Use of nitrate in souring control of an

oil field with low bottom hole

temperature
Sasha Grigoryan, Adewale Lambo, Shiping Lin, Sabrina
Cornish, Tom Jack, Rhonda Clark and Gerrit Voordouw
Petroleum Microbiology Research Group, Department of
Biological Sciences, University of Calgary, Calgary, Alberta,
Canada

ISMOS2, JUNE 19, 2009

Topicstobecovered:

1.

Souringcontrolbynitrateinjectioninlowtemperaturefields

2.

WhatistheelectrondonorfornitratereductionintheEnermarkfield?

3.

Caninjectednitrateoxidizeironsulfideformeddownhole?

4.

Microbialcommunityinlowtemperatureoilfieldundernitrateinjection

 The production of sulfide in oil reservoirs (reservoir

souring) can be remediated by injection of nitrate
nitrate.
Nitrate injection activates 2 new metabolic groups:
SRB
oil organics

SO42SRB

CO2

hNRB

H2S
oil organics

NO3hNRB

CO2

NO2-, N2

NR-SOB
H2S

NO3NR SOB
NR-SOB

S0, SO42-

NO2-, N2

Oil organics: Volatile fatty acids (VFA,

(VFA a mixture of acetate,
acetate propionate and
butyrate) used in tests

Hightemperatureoilfields:
sulfideproductionlimitedtoinjectionwellboreregionbecauseof:
Coolingofinjectorwellboreregionbywaterinjection
oC)elsewhereinreservoir
Hightemperature(6080
h
(
) l
h
Nutrientrichnessbymixingofinjectionandreservoirwaters
Sulfideproductioneffectivelyremediatedbynitratebecauseonlya
limitedregionofthefieldneedstobetreated.
g

Gullfaksfield
Gullfaks
field
Sunde&Torsvik,
2005

Canfieldsat:
lowerdepth(1000m)and,therefore,
lower downhole temperature
lowerdownholetemperature

besuccessfullytreatedwithnitrate?

2 Field Sites in the WCSB

2FieldSitesintheWCSB

Coleville
Coleville
1996
MHGC
2007

Makeup
p water (MW)
(
)

Production
well

Injection water
To pipeline

IW

Injection
well

WP

Oil

W t
Water

Water

PW

Produced water

Water plant

Oil 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)

2.Souringcontrolbynitrateinjectioninonshorefieldsoflowtemperature

NewprojectMHGCfield:

850mdepth,30oCdownholetemperature
Heavyoil(16degreesAPIgravity)
2000:startofwaterinjection
2000: start of water injection
Injectionwater(IW)3500m3/day
Oilproduction1000m3/day
Producedwaterreinjection(PWRI)
Makeupwater4mM(400ppm)sulfate
IW(PW:makeupwater=3:1)is1mMsulfate
(
k
3 )i
lf
PW0mMsulfateandonaverage0.1mMsulfide

EvidenceforSouring:

2006:sulfide(gasphase)increasing
Delaycausedbysulfidescavengingofreservoirrock

Souringcouldhavebeenpreventedby:
Souring could have been prevented by:
usingmakeupwaterwith0sulfate

Gas phase sulfide concentrations determined by field personnel

Gasphasesulfideconcentrationsdeterminedbyfieldpersonnel
Site 6;13-15

H2S (ppm
H
mv)

10
8
6
4
2
0
11-29-06 1-18-07

3-9-07

4-28-07

6-17-07

8-6-07

Date

9-25-07 11-14-07

1-3-08

2-22-08

MHGClongtermfieldwidenitrateinjection:
Injectednitrateconcentration2.4mMfieldwide
= 150 ppm nitrate = 1 2 mM Ca(NO3)2 =200ppmcalciumnitrate
=150ppmnitrate=1.2mMCa(NO
= 200 ppm calcium nitrate
Stillgoingontoday

Weeklynitratesqueezesat14IWfromJanuary2008 April2009

FieldwidenitratepulsesfromJuly2008 March2009toMarch
2009.

23

23-MW

17

17-WP

8 IW
8-IW

9-PW

17

23
21

20

Wemonitor:
3Makeupwaters(MWs)
3Waterplants(WPs)
3 Water plants (WPs)
2Injectionwells(IWs)
15productionwells(PWs)
15 production wells (PWs)

every23weeks

78
15

5 4
18 19
14 13
16

22

11
10

9
12

Sampling at Waterplant 1 WP
SamplingatWaterplant1WP
Waterplant

Nitratetanks

SamplingPoint

Nitrate
Makeupwater
p
22MW

Productionwells
Production
wells
2PW,3PWetc.

Waterplant1WP
Injectionwells
e g 14 IW
e.g.14IW
Waterplant17WP

Injectionwells
e.g.8IW

Nitrate
Productionwells
6PW,7PWetc.

Nitrate

NitrateatSSite1WP
P(mM)

14

y=0,9293x
R=0,9397

12
10
8

1WP

14IW

7% loss of nitrate
7%lossofnitrate

4
2
0
0

10

12

14

NitrateatSite17
7WP(mM
M)

Nitrateat14IW(mM)
25

y=0,8637x
R=0,8458

20
15

17WP

10

8IW

15% loss of nitrate

15%lossofnitrate

5
0
0

10

15

20

25

Nitrate at 8IW (mM)

Nitrateat8IW(mM)

Differenceiscausedbybiocidedosing

Overall conclusions:
Overallconclusions:
Nitratedeliveredeffectivelybytheinjection
i
d li
d ff i l b h i j i
systemtothefield
Lossesduringtransport(duetowallgrowthof
d i
(d
ll
h f
NRB)are715%.

Producingwells
g
15monitored
Mostarehorizontalwellsandreceivewaterfrom
more than one injection well
morethanoneinjectionwell

SamplingPoint

Average sulfide concentration for 12 PWs

Averagesulfideconcentrationfor12PWs

Th fi t 5
Thefirst5weekslookgreatbutwhytherecovery?
k l k
t b t h th
?

IW

PW

1mMsulfate 1mMsulfide

sulfide

sulfide

sulfide

0.1mMsulfide

SRB

Oilorganics

IW

PW

1mMsulfate 1mMsulfate

1mMsulfide

NRB
2mMnitrate 2mMnitrite

SRB
1mMN2

sulfide

Oilorganics

sulfide

0.1mMsulfide

Injectionwatercontains1mMsulfate
j
Thisisreducedto1mMsulfidebySRBpresentasabiofilmclosetothe
injectionwellbore
Nitrate
Nitrateinjectiongivesinitiallystronginhibitionofsulfatereductionin
injection gives initially strong inhibition of sulfate reduction in
thisregion
However,becausethefieldislowtemperaturebacteriacangrow
anywhere
SRBregrowasabiofilmdeeperinthereservoir
Sulfideconcentrationsrecovertoinitiallevels.

HenceNRBandSRBgrowindifferentadjacentzones.
Werefertothisasmicrobialstratification
Canthestratificationbebrokenbychangingthe
continuous
ti
nitrateinjectionintoapulsing
it t i j ti i t
l i nitrate
it t
injectionregime?
Bioreactorstudiessuggestthatthisisso
Bioreactor studies suggest that this is so (seeposterby
(see poster by
CameronCallbeck)

(A)
Site18PW

Site14IW

IKm

Site19PW

Sitte16PW

Site13PW

13PW

(B)

16PW
1WP
nitrate

14IW
nitratesqueezes

18PW
19PW

Nitrate Squeezes at 14 IW
NitrateSqueezesat14IW
Weekly;
Weekly;1000L
1000 L
slugof45%
calciumnitrate
l i
i
injecteddirectly
intoinjectionwell
g
14IWfeeding
producer13PW

NITRATE,mM

WEEKS

Responseat13PW
p

Sulfide production ceased on breakthrough of

nitrate/nitrite

Canapulsingnitrateinjectionstrategyalsoworkfieldwide?

Nitrate (m
mM)

35

25

(A)1WP

30

(C)17WP

20

25
20

15

15

10

10
5

0
0

20

40

60

80

100

120

20

40

60

80

100

Time (weeks)

Highnitratedoseswereinjectedfor1weekatthetwomain
High
nitrate doses were injected for 1 week at the two main
waterplants

120

Thisgavenitrate/nitritebreakthroughat7PW

0,1

(A)

0,05

Csulfatee (mM)

Csulfidde (mM)

0 06
0,06

0,04
0,03
0,02
0,01

0,08
0,06
0,04
0,02

0
0

20

40

60

80

100

120

50

100

(B)

4
3
2
1
0
20

40

60

80

100

150

(D)

0,8

Cnitrite (mM
M)

Su
ulfide (mo
ol/day)

0,02

-1 0

(C)

0,6
0,4
0,2

120

0
0

Time (weeks)

50

100

150

Csulfide (m
mM)

0,5

(D)3PW
0,4

0,4

0,06

0,2

0,2

0,04

0,1

0,1

0,02

0
0,1 0
0

Wate
er (m3/day
y)

(G)12PW

0,08

03
0,3

0,3

0
20

40

60

80

100

20

40

60

80

100

120

0
60

(B)2PW

260

120

300

20

40

60

80

100

120

60

80

100

120

200

(E) 3 PW
(E)3PW

50

(H)12PW

160

40
220

120

30
80

180

20

140

10

40

100

Sulfide (m
S
mol/day)

0,1

0,5

(A)2PW

20

40

60

80

100

120

20

40

60

80

100

100
80

60

40

20

0
0

50

100

150

Fig. 4

12

(F)3PW

10

(C)2PW

20

40

14

12

120

120

(I)12PW

10
8
6
4
2
0

50

100

150

Time (weeks)

50

100

150

CiVi/Vi (mM)

0,200

(A)
0,150
0,100
0,050
0 000
0,000
0

20

40

60

80

100

120

Averageconcentrationandtotal
sulfideproductionforallPWs
show:

V
Vi (m3/day
y)

1600,000

(B)

1400,000

stabilizationduringpulsingnitrate
injection

1200,000
1000 000
1000,000

patterndominatedby2PW

800,000

CiVi(mo
ol/day)

20

40

60

80

100

120

60

80

100

120

250,000

(C)

200,000
150,000
100,000
50,000
0,000
0

20

40

Time(weeks)

Conclusions:
Nitrate(2mM)dosedeffectivelythroughthefield
Fieldwidesulfidedecreased70%inthefirst5weeksfollowedby
recovery;amodelexplainingtherecoverywaspresented
d l
l i i
h
d
Local
Localincreasednitratedosefromweeks33
increased nitrate dose from weeks 33101
101eliminated
eliminated
productionofsulfideatoneproductionwell
Applicationoffieldwidehigherdosesfromweeks6496stabilized
sulfideproduction
WeshouldconcentrateonPWsthatcontributemosttototal
sulfide production
sulfideproduction

Topicstobecovered:

1.

Souringcontrolbynitrateinjectioninlowtemperaturefields

2.

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.
bacteria Appl
Appl. Microbiol
Microbiol. Biotechnol
Biotechnol. 83:369-376
83:369 376.

4.

Microbialcommunityinlowtemperatureoilfieldundernitrateinjection

 Bacterial
BacterialcomponentshowedincreasedNRB
component showed increased NRB
Archaeal(methanogen)componentshowed
d
decreaseddiversity
d di
i

Before

After

Before

After

Thankstotheteam(onfirstsamplingtriptoMHGCfield)

Tom Jack
Adewale Lambo
Sasha Grigoryan
Shiping Lin
Johanna Voordouw
Sabrina Cornish
Rhonda Clark

Adjunct Professor
PDF
PDF
Technician
Technician
Graduate Student
Project
j
Manager
g

MHGC oil field study:

Kirk Miner
Ryan Ertmoed

Baker Petrolite
Baker Petrolite

Pat Stadnicki
Bill Clay

Enerplus
Enerplus

Thanks to Institutional and Corporate

sponsors
NSERC Industrial Research Chair in
Petroleum Microbiology