WO1996012867A1 - Inhibition of sulfate-reducing bacteria via nitrite production - Google Patents
Inhibition of sulfate-reducing bacteria via nitrite production Download PDFInfo
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- WO1996012867A1 WO1996012867A1 PCT/US1995/013298 US9513298W WO9612867A1 WO 1996012867 A1 WO1996012867 A1 WO 1996012867A1 US 9513298 W US9513298 W US 9513298W WO 9612867 A1 WO9612867 A1 WO 9612867A1
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- sulfate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
Definitions
- the present invention is directed to the field of prevention of reservoir fouling, particularly oil and gas reservoir fouling and souring.
- VFA volatile fatty acids
- Nitrate introduction has been used to prevent sulfide formation in waters at ambient temperatures through microbial competition with Thiobacillius denitrifisans (introduced or, if present, in-situ) .
- Thiobacillius denitrifisans introduced or, if present, in-situ
- these specific denitrifying bacteria are used, these specific denitrifying bacteria.
- DNB utilize the VFA' s and the carbon dioxide from dissolved limestone in the reservoir to produce nitrogen and/or ammonia.
- the DNB's would out-compete and more rapidly utilize the VFA's, resulting in lessened sulfide production.
- Bedell is directed to a process for drilling geothermal wells with removal of H 2 S.
- This patent recognizes the problems of H 2 S fouling and souring of oil and gas reservoirs.
- the patent indicates that in the past the problem of H 2 S was treated with metal chelates or iron chelates, or by treatment with hydrogen peroxide.
- Bedell proposes treatment of reservoirs with a ferric chelate prepared using aminocarboxylic acid chelating agents.
- United States Patent No. 4,681,687 to Mouche et al is directed to the use of alkali metal nitrites to inhibit H 2 S formation in flue gas desulfurization system sludges.
- This patent discloses that the use of sodium nitrate has been used for several years to control sulfide odors.
- the patent indicates that in order to control sulfate reducers in sewage wastes, large amounts of nitrate are required.
- the patent solves this problem of controlling sulfate-reducing bacteria and odors produced thereby in flue gas desulfurization scrubber sludges by treating the sludges with biocidal and odor controlling dosages of an alkali metal nitrite, such as sodium nitrite.
- a decrease in nitrate content of water is achieved by treating the water with denitrifying microorganisms in a substrate .
- United States Patent No.4, 879,240 to Sublette is directed to microbial control of hydrogen sulfide production in organic-laden waters by sulfate-reducing bacteria. This patent also recognizes the problem of H 2 S overproduction in oil field and oil well operation. The problem is addressed by Sublette by treatment of wells with Thiobacillius denitrificans to out-compete SRB's.
- United States Patent No.4,880,542 to Sublette is directed to a biofilter for the treatment of sour water.
- This patent also recognizes the problem of H 2 S overproduction in oil field and oil well operation.
- the problem is addressed by Sublette by treatment of wells with Thiobacillus denitrificans in a nutrient medium.
- the nutrient medium includes nitrite as an electron acceptor, i.e., reducing agent .
- United States Patent No. 5,074,991 to Weers is directed to suppression of the evolution of hydrogen sulfide gas by treatment of water or a hydrocarbon containing dissolved hydrogen sulfide with a diamino molecule.
- Biocides have been utilized to try to prevent microbial action, but they have been unsuccessful in preventing sulfide formation in oil reservoir applications. Nitrites are beneficial in reducing sulfate fouling; however, they often lead to human toxicity chemicals by reacting with amino acids to produce harmful nitrosoamine. Thus it is desirable to limit their use to the lowest possible concentrations. Another alternative method is needed.
- the present invention overcomes the above problems by providing a method of treating oil and gas reservoir sulfide souring or fouling by administering a concentration of 5-50 ppm of nitrate or nitrite.
- the present method solves the problems of the prior art, and limits the level of produced nitrite used to minimal concentrations .
- the present invention reduces reservoir fouling, particularly oil and gas reservoir fouling, by adding nitrate at low concentrations to limit sulfate reduction.
- concentrations of nitrate as low as 5-50 ppm, and preferably 5-10 ppm are shown to inhibit sulfate-reducing bacteria from producing H 2 S using VFA substrates with sulfate ions as nitrate is biologically converted to a stoichimeterically equivalent amount of nitrite, the inhibiting agent, by denitrifying bacteria in an oil reservoir.
- the present invention reduces reservoir fouling, particularly oil and gas reservoir fouling, by adding nitrite at low concentrations to limit sulfate reduction.
- concentrations of nitrite as low as 5-50 ppm, and preferably 5-10 ppm, are shown to inhibit sulfate-reducing bacteria from producing H 2 S using VFA substrates with sulfate ions.
- oil/gas reservoir souring (the production of H 2 S) has been shown to be driven by microbial action in secondary water using carbon sources such as fatty acids present in produced and injected water or from oil-water partitioning, this souring can be widespread throughout a reservoir. Nitrite inhibition of SRB's reduces H 2 S and thus souring, corrosion, and sulfide toxicity problems and also reduces biomass production and plugging problems as total microbial action is reduced.
- the invention is comprised of a method for controlling the growth of sulfate reducing bacteria and odors/problems produced thereby by the introduction of nitrate/nitrite at 5-50 ppm into oil recovery operations.
- sulfide production by sulfate-reducing bacteria is inhibited with 5-10 ppm of nitrate/nitrite.
- Nitrate may be present in the form of a salt, selected from a group such as sodium or potassium nitrate .
- the SRB's (mixed population) act by the following reaction (s) at 30-100 * C and sulfate concentrations up to 1000 ppm, to obtain sulfide concentrations of -200 ppm at steady state:
- Nitrite at 5-50 ppm is shown to inhibit the sulfide-formation reaction in SRB's. It can be introduced by essentially stoichiometric reduction of nitrate to nitrite biologically by naturally occurring thermophilic bacteria in the ecosystem.
- the DNB reaction of nitrate to nitrogen gas occurs in steps, first to nitrite, (N0 " 2 ) before proceeding to ammonia or nitrogen.
- the biological reaction preferentially stops at the higher temperatures in a reservoir at pH over neutral at nitrite to act then as an inhibitor of sulfide production by SRB's.
- Higher temperature have been found to reduce subsequent reduction of nitrite to nitrogen or ammonia in consortia found in waters from oil reservoir, while mesophilic DNB's have been found generally to continue reduction to NH 3 or N 2 .
- nitrite remains to act as an inhibitor to SRB's. This is important as reservoirs generally are at temperatures from 60 'C to well over 100° C .
- the in si tu bacteria in a high temperature reservoir do not then reduce nitrate to NH 3 /N 2 , and the inhibitory action of nitrite can act on the hydrogen sulfide.
- Nitrite inhibits H 2 S formation by SRB activity at 5-50 ppm.
- the nitrite can be introduced at the needed active sites in-situ by microbial conversion of nitrate to nitrite. This conversion is important in some applications to restrict the chemical reaction of sulfides with nitrite, which will reduce the nitrite concentration to inactive levels.
- Example 2 Introduction of nitrite at 1-2 ppm to established sulfide-producing chemostats and columns with a North Sea consortium was shown to not stop the sulfide reaction, as sulfide reacts with nitrite in a chemical reaction before inhibition occurs.
- introduction of nitrite at 10-50 ppm results in inhibition of the microbial sulfide formation, and can be continued using only 5-10 ppm nitrite (see Table 4 for results) . (This is in contrast to the at-least 50 ppm required by prior art methods.)
- Previous sulfide precipitate in the sandstone columns reacts with the nitrite and can lower the nitrite concentration below 5 ppm through chemical reaction.
- NOMENCLATURE k of sulfate reduction rate per biofilm volume [M IT 3 t “1 ] K E : half saturation constant for sulfate [M IT 3 ] K s : half saturation constant for substrate [M L "3 ] a ⁇ : cellular maximum growth rate [f 1 ] maximum sulfate reduction rate [M L “3 t "1 ] Y x s : cellular growth yield on substrate [M M "1 ] Y x/E : cellular growth yield on sulfate [M M "1 ]
- a J.B. Zehnder (ed.) Biology of Anaerobic Microorganisms. John Wiley & Sons, Widdel, F. and N. Pfennig. 1981a Studies on dissimilatory sulfate reducing bacteria that decompose fatty acids.
- I Isolation of new sulfate reducing basteria enriched with acetate from saline environments. Description of Desulfobacter postgatei gen. nov., sp. nov.
Abstract
A method for the reduction of sulfide souring caused by sulfate-reducing bacteria in oil, gas reservoirs and wastewater reservoirs by administering 5-50 ppm of nitrate or nitrite to the reservoir.
Description
INHIBITION OF SULFATE-REDUCING BACTERIA VIA NITRITE PRODUCTION
Technical Field
The present invention is directed to the field of prevention of reservoir fouling, particularly oil and gas reservoir fouling and souring.
Background of the Invention
The introduction of sulfate-containing waters into oil fields for secondary oil recovery often leads to sulfide formation by in-situ sulfate-reducing bacteria
(SRB) . The sulfide (H2S) leads to safety, environmental, corrosion and plugging problems, and even premature abandonment of the oil and gas field.
The sulfide formation is initiated with the introduction of the sulfate and the subsequent mixing with inherent volatile fatty acids (VFA) from the reservoir, which serve as the carbon source for indigenous microorganisms to produce the hydrogen sulfide in an anaerobic environment .
Nitrate introduction has been used to prevent sulfide formation in waters at ambient temperatures through microbial competition with Thiobacillius denitrifisans (introduced or, if present, in-situ) . When nitrate is used, these specific denitrifying bacteria
(DNB) utilize the VFA' s and the carbon dioxide from dissolved limestone in the reservoir to produce nitrogen and/or ammonia. The DNB's would out-compete and more rapidly utilize the VFA's, resulting in lessened sulfide production.
Other industrial operations, including wastewater treatment systems, also encounter sulfide formation problems in anaerobic environments with sulfate ions present. Bioside introduction in this situation has met with mixed success.
Methods to avoid oil and gas fouling and wastewater fouling are known. United States Patent No. 4,415,461 to Mansell et al. , discloses a process for treating residual waters containing aromatic amines. The background section of this patent refers to German Patent DE-B-1301279 as disclosing a process for purifying residual waters containing primary aliphatic amines by adding an alkali metal nitrite to the neutral or alkaline residual waters. United States Patent No. 4,696,802 to Bedell is directed to a process for drilling geothermal wells with removal of H2S. This patent recognizes the problems of H2S fouling and souring of oil and gas reservoirs. The patent indicates that in the past the problem of H2S was treated with metal chelates or iron chelates, or by treatment with hydrogen peroxide. Bedell proposes treatment of reservoirs with a ferric chelate prepared using aminocarboxylic acid chelating agents.
United States Patent No. 4,681,687 to Mouche et al is directed to the use of alkali metal nitrites to inhibit H2S formation in flue gas desulfurization system sludges. This patent discloses that the use of sodium nitrate has been used for several years to control sulfide odors. The patent indicates that in order to control sulfate reducers in sewage wastes, large amounts of nitrate are required. The patent solves this problem of controlling sulfate-reducing bacteria and odors produced thereby in flue gas desulfurization scrubber sludges by treating the sludges with biocidal and odor controlling dosages of an alkali metal nitrite, such as sodium nitrite. The addition of sodium nitrite in an amount of at least 50 ppm to the sludge controls the growth of sulfate-producing bacteria and prevents the biogenic production of H2S. This patent using alkali metal nitrites has been used to inhibit SRB formation in desulfurization system sludges. These nitrite concentrations required are indicated to 100-500 ppm, but
may be up to 1000 ppm if the SRB count is very high; the limit on the lower side is stated to be at least 50 ppm. Twenty-five ppm were shown not to restrict SRB activity in the sludge system. United States Patent No. 4,683,064 to Hallberg et al . is directed to a process for decreasing the nitrate content of water. A decrease in nitrate content of water is achieved by treating the water with denitrifying microorganisms in a substrate . United States Patent No.4, 879,240 to Sublette, is directed to microbial control of hydrogen sulfide production in organic-laden waters by sulfate-reducing bacteria. This patent also recognizes the problem of H2S overproduction in oil field and oil well operation. The problem is addressed by Sublette by treatment of wells with Thiobacillius denitrificans to out-compete SRB's.
United States Patent No.4,880,542 to Sublette is directed to a biofilter for the treatment of sour water. This patent also recognizes the problem of H2S overproduction in oil field and oil well operation. The problem is addressed by Sublette by treatment of wells with Thiobacillus denitrificans in a nutrient medium. The nutrient medium includes nitrite as an electron acceptor, i.e., reducing agent . United States Patent No. 5,074,991 to Weers is directed to suppression of the evolution of hydrogen sulfide gas by treatment of water or a hydrocarbon containing dissolved hydrogen sulfide with a diamino molecule. Biocides have been utilized to try to prevent microbial action, but they have been unsuccessful in preventing sulfide formation in oil reservoir applications. Nitrites are beneficial in reducing sulfate fouling; however, they often lead to human toxicity chemicals by reacting with amino acids to produce harmful nitrosoamine. Thus it is desirable to limit their use to
the lowest possible concentrations. Another alternative method is needed.
The present invention overcomes the above problems by providing a method of treating oil and gas reservoir sulfide souring or fouling by administering a concentration of 5-50 ppm of nitrate or nitrite. The present method solves the problems of the prior art, and limits the level of produced nitrite used to minimal concentrations .
Disclosure of the Invention
I. The present invention reduces reservoir fouling, particularly oil and gas reservoir fouling, by adding nitrate at low concentrations to limit sulfate reduction. According to the method, concentrations of nitrate as low as 5-50 ppm, and preferably 5-10 ppm, are shown to inhibit sulfate-reducing bacteria from producing H2S using VFA substrates with sulfate ions as nitrate is biologically converted to a stoichimeterically equivalent amount of nitrite, the inhibiting agent, by denitrifying bacteria in an oil reservoir.
II. The present invention reduces reservoir fouling, particularly oil and gas reservoir fouling, by adding nitrite at low concentrations to limit sulfate reduction. According to the method, concentrations of nitrite as low as 5-50 ppm, and preferably 5-10 ppm, are shown to inhibit sulfate-reducing bacteria from producing H2S using VFA substrates with sulfate ions.
Since oil/gas reservoir souring (the production of H2S) has been shown to be driven by microbial action in secondary water using carbon sources such as fatty acids present in produced and injected water or from oil-water partitioning, this souring can be widespread throughout a reservoir.
Nitrite inhibition of SRB's reduces H2S and thus souring, corrosion, and sulfide toxicity problems and also reduces biomass production and plugging problems as total microbial action is reduced.
Description of the Invention
The invention is comprised of a method for controlling the growth of sulfate reducing bacteria and odors/problems produced thereby by the introduction of nitrate/nitrite at 5-50 ppm into oil recovery operations. In a most preferred embodiment, sulfide production by sulfate-reducing bacteria is inhibited with 5-10 ppm of nitrate/nitrite. Nitrate may be present in the form of a salt, selected from a group such as sodium or potassium nitrate . The SRB's (mixed population) act by the following reaction (s) at 30-100 *C and sulfate concentrations up to 1000 ppm, to obtain sulfide concentrations of -200 ppm at steady state:
S04 + VFA + H2S + C02 + Cells
The activity and stoichiometry has been determined for several populations of bacteria consortia from oil reservoirs in Alaska and the North Sea for formate, acetate, propionate, n-butyrate and i-butyrate (Table 1) . These activities and stoichiometries have been obtained in batch reactors, chemostats and are shown to be applicable in sandstone columns.
Nitrite at 5-50 ppm is shown to inhibit the sulfide-formation reaction in SRB's. It can be introduced by essentially stoichiometric reduction of nitrate to nitrite biologically by naturally occurring thermophilic bacteria in the ecosystem.
The DNB reaction of nitrate to nitrogen gas occurs in steps, first to nitrite, (N0" 2) before proceeding to
ammonia or nitrogen. The biological reaction preferentially stops at the higher temperatures in a reservoir at pH over neutral at nitrite to act then as an inhibitor of sulfide production by SRB's. Higher temperature have been found to reduce subsequent reduction of nitrite to nitrogen or ammonia in consortia found in waters from oil reservoir, while mesophilic DNB's have been found generally to continue reduction to NH3 or N2. Thus (Table 2) nitrite remains to act as an inhibitor to SRB's. This is important as reservoirs generally are at temperatures from 60 'C to well over 100° C . The in si tu bacteria in a high temperature reservoir do not then reduce nitrate to NH3/N2, and the inhibitory action of nitrite can act on the hydrogen sulfide.
Example 1
Introduction of nitrate at 1-2 ppm to established sulfide-producing chemostats systems and columns with an Alaska or North Sea consortium was shown to not stop the sulfide production, as sulfide already present reacts with the produced nitrite in a chemical reaction before inhibition occurs.
However, introduction of nitrate at 10-50 ppm results in inhibition of the microbial sulfide formation, and can be continued using only 5-10 ppm nitrate.
Previous sulfide precipitate reacts in the sandstone columns with the produced nitrite and can lower the nitrite concentration below five ppm through chemical reaction. These scenarios have been demonstrated in chemostats from 30-70*C, and in sandstone columns at 60*C with bacterial consortia from both Alaska and the North Sea oil reservoirs. The free H2S is lowered to zero, and the nitrite concentration can rise to near stoichiometric proportions of the introduced nitrate. This reaction is
limited by nitrate availability, and so all the VFA's are not utilized. Work on bacteria has shown that the enzyme for nitrite to ammonia/nitrogen is restricted at higher temperatures and may not be present or H2S inhibits this enzymatic reaction. Thus the nitrate is not completely reduced because of microbiological limitations, and the produced nitrite acts as an inhibitory agent to the SRB.
For nitrate conversion,denitrifying bacterial activity needs to be started and cell levels raised to sufficient populations to obtain high nitrite concentrations. This has taken as long as three weeks before concentrations are sufficient to inhibit SRB activity. Table 3 shows SRB activity in a column with and without nitrate addition. Inhibition, and not death, of the SRB's has been shown, as removal of the nitrate and subsequent nitrite results again in sulfide production in the column to previously established levels with both SRB consortia. Introduction of nitrate can again stop sulfide formation. Thus, both SRB and DNB activity are possible under the correct nutrient and electrochemical conditions.
Nitrite inhibits H2S formation by SRB activity at 5-50 ppm. The nitrite can be introduced at the needed active sites in-situ by microbial conversion of nitrate to nitrite. This conversion is important in some applications to restrict the chemical reaction of sulfides with nitrite, which will reduce the nitrite concentration to inactive levels.
Example 2 Introduction of nitrite at 1-2 ppm to established sulfide-producing chemostats and columns with a North Sea consortium was shown to not stop the sulfide reaction, as sulfide reacts with nitrite in a chemical reaction before inhibition occurs.
However, introduction of nitrite at 10-50 ppm results in inhibition of the microbial sulfide formation, and can be continued using only 5-10 ppm nitrite (see Table 4 for results) . (This is in contrast to the at-least 50 ppm required by prior art methods.) Previous sulfide precipitate in the sandstone columns reacts with the nitrite and can lower the nitrite concentration below 5 ppm through chemical reaction.
Inhibition, and not death, of the SRB's has been shown, as removal of the nitrite results again in sulfide production in the column to previously established levels with both SRB consortia. Introduction of nitrite can again stop sulfide formation. Thus, both SRB and DNB activity are possible under the correct nutrient and electrochemical conditions.
The purpose of the above description and examples is to illustrate some embodiments of the present invention without implying any limitation. It will be apparent to those skilled in the art that various modifications and variations may be made to the composition and method of the present invention without departing from the spirit or scope of the invention. All publications cited herein are incorporated by reference in their entireties.
Table la. KINETIC PARAMETERS FOR SUSPENDED MESOPHILIC-SRB FOR VFA UTILIZATION IN PURE CULTURE AND MIXED POPULATIONS.
Table lb. KINETIC PARAMETERS FOR SUSPENDED AND BIOFILM THERMOPHILIC-SRB FOR VFA UTILIZATION BY OIL FILED CONSORTIA (RESULTS FROM RESEARCH CONDUCTED BY THE SOURING GROUP AT MSU)
Species T Substrate V M-UX Yχ/B Yχ/s Kβ 1 <°C) (mmol g"'h"1) (h1) (g dry BM g-S1) (g dry BM g1) (g m-') (g-S m') |
Alaska consortium 60 butyrate 181 0.029 0.005 0.008 9.0 5.5 suspended culture
60 propionate 99 0.019 0.006 0.002
50 formate 31 0.010 0.010 0.005
North Sea 60 butyrate 104 0.017 0.006 0.003 2.0 5.0 consortium suspended culture
60 formate 63 0.013 0.010 0.003 2.0 4.0
Alaska consortium 60 VFA 177 0.041 0.007 0.003
10 biofilm culture mixture
NOMENCLATURE kof: sulfate reduction rate per biofilm volume [M IT3 t"1] KE: half saturation constant for sulfate [M IT3] Ks: half saturation constant for substrate [M L"3] aχ: cellular maximum growth rate [f1] maximum sulfate reduction rate [M L"3 t"1] Yx s: cellular growth yield on substrate [M M"1] Yx/E: cellular growth yield on sulfate [M M"1]
Ingvorsen, K. and B.B. Jorgenson. 1984. Kinetics of sulfate uptake of freshwater and marine species of
Desulfovibrio. Arch.Microbial. 139:61-66.
Ingvorsen, K., A.J.B. Zehnder, and B.B. Jorgenson. 1984. Kinetics of sulfate and acetate uptake by Desulfobacter postgatei. Appl.Environ.Microbiol. 47:403-408.
Middleton, A.C. end A.W. Lawrence. 1977. Kinetics of microbial sulfate reduction. JWPCF 49:1659-1670.
Schauder, R., B. Eik anns, R.K. Thauer, F. Widdel, and G. Fuchs. 1986. Acetate oxidation to C02 in anaerobic bacteria via a novel pathway not involving reactions of the citric acid cycle. Arch.Microbial. 145:162-172
Widdel, F. 1988. Microbiology and ecology of sulfate- and sulfur-reducing bacteria, p.469-587. In A J.B. Zehnder (ed.) , Biology of Anaerobic Microorganisms. John Wiley & Sons,
Widdel, F. and N. Pfennig. 1981a Studies on dissimilatory sulfate reducing bacteria that decompose fatty acids. I. Isolation of new sulfate reducing basteria enriched with acetate from saline environments. Description of Desulfobacter postgatei gen. nov., sp. nov.
Arch.Microbial. 129:395-400.
Widdel, F. and N. Pfenning. 1981b. Studies on dissimilatory sulfate-reducing bacteria that decompose fatty acids. II. Incomplete oxidation of propionate by Desulfobulbus propionicus gen. nov., sp. nov.
Arch.Microbiology 131:360-365.
Table 2 NNiittrriittee :recovery from nitrate reduction at various environmental condition
Reactor Sample Conditions Nitrite Recovered
Origin System (%)
Batch North Sea DNB medium, 60"C, salinity 0-2% 85
CSTR Alaska Steady state, 60*C, D - 0.01 h-1 SO
Batch Alaska DNB medium, 40'C, salinity 1% 0-25
Batch Alaska DNB medium, 60*C, salinity 1% 20-30
Batch Alaska produced water + N03-, 40'C 20
Batch Alaska produced water + N03-, 60'C 75-90
Table 3 N. Sea Column Data (1993)
Influent (mg/L) Effluent (mg/L)
NO, NO, SO, H,S NO, NO, SO, H,S
Before
NO, 0 0 269 74 125
After
N03 54 0 390 38 386
Column: 50 cm, sand, reservoir bacteria consortium present Flow Rate: 2 cm/hr Widdell medium solution
Table 4 N. Sea Column Data (1994)
Influent (mg/L) Effluent (m-/L) NO, NO, SO, H.S NO, NO, SO, H,S
Before NO, 300 90 150
After NO, 10 300 290
Column: 50 cm sand, reservoir bacteria consortium present Flow Rate: 2 cm/hr Widdell medium solution
Claims
1. A method for lowering sulfide concentration in a reservoir comprising adding a concentration of 5-50 ppm of nitrate to said reservoir, wherein said nitrate is biolobically converted to nitrite by in situ denitrifying bacteria, and wherein said nitrite inhibits the production of sulfide by sulfate-reducing bacteria in an actively souring system.
2. A method according to claim 1, wherein said concentration of nitrate is 5-10 ppm.
3. A method according to claim 1, wherein said sulfate-reducing bacteria are naturally occurring thermophilic sulfate-reducing bacteria, and wherein said denitrifying bacteria are naturally occurring thermophilic denitrifying bacteria.
4. A method according to claim 1, wherein said reservoir is selected from the group consisting of oil, gas, and wastewater reservoirs.
5. A method according to claim 1, wherein said nitrate is in the form of a salt selected from the group consisting of sodium nitrate and potassium nitrate.
6. A method for lowering sulfide concentration in a reservior comprising adding a concentration of 5-50 ppm of nitrite to said reservoir, wherein said nitrite inhibits the production of sulfide by sulfate-reducing bacteria in an actively souring system.
7. A method according to claim 6, wherein said concentration of nitrite is 5-10 ppm.
8. A method according to claim 6, wherein said sulfate-reducing bacteria are naturally occurring thermophilic sulfate-reducing bacteria.
9. A method according to claim 6, wherein said reservoir is selected from the group consisting of oil, gas, and wastewater reservoirs.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU38334/95A AU3833495A (en) | 1994-10-20 | 1995-10-18 | Inhibition of sulfate-reducing bacteria via nitrite production |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US32649594A | 1994-10-20 | 1994-10-20 | |
| US08/326,495 | 1994-10-20 |
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| Publication Number | Publication Date |
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| WO1996012867A1 true WO1996012867A1 (en) | 1996-05-02 |
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| WO (1) | WO1996012867A1 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5750392A (en) * | 1993-02-16 | 1998-05-12 | Geo-Microbial Technologies, Inc. | Composition for reducing the amount of and preventing the formation of hydrogen sulfide in an aqueous system, particularly in an aqueous system used in oil field applications |
| WO2000008235A1 (en) * | 1998-08-07 | 2000-02-17 | Hahn-Meitner-Institut Berlin Gmbh | Use of di-tert-butylsulphide (tbds) and/or tert-butylmercaptan (tbm) as corrosion inhibitors in microbial corrosion of metals |
| CN100465267C (en) * | 2006-09-13 | 2009-03-04 | 中国科学院沈阳应用生态研究所 | Microorganism for controlling harm of oil field sulfate reductive bacterium and application thereof |
| CN101338662B (en) * | 2007-09-30 | 2013-04-10 | 盎亿泰地质微生物技术（北京）有限公司 | Method for preventing and reducing hydrogen sulfide of aqueous system and promoting oil recovery factor |
| CN103113866A (en) * | 2013-02-06 | 2013-05-22 | 中国石油化工股份有限公司 | Novel biological inhibitor for inhibiting activity of sulfate reducing bacteria in oil well and use method thereof |
| ES2397463R1 (en) * | 2010-02-03 | 2013-06-07 | Eaux De Marseille Soc D | Treatment procedure for the reduction or prevention of the production of hydrogen sulfide compound and corresponding installation |
| US20130168329A1 (en) * | 2010-04-28 | 2013-07-04 | The University Of Queensland | Control of bacterial activity, such as in sewers and wastewater treatment systems |
| CN103304035A (en) * | 2012-03-08 | 2013-09-18 | 中国科学院沈阳应用生态研究所 | Control agent for souring of produced water of onshore oil reservoirs and application method thereof |
| GB2497250B (en) * | 2010-09-21 | 2016-05-11 | Multi-Chem Group Llc | Method for the use of nitrates and nitrate reducing bacteria in hydraulic fracturing |
| WO2023246505A1 (en) * | 2022-06-23 | 2023-12-28 | 华东理工大学 | Method for inhibiting biogenic hydrogen sulfide in oil field |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4049559A (en) * | 1975-10-09 | 1977-09-20 | Merck & Co., Inc. | Composition for secondary and tertiary oil recovery |
-
1995
- 1995-10-18 WO PCT/US1995/013298 patent/WO1996012867A1/en active Application Filing
- 1995-10-18 AU AU38334/95A patent/AU3833495A/en not_active Abandoned
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4049559A (en) * | 1975-10-09 | 1977-09-20 | Merck & Co., Inc. | Composition for secondary and tertiary oil recovery |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5750392A (en) * | 1993-02-16 | 1998-05-12 | Geo-Microbial Technologies, Inc. | Composition for reducing the amount of and preventing the formation of hydrogen sulfide in an aqueous system, particularly in an aqueous system used in oil field applications |
| WO2000008235A1 (en) * | 1998-08-07 | 2000-02-17 | Hahn-Meitner-Institut Berlin Gmbh | Use of di-tert-butylsulphide (tbds) and/or tert-butylmercaptan (tbm) as corrosion inhibitors in microbial corrosion of metals |
| CN100465267C (en) * | 2006-09-13 | 2009-03-04 | 中国科学院沈阳应用生态研究所 | Microorganism for controlling harm of oil field sulfate reductive bacterium and application thereof |
| CN101338662B (en) * | 2007-09-30 | 2013-04-10 | 盎亿泰地质微生物技术（北京）有限公司 | Method for preventing and reducing hydrogen sulfide of aqueous system and promoting oil recovery factor |
| ES2397463R1 (en) * | 2010-02-03 | 2013-06-07 | Eaux De Marseille Soc D | Treatment procedure for the reduction or prevention of the production of hydrogen sulfide compound and corresponding installation |
| US20130168329A1 (en) * | 2010-04-28 | 2013-07-04 | The University Of Queensland | Control of bacterial activity, such as in sewers and wastewater treatment systems |
| GB2497250B (en) * | 2010-09-21 | 2016-05-11 | Multi-Chem Group Llc | Method for the use of nitrates and nitrate reducing bacteria in hydraulic fracturing |
| GB2533493A (en) * | 2010-09-21 | 2016-06-22 | Multi-Chem Group Llc | Method for the use of nitrates and nitrate reducing bacteria in hydraulic fracturing |
| GB2533493B (en) * | 2010-09-21 | 2017-03-22 | Multi-Chem Group Llc | Method for the use of nitrates and nitrate reducing bacteria in hydraulic fracturing |
| US9683433B2 (en) | 2010-09-21 | 2017-06-20 | Multi-Chem Group, Llc | Method for the use of nitrates and nitrate reducing bacteria in hydraulic fracturing |
| US10287487B2 (en) | 2010-09-21 | 2019-05-14 | Multi-Chem Group Llc | Method for the use of nitrates and nitrate reducing bacteria in hydraulic fracturing |
| CN103304035A (en) * | 2012-03-08 | 2013-09-18 | 中国科学院沈阳应用生态研究所 | Control agent for souring of produced water of onshore oil reservoirs and application method thereof |
| CN103113866A (en) * | 2013-02-06 | 2013-05-22 | 中国石油化工股份有限公司 | Novel biological inhibitor for inhibiting activity of sulfate reducing bacteria in oil well and use method thereof |
| CN103113866B (en) * | 2013-02-06 | 2014-12-10 | 中国石油化工股份有限公司 | Novel biological inhibitor for inhibiting activity of sulfate reducing bacteria in oil well and use method thereof |
| WO2023246505A1 (en) * | 2022-06-23 | 2023-12-28 | 华东理工大学 | Method for inhibiting biogenic hydrogen sulfide in oil field |
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|---|---|
| AU3833495A (en) | 1996-05-15 |
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