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)

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• 2014
  • 2014-05-15 FR FR1401088A patent/FR3021052A1/fr active Pending
• 2015
  • 2015-05-04 EP EP15722143.3A patent/EP3143097A1/de not_active Withdrawn
  • 2015-05-04 US US15/311,305 patent/US10370583B2/en not_active Expired - Fee Related
  • 2015-05-04 WO PCT/EP2015/059750 patent/WO2015173052A1/fr not_active Ceased

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