EP2643424A1 - Procédé d'extraction de pétrole en utilisant des copolymères associatifs hydrophobes - Google Patents

Procédé d'extraction de pétrole en utilisant des copolymères associatifs hydrophobes

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Publication number
EP2643424A1
EP2643424A1 EP11793699.7A EP11793699A EP2643424A1 EP 2643424 A1 EP2643424 A1 EP 2643424A1 EP 11793699 A EP11793699 A EP 11793699A EP 2643424 A1 EP2643424 A1 EP 2643424A1
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EP
European Patent Office
Prior art keywords
monomers
copolymer
group
weight
meth
Prior art date
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EP11793699.7A
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German (de)
English (en)
Inventor
Björn LANGLOTZ
Roland Reichenbach-Klinke
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BASF SE
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BASF SE
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Priority to EP11793699.7A priority Critical patent/EP2643424A1/fr
Publication of EP2643424A1 publication Critical patent/EP2643424A1/fr
Withdrawn legal-status Critical Current

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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
    • C09K8/58—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

Definitions

  • the present invention relates to a process for crude oil extraction in which an aqueous formulation comprising at least one water-soluble, hydrophobically associating copolymer is injected through at least one injection well into a crude oil reservoir and crude oil is taken from the deposit through at least one production well, the water-soluble, hydrophobically associating copolymer being at least Acrylamide or derivatives thereof, a monomer having anionic groups, and a monomer capable of causing the copolymer to associate.
  • the invention further relates to a particularly suitable for carrying out the method of water-soluble, hydrophobically associating copolymer, which has only a low shear degradation.
  • a deposit In natural oil deposits, petroleum is present in the cavities of porous reservoirs, which are closed to the earth's surface of impermeable cover layers.
  • the cavities may be very fine cavities, capillaries, pores or the like. Fine pore necks, for example, have a diameter of only about 1 ⁇ .
  • a deposit In addition to oil, including natural gas, a deposit also contains more or less saline water.
  • the autogenous pressure can be caused for example by existing in the deposit gases such as methane, ethane or propane.
  • the autogenous pressure of the deposit generally decreases relatively quickly when crude oil is withdrawn, so that by means of primary production, depending on the type of deposit, only about 5 to 10% of the quantity of crude oil present in the deposit can usually be pumped. After that, the autogenous pressure is no longer sufficient to extract oil.
  • the secondary promotion is used.
  • additional wells will be drilled into the oil-bearing formation in addition to the wells that serve to extract the oil, known as production wells.
  • water flooding water is injected into the reservoir (the so-called "water flooding") to maintain or increase the pressure, and the injection of water causes the oil to slowly move from the injection well into the production well through the cavities in the formation
  • water flooding water flooding
  • tertiary oil recovery measures also known as Enhanced Oil Recovery (EOR)
  • EOR Enhanced Oil Recovery
  • polymer flooding an aqueous solution of a thickening polymer is injected through the injection bores into the oil reservoir, with the viscosity of the aqueous polymer solution being adapted to the viscosity of the crude oil
  • the polymer solution is pressed in, as in the case of water flooding, the oil is forced through the cavities in the formation from the injection bore towards the production well, and the crude oil is conveyed through the production well, but the polymer formulation has about the same viscosity as the oil Crude oil reduces the risk of the polymer formulation breaking through with no effect on production drilling, and thus the mobilization of petroleum is much smoother than with the use of low viscosity water, thus allowing additional oil to be mobilized in the formation Details of polymer flooding and suitable polymers are disclosed, for example, in "Petroleum, Enhanced Oil Recovery, Kirk-Othmer, Encyclopedia of Chemical Technology, Online Edition, John Wiley & Sons, 2010".
  • polyacrylamide For polymer flooding a variety of different, thickening acting polymers have been proposed, in particular high molecular weight polyacrylamide, copolymers of acrylamide and other comonomers such as vinyl sulfonic acid or acrylic acid.
  • polyacrylamide may be partially hydrolyzed polyacrylamide in which a portion of the acrylamide units is hydrolyzed to acrylic acid.
  • naturally occurring polymers for example xanthan or polyglycosylglucan, as described, for example, by US Pat. No. 6,392,596 B1 or CA 832,277.
  • hydrophobically associating copolymers for polymer flooding.
  • water-soluble polymers which have side or terminal hydrophobic groups, for example longer alkyl chains.
  • hydrophobic groups may associate with themselves or with other hydrophobic group-containing substances.
  • an associative network is formed, through which the medium is thickened.
  • EP 705 854 A1, DE 100 37 629 A1 and DE 10 2004 032 304 A1 disclose water-soluble, hydrophobically associating copolymers and their use, for example in the field of construction chemistry.
  • the copolymers described include acidic monomers such as acrylic acid, vinylsulfonic acid, acrylamidomethylpropanesulfonic acid, basic monomers such as acrylamide, dimethylacrylamide or monomers comprising cationic groups, such as monomers containing ammonium groups and also monomers which can cause the hydrophobic association of the individual polymer chains.
  • hydrophobically associating copolymers comprising at least hydrophilic, monoethylenically unsaturated monomers such as, for example, acrylamide and also monoethylenically unsaturated hydrophobically associating monomers.
  • the hydrophobically associating monomers have a block structure and have, in this order, an ethylenically unsaturated group, optionally a linking group, a first polyoxyalkylene block comprising at least 50 mol% of ethyleneoxy groups and a second polyoxyalkylene block consisting of alkyleneoxy groups having at least 4 carbon atoms is on.
  • the application discloses the use of such copolymers as thickeners, for example for polymer flooding, for construction chemical applications or for detergent formulations.
  • an aqueous, viscous polymer formulation is pressed into a hole drilled in the crude oil formation.
  • This well is also called “injection well” and is usually lined with cemented steel tubes that are perforated in the petroleum formation area and thus allow the polymer formulation to exit the injection well into the petroleum formation.
  • the flow rate of the aqueous polymer formulation as it enters the formation is greatest and decreases as the distance from the injection well increases, as shown schematically in Figure 1. Since a petroleum formation is a porous material and the formulation must flow through the pores, very high shear forces act on the aqueous polymer formulation as it enters the formation.
  • the object of the invention was to provide an improved process for polymer flooding, in particular for fine-pored petroleum formations, in which the polymer can be injected particularly well into the formation.
  • a petroleum production process which comprises subjecting an aqueous formulation comprising at least one water-soluble, hydrophobically associating copolymer to at least one injection well in a petroleum deposit having an average porosity of 10 millidarcy to 4 Darcy and a format. Pressed on temperature of 30 ° C to 150 ° C and withdraws the deposit through at least one production well crude oil, and wherein
  • (b1) at least one neutral, monoethylenically unsaturated, hydrophilic monomer (b1) selected from the group of (meth) acrylamide, N-methyl (meth) acrylamide, N, N'-dimethyl (meth) acrylamide or N-methylol (meth ) acrylamide, as well as
  • hydrophilic monomer (b2) which is at least one acidic group selected from the group of -COOH, -SO 3 H or -PO 3 H 2 or salts thereof, the amounts given being based on the total amount of all monomers in the copolymer,
  • the copolymer has a weight-average molecular weight Mw of from 1 ⁇ 10 6 g / mol to 30 ⁇ 10 6 g / mol,
  • the amount of copolymer in the formulation is 0.02 to 2% by weight
  • the viscosity of the formulation is at least 5 mPas (measured at 25 ° C)
  • the aqueous polymer formulation is injected into the formation at a shear rate of at least 30,000 s -1 .
  • water-soluble, hydrophobically associating copolymers having a weight-average molecular weight Mw of from 1 * 10 ⁇ 6 > g / mol to 30 * 10 ⁇ 6 > g / mol were found, comprising at least (A) 0.1 to 15 wt .-% of at least one monoethylenically unsaturated, hydrophobically associating monomer (a), and
  • (b1) at least one neutral, monoethylenically unsaturated, hydrophilic monomer (b1) selected from the group of (meth) acrylamide, N-methyl (meth) acrylamide, N, N'-dimethyl (meth) acrylamide or N-methylol (meth ) acrylamide, as well as
  • (b2) at least one anionic, monoethylenically unsaturated, hydrophilic monomer (b2), which is at least one acidic group selected from the group of -COOH, -SO3H or -PC l- or salts thereof, wherein the amounts given in each case to the total amount of all Monomers are in the copolymer, and wherein the shear degradation of the copolymer measured by a capillary shear test according to API RP 63 is not more than 10%.
  • FIG. 1 Schematic representation of the entry of an injection liquid into the petroleum formation.
  • FIG. 2 Schematic representation of the equipment for determining the shear stability according to API RP 63.
  • an aqueous formulation of at least one water-soluble, hydrophobically associating copolymer is used and injected through an injection well into a crude oil deposit.
  • hydrophobically associating copolymer is known in principle to a person skilled in the art, which is a water-soluble copolymer which, in addition to hydrophilic moieties which ensure sufficient water solubility, has lateral or terminal hydrophobic groups. pen of the polymer with itself or with other, hydrophobic groups having
  • the copolymers used in this invention should be miscible with water in any proportion. However, according to the invention it is sufficient if the copolymers are water-soluble at least at the desired use concentration and at the desired pH. As a rule, the solubility of the copolymer in water at room temperature under the conditions of use should be at least 25 g / l.
  • the water-soluble, hydrophobically associating copolymer comprises 0.1 to 15% by weight of at least one monoethylenically unsaturated, hydrophobically associating monomer (a) and 85 to 99.9% by weight of at least two, thereof different, monoethylenically unsaturated, hydrophilic monomers (b ).
  • ethylenically unsaturated, preferably monoethylenically unsaturated, monomers (c) which are different from the monomers (a) and (b) may optionally be present in an amount of up to 14.9% by weight.
  • the amounts given in each case relate to the sum of all monomers in the copolymer. Preference is given to using exclusively monoethylenically unsaturated monomers.
  • the water-soluble, hydrophobically associating copolymer employed comprises at least one monoethylenically unsaturated monomer (a) which imparts hydrophobically associating properties to the copolymer and is therefore to be referred to hereinafter as the "hydrophobically associating monomer".
  • the hydrophobically associating monomers (a) include, in addition to the ethylenically unsaturated group, a hydrophobic group which, after polymerization, is responsible for the hydrophobic association of the formed copolymer.
  • they further comprise hydrophilic moieties which impart some water solubility to the monomer.
  • any hydrophobically associating, monoethylenically unsaturated monomers (a) can be used, provided that the copolymer can be injected into the formation at a shear rate of at least 30,000 s -1 .
  • the person skilled in the art is familiar with monomers (a) and makes a suitable choice.
  • the hydrophobic group Z is aliphatic and / or aromatic, straight-chain or branched Cs to C32 hydrocarbon radicals, preferably C12 to C3o hydrocarbon radicals.
  • the group Z is a group of alkylene oxide units having at least 3 carbon atoms. atoms, preferably at least 4 and more preferably at least 5 carbon atoms act.
  • Preferred Monomers (a) Preferably at least one of the monoethylenically unsaturated water-soluble monomers (a) is at least one selected from the group of
  • R 1 is H or a methyl group.
  • R 2 represents a single bond or a divalent linking group selected from the group consisting of - (C n H 2n ) - [group R 2a ], -O- (GyH 2l y) - [group R 2b ] - and -C (0) -0- (Cn "H 2n ”) - [Group R 2c ].
  • n, n 'and n "each represent a natural number of 1 to 6.
  • the group R 2a is a group selected from -CH 2 -, - CH 2 - CH 2 - and -CH 2 -CH 2 -CH 2 -, more preferably is a methylene group -CH 2 -.
  • the group R 2b is a group selected from -O-CH 2 -CH 2 -, -O-CH 2 -CH 2 -CH 2 - and -O-CH 2 -CH 2 -CH 2 -CH 2 -, particularly preferably -O- CH2-CH2-CH2
  • the group R 2c is preferably a group selected from -C (O) -O-CH 2 -CH 2 -, -C (O) O-CH (CH 3 ) -CH 2 -, -C (O) O -CH 2 -CH (CH 3 ) -, -C (O) O-CH 2 -CH 2 -CH 2 - and -C (O ) O-CH 2 -CH 2 -CH 2 -CH 2 -CH 2 -, more preferably -C (0) -0-CH 2 -CH 2 - and -C (0) 0-CH2-CH2-CH2-CH 2 -, and most preferably is -C (0) -0-CH 2 - CH 2 -.
  • the group R 2 is particularly preferably a group R 2a or R 2b , more preferably a group R 2b , ie monomers based on vinyl ethers.
  • R 2 is a group selected from -CH 2 - or -O-CH 2 -CH 2 -CH 2 -, very particularly preferably -O-CH 2 -CH 2 -CH 2 -CH 2 -.
  • the monomers (I) furthermore have a polyoxyalkylene radical which consists of the units - (- CH 2 -CH (R 3 ) -O-) k and - (- CH 2 -CH (R 4 ) -O-) i, wherein the units are arranged in block structure in the order shown in formula (I).
  • the transition between the two blocks can be abrupt or continuous.
  • the radicals R 3 independently of one another are H, methyl or ethyl, preferably H or methyl, with the proviso that at least 50 mol% of the radicals R 3 to H acts.
  • at least 75 mol% of the radicals R 3 are H, more preferably at least 90 mol% and most preferably exclusively H.
  • the block referred to is thus a polyoxyethylene block which optionally also contains certain proportions Propylene oxide and / or butylene oxide units may have, preferably a pure polyoxyethylene block.
  • the number of alkylene oxide units k is a number from 10 to 150, preferably from 12 to 100, particularly preferably from 15 to 80, very particularly preferably from 20 to 30 and for example from about 22 to 25.
  • the polyalkylene oxides that these figures are mean values of distributions.
  • the radicals R 4 independently of one another are hydrocarbon radicals of at least 2 carbon atoms, preferably at least 3, more preferably 3 to 10, most preferably 3 to 8 Carbon atoms and, for example, 3 to 4 carbon atoms. It may be an aliphatic and / or aromatic, linear or branched carbon radical. Preference is given to aliphatic radicals.
  • radicals R 4 include ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl and also phenyl.
  • suitable radicals R 4 include n-propyl, n-butyl, n-pentyl and particularly preferred is an n-propyl radical.
  • radicals R 4 may furthermore be ether groups of the general formula -CH 2 -O-R 4 ' , where R 4' is an aliphatic and / or aromatic, linear or branched hydrocarbon radical having at least 2 carbon atoms, preferably at least 3 and more preferably 3 to 10 carbon atoms.
  • radicals R 3 ' include n-propyl, n-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or phenyl.
  • the block - (- CH 2 -CH (R 4 ) -O-) i- is thus a block consisting of alkylene oxide units having at least 4 carbon atoms, preferably at least 5 carbon atoms, in particular 5 to 10 carbon atoms, and / or Glycidyl ethers having an ether group of at least 2, preferably at least 3 carbon atoms.
  • Preferred radicals R 3 are the hydrocarbon radicals mentioned;
  • the building blocks of the second terminal block are particularly preferably alkylene oxide units comprising at least 5 carbon atoms, such as pentenoxide units or units of higher alkylene oxides.
  • the number of alkylene oxide units I is a number from 5 to 25, preferably 6 to 20, particularly preferably 8 to 18, very particularly preferably 10 to 15 and for example about 12.
  • the radical R 5 is H or a preferably aliphatic hydrocarbon radical having 1 to 30 carbon atoms, preferably 1 to 10 and particularly preferably 1 to 5 carbon atoms.
  • R 5 is preferably H, methyl or ethyl, particularly preferably H or methyl and very particularly preferably H.
  • a terminal, monoethylenic group is linked to a block-structured polyoxyalkylene group, first with a hydrophilic block having polyethylene oxide units and this in turn with a second, hydrophobic, terminal block comprising at least butene oxide units, preferably at least Penten oxide units or units of higher alkylene oxides such as dodecene oxide is constructed.
  • the second block has a terminal -OR 5 group, in particular an OH group.
  • the terminal block - (- CH 2 -CH (R 4 ) -O-) i with the radicals R 4 is responsible for the hydrophobic association of the copolymers prepared using the monomers (a).
  • Verethern of the OH end group is an option that can be chosen by the skilled person depending on the desired properties of the copolymer.
  • a terminal hydrocarbon group is not required for hydrophobic association, but hydrophobic association also works for a terminal OH group.
  • the transition between the two blocks may be abrupt or continuous, depending on the nature of the preparation. In a continuous transition, there is still a transition zone between the two blocks, which comprises monomers of both blocks.
  • the first block - (- CH 2 -CH (R 3 ) -0-) k can still contain small amounts of units -CH 2 -CH (R 4 ) -O-. and the second block - (- CH 2 -CH (R 4 ) -O-) i-small amounts of units -CH 2 -CH (R 3 ) -0-, but these units are not statistically distributed throughout the block but are arranged in said transition zone.
  • hydrophobically associating monomers (a) of the formula (I) can be carried out by methods known in the art.
  • monomers (a) in a preferred preparation process, suitable monoethylenically unsaturated alcohols (IV) are used, which are subsequently alkoxylated in a two-stage process, so that the abovementioned block structure is obtained.
  • monomers (a) of formula (I) with R 5 H.
  • the stated starting compounds are alkoxylated, in a two-stage process initially with ethylene oxide, optionally mixed with propylene oxide and / or butylene oxide and in a second step with alkylene oxides of the general formulas (Xa) or (Xb) where R 4 in (Xa) or R 4 'in (Xb) have the meaning defined above.
  • the carrying out of an alkoxylation including the preparation of block copolymers of various alkylene oxides, is known in principle to a person skilled in the art. It is also known to the person skilled in the art that the reaction conditions, in particular the choice of catalyst, can influence the molecular weight distribution of the alkoxylates and the orientation of alkylene oxide units in a polyether chain.
  • the alkoxylates can be prepared, for example, by base-catalyzed alkoxylation.
  • the alcohol used as starting material can be mixed in a pressure reactor with alkali metal hydroxides, preferably potassium hydroxide or with alkali metal such as sodium methylate.
  • alkali metal hydroxides preferably potassium hydroxide or with alkali metal such as sodium methylate.
  • the mixture is then inertized with inert gas (eg nitrogen) and a step in a stepwise addition of ethylene oxide, optionally in admixture with propylene and / or butylene oxide at temperatures of 60 to 180 ° C, preferably 130 to 150 ° C.
  • the addition is typically within 2 to 5 hours, without the invention being limited thereto.
  • the reaction mixture is expediently allowed to react, for example for 1 h to 1 h.
  • metered alkylene oxides of the general formula (Xb) gradually.
  • the reaction temperature in the second stage can be maintained or changed. Proven to have a lower by about 10 to 25 ° C reaction temperature than in the first stage.
  • the alkoxylation can also be carried out by techniques which result in narrower molecular weight distributions than in the base-catalyzed synthesis.
  • double hydroxide clays as described in DE 43 25 237 A1 can be used as the catalyst.
  • the alkoxylation can be carried out particularly preferably using double metal cyanide catalysts (D MC catalysts). Suitable DMC
  • Catalysts are disclosed, for example, in DE 102 43 361 A1, in particular in Sections [0029] to [0041] and in the literature cited therein.
  • Zn-Co type catalysts can be used.
  • the alcohol used as the starting material may be added with the catalyst, the mixture dehydrated as described above and reacted with the alkylene oxides as described.
  • the catalyst may remain in the product due to this small amount.
  • the alkoxylation can also be carried out acid-catalyzed.
  • the acids may be Bronsted or Lewis acids.
  • the alcohol used as the starting material may be added with the catalyst, the mixture dewatered as described above and reacted with the alkylene oxides as described.
  • the acidic catalyst can be neutralized by addition of a base, for example KOH or NaOH, and filtered off as required.
  • the orientation of the hydrocarbyl radicals R 4 and optionally R 3 may depend on the conditions of the alkoxylation, for example the catalyst chosen for the alkoxylation.
  • the alkylene oxide groups can thus be incorporated into the monomer both in the orientation - (- CH 2 -CH (R 4 ) -O-) or in inverse orientation - (- CH (R 4 ) -CH 2 -).
  • the representation in formula (I) should therefore not be regarded as being restricted to a specific orientation of the groups R 3 or R 4 .
  • this can in principle known to the skilled man, the usual alkylating agents take place, for example, alkyl sulfates.
  • alkyl sulfates for etherification, in particular dimethyl sulfate or diethyl sulfate can be used.
  • the described preferred preparation process for the monomers (I) has the advantage that the formation of possibly cross-linking by-products with two ethylenically unsaturated groups is largely avoided. Accordingly, copolymers having a particularly low gel content can be obtained.
  • R 1 , R 3 and k have the meanings already described.
  • R 6 is an aliphatic and / or aromatic, straight-chain or branched hydrocarbon radical having 8 to 40 carbon atoms, preferably 12 to 32 carbon atoms.
  • they may be n-alkyl groups such as n-octyl, n-decyl or n-dodecyl groups, phenyl groups and in particular substituted phenyl groups.
  • Substituents on the phenyl groups may be alkyl groups, for example C 1 - to C 1 -alkyl groups, preferably styryl groups.
  • hydrophobically associating monomers of the formulas (II) or (III) and their preparation are known in principle to the person skilled in the art, for example from EP 705 854 A1.
  • Amounts of monomers (a) The amount of monoethylenically unsaturated, hydrophobically associating monomers (a) is 0.1 to 15 wt .-% based on the total amount of all monomers in the copolymer, in particular 0.1 to 10 wt .-%, preferably 0 , 2 to 5 wt .-% and particularly preferably 0.5 to 2 wt .-%.
  • at least 50% by weight, preferably at least 80% by weight, of the monomers (a) are monomers (a) of the general formula (I), (II) and / or (III) and only monomers are preferred (a) the general formula (I), (II) and / or (III) used.
  • Particular preference is given to using only monomers (a) of the general formula (I) for preparing the copolymers of the invention, very particularly preferably monomers (a) of the general formula (I) in which R 2 is a radical R 2b .
  • the hydrophobically associating copolymer used according to the invention comprises at least two, monoethylenically unsaturated, hydrophilic monomers (b) which are different therefrom.
  • the monoethylenically unsaturated hydrophilic monomers (b) used are miscible with water in any desired ratio, but it is sufficient for carrying out the invention that the hydrophobically associating copolymer according to the invention has the water solubility mentioned in the introduction.
  • the solubility of the monomers (b) in water at room temperature should be at least 50 g / l, preferably at least 150 g / l and particularly preferably at least 250 g / l.
  • the copolymer comprises at least one at least one neutral, monoethylenically unsaturated, hydrophilic monomer (b1) selected from the group of (meth) acrylamide, N-methyl (meth) acrylamide, N, N'-dimethyl (meth) acrylamide or N- Methylol (meth) acrylamide. It is preferably (meth) acrylamide, in particular acrylamide. If mixtures of different monomers (b1) are used, at least 50 mol% of the monomers (b1) should be (meth) acrylamide, in particular acrylamide.
  • the copolymer used further comprises at least one hydrophilic, monoethylenically unsaturated anionic monomer (b2) which comprises at least one acidic group selected from the group of -COOH, -SO3H or -PO3H2 or salts thereof.
  • a hydrophilic, monoethylenically unsaturated anionic monomer (b2) which comprises at least one acidic group selected from the group of -COOH, -SO3H or -PO3H2 or salts thereof.
  • Suitable counterions include in particular alkali metal ions such as Li + , Na + or K + and ammonium ions such as NH 4 + or ammonium ions with organic radicals.
  • COOH group-containing monomers include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid. Preference is given to acrylic acid.
  • Examples of monomers comprising sulfonic acid groups include vinylsulfonic acid, allylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid, 3-acrylamido-3-methylbutanesulfonic acid or 2-acrylamido-2,4,4 -trimethylpentansulfonkla.
  • Examples of monomers comprising phosphonic acid groups include vinylphosphonic acid, allylphosphonic acid, N- (meth) acrylamidoalkylphosphonic acids or
  • the monomers (b1) may under certain circumstances at least partially hydrolyze to (meth) acrylic acid in the course of their preparation and use.
  • the copolymers used according to the invention can accordingly be mentioned.
  • the copolymers used according to the invention may optionally comprise at least one monoethylenically unsaturated, cationic, ammonium ion-containing monomer (b3).
  • Suitable cationic monomers (b3) include, in particular, ammonium-containing monomers, in particular ammonium derivatives of N- (ro-aminoalkyl) (meth) acrylamides or ro-aminoalkyl (meth) acrylic esters.
  • R 8 is H or methyl
  • R 9 is H or a C 1 to C 4 alkyl group, preferably H or methyl
  • R 10 is a preferably linear C 1 to C 4 alkylene group, for example a 1, 2-ethylene group -CH 2 - CH 2 or a 1, 3-propylene group -CH 2 -CH 2 -CH 2 -.
  • the radicals R 11 are each independently C 1 to C 4 alkyl radicals, preferably methyl or a group of the general formula -R 12 -SO 3 H, where R 12 is a preferably linear C 1 to C 4 alkylene group or a phenyl group, with the proviso that it is usually not more than one of the substituents R 11 is a sulfonic acid groups having substituents. Particularly preferably, the three substituents R 11 are methyl groups, ie the monomer has a group --N (CH 3) 3 + .
  • X " in the above formula stands for a monovalent anion, for example CK. Of course, X " can also stand for a corresponding fraction of a polyvalent anion, although this is not preferred.
  • Examples of preferred monomers (b3) of the general formula (Va) or (Vb) include salts of 3-trimethylammonium-propyl (meth) acrylamides or 2-trimethylammoniumethyl (meth) acrylates, for example the corresponding chlorides such as 3-trimethylammoniumpropylacrylamide chloride (DIMAPAQUAT) and 2-trimethylammoniumethyl methacrylate chloride (MADAM E-QU AT).
  • DIMAPAQUAT 3-trimethylammoniumpropylacrylamide chloride
  • MADAM E-QU AT 2-trimethylammoniumethyl methacrylate chloride
  • the copolymers used in the present invention may further comprise other monoethylenically unsaturated hydrophilic monomers (b4) other than the hydrophilic monomers (b1), (b2) and (b3).
  • the radicals R 13 are each independently H, methyl or ethyl, preferably H or methyl, with the proviso that at least 50 mol% of the radicals R 13 is H. Preferably, at least 75 mol% of the radicals R 13 are H, more preferably at least 90 mol% and most preferably exclusively H.
  • the radical R 14 is H, methyl or ethyl, preferably H or methyl .
  • monomers (b4) include N-vinyl derivatives such as, for example, N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone or N-vinylcaprolactam and vinyl esters, such as, for example, vinyl formate or vinyl acetate.
  • N-vinyl derivatives can be hydrolyzed after polymerization to vinylamine units, vinyl esters to vinyl alcohol units.
  • the amount of all hydrophilic monomers (b) in the copolymer of the invention is according to the invention 85 to 99.9 wt .-% based on the total amount of all monomers in the copolymer, preferably 90 to 99.8 wt .-%.
  • the amount of neutral, hydrophilic monomers (b1) is generally 30 to 95 wt.%, Preferably 30 to 85 wt.% And particularly preferably 30 to 70 wt.% With respect to the total amount of all monomers used. If the copolymer comprises only neutral monomers (b1) and anionic monomers (b2), it has been found that the neutral monomers (b1) are present in an amount of 30 to 95% by weight and the anionic monomers (b2) in an amount of 4, 9 to 69.9 wt.% Use, wherein the amount is based in each case on the total amount of all monomers used.
  • the monomers (b1) are used in an amount of 30 to 80% by weight and the anionic monomers (b2) in an amount of 19.9 to 69.9% by weight, and more preferably the monomers (b1 ) in an amount of 40 to 70% by weight and the anionic monomers (b2) in an amount of 29.9 to 59.9% by weight
  • the copolymer comprises neutral monomers (b1), anionic monomers (b2) and cationic monomers (b3)
  • the neutral monomers (b1) in an amount of 30 to 95% by weight and the anionic (b2) and cationic monomers (b3) together in an amount of 4.9 to 69.9 wt.%, with the proviso that the molar ratio (b2) / (b3) is 0.7 to 1.3.
  • the molar ratio (b2) / (b3) is preferably 0.8 to 1.2 and, for example, 0.9 to 1.1.
  • the monomers (b1) are used in an amount of 30 to 80% by weight and the anionic and cationic monomers (b2) + (b3) are used together in an amount of 19.9 to 69.9% by weight, and
  • the monomers (b1) are particularly preferably used in an amount of 40 to 70% by weight and the anionic and cationic monomers (b2) + (b3) together in an amount of 29.9 to 59.9% by weight, in each case the already mentioned molar ratio should be maintained.
  • the copolymers of the invention may optionally comprise ethylenically unsaturated monomers other than the monomers (a) and (b), preferably monoethylenically unsaturated monomers (c).
  • ethylenically unsaturated monomers other than the monomers (a) and (b) preferably monoethylenically unsaturated monomers (c).
  • monoethylenically unsaturated monomers (c) can be used.
  • Such monomers can be used to fine tune the properties of the copolymer used in the present invention. If present at all, the amount of such optionally present monomers (c) may be up to 14.9% by weight, preferably up to 9.9% by weight, more preferably up to 4.9% by weight, based in each case on the total amount all monomers. Most preferably, no monomers (c) are present.
  • the monomers (c) may, for example, be monoethylenically unsaturated monomers which have a more hydrophobic character than the hydrophilic monomers (b) and which accordingly are only slightly water-soluble.
  • the solubility of the monomers (c) in water at room temperature is less than 50 g / l, in particular less than 30 g / l.
  • Examples of such monomers include N-alkyl and N, N'-dialkyl (meth) acrylamides wherein the number of carbon atoms in the alkyl groups taken together is at least 3, preferably at least 4.
  • Examples of such monomers include N-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide or N-benzyl (meth) acrylamide.
  • copolymers used according to the invention can be prepared by methods known in principle to the person skilled in the art by radical polymerization of the monomers (a), (b) and optionally (c), for example by solution or gel polymerization in the aqueous phase.
  • the monomers (a), (b), optionally (c), initiators and optionally further auxiliaries are used for the polymerization in an aqueous medium.
  • the preparation is carried out by means of gel polymerization in aqueous phase.
  • a mixture of the monomers (a), (b) and optionally (c), initiators and, if appropriate, further auxiliaries with water or an aqueous solvent mixture is first provided.
  • Suitable aqueous solvent mixtures include water and water-miscible organic solvents, the proportion of water being generally at least 50% by weight, preferably at least 80% by weight and particularly preferably at least 90% by weight.
  • organic solvents are in particular water-miscible alcohols such as methanol, ethanol or propanol. Acidic monomers can be completely or completely pre-polymerized partially neutralized.
  • the concentration of all components with the exception of the solvents in the course of the polymerization is usually about 20 to 60 wt .-%, preferably about 30 to 50 wt .-%.
  • the polymerization should be carried out in particular at a pH in the range from 5.0 to 7.5 and preferably at a pH of 6.0.
  • the copolymers used are prepared in the presence of at least one non-polymerizable, surface-active compound (T).
  • the non-polymerizable surface-active compound (T) is preferably at least one nonionic surfactant, but anionic and cationic surfactants are also suitable if they do not participate in the polymerization reaction. They may in particular be surfactants, preferably nonionic surfactants of the general formula R 13 -Y ', where R 13 is a hydrocarbon radical having 8 to 32, preferably 10 to 20 and particularly preferably 12 to 18 carbon atoms and Y' is a hydrophilic group , preferably a nonionic hydrophilic group, in particular a polyalkoxy group.
  • the nonionic surfactant is preferably an ethoxylated long-chain aliphatic alcohol which may optionally contain aromatic moieties.
  • C ⁇ C fatty alcohol ethoxylates CissCis fatty alcohol ethoxylates, Ci3-oxoalcohol ethoxylates, Cio-Oxoalkoholethoxylate, Ci3Ci5-Oxoalkoholethoxylate,
  • Cio-Guerbet alcohol ethoxylates and alkylphenol ethoxylates Compounds having 5 to 20 ethyleneoxy units, preferably 8 to 18 Ethylenoxy knewe have proven particularly useful.
  • small quantities of higher alkyleneoxy units, in particular propyleneoxy and / or butyleneoxyoxy units may also be present, but the amount as ethyleneoxy units should generally amount to at least 80 mol% with respect to all alkyleneoxy units.
  • Surfactants selected from the group of the ethoxylated alkylphenyls, the ethoxylated, saturated iso-C 13 -alcohols and / or the ethoxylated C 10 -guerbet alcohols are particularly suitable, in each case 5 to 20 ethyleneoxy units, preferably 8 to 18 ethyleneoxy units in alkoxy radicals being present.
  • the hydrophobically associating comonomers (a) form in the aqueous reaction mixture. onsmedium micelles. In the polymerization, this leads to the fact that the hydrophobically associating regions are incorporated in blocks in the polymer. If, according to the invention, an additional surface-active compound is present in the preparation of the copolymers, mixed micelles form. These mixed micelles contain polymerizable and non-polymerizable moieties. This will then incorporate the hydrophobically associating monomers in shorter blocks. At the same time, the number of these shorter blocks per polymer chain is larger.
  • the non-polymerizable surface-active compounds (T) can generally be used in an amount of from 0.1 to 5% by weight, based on the amount of all the monomers used.
  • the weight ratio of the nonpolymerizable, surface-active compounds (T) used to the monomers (a) is generally 4: 1 to 1: 4, preferably 2: 1 to 1: 2, particularly preferably 1, 5: 1 to 1 : 1, 5 and for example about 1: 1.
  • the required components are first mixed with one another. It does not matter in the order in which the components are mixed for polymerization, it is only important that in the preferred polymerization method the non-polymerizable surfactant compound (T) is added to the aqueous polymerization medium prior to initiation of the polymerization.
  • the mixture is then thermally and / or photochemically polymerized, preferably at -5 ° C to 80 ° C.
  • thermally polymerized preference is given to using polymerization initiators which can initiate the polymerization even at a comparatively low temperature, for example redox initiators.
  • the thermal polymerization can be carried out even at room temperature or by heating the mixture, preferably to temperatures of not more than 50 ° C.
  • the photochemical polymerization is usually carried out at temperatures of -5 to 10 ° C. It is also possible to combine photochemical and thermal polymerization by adding to the mixture both thermal and photochemical polymerization initiators.
  • the polymerization is first started photochemically at low temperatures, preferably -5 to +10 ° C.
  • the liberated heat of reaction heats up the mixture, which additionally initiates thermal polymerization.
  • the reaction can also be carried out with a mixture of a redox initiator system and a thermal initiator which decomposes only at relatively high temperatures.
  • a thermal initiator which decomposes only at relatively high temperatures.
  • This can be for example to be a water-soluble azo initiator, which decomposes in the temperature range of 40 ° C to 70 ° C.
  • the polymerization starts here at low temperatures of, for example, 0 to 10 ° C by the redox initiator system.
  • the mixture heats up and, in addition, the polymerization is started by the initiator which decomposes only at relatively high temperatures.
  • the gel polymerization is usually carried out without stirring. It can be carried out batchwise by irradiating and / or heating the mixture in a suitable vessel at a layer thickness of 2 to 20 cm.
  • the polymerization produces a solid gel.
  • the polymerization can also be carried out continuously.
  • a polymerization apparatus which has a conveyor belt for receiving the mixture to be polymerized. The conveyor belt is equipped with means for heating and / or for irradiation with UV radiation. Thereafter, the mixture is poured on by means of a suitable device at one end of the band, in the course of transport in the band direction, the mixture polymerizes and at the other end of the band can remove the solid gel.
  • the resulting gel is preferably comminuted and dried after the polymerization.
  • the drying should preferably be carried out at temperatures below 100 ° C.
  • a suitable release agent can be used for this step.
  • the hydrophobically associating copolymer is obtained as granules or powder.
  • the copolymers obtained preferably have a weight-average molecular weight M w of from 1 * 10 6 g / mol to 30 * 10 6 g / mol, preferably 5 * 10 6 g / mol to 20 * 10 6 g / mol.
  • such copolymers are used for the process, which is characterized by a particularly low shear degradation.
  • shear degradation is defined as the percent permanent change in viscosity of a polymer solution after shear of the polymer solution under certain conditions. "Permanent” means that the loss of viscosity is retained even after the shear stress has been eliminated and is not reversible, as in the shear-thinning (shear-thinning) behavior when the shear stress is removed due to shear, the polymer solution is large enough to cause breakage of polymer chains (see, for example, JM Maerker, Shear Degradation of partially hydrolyzed Polyacrylamide Solutions, SPE Journal 15 (4), 1975, pages 31 1 - 322 or RS Seright, SPE Journal 23 (3), 1983, pages 475-485), this reduces the proportion of long polymer chains in the polymer solution, and consequently decreases the viscosity of the polymer Polymer solution irreversibly.
  • the shear degradation of polymers can be measured by means of a capillary shear test according to API RP 63.
  • a solution of the polymer is forced under pressure through a narrow capillary.
  • the viscosity of the polymer solution before and after pressing through the capillary is determined in each case.
  • the shear stress of the polymer can be adjusted by the pressure at which the solution is forced through the capillary, the length and diameter of the capillary, and the viscosity of the polymer solution (i.e., ultimately, the concentration of the polymer solution).
  • the details of performing the capillary shear test according to API RP 63 are listed in the examples of this invention, which is incorporated herein by reference.
  • the shear degradation of the copolymers used for the process according to the invention measured by means of a capillary shear test according to API RP 63 under the conditions specified in the example is preferably less than 10%, more preferably less than 8%. Due to this preferred property, the amount of copolymer used can be kept lower than in copolymers which have higher shear degradation.
  • the present invention therefore relates to a hydrophobically associating copolymer of the composition described in the introduction, which is characterized in that the shear degradation measured by means of a capillary shear test according to API RP 63 under the specified conditions in the example part less than 10%, preferably less than 8%.
  • Preferred compositions as well as the preparation of the copolymers according to the invention have also already been described.
  • At least one production well and at least one injection well are sunk into the crude oil deposit.
  • the at least one injection well injects an aqueous formulation of the described copolymer into the oil reservoir and removes oil from the reservoir through at least one production well.
  • the term "petroleum” in this context does not only mean phase-pure oil, but also includes the usual crude oil-water emulsions
  • the petroleum flows through the pressure generated by the pressed-in formulation, the so-called "polymer flood" in the direction of the production well and is funded through the production well.
  • the porosity (more correctly referred to as "permeability") of a petroleum formation is given by the expert in the unit “Darcy” (abbreviated “D” or “mD” for “Millidarcy”) and can be derived from the flow rate of a liquid phase in the petroleum formation.
  • the flow rate can be determined in core flooding experiments with cores taken from the formation of formations, details of which can be found, for example, in K. Weggen, G. Pusch, H. Rischmüller in "Oil and Gas", pages 37 ff. Ulmann's Encyclopedia of Industrial Chemistry, Online Edition, Wiley-VCH, Weinheim 2010. It will be understood by those skilled in the art that the permeability in an oil reservoir need not be homogeneous, but generally has a certain distribution, and it should be noted accordingly Permeability of a petroleum deposit to an average permeability.
  • Permeability of 10 mD to 4 D preferably 100 mD to 2 D and particularly preferably 200 mD to 1 D.
  • the storage temperature is 30 to 150 ° C, preferably 40 to 100 ° C and particularly preferably 50 to 80 ° C.
  • an aqueous formulation which, in addition to water, comprises at least the described hydrophobically associating copolymer.
  • the formulation can be prepared in fresh water but also in salts containing water.
  • seawater can be used or it can be used promoted formation water, which is reused in this way.
  • the formulation is usually applied in seawater.
  • the polymer can advantageously be first dissolved in fresh water and the resulting solution diluted with formation water to the desired use concentration.
  • the formulation may preferably be prepared by initially charging the water, scattering the copolymer as a powder and mixing it with the water.
  • the aqueous formulation may of course comprise further components. Examples of other components include biocides, stabilizers or inhibitors.
  • the concentration of the copolymer is determined so that the aqueous formulation has the desired viscosity for the purpose.
  • the viscosity of the formulation should in any case 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 polymer in the formulation amounts to 0.01 to 2% by weight with respect to the sum of all components of the aqueous formulation.
  • the amount is 0.05 to 0.5 wt.%, Particularly preferably 0.04 to 0.2 wt.% And for example, about 0.1 wt.%.
  • Injecting the aqueous copolymer formulation can be done by conventional means.
  • the formulation can be injected by conventional pumps into one or more injection wells.
  • the injection wells are usually lined with cemented steel tubes, and the steel tubes, including the cement layer, are perforated at the desired location.
  • the formulation enters the petroleum formation through the perforation from the injection well.
  • the pressure applied by means of the pumps the volumetric flow of the formulation and thus also the shear stress with which the aqueous formulation enters the format are determined in a manner known in principle.
  • the shear stress on entering the formation can be calculated by the person skilled in the art in a manner known in principle on the basis of the law of Hagen-Poiseuille using the area through which the formation flows, the mean pore radius and the volume flow.
  • the average porosity of the formation can be determined in a manner known in principle by measurements on cores. Naturally, the shear stress is greater the larger the volume flow of aqueous copolymer formulation injected into the formation.
  • the shear rate when entering the aqueous polymer formulation into the formation is generally at least 30,000 s 1 , preferably at least 60,000 s 1 and particularly preferably at least 90,000 s
  • copolymers to be used according to the invention depending on the desired properties of the formulation to be injected.
  • the copolymers and preferred copolymers have already been described in the introduction. Particular preference is given to using copolymers which have a shear degradation of less than 10%, preferably less than 8%, for the process according to the invention.
  • R 4 is in the zugten variant of a hydrocarbon radical having 3 to 10 carbon atoms, in particular for an n-propyl radical.
  • k is a number from 20 to 30 and I is a number from 6 to 20, preferably 8 to 18.
  • the amount of monomers (a) of formula (Ia) is 0.2 to 5 wt. -%, preferably 0.5 to 2 wt .-%.
  • the preferred copolymer comprises 40 to 60% by weight of acrylamide and as the monomer (b2) 35 to 55% by weight of a sulfonic acid group-having monomer (b2), preferably 2-acrylamido-2-methylpropanesulfonic acid or salts thereof ,
  • Copolymers which are furthermore preferred for carrying out the process likewise comprise 0.2 to 5% by weight, preferably 0.5 to 2% by weight, of monomers (a) of the general formula (Ia) and 30 to 40% by weight of acrylamide. They additionally comprise 25 to 35% by weight of at least one sulfonic acid group-containing monomer (b2), preferably 2-acrylamido-2-methylpropanesulfonic acid or salts thereof and 25 to 35% by weight of at least one cationic monomer containing ammonium ions, preferably salts of 3 Trimethylammonium propyl (meth) acrylamides and 2-trimethylammonium ethyl (meth) acrylates.
  • monomers (a) of the general formula (Ia) and 30 to 40% by weight of acrylamide additionally comprise 25 to 35% by weight of at least one sulfonic acid group-containing monomer (b2), preferably 2-acrylamido-2-methylpropanesulfonic acid or salts thereof and 25 to 35% by
  • the shear stability or shear degradation of polymers for tertiary oil recovery can in principle be measured by means of a core flooding experiment. Due to the high cost of a core flooding experiment, the American Petroleum Institute has defined a simplified standard test in which the polymer solution is sheared in a capillary, comparing the viscosity of the solution before and after shear loading. This test is used in the context of the present invention.
  • Shear degradation of the copolymers is performed by means of a capillary shear test according to API RP 63, entitled “Recommended Practices for Evaluation of Polymers Used in Enhanced Oil Recovery Operations", chapter 6.6 “Evaluation of shear stability of polymer solutions” issued by the American Petroleum Institute at 01 .06.1990 determined.
  • the apparatus for measuring shear degradation consists of a steel cylinder with compressed gas connection (nitrogen) for receiving the polymer solution to be measured, pressure relief valve, venting cock and an outlet valve to which capillaries of different diameters can be attached.
  • the steel cylinder can be subjected to pressure from a nitrogen bomb or a compressed gas line.
  • the essential elements of the apparatus used are shown schematically in Figure 2. It consists of a pressure vessel (2) with a volume of about 1, 5 I, which has an outlet valve (3), a gas inlet (1). Below the outlet valve (3) a replaceable capillary (4) is mounted. A receptacle (5) serves to receive the polymer solution forced through the capillary. Unless otherwise stated below, the capillary used for the measurement has a length of 200 mm and an inner diameter of 0.6 mm.
  • the gas inlet valve can be unscrewed to fill the apparatus with polymer solution.
  • the outlet valve (3) of the apparatus used is closed, the pressureless apparatus is filled with the polymer solution to be measured (about 800 ml) and the apparatus is closed again.
  • the desired measuring pressure is set and the desired measuring pressure is applied to the apparatus.
  • the outlet valve (3) is opened.
  • the polymer solution then flows through the capillary into the collecting vessel (5).
  • a measuring vessel is held in the jet of the polymer solution, and about 60 to 100 g of the solution are collected. After completion of the collection, the measuring vessel is again pulled out of the jet of the polymer solution. With a stopwatch the time to capture the polymer solution is determined and it is determined in each case the mass of the collected polymer solution.
  • Shear degradation is the percentage decrease in viscosity of the polymer solution after shearing as compared to the solution before shearing.
  • the percent shear degradation is calculated from the measured viscosities before and after, as follows: ⁇ before - T
  • the shear degradation is measured at shear rates / s in the range of 1 to 100,000 80000 1 s.
  • the shear rates can be adjusted at the same concentration of the polymer solution in a series of experiments by changing the pressure in the desired range.
  • the viscosity measurements were carried out at room temperature with a Brookfield Viscometer LVDV-UL at a shear rate of 7 s -1 .
  • H 2 C CH-O- (CH 2) 4-O - (- CH 2 -CH 2 -O-) 22 - (- CH 2 -CH (C 3 H 7) -O-) i 2 -H
  • the product has an OH number of 31, 9 mg KOH / g (theory: 26.5 mg KOH / g).
  • the OH number is determined by the ESA method.
  • Example 1 Preparation of a copolymer of 2% by weight of monomer M 1, 50% by weight of acrylamide and 48% by weight of 2-acrylamido-2-methylpropanesulfonic acid
  • the monomer solution After adjusting the pH with a 20% or 2% sulfuric acid solution to a value of 6 and adding the remaining water, the monomer solution is adjusted to the starting temperature of 5 ° C.
  • the total amount of water is such that - after the polymerization - a solids concentration of about 30 to 36 wt.% Is reached.
  • the solution is transferred to a thermos flask, a thermocouple is mounted for temperature recording and purged with nitrogen for 30 minutes.
  • the polymerization is then carried out by adding 1.6 ml of a 10% aqueous solution of a water-soluble, cationic azo initiator 2,2'-azobis (2-amidinopropane) dihydrochloride (Wako V-50), 0.12 ml a 1% aqueous solution of tert-butyl hydroperoxide and 0.24 ml of a 1% sodium sulfite solution started. After addition of the initiators, the temperature rises within 15 to 30 minutes to about 80 ° C. After 30 minutes, the reaction vessel is placed in a drying oven of about 80 ° C. for about 2 hours to complete the polymerization. The total duration of the polymerization is about 2 hours to 2.5 hours.
  • a gel block is obtained, which is comminuted with the help of a meat grinder after completion of the polymerization.
  • the resulting gel granules are dried in a fluidized bed dryer at 55 ° C for two hours. This gives a white, hard granules, which is converted by means of a centrifugal mill in a powdery state. This gives a copolymer having a weight average molecular weight of about 1 * 10 6 g / mol to 30 * 10 6 g / mol.
  • Example 5 The procedure is as in Example 1, except that in addition the cationic monomer DIMAPAQUAT (used as a 60% aqueous solution) is used in the amounts indicated above.
  • the molar ratio (b2) / (b3) is 0.94.
  • the viscosity of the solutions was first determined, then the capillary shear test was carried out, and the sheared solution obtained again measured the viscosity.
  • a first viscosity measurement was carried out about four hours after the shearing load and, in addition, a test measurement was carried out again after 2 days in order to check that the viscosity loss was indeed irreversible.
  • Some polymer solutions were sheared a second time for control purposes after the first shear. All measurements were carried out at room temperature.
  • measurements were carried out at a shear rate in the range of 80000 s 1 to 100000 s 1 .
  • measurements were carried out at a shear rate of more than 100,000 s -1 .
  • the Examples and Comparative Example show that the shear degradation of the copolymers containing hydrophobically associating monomers (a) is significantly lower than that of the comparative polymers without monomers (a). Surprisingly, even with some copolymers, an increase in shear viscosity was observed. Without being bound to any particular theory, we suspect that this effect could be evoked by a conformational change. The polymer solutions which showed an increase in viscosity were then sheared again for testing purposes. On the second shearing, they show a low shear rate of significantly less than 8%.
  • Table 2 Summary of results of shear tests at a shear rate of more than 100,000 s 1

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Abstract

Procédé d'extraction de pétrole consistant à injecter une formulation aqueuse contenant au moins un copolymère associatif hydrophobe et hydrosoluble à travers aux moins un forage d'injection dans un gisement pétrolifère et à extraire du pétrole brut du gisement pétrolifère à travers au moins un forage de production, le copolymère associatif hydrophobe et hydrosoluble comprenant au moins un acrylamide ou des dérivés de celui-ci, un monomère comprenant des groupes anioniques et un monomère qui peut provoquer l'association du copolymère. L'invention porte également sur un copolymère associatif hydrophobe et hydrosoluble qui est adapté à la réalisation de ce procédé par sa faible sensibilité au cisaillement.
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Families Citing this family (48)

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Publication number Priority date Publication date Assignee Title
US8763698B2 (en) 2011-04-08 2014-07-01 Basf Se Process for producing mineral oil from underground formations
EA024382B1 (ru) * 2011-04-08 2016-09-30 Басф Се Способ добычи нефти из подземных пластов
CN103772713B (zh) * 2012-10-17 2016-05-18 中国石油化工股份有限公司 接枝改性聚丙烯酰胺及其制备方法
CA2920987A1 (fr) 2013-08-22 2015-02-26 Basf Se Compositions stabilisees renfermant des polymeres acrylamides et procede de production tertiaire d'huile minerale employant lesdites compositions
BR112016013465B1 (pt) 2013-12-13 2023-01-24 Basf Se Processo para produzir petróleo mineral, copolímero solúvel em água, e, formulação aquosa
EP2933271B1 (fr) * 2014-04-15 2016-03-23 Basf Se Procédé de fabrication de homo- ou copolymères solubles dans l'eau comprenant du (méth)acrylamide
WO2015189060A1 (fr) * 2014-06-11 2015-12-17 Basf Se Macromonomères amphiphiles, procédés de préparation de macromonomères amphiphiles, copolymères contenant des macromonomères amphiphiles et leur utilisation pour la récupération assistée du pétrole
US10450500B2 (en) 2015-01-12 2019-10-22 Ecolab Usa Inc. Thermally stable polymers for enhanced oil recovery
CN107531939B (zh) 2015-02-20 2019-11-12 巴斯夫欧洲公司 制备稳定化聚丙烯酰胺的方法
MX2017010687A (es) 2015-02-20 2017-11-17 Basf Se Proceso para producir composiciones de poliacrilamida estabilizadas.
MX2018008704A (es) * 2016-01-13 2018-09-21 Basf Se Metodo para la recuperacion terciaria de petroleo por medio de un polimero de asociacion hidrofoba.
WO2017162545A1 (fr) 2016-03-24 2017-09-28 Basf Se Procédé pour la préparation d'atbs et de copolymères correspondants
EP3448898A1 (fr) 2016-04-26 2019-03-06 Basf Se Procédé de préparation d'une solution aqueuse de polyacrylamide
WO2017186685A1 (fr) 2016-04-26 2017-11-02 Basf Se Procédé de préparation d'une solution aqueuse de polyacrylamide
WO2017186697A1 (fr) 2016-04-26 2017-11-02 Basf Se Procédé de préparation d'une solution aqueuse de polyacrylamide
AR113374A1 (es) 2017-10-25 2020-04-22 Basf Se Un proceso y aparato para producir soluciones acuosas de polímero
US11384177B2 (en) 2017-10-25 2022-07-12 Basf Se Process for producing aqueous polyacrylamide solutions
WO2019081004A1 (fr) 2017-10-25 2019-05-02 Basf Se Procédé de production de solutions aqueuses de polyacrylamide
AR113378A1 (es) 2017-10-25 2020-04-22 Basf Se Proceso para producir soluciones acuosas de poliacrilamida
CA3076553A1 (fr) 2017-10-25 2019-05-02 Basf Se Procede de production de solutions aqueuses de polyacrylamide
WO2019081003A1 (fr) 2017-10-25 2019-05-02 Basf Se Procédé de production de solutions aqueuses de polyacrylamide
AR113390A1 (es) 2017-10-25 2020-04-29 Basf Se Proceso para producir poliacrilamidas de asociación hidrófoba
WO2019081327A1 (fr) 2017-10-25 2019-05-02 Basf Se Procédé de production de solutions aqueuses de polyacrylamide
WO2019081321A1 (fr) 2017-10-25 2019-05-02 Basf Se Procédé de production de solutions aqueuses de polyacrylamide
EP3728512A1 (fr) * 2017-12-19 2020-10-28 Rhodia Operations Formulations aqueuses de tensioactifs et polymeres associatifs pour la recuperation assistee du petrole
EP3587533A1 (fr) 2018-06-22 2020-01-01 Basf Se Polymères à auto-protection pour la récupération de pétrole
AR115855A1 (es) 2018-07-30 2021-03-03 Ecolab Usa Inc Polielectrolitos de rápido disolución, hidrosolubles y modificados hidrofóbicamente
CA3108176A1 (fr) 2018-07-30 2020-02-06 Championx Usa, Inc. Modificateurs de rheologie solubles dans l'eau, a dissolution rapide et tolerants au sel
WO2020079124A1 (fr) 2018-10-18 2020-04-23 Basf Se Procédé de production de compositions de polyacrylamide aqueuses
WO2020079119A1 (fr) 2018-10-18 2020-04-23 Basf Se Procédé de fourniture de concentrés de polyacrylamide aqueux
WO2020079123A1 (fr) 2018-10-18 2020-04-23 Basf Se Procédé de fracturation de formations souterraines à l'aide de solutions aqueuses comportant des copolymères à association hydrophobe
CA3116246A1 (fr) 2018-10-18 2020-04-23 Basf Se Procede de production de (meth)acrylate d'ammonium
US11725102B2 (en) 2018-10-18 2023-08-15 Basf Se Method of providing homogeneous aqueous polyacrylamide concentrates and use thereof
US11608468B2 (en) 2018-10-18 2023-03-21 Basf Se Process of fracturing subterranean formations
AR116742A1 (es) 2018-10-18 2021-06-09 Basf Se Proceso para producir un concentrado acuoso de poliacrilamida
WO2020216433A1 (fr) 2019-04-23 2020-10-29 Basf Se Procédé et appareil pour la production de compositions aqueuses de polymères solubles dans l'eau
WO2021037579A1 (fr) 2019-08-26 2021-03-04 Basf Se Procédé de fabrication de polyacrylamides contenant de la nvp
WO2021037578A1 (fr) 2019-08-26 2021-03-04 Basf Se Procédé de fabrication de nvp contenant des polyacrylamides
WO2021175760A1 (fr) 2020-03-06 2021-09-10 Basf Se Procédé de fracturation de formations souterraines
WO2021175757A1 (fr) 2020-03-06 2021-09-10 Basf Se Procédé de fabrication d'un prémélange de polyacrylamide aqueux
AU2021245007A1 (en) 2020-03-26 2022-12-01 Basf Se Process and plant for manufacturing aqueous polyacrylamide gels
WO2021204850A1 (fr) 2020-04-09 2021-10-14 Basf Se Synthèse biocatalytique de mélanges de monomères pour la fabrication de polyacrylamide
WO2021209149A1 (fr) 2020-04-17 2021-10-21 Basf Se Procédé et dispositifs de production de fluides aqueux de traitement de puits de forage
WO2021209150A1 (fr) 2020-04-17 2021-10-21 Basf Se Procédés et dispositifs permettant la production de fluides aqueux de traitement de puits de forage
WO2021209148A1 (fr) 2020-04-17 2021-10-21 Basf Se Processus de fabrication de liquide d'injection aqueux
CA3171596A1 (fr) 2020-05-04 2021-11-11 Dennis Loesch Procede et appareil pour la production de compositions aqueuses de polymeres hydrosolubles
WO2022106308A1 (fr) 2020-11-23 2022-05-27 Basf Se Procédé de fabrication de copolymères contenant de la nvp hydrosolubles sous forme de poudre
WO2023156293A1 (fr) 2022-02-17 2023-08-24 Basf Se Procédé et dispositif améliorés de fabrication de fluides de traitement aqueux de puits de forage

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA832277A (en) 1970-01-20 A. Williams Sherrod Waterflood process employing thickened water
US4702854A (en) * 1983-05-02 1987-10-27 The Dow Chemical Company Water-based hydraulic fluids comprising poly-oxazines or poly-oxazolines
US4921902A (en) * 1984-02-02 1990-05-01 The Dow Chemical Company Hydrophobie associative composition containing a polymer of a water-soluble monomer and an amphiphilic monomer
DE3925220C1 (fr) * 1989-07-29 1991-01-03 Th. Goldschmidt Ag, 4300 Essen, De
DE4325237A1 (de) 1993-07-28 1995-02-02 Basf Ag Verfahren zur Herstellung von Alkoxylierungsprodukten in Gegenwart von mit Additiven modifizierten Mischhydroxiden
US5874495A (en) 1994-10-03 1999-02-23 Rhodia Inc. Polymers useful as PH responsive thickeners and monomers therefor
US6166690A (en) 1999-07-02 2000-12-26 Sensor Systems, Inc. Adaptive nulling methods for GPS reception in multiple-interference environments
DE10037629A1 (de) 2000-08-02 2002-02-14 Skw Bauwerkstoffe Deutschland Wasserlösliche oder wasserquellbare sulfogruppenhaltige assoziativverdickende Copolymere, Verfahren zu deren Herstellung und deren Verwendung
DE10243361A1 (de) 2002-09-18 2004-04-01 Basf Ag Alkoxylatgemische und diese enthaltende Waschmittel
DE102004007501A1 (de) * 2004-02-13 2005-09-01 Basf Ag Amphiphile Blockcopolymere enthaltende wässrige Polymerdispersionen, Verfahren zu ihrer Herstellung und ihre Verwendung
DE102004032304A1 (de) 2004-07-03 2006-02-16 Construction Research & Technology Gmbh Wasserlösliche sulfogruppenhaltige Copolymere, Verfahren zu deren Herstellung und ihre Verwendung
CA2760734C (fr) 2009-05-20 2017-05-16 Basf Se Copolymeres associatifs a groupes hydrophobes
EP2287216A1 (fr) 2009-08-06 2011-02-23 Basf Se Polymères associatifs hydrosolubles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012069478A1 *

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RU2013128418A (ru) 2014-12-27
WO2012069478A1 (fr) 2012-05-31
AR083976A1 (es) 2013-04-10
CN103328602A (zh) 2013-09-25
BR112013012869A2 (pt) 2016-09-06
CA2818847A1 (fr) 2012-05-31
MX2013005518A (es) 2013-07-05

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