SPE 56772
Control of Hydrogen Sulfide in Oil and Gas Wells With Nitrite Injection
P.J. Sturman and D.M. Goeres, Center for Biofilm Engineering, Montana State University, and M.A. Winters, BP-Amoco
Copyright 1999, Society of Petroleum Engineers Inc.
This paper was prepared for presentation at the 1999 SPE Annual Technical Conference and
Exhibition held in Houston, Texas, 3–6 October 1999.
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Abstract
The downhole injection of nitrite-containing solutions into
sour oil and gas wells under controlled conditions has been
observed to effectively remove hydrogen sulfide (H2S) from
aqueous and gas phases. Souring control using nitrite has
been successfully applied to a gas well in the San Juan Basin
of New Mexico and to an oil well in the Amoco Netherlands
Rijnfield. H2S removal from topsides water separations
equipment was also facilitated using nitrite. Injected nitrite
(NO2-) scavenges H2S and prevents the activity of sulfate-
reducing bacteria while it is present. H2S production from oil
or gas wells treated with nitrite may be suppressed for much
longer periods of time. In a 36-hour downhole squeeze in a
gas well, injected NO2- removed H2S from produced gas for a
period of 7 months. SRB populations in produced fluids were
reduced for a period of 3 months following treatment. In an
oil dehydrator, the addition of NO2- during regular operation
resulted in a decrease in aqueous-phase H2S from 40-60 mg/l
to less than 1 mg/l. Corrosion rate data indicated a less
corrosive environment during the NO2- addition period than
prior to the addition. In a downhole squeeze in an oil
production well, injected NO2- decreased H2S in associated
gas from 140 ppm to less than 1 ppm for 60 days following
treatment. H2S levels remained below pre-injection levels for
6 months following treatment. Oil production increased
immediately following the treatment, probably due to the
dissolution of precipitated iron sulfides in the zone
surrounding the well bore. This treatment has proven an
effective means of controlling H2S in oil and gas wells as well
as a method of removing iron sulfide scale from the near well-
bore.
Introduction
Hydrogen sulfide (H2S) is commonly found as a dissolved
constituent in produced water from oil wells and as a minor
(though significant) component of natural gas. H2S is toxic,
highly corrosive, and frequently leads to the precipitation of
metal sulfides in both the subsurface and in above-ground
piping and fluid separation equipment. The presence of H2S in
produced water or gas frequently necessitates costly removal
equipment and may reduce the sales value of the product.
Subsurface production of H 2S results from the activity of
sulfate reducing bacteria (SRB) which utilize short chain
volatile fatty acids (VFAs) and other organic compounds for
cellular carbon and catalyze the reduction of sulfate (SO42-) to
hydrogen sulfide (HS- and S2- may also occur depending on
solution pH). SRB presence in subsurface cores has been
demonstrated under a wide variety of temperature and nutrient
conditions1.
H2S control has typically focused on the use of sulfide
scavengers and/or biocides. These chemicals have been used
both in topsides equipment and in downhole applications.
Though typically effective, these chemicals are costly in
application and may exhibit unintended toxicity in produced
fluids. In recent years, nitrate (NO3-) has been used by several
workers as an agent to control H2S in oilfield applications.
Nitrate has been added either at the injection well with the
waterflood2,3 or at the production well in a squeeze treatment
or produced water treatment3. The mechanism of action of
nitrate in removing sulfides from produced waters has been
suggested to be the selective enhancement of denitrifying
bacteria (DNB) at the expense of SRB4,5. This mechanism
relies on the utilization of volatile fatty acids (acetate,
butyrate, formate, etc.) by faster-growing DNB such that these
necessary carbon sources are unavailable for SRB4. Fauque et
al.6 have shown SRB capable of utilizing a wide range organic
compounds as carbon sources, however. Jenneman, et al.2 and
Telang et al.7 have reported that the addition of nitrate into an
injection well did stimulate the indigenous population of
autotrophic nitrate-reducing bacteria (NRB), which are
responsible for the reduction of nitrate to nitrite. Since these
autotrophs do not require organic carbon for growth, their
mechanism of action does not depend on out-competing SRB
for volatile fatty acids (VFAs). In these field studies2,7, sulfide
reduction/removal at the production well was attributed to the
2 P.J. STURMAN, D.M. GOERES, M.A. WINTERS
production of an SRB inhibition agent by the abundant NRB.
This agent was speculated to be nitrite.
Laboratory experimental work to develop an effective,
field-applicable de-souring technology began at the Center for
Biofilm Engineering at Montana State University in 1992 with
support from a consortium of 5 major oil companies (ARCO,
Amoco, Chevron, Conoco, Exxon). Results from laboratory
column experiments using crushed sandstone cores and
microbial inocula from the North Sea and the North Slope of
Alaska, indicated that sulfide production was inhibited when
either nitrate or nitrite was added to soured columns8. Nitrate
addition was only effective , however, after the appearance of
nitrite due to the metabolism of NRB. Further laboratory
characterization of the mechanisms of SRB growth9 led to the
decision to implement souring control using nitrite at 2 field
sites. Since nitrite was found to be the major inhibitory factor
for SRB8, it was chosen over nitrate to eliminate the need for
an active DNB population to reduce nitrate to nitrite.
In addition to its apparent benefits as a SRB inhibitory
agent, nitrite is also an effective scavenger of hydrogen sulfide
according to the following proposed stoichiometry8:
3 H2S + 3 HS- + 4 NO2- + 7 H+ • 0.75 S80 + 2 N2 + 8 H2O
Nitrite was therefore chosen for production well squeeze
treatments at a sour gas well in the San Juan Basin of New
Mexico (USA) and at a sour oil well in the Rijn Field of the
Dutch North Sea.
Gas Well Test
The gas well test was planned and implemented in March
1996 with the support of Amoco and Halliburton.
Site Description
The San Juan Basin of New Mexico is part of the Mesa Verde
formation. Lithology is sandstone with average porosity
10.5% and permeability 0.30 millidarcys. Average water
content is 45%. Gross gas-bearing interval thickness is 688’.
The average well spacing is 160 acres. The well chosen for
this field demonstration was Elliot B2A, which produces 50-
70 MCFD (1996) at a reservoir pressure of 500 psig. H2S
levels in produced gas from Elliot B2A were measured at 30-
50 ppm.
Test Procedure
Prior to the nitrite addition test, water chemistry and SRB
content were determined for produced water from Elliot B2A
(Table 1). Immediately prior to the test, the well was shut in
and a solution of 1400 lb. sodium nitrite was mixed with 1000
gallons de-aerated water. Over a 5 hour period, this
concentrated NaNO2 solution was injected with 800 bbl. of
water for a final concentration of 1000 mg/l NO2- (as
Nitrogen). The fluid was held in place under surface pressure
for 36 hours, then the well was swabbed for production
purposes. Gas production from Elliot B2A was initiated
thereafter, with measurement of H2S (gas phase) and water
constituents for 7 months. Gas phase H2S measurements were
SPE 56772
made on site with Drager Tubes. Temperature and pH were
measured in the water phase on-site, all other water chemistry
analysis was performed at the Halliburton Analytical
Laboratory, Farmington, NM. Iron measurements were not
taken during this field test. SRB were quantified by
inoculation in Postgate B media, serial dilution, incubation at
thermophilic temperature, and quantification via most-
probable-number (MPN) technique.
Results and Discussion
After nitrite injection and a 36 hour shut-in period, Elliot B2A
was brought into production at pre-soak levels (50-70 MCFD).
Following start-up, H2S levels (gas phase) and water
chemistry samples were collected on a daily basis for a week,
and weekly thereafter. The effects of the nitrite treatment were
immediately evident, with no measurable H2S in produced
gas, and no culturable SRB present in produced water (Table
1). One day after the well was brought into production, nitrite
levels in produced water were 380 mg/l (as N), which
indicates that not all the injected nitrite was consumed during
the 36 hour soak period. Analyses indicated that neither
ammonia nor nitrate were present in produced fluids before or
after nitrite treatment. Sulfate levels increased from 680 mg/l
to 927 mg/l immediately following treatment, but dropped
back to 657 mg/l after 30 days of production. The VFA
profile of produced water changed markedly following nitrite
treatment. Prior to nitrite injection, acetate was the dominant
VFA at 127 mg/l. Propionate and formate were also present at
low concentrations (6 mg/l and 1 mg/l, respectively).
Following nitrite treatment, acetate dropped to 48 mg/l while
propionate and formate increased to 480 mg/l and 89 mg/l.
These immediate water chemistry changes are consistent with
the suppression of SRB activity. SRB which utilize higher
molecular weight VFAs in the production of acetate
(incomplete oxidation) typically grow faster than SRB which
mineralize acetate10 (complete oxidation). Suppression of
SRB activity therefore typically results in an increase in
propionate, formate and butyrate and a decrease in acetate, as
compared to pre-suppression conditions8.
The long term effects of the one-time nitrite soak treatment
are shown in Fig. 1. Gas phase H2S levels remained under 5
ppm for 7 months following treatment. SRB levels in
produced water remained below detection for 3 months, then
returned to pre-treatment levels (103 cells/ml). Trace levels of
nitrite were measured in produced fluids for only 10 days
following treatment, indicating that any the long-term benefits
are not due to the continued presence of nitrite in the
subsurface. This long-term beneficial effect was initially
considered to be due to the suppression of SRB by ephemeral
contact with nitrite. Other workers have noted similar
phenomena with injected nitrate, and have attributed it to
DNB or NRB out-competing SRB for available electron
donors5,11 or to the production of nitrite by indigenous NRB
and the subsequent suppression of SRB activity by nitrite2.
Competition of DNB/NRB with SRB for electron donors is
clearly not the causative mechanism here, since nitrite was
present for less than 10 days, and nitrate was never present. It
SPE 56772 CONTROL OF HYDROGEN SULFIDE IN OIL AND GAS WELLS WITH NITRITE INJECTION
is well understood that nitrite inhibits SRB while it is present,
but the mechanism of lasting effect has not been elucidated.
Conversely, Morris et al.12 found no long term benefit to the
addition of a commercial nitrate application in the treatment of
sour cores in laboratory studies. They concluded that nitrate
must be continually present to maintain sulfide suppression.
Subsequent experimentation which involved the application of
100 mg/l nitrite (as N) to sour SRB biofilm reactors here at the
CBE has reinforced the conclusions of Morris et al.11. In these
experiments, sulfide levels rapidly returned to pre-test levels
when nitrite was washed out of the continuous flow biofilm
reactors13.
Reconciliation of this apparently contradictory data may be
possible if one considers the inorganic reactions which likely
take place after the addition of nitrate or nitrite to an actively
souring environment in the subsurface. Injection of high
concentrations of dissolved nitrite or nitrate radically alters the
oxidation-reduction (redox) conditions of the subsurface. It is
well recognized that oxidized nitrogen compounds readily
react with dissolved hydrogen sulfide. Less often quantified
are the redox reactions of nitrate and nitrite with other metal
sulfides, principally iron sulfide. Nitrate reacts with pyrite
(FeS2) according to the following stoichiometry14:
5FeS2 + 14NO3- + 4H+ • 7N2 + 5Fe2+ + 10SO42- + 2H2O
and
10 Fe2+ + 2 NO3- + 14 H2O • 10 FeOOH + N2 + 18 H+
less stable iron sulfide phases (FeS) and nitrite could be
expected to react by similar stoichiometry.
An increase in dissolved iron at a production well treated
with nitrate was noted by Giangiacomo et al.3 and was
attributed to the activity of DNB. The presence of FeS has
been found to facilitate rates of denitrification (and subsequent
Fe liberation) in river sediments15, however denitrification was
found to be totally inhibited by Fe2+ concentrations of 0.1 mM
(5.6 mg/l).
Whether abiotic or biotic, the dissolution of iron sulfide
has the effect of removing a significant solid phase from the
subsurface, which may increase permeability and fluid
recovery. Increased oil recovery was noted by Giangiacomo
et al.3 along with elevated iron following nitrite treatment,
suggesting that iron sulfides which had previously blocked
pore spaces may have been removed. This suggests a
conceptual model which explains the lasting sulfide inhibition
effects of nitrate or nitrite. After the nitrite or nitrite has
reacted or washed out of the subsurface, SRB activity may
immediately resume, but produced sulfides readily react with
formation iron (or other metals) and precipitate as metal
sulfides. The effect of the nitrite or nitrate addition is
therefore analogous to backwashing a filter.
Unfortunately dissolved iron was not measured in the field
test at Elliot B2A, however the results from the field test at the
oil production well in the Rijn Field also support this model.
3
Oil Facility Tests
The oil facility test was performed with the assistance of
Amoco-Netherlands and Baker-Petrolite. The test was
performed at the Rijn Field production facility located
approximately 20 miles off the coast of Den Hague,
Netherlands. The oil facility test was implemented in two
parts. In the first step, a nitrite solution was injected into an
oil dehydrator over a period of 20 hours to determine any
lasting effects on sulfide production in this vessel. In the
second step, a nitrite solution was injected into an oil
production well (Well A2) and held in place for approximately
2 days prior to production of the well.
Site Description
The Rijn Field production facility operates 17 seawater
injection wells and 13 production wells and has been operated
under waterflood conditions for over 10 years. Average well
depth is 6500’ and the oil bearing interval consists of 4 zones
which vary in permeability from 0.5 md in Zone D to 120 md
in the uppermost Zone A. Watercut averages 95% and the
bulk of the remaining oil resides in the lower permeability
zones. Reservoir temperature is 68oC at a pressure of 2000
psi.
The production system utilizes gaslift to assist the flow of
fluids from the subsurface. Produced gas is separated at a
production separator and is then compressed and reinjected.
Produced fluids contain SRB, sulfate and a variable mixture of
VFAs. Water chemistry data for baseline formation water
(prior to seawater flood), injection water, and produced water
are shown in Table 2.
Since 1990, mean H2S levels in produced gas have steadily
increased from 40 to over 200 ppm (1997), necessitating
periodic, unplanned system shut-downs to remove
accumulated solids and biofilm in topsides water separation
equipment. H2S concentrations in the gas blanket of water
separation process units have risen as high as 600 ppm. Initial
microbiological testing and a system engineering analysis
(May-June 1997) indicated that biogenic H2S production was
occurring both in topsides water separation equipment
(principally the oil dehydrator and flotation units), as well as
in the subsurface. Results from these initial tests were used to
determine H2S problem areas within the facility and to design
dosing protocols for effective H2S scavenging and SRB
inhibition using nitrite.
Nitrite treatment of the oil dehydrator was performed in
December 1997. The dehydrator has a gross volume of 10 m3,
evenly divided between water and oil phases. The gas
headspace in the dehydrator is minimal and could not be
accessed for sampling. H2S levels in the oil dehydrator were
typically 40-60 mg/l, the highest water phase levels measured
in the topsides equipment. During periodic system
maintenance, it has been noted that a significant sludge layer
accumulates in the bottom of the oil dehydrator. This layer
was not accessible for sampling prior to testing, but was
expected to harbor high populations of SRB. Sulfate and VFA
data indicate high SRB activity in the oil dehydrator (Table 3)
4 P.J. STURMAN, D.M. GOERES, M.A. WINTERS
Temperature and pH were stable at 40oC and 7.3, respectively
and pressure was atmospheric.
A downhole squeeze of nitrite into oil production well A2
was performed in March 1998. This well typically produced
100-160 ppm H2S in gas and ~6 mg/l H2S in water (95%
watercut). Oil production was approximately 200 BOPD.
Iron in produced water from A2 was 0.5-1 mg/l.
Test Procedure
Highly concentrated aqueous solutions of sodium nitrite were
prepared by Baker-Petrolite on-shore under minimal aeration
conditions and shipped to the platform no more than 5 days
prior to use.
Oil Dehydrator Test. The oil dehydrator influent makeup
is approximately 75% oil, 25% water and is the direct effluent
of the production separator. Water residence time in the
dehydrator is approximately 1.5 hours. The concentrated
nitrite solution was added directly to the oil dehydrator
influent stream via positive displacement pump. Nitrite was
added for a total of 20 hours. The method of nitrite addition
was to start with a high concentration and reduce this in a step
fashion over the 20 hour period. The target NO2- (nitrogen)
concentrations in the oil dehydrator influent were: 650 mg/l
(0-2.75 hr.), 140 mg/l (2.75-11 hr.), 50 mg/l (11-20 hr.).
On-site monitoring of oil dehydrator effluent was begun
immediately following the addition of nitrite. Liquid phase
H2S was measured via Hach Model HS-C kit (effervescence
method). Samples containing >10 mg/l H2S were diluted into
the measurable range 0.2-10 mg/l. H2S in gas was measured
using Drager tubes after collection in a bladder. Aqueous
nitrite was measured via Hach kit (diazotization method) using
a Hach color spectrophotometer to measure absorbance
relative to a standard curve. Total iron was measure via Hach
kit (Phenathroline method), pH was measured via probe and
corrosion rate was monitored using a continuous flow-through
LPR probe.
Samples were also collected for analysis at SGS Redwood
Laboratories (Spijkenisse, Netherlands) for VFAs, sulfate,
iron, nitrate, nitrite, and chloride. SRB samples were analyzed
via MPN (using Postgate B media) and Angus methods.
Oil Well Squeeze Test. Concentrated nitrite solution was
shipped to the platform in 200 L drums. Production well A2
was shut down and deaerated seawater was pumped into the
well. The concentrated nitrite solution was added at the well
head using a positive displacement pump. The average
concentration of NO2- ( as nitrogen) in the injected water was
615 mg/l . A total of 2020 bbl water was injected over a 36
hour period and the solution was held in place for another 18
hours prior to restarting the well. Production from the well
was routed to the test separator following the squeeze
treatment. For the first 2 weeks following the nitrite injection,
well A2 was allowed to produce without gaslift, allowing
accurate determination of H2S levels in produced gas.
Following this period, gaslift was restarted to increase the
fluids production rate. Nitrite, H2S (gas and aqueous), pH,
and Fe were determined at the test separator via the field
methods described above. Laboratory samples for nitrite,
SPE 56772
sulfate, VFAs, and iron were collected at the test separator and
sent to SGS Redwood Laboratories for analysis.
Results and Discussion
Oil Dehydrator Test. Nitrite addition to the oil dehydrator
influent proceeded in the step fashion indicated in Fig. 2 (solid
line). The nitrite concentration measured in the oil dehydrator
effluent peaked at 705 mg/l NO2--N 2 hours after addition
began. At t=33 hours, 4 mg/l nitrite was measured in the
effluent.. Nitrite was completely washed out of the oil
dehydrator 45-50 hours following the start of treatment (Fig.
2, solid diamonds). If the oil dehydrator behaved as a well
mixed continuous stirred tank reactor (CSTR), the nitrite
washout curve should have been well below the actual
measured nitrite concentrations (Fig. 2, dashed line). This
suggests that the dehydrator was either not well mixed, or that
nitrite may diffuse into the bottom sludge layer when present
at high concentrations, then diffuse out again when the
concentration is reduced.
Prior to nitrite treatment, aqueous phase H2S levels in the
dehydrator were typically in the 40-60 mg/l range (several
measurements of ~8 mg/l prior to nitrite addition were
anomalously low according to historic data, Fig. 3).
Following nitrite addition, H2S dropped to <0.5 mg/l for
approximately 40 hours, then increased to 5-6 mg/l for the
next several days. This is approximately tenfold less than the
normal pre-test H2S level. During the test, culturable SRB in
the dehydrator effluent dropped from 103-104 cells /ml to 10
cells/ml. Unfortunately, SRB data were not available after
t=30 hours. The corrosion rate in the dehydrator varied from
0.5-50 mills per year (mpy) prior to the addition of nitrite and
stabilized at 2-3 mpy when nitrite was present and following
nitrite washout (Fig. 4). Concurrently, the total iron
concentration in dehydrator effluent remained between 0.5-2
mg/l before and after nitrite addition.
These data confirm the H2S scavenging and SRB
inhibition effects of nitrite/nitrate observed by other workers2-5
and the authors in prior field and laboratory tests. Although
the inhibition and scavenging effects of the added nitrite
evidently continued beyond the point of nitrite washout, it is
interesting to note that nitrite did not result in the mobilization
of iron. This may be because there is little FeS present in the
oil dehydrator bottom sludge, or because other chemical
species present (H2S and organics) are more easily oxidized by
nitrite. Therefore, the lasting effects of nitrite cannot be
attributed to the oxidation and dissolution of iron sulfide, as
was the case in the downhole treatment. It is probable that the
added nitrite oxidized at least the surface layer of the reduced
organics present in the bottom sludge of the dehydrator, and
this may have had a lasting effect on SRB which reside there.
The apparent suppression of corrosion in the dehydrator after
nitrite treatment is probably the result of the removal of H2S
from the water. At very high concentrations, nitrite may
completely passivate a metal surface. At lower concentrations
nitrite has the potential to enhance localized corrosion via
incomplete anodic passivation, thereby driving the corrosion
SPE 56772 CONTROL OF HYDROGEN SULFIDE IN OIL AND GAS WELLS WITH NITRITE INJECTION
in localized, non-passivated zones16. This was a concern in
adding nitrite to the dehydrator. The highest concentration
used (~700 mg/l as N) was either not sufficiently high to
initiate pitting corrosion, or was not present long enough to
initiate high corrosion rates.
Oil Well Squeeze Test. After the 54 hour injection + hold
period, well A2 was restarted with production routed to the
test separator for analysis. Nitrite was measured in A2
production for approximately 40 hours following restart (Fig.
5). In this case, the corrosion rate as measured by LPR probe
did not respond as it did in the oil dehydrator test. The
corrosion rate dropped as the nitrite concentration in produced
water decreased. Unfortunately, pre-nitrite test corrosion data
are not available at well A2, it is apparent, however, that over
the long term, the corrosion rate did not increase as a result of
nitrite injection. The effects of nitrite injection on gas and
aqueous-phase H2S and dissolved iron are shown in Fig. 6.
Prior to nitrite injection, H2S was present at 120-160 ppm in
produced gas and 6 mg/l in produced water, and the total iron
was 0.5 mg/l. Following nitrite treatment, H2S levels
decreased to below detection limits in both water and gas.
Concurrently, total iron in produced water increased 20-fold to
10 mg/l. H2S in produced water increased to 1 mg/l after 10
days of production at A2 and 2 mg/l after 50 days, where it
remained for the following 4 months. H2S in gas increased
more slowly at first, but eventually returned to pre-test levels
(90 ppm) 6 months after treatment. Iron remained in the 4-10
mg/l range for approximately 30 days, then dropped to 2.5
mg/l for the duration of measurement (6 months). Sulfate and
FVA data collected prior to and following the nitrite addition
indicated a slight increase in sulfate (from 2000-2500 mg/l)
following the addition of nitrite, but the rapid return to pre-test
levels within 3 days. No VFAs were detected above the
quatitation limit (5 mg/l) either before or after the nitrite
addition.
It is apparent that nitrite injection had a significant and
lasting effect on H2S in produced fluids from this well. In
addition, oil production from A2 increased from 200-400
BOPD for approximately 30 days immediately following
nitrite injection. This is thought to be correlated with the
increased iron production from A2. Injected nitrite caused the
dissolution of iron sulfide in the formation, which opened
previously occluded pores, leading to a short term increase in
oil recovery. The long term effects of nitrite injection on
subsurface SRB are not known. Culturable SRB were
measured at very low levels (1-10 cells/ml) at the test
separator before and after nitrite treatment. It is not possible
to say if SRB in the subsurface were inhibited or suppressed.
The observed H2S effects could be due solely to the
dissolution of iron sulfide and creation of an oxidized zone
near and within the wellbore, which then had a large capacity
for precipitation of newly formed FeS. Iron levels in the
formation water of the 4 oil-bearing zones varies from 5-40
mg/l. The measured level of 10 mg/l immediately following
nitrite treatment at A2 was likely due to both the dissolution of
FeS and the breakthrough of background iron which had
formerly precipitated as FeS, when SRB were actively
5
producing H2S. Sulfate data collected during the test indicates
only a short term suppression of SRB was likely (~3 days), if
at all.
Conclusions
Aqueous nitrite solutions were injected for H2S control into a
sour gas well, a sour oil well, and an oil dehydrator. The
results from these field trials indicate that nitrite has an
immediate and significant reduction effect on aqueous- and
gas-phase H2S when so used. Furthermore, H2S reduction in
these systems lasted from days to months beyond the removal
of nitrite. Though nitrate has received much more attention
than nitrite in laboratory and field studies to control souring,
the mechanism of action of each is thought to be similar. Both
are reactive in the subsurface with H2S and iron sulfides, and
both have been observed to inhibit the activity of SRB when
present. Whether nitrate or nitrite is a lasting inhibitor to
SRB, and the mechanism of such inhibition has not yet been
fully elucidated. Past workers3-5 have suggested that this
mechanism is the enhancement of DNB through the addition
of nitrate, which subsequently out-compete SRB for electron
donors (VFA). This may occur when nitrate/nitrite is present,
but does not explain the removal of H2S for days to months
after the reaction/consumption of these compounds. A more
likely mechanism is the oxidation of various reduced
compound in the subsurface, principally FeS in this instance,
which creates a sink for their subsequent precipitation from
solution. An additional benefit to FeS dissolution may be the
increased oil recovery from previously occluded pores. Nitrite
treatment is an economically attractive alternative for the de-
souring of oil and gas wells which are marginal producers due
to high H2S.
Acknowledgments
We thank Stan Kolodzie of BP-Amoco and Ruud Van Dijk of
Amoco-Netherlands for their assistance during and after the
field tests; Henry Nichols of BP-Amoco for his assistance in
corrosion data interpretation; and John Sears of the
Department of Chemical Engineering, Montana State
University for his technological insights.
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6 P.J. STURMAN, D.M. GOERES, M.A. WINTERS SPE 56772

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the SPE/EPA Exploration and Production Environmental pH 7.5 7.7 7.7
Conference, Dallas, TX, 3-5 March 1997. Cl- (mg/l) 10,500 8,800 9,500
6. Fauque, G., LeGall, J., and Barton, L.L.: “Sulfate-Reducing and SO4-2 (as S) (mg/l) 680 927 657
Sulfur-Reducing Bacteria,” in Variations in Autotrophic Life, Acetate (mg/l) 127 48 114
J.M. Shively and L.L. Barton, Eds., Academic Press, London Propionate (mg/l) 6 480 460
(1991) 271.
i-Butyrate (mg/l) ND ND ND
7. Telang, A.J., Ebert, S., Foght, J.M., Westlake, D.W.S., Jenneman,
G.E., Gevertz, D., and Voordouw, G.: “Effect of Nitrate Injection Formate (mg/l) 1 89 160
on the Microbial Community in an Oil Field as Monitored by NO2- (as N) (mg/l) ND 380 ND
Reverse Sample Genome Probing,” Appl. Environ. Microbiol. SRB (cells/ml) 102–106 ND ND
(1997) 63, 1785. ND = not detected.
8. Reinsel, M.A., Sears, J.T., Stewart, P.S., and McInerney, M.J.:
“Control of Microbial Souring by Nitrate, Nitrite or
Gluteraldehyde Injection in a Sandstone Column,” J. Indust.
Microbiol. (1996) 17, 128.
9. Chen, C.I., and Reinsel, M.A.: “Characterization of Microbial Table 2. Rijn Field Water Analysis
Souring in Berea-Sand Porous Medium with a North Sea Oil Baseline Injection Produced
Field Inoculum,” Biofouling (1996) 9, 175. Constituent Formation Water Water Water
10. Widdel, F.: “Microbiology and Ecology of Sulfate- and Sulfur- pH 6.5 7.7 7.1
reducing Bacteria” Biology of Anaerobic Microorganisms, Cl- (mg/l) 41,000 21,300 21,900-
Zehnder, A.J.B. (ed.), Wiley Interscience Pubs., New York 29,500
(1988) 516. SO42- (mg/l) <100 2750 280-1500
11. Hitzman, D.O., and Dennis, D.M.: “Sulfide Removal and
Fe2+ (mg/l) 5-40* 0 0.5-1
Prevention in Gas Wells,” paper SPE 37438 presented at the SPE
Production Operations Symposium, Oklahoma City, OK, 9-11 *Formation water Fe2+ varies between production zones.
March 1997.
12. Morris, E.A., Derr, R.M., Kenney, T.M., and Pope, D.H.: “Field
and Laboratory Tests on Nitrate Treatment for Potential Use in
Natural Gas Operations,” paper SPE 029738 presented at the Table 3. Oil Dehydrator Water Analysis.
SPE/EPA Exploration and Production Environmental Conference, Outlet Outlet
Houston, TX, 27-29 March 1995.
Inlet nitrite absent nitrite present
13. Zelver, N., Hamilton M., Pitts, B., Goeres, G., Walker, D.,
Sulfate (mg/l) 1000-1500 100-250 110-170
Sturman, P., and Heersink, J.: “Methods for Measuring
Acetate (mg/l) 20-60 75-125 40-120
Antimicrobial Effects on Biofilm Bacteria: from
Butyrate (mg/l) 110-180 15-130 10-640
Laboratory to Field”, Biofilms: Methods Enzymology
Lactate (mg/l) 40-50 30-50 30-60
Series, R.J. Doyle (Ed.), Academic Press. (1999).
14. Appelo, C.A.J., and Postma, D.: Geochemistry, Groundwater, and
Total Fe (mg/l) 0-2 0-2 0-1
Pollution, A.A. Balkema, Rotterdam (1994) 275.
15. Garcia-Gil, L.J., and Golterman, H.L.: “Kinetics of FeS-mediated
Denitrification in Sediments from the Camargue Rhone Delta,
Southern France,” FEMS Microbial Ecology (1993) 13, 85.
16. Bregman, J.I.: Corrosion Inhibitors, Macmillan Co., New York
(1963) 145.

SI Metric Conversion Factors

ft x 3.048 E-01 = m
U.S. gal x 3.785 412 E-03 = m3
Darcy x 9.869 233 E-04 = µm2
bbl x 1.589 873 E-01 = m3
hectare x 1.0 E-4 = m2
SPE 56772 CONTROL OF HYDROGEN SULFIDE IN OIL AND GAS WELLS WITH NITRITE INJECTION 7

Figures
70 2.5
60 1.E+08 Nitrite Addition
begin end
NO2 Treatment 60
1.E+07 2

Corrosion Rate (mpy)

50 (36 hours) H2S SRB
50
1.E+06

Fe (mg/l)
1.5

SRB (cells/ml)
40 40
1.E+05
H2S (ppm)

30 1.E+04 30 1
1.E+03 20
20 0.5
1.E+02 10
10
1.E+01 0 0
0 1.E+00 -48 -24 0 24 48
F M A M J J A S O N D Time (hours)
Date (Months) Corr. Rate (mpy) Fe (mg/L)

Fig. 1 – Hydrogen sulfide (gas phase) and SRB in water produced

from Well Elliot B2A before and after treatment with nitrite. Fig. 4 – Corrosion rate and dissolved iron in oil dehydrator before,
during, and after nitrite addition.

800 200
influent
700
Corrosion Rate (MPY), NO2 (mg/l)
effluent (actual) Corrosion Rate NO2
600 effluent (well mixed CSTR) 160
Nitrite (mg/l)

500
120
400

300
80
200

100
40
0
-5 0 5 10 15 20 25 30 35
Hours after start of nitrite addition 0
0 24 48 72
Time (hours after A2 restart)
Fig. 2 – Influent (actual), effluent (actual), and effluent (modeled)
nitrite in oil dehydrator during nitrite addition field trial.
Fig. 5 – Corrosion rate and nitrite in produced water from Well A2
following nitrite treatment.
100 100000
Nitrite Addition 14 200
begin end H2S SRB 18 hr. NO2 H2S (water)
80 10000 12 Treatment Fe
H2S-water (mg/l), Fe (mg/l)

160
H2S (gas)
SRB (cells/ml)

10 H2S-gas (ppm)
H2S (mg/l)

60 1000 120
8

40 100 6 80

4
20 10 40
2

0 1 0 0
0 30 60 90 120 150 180 210
-48 -24 0 24 48 72 96 120
Days
Time (hours)

Fig. 6 – Hydrogen sulfide (gas and aqueous) and iron in produced

Fig. 3 – Hydrogen sulfide (aqueous phase) and SRB in oil water before and after nitrite squeeze treatment in Well A2.
dehydrator before, during, and after nitrite addition.