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    • 专利摘要:
    The present invention relates to an improved method of enhancing oil recovery by use of conformance control. More particularly, the method of conformance control involves the provision of a plugging material which is designed to be formed within an area of high-permeability in preference to an area of low permeability in order that subsequent water, gas or chemical flooding can enhance oil recovery from the area/region of low permeability.
    公开号:DK201570163A1
    申请号:DK201570163
    申请日:2015-03-23
    公开日:2015-04-13
    发明作者:Martin Bennetzen；Kristian Mogensen
    申请人:Mærsk Olie Og Gas As；
    IPC主号:
    专利说明:

    Conformance control In enhanced oil recovery
    OaId.o | ftiinveol! QB
    The present invention relates to an improved method of enhancing oil recovery by using conformance -control Moro particularly, the method of conformance control involves: the provision of a plugging material which is designed to be formed within ah area of high-permeability in-preference to an area of low permeability in order that subsequent water, gas or chemical flooding can enhance oil recovery horn the area / region of low permeability,
    Water flooding as an oil recovery technique has been in use since 1090 when, operators in the US realized that water entering the productive reservoir formation was stimulating production, in some cases, water is supplied from an adjacent Connected aquifer, to push the oil towards the producing wells. In situations where there is no aquifer support, water must be pumped into the reservoir through dedicated injection wells. The water phase replaces the oil and gas in the reservoir and thereby serves to maintain: pressure. Recovery factors from wafer flooding range from 1 -2% in heavy oil reservoirs up to .50% in light oil reservoirs with typically values around 30 * 35%, much lower than the microscopic sweep efficiency of 70 * 09%.
    The reason for sub-optimal recovery factors is related to the macroscopic sweep, which in turn is a reflection of reservoir heterogeneity and fluid mobility ratios. Fluid mobility ratio may be controlled to some extent by adding yiscosifying agents to the injection phase, such as polymers or foams, but the presence of large permeability variations requires a different approach to improve macroscopic sweep; An extreme case is a direct high-permeability conduit, either natural or induced, between an injector and one or more producers, which requires complete or at least partial plugging. This process is known as conformance control.
    Conformance control generally requires a combination of mechanical and chemical solutions. The role of the mechanical part is to ensure that: the chemicals reach the part of the reservoir which they are intended to plug. Although commercial chemicals already exist for plugging high-permeability zones, the chemical mixture has to be tailored to a particular application, depending on salinity, temperature ©, pore size etc. The main challenge lies in conveying the Chemicals to the right place in the reservoir .
    Failure to achieve proper delivery may result in plugging of ilia near well-bore, with reduced production or injection as a result. 2hu el ai. (Journal ol Canadian Petroleum Technology. 1993, 32/9, p 37-43 teaches a salting-out concept in which a. Non-electrolyte {alcohol) is added to water to reduce the solubility of electrolytes (salt). A preliush of highly salt-concentrated brine was followed by a flush with ethanol The brine and ethanol both flow through the water flooded higli permeability zones and will mix there. The ethanol leads to the salt precipitating, which serves to plug these high-permeability zones. In Homogenous and heterogeneous sandpacks the reduction, ot brine permeability was 70% and 50%, respectively, leading to an incremental oil recovery of 15% of oil initially .in place (after wafer flooding). However, there is a concern that the ethanol and brine may not mix only in the desired permeability zone, leading to salt precipitation in an incorrect location. Moreover, the ethanol may mix with other salt bearing solutions which may lead to salt precipitation again occurring in an incorrect location;
    It is among the objects of the present invention to obviate, and / or mitigate, at least, Of the aforementioned disadvantages.
    The present invention is based on a method of conformance control which employs nucleic acid which is capable of forming a complex in order to provide a plug in permeable oil bearing subterranean areas, Typically the plug may be formed in regions of high permeability, such as to facilitate oil recovery from areas of: lower permeability. In a first aspect, the present invention provides a method of selectively reducing the permeability of a. first region of subterranean formation, the method comprising providing first and second conformance. controlling iiusds to the first region, the first conformance controlling fluid comprising a. first nucleic acid molecule and the second conformance controlling fluid comprise a second nucleic acid, and said first and second nucleic acid molecules are capable of hybridizing or otherwise binding to one another under appropriate conditions such that a nucleic acid complex is formed reducing the permeability in at least a portion ol the last region.
    Iha method may further comprise providing displacement or hood fluid to the formation after the complex has been formed, whereby the flood fluid is directed to regions of the formation in which a reduction in permeability has not occurred in the complex formation,
    In a preferred embodiment, flow of the dispiac remover fluid through the first region of the permeable formation is reduced, the fluid flow is preferably directed to flow through a second region of reduced permeability relative to the first region of permeable substrate. As. for example, the method of reducing permeability may reduce flow of a flood fluid through art area of permeability, in order to enhance or increase flood fluid flow through one or more areas of "tow" or reduced permeability compared to the area of " high ”permeability. Although the terms' "higlf and low * are relative terms, their meaning will be clearly understood in the context of the present Invention to relate to areas of a permeable substrate which are understood to display a relatively increased and decreased to the method of the present invention being carried out, in this less oil recovery from the area of low or lower permeability may be enhanced.
    Conveniently, the first and second conformance conduction fluids are provided to the permeable formation separately, such that the first and second conformance fluids only contact one another within the first permeable region. For example, the first: and second superstorm controlling fluids may be provided as How Into tire first region from separate first and second locations adjacent to the first permeable region. For example, the first and second conformance centering fluids may be provided from first and second wellbores located either side or adjacent to the first area of permeability. in this manner, it is expected that the first and second conformance controlling fluids will only come into substantial contact once within the first area of the permeable substrate.
    Advantageously, the first location and the second location may be different. By such provision, in use, the first fluid may preferentially enter and / or may be preferentially directed 'into the first region from the first location ,, and the second composition may preferentially enter and / or may be preferentially directed into the first region from the second location. As a result, the first fluid and the second fluid may contact within the first permeable region in order to form the complex within the first region. The low permeability of the second region may not permit a substance! amount .of the first fluid and / or of the second fluid to enter and / or to be directed into the -second region.
    As a result, present methods may reduce, minimize and / or prevent contact between the first fluid and the second fluid in the second region. Thus, the present method may advantageously assist in at least -partially plugging and / or reducing permeability of the first region (eg region of high permeability), while reducing, minimizing and / or preventing plugging in the second region (eg region of low permeability ). By such provision, the recovery factor during subsequent oil recovery, e.§. by Hooding, may be increased as the displacement substance * e.g. flood fluid, may be forced to displace hydrocarbons in the second region of low permeability, in addition, infecting the first fluid and the second fluid from different locations, e.g., from at least one first or production wellbore and from at least one second. injection wellborn ,. may reduce the amount of reaction product in the first and / or in the second wellbores, thereby reducing the risk of accidentally plugging the • firstand o; second wellbores.
    The first and second locations may be located on substantially opposite sides of the formation and / or first region thereof. It will be appreciated that the precise disposition at the first and second locations may be selected depending on the particular profile and / or characteristics of the formation.
    The first location may comprise and / or may be defined by one of more first wellbores. One or more first wellbores may typically comprise one or more production wellbores or injection wellbores, typically one or more production wellbores.
    The second location may comprise and / or may be defined by one of more second wellbores. One or more first well bores may typically comprise One or more injection wellbores or production wellbores, typically one or more injection wellbores.
    Advantageously, the first fluid may be injected from at least one production wellbore or injection wellbore. The second fluid may be injected from the other or at least one injection wellbore or production wellbore. By such provision, the second and second fluids may be provided to the lust region separately, such that the first and second fluids may preferentially contact one another and / or the. first and. second nucleic, acids to bind / hybridize within the first region of permeability.
    By providing the first and second conformance controlling fluids to separate locations, such as two separate wells adjacent to the permeable substrate, the formation of the nucleic ansi complex, except in the desired location, is avoided and / or reduced. In addition, by first controlling the first and second conformance controlling fluids separately, e.g. From separate locations, it is expected that the ability of the first and second conformance controlling fluids from coming into contact within said second reglonfs} of reduced: permeability is' significantly reduced Compared to the first region of high or enhanced permeability, Iltese features are not expected to achieve wild plugging methods of the prior an winch using a single conformance controlling field and / or a single well or source of fluid provision to the permeable formation.
    As will be described in more detail, the first and second nucleic acid molecules are designed so as to be able to bind to hybridize to one another within the first region of the permeable substrate. Desirably, the first and second nucleic acid molecules are designed to bind strongly to one another under conditions (such as an appropriate pressure and / or temperature) which are expected In the first area of permeability, Bmding / hybridization of the two nuolelo acid molecules may be enconraged / anhanced through the use of salt, well known to the skilled addressee that the stability of hybridized nucleic acid molecules is increased with increasing salt concentrations. Thus, it may be preferable to provide a salt in an amount of between 0.001 - 2M such as 0.01 to 0..3M. In the first region of permeability to enhance and / or stabilize binding / hybridization of the first and second nucleic acids molecules. The salt may be provided separately to the first and second conformance controlling fluids and / or may be present in one or both of the first and second conformance controlling fluids.
    Furthermore, if it is also possible to make the formation of the complex more permanent by introducing a suitable cress · linking agent Suitable nucleic acid cross · linking agents include alkylating agents such as 1, 3-bis {2-chloro! -1-nitrosourea (BCNii) and aldehydes such as acrolein and crofonaldehyde.
    Also, if the complex forms in a region where not desired, or if it is not desirable to remove a non-cross linked complex from a region, this may be achieved by introducing a hydrogen bond ctenaiurant This may be desirable should a complex form in a region of low permeability. Thus, in certain embodiments, a denaturing agent, such as urea or forrnamide and / or increasing pH through the use of an appropriate base, such as NaOH typically In solution may be provided to a region of low permeability in order to reduce any complexes formed therein, ft may also be desirable to encourage mixing of tire first and second, conformance controlling fluids and this may be achieved by ensuring that the first and second conformance control fluids are of different viscosities.
    The first fluid may have a viscosity greater than the viscosity of the second fluid, e, g. water, for example by a factor of approximately 2-2G «e.g., 2-10, e.g. 5-10.- 8y such provision, Infection of the second fluid may displace at least a portion of a displacement substance, e, g. water, present in the first region, out of the first region, for example into a portion of the second region near or adjacent, the first region, in preference to displacing the more viscous first, Advantageously, this may assist in promoting mixing of the first fluid and second fluid within the first region, for example by creating "viscous fingering" of the second fluid through the more viscous first fluid.
    The method may comprise maintaining the first wellbore and / or the second wellbore, typically both the first wellbore and the second wellbore, in a closed configuration, for a predetermined amount of time, The amount of time may be selected for alow reaction between the first composition »and the second composition to occur, ft will be appreciated that the amount of time may depend on the conditions expected in the first region, such as temperature, pressure, pore size, reservoir properties, etc.
    In one embodiment, the method may comprise injecting the first fluid and the second fluid simultaneously, By simultaneously, if is meant that the first fluid and the second fluid may be injected substantially at the same time, although the first location and second location may be different, in another embodiment, the method may comprise injecting the first fluid and the second fluid alternatively. Advantageously, this may permit fling and / or saturation of the first region with the first fluid, prior to injection of the second fluid, in such an embodiment it may not be necessary to employ first and second wellbores and the first and second fluids may be provided. from a single wellbore at different times.
    The method may comprise measuring and / or monitoring pressure, eg, bottom-hole pressure {BMP}, in the 'first location or first wellbore and / or in the- second location or second wellbores, advantageously both in the first wellbore and in the second wellbore. A sharp increase in BHP in the first location, e.g., production-wellbore, may indicate that injection of the first fluid should be released. Without wishing to be bound by theory, it is believed that such an increase in BHP in the first location may indicate that the first fluid has substantially filled or saturated the first 'region (eg, of high permeability), and is about to eater the second region (eg, of tow permeability).
    Typically, the method may comprise injecting the displacement substance from at least one wellbore, e # injection wellbore. The method may comprise recovering oil from at least one wellbore, eg. production wellbore, Advantageously, because the permeability of the first region has been reduced by formation of the complex in the first region of permeability, the recovery factor may be increased, in one embodiment, the present invention provides nucleic acid functionalized nanopastiels for use in a method as defined herein. The nanopastides comprise a nucleic acid molecule attached, conjugated or otherwise bound to the surface of the nanoparticle, in. In accordance with the Invention, first and second nucleic acid functionalized nandparts are provided which are intended to hybridize or otherwise bind to one another, such as through complementary base pairing of the two different nucleic acid molecules to one another. Binding of the two nucleic acids molecules to one another, for example complementary or substantially complementary nodule add molecules, leads to -formation of a complex comprising nenopafticles in combination with hybridized nucleic acid molecules. Many such .complexes are formable where the respective first and second nucleic add functionalized nanoparticles come to contact and hybridize, leading to the formation of a plug, blockage or the like forming in the area of complex formation. A number of abbreviations and definitions are used throughout the specification and may be used for the interpretation of the twentieth it is noted here that, as used herein, the singular forms "a, M" an, "and" the * include plural reference unless the context clearly dictates otherwise.
    It is to be noted that the terms "nucleic add *," "polynucleotide * and" oligonucleotide "are used interchangeably herein and have meanings accepted in the art.
    It is further noted that the terms "attached", "conjugated", "bound" "modified" and notional seed "are also used interchangeably herein and refer to the association of a nucleic acid molecule with a moiety, such as a nanopartide .
    As used herein, a "nucleic act is a polymer of RMA or DNA that is single-stranded, optionally containing synthetic, non-natural or altered nucleotide bases. An isolated nucleic acid in the form of a polymer of DNA may be comprised of one or more segments of cDNA, genomic DNA or synthetic DNA, The nucleic acid may be provided by recombinant expression of the nucleic acid or by de novo poiystucteofide synthesis techniques well known to those skilled in the art.
    The term "nucleotide" or its plural as used herein is interchangeable with modified forms as discussed herein and otherwise known in the art. In certain instances, the art uses the term "nueleobase" which embraces naturally-occurring nucleotide, and non-nafieolly -Ecurring nucleotides which include modified, nucleotides Thus, nucleotide or nucleobase means the naturally occurring nucleobases adenine (A), guanine (8), cytosine (C), thymine (11 and uracil (U). Non-naturally occurring nucleobases include , for example, and without fimitations, xanthine, diaminoptirin, 8-oxo-N6-methyfadenine, 7-deazax.arsi; hine, 7-deaxaguanine, Ml. N4-ethanocytosine, N '^ T-ethanc ^ aiS-'ClIlamnopurine, 5 -methylphysylcytosine (mC), 5- (¾ - GD-alkynylEcytosine, S-fluorocurea, 5-bromouracif, pseudoisocytosine, 2-hydroxy-5-methyl-4-trisazopyridine, isocytosine, isoguanine, inuine and the "nominee" "nucleobases described in Banner et at, US Pat No, 5,432,272 and Susan M, Prefer and Karf-Hemx Altman n, 1997, Nucleic Acids Research, voi 26: pp 4429-4443, The term "nucleophobase" also includes not only the known purine and pyrimidine heferocyclcs, but also heterocyclic analogues and tautomers thereof. Further naturally and non-naturally occurring nucleobases include those disclosed in U.S. Pat. No. 3,687,808 (Ivtehgan, at at.), In Chapter 15 by Sanghvi, in Antisense Research and Application, for T. Crooks and 8, lebieo, CRC Press, 1993, in Engilsch et al., 1991, Angewandte Chemie, International Edition, 30: 613-722 (see especially pages 622 and 623, and In the Concise Encyclopedia of Polymer Science and Engineering, J, I. KroschwiN Ed., John Wiley & Sons, 1990, pages 858-859, Cook, Anil-Cancer Drug Design 1991, 8, 586-607, each of which are incorporated herein by reference in their entirety). In various aspects, polynucleotides also include one or more "nucleic acid bases" or "base units" which are a category of non-nafuraily-occurnog nucleotides that include compounds such as. heterocyclic compounds that can seme like nucleobases, including certain "universal bases" that are not nucleic acid bases in the most classical sense but serve as nucleic acid bases. Universal bases include 3-nitropyrroie, optionally substituted indoles (ag, 5-niiroindois), arte optionally substituted hypoxynthine, Other desirable universal bases include, pyrrole, diazote or trlazoie derivatives, including those universal bases known in the art Modified nucleotides are described in EP 1 072 679 and WO 97/1 £ 096, the disclosures of which are incorporated herein by reference. Modified nucleobases include, without limitation, 5-methylcytosine (S-rae-C), S-hydroxy methyl cytosine, xanthine, hypoxanthine, 2-aminoadenine, 6-methyl and other alkyl derivatives of adenine and guanine, 2-propyl and other alkyl derivatives of adenine and guanine, g-thiouracil, S-lhiothymlno and 2 · tbiooytossne, S-haiouracil and cytosine, S-propynyl uracil and cytosine and other afkynyl derivatives of pyrimidine bases, 6-azo uracil, cytosine and thymine, 6-uracil pseudouracil), 4 · thiouracil, 8-halo, 8-amino, 8-thiol, 8-hydroxyalkyl, 8-hydroxyl and other substituted adenines and guanines, 5-alio especially 5-bromo, 5-trifluoromethyl and other 5-substituted uracils and cytosines, 7-methylgylamine and 7-nitrobyladenine, 2-F-adenylene, 2-amino-adenine, S-azagnaniline and 8-azaadenine, 7-deazagua'nino and 7-deazaadeninO and 3- deazaguanine and 3-deazaadentne.- Further modified bases Include tricyclic pyrimidines such as phenoxazlne cytidineflH- pyrlrnidofS, 4-b | [l, 4Jbeneoxazin-2f3 H} -one), phsnothtazlne oytidlne (1H-pyrimidoido, 4-dipi4] benzothsazin-2 (3H) -one), G-. clamps such as a substituted phenoxazlne cytidine {& .§. 9- (2-Aminoethoxy) -H ~ phenylmethyl [5.4- (b) ii, 4β-benzoxaz-azphn-2 (3H) -one), ambiguous cytidine (2H-oynm-doMS-b-indol-2 ') One), pyrinducedole cytidine (H-pyrido | S4,2 ': 4,5Jpyn-olo (2,3-d | pyrimkio-2-one). Modified bases may also include those in which the purine or pyrimidine base is replaced with other hsterooydes, for example 7-deaia-adenine, 7-deazaguanosylene, 2-aminopyridine and 2-pyridane. Additional nucleobases include those disclosed in U.S. Pat. No. 3,687,808, those disclosed in The Concise Encyclopedia Of Polymer Science And Engineering, pages 858 -859., Krosehwte, J, L, ed. John Wiley & Sons, 1990, these disclosed by Engilsch of ai, 1991, Angewartcte Chemie, International Edition, 30: 813, and those disclosed by Sanghvi, Y. S "Chapter IS , Antisense Research and Applications, pages 289-302, Crodka, BT and Lebleu, B., ed., ORO Press, 1993. Certain of these bases are useful for increasing the binding affinity and include S-substituted pyrimidines, 8-azapyrimlelines and N-2, N-6 and 0-6 -substituted purines, including 2-aminopropyladenines, 5-propynyluracin and 5-propynylcytosine. 5-methylcytosine substitutions have been shown to increase nucleic acid duplex stability at 0.6-1.2 ° C and are, in certain aspects combined with E'-Q-rhethoxyefhyi sugar modifications. See, U.S. Pat, Noe, 3,687,808 U.S. Pat. Nos. 4,845,205; 5,130,302; .5,134,066; 5,175, .273: 5,367,068; 5,432,272; 5,457,107; 5,459,255; 5,464,008; 5,502,177; 5,525,711; 5,552,540; 5,587,469; 5,594,121, 5,598,091. 5,614,617; 5,845,985; 5,830,853; 5,763,538; 6,005,095; 5,750,692 and 5,881,941, the disclosures of which are incorporated herein by reference.
    Methods of making polynucleotides of a predetermined sequence are well known. See, eg, Sambrdok at ai, Molecular Cloning: A Laboratory Manual (2nd ad. 1 Sf89} and F, Eckstein (ed.) Qilgonueieotldes and Analogues * 1st ed. (Oxford University Press, New York, TS91), Solid-phase synthesis methods are well known for doth polyribonucleotides and polydeoxyribonucleotides (the well-known methods of synthesizing DMA are also useful for synthesizing RNA), polyribonucleotides to also be prepared enzymatically, Non-naturally occurring nude sodas to be incorporated into the polynucleotide, as well See, e, gs LIS, Patent No. 7,223,833; Katz, D. Am, Cham. See, 74: 2238 (1951); Yamane, et al., 8 Am. Cham. Soc, 83: 2599 (1991): Kosturko, at Ak, Siohérotstry, 18: 3949 (1374); Thomas, J. Am, Cham. Soc, 76: 6032 (1: 954); Zhang, et al., J, Am. Cham. Soc, 127: 74-75 ( 2005); and Zirømermaoo, et al., J. Am. Cherrt Soo, 124: 13684-13885 (2002), "Hybridization" or "binding" refers to an interaction between two or three strands of nucleic acids by hydrogen bonds in aecdance. with the Watson-Criek DMA complementarity rules, Hoogstein binding, or other sequence-specll Is binding known in the art. Hybridization, or binding of nucleic acids to one another in the context of the present invention can be performed under suitable salt conditions, temperatures and pressures as can be: provided in a particular environmental location, most typically oil bearing permeable substrates:, "Complex" as used herein refers to a structure which forms when the nucleic add molecules, such as nucleic acid functionalized. nanoparticles of the present invention, bind to or hybridize to one another. Typically, a complex wifi comprise many, such as 10s, or 100s, surrounding nucleic acid molecules; "Nanopartides" are herein defined as metallic, metal salt, semiconductor or any other type of particle having an average particle diameter of, for example, between 1 and 800 am. Metallic nanopadiukvs include, but are not. limited to, particles of gold, silver, platinum, palladium, iridium, rhodium, osmium, iron, copper, cobalt, and alloys composed of these metals. "Metal salt or semiconductor nanoparticles" include, but are not limited to, particles of cadmium selenide, cadmium sulfide, silver sulfide, cadmium sulfide, zinc sulfide, zinc selenide, lead sulfide, gallium arsenide, silicon, tin oxide, iron oxide, and indium phosphide. Nanoparticles may also be made from organic matter! and / or polymeric materials such as dextran, polyethylene glycol and the like.
    Preferably, the average particle diameter of the particles is between about 10 and 500 nm. As used herein, "particle size" and "particle diameter" have the same meaning. The nanoparticles may be substantially spherical in shape or may form another type of nanoparticle
    The term Piano structure "means tubes, rods, cylinders, trundles, waters, disks, sheets, plates, planes, cones," livers, grannies, ellipsoids, wedges, polymeric fibers, natural fibers, and other such objects which may have at at least one characteristic dimension less than about cloth or SO nm.
    The nanoparticles of the invention may be coated. The coating can serve as an attachment for the new add or a spacer or binding moiety, and may also serve to render the nanopsrKcie water soluble. Methods for the preparation of, water-soluble nanopasticles are known in the art These panicles can be either charged or neutrai depending on the nature of the organic coating. For example, Templeton at AI, (Langmuir 15: 66-76 (1999)), herein incorporated by reference, describes a method for the preparation of stabilized, charged, water-soluble gold nanoparticles protected by tiopronin or coenzyme A monolayers. A similar method of preparing, water-soluble nanoparticles of the metals gold, silver, platinum, palladium, cobalt and nickel is descried by Heath et al. in the U.S. <Pet Mo. 6103868. herein Incorporated by reference.
    Other suitable methods for the preparation of coated nanoparticles are known (see for example Chen et al. - {CoUdids and Surfaces A 169: 107-116 (2000)}; Hagemeyer et al. In U.S. Pat. No. 6,074,979; Wuelfing et al. ai U Chem Chem Soc 120: 12696-12697 (1996) 2 Oban et al. (Science £ 81: 2016-2018 (1998)); Mitchell et al. id., in Cfmm, See, 121: 8122- 8123 (1998)}; and Napper (J. Goiioid. Interface. Sci 581390-407 (1977)) it may be useful to provide a coal nancpartlcla where one component of the coating provides a point of attachment for the nucleic acid, and the other component acts as a shield against non-specific binding of, for example, identical nanoparticles — which comprise the same nucleic add and hence are not designed to bind to one another.
    The first nucleic acid of the present disclosure may have a T «, when hybridized to the second nucleic acsci sequence, of at least about 45 * C, typically between about 50 * to 60 * G, although the T! TS may be higher , eg, SS ° C, 75 C or 85 C at a pressure of 1 here.
    In one embodiment; the first nucleic acid sequence of the Invention is designed to hybridize: to the second nucleic acid sequence under physiological conditions, with a G substantially greater than 37 ° 0, e.g., at toast 45 * € and, in some aspects , approximately 60 * 0 - 80 * €. in a preferred aspect the first nucleic acid sequence is 100% complementary to the second nucleic acid sequence, or It may include one or more mismatches, Methods are provided in which the first nucleic acid is generally greater than 90%, greater than 95% complementary to the second nucleic acid sequence, greater than 90% complementary, greater than 80% .com complementary, or greater than 75% complementary to the second nucleic add sequence. In one embodiment the first nucto-c acid Is a polyA. molecule (polyA being a nucleic acid chain formed from identical adenine molecules} and the second nucleic acid Is a poiyT molecule (poiyT being a nucleic acid chain formed from Identical thymine molecules). PolyA and poiyT molecules will bind to each other under degrees of high Alternatively, the first nucleic acid may be a poly chain molecule of cytosine molecules} and the second nucleic add a polyG molecule (a chain of guanine molecules) as such molecules will also bind to each other under high stringency due to complementary base pairing of G to O, The skilled addressee is well versed in how to provide different nucleic add molecules which are capable of binding- to one another and hence there is no restriction to the sequences which may be employed in the present invention, rather that they should be capable of binding or hybridizing to one another preferably under conditions appropriate to the invention. recent invention and typically under high stringency conditions known in the ad.
    Also, as described in U.S. Patent Publication No. 2003/0147966, nanoparticles of the invention include those that are commercially available, as well as those that are synthesized, e, §, produced from progressive nudeation in solution (0.9., By colloid reaction} or by various physical and chemical vapor deposition processes, such as sputter deposition See, eg, HaVashi, Vac Sd Teehnoi, A5 (4): 1375-64 (1987) · Hayashf, Physics Today, 44-60 (1987); MRS Bulletin, January 1990, 16-47, As further described in U.S. Patent Publication No, 9098/0147966, nanoparticles contemplated are alternatively produced using a metal salt and a citrate-reducing agent, using methods known in the art. See, e.g., Msbnakos ei a !, Adv. Mater. 1 1: 34-3 (1989); Marioakos et al., Cham. Mater. 10: 1214-19 (1993); Enusfun & Turkevich, J. Am. Cham. Sou. 85: 3317 (1983),
    Nanoparticles provided that are functionalized with a polynucleotide, or a modified form thereof, generally comprise a polynucleotide from about 5 nucleotides to about 1: 000 nucleotides in length. More specifically, nanoparticles are functionalized with polynucleotides that are about 10 to about 900 nucleotides in particular. IS to 200 nucleotides in length.
    As discussed above, modified nucleic acid molecules are contemplated for functionalizing nanoparticles. In various aspects, a nucleic acid molecule functionalized on a nanoparticle is completely or partially modified. Thus, in various aspects, one or more, or all, sugar and / or one or more or all internucleotide linkages of the nucleotide units in the polynucleotide may be replaced by "non-naturally occurring" groups. In one aspect, this embodiment contemplates a peptide nucleic add (PNA). In PNA compounds, the sugar backbone of a polynucleotide is replaced with an amide containing backbone. See, for example, U.S. Patent Nos. 5,539,082; 5,714,331; and 5,719,262, and Nielsen et al Science, 1991, 254, 1497-1500, the disclosures of which are herein incorporated by reference.
    Other linkages between nucleotides and unnatural nucleotides contemplated for the disclosed polynucleotides Include those described in U.S. Patent Nos. 4,981,957; 5,118,800; 5,319,080; 5,359,044: 5,303,878; 5,448,137; 5,486,788; 5,514,785; 5,519,134; 6,567,811; 5,576,427; 5,591,722; 5,597,909; 5,610,300; 5,627,053; 5,639,873; 5,646,265; 5,658,873; 5,670,633; 5,792,747; and 5,700,920; U.S. Patent Publication No. 20040219565; international Patent Publication · Nos. WO 98/39352 and WO 99/14226; Mssmaeksr et. ai., Current Opinion in Structural Biology 5: 343-355 (1995) and Susan M. Prefer and Kart-Heinz AJtniann, Nucleic Acids Research, 25: 4429-4443- (1897), the disclosures of which are incorporated herein by reference . Specific examples of oligonucleotides include those containing modified backbones or non-natural sntemucieosicie linkages. Oligonucleotides - having modified backbones include those that retain a phosphorus atom in the backbone and those that do not have a phosphorus atom in the backbone. Modified oligonucleotides that do not have a phosphorus atom in their intemuelsaslds backbone are considered to be within tbs meaning of "oligonucleotide.1"
    Modified polynucleotides may also contain one or more substituted sugar moieties, in certain aspects, polynucleotides comprise one of the following at the 2 'position: OH; F; O-, S-, or KOatkyi; 0% S-, or fxi-alkenyl; O-, S> or N-alkyl; or G-alkyl-O-alkyl, wherein the alkyl, alkenyl and alkynyl may be substituted or imsutmitted C 1 to C 10 alkyl or C 2; to Go alkenyl and alkynyl. Other embodiments include 0 | {GHsGO]! ISGHa, 0 (GH2},, DGH St OfCHa) ;, NHs, 0 (C> l, pOHa, 0 (GHa) aQNBs, and OfCH ^ ONifCH ^ iiGHsk where n and m are from 1 to about 10, Other polynucleotides comprise one of the following at the 2 'position; Cl to C10 lower alkyl, substituted lower alkyl, alkenyl, alkynyl alkaryj, aralkyl, O-alkaryl or O-aralkyl, SH, SCHa, OGN , Cl, Br, CN, GFa, OGFs, SOGNs, SOsCHs, ΟΝΟ *, N0 & 1%, NH & Sieterocycioalkyi, treterocycloalkaryi, aminoalkylamino, polyaikyiamino, substituted sliyf, and RNA cleaving group, a reporter group the pharmacokinetic properties of a polynucleotide, or a group for improving the pharmacodynamic properties of a polynucleotide, and other substituents having similar properties. In one aspect, a modification Includes X ~ methoxyethoxy (2'-0-GHgCHgOCHs, also known as 2'- 0- {2-methoxyethyl> or S'-MQE) (Martin et al., 1995, Halv. Chim Acta, 78; 486-504) le and aikoxyalkoxy group. Other modifications include g-dirmdh yiaminooxyethoxy, group also known as 2-DMA0E, and 2'-dimethylammoethoxyethoxy (also known in tire art as S'-O-dimethyi-arrsirro-ethoxy-ethyl or 2-QMAEOB
    Still other modifications include G-methoxy (2-0 ~ 0Ha), 2'-amiftopropoxy (T-OCHgCHsCHilNHg), G'-allyi (2'-CHrCH-0HG, 2-0-allyl (WCHs-GH-Ghhi and T-fluoro (2 (-F), The 2'-modif.fcation may be in the arabia (up) position or ribo (down) position. In one aspect, a 2 "arabino modification is 2'-F <Similar modifications may also be made at other positions on the polynucleotide, for example, at the 3 'position of the sugar at the 3' terminal nucleotide or in 2! -5 * linked polynucleotides and the S 'position of S' terminal nucleotide. See also, for example, US Pat. Nos. 4,281,957: 5,118,800; 5,319,080; 5,350,044; 5,393,878; 5,448,137; 5,466,785; 5,514,785; 5,514,785; 5,591,722: 5,597,909; 5,610,300; 5,827,053; 5,639,873; 5,646,265; 6,653,873; 5,670,633; 5,792,747; and 5,700,920, the disclosures of which are incorporated by reference in their entirety heroin. m aspect, a modification of the sugar Includes Locked Nucleic Acids (LMAs) in which the 2'-hydroxyl group Is linked to the 3 'of 4' carbon atom of the sugar ring, thereby forming a hicyciic sugar moiety, The linkage is in certain aspects a methylene (- OH -) n group bridging the 2 'oxygen Mom and the 4' carbon atom while n is 1 or 2. LNAs and preparation thereof are described in WG 38/39352 and WO 99/14226, the disclosures c which are incorporated herein by reference, A surface density adequate to make the nanoparficles stable and the conditions necessary to obtain it for a desired combination of nanoparticles and polynucleotides can be determined empirically, Generally, a surface density of at least 2 pmofea / cirL will be adequate to provide stable nanoparticle-efigonyeteofide compositions, In some aspects, the surface density is at least 15 pmofes / crac Methods also provided the polynucleotide is bound to the nanopartide at a surface density of at least 2 pmol / cnf, at least 4 pmoNm at least 8 pmof / omL at least 9 pmoi / cm *, at least 10 pmol / cm2, at least about 25 pmol / orrf, at least about 50 pmol / cmp at about 75 pmol / em2, at least about 100 pmol / em2, at least about 150 pmol / om2, at least about 200 pmoi / cm5 · at least about 400 pmoi / omg at least about 1000 pmoi / cms or more.
    Nucleic add molecules contemplated for use in the methods described herein Include those bound to the nanoparticle through any means. Regardless of the means by which the nucleic acid molecule is attached to the nanopartide, attachment in various aspects is effected through a 5 'linkage, a 3' linkage, some type of internal linkage, or any combination of these attachments.
    Methods of attachment are known to those of ordinary skill in the art and are described in, for example, US Publication No, 2009/0209629, which is incorporated by reference herein in its entirety, Methods of attaching rna to a nanoparticle are generally described in ΡΟϊ / Ο82009 / 65822, which is incorporated by reference herein in Its entirety. According to some embodiments, the disclosure contemplates that a polynucleotide attached to a nanoparticle is RNA,
    In certain aspects, functionalized nanoparticles are contemplated which include those where a nucleic acid molecule is attached to the nanopartide through a spacer. "Spacer" as used herein means a moiety that does not participate in litter nucleic add binding per se but which serves to increase distance between the nanoparttete and the fonctbnai nucleic acid molecule, or to increase distance between individual nucleic acid molecules when attached to the nanoparticle in multiple copies. Thus, spacers are contemplated to be located between individual nucleic acid redfish in tandem, whether the nucleic acid molecules have the same sequence or have different sequence «; in one aspect, the spacer when present is an organic moiety, in another aspect, the spacer is a polymer including but not limited to a water-soluble polymer, a nucleic acid, a polypeptide, an oligosaccharide, a carbohydrate, a lipid, and ethylglyoel, or combinations thereof.
    In certain aspects, the spacer is a poly nucleotide which is covalently bound to the nanoparticles. These spacer polymers are the same polynucleotides as described above. As a result of the binding of the spacer to the nanoparticles, the firsi / seeond: polynucleotide is spaced away from the surface of the nanopertices and is more accessible for hybridization with its respective second / first nucleic add. In instances where the spacer is a polynucleotide, the length of the spacer in various embodiments is at least about 10 nucleotides, 10-30 nucleotides, or even greater than 30 nucleotides. The spacer may have any sequence which does not interfere with the ability of the firsi / second polynucleotide to become bound to the nanoparticles or to its binding, to a complementary molecule. Typically, the spacers should not have sequences complementary to each other or to that of the first nucleotide, but may be all or in part complementary to the second polynucleotide.
    According to a second aspect, the present invention provides a method for recovering hydrocarbons from a formation comprising · providing a first fluid comprising a first nucleic acid molecule, to a first permeable region of the formation from a first location near or and / or adjacent the first region, providing a second fluid comprising a second nucleic acid molecule to the first permeable region from the first location and / or a second location near and / or adjacent the first region, and allowing the first and second fluids to contact to allow the first and second nucleic .acid.molecules to hybridize, or otherwise bind to one another to form a complex capable of reducing the permeability in at least a portion of the first region; and providing a displacement substance in the formation to displace hydrocarbons from the formation.
    Iha method may comprise injecting a flood fluid »such as water * into the formation, to displace hydrocarbons from the formation.
    Tire method may comprise injecting the first fluid from at least one first wellborn, e.g. production wellbore.
    The method may comprise injecting the second fluid from at least one first wellbore and / or at least one second wellbore, e: g. injection wellbore.
    The method may comprise recovering hydrocarbons from at least one first wellbore, e.g. production wellbore.
    The features described in relation to any other aspect or the invention can be applied in respect of the method according to a second aspect of the present Invention, and are therefore not repeated here for brevity.
    The present invention will now be further described by way of example and with reference to the figures which show:
    Figure i shows a schematic representation of complex formation occurring between two different types of nucleic acid'functionalised nanoparticles which are designed to bind to each other; spirit
    Figure 2 shows a representation of complex formation in an area, of high permeability substrate following introduction of first and second conformation controlling fluids from separate wells adjacent to the high permeability area,
    Heterogeneity in oil reservoirs remains a major challenge for the oil industry in terms of oil recovery related to macroscopic displacement issues. For example, very high-permeability zones may be present due to the sedimentation history of minerals from which the reservoir is made. In the Middle East, for example, zones of reservoirs originating from high-energy zones * such as coral reefs may be highly permeable to certain geological formations. Hence, these zones will lead to adaptation of iow-permeabity pore networks, during water or chemical flooding and will result in low and inefficient macroscopic displacement * The present invention may find particular application in such areas
    The preset invention serves to avoid this bypass selectively plugging these high-permeability zones hence Ping dives the flow path of the flood towards idw-permeability zones.
    This is achieved by way of employing two separate nucleic acid molecules. to a region of high permeability, which are designed to hybridize to one another. Each nucleic acid molecule is bound to a nanoparticle and hybridization of the nucleic acid molecules leads to the formation of a complex which is designed to act as a plug and reduce or eliminate flow of a flood fluid through the region of high permeability.
    Nanoparticles with a given type of polyurethane strand wifi do not aggregate with nanoparticles of the same type (due to incompatible bases prevention; base-pair interaction) and hence plugging is efficiently avoided when nanopaslioies with only one typo of polynucleotide sequence are present, such as In the steer well tore regions. Furthermore, the particles will not adsorb to oil-wet rock material due to the hydrophilic nature of the ONA beaches. Due to the presence of high permeability zones the nanoparticles will preferably be directed to these areas and when lor example polyA- and poly! Nanoparticles meet in these areas, optionally in a. High salt concentration (charge shielding the negative phosphate groups or DMA) will result in very strong Å - T recognition and binding (essentially a salting-out effect, ie, solvation power of water Is highly reduced and base-pair interactions will circumvent solvation offsets). The hybridization of poiyA and poiyT strand will lead to the assembly of nanoparticles in a DNA hybridizailoredinvcted complex with high mechanical strength due to the DMA-DMA interaction enhanced by high salt concentration. This is represented schematically in Figure i,
    Figure 1 shows what happens when nanoparticles (10) which are functionalized with poly-A oligonucleotioes are allowed to come in contact with nanoparticles (12) which are functionalized with poly-T oligonucleotides. The two types of nanoparticles (10, 12) are able to hybridize to one another through complementary base pairing In order to form a complex (14). Due to the fact that each nanoparticle (Id, 12) comprises a plurality of oligonucleotides.bound to the surface of the nanoparticle (1.0, 12), a large complex (16) is capable of being termed which comprises many nanoparticles (10, 12).
    An example of how this would work in practice is shown schematically in Figure 2 for example, which shows how plug (20) formation occurs in the area of high permeability (22) Åcønfermaiføn controlling fluid comprising ionized nanoparticles t26), which comprise a first nucleic acid molecule is provided to a first well (28) and the fluid and nanoparticles enter the area of high permeability. {22}, where the nanopartides (26) form the first conformational tip id are able to come into contact with functionalized nanapartlofes. (30), which comprise a second nucleic acid molecule complementary to the first nucleic acid. The functionalized narsopsrddes (30), which comprise the second nucleic acid molecule, have been provided to the area of high permeability from a second well (32} adjacent to the area of high permeability, tout away from the first well (28),
    Mixing may be promoted as follows. A first conformance coniroll-ng fluid containing the first type of nanoparticles (.26) can be designed to be much less viscous than the second conformance controlling fluid containing the second type of nanopasiioles (30), the latter solution containing eg, a polymer . Hence the. fluid containing the first type of nanoparticle (28) will create viscous lingering through the other nanopartide (30) containing fluid rather than displacing the solution containing the other type of nanopadicles in a piston-like fashion.
    Once the first and second complementary nucleic acid molecules contact each other, they are able to hybridize to one another, thereby forming a complex which may be comprised of many functionalized nanoparticles (26, 30} due to each nanoparticle comprising a plurality of nucleic acid molecules The formation of the complex leads to a plug (20) being formed in the area of high permeability, however, the nanoparticles (26, 30) provided from the first and second wells are not expected to come into substantial contact within an area of low permeability (44), or will do so at a much reduced frequency and such complex formation and hence plug formation is not expected to occur in the area of low permeability (44),
    Plugging In small pores is not expected to be a significant problem. Once the nanoparticles (28, 30} have had time to mix, the complementary nucleic acid molecules will hybridize to one another and ping up the areas where they have mixed, primarily in the high-permeability zones {22). If the two types of nanoparticles (28, 30} have been pumped from opposite sides of the zone of permeability, the risk that they will react in the near well-bore matrix is minimal, it is of course necessary to displace both types of nanoparticles (26, 30) from the wellbore with property sized slugs The probability of two non-aiready-in-piace components to meet in a low-permeability zone - (44) when injected from two different wells (28, 32} will be However, if plugging in low-permeabity zones should occur, these can easily be removed by injection of alkaline water, for example, in order to disrupt the bonds formed between the complementary base pairing.
    When a stable plug has been established in the high permeability zone (22}, the wafer flood or chemical flood can be injected and the flood flow paths will be diverted towards initial low permeability zones (44). Since surfactants and polymers are commonly used For enhanced: oil recovery purposes do not have the ability to participate in Hydrogen bonding, these are not expected to disrupt DNA-DHA interactions. Furthermore, DNA dupiexes will remain stable when alcohol is present (due to the sating out effect as well ) so co-solvents can be included in the chemical flood.
    In accordance with a specific embodiment of the invention, the first and second nucleic acids may be PolyA and polyT respectively and these may be provided from two different wails- (28, 32) to avoid in-between and near well-bore plugging resulting from nonpreferabie DNA-directed nanoparticle assembly.
    Alter the plug (20) has formed it can become permanent through the use of cross-linking agents for example, or If can be removed in a controlled manner such as fey using a denaturing agent known in the art.
    权利要求:
    Claims (10)
    [1] 1. A method of selectively reducing the permeability of a first region of a subterranean formation, the method comprising providing first and second conformance controlling fluids to the first region, wherein the first conformance controlling fluid comprises a first nucleic acid molecule and the second conformance controlling fluid comprises a second nucleic acid, and wherein said first and second nucleic acid molecules are capable of hybridising or otherwise binding to one another under appropriate conditions such that a nucleic acid complex is formed reducing the permeability in at least a portion of the first region.
    [2] 2. The method according to claim 1 wherein the first and second conformance controlling fluids may be provided from first and second wellbores situated on either side and/or adjacent to the first region of permeability.
    [3] 3. The method according to any preceding claim further comprising providing a salt, such as NaCI, in order to faciiitate binding of the first and second nucleic acid molecules.
    [4] 4. The method according to any preceding claim further comprising providing a nucleic acid cross-linking agent to the first permeable region in order to stabilise any complexes formed therein.
    [5] 5. The method according to any preceding claim further comprising providing a denaturing agent, such as urea or formamide and/or increasing pH through use of an appropriate base, such as NaOH, typically in solution, to a region of low permeability in order to reduce any complexes formed therein.
    [6] 6. The method according to any preceding claim wherein the first and second conformance controlling fluids are of different viscosities to encourage mixing of the first and second conformance controlling fluids.
    [7] 7. The method according to any preceding claim wherein the first and second nucleic acid molecules are provided as nanoparticles functionalised with said first and second nucleic acid molecules respectively,
    [8] 8. The method according to any one of the claims 1-7 wherein the first nucleic add is a polyA molecule (polyA being a nucleic acid chain formed from identical adenine molecules) and the second nucleic acid is a poiyT molecule (polyT being a nucleic acid chain formed from identical thymine molecules), or the first nucleic acid is a poiyC molecule {a chain of cytosine molecules) and the second nucleic acid is a polyG molecule (a chain of guanine molecules).
    [9] 9. A method for recovering hydrocarbons from a formation, comprising: providing a first fluid comprising a first nucleic acid molecule, to a first permeable region of the formation from a first location near or and/or adjacent the first region, providing a second fluid comprising a second nucleic acid molecule to the first permeable region from the first and/or from a second location near and/or adjacent the first region, and allowing the first and second fluids to contact to allow the first and second nucleic acid molecules to hybridise or otherwise bind to one another to form a complex capable of reducing the permeability in at least a portion of the first region; and providing a displacement substance in the formation to displace hydrocarbons from the formation.
    [10] 10. The method according to either of claims 1 or 9 further comprising recovering said hydrocarbons from at least one first wellbore, e.g. production wellbore.
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    同族专利:
    公开号 | 公开日
    EP3027705B1|2020-01-22|
    DK178320B1|2015-12-07|
    WO2015014939A1|2015-02-05|
    EP3027705A1|2016-06-08|
    US20160186041A1|2016-06-30|
    GB201313897D0|2013-09-18|
    US9915123B2|2018-03-13|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    GBGB1313897.9A|GB201313897D0|2013-08-02|2013-08-02|Conformance control in enhanced oil recovery|
    GB201313897|2013-08-02|
    PCT/EP2014/066501|WO2015014939A1|2013-08-02|2014-07-31|Conformance control in enhanced oil recovery|
    EP2014066501|2014-07-31|
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