EP3143097A1 - Aminosulphonate foam stabilizers - Google Patents

Aminosulphonate foam stabilizers

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Publication number
EP3143097A1
EP3143097A1 EP15722143.3A EP15722143A EP3143097A1 EP 3143097 A1 EP3143097 A1 EP 3143097A1 EP 15722143 A EP15722143 A EP 15722143A EP 3143097 A1 EP3143097 A1 EP 3143097A1
Authority
EP
European Patent Office
Prior art keywords
formula
aminosulphonate
compound
radical
chr
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Withdrawn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
EP15722143.3A
Other languages
German (de)
French (fr)
Inventor
Mikel Morvan
Max Chabert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Operations SAS
Original Assignee
Rhodia Operations SAS
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 Rhodia Operations SAS filed Critical Rhodia Operations SAS
Publication of EP3143097A1 publication Critical patent/EP3143097A1/en
Withdrawn legal-status Critical Current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
    • 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
    • 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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/92—Compositions for stimulating production by acting on the underground formation characterised by their form or by the form of their components, e.g. encapsulated material
    • C09K8/94—Foams
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
    • E21B43/166—Injecting a gaseous medium; Injecting a gaseous medium and a liquid medium
    • E21B43/168—Injecting a gaseous medium

Definitions

  • the present invention relates to aminosulfonate foam stabilizing compounds, particularly useful in the context of the recovery of hydrocarbons present in an underground formation. These compounds are particularly suitable for enhanced oil recovery (known as EOR, for the English “Enhanced 0/7 Recovery”).
  • hydrocarbon reservoir oil reservoir such as a rock formation or sand, for example
  • a common method is to perform a so-called secondary recovery, namely by injecting a gas or a liquid (sea or river water or production water for example) to in the hydrocarbon reservoir, by injection wells, so as to maintain within the tank a positive pressure to continue to convey the hydrocarbons to the production well.
  • foaming agents have been proposed for this type of application in EOR, among which there may be mentioned, for example, anionic surfactants, especially the sulphonates which are contemplated in US Pat. No. 4,852,653; US 5,046,560 or US 5,076,357, nonionic surfactants such as those proposed in US 5,363,915, or alternatively amphoteric surfactants of the type described in US 5,614,473.
  • anionic surfactants especially the sulphonates which are contemplated in US Pat. No. 4,852,653; US 5,046,560 or US 5,076,357
  • nonionic surfactants such as those proposed in US 5,363,915, or alternatively amphoteric surfactants of the type described in US 5,614,473.
  • foaming agents often has disadvantages associated with a limited stability of the foam in the presence of oil, too high adsorption, or even low solubility in water and / or injection brine or stability low thermal.
  • foaming agents often require the additional use of foam promoters (so-called "foam boosters" in English), the use of which is also likely to have repercussions in terms of costs of process. This is particularly the case for surfactants of the sulfonate type, which often require the use of betaine type foam promoters, as described in particular in US Pat. No. 1 / 2,205,546.
  • the present invention aims to provide foam stabilizers suitable in particular for the formation of stable foams under the conditions employed in operations of enhanced oil recovery (EOR).
  • EOR enhanced oil recovery
  • the present invention proposes the use of an aminosulphonate compound corresponding to the following formula (I):
  • R 1 is an alkyl or alkylamido radical
  • R 2 is an alkyl radical, optionally hydroxylated
  • R 3 , R 4 and R 5 are, independently of one another, H or OH; it being understood that at least one of the groups R 3 ; R 4 and / or R 5 is OH, for stabilizing a foam, in particular a foam used for the recovery of hydrocarbons present in a subterranean formation.
  • the compound of formula (I) may optionally be used together with its protonated form of formula ( ⁇ ) as follows: R 1 R 2 NH + -CHR 3 -CHR 4 -CHR 5 -SO 3 " .
  • the aminosulphonate compound is employed only in its "unprotonated amine" form (I).
  • a mixture of the non-protonated form (I) and the protonated form ( ⁇ ) is used, with a molar ratio (1 ') / (l) of the protonated form ( ⁇ ) to the unprotonated form (I) preferably lower 1.
  • aminosulphonate of the invention is used essentially in its unprotonated form of formula (I), typically with a protonated form ( ⁇ ) / non-protonated form (I) molar ratio of less than 10%, more preferably less than 1%.
  • the aminosulphonate compounds used according to the invention are foaming agents which make it possible to form a foam which is sufficiently stable to be used for the recovery of hydrocarbons present in an underground formation, this foam being able to be preformed before injection into the subterranean formation or well formed in situ. .
  • the stability of the foams obtained in the context of the invention is comparable to that of foams obtained with the most common commercial foaming agents, in particular with very good thermal stability.
  • the aminosulphonate compounds used according to the invention and the foams they form are stable at temperatures which can reach up to
  • the aminosulphonate compounds used according to the invention have good foaming performance even when used alone, which is advantageous in terms of application because it is not necessary to premix the constituents (as for commercial products, typically employing surfactant mixtures).
  • the aminosulphonate compounds according to the invention when used alone, have the advantage of preventing the chromatographic effects potentially obtained with multiple compounds.
  • aminosulphonate compounds used according to the invention also have, in general, a relatively low adsorption on most of the rocks of the underground formations, generally lower than that of the usual commercial foaming agents.
  • aminosulphonate compounds used according to the invention have another advantage, namely a good solubility in water, including in the presence of salts (hard water), in which they constitute according to yet another aspect a very alternative. interesting to many other foaming agents.
  • the compounds used according to the invention of formula (I) are present at least partly in their form (I), said non-protonated, where the nitrogen atom of the amino group is not charged.
  • the protonated form ( ⁇ ) above, where the nitrogen atom of the amino group is positively charged can be employed.
  • aminosulphonate compounds of formula (I) and ( ⁇ ) of the invention are typically used in combination with one or more counterion of the sulfonate ion.
  • suitable counterions there may be mentioned sodium, potassium, ammonium or alkylammonium cations, especially isopropylammonium.
  • alkyl denotes a hydrocarbon radical, preferably saturated, linear or branched, optionally cyclized in whole or in part, and most often monovalent.
  • alkyl radical in the sense of the present description can thus in particular be a saturated monovalent hydrocarbon radical comprising, from 1 to 24, preferably from 1 to 20, in particular from 6 to 12, carbon atoms, for example the methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, pentyl, or n-hexyl radicals.
  • alkyl radical according to the present description may be unsubstituted (totally composed of carbon and hydrogen atoms) or, alternatively, be substituted on one or more carbon atoms, where appropriate preferably by at least one chosen substituent. in the group consisting of the following substituents: hydroxy, alkoxy, amino, halo, carboxy, or phosphono.
  • the alkyl radicals according to the invention may for example be chosen from hydroxymethyl, hydroxyethyl, methoxymethyl, ethoxymethyl, isopropoxyethyl, aminomethyl, chloromethyl or trichloromethyl, carboxyethyl or phosphonomethyl radicals.
  • alkoxy refers to an oxy radical substituted by an alkyl group as defined above.
  • alkoxyl radicals that may especially be mentioned are the methoxyl, ethoxyl, propoxyl, isopropoxyl or butoxyl radicals, which radicals may also be substituted on one or more of their carbon atoms.
  • cycloalkyl denotes a cyclic saturated hydrocarbon radical, in particular a saturated cyclic hydrocarbon radical comprising from 1 to 18 carbon atoms, for example cyclohexyl or cyclooctyl radicals, which may be optionally substituted on one or more of their carbon atoms.
  • aryl designates a monovalent unsaturated hydrocarbon radical containing one or more carbon rings comprising 6 atoms in which the unsaturation may be represented by three conjugated double bonds, for example the phenyl, naphthyl or anthryl radicals, phenanthryl or biphenyl, which may be substituted on one or several carbon atoms of the cycle.
  • an aryl radical is substituted on one or more of its carbon atoms by one or more substituents chosen from: hydroxy, alkyl, halo, haloalkyl, or amino. These substituted aryl radicals may then be chosen from methylphenyl, dimethylphenyl, hydroxyphenyl, chlorophenyl, trichloromethylphenyl or aminophenyl radicals.
  • aralkyl denotes an alkyl radical as defined above substituted with one or more aryl radicals. Mention may especially be made of phenylmethyl, phenylethyl or triphenylmethyl radicals, which may be optionally substituted on one or more of their carbon atoms.
  • alkaryl denotes an aryl radical substituted with one or more alkyl radicals as defined above. Mention may be made, for example, of methylphenyl, dimethylphenyl or trimethylphenyl radicals, which may be optionally substituted on one or more of their carbon atoms.
  • a radical may be "optionally substituted” means, in general, unless otherwise stated, that said radical may be substituted by one or more inorganic or organic substituents, such as, for example, alkyl, aryl, aralkyl, alkaryl, a heteroatom, or a heterocyclyl, or with one or more functional groups capable of coordinating metal ions, such as, for example, hydroxyl, carbonyl, carboxyl, amino, imino, amido, phosphonic acid, sulphonic acid, or arsenate groups, or their inorganic and organic esters, such as, for example, sulphate or phosphate, or their salts.
  • inorganic or organic substituents such as, for example, alkyl, aryl, aralkyl, alkaryl, a heteroatom, or a heterocyclyl
  • functional groups capable of coordinating metal ions such as, for example, hydroxyl, carbonyl, carboxyl, amino, imino, amido, phospho
  • R 1 represents an alkyl radical preferably comprising from 1 to 24, and preferably from 6 to 18 carbon atoms. According to another embodiment, in formula (I) mentioned above, R 1 represents an alkylamido radical, preferably comprising from 2 to 24 carbon atoms.
  • alkylamido denotes an alkyl radical substituted by an amido radical -NHC (O) R 6 , R 6 representing an alkyl radical as defined above, comprising in particular from 1 to 24, preferably from 6 to 18 carbon atoms.
  • alkylamido radical within the meaning of the present description can for example be the following formula (A):
  • R 6 represents a linear or branched alkyl radical comprising from 2 to 24 carbon atoms, for example from 6 to 18 carbon atoms, and preferably from 8 to 12 carbon atoms,
  • n is an integer ranging from 2 to 5, and preferably equal to 2, 3 or 4.
  • R 1 represents a radical of the above-mentioned formula (A) in which n is 2.
  • R 1 represents a radical of formula (A) mentioned above in which R 6 represents an alkyl radical, preferably linear, comprising 1 1 carbon atoms.
  • R 1 represents a radical of formula (A) mentioned above wherein n is 2 and R 6 represents an alkyl radical, preferably linear, comprising 1 1 carbon atoms.
  • a family of preferred compounds used according to the invention consists of compounds of general formula (1-1) below:
  • R 2 , R 3 , R 4 , R 5 , R 6 and n being as defined above.
  • R 2 is an alkyl radical, in particular a non-hydroxylated radical, that is to say one which is not substituted by a hydroxyl group, preferably comprising 2 to 20, preferably 2 to 10, carbon atoms.
  • R 2 is a hydroxyalkyl radical.
  • hydroxyalkyl or “hydroxylated alkyl” refers to an alkyl radical substituted with a hydroxyl group.
  • Such a radical may for example be represented by the formula -A-OH, A representing a linear or branched alkylene radical comprising from 2 to 20, preferably from 2 to 10, carbon atoms.
  • R 2 is a hydroxyalkyl radical comprising from 2 to 20, preferably from 2 to 10 carbon atoms.
  • R 2 is a hydroxyethyl radical.
  • a family of interesting compounds used according to the invention consists of compounds of the following eneral formula (I-2):
  • R 3 , R 4 , R 5 , R 6 and n being as defined above, and m being an integer ranging from 1 to 10, preferably from 2 to 6.
  • a family of preferred compounds used according to the invention consists of compounds of general formula (I-3) below:
  • R 3 , R 4 , R 5 , R 6 and n being as defined above.
  • R 4 is OH and R 3 and R 5 are, independently from each other, H or OH.
  • a family of preferred compounds used according to the invention consists of compounds of the following eneral formula (I-4):
  • R 3 , R 5 , R 6 and n being as defined above.
  • n is equal to 2.
  • a family of preferred compounds used according to the invention consists of compounds of the following general formula (I-5):
  • R 3 , R 5 and R 6 being as defined above.
  • a family of preferred compounds used according to the invention consists of compounds of the following general formula (I-6):
  • aminosulphonate compound employed according to the present invention corresponds to one of the following formulas:
  • aminosulphonate compound one of the following commercial products can be used according to the invention: Mackam LS, MAckterra LS, Miranol CS, or Miranol
  • the present invention relates to the use of the Mackam product
  • the aminosulphonate is used essentially in its unprotonated form of formula (I), with a molar ratio protonated form / unprotonated form less than 10%, preferably less than 1%.
  • the unprotonated form is the major compound.
  • protonated form / non-protonated form molar ratio refers to the ratio of the number of moles of the protonated form of formula ( ⁇ ) to the number of moles of the unprotonated form of formula (I).
  • the present invention also relates to a method for extracting hydrocarbons contained in a subterranean formation, comprising the injection under pressure within said formation of a foaming composition and a gas capable of inducing the expansion of said foaming composition, said foaming composition comprising a compound of formula (I) as defined above, optionally in combination with its protonated form of formula ( ⁇ ) as defined above.
  • the above extraction method can be implemented either by forming the foam after injection in the underground formation (in situ formation of foam) or by preforming the foam before injection into the subterranean formation (ex formation). foam).
  • the above method is implemented with a foaming composition not comprising anionic surfactant.
  • the above method is implemented with a foaming composition that does not include additional foam stabilizer. According to one embodiment, the above method is implemented with a foaming composition comprising no foam stabilizer other than the aminosulfonate compound according to the invention.
  • the aforementioned method is carried out with a foaming composition comprising a compound of formula (I-1), (I-2), (I-3), (I-4), (I-5), ) or (I-6) as defined above.
  • the foaming composition is an aqueous composition, which preferably comprises the compound of formula (I), and optionally its protonated form ( ⁇ ), at the level of 0.01% to 10% by weight, more preferably from 0.1% to 1% by weight relative to the total weight of water.
  • a foaming composition according to the invention comprises the compound of formula (I), and optionally its protonated form ( ⁇ ), in an amount of 0.5% to 2% by weight relative to the total weight of said composition.
  • the aforementioned method is implemented with a following cost:
  • the present invention also relates to a method for extracting hydrocarbons contained in an underground formation, comprising the following steps:
  • the foaming composition may comprise water. It may also include a mixture of clean gases to induce expansion.
  • the constituents in particular the aminosulphonate and the gas, are mixed before being introduced into the subterranean formation. According to another embodiment, they can be injected at different times, for example sequentially.
  • the present invention also relates to a method for extracting hydrocarbons contained in an underground formation, comprising the following steps: (a) forming a foam from a foaming composition comprising an aminosulphonate compound as defined above and a gas capable of inducing the expansion of said foaming composition,
  • the present invention also relates to a method for improving the extraction of hydrocarbons contained in an underground formation, comprising the following steps:
  • gas capable of inducing expansion designates a gas such as air, carbon dioxide, nitrogen, water vapor or natural gas, in particular present in the underground formation. Typically, this gas is carbon dioxide or natural gas present in the underground formation.
  • the present invention also relates to a method for improving the stability of foams in an aqueous foaming composition, comprising a step of adding to said aqueous foaming composition an aminosulphonate compound as defined above.
  • the foam stabilizer according to the invention increases the stability of the foam of a treatment fluid of an oil well ("o / V well treatment fluid ").
  • the foam stabilizer described herein increases the foam stability of a foaming composition that can be used as part of a petroleum well processing fluid.
  • the foaming composition may also be used in combination with an oil well treating fluid in a multi-step process for recovering oil from a subterranean formation.
  • the foam stabilizer may be an element of an assembly introduced alone into the subterranean formation or with another fluid or other composition, for example with the foaming composition or the oil well treatment fluid.
  • the present invention also relates to a method for improving the oil extraction contained in an oil formation comprising the addition of a foam stabilizer according to the invention to an aqueous foaming composition or to a treatment fluid of an oil well. .
  • a foaming composition comprising at least one foam stabilizer according to the invention is introduced, for example injected, into a tank or an underground formation at high pressure to push or release the oil.
  • the foaming composition which gives a foam-like shape or consistency, enters and settles in formation fractures (ie in areas of high permeability) and substantially diverts one or more gases, or a gas / surfactant mixture or an aqueous gas / fluid mixture to the less permeable oil matrix (ie in areas of low permeability).
  • the foaming composition acts as a barrier to enter the fracture network.
  • the gas infiltrates the porous matrix of the formation in place of the fracture network. The gas pushes the trapped oil into the matrix towards the fracture network, where it can be easily recovered by conventional means.
  • the gas used in the gas flooding operation described herein is a gas or a combination of a gas and aqueous fluids.
  • the fluid can be in a supercritical state.
  • the gas or the gas / fluid mixture can be injected, for example by continuous injection.
  • WAG water-alternating-gas
  • the term “reservoir” encompasses the term “oil formation” (including but not limited to carbonate oil formations) since such formation is typically located in a reservoir.
  • One or more wells may be located near the reservoir and / or formation for the purpose of extracting oil.
  • the treatment fluid may be introduced via a well, a borehole, or an opening in the reservoir.
  • the treatment fluid will then be introduced at a pressure high enough to ensure substantial infiltration of the treatment fluid into the fracture network of the formation and substantial exposure of the porous matrix of this formation.
  • the oil may be extracted at the same location or at a location other than the point of introduction of the process fluid.
  • the present invention also relates to the use of the aminosulphonate compounds mentioned above in the petroleum field.
  • these compounds can be used in the implementation of enhanced oil recovery processes for the control of gas mobility ("gas mobility controi" in English).
  • the term "mobility control” is to be interpreted in the broadest sense and also includes a method in which the sweep efficiency of a reservoir or oil formation is improved.
  • foam fracturing which consists in injecting a liquid comprising the compounds of the invention under very high pressure in order to break the well.
  • Example 1 the compounds of the invention can also be used to form foams for cleaning floors.
  • Example 1 the compounds of the invention can also be used to form foams for cleaning floors.
  • the stability of the foam formed with a given formulation is directly related to the effectiveness of this formula in controlling the mobility of the gas in a porous medium.
  • the formulations are prepared at 0.5% by weight in brine at 50 g / l NaCl. They are equilibrated at 90 ° C for one hour in closed containers and the foam is then generated in these closed containers by a very strong mechanical agitation.
  • Rhodacal A246L / Mackam CBS cocamidopropyl hydroxysultaine
  • the Mackam LS product corresponding to a compound according to the invention, makes it possible to obtain foaming performance equal to or even greater than that obtained with the two commercial mixtures, even when it is used as a compound. unique.
  • this product provides excellent performance compared to commercial products, while having the added benefit of being much easier to prepare (single compound).
  • the formulations are prepared at 0.5% by weight in brine at 50 g / L NaCl and in standard seawater.
  • the formulations are brought into contact with a crushed reservoir rock calibrated at 50 ° C. for 24 hours.
  • the supernatant liquid is then titrated and adsorption is evaluated using the difference in concentration between the supernatant and the initial solution.
  • Rhodacal A246L / Mackam CBS cocamidopropyl hydroxysultaine
  • a solution at pH 7 (mixture 2).
  • aminosulfonate formulations according to the invention provide under certain conditions a foam stability comparable to that obtained with commercial foaming formulations having a lower adsorption, which results in a better efficiency of the process from a point of view economic.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Geology (AREA)
  • Mining & Mineral Resources (AREA)
  • Physics & Mathematics (AREA)
  • Environmental & Geological Engineering (AREA)
  • Fluid Mechanics (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

The present invention relates to the use of an aminosulphonate compound corresponding to the following formula (I): R1R2N-CHR3-CHR4-CHR5-SO3 - (I) where: • R1 is a preferably C2 to C24 alkyl or alkylamido radical; • R2 is an optionally hydroxylated alkyl radical; • R3, R4 and R5 are, independently of one another, H or OH; it being understood that at least one of the R3, R4 and/or R5 groups is OH, for stabilizing a foam, in particular a foam used to extract hydrocarbons in an underground formation.

Description

STABILISATEURS DE MOUSSE DE TYPE AMINOSULFONATE  FOAM STABILIZERS OF THE AMINOSULFONATE TYPE
La présente invention a pour objet des composés aminosulfonates stabilisateurs de mousse, notamment utiles dans le cadre de la récupération d'hydrocarbures présents dans une formation souterraine. Ces composés s'avèrent tout particulièrement adaptés pour la récupération assistée du pétrole (dite EOR, pour l'anglais "Enhanced 0/7 Recovery"). The present invention relates to aminosulfonate foam stabilizing compounds, particularly useful in the context of the recovery of hydrocarbons present in an underground formation. These compounds are particularly suitable for enhanced oil recovery (known as EOR, for the English "Enhanced 0/7 Recovery").
Lors de l'extraction du pétrole brut hors d'un réservoir hydrocarboné (réservoir pétrolifère telle qu'une formation rocheuse ou de sable, par exemple), à l'issue de l'étape de récupération primaire lors de laquelle les hydrocarbures sont entraînés hors d'un puits de production par la surpression régnant naturellement au sein du sol, seule une très faible quantité des hydrocarbures est extraite, typiquement de l'ordre de 10%. Pour améliorer l'extraction des hydrocarbures suite à une telle récupération primaire, une méthode usuelle consiste à réaliser une récupération dite secondaire, à savoir en injectant un gaz ou un liquide (eau de mer ou de rivière ou encore eau de production par exemple) au sein du réservoir hydrocarboné, par des puits d'injection, de façon à maintenir au sein du réservoir une surpression propre à continuer à véhiculer les hydrocarbures vers le puits de production. Ce type de récupération secondaire ne permet toutefois d'extraire qu'une partie relativement faible des hydrocarbures résiduels (typiquement de l'ordre de 30%), et ce notamment du fait des différences de viscosité et de densité existant entre le fluide injecté et les hydrocarbures en place, qui n'induisent qu'un balayage partiel des zones renfermant des hydrocarbures. When extracting crude oil from a hydrocarbon reservoir (oil reservoir such as a rock formation or sand, for example), at the end of the primary recovery stage during which hydrocarbons are driven out of a production well by the pressure naturally prevailing in the soil, only a very small amount of hydrocarbons is extracted, typically of the order of 10%. To improve the extraction of hydrocarbons following such primary recovery, a common method is to perform a so-called secondary recovery, namely by injecting a gas or a liquid (sea or river water or production water for example) to in the hydrocarbon reservoir, by injection wells, so as to maintain within the tank a positive pressure to continue to convey the hydrocarbons to the production well. This type of secondary recovery, however, makes it possible to extract only a relatively small portion of the residual hydrocarbons (typically of the order of 30%), and this in particular because of the differences in viscosity and density existing between the injected fluid and the hydrocarbons in place, which only result in a partial sweep of the hydrocarbon zones.
Pour améliorer encore l'efficacité de la récupération par balayage au gaz, il a été proposé, notamment dans le brevet US 1 658 305, de réaliser des injections séquentielles, alternées, d'eau puis de gaz (procédé dit « WAG » pour « water alternating gas »). De façon encore plus intéressante, il est connu d'effectuer d'autres étapes de récupération dites de "récupération assistée du pétrole" (EOR), autres que des injections « WAG » du type précité, notamment en poursuivant la récupération en présence d'agents moussants capables de former une mousse au sein du réservoir hydrocarboné. On suppose que la mousse ainsi formée permet d'optimiser la mise en contact entre le flux vecteur injecté au niveau des puits d'injection et les zones du réservoir renfermant du pétrole. Il a été proposé dans ce cadre d'employer des agents moussants pour former une mousse ex situ, qui est ensuite injectée dans les puits d'injection (voir par exemple le brevet US 3 185 634). Alternativement, il a été décrit des procédés propres à générer la mousse in situ, dans lesquels on injecte séquentiellement, de façon alternée, un milieu aqueux contenant les agents moussants puis un gaz (procédé dit « SAG » pour « surfactant alternating gas » du type décrit notamment dans US 2 866 507). Pour plus de détails concernant l'intérêt de l'emploi de mousses pour la récupération assistée de pétrole brut, on pourra notamment se reporter à WO2010/084369. To further improve the efficiency of the gas scavenging recovery, it has been proposed, in particular in US Pat. No. 1,658,305, to perform sequential, alternating injections of water and then of gas ("WAG" process for " water alternating gas "). Even more interestingly, it is known to perform other so-called "enhanced oil recovery" (EOR) recovery steps, other than "WAG" injections of the aforementioned type, in particular by continuing the recovery in the presence of foaming agents capable of forming a foam within the hydrocarbon reservoir. It is assumed that the foam thus formed makes it possible to optimize contact between the injected vector stream at the injection wells and the areas of the tank containing oil. It has been proposed in this the framework of using foaming agents to form an ex situ foam, which is then injected into the injection wells (see for example US Pat. No. 3,185,634). Alternatively, processes have been described that are capable of generating the foam in situ, in which an aqueous medium containing the foaming agents and then a gas (so-called "SAG" process for "surfactant alternating gas" of the following type is injected sequentially, alternately described in particular in US 2,866,507). For more details on the interest of the use of foams for the enhanced recovery of crude oil, it will be possible to refer in particular to WO2010 / 084369.
Différents types d'agents moussants ont été proposés pour ce type d'application en EOR, parmi lesquels on peut par exemple citer des tensioactifs anioniques, notamment les sulfonates qui sont envisagés dans les brevets US 4 852 653 ; US 5 046 560 ou US 5 076 357, des tensioactifs non ioniques comme ceux proposés dans US 5 363 915, ou bien encore des tensioactifs amphotères du type décrits dans US 5 614 473.  Various types of foaming agents have been proposed for this type of application in EOR, among which there may be mentioned, for example, anionic surfactants, especially the sulphonates which are contemplated in US Pat. No. 4,852,653; US 5,046,560 or US 5,076,357, nonionic surfactants such as those proposed in US 5,363,915, or alternatively amphoteric surfactants of the type described in US 5,614,473.
L'utilisation d'agents moussants présente souvent des inconvénients associés à une stabilité limitée de la mousse en présence de pétrole, une adsorption trop élevée, voire aussi une faible solubilité dans l'eau et/ou la saumure d'injection ou encore une stabilité thermique faible. The use of foaming agents often has disadvantages associated with a limited stability of the foam in the presence of oil, too high adsorption, or even low solubility in water and / or injection brine or stability low thermal.
Aussi, des agents moussants à base de sulfonate avec une stabilité élevée à haute température ont été mis au point (US 4 393 937). L'utilisation de sulfonates alkoxylés a permis d'améliorer la solubilité dans l'eau et les saumures d'injection (US 5 046 560, US 4 856 589, US 4 540 050 ou US2012/220502).  Also, sulfonate foaming agents with high stability at high temperature have been developed (US 4,393,937). The use of alkoxylated sulfonates has improved solubility in water and injection brines (US 5,046,560, US 4,856,589, US 4,540,050 or US2012 / 220502).
En outre, pour obtenir des mousses satisfaisantes, les agents moussants nécessitent souvent l'emploi additionnel de promoteurs de mousse (dits « foam boosters » en anglais), dont l'emploi est, lui aussi, susceptible de se répercuter en termes de coûts de procédé. C'est en particulier le cas des tensioactifs de type sulfonates, qui nécessitent souvent la mise en œuvre de promoteurs de mousses de type bétaines, comme décrit notamment dans US 201 1/275546. In addition, to obtain satisfactory foams, foaming agents often require the additional use of foam promoters (so-called "foam boosters" in English), the use of which is also likely to have repercussions in terms of costs of process. This is particularly the case for surfactants of the sulfonate type, which often require the use of betaine type foam promoters, as described in particular in US Pat. No. 1 / 2,205,546.
La présente invention a pour but de fournir des stabilisateurs de mousse adaptés notamment à la formation de mousses stables dans les conditions employées dans des opérations de récupération assistée du pétrole (EOR). A cet effet, la présente invention propose l'utilisation d'un composé aminosulfonate répondant à la formule (I) suivante : The present invention aims to provide foam stabilizers suitable in particular for the formation of stable foams under the conditions employed in operations of enhanced oil recovery (EOR). For this purpose, the present invention proposes the use of an aminosulphonate compound corresponding to the following formula (I):
R1R2N-CHR3-CHR4-CHR5-S03 " (I) R 1 R 2 N-CHR 3 -CHR 4 -CHR 5 -S0 3 " (I)
dans laquelle : in which :
• R1 est un radical alkyle ou alkylamido ; R 1 is an alkyl or alkylamido radical;
• R2 est un radical alkyle, éventuellement hydroxylé ; R 2 is an alkyl radical, optionally hydroxylated;
• R3, R4 et R5 sont, indépendamment les uns des autres, H ou OH ; étant entendu qu'au moins un des groupes R3 ; R4 et/ou R5 est OH, pour stabiliser une mousse, en particulier une mousse employée pour la récupération d'hydrocarbures présents dans une formation souterraine. R 3 , R 4 and R 5 are, independently of one another, H or OH; it being understood that at least one of the groups R 3 ; R 4 and / or R 5 is OH, for stabilizing a foam, in particular a foam used for the recovery of hydrocarbons present in a subterranean formation.
Dans le cadre de cette utilisation, le composé de formule (I) peut optionnellement être employé conjointement avec sa forme protonée de formule (Γ) suivante : R1R2NH+-CHR3-CHR4-CHR5-S03 ". In the context of this use, the compound of formula (I) may optionally be used together with its protonated form of formula (Γ) as follows: R 1 R 2 NH + -CHR 3 -CHR 4 -CHR 5 -SO 3 " .
Ainsi, selon un mode de réalisation, le composé aminosulfonate est employé uniquement sous sa forme « aminé non protonée » (I). Thus, according to one embodiment, the aminosulphonate compound is employed only in its "unprotonated amine" form (I).
Selon un autre mode de réalisation, on emploie selon l'invention un mélange de la forme non protonée (I) et de la forme protonée (Γ), avec un rapport molaire (l')/(l) de la forme protonée (Γ) à la forme non protonée (I) de préférence inférieur 1 . According to another embodiment, according to the invention a mixture of the non-protonated form (I) and the protonated form (Γ) is used, with a molar ratio (1 ') / (l) of the protonated form (Γ ) to the unprotonated form (I) preferably lower 1.
On préfère que l'aminosulfonate de l'invention soit employé essentiellement sous sa forme non protonée de formule (I), typiquement avec un rapport molaire forme protonée (Γ) / forme non protonée (I) inférieur à 10%, plus préférentiellement inférieur à 1 %. It is preferred that the aminosulphonate of the invention is used essentially in its unprotonated form of formula (I), typically with a protonated form (Γ) / non-protonated form (I) molar ratio of less than 10%, more preferably less than 1%.
Les composés aminosulfonates utilisés selon l'invention sont des agents moussants permettant de former une mousse suffisamment stable pour être employée pour la récupération d'hydrocarbures présents dans une formation souterraine, cette mousse pouvant être préformée avant injection dans la formation souterraine ou bien formée in situ. La stabilité des mousses obtenues dans le cadre de l'invention est comparable à celle des mousses obtenues avec les agents moussants commerciaux les plus usuels, notamment avec une très bonne stabilité thermique. Typiquement, les composés aminosulfonates utilisés selon l'invention et les mousses qu'ils forment sont stables à des températures qui peuvent aller jusqu'àThe aminosulphonate compounds used according to the invention are foaming agents which make it possible to form a foam which is sufficiently stable to be used for the recovery of hydrocarbons present in an underground formation, this foam being able to be preformed before injection into the subterranean formation or well formed in situ. . The stability of the foams obtained in the context of the invention is comparable to that of foams obtained with the most common commercial foaming agents, in particular with very good thermal stability. Typically, the aminosulphonate compounds used according to the invention and the foams they form are stable at temperatures which can reach up to
100°C, voire jusqu'à 150°C. 100 ° C or up to 150 ° C.
De façon surprenante, les composés aminosulfonates utilisés selon l'invention ont de bonnes performances moussantes y compris lorsqu'ils sont utilisés seuls, ce qui est avantageux en termes d'application car il n'est pas nécessaire d'effectuer un pré-mélange des constituants (comme pour les produits commerciaux, employant typiquement des mélanges de tensioactifs). De plus, lorsqu'ils sont utilisés seuls, les composés aminosulfonates selon l'invention présentent l'avantage d'empêcher les effets chromatographiques potentiellement obtenus avec des composés multiples. Surprisingly, the aminosulphonate compounds used according to the invention have good foaming performance even when used alone, which is advantageous in terms of application because it is not necessary to premix the constituents (as for commercial products, typically employing surfactant mixtures). In addition, when used alone, the aminosulphonate compounds according to the invention have the advantage of preventing the chromatographic effects potentially obtained with multiple compounds.
Les composés aminosulfonates utilisés selon l'invention présentent en outre, en règle générale, une adsorption relativement faible sur la plupart des roches des formations souterraines, généralement plus faible que celle des agents moussants commerciaux usuels. The aminosulphonate compounds used according to the invention also have, in general, a relatively low adsorption on most of the rocks of the underground formations, generally lower than that of the usual commercial foaming agents.
De plus, les composés aminosulfonates utilisés selon l'invention présentent un autre avantage, à savoir une bonne solubilité dans l'eau, y compris en présence de sels (eau dure), ce en quoi ils constituent selon encore un autre aspect une alternative très intéressante à nombre d'autres agents moussants. In addition, the aminosulphonate compounds used according to the invention have another advantage, namely a good solubility in water, including in the presence of salts (hard water), in which they constitute according to yet another aspect a very alternative. interesting to many other foaming agents.
Les composés utilisés selon l'invention de formule (I) sont présents au moins en partie sous leur forme (I), dite non protonée, où l'atome d'azote du groupe amino n'est pas chargé. En association à cette forme non protonée (I), on peut employer la forme protonée (Γ) précitée, où l'atome d'azote du groupe amino est chargé positivement. The compounds used according to the invention of formula (I) are present at least partly in their form (I), said non-protonated, where the nitrogen atom of the amino group is not charged. In combination with this non-protonated form (I), the protonated form (Γ) above, where the nitrogen atom of the amino group is positively charged, can be employed.
Les composés aminosulfonates de formule (I) et (Γ) de l'invention sont typiquement utilisés en association avec un ou plusieur contre-ion de l'ion sulfonate. Parmi les contre-ions adaptés, on peut notamment citer les cations sodium, potassium, ammonium ou alkylammonium, notamment isopropylammonium. Dans le cadre de la présente description, le terme "alkyle" désigne un radical hydrocarboné de préférence saturé, linéaire ou ramifié, éventuellement cyclisé en tout ou partie, et le plus souvent monovalent. The aminosulphonate compounds of formula (I) and (Γ) of the invention are typically used in combination with one or more counterion of the sulfonate ion. Among the suitable counterions, there may be mentioned sodium, potassium, ammonium or alkylammonium cations, especially isopropylammonium. In the context of the present description, the term "alkyl" denotes a hydrocarbon radical, preferably saturated, linear or branched, optionally cyclized in whole or in part, and most often monovalent.
Un "radical alkyle" au sens de la présente description peut ainsi notamment être un un radical hydrocarboné monovalent saturé comprenant, de 1 à 24, de préférence de 1 à 20, en particulier de 6 à 12, atomes de carbone, comme par exemple les radicaux méthyle, éthyle, n-propyle, iso-propyle, n-butyle, sec-butyle, t- butyle, pentyle, ou n-hexyle. An "alkyl radical" in the sense of the present description can thus in particular be a saturated monovalent hydrocarbon radical comprising, from 1 to 24, preferably from 1 to 20, in particular from 6 to 12, carbon atoms, for example the methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, pentyl, or n-hexyl radicals.
Un radical alkyle selon la présente description peut être non substitué (totalement constitué d'atomes de carbone et d'hydrogène) ou bien, alternativement, être substitué sur un ou plusieurs atomes de carbone, le cas échéant de préférence par au moins un substituant choisi dans le groupe constitué des substituants suivants : hydroxy, alkoxy, amino, halo, carboxy, ou phosphono. Ainsi, les radicaux alkyles selon l'invention peuvent par exemple être choisis parmi les radicaux hydroxyméthyle, hydroxyéthyle, méthoxyméthyle, éthoxyméthyle, isopropoxyéthyle, aminométhyle, chlorométhyle ou trichlorométhyle, carboxyéthyle ou phosphonométhyle.  An alkyl radical according to the present description may be unsubstituted (totally composed of carbon and hydrogen atoms) or, alternatively, be substituted on one or more carbon atoms, where appropriate preferably by at least one chosen substituent. in the group consisting of the following substituents: hydroxy, alkoxy, amino, halo, carboxy, or phosphono. Thus, the alkyl radicals according to the invention may for example be chosen from hydroxymethyl, hydroxyethyl, methoxymethyl, ethoxymethyl, isopropoxyethyl, aminomethyl, chloromethyl or trichloromethyl, carboxyethyl or phosphonomethyl radicals.
Selon la présente invention, le terme "alkoxy" désigne un radical oxy substitué par un groupe alkyle tel que défini ci-dessus. Parmi les radicaux alkoxyles, on peut notamment citer les radicaux méthoxyle, éthoxyle, propoxyle, isopropoxyle ou butoxyle, ceux-ci pouvant également être substitués sur un ou plusieurs de leurs atomes de carbone. According to the present invention, the term "alkoxy" refers to an oxy radical substituted by an alkyl group as defined above. Among the alkoxyl radicals that may especially be mentioned are the methoxyl, ethoxyl, propoxyl, isopropoxyl or butoxyl radicals, which radicals may also be substituted on one or more of their carbon atoms.
Selon la présente invention, le terme "cycloalkyle" désigne un radical hydrocarboné saturé cyclique, notamment un radical hydrocarboné cyclique saturé comprenant de 1 à 18 atomes de carbone, comme par exemple les radicaux cyclohexyle ou cyclooctyle, qui peuvent être éventuellement substitués sur un ou plusieurs de leurs atomes de carbone. According to the present invention, the term "cycloalkyl" denotes a cyclic saturated hydrocarbon radical, in particular a saturated cyclic hydrocarbon radical comprising from 1 to 18 carbon atoms, for example cyclohexyl or cyclooctyl radicals, which may be optionally substituted on one or more of their carbon atoms.
Selon la présente invention, le terme "aryle" désigne un radical hydrocarboné insaturé monovalent contenant un ou plusieurs cycles carbonés comprenant 6 atomes dans lesquels l'insaturation peut être représentée par trois doubles liaisons conjuguées, comme par exemple les radicaux phényle, naphthyle, anthryle, phénanthryle ou biphényle, qui peuvent éventuellement être substitués sur un ou plusieurs atomes de carbone du cycle. Selon un mode de réalisation, un radical aryle est substitué sur un ou plusieurs de ses atomes de carbone par un ou plusieurs substituants choisis parmi : hydroxy, alkyle, halo, haloalkyle, ou amino. Ces radicaux aryles substitués peuvent alors être choisis parmi les radicaux méthylphényle, diméthylphényle, hydroxyphényle, chlorophényle, trichlorométhylphényle ou aminophényle. According to the present invention, the term "aryl" designates a monovalent unsaturated hydrocarbon radical containing one or more carbon rings comprising 6 atoms in which the unsaturation may be represented by three conjugated double bonds, for example the phenyl, naphthyl or anthryl radicals, phenanthryl or biphenyl, which may be substituted on one or several carbon atoms of the cycle. According to one embodiment, an aryl radical is substituted on one or more of its carbon atoms by one or more substituents chosen from: hydroxy, alkyl, halo, haloalkyl, or amino. These substituted aryl radicals may then be chosen from methylphenyl, dimethylphenyl, hydroxyphenyl, chlorophenyl, trichloromethylphenyl or aminophenyl radicals.
Selon la présente invention, le terme "aralkyle" désigne un radical alkyle tel que défini ci-dessus substitué par un ou plusieurs radicaux aryles. On peut notamment citer les radicaux phénylméthyle, phényléthyle ou triphénylméthyle, qui peuvent être éventuellement substitués sur un ou plusieurs de leurs atomes de carbone. According to the present invention, the term "aralkyl" denotes an alkyl radical as defined above substituted with one or more aryl radicals. Mention may especially be made of phenylmethyl, phenylethyl or triphenylmethyl radicals, which may be optionally substituted on one or more of their carbon atoms.
Selon la présente invention, le terme "alkaryle" désigne un radical aryle substitué par un ou plusieurs radicaux alkyles tels que définis ci-dessus. On peut par exemple citer les radicaux méthylphényle, diméthylphényle ou triméthylphényle, qui peuvent être éventuellement substitués sur un ou plusieurs de leurs atomes de carbone. According to the present invention, the term "alkaryl" denotes an aryl radical substituted with one or more alkyl radicals as defined above. Mention may be made, for example, of methylphenyl, dimethylphenyl or trimethylphenyl radicals, which may be optionally substituted on one or more of their carbon atoms.
Selon la présente invention, l'indication selon laquelle un radical peut être "éventuellement substitué" signifie, en général, sauf indication contraire, que ledit radical peut être substitué par un ou plusieurs substituants inorganique ou organique, comme par exemple, alkyle, aryle, aralkyle, alkaryle, un hétéroatome, ou un hétérocyclyle, ou par un ou plusieurs groupes fonctionnels pouvant coordiner des ions métallique, comme par exemple les groupes hydroxyle, carbonyle, carboxyle, amino, imino, amido, acide phosphonique, acide sulfonique, ou arséniate, ou leurs esters inorganique et organique, comme par exemple les sulfate ou phosphate, ou leurs sels. According to the present invention, the indication that a radical may be "optionally substituted" means, in general, unless otherwise stated, that said radical may be substituted by one or more inorganic or organic substituents, such as, for example, alkyl, aryl, aralkyl, alkaryl, a heteroatom, or a heterocyclyl, or with one or more functional groups capable of coordinating metal ions, such as, for example, hydroxyl, carbonyl, carboxyl, amino, imino, amido, phosphonic acid, sulphonic acid, or arsenate groups, or their inorganic and organic esters, such as, for example, sulphate or phosphate, or their salts.
Selon la présente invention, la terminologie "(Cx-Cy)" en référence à un groupe organique, dans lequel x et y sont des nombres entiers, indique que ce groupe peut contenir de x atomes de carbone à y atomes de carbone par groupe. According to the present invention, the terminology "(Cx-Cy)" with reference to an organic group, wherein x and y are integers, indicates that this group may contain x carbon atoms at y carbon atoms per group.
Selon un mode de réalisation, dans la formule (I) susmentionnée, R1 représente un radical alkyle comprenant de préférence de 1 à 24, et préférentiellement de 6 à 18 atomes de carbone. Selon un autre mode de réalisation, dans la formule (I) susmentionnée, R1 représente un radical alkylamido, comprenant de préférence de 2 à 24 atomes de carbone. According to one embodiment, in formula (I) mentioned above, R 1 represents an alkyl radical preferably comprising from 1 to 24, and preferably from 6 to 18 carbon atoms. According to another embodiment, in formula (I) mentioned above, R 1 represents an alkylamido radical, preferably comprising from 2 to 24 carbon atoms.
Selon l'invention, le terme "alkylamido" désigne un radical alkyle substitué par un radical amido -NHC(0)R6, R6 représentant un radical alkyle tel que défini ci- dessus, comprenant notamment de 1 à 24, de préférence de 6 à 18 atomes de carbone. According to the invention, the term "alkylamido" denotes an alkyl radical substituted by an amido radical -NHC (O) R 6 , R 6 representing an alkyl radical as defined above, comprising in particular from 1 to 24, preferably from 6 to 18 carbon atoms.
Un radical alkylamido au sens de la présente description peut être par exemple répondre à la formule (A) suivante :  An alkylamido radical within the meaning of the present description can for example be the following formula (A):
dans laquelle :  in which :
- R6 représente un radical alkyle, linéaire ou ramifié, comprenant de 2 à 24 atomes de carbone, par exemple de 6 à 18 atomes de carbone, et de préférence de 8 à 12 atomes de carbone, R 6 represents a linear or branched alkyl radical comprising from 2 to 24 carbon atoms, for example from 6 to 18 carbon atoms, and preferably from 8 to 12 carbon atoms,
- n est un nombre entier allant de 2 à 5, et de préférence égal à 2, 3 ou 4.  n is an integer ranging from 2 to 5, and preferably equal to 2, 3 or 4.
Selon un mode de réalisation, dans la formule (I) susmentionnée, R1 représente un radical de formule (A) susmentionnée dans laquelle n est 2. According to one embodiment, in the aforementioned formula (I), R 1 represents a radical of the above-mentioned formula (A) in which n is 2.
Selon un mode de réalisation, dans la formule (I) susmentionnée, R1 représente un radical de formule (A) susmentionnée dans laquelle R6 représente un radical alkyle, de préférence linéaire, comprenant 1 1 atomes de carbone. According to one embodiment, in formula (I) mentioned above, R 1 represents a radical of formula (A) mentioned above in which R 6 represents an alkyl radical, preferably linear, comprising 1 1 carbon atoms.
Selon un mode de réalisation, dans la formule (I) susmentionnée, R1 représente un radical de formule (A) susmentionnée dans laquelle n est 2 et R6 représente un radical alkyle, de préférence linéaire, comprenant 1 1 atomes de carbone. According to one embodiment, in formula (I) above, R 1 represents a radical of formula (A) mentioned above wherein n is 2 and R 6 represents an alkyl radical, preferably linear, comprising 1 1 carbon atoms.
Une famille de composés préférés utilisés selon l'invention est constituée de composés de formule générale (1-1 ) suivante : A family of preferred compounds used according to the invention consists of compounds of general formula (1-1) below:
R2, R3, R4, R5, R6 et n étant tels que définis ci-dessus. R 2 , R 3 , R 4 , R 5 , R 6 and n being as defined above.
Selon un mode de réalisation, dans la formule (I) ou (1-1 ) susmentionnée, R2 est un radical alkyle, en particulier non hydroxylé, c'est-à-dire non substitué par un groupe hydroxyle, comprenant de préférence de 2 à 20, préférentiellement de 2 à 10, atomes de carbone. According to one embodiment, in the above-mentioned formula (I) or (1-1), R 2 is an alkyl radical, in particular a non-hydroxylated radical, that is to say one which is not substituted by a hydroxyl group, preferably comprising 2 to 20, preferably 2 to 10, carbon atoms.
Selon un mode de réalisation, dans les formules (I) ou (1-1 ) susmentionnées, R2 est un radical hydroxyalkyle. Le terme "hydroxyalkyle" ou "alkyle hydroxylé" désigne un radical alkyle substitué par un groupe hydroxyle. Un tel radical peut par exemple être représenté par la formule -A-OH, A représentant un radical alkylène linéaire ou ramifié comprenant de 2 à 20, de préférence de 2 à 10, atomes de carbone. De préférence, R2 est un radical hydroxyalkyle comprenant de 2 à 20, de préférence de 2 à 10 atomes de carbone. According to one embodiment, in the formulas (I) or (1-1) mentioned above, R 2 is a hydroxyalkyl radical. The term "hydroxyalkyl" or "hydroxylated alkyl" refers to an alkyl radical substituted with a hydroxyl group. Such a radical may for example be represented by the formula -A-OH, A representing a linear or branched alkylene radical comprising from 2 to 20, preferably from 2 to 10, carbon atoms. Preferably, R 2 is a hydroxyalkyl radical comprising from 2 to 20, preferably from 2 to 10 carbon atoms.
Selon un mode de réalisation, R2 est un radical hydroxyéthyle. According to one embodiment, R 2 is a hydroxyethyl radical.
Une famille de composés intéressants utilisés selon l'invention est constituée de composés de formule énérale (I-2) suivante : A family of interesting compounds used according to the invention consists of compounds of the following eneral formula (I-2):
R3, R4, R5, R6 et n étant tels que définis ci-dessus, et m étant un nombre entier allant de 1 à 10, de préférence de 2 à 6. R 3 , R 4 , R 5 , R 6 and n being as defined above, and m being an integer ranging from 1 to 10, preferably from 2 to 6.
Une famille de composés préférés utilisés selon l'invention est constituée de composés de formule générale (I-3) suivante : A family of preferred compounds used according to the invention consists of compounds of general formula (I-3) below:
R3, R4, R5, R6 et n étant tels que définis ci-dessus. R 3 , R 4 , R 5 , R 6 and n being as defined above.
Selon un mode de réalisation, dans les formules (I), (1-1 ), (I-2) ou (I-3) telles que définies ci-dessus, R4 est OH et R3 et R5 sont, indépendamment les uns des autres, H ou OH. According to one embodiment, in formulas (I), (1-1), (I-2) or (I-3) as defined above, R 4 is OH and R 3 and R 5 are, independently from each other, H or OH.
Une famille de composés préférés utilisés selon l'invention est constituée de composés de formule énérale (I-4) suivante : A family of preferred compounds used according to the invention consists of compounds of the following eneral formula (I-4):
R3, R5, R6 et n étant tels que définis ci-dessus. R 3 , R 5 , R 6 and n being as defined above.
Selon un mode de réalisation, dans les formules (I), (1-1 ), (I-2), (I-3) ou (I-4) telles que définies ci-dessus, n est égal à 2. According to one embodiment, in formulas (I), (1-1), (I-2), (I-3) or (I-4) as defined above, n is equal to 2.
Une famille de composés préférés utilisés selon l'invention est constituée de composés de formule générale (I-5) suivante : A family of preferred compounds used according to the invention consists of compounds of the following general formula (I-5):
R3, R5 et R6 étant tels que définis ci-dessus. R 3 , R 5 and R 6 being as defined above.
Une famille de composés préférés utilisés selon l'invention est constituée de composés de formule générale (I-6) suivante : A family of preferred compounds used according to the invention consists of compounds of the following general formula (I-6):
Selon un mode de réalisation avantageux, le composé aminosulfonate employé selon la présente invention répond à l'une des formules suivantes : According to an advantageous embodiment, the aminosulphonate compound employed according to the present invention corresponds to one of the following formulas:
De pré ule suivante Next pre ule
A titre de composé aminosulfonate, on peut utiliser selon l'invention l'un des produits commerciaux suivants : Mackam LS, MAckterra LS, Miranol CS, ou MiranolAs aminosulphonate compound, one of the following commercial products can be used according to the invention: Mackam LS, MAckterra LS, Miranol CS, or Miranol
JS. JS.
De préférence, la présente invention concerne l'utilisation du produit Mackam Preferably, the present invention relates to the use of the Mackam product
LS. Selon un mode de réalisation, l'aminosulfonate est employé essentiellement sous sa forme non protonée de formule (I), avec un rapport molaire forme protonée/forme non protonée inférieur à 10%, de préférence inférieur à 1 %. LS. According to one embodiment, the aminosulphonate is used essentially in its unprotonated form of formula (I), with a molar ratio protonated form / unprotonated form less than 10%, preferably less than 1%.
De préférence, la forme non protonée est le composé majoritaire.  Preferably, the unprotonated form is the major compound.
L'expression "rapport molaire forme protonée/forme non protonée" désigne le rapport entre le nombre de moles de la forme protonée de formule (Γ) et le nombre de moles de la forme non protonée de formule (I).  The expression "protonated form / non-protonated form molar ratio" refers to the ratio of the number of moles of the protonated form of formula (Γ) to the number of moles of the unprotonated form of formula (I).
La présente invention concerne également une méthode d'extraction d'hydrocarbures contenus dans une formation souterraine, comprenant l'injection sous pression au sein de ladite formation d'une composition moussante et d'un gaz propre à induire le foisonnement de ladite composition moussante, ladite composition moussante comprenant un composé de formule (I) tel que défini ci- dessus, optionnellement en association avec sa forme protonée de formule (Γ) telle que définie ci-dessus. The present invention also relates to a method for extracting hydrocarbons contained in a subterranean formation, comprising the injection under pressure within said formation of a foaming composition and a gas capable of inducing the expansion of said foaming composition, said foaming composition comprising a compound of formula (I) as defined above, optionally in combination with its protonated form of formula (Γ) as defined above.
Selon l'invention, la méthode d'extraction ci-dessus peut être mise en œuvre soit en formant la mousse après injection dans la formation souterraine (formation in situ de mousse) soit en préformant la mousse avant injection dans la formation souterraine (formation ex situ de mousse).  According to the invention, the above extraction method can be implemented either by forming the foam after injection in the underground formation (in situ formation of foam) or by preforming the foam before injection into the subterranean formation (ex formation). foam).
Selon un mode de réalisation particulier, la méthode ci-dessus est mise en œuvre avec une composition moussante ne comprenant pas de tensioactif anionique. According to a particular embodiment, the above method is implemented with a foaming composition not comprising anionic surfactant.
Selon un mode de réalisation, la méthode ci-dessus est mise en œuvre avec une composition moussante ne comprenant pas de stabilisateur de mousse additionnel. Selon un mode de réalisation, la méthode ci-dessus est mise en œuvre avec une composition moussante ne comprenant pas de stabilisateur de mousse autre que le composé aminosulfonate selon l'invention.  According to one embodiment, the above method is implemented with a foaming composition that does not include additional foam stabilizer. According to one embodiment, the above method is implemented with a foaming composition comprising no foam stabilizer other than the aminosulfonate compound according to the invention.
Selon un mode de réalisation, la méthode susmentionnée est mise en œuvre avec une composition moussante comprenant un composé de formule (1-1 ), (I-2), (I- 3), (I-4), (I-5) ou (I-6) telles que définies ci-dessus. According to one embodiment, the aforementioned method is carried out with a foaming composition comprising a compound of formula (I-1), (I-2), (I-3), (I-4), (I-5), ) or (I-6) as defined above.
Selon un mode de réalisation, dans la méthode susmentionnée, la composition moussante est une composition aqueuse, qui comprend de préférence le composé de formule (I), et optionnellement sa forme protonée (Γ), à hauteur de 0,01 % à 10% en masse, plus préférentiellement de 0,1 % à 1 % en masse par rapport à la masse totale d'eau. According to one embodiment, in the abovementioned method, the foaming composition is an aqueous composition, which preferably comprises the compound of formula (I), and optionally its protonated form (Γ), at the level of 0.01% to 10% by weight, more preferably from 0.1% to 1% by weight relative to the total weight of water.
Typiquement, une composition moussante selon l'invention comprend le composé de formule (I), et optionnellement sa forme protonée (Γ), à hauteur de 0,5% à 2% en masse par rapport à la masse totale de ladite composition.  Typically, a foaming composition according to the invention comprises the compound of formula (I), and optionally its protonated form (Γ), in an amount of 0.5% to 2% by weight relative to the total weight of said composition.
Selon un mode de réalisation, la méthode susmentionnée est mise en œuvre avec une co ule suivante : According to one embodiment, the aforementioned method is implemented with a following cost:
La présente invention concerne également une méthode d'extraction d'hydrocarbures contenus dans une formation souterraine, comprenant les étapes suivantes : The present invention also relates to a method for extracting hydrocarbons contained in an underground formation, comprising the following steps:
(a) l'injection sous pression au sein de ladite formation d'une composition moussante comprenant un composé aminosulfonate tel que défini ci-dessus,  (a) the injection under pressure within said formation of a foaming composition comprising an aminosulphonate compound as defined above,
(b) l'introduction sous pression au sein de ladite formation d'un gaz propre à induire le foisonnement de ladite composition moussante, et  (b) introducing under pressure into said formation a gas capable of inducing the expansion of said foaming composition, and
(c) l'extraction des hydrocarbures via un puits dans la formation souterraine. Selon un mode de réalisation, dans la méthode susmentionnée, la composition moussante peut comprendre de l'eau. Elle peut également comprendre un mélange de gaz propre à induire le foisonnement.  (c) the extraction of hydrocarbons via a well in the underground formation. According to one embodiment, in the aforementioned method, the foaming composition may comprise water. It may also include a mixture of clean gases to induce expansion.
Selon un mode de réalisation, les constituants, en particulier l'aminosulfonate et le gaz, sont mélangés avant d'être introduits dans la formation souterraine. Selon un autre mode de réalisation, ils peuvent être injectés à des instants différents, par exemple de façon séquentielle.  According to one embodiment, the constituents, in particular the aminosulphonate and the gas, are mixed before being introduced into the subterranean formation. According to another embodiment, they can be injected at different times, for example sequentially.
La présente invention concerne également une méthode d'extraction d'hydrocarbures contenus dans une formation souterraine, comprenant les étapes suivantes : (a) la formation d'une mousse à partir d'une composition moussante comprenant un composé aminosulfonate tel que défini ci-dessus et d'un gaz propre à induire le foisonnement de ladite composition moussante, The present invention also relates to a method for extracting hydrocarbons contained in an underground formation, comprising the following steps: (a) forming a foam from a foaming composition comprising an aminosulphonate compound as defined above and a gas capable of inducing the expansion of said foaming composition,
(b) l'injection de ladite mousse au sein de ladite formation, et  (b) injecting said foam into said formation, and
(c) l'extraction des hydrocarbures via un puits dans la formation souterraine.  (c) the extraction of hydrocarbons via a well in the underground formation.
La présente invention concerne également une méthode pour améliorer l'extraction d'hydrocarbures contenus dans une formation souterraine, comprenant les étapes suivantes : The present invention also relates to a method for improving the extraction of hydrocarbons contained in an underground formation, comprising the following steps:
(a) l'injection sous pression au sein de ladite formation d'une composition moussante comprenant un composé aminosulfonate tel que défini ci-dessus,  (a) the injection under pressure within said formation of a foaming composition comprising an aminosulphonate compound as defined above,
(b) l'introduction sous pression au sein de ladite formation d'un gaz propre à induire le foisonnement de ladite composition moussante, et  (b) introducing under pressure into said formation a gas capable of inducing the expansion of said foaming composition, and
(c) l'extraction des hydrocarbures via un puits dans la formation souterraine.  (c) the extraction of hydrocarbons via a well in the underground formation.
Dans le cadre des méthodes susmentionnées, le terme "gaz propre à induire le foisonnement" désigne un gaz tel que l'air, le dioxyde de carbone, l'azote, de la vapeur d'eau ou du gaz naturel, notamment présent dans la formation souterraine. Typiquement, ce gaz est du dioxyde de carbone ou du gaz naturel présent dans la formation souterraine. In the context of the abovementioned methods, the term "gas capable of inducing expansion" designates a gas such as air, carbon dioxide, nitrogen, water vapor or natural gas, in particular present in the underground formation. Typically, this gas is carbon dioxide or natural gas present in the underground formation.
La présente invention concerne également une méthode pour améliorer la stabilité des mousses dans une composition moussante aqueuse, comprenant une étape d'addition à ladite composition moussante aqueuse d'un composé aminosulfonate tel que défini ci-dessus. The present invention also relates to a method for improving the stability of foams in an aqueous foaming composition, comprising a step of adding to said aqueous foaming composition an aminosulphonate compound as defined above.
Selon un mode de réalisation, le stabilisateur de mousse selon l'invention, à savoir l'aminosulfonate tel que défini ci-dessus, augmente la stabilité de la mousse d'un fluide de traitement d'un puits de pétrole ("o/V well treatment fluid"). Selon un autre mode de réalisation, le stabilisateur de mousse décrit ici augmente la stabilité de la mousse d'une composition moussante qui peut être utilisée comme une partie d'un fluide de traitement d'un puits de pétrole. La composition moussante peut également être utilisée en combinaison avec un fluide de traitement d'un puits de pétrole dans un procédé à plusieurs étapes pour récupérer du pétrole d'une formation souterraine. Le stabilisateur de mousse peut être un élément d'un ensemble introduit seul dans la formation souterraine ou avec un autre fluide ou une autre composition, par exemple avec la composition moussante ou le fluide de traitement du puits de pétrole. According to one embodiment, the foam stabilizer according to the invention, namely the aminosulphonate as defined above, increases the stability of the foam of a treatment fluid of an oil well ("o / V well treatment fluid "). In another embodiment, the foam stabilizer described herein increases the foam stability of a foaming composition that can be used as part of a petroleum well processing fluid. The foaming composition may also be used in combination with an oil well treating fluid in a multi-step process for recovering oil from a subterranean formation. The foam stabilizer may be an element of an assembly introduced alone into the subterranean formation or with another fluid or other composition, for example with the foaming composition or the oil well treatment fluid.
La présente invention concerne également une méthode pour améliorer l'extraction de pétrole contenu dans une formation pétrolifère comprenant l'addition d'un stabilisateur de mousse selon l'invention à une composition moussante aqueuse ou à un fluide de traitement d'un puits de pétrole. The present invention also relates to a method for improving the oil extraction contained in an oil formation comprising the addition of a foam stabilizer according to the invention to an aqueous foaming composition or to a treatment fluid of an oil well. .
Selon un mode de réalisation, une composition moussante comprenant au moins un stabilisateur de mousse selon l'invention est introduite, par exemple injectée, dans un réservoir ou une formation souterraine à pression élevée pour pousser ou dégager le pétrole. La composition moussante, qui donne une forme ou une consistance de type mousse, entre et s'installe dans les fractures de la formation (i.e. dans les zones de perméabilité élevée) et détourne substantiellement un ou plusieurs gaz, ou un mélange gaz/tensioactif ou un mélange gaz/fluide aqueux vers la matrice pétrolifère moins perméable (i.e. dans les zones de faible perméabilité). According to one embodiment, a foaming composition comprising at least one foam stabilizer according to the invention is introduced, for example injected, into a tank or an underground formation at high pressure to push or release the oil. The foaming composition, which gives a foam-like shape or consistency, enters and settles in formation fractures (ie in areas of high permeability) and substantially diverts one or more gases, or a gas / surfactant mixture or an aqueous gas / fluid mixture to the less permeable oil matrix (ie in areas of low permeability).
Ceci peut ensuite mobiliser le pétrole et/ou gaz piégé de la matrice à travers le réseau de fractures. La composition moussante agit comme une barrière pour entrer dans le réseau de fractures. Lorsque le réseau de fractures est efficacement ou substantiellement colmaté, le gaz s'infiltre dans la matrice poreuse de la formation à la place du réseau de fractures. Le gaz pousse le pétrole piégé dans la matrice vers le réseau de fractures, où il peut être facilement récupéré par des moyens conventionnels.  This can then mobilize oil and / or trapped gas from the matrix through the fracture network. The foaming composition acts as a barrier to enter the fracture network. When the fracture network is effectively or substantially clogged, the gas infiltrates the porous matrix of the formation in place of the fracture network. The gas pushes the trapped oil into the matrix towards the fracture network, where it can be easily recovered by conventional means.
Selon un mode de réalisation, d'autres tensioactifs ou polymères peuvent être présents dans la composition moussante. Les tensioactifs peuvent agir pour diminuer la tension interfaciale entre le fluide de traitement et le pétrole piégé dans la matrice de la formation et/ou augmenter la viscosité de l'eau injectée pendant le traitement. Dans certains modes de réalisation, le gaz utilisé dans l'opération d'inondation/d'injection de gaz ("gas flooding" en anglais) décrite ici est un gaz ou une combinaison d'un gaz et de fluides aqueux. Le fluide peut être dans un état supercritique. Le gaz ou le mélange gaz/fluide peut être injecté par exemple par injection continue. Dans certains modes de réalisation, on utilise une injection de gaz en combinaison avec une injection d'eau dans un procédé dit WAG ("water- alternating-gas" en anglais). According to one embodiment, other surfactants or polymers may be present in the foaming composition. The surfactants may act to decrease the interfacial tension between the process fluid and the oil entrapped in the matrix of the formation and / or increase the viscosity of the water injected during the treatment. In some embodiments, the gas used in the gas flooding operation described herein is a gas or a combination of a gas and aqueous fluids. The fluid can be in a supercritical state. The gas or the gas / fluid mixture can be injected, for example by continuous injection. In some embodiments, an injection of gas in combination with an injection of water in a process called WAG ("water-alternating-gas" in English).
Selon l'invention, le terme "réservoir" englobe le terme "formation pétrolifère" (incluant mais non limitée aux formations pétrolifères carbonate) étant donné qu'une telle formation est typiquement située dans un réservoir. Un ou plusieurs puits peuvent être situés à proximité du réservoir et/ou de la formation dans le but d'extraire du pétrole. Le fluide de traitement peut être introduit via un puits, un trou de forage ou une ouverture dans le réservoir. Le fluide de traitement sera alors introduit à une pression suffisamment élevée pour assurer une infiltration substantielle du fluide de traitement dans le réseau de fractures de la formation et une exposition substantielle de la matrice poreuse de cette formation. Le pétrole peut être extrait au même endroit ou à un endroit autre que le point d'introduction du fluide de traitement.  According to the invention, the term "reservoir" encompasses the term "oil formation" (including but not limited to carbonate oil formations) since such formation is typically located in a reservoir. One or more wells may be located near the reservoir and / or formation for the purpose of extracting oil. The treatment fluid may be introduced via a well, a borehole, or an opening in the reservoir. The treatment fluid will then be introduced at a pressure high enough to ensure substantial infiltration of the treatment fluid into the fracture network of the formation and substantial exposure of the porous matrix of this formation. The oil may be extracted at the same location or at a location other than the point of introduction of the process fluid.
Ainsi, la présente invention concerne également l'utilisation des composés aminosulfonates susmentionnés dans le domaine pétrolier. En particulier, comme indiqué ci-dessus, ces composés peuvent être utilisés dans la mise en œuvre de procédés de récupération assistée du pétrole pour le contrôle de la mobilité des gaz ("gas mobility controi' en anglais). Thus, the present invention also relates to the use of the aminosulphonate compounds mentioned above in the petroleum field. In particular, as indicated above, these compounds can be used in the implementation of enhanced oil recovery processes for the control of gas mobility ("gas mobility controi" in English).
Selon la présente invention, le terme "contrôle de la mobilité" doit être interprété selon la signification la plus large et inclut également un procédé dans lequel l'efficacité de balayage ("sweep efficiency" en anglais) d'un réservoir ou d'une formation pétrolifère est améliorée.  According to the present invention, the term "mobility control" is to be interpreted in the broadest sense and also includes a method in which the sweep efficiency of a reservoir or oil formation is improved.
Ces composés peuvent également être utilisés dans des mousses destinées à enlever l'eau des puits ("dewatering" en anglais). These compounds can also be used in foams for removing water from the wells ("dewatering" in English).
Ils peuvent être utilisés en outre pour la fracturation avec des mousses ("foam fracturing" en anglais), ce qui consiste à injecter un liquide comprenant les composés de l'invention sous de très fortes pressions afin de casser le puits.  They can also be used for foam fracturing, which consists in injecting a liquid comprising the compounds of the invention under very high pressure in order to break the well.
Enfin, les composés de l'invention peuvent également être utilisés pour former des mousses destinées au nettoyage de sols. Exemple 1 : Finally, the compounds of the invention can also be used to form foams for cleaning floors. Example 1
Stabilité de mousses obtenues avec les aminosulfonates de l'invention à 90°C  Stability of foams obtained with the aminosulphonates of the invention at 90 ° C.
La stabilité de la mousse formée avec une formulation donnée est directement liée à l'efficacité de cette formule à contrôler la mobilité du gaz dans un milieu poreux. The stability of the foam formed with a given formulation is directly related to the effectiveness of this formula in controlling the mobility of the gas in a porous medium.
Dans cet exemple, on obtient une stabilité comparable à celle obtenue avec des formulations moussantes commerciales comprenant plusieurs composés. Ceci est particulièrement intéressant car les formulations moussantes à composé unique selon l'invention sont très faciles à préparer. In this example, a stability comparable to that obtained with commercial foaming formulations comprising several compounds is obtained. This is particularly interesting since the single compound foaming formulations of the invention are very easy to prepare.
Les formulations sont préparées à 0,5% en poids dans une saumure à 50 g/L de NaCI. Elles sont équilibrées à 90°C pendant une heure dans des récipients fermés et la mousse est alors générée dans ces récipients fermés par une agitation mécanique très forte. The formulations are prepared at 0.5% by weight in brine at 50 g / l NaCl. They are equilibrated at 90 ° C for one hour in closed containers and the foam is then generated in these closed containers by a very strong mechanical agitation.
La hauteur de la mousse est mesurée au cours du temps afin d'évaluer la résistance de la mousse vis-à-vis de la coalescence. Les résultats sont résumés dans le tableau 1 pour les composés suivants : The height of the foam is measured over time to evaluate the resistance of the foam to coalescence. The results are summarized in Table 1 for the following compounds:
- Mackam LS, un cocoyl sulfonate selon la présente invention, dans une solution à pH=10 et dans une solution ajustée à pH=7 en utilisant de l'acide chlorhydrique ;  Mackam LS, a cocoyl sulfonate according to the present invention, in a solution at pH = 10 and in a solution adjusted to pH = 7 using hydrochloric acid;
- un mélange 1 :1 Rhodacal A246L (C14-C16 alpha oléfine sulfonate)/Mackam 35 (cocamidopropyl bétaïne), connu comme une excellente formulation moussante grâce à l'effet de la bétaïne pour améliorer les propriétés de la mousse, dans une solution à pH=7 et dans une solution ajustée à pH=10 en utilisant de l'hydroxyde de sodium ; et  a 1: 1 mixture Rhodacal A246L (C14-C16 alpha olefin sulfonate) / Mackam (cocamidopropyl betaine), known as an excellent foaming formulation thanks to the effect of betaine to improve the properties of the foam, in a solution with pH = 7 and in a solution adjusted to pH = 10 using sodium hydroxide; and
- un mélange 1 :1 Rhodacal A246L/Mackam CBS (cocamidopropyl hydroxysultaïne), connu également comme une excellente formulation moussante, dans une solution à pH=7 et dans une solution ajustée à pH=10 en utilisant de l'hydroxyde de sodium.  a 1: 1 mixture of Rhodacal A246L / Mackam CBS (cocamidopropyl hydroxysultaine), also known as an excellent foaming formulation, in a solution at pH = 7 and in a solution adjusted to pH = 10 using sodium hydroxide.
Tableau 1 : Etude comparative de la stabilité des mousses pour plusieurs formulations Temps de demi-vie Temps de demi-vie Table 1: Comparative study of foam stability for several formulations Half-life time Half-life time
Produit de la mousse de la mousse à  Product of the mousse of the foam to
à pH 10 (minutes) pH 7 (minutes)  at pH 10 (minutes) pH 7 (minutes)
Mackam LS 210 210  Mackam LS 210 210
Rhodacal A246L / Rhodacal A246L /
210 240  210,240
Mackam 35 1 :1  Mackam 35 1: 1
Rhodacal A246L / Rhodacal A246L /
70 240  70,240
Mackam CBS 1 :1  Mackam CBS 1: 1
Au vu des résultats, on observe que le produit Mackam LS, correspondant à un composé selon l'invention, permet d'obtenir des performances moussantes égales voire supérieures à celles obtenues avec les deux mélanges commerciaux, même lorsque celui-ci est utilisé comme composé unique. In view of the results, it is observed that the Mackam LS product, corresponding to a compound according to the invention, makes it possible to obtain foaming performance equal to or even greater than that obtained with the two commercial mixtures, even when it is used as a compound. unique.
Ainsi, ce produit fournit d'excellentes performances en comparaison aux produits commerciaux, tout en présentant l'avantage supplémentaire d'être beaucoup plus facile à préparer (composé unique).  Thus, this product provides excellent performance compared to commercial products, while having the added benefit of being much easier to prepare (single compound).
Exemple 2 : Example 2
Adsorption sur des roches-réservoirs de formulations à base d'aminosulfonates selon l'invention et comparaison avec des formulations commerciales  Rock adsorption of aminosulphonate-based formulations according to the invention and comparison with commercial formulations
En plus de la performance technique, les performances économiques liées à la perte de produit par adsorption sur les roches-réservoirs jouent un rôle clé dans les procédés de récupération assistée du pétrole. In addition to technical performance, the economic performance of adsorptive adsorption on reservoir rocks plays a key role in enhanced oil recovery processes.
Dans cet exemple, on démontre l'adsorption moindre du produit Mackam LS par rapport aux produits commerciaux. In this example, the lower adsorption of Mackam LS product compared to commercial products is demonstrated.
Les formulations sont préparées à 0,5% en poids dans une saumure à 50 g/L de NaCI et dans de l'eau de mer standard. The formulations are prepared at 0.5% by weight in brine at 50 g / L NaCl and in standard seawater.
Les formulations sont mises en contact avec une roche-réservoir broyée calibrée à 50°C pendant 24 heures. Le liquide surnageant est ensuite titré et l'adsorption est évaluée en utilisant la différence de concentration entre le liquide surnageant et la solution initiale. The formulations are brought into contact with a crushed reservoir rock calibrated at 50 ° C. for 24 hours. The supernatant liquid is then titrated and adsorption is evaluated using the difference in concentration between the supernatant and the initial solution.
Les résultats sont présentés dans le tableau 2 pour l'adsorption sur du grès de Berea et du carbonate de Lavoux, pour les trois formulations suivantes : The results are shown in Table 2 for adsorption on Berea sandstone and Lavoux carbonate, for the following three formulations:
- Mackam LS, un cocoyl sulfonate selon la présente invention, dans une solution à pH=10 ;  Mackam LS, a cocoyl sulfonate according to the present invention, in a solution at pH = 10;
- un mélange 1 :1 Rhodacal A246L (C14-C16 alpha oléfine sulfonate)/Mackam 35 (cocamidopropyl bétaïne), connu comme une excellente formulation moussante grâce à l'effet de la bétaïne pour améliorer les propriétés de la mousse, dans une solution à pH=7 (mélange 1 ) ; et  a 1: 1 mixture Rhodacal A246L (C14-C16 alpha olefin sulfonate) / Mackam (cocamidopropyl betaine), known as an excellent foaming formulation thanks to the effect of betaine to improve the properties of the foam, in a solution with pH = 7 (mixture 1); and
- un mélange 1 :1 Rhodacal A246L/Mackam CBS (cocamidopropyl hydroxysultaïne), connu également comme une excellente formulation moussante, dans une solution à pH=7 (mélange 2).  a 1: 1 mixture of Rhodacal A246L / Mackam CBS (cocamidopropyl hydroxysultaine), also known as an excellent foaming formulation, in a solution at pH = 7 (mixture 2).
Tableau 2 : Adsorption moyenne de formulations moussantes sur des roches grès et carbonate dans deux conditions de salinité Table 2: Average adsorption of foaming formulations on sandstone and carbonate rocks under two salinity conditions
On peut donc constater que l'adsorption de formulations à base de Mackam LS est systématiquement inférieure ou égale à celle obtenue avec des formulations commerciales (mélanges 1 et 2). It can therefore be seen that the adsorption of Mackam LS formulations is systematically less than or equal to that obtained with commercial formulations (mixtures 1 and 2).
On observe une forte amélioration dans l'eau de mer et sur des roches carbonate, ce qui représente un très grand challenge pour les formulations moussantes en termes d'adsorption.  There is a strong improvement in seawater and on carbonate rocks, which represents a great challenge for foaming formulations in terms of adsorption.
Ainsi, les formulations à base d'aminosulfonate selon l'invention fournissent dans certaines conditions une stabilité de mousse comparable à celle obtenue avec des formulations moussantes commerciales présentant une adsorption inférieure, ce qui résulte en une meilleure efficacité du procédé d'un point de vue économique.  Thus, the aminosulfonate formulations according to the invention provide under certain conditions a foam stability comparable to that obtained with commercial foaming formulations having a lower adsorption, which results in a better efficiency of the process from a point of view economic.

Claims

REVENDICATIONS
1. Utilisation d'un composé aminosulfonate répondant à la formule (I) suivante : 1. Use of an aminosulphonate compound corresponding to the following formula (I):
R1R2N-CHR3-CHR4-CHR5-S03 " (I) R 1 R 2 N-CHR 3 -CHR 4 -CHR 5 -S0 3 " (I)
où : or :
• R1 est un radical alkyle ou alkylamido ; R 1 is an alkyl or alkylamido radical;
• R2 est un radical alkyle, éventuellement hydroxylé ; R 2 is an alkyl radical, optionally hydroxylated;
• R3, R4 et R5 sont, indépendamment les uns des autres, H ou OH ; étant entendu qu'au moins un des groupes R3 ; R4 et/ou R5 est OH, pour stabiliser une mousse, en particulier une mousse employée pour la récupération d'hydrocarbures présents dans une formation souterraine, ledit composé de formule (I) pouvant optionnellement être employé conjointement avec sa forme protonée de formule (Γ) suivante : R1R2NH+-CHR3-CHR4-CHR5-S03 ". R 3 , R 4 and R 5 are, independently of one another, H or OH; it being understood that at least one of the groups R 3 ; R 4 and / or R 5 is OH, for stabilizing a foam, in particular a foam used for the recovery of hydrocarbons present in a subterranean formation, said compound of formula (I) optionally being able to be used together with its protonated form of formula (Γ) R 1 R 2 NH + -CHR 3 -CHR 4 -CHR 5 -S0 3 " .
2. Utilisation selon la revendication 1 , dans laquelle l'aminosulfonate est employé essentiellement sous sa forme non protonée de formule (I), avec un rapport molaire forme protonée (Γ) /forme non protonée (I) inférieur à 10%, de préférence inférieur à 1 %. 2. Use according to claim 1, wherein the aminosulphonate is used essentially in its unprotonated form of formula (I), with a molar ratio protonated form (Γ) / unprotonated form (I) of less than 10%, preferably less than 1%.
3. Utilisation selon la revendication 1 ou 2, dans laquelle R1 est un radical alkylamido comprenant de 2 à 24 atomes de carbone. 3. Use according to claim 1 or 2, wherein R 1 is an alkylamido radical having 2 to 24 carbon atoms.
4. Utilisation selon l'une quelconque des revendications 1 à 3, dans laquelle R2 est un radical hydroxyalkyle comprenant de 2 à 20, de préférence de 2 à 10, atomes de carbone. 4. Use according to any one of claims 1 to 3, wherein R 2 is a hydroxyalkyl radical comprising from 2 to 20, preferably from 2 to 10, carbon atoms.
5. Utilisation selon l'une quelconque des revendications 1 à 4, dans laquelle R2 est un radical hydroxyéthyle. 5. Use according to any one of claims 1 to 4, wherein R 2 is a hydroxyethyl radical.
6. Utilisation selon l'une quelconque des revendications 1 à 5, dans laquelle le composé aminosulfonate ré ond à la formule suivante : The use according to any one of claims 1 to 5, wherein the aminosulphonate compound has the following formula:
R2, R3, R4 et R5 étant tels que définis dans l'une quelconque des revendications 1 à 5, R 2 , R 3 , R 4 and R 5 being as defined in any one of claims 1 to 5,
R6 représentant un radical alkyle, linéaire ou ramifié, comprenant de 2 à 24 atomes de carbone, et R 6 represents a linear or branched alkyl radical comprising from 2 to 24 carbon atoms, and
n représentant un nombre entier allant de 2 à 5.  n represents an integer ranging from 2 to 5.
7. Utilisation selon l'une quelconque des revendications 1 à 6, dans laquelle le comp nte : 7. Use according to any one of claims 1 to 6, wherein the compnte:
R6 représentant un radical alkyle, linéaire ou ramifié, comprenant de 2 à 24 atomes de carbone. R 6 represents a linear or branched alkyl radical comprising from 2 to 24 carbon atoms.
8. Utilisation selon l'une quelconque des revendications 1 à 7, dans laquelle le composé aminosulfonate répond à l'une des formules suivantes : Use according to any one of claims 1 to 7, wherein the aminosulphonate compound has one of the following formulas:
9. Utilisation selon l'une quelconque des revendications 1 à 8, dans laquelle le c : Use according to any one of claims 1 to 8, wherein the c:
10. Méthode d'extraction d'hydrocarbures contenus dans une formation souterraine, comprenant l'injection sous pression au sein de ladite formation d'une composition moussante et d'un gaz propre à induire le foisonnement de ladite composition moussante, ladite composition moussante comprenant un composé aminosulfonate de formule (I) tel que défini dans l'une quelconque des revendications 1 à 9, optionnellement en association avec sa forme protonée (Γ). 10. A method for extracting hydrocarbons contained in a subterranean formation, comprising the injection under pressure within said formation of a foaming composition and a gas adapted to induce the expansion of said foaming composition, said foaming composition comprising an aminosulphonate compound of formula (I) as defined in any one of claims 1 to 9, optionally in combination with its protonated form (Γ).
11. Méthode selon la revendication 10, dans laquelle la composition moussante est une composition aqueuse, qui comprend de préférence le composé aminosulfonate de formule (I) et optionnellement sa forme protonée (Γ), à hauteur de 0,01 % à 10% en masse, plus préférentiellement de 0,1 % à 1 % en masse par rapport à la masse totale d'eau. 11. The method of claim 10, wherein the foaming composition is an aqueous composition, which preferably comprises the aminosulfonate compound of formula (I) and optionally its protonated form (Γ), from 0.01% to 10% by weight. mass, more preferably from 0.1% to 1% by weight relative to the total mass of water.
12. Méthode selon la revendication 10 ou 1 1 , dans laquelle le composé aminosulfon The method of claim 10 or 11, wherein the aminosulfon compound
13. Méthode selon l'une des revendication 10 à 12, dans laquelle la composition moussante ne comprend pas de stabilisateur de mousse autre qu'un ou plusieurs composés aminosulfonate de formule (I). 13. Method according to one of claims 10 to 12, wherein the foaming composition does not comprise foam stabilizer other than one or more aminosulphonate compounds of formula (I).
14. Méthode selon l'une des revendication 10 à 12, dans laquelle la composition moussante ne comprend pas de tensioactif anionique. 14. Method according to one of claims 10 to 12, wherein the foaming composition does not include anionic surfactant.
EP15722143.3A 2014-05-15 2015-05-04 Aminosulphonate foam stabilizers Withdrawn EP3143097A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1401088A FR3021052A1 (en) 2014-05-15 2014-05-15 FOAM STABILIZERS OF THE AMINOSULFONATE TYPE
PCT/EP2015/059750 WO2015173052A1 (en) 2014-05-15 2015-05-04 Aminosulphonate foam stabilizers

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WO (1) WO2015173052A1 (en)

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US10370583B2 (en) 2019-08-06
US20170107421A1 (en) 2017-04-20
WO2015173052A1 (en) 2015-11-19

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