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WO2014064152A1 - Procédé d'extraction de pétrole utilisant des tensioactifs contenant au moins un alcanesulfonate secondaire et un alkyléthersulfate/alkyléthersulfonate/alkyléthercarboxylate/alkylétherphosphate - Google Patents

Procédé d'extraction de pétrole utilisant des tensioactifs contenant au moins un alcanesulfonate secondaire et un alkyléthersulfate/alkyléthersulfonate/alkyléthercarboxylate/alkylétherphosphate Download PDF

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Publication number
WO2014064152A1
WO2014064152A1 PCT/EP2013/072171 EP2013072171W WO2014064152A1 WO 2014064152 A1 WO2014064152 A1 WO 2014064152A1 EP 2013072171 W EP2013072171 W EP 2013072171W WO 2014064152 A1 WO2014064152 A1 WO 2014064152A1
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carbon atoms
surfactant
surfactants
general formula
saturated
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German (de)
English (en)
Inventor
Christian Bittner
Günter OETTER
Jack Tinsley
Christian Spindler
Gabriela ALVAREZ JÜRGENSON
Sophie Maitro-Vogel
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—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 present invention relates to a surfactant mixture, its use and preparation, and to aqueous surfactant formulations containing the surfactant mixture and processes for producing oil by means of Winsor Type III microemulsion flooding, in which the aqueous surfactant formulation is injected through injection wells into a crude oil deposit and crude oil is removed from the deposit through production wells.
  • 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 crude oil, including natural gas, 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.
  • the 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.
  • injection wells water is injected into the reservoir to maintain or increase the pressure.
  • the oil is slowly forced through the cavities into the formation, starting from the injection well, in the direction of the production well. But this works only as long as the cavities are completely filled with oil and the viscous oil is pushed through the water in front of him.
  • the low-viscosity water breaks through cavities, it flows from this point on the path of least resistance, ie through the channel formed, and no longer pushes the oil in front of it.
  • Tertiary oil production includes heat processes in which hot water or superheated steam is injected into the deposit, which reduces the viscosity of the oil 2 or use nitrogen.
  • Tertiary oil production further includes processes in which suitable chemicals are used as auxiliaries for oil extraction. 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.
  • Viscous and capillary forces act on the oil trapped in the pores of the reservoir rock towards the end of the secondary production, and the ratio of these two forces to one another determines the microscopic oil removal.
  • capillary number the influence of these forces is described. It is the ratio of the viscosity forces (velocity x viscosity of the pressing phase) to the capillary forces (interfacial tension between oil and water x wetting of the rock):
  • ⁇ is the viscosity of the oil mobilizing fluid
  • v the Darcy velocity (flow per unit area)
  • ⁇ the interfacial tension between petroleum mobilizing liquid and petroleum
  • ⁇ the contact angle between petroleum and rock
  • capillary number " is 6, and that it is necessary for the capillary to about 10" near the end of secondary oil recovery in the range of about 10 to increase from 3 to 10 "2 to mobilize additional mineral oil.
  • Winsor type III microemulsion flooding the injected surfactants are expected to form a microemulsion Windsor Type III with the water and oil phases present in the reservoir.
  • a microemulsion Windsor Type II I is not an emulsion with particularly small droplets, but a thermodynamically stable, liquid mixture of water, oil and surfactants. Your three advantages are that thereby achieving a very low interfacial tension ⁇ between petroleum and aqueous phase,
  • microemulsion Winsor Type III 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 surfactant-sion) are particularly preferred in. In order to achieve an optimum result, the proportion should the Microemulsion in the system water-microemulsion oil with a defined amount of surfactant naturally be as large as possible, since thereby the lower interfacial tensions can be achieved.
  • the shape of the oil droplets can be changed (interfacial tension between oil and water is lowered so far that the state of the smallest boundary surface is no longer sought and the spherical shape is no longer preferred) and by the flood water through the capillary openings squeeze through.
  • 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.
  • surfactants which accomplish a very low interfacial tension between oil and water phase.
  • 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 oil droplets located there can merge with the bank. Furthermore, the oil-water interface is significantly reduced by the union of the oil drops to an oil bank and thus released no longer needed surfactant.
  • 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 are the interfacial tension between water and oil (usually approx. 20 mN / m) to particularly low values of less than 10 ". 2 mN / m to allow sufficient mobilization of the petroleum at the usual deposit temperatures of about 15 ° C to 130 ° C and in the presence of high salty water, especially in the presence of high levels of calcium and or magnesium ions, the surfactants must therefore also be soluble in strongly salty deposit water.
  • mixtures of surfactants have frequently been proposed, in particular mixtures of anionic and nonionic surfactants.
  • No. 3,811,1507 describes the combination of linear alkyl sulfonates or alkylaryl sulfonates with alkyl ether sulfates, where the alkyl ether sulfate is an alkyl polyethylene oxysulfate.
  • GB 2,168,094 describes the combination of internal olefin sulfonates with alkyl ether sulfonates.
  • No. 7,119,125 B1 describes a mixture of sulfated Guerbet alcohol alkoxylate and low molecular weight sulfated alkyl alkoxylate in oil production.
  • the bimodal distribution is assigned particularly good emulsifying properties.
  • These Emulsifying properties do not play a major role in microemulsion flooding according to Winsor type III. One would need too much surfactant for the emulsification of oil and the required shear forces are hardly in the flood process before (apart from the area around the injector).
  • US-A 2009/270281 describes the use of a surfactant mixture for crude oil production, which contains at least one surfactant having an alkyl radical of 12 to 30 carbon atoms and a branched cosurfactant having an alkyl radical of 6 to 1 1 carbon atoms.
  • the degree of branching of the alkyl radical in the cosurfactant ranges from 1 to 2.5 and may thus include Guerbet alcohols of the type 2-ethylhexyl or 2-propylheptyl.
  • the cosurfactants may be alcohol ethoxylates or anionic modified alcohol ethoxylates (for example, alkyl ether sulfate).
  • No. 201 1 / 247,830 A1 describes surfactant mixtures containing surfactants based on a branched C 17 H 35 -alkyl radical.
  • WO 201 1/1 10502 A1 describes surfactant mixtures containing surfactants based on a linear C16H33 and C18H37-alkyl radical.
  • WO 201 1/1 10503 A1 describes surfactant mixtures containing anionically modified alkyl alkoxylates which contain butyleneoxy units.
  • the parameters of use such as the type, concentration and mixing ratio of the surfactants used, are adapted by the person skilled in the art to the conditions prevailing in a given oil formation (for example temperature and salinity).
  • 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.
  • surfactants are suitable which have a long hydrophobicity. This hydrophobic group may be an alkyl group or an alkyl group extended with hydrophobic alkyleneoxy units. The longer the hydrophobicity is, the better the interfacial tensions can be reduced, but the solubility of the compound usually decreases. Therefore, a second surfactant is usually needed to improve the solubility or the interfacial tension.
  • An object of the present invention is therefore to provide a particularly efficient surfactant mixture for use in surfactant flooding, as well as an improved process for tertiary mineral oil production.
  • the object is achieved by a surfactant mixture, wherein the surfactant mixture contains at least one secondary alkanesulfonate of the general formula (I)
  • R 1 and R 2 independently represent a linear or branched, saturated aliphatic hydrocarbon radical, wherein the radical R 1 CHR 2 has 14 to 17 carbon atoms;
  • R 3 is a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical
  • R 4 is H or a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical, the radical R 3 R 4 CHCH 2 having from 8 to 44 carbon atoms;
  • each A ° independently for ethylene, propylene or butylene
  • k is an integer from 1 to 99
  • X is a branched or unbranched alkylene group having 1 to 10 carbon atoms which may be substituted with an OH group;
  • Y a represents a sulfate group, sulfonate group, carboxylate group or a phosphate group
  • a stands for 1 or 2.
  • Another aspect of the present invention relates to an aqueous surfactant formulation comprising a surfactant mixture according to the invention, wherein preferably the aqueous surfactant formulation has a total surfactant content of 0.05 to 5 wt.% Relative to the total amount of the aqueous surfactant formulation.
  • a further aspect of the present invention relates to the use of a surfactant mixture according to the invention or an aqueous surfactant formulation according to the invention in the field of mineral oil production by means of Winsor Type III microemulsion flooding.
  • Another aspect of the present invention relates to methods for oil production, by Winsor type III microemulsion flooding, wherein an aqueous surfactant formulation according to the invention containing a surfactant mixture to lower the interfacial tension between oil and water to ⁇ 0.1 mN / m, by at least one injection well into a Erdöllager GmbH pressed and crude oil is removed from the deposit through at least one production well.
  • a mixture of at least one surfactant of the general formula (I) and at least one surfactant of the general formula (II) and a process for tertiary mineral oil production by means of Winsor Type III microemulsion flooding are provided, wherein an aqueous surfactant formulation comprising at least one surfactant of general formula (I) and at least one surfactant of the general formula (II) is injected into at least one injection well in a Erdöllager Too, the interfacial tension between oil and water to values ⁇ 0.1 mN / m, preferably to values ⁇ 0.05 mN / m, more preferably to values ⁇ 0.01 mN / m is lowered, and the deposit is withdrawn through at least one production well crude oil.
  • the weight-based ratio of surfactant of the general formula (I) to surfactant of the general formula (II) is between 1:19 and 19: 1. More preferably, the ratio of (I) to (II) is between 1: 9 and 9: 1. Even more preferably, the ratio of (I) to (II) is between 1: 9 and 1: 1 .01.
  • R 1 is a linear saturated aliphatic hydrocarbon radical and R 2 is a linear saturated aliphatic hydrocarbon radical, wherein the alkyl radical R 1 CHR 2 is a hydrocarbon radical having 14 to 17 carbon atoms.
  • M b + is preferably Na + .
  • a mixture of 4 surfactants of the general formula (I) with different numbers of carbon atoms is present.
  • the proportion of surfactants of the formula (I) in each case based on the radical R 1 R 2 CH- with 14 carbon atoms at 20-30 mol%, the proportion of surfactants of the formula (I) with 15 carbon atoms at 25-30 mol.
  • R 3 is a linear, saturated or unsaturated aliphatic hydrocarbon radical having 14 to 16 carbon atoms and R 4 is a hydrogen atom.
  • R 3 is a linear, saturated aliphatic hydrocarbon radical having 14 or 16 carbon atoms and R 4 is a hydrogen atom. It is further preferred that the proportion by weight of these 2 ionic surfactants of the formula (II), based on the total weight of the surfactant mixture according to the invention, is greater than 50% by weight, more preferably greater than 60% by weight, more preferably greater than 70% by weight. , more preferably greater than 80 wt .-%, more preferably greater than 90 wt .-% is.
  • R 3 is a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical having 10 or 12 carbon atoms and R 4 is a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical having 12 or 14 carbon atoms ,
  • R 3 is a linear, saturated or unsaturated (preferably saturated) aliphatic hydrocarbon radical having 10 or 12 carbon atoms and R 4 is a linear, saturated or unsaturated (preferably saturated) aliphatic hydrocarbon radical 12 or 14 carbon atoms, and in particular by at least 3 ionic surfactants of the formula (II) having a hydrocarbon radical having 24 carbon atoms, 26 carbon atoms and 28 carbon atoms.
  • the C 2 4 surfactant of the formula (II) is particularly preferably-in each case based on the radical R 3 R 4 CHCH 2 -in a range from 40 mol% to 60 mol .-%, the C 26 surfactant of formula (II) in a range of 30 mol% to 50 mol .-% and the C 2 8 surfactant of formula (II) in a range of 1 mol .-% to 20 mol .-% based on the sum of the proportions of these surfactants before.
  • R 3 is a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical having 14 or 16 carbon atoms and R 4 is a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical having 16 or 18 carbon atoms ,
  • R 3 is a linear, saturated or unsaturated (preferably saturated) aliphatic hydrocarbon radical having 14 or 16 carbon atoms and R 4 is a linear, saturated or unsaturated (preferably saturated) aliphatic hydrocarbon radicals having 16 or 18 carbon atoms, and in particular characterized in that at least 3 ionic surfactants of the formula (II) having a hydrocarbon radical based on the radical R 3 R 4 CHCH 2 having 32 carbon atoms, 34 carbon atoms and 36 carbon atoms.
  • the C 32 surfactant of the formula (II) is particularly preferably in a range from 20% to 40%, and the C 3 4 surfactant of the formula (II) in a range of 41 % to 60% and the C 3 6 surfactant of formula (II) in a range of 10% to 35% based on the total.
  • the proportion by weight of these 3 ionic surfactants based on the total weight of the surfactant mixture according to the invention greater than 50 wt .-%, more preferably greater than 60 wt .-%, more preferably greater than 70 wt .-%, more preferably greater than 80 wt .-%, more preferably greater than 90 wt .-% is.
  • alkyleneoxy (AO) groups OA ° in general formula (II), which occur k-fold, may be the same or different. If these are different, they may be distributed statistically, alternately or in blocks, i. be arranged in two, three, four or more blocks.
  • the n-butylene, m-propylene and ethyleneoxy groups are at least partially (preferably in numbers of at least 50 mol%, more preferably at least 60%, more preferably at least 70%, more preferably at least 80%, more preferably at least 90%, in particular completely) arranged in blocks.
  • Arranged in blocks means in the context of the present invention that at least one AO has a neighboring group AO, which is chemically identical, so that these form at least two AO a block.
  • R 3 radical
  • k or the variables I, m and n stand for natural numbers including 0, ie for 0, 1, 2, etc.
  • the numbers I, m and n are average values over all molecules of the surfactants, since in the alkoxylation of alcohol with ethylene - Lenoxid or propylene oxide or butylene 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.
  • D M w / M n is the quotient of the weight average molecular weight and the number average molar mass.
  • the polydispersity can be determined by means of the methods known to the person skilled in the art, for example by means of gel permeation chromatography.
  • k is an integer in the range of 4 to 50, more preferably in the range of 8 to 39.
  • the variable I represents a number from 0 to 99, preferably from 1 to 40, more preferably from 1 to 20; m is a number from 0 to 99, preferably from 1 to 20, particularly preferably from 4 to 15; n stands for a number from 0 to 99, preferably for 0 to 20, particularly prefers for 1 to 15, whereby furthermore the sum of the variables I, m, n gives a number from (in each case inclusive) 1 to 99.
  • m is an integer from 4 to 15 (more preferably 5 to 9) and / or I is an integer from 0 to 25 (more preferably 4 to 15) and / or n is 0.
  • m is an integer of 4 to 15 (more preferably 5 to 9) and / or I is an integer of 0 to 25 (more preferably 4 to 15) and / or n is an integer of 1 to 15 (more preferably 5 to 9).
  • X represents a branched or unbranched alkylene group having 1 to 10, preferably 2 to 4, carbon atoms which may be substituted with an OH group.
  • the alkylene group is preferably a methylene, ethylene or propylene group.
  • X is preferably CH 2 CH 2 , CH 2 CH (OH) CH 2 , (CH 2 ) 3 , CH 2 or CH 2 CH (R '), where R' is hydrogen or an alkyl radical having 1 to 4 carbon atoms (for example methyl ).
  • M + is independently a cation, preferably the cation is selected from the group consisting of Na + ; K + , Li + , NH 4 + , H + , Mg 2+ and Ca 2+ (preferably Na + , K + or NH 4 + ).
  • B is preferably 1 or 2, in particular 1.
  • Each M + may be the same or different for formula (I); but prefers the same.
  • Each M + may be the same or different for formula (II); but prefers the same.
  • the cations M + may be the same or different in comparison with formula (I) and formula (II); but prefers the same.
  • Y a represents a sulfonate, sulfate, carboxylate or phosphate group (preferably sulfonate, sulfate or carboxylate group, particularly preferably sulfate or carboxylate)
  • a can be 1 or 2 stand.
  • the radical (OX) 0 Y a " is OS (0) 2 0 " , OCH 2 CH 2 S (O) 2 O " , OCH 2 CH (OH) CH 2 S (0) 2 0 " , 0 (CH 2 ) 3 S (0) 2 0 " , 0 (CH 2 ) 4 S (0) 2 0 " , S (0) 2 0 “ , CH 2 C (0) 0 “ or CH 2 CH (R ') C (O) O " , where R' is hydrogen or an alkyl radical having 1 to 4 carbon atoms (for example methyl).
  • the invention relates to a mixture of at least one surfactant of the general formula (I) and at least one surfactant of the general formula (II) and their use in oil production by means of Winsor type III microemulsion flooding, where I is an integer from 0 to 99, m is a number from 4 to 15 and n is a number from 0 to 15, and Y a "is selected from the group consisting of sulfate group, sulfonate group and carboxylate group, the groups BuO, PO and EO to more than 80% are in block form in the order BuO, PO, EO starting from (R 3 ) (R 4 ) -CH-CH 2 and the sum I + m + n is in the range from 5 to 49.
  • a particularly preferred embodiment is when I is an integer from 0 to 99, m is a number from 5 to 9 and n is a number from 1 to 15, and Y a "is selected from the group consisting of sulfate group, Sulfonate group and carboxylate group, wherein the groups BuO, PO and EO are more than 80% in block form in the order BuO, PO and EO starting from (R 3 ) (R 4 ) -CH-CH 2 , the Sum I + m + n is in the range of 4 to 50 and the block BuO consists of more than 80% of 1, 2-butylene oxide.
  • a preferred surfactant mixture according to the invention additionally contains, in addition to at least one surfactant of the general formula (I) and at least one surfactant of the general formula (II), at least one surfactant of the general formula (III)
  • R 3 is a linear, saturated aliphatic hydrocarbon radical having 10 or 12 carbon atoms and in the general formula (IV) R 4 is a linear, saturated aliphatic hydrocarbon radical having 12 or 14 carbon - atoms.
  • R 3 is a linear, saturated aliphatic hydrocarbon radical having 14 or 16 carbon atoms and in the general formula (IV) R 4 is a linear, saturated aliphatic hydrocarbon radical having 16 or 18 carbon atoms ,
  • more than one surfactant of the general formula (II) may also be present in the surfactant mixture.
  • the relative to the hydrocarbon moiety (R 3 ) (R 4 ) -CH-CH 2 - different surfactants can be subsumed under the general formula (II). The difference may be due to the number of carbon atoms, the number the unsaturated bonds, the branching frequency and / or the degree of branching. In particular, the surfactants differ in chain length given for R 3 and R 4 .
  • the alkyl radical R 3 R 4 CHCH 2 is a hydrocarbon radical having 8 to 44 carbon atoms.
  • R 4 may be linear or branched, saturated or unsaturated aliphatic hydrocarbon radicals of the type R 3 R 4 CHCH 2 .
  • R 4 can also be a hydrogen atom.
  • branching degrees of 0.1 to 5 are preferred. More preferred are degrees of branching from 0.1 to 3.5 (more preferably 0.1 to 2.5).
  • degree of branching is hereby defined in a manner known in principle as the number of methyl groups in a molecule of the alcohol minus 1.
  • the mean degree of branching is the statistical average of the degrees of branching of all molecules in a sample.
  • R 3 is a linear, saturated or unsaturated aliphatic hydrocarbon radical having 14 to 16 carbon atoms and R 4 is a hydrogen atom.
  • R 3 is a linear saturated aliphatic hydrocarbon radical having 14 or 16 carbon atoms and R 4 is a hydrogen atom.
  • Exemplary accessible by dimerization of alcohols compounds lead to R 3 / R 4 hydrocarbon chains with 10/12, 10/13, 10/14, 1 1/12, 1 1/13, 1 1/14, 12/12, 12 / 13, 12/14, preferably 10/12, 10/14, 12/12, 12/14 carbon atoms.
  • the radical R 3 is a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical having 10 to 12 carbon atoms.
  • the radical R 4 is a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical having 12 to 14 carbon atoms.
  • R 3 is either identical to R 4 or preferably has at most two C atoms (more preferably exactly two C atoms) less than R 4 .
  • the degree of branching in R 3 or R 4 is preferably in the range from 0.1 to 5 (preferably from 0.1 to 1.5).
  • the degree of branching in R 3 or R 4 is preferably in the range from 0.1 to 5 (preferably from 0.1 to 1.5).
  • the degree of branching in R 3 or R 4 is preferably in the range from 0.1 to 5 (preferably from 0.1 to 1.5).
  • the degree of branching in R 3 or R 4 is preferably in the range from 0.1 to 5 (preferably from 0.1 to 1.5).
  • the degree of branching in R 3 or R 4 is preferably in the range from 0.1 to 5 (preferably from 0.1 to 1.5).
  • the degree of branching in R 3 or R 4 is preferably in the range from 0.1 to 5 (preferably from 0.1 to 1.5).
  • the degree of branching in R 3 or R 4 is preferably in the range from 0.1 to 5 (preferably from 0.1 to 1.5).
  • the degree of branching in R 3 or R 4 is preferably in the range from 0.1 to 5 (preferably from 0.1 to 1.5).
  • Exemplary compounds obtainable by dimerization of alcohols lead to R 3 / R 4 alkyl chains having 14/16, 14/17, 14/18, 15/16, 15/17, 15/18, 16/16, 16/17, 16 / 18 - especially 14/16, 14/18, 16/16, 16/18 carbon atoms.
  • more than three different surfactants of the general formula (II) may also be present in the surfactant mixture.
  • the three surfactants form the major components of the surfactant mixture.
  • the radical R 3 is a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical having 14 to 16 carbon atoms.
  • the radical R 4 is a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical having 16 to 18 carbon atoms.
  • R 3 is either identical to R 4 or has at most two C atoms (more preferably exactly two C atoms) less than R 4 .
  • the degree of branching at R 3 or R 4 is preferably in the range from 0.1-5 (preferably from 0.1-1.5).
  • the degree of branching at R 3 or R 4 is preferably in the range from 0.1-5 (preferably from 0.1-1.5).
  • the degree of branching at R 3 or R 4 is preferably in the range from 0.1-5 (preferably from 0.1-1.5).
  • the degree of branching at R 3 or R 4 is preferably in the range from 0.1-5 (preferably from 0.1-1.5).
  • the degree of branching at R 3 or R 4 is preferably in the range from 0.1-5 (preferably from 0.1-1.5).
  • the degree of branching at R 3 or R 4 is preferably in the range from 0.1-5 (preferably from 0.1-1.5).
  • the degree of branching at R 3 or R 4 is preferably in the range from 0.1-5 (preferably from 0.1-1.5).
  • the degree of branching at R 3 or R 4 is preferably in the range from 0.1-5 (preferably from 0.1-1.5).
  • the alcohols (R 3 ) (R 4 ) -CH-CH 2 -OH which can serve as starting compound for the preparation of the surfactants of the invention are, for example, by hydrogenation of fatty acid methyl esters (R 4 is a hydrogen atom), Oxoalkoholsynthese or dimerization of alcohols of the type R 3 CH 2 CH 2 OH and R 4 OH (R 4 is not a hydrogen atom) accessible with elimination of water. Accordingly, a further aspect of the present invention is a process for preparing a surfactant mixture according to the invention comprising the steps:
  • the preparation of the surfactant of the general formula (I) in process step (a) is known to the person skilled in the art.
  • an alkane mixture is mixed with water and irradiated at 20-40 ° C with UV light (eg 10 - 40 kW mercury vapor lamps), wherein a mixture of sulfur dioxide and oxygen (molar ratio preferably 2: 1) is passed.
  • the conversion is preferably limited to ⁇ 5% (preferably ⁇ 1%) and the target compounds are discharged.
  • Unreacted alkane is returned to the process.
  • the process is preferably continuous.
  • the separation of the alkanesulfonic acids obtained from the residual alkane is carried out by phase separation. After removal of gases (S0 2 , S0 3 ), the alkanesulfonic acid is reacted with lye - preferably sodium hydroxide solution - to the surfactant.
  • step (c ) Reaction of the alcohol alkoxylates obtained in step (b") with a group Y a " , if appropriate with formation of a spacer group OX.
  • step (c ') Reaction of the obtained in step (b') alcohol alkoxylates with a group Y a " , optionally to form a spacer group OX.
  • the alcohols according to the formula R-CH 2 CH 2 -OH may be a mixture of alcohols.
  • This may include a C12C14 fatty alcohol mixture (linear, saturated), a C12C14 mixture of Ziegler alcohols having 12 or 14 carbon atoms, a C12C14 fatty alcohol mixture (linear and partially unsaturated) or a mixture of C12C14-oxoalcohol.
  • R is a linear saturated or unsaturated (preferably saturated) aliphatic hydrocarbon radical having 10 or 12 carbon atoms.
  • C16C18 fatty alcohol mixture linear, saturated
  • C16C18 mixture of Ziegler alcohols having 16 or 18 carbon atoms a C16C18 fatty alcohol mixture (linear and partially unsaturated) or a mixture of C16C18 oxo alcohol.
  • R is a linear saturated or unsaturated (preferably saturated) aliphatic hydrocarbon radical having 14 or 16 carbon atoms.
  • the condensation of alcohols of the formula R-CH 2 CH 2 -OH to Guerbet alcohols is preferably carried out in the presence of from 0.5 to 10% by weight, based on the alcohol, alkali or alkaline earth hydroxide, for example lithium hydroxide, sodium hydroxide, cesium hydroxide or potassium hydroxide, preferably potassium hydroxide.
  • alkali or alkaline earth metal hydroxide for example lithium hydroxide, sodium hydroxide, cesium hydroxide or potassium hydroxide, preferably potassium hydroxide.
  • the alkali or alkaline earth metal hydroxide can be used in solid form (flakes, powder) or in the form of a 30 to 70%, preferably 50%, aqueous solution.
  • the alcohols of the formula R-CH 2 CH 2 -OH are condensed in the presence of NaOH and / or KOH.
  • Suitable catalysts are the catalysts known from the prior art, for example nickel, lead salts (US Pat. No. 3,119,880), copper, lead, zinc, chromium, molybdenum, tungsten and magane oxides (US Pat. US 3,558,716), palladium complexes (US 3,979,466) or silver complexes (US 3,864,407).
  • ZnO is preferably used as the catalyst for the dimerization.
  • the catalyst or catalysts are preferably ZnO catalysts generally added to the mixture from which the Guerbet alcohols are made.
  • the mixture of Guerbet alcohols can be prepared by the process known from DE 3901095 A1.
  • the Guerbet alcohols are in process step (a '") at a temperature in the range of 150 to 320 ° C, preferably at a temperature in the range of 180 to 280 ° C optionally in the presence of a catalyst or a plurality of catalysts synthesized.
  • the alcohols (R 3 ) (R 4 ) -CH-CH 2 -OH obtained in process step (a), (a '") can be prepared in a manner known in principle by alkoxylation in process step (b ⁇ b", b'"). ) are converted to alcohol alkoxylates.
  • the implementation of such alkoxylations 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.
  • the alcohol alkoxylates can be prepared in process step (b ⁇ b ", b '") preferably by base-catalyzed alkoxylation.
  • the alcohol (R 3 ) (R 4 ) -CH-CH 2 - OH in a pressure reactor with alkali metal hydroxides, preferably potassium hydroxide, or with alkali alcoholates, such as sodium methylate, are added.
  • alkali metal hydroxides preferably potassium hydroxide
  • alkali alcoholates such as sodium methylate
  • the mixture is then inertized with inert gas (for example nitrogen) and the alkylene oxide (s) is added stepwise at temperatures of 60 to 180 ° C up to a maximum pressure of 10 bar.
  • the alkylene oxide is initially metered in at 130.degree. In the course of the reaction, the temperature rises up to 170 ° C due to the released heat of reaction.
  • the butylene oxide is first added at a temperature in the range of 125 to 145 ° C, then the propylene oxide is added at a temperature in the range of 130 to 145 ° C and then the ethylene oxide at a temperature in the range of 125 to 155 ° C was added.
  • the catalyst can be neutralized, for example by addition of acid (for example acetic acid or phosphoric acid) and filtered off as required.
  • the alkoxylation of the alcohols (R 3 ) (R 4 ) -CH-CH 2 -OH can also be carried out by other methods, for example by acid-catalyzed alkoxylation.
  • DMC catalysts are disclosed, for example, in DE 10243361 A1, in particular in sections [0029] to [0041] and the literature cited therein.
  • Zn-Co type catalysts can be used.
  • the catalyst can be added to the alcohol (R 3 ) (R 4 ) -CH-CH 2 -OH, the mixture is dehydrated as described above and reacted with the alkylene oxides as described. It is usually not more than 1000 ppm catalyst used with respect to the mixture and the catalyst may remain in the product due to this small amount.
  • the amount of catalyst can typically be less than 1,000 ppm, for example 250 ppm or less.
  • the process step (c ⁇ c ", c ') relates to the reaction of the in step (b ⁇ b ", b'") obtained alcohol alkoxylates having a group Y a " , optionally forming a spacer group OX.
  • sulfate and phosphate groups can be introduced by reacting them directly (optionally after activation) with the alcohol alkoxylate.
  • Sulfonate groups can be introduced by vinyl addition, substitution reaction or aldol reaction, if appropriate with subsequent hydrogenation, with corresponding spacer OX being produced.
  • the alcohol alkoxylate may also be previously converted to a chloride, which is then subjected to a direct sulfonation reaction. phonation is accessible.
  • a sulphonate group for example, the reaction with propanesultone and subsequent neutralization, with butane sultone and subsequent neutralization, with vinylsulphonic acid sodium salt can be resorted to for example in the case of a sulphate group or with 3-chloro-2-hydroxypropanesulfonic acid sodium salt.
  • the termin ale OH group in a chloride for example, with phosulfonates
  • carboxylate group In the case of a carboxylate group, it is possible, for example, to resort to the oxidation of the alcohol with oxygen and subsequent neutralization or the reaction with sodium chloroacetate.
  • Carboxylates can also be obtained, for example, by Michael addition of (meth) acrylic acid or esters.
  • Phosphates can be obtained, for example, by esterification reaction with phosphoric acid or phosphorus pentachloride.
  • the surfactant mixture may furthermore optionally comprise further surfactants.
  • further surfactants for example, secondary alkanesulfonates having 12, 13 or 18 carbon atoms or primary alkanesulfonates having 12 to 18 carbon atoms may be present.
  • Other surfactants may also be alkanedisulfonates. These may, for example, have 12 to 18 carbon atoms.
  • anionic surfactants of the type alkylarylsulfonate or olefinsulfonate (alpha-olefinsulfonate or internal olefinsulfonate), alkyl ether sulfonate, alkyl ether carboxylate, alkyl ether sulfate and / or nonionic surfactants of the alkyl ethoxylate or alkyl polyglucoside type can also be used, for example.
  • Betainic surfactants may also be used.
  • These other surfactants may in particular also be oligomeric or polymeric surfactants.
  • Such polymeric co-surfactants can advantageously reduce the amount of surfactants necessary to form a microemulsion.
  • polymeric cosurfactants are also referred to as "microemulsion boosters.”
  • polymeric surfactants include amphiphilic block copolymers comprising at least one hydrophilic and at least one hydrophobic block, examples of which include polypropylene oxide-polyethylene oxide block copolymers, polyisobutene polyethylene oxide Block copolymers and comb polymers with polyethylene oxide side chains and a hydrophobic main chain, wherein the main chain preferably substantially olefins or (Meth) acrylates as structural units.
  • polyethylene oxide is intended to include polyethylene oxide blocks comprising propylene oxide units as defined above Further details of such surfactants are disclosed in WO 2006/131541 A1.
  • a suitable aqueous surfactant formulation of the surfactant mixture according to the invention is injected into the crude oil deposit through at least one injection well and crude oil is taken from the deposit through at least one production well.
  • the term "crude oil” in this context does not mean phase-pure oil, but rather the customary crude oil-water emulsions, as a rule, a deposit is provided with several injection wells and several production wells
  • Winsor Type III microemulsion flooding the surface tension between oil and water is reduced to values of ⁇ 0.1 mN / m, preferably to ⁇ 0.05 mN / m, particularly preferably to ⁇ 0.01 mN / m, by using the aqueous surfactant formulation according to the invention
  • the interfacial tension between oil and water will be in the range of 0.1 mN / m to 0.0001 mN / m, preferably values in the range of 0.05 mN /
  • the main effect of the surfactant mixture according to the invention lies in the reduction of the interfacial tension between water and oil - desirably to values clearly ⁇ 0.1 mN / m.
  • surfactant flooding or preferably the Winsor type III "microemulsion flooding”
  • water can be injected into the formation to maintain the pressure ("water flooding") or, preferably, a higher viscous aqueous solution of a strong thickening polymer (“polymer flooding”).
  • water flooding water flooding
  • polymer flooding a higher viscous aqueous solution of a strong thickening polymer
  • an aqueous surfactant formulation which contains at least surfactants of the general formula (I) and formula (II) is used.
  • the aqueous surfactant formulation may comprise further components besides the surfactant mixture.
  • the formulations may optionally also contain water-miscible or at least water-dispersible organic or other agents as co-solvent.
  • Such additives are used in particular for stabilizing the surfactant solution during storage or transport to the oil field.
  • the amount of such cosolvents should as a rule not exceed 50% by weight, preferably 20% by weight, based on the total weight of the aqueous surfactant formulation.
  • cosolvents examples include, in particular, alcohols such as methanol, ethanol and n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, n-pentanol, isopentanol, butylmonoethylene glycol, butyldiethylene glycol or butyltriethylene glycol.
  • alcohols such as methanol, ethanol and n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, n-pentanol, isopentanol, butylmonoethylene glycol, butyldiethylene glycol or butyltriethylene glycol.
  • water is used for formulation.
  • the surfactants of general formula (II) in the aqueous formulation, which is ultimately injected into the deposit are said to constitute the major component among all surfactants. These are preferably at least 25% by weight, more preferably at least 30% by weight, very preferably at least 40% by weight and very, very preferably at least 50% by weight, based on the total weight of all surfactants used.
  • the aqueous surfactant formulation 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.
  • the aqueous surfactant formulation may also contain other components, such as, for example, C 4 -C 8 -alcohols and / or basic salts (so-called "alkaline surfactant flooding") . These additions may be used, for example, to reduce the retention in the formation.
  • the quantitative ratio of the alcohols with respect to the total amount of surfactant used is generally at least 1: 1 - however, a significant excess of alcohol can also be used
  • Suitable basic salts are sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide or silicates basic salts is typically from 0.1% to 5% by weight, based on the total amount of the aqueous surfactant formulation. At least one chelating agent can be added to the basic salts.
  • the deposits in which the process is used have a temperature of at least 10 ° C, for example 10 to 150 ° C, preferably a temperature of at least 15 ° C to 120 ° C.
  • the total concentration of all surfactants together is 0.05 to 5 wt .-% relative to the total amount of the aqueous Surfactant formulation, preferably 0.1 to 2.5 wt .-%.
  • 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.
  • the surfactants lead to a particularly good lowering of the interfacial tension. It is of course possible and also advisable to first produce a concentrate which is diluted on site to the desired concentration for injection into the formation. As a rule, the total concentration of the surfactants in such a concentrate is 10 to 45% by weight.
  • the alkylene oxide is metered in so that the temperature between 125 ° C to 155 ° C (for ethylene oxide) and 130 to 145 ° C (for propylene oxide) and 125 to 145 ° C. (at 1, 2-butylene oxide) remains.
  • the mixture is then stirred for 5 h at 125 to 145 ° C, rinsed with N 2 , cooled to 70 ° C and the reactor emptied.
  • the basic crude product is neutralized with acetic acid. Alternatively, the neutralization can be carried out with commercially available Mg silicates, which are then filtered off.
  • the bright product is characterized by means of a 1 H-NMR spectrum in CDCl 3 , a gel permeation chromatography and an OH number determination, and the yield is determined.
  • the alcohol to be alkoxylated (1, 0 eq) with a double metal cyanide catalyst eg DMC catalyst from BASF type Zn-Co
  • a double metal cyanide catalyst eg DMC catalyst from BASF type Zn-Co
  • the amount of DMC is 0.1% by weight and less of the product to be produced.
  • the mixture is then flushed three times with N 2 , a pre-pressure of about 1.3 bar N 2 is set and the temperature is increased to 120 to 130 ° C.
  • the alkylene oxide is metered in such that the temperature remains between 125 ° C to 135 ° C (for ethylene oxide) and 130 to 140 ° C (for propylene oxide) and 135 to 145 ° C (for 1, 2-butylene oxide).
  • the mixture is then stirred for 5 h at 125 to 145 ° C, rinsed with N 2 , cooled to 70 ° C and the reactor emptied.
  • the bright product is characterized by means of a 1 H-NMR spectrum in CDCl 3 , a gel permeation chromatography and an OH number determination, and the yield is determined.
  • the alkyl alkoxylate (1, 0 eq) to be sulfated is dissolved in 1.5 times the amount of dichloromethane (on a weight percent basis) and cooled to 5-10 ° C. Thereafter, chlorosulfonic acid (1, 1 eq) is added dropwise so that the temperature does not exceed 10 ° C.
  • the mixture is allowed to warm to room temperature and stirred under N 2 flow at this temperature for 4 h, before the above reaction mixture is poured into a half-volume aqueous NaOH solution at max. 15 ° C is dropped.
  • the amount of NaOH is calculated so that there is a slight excess with respect to the chlorosulfonic acid used.
  • the resulting pH is about pH 9 to 10.
  • the dichloromethane is added under a slight vacuum on a rotary evaporator at max. 50 ° C removed.
  • the product is characterized by 1 H-NMR and determines the water content of the solution (about 80%).
  • the following alcohols were used for the synthesis. Alcohol description
  • the interfacial tension between water and oil can be determined in a known manner by measuring the solubilization parameter SP * .
  • the determination of the interfacial tension via the determination of the solubilization parameter SP * is a method accepted in the art for the approximate determination of the interfacial tension.
  • the solubilization parameter SP * indicates how much ml of oil per ml of surfactant used is dissolved in a microemulsion (Windsor type III).
  • the interfacial tension ⁇ (interfacial tension, IFT) can be calculated from the approximate formula IFT "0.3 / (SP * ) 2 if equal volumes of water and oil are used (C. Huh, J. Coli., Interf. Sc, Vol. 71, No. 2 (1979)).
  • the formation of the microemulsion can be visually observed or by means of conductivity measurements. It forms a three-phase system (upper phase Oil, medium phase microemulsion, lower phase water). If the upper and lower phases are the same size and no longer change over a period of 24 h, then the optimum temperature (T opt ) of the microemulsion has been found. The volume of the middle phase is determined. From this volume, the volume of added surfactant is subtracted. The value obtained is then divided by two. This volume is now divided by the volume of added surfactant. The result is noted as SP * .
  • the type of oil and water used to determine SP * is determined according to the system under investigation. On the one hand petroleum itself can be used, or even a model oil such as decane. Both pure water and saline water can be used as water to better model the conditions in the oil formation.
  • the composition of the aqueous phase can be adjusted, for example, according to the composition of a particular reservoir water.
  • interfacial tensions of crude oil in the presence of the surfactant solution at the particular temperature can be determined by spinning-drop method on an SVT20 from DataPhysics.
  • an oil drop is injected into a capillary filled with saline surfactant solution at the respective temperature and the expansion of the drop is observed at approximately 4500 revolutions per minute until a constant value is established. This is usually the case after 2 hours.
  • the interfacial tension IFT (or s H) is calculated here - as described by Hans-Dieter Dörfler in "Interfacial and Colloidal Disperse Systems” Springer Verlag Berlin Heidelberg 2002 - using the following formula from the cylinder diameter d z , the speed w, and the density difference (drd 2 ):
  • a 1: 1 mixture of decane and a NaCl solution with butyl diethylene glycol (BDG) is added.
  • Butyl diethylene glycol (BDG) acts as a cosolvent and is not included in the calculation of SP * .
  • a surfactant mixture of alkylalkoxysulfate and anionic surfactant is added. The total surfactant concentration is given in weight percent of the aqueous phase.
  • Example 5 when using the claimed surfactant of the formula (I), it is possible to achieve an ultra-low interfacial tension with respect to decane. In the comparative examples, the interfacial tension is always higher.
  • Example 6 shows that also other surfactant combinations of surfactant of formula (I) and formula (II) give ultra low interfacial tensions.
  • the crude oil has about 16 ° API
  • the deposit temperature is around 20 ° C
  • the reservoir water has about 16100 ppm TDS (total dissolved salt) on.
  • Petrostep S2 surfactant mixture of olefin sulfonates prepared by sulfonation of alkenes with internal double bond (C15H30, C16H32, Ci7H3 4 and C18H36) followed by neutralization with NaOH.
  • the main product is unsaturated aliphatic sulfonates with the sulfonate group distributed along the carbon chain.
  • Example 12 of Table 5 a low interfacial tension of 0.007 mN / m can be achieved even with high salinities of 150000 ppm TDS on a simple crude oil (API grade of 33 °) with the aid of the claimed surfactants.
  • the surfactant solution is very slightly scattering and allows injection into a porous rock of suitable permeability.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention concerne un mélange de tensioactifs contenant au moins un alcanesulfonate secondaire comportant 14 à 17 atomes de carbone de formule générale (I) et au moins un tensioactif anionique de formule générale (II), R1, R2, R3, R4, A0, k, X, o, Y, a, b, M ayant la signification donnée dans la description et dans les revendications. L'invention concerne également l'utilisation et la production dudit mélange de tensioactifs, ainsi que des formulations de tensioactifs aqueuses contenant ce mélange, et un procédé d'extraction de pétrole par injection de micro-émulsions Winsor de type III, selon lequel la formulation de tensioactifs aqueuse est injectée dans un gisement pétrolifère par des trous d'injection et du pétrole brut est prélevé du gisement pétrolifère par des trous de production.
PCT/EP2013/072171 2012-10-26 2013-10-23 Procédé d'extraction de pétrole utilisant des tensioactifs contenant au moins un alcanesulfonate secondaire et un alkyléthersulfate/alkyléthersulfonate/alkyléthercarboxylate/alkylétherphosphate Ceased WO2014064152A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0302404A1 (fr) * 1987-08-05 1989-02-08 Hoechst Aktiengesellschaft Mélanges appropriés d'agents suractifs et leur utilisation pour la récupération d'huile
WO2003054125A1 (fr) * 2001-12-20 2003-07-03 Henkel Kommanditgesellschaft Auf Aktien Agent de nettoyage a microcapsules
US20080070823A1 (en) * 2006-09-15 2008-03-20 Philip Gorlin Liquid Detergent Composition
US20090048137A1 (en) * 2004-10-20 2009-02-19 Frank-Peter Lang Liquid detergent comprising secondary alkyl sulphonates and colour fixing agent
US20110083847A1 (en) * 2009-10-14 2011-04-14 Basf Se Process for tertiary mineral oil production using surfactant mixtures
WO2011110503A1 (fr) * 2010-03-10 2011-09-15 Basf Se Procédé d'extraction du pétrole au moyen de tensioactifs à base d'alcoxylates d'alkyle contenant de l'oxyde de butylène
WO2012084149A1 (fr) * 2010-12-22 2012-06-28 Clariant International Ltd Compositions contenant un sulfonate de paraffine secondaire et une tétrahydroxypropyl éthylène diamine

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0302404A1 (fr) * 1987-08-05 1989-02-08 Hoechst Aktiengesellschaft Mélanges appropriés d'agents suractifs et leur utilisation pour la récupération d'huile
WO2003054125A1 (fr) * 2001-12-20 2003-07-03 Henkel Kommanditgesellschaft Auf Aktien Agent de nettoyage a microcapsules
US20090048137A1 (en) * 2004-10-20 2009-02-19 Frank-Peter Lang Liquid detergent comprising secondary alkyl sulphonates and colour fixing agent
US20080070823A1 (en) * 2006-09-15 2008-03-20 Philip Gorlin Liquid Detergent Composition
US20110083847A1 (en) * 2009-10-14 2011-04-14 Basf Se Process for tertiary mineral oil production using surfactant mixtures
WO2011110503A1 (fr) * 2010-03-10 2011-09-15 Basf Se Procédé d'extraction du pétrole au moyen de tensioactifs à base d'alcoxylates d'alkyle contenant de l'oxyde de butylène
WO2012084149A1 (fr) * 2010-12-22 2012-06-28 Clariant International Ltd Compositions contenant un sulfonate de paraffine secondaire et une tétrahydroxypropyl éthylène diamine

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