WO2013036316A1 - Réduction du soufre dans des fluides de production pendant l'extraction de pétrole - Google Patents

Réduction du soufre dans des fluides de production pendant l'extraction de pétrole Download PDF

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Publication number
WO2013036316A1
WO2013036316A1 PCT/US2012/044626 US2012044626W WO2013036316A1 WO 2013036316 A1 WO2013036316 A1 WO 2013036316A1 US 2012044626 W US2012044626 W US 2012044626W WO 2013036316 A1 WO2013036316 A1 WO 2013036316A1
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WIPO (PCT)
Prior art keywords
well
production
sulfide
nitrate
oil
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PCT/US2012/044626
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English (en)
Inventor
Albert W. Alsop
Scott Christopher Jackson
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E. I. Du Pont De Nemours And Company
Fallon, Robert D.
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Publication date
Application filed by E. I. Du Pont De Nemours And Company, Fallon, Robert D. filed Critical E. I. Du Pont De Nemours And Company
Priority to CN201280042742.XA priority Critical patent/CN103764949A/zh
Priority to RU2014113394/03A priority patent/RU2014113394A/ru
Priority to CA2846805A priority patent/CA2846805A1/fr
Priority to MX2014002575A priority patent/MX2014002575A/es
Priority to EP12830293.2A priority patent/EP2753795A1/fr
Priority to BR112014005154A priority patent/BR112014005154A2/pt
Publication of WO2013036316A1 publication Critical patent/WO2013036316A1/fr

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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 (H 2 S) is commonly found in oil reservoirs due to its production by sulfate-reducing bacteria (SRB), which may be
  • sulfate 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.
  • 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.
  • One method used to reduce sulfide has been to add nitrate to injection water that is administered field-wide to an oil reservoir through multiple injection wells (Griroryan et al. (2009) J. Can. Petrol Technol. 48:58-61 ).
  • US 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.
  • US 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. Accordingly, the invention provides a method for treating an oil production well comprising: a) providing an oil production well in an oil reservoir having a well casing and a production pipe;
  • step (b) wherein the sulfide concentration in the production fluid is reduced as compared to the sulfide concentration in production fluid obtained with omission of step (b).
  • the inorganic oxidizing agent is nitrate ions, nitrite ions, or a mixture of nitrate and nitrite ions.
  • the inorganic oxidizing agent is selected from permanganates, persulfates, inorganic peracids, chromates, bromates, iodates, chlorates, perchlorates, chlorites, hypochlorites, inorganic peroxides, and oxides.
  • Figure 1 is a schematic representation of a production well, the subterranean sites adjacent to the production well, and fluids in the well.
  • compositions, 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.
  • indefinite articles "a” and “an” preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component.
  • 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.
  • wash 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.
  • 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.
  • 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
  • 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 (NO3 " ) and nitrite (NO 2 ⁇ ), respectively.
  • bioplugging refers to making permeable material less permeable due to the biological activity, particularly 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 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.
  • 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
  • the present invention relates to methods for reducing sulfide in production fluid that include adding a treatment solution that is an aqueous solution containing another strong inorganic oxidizing agent to the well casing of an oil production well.
  • the treatment solution mixes with production fluid containing oil and water whereby sulfide is removed by oxidation.
  • an aqueous solution containing nitrate ions and/or nitrite ions, or another inorganic oxidizing agent is added to the well casing of a production well.
  • the total concentration of nitrate and/or nitrite ions, or of other inorganic oxidizing agent, is sufficient to reduce sulfide concentration in production fluid.
  • the nitrate/nitrite or other inorganic oxidizing agent-containing 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 or other inorganic oxidizing agent-containing 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 or other inorganic oxidizing agent-containing solution that is added is sufficient to fill the well casing.
  • the concentrated nitrate/nitrite or other inorganic oxidizing agent-containing 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 or a production fluid mixture containing the other inorganic oxidizing agent.
  • the production fluid mixed with nitrate/nitrite or other inorganic oxidizing agent-containing 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 or other inorganic oxidizing agent-containing 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 nitrate/nitrite 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.
  • concentration of nitrite ions supplied or formed from nitrate is sufficient to oxidize the majority of sulfide to remove it from the production fluid.
  • 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-fold 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 (#481 197-1 , Industrial Test Systems, Inc., Rock Hill, SC 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
  • 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.
  • An aqueous solution of the present method may contain a different inorganic oxidizing agent, other than nitrate/nitrite.
  • the inorganic oxidizing agent may be any water soluble strong inorganic oxidizing agent, with strong meaning that the inorganic oxidizing agent has reaction standard half-cell potential of greater than -0.478 volts.
  • a strong inorganic oxidizing agent examples of which include, but are not limited to, permanganates, persulfates, inorganic peracids, chromates, bromates, iodates, chlorates, perchlorates, chlorites, hypochlorites, inorganic peroxides, and certain oxides.
  • Some specific examples include ammonium dichromate, ammonium perchlorate, ammonium permanganate, barium bromate, barium chlorate, barium peroxide, cadmium chlorate, calcium chlorate, calcium chromate, calcium perchlorate, chlorine dioxide, potassium persulfate, and hydrogen peroxide.
  • the inorganic oxidizing agent is chlorine dioxide, hypochlorite, persulfate, or hydrogen peroxide.
  • At least one inorganic oxidizing agent is included in the aqueous solution. Typically oxidizing agents are used separately.
  • the agent diffuses into the production fluid and is diluted.
  • the agent diffuses into the production fluid and is diluted.
  • concentration of the agent is sufficient to oxidize the majority of sulfide to remove it from the production fluid.
  • Sulfide is directly oxidized by the agent by direct chemical conversion of sulfide to sulfur or sulfate.
  • the inorganic oxidizing agent concentration following mixing of the inorganic oxidizing agent-containing solution with oil and water production fluid from the oil reservoir is at least about 1 .5 to 6 times greater than the concentration of sulfide in the production fluid in the well.
  • the agent concentration may be at least about 1 .5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, or 6 times greater than the concentration of sulfide in the production fluid in the well.
  • the exact agent concentration needed to oxidize the majority of the sulfide may be readily determined for a specific agent by one skilled in the art, as shown in examples herein for chlorine dioxide, potassium persulfate, and hydrogen peroxide.
  • ratios of 1 .71 :1 , 5.3:1 , and 3.76:1 are effective in causing rapid and complete or almost complete oxidation of sulfide by these agents, respectively.
  • 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 (#481 197-1 , Industrial Test Systems, Inc., Rock Hill, SC).
  • inorganic oxidizing agent-containing solution from the well casing with the oil and water production fluid in the well below the production pipe will dilute the agent solution.
  • the 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 inorganic oxidizing agent in the solution added to the well casing may be adjusted to accommodate any dilution factor.
  • the inorganic oxidizing agent-containing solution may be made using any of the agents, as exemplified above, in a form that is soluble in water.
  • the agent is 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.
  • 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.
  • it may be desired to remove 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 or other inorganic oxidizing agent-containing 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 or other inorganic oxidizing agent-containing 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 or other inorganic oxidizing agent-containing 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 or other inorganic oxidizing agent-containing 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 or other inorganic oxidizing agent-containing 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, and of another inorganic oxidizing agent, delivered to the production fluid.
  • the nitrate/nitrite or other inorganic oxidizing agent-containing 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, or other inorganic oxidizing agent concentration, in the mixture are those described above.
  • nitrite and nitrate ions or other inorganic oxidizing agent may be added to power water used to drive a jet type production well pump.
  • a more concentrated nitrate/nitrite or other inorganic oxidizing agent-containing solution may be prepared and diluted into another fluid to be added to the well casing.
  • the nitrate/nitrite or other inorganic oxidizing agent-containing 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 or other inorganic oxidizing agent-containing 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 or other inorganic oxidizing agent-containing solution is typically added to the production well casing prior to and/or during the period when production fluids are being recovered. Combination of nitrate/nitrite or other inorganic oxidizing agent-containing solution and MEOR treatments
  • the present method may be used in oil reservoirs where
  • MEOR microbially enhanced oil recovery
  • 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 US 7,776,795, US 7,708,065, and commonly owned and co-pending US Pat. Appl. Pub. #20090263887, which are each incorporated herein by reference.
  • 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 or other inorganic oxidizing agent- containing 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 in a nitrate/nitrite solution or other inorganic oxidizing agent in 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: CaCl2.2H 2 O, 6.75 g, NaCI, 26.1 g, Na 2 SO 4 , 0.015 g, MgCI 2 .6H 2 O g, 4.45, KCI, 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 ratio should be in excess of 2.1 :1 .
  • Table 1 Changes in sulfide concentrations with time following the addition of nitrite.
  • 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
  • Table 2 Changes in sulfide concentrations with time following the addition of nitrite at NO2 ⁇ :S 2 ⁇ ratios from 2:1 to 35:1 .
  • Production well treatment usinq continuous addition of nitrate/nitrite solution in well casing to mitigate sulfide present in production fluid of soured wells
  • 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 NaNO2 or NaNO3 , in water. This solution is continuously pumped into the well casing of a production well. The production fluid flow entrains the casing
  • the nitrate/nitrite solution is
  • production fluids at a ratio of at most 5 parts production fluids per 1 part nitrate/nitrite solution.
  • Nitrate/nitrite treatment combined with a MEOR process that utilizes organic nutrients
  • 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. It is therefore anticipated that some sulfide will be produced from the sulfate reducing bacteria
  • nitrate/nitrite solution in the well casing becomes mixed with the production fluids and analysis of the well effluent shows no signs of sulfide in the produced water.
  • Chlorine dioxide removal of sulfide Titration of molar ratios needed
  • Example 1 Experiments were performed as described in Example
  • Table 3 Changes in sulfide concentrations after a10 minute reaction time following the addition of chlorine dioxide at various molar ratios.
  • Persulfate removal of sulfide Titration of molar ratios needed for a
  • Table 4 Changes in sulfide concentrations after a10 minute reaction time following the addition of a persulfate solution at various molar ratios.
  • Table 5 Changes in sulfide concentrations after a 10 minute reaction time following the addition of hydrogen peroxide at various molar ratios.

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Abstract

L'invention concerne des procédés pour traiter un fluide de production dans un puits de production dans un gisement de pétrole afin de réduire la quantité de soufre dans le fluide de production. Le fluide de production est traité avec des ions nitrate et/ou des ions nitrite ou un agent oxydant inorganique dans une solution aqueuse qui est ajoutée au tubage.
PCT/US2012/044626 2011-09-07 2012-06-28 Réduction du soufre dans des fluides de production pendant l'extraction de pétrole WO2013036316A1 (fr)

Priority Applications (6)

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CN201280042742.XA CN103764949A (zh) 2011-09-07 2012-06-28 采油期间减少采出液中的硫化物
RU2014113394/03A RU2014113394A (ru) 2011-09-07 2012-06-28 Снижение содержания сульфидов в технических жидкостях в процессе извлечения нефти
CA2846805A CA2846805A1 (fr) 2011-09-07 2012-06-28 Reduction du soufre dans des fluides de production pendant l'extraction de petrole
MX2014002575A MX2014002575A (es) 2011-09-07 2012-06-28 Reduccion de sulfuro en los fluidos de produccion durante la recuperacion de petroleo.
EP12830293.2A EP2753795A1 (fr) 2011-09-07 2012-06-28 Réduction du soufre dans des fluides de production pendant l'extraction de pétrole
BR112014005154A BR112014005154A2 (pt) 2011-09-07 2012-06-28 método de tratamento de produção de fluido em um poço de produção de petróleo

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US13/226,717 US20130056214A1 (en) 2011-09-07 2011-09-07 Reducing sulfide in production fluids during oil recovery

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US11814587B2 (en) 2016-12-22 2023-11-14 Rainer TESCH Method for treating petroleum or natural gas

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WO2014046769A1 (fr) * 2012-09-19 2014-03-27 Exxonmobil Upstream Research Company Retrait de h2s à l'aide de matériau d'épuration pour massif de gravier
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
US9238587B2 (en) 2013-03-15 2016-01-19 Sabre Intellectual Property Holdings Llc Method and system for the treatment of water and fluids with chlorine dioxide
US8991500B2 (en) * 2013-04-24 2015-03-31 Sabre Intellectual Property Holdings Llc Fracturing operations employing chlorine dioxide
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
US11732560B1 (en) 2022-03-14 2023-08-22 Saudi Arabian Oil Company Nitrate treatment for injectivity improvement

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US4905761A (en) * 1988-07-29 1990-03-06 Iit Research Institute Microbial enhanced oil recovery and compositions therefor
US5789236A (en) * 1995-07-07 1998-08-04 Phillips Petroleum Company Process of using sulfide-oxidizing bacteria
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CO6930348A2 (es) 2014-04-28
BR112014005154A2 (pt) 2017-03-28
RU2014113394A (ru) 2015-10-20
CA2846805A1 (fr) 2013-03-14
EP2753795A1 (fr) 2014-07-16
MX2014002575A (es) 2014-06-05
US20130056214A1 (en) 2013-03-07

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