Use of nitrate in souring control of an oil field with low bottom hole temperatureSasha Grigoryan, Adewale Lambo, Shiping Lin, Sabrina Cornish, Tom J ack, Rhonda Clark and Gerrit VoordouwPetroleum Microbiology Research Group, Department of Biological Sciences, University of Calgary, Calgary, Alberta, Canada CanadaISMOS2, JUNE 19, 2009Topicstobecovered:1. Souringcontrolbynitrateinjectioninlowtemperaturefields2. WhatistheelectrondonorfornitratereductionintheEnermarkfield?3. Caninjectednitrateoxidizeironsulfideformeddownhole?4. Microbialcommunityinlowtemperatureoilfieldundernitrateinjection The production of sulfide in oil reservoirs (reservoir souring) can be remediated by injection of nitrate souring) can be remediated by injection of nitrate. Nitrate injection activates 2 new metabolic groups: oil organics SO42-SRBSRBCO2H2Soil organics NO3-hNRBhNRBCO2NO2-, N2H2SNO3-NR SOBNR-SOBNR-SOBS0, SO42-NO2-, N2Oil organics: Volatile fatty acids (VFA a mixture of acetate propionate and Oil organics: Volatile fatty acids (VFA, a mixture of acetate, propionate and butyrate) used in testsHightemperatureoilfields:sulfideproductionlimitedtoinjectionwellboreregionbecauseof: Coolingofinjectorwellboreregionbywaterinjectionh ( ) l h Hightemperature(6080oC)elsewhereinreservoir NutrientrichnessbymixingofinjectionandreservoirwatersSulfideproductioneffectivelyremediatedbynitratebecauseonlyalimitedregionofthefieldneedstobetreated. gGullfaks field GullfaksfieldSunde&Torsvik,2005Canfieldsat:lowerdepth(1000m)and,therefore,lower downhole temperature lowerdownholetemperaturebesuccessfullytreatedwithnitrate?2 Field Sites in the WCSB 2FieldSitesintheWCSBColevilleMHGC2007Coleville19962007Makeup water (MW) p ( )OilW tTo pipelineInjection wellProduction wellPWIWWPInjection water Produced waterWater Water Water WaterWater plantOil bearing rock In a water plant produced water and makeup water are mixed to give injection water The field is operated by produced water reinjection (PWRI)NewprojectMHGCfield:2.Souringcontrolbynitrateinjectioninonshorefieldsoflowtemperature850mdepth,30oCdownholetemperatureHeavyoil(16degreesAPIgravity)2000: start of water injection 2000:startofwaterinjectionInjectionwater(IW)3500m3/dayOilproduction1000m3/dayProducedwaterreinjection(PWRI)Makeupwater4mM(400ppm)sulfate( k 3 ) i lf IW(PW:makeupwater=3:1)is1mMsulfatePW0mMsulfateandonaverage0.1mMsulfide2006:sulfide(gasphase)increasingEvidenceforSouring:DelaycausedbysulfidescavengingofreservoirrockSouring could have been prevented by: Souringcouldhavebeenpreventedby: usingmakeupwaterwith0sulfateGas phase sulfide concentrations determined by field personnelSite 6;13-15Gasphasesulfideconcentrationsdeterminedbyfieldpersonnel10Site 6;13-15 810mv)46H2S (ppm2H011-29-06 1-18-07 3-9-07 4-28-07 6-17-07 8-6-07 9-25-07 11-14-07 1-3-08 2-22-08Date DateMHGClongtermfieldwidenitrateinjection:Injectednitrateconcentration2.4mMfieldwide= 150 ppm nitrate = 1 2 mM Ca(NO3)2 = 200 ppm calcium nitrate =150ppmnitrate=1.2mMCa(NO3)2 =200ppmcalciumnitrateStillgoingontodayWeeklynitratesqueezesat14IWfromJanuary2008 April2009FieldwidenitratepulsesfromJuly2008 March2009toMarch2009.6172323 23-MW208157211717-WP88 IW15185 4988-IW9-PW1431316181922Wemonitor:123911223Makeupwaters(MWs)3 Water plants (WPs)10 1293Waterplants(WPs)2Injectionwells(IWs)15 production wells (PWs) 15productionwells(PWs)every23weeksSampling at Waterplant 1 WP SamplingatWaterplant1WPWaterplantSamplingPointNitratetanksProduction wellsMakeupwaterNitrateProductionwells2PW,3PWetc.p22MWWaterplant1WPInjectionwellse g 14 IWNitrateWaterplant17WPe.g.14IWInjectionwellsNitratee.g.8IWProductionwells6PW,7PWetc.P(mM)y=0,9293xR=0,939712141WP14IW7% loss of nitrateSite1WP68107%lossofnitrateitrateatS024NNitrateat14IW(mM)0 2 4 6 8 10 12 14M)257WP(mMy=0,8637xR=0,8458152017WP8IWatSite1751015% loss of nitrateNitrateNitrate at 8IW (mM)00 5 10 15 20 2515%lossofnitrateNitrateat8IW(mM)DifferenceiscausedbybiocidedosingOverall conclusions: Overallconclusions:i d li dff i l b h i j i Nitratedeliveredeffectivelybytheinjectionsystemtothefieldd i (d ll h f Lossesduringtransport(duetowallgrowthofNRB)are715%.Producingwells 15monitored gMostarehorizontalwellsandreceivewaterfrommorethanoneinjectionwell more than one injection wellSamplingPointAverage sulfide concentration for 12 PWs Averagesulfideconcentrationfor12PWsTh fi t 5 k l k t b t hth ? Thefirst5weekslookgreatbutwhytherecovery?A B C DIWPWIW1mMsulfatePW0.1mMsulfide 1mMsulfideSRBsulfide sulfide sulfideSRBOilorganicsA B C DIWPWIW1mMsulfatePW0.1mMsulfide 1mMsulfateNRB1mMsulfideSRBsulfide sulfide2mMnitrate 2mMnitrite 1mMN2OilorganicsInjectionwatercontains1mMsulfate jThisisreducedto1mMsulfidebySRBpresentasabiofilmclosetotheinjectionwellboreNitrate injection gives initially strong inhibition of sulfate reduction in NitrateinjectiongivesinitiallystronginhibitionofsulfatereductioninthisregionHowever,becausethefieldislowtemperaturebacteriacangrowanywhere anywhereSRBregrowasabiofilmdeeperinthereservoirSulfideconcentrationsrecovertoinitiallevels.HenceNRBandSRBgrowindifferentadjacentzones.WerefertothisasmicrobialstratificationCanthestratificationbebrokenbychangingtheti it t i j ti i t l i it t continuous nitrateinjectionintoapulsing nitrateinjectionregime?Bioreactor studies suggest that this is so (see poster by Bioreactorstudiessuggestthatthisisso (seeposterbyCameronCallbeck)(A)Site14IWSite18PWSite19PWIKmSit Site13PW te16PW13PW16PW(B)1WP 14IW18PW19PWnitrate nitratesqueezesNitrate Squeezes at 14 IW NitrateSqueezesat14IW Weekly; 1000 LNITRATE,mM Weekly;1000Lslugof45%l i iNITRATE,mMcalciumnitrateinjecteddirectlyintoinjectionwell14IWfeeding gproducer13PWWEEKSResponseat13PW pSulfide production ceased on breakthrough of nitrate/nitriteCanapulsingnitrateinjectionstrategyalsoworkfieldwide?253035(A)1WP2025(C)17WPmM)101520251015itrate (m050 20 40 60 80 100 120050 20 40 60 80 100 120NTime (weeks)High nitrate doses were injected for 1 week at the two main Highnitratedoseswereinjectedfor1weekatthetwomainwaterplantsThisgavenitrate/nitritebreakthroughat7PW0 06de (mM)e(mM)0,030,040,050,06(A)0,060,080,1(C)CsulfidCsulfate00,010,020 20 40 60 80 100 12000,020,04ol/day)M)0 20 40 60 80 100 1200,8(D)5(B)0,020 50 100 150ulfide (moCnitrite(mM0,20,40,601234(B)SuC00 50 100 150-100 20 40 60 80 100 120Time (weeks)0,40,5(A)2PWmM)0 30,40,5(D)3PW0,080,1(G)12PW0,10,20,3Csulfide (m00,10,20,30,020,040,0600 20 40 60 80 100 120300y)0,10 20 40 60 80 100 12060(E) 3 PW00 20 40 60 80 100 120200180220260(B)2PWer (m3/day20304050(E)3PW80120160(H)12PW1001400 20 40 60 80 100 120Wate010200 20 40 60 80 100 1200400 20 40 60 80 100 12080100120(C)2PWmol/day)81012(F)3PW101214(I)12PW020406080Sulfide (m024680246800 50 100 150SFig. 4Time (weeks)00 50 100 15000 50 100 1500,1500,200(A)(mM)0 0000,0500,100CiVi/ViAverageconcentrationandtotal0,0000 20 40 60 80 100 1201600,000(B) y)sulfideproductionforallPWsshow:1000 0001200,0001400,000(B)Vi(m3/daystabilizationduringpulsingnitrateinjection800,0001000,0000 20 40 60 80 100 120Vpatterndominatedby2PW150,000200,000250,000(C)ol/day)0,00050,000100,000CiVi(mo0 20 40 60 80 100 120Time(weeks)Conclusions: Conclusions:Nitrate(2mM)dosedeffectivelythroughthefieldFieldwidesulfidedecreased70%inthefirst5weeksfollowedbyd l l i i h d recovery;amodelexplainingtherecoverywaspresentedLocal increased nitrate dose from weeks 33101 eliminated Localincreasednitratedosefromweeks33 101eliminatedproductionofsulfideatoneproductionwellApplicationoffieldwidehigherdosesfromweeks6496stabilizedsulfideproductionWeshouldconcentrateonPWsthatcontributemosttototalsulfide production sulfideproductionTopicstobecovered:1. Souringcontrolbynitrateinjectioninlowtemperaturefields2. WhatistheelectrondonorfornitratereductionintheEnermarkfield?Lambo, A. J ., Noke,K., Larter, S. R., and Voordouw, G. (2008) Competitive, microbially mediated reduction of nitrate with sulfide and aromatic oil components in a low temperature, western Canadian oil reservoir. Environ. Sci. Technol. 42:8941-8946.3. Caninjectednitrateoxidizeironsulfideformeddownhole?Lin, S., Krause, F., and Voordouw, G. (2009) Transformation of iron sulfide to greigite by nitrite produced by oil field bacteria Appl Microbiol Biotechnol 83:369-376 nitrite produced by oil field bacteria. Appl. Microbiol. Biotechnol. 83:369 376. 4. Microbialcommunityinlowtemperatureoilfieldundernitrateinjection Bacterial component showed increased NRB BacterialcomponentshowedincreasedNRB Archaeal(methanogen)componentshowedd d di i decreaseddiversityBefore AfterBefore AfterThankstotheteam(onfirstsamplingtriptoMHGCfield)Tom Jack Adjunct ProfessorAdewale Lambo PDFSasha Grigoryan PDFShiping Lin TechnicianJohanna Voordouw Technician Johanna Voordouw TechnicianSabrina Cornish Graduate StudentRhonda Clark Project Manager j gMHGC oil field study:Kirk Miner Baker PetroliteRyan Ertmoed Baker PetrolitePat Stadnicki EnerplusBill Clay EnerplusThanks to Institutional and Corporate sponsorsNSERC Industrial Research Chair in Petroleum Microbiology Petroleum Microbiology