EP3884010A1

EP3884010A1 - Method for extracting petroleum from underground deposits having high salinity

Info

Publication number: EP3884010A1
Application number: EP19801916.8A
Authority: EP
Inventors: Christian Bittner; Christian Spindler; Günter OETTER; David Ley; Lorenz Siggel
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2018-11-23
Filing date: 2019-11-19
Publication date: 2021-09-29
Also published as: WO2020104449A1; US20220002614A1

Abstract

The invention relates to a method for extracting petroleum from an underground petroleum reservoir, wherein, for the purposes of lowering the interface tension between oil and water to < 0.1 mN/m, an aqueous, saline tenside formulation comprising a tenside mixture is pressed through at least one injection bore into the petroleum reservoir and crude oil is extracted from the reservoir through at least one production bore, characterized in that the petroleum reservoir has a temperature of ≥25 °C and <130 °C and a formation water having a salinity of ≥50000 ppm of dissolved salts and the tenside mixture contains at least one anionic tenside (A) of the general formula R¹-O-(CH²-CH₂O)_o-(CH₂)_p-Y-M⁺(Il) and at least one anionic tenside (B) of the general formula R²-O-(CH₂CH₂O)_o-(CH₂)_p-Y-M⁺(II), wherein, upon injection in the tenside mixture, there is a molar ratio of anionic tenside (A) to anionic tenside (B) of 90 : 10 to 10: 90, and wherein the tenside mixture contains no ionic tenside of the general formula (R^1a)_k-N⁺(R^2a)_(3-k)R^3a (X-)_l(III). The invention further relates to a concentrate of the tenside mixture and to use thereof.

Description

Process for oil production of underground deposits with high salinity

description

The present invention relates to a method for the extraction of petroleum from a subterranean petroleum deposit, in which an aqueous, saline surfactant formulation comprising a surfactant mixture for the purpose of reducing the interfacial tension between oil and water to <0.1 mN / m, through at least one injection hole in the petroleum deposit pressed in and crude oil is extracted from the deposit through at least one production well, characterized in that the petroleum deposit has a temperature of> 25 ° C and <130 ° C and formation water with a salinity of> 50,000 ppm of dissolved salts and that the surfactant mixture has at least one contains anionic surfactant (A) and at least one anionic surfactant (B). The invention further relates to a concentrate of the surfactant mixture and the use thereof.

Surfactants for oil production (tertiary oil production) should be used in saline water at reservoir temperature, among other things. be readily soluble and provide very low interfacial tensions (less than 0.1 mN / m) compared to the crude oil. Ideally, the surfactant solution should form a Winsor Type III microemulsion when in contact with crude oil. The use of only one surfactant is usually very difficult because it is either readily soluble or provides low interfacial tensions (or microemulsions Winsor Type III), but very often does not have both properties at the same time. This applies in particular to petroleum deposits if it is formation water with high salinity (e.g. 100000 ppm of dissolved salts (TDS = total dissolved salt) and more. Medium temperatures (e.g. 50 ° C - 89 ° C) and higher temperatures (e.g. 90 up to 130 ° C) in the deposit exacerbate the problem.

Olefin sulfonates or alkylarylsulfonates alone are not sufficiently tolerant of salt - especially when polyvalent cations such as calcium ions and magnesium ions are present. When used alone, alkyl alkoxylates have a cloud point that is below 90 ° C at 100,000 ppm TDS. Anionically modified alkyl alkoxylates, which may have propyleneoxy groups, may also have solubility problems in the combination of elevated temperature and high salinity. Solubility is usually not a problem at low temperatures and low salinity.

Due to the high temperatures, thermostable connections are required, which do not decompose in the course of the flood process. Depending on the distance from the injection well to the production well, this flood process can result in the surfactants being exposed to high temperatures over a period of half a year to four years.

The conditions of high salinity described can be found in many oil deposits made of carbonate rock (e.g. in Russia oil deposits in carbonate rock known as carbonate deposits). Sites with> 50 ° C and> 100000 ppm TDS; or e.g. in the Middle East: oil deposits in carbonate rock so-called carbonate deposits with> 90 ° C and> 100000 ppm TDS). The surfactants used should have an acceptable or minimal tendency to adsorb on the carbonate rock.

US 4886120 mentions anion surfactants of the type R- (0CH ₂ CH ₂ ) _n -0S0 ₃ M, which are based on an alkyl radical R having 16 and 18 carbon atoms, in tertiary petroleum production. In the repeat units, n stands for a number from 2 to 5. M stands for sodium. In the examples there is only information for a deposit with 30 ° C and sea water.

EP 0177098 describes a surfactant mixture for tertiary oil production, which consists of an alkyl ether carboxylate and an alkylarylsulphonate. In the examples, tensides of the type C12C13 - 4.5 EO - CH ₂ C0 ₂ Na, C12C13 - 6 EO - CH ₂ C0 ₂ Na and C12-C15 - 9 EO - CH ₂ C0 ₂ Na are found. It is explicitly mentioned in Table 1 that the sole use of these alkyl ethoxy carboxylates does not lead to a Winsor type III microemulsion.

EP 0047370 describes the use of anionic surfactants of the type R- (OCH2CH2) _n -OCH2COOM, which are based on an alkyl radical R having 6 to 20 carbon atoms or an alkylated aromatic radical in which the total number of carbon atoms in the alkyl radicals is 1 to 14 , are based in tertiary oil production. In the repeat units, n stands for a number from 3 to 30. M stands for an alkali metal atom. The examples only show the use of carboxymethylated nonylphenol ethoxylate sodium salt with, for example, n = 6 (degree of carboxymethylation 80%) or carboxymethylated fatty alcohol ethoxylate sodium salt with, for example, R = C12C14 and n = 4.5 (degree of carboxymethylation 65%) or carboxymethylated fatty alcohol salt with, for example, R = C16 and n = 4.5 (degree of carboxymethylation 65%).

EP 0047369 describes the use of anionic surfactants of the type R- (OCH2CH2) _n -OCH2COOM, which are based on an alkyl or alkylaryl radical R having 4 to 20 carbon atoms or an alkylated aromatic radical in which the total number of carbon atoms in the alkyl radicals is 1 to 14 is based in the tertiary oil production. In the repeat units, n stands for a number from 3 to 15. M stands for an alkali metal atom or alkaline earth metal tallatom. The examples contain only information on compounds in which the alkylaryl radical is a nonylphenyl radical.

US 4457373 A describes the use of water-oil emulsions of anionic surfactants of the type R- (OCH2CH2) _n -OCH2COOM, which are based on an alkyl radical R having 6 to 20 carbon atoms or an alkylated aromatic radical in which the total number of carbon atoms in the alkyl radicals is 3 to 28, based in the tertiary oil production. In the repeat units, n stands for a number from 1 to 30. The surfactants are prepared by reacting the corresponding alkoxylates with chloroacetic acid sodium salt and sodium hydroxide or aqueous sodium hydroxide solution. The degree of carboxymethylation can range from 10% to 100% (preferably 90-100%). The examples only show the use of water-oil emulsions with carboxymethylated nonylphenol ethoxylate sodium salt with, for example, n = 6 (Car- boxymethylation degree 80%) or carboxymethylated fatty alcohol ethoxylate sodium salt with e.g. R = C12C14 and n = 4.5 (carboxymethylation degree 94%) or carboxymethylated fatty alcohol ethoxylate sodium salt with e.g. R = C16 and n = 4.5 (carboxymethylation degree 65%) or carboxymethylated fatty alcohol ethoxylate Sodium salt with, for example, R = C16 and n = 7 (degree of car boxymethylation 90%) compared to crude oil in salt water at temperatures from 46 to 85 ° C. The surfactant concentration used (> 5 percent by weight) was very high in the flood tests, which were carried out at <55 ° C. A polymer (polysaccharide) was used in the flood tests.

US Pat. No. 4,485,873 A describes the use of anionic surfactants of the R- (OCH2CH2) _n -OCH2COOM type, which are based on an alkyl radical R having 4 to 20 carbon atoms or an alkylated aromatic radical in which the total number of carbon atoms in the alkyl radicals 1 to 28 is based in tertiary oil production. In the repeat units, n stands for a number from 1 to 30. The surfactants are prepared by reacting the corresponding alkoxylates with sodium chloroacetate and sodium hydroxide or aqueous sodium hydroxide solution. The degree of carboxymethylation can range from 10% to 100% (preferably 50-100%). The examples only show the use of carboxymethylated nonylphenol ethoxylate sodium salt with, for example, n = 5.5 (degree of carboxymethylation 70%) or carboxymethylated fatty alcohol ethoxylate sodium salt with, for example, R = C12C14 and n = 4.4 (degree of carboxymethylation 65%) or carboxymethylated fatty alcohol ethoxylate with sodium salt R = C16 and n = 4.5 (degree of carboxymethylation 65%) compared to model oil in salt water at temperatures from 37 to 74 ° C. The surfactant concentration used (> 5% by weight) was very high in the flood tests, which were carried out at <60 ° C. Hydroxyethyl cellulose was used as the polymer in the flood tests.

US 4542790 A describes the use of anionic surfactants of the type R- (OCH2CH2) _n -OCH2COOM, which are based on an alkyl radical R having 4 to 20 carbon atoms or an alkylated aromatic radical in which the total number of carbon atoms in the alkyl radicals 1 to 28 is based in tertiary oil production. In the repeat units, n stands for a number from 1 to 30. The surfactants are prepared by reacting the corresponding alkoxylates with sodium chloroacetate and sodium hydroxide or aqueous sodium hydroxide solution. The degree of carboxymethylation can range from 10% to 100%. The examples show the use of carboxymethylated nonylphenol ethoxylate sodium salt with, for example, n = 5.3 (degree of carboxymethylation 76%) or carboxymethylated C12C14 fatty alcohol ethoxylate sodium salt compared to low-viscosity crude oil (10 mPas at 20 ° C.) in salt water at temperatures of 46 to 85 ° C. The surfactant concentration used (2% by weight) was relatively high in the flood tests, which were carried out at <60 ° C.

US 481 1788 A1 discloses the use of R- (OCH2CH2) _n -OCH2COOM, which are based on the alkyl radical 2-hexyldecyl (derived from C16-Guerbet alcohol) and in which n stands for the numbers 0 or 1, in tertiary oil production. EP 0207312 B1 describes the use of anionic surfactants of the type R- (OCH ₂ C (CH3) H) _m (OCH2CH2) _n -OCH ₂ COOM, which are based on an alkyl radical R having 6 to 20 carbon atoms or an alkylated aromatic radical which the total number of carbon atoms in the alkyl radicals is 5 to 40, based on a mixture with a hydrophobic surfactant in tertiary oil production. In the repeat units, m stands for a number from 1 to 20 and n for a number from 3 to 100. The surfactants are prepared by reacting the corresponding alkoxylates with chloroacetic acid sodium salt and sodium hydroxide or aqueous sodium hydroxide solution. The degree of carboxymethylation can range from 10% to 100%. The examples show the use of carboxymethylated dinonylphenol block propoxyoxyethylate sodium salt with m = 3 and n = 12 (degree of carboxymethylation 75%) together with alkylbenzenesulfonate or alkanesulfonate compared to model oil in sea water at temperatures of 20 or 90 ° C. The deoiling at 90 ° C in core flood tests gave worse values than at 20 ° C and the surfactant concentration used (4% by weight) was very high.

WO 2009/100298 A1 describes the use of anionic surfactants of the type R ¹ -0- (CH ₂ C (CH ₃ ) H0) _m (CH ₂ CH ₂ 0) _n -XY M ⁺ , which are based on a branched alkyl radical R ¹ with 10 up to 24 carbon atoms and a degree of branching of 0.7 to 2.5 are based in tertiary oil production. Y- can represent a carboxylate group. In the examples of the alkyl ether carboxylates, R1 always stands for a branched alkyl radical with 16 to 17 carbon atoms and X is always a CH ₂ group. The repetition units list examples with m = 0 and n = 9 or m = 7 and n = 2 or m = 3.3 and n = 6. The surfactants are prepared by reacting the corresponding alkoxylates with sodium chloroacetate and aqueous sodium hydroxide solution. The degree of carboxymethylation is disclosed at 93% for the example with m = 7 and n = 2. In the examples, the alkyl ether carboxylates are tested as sole surfactants (0.2 percent by weight) in sea water at 72 ° C. compared to crude oil. The interfacial tensions reached were always above 0.1 mN / m.

WO 09124922 A1 describes the use of anionic surfactants of the type R ¹ -0- (CH ₂ C (R ² ) HO) _{n "} (CH ₂ CH ₂ 0) _m" -R ⁵ -C00M, which are based on a branched, saturated alkyl rest R ¹ with 17 carbon atoms and a degree of branching of 2.8 to 3.7 are based in the tertiary oil production. R ² represents a hydrocarbon radical with 1 to 10 carbon atoms. R ₅ stands for a divalent hydrocarbon radical with 1 to 12 carbon atoms. Further, n "stands for a number from 0 to 15 and m" for a number from 1 to 20. These anionic surfactants can be obtained, inter alia, by oxidation of corresponding alkoxylates, a terminal group -CH ₂ CH ₂ OH being in a terminal group - CH ₂ C0 ₂ M is converted.

WO 1 1 1 10502 A1 describes the use of anionic surfactants of the type R ¹ -0- (CH ₂ C (CH ₃ ) H0) _m (CH ₂ CH ₂ 0) _n -XY M ⁺ , which are based on a linear saturated or unsaturated Alkyl radical R ¹ with 16 to 18 carbon atoms are based in the tertiary oil production. Y- can be a carboxylate group or a sulfate group and X can be an alkyl or alkylene group with up to 10 carbon atoms. Furthermore, m is preferably a Number from for 3 to 20 and n for a number from 0 to 99. These anionic surfactants can be obtained, inter alia, by reacting corresponding alkoxylates with sodium chloroacetate.

WO 2012/027757 A1 claims surfactants of the type R ¹ -0- (CH ₂ C (R ² ) H0) _n (CH (R ³ ) _z -C00M and their use in tertiary oil production. R ¹ stands for alkyl radicals or optionally substituted cycloalkyl or optionally substituted aryl radicals each having 8 to 150 carbon atoms. R ² or R ³ can be H or alkyl radicals having 1 to 6 carbon atoms. The value n stands for a number from 2 to 210 and z for a number from 1 to 6. Examples are only surfactant mixtures containing at least one sulfonate-containing surfactant (e.g. internal olefin sulfonates or alkylbenzenesulfonates) and an alkyl ether carboxylate, in which R1 is a branched, saturated alkyl radical with 24 to 32 carbon atoms and is known from Guer - derived alcohols with only one branch (in the 2-position). Said alkyl ether carboxylates have at least 25 repeat units in which R ^{2 is} CH3 and at least 10 repeat units in which R ^{2 is} H, ie ass n stands at least for a number greater than 39. In all examples, R ³ stands for H and z for the number 1. The surfactant mixtures contain at least 0.5% by weight of surfactant and are tested against crude oils at temperatures of 30 to 105 ° C.

WO 2013/159027 A1 claims surfactants of the type R ¹ -0- (CH2C (R ² ) H0) _n -X and their use in tertiary oil production. R ¹ stands for alkyl radicals each having 8 to 20 carbon atoms or for optionally substituted cycloalkyl or optionally substituted aryl radicals. R ² can be H or CH3. The value n stands for a number from 25 to 115. X stands for SO3M, SO3H, CH2CO2M or CH2CO2H (M ⁺ is a cation). Furthermore, structures of the type Ri-0- (CH2C (CH3) H0) _x - (CH2CH20) _y -X are disclosed, where x is a number from 35 to 50 and y is a number from 5 to 35. As an example, the surfactant C18H35-O- (CH2C (CH3) HO) 45- (CH2CH2O) 30-CH ₂ CO2M (C18H35 stands for oleyl) in a mixture with an internal C19-C28-olefin sulfonate and phenyldiethylene glycol. The surfactant mixtures contain at least 1.0 percent by weight of surfactant and are tested at temperatures of 100 ° C. and 32500 ppm total salinity in the presence of the base sodium metaborate against crude oils.

WO 2016/079121 A1 claims a surfactant mixture of R ¹ -0- (CH ₂ C (R ² ) H0) _x - (CH ₂ C (CH ₃ ) H0) y- (CH ₂ CH ₂ 0) _z -CH ₂ C0 ₂ M and R ¹ -0- (CH ₂ C (R ² ) H0) _x - (CH ₂ C (CH ₃ ) H0) y- (ChhChhOj _z -H in a molar ratio of 51: 49 to 92: 8 and their Use in tertiary oil production in deposits with temperatures from 55 ° C to 150 ° C. R ¹ stands for alkyl residues with 10 to 36 carbon atoms each, in the examples there are deposit conditions with 148200 ppm TDS and 100 ° C.

Despite the surfactants and surfactant mixtures known in the prior art, there is a need for improved surfactant mixtures, in particular for use in processes for petroleum production in petroleum deposits with high salinity and temperatures of below 90 ° C. Both solubility and the properties for lowering the interfacial tension should be improved ver. An object of the present invention is therefore to provide such a method and a concentrate.

The object is achieved by a process for extracting crude oil from an underground oil deposit, in which an aqueous, salt-containing surfactant formulation comprising a surfactant mixture in order to reduce the interfacial tension between oil and water to <0.1 mN / m, through at least one injection hole in the The oil deposit is pressed in and crude oil is extracted from the deposit through at least one production well, characterized in that the oil deposit has a temperature of> 25 ° C and <130 ° C and a formation water with a salinity of> 50,000 ppm of dissolved salts and that the surfactant mixture has at least an anionic surfactant (A) of the general formula

(i)

R ¹ -0- (CH ₂ CH ₂ 0) o- (CH2) pY- M ⁺ (I) and at least one anionic surfactant (B) of the general formula (II)

R ² -0- (CH ₂ CH ₂ 0) _O - (CH ₂ ) _P -Y- M ⁺ (II), with a molar ratio of anionic surfactant (A) to anionic surfactant (B) when injected in the surfactant mixture from 90:10 to 10:90, where

R ^{1 represents} a linear, saturated or unsaturated, aliphatic hydrocarbon radical with 16 carbon atoms;

R ^{2 represents} a linear, saturated or unsaturated, aliphatic hydrocarbon radical which has two methylene groups more than R ¹ ;

each Y is independently SO3 or C0 ₂ ;

each M independently for Na, K, N (CH ₂ CH ₂ OH) ₃ H, N (CH ₂ CH (CH ₃ ) OH) ₃ H,

N (CH ₃ ) (CH ₂ CH ₂ OH) ₂ H, N (CH ₃ ) ₂ (CH ₂ CH ₂ OH) H, N (CH ₃ ) ₃ (CH ₂ CH ₂ OH), N (CH ₃ ) ₃ Is H, N (C ₂ H ₅ ) ₃ H or NH ₄ ;

each o is independently a number from 6 to 20;

each p independently represents a number from 0 to 3; where p is the number 1 if Y is C0 ₂ ;

p represents the number 0, 2 or 3 if Y represents S0 ₃ ; wherein the surfactant mixture is not an ionic surfactant of the general formula (III)

(R ^{1 a} ) _k - N ⁺ (R ^2a ) ₍₃ -k) R ^3a (X-) i (III), where each R ^{1a is} independently a linear or branched, saturated or unsaturated, aliphatic hydrocarbon radical with 8 to 22 carbon atoms or represents the radical R ^4a - 0- (CH2C (R ^5a ) HO) _ma - (CH2C (CH3) HO) na- (CH2CH20) oa- (CH ₂ CH2) - or R ^4a -0- (CH ₂ C (R ^5a ) H0) _ma - (CH ₂ C (CH ₃ ) HO) _na - (CH ₂ CH ₂ 0) _oa - (CH ₂ C (CH ₃ ) H) -;

each R ^{2a is} CH3;

R ^{3a is} CH ₃ or (CH2CO2) -;

each R ^4a independently represents a linear or branched, saturated or unsaturated, aliphatic hydrocarbon radical having 8 to 36 carbon atoms or an aromatic or aromatic-aliphatic hydrocarbon radical having 8 to 36 carbon atoms; each R ^5a independently represents a linear or branched, saturated or unsaturated, aliphatic hydrocarbon radical having 2 to 16 carbon atoms or an aromatic or aromatic-aliphatic hydrocarbon radical having 6 to 10 carbon atoms;

X represents CI, Br, I or H3CO-SO3;

k represents the number 1 or 2,

I represents the number 0 or 1;

each ma independently represents a number from 0 to 15;

each na independently represents a number from 0 to 50;

each of the above is independently a number from 1 to 60; where the sum of na + oa stands for a number from 7 to 80

I stands for the number 0 if R ^{3 is} (CH2CO2) - or stands for 1 if R ^{3 is} CH ₃ .

A surfactant mixture - also referred to as a surfactant mixture - as described above surprisingly shows very good temperature stability and can therefore be used in the process according to the invention. A corresponding concentrate also has advantages.

Accordingly, the present invention further provides a concentrate, based in each case on the total amount of the concentrate

20% by weight to 90% by weight of a surfactant mixture according to the invention, where the molar ratio of anionic surfactant (A) to anionic surfactant (B) can be as desired, 5% by weight to 40% by weight of water and 5 % By weight to 40% by weight of a cosolvent. Surprisingly, particularly good properties can be achieved even under the most difficult conditions if a surfactant mixture as described herein with surfactants (A) and (B) is used. Sufficient solubility of the surfactants in storage water can be achieved and at the same time the formation of a microemulsion Winsor type III in the presence of crude oil can be effected. It is also surprising that the positive properties of the surfactant mixture can be further improved if surfactants (C) are also present in the surfactant mixture.

Surfactant mixtures with anionic surfactant (A) of the general formula (I) and anionic surfactant (B) of the general formula (II) are suitable for deposits made of carbonate rock (preferably weakly negatively charged or neutral carbonate rock with a zeta potential of -4 to 0 mV and particularly preferably positively charged carbonate rock with a zeta potential> 0 mV).

In the process according to the invention, the surfactant mixture has at least one surfactant (A) of the general formula (I) and at least one surfactant (B) of the general formula (II) and preferably at least one anionic surfactant (C) of the general formula (IV). During the injection, i.e. at the time when the surfactant mixture together with the injection water forms the aqueous, salt-containing surfactant formulation and this is brought into the interior of the earth ("injection"), the molar ratio of surfactant (A) to surfactant (B) is 90 : 10 to 10: 90. Accordingly, the surfactant formulation comprises (contains) at least the surfactant mixture and water and, if appropriate, further salts, in particular those which are present in saline water, such as sea water, and optionally at least one anionic surfactant (C).

Accordingly, the aqueous, salt-containing surfactant formulation means a surfactant mixture, optionally with at least one anionic surfactant (C), which is dissolved in salt-containing water (e.g. during the pressing-in process). The saline water can include river water, sea water, water from an aquifer near the deposit, so-called injection water, deposit water, so-called production water, which is re-injected, or mixtures of the water described above. However, it can also be saline water obtained from a more saline water: e.g. partial desalination, depletion of the polyvalent cations or by dilution with fresh water or drinking water. The surfactant mixture can preferably be provided as a concentrate, which, due to the manufacture, can also contain salt. This is continued in the following sections.

When the surfactant mixture is injected, a molar ratio of ionic surfactant (A) to anionic surfactant (B) is preferably from 80:20 to 20:80, preferably 40:60 to 20:80, more preferably 30:70.

The surfactant mixture has at least one anionic surfactant (A) of the general formula (I) R ¹ -0- (CH ₂ CH ₂ 0) o- (CH2) pY- M ⁺ (I) and at least one anionic surfactant (B) of the general formula (II)

R ² -0- (CH ₂ CH ₂ 0) _O - (CH ₂ ) _P -Y- M ⁺ (II). Accordingly, one or more anionic surfactants (A), such as two, three or more ionic surfactants (A), may be present. The same applies to the anionic surfactant (B).

The radical R ¹ is a linear, saturated or unsaturated, aliphatic hydrocarbon radical with 16 carbon atoms. It is preferred that the radical that R ^{1 stands} for a linear, saturated ge aliphatic primary hydrocarbon radical with 16 carbon atoms.

The radical R ² stands for a linear, saturated or unsaturated, aliphatic Kohlenwas serstoffrest, which has two methylene groups more than R ¹ . It is preferred that the radical R ^{2 stands} for a linear saturated aliphatic primary hydrocarbon radical with 18 carbon atoms.

The variable o indicates how many ethylene oxide units are present in the surfactants of the formulas (I) and (II). There are 6 to 20 ethylene oxide units. These can be the same or different for formula (I) compared to formula (II), preferably they are the same. Before o is preferably a number from 6 to 15, preferably a number from 8 to 12, in particular special for 10.

The variable p indicates whether there are no (p = 0), one (p = 1), two (p = 2) or three (p = 3) methylene groups in formulas (I) and (II). These can be present in both formulas independently of one another (p = 1, 2 or 3) or not (p = 0). This is preferably the same for both formulas or not, more preferably it is available for both formulas (p = 1, 2 or 3), more preferably p = 1. Accordingly, it is preferred that at least one anionic surfactant (A) or (B) is a carboxyate. The anionic surfactants (A) and (B) are more preferably a carboxylate.

The remainder Y indicates the anion Y-. It can be a sulfate (Y = S0 ₃ , p = 0), a sulfonate (Y = S0 ₃ , p = 2 or 3) or a carboxylate (Y = C0 ₂ , p = 1). Carboxyate is preferred.

The variable M denotes the cation in the formulas (I) and (II). The cation of formula (I) can be the same or different compared to the cation of formula (II), but it is preferably the same. The cation is Na, K, N (CH ₂ CH ₂ OH) 3H,

N (CH ₂ CH (CH ₃ ) OH) ₃ H, N (CH ₃ ) (CH ₂ CH ₂ OH) ₂ H, N (CH ₃ ) ₂ (CH ₂ CH ₂ OH) H, N (CH ₃ ) ₃ (CH ₂ CH ₂ OH), N (CH ₃ ) ₃ H, N (C ₂ H ₅ ) ₃ H or NFU. The cation is preferably selected from Na, K or NFU. Na is more preferred. The anionic surfactants (A) and (B) of the surfactant mixture in the process according to the invention are present in the aqueous, salt-containing surfactant formulation in undissolved, partially dissolved or completely dissolved form, preferably in completely dissolved form.

Ionic surfactants (A) and (B) are either commercially available or can be prepared by known methods known to those of ordinary skill in the art. As an example, reference is made to WO 2016/079121 A1. The same applies to the preferably also present surfactants (C).

The surfactant mixture in the process according to the invention preferably contains no ionic surfactant of the general formula (III)

(R ^{1 a} ) _k - N ⁺ (R ^2a ) ₍₃ -k) R ^3a (X-) i (III), where each R ^{1a is} independently a linear or branched, saturated or unsaturated, aliphatic hydrocarbon radical with 8 to 22 carbon atoms or represents the radical R ^4a - 0- (CH2C (R ^5a ) HO) _ma - (CH2C (CH3) HO) na- (CH2CH20) oa- (CH ₂ CH2) - or R ^4a -0- (CH ₂ C (R ^5a ) H0) _ma - (CH ₂ C (CH ₃ ) HO) n _a - (CH ₂ CH ₂ 0) _oa - (CH ₂ C (CH ₃ ) H) -; each R ^{2a is} CH3;

R ^{3a is} CH ₃ or (CH2CO2) -; each R ^4a independently represents a linear or branched, saturated or unsaturated, aliphatic hydrocarbon radical having 8 to 36 carbon atoms or an aromatic or aromatic-aliphatic hydrocarbon radical having 8 to 36 carbon atoms; each R ^5a independently represents a linear or branched, saturated or unsaturated, aliphatic hydrocarbon radical having 2 to 16 carbon atoms or an aromatic or aromatic-aliphatic hydrocarbon radical having 6 to 10 carbon atoms;

X represents CI, Br, I or H3CO-SO3; k represents the number 1 or 2,

I represents the number 0 or 1; each ma independently represents a number from 0 to 15; each na independently represents a number from 0 to 50; each of the above is independently a number from 1 to 60; where the sum of na + oa stands for a number from 7 to 80

I stands for the number 0 if R ^{3 is} (CH ₂ C0 ₂ ) - or stands for 1 if R ^{3 is} CH ₃ .

Surfactant mixtures of individual anionic surfactants (A) and (B) with the ionic surfactant of the formula (III) are known from WO 2018/219654 A1. Accordingly, ionic surfactants of the formula (III), as described in WO 2018/219654 A1, are preferably not present. However, surfactant mixtures of anionic surfactants (A), (B) and (C) are from WO

2018/219654 A1 is not known, so that for this combination the surfactant mixture according to the present invention may also contain surfactants of the formula (III).

In addition to at least one surfactant of the formula (I) and at least one surfactant of the formula (II), the surfactant mixture according to the present invention preferably also comprises at least one anionic surfactant (C) of the general formula (IV)

R ^3b -0- (CH ₂ CHCH30) nb- (CH2CH20) ob- (CH ₂ ) pb-Yb- M _b ⁺ (IV), where

R ^{3b represents} a linear or branched, saturated or unsaturated, aliphatic, primary hydrocarbon radical having 16 to 18 carbon atoms;

Y _{b represents} S0 ₃ or C0 ₂ ;

M _b for Na, K, N (CH ₂ CH ₂ OH) ₃ H, N (CH ₂ CH (CH ₃ ) OH) ₃ H, N (CH ₃ ) (CH ₂ CH ₂ OH) ₂ H,

N (CH ₃ ) ₂ (CH ₂ CH ₂ OH) H, N (CH ₃ ) ₃ (CH ₂ CH ₂ OH), N (CH ₃ ) ₃ H, N (C ₂ H ₅ ) ₃ H or NH ₄ ; nb stands for a number from 3 to 10

whether independently represents a number from 8 to 20;

pb independently represents a number from 0 to 3; where pb is the number 1 if Y _{b is} C0 ₂ ;

pb stands for the number 0, 2 or 3 if Y _b stands for SO3.

Accordingly, one or more anionic surfactants (C), such as two, three or more anionic surfactants (C), may be present.

The radical R ^{3b here is} a linear or branched, saturated or unsaturated, aliphatic, primary hydrocarbon radical having 16 to 18 carbon atoms. The radical R ^{3b is} preferably a linear, saturated or unsaturated, aliphatic, primary hydrocarbon radical having 16 to 18 carbon atoms. The radical R ^{3b more} preferably stands for a linear, saturated, aliphatic, primary hydrocarbon radical with 16 to 18 carbon atoms. There are preferably at least two radicals R ^3b for two surfactants which have 16 and 18 carbon atoms and, with the exception of the ethyleneoxy and propyleneoxy units present, correspond to surfactants (A) and (B). This also applies to the molar relationship to one another. This can be achieved in particular by using the same alcohol mixture to prepare the surfactants of the formulas (I) and (II) and (IV).

The variable pb indicates whether there are no (pb = 0), one (pb = 1), two (pb = 2) or three (pb = 3) methylene groups in formula (IV). These can be present (pb = 1, 2 or 3) or not (pb = 0). This is preferably present (pb = 1, 2 or 3), more preferably pb = 1.

The rest Y _b indicates the anion Y _b -. It can be a sulfate (Y _b = S0 ₃ , pb = 0), a sulfonate (Y _b = S0 ₃ , pb = 2 or 3) or a carboxylate (Y _b = C0 ₂ , pb = 1). Carboxyate is preferred. Accordingly, Y _b and pb are preferably CO2 and 1.

The variable whether indicates how many ethylene oxide units are present in the surfactant of the formula (IV). There are 8 to 20 ethylene oxide units. Preferably, whether is a number from 8 to 18, more preferably a number from 8 to 15, more preferably a number from 8 to 12, more preferably a number from 9 to 11, in particular 10.

The variable Mb denotes the cation in formula (IV). The cation is Na,

K, N (CH ₂ CH ₂ OH) ₃ H, N (CH ₂ CH (CH ₃ ) OH) ₃ H, N (CH ₃ ) (CH ₂ CH ₂ 0H) ₂ H, N (CH ₃ ) ₂ (CH ₂ CH ₂ OH) H, N (CH ₃ ) 3 (CH ₂ CH ₂ OH), N (CH ₃ ) ₃ H, N (C ₂ H ₅ ) ₃ H or NH ₄ . The cation is preferably selected from Na, K or NH ₄ . Na is more preferred. In particular, it is preferred that “Mb” has the same value as the variable M in formula (I) or formula (II), in particular in formulas (I) and (II).

The number nb indicates the number of propyleneoxy units in formula (IV). It is in the range of 3 to 10. Accordingly, 3, 4, 5, 6, 7, 8, 9 or 10 propyleneoxy units are present in formula (IV). Preferably 4, 5, 6, 7, 8 or 10 propyleneoxy units are present in formula (IV). More preferably 5, 6, 7, 8 or 9 propyleneoxy units are present in formula (IV). More preferably 6, 7 or 8, in particular 7, propyleneoxy units are present in formula (IV).

In the presence of surfactant mixtures which comprise several surfactants (A) / (B) and, if appropriate, (C) of the general formula (I) / (II) or (IV), the numbers o, nb, whether, as has already been stated above, mean values for all molecules of the surfactants. In particular in the alkoxylation of alcohol with ethylene oxide or propylene oxide, a certain distribution of chain lengths is usually obtained in each case. 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 of the molar mass and the number average of the molar mass. The polydispersity can be determined using the methods known to the person skilled in the art, for example using gel permeation Chromatography. If a single formula for a surfactant is given, it is the most frequently occurring compound in the mixture without further details.

The alkyleneoxy groups can thus be randomly distributed, alternating or in blocks, i.e. be arranged in two, three, four or more blocks.

Preferably, the nb propylene and whether ethyleneoxy groups in formula (IV) are at least partially preferred (preferably numerically at least 50%, 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 in the context of the present invention means that at least one alkyleneoxy has a neighboring alkyleneoxy group which is chemically identical, so that these form at least two alkyleneoxy units in a block. Particularly preferably, a R ^3b -0 group is followed by a propyleneoxy block with nb propyleneoxy groups and then an ethyleneoxy block with ethylene oxide groups.

Preferably the molar ratio of the sum of surfactant (A) and surfactant (B) to surfactant (C) ((A) + (B): (C)) is in the range of 100: 0 to 50:50, more preferably 90 : 10 to 50:50.

The method according to the invention is used to extract crude oil from underground crude oil storage sites in which an aqueous, salt-containing surfactant formulation comprising a tenside mixture is used to lower the interfacial tension between oil and water

<0.1 mN / m is used. The formulation is pressed into an oil deposit through at least one injection hole and crude oil is extracted from the deposit through at least one production hole, the oil deposit having a temperature of> 25 ° C and <130 ° C and formation water with a salinity of> 50,000 ppm ( Weight fraction based on total weight) of dissolved salts (TDS). The oil reservoir preferably has formation water with a salinity of> 75,000 ppm of dissolved salts, preferably> 100,000 ppm, more preferably> 120,000 ppm, further more preferably> 130,000 ppm, of dissolved salts. The oil deposit preferably has a temperature of> 50 ° C, preferably> 65 ° C, and preferably <90 ° C.

For the determination of the oil reservoir temperature, for example, borehole measurements are carried out in which a thermometer is suspended from a cable in the bores and the temperature of the oil carrier is measured at two or more depths. From this, the average temperature is determined, which represents the oil reservoir temperature. Oil reservoir temperature measurements are often carried out using light guides (see also http://petrowiki.Org/Reservoir_pressure_and_temperature#Measurement_of_reservoir_pressure_ andjemperature).

The salinity can be determined using mass spectrometry with inductively coupled plasma mass spectrometry (ICP-MS). In a further preferred embodiment of the invention, a thickening polymer from the group of biopolymers or from the group of copolymers based on acrylamide is added to the aqueous, salt-containing surfactant formulation. The copolymer can consist, for example, of the following building blocks:

Acrylamide and acrylic acid sodium salt

Acrylamide and acrylic acid sodium salt and N-vinyl pyrolidone

Acrylamide and acrylic acid sodium salt and AMPS (2-acrylamido-2-methylpropanesulfonic acid sodium salt)

Acrylamide and acrylic acid sodium salt and AMPS (2-acrylamido-2-methylpropanesulfonic acid sodium salt) and N-vinyl pyrolidone

The copolymer which was built up from acrylamide and acrylic acid sodium salt and AMPS (2-acrylamido-2-methylpropanesulfonic acid sodium salt) and N-vinylpyrolidone is particularly preferred. The copolymer can also contain additional groups.

In a particularly preferred embodiment, the process according to the invention is a Winsor type III microemulsion polymer flooding.

Additional additives such as biocides, stabilizers, radical scavengers and inhibitors can be added to stabilize the polymers.

Instead of or in addition to the addition of a polymer, a foam can also be added for the purpose of mobility control. The foam can be generated on the surface of the deposit or in situ in the deposit by injecting gases such as nitrogen or gaseous hydrocarbons such as methane, ethane or propane. The gaseous hydrocarbons can also be mixtures containing methane, ethane or propane. To generate and stabilize the foam, the surfactant mixture described here or other surfactants can be added.

Optionally, a base such as alkali metal hydroxide or alkali metal carbonate can also be added to the surfactant formulation, it being combined with complexing agents or polyacrylates in order to avoid precipitation due to the presence of polyvalent cations. A cosolvent can also be added to the formulation.

This results in the following (combined) procedures:

Surfactant floods

Winsor type III microemulsion floods

Surfactant polymer floods

Winsor Type III microemulsion polymer flooding

Alkali surfactant polymer flooding

Alkaline Winsor Type III microemulsion polymer flooding

Surfactant foam floods Winsor Type III microemulsion foam flooding

Alkali surfactant foam flooding

Alkaline Winsor Type III microemulsion foam flooding

In a preferred embodiment of the invention, one of the first four methods is used (surfactant flooding, Winsor type III microemulsion flooding, surfactant polymer flooding or Winsor type III microemulsion polymer flooding). Winsor type III microemulsion polymer flooding is particularly preferred.

With Winsor Type III microemulsion polymer flooding, a surfactant formulation with or without polymer is injected in the first step. When in contact with crude oil, the surfactant formulation causes the formation of a Winsor type III microemulsion. In the second step, only polymer is injected. Aqueous formulations with higher salinity than in the second step can be used in each case in the first step. Alternatively, both steps can also be carried out with water of the same salinity. In the first step, a gradient procedure can also be carried out in the surfactant mixture. This will be explained using an example. Under storage conditions, for example, a surfactant mixture containing 30 mol% anionic surfactant (A) of the general formula (I) and 70 mol% anionic surfactant (B) of the general formula (II) forms a microemulsion Winsor type III with the crude oil. The salinity of the injection water corresponds to that of the formation water. In addition, for example, surfactant (C) of the general formula (IV) should be 50%. For the injection, a surfactant mixture is first mixed from a constant 30 mol% anionic surfactant (A) of the general formula (I) to 70 mol% anionic surfactant (B) of the general formula (II) and varying and starting with 0% ten sid ( C) started. In the course of the injection, the ratio (A) + (B): (C) is changed so that the ratio is 30 mol% ionic surfactant (A) of the general formula (I) to 70 mol% anionic surfactant (B) general formula (II) remains and (A) + (B): (C) 90:10 he is enough. The injection is then continued, with the surfactant ratio (A) + (B): (C) 50:50 finally being achieved by further step-wise changing of the surfactant ratio. This process can optionally be carried out in the presence of other surfactants, polymer and / or foam and other additives described above.

In one embodiment, the methods can of course also be combined with water floods. When water is flooded, water is injected through at least one injection well into an oil storage facility and crude oil is extracted from the reservoir through at least one production well. The water can be fresh water or saline water such as sea water or reservoir water. After flooding the process according to the invention can be used.

To carry out the method according to the invention, at least one production well and at least one injection well are drilled into the oil deposit. As a rule, a deposit is provided with several injection wells and with several production wells. There may be vertical and / or horizontal bores. An aqueous formulation of the water-soluble described is through the at least one injection hole Components injected into the oil deposit and extracted oil from the deposit through at least one production well. Due to the pressure generated by the pressed-in aqueous formulation, the so-called "flood", the petroleum flows in the direction of the production well and is extracted via the production well. In this context, the term "petroleum" is of course not only meant to be single-phase oil, but also includes the usual crude oil-water emulsions. It is clear to the person skilled in the art that an oil storage facility can also have a certain temperature distribution. The above-mentioned deposit temperature refers to the area of the deposit between the injection and production holes, which is covered by flooding with aqueous solutions. Methods for determining the temperature distribution of a petroleum deposit are known in principle to the person skilled in the art. The temperature distribution is usually determined from temperature measurements at certain points in the formation in combination with simulation calculations, whereby the simulation calculations also take into account the heat quantities introduced into the formation and the heat quantities dissipated from the formation.

The method according to the invention can be used in particular in petroleum deposits with an average porosity of 1 mD to 4 D, preferably 2 mD to 2 D and particularly preferably 5 mD to 500 mD. The permeability of an oil formation is specified by a specialist in the unit "Darcy" (abbreviated "D" or "mD" for "Millidarcy") and can be determined from the flow rate of a liquid phase in the oil formation depending on the pressure difference applied. The flow rate can be determined in core flood tests with drill cores taken from the formation. Details on this can be found, for example, in K. Weggen, G. Pusch, H. Rischmüller in “Oil and Gas”, pages 37 ff., Ullmann's Encyclopedia of Industrial Chemistry, online edition, Wiley-VCH, Weinheim 2010. For the specialist it is clear that the permeability in an oil deposit does not have to be homogeneous, but generally has a certain distribution and accordingly the indication of the permeability of an oil deposit is an average permeability.

To carry out the process, an aqueous formulation is used which, in addition to water, contains at least the described surfactant mixture of anionic surfactant (A) of the general formula (I) and the anionic surfactant (B) of the general formula (II) and, if appropriate, surfactant (C) includes.

The formulation is prepared in water containing salts. Of course, it can be mixtures of different salts. For example, sea water can be used to set the aqueous formulation or it can be used formation water, which is reused in this way. However, the injection water can also be formation water from other nearby reservoirs or aquifers. In the case of production platforms in the sea, the formulation is usually applied in sea water. In the case of conveyors on land, the surfactant or polymer can advantageously first be dissolved in fresh water or lower salt water and the solution obtained can be diluted with formation water to the desired use concentration. At the Injection water can also be water that comes from a desalination plant. Alternatively, the proportion of sulfate ions could be reduced from sea water, for example, so that modified sea water can be injected into a deposit rich in calcium ions without precipitation.

In a preferred embodiment, the reservoir water or the sea water should have at least 100 ppm of divalent cations.

The salts can in particular be alkali metal salts and alkaline earth metal salts. Examples of typical cations include Na ⁺ , K ⁺ , Mg ²⁺ and / or Ca ²⁺ and examples of typical anions include chloride, bromide, hydrogen carbonate, sulfate or borate.

As a rule, at least one or more alkali metal ions, in particular at least Na ^+, are present. In addition, alkaline earth metal ions are also present, the weight ratio of alkali metal ions / alkaline earth metal ions generally being> 2, preferably> 3. At least one or more halide ions, in particular at least Ch, are generally present as anions. As a rule, the amount of Ch is at least 50% by weight, preferably at least 80% by weight, based on the sum of all anions.

Additives can be used, for example, to reduce undesirable side effects, e.g. to prevent the unwanted precipitation of salts or to stabilize the surfactant or polymer used. The polymer-containing formulations injected into the formation during flooding flow very slowly in the direction of the production well, i.e. they remain in the formation for a long time under formation conditions. Degradation of the polymer results in a decrease in viscosity. This must either be taken into account by using a higher amount of polymer or it must be accepted that the efficiency of the process deteriorates. In any case, the economics of the process deteriorate. A variety of mechanisms can be responsible for the degradation of the polymer. Suitable additives can prevent or at least delay the polymer degradation depending on the conditions.

In one embodiment of the invention, the aqueous formulation used comprises at least one oxygen scavenger. Oxygen scavengers react with oxygen, which may possibly be contained in the aqueous formulation, and thus prevent the oxygen from attacking the polymer or polyether groups. Examples of oxygen scavengers include sulfites such as Na ₂ S0 ₃ , bisulfites, phosphites, hypophosphites or dithionites.

In a further embodiment of the invention, the aqueous formulation used comprises at least one radical scavenger. Radical scavengers can be used to counteract the degradation of the polymer or the polyether group-containing surfactant by radicals. Such compounds (radical scavengers) can form stable compounds with radicals. Radical scavengers are known in principle to the person skilled in the art. For example, stabilizers selected from the group of sulfur-containing compounds, secondary amines, sterically hindered amines, N-oxides, nitroso compounds, aromatic hydrocarbons Trade xy compounds or ketones. Examples of sulfur compounds include thiourea, substituted thioureas such as N, N'-dimethylthiourea, N, N'-diethylthiourea, N, N'-diphenylthiourea, thiocyanates such as, for example, ammonium thiocyanate or potassium thiocyanate, tetramethylthiuram disothiazole or mercaptob 2-mercaptobenzimidazole or its salts, for example the sodium salts, sodium dimethyldithiocarbamate, 2,2'-dithiobis (benzothiazole), 4,4'-thiobis (6-t-butyl-m-cresol). Other examples include phenoxazine, salts of carboxylated phenoxazine, carboxylated phenooxazine, methylene blue, dicyandiamide, guanindine, cyanamide, paramethoxyphenol, sodium salt of para methoxyphenol, 2-methylhydroquinone, salts of 2-methylhydroquinone, 2,6-di-t-butyl- 4-methylphenol, butylhydroxyanisole, 8-hydroxyquinoline, 2,5-di (t-amyl) hydroquinone, 5-hydroxy-1, 4-naphthoquinone, 2,5-di (t-amyl) hydroquinone, dimedone, propyl-3, 4,5-trihydroxybenzoate, ammonium N-nitrosophenylhydroxylamine, 4-hydroxy-2,2,6,6-tetramethyoxylpiperidine, (N- (1,3-dimethylbutyl) N'-phenyl-p-phenylenediamine or 1,2,2 , 6, 6-pentamethyl-4-piperidinol, preferably sterically hindered amines such as 1, 2,2,6,6-pentamethyl-4-piperidinol and sulfur compounds, mercapto compounds, especially 2-mercaptobenzothiazole or 2-mercaptobenzimidazole or the salts thereof, for example the sodium salts, and particularly preferred are 2-mercaptobenzothiazole or salts thereof.

In a further embodiment of the invention, the aqueous formulation used comprises at least one sacrificial reagent. Victim reagents can react with radicals, rendering them harmless. Examples particularly include alcohols. Alcohols can be oxidized by radicals, for example to ketones. Examples include monoalcohols and polyalcohols such as 1-propanol, 2-propanol, propylene glycol, glycerin, butanediol or pentaerythritol.

In a further embodiment of the invention, the aqueous formulation used comprises at least one complexing agent. Mixtures of different complexing agents can of course be used. Complexing agents are generally anionic compounds which, in particular, can complex two or higher metal ions, for example Mg ²⁺ or Ca ²⁺ . In this way, possibly undesired precipitations can be avoided. Furthermore, it can be prevented that any polyvalent metal ions that are present crosslink the polymer via acidic groups, in particular COOH groups. The complexing agents can in particular be carboxylic acid or phosphonic acid derivatives. Examples of complexing agents include ethylenediaminetetraacetic acid (EDTA), ethylenediaminodisuccinic acid (EDDS), diethylenetriaminepentamethylenephosphonic acid (DTPMP), methylglycinediacetic acid (MGDA) or nitrilotriacetic acid (NTA). Of course, it can also be the corresponding salts, for example the corresponding sodium salts. In a particularly preferred embodiment of the invention, MGDA is used as a complexing agent.

Polyacrylates can also be used as an alternative or in addition to the chelating agents mentioned above. In a further embodiment of the invention, the formulation contains at least one organic cosolvent. Solvents which are completely miscible with water are preferred, but solvents which are only partially miscible with water can also be used. In normal cases, the solubility should be at least 0.5 g / l preferably at least 1 g / l Betra gene. Examples include aliphatic C4 to Cs-alcohols, C4 alcohols, preferably ₆ to C wel che to achieve sufficient solubility in water of 1 to 5, preferably 1 to 3 ethylene oxy units can be substituted. Further examples include aliphatic diols with 2 to 8 carbon atoms, which can optionally also be further substituted. For example, it can be at least one cosolvent selected from the group of 2-butanol, 2 methyl-1-propanol, butyl glycol, butyl diglycol or butyl triglycol.

The concentration of the polymer in the aqueous formulation is determined such that the aqueous formulation has the desired viscosity or mobility control for the intended use. The viscosity of the formulation should generally be at least 5 mPas (measured at 25 ° C. and a shear rate of 7 S ¹ ), preferably at least 10 mPas.

According to the invention, the concentration of the polymer in the formulation is 0.02 to

2% by weight based on the sum of all components of the aqueous formulation. The amount is preferably 0.05 to 1% by weight, particularly preferably 0.1 to 0.8% by weight and, for example, 0.1 to 0.4% by weight.

The formulation containing the possible aqueous polymer can be prepared by introducing the water, sprinkling the polymer in powder and mixing it with the water. Before the devices for dissolving polymers and injecting the aqueous solutions into underground formations are known in principle to the person skilled in the art.

The aqueous formulation can be injected using conventional devices. The formulation can be injected into one or more injection bores using conventional pumps. The injection bores are usually lined with cemented steel pipes, and the steel pipes are perforated at the desired location. The formulation enters through the perforation from the injection well into the petroleum formation. The flow rate of the formulation and thus also the shear stress with which the aqueous formulation enters the formation is determined in a known manner via the pressure applied by means of the pumps. The shear stress when entering the formation can be calculated by the person skilled in the art in a manner known in principle on the basis of the Hagen-Poiseuille law, using the area through which the entry enters the formation, the mean pore radius and the volume flow. The average permeability of the formation can be determined in a manner known in principle as described. Naturally, the greater the volume flow of aqueous polymer formulation injected into the formation, the greater the shear stress.

The speed of the injection can be determined by the person skilled in the art depending on the conditions in the formation. The shear rate at the entry of the aqueous polymer form is preferably formulation into the formation at least 30,000 s ^-1 , preferably at least 60,000 S ¹ and particularly preferably at least 90,000 s ^-1 .

In one embodiment of the invention, the process according to the invention is a flood process in which a base and usually a complexing agent or a polyacrylate is used. This is usually the case when the proportion of polyvalent cations in the reservoir water is low (100 - 400 ppm). An exception is sodium metaborate, which can also be used as a base without complexing agents in the presence of significant amounts of polyvalent cations.

The pH of the aqueous formulation is generally at least 8, preferably at least 9, in particular 9 to 13, preferably 10 to 12 and, for example, 10.5 to 11.

In principle, any type of base can be used with which the desired pH can be achieved and the person skilled in the art makes a suitable selection. Examples of suitable bases include alkali metal hydroxides, for example NaOH or KOH, or alkali metal carbonates, for example Na ₂ CO ₃ . The bases can furthermore be basic salts, for example alkali metal salts of carboxylic acids, phosphoric acid or, in particular, complexing agents comprising base groups such as EDTANa4.

Petroleum usually also contains various carboxylic acids such as naphthenic acids, which are converted into the corresponding salts by the basic formulation.

The salts act as naturally occurring surfactants and thus support the process of deoiling.

With complexing agents, undesirable precipitation of sparingly soluble salts, in particular calcium and magnesium salts, can advantageously be prevented if the alkaline aqueous formulation comes into contact with the corresponding metal ions and / or aqueous formulations containing corresponding salts are used for the process. The amount of complexing agents is chosen by the person skilled in the art. It can be, for example, 0.1 to 4% by weight based on the sum of all components of the aqueous formulation.

In a particularly preferred embodiment of the invention, however, a method for oil production is used in which no base (e.g. alkali metal hydroxides or alkali metal carbonates) is used.

In a preferred embodiment of the invention, the method is characterized in that the extraction of the oil from underground petroleum deposits is based on a surfactant flood method or a surfactant polymer flood method and not an alkali surfactant polymer flood method or not is a flood process in which Na ₂ C0 _{3 is} injected.

In a particularly preferred embodiment of the invention, the method is characterized in that it involves the extraction of oil from underground oil deposits a Winsor type III microemulsion flooding or a Winsor type III microemulsion polymer flooding and not an alkali Winsor type III microemulsion polymer flooding process or not a flooding process in which Na ₂ CO _{3 is} injected .

Oil is preferably extracted from underground oil deposits using the method according to the invention, ie by means of Winsor type III microemulsion floods. The oil deposit is also carbonate rock. Exemplary compositions of carbonate rock can be found in Example 5 on page 17 of WO 2015/173 339 A1. These compositions are also the subject of the present invention. The temperature of the deposit is preferably> 50 ° C, preferably> 65 ° C, and preferably <90 ° C. The salinity of the formation water is preferably ^ 75000 ppm of dissolved salts, preferably> 100000 ppm, more preferably> 120,000 ppm, further more preferably> 130,000 ppm of dissolved salts (TDS).

The salts in the reservoir water can be, in particular, alkali metal salts and alkaline earth metal salts. Examples of typical cations include Na ⁺ , K ⁺ , Mg ²⁺ and / or Ca ²⁺ and examples of typical anions include chloride, bromide, hydrogen carbonate, sulfate or borate. According to the invention, the reservoir water should have at least 100 ppm of divalent cations. The amount of alkaline earth metal ions can preferably be 100 to 53,000 ppm, particularly preferably 120 ppm to 20,000 ppm and very particularly preferably 150 to 6000 ppm.

As a rule, at least one or more alkali metal ions, in particular at least Na ^+, are present. In addition, alkaline earth metal ions may also be present, the weight ratio of alkali metal ions / alkaline earth metal ions generally being> 2, preferably> 3. At least one or more halide ions, in particular at least Ch, are generally present as anions. As a rule, the amount of Ch is at least 50% by weight, preferably at least 80% by weight, based on the sum of all anions.

The pH value of the formation water of the carbonate deposit is 3 to 10, preferably 5 to 9. The pH value of the deposit is influenced, among other things, by dissolved CO2.

The concentration of all surfactants is preferably 0.05 to 2% by weight, based on the total amount of the aqueous formulation injected. The total surfactant concentration is preferably 0.06 to 1% by weight, particularly preferably 0.08 to 0.5% by weight.

In a further preferred embodiment of the invention, at least one organic cosolvent can be added to the surfactant mixture according to the invention. It is preferably a completely water-miscible solvent, but it is also possible to use solvents which are only partially miscible with water. As a rule, the solubility should be at least 1 g / l, preferably at least 5 g / l. Examples include aliphatic C3 to C8 alcohols, preferably C4 to C6 alcohols, more preferably C3 to C6 alcohols, which are used to achieve sufficient water solubility with 1 to 5, preferably 1 to 3, ethyleneoxyein alcohols. units may be substituted. Further examples include aliphatic diols with 2 to 8 carbon atoms, which can optionally also be further substituted. For example, it can be at least one cosolvent selected from the group of 2-butanol, 2 methyl-1-propanol, butylethylene glycol, butyldiethylene glycol or butyltriethylene glycol.

In the context of the method according to the invention for tertiary oil production, the interfacial 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 /, by using the surfactant mixture according to the invention. m lowered. Thus, the interfacial tension between oil and water is set to values in the range from 0.1 mN / m to 0.0001 mN / m, preferably to values in the range of

0.05 mN / m to 0.0001 mN / m, particularly preferably reduced to values in the range from 0.01 mN / m to 0.0001 mN / m. The values given refer to the prevailing storage device temperature.

There may be further surfactants (D) in the aqueous, salt-containing surfactant formulation which

are not identical to surfactants (A), (B) or (C), and

are from the group of alkylbenzenesulfonates, alpha-olefin sulfonates, internal olefin sulfonates, paraffin sulfonates, the surfactants having 14 to 28 carbon atoms; and or

are selected from the group of alkyl ethoxylates and alkyl polyglucosides, the respective alkyl radical having 8 to 18 carbon atoms.

Particularly preferred for the surfactants (D) are alkyl polyglucosides which have been built up from primary linear fatty alcohols with 8 to 14 carbon atoms and have a degree of glucosidation of 1 to 2, and alkyl ethoxylates which have been built up from primary alcohols with 10 to 18 carbon atoms and a degree of ethoxylation have from 5 to 50.

The amount of surfactants (A) and (B) and, if present (C), based on the total amount of all surfactants in the surfactant mixture is preferably at least 25% by weight, more preferably at least 50% by weight, more preferably more than 50% by weight, more preferably at least 60% by weight, more preferably at least 70% by weight, more preferably at least 80% by weight, more preferably at least 90% by weight and ins special 100% by weight (only from (A), (B) and possibly (C)).

Another object of the present invention is a concentrate containing a surfactant mixture as indicated above, the concentrate 20% by weight to 90% by weight of the surfactant mixture, 5% by weight to 40% by weight of water and 5% by weight .-% to 40 wt .-% of a cosolvent, based in each case on the total amount of the concentrate, the concentrate of the surfactant mixture of ionic surfactant (A) of the general formula (I) and anionic surfactant (B) of the general formula (II ) can be contained in any molar ratio, but is preferably contained in the ratio specified for the process according to the invention. The water can be saline water, as detailed above.

Accordingly, the pressed-in aqueous, salt-containing surfactant formulation can be obtained in the process according to the invention by mixing a concentrate with surfactant mixture or by mixing individual concentrates.

Accordingly, the surfactants can be administered from ionic surfactant (A) of the general formula (I) and anionic surfactant (B) of the general formula (II), for example in the form of concentrates. For example, the ionic surfactant (A) of the general formula (I) can be supplied as a concentrate, the concentrate comprising 20% by weight to 90% by weight of the surfactant (A), 5% by weight to 40% by weight. % Water and 5 wt .-% to 40 wt .-% of a cosolvent, each based on the total amount of the concentrate. The same applies to the anionic surfactant (B) of the general formula (II). It can be supplied as a concentrate, the concentrate comprising 20% by weight to 90% by weight of the surfactant (B), 5% by weight to 40% by weight of water and 5% by weight to 40% by weight. % of a cosolvent, based in each case on the total amount of the concentrate. For the process according to the invention, both concentrates can be added to the injection water in the desired ratio and dissolved.

Another object of the present invention is therefore a concentrate, based in each case on the total amount of the concentrate

20% by weight to 90% by weight of at least one ionic surfactant (A) of the general formula (I) as indicated above or at least one anionic surfactant (B) of the general formula (II) as indicated above or a surfactant mixture as given above , the molar ratio of ionic surfactant (A) to anionic surfactant (B) can be any,

5% by weight to 40% by weight of water and

5% to 40% by weight of a cosolvent.

For the surfactant mixture, the ionic surfactant (A) and the anionic surfactant (B) and surfactant (C), what has been said above in connection with the process according to the invention also applies to the concentrate according to the invention.

The cosolvent is preferably selected from the group of aliphatic alcohols with 3 to 8 carbon atoms or from the group of alkyl monoethylene glycols, alkyl diethylene glycols or alkyl triethylene glycols, the alkyl radical being an aliphatic hydrocarbon radical with 3 to 6 carbon atoms. Furthermore, the concentrate according to the invention is preferably flowable or pumpable at 20 ° C. and has a viscosity of <5000 mPas at 10 S ¹ at 40 ° C. Accordingly, it is preferred that the cosolvent is selected from the group of aliphatic alcohols having 3 to 8 carbon atoms or from the group of alkyl monoethylene glycols, alkyl diethylene glycols or alkyl triethylene glycols, the alkyl radical being an aliphatic hydrocarbon radical having 3 to 6 carbon atoms.

It is further preferred that the concentrate is flowable at 20 ° C and has a viscosity of <10000 mPas at 10 S ¹ at 50 ° C.

The concentrate may also contain alkali chloride and diglycolic acid dialkali salt. Optionally, it also contains chloroacetic acid alkali salt, glycolic acid alkali salt, water and / or a cosolvent. The cosolvent is, for example, butyl ethylene glycol, butyl diethylene glycol or butyl triethylene glycol.

The concentrate preferably contains 0.5 to 15% by weight of a mixture comprising NaCl and diglycolic acid disodium salt, NaCl being present in excess of diglycolic acid disodium salt.

The concentrate further preferably contains butyldiethylene glycol as cosolvent.

Another object of the present invention relates to the use of a surfactant mixture or a concentrate according to the invention for the extraction of petroleum from underground petroleum deposits.

Another object of the present invention relates to the use of a surfactant formulation as indicated above for the extraction of petroleum from underground petroleum deposits, in particular under conditions as described herein.

For the surfactant mixture, the statements made above in the process according to the invention also apply to the use according to the invention.

Oil is preferably extracted from underground oil deposits using the method according to the invention by means of Winsor type III microemulsion floods. Furthermore, the oil deposit is carbonate rock.

SN Ehrenberg and PH Nadeau compare sandstone deposits and carbonate deposits with regard to their porosity and deposit depth (AAPG Bulletin, V. 89, No. 4 (April 2005), pages 435-445). Carbonate deposits have lower porosities on average than sandstone deposits. In addition, so-called 'fractures' with a correspondingly high permeability can be present, while at the same time there are so-called matrix blocks with a lower permeability. Carbonate deposits can therefore have areas with permeabilities of 1 - 100 mD (milidarcy) or areas with permeabilities of 10 - 100 mD as well as areas with permeabilities of »100 mD. There are also deposits with a small number of fractures and relatively homogeneous matrix areas. For example, a carbonate deposit can tat of 10 - 40% (preferably 12 - 35%) and permeabilities of 1 - 4000 mD (preferably 2 - 2000 mD, particularly preferably 5 - 500 mD).

Further descriptions of carbonate deposits can also be found in the two following publications:

Archie, Gustave Erdman. "Classification of carbonate reservoir rocks and petrophysical considerations." Aapg Bulletin 36.2 (1952): 278-298.

Lucia, F. Jerry. Carbonate reservoir characterization: an integrated approach. Springer Science & Business Media, 2007.

The composition of carbonate rocks can vary. In addition to calcite and / or dolomite, this also includes, for example, anchorite, feldspar, quartz, clay minerals (e.g. kaolin, illite, smectite, chlorite), halites, iron oxides, pyrite, gypsum and / or epsom salt. Preference is given to deposits with a high proportion of calcite (> 90%, particularly preferably> 95%) and a low quartz content (<5%, particularly preferably <2%) and a low proportion of clay minerals (<5%, particularly preferably <2 %). For example, a preferred deposit could have 98% calcite, 1% dolomite and 1% halite. Further exemplary compositions of carbonate rock can be found e.g. in Table 2 of Colloids and Surfaces A: Physicochem. Closely. Aspects 450 (2014) 1-8 or in Example 5 on page 17 of WO 2015/173 339 A1. The selection of surfactant mixtures depending on rock compositions, temperature and salinity are also the subject of the present invention. Preferably, the temperature of the deposit is> 90 ° C, more preferably> 100 ° C, more preferably> 110 ° C. The salinity of the formation water is preferably> 50,000 ppm, more preferably> 100,000 ppm and more preferably <210,000 ppm TDS.

In particular, the use according to the invention relates to a method according to the present invention, the statements made above correspondingly applying to the method according to the invention for the use according to the invention.

Experimental examples:

Synthesis examples:

The following examples are intended to illustrate the invention and its advantages:

Preparation of the anionic surfactants (A) and (B) and (C):

Used abbreviations:

EO ethyleneoxy

PO propyleneoxy

The following alcohols were used for the synthesis:

1 a) C16C18 - 10 EO - CH ₂ C0 ₂ Na corresponds to the mixture of anionic surfactant A and anionic surfactant B in a molar ratio of approx. 30 to 70, consisting of anionic surfactant (A) of the general formula (I) R ¹ - 0- (CH ₂ CH ₂ 0) o- (CH2) pY- M ⁺ with R ¹ = n-Ci ₆ H ₃₃ , o = 10, p = 1, Y = C0 ₂ and M = Na and anionic surfactant (B ) of the general formula (II) R ² -0- (CH ₂ CH ₂ 0) _O - (CH ₂ ) _P -Y- M ⁺ with R ² = n-Ci ₃ H ₃ 7, o = 10, p = 1 , Y = C0 ₂ and M = Na.

In a 2 l pressure autoclave with anchor stirrer, 392.4 g (1.5 mol) of C16C18 alcohol were introduced and the stirrer switched on. Then 4.2 g of 50% aqueous KOH solution (0.038 mol KOH, 2.1 g KOH) were added, a vacuum of 25 mbar was applied, the mixture was heated to 120 ° C. and held for 120 minutes in order to distill off the water. One flushed three times with N ₂ . The container was then checked for pressure tightness, 1.0 bar gauge pressure (2.0 bar absolute), heated to 130 ° C. and then the pressure set to 2.3 bar absolute. 660.8 g (15 mol) of ethylene oxide were metered in at 130 ° C. in the course of 7 h, p _max was 6.0 bar absolute. The mixture was left to react for 6 h until the pressure was constant, cooled to 100 ° C. and relaxed to 1.0 bar absolute. A vacuum of <10 mbar was applied and residual oxide was drawn off for 2 h.

The vacuum was released with N ₂ and the filling was carried out at 80 ° C. under N ₂ . The analysis (mass spectrum, GPC, 1 H-NMR in CDCI ₃ , 1 H-NMR in MeOD) confirmed the average composition C16C18 - 10 EO - H.

In a 250 ml flat-ground reactor with a three-stage bar stirrer, 160 g (0.228 mol,

1 .0 eq) C16C18 - 10 EO - H containing 0.006 mol C16C18 - 10 EO - K and 36.6 g (0.308 mol,

1, 35 eq) chloroacetic acid sodium salt (98% purity) and stirred at 45 ° C for 15 min at 400 revolutions per minute under normal pressure. The following procedure was then carried out eight times: 1.54 g (0.0384 mol, 0.1686 eq) of NaOH microprills (diameter 0.5-1.5 mm) were introduced, a vacuum of 30 mbar absolute for removal of the water of reaction, stirred for 50 min, and then the vacuum released with N ₂ . A total of 12.3 g (0.308 mol, 1.35 eq) NaOH microprills were used over a period of approx.

Added 7 h. During the first hour of this period, the speed of rotation was increased to approximately 1000 revolutions per minute. The mixture was then stirred for 45 min at 45 ° C and 45 mbar absolute and 15 h at 45 ° C and 60 mbar absolute. The vacuum was released with N ₂ and the experiment was completed (yield> 95%).

A white-yellowish viscous liquid was obtained at 20 ° C. The pH (5% in water) was 8.9. The water content was 1.5%. The molar proportion of chloroacetic acid sodium salt is approx. 2 mol%. The NaCI content is approx. 8.7% by weight. The OH number of the reaction mixture is 5.8 mg KOH / g. The molar proportion of glycolic acid sodium salt is approx. 2 mol%. In addition, a 1 H-NMR spectrum (with and without shift reagent trichloroacetylene isocyanate) was prepared. The degree of carboxymethylation is 93%. The desired structure has been confirmed.

106.9 g of the above crude carboxylate were stirred at 25 ° C. to produce a surfactant concentrate. 52.7 g of butydiethylene glycol and 51.1 g of water were added. The surfactant content is 42 percent by weight. Further information on the properties of the surfactant concentrate can be found in Table 5.

1 b) C16C18 - 8 EO - CH ₂ C0 ₂ Na corresponds to the mixture of anionic surfactant A and anionic surfactant B in a molar ratio of approx. 30 to 70, consisting of anionic surfactant (A) of the general formula (I) R ¹ - 0- (CH ₂ CH ₂ 0) o- (CH2) pY- M ⁺ with R ¹ = n-Ci ₆ H ₃₃ , o = 8, p = 1, Y = C0 ₂ and M = Na and anionic surfactant (B ) of the general formula (II) R ² -0- (CH ₂ CH ₂ 0) _O - (CH ₂ ) _P -Y- M ⁺ with R ² = n-Ci ₃ H ₃ 7, o = 8, p = 1 , Y = C0 ₂ and M = Na.

In a 2 l pressure autoclave with anchor stirrer, 392.4 g (1.5 mol) of C16C18 alcohol were introduced and the stirrer switched on. Thereafter, 3.7 g of 50% aqueous KOH solution (0.029 mol KOH, 1.65 g KOH) were added, a vacuum of 25 mbar was applied, the mixture was heated to 120 ° C. and held for 120 minutes in order to distill off the water. One flushed three times with N ₂ . Then the container was checked for pressure tightness, 1.0 bar overpressure (2.0 bar absolute), heated to 130 ° C. and then the pressure set to 2.4 bar absolute. 528.6 g (12 mol) of ethylene oxide were metered in at 130 ° C. in the course of 7 h, p _max was 6.0 bar absolute. The mixture was left to react for 6 h until the pressure was constant, cooled to 100 ° C. and relaxed to 1.0 bar absolute. A vacuum of <10 mbar was applied and residual oxide was drawn off for 2 h. The vacuum was released with N ₂ and it was filled at 80 ° C under N ₂ . The analysis (mass spectrum, GPC, 1 H-NMR in CDCI ₃ , 1 H-NMR in MeOD) confirmed the mean composition C16C18 - 8 EO - H.

In a 250 ml flat-ground reactor with a three-stage bar stirrer, 148.2 g (0.241 mol,

1 .0 eq) C16C18 - 8 EO - H containing 0.005 mol C16C18 - 8 EO - K and 37.7 g (0.317 mol, 1.35 eq) chloroacetic acid sodium salt (98% purity) added and at 45 ° C for 15 min at 400 revolutions per minute under normal pressure. The following procedure was then carried out eight times: 1.59 g (0.0397 mol, 0.1688 eq) of NaOH microprills (diameter 0.5-1.5 mm) were introduced, a vacuum of 30 mbar absolute for removal of the water of reaction, stirred for 50 min, and then the vacuum released with N ₂ . A total of 12.7 g (0.317 mol, 1.35 eq) NaOH microprills were used over a period of approx.

A white-yellowish viscous liquid was obtained at 20 ° C. The pH (5% in water) was 8.8. The water content was 1.5%. The molar proportion of chloroacetic acid sodium salt is about 2 mol%. The NaCI content is approx. 9.2% by weight. The OH number of the reaction mixture is 5.8 mg KOH / g. The molar proportion of glycolic acid sodium salt is approximately 2 mol%. In addition, a 1 H-NMR spectrum (with and without shift reagent trichloroacetylene isocyanate) was prepared. The degree of carboxymethylation is 93%. The desired structure has been confirmed. 134 g of the above crude carboxylate were stirred at 25 ° C. 67 g of butydiethylene glycol and 67 g of water were added. The surfactant content is 46 percent by weight.

1 c) C 16C 18 - 9 EO - CH ₂ C0 ₂ Na

C16C18 - 9 EO - CH ₂ C0 ₂ Na is prepared analogously to 1 b).

1 d) C16C18 - 7 EO - CH ₂ C0 ₂ Na

C16C18 - 7 EO - CH ₂ C0 ₂ Na is prepared analogously to 1 b).

1 e) C16 - 7 EO - CH ₂ C0 ₂ Na

C16 - 7 EO - CH ₂ C0 ₂ Na is produced analogously to 1 d), with the difference that C16 alcohol is used as the starting material instead of C16C18 alcohol.

2 a) C16C18 - 7 PO - 10 EO - CH ₂ C0 ₂ Na corresponds to the anionic surfactant (C) of the general formula (III) R ³ -0- (CH ₂ CHCH ₃ 0) _n - (CH ₂ CH ₂ 0) _O - (CH ₂ ) _P -Y- M ⁺ with R ³ = CieHss / CisHsr, n = 7, o = 10, p = 1, Y = C0 ₂ and M = Na.

In a 2 l pressure autoclave with anchor stirrer, 304 g (1.19 mol) of C16C18 alcohol were introduced and the stirrer switched on. Then 4.13 g of 50% aqueous KOH solution (0.037 mol KOH, 2.07 g KOH) were added, a vacuum of 25 mbar was applied, the mixture was heated to 100 ° C. and held for 120 minutes in order to distill off the water. One flushed three times with N ₂ . The container was then checked for pressure tightness, 1.0 bar overpressure (2.0 bar absolute), heated to 130 ° C. and then the pressure set to 2.0 bar absolute. 482 g (8.31 mol) of propylene oxide were metered in at 150 revolutions per minute at 130 ° C. in the course of 6 h, p _max was 6.0 bar absolute. The mixture was stirred at 130 ° C for 2 h. 522 g (11.9 mol) of ethylene oxide were metered in over the course of 10 h at 130 ° C., p _max was 5.0 bar absolute. The mixture was left to react for 1 h until the pressure was constant, cooled to 100 ° C. and let down to 1.0 bar absolute. A vacuum of <10 mbar was applied and residual oxide was drawn off for 2 h. The vacuum was released with N ₂ and the filling was carried out at 80 ° C. under N ₂ . The analysis (mass spectrum, GPC, 1 H-NMR in CDCh, 1 H-NMR in MeOD) confirmed the average composition C16C18 - 7 PO - 10 EO - H. In a 250 ml flat-ground reactor with a three-stage bar stirrer, 165.3 g (0.150 mol,

1 .0 eq) C16C18 - 7 PO - 10 EO - H containing 0.005 mol C16C18 - 7 PO - 10 EO - K and 24.1 g (0.203 mol, 1.35 eq) chloroacetic acid sodium salt (98% purity) and added at 45 ° C for 15 min at 400 revolutions per minute under normal pressure. The following procedure was then carried out eight times: 1.02 g (0.0253 mol, 0.1688 eq) NaOH microprills (diameter 0.5-1.5 mm) were introduced, a vacuum of 30 mbar to remove the Applied water of reaction, stirred for 50 min, and then released the vacuum with N ₂ . A total of 8.1 g (0.203 mol, 1.35 eq) NaOH microprills were added over a period of about 6.5 hours. During the first hour of this period, the speed of rotation was increased to approximately 1000 revolutions per minute. The mixture was then stirred at 45 ° C and 30 mbar for 3 h. The vacuum was released with N ₂ and the test was carried out (yield> 95%).

A white-yellowish viscous liquid was obtained at 20 ° C. The pH (5% in water) was 7.5. The water content was 1.5%. The molar proportion of chloroacetic acid sodium salt is approx. 2 mol%. The NaCI content is approximately 6.0% by weight. The OH number of the reaction mixture is 8.0 mg KOH / g. The molar proportion of glycolic acid sodium salt is approx. 3 mol%. In addition, a 1 H-NMR spectrum (with and without shift reagent trichloroacetylene isocyanate) was prepared. The degree of carboxymethylation is 85%. The desired structure has been confirmed. 99 g of butydiethylene glycol and 99 g of water were added. The surfactant content is 45 percent by weight.

2 b) C16C18 - 7 PO - 15 EO - CH ₂ C0 ₂ Na corresponds to the anionic surfactant (C) of the general formula (III) R ³ -0- (CH ₂ CHCH ₃ 0) _n - (CH ₂ CH ₂ 0) o- (CH2) pY- M ⁺ with R ³ = CieHss / CisHsr, n = 7, o = 15, p = 1, Y = C0 ₂ and M = Na.

In a 2 l pressure autoclave with anchor stirrer, 261.6 g (1.0 mol) of C16C18 alcohol were introduced and the stirrer switched on. Then 4.5 g of 50% aqueous KOH solution (0.04 mol KOH, 2.25 g KOH) were added, a vacuum of 25 mbar was applied, the mixture was heated to 100 ° C. and held for 120 minutes in order to distill off the water. One flushed three times with N ₂ . Then the container was checked for pressure tightness, 1.0 bar overpressure (2.0 bar absolute), heated to 135 ° C and then the pressure set to 2.2 bar absolute. 412.4 g (7.1 mol) of propylene oxide were metered in at 125 revolutions per minute at 135 ° C. in the course of 6 h, p _max was 6.0 bar absolute. The mixture was stirred at 135 ° C for 4 h. 674 g (15.3 mol) of ethylene oxide were metered in over 8 hours at 135 ° C., p _max was 5.0 bar absolute. The mixture was left to react for 6 h until the pressure was constant, cooled to 100 ° C. and relaxed to 1.0 bar absolute. A vacuum of <10 mbar was applied and residual oxide was drawn off for 2 h.

The vacuum was released with N ₂ and the filling was carried out at 80 ° C. under N ₂ . The analysis (mass spectrum, GPC, 1 H-NMR in CDCh, 1 H-NMR in MeOD) confirmed the average composition C16C18 - 7 PO - 15 EO - H.

In a 750 ml flat-ground reactor with a three-stage bar stirrer, 400 g (0.30 mol,

1.0 eq) C16C18 - 7 PO - 15 EO - H containing 0.012 mol C16C18 - 7 PO - 15 EO - K and stirred at 70 ° C (750 revolutions per minute). The following procedure was then carried out 12 times: 5.34 g of 50% strength aqueous sodium hydroxide solution were metered in at 70 ° C. and a reduced pressure of 12 mbar absolute was applied at 70 ° C. for 15 minutes to remove the water, which was again achieved by adding nitrogen was lifted, then 3.94 g of chloroacetic acid 80% in water was metered in at 70 ° C and for 15 minutes a reduced pressure of 12 mbar absolute at 70 ° C for water removal, which was canceled by the addition of nitrogen as that. A total of 64.10 g (0.80 mol, 32.05 g NaOH, 2.67 eq) 50% aqueous sodium hydroxide solution and 47.32 g (0.40 mol, 1.33 eq) chloroacetic acid 80% in Water metered in at 70 ° C within 7 h. The mixture was then stirred for 20 minutes. The experiment was completed (yield> 95%).

A white-yellowish viscous liquid was obtained at 20 ° C. The pH (5% in water) was 12. The water content was 0.45%. The molar proportion of chloroacetic acid sodium salt is approx. 2 mol%. The NaCI content is approximately 5.1% by weight. The OH number of the reaction mixture is 8.3 mg KOH / g. The molar proportion of glycolic acid sodium salt is approx. 3.5 mol%. In addition, a 1 H-NMR spectrum (with and without shift reagent trichloro-racetyl isocyanate) was prepared. The degree of carboxymethylation is 83%. The desired structure has been confirmed.

365 g of the above crude carboxylate were stirred at 25 ° C. The pH was adjusted to 7.6 by adding acetic acid. 182.5 g of butydiethylene glycol and 182.5 g of water were added. The surfactant content of the concentrate is approx. 45 percent by weight.

Application tests:

Preparation of the aqueous salt solutions

Three different aqueous salt solutions were made. For this purpose, salts were weighed into the distilled water and dissolved by stirring at 20 ° C. Finally, the pH was adjusted, stored closed and the saline solution checked for clarity for several days:

- Synthetic Seawater with 43910 ppm TDS containing 30.53 g / l NaCl, 2.1 1 g / l CaCl x 2 H2O, 13.97 g / l MgCl x 6 H2O, 5.03 g Na ₂ S0 _4, 0, 21 g NaHCOs - pH adjusted to 8.0

- Exemplary synthetic reservoir water I with 138656 ppm TDS containing 103.50 g / l NaCl, 35.59 g / l CaCI ₂ x 2 H ₂ 0, 17.14 g / l MgCl ₂ x 6 H ₂ 0, 0.25 g NaHCOs - pH adjusted to 7.0

- Exemplary synthetic reservoir water II with 234 370 ppm TDS containing 171.99 g / l NaCl, 69.06 g / l CaCl ₂ x 2 H ₂ 0, 20.33 g / l MgCl ₂ x 6 H ₂ 0, 0.41 g Na ₂ S0 ₄ , 0.29 g NaHCOs - pH adjusted to 6.0

- Exemplary synthetic reservoir water III with 209684 ppm TDS containing 164.147 g / l NaCI, 48.239 g / l CaCI ₂ x 2 H ₂ 0, 16.971 g / l MgCI ₂ x 6 H ₂ 0, 1, 150 g Na ₂ S0 ₄ - pH Value set to 6.9 - Exemplary synthetic reservoir water X produced by mixing reservoir water II with distilled water or by gently distilling off water to salinities of 138000 ppm TDS, 160000 ppm TDS, 180000 ppm TDS, 199317 ppm TDS, 220000 ppm TDs and 240000 ppm TDS

Determination of solubility

The surfactants were dissolved in saline water in the concentration to be investigated. In order to avoid degradation of the surfactants by oxygen at high temperatures, NaMBT and Na ₂ S0 _{3 were} used as radical scavengers and as oxygen scavengers. In addition, work was carried out under an argon atmosphere and the aqueous surfactant solutions were freed of oxygen by introducing argon for 30 minutes. A glass jar with screw cap was used, which is absolutely approved for pressures up to 5 bar.

The surfactants in the concentration to be investigated were stirred in saline water with the respective salt composition at 20-30 ° C. for 30 minutes. For surfactant mixtures, for example, the ionic surfactant (A) of the general formula (I) (optionally in the form of a concentrate) was dissolved in the desired salt water (which contained free radical scavengers and oxygen scavengers) in a first vessel. In a second vessel, the anionic ten sid (B) of the general formula (II) (optionally in the form of a concentrate) was dissolved in the desired salt water (which contained free radical scavengers and oxygen scavengers). Then both solutions were combined at 20-30 ° C and then heated to the target temperature. Alternatively, the ionic surfactant (A) of the general formula (I) and the anionic surfactant (B) of the general formula (II) were predissolved in deionized water or water with low salinity (<10,000 ppm) (addition in the form of the concentrated individual surfactants or as concentrated mixture) and then mixed with a salt water solution (which contained radical scavengers and oxygen scavengers) only in exceptional cases was the surfactant dissolved in water, if necessary the pH was adjusted to a range of 6 to 8 by adding aqueous hydrochloric acid and corresponding amounts with the respective salt at 20 ° C). It was then heated. The mixture was then gradually warmed until turbidity or phase separation began. Then it was carefully cooled and the point was noted at which the solution became clear or slightly scattering again. This was noted as a cloud point.

At certain fixed temperatures, the appearance of the surfactant solution in saline water was noted. Clear solutions or solutions that are slightly scattering and that become slightly lighter (but do not frame over time) due to slight shear are considered acceptable. Said lightly scattering surfactant solutions were filtered through a filter with a pore size of 2 mm. There was no separation.

The surfactant quantities were given as grams of the active substance (calc. 100% surfactant content) per liter of salt water. Determination of the phase behavior

The surfactant solutions (10 g surfactant in terms of active content in 1 liter of the aqueous salt solution containing 50 ppm Na ₂ S0 ₃ and 20 ppm NaMBT), which were prepared for the above solubility determinations, were mixed with a certain amount of oil (water-oil ratio of 4: 1 or 1: 1 by volume) and stored under an argon atmosphere in a sealable, graduated vessel at 125 ° G for seven or 14 days. During this time, the vessels were turned upside down and back once a day. The grading was used to note whether emulsions or microemulsions had formed. In the case of mobile middle phases (microemulsion Winsor type III), the SP ^* or SPo was determined (see the following section).

Determination of the interfacial tension

The interfacial tension between water and oil was 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 by experts for the approximate determination of the interfacial tension. The solubilization parameter SP ^* indicates how many ml of oil per ml of surfactant used is dissolved in a microemulsion (Windsor Type III). The interfacial tension o (interfacial tension; IFT) can be calculated from this using the approximation formula IFT = 0.3 / [(SP ^* ) ² ] if the same volumes of water and oil are used. (C. Huh, J. Coli. Interf. Sc., Vol. 71, No. 2 (1979)).

If different volumes of water and oil were used, the solubilization parameter SPo was determined. This indicates how much oil was microemulsified in the middle phase (microemulsion Winsor type III) per amount of surfactant used. The interfacial tension can be estimated analogously using the above equation. For unbalanced Winsor type III microemulsions, SP ^* can be calculated using the formula 2 / [SP ^* ] = 1 / [SPo] + 1 / [SPw] (S. Gosh, RT Johns, Langmuir 2016, 32, 8969-8979) . The interfacial tension can in turn be calculated using the above approximation formula IFT = 0.3 / [(SP ^* ) ² ].

Alternatively, interfacial tensions of crude oil versus saline water in the presence of the surfactant solution at temperature were determined using a spinning-drop method on a SVT20 from DataPhysics. For this purpose, an oil drop was injected into a capillary filled with saline surfactant solution at temperature and the expansion of the drop was observed at about 4500 revolutions per minute and the temporal development of the interfacial tension was noted. The interfacial tension IFT (or s H) is calculated - as described by Hans-Dieter Dörfler in "Interfaces and colloid-disperse systems" Springer Verlag Berlin Heidelberg 2002 - using the following formula from the cylinder diameter d _z , the speed w, and the You difference

(di-d2): s ii = 0.25 * d _z ³ * w2 * (di-d2). The surfactant quantities were given as grams of the active substance (calc. 100% surfactant content) per liter of salt water.

Specification of the API level

The API (American Petroleum Institute) level is a conventional sealing unit for crude oils that is commonly used in the United States. It is used worldwide for the characterization and quality standard of crude oil. The API grade results from the relative density p, _{e \ of} the crude oil at 60 ° F (15.56 ° C) based on water

API grade = (141, 5 / _ei ) - 131, 5.

The test results for solubility and interfacial tension are shown below.

Table 1 interfacial tension after 30 min with a surfactant mixture of anionic surfactant (A) of the general formula (I) and anionic surfactant (B) of the general formula (II) on crude oil with API grade 33 at 80 ° C. and various salinities

^b from Ex. 1a) [corresponds to the mixture of anionic surfactant A to anionic surfactant B in a molar ratio of approximately 30 to 70, consisting of anionic surfactant (A)

general formula (I) R ¹ -0- (CH ₂ CH ₂ 0) o- (CH2) pY- M ⁺ with R ¹ = n-Ci ₆ H ₃₃ , o = 10, p = 1, Y =

C0 ₂ and M = Na and anionic surfactant (B) of the general formula (II) R ² -0- (CH ₂ CH ₂ 0) ₀ - (CH ₂ ) _P -Y- M ⁺ with R ² = n-Ci ₈ H ₃₇ , o = 10, p = 1, Y = C0 ₂ and M = Na]

c corresponds to anionic surfactant (A) of the general formula (I) R ¹ -0- (CH ₂ CH ₂ 0) _O - (CH ₂ ) _P -Y- M ⁺ with R ¹ = n-Ci ₆ H ₃₃ , o = 10, p = 1, Y = C0 ₂ and M = Na

d corresponds to anionic surfactant (B) of the general formula (II) R ² -0- (CH ₂ CH ₂ 0) _O - (CH ₂ ) _P -Y- M ⁺ with R ² = n-Ci ₃ H ₃ 7, o = 10, p = 1, Y = C0 ₂ and M = Na

'from Ex 2 a) [corresponds to the anionic surfactant (C) of the general formula (III) R ³ -0- (CH ₂ CHCH ₃ 0) _n - (CH ₂ CH ₂ 0) _o - (CH ₂ ) _p -Y - M ⁺ with R ³ = C _I6 H ₃₃ / C _I8 H ₃ 7, n = 7, o = 10, p = 1, Y = C0 ₂ and M = Na]

As can be seen in Examples 1 to 11 of Table 1, claimed surfactant mixtures at 80 ° C. and different salinities provide low to ultra-low interfacial tensions: 0.054 to 0.0015 mN / m. Example 2 in Table 1 shows that ultra-low interfacial tension values of 0.0096 mN / m can also be achieved with a mixture of anionic surfactant (A) and anionic surfactant (B). Examples 3 to 1 1 show a significant robustness when the anionic surfactant (C) is added as a further component. Ultimately low interfacial tensions are achieved with the same surfactant mixture ratios but different salinities (e.g. examples 5, 10 and 11) or ultra-low interfacial tensions are achieved with the same salinity but different surfactant mixture ratios (e.g. examples 7, 9 and 11). Due to the average temperature of 80 ° C, in contrast to Table 1, the addition of a cationic or betaine surfactant is not necessary. All formulations described in Table 2 based on the alkyl ether carboxylates were clearly soluble at 80 ° C and the respective salinity.

In order to demonstrate the broad applicability of the claimed formulations, further tests were carried out at 70 ° C.

Table 2 interfacial tension after 30 min with a surfactant mixture of anionic surfactant (A) of the general formula (I) and anionic surfactant (B) of the general formula (II) and anionic surfactant (C) of the general formula (III) on crude oil with API grade 33 at 70 ° C

b from Example 1a) [corresponds to the mixture of anionic surfactant A to anionic surfactant B in a molar ratio of approximately 30 to 70, consisting of anionic surfactant (A) of the general formula (I) R ¹ -0- (CH ₂ CH ₂ 0) o- (CH2) pY- M ⁺ with R ¹ = n-Ci ₆ H ₃₃ , o = 10, p = 1, Y = C0 ₂ and M = Na and anionic surfactant (B) of the general formula (II ) R ² -0- (CH ₂ CH ₂ 0) ₀ - (CH ₂ ) _P -Y- M ⁺ with R ² = n-Ci ₈ H ₃₇ , o = 10, p = 1, Y = C0 ₂ and M = Na]

i from Example 2 b) [corresponds to the anionic surfactant (C) of the general formula (III) R ³ -0- (CH ₂ CHCH ₃ 0) _n - (CH ₂ CH ₂ 0) _o - (CH ₂ ) _p -Y - M ⁺ with R ³ = C _I6 H ₃₃ / C _I8 H ₃ 7, n = 7, o = 15, p = 1, Y = C0 ₂ and M = Na]

As can be seen in Examples 1 to 8 of Table 2, claimed surfactant mixtures containing a mixture of anionic surfactant (A), anionic surfactant (B) and anionic surfactant (C), even at 70 ° C. and different salinities, provide ultra-low Interface tensions: 0.001 to 0.007 mN / m. Examples 1 to 3 in Table 2 show that the interfacial tensions are in the ultra-low range even when the surfactant formulation is diluted from 10 g / l to 1 g / l of active substance. Example 4 from Table 2 and Example 10 from Table 1 both have ultra-low interfacial tensions with the identical surfactant formulations at the same salinity - but once at 70 ° C and once at 80 ° C. Example 5 from Table 2 shows, in comparison to Example 1 from Table 2, that even a variation of the mixing ratio continues to lead to ultra-low interfacial tensions. Examples 6 to 8 demonstrate the robustness with variation of the surfactant mixture ratio even when using another anionic surfactant (C) of the general formula (IV). In the following test, claimed surfactant formulations were compared with other alkyl ethoxy carboxylates which have a degree of ethoxylation or a branched alkyl radical which is not according to the invention.

Table 3 Solubilities of the surfactant mixture of anionic surfactant (A) of the general formula (I) and anionic surfactant (B) of the general formula (II) in comparison to other alkyl ethoxy carboxylates based on branched alkyl radicals

b from Ex. 1a) [corresponds to the mixture of anionic surfactant A to anionic surfactant B in a molar ratio of approximately 30 to 70, consisting of anionic surfactant (A)

As can be seen from Examples 1 and 2 in Table 3, the claimed surfactant formulations are clearly soluble in a salt-containing water (150,000 ppm salt content consisting of 135,000 ppm NaCl and 15,000 ppm CaCl ₂ ) both at 25 ° C. and 90 ° C. Comparative examples V4 to V8 show that, surprisingly, not

Although surfactants according to the invention are still predominantly clearly soluble at a low temperature of 25 ° C., this is no longer the case at 90 ° C. These surfactants not according to the invention are based on a branched alkyl radical of the Guerbet type (ie they have a branching in the 2-position and were produced by the dimerization of linear alcohols (see also WO2013 / 060670). Furthermore, comparison with Example 2 also shows the

Comparative Examples V4 and V8 that a higher degree of ethoxylation with V4 and V8 was not sufficient to achieve clear solubility at 90 ° C. Clear solubility is important to avoid clogging of the narrow pore reservoir or high retention of the surfactant in the formation.

In the next test, the robustness of the surfactant formulation according to the invention should be explored.

Table 4 interfacial tension after 30 min with a surfactant mixture of anionic surfactant (A) of the general formula (I) and anionic surfactant (B) of the general formula (II) and anionic surfactant of the general formula (IV) on crude oil with API grade 33 at 70 ° C at various concentrations ^b from Ex. 1a) [corresponds to the mixture of anionic surfactant A to anionic surfactant B in a molar ratio of approximately 30 to 70, consisting of anionic surfactant (A)

As can be seen from Examples 1 to 4 in Table 4, to a great surprise the interfacial tension between oil and water remains in the ultra-low range of 0.0006 to 0.005 mN / m, although the concentration of active substance claimed

Surfactant formulation is changed by a factor of 20 (from 500 to 10,000 ppm). This is a very big advantage when flooding the deposit, since the desired lowering of the interfacial tension can also be achieved with high dilution. For example, possible surfactant losses due to adsorption are of little or no importance.

Table 5 Appearance and properties of the surfactant concentrate

general formula (I) R ¹ -0- (CH ₂ CH ₂ 0) ₀ - (CH ₂ ) _P -Y- M ⁺ with R ¹ = n-Ci ₆ H ₃₃ , o = 10, p = 1, Y =

c corresponds to anionic surfactant (A) of the general formula (I) R ¹ -0- (CH ₂ CH ₂ 0) ₀ - (CH ₂ ) _P -Y- M ⁺ with R ¹ = n-Ci ₆ H ₃₃ , o = 10, p = 1, Y = C0 ₂ and M = Na

d corresponds to anionic surfactant (B) of the general formula (II) R ² -0- (CH ₂ CH ₂ 0) ₀ - (CH ₂ ) _P -Y- M ⁺ with R ² = n-Ci ₃ H ₃ 7, o = 10, p = 1, Y = C0 ₂ and M = Na

As can be seen in Table 5, the claimed surfactant concentrate from Example 1a) can be handled very well at 40 ° C. It is a homogeneous, low-viscosity liquid, which can be pumped and dosed very easily (ie without high energy expenditure) in view of 60 mPas (high dosing accuracy, no lumps remaining). Further surfactants according to the invention were investigated in order to substantiate the breadth of the invention. The degree of ethoxylation was varied. Table 6 interfacial tension after 30 min with a surfactant mixture of anionic surfactant (A) of the general formula (I) and anionic surfactant (B) of the general formula (II) on crude oil with API grade 33 at 70 ° C. at various concentrations

¹ corresponds to the mixture of anionic surfactant A to anionic surfactant B in a molar ratio of about 30 to 70, consisting of anionic surfactant (A) of the general formula (I) R ¹ -0- (CH ₂ CH ₂ 0) o- ( CH2) pY- M ⁺ with R ¹ = n-Ci ₆ H ₃₃ , o = 9, p = 1, Y = C0 ₂ and M = Na and anionic surfactant (B) of the general formula (II) R ² -0- (CH ₂ CH ₂ 0) _O - (CH ₂ ) _P -Y- M ⁺ with R ² = n-Ci ₃ H ₃ 7, o = 9, p = 1, Y = C0 ₂ and M = Na]

As can be seen in Table 6, claimed surfactant formulations, which contain surfactants with a degree of ethoxylation of 8 or 9, also deliver ultra-low interfacial tensions of 0.001 or 0.008 mN / m (Ex. 1 or 2).

Table 7 Interfacial tension after 30 min with a surfactant mixture of anionic surfactant (A) of the general formula (I) and anionic surfactant (B) of the general formula (II) and anionic surfactant (C) of the general formula (III) on crude oil with API grade 33 at 70 ° C

m from Example 1d) [corresponds to the mixture of anionic surfactant A to anionic surfactant B in a molar ratio of about 30 to 70, consisting of anionic surfactant (A)

general formula (I) R ¹ -0- (CH ₂ CH ₂ 0) _o - (CH ₂ ) pY- M ⁺ with R ¹ = n-Ci ₆ H ₃₃ , o = 7, p = 1, Y = C0 ₂ and M = Na and anionic surfactant (B) of the general formula (II) R ² -0- (CH ₂ CH ₂ 0) _o - (CH ₂ ) _p - Y- M ⁺ with R ² = n-Ci ₃ H ₃ 7, o = 7, p = 1, Y = C0 ₂ and M = Na]

n from Example 1 e) [corresponds to anionic surfactant (A) of the general formula (I) R ¹ -0- (CH ₂ CH ₂ 0) ₀ - (CH ₂ ) _P -Y- M ⁺ with R ¹ = n- Ci ₆ H ₃₃ , o = 7, p = 1, Y = C0 ₂ and M = Na]

As can be seen in Example 1 and Comparative Example V2 of Table 7, claimed surfactant mixtures comprising a mixture of anionic surfactant (A) and the anionic surfactant (B) provide an interfacial tension almost half as low as the anionic surfactant (A) alone. In addition, ultra-low interfacial tensions are achieved in Example 1 (0.0085 mN / m), while in Comparative Example V2 the interfacial tensions remain above 0.01 m / N. The surfactants in Example 1 and Comparative Example V2 have the same degree of ethoxylation and were prepared analogously to the other compounds. The results obtained show that a claimed mixture of the surfactants (A) and (B) is more advantageous than the sole use of the corresponding surfactant (A). In the case of the surfactant C16 - 7 EO - CH ₂ CO ₂ Na from comparative example V2, it is a surfactant which was disclosed in US 4,457,373 A.

Claims

1. A method for extracting petroleum from an underground petroleum deposit, in which an aqueous, salt-containing surfactant formulation comprising a surfactant mixture in order to reduce the interfacial tension between oil and water to <0.1 mN / m, is pressed into the petroleum deposit and the deposit through at least one injection hole crude oil is extracted through at least one production well, characterized in that the petroleum deposit has a temperature of> 25 ° C and <130 ° C and formation water with a salinity of> 50,000 ppm of dissolved salts and that the surfactant mixture has at least one anionic surfactant ( A) of the general formula (I)

R ² -0- (CH ₂ CH ₂ 0) _O - (CH ₂ ) _P -Y- M ⁺ (II), with a molar ratio of anionic surfactant (A) to anionic surfactant (B ) from 90:10 to 10:90, where

R ^{1 represents} a linear, saturated or unsaturated, aliphatic hydrocarbon radical having 16 carbon atoms;

R ^{2 represents} a linear, saturated or unsaturated, aliphatic hydrocarbon residue which has two methylene groups more than R ¹ ;

each Y is independently SO3 or C0 ₂ ;

each o is independently a number from 6 to 20; where p is the number 1 if Y is CO2;

p stands for the number 0 if Y stands for SO3;

wherein the surfactant mixture is not an ionic surfactant of the general formula (III) (R ^{1 a} ) _k - N ⁺ (R ^2a ) ₍₃ -k) R ^3a (X-) i (III), where each R ^1a independently represents a linear or branched, saturated or unsaturated, aliphatic hydrocarbon radical with 8 up to 22 carbon atoms or for the radical R ^4a -0- (CH ₂ C (R ^5a ) HO) _ma - (CH2C (CH3) HO) na- (CH2CH ₂ 0) oa- (CH ₂ CH ₂ ) - or R ^4a -0- (CH ₂ C (R ^5a ) HO) _ma - (CH2C (CH3) HO) na- (CH2CH ₂ 0) oa- (CH ₂ C (CH ₃ ) H) -;

each R ^{2a is} CH3;

R ^{3a is} CH ₃ or (CH2CO2) -;

each R ^4a independently represents a linear or branched, saturated or unsaturated, aliphatic hydrocarbon radical having 8 to 36 carbon atoms or an aromatic or aromatic-aliphatic hydrocarbon radical having 8 to 36 carbon atoms;

each R ^5a independently represents a linear or branched, saturated or unsaturated, aliphatic hydrocarbon radical having 2 to 16 carbon atoms or an aromatic or aromatic-aliphatic hydrocarbon radical having 6 to 10 carbon atoms;

X represents CI, Br, I or H ₃ CO-SO ₃ ;

k represents the number 1 or 2,

I represents the number 0 or 1;

each ma independently represents a number from 0 to 15;

each na independently represents a number from 0 to 50;

2. The method according to claim 1, characterized in that when injected in the tenside mixture, a molar ratio of anionic surfactant (A) to anionic surfactant (B) from 80:20 to 20:80, preferably 40:60 to 20:80, especially 30:70.

3. The method according to claim 1 or 2, characterized in that R ^{1 is} a linear, saturated aliphatic primary hydrocarbon radical having 16 carbon atoms.

4. The method according to any one of claims 1 to 3, characterized in that R ^{2 is} a linear saturated aliphatic primary hydrocarbon radical with 18 carbon atoms.

5. The method according to any one of claims 1 to 4, characterized in that o stands for a number from 6 to 15, preferably for a number from 8 to 12, in particular for 10.

6. The method according to any one of claims 1 to 5, characterized in that p stands for the number 1 and Y for CO2.

7. The method according to any one of claims 1 to 6, characterized in that the surfactant mixture at least one anionic surfactant (C) of the general formula (IV)

R ^3b contains -0- (CH ₂ CH (CH3) 0) nb- (CH2CH20) ob- (CH ₂ ) pb-Yb- M _b ⁺ (IV), where

Y _{b represents} SO3 or C0 ₂ ;

whether independently represents a number from 8 to 20;

pb stands for the number 0, 2 or 3 if Y _b stands for SO3.

8. The method according to any one of claims 1 to 7, characterized in that the petroleum storage facility a formation water with a salinity of> 75000 ppm of dissolved salts, preferably> 100000 ppm, more preferably> 120,000 ppm, further more preferably>

130,000 ppm, of dissolved salts.

9. The method according to any one of claims 1 to 8, characterized in that the petroleum storage facility has a temperature of> 50 ° C, preferably> 65 ° C, and preferably <90 ° C.

10. The method according to any one of claims 1 to 9, characterized in that the extraction of petroleum from underground petroleum deposits by means of Winsor type III microemulsion flooding.

1 1. The method according to any one of claims 1 to 10, characterized in that the oil deposit is carbonate rock.

12. Concentrate, based in each case on the total amount of the concentrate

20 wt .-% to 90 wt .-% of a surfactant mixture as specified in one of claims 1 to 11, wherein the molar ratio of anionic surfactant (A) to anionic

Surfactant (B) can be any

5% by weight to 40% by weight of water and 5% by weight to 40% by weight of a cosolvent.

13. Concentrate according to claim 12, characterized in that the cosolvent is selected from the group of aliphatic alcohols having 3 to 8 carbon atoms or from the group of alkyl monoethylene glycols, alkyl diethylene glycols or alkyl triethylene glycols, the alkyl radical being an aliphatic hydrocarbon radical having 3 to 6

Is carbon atoms.

14. Concentrate according to claim 13 or 14, characterized in that the concentrate is flowable at 20 ° C and at 50 ° C has a viscosity of <10000 mPas at 10 S ¹ .

15. Use of a surfactant mixture as specified in one of claims 1 to 11 or a concentrate according to one of claims 12 to 14 for the extraction of petroleum from un-underground petroleum deposits.