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