WO2015140102A1 - Procédé de production de pétrole brut tertiaire à l'aide d'alkoxylates à groupe propylénoxy moyen - Google Patents

Procédé de production de pétrole brut tertiaire à l'aide d'alkoxylates à groupe propylénoxy moyen Download PDF

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WO2015140102A1
WO2015140102A1 PCT/EP2015/055428 EP2015055428W WO2015140102A1 WO 2015140102 A1 WO2015140102 A1 WO 2015140102A1 EP 2015055428 W EP2015055428 W EP 2015055428W WO 2015140102 A1 WO2015140102 A1 WO 2015140102A1
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surfactant
general formula
oil
carbon atoms
mixture
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PCT/EP2015/055428
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German (de)
English (en)
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Christian Bittner
Günter OETTER
Sebastian Alexander WEISSE
Hans-Christian Raths
Gabriela ALVAREZ JÜRGENSON
Marcel Patrik KIENLE
Stefan Stein
Sophia Ebert
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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
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584—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 surfactants

Definitions

  • the invention relates to a process for producing oil by means of Winsor Type III microemulsion flooding, in which an aqueous surfactant formulation containing a surfactant mixture is injected through injection bores into an oil reservoir and the crude oil is removed from the deposit through production wells.
  • the invention further relates to a nonionic surfactant, a surfactant mixture containing the nonionic surfactant, a surfactant formulation containing the surfactant mixture, and concentrates of the surfactant or of the surfactant mixture.
  • a deposit contains more or less saline water.
  • Oil production generally distinguishes between primary, secondary and tertiary production.
  • primary production after drilling the deposit, petroleum automatically streams through the borehole due to the inherent pressure of the deposit.
  • secondary funding 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.
  • Tertiary oil production includes, on the one hand, heat processes in which hot water or superheated steam is introduced into the oil. is squeezed. As a result, the viscosity of the oil is reduced. As flooding medium also gases such as CO2 or nitrogen can be used.
  • Tertiary oil production also includes processes which use suitable chemicals as auxiliaries. With these, the situation can be influenced towards the end of the flood and thus also promote oil that was previously held in the rock formation.
  • ⁇ is the viscosity of the oil mobilizing the oil
  • v is the Darcy velocity (flow per unit area)
  • ⁇ is the interfacial tension between petroleum mobilizing liquid and petroleum
  • ⁇ is the contact angle between petroleum and rock (C. Melrose, CF Brandner, J. Canadian Petr. Techn. 58, October-December, 1974).
  • C. Melrose, CF Brandner, J. Canadian Petr. Techn. 58, October-December, 1974 The higher the capillary number, the greater the mobilization of the oil and thus also the degree of de-oiling.
  • the capillary number is in the range of about 10 -6 at the end of the secondary petroleum production and that for the mobilization of additional petroleum it is necessary to increase the capillary number to about 10 -3 to 10 -2 .
  • Winsor type III microemulsion flooding the so-called Winsor type III microemulsion flooding.
  • the injected surfactants are expected to form a Winsor Type III microemulsion with the water and oil phases present in the reservoir.
  • a Winsor Type III microemulsion is not an emulsion with particularly small droplets but a thermodynamically stable, liquid mixture of water, oil and surfactants. Its three advantages are that it achieves a very low interfacial tension ⁇ between oil and aqueous phase,
  • the Winsor Type III microemulsion is in equilibrium with excess water and excess oil. Under these conditions, the microemulsion formation, the surfactants demonstrate the oil-water interface and lower the interfacial tension ⁇ values of ⁇ 10 "2 mN / m (ultralow interfacial tension) is particularly preferred in. In order to achieve an optimum result, the proportion of microemulsion should Naturally, the system water microemulsion oil should be as large as possible at a defined amount of surfactant, since in this way the lower interfacial tensions can be achieved.
  • the oil droplets can change in shape (the interfacial tension between oil and water is lowered so far that no longer the state of the smallest boundary surface is desired and not the spherical shape is preferred) and by the flood water through the Squeeze capillary openings.
  • Winsor Type III microemulsion will be formed if there is an excess amount of surfactant. It thus represents a reservoir for surfactants, which accomplish a very low interfacial tension between oil and water phase. Due to its low viscosity, Winsor Type III microemulsion migrates through the porous reservoir rock during the flood process. Emulsions, on the other hand, can get stuck in the porous matrix and clog reservoirs.
  • the surfactant from the microemulsion can significantly lower the interfacial tension of this new interface and result in mobilization of the oil (for example, by deformation of the oil droplets).
  • the oil droplets can then combine to form a continuous oil bank. This has two advantages:
  • the released surfactant may thereafter mobilize residual oil remaining in the formation as described above.
  • Winsor Type III microemulsion flooding is an extremely efficient process and, unlike an emulsion flooding process, requires significantly less surfactant.
  • the surfactants are usually optionally injected together with cosolvents and / or basic salts (optionally in the presence of chelating agents). Subsequently, a solution of thickening polymer is injected for mobility control.
  • Another variant is the injection of a mixture of thickening polymer and surfactants, cosolvents and / or basic salts (optionally with chelating agent) and subsequently a solution of thickening polymer for mobility control. These solutions should usually be clear to avoid blockage of the reservoir.
  • Suitable surfactants for tertiary oil production should be the interfacial tension between water and oil (usually about 20 mN / m) to particularly low values of less than 10 ".
  • mixtures of surfactants have frequently been proposed, in particular mixtures of anionic and nonionic surfactants.
  • AO alkylene oxide having 2 to 6 carbon atoms
  • anionic surfactants of the type C8-C20-AO-sulfate or C8-C20-AO-sulfonate disclosed The indication of the alkylene oxides is only very general in the context of the disclosure of US Pat. No. 3,890,239.
  • CA 1, 026,666 describes the combination of alpha-olefinsulfonates with alkoxylates of the type RPhO- (R'O) x -H for tertiary mineral oil extraction, where R is an alkyl radical having 6 to 15 carbon atoms, R'O is alkoxy groups having 2 to 20 carbon atoms and x is a number from 2 to 20.
  • WO 09/124922 A1 describes the use of surfactants of the type 1C17H35O- (CH 2 CH (R 2 ) O) n (CH 2 CH 2 O) m H for tertiary mineral oil extraction, where R 1 has a degree of branching of 2.8 to 3.5, R 2 for one Hydrocarbon radical having 1 to 10 carbon atoms, n is a number from 0 to 15 and m is a number from 1 to 20.
  • the alkoxy and ethoxy groups may be arranged randomly, alternately or in blocks.
  • the oil production is proportional to the capillary number. This is the higher the lower the interfacial tension between oil and water. Low interfacial tensions are the more difficult to achieve the higher the average number of carbon atoms in the crude oil molecules.
  • surfactants are suitable which have a long alkyl radical. The longer the alkyl radical is, the better the interfacial tensions can be reduced.
  • the availability of such compounds is very limited.
  • alkyl ethoxylates having more than 10 ethyleneoxy units or alkyl ethoxylate-containing formulations containing alkyl ethoxylates having more than 10 ethyleneoxy units are present in a waxy to solid state at a temperature of 20 ° C. Accordingly, they are in a solid or waxy state at the temperatures prevailing in cold or temperate climates. This complicates, inter alia, the preparation of the surfactant formulations used in tertiary mineral oil production. Thus, such alkyl ethoxylates would have to be melted on site.
  • alkyl ethoxylates in the form of concentrates is also problematic since these concentrates have a comparatively low storage stability, especially at low temperatures.
  • the preparation of concentrates comprising a lower alcohol as a solvent is complicated because the correct mixing ratio must be found to solidify the concentrate, or in the worst case, the crystallization of the alkyl ethoxylate in a sometimes several weeks of transport or at a storage for months at temperatures less than 20 ° C.
  • These disadvantageous properties lead to increased technical complexity when using alkyl ethoxylate concentrates in tertiary mineral oil production. For example, heating must take place at the reservoir surface or the concentrate during transport in order to ensure the formability or usability of the concentrate.
  • An object of the present invention is therefore to provide an improved process for tertiary mineral oil production. Furthermore, it was an object of the invention to provide surfactants or surfactant mixtures and concentrates thereof for processes for oil production, which are characterized by improved handling, especially in temperate and cold climates. In particular, by the comparatively high Melting points and the low storage stability caused disadvantages when using known alkyl ethoxylates are avoided.
  • a process for tertiary mineral oil production by Winsor Type III microemulsion flooding comprising: forcing an aqueous surfactant formulation comprising a surfactant mixture to lower the interfacial tension between oil and water to ⁇ 0.1 mN / m, injected through at least one injection well into an oil reservoir, and the deposit is taken by at least one production well crude oil, characterized in that the surfactant mixture
  • At least one anionic surfactant (A) comprising at least one functional group selected from the group consisting of sulfate, sulfonate and carboxylate;
  • R is a linear or branched, saturated or unsaturated, aliphatic, aromatic-aliphatic or aliphatic-aromatic hydrocarbon radical having from 10 to 36 carbon atoms;
  • PO is propyleneoxy
  • x is a number from 5 to 25;
  • y is a number from 1 to 9;
  • z is a number from (x-4) to (x + 4) but is at least 5 and at most 25; wherein the sum of x + y + z is a number from 1 1 to 49; and wherein the units (EO) x, (PO) y and (EO) z are arranged blockwise in the order given in formula (I).
  • Another aspect of the invention relates to a nonionic surfactant (B) of the formula (I).
  • a further aspect of the present invention relates to a particularly efficient surfactant mixture for use for surfactant flooding, which comprises at least one anionic surfactant (A) and at least one nonionic surfactant (B) of the general formula (I) as indicated above.
  • Another aspect of the present invention relates to an aqueous surfactant formulation comprising the surfactant mixture according to the invention.
  • a further aspect of the invention relates to an aqueous concentrate of the surfactant mixture according to the invention, and to an aqueous concentrate of the at least one surfactant (B) of the general formula (I).
  • a further aspect of the present invention relates to the use of the nonionic surfactant, a surfactant mixture containing the nonionic surfactant, a surfactant formulation containing the surfactant mixture, and concentrates of the surfactant or surfactant mixture in oil production by means of Winsor Type III microemulsion flooding.
  • the surfactant mixture according to the invention containing at least one nonionic surfactant (B) of the general formula (I) with a propyleneoxy middle block than with surfactants in which propyleneoxy present - Units are not arranged as a middle-class block.
  • the at least one surfactant (B) of the general formula (I) can be provided for the process according to the invention in the form of a cold-stable, liquid concentrate.
  • the surfactant (B) has a low melting point and at the same time a comparatively high cloud point.
  • an aqueous surfactant formulation comprising a surfactant mixture containing at least one anionic surfactant (A) and at least one nonionic surfactant (B) of the general formula (I) is used .
  • the surfactant formulation may further comprise other surfactants and / or other components.
  • the interfacial tension between oil and water is brought to values ⁇ 0.1 mN / m, preferably to ⁇ 0.05 mN / m, particularly preferably to ⁇ by the use of the surfactant mixture according to the invention 0.01 mN / m lowered.
  • the interfacial tension between oil and water becomes particularly in the range of 0.1 mN / m to 0.0001 mN / m, preferably values in the range of 0.05 mN / m to 0.0001 mN / m preferably lowered to values in the range of 0.01 mN / m to 0.001 mN / m.
  • the at least one surfactant (A) is an anionic surfactant comprising at least one functional group selected from the group consisting of sulfate, sulfonate and carboxylate.
  • the at least one anionic surfactant (A) is a surfactant of the general formula (II)
  • R 1 is a linear or branched, saturated hydrocarbon radical having 12 to 36 carbon atoms; R 2 independently represent a linear, saturated hydrocarbon radical having 1 to 5
  • n is a number from 0 to 99;
  • n is a number from 0 to 99;
  • X represents an -SO 3 - or -Ch CC group
  • M + is a cation; wherein the sum of m + n is a number from 3 to 99; and where the units
  • surfactants (A) of the general formula (I I) present in the surfactant formulation and the surfactant mixture, as a result of the preparation.
  • the radical R 1 is a linear or branched saturated hydrocarbon radical having 12 to 36 carbon atoms, preferably 14 to 25 carbon atoms, particularly preferably 16 to 18 carbon atoms.
  • the radical R 1 is 1SO-C 17 H 35 or a commercial fatty alcohol mixture consisting of linear C 16 H 33 and C 18 H 37, derived from the commercially available C 16 Guerbet alcohol 2-hexyldecyl-1-ol, derived from the commercially available Cis-Guerbet alcohol 2-octyldodecyl-1-ol, derived from the commercially available C24 Guerbet alcohol 2-decyl-tetradecanol, derived from the commercially available C28 Guerbet alcohol 2-dodecyl-hexadecanol or derived from the commercially available Neodol 67 from Shell (Ci 6 Ci 7 alcohol).
  • a branched aliphatic hydrocarbon radical R 1 generally has a degree of branching of 0, 1 to 5.5, preferably 1 to 3.5.
  • degree of branching is hereby defined in a manner known in principle as the number of methyl groups in a molecule of the underlying hydrocarbon radical minus 1.
  • the mean degree of branching is the statistical mean of the degrees of branching of all molecules in a sample.
  • mixtures or surfactant formulations comprising a plurality of surfactants (A) of the general formula (II), the numbers m and n are average values over all molecules of the surfactants, since in the alkoxylation of an alcohol with alkylene oxides each obtain a certain distribution of chain lengths This distribution can be in principle known by the so-called polydispersity D could be described.
  • D M w / M n is the quotient of the weight average molecular weight and the number average the molar mass.
  • the polydispersity can be determined by methods known to those skilled in the art, for example by gel permeation chromatography.
  • R 2 independently represents a linear saturated hydrocarbon radical having 1 to 5 carbon atoms, for example, a methyl, ethyl, n-propyl, iso-propyl, n-butyl, n - or iso-pentyl radical.
  • R 2 is a hydrocarbon radical having 1 to 3 carbon atoms, in particular a methyl, ethyl or n-propyl radical.
  • the alkyleneoxy moiety - (CH 2 CH (R 2 ) -O) - is preferably a propyleneoxy, - (CH 2 CH (CH 3 ) -O) -; Butyleneoxy-, - (CH 2 CH (CH 2 CH 3) -O) -; or pentylenoxy unit, - (CH 2 CH (CH 2 CH 2 CH 3) -O) -.
  • the alkyleneoxy moiety - (CH 2 CH (R 2 ) -O) - is a propyleneoxy moiety - (CH 2 CH (CH 3 ) -O) -.
  • m is a number from 0 to 99, preferably from 1 to 20, particularly preferably from 5 to 9.
  • n is a number from 0 to 99, preferably from 0.1 to 30, particularly preferably from 2 to 10.
  • the sum m + n is a number which is in the range of 3 to 99, preferably in the range of 5 to 50, particularly preferably in the range of 7 to 19.
  • X represents an -SO 3 or -Ch CC group, more preferably a -SCV group.
  • Y represents a single bond or a divalent linking group - (C 1 H 21) - wherein I is a natural number from 1 to 5.
  • Y is a methylene, -CH 2 -, ethylene, -CH 2 CH 2 - or propylene group, "Ch Ch Cl-.
  • Y represents a single bond and X "represents an -SO group, thereby resulting in a surfactant having a sulfate group as a functional end group.
  • Y stands for a single bond or a divalent, linking group (C1H21) -, where I is a natural number from 1 to 5, preferably 1 to 3, particularly preferably 1 and X is a -Ch CC group.
  • Y is a single bond and X is a -Ch CC group.
  • M + is a cation which is preferably selected from the group consisting of Na + , K + , Li + , NH 4 + , H + , Mg 2+ and Ca 2+ .
  • M + is Na + .
  • the at least one anionic surfactant (A) of the general formula (II) is C 6 C 8 - O - 7 PO - S0 3 Na, C 6 C 7 - O - PO 7 S0 3 Na, C 6 Cie - O
  • the at least one anionic surfactant (A) is an alkylbenzenesulfonate wherein the alkyl moiety has 10 to 30 carbon atoms, preferably 12 to 18 carbon atoms; or an olefin sulfonate having 12 to 28 carbon atoms.
  • the alkylbenzenesulfonate is particularly preferably dodecylbenzenesulfonate, tetradecylbenzenesulfonate, hexadecylbenzenesulfonate, hexadecyltoluenesulfonate or octadecylbenzenesulfonate.
  • Preferred olefin sulfonates are Cu-alpha-olefinsulfonate, Ci6-alpha-olefinsulfonate and internal C15C18, C 2 oC 24 and C 2 4C 2 8-olefinsulfonates.
  • mixtures of at least one alkylbenzenesulfonate and at least one olefinsulfonate are possible, and mixtures of at least one alkylbenzenesulfonate and / or at least one olefinsulfonate with one or more surfactants (A) of the general formula (II).
  • the surfactant mixture according to the invention contains at least one surfactant (B) of the general formula (I)
  • the radical R in the surfactant (B) according to the invention of the formula (I) according to the invention is a linear or branched, saturated or unsaturated, aliphatic, aromatic-aliphatic or aliphatic-aromatic hydrocarbon radical having 10 to 36 carbon atoms. It is preferably a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical having 10 to 28 carbon atoms.
  • the radical R is preferably a linear or branched, saturated aliphatic hydrocarbon radical having 10 to 28 carbon atoms, preferably having 15 to 22 carbon atoms, particularly preferably having 16 to 18 carbon atoms.
  • the radical R is preferably a linear or branched alkyl radical having 10 to 28 carbon atoms, preferably having 15 to 22 carbon atoms, particularly preferably having 16 to 18 carbon atoms.
  • the radical R is a branched, saturated, aliphatic hydrocarbon radical having 12 to 28 carbon atoms, preferably 15 to 22, particularly preferably 16 to 18 carbon atoms.
  • R is a branched, saturated, hydrocarbon radical having an average degree of branching of 0.9 to 3.9, preferably from 1, 0 to 3.5.
  • degree of branching is defined here as already in connection with surfactants (A) of the formula (I).
  • R is selected from the group consisting of 1C13H27-, 1C13H27-, 1C15H31-, n-Ci6H 3 3-, 1C16H33-, 1C17H35-, n-Ci8H 7- 3, 2-hexyldecyl and 2- octyldodecyl.
  • x, y and z are integers. However, it will be apparent to those skilled in the art of polyalkoxylates that these definitions are each defining a single surfactant (B).
  • the numbers x, y and z are averages over all molecules of the surfactants, as in the alkoxylation of alcohol with ethylene oxide or propylene oxide in each case a certain distribution of chain lengths is obtained.
  • This distribution can be described in a manner known in principle by the so-called polydispersity D. Details have already been given in connection with the surfactants (A) of the general formula (II).
  • x is a number from 5 to 25, preferably from 6 to 15, particularly preferably from 8 to 11.
  • y is a number from 1 to 9, preferably from 1 to 5.
  • z is a number from (x-4) to (x + 4), but is at least 5 and at most 25, preferably from 6 to 15, particularly preferably from 8 to 11.
  • the number of (EO) x units corresponds to the number of (EO) z units.
  • the sum x + y + z is a number in the range of 1 1 to 49.
  • y is a number from 1 to 3
  • the sum of x + y + z gives a number from 1 1 to 25.
  • the units (EO) x , (PO) y and (EO) z are arranged blockwise in the order given in formula (I).
  • the surfactant (B) of the general formula (I) is therefore a surfactant which contains a medium propyleneoxy block (PO) y between two ethyleneoxy blocks (EO) x and (EO) z.
  • Block structure in the context of the present invention means that the blocks to at least 85 mol%, preferably at least 90 mol%, more preferably at least 95 mol%, particularly preferably at least 99 mol%, based on the total amount of substance of the respective Blocks, are composed of the corresponding units. This means that the respective blocks, in addition to the corresponding alkyleneoxy units, can have small amounts of other alkyleneoxy units.
  • the transition between the blocks may be abrupt or continuous, depending on the nature of the preparation.
  • a continuous transition there is still a transition zone between the blocks, which comprises monomers of both blocks.
  • the first ethyleneoxy block (EO) x may still contain small amounts of propyleneoxy units and the propyleneoxy block (PO) y small amounts of ethyleneoxy units, but these units are not statistically distributed over the block, but are arranged in said transition zone.
  • the ethyleneoxy block (EO) z may also contain small amounts of propyleneoxy units.
  • the transition between the blocks in the surfactant (B) of the general formula (I) is abrupt.
  • the surfactants (B) of the general formula (I) according to the invention preferably have a melting point of below 15 ° C.
  • the nonionic surfactants (B) according to the general formula (I) can be prepared in a manner known in principle by alkoxylation of corresponding alcohols R-OH.
  • the implementation of such alkoxylations is known in principle to the person skilled in the art. It is likewise known to the person skilled in the art that the molecular weight distribution of the alkoxylates obtained can be influenced by the reaction conditions, in particular by the choice of the catalyst.
  • the surfactants according to the general formula (I) can preferably be prepared by base-catalyzed alkoxylation.
  • the alcohol R-OH in a pressure reactor with alkali metal hydroxides, preferably potassium hydroxide (KOH), or with alkali metal such as sodium methylate (NaOMe), are added.
  • the alkoxylation of the alcohols R-OH can also be carried out by other methods, which lead to narrower molecular weight distributions than in the base-catalyzed synthesis.
  • double hydroxide clays as described in DE 4325237 A1
  • the alkoxylation is particularly preferably carried out using double metal cyanide catalysts (DMC catalysts).
  • DMC catalysts are disclosed, for example, in DE 10243361 A1, in particular in sections [0029] to [0041] and in the literature cited therein.
  • catalysts of the Zn-Co type can be used.
  • the catalyst is added to the alcohol R-OH, the mixture is dehydrated as described above and reacted with the alkylene oxides as described. It is usually not more than 250 ppm catalyst used with respect to the mixture. Due to this small amount of catalyst may remain in the product.
  • the alkoxylates of the general formula (I) can furthermore be prepared by acid-catalyzed alkoxylation.
  • the acids may be Bronsted or Lewis acids.
  • the catalyst can be added to the alcohol R-OH and the mixture is dehydrated as described above and reacted with the alkylene oxides as described.
  • the catalyst can be neutralized by addition of a base, for example KOH or NaOH, and filtered off as required.
  • the preparation of the surfactants (A) of the general formula (II) can first according to the procedure described above, starting from alcohols R 1 -OH, take place.
  • the conversion of the respective alkoxylates into the corresponding sulfates, sulfonates or carboxylates can be carried out, for example, in accordance with the methods described in WO 2009/124922.
  • the weight ratio of the at least one surfactant (A) to the at least one surfactant (B) of the formula (I) in the surfactant mixture according to the invention is preferably in the range from 51: 49 to 95: 5, more preferably from 60: 40 to 90: 10, furthermore preferably more preferably from 70:30 to 80:20.
  • the weight ratio of the at least one surfactant (A) to the at least one surfactant (B) of the formula (I) in the surfactant mixture according to the invention is also preferably in the range from 85: 15 to 90: 10th
  • the surfactant mixture according to the invention preferably contains 51 to 95% by weight, preferably 60 to 90% by weight, particularly preferably 70 to 80% by weight of at least one anionic surfactant (A) and 5 to 49% by weight, preferably 10 to 40 wt .-%, particularly preferably 20 to 30 wt .-% of at least one nonionic surfactant B of the general formula (I), wherein the weights are based on the total surfactant mixture.
  • the invention includes surfactant mixture according to the invention 85 to 90 wt .-% of at least one anionic surfactant (A) and 10 to 15 wt .-% of at least one nonionic surfactant B of the general formula (I), wherein the weights are based on the total surfactant mixture.
  • the sum of the weight proportions of the at least one surfactant (A) and the at least one surfactant (B) of the general formula (I) gives 100 wt .-%.
  • the surfactant mixture according to the invention can preferably be used for the surfactant flooding of deposits. It is particularly suitable for Winsor type III microemulsion flooding (flooding in the Winsor III area or in the area of existence of the bicontinuous microemulsion phase). The technique of microemulsion flooding has already been described in detail at the beginning.
  • a suitable aqueous formulation of the surfactant mixture containing at least one surfactant (A) and at least one surfactant (B) of the general formula (I) is injected through at least one injection well into the oil reservoir and the deposit by at least one Production well crude oil taken.
  • the term "crude oil” in this context does not mean phase-pure oil, but means the usual crude oil-water emulsions, as a rule, a deposit is provided with several injection wells and several production wells.
  • the main effect of the surfactants lies in the reduction of the interfacial tension between water and oil - desirably to values significantly ⁇ 0.1 mN / m.
  • surfactant flooding or, preferably, the Winsor type III "microemulsion flooding”
  • water flooding can be injected into the formation ("water flooding") to maintain the pressure or, preferably, a highly viscous aqueous solution of a strongly thickening acting polymer ("polymer flooding”).
  • polymer flooding a highly viscous aqueous solution of a strongly thickening acting polymer
  • the formulations according to the invention may optionally also contain water-miscible or at least water-dispersible organic or other agents
  • Such additives serve, in particular, to stabilize the surfactant solution during storage or transport to the oil field.
  • the amount of such additional solvents should normally be In a particularly preferred embodiment of the invention, only water is used for formulating
  • water-miscible solvents include in particular alcohol e such as methanol, ethanol and propane nol, butanol, sec-butanol, pentanol, butyl ethylene glycol, butyl diethylene glycol or butyl triethyl englycol.
  • the surfactant formulation may also contain other components, such as, for example, C 4 - to Cs-alcohols and / or basic salts (so-called "alkali surfactant flooding") .
  • alkali surfactant flooding for example, the retention in the formation can be reduced
  • the alcohols with respect to the total amount of surfactant used is generally at least 1: 1 - but it can also be a significant excess of alcohol can be used.
  • the aqueous surfactant formulation contains at least one basic salt.
  • the at least one basic salt is preferably selected from the group consisting of sodium carbonate, sodium bicarbonate, potassium hydroxide and silicates.
  • the amount of basic salts is typically from 0.1% to 5% by weight, based on the total aqueous surfactant formulation.
  • At least one chelating agent for example EDTA is added to the at least one basic salt - typically from 0.03% by weight to 5% by weight, based on the total aqueous surfactant formulation.
  • the aqueous surfactant formulation of the invention may further contain at least one acrylamide-based homopolymer or copolymer.
  • acrylamide and methacrylamide and derivatives thereof such as N-methyl (meth) acrylamide, ⁇ , ⁇ '-dimethyl (meth) acrylamide and N-methylolacrylamide.
  • acrylamido-2-methylpropanesulfonic acid APMS
  • 2-methacrylamido-2-methylpropanesulfonic acid 2-acrylamidobutanesulfonic acid, 3-acrylamido-3-methylbutanesulfonic acid or 2-acrylamido-2,4,4-trimethylpentanesulfonic acid or phosphonic acid groups
  • Monomers such as vinylphosphonic acid, allylphosphonic acid, N- (meth) acrylamidoalkylphosphonklaren or (meth) acryloyloxyalkylphosphonklaren call.
  • the abovementioned compounds can be used not only in the acid form shown, but also in the form of corresponding salts.
  • the surfactant formulation according to the invention may also comprise further surfactants.
  • These other surfactants may in particular also be oligomeric or polymeric surfactants. With such polymeric cosurfactants can be advantageous to reduce the necessary to form a microemulsion amount of surfactants.
  • Such polymeric cosurfactants are therefore also referred to as "microemulsion"
  • polymeric surfactants include amphiphilic block copolymers comprising at least one hydrophilic and at least one hydrophobic block
  • amphiphilic block copolymers comprising at least one hydrophilic and at least one hydrophobic block
  • examples include polypropylene oxide-polyethylene oxide block copolymers, polyisobutene-polyethylene oxide block copolymers, and polyethylene oxide sidechain comb polymers and a hydrophobic main chain, wherein the main chain preferably comprises essentially olefins or (meth) acrylates as structural units
  • polyethylene oxide is here intended to include in each case polyethylene oxide blocks comprising propylene oxide units as defined above. Further details of such surfactants are disclosed in WO 2006/131541 A1.
  • the proportion is preferably at least 50% by weight, particularly preferably at least 70% by weight.
  • the deposits in which the process of the invention is used have a temperature of at least 10 ° C., for example from 10 to 150 ° C., preferably from 15 to 120 ° C.
  • the total concentration of all surfactants together is 0.05 to 5 wt .-% with respect to the total amount of the aqueous surfactant formulation, preferably 0, 1 to 2.5 wt .-%, particularly preferably 0, 1 to 0.5 wt .-%.
  • the person skilled in the art depending on the desired properties, in particular depending on the conditions in the petroleum formation, a suitable choice.
  • the concentration of surfactants may change upon injection into the formation because the formulation may mix with formation water or absorb surfactants also on solid surfaces of the formation. It is the great advantage of the surfactant mixture used according to the invention that it leads to a particularly high lowering of the interfacial tension.
  • the surfactant mixture according to the invention containing at least one anionic surfactant (A) and at least one nonionic surfactant (B) of the general formula (I) for the process according to the invention is in the form of an aqueous concentrate containing not more than 20% by weight. , preferably not more than 15 wt .-%, particularly preferably not more than 10 wt .-% water and at least 80 wt%, preferably at least 85 wt .-%, particularly preferably at least 90 wt .-% of the surfactant mixture, based on the total amount of concentrate, provided.
  • a further aspect of the invention relates to an aqueous concentrate of the surfactant mixture according to the invention, comprising at least one surfactant (A) and at least one surfactant (B) of the general formula (I).
  • the concentrate according to the invention contains not more than 20% by weight, preferably not more than 15% by weight, more preferably not more than 10% by weight of water and at least 80% by weight, preferably at least 85% by weight. -%, particularly preferably at least 90 wt .-% of the surfactant mixture, based on the total amount of the concentrate.
  • the weight ratio of surfactant (A) to surfactant (B) in the concentrate ranges from 51:49 to 95: 5.
  • the concentrate according to the invention can be mixed on site with the other components of the surfactant formulation used in the process according to the invention and adjusted to the desired final concentration of the surfactant mixture comprising at least one surfactant (A) and at least one surfactant (B) of the formula (I).
  • the at least one nonionic surfactant (B) of the general formula (I) for the process according to the invention is in the form of an aqueous concentrate containing not more than 20% by weight, preferably not more than 15% by weight, more preferably not more than 10% by weight of water and at least 80% by weight, preferably at least 85% by weight, particularly preferably at least 90% by weight of at least one surfactant (B), based on the total amount of the concentrate.
  • a further aspect of the invention relates to an aqueous concentrate containing not more than 20% by weight, preferably not more than 15% by weight, more preferably not more than 10% by weight of water and at least 80% by weight, preferably at least 85% by weight, particularly preferably at least 90% by weight, of at least one nonionic surfactant (B) of the general formula (I)
  • R is a linear or branched, saturated or unsaturated, aliphatic, aromatic-aliphatic or aliphatic-aromatic hydrocarbon radical having from 10 to 36 carbon atoms;
  • PO is propyleneoxy
  • x is a number from 5 to 25;
  • y is a number from 1 to 9;
  • z is a number from (x-4) to (x + 4) but is at least 5 and at most 25; wherein the sum of x + y + z is a number from 1 1 to 49, and wherein the units (EO) x, (PO) y and (EO) z are arranged blockwise in the order given in formula (I).
  • the preferred embodiments mentioned in connection with the process according to the invention apply to the at least one surfactant (B) of the general formula (I).
  • the concentrate contains no further components in addition to water and the at least one surfactant (B) of the general formula (I).
  • the water may be water containing less than 1% by weight salinity, tap water or demineralized water.
  • the addition of small amounts of not more than 20% by weight of water to the at least one surfactant (B) of the formula (I) gives a cold-stable, liquid concentrate which in one preferred embodiment has a melting point of less than 4 ° C.
  • the concentrate according to the invention comprising water and the at least one surfactant (B) of the general formula (I) at a temperature of 4 ° C has a viscosity of less than 3000 mPas, preferably less than 2600 mPas and more preferably less than 2000 mPas on.
  • the concentrate according to the invention can be mixed on site with the other components of the surfactant formulation used in the process according to the invention and adjusted to the desired final concentration of the at least one surfactant (B) of the formula (I).
  • the preparation of the iCi7-alkyl alkoxylates with a degree of branching of 3.1 can be carried out analogously to the procedure described in WO 2009/124922 A1.
  • the radical 1C17 represents the branched alkyl radical 1C17H35.
  • the derived iCi7 alcohol is a primary alcohol.
  • the ethylene oxide (465.8 g, 10.6 mol, 9 eq) was metered at 125 ° C-135 ° C to 3 bar absolute. The mixture was then stirred for 0.5 h at 130 ° C and relaxed to 1, 3 bar absolute.
  • the propylene oxide (136.4 g, 2.35 mol, 2.0 eq) was metered at 125- 135 ° C to 3 bar absolute and post-reacted at 130 ° C for 2 h. It was again relaxed to 1, 3 bar absolutely.
  • the ethylene oxide (465.8 g, 10.6 mol, 9 eq) was metered at 125 ° C-135 ° C to 3 bar absolute. Subsequently, 0.5 h at 130 ° C was stirred.
  • the bright product was characterized by means of a 1 H-NMR spectrum in CDC, a gel permeation chromatography and an OH number determination, and the yield (1362 g, 99%) was determined.
  • the analysis confirmed the desired structure 1C17-0.9 EO.2 PO-9 EO-H.
  • iCi7 alcohol 256, 1 g, 1.00 mol, 1.0 eq
  • an aqueous KOH solution containing 50% by weight of KOH.
  • the amount of KOH was 0.2% by weight of the product to be produced.
  • the mixture was dehydrated at 100 ° C and 20 mbar for 2 h.
  • the mixture was then flushed three times with N 2, a pre-pressure of about 1.3 bar N 2 was set and the temperature was increased to 140 ° C. It was again relaxed to 1, 3 bar absolutely.
  • the ethylene oxide 796.0 g, 18, 1 mol, 18 eq
  • the mixture was then stirred for 0.5 h at 140 ° C and relaxed to 1, 3 bar absolute.
  • the propylene oxide (1 16, 1 g, 2.00 mol, 2.0 eq) was metered at 135-145 ° C to 3 bar absolute and post-reacted at 140 ° C for 2 h. It was then rinsed with N2, cooled to 80 ° C and the reactor emptied.
  • the basic crude product was neutralized with the aid of acetic acid.
  • the neutralization can be carried out with commercially available magnesium silicates, which are then filtered off.
  • the bright product was characterized by means of a 1 H-NMR spectrum in CDC, a gel permeation chromatography and an OH number determination, and the yield (990 g, 99%) was determined.
  • the analysis confirmed the desired structure 1C17 - O - 2 PO - 18 EO - H.
  • Synthesis Example 4 1C17 - O - 18 EO - HI in a 21 autoclave with stirrer was added iCi7 alcohol (256.5 g, 1, 00 mol, 1.0 eq) with 4.9 g of an aqueous KOH solution, the Contains 50 wt .-% KOH, added. The amount of KOH was 0.2% by weight of the product to be produced. While stirring, the mixture was dehydrated at 100 ° C and 20 mbar for 2 h. The mixture was then flushed three times with N 2, a pre-pressure of about 1.3 bar N 2 was set and the temperature was raised to 120 ° C.
  • the ethylene oxide (792 g, 18.0 mol, 18 eq) was metered at 125-135 ° C to 3 bar absolute. The mixture was then stirred for 0.5 h at 125-135 ° C, rinsed with N2, cooled to 80 ° C and the reactor emptied. The basic crude product was neutralized with the aid of acetic acid.
  • the neutralization can be carried out with commercially available magnesium silicates, which are then filtered off.
  • the bright product was characterized by 1 H NMR spectroscopy in CDCb, gel permeation chromatography and OH number determination, and the yield (1039 g, 99%) was determined.
  • the analysis confirmed the desired structure 1C17-0-18 EO-H.
  • Cloud points of the surfactants in saline water were measured. To this was dissolved 1 g of surfactant in 100 g of a 10% NaCl solution and warmed until turbidity occurred. It was allowed to cool slowly and recorded the temperature at which the solution became clear again (cloud point method C according to EN 1890).
  • the cloud point indicates with alkyl alkoxylates, from which temperature they are no longer dissolved in water or salt water. If the cloud point of an alkyl alkoxylate of specific concentration in water is at a certain temperature, then the surfactant is clearly dissolved below this temperature, while it separates over it as a second phase. If such a solution were to be injected at temperatures which are above the cloud point, then the surfactant would be separated from the remaining injected liquid during the flooding process and possibly clog the pores of the rock.
  • Alkyl ethoxylates which have a melting point of more than 15 ° C. are disadvantageous in their handling since they are transported in heatable transport containers to the place of use or have to be melted again at the place of use, which causes a high expenditure of time and energy. For example, melting a jar with a ton of contents would take several weeks. This process could be accomplished by applying higher tempera- However, this would be at the expense of Alalkylalkoxylates and its packaging material.
  • the compound of the invention (Example 1) at 9 to 14 ° C to a much lower melting point or lower melting point range than the compounds in Comparative Examples V2, V3 and V4.
  • the compounds in Comparative Examples V2 and V3 are significantly higher in melting than the compound in Example 1: at room temperature (20 ° C), the compound in Example 1 is liquid, while the compounds of Comparative Examples V2 and V3 are waxy to solid.
  • the alkyl ethoxylate in Comparative Example C4 is still in a solid state even at 25 ° C.
  • the melting point of a concentrate thereof is below 4 ° C. This facilitates transport in cold o the temperate climates, as well as at temperatures as they prevail in the spring or fall or when used in the off-shore promotion, since the already mentioned under point B) high time and energy costs for melting the concentrate can be avoided.
  • the surfactant concentrate has a high active content in order to avoid increased energy consumption during transport to the place of use and the associated increased transport costs.
  • the concentrate should have a viscosity of less than 3000 mPas in order to be pumpable.
  • the compounds according to the invention are already obtained by the addition of small amounts of water (15 or 10 wt .-%) at 20 ° C clear, stable concentrates, which surprisingly even at low Temperatures of 4 ° C remained clear and stable.
  • the concentrates solidify at low temperatures of 4 ° C.
  • Comparative Examples V7 and V8 further show that a corresponding alkyl ethoxylate does not provide stable concentrates by adding small amounts of water.
  • the viscosities in Examples 1 and 2 are within the acceptable range and allow pumping both at temperatures greater than 20 ° C and especially at temperatures below 4 to 20 ° C.
  • the crude oil has about 16 ° API
  • the deposit temperature is around 20 ° C
  • the reservoir water has about 16100 ppm of TDS (total dissolved salt).
  • Example 1 As can be seen in Table 4, a compound of the invention in Example 1 at 0.0057 mN / m provides extremely low interfacial tension. This is even lower than in Comparative Examples V2 and V3, in each of which a surfactant having a different arrangement of the propyleneoxy groups was tested under identical conditions. One sees a surprising influence of the position of the PO block by the effect on the interfacial tension.

Abstract

L'invention concerne un procédé de production de pétrole brut par écoulement de microémulsions de type Winsor III, dans lequel on injecte une formulation aqueuse d'agent tensioactif, contenant un mélange d'agents tensioactifs, dans un gisement pétrolifère par des forages d'injection et on extrait le pétrole brut du gisement par des forages de production, le mélange d'agents tensioactifs contenant au moins un agent tensioactif anionique (A), comprenant au moins un groupe fonctionnel choisi parmi le sulfate, le sulfonate et le carboxylate ; et au moins un agent tensioactif non ionique (B) de la formule générale (I) R-O-(EO)x-(PO)y-(EO)z-H (I). L'invention concerne en outre un agent tensioactif non ionique (B), un mélange d'agents tensioactifs contenant ledit agent tensioactif non-ionique (B), une formulation d'agents tensioactifs contenant le mélange d'agents tensioactifs, ainsi que des concentrés de l'agent tensioactif (B) ou du mélange d'agents tensioactifs.
PCT/EP2015/055428 2014-03-20 2015-03-16 Procédé de production de pétrole brut tertiaire à l'aide d'alkoxylates à groupe propylénoxy moyen WO2015140102A1 (fr)

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Publication number Priority date Publication date Assignee Title
CN106590586A (zh) * 2015-10-20 2017-04-26 中国石油化工股份有限公司 用于三次采油的驱油剂
US10238106B2 (en) 2014-03-12 2019-03-26 Basf Se Carbonates of alcohol alkoxylates as adjuvants for crop protection
US10266751B2 (en) 2014-11-18 2019-04-23 Basf Se Method of mineral oil production
US11051510B2 (en) 2014-01-30 2021-07-06 Basf Se Asymmetric formales and acetales as adjuvants for crop protection

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EP0882784A1 (fr) * 1996-12-02 1998-12-09 Kao Corporation Composition tensio-active
JP2000345191A (ja) * 1999-06-03 2000-12-12 Kao Corp 界面活性剤
WO2009124922A1 (fr) * 2008-04-10 2009-10-15 Basf Se Nouveaux tensioactifs à base d'alcools ramifiés, destinés à l'exploitation tertiaire de pétrole
WO2011045205A1 (fr) * 2009-10-14 2011-04-21 Basf Se Procédé d'extraction de pétrole tertiaire au moyen de mélanges de tensioactifs

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EP0882784A1 (fr) * 1996-12-02 1998-12-09 Kao Corporation Composition tensio-active
JP2000345191A (ja) * 1999-06-03 2000-12-12 Kao Corp 界面活性剤
WO2009124922A1 (fr) * 2008-04-10 2009-10-15 Basf Se Nouveaux tensioactifs à base d'alcools ramifiés, destinés à l'exploitation tertiaire de pétrole
WO2011045205A1 (fr) * 2009-10-14 2011-04-21 Basf Se Procédé d'extraction de pétrole tertiaire au moyen de mélanges de tensioactifs

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11051510B2 (en) 2014-01-30 2021-07-06 Basf Se Asymmetric formales and acetales as adjuvants for crop protection
US10238106B2 (en) 2014-03-12 2019-03-26 Basf Se Carbonates of alcohol alkoxylates as adjuvants for crop protection
US10827748B2 (en) 2014-03-12 2020-11-10 Basf Se Carbonates of alcohol alkoxylates as adjuvants for crop protection
US10266751B2 (en) 2014-11-18 2019-04-23 Basf Se Method of mineral oil production
US10961432B2 (en) 2014-11-18 2021-03-30 Basf Se Method of mineral oil production
CN106590586A (zh) * 2015-10-20 2017-04-26 中国石油化工股份有限公司 用于三次采油的驱油剂

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