Alkyl polyether oxidized salicylanilide, preparation method of alkyl polyether oxidized salicylanilide, imbibition agent composition, oil displacement agent and application of oil displacement agent

Abstract

The invention discloses alkyl polyether oxidized salicylanilide, a preparation method of the alkyl polyether oxidized salicylanilide, an imbibition agent composition, an oil-displacing agent and application of the oil-displacing agent. The structural formula of the alkyl polyether oxidized salicylanilide is shown in the formula (I). In the formula (I), R is a polyether group. The alkyl polyether oxidized salicylanilide disclosed by the invention is used as an imbibition agent component and has super-strong interface wetting change performance. By using the alkyl polyether oxidized salicylanilide, the imbibition efficiency in oil reservoirs, especially in the field of oil displacement recovery of low-permeability, ultra-low-permeability, ultra-low-permeability and unconventional tight oil reservoirs, is improved, so that the recovery efficiency of the oil reservoirs is improved, and the alkyl polyether oxidized salicylanilide has extremely high economic value. The imbibition agent adopting the alkyl polyether oxidized salicylanilide disclosed by the invention has good high temperature resistance and high salt resistance.

Description

Technical Field

[0001] This invention relates to an alkyl polyether oxidized salicylaniline, its preparation method, its permeation agent composition, its oil displacement agent, and their applications. Background Technology

[0002] Surfactants are substances that spontaneously adsorb onto the interface between two phases in solution, significantly reducing interfacial tension. Surfactants possess a range of physicochemical functions, including dissolution, emulsification, and wetting, and are often used in fracturing fluids in the oil extraction field.

[0003] Currently, sodium-based anionic surfactants are widely used. These surfactants have high interfacial activity and low adsorption in formations, but they also suffer from poor salt tolerance. Compound surfactants, through self-assembly regulation, avoid the problems of liquid crystal formation and precipitation that easily occur when multiple surfactants are mixed. Furthermore, their tight interfacial arrangement gives them extremely high surface activity, making them promising for oil displacement in conventional reservoirs. However, the inherent limitations of conventional quaternary ammonium cationic surfactants significantly restrict the further application of compound surfactants.

[0004] Furthermore, ultra-low permeability and tight reservoirs have small porosity and low permeability, resulting in significant losses of surfactants during migration due to adsorption, retention, and precipitation, which greatly reduces migration distance and oil displacement efficiency. Therefore, developing a spontaneous adsorption oil displacement agent with high recovery rate, high temperature resistance, and high salinity resistance in ultra-low permeability reservoirs is of great significance for improving the recovery rate of ultra-low permeability and tight reservoirs. Summary of the Invention

[0005] To address the aforementioned problems in the existing technology, this invention provides an alkyl polyether oxidized salicylaniline, its preparation method, a percolator composition, an oil displacement agent, and their applications. The alkyl polyether oxidized salicylaniline can form a percolator composition with anionic surfactants, solvent oils, etc., exhibiting spontaneous percolation and oil displacement effects, and possesses superior interfacial wetting modification properties.

[0006] To achieve the above objectives, the first aspect of the present invention provides an alkyl polyether oxidized salicylaniline, the alkyl polyether oxidized salicylaniline having the structural formula shown in formula (I);

[0007]

[0008] In formula (Ⅰ), R is a polyether group.

[0009] A second aspect of this invention provides a method for preparing alkyl polyether oxidized salicylaniline, the method comprising:

[0010] (1) In the presence of a first catalyst, salicylaniline is first contacted with an unsaturated hydroxyl-terminated alkyl polyether to obtain alkyl polyether salicylaniline; the unsaturated hydroxyl-terminated alkyl polyether has the structural formula shown in formula (II), where R' is a polyether group.

[0011]

[0012] (2) In the presence of a second catalyst, alkyl polyether salicylaniline is subjected to a second contact with an oxidant to obtain alkyl polyether oxidized salicylaniline.

[0013] A third aspect of the present invention provides an absorbent composition comprising at least one of the alkyl polyether oxidized salicylaniline described in the present invention.

[0014] A fourth aspect of the present invention provides an oil displacement agent comprising: the permeabilizing composition described in the present invention and water.

[0015] The fifth aspect of the present invention provides the application of alkyl polyether oxidized salicylaniline and / or the alkyl polyether oxidized salicylaniline prepared by the preparation method of the present invention, and / or the permeabilizing agent composition and / or the oil displacement agent of the present invention in oil reservoir development.

[0016] The alkyl polyether oxidized salicylaniline of the present invention is used as a permeabilizing agent and has excellent interfacial wetting and alteration properties.

[0017] The use of alkyl polyether oxidized salicylaniline of the present invention improves the percolation efficiency in oil reservoirs, especially in low-permeability, ultra-low-permeability, extra-low-permeability, and unconventional tight oil reservoirs, thereby improving reservoir recovery efficiency and having extremely high economic value. The percolator using alkyl polyether oxidized salicylaniline of the present invention exhibits good high-temperature resistance (up to 150°C) and excellent salt resistance, showing promising application prospects. Detailed Implementation

[0018] 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.

[0019] The specific embodiments of the present invention will be described in detail below. However, it should be noted that the scope of protection of the present invention is not limited to these specific embodiments, but is determined by the claims in the appendix.

[0020] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0021] When this specification uses the prefixes "known to those skilled in the art," "prior art," or similar terms to derive materials, substances, methods, steps, apparatus, or components, the objects derived from such prefixes cover those conventionally used in the art at the time the invention was proposed, but also include those that are not currently commonly used but will become generally recognized in the art as suitable for similar purposes.

[0022] It should be noted that the two or more aspects (or embodiments) disclosed in the context of this specification can be arbitrarily combined with each other, and the resulting technical solutions (such as methods or systems) are part of the original disclosure of this specification and also fall within the protection scope of this invention.

[0023] The present invention provides an alkyl polyether oxidized salicylaniline, the structural formula of which is shown in formula (I);

[0024]

[0025] In formula (Ⅰ), R is a polyether group.

[0026] The alkyl polyether oxidized salicylaniline described in this invention is used as a permeabilizer component and exhibits superior interfacial wetting modification properties. Permeabilizer compositions prepared using the alkyl polyether oxidized salicylaniline described in this invention possess excellent high-temperature resistance and superior salt resistance, improving permeabilization efficiency in oil reservoirs, particularly in low-permeability, ultra-low-permeability, extra-low-permeability, and unconventional tight oil reservoirs, thereby enhancing oil recovery efficiency and demonstrating promising application prospects.

[0027] In this invention, the range of n in formula (I) is relatively wide. As long as the purpose of this invention can be achieved, any suitable value of n can be selected. According to a preferred embodiment of this invention, the value of n in formula (I) is 8-18, for example, 9, 10, 11, 12, 13, 14, 15, 16, 17.

[0028] In this invention, the polyether group R includes one or more of the following structural units;

[0029]

[0030] In the polyether group R, a, b, and c are each 0-50, preferably 2-20, more preferably 6-10, and a, b, and c are not all 0 simultaneously. According to a preferred embodiment of the present invention, in the preferred formula (Ⅰ) of the alkyl polyether oxidized salicylaniline, n is 13, and R is... a is 7; or n is 13, R is... a is 5; or n is 13, R is... c is 7; or n is 13, R is... a is 14; or n is 13, R is... c is 14; or n is 13, R is... a is 7, b is 5; or n is 8, R is a is 7; or one or more of the following; more preferably n is 13, R is a is 7; or n is 13, R is... a is 5; or n is 13, R is... a is 14; or n is 13, R is... c is 14; or n is 13, R is... a is 7, b is 5; or n is 8, R is a is 7; or one or more of the following; more preferably n is 13, R is... a is 7.

[0031] This invention provides a method for preparing alkyl polyether oxidized salicylaniline, the method comprising:

[0032] (1) In the presence of a first catalyst, salicylaniline is first contacted with an unsaturated hydroxyl-terminated alkyl polyether to obtain alkyl polyether salicylaniline; the unsaturated hydroxyl-terminated alkyl polyether has the structural formula shown in formula (II), where R' is a polyether group.

[0033]

[0034] (2) In the presence of a second catalyst, alkyl polyether salicylaniline is subjected to a second contact with an oxidant to obtain alkyl polyether oxidized salicylaniline.

[0035] In this invention, the structural formula of salicylaniline is as follows:

[0036]

[0037] Using the preparation method described in this invention, the alkyl polyether oxidized salicylaniline obtained can be formulated into a permeabilizing agent composition. This permeabilizing agent composition has good high temperature resistance and excellent salt resistance, which improves the permeabilization efficiency in oil reservoirs, especially in the field of low-permeability, ultra-low-permeability, extra-low-permeability, and unconventional tight oil reservoirs, thereby improving oil recovery efficiency and showing good application prospects.

[0038] According to a preferred embodiment of the present invention, in the unsaturated hydroxyl-terminated alkyl polyether of preferred formula (II), n is 13 and R' is... d is 7; or n is 13, R' is The value is 5; or n is 13, and R' is... f is 7; or n is 13, R' is... d is 14; or n is 13, R' is f is 14; or n is 13, R' is... d is 7, e is 5 and n is 8, R' is d is 7; or one or more of the following; more preferably n is 13, R' is d is 7; or n is 13, R' is The value is 5; or n is 13, and R' is... d is 14; or n is 13, R' is f is 14; or n is 13, R' is... d is 7, e is 5 and n is 8, R' is d is 7; or one or more of the following; more preferably n is 13, R' is d is 7.

[0039] In this invention, the range of n in formula (ⅠI) is relatively wide. As long as the purpose of this invention can be achieved, any suitable value of n can be selected. According to a preferred embodiment of this invention, the value of n in formula (Ⅰ) is 8-18, for example, 9, 10, 11, 12, 13, 14, 15, 16, 17.

[0040] In step (1) of this invention, R' includes one or more of the following structural units;

[0041]

[0042] In R', d, e and f are each 0-50, preferably 2-20, more preferably 6-10, and d, e and f are not all 0 at the same time.

[0043] In step (1) of this invention, the molar ratio of the total amount of salicylaniline to the total amount of unsaturated hydroxyl-terminated alkyl polyether can be selected within a wide range. The following is an illustrative example, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the molar ratio of the total amount of salicylaniline to the total amount of unsaturated hydroxyl-terminated alkyl polyether is 1:(1-1.06), for example, 1:1.01, 1:1.02, 1:1.03, 1:1.04, or 1:1.05.

[0044] In step (1) of the present invention, the first catalyst can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the present invention. According to a preferred embodiment of the present invention, the first catalyst is selected from platinum-based catalysts.

[0045] According to the present invention and in conjunction with the prior art, it can be understood that the platinum-based catalyst includes, for example, platinum salts, metallic platinum, platinum nanoparticles, and platinum metal alloys.

[0046] In step (1) of the present invention, the amount of the first catalyst can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the present invention. According to a preferred embodiment of the present invention, the amount of the first catalyst, based on platinum, is 0.001wt%-1wt% of the total amount of salicylaniline and unsaturated terminal hydroxyl alkyl polyether, for example, 0.005wt%, 0.080wt%, 0.100wt%, 0.500wt%, 0.600wt%, 0.800wt%, and 0.900wt%.

[0047] In step (1) of the present invention, the conditions for the first contact are not particularly limited. As long as the purpose of the present invention can be achieved, any suitable conditions for the first contact can be selected. According to a preferred embodiment of the present invention, the conditions for the first contact include: a temperature of 80-100°C. In the embodiment, 100°C is used as an example to illustrate the advantages of the present invention, but this does not limit the scope of the present invention.

[0048] In step (1) of this invention, the pressure conditions of the first contact are not particularly limited, as long as they can achieve the purpose of this invention. This is an illustrative example, but does not limit the scope of this invention. For example, the pressure is 0-5 MPa. In the examples, experiments are conducted under normal pressure to illustrate the advantages of this invention, but does not limit the scope of this invention.

[0049] In step (1) of the present invention, the time condition of the first contact is not particularly limited, as long as it can achieve the purpose of the present invention. This is an illustrative example, but does not limit the scope of the present invention. For example, the time is 4-6 hours. In the embodiment, 4 hours is used as an illustrative example to illustrate the advantages of the present invention, but does not limit the scope of the present invention.

[0050] In step (2) of the present invention, the oxidant is not specifically limited. Any suitable oxidant can be selected as long as it can achieve the purpose of the present invention. According to a preferred embodiment of the present invention, the oxidant is selected from one or more of hydrogen peroxide, peroxyacetone, and peroxybenzoyl.

[0051] In step (2) of this invention, the amount of oxidant can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the molar ratio of the total amount of alkyl polyether salicylaniline to the oxidant is 1:(0.8-2), for example, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, or 1.9.

[0052] In step (2) of the present invention, there is no special limitation on the type of the second catalyst. Any suitable second catalyst can be selected as long as it can achieve the purpose of the present invention. According to a preferred embodiment of the present invention, the second catalyst is selected from at least one of citric acid and disodium EDTA.

[0053] In step (2) of the present invention, the amount of the second catalyst can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the present invention. According to a preferred embodiment of the present invention, the weight ratio of the amount of the second catalyst to the amount of polyether salicylaniline is (0.1 to 0.5):1, for example, 0.2:1, 0.3:1, or 0.4:1.

[0054] In step (2) of this invention, the conditions for the second contact are not particularly limited. Any suitable conditions for the second contact can be selected as long as they can achieve the purpose of this invention. According to a preferred embodiment of this invention, the conditions for the second contact include a temperature of 50-80°C. In this embodiment, 50°C is used as an example to illustrate the advantages of this invention, but this does not limit the scope of this invention.

[0055] In step (2) of this invention, the pressure conditions of the second contact are not particularly limited, as long as they can achieve the purpose of this invention. This is an illustrative example, but does not limit the scope of this invention. For example, the pressure is 0-5 MPa. In the example, the experiment was conducted at 1 MPa to illustrate the advantages of this invention, but does not limit the scope of this invention.

[0056] In step (2) of this invention, the time condition for the second contact is not particularly limited, as long as it can achieve the purpose of this invention. This is an illustrative example, but it does not limit the scope of this invention. For example, the time is 1-2 hours. In the embodiment, 1 hour is used as an illustrative example to illustrate the advantages of this invention, but it does not limit the scope of this invention.

[0057] The present invention provides an adsorbent composition comprising at least one of the alkyl polyether oxidized salicylaniline described in the present invention.

[0058] According to a preferred embodiment of the present invention, the composition comprises the alkyl polyether oxidized salicylaniline, an anionic surfactant, and a solvent oil.

[0059] The permeabilizer composition of this invention has good high temperature resistance and excellent salt resistance. The use of this permeabilizer composition improves the permeabilization efficiency in oil reservoirs, especially in the field of low-permeability, ultra-low-permeability, extra-low-permeability, and unconventional tight oil reservoirs, thereby improving oil recovery efficiency and showing good application prospects.

[0060] In this invention, the anionic surfactant is not specifically limited. Any suitable anionic surfactant can be selected as long as it can achieve the purpose of this invention. According to a preferred embodiment of this invention, the anionic surfactant is selected from fatty alcohol anionic surfactants, preferably one or more of fatty alcohol polyoxyethylene ether carboxylates, fatty alcohol polyoxypropylene ether carboxylates, fatty alcohol polyoxyethylene ether sulfonates, and fatty alcohol polyoxypropylene ether sulfonates, and preferably sodium tridecyl alcohol polyoxyethylene ether (7EO) carboxylate.

[0061] In this invention, the solvent oil is not specifically limited. Any suitable solvent oil can be selected as long as it can achieve the purpose of this invention. According to a preferred embodiment of this invention, the solvent oil is selected from one or more of C6-C14 alkanes (e.g., dodecane), xylene, and white oil, preferably dodecane.

[0062] In this invention, the molar ratio of the alkyl polyether oxidized salicylaniline to the anionic surfactant can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the molar ratio of the alkyl polyether oxidized salicylaniline to the anionic surfactant is 1:(0.01-100), preferably 1:(0.1-10), and more preferably 1:1-3.

[0063] In this invention, the mass ratio of the sum of the anionic surfactant and the alkyl polyether oxidized salicylaniline to the solvent oil can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of this invention. According to a preferred embodiment of this invention, the mass ratio of the sum of the anionic surfactant and the alkyl polyether oxidized salicylaniline to the solvent oil is 1:(0.01-50); preferably 1:(0.8-20), more preferably 1:1-10, and more preferably 1:1-3.

[0064] The present invention provides an oil displacement agent comprising: the permeabilizing composition described in the present invention and water.

[0065] The oil displacement agent described in this invention has good high-temperature resistance and excellent salt resistance. The use of this oil displacement agent improves the permeation efficiency in oil reservoirs, especially in the field of low-permeability, ultra-low-permeability, extra-low-permeability, and unconventional tight oil reservoirs, thereby improving the oil recovery efficiency and showing good application prospects.

[0066] In this invention, the mass ratio of the permeabilizer composition to water in the oil displacement agent can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the mass ratio of the permeabilizer composition to water in the oil displacement agent is not greater than 1:10, preferably not greater than 1:100, and more preferably (0.05-0.3):100. In the examples, 0.1:100 is used as an example to illustrate the advantages of the invention.

[0067] According to the present invention, it is understood that the mineralization degree of water refers to the content of soluble salts in an aqueous solution. For example, a sodium chloride aqueous solution with a mineralization degree of 100,000 mg / L means that the concentration of sodium chloride in the aqueous solution is 100,000 mg / L.

[0068] In this invention, the mineralization of the water can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the mineralization of the water is 0-150000 mg / L, preferably 100000 mg / L, 110000 mg / L, 120000 mg / L, 130000 mg / L, or 140000 mg / L. In the examples, a 100000 mg / L sodium chloride aqueous solution is used as an example to illustrate the advantages of the invention.

[0069] This invention provides the application of the alkyl polyether oxidized salicylaniline and / or the alkyl polyether oxidized salicylaniline prepared by the preparation method and / or the permeabilizer composition and / or the oil displacement agent in oil reservoir development.

[0070] The present invention will be described in detail below through embodiments. In the following embodiments,

[0071] 1. Raw materials

[0072] The reagents used in the embodiments of the present invention can all be obtained by commercially available materials or by preparation methods disclosed in the prior art. For example, salicylaniline, tridecyl hydroxyl-terminated polyoxyethylene ether (7EO), fatty alcohol polyoxyethylene ether, etc. are all purchased from BASF. The purchased fatty alcohol polyoxyethylene ether is then acidified according to the prior art to obtain anionic surfactants.

[0073] The crude oil used in the test was selected from Jiangsu Oilfield.

[0074] 2. Testing Method

[0075] Surface tension test: The surface tension was measured using the hanging plate method at 20°C using a German Kruss K100.

[0076] Interfacial tension test: The test was conducted using a TX-500C rotating drop interfacial tension meter from the USA at a speed of 5000 rpm, at the corresponding reservoir temperature (120℃) and corresponding brine salinity.

[0077] Wetting angle test: The test was conducted at room temperature using a German Kruss DSA100 instrument. The test procedure included:

[0078] The aged core slices were soaked in the experimentally prepared oil displacement agent for 1 hour and then dried. Distilled water was then dropped onto the slice surface using the sitting drop method, and the wetting angle was measured.

[0079] Spontaneous absorption test:

[0080] A) Preparation of aged rock cores: First, the dried rock cores are vacuumed and then injected with concentrated brine, at which point the rock cores are 100% brine saturated; the saturated rock cores are then subjected to crude oil saturation through a centrifuge (10000 rpm, 48 h), and the brine scale is read to obtain the crude oil saturation of the rock cores; then the crude oil saturated rock cores are aged at reservoir temperature for two weeks to finally obtain aged rock cores.

[0081] B) Self-absorption test: The oil recovery rate is obtained by placing aged rock cores in Amott Cell at reservoir temperature and using concentrated brine or oil displacement agent to conduct a self-absorption test.

[0082] Example 1

[0083] Preparation of alkyl polyether oxidized salicylaniline

[0084] At a temperature of 100℃ and atmospheric pressure, in the presence of platinum catalyst, salicylaniline and unsaturated hydroxyl-terminated alkyl polyether (n=13, R'=) are reacted. (d=7) The reaction was carried out at a molar ratio of 1:1 for 4 hours, with the amount of platinum metal being 0.2 wt% of the total amount of salicylaniline and unsaturated terminal hydroxyl alkyl polyether, to obtain tridecyl polyether salicylaniline (7EO), with the following structural formula:

[0085]

[0086] At a temperature of 50℃, a pressure of 1 MPa, and in the presence of citric acid as a catalyst, hydrogen peroxide was added to tridecyl polyether salicylaniline (7EO) in a molar ratio of 1:1 to hydrogen peroxide. The reaction time was 1 hour, and the weight ratio of citric acid to polyether salicylaniline was 0.3:1. This yielded tridecyl polyether oxidized salicylaniline (7EO) with the following structural formula:

[0087]

[0088] Preparation of permeabilizing agent composition

[0089] Tridecyl polyether oxidized salicylaniline (7EO) and tridecyl alcohol polyoxyethylene ether (7EO) carboxylate sodium were mixed in a molar ratio of 1:2. Dodecane was then added in a molar ratio of 1:1 between the total mass of tridecyl polyether oxidized salicylaniline (7EO) and the mass of tridecyl alcohol polyoxyethylene ether (7EO) carboxylate sodium and dodecane to obtain a percolator composition.

[0090] Preparation of oil displacement agents

[0091] The prepared percolator composition was diluted with an aqueous sodium chloride solution with a salinity of 100,000 mg / L to a mixed solution containing 0.1 wt% total mass fraction of tridecyl polyether oxidized salicylaniline (7EO), sodium tridecyl alcohol polyoxyethylene ether (7EO) carboxylate, and dodecane to obtain the oil displacement agent.

[0092] The obtained oil displacement agent was used to treat the aged core. Then, surface tension, interfacial tension, wetting angle, and percolation rate were tested, and the morphology of the oil displacement agent at 20℃ and 150℃ was observed. The results are shown in Table 1.

[0093] Example 2

[0094] The difference from Example 1 is that the alkyl polyether oxidized salicylaniline prepared is tridecyl polyether oxidized salicylaniline (5EO).

[0095] The obtained oil displacement agent was used to treat the aged core. Then, surface tension, interfacial tension, wetting angle, and percolation rate were tested, and the morphology of the oil displacement agent at 20℃ and 150℃ was observed. The results are shown in Table 1.

[0096] Example 3

[0097] The difference from Example 1 is that the alkyl polyether oxidized salicylaniline prepared is tridecyl polyether oxidized salicylaniline (7BO).

[0098] The obtained oil displacement agent was used to treat the aged core. Then, surface tension, interfacial tension, wetting angle, and percolation rate were tested, and the morphology of the oil displacement agent at 20℃ and 150℃ was observed. The results are shown in Table 1.

[0099] Example 4

[0100] The difference from Example 1 is that the alkyl polyether oxidized salicylaniline prepared is tridecyl polyether oxidized salicylaniline (14EO).

[0101] The obtained oil displacement agent was used to treat the aged core. Then, surface tension, interfacial tension, wetting angle, and percolation rate were tested, and the morphology of the oil displacement agent at 20℃ and 150℃ was observed. The results are shown in Table 1.

[0102] Example 5

[0103] The difference from Example 1 is that the alkyl polyether oxidized salicylaniline prepared is tridecyl polyether oxidized salicylaniline (14BO).

[0104] The obtained oil displacement agent was used to treat the aged core. Then, surface tension, interfacial tension, wetting angle, and percolation rate were tested, and the morphology of the oil displacement agent at 20℃ and 150℃ was observed. The results are shown in Table 1.

[0105] Example 6

[0106] The difference from Example 1 is that tridecyl polyether oxidized salicylaniline (7EO) and tridecyl alcohol polyoxyethylene ether (7EO) sodium carboxylate are mixed in a molar ratio of 1:0.5.

[0107] The obtained oil displacement agent was used to treat the aged core. Then, surface tension, interfacial tension, wetting angle, and percolation rate were tested, and the morphology of the oil displacement agent at 20℃ and 150℃ was observed. The results are shown in Table 1.

[0108] Example 7

[0109] The difference from Example 1 is that tridecyl polyether oxidized salicylaniline (7EO) and tridecyl alcohol polyoxyethylene ether (7EO) sodium carboxylate are mixed in a molar ratio of 1:8.

[0110] The obtained oil displacement agent was used to treat the aged core. Then, surface tension, interfacial tension, wetting angle, and percolation rate were tested, and the morphology of the oil displacement agent at 20℃ and 150℃ was observed. The results are shown in Table 1.

[0111] Example 8

[0112] The difference from Example 1 is that dodecane was added at a mass ratio of 1:8 between the total mass of tridecyl polyether oxidized salicylaniline (7EO) and sodium tridecyl alcohol polyoxyethylene ether (7EO) carboxylate and dodecane to obtain a permeabilizing agent composition.

[0113] The obtained oil displacement agent was used to treat the aged core. Then, surface tension, interfacial tension, wetting angle, and percolation rate were tested, and the morphology of the oil displacement agent at 20℃ and 150℃ was observed. The results are shown in Table 1.

[0114] Example 9

[0115] The difference from Example 1 is that, dodecane was added at a mass ratio of 1:18 between the total mass of tridecyl polyether oxidized salicylaniline (7EO) and sodium tridecyl alcohol polyoxyethylene ether (7EO) carboxylate and dodecane to obtain a permeabilizing agent composition.

[0116] The obtained oil displacement agent was used to treat the aged core. Then, surface tension, interfacial tension, wetting angle, and percolation rate were tested, and the morphology of the oil displacement agent at 20℃ and 150℃ was observed. The results are shown in Table 1.

[0117] Example 10

[0118] The difference from Example 1 is that the prepared alkyl polyether oxidized salicylaniline is tridecyl polyether oxidized salicylaniline (7EO+5PO).

[0119] The obtained oil displacement agent was used to treat the aged core. Then, surface tension, interfacial tension, wetting angle, and percolation rate were tested, and the morphology of the oil displacement agent at 20℃ and 150℃ was observed. The results are shown in Table 1.

[0120] Example 11

[0121] The difference from Example 1 is that the alkyl polyether oxidized salicylaniline prepared is octyl polyether oxidized salicylaniline (7EO).

[0122] The obtained oil displacement agent was used to treat the aged core. Then, surface tension, interfacial tension, wetting angle, and percolation rate were tested, and the morphology of the oil displacement agent at 20℃ and 150℃ was observed. The results are shown in Table 1.

[0123] Example 12

[0124] The difference from Example 1 is that tridecyl polyether oxidized salicylaniline (7EO) and sodium tridecyl alcohol polyoxyethylene ether (7EO) sulfonate are mixed in a molar ratio of 1:2.

[0125] The obtained oil displacement agent was used to treat the aged core. Then, surface tension, interfacial tension, wetting angle, and percolation rate were tested, and the morphology of the oil displacement agent at 20℃ and 150℃ was observed. The results are shown in Table 1.

[0126] Example 13

[0127] The difference from Example 1 is that tridecyl polyether oxidized salicylaniline (7EO) and tridecyl alcohol polyoxypropylene ether (5PO) sodium carboxylate are mixed in a molar ratio of 1:2.

[0128] The obtained oil displacement agent was used to treat the aged core. Then, surface tension, interfacial tension, wetting angle, and percolation rate were tested, and the morphology of the oil displacement agent at 20℃ and 150℃ was observed. The results are shown in Table 1.

[0129] Example 14

[0130] The difference from Example 1 is that tridecyl polyether oxidized salicylaniline (7EO) and tridecyl alcohol polyoxyethylene propylene ether (7EO+5PO) sodium carboxylate are mixed in a molar ratio of 1:2.

[0131] The obtained oil displacement agent was used to treat the aged core. Then, surface tension, interfacial tension, wetting angle, and percolation rate were tested, and the morphology of the oil displacement agent at 20℃ and 150℃ was observed. The results are shown in Table 1.

[0132] Example 15

[0133] The difference from Example 1 is that dodecane is replaced with xylene.

[0134] The obtained oil displacement agent was used to treat the aged core. Then, surface tension, interfacial tension, wetting angle, and percolation rate were tested, and the morphology of the oil displacement agent at 20℃ and 150℃ was observed. The results are shown in Table 1.

[0135] Example 16

[0136] The difference from Example 1 is that the sodium chloride aqueous solution with a mineralization of 100,000 mg / L was replaced with water.

[0137] The obtained oil displacement agent was used to treat the aged core. Then, surface tension, interfacial tension, wetting angle, and percolation rate were tested, and the morphology of the oil displacement agent at 20℃ and 150℃ was observed. The results are shown in Table 1.

[0138] Example 17

[0139] The difference from Example 1 is that the sodium chloride aqueous solution with a mineralization of 100,000 mg / L is replaced with an aqueous solution of sodium chloride and magnesium chloride with a sodium chloride mineralization of 100,000 mg / L and a magnesium chloride mineralization of 2,000 mg / L.

[0140] The obtained oil displacement agent was used to treat the aged core. Then, surface tension, interfacial tension, wetting angle, and percolation rate were tested, and the morphology of the oil displacement agent at 20℃ and 150℃ was observed. The results are shown in Table 1.

[0141] Comparative Example 1

[0142] The difference from Example 1 is that in the oil displacement agent, alkyl polyether oxidized salicylaniline is replaced with hexadecyltrimethylammonium chloride.

[0143] The obtained oil displacement agent was used to treat the aged core. Then, surface tension, interfacial tension, wetting angle, and percolation rate were tested, and the morphology of the oil displacement agent at 20℃ and 150℃ was observed. The results are shown in Table 1.

[0144] Comparative Example 2

[0145] The difference from Example 1 is that the oil displacement agent used is distilled water.

[0146] The aged core samples were treated with distilled water. Then, surface tension, interfacial tension, wetting angle, and percolation rate were tested, and the morphology of the oil displacement agent at 20℃ and 150℃ was observed. The results are shown in Table 1.

[0147] Comparative Example 3

[0148] The difference from Example 1 is that no oil displacement agent is used.

[0149] The results of direct wetting angle testing of aged core samples are shown in Table 1.

[0150] Comparative Example 4

[0151] The difference from Example 1 is that the sodium chloride aqueous solution with a mineralization of 100,000 mg / L is replaced with an aqueous solution of sodium chloride and magnesium chloride with a sodium chloride mineralization of 100,000 mg / L and a magnesium chloride mineralization of 2,000 mg / L.

[0152] The obtained oil displacement agent was used to treat the aged core. Then, surface tension, interfacial tension, wetting angle, and percolation rate were tested, and the morphology of the oil displacement agent at 20℃ and 150℃ was observed. The results are shown in Table 1.

[0153] Table 1

[0154]

[0155]

[0156] The above results indicate that the permeabilizer composition prepared by alkyl polyether oxidized salicylaniline, sodium tridecyl alcohol polyoxyethylene ether (7EO) carboxylate and dodecane has excellent wetting modification ability, which can change the wetting angle from 150.2° (highly hydrophobic) to 22.2° (hydrophilic) and significantly improve the permeation rate.

[0157] 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 combining the 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 alkyl polyether oxidized salicylaniline, characterized in that, The structural formula of the alkyl polyether oxidized salicylaniline is shown in formula (Ⅰ); In formula (Ⅰ), R is a polyether group.

2. The alkyl polyether oxidized salicylaniline according to claim 1, wherein, In equation (Ⅰ), n is 8-18; and / or The polyether group R includes one or more of the following structural units; In the polyether group R, a, b and c are each 0-50, preferably 2-20, more preferably 6-10, and a, b and c are not all 0 at the same time; In the preferred formula (Ⅰ), n is 13 and R is a is 7; or n is 13, R is... a is 5; or n is 13, R is... c is 7; or n is 13, R is... a is 14; or n is 13, R is... c is 14; or n is 13, R is... a is 7, b is 5; or n is 8, R is a is 7; one or more of the following. More preferably, n is 13, and R is... a is 7; or n is 13, R is... a is 5; or n is 13, R is... a is 14; or n is 13, R is... c is 14; or n is 13, R is... a is 7, b is 5; or n is 8, R is a is 7; or one or more of the following; A further preferred value is n = 13, R = a is 7.

3. A method for preparing alkyl polyether oxidized salicylaniline, characterized in that, The method includes: (1) In the presence of a first catalyst, salicylaniline is first contacted with an unsaturated hydroxyl-terminated alkyl polyether to obtain alkyl polyether salicylaniline; the unsaturated hydroxyl-terminated alkyl polyether has the structural formula shown in formula (II), where R' is a polyether group. (2) In the presence of a second catalyst, alkyl polyether salicylaniline is subjected to a second contact with an oxidant to obtain alkyl polyether oxidized salicylaniline.

4. The preparation method according to claim 3, wherein, In step (1), n is 8-18; and / or R' includes one or more of the following structural units; In R', d, e and f are each 0-50, preferably 2-20, more preferably 6-10, and d, e and f are not all 0 at the same time; In the preferred formula (II), n is 13, and R' is... d is 7; or n is 13, R' is The value is 5; or n is 13, and R' is... f is 7; or n is 13, R' is... d is 14; or n is 13, R' is f is 14; or n is 13, R' is... d is 7, e is 5 and n is 8, R' is d is 7; or one or more of the following; More preferably, n is 13, and R' is... d is 7; or n is 13, R' is The value is 5; or n is 13, and R' is... d is 14; or n is 13, R' is f is 14; or n is 13, R' is... d is 7, e is 5 and n is 8, R' is d can be one or more of the seven; A further preferred value is n = 13, R' = d is 7; and / or The molar ratio of the total amount of salicylaniline to the total amount of unsaturated hydroxyl-terminated alkyl polyether is 1:(1-1.06); and / or The first catalyst is selected from at least one of platinum-based catalysts; and / or The amount of the first catalyst, calculated as platinum, is 0.001 wt% to 1 wt% of the total amount of salicylaniline and unsaturated hydroxyl-terminated alkyl polyether. and / or The conditions for the first contact include: a temperature of 80-100℃, a pressure of 0-5MPa, and a time of 4-6h.

5. The preparation method according to claim 3 or 4, wherein, In step (2), The oxidant is selected from one or more of hydrogen peroxide, peroxyacetone, and peroxybenzoyl; and / or The total amount of alkyl polyether salicylaniline used to the molar ratio of oxidant is 1:(0.8-2); and / or The second catalyst is selected from at least one of citric acid and disodium EDTA. and / or The weight ratio of the second catalyst to the polyether salicylaniline is (0.1-0.5):1; and / or The conditions for the second contact include: a temperature of 50-80℃, a pressure of 0-5MPa, and a time of 1-2h.

6. A permeabilizing agent composition, characterized in that, The permeating agent composition comprises at least one of the alkyl polyether oxidized salicylaniline as described in claim 1 or 2; Preferably, the percolator composition comprises the alkyl polyether oxidized salicylaniline, anionic surfactant, and solvent oil.

7. The permeabilizing composition according to claim 6, wherein, The anionic surfactant is selected from fatty alcohol anionic surfactants; Preferably, the anionic surfactant is selected from one or more of fatty alcohol polyoxyethylene ether carboxylates, fatty alcohol polyoxypropylene ether carboxylates, fatty alcohol polyoxyethylene ether sulfonates, and fatty alcohol polyoxypropylene ether sulfonates, and is preferably sodium tridecyl alcohol polyoxyethylene ether (7EO) carboxylate; and / or The solvent oil is selected from one or more of C6-C14 alkanes, xylene, and white oil, preferably dodecane; and / or The molar ratio of the alkyl polyether oxidized salicylaniline to the anionic surfactant is 1:(0.01-100), preferably 1:(0.1-10), more preferably 1:1-3; and / or The mass ratio of the sum of the anionic surfactant and the alkyl polyether oxidized salicylaniline to the solvent oil is 1:(0.01-50); preferably 1:(0.8-20); more preferably 1:1-10; and even more preferably 1:1-3.

8. An oil displacement agent, characterized in that, The oil displacement agent comprises: the permeabilizing composition of claim 6 or 7 and water.

9. The oil displacement agent according to claim 8, wherein, In the oil displacement agent, the mass ratio of the permeabilizing agent composition to water is not greater than 1:10; Preferably, the mass ratio of the permeabilizing agent composition to water is not greater than 1:100; More preferably, the mass ratio of the permeabilizing agent composition to water is (0.05-0.3):100; and / or The mineralization of the water is 0-150000 mg / L.

10. The application of the alkyl polyether oxidized salicylaniline as described in claim 1 or 2 and / or the alkyl polyether oxidized salicylaniline prepared by the preparation method described in any one of claims 3-5 and / or the percolator composition as described in claim 6 or 7 and / or the oil displacement agent as described in claim 8 or 9 in oil reservoir development.

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