EP3820963A1 - Sulphonated internal ketone-based formulations for assisted recovery of oil - Google Patents

Sulphonated internal ketone-based formulations for assisted recovery of oil

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Publication number
EP3820963A1
EP3820963A1 EP19734440.1A EP19734440A EP3820963A1 EP 3820963 A1 EP3820963 A1 EP 3820963A1 EP 19734440 A EP19734440 A EP 19734440A EP 3820963 A1 EP3820963 A1 EP 3820963A1
Authority
EP
European Patent Office
Prior art keywords
ketones
sulfonated
composition according
internal
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19734440.1A
Other languages
German (de)
French (fr)
Inventor
Mikel Morvan
Pascal Pitiot
Loïc BAUSSARON
Roberto COMPANY
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
IFP Energies Nouvelles IFPEN
Rhodia Operations SAS
Original Assignee
IFP Energies Nouvelles IFPEN
Rhodia Operations SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by IFP Energies Nouvelles IFPEN, Rhodia Operations SAS filed Critical IFP Energies Nouvelles IFPEN
Publication of EP3820963A1 publication Critical patent/EP3820963A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16—Enhanced recovery methods for obtaining hydrocarbons

Definitions

  • the present invention relates to the field of petroleum extraction, and more particularly to techniques known as enhanced oil recovery.
  • a fluid is injected (re-injection of the water produced diluted or not, injection of sea or river water, or injection of gas, for example) into the hydrocarbon tank, with a view to exerting within the tank, an overpressure capable of entraining the oil towards the production well (s).
  • a common technique in this context is the injection of water (also known as flooding or “waterflooding”), in which large volumes of water are injected under pressure into the reservoir via injector wells. The injected water entrains part of the oil it encounters and pushes it towards one or more producing wells.
  • the surfactants usually recommended for EOR are typically anionic surfactants, generally of the sulfate or sulfonate type.
  • anionic surfactants generally of the sulfate or sulfonate type.
  • compositions useful for EOR which comprise particular sulfonates, namely internal ketones sulfonated in alpha of the ketone group, more precisely mixtures of mono-sulfonated ketones (c that is to say sulfonated on only one of the alpha positions of the carbonyl group) and di-sulfonated (sulfonated on both positions).
  • the compositions of WO 2016/177817 are typically obtained by sulfonation of internal ketones.
  • the “Mobility Reduction” (noted Rm), to which reference is made in the present description, is a well-known parameter in the field of petroleum extraction, and it is applied here to the injection of an aqueous solution surfactant.
  • Rm aqueous solution of surfactant comprising at least one surfactant and an aqueous solvent medium (which can typically be water or brine)
  • the value of the reduction in mobility is obtained from the Darcy relation: it corresponds the ratio between the value of the pressure drop measured during the injection of the aqueous solution of surfactants considered at a given flow rate (DR solution) compared to the value of the pressure drop measured, before injection of the surfactant solution, during the injection of the aqueous solvent medium without the surfactants (DR solvent):
  • Q represents the flow rate of a fluid of viscosity h
  • DR represents the pressure drop caused by the fluid flow
  • k represents the permeability which can be defined as the hydraulic conductivity of the porous medium, which is expressed in Darcy (1 D "0.987 pm 2 ).
  • the reduction in mobility Rm defined above corresponds to the effective viscosity of the surfactant solution in the porous medium and it is by definition greater than 1.
  • a surfactant solution proves to be all the more difficult to inject as its value of Rm is high.
  • An object of the present invention is to provide compositions based on sulfonated internal ketones, but not leading to this phenomenon of amplification of the reduction in mobility over time.
  • the inventors have demonstrated an original technical solution: it turns out that the effect of increasing the reduction in mobility can be counteracted by using the internal sulfonated ketones together with a sufficient quantity of non-internal ketones. sulfonated.
  • the work carried out by the inventors in the context of the present invention shows that, if non-sulfonated internal ketones are added to a composition based on sulfonated internal ketones, there is a limit value of the molar concentration of non-sulphonated ketones (defined by the ratio of the quantity of non-sulphonated ketones compared to the total quantity of sulphonated and non-sulphonated ketones), hereinafter called "limit molar concentration" such that:
  • the reduction in mobility reaches a limit value after a short stabilization period, and the reduction mobility then remains substantially stable over time.
  • the limiting molar concentration of non-sulfonated ketones can vary to a large extent depending on the sulfonated ketones and non-sulfonated ketones used.
  • the limit molar concentration can be established experimentally by iteration, by testing a molar concentration of non-sulfonated ketones and by observing for this concentration the evolution obtained for the reduction mobility. If the reduction in mobility stabilizes, the molar concentration tested is greater than or equal to the limit ratio, otherwise it is lower.
  • the limit molar concentration of non-sulfonated ketones for a given sulfonated ketone / non-sulfonated ketone system is typically greater than 10% (it is for example of the order of 15% for the composition of the example illustrative described in more detail at the end of this description).
  • non-sulfonated ketones are preferably used as an additive, with a molar concentration of ketones not preferably less than 50%, typically less than or equal to 30%, or even 25 %.
  • the subject of the present invention is the advantageous compositions identified by the inventors, namely the compositions of sulfonated internal ketones comprising non-sulfonated ketones in an amount greater than or equal to the limit value allowing stabilization of the reduced mobility.
  • compositions comprising:
  • (B) non-sulfonated internal ketones with a molar ratio B / (A + B), corresponding to the molar concentration of non-sulfonated ketones, which is greater than or equal to the limit molar concentration of non-sulfonated ketones from which a stabilization of the reduction in mobility is observed when injecting the mixture of said sulfonated internal ketones and said non-sulfonated internal ketones into a porous medium.
  • the molar ratio B / (A + B) is between 10% and 50%, and it is preferably less than 50%, in particular between 10 and
  • the invention relates to the use of the aforementioned compositions for enhanced oil recovery.
  • the invention more specifically relates to an enhanced oil recovery process from an underground formation, in which:
  • the ratio of mono-sulfonated internal ketones / internal di-sulfonated ketones is advantageously between 1: 99 and 99: 1, for example between 3: 97 and 97: 3; especially between 5: 95 and 95: 5
  • the compounds A present in the composition of the invention comprise a mixture of at least one mono-sulfonate and at least one disulfonate corresponding respectively to formulas (1) and (2) below :
  • each of Ri, R 3 and R 5 is, independently, a hydrogen or a linear or branched alkyl chain having from 1 to 20 carbon atoms;
  • each of R 2 and R 4 which may be identical or different, is independently a linear alkyl chain or having from 4 to 24 carbon atoms, said alkyl chain possibly comprising cycloaliphatic groups;
  • X is H; or -S0 3 X is a sulfonate salt formed with 1 / n mole of a cation X n + where n is the valence of the cation, this cation being advantageously chosen from the group consisting of ammonium cations NH and metal cations, especially alkaline and alkaline earth metals such as sodium, potassium, calcium and magnesium cations.
  • each of R 1; R 3 and R 5 is hydrogen or an alkyl group having 1 to 6 carbon atoms, and it is preferred that each of R 1; R 3 and R 5 denote hydrogen, methyl, ethyl, propyl, butyl, pentyl or hexyl groups; and advantageously hydrogen.
  • Each of R 2 and R 4 preferably contains from 6 to 18 carbon atoms and more preferably from 6 to 14 carbon atoms.
  • the compounds of formula (1) and (2) are preferably obtained by sulfonation of internal ketones obtained from fatty acids or else from a mixture of fatty acids, typically using the Piria reaction.
  • Fatty acids well suited as a starting point for the synthesis of the compounds of formula (1) and (2) include caprylic, capric, lauric, myristic, palmitic, stearic, arachidic, behenic, lignoceric, cerotic acids and their mixtures. One can also start from some of their derivatives, such as their esters and their anhydrides.
  • Preferred fatty acids are caprylic, capric, lauric, myristic, palmitic, stearic, naphthenic, isostearic acids and their mixtures.
  • Good candidates are fatty acids from coconut oil or palm oil, which include fatty acids with 8 to 18 carbon atoms.
  • the starting fatty acids can optionally comprise one or more ethylenic unsaturations, as is the case for example with oleic, linolenic or erucic acids. In general, however, it is preferred to avoid the presence of such unsaturations in view of the fact that the double bonds are subjected to sulfonation and therefore lead to mixtures of less defined structures than with alkyl chains devoid of double Nasions.
  • ketones suitable for the preparation of internal sulfonated ketones according to the invention are those derived from naphthenic acids.
  • the sulfonates of formula (1) or (2) can be obtained from a single internal ketone of well defined composition. Most often, the sulfonates of formula (1) or (2) are obtained from a mixture of several distinct internal ketones, whereby the sulfonated internal ketones are mixtures comprising several compounds of formula (1) and (2 ) with separate chain lengths.
  • the compounds B present in a composition according to the invention correspond to the unsulfonated version of the compounds A present elsewhere.
  • the compounds B preferably correspond to the formula (3) below:
  • R 1; R 2, R 3 , R 4 and R 5 have the abovementioned meanings;
  • R 6 is hydrogen or a linear or branched alkyl chain having from 1 to 20 carbon atoms, preferably hydrogen.
  • a composition according to the invention is prepared by only partially sulfonating a compound of formula (3) or else a mixture of compounds of formula (3) using a sulfonating agent.
  • a mixture of compounds of formulas (1) and (2) constituting the compounds A of the composition and residual compounds of formula (3) constituting the compounds B of the composition is then obtained.
  • the partial sulfonation of the compounds of formula (3) is advantageously carried out so that the molar concentration of non-sulfonated ketones at the end of the sulfonation is at least equal to the limit molar concentration ensuring stabilization reduced mobility.
  • the partial sulfonation of the compounds of formula (3) can, in absolute terms, be carried out using any suitable sulfonating agent.
  • a sulfonating agent advantageously concentrated, chosen from sulfuric acid, sulfuric acid monohydrate, an oleum, chlorosulfonic acid, sulfamic acid and sulfur trioxide S0 3 .
  • the sulfonation is carried out using gaseous sulfur trioxide S0 3 as sulfonating agent, preferably using the falling film technique.
  • the reaction mixture can advantageously be subjected to ripening. Furthermore, it is generally advantageous to neutralize the reaction medium with a basic compound, typically NaOH, this neutralization being advantageously carried out with stirring, and preferably at a temperature of 40 to 100 ° C for 15 minutes to 5 hours, typically between 40 minutes and 3 hours.
  • a basic compound typically NaOH
  • composition according to the invention can advantageously comprise a certain number of additives in addition to compounds A and B.
  • composition according to the invention comprises the compounds A and B within an aqueous medium comprising dissolved salts, typically a brine.
  • This aqueous medium containing dissolved salts preferably has a salinity similar to that of the underground formation in which the composition according to the invention is intended to be injected, which tends to improve the efficiency of the recovery of petroleum.
  • the total salt content in a composition according to the invention is advantageously in the range between 1 to 200 g / L, preferably from 5 to 150 g / L.
  • salts advantageously present in the composition of the invention mention may in particular be made, without limitation, of the halides of alkali and alkaline-earth metals, such as NaCI, KCI, RbCI, CsCI, MgCI, BeCI2, CaCI 2 .
  • a composition according to the invention generally comprises several distinct types of salt and the salt concentration to which reference is made corresponds to the total amount of all the salts present.
  • the total concentration of compounds A and B within said saline aqueous medium is between 0.5 and 50 g / L, preferably between 1 and 30 g / L, for example between 2 and 20 g / L.
  • composition according to the invention can advantageously comprise other additives, in particular additives improving the quality of oil recovery.
  • a composition according to the invention may advantageously comprise additional surfactants, for example nonionic surfactants, chosen for example, if appropriate, from alkoxylated nonyl phenol, alkoxylated dinonylphenol, alkoxylates, in particular alcohol, branched at C8 to C20. Carboxylated, phosphated, sulfated surfactants, or other sulfonated surfactants than Compounds A.
  • surfactants of interest in the context of the present invention are the alkyl glyceryl ether sulfonates (AGES), for example obtained according to the methods described in US 3,024,273 or US 2,989,547.
  • AGES alkyl glyceryl ether sulfonates
  • AGES can be described by the following general formula:
  • R 7 represents a linear or branched alkyl or alkenyl chain typically having from 3 to 32 carbon atoms; m is equal to 0 or else m is an integer ranging from 1 to 20, preferably from 2 to 15; The cation is preferably chosen from the group consisting of sodium, potassium, ammonium, calcium or magnesium.
  • alkoxylated alkyl glyceryl ether sulfonates or AAGES (for the alkoxylated alkyl glyceryl ether sulfonates) which correspond to the following formula (5):
  • R 7 , m and Y have the meanings given for the above formula (4); and each of n and p, identical or different, is an integer ranging from 0 to 20, preferably from 2 to 15, it being understood that n + p is not zero.
  • compounds of AGES or AAGES type are present in a composition according to the invention, they are typically present at a content of between 0.5 and 50 g / L, preferably between 1 and 25 g / L.
  • AGES or AAGES can be used jointly, if necessary with an AGES / AAGES mass ratio between 1: 10 and 10: 1, preferably from 1: 5 to 5: 1.
  • the internal ketone used is an internal C23-35 ketone which was obtained by Piria reaction catalyzed with magnetite.
  • Partial sulfonation was carried out using SO 3 gas in a falling film reactor cooled by a double jacket with water, under the following conditions:
  • Composition C Composition CO: Mixture M: 2 g / l Mixture MO: 2 g / l
  • compositions C and CO By mixing compositions C and CO in variable proportions, five Solutions 1 to 5 described in the table below were obtained, which have variable contents of residual internal ketones, reported in the column on the far right: the value reported , expressed as a percentage, corresponds to the molar concentration of compound A, namely the ratio A / (A + B).
  • Solution 1 corresponds to composition C -
  • Solution 2 corresponds to composition C0
  • the system is maintained at 60 ° C in an oven.
  • the fluid injection rate is 0.0165 ml / min (which corresponds to 15s 1 shear suffered by the fluid during its propagation in the medium).
  • Pressure sensors are used to measure the pressure difference across the porous medium. From the pressure measurements, the reduction in mobility Rm of the surfactant solution is determined.

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Abstract

The present invention relates to compositions for assisted recovery of oil, comprising: (A) alpha-sulphonated internal ketones of the ketone group; and (B) non-sulphonated internal ketones, with a molar ratio B/(A+B) greater than or equal to the limit molar concentration of non-sulphonated ketones, from which a stabilisation of the reduction in mobility is observed when the mixture of said ketones is introduced into a porous medium.

Description

Formulations à base de cétones internes sulfonées  Formulations based on sulfonated internal ketones
pour la récupération assistée du pétrole  for enhanced oil recovery
La présente invention a trait au domaine de l’extraction pétrolière, et plus particulièrement aux techniques dites de récupération assistée du pétrole. The present invention relates to the field of petroleum extraction, and more particularly to techniques known as enhanced oil recovery.
Lors de l’extraction du pétrole hors d’un réservoir hydrocarboné (réservoir pétrolifère telle qu’une formation rocheuse, consolidée ou non, ou un sable, par exemple), selon une première étape dite de « récupération primaire », le pétrole est entraîné hors d’un puits de production par la surpression régnant naturellement au sein du réservoir. Cette récupération primaire ne permet d’accéder qu’à une faible quantité du pétrole contenu dans le réservoir, typiquement de l’ordre de 10 à 15% tout au plus. During the extraction of petroleum from a hydrocarbon reservoir (petroleum reservoir such as a rock formation, consolidated or not, or a sand, for example), according to a first stage called "primary recovery", the petroleum is entrained out of a production well by the overpressure prevailing naturally within the reservoir. This primary recovery only gives access to a small quantity of the oil contained in the reservoir, typically of the order of 10 to 15% at most.
Pour permettre de poursuivre l’extraction du pétrole suite à cette récupération primaire, des méthodes secondaires de production sont employées, quand la pression du réservoir devient insuffisante pour déplacer le pétrole encore en place. Typiquement, on injecte un fluide (ré-injection de l'eau produite diluée ou non, injection d'eau de mer ou de rivière, ou encore injection de gaz, par exemple) au sein du réservoir hydrocarboné, en vue d'exercer au sein du réservoir une surpression propre à entraîner le pétrole vers le(s) puits de production. Une technique usuelle dans ce cadre est l'injection d'eau (désignée également par inondation ou « waterflooding »), dans laquelle de grands volumes d'eau sont injectés sous pression dans le réservoir via des puits d'injecteurs. L'eau injectée entraîne une partie du pétrole qu'elle rencontre et le pousse vers un ou plusieurs puits producteur(s). Les méthodes secondaires de production telles que l’injection d'eau ne permettent toutefois d’extraire qu’une partie relativement faible des hydrocarbures en place (typiquement de l’ordre de 30%). Ce balayage partiel est dû notamment au piégeage de l’huile par les forces capillaires, aux différences de viscosité et de densité existant entre le fluide injecté et les hydrocarbures en place, ainsi qu’à des hétérogénéités à des échelles micro- ou macroscopiques (échelle des pores et aussi échelle du réservoir). To allow further extraction of the oil following this primary recovery, secondary production methods are used, when the reservoir pressure becomes insufficient to move the oil still in place. Typically, a fluid is injected (re-injection of the water produced diluted or not, injection of sea or river water, or injection of gas, for example) into the hydrocarbon tank, with a view to exerting within the tank, an overpressure capable of entraining the oil towards the production well (s). A common technique in this context is the injection of water (also known as flooding or “waterflooding”), in which large volumes of water are injected under pressure into the reservoir via injector wells. The injected water entrains part of the oil it encounters and pushes it towards one or more producing wells. Secondary production methods such as water injection, however, only allow a relatively small portion of the hydrocarbons in place to be extracted (typically around 30%). This partial sweeping is due in particular to the trapping of the oil by the capillary forces, to the differences in viscosity and density existing between the injected fluid and the hydrocarbons in place, as well as to heterogeneities. at micro- or macroscopic scales (pore scale and also reservoir scale).
Pour essayer de récupérer le reste du pétrole, qui demeure dans les formations souterraines à l’issue de la mise en œuvre des méthodes primaires et secondaires de production, il a été proposé différentes techniques dites de « récupération assistée du pétrole » (ou récupération assistée (ou améliorée) d’hydrocarbures RAH), ou bien encore « EOR » (pour l’anglais « Enhanced OU Recovery »). Parmi ces techniques, on peut citer des techniques s’apparentant à l’injection d'eau (inondation) précitée, mais employant une eau comprenant des additifs tels que, par exemple, des agents tensioactifs solubles dans l’eau (on parle alors typiquement de « surfactant flooding »). L’emploi de tels agents tensioactifs induit notamment une diminution de la tension interfaciale eau/pétrole, qui est propre à assurer un entraînement plus efficace du pétrole piégé dans les constrictions de pores. To try to recover the rest of the oil, which remains in the underground formations at the end of the implementation of the primary and secondary methods of production, it has been proposed different techniques called "enhanced oil recovery" (or enhanced recovery (or improved) of RAH hydrocarbons), or even "EOR" (for English "Enhanced OR Recovery"). Among these techniques, mention may be made of techniques akin to the aforementioned injection of water (flooding), but employing water comprising additives such as, for example, water-soluble surfactants (this is typically referred to as of "surfactant flooding"). The use of such surfactants in particular induces a reduction in the water / oil interfacial tension, which is capable of ensuring a more effective entrainment of the oil trapped in the pore constrictions.
Les tensioactifs usuellement préconisés pour l’EOR sont typiquement des tensioactifs anioniques, en général de type sulfate ou sulfonate. En particulier, il a été décrit dans la demande WO 2016/177817 des compositions utiles pour l’EOR qui comprennent des sulfonates particuliers, à savoir des cétones internes sulfonées en alpha du groupement cétone, plus précisément des mélanges de cétones mono-sulfonées (c’est-à-dire sulfonées sur une seule des positions en alpha du groupe carbonyle) et di- sulfonées (sulfonées sur les deux positions). Les compositions de WO 2016/177817 sont typiquement obtenues par sulfonation de cétones internes. The surfactants usually recommended for EOR are typically anionic surfactants, generally of the sulfate or sulfonate type. In particular, there has been described in application WO 2016/177817 compositions useful for EOR which comprise particular sulfonates, namely internal ketones sulfonated in alpha of the ketone group, more precisely mixtures of mono-sulfonated ketones (c that is to say sulfonated on only one of the alpha positions of the carbonyl group) and di-sulfonated (sulfonated on both positions). The compositions of WO 2016/177817 are typically obtained by sulfonation of internal ketones.
Dans le cadre des travaux qui ont conduit à la présente invention, les inventeurs ont maintenant mis en évidence que, dans le cas le plus général, les mélanges du type décrits dans WO 2016/177817, et en particulier les mélanges des exemples de cette demande de brevet, présentent un inconvénient en termes de transport en milieu poreux. Plus précisément, il s’avère que l’injection des mélanges de WO 2016/177817 conduit à une augmentation constante de la réduction de mobilité lors de l’injection du mélange, ce qui traduit un endommagement du milieu poreux. In the context of the work which led to the present invention, the inventors have now demonstrated that, in the most general case, mixtures of the type described in WO 2016/177817, and in particular the mixtures of the examples of this application patent, have a drawback in terms of transport in porous medium. More specifically, it turns out that the injection of mixtures of WO 2016/177817 leads to a constant increase in the reduction in mobility during the injection of the mixture, which translates into damage to the porous medium.
La « Réduction de Mobilité » (notée Rm), à laquelle il est fait référence dans la présente description, est un paramètre bien connu dans le domaine de l’extraction pétrolière, et il est appliqué ici à l’injection d’une solution aqueuse de tensioactif. Pour une solution aqueuse de tensioactif donnée comprenant au moins un tensioactif et un milieu aqueux solvant (qui peut typiquement être de l’eau ou une saumure), la valeur de la réduction de mobilité est obtenue à partir de la relation de Darcy : elle correspond au rapport entre la valeur de la perte de charge mesurée lors de l’injection de la solution aqueuse de tensioactifs considérée à un débit donné (DR solution) rapportée à la valeur de la perte de charge mesurée, avant injection de la solution de tensioactif, lors de l’injection du milieu aqueux solvant sans les tensioactifs (DR solvant) : The “Mobility Reduction” (noted Rm), to which reference is made in the present description, is a well-known parameter in the field of petroleum extraction, and it is applied here to the injection of an aqueous solution surfactant. For a given aqueous solution of surfactant comprising at least one surfactant and an aqueous solvent medium (which can typically be water or brine), the value of the reduction in mobility is obtained from the Darcy relation: it corresponds the ratio between the value of the pressure drop measured during the injection of the aqueous solution of surfactants considered at a given flow rate (DR solution) compared to the value of the pressure drop measured, before injection of the surfactant solution, during the injection of the aqueous solvent medium without the surfactants (DR solvent):
Rm = DR solution/ DR solvant Dans le cas d'un écoulement laminaire de liquide dans in milieu poreux de sectionRm = DR solution / DR solvent In the case of a laminar flow of liquid in a porous section medium
S et de longueur L, la loi de Darcy s'écrit : où : S and of length L, Darcy's law is written: or :
Q représente le débit d'un fluide de viscosité h,  Q represents the flow rate of a fluid of viscosity h,
DR représente la perte de charge provoquée par l'écoulement du fluide DR represents the pressure drop caused by the fluid flow
k représente la perméabilité qui peut être définie comme étant la conductivité hydraulique du milieu poreux, qui s'exprime en Darcy (1 D « 0.987 pm2). La réduction de mobilité Rm définie ci-dessus correspond à la viscosité effective de la solution de tensioactif dans le milieu poreux et elle est par définition supérieure à 1. Une solution de tensioactif s’avère d’autant plus difficile à injecter que sa valeur de Rm est élevée. k represents the permeability which can be defined as the hydraulic conductivity of the porous medium, which is expressed in Darcy (1 D "0.987 pm 2 ). The reduction in mobility Rm defined above corresponds to the effective viscosity of the surfactant solution in the porous medium and it is by definition greater than 1. A surfactant solution proves to be all the more difficult to inject as its value of Rm is high.
Sauf à ce que le rapport Rm soit indûment élevé, l’existence d’un Rm ne reflète pas en soi une problématique particulière en termes de propagation du fluide. En revanche, une augmentation de la valeur de la réduction de mobilité à mesure qu’on poursuit l’injection reflète une autre problématique, à savoir un endommagement du milieu poreux au cours du temps lors de l’injection. Il peut typiquement s’agir de phénomène de colmatage de la structure poreuse. C’est cette problématique qui est rencontrée dans le cas le plus général avec les compositions du type décrites dans WO 2016/177817. Cette problématique est tout particulièrement marquée pour les débits relativement faibles qui sont obtenus de facto au sein de la formation poreuse. Unless the ratio Rm is unduly high, the existence of an Rm does not in itself reflect a particular problem in terms of propagation of the fluid. On the other hand, an increase in the value of the reduction in mobility as the injection is continued reflects another problem, namely damage to the porous medium over time during the injection. It can typically be a clogging phenomenon of the porous structure. It is this problem which is encountered in the most general case with the compositions of the type described in WO 2016/177817. This problem is particularly marked for the relatively low flow rates which are obtained de facto within the porous formation.
Un but de la présente invention est de fournir des compositions à base de cétones internes sulfonées, mais ne conduisant pas à ce phénomène d’amplification de la réduction de mobilité au cours du temps. An object of the present invention is to provide compositions based on sulfonated internal ketones, but not leading to this phenomenon of amplification of the reduction in mobility over time.
A cet effet, les inventeurs ont mis en évidence une solution technique originale : il s’avère qu’on peut contrecarrer l’effet d’augmentation de la réduction de mobilité en employant les cétones internes sulfonées conjointement à une quantité suffisante de cétones internes non sulfonées. To this end, the inventors have demonstrated an original technical solution: it turns out that the effect of increasing the reduction in mobility can be counteracted by using the internal sulfonated ketones together with a sufficient quantity of non-internal ketones. sulfonated.
Ce résultat est d’autant plus surprenant qu’on se serait davantage attendu, a priori, à ce que la présence de composés de type cétones internes induisent une augmentation de la réduction de la mobilité : en effet, les cétones internes s’apparentent à des composés hydrophobes, et il était dès lors plus logique de penser que leur mise en oeuvre induirait le phénomène inverse de celui obtenu. Plus singulier encore, il s’avère que les cétones internes non sulfonées ne fournissent leur effet d’inhibition de l’augmentation de la réduction de mobilité que lorsqu’elles sont employées en une teneur suffisante. En d’autres termes, et contrairement à ce qu’on aurait pu intuitivement supposer, la solution mise en lumière par les inventeurs pour éviter l’augmentation de la réduction de mobilité ne consiste pas seulement à employer des additifs qui, en soi, sont plutôt de de nature à induire une augmentation, mais aussi à mettre en œuvre ces additifs en une proportion notable. This result is all the more surprising since one would have expected, a priori, that the presence of compounds of the internal ketone type would induce an increase in the reduction in mobility: in fact, the internal ketones are similar to hydrophobic compounds, and it was therefore more logical to think that their use would induce the opposite phenomenon to that obtained. Even more remarkable, it turns out that the internal, unsulfonated ketones provide their inhibitory effect on the increase in the reduction in mobility only when they are used in a sufficient content. In other words, and contrary to what one could have intuitively supposed, the solution put forward by the inventors to avoid the increase in the reduction of mobility does not consist only in using additives which, in themselves, are rather likely to induce an increase, but also to use these additives in a significant proportion.
Plus précisément, et sans vouloir être lié à une théorie particulière, les travaux réalisés par les inventeurs dans le cadre de la présente invention montrent que, si on ajoute des cétones internes non sulfonées à une composition à base de cétones internes sulfonées, il existe une valeur limite de la concentration molaire en cétones non sulfonées (définie par le rapport de la quantité de cétones non sulfonées rapportée à la quantité totale de cétones sulfonées et non sulfonées), dite ci-après « concentration molaire limite » telle que: More specifically, and without wishing to be bound to a particular theory, the work carried out by the inventors in the context of the present invention shows that, if non-sulfonated internal ketones are added to a composition based on sulfonated internal ketones, there is a limit value of the molar concentration of non-sulphonated ketones (defined by the ratio of the quantity of non-sulphonated ketones compared to the total quantity of sulphonated and non-sulphonated ketones), hereinafter called "limit molar concentration" such that:
- pour les mélange à base des cétones sulfonées et non sulfonées avec une concentration molaire en cétones non sulfonées en deçà de la concentration molaire limite, on observe une augmentation de la réduction de la mobilité au cours du temps lorsqu’on injecte le mélange dans un milieu poreux ; - for mixtures based on sulfonated and non-sulfonated ketones with a molar concentration of non-sulfonated ketones below the limit molar concentration, an increase in the reduction in mobility is observed over time when the mixture is injected into a porous medium;
- pour les mélange à base des cétones sulfonées et non sulfonées avec une concentration molaire en cétones non sulfonées supérieur ou égal à la de la concentration molaire limite, la réduction de la mobilité atteint une valeur limite après une courte période de stabilisation, et la réduction de mobilité reste ensuite sensiblement stable au cours du temps. - for mixtures based on sulphonated and non-sulphonated ketones with a molar concentration of non-sulphonated ketones greater than or equal to that of the limit molar concentration, the reduction in mobility reaches a limit value after a short stabilization period, and the reduction mobility then remains substantially stable over time.
Pour une composition donnée de cétones sulfonées et de cétones non sulfonées, la concentration molaire limite en cétones non sulfonées peut varier en une large mesure en fonction des cétones sulfonées et de cétones non sulfonées employées. Pour une composition donnée, à base de cétones sulfonées et de cétones non sulfonées spécifiques, la concentration molaire limite peut être établie expérimentalement par itération, en testant une concentration molaire en cétones non sulfonées et en observant pour cette concentration l’évolution obtenue pour la réduction de mobilité. Si la réduction de la mobilité se stabilise, la concentration molaire testée est supérieure ou égal au rapport limite, sinon elle est inférieure. En testant plusieurs concentrations molaires, on peut ainsi déterminer aisément la concentration molaire limite en cétones non sulfonées pour un système cétones sulfonées / cétones non sulfonées donné, en l’encadrant par approches successives. For a given composition of sulfonated ketones and non-sulfonated ketones, the limiting molar concentration of non-sulfonated ketones can vary to a large extent depending on the sulfonated ketones and non-sulfonated ketones used. For a given composition, based on sulfonated ketones and specific non-sulfonated ketones, the limit molar concentration can be established experimentally by iteration, by testing a molar concentration of non-sulfonated ketones and by observing for this concentration the evolution obtained for the reduction mobility. If the reduction in mobility stabilizes, the molar concentration tested is greater than or equal to the limit ratio, otherwise it is lower. By testing several molar concentrations, it is thus possible to easily determine the limit molar concentration of non-sulphonated ketones for a given sulphonated ketone / non-sulphonated ketone system, by framing it by successive approaches.
Dans le cas le plus général, la concentration molaire limite en cétones non sulfonées pour un système cétones sulfonées / cétones non sulfonées donné est typiquement supérieur à 10% (elle est par exemple de l’ordre de 15% pour la composition de l’exemple illustratif décrit plus en détails à la fin de la présente description). Par ailleurs, dans la cadre de la présente invention, on utilise de préférence les cétones non sulfonées à titre d’additif, avec une concentration molaire en cétones non de préférence inférieure à 50%, typiquement inférieure ou égal à 30%, voire à 25%. In the most general case, the limit molar concentration of non-sulfonated ketones for a given sulfonated ketone / non-sulfonated ketone system is typically greater than 10% (it is for example of the order of 15% for the composition of the example illustrative described in more detail at the end of this description). Furthermore, in the context of the present invention, non-sulfonated ketones are preferably used as an additive, with a molar concentration of ketones not preferably less than 50%, typically less than or equal to 30%, or even 25 %.
Selon un premier aspect, la présente invention a pour objet les compositions avantageuses identifiées par les inventeurs, à savoir les compositions de cétones internes sulfonées comprenant des cétones non sulfonées en une quantité supérieure ou égale à la valeur limite permettant d’obtenir une stabilisation de la réduction de mobilité. According to a first aspect, the subject of the present invention is the advantageous compositions identified by the inventors, namely the compositions of sulfonated internal ketones comprising non-sulfonated ketones in an amount greater than or equal to the limit value allowing stabilization of the reduced mobility.
Plus précisément, la présente invention a pour objet des compositions comprenant : More specifically, the subject of the present invention is compositions comprising:
(A) des cétones internes sulfonées en alpha du groupement cétone ; et (A) internal ketones sulfonated in alpha of the ketone group; and
(B) des cétones internes non sulfonées, avec un rapport molaire B/(A+B), correspondant à la concentration molaire en cétones non sulfonées, qui est supérieur ou égal à la concentration molaire limite en cétones non sulfonées à partir de laquelle on observe une stabilisation de la réduction de la mobilité lorsqu’on injecte le mélange desdites cétones internes sulfonées et desdites cétones interne non sulfonées dans un milieu poreux. (B) non-sulfonated internal ketones, with a molar ratio B / (A + B), corresponding to the molar concentration of non-sulfonated ketones, which is greater than or equal to the limit molar concentration of non-sulfonated ketones from which a stabilization of the reduction in mobility is observed when injecting the mixture of said sulfonated internal ketones and said non-sulfonated internal ketones into a porous medium.
Typiquement, dans une composition selon l’invention, le rapport molaire B/(A+B) est compris entre 10% et 50%, et il est de préférence inférieur à 50%, notamment entre 10 etTypically, in a composition according to the invention, the molar ratio B / (A + B) is between 10% and 50%, and it is preferably less than 50%, in particular between 10 and
30%. 30%.
Selon un autre aspect, l’invention a pour objet l’utilisation des compositions précitées pour la récupération assistée de pétrole. According to another aspect, the invention relates to the use of the aforementioned compositions for enhanced oil recovery.
Dans ce cadre, l’invention a notamment pour objet plus spécifique un procédé de récupération assistée du pétrole d’une formation souterraine, dans lequel : In this context, the invention more specifically relates to an enhanced oil recovery process from an underground formation, in which:
- on injecte dans ladite formation souterraine, par au moins un puits d’injection, une composition du type précité ; et - on récupère, par au moins un puits de production, un fluide véhiculant le pétrole sortant de la formation souterraine. - Is injected into said underground formation, by at least one injection well, a composition of the aforementioned type; and - recovering, by at least one production well, a fluid carrying the oil leaving the underground formation.
Différentes caractéristiques et modes de réalisation particuliers de l’invention vont maintenant être décrits plus en détails. Les cétones internes sulfonées en alpha du groupement cétone Various particular characteristics and embodiments of the invention will now be described in more detail. The internal ketones sulfonated in alpha of the ketone group
(composés A)  (compounds A)
Les composés A de type cétones internes sulfonées qui sont présents dans les compositions de l’invention sont avantageusement présents sous la forme d’un mélange incluant (i) des cétones internes mono-sulfonées (c’est-à-dire sulfonées sur une seule des positions en alpha du groupe carbonyle C=0) ; et (ii) de cétones internes di-sulfonées (à savoir sulfonées sur les deux positions en alpha du groupe carbonyle). The compounds A of the sulfonated internal ketone type which are present in the compositions of the invention are advantageously present in the form of a mixture including (i) mono-sulfonated internal ketones (that is to say sulfonated on a single alpha positions of the carbonyl group C = 0); and (ii) internal di-sulfonated ketones (ie sulfonated at the two alpha positions of the carbonyl group).
Le rapport cétones internes mono-sulfonées/ cétones internes di-sulfonées est avantageusement compris entre 1 :99 et 99 :1 , par exemple entre 3 :97 et 97 :3 ; notamment entre 5 :95 et 95 :5 The ratio of mono-sulfonated internal ketones / internal di-sulfonated ketones is advantageously between 1: 99 and 99: 1, for example between 3: 97 and 97: 3; especially between 5: 95 and 95: 5
Selon un mode de réalisation intéressant, les composés A présents dans la composition de l’invention comprennent un mélange d’au moins un mono-sulfonate et d’au moins un disulfonate répondant respectivement aux formules (1 ) et (2) ci-dessous : According to an interesting embodiment, the compounds A present in the composition of the invention comprise a mixture of at least one mono-sulfonate and at least one disulfonate corresponding respectively to formulas (1) and (2) below :
où : or :
chacun de Ri , R3 et R5, identiques ou différents, est, indépendamment, un hydrogène ou une chaîne alkyle linéaire ou ramifiée ayant de 1 à 20 atome(s) de carbone ; each of Ri, R 3 and R 5 , identical or different, is, independently, a hydrogen or a linear or branched alkyl chain having from 1 to 20 carbon atoms;
chacun de R2 et R4, identiques ou différents, est indépendamment un chaîne alkyle linéaire ou ayant de 4 à 24 atome(s) de carbone , ladite chaîne alkyle pouvant comprendre des groupes cycloaliphatiques ; et each of R 2 and R 4 , which may be identical or different, is independently a linear alkyl chain or having from 4 to 24 carbon atoms, said alkyl chain possibly comprising cycloaliphatic groups; and
X est H ; ou bien -S03X est un sel de sulfonate formé avec 1/n mole d’un cation Xn+ où n est la valence du cation, ce cation étant avantageusement choisi dans le groupe consistant en les cations ammonium NH et les cations métalliques, notamment alcalins et alcalino-terreux tels que les cations sodium, potassium, calcium and magnésium. X is H; or -S0 3 X is a sulfonate salt formed with 1 / n mole of a cation X n + where n is the valence of the cation, this cation being advantageously chosen from the group consisting of ammonium cations NH and metal cations, especially alkaline and alkaline earth metals such as sodium, potassium, calcium and magnesium cations.
De préférence, chacun de R1 ; R3 et R5 est un hydrogène ou bien un groupe alkyle ayant de 1 à 6 atomes de carbone, et on préfère que chacun de R1 ; R3 et R5 désigne un hydrogène, un goupe méthyle, éthyle, propyle, butyle, pentyle or hexyle ; et avantageuseemnt un hydrogène. Preferably, each of R 1; R 3 and R 5 is hydrogen or an alkyl group having 1 to 6 carbon atoms, and it is preferred that each of R 1; R 3 and R 5 denote hydrogen, methyl, ethyl, propyl, butyl, pentyl or hexyl groups; and advantageously hydrogen.
Chacun de R2 et R4 contient de préférence de 6 à 18 atomes de carbone et plus préférentiellement de 6 à 14 atomes de carbone. Each of R 2 and R 4 preferably contains from 6 to 18 carbon atoms and more preferably from 6 to 14 carbon atoms.
Les composés de formule (1 ) et (2) sont de préférence obtenus par sulfonation de cétones internes obtenues à partir d’acides gras ou bien de mélange d’acides gras, typiquement en employant la réaction de Piria. Des acides gras bien adaptés comme point de départ pour la synthèse des composés de formule (1 ) et (2) incluent les acides caprylique, caprique, laurique, myristique, palmitique, stéarique, arachidique, béhénique, lignocerique, cérotique et leurs mélanges. On peut également partir de certains de leurs dérivés, comme leurs esters et leurs anhydrides. Des acides gras préférés sont les acides caprylique, caprique, laurique, myristique, palmitique, stearique, naphthénique acids, isostéariques et leurs mélanges. On peut notamment partir de mélanges d’acides gras sous la forme de « coupes » obtenues à partir d’huiles végétales ou animales notamment par saponification ou alcoolyse. De bons candidats sont les acides gras issus de l’huile de coco ou de l’huile de palme, qui comprennent des acides gras comportant de 8 à 18 atomes de carbone. Les acides gras de départ peuvent éventuellement comprendre une ou plusieurs insaturations éthyléniques, comme c’est le cas par exemple avec les acides oléique, linolenique ou érucique. En général cependant, on préféré éviter la présence de telles insaturations compte tenu du fait que les doubles liaisons sont soumise à la sulfonation et conduisent de ce fait à des mélanges de structures moins définies qu’avec les chaînes alkyles dépourvues de doubles Nasions. The compounds of formula (1) and (2) are preferably obtained by sulfonation of internal ketones obtained from fatty acids or else from a mixture of fatty acids, typically using the Piria reaction. Fatty acids well suited as a starting point for the synthesis of the compounds of formula (1) and (2) include caprylic, capric, lauric, myristic, palmitic, stearic, arachidic, behenic, lignoceric, cerotic acids and their mixtures. One can also start from some of their derivatives, such as their esters and their anhydrides. Preferred fatty acids are caprylic, capric, lauric, myristic, palmitic, stearic, naphthenic, isostearic acids and their mixtures. One can in particular start from mixtures of fatty acids in the form of "cuts" obtained from vegetable or animal oils, in particular by saponification or alcoholysis. Good candidates are fatty acids from coconut oil or palm oil, which include fatty acids with 8 to 18 carbon atoms. The starting fatty acids can optionally comprise one or more ethylenic unsaturations, as is the case for example with oleic, linolenic or erucic acids. In general, however, it is preferred to avoid the presence of such unsaturations in view of the fact that the double bonds are subjected to sulfonation and therefore lead to mixtures of less defined structures than with alkyl chains devoid of double Nasions.
D’autres cétones internes adaptées pour la préparation de cétones internes sulfonées selon l’invention sont ceux dérivés des acides naphténiques. Other internal ketones suitable for the preparation of internal sulfonated ketones according to the invention are those derived from naphthenic acids.
Les sulfonates de formule (1 ) ou (2) peuvent être obtenues à partir d’une unique cétone interne de composition bien définies. Le plus souvent, les sulfonates de formule (1 ) ou (2) sont obtenues à partir d’un mélange de plusieurs cétones internes distinctes, ce par quoi les cétones internes sulfonées sont des mélanges comprenant plusieurs composés de formule (1 ) et (2) avec des longueurs de chaînes distinctes. The sulfonates of formula (1) or (2) can be obtained from a single internal ketone of well defined composition. Most often, the sulfonates of formula (1) or (2) are obtained from a mixture of several distinct internal ketones, whereby the sulfonated internal ketones are mixtures comprising several compounds of formula (1) and (2 ) with separate chain lengths.
Les cétones internes non sulfonées Non-sulfonated internal ketones
(composés B) (compounds B)
Selon un mode de réalisation intéressant, les composés B présents dans une composition selon l’invention correspondent à la version non sulfonée des composés A présents par ailleurs. Ainsi, typiquement, lorsque les composés A sont des composés mono-sulfonates et di-sulfonates répondant respectivement aux formules (1 ) et (2) précitées, les composés B répondent de préférence à la formule (3) ci-dessous : According to an advantageous embodiment, the compounds B present in a composition according to the invention correspond to the unsulfonated version of the compounds A present elsewhere. Thus, typically, when the compounds A are mono-sulfonate and di-sulfonate compounds corresponding respectively to the formulas (1) and (2) above, the compounds B preferably correspond to the formula (3) below:
où : or :
R1 ; R2 , R3 , R4 et R5 ont les significations précités ; et R 1; R 2, R 3 , R 4 and R 5 have the abovementioned meanings; and
R6 est un hydrogène ou bien une chaîne alkyle linéaire ou branchée ayant de 1 à 20 atomes de carbone, de préférence un hydrogène. R 6 is hydrogen or a linear or branched alkyl chain having from 1 to 20 carbon atoms, preferably hydrogen.
Selon un mode de réalisation particulièrement intéressant, une composition selon l’invention est préparée en sulfonant seulement partiellement un composé de formule (3) ou bien un mélange de composés de formule (3) à l’aide d’un agent de sulfonation. On obtient alors un mélange de composés de formules (1 ) et (2) constituant les composés A de la composition et des composés de formule (3) résiduels constituant les composés B de la composition. According to a particularly advantageous embodiment, a composition according to the invention is prepared by only partially sulfonating a compound of formula (3) or else a mixture of compounds of formula (3) using a sulfonating agent. A mixture of compounds of formulas (1) and (2) constituting the compounds A of the composition and residual compounds of formula (3) constituting the compounds B of the composition is then obtained.
Selon ce mode de réalisation, la sulfonation partielle des composés de formule (3) est avantageusement conduite de façon à ce que la concentration molaire en cétones non sulfonées à l’issue de la sulfonation soit au moins égale à la concentration molaire limite assurant la stabilisation de la réduction de mobilité. La sulfonation partielle des composés de formule (3) peut, dans l’absolu, être effectuée en employant tout agent de sulfonation adapté. Par exemple en employant un agent de sulfonation, avanatageusement concentré, choisi parmi l’acide sulfurique, l’acide sulfurique monohydrate, un oleum, l’acide chlorosulfonique, l’acide sulfamique et le trioxyde de soufre S03. According to this embodiment, the partial sulfonation of the compounds of formula (3) is advantageously carried out so that the molar concentration of non-sulfonated ketones at the end of the sulfonation is at least equal to the limit molar concentration ensuring stabilization reduced mobility. The partial sulfonation of the compounds of formula (3) can, in absolute terms, be carried out using any suitable sulfonating agent. For example by using a sulfonating agent, advantageously concentrated, chosen from sulfuric acid, sulfuric acid monohydrate, an oleum, chlorosulfonic acid, sulfamic acid and sulfur trioxide S0 3 .
Selon un mode de réalisation intéressant, la sulfonation est conduite en utilisant le trioxyde de soufre gazeux S03 à titre d’agent de sulfonation, de préférence en utilisant la technique du film tombant. According to an advantageous embodiment, the sulfonation is carried out using gaseous sulfur trioxide S0 3 as sulfonating agent, preferably using the falling film technique.
A l’issue de la sulfonation, le mélange réactionnel peut avantageusement être soumis à un mûrissement. Par ailleurs, il est en général intéressant de neutraliser le milieu réactonnel avec un composé basique, typiquement NaOH, cette neutralisation étant avantageusement conduite sous agitation, et de préférence à une température de 40 à 100°C pendant 15 minutes à 5 heures, typiquement entre 40 minutes et 3 heures. After the sulfonation, the reaction mixture can advantageously be subjected to ripening. Furthermore, it is generally advantageous to neutralize the reaction medium with a basic compound, typically NaOH, this neutralization being advantageously carried out with stirring, and preferably at a temperature of 40 to 100 ° C for 15 minutes to 5 hours, typically between 40 minutes and 3 hours.
Additifs possibles Possible additives
Une composition selon l’invention peut avantageusement comprendre un certains nombre d’additifs en plus des composés A et B. A composition according to the invention can advantageously comprise a certain number of additives in addition to compounds A and B.
Ainsi, il est notamment intéressant que la composition selon l’invention comprenne les composés A et B au sein d’un milieu aqueux comprenant des sels dissous, typiquement une saumure. Thus, it is particularly advantageous for the composition according to the invention to comprise the compounds A and B within an aqueous medium comprising dissolved salts, typically a brine.
Ce milieu aqueux contenant des sels dissous a de préférence une salinité similaire à celle de la formation souterraine où la composition selon l’invention est destinée à être injectée, ce qui tend à améliorer l’efficacité de la récupération du pétrole. Typiquement, la teneur totale en sels dans une composition selon l’invention est avantageusement dans la gamme comprise entre 1 to 200 g/L, de préférence de 5 to 150 g/L. This aqueous medium containing dissolved salts preferably has a salinity similar to that of the underground formation in which the composition according to the invention is intended to be injected, which tends to improve the efficiency of the recovery of petroleum. Typically, the total salt content in a composition according to the invention is advantageously in the range between 1 to 200 g / L, preferably from 5 to 150 g / L.
A titre de sels avantageusement présents dans la composition de l’invention, on peut notamment citer à titre non limitatif les halogénures des métaux alcalins et alcalino- terreux, tels que NaCI, KCI, RbCI, CsCI, MgCI, BeCI2, CaCI2. As salts advantageously present in the composition of the invention, mention may in particular be made, without limitation, of the halides of alkali and alkaline-earth metals, such as NaCI, KCI, RbCI, CsCI, MgCI, BeCI2, CaCI 2 .
Une composition selon l’invention comprend en général plusieurs types de sels distincts et la concentration en sels à laquelle il est fait référence correspond à la quantité totale de tous les sels présents. Typiquement, dans une composition selon l’invention comprenant une milieu aqueux salin du type précité, la concentration totale en composés A et B au sein dudit milieu aqueux salin est entre 0,5 et 50 g/L, de préférence entre 1 et 30 g/L, par exemple entre 2 et 20 g/L. A composition according to the invention generally comprises several distinct types of salt and the salt concentration to which reference is made corresponds to the total amount of all the salts present. Typically, in a composition according to the invention comprising a saline aqueous medium of the aforementioned type, the total concentration of compounds A and B within said saline aqueous medium is between 0.5 and 50 g / L, preferably between 1 and 30 g / L, for example between 2 and 20 g / L.
Par ailleurs, une composition selon l’invention peut avantageusement comprendre d’autres additifs, notamment des additifs améliorant la qualité de la récupération du pétrole. Furthermore, a composition according to the invention can advantageously comprise other additives, in particular additives improving the quality of oil recovery.
Ainsi, à titre d’exemple non limitatif, une composition selon l’invention peut avantageusement comprendre des agents tensioactifs additionnels, par exemple des agents tensioactifs non ioniques, choisis par exemple, le cas échéant, parmi les nonyl phénol alkoxylés, les dinonylphenol alcoxylés, les alcoxylates notamment d’alcool branchés en C8 à C20. Des agents tensioactifs carboxylés, phosphatés, sulfatés additionnels, ou d’autres tensioactif sullfonatés que les composés A. Des agents tensioactifs intéressants dans le cadre de la présente invention sont les alkyl glyceryl ether sulfonates (AGES), par exemple obtenus selon les procédés décrits dans US 3,024,273 ou US 2,989,547. Thus, by way of nonlimiting example, a composition according to the invention may advantageously comprise additional surfactants, for example nonionic surfactants, chosen for example, if appropriate, from alkoxylated nonyl phenol, alkoxylated dinonylphenol, alkoxylates, in particular alcohol, branched at C8 to C20. Carboxylated, phosphated, sulfated surfactants, or other sulfonated surfactants than Compounds A. Surfactants of interest in the context of the present invention are the alkyl glyceryl ether sulfonates (AGES), for example obtained according to the methods described in US 3,024,273 or US 2,989,547.
Les AGES peuvent être décrits par la formule général suivante : AGES can be described by the following general formula:
R7-0-[-CH2-CH(0H)-CH2-0-]m-CH2CH(0H)-CH2-S03Y (4) dans laquelle : R 7 -0 - [- CH2-CH (0H) -CH2-0-] m-CH2CH (0H) -CH2-S0 3 Y (4) in which:
R7 représente une chaîne alkyle ou alcényle linéaire ou ramifiée ayant typiquement de 3 à 32 atomes de carbone ; m est égal à 0 ou bien m est un entier allant de 1 à 20, de préférence de 2 à 15 ; Y is a cation de préférence choisi dans le groupe consistant en sodium, potassium, ammonium, calcium or magnésium. R 7 represents a linear or branched alkyl or alkenyl chain typically having from 3 to 32 carbon atoms; m is equal to 0 or else m is an integer ranging from 1 to 20, preferably from 2 to 15; The cation is preferably chosen from the group consisting of sodium, potassium, ammonium, calcium or magnesium.
D’autres tensioactifs additionnels potentiellement intéressants dans le cadre de la présente invention sont les alkyl glyceryl ether sulfonates alcoxylés ou AAGES ( pour l’anglais alkoxylated alkyl glyceryl ether sulfonates ) qui répondent à la formule (5) suivante : Other potentially useful additional surfactants in the context of the present invention are the alkoxylated alkyl glyceryl ether sulfonates or AAGES (for the alkoxylated alkyl glyceryl ether sulfonates) which correspond to the following formula (5):
R7-0-[-CH2-CH(0H)-CH2-0-]m-[-CH2-CH(CH3)-0]n-[-CH2-CH2-0]p-CH2CH(0H)-H2-S03Y R7-0 - [- CH2-CH (0H) -CH2-0-] m - [- CH2-CH (CH3) -0] n - [- CH2-CH2-0] p-CH 2 CH (0H) - H2-S03Y
(5) dans laquelle : (5) in which:
R7, m and Y ont les significations données pour la formule (4) précitée ; et chacun de n and p, identiques ou différents, est un entier allant de 0 à 20, de préférence de 2 à 15 , étant entendu que n+p n’est pas nul. R 7 , m and Y have the meanings given for the above formula (4); and each of n and p, identical or different, is an integer ranging from 0 to 20, preferably from 2 to 15, it being understood that n + p is not zero.
Lorsque des composés de type AGES ou AAGES sont présents dans une composition selon l’invention, ils sont typiquement présent à une teneur comprise entre 0,5 et 50 g/L, de préférence entre 1 et 25 g/L. When compounds of AGES or AAGES type are present in a composition according to the invention, they are typically present at a content of between 0.5 and 50 g / L, preferably between 1 and 25 g / L.
Selon un mode partciulier, on peut employer conjointement AGES or AAGES, le cas échéant avec un rapport massique AGES/ AAGES entre 1 :10 et 10:1 , de préférence de 1 :5 à 5:1 . According to a particular mode, AGES or AAGES can be used jointly, if necessary with an AGES / AAGES mass ratio between 1: 10 and 10: 1, preferably from 1: 5 to 5: 1.
Différents aspects et avantages de l’invention seront encore illustrés par l’ExempleVarious aspects and advantages of the invention will be further illustrated by the example.
Illustratif donné ci-après Illustrative given below
EXEMPLE EXAMPLE
Dans cet exemple, on a utilisé un mélange de cétones issues de la sulfonation partielle d’une cétone interne. In this example, a mixture of ketones from the partial sulfonation of an internal ketone was used.
La cétone interne utilisée est une cétone interne en C23-35 qui a été obtenue par réaction de Piria catalysée à la magnétite The internal ketone used is an internal C23-35 ketone which was obtained by Piria reaction catalyzed with magnetite.
La sulfonation partielle a été réalisée à l’aide de S03 gazeux dans un réacteur à film tombant refroidit par une double enveloppe avec de l'eau, dans les conditions suivantes : Partial sulfonation was carried out using SO 3 gas in a falling film reactor cooled by a double jacket with water, under the following conditions:
• concentration de S03 dans l'air : 5%v/v • S03 concentration in the air: 5% v / v
• débit d'alimentation en soufre : 1 ,5 kg S / h « conversion supposée S02 --> S03 : 97% • sulfur feed rate: 1.5 kg S / h "assumed conversion S02 -> S03: 97%
• Débit d'alimentation en cétone interne : 12.3 kg/h • Internal ketone feed rate: 12.3 kg / h
A l’issue de la sulfonation, on a obtenu un mélange M de cétones internes sulfonées et non sulfonées avec les concentrations suivantes (déterminées par analyses RMN) : At the end of the sulfonation, a mixture M of sulfonated and non-sulfonated internal ketones was obtained with the following concentrations (determined by NMR analyzes):
A. Cétones interne sulfonées Cétone internes mono-sulfonées : 43,7% en mole A. Internal sulfonated ketones Internal mono-sulfonated ketones: 43.7% by mole
Cétones internes di-sulfonées : 32,4% en mol e Internal sulfonated ketones: 32.4% by mol
B. Cétones internes résiduelles non sulfonées : B. Residual non-sulfonated internal ketones:
24 % en mole Une partie du mélange M ainsi obtenu a ensuite été traité selon le protocole ci-dessous pour en éliminer les cétones internes résiduelles non sulfonées : 24% by mole Part of the mixture M thus obtained was then treated according to the protocol below to remove the residual internal non-sulfonated ketones from it:
Dispersion de 30 g de mélange M sur 70 g de silice dans un solvant (CHCI3). Dispersion of 30 g of mixture M on 70 g of silica in a solvent (CHCI3).
• Elimination du solvant à l’aide d’un rotavapeur. • Removal of the solvent using a rotary evaporator.
• Dépôt sur colonne de silice 330g (flash chromatographie) conditionnée avec du cyclohexanel 00%. • Deposition on 330g silica column (flash chromatography) conditioned with 00% cyclohexanel.
• Élution des cétones internes résiduelles non sulfonées avec • Elution of non-sulfonated residual internal ketones with
cyclohexane/AcOEt (80:20). Après évaporation à sec de cette fraction on récupère 4,4 g de cire orange (IK caractérisée en RMN 1 H)  cyclohexane / AcOEt (80:20). After evaporation to dryness of this fraction, 4.4 g of orange wax are recovered (IK characterized in 1 H NMR)
• Élution du reste de l'échantillon avec CH2CI2/MeOH (80:20). Après évaporation à sec de cette fraction on récupère 24,1 g d'une huile noire. • Elution of the rest of the sample with CH2CI2 / MeOH (80:20). After evaporation to dryness of this fraction, 24.1 g of a black oil are recovered.
• 23 g de cette huile sont introduits dans un ballon de 500 ml et neutralisés à 60°C avec 2.2 équivalents de soude 2N rapportées à l'acidité de l'échantillon mesurée en potentiomètrie. • 23 g of this oil are introduced into a 500 ml flask and neutralized at 60 ° C with 2.2 equivalents of 2N sodium hydroxide based on the acidity of the sample measured in potentiometry.
• Le brut neutralisé est ramené à température ambiante et lyophilisé pour récupérer 26,3 g de solide marron. • The neutralized crude is brought to room temperature and lyophilized to recover 26.3 g of brown solid.
A l’issu du protocole on a obtenu un mélange MO sensiblement exempt de cétones internes résiduelles et constitué essentiellement des cétones internes sulfonées contenu dans le mélange M. A partir des mélanges M et MO, on a préparé deux compositions C et C0 destinées aux tests d’injection et ayant les formulations ci-dessous : At the end of the protocol, a MO mixture was obtained which is substantially free of residual internal ketones and essentially consists of the internal sulfonated ketones contained in the mixture M. From the mixtures M and MO, two compositions C and C0 were prepared for the tests. injection and having the formulations below:
Composition C : Composition CO : Mélange M : 2 g/l Mélange MO : 2 g/l Composition C: Composition CO: Mixture M: 2 g / l Mixture MO: 2 g / l
AGES Exx C13 7 PO 6 EO : 6 g/l AGES Exx C13 7 PO 6 EO : 6 g/l AGES Exx C13 7 PO 6 EO: 6 g / l AGES Exx C13 7 PO 6 EO: 6 g / l
NaCI : 81 g/l NaCI : 81 g/l NaCI: 81 g / l NaCI: 81 g / l
En mélangeant les compositions C et CO en proportions variables, on a obtenu cinq Solutions 1 à 5 décrites dans le tableau ci-dessous, qui ont des teneurs variables en cétones internes résiduelles, reportées dans la colonne à l’extrême droite : la valeur reportée, exprimée en pourcentage correspond à la concentration molaire en composé A, à savoir le rapport A/(A+B). By mixing compositions C and CO in variable proportions, five Solutions 1 to 5 described in the table below were obtained, which have variable contents of residual internal ketones, reported in the column on the far right: the value reported , expressed as a percentage, corresponds to the molar concentration of compound A, namely the ratio A / (A + B).
Tableau 1 Composition des solutions injectés dans le milieu poreaux Table 1 Composition of the solutions injected into the porous medium
Note : la Solution 1 correspond à la composition C - la Solution 2 à la composition C0 Note: Solution 1 corresponds to composition C - Solution 2 corresponds to composition C0
Les cinq solutions ainsi préparées ont été soumises à un test d’injection dans les conditions suivantes. Des échantillons de roche type Bentheimer de forme cylindrique et dont les caractéristiques sont décrites dans le tableau 2 ont été utilisés comme milieux poreux pour étudier l’écoulement des solutions décrites dans le tableau 1 . The five solutions thus prepared were subjected to an injection test under the following conditions. Bentheimer-type rock samples of cylindrical shape and the characteristics of which are described in Table 2 were used as porous media to study the flow of the solutions described in Table 1.
Tableau 2 Caractéristiques du milieu poreux Table 2 Characteristics of the porous medium
Le test a été réalisé dans les conditions suivantes : The test was carried out under the following conditions:
Le système est maintenu à 60°C dans une étuve. Le débit d’injection du fluide est de 0.0165 ml/min (ce qui correspond à cisaillement de 15s 1 subit par le fluide lors de sa propagation dans le milieu). Des capteurs de pression permettent de mesurer la différence de pression aux bornes du milieu poreux. A partir des mesures de pression on détermine la réduction de mobilité Rm de la solution de tensioactif The system is maintained at 60 ° C in an oven. The fluid injection rate is 0.0165 ml / min (which corresponds to 15s 1 shear suffered by the fluid during its propagation in the medium). Pressure sensors are used to measure the pressure difference across the porous medium. From the pressure measurements, the reduction in mobility Rm of the surfactant solution is determined.
Les résultats des courbes de Rm en fonction du volume de pore injecté (VP) permettent d’établir pour chaque solution le profil adopté pour l’évolution de la Rm. The results of the Rm curves as a function of the volume of pore injected (VP) make it possible to establish for each solution the profile adopted for the evolution of the Rm.
Ces tests montrent que sur cet exemple précis, la valeur de la concentration molaire limite en cétones interne non sulfonée est de l’ordre de 15% mol. These tests show that in this specific example, the value of the limit molar concentration of non-sulfonated internal ketones is of the order of 15% mol.
Pour les solutions 1 , 4 et 5 qui correspondent à des compositions selon la présente invention, et où la teneur en cétones internes résiduelles non sulfonées est suffisante, on obtient une stabilisation de la valeur de la Rm qui cesse rapidement de diverger. Au contraire, pour les solutions 2 et 3, où la teneur est plus faible, le profil d’évolution est différent, avec une augmentation continue de la réduction de mobilité lors de l’injection de la solution de tensioactif, ce qui traduit que la solution de tensioactif endommage le milieu poreux. For solutions 1, 4 and 5 which correspond to compositions according to the present invention, and where the content of non-sulfonated residual internal ketones is sufficient, a stabilization of the value of Rm is obtained which rapidly ceases to diverge. On the contrary, for solutions 2 and 3, where the content is lower, the evolution profile is different, with a continuous increase in the reduction in mobility during the injection of the surfactant solution, which translates that the surfactant solution damages the porous medium.

Claims

REVENDICATIONS
1 . Composition adaptée pour la récupération assistée de pétrole, comprenant : (A) des cétones internes sulfonées en alpha du groupement cétone ; et 1. A composition suitable for enhanced petroleum recovery, comprising: (A) alpha-sulfonated internal ketones of the ketone group; and
(B) des cétones internes non sulfonées, avec un rapport molaire B/(A+B), correspondant à la concentration molaire en cétones non sulfonées, qui est supérieur ou égal à la concentration molaire limite en cétones non sulfonées à partir de laquelle on observe une stabilisation de la réduction de la mobilité lorsqu’on injecte le mélange desdites cétones internes sulfonées et desdites cétones interne non sulfonées dans un milieu poreux. (B) non-sulfonated internal ketones, with a B / (A + B) molar ratio, corresponding to the molar concentration of non-sulfonated ketones, which is greater than or equal to the limit molar concentration of non-sulfonated ketones from which a stabilization of the reduction in mobility is observed when the mixture of said sulfonated internal ketones and of said non-sulfonated internal ketones is injected into a porous medium.
2. Composition selon la revendication 1 , où le rapport molaire B/(A+B) est compris entre 10% et 50%. 2. Composition according to claim 1, wherein the molar ratio B / (A + B) is between 10% and 50%.
3. Composition selon la revendication 1 ou 2, où les composés A comprennent un mélange d’au moins un mono-sulfonate et d’au moins un disulfonate répondant respectivement aux formules (1 ) et (2) ci-dessous : 3. Composition according to claim 1 or 2, in which the compounds A comprise a mixture of at least one mono-sulfonate and of at least one disulfonate corresponding respectively to formulas (1) and (2) below:
ou : or :
chacun de R1 ; R3 et R5, identiques ou différents, est, indépendamment, un hydrogène ou une chaîne alkyle linéaire ou ramifiée ayant de 1 à 20 atome(s) de carbone ; each of R 1; R 3 and R 5 , which may be identical or different, is, independently, hydrogen or a linear or branched alkyl chain having from 1 to 20 carbon atoms;
chacun de R2 et R4, identiques ou différents, est indépendamment un chaîne alkyle linéaire ou ayant de 4 à 24 atome(s) de carbone , ladite chaîne alkyle pouvant comprendre des groupes cycloaliphatiques ; et each of R 2 and R 4 , which may be identical or different, is independently a linear alkyl chain or having from 4 to 24 carbon atoms, said alkyl chain possibly comprising cycloaliphatic groups; and
X est H ; ou bien -S03X est un sel de sulfonate formé avec 1/n mole d’un cation Xn+ où n est la valence du cation. X is H; or -S0 3 X is a sulfonate salt formed with 1 / n mole of a cation X n + where n is the valence of the cation.
4. Composition selon la revendication 3, où les composés B répondent à la formule4. Composition according to claim 3, in which the compounds B correspond to the formula
(3) ci-dessous : ou : (3) below: or :
R1 ; R2 , R3 , R4 et R5 sont tels que définis dans la revendication 3 ; et R6 est un hydrogène ou bien une chaîne alkyle linéaire ou branchée ayant de 1 à 20 atomes de carbone. R 1; R 2, R 3 , R 4 and R 5 are as defined in claim 3; and R 6 is hydrogen or a linear or branched alkyl chain having from 1 to 20 carbon atoms.
5. Composition selon la revendication 4, qui est préparée en sulfonant seulement partiellement un composé de formule (3) ou bien un mélange de composés de formule (3) tels que définis dans la revendication 4, à l’aide d’un agent de sulfonation. 5. Composition according to claim 4, which is prepared by only partially sulfonating a compound of formula (3) or a mixture of compounds of formula (3) as defined in claim 4, using a sulfonation.
6. Composition selon la revendication 5, où la sulfonation est conduite en utilisant le trioxyde de soufre gazeux S03 à titre d’agent de sulfonation 6. Composition according to claim 5, in which the sulfonation is carried out using gaseous sulfur trioxide S0 3 as sulfonating agent.
7. Composition selon la revendication 6, où la sulfonation est en outre conduite en utilisant la technique du film tombant. 7. The composition of claim 6, wherein the sulfonation is further conducted using the falling film technique.
8. Composition selon l’une des revendications 1 à 7, qui comprend en outre : 8. Composition according to one of claims 1 to 7, which further comprises:
- un milieu aqueux comprenant des sels dissous ; et/ou un tensioactif anionique, de préférence un AGES ou un AAGES - an aqueous medium comprising dissolved salts; and / or an anionic surfactant, preferably an AGES or an AAGES
9. Utilisation d’une composition selon l’une des revendications 1 à 8 pour la récupération assistée de pétrole. 9. Use of a composition according to one of claims 1 to 8 for enhanced oil recovery.
10. Procédé de récupération assistée du pétrole d’une formation souterraine, dans lequel : 10. Process for the enhanced recovery of petroleum from an underground formation, in which:
- on injecte dans ladite formation souterraine, par au moins un puits d’injection, une composition selon l’une des revendications 1 à 8 ; et - Is injected into said underground formation, by at least one injection well, a composition according to one of claims 1 to 8; and
- on récupère, par au moins un puits de production, un fluide véhiculant le pétrole sortant de la formation souterraine. - Recovering, by at least one production well, a fluid carrying the oil leaving the underground formation.
EP19734440.1A 2018-07-09 2019-07-05 Sulphonated internal ketone-based formulations for assisted recovery of oil Pending EP3820963A1 (en)

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US2989547A (en) 1956-12-10 1961-06-20 Procter & Gamble Method for preparing detergent compositions
DE1249434B (en) 1957-05-14 1968-03-28 The Procter S. Gamble Company, Cincinnati, Ohio (V. St. A.) laundry detergent
US3268563A (en) * 1962-05-03 1966-08-23 Petrolite Corp Esters of an alpha-sulfo carboxylic acid and a glycol
US4022699A (en) * 1972-06-26 1977-05-10 Union Oil Company Of California Soluble oil composition
US5223166A (en) * 1986-11-17 1993-06-29 Henkel Kommanditgesellschaft Auf Aktien Preparations and processes for cleaning and disinfecting endoscopes
DE3639322A1 (en) * 1986-11-17 1988-05-26 Henkel Kgaa METHOD FOR CLEANING AND DISINFECTING ENDOSCOPES AND MEANS FOR IMPLEMENTING THE METHOD
DE4220580A1 (en) * 1992-06-24 1994-01-13 Henkel Kgaa New alpha-sulpho carbonyl cpds. useful as surfactants - prepd. by sulphonating higher aldehyde or ketone with sulphur tri:oxide
ATE165251T1 (en) * 1993-02-02 1998-05-15 North West Water Group Plc POROETIC POLYMER STRUCTURE AND METHOD
US6828281B1 (en) * 2000-06-16 2004-12-07 Akzo Nobel Surface Chemistry Llc Surfactant blends for aqueous solutions useful for improving oil recovery
US20050153853A1 (en) * 2002-01-31 2005-07-14 Stepan Company Soap bar compositions comprising alpha sulfonated alkyl ester or sulfonated fatty acid and synthetic surfactant and processes for producing same
DE102006047091A1 (en) * 2006-10-05 2008-04-10 Basf Construction Polymers Gmbh New composition based on polyvinyl alcohol
CN101659861B (en) * 2008-08-29 2012-12-12 中国石油天然气股份有限公司 Method for preparing petroleum sulfonate oil displacement agent
DE102010038496A1 (en) * 2010-07-27 2012-02-02 Henkel Ag & Co. Kgaa Stabilized liquid enzyme-containing surfactant preparation
WO2016003460A1 (en) * 2014-07-02 2016-01-07 Multi-Chem Group, Llc Surfactant formulations for reduced and delayed adsorption
WO2016177817A1 (en) * 2015-05-07 2016-11-10 Rhodia Operations Formulations for enhanced oil recovery comprising sulfonates
CN105037223A (en) * 2015-07-07 2015-11-11 陕西延长石油(集团)有限责任公司研究院 Continuous extraction separation method of unsulfonated oil in petroleum sulfonate
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