EP3884010A1 - Procédé pour l'exploitation pétrolière de gisements souterrains dotés d'une salinité élevée - Google Patents

Procédé pour l'exploitation pétrolière de gisements souterrains dotés d'une salinité élevée

Info

Publication number
EP3884010A1
EP3884010A1 EP19801916.8A EP19801916A EP3884010A1 EP 3884010 A1 EP3884010 A1 EP 3884010A1 EP 19801916 A EP19801916 A EP 19801916A EP 3884010 A1 EP3884010 A1 EP 3884010A1
Authority
EP
European Patent Office
Prior art keywords
surfactant
anionic surfactant
carbon atoms
water
general formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19801916.8A
Other languages
German (de)
English (en)
Inventor
Christian Bittner
Christian Spindler
Günter OETTER
David Ley
Lorenz Siggel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP3884010A1 publication Critical patent/EP3884010A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/02—Well-drilling compositions
    • C09K8/04—Aqueous well-drilling compositions
    • C09K8/26—Oil-in-water emulsions
    • C09K8/28—Oil-in-water emulsions containing organic additives

Definitions

  • 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 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.
  • TDS total dissolved salt
  • Olefin sulfonates or alkylarylsulfonates alone are not sufficiently tolerant of salt - especially when polyvalent cations such as calcium ions and magnesium ions are present.
  • alkyl alkoxylates 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.
  • thermostable connections are required, which do not decompose in the course of the flood process.
  • 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.
  • EP 0177098 describes a surfactant mixture for tertiary oil production, which consists of an alkyl ether carboxylate and an alkylarylsulphonate.
  • a surfactant mixture for tertiary oil production which consists of an alkyl ether carboxylate and an alkylarylsulphonate.
  • 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.
  • 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.
  • n stands for a number from 3 to 30.
  • M stands for an alkali metal atom.
  • 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.
  • 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.
  • 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 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.
  • 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%).
  • 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.
  • 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 surfactant concentration used (2% by weight) was relatively high in the flood tests, which were carried out at ⁇ 60 ° C.
  • 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.
  • 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 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.
  • R1 always stands for a branched alkyl radical with 16 to 17 carbon atoms and X is always a CH 2 group.
  • 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.
  • n stands for a number from 0 to 15 and m" for a number from 1 to 20.
  • 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.
  • m is preferably a Number from for 3 to 20 and n for a number from 0 to 99.
  • 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.
  • 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.
  • 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.
  • n stands for a number from 25 to 115.
  • X stands for SO3M, SO3H, CH2CO2M or CH2CO2H (M + is a cation).
  • 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.
  • 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.
  • 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
  • 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,
  • 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)
  • 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 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.
  • the present invention further provides a concentrate, based in each case on the total amount of the concentrate
  • a surfactant mixture 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.
  • 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.
  • 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).
  • 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).
  • the molar ratio of surfactant (A) to surfactant (B) is 90 : 10 to 10: 90.
  • 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).
  • 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.
  • 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)
  • anionic surfactants such as two, three or more ionic surfactants (A), may be present.
  • anionic surfactant (B) may be present.
  • 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.
  • 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.
  • 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,
  • 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)
  • 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;
  • 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.
  • surfactant mixture according to the present invention may also contain surfactants of the formula (III).
  • the surfactant mixture according to the present invention preferably also comprises at least one anionic surfactant (C) of the general formula (IV)
  • 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 ;
  • nb stands for a number from 3 to 10
  • 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.
  • 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.
  • variable Mb denotes the cation in formula (IV).
  • the cation is Na
  • the cation is preferably selected from Na, K or NH 4 . Na is more preferred.
  • 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).
  • the numbers o, nb mean values for all molecules of the surfactants.
  • the numbers o, nb mean values for all molecules of the surfactants.
  • 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.
  • 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.
  • a R 3b -0 group is followed by a propyleneoxy block with nb propyleneoxy groups and then an ethyleneoxy block with ethylene oxide groups.
  • the molar ratio of the sum of surfactant (A) and surfactant (B) to surfactant (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
  • 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.
  • oil reservoir temperature 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).
  • ICP-MS inductively coupled plasma mass spectrometry
  • 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:
  • 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.
  • 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.
  • 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.
  • 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.
  • the surfactant mixture described here or other surfactants can be added.
  • 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.
  • 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.
  • a surfactant formulation with or without polymer is injected in the first step.
  • the surfactant formulation causes the formation of a Winsor type III microemulsion.
  • 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.
  • both steps can also be carried out with water of the same salinity.
  • a gradient procedure can also be carried out in the surfactant mixture. This will be explained using an 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.
  • surfactant (C) of the general formula (IV) should be 50%.
  • 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.
  • 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.
  • the methods can of course also be combined with water floods.
  • 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.
  • At least one production well and at least one injection well are drilled into the oil deposit.
  • 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.
  • the term "petroleum” is of course not only meant to be single-phase oil, but also includes the usual crude oil-water emulsions.
  • 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.
  • an aqueous formulation 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.
  • water containing salts can be mixtures of different salts.
  • sea water can be used to set the aqueous formulation or it can be used formation water, which is reused in this way.
  • the injection water can also be formation water from other nearby reservoirs or aquifers.
  • the formulation is usually applied in sea water.
  • 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.
  • the Injection water can also be water that comes from a desalination plant.
  • 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.
  • 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.
  • At least one or more alkali metal ions are present.
  • 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.
  • 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.
  • 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.
  • oxygen scavengers include sulfites such as Na 2 S0 3 , bisulfites, phosphites, hypophosphites or dithionites.
  • 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.
  • 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).
  • substituted thioureas such as N, N'-dimethylthiourea, N, N'-diethylthiourea, N, N'-diphenylthiourea
  • thiocyanates such as, for example, ammonium thiocyanate or potassium thiocyanate
  • 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
  • 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.
  • the aqueous formulation used comprises at least one complexing agent.
  • 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.
  • complexing agents examples include ethylenediaminetetraacetic acid (EDTA), ethylenediaminodisuccinic acid (EDDS), diethylenetriaminepentamethylenephosphonic acid (DTPMP), methylglycinediacetic acid (MGDA) or nitrilotriacetic acid (NTA).
  • EDTA ethylenediaminetetraacetic acid
  • EDDS ethylenediaminodisuccinic acid
  • DTPMP diethylenetriaminepentamethylenephosphonic acid
  • MGDA methylglycinediacetic acid
  • NTA nitrilotriacetic acid
  • MGDA methylglycinediacetic acid
  • NTA nitrilotriacetic acid
  • 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.
  • aliphatic diols with 2 to 8 carbon atoms which can optionally also be further substituted.
  • 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.
  • the concentration of the polymer in the formulation is 0.02 to
  • 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.
  • 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 .
  • 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.
  • 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.
  • 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.
  • 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.
  • a method for oil production is used in which no base (e.g. alkali metal hydroxides or alkali metal carbonates) is used.
  • no base e.g. alkali metal hydroxides or alkali metal carbonates
  • 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.
  • 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.
  • 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.
  • At least one or more alkali metal ions are present.
  • 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.
  • 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.
  • 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.
  • 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.
  • aliphatic diols with 2 to 8 carbon atoms which can optionally also be further substituted.
  • 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.
  • 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.
  • 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.
  • surfactants (A), (B) or (C) are not identical to surfactants (A), (B) or (C), and
  • alkylbenzenesulfonates are from the group of alkylbenzenesulfonates, alpha-olefin sulfonates, internal olefin sulfonates, paraffin sulfonates, the surfactants having 14 to 28 carbon atoms; and or
  • alkyl ethoxylates and alkyl polyglucosides are selected from the group of alkyl ethoxylates and alkyl polyglucosides, the respective alkyl radical having 8 to 18 carbon atoms.
  • 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.
  • 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.
  • 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.
  • 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.
  • anionic surfactant (B) of the general formula (II) The same applies to the anionic surfactant (B) of the general formula (II).
  • 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.
  • 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
  • the molar ratio of ionic surfactant (A) to anionic surfactant (B) can be any,
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Carbonate deposits have lower porosities on average than sandstone deposits.
  • 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.
  • 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).
  • the composition of carbonate rocks can vary.
  • 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.
  • a preferred deposit could have 98% calcite, 1% dolomite and 1% halite.
  • 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.
  • 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.
  • 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.
  • anionic surfactant (A) of the general formula (I) R 1 - 0- (CH 2 CH 2 0) o- (CH2) pY- M + with R 1
  • 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.
  • 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%.
  • 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.
  • 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%.
  • 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.
  • 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.
  • 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 .
  • 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%.
  • 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.
  • 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.
  • 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%.
  • 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.
  • the surfactants were dissolved in saline water in the concentration to be investigated.
  • NaMBT and Na 2 S0 3 were used as radical scavengers and as oxygen scavengers.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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 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.
  • 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
  • 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.
  • 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.
  • 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).
  • 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.
  • 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
  • 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.
  • 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
  • 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).
  • 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)
  • 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.
  • 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).
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

La présente invention concerne un procédé pour l'exploitation de pétrole d'un gisement de pétrole souterrain, dans lequel une formulation aqueuse, contenant un sel, de tensioactifs comprenant un mélange de tensioactifs est injectée dans le gisement de pétrole par l'intermédiaire d'au moins un puits d'injection, pour l'abaissement de la tension de surface entre l'huile et l'eau à < 0,1 mN/m, et de l'huile brute est extraite du gisement par l'intermédiaire d'au moins un puits de production, caractérisé en ce que le gisement de pétrole présente une température de ≥ 25 °C et <130 °C et une eau de formation dotée d'une salinité de ≥ 50 000 ppm de sels dissous et en ce que le mélange de tensioactifs contient au moins un tensioactif anionique (A) de formule générale R1-O-(CH2-CH2O)o-(CH2)p-Y-M+(Il) et au moins un tensioactif anionique (B) de formule générale R2-O-(CH2CH2O)o-(CH2)p-Y-M+(II), où lors de l'injection, un rapport molaire de tensioactif anionique (A) à tensioactif anionique (B) dans le mélange de tensioactifs de 90:10 à 10:90 est présent, et le mélange de tensioactifs ne contenant aucun tensioactif ionique de formule générale (R1a)k-N+(R2a)(3-k)R3a (X-)l (III). L'invention concerne en outre un concentré du mélange de tensioactifs et son utilisation.
EP19801916.8A 2018-11-23 2019-11-19 Procédé pour l'exploitation pétrolière de gisements souterrains dotés d'une salinité élevée Withdrawn EP3884010A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP18207957 2018-11-23
PCT/EP2019/081782 WO2020104449A1 (fr) 2018-11-23 2019-11-19 Procédé pour l'exploitation pétrolière de gisements souterrains dotés d'une salinité élevée

Publications (1)

Publication Number Publication Date
EP3884010A1 true EP3884010A1 (fr) 2021-09-29

Family

ID=64456801

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19801916.8A Withdrawn EP3884010A1 (fr) 2018-11-23 2019-11-19 Procédé pour l'exploitation pétrolière de gisements souterrains dotés d'une salinité élevée

Country Status (3)

Country Link
US (1) US20220002614A1 (fr)
EP (1) EP3884010A1 (fr)
WO (1) WO2020104449A1 (fr)

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3811508A (en) * 1972-07-10 1974-05-21 Getty Oil Co Methods for selective plugging
US4018278A (en) * 1974-11-25 1977-04-19 Texaco Inc. Surfactant oil recovery process usable in high temperature formations
DE3105912C1 (de) * 1981-02-18 1982-09-30 Chemische Werke Hüls AG, 4370 Marl Verfahren zur Gewinnung von OEl aus einer unterirdischen Lagerstaette
DE3033927C2 (de) 1980-09-10 1982-09-09 Chemische Werke Hüls AG, 4370 Marl Verfahren zur Gewinnung von weitgehend emulsionsfreiem Öl aus einer unterirdischen Lagerstätte
ATE4468T1 (de) 1980-09-10 1983-09-15 Chemische Werke Huels Ag Verfahren zur gewinnung von oel aus einer unterirdischen lagerstaette.
DE3105913C2 (de) 1981-02-18 1983-10-27 Chemische Werke Hüls AG, 4370 Marl Verfahren zur Gewinnung von Öl aus unterirdischen Lagerstätten durch Emulsionsfluten
EP0073894B1 (fr) 1981-09-01 1986-01-29 Hüls Aktiengesellschaft Procédé pour la récupération d'huile à partir d'un réservoir souterrain
GB2165281B (en) 1984-10-05 1988-01-20 Shell Int Research Surfactant composition and process for the production of oil using such a composition
DE3523355A1 (de) 1985-06-29 1987-01-08 Huels Chemische Werke Ag Verfahren zur gewinnung von oel aus unterirdischem speichergestein
US4811788A (en) 1986-02-13 1989-03-14 The Standard Oil Company Surfactant combinations and enhanced oil recovery method employing same
US4886120A (en) 1989-02-01 1989-12-12 Conoco Inc. Process for secondary oil recovery utilizing propoxylated ethoxylated surfactants in seawater
EP2250232A1 (fr) 2008-02-07 2010-11-17 Shell Internationale Research Maatschappij B.V. Procédé et composition pour une récupération accrue d hydrocarbures
CN102057013B (zh) 2008-04-10 2014-04-09 巴斯夫欧洲公司 用于三级原油回收的基于支化醇的表面活性剂
US8853136B2 (en) * 2009-10-14 2014-10-07 Basf Se Process for tertiary mineral oil production using surfactant mixtures
US8596367B2 (en) * 2010-03-10 2013-12-03 Basf Se Process for producing mineral oil using surfactants based on C16C18-containing alkyl propoxy surfactants
ES2921885T3 (es) 2010-03-10 2022-09-01 Basf Se Formulaciones de tensioactivos acuosos para procesos de recuperación de petróleo que usan tensioactivos alquilpropóxicos que contienen C16C18
AR082740A1 (es) 2010-08-27 2012-12-26 Univ Texas Tensioactivos de alcoxi carboxilicos, composicion acuosa y eliminacion de material hidrocarbonado
EA028023B1 (ru) 2011-10-24 2017-09-29 Басф Се Смесь пав, способ ее получения и ее применение, водная композиция пав, ее применение и способ добычи нефти с применением композиции пав
AR090723A1 (es) 2012-04-19 2014-12-03 Univ Texas Tensioactivos hidrofobos cortos
US20160215200A1 (en) * 2013-09-26 2016-07-28 Shell Oil Company Composition and method for enhanced hydrocarbon recovery
FR3021053A1 (fr) 2014-05-13 2015-11-20 Total Sa Compositions de tensio-actifs et de polymeres et leurs utilisations pour la recuperation amelioree d'hydrocarbures
EP3221417B2 (fr) 2014-11-18 2025-12-10 Basf Se Procédé pour le transport de pétrole
MX2019014431A (es) 2017-05-30 2020-08-17 Basf Se Método de producción de aceite mineral de depósitos subterráneos que tienen alta temperatura y salinidad.
WO2019057769A1 (fr) * 2017-09-21 2019-03-28 Basf Se Mélange de sulfate d'éther alkylique robuste pour récupération améliorée d'huile
CN108485631B (zh) * 2018-05-14 2020-12-01 中国日用化学研究院有限公司 一种耐高温和高矿化度的无碱驱油剂及制备方法

Also Published As

Publication number Publication date
US20220002614A1 (en) 2022-01-06
WO2020104449A1 (fr) 2020-05-28

Similar Documents

Publication Publication Date Title
EP3221417B2 (fr) Procédé pour le transport de pétrole
EP3630915A1 (fr) Procédé à haute température et à haute salinité pour l&#39;exploitation pétrolière de gisements souterrains
DE60212427T2 (de) Gegenseitige lösungsmittel für hochkonzentrierte behandlungsflüssigkeiten
EP3080227B1 (fr) Procédé d&#39;extraction de pétrole
DE69418097T2 (de) Schäumende zusammensetzung und verfahren zur bohrlochbehandlung
DE69303214T2 (de) Zusammensetzungen und Methoden zur Gaslochbehandlung
EP3402858A1 (fr) Procédé d&#39;extraction tertiaire de pétrole à l&#39;aide d&#39;un polymère à groupes hydrophobes associatifs
DE69600687T2 (de) Chemikalien für erdöl-und erdgaslagerstätte
EP0073894B1 (fr) Procédé pour la récupération d&#39;huile à partir d&#39;un réservoir souterrain
EP1446459B1 (fr) Methode de forage de puits et fluide de forage
EP0047370B1 (fr) Procédé pour la récupération de pétrole d&#39;une formation souterraine
DE69613981T2 (de) Verwendung von imidazolin abgeleiter amphoacetate tenside von hohen reinheit als schaummittel in olbohrungen
DE2543239A1 (de) Verfahren zur gewinnung von oel aus untertaegigen formationen
US11066914B2 (en) Foam from low cost petroleum sulfonate surfactants for fracturing along with wettability alteration
DE2753091A1 (de) Verfahren zur sekundaergewinnung von erdoel
CA1230960A (fr) Methode modifiee d&#39;extraction par injection d&#39;eau des hydrocarbures contenus dans des gisements souterrains argileux
EP0047369B1 (fr) Procédé pour la récupération de pétrole largement dépourvu d&#39;émulsion d&#39;une formation souterraine
EP3652268B1 (fr) Agents d&#39;amélioration de la solubilité à base d&#39;alcool allylique de formulations de tensioactifs aqueux pour améliorer la récupération d&#39;huile
EP0264867B1 (fr) Sulfonates de styrylaryloxy-éthers, leur procédé de préparation et leur emploi dans l&#39;extraction du pétrole
EP0213321B1 (fr) Procédé pour augmenter l&#39;injectivité de trous de forage pour la récupération d&#39;huile par noyage à l&#39;eau
EP3884010A1 (fr) Procédé pour l&#39;exploitation pétrolière de gisements souterrains dotés d&#39;une salinité élevée
WO2022036362A1 (fr) Mousse à base de tensioactifs de sulfonate de pétrole à faible coût pour fracturation avec modification de la mouillabilité
WO2015189060A1 (fr) Macromonomères amphiphiles, procédés de préparation de macromonomères amphiphiles, copolymères contenant des macromonomères amphiphiles et leur utilisation pour la récupération assistée du pétrole
EP0088206B1 (fr) Procédé pour l&#39;extraction de pétrole d&#39;un réservoir souterrain
US11078405B2 (en) 3 in 1 foam formulation for enhanced oil recovery including conformance control, ultra-low interfacial tension, and wettability alteration

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20210623

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20220729

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20221209