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WO2021175757A1 - Procédé de fabrication d'un prémélange de polyacrylamide aqueux - Google Patents

Procédé de fabrication d'un prémélange de polyacrylamide aqueux Download PDF

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Publication number
WO2021175757A1
WO2021175757A1 PCT/EP2021/054990 EP2021054990W WO2021175757A1 WO 2021175757 A1 WO2021175757 A1 WO 2021175757A1 EP 2021054990 W EP2021054990 W EP 2021054990W WO 2021175757 A1 WO2021175757 A1 WO 2021175757A1
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Prior art keywords
premix
aqueous
polyacrylamide
polyacrylamides
weight
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Inventor
Daniel Barrera-Medrano
Faissal-Ali El-Toufaili
Anna-Corina SCHMIDT
Jack F TINSLEY
Brent Busby
Dennis Loesch
Markus OSTERMAYR
Tobias Joachim Zimmermann
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/66—Compositions based on water or polar solvents
    • C09K8/68—Compositions based on water or polar solvents containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/54—Aqueous solutions or dispersions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/28—Friction or drag reducing additives

Definitions

  • the present invention relates to a method of manufacturing an aqueous polyacrylamide premix, wherein the aqueous polyacrylamide premix is prepared by mixing a polyacrylamide inverse emulsion or a liquid dispersion polymer comprising polyacrylamides with an aqueous fluid thereby obtaining an aqueous premix comprising at least water, an organic hydrophobic liquid and polyacrylamides, wherein the polyacrylamide concentration is from 2 to 19.9 % by weight and allowing the aqueous premix to ripen for a certain time.
  • the invention furthermore relates to the use of such an aqueous premix for various applications, in particular for hydraulic fracturing and enhanced oil recovery.
  • a fracturing fluid is injected into the well at a pressure sufficient to penetrate into the subterranean formation and to generate new fractures or fissures in the subterranean formation and/or to extend existing fractures of fissures thereby enhancing its permeability.
  • a fracturing fluid usually comprises so-called proppants.
  • Proppants are small hard particles, typically having dimensions in the range from 0.1 mm to 2.5 mm, such as for example, naturally-occurring sand grains which are deposited in the fractures by the fracturing fluid and remain in the created fractures after the fluid is removed, thereby keeping the fractures open and allowing hydrocarbons to flow more easily from the formation to the production wellbore.
  • proppants such as sand particles
  • the suspension of the proppants in the fracturing fluid and the transport by the fluid requires particular attention. It is necessary to avoid that proppants settle in course of transport, for example in the wellbore or in pipe which transport the fracturing fluid.
  • two different techniques are known in the art for avoiding such settlement of proppants.
  • One method comprises increasing the viscosity of the fluid using a suitable viscosifier, such as guar gum.
  • Another method comprises flowing the fluid at very high speed.
  • the latter method also known as slickwater fracturing, is often preferred, but the high speeds employed create turbulent flow with excessive pumping pressure. Necessary pressures often are too high for the field equipment and the net effect is that the required flow rate is not achieved. For example, typical injection rates for slickwater hydraulic fracturing can reach about 15 m 3 per minute, but turbulence can restrict it to 1,5 m 3 per minute.
  • friction reducers that dampen the turbulent eddies, creating pressure drops approaching those of laminar flow.
  • friction reducers comprise high molecular weight polymers, for example high molecular weight polyacrylamides.
  • Such polyacrylamide friction reducers may be applied in various kinds, for instance as powders or as diluted aqueous solutions.
  • polyacrylamides for use as friction reducer as inverse emulsion
  • Inverse emulsions of polyacrylamides for used as friction reducer are commercially available.
  • a discontinuous aqueous phase comprising water-soluble polymers such as polyacrylamides is dispersed a continuous organic phase not miscible with the aqueous phase.
  • the inverse emulsions comprise suitable surfactants which stabilize the aqueous droplets in the continuous organic phase.
  • Liquid Dispersion Polymers also abbreviated as LDP and usually their water contents is less than 5 wt. %.
  • the polymer contents of LDPs may be up to more than 50 wt. %.
  • Liquid dispersion polymers and their manufacture are disclosed for example in DE 24 19764 A1, US 4,052,353, US 4,528,321, US 6,365,656 B1, or US 6,833,406 B1.
  • US 2014/0131039 A1 discloses the use of such liquid dispersion polymers for mineral oil production.
  • the inverse emulsion may be metered into a flowing aqueous fluid in which it is intended to act as friction reducer, for example into a flowing aqueous fracturing fluid.
  • the inverse emulsion needs to become inverted so that the polyacrylamide friction reducers can become released from the discontinuous aqueous phase.
  • Said step is typically carried out by adding so-called “inverting surfactants”.
  • inverting surfactants enable conversion or at least speed up the step of inversion.
  • Liquid dispersion polymers may be used as friction reducer basically in the same manner.
  • Such a process of inverting inverse emulsions or liquid dispersion polymers may be a 1-step process. It is also known in the art to apply 2-step processes or multi-step processes to invert such inverse emulsions or liquid dispersion polymers.
  • US 2011/0118153 A1 discloses an enhanced oil recovery method in which an aqueous solution of polyacrylamides is used as flooding medium.
  • the method comprises mixing an inverse emulsion of polyacrylamides with water.
  • an apparatus comprising two static mixers is used, one of them mounted in the main injection line and one of them in a bypass to the main injection line.
  • the method comprises pre-diluting an inverse emulsion with water in the first static mixer mounted on said bypass of the main injection water line, thereby obtaining a mixture comprising at least 0.5 % by weight of polyacrylamides, preferably from 0.5 % by weight to 2 % by weight, and diluting the mixture obtained with additional water in the second static mixer mounted on the main water injection circuit, thereby obtaining a diluted mixture for injection having a polyacrylamide concentration from 0.05 % by weight to 0.3 % by weight.
  • the mixing process is a quick process:
  • the overall residence time in the apparatus described above is from about 2 s to 10 s.
  • US 2014/0131039 A1 discloses an enhanced oil recovery method wherein the injection fluid comprising at least water and a polyacrylamide is made by mixing a liquid dispersion polymer with water. Mixing may be carried out in a 2-step process comprising a pre-dilution step thereby obtaining a polyacrylamide concentrate and thereafter further diluting the concentrate with additional water in a second step. Static mixers may be used for mixing.
  • the concentrate obtained from pre-dilution may have a concentration from 0.51 % by weight to 5 % by weight of polyacrylamides.
  • US 2017/0158948 A1 discloses a method of preparing an inverted polymer solution for use as friction reducer in hydraulic fracturing comprising providing a liquid polymer solution and inverting it in an aqueous fluid, thereby obtaining an inverted polymer solution having a concentration from 0.005 % by weight to 1.5 % by weight of (co)polymer such polymer.
  • the inversion may be a one-step process but also a multi-step process.
  • a concentrate having a concentration of up to 1.5 % by weight of polymer for example from 0.5 to 1.5 % by weight may be formed, which is further diluted with additional liquid second step.
  • the document also discloses a process of fracturing in which such an inverted polymer solution is used as friction reducer.
  • US 2019/0002754 A1 discloses a method for hydrogen recovery which comprises preparing an inverted polymer solution, e.g. an inverted polyacrylamide solution from a liquid polymer or an inverse polymer emulsion by mixing it with an aqueous liquid.
  • the inversion may be a 2-step process, wherein in the first step a concentrate having a concentration of up to 1.5 % by weight of polymer, for example from 0.5 to 1.5 % by weight is be formed, which is further diluted with additional liquid second step.
  • WO 2017/187150 A1 discloses a formulation for use in a fracturing fluid comprising a fluid comprising an oil phase and particles of a water-soluble polymer.
  • the fluid comprising an oil phase preferably is an inverse emulsion.
  • the formulation preferably is an inverse emulsion in which additionally particles of a water-soluble polymer are dispersed.
  • the document does not disclose ripening a mixture of the formulation and water before use. There is still a need for improving the performance of friction reducers in slickwater fracturing processes.
  • the present invention relates to a method of manufacturing an aqueous polyacrylamide premix (P) comprising at least the following steps:
  • composition (C) comprising at least 20 % by weight of polyacrylamides, relating to the total of all components of the composition, wherein the composition (C) is selected from
  • a water-in-oil emulsion comprising at least an oil phase comprising an organic, hydrophobic liquid and an aqueous phase comprising polyacrylamides
  • a liquid dispersion polymer composition (C-l I) comprising an organic, hydrophobic liquid and particles of polyacrylamides dispersed therein, wherein the amount of water in the composition is less than 10 % by weight, relating to the total of all components of the composition (C-ll),
  • an aqueous polyacrylamide premix (P) comprising at least water, an organic hydrophobic liquid and polyacrylamides, wherein the concentration of polyacrylamides in the premix (P) is from 2 % to 19.9 % by weight, relating to the total of all components of the premix (P),
  • step (3) allowing the aqueous polyacrylamide premix (P) to ripen by allowing the components of the aqueous premix (P) to interact with each other for a period of time after the components have been mixed in step (2), wherein the time period is at least 1 min.
  • the aqueous polyacrylamide premix (P) comprises at least on polyacrylamide. It may of course comprise a mixture of two or more different polyacrylamides. Polvacrylamides
  • polyacrylamides as used herein means water-soluble homopolymers of acrylamide, or water-soluble copolymers comprising at least 10 mole %, preferably at least 20 mole %, and more preferably at least 30 mole % of acrylamide and at least one additional water-soluble, monoethylenically unsaturated monomer different from acrylamide, wherein the amounts relate to the total amount of all monomers in the polymer. Copolymers are preferred.
  • water-soluble monomers in the context of this invention means that the monomers are to be soluble in the aqueous monomer solution to be used for polymerization in the desired use concentration. It is thus not absolutely necessary that the monomers to be used are miscible with water without any gap; instead, it is sufficient if they meet the minimum requirement mentioned. It is to be noted that the presence of acrylamide in the monomer solution might enhance the solubility of other monomers as compared to water only. In general, the solubility of the water-soluble monomers in water at room temperature should be at least 50 g/l, preferably at least 100 g/l.
  • the kind and amount of water-soluble, monoethylenically unsaturated comonomers to be used besides acrylamide is not limited and depends on the desired properties of the polyacrylamide friction reducer to be used within the contact of the present invention.
  • comonomers may be selected from uncharged water- soluble, monoethylenically unsaturated monomers.
  • examples comprise methacrylamide, N- methyl(meth)acrylamide, N,N’-dimethyl(meth)acrylamide, N-methylol(meth)acrylamide or N- vinylpyrrolidone. Further examples have been mentioned in WO 2015/158517 A1 page 7, lines 9 to 14.
  • comonomers may be selected from water-soluble, monoethylenically unsaturated monomers comprising at least one acidic group, or salts thereof.
  • the acidic groups are preferably selected from the group of -COOH, -SO3H and -PO3H2 or salts thereof. Preference is given to monomers comprising COOH groups and/or -SO3H groups or salts thereof.
  • Suitable counterions include earth alkaline metal ions such as Ca 2+ ions, especially alkali metal ions such as Li + , Na + or K + , and also ammonium ions such as NH 4 + or ammonium ions having organic radicals.
  • ammonium ions having organic radicals include [NH(CH 3 )3] + , [NH 2 (CH 3 )2] + , [NH 3 (CH 3 )] + , [NH(C 2 H 5 )3] + , [NH 2 (C 2 H 5 )2] + , [NH 3 (C 2 H 5 )] + , [NH 3 (CH 2 CH 2 OH)] + , [H3N-CH2CH2-NH3P or [H(H 3 C) 2 N- CH2CH2CH2NH3P.
  • Examples of monomers comprising -COOH groups include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid or salts thereof. Preference is given to acrylic acid or salts thereof.
  • Examples of monomers comprising -SO 3 H groups or salts thereof include vinylsulfonic acid, allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (ATBS), 2-methacrylamido-2- methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid, 3-acrylamido-3- methylbutanesulfonic acid or 2-acrylamido-2,4,4-trimethylpentanesulfonic acid. Preference is given to 2-acrylamido-2-methylpropanesulfonic acid (ATBS) or salts thereof.
  • ATBS 2-acrylamido-2-methylpropanesulfonic acid
  • Examples of monomers comprising -PO 3 H 2 groups or salts thereof include vinylphosphonic acid, allylphosphonic acid, N-(meth)acrylamidoalkylphosphonic acids or (meth)acryloyloxyalkylphosphonic acids, preferably vinylphosphonic acid.
  • Preferred monomers comprising acidic groups comprise acrylic acid and/or ATBS or salts thereof.
  • comonomers may be selected from water-soluble, monoethylenically unsaturated monomers comprising cationic groups.
  • comonomers may be selected from associative monomers.
  • Associative monomers impart hydrophobically associating properties to polyacrylamides.
  • Associative monomers to be used in the context of this invention are water-soluble, monoethylenically unsaturated monomers having at least one hydrophilic group and at least one, preferably terminal, hydrophobic group. Examples of associative monomers have been described for example in WO 2010/133527, WO 2012/069478, WO 2015/086468 or WO 2015/158517.
  • “Hydrophobically associating copolymers” are understood by a person skilled in the art to mean water-soluble copolymers which, as well as hydrophilic units (in a sufficient amount to assure water solubility), have hydrophobic groups in lateral or terminal positions.
  • the hydrophobic groups can associate with one another. Because of this associative interaction, there is an increase in the viscosity of the aqueous polymer solution compared to a polymer of the same kind that merely does not have any associative groups.
  • the hydrophilic linking group R 2 may be a group comprising quaternary ammonium groups.
  • R 3a is an aliphatic and/or aromatic, straight-chain or branched hydrocarbyl radical having 8 to 40 carbon atoms, preferably 12 to 32 carbon atoms.
  • groups include n-octyl, n- decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl groups.
  • the groups are aromatic groups, especially substituted phenyl radicals, especially distyrylphenyl groups and/or tristyrylphenyl groups.
  • n is a natural number from 2 to 6, for example 4
  • x is a number from 10 to 50, preferably from 12 to 40, and for example, from 20 to 30
  • y is a number from 5 to 30, preferably 8 to 25.
  • z is a number from 0 to 5, for example 1 to 4, i.e. the terminal block of ethylene oxide units is thus merely optionally present.
  • it is possible to use at least two monomers (V), wherein the R 1 and R 6 radicals and indices n, x and y are each the same, but in one of the monomers z 0 while z > 0 in the other, preferably 1 to 4.
  • the associative monomers are cationic monomers.
  • cationic associative monomers have been disclosed in WO 2015/158517 A1, page 11, line 20 to page 12, lines 14 to 42.
  • water-soluble monoethylenically unsaturated monomers also water-soluble, ethylenically unsaturated monomers having more than one ethylenic group may be used.
  • Monomers of this kind can be used in special cases in order to achieve easy crosslinking of the acrylamide polymers.
  • the amount thereof should generally not exceed 2 mole %, preferably 1 mole % and especially 0.5 mole %, based on the sum total of all the monomers. More preferably, the monomers to be used in the present invention are only monoethylenically unsaturated monomers.
  • compositions for use in the process of slickwater fracturing according to the present invention may be selected by the skilled artisan according to his/her needs.
  • Preferred polyacrylamides comprise, besides at least 10 mole % of acrylamide, at least one comonomer, preferably at least one comonomer selected from the group anionic comonomers, cationic comonomers or associative comonomers as described above.
  • such preferred polyacrylamides comprise at least one comonomer selected from the group of acrylic acid or salts thereof, ATBS or salts thereof, associative monomers, in particular those of formula (V) or DMA3Q, more preferably at least one comonomer selected from acrylic acid or salts thereof, ATBS or salts thereof, associative monomers, in particular those of formula (V).
  • the polyacrylamides comprise 20 mole % to 95 mole % of acrylamide and 5 mole % to 80 mole % of acrylic acid and/or salts thereof, wherein the amounts of the monomers relate to the total of all monomers in the polymer.
  • the polyacrylamides comprise 70 mole % to 95 mole % of acrylamide and 5 mole % to 30 mole % of acrylic acid and/or salts thereof. In one embodiment, the polyacrylamides comprise 40 mole % to 90 mole % of acrylamide, 5 mole % to 30 mole % of acrylic acid and/or salts thereof, and 5 mole % to 30 mole % of ATBS and/or salts thereof.
  • the polyacrylamides comprise 69 mole % to 94.995 mole % of acrylamide, 0.005 mole % to 1 mole % of at least one associative monomer of the general formula (V) mentioned above, including the preferred embodiments, and 5 mole % to 30 mole % of acrylic acid or salts thereof.
  • the polyacrylamides comprise 70 mole % to 99 mole% of acrylamide and 1 mole % to 30 mole % of a cationic comonomer, preferably DMA3Q.
  • the polyacrylamides comprise 69 mole % to 99.995 mole % of acrylamide, 0.005 mole % to 1 mole % of at least one associative monomer, and 0 mole % to 30 mole % of an anionic monomer, for example ATBS or a cationic monomer, for example DM3AQ.
  • the associative monomer(s) have the general formula (V) including the preferred embodiments mentioned above.
  • the amount of the monomers relates to the total of all monomers in the polyacrylamide.
  • Further water-soluble, monoethylenically unsaturated monomers may be present besides those specifically mentioned, however, the embodiments each include also one embodiment in which besides the monomers specifically mentioned no further monomers are present, i.e. in these embodiments the total amount of the monomers specifically mentioned is 100 mole %.
  • the intrinsic viscosity of the polyacrylamides to be used in the process of slickwater fracturing may be selected by the skilled artisan according to his/her needs. In general, for use as friction reducer, higher intrinsic viscosities are advantageous. In one embodiment of the invention, the intrinsic viscosity may be at least 17 deciliter/gram (dl_/g), in particular 19 dL/g to 28 dl_/g.
  • the method of manufacturing an aqueous polyacrylamide premix (P) according to the present invention comprises at least three steps (1), (2), and (3). Of course, the process may also comprise further steps.
  • Step (1) comprises providing a composition (C) comprising at least 20 % by weight, preferably at least 25 % by wt. of polyacrylamides, relating to the total of all components of the composition, wherein the composition (C) is selected from
  • a water-in-oil emulsion comprising at least an oil phase comprising an organic hydrophobic liquid and an aqueous phase comprising polyacrylamides
  • a liquid dispersion polymer composition (C-l I) comprising an organic, hydrophobic liquid and particles of polyacrylamides dispersed therein, wherein the amount of water in the composition is less than 10 % by weight, relating to the total of all components of the composition (C-ll).
  • compositions (C-l) or compositions (C-ll) are used, however, in exceptional cases also both compositions (C-1) and (C-ll) may be used together.
  • a composition (C-l) is used.
  • composition (C-l) Composition (C-l)
  • composition (C-l) is a water-in-oil-emulsion comprising an oil phase and an aqueous phase comprising at least one polyacrylamide.
  • Water-in-oil emulsions are also known as inverse emulsions.
  • the oil phase of the water-in-oil-emulsion comprises an organic hydrophobic liquid which usually has a boiling point of at least 100°C, preferably at least 150°C.
  • the organic hydrophobic liquid basically may be any kind of mineral oil.
  • aliphatic mineral oils with a content of aromatic hydrocarbons of less than 5 % by wt., preferably less than 1 % by wt. may be used.
  • the flash point of the mineral oil should be at least 70°C.
  • the aqueous phase comprises at least one polyacrylamide.
  • the emulsion is stabilized in known manner by suitable surfactants.
  • the manufacture of water-in- oil emulsions comprising polyacrylamides basically is known in the art and such emulsions are commercially available.
  • the water-in-oil-emulsion may additionally comprise additives for accelerating the inversion of the polyacrylamides into the aqueous solution after mixing the water-in-oil emulsion with water.
  • additives also known as activating surfactants or boosters are basically is known in the art.
  • Examples comprise nonionic surfactants, in particular polyalkoxylated alcohols, in particular polyalkoxylates of Cs to C22 alkohols.
  • the polyalkoxy groups preferably may be selected from ethoxy, propopxy or butoxy groups. In one embodiment, the polyalkoxy groups comprise at least ethoxy groups and optionally propoxy and/or butoxy groups.
  • surfactants based on oxo alcohols in particular based on C13/15 oxo alcohols and comprising 5 to 15 EO units and optionally PO and/or BuO with the proviso that the number of PO and/or BuO units is less than the number of EO units.
  • the amount of such additives may for example be from 1 % to 5 % by weight relating to total weight of the water-in-oil emulsion.
  • the amounts of the aqueous phase and the oil phase in the composition (C-l) may be selected by the skilled artisan according to his/he needs. In one embodiment, the amount of the oil phase may be from 25 to 40 % by weight and the amount of the aqueous phase (except the polymer) may be from 35 to 50 % by weight, relating to the total of all components of the composition (C-l).
  • the composition (C-l) comprises at least 20 % by weight of polyacrylamides relating to the total of all components of the composition (C-l), preferably at least 25 % by weight.
  • the composition (C-l) comprises from 20 to 45 % by weight of polyacrylamides, in particular from 25 to 45 % by weight, preferably from 25 to 40 % by weight and for example from 25 to 35 % by weight.
  • composition (C-ll) Composition (C-ll)
  • the composition (C-ll) is a liquid dispersion polymer composition comprising at least an organic, hydrophobic liquid which usually has a boiling point of at least 100°C, preferably at least 150°C and particles of polyacrylamides dispersed therein.
  • the composition may also comprise additionally small amounts of water, however, the amount of water in the composition is less than 10 % by weight, relating to the total of all components of the composition (C-ll), preferably less than 5% by weight.
  • the organic hydrophobic liquid basically may be any kind of mineral oil. Details about such mineral oils have already been disclosed in the paragraph about the compositions (C-l) above and we refer to said paragraph.
  • the particles of the polyacrylamides may an average particle size of 0.4 mhi to 5 mhi, preferably 0.5 mhi to 2 mhi.
  • Average particle size here means the d50 value of the particle size distribution (number average) which may be measured by the skilled artisan using known techniques for determining the particle size distribution.
  • Compositions (C-ll) may preferably be manufactured by inverse emulsion polymerization followed by removing water from the inverse emulsion until the amount of water is at least less than 10 % by weight.
  • the removal of water preferably is carried out at reduced pressure, for example at a pressure of 30 hPa to 500 hPa.
  • a suitable manufacturing procedure is for example disclosed in US 2014/0131039 A1. Liquid dispersion polymer compositions are commercially available.
  • compositions (C-ll) may be manufactured by dispersing dry powders of polyacrylamides in organic, hydrophobic liquids.
  • the dry powders should be ground to the desired particle size before use. In such products, typically no water is added additionally. Nevertheless, the obtained compositions (C-ll) may comprise small amounts of water because even “dry” polyacrylamide powders, especially if they are fine particles, typically comprise up to a few percent of water.
  • composition (C-ll) may comprise additives for accelerating inversion. Examples have already been mentioned above.
  • the composition (C-ll) comprises at least 20 % by weight of polyacrylamides relating to the total of all components of the composition (C-ll), preferably at least 25 % by weight.
  • the composition (C-l) comprises from 20 to 70 % by weight of polyacrylamides, in particular from 30 to 60 % by weight, preferably from 40 to 60 % by weight and for example from 45 to 55 % by weight.
  • step (2) at least one composition (C) is mixed with an aqueous liquid, thereby obtaining an aqueous polyacrylamide premix (P).
  • the premix (P) is a concentrate, in which the polyacrylamides usually not yet have the final concentration for use.
  • the aqueous premix (P) is further diluted although it is not absolutely ruled out to use the premix (P) as such.
  • Aqueous liquids comprise water. Besides water also small amounts of organic liquid miscible with water may be used, however, their extent should not exceed 20 wt. %, preferably not 10 wt. %. Preferably, no organic liquids are present. Water may be fresh water but also water comprising salts such as sea water or formation water or mixtures thereof may be used. In one embodiment of the invention, fresh water is used.
  • aqueous polyacrylamide premix (P) is a homogeneous mixture.
  • compositions (C-1) and (C-ll) comprise on organic, hydrophobic liquid
  • aqueous polyacrylamide premix (P) comprises an oil. So, the aqueous polyacrylamide premix (P) comprises at least water, an organic hydrophobic liquid and a polyacrylamide.
  • the concentration of polyacrylamides in the aqueous premix (P) is from 2 % to 19.9 % by weight, relating to the total of all components of the aqueous premix (P), in particular from 2 to 10 % by weight, preferably from 2 % to 8 % by weight and for example from 3 to 6 % by weight.
  • the amount of polyacrylamides in the aqueous premix (P) is from 2 % to 19.9 % by weight
  • the amount of water is from 50 to 96 % by weight
  • the amout of organic hydrophobic liquid is from 2 to 30 % by weight, in each case relating to the total of all components of the aqueous premix (P)
  • the amount of polyacrylamides in the aqueous premix (P) is from 2 % to 8 % by weight, the amount of water is from 80 to 96 % by weight, and the amout of organic hydrophobic liquid is from 2 to 12 % by weight, in each case relating to the total of all components of the aqueous premix (P),
  • the aqueous polyacrylamide premix (P) obtained in course of step (2) is allowed to ripen for at least 1 min.
  • the ripening time is at least 5 min, in other embodiments, it is at least 1 ⁇ 2 h.
  • the ripening step (3) increases the performance of the polyacrylamide as friction reducer in the method of fracturing.
  • the ripening time is from 1 min to 1 day, in particular from 5 min to 1 day, and for example from 5 min to 2 h. In other embodiments, the ripening time is from 1 ⁇ 2 to 1 day, for example from 1 ⁇ 2 h to 2 h.
  • ripening simply means, that the components of the aqueous premix (P) obtained in course of step (2) by mixing an aqueous liquid and the composition (C) are allowed to interact for an additional period of time after the components have been mixed with each other and before the premix is further processed, e.g. by further dilution.
  • step (3) is carried out by allowing the aqueous premix (P) to rest in a vessel.
  • the contents of the vessel is mixed for example by an internal stirrer and/or the contents of the vessel may be circulated through an external mixing circuit by means of a pump.
  • the external loop may comprise a static mixer.
  • the vessel for ripening the aqueous premix (P) may be the same vessel as used for mixing. In other embodiments ripening may be carried by pumping the aqueous premix (P) through a pipe which comprises static mixers.
  • steps (2) and (3) may be carried out on-site, i.e. at the site at which the ripened polyacrylamide premix (P) is used, for example at a well-site.
  • the premix (P) is filled into a transport unit after step (2) at a location A and the transport unit filled with the premix (P) is transported from said location A to a different location B, so that ripening of the premix (P) (step 3) happens in course of the transport.
  • Location B may be for example at an oil well to be fractured and location A may be a plant for making an aqueous polyacrylamide premix (P) as described above which serves a number of oil wells on an oilfield with aqueous polyacrylamide premix. Such a plant may be erected at a central location on an oilfield. Locations A and B may be -by the way of example- from 1 to 500 km, or from 10 km to 100 km apart from each other. In such a case, the ripening times correspond to the transport time and may also be a few days.
  • P aqueous polyacrylamide premix
  • the transport may be carried out by any transport means suitable for transporting the transport unit, for example by trucks, railcars or ships. In one embodiment, the transport is carried out by trucks.
  • step (2) may be carried out in a transportable mixing unit at a location A and the transportable mixing unit filled with the premix (P) is transported from location A to a different location B, so that ripening of the premix (P) (step 3) happens in course of the transport.
  • a tank fixed on a truck may be used.
  • the tank comprises an outlet opening at the rear end of the truck and for supporting removal of the contents the tank may be tilted.
  • the tank comprises an outlet opening at the bottom side of the tank.
  • the tank may comprise a conus at the bottom side of the tank and the outlet opening in located at the lower end of the conus.
  • the tank may be rotatable.
  • a concrete mixer may be used for transporting the concentrate.
  • step (2) is carried out at a location A and the aqueous premix (P) is transported in a pipeline to another location B, so that ripening of the premix (P) (step 3) happens in course of the pipeline transport.
  • aqueous polyacrylamide premix (P) manufactured according to the present invention may be used for various purposes, for example for mining applications, oilfield applications, water treatment, waste water cleanup, paper making or agricultural applications.
  • the aqueous polyacrylamide premix (P) may be further diluted at the site-of- use thereby obtaining diluted aqueous polyacrylamide solutions.
  • the aqueous polyacrylamide premix (P) advantageously may be used as such without further dilution.
  • the aqueous polyacrylamide premix (P) may also be formulated with further components. Further components may be selected by the skilled artisan according to the intended use. Oilfield applications
  • aqueous polyacrylamide premix (P) manufactured according to the present invention examples include enhanced oil recovery, oil well drilling, the use as viscosifier for various purposes or the use as friction reducers, for example friction reducers for fracturing fluids.
  • the aqueous polyacrylamide premix (P) manufactured according to the present invention may be used for enhanced oil recovery.
  • the present invention also relates to the use of an aqueous polyacrylamide premix (P) comprising at least water, an organic hydrophobic liquid and polyacrylamides, wherein the concentration of the polyacrylamides is from 2 to 19.9 % by weight, relating to the total of all components of the aqueous polyacrylamide premix (P) in a process of enhanced oil recovery, wherein the process comprises at least the following steps:
  • a homopolymer of acrylamide may be used, however preferably water-soluble copolymers comprising at least 10 %, preferably at least 20 %, and more preferably at least 30 % by weight of acrylamide and at least one additional water-soluble, monoethylenically unsaturated monomer different from acrylamide are used.
  • Suitable water- soluble comonomers have already been mentioned above and we refer to the disclosure above.
  • water-soluble comonomers may be selected from water-soluble, monoethylenically unsaturated monomers comprising at least one acid group, or salts thereof.
  • the acidic groups are preferably selected from the group of -COOH, -SO3H and -PO3H2 or salts thereof. Preference is given to monomers comprising COOH groups and/or -SO3H groups or salts thereof. Suitable counterions have already been mentioned above.
  • Examples of such comonomers comprise acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, vinylsulfonic acid, allylsulfonic acid, 2-acrylamido-2- methylpropanesulfonic acid (ATBS), 2-methacrylamido-2-methylpropane-sulfonic acid, 2- acrylamidobutanesulfonic acid, 3-acrylamido-3-methylbutane-sulfonic acid, 2-acrylamido- 2,4,4-trimethylpentanesulfonic acid, vinylphosphonic acid, allylphosphonic acid, N- (meth)acrylamidoalkylphosphonic acids and (meth)acryloyloxyalkyl-phosphonic acids.
  • ATBS 2-acrylamido-2- methylpropanesulfonic acid
  • 2-methacrylamido-2-methylpropane-sulfonic acid 2- acrylamidobutanesulfonic acid
  • acrylic acid and/or ATBS or salts thereof may be used as comonomers.
  • the amount of acrylamide usually is from 20 % by wt. to 90 % by wt. and the amount of acrylic acid and/or ATBS or salts thereof is from 10 % by wt. to 80 % by wt., relating to the amount of all monomers in the copolymer.
  • the amount of acrylamide is from 60 % by wt. to 80 % by wt. and the amount acrylic acid and/or ATBS or salts thereof is from 20 % by wt. to 40 % by wt..
  • the copolymers to be used for enhanced oil recovery comprise at least one water-soluble, monoethylenically unsaturated monomer comprising at least one acid group, or salts thereof, preferably acrylic acid and/or ATBS or salts thereof, and at least one associative monomer.
  • associative monomers have already been disclosed above.
  • at least one associative monomer of the general formula (III), (IV), or (V) is used, preferably at least one associative monomer of the general formula (V).
  • Preferred embodiments of the associative monomers (III), (IV), and (V) have already been disclosed above and it is explicitly referred to that description.
  • the amount of acrylamide usually is from 40 % by wt. to 89.9 % by wt.
  • the amount of acrylic acid and/or ATBS or salts thereof is from 10 % by wt. to 59.9 %
  • the amount of associative monomers is from 0.1 to 5 % by wt., relating to the amount of all monomers in the copolymer.
  • the polyacrylamides for EOR comprise 45 % to 55 % by weight of acrylamide, 0.1 to 5 %, preferably 0.1 to 2 % by weight of at least one associative monomer of the general formula (V) mentioned above, including the preferred embodiments, and 40 to 54.9 % by weight of acrylic acid or salts thereof.
  • At least one production well and at least one injection well are sunk into the mineral oil deposit.
  • a deposit will be provided with a plurality of injection wells and with a plurality of production wells.
  • An aqueous fluid is injected into the mineral oil deposit through the at least one injection well, and mineral oil is withdrawn from the deposit through at least one production well.
  • the polymer flood By virtue of the pressure generated by the aqueous fluid injected, called the “polymer flood”, the mineral oil flows in the direction of the production well and is produced through the production well.
  • the term “mineral oil” does not of course just mean a single-phase oil; instead, the term also encompasses the customary crude oil-water emulsions.
  • the aqueous injection fluid comprises an aqueous base fluid such as freshwater or water comprising salts, such as seawater or formation water.
  • the base fluid is mixed with the premix (P) and optionally further components.
  • further components include biocides, stabilizers, free-radical scavengers, initiators, surfactants, cosolvents, bases and complexing agents.
  • the aqueous polyacrylamide premix (P) may be used or the aqueous polyacrylamide premix (P) may be diluted in a first step with additional aqueous liquid and thereafter used for making the aqueous injection fluid.
  • the aqueous polyacrylamide premix (P) is mixed with the aqueous base fluid and optionally further components.
  • such mixing may be carried out by means of suitable mixing means, for example static mixers or mixing vessels.
  • the aqueous polyacrylamide premix (P) are injected into the pipeline(s) which transport(s) the aqueous injection fluid to the injection well(s) at the desired concentration.
  • Such pipelines may have a length of up to some kilometers. It has been found that the time needed for flowing through such pipeline often is sufficient for complete dissolution of the concentrate in the fluid.
  • the pipeline may comprise mixing elements such as static mixers.
  • the final concentration of the polyacrylamide in the injection fluid is fixed such that the aqueous formulation has the desired viscosity for the end use.
  • the viscosity of the formulation should generally be at least 5 mPas (measured at 25°C and a shear rate of 7 s _1 ), preferably at least 10 mPas.
  • the concentration of the polyacrylamides in the injection fluid is 0.02 % to 2 % by weight based on the total sum of all the components in the aqueous formulation.
  • the amount is preferably 0.05 % to 0.5% by weight, more preferably 0.1% to 0.3% by weight and, for example, 0.1 % to 0.2% by weight.
  • the aqueous polyacrylamide premix (P) may be used as such for the enhanced oil recovery process.
  • the premix (P) may have a concentration from 2.5 % by weight to 10 % by weight, preferably, the concentration is from 3.1 % by weight to 7 % by weight, and for example from 4 % by weight to 6 % by weight. Friction reducers for hydraulic fracturing
  • Hydraulic fracturing involves injecting fracturing fluid through a wellbore and into a formation under sufficiently high pressure to create fractures, thereby providing channels through which formation fluids such as oil, gas or water, can flow into the wellbore and thereafter be withdrawn.
  • Fracturing fluids are designed to enable the initiation or extension of fractures and the simultaneous transport of suspended proppant into the fracture to keep the fracture open when the pressure is released.
  • hydraulic fracturing operations it is important to ensure that the proppants are transported with the fracturing fluid into the formation and that they do not settle. Said effect can be achieved by using a thickened fluid having a high viscosity.
  • fluids having only a low viscosity are used. Such fluids mainly comprise water.
  • the pumping rates and the pressures used are significantly higher than for high-viscosity fluids. The high flow ensures proppant transport.
  • the turbulent flow of the fracking fluid causes significant energy loss due to friction.
  • friction reducers for example high molecular weight polyacrylamides may be used which change turbulent flow to laminar flow.
  • the aqueous polyacrylamide premix (P) manufactured according to the present invention is used as friction reducer in slickwater fracturing applications.
  • the present invention also relates to the use of aqueous polyacrylamide premix (P) as friction reducer in a process for fracturing subterranean formations comprising at least the following steps:
  • the aqueous base fluid may be freshwater or water comprising salts, such as seawater or formation water or produced water.
  • suitable proppants comprise naturally-occurring sand grains, resin-coated sand, sintered bauxite, glass beads or ultra-lightweight polymer beads.
  • Fracturing fluids may be mixed using so-called blenders (often mounted on trucks), in which an aqueous base fluid, proppants, friction reducers and optionally further components are mixed.
  • blenders often mounted on trucks
  • an aqueous base fluid, proppants, the aqueous polyacrylamide premix (P) as described above and optionally further components are mixed with each other by means of a customary blender thereby obtaining an aqueous fracturing fluid.
  • the concentration of proppants in the fracturing fluid may be constant in course of the fracturing process. In other embodiments, the concentration of proppants in the fracturing fluid may be varied in course of the fracturing process.
  • the slickwater fracturing process may start with injection of a certain amount of fracturing fluid which does not comprise any proppants and proppants are added to the fracturing fluid only at a later stage of the fracturing process.
  • the concentration of the polyacrylamide friction reducer in the aqueous fracturing fluid is selected by the skilled artisan according to his/her needs. Usually, it is in the range from 20 ppm to 1200 ppm, in particular from 20 ppm to 300 ppm, and for example from 125 ppm to 250 ppm of polyacrylamides relating to the total of all components of the aqueous fracturing fluid except the proppants. The amount of the aqueous polyacrylamide premix (P) for making the aqueous fracturing fluid is selected accordingly.
  • the aqueous polyacrylamide premix (P) manufactured by the method according to the present invention is used for applications in the field of mining, mineral processing and/or metallurgy.
  • the present invention relates to the use of an aqueous polyacrylamide premix (P) comprising at least water, an organic hydrophobic liquid and polyacrylamides, wherein the concentration of the polyacrylamides is from 2 to 19.9 % by weight, preferably from 2 % to 8 % by weight, relating to the total of all components of the aqueous polyacrylamide premix (P) for mining, mineral processing and/or metallurgy activities comprising the use for solid liquid separation, for tailings disposal, for polymer modified tailings deposition, for tailings management, as density and/or rheology modifier, as agglomeration aid, as binder and/or for material handling, wherein the aqueous polyacrylamide premix (P) is prepared by the method as described above.
  • the polyacrylamide premix (P) may comprise homopolymers of acrylamide or anionic, cationic or non-ionic copolymers. Suitable comonomers have already been described above.
  • Anionic copolymers of acrylamide can in particular be used for waste-water treatment in metallurgy like iron ore plants, steel plants, plants for electroplating, for coal washing or as flocculants.
  • Non-ionic polymers and/or copolymers of acrylamide can be used for example as non-ionic flocculants suitable as settlement aids in many different mineral processing applications and are particularly effective under very low pH conditions, as encountered for example in acidic leach operations.
  • the aqueous polyacrylamide premix (P) is used as flocculant in a process in which individual particles of a suspension form aggregates.
  • the polyacrylamide forms for example bridges between individual particles in the way that segments of the polymer chain adsorb on different particles and help particles to aggregate. Consequently, the polyacrylamides act as agglomeration aid, which may be a flocculant that carries active groups with a charge and which may counterbalance the charge of the individual particles of a suspension.
  • the polymeric flocculant may also adsorb on particles and may cause destabilization either by bridging or by charge neutralization.
  • the polymer in case the polymer is an anionic flocculant, it may react against a positively charged suspension (positive zeta potential) in presence of salts and metallic hydroxides as suspension particles, for example.
  • the polymer of the present invention is for example a cationic flocculant, it may react against a negatively charged suspension (negative zeta potential) like in presence of for example silica or organic substances as suspension particles.
  • the polymer obtained from the method of the present invention may be an anionic flocculant that agglomerates clays which are electronegative.
  • the aqueous polyacrylamide premix (P) is used in the Bayer process for alumina production.
  • the polyacrylamide can be used as flocculant in the first step of the Bayer-Process, where the aluminum ore (bauxite) is washed with NaOH and soluble sodium aluminate as well as red mud is obtained.
  • the flocculation of red mud is enhanced and a faster settling rate is achieved when acrylamide polymers and/or co-polymers are added.
  • polyacrylamide may be used for settling aluminum red mud slurries in alumina plants, provides high settling rates, offers better separation performance and reduces suspended solids significantly.
  • the liquor filtration operations are improved and with that the processing is made economically more efficient.
  • the polyacrylamides are used in decanters, in washers, for hydrate thickening, for green liquor filtration, as crystal growth modifiers, as thickener and/or as rheology modifier.
  • the aqueous polyacrylamide premix (P) is used in processes for solid liquid separation as for example flocculant or dewatering aid, which facilitate thickening, clarifying, filtration and centrifugation in order to enhance settling rates, to improve clarities and to reduce underflow volumes.
  • the polyacrylamide homo- or co-polymer of the present invention increase filtration rates and yields, as well as reducing cake moisture contents.
  • the aqueous polyacrylamide premix (P) is used for material handling and as binder.
  • the movement of large volumes of material is required for processing the rock and/or ores which have been extracted from the deposits.
  • the typical rock and/or ore processing for example starts with ore extraction, followed by crushing and grinding the ore, subsequent mineral processing (processing or the desired/valuable mineral material), then for example metal production and finally the disposal of waste material or tailings
  • the aqueous polyacrylamide premix (P) is used thickener, as density and/or rheology modifier, for tailings management.
  • the aqueous polyacrylamide premix can modify the behavior of the tailings for example by rheological adjustment.
  • the polyacrylamide polymers are able to rigidify tailings at the point of disposal by initiating instantaneous water release from the treated slurry. This accelerates the drying time of the tailings, results in a smaller tailings footprint and allows the released water to be returned to the process faster. This treatment is effective in improving tailings properties in industries producing alumina, nickel, gold, iron ore, mineral sands, oil sands or copper for example.
  • the aqueous polyacrylamide premix (P) is used for agglomeration of fine particulate matter and for the suppression of dust.
  • polyacrylamide polymers or copolymers are used as organic binders to agglomerate a wide variety of mineral substrates.
  • the polyacrylamide polymers or copolymers are used for iron ore pelletization as a full or partial replacement for bentonite.
  • the product from the method of the present invention can be used as binder, in particular as solid and liquid organic binders in briquetting, extrusion, pelletization, spheronization and/or granulation applications and gives for example excellent lubrication, molding and/or binding properties for processes such as coal-fines briquetting, carbon extrusion, graphite extrusion and/or nickel briquetting.
  • the method of the present invention and in particular the aqueous polyacrylamide premix (P) obtained by the method is used for the beneficiation of ores which comprise for example coal, copper, alumina, gold, silver, lead, zinc, phosphate, potassium, nickel, iron, manganese, or other minerals.
  • ores comprise for example coal, copper, alumina, gold, silver, lead, zinc, phosphate, potassium, nickel, iron, manganese, or other minerals.
  • the steps of preparing an aqueous premix (P) followed by ripening the aqueous premix (P) yields an improved performance as friction reducer as compared to a process without such a ripening step. Consequently, the amount of inverse emulsion or liquid dispersion polymer needed may be reduced without loss of performance, thereby yielding a more economic process.
  • Step 1 Preparation of a polyacrylamide inverse emulsion (IE)
  • a 600 ml_ beaker with magnetic stirrer, pH meter and thermometer was charged with 150.44 g of sodium acrylate (35% by weight in water), 128.97 g of distilled water, 229.65 g of acrylamide (52% by weight in water), 0.5 g of diethylenetriaminepentaacetic acid pentasodium salt (Trilon C; 5% by weight in water), and 0.86 g of the stabilizer sodium 2- mercaptobenzothiazole (Na-MBT; 50% by weight in water).
  • Trilon C diethylenetriaminepentaacetic acid pentasodium salt
  • Na-MBT stabilizer sodium 2- mercaptobenzothiazole
  • a high 1 L beaker was charged with 12.2 g sorbitan monooleate (Span® 80) and 189.9 g of a high-boiling dearomatized hydrocarbon mixture (Exxsol ® D100) was added and stirred with a spatula.
  • the beaker with the oil solution was fixed in a Silverson high shear mixer. While mixing the oil solution at 4000 rpm, the aqueous solution was poured in quickly. Then, the Silverson high shear mixer is turned up to 8000 rpm for 2 min 48 sec. The emulsion was transferred to a double jacketed reactor, stirred at 200 rpm and adjusted to the initiation temperature of 10 °C.
  • the initiators were added with a squeezing pump, controlled by hand. When the respective 0.1% solutions were empty, the initiators were changed to 9 g of a 1% sodium bisulfite solution and 5 g of a 1% t -butyl hydroperoxide solution. Thereby, the temperature rose 1 °C per minute up to 40 °C, from there the temperature was maintained at 40 °C. When the second initiator was added completely, the emulsion was stirred for additional 60 minutes at 40 °C. The emulsion was then filtered through a 190 pm filter prior to use.
  • the obtained mixture was allowed to ripen for 60 min. Ripening was carried out by continuing mixing at 300 rpm for 1 min. After 1 min, the mixing rate was lowered to 50 rpms for an additional 59 minutes, thereby obtaining an aqueous polyacrylamide premix comprising 2.5 % by weight of the polyacrylamide relating to the total of all components of the aqueous polyacrylamide premix.
  • the aqueous polyacrylamide premix was used in subsequent Friction Flow Loop testing immediately following the 60 minutes total ripening time.
  • the aqueous polyacrylamide premix was used in subsequent Friction Flow Loop testing immediately following the 1.0 minute total ripening time.
  • the friction reduction performance of the friction reducing agent was assessed using a Chandler model M5600 friction loop, which circulates fluid through a section of known diameter pipe to determine the effectiveness and longevity of a friction reducing agent added to a test fluid. Fluid in the loop flows from a -37.8 I ( ⁇ 10 gallon) reservoir through a pump, mass flow meter and then two - 250 cm (10 feet) long sections of pipe before returning to the reservoir to be recirculated. Pressure drop is measured over the two sections of pipe. One is 1.27 cm outer diameter (1/2 inch), the other is 1.91 cm outer diameter (3/4” inch), giving different ranges of Reynolds number.
  • the friction loop was loaded with 37.85 I (10 gallons) of aqueous test fluid (fresh water or brines).
  • the flow rate was set to 37.85 I per minute (10 gallons per minute) and once a stable, initial pressure was recorded. Thereafter, the friction reducing composition to be tested was injected, using a plastic syringe, into the vortex of the fluid reservoir, mixing at 600 rpms using an overhead mixer with a 2 inch 3-blade propeller.
  • the subsequent drop in pressure measured the performance of the friction reducing composition.
  • the pressure data from the 1.27 cm pipe is reported, because it reflected a higher Reynolds number than the 1.91 cm pipe.
  • the friction loop apparatus was charged with 10 gal (37.8 I) of fresh tap water. 3.78 ml of polyacrylamide inverse emulsion (equating to 25 ppm of polyacrylamide polymer once fully dispersed in the 10 gal (37.8 I) of aqueous fluid) was directly added to the reservoir undergoing agitation to disperse the inverse emulsion. At the same time the aqueous fluid containing the polyacrylamide friction reducer was circulated through the instrument while measuring differential pressure. The change in differential pressure was then recorded over time by the instrument’s software and reported as Friction Reduction (%). The results are shown in figure 1.
  • step 2 example 1 37.80 g of the aqueous polyacrylamide premix (2.3 wt. %) obtained in course of step 2 example 1 was injected into the reservoir via a syringe (equating to 25 ppm of polyacrylamide polymer once fully dispersed in the 10 gal (37.8 I) of aqueous fluid). The results are shown in figure 1.
  • Figure 1 shows the results of the three tests. It represents the Friction Reduction (%) as a function of time.
  • Example 3 represents the procedure according to the present invention. At first an aqueous premix (P) comprising 2.3 wt. % of polyacrylamides was prepared and thereafter allowed to ripen for 1 min. After 1 min of ripening, the aqueous premix (P) was injected into the friction loop in the same manner as described above. The friction reduction effect was about 77 % and it took less than one minute to reach at the number.
  • P aqueous premix
  • Example 4 also represents the procedure according to the present invention.
  • the test was carried out as example 3, except that the ripening time was increased from 1 min to 30 min. After 30 min of ripening, the aqueous premix (P) was injected into the friction loop in the same manner as described above. The friction reduction effect increased again to about 80 % and it took less than one minute to reach at the number.

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Abstract

L'invention concerne un procédé de fabrication d'un prémélange de polyacrylamide aqueux, le prémélange de polyacrylamide aqueux étant préparé par mélange d'une émulsion inverse de polyacrylamide ou d'un polymère de dispersion liquide comprenant des polyacrylamides avec un fluide aqueux, ce qui permet d'obtenir un prémélange aqueux comprenant au moins de l'eau, un liquide organique hydrophobe et des polyacrylamides, la concentration de polyacrylamide étant de 2 à 19,9 % en poids de polyacrylamides et permettant au prémélange aqueux de maturer pendant un certain temps. L'invention concerne également l'utilisation d'un tel prémélange aqueux pour diverses applications, en particulier pour la fracturation hydraulique et la récupération d'huile améliorée.
PCT/EP2021/054990 2020-03-06 2021-03-01 Procédé de fabrication d'un prémélange de polyacrylamide aqueux Ceased WO2021175757A1 (fr)

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Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2419764A1 (de) 1974-04-24 1975-12-18 Bayer Ag Nichtwaessrige polymerdispersionen wasserloeslicher monomerer
US4052353A (en) 1974-01-02 1977-10-04 Scanley Clyde S Dispersions of water soluble polymers in oil
US4528321A (en) 1983-04-06 1985-07-09 Allied Colloids Limited Polymer dispersions and their preparation
US5067508A (en) 1990-11-16 1991-11-26 Conoco Inc. Activation of water-in-oil emulsions of friction reducing polymers for use in saline fluids
US6365656B1 (en) 1999-04-07 2002-04-02 Ciba Specialty Chemicals Corporation Liquid dispersion polymer compositions, their preparation and their use
US6833406B1 (en) 2000-11-30 2004-12-21 Ciba Specialty Chemicals Corporation Liquid dispersion polymer compositions, their preparation and their use
WO2010133527A2 (fr) 2009-05-20 2010-11-25 Basf Se Copolymères associatifs à groupes hydrophobes
US20110118153A1 (en) 2009-08-07 2011-05-19 Pich Rene Method of continuous dissolution of polyacrylamide emulsions for enhanced oil recovery (eor)
WO2012069478A1 (fr) 2010-11-24 2012-05-31 Basf Se Procédé d'extraction de pétrole en utilisant des copolymères associatifs hydrophobes
US20120214714A1 (en) 2011-02-18 2012-08-23 Snf Holding Company Process for achieving improved friction reduction in hydraulic fracturing and coiled tubing applications in high salinity conditions
CA2864159A1 (fr) 2012-02-10 2013-08-15 Soane Energy, Llc Inversion de phase rapide d'emulsions de polymere eau dans huile
US20140131039A1 (en) 2012-11-14 2014-05-15 Basf Se Process for tertiary mineral oil production
US8841240B2 (en) 2011-03-21 2014-09-23 Clearwater International, Llc Enhancing drag reduction properties of slick water systems
WO2015086468A1 (fr) 2013-12-13 2015-06-18 Basf Se Procédé d'extraction de pétrole
US20150240144A1 (en) 2013-05-17 2015-08-27 Momentive Performance Materials Inc. Friction reducer compositions
WO2015158517A1 (fr) 2014-04-15 2015-10-22 Basf Se Procédé de production d'homo- ou de copolymères hydrosolubles comprenant du (méth)acrylamide
US9315722B1 (en) 2011-09-30 2016-04-19 Kemira Oyj Methods for improving friction reduction in aqueous brine
WO2016109333A1 (fr) 2014-12-31 2016-07-07 Paul Waterman Émulsions, fluides de traitement et procédés de traitement de formations souterraines
US20170121590A1 (en) 2015-11-04 2017-05-04 Ecolab Usa Inc. Friction-reducing compositions formulated with highly concentrated brine
US20170158948A1 (en) 2015-12-08 2017-06-08 Chevron U.S.A. Inc. Methods for hydrocarbon recovery
WO2017143136A1 (fr) 2016-02-17 2017-08-24 Ecolab Usa Inc. Sirop de maïs, auxiliaire d'inversion pour émulsions de polymères eau-dans-l'huile
WO2017187150A1 (fr) 2016-04-26 2017-11-02 Independence Oilfield Chemicals Llc Formulations et procédés
US20190002754A1 (en) 2017-06-30 2019-01-03 Chevron U.S.A. Inc. High stability polymer compositions for enhanced oil recovery applications
WO2019081320A1 (fr) * 2017-10-25 2019-05-02 Basf Se Procédé de production de solutions aqueuses de polyacrylamide

Patent Citations (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4052353A (en) 1974-01-02 1977-10-04 Scanley Clyde S Dispersions of water soluble polymers in oil
US4052353B1 (en) 1974-01-02 1990-01-30 Dispersions of water soluble polymers in oil
DE2419764A1 (de) 1974-04-24 1975-12-18 Bayer Ag Nichtwaessrige polymerdispersionen wasserloeslicher monomerer
US4528321A (en) 1983-04-06 1985-07-09 Allied Colloids Limited Polymer dispersions and their preparation
US5067508A (en) 1990-11-16 1991-11-26 Conoco Inc. Activation of water-in-oil emulsions of friction reducing polymers for use in saline fluids
US6365656B1 (en) 1999-04-07 2002-04-02 Ciba Specialty Chemicals Corporation Liquid dispersion polymer compositions, their preparation and their use
US6833406B1 (en) 2000-11-30 2004-12-21 Ciba Specialty Chemicals Corporation Liquid dispersion polymer compositions, their preparation and their use
WO2010133527A2 (fr) 2009-05-20 2010-11-25 Basf Se Copolymères associatifs à groupes hydrophobes
US20110118153A1 (en) 2009-08-07 2011-05-19 Pich Rene Method of continuous dissolution of polyacrylamide emulsions for enhanced oil recovery (eor)
WO2012069478A1 (fr) 2010-11-24 2012-05-31 Basf Se Procédé d'extraction de pétrole en utilisant des copolymères associatifs hydrophobes
US20120214714A1 (en) 2011-02-18 2012-08-23 Snf Holding Company Process for achieving improved friction reduction in hydraulic fracturing and coiled tubing applications in high salinity conditions
US8841240B2 (en) 2011-03-21 2014-09-23 Clearwater International, Llc Enhancing drag reduction properties of slick water systems
US9315722B1 (en) 2011-09-30 2016-04-19 Kemira Oyj Methods for improving friction reduction in aqueous brine
CA2864159A1 (fr) 2012-02-10 2013-08-15 Soane Energy, Llc Inversion de phase rapide d'emulsions de polymere eau dans huile
US20140131039A1 (en) 2012-11-14 2014-05-15 Basf Se Process for tertiary mineral oil production
US20150240144A1 (en) 2013-05-17 2015-08-27 Momentive Performance Materials Inc. Friction reducer compositions
WO2015086468A1 (fr) 2013-12-13 2015-06-18 Basf Se Procédé d'extraction de pétrole
WO2015158517A1 (fr) 2014-04-15 2015-10-22 Basf Se Procédé de production d'homo- ou de copolymères hydrosolubles comprenant du (méth)acrylamide
WO2016109333A1 (fr) 2014-12-31 2016-07-07 Paul Waterman Émulsions, fluides de traitement et procédés de traitement de formations souterraines
US20170121590A1 (en) 2015-11-04 2017-05-04 Ecolab Usa Inc. Friction-reducing compositions formulated with highly concentrated brine
US20170158948A1 (en) 2015-12-08 2017-06-08 Chevron U.S.A. Inc. Methods for hydrocarbon recovery
WO2017143136A1 (fr) 2016-02-17 2017-08-24 Ecolab Usa Inc. Sirop de maïs, auxiliaire d'inversion pour émulsions de polymères eau-dans-l'huile
WO2017187150A1 (fr) 2016-04-26 2017-11-02 Independence Oilfield Chemicals Llc Formulations et procédés
EP3448956A1 (fr) * 2016-04-26 2019-03-06 Independence Oilfield Chemicals, LLC Formulations et procédés
US20190002754A1 (en) 2017-06-30 2019-01-03 Chevron U.S.A. Inc. High stability polymer compositions for enhanced oil recovery applications
WO2019081320A1 (fr) * 2017-10-25 2019-05-02 Basf Se Procédé de production de solutions aqueuses de polyacrylamide

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