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    • 专利摘要:
    fluids for oil field treatment. the present invention is directed to a method comprising: mixing (i) a zwitterionic polymer prepared by inverse emulsion polymerization of at least one ab manometer comprising a betaine group and optionally one or more non-ionic monometers ba, (ii) a surfactant and (iii) water produced to form a well maintenance and repair fluid. the resulting well maintenance and repair fluid is introduced into a hydrocarbon well.
    公开号:BR112013012457B1
    申请号:R112013012457-1
    申请日:2011-11-15
    公开日:2021-03-30
    发明作者:D.V. Satyanarayana Gupta；Madhukar Chetty；Paul Scott Carman
    申请人:Baker Hughes Incorporated；
    IPC主号:
    专利说明:

    BACKGROUND
    The present disclosure relates generally to a well bore maintenance and repair fluid, and more particularly to the viscosification of a well bore maintenance and repair fluid using polymers comprising betaine units.
    In the past, well drilling and development operations used large amounts of drinking water. In some areas, obtaining drinking water for these operations has become more expensive and difficult due to lack of water and government regulation. On the other hand, a vast amount of water produced can be generated from hydrocarbon wells. Generally speaking, this water produced must be disposed of at a significant cost. Given the volume of drinking water needed for well operations, the ability to recover and use water produced as a well maintenance and repair fluid can alleviate the impact of well operations in the absence of drinking water, reduce environmental concerns of contaminating water reserves. drinking water, and potentially lower the cost of well maintenance and repair operations.
    However, produced water often has high concentrations of total dissolved solids (“TDS”), including high salinity and hardness content. Many conventional viscosification polymers, including slick water fracture polymers based on polyacrylamide, do not work well in such waters with high salinity, especially in the presence of metals, 2/44 such as iron, which are often present in produced water. In addition, many surfactants commonly used in well maintenance and repair fluids have reduced solubility in water produced due to the high TDS content. The reduced solubility of surfactants can increase mixing times and / or reduce the viscosification effect of viscosification polymers in the water produced. Therefore, it would be a breakthrough in the technique to discover a new viscosification system that works well in produced water, especially in produced water having relatively high TDS content.
    The use of polymers comprising betaine units to viscosify hydrocarbon well fluids has been disclosed by D.V. Satynarayana Gupta et al., In the publication of the copending US patent application no. 2010/0197530 (“order 530”) published on August 5, 2010, the disclosure of which is hereby incorporated by reference in its entirety for reference. The order reveals a maintenance and repair fluid for use in oil or natural gas field wells. The well maintenance and repair fluid includes an aqueous brine medium and a zwitterionic polymer. The zwitterionic polymer is prepared by polymerizing at least one monomer, Ab, comprising a betaine group and optionally one or more nonionic monomers, Ba. The pickles used in the '530 order examples were pick-up pickles, which are pickles of high purity and mixtures without significant amounts of contaminants such as iron, barium, strontium, sulphates and other contaminants that are often contained in produced water.
    The zwitterionic polymers of order '530 can be mixed with brines using a batch mixing process. For example, pickles can be mixed in high shear with a surfactant, such as ammonium salts of polyaryl phenyl ether sulphate in a batch process for approximately 15 minutes until a desired fluid viscosity is achieved.
    It is well known in the art that well fluid can be mixed “in motion” as it is pumped to the bottom of the well. Moving processes generally involve mixing components, such as the visoosification polymer, for a relatively short period of time compared to batch mixing processes, and then pumping the well fluid to the bottom of the well. To mix moving fluids, surfactants can be used to allow the viscosification polymer to mix quickly and thereby quickly allow the well maintenance and repair fluid to reach an appropriate viscosity. The ability to mix viscosification polymers in motion can have certain benefits, including saving time and / or allowing reduced size and cost of mixing equipment over batch mixing processes. The ability to employ viscosification polymers in batch or moving mixing processes also increases the flexibility of the process.
    Therefore, there is a need for improved viscosifying agents for use as well hole maintenance and repair fluids that have one or more of the following properties: reduced mixing time, ability to allow mixing in motion in water with high salinity or produced water , good viscosification power in produced waters, good rheological stabilization at increased temperatures in produced waters, good stability in a relatively high ionic resistance and / or good stability in a relatively saline medium, such as water produced with high total dissolved solids; good thickening power for media comprising a relatively high ionic resistance, such as saline medium, including highly saline medium, and / or a thickening power at low polymer contents. SUMMARY
    One embodiment of the present disclosure is directed to a method comprising: mixing (i) a zwitterionic polymer prepared by reverse emulsion polymerization of at least one Ab monomer comprising a betaine group and optionally one or more nonionic monomers, Ba, (ii) a surfactant and (iii) water produced to form a well maintenance and repair fluid. The resulting well maintenance and repair fluid is introduced into a hydrocarbon well.
    Another embodiment of the present disclosure is directed to a method of maintaining and repairing a hydrocarbon well. The method comprises introducing into a hydrocarbon well a fluid comprising (i) a zwitterionic polymer prepared by inverse emulsion polymerization of at least one Ab monomer comprising a betaine group and optionally one or more nonionic Ba monomers, (ii) a surfactant chosen from ammonium C4-C12 alkyl ether sulfates, ammonium C4C12 alkyl ether sulfonates and 5/44 ammonium C4-C12 alkyl ether phosphates; and (iii) an aqueous-based saline solution. BRIEF DESCRIPTION OF THE DRAWINGS
    Figures 1 to 9 illustrate viscosity data for various mixtures, according to the modalities of the present disclosure.
    Although the disclosure is susceptible to several modifications and alternative forms, specific modalities have been shown as an example in the drawings and will be described in detail here. However, it must be understood that the disclosure is not intended to be limited to the specific forms disclosed. Instead, the intention is to cover all modifications, equivalents and alternatives understood in the spirit and scope of the invention as defined by the appended claims. DETAILED DESCRIPTION
    The present disclosure is directed to a maintenance and repair fluid for use in an oil or natural gas well borehole. In one embodiment, the maintenance and repair fluid includes a zwitterionic polymer, a surfactant and produced water. In another embodiment, the maintenance and repair fluid includes a zwitterionic polymer; a surfactant chosen from ammonium C4C12 alkyl ether sulfates, ammonium C4-C12 alkyl ether sulfonates and ammonium C4-C12 alkyl ether phosphates; and an aqueous-based saline solution. The zwitterionic polymer is prepared by polymerizing at least one monomer, Ab, comprising a betaine group and optionally one or more nonionic monomers, Ba.
    According to the present disclosure, the monomer, Ab, can be chosen from at least one of the following monomers: A) Substituted or unsubstituted alkyl sulfonates or alkyl phosphonates of ammonioalkyl dialkyl acrylates, dialkylammonioalkyl methacrylates, dialkylammonioalkyl acrylamides, dialkylammonioalkyl acrylates, dialkylammonioalkoxy alkyl acrylates, dialkylammonioalkoxy alkyl methacrylates, dialkylammonioalkoxy alkyl acrylamides, and dialkylammonio alkoxyalkyl methacrylamides, such as: 1) SPOYDROYETHYLETHYL METHYL;
    2) Sulfoethyldimethyl ammonioethyl methacrylate (formula 2) and sulfobutyldimethyl ammonioethyl methacrylate (formula 3):
    The synthesis of which is described in the article “Sulfobetaine zwiterionomers based on n-butyl acrylate and 2-ethoxyethyl acrylate: monomer synthesis and copolymerization behavior”, Journal of Polymer science, 40, 511-523 (2002), the disclosure of which is incorporated here as reference in full. 3) Sulfohydroxy propyl dimethyl ammonioethyl methacrylate (SHPE) (formula 4):
    4) Sulfopropyl dimethyl ammoniopropyl acrylamide (formula 5):
    The synthesis of which is described in the article “Synthesis and solubility of the poly (sulfobetaine) s and the corresponding cationic polymers: 1. Synthesis and characterization of sulfobetaines and the corresponding cationic monomers by nuclear magnetic resonance spectra”, Wen-Fu Lee and Chan- Chang Tsai, Polymer, 35 (10), 2210-2217 (1994), the disclosure of which is hereby incorporated by way of reference in its entirety. 5) Sulfopropyl dimethylammonium propyl methacrylamide, sold by Raschig under the name SPP (formula 6):
    6) Ammonioethyl sulfopropyl dimethyl acrylate, sold by Raschig under the name SPDA (formula 7)
    7) Sulfohydroxy propyl dimethyl ammonium propyl methacrylamide (“SHPP”) (formula 8)
    8) ethoxyethyl sulfopropyl diethylammonium methacrylate (formula 9)
    The synthesis of which is described in the article “Poly (sulphopropylbetaines): 1. Synthesis and characterization”, VM Monroy Soto and JC Galin, Polymer, 1984, vol. 25, 121-128, the disclosure of which is incorporated herein by way of reference in its entirety. 9) Ethyl sulfohydroxypropyl diethylammonium methacrylate (formula 10)
    B) Substituted or unsubstituted heterocyclic betaine monomers, such as: 1) Sulfobetaines derived from piperazine, examples of which include compounds of formulas 11, 12 and 13,
    The synthesis of which is described in the article “Hydrophobically modified zwitterionic polymers: synthesis, bulk properties and miscibility with inorganic salts”, P. Koberle and A. Laschewsky, Macromolecules, 27, 2165-2173 (1994), the disclosure of which is incorporated here as 10/44 reference in full. 2) Sulfobetaines derived from vinyl substituted pyridines, such as 2-vinylpyridine and 4-vinylpyridine, whose examples include: a) 2-vinyl-1- (3-sulfopropyl) pyridinium betaine (2SPV or “SPV”) (formula 14), sold by Raschig under the name SPV:
    b) 4-vinyl-1- (3-sulfopropyl) pyridinium betaine (“4SVP”) (formula 15),
    The synthesis of which is revealed in the article “Evidence of ionic aggregates in some ampholytic polymers by transmission electron microscopy”, VM Castanho and AE González, J. Cardoso, O. Manero and VM Monory, J. Mater. Res. 5 (3), 654-657 (1990), the disclosure of which is incorporated herein by way of reference in its entirety. 3. sulfobetaines derived from imidazois, such as: a) 1-vinyl-3- (3-sulfopropyl) imidazolium betaine (formula 16)
    The synthesis of which is described in the article “Aqueous solution properties of a poly (vinyl imidazolium sulphobetaine)”, JC Salamone, W. Volkson, AP Oison, SC Israel, Polymer, 19, 1157-1162 (1978), the disclosure of which is incorporated here full reference title. c) Alkylsulfonates or substituted or unsubstituted alkylphosphonates of dialkylammonioalkylalkyls, such as: 1) Sulfopropylmethyldialylammonium betaine (17):
    The synthesis of which is described in the article “New poly (carbobetaine) s made from zwitterionic diallylammonium monomers”, Favresse, Philippe; Laschewsky, Andre, Macromolecular Chemistry and Physics, 200 (4), 887-895 (1999), the disclosure of which is incorporated here by way of reference in its entirety. D) Alkyl sulfonates or substituted or unsubstituted alkylphosphonates of dialkylammonioalkyl styrenes, such as the compounds of formulas 18 and 19:
    The synthesis of which is described in the article “Hydrophobically modified zwitterionic polymers: Synthesis, bulk properties, and miscibility with inorganic salts”, P. Koberle and A. Laschewsky, Macromolecules, 27, 2165-2173 (1994), the disclosure of which is incorporated here as title reference text in its entirety. E) Substituted or unsubstituted betaines resulting from ethylenically unsaturated anhydrides and dienes, such as the compounds of formulas 20 and 21:
    The synthesis of which is described in the article “Hydrophobically modified zwitterionic polymers: synthesis, bulk Properties and miscibility with inorganic salts”, P. Koberle and A. Laschewsky, Macromolecules, 27, 2165-2173 (1994), the disclosure of which is incorporated here as reference in full. F) Substituted or unsubstituted phosphobetaines, such as the compounds of formula 22 (“MPC”) and formula 23 (“VPC”):


    The synthesis of MPC and VPC is described in EP 810 239 B1 (Biocompatibles, Alister and others), the disclosure of which is incorporated herein by reference in its entirety.
    In embodiments where the Ab monomers described above are substituted, the substituents can be chosen from any appropriate groups that will not be significantly detrimental to a desired function of these compounds, such as the ability to provide viscosification of a well bore maintenance and repair fluid. The substituents can be attached to, for example, cyclic fractions and / or linear carbon chain fractions of the compounds. Examples of suitable substituents can include hydroxyl groups, as in formulas 4, 8 and 10 above, as well as C1 to C6 alkyl groups.
    In one embodiment, betaines can be monomers of formula 24:
    Or formula 25:
    Where: R1 is hydrogen or methyl, R2 and R3 which are identical or different are hydrogen or alkyl having 1 to 6 carbon atoms, Y1 is -O- or NR2, Z- is SO3-, M is 1 or 3, and N is 1-6.
    In one embodiment, the monomer Ab can be chosen from sulfopropyl dimethyl ammonioethyl methacrylate (SPE), sulfoethyl dimethyl ammonioethyl methacrylate, sulfobutidimethyl ammonioethyl amide, propionyl sulfide, methyl amide, propionyl sulfide, methacrylamide ), Sulfohydroxypropyl dimethyl ammoniopropyl methacrylamide (SHPP), sulfopropyl dimethylammonioethyl acrylate (SPDA), sulfopropyl diethylammonium ethoxyethyl methacrylate, 2-vinyl-1- (3-sulfopropyl) pyridinium betaine, 4-vinyl-1- (3-sulfopyridine) -pyridine betaine , 1-vinyl-3- (3-sulfopropyl) imidazolium betaine, sulfopropyl methyldialyl ammonium betaine. In another exemplary modality, monomer Ab corresponds to one of the following formulas:


    The hydrophilic nonionic monomer Ba can be chosen to be one or more of: hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxylpropyl methacrylate, acrylamide (AM), methacrylamide, N-methylolacrylamide, dimethylacrylamide, polyethylacrylamide, dimethylacrylamide, dimethylacrylamide , polypropylene oxide, polypropylene / polyethylene oxide copolymers (which can be any appropriate type of copolymer, such as block or random copolymers), α-methacrylates, vinyl alcohol or pyrrolidone vinyl.
    In one embodiment, the hydrophilic non-ionic monomer Ba is acrylamide (AM) and / or monomer Ab includes one or both of sulfopropyl dimethyl ammonioethyl methacrylate 16/44 (SPE) and sulfopropyl dimethylammonium propyl methacrylamide (SPP). In one embodiment, the hydrophilic non-ionic monomer Ba is acrylamide (AM) and the monomer Ab is SPP.
    The polymers are thus prepared by a process of reverse polymerization which comprises the following stages: a1) preparation of the reverse emulsion, and a2) polymerization. In one embodiment, stage a1) is carried out by emulsifying a mixture comprising the aqueous phase comprising the monomers, the external phase and at least one emulsifying agent. Polymerization is carried out by joining the monomers Ab and optionally the monomers Ba with an initiator compound that can generate free radicals.
    The temperature employed for the polymerization can be any appropriate temperature. For example, the temperature can vary from approximately room temperature to approximately 75 ° C, depending on the chosen initiation system.
    Any appropriate concentration of monomers can be used in the polymerization process. In one embodiment, the molar ratio of Ab monomers to Ba monomers ranges from approximately 4:96 to approximately 40:60, as from approximately 7:93 to approximately 30:70.
    Like the external phase, any suitable inert hydrophilic liquid can be employed. Examples of suitable hydrophobic liquids may include aliphatic and aromatic hydrocarbons and halocarbons, such as toluene, xylene, o-dichlorobenzene, perchlorethylene, hexane, heptane, kerosene, a mineral oil and Isopar M (a high purity isoparaffin type substance 17/44 sold by Exxon Corporation). Similarly, any suitable water-in-oil emulsifying agent, such as sodium hexadecyl phthalate, sorbitan monooleate, sorbitan monostearate, mono- and diglycerides, polyethoxylated sorbitol hexaoleate, octyl sodium phthalate or stearyl sodium phthalate. In one embodiment, the emulsifying agent is sorbitan monooleate. Example concentrations of the emulsifying agent can vary from approximately 0.5% to approximately 10%, as from approximately 1% to approximately 5% by weight of the emulsion.
    The ratio of the aqueous phase to the external phase can vary over wide limits. For example, the water-in-oil emulsion may comprise approximately 20% to approximately 80% aqueous phase and thereby approximately 80% to approximately 20% oil phase, these percentages being based on the total weight of the water-in-oil emulsion . In one embodiment, a ratio of the aqueous phase to the oil phase is approximately 70% to approximately 75% aqueous phase to approximately 30% to approximately 25% oil phase, where percentages are based on the total weight of the water emulsion in oil.
    As discussed above, polymerization is initiated by means of a chemical initiator comprising free radicals. This initiator can be dissolved in the oil phase or in the aqueous phase, according to its solubility characteristics. Examples of water-soluble initiators may include 4,4'-azobis [4-cyanovaleric acid] (abbreviated as ACVA), potassium persulfate (K2S2O8) and 18/44 t-butyl hydroperoxide. Redox-type water-soluble initiators, such as bromate / bisulfite or metabisulfite (for example, KBrO3 / NaHSO3 or KBrO3 / NaS2O5) or persulfate / bisulfite initiators, can also be used. Examples of oil-soluble initiators include azobisisobutyronitrile (AIBN) and 2,2'-azobis (2,4-dimethylvaleronitrile) (ADVN).
    The proportion of chemical initiator used depends on several factors. For example, if it is necessary to maintain a desired reaction rate, the proportion of initiator can be increased as the reaction temperature drops. By adjusting the reaction temperature and the proportion of initiator, it may be possible to carry out the polymerization in a reasonable time and with a reasonable conversion from monomer to polymer, retaining the advantages of a polymerization at low temperatures.
    The water-soluble zwitterionic polymers of the present invention can be used as viscosifying agents for aqueous solutions over a wide range of salinity and temperature and as an agent for modifying particle surfaces in aqueous suspensions. For these uses / applications, the polymer can be supplied in any practical form. For example, the polymer can be supplied in a dry solid form or in a vectorized form, such as in a solution, emulsion or suspension. In one embodiment, the polymer is supplied in the form of an aqueous solution. In one example, the aqueous solution may comprise approximately 5 to approximately 50% by weight, as well as from approximately to approximately 30% by weight of the polymer.
    The present disclosure also relates to compositions comprising the polymer. The polymer can help to increase the viscosity of the compositions. The polymer may be in the form of an aqueous composition comprising the reverse emulsion with the aqueous phase comprising the polymer dispersed in the form of droplets in an external hydrophobic phase and other ingredients chosen from a surfactant, an organic salt, an inorganic salt, a detergent and a thickener.
    The aqueous composition may additionally comprise ionic entities, such as inorganic salts or organic salts, such as acid salts, and it is possible for the salts to have a superficially active or non-superficially active nature. The composition can be a "saline" composition. In one embodiment, the polymer may make it possible to increase the viscosity of compositions comprising ions, such as saline compositions and in particular, compositions of relatively high ionic strength. For example, the polymer may make it possible to increase the viscosity of compositions comprising relatively large amounts of salts, such as compositions based on seawater or brines, including produced water.
    The ionic strength of the composition can vary from low to high, depending on the application. It has been found that the polymer can be effective as a thickening agent at zero or low ionic resistance and that, surprisingly, it can remain effective at high ionic resistance. Ionic resistance can, for example, be at least approximately 0.7 mol / l or at least approximately 1 mol / l, or even greater than 2 mol / l, after saturation of the salt or mixture of salts. In a 20/44 embodiment, the composition may comprise at least 25 g / l of a salt (11 pounds per gallon of density), such as, for example, approximately 35 g / l of a salt or more.
    Any suitable salts can be used in the compositions of the present application. Suitable salts include monovalent, divalent and polyvalent salts. In one embodiment, the salts may include a cation selected from alkali metal, alkaline earth metal, ammonium, manganese and zinc cations, and an anion selected from halides, oxides, carbonates, nitrates, sulfates, acetates and anions of shape. For example, the salt may be potassium chloride, sodium chloride, sodium bromide, calcium chloride, calcium bromide, zinc bromide, zinc formate, zinc oxide and mixtures of these salts.
    In one embodiment, the composition can be formed from sea water or a brine comprising the polymer. In one embodiment, the composition is a brine comprising divalent ions, such as those formed from the dissociation of alkaline earth metal salts, such as calcium or magnesium salts, including CaCl2, CaBr2, MgCl2 or MgBr2; or other salts that form a divalent ion, such as zinc salts (for example, ZnCl2 or ZnBr2). The concentration of divalent ions in the brine can vary. In one example, the brine may comprise divalent salts in an amount greater than approximately 25% by weight of the total salts in the brine.
    In one embodiment, the composition may comprise produced water. The water produced can have a relatively high content of total dissolved solids (“TDS”). Examples of TDS content can range from approximately 50,000 mg / L to saturation, such as approximately 100,000 mg / L to approximately 300,000 mg / L, based on the total volume of the composition.
    The elements contained in the produced water can vary significantly depending on the source of the water. In one embodiment, the water produced can comprise at least one of calcium, potassium, iron, magnesium, strontium, sodium, sulfate and chloride. Examples of appropriate dissolved calcium concentrations can range from approximately 5000 mg / L to saturation, such as approximately 10,000 or 15,000 mg / L to approximately 50,000 mg / L. examples of appropriate dissolved potassium concentrations can range from approximately 1000 mg / L to saturation, with approximately 2000 or 3000 mg / L to approximately 10,000 mg / L. examples of appropriate dissolved iron concentrations can range from approximately 2 mg / L to saturation, such as approximately 5 or 10 mg / L to approximately 100 mg / L. examples of appropriate concentrations of dissolved magnesium can range from approximately 5 mg / L to saturation, such as approximately 100 or 1000 mg / L to approximately 2500 mg / L. examples of appropriate dissolved strontium concentrations can range from approximately 5 mg / L to saturation, such as approximately 100 or 1000 mg / L to approximately 2500 mg / L. examples of appropriate dissolved sodium concentrations can range from approximately 10,000 mg / L to saturation, such as approximately 25,000 or 50,000 mg / L to approximately 100,000 mg / L. examples of appropriate dissolved sulfate concentrations can range from approximately 100 mg / L to approximately 50,000 mg / L, or even saturation. Examples of appropriate dissolved chloride concentrations can range from approximately 10,000 mg / L to saturation, such as approximately 50,000 or 100,000 mg / L to approximately 300,000 mg / L.
    In addition to those listed above, water produced can include a variety of other species. Examples of such species include barium, boron, copper, manganese, molybdenum, phosphorus, silica, zinc, aluminum, carbonate and bicarbonate.
    The well maintenance and repair fluid composition can comprise any appropriate amount of water produced. In one embodiment, the water produced can be 50% by weight or more of the well maintenance and repair fluid. For example, the water produced can vary from approximately 75% to approximately 99.9% by weight of the composition.
    In one embodiment, the well maintenance and repair fluid comprises at least one surfactant. Any suitable surfactant that is soluble in the brine or water produced can be used. Examples of surfactants include ammonium organosulfates, such as ammonium C4-C12 alkyl ether sulfates; ammonium organosulfonates, such as ammonium C4-C12 alkyl ether sulfonates, and ammonium organophosphates, such as ammonium C4-C12 alkyl ether phosphates. In one embodiment, the surfactant is an ammonium C8-C10 alkyl ether sulfate. An example of an appropriate ammonium C8-C10 alkyl ether sulfate is RHODAPEX® CD128 / I, available from Rhodia based in Cranbury, New Jersey.
    The above surfactants can be used in any appropriate concentration that will result in a desired viscosity. Examples of appropriate concentrations can range from approximately 0.5 gallon per thousand ("gpt") or more, such as approximately 1 gpt to approximately 20 gpt, or approximately 2 gpt to approximately 8 gpt.
    By employing one or more of the surfactants discussed above, it may be possible to reduce the mixing time of the zwitterionic polymers of the present application compared to the time it would take to mix the polymers without a surfactant. In one embodiment, mixing times can be shortened sufficiently to allow for mixing on the go. Examples of suitable mixing times can range from approximately 1 to approximately 2 minutes or less. Of course, longer mixing times can be employed if desired.
    The short mixing times can allow the well maintenance and repair fluids of the present application to reach a desired viscosity relatively quickly, such as, for example, in the mixing time of 1 to 2 minutes or less.
    Other suitable surfactants that are soluble in the brine or produced water used in the well maintenance and repair fluid can also be used in addition to or as an alternative to those listed above, including surfactants used during the preparation of the polymer. These other surfactants can be used, for example, in batch mixing processes. Examples of such surfactants are the ammonium salts of 24/44 polyaryl phenyl ether sulphate, such as the ammonium salt of tristyrylphenol ethoxylate sulphate, which is sold under the trade name SOPROPHOR 4 D 384 by RHODIA. Surfactants other than ammonium-based salts can also be used.
    In one embodiment, all or a portion of the surfactant can be introduced with the polymer, if a surfactant was used during the preparation of the polymer. In one embodiment, a surfactant can be added to the composition in addition to the surfactant used during polymer preparation. Alternatively, any surfactant can be added separately from the polymer.
    The total amount of surfactant included in the composition may vary depending on the use of the composition. For example, the amount can vary from the values indicated above up to approximately 20% by weight, such as from approximately 5% to approximately 15% by weight of surfactant with respect to the polymer.
    The amount by weight of polymer in the compositions may depend on the desired rheological behavior and / or the desired thickening resistance for the compositions and on the possible presence of other compounds, in particular ionic compounds, such as salts. In one embodiment, the amount by weight may be greater than approximately 0.01% by weight, with respect to the composition, for example, greater than approximately 0.1% by weight and often greater than or equal to approximately 0, 5% or approximately 1% by weight. The amount will generally be less than or equal to approximately 20% by weight, with approximately 10% by weight. Advantageous 25/44 thickening may in some cases be observed at polymer concentrations ranging from approximately 0.1% to approximately 1% by weight, and / or from approximately 1% to approximately 2% by weight, and / or approximately 2 % to approximately 3% by weight, and / or from approximately 3% to approximately 4% by weight, and / or from approximately 4% to approximately 5% by weight.
    As discussed above, the compositions of the present application can be employed as a well bore maintenance and repair fluid for oil wells and natural gas wells, including subsea wells. In one embodiment, the zwitterionic and surfactant polymers of the present disclosure are used as viscosifying agents in produced water or other brine formulations used in oil and gas well boreholes. Examples of such fluids include: drilling fluids, gravel conditioning fluids, fracture fluids, frac conditioning fluids, completion fluids, and fluids used for completion pills.
    Accordingly, the present disclosure can be directed to a method of drilling a natural gas or oil well bore in which the fluids of the present application are used as a drilling fluid. In one embodiment, well hole maintenance and repair fluids of the present disclosure comprising an aqueous medium, such as produced water or other brines, a zwitterionic polymer and a surfactant can be circulated through a well hole as it is drilled into a well. underground formation. The drilling fluid can carry drilling chips created by the drilling process in a return flow back to the well drilling platform. The drilling fluid circulation can be terminated after stopping drilling. Then a tube column, such as an annular tube liner, can be lowered into the well hole. In an optional second stage of the process, the well hole maintenance and repair fluid of the present order can then be circulated through the well hole to remove additional drilling chips. For example, well hole maintenance and repair fluid can be pumped down through the inside of the pipe and up through an annular space, which is located between the outside of the pipe and the walls of the well hole, for that purpose. how to load the shavings out of the well hole.
    In one embodiment, the drilling fluid used during the second stage of the process may be different from the drilling fluid used during the drilling stage. For example, the well hole maintenance and repair fluids of the present disclosure can be used during the drilling stage, while a second drilling fluid other than the well hole maintenance and repair fluids of the present disclosure can be used during the drilling stage. second stage or vice versa.
    The well hole maintenance and repair fluids of the present application can be used as gravel conditioning fluids. In one embodiment, a well bore maintenance and repair fluid comprising an aqueous medium, such as produced water or other brines, a zwitterionic polymer and a surfactant can further comprise gravel suspended in it. As part of the gravel conditioning process, a permeable mesh can be placed against the face of the underground formation, followed by pumping the maintenance fluid and repairing the borehole comprising the gravel in the annular space of the borehole in such a way that gravel becomes wrapped against the outside of the screen.
    The well hole maintenance and repair fluids of the present application can also be used as fracture fluids. In one embodiment, the well bore maintenance and repair fluid of the present disclosure comprising a zwitterionic polymer, a surfactant and an aqueous medium, such as produced water or other brines, can be used to fracture an underground formation. Well hole maintenance and repair fluid is pumped into the well hole at a rate and pressure sufficient to form fractures that extend into the underground formation, providing additional paths through which fluids being produced can flow into the wells. well holes. In one embodiment, the well hole maintenance and repair fluid may include a propant. Well-known propellants used in fracture include separate sand, bauxite, or resin-coated sand, any of which can be suspended in the fracture fluid. The propellant becomes deposited on the fractures and thus keeps the fractures open after the pressure exerted on the fracture fluid has been released.
    The compositions of the present disclosure, whatever the use, may comprise dispersed liquid particles (emulsified droplets) or dispersed solid particles. Liquid particles can, for example, be synthetic oils (for example, silicone oils) or oils of mineral or vegetable origin. The solid particles can in particular be sand, density modifying particles, residue and / or polymeric particles. The polymer can promote the suspension of these particles for the time necessary for the use of the composition and / or for a period of storage. It can also alternatively contribute to easy transport of the particles, to position them in or move them to an appropriate point.
    The fluids of the present disclosure can include additional ingredients to modify the rheological and chemical properties of the fluid. Clay materials such as bentonite, atapulgite, sepiolite or other material commonly used in drilling fluids can be included to provide drilling muds to lubricate drilling columns and suspend drilling chips. The fluid can also include buffering agents or pH control additives. Buffering agents can be used in well hole maintenance and repair fluids to maintain the desired fluid pH. If the pH of the well bore maintenance and repair fluid becomes too low, severe degradation of the included polymers, such as viscosifying agents, may result. Examples of suitable buffering agents include, but are not limited to: sodium phosphate, sodium hydrogen phosphate, sodium hydroxide-boric acid, sodium hydroxide-citric acid, boric acid-boric acid, sodium bicarbonate, sodium salts ammonium, sodium salts, potassium salts, dibasic phosphate, tribasic phosphate, lime, off-white 29/44, magnesium oxide, basic magnesium carbonate, calcium oxide and zinc oxide.
    The temperature and pressure of the fluid may vary according to the use that is made of the fluid and its environment. The polymer can remain effective over a relatively wide range of temperatures, including under conditions that require relatively high temperatures, particularly in the fields of oil and / or gas extraction. For example, the composition may have a temperature ranging from approximately 20 ° C to relatively high temperatures, such as greater than or equal to 50 ° C, greater than or equal to 70 ° C, greater than or equal to 100 ° C, greater than or equal to 150 ° C or greater than or equal to 180 ° C. the pressure can be any appropriate pressure, such as atmospheric pressure or a higher pressure.
    A reduced specific viscosity can be measured by dissolving the polymer in a 20% by weight aqueous NaCl solution. The intrinsic viscosity n can then be obtained by linear extrapolation from the reduced specific viscosity to zero polymer concentration. The slope of this extrapolation is equal to k '(^) 2, k' being the Huggins coefficient. This method of calculating n is described in detail in the publication Polymer handbook (4th edition), J. Brandrup, EH Immergut and EA Grulke, Wiley (1999), the description of calculating ^ in the Polymer Handbook being incorporated here by way of reference in its entirety. . The specific viscosity makes it possible to have indirect access to molecular weights greater than approximately 2,000,000, which cannot be directly determined experimentally. In one embodiment of the present application, the 30/44 zwitterionic polymers have an intrinsic viscosity of approximately 600 or greater, such as approximately 1000 or greater, where the reduced specific viscosity is measured by dissolving the polymer in a 20% aqueous Nal solution in weight as described above.
    Other features or advantages of the invention may become apparent in the light of the examples that follow, given by way of illustration without a limiting nature. EXAMPLES
    Example 1 (comparative) - solution polymerization - poly (acrylamide / SPP) 90/10 mol / mol Copolymerization 82.4 g of 50% acrylamide in water, 18.8 g of
    SPP and 94.4 g of water are added to a 500 ml three-necked round-bottom flask equipped with a nitrogen inlet, a mechanical stirrer (anchor), a reflux condenser and temperature regulation through an oil bath thermostatically controlled. The temperature of the reaction medium is brought to 65 ° C while washing with nitrogen, 0.3 g of sodium persulfate dissolved in 5 g of water is added at 65 ° C. The temperature of the reaction medium is maintained for 24 h. the combined mixture is subsequently cooled to room temperature. The final product exists in the form of a translucent gel.
    The molar mass of the obtained polymer can be conventionally adjusted by changing the amount of initiator introduced, the reaction temperature or the addition of a transfer agent. The concentrations of initiator and the corresponding molar masses, determined by steric exclusion chromatography (+ CVG ref) are referenced in Table 1 below:
    Table 1
    Example 2 - reverse emulsion polymerization - poly (acrylamide / SPP) 90/10 mol / mol
    The synthesis occurs in two stages: preparation of an emulsion comprising monomers and surfactants, followed by copolymerization.
    Preparation of an emulsion comprising monomers and surfactants: 110.2 g of Shellsol D80 (Shell Chemicals), 18.5 g of G946 (ICI), 9.3 g of Rhodasurf LA-3 (Rhodia) and 4.9 g of Hypermer B261 (Uniquema) are added to a 250 ml glass beaker with magnetic stirring. Stirring is continued until a clear solution is obtained (mixture 1), 199.8 g of 50% acrylamide in water, 91.3 g of 50% SPP in water, 0.2 g of Versene 100 (Dow) and 2.9 g of sodium sulfate are added to a 500 ml glass beaker with magnetic stirring. Stirring is continued until a clear solution is obtained (mixture 2). Mixture 2 is subsequently introduced into mixture 1 with magnetic stirring. Stirring is maintained for 5 min. and then all liquid is added to a rotor / stator type mixer to be mixed for 10 s (6000 turns / min.) the stable 32/44 emulsion is thus obtained.
    Copolymerization all emulsion prepared immediately above is added to a glass reactor with a 1 liter jacket equipped with a nitrogen inlet, a mechanical stirrer, a reflux condenser and temperature regulation through a thermostatically controlled bath. The temperature of the reaction medium is brought up to 45 ° C while washing with nitrogen. 0.2 g of Trigonox 25C75 (Akzo Nobel) is added at 45 ° C. An additional 0.2 g of Trigonox 25C75 is added 4 hours after that addition. The temperature of the reaction medium is subsequently raised to 55 ° C for 3 h. the combined mixture is cooled to room temperature.
    The final emulsion exists in the form of a translucent, slightly colored liquid that is not very viscous.
    By following the procedure described above, polymers of varying molar masses are produced by modifying the initiator level. However, for countless tests, the molar masses are too high to be measured by steric exclusion chromatography. Molar masses are likely to be significantly greater than 3 x 106 g / mol. In addition, copolymers with varying SPP / acrylamide ratios are also synthesized. The characteristics of the products are referenced in table 2 below: Table 2


    Example 3 - evaluations
    The viscosities of the polymer solutions are evaluated using an AR2000 rheometer (TA Instrument,
    Surrey, United Kingdom) supplied with Couette type geometry (internal radius = 14 mm; external radius = 15 mm and height = 42 mm).
    Molar masses The viscosity contributed by the dissolution of a polymer is represented by its intrinsic viscosity (the linear extrapolation to zero concentration of the reduced specific viscosity)
    ,
    Where q is the viscosity of the solution comprising the polymer, q is the viscosity of the solvent and c is the polymer concentration.
    The intrinsic viscosity, for a polymer chemical composition under given solvent conditions, is related to the molar mass by the Mark-Houwink relationship. See Polymer Handbook (4th edition), J. Brandrup, E.H. Immergut and E.A. Grulke, Wiley (1999), the description of the Mark-Houwink relationship in the Polymer handbook being hereby incorporated by reference in its entirety. [q] = KMa with “K” and “a constants that depend on the chemical composition of the polymer and the solvent and temperature.
    The polymers of examples 1 and 2 are purified and dried and then dissolved in a 20% by weight NaCl solution in different polymer concentrations. The curves of reduced specific viscosity as a function of the polymer concentration make it possible to determine the intrinsic viscosity given in table 3 below. Table 3

    Rheology in saline solutions The copolymers described in examples 1 and 2 are used in the variable salinity solutions described 10 in table 4 below. Table 4

    The polymers are purified and dried. The powders obtained are dissolved in 10 g / l with magnetic stirring.
    Viscosities are measured 72 h after sample preparation and the values obtained are compared in table 5 below. 5 Table 5

    These results demonstrate that the viscosification power of the polymers according to the invention 10 increases as the molar mass (and the intrinsic viscosity) increases and as the salinity increases.
    Direct dispersion The polymers of example 2, sintered by reverse emulsion polymerization with the composition AM / SPP 15 (90/10), are dispersed directly in the brines. 5% by weight of Soprophor 4D384 surfactant (Rhodia) are added to the reverse emulsion 5 minutes before mixing with the brines. The amount needed to obtain 10 g / l of polymer is dispersed in the brines. These preparations are, in the first stage, shaken vigorously by hand for a few moments and then shaken with a magnetic bar until used.
    Relative viscosities at a polymer concentration of 10 g / l are measured here 24 h after sample preparation (gradient from 1 s-1 to 25 ° C) and the values are compared in table 6 below. Table 6

    These results demonstrate that the viscosification power of the polymers according to the invention is very high in brines highly concentrated in salt.
    High temperature stability Polymer solutions comprising varying levels of SPP are prepared according to the protocol described in example 2 at a weight concentration of 0.5% in the ZnBr2 / CaBr2 brine.
    The viscosities of these solutions are measured after mixing at room temperature and then after aging in pressurized cells (acid digestion pumps - Parr instruments) in a rolling oven at 160 ° C for 6 h.
    Aged solutions may have solid residues; if appropriate, these solutions are filtered through a 100 μm cloth. The viscosities are then measured at 90 ° C and the values are compared in table 7 below. Table 7
    These results demonstrate that the high temperature stability of the polymers according to the invention dissolved in brines is directly related to the level of SPP incorporated in the polymer. In this case, a minimum level of 10 mol% is necessary to maintain the homogeneity of the solution if the latter is exposed for a long time to elevated temperatures. Example 4 - optimization of polymer-surfactant ratio:
    A surfactant, SOPROPHOR 4 D 384, made by Rhodia, was first dissolved in the polymer of example 2-5 (polymer concentration of 30% by weight) above, in varying concentrations - 2% to 5% in total volume. Next, 40 gpt of each mixture was tested in HyCal II (14.2 ppg CaBr2), NoCal II (11.0 - 12.5 ppg NaBr) and HyCal III (19.2 ppg ZnBr2). The polymer / surfactant mixture was added to the different pickles and allowed to hydrate for 15 minutes at a constant shear rate of approximately 700 RPM using a standard servodyne mixer. After that, the samples were tested at 200 ° F using a Chandler 5550 viscometer. From the data obtained, it was determined that the 5% surfactant concentration was optimal. The optimal concentration was also confirmed to be 5% surfactant concentration after testing with 50 gpt of polymer load with 4 and 5% surfactant concentration. See figures 1-3. Example 5
    The 5% polymer / surfactant mixture of example 4 was then tested at various temperatures (150 ° F - 350 ° F) (65.6 ° C - 176.7 ° C) on loads of 40 gpt to 50 gpt with all the three pickles (HyCal II (14.2 ppg CaBr2), NoCal II (11.0 - 12.5 ppg NaBr), and HyCal III (19.2 ppg ZnBr2)). The polymer mixture was added to the various brines and allowed to hydrate for 15 minutes. The samples were then tested at different temperatures using a Chandler 5550 viscometer. The resulting data for HyCal II, NoCal II and HyCal III are shown in Figures 4, 5 and 6 respectively. From the data it was determined that the brine viscometer is stable up to approximately 350 ° F for 1 hour. All other temperatures showed stability for 3 hours. The data show that good viscosities were obtained at various temperatures for all three brines. Example 6 - analysis of produced water
    Samples of water produced from the Bakken formation and Marcellus formation were analyzed using API 45 Recommended practice available from the American Petroleum Institute. The results are shown in table 8 below. Table 8


    The water analysis above indicates very high amounts of dissolved solids and total hardness for the Bakken and Marcellus produced water samples. The water was filtered through a Whatman no paper filter. 42. The filtered Bakken and Marcellus water was used in the examples below. Example 7
    Apparent viscosity test was performed at room temperature using an OFITE M900 viscometer for both Bakken and Marcellus water. The order of addition of the ingredients Rhodapex CD-1281 and BVP-1 during mixing was tested for effect on apparent viscosity. The results are shown in figures 1 and 2. The test for figure 1 included the following compositions, with ingredients listed in the mixing order: 7A. 9.9 ppg of water Bakken 4 gpt Rhodapex CD-1281 50 gpt BVP-1 7B. 9.9 ppg of water Bakken 50 gpt BVP-1 4 gpt Rhodapex CD-1281 7C. 9.9 ppg Bakken water 50 gpt BVP-1 The test for figure 2 included the following compositions, with ingredients listed in order of mixing: 7D. 9.9 ppg of water Marcellus 6 gpt Rhodapex CD-1281 50 gpt BVP-1 7E. 9.9 ppg of water Marcellus 50 gpt BVP-1 6 gpt Rhodapex CD-1281 7F. 9.9 ppg water Marcellus 50 gpt BVP-1
    The results showed that using Rhodapex CD-1281 and BVP-1 combined provided a significant increase in apparent viscosity at room temperature when compared to the use of BVP-1 individually. The results also showed when when using Bakken or Marcellus water, the addition of BVP-1 before the addition of Rhodapex CD-1281 provided a marginal increase in apparent viscosity when compared to the same composition in which Rhodapex CD1281 was added before BVP -1. Examples 8 and 9
    All fluids in the examples below were prepared by the following procedure: 250 ml of produced water was added to a 16-ounce jar. The jar was placed under a stirrer suspended at 1000 rpm. After vortexing, the BVP-1 brine viscosifier concentration was added. Then the Rhodopex CD-1281 surfactant was added. Finally, a rupture agent was added if necessary. The resulting composition was mixed for 1 minute and then removed from the suspended stirrer for testing. The test was performed using an OFITE M900 viscometer for measurements at room temperature. A Chandler 5550 HPHT viscometer was used for measurements at elevated temperature.
    Example 8: fluid in Bakken produced water at 43/44 elevated temperatures The following example well maintenance and repair fluid compositions were prepared using Bakken produced water. 8A. Bakken water produced 60 gpt BVP-1 6 gpt Rhodapex CD-1281 8B. Bakken water produced 50 gpt BVP-1 8 gpt Rhodapex CD-1281 8C. Bakken water produced 40 gpt BVP-1 8 gpt Rhodapex CD-1281
    The compositions of examples 8A, 8B and 8C were heated to 200 ° F (93.3 ° C) and 250 ° F (121.1 ° C). as shown in the figures, various amounts of GBB-1 oxidizing rupture agent, available from BJ Services Company, have also been added to these compositions. Apparent viscosity data was then measured using a Chandler 5550 viscometer at a shear rate of 100 s-1.
    The results at 200 ° F (93.3 ° C) for compositions 8A to 8C are respectively shown in figures 3-5. The results at 250 ° F (121.1 ° C) for compositions 8A to 8C are respectively shown in figures 6-8. The results indicate that the viscosity at temperature can be controlled by varying the amounts of BVP-1 and Rhodapex CD-1281. In addition, the viscosity can be disrupted (reduced) in a controlled manner by varying the amount of disrupting agent added to the compositions. Example 9: fluid in water produced by Marcellus at elevated temperatures
    The following sample well maintenance and repair fluid compositions were prepared using Marcellus produced water. 9. water produced Marcellus 50 gpt BVP-1 6 gpt Rhodapex CD-1281
    As shown in figure 9, varying amounts of GBW-7 oxidation disrupting agent, available from BJ Services Company, have been added to these compositions. The fluid in these compositions was heated to 150 ° F (65.6 ° C). the apparent viscosity data was then measured using a Chandler 5550 viscometer at a shear rate of 100 s-1. The results are shown in figure 10. The results indicate that the fluid has good viscosity at temperature. In addition, viscosity can be disrupted (reduced) in a controlled manner by varying the amount of disrupting agent added to the fluid.
    Although various modalities have been shown and described, the present disclosure is not limited in this way and will be understood to include all such modifications and variations as would be evident to a person skilled in the art.
    权利要求:
    Claims (15)
    [0001]
    1. Method of obtaining well hole maintenance and repair fluid characterized by comprising: obtaining produced water that contains a total dissolved solids content of at least 50,000 mg / L from a hydrocarbon well formation and then , thicken the water produced by mixing (i) 0.01% to 20% by weight of a zwitterionic polymer prepared by reverse emulsion polymerization of at least one Ab monomer comprising a betaine group and optionally one or more nonionic monomers Ba , (ii) 0.05% to 2% by volume of a surfactant chosen from ammonium C4-C12 alkyl ether sulphates, ammonium C4-C12 alkyl ether sulphonates and ammonium C4-C12 alkyl ether phosphates , providing up to 20% by weight of surfactant relative to the polymer, and (iii) 50% by weight or more of water produced to form a well maintenance and repair fluid, and introducing the well maintenance and repair fluid into a well. hydrocarbon well.
    [0002]
    2. Method according to claim 1, characterized by the fact that the surfactant is an ammonium C4-C10 alkyl ether sulfate.
    [0003]
    3. Method according to claim 1, characterized by the fact that the surfactant is an ammonium C8-C10 alkyl ether sulfate.
    [0004]
    Method according to any one of claims 1 to 3, characterized in that the well maintenance fluid comprises 0.1% to 10% by weight of a zwitterionic polymer, 0.2% to 0.8% in volume of surfactant providing 5% to 15% of the surfactant in relation to the polymer, and 75% by weight or more of water produced.
    [0005]
    Method according to any one of claims 1 to 4, characterized by the fact that the zwitterionic polymer has an intrinsic viscosity of 600 or greater, in which the intrinsic viscosity is obtained by linear extrapolation of the reduced specific viscosity to zero concentration of the polymer, being measured by dissolving the polymer in a 20% by weight aqueous NaCl solution.
    [0006]
    Method according to any one of claims 1 to 5, characterized in that the at least one monomer Ab is chosen from sulfobetaines and phosphobetaines; or the fact that the at least one Ab monomer is a substituted or unsubstituted compound chosen from dialkyl ammonioalkyl acrylate alkyl phosphonates, dialkylammonioalkyl methacrylate alkyl phosphonates, dialkylammonioalkyl alkyl phosphonates, dialkyl alkyl alkyl phosphonates, dialkyl alkyl alkyl phosphates acrylates dialquilamonioalquila, alkyl sulfonates methacrylates dialquilamonioalquila, alkylsulfonates acrylamides dialquilamonioalquila, alkylsulfonates methacrylamides of amonioalquila dialkyl alkyl phosphonates acrylates dialquilamonioalcoxialquila, alkylphosphonates methacrylates of amonioalcoxialquila dialkyl, alkylphosphonates of acrylamide dialquilamonioalcoxialquila, alkylphosphonates of methacrylamides of dialquilamonioalcoxialquila , alkyl sulfonates of dialkyl ammonioalkoxyalkyl acrylates, alkyl sulfonates of dialkylammonioalkoxyalkyl methacrylates, alkyl sulfonates of acrylamides of dialquilamonioalcoxi alkyl, alkylsulfonates methacrylamides of dialquilamonioalcoxialquila, monomers heterocyclic betaine, alkylphosphonates of dialquilamonioalquilalílicos, alkylsulfonates dialquilamonioalquilalílicos, alkylphosphonates of dialquilamonioalquilestirenos, alkylsulfonates dialquilamonioalaquilestirenos, betaines resulting from ethylenically unsaturated anhydrides and dienes, preferably in that the at least one monomer Ab is a heterocyclic betaine chosen from sulfobetaines derived from piperazine, sulfobetaines derived from pyridines substituted by vinyl and sulfobetaines derived from imidazois; or the fact that at least one monomer Ab is chosen from the compounds of formulas 10, 11, 12, 13, 18, 19, 20, 21, 22 and 23:
    [0007]
    Method according to any one of claims 1 to 6, characterized by the fact that during polymerization, the monomer Ba is a hydrophilic monomer.
    [0008]
    Method according to any one of claims 1 to 7, characterized in that the zwitterionic polymer is prepared by reverse emulsion polymerization of at least one Ab monomer and one or more non-ionic monomers Ba, in which one or more nonionic monomers Ba is chosen from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxylpropyl methacrylate, glycerol monomethacrylate, acrylamide, methacrylamide, N-methylolacrylamide, dimethylacrylamide, polyethylene oxide, polyethylene oxide, polyethylene oxide, dimethylacrylate polypropylene / polyethylene, α-methacrylates, vinyl alcohol or vinyl pyrrolidone, preferably due to the fact that at least one Ab monomer is chosen from sulfopropyl dimethyl ammonioethyl methacrylate and sulfopropyl dimethylammonium propyl methacrylamide and one or more nonionic monomers Ba is acrylamide.
    [0009]
    Method according to any one of claims 1 to 8, characterized in that the inversion emulsion polymerization comprises: preparing an inverse emulsion comprising at least one monomer Ab and one or more nonionic monomers Ba in one aqueous phase dispersed in the form of droplets in a hydrophobic external phase of an inverse emulsion, preferably by mixing at least one emulsifying agent, at least one Ab monomer, one or more non-ionic monomers Ba, the aqueous phase and the external phase hydrophobic; and after preparing the reverse emulsion, form the zwitterionic polymer by polymerizing at least one Ab monomer and one or more nonionic Ba monomers.
    [0010]
    Method according to any one of claims 1 to 9, characterized in that the polymer is in the form of an aqueous composition comprising the reverse emulsion with an aqueous phase comprising the polymer dispersed in the form of droplets in an external hydrophobic phase and other ingredients chosen from a surfactant, an organic salt, an inorganic salt, a detergent and a thickener, preferably because the aqueous composition is a saline composition comprising at least 25 g / l of a salt.
    [0011]
    11. Method according to any one of claims 1 to 10, characterized by the fact that the fluid is used to fracture the well.
    [0012]
    12. Method according to any one of claims 1 to 11, characterized by the fact that the fluid is used simultaneously with the drilling of the well.
    [0013]
    13. Method according to any one of claims 1 to 12, characterized in that the fluid further comprises gravel, the fluid causing the gravel to be stored in the well.
    [0014]
    14. Method according to any one of claims 1 to 13, characterized in that the water comprises a total dissolved solids content ranging from 100,000 mg / L to 300,000 mg / L.
    [0015]
    Method according to any one of claims 1 to 14, characterized in that it further comprises mixing the fluid comprising the zwitterionic and surfactant polymer for 2 minutes or less before introducing the fluid into the hydrocarbon well.
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    同族专利:
    公开号 | 公开日
    CN103221505B|2016-05-11|
    EP2455441B1|2018-12-26|
    EP2455441A1|2012-05-23|
    CA2812850A1|2012-05-24|
    US8183181B1|2012-05-22|
    PL2455441T3|2019-09-30|
    AU2011329089A1|2013-04-18|
    CA2812850C|2015-02-03|
    CN103221505A|2013-07-24|
    MX2013004418A|2013-07-17|
    BR112013012457A2|2016-08-30|
    RU2013127675A|2014-12-27|
    AR083917A1|2013-04-10|
    WO2012068080A1|2012-05-24|
    HUE042642T2|2019-07-29|
    US20120129738A1|2012-05-24|
    CO6690802A2|2013-06-17|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-08| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-06-02| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-03-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-03-30| 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 15/11/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US12/950,756|US8183181B1|2010-11-19|2010-11-19|Oil field treatment fluids comprising zwitterionic betaine-group-containing polymers|
    US12/950,756|2010-11-19|
    PCT/US2011/060748|WO2012068080A1|2010-11-19|2011-11-15|Oil field treatment fluids|
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