[go: up one dir, main page]

US20130056214A1 - Reducing sulfide in production fluids during oil recovery - Google Patents

Reducing sulfide in production fluids during oil recovery Download PDF

Info

Publication number
US20130056214A1
US20130056214A1 US13/226,717 US201113226717A US2013056214A1 US 20130056214 A1 US20130056214 A1 US 20130056214A1 US 201113226717 A US201113226717 A US 201113226717A US 2013056214 A1 US2013056214 A1 US 2013056214A1
Authority
US
United States
Prior art keywords
well
production
nitrate
nitrite
oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US13/226,717
Other languages
English (en)
Inventor
Albert W. Alsop
Robert D. Fallon
Scott Christopher Jackson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US13/226,717 priority Critical patent/US20130056214A1/en
Assigned to E. I. DU PONT DE NEMOURS AND COMPANY reassignment E. I. DU PONT DE NEMOURS AND COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ALSOP, ALBERT W., FALLON, ROBERT D., JACKSON, SCOTT CHRISTOPHER
Priority to RU2014113394/03A priority patent/RU2014113394A/ru
Priority to US13/535,416 priority patent/US20130160994A1/en
Priority to BR112014005154A priority patent/BR112014005154A2/pt
Priority to MX2014002575A priority patent/MX2014002575A/es
Priority to PCT/US2012/044626 priority patent/WO2013036316A1/en
Priority to CN201280042742.XA priority patent/CN103764949A/zh
Priority to CA2846805A priority patent/CA2846805A1/en
Priority to EP12830293.2A priority patent/EP2753795A1/en
Publication of US20130056214A1 publication Critical patent/US20130056214A1/en
Priority to CO14070790A priority patent/CO6930348A2/es
Abandoned legal-status Critical Current

Links

Images

Classifications

    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B21/00—Methods or apparatus for flushing boreholes, e.g. by use of exhaust air from motor
    • E21B21/06—Arrangements for treating drilling fluids outside the borehole
    • E21B21/062—Arrangements for treating drilling fluids outside the borehole by mixing components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456—Removing acid components
    • B01D53/1468—Removing hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • 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
    • C09K8/532—Sulfur
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/106—Peroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/108—Halogens or halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/95—Specific microorganisms

Definitions

  • This disclosure relates to the field of oil recovery. More specifically, it relates to reducing sulfide in production fluids recovered from oil reservoirs.
  • Hydrogen sulfide is commonly found in oil reservoirs due to its production by sulfate-reducing bacteria (SRB), which may be indigenous to an oil reservoir and/or introduced such as during water injection in water flooding secondary oil recovery methods.
  • SRB sulfate-reducing bacteria
  • the metabolism of these SRB converts sulfate that is typically present in injection water to sulfide, which results in souring of a reservoir and the oil produced, thereby reducing the value of the recovered crude oil.
  • SRB sulfate-reducing bacteria
  • sulfate-reducing bacteria converts sulfate that is typically present in injection water to sulfide, which results in souring of a reservoir and the oil produced, thereby reducing the value of the recovered crude oil.
  • sulfide in production water causes corrosion of equipment used to recover oil including storage reservoirs, surface facilities, and pipelines, and it can cause plugging by the formation of iron sulfide, as well as causing health and environmental hazards.
  • SRB and nitrate-reducing bacteria may be present, either as indigenous populations or through introduction. When both are present, there may be competition for nutrients between SRB and nitrate-reducing bacteria (NRB).
  • NRB nitrate-reducing bacteria
  • the presence of SRB and NRB, the presence and types of nutrients available, as well as the balance of sulfate, nitrate, and nitrite are all factors affecting levels of sulfide in the reservoirs and fluids.
  • U.S. Pat. No. 5,405,531 discloses removing H 2 S and preventing SRB production of H 2 S in an aqueous system by introducing nitrite and nitrate and/or molybdate ions in concentrations where denitrifying microorganisms outcompete SRB for available nutrients. Generally less than about 3000 ppm of total nitrate and nitrite ions is added to the aqueous system that is then injected into an oil-bearing formation, more particularly between about 25 and 500 ppm.
  • U.S. Pat. No. 7,833,551 discloses inhibiting sulfide production by SRB by treating SRB with a non-oxidizing biocide and a metabolic inhibitor, which requires lower concentrations of biocide and inhibitor than when each is used alone.
  • the invention relates to methods that lead to reduced sulfide in production fluid obtained from an oil reservoir.
  • the invention provides a method for treating an oil production well comprising:
  • FIG. 1 is a schematic representation of a production well, the subterranean sites adjacent to the production well, and fluids in the well.
  • the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “contains” or “containing,” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a composition, a mixture, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process, method, article, or apparatus.
  • “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • invention or “present invention” as used herein is a non-limiting term and is not intended to refer to any single embodiment of the particular invention but encompasses all possible embodiments as described in the specification and the claims.
  • the term “about” modifying the quantity of an ingredient or reactant of the invention employed refers to variation in the numerical quantity that can occur, for example, through typical measuring and liquid handling procedures used for making concentrates or use solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of the ingredients employed to make the compositions or carry out the methods; and the like.
  • the term “about” also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term “about”, the claims include equivalents to the quantities.
  • the term “about” means within 10% of the reported numerical value, preferably within 5% of the reported numerical value.
  • oil reservoir and “oil-bearing stratum” may be used herein interchangeably and refer to a subterranean or sub sea-bed formation from which oil may be recovered.
  • the formation is generally a body of rocks and soil having sufficient porosity and permeability to store and transmit oil.
  • well bore refers to a channel from the surface to an oil-bearing stratum with enough size to allow for the pumping of fluids either from the surface into the oil-bearing stratum, called an “injection well”, or from the oil-bearing stratum to the surface, called a “production well”.
  • denitrifying and “denitrification” mean reducing nitrate for use in respiratory energy generation.
  • water flooding refers to injecting water through well bores into an oil reservoir. Water flooding is performed to flush out oil from an oil reservoir when the oil no longer flows on its own out of the reservoir.
  • sweep efficiency relates to the fraction of an oil-bearing stratum that has seen fluid or water passing through it to move oil to production wells during water flooding.
  • One problem that can be encountered with water flooding operations is the relatively poor sweep efficiency of the water, i.e., the water can channel through certain portions of a reservoir as it travels from injection well(s) to production well(s), thereby bypassing other portions of the reservoir. Poor sweep efficiency may be due, for example, to differences in the mobility of the water versus that of the oil, and permeability variations within the reservoir which encourage flow through some portions of the reservoir and not others.
  • pure culture means a culture derived from a single cell isolate of a microbial species.
  • the pure cultures specifically referred to herein include those that are publicly available in a depository, and those identified herein.
  • electron acceptor refers to a molecular compound that receives or accepts an electron(s) during cellular respiration. Microorganisms obtain energy to grow by transferring electrons from an “electron donor” to an electron acceptor. During this process, the electron acceptor is reduced and the electron donor is oxidized. Examples of acceptors include oxygen, nitrate, fumarate, iron (III), manganese (IV), sulfate or carbon dioxide. Sugars, low molecular weight organic acids, carbohydrates, fatty acids, hydrogen and crude oil or its components such as petroleum hydrocarbons or polycyclic aromatic hydrocarbons are examples of compounds that can act as electron donors.
  • biofilm means a film or “biomass layer” of microorganisms.
  • Biofilms are often embedded in extracellular polymers, which adhere to surfaces submerged in, or subjected to, aquatic environments. Biofilms consist of a matrix of a compact mass of microorganisms with structural heterogeneity, which may have genetic diversity, complex community interactions, and an extracellular matrix of polymeric substances.
  • plying biofilm means a biofilm that is able to alter the permeability of a porous material, and thus retard the movement of a fluid through a porous material that is associated with the biofilm.
  • nitrates and “simple nitrites” refer to nitrate (NO 3 ⁇ ) and nitrite (NO 2 ⁇ ), respectively.
  • bioplugging refers to making permeable material less permeable due to the biological activity, particlularly by a microorganism.
  • injection water refers to fliud injected into oil reservoirs for secondary oil recovery.
  • Injection water may be supplied from any suitable source, and may include, for example, sea water, brine, production water, water recovered from an underground aquifer, including those aquifers in contact with the oil, or surface water from a stream, river, pond or lake.
  • it may be necessary to remove particulate matter including dust, bits of rock or sand and corrosion by-products such as rust from the water prior to injection into the one or more well bores. Methods to remove such particulate matter include filtration, sedimentation and centrifugation.
  • production water means water recovered from production fluids extracted from an oil reservoir.
  • the production fluids contain both water used in secondary oil recovery and crude oil produced from the oil reservoir.
  • inoculating an oil well means injecting one or more microorganisms or microbial populations or a consortium into an oil well or oil reservoir such that microorganisms are delivered to the well or reservoir without loss of viability.
  • venting refers to an increase in free sulfide concentration with time, which can be measured by recording the H 2 S concentration in the gas phase of a sample.
  • the present invention relates to methods for reducing sulfide in production fluid that include adding a treatment solution that is an aqueous solution containing nitrate ions or nitrite ions or a mixture of nitrate and nitrite ions, where any of these compositions is herein called a “nitrate/nitrite solution”, to the well casing of a oil production well.
  • the treatment solution mixes with production fluid containing oil and water whereby sulfide is removed by oxidation.
  • removing sulfide occurs rapidly in the production fluid in the well as compared to slow sulfide removal when injecting a solution into an injection well where it flows into an oil reservoir.
  • An additional benefit is limited biodegradation of oil components during the short residence time in the well pipe.
  • an aqueous solution containing nitrate ions and/or nitrite ions is added to the well casing of a production well.
  • the total concentration of nitrate and/or nitrite ions is sufficient to reduce sulfide concentration in production fluid.
  • the ions move by mixing and diffusion into the production fluid of oil and water as shown in one embodiment that is diagrammed in FIG. 1 .
  • the nitrate/nitrite treatment solution ( 11 ) is added into the water production well casing ( 7 ) which is inside the well bore ( 6 ) drilled through rock layers ( 2 and 3 ).
  • Rock layer ( 2 ) represents impermeable rock above and below a permeable rock layer ( 3 ) that holds or traps oil.
  • Perforations in the casing ( 5 ) allow oil containing production fluid to flow from fractures ( 4 ) in the permeable rock ( 3 ) into the well casing that extends through the permeable rock that is the oil reservoir ( 3 ) near the bottom of the well hole ( 8 ).
  • the nitrate/nitrite solution flows down the well casing outside of the production tubing or production pipe ( 9 ) and contacts the oil and water production fluid from the oil reservoir ( 12 ) below the production pipe in the well bore as both fluids enter the lower part of the well ( 14 ).
  • the volume of nitrate/nitrite solution that is added is sufficient to fill the well casing.
  • the concentrated nitrate/nitrite solution mixes down into the production fluid towards the bottom of the well forming a production fluid mixture containing nitrate ions, nitrite ions, or a mixture of nitrate and nitrite ions.
  • the production fluid mixed with nitrate/nitrite solution flows up ( 1 ) through the production tubing or production pipe ( 9 ) inside the well casing ( 7 ) through action of the pump rod with check valves ( 10 ).
  • the nitrate/nitrite treatment solution is thus in contact with the production fluid and removes sulfide from the production fluid as the mixture flows up in the production pipe to the surface and is recovered. Sulfide in the production fluid is removed before it gets to the fluid processing unit on the surface.
  • Nitrite ions are either supplied in the treatment solution and/or are formed during contact with the production fluid as a product of nitrate ion metabolism by nitrate-reducing bacteria (NRB) in the production fluid.
  • NRB nitrate-reducing bacteria
  • at least a portion of nitrate ions are reduced to nitrite ions by NRB in the production fluid.
  • Sulfide concentration is reduced by direct chemical conversion of sulfide by nitrite (oxidation to sulfur or sulfate). Sulfide concentration is also reduced by promoting growth of sulfide oxidizing nitrate reducing bacteria (SONRB) by nitrate.
  • production of sulfide is reduced by promoting growth of NRB by nitrate, resulting in reduced growth and therefore activity of sulfate-reducing bacteria (SRB) which produce sulfide.
  • nitrate and/or nitrite ions diffuse into the production fluid and are diluted. If no nitrite is provided in the nitrate/nitrite solution, nitrite ions are generated by NRB in the well. In the mixture of oil and water production fluid with nitrate/nitrite solution the concentration of nitrite ions (supplied or formed from nitrate) is sufficient to oxidize the majority of sulfide to remove it from the production fluid.
  • the concentration of nitrate ions is sufficient to promote growth of nitrate reducing bacteria (NRB) so that dissolved organic carbon (DOC) nutrients are used by NRB instead of by sulfate-reducing bacteria (SRB) to reduce new production of sulfide.
  • NRB nitrate reducing bacteria
  • DOC dissolved organic carbon
  • the nitrite concentration following mixing of the nitrate/nitrite solution with oil and water production fluid from the oil reservoir is at least about 5 times greater than the concentration of sulfide in the production fluid in the well.
  • a ratio of at least about 5:1 of nitrite ions:sulfide ions supports rapid oxidation of the sulfide, as shown herein in Example 2.
  • the concentration of sulfide in the oil and water production fluid of an oil reservoir may be readily measured by one skilled in the art, for example, by using a colorimetric assay based on methylene blue formation (Cline (1969) Limnol. Oceanogr. 14:454-458) or a paper strip assay such as Hydrogen Sulfide Test strips (#481197-1, Industrial Test Systems, Inc., Rock Hill, S.C. USA).
  • nitrate/nitrite solution from the well casing with the oil and water production fluid in the well below the production pipe will dilute the nitrate/nitrite solution.
  • rate and amount of dilution will depend on factors including the method of adding the solution to the well casing (such as pulse, continuous, or single addition), and the density of the production fluid in the bottom of the well. Typically dilution may be by about 1-fold to about 5-fold or more.
  • concentration of nitrate and/or nitirite ions in the solution added to the well casing may be adjusted to accommodate any dilution factor.
  • nitrite may be supplied in the nitrate/nitrite solution directly, or formed by reduction of nitrate by NRB.
  • the total molar concentration of nitrate and/or nitrite ions in the nitrate/nitrite solution is 25-fold greater than the molar concentration of sulfide in the production fluid.
  • a nitrate/nitrite solution added to the well casing has a total concentration of nitrate and/or nitrite ions of at least about 897 ppm or 19.5 mMoles per liter.
  • Additional nitrate may be included in the nitrate/nitrite solution to promote growth of NRB so that available carbon source in production fluid is used up by NRB thereby suppressing growth and production of sulfide by SRB.
  • nitrate/nitrite solution for example, about 93 ppm nitrate would be used in metabolism of about 50 ppm glucose, as calculated based on the assumption that all glucose carbon is converted to carbon dioxide.
  • about 465 ppm of nitrate would support growth of NRB to metabolize 50 ppm of available carbon source.
  • SONRB sulfide oxidizing, nitrate reducing organisms
  • SONRB sulfide oxidizing, nitrate reducing organisms
  • growth and metabolism of SONRB are supported by the nitrate provided in the nitrate/nitrite solution.
  • These bacteria may contribute to reducing the amount of sulfide in production fluid such that the concentration of nitrite needed to oxidize sulfide is reduced.
  • a lower amount of nitrite ions, or nitrate ions that are reduced to nitrite ions by NRB is needed in the presence of SONRB.
  • the nitrate/nitrite solution has a combined concentration of nitrate and/or nitrite ions of at least about 700 ppm. Typically excess concentration is used.
  • the nitrate and/or nitrite combined concentration may be about 800, 900, 1000 ppm or more, up to a limit where toxic effects of the salts on the desired microbial populations becomes an issue, which is approximately 1500 ppm for nitrite and 3000 ppm for nitrate.
  • nitrite concentrations in excess of 100,000 ppm may be used as limited by concentrations that do not adversely corrode metal parts of the system and/or cause problems in down stream oil processing.
  • the nitrate/nitrite solution may be made using nitrate ions and/or nitrite ions in any form that are released in solution, such as in any soluble salt form such as calcium, sodium, potassium, ammonium, and any combination mixtures of salts.
  • any soluble salt form such as calcium, sodium, potassium, ammonium, and any combination mixtures of salts.
  • sodium salts of nitrate and/or nitrite are used.
  • These salts are dissolved in an aqueous solution from any suitable source such as for example, sea water, brine, production water, water recovered from an underground aquifer, including those aquifers in contact with the oil, or surface water from a stream, river, pond or lake.
  • particulate matter including dust, bits of rock or sand and corrosion by-products such as rust from the water prior to use in a treatment solution.
  • Methods to remove such particulate matter include filtration, sedimentation and centrifugation.
  • the nitrate/nitrite solution is first added to the well casing prior to producing from the well. Typically the first addition is just prior to producing from the well. Addition of the nitrate/nitrite solution to the well casing of a production well may be by any method typically used to add fluids to the well casing such as by pumping.
  • the nitrite/nitrate solution may be added to the well casing only once, or intermittently by periodic filling of the well casing before and during production from the well (pulsed).
  • the nitrite/nitrate solution may be added to the well casing continuously by continuous introduction of the solution into the well casing at the top of the production well casing at the surface, before and during production from the well.
  • a separate delivery tubing or pipe within the well casing that is outside of the production tubing or production pipe.
  • This delivery tubing extends from the surface to the lower part of the well to deliver the nitrate/nitrite solution to the point where it mixes with the production fluid below the production pipe.
  • this system for addition requires a separate tubing, it allows more specific control of the concentration of nitrate and/or nitrite ions delivered to the production fluid.
  • the nitrate/nitrite solution may be added alone, or as a mixture with one or more other fluids added to the well casing. When mixed with other fluids, the final nitrite and nitrate ion concentrations in the mixture are those described above. For example, nitrite and nitrate ions may be added to power water used to drive a jet type production well pump. A more concentrated nitrate/nitrite solution may be prepared and diluted into another fluid to be added to the well casing.
  • the nitrate/nitrite solution may be added to the casing of a production well that is a single well oil recovery system or a production well in a multiple well oil recovery system.
  • a production well In a single well oil recovery system the production well is alternately the production well and the injection well.
  • This type of well is typically used in a “Huff and Puff” process.
  • the nitrate/nitrite solution is typically added to the well casing after a well treatment is injected or introduced to the well when the well is returned to production.
  • the nitrate/nitrite solution is typically added to the production well casing prior to and/or during the period when production fluids are being recovered.
  • the present method may be used in oil reservoirs where microbially enhanced oil recovery (MEOR) methods (Brown, L. R., Vadie, A. A,. Stephen, O. J. SPE 59306, SPE/DOE Improved Oil Recovery Symposium, Oklahoma, Apr. 3-5, 2000) are practiced.
  • MEOR methods are used to improve oil recovery by the actions of microorganisms in an oil reservoir, which may include releasing oil from substrates and/or plugging highly permeable zones by formation of plugging biofilms.
  • MEOR methods include injecting oil reservoirs with nutrient solutions that support microbial growth, and also may include inoculation of oil reservoirs with one or more microorganisms as disclosed for example in U.S. Pat. No. 7,776,795, U.S.
  • the production fluid may contain relatively higher levels of one or more carbon substrates to support growth of indigenous microorganisms. Carbon substrates may be in excess in the oil reservoir, and in the oil and water mixture that enters the well becoming production fluid.
  • microorganisms When microorganisms are introduced in MEOR, there may be higher levels of microorganisms, and/or different populations of microorganisms, than without MEOR.
  • the nitrate/nitrite solution is first added to the well casing of a production well after the MEOR treatment to the production well or to an injection well in the same oil reservoir and connected to the production well, but prior to producing from the well.
  • nitrate and/or nitrite ions may be advised to use higher concentrations of nitrate and/or nitrite ions in a nitrate/nitrite solution in conjunction with a MEOR process.
  • concentration needed may be determined by one skilled in the art by analysis of the concentration of sulfide in production fluids, and following ratios described above.
  • a sodium nitrite solution was used to oxidize a sodium sulfide solution at room temperature in a closed system in order to look at the kinetics of the reaction and to prevent the volatilization of sulfide. Based on a balanced redox reaction, 1 mole of nitrite should be able to oxidize at least 0.5 mole of hydrogen sulfide.
  • the nitrite and sulfide solutions used in the experiment were made up in artificial brine, which mimics the moderately high salinity of many oil reservoirs.
  • the brine had the following composition: CaCl 2 .2H 2 O, 6.75 g, NaCl, 26.1 g, Na 2 SO 4 , 0.015 g, MgCl 2 .6H 2 O g, 4.45, KCl, 0.7 g plus enough water to make a total of 500 ml of brine solution.
  • the sulfide solution in brine was approximately 15 ppm S 2 ⁇ .
  • the nitrite solutions were approximately 50 ppm and 725 ppm NO 2 ⁇ .
  • Two different treatments were run. In treatment 1 (Table 1) the nitrite:sulfide molar ratio was 29:1, which resulted in reaction conditions where nitrite was approximately 14.5 (i.e.
  • nitrite:sulfide ratios were tested to determine the molar ratio needed to cause a rapid oxidation of sulfide.
  • the nitrite and sulfide solutions used in the experiments were made up in artificial brine as described in Example 1. Experiments were performed as described in Example 1 using eight different treatments. The nitrite/sulfide molar ratios used were 2, 5, 10, 15, 20, 25, 30, and 35. Results given in Table 2 showed that the reaction rate remained slow at a ratio of 2, as seen in the previous Example, but at a ratio of 5:1 or higher the reaction occurred rapidly with sulfide becoming undetectable in 10 minutes or less. The ability to rapidly remove sulfide at lower nitrite:sulfide ratios makes the process more economical
  • a producer well is continuously treated to mitigate sulfide present in the production water using a nitrate/nitrite mixture.
  • Sulfide in the production fluids often results from well souring, following the start of water injection for secondary oil recovery.
  • a process is used that treats the smaller produced water volume, making it more economical, while still sweetening the produced fluids by removing sulfide.
  • a nitrate/nitrite solution is produced by dissolving any inexpensive nitrate and nitrite salts, such as NaNO 2 or NaNO 3 , in water. This solution is continuously pumped into the well casing of a production well. The production fluid flow entrains the casing solution of nitrate/nitrite into the production fluid moving up the well pipe or, in the case of a jet pump, the nitrate/nitrite solution is incorporated into the power water, which joins the produced fluid flow after passing through the jet pump drive.
  • any inexpensive nitrate and nitrite salts such as NaNO 2 or NaNO 3
  • the nitrate/nitrite mixture contains nitrite (NO 2 ⁇ ) at a molar ratio of approximately 25:1 with respect to the molar concentration of sulfide (S 2 ⁇ ) in the produced water and contains nitrate at a concentration of about 7.5 mMoles NO 3 ⁇ /L per 50 ppm of dissolved organic carbon (DOC) in the production water.
  • This fluid is pumped down the casing at a rate such that the nitrate/nitrite solution is entrained into the production fluids at a ratio of at most 5 parts production fluids per 1 part nitrate/nitrite solution.
  • Two production wells in a soured field are found to contain approximately 25 ppm S 2 ⁇ and 50 ppm DOC.
  • a solution containing 900 ppm NO 2 ⁇ +465 ppm NO 3 ⁇ is pumped into the well casing to treat one of the wells as described above. After a week, S 2 ⁇ concentration is observed to have dropped to 5 ppm, and a week later sulfide is found to be undetectable in the treated well.
  • the neighboring, untreated production well, producing oil from the same soured reservoir is observed to still contain approximately 25 ppm S 2 ⁇ in its produced water after the same two week period.
  • a producer well is treated for microbial enhanced oil recovery using an organic nutrient.
  • a solution of 100 ppm yeast extract plus 4000 ppm of disodium malate is fed batch wise to an oil reservoir through a production well. This is accomplished by pumping this nutrient solution down the casing of the well and into the oil reservoir. The intent of this treatment is to improve oil recovery from this single well.
  • the oil well is shut in for a period of 2 weeks while the microbial population in the well consumes the malate carbon substrate.
  • Analysis of water in the reservoir and of the injection water pumped into the reservoir before and after the nutrient treatment show that there are sulfate reducing bacteria present and that there is 100 ppm sulfate in these waters.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Mining & Mineral Resources (AREA)
  • Geology (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Fluid Mechanics (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Biomedical Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
US13/226,717 2011-09-07 2011-09-07 Reducing sulfide in production fluids during oil recovery Abandoned US20130056214A1 (en)

Priority Applications (10)

Application Number Priority Date Filing Date Title
US13/226,717 US20130056214A1 (en) 2011-09-07 2011-09-07 Reducing sulfide in production fluids during oil recovery
EP12830293.2A EP2753795A1 (en) 2011-09-07 2012-06-28 Reducing sulfide in production fluids during oil recovery
MX2014002575A MX2014002575A (es) 2011-09-07 2012-06-28 Reduccion de sulfuro en los fluidos de produccion durante la recuperacion de petroleo.
US13/535,416 US20130160994A1 (en) 2011-09-07 2012-06-28 Reducing sulfide in production fluids during oil recovery
BR112014005154A BR112014005154A2 (pt) 2011-09-07 2012-06-28 método de tratamento de produção de fluido em um poço de produção de petróleo
RU2014113394/03A RU2014113394A (ru) 2011-09-07 2012-06-28 Снижение содержания сульфидов в технических жидкостях в процессе извлечения нефти
PCT/US2012/044626 WO2013036316A1 (en) 2011-09-07 2012-06-28 Reducing sulfide in production fluids during oil recovery
CN201280042742.XA CN103764949A (zh) 2011-09-07 2012-06-28 采油期间减少采出液中的硫化物
CA2846805A CA2846805A1 (en) 2011-09-07 2012-06-28 Reducing sulfide in production fluids during oil recovery
CO14070790A CO6930348A2 (es) 2011-09-07 2014-04-02 Reducción de sulfuro en los fluidos de producción durante la recuperación de petróleo

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US13/226,717 US20130056214A1 (en) 2011-09-07 2011-09-07 Reducing sulfide in production fluids during oil recovery

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/535,416 Continuation-In-Part US20130160994A1 (en) 2011-09-07 2012-06-28 Reducing sulfide in production fluids during oil recovery

Publications (1)

Publication Number Publication Date
US20130056214A1 true US20130056214A1 (en) 2013-03-07

Family

ID=47752242

Family Applications (1)

Application Number Title Priority Date Filing Date
US13/226,717 Abandoned US20130056214A1 (en) 2011-09-07 2011-09-07 Reducing sulfide in production fluids during oil recovery

Country Status (9)

Country Link
US (1) US20130056214A1 (es)
EP (1) EP2753795A1 (es)
CN (1) CN103764949A (es)
BR (1) BR112014005154A2 (es)
CA (1) CA2846805A1 (es)
CO (1) CO6930348A2 (es)
MX (1) MX2014002575A (es)
RU (1) RU2014113394A (es)
WO (1) WO2013036316A1 (es)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8789592B2 (en) 2013-04-24 2014-07-29 Sabre Intellectual Property Holdings Llc Flooding operations employing chlorine dioxide
US20150211348A1 (en) * 2012-09-19 2015-07-30 John J. Lawrence H2S Removal Using Scavenging Material for Gravel Pack
US10308533B2 (en) 2013-03-15 2019-06-04 Sabre Intellectual Property Holdings Llc Method and system for the treatment of water and fluids with chlorine dioxide
US10442711B2 (en) 2013-03-15 2019-10-15 Sabre Intellectual Property Holdings Llc Method and system for the treatment of produced water and fluids with chlorine dioxide for reuse
US11732560B1 (en) 2022-03-14 2023-08-22 Saudi Arabian Oil Company Nitrate treatment for injectivity improvement

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3339399A1 (en) 2016-12-22 2018-06-27 Rainer Tesch A method for treating petroleum or natural gas
CN111662700B (zh) * 2020-06-17 2023-08-08 华辰环保能源(广州)有限责任公司 一种调控油田采出水配制的聚合物中微生物群落结构组成来减少粘度损失的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2801697A (en) * 1953-08-03 1957-08-06 Crest Res Lab Inc Methods and means for introducing corrosion inhibitors into oil wells
US5044435A (en) * 1990-07-16 1991-09-03 Injectech, Inc. Enhanced oil recovery using denitrifying microorganisms
US6309597B1 (en) * 1997-05-12 2001-10-30 Arkion Life Sciences Method for reducing hydrogen sulfide level in water containing sulfate-reducing bacteria and hydrogen sulfide-metabolizing bacteria

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4507212A (en) * 1982-11-15 1985-03-26 The Standard Oil Company Nitrile compounds as oil field biocides
US4905761A (en) * 1988-07-29 1990-03-06 Iit Research Institute Microbial enhanced oil recovery and compositions therefor
US5686293A (en) * 1995-07-07 1997-11-11 Phillips Petroleum Company Sulfide-oxidizing bacteria
US20040007501A1 (en) * 2002-07-08 2004-01-15 Sughrue Edward L. Hydrocarbon desulfurization with pre-oxidation of organosulfur compounds
US20050040078A1 (en) * 2003-08-20 2005-02-24 Zinnen Herman A. Process for the desulfurization of hydrocarbonacecus oil

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2801697A (en) * 1953-08-03 1957-08-06 Crest Res Lab Inc Methods and means for introducing corrosion inhibitors into oil wells
US5044435A (en) * 1990-07-16 1991-09-03 Injectech, Inc. Enhanced oil recovery using denitrifying microorganisms
US6309597B1 (en) * 1997-05-12 2001-10-30 Arkion Life Sciences Method for reducing hydrogen sulfide level in water containing sulfate-reducing bacteria and hydrogen sulfide-metabolizing bacteria

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Penberthy Jet Pumps, "Jet Pump Technical Data" May 1987 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150211348A1 (en) * 2012-09-19 2015-07-30 John J. Lawrence H2S Removal Using Scavenging Material for Gravel Pack
US10308533B2 (en) 2013-03-15 2019-06-04 Sabre Intellectual Property Holdings Llc Method and system for the treatment of water and fluids with chlorine dioxide
US10442711B2 (en) 2013-03-15 2019-10-15 Sabre Intellectual Property Holdings Llc Method and system for the treatment of produced water and fluids with chlorine dioxide for reuse
US8789592B2 (en) 2013-04-24 2014-07-29 Sabre Intellectual Property Holdings Llc Flooding operations employing chlorine dioxide
US8991500B2 (en) * 2013-04-24 2015-03-31 Sabre Intellectual Property Holdings Llc Fracturing operations employing chlorine dioxide
US8997862B2 (en) 2013-04-24 2015-04-07 Sabre Intellectual Property Holdings Llc Flooding operations employing chlorine dioxide
US10526530B2 (en) 2013-04-24 2020-01-07 Sabre Intellectual Property Holdings Llc Flooding operations employing chlorine dioxide
US11732560B1 (en) 2022-03-14 2023-08-22 Saudi Arabian Oil Company Nitrate treatment for injectivity improvement

Also Published As

Publication number Publication date
EP2753795A1 (en) 2014-07-16
CA2846805A1 (en) 2013-03-14
RU2014113394A (ru) 2015-10-20
BR112014005154A2 (pt) 2017-03-28
WO2013036316A1 (en) 2013-03-14
CO6930348A2 (es) 2014-04-28
MX2014002575A (es) 2014-06-05
CN103764949A (zh) 2014-04-30

Similar Documents

Publication Publication Date Title
US20130160994A1 (en) Reducing sulfide in production fluids during oil recovery
US20130056214A1 (en) Reducing sulfide in production fluids during oil recovery
Larsen Downhole nitrate applications to control sulfate reducing bacteria activity and reservoir souring
CN101746897B (zh) 一种抑制油田水中硫酸盐还原菌的营养物及其应用
Larsen et al. Prevention of reservoir souring in the Halfdan field by nitrate injection
RU2559978C2 (ru) Системы и способы микробиологического повышения нефтеотдачи пластов
US20120273189A1 (en) Prevention of biomass aggregation at injection wells
CN101338662B (zh) 预防和降低含水体系中的硫化氢和提高石油采收率的方法
US20140000874A1 (en) Reducing sulfide in oil reservoir production fluids
Nixon et al. Guar gum stimulates biogenic sulfide production at elevated pressures: implications for shale gas extraction
US8573300B2 (en) Reducing sulfide in oil reservoir production fluids
US4879240A (en) Microbial control of hydrogen sulfide production by sulfate reducing bacteria
Eckford et al. Using nitrate to control microbially-produced hydrogen sulfide in oil field waters
Jenneman et al. Field demonstration of sulfide removal in reservoir brine by bacteria indigenous to a Canadian reservoir
US8403041B2 (en) Method for pre-treatment of subterranean sites adjacent to water injection wells
MX2013000292A (es) Metodo para tratamiento de sitios subterraneos adyacentes a pozos de inyeccion de agua.
Voordouw Emerging oil field biotechnologies: prevention of oil field souring by nitrate injection
McInerney et al. Causes and control of microbially induced souring
US8397806B2 (en) Method for pre-treatment of subterranean sites adjacent to water injection wells
Labena et al. Biological souring and mitigation strategies in oil reservoirs
US20230287773A1 (en) Nitrate treatment for injectivity improvement
WO2014165436A1 (en) Method for the use of nitrates and nitrate reducing bacteria for mitigating biogenic sulfide production
US8371378B2 (en) Method for pre-treatment of subterranean sites adjacent to water injection wells
Yin et al. Combined effects of microbes and nitrate on SRB growth, souring and corrosion
Xue Control of Microbial Sulfide Production with Nitrate and Biocide in Oilfield-Simulating Bioreators

Legal Events

Date Code Title Description
AS Assignment

Owner name: E. I. DU PONT DE NEMOURS AND COMPANY, DELAWARE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ALSOP, ALBERT W.;JACKSON, SCOTT CHRISTOPHER;FALLON, ROBERT D.;SIGNING DATES FROM 20110922 TO 20110926;REEL/FRAME:027059/0720

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION