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7.1MaterialSelectioninWetCO2 Overview

Environments CorrosionandMaterials
SelectioninCCSSystems
Thissectionconsidersthematerialsselectedforhandlingwetcorrosiveenvironmentsof ExecutiveSummary
varioustypescontainingCO2.Thetermssweetandsourarecommonlyappliedwithin 1Introduction
theoilandgasindustrytodescribeCO2containingfluidsrespectivelylackingorcontaining
hydrogensulphide.ThematerialsselectionrulesdescribedinthisChapterhavebeen 2GeneralInformation
drawnfromotherindustries(principallyOilandGas)andhaveformedthebasisformaterial 3ScopeofWork
selectionforthevariouscarboncaptureprocesseswithinthisreport.
4Methodology
Socalledsweetenvironmentscharacteristicallycausecorrosionwhichisdominatedbythe 5ProcessDescriptions
presenceofCO2,asdescribedinSection6.4.1(/node/108256/node/108256#h4_3).
6CorrosionMechanisms
TheadditionofhydrogensulphidetoaCO2containingstreamchangesnotonlytheformof 7MaterialSelectionand
corrosionincarbonsteels,butalsoaffectsthechoiceofmaterialsappliedformitigatingthe Experience
corrosionprocess.ISO15156/NACEMR0175providesthestartingpointformaterials
7.1MaterialSelectioninWet
selectioninthesesourconditions,althoughstrictlythescopeofthestandardisrestricted
CO2Environments
tooilandgasproductionenvironments.Thestandarddoesallowtheuseofmaterialsoutside
thepublishedlimitsonthebasisofsuitableexperimentaldataorserviceexperience. 7.2MaterialSelectionfor
FlueGasEnvironments
ISO15156/NACEMR0175onlycoversoxygenfreeenvironments.ThecombinationofCO2
7.3MaterialSelectionfor
andH2Swithoxygenpresentisalsoconsideredinthissection.Corrosioninpartially
AmineEnvironments
deaeratedbrineshasbeenstudiedinconnectionwithseawaterhandlinganddownhole
injection,andalsowithdownholestorageofnaturalgasinsaltcaverns,amongother 8MaterialSelectionforPost
situations[44,45].TheCCSconditionsaremoresevereinsomerespectsduetothehighCO2 CombustionCaptureProcess
levelsandacidity. 9MaterialSelectionforPre
CombustionCaptureProcess
7.1.1Carbonsteel 10MaterialsSelectionforOxy
Carbonsteelisusedinthisreportinthecontextofcorrosionpropertiestorefertomildsteel, FuelCombustionProcess
CMnsteels,microalloyedsteelsandalsolowalloysteelswherethealloycontentdoesnot 11MaterialSelection
produceasignificantdifferenceincorrosionbehaviourfromthatofmildsteel.Carbonsteel DiagramsandMaterial
iscommonasthematerialofconstructioninnoncorrosiveenvironmentsevenin SelectionTables
moderatelycorrosiveconditionsthismaterialisstillpreferredowingtoitsrelativelylow
12AspectsofMaterials
price,strengthandreadyavailabilityinternationally.
SelectionCommontoSeveral
BarecarbonsteelisvulnerabletoCO2corrosionandO2corrosionthecorrosionratesof Processes
carbonsteelcanbeestimatedusingtheapproachexplainedinSections6.4.1 13PipelineTransport
(/node/108256/node/108256#h4_3)6.4.2(/node/108256#h4_4).
14InjectionWells
ThethresholdofH2Sconcentrationatwhichanenvironmentisconsideredtobesourfor 15FurtherResearch
carbonandlowalloysteelsisdefinedbyISO15156/NACEMR0175.Inoxygenfree,sour
16Conclusions
environments,thecorrosionproduct(ironsulphide)canbehighlyprotectiveandcarbon
steelcanberemarkablysuccessfulaslongastheguidanceofISO15156/NACEMR0175is References
followedforavoidingSSCandHICcracking,sections6.8.2(/node/108276#h4_8)6.8.4 AppendixA
(/node/108276#h4_10).
Corrosionratesofcarbonsteelinwetsourconditionswithtraceoxygenaredifficultto
predict,butaretypicallytheseareverysevereconditionsforcarbonsteel.Elementalsulphur
andsulphuracidsmaybeproducedbyreactionofH2SandO2,leadingtohighratesof
corrosion,oftenwithseverelocalisedcorrosion,section6.4.3(/node/108256#h4_5).Carbon
steelisusuallyunsuitable,andothermaterialsormodificationoftheenvironmenthavetobe
considered.

7.1.2Lowtemperaturecarbonsteel
Fromacorrosionviewpoint,lowtemperaturecarbonsteels(LTCS)behaveidenticallytothe
standardcarbonsteelstheyhavebeendevelopedchieflyforuseinlowtemperature
equipmentwhichmayhavelowminimumdesigntemperature.Thisusuallyincludeshigher
pressureequipmentespeciallyforweldedpressurevessels,highpressureflareandsomepipe
Backtodownloadpagefor
systemswhereasuddendepressurisationcouldresultintemperaturedrop.Selectionof
Corrosionandmaterialsselection
particularsteelgradesforanyitemofequipmentdependsuponthespecifiedlow
temperatureproperties. inCCSsystems
Copyright
7.1.3CorrosionResistantAlloys
Wehavetakenreasonablecareto
Wherepredictedcorrosionratesforcarbonsteelaretoohighandwhereliningorother ensurethisinformationiscorrect
protectionofthecarbonsteelisnotpracticable,CorrosionResistantAlloy(CRA)materials andcurrentatthetimeof
willbeselectedinplaceofCS.CorrosionResistantAlloys(CRAs)areessentialforproviding publicationcheckwiththe
longtermresistancetocorrosionformanycomponentsexposedtocorrosiveenvironments. publisherforupdates.
TherearemanyCRAstoselectfromandthisdiscussionislimitedtothecommonoptions.

KeyenvironmentalparametersinfluencingthecorrosionpropertiesofCRAsare:

Temperature
Chlorideionconcentration
PartialpressureCO2
PartialpressureH2S
EnvironmentpH
Presenceofothercontaminants,principallyoxygenandotheracidicoroxidising
contaminants.

Betweenthemtheseparametersinfluence

thestabilityofthepassivefilm(initiationofpitting)
easeofrepassivationofinitiatedpits
rateofdissolutionofmetalfrompits(pittingrate)
theriskofstresscorrosioncracking(SCC)initiatingandpropagating(orSSCinferritic
&martensiticCRAs)

TheaiminselectingCRAsforagivenenvironmentistochoosethemostcosteffectiveone
forwhichthereisnoriskofpassivefilmbreakdown.Sothechoiceofalloyshouldbeonefor
whichtheexpectedoperatingconditionsarewithinthesafeoperatingenvelopeofnopitting
orcracking.Thefollowingsubsectionsdiscussthesafeoperatingenvelopeforseveral
standardCRAgrades.Inallcases,theenvironmentisconsideredtobewet.

7.1.4MartensiticStainlessSteel
7.1.4.1SweetConditions

Martensiticstainlesssteelisusuallyusedfornonweldedcomponentssuchasforgedpartsin
compressorsorasseamlessthreadedpipefordownholeproduction/injectiontubing.Itis
notusedforweldeditemssuchaspipingorvesselsasitrequiresalengthy2stagepost
weldingheattreatmentwhichisofteninconvenientorcostly.Thetypical13%chromium
containinggradeshavegoodresistancetocarbondioxide.Figure7.1representsthesafe
operatingenvelopeforAPI13CrstainlesssteelexposedtowetCO2containingNaClbut
withoutanycontaminantspresent[46].Reviewofpublisheddatasuggeststhatthe
proprietaryS13Cralloys,referredtoasSuper13Cr,Hyper13CrorModified13Crand
generallystrongerthanthebasicAPI13Crgrade,aresuitableuptoabout30Chigher
operatingtemperaturethanthestandard13CrgradesinH2Sfreeenvironments.

Figure7.1:Safeoperatingenvelopeforof13Crstainlesssteelinsweetservice
(basedonalimitingcorrosionrateof0.05mm/yr).

InhighCO2concentrationstheenvironmentpHcandropbelow3.5andthenthereisahigh
riskofpittingbecauseoftheeaseofbreakingdownthepassivefilminthemartensitic
stainlesssteels.Initiationofpittingisalsoaffectedbythepresenceofchlorideionsathigh
concentration,soabove200g/lsodiumchloride,the13Crgroupofmaterialscannotbe
considered.Suchextremelyconcentratedchloridelevelsmayariseunderupsetconditionsat
timeswithinplant(byevaporationofawaterphasewithhighlevelofdissolvedsolidsleaving
ahygroscopicsaltdeposit),or,morecommonly,atthebottomofinjectionwellsdisposing
intoconcentratedbrineaquifers.

7.1.4.2SourConditions

NACEMR0175/ISO151563specifiesamaximumH2Scontentof0.1bar(1.5psi)and
minimumpHof3.5formartensiticstainlesssteelsintubingandgeneralequipment.This
alsoappliestothelowcarbon,supermartensiticstainlesssteelgrades.Thelatestconsensus
fromlaboratoryworkandfielddataisthatstandardmartensiticAPI13CrL80cantoleratea
littlehigherH2SthanearlypublicationsseemedtosuggestorthanNACE
MR0175/ISO151563allows[ii].Figure7.2showstherangeofconditionswheredata
indicatesthematerialisresistanttosulphidestresscracking(SSC)andtheregionatlowpH
orhigherH2SwherethematerialwillcrackinstandardSSCtestconditions.Thisfigureis
basedonavarietyofdataatchloridelevels>50,000ppm,anddifferentservicerangescanbe
expectedforextremelyloworextremelyhighchloridecontents.
Figure7.2:APIL8013Crsulphidestresscracking(redregion)resistant
(greenregion)yellowarearepresentsconditionsrequiringfurthercheckingof
alloybehaviour.ISO151563limitsshownbyheavyblacklines

ThecriticalfeatureofthisFigure7.2isthetransitionbetweennocrackingandcracking
whicharisesatpH3.5(testdataestablishedatroomtemperature).Recentpublicationsalso
confirmthetendencyfor13CrfamilyofmaterialstodepassivateatbelowaboutpH3.5
dependinguponheattreatmentconditionandalloyingcomposition[47].

ThehigherstrengthSuper13CrgradeshavebeenfoundtobemoresusceptibletoH2Sthan
thestandard13Crgrade,probablyreflectingitshigherstrength.Onepublicationindicates
theinfluenceofmaterialyieldstrengthonperformance,illustratingthatthehigherstrength
materialhasagreaterriskforenhancedinitiationofpitting,hydrogenembrittlementand
sulphidestresscracking(Figure7.3).
Figure7.3:3DimensionalSSCsusceptibilitydiagramofaSuper13%CrSS
(specimenswerestressedat90%AYS).[47]

7.1.4.3O2containingconditions

Inthepresenceofoxygenthe13Crstainlesssteelsareconsideredtobejustpassive,but
overtimethesurfacedoesrust.

InthecomplexenvironmentofCO2plussomeH2Sandoxygenthereisasignificantpitting
riskbecausetheoxidisedhydrogensulphideformssulphuronthesteelsurfacewhichisa
potentpitinitiator.Martensiticstainlesssteelswouldnotbeconsideredsuitablefor
corrosive(wet)serviceinthepresenceofH2SandO2withchlorideionsaspitswouldreadily
initiate.ThereisalsoangreatlyincreasedriskofSSCwithoxygenpresent.

7.1.5AusteniticStainlessSteels
7.1.5.1SweetConditions

The300seriesstainlesssteelsareabroadrangeofmaterialsbasedaroundthestandard
AISI304LgradeandthehigherMolybdenumcontainingAlloy316L.Allthesematerialsare
resistanttocorrosioninsweetenvironmentsthemoreMorichgradeshavingamorestable
passivelayerandthereforebeingmoresuitableforCO2environmentswithchlorideions
present.ThelimitsofenvironmentalparametersforAlloy316LintermsofNaCl%,partial
pressureofCO2andtemperatureareshowninFigure7.4.Thisgraphindicatesaratherhigh
sensitivitytochloridecontentswhenthepartialpressureofCO2isveryhigh.
Figure7.4:LimitsofuseofAISI316Lstainlesssteelinsweetenvironments

7.1.5.2SourConditions

ISO151563waspublishedinfirsteditionon15/12/2003.Itissubjecttocontinuousrevision
withTechnicalCorrigendabeingpublishedfromtimetotimeandthesehavefrequently
affectedthelimitsforausteniticsteel.Thetablebelowsummarisesthecurrentlypublished
operatinglimitsofausteniticstainlesssteelsapplicableinISO151563.Valuesstatedare
maximumlimitsofparametersallowed.Thetestingrequiredforalloystobeincludedin
ISO15156nowadaysrequiresrigorousexclusionofairfromthetestmedium.Alternatively,
materialsarelistedbecauseofprovenlongexperienceinservice.

Table7.1:SAFEOPERATINGLIMITS15/12/2007(Source:NACEMR0175/ISO
151563:2003TechnicalCircular1)

Temperature,Partialpressure Chlorideconc.
MaterialType pH
C H2S(psi) (mg/l)
Austeniticstainlesssteels 60 15 Any Any
(including304L) Any Any 50 Any
93 1.5 5,000 5
S31600,S31603
149 1.5 1,000 4
S20910 66 15 Any Any

Notethatthesematerialsarenotsuitableinsourconditionswithelementalsulphurpresent.

ThelimitsofuseofAlloy316LinenvironmentscontainingH2Sandhighchloridelevelswere
establishedinanextensivereviewbyTWI[48].Inprinciplethesetestsweremadewith
oxygenpurging,buttheypredatedrigorouslaboratorycontrolsanditisconsideredthatthe
lowerlimitstheyobtainedareindicativeoftheimpactofsome(undefinedsmallquantity)of
air.Thisindicatedthatforchloridecontentsof10g/lthelimitingpartialpressureofH2S
abovewhichtherewasalikelihoodofsulphidestresscrackingwas0.9baroverawide
temperaturerangefromroomtemperaturetoabout225C.

AthigherchloridecontentstheamountofH2Swhichcouldcausecrackingwasmuchless
andisalsosensitivetotemperatureincreasingthetemperatureincreasedtheriskof
crackinguptoabout100C.Thusthemaximumsensitivitytocrackingwasfoundtobewith
chloridecontentsabove100g/latatemperatureof100C.Attheseconditionsonly0.009
barH2Swassufficienttocausesulphidestresscracking.Betweenroomtemperatureand100
CthemaximumtolerablepartialpressureofH2Sdecreasedfrom0.9barto0.009barwhen
thechloridecontentis100g/l.

Attemperaturescontinuouslyhigherthan100Claboratorytestdatashowsthatthe
materialcantolerateexposuretohigherlevelsofH2S.However,inapplicationsat
temperaturesabove100CitisconsidereddangeroustoassumeahigherlimitforH2S
becausetheequipmentmayexperiencelowertemperaturesatcertaintimes,andcracking
couldariseintheseperiods,evenifonlyfairlyshortinduration.

Sofortemperaturesatorabove100C,themaximumallowedlevelofH2Sistakentobe
0.009barwhenthechloridecontentisabove100g/l.

7.1.5.3O2containingconditions

InthecompleteabsenceofchlorideionstheAISI300seriesmaterialsremainpassivein
environmentsrichinCO2andwithoxygenandhencetherecanbeusefulnicheswhereAISO
304Lstainlessisappropriate.However,suchenvironmentsarerareaschlorideionsare
ubiquitous.

Wherethereisanysubstantialamountofoxygenpresentintheenvironment,alongwith
chlorideions,AISI300seriesmaterialsreadilypitandcrevicecorrodeatahighrate,evenat
temperaturesaslowas10C.Thisclassofmaterialsisconsideredunsuitableforapplication
wherethereisoxygenintheenvironmentwithchlorides,andparticularlywherethereisalso
H2Sorothersulphidespeciesoracids.

Possibleausteniticgradeswhichmaybeconsideredforconditionswithoxygenandlow
chlorideionconcentrationsarethosewithincreasedmolybdenumcontentrelativeto316L
(2.0%Mo),suchasAISI317(3.0%Mo)andAISI904L(4.5%Mo).

7.1.622Crand25Cr(DuplexStainlessSteel)
7.1.6.1SweetConditions

Insweetenvironmentstheresistanceof22Crduplexstainlesssteelisverygood.Thereisno
riskofpittingorstresscorrosioncrackingofduplexstainlesssteelsatupto200C,even
withsodiumchloridecontentinthebrineof200g/l(200,000ppm).Thisequatestoa
chlorideionconcentrationofabout125g/l.

TheSuperduplex25Crsteelshaveagreaterresistancetopittingthanthe22Crduplexsteels,
addingprobablyaround30Cgenerallyatanysetofconditionscomparedtothe22Crgrade
(Figure7.5).
Figure7.5:Temperaturelimitsforduplexstainlesssteelsasafunctionof
sodiumchlorideconcentration(<0.05mm/yrcorrosionandnoSCCorSSC,
basedon[46])

Atmoreextremechlorideionconcentrationsmadefrommixedsodium,magnesiumand
calciumchloridesaltsevaporatedtoformaconcentratedbrineslurry(230g/lChlorideion
concentration),itwasshownthatboth22Crand25Crduplexstainlesssteelswere
susceptibletostresscorrosioncrackingintheabsenceofoxygenat140C.Theseconditions
wereestimatedtohaveariseninsomeduplexstainlesssteeltopsidepipingdownstreamofa
chokevalvewithahighpressuredropandcarryingasmallvolumeofconcentratedbrinein
thegasstream.Internalstresscorrosioncrackingwasobservedassociatedwiththe
concentratedbrineformedbyevaporationoftheproducedwater[49].Thecrackingproblem
wasmitigatedbyupgradingmaterialtoAlloy625.IntheCCScontext,similarconditions
mightoccurwithintheinjectionwell.

7.1.6.2SourConditions

ISO151563/NACEMR0175allows22Crduplexalloys(Pren>30)withupto0.1barH2S
and25Crsuperduplexalloys(Pren>40)withupto0.2barH2S,andwithoutlimitson
chloridecontentorpH.VariouspublisheddatahasshownthattheH2Slevelscanbe
extendedwithrestrictedpHorchloridelevels[50].Ontheotherhand,atlowpHvalues
belowpH3(whichareunusualinoilandgasproduction),thematerialsarelessresistant
thanISO151563/NACE0175suggestsiii .

Duplexstainlesssteelsaremostsensitivetosulphidestresscrackingataround80100C
andsotestdataatthattemperaturehasbeencheckedtoestablishthesafeenvironmental
limits.CrackingisalsodependentonthepHandonthechloridecontent.ThepHvalueis
takenatroomtemperaturesincethisisthevaluereportedforthelaboratorytestdataon
whichthelimitsarebased.ThelimitsofH2SasafunctionofpHandchloridecontentare
givenbythefollowinggraph(Figure7.6).
Figure7.6:Safeoperatingenvelopeof22CrduplexstainlesssteelsinCO2
environmentscontainingH2 Sandchlorideions.

Consideringthe25Crsuperduplexstainlesssteel,thisismoreresistanttohydrogensulphide
ingeneral,but,aswiththe22Crgrade,thelimitsofH2Sallconvergetogetherathigh
chloridecontentandlowpH(Figure7.7).
Figure7.7:Safeoperatingenvelopeof25CrduplexstainlesssteelsinCO2
environmentscontainingH2 Sandchlorideions.

7.1.6.3O2containingconditions

The22Crduplexstainlesssteelsarenothighlypittingresistantandwouldnotgenerallybe
selectedforconditionscontainingoxygenifchlorideionswerepresentattemperatures
above1020C.Thesuperduplex(25Cr)gradesareusedupto30Cinaeratedseawater
andsowouldprovidepittingresistanceinsomecombinationsofchlorideionsandoxygen.
Aswiththeotherstainlesssteels,thecombinationofCO2/H2SandO2couldbedangerousif
elementalsulphurwasformedandadheredtothesteelsurfaceasitwillinitiatepittinginthe
duplexgrades,withorwithoutchlorideionspresent.

7.1.7NickelAlloysandTitanium
Thenickelalloys(generallyconsideredtoincludethe40%NicontainingAlloy825andmore
highlyalloyedgrades)areeffectivelyimmunetoCO2corrosionandhighlyresistanttothe
presenceofH2Sastheyhaveastrongpassivelayerwhichisrelativelypittingresistant.

However,inthepresenceofoxygenandchlorides,eventhesematerialshavelimitsas
regardspittingandstresscorrosioncracking.Infullyaeratedwarmbrines,Alloy625is
resistanttoabout60CandAlloyC276uptoabout80C.Above90Citisgenerally
necessarytoconsiderpuretitaniumoritsalloysforhandlinghotaeratedbrines.

InthecombinedpresenceofH2Sandoxygen,thereisasignificantpittingrisk,becauseof
thepotentialformationofelementalsulphur,apotentpittingagent.Wherethisarises,the
mosthighlypittingresistantgrades,suchasAlloyC22,AlloyC276andAlloy59havetobe
considered.
iiIntetechinternalreviewofcrackingdatapublishedintheperiod19982008

iiiISO151563wordingisanycombinationofchlorideconcentrationandinsitupHoccurringinnormal

productionenvironmentsareacceptable:CCSenvironmentswithhighCO2 pressuresarearguablymore
severethanproductionenvironments.

7MaterialSelectionandExperience up 7.2MaterialSelectionforFlueGas
Environments

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