WO2015135708A1 - Procédé d'injection de co2 associé à des al(k/cén)ylpolyéthersulfonates - Google Patents

Procédé d'injection de co2 associé à des al(k/cén)ylpolyéthersulfonates Download PDF

Info

Publication number
WO2015135708A1
WO2015135708A1 PCT/EP2015/052711 EP2015052711W WO2015135708A1 WO 2015135708 A1 WO2015135708 A1 WO 2015135708A1 EP 2015052711 W EP2015052711 W EP 2015052711W WO 2015135708 A1 WO2015135708 A1 WO 2015135708A1
Authority
WO
WIPO (PCT)
Prior art keywords
surfactant
surfactants
water
radicals
och
Prior art date
Application number
PCT/EP2015/052711
Other languages
German (de)
English (en)
Inventor
Christian Bittner
Günter OETTER
Benjamin Wenzke
Sebastian Alexander WEISSE
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 WO2015135708A1 publication Critical patent/WO2015135708A1/fr

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
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/594—Compositions used in combination with injected gas, e.g. CO2 orcarbonated gas
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the invention relates to a method for producing crude oil by means of C02 flooding, in which liquid or supercritical CO2 and at least one alk (en) ylpolyethersulfonate are injected through at least one injection well into an oil reservoir and the crude oil is removed from the deposit by at least one production well.
  • the alk (en) yl polyether sulfonate is preferably dissolved in the CO 2 phase.
  • the invention furthermore relates to a process for crude oil production by means of CO 2 flooding, in which mixtures of the alk (en) ylpolyethersulfonates with alk (en) ylpolyalkoxylates and / or alkylphenolpolyalkoxylates are used.
  • a deposit In natural oil deposits, petroleum is present in the cavities of porous reservoirs, which are closed to the earth's surface by impermeable cover layers.
  • the cavities may be very fine cavities, capillaries, pores or the like. Fine pore necks, for example, have a diameter of only about 1 ⁇ .
  • a deposit In addition to crude oil, including natural gas, a deposit usually contains more or less saline water. After tapping a petroleum deposit, oil may first flow to the surface by itself through the borehole due to the inherent pressure of the reservoir.
  • the autogenous pressure can be caused by gases present in the deposit such as methane, ethane or propane. This type of promotion is usually referred to as primary oil production.
  • Tertiary oil extraction includes heat processes in which hot water or superheated steam is injected into the reservoir, thereby increasing the viscosity of the oil
  • Tertiary oil extraction also includes processes involving the use of suitable chemicals, such as surfactants or thickening polymers, as an aid to oil production, which can be used to influence the situation towards the end of the flood and thereby promote the capture of crude oil previously held in the rock formation.
  • suitable chemicals such as surfactants or thickening polymers
  • C02 flooding liquid or supercritical CO2 is injected through one or more injection wells into a petroleum formation, flows from there to production wells, and mobilizes existing oil in the formation.
  • the production wells are extracted from mobilized petroleum.
  • This technology is also known as “CO2 enhanced oil recovery (EOR)” or “CO2 improved oil recovery (IOR)” and has great economic importance:
  • EOR CO2 enhanced oil recovery
  • IOR improved oil recovery
  • CO2 is soluble in and lowers petroleum Viscos
  • Another delivery mechanism may be the dissolution of preferably light levels of crude oil into the C02 phase rather than a type of extraction.
  • Another aspect is the low interfacial tension between crude oil and liquid or supercritical CO2, which helps to overcome capillary forces: an oil drop can more easily deform in a C02 phase and pass through narrow pore necks than it could in a water phase.
  • the critical point of CO2 is 30.98 ° C and 73.75 bar. Above these values, CO2 is supercritical, ie it is almost as dense as a liquid but still has a very low viscosity similar to that of a gas.
  • the viscosity of supercritical CO2 is typically several orders of magnitude lower than that of the oil in the reservoir.
  • the low viscosity of supercritical CO2 is one of the key problems of C02 flooding, making mobility mobility of CO2 in the reservoir much more difficult.
  • the CO2 should flow in a uniform front from the injection well towards the production wellbore, flowing through all (still) oil filled areas of the formation.
  • the porosity of an underground oil deposit is generally not homogeneous, and in addition to fine-pored areas, an underground petroleum formation may also have areas of high porosity, cracks or fractures.
  • the flow resistance for CO2 still filled with oil areas of the formation is significantly greater than the flow resistance of already de-oiled areas.
  • the density of liquid or supercritical CO 2 is significantly lower than the density of crude oil and formation water. Due to the buoyancy, therefore, CO2 preferably collects in the upper layers of the formation or preferably flows through the upper layers. The de-oiling is thus preferably carried out in the upper layers of the formation, while deeper layers are not detected by the CO2.
  • CC n-water emulsions or CC n-water foams in the deposit of CO 2 and formation water and / or injected water.
  • the CO2 is in a discontinuous phase, while water forms the continuous phase.
  • Such emulsions have a significantly higher viscosity than supercritical or liquid CO2 and thus no longer follow only the paths of least flow resistance, but flow much more uniformly through the formation.
  • Mobility control by formation of C02-in-water emulsions allows for increased exploitation of the deposit through macroscopic displacement (mobility control) and microscopic displacement (interfacial tension)
  • the requirements for surfactants for CO 2 flooding are clearly different from requirements for surfactants for other applications, for example detergent applications; however, they also differ, in particular, from the requirements for surfactants for surfactant flooding, i. an EOR technique that injects aqueous solutions of surfactants but no CO2 into the deposit.
  • the primary role of surfactants in surfactant flooding is to reduce the interfacial tension between water and petroleum.
  • petroleum droplets trapped in the formation are mobilized.
  • the primary role of surfactants in C02 flooding to form C02-in-water emulsions is to stabilize the C02-water interfaces to generate long-term stable CC n-water emulsions in the deposit.
  • the hydrophobic radicals of the surfactants protrude into the liquid or supercritical CO 2 phase and must therefore have good interaction with the CO 2 in order to ensure good stabilization of the CO 2 -water interface.
  • the formation of CC n-water emulsions at the usual reservoir temperatures (typically about 15 ° C to 130 ° C) and in the presence of highly saline water, especially in the presence of high levels of calcium and / or magnesium ions guaranteed be. If the highly viscous CC n-water emulsion collapses, the low-viscosity supercritical CO 2, as described above, preferably follows the paths of lowest flow resistance and / or accumulates in the upper regions of the formation.
  • suitable surfactants must also be sufficiently soluble and sufficiently stable in reservoir water and / or injected water.
  • the water is acidic due to dissolved CO2 (pH values of approx. 3).
  • Suitable surfactants must therefore be soluble in an acidic environment and have sufficient long-term stability against hydrolysis.
  • popular surfactants such as alkyl sulfates or alkyl ether sulfates are therefore less suitable for CO 2 flooding, since they are less soluble on the one hand by protonation and the sulfate group can be split off hydrolytically under the conditions mentioned.
  • Amide group-containing compounds also tend to hydrolyze under the conditions mentioned.
  • the adsorption tendency of the surfactants on the rock should be as low as possible in order to minimize the loss of surfactant.
  • US 3,342,256 describes the improvement of oil production with the aid of CO2 and a surfactant for mobility control.
  • the surfactant may optionally be injected via the CO2 phase or via the water phase.
  • Suitable surfactants include octylphenol ethoxylates, dioctylsulfosuccinate sodium salt, laurylsulfate sodium salt or isopropylnaphthalenesulfonate sodium salt.
  • US Pat. No. 4,113,011 1 describes a process for oil extraction with injection of CO2 and an aqueous surfactant solution.
  • the surfactant disclosed is an alkyl ether sulfate of the RO-EO sulfate type, which is composed of an alcohol having 9 to 11 carbon atoms and 1 to 5 EO units. Reference is made to a higher salt tolerance compared to the use of alkyl sulfates. However, sulfates are not sufficiently stable in the long term to hydrolysis under the conditions of CO 2 flooding.
  • No. 4,380,266 describes a process for the extraction of crude oil by injection of a mixture of CO 2 and EO-PO block polymers or alkyl ethoxylates or alkylphenol ethoxylates or alkyl alkoxylates, the conditions being selected so that the CO 2 is liquid under the reservoir conditions.
  • Polytergent ® Called SL-62 This is a linear alcohol of 6 to 10 carbon atoms, which is propoxylated and ethoxylated.
  • US 5,033,547 discloses a process for oil recovery by injecting a mixture of CO 2 and a surfactant into a petroleum formation, forming an emulsion of CO 2, water and the surfactant in the formation together with formation water.
  • the surfactants are alkyl ethoxylates or alkylphenol ethoxylates which have a hydrophobic group having 7 to 15 carbon atoms and a degree of ethoxylation of 4 to 8.
  • DE 30 454 26 A1 discloses the improvement of oil production by the injection of gaseous CO2 and surfactant to form a foam.
  • surfactants alkylphenol alkoxylates, sodium dodecylsulfonate, sodium polyglycol ether sulfonate and polypropylene oxide ethylene oxide polymers are proposed, inter alia.
  • US 5,046,560 discloses a method for oil production with injection of a gas selected from the group of hydrocarbons, inert gases, steam or carbon dioxide and an aqueous Alkylarylpolyalkoxysulfonat solution.
  • a gas selected from the group of hydrocarbons, inert gases, steam or carbon dioxide and an aqueous Alkylarylpolyalkoxysulfonat solution.
  • the sulfonate group is located on the aryl radical.
  • DE 32 086 62 A1 discloses a process for oil extraction by injection of a formulation comprising water, CO2 and nonionic surfactants.
  • surfactants alcohol ethoxylates based on octylphenol, nonylphenol or C 12 -C 15 -alcohol are mentioned.
  • US Pat. No. 7,842,650 describes a process for producing crude oil, which comprises producing foams from liquids using a surfactant mixture from a foaming agent (a) selected from the group of sulfates, sulfonates, phosphates, carboxylates, sulfosuccinates, betaines, quaternary ammonium salts, amine oxides, amines - Nethoxylaten, amide ethoxylates, acid ethoxylates, alkyl glucosides, EO-PO block copolymers and long-chain fatty alcohol ethoxylates and a cosurfactant (b) of the general formula RO- (AO) y -H or RO- (AO) y -Z, where R is a hydrocarbon radical with 6 to 12 carbon atoms, (AO) y is an alkyleneoxy block, y is a number from 5 to 25 and Z is an anionic group, eg sulfate, phosphate
  • WO 2010/044818 A1 describes a process for producing oil by C0 2 fl ows by injecting a nonionic surfactant having a CO 2 Philicity of 1.5 to 5.0 into the formation, wherein the surfactant is to form a stable foam with formation water but not an emulsion with crude oil.
  • the nonionic surfactant preferably has the formula RO- (AO) x- (EO) y -H, where AO is an alkoxy group having 3 to 10 carbon atoms and EO is ethoxy groups, where R, AO, x and y are the following groups: Combinations can be selected:
  • R AO x y branched alkyl, alkylaryl or cycloalkyl C3 1, 5 - 1 1 6 - 25th
  • surfactants selected from the group of C 8 Hi7- (PO) 5 - (EO) 9 -H, C 8 Hi 7 - (PO) 5 - (EO) i iH, C 8 Hi7- (PO ) 9- (EO) 9 -H,
  • US 4,502,538 discloses a process in which liquefied CO2, an aqueous medium and a surfactant are injected into an underground formation containing oil and water.
  • the surfactant may be an alkylpolyalkoxysulfonate which has, as the hydrophobic part, an aliphatic and / or aromatic hydrocarbon radical having 6 to 25 carbon atoms.
  • WO 201 1/005246 A1 describes surfactants for crude oil production, which can be injected with C0 2 and water into a deposit.
  • the nonionic surfactants are glycerin derivatives wherein two of the alcohol groups of the glycerol are capped with a hydrocarbon group which may include from 4 to 18 carbon atoms.
  • the third alcohol group can be ethoxylated, propoxylated or butoxylated and have a degree of alkoxylation of 9-40.
  • WO 201 1/152856 A1 discloses a method for oil production with the aid of supercritical CO2 and a surfactant which is injected into a CO 2 stream and dissolved in the CO 2.
  • the reservoir is made up of reservoir water, surfactant and CO2 to form an emulsion.
  • nonionic surfactants eg, alkylphenol ethoxylates
  • cationic surfactants such as ethoxylated talc fatty amine
  • anionic surfactants eg, alkyl ether sulfates
  • betaine surfactants eg, betaine surfactants
  • WO 2012/170835 A1 claims a process in which a nonionic surfactant formulation having a pour point of from -3 to -54 ° C. is used, dissolved in CO 2 and injected into the formation to form emulsions with water. To lower the pour point, alcohols such as methanol, ethanol, glycol or glycol ethers are proposed.
  • WO 2013/043838 A1 describes an oil production process with liquid or supercritical surfactant and an alkoxylated amine which is based on a secondary alkyl radical having 4 to 30 carbon atoms.
  • WO 2013/048860 A1 describes a process for crude oil production which claims the use of CO 2 and an alkyl alkoxylate which is based on a branched alkyl radical having 3 to 9 carbon atoms and the alkoxylation by means of double metal cyanide catalysis
  • Tertiary oil production by means of C02 flooding is a large-scale process.
  • the surfactants are only used as dilute solutions in water or CO2, the volumes injected per day are high and the injection is typically continued for months to several years.
  • the surfactant requirement for an average oil field can be about 2000 to 3000 t / a. Even a slightly better surfactant can significantly increase the efficiency of C02 flooding.
  • the CO 2 flooding is said to form a viscous C02-in-water emulsion. In the C02-in-water emulsion, water forms the continuous phase and thus acts as a buffer between discrete CO 2 phases.
  • surfactants depend on the reservoir temperatures, in particular on the salinity of the reservoir water and the reservoir temperature. While many surfactants are found at low salinities and / or low Temperatures still yield satisfactory results, they do not provide good results at high temperatures and / or high salinities.
  • the object of the invention was to provide an improved process for CO 2 flooding, in particular for oil reservoirs with high salinity and / or high reservoir temperature. Even under such demanding conditions, stable CC n-water emulsions should be formed.
  • liquid or supercritical CO2 and at least one anionic surfactant (I) or a surfactant mixture comprising at least one anionic surfactant (I) are injected through at least one injection well into a crude oil deposit and the Deposits by at least one production well crude oil, characterized in that the at least one surfactant (I) or the at least one surfactant (I) comprising surfactant mixture is dissolved in liquid or supercritical CO2 and injected and / or dissolved in an aqueous medium and injected
  • the deposit has a deposit temperature of 15 ° C to 140 ° C
  • the deposit water has a salinity of 20,000 ppm to 350,000 ppm
  • the density of CO2 under deposit conditions is 0.70 g / mL to 0.90 g / mL
  • the at least one anionic surfactant is an alk (en) ylpolyalkoxysulfonate of general formula
  • R 1 is a branched or linear, saturated or unsaturated aliphatic hydrocarbon radical having 8 to 22 carbon atoms
  • R 2 , R 3 , R 4 , R 5 are each H or a linear or branched alkyl radical having 1 to 8
  • R 7 is an alkylene radical having 2 to 4 carbon atoms, which may optionally be substituted by an OH group,
  • n for a number from 5 to 30, and
  • Figure 1 Schematic representation of fingering in C02 flooding.
  • Figure 2 Schematic representation of the high pressure reactor with viewing windows used for the examples and comparative examples.
  • Figure 3 View through the viewing window of the high-pressure reactor before mixing: C02 phase and water phase (schematic representation).
  • Figure 4 View through the viewing window of the high-pressure reactor after mixing: C02 phase, CC n-water emulsion and water phase (schematic representation).
  • liquid or supercritical CO 2 and at least one anionic surfactant (I) are injected into a crude oil deposit.
  • at least one anionic surfactant (I) other surfactants and other components can be used.
  • the anionic surfactants (I) are used in combination with nonionic surfactants (II) and / or different anionic surfactants (III).
  • Anionic surfactants (I) are alk (en) yl ether sulfonates of the general formula
  • R 1 is a branched or linear, saturated or unsaturated aliphatic hydrocarbon radical having 8 to 22 carbon atoms, preferably 8 to 18 carbon atoms, particularly preferably 10 to 14 carbon atoms.
  • radicals R 1 include linear alkyl radicals such as in particular n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl or n-docosyl residues. It may also be surfactants comprising mixtures of different radicals R 1 .
  • radicals R 1 include branched alkyl radicals such as 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl radicals and radicals derived from oxo alcohols, such as i-tridecyl radicals.
  • R 1 is a branched alkyl radical of the formula C 5 Hn-CH (C 3 H 7) -CH 2 -, where at least 70 mol% of the pentyl radicals C 5 H 11 - is an n-CsHu radical.
  • the substituent in 2-position, the propyl radical C3H7- may be in an n-C3H 7 group or an i-C3H 7 act radical. It is preferably an n-C3H 7 radical.
  • the pentyl radicals which are not n-pentyl radicals are preferably branched 1-alkyl radicals, preferably a 2-methyl-1-butyl radical C2H 5 CH (CH 3) CH 2 - and / or a 3-methyl-1 - butyl CH 3 CH (CH 3) CH 2 CH 2.
  • 70 to 99 mol% of the C5H11- radicals are n-C5Hn radicals, and from 1 to 30 mol% of the C5H11 radicals are C 2 H 5 CH (CH 3 ) CH 2 radicals and / or CH 3 CH (CH 3 ) CH 2 CH 2 radicals.
  • R 1 is a 2-propyl-n-heptyl radical
  • radicals R 2 , R 3 , R 4 and R 5 are each independently H or a linear or branched alkyl radical having 1 to 8 carbon atoms, for example methyl, ethyl or propyl radicals, with the proviso in that the sum of the carbon atoms of the radicals R 2 + R 3 + R 4 + R 5 is 2 to 8, preferably 2 or 3 and particularly preferably 2.
  • R 6 is methyl, -OCH 2 CHR 6 - is thus a propoxy group and -OCH 2 CH 2 - an ethoxy group.
  • R 7 is an alkylene radical having 2 to 4 carbon atoms, which may optionally be substituted by an OH group. It is preferably a group selected from the group of 1, 2-ethylene groups -CH 2 -CH 2 -, 1, 2-propylene groups -CH 2 -CH (CH 3 ) - or -CH (CH 3 ) -CH 2 - , 1, 3-propylene groups
  • I is a number from 0 to 5, preferably 0, m is a number from 0 to 15, preferably 0 to 9 and n is a number from 5 to 30, preferably 5 to 20 and the sum of I + m + n is from 5 to 35, preferably from 8 to 29.
  • indices I, m and n are further chosen with the proviso that n> (l + m) and particularly preferably n> 2 (l + m).
  • n> (l + m) and particularly preferably n> 2 (l + m).
  • I, m, and n are averages over all molecules. Accordingly, I, n and m are not natural numbers but rational numbers.
  • a distribution of chain lengths can be described in a manner known in principle by the so-called polydispersity D.
  • D M w / M n is the quotient of the weight average molecular weight and the number average molar mass.
  • the polydispersity can be determined by means of the methods known to the person skilled in the art, for example by means of gel permeation chromatography. It is further clear to the person skilled in the art that the orientation of the propoxy and / or butoxy groups depends on the reaction conditions -OCR 2 R 3 CR 4 R 5 - or -OCH 2 CHR 6 - or else -OCR 5 R 4 CR 3 R 2 -b. -OCHR 6 CH 2 - can be.
  • the representation in formula (I) is not intended to indicate the orientation of the alkoxy units.
  • the radicals -OCR 2 R 3 CR 4 R 5 -, -OCH 2 CHR 6 - and -OCH 2 CH 2 - are arranged blockwise in the order given in formula (I). It is known to the person skilled in the art that small residues of alkylene oxides can remain in the course of an alkoxylation. After addition of the next alkylene oxide, these can then be copolymerized into the second block so that small amounts of an alkylene oxide are in the "wrong" block. [. In] As a rule, at least 90% of the above radicals are arranged in the order given in formula (I), ie at least 90% of the radicals are also found in the "right" block.
  • Examples of preferred anionic surfactants (I) include
  • EO stands for an ethyleneoxy group
  • PO for a propyleneoxy group
  • 1C13H27- for a branched C 13 -alkyl radical
  • n (C 12 H 25 C 4 H 29) - for a mixture of linear C 12 - and C 6 -alkyl radicals.
  • 1, 2-butene oxide, 2,3-butene oxide or isobutene oxide can be used.
  • Suitable alcohols R 1 OH are known to the person skilled in the art and are commercially available.
  • linear alcohols can be fatty alcohols or mixtures of different fatty alcohols.
  • linear alcohols can also be prepared by oligomerization of ethylene and subsequent functionalization (eg Ziegler process).
  • surfactants with branched hydrocarbon radicals oxo alcohols or Guerbet alcohols can be used.
  • Alcohols C5HnCH (C3H7) CH20H can be prepared by aldol condensation of valeraldehyde followed by hydrogenation.
  • the preparation of valeraldehyde and the corresponding isomers is carried out by hydroformylation of butene, as described for example in US 4,287,370; Beilstein E IV 1, 32 68, Ullmanns Encyclopedia of Industrial Chemistry, 5th edition, volume A1, pages 323 and 328 f.
  • the subsequent aldol condensation is described, for example, in US Pat. No. 5,434,313 and Römpp, Chemie Lexikon, 9th edition, keyword "aldol addition” on page 91.
  • the hydrogenation of the aldol condensation product follows general hydrogenation conditions.
  • Alcohols C5HnCH (C3H 7) CH20H can also be prepared from 1 pentanol by the Guerbet reaction.
  • technical 1-pentanols can be used, which usually contain certain amounts of methyl-1-butanols.
  • the 1-pentanols are reacted in the presence of KOH at elevated temperatures, see, eg, Marcel Guerbet, CR. Acad Sei Paris 128, 51 1, 1002 (1899), Rompp, Chemie Lexikon, 9th edition, Georg Thieme Verlag Stuttgart, and the literature mentioned there and Tetrahedron, Vol 23, pages 1723-1733.
  • the alcohol R 1 OH used is C 5 Hich (C 3 H 7 ) CH 2 OH, where 70 to 99 mol% of the alcohol C 5 Hn have the meaning n-CsHn and 1 to 30 percent by weight of the alcohol C5H11- the importance C2H 5 CH (CH 3) CH 2 and / or CH 3 CH (CH 3) CH 2 CH 2 has.
  • Such alcohols are commercially available.
  • R 1 OH is 2-propylheptanol-1 HsCCHzCHzCHzCHzCH vCsH ⁇ CHzOH.
  • the alcohols according to the general formula (Ia) can be prepared, for example, by base-catalyzed alkoxylation.
  • the alcohol R 1 OH can be mixed in a pressure reactor with alkali metal hydroxides, preferably potassium hydroxide, sodium hydroxide, alkaline earth metal hydroxides or with alkali metal alkoxides, such as, for example, sodium methylate.
  • alkali metal hydroxides preferably potassium hydroxide, sodium hydroxide, alkaline earth metal hydroxides or with alkali metal alkoxides, such as, for example, sodium methylate.
  • reduced pressure for example ⁇ 100 mbar
  • water or methanol still present in the mixture can be removed.
  • the alcohol is then partly present as the corresponding alkoxide.
  • the mixture is then inertized with inert gas (for example nitrogen) and the alkylene oxide (s) is added stepwise at temperatures of 90 to 180 ° C up to a maximum pressure of 10 bar.
  • inert gas for example nitrogen
  • the alkylene oxide is initially metered in at 120 ° C. In the course of the reaction, the temperature rises up to 170 ° C due to the released heat of reaction.
  • the delay between injection of the various alkylene oxides can be shortened in one embodiment, so that the last injected alkylene oxide is not fully reacted and form by the newly injected alkylene oxide mixing blocks with small amounts of the previously added alkylene oxide.
  • butylene oxide can be added first at a temperature in the range of 125 to 145 ° C, then the propylene oxide at a temperature in the range of 125 to 145 ° C and then the ethylene oxide at a temperature in the range of 120 to 155 ° C. In the case of the absence of butyleneoxy units in the molecule, first propylene oxide and then ethylene oxide are metered in.
  • the catalyst can be neutralized, for example by addition of acid (for example acetic acid, citric acid or phosphoric acid) and filtered off if necessary.
  • acid for example acetic acid, citric acid or phosphoric acid
  • the alkoxylation of the alcohols R 1 OH can of course be carried out by other methods, for example by acid-catalyzed alkoxylation.
  • double hydroxide clays as described in DE 4325237 A1 or it is possible to use double metal cyanide catalysts (DMC catalysts).
  • DMC catalysts are disclosed, for example, in DE 10243361 A1, in particular in sections [0029] to [0041] and in the literature cited therein.
  • Zn-Co type catalysts can be used.
  • the alcohol R 1 OH is admixed with the catalyst, the mixture is dehydrated as described above and reacted with the alkylene oxides as described. It is usually not more than 1000 ppm catalyst used with respect to the mixture and the catalyst may remain in the product due to this small amount.
  • the amount of catalyst can be in typically less than 1000 ppm, for example 250 ppm or 100 ppm or less.
  • the resulting alk (en) ylpolyalkoxylates (Ia) are sulfonated in one or more further reaction steps, the surfactants (I) being obtained.
  • the sulfonation can be carried out, for example, by substitution of the OH group of the alkoxylate for Cl using phosgene or thionyl chloride.
  • the reaction can be carried out in the presence of a solvent such as chlorobenzene.
  • HCl liberated as well as liberated CO2 or SO2 can advantageously be removed from the system by stripping with nitrogen so that ether cleavage is prevented.
  • the alkylalkoxychlor compound is then reacted with an aqueous solution of sodium sulphite, the chloride being substituted by sulphite and the alkyl ether sulphonate being obtained.
  • substitution may be carried out in the presence of a phase mediator (eg Cr to Cs alcohols) at a temperature of 100-180 ° C and pressure.
  • a phase mediator eg Cr to Cs alcohols
  • R 10 is an ethylene group -CH 2 CH 2 -.
  • An alternative to chlorination is the sulfation of the alkyl alkoxylates with SO3 in a falling film reactor and subsequent neutralization with NaOH.
  • the alkyl ether sulfate formed can be converted into the alkyl ether sulfonate by nucleophilic substitution of the sulfate group by sodium sulfite analogously to the above description.
  • the alkyl ether sulfonates (III) can alternatively be obtained by addition of vinyl sulfonic acid to the alkyl alkoxylate. Details of this are described for example in EP 31 1 961 A1. In this case, an alkyl ether sulfonate having a terminal group -CH2CH2-SO3M is obtained.
  • Alk (en) ylpolyethersulfonates of the general formula (I) have, in comparison to corresponding The advantage of these alk (en) ylpolyether sulfates is that they do not hydrolyze in the acidic state and thus fulfill the requirement for adequate long-term stability.
  • nonionic surfactants (II) is alk (en) ylkoxylate the general formula (II) R 8 - (OCR 2 R 3 CR 4 R 5) x (OCH 2 CHR 6) y - (OCH 2 CH 2) z-OH (II).
  • R 8 is a branched or linear, saturated or unsaturated aliphatic hydrocarbon radical having 8 to 22 carbon atoms, preferably 8 to 18 carbon atoms, particularly preferably 8 to 14 carbon atoms.
  • radicals R 8 include linear alkyl radicals such as in particular n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl or n-docosyl residues. It may also be surfactants comprising mixtures of different radicals R 1 . Particularly noteworthy here are mixtures which derive from the use of natural fatty alcohols as starting material for the surfactants (I). For example, it may be a mixture of n-dodecyl and n-tetradecyl.
  • radicals R 1 include branched alkyl radicals such as 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl radicals and radicals derived from oxo alcohols, such as i-tridecyl radicals.
  • R 8 is a branched alkyl radical of the formula C 5 Hn-CH (C 3 H 7) -CH 2 -, where at least 70 mol% of the pentyl radicals C 5 H 11 - is an n-CsHu radical.
  • the substituent in 2-position, the propyl radical C3H7- may be in an n-C3H 7 group or an i-C3H 7 act radical. It is preferably an n-C3H 7 radical.
  • the pentyl radicals which are not n-pentyl radicals are preferably branched 1-alkyl radicals, preferably a 2-methyl-1-butyl radical C2H 5 CH (CH 3) CH 2 - and / or a 3-methyl-1 - butyl CH 3 CH (CH 3) CH 2 CH 2.
  • 70 to 99 mol% of the C5H11- radicals are n-C5Hn radicals, and from 1 to 30 mol% of the C5H11 radicals are C 2 H 5 CH (CH 3 ) CH 2 radicals and / or CH 3 CH (CH 3 ) CH 2 CH 2 radicals.
  • R 8 is a 2-propylheptyl radical HsCCHzCHzCHzCHzCH n-CsH ⁇ Ch -. In a further preferred embodiment, R 8 is a 2-ethylhexyl radical.
  • R 8 is a linear, saturated hydrocarbon radical having 12 to 14 carbon atoms, in particular a mixture comprising n-dodecyl and n-tetradecyl radicals.
  • R 2 , R 3 , R 4 , R 5 and R 6 have the meanings given above and the preferred ranges given.
  • the subscript x stands for a number from 0 to 5, preferably 0, the index y for a number from 1 to 15, preferably 1 to 9, for example 2 to 8 and the index z for a number from 1 to 30, preferably 2 to 20, particularly preferably 5 to 18, for example 8 to 16, wherein the sum of x + y + z is 5 to 35, preferably 8 to 29, for example 10 to 25.
  • indices x, y and z are furthermore selected with the proviso that z> (x + y), preferably z> (x + y) and particularly preferably z> 2 (x + y).
  • the values x, y and z are of course average values. Please refer to the illustration for surfactant (I). It is further clear to the person skilled in the art that the orientation of the propoxy and / or butoxy groups depends on the reaction conditions -OCR 2 R 3 CR 4 R 5 - or -OCH 2 CHR 6 - or -OCR 5 R 4 CR 3 R 2 - respectively. -OCHR 6 CH 2 - can be. The representation in formula (II) is not intended to indicate the orientation of the alkoxy units.
  • the radicals -OCR 2 R 3 CR 4 R 5 -, -OCH 2 CHR 6 - and -OCH 2 CH 2 - are arranged blockwise in the order given in formula (I).
  • small amounts of alkylene oxides can remain in the course of an alkoxylation. After addition of the next alkylene oxide, these can then be copolymerized into the second block so that small amounts of an alkylene oxide are in the "wrong" block.
  • at least 90% of the above radicals are arranged in the order given in formula (I), ie at least 90% of the radicals are also found in the "right" block.
  • the preparation of the surfactants (II) is carried out by alkoxylation of branched aliphatic alcohols R 8 OH with -soof existing alkylene oxides having 4 to 10 carbon atoms, preferably butylene oxide, propylene oxide and ethylene oxide, wherein the alkylene oxides are used in the order mentioned. Details of the preparation have already been described in detail in connection with the preparation of the alk (en) ylpolyalkoxylates of the general formula (Ia). This presentation is expressly referred to.
  • the alcohol R 8 OH is an alcohol R 1 OH.
  • This is first alkoxylated in the manner described and then sulfonated as described above, but only partially, ie he remains not yet sulfonated terminal OH groups.
  • nonionic surfactants (II) are alkylphenol polyakoxylates of the general formula (II I)
  • R 9 is a linear or branched alkyl radical having 8 to 12 carbon atoms.
  • the group - ⁇ 4 - represents a phenylene group, preferably a 1, 4-phenylene group.
  • R 2 , R 3 , R 4 , R 5 and R 6 have the abovementioned meaning and the preferred ranges given.
  • the subscript u stands for a number from 0 to 5, preferably 0, the index v for a number from 0 to 15, preferably 0 and the index w for a number from 5 to 30, preferably 6 to 20, particularly preferably 8 to 18 where the sum of u + v + w is 5 to 35, preferably 6 to 29, for example 8 to 20.
  • the subscripts u, v and w are further selected with the proviso that u a (v + w), preferably u> (v + w), and particularly preferably u ä 2 (v + w).
  • u, v and w are of course average values. Please refer to the illustration for surfactant (I).
  • radicals -OCR 2 R 3 CR 4 R 5 -, -OCH 2 CHR 6 - and -OCH 2 CH 2 - are arranged blockwise in the order given in formula (III).
  • Other cosurfactants are arranged blockwise in the order given in formula (III).
  • nonionic surfactants according to the general formula (I) and optionally the surfactants (II) and / or (III), it is optionally possible to use further surfactants.
  • additional cosurfactants include anionic surfactants such as paraffin sulfonates, olefin sulfonates (alpha-olefin sulfonates or internal olefinsulfonates), nonionic surfactants such as alkyl ethoxylates other than the surfactants (II) or polyalkoxylates composed of propylene oxide and ethylene oxide or surfactants which are permanently cationic (with alkyl or alkoxy) Hydroxyalkyl-quaternized alkylamines such as ⁇ , ⁇ , ⁇ -trimethyl-dodecylammonium chloride) or cationic under the conditions of the reservoir (eg alkylamine alkoxylates which are cationic at pH 3).
  • anionic surfactants such as paraffin sulf
  • the surfactants (I), optionally further surfactants, especially the surfactants (II) and (III) and optionally further components can be used as such, for example, the surfactants and / or other components mentioned directly in liquid or supercritical C0 2 are solved.
  • aqueous formulation (F) a suitable aqueous formulation
  • This aqueous formulation (F) can be metered into liquid or supercritical CO2 and injected or the aqueous formulation can be injected as such or after further dilution into the formation.
  • the stated formulation (F) may in particular be an aqueous concentrate which can be produced on site or else in a chemical production plant remote therefrom.
  • the total concentration of all surfactants in such an aqueous concentrate is chosen by the skilled person depending on the desired properties. It may be 20 to 90 wt .-% with respect to all components of the concentrate.
  • the concentrate may be liquid or liquid prior to injection supercritical CO2 and / or other aqueous solvents are diluted to the desired use concentration as will be described below.
  • formulations (F) may optionally also comprise water-miscible or at least water-dispersible organic solvents.
  • Such additives serve in particular to stabilize the Tensidlosung during storage or transport to the oil field.
  • the amount of such additional solvents should as a rule not exceed 50% by weight, preferably 20% by weight.
  • water-miscible solvents include in particular alcohols such as methanol, ethanol and propanol, butanol, sec-butanol, methoxypropanol, pentanol, ethylene glycol, diethylene glycol, propylene glycol, methylpropylene glycol, dipropylene glycol, methyldipropylene glycol, butyl ethylene glycol, butyldiethylene glycol or butyltriethylene glycol.
  • alcohols such as methanol, ethanol and propanol, butanol, sec-butanol, methoxypropanol, pentanol, ethylene glycol, diethylene glycol, propylene glycol, methylpropylene glycol, dipropylene glycol, methyldipropylene glycol, butyl ethylene glycol, butyldiethylene glycol or butyltriethylene glycol.
  • only water is used for formulation.
  • the aqueous formulations (F), in particular the aqueous concentrates may also comprise further components, for example scale inhibitors, biocides, radical scavengers, stabilizers, tracers or pour-point depressants.
  • Particularly suitable pour point depressants are the abovementioned alcohols.
  • At least one injection well and at least one production well removed therefrom are drilled into a crude oil deposit.
  • a deposit is provided with multiple injection wells and multiple production wells.
  • the crude oil deposits to which the method according to the invention is applied may, in principle, be any deposits, for example formations comprising carbonate rocks or formations comprising sandstone.
  • the oil reservoirs include oil and saline reservoir water, with petroleum, reservoir water and possibly natural gas stored in pores, crevices or interstices of the formation.
  • the storage temperature is usually at least 10 ° C, in particular 15 ° C to 140 ° C, preferably 31 ° C to 120 ° C, more preferably 40 ° C to 120 ° C, most preferably 50 ° C to 100 ° C and for example 60 ° C to 90 ° C. It will be clear to those skilled in the art that the reservoir temperature may have some distribution about an average, with large deviations generally less caused by natural circumstances, but especially by human intervention, eg by prolonged flooding or prolonged steam flooding.
  • the total salinity of the reservoir water can be up to 350,000 ppm, for example 20,000 ppm to 350,000 ppm.
  • the method may preferably be applied to deposits having a total salinity of 30,000 ppm to 250,000 ppm, preferably 35,000 ppm to 200,000 ppm, more preferably 35,000 ppm to 180,000 ppm, for example 120,000 ppm to 170,000 ppm.
  • the salts in the deposit may be in particular alkali metal salts and alkaline earth metal salts. Examples of typical cations include Na + , K + , Mg 2+ or Ca 2+ and examples of typical anions include chloride, bromide, bicarbonate, sulfate or borate.
  • alkali metal ions in particular at least Na +
  • alkaline earth metal ions may also be present, the weight ratio of alkali metal ions / alkaline earth metal ions generally being> 5, preferably> 8.
  • Suitable anions are usually at least one or more of halide ions, in particular at least Cl "available.
  • the amount of Ch is at least about 50 wt.%, Preferably at least 80 wt.% Relative to the total of all anions.
  • Liquid or supercritical CO2 and at least one anionic surfactant (I) or a surfactant mixture comprising at least one anionic surfactant (I) are injected into the petroleum formation through the at least one injection well and petroleum is taken from the deposit through at least one production well, the at least one Surfactant (I) or at least one surfactant (I) comprising dissolved in liquid or supercritical CO2 and is injected and / or dissolved in an aqueous medium and injected.
  • phase-pure oil does not only mean phase-pure oil, but also includes the usual crude oil-water emulsions, and also injects injected CO2 into the production well, depending on the stage of the process.
  • CO2 When pumping CO2 into a reservoir, pressure and temperature determine the physical state of CO2.
  • the phase diagram of CO2 is known to the person skilled in the art.
  • CO2 can be liquefied in the temperature range of -56.6 ° C to 30.98 ° C using a pressure of at least 5.2 bar. At less than 5.2 bar, depending on the temperature, only solid or gaseous CO2 exists.
  • the critical point of CO2 is 30.98 ° C and 73.75 bar.
  • CO2 is supercritical, ie the phase boundary liquid-gaseous disappears. and the CO2 is almost as dense as a liquid but still has a very low viscosity similar to that of a gas.
  • gaseous CO2 can be compressed on-site, for example from CO2 produced, or CO2 can already be delivered in a compressed state.
  • the minimum pressure required for injection results from the reservoir temperature and is selected such that the injected CO2 is in a liquid or supercritical state at the respective reservoir temperature. It has proven useful to adjust the CO 2 flooding the density of CO2 under reservoir conditions to 0.65 g / ml to 0.95 g / ml, preferably 0.70 g / ml to 0.90 g / ml.
  • the density of CO2 as a function of pressure and temperature can be found in relevant tables.
  • Injecting the at least one nonionic surfactant (I) or the surfactant mixture comprising at least one nonionic surfactant (I) can be carried out by various techniques.
  • the surfactants or surfactant mixtures used as well as optionally further components are dissolved in liquid or supercritical CO 2 and the CO 2 solution is injected into the subterranean crude oil deposit.
  • Such processes are also referred to as surfactant-in-gas (SinG) processes.
  • the surfactant (I) or the surfactant (I) comprising surfactant mixture can be mixed as such with the CO2, dissolved and injected, or it can be a suitable formulation of the surfactants used.
  • the formulations (F) described above in particular as concentrates having a surfactant content of from 20 to 90% by weight with respect to the sum of all components, can be used and metered into a stream of liquid or supercritical CO 2 and mixed with the stream.
  • the amount of the surfactants or of the formulation (F) or of the concentrate is such that the amount of all surfactants together 0.02 to 2 wt.%, Preferably 0.02 to 0.5 wt .-% with respect to the sum of all components the solution of surfactants in liquid or supercritical CO2.
  • the CO2 After entering the formation, the CO2 flows in the direction of the production well or the production wells, mobilizing oil according to the mechanisms described above. If the liquid or supercritical CO2 with the dissolved surfactants hits deposit water after being injected into the formation, CO2 in-water emulsions, which are stabilized by the one or more surfactants (I) or surfactants (I) comprising mixtures and optionally other surfactants.
  • CC n-water emulsions are occasionally referred to in the literature as CC n-water foams, and the term C02-in-water dispersions can also in the literature can be found. In the following, however, the term CC n-water emulsion is to be used uniformly.
  • the C02-in-water emulsions have a significantly higher viscosity than the CO2 itself, and thus the difference between the viscosity of the CC n-water emulsion and the petroleum is lower, usually much less than the difference between the viscosity of liquid or supercritical CO2 and petroleum.
  • C02-in-water emulsions also flow towards production wells or production wells.
  • Liquid or supercritical CO2 which is incorporated in the emulsion, can also mobilize the oil in the same way as already mentioned when it encounters oil.
  • the surfactants (I) and optionally further surfactants also lower the interfacial tension between oil and CO2 and thus also facilitate the miscibility of these two phases.
  • the injected liquid or supercritical CO2 naturally flows first into the higher permeable zones. As soon as more viscous C02-in-water emulsions form on the water, flow through the permeable zones becomes much more difficult, so that pumped-up CO2 can find its way through low-permeability zones and mobilize previously unreachable oil. This increases the oil production rate. If the capillary pressure in the very low-permeable zones becomes too high, the CO2-water aggregate may collapse. However, this is not a disadvantage since the very low-permeability zones would have been barely accessible to the CO2 if flooded alone with CO2 or in the water-alternating gas process.
  • water or saline water such as, for example, seawater or produced deposit water, is first injected into the deposit through the injection well.
  • a solution of the surfactants or surfactant mixtures used and optionally further components is injected in liquid or supercritical CO2.
  • the amount of surfactants or formulation (F) or of the concentrate is such that the amount of all surfactants together 0.02 to 2 wt .-%, preferably 0.02 to 0.5% by weight with respect to the sum of all components of the solution of surfactants in liquid or supercritical CO2.
  • an aqueous formulation of the surfactants (I) or surfactants (I) comprising surfactant mixtures is injected into the formation and separately liquid or supercritical CO2.
  • the above-described concentrates of formulation (F) may be mixed with water or saline water and injected into the formation.
  • the amount of surfactants is calculated so that the concentration of all surfactants together is 0.02 to 2 wt .-%, preferably 0.02 to 0.5 wt .-% with respect to the sum of all components of the injected aqueous solution.
  • liquid or supercritical CO2 is injected into the deposit.
  • the sequence of these two process steps can be repeated once or several times.
  • CC n-water emulsions form.
  • Such processes are also referred to as Surfactant in Water Alternating Gas (SAG) processes.
  • the water phase may be thickened with a water-soluble, thickening polymer such as polyacrylamide, partially hydrolyzed polyacrylamide, acrylamide-containing copolymers, acrylamide and sulfonate group-containing copolymers or biopolymers such as xanthan ,
  • a water-soluble, thickening polymer such as polyacrylamide, partially hydrolyzed polyacrylamide, acrylamide-containing copolymers, acrylamide and sulfonate group-containing copolymers or biopolymers such as xanthan ,
  • the described CC n-water emulsions can be formed before injection from liquid or supercritical CO2, tensides (I) and optionally further surfactants, and the CC n-water emulsions injected.
  • the main effect of the surfactants (I) used according to the invention lies in the stabilization of the CO 2 -water interface and thus in long-term stable CC n-water emulsions.
  • the surfactants (I) stabilize the CC n-water emulsions better than surfactants according to the prior art.
  • the CC n-water emulsions remain stable much longer than is the case with known surfactants. Selection of surfactants
  • the person skilled in the art selects at least one surfactant (I) for carrying out the process according to the invention.
  • the surfactants (I) may be used in admixture with other surfactants (I), at least one surfactant (II) and / or at least one surfactant (III).
  • other surfactants and other components can be used.
  • surfactant (I) to be used and possibly other surfactants depends on the conditions of the reservoir, in particular on the temperature of the reservoir and the salinity of the reservoir water. The skilled person will make an appropriate choice depending on the reservoir conditions.
  • the cloud point of the surfactant or of the surfactant mixture used should be at least 1 ° C., preferably at least 3 ° C., above the reservoir temperature under reservoir conditions. If the deposit has a distribution of store temperatures, this means the highest store temperature in the area through which the liquid or supercritical CO2 or the C02-in-water emulsion flows.
  • the cloud point of a nonionic surfactant is the temperature at which the solution becomes cloudy. The reason for this is that the surfactant increases with increasing temperature. hydrated and thus insoluble. This separates the solution into a cloudy surfactant and a clear, low-surfactant phase. This phase behavior is found not only with nonionic surfactants, but also with surfactants which have a nonionic, hydrophilic moiety, for example a polyalkoxy group and an anionic group. Cloud points are also measurable with the anionic surfactants (III) of this invention.
  • the cloud point is measured by slowly heating a clear aqueous solution of the surfactant in water.
  • the cloud point of a surfactant depends on the concentration of the surfactant and the salt content of the aqueous solution.
  • a specific measurement instruction for the cloud point is contained in the example part of this application.
  • under reservoir conditions means that the cloud point of the surfactant (I) or surfactant (I) surfactant mixture in reservoir water at the concentration intended for injection, ie the concentration of surfactant in the aqueous medium to be injected or the concentration in the liquid or supercritical CO2 to be injected.
  • R 1 - OCR 2 R 3 CR 4 R 5
  • i OH 2 CHR 6
  • m OH 2 CH 2
  • n-0-R 7 V a -S03- M a + can be well adapted to the conditions in the deposit by the nature of the alkoxylation scheme.
  • Such surfactants are particularly suitable for deposits with a temperature of 40 ° C to 120 ° C, especially 50 ° C to 100 ° C and for example 60 ° C to 90 ° C and a salinity of the reservoir water of 35000 ppm to 180000 ppm, in particular 120,000 ppm to 170000 ppm
  • a mixture of at least one anionic surfactant (I) and at least one nonionic surfactant (II) which is different therefrom is used.
  • anionic surfactants of the formula (I) with the nonionic surfactants (II) are particularly economical.
  • the anionic surfactants (I) have excellent en technical characteristics. They are still very useful especially at higher salinities and / or higher reservoir temperatures and have good long-term stability under reservoir conditions.
  • the preparation of alk (en) ylpolyalkoxysulfonaten (surfactants (I)) is expensive. To prepare them, it is necessary first of all to prepare alk (en) ylpolyalkoxylates (surfactants (II)) which then have to be converted into alk (en) ylpolyalkoxysulphonates in a one- or two-stage process. Details of this have already been described above.
  • the surfactants (II) are therefore necessarily more expensive than the surfactants (I). A mixture of the surfactants (I) with the surfactants (II) thus reduces the cost.
  • Such a mixture can be prepared by only partially surfactants (II) sulfonated to surfactants (I).
  • the weight ratio of surfactants of formula (I) to (II) in the mixture is chosen by the skilled person depending on the requirements.
  • the weight ratio (I) / (II) is 19: 1 to 1:19, preferably 4: 1 to 1: 9, more preferably 2: 1 to 1: 9 and for example 1: 1 to 1: 4.
  • Preferred total amounts have already been mentioned.
  • the mixture of the surfactants (I) and (II) is still very soluble in water even at high salinity and also the solubility in CO2 is good.
  • a mixture of at least one anionic surfactant (I) and at least one surfactant (III) is used.
  • the weight ratio of surfactants of the formula (I) to (III) in the mixture is chosen by the person skilled in the art according to the requirements.
  • the weight ratio (I) / (II) is 19: 1 to 1:19, preferably 4: 1 to 1: 9, more preferably 2: 1 to 1: 9 and for example 1: 1 to 1: 4.
  • Preferred total amounts for the amount of all surfactants have already been mentioned.
  • the mixture of the surfactants (I) and (III) is still very soluble in water even at high salinity and also the solubility in CO2 is good.
  • the adsorption of the mixture is low on both carbonate rock and sandstone.
  • the alcohol (1, 0 eq) to be alkoxylated is optionally mixed with an aqueous KOH solution containing 50% by weight of KOH.
  • the amount of KOH is 0.2% by weight of the product to be produced.
  • the mixture is dehydrated at 100-120 ° C and 20 mbar for 2 h.
  • N2 a pre-pressure of about 1.3 bar N2 is set and the temperature is increased to 130.degree.
  • the alkylene oxides are then metered in succession in the respectively desired amount, so that the temperature remains between 135 to 145 ° C.
  • the mixture is stirred for 1 h at 135 to 145 ° C, rinsed with N2, cooled to 80 ° C and the reactor emptied.
  • the basic crude product is neutralized with acetic acid.
  • the neutralization can be carried out with commercially available Mg silicates, which are then filtered off.
  • the bright product is characterized by means of a 1 H-NMR spectrum in CDCl 3, a gel permeation chromatography and an OH number determination, and the yield is determined.
  • an alk (en) ylpolyalkoxylate was first synthesized according to the above general procedure.
  • the alk (en) ylpolyalkoxylate obtained in the 1st stage is sulfonated according to the following procedure:
  • the alkyl alkoxylate (1, 0 eq) to be sulfonated is mixed with KOH flakes (1.1 eq) in a 500 ml flat-section glass reactor with three-stage bar stirrer and flow breakers and stirred at 60 ° C. under N 2.
  • propane sulphone (1, 0 eq) was added at 60 ° C and stirred for a further 3 h at 60 ° C.
  • Unreacted propane sultone is destroyed by boiling with water.
  • the basic crude product is neutralized at 60 ° C with the aid of hydrochloric acid. Ethanol may be added to the reaction mixture to lower the viscosity of the mixture.
  • the bright product is characterized by means of a 1 H-NMR spectrum in CDCl 3 and MeOD, a 1 H-TAI-NMR, an Epton titration and an OH number determination and the yield is determined.
  • the surfactants used (III), 4-octylphenol-10 EO, 4-octylphenol -16 EO are commercially available.
  • the measurements were carried out with aqueous surfactant solutions both in fresh water and in salt water of various salt concentrations.
  • the salt water used was aqueous solutions containing NaCl and CaC in a ratio of 9 to 1 (by weight).
  • the salinity ranges from 0 to 250,000 ppm TDS (total dissolved salt).
  • the object of the invention was to provide an improved process for CO 2 flooding for oil refineries, in which the most stable CC n-water emulsions are formed.
  • Table 1 shows the influence of the structure of the surfactants (I) used according to the invention and the salinity on the measured cloud points.
  • Table 1 shows that the alkyl polyalkoxy sulfonate 2-PH-I 4-EO-C3H6-SO3K has a very high cloud point of greater than 95 ° C at higher concentrations. It is thus also suitable for C02 floods in formations with a particularly high reservoir temperature. It is noteworthy that this also occurs at a salinity of 160000 ppm. Even at a salinity of 200,000 ppm, the cloud point is still 77 ° C.
  • the solubility of the surfactants in supercritical CO2 was then investigated.
  • the apparatus used was a 280 ml high-pressure reactor with two viewing windows in the lower region of the reactor.
  • the construction of the apparatus is shown schematically in Figure 2.
  • the reactor comprises a CO 2 inlet (1), a manometer (2), a CO 2 pressure relief valve (325 bar) and two opposing viewing windows (4) mounted in the lower reactor area.
  • the reactor can be stirred via a stirrer.
  • the above reactor was used.
  • Surfactant was prepared at the concentrations shown in the tables below and made up to 40 ml with saline water.
  • the high pressure apparatus was filled with the aqueous solution exactly to the middle of the viewing window.
  • the reactor was then charged to 280 ml with supercritical CO2.
  • the water phase and the C02 phase are clear and the viewing window shows clearly the phase boundary between CO2 and water. This is shown schematically in Figure 3a. Then the mixture is stirred.
  • the proportion of the visible part of the CO2 in the window, which is bound in the emulsion can be determined in an analogous manner.
  • Deterioration of the emulsion in the petroleum formation is highly undesirable because the emulsion has a significantly higher viscosity than the supercritical CO2 (see above) and this higher viscosity is needed to avoid "fingering.” It is therefore advantageous if the CC n Water emulsion in a given amount of CO2 binds the largest possible amount of water in the emulsion to keep the emulsion stable for as long as possible. The more water is bound, the more water can lose the emulsion without the emulsion decomposes, and accordingly, it takes longer for the emulsion to disintegrate.
  • the surfactant (I) 2-PH-14 EO-C 3 H6-S0 3 K has more excellent cloud points of> 95 ° C (tests 20 and 21), even at high salinity of 160,000 ppm. Furthermore, it binds at 50 ° C and a salinity of 160,000 ppm 60% water in the CC n-water emulsion. At 65 ° C even 85% water are bound. It is therefore ideal for CO2 floods.

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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Procédé d'extraction de pétrole au moyen de l'injection de CO2, qui consiste à injecter du CO2 liquide ou supercritique et au moins un al(k/cén)ylpolyéthersulfonate par au moins un trou d'injection dans un gisement pétrolifère, et à extraire du pétrole dudit gisement par au moins un trou de production, l'al(k/cén)ylpolyéthersulfonate étant de préférence dissous dans la phase CO2. La présente invention concerne en outre un procédé d'extraction de pétrole au moyen de l'injection de CO2, selon lequel on utilise des mélanges des al(k/cén)ylpolyéthersulfonates avec des al(k/cén)ylpolyalcoxylates ou des alkylphénolpolyalcoxylates.
PCT/EP2015/052711 2014-03-12 2015-02-10 Procédé d'injection de co2 associé à des al(k/cén)ylpolyéthersulfonates WO2015135708A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14159146 2014-03-12
EP14159146.1 2014-03-12

Publications (1)

Publication Number Publication Date
WO2015135708A1 true WO2015135708A1 (fr) 2015-09-17

Family

ID=50239541

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2015/052711 WO2015135708A1 (fr) 2014-03-12 2015-02-10 Procédé d'injection de co2 associé à des al(k/cén)ylpolyéthersulfonates

Country Status (2)

Country Link
AR (1) AR100669A1 (fr)
WO (1) WO2015135708A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10266751B2 (en) 2014-11-18 2019-04-23 Basf Se Method of mineral oil production
CN115711110A (zh) * 2022-10-27 2023-02-24 新疆敦华绿碳技术股份有限公司 一种在致密油藏中提高co2混相驱采收率的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4088190A (en) * 1977-02-10 1978-05-09 Union Oil Company Of California Carbon dioxide foam flooding
US4502538A (en) * 1984-01-09 1985-03-05 Shell Oil Company Polyalkoxy sulfonate, CO2 and brine drive process for oil recovery
US20120220502A1 (en) * 2011-02-24 2012-08-30 Basf Se Compositions comprising alkylalkoxysulfonates for the production of high temperature stable foams
US20130196886A1 (en) * 2010-02-15 2013-08-01 Julian Richard BARNES Surfactant systems for enhanced oil recovery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4088190A (en) * 1977-02-10 1978-05-09 Union Oil Company Of California Carbon dioxide foam flooding
US4502538A (en) * 1984-01-09 1985-03-05 Shell Oil Company Polyalkoxy sulfonate, CO2 and brine drive process for oil recovery
US20130196886A1 (en) * 2010-02-15 2013-08-01 Julian Richard BARNES Surfactant systems for enhanced oil recovery
US20120220502A1 (en) * 2011-02-24 2012-08-30 Basf Se Compositions comprising alkylalkoxysulfonates for the production of high temperature stable foams

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"Isothermal Properties for Carbon Dioxide", 31 December 2011 (2011-12-31), XP055182867, Retrieved from the Internet <URL:http://webbook.nist.gov/chemistry/fluid/> [retrieved on 20150414] *
J K BORCHARDT ET AL: "Surfactants for C02 Foam Flooding", SPE, 25 September 1985 (1985-09-25), XP055114897 *
R M ENICK: "SPE 154122 Mobility and Conformance Control for CO 2 EOR via Thickeners, Foams, and Gels -A Literature Review of 40 Years of Research and Pilot Tests", SPE, 18 April 2012 (2012-04-18), pages 14 - 18, XP055114669 *
S L WELLINGTON ET AL: "SPE 14393 CT Studies of Surfactant-induced C02 Mobility Control", SPE, 25 September 1985 (1985-09-25), XP055114896 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10266751B2 (en) 2014-11-18 2019-04-23 Basf Se Method of mineral oil production
US10961432B2 (en) 2014-11-18 2021-03-30 Basf Se Method of mineral oil production
CN115711110A (zh) * 2022-10-27 2023-02-24 新疆敦华绿碳技术股份有限公司 一种在致密油藏中提高co2混相驱采收率的方法

Also Published As

Publication number Publication date
AR100669A1 (es) 2016-10-26

Similar Documents

Publication Publication Date Title
EP2488599B1 (fr) Procédé d&#39;extraction de pétrole tertiaire au moyen de mélanges de tensioactifs
EP2738236B1 (fr) Nouveaux groupes de polyalkoxy anionique contenant des tensioactifs à base d&#39;alcool de guerbet et d&#39;utilisation dans des applications de récupération améliorée de pétrole (eor)
EP2545137B1 (fr) Procédé d&#39;extraction du pétrole au moyen de tensioactifs à base de tensioactifs alkylpropoxylés renfermant c16c18
US8853136B2 (en) Process for tertiary mineral oil production using surfactant mixtures
EP2545138A1 (fr) Utilisation de mélanges de tensioactif(s) et de polycarboxylate(s) pour l&#39;injection de microémulsions
WO2011110503A1 (fr) Procédé d&#39;extraction du pétrole au moyen de tensioactifs à base d&#39;alcoxylates d&#39;alkyle contenant de l&#39;oxyde de butylène
EP2488598B1 (fr) Procédé d&#39;extraction de pétrole au moyen de mélanges de tensioactifs
EP2561036A1 (fr) Procédé de production de pétrole utilisant des tensioactifs à base d&#39;un mélange d&#39;alcoxylates d&#39;alkyle contenant un alcool de guerbet en c32, un alcool de guerbet en c34, un alcool de guerbet en c36
EP2771428B1 (fr) Procédé d&#39;extraction de pétrole à l&#39;aide de tensioactifs à base d&#39;un mélange d&#39;alcoxylates d&#39;hydrocarbures contenant un guerbet en c24, un guerbet en c26, un guerbet en c28
EP3221417A1 (fr) Procédé pour le transport de pétrole
WO2009050179A1 (fr) Nouveaux tensioactifs à structure polyéthersulfonate, procédé de production et utilisation desdits tensioactifs pour la récupération tertiaire du pétrole
WO2015135860A1 (fr) Procédé d&#39;injection de co2 associé à des al(k/cén)ylpolyglucosides
EP2488600B1 (fr) Procédé d&#39;extraction de pétrole tertiaire au moyen de mélanges de tensioactifs
EP2771427B1 (fr) Procédé d&#39;extraction de pétrole à l&#39;aide de tensioactifs à base d&#39;un mélange d&#39;alcoxylates d&#39;hydrocarbures contenant un guerbet en c32, un guerbet en c34, un guerbet en c36
EP2268764B1 (fr) Utilisation de mélanges tensioactifs pour la récupération tertiaire
EP2544810A2 (fr) Procédé d&#39;extraction du pétrole au moyen de tensioactifs cationiques qui renferment un bloc hydrophobe possédant une longueur de chaîne de 6 à 10 atomes de carbone
WO2015135851A1 (fr) Procédé d&#39;injection de co2 associé à des alkylpolyalcoxylates c10 ramifiés
WO2015135855A1 (fr) Procédé d&#39;injection de co2 associé à des al(k/cén)ylpolyalcoxylates c12-14
US20120241151A1 (en) Process for mineral oil production using surfactants from the class of the alkyl polyglucosides
WO2015135708A1 (fr) Procédé d&#39;injection de co2 associé à des al(k/cén)ylpolyéthersulfonates
US9475979B2 (en) Process for producing mineral oil using surfactants based on a mixture of C20 Guerbet-, C22 Guerbet-, C24 Guerbet-containing hydrocarbyl alkoxylates
US9475977B2 (en) Process for producing mineral oil using surfactants based on a mixture of C28 Guerbet, C30 Guerbet, C32 Guerbet-containing hydrocarbyl alkoxylates
WO2013057044A1 (fr) Utilisation de dérivés de tris(2-hydroxyphényl)méthane pour la récupération tertiaire de pétrole
WO2013060622A1 (fr) Procédé d&#39;extraction de pétrole à l&#39;aide de tensioactifs à base d&#39;un mélange d&#39;alcoxylates d&#39;hydrocarbures contenant du guerbet en c28, guerbet en c30, guerbet en c32
WO2014063933A1 (fr) Procédé d&#39;extraction du pétrole au moyen de tensioactifs à base d&#39;alcoxylates d&#39;alkyle anioniques provenant d&#39;éthers glycidyliques

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15703293

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15703293

Country of ref document: EP

Kind code of ref document: A1