Amino carboxylate alkyl alcohol ether monoester, preparation method and application thereof, imbibition agent composition, imbibition agent and application thereof

Abstract

The invention relates to the field of oil field low-permeability and unconventional tight oil reservoir and shale oil reservoir exploitation, and provides amino carboxylate alkyl alcohol ether monoester, the structural formula of which is shown in the specification, in the formula, m is 2-30; n is 0 to 30; r is selected from C4-C22 alkyl groups; m is selected from positive ions or positive ion groups enabling the molecules shown in the formula (1) to be electrically neutral. According to the imbibition agent composition formed by compounding the amino carboxylate alkyl alcohol ether monoester and the auxiliaries, the temperature resistance of the imbibition agent composition can be improved to 120 DEG C, the salt resistance of the imbibition agent composition can be improved to 250000mg / L, and the calcium and magnesium ion resistance of the imbibition agent composition can be improved to 2000mg / L; meanwhile, good injection performance and super-strong wetting change performance are achieved, and the imbibition efficiency of low-permeability and compact oil reservoirs can be greatly improved.

Description

Technical Field

[0001] This invention relates to an aminocarboxylate alkyl alcohol ether monoester, its preparation method and application, an absorbent composition, an absorbent and its application. Background Technology

[0002] For crude oil extraction from low-permeability, ultra-low-permeability, and tight / shale reservoirs, capillary forces are playing an increasingly prominent role. The wetting reversal effect of surfactants is even more crucial for improving the recovery rate of these oil-wet reservoirs. Studies have found that wetting reversal is a primary condition for improving the permeable oil recovery of low-permeability, ultra-low-permeability, and tight reservoirs. To enhance reservoir permeability, the selection of surfactants should not simply pursue ultra-low interfacial tension, but should focus more on the effectiveness of wetting reversal while maintaining a certain level of interfacial tension.

[0003] The mechanisms by which surfactants alter the wettability of rock surfaces are generally categorized into two types: coating, where hydrophobic groups adsorb onto the oily rock surface while hydrophilic groups are exposed, thus reversing wetting; and cleaning, where surfactants remove the oily adsorbed layer from the rock surface to expose the original water-wetted surface, achieving wetting reversal. Studies have shown that the cleaning mechanism, which forms induced ion pairs between surfactants with the same charge as the formation and polar substances adsorbed on the rock surface, ultimately reversing wetting, is more efficient and stable than the coating mechanism, which relies on surfactant adsorption.

[0004] Salehi et al., working with Berea sandstone, found that bipolar hydrophilic anionic surfactants outperformed monopolar hydrophilic surfactants in enhancing spontaneous adsorption, and were even more effective than cationic surfactants. This, to some extent, demonstrates the mechanism by which surfactant molecules interact with adsorbed organic matter through an electric field to form "ion pairs," thus altering wettability. Furthermore, compared to traditional monopolar anionic surfactants, bipolar anionic surfactants exhibit lower critical micelle concentrations (CMC), higher interfacial properties, and better emulsifying properties. Summary of the Invention

[0005] The purpose of this invention is to provide an aminocarboxylate alkyl alcohol ether monoester, its preparation method and application, a percolator composition, and a percolator and its application. The aminocarboxylate alkyl alcohol ether monoester of this invention is a multi-headed anionic surfactant. The aminocarboxylate alkyl alcohol ether monoester and the additive form a composition that can regulate the wettability of rock formations, making it particularly suitable for oil reservoir development and able to significantly improve oil displacement efficiency.

[0006] To achieve the above objectives, the first aspect of the present invention provides an aminocarboxylic acid alkyl alcohol ether monoester, with the structural formula shown in formula (1):

[0007]

[0008] Where m is 2-30; n is 0-30;

[0009] R is selected from C4-C22 alkyl groups;

[0010] M is selected from cations or cationic groups that make the molecule shown in formula (1) electrically neutral.

[0011] A second aspect of this invention provides a method for preparing the aminocarboxylate alkyl alcohol ether monoester of this invention, comprising the following steps:

[0012] (1) In the presence of a catalyst, N,N-bis(carboxymethyl)-L-glutamic acid is first contacted with the alkyl alcohol polyoxyethylene polyoxypropylene ether shown in formula (2) to obtain an aminocarboxylic acid alkyl alcohol ether monoester.

[0013]

[0014] In formula (2), m is 2-30; n is 0-30; R is selected from C4-C22 alkyl groups; alkyl refers to straight-chain alkyl or branched alkyl;

[0015] (2) The aminocarboxylic acid alkyl alcohol ether monoester is subjected to a second contact with an M-containing basic compound to obtain an aminocarboxylic acid salt alkyl alcohol ether monoester.

[0016] A third aspect of the present invention provides an application of the aminocarboxylic acid alkyl alcohol ether monoester described in the present invention as a surfactant.

[0017] A fourth aspect of the present invention provides an absorbent composition comprising the aminocarboxylate alkyl alcohol ether monoester described in the present invention and an adjuvant selected from carboxylates.

[0018] A fifth aspect of the present invention provides an absorbent comprising the absorbent composition described herein and water.

[0019] The sixth aspect of this invention provides an application of the permeabilizer described herein in oil reservoir development.

[0020] The aminocarboxylate alkyl alcohol ether monoester of this invention is a multi-headed anionic surfactant. The aminocarboxylate alkyl alcohol ether monoester, when combined with additives, forms a composition that can regulate rock wettability, making it particularly suitable for oil reservoir development. It can significantly improve oil displacement efficiency, presumably because the introduction of multi-headed carboxylate, compared to single-headed surfactants, enhances the surfactant's ability to strip crude oil adhering to the sandstone surface, promoting wettability reversal. Simultaneously, by introducing alkyl alcohol ethers and adjusting the alkyl carbon chain length and polyether number, the hydrophilic and oleophilic properties of the aminocarboxylate alkyl alcohol ether monoester can be flexibly controlled, enhancing the system's temperature and salt resistance.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] (1) The present invention provides a novel aminocarboxylic acid alkyl alcohol ether monoester as a surfactant, which greatly improves the wetting reversal ability of sandstone surface;

[0023] (2) The temperature resistance of the permeating agent composition using the novel aminocarboxylate alkyl alcohol ether monoester of the present invention as a surfactant can be improved to 120°C, the salt resistance can be improved to 250,000 mg / L, and the calcium and magnesium ion resistance can be improved to 2,000 mg / L.

[0024] (3) The permeation agent composition using the novel aminocarboxylate alkyl alcohol ether monoester of the present invention as a surfactant has good injection performance and can greatly improve the permeation efficiency of low-permeability and tight oil reservoirs.

[0025] (4) The novel aminocarboxylic acid alkyl alcohol ether monoester of the present invention is used as a permeating agent for surfactants and is environmentally friendly and easily degradable. Detailed Implementation

[0026] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0027] In this invention, alkyl refers to straight-chain alkyl or branched alkyl.

[0028] The first aspect of this invention provides an aminocarboxylic acid alkyl alcohol ether monoester, with the structural formula shown in formula (1):

[0029]

[0030] Where m is 2-30; n is 0-30;

[0031] R is selected from C4-C22 alkyl groups;

[0032] M is selected from cations or cationic groups that make the molecule shown in formula (1) electrically neutral.

[0033] The aminocarboxylate alkyl alcohol ether monoester of the present invention has a polyhead carboxylate, which can be used as a surfactant to improve the ability to remove crude oil adhering to the surface of sandstone. At the same time, the substance has an alkyl alcohol ether structure, and the hydrophilic and oleophilic properties of the aminocarboxylate alkyl alcohol ether monoester can be flexibly controlled by adjusting the alkyl carbon chain length and the number of polyethers.

[0034] In this invention, the structural formula (1) is an exemplary structural formula used to illustrate that the aminocarboxylic acid alkyl alcohol ether monoester has the above-mentioned groups and each structural unit, and there is no particular limitation on the connection method between the structural units.

[0035] In this invention, m is the number of additions of the ethoxy group EO, and n is the number of additions of the propoxy group.

[0036] In the aminocarboxylate alkyl alcohol ether monoester of the present invention, according to a preferred embodiment of the present invention, m is 2-30, preferably 2-25, more preferably 2-20, illustrative but not limiting the scope of the present invention, for example m is 2, 5, 8, 10, 12, 15, 18, 20.

[0037] In the aminocarboxylate alkyl alcohol ether monoesters of the present invention, according to a preferred embodiment of the present invention, n is 0-30, more preferably 0-15, as illustrative but not limiting the scope of the present invention, for example n is 0, 3, 5, 7, 9, 11, 13, 15.

[0038] In the aminocarboxylate alkyl alcohol ether monoester of the present invention, R is selected from C4-C22 alkyl groups. Alkyl refers to straight-chain alkyl or branched alkyl. According to a preferred embodiment of the present invention, R is selected from C8-C18 alkyl groups. This is an illustrative example, but does not limit the scope of the present invention. For example, R is C8 alkyl, C10 alkyl, C12 alkyl, C16 alkyl, or C18 alkyl.

[0039] In this invention, the range of possible types of M is relatively wide. This is an illustrative example and does not limit the scope of the invention. According to a preferred embodiment of the invention, M is selected from any one of alkali metals, alkaline earth metals, or ammonium ions; preferably, M is selected from Na, K, Mg, Ca, or NH4. + Any of the following, in this embodiment of the invention, Na is used as an example to illustrate the advantages of the invention, but this does not limit the scope of the invention.

[0040] A second aspect of this invention provides a method for preparing the aminocarboxylate alkyl alcohol ether monoester of this invention, comprising the following steps:

[0041] (1) In the presence of a catalyst, N,N-bis(carboxymethyl)-L-glutamic acid is first contacted with the alkyl alcohol polyoxyethylene polyoxypropylene ether shown in formula (2) to obtain an aminocarboxylic acid alkyl alcohol ether monoester.

[0042]

[0043] In formula (2), m is 2-30; n is 0-30; R is selected from C4-C22 alkyl groups;

[0044] (2) The aminocarboxylic acid alkyl alcohol ether monoester undergoes a second contact with an M-containing basic compound to obtain an aminocarboxylic acid alkyl alcohol ether monoester. The aminocarboxylic acid alkyl alcohol ether monoester prepared by the above method, by introducing a multi-headed carboxylate, improves the surfactant's ability to strip crude oil adhering to the sandstone surface compared to a single-headed surfactant, promoting wetting reversal; by introducing alkyl alcohol ethers and adjusting the alkyl carbon chain length and polyether number, the hydrophilic and lipophilic properties of the aminocarboxylic acid alkyl alcohol ether monoester can be flexibly controlled, enhancing the system's temperature and salt resistance.

[0045] In this invention, structural formula (2) is an exemplary structural formula used to illustrate that the alkyl alcohol polyoxyethylene polyoxypropylene ether has the above-mentioned groups and structural units, and there is no particular limitation on the connection method between the structural units. In formula (2), m is the number of additions of the ethoxy group EO, and n is the number of additions of the propoxy group.

[0046] In this invention, as long as the purpose of this invention can be achieved, there is no particular limitation on the preparation method of alkyl alcohol polyoxyethylene polyoxypropylene ether shown in formula (2), and conventional methods in the art are acceptable.

[0047] According to a preferred embodiment of the present invention, in formula (2), m is 2-30, preferably 2-25, more preferably 2-20, as an example but not limiting the scope of the invention, for example m is 2, 5, 8, 10, 12, 15, 18, 20.

[0048] According to a preferred embodiment of the present invention, in formula (2), n is 0-30, more preferably 0-15, as illustrative but not limiting the scope of the invention, for example n is 0, 3, 5, 7, 9, 11, 13, 15.

[0049] In the alkyl alcohol polyoxyethylene polyoxypropylene ether of the present invention, in formula (2), R is selected from C4-C22 alkyl groups. Alkyl refers to straight-chain alkyl or branched alkyl. According to a preferred embodiment of the present invention, R is selected from C8-C18 alkyl groups. This is an illustrative example, but does not limit the scope of the present invention. For example, R is C8 alkyl, C10 alkyl, C12 alkyl, C16 alkyl, or C18 alkyl.

[0050] According to a preferred embodiment of the present invention, the alkyl alcohol polyoxyethylene polyoxypropylene ether is one or more of tridecyl alcohol polyoxyethylene (5EO) polyoxypropylene ether (5PO), octadecyl alcohol polyoxyethylene (20EO), and octyl alcohol polyoxyethylene (2EO) polyoxyethylene (15PO), more preferably, the alkyl alcohol polyoxyethylene polyoxypropylene ether is octyl alcohol polyoxyethylene (2EO) polyoxyethylene (15PO).

[0051] In this invention, the range of catalysts that can be selected is relatively wide. This is an illustrative example, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the catalyst is selected from one or more of p-toluenesulfonic acid, concentrated sulfuric acid, aminosulfonic acid, potassium hydrogen sulfate, titanium chloride, tin chloride, and ferric chloride. In this embodiment of the invention, p-toluenesulfonic acid is used as an example to illustrate the advantages of the invention, but it does not limit the scope of the invention.

[0052] In this invention, the amount of catalyst added can be selected from a wide range. According to a preferred embodiment of this invention, the amount of catalyst added is 0.2%-1% of the mass of alkyl alcohol polyoxyethylene polyoxypropylene ether. For example, the amount of catalyst added is 0.3%, 0.5%, 0.7%, or 0.9% of the mass of alkyl alcohol polyoxyethylene polyoxypropylene ether. In this embodiment of the invention, 0.5% is used as an example to illustrate the advantages of the invention, but this does not limit the scope of the invention.

[0053] In this invention, in step (1), when the molar ratio of N,N-bis(carboxymethyl)-L-glutamic acid to alkyl alcohol polyoxyethylene polyoxypropylene ether is about 1:1 in the presence of a catalyst, an aminocarboxylic acid alkyl alcohol ether monoester is prepared, with the structural formula shown in formula (3).

[0054]

[0055] In equation (3), the definitions of m, n, and R are as shown in equation (2).

[0056] In this invention, there is no particular limitation on the first contact condition; conventional contact conditions in the art are acceptable. This is an illustrative example, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the contact conditions include: a temperature of 110-150°C; for example, 110°C, 120°C, 130°C, 140°C, or 150°C; the contact time of the first contact can be reasonably adjusted according to the actual situation, for example, the contact time is 0.5-4 hours. In this embodiment of the invention, a contact time of 140°C for 1 hour is used as an example to illustrate the advantages of the invention, but it does not limit the scope of the invention.

[0057] In this invention, according to a preferred embodiment, the first contact is carried out in the presence of a solvent.

[0058] In this invention, the range of solvents that can be selected is relatively wide. This is an illustrative example, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the solvent is selected from one or more of n-hexane, benzene, and ethanol. In this embodiment, n-hexane is used as an example to illustrate the advantages of the invention, but it does not limit the scope of the invention.

[0059] In this invention, the amount of solvent can be selected from a wide range. According to a preferred embodiment of this invention, the volume ratio of the solvent is 1-1.5 times the total volume of N,N-bis(carboxymethyl)-L-glutamic acid and alkyl alcohol polyoxyethylene polyoxypropylene ether. In the embodiments of this invention, the solvent volume is 1 times the total volume of N,N-bis(carboxymethyl)-L-glutamic acid and alkyl alcohol polyoxyethylene polyoxypropylene ether as an example to illustrate the advantages of this invention, but it does not limit the scope of this invention.

[0060] In this invention, the range of alkaline compounds containing M is relatively wide. This is an illustrative example, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the alkaline compound containing M is selected from one or more of hydroxides and bicarbonates of M.

[0061] In this invention, the purpose of the second contact in step (2) is to neutralize the aminocarboxylic acid alkyl alcohol ether monoester with the basic compound containing M to obtain the aminocarboxylic acid alkyl alcohol ether monoester surfactant shown in formula (1). There are no special requirements for the second contact conditions, as long as the neutralization reaction can be carried out to obtain the aminocarboxylic acid alkyl alcohol ether monoester surfactant shown in formula (1). This invention will not describe it in detail here.

[0062] In this invention, step (2) further includes washing the product after the second contact, separating oil and water, and removing the solvent from the oil phase. For example, the product is washed with a saturated sodium carbonate solution until no bubbles are generated, the mixture is centrifuged to separate the layers and remove the water layer, and the resulting oily product is distilled under reduced pressure to remove impurities and obtain the final product, a carboxylate-type alkyl alcohol ether amino acid ester.

[0063] A third aspect of the present invention provides an application of the aminocarboxylic acid alkyl alcohol ether monoester described in the present invention as a surfactant.

[0064] A fourth aspect of this invention provides a permeabilizing composition comprising the aminocarboxylate alkyl alcohol ether monoester described in this invention and an additive selected from carboxylates. The permeabilizing composition of this invention exhibits strong wetting modification properties and can improve oil displacement efficiency.

[0065] In this invention, the additive is a carboxylate, which can further enhance the system's temperature and salt resistance, injection performance, and anti-adsorption performance; preferably, the additive is selected from one or more of N,N-bis(carboxymethyl)-L-glutamic acid tetrasodium salt, sodium aspartate, sodium polyacrylate, and sodium gluconate, and more preferably, the additive is N,N-bis(carboxymethyl)-L-glutamic acid tetrasodium salt.

[0066] In this invention, the amount of aminocarboxylate alkyl alcohol ether monoester and the auxiliary agent can be selected within a wide range. According to a preferred embodiment of this invention, the mass ratio of aminocarboxylate alkyl alcohol ether monoester to auxiliary agent is 1:0.001-10; preferably, the mass ratio is 1:0.01-0.2. This is an illustrative example, but does not limit the scope of the invention. For example, the mass ratios are 1:0.01, 1:0.04, 1:0.08, 1:0.11, 1:0.14, 1:0.17, and 1:0.2.

[0067] In this invention, the type of sodium polyacrylate is not particularly limited. According to a preferred embodiment of the invention, the number-average molecular weight of sodium polyacrylate is 500-2000 g / mol. In this embodiment, sodium polyacrylate with a molecular weight of 1200 g / mol is used as an example to illustrate the advantages of the invention, but this does not limit the scope of the invention. For example, the number-average molecular weight of sodium polyacrylate is 500 g / mol, 700 g / mol, 900 g / mol, 1200 g / mol, 1500 g / mol, 1800 g / mol, or 2000 g / mol.

[0068] A fifth aspect of this invention provides a percolator comprising the percolator composition described herein and water. The percolator of this invention exhibits excellent injection performance and can significantly improve the percolation efficiency of low-permeability, tight oil reservoirs.

[0069] In this invention, the permeabilizer composition is the core component of the permeabilizer, the component that produces the actual effect. There is no particular limitation on the amount of water used. According to a preferred embodiment of the invention, the amount of water used is such that the mass concentration of the permeabilizer composition in the permeabilizer is not higher than 10%; preferably, the mass concentration of the permeabilizer composition is not higher than 1%; more preferably, the mass concentration of the permeabilizer composition is 0.05%-0.3%, for example, 0.05%, 0.07%, 0.10%, 0.14%, 0.18%, 0.22%, 0.26%, or 0.3%.

[0070] The permeabilizer composition of the present invention has excellent temperature and salt resistance. When used, the permeabilizer composition can be mixed with water, which can be salt-containing or salt-free water.

[0071] The present invention does not have any special requirements for the preparation method of the permeabilizer; generally, the permeabilizer composition is simply mixed with water.

[0072] In this invention, there is no particular limitation on the way the permeabilizer composition is mixed with water. For example, the aminocarboxylate alkyl alcohol ether monoester and the auxiliary agent can be mixed first and then mixed with water to form the permeabilizer; or, the aminocarboxylate alkyl alcohol ether monoester and water can be mixed separately to obtain a solution, the auxiliary agent and water can be mixed separately to obtain a solution, and then the two solutions can be mixed to obtain the permeabilizer.

[0073] The sixth aspect of this invention provides an application of the permeabilizer described herein in oil reservoir development.

[0074] The permeabilizer composition of the present invention has excellent temperature and salt resistance. When used in oil reservoir development, the permeabilizer can be used in mines and oil fields with a water salinity of 0-25wt%, and further, the calcium and magnesium ion concentration is 0-2000mg / L.

[0075] The permeabilizer described in this invention has improved temperature resistance to 120℃, salt resistance to 250,000 mg / L, and calcium and magnesium ion resistance to 2,000 mg / L, while also exhibiting superior wetting and alteration properties.

[0076] To further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, and not for limiting the scope of the claims of the present invention.

[0077] In the following examples, unless otherwise specified, R in formula (1) is a straight-chain alkyl group.

[0078] The testing methods, testing standards, and equipment used in this invention are as follows:

[0079] (1) Method for determining the interfacial tension of oil and water: The TX-500C rotating drop interfacial tension meter from the United States was used for the determination.

[0080] (2) Spontaneous Immersion Experiment: The oil recovery rate was obtained by conducting a spontaneous immersion experiment on aged cores in Amott Cell at reservoir temperature using concentrated brine or immersion agent solution. The preparation of aged cores was as follows: the dried cores were first vacuumed, and then concentrated brine was injected, at which point the cores were 100% brine saturated; the saturated cores were then centrifuged to saturate with crude oil (10,000 rpm, 48 h), and the brine scale was read to obtain the crude oil saturation of the cores; then the crude oil saturated cores were aged at reservoir temperature for two weeks to finally obtain aged cores.

[0081] Preparation Example 1

[0082] (1) In the presence of the catalyst p-toluenesulfonic acid, N,N-bis(carboxymethyl)-L-glutamic acid and tridecyl alcohol polyoxyethylene (5EO) polyoxypropylene ether (5PO) reacted at 140°C for 1 hour in a molar ratio of 1:1. The mass of the catalyst was 0.5% of the mass of the alkyl alcohol polyoxyethylene polyoxypropylene ether, and the solvent was n-hexane, with a solvent volume equal to the volume of the raw material. The reaction yielded an aminocarboxylic acid alkyl alcohol ether monoester.

[0083] (2) The aminocarboxylic acid alkyl alcohol ether monoester reacts with sodium hydroxide. After the reaction is completed, the mixture is cooled to 70°C and washed with saturated sodium carbonate solution until no bubbles are generated. The mixture is centrifuged to separate the layers and remove the water layer. The resulting oily product is distilled under reduced pressure to remove impurities and obtain the final product (in formula (1), M is Na; m = 5; n = 5; R = C13 alkyl).

[0084] Preparation Example 2

[0085] (1) In the presence of the catalyst p-toluenesulfonic acid, N,N-bis(carboxymethyl)-L-glutamic acid and octadecyl alcohol polyoxyethylene (20EO) reacted at 140°C for 1 hour in a molar ratio of 1:1. The mass of the catalyst was 0.5% of the mass of alkyl alcohol polyoxyethylene polyoxypropylene ether, and the solvent was n-hexane with a volume equal to the volume of the raw material. The reaction yielded an aminocarboxylic acid alkyl alcohol ether monoester.

[0086] (2) The aminocarboxylic acid alkyl alcohol ether monoester reacts with sodium hydroxide. After the reaction is completed, the mixture is cooled to 70°C and washed with saturated sodium carbonate solution until no bubbles are generated. The mixture is centrifuged to separate the layers and remove the water layer. The resulting oily product is distilled under reduced pressure to remove impurities and obtain the final product (in formula (1), M is Na; m = 20; n = 0; R = C18 alkyl).

[0087] Preparation Example 3

[0088] (1) In the presence of the catalyst p-toluenesulfonic acid, N,N-bis(carboxymethyl)-L-glutamic acid and octyl alcohol polyoxyethylene (2EO) polyoxyethylene (15PO) reacted at 140°C for 1 hour in a molar ratio of 1:1. The mass of the catalyst was 0.5% of the mass of alkyl alcohol polyoxyethylene polyoxypropylene ether, and the solvent was n-hexane with a volume equal to the volume of the raw material. The reaction yielded an aminocarboxylic acid alkyl alcohol ether monoester.

[0089] (2) The aminocarboxylic acid alkyl alcohol ether monoester reacts with sodium hydroxide. After the reaction is completed, the mixture is cooled to 70°C and washed with saturated sodium carbonate solution until no bubbles are generated. The mixture is centrifuged to separate the layers and remove the water layer. The resulting oily product is distilled under reduced pressure to remove impurities and obtain the final product (in formula (1), M is Na; m = 2; n = 15; R = C8 alkyl).

[0090] Example 1

[0091] The aminocarboxylic acid alkyl alcohol ether monoester (in formula (1), M is Na; m = 5; n = 5; R = 13) obtained in Example 1 was dissolved in a deionized aqueous solution at 20°C to obtain an absorbent with a mass concentration of 0.1 wt%.

[0092] The obtained permeating agent was subjected to oil-water interfacial tension testing. The crude oil used for oil-water interfacial tension testing was crude oil from Jiangsu Oilfield. The test results are shown in Table 1.

[0093] Example 2

[0094] The aminocarboxylate alkyl alcohol ether monoester obtained in Preparation Example 1 (in Formula (1), M is Na; m = 5; n = 5; R = 13 alkyl) was mixed with sodium polyacrylate (MW = 1200) at a mass ratio of 1:0.01 to obtain an absorbent composition, which was then dissolved in a deionized aqueous solution at 20°C to obtain an absorbent composition with a mass concentration of 0.1 wt%.

[0095] The obtained permeating agent was subjected to oil-water interfacial tension testing. The crude oil used for oil-water interfacial tension testing was crude oil from Jiangsu Oilfield. The test results are shown in Table 1.

[0096] Example 3

[0097] The implementation process is the same as in Example 2, except that the mass ratio of aminocarboxylate alkyl alcohol ether monoester to sodium polyacrylate is 1:0.1.

[0098] Example 4

[0099] The implementation process is the same as in Example 2, except that the mass ratio of aminocarboxylate alkyl alcohol ether monoester to sodium polyacrylate is 1:0.2.

[0100] Example 5

[0101] The aminocarboxylic acid alkyl alcohol ether monoester obtained in Preparation Example 2 (in Formula (1), M is Na; m = 20; n = 0; R = C18 alkyl) was mixed with N,N-bis(carboxymethyl)-L-glutamic acid tetrasodium salt at a mass ratio of 1:0.05 to obtain an absorbent composition, which was then dissolved in a deionized aqueous solution at 20°C to obtain an absorbent composition with a mass concentration of 0.3 wt%.

[0102] Example 6

[0103] The aminocarboxylic acid alkyl alcohol ether monoester (in formula (1), M is Na; m = 2; n = 15; R = C8 alkyl) obtained in Preparation Example 3 was mixed with sodium gluconate at a mass ratio of 1:0.2 to obtain an absorbent composition, which was then dissolved in a deionized aqueous solution at 20°C to obtain an absorbent composition with a mass concentration of 0.05 wt%.

[0104] Example 7

[0105] The implementation process is the same as in Example 2, except that sodium polyacrylate (MW=1200) is replaced with tetrasodium N,N-bis(carboxymethyl)-L-glutamic acid.

[0106] Example 8

[0107] The implementation process is the same as in Example 2, except that sodium polyacrylate (MW=1200) is replaced with sodium gluconate.

[0108] Comparative Example 1

[0109] The implementation process is the same as in Example 1, except that the aminocarboxylate alkyl alcohol ether monoester is replaced with the surfactant sodium tridecyl alcohol polyether carboxylate (5EO+5PO).

[0110] Comparative Example 2

[0111] The implementation process is the same as in Example 2, except that the aminocarboxylate alkyl alcohol ether monoester is replaced with sodium tridecyl alcohol polyether carboxylate (5EO+5PO).

[0112] Table 1

[0113]

[0114]

[0115] The above results indicate that multi-headed aminocarboxylate alkyl alcohol ether monoesters exhibit lower surface tension and interfacial tension than monoheaded tridecyl alcohol polyether sodium carboxylate. The percolator described in this invention also exhibits lower surface tension and interfacial tension.

[0116] Wetting angle and absorption rate related tests

[0117] Aged core slices were placed in the aforementioned permeabilizer sample and soaked for one hour. After removal and surface drying, distilled water was dropped onto the slice surface using the sitting drop method, and the wetting angle was measured. Aged core slices were then placed in Amott Cells, and the aforementioned permeabilizer sample was added; the permeation rate was measured. Simultaneously, the wetting angle and permeation rate of untreated aged core slices and distilled water were measured. The measurement results are shown in Table 2.

[0118] Table 2

[0119] serial number Wetting angle ° Permeation rate % Example 1 42.5 19.4 Example 2 42.9 30.4 Example 3 43.5 32.8 Example 4 41.2 34.5 Example 5 31.7 33.2 Example 6 45.3 42.5 Example 7 38.4 31.7 Example 8 45.8 29.8 Comparative Example 1 89.4 9.9 Comparative Example 2 76.4 12.4 distilled water 140.0 0.1 Aging core slices 140.5 /

[0120] The above results indicate that polyhead aminocarboxylate alkyl alcohol ether monoesters possess excellent wetting modification capabilities, changing the wetting angle from 140° (oil-wet) to 42.5° (water-wet). Simultaneously, polyhead aminocarboxylate alkyl alcohol ether monoesters exhibit excellent permeation efficiency, which is further improved upon the addition of additives.

[0121] Performance testing of permeabilizer in high temperature and high salt solutions

[0122] The above-mentioned permeabilizer composition was dissolved in a 10% NaCl + 2% CaCl2 aqueous solution at 120°C to obtain a permeabilizer solution with a mass concentration of 0.1 wt%. The solution properties were observed and compared with those of the solution at 20°C. The results are shown in Table 3.

[0123] Table 3

[0124] serial number 20℃ 120℃ Example 1 clear A small amount of precipitate was found. Example 2 clear clear Example 3 clear clear Example 4 clear A small amount of precipitate was found. Example 5 clear clear Example 6 clear clear Example 7 clear clear Example 8 clear A small amount of precipitate was found. Comparative Example 1 clear turbid Comparative Example 2 clear turbid

[0125] The above results show that, under certain mixing ratios, the permeabilizer can remain clear under high temperature and high salinity conditions, proving that the permeabilizer has excellent injection performance and will not cause formation pore blockage.

[0126] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. An aminocarboxylate alkyl alcohol ether monoester, characterized in that, The structural formula is shown in equation (1): Where m is 2-30; n is 0-30; R is selected from C4-C22 alkyl groups; M is selected from cations or cationic groups that make the molecule shown in formula (1) electrically neutral.

2. The aminocarboxylate alkyl alcohol ether monoester according to claim 1, wherein, m is 2-25, preferably 2-20; and / or n is 0-15; and / or R is selected from C8-C18 alkyl groups; alkyl refers to straight-chain alkyl or branched alkyl; and / or M is selected from any one of alkali metals, alkaline earth metals, or ammonium ions, preferably Na, K, Mg, Ca, or NH4. + Any one of them.

3. The method for preparing the aminocarboxylate alkyl alcohol ether monoester according to claim 1 or 2, characterized in that, Includes the following steps: (1) In the presence of a catalyst, N,N-bis(carboxymethyl)-L-glutamic acid is first contacted with the alkyl alcohol polyoxyethylene polyoxypropylene ether shown in formula (2) to obtain an aminocarboxylic acid alkyl alcohol ether monoester. In formula (2), m is 2-330; n is 0-30; R is selected from C4-C22 alkyl groups, where alkyl refers to straight-chain alkyl or branched alkyl; (2) The aminocarboxylic acid alkyl alcohol ether monoester is subjected to a second contact with an M-containing basic compound to obtain the aminocarboxylic acid alkyl alcohol ether monoester.

4. The preparation method according to claim 3, wherein, In step (1), m is 2-25, preferably 2-20; and / or n is 0-15; and / or R is selected from C8-C18 alkyl groups; and / or The catalyst is selected from one or more of p-toluenesulfonic acid, concentrated sulfuric acid, aminosulfonic acid, potassium hydrogen sulfate, titanium chloride, tin chloride, and ferric chloride; and / or The amount of catalyst added is 0.2%-1% of the mass of alkyl alcohol polyoxyethylene polyoxypropylene ether; and / or The initial contact conditions include: a temperature of 110-150℃ and a contact time of 0.5-4 hours. Preferably, the first contact is carried out in the presence of a solvent selected from one or more of n-hexane, benzene, and ethanol; and / or The solvent volume is 1-1.5 times the total volume of N,N-bis(carboxymethyl)-L-glutamic acid and alkyl alcohol polyoxyethylene polyoxypropylene ether; and / or The alkyl alcohol polyoxyethylene polyoxypropylene ether is one or more of tridecyl alcohol polyoxyethylene (5EO) polyoxypropylene ether (5PO), octadecyl alcohol polyoxyethylene (20EO), and octyl alcohol polyoxyethylene (2EO) polyoxyethylene (15PO), preferably octyl alcohol polyoxyethylene (2EO) polyoxyethylene (15PO).

5. The use of the aminocarboxylate alkyl alcohol ether monoester of claim 1 or 2 as a surfactant.

6. A permeabilizing agent composition, characterized in that, The composition comprises the aminocarboxylate alkyl alcohol ether monoester of claim 1 or 2 and an auxiliary agent selected from carboxylate salts.

7. The permeabilizing composition according to claim 6, wherein, The mass ratio of the aminocarboxylate alkyl alcohol ether monoester to the auxiliaries is 1:0.001-10, preferably 1:0.01-0.2; and / or The additive is selected from one or more of N,N-bis(carboxymethyl)-L-glutamic acid tetrasodium salt, sodium aspartate, sodium polyacrylate and sodium gluconate, preferably N,N-bis(carboxymethyl)-L-glutamic acid tetrasodium salt.

8. An absorbent, characterized in that, The permeabilizer comprises the permeabilizer composition of claim 6 or 7 and water.

9. The permeabilizer according to claim 8, wherein, The permeabilizer composition has a mass concentration of not more than 10%; preferably, the mass concentration of the permeabilizer composition is not more than 1%; more preferably, the mass concentration of the permeabilizer composition is 0.05%-0.3%.

10. The use of the permeabilizer composition of claim 6 or 7 or the permeabilizer of claim 8 or 9 in oil reservoir development.

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