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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.


Introduction
This paper was prepared for presentation at the 1999 SPE Annual Technical Conference and Hydrogen sulfide (H2S) is commonly found as a dissolved
Exhibition held in Houston, Texas, 3–6 October 1999.
constituent in produced water from oil wells and as a minor
This paper was selected for presentation by an SPE Program Committee following review of (though significant) component of natural gas. H2S is toxic,
information contained in an abstract submitted by the author(s). Contents of the paper, as
presented, have not been reviewed by the Society of Petroleum Engineers and are subject to highly corrosive, and frequently leads to the precipitation of
correction by the author(s). The material, as presented, does not necessarily reflect any
position of the Society of Petroleum Engineers, its officers, or members. Papers presented at metal sulfides in both the subsurface and in above-ground
SPE meetings are subject to publication review by Editorial Committees of the Society of
Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper
piping and fluid separation equipment. The presence of H2S in
for commercial purposes without the written consent of the Society of Petroleum Engineers is produced water or gas frequently necessitates costly removal
prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300
words; illustrations may not be copied. The abstract must contain conspicuous equipment and may reduce the sales value of the product.
acknowledgment of where and by whom the paper was presented. Write Librarian, SPE, P.O. Subsurface production of H 2S results from the activity of
Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.
sulfate reducing bacteria (SRB) which utilize short chain
volatile fatty acids (VFAs) and other organic compounds for
Abstract cellular carbon and catalyze the reduction of sulfate (SO42-) to
The downhole injection of nitrite-containing solutions into hydrogen sulfide (HS- and S2- may also occur depending on
sour oil and gas wells under controlled conditions has been solution pH). SRB presence in subsurface cores has been
observed to effectively remove hydrogen sulfide (H2S) from demonstrated under a wide variety of temperature and nutrient
aqueous and gas phases. Souring control using nitrite has conditions1.
been successfully applied to a gas well in the San Juan Basin H2S control has typically focused on the use of sulfide
of New Mexico and to an oil well in the Amoco Netherlands scavengers and/or biocides. These chemicals have been used
Rijnfield. H2S removal from topsides water separations both in topsides equipment and in downhole applications.
equipment was also facilitated using nitrite. Injected nitrite Though typically effective, these chemicals are costly in
(NO2-) scavenges H2S and prevents the activity of sulfate- application and may exhibit unintended toxicity in produced
reducing bacteria while it is present. H2S production from oil fluids. In recent years, nitrate (NO3-) has been used by several
or gas wells treated with nitrite may be suppressed for much workers as an agent to control H2S in oilfield applications.
longer periods of time. In a 36-hour downhole squeeze in a Nitrate has been added either at the injection well with the
gas well, injected NO2- removed H2S from produced gas for a waterflood2,3 or at the production well in a squeeze treatment
period of 7 months. SRB populations in produced fluids were or produced water treatment3. The mechanism of action of
reduced for a period of 3 months following treatment. In an nitrate in removing sulfides from produced waters has been
oil dehydrator, the addition of NO2- during regular operation suggested to be the selective enhancement of denitrifying
resulted in a decrease in aqueous-phase H2S from 40-60 mg/l bacteria (DNB) at the expense of SRB4,5. This mechanism
to less than 1 mg/l. Corrosion rate data indicated a less relies on the utilization of volatile fatty acids (acetate,
corrosive environment during the NO2- addition period than butyrate, formate, etc.) by faster-growing DNB such that these
prior to the addition. In a downhole squeeze in an oil necessary carbon sources are unavailable for SRB4. Fauque et
production well, injected NO2- decreased H2S in associated al.6 have shown SRB capable of utilizing a wide range organic
gas from 140 ppm to less than 1 ppm for 60 days following compounds as carbon sources, however. Jenneman, et al.2 and
treatment. H2S levels remained below pre-injection levels for Telang et al.7 have reported that the addition of nitrate into an
6 months following treatment. Oil production increased injection well did stimulate the indigenous population of
immediately following the treatment, probably due to the autotrophic nitrate-reducing bacteria (NRB), which are
dissolution of precipitated iron sulfides in the zone responsible for the reduction of nitrate to nitrite. Since these
surrounding the well bore. This treatment has proven an autotrophs do not require organic carbon for growth, their
effective means of controlling H2S in oil and gas wells as well mechanism of action does not depend on out-competing SRB
as a method of removing iron sulfide scale from the near well- for volatile fatty acids (VFAs). In these field studies2,7, sulfide
bore. reduction/removal at the production well was attributed to the
2 P.J. STURMAN, D.M. GOERES, M.A. WINTERS SPE 56772

production of an SRB inhibition agent by the abundant NRB. made on site with Drager Tubes. Temperature and pH were
This agent was speculated to be nitrite. measured in the water phase on-site, all other water chemistry
Laboratory experimental work to develop an effective, analysis was performed at the Halliburton Analytical
field-applicable de-souring technology began at the Center for Laboratory, Farmington, NM. Iron measurements were not
Biofilm Engineering at Montana State University in 1992 with taken during this field test. SRB were quantified by
support from a consortium of 5 major oil companies (ARCO, inoculation in Postgate B media, serial dilution, incubation at
Amoco, Chevron, Conoco, Exxon). Results from laboratory thermophilic temperature, and quantification via most-
column experiments using crushed sandstone cores and probable-number (MPN) technique.
microbial inocula from the North Sea and the North Slope of
Alaska, indicated that sulfide production was inhibited when Results and Discussion
either nitrate or nitrite was added to soured columns8. Nitrate After nitrite injection and a 36 hour shut-in period, Elliot B2A
addition was only effective , however, after the appearance of was brought into production at pre-soak levels (50-70 MCFD).
nitrite due to the metabolism of NRB. Further laboratory Following start-up, H2S levels (gas phase) and water
characterization of the mechanisms of SRB growth9 led to the chemistry samples were collected on a daily basis for a week,
decision to implement souring control using nitrite at 2 field and weekly thereafter. The effects of the nitrite treatment were
sites. Since nitrite was found to be the major inhibitory factor immediately evident, with no measurable H2S in produced
for SRB8, it was chosen over nitrate to eliminate the need for gas, and no culturable SRB present in produced water (Table
an active DNB population to reduce nitrate to nitrite. 1). One day after the well was brought into production, nitrite
In addition to its apparent benefits as a SRB inhibitory levels in produced water were 380 mg/l (as N), which
agent, nitrite is also an effective scavenger of hydrogen sulfide indicates that not all the injected nitrite was consumed during
according to the following proposed stoichiometry8: the 36 hour soak period. Analyses indicated that neither
ammonia nor nitrate were present in produced fluids before or
3 H2S + 3 HS- + 4 NO2- + 7 H+ • 0.75 S80 + 2 N2 + 8 H2O after nitrite treatment. Sulfate levels increased from 680 mg/l
to 927 mg/l immediately following treatment, but dropped
Nitrite was therefore chosen for production well squeeze back to 657 mg/l after 30 days of production. The VFA
treatments at a sour gas well in the San Juan Basin of New profile of produced water changed markedly following nitrite
Mexico (USA) and at a sour oil well in the Rijn Field of the treatment. Prior to nitrite injection, acetate was the dominant
Dutch North Sea. VFA at 127 mg/l. Propionate and formate were also present at
low concentrations (6 mg/l and 1 mg/l, respectively).
Gas Well Test Following nitrite treatment, acetate dropped to 48 mg/l while
The gas well test was planned and implemented in March propionate and formate increased to 480 mg/l and 89 mg/l.
1996 with the support of Amoco and Halliburton. These immediate water chemistry changes are consistent with
the suppression of SRB activity. SRB which utilize higher
Site Description molecular weight VFAs in the production of acetate
The San Juan Basin of New Mexico is part of the Mesa Verde (incomplete oxidation) typically grow faster than SRB which
formation. Lithology is sandstone with average porosity mineralize acetate10 (complete oxidation). Suppression of
10.5% and permeability 0.30 millidarcys. Average water SRB activity therefore typically results in an increase in
content is 45%. Gross gas-bearing interval thickness is 688’. propionate, formate and butyrate and a decrease in acetate, as
The average well spacing is 160 acres. The well chosen for compared to pre-suppression conditions8.
this field demonstration was Elliot B2A, which produces 50- The long term effects of the one-time nitrite soak treatment
70 MCFD (1996) at a reservoir pressure of 500 psig. H2S are shown in Fig. 1. Gas phase H2S levels remained under 5
levels in produced gas from Elliot B2A were measured at 30- ppm for 7 months following treatment. SRB levels in
50 ppm. produced water remained below detection for 3 months, then
returned to pre-treatment levels (103 cells/ml). Trace levels of
Test Procedure nitrite were measured in produced fluids for only 10 days
Prior to the nitrite addition test, water chemistry and SRB following treatment, indicating that any the long-term benefits
content were determined for produced water from Elliot B2A are not due to the continued presence of nitrite in the
(Table 1). Immediately prior to the test, the well was shut in subsurface. This long-term beneficial effect was initially
and a solution of 1400 lb. sodium nitrite was mixed with 1000 considered to be due to the suppression of SRB by ephemeral
gallons de-aerated water. Over a 5 hour period, this contact with nitrite. Other workers have noted similar
concentrated NaNO2 solution was injected with 800 bbl. of phenomena with injected nitrate, and have attributed it to
water for a final concentration of 1000 mg/l NO2- (as DNB or NRB out-competing SRB for available electron
Nitrogen). The fluid was held in place under surface pressure donors5,11 or to the production of nitrite by indigenous NRB
for 36 hours, then the well was swabbed for production and the subsequent suppression of SRB activity by nitrite2.
purposes. Gas production from Elliot B2A was initiated Competition of DNB/NRB with SRB for electron donors is
thereafter, with measurement of H2S (gas phase) and water clearly not the causative mechanism here, since nitrite was
constituents for 7 months. Gas phase H2S measurements were 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 3

is well understood that nitrite inhibits SRB while it is present, Oil Facility Tests
but the mechanism of lasting effect has not been elucidated. The oil facility test was performed with the assistance of
Conversely, Morris et al.12 found no long term benefit to the Amoco-Netherlands and Baker-Petrolite. The test was
addition of a commercial nitrate application in the treatment of performed at the Rijn Field production facility located
sour cores in laboratory studies. They concluded that nitrate approximately 20 miles off the coast of Den Hague,
must be continually present to maintain sulfide suppression. Netherlands. The oil facility test was implemented in two
Subsequent experimentation which involved the application of parts. In the first step, a nitrite solution was injected into an
100 mg/l nitrite (as N) to sour SRB biofilm reactors here at the oil dehydrator over a period of 20 hours to determine any
CBE has reinforced the conclusions of Morris et al.11. In these lasting effects on sulfide production in this vessel. In the
experiments, sulfide levels rapidly returned to pre-test levels second step, a nitrite solution was injected into an oil
when nitrite was washed out of the continuous flow biofilm production well (Well A2) and held in place for approximately
reactors13. 2 days prior to production of the well.
Reconciliation of this apparently contradictory data may be
possible if one considers the inorganic reactions which likely Site Description
take place after the addition of nitrate or nitrite to an actively The Rijn Field production facility operates 17 seawater
souring environment in the subsurface. Injection of high injection wells and 13 production wells and has been operated
concentrations of dissolved nitrite or nitrate radically alters the under waterflood conditions for over 10 years. Average well
oxidation-reduction (redox) conditions of the subsurface. It is depth is 6500’ and the oil bearing interval consists of 4 zones
well recognized that oxidized nitrogen compounds readily which vary in permeability from 0.5 md in Zone D to 120 md
react with dissolved hydrogen sulfide. Less often quantified in the uppermost Zone A. Watercut averages 95% and the
are the redox reactions of nitrate and nitrite with other metal bulk of the remaining oil resides in the lower permeability
sulfides, principally iron sulfide. Nitrate reacts with pyrite zones. Reservoir temperature is 68oC at a pressure of 2000
(FeS2) according to the following stoichiometry14: psi.
The production system utilizes gaslift to assist the flow of
5FeS2 + 14NO3- + 4H+ • 7N2 + 5Fe2+ + 10SO42- + 2H2O fluids from the subsurface. Produced gas is separated at a
production separator and is then compressed and reinjected.
and Produced fluids contain SRB, sulfate and a variable mixture of
VFAs. Water chemistry data for baseline formation water
10 Fe2+ + 2 NO3- + 14 H2O • 10 FeOOH + N2 + 18 H+ (prior to seawater flood), injection water, and produced water
are shown in Table 2.
less stable iron sulfide phases (FeS) and nitrite could be Since 1990, mean H2S levels in produced gas have steadily
expected to react by similar stoichiometry. increased from 40 to over 200 ppm (1997), necessitating
An increase in dissolved iron at a production well treated periodic, unplanned system shut-downs to remove
with nitrate was noted by Giangiacomo et al.3 and was accumulated solids and biofilm in topsides water separation
attributed to the activity of DNB. The presence of FeS has equipment. H2S concentrations in the gas blanket of water
been found to facilitate rates of denitrification (and subsequent separation process units have risen as high as 600 ppm. Initial
Fe liberation) in river sediments15, however denitrification was microbiological testing and a system engineering analysis
found to be totally inhibited by Fe2+ concentrations of 0.1 mM (May-June 1997) indicated that biogenic H2S production was
(5.6 mg/l). occurring both in topsides water separation equipment
Whether abiotic or biotic, the dissolution of iron sulfide (principally the oil dehydrator and flotation units), as well as
has the effect of removing a significant solid phase from the in the subsurface. Results from these initial tests were used to
subsurface, which may increase permeability and fluid determine H2S problem areas within the facility and to design
recovery. Increased oil recovery was noted by Giangiacomo dosing protocols for effective H2S scavenging and SRB
et al.3 along with elevated iron following nitrite treatment, inhibition using nitrite.
suggesting that iron sulfides which had previously blocked Nitrite treatment of the oil dehydrator was performed in
pore spaces may have been removed. This suggests a December 1997. The dehydrator has a gross volume of 10 m3,
conceptual model which explains the lasting sulfide inhibition evenly divided between water and oil phases. The gas
effects of nitrate or nitrite. After the nitrite or nitrite has headspace in the dehydrator is minimal and could not be
reacted or washed out of the subsurface, SRB activity may accessed for sampling. H2S levels in the oil dehydrator were
immediately resume, but produced sulfides readily react with typically 40-60 mg/l, the highest water phase levels measured
formation iron (or other metals) and precipitate as metal in the topsides equipment. During periodic system
sulfides. The effect of the nitrite or nitrate addition is maintenance, it has been noted that a significant sludge layer
therefore analogous to backwashing a filter. accumulates in the bottom of the oil dehydrator. This layer
Unfortunately dissolved iron was not measured in the field was not accessible for sampling prior to testing, but was
test at Elliot B2A, however the results from the field test at the expected to harbor high populations of SRB. Sulfate and VFA
oil production well in the Rijn Field also support this model. data indicate high SRB activity in the oil dehydrator (Table 3)
4 P.J. STURMAN, D.M. GOERES, M.A. WINTERS SPE 56772

Temperature and pH were stable at 40oC and 7.3, respectively sulfate, VFAs, and iron were collected at the test separator and
and pressure was atmospheric. sent to SGS Redwood Laboratories for analysis.
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% Results and Discussion
watercut). Oil production was approximately 200 BOPD. Oil Dehydrator Test. Nitrite addition to the oil dehydrator
Iron in produced water from A2 was 0.5-1 mg/l. influent proceeded in the step fashion indicated in Fig. 2 (solid
line). The nitrite concentration measured in the oil dehydrator
Test Procedure effluent peaked at 705 mg/l NO2--N 2 hours after addition
Highly concentrated aqueous solutions of sodium nitrite were began. At t=33 hours, 4 mg/l nitrite was measured in the
prepared by Baker-Petrolite on-shore under minimal aeration effluent.. Nitrite was completely washed out of the oil
conditions and shipped to the platform no more than 5 days dehydrator 45-50 hours following the start of treatment (Fig.
prior to use. 2, solid diamonds). If the oil dehydrator behaved as a well
Oil Dehydrator Test. The oil dehydrator influent makeup mixed continuous stirred tank reactor (CSTR), the nitrite
is approximately 75% oil, 25% water and is the direct effluent washout curve should have been well below the actual
of the production separator. Water residence time in the measured nitrite concentrations (Fig. 2, dashed line). This
dehydrator is approximately 1.5 hours. The concentrated suggests that the dehydrator was either not well mixed, or that
nitrite solution was added directly to the oil dehydrator nitrite may diffuse into the bottom sludge layer when present
influent stream via positive displacement pump. Nitrite was at high concentrations, then diffuse out again when the
added for a total of 20 hours. The method of nitrite addition concentration is reduced.
was to start with a high concentration and reduce this in a step Prior to nitrite treatment, aqueous phase H2S levels in the
fashion over the 20 hour period. The target NO2- (nitrogen) dehydrator were typically in the 40-60 mg/l range (several
concentrations in the oil dehydrator influent were: 650 mg/l measurements of ~8 mg/l prior to nitrite addition were
(0-2.75 hr.), 140 mg/l (2.75-11 hr.), 50 mg/l (11-20 hr.). anomalously low according to historic data, Fig. 3).
On-site monitoring of oil dehydrator effluent was begun Following nitrite addition, H2S dropped to <0.5 mg/l for
immediately following the addition of nitrite. Liquid phase approximately 40 hours, then increased to 5-6 mg/l for the
H2S was measured via Hach Model HS-C kit (effervescence next several days. This is approximately tenfold less than the
method). Samples containing >10 mg/l H2S were diluted into normal pre-test H2S level. During the test, culturable SRB in
the measurable range 0.2-10 mg/l. H2S in gas was measured the dehydrator effluent dropped from 103-104 cells /ml to 10
using Drager tubes after collection in a bladder. Aqueous cells/ml. Unfortunately, SRB data were not available after
nitrite was measured via Hach kit (diazotization method) using t=30 hours. The corrosion rate in the dehydrator varied from
a Hach color spectrophotometer to measure absorbance 0.5-50 mills per year (mpy) prior to the addition of nitrite and
relative to a standard curve. Total iron was measure via Hach stabilized at 2-3 mpy when nitrite was present and following
kit (Phenathroline method), pH was measured via probe and nitrite washout (Fig. 4). Concurrently, the total iron
corrosion rate was monitored using a continuous flow-through concentration in dehydrator effluent remained between 0.5-2
LPR probe. mg/l before and after nitrite addition.
Samples were also collected for analysis at SGS Redwood These data confirm the H2S scavenging and SRB
Laboratories (Spijkenisse, Netherlands) for VFAs, sulfate, inhibition effects of nitrite/nitrate observed by other workers2-5
iron, nitrate, nitrite, and chloride. SRB samples were analyzed and the authors in prior field and laboratory tests. Although
via MPN (using Postgate B media) and Angus methods. the inhibition and scavenging effects of the added nitrite
Oil Well Squeeze Test. Concentrated nitrite solution was evidently continued beyond the point of nitrite washout, it is
shipped to the platform in 200 L drums. Production well A2 interesting to note that nitrite did not result in the mobilization
was shut down and deaerated seawater was pumped into the of iron. This may be because there is little FeS present in the
well. The concentrated nitrite solution was added at the well oil dehydrator bottom sludge, or because other chemical
head using a positive displacement pump. The average species present (H2S and organics) are more easily oxidized by
concentration of NO2- ( as nitrogen) in the injected water was nitrite. Therefore, the lasting effects of nitrite cannot be
615 mg/l . A total of 2020 bbl water was injected over a 36 attributed to the oxidation and dissolution of iron sulfide, as
hour period and the solution was held in place for another 18 was the case in the downhole treatment. It is probable that the
hours prior to restarting the well. Production from the well added nitrite oxidized at least the surface layer of the reduced
was routed to the test separator following the squeeze organics present in the bottom sludge of the dehydrator, and
treatment. For the first 2 weeks following the nitrite injection, this may have had a lasting effect on SRB which reside there.
well A2 was allowed to produce without gaslift, allowing The apparent suppression of corrosion in the dehydrator after
accurate determination of H2S levels in produced gas. nitrite treatment is probably the result of the removal of H2S
Following this period, gaslift was restarted to increase the from the water. At very high concentrations, nitrite may
fluids production rate. Nitrite, H2S (gas and aqueous), pH, completely passivate a metal surface. At lower concentrations
and Fe were determined at the test separator via the field nitrite has the potential to enhance localized corrosion via
methods described above. Laboratory samples for nitrite, incomplete anodic passivation, thereby driving the corrosion
SPE 56772 CONTROL OF HYDROGEN SULFIDE IN OIL AND GAS WELLS WITH NITRITE INJECTION 5

in localized, non-passivated zones16. This was a concern in producing H2S. Sulfate data collected during the test indicates
adding nitrite to the dehydrator. The highest concentration only a short term suppression of SRB was likely (~3 days), if
used (~700 mg/l as N) was either not sufficiently high to at all.
initiate pitting corrosion, or was not present long enough to
initiate high corrosion rates. Conclusions
Oil Well Squeeze Test. After the 54 hour injection + hold Aqueous nitrite solutions were injected for H2S control into a
period, well A2 was restarted with production routed to the sour gas well, a sour oil well, and an oil dehydrator. The
test separator for analysis. Nitrite was measured in A2 results from these field trials indicate that nitrite has an
production for approximately 40 hours following restart (Fig. immediate and significant reduction effect on aqueous- and
5). In this case, the corrosion rate as measured by LPR probe gas-phase H2S when so used. Furthermore, H2S reduction in
did not respond as it did in the oil dehydrator test. The these systems lasted from days to months beyond the removal
corrosion rate dropped as the nitrite concentration in produced of nitrite. Though nitrate has received much more attention
water decreased. Unfortunately, pre-nitrite test corrosion data than nitrite in laboratory and field studies to control souring,
are not available at well A2, it is apparent, however, that over the mechanism of action of each is thought to be similar. Both
the long term, the corrosion rate did not increase as a result of are reactive in the subsurface with H2S and iron sulfides, and
nitrite injection. The effects of nitrite injection on gas and both have been observed to inhibit the activity of SRB when
aqueous-phase H2S and dissolved iron are shown in Fig. 6. present. Whether nitrate or nitrite is a lasting inhibitor to
Prior to nitrite injection, H2S was present at 120-160 ppm in SRB, and the mechanism of such inhibition has not yet been
produced gas and 6 mg/l in produced water, and the total iron fully elucidated. Past workers3-5 have suggested that this
was 0.5 mg/l. Following nitrite treatment, H2S levels mechanism is the enhancement of DNB through the addition
decreased to below detection limits in both water and gas. of nitrate, which subsequently out-compete SRB for electron
Concurrently, total iron in produced water increased 20-fold to donors (VFA). This may occur when nitrate/nitrite is present,
10 mg/l. H2S in produced water increased to 1 mg/l after 10 but does not explain the removal of H2S for days to months
days of production at A2 and 2 mg/l after 50 days, where it after the reaction/consumption of these compounds. A more
remained for the following 4 months. H2S in gas increased likely mechanism is the oxidation of various reduced
more slowly at first, but eventually returned to pre-test levels compound in the subsurface, principally FeS in this instance,
(90 ppm) 6 months after treatment. Iron remained in the 4-10 which creates a sink for their subsequent precipitation from
mg/l range for approximately 30 days, then dropped to 2.5 solution. An additional benefit to FeS dissolution may be the
mg/l for the duration of measurement (6 months). Sulfate and increased oil recovery from previously occluded pores. Nitrite
FVA data collected prior to and following the nitrite addition treatment is an economically attractive alternative for the de-
indicated a slight increase in sulfate (from 2000-2500 mg/l) souring of oil and gas wells which are marginal producers due
following the addition of nitrite, but the rapid return to pre-test to high H2S.
levels within 3 days. No VFAs were detected above the
quatitation limit (5 mg/l) either before or after the nitrite Acknowledgments
addition. We thank Stan Kolodzie of BP-Amoco and Ruud Van Dijk of
It is apparent that nitrite injection had a significant and Amoco-Netherlands for their assistance during and after the
lasting effect on H2S in produced fluids from this well. In field tests; Henry Nichols of BP-Amoco for his assistance in
addition, oil production from A2 increased from 200-400 corrosion data interpretation; and John Sears of the
BOPD for approximately 30 days immediately following Department of Chemical Engineering, Montana State
nitrite injection. This is thought to be correlated with the University for his technological insights.
increased iron production from A2. Injected nitrite caused the
dissolution of iron sulfide in the formation, which opened References
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formerly precipitated as FeS, when SRB were actively
6 P.J. STURMAN, D.M. GOERES, M.A. WINTERS SPE 56772

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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.