WO2013150131A1

WO2013150131A1 - Surfactant compounds, compositions comprising same, method for synthesizing same, and uses thereof, in particular for the assisted recovery of hydrocarbons

Info

Publication number: WO2013150131A1
Application number: PCT/EP2013/057181
Authority: WO
Inventors: Maurice Bourrel; Nadège LAGASSE
Original assignee: Total S.A.
Priority date: 2012-04-06
Filing date: 2013-04-05
Publication date: 2013-10-10
Also published as: FR2989093A1; FR2989093B1; RU2014139991A

Abstract

The present invention relates to surfactant compounds of formula (I): R (OB)_p (OP)_m (OE)_n CH (SO₃M) - COOR', where R is an alkyl or alkylaryl radical having a C3-C30 alkyl chain or a mixture of said radicals; R' is an alkyl or alkylaryl radical having a C1-C30 alkyl chain, a - [(CH₂)_xO]_y-Z radical, where x is an integer from 1-20, y is an integer from 1-75, and Z is H or a C1-C5 alkyl radical, or a -(ΟΕ)_n' (OP)_m' (ΟΒ)_p' R" radical, where n' is an integer from 1-75, m' is an integer from 1-75, p' is an integer from 0-75, and R" is an alkyl or alkylaryl radical having a C1-C30 alkyl chain, a - [(CH₂)_x'O]_y-Z' radical, where x' is an integer from 1-20, y' is an integer from 1-75, and Z' is H, or a C1-C5 alkyl radical; m is an integer from 1-75; n is an integer from 1-75; p is an integer from 0-75; and M is an alkali metal or alkaline earth metal cation or a bivalent alkaline earth metal half-cation or an onium ion. The invention further relates to a method for preparing said compounds and to aqueous surfactant compositions comprising one or more of said compounds, in particular a distribution of said compounds. The invention also relates to the use of said compounds and composition for the assisted recovery of hydrocarbons. The invention relates to a method for extracting hydrocarbons in an underground formation.

Description

SURFACTANT COMPOUNDS, COMPOSITIONS COMPRISING THE SAME, PROCESS FOR SYNTHESIS AND USES, IN PARTICULAR FOR ASSISTED RECOVERY

The present invention relates to compounds of the alkoxylated sulphonated ester type, to compositions comprising these esters, to a process for their preparation and to their use as surfactants, especially in the context of petroleum production, in particular the tertiary recovery of hydrocarbons. PRIOR ART

Crude oil accumulated in an underground reservoir is initially produced by drilled wells in the reservoir, with the crude oil ejected. This primary recovery due to the natural forces of the deposits, is carried out with an average recovery rate of the order of 5 to 10%: a significant portion of crude oil remains in the reservoir, trapped in the pores of the porous medium that Training ".

Many enhanced oil recovery (EOR) techniques have been developed and used to increase the recovery rate of conventional oils. The injection of water or gas, especially immiscible hydrocarbon gases, allows the secondary recovery of an additional quantity of crude oil.

The injection of water makes it possible to push the hydrocarbons towards one or more wells through which the oil is recovered. The rates of these recoveries remain however insufficient, especially in the case of oils of high viscosity, in particular because of the immiscibility of the water and the oil and the great interfacial tension between the two phases which leads to the capillary trapping of hydrocarbon droplets.

To increase the microscopic efficiency of enhanced recovery by effectively mobilizing the hydrocarbons trapped in the pores of the rock, it has been proposed to use surfactants injected with water, for tertiary recovery. They come to the oil / water interface and are intended to reduce the oil / water interfacial tension - microemulsions can be formed which have a reduced or zero interfacial tension with the oil, and lower the capillary pressure. Indeed, in an oil / water system, it is at the interface that the energy is highest, and the oil or water adopts a spherical shape to limit the contact surface. But the oil molecules located on the periphery, unbalanced by the contiguity with water, tend to enter the drop to find their equilibrium, which generates a capillary pressure that prevents the drop from being deformed. By lowering the interfacial tension, the surfactants lower the capillary pressure and the droplets of oil can deform and, more easily, pass pore thresholds and move into the porous channels of the formation and be ejected, and ultimately recovered.

Many surfactants have been proposed for this purpose. The surfactants must be adapted to the tertiary recovery conditions considered and according to the parameters of the reservoir considered (water quality, salinity, pH, composition and viscosity of the hydrocarbons, temperature, ...) to obtain optimal recovery rates, by the collapse of the oil / water interfacial tension.

The surfactants have a polar hydrophilic part (called "head"), which has an affinity for water and a lipophilic part (called "tail") which has an affinity for oil.

To improve the effectiveness of a surfactant, it is necessary to obtain the strongest possible interactions and of equal energy between the tail of the surfactant and the oil, on the one hand, and between the head of the surfactant and the water, on the other hand. In addition, the microemulsion must remain fluid, and therefore free of microgels that may be induced by the spatial arrangement of the surfactants at the oil / water interface.

In low-temperature and low-salt tanks (salinity of the order of 35 g / l), the surfactants known in the field of detergency are usually used. The hydrophilic part of these detergents is however not very active under high salinity conditions, and for the recovery of oils in carbonated tanks, which are hot, very salty, other surfactants must be used, where the hydrophilic head is reinforced. .

For example, it has been proposed nonionic surfactants whose lipophilic hydrocarbon tail, usually a long chain (about C20), in strong interaction with the oil, is bonded to a portion of ethylene oxide units [EO] - which gives hydrophilicity

[tail] - O [OE] _z H

where z can vary from 5 to 50, depending on the nature of the lipophilic tail, but they are not very effective at high temperature and their hydrophilicity, for example above 80 ° C remains insufficient even increasing z. It has been proposed to sulfate the terminal ethylene oxide unit

[tail] - O [OE] _z S0 ₃ ^" , Na ⁺ ,

this reinforcing the hydrophilicity, but this function hydrolyzes and is not stable at high temperature, and the carboxylate alternative

[tail] - O [OE] _z CH ₂ COO ^" , Na ⁺ ,

if it is more stable, requires basic pHs for good ionization. It has also been proposed to insert, between the tail and the etherified tail portion, propylene oxide - [OP] - units, which are lipophilic, reinforcing the lipophilic character of the tail, but the resulting surfactants [tail] - O- [OP] _z - [EO] _z - CH2 - COO ^" , Na ⁺ ,

where z 'can vary from 5 to 30 require very high z numbers to achieve sufficient hydrophilicity and the ionic character of the molecule tends to disappear, according to WO 2012/027757.

Like most surfactants described above, however, they must be used in admixture with others to give interesting results. Indeed, to adjust to the conditions related to the reservoir (water quality, salinity, pH, composition and viscosity of hydrocarbons, temperature, ...), mixtures of hydrophilic and hydrophobic compounds are usually used by adjusting their concentrations. .

For example, US Pat. No. 4,077,471 proposes the use of aqueous compositions of alkylpolyalkoxysulphonates or of alkylarylpolyalkoxy-sulfonates having C8-C24 alkyl chains and alkoxy portions containing 1 to 20 alkoxy units, mixed with a nonionic surfactant such as a polyethoxylated aliphatic alcohol or a polyethoxylated alkylphenol. The synthesis of these sulfonates is difficult and is not carried out on an industrial scale.

Furthermore, FR 2 549 524 discloses α-sulfocarboxylic acid esters, resistant to hydrolysis, compared to fatty esters, in a wide pH range and at high temperatures. To form microemulsions, they are implemented with a co-surfactant.

In summary, mixtures of hydrophilic and hydrophobic compounds are usually proposed whose respective concentrations are adjusted to the reservoir (water quality, salinity, pH, composition and viscosity of the hydrocarbons, temperature, etc.). The mixture of surfactants with characteristics very different hydrophilic-lipophilic properties, however, fears a fractionation in transport in porous media and consequently a decrease in the effectiveness of the mixture.

There is therefore a need for compounds capable of adjusting, in a single molecule, the hydrophilic and hydrophobic properties, which avoids having to adjust surfactant mixtures to meet the criteria imposed by the recovery site.

The present invention provides novel compounds whose formula combines the surfactant properties and the advantages of the adjustment of its different portions, and whose synthesis allows to modulate these properties and advantages. They appear schematically with the following portions:

[.. hydrocarbon tail ..] - [OP or OB-OP portion] - [EO portion] - [sulfonated head C (S0 ₃ M) H - COO ester] - [pref. branched], where OB is butylene oxide.

Thus, the present invention relates to compounds of formula (I)

R (OB) p (OP) _m (EO) _n CH (SO ₃ M) - COOR '(I) in which

R is an alkyl or alkylaryl radical whose alkyl chain has from 3 to 30 carbon atoms or a mixture of such radicals,

R 'is an alkyl or alkylaryl radical whose alkyl chain has from 1 to 30 carbon atoms; a radical - [(CH ₂ ) _x O] _y -Z where x is an integer from 1 to 20, y is an integer from 1 to 75, and Z is H or a C1-C5 alkyl radical; or a radical - (ΟΕ) _η ·

(OP) _m '(OB) p' R "where n 'is an integer from 1 to 75, m' is an integer from 1 to 75, p 'is an integer from 0 to 75, and R "is an alkyl or alkylaryl radical whose alkyl chain has from 1 to 30 carbon atoms, a radical - [(CH2) xO] yZ 'where x' is an integer ranging from 1 to 20, y 'a whole number ranging from 1 to

75, and Z 'is H or a C1-C5 alkyl radical,

m is an integer from 1 to 75,

n is an integer from 1 to 75,

p is an integer from 0 to 75,

M is an alkali or alkaline earth metal cation or a half-cation, in the case of divalent alkaline earth metals, or an onium ion.

In the compounds of the invention, at least two of the three units EO, OP and OB are present. In other words, according to the invention, the values p, m, n, n ', m' and p 'are not zero at the same time. Their formula is designed to combine the advantages of sulphonated fatty esters and those of alkoxylated acids in their salified neutralized form, without the disadvantages.

In fact, on the one hand, the sulphonated fatty acids exhibit an excellent behavior with respect to the salinity of the water, thanks to the sulphonate function associated with the ester function, as well as a good temperature stability, but their performance is limited by the choice of lipophilic chains usually available and the insufficient length of these usual lipophilic chains (C16-C22). On the other hand, the hydrophobic part of the alkoxylated acids, thanks to the diversity of the R radicals that can be envisaged and to the adjustable number of propylene oxide (PO) units, allows a great adaptability of the interactions with the oil. In addition, their hydrophilic part is mainly due to ethylene oxide (EO) units, which give the molecule a non-ionic character, despite the carboxylate function, which sometimes has drawbacks related to the temperature of use.

Among these compounds, there are preferred compounds of formula (I) for which R is an alkyl or alkylaryl radical whose alkyl chain has 5 to 25 carbon atoms, R 'is an alkyl or alkylaryl radical whose alkyl chain has 1 at 25 carbon atoms, or a radical - [(CH ₂ ) _x O] _y -Z where x is an integer from 2 to 5, y is an integer from 1 to 5, and Z is H or a C1-C5 alkyl radical, m is a number integer from 1 to 15, n is an integer from 1 to 5, p is an integer from 0 to 5, M is an alkali or alkaline earth metal cation or a half-cation in the case of divalent alkaline earth metals or an onium ion.

The compounds where R 'is a radical (ΟΕ) _η · (OP) _m ' (ΟΒ) _ρ · R "are particularly preferred according to the invention.

These new compounds are surfactants. They are easy to synthesize, stable, and their formula overcomes the problems associated with mixtures of two different molecules usually used, molecules that can each act without an expected collective result or whose arrangement can induce the formation of gels, liquid crystals, etc. that hinder recovery because they increase the viscosity.

Moreover, the formula of these compounds has the advantage of being flexible according to the needs related to the deposits and the conditions of realization of the assisted recovery. Depending on the type of oil to be recovered, and this for all types of oils, including viscous oils, depending on the reservoir (viscosity, salinity, temperature, etc ...), and conditions of extraction, it is possible to adapt the synthesis and the compounds obtained, on a case-by-case basis, by modulating the choice of the R radical of the lipophilic tail, the number p, m and n of units of the ethoxylated and propoxylated (and optionally butoxylated) portion. and the alkyl radical R 'of the ester.

In a particular advantageous embodiment of the surfactant molecules of the invention, R and / or R 'and / or R "are branched alkyl radicals, such as radicals derived from Guerbet alcohols or isostearyl alcohol. to avoid the formation of gels which could appear by alignment of linear chains, as is the case when using surfactants comprising long carbon chains.

According to a second aspect, the invention relates to surfactant compositions comprising one or more compounds of formula (I) or a distribution of these compounds.

In addition, the invention relates to a process for preparing a compound of formula R (OB) p (OP) _m (EO) _n CH (SO ₃ M) -COOR '(I) according to the invention or a mixture or a distribution of compounds of formula (I) or a surfactant composition according to the invention comprising at least the steps of: a) etherifying the alcohol or mixture of alcohols of formula ROH (II) in a first optional butoxylation step and a second propoxylation step, and a third ethoxylation step; b) carbomethylating the compound (s) R (OB) p (OP) _m (EO) _n H (III) obtained in step a); then c) sulfonating the compound (s) R (OB) _p (OP) _m (EO) _n CH ₂ -C (O) OH (IV) obtained in b) and d) esterifying the compound (s) R (OB) _p ( OP) _m (EO) _n CH (SO ₃ H) -C (O) OH (V) obtained in c) with the aid of the alcohol R'OH [or c ') esterifying the compound (s) R- ( OB) _p (OP) _m (EO) _n CH ₂ -C (O) OH (IV) obtained in b) with the aid of alcohol R'OH and (d) sulfonating the compound (s) R (OB) _p (OP) _m (EO) _n CH ₂ -C (O) OR '(VII) obtained in c')]; then e) neutralize the reaction mixture obtained.

Since p may be zero, the butoxylation step is optional. Moreover, the first and second steps can be carried out simultaneously in a propoxylation / butoxylation step. Thus, the OB and OP patterns can be mixed. In a preferred embodiment of the invention, the addition is sequential. OB motifs and then OP motifs are preferably added.

The method of the invention has the advantage of leading to usable compounds regardless of the tanks whose exploitation is targeted, including carbonated reservoirs, under the conditions of salinity, temperature and viscosity of the various concerned oils.

In addition, the invention relates to a process for extracting hydrocarbons present in a subterranean formation, comprising injecting an aqueous composition into the subterranean formation and producing hydrocarbons displaced by the injected aqueous composition, wherein implementation of an aqueous surfactant composition according to the invention, in particular for a tertiary recovery phase.

Finally, the invention relates to the use of the compounds according to the invention as surfactants. It also relates to the use of a composition according to the invention for the enhanced recovery of hydrocarbons, and in particular for the tertiary recovery phase.

The invention will be better understood on reading the following detailed description and the attached figure, which illustrates the preparation process in the case of the compound of formula (I) where R is a C17 linear chain, p is 0, m is 9, n is 4 and R 'is methyl and M ⁺ is Na ⁺ . The compounds of the invention of formula (I) may, according to one or more embodiments of the invention, be defined by one of the following characteristics or by any combination of minus two of the following characteristics:

- p is 0;

M is an onium ion selected from triethanolammonium, triethylammonium, pyridinium or a cation or half-cation of a metal selected from the group comprising lithium, sodium, potassium, magnesium and calcium;

M is a monovalent cation;

- M is Na;

R is a linear alkyl chain;

- R is a C12 to C30 alkyl chain;

- R is a C16 to C20 alkyl chain; R is a C17 alkyl chain;

- R is a branched alkyl chain C12 to C30;

- R is a C16 to C20 branched alkyl chain;

x is between 2 and 5;

- is between 1 and 5;

R 'is a C1 to C8 alkyl chain,

- R 'is a branched alkyl chain C3 to C5;

- R 'is ethyl or methyl;

Z is H, Me or Et;

m is between 1 and 15, preferably 1 and 10;

n is between 1 and 10, preferably 1 and 5;

p is between 0 and 10, preferably 0 and 5;

R 'is (OE) _n (OP) _m . (OB) _p . R "and

n is between 1 and 10, preferably between 1 and 5;

- m 'is between 1 and 15, preferably between 1 and 10;

p 'is between 0 and 10, preferably between 0 and 5;

- R "is a C1 to C8 alkyl chain;

- R "is a branched alkyl chain C3 to C5;

- R "is ethyl or methyl;

Z 'is H, ethyl or methyl;

- R "is an alkyl or alkylaryl radical whose alkyl chain has 1 to 25 carbon atoms;

- R "is a radical - [(CH ₂ ) _X '0] _γ · -Ζ', where x 'is an integer ranging from 2 to 5, y' is an integer ranging from 1 to 5 and Z 'is H or a C1 to C5 alkyl radical.

By "alkyl" radical is meant here a radical having a linear or branched, saturated or unsaturated hydrocarbon-based chain of 3 to 30 carbon atoms, preferably 5 to 25 carbon atoms, more preferably 5 to 22 carbon atoms. . Nonlimiting examples of R alkyl groups are in particular linear C16 and C18 fatty chains.

By "aryl" is meant a monocyclic or multicyclic aromatic group system comprising at least one aromatic ring comprising from 6 to 16 carbon atoms, and preferably from 6 to 10 carbon atoms. A nonlimiting example of an aryl group is phenyl.

By "alkylaryl" is meant alkyl attached to an aryl group, as defined above, the link to the parent group being effected by the aryl group. Non-limiting examples of R alkylaryl groups are in particular nonylbenzene, dodecylbenzene, hexadecylbenzene, dodecyltoluene, dodecylorthoxylene.

By "distribution" is meant here the collection of the compounds obtained according to a distribution related to the reaction conditions and the quantities of eq. of oxides used at each time of the etherification, as will appear below.

In the definition of R specifying the formula of the compounds (I), although the chains may be unsaturated or comprise unsaturated cyclic links or substituents, the linear or branched saturated alkyl chains are preferred according to the invention, in particular for reasons related to synthesis. Indeed, unsaturations or unsaturated rings are likely to react during certain stages of their preparation, especially during the sulphonation step and are therefore preferably not present in the R chain.

By way of example of modulation of the formula by the choice of R ', in the case of the methyl ester (R' is Me) the methyl ester part is very hydrophilic, and it is possible to carry out an ethyl ester to lower the hydrophilicity.

For the case where the alkyl chain is too weakly hydrophobic, as is the case with shorter chains, this can be compensated for by the presence of propylene oxide (PO) and / or butylene oxide (OB) units in the alkoxylated portion.

The method of synthesis of the compounds of the invention appears in Table I below.

R - OH (II)

i ETHERIFICATION ΟΡ, ΟΒ)

) at)

I OE ETHERIFICATION

R - [OB] - - [OP] _I- - [OE] _n - H (III)

CARBOMETHYLATION b)

R - [OB - [OP] _m - [OE] - CH ₂ - COOH (IV)

SULFONATION c) ESTERIFICATION C) ~ [OB] _p - OP] _m .- [OE] "- C (S0 ₃ H) H - COOH (] _p - [OP] _m - [OE] _n - C¾ - COOR '( VII) ESTERIFICATION d) SULFONATION <T)

R - [OB] "- [OP] _r - [EO]" - C (S0 ₃ H) H - COOR '(VI)

NEUTRALIZATION

R - [OB] _p - [OP] _m - [EO] "- C (S0 ₃ M) H - COOR '(I)

TABLE 1

To carry out the first etherification step of the alcohol or mixtures of alcohols of formula ROH, ROH (II) alcohols or R-OH (II) mixtures are treated in two stages. ROH alcohols are preferably commercial and available. In a first step, ROH is treated by usual methods of butoxylation and then propoxylation, or possibly simultaneous propoxylation and butoxylation, to react this alcohol or mixture of alcohols in the presence of a suitable catalyst, with butylene oxide and then propylene (or a mixture of propylene oxide and butylene oxide).

As a catalyst, it is possible to use, for example, sodium hydroxide, or sodium in pellets, or potassium hydroxide. Butylene oxide generates OB units: -CH (CH ₃ ) CH (CH ₃ ) O-. Propylene oxide generates units or units OP: -CH (CH ₃ ) CH ₂ O-. The amount of butylene oxide (respectively propylene oxide), and the reaction time determine the degree of butoxylation (respectively degree m of propoxylation) which also partly determine the properties of the surfactant product.

Thus, the units OP and OB can be mixed to give a portion [(OB) _p (OP) _m ], when OP and OB are introduced together into the reactor or be in two distinct portions, when reacting successively OB and OP. According to the invention, it is preferred to react OB and OP to give the portions (OB) _p and (OP) _m .

In a third step, ethylene oxide is added to the reaction medium under customary reaction conditions, to fix the [EO] _n portion and to obtain the corresponding compound. The amount of ethylene oxide, which generates OE units or units: - CH ₂ CH ₂ 0-, and the reaction time determine the degree of ethoxylation (the value of n), which also partly determines the properties surfactant product.

The alkoxylation reactions generally lead to a distribution of molecules with different degrees of aikoxylation. For example, in the case of the ethoxylation of an alcohol ROH, the ethoxylated molecules obtained have a degree of ethoxylation distributed according to a Poisson distribution:

[RO (CH ₂ CH ₂ 0) _n H] = [ ^R Q ^H (In [ ^{R 0H} ] Q) ", where [] indicates the concentration of the species n \ R OH

considered, of degree of ethoxylation n, [R OH] ₀ and [R OH] are the initial and unreacted alcohol concentrations, respectively.

Catalysts and reaction conditions suitable for carrying out the etherification are described in particular in US 2007/0100097 or in the "Nonionic surfactants", M.J. Schick Ed. M. Dekker, 1967.

It is during these etherification steps that the distribution of the mixtures of compounds of formula (I) obtained is obtained, generally a portion (OE) _n contiguous to a portion

[(OB) _p (OP)

A mixture of molecules of formula (III) R (OB) _p (OP) _m (EO) _n H, the distribution of which is preserved at the subsequent stages, is obtained. In order to carry out the carbomethylation of the compound or compounds of formula (III) obtained in the etherification step, chloroacetic acid may be used and the method described in US 2010/0081716 may be used.

However, any other suitable method or reagent for this carbomethylation may be chosen.

The compounds of formula (IV), obtained with the same distribution as the corresponding compounds (III), are then sulphonated and then esterified. The sulphonation step may be carried out under the usual conditions compatible with the structure of the compounds (IV) and (VII). In particular, the method described in Organic Syntheses, Coll. Vol 4 p 862 (1963), Vol 36 p83 (1956), or sulfur trioxide gas phase, according to WO 2009/098176 A1, to obtain the sulfonated acids of formula (V).

Esterification of these compounds can then be carried out in the usual manner using the alcohol R'OH to obtain compounds or mixtures of compounds of formula (VI). The esterification reaction takes place in the presence of p-toluene sulfonic acid catalyst or other organic sulfonic acids such as o-toluenesulphonic acid, naphthalenesulphonic acid, for example, or in the presence of acid. sulfuric. Since the esterification reaction takes place in a solvent medium, the alcohol R'OH may, according to the invention, act as a solvent.

At the end of the sulfonation and esterification steps, the reaction medium is neutralized by any suitable means to obtain a neutral pH. For example, one can use sodium hydroxide, optionally in pellets or potash added to the reaction medium.

In a second variant, however, the compounds of formula (IV) can initially be esterified to R (OB) _p (OP) _m (EO) _n CH ₂ -C (O) OR '(VII) and then sulphonated, for to the compounds or mixtures of compounds of formula (VI), neutralized if necessary in the same way as in the first variant, in the form of compounds or mixtures of final compounds of formula (I).

The compositions of the invention comprise at least one compound of formula (I). Taking into account in particular their method of obtaining, the compositions generally however comprise a mixture of products having the basic formula (I) with variations of m, n and R ', and possibly p, and possible variations of R if the ROH starting compounds are "variegated". This mixture, with regard to m, n, p and R, is constituted as of the etherification step, according to a distribution depending on the conditions of realization of step a) in its two or three times.

The surfactant compositions of the invention may be in the form of an aqueous solution. In this case, the mass proportion of the compounds of formula (I) in the aqueous solution is preferably between 0.01% and 30%, preferably between 0.1 and 20%, more preferably between 0.1. and 5%. The compositions may further comprise one or more additives such as co-surfactants, co-solvents or adjuvant (s). Their addition can be made originally, before storage, or extemporaneously during injection. They can be chosen from salts, surfactants of different formula of formula (I), sacrificial agents, mobility control polymers, pH adjusting agents.

As an adjuvant, a hydrocarbon can be used.

As an additive of the polymer type, it is possible, for example, to use the polyacrylamide products described in US Pat. No. 2,731,414 or US Pat. No. 2,827,964.

As additive of the polysaccharide type, it is possible, for example, to use the products described in documents US Pat. No. 4,006,058 or US Pat. No. 4,233,438.

The compounds of the invention are useful as surfactants in various fields, such as detergents, emulsion lubricants, and more generally as emulsifiers, dispersants, foaming agents, detergents and cleaners in industry, including industry. oil, but also that of textiles or cosmetics, in agriculture, for the inhibition of corrosion, in the lubricants industry, the cement industry, for example.

In petroleum exploitation in particular, the surfactant compositions according to the invention are particularly useful for assisted tertiary hydrocarbon recovery. To recover crude oil, at least one injection well is injected with a surfactant composition according to the invention, in the form of an aqueous solution, into the subterranean formation containing hydrocarbons, especially crude oil.

The surfactant composition displaces the oil, in particular by forming an oil / water microemulsion. This area of reduced interfacial tension then propagates in the formation.

Beforehand, it is possible to inject water, hydrocarbon and / or brine fluids or a composition of the invention with a separate formulation. The hydrocarbons are recovered by means of at least one remote production well (s) from the injection well (s).

In order for the injection of surfactants to be optimized, it is preferable to have a salinity gradient. In particular, in the presence of polymers, the surfactants are injected with a polymer at a given salinity, and the stopper formed is pushed with salt water, possibly containing a polymer, at a lower salinity than that of the stopper. Generally, to adjust the surfactant compositions and their additives, and adjust their characteristics to the target formation, the compositions are tested pipette, then carrots and / or models of porous rock. Given the adaptability of the molecules of the invention, the compositions and production method are useful for tertiary recovery in all types of formation, hydrocarbons and operating conditions. They are particularly useful in pH ranges of the order of 5 to 9, more particularly 6 to 8. They are particularly useful for recovering oils from carbonate reservoirs, and particularly under conditions of high salinity and / or for oils with high viscosity. Thus, they can be used for conventional viscosity oils ranging from 0.5 to 100 cP, but also for the recovery of more viscous oils, up to 1000 cP or more. They can be used for normal salinities and also salinities strong training water, it can go up to 200-250g / l, that is to say the near-saturation.

EXAMPLES Example 1

The scheme of FIG. 1 illustrates a procedure for the synthesis of a sulphonated ester of formula (I) according to the invention for which R is a C17 linear chain, p is 0, m is 9, n is

And R 'is methyl and M is Na.

C ₇ H ₃₅ - [OP] ₉ - [OE] ₄ - CH (SO ₃ Na) - C (O) O-CH ₃ (1)

a) Etherification:

In a tricolor, at 1, 15 eq. of potassium metal, previously washed with ethanol then with toluene, in 23 ml of cyclohexane, was added 1 eq. of alcohol CH ₃ - (CH 2) 5-CH ₂ OH: compound (2), and brought the mixture to 80 ° C for 3 days. A solution of potassium alkoxide in cyclohexane was obtained.

1, 1 eq. Propylene oxide (PO) was introduced into a volume of heptane (8 ml of propylene oxide per 14 ml of heptane) and 1 eq. potassium alcoholate solution and 0.13 eq. triisobutylaluminum (25% by weight solution in toluene). The reaction was conducted at 0 ° C for 15 hours.

A similar procedure was then followed with ethylene oxide and thus the compound (3) was obtained.

b) Carbomethylation:

In the tricol with a thermometer and a condenser, 1 eq. alcohol at 70 ° C, and added 1, 1 eq. sodium salt of chloroacetic acid and 1.1 eq. sodium hydroxide (in pellet). The reaction medium is colored. It was heated at 75 ° C for 1 hour and then at 85 ° C for 1 hour.

After cooling the medium and adding a solution of 10% hydrochloric acid until a pH of 2 is obtained, the reaction medium comprising the acid (4) was concentrated.

c) Sulfonation:

In the three-necked flask equipped with a thermometer and a refrigerant connected to the traps, 1 eq. acid (4) diluted in a volume of chloroform (for 20 g, 60 ml of chloroform), then slowly added 1, 1 eq. of chlorosulfonic acid, introduced from the addition funnel, the reaction mixture was colored and the mixture was refluxed for 1 hour.

The reaction mixture was cooled and the chloroform distilled at atmospheric pressure. The product was allowed to dry in the desiccator for 24 hours.

This reaction was conducted according to the synthesis described in Organic Syntheses, Coll. Vol 4 p 862 (1963), Vol 36 p83 (1956).

d) Esterification and neutralization:

1.5 eq. CH ₃ OH alcohol and 1 eq. sulfonated acid (5) in the reactor and then added a spatula tip of p-toluenesulfonic acid and brought the mixture to reflux for 2h. When the reaction was complete, the medium containing the compound (6) was cooled, then the solution was neutralized with sodium hydroxide solution to reach a neutral pH, and then the alcohol and water were distilled off. to obtain the neutralized sulfonated ester (1).

To increase the purity of the product (1), the di-salt is precipitated in distilled water by introducing 10 ml of distilled water to 3 g of hot-dissolved product. The di-salt is then precipitated by cooling, filtered and the product (6) is concentrated in the aqueous phase.

Example 2

The synthesis of the product (6) of Example 1 is carried out in the same way, except that the sulfonation step and the esterification step are reversed, the esterification d) being carried out before the sulfonation c) .

Claims

1. Compounds of formula (I)

R (OB) p (OP) _m (EO) _n CH (SO ₃ M) - COOR '(I)

in which

(OP) _m '(OB) p' R "where n 'is an integer from 1 to 75, m' is an integer from 1 to 75, p 'is an integer from 0 to 75, and R "is an alkyl or alkylaryl radical whose alkyl chain has from 1 to 30 carbon atoms, a radical - [(CH ₂ ) _x O] _y -Z 'where x' is an integer ranging from 1 to 20, y an integer ranging from 1 to 75, and Z 'is H or a C 1 -C 5 alkyl radical,

m is an integer from 1 to 75,

n is an integer from 1 to 75,

p is an integer from 0 to 75, and

M is an alkali or alkaline earth metal cation or a half-cation of a divalent alkaline earth metal or an onium ion.

2. Compounds according to claim 1, having the formula (I) in which

R is an alkyl or alkylaryl radical whose alkyl chain has from 5 to 25 carbon atoms,

R 'is an alkyl or alkylaryl radical whose alkyl chain has 1 to 25 carbon atoms, or a radical - [(CH ₂ ) _x O] _y -Z where x is an integer ranging from 2 to 5, y an integer ranging from 1 to 5, and Z is H or a C 1 -C 5 alkyl radical,

m is an integer from 1 to 15,

n is an integer from 1 to 5,

p is an integer from 0 to 5, and

3. Compounds according to claim 1 having the formula

R (OB) _p (OP) _m (EO) _n CH (SO ₃ M) -COO (EO) _n . (OP) _m - (OB) _p - R ", wherein

m is an integer from 1 to 15, n is an integer from 1 to 5,

p is an integer from 0 to 5,

n 'is an integer from 1 to 5,

m 'is an integer from 1 to 15,

p 'is an integer from 0 to 5,

"is an alkyl or alkylaryl radical whose alkyl chain has 1 to 25 carbon atoms, or a radical - [(CH ₂ ) _X '0] _γ · -Ζ', where x 'is an integer ranging from 2 to 5, y 'is an integer from 1 to 5 and Z' is H or a C1 to C5 alkyl radical, and M is an alkali or alkaline earth metal cation or a half cation of a divalent alkaline earth metal or an onium ion .

4. Compounds according to claim 1 to 3, characterized in that p is 0.

5. Compounds according to one of claims 1 to 4, characterized in that M is an onium ion selected from triethanolammonium, triethylammonium, pyridinium or a cation or half cation of a metal selected from the group comprising lithium, sodium, potassium, magnesium and calcium, preferably a monovalent cation, more preferably Na ⁺ .

6. Compounds according to one of claims 1 to 5, characterized in that R is a C12 to C30 alkyl chain, preferably C16 to C20, more preferably C17 or a C12 to C30 branched chain, preferably in C16 to C20.

7. Compounds according to one of claims 1 to 6, characterized in that R 'is a C1 to C8 alkyl chain, and preferably ethyl or methyl or a branched alkyl chain C3 to C5.

8. Compounds according to one of claims 1 to 7, characterized in that Z is H, Me or Et.

9. Surface-active composition, characterized in that it comprises a compound or several compounds of formula (I) according to one of claims 1 to 8 or a distribution of these compounds.

10. Surface-active composition according to claim 9, in the form of an aqueous solution, the mass proportion of the compounds of formula (I) in the aqueous solution being preferably between 0.01% and 30%, preferably between 0.1 and 20% and more preferably between 0.1 and 5%.

1 1. An aqueous surfactant composition according to claim 9 or 10, characterized in that it further comprises one or more additives selected from salts, additional surfactants, sacrificial agents, mobility control polymers, pH and mixtures thereof.

12. aqueous surfactant composition according to one of claims 9 to 1 1, characterized in that it comprises one or more additives of the polymer type, preferably polyacrylamide or polysaccharide type and mixtures thereof.

13. Process for preparing a compound of formula

R (OB) p (OP) _m (EO) _n CH (SO ₃ M) -COOR '(I) according to one of claims 1 to 8 or a mixture or a distribution of compounds of formula (I ) or a composition according to one of claims 9 to 11, characterized in that, R, p, m, n and R 'being defined as in claims 1 to 8, it comprises at least the steps of

a) etherifying the alcohol or mixture of alcohols of formula ROH (II) in a first optional butoxylation step and a second propoxylation step, the first and second steps being able to be carried out simultaneously, and a third ethoxylation step,

b) carbomethylating the compound (s) R (OB) _p (OP) _m (EO) _n H (III) obtained in step a), and then

[c) sulfonating the compound (s) R (OB) _p (OP) _m (EO) _n CH ₂ -C (O) OH (IV) obtained in b) and d) esterifying the compound (s) R (OB) _p ( OP) _m (EO) _n CH (SO ₃ H) -C (O) OH (V) obtained in c) using R'OH] or

[c ') esterifying the compound (s) R (OB) _p (OP) _m (EO) _n CH ₂ -C (O) OH (IV) obtained in b) using R'OH and

to sulphonate the compound (s) R (OB) _p (OP) _m (EO) _n CH ₂ -C (O) OR '(VII) obtained in c')] and

e) neutralizing the reaction mixture obtained.

14. A process for extracting hydrocarbons present in a subterranean formation, comprising injecting an aqueous composition into the subterranean formation and producing hydrocarbons displaced by the injected aqueous composition, characterized in that the composition comprises at least a compound or a mixture of compounds according to one of claims 1 to 8 or a surfactant composition according to one of claims 9 to 12.

15. Use of a composition according to one of claims 9 to 12 for the enhanced recovery of hydrocarbons.