Alkyl benzene sulfonic acid and corresponding salt for enhanced oil recovery

Abstract

The present invention relates to a composition comprising alkyl benzene sulfonate isomers, wherein the composition comprises ABS (I) and ABS (II) structural isomers in a molar ratio of 10:90 to 30:70 and comprises one or more additional alkyl benzene sulfonates selected from ABS (III), ABS (IV) and ABS (V). The present invention also relates to a method for preparing such a composition and to the use of such a composition in oil fields and in enhanced oil recovery applications.

Description

Background Technology

[0001] In industrialized economies, crude oil has been used as the most important energy source and a raw material for numerous chemical industry products since the early 20th century. It is generally produced from underground deposits formed over millions of years. Consequently, global reserves are limited and are generally expected to be depleted within the next few decades. For this reason, it is generally desirable to recover as much crude oil as possible from developed deposits. The process of recovering crude oil from underground deposits can generally be broadly divided into primary, secondary, and tertiary recovery stages.

[0002] Primary recovery refers to the process in which oil is pushed to the surface by the natural pressure of underground reserves during the oil production stage and extracted through a borehole. Generally, about 5 to 10 percent of the reserves can be extracted through primary recovery.

[0003] When the natural pressure of an oil field is depleted and oil can no longer be extracted using primary recovery methods, or when the naturally occurring pressure in the field is insufficient for extraction, a secondary recovery method is generally used. This involves injecting high-pressure water or gas into the oil field to extract the oil remaining after the primary recovery. This is achieved through so-called pore displacement, which means increasing or restoring the natural pressure present at the start of oil extraction and moving the oil out of the field to a well that transports it to the surface. When the injected material is water, this method is also called hydraulic fracturing. Through the secondary recovery method, an additional 20 to 30 percent of the oil in the field can generally be extracted.

[0004] Tertiary recovery refers to a crude oil production step in which chemicals, such as polymers, alkali agents, surfactants, or combinations of these chemicals, are injected into a reserve to improve the fluidity of the crude oil remaining after the primary and secondary recovery steps. This is also known as chemical injection or chemically enhanced oil recovery (commonly abbreviated as EOR). Through tertiary recovery, an additional 10 to 20 percent of the reserve can generally be extracted.

[0005] When a surfactant is injected into the precipitate, the interfacial tension between the oil and water or the precipitate is lowered. Consequently, the movement of oil droplets through the precipitate is facilitated.

[0006] Alkyl benzene sulfonates are currently one of the most widely known surfactants and are used in various fields requiring surfactants (detergents, hard surface cleaners, drilling fluids, cutting fluids, wetting agents, emulsifiers for agricultural herbicides, emulsion polymerization, etc.). They are also recognized as promising materials for enhancing petroleum recovery using surfactant injection and surfactant-polymer injection methods. The key differences between alkyl benzene sulfonates used in household detergents and those used in EOR applications are explained in detail later in this introduction.

[0007] Alkyl benzene sulfonates are generally produced by alkylating benzene with an olefin or a partially dehydrogenated paraffin to form a linear alkyl benzene (LAB) in which a hydrocarbon radical is bonded to a benzene ring. Subsequently, the LAB is sulfonated to chemically bond a sulfonate group to a carbon atom within the benzene ring structure of the LAB. Thus, the resulting linear alkyl benzene sulfonate (LAS) comprises a hydrophilic sulfonate group and a hydrophobic hydrocarbon moiety. Alkylation and sulfonation processes useful for forming LAB and LAS compositions are well known. For example, refer to U.S. Patent No. 6,887,839.

[0008] LAS is commonly used in EOR applications because it not only lowers the interfacial tension between oil and water but also exhibits desirable phase behavior when used with other salts such as sodium chloride. Deposited crude oil forms a microemulsion with a well-tailored EOR composition containing LAS (matching optimal phase behavior), and the large amount of oil and water dissolved in this microemulsion induces extremely low interfacial tension, providing the possibility of achieving high oil recovery rates from storage.

[0009] However, some LAS exhibit several characteristics that make them unsuitable for EOR applications or for the preparation of surfactant concentrates used in the manufacture of final compositions for EOR applications. These undesirable characteristics include high viscosity, high pour point, low solubility of sodium sulfate and / or calcium sulfate, or the inability to achieve low interfacial tension (IFT) between crude oil and brine. Therefore, research is needed to develop LAS compositions that do not exhibit these undesirable characteristics.

[0010] Returning to the previously mentioned point, the difference between LAS used in household detergents or similar applications and LAS currently on the market for EOR applications lies in the length of the alkyl chain. LAS currently used in household detergents generally contains C10-C13 alkyl chains and is the world's largest synthetic surfactant, with approximately 4.7 million tons sold as of 2022. Globally, there are many facilities well-equipped with processes for efficiently producing C10-13 LAS. This is a well-known fact in LAB and LAS market analyses. For example, Decode the Future of Linear Alkyl Benzene (LAB) (Sep 2023) in Refer to Chemanalyst, https: / / www.chemanalyst.com / industry-report / linear-alkyl-benzene-market-278 and Linear alkyl benzene sulfonic acid (LABSA) in STPP Group, https: / / stppgroup.com / products / detergent-chemicals / labsa / .

[0011] On the other hand, LAS used in EOR applications generally contain C15-C17 alkyl chains. Due to the low demand for C15-C17 LAS, current production facilities are non-existent or extremely limited. If large quantities of C15-C17 LAS are required, constructing a new manufacturing plant necessitates massive investments in energy and construction materials. Therefore, in terms of resource efficiency (i.e., maximizing the utilization of existing resources), a LAS composition that can be successfully used in EOR applications and manufactured by utilizing at least partially existing "detergent" LAS will help minimize energy and material consumption. Furthermore, since there is no need to construct a new manufacturing plant for the production of C15-C17 LAS for "EOR," indirect energy and material savings can be achieved, resulting in a positive environmental impact.

[0012] Prior art

[0013] US 2009 / 0111717 A1 and WO 2009 / 058889 A1 describe an improved petroleum recovery formulation comprising an alkyl aryl sulfonate as a primary surfactant, an aliphatic sulfonate as a secondary surfactant, a cosolvent, a passivator, and a polymer.

[0014] WO 2009 / 079289 A1 describes an improved oil recovery method in which a surfactant-polymer formulation described in US 2009 / 0111717 A1 and WO 2009 / 058889 A1 is injected into a storage tank through a well, followed by the injection of a tracer solution.

[0015] WO 2017 / 174770 A1 describes an improved composition and method for petroleum recovery comprising a dialkylated benzene sulfonate salt, an alkyl diphenyl ether disulfonate salt, a polyacrylamide, an alkali agent, and water.

[0016] US 2018 / 0057453 A1 describes a method for preparing a surfactant composition comprising a dialkyl benzene sulfonate (where the alkyl portion independently has 15 or fewer carbon atoms) and a linear alkyl benzene sulfonate.

[0017] WO 2014 / 055225 A1 describes a surfactant composition for treating oil-containing underground layers comprising a biodegradable chelating agent comprising an alkyl aryl sulfonate salt and ethylenediamine disuccinic acid or a salt thereof.

[0018] WO 2013 / 000571 A1 relates to a surfactant composition comprising an alkyl aryl sulfonate salt and its use in enhancing petroleum recovery. The alkyl chain of the alkyl aryl sulfonate salt comprises 9 to 10 carbon atoms, and at least 20% of the molecule has a branched alkyl chain having a methyl or ethyl group as a side chain substituent.

[0019] WO 2000 / 037775 A1 describes an improved petroleum recovery method using an alkyl aryl sulfonate salt prepared by alkylating an aromatic compound with an alpha-olefin stream having a wide distribution of olefin carbon numbers.

[0020] WO 2015 / 138275 A1 describes a surfactant composition that may include an alkylbenzene sulfonic acid. means of solving the problem

[0021] The present invention relates to a composition comprising the following alkylbenzene sulfonate ABS (I) and ABS (II):

[0022]

[0023] [During the meal,

[0024] R 1 and R 2 is independently selected from saturated alkyl groups containing 2 to 13 carbon atoms;

[0025] R 1 and R 2 It has a total of 15 carbon atoms together;

[0026] M + is H + , NH4 + or a monovalent cation, preferably H + , NH4 + , Na + or K + Selected independently from];

[0027] The molar ratio of the above ABS (I) : ABS (II) is in the range of 10:90 to 30:70.

[0028] In one embodiment, the composition comprises one or more additional alkylbenzene sulfonate molecules selected from the following ABS (III), ABS (IV), ABS (V) and mixtures thereof:

[0029]

[0030] [During the meal,

[0031] M + is H + , NH4 + or a monovalent cation, preferably H + , NH4 + , Na + or K + Selected independently from];

[0032] The molar ratio of the above alkyl benzene sulfonate [(I)+(II)] : [(III)+(IV)+(V)] is in the range of 90:10 to 99.9:0.1;

[0033] The above alkyl benzene sulfonates (I) - (V) are collectively referred to as ABS mixtures "Group A".

[0034] The present invention also relates to a concentrated mixture and an EOR composition prepared from the ABS composition of the present invention, the use of these in oil fields and EOR applications, and a method of treating an underground oil well with an EOR composition to form a Winsor type III emulsion to successfully recover crude oil. Effects of the invention

[0035] Surprisingly, the ABS composition of the present invention was found to provide various advantages.

[0036] First, the ABS composition (M) of the present invention + = H + The material is in a liquid state at ambient temperature and has low viscosity. This allows the material to be easily pumped and discharged onto a transport vehicle (e.g., a container truck), thereby facilitating the transport of the ABS composition to another location (e.g., a remote storage facility). If the ABS composition cannot be pumped at a high concentration, it must be diluted so that it can be easily pumped and discharged onto a transport vehicle. Thus, when the composition contains a high concentration of ABS (e.g., more than 60 wt%, preferably more than 80 wt%) while having low viscosity and low moisture content (e.g., less than 5 wt%, preferably less than 2.5 wt%), the required transport capacity (e.g., number of trucks) is reduced compared to transporting a diluted aqueous solution containing only about 10 to 20 wt% of the active material. Consequently, a significant amount of energy savings can be achieved.

[0037] Second, the ABS composition (M) of the present invention + = H+ ) has a low pour point, that is, the pour point is less than -21 ℃.

[0038] Thanks to its low viscosity and pour point, surfactant compositions can be easily handled even in remote storage areas with limited infrastructure: heating is not required to store the mixture at ambient temperature, and standard pumps can be used due to its relatively low viscosity. Additionally, the low pour point enables easy handling of ABS compositions even in environments with low ambient temperatures, such as winter or cold regions.

[0039] Third, by mixing the ABS composition (acidic form) of the present invention, a neutralizing agent, and a second surfactant, a concentrated mixture can be prepared having a low viscosity at 65°C and a pour point of less than 20°C, and containing a high surfactant concentration and a low water content. In addition to supplying a single surfactant component (e.g., the ABS composition), it is also possible to supply a surfactant mixture in the form of a concentrated solution. In EOR applications, alkylbenzenesulfonic acid is often neutralized, for example with Na2CO3 or NaOH, to obtain the corresponding sodium salt, which is then mixed with other surfactants such as polyalkoxylate-based surfactants. Since the preparation of such concentrated mixtures may be carried out at a manufacturing facility located away from the underground oil well, the transport of the concentrated mixture is required. For the reasons described above, it is desirable for the highly concentrated active surfactant content to be low and the pour point low, as this allows for easy pumping into a transport means and saves transport capacity and energy. This is achieved through a concentrated mixture prepared by mixing the ABS composition of the present invention with one or more additional surfactants.

[0040] Fourth, a transparent and stable composition suitable for EOR applications can be prepared from the ABS composition of the present invention, containing between 0.05 and 2 weight percent of a surfactant. The EOR composition comprises at least an alkylbenzene sulfonate salt, impurities generated during the ABS manufacturing step (e.g., sulfonic acid), Na2CO3 or NaOH remaining from the neutralization step, and, if necessary, a second surfactant. For a successful EOR process, the EOR composition must be transparent, homogeneous, and stable. If the EOR composition is turbid and tends to precipitate, for example, when sodium sulfate (from the residue of sulfonic acid and Na2CO3 or NaOH) or calcium sulfate (from the residue of sulfonic acid in contact with groundwater containing divalent cations such as calcium cations) is generated, there is a risk that porous reservoirs, such as sandstone or carbonate reservoirs, will become clogged, causing the oil recovery method to fail.

[0041] The ABS composition of the present invention contains less than 2 weight percent of sulfuric acid. This not only contributes to the transparent and stable appearance of the ABS composition but also reduces the risk of clogging in porous reservoirs such as sandstone or carbonate reservoirs.

[0042] And fifth, using an EOR composition prepared from the ABS composition of the present invention allows for the achievement of an ultra-low IFT (less than 0.01 mN / m) between crude oil and brine. When the EOR composition prepared from the ABS composition of the present invention comes into contact with crude oil, a Winsor type III microemulsion is formed. This type of microemulsion enables highly efficient transport of crude oil during the EOR operation. Specific details for implementing the invention

[0043] In one embodiment of the present invention, the ABS composition further comprises "Group B" alkylbenzenesulfonic acid or a salt form thereof, and the weight ratio of the ABS mixture "Group A" : "Group B" is in the range of 95:5 to 70:30. The composition of the present invention exhibits all the desirable characteristics mentioned above for an ABS composition comprising "Group A" ABS.

[0044] "Group B" ABS is based on by-products / unnecessary by-products generated during the manufacturing process of C10-C13-Ph, which serve as the raw material for the synthetic surfactant C10-C13 ABS used, for example, in detergent applications. As previously mentioned in the "Background Technology" section, C10-C13 ABS is currently the most widely sold synthetic surfactant worldwide, with approximately 4.7 million tons sold as of 2022. By mixing "Group B" ABS, which is based on already secured alkylbenzene raw materials, with "Group A" ABS, for which efficient manufacturing facilities are currently insufficient, the total production requirement for "Group A" ABS can be reduced. This results in savings in the energy and materials required to construct new manufacturing facilities for the production of "EOR" C15-C17 LAS. Consequently, it has a positive impact on the environment.

[0045] In one embodiment of the present invention, the ABS composition further comprises "Group C" alkylbenzenesulfonic acid or a salt form thereof, and the weight ratio of the ABS mixture "Group A" to "Group C" is in the range of 25:75 to 97.5:2.5, preferably 50:50 to 97.5:2.5, more preferably 70:30 to 95:5, and even more preferably 85:15 to 95:5. It was surprisingly discovered that the composition of the present invention not only exhibits all the desirable characteristics mentioned above for an ABS composition containing "Group A" ABS, but also that when a "Group C" ABS surfactant is added, the water solubility of the surfactant concentrate is further improved and the viscosity of the surfactant concentrate is reduced, making it easier to prepare the EOR composition.

[0046] definition

[0047] The following terms used in this specification have the following meanings unless otherwise explicitly stated:

[0048] The term "LAB" as used in this specification means a linear alkyl benzene compound.

[0049] The term "LAS" as used in this specification means linear alkylbenzenesulfonic acid or a corresponding salt thereof.

[0050] The term "ABS" as used in this specification means an alkylbenzene sulfonic acid or a corresponding salt thereof that may be linear or branched.

[0051] The terms “Enhanced Oil Recovery” or “EOR” as used in this specification refer to a process that enhances the recovery of hydrocarbons from underground storage.

[0052] The term “active” as used in this specification refers to the concentration of a type of surfactant (i.e., LAS or a secondary surfactant or an auxiliary surfactant).

[0053] The terms “interfacial tension” or “IFT” as used in this specification refer to the surface tension between water of various salinity containing surfactant compositions of various concentrations and test oil.

[0054] The term "2-alkyl isomer" refers to a form in which an alkyl group is bonded to an aromatic ring, wherein the longest alkyl chain is bonded to the 2-position of the aromatic ring.

[0055] The term "TSP" as used in this specification means industrial tristyrylphenol (industrial TSP contains small amounts of distyrylphenol and monostyrylphenol in addition to tristyrylphenol). It may also be referred to as styrinated phenol instead of industrial TSP.

[0056] The term "ABS composition" as used in this specification refers to a composition containing a high amount of alkylbenzene sulfonic acid or a salt thereof as a single surfactant and having a low water content.

[0057] The term "concentrated mixture" as used in this specification refers to a composition having a high surfactant content and a low water content, said composition comprising an alkyl benzene sulfonated salt and a second surfactant.

[0058] As used herein, the term "EOR composition" means a composition having a low surfactant content, i.e., between 0.05 and 2 weight percent, which can be directly injected into one or more injection wells during EOR operation, wherein the composition comprises at least an alkylbenzene sulfonated salt as a surfactant and optionally comprises a second surfactant.

[0059] Unless otherwise specified, all percentages are by weight, and pressure is in atmospheric units.

[0060] Description of the invention

[0061] In one embodiment of the present invention, the ABS composition comprises an alkyl benzene sulfonic acid or a salt thereof according to the ABS mixture “Group A”.

[0062] In another embodiment, the ABS composition further comprises an ABS mixture "Group B", an ABS mixture "Group C", or an ABS mixture "Group B" and "Group C".

[0063] ABS mixtures "Group A", "Group B", and "Group C" will be explained in more detail below.

[0064] In one embodiment of the present invention, a pumpable concentrated mixture can be prepared by mixing any ABS composition comprising an alkyl benzene sulfonated salt with a second surfactant, or by mixing an ABS composition comprising an alkyl benzene sulfonic acid with a neutralizing agent and a second surfactant.

[0065] In one embodiment of the present invention, the EOR composition may be prepared by diluting any ABS composition or concentrated mixture with at least water or brine. The EOR composition comprises a low surfactant content, i.e., between 0.05 and 2 weight percent, and may optionally include a second surfactant in addition to the ABS surfactant.

[0066] Any composition described herein may include additional components selected from a list including, but not limited to, a second surfactant, a polymer, a solvent, an alkali agent, a disinfectant, an oxygen scavenger, an antiscaling agent, and a corrosion inhibitor. Suitable examples of such additional components are provided in more detail below.

[0067] ABS mixture "Group A"

[0068] The surfactants of group (A) are selected from the structures ABS (I) - (V) below:

[0069]

[0070] [During the meal,

[0071] R 1 and R 2is independently selected from saturated alkyl groups containing 2 to 13 carbon atoms;

[0072] R 1 and R 2 It has a total of 15 carbon atoms together;

[0073] M + is H + , NH4 + or independently selected from monovalent cations, preferably M + is H + , NH4 + , Na + or K + am].

[0074] In one embodiment of the present invention, the molar ratio of ABS (I) : ABS (II) in the ABS composition is in the range of 10:90 to 30:70, preferably 13:87 to 27:73, more preferably 15:85 to 25:75.

[0075] In one embodiment of the present invention, the molar ratio of alkyl benzene sulfonate [(I)+(II)] : [(III)+(IV)+(V)] in the ABS composition is in the range of 90:10 to 99.9:0.1.

[0076] In another embodiment, the ABS composition may include other alkylbenzene sulfonate molecules different from ABS mixture “Group A”, in which case the amount of ABS mixture “Group A” is 50 weight% or more, preferably 60 weight% or more, more preferably 70 weight% or more, with respect to the total weight of all alkylbenzene sulfonate molecules present in the composition.

[0077] In another embodiment, at least 90% of the alkyl chains of the alkyl benzene sulfonic acid or its salts in "Group A" are linear, preferably at least 95% are linear.

[0078] In a preferred embodiment, the SO3M groups in ABS (I) and ABS (II) are independently located at the ortho or para position, preferably at the para position.

[0079] Surfactants of group (A) can be obtained by alkylating benzene primarily with linear C16 alpha-olefins using an HF catalyst (alternatively, a DETAL catalyst may be used). The alkylbenzene mixture obtained by alkylating benzene with 16-carbon alpha-olefins may further contain higher alkylated compounds that are not removed during a purification step (e.g., distillation). The obtained alkylbenzene mixture is in a liquid state at room temperature and exhibits a refractive index of 1.479 to 1.482 (at 20 °C, according to ASTM D-1218).

[0080] Subsequently, the alkyl benzene mixture can be sulfonated with a sulfonating agent (e.g., sulfur trioxide) in a falling membrane reactor.

[0081] Optionally, alkylbenzene sulfonic acid can be neutralized with a base (e.g., sodium hydroxide) to form the corresponding salt.

[0082] ABS mixture "Group B"

[0083] The surfactants of group (B) are selected from dialkylated or trialkylated alkyl benzene sulfonic acids or corresponding salts in which the sum of all carbon atoms in the alkyl chain is mainly in the range of 10 to 20, but no alkyl chain has more than 15 carbon atoms, and optionally monoalkylated alkyl benzene sulfonic acids or salts thereof having C14-C15 alkyl chains.

[0084] The surfactants of group (B) are selected from the structures ABS (VI) - (VIII) below:

[0085]

[0086] [During the meal,

[0087] R3 is a saturated alkyl group containing 14 to 15 carbon atoms;

[0088] R 4 , R 5 , R 6 , R 7 , R 8 is independently selected from saturated alkyl groups containing two or more carbon atoms;

[0089] R 4 and R 5 The sum of all carbon atoms in is in the range of 10 to 20, but the single alkyl group does not contain more than 15 carbon atoms;

[0090] R 6 , R 7 and R 8 The sum of all carbon atoms in is in the range of 10 to 20, but the single alkyl group does not contain more than 15 carbon atoms;

[0091] M + is H + , NH4 + or a monovalent cation, preferably H + , NH4 + , Na + or K + [Selected independently from].

[0092] In one embodiment of the present invention, the weight ratio of "Group A" to "Group B" of the ABS mixture in the ABS composition is in the range of 95:5 to 70:30, preferably 90:10 to 70:30, and more preferably 85:15 to 75:25.

[0093] In another embodiment, the molar ratio of alkyl benzene sulfonate (VI) : [(VII)+(VIII)] in the ABS composition is in the range of 0:100 to 20:80.

[0094] In another preferred embodiment, the content of ABS (VII) in the ABS composition is greater than the content of ABS (VIII).

[0095] In one preferred embodiment, at least 50% of the alkyl chains of the alkyl benzene sulfonic acid or its salts in "Group B" are linear, preferably at least 90% are linear.

[0096] In one preferred embodiment, the SO3M group is ABS (VI) and is in the ortho or para position, preferably in the para position.

[0097] To prepare a "Group B" ABS mixture, an alkylbenzene mixture is first obtained through the following steps:

[0098] (1) A step of dehydrogenating a paraffin mixture having mainly 10 to 13 carbon atoms to obtain a corresponding olefin. Generally, the content of the compound having 10 to 13 carbon atoms is 98% or more.

[0099] (2) A step of alkylating the formed olefin with benzene (e.g., using an HF catalyst or a DETAL catalyst). At this step, transalkylation may occur.

[0100] (3) A step to remove most of the monoalkylated alkyl benzene through distillation.

[0101] (4) A step of distilling the fraction rich in higher alkylated benzenes and separating the fraction. The boiling point of the first 5% of the desired fraction is at least 320 °C, and the boiling point of the remaining 95% is at most 370 °C (at atmospheric pressure, according to ASTM D-86).

[0102] (5) The separated alkylbenzene mixture is liquid at room temperature and has a refractive index of 1.488 - 1.493 (at 20°C, according to ASTM D-1218).

[0103] Next, the alkylbenzene mixture can be sulfonated with a sulfonating agent (e.g., sulfur trioxide) in a falling membrane reactor. Optionally, the alkylbenzene sulfonic acid is neutralized with a base (e.g., sodium hydroxide).

[0104] An alternative synthesis method is to mix the alkylbenzene compound that is the raw material for the surfactant of group (A) with the alkylbenzene that is the raw material for the surfactant of group (B). Subsequently, the obtained mixture can be sulfonated with a sulfonating agent (e.g., sulfur trioxide) in a falling membrane reactor. Optionally, the alkylbenzene sulfonic acid can be neutralized with a base (e.g., sodium hydroxide).

[0105] ABS mixture "Group C"

[0106] The surfactant of group (C) is a monoalkylated linear alkylbenzene sulfonic acid or a corresponding salt in which the alkyl chain mainly contains 10 to 13 carbon atoms.

[0107] The surfactant of group (C) is selected from the following structure ABS (IX):

[0108]

[0109] [During the meal,

[0110] R 9 is a saturated alkyl group containing 10 to 13 carbon atoms;

[0111] M + is H + , NH4 + or a monovalent cation, preferably H + , NH4 + , Na + or K + am].

[0112] In another embodiment, the ABS (XI) surfactant is selected from the following ABS (X) and ABS (XI):

[0113]

[0114] [During the meal,

[0115] R 10 It is a saturated alkyl group containing 8 to 11 carbon atoms;

[0116] R 11 and R 12 is independently selected from saturated alkyl groups containing 2 to 10 carbon atoms;

[0117] R 11 and R 12 It has a total of 9 to 12 carbon atoms together;

[0118] M + is H + , NH4 + or a monovalent cation, preferably H + , NH4 + , Na + or K + [Selected independently from].

[0119] In one embodiment of the present invention, the ABS composition comprises ABS mixtures “Group A” and “Group C”, and the weight ratio of ABS mixture “Group A” : “Group C” is in the range of 25:75 to 97.5:2.5, preferably 50:50 to 97.5:2.5, more preferably 70:30 to 95:5, and even more preferably 85:15 to 95:5.

[0120] In another embodiment of the present invention, the ABS composition comprises ABS mixtures “Group A”, “Group B” and “Group C”, and the weight ratio of the ABS mixture (“Group A” + “Group B”) : “Group C” is in the range of 80:20 to 97.5:2.5, preferably 85:15 to 97.5:2.5, and more preferably 85:15 to 95:5.

[0121] In another embodiment of the present invention, the weight ratio of ABS (X) to ABS (XI) in the ABS composition is in the range of 10:90 to 25:75, preferably 14:86 to 21:79.

[0122] In one preferred embodiment, at least 90% of the alkyl chains of the alkyl benzene sulfonic acid or its salts in "Group C" are linear, preferably at least 95% are linear.

[0123] In one preferred embodiment, the SO3M group is ABS (IX) - ABS (XI) and is independently located at the ortho position or the para position, preferably at the para position.

[0124] ABS surfactants of "Group C" can be obtained in the following steps:

[0125] (a) a step of obtaining an olefin by dehydrogenating a paraffin mixture having mainly 10 to 13 carbon atoms, wherein the content of the compound having 10 to 13 carbon atoms is 98% or more, or

[0126] (b) a step of obtaining a suitable mixture of linear olefins containing mainly C10 to C13 carbon atoms from ethylene oligomerization and olefin double decomposition.

[0127] The obtained olefin is alkylated with benzene (using an HF catalyst or a DETAL catalyst) and then distilled. The first 5% of the monoalkylated benzene mixture obtained from the distillation process has a boiling point of at least 280 °C, and the remaining 95% has a boiling point of up to 310 °C (at atmospheric pressure, according to ASTM D-86). The distilled monoalkylated benzene fraction is in a liquid state at room temperature and has a refractive index of 1.481 to 1.485 (at 20 °C, according to ASTM D-1218). The average molecular weight of the distilled monoalkylated benzene mixture is in the range of 238 to 243 g / mol.

[0128] Next, the monoalkylated benzene fraction is sulfonated with a sulfonating agent (e.g., sulfur trioxide) in a falling membrane reactor. Optionally, the alkylbenzene sulfonic acid is neutralized with a base (e.g., sodium hydroxide).

[0129] Additional additives

[0130] The initial ABS composition, concentrate mixture, or EOR composition may further include one or more additives selected from the following:

[0131] ● A second or additional surfactant different from surfactant ABS (I) - (XI),

[0132] ● Polymer,

[0133] ● Solvent,

[0134] ● Alkaline agent,

[0135] ● Disinfectant,

[0136] ● Oxygen remover,

[0137] ● Radical remover,

[0138] ● Anti-scaling agent, and

[0139] ● Corrosion inhibitor.

[0140] The composition may optionally include a second or additional surfactant different from the surfactant ABS (I) - (XI) already described. This second or additional surfactant may include one or more anionic, nonionic, cationic, or amphoteric surfactants generally known in the art to be effective in reducing interfacial tension between the composition injected into the subsurface oil bed for oil recovery and the residual oil. Cationic surfactants may also be used, but they are generally less effective and more expensive. Examples of anionic surfactants include, but are not limited to, aryl ether sulfates, alkyl ether sulfates, alkyl ether sulfonates, alkyl ether hydroxypropyl sulfonates, aryl ether carboxylates, alkyl ether carboxylates, carboxymethylated alkyl polyglucosides, alkyl phenol ether sulfonates, alkyl diphenyl ether disulfonates, sulfonated alpha-olefins, and sulfonated internal olefins. Examples of nonionic surfactants include, but are not limited to, alkoxylated alkylphenols, alkoxylated linear or branched alcohols, and alkyl polyglucosides. Examples of cationic surfactants include, but are not limited to, alkyl trimethylammonium chloride or alkyl trimethylammonium bromide. Examples of amphoteric surfactants include, but are not limited to, betaine, sulfobetaine, amidopropyl betaine, and amine oxide.

[0141] In one embodiment, the composition of the present invention does not contain [Glu1, Asp5]-C15 surfactin. In another embodiment, the composition of the present invention does not contain a biosurfactant.

[0142] The composition may optionally include a polymer. Examples of polymers include, but are not limited to, high molecular weight acrylic acid-acrylamide copolymer, acrylic acid-acrylamide-diacetone-acrylamide terpolymer, acrylic acid-acrylamide-AMPS terpolymer, partially hydrolyzed polyacrylamide, hydroxyethyl cellulose, carboxymethyl cellulose, polyacrylamide, polyoxyethylene, modified starch, heteropolysaccharides obtained by fermentation of starch-derived sugars, polyvinyl alcohol, polyvinylpyrrolidone, and polystyrene sulfonate.

[0143] The composition may optionally include a solvent. Examples of suitable solvents include, but are not limited to, lower carbon chain alcohols, e.g. isopropyl alcohol, ethanol, n-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, n-amyl alcohol, sec-amyl alcohol, n-hexyl alcohol and sec-hexyl alcohol, alcohol ethers, polyalkylene alcohol ethers, e.g. ethylene glycol monobutyl ether or diethylene glycol monobutyl ether, polyalkylene glycols, e.g. ethylene glycol and propylene glycol, poly(oxyalkylene) glycols, e.g. diethylene glycol, poly(oxyalkylene) glycol ether, or any mixture thereof.

[0144] The composition may optionally include an alkali agent. Examples of suitable alkali agents include, but are not limited to, sodium metaborate, sodium hydroxide, sodium tetraborate, or sodium carbonate.

[0145] The composition may optionally include a disinfectant. Examples of suitable disinfectants include, but are not limited to, glutaraldehyde and quaternary ammonium compounds, compounds containing long alkyl chains that may be derived particularly from fatty acids and have antibacterial activity. Examples of such quaternary ammonium compounds include compounds containing one or more of benzalkonium, benzethonium, methylbenzethonium, cetalkonium, cetylpyridinium, cetrimonium, cetrimid, dophanium, tetraethylammonium, didecyldimethylammonium, and domifene as quaternary ammonium ions and chloride or bromide as anions.

[0146] The composition may optionally include an oxygen scavenger. The oxygen scavenger may react with oxygen that may be present in the aqueous formulation to prevent the oxygen from attacking the polymer or polyether groups. Examples of oxygen scavengers include sulfites, e.g., Na2SO3, bisulfites, phosphites, hypophosphites, or dithionites.

[0147] The composition may optionally include an anti-scaling agent. Examples of suitable anti-scaling agents include, but are not limited to, phosphonate compounds (e.g., hexamethylene tetramethylene phosphonate (HMDP), diethylenetriamine penta(methylphosphonate) (DETPMP), bis(hexamethylene)triamine pentabis(methylene phosphonate) (HMTPMP), nitrilotris((methylene)triphosphonate (NTP), pentaethylenehexamineoctakis(methylene phosphonate) (PEHOMP)) and / or polyphosphinocarboxylic acids (PPCA).

[0148] Application of EOR composition

[0149] In one embodiment of the present invention, an EOR composition is prepared comprising water, a surfactant ABS “Group A”, optionally a surfactant “Group B” and / or “Group C”, a basic ionic salt, and a second surfactant different from any of the surfactants ABS (I)-(IX). The total active surfactant present in the EOR composition is between 0.05 and 2 weight percent with respect to the total weight of the EOR composition.

[0150] EOR compositions can be used in oil fields or enhanced oil recovery (EOR) applications.

[0151] In a preferred embodiment, the EOR composition is used as an EOR surfactant, a flow recovery improver, a wetting agent, a dispersant, an emulsifier, a drilling fluid, a fracturing fluid, a spacer fluid, a drilling cut cleaner, a borehole cleaner, and a foaming agent for drilling fluids.

[0152] Another embodiment of the present invention is a method for recovering crude oil from an oil-containing underground geological formation, comprising injecting the EOR composition mentioned above into one or more injection wells, forming a Winsor type III microemulsion, lowering the interfacial tension between the crude oil and the aqueous surfactant solution to less than 0.1 mN / m, and producing crude oil from one or more production wells. The oil-containing underground geological formation may include a sandstone or carbonate reservoir having a reservoir temperature of 15 to 130°C.

[0153] In a preferred embodiment of the present invention, the ore deposit is a sandstone ore deposit, and more than 70 weight% of sand (quartz and / or feldspar) is present, and other minerals selected from kaolinite, smectite, illite, chlorite and / or pyrite may be present in up to 25 weight%. Preferably, more than 75 weight% of sand (quartz and / or feldspar) is present, and other minerals selected from kaolinite, smectite, illite, chlorite and / or pyrite may be present in up to 20 weight%. Particularly preferably, more than 80 weight% of sand (quartz and / or feldspar) is present, and other minerals selected from kaolinite, smectite, illite, chlorite and / or pyrite may be present in up to 15 weight%.

[0154] API Specific Gravity (American Petroleum Institute Specific Gravity) is the standard unit commonly used in the United States to measure the density of crude oil. It is used globally as a standard for crude oil characterization and quality. API Specific Gravity is the relative density P of crude oil relative to water at 60°F (15.56°C). rel It is calculated from using the following formula:

[0155] API Weight = (141.5 / P rel ) - 131.5.

[0156] According to the present invention, crude oil extracted from a corresponding oil field must have a hardness of 10° API or higher. It is preferable that it have a hardness of 12° API or higher. It is particularly preferable that it have a hardness of 15° API or higher. It is highly preferable that it have a hardness of 20° API or higher.

[0157] To carry out the method of the present invention, one or more production wells and one or more injection wells are drilled in a mineral oil deposit. Generally, multiple injection wells and multiple production wells are installed in a single deposit. An aqueous formulation of the water-soluble component described above is injected into the mineral oil deposit through one or more injection wells, and crude oil is extracted from the deposit through one or more production wells. Due to the pressure generated by the injected aqueous formulation, i.e., the "flood," the mineral oil flows toward the production wells and is produced through the production wells.

[0158] In this context, the terms “crude oil” or “mineral oil” refer not only to single-phase oil but also include general crude oil-water emulsions. Those skilled in the art will easily understand that mineral oil deposits can have a specific temperature distribution. The temperature of such deposits is based on the deposit area filled with an aqueous solution between the injection well and the production well. The method for determining the temperature distribution of mineral oil deposits is, in principle, well known to those skilled in the art. The temperature distribution is generally determined by combining temperature measurements at specific points within the formation with simulation calculations, and the simulation calculations also take into account the amount of heat entering the formation and the amount of heat removed from the formation.

[0159] The injection of the EOR composition can be performed using conventional equipment. The composition may be injected into one or more injection wells using a conventional pump. The injection wells are generally lined with steel pipes fixed in cement and are drilled at desired locations. The formulation flows into the mineral oil layer through the drilled portions of the injection wells. The pressure applied by the pump is used to fix the flow rate of the composition in principle, as is known, and thus the shear stress generated when the aqueous formulation flows into the soil is also fixed. The shear stress upon inflow into the soil can be calculated by a person skilled in the art in principle according to the Hagen-Poiseuille law, using the area through which the flow passes, the average pore radius, and the volumetric flow rate. The average permeability of the soil can be determined in principle according to a known method.

[0160] Naturally, the greater the volumetric flow rate of the EOR composition injected into the stratum, the greater the shear stress. The injection rate can be determined by a person skilled in the art according to the conditions of the stratum.

[0161] The crude oil production method described above using an EOR composition comprising water, a surfactant ABS "Group A", and optionally a surfactant "Group B" and / or "Group C" may be carried out optionally by adding additional methods. For example, a polymer or foam may optionally be added for fluidity control. The polymer may optionally be injected into the deposit together with the surfactant formulation, and then the surfactant formulation may be injected. This may also be injected together with the surfactant formulation or only after the surfactant formulation is injected. The polymer may be a copolymer based on acrylamide or a biopolymer. The copolymer may comprise, for example, the following units:

[0162] - Acrylamide and sodium acrylate salts

[0163] - Acrylamide and sodium acrylate salts and N-vinylpyrrolidone

[0164] - Acrylamide and sodium acrylate salts and AMPS (2-acrylamido-2-methylpropanesulfonate sodium salt)

[0165] - Acrylamide and sodium acrylate salts and AMPS (2-acrylamido-2-methylpropanesulfonate sodium salt) and N-vinylpyrrolidone.

[0166] The copolymer may additionally include linking groups. Available copolymers are described in EP 2432807 or WO 2014095621. Additional available copolymers are described in US 7700702.

[0167] Examples

[0168] In the following examples and comparative examples of the present invention, various alkylbenzene sulfonic acid compositions, concentrated mixtures, and EOR compositions were prepared and tested. The methods for preparing and testing these compositions are described below. The experimental results obtained from the tests are summarized in Table 1.

[0169] The following examples are intended to illustrate specific embodiments of the present invention and should not be construed as limiting the scope of the invention. Alkylation of benzene is S. Karimi et al. in Russian Journal of Applied Chemistry 2021 It is described in , Vol. 94, No. 11, pp. 1546-1559.

[0170] Preparation of the ABS composition of Comparative Example 1 (C1):

[0171] In the first step, C16 alpha olefin (linearity 95%, C16 content 99%, alpha olefin content 95%) AlCl 3 Using as a catalystIt is reacted with benzene. Unreacted raw material is removed by distillation. The obtained alkylbenzene mixture was analyzed (by proton NMR spectroscopy, carbon NMR spectroscopy, gas chromatography, and mass spectrometry), and the results showed that the 2-phenyl isomer content was 36% and the degree of monoalkylation was 99.7%. The benzene content was less than 100 ppm.

[0172] In the second step, 1.0 equivalent of the obtained C16-Ph is converted by reacting it with approximately 1.03 equivalents of sulfur trioxide in a falling membrane reactor (glass reactor, length 1 m) at 50 °C in the presence of a nitrogen stream. The C16-Ph flows from the top to the bottom of the glass reactor. During this process, a membrane of organic material is formed. The nitrogen stream is controlled to generate fine waves on the organic membrane. The nitrogen stream contains approximately 1.03 equivalents of gaseous sulfur trioxide. At the bottom of the reactor, the obtained liquid is collected and stored at 50 °C for 2 hours. The sulfonation reaction is terminated by adding 0.3 to 0.5 weight percent of water. The obtained material is analyzed through proton NMR spectroscopy (determination of ABS and alkylbenzene content), carbon NMR spectroscopy (determination of ABS and alkylbenzene content), gas chromatography and HPLC (determination of structural ratios), ion chromatography (determination of sulfuric acid content), Hyamine titration (determination of anionic surfactant content), and Karl Fischer analysis (determination of moisture content).

[0173] Obtained composition, C1:

[0174]

[0175] Preparation of the ABS composition of Example 2 of the present invention:

[0176] In the first step, C16 alpha olefin (linearity 95%, C16 content 99%, alpha olefin content 95%) Using HF as a catalystIt is reacted with benzene. Unreacted raw materials are removed by distillation, and the desired alkylbenzene mixture is retained. The obtained alkylbenzene mixture was analyzed (by proton NMR spectroscopy, carbon NMR spectroscopy, gas chromatography, and mass spectrometry), and the results showed that the 2-phenyl isomer content was 17% and the degree of monoalkylation was 98.7%. The benzene content was less than 100 ppm.

[0177] In the second step, 1.0 equivalent of the obtained C16-Ph is converted by reacting it with approximately 1.03 equivalents of sulfur trioxide in a falling membrane reactor (glass reactor, length 1 m) at 50 °C in the presence of a nitrogen stream. The C16-Ph flows from the top to the bottom of the glass reactor. During this process, a membrane of organic material is formed. The nitrogen stream is controlled to generate fine waves on the organic membrane. The nitrogen stream contains approximately 1.03 equivalents of gaseous sulfur trioxide. At the bottom of the reactor, the obtained liquid is collected and stored at 50 °C for 2 hours. The sulfonation reaction is terminated by adding 0.3 to 0.5 weight percent of water. The obtained material is analyzed through proton NMR spectroscopy (determination of ABS and alkylbenzene content), carbon NMR spectroscopy (determination of ABS and alkylbenzene content), gas chromatography and HPLC (determination of structural ratios), ion chromatography (determination of sulfuric acid content), Hyamine titration (determination of anionic surfactant content), and Karl Fischer analysis (determination of moisture content).

[0178] Obtained composition, Example 2:

[0179]

[0180] Preparation of the ABS composition of Comparative Example 3 (C3):

[0181] In the first step, the so-called heavy alkylbenzene (HAB) fraction from detergent manufacturing was used.

[0182] The heavy alkylbenzene fraction is obtained by the following method: a paraffin fraction, mainly having 10 to 13 carbon atoms, is partially dehydrogenated, and the resulting olefins (mainly monoolefins and mainly linear) are reacted with benzene using HF as a catalyst. The alkylbenzene mixture is purified from the unreacted raw material. Subsequently, the fraction of C10-C13 monoalkylated alkylbenzene is removed by distillation. This monoalkylated alkylbenzene fraction contains 10 to 13 carbon atoms in the alkyl chain, has an average molecular weight of 242 g / mol, a 2-phenyl isomer content of 15%, and a boiling point at an absolute pressure of 1 atm ranging from 288 °C (the first 5% of the fraction) to 304 °C (95% of the fraction).

[0183] After removing the fraction of C10-C13 monoalkylated benzenes, the so-called heavy alkylbenzene fraction (HAB fraction) remains. From this HAB fraction, the low-boiling-point component was separated by distillation. The desired fraction was characterized to have a boiling point in the range of 329 °C (first 5%) to 350 °C (95%) at an absolute pressure of 1 atm. The obtained alkylbenzene mixture is analyzed (by proton NMR spectroscopy, carbon NMR spectroscopy, gas chromatography, and mass spectrometry). The content of monoalkylated alkylbenzenes containing 14 to 15 carbon atoms in the alkyl group was about 10%. The sum of carbon atoms in the alkyl groups of dialkylated and trialkylated benzenes ranges from 12 to 18, whereas the single alkyl groups of polyalkylated benzenes do not contain more than 15 carbon atoms.

[0184] The obtained fraction was sulfonated in two steps. 1.0 equivalent of the obtained alkylbenzene was converted by reacting it with approximately 1.03 equivalents of sulfur trioxide in a falling membrane reactor (glass reactor, length 1 m) at 50 °C in the presence of a nitrogen stream. The alkylbenzene flows from the top to the bottom of the glass reactor. During this process, a membrane of organic material is formed. The nitrogen stream is controlled to generate fine waves on the organic membrane. The nitrogen stream contains approximately 1.03 equivalents of gaseous sulfur trioxide. At the bottom of the reactor, the obtained liquid is collected and stored at 50 °C for 2 hours. The sulfonation reaction is terminated by adding 0.3 to 0.5 weight percent of water. The obtained material is analyzed through proton NMR spectroscopy (determination of ABS and alkylbenzene content), carbon NMR spectroscopy (determination of ABS and alkylbenzene content), gas chromatography and HPLC (determination of structural ratios), ion chromatography (determination of sulfuric acid content), Hyamine titration (determination of anionic surfactant content), and Karl Fischer analysis (determination of moisture content).

[0185] Obtained composition, C3:

[0186]

[0187] Preparation of the ABS composition of Comparative Example 4 (C4):

[0188] In a 250 ml round-bottom glass flask equipped with a stirrer, 100 g of an ABS mixture was prepared by mixing the ABS composition of C1 (45 g) and the ABS composition of C3 (55 g) at 50°C. The two ABS compositions were added to the flask and stirred at 50°C for 1 hour to obtain a homogeneous mixture.

[0189] Obtained composition, C4:

[0190]

[0191] Preparation of the ABS composition of Example 5 of the present invention:

[0192] In the first step, a mixture of alkylbenzenes was prepared.

[0193] C16 alpha olefin (linearity 95%, C16 content 99%, alpha olefin content 95%) Using HF as a catalyst It is reacted with benzene. Unreacted raw materials are removed by distillation. The obtained alkylbenzene mixture was analyzed (by proton NMR spectroscopy, carbon NMR spectroscopy, gas chromatography, and mass spectrometry) and found to have a 2-phenyl isomer content of 17% and a degree of monoalkylation of 97.7%. The benzene content was less than 100 ppm. 800 g of this C16 alkylbenzene was mixed at 50°C in a glass container with a stirrer with 200 g of the alkylbenzene mixture obtained during the first step of Example C3 (i.e., the alkylbenzene mixture obtained before the sulfonation step in C3).

[0194] In the second step, an 80:20 mixture of alkylbenzenes (80 wt% C16-alkylbenzene and 20 wt% C12-C18 alkylbenzene) was sulfonated.

[0195] 1.0 equivalent of an 80:20 alkylbenzene mixture is reacted with approximately 1.03 equivalents of sulfur trioxide in a falling membrane reactor (glass reactor, length 1 m) at 50 °C in the presence of a nitrogen stream. The alkylbenzene flows from the top to the bottom of the glass reactor. During this process, a membrane of organic material is formed. The nitrogen stream is controlled to generate fine waves on the organic membrane. The nitrogen stream contains approximately 1.03 equivalents of gaseous sulfur trioxide. At the bottom of the reactor, the obtained liquid is collected and stored at 50 °C for 2 hours. The sulfonation reaction is terminated by adding 0.3 to 0.5 weight percent of water. The obtained material is analyzed through proton NMR spectroscopy (determination of ABS and alkylbenzene content), carbon NMR spectroscopy (determination of ABS and alkylbenzene content), gas chromatography and HPLC (determination of structural ratios), ion chromatography (determination of sulfuric acid content), Hyamine titration (determination of anionic surfactant content), and Karl Fischer analysis (determination of moisture content).

[0196] Obtained composition, Example 5:

[0197]

[0198] Preparation of the ABS composition of Example 6 of the present invention:

[0199] An ABS composition containing the detergent surfactant C10-C13-Ph-SO3H was obtained in the following manner:

[0200] In the first step, a paraffin fraction containing mainly 10 to 13 carbon atoms was partially dehydrogenated, and the resulting olefins (mainly monoolefins and mainly linear) were reacted with benzene using HF as a catalyst. Unreacted raw materials were removed by distillation. Subsequently, a fraction of C10-C13 monoalkylated alkylbenzene was removed by distillation. This monoalkylated alkylbenzene fraction contains mainly 10 to 13 carbon atoms (average 11.6 carbon atoms) within the alkyl chain, has an average molecular weight of 241 g / mol, a 2-phenyl isomer content of 15%, and a boiling point range at an absolute pressure of 1 atm from 288 °C (first 5% of the fraction) to 304 °C (95% of the fraction).

[0201] In the second step, the obtained C10-C13 ABS mixture was sulfonated. 1.0 equivalent of the obtained alkylbenzene was converted by reacting it with approximately 1.03 equivalents of sulfur trioxide in a falling membrane reactor (glass reactor, length 1 m) at 50 °C in the presence of a nitrogen stream. The alkylbenzene flows from the top to the bottom of the glass reactor. During this process, a membrane of organic material is formed. The nitrogen stream is controlled to generate fine waves on the organic membrane. The nitrogen stream contains approximately 1.03 equivalents of gaseous sulfur trioxide. At the bottom of the reactor, the obtained liquid is collected and stored at 50 °C for 2 hours. The sulfonation reaction is terminated by adding 0.3 to 0.5 weight percent of water. The obtained material is analyzed through proton NMR spectroscopy (determination of ABS and alkylbenzene content), carbon NMR spectroscopy (determination of ABS and alkylbenzene content), gas chromatography and HPLC (determination of structural ratios), ion chromatography (determination of sulfuric acid content), Hyamine titration (determination of anionic surfactant content), and Karl Fischer analysis (determination of moisture content).

[0202] Finally, in a 250 ml round-bottom glass flask equipped with a stirrer, 100 g of the ABS mixture was prepared by mixing the ABS composition of Example 5 (92.5 g) with the ABS composition prepared above containing the detergent surfactant C10-C13-Ph-SO3H (7.5 g) at 50 °C. The two ABSs were added to the flask and stirred at 50 °C for 1 hour to obtain a homogeneous mixture. The obtained material was analyzed by proton NMR spectroscopy (determination of ABS and alkylbenzene content), carbon NMR spectroscopy (determination of ABS and alkylbenzene content), gas chromatography and HPLC (determination of structural ratios), ion chromatography (determination of sulfate content), Hyamine titration (determination of anionic surfactant content), and Karl Fischer analysis (determination of moisture content).

[0203] Obtained composition, Example 6:

[0204]

[0205] Preparation of the ABS composition of Example 7 of the present invention:

[0206] An ABS composition containing the detergent surfactant C10-C13-Ph-SO3H was obtained in the following manner:

[0207] In the first step, a paraffin fraction containing mainly 10 to 13 carbon atoms was partially dehydrogenated, and the resulting olefins (mainly monoolefins and mainly linear) were reacted with benzene using HF as a catalyst. Unreacted raw materials were removed by distillation. Subsequently, a fraction of C10-C13 monoalkylated alkylbenzene was removed by distillation. This monoalkylated alkylbenzene fraction contains mainly 10 to 13 carbon atoms (average 11.6 carbon atoms) within the alkyl chain, has an average molecular weight of 241 g / mol, a 2-phenyl isomer content of 15%, and a boiling point range at an absolute pressure of 1 atm from 288 °C (first 5% of the fraction) to 304 °C (95% of the fraction).

[0208] In the second step, the obtained C10-C13 ABS mixture was sulfonated. 1.0 equivalent of the obtained alkylbenzene was converted by reacting it with approximately 1.03 equivalents of sulfur trioxide in a falling membrane reactor (glass reactor, length 1 m) at 50 °C in the presence of a nitrogen stream. The alkylbenzene flows from the top to the bottom of the glass reactor. During this process, a membrane of organic material is formed. The nitrogen stream is controlled to generate fine waves on the organic membrane. The nitrogen stream contains approximately 1.03 equivalents of gaseous sulfur trioxide. At the bottom of the reactor, the obtained liquid is collected and stored at 50 °C for 2 hours. The sulfonation reaction is terminated by adding 0.3 to 0.5 weight percent of water. The obtained material is analyzed through proton NMR spectroscopy (determination of ABS and alkylbenzene content), carbon NMR spectroscopy (determination of ABS and alkylbenzene content), gas chromatography and HPLC (determination of structural ratios), ion chromatography (determination of sulfuric acid content), Hyamine titration (determination of anionic surfactant content), and Karl Fischer analysis (determination of moisture content).

[0209] Finally, in a 250 ml round-bottom glass flask equipped with a stirrer, 100 g of the ABS mixture was prepared by mixing the ABS composition of Example 2 (92.5 g) with the ABS composition prepared above containing the detergent surfactant C10-C13-Ph-SO3H (7.5 g) at 50 °C. The two ABSs were added to the flask and stirred at 50 °C for 1 hour to obtain a homogeneous mixture. The obtained material was analyzed by proton NMR spectroscopy (determination of ABS and alkylbenzene content), carbon NMR spectroscopy (determination of ABS and alkylbenzene content), gas chromatography and HPLC (determination of structural ratios), ion chromatography (determination of sulfate content), Hyamine titration (determination of anionic surfactant content), and Karl Fischer analysis (determination of moisture content).

[0210] Obtained composition, Example 7:

[0211]

[0212] Preparation of concentrated mixtures

[0213] To prepare a concentrated mixture having a high active surfactant content and a low moisture content, the alkylbenzenesulfonic acid prepared in Comparative Examples 1, 3, and 4 and Examples 2, 5, 6, and 7 of the present invention is TSP-(PO) 35 -(EO) 20 - It is neutralized with 50 wt% NaOH in water in the presence of SO4NH4 (polyalkoxylate-based surfactant). The obtained concentrated mixture has a pH of 7.5 or higher.

[0214] TSP-(PO) 35 -(EO) 20 -Preparation of SO4NH4:

[0215] Styrinized phenol (tristyrylphenol 80%, distyrylphenol 15%, and monostyrylphenol 5%) is first propoxylated with 35 equivalents of propylene oxide at 130 °C using a KOH catalyst, and then ethoxylated with 20 equivalents of ethylene oxide. Subsequently, this is sulfated with sulfamic acid at 95 °C in the presence of a catalytic amount of urea. 1 H-NMR analysis results yielded a sulfation degree of 98%. The obtained TSP-(PO) 35 -(EO) 20 -SO4NH4 has an active content of 98%, a pour point of less than 20°C, and a viscosity of 9000 to 14000 mPa·s at 25°C.

[0216] Active ABS surfactant (acidic form), TSP-(PO) used in each concentrated mixture 35 -(EO) 20 The exact weight ratios of -SO4NH4 and 50 wt.% NaOH aqueous solution are shown in Table 1. In all cases, TSP-(PO) in the concentrated mixture 35 -(EO) 20The weight ratio between SO4NH4 and active ABS (acidic form) is approximately 1.5:1. This is TSP-(PO) 35 -(EO) 20 This means that the weight ratio between SO4NH4 and active ABS (salt form, i.e., ABS neutralized with sodium hydroxide) is 1.5:1.056.

[0217] Preparation of EOR composition

[0218] To prepare the EOR composition, the concentrated mixture is dissolved in brine to obtain the desired surfactant concentration: 2556 ppm of active surfactant (1500 ppm of TSP-(PO) 35 -(EO) 20 Active ABS (salt form) of -SO4NH4+ 1056 ppm.

[0219] The brine used in the appearance / solubility test consists of water, 0.45% NaCl, 0.01% KCl, 0.1% NaHCO3, 0.05% Na2SO4, and 2.75% Na2CO3.

[0220] The brine used in the IFT test consists of water, 0.45% NaCl, 0.01% KCl, 0.1% NaHCO3, 0.05% Na2SO4, and 2.5% Na2CO3.

[0221] Viscosity measurement

[0222] The viscosity of the alkyl benzene sulfonic acid composition and the concentrated mixture was measured. An Anton Parr viscometer with a double gap shape was used. The results are shown in Table 1.

[0223] 25 ℃ and 10 s -1 If the viscosity is less than 5000 mPa·s, it means that the substance is pumpable.

[0224] Flow point measurement

[0225] The pour points of the alkyl benzene sulfonic acid composition and the concentrated mixture were measured according to ASTM D7346. The results are shown in Table 1.

[0226] A low pour point means that a substance maintains fluidity and can be pumped even at low temperatures.

[0227] Evaluation of the appearance of the EOR composition at 65 ℃

[0228] TSP-(PO) in the presence of Na2CO3 at 65 ℃ 35 -(EO) 20 The solubility of alkyl benzene sulfonate salts combined with -SO4NH4 was investigated.

[0229] To use alkyl benzene sulfonic acids in EOR applications, they are neutralized with, for example, Na2CO3 or NaOH to obtain the corresponding salt.

[0230] The EOR composition will comprise at least an alkylbenzene sulfonate salt, any impurities from the ABS manufacturing step (e.g., sulfonic acid), any residue of Na2CO3 or NaOH from the neutralization step, and, if necessary, a second surfactant. For a successful EOR process, it is important that the EOR composition is clear, homogeneous, and stable. If the EOR composition is turbid and tends to precipitate, for example, sodium sulfate (from the residue of sulfonic acid and Na2CO3 or NaOH) or calcium sulfate (from the residue of sulfonic acid in contact with the water containing divalent cations such as calcium cations) is formed, there is a risk that the porous reservoir will become clogged and the oil recovery method will fail.

[0231] The evaluation was performed visually.

[0232] Measurement of Interfacial Tension (IFT) between EOR Composition and Crude Oil

[0233] The interaction between 10 vol.% crude oil (high paraffin content from Northwest India) and 90 vol.% EOR composition was investigated. To match solubility and optimal phase behavior, an EOR composition with a Na2CO3 content of only 2.5% was used. Upon storage for several days or weeks without stirring under optimal conditions, a Winsor III type microemulsion is formed. In Winsor III type microemulsions, ultra-low interfacial tensions of generally less than 0.01 mN / m are achieved. From the phase behavior tests, SP * The interfacial tension can be calculated using the Huh equation. Measurements were performed at 65 ℃.

[0234] Table 1: Experimental results of ABS composition, concentrate mixture, and EOR composition

[0235]

[0236] 1 ABS composition, TSP-(PO) used as a second surfactant 35 -(EO) 20 - A concentrated mixture prepared by mixing SO4NH4 and 50 wt.% NaOH aqueous solution in the indicated amounts.

[0237] 2 EOR composition: TSP-(PO) 35 -(EO) 20 - SO4NH4 1500 ppm, active neutralizing ABS surfactant 1056 ppm and brine containing water, 0.45% NaCl, 0.01% KCl, 0.1% NaHCO3, 0.05% Na2SO4 and 2.75% Na2CO3.

[0238] 3 EOR composition: Same as above, but the brine contains 2.5% Na2CO3.

[0239] 4 High-paraffin content crude oil from Northwest India

[0240] 5 nd = Undetermined

[0241] 6 Unwanted foam formation was observed (due to some ammonia release), and additional NaOH solution was required to completely neutralize the ABS composition.

[0242] Comments on the experimental results presented in Table 1:

[0243] There are two main methods for obtaining an EOR composition containing between 0.05 and 2 weight percent of a surfactant, including at least an ABS surfactant, that can be used directly at the oilfield. During the EOR operation, the alkylbenzenesulfonic acid is neutralized, for example, with Na2CO3 or NaOH to obtain the corresponding sodium salt, and this is TSP-(PO) 35 -(EO) 20 It is mixed with at least a second surfactant based on a polyalkoxylate, such as SO4NH4.

[0244] The first option is an acidic ABS composition (M + = H + The method involves transporting the product from the manufacturing site to a storage area or nearby location to perform a neutralization step and, if necessary, mixing it with a second or additional surfactant. For this option to be successful and efficient, it is desirable that the acidic ABS composition be easy to transport and handle. This was tested in columns 3 and 4 of Table 1 and is described below.

[0245] The second option is to transfer a high-activity surfactant concentrate mixture, containing neutralized ABS and, if necessary, a second or additional surfactant, to a storage facility or a nearby location. There, the surfactant concentrate mixture can then be dissolved to obtain a ready-to-use EOR composition. For this option to be successful and efficient, it is desirable that the concentrate mixture possesses optimal transport and handling characteristics. Specifically, the concentrate mixture should be fluid at 20°C (a pour point below 20°C), and, for example, its viscosity at 65°C should be sufficiently low to allow for smooth pumping of the material (sulfurizing surfactants are stable up to at least 60 to 65°C depending on pH). This was tested in columns 6 and 7 of Table 1 and is described below.

[0246] Furthermore, the EOR composition of the present invention must be suitable for EOR operations to successfully perform crude oil recovery. To this end, the EOR composition must have a transparent appearance, be homogeneous, and stable. This is because a turbid solution can cause clogging of porous reservoirs. Additionally, it is highly desirable that when the EOR composition is added to underground strata, a Winsor Type III emulsion is formed that achieves an ultra-low IFT (i.e., less than 0.01 mN / m) between water and oil. This was tested in columns 8 and 9 of Table 1 and is described below.

[0247] First option - Transport of individual components:

[0248] Column 3 of Table 1 is the acidic ABS composition with high activity content of the present invention (M + = H + ) shows that it is a liquid at room temperature and has low viscosity. The tested composition has an active content of more than 90 wt%, and at 25 ℃ and 10 s -1It exhibits a viscosity of less than 5000 mPa·s. This demonstrates that acidic ABS compositions with a high active content can be transported to another location (e.g., a remote storage facility) in an efficient manner; in other words, when transporting such ABS compositions to another location (e.g., a remote storage facility), a diluted aqueous neutralized ABS solution having a low storage capacity (e.g., a low truck) and thus about 10 to 20 weight% of active material (e.g., M + = It requires less energy than transporting Na.

[0249] ABS composition (M) located close to the storage facility + = H + When this is reached, the acidic ABS composition must be neutralized with a base, such as Na2CO3 or NaOH, to obtain the corresponding sodium salt before being injected into the underground well. It should be noted that many oil and gas recovery operations are carried out during the winter or in regions with very low ambient temperatures. To facilitate the handling of the acidic ABS composition and its neutralization step, and to reduce heating requirements, it is highly desirable for the acidic ABS composition to maintain fluidity and pumpability even at very low temperatures—that is, to have a low pour point. Column 4 of Table 1 clearly shows that the ABS composition of the present invention has a much lower pour point than the comparative composition. Examples 2, 5, 6, and 7 of the present invention exhibit pour points between -30°C and -33°C, whereas the comparative example exhibits a high pour point of -9°C (C1).

[0250] Second option - Transport of surfactant concentrate mixtures:

[0251] When transporting a surfactant concentrate mixture directly to a storage location or a nearby location, in order to reduce energy costs for transporting and storing such mixtures, it is desirable that the concentrate mixture has a low moisture content, a high active content, and is flowable at 20°C (pour point less than 20°C). In addition, it is important that the viscosity at, for example, 65°C is sufficiently low so that the material can be pumped smoothly.

[0252] To obtain high activity content and low moisture content, alkylbenzenesulfonic acid is the TSP-(PO) described above 35 -(EO) 20 It was neutralized with 50 wt% NaOH in water in the presence of SO4NH4.

[0253] As shown in columns 6 and 7 of Table 1, the concentrated mixture of the present invention has a desirable pour point of less than 20 °C and a viscosity of about 1000 to 650 mPa·s at 65 °C. This means that the material has excellent pumpability. In contrast, Comparative Examples C1 and C4 show that undesirable waxy materials with a pour point greater than 40 °C are obtained. In these cases, unwanted foaming was also observed (due to some ammonia release), and a larger amount of NaOH solution was required for the complete neutralization of the alkylbenzenesulfonic acid.

[0254] Suitability of EOR composition for EOR application:

[0255] TSP-(PO) in the presence of Na2CO3 at 65 ℃ 35 -(EO) 20The solubility of neutralized alkylbenzenesulfonic acid combined with -SO4NH4 was investigated. Column 8 of Table 1 shows the appearance of the aqueous surfactant solution (i.e., EOR composition) at 65 °C. In all examples except Comparative Example 3, a clear, stable, and homogeneous solution was observed, meaning sufficient solubility was obtained. "Group B" ABS compounds without "Group A" ABS compounds showed insufficient solubility, resulting in the formation of a turbid solution. This is highly undesirable in crude oil recovery operations, as the turbid solution can cause clogging of porous reservoirs. Turbid solutions must be avoided.

[0256] Interaction with crude oil was investigated. In this experiment, a brine with a low Na2CO3 content was selected to match solubility and optimal phase behavior. When the EOR composition is added to the underground layer, it is desirable to form a Winsor type III emulsion with a very low IFT between water and oil (i.e., less than 0.01 mN / m).

[0257] When crude oil is mixed with an aqueous surfactant solution under optimal conditions, the formation of golden streaks indicates that a Winsor type III microemulsion is formed. Once the Winsor type III microemulsion is obtained, SP * was measured, and the interfacial tension was calculated using the Huh equation. Column 9 of Table 1 shows that the EOR composition of the present invention successfully achieves an ultra-low interfacial tension of less than 0.01 mN / m.

[0258] Comparative Example C1 failed to produce a Winsor type III microemulsion, and only a higher ITF was obtained. The EOR composition of Comparative Example 3 (C3) was not tested because it did not provide sufficient solubility.

[0259] Accordingly, the experimental results in Table 1 show that Examples 2, 5, 6, and 7 of the present invention provide a desirable combination of handling properties (low pour point and low viscosity), solubility, and interfacial tension with respect to crude oil. On the other hand, the single compounds of Comparative Examples C1, C3, and C4 do not provide desirable properties and fail in at least one aspect.

[0260] Embodiments of the present invention:

[0261] 1. A composition comprising the following alkyl benzene sulfonate ABS (I) and ABS (II):

[0262]

[0263] [During the meal,

[0264] R 1 and R 2 is independently selected from saturated alkyl groups containing 2 to 13 carbon atoms;

[0265] R 1 and R 2 It has a total of 15 carbon atoms together;

[0266] M + is H + , NH4 + or a monovalent cation, preferably H + , NH4 + , Na + or K + [Selected independently from]

[0267] The molar ratio of the above ABS (I) : ABS (II) is in the range of 10:90 to 30:70;

[0268] The above composition is the following ABS (III), ABS (IV), ABS (V)

[0269]

[0270] [During the meal,

[0271] M + is H + , NH4 +or a monovalent cation, preferably H + , NH4 + , Na + or K + [Selected independently from]

[0272] and comprises one or more additional alkylbenzene sulfonate molecules selected from mixtures thereof;

[0273] The molar ratio of the above alkyl benzene sulfonate [(I)+(II)] : [(III)+(IV)+(V)] is in the range of 90:10 to 99.9:0.1;

[0274] The above alkyl benzene sulfonates (I) - (V) together may be referred to as ABS mixture "Group A".

[0275] 2. In a preferred embodiment of the present invention, the composition further comprises other alkyl benzene sulfonate molecules different from ABS mixture “Group A”, and the amount of ABS mixture “Group A” is 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, with respect to the total weight of alkyl benzene sulfonate molecules present in the composition.

[0276] 3. In a preferred embodiment of the present invention, the composition is the following ABS (VI), ABS (VII), ABS (VIII)

[0277]

[0278] [During the meal,

[0279] R 3 is a saturated alkyl group containing 14 to 15 carbon atoms;

[0280] R 4 , R 5 , R 6 , R 7 , R 8 is independently selected from saturated alkyl groups containing two or more carbon atoms;

[0281] R 4 and R5 The sum of all carbon atoms in is in the range of 10 to 20, but the single alkyl group does not contain more than 15 carbon atoms;

[0282] R 6 , R 7 and R 8 The sum of all carbon atoms in is in the range of 10 to 20, but the single alkyl group does not contain more than 15 carbon atoms;

[0283] M + is H + , NH4 + or a monovalent cation, preferably H + , NH4 + , Na + or K + [Selected independently from]

[0284] and one or more additional alkylbenzene sulfonate molecules selected from mixtures thereof;

[0285] The above alkyl benzene sulfonates (VI) - (VIII) together may be referred to as ABS mixture "Group B";

[0286] The weight ratio of the above ABS mixture “Group A” : “Group B” is in the range of 95:5 to 70:30, preferably 90:10 to 70:30, more preferably 85:15 to 75:25.

[0287] 4. In a preferred embodiment of the present invention, the molar ratio of alkyl benzene sulfonate (VI) : [(VII)+(VIII)] is in the range of 0:100 to 20:80.

[0288] 5. In a preferred embodiment of the present invention, the composition is the following ABS (IX)

[0289]

[0290] [During the meal,

[0291] R 9is a saturated alkyl group containing 10 to 13 carbon atoms;

[0292] M + is H + , NH4 + or a monovalent cation, preferably H + , NH4 + , Na + or K + am]

[0293] Including;

[0294] The above alkyl benzene sulfonate (IX) may be referred to as ABS mixture "Group C";

[0295] The weight ratio of the above ABS mixture “Group A” : “Group C” is in the range of 25:75 to 97.5:2.5, preferably 50:50 to 97.5:2.5, more preferably 70:30 to 95:5, and even more preferably 85:15 to 95:5.

[0296] 6. In a preferred embodiment of the present invention, the composition further comprises an ABS mixture “Group C” as described above, and the weight ratio of the ABS mixture (“Group A” + “Group B”) : “Group C” is in the range of 80:20 to 97.5:2.5, preferably 85:15 to 97.5:2.5, more preferably 85:15 to 95:5.

[0297] 7. In a preferred embodiment of the present invention, ABS (IX) is the following ABS (X) and ABS (XI)

[0298]

[0299] [During the meal,

[0300] R 10 It is a saturated alkyl group containing 8 to 11 carbon atoms;

[0301] R 11 and R 12is independently selected from saturated alkyl groups containing 2 to 10 carbon atoms;

[0302] R 11 and R 12 It has a total of 9 to 12 carbon atoms together;

[0303] M + is H + , NH4 + or a monovalent cation, preferably H + , NH4 + , Na + or K + [Selected independently from]

[0304] Selected from;

[0305] The weight ratio of the above ABS (X) : ABS (XI) is in the range of 10:90 to 25:75, preferably 14:86 to 21:79.

[0306] 8. In a preferred embodiment of the present invention, any one of the alkyl chains of ABS (I) - (V) and (IX) - (XI) is at least 90 wt.% linear, preferably at least 95 wt.% linear.

[0307] 9. A concentrated mixture comprising an ABS composition according to any one of the above embodiments, a basic ionic salt, and a second surfactant different from any of ABS (I) - (XI).

[0308] 10. In a preferred embodiment of the present invention, the second surfactant in the concentrated mixture is a polyalkoxylate-based surfactant, preferably a tristyrylphenol alkoxysulfate surfactant, more preferably a TSP-(PO) 35 -(EO) 20 It is SO4NH4.

[0309] 11. In a preferred embodiment of the present invention, the weight ratio of the second surfactant to the acidic form of the ABS composition in the concentrated mixture is 1:1 to 2:1, preferably 1.4:1 to 1.6:1.

[0310] 12. An EOR composition comprising an additional surfactant different from any of the ABS composition, basic ionic salt, and ABS (I) - (XI) according to any one of the above embodiments, wherein the total amount of all surfactants present in the EOR composition is between 0.05 wt.% and 2 wt.% with respect to the total weight of the EOR composition.

[0311] 13. Use of the EOR composition according to the above embodiment in oilfield or enhanced oil recovery (EOR) applications.

[0312] 14. In a preferred embodiment of the present invention, the oil field or EOR application field is selected from the group consisting of EOR surfactants, flow recovery improvers, wetting agents, dispersants, emulsifiers, drilling fluids, fracturing fluids, spacer fluids, drilling cut cleaners, borehole cleaners, and foaming agents for drilling fluids.

[0313] 15. A method for recovering crude oil from an oil-containing underground geological layer, comprising injecting an EOR composition according to the above embodiment into one or more injection wells, forming a Winsor type III microemulsion, achieving an interfacial tension between the crude oil and an aqueous surfactant solution of less than 0.1 mN / m, and producing crude oil in one or more production wells.

[0314] 16. In a preferred embodiment of the present invention, the oil-containing underground layer comprises a sandstone or carbonate storage layer with a storage temperature of 15 to 130°C.

Claims

Claim 1 A composition comprising the following alkyl benzene sulfonate ABS (I) and ABS (II): [In the middle of the meal, R 1 and R 2 is independently selected from saturated alkyl groups containing 2 to 13 carbon atoms; R 1 and R 2 It has a total of 15 carbon atoms together; M + is H + , NH4 + or a monovalent cation, preferably H + , NH4 + , Na + or K + [Selected independently from]; the molar ratio of ABS (I) : ABS (II) is in the range of 10:90 to 30:

70. Claim 2 A composition according to claim 1, wherein the composition comprises one or more additional alkylbenzene sulfonate molecules selected from ABS (III), ABS (IV), ABS (V) and mixtures thereof: [In the middle of the meal, M + is H + , NH4 + or a monovalent cation, preferably H + , NH4 + , Na + or K + [Independently selected from]; the molar ratio of the alkyl benzene sulfonate [(I)+(II)] : [(III)+(IV)+(V)] is in the range of 90:10 to 99.9:0.1; and the alkyl benzene sulfonate (I) - (V) together may be referred to as ABS mixture “Group A”. Claim 3 A composition according to claim 2, wherein the composition further comprises other alkyl benzene sulfonate molecules different from ABS mixture "Group A", and the amount of ABS mixture "Group A" is 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more, based on the total weight of all alkyl benzene sulfonate molecules present in the composition. Claim 4 A composition according to claim 2 or 3, wherein the composition comprises one or more additional alkylbenzene sulfonate molecules selected from the following ABS (VI), ABS (VII), ABS (VIII) and mixtures thereof: [In the middle of the meal, R 3 is a saturated alkyl group containing 14 to 15 carbon atoms; R 4 , R 5 , R 6 , R 7 , R 8 is independently selected from saturated alkyl groups containing two or more carbon atoms; R 4 and R 5 The sum of all carbon atoms in is in the range of 10 to 20 carbon atoms, but the single alkyl group does not contain more than 15 carbon atoms; R 6 , R 7 and R 8 The sum of all carbon atoms in is in the range of 10 to 20 carbon atoms, but the single alkyl group does not contain more than 15 carbon atoms; M + is H + , NH4 + or a monovalent cation, preferably H + , NH4 + , Na + or K + [Independently selected from]; the above alkyl benzene sulfonate (VI) - (VIII) together may be referred to as ABS mixture “Group B”; the weight ratio of the above ABS mixture “Group A” : “Group B” is in the range of 95:5 to 70:30, preferably 90:10 to 70:30, more preferably 85:15 to 75:

25. Claim 5 A composition according to claim 4, wherein the molar ratio of alkyl benzene sulfonate (VI) : [(VII)+(VIII)] is in the range of 0:100 to 20:

80. Claim 6 A composition according to any one of claims 2 to 5, wherein the composition comprises the following ABS (IX): [In the middle of the meal, R 9 is a saturated alkyl group containing 10 to 13 carbon atoms; M + is H + , NH4 + or a monovalent cation, preferably H + , NH4 + , Na + or K + [is]; the above alkyl benzene sulfonate (IX) may be referred to as ABS mixture “Group C”; the weight ratio of the above ABS mixture “Group A” : “Group C” is in the range of 25:75 to 97.5:2.5, preferably 50:50 to 97.5:2.5, more preferably 70:30 to 95:5, and even more preferably 85:15 to 95:

5. Claim 7 A composition according to claim 4 or 5, wherein the composition further comprises an ABS mixture "Group C" as defined above, and the weight ratio of the ABS mixture ("Group A" + "Group B") : "Group C" is in the range of 80:20 to 97.5:2.5, preferably 85:15 to 97.5:2.5, and more preferably 85:15 to 95:

5. Claim 8 In claim 6 or 7, the composition wherein ABS (IX) is selected from the following ABS (X) and ABS (XI): [In the middle of the meal, R 10 is a saturated alkyl group containing 8 to 11 carbon atoms; R 11 and R 12 is independently selected from saturated alkyl groups containing 2 to 10 carbon atoms; R 11 and R 12 It has a total of 9 to 12 carbon atoms together; M + is H + , NH4 + or a monovalent cation, preferably H + , NH4 + , Na + or K + [Independently selected from]; the weight ratio of ABS (X) : ABS (XI) is in the range of 10:90 to 25:75, preferably 14:86 to 21:

79. Claim 9 A composition according to any one of claims 1 to 8, wherein at least one of the alkyl chains of ABS (I) - (V) and (IX) - (XI) is 90% linear. Claim 10 A composition according to any one of claims 1 to 9, wherein the composition further comprises a basic ionic salt and a second surfactant. Claim 11 In claim 9, the second surfactant is a polyalkoxylate-based surfactant, preferably a tristyrylphenol alkoxysulfate surfactant, more preferably TSP-(PO) 35 -(EO) 20 - A composition of SO4NH4. Claim 12 A composition according to claim 9 or 10, wherein the weight ratio of the second surfactant to the acidic form of the ABS composition is between 1:1 and 2:1, preferably between 1.4:1 and 1.6:

1. Claim 13 An EOR composition comprising an ABS composition according to any one of claims 1 to 8, a basic ionic salt, and an additional surfactant different from any one of ABS (I) - (XI) according to any one of claims 1 to 9, wherein the total amount of all surfactants present in the EOR composition is between 0.05 and 2 wt.% with respect to the total weight of the EOR composition. Claim 14 Use of the EOR composition according to claim 12 in oil fields or enhanced oil recovery (EOR) applications. Claim 15 In claim 14, the oil field or EOR application is a use selected from the group consisting of EOR surfactants, flow recovery improvers, wetting agents, dispersants, emulsifiers, drilling fluids, fracturing fluids, spacer fluids, drilling material cleaners, borehole cleaners, and foaming agents for drilling fluids. Claim 16 A method for recovering crude oil from an oil-containing underground layer, comprising injecting a composition according to claim 13 into one or more injection wells, forming a Winsor type III microemulsion, achieving an interfacial tension between the crude oil and an aqueous surfactant solution of less than 0.1 mN / m, and producing crude oil in one or more production wells. Claim 17 A method for recovering petroleum according to claim 16, wherein the oil-containing underground layer comprises a sandstone or carbonate storage tank having a storage temperature of 15 to 130°C.

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