• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    The present invention relates to an improved method of oil recovery using aptamers which are designed to adhere or bind to subterranean surfaces, such as hydrocarbon-bearing rock surfaces. There is also provided a method of obtaining suitable aptamers for use in a method of hydrocarbon, such as oil recovery.
    公开号:DK201570245A1
    申请号:DK201570245
    申请日:2015-04-28
    公开日:2015-05-11
    发明作者:Kristian Mogensen；Martin Bennetzen
    申请人:Mærsk Olie Og Gas As；
    IPC主号:
    专利说明:

    modifiers
    The present invention relates to an Improved method of oil recovery using aptamers which are designed to adhere or bond to subterranean surfaces, sued as hydrocarbon bearing rock surfaces. There is also a method of obtaining suitable aptamers for use in: a method of hydrocarbon, such as oil recovery, iackpimndtotheihVBntion
    Water flooding · as an oil recovery technique has been in use since 1880 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 th © oil and gas in the reservoir and thereby serves to maintain pressure. Recovery factors from water flooding vary from 1-2% In heavy oil reservoirs up to 50% with typically values around 30-35%, compared to 5-40% obtained from primary depletion without water flooding.
    Techniques designed to modify the wettability of rock within the reservoir have been sought. Wettability refers to the tendency of a fluid to preferentially cover the surface of a solid, in this case the reservoir rock »and is often estimated by measuring the contact angle. If a water droplet has a contact angle below 90®, the rock is said to be water-wet. On the other hand, if oil prefers the rock surface, the rock is referred to as oil-wet Many rocks, however * contain some surfaces that are water-wet and others that are oil-wet; such rocks are called mixed-wet When a fluid such as water wets the rock surface, it forms a film layer, which maintains hydraulic connectivity throughout the rock, in a mixed-wet system, both oil and water can maintain hydra «lie continuity at the same time over a large saturation span. Wettability is thought to be one of the most important factors governing oil recovery (Morrow, NR, "Wettability and its Effect on Oil Recovery ** JPT {Deo. 1990), 1478-1484.} A large amount of oxperirnentat evidence suggests that oil recovery Increases as the contact angle approaches 8Ge "a situation called neutral wettability, where neither of the fluids tends to wet the rock. Research efforts aimed at altering wettability to improve oil recovery are known.
    Current methods for altering reservoir rock wettability from strongly oil-wet or strongly waten-wei to neutral-wet have so far been water-based. Since wettability reflects the interplay between fluids and: rock surface, if it is important to realize that methods that have been shown to work for sandstones may not reveal a similar potential in carbonate rocks and vice versa.
    Caustic Flooding (& foci of pH}: Caustic flooding has been reported to change the wettability as a change in pH will affect the surface charge of the rock and hence the tome balance at the fluid-rock interface (Nirasaki, G, J "Milter , CA and Puerto, M.> "Recent Advances in Surfactant EEA * SPE 116388 {2008).
    Surfactant Flooding: Several researchers have .reported wettability alteration effects with anionic as well as non-ionic surfactants for both sandstone and carbonate rocks. One such study was reported by Mohan et al ,, (Mohan, It, Gupia, R. and Mohanty, KK. "Surfactant Flooding for a Maersk Carbonate Reservoir *, UT Austin Final Report 2009). removal of adsorbed naphthenic acids through ion pairing with the surfactant
    Lcm-Saiiniiy Flooding in Sandstones: Low-salinity effects were reported back in the 1960's but it was the work by Tang and Morrow (Tang, GQ and Morrow, NB, "Salinity, Temperafere, Oil Composition, and Oil-Recovery by Waterflooding" , SPE '35860, 1S9.7), which kick-started research to understand the physical medianishis behind low-salinity effects. BP has demonstrated field examples that show improved oil recovery from their io-sal ™ recovery technique,
    Smart Wafer ø Ghaik: Work fey Professor Tor Austad's group at the University of Stavanger has shown that potential determining ions to calcium and sulphate Influence the surface charge of some North Sea chalk samples (Zhang, P. and Austad, 1 ,, '' Wettability and oil recovery from carbonates: Effects of temperature and potential determinants *, Colloids and Surfaces A: Physicochem. Eng, Aspects 278 (2006), 179-187). An alternative explanation was proposed by Hiorth et ah (Hlorth, A ,, Cathies, t.fvt.s Madiand, MV, "The Impact of Pore Water Chemistry on Carbonate Surface Charge and 03 Wettability *, Transport in Porous Media 2010), who claimed that rock dissolution was responsible for the improved oil recovery.
    Modified Seawater Flooding in Carbonates: Recent Publications by Saudi Aramco and ExxonMobil (Yousef, AA, Ai-Saieh, S, t and Al-Jawfi, M. (2011)), "New Recovery Method for Carbonate Reservoirs through Tuning the Injection Water Salinity : Smart Waterflooding ", SPE 143550 (2011) and Gupta, R. et: at," Enhanced Waterflood for Middle East Carbonate Cores - Impact of Injection Water Composition ", SPE 142668 (2011) indicate that a modified seawater composition may lead to wettability alteration In certain limestone and dolomite rocks Exxon concluded that phosphate should be added to the injection water
    Although a number of techniques have been described, there is a desire to provide an improved method of modifying rock surface wettability. Indeed, there is a need to provide a method, which may find application in a variety of situations.
    The present invented Is based on the development of aptamers which are designed to adhere or bind to surfaces such as rock surfaces so as to preferentially reduce the ability of. hydrocarbons, such as oil (including crude oil), to wet the surface, By reducing the ability of hydrocarbons / oil to wet a surface, for example, a rock surface, • oil recovery from a particular hydrocarbon-bearing reservoir w rods formation may be enhanced or made easier. As described in the background of the present invention, it may be desirable to render the surface or rock surface more neutral in terraces: .of its wettability to water and oil ..
    In a first aspect there is provided a method of selectively modifying wettability of a surface or substrate, the method comprising providing one or more aptamer molecules to the surface or substrate, said aptamer moiecu1e {s) is / are designed to. the surface or substrate,: n order to modify said wettability of the surface or substrate.
    The surface or substrate may comprise a subterranean surface or substrate, for example a rock surface, as may be found in a hydrocarbon bearing reservoir and / or rock formation. Hereinafter, the term "substrate" shall encompass both the terms "surface * and" substrate *.
    Desirably, the said aptamer raolecute (s) are Intended to modify the wettability of the (subterranean) substrate to make the substrate closer to neutral wettability is a hydrocarbon, such as oil and / or water, than before the aptamer (s) was added. . The skilled reader can easily measure and test for the wettability of a substrate.
    Wettability may be measured, for example, according to the Amott-Harvey imbibition test, as described in Arnett E Transactions ΑΙΜΕ 216 (19S9); 158-162 and / or a US
    Bureau of Mines (USSM) test (Donaldson et al, {1969} Society of Petroleum Engineers Journal, pi 3-20). Wettability may also be derived from tracer testa where chromatographic separation of unreactive thlocy moieties that do not adhere to a rock surface and sulphate (or another tracer) that binds to a water-wet area of a smoke is a proxy for water-wetness of the rock system (see Strand, S, t Standees, DC, and Ausiad ·, T>, 2006b. New wettability test for chalk based cm chromatographic separation of SON "and 80.52, Journal of Petroleum Science and Engineering, 62: 187-197.
    It will be appreciated that generally a large quantity of aptamer molecules may be used and the amount used will depend on the surface area (namely - the total target surface area) of the surfaces of the reservoir and / or rock formation. Furthermore, the actual or most appropriate amount of aptamer also depends on the ohemistry / physscal properties of the surfaced) of the reservoir / forrnatlon (charge / porosity and the like). For example,: sufficient aptamers to provide at least about 1, IQ, 100, 10s, 104 10δ »10®, Iff, W ™ aptamer molecules per cm% urface (target surface area) may be used.
    The aptamer motecufes may be identical or different so as to take account of different surfaces which may be present in a particular formation. For example, in a particular subterranean location or formation, many different substrate surfaces, each with different chemistries and / or physical features, may be found. As such, the present invention may provide for a population or pool of aptamer molecules designed to bind to such a variety of surfaces. Thus, unlike other known applications in which extremely specific aptamers are developed and employed, the present Invention- may use a population or pool of aptamers of differing affinities to a particular substrate surface. Thus, a population of aptamers which are able to bind slightly different surfaces may be provided. Such a population of aptamers may allow for minor or natura! alterations in the surface of the substrate which may be observed and different apfambte within the population of aptamers will be capable of binding to different locations on the surface of the substrate, in contrast, a single very specific aptamer may not be capable of binding a surface displaying a variety of surface chemistries and / or physical attributes.
    The terms "substrate1" and / or "surface" as used herein may encompass any type or form of inorganic and / or organic surface, using a particular hydrocarbon reservoir may be formed and / or comprise a variety of rock surfaoes / sfrucfures / and / or types / compositions of rock ag. sandstone and carbonate. Thus, the aptamers of the present Invention may be selected on the basis of a particular hydrocarbon reservoir from where it is desirable to be able to recover particular hydrocarbon (s), such One or more samples of rock from the reservoir may be obtained © In order to identify said one or more aptamers which are designed to adhere to the rock surfaces found within the particular reservoir Alternatively, representative aptamers may be obtained which bind to a particular type of rock Such representative aptamers may be used If a reservoir is known to be formed of a particular rock type. In this less previously obtained aptamers may be used for use in reservoir rock formations of a similar smoke type, For example, panels of aptamers may be developed based on types of different rock surfaces and stored for use at a later date. Once the type of rock in a particular reservoir is known, the skilled person may select a desired apfamer, or population of aptamers from a panel of aptamers previously made. In use, the aptamers of the present Invention are intended to adhere and / or bind to the surface of rock found within a hydrocarbon bearing reservoir in preference to the hydrocarbon itself. In this manner, the aptamers are intended to modify the ability of the hydrocarbon, such as oil, to wet the surface of the rock. Without wishing to be bound by theory, it is expected that if a rock surface becomes more neutral in terms of its ability to be water wet 'and / or oil wet »there is a reduction in the -degree of oil binding to the rock surface. and more hydrocarbon (ag, oil) may be available for recovery from the reservoir.
    The one or more aptamers of the present invention may be added / provided to the reservoir by way of a fluid comprising said one or more aptamers. Said one or more aptamers may be allowed to adhere / bind to the rock surface for a period of time, before any hydrocarbon recovery is commenced. Alternatively, one or more aptamers may be provided to the reservoir by a displacement substance which is Intended to facilitate recovery of any hydrocarbon from the reservoir.
    Thus, in a further aspect the present invention provides a fluid or displacement substance, such as a flood fluid for use in hydrocarbon, such as {crude) oil recovery, the displacement substance comprising one of more aptamers designed to specifically bind to a (subterranean) ) surface, such as a rock surface. Typically the fluid or displacement substance is wafer, brine or sea water. The fluid or displacement fluid may comprise other components such as extraction aptamers. These are aptamers with an affinity for hydrocarbons which are bound, adsorbed and / or otherwise associated with or with a surface), polymers, alcohols, baste (alkali) agents, acidic agents, gels, including water sweliabie gels, cross-linker molecules, surfactants, materials / compounds for fracking, salts and / or dissolved gases. By way of example, a fluid or displacement substance may comprise an apiamer based hydrocarbon extraction moiety designed to affect the release of hydrocarbons which are bound, adsorbed or otherwise associated with or with a surface (for example a rock surface as might be present in a subterranean formation or hydrocarbon-bearing rock formation).
    The aptamer (s) may be provided with at least one wellbore, e, g, injection wellbore. The methods of the present Invention may comprise recovering oil from at least one wellbore, e.g. production wellbore. Desirably the wettability of the surface is modified by application of said one or more aptamers, such as to make the surface more, neutral hydrocarbon (e.g. oil) viable. In this manner, the recovery factor of said hydrocarbons may be increased. Typically, the apiamer (a) of the present Invention, which are designed to bind to a substrate surface, such as rock, may also be chosen so as not to be able to bind with any degree of high affinity to the hydrocarbon, such as oil which is desired to be extracted. Thus, when identifying an aptamer or aptamers for use in a method of this invention, potential aptamer (s) may be screened for binding against a sample of hydrocarbon from a target: hydrocarbon-containing reservoir or rock formation.
    In a further aspect there is provided a method of producing one of more aptamers for use in enhancing hydrocarbon (such as (erode) oil) recovery from a hydrocarbon bearing reservoir or rock formation (for example a subterranean formation), the method comprising a mixture of aptamers to a surface of a substrate representative of substrate found within the hydrocarbon bearing reservoir, or rock formation (for example, subterranean formation), each aptamer comprising a region of randomized nucleotides; and isolating said optamerfs) which bind to the surface of the substrate.
    Typically, the aptamers are in the form of an oligonucleotide comprising a central region comprising the randomized nucleotides and 3 'and / or 5' regions of known sequence. Typically the region of randomized nucleotides is from 8 to 250 nucleotides in length. The 3! and / or S 'regions of known sequence may facilitate Isolation and / or amplification of the aptamers, as will be described in more detail.
    The above method of identifying apfamers is generally based on the Systematic Evolution of Ligands by 'Exponential enrichment method, termed SELEX, as described in WO 911S813 which is herein incorporated specifically by reference. The SELEX method involves selection from a mixture of candidate oligonucleotides and generally step-wise iterations of binding, separation, and amplification using the same general selection scheme to achieve virtually any desired criterion of binding affinity and selectivity; Starting from a mixture of nuefelc acids, preferably comprising a segment of randomized sequence, the 8ELEX method includes steps of contacting the mixture with a target, which In the ease of the. present "invention is typically a rock surface, under conditions favorable for binding; separating unbound nucleic acids from those nucleic acids which have bound specifically to target molecules; dissociating the nucleic acid-target complexes; often amplifying the nucleic acids dissociated from the nucleic acid. target complexes to yield a ligand-enriched mixture of nucleic acids; and then reiterate the steps of binding, separating, dissociating and amplifying through as many cycles as desired to yield highly specific, high affinity nucleic add ligands to the target molecule.
    The basic SELEX. method described in W09119813 has been improved and modified over the years and Dua et al (Recent Patents on DMA & Gene sequence 2008, 2,172-188) provide a review of relevant patents related to SELEX. Each of the Identified pafenf / pateni applications identified in the above paper by Qua ei a15 are incorporated herein by way of reference.
    Certain terms used to describe the invention herein are defined as follows; "SELEX" methodology refers to a method of selecting nucleic add aptamers which interact with a substrate / surfactant in a desirable manner, for example binding to the substrate / surface, with amplification / isoiation of those selected nucleic acids as described in detail above and In the SELEX Patent Applications and papers referred to above, iterative cycling of the selefion / amplifieatlon steps allows selection of one or a small number of nucleic · adds which interact most strongly with the substrate / surface from a pool containing a very large number of nucleic acids. Cycling of the selecflon / amplification procedure · Is continued until a selected goal is achieved Although oyding / amplification is .often · employed Hoon et at (Bloteohnlques, 2011, 51: 413-416}, to which the skilled 'reader is directed and the contents of which are herfey Incorporated, describe a method of selecting aptamers by high-throughput sequencing and informatics analysis, which only requires one round of positive selection followed by high-throughput DMA sequencing and Informatics analysis In order to select high-affinity apiamem. Thus, cycling and / or amplification is seen as optional although desirable in many cases. "Nucleic acid" means DMA, RNA, single-stranded or double-stranded, and any chemical modifications thereof. Modifications include, but are not limited to, those that provide other chemical groups that incorporate additional charge, polarizability, hydrogen bonding, electrostatic Infcracflpft, and fluxionslify to the individual nucleic acid bases or to the nucleic acid as a whole. Such modifications include, but are not limited to, modified bases such as.2! ~ Poslfton. sugar modifications, 6-position pyrimidine modifications, S-posifion purine modifications, cytosine exocyciic amines modifications, substitution of S-bromo-uradl; backbone modifications, methyiations, unusual base-pairing combinations such as the isobases isoeyfidine and Isoguanldine and the like. Modifications can also include 3 · and 5! modifications such as capping. Modifications that occur after each round of amplification are also compatible with this invention. Post-amplification modifications can be reversibly or irreversibly added after each round of amplification. Virtually any modification of the nucleic acid is contemplated by this invention. "Mixture of aptamers" is a mixture of nucleic adds of differing, randomized sequence. The source of a "reek of apiamers" is from naturally occurring · nudele adds or fragments thereof, 'chemically synthesized nucleic adds, enzymatically synthesized noodle acids or nucleic acids made by a combination of the foregoing techniques. In a preferred embodiment, eeeb nucleic acid has feed sequences surrounding a randomized region to facilitate the amplification process. The length of the randomized section of the nucleic add is generally between S and 250 nucleotides, preferably between 8 and 60 nucleotides,
    Said "one or more aptamerCsf is a nucleic acid molecule (s): which has / been isolated from the mixture of apiarners and which binds to the desired surface," Separating "means any process for separating bound nucleic acid aptamers from the remainder of the unbound aptamers, Separating can be accomplished by various methods known in the art, Filter binding, affinity chromatography, liquid-liquid partitioning, filtration, gel shift, equilibrium - partitioning density gradient centrifugation are all examples of suitable-separating methods, "Amplifying "means any process or combination of process steps that increases the amount or number of copies of a molecule or class of molecules, in preferred embodiments, amplification occurs after members of the apfamer mixture have been separated, and it is the surface bound nucleic add aptamers For example, amplifying RNA molecules can be carried out by a sequence of three reactions · making cOMA copies of selected RNAs, usin g the polymerase chain reaction to increase the copy number of each cPRA, and transcribing the cDNA copies to obtain RNA molecules having the same sequences as the selected RNAs. Any reaction or combination of reactions known in the art can be used as appropriate, including direct DNA replication, direct RNA amplification and the like, as will be recognized by those in the art. The amplification method should result in the proportions of the amplified mixture being essentially 'representative of the proportions of different sequences in the mixture prior to amplification. It is known that mariy modifications to nucleic adds are compatible with enzymatic amplification. Modifications that are not compatible with amplification can be made after each round of amplification, if necessary. "Randomized" is. a term used to describe a segment of a nucleic acid having, in principle, any possible sequence over a given length. Randomized sequences will be of various lengths, if desired, ranging from about eight to more than one hundred nucleotides. The chemical or enzymatic reactions by which random sequence segments are made may not weld mathematically random sequences due to unknown biases or nucleotide preferences that may exist. The term Randomized "is used instead of" random "to reflect the possibility of such deviations from non-ideality. In the techniques presently known, for example sequential chemical synthesis, large deviations are not known to .occur. For short segments of 20 nucleotides or less ,: any minor bias that might exist would have negligible consequences. The longer the sequences of a single synthesis, the greater the effect of any bias. A bias may be deliberately introduced Into a randomized sequence, for example, by altering the molar ratios of precursor nucleoside. {or deoxpudeoside) triphosphates, in the synthesis reaction or the ratio of phosphoramidites in the chemical synthesis. A deliberate bias may be desired, for example, to affect secondary structure, to introduce bias toward molecules known to have facilitating activity , to introduce certain structural characteristics, or based on preliminary results.
    In a basic form, the SELEX process for use in accordance with the. present invention may be defined by the following series of steps: 1) A candidate mixture of different sequence sequences is prepared The candidate mixture generally includes regions of fixed sequences (each member of the candidate mixture contains the same sequences in the same sequence). Ideation) and regions of randomized sequences. The fixed sequence regions are selected either: (a) to -assist in the amplification steps described below, (jh) to mimic a sequence known to bind to the target, and / or (o ) to enhance the concentration of a given structural arrangement of the nucleic acids in the candidate mixture. The randomized sequences can be totally randomized (ie, the probability of finding a base at any position being one in four) or only partially randomized the probability of finding a base at any location'can fee selected at any level between 0 and 100 percent ). 2) The candidate mixture is contacted with a sample of substrate under conditions favorable for bonding between the target and members of the candidate mixture. Typically the sample substrate may be a rock surface, sample obtained from a hydrocarbon: such as an oil reservoir where it may be desired to apply an enhanced oil recovery technique. Under these circumstances, the interaction between the target: and the nucleic acids of the candidate mixture can be considered as forming nucleic aoid-added pairs between the target and those nucleic add having the strongest affinity for the target, 3) the nucleic acids with the highest affinity for the target are separated from: those noodle acids with less affinity to the target. Because only an extremely small number of sequences (and possibly only one molecule of nucleic add) correspondingly, to the highest affinity nucleic add exists in the candidate mixture, it is generally desirable to set the separating criteria so that a significant amount of the noodle acids in the candidate mixture (approximately 5-50%) are retained during separation. 4) Those nucleic adds selected during separation as flaying the relatively higher affinity to the target are then amplified to create a new candidate mixture that is enriched in nucleic adds having a relatively higher affinity for the target, 5} By repeating the separation and amplifying steps Above, the newly formed candidate mixture contains fewer and fewer unique sequences, and the average degree of affinity of the noodle acids to the target will generally increase. Taken to Its extreme, the SELEX. process will yield a candidate mixture containing one or a small number of unique nucleic acids representing those nucleic adds from the original candidate mixture having the highest affinity to the target molecule.
    The SELEX process when used in accordance with the present Invention thus provides high affinity aptsmers for binding to a subterranean substrate, such as a rock surfaca.
    The present application is concerned with identifying nucleic add aptamers to subterranean substrates, typically rock, surfaces. The aptamers so Identified can be used in enhanced oii recovery techniques known in the art. The aptamers of the present invention may be identified generally by the above method known as the SELEX process,
    According to a further aspect, a method of recovering hydrocarbons from a formation comprising; providing one or more aptamer mofeeuie (s) to the formation, said aptamer mdecuie (s) js / are designed to adhere to a rock surface within the formation, in order to modify said hydrocarbon wettability of the rock surface; and providing a displacement substance in the formation to displace hydrocarbons from the formation.
    The method may comprise Injecting a flood fluid, such as wafer, into the formation, to displace hydrocarbons from the formation.
    The method may comprise Injecting the flood fluid from at least one first 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 invention, apply in respect of the method according to a second aspect of the present Invention, and are therefore not repeated here for brevity.
    Detailed Inscription
    The present invention will now be further described with reference to the following figure which shows:
    Figure 1 shows a schematic form of the 8EWEX process as described by the present inventors. 8EWEX stands for systemic evolution of wettability modifiers by exponential enrichment and is based on the known SELEX process.
    Briefly and with reference to Figure 1, a DMA library (10) comprising 100s - 1000s of different oligonucleotides comprising different randomized sequences is provided. The large, oligonucleotide library (10) comprises randomly generated sequences of fixed length flanked by constant 5 * and 3 'ends that serve as primer binding sites. Thls DMA library (10) is provided in brine and contacted with a sample, of rock ( 12) An order that oligonucleotides (14) within the DMA library (10) are able to bind to the surface. (16) of the rock sample (12), the rock sample may be taken directly from a particular by-pass bearing reservoir, or could be a sample of smoke which is representative of rock within hydrocarbon bearing reservoirs. Some of the oligonucleotides (IB) within the library (10) do not bind to: the surface (16) of the sample of rock ¢ 12) and can be washed away using brine, for example.
    The bound oligonucleotides (14) are then eluted from the surface (18} of the sample of rock (12) using, for example, urea, iriofluoroacetic acid (TFÅ) or ihfjyoroethsno] fTFE) in order to provide isolated oligonucleotides (20) The isolated oligonucleotides (20) are then enriched by an amplification technique, such as P € R, in order to make more copies of the Isolated oligonucleotides (20) and provide an enriched sample of oligonucleotides (22). Thereafter the enriched oligonucleotides (22) are allowed to bind the surface (16) of the sample of smoke (12), but the conditions employed for washing the surface (18) of the sample of rock (12) are more stringent that the previous round, so that some of the enriched oligonucleotides (22) will not be capable of binding to the surface (18) of the sample of rock (12) when the more stringent conditions are employed. (but not limited to) urea, TFA or TFE to the brine used for washing the surface (16) of the sample of rock · (12), Thereafter the bound oligonucleotides can be eluted, amplified and enriched as before.
    The cycle of bonding to the surface (16) of the sample of rock (12) followed by elution, amplification and enrichment can be repeated a number of times, such as S - 15 times, but at each successive round or bond, the Conditions for binding are made more stringent, by increasing the concentration of the urea. TFA or TFE, .Eventually, after the successive rounds of binding, eluting, amplification and enrichment, a small number or even a single highly specific oligonucleotide (s) (24) is / are obtained which will be capable of binding to the surface ( 16) of the sample of smoke (12) with very high affinity, Such oiigopuoieotlde (s) may then be made In large quantities by, for example * cloning the © iigonucieotidefs) into a vector, such as a plasmid and expressing the cloned oiigonudeotide (s) and purifying the oligonue! eotide (s) using recombinant techniques well known to the skilled reader Ssmbrook and Russell {2001}. Molecular Cloning: A Laboratory Manual Ø'4 ed.) CSHt press.
    An exemplary method for generation of DMA aptamer (s) with high adsorption affinity to reservoir rock is described below: 1. A thin surface s's) is prepared from rock sample from an oil reservoir collected No washing should be done. Size: approx. Icml 2. S is placed in brine 3. Measure absorbance at 230nm (at. 260nm DNA absorbs) (At), Molecular extinction coefficient of single-stranded or double-stranded DNA. is 0.027 (pg / m) '1 cm'1 and 0.02 {pg / ml)' 1 cm "1 naspectiveiy, 4. Add a library of DMA molecules with 0 (10,000} different sequences. Equilibrate. Measure absorbance, A * 5. Remove supernatant, Measure absorbance in supernatant 6. Wash S with brine, 3-4 times Measure absorbances, Aj ^ i.3. 7 «Elute remaining DMA from S using eg urea, TFA (trifluoroacetic acid) or TFE (trifluoroethanol) - other interaction disrupters can be used 8. Desalt the © iuate and concentrate sample using e, e.g., CentnCon spin sites or gel electrophoresis 0, Amplify DNA using PCR (polymerase chain reaction) 10, Measure absorbance after amplification (Absorbances are used to estimate DNA kept at surface and washed away in each step using Lambert Beer law, respectively).
    Repeat steps (1-10) 10 -15 times using increasing concentrations of area, TFE, TFA or surfactant added to the brine for the wash in step 6, in this way DMA with continuous increasing binding affinity to the smoke surface is greatly enriched. Note than in step 4 the eluate from the previous round is used instead of the Initial huge DMA. library.
    After final round DMA apiamerCs) with extremely strong affinity to the rock is generated due to the very hard selection pressure in the successive washing steps.
    Optionally aptamer (s) with a desired affinity for the substrate, e.g., rock surface maybe contacted with the hydrocarbon e.g., oil, to be extracted in order to ensure that the aptamer (s) do not substantially bind to the hydrocarbon,
    This final pool is amplified by PGR and the nucleotide sequence can be determined by DMA sequencing (e, g, Sanger or Soiexa techniques). Large scale production of the high affinity aptamer (s) can be performed using recombinant techniques as described above.
    As mentioned previously, in certain embodiments it may not be necessary to have only a single aptamer and a pool os aptsmsrs which may show affinity to the surface (18) of the sample of rock (12).
    The apfamers or pool of aptamers of the present invention are intended to modify the ability of a hydrocarbon, such as oil, to wet the surface of rock within a particular hydrocarbon hearing reservoir. Typically, the aptarner or pool of aptamers are intended to decrease the hydrocarbon's ability to wet the rock surface and / or increase the ability of a flood fluid, such as water to wet the rock surface. In this less loss hydrocarbon, such as oil, is expected to adhere to the surface of the rock, enhancing the ability of the hydrocarbon to be extracted.
    For example, the aptamer or pool of aptamers may be added to the hydrocarbon bearing reservoir, typically by adding a fluid such as water. The ap1amer {s) are allowed a period of time to adhere to file rock surfaces within the reservoir iri order to displace any bound hydrocarbon from the rock surface. Thereafter a water flood or chemical flood can be injected into the reservoir in order to allow the displaced hydrocarbon such as oil to be recovered, typically by way of a production well
    权利要求:
    Claims (21)
    [1]
    A method of selectively modifying the wettability of a substrate in an underground formation, comprising providing one or more aptamer molecules to the substrate, wherein the aptamer or aptamer molecules are designed to adhere to the substrate to modify the wettability of the substrate.
    [2]
    The method of claim 1, wherein the aptamer molecule or aptamer molecules are intended to modify the wettability of the substrate to render the substrate closer to neutral wettability to a hydrocarbon such as oil and / or water than before adding the aptamer (s).
    [3]
    The method of claim 1 or 2, wherein at least 1, 10, 100, ΙΟ3, 104, ΙΟ5, ΙΟ5, ΙΟ7, 108 " are provided for 15 aptamer molecules for each cm 2 of substrate.
    [4]
    A method according to any one of the preceding claims, wherein the apatamer molecules are identical.
    [5]
    A method according to any one of claims 1-3, wherein a pool of different aptamer molecules is provided to take account of different surfaces that may be present in the particular formation.
    [6]
    A process according to any one of the preceding claims, wherein the aptamer molecule or aptamer molecules do not substantially bind or have low hydrocarbon binding affinity within the formation.
    [7]
    A method according to any one of the preceding claims, wherein the aptamer molecule or aptamer molecules are provided to the formation via a fluid.
    [8]
    A method according to any one of the preceding claims, wherein the aptamer molecule or aptamer molecules are provided to the formation by means of one or more injection wells extending within the formation.
    [9]
    A process according to any one of the preceding claims, further comprising recovering the hydrocarbon, such as oil, from the formation.
    [10]
    A displacer, such as flood fluid for use in hydrocarbon, such as oil recovery, the displacer comprising one or more aptamers designed to specifically bind to an underground surface, such as a rock surface.
    [11]
    The displacer of claim 10, wherein the displacer is water or sea water which may comprise other components such as salts or dissolved gases.
    [12]
    A method of producing one or more aptamers for use in increasing hydrocarbon (such as oil) recovery from an underground formation, which comprises providing a mixture of aptamers to a substrate representative of substrate found inside the underground formation, each aptamer comprising a region of randomized nucleotides; and isolating the aptamer or aptamers which bind to the substrate surface.
    [13]
    The method of claim 12, wherein the substrate has been obtained from one or more locations of the formation.
    [14]
    The method of claim 12 or 13, wherein the aptamers are selected to have a high affinity for the substrate.
    [15]
    The method of claims 12 - 14, wherein the aptamers are selected to have a low affinity for the hydrocarbon.
    [16]
    A method of recovering hydrocarbons from a formation, comprising: providing one or more aptamer molecules for the formation, wherein the aptamer (s) is designed to adhere to a rock surface within the formation, to modify the hydrocarbon wettability of the rock surface; and providing a displacer in the formation to displace hydrocarbons from the formation.
    [17]
    The method of claim 16, further comprising injecting a flood fluid, such as water, into the formation to displace hydrocarbons from the formation.
    [18]
    The method of claim 16 or 17, further comprising injecting the flood fluid from at least a first wellbore, e.g. injection wellbore.
    [19]
    A method according to any one of claims 16 - 18, further comprising recovering hydrocarbons from at least a first wellbore, e.g. production wellbore.
    [20]
    A method or displacer according to any one of the preceding claims, wherein the aptamer or aptamers is in the form of an oligonucleotide comprising a central region comprising randomized nucleotides and 3 'and / or 5' regions of known sequence.
    [21]
    The method or displacer of claim 20, wherein the region of randomized nucleotides has a length of from 8 to 250, such as 10 - 100, 15 - 50, 20 - 40 nucleotides.
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    同族专利:
    公开号 | 公开日
    WO2015032723A1|2015-03-12|
    GB201315743D0|2013-10-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    KR970002255B1|1990-06-11|1997-02-26|넥스스타 파아마슈티컬드, 인크.|Nucleic acid ligands|
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    MX2010012348A|2010-11-12|2012-05-15|Mexicano Inst Petrol|Composition based on germinal zwitterionic liquids as wettability modifiers in processes for the improved recovery of oil.|
    法律状态:
    2017-02-06| PHB| Application deemed withdrawn due to non-payment or other reasons|Effective date: 20161213 |
    优先权:
    申请号 | 申请日 | 专利标题
    GB201315743|2013-09-04|
    GB201315743A|GB201315743D0|2013-09-04|2013-09-04|Provision and uses of wettability modifiers|
    PCT/EP2014/068532|WO2015032723A1|2013-09-04|2014-09-01|Provision and uses of wettability modifiers|
    EP2014068532|2014-09-01|
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