WO2016110655A1

WO2016110655A1 - Injectivity additive

Info

Publication number: WO2016110655A1
Application number: PCT/FR2016/050029
Authority: WO
Inventors: Gilles Barreto; Patrice Robert
Original assignee: Ceca S.A.
Priority date: 2015-01-08
Filing date: 2016-01-07
Publication date: 2016-07-14
Also published as: FR3031521A1

Abstract

The present invention relates to the use, in order to improve the permeability of porous media containing a hydrocarbon, of at least one alkoxylated fatty amine. The invention also relates to the process for treating an injection well penetrating subterranean formations containing hydrocarbons, in order to improve and/or maintain the injectivity thereof, and also to the compositions comprising at least one compound bearing a quaternary nitrogen atom, at least one hydrocarbon, solid inorganic particles and water.

Description

ADDITIVE FOR INJECTIVENESS

The present invention relates to the field of water injection to help the recovery of hydrocarbons in the groundwater (oil, gas, bitumen, and others). More particularly, the present invention relates to the use of specific additives in aqueous formulations for injection into hydrocarbon wellbores.

The present invention also relates to the hydrocarbon recovery process using aqueous formulations containing said specific additives, and more particularly in the context of primary recovery, secondary or tertiary or in the context of hydraulic fracturing or in the context of acidification. Tertiary recovery is also called assisted recovery.

[0003] The primary recovery of hydrocarbons uses the energy present in the reservoir to extract the hydrocarbons. Associated with hydrocarbons, so-called production water can accompany hydrocarbons on the surface. This water after treatment is not always pure, and may contain hydrocarbons. Its release into the wild is therefore excluded, and it is then necessary to inject this production water containing hydrocarbons into a well not connected to the tank containing the hydrocarbons, to avoid pollution and to continue the extraction of the hydrocarbons.

The principle of secondary or tertiary recovery of hydrocarbons is to inject water with one or more injection wells for the purpose of moving a maximum volume of hydrocarbon to the producing well or wells. In the case of viscous, heavy, extra heavy and oil sands oils, the injected water is heated before injection to heat the hydrocarbon in the underground reservoir by contact and thus reduce its viscosity to facilitate its movement towards the producing wells.

In the case of tertiary recovery, one or more additives are commonly added to the water to modify its different properties physico-chemical, for example to increase its viscosity, increase its pH, lower its surface tension, and others, this to further improve the recovery of hydrocarbon compared to the secondary recovery technique defined above.

In the case where the underground reservoir containing hydrocarbons is not sufficiently permeable to economically produce hydrocarbons with primary, secondary or tertiary recovery techniques, hydraulic fracturing or acidification is employed.

In the hydraulic fracturing technique, water is injected at a high flow rate into an injection well so as to fracture the rock of the underground reservoir. This fracturing makes it possible to increase the permeability of the reservoir to produce the hydrocarbons. The injected water most often contains proppants, in varying concentrations, proppants which are assimilated to mineral solid particles whose median diameter is generally greater than 100 μιτι. These particles are transported to the fractures so as to keep them open by jamming as soon as the injection pressure is reduced. Without this maintenance, the created fractures would close and the well would not receive hydrocarbons.

The fracturing fluid is then pumped to the surface where it rises in mixture with the water initially present in the tank, and with hydrocarbons and solid particles divided as the clays from the tank. Once this mixture (or "flowback water" in English) surfaced, it is treated in settling ponds to separate water from other solid components and divided hydrocarbons. This treatment then allows reuse for a new hydraulic fracturing operation.

In the case of the acidification technique, the permeability of the underground reservoir is increased without using the fracturing technique, but by attacking the reservoir rock using an acid or a mixture of acids. added with water that may contain hydrocarbons and inorganic solid particles. At the end of the treatment the fluid is also pumped towards the surface where it rises in mixture with the water initially present in the tank, hydrocarbons and inorganic solid particles such as clays from the tank to then be stored to separate the water.

Pumping in producing wells is also a technique used to increase productivity. It is also possible to use the same well alternatively as an injection well and as a producing well. The injected water can come from a surface source (river, pond, lake, sea, ocean, and others) or from an underground source. The underground source may be a reservoir of water containing or not containing hydrocarbons. The injected water may also be a mixture of water from several sources.

It is important in the secondary or tertiary recovery operations that the water is injected at the desired rate to also obtain the desired flow rate of hydrocarbons.

In some cases, however, the injectivity, that is to say the ability to inject water at a certain rate, is not sufficient or is initially sufficient and then degrades over time. This loss of injectivity corresponds to a decrease in the permeability of the rock located around the injection well (s) and can have multiple causes.

One of the causes is the presence, permanent or temporary, in the injected water of inorganic solids, especially divided inorganic solids (or inorganic solid particles) associated with hydrocarbons. In the present invention, the term "inorganic solid particle" means an inorganic solid of size less than 5 mm, preferably less than 1 mm, more preferably less than 500 μιτι, more particularly less than 100 μιτι. One possible solution to limit this problem is to decant the water so as to separate it from solids and hydrocarbons. However, the settling times can be very long, in particular when the inorganic solid particles are smaller than a few micrometers.

These long settling times result in the storage of very large amounts of water. However, in areas where water is scarce, for example in Texas where hydraulic fracturing is already widely used, or in Alberta where the oil sands are exploited, this immobilization of large quantities of water pending effective decantation is problematic because it can lead to take water from a source useful to living beings. In addition, open storage can lead to the emission of hydrocarbons into the atmosphere. Finally, when space is limited, for example on offshore hydrocarbon production units (offshore), the installation of large settling units is problematic.

The presence of inorganic solids associated with hydrocarbons in the injected water is encountered in many cases. By way of example, mention may be made of the cases where the underground reservoir containing the water to be injected contains hydrocarbons and is naturally poorly consolidated which, when pumping water, results in the arrival of divided solids initially present in the reservoir. .

By way of examples, mention may be made of the cases in which the underground reservoir containing the water to be injected contains hydrocarbons and is thus naturally consolidated and therefore not mobile, with the exception of hydrothermal degradation products of the inorganic solids of the reservoir. as for example clays. It is also possible to mention the cases where hydrocarbons are present in the water that will be injected and where divided solids appear because of a change of pressure and / or temperature leading to precipitation or because of a mixture of waters leading to precipitation. We can also mention cases where hydrocarbons are present in the water that will be injected and where split solids appear because of a corrosion problem of the metal parts present in the path of the water that will be injected.

US Pat. No. 4,690,217 describes a method for improving the injectivity of the water injected into wells. This method involves injecting an aqueous fluid containing an effective amount of anionic surfactants into the wells. One of the drawbacks associated with this method is that the anionic surfactants are poorly soluble or insoluble in saline media. It is therefore necessary to be able to provide products that are even more efficient.

US6972274 discloses generally a method for restoring the permeability of a porous, oil-containing subterranean formation, and accelerating oil recovery, said method comprising treating said formation with an effective amount of a mixture of at least one nonionic compound and at least one cationic compound. In the request US20090149356 are described corrosion inhibitor compounds and useful for removing hydrocarbon deposits. These compounds are derivatives of bis-quaternary heterocyclic compounds with an imidazoline structure.

These two documents show that compounds with quaternary ammonium structure must be used in combination with a nonionic compound or have a bis-quaternary function.

This seems confirmed by CN10231 1728 which relates to a formulation comprising a quaternary ammonium surfactant, in combination with a corrosion inhibitor, a polyamino-polyether methylene phosphonate, citric acid, hydrochloric acid and some water. This formulation is used at 0.1% to 0.3% by weight of the injected water to allow a pressure reduction of about 15% per well. This formulation, however, has the drawbacks of containing acids and being used in too large quantities, so that its use could be considered harmful to the environment.

There remains a need for specific compounds that are effective to improve the injectivity or at least to maintain it at a good level in the case of the presence of divided inorganic solids and hydrocarbons in the water injected into the wells penetrating underground formations containing hydrocarbons, while combining a high efficiency, to limit the effective amounts used, and a low toxicity, or even absence of toxicity of the water injected vis-à-vis the environment.

Another object of the present invention is to provide a method using at least one specific compound which thus improves the injectivity of one or more wells, or at least to maintain a good level in the case of presence of divided inorganic solids and hydrocarbons in the injected water, in a curative or preventive manner. Yet another objective is to minimize on the surface the quantities of stored water containing divided inorganic solids and hydrocarbons.

The inventors have now discovered that the aforementioned objectives can be achieved in whole or at least in part through the use of at least one specific compound that improves the injectivity or at least the to maintain a good level in the case of the presence of divided inorganic solids and hydrocarbons in the water injected into the underground formations containing hydrocarbons.

[0024] Thus, and according to a first aspect, the present invention consists in the use, for improving the permeability of a porous medium containing at least one hydrocarbon, of at least one compound of general formula (1):

in which

R represents a hydrocarbon fatty chain, preferably a hydrocarbon chain, linear or branched, saturated or unsaturated, comprising from 8 to 30 carbon atoms, and optionally comprising one or more rings,

R ^a is chosen from an alkyl radical, linear or branched, having from 1 to 6 carbon atoms and an alkoxylated unit consisting of one or more alkoxylated link (s), preferably chosen from ethylene- oxy (OE), propyleneoxy (OP) and butyleneoxy (OB), said alkoxylated unit being terminated by the hydrogen atom or linear or branched alkyl radical containing from 1 to 6 carbon atoms,

R ^b and R ^c , which are identical or different, are chosen, independently of one another, from a hydrogen atom, a linear or branched alkyl radical containing from 1 to 6 carbon atoms, and an alkoxylated unit; consisting of one or more alkoxylated link (s), preferably chosen from ethylene-oxy (OE), propylene-oxy (OP) and butylene-oxy (OB), said alkoxylated unit being terminated by hydrogen atom or linear or branched alkyl radical containing from 1 to 6 carbon atoms,

X is chosen from divalent radicals chosen from alkylene-esters (-C (= O) -O- (CR ¹ R ² ) _n -L alkylene amines [-NR _c - (CR ¹ R ² ) _n - the L alkylene- (amino) - amide {-C (= O) - [NR ^c - (CR ¹ R ²⁾ _n] _P -}, amino-alkylene-amides {-C (= O) -NH- - [(CR ¹ R ² ) _n -NR ^c ] p-}, alkylene phosphates [-OP (OH) (= O) -O- (CR ¹ R ² ) _n -], alkylene phosphonates [-P] (OH) (= O) -O- (CR ¹ R ² ) _n -, or -OP (OH) (= O) - (CR ¹ R ² ) _n -], the alkylene sulphates [-OS (= O ) ₂ -O- (CR ¹ R ² ) _n -], alkylene sulfonates [-S (= O) ₂ - O- (CR ¹ R ² ) _n -, or -OS (= O) ₂ - (CR ¹ R ² ) _n -L alkylene-phosamides [-OP (OH) (= O) - NH- (CR ¹ R ² ) nL alkylene sulfonamides [-OS (= O) ₂ -NH- (CR ¹ R ² ) _n -L alkylene ethers [-O- (CR ¹ R ² ) _n -] , and the alkylene-ether-alkylene amines [-O- (CH ₂ ) _m -NH- (CR ¹ R ² ) _n -]>

R ¹ and R ² , which may be identical or different, represent, independently of one another, the hydrogen atom or a linear or branched alkyl radical containing from 1 to 6 carbon atoms,

N is an integer selected from 1, 2, 3, 4, 5 and 6, preferably from 1, 2 and 3,

M is selected from 0, 1, 2, 3, 4, 5 and 6, preferably from 0, 1, 2 and 3, and

P is chosen from 1, 2, 3, 4, 5 and 6, preferably from 1, 2 and 3,

It being understood that at least one alkoxylated unit as defined above for R ^a , R ^b and R ^c , is present in the compound of formula (1).

In the present description, "ethylene-oxy" represents - (CH2-CH2-O) -, propyleneoxy represents - (C3H6-O) -, and preferably - (CH ₂ -CH (CH ₃ ) - O) - or - (CH (CH ₃ ) -CH ₂ -O) -, and "butylene-oxy" represents - (C ₄ H ₈ -O) -, and preferably - (CH ₂ -CH (C ₂ H ₅ ) -O) or - (CH (C ₂ H ₅ ) -CH ₂ -O) -.

More preferably, the fatty hydrocarbon chain R- is a hydrocarbon chain, advantageously of natural origin, for example chosen from caprylyl, capryl, lauryl, myristyl, palmityl, stearyl, oleyl and linoleyl radicals.

In the present description, the term "linear or branched alkyl radical comprising 1 to 6 carbon atoms" is preferably understood to mean a linear or branched saturated hydrocarbon-based chain chosen from methyl, ethyl, propyl, butyl and pentyl radicals. and hexyls, and preferably from methyl and ethyl radicals.

According to a preferred aspect X is chosen from divalent radicals chosen from alkylene esters [-C (= O) -O- (CR ¹ R ² ) _n -], alkylene amines [-NR _c - ( CR ¹ R ² ) nL Alkylene- (amino) -amides {-C (= O) - [NR ^c - (CR ¹ R ² ) _n ] _P -}, alkylene ethers [-O- (CR ¹ R ² ) _n -], and the alkylene-ether-alkylene-amines [-O- (CH ₂ ) _m -NH- (CR ¹ R ² ) _n -], more preferably from the alkylene amines [-NR _c - (CR ¹ R ² ) _n -] and alkylene- (amino) amides {C (= O) - [NR ^c - (CR ¹ R ² ) _n ] _P -}.

According to one embodiment of the present invention, the radicals R ¹ and R ² are chosen, independently of one another, from the hydrogen atom and the methyl, ethyl, propyl, butyl, and pentyl radicals. and hexyls, and preferably among the hydrogen atom and the methyl and ethyl radicals, and most preferably, R ¹ and R ² each represent the hydrogen atom.

According to another embodiment, the number of alkoxylated links in each of the radicals R ^a , R ^b and R ^c is between 1 and 20. In a preferred embodiment, R ^a and R ^b each independently represent one of the other an alkoxylated unit consisting of one or more alkoxylated link (s) as defined above. In another preferred embodiment, R ^a , R ^b and R ^c are each independently of one another an alkoxylated unit consisting of one or more alkoxylated link (s) as defined above.

According to another preferred embodiment of the present invention, the value of m in the compound of formula (1) is zero (0), and in this case the compound of formula (1) can be written according to the following formula (1 '):

R ^a

R N

R ₍₎

[0032] An example of compound of formula (1) most preferred for use in the present invention is represented by polyoxyethylene (15) cocoamine (C15 Noramox ^®, available from CECA), CAS No. 61791 -14 -8.

The present invention is therefore related to improving the permeability of porous media containing a hydrocarbon, and in particular oil or gas, and more particularly oil, especially porous media such as underground formations containing oil. and divided inorganic solids. The use according to the present invention makes it possible in particular to increase the permeability, which has the direct consequence of improving the injectivity of the water injection wells, and thus the acceleration of the recovery of the hydrocarbons, and in particular the oil.

Without wishing to be bound by theory, it may be thought that the use of cationic surfactants of formula (1) defined above makes it possible to interact with the particles present in said formation. The clogging of the pores is thus delayed, which makes it possible to ensure good prevention of the loss of injectivity. In in addition, the pores are also opened under the effect of said cationic surfactants of formula (1), which allows concomitantly to restore the injectivity.

It has also been found that the surfactants of formula (1) are soluble or very soluble in aqueous saline media and even in highly saline media. This great advantage thus makes it possible to avoid the use of organic solvents in order to improve their solubility in water, and consequently a simpler and more environmentally friendly use (without the use of solvents, large volumes of liquids, blending facilities). The saline solubility of the compounds of formula (1) also has the particularly advantageous advantage of avoiding the risk of loss of permeability related to the precipitation of said compound of formula (1) in the injected water.

The compounds of formula (1) defined above are effective at particularly low doses, especially from 0.5 ppm by volume relative to the volume of water injected. As a general rule, the compound of formula (1) is added to the injection water at a dose of between 0.5 ppm and 10,000 ppm, preferably between 0.5 ppm and 5000 ppm, advantageously between 0.5 ppm. and 2000 ppm, and for example between 2 ppm and 500 ppm, by volume relative to the volume of water injected.

In one embodiment, the present invention relates to the use as defined above to improve the permeability in the case of primary, secondary or tertiary recovery to improve the permeability in the case of primary recovery, secondary or tertiary hydrocarbon. In another embodiment, the present invention relates to the use as defined above for improving permeability in the case of hydraulic fracturing and / or acidification.

According to another aspect, the present invention relates to a method of treating an injection well penetrating underground formations containing one or more hydrocarbons, and in particular oil, to improve and / or maintain the injectivity thereof, said method comprising at least one step of adding to the injection water an effective amount of at least one compound of formula (1) as defined above. By effective amount is meant an amount as defined above, generally greater than 0.5 ppm by volume relative to the volume of water injected and preferably between 0.5 ppm and 10000 ppm, preferably between 0.5 ppm and 5000 ppm, more preferably between 0.5 ppm and 2000 ppm, and advantageously between 2 ppm and 500 ppm, by volume relative to the volume of water injected.

The process of the invention is particularly suitable in cases where the injection water contains at least one hydrocarbon and inorganic solid particles.

The method according to the invention advantageously further comprises a decantation step and / or separation of hydrocarbons and inorganic solid particles present in water, decantation traditionally used in the production of hydrocarbons. This decantation is intended to separate some or all of the hydrocarbons and solids present in the water in separation facilities. These installations are closed or open tanks that are well known to those skilled in the art, such as, for example, two-phase separators, three-phase separators, hydrocyclones, centrifuges, flotation cells, filtration equipment, tanks, or even basins, installations that can be mounted in series and / or in parallel. The size of these facilities is adapted to the speed of separation of the different constituents. The lower the separation rate, the greater the size of the installation, so that the residence time in the installation allows efficient separation of hydrocarbons and solids from the water.

The injection point of said at least one compound of formula (1) may be located at all appropriate locations upstream of the injection well bottom, and for example, and not limited to: at the head of wells of production or in the bottom of production wells in the case where the water coming out is reinjected, but also upstream or downstream of the multiphase separators, upstream or downstream of the de-oiling units, in water which will be reinjected and which does not contain solid, divided minerals or that does not contain hydrocarbons. The method according to the present invention may also include two or more injection points. The person skilled in the art will know how to adapt the number of injection points and the places precise injection of said at least one compound of formula (1), according to the nature of the terrain, the nature of the hydrocarbon to be extracted, the desired flow rates, the nature and configuration of fluid treatment facilities produced and other parameters to be taken account for efficient and cost-effective hydrocarbon extraction.

The method according to the present invention may be implemented in a preventive or curative manner. When it is implemented in a curative manner, the method consists in temporarily injecting the injection water containing at least one compound of formula (1) and not containing divided inorganic solids and / or not containing hydrocarbons. When implemented preventively, the method consists of injecting temporarily or continuously the injection water, which contains at least one compound of formula (1), divided inorganic solids and hydrocarbons. It should be understood that the invention also comprises the implementation of the method in a curative manner followed by a preventive implementation and also the implementation of the method in a preventive manner followed by a curative implementation .

In one embodiment, the present invention relates to the method as defined above for improving and / or maintaining the permeability implemented in the case of primary, secondary or tertiary recovery.

In the case of primary recovery, the process comprises at least one step of adding to the production water an effective amount of at least one compound of formula (1) before the production water thus treated is injected into a reservoir.

In the case of primary recovery, the injection water is injected into a well not connected to the reservoir containing the hydrocarbons that it is desired to recover. In the case of secondary or tertiary recovery, the process comprises at least one step of adding in at least a portion of the injection water an effective amount of at least one compound of formula (1) before the production water thus treated is injected into the reservoir containing the hydrocarbons that it is desired to recover.

In another embodiment, the present invention relates to the method for improving and / or maintaining the permeability implemented in the case hydraulic fracturing and / or acidification. In the case of hydraulic fracturing and acidification, the process comprises at least one step of adding in at least a portion of the injection water an effective amount of at least one compound of formula (1 ) before the injection water thus treated is injected into the reservoir containing the hydrocarbons that it is desired to recover.

The present invention is particularly advantageous when the water recovered following previous operations of hydraulic fracturing or acidification is again used as injection water for a new operation of fracturing or acidification. Indeed, this recovered water may contain inorganic solids and hydrocarbons that are difficult to separate, which requires the use of settling ponds. According to the process of the invention, the decantation step before injection can thus be suppressed or at least the settling time can be reduced. This advantage therefore makes it possible either to eliminate the settling basins or at least to limit their size.

The term "inorganic solids" means inorganic solids as well as metal or alkaline or alkaline earth metal salts of organic acids, such as for example the salts of naphthenic acids.

Thus, the inorganic solid particles that may be present in the injection water may be of various natures, and most often consist of sand, clays, corrosion products, finely divided residues of rocks. subterranean and precipitated mineral products such as metal oxides, metal sulphides, sodium, potassium, magnesium, calcium, strontium, barium and iron salts, but also salts of organic acids, such as, for example, the salts of naphthenic acids .

The hydrocarbons that may be present in the injection water come mainly and most often hydrocarbon production wells and are in particular made of crude oil of API gravity between 8 ° and 60 °. Indeed, most hydrocarbons that are extracted, in addition to the use and the process according to the present invention, are extracted crudes having API densities of between about 20 ° API (very heavy) and about 60 ° API (very high). lightweight). Other hydrocarbons, the extraction of which may also include the use and method of the invention, are the bitumens, whose API index is generally below 15 ° API.

For the record, the API density is a scale to express the density of crude oil, in API degrees, calculated from the density, by the following formula of the American Petroleum Institute (API) and the National Institute of Standards and Technology (NIST):

Density API = (141.5 / (density at 60 ° F)) - 131.5.

The lower a crude is, the lower its density, the higher its API density. For comparison, water with a density of 1 has a API gravity of 10 ° API.

The method according to the present invention allows, thanks to the use of at least one compound of formula (1) as described above, to limit the time left to the decantation stage of the water to be injected. and which contains inorganic solid particles and hydrocarbons, because the finest particles (generally smaller than 100 μιτι) can be kept in suspension because they no longer impede the injection.

Therefore, and this is another advantage of the present invention, the size of the settling ponds or closed separation equipment can be reduced substantially and not negligible. On offshore installations (at sea), where space is limited, this represents a very interesting advantage. Since the size of the water treatment equipment that will be injected is limited, the quantities of water withdrawn are reduced and limited, which is also a considerable advantage, especially in areas where water is scarce. and vital for the life of human beings, fauna and flora.

The process according to the present invention also allows, thanks to the use of at least one compound of formula (1) as described above, to improve the quality of the separation between the hydrocarbons and the water in the presence inorganic solid particles when the time left in the separation step is kept constant.

Without wishing to be bound by the theory, it is estimated that the drop in permeability of the formation at the level of the injection wells before treatment could come from partial clogging over time of the pores by solid particles. inorganic, in contact with both hydrocarbons and water, thus at the water-oil interface, hydrocarbons initially contained as a suspension (droplets) in the injected water. The use of at least one compound of formula (1) according to the invention surprisingly makes it possible to significantly reduce the concentration of particles present at the oil-water interface in the injection compositions, and thus to reduce even avoid clogging by inorganic solid particles or simple deposition of inorganic solid particles (schmoo).

The method of the present invention also makes it possible to prevent the fouling of the installations located on the path of the injected water to the injection wells or to clean them in the case of presence of inorganic solid particles and hydrocarbons. in the injected water. Examples of installations include two-phase separators, three-phase separators, desalters, hydrocyclones, centrifuges, flotation cells, filtration equipment, tanks, or tanks, and other facilities useful at hydrocarbon extraction sites and from in contact with said hydrocarbons, and which can be mounted in series and / or in parallel. These inorganic solid particles form mixed deposits with hydrocarbons which also bear the name "schmoo".

Thus, and according to one embodiment, the method of the invention further comprises a step of decantation and / or separation of hydrocarbons and inorganic solid particles present in the water, using facilities. separation, such as for example those listed above, which can optionally be mounted in series and / or in parallel.

In the case of the water treatment of high salinity hydrocarbon extraction fields, the compounds of formula (1) have proved particularly effective, and more particularly more effective than the additives of the invention. injectivity known from the prior art, and in particular that the alkoxylated compounds carrying quaternary ammonium function, alone or in admixture with one or more fatty alcohol (s), in particular ethoxylated (s), but also that more electronically charged compounds such as compounds having two or more quaternary ammonium functions. In particular, the use according to the present invention implements at least one compound of formula (1) in contents lower than those required with the compounds of the prior art, for a similar efficiency or even greater. In addition, the compounds of formula (1) used in the context of the present invention may be used alone in the injected water, advantageously in the form of a solution in water and / or one or more organic solvents.

In addition, one or more additives may be added, these additives being well known to those skilled in the art of hydrocarbon extraction; these additives may be chosen from, by way of non-limiting examples, water-soluble organic solvents, colorants, tracers, anti-corrosion agents, flocculating agent, anti-deposition agents, demulsifying agents, non-emulsifying agents, wetting agents, rheology modifiers , drag reducers, crosslinking agents, oxidants, anti-caking agents, kinetic hydrate inhibitors, oxygen scavengers, coagulation agents, biocides, pH control agents, mineral salts and other.

The injection water that is injected into the wells is in general, and most often, consisting of production water, sea water, spring water, condensation water, water, water and water. rain water or a mixture of water from these different sources. In general, the water may be a high salinity water, and in particular a high salinity production water and more particularly a high salinity production water of hydrocarbon extraction fields. In particular, in the context of the present invention, the injection water consists of production water comprising an amount of sodium chloride greater than 30 gL ^-1 or even greater than 50 gL ^-1 , and even greater than 100 gL ^-1 .

According to yet another aspect, the present invention relates to a composition comprising at least one compound of formula (1) as defined above, at least one hydrocarbon, inorganic solid particles and water.

Preferably, the composition according to the invention is such that the mass ratio compound (s) of formula (1) / inorganic solid particles is included between 5.10 ^"6 and 1, preferably between 10 ^{" 5} and 10 ^"1 , more preferably between 5.10 ^{" 5} and 10 ^"1 , and most preferably between 5.10 ^{" 3} and 5.10 ^"2 .

According to an even more preferred aspect, in the composition according to the invention, the amount of hydrocarbon (s) is generally between 0.5 ppm and 10%, by weight relative to water, the amount in inorganic solid particles is generally between 0.5 ppm and 10%, by weight relative to water, the amount of compound of formula (1) corresponds to the dose defined above, typically between 0.5 ppm and 10000 ppm preferably between 0.5 ppm and 5000 ppm, more preferably between 0.5 ppm and 2000 ppm, and preferably between 2 ppm and 500 ppm, by volume relative to the volume of water.

The following examples illustrate the object of the invention, and are provided for information only, without however being intended in any way to limit the various embodiments of the present invention.

Example 1

The test described below makes it possible to simulate the clogging of a water injector well, followed by a curative treatment. This simulation is carried out by impregnation of a sinter of porosity No. 2, ie having a pore size of between 40 μιτι and 100 μιτι, and the so-called "clogging" composition is a composition comprising a hydrocarbon A, water , and a divided solid which is a colloidal clay (bentonite from ICMC).

Before carrying out the tests, the sinter is cleaned with acetone and dried with compressed air. The water injection is then simulated by the flow of water through the sintered sinter. The injectivity of the reservoir is simulated by the flow time of 40 mL of water. The decrease of the flow time means the improvement of the permeability of the sinter which simulates the improvement of the injectivity of the reservoir.

The water used for the sealing composition is a high salinity water of the following saline composition:

MgCl ₂ , 6H ₂ O: 25.65 g. L ^1, · NaHCO: 1, 42 g. L ¹ ,

• KCl: 0.63 g. L ^"1 · NaCl: 94.08 g L ^-1 ,

• CaCl ₂ , 2H ₂ O: 4. 09 gL ¹ , · NaF: nd, • SrCI ₂ , 6H ₂ O: nd • NaAc, 3H ₂ O: nd

• BaCI ₂ , 2H ₂ O: nd • NH ₄ CI: nd

• Na ₂ SO: nd • Na ₂ CO ₃ : nd

• KBr: nd • FeCl ₂ , 4H ₂ O: nd where "nd" means, undetectable.

The hydrocarbon A (oil originating in Angola having a density equal to

25 ° API) is preheated to 45 ° C. A 40 mL sample of this hydrocarbon is removed and emulsified, with an Ultra-Turrax ^® shaker in a 100 mL Schott ^® vial, with 10 mL of high salinity water defined above. Stirring is maintained for 3 minutes at a speed of 15,000 rpm- ¹ .

After this emulsification, 450 mg of colloidal bentonite are added.

The whole is stirred for 30 minutes with a magnetic bar.

Half of this mixture is poured on a first sintered and the second half on a second sintered identical. We then let each sinter impregnate during

5 minutes, after which time the excess of sintered surface mixture is removed.

We then leave 15 minutes at rest.

Then poured 50 mL of high salinity water defined above, alone or additive with one of the compounds to be tested, on each of the sintered. The elapsed volume is measured as a function of the flow time by reading on a graduated cylinder.

The compounds tested are as follows:

• Compound A (according to the invention): polyoxyethylene (15) cocoamine

(Noramox ^® C15, marketed by CECA), CAS 61 791-14-8,

• Compound B (comparative) N-methyl-coconut alkyl-di (pentadeca- hydroxyethyl) methylammonium (NOXAMIUM C15M ^®, marketed by CECA), CAS 68989-03-7,

• Compound C (comparative): Oleyl-cetyl alcohol polyoxyethylene-ether

(Surfaline OC5 ^®, marketed by CECA), CAS 68920-66-1.

The results are expressed by the time elapsed to collect 40 mL of water passed through the sintered. These results are collated in the following Table 1: - Table 1 -

Flow time of

Quantity (ppm by volume

Compound tested 40 ml_ of water

ratio to the volume of water)

(minutes)

Water not additive - 180

Compound A 300 80

Compound A 1000 31

Sintered clogged, not

Compound B 1000

flow

Sintered clogged, not

Compound C 1000

flow

Compound B +

Sintered clogged, not Compound C 1000

flow (50/50 by volume)

Among all the products tested, only the compounds according to the invention (here polyoxyethylene (15) cocoamine) makes it possible to improve the permeability of the sintered material.

Claims

1. Use, for improving the permeability of a porous medium containing at least one hydrocarbon, of at least one compound of general formula (1):

in which

X is chosen from divalent radicals chosen from alkylene-esters (-C (= O) -O- (CR ¹ R ² ) _n -L alkylene amines [-NR _c - (CR ¹ R ² ) _n - ], the alkylene (amino) - amide {-C (= O) - [NR ^c - (CR ¹ R ²⁾ _n] _P -}, amino-alkylene-amides {-C (= O) -NH- - [(CR ¹ R ² ) _n -NR ^c ] p-}, the alkylene phosphates [-OP (OH) (= O) -O- (CR ¹ R ² ) _n -], the alkylene phosphonates [- P (OH) (= O) -O- (CR ¹ R ² ) _n -, or -OP (OH) (= O) - (CR ¹ R ² ) _n -], the alkylene sulfates [-OS (= O) ₂ -O- (CR ¹ R ² ) _n -], the alkylene sulfonates [-S (= O) ₂ -O- (CR ¹ R ² ) _n -, or -OS (= O) ₂ - ( CR ¹ R ² ) _n -L alkylene phosamides [-OP (OH) (= O) -NH- (CR ¹ R ² ) _n -L alkylene sulfonamides [-OS (= O) ₂ -NH- ( CR ¹ R ² ) _n -], the alkylene ethers [-O- (CR ¹ R ² ) _n -], and the alkylene-ether-alkylene-amines [-O- (CH 2) _m - NH- (CR ¹ R ² ) _n -]>

N is an integer selected from 1, 2, 3, 4, 5 and 6, preferably from 1, 2 and 3,

M is selected from 0, 1, 2, 3, 4, 5 and 6, preferably from 0, 1, 2 and 3, and

P is chosen from 1, 2, 3, 4, 5 and 6, preferably from 1, 2 and 3,

2. Use according to claim 1, wherein the fatty hydrocarbon chain R- of the compound of formula (1) is a hydrocarbon chain selected from caprylyl, capryl, lauryl, myristyl, palmityl, stearyl, oleyl and linoleyl radicals.

3. Use according to claim 1 or claim 2, wherein, in the compound of formula (1), X is chosen from divalent radicals chosen from alkylene-esters [-C (= O) -O- (CR ¹ R ² ) _n -], alkylene amines [-NR _c - (CR ¹ R ² ) _n -], alkylene- (amino) -amides {C (= O) - [NR ^c - (CR ¹ R ² ) _n ] _P -}, the alkylene-ethers [-O- (CR ¹ R ² ) _n -L and the alkylene-ether-alkylene-amines [-O- (CH ₂ ) m -NH- (CR ¹ R ² ) _n -], more preferably from alkylene amines [-NR _c - (CR ¹ R ² ) _n -] and alkylene- (amino) amides {-C (= O) - [NR ^c - ( CR ¹ R ² ) _n ] _P -}.

4. Use according to any one of the preceding claims, wherein the radicals R ¹ and R ² of the compound of formula (1) are chosen independently of each other from a hydrogen atom and methyl radicals. ethyl, propyl, butyl, pentyl and hexyl, and preferably from hydrogen, methyl and ethyl, and most preferably R ¹ and R ² are each hydrogen.

5. Use according to any one of the preceding claims, wherein the number of alkoxylated links in each of R ^a , R ^b and R ^c of the compound of formula (1) is between 1 and 20.

Use according to any one of the preceding claims, wherein the value of m in the compound of formula (1) is zero (0).

Use according to any one of the preceding claims, wherein the compound of formula (1) is polyoxyethylene (15) cocoamine.

8. Use according to any one of the preceding claims, for improving the permeability in the case of primary, secondary or tertiary recovery.

9. Use according to any one of claims 1 to 7, to improve the permeability in the case of hydraulic fracturing and / or acidification.

A method of treating an injection well penetrating subterranean formations containing one or more hydrocarbons, for improving and / or maintaining injectivity thereof, said method comprising at least one step of adding to the water of injecting an effective amount of at least one compound of formula (1) defined in any one of claims 1 to 7.

11. The method of claim 10, wherein the injection water contains at least one hydrocarbon and inorganic solid particles.

The method of claim 10 or claim 11, wherein the effective amount is a dose of from 0.5 ppm to 10,000 ppm, preferably from 0.5 ppm to 5000 ppm, more preferably from 0.5 ppm. and 2000 ppm, and advantageously between 2 ppm and 500 ppm, by volume relative to the volume of water injected.

13. A method according to any one of claims 10 to 12, further comprising a step of decanting and / or separation of hydrocarbons and inorganic solid particles present in the water using two-phase separators, triphasic separators, desalters , hydrocyclones, centrifuges, flotation cells, filtration equipment, tanks, or basins, which can be mounted in series and / or in parallel.

14. Process according to any one of Claims 10 to 13, implemented in a preventive or curative manner.

15. Method according to any one of claims 10 to 13, wherein the injection water consists of production water, sea water, spring water, water of condensation, rain water or a mixture of water from these different sources.

16. Process according to any one of claims 10 to 15, in which the injection water consists of production water comprising a quantity of sodium chloride greater than 30 gL ^-1 , or even greater than 50 gL ^-1. , and even greater than 100 gL ^-1 .

17. Method according to any one of claims 10 to 16, implemented in the case of primary, secondary or tertiary recovery.

18. A method according to any one of claims 10 to 16, implemented in the case of hydraulic fracturing and / or acidification.

19. Composition comprising at least one compound of formula (1) defined in any one of claims 1 to 7, at least one hydrocarbon, inorganic solid particles and water.

20. The composition of claim 19, wherein the mass ratio compound (s) of formula (1) / inorganic solid particles is between 5.10 ^"6 and 1, preferably between 10 ^"5 and ^{10" 1,} more preferably between 5.10 ^"5 and ^{10" 1,} and most most preferably between 5.10 ^"and 5.10 ^{^3" 2.}

21. A composition according to claim 19 or claim 20, wherein the amount of hydrocarbon (s) is between 0.5 ppm and 10% by weight relative to water, the amount of inorganic solid particles is between 0.5 ppm and 10% by weight relative to water, and the amount of compound of formula (1) is between 0.5 ppm and 10000 ppm, preferably between 0.5 ppm and 5000 ppm, preferably still between 0.5 ppm and 2000 ppm, and advantageously between 2 ppm and 500 ppm, by volume relative to the volume of water.