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    • 专利摘要:
    PROCESS FOR INTENSIFIED OIL RECOVERY. Process for the enhanced recovery of petroleum employing an aqueous solution comprising at least one water-soluble linear or structured copolymer obtained by polymerization: - of at least 10% by moles of 2-acrylamido-2-methylpropanesulfonic acid monomer in free acid form and/or salified, - of at least 10% by moles of at least one comonomer chosen from the group consisting of acrylamide, N-vinylpyrrolidone (NVP) and acrylamide derivative monomers of formula (I): R = H or CH3 or CH2COOR ', where R' is an alkyl comprising at most 3 carbon atoms, A is a heterocycle N comprising, in its ring, from 4 to 6 carbon atoms and optionally a functional ether group or a functional ketone group.
    公开号:BR112014015118B1
    申请号:R112014015118-0
    申请日:2013-01-14
    公开日:2021-07-06
    发明作者:Cédrick Favero；Sylvain Darras；Bruno Giovannetti
    申请人:S.P.C.M. S.A.；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the technical field of intensified oil recovery in an underground formation. More specifically, a subject of the present invention is an improved process for the enhanced recovery of oil which consists of introducing, into the underground formation, a fluid comprising ferrous ions, and/or hydrogen sulfide, and dissolved oxygen, said fluid being made viscous by through an aqueous polymer solution, without the use of stabilizing compounds.
    [0002] More specifically, the invention relates to an improved process for the enhanced recovery of oil employing specific polymers that makes it possible to obtain an improved performance under degrading conditions for the polymer or polymers, this being obtained without using compounds that stabilize the polymer or polymers.
    [0003] Most of the oil fields currently in operation are becoming aged and, in fact, have started to decline in production or are about to start. The degree of recovery of these fields is currently in the order of 15 to 35% on average. They thus offer still considerable production potential.
    [0004] The recovery of crude oil present in underground formations is usually carried out in several stages.
    [0005] Production results first from the natural energy of fluids and rock, which are decompressed. At the end of this depletion phase, the rate of oil recovered on the surface represents an average of 5 to 15% of the initial reserve. Thus it is necessary, in a second step, to employ techniques aimed at increasing the recovery field while maintaining field pressure.
    [0006] The method most frequently employed is to inject water and more generally brine into the underground formation via injection wells dedicated for this purpose. The term used is then secondary recovery. This second phase stops when the water content of the mixture produced by the output wells is too high. The gain here, in terms of the degree of additional oil recovery, is on the order of 10 to 20%.
    [0007] The other techniques that can be used are combined under the name of enhanced oil recovery (EOR). Your goal is to recover between 10 and 35% additional oil compared to the initial amount. The term “enhanced oil recovery” encompasses various thermal and non-thermal techniques, such as “electrical”, “miscible”, “steam” or “chemical” techniques, for the intensified recovery of oil remaining at the site (see “Oil & Gas Science and Technology” - IFP review, vol. 63 (2008), No. 1, pp. 9-19). Oil denotes any type of oil, ie light oil and heavy oil as well as bituminous oil.
    [0008] The invention relates more specifically to the intensified recovery of oil by chemical route involving at least the injection into the underground formation of an aqueous fluid comprising one or more water-soluble polymers.
    [0009] Techniques of intensified oil recovery (EOR) are distinct from operations for the stimulation of a reservoir. The latter are characterized by injections limited in volume of polymer solution in order to create a phenomenon located in the reservoir, that is, for compliance, a blockage of high permeability zones and, for water closure, a blockage of the zone where water enters the formation. Injections are usually carried out either via an injection well or via a production well for very short times of a few days and generally less than a month, and with volumes representing less than 5% of the reservoir pore volume. The pore volume corresponds to the volume not occupied by the rock in the reservoir, which provides a correlation with the permeable zone.
    [00010] Conversely, intensified oil recovery (EOR) techniques using polymers involve a continuous and prolonged injection of polymer solution in order to sweep the reservoir of an injection well as well as a production well. The objective is not to treat a reservoir zone, but the reservoir as a whole, in order to recover the maximum amount of oil. For this, it is necessary to inject a much larger volume of aqueous solution generally representing at least 50% to 500%, in fact even more, of the pore volume. Oily and sometimes gaseous and aqueous mixtures are then recovered on the production side or sides.
    [00011] The injection of viscous polymer fluid, according to the technique employed, occurs alone or in combination with other chemical compounds for use in improved oil recovery.
    [00012] In all these techniques, the addition of water-soluble polymers allows to improve the scanning efficiency compared to water injection. The expected and proven benefits of using polymers, through making injected water “more viscous”, are improved areal sweeping and control of mobility in the field in order to recover oil more quickly and efficiently. These polymers make it possible to increase the viscosity of the injection water.
    [00013] The person skilled in the art knows that synthetic water-soluble polymers and in particular water-soluble polymers based on acrylamide are highly advantageous polymers for increasing the viscosity of aqueous solutions and are widely used in the intensified recovery of oil.
    [00014] The polyacrylamides used are predominantly anionic and are obtained by: • copolymerization of acrylamide and acrylic acid, • co-hydrolysis or post-hydrolysis of a polyacrylamide, • copolymerization or terpolymerization of acrylamide with other ionic or non-ionic functional monomers.
    [00015] Polyacrylamides are already widely used in the intensified recovery of oil in the techniques of "polymer", "surfactant polymer" and "alkaline surfactant polymer" (P, SP and ASP).
    [00016] However, the water and brine used in oil fields comprise other chemical compounds that can degrade the viscosity of the polymers used and thus the desired efficiency is not achieved as the viscosity of the fluid actually propagating in the field is lower than the that needed.
    [00017] In practice, in oil fields, the polymer is injected via an injection fluid (water, brine) whose content of oxygen, dissolved metals, hydrogen sulfide and other entities, which interact with the polymer chain , is not always controlled or controllable. These conditions result in a very significant deterioration in the properties of the injection fluid comprising the polymer, this being related, in particular, to degradations of the following types: - biological, - mechanical, and - chemical.
    [00018] The chemical degradation of polymers corresponds to the mechanism that is the most difficult to anticipate and quantify. This is because this type of degradation can occur according to multiple mechanisms during injection of the fluid comprising the polymer and/or in the reservoir used to store the injection fluid comprising the polymer prior to injection, or in the wellbore area close to the underground formation.
    [00019] Chemical degradation is primarily due to the formation of free radicals that will react with the main chain of the polymer reducing its molecular weight. This then results in a decrease in injection fluid viscosity associated with a decrease in the hydrodynamic volume of the polymer chain in solution. Free radicals can originate from several sources: they can be generated by the cleavage of weak bonds in the polymer chain under the effect of heating/attrition or by initiator residues or by-product impurities present in the polymer. Redox systems also generate free radicals. The presence of oxygen is the most harmful factor in relation to polymer degradation. Furthermore, the reaction in which polymers are degraded by oxygen is accentuated by the presence of certain metals, such as iron, particularly ferrous Fe“ ions, or by the presence of hydrogen sulfide.
    [00020] It is important to note that in the case of operations for the stimulation of reservoirs such as blocking zones of high permeability, it is sought to gel the polymer as much as possible in order to block the preferential passages of the well. One way to do this is to oxidize the ferrous ions present in the injection fluid into ferric ions in the presence of oxygen. The addition of oxygen is generally carried out when the polymer has reached the preferential passage so that crosslinking of the polymer takes place in the presence of Fe3+ ion in situ. This technology is more particularly described in US-A-4 951 921.
    [00021] In the case of intensified oil recovery, during its injection into and its propagation in the porous medium, the polymer is thus subjected to an unwanted chemical degradation. In order to overcome this problem, several solutions have been described in order to stabilize the polymers and thus reduce the extent of chemical degradation.
    [00022] For example, patent US 4 653 584 provides a copolymer based on acrylamide and maleimide, for application in EOR, having a high temperature resistance, for high salinities and for high concentrations of di- and trivalent metal ions.
    [00023] The application WO 2011/100665 provides two solutions to solve the problem of the presence of Fe“ ions: reverse osmosis or the addition of chelating agents, otherwise known as metal complexing agents.
    [00024] Patent US 4,563,290 describes copolymers that are resistant to mechanical degradation and that are resistant to impurities generally present in water. These copolymers comprise at least 10% by moles of acrylic acid and less than 10% by moles of 2-acrylamido-2-methylpropanesulfonic acid.
    [00025] In an EOR application, resistance to ferrous ions and/or hydrogen sulfide represents a very particular problem to which the prior art establishes, as unique solutions, the addition of a complexing agent or water treatment by reverse osmosis.
    [00026] Applicant's WO 2010/133258 describes the protection of the water-soluble polymer or polymers due to the combination of at least three stabilizing agents in one and the same formulation comprising the polymer before being dissolved with the injection fluid.
    [00027] Even so, this efficient solution requires the preparation of a composition of at least four chemical compounds, which can sometimes prove to be problematic in oil fields, in particular, for logistical reasons.
    [00028] There is thus a need for new solutions that allow to improve the intensified recovery of oil chemically without using stabilizing agents and without the need to install water treatment processes such as reverse osmosis.
    [00029] The Applicant demonstrated that, surprisingly and completely unexpectedly, the selection of certain monomers, in specific proportions and, where appropriate, the adjustment of the composition of the injection fluid allowed to limit the degradation of polymers in intensified oil recovery processes .
    [00030] Document US-A-4 563 290 describes AMPS/NVP or AMPS/AM/NVP copolymers that are tested for their use in EOR for their ability to thicken synthetic seawater samples, i.e., a simple mixture of water and salt. The ability of polymers to withstand free radical degrading conditions is not described.
    [00031] Document WO 97/22638 describes copolymers based on ATBS and on acryloyl piperazine derivatives (eg XIX, XXI), whose stability is tested in synthetic seawater samples. Here too, the ability of polymers to withstand degrading conditions in the presence of Fe“ ions and oxygen or hydrogen sulfide and oxygen is not described. Other polymers based on ATBS and acryloyl morpholine (eg XXIII) are used for drilling, shaping or other "reconditioning" operations for which the polymer is sought to gel or are intended to maintain sufficient viscosity to sweep the well. Enhanced oil recovery under polymer-degrading conditions is not envisioned.
    [00032] Document US-A-4 563 290 describes copolymers that can be used for the enhanced recovery of petroleum. They contain 10 to 30% by moles of acrylic acid, less than 10% by moles of AMPS and 60 to 89% by moles of acrylamide.
    [00033] The present invention relates to an improved process for the enhanced recovery of oil that consists of taking a viscous fluid through an aqueous polymer solution, then injecting the fluid into the underground formation and recovering the aqueous and oily mixture from the production well or wells.
    [00034] More specifically, a subject of the invention is a process for the enhanced recovery of oil, which consists of: - preparing, without the addition of stabilizing agent to the polymer, an aqueous solution comprising at least one linear or structured copolymer soluble in water obtained by polymerization: - of at least 10% in moles of 2-acrylamido-2-methylpropanesulfonic acid monomer in free and/or salified acid form, of at least 10% in moles of at least one comonomer chosen from the group consisting of acrylamide, N-vinylpyrrolidone (NVP) and acrylamide derivative monomers of formula (I):
    where: - R = H or CH3 OR CH2COOR', where R' is an alkyl comprising at most 3 carbon atoms, - A is an N heterocycle comprising, in its ring, from 4 to 6 carbon atoms and optionally an ether group functional or a functional ketone group, - optionally less than 10% by moles of acrylic acid in free and/or salified acid form, - in introducing the aqueous solution into the injection fluid, without prior or subsequent addition, into the fluid , of stabilizing agent for the polymer, - in injecting the injection fluid, then taken viscous, in the reservoir, - in recovering the aqueous and oily and/or gaseous mixture.
    [00035] In practice, the injection fluid comprises at least 500 ppb of ferrous ions and/or 10 ppm of hydrogen sulfide, and at least 50 ppb of dissolved oxygen without exceeding 10 ppm of dissolved oxygen.
    [00036] In other words, the composition of the injection fluid guarantees the absence of crosslinking and gelling of the polymer. More specifically, the composition of the fluid is such that the combination of dissolved oxygen with Fe2+ does not lead to an amount of Fe3+ so that the polymer crosslinks or gels. Of course, the composition of the injection fluid will be adjusted if necessary depending on its original composition. More specifically, the commonly used injection fluid is obtained using the water phase of the by-product fluid after oil separation at the end of the EOR process. When this fluid contains a lot of oxygen, the composition of the fluid is adjusted. In other cases, the composition of the injection fluid obtained after separation does not need to be adjusted.
    [00037] In the injection fluid, the weight ratio between the amount of Fe ions (expressed in ppm) and the amount of dissolved oxygen in this fluid (expressed in ppm) is advantageously greater than 10, preferably greater than 15.
    [00038] According to an essential feature, the process is carried out without adding stabilizing agent, without adding complexing agent and without injection water treatment being necessary to protect the polymer or polymers used.
    [00039] However, in order to overcome the specific stresses inherent in the EOR process, it remains possible to use certain "stabilizing" agents, such as scale inhibitors, in order to treat the harmful presence of barium in water, or radical scavenging agents in order to treat pipe corrosion.
    [00040] In other words, the injection fluid does not comprise additional stabilizing agents or deliberately added stabilizing agents. It should be understood that compounds corresponding to the definition of a stabilizing agent may be present in the injection fluid, but in amounts such that the stabilizing effect is not obtained.
    [00041] The percentages, parts per million (ppm) and parts per billion (ppb) are all expressed in relation to the total weight of the injection fluid, that is, in relation to the weight of the injection fluid comprising the polymer(s)( s).
    [00042] 2-Acrylamido-2-methylpropanesulfonic acid (ATBS) and acrylic acid monomers can be salified as an alkali metal salt, such as, for example, the sodium salt or the potassium salt, the ammonium salt a salt having an amino alcohol, such as the monoethanolamine salt, or an amino acid salt.
    [00043] Stabilizing agents for the polymer denote the stabilizing agents described in patent application WO 2010/133258, that is, deoxygenating agents, precipitating agents, radical scavenging agents, sacrificial agents and complexing agents. They are, in particular, but without implied limitation, sulfites in all forms, carbohydrazides and hydrazine derivatives, sodium erythorbate, sodium carbonate and sodium phosphate, diethylthiourea, dimethylthiourea, mercaptobenzothiazole and mercaptobenzimidazole, glycerol, propylene glycol, trimethylene glycol, isopropanol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2,4-butanetriol, pentaerythritol (PETA), trimethylolethane, neopentyl glycol, 1.2 - pentanediol, 2,4-pentanediol, 2,3-pentanediol, trimethylolpropane, 1,5-pentanediol, polyacetates and polycarboxylates, polyaspartates, polyphosphates and polyphosphonates, polysuccinates, ethylenediaminetetraacetic acid (EDTA), hepta sodium salt of diethylenetriaminepenta acid DTPMP»Na7), maleic acid, nitriloacetic acid (NTA), or oxalic acid.
    [00044] According to another specific aspect of the present invention, the polymer of the aqueous solution is derived from the polymerization of: - at least 15% by moles, preferably at least 20% by moles, of 2-acrylamido-2-methylpropanesulfonic acid ( ATBS) in free and/or salified acid form; - at least 20% by moles, preferably at least 30% by moles, most preferably at least 40% by moles, of at least one monomer chosen from the group consisting of acrylamide, N-vinylpyrrolidone and monomers of formula (I) .
    [00045] In a specific embodiment, the polymer is also derived from polymerization of the same monomers and in the same proportions as mentioned above and also contains less than 8% by moles, preferably less than 4% by moles and very much less than 1% by moles of acrylic acid in free and/or salified acid form is preferred.
    [00046] In a specific embodiment, the A-radical of the acrylamide derivative monomer of formula (I) is chosen from the group consisting of 2-pyrrolidone, pyrrolidine and 4-morpholine.
    [00047] Advantageously, the acrylamide derivative monomer of formula (I) is chosen from the group consisting of acryloylpyrrolidone, acryloylpyrrolidine and acryloylmorpholine.
    [00048] The Applicant, surprisingly and completely unexpectedly, has demonstrated that polymers meeting these conditions allow to obtain incomparable performances in terms of chemically enhanced petroleum recovery, even when the water or brine compositions comprise ferrous Fe2 and/ or hydrogen sulfide in combination with dissolved oxygen.
    [00049] The polymers according to the invention exhibit an intrinsic resistance when, in an aqueous solution, they are brought into contact either: - with ferrous Fe2+ ions and with dissolved oxygen, or - with hydrogen sulfide and with dissolved oxygen, or - with Fe2+ ions, with hydrogen sulfide and with dissolved oxygen.
    [00050] In other words, the performance associated with the viscosity of the injected fluid is not significantly affected during the oil well sweep. The polymer retains its properties, in particular its viscosity promoting properties. Consequently, oil can be pushed more efficiently, thus improving the rate of recovery.
    [00051] During an intensified oil recovery operation, the polymer may remain in the underground formation and thus may encounter these degrading conditions for several months, sometimes more than 6 months. Thus it is essential for the polymer not to degrade or degrade only slightly over time in order to retain its viscosifying properties in order to push the oil as far as possible into the production well. The polymers according to the invention make it possible to achieve this objective.
    [00052] It was also verified that these polymers offer good resistance to these degrading conditions, including when the latter reaches high levels of degradation agent, that is, when the viscosified injection fluid comprises: - more than 1000 ppb of Fe ions“ ' ferrous, preferably even more than 2000 ppb Fe ions, and still preferably more than 5000 ppb Fe ions, and up to 100 ppm, and/or - more than 20 ppm hydrogen sulfide, preferably still more than 40 ppm hydrogen sulfide, and up to 400 ppm, and - more than 100 ppb dissolved oxygen, preferably even more than 200 ppb dissolved oxygen, and still preferably more than 1000 ppb dissolved oxygen, up to 10 ppm.
    [00053] In practice, the amount of dissolved oxygen should be between 500 ppb and 10 ppm, advantageously less than 4 ppm, preferably less than 2 ppm.
    [00054] The water used to prepare the polymer solution and the water constituting the viscosified injection fluid can be an aquifer water, a water recovered from the production well and then treated, a sea water or a brine comprising salts inorganics more dissolved than conventional seawater, which on average contains between 20 and 50 g/1 of it. Inorganic salts can be, for example, calcium chloride, potassium chloride, sodium chloride or mixtures thereof.
    [00055] The aqueous solution of polymers that makes it possible to take the viscous injection fluid advantageously comprises between 2000 and 50,000 ppm of polymers.
    [00056] Furthermore, the injection fluid viscosified by the polymer or polymers comprises between 200ppm and 5000ppm of one or more water-soluble polymers resulting from the polymer-based solution, preferably between 300ppm and 4000ppm.
    [00057] The viscosified injection fluid may additionally comprise: one or more surfactants. The surfactant may, for example, be chosen from the group consisting of anionic surfactants and their zwitterionics chosen from the group consisting of alkyl sulfate, alkyl ether sulfates, arylalkyl sulfate, arylalkyl ether sulfate, alkyl sulfonate, alkyl ether sulfonate, arylalkyl sulfonate, arylalkyl ether sulfonate, alkyl phosphate, alkyl ether phosphate, arylalkyl phosphate, arylalkyl ether phosphate, alkyl phosphonate, alkyl ether phosphonate, arylalkyl phosphonate, arylalkyl ether phosphonate, alkylcarboxylate, alkyl ether carboxylate, arylalkyl carboxylate, arylalkyl ether carboxylate, and polyalkyl ether derivatives . In the context of the invention, "alkyl" is understood to mean a saturated or unsaturated hydrocarbon group having from 6 to 24 carbon atoms which is branched or unbranched, which is linear or which optionally comprises one or more cyclic units, which may optionally comprise a or more heteroatoms (O, N, S).
    [00058] Arylalkyl group defines an alkyl group as defined above comprising one or more aromatic ring systems, it being possible for said aromatic ring systems to optionally comprise one or more heteroatoms (O, N, S). - one or more alkaline agents, for example chosen from alkali metal or ammonium hydroxides, carbonates and bicarbonates, such as sodium carbonate. - one or more petroleum dispersing agents, such as hydroxylated polymers having low molecular weights.
    [00059] In the end, with advantage, the viscosified injection fluid obtained exhibits an optimal viscosity that can be between 2 and 200 cPs (centipoises). Viscosity measurement is carried out at 20°C with a Brookfield viscometer, and with a UL module and a speed of 6 rpm (revolutions per minute).
    [00060] In the context of the invention, the viscosified injection fluid comprising the desired polymer or polymers is subsequently injected into an underground formation containing oil deposits, according to any technique known to the person skilled in the art of intensified oil recovery processes, also known as EOR processes. It is prepared on the spot, just before your injection into the formation. Generally, all components introduced into the aqueous solution are added in a main line containing the aqueous solution or brine.
    [00061] The polymer according to the invention may also comprise: - monomers having a hydrophobic nature, such as, for example, undecanoic acid acrylamide, undodecyl acid methyl acrylamide, or acrylic acid derivatives, such as alkyl acrylates or methacrylates, as, for example, behenyl ethoxy methacrylate (25); branching agents such as polyvalent metal salts, formaldehyde, glyoxal, or also, and preferably, covalent crosslinking agents capable of copolymerizing with the monomers and preferably monomers having polyethylene unsaturation (having a minimum of two unsaturated functional groups), as per for example vinyl, allyl, acrylic and epoxy functional groups, and mention may be made of, for example, methylenebisacrylamide (MBA) or triallylamine.
    [00062] According to the invention, the polymer can be linear or structured, that is, star-branched (in the shape of a star) or comb-branched (in the shape of a comb). Structured polymer denotes a non-linear polymer that has side chains, so as to obtain, when this polymer is dissolved in water, a strong entangled state, resulting in very high viscosities in a low gradient.
    [00063] The water-soluble polymer used exhibits a molecular weight greater than or equal to 1 million g/mol, in particular, belonging to the range extending from 1 to 25 million g/mol, and preferably greater than 2, 5 million g/mol.
    [00064] According to a specific embodiment of the present invention, the polymer can be chosen from the group consisting of: copolymers comprising from 10 to 50% in moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its form salified, and from 10 to 50% by moles of acrylamide; copolymers comprising from 10 to 50% by moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, and from 10 to 50% by moles of acryloylpyrrolidone; copolymers comprising from 10 to 50% by moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, and from 10 to 50% by moles of acryloylpyrrolidine; copolymers comprising from 10 to 50% by moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, and from 10 to 50% by moles of acryloylmorpholine; copolymers comprising from 10 to 50% by moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, and from 10 to 50% by moles of N-vinylpyrrolidone.
    [00065] According to another embodiment, the copolymer is a terpolymer, the two comonomers besides ATBS being chosen from the group consisting of acrylamide, N-vinylpyrrolidone and the formula (I) monomers.
    [00066] They can, for example, be: terpolymers comprising from 10 to 50% in moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, from 10 to 80% in moles of acrylamide and from 10 to 50% by moles of acryloylpyrrolidone; terpolymers comprising from 10 to 50% by moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, from 10 to 80% by moles of acrylamide and from 10 to 50% by moles of N-vinylpyrrolidone; terpolymers comprising from 10 to 50% by moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, from 10 to 80% by moles of acrylamide and from 10 to 50% by moles of acryloylpyrrolidine; terpolymers comprising from 10 to 50% by moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, from 10 to 80% by moles of acrylamide and from 10 to 50% by moles of acryloylmorpholine; terpolymers comprising from 10 to 50% by moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, from 10 to 50% by moles of N-vinylpyrrolidone and from 10 to 50% by moles of acryloylpyrrolidone; terpolymers comprising from 10 to 50% by moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, from 10 to 50% by moles of N-vinylpyrrolidone and from 10 to 50% by moles of N-vinylpyrrolidone; terpolymers comprising from 10 to 50% by moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, from 10 to 50% by moles of N-vinylpyrrolidone and from 10 to 50% by moles of acryloylpyrrolidine; terpolymers comprising from 10 to 50% by moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, from 10 to 50% by moles of N-vinylpyrrolidone and from 10 to 50% by moles of acryloylmorpholine.
    [00067] According to another embodiment, the copolymer is a tetrapolymer, the three comonomers in addition to ATBS being chosen from the group consisting of acrylamide, N-vinylpyrrolidone and the formula (I) monomers.
    [00068] According to the present invention, the water-soluble polymers used do not require the development of a specific polymerization process. They can be obtained by any polymerization technique well known to the person skilled in the art (solution polymerization, suspension polymerization, gel polymerization, precipitation polymerization, emulsion polymerization (aqueous or inverted), followed or not by a drying stage by spraying, suspension polymerization, micelle polymerization, whether or not followed by a stage of polymerization in precipitation, post-hydrolysis or co-hydrolysis, “template”, radical or also controlled radical type polymerization).
    [00069] The polymer is preferably supplied in the form of a powder or inverse emulsion. In the case that it is in the form of an inverse emulsion, it can be dissolved either directly in the brine or by using the method described in patent application US 2011/0118153, which provides for the in-line and continuous dissolution of inverse emulsions of water-soluble polymers.
    [00070] In the case where the polymer is supplied in the form of a powder, this dissolution can be carried out, in particular, using a unit as described in patent application WO 2008/107492 and sold by the applicant company under the reference PSU “Polymer Slicing Unit".
    [00071] Reference can be made to patent application WO 2008/107492 for further details regarding the unit that can be employed in the context of the invention for the incorporation of the polymer-based composition in the aqueous solution. This unit operates under an inert atmosphere and makes it possible to reduce the risks of introducing oxygen at this stage of polymer dissolution in the aqueous solution.
    [00072] The invention and the advantages resulting therefrom will appear more fully from the following examples, given in order to illustrate the invention and without implied limitation. A- Resistance of polymers under highly degrading conditions (fully aerobic conditions)
    [00073] A number of polymers were tested under highly degrading conditions. 2000 ppm of each of the polymers are dissolved in an aqueous saline solution containing 7 ppm of dissolved oxygen (aerobic condition) and 10 ppm of Fe“ ions. The aqueous saline solution contains 30 g/1 of NaCl and 3 g/l of CaCl2.
    [00074] The solutions are stored at a temperature of 20°C and viscosity measurements are carried out, also at 20°C, after 7 days and after 30 days with a Brookfield viscometer, UL spindle and speed of 6 revolutions per minute (rpm).
    [00075] Losses in viscosity, expressed as %, correspond to the difference between the initial viscosity and the viscosity after aging for 7 days or 30 days, the total being divided by the initial viscosity.
    [00076] The results are recorded in the following table 1:
    ATBS = 2-acrylamido-2-methylpropanesulfonic acid AA = acrylic acid AM = acrylamide NVP = N-vinylpyrrolidone
    [00077] The polymers according to the invention (D to I) allow to obtain aqueous solutions having a viscosity that is not significantly affected by the simultaneous presence of Fe ions and dissolved oxygen in a very large amount, this being the case even without the presence of “stabilizing” agents. This thus results in an improved ability of the injected fluid to efficiently sweep the reservoir and improve the rate of enhanced oil recovery. B- Resistance of polymers under degrading conditions that can be found in an oil field
    [00078] The same series of polymers was tested under field conditions. 2000 ppm of each of the polymers are dissolved in an aqueous saline solution containing 1000 ppm dissolved oxygen and 20 ppm Fe." The aqueous saline solution contains 30 g/1 NaCl and 3 g/1 CaCl2.
    [00079] The solutions are stored at a temperature of 75°C and without the reintroduction of oxygen, and viscosity measurements are carried out at 20°C after 7 days and after 30 days with a Brookfield viscometer, UL spindle and speed of 6 revolutions per minute (rpm) in a glove box to protect from degradation during measurement.
    [00080] The results are recorded in the following table 2:

    [00081] These results confirm that polymers from D to I according to the invention are in fact resistant to conditions under which the presence of dissolved oxygen is combined with the presence of Fe" ions, this being the case even without the presence of “stabilizing” agents. C- Resistance of polymers in the presence of hydrogen sulfide
    [00082] Polymers A, E and G were tested under the following conditions: 2000 ppm of each of the polymers are dissolved in an aqueous saline solution containing 7 ppm of dissolved oxygen (aerobic condition) and 25 ppm of hydrogen sulfide. The aqueous saline solution contains 30 g/l of NaCl and 3 g/l of CaCl^.
    [00083] The solutions are stored at a temperature of 20°C and viscosity measurements are carried out, also at 20°C, after 15 days with a Brookfield viscometer, UL module and speed of 6 revolutions/min.
    [00084] The results are recorded in the following table 3:
    [00085] These results clearly show the superiority of polymers E and G when these polymers are subjected to the joint presence of oxygen and hydrogen sulfide.
    权利要求:
    Claims (18)
    [0001]
    1. Process for the intensified recovery of oil, said process being characterized by comprising the steps of: - preparing, without the addition of stabilizing agent for polymer, an aqueous solution comprising at least one linear or structured water-soluble copolymer obtained by polymerization: - of at least 10% in moles of monomer of 2-acrylamido-2-methylpropanesulfonic acid (ATBS) in free acid form and/or salified form, - of at least 10% in moles of at least one comonomer chosen from group consisting of acrylamide, N-vinylpyrrolidone (NVP) and acrylamide derivative monomers of formula (I):
    [0002]
    2. Process according to claim 1, characterized in that A is a heterocycle N comprising, in its ring, from 4 to 6 carbon atoms and a functional ether group or a functional ketone group.
    [0003]
    3. Process according to claim 1, characterized in that the polymer contains less than 10% in moles of acrylic acid in free acid form and/or salified form.
    [0004]
    4. Process according to claim 1, characterized in that the injection fluid comprises between 500 ppb and 4 ppm dissolved oxygen, preferably between 500 ppb and 2 ppm dissolved oxygen.
    [0005]
    5. Process according to claim 1, characterized in that the copolymer is obtained by polymerization of: - at least 15% by moles, preferably at least 20% by moles, of 2-acrylamido-2-methylpropanesulfonic acid (ATBS ) in free acid form and/or salified form; - at least 20% by moles, preferably at least 30% by moles, more preferably at least 40% by moles, of at least one monomer chosen from the group consisting of acrylamide, N-vinylpyrrolidone and monomers of formula (I).
    [0006]
    6. Process according to claim 1, characterized in that the copolymer is obtained by polymerization of: - at least 15% by moles, preferably at least 20% by moles, of 2-acrylamido-2-methylpropanesulfonic acid (ATBS ) in free acid form and/or salified form; - at least 20% by moles, preferably at least 30% by moles, more preferably at least 40% by moles, of at least one monomer chosen from the group consisting of acrylamide, N-vinylpyrrolidone and monomers of the formula (I), - less than 8% by moles, preferably less than 4% by moles, more preferably less than 1% by moles, of acrylic acid in free acid form and/or salified form.
    [0007]
    7. Process according to claim 1, characterized in that the radical A of the acrylamide derivative monomer of formula (I) is chosen from the group consisting of 2-pyrrolidone, pyrrolidine and 4-morpholine.
    [0008]
    8. Process according to claim 1, characterized in that the acrylamide derivative monomer of formula (I) is chosen from the group consisting of acryloylpyrrolidone, acryloylpyrrolidine and acryloylmorpholine.
    [0009]
    9. Process according to claim 1, characterized in that the polymer is chosen from the group consisting of: - copolymers comprising from 10 to 50% in moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its form salified, and from 10 to 50% by moles of acrylamide; - copolymers comprising from 10 to 50% by moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, and from 10 to 50% by moles of acryloylpyrrolidone; - copolymers comprising from 10 to 50% by moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, and from 10 to 50% by moles of acryloylpyrrolidine; - copolymers comprising from 10 to 50% by moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, and from 10 to 50% by moles of acryloylmorpholine; and - copolymers comprising from 10 to 50% by moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, and from 10 to 50% by moles of N-vinylpyrrolidone.
    [0010]
    10. Process according to claim 1, characterized in that the copolymer is a terpolymer, the two comonomers, in addition to ATBS, being chosen from the group consisting of acrylamide, N-vinylpyrrolidone (NVP) and the monomers of the formula (I ).
    [0011]
    11. Process according to claim 1, characterized in that the copolymer is chosen from the group consisting of: - terpolymers comprising 10 to 50% in moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its form salified, from 10 to 80% by moles of acrylamide and from 10 to 50% by moles of acryloylpyrrolidone; - terpolymers comprising from 10 to 50% by moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, from 10 to 80% by moles of acrylamide and from 10 to 50% by moles of N-vinylpyrrolidone; - terpolymers comprising from 10 to 50% by moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, from 10 to 80% by moles of acrylamide and from 10 to 50% by moles of acryloylpyrrolidine; - terpolymers comprising from 10 to 50% by moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, from 10 to 80% by moles of acrylamide and from 10 to 50% by moles of acryloylmorpholine; - terpolymers comprising from 10 to 50% by moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, from 10 to 50% by moles of N-vinylpyrrolidone and 10 to 50% by moles of acryloylpyrrolidone; - terpolymers comprising from 10 to 50% by moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, from 10 to 50% by moles of N-vinylpyrrolidone and 10 to 50% by moles of N-vinylpyrrolidone; - terpolymers comprising from 10 to 50% by moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, from 10 to 50% by moles of N-vinylpyrrolidone and 10 to 50% by moles of acryloylpyrrolidine; and - terpolymers comprising from 10 to 50% by moles of 2-acrylamido-2-methylpropanesulfonic acid and/or its salified form, from 10 to 50% by moles of N-vinylpyrrolidone and 10 to 50% by moles of acryloylmorpholine.
    [0012]
    12. Process according to claim 1, characterized in that the copolymer is a tetrapolymer, the three comonomers, in addition to ATBS, being chosen from the group consisting of acrylamide, N-vinylpyrrolidone and the monomers of formula (I).
    [0013]
    13. Process according to claim 1, characterized in that the polymer solution comprises between 2000 ppm and 50,000 ppm of polymers.
    [0014]
    14. Process according to claim 1, characterized in that the injection fluid comprises between 200 and 5000 ppm of polymer resulting from the polymer-based solution.
    [0015]
    15. Process according to claim 1, characterized in that the injection fluid additionally comprises at least one surfactant and/or at least one alkaline agent and/or at least one fluidizer.
    [0016]
    16. Process according to claim 1, characterized in that the polymer additionally comprises at least one hydrophobic monomer chosen from the group consisting of undecanoic acid acrylamide, undodecyl acid methyl acrylamide and ethoxy behenyl methacrylate (25).
    [0017]
    17. Process according to claim 1, characterized in that the viscosified injection fluid comprises: - more than 1000 ppb of ferrous Fe2+ ions, in fact even more than 2000 ppb of ferrous Fe2+ ions, and even more of the than 5000 ppb of ferrous Fe2+ ions, and up to 100 ppm, and/or - more than 20 ppm hydrogen sulfide, in fact even more than 40 ppm hydrogen sulfide, and up to 400 ppm, and - between 500 ppb and 10 ppm dissolved oxygen, and in fact even more than 1000 ppb dissolved oxygen.
    [0018]
    18. Process according to claim 1, characterized in that the weight ratio between the amount of Fe2+ ions, expressed in ppm, and the amount of dissolved oxygen in the injection fluid, expressed in ppm, is greater than 10 .
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    法律状态:
    2019-05-14| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-04-06| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-06-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-07-06| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 14/01/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1250585|2012-01-20|
    FR1250585A|FR2986034B1|2012-01-20|2012-01-20|PROCESS FOR ASSISTED OIL RECOVERY BY INJECTION OF A POLYMERIC SOLUTION|
    PCT/IB2013/050350|WO2013108174A1|2012-01-20|2013-01-14|Process for the enhanced recovery of oil by injection of a polymer solution|
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