The hydrogen molecule (He) ie much bigger than the two bydrogen atoms from which itis formed. The molecule is not able to difuse away through the metat lattice. Hence Ha gas accumulates and generates pressure. This results in © blistering: steel strength < ~ $50 MPa (~80 ksi » cracking: steel strength > ~ $50 MPa ‘Terminology for eral 1. hydrogen bister tracking 2. hydrogen pressure cracking (HPC) 3. hydrogen induced cracking (HIC) 4, hydrogen induced stepwise cracking (HISC) 5. stepwise cracking [SWO) 6. hydrogen pressure induced cracking (HPIC) Exam brcasin Engncerg Lied a4 usa Lumpur 27-30 Ag 2008CORROSION IN PRODUCED FLUIDS age due to Atomic Hydrogen ‘Atomic hydrogen can give sise ta hydrogen embrittlement (HE): ‘+ metals undergo plastic strain by the movement of distoctions through the latice 1+ Prin te iatice embritlement and cracking © fast strain: dislocations move too fast to interact with He ‘+ co embritlement or cracking For susceptible materials the risk of HE increases with: + strength (hardnoss) cold work (plastic deformation) ‘stress level (residual or applied) ‘Steels potentially subject to HE: + severely cold worked © plain carbon steel © fate stainless steels 2 austenitic stainless staols ‘+ heat treated to strength > 790 MPa (Re=22) ‘© plain carbon slae! (©. martensite stainless steel + as-welded stoa! ©. plain carbon stool (0<0.22%) © martensitic stainiess ste! © oretion Engineer ints a8 una arpa 27-20 ap 2008CORROSION IN PRODUCED FLUIDS ‘Terminology of embitioment-related phenomen: 1 hydrogen assisted stress corrosion cracking (HSCC) ‘+ hydrogen induced stress cracking (HISC) ~leasily confused with hydrogen, induced stepwise cracking). + hydrogen assisted cracking (HAC) © the above terms are broadly synonymous + sulphide stress corrosion cracking (SSC or SSCC) ‘0 @ particular case of HAC (or HSCO) ‘2 mary cause is cathodic hydrogen enty as a result of: + acid attack (e.g. COz corosion) * cathodic poison (sulphide) + stress orientated hydrogen induced cracking (SOHIC) © related to SSC and to SWC. © categorized as SSC caused by: ‘external stress combined with * local straining around hydrogen pressure induced cracks 1 soft zone cracking © similar to SOHIC (©. Occurs in softened heat affected zones of welds on plates AnicorosonEngineing Lined a8 Kuss Lumpur 27-90 Ap 2008MICROBIOLOGICALLY INFLUENCED CORROSION Note There is no such thing as microbiological comosion, but there is microbiological influenced corrosion (MIC) [Background 1891 First report of micro-organisms influencing the corrosion of lead cable sheathing 1834. Report that corrosion of cast iron in anaerobic clay Involved the action of sulphate reducing bacteria (SRB) Influences: Microbiological species affect corrosion by: ‘producing aggressive species (e.g. S*, acid) ‘biodegradation of protective ols or waxes forming deposits ‘+ stizuating the cathodic process ‘+ interfering withthe action of conosion inhibitors Examples: ‘+ Cladosporium Resinae (now re-classiied as Hormoconis Resinae) ‘0. Fungus (mould) that produces organic acids ‘+ Thiobacilus Ferro-oxidans ‘2 oxidizes sulphides (or sulphur) to sufphuric acid + Desuttovitrio (© produces sulphide and can stimulate the cathodic reaction Microbiologically related problems in oilfield production Operational Area Potential problems Fesenor sourng hugging Production corrosion HES production (ate) Uuities corrosion fouling Storage conosion HS production (safety) Ofshore Stuctures _corosion { Anconosion Engng Unt a ela Lumpur 27-30 Ap 2000MICROBIOLOGICALLY INFLUENCED CORROSION ‘Sulphate Reducing Bacteria (SRB) ‘+ the ype of arganism most commonly implicated in MIC problems in the petroleum production indus. ‘+ SRB have an important role in the natural sulphur cycle. The Sulphur Cycle Sulphate | __ subhate reducing bacteria Lsoe_J aerobic ‘anaerobic oxidation ‘oxidation (thiobacis) (photosynthesis) ‘Sulphur 8 spontanecus biological ‘onation oxidation (thiobacius) ‘mineralization. Sulphide s There are many types of SAB + genus ‘2 Desulfovibrio, Desuifotomaculum, Desutobulbus, Desulfobacter, Desulfococus, Desulfosarcina, Desutiobacterium, Desulfonema, + call forms ‘© curved, rod-shaped, oval, spherical, coll packets, flamentous + dimensions © length 1-5 pm © diameter 0.2~2 um + optimum growth temperature ‘© 30-70 °C (depends on species) Anconosin Engineering Lintes 2 ula Lr 2730 Ag 2008MICROBIOLOGICALLY INFLUENCED CORROSION Nutritional Requirements for SRB + water ‘©. common requirement for all living organisms © source: produced water, seawater, ground water © organic matter ‘require a organic carbon ‘S0UrCe: crude ol, biological matter in natural waters ‘some SAB metabolize organics completely (to CO, and water) ‘other SAB metabolize organics incompletely {to acetates} in natural SRB colonies bot types co-operate + trage elements (2. 9, P, N) ‘>. common requirement for all lving organisms source: produced water, seawater, ground water, + sulphate ‘reduction ¢ sulphide or organic sulphur compounds isa defining characteristic of SRB © source: produced water, seawater, ground water hydrogen ‘© (some) SRB oxidize use the enzyme hydrogenase to oxidize hydragen {a8 part oftheir metabolic energy-generation process, © source: cathodic sites on the corroding metal ‘anaerobic conditions: (© SRB are strict anaerobes (i.e. they can only grow ln an oxygen-free ‘environment © They can survive aerobic conditions and become active if conditions, become anaerobic (e.g. under a decaying biomass deposi) ‘Temperature Limits ‘+ most strains are mesophilic (metabolize in the temperature range 20-40 °C) some strains are thermophifc anc can grow at up to °85 C Prossure Effects high pressure does not seem to present a survival problem * e4. one strain does not grow al 75 °C (7 bar pressure), but does grow 95 °C ifthe pressure is increased to 570 bar. Arcsin Engineang Lites “9 eal ure 27-30 Ap 208MICROBIOLOGICALLY INFLUENCED CORROSION ‘SRB and corrosion There are many theorias on how SAB influence corrosion * cathaaio stimulation ‘©. consume (oxidize) cathodic He (encouraging further He generation) © produce S* ions “> FeS (an effectie cathode surface) + anodic stimulation © In the presence of Fe ions (in sols), SRB inhibit the formation of ‘protective suiphides 1009+ 28,0 sa soe Corrosion rates’ * Laboratory experiments invariably produce corrosion rates ate wer than found in service, This is thought to reflect the impractcalty of replicating ‘complex mult-onganism systems. ‘+ Maximum pitting rates in the range 2 to 10 mmiyear have been ascribed to Mic. + However, care must be exercised when considering MIC rates reported from Service experience. This is because of the uncertainty over when the MIC initiated Aniconosen Engaetng Uintes “4 la Lurou 27-30 Ap 2008,ICROBIOLOGICALLY INFLUENCED CORROSION MIC Management Overview Biocide oF pH control aa Gheplace) CHapair) [An SRB monitoring programme may attempt to cover: + SRB rumbersiactvity ‘sulphide concentration metal surface condition Note: ‘SRB activity is not the same as SAB numbers most techniques enumerate numbers rather than activty "the presence of SRB does not confirm MIC Bacteria Type Location Sampling Corrosion Implication seaale Biome Bie probes, Taporant planktonic flowing uids fluid samples questionable ae ela Lumpur 27-90 Ag 208 (© Ancorsin Ergnaing ntsMICROBIOLOGICALLY INFLUENCED CORROSION Enumeration Techniques + cuture methods ‘© single serial diution © triplicate MPN (most probable number) technique (preferred) ‘+ fluorescence microscopy © direct counting of ces (ving and dead) ‘© not possible to identity species + immunofiuorescence microscopy ‘9 permits SRB to be differentiated trom other bacteria + ELISA technique ‘0 Test kit (RapidChek®) gone microprobe © technique under development ‘Activity Measurement - (very dificult o achieve in the fleld) + radiorespirometry © radioactively labeled cell orowth nultient is added to the system such that the metaboltes can be ienttied and quantitied ‘2 some success in water injection systems (neads skilled microbiologist) + hydrogenase activity ‘© test kils have been developed that determine hydrogen uptake in the biotii © hydrogenase is not SRB-specits, otter microbes wil be detected ‘Some Biocides Biocide ‘mg/l (residual) Comment orine @2_contivous oxidizing, contamed by ammonia and 5-1 intermittent amino groups looses effectiveness pH>7 chlorine dioxide 0.2 intermittent oxidizing; not consumed by ammonia and amino groups insensitive to pH quaternary ammonium §-38 intermittent surfactant, nor-oxidizing ‘compounds, ca produce foaming glutaraldehyde 10.75 rnon-oxidizing; consumed by ammonia and amino groups Insensitive to plt (no longer used in North Sea due to health warnings) formaldehyde attemative to glutaraldehyde ‘Note: bacteria can baconte resi biocides andlor treatment regimes. ‘a Bioeide. Way be necessary to change (© Ancorsion Egraeiog Linteg “6 una Lump 27-90 Ap 2000MICROBIOLOGICALLY INFLUENCED CORROSION MIC Corrosion Rate Prediction tor Pipelines (Shell Model Based on field experience Mic Corrosion Rate = CFP Where: C= 2mmy P= 957 (exponent) F f)xfeX footy. (Factors see Table below) Factor iTrue_| Factor it False SpH=95 i ‘0.001 TOS < 60 gi 1 o2 I TOS>60 gil do SRB grow? 02 0007 10°C << 45°C i 02 TT > 45°C do SAB gow? 1 02. ‘SO, > 10 mgi 1 02, “Total C (from fay aid) 320 mgih 1 02 Uniizable A> 5 mg t 02 CN ratio <10 1 04 Flow velocity <1 mie 1 Tis « flow velocity <2 me 06 2mis 0.5 yr, down-ime <1 +f week, Pipeline age >05 yi down ine 550 2 fe: FM ots a vera ne do Waid ac llane CaosonPredcten and Appleton 0 ‘Cones napamar Pope !35 CORAOSON age pus NACE (Houta {© Anicaroson Eien Lined “7 sa Lumpur 2790 Api 2008CORROSION UNDER INSULATION (CUI) WHY DOES cul occuR? Cause: + water © trapped during construction © leaking weather-proofing © spillage Exacorbating Factors: + aggressive ions ‘© contaminants present in the insulation material © atmospheric polutants (© decomposttion/ydrolyss of organic materials ©. spillage + temperature ‘© problems encountered in equipment operating at § - 200°C (© exacerbated by cyclic wetting/drying > concentration mechanisms * carbon steo!s ‘© accelerated corrosionpiting © SOC (iow risk: hot nitrate) stainless steels ‘© crevice/piting corosion © SCC (high risk: chloride + T>60 °C) + othere ‘© comparatively litle experience ‘Areas of Concern: vortal srs ct ‘tered XN Jolt in suas mifoins ( Ardconosion Engen Lid 1 nla mp 27 20 Ae 2009CORROSION UNDER INSULATION (CUI) Corrosion implications of Insulation Type Water Extract Chloride calcium aicate ‘akaline (pH 7-10) possibly high fibre glass (-500 mgt) cellular glass ‘ceramic fibre ‘mineral wool neutral (pH6-7) low (-2 mg) organic foams cid (pH possibly high CORROSION RATES Itis at possible to predict rates of CUI. The following are ballpark worst case estimates: + 50-110°C > upto 1 mmyear + <60°Cor> 110°C > up 0.25 mmiyear CONTROLLING Cul + insulation specification ‘2 closed cell foams > low chloride 5 lew moisture + dry construction © dry storage during shipment and storage protection during construction © vapour barrier + design deta o prover water ingress top hats to shed water arrange cladding to shed water © drain points at the base of long vertical sections © waterproof seals on pipe hangers and supports © avoid joints in steam tracing lines + protect the substrate ‘© organic coatings (carbon and stainless stesis) © aluminium fol (austenitic stainless stoe!) © Inhibited insulation (slicatas for the SCC of austenitic stainless steel) ‘© prompt maintenance/repalr of damaged cladding ‘ Aricoosion Engng Lines se ada impr 27-90 A 2000CORROSION UNDER INSULATION (CUI) + warm air drying (recent development - ited application) + Review the need for insulation: ‘© lower temperatures later in fe ‘© Use guards rather than insulation for personnel protection, © But: beware the possibilty of introducing internal dew'point corrosion risks INSPECTION ‘+ remove insulation (common practice) ‘+ remavable “windows” in cladding/insulation (compromises barrier) ‘With insulation in place: ‘+ neutron back-scater radioactive source of “fast” neutrons. detector for back-scattored ‘thermal neutrons NN telescopic pole Insulation electronic controll © low activity radioactive source emits “fast” neutrons © some neutrons intact with hydrogen and produce back-scattered “thermaY neutrons © back-scattered neutrons are detected and the signals analysed © presence of water inferred from the presence of hydrogen © measurements are relative In nature (operator usually calibrates the ‘equipment by comparing known wet and dry areas). ‘+ thermal imaging ‘o _detects insulation breakdown (imples water present) + radiography © detects corrosion thinning of pipelvessel wal (© Anicanson Erineing Uintos eo ua rp 2720 Apt 2008CORROSION UNDER INSULATION (CUI) NOTE: Statistics show thatthe highest incidence of leaks in the refining and chemical Industry is due to CUI, not process side corrosion, 81% in lines < 4° 40 60% of maintenance costs Source : Minutes of meeting: EFC WP 15 Corrosion in the Refining Industry -30/09/2000, ‘© Anconosten Ermer Lied oe stupor 7 90 Ap 000CORROSION ENGINEERING OVERVIEW TYPICAL SCHEME GOOD CORROSION ENGINEERING DESIGN + recognizes that: >” corrosion can be either designedtin or designedt-out + avoids © locations where deposts can sete out © impingement or wear condensation of aggressive ids ‘0 drainage © flow rates ‘+ stagnation ‘= turbulence © stresses ‘residual and applied + static and dynamic © galvanic (bimetalic) couples { Anicoroson Engineering Lntes a a Lumpar 27-30 Ap z008CORROSION ENGINEERING OVERVIEW DESIGNING FOR GALVANIC CORROSION (itpossible) construct of one material tise metals close together in the galvanic series make key components trom the more noble metal make the base metal thicker section ‘ensure large anode/small cathode area ratio. consider: ‘© coating the cathode (but net the anode!) © insulating the two metals © cathodic protection MATERIALS ‘= Good corrosion engineering ¢esign may permit construction from less, ‘expensive materials ‘+ Bad design may result in expensive materials performing worse than theie cheaper alternatives. Materials Selection Considerations: ‘mechanical properties physical properties fase of fabrication cost ‘ease of maintenance and repair availabilty of design data and specifications appearance corrosion resistance amenabilty to corrosion contro! Incil and gas production the material of first choice is carbon steel Usually, its onl ifthe lack of corasion resistance combined with the impracticabilly andior expense of providing corrosion protection, that @ move is made to more ‘corrosion resistant materials (see notes on materials selection) ‘© AnconsinErgnsting Lents ne uta Lumpur 27-90 Agr 2008CORROSION ENGINEERING OVERVIEW CORROSION ENGINEERING OPTIONS - SWEET SYSTEMS Carbon Stee! ‘+ no protection (renew itwhen necessary) ‘© corrosion allowance ‘+ corrosion allowance + inhibitors (+ ontine monitoring) dehydration: ‘© glyool contactors © molecular sieves © refrigeration techniques #002 removal © absorption towers + polymeric linings Corrosion Resistant Alloy + as bulk alloy as cladding CORROSION ENGINEERING OPTIONS - SOUR SYSTEMS Hydrogen Pressure Induced Etfects (blistering or pressure cracking) ‘+ Ingoneral HPIC/biistering probloms are manageable because: © the damage occurs slowly (typically over many years) © the cracksiblsters are in the plane of the plate and, therefore, less. ‘ttl from an integrity point of view. ‘+ Itmay therefore be acceptable to reduce the rate ofthe phenomenon, without the need to eliminate it altogather: ‘+ Fleduce surface hydrogen generation andlor enty into the meta: ‘© corrosion resistant alloy © protective lining © corrasion inhibition * Avoid hydrogen gas formation within the stee! ‘© reduce the instances of second phase surfaces + “clean steels + steels tested for HPIC resistance © AniconosonEninirg Ltt ra eal Lumpur 27-30 Api 000CORROSION ENGINEERING OVERVIEW Hydrogen Embrittlement (HE) Etfects (Sulphide Stress Corrosion Cracking) ‘+ HE problems are potentially more dangerous because '© damage may occur very rapialy indeed (within hours!) '© cracks propagate through the plane of the plate > compromising integrity. ‘= Safe Option: ‘© Select material that is not at isk * NACE MR 0175/I80 15156 * testing track record ‘+ Reduce surface hydrogen generation andior entry into the metal ‘© corrosion resistant alloy © protective lining © Gorrasion inhibition © (latter options must be selected for very high pertormancelrelabiity) + avoid interaction of atomic hyérogen with dislocations ‘restrict hardnessistrength (Re <22 for carbon steel) requires care aver welding procedures © lower the applied stress * de-ate vesselspipelines (impacts on production) * thicker plate (empacts on capital cost and weight) © lower residual stress * stress rlieve wolds ‘© minimize plastic deformation * do nat over-tighten bolts + do not over-restrain pipework * alloys resistant to HE (used in hydrocarbon production) low alloy steel (0.3C 1.0 Cr 0.2 Mo 0.5Mn) marionste stainless steels © duplex stainless stee!s ‘austenite and "super-avstenitc” stainless steels ‘ickel based alloys + gas sweetening © HS (and in some cases CO) can be removes ‘akaline reactants (amines or activated KCOs) + solvenis (propylene carbonate) + molecular sieves HS scavengers (triazines) + H,S polishers (2n0 packed columns) © Antconosion Erin Lined pa ua Lump 27-90 Ap 2008CORROSION ENGINEERING OVERVIEW CORROSION ENGINEERING DESIGN ~ THE DETAIL IS CRITICAL Delusion: Boller Feed Water (BFW) Heat Exchanger % niet _[¥, [80°C (Outlet [T, [120°C BFW ‘cla Waste Gas Inlet_1¥,]00°C fOutiet [T, [200°C Ts Acid 4 Gas, [Dew Point | 110°C ‘According tothe process engineer, the acid waste gas is always above its due point no corrosion. | impingement attack local condensation acid attack g9e¢ 20°C. Local cacling at the bolle feed water inlet causes condensation in the acid gas stream > impingement attack on the heat-exchanger shell. © pncorsin Engine Utes rs uta Lp 27-90 At 2000MATERIALS SELECTION MATERIALS COMMONLY USED IN THE HYDROCARBON PRODUCTION INDUSTRY ‘CARBON STEEL ‘Also known as carbon-manganese steels. Contain C (<0.35%) and traces of P, Mn, Si, and $ but no deliberate additions. Referred to as pan or Kile. Usually the material of first choice: ‘cheap versatile mechanical properties seadily avaliable (multiple suppliers) ceaily formed and fabricated comprehensive standards, codes and specifications ‘ot intrinsically corrosion resistant; but readily protected by: ‘© coating © cladding © Inhibition © cathodic protection (CP) + often satisfactory corrosion ife may be achieved by the addition of a corrosion allowance (possibly in combination with inhibition oF coating) ‘Some examples of corrosion engineering in carbon stee! ‘Siructure/Equipment Corrodant Protection aler WbeS Water (high TP) Oz scavenging ‘BH control petroleum production seawater ‘coatings - sometimes, platforms GP- always: marine coatings atmosphere ‘sweet gas pipelines CO (uH-0) dehydration, or (internal) inhibition + cortosion allowance, or intemal cladding sour gas pipelines HS + COp hardness control (welds) + (interna (HO) dehydration, of Inhibition + corrosion allowance, or internal cladcing jpelines (external) _sollor seawater __coating + CP Note: ‘= often it requires only a small change in corrosion circumstances to make ‘carbon steel aoceptable. (© AntesrsonEngetng Ln mH ua Lumpur 27—3¢ Ap 000MATERIALS SELECTION Carbon steel is used for the vast majority of structures, ‘employed in petroleum production ‘The Etfects of Alloying Additions on Carbon Steels Cle] N] Ss [Mn] Si] P| Cul Mo | Se] Ti corrosion m/e eran eee) ‘mechanical eae Fares eens 7a Thigh temperature | = | = ani Koni cu eealess machinabilty |. | - |= | + aia een eel weldability a= [kon een ere Renee 2 cold work ~pefet- t= b=b=bet= Pe key] = ite orno effect + benefit - deleterious Killed Steels ‘molten steel is saturated wth oxygen 0 0: 426 > 200 (gas) © adverse etfect during soiification “king with $i 2 O: 4 SI > SiOz (sold) © residual sicon 0.15-0.30% © coarse grain structure © brie ow temperature problems) “fling” with Al (or Al+ Si © residual Al (0.02 0.05%) © fine grained structure © improved low temperature toughness, Low Alloy Steels, Often refered to as High Strength Low Allo (HSLA) steels + selected for higher strength (particularly at 7>425 0) * not usvally selected for corrosion resistance numerous alloys: 0 Cr 110.9% © Mo 010 1% ‘+ examples of applications in hydrocarbon production: ‘2 lowerafoys: fasteness, wellhead components © 9Cr1Mo:" downhole tubing Antoonosn Erasing Lint 72 la Lumput 27-30 Ao 2008,MATERIALS SELECTION UNIFIED NUMBERING SYSTEM (UNS) Historically there has been considerable confusion in the designation of alloys due te the multiplicity of organisations involved + AIS! + ODA ASME + Trade Names ASTM ACI + Mlitary Specs. + Industry codes: + SAE + Aws = National + tc Standards This led to @ move towards a single, untied system > UNS. UNS Designations. ATX] XX] xX1x XXKKX single alpha character | |{ive digit number [denotes alloy group Identities specitic alloy Ferrous Alloys Non-ferrous Alloys Group Alloy Type Group Alloy Type 1D specified mechanical properties © A aluminium F castirons © copper G Carbon and low alloy steels E rare earth metals H AISIH-steals L low metting point metals J castssteels MM. miscellaneous K miscellaneous stools N nickel S stainless steels Fl reactvelretractory metals T tool steals precious metals W wold filers 2 zine ( Ardconosn Erinn Lad ra a Lumpur 27-90 Ap 2000MATERIALS SELECTION STAINLESS STEELS Usually the frst top-up" from carbon steel increased corrosion resistance. Four Crystal Types: Type Composition UTS Yield Elong. % __(MPa)__(MPa) ‘Rusieniic Gr 15.27 490-860 205.575 36-60 No 835 Mo 0-68 N Fenttic cr 11-30 415.650 275-550 10-25, Ni Oe Mo 04 Martensite —Gr_-—«11-18 480-1000 275-860 14.0 Ni 08 Mo 02 Duplex Cr 18.27 680-909 410-900 10-48, No 47 Mo 27 NCuw Goneral Properties: Austenitic: ‘stabilized by fo elements (Ni) ‘+ gonerally good corrosion resistance ‘+ most widely used stainless steel = nonmagnetic Feritie + stabilzed by bec elements (Cr) resistant to chioride stress corrosion cracking Marensite ‘+ high carbon, body-centred-tetragonal (bet) ‘+ high strengthyhardness ‘+ used in pumps and valves Duplex ‘= twin phase (austen + fertti) ‘+ specialist use in corrosion service. Popular in hydrocarbon production (© ancorsion Engetng Lite ne la Lepr 27~90 Ag 208MATERIALS SELECTION AUSTENITIC STAINLESS STEELS + mosty designated UNS 5 3xXXX (or AISI 300 series) + can be hardened by cold working (not by heat treatment) > non-magnetc (inthe annealed condition) * 00d formabilty + weldabie (but beware possbity of sensitization) * good general corrosion resistance i used propery) ‘Compositions ~ Selected Austenitic Stainless Steels “UNSNo. Cr +=*Ni+*Mo © Others Notes” “ssoi00 20 0S RSS s30403 18:20 8405, 0.03 1 s31000 24.26 19-22 0.25 S31254 195.205 175185 665 002 O51Cu 3 831600 1618 © 1014-23008 3 S31603 1618 104 «230.03 13 $31700 1820 1115 840.08 3 $3170 18-20 1118 340.03 13 sa2100 1719812008 Th 2 34700 1719 «913 008.NB 2 $3810 17-19 175485 0.08 Notes: 1. low carbon (reduces risk of sensiization during welding) 2. stabilized with carbide formers(avoids sensitization) 3, molyodenum for improved pitinglcevice resistance 44, 537603 is usualy in minimum grade of austenite stainless steel that is ‘sed in a hydrocarbon production environment Caution: ‘+ good resistance to hydrogen embritlement and related forms of cracking (H:S environments) «+ Sltcot te cords (pting and SCO) parla elavates temperatures. ‘+ (additional risk) liquid metal embrittement (LME) due to molten zinc. (Do not route galvanized cable trays above austenitc stainless steel piping. Molten 2inc could drip onto the piping and cause LME ~ re: Flixborough disaster (1974), © Ancotoson Ergnotng Lint ns Kula Lumpur 2730 Ae 2200MATERIALS SELECTION ““Super-Austenitics" (Designated Ni-based alloys in UNS) UNSNo. Gr N_Mo__C Others ‘Trade Namo Nog020 19-21 G28 23 0.07 _(Bx%0)ND Carpenter 20063 Nos028 26-28 205925 34 0.02 CuD61 Sanicroze Noes 20.22 235255 67 0.25 ALOX ‘high Ni greatly reduces the susceptibility to chloride SCC ‘+ Mo increases resistance to chloride induced pitting Pitting resistance equivalent number PRE} or austenitic stainless steels PREs tuer + 3.3%Mo PRE is an empirical ranking the higher tha PRE, the better the resistance to pitting and crevice corosion the minimum PREy for seawater service is 40 (experience based) PRE, has no influence on resistance to chloride SCC Stools Family Tree of Austenitic Staink ose00 iting stabilized [ssoe00 } resistance [momp—! fe +e ware ‘s0000 "390923 Improved machinabllty reduced sensitization ‘© Anicoroton Erinn Les 6 uta Lumpur 27-30 Ap 2000MATERIALS SELECTION Notes: 1. $30400 (AISI type 304) isthe “workhorse” alloy 2. PREx (piting/erevice resistance) inereases with Mo, Cr 3. oxidation resistance increases with Cr (but require more Ni to maintain austenite structure) 4. chloride SCC resistance increases with Ni 5, stabilization teduced sensitization prevents intergranular atack at welds FERRITIC STAINLESS STEELS + 11-80% Gr (+ few other additions) ‘cannot be hardened by heat treatment ‘+ can be hardened by cold working ‘+ magnetic ductile ‘+ teasonable resistance to aqueous corrosion and oxidation + high resistance to chloride stress corosion cracking © Potentially at risk from hydrogen embritlement, sulphide SCC ‘Compositions - Selected Ferrtic Stainless Steels, UNSNo_cr_—S=SswNSC~=‘iO Chore ‘S40500 116145 008 01-030 840800 105-1175 08 - 008 Ti $44d00 175195 1.0. ‘1.75.25 0.025 N, Ti, Nb Su4627 2527 0875-1 0.01_N,ND 844623 245-26 25.45 95-45 0.025 Ti, Nb S44660 25-27 15:35 © 25:3 0025 Ti,Nb 44735 28-30 1 0.03 Nb, Ta 844300 28.0 2025 35-42 0.01 MARTENSITIC STAINLESS STEELS ‘Steels transform from austenitic structure at high temperature to ferric structure at low temperature. However, if the cooling is rapid (quenching) then the transformation does not proceed to completion. The result is @ martensitic (body ‘centred tetragonal) structure of high strengthinardness. magnetic moderately ductile can be hardened by heat treatment ‘moderate general corrosion resistance restricted composition range Artconsin Engnera Lnaas rs Kala Lumpur 27-30 Apt 2008MATERIALS SELECTION © >11%% Cro ensure corrosion resistance (passivity) © <18% Gr to prevent transformation to ferite © no Ni, Mo (austenite formers) Compositions ~ Selected Martensitic Stainless Steels, UNS No. or Wr WoC Others 41000118435 IS 01-03 Al S408 115135 = 008 Ti 842000 12.0140 2018; Martensitic stainless steels in petroleum production 18 Gr Steels (UNS $41000 and $42000) ‘production tubular (L80 in API SCT) temperature mit 120-150 C (depends on pH, [Ct] and Pics) ‘cannot be welded ‘approved by NACE M0175 (Pas <0.1 bar, pH>3.5) “Super-martensiti” Stainless Steels + typica! composition © 12-43% Cr © S%Ni © 2%Mo © <0.02%C * recent developments simed at increasing service applicabilly of martensiics ‘production ‘ubulars (deep/hot wes) + welded flowines reduced carton level > ‘2 improved general corrosion resistance © permits welding + requires post wold heat treatment + 22C1/25Cr (duplex stainless sige) welding consumables temperature limit raised-> © 2006 ‘+ depends on pH and Pras ‘© general corrosion <0.1 mmly but + sulphi SCC resistance worse than standard martensitics (© Anteorosion Engines Led na uta Luror 27-30 Ap 2002MATERIALS SELECTION DUPLEX STAINLESS STEELS ‘+ structure: austenite + fete tougher than feriios + CSCC resistance better than austerites © worse than feritcs| + 8 SOC resistance better than ferries © worse than austenitics + require considerable care when weiding ‘9 thermal tendency: austenite-> ferrite (©_use high Ni (+Mo) welding consumables “+ austenite former + Mo maintains high PRE at wold Pitting resistance equivalent number PRE for duplex stainless steels PREN = Kr + 3.9% Mo+ 16%N Compositions - Some Examples of Duplex Stainless Steels, UNS WoO Wi Wo © Others Sates 210280 4565 2555 003 NO0BOZ0 32208 322 45.65 33.20.03 30.18, $3230 21.5.245 3055 0.05.06 0.03 N0.05~0.20, Cu0.0s. 06 892550 24.0270 4565 20-40 0.04 NO.1-0.25,Cu1.5- 25 832760 240260 6089 3.040 008 N0.203, Cu05-1.0 wo51.0 notes: ‘+ $32208 isthe top end of the $21803 specication ‘+ $31903, $3208, $32904 are referred to as the 22Cr duplex stainless steals + 892550, $32760 are referred to as 25Cr duplex stainiess steels, of “superiuplex’ ‘2 Aatoroson Erne Ld ra ta Lumpur £720 ge 2008MATERIALS SELECTION NICKEL ALLOYS ‘= very good general corrosion resistance (non-oxidzing environments) ‘+ high resistance to Cr SCC (Ni2A%) ‘+ high NiMo alloys are expensive > economically used in thin sections as intemal lading Compositions - Selected Nickel Based Steels. UNSNe.__NI Gr WoGu Fe Trade Name No2200 «986 5 : ~ Alloy 200 Noasoo 87, : 31 1.5. Monel 400 Noss2s 42 3 23 30 Incolloy 825 Noss Gt oS = 4 Inconel 625 Nossss 57 16 16 : - — Hastelloy C4 Ntooot 68 : 28 1.5 Hastelloy 8-2 Nioz7 87 16 16 Hasteloy C276 Note: Inhigh Cop, high HeS, high Cr wet hydrocarbon systems: + N08825 is used as either solid alloy or as cladding (on carbon steel) + NO6625 used as cladding (© Ancorosien Engineering Linted 710 ala Lumpur 27-30 Ae 008MATERIALS SELECTION ‘COPPER ALLOYS: [Not used in hydrocarbon service; but useful properties for tity (water) systems: ease of fabrication and joining high thermal consductivity resistance to fouling Copper alloys in hydrocarbon production: + potabie water + seawater service ‘© heat exchangers © condensers vale tie + atmospheric exposure © splash zone cladding Brasses © Gus2n + >15% Zn > susceptible to dezinctiation ‘©. occur in slow moving brines, brackish water, weak acids | ©. counteracted by P, AS of Sb additions tothe alloy ‘+ Sn additions improves corrosion resistance ‘+ Al additions increase resistance to impingement attack (in high flow rate systems) Phosphor Bronzes (ous Sn (8410%) +P {00d resistance to flowing Seawater (and mineral acids) resistant to impingement attack usually used in cast form ‘Cupro-nickels Contain 10% or 30% Ni aqueous corrosion resistance 30%>10% 10% Ni alloy is cheaper applications: ‘© heat exchangers and condensers © seawater piping systems ‘© splash zone cladding ‘© Arenson Ene inte mn uta Lumpur 27-30 Ap 200MATERIALS SELECTION CAST IRONS [Not used for hydrocarbon service. Used for some components in utility systems + >2%C and>1%Si ‘+ the form of the carbon determines the type of cast ron ‘© increasing %Si > C as graphite: ‘Castiron Type Carbon Gontent white Foie grey ‘graphite fakes maileable graphite - ireguiar nodules uct graphite ~ regular nodules Unalloyed Cast Irons Cre 9% Si ‘+ most common type ‘© corrosion resistance comparable 1o carbon steel Low Alloy Cast irons ‘© up 10.5% Ni, Cu, Cr or Mo second major group ‘+ improved corrosion resistance High Nickel Cast irons * usually up to 12% Ni (gome >18% Ni} + Cu * good acid resistance ‘good alkali resistance (high Ni alloys) High Chromium Cast Irons white cast irons with 12-30% Cr ‘900d resistance to oxidizing acids (220% Cr) ‘ot resistant to reducing conditions excellent abrasion resistance ‘Graphite Conosion * a form of selective leaching + affect gray cast ron (graphite flakes are cathode to Fe) + difficult te detect (lle obvious change in appearance cr dimension) Erosion Corrosion, ‘+ grey cast iron beter than carbon stee! ‘high Si (24%) 3 hard matric ‘+ increasing corrosion resistance (e.g, high N} can improve erosion resistance, ( Anicosin Eraneing Line roe ea Lumpur 27~ 30 Ap 2008MATERIALS SELECTION MATERIALS SELECTION FOR PRODUCTION SYSTEMS. il and Gas Production Systems (Wet) Sources of guidance: 180 18156 Petroleum and Natural Gas Industries ~ Materials for use in HeS- ‘containing environments in ol and gas production (2001 to 2005) Part 1 General principles for selection of cracking-tesistant materials. Part 2 Cracking resistant carbon and low alloy steels and cast irons. Part’ Cracking resistant CRAs (corrosion resistant alloys) and other alloys EEMUA: Guidelines for Materials Selection and Corrosion Control for Subsea Oil and Gas Preduction Equipment. (Publ. No. 184 2004) NORSOK M-001 Matetials Selection (Rev 2 1997). Inhouse standards ‘Suppliers data Testing see notes) First Choice: Carbon Stee! Trae cations — © [cont | se carbon steal + (© Aniconosn Ernst Los ay Yoala Lumpur 27—30 At 2008MATERIALS SELECTION Notes: ‘+ Carbon stee! suitably is usualy determined by the predicted CO2 corrosion rate. The presence of HS is unlikely to be a problem. This is providing the system is engineered for service In H,S-containing environments per SO 15156 (.e. control of hardness at welds). ‘+ free sulphur is present (increasingly likely in high HeS enviconments) then ‘carbon steel is unlikely to be an option, + The repaidreplacement option requires a full risk assessment Selection of CRA * {oeary) all of the corrosion resistant alloys considered for hydracarbon production servine have adequate resistance to C2 corosion at the Temperatures and pressures encountered in production systems. ‘+ Selection is therefore based on: © ‘resistance to (combinations of) HS and chloride (at design temperature) (© resistance to elemental sulphur © cost, availabilty, fabricabilty ‘+ For high cost nickel-based alloys, the use of the allay as an internal cladding (2-3 mm thick) on carbon steel may be economically attractive. ‘+ 180 15156 dominates selection process. Relative Costs of Alloys Used In Wet hydrocarbon Systems Toy Relative Cost] | approx) _ Carbon steal 1.0 ‘331603 austenitic staniass steel 40 [22 Gr duplex stainless steel 43 [25 Cr superduplex stainless steel 53 8 Mo super austenitic stainless steal 33 ‘Nickel alloy NO8625 (Alloy 825) 80 ‘Nickel allay NO6625 (Aloy 625) 33 Higher nickel alloys Uptois | © Ancooson Engines Lino nu Koala Lepr 27-90 Ap 2008MATERIALS SELECTION Example of @ CRA selection scheme (suggested by alloy supplier) (but should now be reviewed inthe light of ISO 15156) Giaog ero? | ns ara 2 eens Prgse0.02 bar? UNS 31803 2 caer easier TRS 32550 i Sipeepler sneer ao asx 20 bat & [GI] <120 91 or | yp UNS 82760 Proset.0 bar & [Ct] <15 9! (ea 2000 100) “se Ni- alloy Materials Selection for Water Systems (Oxygenated Seawater systems + Comentsined carbon stee! in some large diameter seawater systoms ‘+ Gui alloys (beware erosion-corrosion at high flow rates) ‘+ Stainloss steels (require a minimum PRE, of 40) (© 6%Mo austenitic stainless stools © 25 Gr duplex stainless steels ‘© qualification needed tr * high chlorination levels (> 0.8 ppm residual chirine) + temperatures > 30°C. ‘+ Titanium may be required for process/seawater heatexchangers (Deaerated) Seawater Injection Systems: ‘Carbon steel (subject to strict control on residual oxygen levels) ‘+ Polyethylenesined carbon steel ‘ArtoonosonEnpsotng Ln 78 Kua Lumpar 2790 Ap 202CATHDOIC PROTECTION BASICS Overview We have already learned that, for steel corroding in a natural envionment such as soll or seawater: ‘+ anodic process (the metal) 2Fe > Fe + Be * catnodic process (the environment) 20 + Q + 4 > 40H Because these processes are electrochemical in nature, ther rates willbe influenced we make an electrical intevention. I we seek to make the syslem more electrically positive (or more negative) then these processes will tend to react to ‘oppose the applied change: “System Change > Positive > Negative electrons Temnoved ‘added anodic process faster slower ‘cathode process slower faster corrosion, worse! reduced Making the system more negative > eathodlc protection Free Corrosion In a freely coroding system + surface supports both anodic and cathodic sites ‘+ anodie current» cathodie current © niorosonEngnerhg Lint a aia Lumpur 27-20 hot 208CATHDOIC PROTECTION BASICS Partial Cathedie Protection ‘As we stat to apply CP. ‘cathodic sites and cathodic current increase ‘© anodic sites and anodic current decrease Full Cathodic Protection When the surface is fully cathodically protected: * surface consists of cathodic sites only * cathodic currents increased + anodic current = zero (> no corrosion) (© Ariconosion Enea ies oe ea Lamp 27-90 Agr 2008CATHDOIC PROTECTION BASICS Where can we use CP? Metals: ‘+ most metals canbe protected ‘9996+ ofall OP is used to protect carbon steel Environments: + must be a continuous electrolyte: © natural waters © soil (including sand, mud etc.) ‘© concrete (contains electrolyte in its porous structure) ‘+ CP is impractical in highly corrosive solutions e.g. strong acids) Structures: © ships, jeties, pers, moorings etc. offshore © platforms, pipelines, subsea procicion equipment © onshore © pipelines, tank farms, earthing systems, well casings + covert © reinforcement What are the requirements for CP? ‘+ metal to be protected (cathode) ‘© electcally continuous, ‘© corroding by an electrochemical mechanism, © ian electrolytically conducting environment ‘+ means of introducing electrical current tothe environment (anode) ‘a voltage (natural or applied) to drive the current ‘Two Views of CP: ‘There are two ways at looking atthe act of making the structure more negative with respect to its environment (i.e. achieving CP); 1. causing electrons to flow from an external source int the structure ta be protected, 2. causing conventional (6. positive -> negative) current to iow from the environment onto the surtace of the structure. Both views are equally valid '© peteerotion Egiraeg Lining es na Lumpur 27-90 Ap 2008CATHDOIC PROTECTION BASICS POWER SOURCES FOR CP 1 Secrifictal Anodes € ectrone €0,+240 zine anode (sacrificial) steel cathode (protected) ‘What metals can we use as sacrificial anodes to protect steel? Anode potential ‘©. must be more negative than the protected potential of the cathode ‘© must also deliver current with minimal pesive shit in potential ‘+ Anode curent capacity ‘> @8379 concemed with the capacity (Ah/kg) which isthe current available per unit weigh of alloy © a high capacity is desirable for economic reasons. Sacrificial Anodes for Marine Service “Frode Type ‘Potential (V) Capacity” (vs AglAgCliseawater) —(Anikg) “Gumnaam aly “105205 2ine alloy 4:00 780 magnesium allog 1.50 1100 {© htonoson Eagan td es uta Lumpur 27-20 Apt 208CATHDOIC PROTECTION BASICS POWER SOURCES FOR CP (Cont) 2 Impressed Current impressed current anode cathode What are the anodic reactions? consumable anodes: © usually scrap iron ors © provide anodic current through the dissolution ofthe anode + Fo > Fe + 20 ‘+ Non-consumatle (and semi-consumable) anodes ‘© anodic current produced by the decomposition ofthe environment: * electrolysis of water: BHO 8 >On + AH + ae! * andlor liberation of chlorine: cr > Ch + 26 2 anodes do not undergo an anodie cissolution process (© tcoroson Engioarng Lites as ui Lumpur 27-90 Ap 2008CATHDOIC PROTECTION BASICS ‘Some Impressed Current Anodes “inode Material Current Consumption Carbonaceous Density kalAy Backfill ‘Aim? (max) scrap ironstee! 5 0 semi-consumable FeSi&FeSiCraloys 10 10 prefered oraphite 10 on yes “non-consumable” magnetite 115 0.001 prefered Pt (on Tior Nb) 1000 0.000 001 yes electro-actve oxide, +1000, 0.000 004 preferred, CP CRITERIA Potential: ‘+ aim to make the potential ofthe metal with respect tis environment more negative ‘+ need to know how negative the potential needs to be. ‘Some Protection Potentials (mV vs AglAgCi|seawater) Cathode Timits Comments positive negative Tron and steal 300 “1100 erabie environments Iron and stee! “900 1100 anaerobic environments High strength tee! -800 950 (Ye>700MPa)-700t0-800 -830-—risk of hydrogen embrittement Stainless steels austenitic -300 0-600 no limit duplex -600 Test microstructure ottical feritie nla a donot apply CP ! Lead -600 1700 amphoteric Cualloys -450 10-600 no limit Gu-Al alloys "45010600 -1100 50 1200 __amphoter ‘Arcsin Engnsirg Lined ee ue Lumpur 27-90 Agr 2008CATHDOIC PROTECTION BASICS What happens i we fal to achieve the fll protection potential? + we can sill achieve useful protection: ‘typical polarization behaviour of see! in seawater: Cathodic Approx. Corrosion Polarization (mV) _rate (mmiyear) a Oa 60 0.01 120 0.001 180 0.0001 ‘+ CP obeys the law ofciminishing retums ‘+ Loss than compiete protection is adequate for most practical purposes ‘What happens if we apply excessive polarization? ‘+ needless consumption of power ‘+ reduces CP system fe ‘+ possibilty of deleterious effects: ‘© hydrogen embrittement (susceptible materials) © disbondment of protective coatings © dissolution of amphoteric metals (@.9. aluminium) © hydrogen gas hazard ‘© inereased risk of damage to third party structures Current + rate of supply of electrons » current ‘current proportional to surface area, so we usually deal wth current per unit area: current density (Aim?) + current density depends on the magnitude ofthe cathodic current a the Protection potential. This depends on: ‘© environment chemist: [Or], pH, et. © environment conditions: temperature, flow © coatings: type and condition © time * current density ranges forthe protection of tee! “Environment Tp (RAT) “Seawater 50-300 sols 10-50 concrete 1-20 sulphuric acid __>400 000 impossibe (© AricorosonEagnestrg Litas °7 Kata Lumpur 27-90 2008CATHDOIC PROTECTION BASICS Coatings and CP ‘+ combination of CP and coating is often economic ‘coating provides primary protection forthe major ofthe surface ‘+ OP protects where the coating is defeciveldamaged = example: Protection of 16 km of 36” dia. buried pipe (lp = 10 mA/m* for bare steel) Coating Bare steel Top (A) Resistance Quality % (ohm.m’) 0 are pps 700 500 10? ‘poor 3 15 10 good 0.008 0.015 Chemical Changes at the Cathode Surface The cathodic reaction generates akali (raises pH) at the metal surface: +O, + 20 + 4 > 40H + PHO + 20 > He + 20K + inseawater ‘© local pH increase disturbs the chemical equilibrium of the dissolved carbonate species: Hoo; HY + CO © calcium ions dissolved in seawater react with carbonate to form a sold deposit on the surface: ca + COF > CaC05 ‘© magnesium ions may also precipitate as magnesium hydroxide: Mg + 20H > Mg(OH)e © > calcareous deposits reduce subsequent cathodic current demand «in sols: © diffusion processes are slow © OH accumulates atthe surface rendering conditiors less aggressive and reducing the current needed for protection ‘2 some degree of protection is afforded ifthe CP currents interupted © calcareous deposits may form in Ca-rich sols, © Arcanoson Erinering Utes oe en Lumpur 2-90 A 2008CATHDOIC PROTECTION BASICS ‘SACRIFICIAL, ANODE VERSUS IMPRESSED CURRENT SYSTEMS Sacrificial Anodes ‘Ravantages Disadvantages Tio external power required Tinlied power output ‘easy to install ‘multiple anode installations interference unlikely finite anode ite all connections protected weight Sfitand-forget" hydrodynamic drag Impressed Current ‘Ravaniages Disadvantage Tigh current 'SK of correct connection high voltage tisk of maloperation long life anodes Interference possible ow weight, ‘anode-side connections at risk low profile needs engineering ADVANTAGES AND DISADVANTAGES OF CP Property applied: + the only technique that can reduce corrosion rate to zero. + considerable reduction in corrosion rate is achieved even if total protection is ‘ot possibleipractieabe, Improperly applied + can damage protective coatings (cathodic disbondment) cracking: ‘© hydrogen embritiement (susceptible metas): + duplex stainless steels 1 high strength steels + (certain) precipitation hardened Ni alloys + (c5rtain) ttanium alloys (hydriding) © carbonate/bicerbonate cracking (certain pipeline applications) + stray current interference. {© Aneorosin Enger Uintos oy Ks Lumpur 2730 At 208CATHDOIC PROTECTION BASICS ‘OFFSHORE STRUCTURE CP DESIGN EXAMPLE ~ TYPICAL STAGES Design Process ‘The folowing stops are involved in the design of a marine GP system. 1. cont the CP syetem ie 2. solact applicable codes 2. allocate the structure nto ones 4. reviow interaoes 5. calulato the surface area(s) 6. assign the protection potentials) 7. allocate the bare stool curren densities 8. account forthe eect of coatings (i present) cealeulat the total curent demand for each zone 10. select system ype and anode alloy 11 calculate anode (minimum) mass requirement 12, caleulate instantaneous anode output 13. optimize anode design 14, determine anode locations 15, anode design and specification ‘Step 1 Confirm the CP system ite ‘+ This Is usually the same as the stucture/equipment design We. However, (may) aso need to consider: © Possibly of fet extension ‘© possibilty of recovery and maintenance (opportunity to replace anodes) Step # Select Applicable Codes ‘+ DNV AP B401 Cathodle Protection Design (2008) 1 this isthe dominant code forthe design of CP systems for offshore theads, xmas trees and related equipment ‘© some operators issue supplements which modiy this code ‘+ NORSOK me-03 Cathocte Protection (1987) © sill curnt, but generally superseded by latest sue of ONV RP B401 "© Anicorasion Engi ned 10 ala Lumpur 27-20 Apt 2008CATHDOIC PROTECTION BASICS + NACE RPOIG® Corrosion Control on Undeground or Submerged Metalic Piping ‘Systems (2002) © very limited relevance to subsea wols and equipment + DNV Report No, 2005-9287 (Draft) Design Guideline for Duplex Stainless Stee! Used For Subsea Equioment Exposed to Cate Protection (2005) 12 Does not deal with CP design issues. Rather i looks at the mechanical and ‘etalurgical conditions requied of OSS to be compatible with normally designed OP systems. ‘+ BSEN 12478 General principles o cathodic protection n sea water (2000) ‘© general document; limited practical advice Stop 3 Allocate Structure into Zones * Usual apples to massive stctures such as deep water platforms where liferent depth zones will require ferent curent densites, For subsea production ‘equipment, it might uo use (for design purposes) to cde the structure into zones. based on areas: (© exposed o open seawater © in contact with/buned in seabed mud © hot pipework © flooded compartments ‘Wh dealing with individual components whore electical continuity is uncertain (toe ‘example the xmas tee and its protection cover It's best assume that thre Is no continuity, and provide stand-alone GP designs for each. ‘Stop 4 Review Interfaces + It's necessary W review the impact of other components of the overall subsea, system on the CP design requirement for the subsea component under ‘consideration. For example, a subsea xmas tee such interfaces might include: lowines (tlexe and rgd), and the well ist (soe later) (© Anconosion Engen Les en a Lumpur 27-30 Ap 2508CATHDOIC PROTECTION BASICS ‘Step 5 Calculat ‘Surface Aress ‘3.dimensional stuctual areas can now usualy be calculated by CAD programmes, but we also need to account fr + roughness (welds, treads on fasteners et) + apourtens © mudimats © plle-quides, “connected thic-pary items (permanent andlor temporary) ‘components to be bonded in .9, moving clamp components) ‘Step 6 Assign Protection Potent + cated by codes 5 oslve Potential | Negative Potenla Matera ars Limit (v) ‘Carbon seat (eerebie environmen) a8 7 (ate Caron sea (aneabi enorme) ae TF nate] [High srngihatal(SMYS > S50 Pay ees ‘Rasen ass sil 73% 95 “Ti ee ay Duplo sanass saat 35 nee rere sarioss et 35 7088 Notes: ll potent rarencedto the Aa/AgClsawater Malco negative lint determined by risk of damage to coatings May requite testing oascensin he most negatve tolerable potential ‘Some relaxation of the positive poten it may b required to prevent the risk of excessive polarization and hyeogon nau ses cracking (ydogen ombritlement ects ‘© Aneorotion Engnesng Linted on Ala Limp 27-20 Ap 208CATHDOIC PROTECTION BASICS ‘Step 7 Alocate Bare Metal Current Densities ‘There are tree circumstances to consider: ita the current deny needed to achieve polarization, “This is important for an uncoated structure, but largely Irelevant for wel coated equipment. + mean the current density needed to maintain polarization once it is ‘achieved, Ths inputs to the calculation ofthe (minimum) mass of saciical anode alloy equied fal the current density requited to re-poarzation if necessary (e.g. aor storm damage). Note: Although this parameter is described inthe codes, it is not parcuary relevant to the relatively quiescent ‘coneltions encountered in deep waters. Consideration should always be given to seting the final curent equal to the mean current for design purposes. DNV RP B401 Recommended Current Densities (30 ~ 100 m) — ‘Current Density malm® itial__Mean_ Final Tropleal = 20°C 2 6080 Sub-Tropleal 12-20" “0 7% Temperate 711°C 7% 0 © 110 Arete re 200100130 (refer to code for curtent densities st other depths) ‘© Aniconosen Enaerg Lmted ons da Lume 27-20 Ap 2008CATHDOIC PROTECTION BASICS NORSOK M-50 Recommended Current Densities ‘Current Density mam? Region “ Iniat Mean _ Fina ‘Soatom Nah Sea rN 160 6105 Nertorn North Sea S762 10 © 90 120 Norwegian Sea 62-68°N 200 100190 we algo need to consider: ‘current densities on hot pipowork(ypicaly add 1 mAlm’ ze "C above 25°C) ‘+ areas in seabed mu (ypcaly 20 m AV?) ‘Step 8 Account forthe effect of coatings (it present) + RP-B4O1 give the folowing coating categotes: 12 Category 1: 1 cost epoxy OFT > 20 um 12 Category II: 1 (or2) coats epoxy DFT > 250 pm (© Category I: 2 (or mare) coats epoxy DFT > 350 ym DNV RP B401 Mean Coating Factors (+30 m) cate category # = Catagory aaeEER SRS o 5 0 6 mo & % Design Life (years) 2 Artcoosin Engng Uinta ew Kuss Lumpur 27-20 Apt 2008CATHDOIC PROTECTION BASICS DNV RP B401 Final Coating Factors (-30 m) 100% catego on tea # : = Cato i som ; 8 am ~ Dasgn Lite (year) DNV RP B401 vs NORSOK m-503 Moan Coating "Breakdown" ° 0 20 0 0 50 Design Life (ears) © Ariconaion Engiceng Lined eas ala Lumpur 27-30 Port 2008CATHDOIC PROTECTION BASICS DNV RP B401 vs NORSOK M503 0 «© Py Dedgn Lite years) ‘Step 9 Ca late the total current demand for each zone Process needs tobe carried out final, mean and final eurents. (However, for @ coated structure the inital curentrequcement can usualy be ignored) current = area x curent density x coating factor © (donat confuse mA with A et.) RP B40 presents the coating factor in two parts: ‘2 the intial coating breakdown (Le. nsalaion damage etc.) bi. the rate of coating breakdown ‘The exting breakdown factors ar: trial a Mean av br(L2) Fil a BL Where L» CP system te se Artconsin Engrg Ut oe la Lumpur 27-30 Ape 2008CATHDOIC PROTECTION BASICS ‘+ Allow for adetional tent dain (at interfaces) © codes usualy require 5A allowance fora subsea wel. This Is a "commites ‘Questimato" ofthe amount of current a sub-sea wel casing will drain from a wellhead CP system, I is not the current needed to fuly protect the wall (which depends in tun on the nature ofthe stata the well passes through ‘and the quality ofthe cement jo. ‘Step 10 Select system type and anode alloy +The majority o xed ottshoreinsalatons are protected by sacrificial anode systems. ‘+ It woull be very unusual to use any sacrificial anode alloy other than one based on ‘aluminium (magnesium is too reactive fr conventional use in seawater, and zine has generally less zalfactory capacity and potential properties than aluminium}. Given (unproven) envirorenental concerns over alloys containing mercury, Al-Znn afoys ‘are now the standard choice ‘Step 11 Calculate anode (minimum) mass required ‘the minimum mass of alloy (for each zone ic gven by woe 87607 cu where W = weight of alloy (ka) T= osign tte (years) Ie ‘mean curent requirement (A) ° ally curent capacity (Ang) U = anede utlzaton factor (© Anconoson Enger Lt on ua Lumpur 27-90 A 2008CATHDOIC PROTECTION BASICS + cytentcapacy (C8 given by the FP B40 “anode Type Environment Capacity Ponta Anikg My Avatay So=vaio 2000 7105 seciments 1500 095 zn-aley seawater 700 1.00 sediments 700 298 ‘+ Note curentcapacty decreases wit © elevated temperature 2 burialin seabed mud © low eurrent output 1 anodes s#® installed under these conditions manulacure’s test data on Performance should be consited, or else conservative design assumptions should bbe made. Example of suppliers test dats (Dow Corporation 1977) perfomance of Gtr In tlie mut (357-420) bibad CURRENT DENSITY am) “+ Uivtion factor (U1 is the proportion o the anode that willbe dissolved by the end of le It depends on anode geometry. Typical vals: AnceesionErgnstng Let oe Kat par 27-90 Agr 2008CATHDOIC PROTECTION BASICS © bracelet anode or short fash mounted anode U= 08 9 standoff anode u-09 ‘Step 12 Calculate nstantaneous anode output ‘+ Inaction o boing able to provide enough current to saisy the etme demand of the cathode, the sacrificial anode must beable osasy the maximum instantaneous ‘current demand. For CP systems on uncoated suctures the maximum current demand comes atthe start of ie where high cathode current densities are required to polarize the stvcture (and form calcareous deposits). For coated stuctures and equipment, on the other hard, the maximum eurent demand usually comes atthe ‘ond of life when the coating breakdown isa it maximum. Thus the anode must be capable of cutputing the maximum curent reauiroment when it Is nearly fully consumed, ‘+The instantanaous anode auutis determined by: — Led E - —_avallable CP voiage Re = anode resistance © The CP voage (Eis the potential difrence between the anode and the cathode E = Evanode - E arose |Wet the protection potential of soe at-0.8V, and an anode operating polenta sf 1.05 V, the value of Els 0.25 V. 1° Tho anode resistance (R,) is function ofthe anode size and shape, ae the resitvity ofthe environment "Potenals in marine GP ae (usualy eerences to AagCiceawater ‘© atconsien Ernst Lites ow ua Lumpur 27-9 a 2008CATHDOIC PROTECTION BASICS ‘Long stand-off anode ‘owight Formula vere len a whore: s = (a+bi2 and beza ‘© Aetzoroson Engeeing Untod 20 ua Lumper 27-90 At 208CATHDOIC PROTECTION BASICS ‘Step 13 Anode Cptimization “+ Usually involves computer iteration on practical anda sizes and geomet to come ‘up wit anodes such that: (9 Individual anode aly mass x anode number + salisties the mean currant quirement ‘© ndvitsal anode outpt x anode number + salisios the maximum instantaneous Curent requroment with minimum alloy wastage ‘Stop 14 Determine anode locations + uncoated spate tame stricture: ~ 1 anode per 30 m* steelwork ‘+ coatodicomplex structures: anode postoning may be dificult de to concentration of hardware. However, it important to remember that CP is not 3 lneotsight application ‘+ For small components such as tees, marital, protection covers ett would bo normal to choose an of-he-shelt anode. Thetis, theretre lie resson to get involved withthe etal of anode specication. ‘+ ‘¢esigning an anede need fo take account of castablty and cove desig: -—} O-T1 bowed tubular eae tubular core with T-secton "book-onds" © Arcorsien Engrg Lites en ada angur27 90 Apt 2008CATHDOIC PROTECTION BASICS + anode specication needs to ake account ot dimensions (tolerances) and weight ‘aloy compositon (tolerances) (QALOC procedures ‘ote preparation ‘2 git basting (Alloy anodes) ‘galvanizing (zinc erodes) ‘2 destructive testing cul sections to examine: care bonding, cracks, voids ‘© marking, handling and packaging © Insalabon and welding (pin brazing pretered to thermit welding) © Antconosten Enger Unie on una Lumpar 2-90 At 2008INTRODUCTION TO PROTECTIVE COATINGS way coaT? Colour Chemical effects decoration ‘+ antifouting * information fie retardation © visibilty e.9 uorescence) © ablative © signs © intumescence + lightanidarken ‘= anticorrosion ‘white (reflect heat) ‘+ thermochromic Profile Physical effects smooth ‘antistatic (© abrasion resistance © electrical insulation © hygiene ‘+ radar absorbing © hydrodynamic performance «acoustic + rough ‘© environmental barier © non-sip surfaces. © anticorrosion Examples of Corrosion Contro! By Coating environmental barter «vitreous enamel nickel plating mechanical duty + corrosion resistant alloy > protection ‘combination often cheaper than CRA alone (CRA must be thick enough (2-3 mm to guarantee integrity (GRA may (or may not) be metallugically bonded (weld overlay, rol cladding) Coating ‘© much thinner than cladding (ypicaly 0.01 to 0.25 mm thick) ‘= protection depends on ceosion resistance of coating ‘= galvanic effects must be considered: © anodic coating (e.g. zinc) * low natural corrasion resistance + coating ite depends on thickness + provides sacriicial protection at points of coating damage © cathodic coating (e.g. nickel plating) + high natural corrosion resistance + thickness required to resist mechanical damage + may promote piting (galvanic attack) at any points of damage INORGANEC COATINGS Vitreous enamels + barier coating produced by forming glass at high temperature on the surface factory application requires careul design of the item to be coated very good resistance to acia attack very poor resistance to mechanical damage expensive rarely used in hydrocarbon production Coment ‘protection mode © barrier ‘©. chemical (alkalinity ofthe pore water the hydrated cement) ‘+ some applications in onshore hycrocarbon production © lining low pressure knock-out vessels © lining fire/cooling/domestic water supply trunk tines ‘= can be easily repaired in the field ‘ORGANIC COATINGS Organic (or polymeric) materials constitute the largest range of anticorosive coatings, ‘= thermoplastics = thermosets elastomers ‘Arico Engine Litas oe Kosi Lumpur 27-90 Api 2008INTRODUCTION TO PROTECTIVE COATINGS POLYMERIZATION Well known. cample Biunctional Monomers * produce linear, long chain polymers without branching Cue Soo sero sassssss90dsses- nto oor Jsscosscsisees ssesccisissss Flexibility carbon-carbon single bond rotation vibration > ttexiinty 3 Polymers. non-rigid structure ‘+ heat increases vibration and rotation carbon-carbon bonds ‘+ polymer becomes “uid” © STHERMOPLASTIC ‘© Anconsion Egeeng Lied a8 uta Lumpur 27-30 Apt 209INTRODUCTION TO PROTECTIVE COATINGS Linear (Thermoplastic) Polymers : © polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC) © polyvinylidene flucride (PVDF), poytetafluoroethylene (PTFE) ‘Three-Dimensional Polymers, ‘+ introduction of tr-functional monomer produces branching > three- dimensional structure: ‘meas “nonomer ‘+ carbon-carbon bonds are not free to vibrate or rotate ‘= structure has greater rigidity than thermoplastic. ‘+ heat does not cause the polymer to become “uid + STHERMOSET = examples ‘© heat cured ‘+ chemically cured ‘phenolics epoxy furan polyurethane fusion bonded epoxy polyester Elastomers ‘© polymers that may be thought of as intermediate between finear (thermoplastic) and fly cross-inked (thermoset) ‘linear polymer chain naturally forms into spiral shapes ‘© hydrogen bonds between loops of spirals can stvetchlcontract under the application of a physical load giving coils spring like properties > ELASTOMER, + examples ‘natural rubber, poly-isochloroprene (neoprene), styrene-butadiene rubber (SBA), Buty eubber, nite rubberINTRODUCTION TO PROTECTIVE COATINGS Polymer Types ‘Thermoplastic Elastomer ‘Thermoset a & % random ‘spring’ ike rigid structure Conformation... H-bonds (weak) — cross-links PAINT ‘What is Paint? colour thixotropes anticorrosion flow agents antitouting Wetting agents fillers stabilizers extenders etc. ( Anzareion Egan Lined os na Lupe 27-90 Ao 2003INTRODUCTION TO PROTECTIVE COATINGS Paint Terminology “Component Aternative Namo(@) Function Binder polymer, resin Tim forming component solvent ‘enables application infu form vohicle ‘medium binder + solvent pigment imparts spect properties filer (solid) bulks out the paint fl ‘extender (fui) bulks out the ait fn thixotropes impart "non- skin formation) low volume solids > low fi bulld Examples (ames = very widely used | arying * slow drying + surface tolerant (e.g, aditional red lead in inseed oil type paints) ing of * good water resisiance modified with | « poor UV resistance phenol resin ‘epoxy ester ‘not fo be contused with two-pack epoxies) ‘faster deyng than the oils + surface tolerant ‘rathane ol forms relatively tough fms silcone aly 00d gloss retention *# good UV resistance © Anconon Erggoting Lins oe Ka Lumpur 27-90 Ae 2008INTRODUCTION TO PROTECTIVE COATINGS Convertible Binder (8) Single Pack ~ Moisture Cure + atmospheric moisture iniats a chemical curing process Slates * very iti invinsio valve as protective fms {used for pains pigmented wth > 90% far) ine dust (zine ch paints), Moisture Cured Polyurethanes © nat widely used as an anticorrasve, Converts Binder (4) Emulsion Polymerization ‘+ new water-based paint technology being developed to overcome enviconmenial restrictions on organic solvents ‘Useful build coat and top coat materials now available ‘+ further development needed to produce usetul primers Generic Binder Properties Caution The folowing comments are for illustration only. There can be more variation between commercial paints of nominally the same generic. type than between paints of diferent binder chemistries. Corrosive service vinyl epoxy alld “Toninuos inmewion some OK splashes and fumes ‘OK OK x mig fumes, Ok OK some temperature limits (0) 6 #0 80 ‘Application Characteristics (Primers) vinyl epoxy alkyd Teel ast ceaned OK OK OK se0!- rusty OK x OK steel—gahanized (new) some some X 2ine rch paint some OK x aged paint some some—somne concrete ‘ok Ok x © Anicorosion Engineering Lint 0 uta Limp 27-90 Apa 2000INTRODUCTION TO PROTECTIVE COATINGS ‘Chemical and Physical Properties vinyl epoxy alkyd urethane acrylic, latex acids Geo? goad por good poor alkalis ‘OK = good. «poor = good. «SOK salts OK — good. = poor «OK = (OK water good good. «poor, OK OK solvents Poor goed -—=«poot_ = goad-—_poor weathering ocd poor good-« good. «SOK flexibility good = OK_=— good. «SOK OK abrasion resistance __OK__good__ OK __good__OK. overcoating * not all paint types are compatible for overcoating © problems can include: ‘o. solvent entrapment "2.9, epoxy applied over a single pack thermoplastic paint © poor inter-coat adhesion * e.g. application of topevats to over-aged epoxies © component bleed:through * @4g, bituminous paints Topfaumen]vmt Tepowy [PU [and [epoxy | ame Base Stor" |sticate feiumen | OK |X | x | x | * 1 x | x vin x pt xp[x}x] «|x soy fx Tp? ttt? [Por xp? pa? pe, ? |p als x pop x |x]? | px spony |X POR] x [x [OK] OK [x no x POR Pe a ee tate L ‘@ Anicension Ennoning ied 2-10 a Lumpur 27-90 A 2008INTRODUCTION TO PROTECTIVE COATINGS, FACTORY APPLIED PIPELINE COATINGS ‘Traditional tuminous Coatings ‘coal tar enamel (CTE) Widely used until the 1980's thickness 3-5 mm applied ht onto primed pipe reinforced with fabric layers Satisfactory performance inexpensive pphasad aut on health and safety ‘rounds ‘Thermosetting Coating fusion FE! ‘chemically cured coating thickness 0.3 - 0.5 mm applied electrostatically onto hot Pipe thin coating > risk of mechanical ‘damage requires rigorous quality contro! expensive (per unit thickness) Modern 3-Layer Polyolefins ‘toot ~ grt bated (S214) asphalt enamel similar to CTE thickness ~8 mm applied hot onto primed steel reinforced with fabvic layers poorer performance than CTE inexpensive acceptable on health and safety grounds ‘Thermoplastic Coatings polyethviene and polypropylene ‘+ thermoplastic coating + thickness 1.5-3.0 mm ‘polyethylene or polypropylene 3mm ‘co- polymer adhesive ‘© Antcoroion Engen nad on ‘extruded onto primed pipe thick coating > lower risk of mechanical damage moderate anticorrasion performance less expensive than FBE fusion bonded epoxy (-504m) a Lumpur 27-3 A 2008INTRODUCTION TO PROTECTIVE COATINGS + makes use of © the excellent adhesion/anticorrasion performance of FBE © the impact resistance (and relative cheapness) of thicker polyolefin ‘+ corpolymer required to promote adhesion between non-polar polyolefin and polar epoxy ‘+ system of choice far modem, high merit hydrocarbon carrying pipelines Polyethylene versus Polypropylene “Properly Polyethylene Polypropylene “hax Service Temperature (0) 5100 impact resistance Nmimm (at 23 C) 10 20 water absorption (% in 24 hours} 0.01 0,005 Elastomeric Coatings + Paly-isochioroprene (neoprene)! EPDM rubber ‘© applied at up to 25 mm © excellent resistance to impact damage ‘© excellent antceyrosion performance ‘> employed in very arduous service © very expensive indeed (use restricted to high mertrisk components) FIELD APPLIED PIPELINE COATINGS Cold applied tapes + over-the-lich appiication © pipefines © field joints ‘+ hand or machine applied ‘© thermoplastic backing (polyethylene or polyviny chloride) © co-polymer adhesive ‘© lower performance expectation than factory-applied coating systems. Pipe Diameter Backing Adhesive 100 Fier OFmm 020mm 400-150 mm 03mm 025mm >150 mm 1.0mm 0.25 mm ArtconoenEagngoting Les oe ala arr 27-20 2000CORROSION INHIBITION Definition Inhibition is corrosion control by the addition of small quantities of chemical othe environment Inhibitor Efficiency CP ~ Pen OR ne e- x 100% E cfcincy (%) ‘CR nene uninhibited corrostan rate (CRs inhibited corrosion rate 2 uselul concept forthe laboratory testing of inhibitors; but inhibitor availabilty (see ater) is @ more relevant concept for corrosion management ‘Approaches to Inhibition Thibtion (NEGATIVE INHIBITION Remove corrosive agent by chemical treatment. + Examples in hydrocarbon production: ‘© neutralizing of acids (pH control) ‘pH contol in t-ethylene glycol (TEG) regeneration systems. ‘+ TEG contactors used to dry gas TEG regenerated by thermally dstiling off the water (some) decomposition of TEG > low mot wt. organic acids ‘need to monitor and adjust pH in glyeol circuit case history (UAE) ‘+ fallure to manage pH > ‘+ fallure of carbon steel heat exchanger > replaced with a Ti unit ‘© Antcoron Engng Ud tor eta Lumpur 27-90 Ap 2008CORROSION INHIBITION © control of ‘carbonic acid” corrosion: = BH (1970s) ‘+ NaOH, NazOOs, NaHCO;, NaMBT (sodium ‘mercaptobenzothiazole), MDEA (methy| dietanol amine) ‘+ works by promoting FeCO, scale deposition ‘+ need to shift pH by +1.5 units (H activity reduced ~ 90-fold) ‘= only works in presence of condensed water (not formation Ww best injected with hydrate suppressant (MEG or MeOH) ‘no experience i sour systems ‘© case history: Stall (Trol) ‘+ 22% NaOH added with MEG + pHED74 corrosion rate > 0.1 mmiyear © oxygen scavenging: BINH}SSO, + ©, > (NH,):SO4 Applicaton: treatment of seawater for reservoir injection Ney + Oz > Ne + 21.0 (athigher temperatures) ‘Application: treatment of bole feed water. oH, scavenging (gas) '+ removal of HsS for product quality andior corrosion reasons: R R N wc’ Yen, Hs wc” on, |) => | | NOON, N85, ONG N ONL N oe Thiadiazine Aiqui) (liquia) Anconoson Eraneing Ltd 10-2 ala umpur27~ 90 Ap 2008CORROSION INHIBITION POSITIVE INHIBITION Anodic Inhibitors not common in hydrocarbon production also referred to as passivating inhibitors mainly employed in near-neutralakaline environments only used in small, closed or recirculating systems very high efficiencies (>99%) concentrations: relatively high (0,01 to 1%) ‘mechanisms: © firm formers (e.g. acid phosphate) 3Fe + 2HPO, > FelPO)2 + BHT + be film repairers (e.g. nitte — used for closed circuit heating/cooling ids). 2Fe + NaNO, + 2:0 > FeO; + NaOH + NHy + unsate: can cause severe localized corrosion (piting) if under-dosed + performance sensitive to: ‘© aggressive ion concentration (Gr) © pH © temperature Cathodic Inhibitors: ‘+ not common in hydrecarbon production + moderate efficiencies (~70%) ++ normally function by precipitating metal hydroxides at cathodic sites: zn 4 20H > Zn(OH)s onto aoe ert tet ‘not suitable for acid solutions (precipitate dissolves) effective for a wide range of metals, not greatly affected by aggressive ions ssafe: under-dosing does not result in localized corrosion Neither eathodic nor anodic inhibitors are much used in hydrocarbon production Anicoeson Engage 10.9 aula Lumpur 27-30 Ape 000CORROSION INHIBITION Mixed inhibitors ‘Schematic representation Onnnnen eter group non-polar hydrocarbon chain + hydrophilic + hydrophobic dsorbs on metal *oleophil Operation: Inhibitor tn eta surtace Characteristics \widely used in hydrocarbon production (neutral and acidic environments) ‘tficioncies >80% at dose rates: 2-100 ppm very wide range of proprietary products (usually mixtures of compounds) formulations are taliored to individual fuid chemistries and crcumstanoes ‘optimum performance on clean metal surtaces (pre-comraded surfaces are ‘moee dificult to inhibit) ‘+ surface active: may cause process upsets (foaming, emulsion formation), so blends often algo include components to counter-act side effects. ‘ Arscoroson Engine Unies saa ua Lungur27~90 Ap 2008CORROSION INHIBITION ‘Some inhibitors for Oil and Gas Systems R—CH, ~ NH, ° R,— CH,— C—NH—R pn OO (0- ciy—chis- OF JN R—ch, ‘CH, — CH, — NH, CH \2 oy, —r | ee a) I ( Arscorosion Engng Ud 10-8 Kowa Lumpur t?~90 Ap 2000CORROSION INHIBITION Inhibitor Blends ‘Active components (N, Por Compound) 10 ~ 259% ‘Co-actve compound <10% Surfactant 5% Carter’Solvent balance Note: when an inhibitor supplier refers to a dose rate (0.9.60 ppm) they are refering to the dosing of the product blend. (The active component may be as litle as 5 ppm) ‘Combining Inhibitors adéiive: inhibitors A and B do not interact Synergistic: small addtions of A greatly improve the performance of B ‘antagonistic: A and 8 counteract each others inhibitve effect. synergistic Inhibitar efciency 0% Inhibitor A 100% 100% Inhibitor 8 0% Never combine inhibitors without conducting tests frst. [2 Antconosin Engages 0-6 ula Lp £720 pl 2000CORROSION INHIBITION APPLICATIONS: HYDROCARBON PRODUCTION AND PROCESSING Downhate Piping Process Pipelines Batch gravity placement Slug between pigs pumped displacement ccolied tubing Semi- squeeze Continuous annulus displacement Continuous capillary tubing > wellhead export uid Injection via gas lit > separators 3 off-gas > compression gas APPLICATIONS: WATER INJECTION SYSTEMS - CONTINUOUS TREATMENT ‘Seawater Produced Water Ga stavenger yes Teonatimes) blociae yes (sometimes) filming inhibitor (only occasionally) carried through + make-up APPLICATIONS: HYDRO-TESTING & WET STORAGE (SEAWATER) ‘corrosion products acceptable ? yes yes no ‘exposure duration <1 month 1-24 months <24 months biocide no yes yes ‘oxygen scavenger no no. cy {@ Arteaosien Engrg Led 10.7 Xa Lipa 2790 Ao 208‘CORROSION INHIBITION INHIBITOR SELECTION Inhibitor suppliers do not disclose formulation details. Even it they did, the information would be of litle value because there is insufficient knowledge to ‘translate known inhibitor chemists into antcorrasion performance predictions in “complex hydrocarbon systems, Oil and gas company corrosion engineers are therefore concemed with managing the activites oftheir chemical supply and service companies. ‘Stages in inhibitor selection ‘elect inhibitor supply/serice company draw up a shor list of candidate inhibitors conduct laboratory evaluations ‘condlt (ited) field tests ‘cary out fied tials and final evaluation Inhibitor Supplier Selection needs to take account of numerous factors: substantia! well-funded and resourced business * technical support available tothe project ‘© laboratory facilties ‘© technical staff ‘track record/experience OK and HSE systems Selection of Candidate Mnhibltors Examine suppliers’ responses to a performance specication detailing ‘compositions of fluids to be inhibited process flow conditions Fequited inhibitor performance (corrasion allowance/design life) other treating chemicals facilities avaiable for managing the inhibition programme: ‘© handling and storage © pumping, injection, civents © disposal ‘© Anconcsin Engrg Lmtd 10-8 usa Lumpur 27~20 A 2009CORROSION INHIBITION Analyse available inhititor data ‘= corrosion control performance (CO2, HeS) * solubilty/miscbilty charactersties ‘possible deleterious intaractons: ‘2 emulsion forming © foaming © gunking + film persistency data ‘treatment costs ‘© dose rate x unit volume price Laboratory Screening Tests Carried out in a simulated process environment + bubble test ‘Wheel test recirculating loop high fuid velocity test (otatng cylinder specimen) high pressure‘high temperature (autoclave) * compatibility with other process chemicals + compatibility with other metals it present) + compatibilty with elastomer seals (i present) Field Tests. (optional stage) Cartied out on water stream from water separator limited ecope and duration electrochemical measurements © rapid response ‘© comparison of shortisted inhibitors. Field Tri pd Final Evaluation + may require systerh to be cleaned prior to trials * typical duration 3 ~6 months + scope of tia! single wellfiowline ©. entire facility inhibitor evaluation ‘© on-line carasion monitoring ‘© chemical testing * iron counts + inhibitor carry-trough ‘© NOT (e<9. caliper survey on tubulars) ‘© Ancorsin Engnetng Linked 10-9 ua Lume 27~90 Ag 2008CORROSION INHIBITION Note: The selection of an inhibitor (and dose rate) ie nota once-and-for-all process. * process conditions are likely to change through field ite (© temperatures, pressures, flow rates © water cuts © possiblity of souring © Introduction of enhanced recovery techniques © new reservoirs tedin INHIBITOR AVAILABILITY The inhibitor efficiency (defined above) provides a handy means of comparing laboratory test results on inhibitors. Its not, however, a particulary useful method for making corrosion engineering decisions. However, itis widely recognized that, it the right inhibitor is delivered at the right dose rate, then the corrosion rato is very low Toa fst approximation, is hols respective ofthe uninhibited corosion tis more useful to consider: Inhibitor availability = % of production period for which the inhibitors injected al (oF above} the recommended dosage. It reflects the operator's performance in: ‘+ maintaining inhibitor injection equipment (pumps, nozzles etc.) ‘+ managing the procurement, transport, storage and handling of Inhibitor chemicals, ‘As a matter of experience, a well managed petroleum production facity should be able to achiever inhibitor availabiles of >90% over the operating period. Use of the Inhibitor Availability Mode! “The mode! is used in predicting the average corrosion rate in an inhibited system: cr, CPx inhibitor availabilty + CR, x(1— inhibitor availabilty) Where: CR, CR,,8 CR, are the average, inhibited and uninhibited corrosion rates. Example: ‘A materials selection decision has to be made between using a corrosion resistant allay oF carbon stee! (with a corrosion allowance) plus inhibition for a crude gas pipeline. To make this decision itis required to determine whether the carbon steel ‘option is viable. The folowing hypothetical example ilusirates the process. © Anicanosion Engoeing Lines 10-10 Kats Lumpur 27-90 Ap 2008‘CORROSION INHIBITION Parameter Value ‘Comment Design We 20 years ‘Corrosion alowance | mm oR Omni “This isa conservative value offer Used in such exercises, In eal, Well inhibited systems thould corrode at <0.5 mmiy [CR Orem This vaive would be calcutated sing an appropriate model Inhibitor avallabiity | 60% ‘Conservative assumption “The aggragate ife-time corrosion (CR, x Design Life) is calculated and compared to the corrosion afowance. CR, = (01x 80%) +(0.75x20%) = 0.28 mmly ‘Aggregate life-time corrosion = 4.6 mm (Le. within the corosion allowance) INHIBITOR PERSISTENCY This is a measure ofthe length of time the inhibitor remains effecthe.Itis the time taken for an inhibitor fm to desorb from the metal surface under a given set of low ‘conditions. Its a consideration when timing batch treatments INHIBITOR RISK CATEGORIES EFC Publication No, 39 The Use of Corrosion inhibitors in Oil and Gas Production (SBN 1-904350-33-X) 2004 ‘Shell Approach Grimm | TP) | Rowe) | ison] Tabor ‘bese (ppm) | Quatty [oso es [a0 50sec 10-80 | gore | S18 | soem | sate 3 |e 3200 leading edge Anconeion Engen Lt wont usta Lumpur 2? 20 A 2008CORROSION INHIBITION BP Approach Categery | GR mm) | wax | Comment Recuiod | avaaaciy | 7 oA o% 2 oF oe 3 3 30% se = igh = 7 some | Uneccepabie Why Do Some Corrosion Inhibition Systems Fall to Deliver the Required Availabilty? * Target ‘© Over-ambition inhibitor availabiliy requirements set at the design stage (In Order fo permit CAPEX savings by selecton carbon steal instoad of Corrosion resistant alloys, ‘+ Design, Specification, Installation and Commissioning ‘© Tendency for the chemical injection equipment is rarely a high priory during the design stage of a project © Equipment invariable selected on the basis of price © Installation and commissioning can be over-iooked in the rush to bring production on-stream, There is more immediate incentive to bring a new well on-stream than to complete the installation and commissioning ofthe inhibitor injection ski. + Maintenance. ‘© Corrosion inhibition is not usually classified as safety- or production: critical, Where maintenance is trimmed for budgetary reasons the ‘chemical injection system (viewed as non-critical) tends to get over looked. ‘0 There are particular problems when injection equipment isin remote or un-manned locations. © Often on a "Txed-when-broke” maintenance regime: but how long ‘before we notice that itis broke? ‘+ Management and Training ‘© Lack of ownership of the inhibitor injection system. © Lack of awareness ofits importance. ‘© Anicoroson Engineering Linas wat? eta Lumpur 2790 Ag 2008CORROSION INHIBITION ean ieee Azo EAS oss zAsoarT 1991675 equivalent igh eat, metal dapteapn spel] oe APrersorequiviert | Teton eal das, adn pckhg, 2 un down ao Bacuppanes | Ne speereauranen gure ‘ars pump wih dedicates Detvarysytem | fom cnnralave ech | Cedatod pump a tow cent va or each jeton pin ijeton por Takei montane Sones Tolono Ripa ns coro ayo ee ampere | cain ot one | Stain cease. | ona nse nee vst sate scnngatenawton | "tre any mages convo eyeer — Toi maven cpa Shoe, game este. Sar fe brome ‘sranjomantequredin event bockape Neston dare Ta Vndar sa Feared ‘ii Tow ear on Ba ‘oma amon are eek puro opera decree ine Ver ata Slantapae oan Deoa | Sandia pha ova Some eee) * — sl dughagrs sels dapiragns pec 9% eaalty (0) Wher sons ae sass How Can Corrosion Inhibition Systems Achieve High Availability? + Improved design ‘> Engure that dasign team is aware ofthe detaled requirements for injecting inhijitors (implies thatthe inhibitor is defines before project startup). * quils!nozzles appropriate to the fluids handled * high reliability of pumps (pumps need tobe sized so that they ‘are controllable at the required pumping rates) back-up pumps with automatcrapid switch-over security of power supplies (lor elactrcal pumps, consider Fooking-up via the emergency supply pane!) ‘+ tanks sized go as to hold suficlent chemical it case of suppliers logistical problems © Maintenance ‘+ frequentiautomatic monitoring + spares in stock © Management ‘assign a senior manager as Process Owner ralis and responsibilities defined, ‘+ make the corrosion inhibition system safety-oF production critical ‘delivery performance measured and reviewed + effective (performance related) chemical supply contracts (© Antconosion Engen Ute 0-19 as Lamour 2790 Agr 2008CORROSION INHIBITION © Education +The importance of corrosion and its contol isnot always fully, appreciated by operations stat. (Case History: a facility failed to injact any inhibitor one month, so attempted to “remedy” the problem by delivering double the dose the following month!) Environmental Issues. + Inhibitors added to a crude stream wil evontully find their way into the tervironment (fr example with produced water discharged offshore). ‘© Previously inhibitor sugpters issued product data, Since 2004, they have bboen required fo submit component data. ‘+ Forpermissile discharge to the environment each component ofthe inhibitor blend must be demonstrated to be: ‘© low toxity (Eves »10 ppm) © highly biodegradable (60% in 28 days) © low bioaccumulation potential (1og Pow <3 of MW >600) ‘+ Development of “green” inhibitors is a major challenge forthe inhibitor ‘manufacturers ‘+ Management of inhibitor change over fo environmentally acceptable products is a significant issue for operators, ArceosionErgjosing Lied wou ain Lumpur 27-90 Ap 2000CORROSION MONITORING CORROSION MONITORING AND RELATED ACTIVITIES Corrosion Observations ‘Surveying Tnspection Monitoring “Frequency occasional periodic frequent Locations. most many few Planning fle important ctical Information superficial extensive intensive Corrosion ~ Related Information Trspection Monitoring Fisk 70 yes Extent yes yes Morphology yes 79 Rate ro yes ‘Management Objectives Taspection ‘onitoring Corrasion Control Adjustment 70 ves Maintenance Planning yes 0 Integrity Assurance ys 2 AntoonosinExgeing Lies wt ut Lamour 27-20 Ap 208CORROSION MONITORING Principal Techniques Trspection Wonitaring Fisk ‘reutron backscater (UN potential thermography (CU!) sgavanic probes chemical analysis rmicrobial analysis, Extent uitrasonics coupons raciography electrical resistance thermography chemical analysis FSM TA Morphology visual (+ dye pen) uiasonies eddy currents radography magnetic methods Rate linear potarzation resistance (otter electrochemical techni Note: ‘+ determining the extent of corrosion ever ime intrvals > rate Potential Benefits of Corrosion Monitoring ‘+ reduced capital cost ‘2 may favour carbon steel option (©. may permit lower corrosion allwances (-> lower weight) ‘optimization of chemical treatment reduced risk of unscheduled shut-downs reduced risk of corrasion failures improved safety and integrity assurance ans Egiing Utes 12 sala Lumpur 27-90 het 2009CORROSION MONITORING WEIGHT Loss COUPONS. Dise Type Stip Type (flush mounting) (inttusive mounting) Materials: usually carbon steel (+100 othe’ alloys avaliable) Specials: welded specimens, stressed specimens, bimetallic couples, dual probes (erosion) Features: ‘corrosion averaged over (lengthy) exposure period ‘visual record of corrosion morphology, scale deposition ete. + straightforward interpretation ‘Coupon Holders (source: Carman Unies) {ArsconosonEngheoing Lid wa ale Lurgur 27-30 Ap 2009CORROSION MONITORING ELECTRICAL RESISTANCE (ER) PROBES Principle of operation cross-section of metal element Resistance = ~S22elle Resistivity x Length ‘cross-sectional area 'As the cross-sectional area ofthe metal is reduced by corrosion its resistance increases proportionally Materials: almost always carbon steal Specials: not normally practicable Shapes: + wire (intrusive) + spiral strip (flush mounted) Features: + _sensitvty depends on sensor element thickness (typicaly 0.1 of 0.5 mm): Colvoston | Approx. Time for 1% Change Probe Life mmiyear | in Element Resistance 0.4 mm osmm | oAmm 0.5mm aot Tmonth 6months | Syears 25 years, 0.05 1 week 1 month tyear Sears o10 days 2weeks | Smonths 2-9 years so change of rate * care needed: electrical resistance affected by changes in system temperature readings may be affected by conductive scale (e.9. sulphide) Artconoon Enigmas tea ain uno 27-90 Ae 2008CORROSION MONITORING ADVANCED ER-TYPE TECHNIQUES FsMe + FSM = Field Signature method + Developed by CortQcean (now IICar) + Principle: ‘0 Alpe section (~1 m) is wired with multiple sensors (© The resistance between each ofthe (many) pairs of sensors is measured ‘0 The results are processed to give both meta oss and location of metal loss (graphical representation) ‘+ Can be deployed sub-sea (with communication to topsides data, recordingiprocessing units, colon ® + Daveloped by Coron Limited + Hioh sensitiv varant ofan ER probe LINEAR POLARIZATION RESISTANCE (LPR) PROBES Principle of Operation ‘+ depends on the Ster-Geary approximation forthe behaviour of a coroding ‘electrode under small (~10 mV) levels of externally applied polarization. Potential Tana = Rp (Linear Polarization Resistance) Rp = constant _ errosion rate {© fotcorsionEngianng Lite ws Xo Lmpue 27-9 A 2000CORROSION MONITORING LPR Types Available + 2.073 pin type (almost always intrusive) ‘+ material: usually carbon steel Features: ‘+ electrochemical technique (© Tequires a continuous aqueous phase will 991 workin a hydrocarbon line (unless in dropped-out water) instantaneous measurement of corrosion rate © not necessary to compare readings taken aver a fixed time interval + Identifies corrosion rate changes due to changes in process conditions (e.9, reflects changes in inhibitor type or dosing) LAP: Sources of Error ‘+ LPRis an approximation ‘© Fycan be confused with solution resistance ‘© high Solution resistance - corrosion rate underestimated ‘+ uncertainties inthe value ofthe proportionaty constant ‘+ can react to other (non-corrasion) electrochemical processes. ‘Schematic representation of data available from coupons, ER and LPR: Metal Loss (Coupon and ER) Corrosion Rate (LPR) ‘@ Ansconoson Ergneing Lina ws ula Lumpur 27-20 Ae 2000INTRODUCTION TO RISK BASED INSPECTION Underlying principl Corrosion does not matter! (butts consequences usually do!) ‘Some Costs of Corrosion Failure ately hazards | alion deena ost oss of capital plant or equipment | increased insurance premiums Trelasision Toss of consumer contidence loss of producien capacity onan fhe work oes 1o08 of product ality increas rogue pressure ‘maltonancarepatieplacement | puble image [bsotconmisean | id = loss of profit ‘Some Costs of Over-Protection rnecessaly expensive matrals | evoessive data handing ‘rersiang of metal sectons | overesiqned GP ayers exceecve weight over operated 6Peysions ‘cessive nor coneumplon | excessive spares inventon excaesive mnoing Premature replacement ‘cee inspection ‘ie-pectie protctve coatings = loss of poft ‘What is Risk Based Inspection (RBI)? RBIs the implementation cf a strategy aimed at: ‘© reducing failure 1o an acceptable lever + avoiding excessive monitoring and inspection Benefits of RBI [A successful programme shld yl ‘© an improvement in plant availabilty ‘more focussed inspection acivty reduction in tumaround costtime a performance based approach to plant safety proven compliance wi legslatvrinsurance requirements ‘© Arcooson Engnoeng Lintos wes ut Lupa 27-30 Ap 208INTRODUCTION TO RISK BASED INSPECTION ‘As tha RBI programme i followed, it should lead to an enduring process that: + asseeses risk ‘+ lates the inspection interval to that risk * comes bet ntmad with me as beter quality nepecton data become available * permits re-appraisal of risk and adjustment of the inspection interval on the basis of sound information ‘+ can be modified as the owner's operating phlosopty changes. Risk Assessment ‘mn order to prioritize corrosion management actions (including setting inspection and maintenance intervals) we can carry out a corrosion risk assessment to quantily the consequences of all predicted faliures. isk Probabilly f Failure x Consequence of Faliure allure is any event that leads to an adverse consequence, ‘There will aways be: = a.cause of fallure (e.g. corosion, fatigue, loss of mechanical property) + and an associated fallure mode (e.9. cracking, metal thinning) Note: ‘When examining fallur” an operator needs to consider all falure modes, not just ‘+ mechanical falure:faique, overloading, bite facture ‘third pary incidents: sabotage, vandalam, accidental collision ‘= human error: maloperation + etc. Probability of falure can be estimated by various means: + Deterministic ‘© corrosion rate algorithms © published corrosion rate databases ‘© mouse irepection and monitoring records * Probabilistic: e.g. published tale histories for pipeline [BAnicoodon Engst Lined we Kut Lump 2790 Ag 2008INTRODUCTION TO RISK BASED INSPECTION ‘Data Source | —eiperenes Fares token io Earapean ga ines (970-1992) 70 [US gas ines 1970588) utah Gas 67 _ Consequence will usually be one or more of: + sate (injury or etl) ‘+ economic loss of product or equipment, legal damages or fines) ‘environmental +public relations (adverse publicity) ‘formal risk assessment requires any particular consequence to be quantified. Usually tis involves a ranking of the Undesicabilty of all the consequences. Typical consequence matrix: Calgary of Consequence rity ‘People | Environment | Asset ‘Reputation | 1 | stghtinury | sigrtotcr | Nisupton | stort impact 2 [wioriiay [rirorotes | elon | inter inp Caratenun | Considers | 3 | Maorinixy | ocatzedetecr )amaten | | Con ‘atatance [awretece | Sh#down | Regions 4 | r3tatatios | valor ott cea ewer > Is Substantial oes | Iiomatonal ass ettct | Sst i Use the maximum severity rank derived from the four catagories. ‘The probabily of fallure (or the anticipated time to failure) is then combined withthe consequence severity ranking far each failure mode. (© Artoonsin Erooeng Ln wa Ks Lumpur 27-90 Ast 208,INTRODUCTION TO RISK BASED INSPECTION [— raga -] ‘Senseauence |Trknawn 7 | Has occured | Has occured | Has occured | ~ Relay Bias [eecuaay| “eee [eee | ee | ae, | ao | ee, fw few fw oe fw tt | “ en ee ee ee oe Fisk management involves shift risk (rom high -> low Inspection Planning ime to Fist Repair (TFR) TF (allowable wall loss ~ wall oss to dxte) corrosion rate where the allowable wall loss may simply the specfcaly allocated corrosion allowance, or may be calculated from defect assessments (rom IP data) ‘Typical scheme for the assessment of isolated detects (the red marker represents the dimensions of a detected detect) na corrosion mitigation measure is, Introduced then the deterioration rate is assumed to continue uniformly. This generates the TFR, {nspecton frequency may be set a follows ‘nspecton due date = TFR x Frequency Factor. Frequency Factor ranges between ‘0 foc high risk tem with alow confidence n the estimated corrosion rata and (0.8 for a low risk item with high confidence in the estimated corrosion rate "© Aetetion Engen ints st la Lumpur 27-90 Ao 208INTRODUCTION TO RISK BASED INSPECTION ° 2 4 6 a 10 Non: Dimensional Length ‘2 AreconosenEnpneeirg Lined ms eal umpur27~ 30 Ap 2008