STEEL-COMPATIBLE FOAMING COMPOSITION FOR ASSISTED HYDROCARBON RECOVERY

Abstract

STEEL-COMPATIBLE FOAMING COMPOSITION FOR AID-ASSISTED HYDROCARBON RECOVERY The present invention relates to a corrosion-inhibiting foaming composition comprising a) a surfactant composition including at least one amphoteric compound and optionally one or more additional surfactants selected from ionic and non-ionic surfactants, and b) at least one sulfur compound. The invention also relates to the use of said foaming composition to prevent corrosion formation, as well as the process for assisted hydrocarbon recovery employing said foaming composition. Fig.: none

Description

Title of the invention: STEEL-COMPATIBLE FOAMING COMPOSITION FOR ENHANCED HYDROCARBON RECOVERY

[0001] The present invention relates to the field of enhanced recovery of hydrocarbons, in particular oil and gas, and relates more particularly to foaming additives used for enhanced recovery of hydrocarbons.

[0002] Foaming compositions for the enhanced recovery of hydrocarbons, mainly oil and gas, are currently commonly used by injection into production wells. Indeed, the drop in pressure of the hydrocarbon reservoir over time implies a reduction in the flow rates of the produced fluids, such as water, liquid hydrocarbons and gas. This can result in poor entrainment of the densest fluids in the wells, whether vertical or not, and thus an accumulation of said densest fluids. This accumulation in turn leads to an increase in the hydrostatic column pressure, which tends to reduce production. The addition of foaming composition, for example via the installation of a gas injection extraction system ("gas lift" in English), makes it possible to entrain the fluids, reduce the column pressure and thus increase production.

[0003] However, certain foaming compositions may be incompatible with the various metallic materials of the wells, pipes, injection lines and others, into which they are injected. This incompatibility is all the more frequent when the metal is unalloyed steel. This incompatibility results in particular in a risk of corrosion of the steel, corrosion which must be avoided as much as possible.

[0004] Corrosion problems are indeed frequent, whether due to generalized corrosion and / or crevice corrosion (also called "crevice corrosion" or "under-joint corrosion"). These corrosion phenomena particularly impact steel installations, more specifically non-alloy steels, and most often where the products are concentrated. Corrosion points thus often appear in storage, in injection lines, at injection points, or elsewhere.

[0005] The literature provides numerous examples of foaming compositions for enhanced hydrocarbon recovery, such as for example patents US7422064 or US7823647. However, these documents do not address corrosion problems, particularly in storage and injection lines, corrosion problems which are often linked to the use of such foaming compositions.

[0006] Document US8551925 discloses foaming agents comprising imidazoline derivatives and more particularly formulations comprising an imidazoline with a betaine, an alcohol and water. These formulations are also indicated as having anti-corrosive properties, however, crevice (or under-joint) corrosion is not mentioned. Only problems of generalized corrosion once the product is injected into the production lines are envisaged.

[0007] Patent EP3103852 also discloses a foaming and non-corrosive composition, without however mentioning the problems of crevice corrosion.

[0008] However, there remains a need for foaming compositions which are effective on the one hand in combating generalized corrosion, but also against crevice corrosion of steels, and in particular non-alloyed steels.

[0009] Still other objectives will appear in the remainder of this disclosure. The inventors have now discovered that the aforementioned objectives are solved in whole or at least in part thanks to the present invention, the description of which follows.

[0010] Thus, and according to a first aspect, the present invention relates to a foaming, corrosion-inhibiting composition, comprising:

[0011] a) a surfactant composition comprising at least one amphoteric surfactant compound and optionally one or more additional surfactant compounds chosen from ionic and non-ionic surfactant compounds, and

[0012] b) at least one sulfur molecule.

[0013] In the context of the present invention, a foaming composition is a composition comprising at least one surfactant whose surface tension value is sufficiently low to produce a foam. This "foam" allows in particular the reduction of the density of the production fluid and the reduction of the hydrostatic pressure of the fluid column in the hydrocarbon production well. Thus, the presence of a foaming composition generally makes it possible to observe a potential increase in the production of the wells.

[0014] By "amphoteric surfactant compound" is meant a surfactant compound which can have a role which is sometimes acidic, sometimes basic, according to the classical definition used in the field of chemistry. An amphoteric surfactant compound which is particularly suitable for the present invention is a zwitterion. A particularly preferred zwitterion is chosen from betaines and sultaines. A preferred group of betaines and sultaines particularly suitable for the purposes of the invention includes, by way of non-limiting example, alkylbetaines, alkylarylbetaines, arylalkylbetaines, alkylamidopropylbetaines, alkylarylamidopropylbetaines, arylalkylamidopropylbetaines, alkylaminopropylbetaines, alkylarylaminopropylbetaines, arylalkylaminopropylbetaines, alkylsultaines, alkylarylsultaines, arylalkylsultaines, alkylamidopropylhydroxysultaines, as well as mixtures of two or more of them in any proportions.

[0015] As another amphoteric surfactant compound which may be included in the composition of the present invention, in addition to or as a substitute for the zwitterions cited above, mention may be made, as non-limiting examples, of alkylamphoacetates, alkylamphodiacetates, alkylamphopropionates, as well as mixtures of two or more of them in all proportions.

[0016] The additional surfactant(s) which may be present in composition a) are chosen from ionic surfactants (i.e. cationic or anionic), and non-ionic surfactants.Preferred additional surfactants include, but are not limited to, alkyl(aryl)(ether)sulfates, alkyl(aryl)sulfonates, alkyl(aryl)ester phosphates, alkyl(aryl)carboxylates, alkylsulfosuccinates, quaternary ammonium salts, alkylamine oxides, alkylamine ethoxylates, alkylamide ethoxylates, fatty acid ethoxylates, fatty alcohol ethoxylates, alkylethercarboxylates, alkylamide carboxylates, alkyl(poly)glucosides, alkylsorbitan esters, ethyleneoxy-propyleneoxy (EO-PO) block copolymers, alkylisothionates, alkylglycinates, alkylsarcosinates, alkylsulfosuccinates, alkylglutamates, alkyllactilates, alkyltaurates, alkylsulfoacetates, as well as mixtures of two or more of them in any proportions.

[0017] By sulfur molecule as component b), we preferably mean sulfur molecules chosen from: - mercaptans of formula RSH, where R represents a hydrocarbon chain, linear or branched, saturated or unsaturated, containing from 1 to 12 carbon atoms, and optionally one or more heteroatoms, chosen from nitrogen, oxygen and sulfur, and optionally one or more cycle(s), - mercapto acids of formula HOOC-R'-SH, where R' represents a divalent, linear or branched, saturated or unsaturated hydrocarbon radical, containing from 1 to 12 carbon atoms, and optionally one or more heteroatoms, chosen from nitrogen, oxygen and sulfur, and optionally one or more cycle(s), as well as the salts of said mercapto acids, - dithiols and disulfides of formula RrS-S-R2, where Ri and R2 each represent, independently of one another, a linear or branched, saturated or unsaturated hydrocarbon chain, containing from 1 to 12 carbon atoms, which may contain one or more heteroatoms chosen from nitrogen, oxygen and sulfur, and optionally one or more cycle(s), - as well as mixtures of two or more of said sulfur molecules, in all proportions.

[0018] Examples of sulfur molecules suitable for the purposes of the present invention include thioglycolic acid, sodium thioglycolate, sodium thiosulfate, sodium thiocyanate, mercaptopropionic acid, tert-butyl mercaptan, ethylhexyl thioglycolate, mercaptoethanol, thioglycolic acid disulfides, 3-mercaptopropionic acid (AMP) and its salts, 1,8-dhnercapto-3,6-di-oxa-octane (DMDO), bis-(2-mercaptoethyl)ether, thiourea, mercaptobenzothiazolates, 2-[(dithiocarboxy)thio]-acetic acid sodium salt (D8) (CAS no. 86932-91-4), as well as mixtures of two or more of them. in all proportions.

[0019] Still other examples include ammonium thiosulfite, ammonium thiosulfate, potassium thiosulfate, potassium thiosulfite, ammonium thiocyanate, calcium thiocyanate, sodium thioglycolate, ammonium thioglycolate, 1,2-diethylthiourea, propylthiourea, 1,1-diphenylthiourea, thiocarbanilide, 1,2-dibutylthiourea, dithiourea thioacetamide, thionicotimide, thiobenzamide, 2-mercaptoethanol, 3-(methylthio)propanal, thioacetic acid, cysteamine, 3-chloro-1-propanethiol, 1-mercapto-2-propanol, 2,3-dimercapto-l,10-propanol, 2-methoxyethanethiol, 3-mercapto-1-propanol, 2,3-dimercapto-l-propanol, 1-thioglycerol, 1,3-propanedithiol, mercaptosuccinic acid, N-carbamoyl-L-cysteine, N-acetylcysteamine, 4-mercapto-l-butanol, 1-butanedithiol, 1,4-butanedithiol, 2,2'-thiodiethanethiol, 4-cyano-l-butanethiol, cyclopentanethiol, 1,5-pentanedithiol,2-methyl-1-butanethiol, 2,3,5,6-tetrafluorobenzenethiophenol, 4-chlorothiophenol, 2-mercaptophenol, thiophenol, cyclohexylthiol, 4-mercaptobenzoic acid, thiosalicylic acid, 2-ethylhexanethiol, compounds of formula CnH2n+iSH, with n between 1 and 10, limits inclusive, as well as mixtures of two or more of them in all proportions.

[0020] It is also possible to use, as sulfur molecule, amino acids carrying a sulfur atom, and for example and in a non-limiting manner cysteine, homocysteine, cystine, homocystine, penicillamine, thiorphan, tiopronin.

[0021] The sulfur molecule is preferably present in the composition according to the present invention at a dose of between 0.001% and 2%, preferably 0.005% and 1%, more preferably 0.005% to 0.1%, and advantageously 0.005% and 0.01%, limits included, the percentages being expressed by weight, relative to the total weight of the composition.

[0022] According to a preferred aspect, the composition of the invention further comprises at least one solvent, preferably a polar solvent, or a non-polar solvent or a combination thereof. Examples of solvents particularly suited to the needs of the invention include: - water, including salt water, sea water, - alcohols, including alcohols of formula R-OH, where R is as defined above, and such as methanol, ethanol, propanol, isopropanol, butanol, 2-ethoxyethanol, hexanol, octanol, 2-butoxyethanol, - glycols, glycol ethers and their derivatives, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, ethylene glycol monobutyl ether, and others, - ketones, such as cyclohexanone, di-isobutyl ketones, N-methylpyrrolidinone, N,N-dimethylformamide, and others, as well as the mixture of two or more of them in any proportions.

[0023] Preferably, the solvent(s) are chosen from water-miscible solvents (including salt water and sea water), such as, for example, glycols, glycol ethers, methanol, ethanol, propanol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, to name only the main ones among them, in a non-limiting manner.

[0024] In addition to the presence of possible solvents, in particular such as water and / or organic solvent(s) as indicated above, the composition according to the present invention may also comprise one or more other additives commonly used in the field of enhanced hydrocarbon recovery.

[0025] Among these additives we can for example cite: - pH modifiers, - mineral anti-deposits, - corrosion inhibitors, - hydrogen sulfide inhibitors, - oxygen scavengers, - demulsifiers, - anti-asphaltenes, - anti-paraffins, - oil removers, - “pour point reducers” (or “pour point depressants” in English), - biocides, - gas hydrate anti-caking agents, - thermodynamic inhibitors of gas hydrates, - gas hydrate kinetic inhibitors, - as well as mixtures of two or more of these additives in any proportions.

[0026] The pH modifiers may for example be alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, alkaline earth metal bicarbonates, as well as households thereof and combinations of two or more thereof. Preferably, examples of pH modifiers include sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, magnesium oxide, and magnesium hydroxide. According to one aspect of the invention, examples of pH modifiers are basic compounds used to increase the pH of the composition, and are, for example, inorganic or organic bases, such as sodium hydroxide, potassium hydroxide, neutralizing amines, and the like.

[0027] Among the mineral anti-deposit agents useful in the context of the present invention, mention may be made, by way of non-limiting examples, of phosphates, phosphate esters, phosphoric acids, phosphonates, phosphonic acids, polyacrylamides, acrylamidomethylpropanesulfonate / acrylic acid copolymers (AMPS / AA), phosphinate / maleic acid copolymers (PHOS / MA), sulfonates of polymaleic acid / acrylamidomethylpropanesulfonate terpolymers (PMA / AA / AMPS).

[0028] The anti-corrosion agents which can be used in the context of the present invention are, for example, those described in the work “Production Chemicals for the OU and Gas Industry”, Malcolm A. Kelland, CRC Press, 2nd edition, (2014), 194-212. More specifically, non-limiting examples of anti-corrosion agents include phosphoric esters, organonitrogen compounds, sulfur molecules generally comprising one or more heteroatoms such as nitrogen and oxygen, carboxylic salts of amines, quaternary ammoniums, amidoamines and imidazolines, ethoxylated and / or propoxylated amines and amidoamines, amides, heterocyclic compounds bearing a charged nitrogen atom (such as pyrimidinium, pyridinium, quinolinium, piperazinium), ionic salts of the cationic and anionic species cited in this paragraph, polymeric amine esters, quaternized polymeric amine esters, and combinations of all these molecules.

[0029] Non-limiting examples of hydrogen sulfide inhibitors include oxidants (e.g., inorganic peroxides, such as sodium peroxide or chlorine dioxide), aldehydes (e.g., comprising 1 to 10 carbon atoms such as formaldehyde, glyoxal, glutaraldehyde, acrolein, methacrolein), triazines (e.g., monoethanolamine triazine, monomethylamine triazine, and triazines of several amines and mixtures thereof), condensation products of secondary or tertiary amines with aldehydes, and condensation products of alkyl alcohols with aldehydes.

[0030] The oxygen traps that can be used in the context of the present invention are, for example, those described in the work "Production Chemicals for the OU and Gas Industry", Malcolm A. Kelland, CRC Press, 2nd edition, (2014), 369-373. More specifically, non-limiting examples of oxygen traps that can be used in the context of the present invention include, by way of non-limiting examples, bisulfites, metabisulfites, sulfite salts, dithionite salts, hydrazine, 1-aminopyrrolidine, guanidines, carbonydrazides and semicarbazide, hydroxylamines, oximes, activated aldehydes, polyhydroxyl compounds.

[0031] The demulsifiers which can be used in the context of the present invention are, for example, those described in the work “Production Chemicals for the OU and Gas Industry”, Malcolm A. Kelland, CRC Press, 2nd edition, (2014), 291-301. More specifically, non-limiting examples include dodecylbenzylsulfonic acid (DDBSA), xylenesulfonic acid sodium salt (NAXSA), ethoxylated and propoxylated compounds, polyalkoxylated co- and ter-block polymers, polyalkoxylate or diglycidyl ether polyols, polyalkoxylated polyamines and related cationic polymers, polyurethanes (carbamates) and polyalkoxylated derivatives, hyperbranched polymers, vinyl polymers, polysilicones, and resins, such as phenolic resins and epoxy resins, and demulsifiers comprising a polyoxyalkylate, such as polyalkylene glycol, or formaldehyde-cardanol resins.

[0032] As non-limiting examples of anti-asphaltenes, mention may be made of aliphatic sulfonic acids, alkylarylsulfonic acids, arylsulfonates, lignosulfonates, alkylphenol / aldehyde resins and other similar sulfonated resins, polyolefin esters, polyolefin imides, polyolefin esters with alkyl, alkylenephenyl or alkylenepyridyl functional groups, polyolefin amides, polyolefin amides with alkyl, alkylenephenyl or alkylenepyridyl functional groups, alkenyl / vinylpyrrolidone copolymers, graft polymers of polyolefins with maleic anhydride or vinylimidazole, hyperbranched polyesteramides, polyalkoxylated asphaltenes, amphoteric fatty acids, salts alkyl succinates, sorbitan monooleate, and succinic anhydride and polyisobutylene.

[0033] Suitable anti-waxing agents include paraffin crystal modifiers, and combinations of dispersants and crystal modifiers, and by way of non-limiting examples, as crystal modifiers, alkylacrylate copolymers, alkylacrylate / vinylpyridine copolymers, ethylene / vinylacetate copolymers, maleic anhydride ester copolymers, branched polyethylenes, naphthalenes, anthracenes, microcrystalline waxes, and asphaltenes, and as paraffin dispersants, dodecylbenzene sulfonate, oxyalkylated alkylphenols, and oxyalkylated alkylphenol resins.

[0034] As non-limiting examples of de-oilers, mention may be made of organic salts of metals, such as alums, aluminum chloride, and aluminum chlorohydrate, organic polymers such as acrylic acid-based polymers, acrylamide-based polymers, polymerized amines, alkanolamines, thiocarbamates, and cationic polymers, such as diallyldimethylammonium chloride (DADMAC).

[0035] Pour point reducers (or "pour-point depressants") that can be used in the context of the present invention are, for example, those described in the work "Production Chemicals for the OU and Gas Industry", Malcolm A. Kelland, CRC Press, 2nd edition, (2014), 267-278. Among these, we can cite, by way of non-limiting examples, ethylene / vinylacetate (EVA) copolymers, polyacrylates, poly alpha-olefins, ethylene / acrylonitrile copolymers, ethylene / alkene copolymers, polymers of acrylic or methacrylic esters, polymers of maleic anhydride, copolymers of maleic anhydride with vinyl comonomers, and others and mixtures thereof.

[0036] Among the biocides which may advantageously be used in the context of the present invention, mention may be made, by way of non-limiting examples, of oxidizing biocides and non-oxidizing biocides. Examples of non-oxidizing biocides include aldehydes (for example formaldehyde, glutaraldehyde, and acrolein), amine compounds (for example quaternary ammoniums and cocodiamines), halogenated compounds (such as 2-bromo-2-nitropropane-3-diol (better known as bronopol) and 2-2-dibromo-3-nitrilopropionami (DBNPA)), sulfur compounds (such as isothiazolone, carbamates, metronidazole), quaternary phosphonium salts (such as tetrakis(hydroxymethyl)phosphonium sulfate (THPS)).Examples of oxidizing biocides include sodium hypochlorite, trichloroisocyanuric acid, dichloroisocyanuric acid, calcium hypochlorite, lithium hypochlorite, chlorinated hydantoins, stabilized sodium hypobromite, activated sodium bromide, brominated hydantoins, chlorine dioxide, ozone, and peroxides. Examples of biocides that may be used in the present invention are, for example, those described in "Production Chemicals for the OU and Gas Industry," Malcolm A. Kelland, CRC Press, 2nd Edition, (2014), 330-344.

[0037] Among the thermodynamic inhibitors of gas hydrates, mention may be made, by way of non-limiting examples, of sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sodium bromide, brines based on formates (such as potassium formate), polyols (such as glucose, sucrose, fructose, maltose, lactose, gluconate, monoethylene glycol, diethylene glycol, triethylene glycol, mono-propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, monobutylene glycol, dibutylene glycol, tributylene glycol, glycerol, diglycerol, triglycerol, and sugars (e.g. sorbitol, mannitol)), methanol, propanol, ethanol, glycol ethers (such as diethylene glycol monomethyl ether, ethylene glycol monobutyl ether), alkyl and cyclic esters (such as ethyl lactate, butyl lactate, methyl ethyl benzoate).

[0038] The gas hydrate kinetic inhibitors and anti-caking agents which can be used in the context of the present invention are, for example, those cited in "Production Chemicals for the OU and Gas Industry", Malcolm A. Kelland, CRC Press, 2nd edition, (2014), 224-244.More specifically, the gas hydrate kinetic inhibitors and anti-caking agents may be selected from polysaccharides (such as hydroxyethylcellulose (HEC), carboxymethylcellulose (CMC), starch and its derivatives, xanthan), lactams (such as polyvinylcaprolactam, polyvinyllactam), pyrrolidones (such as polyvinylpyrrolidone of various molecular weights), surfactants (such as fatty acid salts, ethoxylated alcohols, propoxylated alcohols, sorbitan esters, ethoxylated sorbitan esters, fatty acid polyglycerol esters, alkylglucosides, alkylpolyglucosides, alkylsulfates, alkylsulfonates, alkylestersulfonates, aromatic alkylsulfonates, alkylbetaines, alkylamidobetaines, hydrocarbon-based dispersants (such as lignosulfonates, iminodisuccinates, polyaspartates), amino acids, proteins.

[0039] According to a very particularly preferred aspect of the present invention, the pH of the composition is between 1 and 14, inclusive, preferably between 4 and 14, and more preferably the pH of the composition is strictly greater than 7, for example between the values ​​strictly greater than 7 and less than or equal to 14.

[0040] The pH can advantageously be adjusted within the above-mentioned value range by adding one or more pH modifiers and / or basic compounds, as indicated above.

[0041] The composition of the invention, which is a foaming composition intended for the enhanced recovery of hydrocarbons, has also been shown to be particularly effective in reducing corrosion on non-alloyed steel, whether during storage, in injection lines and at injection points. It has also been demonstrated that the composition of the invention makes it possible to prevent generalized corrosion and more particularly crevice corrosion, also known as cavernous corrosion.

[0042] Thus, and according to a second aspect, the present invention relates to the use of at least one composition as just defined for assisted recovery. of hydrocarbons, in particular oil and / or gas. More particularly, the present invention relates to the use for the enhanced recovery of hydrocarbons, by injection of said at least one composition into the production wells. More specifically still, the present invention relates to the use of at least one composition as just defined to prevent the formation of corrosion, whether generalized corrosion, but more particularly crevice corrosion, also known as crevice corrosion, but also to inhibit the corrosion of steels, more particularly non-alloy steels, and in particular the corrosion of equipment intended for the enhanced recovery of hydrocarbons, such as oil and / or gas.

[0043] The composition useful for the use according to the present invention can be used pure, that is to say without dilution, or else diluted in one or more solvents, as defined above. According to a preferred aspect, the composition which is the subject of the use according to the invention is used pure (without dilution) or else diluted in one or more solvents in proportions ranging from 0.1% to 99.9%, preferably from 0.5% to 99%, by weight relative to the total weight of (composition + solvent(s)). According to a preferred aspect, the composition can be diluted in one or more solvents in proportions ranging from 10% to 70%, preferably from 10% to 60%, by weight relative to the total weight of (composition + solvent(s)). According to another preferred aspect, the composition may be diluted in one or more solvents in proportions ranging from 1% to 30%, preferably from 5% to 20%, by weight relative to the total weight of (composition + solvent(s)).

[0044] Finally, and according to a third aspect, the present invention relates to a method for the enhanced recovery of hydrocarbons, in particular oil and / or gas, using at least one composition as defined above. The enhanced recovery method of the invention comprises at least one step of adding to the injection fluid at least one foaming composition, as defined above, via an injection line (or umbilical) or via the extraction installation, by gas injection. The injected gas and the composition flow together in the internal annular space between the casing and the well in the form of a multi-phase mixture, until reaching a gas injection valve which injects the mixture into the casing of the well.

[0045] The quantity of foaming and non-corrosive composition of the invention is generally between 0.001% and 20%, preferably between 0.01% and 10%, preferably between 0.01% and 5%, by weight, relative to the weight of aqueous phase contained in the fluids produced which it is desired to extract from the subsoil and entrain in the production wells.

[0046] The composition of the invention can be injected via the injection lines or the gas injection extraction installation (“gas lift” in English), in at the same time as other additive(s) or solvent(s), and for example at the same time as other additives, such as corrosion inhibitors, anti-hydrates etc., or solvents, such as monoethylene glycol (MEG).

[0047] For example, the composition of the invention can for example be injected via the same existing injection line used for the injection of a corrosion inhibitor.

[0048] The following examples illustrate the invention without, however, limiting its scope which is defined by the appended claims. Example 1#:

[0049] The following compositions are prepared by simple mixing of the components: Composition R (Reference composition), Compositions A, B and C, according to the invention and comparative Composition D which is a surfactant composition comprising a) at least one amphoteric (like the compositions according to the invention), but which does not comprise b) a sulfur molecule.

[0050] All the compositions tested are detailed in the following table 1, where the contents of each component are expressed in mass percentages. - Table 1 - Composition CAPB Sulfur molecule Surfactants, solvents R 43.00 - water: 57.00 A 38.00 ATG: 0.01 water: 56.99 B 19.00 MBTNa: 0.02 water: 31.28 / BuOH: 49.00 DDD: MEG / 50.50. C 19.00 TGNa :0.11 water: 31.00 / BuOH : 49.60 ITODETA : 0.19 / TEG : 0.10 D 89.50 - Water : 9.50 / NaOH : 0.40 / DDBMAC1 : 0.20 / Amphoram® CPI® : Noramox 101 : 101 0.03 / PBTC :0.16 / MEG :0.18 CAPB = coco-amidopropylbetaine chloride (Stepan)

[0052] ATG = thioglycolic acid (Arkema)

[0053] MBTNa = 2-mercaptobenzothiazolate de sodium (MLPC International)

[0054] TGNa = Sodium thioglycolate (Bruno Bock)

[0055] BuOH = 2-Butoxyethanol (Merck)

[0056] DDBMAC1 = Dodecyldimethylbenzylammonium chloride (Stepan's BTC 50)

[0057] MEG = Monoethylene glycol (Merck)

[0058] ITODETA = Imidazoline TallOil DETA (Arkema)

[0059] Amphoram® CPI = N-coco-aminopropionic acid (Arkema)

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069] Noramox® Cil = ethoxylated fatty amine (Arkema) PTBC = phosphonobutane tricarboxylic acid (Italmatch) Crevice corrosion inhibition capabilities are evaluated by immersing a 17 cm2 unalloyed steel coupon (reference UNS G10180) in 100 mL of a foaming test solution (Compositions R, A, B, C and D) in a closed bottle. The immersion time is 15 days at a temperature of 60°C. The metal coupon has a confined area covered with a polytetrafluoroethylene (PTFE) tape, adhering to the surface. Crevice corrosion is assessed by microscopic observation. The depth of corrosion, under the PTFE tape relative to the initial surface, constitutes the crevice depth. The results are shown in Table 2 below. - Table 2 - Composition Crevice depth (pm) R 100 A <5 B <5 C <5 D 50 It is noted that the compositions according to the invention do not produce crevice corrosion, unlike the reference Composition R, but also and above all, compared to the comparative Composition D. Example 2#: Foaming test A mixture of crude oil, from the Persian Gulf and with an API gravity (https: / / fr.wikipedia.org / wiki / Densit%C3%A9_API) between 20 and 30, and salt water, the composition of which is detailed in Table 3, is prepared in a glass bottle at different ratios (see Table 4). Foaming compositions B and reference R are each introduced into the mixture at 0.15% or 0.30% respectively. The bottle is closed and the mixture is shaken for 1 minute (200 movements per minute) on an oscillating table. 200 g of this mixture are then introduced into a 1000 mL glass column, with a double jacket, previously heated to the desired temperature, i.e. 60°C, with a thermostatic bath connected to the double jacket. The column includes a carbon dioxide (CO2) feed, composed of a class 2 porosity glass frit, positioned at the bottom of the column for gas flow, a flow meter. The column head includes a condenser to transport the liquid overflowing from there, towards another container placed on a scale intended to record, as a function of time, the quantity of liquid recovered. The gas flow rate is kept constant at 2 L.min *. — Table 3 -

[0070] Minerals* g-L1 SrCl2, 6 H2O 0.02 MgCl2, 6 H2O 23.42 Na2SO4 1.35 KBr 0.32 KC1 1.44 CaCl2, 2 H2O 21.94 NaHCO3 1.03 NaCl 57.40

[0071]

[0072] * These mineral salts are available from Sigma Aldrich The percentage of liquid recovered at the top of the column after 5 min is calculated by dividing the weight of the liquid collected in the container by the initial weight placed in the cylinder, multiplied by 100. The results are presented in the following Table 4: - Table 4 - Salt water / crude oil ratio (v / v) Composition Percentage of liquid recovered by foaming after 5 min 100 / 0 R 82% 70 / 30 R 61% 100 / 0 B 84% 70 / 30 B 60% It is found that the compositions according to the invention, in addition to their ability to inhibit crevice corrosion, allow enhanced oil recovery by entrainment of fluids by foaming, just like the compositions commonly used which, however, suffer from the disadvantage of not inhibiting said crevice corrosion.

[0073]

Claims

Claims

1. Foaming, corrosion-inhibiting composition comprising: a) a surfactant composition comprising at least one amphoteric surfactant compound and optionally one or more additional surfactant compounds chosen from ionic and non-ionic surfactant compounds, and b) at least one sulfur-containing molecule chosen from: - mercaptans of formula RSH, where R represents a linear or branched, saturated or unsaturated hydrocarbon chain containing from 1 to 12 carbon atoms, and optionally one or more heteroatoms, chosen from nitrogen, oxygen and sulfur, and optionally one or more cycle(s), - mercapto acids of formula HOOC-R'-SH, where R' represents a divalent, linear or branched, saturated or unsaturated hydrocarbon radical containing from 1 to 12 carbon atoms, and optionally one or more heteroatoms, chosen from nitrogen, oxygen and sulfur, and optionally one or more cycle(s), as well as the salts of said mercapto acids,- dithiols and disulfides of formula RrS-S-R2, where Ri and R2 each represent, independently of one another, a linear or branched, saturated or unsaturated hydrocarbon chain, containing from 1 to 12 carbon atoms, which may contain one or more heteroatoms chosen from nitrogen, oxygen and sulfur, and optionally one or more cycle(s), - as well as mixtures of two or more of said sulfur molecules, in all proportions, and the sulfur molecule being present at a dose of between 0.001% and 2% by weight, relative to the total weight of the composition.,

2. A composition according to claim 1, wherein the amphoteric surfactant compound is a zwitterion, preferably selected from betaines and sultaines.

3. A composition according to claim 1 or claim 2, wherein the amphoteric surfactant compound is selected from the group of betaines and sultaines comprising alkylbetaines, alkylarylbetaines, arylalkylbetaines, alkylamidopropylbetaines, alkylarylamidopropylbetaines, arylalkylamidopropylbetaines, alkylaminopropylbetaines, alkylarylaminopropylbetaines, arylalkylaminopropylbetaines, alkylsultaines, alkylarylsultaines, arylalkylsultaines, alkylamidopropylhydroxysultaines, as well as mixtures of two or more of them in any proportions.

4. A composition according to any one of the preceding claims, wherein the additional surfactant is selected from alkyl(aryl)(ether)sulfates, alkyl(aryl)sulfonates, alkyl(aryl)ester phosphates, alkyl(aryl)carboxylates, alkylsulfosuccinates, quaternary ammonium salts, alkylamine oxides, alkylamine ethoxylates, alkylamide ethoxylates, fatty acid ethoxylates, fatty alcohol ethoxylates, alkylethercarboxylates, alkylamide carboxylates, alkyl(poly)glucosides, alkylsorbitan esters, ethyleneoxy-propyleneoxy (EO-PO) block copolymers, alkylisothionates, alkylglycinates, alkylsarcosinates, alkylsulfosuccinates, alkylglutamates, alkyllactilates, alkyltaurates, alkylsulfoacetates, as well as mixtures of two or more of them in any proportions.

5. A composition according to any one of the preceding claims, wherein the sulfur molecule is selected from thioglycolic acid, sodium thioglycolate, sodium thiosulfate, sodium thiocyanate, mercaptopropionic acid, tert-butyl mercaptan, ethylhexyl thioglycolate, mercaptoethanol, thioglycolic acid disulfides, 3-mercaptopropionic acid and its salts, 1,8-dimercapto-3,6-di-oxa-octane, bis-(2-mercaptoethyl)ether, mercaptobenzothiazolates, the sodium salt of 2-[(dithiocarboxy)thio]-acetic acid, as well as mixtures of two or more of them in all proportions.

6. A composition according to any one of claims 1 to 4, wherein the sulfur molecule is selected from ammonium thiosulfite, ammonium thiosulfate, potassium thiosulfate, potassium thiosulfite, ammonium thiocyanate, calcium thiocyanate, sodium thioglycolate, ammonium thioglycolate, 1,2-diethylthiourea, propylthiourea, 1,1-diphenylthiourea, thiocarbanilide, 1,2-dibutylthiourea, dithiourea thioacetamide, thionicotimide, thiobenzamide, 2-mercpatoethanol, 3-(methylthio)propanal, thioacetic acid, cysteamine, 3-chloro-1-propanethiol, l-mercapto-2-propanol, 2,3-dimercapto-l,10-propanol, 2-methoxyethanethiol, 3-mercapto-l-propanol, 2,3-dimercapto-l-propanol, 1-thioglycerol, 1,3-propanedithiol, mercaptosuccinic acid, N-carbamoyl-L-cysteine, N-acetylcysteamine, 4-mercapto-l-butanol, 1-butanedithiol, 1,4-butanedithiol, 2,2'-thiodiethanethiol, 4-cyano-l-butanethiol, cyclopentanethiol, 1,5-pentanedithiol, 2-methyl-l-butanethiol, 2,3,5,6-tetrafluorobenzenethiophenol, 4-chlorothiophenol, 2-mercaptophenol, thiophenol, cyclohexylthiol, 4-mercaptobenzoic acid, thiosalicylic acid, 2-ethylhexanethiol, compounds of formula CnH2n+iSH, with n between 1 and 10, limits inclusive, as well as mixtures of two or more of them in all proportions.

7. Composition according to any one of the preceding claims, in which the sulfur molecule is present at a dose of between 0.005% and 1%, preferably between 0.005% and 0.1%, and advantageously between 0.005% and 0.01%, limits included, by weight, relative to the total weight of the composition.

8. Composition according to any one of the preceding claims, further comprising at least one solvent, preferably a polar solvent, or a non-polar solvent or a combination thereof, preferably chosen from: - water, including salt water, sea water, - alcohols, including alcohols of formula R-OH, where R is as defined above, and such as methanol, ethanol, propanol, isopropanol, butanol, 2-ethoxyethanol, hexanol, octanol, 2-butoxyethanol, - glycols, glycol ethers and their derivatives, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, ethylene glycol-monobutyl ether, and others, - ketones, such as cyclohexanone, di-isobutyl ketones, N-methylpyrrolidinone, N,N-dimethylformamide, and others, as well as the mixture of two or more of them in any proportions.

9. Composition according to any one of the preceding claims, further comprising one or more other additives, preferably chosen from: - pH modifiers, - mineral anti-deposits, - corrosion inhibitors, - hydrogen sulfide inhibitors, - oxygen scavengers, - demulsifiers, - anti-asphaltenes, - anti-paraffins, - oil removers, - pour point reducers, - biocides, - gas hydrate anti-caking agents, - thermodynamic gas hydrate inhibitors, - gas hydrate kinetic inhibitors, - as well as mixtures of two or more of these additives in any proportion.

10. Use of at least one composition according to any one of claims 1 to 9, for the enhanced recovery of hydrocarbons, in particular oil and / or gas.

11. Use according to claim 10, for preventing the formation of generalized corrosion, and more particularly for preventing crevice corrosion.

12. Process for the enhanced recovery of hydrocarbons, comprising at least one step of adding to the injection fluid at least one composition according to any one of claims 1 to 9, via an injection line or via the extraction installation, by gas injection.