EP2545136A1 - Procédé d'extraction du pétrole au moyen de tensioactifs à base d'alcoxylates d'alkyle contenant de l'oxyde de butylène - Google Patents

Procédé d'extraction du pétrole au moyen de tensioactifs à base d'alcoxylates d'alkyle contenant de l'oxyde de butylène

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Publication number
EP2545136A1
EP2545136A1 EP11706292A EP11706292A EP2545136A1 EP 2545136 A1 EP2545136 A1 EP 2545136A1 EP 11706292 A EP11706292 A EP 11706292A EP 11706292 A EP11706292 A EP 11706292A EP 2545136 A1 EP2545136 A1 EP 2545136A1
Authority
EP
European Patent Office
Prior art keywords
groups
butylene oxide
surfactant
oil
carbon atoms
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Withdrawn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
EP11706292A
Other languages
German (de)
English (en)
Inventor
Christian Bittner
Günter OETTER
Jack Tinsley
Christian Spindler
Gabriela ALVAREZ-JÜRGENSON
Sophie Maitro-Vogel
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP11706292A priority Critical patent/EP2545136A1/fr
Publication of EP2545136A1 publication Critical patent/EP2545136A1/fr
Withdrawn legal-status Critical Current

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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
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C11D1/345—Phosphates or phosphites
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S507/00—Earth boring, well treating, and oil field chemistry
    • Y10S507/935—Enhanced oil recovery
    • Y10S507/936—Flooding the formation

Definitions

  • the invention relates to processes for crude oil production, by means of Winsor type III microemulsion flooding, in which an aqueous surfactant formulation containing at least one ionic surfactant of the general formula R 1 -O- (D) n - (B) m - (A), - XY-M + , injected through injection wells in a Erdöllagerstatte and the production site boring crude oil takes.
  • the invention further relates to ionic surfactants according to the general formula and to processes for the preparation of these.
  • a deposit In natural oil deposits, petroleum is present in the cavities of porous reservoirs, which are closed to the earth's surface of impermeable cover layers.
  • the cavities may be very fine cavities, capillaries, pores or the like. Fine pore necks can have, for example, a diameter of only about 1 ⁇ m.
  • a deposit In addition to crude oil, including natural gas, a deposit contains more or less saline water.
  • Oil production generally distinguishes between primary, secondary and tertiary production.
  • primary production after drilling the deposit, petroleum automatically streams through the borehole due to the inherent pressure of the deposit.
  • the secondary funding is used.
  • secondary production in addition to the wells used to extract oil, the so-called production wells, additional wells will be drilled into the oil-bearing formation.
  • injection wells water is injected into the reservoir to maintain or increase the pressure.
  • the oil is slowly forced through the cavities into the formation, starting from the injection well, toward the production well. But this works only as long as the cavities are completely filled with oil and the viscous oil is pushed through the water in front of him.
  • the low-viscosity water breaks through cavities, it flows from this point on the path of least resistance, ie through the channel formed, and no longer pushes the oil in front of him.
  • primary and secondary production as a rule only about 30-35% of the quantity of crude oil in the deposit can be extracted.
  • 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
  • gases such as CO 2 or nitrogen can also be used.
  • Tertiary oil production further includes processes in which suitable chemicals are used as auxiliaries for oil extraction. With these, the situation can be influenced towards the end of the flood and thus also promote oil that was previously held in the rock formation.
  • Viscous and capillary forces act on the oil trapped in the pores of the reservoir rock towards the end of the secondary production, and the ratio of these two forces to one another determines the microscopic oil removal.
  • capillary number the influence of these forces is described. It is the ratio of the viscosity forces (velocity x viscosity of the pressing phase) to the capillary forces (interfacial tension between oil and water x wetting of the rock):
  • ⁇ is the viscosity of the oil mobilizing fluid
  • v the Darcy velocity (flow per unit area)
  • ⁇ the interfacial tension between petroleum mobilizing liquid and petroleum
  • ⁇ the contact angle between petroleum and rock
  • capillary number " is 6, and that it is necessary for the capillary to about 10" near the end of secondary oil recovery in the range of about 10 to increase from 3 to 10 "2 to mobilize additional mineral oil.
  • Winsor type III microemulsion flooding the injected surfactants should interact with the water and water reservoirs present in the reservoir Oil phase form a microemulsion Windsor type III.
  • a Microemulsion Windsor Type III is not an emulsion with very small droplets, but a thermodynamically stable, liquid mixture of water, oil and surfactants.
  • the microemulsion Winsor Type III is in equilibrium with excess water and excess oil. Under these conditions, the microemulsion formation, the surfactants demonstrate the oil-water interface and lower the interfacial tension ⁇ particularly preferably to values of ⁇ 10 "2 mN / m (ultralow interfacial surfactant-sion). In order to achieve the best results, should the Proportion of the microemulsion in the system water microemulsion oil with a defined amount of surfactant naturally be as large as possible, since thereby the lower interfacial tensions can be achieved.
  • the oil droplets in shape change (interfacial tension between oil and water is lowered so far that no longer the state of the smallest boundary surface is desired and not the spherical shape is preferred) and squeeze through the flood water through the capillary.
  • Winsor Type III microemulsion will be formed if there is an excess amount of surfactant. It thus represents a reservoir for surfactants, which accomplish a very low interfacial tension between oil and water phase.
  • surfactants which accomplish a very low interfacial tension between oil and water phase.
  • the surfactant from the microemulsion can markedly lower the interfacial tension of this new interface and result in the mobilization of the oil (for example by deformation of the oil droplets) ,
  • the oil droplets can then combine to form a continuous oil bank. This has two advantages: On the one hand, as the continuous oil bank advances through new porous rock, the oil droplets located there can merge with the bank.
  • the union of the oil droplets to an oil bank significantly reduces the oil-water interface, thus releasing unneeded surfactant.
  • the released surfactant may thereafter mobilize residual oil remaining in the formation as described above.
  • Winsor Type III microemulsion flooding is an extremely efficient process and unlike an emulsion flooding process, it requires significantly less surfactant.
  • the surfactants are usually optionally injected together with cosolvents and / or basic salts (optionally in the presence of chelating agents). Subsequently, a solution of thickening polymer is injected for mobility control.
  • Another variant is the injection of a mixture of thickening polymer and surfactants, cosolvents and / or basic see salts (optionally with chelating agent) and subsequently a solution of thickening polymer for mobility control. These solutions should usually be clear to avoid blockage of the reservoir.
  • Suitable surfactants for tertiary oil production are the interfacial tension between water and oil (usually approx. 20 mN / m) to particularly low values of less than 10 "2 mN / m to allow adequate oil mobilization at normal storage temperatures of about 15 ° C to 130 ° C and in the presence of high salty water, especially in the presence of high levels of calcium and / or magnesium ions, the surfactants must therefore also be soluble in strongly saline deposit water.
  • AO alkylene oxide having 2 to 6 carbon atoms
  • the indication of the alkylene oxides is within the scope of the disclosure of US 3,890,239 only very general. But there are only examples that contain only EO.
  • AO alkyl alkoxylates of the type CrC 6 (AO) i-4o-EO> io-H in combination with an anionic surfactant.
  • AO can be 1, 2-butylene oxide or 2,3-butylene oxide.
  • alkylene oxide may be ethylene oxide, propylene oxide or butylene oxide. There is the proviso that ethylene oxide makes up the major part of the alkylene oxides. A more detailed description of butylene oxide is not found.
  • the use parameters such as, for example, type, concentration and the mixing ratio of the surfactants used with one another, are therefore adapted by the person skilled in the art to the conditions prevailing in a given oil formation (for example temperature and salinity).
  • the oil production is proportional to the capillary number. This is the higher the lower the interfacial tension between oil and water. Low interfacial tensions are the more difficult to achieve the higher the average number of carbon atoms in the crude oil.
  • surfactants are suitable which have a long alkyl radical. The longer the alkyl radical, the better the interfacial tensions can be reduced. However, the availability of such connections is very limited.
  • the object of the invention is therefore to provide a particularly efficient surfactant for use for surfactant flooding, as well as an improved process for tertiary mineral oil production.
  • a process for tertiary mineral oil production by means of Winsor Type III microemulsion flooding in which an aqueous surfactant formulation comprising at least one ionic surfactant is injected through at least one injection well into a crude oil deposit, the interfacial tension between oil and water to values ⁇ 0.1 mN / m, is preferably lowered to values ⁇ 0.05 mN / m, more preferably to values ⁇ 0.01 mN / m, and the deposit is withdrawn through at least one production well crude oil, wherein the surfactant formulation at least one surfactant of the general formula
  • A is ethyleneoxy
  • n is a number from 1 to 99
  • X is an alkyl or alkylene group having 0 to 10 carbon atoms
  • M + is a cation
  • Y is selected from the group of sulfate groups, sulfonate groups, carboxylate groups and phosphate groups, wherein the groups A, B and D can be randomly distributed, alternating or in the form of two, three, four or more blocks in any order, the sum I + m + n is in the range of 3 to 99 and the proportion of 1, 2-butylene oxide based on the total amount of butylene oxide is at least 80%.
  • a surfactant mixture for crude oil production which contains at least one ionic surfactant according to the general formula defined above.
  • Winsor Type III microemulsion flooding crude oil production process employs an aqueous surfactant formulation containing at least one surfactant of the general formula. It may also include other surfactants and / or other components.
  • the interfacial tension between oil and water is particularly preferred due to the use of the surfactant according to the invention Lowered ⁇ 0.01 mN / m.
  • the interfacial tension between oil and water will be in the range of 0.1 mN / m to 0.0001 mN / m, preferably values in the range of 0.05 mN / m to 0.0001 mN / m, more preferably Values lowered in the range from 0.01 mN / m to 0.0001 mN / m.
  • the at least one surfactant can be subsumed under the general formula R 1 -O- (D) n - (B) m - (A) i -XY " M +
  • several different surfactants of the general formula can also be used Formula be present.
  • the radical R 1 is a straight-chain or branched aliphatic and / or aromatic hydrocarbon radical having 8 to 30 carbon atoms, preferably 9 to 30 carbon atoms, particularly preferably 10 to 28 carbon atoms.
  • the radical R 1 is iso-Ci 7 H 35 - or a commercial fatty alcohol mixture consisting of linear Ci 6 H 33- and Ci 8 H 37 - or derived from the commercially available Ci 6 -Guerbetalkohol 2-hexyldecyl -1 -ol or derived from the commercially available C 2 4-Guerbet alcohol 2-decyl-tetradecanol or derived from the commercially available C 2 8-Guerbet alcohol 2-dodecyl-hexadecanol.
  • D is more than 80% 1, 2-butylene oxide and that the alkylene oxides starting from the alcohol have the sequence D - B - A.
  • the alkylene oxides are more than 90% arranged in blocks.
  • a straight-chain or branched aliphatic hydrocarbon radical in particular a straight-chain or branched aliphatic hydrocarbon radical having from 10 to 28 carbon atoms.
  • a branched aliphatic hydrocarbon radical generally has a degree of branching of from 0.1 to 5.5, preferably from 1 to 3.5.
  • degree of branching is hereby defined in a manner known in principle as the number of methyl groups in a molecule of the alcohol minus 1.
  • the mean degree of branching is the statistical average of the degrees of branching of all molecules in a sample.
  • A has the meaning of ethyleneoxy.
  • B is propyleneoxy and D is butyleneoxy.
  • I, m and n are integers. However, it will be apparent to those skilled in the art of polyalkoxylates that this definition is the definition of a single surfactant.
  • the numbers I, m and n are values for all molecules of the surfactants, since in the alkoxylation of alcohol with ethylene oxide or propylene oxide or butylene oxide, a certain distribution of chain lengths is obtained in each case. This distribution can be described in a manner known in principle by the so-called polydispersity D.
  • D M w / M n is the quotient of the weight average 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.
  • I is a number from 0 to 99, preferably 1 to 40, particularly preferably 1 to 20.
  • m is a number from 0 to 99, preferably 1 to 20, particularly preferably 5 to 9.
  • n is a number from 1 to 99, preferably from 2 to 30, particularly preferably from 2 to 10.
  • the sum I + m + n is a number which is in the range of 3 to 99, preferably in the range of 5 to 50, particularly preferably in the range of 8 to 39.
  • the proportion of 1, 2-butyleneoxy based on the total amount of butyleneoxy (D) is at least 80%, preferably at least 85%, preferably at least 90%, particularly preferably at least 95% 1, 2-butyleneoxy ,
  • the ethyleneoxy- (A), propyleneoxy- (B) and butyleneoxy group (s) (D) are randomly distributed, alternately distributed or are in the form of two, three, four, five or more blocks in any order.
  • the sequence R1 in the presence of a plurality of different alkyleneoxy blocks, the sequence R1, butyleneoxy block, propyleneoxy block, ethyleneoxy block is preferred.
  • the butylene oxide used is intended
  • X is an alkylene group or alkenylene group having 0 to 10, preferably 0 to 3, carbon atoms.
  • the alkylene group is preferably a methylene, ethylene or propylene group.
  • C 4 - epoxides there are often no specific details regarding the description of C 4 - epoxides. It may generally be understood as 1,2-butylene oxide, 2,3-butylene oxide, iso-butylene oxide, and mixtures of these compounds.
  • the composition is generally dependent on the C 4 olefin used, and to some extent on the oxidation process.
  • Y is a sulfonate, sulfate or carboxyl group or phosphate group.
  • M + is a cation, preferably a cation selected from the group Na + ; K + , Li + , NH 4 + , H + , g 2+ and Ca 2 ⁇
  • the surfactants according to the general formula can be prepared in a manner known in principle by alkoxylation of corresponding alcohols R 1 -OH.
  • the implementation of such alkoxylations is known in principle to the person skilled in the art. It is also known to the person skilled in the art that the molar weight distribution of the alkoxylates can be influenced by the reaction conditions, in particular the choice of the catalyst.
  • the surfactants according to the general formula may preferably be prepared by base-catalyzed alkoxylation.
  • the alkylene oxide is initially metered in at 130.degree. In the course of the reaction, the temperature rises up to 170 ° C due to the released heat of reaction.
  • the butylene oxide is first added at a temperature in the range of 135 to 145 ° C, then the propylene oxide is added at a temperature in the range of 130 to 145 ° C and then the ethylene oxide at a temperature in the range of 125 to 145 ° C was added.
  • the catalyst can be neutralized, for example by addition of acid (for example acetic acid or phosphoric acid) and filtered off as required.
  • the alkoxylation of the alcohols R 1 -OH can also be carried out by other methods, for example by acid-catalyzed alkoxylation.
  • double hydroxide clays as described in DE 4325237 A1
  • double metal cyanide (DMC) catalysts can be used.
  • Suitable 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 may be added with the catalyst, the mixture 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 may typically be less than 1000 ppm, for example 250 ppm or less.
  • the anionic group is finally introduced.
  • a sulphate group it is possible, for example, to resort to the reaction with sulfuric acid, chlorosulphonic acid or sulfur trioxide in the falling film reactor with subsequent neutralization.
  • a sulphonate group for example, the reaction with propanesultone and subsequent neutralization, with butanesultone and subsequent neutralization, with vinylsulfonic acid sodium salt or with 3-chloro-2-hydroxy-propanesulfonic sodium salt.
  • a carboxylate group for example, one can resort to the oxidation of the alcohol with oxygen and subsequent neutralization or the reaction with chloroacetic acid sodium salt.
  • the formulation may additionally optionally comprise further surfactants.
  • surfactants are, for example, anionic surfactants of the type alkylarylsulfonate or olefinsulfonate (alpha-olefinsulfonate or internal olefinsulfonate) and / or nonionic surfactants of the type alkylethoxylate or alkylpolyglucoside.
  • surfactants may in particular also be oligomeric or polymeric surfactants. With such polymeric cosurfactants can be advantageous to reduce the necessary to form a microemulsion amount of surfactants.
  • polymeric cosurfactants are also referred to as "microemulsion boosters.”
  • polymeric surfactants include amphiphilic block copolymers comprising at least one hydrophilic and at least one hydrophobic block Examples include polypropylene oxide-polyethylene oxide block copolymers, polyisobutylene-polyethylene oxide block
  • the main chain preferably comprises substantially olefins or (meth) acrylates as building blocks
  • polyethylene oxide is here intended to include polyethylene oxide blocks comprising propylene oxide units as defined above. Further details of such surfactants are disclosed in WO 2006/131541 A1. Process for the extraction of oil
  • a suitable aqueous formulation of the surfactants according to the general formula is injected into the crude oil deposit through at least one injection well and crude oil is taken from the deposit through at least one production well.
  • crude oil in this context does not mean phase-pure oil, but rather the usual crude oil-water emulsions.
  • the main effect of the surfactant is to reduce the interfacial tension between water and oil - desirably to values significantly ⁇ 0.1 mN / m.
  • water flooding or preferably the Winsor type III "microemulsion flooding”
  • polymer flooding a higher-viscosity aqueous solution of a strong one to maintain the pressure thickening polymer
  • surfactant flooding or preferably the Winsor type III "microemulsion flooding
  • water flooding water flooding
  • polymer flooding preferably a higher-viscosity aqueous solution of a strong one to maintain the pressure thickening polymer
  • polymer flooding a higher-viscosity aqueous solution of a strong one to maintain the pressure thickening polymer
  • surfactants are first allowed to act on the formation.
  • Another known technique is the injection of a solution of surfactants and thickening polymers followed by a solution of thickening polymer.
  • the person skilled in the art knows details of the technical implementation of "surfactant flooding
  • an aqueous formulation which contains surfactants of the general formula is used.
  • the formulations may optionally also comprise water-miscible or at least water-dispersible organic or other agents.
  • Such additives are used in particular for stabilizing the surfactant solution 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.
  • only water is used for formulation.
  • water-miscible solvents include, in particular, alcohols, such as methanol, ethanol and propanol, butanol, sec-butanol, pentanol, butyl ethylene glycol, butyl diethylene glycol or butyl triethylene glycol.
  • the proportion of surfactants according to the general formula is at least 30% by weight with respect to the proportion of all surfactants present, that is to say the surfactants according to the general formula and optionally existing surfactants.
  • the proportion is preferably at least 50% by weight.
  • the mixture used according to the invention can preferably be used for the surfactant flooding of deposits. It is particularly suitable for Winsor type III microemulsion flooding (flooding in the Winsor III range or in the area of existence of the bicontinuous microemulsion phase). The technique of microemulsion flooding has already been described in detail at the beginning.
  • the formulations may also contain other components, such as, for example, C 4 -C 8 -alcohols and / or basic salts (so-called "alkaline surfactant flooding") .
  • these additives can be used, for example, to reduce the retention in the formation
  • the amount ratio of the alcohols with respect to the total amount of surfactant used is usually at least 1: 1 - however, a significant excess of alcohol can also be used
  • the amount of basic salts can typically be from 0.1% by weight to 5% by weight .-% pass.
  • the deposits in which the process is used have a temperature of at least 10 ° C, for example 10 to 150 ° C, preferably a temperature of at least 15 ° C to 120 ° C.
  • the total concentration of all surfactants together is 0.05 to 5 wt .-% with respect to the total amount of the aqueous surfactant formulation, preferably 0.1 to 2.5 wt .-%.
  • concentration of surfactants may change upon injection into the formation because the formulation may mix with formation water or absorb surfactants also on solid surfaces of the formation. It is the great advantage of the mixture used according to the invention that the surfactants lead to a particularly good lowering of the interfacial tension.
  • the total concentration of the surfactants in such a concentrate is 10 to 45% by weight.
  • the amount of KOH is 0.2 wt .-% of the product to be produced.
  • the mixture is dehydrated at 100 ° C and 20 mbar for 2 h.
  • the mixture is then flushed three times with N 2 , a pre-pressure of about 1, 3 bar N 2 is set and the temperature is increased to 120 to 130 ° C.
  • the alkylene oxide is metered in such that the temperature remains between 125 ° C to 135 ° C (for ethylene oxide) and 130 to 140 ° C (for propylene oxide) and 135 to 145 ° C (for 1, 2-butylene oxide).
  • the mixture is then stirred for 5 h at 125 to 145 ° C, rinsed with N 2 , cooled to 70 ° C and the reactor emptied.
  • the basic crude product is neutralized with acetic acid. Alternatively, the neutralization can be carried out with commercially available Mg silicates, which are then filtered off.
  • the bright product is characterized by means of a 1 H-NMR spectrum in CDCl 3, a gel permeation chromatography and an OH number determination, and the yield is determined.
  • the alcohol (1, 0 eq) to be alkoxylated is mixed with a double metal cyanide catalyst (for example DMC catalyst from BASF Type Zn-Co) at 80 ° C.
  • a double metal cyanide catalyst for example DMC catalyst from BASF Type Zn-Co
  • DMC catalyst from BASF Type Zn-Co
  • the amount of DMC is 0.1% by weight and less of the product to be produced.
  • the mixture is then flushed three times with N 2 , a pre-pressure of about 1.3 bar N 2 is set and the temperature is increased to 120 to 130 ° C.
  • the alkylene oxide is metered in such that the temperature remains between 125 ° C to 135 ° C (for ethylene oxide) and 130 to 140 ° C (for propylene oxide) and 135 to 145 ° C (for 2,3-butylene oxide).
  • the mixture is then stirred for 5 h at 125 to 145 ° C, rinsed with N 2 , cooled to 70 ° C and the reactor emptied.
  • the bright product is characterized by means of a 1 H NMR spectrum in CDCl 3, a gel permeation chromatography and an OH number determination, and the yield is determined.
  • the alkyl alkoxylate (1, 0 eq) to be sulfated is dissolved in 1.5 times the amount of dichloromethane (on a weight percent basis) and cooled to 5-10 ° C. Thereafter, chlorosulfonic acid (1, 1 eq) is added dropwise so that the temperature does not exceed 10 ° C.
  • the mixture is allowed to warm to room temperature and stir for 4 h at this temperature under N 2 stream, before the above reaction mixture in an aqueous NaOH solution with half volume at max. 15 ° C is dropped.
  • the amount of NaOH is calculated so that there is a slight excess with respect to the chlorosulfonic acid used.
  • the resulting pH is about pH 9 to 10.
  • the dichloromethane is added under a slight vacuum on a rotary evaporator at max. 50 ° C away.
  • the product is characterized by 1 H-NMR and determines the water content of the solution (about 70%).
  • 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 in the art for the approximate determination of the interfacial tension.
  • the solubilization parameter SP * indicates how many ml of oil per ml of surfactant used is dissolved in a microemulsion (Windsor type III).
  • the interfacial tension ⁇ can be calculated from the approximate formula IFT "0.3 / (SP * ) 2 if equal volumes of water and oil are used (C. Huh, J. Coli., Interf. Sc, Vol. 71, No. 2 (1979)).
  • the concentrations of the respective surfactants are given.
  • the temperature is gradually increased from 20 to 90 ° C, and it is observed in which temperature window forms a microemulsion.
  • the formation of the microemulsion can be visually observed or by means of conductivity measurements. It forms a three-phase system (upper phase oil, middle phase microemulsion, lower phase water). If the upper and lower phases are the same size and no longer change over a period of 12 h, then the optimal temperature (T opt ) of the microemulsion has been found.
  • the volume of the middle phase is determined. From this volume, the volume of added surfactant is subtracted. The value obtained is then divided by two. This volume is now divided by the volume of added surfactant. The result is noted as SP * .
  • the type of oil and water used to determine SP * is determined according to the system under investigation.
  • petroleum itself can be used, or even a model oil such as decane.
  • Both pure water and saline water can be used as water to better model the conditions in the oil formation.
  • the composition of the aqueous phase may be adjusted according to the composition of a particular reservoir water. Information on the aqueous phase used and the oil phase can be found below in the concrete description of the experiments.
  • a 1: 1 mixture of decane and a NaCl solution was added with butyldiethylene glycol (BDG).
  • Butyl diethylene glycol (BDG) acts as a cosolvent and is not included in the calculation of SP * .
  • a surfactant mixture of 3 parts of alkylalkoxysulfate and 1 part of dodecylbenzenesulfonate (Lutensit A-LBN 50 ex BASF). The total surfactant concentration is given in weight percent of the total volume.
  • Comparative Example C1 and Example 2 show very clearly that with surfactants having the same degree of alkoxylation, the use of 1,2-butylene oxide instead of propylene oxide is of considerable advantage.
  • the SP * is three times larger.
  • the placement of the 1, 2 BuO directly on the alkyl moiety provides lower interfacial tensions than any other arrangement such as in Example 4.
  • Example 2 compared to Examples 3 and 4 show the difference between the surfactant based on the linear Ci 6 Ci 8 -alcohol and the surfactant based on the branched Ci 6 -Guerbet- alcohol.
  • the Guerbet-based surfactant incorporation of 2 units of 1,2-butylene oxide achieves a significantly better SP * than that of a linear alcohol of similar chain length.
  • an approximately identical SP * level as in Example 4 can be achieved.
  • Example 6 it can be seen that the incorporation of 10 EO between sulfate group and PO block, the additional hydrophobicity of the 7-BuO block can be almost compensated, so that a comparison with Comparative Example V1 under similar conditions (similar salinity, similar Temperature T opt ) can make.
  • Example 1 1 shows that the incorporation of 1 eq 1, 2 BuO gives only some improvement in SP * . Only by incorporation of 2 eq 1, 2 BuO results in the C16 Guerbet-based surfactant, a significant improvement (Example 3).
  • Table 4 Experiments with southern German crude oil
  • Comparative Example C1 gives significantly lower SP * values and thus higher interfacial tensions than the BuO-containing Surfactant in Example 2 at comparable temperature. Comparative Example C3 and Example 4 show in a similar manner the advantage of 1,2-butylene oxide.
  • aqueous surfactant solutions mixed with BDG are clearly dissolved under the optimum conditions (salinity and T opt ) and, when added to the oil, give a three-phase system (Winsor type III).
  • the optimal conditions (salinity and T opt ) are very close to each other. If the degree of alkoxylation is correctly matched, a surfactant is obtained as in Example 2 which has a similar hydrophilic-hydrophobic balance to the surfactant in Comparative Example C1. However, SP * is much larger in Example 2. Correspondingly lower is the interfacial tension.
  • aqueous surfactant solutions mixed with BDG are clearly dissolved under the optimum conditions (salinity and T opt ) and, when added to the oil, give a three-phase system (Winsor type III).
  • the optimal conditions (salinity and T opt ) are very close together. If the degree of alkoxylation is correctly matched, a surfactant is obtained as in Example 2 which has a similar hydrophilic-hydrophobic balance to the surfactant in Comparative Example C1. However, SP * is much larger in Example 2. Correspondingly lower is the interfacial tension.

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Abstract

L'invention concerne un procédé d'extraction du pétrole par injection de microémulsions Winsor de type III, selon lequel une formulation de tensioactif(s) aqueuse, renfermant au moins un tensioactif ionique de formule générale R1-O-(D)n-(B)m-(A)I-XY- M+, est injectée dans un gisement de pétrole brut par des puits d'injection et le pétrole brut est extrait du gisement par des puits de production.
EP11706292A 2010-03-10 2011-03-04 Procédé d'extraction du pétrole au moyen de tensioactifs à base d'alcoxylates d'alkyle contenant de l'oxyde de butylène Withdrawn EP2545136A1 (fr)

Priority Applications (1)

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EP11706292A EP2545136A1 (fr) 2010-03-10 2011-03-04 Procédé d'extraction du pétrole au moyen de tensioactifs à base d'alcoxylates d'alkyle contenant de l'oxyde de butylène

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EP10002488 2010-03-10
EP11706292A EP2545136A1 (fr) 2010-03-10 2011-03-04 Procédé d'extraction du pétrole au moyen de tensioactifs à base d'alcoxylates d'alkyle contenant de l'oxyde de butylène
PCT/EP2011/053321 WO2011110503A1 (fr) 2010-03-10 2011-03-04 Procédé d'extraction du pétrole au moyen de tensioactifs à base d'alcoxylates d'alkyle contenant de l'oxyde de butylène

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JP (1) JP2013528720A (fr)
KR (1) KR20130016266A (fr)
CN (2) CN102791824B (fr)
AR (1) AR080479A1 (fr)
AU (1) AU2011226215A1 (fr)
BR (1) BR112012022670A2 (fr)
CA (1) CA2791119C (fr)
EA (1) EA201401362A1 (fr)
EC (1) ECSP12012146A (fr)
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MY (1) MY161638A (fr)
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RU2585322C2 (ru) 2011-03-18 2016-05-27 Басф Се Способ получения интегральных схем, оптических устройств, микромашин и механических высокоточных устройств, имеющих слои структурированного материала со строчным интервалом 50 нм и менее
CA2848961A1 (fr) 2011-10-24 2013-05-02 Basf Se Procede d'extraction de petrole a l'aide de tensioactifs a base d'un melange d'alcoxylates d'hydrocarbures contenant du guerbet en c28, guerbet en c30, guerbet en c32
US9475977B2 (en) * 2011-10-24 2016-10-25 Basf Se Process for producing mineral oil using surfactants based on a mixture of C28 Guerbet, C30 Guerbet, C32 Guerbet-containing hydrocarbyl alkoxylates
CA2851421A1 (fr) * 2011-10-24 2013-05-02 Basf Se Procede d'extraction de petrole a l'aide de tensioactifs a base d'un melange d'alcoxylates d'hydrocarbures contenant un guerbet en c32, un guerbet en c34, un guerbet en c36
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
US9475978B2 (en) * 2011-10-24 2016-10-25 Basf Se Process for producing mineral oil using surfactants based on a mixture of C24 guerbet-, C26 guerbet-, C28-guerbet containing hydrocarbyl alkoxylates
US9475979B2 (en) * 2011-10-24 2016-10-25 Basf Se Process for producing mineral oil using surfactants based on a mixture of C20 Guerbet-, C22 Guerbet-, C24 Guerbet-containing hydrocarbyl alkoxylates
JP6329153B2 (ja) * 2012-09-29 2018-05-23 ダウ グローバル テクノロジーズ エルエルシー アニオン性界面活性剤組成物およびその使用
WO2014064152A1 (fr) * 2012-10-26 2014-05-01 Basf Se Procédé d'extraction de pétrole utilisant des tensioactifs contenant au moins un alcanesulfonate secondaire et un alkyléthersulfate/alkyléthersulfonate/alkyléthercarboxylate/alkylétherphosphate
WO2014063933A1 (fr) * 2012-10-26 2014-05-01 Basf Se Procédé d'extraction du pétrole au moyen de tensioactifs à base d'alcoxylates d'alkyle anioniques provenant d'éthers glycidyliques
EP2964609B1 (fr) 2013-03-08 2018-07-18 Dow Global Technologies LLC Compositions de tensioactifs anioniques et applications associées
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
CN113801316B (zh) * 2020-06-15 2024-01-26 中国石油化工股份有限公司 烷氧基嵌段聚醚磺酸盐阴离子表面活性剂及其制备方法
CN113797842B (zh) * 2020-06-15 2023-08-29 中国石油化工股份有限公司 烃基芳基阴非离子表面活性剂及其制备方法

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EA201401362A1 (ru) 2015-05-29
ECSP12012146A (es) 2012-10-30
AU2011226215A1 (en) 2012-09-20
JP2013528720A (ja) 2013-07-11
RU2563642C2 (ru) 2015-09-20
BR112012022670A2 (pt) 2020-08-11
KR20130016266A (ko) 2013-02-14
CN104726084A (zh) 2015-06-24
RU2012142936A (ru) 2014-04-20
MX340884B (es) 2016-07-29
CN102791824B (zh) 2016-03-02
CA2791119C (fr) 2018-05-22
MX2012010276A (es) 2012-09-28
CN102791824A (zh) 2012-11-21
AR080479A1 (es) 2012-04-11
MY161638A (en) 2017-04-28
WO2011110503A1 (fr) 2011-09-15
CA2791119A1 (fr) 2011-09-15

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