Edwin H. (Ned) Niccolls Sr.

Consulting Materials Engineer Chevron Fellow

Materials and Equipment Engineering Chevron Energy Technology Company 100 Chevron Way, 10-3506 Richmond, CA 94801 Tel 510-242-4539 ehni@chevron.com

MATERIALSELECTIONFORREPAIROFDAMAGEDPROCESSPIPINGINHIGHTEMPERATURE SULFIDATIONSERVICEINTHENO.4CRUDEUNIT1 ExecutiveSummary OnAugust6,2012,afireoccurredintheNo.4CrudeUnit(CrudeUnit)attheRichmondRefinery, ownedandoperatedbyChevronU.S.A.Inc.(CUSA).Whiletheinvestigationintothecauseofthefire isongoing,preliminaryinformationindicatesthatthefireoccurredintheareaofaleakina5feetlong sectionofthe200feetlong4sidecutcarbonsteelpipeinhightemperatureservice.Itisbelievedthat theleakresultedfromacceleratedsulfidationcorrosioninthe5feetlongsectionofpipe,whichhad lowsiliconcontent(lessthan0.10wt%Si). CUSAhassubmittedapplicationstotheCityofRichmondforpermitspursuanttotheCaliforniaFire Code(CFC)toreplacefiredamagedpipinginhightemperaturesulfidation(HTS)serviceinthe CrudeUnitwith9Chromealloypipe(9Cr).Becausequestionshavebeenraisedbycertainmembers ofthepublicaboutCUSAsselectionof9Cr,theCityhastemporarilydelayedissuingpermitsforsuch workandBillLindsay,RichmondCityManager,hasrequestedadditionalinformationconcerningCUSAs selectionofmaterial. Asexplainedbelow,CUSAsselectionof9CrpipetoreplacefiredamagedpipeinHTSservicesatisfiesall engineeringandfiresafetystandards,andotherindustryrecommendedpractices,fortheuseinthe CrudeUnit.WhilecertainmembersofthepublicandtheChemicalSafetyBoard(CSB)havesuggested 300seriesstainlesssteel(300SS)asanalternativematerialbasedonitsincreasedresistanceto sulifdationcorrosion,theuseof300SSwouldintroduceanewdamagemechanismnotpresentwith9Cr thatismoredifficulttomonitorandinspectthansulfidationcorrosion. MaterialsSelectionProcess AstheownerandoperatoroftheRefinery,CUSAhastheresponsibilityandtechnicalexpertise necessaryforselectingmaterialsforaparticularservicebasedonsoundengineeringandindustry practices.Inselectingmaterials,CUSAreliesuponexperiencedmaterialsengineers,whousetheir expertjudgmenttochooserobustandpredictablematerialssuitablefortheplannedservice,takinginto accounttheriskspresented.Anymaterialselectionmustbesupportedbyacomprehensivemonitoring andinspectionprogramtoensurethattheselectedmaterialisperformingconsistentwithexpectations.
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PreparedwiththeassistanceofBarbaraSmith,SeniorBusinessManager,RichmondRefinery,CUSA.

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Thematerialselectionprocessiscomplexandbaseduponconsiderationofmultiplefactors,including operatingconditions(particularlytemperature),operatinghistory,processchemistry,velocitiesand otherflowconditions,localunitconditions,potentialunusualoperatingconditions,andturnaround considerations.Itisalsoimportanttoconsidertheriskfromallpossibledamagemechanisms,aswellas theabilitytomonitortheequipmentagainstthosedamagemechanisms.Otherwise,adecisioncould inadvertentlyshifttheriskfromonedamagemechanismtoanother.Wheneverpossible,CUSAselectsa materialthatbestaddressesthesemultipleconsiderations. TheCitysScopeofReview Oncematerialsareselectedfortherepairwork,CUSAappliesforpermitsfromtheCity,whichreviews thepermitsforcompliancewiththeCaliforniaBuildingStandardsCode,inclusiveoftheCalifornia BuildingCode(CBC)andtheCFC,asimplementedbytheCity.2Theinstallationofprocesspiping suchasthepipingbeingreplacedaspartoftheCrudeUnitrepairisregulatedintwoways: SupportstructuresforthepipingsystemsrequireabuildingpermitpursuanttotheCBC; Thematerialsforprocesspipingandthedesignofthepipingsystemarereviewedfor compliancewiththeCFC. PursuanttotheCFC,theCityspermittingroleistoconfirmthatthematerialsCUSAhasselectedto replacefiredamagedpipinginHTSserviceintheCrudeUnitcomplywiththeengineeringstandardsof theAmericanSocietyofMechanicalEngineers(ASME)CodeforProcessPiping(ASMEB.31.3)and thefiresafetystandardsoftheNationalFireProtectionAssociation(NFPA)Flammableand CombustibleLiquidsCode(NFPA30).3 TechnicalAnalysisforReplacementofFireDamagedPipeinHTSServiceintheCrudeUnit PursuanttoASMEB31.3andNFPA30,carbonsteel,5Chromealloy(5Cr),9Cr,and300SSaresuitable forserviceintheCrudeUnit.Inadditiontoadheringtotheseengineeringandfiresafetystandards,itis importanttoconsideramaterialssulfidationresistancewhenselectingmaterialsforHTSservice.API 939Cidentifiescarbonsteelwithadequatesilicon,5Cr,9Cr,and300SSasexamplesofmaterials suitableforHTSservice,dependingonvariousfactors.4Anadditionalconsiderationinselecting materialsforHTSserviceispriorexperienceandinformationconcerningamaterialspastperformance inthatservice.5
SeeRichmondMunicipalCode(RMC)6.02etseq. Afurtherdescriptionofthemannerinwhichengineeringandfiresafetystandardsarepromulgatedandincorporatedinto theCitysreviewisprovidedinAppendixI. 4 SeeAppendixII. 5 Id.
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Takingintoaccounttheabovedescribedfactors,aswellastheriskspresented,theRefineryMaterials Engineerexercisedherexpertjudgmentandselected9Crastheappropriatematerialforreplacement offiredamagedpipingsystemsinHTSserviceintheCrudeUnit.Thisdecisionwaslaterconfirmedby otherexpertswhohavesincereviewedthedecision. Asnoted,9Crsatisfiesallregulatoryengineeringandfiresafetystandardsforcontainmentand processingofcrudeoil.Further,asshownbytheModifiedMcConomyCurvesintheAPI939C,the sulfidationcorrosionratesofcarbonsteelwithadequatesilicon,5Cr,9Cr,and300SSdemonstratethat eachmaybesuitableforHTSserviceintheCrudeUnit,inparticularwhenonetakesintoaccountthe CrudeUnitsoperationalhistory.6Thus,basedonallapplicabletechnicalstandardsandrecommended practices,9CrisasuitablematerialforreplacingthefiredamagedpipingsystemsinHTSserviceinthe CrudeUnit,andprovidessignificantlyincreasedresistancetosulfidationcorrosionwhencomparedto thelowsiliconcarbonsteelcomponentinvolvedintheAugust6incident. CUSAunderstandsthatcertainmembersofthepublicandtheCSBhavecommentedthat300SSmight beabettermaterialfortherepairworkbasedonitshighersulfidationresistanceascomparedto9Cr,in particularinlightoftheFebruary2012lossofcontainmentthatoccurredattheBPCherryPoint Refinery,wherethepipethatfailedwas9Crandthedamagemechanismwassulfidationcorrosion. WhiletheBPCherryPointincidentmayseemrelevanttotheselectionof9Crforpartsoftherepair work,basedonthepubliclydisclosedBPinvestigationofthisincident,wedonotbelievetheincident presentsananalogoussituationtotheRichmondCrudeUnit.Thepipinginthatinstanceappearsto havebeenasemistagnantdeadlegwhich,after29yearsinhightemperatureservice,allowed corrosivestobuildupinavaporspaceatthetopofthepiping,leadingtothefailure.Weunderstand thattheflowinglinesinHTSserviceintheBPCherryPointrefineryhadnoproblems,andthatBP replacedthepipeinquestionwith9Cr.Thus,thisincidentdoesnotsupportaconclusionthat9Crisnot suitableforHTSservice,butrathersupportsindustryeffortstoeliminatedeadlegsystemsasmuchas possibleandemphasizestheimportanceofexistingindustrystandardsrequiringaspecificdeadleg inspectionprogramfordeadlegsremaininginservice. Importantly,theselectionof300SSwouldalsointroduceanewdamagemechanismtotheCrudeUnit intheformofstresscorrosioncracking(SCC)fromchlorides,andpotentiallyfrompolythionicacids, thatwouldnotoccurwith9Cr. Whereas9CrisimmunetoSCC,chloridesinthepresenceofwatermaycauseSCCofany300SSpiping attemperaturesaboveabout140F.LossesofcontainmentduetochlorideSCCarewelldocumented intheliterature.7Further,CUSAhasidentified10instancesofSCCinstainlesssteelpipesinhigh
Id. ASMMetalsHandbook,Volume13CCorrosion:EnvironmentsandIndustries;CorrosioninPetroleumRefiningand PetrochemicalOperations,R.D.Kaneeditor
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temperatureserviceincrudeunits,mostlyfromchlorides.8Thepipesthatcrackedintheseinstances wereinsimilaroranalogousservicetothepipingbeingreplacedaspartoftherepairoftheCrudeUnit, whichissubjecttopotentialrisksfromchlorideSCCbecausethecrudeoilsprocessedcontainchlorides, asdoesambientmoisturesuchasthatfromthedriftfromtheadjacentNo.3CATCoolingTower. Anotherpotentialdamagemechanismwith300SSispolythionicSCC,whichoccurswhensulfurscales combinewithoxygenandwatertoformsulfurousacidsthatcancracksensitizedstainlesssteel. Althoughthepotentialforthisdamagemechanismcanbemitigatedbyusingtheappropriategradeof stainlesssteel,itisstillarelevantconsideration.9 Afinalbutvitallyimportantconsiderationinselectingmaterialsforaparticularserviceistheabilityto monitortheequipmentagainstdamagemechanisms.Akeyreasonfortheselectionof9Crisits predictablecorrosionrate,whichmakesmonitoringofsulfidationcorrosionmoreeffective.Onthe otherhand,SCCfromchloridesorpolythionicacidsresultsinmicroscopiccracksthataredifficultto detectpriortofailure.Thus,theuseof9Crpresentslessoverallriskthat300SSwhenitcomesto detectingandpredictingcorrosion,anddoesnotintroduceanewdamagemechanismtotheCrude Unit. CUSAsselectionof9Cradherestotheapplicableengineeringandfiresafetycodesandisthebest choiceforpurposesoffireandoperationalsafetybecauseiteffectivelyreducestheriskfrom,and providestheabilitytoeffectivelymonitor,sulfidationcorrosion,whileavoidingtheriskofSCC altogether.

SeeAppendixIII. ThebenefitsofstainlesssteeldosometimesoutweighthepotentialforSCC,suchaswhenarefineryprocessesnaphthenic acidcrudes.TheRichmondRefinerydoesnotprocesssuchnaphtheniccrudes,however,sothisisnotaconsiderationfor theselectionofmaterialsforrepairoftheCrudeUnit.

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