Akzo-Chelates-and-GL-for-Stimulation

HenryChenAgnesGohJimLePageChelatesinOilfieldApplicationsDevelopmentofanEnvironmentallyFriendlyHighTemperatureStimulationFluidBasedonGLDAChelateJune2010OverviewWhatarechelatesChelatesinoilfieldapplications:ScaleStimulation-acidsandneedforalternatives-GLDAcarbonatecoreflooding-GLDAsandstonecorefloodingConclusionsBusinessUnit|Title3Whatarechelates?•Chelatesarechemicalagentsthatinteract(complex)withmetalions,changingthechemicalpropertyofthemetalion.•Almostallmultivalentmetalionscanbechelated(Ca2+,Fe3+etc).•Usuallyallowsforgreatersolubilityofthemetalions.•Thechelatemetalionbondisreversible.•ImportantparametersarepHandsolubilityofmetalion&chelateMetalionChelate[Metal-complex]BusinessUnit|Title4SpecialPropertiesYieldManyUsesHardsurfacecleanersLaundryWatersofteningScaleremovalPeroxidebleachingPersonalcareFoodpreservationNutrition&healthSanitizersPhotofilmprocessingAgriculturePolymerizationElectroplatingEnvironmentalremediationOilfield:ScalecontrolStimulationCompletionsCementingH2Streatment5OHCCH2NCH2COHOCH2CH2NCH2CH2COHCOHOOOStructureofEDTA6HowdoesEDTAwork?BusinessUnit|Title7UseofChelatesintheOilFieldStimulationMatrixTreatmentCompletionFilterCakeRemovalCementingCementretardationProductionScaleRemovalProductionScaleRemovalScaleRemovalProductionScaleRemovalGastreatmentH2SremovalBusinessUnit|Title8StructuresofCommonAminocarboxylicAcidChelatesNNCOOHCOOHHOOCHOOCNNNCOOHCOOHCOOHHOOCHOOCNNCOOHCOOHHOOCOHNNHOOCHOOCCOOHCOOHNCOOHCOOHHOOCNCOOHCOOHOHNCOOHCOOHCOOHHOOCDTPAEDTAHEDTAPDTANTAEDGGLDABusinessUnit|Title9Scaletodissolve?DTPAEDTAGLDALiquidvssolutionEDTA:10liquids/5solidSolubilityNH4andKNachelatesSolubilityinHClGLDAHEDTAEDTABiodegradabilityGLDAvsEDTACostNTAEDTADTPAWhySoManyChelateProducts?CriteriaforselectingtherightoneBusinessUnit|Title10SolubilityofEDTANa(sodium)K(potassium)andNH4+(ammonium)10FunctionalChemicals010203040506023456789101112pH4+SolubilityasEDTAacidpHpHBusinessUnit|Title11DissolvingScaleDissolvingscalesofvarioussolubility:BaSO4CaOxalateCaCO3CaSoapScumChelatestrength:DTPAEDTANTAEDG11FunctionalChemicalsCaCO3(solid)+EDTA4--[EDTA-Ca]2-(solution)+CO32-BusinessUnit|Title12ChelateEfficiencyonVariousScalesMatchthestrengthofthechelatetothenatureofthescale-thisreasoningappliestomostapplications,frombathroomcleanerstooilwelldescaling.BaSO4CaOxCaCO3CaSoapDTPA75TO90+100100100EDTA~50100100100NTA~50~80100100EDG~1~45~9810012FunctionalChemicalsBaSO4DissolutionWhatimpactsthefollowingreaction:BaSO4+Chelate[Chelate-Ba]+SO42--thetypeofchelate:DTPA,EDTA,etc-salttype:sodium,potassium,etc-pHStudyMethodologyThemajorityofourlabstudieswereperformedonanalyticalreagentgradeBaSO4powder(‘ARBaSO4‘)at20C.Someworkwasdoneonpowdered‘naturalBarite‘thatcontainedSrSO4.Highpuritychelatesolutionswereusedatuseconcentrationsof~0.10molarinthepresenceofexcessof‘BaSO4’.DissolvedBawasmeasuredtodetermineextentofBaSO4dissolution.BaSO4Dissolution–TypeofChelateBaSO4+Chelate[Chelate-Ba]+SO42-0102030405060708090020406080time(hr)[Ba](mmol/l)TTHA-K6DTPA-K5EGTA-K4EDTA-K4HEDTA-K3DTPMP-KxNTA-K3PDTA-K4GLDA-Na4BaSO4dissolution:Chelateandsalttype01020304050607080020406080time(hr)[Ba](mmol/l)DTPA-KDTPA-NaEDTA-KEDTA-NaDTPAEDTAKNaBaSO4Dissolution:pHBaSO4+DTPA5-[DTPA-Ba]3-+SO42-0102030405060708090020406080time[h]Ba[mmol/l]pH11pH=10.3pH=9.5BaSO4Dissolution-ConclusionsPotassiumDTPAathighpHwilldissolveBaSO4tothegreatestextentandmostquickly.-DissolvineD-K5-40Alternativesofferinglessspeedandefficiency:-SodiumDTPA(DissolvineD-40)-PotassiumEDTA(DissolvineK4-100S)-SodiumEDTA(Dissolvine100-SorE-39)‘NaturalBarite’ismoredifficulttodissolvethan‘ARBaSO4butadditivesappeartohelp.CalciteDissolution:CaCO3EDTA-KHEDTAEDTA-NaGLDA*NTA-K*EDG*EDTMPNTMP020406080100120DissolvedCaafter10minutes(mmol/l)pH=11pH=8pH=5*ReadilybiodegradableinOECD301DAthighpHstrongchelatesarethebestchoiceforCaCO3.GLDAisthebestbiodegradableoption.0.020.040.060.080.0100.0120.0140.0EDTADTPAHEDTAGLDAEDGNTADissolvedCaafter5min(mmol/L)pH5pH8pH11CalciumSulfateDissolution:CaSO4·2H2OMostchelatesworkwellonCaSO4·2H2O.GLDAisthebestbiodegradableoption.Vrecommendedproduct*Akzolabresults**PatentorliteraturedataDissolvine®scaledissolversV(synergist)CSAVVGL-47-SVVH-AM-45VVVVH-40VVVVD-K5-45VVVVD-K5-40VVVVVD-50VVVVVD-40VVAM3-40VVAM2-45VVVVVK4-100SVVVVVE-39Alscales**Siscales**Fescales**CaCO3*CaSO4*SrSO4**BaSO4*Dissolvine®V(synergist)CSAVVGL-VVH-AM-45VVVVH-40VVVVD-K5-45VVVVD-K5-40VVVVVD-50VVVVVD-40VVAM3-40VVAM2-45VVVVVK4-100SVVVVVE-39Alscales**Siscales**Fescales**CaCO3*CaSO4*SrSO4**BaSO4*Dissolvine®VVOverviewWhatarechelatesChelatesinoilfieldapplications:ScaleStimulation-acidsandneedforalternatives-GLDAcarbonatecoreflooding-GLDAsandstonecorefloodingConclusionsAcidStimulationProcessAcidsareusedtocreatewormholestoconnecttheformationtothewellbore.Successdependshowdeepthisacidwillpenetrateintotheformationcreatinguniformwormholes.Propagationofwormholesthroughthedamagedzoneyieldsnegativeskin.23NeedforAlternativeFluidsProblemsassociatedwithHCl:Highreactivityandcorrosionofwelltubularsathightemperatures(200oF).HClcannotbeusedinw