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    • 专利摘要:
    The present invention relates to the development of aptamers which exhibit an affinity for, or which adhere or bind to, hydrocarbons adsorbed, bound or otherwise associated to/with a surface. The aptamers for use in this invention are capable of affecting the release of the hydrocarbon they bind, from said surface. Aptamers of this type are particularly useful in, for example, processes used to recover hydrocarbons from reservoirs or hydrocarbon-bearing rock formations where, even after primary extraction, a large quantity of residual hydrocarbon can remain adsorbed and/or bound to surfaces of the reservoir or formation. This aptamer based technology may be used in isolation or together with existing hydrocarbon recovery processes to further reduce residual hydrocarbon saturation and improve hydrocarbon production.
    公开号:DK201570226A1
    申请号:DK201570226
    申请日:2015-04-17
    公开日:2015-04-27
    发明作者:Kristian Mogensen；Martin Bennetzen
    申请人:Mærsk Olie Og Gas As；
    IPC主号:
    专利说明:

    The present invention is based on the development of aptamers which exhibit an affinity for, or which adhere or bind to, hydrocarbons adsorbed, bound or otherwise associated tp / wiiii a sitoacSv A method is also provided; or obtaining suttabie aptamers for use in a method of hydrocarbon recovery, as well as aptamers obtainable thereby,
    BACKGROUND TO THE INVENTION
    Water flooding as a da'fecø & ery léchniQu & fta & lbiié «in use since 1890 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 dll towards the producing welis 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 mainfain pressure ,: Recovery laotbrs from water flooding vary from 1: -¾% in heavy oii reservoirs up to 60% With typical values I around 30-3S%, compared to 5-10% obtained froth primary depletion without water flooding.
    However, a proportion of the oil is often retained within the formation adsorbed or bound to the subterranean smoke surfaces - the ultimate aim of any oii recovery process is to reduce this residue! oil saturation and increase production, W09117285A1 discloses methods and procedures for tracing the passage or flow of materials from one location to another. This technology may be applied to the tracing of petroleum products Speeiflcaliy, the methods provide biofogical maferiais, such as DMA, which can be added in smaii quantities to a material to be traced. U823DSCf282228A1 provides nucleic acid aptamers for binding to and absorbing the hydrooaitXih compound, bisphenol Å and mention is made of the 8ELEX procedure- However, it is acknowledged that% pitopes for roedgnltfofd on hydrocarbons are imitated ". WQ2G12138734 describes another form of tracer technology Specifically, the disclosure concerns the traceability of fields introduced and returned from, a production well.The invention provides an Unto identification system which takes the form of: particles encapsulating idehtltlabie :: DMA US6645769B2: these documents provide: a method of addition for the: hydrocarbon and water production from; a hydrocarbon reservoir, in particular, the inyentioh described in this patent inoives dividing the wells within a reservoir into a number of zones and adding a unique tracer: compound to each zone The tracers are chemically fixed or immobilised into the on and. are described as "Chemicaity Intelligent" such that they are released in response to certain events. The tracers ears are detected downstream to provide information about the zones within the reservoir. DNA is cited as an example at «suitable tracer.
    Craig & isenberg {1S70, F ^ IAS; v8 f3) pT337-1344} describe the binding of polycyclic aromatic hydrocarbons to double stranded poiyadenylic acid (poly A); specifically really, the intercalation of polycyclic arom atic hydrocarbons with poly A.
    Although a number of techniques for achieving enhanced oil recovery have been described, there is a desire to provide improved methods which Sower the residual oil saturation, indeed, there is a need to provide a method which may find application in a variety of situations.
    SUMMARY GF THE INVENTION
    The present Invention is based on the development of aptamers which exhibit an affinity for, or which adhere to or bind to, hydrocarbons adsorbed, bound or otherwise associated with / with a surface, Further, the aptamers for use in this invention are capable of affecting the release of the hydrocarbon they bind, from said surface. Aptamers of this type are particularly useful in, for example, processes used to recover hydrocarbons, for example in the form of oil, from reservoirs or hydrocarbon-bearing rock formations where, even after primary extraction, a large quantity of residual hydrocarbon can remain adsorbed and / or bound to surfaces of the reservoir or formation. The aptamer based technology described herein represents a further development in this field and may be used in isoiatlott or together with existing hydrocarbon recovery processes to further reduce residual hydrocarbon saturation and improve hydrocarbon production, should this be noted throughout this specification the term used to denote that embodiments of the invention "comprise" the noted features and as such, may also include other features. However, in the context of this invention, the term "comprising" may encompass embodiments in which the invention consists essentially of the relevant features .oPc ^ mfets' ^ '' fe-f ^ ev «nfføafem
    Thus, in a first aspect there is provided a method of recovering a hydrocarbon from a hydrocarbon-bearing reservoir or formation, said method comprising providing one or more aptamer molecules to the hydrocarbon-hearing reservoir or formation under conditions permitting the formation of aptamer hydrocarbon complexes ; and recovering the aptamer hydrocarbon complexes. A-more according to the first aspect of this; Invention.'may fee exploited as a method of recovering; a hydrocarbon from a surface of a hydrocarbon-bearing reservoir of a surface Of a hydrocaFtxjn-feearmg rock: formation.
    At least, a proportion of the hydrocarbons to be recovered may be bound, adsorbed and / or otherwise: associated with a surface of the hydrocarbon bearing: reservoir or formation. Such bound, adsorbed and / or in other ways associated or attached hydrocarbons wiii be referred to herein as "adsorbed hydrocarbons", Thus "adsorbed hydrocarbons" are hydrocarbons which are associated, bound and / or adsorbed to the serf aces of a hydrocarbon. bearing reservoirs rock formation.
    The aptamers for use in this invention may be designed to bind and / or adhere to adsorbed hydrocarbons (see definition of 'adsorbed' above). Aptamers of this type may otherwise be described as having; (or exhibiting) an affinity for hydrocarbons. Collectively, aptamers with these prbpenies may be referred to as "extraction aptamers>".
    Optamers used in this invention may exhibit an affinity for adsorbed hydrocarbons. Aptamers with an "affinity" for acne hydrocarbons may exhibit an ability to bind or adhere to hydrocarbons which are bound and / or adsorbed to a surface. The aptamers for use in this invention may be further capable of affecting the release of adsorbed hydrocarbon " that is, once the aptamer has bound an adsorbed hydrocarbon, if further affects its release from the surface to which if it is adsorbed: Hydrocarbon is released as a complex with an aptamer - a hydrooarbon / aptamer complex.
    The aptamers may have low / no affinity or substantially iow / nd affinity for a hydrocarbon · bearing reservoir or rock formation surface.
    Aptamers suitable for use in this Invention exhibit an affinity for adsorbed hydrocarbons and an ability to release hydrocarbons from a surface to which they are adsorbed. It should be understood that references to apfamers which exhibit an "affinity" for hydrocarbons embrace aptamers which bind to adsorbed hydrocarbons (of any type and adsorbed for any surface) and which release the hydrocarbon from the surface to which they are adsorbed.
    Without wishing to be bound by theory, aptamers suitable for use in this invention may exhibit an affinity for adsorbed hydrocarte greater than the affinity of the surface for the hydrocarbon. Thus, under such circumstances and in the presence of an aptamer designed for use in this invention, an adsorbed hydrocarbon is not only bound by the aptamer, but is released from the surface to which it was adsorbed. The released hydrocarbon is present as a complex with the aptamer. in this way the reieased, hyxdrocarbon / aptamer compiexes can be reeovered.
    Typically, aptms for use of this invention are in the form of a dlfgonudleot ^ e pnpriig a, # ntr $ regiéh comprising: randomized nucleotides and: 3 'and / or §! regions of Known Cuenca. Typically: the: .region of randomized nucleotides is from § to: 2oh nucleotides In length, a person of ski will appreciate: that the region corrtprisfng "mndonitsed" nucleic acids may delermide th ©; Sinding specificity of the aptamer. The 3 'and / or 5 * regions of known sequence can facilitate isolation and / or amplification of the aptamers, as described in more detail · A hydrocarbon to be recovered may comprise 0¾ crude of! or petroieorn containing many chemical comporsents and thus the invention finds particular application in tile field: Of (crude} oil recovery from, for example, pi hearing reservoirs and / or rock formations, including subterranean rock formations, in particular, this invention may be exploited .in.art enhanced off recovery procedure.
    Thus, there is provided a: method of enhanced oil recovery from an oil bearing reservoir or took: formation, said method comprising providing one or more aptamer molecules to the oil bearing reservoir or rock formation under conditions permitting the formation of aptamer oil complexes; and recovering the aptamer oil complexes,
    The methods of this Invention may be applied to the recovery of hydrocarbons and / or oils from surfaces including, for example, the surfaces present within a hydrocarbon dr oil bearing reservoir fiber formation. Suitably, the invention may provide a method of recovering a hydrocarbon from a surface, said method comprising providing one or more apiamer molecules to the surface under conditions permitting the formation of aptamer hydrocarbon opmpiexes; andrecovering: the aptamer hydrocarbon complexes.
    The term "surface® as used herein may encompass any type or form: of inorganic and / or '.organic surface to which a hydrocarbon may become adsorbed. Examples include rock surfaces (as might exist in hydrpcaitsbn-béaring reservoirs or rock formations) audit A person of skill will appreciate that a surface from which a hydrocarbon may be recovered may comprise one or more different types of surface each formed of and / or composed, a variety of rock with different chemistries and / or physical features. Furthermore, the hydrocarbon may comprise a heterogeneous mix of hydrocarbons and thus the surface of the reservoir or reck formation may comprise many different types of hydrocarbon each with different chemistries and properties. : and the like), therefore:, while the methods of ibis invention might exploit a Single type of ^ afoerwith :: - an;.: - affin '# fbr a particular type of adsorbed hydrocarbon and / or Hyd rocarbon adsorbed to a particular type of surface, ten methods may exploit a selection or pool of aptamers, each of which exhibits art affinity for rlffemnt adsorbed hydrocarbons and / or hydrocarbons adsorbed to one or more different types of surface.
    Thus, the invention may further provide a population, or poof of aptamers, cspmsing aptamers which exhibit affinity for specific types of adsorbed hydrocarbon or hydrocarbon adsorbed to dlfferent surface types., In contrast to single aptamers which may only have affinity for hydrocarbons bound or adsorbed to specific types of surface, a population of aptamers: vvith a variety of afilhies / specifieitles may allow for the natura! surface variation and / or alterations in surface composition, chemistry and geometry which might exist within, for example, a hydrocartion-bearing reservoir or rock formation.
    The aptamers for use in a method of this invention may be tailored or selected: for use in a specific reservoir or formation from which: is desirable fb recover a Hydrocarbon such as, for example, oil. The aptamers for use may be selected on the basis of their abifyto bind fa) specific types of hydrocarbon and / or (b): hydrocarbons adsorbed to the surface or surfaces present in the reservoir and / or formation. Thus the aptamers may be selected on the basis of the hydrocarbon content of the reservoir / fermaiion and / br on the basis pf lhe geofogy or surface frock) chemistry thereof; When selecting aptamers for use, one or more samples of rock and / or hydrocarbon from the hydrocarbon-bearing reservoir or rock formation may be obtained in order to identity aptamers which might exhibit affinity for the specific: hydrocarbon type (s | present and / or fo hydrocarbons adsorbed to the: specific rock type present Crucially, recovered samples of rock may be used to: Identify aptamers: which Shown rfo / iow / stfosianflaiiy low affinity for the smoke: ~ aptamers of thistype may be of most use,
    Previously obtained and / or developed aptamers: may be kept for use In reservoir rock / formations of a similar smoke: and / br hydrocarbon type. For example, panels of aptamers with affinity for different hydrocarbons may be developed and stored for use at a later date. Once the hydrocarbon content and / or geology of a reservoir or rock formation is known, the skilled person may select a desired apfamer, or population of aptamers from a panel of aptamers previously made / devetoped. Thus aptamers for use may be selected from a catalog of previously developed / obtalned aptamers. The previously obtained optimized aptamers may comprise a selection of 'representative aptamers * known to exhibit affinity' for particular types of hydrocarbon and / or hydrocarbons bound or adsorbed to specific «types of surface.
    The methods of this invention may use one or more representative aptamers known to have affinity for hydrocarbons of the type present: in tire: relevant ireseirvoipforaration and / br hydrocarbons bound to a surface or surfaces present therein. It will be appreciated that the methods of this invention may require: the use of a large quantity of aptamer moiecules; however, the actual or most appropriate amount will depend on the target surface area (namely - the total surface area of the reservoir and / or rock formation to which hydrocarbon is adsorbed and from which it requires recovery). The actual or most appropriate amount of aptamer will also depend on the ehemistry / physical properties of the surface (s) of the reservoir / tohnatlon (charga / porosity a $: The same). For example, sufficient aptamers ίο, pilpWde'atteast.abputl ^ lOyiOOy ΙΟ5,10Λ, 10b i0®, 10 1aptamer molecules per om% Uff ace (target surface area) may be used.
    The one or more; aptamers of the present invention may be provided with a reservoir, smoke formation of surface from which: It is desired to recover a hydrocarbon by way of a fluid comprising said one or more: aptamers. Said one or more aptamers rhay be.:$iqv^tQ· adhere ^ bd id hydrate adsorbed to a surface for a period of time, before any hydrocarbon recovery is commenced. The period of time may further correspond to the time required to ensure that adsorbed hydrocarbon bound by the aptamer (s) is / hasbeen released from the surface to which it was adsorbed.
    Additionally or alternatively, one or more aptamers may be provided with a reservoir, rock formation or surface by a displacement substance which is intended to facilitate recovery of any hydrocarbon from the reservoir.
    Thus, in a second aspect the present invention provides a fluid or displacement substance, such as a flood fluid for use in hydrocarbon, such as oil, recovery, the field or displacement substance comprising one of more aptamers exhibiting an affinity for adsorbed hydrocarbons.
    Typically the fluid or displacement substance comprises aqueous phases such as water or brine the 'fluid or displacement substance may further comprise other components such as wettability modifiers, polymers, alcohols, basic (alkali) agents, acidic agents, cpis, including water swellabie gels, cross linker molecules, surfactants, matedais / pbmpounds for tracking, salts and / or dissolved gases. By way of example, a fluid or displacement substance may comprise an aptamer based wettability modifier designed to make the surface closer to neutral wettability to hydrocarbon :,
    The aptametfo), such as may be provided by an injection or displacement substance of: this invention, may be provided with a surface (for example, a surface within a hydrocarbon reservoir) from at least one wellbore, for example, an Injection wellbore , The methods of the present. inven to may comprise recovering ell: from at least one (production) wellbore, Desirably the recovery of hydrocarbon adsorbed fp surfaces within fse reservoir is enhanced .through the preferable 01000¾ between: hydrocarbon adsorbed to 0: surface, for example a rock surface, and the aptamarfs).
    Recovered hydrocarbon peptide complexes may be subjected to a dissociation process to release the hydrocarbon from the: apfamer. For example complexes may be contacted with, for example (and not limited to) urea, TEA (trifluoroacetic acids) is TFE (trifluoroethahoi). Additionally, or alternatively, the complexes may be dissociated by the application of heM and / or the: use of distillation procedures.
    Aptamers which have been used in the methods described herein may be recycled for further use. For examples, alpha dissociation »the apfamer (s) may be recoveredand recycled for further use, in a third aspect there is provided a method of producing one of more aptamers for use in a method of recovering hydrocarbon (s) from hydrocarbon * bearing reservoirs and / or rock formations, the method cmnipnslr ^ providing a htlxture Of aptamers to a hydrocarbon or hydrorbons adsorbed or bound to a surface representative of a surface or surfaces of the reservoir or rock formation, each aptamei comprising a region 0! randomized nueleotrdes; and Isolating said apiamer (s) which bind to the adsorbed hydrocarbon and release it from the surface. The isolated aptametS: may exhibitlow / np affinity for the surface.
    Typically the apfamerb are in the form of an otigonueleotide eomprislng a central region comprising the rshdomised nucleotides and 3 * and / or 5V regions of known sequence »Typically the region of randomized nucleotides is from 8 to 250 nucleotides in length, The 3 'and / or 5- regions of known sequence can facilitate isolation and amplification of the aptamers, if wifi is desoribed in more detail
    The above method of identifying aptamers is generally based on the Systematic Evolution oi Ligands by Exponential enrichment method, termed SELEX. described in WO 911S813 which is herein incorporated by reference. The SELEX method enables selection of a mixture of candidate oligonucleotides and complete step wise iterations of binding, separation and amplification, using the same general selection scheme, to achieve virtually any desired criterion of binding affinity and setectivity, starting from a mixture of nucleic acids, Preferably, a randomized segment of randomized sequence, the SELEX method includes steps of contacting the mixture with a larged whieh. In the case of the present invention: is typically a surface, for example a smoke surface comprising a hydrocarbon adsorbed or bound thereto {the target beifig the adsorbed abd / or bound hydrocarbon), under conditions favorable for binding between the nucleic acids and the adsorbed / bound hydrocarbons and subsequent release of nucleic acid / target complexes from the surface; separating unbound nucleic acids and nucleic acids which bound the target (the adsorbed / bound hydrocarbon) but did not affect its release from the surface, from those nucleic acids which traverse bound specifically St target molecules and affected their release from the surface; dissociating the nucleic acid-target complexes * often amplifying the nucleic adds dissociated from the nucleic acid-target complexes to yield a ligand-enriched mixture of nucleic acids; and then reiterating / repeating the steps; of binding, separating, dissociating and amplifying log through as many cycles as desired to yield highly specific: high affinity nucleic acid ligands which not only bind the target molecule but further affect its release from a surface: to which it was adsorbed and / or bound.
    The basic SELEX method described in W09119811 has been improved and modified over the years and Dua ef a! (Recent Patents on DMA & Gene sequence 20 () 8,2,172-186) provide a review of relevant patents related to 8ELEX. Each of the icfpntlfied: pafenf ^ o ^ teht appflcsfiorts idernified in the above paper by Dua of a /, are Incorporated herein by way of reference.
    Certain teens used to describe the invention herein are defined as follows: "SELEX" methodology refers to a method of selecting nucleic acid aptamers which interact with a target molecule in a desirable manner, for example binding to the molecule and / or release of the molecule from a surface, with amplification / isolation 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 saieetfon / affiplification steps allows selection of one or a small number of nucleic acids which interact most strongly with the target from a pool containing a very low number of nucleic acids. Cycling o! Hour selection / amplification procedure is continued until a selected goal is achieved. Although cyciing / amplification is often employed, Moorvet ai (Ssoroehniques, 2011, 51: 413-416) - to which the ski reader is directed and the contents of which are herein incorporated, describe a method of selecting apfamets by high-throughput sequencing and informatics analysis, which only requires one round of positive selection followed by high-throughput DNA sequencing: and informatics analysis in order to select high-affinity aptamers. Thus, cycling fstnd / df ^ pliffoatipp.pseen as optional, although desired In many cases; "Nucleic acid" means either DNA and / or RNA and encompasses. singie-stranded or ^ ubie strar ^ ed moleouies. Further, the term encompasses molecules comprising natural and / or synthetic bases, peptide nucleic acids, locked nucleic acids and any form of chemical modification to one or more bases. Modifications include, but are not limited to, those that provide other Chemical groups that incorporate additional charge, polarizability, hydrogen bonding, electrostatic interaction, and fluxionafity to the individual nucleic acid bases or to the nucleic acid as a whole. Such modifications include. Put are not limited to modi red bases such as ^ '- position sugar modifications, 5-position pyrimidine modifications. 8-position purine modifications, modifications to cytosine exocycilc amines, substitution of 5 · bromo-uraoii; backbone modifications, methylations, unusual base-pairing combinations such as the isobases isocytidine and isoguanidine and the like. Modifications can also include the inclusion of restriction sites and 3 'and 5' modifications such as capping. Modifications that occur after each round of amplification are all 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 thisinvention. "Mixture of aptamers" is a mixture of nucleic acids of differing, randomized seguehce. The source of a "mixture of aptamers" can be from naturaily-oceurfing nucleic acids or fragments thereof, chemfealiy synthesized nucleic acids, enzymatically synthesized nucleic acids or nucleic acids made by a combination of the foregoing techniques, - in a preferred emfedimehtj each nucfefe :, acid has sequences around a randomized region to facilitate the amplification process, The length of the randomized section of the nucleic acid is generally between 8 and 250 nucleotides , preferably between: B and 60 nucleotides.
    Said "one or more aptarnerfs}" is (are) nucleic acid moieeofe (s) which has / haye been isolated from the: mixture of aplamers and which (ip bind to a hydrocarbon adsorbedpnd / br boundle a surface and / or p) affect the release of the adsorbed / bound hydrocarbon from the surface, "Separating" means any process for separating: potentially useful aptamers from those who do not exhibit the desired properties: For example; "separating" may comprise sorting those nucleic acids: which bind hydrocarbons adsorbed or bound to a surface and release them therefrom, from those that (I) do not bind adsorbed hydrocarbons and / or (ii) do not release hydrocarbons from the surface to which they are adsorbed and / or bound. Riter binding, affinity chromatography, liquid-liquid partitioning, filtration, gel shift, equilibrium partitioning density gradient centrifugation are all examples of suitable separating methods. rocess or cornblifasion of process steps that increase (s) the amount or number of copes of a molecule or class of molecules preferred: embodfmehtSj arhpilfication occurs alter members of the aptamer mixture have been separated * and it is the aptamers who exhibit the requisite bonding and release properties thai are amplified. For example, amplifying DNA may be carried by, for example,; technologies that exploit the polymerase chain reaction (PGR), amplification of RNA molecules can be carried out by a sequence of three reactions; making cDNA copies of selected RNAs, using the PGR to increase the copy number of each cDNA, and transcribing the cDIMA 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 DMA replication, direct RNA amplification and the tike, as will be recognized by those skilled 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 many modifications to nucleic acids are compatible with enzymatic amplification, yodifieaflons 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 TO to more than about 250 nucleotides, The ehenilcai or enzymatic reactions by which random sequence segments are made may not yield mathematically random sequences due to unknown biases or nucleotide preferences: that may exist. The term "rahdomlzad" is "used instead of" ΤοηΟοηΤ "id to reflect the possibility of: such deviations from non-ideality, in the techniques presently known, for example sequential chemical synthesis, large deviations: are: hot known to occur. For short segments of 20 nucleotides or less, any minor bias that might exist would have negligible consequences. The longer the sequence 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 deoxynucleoside) triphosphates in the synthesis reaction or the ratio of phosphoramidiles 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 aptamers of differing sequence is prepared: The candidate mixture generaii indudes regions of fixed sequences | l e >>. each of the methods of (he candidate mixture ctontairiS: thb same sequences in the same location) and regions of randomized sequences, the fixed sequence regions are selected either: (a) to assist in the amplification: steps described below, (b) to mimic a sequence known to bind to tire target, and / or (c) enhance the concentration of a given structural arrangement of the nucleic acids in the candidate mixture. He randomized: sequences; can be totally randomized (re., the probability of finding a base at any position being one in four) or only randomly randomized fe.g ,, the probability of finding a base at any location can be selected at any level between 0 and too percent), 2} The candidate mixture is contacted with a target. Typically the target comprises a surface comprising a hydrocarbon bound or adsorbed thereto, in this case, the. target is the bound and / or adsorbed hydrocarbon. The surface may comprise a substrate, for example a smoke surface obtained from a hydrocarbon reservoir or subterranean formation, where it may be desired to apply an (enhanced) oil recovery technique. The candidate mixture is contacted with the target under favorable conditions for bonding between the target (adsorbed and / or bound hydrocarbon) and members of the candidate mixture and subsequent release of the target from the surface to which it is adsorbed and / or bound. Under these circumstances, the interaction between the target and the nucleic acids of the candidate mixture can be considered to form nueic acid-target pairs between the target and those nucleic acids having the strongest affinity for the target. In some cases, the interaction between the target and high affinity acids for the target will further bring about the release of the target from the surface to which if was adsorbed and / or bound, 3) The nucleic acids with tire highest afhnily for the target and an ability to affect the release of the target from the surface to which it is bound anchor adsorbed are separated from those nucleic acids with less affinity to the target and / or an inability to affect release. Because only an extremely smsif number of sequences (and possibly only one molecule of nucleic acid) corresponding to the highest affinity nucleic acids exist in the candidate mixture, it is generally desirable to set the separating criteria so that a significant amount of the nucleic acids in the candidate mixture (approximately 5-50%) is retained during separation. 4) Those niicleic acids selected during separation have relatively higher affinity to the target and / or some ability. affect release of the hy ^ reearbon from the surface to which it is high, are then amplified to create a hew candidate mixture enriched in nucleic acids having a relatively higher affinity for the target and an ability to affect release, 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 nucleic acids to the target and / or their ability to affect release of the hydrocarbon from the surface to which they are adsddieda ^ and wi genemiiy increase. Taken to its extreme, the 8ELEX process will yield a candidate mixture containing one or a small number of unique nucleic acids representing those nucleic acids of the original candidate mixture having the highest affinity to the target moie and the greatest ability to affect the release of the adsorbed. / bound hydrocarboh.
    The SB. EX process when used in accordance with the present -invention thus provides high affinity apiamere; for bonding to and releasing a hydrocarbon, for example oil adsorbed and / or bound to a subterranean substrate, such as a rock surface.
    The present application is concerned with identifying nucleic acid aptamers to hydrocarboh | sf} for example oil, which are adsorbed and / or bound: to subterranean substrates, typically rack surfaces. The aptamers. so Identified can be used in enhanced oil recovery techniques known in the art. The aptamers of the present invention may be identified generally according to the above method known as the SELEX process. A fourth aspect of this invention provides an gptamer with an affinity for an adsorbed hydrocarbon obtainable by a method according to the third aspect of the Invention. Aptamers according to the: fourth aspect of this invention may further affect the: release of an adsorbed hydrocarbon from a surface, for example a subterranean substrate, such as a smoke surface.
    According to a fifth aspect, thefe is providing a rhythm of recovering hydrocarbons from a hydrocarbon bearing reservoir or rock formation, composing providing tone or more aptamer moiecufefs) to the reservoir or formation, which apiamef molecules exhibit an affinity for hydrocarbon adsorbed to a rock surface within the reservoir or formation such as: form aptamer / hydrocarbob complexes ;: and providing a displacement, substance in tfrø. formation to: displace the aptamb # ydroOarbah complexes from the formation.
    The method may involve injecting a Hood fluid, such as water, into the formation, to displace hydrocarbons from the formation.
    The method may be to inject the flood field from at least eoe: first wellbore, for example an injection wellbore.
    The method may compose: recovering hydrocarbons from at least one first wellbore, for example a production wellbore; It should be understood that any of the methods described in this invention: may fee: combined with one or more other methods (and / or existing technologies) to offer further improved methods of hydrocarbon and / or erode oii recovery from hydrocarbon (crude difjfoeariog reservoirs : and / or took formations.
    For example: a Sixth aspect of this Invention may provide a method of 'recovering a: hydrocarbon from a surface, said method comprising: modifying the wettability of a surface from which a; hydrocarbon Is to be mcovsred; provfdihg one: or more aplarner molecules to the surface under conditions permitting the formation of aptamer hydrocarbon complexes; and recovering the aptamer hydrocarbon complexes.
    The surface from which the hydrocarbon is recovered may be any surface of a hydrocarbori bearing reservoir or mk formation, Furthermore, the wettability of one or more surfaces (of the hydrocarbon bearing reservoir or rock formation) may be modified by the provision of one or more aptamer molecules to the surface, said aptamer moieculefs) are designed to adhere to a surface of the hydrocarbon -bearing reservoir or smoke formation substrate, so as to modify its wettability!
    Typically, aptamers lor use as wettability modifiers are in the form of an ofgormeleotlde as described: above * comprising a central region comprising the randomized rfueieotidés and 3 'and / br S' regions of known: seguerm However, rather than exhibiting an affinity for - adsorbed: bydfocartrøh *; aptamers which are suited: to modify the wettability of a surface, for example a smoke surfacing adhering to said surface rendering it closer to neutral wettability to a hydrocarbon, such as oil {for example crude oil) and / or water,:; than before the apfamer (s) is added. Without wishing to be bound t / y theory, it is expected that as a surface (for example a rock; surface) becomes more neutral in: terms of its ability to be water wet and / or off wet, there is a seduction in the degree of oil bonding to the sock surface and more hydrocarbon (eg, oil) p $ bte.ayafiafofefgfr ^ sopiTy'ίίτοφ the reservoir.
    The steps of the method according to the sixth aspect of this invention may be practiced in any order. For example, wettability modifying aptamers may be provided to the surface before and / or after extraction aptamers (the "extractiotf aptamem feeing those with an affinity for adsorbed hydrocarbon as described above). Additionally or aifernatively, the method may comprise a step in which the wettability and extraction aptamers are provided to the reservoir and / or for mation (or surfaces thereof) at the same time for / competitively) - the method or any individual step thereof (for example, the step of adding wettability modifying aptamers and / or extraction aptamers) may be repeated one or more times.
    The features of: aptamers suitable for: use in modifying the methods of this invention as well as methods for identifying suitable wettability modifying aptamers described in detail in GB1315743,3 and PGT application No: _pad on and published; AS; ). The entire contents of ibothof these applications are incorporated herein by reference.
    It should be noted that the features described in relation to any aspect of this invention may apply in respect of the corresponding features of any other aspect of this Invention.
    DETAILED DESCRIPTION
    Figure .T shows in schematic form the SEPEX process as described by the present inventors, SEPEX stands for Systematic Evolutionof Petfoleum Compound Extractors by Exponentiai Enrichment and is based on the known SELEX process (described above). The SEPEX procedure described below ultimately relies on a .molecular micro-evolution via an extreme selection pressure bf DNA molecules. Eventually DNA whose very high affinity to oil adsorbed to a reservoir rock is isophagated, amplified, sequenced and cloned.
    Briefly and with reference to Figure 1, a DNA library (id) comprising many (perhaps 100s-HX) 0s) Of different; oligonucleotides (test aptamers) comprising different; randomized sequences Is provided. The large oligonucleotide library (10) comprises randomly generated: sequences of fixed lengthllanked by constant 5 'and 3' ends that serve as primer binding sites. The DNA library (10) is contacted with a sample of rock (12) to which hydrocarbons are adsorbed (14). The DNA library: and the sample of rock. :( 1: .2) are contacted; under conditions which allow oligonucleotides to die within the DNA library (10) to bind to the adsorbed hydrocarbons (14). The rock sample may be taken directly from a particular hydrocarbon bearing reservoir, or .couW be a sample of rock which is representative of smoke withlr hydrocarbon bearing reservoirs. Some of the oligonucleotides: (1¾) within the library (10) do not bi nd factbe: adsorbed hydrocarbons and these can be washed away using, for example, brine: Others ¢ 20} bind adsorbed hydrocarbons but do not affect their release from the surface (¢ 12), these: pan removed by simply removing the: surface. This will also have the effect of removing any apfamers which bind: directly to thesurface.
    Some of the oligonucleotides (22) have bound the adsorbed hydrocarbon ¢ 14) adding affected its release form to the surface (12). These form free oligonucleotide dihydrogen complexes ¢ 24) which are isolated amitor purified by, for example, reverse-phase chemistry or hydration: Sitpd interaction chromatography. The ofigonneeofide / hydrooarbon complexes (24) may be separated using, for © camp! ©, urea, fluoroacetic acid (TFA) or trifluoroethanoi {TFE), in order to provide: lsoiated :: oligonucteof! D: es:
    The isolated oligonucleotides {2: 8} then enriched by an amplification technique, such as PGR, in order to make more copies of the isolated Glfgphuclebfidas (26a) and provide ah single sahipie of oligonucleotides. Thereafter the endched oligonuclebtides (28a): are allowed to bind the sample of rock {12} to which hydrocarbons are adsorbed ¢ 14} in a repeat of the initial process steps. it; shoo id note that the sample of rock (12) may be the same or a different sample to that used in the Initial process steps, it should further be noted that the conditions under which the enriched oligonucleotides (26a) are contacted with the mushroom of rock (12) are more stringent than in previous rounds, so that some of the enriched oligonucleotides (28a) will not be capable of binding to the adsorbed hydrocarbons (14) of the sample of rack (12). conditions may be provided by contacting the oligonucleotides (28a) with the tpek sample (12} in the presence of, for example (but not limited to) urea, TFA or TFE. Compounds of this type may be added to a buffer in which the oilgonuciectides (28a) are diluted Thereafter pyigonuclaofides which bind and release adsorbed hydrocarbons can be eluted amplified, and enriched as before.
    The cycle of binding to adsorbed hydrocarbons {14} on the surface ¢ 12} followed by elution, amplification and enrichment, can be repeated a number of times, such as..5-15 times, but at each successive round of binding, the Conditions for binding are made more stringent, by increasing the concentration of urea, TFA or TFE, Eventually, after the successive rounds of binding, eluting, amplification and enrichment, a small number or even a single or more Highly specific oifgonue leotide {: s) (28b) ls / are obtained which will be capable of binding to the hydrocarbons (14) adsorbed to the smoke surface ¢ 12} with very high affinity and .affecting Wf release therefrom. Such oligonucleotides may: be made in large quantities. By, for example, cloning the: qligonueleDtide (s) into a vector, sudh: as a plasmid and expressing the cloned oligonucleotide (s) and purifying leg tit (oilgonucleofidefs) using recombinant techniques known to the skilled reader -see for example Sambrook and Russen (3001); Molecular Cloning: A Laboratory Manual (3 ^ ed.) GSNt press.
    An exemplary method for the generation of high-affinity DMA apfamers for adsorbed hydrbearbons is described below: 1. A thin surface (8) prepared from a rack sample from an oil reservoir Is. colieoted / obtained. No washing should be done. Size: approx, in island. 2. S is placed in brine 3. Add a library of DMA molecules with Of 10,000) different sequences: Equilibrate. 4. Remove supernatant, 5. Measure absorbance in supernatant at 200nm (at 260nrn DMA absorbs) (A;). Molecular extinction coefficient o single-stranded or double-stranded DMA is 0.027 (pg / mD: cm - and 0.02 (µg / mrr cm "1, respectively) 6. Enrich for hydrodoser DNA complexes by reverse-phase chromatography (eg using a Gi8 ~ eelumn), Make solvent exchange so the supernatant is dissolved in 0.5% acetic acid (it should be checked whether brine would be sufficient for this enrichment: step so solvent exchange can be avoided bp) and s (fcj ^ the # f ^ n..tp ^ C18: oøfu ^ n. The hydrocarbon complexes bind to the hydtopbobic rssin whereas the hydrophilic · DMA does not adsorb to hydrocarbons will not adsorb. Wash 3-4 times with e, g .: 0. 5% acetic acid to rempveiynspecific bound species. containing complexes: can be eluted by (95% AceionknL 0.5% acetic acid) a. NOTE: Aiteimativeiy hydtopblc liquid interaction chromatography (HiLiC) can be used which is essentially the opposite chromatographic scheme as for reverse-phase chromatography, re. hydrocarbon complexes will be in the flow-through, whether feverse-phase or HiLiC chromatography used should depend on praciieaiiiSes since both types of chromatogmphy at e adequate to enrich tor hydrocarfeon-DNA complexes. 7; Measurøafesorbanoe. 8. Add urea, TEA (influent acetic acid) or TEE (trifiuoraethanoi) to release hydrocarbons from DMA, 9. Submit the solution to a reverse phase column. This time, the ON A will be: in the itpw-through due to hydrophilicity (Le; st is not bound to hydrophobic hydrocarbons after deriaiurant treatment) 10. Desalt iheflowrth rough and cosiGenfs'ate the: sample using e.g. GentriGon spin spiters or gel electrophoresis Pleasure absorb. 11. Amplify o n A. using OCR (polymerase chain reaction}: 12. Measure absorbance after amplification (Absorbances are used to estimate DNA cenentratlons in each step using Lambert Beer taw} :,
    Repeat step {1-12} a number (for example 15} times: using increasing (but still semi-homeopathic) concentrations of urea, TFE, If A or surfactant added to the brine tor the wash in step 6. In this way DNA with continuous increasing · binding affinity ίο: the hydrocarbons are enriched heavily Note: than in step 3 the eiuate from the previous round is used instead of the initial huge DMA library,
    Alter the: last (tor example 15 *} round, DNA with extremely strong affinity to; the hydrocarbons adsorbed to the rock and (importantly) with the ability to release the bound hydrocarbon Is generated due to the very hard seleetion pressure: in the successive washing step.
    This final pool is amplified by PGR and the nucleotide sequence is determined by DNA sequencing (e.g., Sanger or Soiexa techniques). Large scale production of high affinity aptamers can be carried out using recombinant techniques as described above.
    As previously mentioned, it may not be necessary to have only a single apfamer and a pool of aptamers may be provided which show affinity to different types of adsorbed hydrocarbon (14} and / or hydrocarbons adsorbed to different types of surface (12).
    The aptamers or poof or aptamers of the present invention are intended to bind and release adsorbed hydrocarbon from the sudaces o! a hydrocarbon reservoir or rock formation. Thus, after primary oil extraction, enhanced oil recovery of the residual hydrocarbon (much of which is adsorbed to the sudaces of; the reservoir or formation) can be achieved with the use of the aptamers disclosed herein which are designed to exhibit high affinity for adsorbed hydrocarbons. One of skill will appreciate that this technology may significantly increase off production.
    The apiarner or pool of aptamers may be added to the hydrocar e.g., bearing-reservoir or rock formation, typically by adding a fluid such as water. The aptamer (s) are allowed; a period of time to adhere to and release the adsorbed hydrocarbon. Thereafter, a water flood or chemical flood can be injected Into the reservoir in order to allow the released hydrocarbon / apiafner complexes to be recovered, typically by way of a production well.
    权利要求:
    Claims (37)
    [1] 1. A method of recovering a hydrocarbon from a hydrocarbon-bearing reservoir or formation, said method comprising providing one or more aptamer molecules to the hydrocarbon-bearing reservoir or formation under conditions permitting the formation of aptamer hydrocarbon complexes; and recovering the aptamer hydrocarbon complexes.
    [2] 2. The method of claim 1, wherein the method is a method of recovering a hydrocarbon from a surface of a hydrocarbon-bearing reservoir or a surface of a hydrocarbon-bearing rock formation.
    [3] 3. The method of any preceding claim, wherein the hydrocarbons to be recovered are bound, adsorbed and/or otherwise associated with a surface of the hydrocarbon-bearing reservoir or formation.
    [4] 4. The method of any preceding claim, wherein the aptamers are designed to bind and/or adhere to adsorbed hydrocarbons.
    [5] 5. The method of claim 4, wherein the aptamers are further capable of affecting the release of adsorbed hydrocarbons.
    [6] 6. The method of claim 5, wherein the adsorbed hydrocarbons are released as hydrocarbon/aptamer complexes.
    [7] 7. The method of any preceding claims, wherein the aptamers have low/no affinity or substantially low/no affinity for a surface of a hydrocarbon-bearing reservoir or rock formation.
    [8] 8. The method of any preceding claim, wherein the aptamers are in the form of an oligonucleotide comprising a central region comprising randomised nucleotides and 3! and/or 5’ regions of known sequence.
    [9] 9. The method of claim 9, wherein the region of randomised nucleotides is from 8 to 250 nucleotides in length.
    [10] 10. The method of any preceding claim, wherein the hydrocarbon comprises crude oil containing many chemical components.
    [11] 11. The method of claim 3, wherein the surface is a rock surface.
    [12] 12. The method of any preceding claim, wherein the aptamers comprise a single type of aptamer or multiple different types of aptamer.
    [13] 13. The method of any preceding claim, wherein sufficient aptamer to provide at least about 1, 10, 100, 103, 104, 105, 106, 107, 108"15 aptamer molecules per cm2/surface are provided to the hydrocarbon-bearing reservoir or formation.
    [14] 14. The method of any preceding claim, where the aptamers are provided to the reservoir or rock formation by way of a fluid comprising said aptamers.
    [15] 15. The method of any preceding claim, wherein the aptamer(s) are provided to the reservoir or rock formation via at least one wellbore or injection wellbore.
    [16] 16. The method of any preceding claim, wherein recovered hydrocarbon/aptamer complexes are subjected to a dissociation process to release the hydrocarbon from the aptamer.
    [17] 17. The method of claim 16, wherein the dissociated aptamers are recycled for further use.
    [18] 18. A fluid or displacement substance for use in hydrocarbon recovery, the fluid or displacement substance comprising one of more aptamers exhibiting an affinity for adsorbed hydrocarbons.
    [19] 19. The fluid or displacement substance of claim 18, wherein the fluid or displacement substance comprises water, brine or sea-water.
    [20] 20. The fluid or displacement substance of claims 18 or 19, wherein the fluid or displacement substance comprises one or more additional components selected from the group consisting of: (i) wettability modifiers; (ii) polymers; (iii) alcohols; (iv) basic (alkali) agents; (v) acidic agents; (vi) gels, including water swellable gels; (vii) cross-linker molecules; (viii) surfactants; (ix) materials/compounds for fracking; (x) salts; and (xi) dissolved gases.
    [21] 21. A method of producing one of more aptamers for use in a method of recovering hydrocarbon(s) from hydrocarbon-bearing reservoirs and/or rock formations, the method comprising: providing a mixture of aptamers to a hydrocarbon adsorbed or bound to a surface representative of a surface or surfaces of the reservoir or rock formation, each aptamer comprising a region of randomised nucleotides; and isolating aptamer(s) which bind to the adsorbed hydrocarbon and release it from the surface.
    [22] 22. The method of claim 21, wherein the aptamers are in the form of an oligonucleotide comprising a central region comprising the randomised nucleotides and 3! and/or 5’ regions of known sequence.
    [23] 23. The method of claim 21 or 22, wherein the region of randomised nucleotides is from 8 to 250 nucleotides in length.
    [24] 24. An aptamer with an affinity for an adsorbed hydrocarbon, obtainable by a method according to any one of claims 20-23.
    [25] 25. A method of enhanced oil recovery from an oil-bearing reservoir or rock formation, said method comprising: providing one or more aptamer molecules to the oil-bearing reservoir or rock formation under conditions permitting the formation of aptamer oil complexes; and recovering the aptamer oil complexes.
    [26] 26. A method of recovering a hydrocarbon from a surface, said method comprising: providing one or more aptamer molecules to the surface under conditions permitting the formation of aptamer hydrocarbon complexes; and recovering the aptamer hydrocarbon complexes.
    [27] 27. The method of claim 25 or 26, wherein the aptamer(s) exhibit an affinity for hydrocarbon adsorbed to a rock surface within the reservoir or formation
    [28] 28. The method of claim 27, wherein the hydrocarbon is adsorbed to the surface.
    [29] 29. The method of any one of claims 25-28, wherein the aptamer(s) is/are further capable of affecting the release of adsorbed hydrocarbons.
    [30] 30. The method of claim 29, wherein the adsorbed hydrocarbons are released as hydrocarbon/aptamer complexes.
    [31] 31. The method of any one of claims 25-30, wherein the aptamer(s) have low/no affinity or substantially low/no affinity for a surface of a hydrocarbon-bearing reservoir or rock formation.
    [32] 32. The method of any one of claims 25-31, wherein the hydrocarbon comprises oil.
    [33] 33. A method of recovering hydrocarbons from a hydrocarbon-bearing reservoir or rock formation, comprising: providing one or more aptamer molecule(s) to the reservoir or formation, wherein said aptamer molecule(s) exhibit an affinity for hydrocarbon adsorbed to a rock surface within the reservoir or formation so as to form aptamer/hydrocarbon complexes; and providing a displacement substance in the formation to displace the aptamer/hydrocarbon complexes from the formation.
    [34] 34. A method of recovering a hydrocarbon from a surface, said method comprising: modifying the wettability of a surface from which a hydrocarbon is to be recovered; providing one or more aptamer molecules to the surface under conditions permitting the formation of aptamer hydrocarbon complexes; and recovering the aptamer hydrocarbon complexes.
    [35] 35. The method of claim 34, wherein the surface is a surface of a hydrocarbonbearing reservoir or rock formation.
    [36] 36. The method of any one of claims 34 or 35, wherein the wettability of the surface is modified by the provision of one or more aptamer molecules to the surface, wherein said aptamer molecule(s) is/are designed to adhere to the surface, so as to modify the wettability thereof.
    [37] 37. The method of any one of claims 33-37, wherein the aptamers for use as wettability modifiers are in the form of an oligonucleotide comprising a central region comprising randomised nucleotides and 3' and/or 5' regions of known sequence.
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    同族专利:
    公开号 | 公开日
    GB201315745D0|2013-10-16|
    WO2015032836A1|2015-03-12|
    引用文献:
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    WO1990014441A1|1989-05-22|1990-11-29|Cetus Corporation|Methods for tagging and tracing materials with nucleic acids|
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    US8658412B2|2009-05-22|2014-02-25|E I Du Pont De Nemours And Company|Altering the interface of hydrocarbon-coated surfaces|CN108114574A|2016-11-29|2018-06-05|中国石油化工股份有限公司|A kind of processing method and processing device of refinery VOCs exhaust gas|
    法律状态:
    2017-04-24| PHB| Application deemed withdrawn due to non-payment or other reasons|Effective date: 20160930 |
    优先权:
    申请号 | 申请日 | 专利标题
    GB201315745|2013-09-04|
    GBGB1315745.8A|GB201315745D0|2013-09-04|2013-09-04|Enhanced hydrocarbon recovery|
    PCT/EP2014/068767|WO2015032836A1|2013-09-04|2014-09-03|Enhanced hydrocarbon recovery|
    EP2014068767|2014-09-03|
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