CN103080468A

CN103080468A - A method for treatment of subterranean sites adjacent to water injection wells

Info

Publication number: CN103080468A
Application number: CN2011800434185A
Authority: CN
Inventors: A.W.阿尔索普; R.D.法伦; S.C.杰克逊
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 2010-07-09
Filing date: 2011-07-08
Publication date: 2013-05-01
Also published as: BR112013000479A2; GB201300295D0; MX2013000292A; RU2013105468A; WO2012006489A2; NO20130128A1; CA2804607A1; CO6650382A2; WO2012006489A3; GB2497212A; CA2804607C

Abstract

A method to improve the effectiveness of MEOR or bioremediation processes has been disclosed. In this method toxic chemicals accumulated in subterranean sites adjacent to the water injection wells are either dispersed or removed prior to introduction of microbial inocula for enhanced microbial oil recovery or bioremediation of these sites.

Description

For the treatment of with the method in the contiguous underground site of water injection well

The application requires to submit to and the separately whole American National application 12/833,018,12/833,020,12/833 that is incorporated herein by reference on July 9th, 2010 separately, 039,12/833,041,12/833,043,12/833,050,12/833,058 and 12/833,070 interests.

Invention field

The oil that the present invention relates to the microorganism enhancing in underground pollution site reclaims and the bioreediation field.Particularly, it related to before the oil recovery or bioreediation of introducing microbial inoculant thing for the microorganism enhancing in these sites, the method for the cytotoxic chemical goods of accumulating in the underground site of processing and water injection well vicinity.

Background of invention

The elemental traditional oils recovery technology of only utilizing the oil well site to exist only allows to reclaim the smaller portions crude oil that is present in the storage tank farm.The oil well site refers generally to well wherein and has been drilled into any position in the oil-containing subsurface rock, and purpose is to produce oil by that subsurface rock.Storage tank farm refers generally to the deposition of subterranean oil.Additional recovery method for example water flood be used for forcing oil by underground site towards producing well, thereby and improve recovery (Hyne, the N.J. of crude oil, 2001, " Non-technical guide to petroleum geology, exploration, drilling; and production ", the 2nd edition, Pen Well Corp., Tulsa, OK, USA).

In order to satisfy the global demand to the rising of energy, need further to increase the crude oil production from storage tank farm.Be used for to strengthen the technology of replenishing in addition that the oil from storage tank farm reclaims and be called microorganism and strengthen oil and reclaim (Microbial Enhanced Oil Recovery) (MEOR), such as U.S. Patent number 7,484, described in 560.The potential MEOR that strengthens the cost effective ways that oil reclaims that becomes relates to the microorganism that stimulates native country storage tank farm microorganism or will select especially and injects in the storage tank farm metabolic effect that the oil that causes improving with generation reclaims.

Produce oil and gas by underground oil storage and require to install on the surface of storage tank farm or in the underground site plurality of devices and pipeline, it contacts with corrosive fluid in the field use with natural gas.Therefore, oil reclaims and is provided for the water of water injection well and transports from the oil of producing well and the integrality of water equipment needed thereby being promoted by preservation.Therefore, corrosion can be the significant problem in the petroleum industry, because cost and the downtime relevant with the replacement of the equipment that is corroded.

Produce hydrogen sulfide (H ₂S) SRB is one of the main contributions person of the corrosion of ferrous metal surface and oily reclaimer.These microorganisms can cause turn sour, Corrosion blockage, therefore and can have negative effect to MEOR or bioreediation process.Bioreediation refers to use the microorganism removing from the process of oil spilling or other pollutants in soil surface or underground site.

For to anticorrosive, corrosion inhibitor is used for preserving water filling and the oily reclaimer of this type of well, described corrosion inhibitor is to reduce the rate of corrosion of metal or alloy and is chemicals or the reagent of toxicity usually for microorganism.In practice of the present invention, water injection well be by its with water take out downwards that pump is used for that pressure is kept in the produce oil bank, water filling or strengthen the well that oil reclaims.The important kind of corrosion inhibitor comprises that compound for example: inorganic and organic corrosion inhibitor.For example, Organophosphonate, organonitrogen compound, organic acid and salt thereof and ester (Chang, the people such as R. J., Corrosion Inhibitors, 2006, Specialty Chemicals, SRI Consulting).

U.S. Patent Application Publication No. 2006/0013798 has been described and has been used bi-quaternary ammonium salt as the metal surface of corrosion inhibitor with preservation and fluid contact, to prolong the life-span of these capital assets.

U.S. Patent number 6,984,610 have described that application, pressure by acid fractures and based on the microemulsified of acid, have removed the greasy filth of artesian well cutting, the probing of surperficial oil well and production equipment and probing body refuse to be used for strengthening the method that oil reclaims.

WO2008/070990 has described and used for example oil well preliminary treatment of methyl ethyl ketone, methyl propyl ketone and methyl tertiary butyl ether of pretreating reagent in water filling, reclaims to improve oil.Mechanism for example changes the oil viscosity in the bank and makes that heavy oil is active to be attributed to this method.

US2009/0071653 has described and has used surfactant, mordant, anticaking agent and grinding agent with prevention or remove the capacity that fluid film on treatment facility accumulates to increase well.

Research points out that for example the chemicals of corrosion and scaling, microbial activity and formation of foam or the long-term interpolation of reagent do not cause it with the accumulation of enough high concentrations for the undesirable event of water supply for the control water injection well, adversely to affect the microorganism (Carolet that in MEOR, uses, J-L. in:Ollivier and Magot edit, " Petroleum Microbiology ", the 8th chapter, 165 pages of the 164th –, 2005, ASM press, Washington, DC).

Yet the vigor of the microorganism of using in MEOR or bioreediation process is problem.Possible desired modifications MEOR or bioreediation are processed, thereby so that the vigor of the microorganism of using kept from start to finish in these processes, thereby so that MEOR or bioreediation process become more effective.

Summary of the invention

Present disclosure relates to the method that is used for improving the validity of MEOR or bioreediation process by the contiguous underground site of detoxifcation and oil well, and wherein before the required microbial inoculant of MEOR or bioreediation, described well was before processed with corrosion inhibitor.

In one aspect, the present invention is the method that comprises following in-order step:

A) with the underground site of antidote processing with the area of water injection well vicinity; With

B) be added on the inoculum that microorganism strengthens microorganism useful in the oil recovery in water injection well, wherein said microorganism comprises following one or more species: Comamonas ( Comamonas), fusobacterium ( Fusibacter), extra large bacterium belong to ( Marinobacterium), stone robe Pseudomonas ( Petrotoga), genus Shewanella ( Shewanella), pseudomonas ( Pseudomonas), vibrio ( Vibrio), stone robe Pseudomonas, Soxhlet Pseudomonas ( Thauera) and product microballoon Caulobacter ( Microbulbifer);

Wherein at least a corrosion inhibitor and catabolite thereof before (a) processes, if present, absorbed in the described area, and be accumulate to for microorganism and strengthen the virose concentration of microorganism tool of using in the oily removal process, thereby formed the toxicity area.

The accompanying drawing summary

Fig. 1 be water injection well and with the diagram in the contiguous underground site of water injection well.(1) be that injected water enters the stream in the casing (7), (2 and 3) are lithospheres, (5) be perforation in the sleeve pipe, (4) be crack in the lithosphere, (6) be the rock aspect that is caused by well boring, (7) be casing, (8) are and a side of the axisymmetric water-bearing zone of Injection Well, are shown by the dotted line frame in the lithosphere (3).

Fig. 2 is the schematic diagram for the model system of simulation toxicity area formation.(9) be elongated tubular; (10) be the pressure vessel of constraint tubule; (11 and 12) are the relative terminal of pressurizing vessel; (13) be pump; (14) be the feed supplement bank; (15) be water inlet for pressure vessel; (16) be back pressure regulator; (17) be that pressure-air is supplied with; (18) be the interior tubule of Bonding pressure container and the inlet fitting of pump and pressure sensor; (21) be the outlet accessory of the downside of the interior tubule of Bonding pressure container and back pressure regulator and differential pressure pick-up; (19) be the difference sensor; And (20) be absolute pressure transducer.

Fig. 3 has described the titration of the sand of amine coating;

The amine of sand in solution that representative is coated with from amine, and Represent the first derivative (centered difference) of titration curve.

Fig. 4 has described with 1N HCl titration bittern and sand grains;

Representative has the pH of the bittern #1 of 10 gram sand grains; Represent the only pH of bittern #1;

Figure 2011800434185100002DEST_PATH_IMAGE010

Representative has the pH slope of the bittern #1 of 10 gram sand grains; And

Represent the only pH slope of bittern #1.

Fig. 5 has described bittern and the sand grains that is polluted by amine with 10% nitric acid titration;

The amine concentration that representative is observed in solution for given pH.

Fig. 6 has described with 10% acetic acid titration bittern and core sand; The amine concentration that representative is observed in solution for given pH.

Detailed Description Of The Invention

In one aspect, the present invention is the method for detoxifcation corrosion inhibitor and catabolite (if present) thereof, and it is accumulated in the underground site that the water injection well with the oil well site is close to.The applicant has found to reclaim processing aid by oil, and for example corrosion inhibitor for example can be in the area accumulation adjacent with water injection well, and builds up to the concentration for the Ecotoxicology that uses in MEOR or bioreediation.Use in this article such as this term, " detoxifcation " water injection well site means to remove or reduce the toxicity for microorganism that is caused by corrosion inhibitor and catabolite thereof, with described microbial growth and the activity that allows to use in MEOR or bioreediation.

For the purposes of the present invention, term " toxicity area " refers to comprise for example underground site toxic concentration and that water injection well is contiguous of corrosion inhibitor or its catabolite of reagent, and described reagent has detrimental effect to microbial growth and the metabolic activity that uses in MEOR and/or bioreediation.These reagent can be in rock sand grains, rock, clay and/or the oil combination of being combined with rock, produce the toxicity area.Use in this article such as this term, toxic agent is adversely to affect the microbial growth that uses in MEOR and/or bioreediation and any chemistry or the biological reagent of metabolic function.

Fig. 1 is the schematic diagram with the contiguous underground site of water injection well.Injected water (1) flows in the casing (7), and it is in the well boring (6) of probing by lithosphere (2 and 3).Between the face (6) of casing (7) and the lithosphere that caused by well boring (5), there is breach.Lithosphere (2) representative is at the upper and lower impermeable rock of permeable rock (3) that holds or entrap oil.Injected water (1) flows to casing (7), and through the perforation (5) in the sleeve pipe (7) and enter in the crack (4) in the permeable rock (3).This injected water flow through subsequently permeable stratum (3) and replace from the oil of the contiguous water-bearing zone (8) of well boring.(6) are radial stretches out from well boring with all directions in permeable stratum (3) in this area.Although the volume of the permeable rock (3) that is surrounded by dotted line (8) only illustrates in a side of well boring, in fact it be present on all sides of well boring.The underground site that this water-bearing zone representative is contiguous with water injection well.

The corrosion inhibitor that can be accumulate to for the level of the Ecotoxicology that uses in MEOR for example is together with its catabolite (if present): inorganic corrosion inhibitor is chlorine, hypochlorite, bromine, hypobromite and chlorine dioxide for example.The inorganic corrosion inhibitor of accumulation that is used for the other genotoxic potential of the corrosion that antagonism causes by SRB includes but not limited to: hydrazine, anthraquinone, phosphate, sodium sulfite and contain salt (Sanders and the Sturman of molybdic acid, chromium or zinc, the 9th chapter, the 191st page, in: " Petroleum microbiology " the 191st page, the same, and Schwermer, C. U. waits the people, Appl. Environ. Microbiol., 74:2841-2851,2008).

The organic compound as corrosion inhibitor that can accumulate to form the toxicity area comprises: alkynol, organic pyrrole, glutaraldehyde, tetrakis hydroxymetyl phosphonium sulfuric (THPS), two thiocyanates methacrylaldehyde, dodine hydrochloride, formaldehyde, chlorophenol, organic oxygen scavenger and multiple nonionic surface active agent.

Other organic corrosion inhibitor that can accumulate to form the toxicity area comprise but are not limited to: Organophosphonate, organonitrogen compound comprises primary, secondary, uncle or quaternary ammonium compound (hereinafter being called generically " amine "), organic acid and salt thereof and ester, carboxylic acid and salt thereof and ester, sulfonic acid and salt thereof.

The applicant has measured corrosion inhibitor and can be accumulated in the underground site (for example rock, clay, sandstone, loose sand grains or limestone) or on it or in the oil, described oil has been entrapped in the underground site of storage tank farm by absorption.The long-term interpolation of these chemicals cause its with the contiguous underground site of well in accumulation and toxicity area form, expection is used for the microbial inoculant thing that MEOR and/or bioreediation use has detrimental effect.

The model system that simulation toxicity area forms can be used for its effect to microbial survival of research.For example, the model system that is called tubule and use from the core sand in oil well site and fill can be set.As described herein can use compatible with the hydraulic pressure solution of crude oil or use pipe-line system, valve and the accessory setting of model system, it can stand applied pressure scope during process.For example by Cole Plamer(Vernon Hill, IL) and Serta(Boxborough, Mass) absolute pressure transducer, differential pressure pick-up and the back pressure regulator made be used for model system and be obtained commercially.

Model toxicity area can be used amine and/or amine blends solution and be washed away them and set up by filling pipe from the core sand of storage tank farm.Other corrosion inhibitors that are suitable for using in making up model can comprise Organophosphonate or anthraquinone or phosphate.Concentration for generation of the corrosion inhibitor in model toxicity area can be 0.01 to 100 PPM.

Relate to the cytotoxic chemical goods that use antidote degraded, desorb and/or disperse accumulation in model system or with the detoxifcation in toxicity area in the contiguous underground site of water injection well.Term " antidote " therefore refers to disperse or destroy cytotoxic chemical goods described herein and reagent and cause it for the nontoxic any chemicals of microorganism.

By finishing for any method that chemicals is introduced in the underground site, described method is that those skilled in the art are well-known with the toxicity area in the underground site that antidote is processed and water injection well is contiguous.Usually, the composition introducing of processing by containing antidote is used in the well of injected water (1) as shown in Fig. 1 diagram.The antidotes composition casing (7) of flowing through is by perforation (5) and enter in the crack (4) in the permeable stratum (3) in the water-bearing zone (8).This is the area contiguous with water injection well, and its Poisoning area can form and process by antidote.

The detoxifcation of the chemicals of accumulating in the toxicity area can realize with degradation agent.Use in this article such as this term, degradation agent is the reagent that the toxic agent destroying or help to find in the toxicity area is destroyed.Degradation agent for example can comprise the strong oxidizer with the corrosion inhibitor chemical reaction, when adding when flowing in the intrazonal injected water of toxicity, it is degraded to still less toxicity or non-toxic products.Degradation agent comprises strong oxidising agent for example nitrate, nitrite, chlorate, perchlorate and chlorite.

The detoxifcation of the chemicals of accumulating in the toxicity area can also realize with dispersing agent.The dispersing agent that uses in this article such as this term comprises any chemicals, its toxic agent that causes absorption from the toxicity area the bank rock and/or sand grains in remove and in the injecting process, it be dissolved in the water, thereby allow nature to disperse and diffusion it no longer is the concentration of toxicity for MEOR or bioreediation microorganism to be reduced to wherein.

In one embodiment, dispersing agent comprises any chemicals, the pH that it reduces solution makes amine ionization and in the injecting process it is dissolved in the water, and allow nature to disperse and diffusion it no longer is the concentration of toxicity for MEOR or bioreediation microorganism to be reduced to wherein.For example, amine is quite unresponsive under weak condition, yet they are hanging down the ionization that becomes under the pH.Therefore, increase its solubility with acid treatment amine and it is discharged from oil and/or rock and it is disperseed from the toxicity area.Therefore the amine of dissolving can enter in the water that flows through well.Radially flow, the combination of dispersion and desorb can allow the amine dilution of dissolving and disperse large tracts of land (at least 10 to approximately 200 feet (at least 3 meters to approximately 7 meters)) through oil well.Through after the dilution of much bigger area and disperseing, its concentration in the underground site of well thereby be reduced to for MEOR or the nontoxic level of bioreediation microorganism at amine.In another embodiment, can be with by about 1,000 PPM to 70 of the stereometer of water, the hydrogen peroxide of 000 PPM adds the toxicity area, as degraded and dispersing agent.In another embodiment, can add approximately 1 PPM to the about perchlorate of 10,000 PPMs, as degraded and dispersing agent.

In another embodiment, can use and to reduce pH less than any acid of at least 1 unit of amine equivalent point (as measuring among the embodiment hereinafter).Be used for making the acid of amine ionization can include but not limited to nitric acid, acetic acid, oxalic acid, hydrofluoric acid and hydrochloric acid.About 0.1 % by weight to the about acid of 20 % by weight can be added pump in the intrazonal water of toxicity.

In the MEOR process, with the water (referring to Fig. 1) in the inoculum adding injection water injection well of viable microbial.Term " inoculum of microorganism " refers to contain the composition of viable microbial.These microorganisms are building group's (i.e. growth and breeding) with the underground site of water injection well vicinity, to promote MEOR.The recovery of oil can be enhanced by the effect of microorganism, for example discharges oil from subsurface rock and/or sand grains, and forms the obstruction biomembrane that will strengthen the sweeping efficiency in the recovery of water filling secondary oil.

Microorganism for this application can comprise facultative aerobe, obligate anaerobe and denitrifier kind.For in underground site, using preferably effective microorganism under anoxic denitrogenation condition.Inoculum only can comprise, and a specialized species maybe can comprise two or more species of same genus or the combination that different microorganisms belongs to.

Inoculum can produce under aerobic or anaerobic condition, depends on one or more concrete microorganisms of use.Well-known in the art about the growth of aerobic and anaerobism culture and the technology of keeping and multiple suitable growth medium, and at " Manual of industrial microbiology and biotechnology " (A. L. Demain and N. A. Solomon, ASM Press, Washington, DC, 1986) and " Isolation of Biotechnological Organisms from Nature ", (Labeda, D. P. edits, 140 pages of 117-, McGraw-Hill Publishers, 1990) the middle description.

The inoculum of microorganism adds underground site by any method that is used for the microorganism introducing, and described method is that those skilled in the art are well-known.Usually, inoculum adds water injection well as the part of injected water (1), and described injected water is introduced in the casing (7) as shown in fig. 1.

The example of useful microorganism includes but not limited to one or more species of following genus in the method: Comamonas, fusobacterium, extra large bacterium genus, stone robe Pseudomonas, genus Shewanella, pseudomonas, vibrio, stone robe Pseudomonas, Soxhlet Pseudomonas and product microballoon Caulobacter.The microorganism of using in the method in one embodiment, be selected from Comamonas terrigena ( Comamonas terrigena), Fusibacter paucivorans, Marinobacterium georgiense, Petrotoga miotherma, Shewanella putrefaciens ( Shewanella putrefaciens), pseudomonas stanieri ( Pseudomonas stutzeri), vibrio alginolyticus ( Vibrio alginolyticus), fragrant Soxhlet bacterium ( Thauera aromatica), Thauera chlorobenzoicaWith Microbulbifer hydrolyticusIn one or more.

In one embodiment, inoculum at US 7,776, the Shewanella putrefaciens LH4:18(ATCC PTA-8822 that describes in 795) can use in the method.In another embodiment, own together and common unsettled U.S. Patent Application Publication No. US20090263887 in the pseudomonas stanieri (ATCC PTA8823) described can use in the method.In another embodiment, own together with co-pending patent application publication number US 20100078162 in the fragrant Soxhlet bacterium AL9:8(ATCC 9497 that describes) can use in the method.

Embodiment

The present invention further limits in the following embodiments.Although be to be understood that these embodiment indication the preferred embodiments of the invention, only explanation provides as an example.According to manual above and these embodiment, those skilled in the art can determine essential characteristic of the present invention, and utilize multiple variation of the present invention and modification so that it adapts to multiple use and condition.

Conventional method:

Chemicals and material

Except as otherwise noted, all reagent and the material that are used for the microbial cell growth and keep all derive from Aldrich Chemicals(Milwaukee, WI), DIFCO Laboratories(Detroit, MI), GIBCO/BRL(Gaithersburg, MD) or Sigma Chemical Company(St. Louis, MO).

Amine analysis

Amine concentration in medium and water is analyzed by gas chromatography (GC).Agilent model 5890(Agilent, Wilmington, DE), be equipped with flame photoionization detector and shunting/without the GC of split stream injector, DB-FFAP post (0.32 millimeter (mm) degree of depth x of 30 meters length x, 0.25 micro particles size).This equipment has Agilent ALS automatic sampler, has 6890 ranges of models of 10 milliliters of (ml) syringes.This system uses N, and the sample of N-dimethyl-1-lauryl amine (Aldrich) is calibrated.Helium is as carrier gas.Use with 30 ℃ of increments/minute (minute) 50 degrees centigrade (℃) to 250 ℃ temperature gradients.Comprise retention time for multiple purpose chemicals (with a minute expression, minute): N, N-dimethyl-1-lauryl amine (8.08 minutes); N, N-dimethyl-1-tetradecylamine (8.85 minutes); N, N-dimethyl-1-hexadecylamine (9.90 minutes); N, N-dimethyl-1-octadecylamine (10.26 minutes) and N-methyl, N-benzyl-1-tetradecylamine (11.40 minutes).

Embodiment 1

In model system, use amine blends in the sand grains from oil well, to set up the toxicity area

The sand grains sample of Schrader Bluff structure of comfortable Milne Point Unit of the Alaska North Slope by using the 50/50(volume/volume by methyl alcohol and toluene) solvent wash of compositions of mixtures cleans.Subsequently solvent is drained and from sand grains, evaporate, to produce cleaning, dry, flowable sand grains.This sand grains sieved to remove have size less than one micron particle and closely be filled into subsequently in four feet (121.92 cm) long elastic tubule (9), and use the laboratory checkering machine to pass through vibrating compacting.Two ends of tubule are all added a cover, to keep sand grains therein.Instrument display is in Fig. 2 fully.The pipe-line system of the amount of pressure that can stand to use in the tubule is connected to end cap.Tubule (9) is fixed in the pressure vessel (10), and wherein pipe-line system working pressure accessory (18 and 21) is through the end (11 and 12) of pressure vessel.Other accessory is connected connecting the entrance (11) and compression pump (13) and feed supplement bank (14) of tubule with pipe-line system.

Other accessory is connected the entrance of tubule and the high pressure side of absolute pressure transducer (20) and differential pressure pick-up (19) with pipe-line system.Accessory is connected the outlet (12) of tubule and low pressure side and the back pressure regulator (16) of differential pressure pick-up (19) with pipe-line system.Signal port from differential pressure and absolute pressure transducer exports computer to, and monitoring and periodic logging pressure reading.Pressure vessel (10) around tubule is full of water by water hole (15).This water slowly is forced into the approximately pressure of 105/ square inch (psi) (0.72 Megapascal) by air (17) subsequently, and from the bittern #1(of feed supplement bank (14) table) tubule and leave tubule by back pressure regulator (16) of flowing through.This operation is carried out like this, thereby so that the pressure in the tubule always is lower than pressure 20 psi(0.034 – 0.137 Megapascal in the pressure vessel (10)).

With HCl or NaOH the pH of bittern #1 is adjusted to 7.0, and solution filter is sterilized.

Table 2

The concentration that adds the amine among the bittern #1

In case in the tubule and outer pressure determine, just will be from the crude oil pump of a pore volume of the storage tank farm of Milne Point Unit of the Alaskan North in tubule.This process several hours (hour) in carry out.In case the sand grains in the saturated tubule of crude oil and observing in effluent just stops to flow and allows oil aging 3 weeks in core sand.When this finishes time, bittern #1 is crossed tubule with the speed of ~ 1.5 – 3.5 ml/hours (ml/h) (~ 1 pore volume/20 hour) pump.From effluent, obtain the concentration of sample and mensuration natural microbial fauna wherein.

After 51 pore volumes were flowed through tubule, the concentration of the natural microbial fauna in the system was about 1x10 ⁷CFU/milliliter (CFU/ml).On this aspect, amine blends (thereafter amine/bittern mixture) is added among the bittern #1 with 150 ppm concentration.The proximate composition (table 2) of amine blends is comprised of 7 kinds of different amine components identifying.Five kinds by mass spectrography (Agilent Technologies, Inc. Santa Clara, CA) identify N-N-dimethyl-1-lauryl amine, N-N-dimethyl-1-tetradecylamine, N-N-dimethyl-methane-thioamides, caprolactam and N-methyl-N-benzyl-1-tetradecylamine.Two kinds of components be accredited as by, but specific chemical formula can't be assigned to it, because the mass spectrum fracture mode can't be deciphered.These are labeled as " less amine " and " other amine " in table 2.Do not indicate the wherein existence of any amine from the effluent analysis of tubule.Continue experiment by the 150 ppm amine blends of taking out among the pump bittern #1 by tubule.

The bittern #1 of 77 pore volumes with 150 ppm amine blends mixture take out pump in tubule after, in effluent, do not observe amine.

The bittern #1 of 80 pore volumes with 150 ppm amine blends mixture take out pump in the tubule after, the about 1 donaxine mixture tubule of having flowed through altogether.On this aspect, finally in the effluent of tubule, observe 80 ppm amine.See that in effluent this very long delay in the amine means in fact all amine and entraps in tubule.In addition, at this moment, in effluent, can't see the natural microbial flora, point out the tubule enough toxicity that become, to kill all existing microbial floras.On this aspect, at flushing amine from tubule and so that it still less begins to take out pump without amine bittern #1 in the trial of toxicity.

After pump has been crossed tubule without amine bittern #1 of 24 pore volumes, in effluent, detect the amine of 51 ppm.Subsequently with tubule in order to about 1x10 ⁹The Shewanella putrefaciens of one pore volume of CFU/ml concentration (ATCC PTA-8822) inoculation.Do not allow this inoculum to be retained in the tubule.On the contrary, after inoculation, will pass through tubule without amine bittern #1 flushing immediately.Therefore, microorganism only stops a few hours in tubule in by its transportation.Therefore, the concentration of the microorganism in the expection effluent can be measured in the effluent of wash-out tubule.Yet unusual ground does not detect microorganism (representing approximately, 9 logarithms kill), although the short residence time of inoculum in tubule in the tubule effluent.This experiment confirm toxicity area is set up in tubule.In the continuation of detoxifcation tubule is attempted, independent bittern #1 is continued pump cross it.

After pump has been crossed tubule without amine bittern #1 of 79 pore volumes, the amine measurement of concetration in the effluent of tubule is 30 ppm.Tubule with the Shewanella putrefaciens of another pore volume (with 1 x10 ⁹CFU/ml) inoculation.CFU/ml in the effluent sample is about 1x10 ⁴, show that 5 logarithms that surpass of this microorganism kill immediately generation after inoculation.The continuous toxic action of amine has been emphasized in this experiment, prolongs sluicing pipe although use without amine bittern #1 solution.

After pump has been crossed tubule without amine bittern #1 of 108 pore volumes, the amine measurement of concetration in the effluent is 5 ppm.Tubule is with containing 1 x10 ⁹The Shewanella putrefaciens inoculation of another pore volume of CFU/ml.The CFU/ml that immediately tubule flows out in the matter sample after inoculation indicates 4-5 logarithms of this microorganism to kill, although use the prolongation washing without amine bittern #1 solution, and the reduction in the amine concentration in the effluent.The continuous toxic action of the amine blends that the further confirmation of these results is accumulated in tubule.

After pump has been crossed tubule without amine bittern #1 of 143 pore volumes, in the trial of removing the residue amine blends, with odorless mineral spirits (OMS) (Parks OMS, the Zinsser Co. of the cheapness of a pore volume, Inc., Somerset Jew Jersey #2035 CAS #8052-41-3) pump is crossed tubule.After the current flushing of OMS, continue without the take out pump of amine bittern #1 by tubule.

After pump has been crossed tubule without amine bittern #1 of 149 pore volumes, the amine measurement of concetration in the effluent is 4 ppm, and tubule is with Shewanella putrefaciens (1 x10 of another pore volume ⁹CFU/ml) inoculation.Microorganism count in the effluent sample of tubule shows that 2-3 logarithms kill (99 to 99.9%), although OMS washes and uses without the prolongation of amine bittern #1 solution and wash.These results confirm that the toxicity area in the tubule still kills basically all microorganisms that add in the pipe.

After pump has been crossed tubule without amine bittern #1 of 168 pore volumes, with the meticulous pipe of the water-soluble liquid pump of 10% HCl of a pore volume, to remove amine.Behind current acid elution, will continue pump without amine bittern #1 and cross tubule.

After acid elution is processed, with other 2 pore volumes cross tubule without amine bittern #1 pump, and the amine measurement of concetration in the effluent is 0.5 ppm.Tubule is used Shewanella putrefaciens (1 x10 of another pore volume subsequently ⁹CFU/ml) inoculation.CFU/ml in the effluent indicates approximately 0.4 logarithm of this microorganism to kill.These results highlight the survival of more microorganisms behind the acid elution of tubule, and use the validity in the toxicity area in the acidolysis poison tubule.Following table 3 overviews the result of above-described multiple test.

Table 3

The summary of the microorganism cut (logarithm kills) that kills in the amine amount of in the effluent of tubule, observing and the stop process in tubule.PV=pore volume; Nd=do not detect

Embodiment 2

Use hydrochloric acid from sand grains, to remove N N-dimethyl-1-lauryl amine at low pH by its ionization

38 milligrams of (mg) N N-dimethyl-1-lauryl amine (hereinafter referred to as " amine ") is added in the 10.210 gram pentanes.This solution is added the special sand grains layer (Oa and Ob) that 10.1845 grams derive from the Schrader Bluff structure on Milne Point Unit of the Alaskan North slope.The oil content of sand grains at first uses the mixture (50/50, volume/volume) of methyl alcohol and toluene to remove as solvent wash.Subsequently solvent mixture is evaporated from sand grains, to produce cleaning, dry, flowable sand grains.This sand grains is mixed to produce slurry with amine and pentane solution.This slurry is fully mixed and pentane is evaporated, stay amine (hereinafter referred to as sand grains/amine blends) on sand grains.100 ml bittern #2(are hereinafter filled a prescription) add in sand grains/amine blends, to produce sand grains/amine/bittern mixture.The initial pH of sand grains/amine/bittern mixture is 8.4.Amine concentration in the water should be 380 ppm, if all amine have been dissolved among the bittern #2.The sample of analyzing sand grains/amine/bittern mixture by GC does not disclose exist (being amine concentration ~＜1 ppm) of any amine in the specimen.The undetected fact of amine has been emphasized the strong combination of itself and sand particle.0.1 ml, 1 equivalent HCl is added in this solution, and again measure pH and the amine concentration of solution.This step is repeated several times, and analysis result is shown among table 4 and Fig. 3.Be lower than ~ 6.0 pH observes fully ionization and the dissolving of amine in water.This is surprising discovery, because the pKa of HCl is-6.2(Langes Handbook of Chemistry, and the 14th edition, the 8.14th page, 1992, McGraw-Hill, Inc., New York).Therefore, ionize amine and HCl concentration that its this step of removing is required fully from the toxicity sand grains and can further reduce several orders of magnitude by 10% concentration of using in this experiment.Data have been emphasized acid in ionization and have been removed from the remarkable efficient in the amine of sand grains.

The composition of bittern #2 (gram of deionized water/L)

Table 4

The amine concentration of measuring among the embodiment 2

Embodiment 3

The antacid ability of sand grains

A. in the situation that there is not the titration of the bittern #2 of sand grains

This experiment be intended that in the sand grains that mensuration describes in an embodiment and expection makes the ability of the HCl of the amine ionization of accumulating in the sand grains.

For the contrast test is set, 100 ml bittern #2 are titrated to 8.1 initial pH with 1N HCl.Add among the bittern #2 aliquot (0.1 ml) of 1N HCl and measurement pH.The HCl interpolation is repeated several times, and behind each the interpolation, measure pH.The results are shown among table 5 and Fig. 4 of these analyses.Data indications needs approximately 2.25 millinormal HCl to reach the approximately stoichiometric point of pH 4, corresponding to approximately 100% reclaiming of the carbonate that exists among the bittern #2.

Table 5

In the situation that there is not the titration of the synthetic injection of amine bittern #2

B. the titration that has the bittern #2 of sand grains

Add the identical sand grains (bittern/sand grains mixture) that 10 grams use with 1N HCl titration 100 ml bittern #2 in embodiment 2.The initial pH of bittern/sand grains mixture is 7.88.The 1N HCl of 0.1 ml aliquot is repeated to add in this mixture, and behind each the interpolation, measure pH.The result who is shown among table 6 and Fig. 4 indicates the existence of following 10 gram sand grains, needs the interpolation of 0.3 milliequivalent HCl to reach stoichiometric point.The results highlight that in this experiment, obtains in the sand grains and the slight ability of the HCl that adds.Thereby the acid of the small concentration HCl ionization amine of being combined with sand grains for example, and not by the neutralization that becomes of the reaction with sand grains.

Table 6

The titration of

bittern #

2 and 10 gram sand grains

Embodiment 4

Use 10% nitric acid from sand grains, to remove N N-dimethyl-1-lauryl amine at low pH by its ionization

The program of general introduction is for generation of sand grains/amine blends, except using 519 mg amine, 10 gram pentanes and the sand grains of 60.062 grams from Oa and Ob layer in embodiment 2.This sand grains/amine blends of 29.065 grams is added 100 ml bittern #2(above), to produce sand grains/amine/bittern mixture.The initial pH of sand grains/amine/bittern mixture is 8.28.Amine concentration in the water should be about 2000 ppm, if all amine all are dissolved among the bittern #2.On the contrary, the sample analysis of the bittern #2 that contacts with sand grains/amine/bittern mixture as mentioned above shows that amine concentration is ~ 85 ppm namely to be far smaller than the sort of of expection.Only the fact that detects in bittern #2 of a small amount of amine has been emphasized the strong combination of amine and sand particle.0.1 ml, 10 percentage by weights (% by weight) aqueous solution of nitric acid is added in this solution, and again measure pH and amine concentration.This step is repeated several times, and analysis result is shown among table 7 and Fig. 5.Be lower than ~ 6.7 pH observes fully ionization and the dissolving of amine in water.This is surprising discovery, because the pKa of nitric acid is-1.37(Langes Handbook of Chemistry, the 14th edition, the 8.15th page, 1992, McGraw-Hill, Inc., New York), the required concentration of nitric acid of this step can further reduce several orders of magnitude by 10 % by weight of using in this experiment, and to from sand grains, removing amine without any negative effect.

Table 7

The amine concentration of measuring among the embodiment 4

Embodiment 5

Use 10% acetic acid from sand grains, to remove N N-dimethyl-1-lauryl amine at low pH by its ionization

Repeat the same program of general introduction among the embodiment 4 herein, to produce sand grains/amine blends.30.85 gram (gram) sand grains/amine blends are added 100 ml bittern #2(above), to produce sand grains/amine/bittern mixture.The initial pH of sand grains/amine/bittern mixture is 8.52.Amine concentration in the water should be about 2000 ppm, if all amine all are dissolved among the bittern #2.On the contrary, the analysis of the bittern #2 that contacts with sand grains/amine/bittern mixture as mentioned above shows that amine concentration is ~ 67 ppm namely to be far smaller than the sort of of expection.Only the fact that detects in bittern #2 of a small amount of amine has been emphasized the strong combination of amine and sand particle.0.1 ml, 10 % by weight acetic acid are added in this solution, and again measure pH and amine concentration.This step is repeated several times, and analysis result is shown among table 8 and Fig. 6.Be lower than ~ 6.7 pH observes fully ionization and the dissolving of amine in water.This is surprising discovery, because the pKa of acetic acid is 4.756(Langes Handbook of Chemistry, and the 14th edition, the 8.19th page, 1992, McGraw-Hill, Inc., New York).Therefore, the required acetic acid concentration of this step can further significantly reduce by use is the sort of in this experiment, and to from sand grains, removing amine without any negative effect.

Above-described observation illustrate weak organic acid as acetic acid ionization with make amine and the toxicity sand grains separate aspect can be the same with the strong inorganic acid example hydrochloric acid effective.Therefore can reach a conclusion in order to remove the toxicity area from underground site, can use the pH of solution to be reduced in approximately any acid under 6.7.

Table 8

The amine concentration of measuring in an embodiment

Claims

1. method that comprises following in-order step:

A) with the underground site of at least a antidote processing with the area of water injection well vicinity; With

B) be added on the inoculum that microorganism strengthens microorganism useful in the oil recovery in water injection well, wherein said microorganism comprises following one or more species: Comamonas, fusobacterium, extra large bacterium genus, stone robe Pseudomonas, genus Shewanella, pseudomonas, vibrio, Soxhlet Pseudomonas and product microballoon Caulobacter;

2. the process of claim 1 wherein that described corrosion inhibitor is to be selected from following organic compound: Organophosphonate, organonitrogen compound be amine, organic acid and salt thereof and ester, carboxylic acid and salt thereof and ester, sulfonic acid and salt thereof, alkynol, organic pyrrole, glutaraldehyde, tetrakis hydroxymetyl phosphonium sulfuric (THPS), two thiocyanates methacrylaldehyde, dodine hydrochloride, formaldehyde, chlorophenol, organic oxygen scavenger and multiple nonionic surface active agent and combination thereof for example.

3. the method for claim 2, wherein said corrosion inhibitor comprises quaternary ammonium compound or its catabolite.

4. the method for claim 3, wherein said quaternary ammonium compound is selected from benzalkonium chloride, bi-quaternary ammonium salt, quaternary nitrogen compound and imidazolinium compounds.

5. the process of claim 1 wherein that described corrosion inhibitor is to be selected from following inorganic compound: chlorine, hypochlorite, bromine, hypobromite, chlorine dioxide, hydrazine, anthraquinone, phosphate, sodium sulfite, the salt that contains chromium, molybdic acid or zinc and combination thereof.

6. the process of claim 1 wherein that the antidote of described (a) is dispersing agent.

7. the method for claim 6, wherein said dispersing agent is the acid that is selected from hydrochloric acid, nitric acid, hydrofluoric acid, acetic acid and oxalic acid.

8. the method for claim 6, wherein said dispersing agent causes separating of underground site that corrosion inhibitor and water injection well are contiguous, and with its dispersion and dilution, thereby so that described corrosion inhibitor becomes nontoxic for described microorganism, and the described underground site detoxifcation contiguous with water injection well.

9. the process of claim 1 wherein that described antidote is degradation agent.

10. the method for claim 9, wherein said degradation agent is the strong oxidizer that is selected from nitrate, nitrite, chlorate, perchlorate, chlorite and combination thereof.

11. the process of claim 1 wherein that described antidote is dispersing agent and degradation agent.

12. the method for claim 11, wherein said antidote are hydrogen peroxide or perchlorate.

13. the process of claim 1 wherein that described corrosion inhibitor is the growth inhibitor of SRB.

14. the process of claim 1 wherein that described microorganism building the group with the underground site of the contiguous detoxifcation of water injection well, strengthen oil and reclaim to carry out microorganism.

15. the process of claim 1 wherein described inoculum comprise Comamonas terrigena, Fusibacter paucivorans, Marinobacterium georgiense, Petrotoga miotherma, Shewanella putrefaciens, pseudomonas stanieri, vibrio alginolyticus, fragrant Soxhlet bacterium, Thauera chlorobenzoicaWith Microbulbifer hydrolyticusIn one or more.

16. the method for claim 15, wherein said fragrant Soxhlet bacterium is strains A TCC9497, and described pseudomonas stanieri is strains A TCC PTA8823, and described Shewanella putrefaciens is strains A TCC PTA-8822.