CN103541703A - Microorganism oil extraction method - Google Patents
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- CN103541703A CN103541703A CN201310052884.0A CN201310052884A CN103541703A CN 103541703 A CN103541703 A CN 103541703A CN 201310052884 A CN201310052884 A CN 201310052884A CN 103541703 A CN103541703 A CN 103541703A
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Abstract
The invention provides a microorganism oil extraction method. The method comprises the steps of introducing denitrifying microorganism (a), aqueous solution carrier (b) and a non-oxygen electron acceptor (c) into a reservoir rock stratum on the anaerobic environment conditions; enabling the denitrifying microorganism to restore the non-oxygen electron acceptor on the condition that elemental sulfur and/or sulfocompound exists, and generating sulfuric acid, wherein the sulfuric acid has a dissolution function on the reserving rocks so as to enable oil to be released easily. According to the method, the denitrifying microorganism (a), the aqueous solution carrier (b) and the non-oxygen electron acceptor (c) are introduced into the reservoir rock stratum, so that the denitrifying microorganism can restore the non-oxygen electron acceptor on the condition that the elemental sulfur and/or sulfocompound exists, the amount of sulfuretted hydrogen in water containing systems is reduced, further forming of sulfuretted hydrogen can be prevented, and growth of sulfate reducting bacteria possibly existing in the water containing systems can be restrained, sulfuric acid can be generated, and oil can be released easily, so that the oil extraction rate is improved..
Description
The application is the dividing an application for the invention that is 200710161388.3 of " prevention and reduce hydrogen sulfide in Aquo System and improve the method for oil recovery ", application number that be 2007.09.30, denomination of invention the applying date.
Technical field
The present invention relates to the technical field of recovering the oil, relate in particular to a kind of microbe oil production method.
Background technology
Oil is to collect after being transported to ground by one or more drilling wells that penetrate underground petroliferous bed.If underground petroliferous bed has enough large pressure to exist, oil will not need pump and spontaneously from earth's surface, overflow.Generally, along with the exploitation in oil field, strata pressure can progressively decline, and then need to adopt pump exploitation.
At present, the recovery ratio of crude oil, 10% to 50% not etc., is on average about 33%.The Oil reserves computed of having found according to China, oil recovery factor improves 1%, just can increase the recoverable reserves of more than 200,000,000 ton.This will bring great economic interests, and can reduce the dependence to foreign oil.Therefore, a kind of method of cost-effective raising oil recovery factor solves energy shortage to China, ensures that energy resource supply tool is of great significance.
As everyone knows, the acidifying of many oil reservoirs is the hydrogen sulfide (H due to microorganisms
2s) cause.The generation of hydrogen sulfide is the result that sulfate reducing bacteria is sulfide by the sulfate conversion in system.These bacteriums are existing primary in oil reservoir, also have to introduce in oil drilling process." sulfate reducing bacteria " that J.R.Postgate shows, second edition, 1984, Cambridge University Press, has introduced these microorganisms and the impact on oil field thereof.
Sulfuration Hydrogen Energy causes the heavy corrosion of oil production equipment, greatly destroys the production capacity in oil field, and reduces the commercial value of crude oil.Therefore,, for prevention and the removing of hydrogen sulfide, forefathers have done a large amount of deep research.In some cases, the hydrogen sulfide problem that industrial quarters generally adopts various bactericide to solve to be caused by sulfate reducing bacteria.Although adopt bactericide to administer hydrogen sulfide effect, differ, and if the nitrate mentioned of the present invention and/or the system for handling of nitrite combine, bactericide is administered hydrogen sulfide effect and will be significantly improved.
As everyone knows, molybdate can suppress or kill the sulfate reducing bacteria (SRB) that produces hydrogen sulfide in the natural environments such as lacustrine deposit.But this method needs a large amount of molybdates, for example the molybdate concentration in water need to surpass the generation that 3000ppm could control hydrogen sulfide effectively.This method is used a large amount of molybdates, and not only expense is high but also inefficiency.
Therefore, a kind ofly eliminate cost-effectively the method for already present hydrogen sulfide in Aquo System and be very important.Meanwhile, this method also must be able to prevent sulfate reducing bacteria further to produce hydrogen sulfide.
The present invention is just being to provide a kind of like this method, it can not only eliminate existing hydrogen sulfide in Aquo System, inhibiting sulfate reduction bacterium further produces hydrogen sulfide, and can be by adopting without hydrogen sulfide or being subject to Aquo System that hydrogen sulfide contamination is less to improve the recovery ratio of oil.
Summary of the invention
One of object of the present invention is to provide a kind of method of practicality oil is exploited out the Oil Trap of each in stratum.
Two of object of the present invention is to provide the pressure that a kind of method can increase subterranean oil gas reservoir, so that oil exploitation.
Three of object of the present invention is to provide a kind of method of oil recovery that more effectively improves under underground anaerobic environment.
More specifically, the invention provides a kind of particularly method of the hydrogen sulfide in the Aquo System of oil field of Aquo System that reduces.The present invention also provides a kind of effective ways that thereby inhibiting sulfate reduction bacterium prevention hydrogen sulfide produces in Aquo System.The present invention also provides to adopt without hydrogen sulfide and maybe may be subject to Aquo System that hydrogen sulfide contamination is less to improve the method for oil recovery.The present invention also provides useful component in said method and a kind of method of microbe oil production, in the stratum under anaerobic environment, inject denitrifying microorganism, water and nitrate anion and/or nitrite ion, thereby promoted microbial metabolic products as biopolymer, biosurfactant, the formation of acid, solvent, nitrogen and carbon dioxide, these metabolites contribute to improve oil recovery factor.
The invention provides a kind of method of microbe oil production, be included in stratum and introduce following factor to determine anaerobic environment: (a) denitrifying microorganism, (b) aqueous carrier, (c) non-positro acceptor.In such environment and system, microorganism can, in the situation that elementary sulfur and/or sulfur-containing compound (the especially sulphur-containing substance of reduction-state) exist, consume this non-positro acceptor.The present invention has determined that preferred microorganism is that denitrifying microorganism comprises that Thiobacillus is as denitrifying bacterias such as T denitrifiers, and preferred non-positro acceptor is a kind of nitrate anion and/or nitrite ion source.
After nitrate anion and/or nitrite ion source are reduced, can produce nitrogen, increase the pressure in petroliferous bed space, thereby contribute to drive oil to discharge from rock stratum.
First aspect, the present invention by the compound introducing nitrate anion and/or nitrite ion maybe can produce above-mentioned ion in Aquo System to reduce the amount of hydrogen sulfide in Aquo System and the further formation of prevention hydrogen sulfide.The concentration of these ions or compound is enough to set up and promote the growth of denitrifying microorganism.Wherein, some denitrifying microorganisms were just present in Aquo System before adding ion or compound, also had plenty of when introducing ion or supplemented later and go in joining Aquo System.
Second aspect, the present invention is by introduce molybdenum acid ion in Aquo System, and nitrate anion and/or nitrite ion maybe can produce the compound of above-mentioned ion to reduce the amount of hydrogen sulfide in Aquo System and the further formation of prevention hydrogen sulfide.The concentration of these ions or compound is enough to suppress or kill sulfate reducing bacteria.
The third aspect, utilize the method processing of described introducing nitrite ion and/or nitrate ion and/or molybdenum acid ion can obtain a kind of Aquo System, so, the present invention also provides a kind of method that makes oilfield stimulation, and the method comprises the above-mentioned Aquo System of processing through nitrite ion and/or nitrate ion and/or molybdenum acid ion is injected into the process in underground petroleum-containing formation.The present invention and then provide a kind of Aquo System of processing through nitrite ion and/or nitrate ion and/or molybdenum acid ion that adopts to carry out the method that microorganism is improved oil recovery.This microbe oil production technique comprises above-mentioned treated Aquo System is injected into underground petroliferous bed with the oil in space, displacement rock stratum.
According to a further aspect in the invention, a kind of mixture (useful component that said method is related) that is applicable to said method is also provided, comprise that (a) nitrite ion maybe can produce the compound of this ion, and (b) have at least a kind of nitrate ion and/or molybdenum acid ion maybe can produce the compound of these ions.
The invention provides a kind of method of microbe oil production, the method comprising the steps of: by (a) denitrifying microorganism, (b) aqueous carrier, (c) non-positro acceptor is incorporated into the reservoir rock stratum under anaerobic environment condition, make denitrifying microorganism under the condition of elementary sulfur and/or sulfur-containing compound existence, by described non-positro acceptor reduction, and produce sulfuric acid, thereby and sulfuric acid has to reservoir rock the release that corrosion is easy to oil.
Preferably, described non-positro acceptor is selected from following ion gun: one or more in nitrate ion source, nitrite ion source, nitric oxide and nitrous oxide.
Preferably, described non-positro acceptor is a kind of nitrate ion source.
Preferably, described elementary sulfur and/or sulfur-containing compound are contained in described reservoir rock stratum.
Preferably, also comprise elementary sulfur and/or sulfur-containing compound are incorporated into the step in reservoir rock stratum.
Preferably, also comprise described elementary sulfur and/or sulfur-containing compound are incorporated in reservoir rock stratum, and this sulfur-containing compound is to be selected from thiosulfate, four sulphur hydrochlorate or sulfide.
Preferably, described denitrifying microorganism is denitrification Thiobacillus.
Preferably, the described dissolving to reservoir rock stratum, the mixture that makes to consist of described denitrification Thiobacillus, described aqueous carrier and described non-positro acceptor is buffered to pH value and approaches 6.5.
Preferably, also comprise the step that phosphate compounds is incorporated into described reservoir rock stratum, the addition of this phosphate compounds meets microorganism to the nutraceutical needs of phosphate.
Preferably, driven water-replacing is as described aqueous carrier.
Preferably, described introducing step comprises the mixture that contains described microorganism, described non-positro acceptor and described aqueous carrier and driven water-replacing is injected into respectively in described reservoir rock stratum individually.
Preferably, described reservoir rock stratum comprises clastic reservoir, carbonate reservoir, Potential Volcanic Reservoir, and clastic, carbonate rock, lava and argillaceous rocks mixing reservoir.
Preferably, also comprised the step that metal nutritional agents is incorporated into described reservoir rock stratum, the amount of this metal nutritional agents meets the requirement of described microorganism to metal nutritional agents.
Preferably, also comprised the step of a kind of nitrogenous source being introduced to described reservoir rock stratum.
Preferably, the reduction of described nitrate ion source produces nitrogen, and nitrogen is being oppressed the oil in described reservoir rock stratum, and this compressing contributes to oil to depart from from reservoir rock stratum.
Preferably, described reservoir rock and CO
2in chemical balance, and described microorganism removes CO
2can cause that reservoir rock further dissolves to maintain chemical balance.
The invention provides a kind of method of microbe oil production, the method comprising the steps of: by (a) denitrifying microorganism, (b) aqueous carrier, (c) non-positro acceptor is incorporated into the reservoir rock stratum under anaerobic environment condition, make denitrifying microorganism under the condition of elementary sulfur and/or sulfur-containing compound existence, by described non-positro acceptor reduction, and produce sulfuric acid, thereby and sulfuric acid has to reservoir rock the release that corrosion is easy to oil.Method provided by the invention is incorporated into denitrifying microorganism, aqueous carrier and non-positro acceptor in reservoir rock stratum, thereby under elementary sulfur and/or the condition containing compound existence, described denitrifying microorganism is by described non-positro acceptor reduction, reduce the amount of hydrogen sulfide in Aquo System, and can prevent the further formation of hydrogen sulfide, and can suppress the growth of the sulfate reducing bacteria that may exist in Aquo System, and produce sulfuric acid, be easy to the release of oil, thereby improved the acquisition rate of oil.Experimental result shows, method provided by the invention is the growth of inhibiting sulfate reduction bacterium effectively, thereby reduce and prevented the content of hydrogen sulfide in Aquo System, make in a bite typical case well to have every day that 15kg limestone is dissolved nearly, this solubility is equivalent to dissolve every year 2-3 ton limestone, has absolutely proved the effect of the Microbial Enhanced Oil Recovery extracting according to the present invention.
Below elaborating that specific embodiments of the present invention are carried out.Other object, feature and superiority of the present invention is by very clear.
Accompanying drawing explanation
The microbe oil production apparatus structure schematic diagram that Fig. 1 provides for the embodiment of the present invention.
The specific embodiment
The invention provides a kind of method of microbe oil production, the method comprising the steps of: by (a) denitrifying microorganism, (b) aqueous carrier, (c) non-positro acceptor is incorporated into the reservoir rock stratum under anaerobic environment condition, make denitrifying microorganism under the condition of elementary sulfur and/or sulfur-containing compound existence, by described non-positro acceptor reduction, and produce sulfuric acid, thereby and sulfuric acid has to reservoir rock the release that corrosion is easy to oil.
The present invention's oil production method provided by the invention has reduced the content of hydrogen sulfide in reservoir rock stratum, has improved the acquisition rate of oil.The present invention is incorporated into the reservoir rock stratum under anaerobic environment condition by denitrifying microorganism, aqueous carrier and non-positro acceptor, the present invention does not have special restriction to the mode of described introducing, preferably described denitrifying microorganism, aqueous carrier and non-positro acceptor is injected into respectively to the reservoir rock stratum under anaerobic environment condition individually;
In the present invention, described reservoir rock stratum preferably includes clastic reservoir, carbonate reservoir, Potential Volcanic Reservoir, and clastic, carbonate rock, lava and argillaceous rocks mixing reservoir; The present invention does not have special restriction to described denitrifying microorganism, adopts denitrifying microorganism well known to those skilled in the art, and in the present invention, described denitrifying microorganism is preferably denitrification Thiobacillus; Described aqueous carrier is preferably driven water-replacing; Described non-positro acceptor is preferably selected from following ion gun: one or more in nitrate ion source, nitrite ion source, nitric oxide and nitrous oxide, more preferably a kind of nitrate ion source.In the present invention, the mass ratio of described denitrifying microorganism, aqueous carrier, non-positro acceptor is preferably adopted the mass ratio of described denitrifying microorganism, aqueous carrier and non-positro acceptor described in technique scheme;
In the present invention, nitrite ion in described non-positro acceptor and the ratio of described nitrate ion are preferably between 50:1 to 1:50, more preferably between 10:1 to 1:10, most preferably be between 1:1 to 1:5, in the present invention, the ratio of described nitrite ion and described nitrate ion refers to the mol ratio of nitrite ion and nitrate ion;
In the present invention, the amount of described nitrate anion, nitrite ion must be enough large to promote the amount reproduction of denitrifying microorganism, thereby consume competitively the required carbon source of Growth of Sulfate Reducing Bacteria, and then suppressed the conversion of sulfate to sulfide.Therefore, the addition of nitrate anion, nitrite ion depends on the amount that in pending system, carbon source exists.For example, if contain the acetate of 1000ppm in pending Aquo System, and before all by sulfate reducing bacteria, to be used for sulfate conversion be sulfide, so, nitrate anion, nitrite ion addition must be wide enough so that denitrifying microorganism can first consume the acetate of all 1000ppm before sulfate reducing bacteria utilizes acetate.The present invention studies the about 200ppm nitrate anion of discovery and about 100ppm nitrite ion has been realized expected effect.In the present invention, described mixture is preferably the described ionogenic aqueous solution, and in the described aqueous solution, those of ordinary skill in the art can be according to the amount of carbon source in pending the system reasonably required nitrate ion of compatibility and the amount of nitrite ion.In the present invention, the total mass concentration of described nitrite ion and/or described nitrate ion is preferably no more than 3000ppm; When the described aqueous solution comprises nitrate ion and nitrite ion, the total mass concentration of described nitrate ion and nitrite ion preferably about 25ppm between 500ppm, the mass concentration of described nitrite ion is preferably 1ppm ~ 50ppm, and the mass concentration of described nitrate ion is preferably 1ppm ~ 500ppm;
Nitrate anion and nitrite ion can any suitable form join in pending system.For example, the nominal price counter ion of nitrate anion and nitrite ion is not key factor, as long as after suitable nitrate and nitrite are added, nitrate ion and nitrite ion can play corresponding effect.At present, from the viewpoint of economy and raw material supply, sodium salt or calcium salt are proved to be more favourable.But other nominal price counter ions also can be used as ammonium salt etc.In addition, joining the compound that can produce nitrite ion or nitrate ion in water solution system also can use.
The present invention to described by described denitrifying microorganism, aqueous carrier and non-positro acceptor are incorporated into the reservoir rock stratum under anaerobic environment condition, described reservoir rock stratum is dissolved, and the mixture that preferably makes described denitrification Thiobacillus, described aqueous carrier and described non-positro acceptor form is buffered to pH value and approaches 6.5;
By described denitrifying microorganism, aqueous carrier, be incorporated into behind the reservoir rock stratum under anaerobic environment condition with non-positro acceptor, under the condition of elementary sulfur and/or sulfur-containing compound existence, described denitrifying microorganism is by described non-positro acceptor reduction, and produce sulfuric acid, thereby and sulfuric acid has to reservoir rock the release that corrosion is easy to oil.The present invention does not have special restriction to the source of described elementary sulfur and sulfur-containing compound, for reservoir rock stratum itself that contain elementary sulfur and/or sulfur-containing compound, can add wherein elementary sulfur and/or sulfur-containing compound again; For the reservoir rock stratum of not containing elementary sulfur and/or sulfur-containing compound, the present invention preferably includes elementary sulfur and/or sulfur-containing compound is incorporated into the step in reservoir rock stratum, and described sulfur-containing compound is preferably selected from thiosulfate, four sulphur hydrochlorate or sulfide;
In order to provide nutriment to denitrifying microorganism, the method of microbe oil production provided by the invention preferably also comprises the step that phosphate compounds is incorporated into described reservoir rock stratum, the present invention does not have special requirement to the addition of described phosphate compounds, can meet microorganism to the nutraceutical needs of phosphate; The order that the present invention introduces described phosphate compounds does not have special restriction, can before introducing, above-mentioned denitrifying microorganism, aqueous carrier and non-positro acceptor add, also can add with described denitrifying microorganism, aqueous carrier and non-positro acceptor simultaneously, can also after described denitrifying microorganism, aqueous carrier and non-positro acceptor inject, add again;
The method of microbe oil production provided by the invention preferably also comprises the step that metal nutritional agents is incorporated into described reservoir rock stratum, the present invention does not have special restriction to the addition of described metal nutritional agents, can meet the requirement of described microorganism to metal nutritional agents; The present invention does not have special requirement to the kind of described metal nutritional agents, adopts metal nutritional agents well known to those skilled in the art; The order that the present invention introduces described metal nutritional agents does not have special restriction, described metal nutritional agents can be added under random order;
The method of microbe oil production provided by the invention preferably also comprises the step of a kind of nitrogenous source being introduced to described reservoir rock stratum, and the present invention does not have special restriction to the addition of described nitrogenous source, can meet the vital movement needs of microorganism; The present invention does not have special restriction to the kind of described nitrogenous source, adopts the kind of nitrogenous source well known to those skilled in the art, and in the present invention, described non-positro acceptor both can be used as electron acceptor, can be used as again the nitrogenous source of microorganism simultaneously;
Under the condition of described elementary sulfur and/or sulfur-containing compound existence, described denitrifying microorganism reduces described non-positro acceptor, and produces sulfuric acid, and described sulfuric acid has corrosion to reservoir rock, thereby is beneficial to the release of oil, has improved tar productivity; And can produce nitrogen as the reduction of the nitrate ion source of non-positro acceptor, and nitrogen is being oppressed the oil in described reservoir rock stratum, this compressing contributes to oil to depart from from reservoir rock stratum, has further improved tar productivity; In addition, in the present invention, described denitrifying microorganism, aqueous carrier and non-positro acceptor are incorporated into behind the reservoir rock stratum under anaerobic environment condition, the dissolved CO that produced of reservoir rock
2, this CO
2provide growth of microorganism necessary CO
2source, described reservoir rock and CO
2state in chemical balance, and microorganism removes CO
2can cause that reservoir rock further dissolves to maintain chemical balance.
The present invention preferably adopts the device shown in Fig. 1 to carry out microbe oil production, the microbe oil production apparatus structure schematic diagram that Fig. 1 provides for the embodiment of the present invention, wherein, 10 is water injecting pump, 20 is water injection well, 30 is reservoir rock stratum, 40 is oil extraction pump, the present invention adopts water injecting pump 10 will contain denitrifying microorganism, water, non-positro acceptor, and nutraceutical mixture is through water injection well 20, be injected into reservoir rock stratum 30, in stratum, a series of chemical agents with Oil Displacing Capacity will be produced thereupon, comprise acid, solvent, biopolymer, biosurfactant, and carbon dioxide and nitrogen, these chemical agents are by displacement oil and by oil extraction pump 40 extraction ground,
In method provided by the invention, the nitrogen of microorganisms and carbon dioxide increase petroliferous bed pressure, contribute to the exploitation of oil; Nitrate is electron acceptor, is again a kind of nitrogenous source of microorganism.Be accompanied by the formation of microbial product, nitrate will be reduced, and form nitrogen, can increase the pressure of petroliferous bed and improve recovery ratio; In addition, a kind of material of nitrite ion, nitric oxide or nitrous oxide that can provide also can be used as non-positro acceptor.Nitrous oxide and nitric oxide add after can be water-soluble with the form of gas.So the non-positro acceptor that the present invention adopts at least can comprise the material that these can provide nitrate anion or nitrite ion.
An important applied field of the present invention is to solve a series of serious problems that cause because of sulfate reducing bacteria in oil exploitation process.The sulfuration Hydrogen Energy that sulfate reducing bacteria produces causes the heavy corrosion of oil production equipment, greatly destroys the production capacity of oil extraction system, and reduces the market value of crude oil.Therefore, below discuss mainly for oil exploitation aspect.Certainly, as above-mentioned, the present invention is not limited to the application of oil exploitation aspect.The present invention can be applicable to remove hydrogen sulfide and/or take any field that sulfate reducing bacteria continuation generation hydrogen sulfide is target of controlling.For example, the present invention can be used for controlling petroleum storage tank, oil and natural gas pipeline, cooling tower, coal slurry pipeline, and the hydrogen sulfide in other moisture storage tanks and device.Also can be used for pit, refuse landfill, topple over facility, cofferdam and toward the system of underground flooding.
According to the first embodiment of the present invention, nitrate anion and/or nitrite ion are joined to content and/or the prevention sulfate reducing bacteria that need to reduce hydrogen sulfide and continue to generate in the system (system) of hydrogen sulfide.Add and can adopt in any suitable manner.For example, nitrate and nitrite can be configured to mixed solution or be made into separately the single aqueous solution, and then join in pending system and go with intermittence or mode continuously.The concrete method of implementing depends on pending system.For example, if only process a bite individual well, so disposable injection (may reach 3 days) nitrate and/or nitrite may be the most easily.If pending system is whole oil recovery system, it may be best adopting so operating procedure continuously.
Here there is a very important consideration, the nitrate anion adding, the amount of nitrite ion.Should say, the nitrate anion adding, the amount of nitrite ion be the large amount reproduction with promotion denitrifying microorganism enough, thereby consumes competitively the required carbon source of Growth of Sulfate Reducing Bacteria, and then has suppressed the conversion of sulfate to sulfide.Therefore, the addition of nitrate anion, nitrite ion depends on the amount that in pending system, carbon source exists.For example, if contain the acetate of 1000ppm in pending Aquo System, and before all by sulfate reducing bacteria, to be used for sulfate conversion be sulfide, so, nitrate anion, nitrite ion addition must be wide enough so that denitrifying microorganism can first consume the acetate of all 1000ppm before sulfate reducing bacteria utilizes acetate.Found that about 200ppm nitrate anion and about 100ppm nitrite ion realized expected effect.
The standard of stating with reference to the present invention and principle, those of ordinary skill in the art can be according to the amount of carbon source in pending the system reasonably required nitrate ion of compatibility and the amount of nitrite ion.In general, join nitrate ion in Aquo System and/or the total amount of nitrite ion and should be no more than 3000ppm.Or rather, the total amount that joins nitrate ion in Aquo System and nitrite ion about 25ppm between 500ppm, wherein the amount of nitrate ion about 1ppm between 500ppm and the amount of nitrite ion about 1ppm to 500ppm.Preferably above two kinds of ions respectively add 10ppm-200ppm.Ratio between nitrate ion and nitrite ion is generally about 50:1 to about 1:50, especially at about 1:10, arrives about 10:1.In field use field, the optimal ratio of nitrate anion and nitrite ion is about 5:1 to about 1:1.
Nitrate anion and nitrite ion can any suitable form join in pending system.For example, the nominal price counter ion of nitrate anion and nitrite ion is not key factor, as long as after suitable nitrate and nitrite are added, nitrate ion and nitrite ion can play corresponding effect.At present, from the viewpoint of economy and raw material supply, sodium salt or calcium salt are proved to be more favourable.But other nominal price counter ions also can be used as ammonium salt etc.In addition, joining the compound that can produce nitrite ion or nitrate ion in water solution system also can use.
As above mentioned, this nitrate/nitrite system is by promoting the growth of denitrifying microorganism to work.Conventionally, denitrifying microorganism and sulfate reducing bacteria are present in Aquo System jointly.If in pending Aquo System, these denitrifying microorganisms do not exist or quantity is inadequate, and that just need to together join they and nitrate/nitrite in pending Aquo System and go.
For obtain be originally present in system or joined afterwards the carbon back nutrients in system, denitrifying microorganism will be vied each other with sulfate reducing bacteria.That is to say, two kinds of microorganisms are competed for fighting for same nutrients.From thermodynamics and physiological angle, among the two, denitrifying microorganism is more favorably competitor.Therefore, the result of competition is that sulfate reducing bacteria can not get enough carbon sources and produces hydrogen sulfide.Lack carbon back nutrients and may not necessarily directly kill sulfate reducing bacteria, but can continue to produce hydrogen sulfide by inhibiting sulfate reduction bacterium.
Carbon back nutrients is acetate normally.They may just be present in pending system originally, may be also to join in system afterwards.Because sulfate reducing bacteria generally needs carbon back nutrients, grow and produce hydrogen sulfide, if there is active sulfate reducing bacteria to have and generating hydrogen sulfide, the carbon back nutrients that just exists denitrifying microorganism to grow required in this system so in an individual system.Therefore, generally speaking, in such system, do not need to add again extra carbon back nutrients.
But, if the problem of hydrogen sulfide is not due to the activity of current sulfate reducing bacteria, for example, these hydrogen sulfide are produced by the activity of the sulfate reducing bacteria in what past, and in system, there is no enough carbon back nutrients, so, in this system, just need to add carbon back nutrients to support the growth of denitrifying microorganism.
Similarly, if although in an individual system, do not have sulfate reducing bacteria generating hydrogen sulfide at present, likely in the impact that has in the future sulfate reducing bacteria.As a kind of preventative processing, thereby can add nitrate/nitrite and denitrifying microorganism as required to hinder the activity of sulfate reducing bacteria in the future.In this case, a kind of carbon back nutrients may together inject to promote with denitrifying microorganism the growth of denitrifying microorganism, thus avoid may occurring future produce the phenomenon of hydrogen sulfide because of sulfate reducing bacteria.
Therefore, the present invention can be used for processing the system have sulfate reducing bacteria generating hydrogen sulfide, also can process the system that contains the hydrogen sulfide that the activity due to the sulfate reducing bacteria in past produces, and the following system that may contain sulfate reducing bacteria.The denitrifying microorganism existing in system, nitrate and nitrite not only can be eliminated any hydrogen sulfide having generated but also can prevent following sulfate reducing bacteria to generate hydrogen sulfide.
Except acetate, the carbon source in system comprises the carbon back nutrients of any known denitrifying microorganism.For example, simple hydrocarbon can be used as the nutrients of denitrifying microorganism as Krebs intercycle body, malonic acid, citric acid, lactic acid, ethanol, glycerine etc.Most of oil fields are all contained denitrifying microorganism and are grown required carbon source as acetate, propionate and butyrate.Meanwhile, in the production management process in oil field, usually can supplement the compound as nutrition composition.But, also may add more carbon-source cpd and other nutrients as balanced in nutrition to guarantee in phosphate, promote the growth of denitrifying microorganism.
The nitrate growth that denitrifying microorganism utilizes carbon back nutrients and adds.Add nitrite from thermodynamics aspect, contribute to the growth of denitrifying microorganism and consumed carbon source.In addition, nitrite can react with the hydrogen sulfide having generated, and reduces immediately the amount of hydrogen sulfide.Nitrite can also further produce hydrogen sulfide by inhibiting sulfate reduction bacterium.
Denitrifying microorganism is bacterium.For the system of a field use, these bacteriums are origin often, is originally just present in the system of oil field.If not, also can be before adding nitrate anion and nitrite ion, add denitrifying microorganism (denitrifying bacteria) afterwards or simultaneously.Its mode that adds can adopt batch (-type) (Aquo System is only contacted once with the compound that nitrate anion and/or nitrite ion maybe can produce these ions) or continous way (compound that makes Aquo System maybe can be produced these ions by nitrate anion and/or nitrite ion is processed repeatedly).Denitrifying bacteria is understood by professional person and is described to some extent in relevant books, for example " prokaryotes: the growing environment of bacterium, separated and identification handbook ”，Juan 1-4(Springer-Verlag publishing house, 1981).These bacteriums utilize nitrate or nitrite as final electron acceptor, by breathing its acquisition energy, just look like that animal breath oxygen is the same.Have some bacteriums can be by nitrate transformation nitrogen other be converted into ammonia.Although denitrifying bacteria and sulfate reducing bacteria utilize same carbon source/energy, but as previously mentioned, denitrifying bacteria can more effectively obtain carbon source/energy in competition, makes sulfate reducing bacteria cannot obtain carbon source/energy, thus inhibiting sulfate reduction bacteria growing and later formation sulfide.Although nitrite or nitrate can adopt respectively, the two adds together and has beat all cooperative effect.Adding together needs the amount of the two all can be smaller.As previously mentioned, add the amount of ion to depend on that some parameters of pending system comprise carbon source level, hydrogen sulfide levels, current sulfate reducing bacteria level etc.The principle of narrating according to the present invention, relevant speciality personnel can determine the amount that will add ion.Here need to consider that allow denitrifying bacteria use up all carbon sources also needs to eliminate all hydrogen sulfide having generated in order to avoid sulfate reducing bacteria produces hydrogen sulfide simultaneously.
Another benefit that the growth of denitrifying bacteria brings is that they can utilize remaining hydrogen sulfide in system, and the part of not reacting with nitrite, as nutrient.Denitrifying microorganism has consumed the hydrogen sulfide being present in Aquo System as nutritional agents, thereby this effect will further reduce amount and the harmful effect thereof of hydrogen sulfide in this Aquo System.
In addition, the growth of denitrifying microorganism also contributes to the release of oil.The oil machine reason of releasing of this microbe oil production technique (MEOR) comprises water blockoff, generates biopolymer and biosurfactant, produces nitrogen and carbon dioxide, changes change pH values etc.That is to say, denitrifying bacteria and metabolite thereof are realized the release of oil by above-mentioned mechanism, and wherein plugging function occurs in high permeability zones, and water filling is preferentially guided to hyposmosis district, improve oil displacement efficiency.
Therefore, in Aquo System, the growth of denitrifying bacteria can not only be eliminated the hydrogen sulfide having generated, the further formation of prevention hydrogen sulfide, and also this Aquo System also can be used for carrying out microbe oil production.Adopt nitrate ion and/or nitrite ion to Aquo System process should be before oil recovery process be carried out or during, thereby make hydrogen sulfide can not enter into subsurface deposit.The present invention is used for improving oil recovery by this Aquo System.For example, treated Aquo System is injected to oilbearing stratum oil is formed to displacement.
The system that contains denitrifying microorganism only has less or there is no hydrogen sulfide.So, oil just can, by acidifying, can even finally not abandoned oil field because seriously corroded increases face cost yet.Therefore, such system can more effectively be recovered the oil.In addition,, owing to there is no or only having less hydrogen sulfide, just can not react and generate ferrous sulfide with iron because of hydrogen sulfide.Ferrous sulfide can cause oil field blockage problem.
As the more optimization method of first embodiment of the invention, molybdate will together add with nitrite and nitrate.Molybdate can kill or inhibiting sulfate reduction bacterium.Yet, add the amount needs appropriateness of molybdate in order to avoid kill or suppress denitrifying bacteria.Meanwhile, in order to obtain the effect of desirable inhibiting sulfate reduction bacterium, the needed amount of molybdate together adding with nitrate, nitrite is than the independent molybdate much less of using.
Therefore, molybdenum acid ion, nitrite anions are added together with nitrate ion more superior than independent use molybdenum acid ion.If use separately, need the amount of molybdenum acid ion to be often greater than 3000ppm.If together add with nitrate anion, nitrite ion, need the amount of molybdenum acid ion only to have an appointment 1ppm to 250ppm, preferably about 2ppm is to 100ppm, and preferably about 5ppm is to 50ppm.The form that molybdenum acid ion can molybdate maybe can produce the compound of molybdenum acid ion adds.From the viewpoint of economy and availability, can use sodium molybdate and lithium molybdate.
According to the second embodiment of the present invention, except adding nitrate ion and nitrite ion and optionally using molybdate, only use nitrite and molybdate and do not add nitrate, for can effectively eliminating the hydrogen sulfide in Aquo System and/or preventing that sulfate reducing bacteria forms hydrogen sulfide from now on.
Except not adding nitrate, the second embodiment and the first embodiment are similar.In this embodiment, not needing to add nitrate ion, is because the growth of denitrifying microorganism can rely on nitrate or nitrite.The addition of nitrite ion generally arrives about 500ppm at 1ppm.According to principle of the present invention, thereby person skilled can be determined and need to add the growths that nutraceutical amount promotes denitrifying bacteria based on nutrient in Aquo System and ion concentration how much.
As previously mentioned, nitrite can react with the hydrogen sulfide having generated, and reduces immediately the amount of hydrogen sulfide.Therefore, the addition of nitrite is the function of the amount of the hydrogen sulfide that generated.
Similar to the first embodiment, a very important feature is exactly the growth that promotes denitrifying bacteria.Nitrite ion, carbon source and other nutrients have promoted this growth.Once denitrifying microorganism appearance, they will seize the required carbon source of sulfate reducing bacteria in competition, thereby prevent that sulfate reducing bacteria from generating hydrogen sulfide.
Similar to the first embodiment, perhaps denitrifying bacteria and carbon source exist in pending system, perhaps need additionally to add.In addition, nitrite ion and molybdenum acid ion can be any desirable form intermittently or continuity ground add.
Add appropriate molybdenum acid ion to kill or inhibiting sulfate reduction bacterium, but can't have a negative impact to denitrifying microorganism.This quantity is general as said in the first embodiment, and about 1ppm is to about 250ppm, preferably about 2ppm to 100ppm, preferably about 5ppm to 50ppm.
Nitrite anions and molybdenum acid ion can contain the system that active sulfate reducing bacteria is producing the system of hydrogen sulfide or having sulfate reducing bacteria in the future with dealing with, or the system that processing contains hydrogen sulfide is beneficial to remove hydrogen sulfide.This processed system can be applied to oil recovery process, as system processed in the first embodiment.
Nitrite ion and molybdenum acid ion have unexpected synergy, and the smaller amounts in the time of only need to be than its independent use, just can suppress the generation of hydrogen sulfide and remove any existing hydrogen sulfide.For example, according to a specific embodiments of the present invention, approximately there is 1ppm to have 1ppm to be added in Aquo System to about 250ppm molybdenum acid ion to the nitrite ion peace treaty of about 250ppm.The present invention will illustrate by following embodiment.Should say, this example is only for purpose of illustration, and should not be construed as limiting this invention.
The invention provides a kind of method of microbe oil production, the method comprising the steps of: by (a) denitrifying microorganism, (b) aqueous carrier, (c) non-positro acceptor is incorporated into the reservoir rock stratum under anaerobic environment condition, make denitrifying microorganism under the condition of elementary sulfur and/or sulfur-containing compound existence, by described non-positro acceptor reduction, and produce sulfuric acid, thereby and sulfuric acid has to reservoir rock the release that corrosion is easy to oil.Method provided by the invention is incorporated into denitrifying microorganism, aqueous carrier and non-positro acceptor in reservoir rock stratum, thereby under elementary sulfur and/or the condition containing compound existence, described denitrifying microorganism is by described non-positro acceptor reduction, reduce the amount of hydrogen sulfide in Aquo System, and can prevent the further formation of hydrogen sulfide, and can suppress the growth of the sulfate reducing bacteria that may exist in Aquo System, and produce sulfuric acid, be easy to the release of oil, thereby improved the acquisition rate of oil.Experimental result shows, method provided by the invention is the growth of inhibiting sulfate reduction bacterium effectively, thereby reduce and prevented the content of hydrogen sulfide in Aquo System, make in a bite typical case well to have every day that 15kg limestone is dissolved nearly, this solubility is equivalent to dissolve every year 2-3 ton limestone, has absolutely proved the effect of the Microbial Enhanced Oil Recovery extracting according to the present invention.In order to further illustrate the present invention, below in conjunction with embodiment, method and the microbe oil production method of the hydrogen sulfide in prevention provided by the invention and reduction Aquo System are described in detail, but they can not be interpreted as to limiting the scope of the present invention.
Embodiment 1
Data in following form are by laboratory reaction bottle test gained.Utilize the sulfate reducing bacteria synthetic media assay flask of a series of sterilizings to inoculate the microorganism of constant number, the i.e. sulfate reducing bacteria of constant number and denitrifying microorganism.The chemical agent to be tried that adds variable concentrations in different assay flask (sample).The growth of sulfate reducing bacteria judges with the generation of sulfide, and in other words, sulfate reducing bacteria is not grown can be by not having the generation of sulfide to judge.These the results are shown in following table.
Sample 1-6 is comparative sample, from these samples, can find out, adds separately nitrate ion or nitrite ion, and its concentration 100ppm or 200ppm can not stop Growth of Sulfate Reducing Bacteria, and 500ppm could effectively control its growth.
Sample 7,8,9 and 13 is in the first embodiment of the present invention.Can find out, adopt nitrite anions and nitrate ion simultaneously, even if reduce to 100ppm or 50ppm can stop Growth of Sulfate Reducing Bacteria, such result be use separately nitrate or nitrite institute inaccessiable.
Sample 9 is the comparative examples that adopt nitrate and molybdate.This combination can not stop Growth of Sulfate Reducing Bacteria.Yet, according to the second embodiment of the present invention, in embodiment 10-13, adopt the mixture of molybdate and nitrite can effectively stop the growth of sulfate reducing bacteria.
Example is below for utilizing a kind of method of the product raising oil recovery of denitrifying microorganism that illustrative explanation is provided.
Oil is usually present in underground reservoir rock stratum, clastic reservoir for example, and carbonate reservoir, in Potential Volcanic Reservoir etc.In these rock stratum, most of oil are included among the small hole seam that rock and the space that leads to wellhole be separated by.Yet.Have found that, acid has corrosion to rock, can make these hole seams be communicated with, and the oil of trapping can be flushed out effectively.This connection has increased the oil recovery the oil well from being commonly referred to be exhausted.
According to the present invention, acid utilizes microorganism to produce in original place, and this microorganism is exactly an acidic kind of energy in denitrifying microorganism.Thiobacillus and other acid-producing bacterias are never considered to can be applicable to microbe oil production process, and this is because mostly they are aerobic bacteria, that is needs oxygen as electron acceptor, thereby, be unsuitable for surviving under the anaerobic environment of oil well.
Yet, have now found that, if adopt non-positro acceptor, as nitrate, nitrite, nitric oxide or nitrous oxide, just can make acid-producing bacteria deacclimatize the environment of subterranean strata in microbe oil production (MEOR) process as Thiobacillus.Therefore.The invention provides a kind of method of microbe oil production.This method is that acid-producing microorganisms and non-positro acceptor are introduced and be defined as among the subsurface rock stratum (as reservoir rock stratum) of anaerobic environment, these microorganisms are reduced this non-positro acceptor, and produce sour, thereby dissolve part lithostratigraphy, the oil-containing hole seam of isolation is mutually communicated with.
The stratum of reservoir rock described in the present invention can be clastic reservoir, carbonate reservoir, Potential Volcanic Reservoir, and clastic, carbonate rock, lava and argillaceous rocks mixing reservoir etc.The present invention especially comprises that for improving carbonato rock (carbonate rock) oil recovery of limestone-sandstone formation of limestone and mixing is effective especially.The present invention also can be applied to underground shale-lime rock stratum, although its validity depends on rock permeability to a certain extent.
According to the present invention, various microorganisms can be for producing acid to dissolve the relevant rock stratum in subsurface formations.Adopted in a preferred embodiment denitrification Thiobacillus.The discussion of relevant Thiobacillus, please refer to the < < prokaryotic micro-organisms of Kuenen and Tuovienen and learn > > (Spriger--Verlag) first volume (second portion) 1023-36 page, the present invention is incorporated herein by reference these contents.Representative in applicable multiple denitrification Thiobacillus kind of producing sour object is T. denitrifier (T.denitrificans).As Kuenen and Tuovien, at 1023-36 page, pointed out, T. Thiobacillus (T.thioparas) also can denitrification, because should be also microorganism applicable in the present invention.
After the obvious exhaustion of oil reservoir, subsurface deposit needs often to adopt water drive to help oil extraction with supplementary pressure.The microorganism that the method according to this invention can adopt needs injects into well together with driven water-replacing with non-positro acceptor.The driven water-replacing has here played liquid carrier.Another kind of way is that microorganism and non-positro acceptor also can inject into well respectively with driven water-replacing.Under latter event, need to adopt the another kind of liquid that is different from driven water-replacing as carrier.
Table 1
* can be: Na
2s, Na
2s
2o
3, S
0, Na
2s
4o
6, H
2s, SO
3, or SCN
-
The culture medium that table 1 is described comprises sulfide or elementary sulfur, ammonium nitrate, potassium dihydrogen phosphate, carbonate rock (as limestone) and the water of microorganism, reduction-state.The reactant that the sulfide of reduction-state or elementary sulfur dissolve the sulfuric acid of limestone as the energy (sulphur source) and the generation of microorganism.Except elementary sulfur, following any sulfur-containing compound can be as sulphur source: Na
2s, Na
2s
2o
3, Na
2s
4o
6, H
2s, SO
3, or SCN
-.
When limestone dissolves, produced CO
2.And this carbon dioxide provides these growth of microorganism necessary CO
2source.Here CO
2in chemical balance, described microorganism removes CO with reservoir rock
2, can cause that described reservoir rock further dissolves to maintain chemical balance, as following equation, represent (with carbonate rock (CO
3 =) be example):
The dissolution of carbonate rock provides the benefit of four aspects for improving oil recovery.One, dissolution buffering microorganism, water and the nitrate ion mixture of carbonate are in constant pH value approximately 6.5.And this pH value that bacterium grows best as T. denitrifier (T.denitrificans) just.Its two, sulfuric acid is neutralized because of the dissolving of limestone.Its three, as aforesaid equation, point out, these microorganisms have consumed CO from mixture
2and formation cell carbon, the dissolving of limestone is not only due to limestone and sour reacting, and because CO
2generation for maintaining this balance, be necessary.In other words, whenever a carbon becomes in cell carbon, another carbonate will enter in mixed solution.Its four, CO
2the generation of gas has increased the pressure of oil in oil well, thereby further contributes to oil output.
If oil acidifying, some oil well may contain enough sulfide to meet the needs of microorganism to sulphur.Most of bittern contains the trace meter that concentration is quite high can meet the needs of typical denitrifying microorganism to trace meter.Therefore, under ideal conditions, the composition that need to be injected in well has nitrate, phosphate and microorganism.
The amount that limestone dissolves is unimportant, and this is just likely to affect huge because only open a mobile duct of profit.Except causing that supercharging and limestone dissolve, microorganism is also optionally stopped up the duct of fully rinsing, and this contributes to dissolve more duct.
Table 2 has been enumerated with different microorganisms and different energy source dissolving situation that pulverized and limestone solid to table 5.In the thin row embodiment of these forms, bacterium used is all T. denitrogenation Pseudomonas (T.denitrificans), they are all stored in American type culture collection (ROEKVILLE, MD.), it is numbered ATCC25259 and ATCC23642, and field separator, comprise the thermophilic separator of moderate.In table, be numbered " BuckTail " and " Meadow Creek " and enumerated the situation that adopts the solubility test that the water that contains origin denitrifying microorganism from these two places of Idaho does.
Table 2 has also been enumerated the acid that adopts 1N hydrochloric acid rather than generated by bacterium and has been dissolved the caused dissolution of limestone.By the resulting dissolving result of hydrochloric acid, show that the limestone sample of about 12-17% is to form by being insoluble to sour material.
Table 2
Table 3
Table 4
Table 5
Under the condition of relatively optimizing in other physical property of culture medium condition, nutritional agents concentration, culture medium etc., the limestone of every liter of solvable 1 grammes per square metre of terminating an agreement of the culture medium that contains T. denitrogenation Pseudomonas (T.denitrificans).If every day is on average to 15000 liters of stratum water fillings.This means in a bite typical case well has that 15kg limestone is dissolved every day nearly.This solubility is equivalent to dissolve every year 2-3 ton limestone, has absolutely proved the effect of the Microbial Enhanced Oil Recovery extracting according to the present invention.
As seen from the above embodiment, the invention provides a kind of method of microbe oil production, the method comprising the steps of: by (a) denitrifying microorganism, (b) aqueous carrier, (c) non-positro acceptor is incorporated into the reservoir rock stratum under anaerobic environment condition, makes denitrifying microorganism under the condition of elementary sulfur and/or sulfur-containing compound existence, by described non-positro acceptor reduction, and produce sulfuric acid, thereby and sulfuric acid has to reservoir rock the release that corrosion is easy to oil.Method provided by the invention is incorporated into denitrifying microorganism, aqueous carrier and non-positro acceptor in reservoir rock stratum, thereby under elementary sulfur and/or the condition containing compound existence, described denitrifying microorganism is by described non-positro acceptor reduction, reduce the amount of hydrogen sulfide in Aquo System, and can prevent the further formation of hydrogen sulfide, and can suppress the growth of the sulfate reducing bacteria that may exist in Aquo System, and produce sulfuric acid, be easy to the release of oil, thereby improved the acquisition rate of oil.Experimental result shows, method provided by the invention is the growth of inhibiting sulfate reduction bacterium effectively, thereby reduce and prevented the content of hydrogen sulfide in Aquo System, make in a bite typical case well to have every day that 15kg limestone is dissolved nearly, this solubility is equivalent to dissolve every year 2-3 ton limestone, has absolutely proved the effect of the Microbial Enhanced Oil Recovery extracting according to the present invention.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (16)
1. the method for a microbe oil production, the method comprising the steps of: by (a) denitrifying microorganism, (b) aqueous carrier, (c) non-positro acceptor is incorporated into the reservoir rock stratum under anaerobic environment condition, make denitrifying microorganism under the condition of elementary sulfur and/or sulfur-containing compound existence, by described non-positro acceptor reduction, and produce sulfuric acid, thereby and sulfuric acid has to reservoir rock the release that corrosion is easy to oil.
2. method according to claim 1, is characterized in that, described non-positro acceptor is selected from following ion gun: one or more in nitrate ion source, nitrite ion source, nitric oxide and nitrous oxide.
3. method according to claim 2, is characterized in that, described non-positro acceptor is a kind of nitrate ion source.
4. method according to claim 1, is characterized in that, described elementary sulfur and/or sulfur-containing compound are contained in described reservoir rock stratum.
5. method according to claim 1, is characterized in that, also comprises elementary sulfur and/or sulfur-containing compound are incorporated into the step in reservoir rock stratum.
6. method according to claim 1, is characterized in that, also comprise described elementary sulfur and/or sulfur-containing compound are incorporated in reservoir rock stratum, and this sulfur-containing compound is to be selected from thiosulfate, four sulphur hydrochlorate or sulfide.
7. method according to claim 1, is characterized in that, described denitrifying microorganism is denitrification Thiobacillus.
8. method according to claim 7, is characterized in that, the described dissolving to reservoir rock stratum, and the mixture that makes to consist of described denitrification Thiobacillus, described aqueous carrier and described non-positro acceptor is buffered to pH value and approaches 6.5.
9. method according to claim 1, is characterized in that, also comprises the step that phosphate compounds is incorporated into described reservoir rock stratum, and the addition of this phosphate compounds meets microorganism to the nutraceutical needs of phosphate.
10. method according to claim 1, is characterized in that, driven water-replacing is as described aqueous carrier.
11. methods according to claim 1, is characterized in that, described introducing step comprises the mixture that contains described microorganism, described non-positro acceptor and described aqueous carrier and driven water-replacing are injected into respectively in described reservoir rock stratum individually.
12. methods according to claim 1, is characterized in that, described reservoir rock stratum comprises clastic reservoir, carbonate reservoir, Potential Volcanic Reservoir, and clastic, carbonate rock, lava and argillaceous rocks mixing reservoir.
13. methods according to claim 1, is characterized in that, have also comprised the step that metal nutritional agents is incorporated into described reservoir rock stratum, and the amount of this metal nutritional agents meets the requirement of described microorganism to metal nutritional agents.
14. according to the method described in claim 1 or 3 any one, it is characterized in that, has also comprised the step of a kind of nitrogenous source being introduced to described reservoir rock stratum.
15. according to the method described in claim 1 or 3 any one, it is characterized in that, the reduction of described nitrate ion source produces nitrogen, and nitrogen is being oppressed the oil in described reservoir rock stratum, and this compressing contributes to oil to depart from from reservoir rock stratum.
16. according to the method described in claim 1 or 3 any one, it is characterized in that described reservoir rock and CO
2in chemical balance, and described microorganism removes CO
2can cause that reservoir rock further dissolves to maintain chemical balance.
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