Hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent, its preparation method and application

Abstract

This invention provides a hydrocarbon-based naphthalene-based polyether sulfonate heavy oil displacement agent, its preparation method, and its application. The hydrocarbon-based naphthalene-based polyether sulfonate heavy oil displacement agent is shown in formula (I), where R1 is C6~C6. 30 Hydrocarbon group, R2 is H or C1~C 30 Hydrocarbon groups, R3 and R4 are independently selected from H, C1 to C1. 10 hydrocarbon group, C1-C 10 hydrocarbon carbonyl group, C1-C 10 alkyl sulfonic acid group, C1~C 10 Hydroxyl alcohol sulfonic acid group or C1~C 10 Hydrocarbon group, carboxylic acid group, or -SO3(M) n ,‑(Polyoxyalkylene)2‑is‑(PO) x2 -、-(EO) y2 ‑and‑(BO) z2 One or more of the following: x1+x2=0~30, y1+y2=1~30, z1+z2=0~30, M is selected from any one of alkali metal ions and alkaline earth metal ions. When M is an alkali metal ion, n is 1; when M is an alkaline earth metal ion, n is 0.5. The hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent of this invention has high interfacial activity and can be used in oil reservoir development, especially in high-temperature and high-salinity oil reservoir development, with improved crude oil recovery.

Description

Technical Field

[0001] This invention belongs to the field of oil displacement agent technology, and particularly relates to hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent, its preparation method and application. Background Technology

[0002] The method of enhancing oil recovery by using surfactants as displacement agents is called "surfactant flooding." Surfactant flooding is a widely used, effective, and suitable method for enhancing oil recovery in tertiary oil recovery. There are many types of surfactants, mainly including anionic, cationic, nonionic, and amphoteric surfactants. Surfactants improve oil displacement efficiency by altering the interfacial tension and emulsification between the oil displacement system and the crude oil, as well as by solubilizing the crude oil. Surfactants play a crucial role in chemical flooding for enhanced oil recovery, and the development of efficient, inexpensive, temperature- and salt-resistant surfactants is of great significance for promoting the development of chemical flooding technology.

[0003] Commonly used surfactants both domestically and internationally include anionic surfactants such as petroleum sulfonates, alkylbenzene sulfonates, and olefin sulfonates. These surfactants are effective in conventional oil reservoirs with temperatures below 80℃ and salinity below 30,000 mg / L. Currently, many surfactants have been successfully applied in ordinary oil reservoirs (Class I and II reservoirs). However, over 60% of the remaining oil reserves are in demanding reservoirs that are difficult to extract, characterized by high temperature, high salinity, high water content, high clay content, low permeability, and heavy oil. The aforementioned surfactants are ineffective or even useless due to their low activity and poor salt tolerance. Summary of the Invention

[0004] To address at least one of the aforementioned problems in the prior art, the present invention provides a hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent, its preparation method, and its application. The hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent of the present invention has high surface activity and can improve the recovery rate of crude oil.

[0005] The objective of this invention is achieved through the following technical solutions.

[0006] In a first aspect, the present invention provides a hydrocarbon-based naphthalene-based polyether sulfonate heavy oil displacement agent, wherein the hydrocarbon-based naphthalene-based polyether sulfonate heavy oil displacement agent is as shown in formula (I).

[0007]

[0008] In equation (I), R1 is C6~C 30 Hydrocarbon group, R2 is H or C1~C 30 Hydrocarbon groups, R3 and R4 are independently selected from H, C1 to C1. 10 hydrocarbon groups, C1-C 10 hydrocarbon carbonyl group, C1-C 10alkyl sulfonic acid group or C1~C 10 Hydroxyl alcohol sulfonic acid group, C1~C 10 Hydrocarbon carboxylic acid group or -SO3(M) n ,-(Polyoxyalkylene)1-is-(PO) x1 -、-(EO) y1 -and-(BO) z1 -One or more of the following, -(Polyoxyalkylene)2- is -(PO x2 -、-(EO) y2 -and-(BO) z2 - One or more of the following: x1+x2=0~30, y1+y2=1~30, z1+z2=0~30, M is selected from any one of alkali metal ions and alkaline earth metal ions. When M is an alkali metal ion, n is 1, and when M is an alkaline earth metal ion, n is 0.5.

[0009] In this invention, "PO" represents the repeating unit -CH2-CH(CH3)-O-, "EO" represents the repeating unit -CH2-CH2-O-, and "BO" represents the repeating unit -CH2-CH(CH2CH3)-O-.

[0010] The heavy oil displacement agent of hydrocarbon-based naphthalene polyether sulfonate provided according to the present invention, wherein -(Polyoxyalkylene)- is -(PO). x1 -、-(EO) y1 -and-(BO) z1 When there are two or more of the following, the present invention does not have special requirements on their connection order, for example, but not limited to, preferably -(BO). z1 -(PO) x1 -(EO) y1 -、-(BO) z1 -(EO) y1 -(PO) x1 -、-(PO) x1 -(EO) y1 -(BO) z1 -、-(PO) x1 -(BO) z1 -(EO) y1 -、-(EO) y1 -(BO) z1 -(PO) x1 -、-(EO) y1 -(PO) x1 -(BO) z1 Similarly, -(Polyoxyalkylene2)- is -(PO). x2-、-(EO) y2 -and-(BO) z2 When there are two or more of the following, the present invention does not have any special requirements on their connection order, for example, but not limited to, preferably -(BO). z2 -(PO) x2 -(EO) y2 -、-(BO) z2 -(EO) y2 -(PO) x2 -、-(PO) x2 -(EO) y2 -(BO) z2 -、-(PO) x2 -(BO) z2 -(EO) y2 -、-(EO) y2 -(BO) z2 -(PO) x2 -、-(EO) y2 -(PO) x2 -(BO) z2 -

[0011] The heavy oil displacement agent of hydrocarbon-based naphthalene polyether sulfonate provided according to the present invention, wherein, in formula (I), R1 can be alkyl, alkenyl or aryl.

[0012] According to the hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent provided by the present invention, wherein, in formula (I), R1 is C8~C 16 Hydrocarbon group, preferably C8-C 12 Hydrocarbon group.

[0013] In some preferred embodiments, R1 is C8 to C 16 Alkyl; and in some preferred embodiments, R1 is C8 to C1. 12 Alkyl groups. Examples of such alkyl groups include, but are not limited to, octyl, nonyl, decyl, undecyl, and dodecyl.

[0014] According to the hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent provided by the present invention, wherein, in formula (I), R2 is H or C1~C 30 alkyl.

[0015] In some implementations, R2 is H or Cl~C 12 Alkyl; and in some embodiments, H or C1-C8 alkyl. Examples of such R2 alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl.

[0016] According to the hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent provided by the present invention, wherein, in formula (I), R3 and R4 are independently selected from H, C1 to C4. 10 Alkyl groups, C1-C 10 alkyl carbonyl, C1-C 10 alkyl sulfonic acid group, C1~C 10 Alkyl alcohol sulfonic acid group, C1-C 10 Alkyl carboxylic acid group or -SO3(M) n .

[0017] In some embodiments, in formula (I), R3 and R4 are independently selected from H, C1-C6 alkyl groups, or -SO3(M). n .

[0018] The heavy oil displacement agent of the hydrocarbon-based naphthalene polyether sulfonate provided according to the present invention includes, among the examples of R3, R4, and C1 to C6 alkyl groups, including but not limited to: methyl, ethyl, propyl, butyl, pentyl, and hexyl.

[0019] In some implementations, in formula (I), R3 and R4 are independently selected from H, -CH3, -CH2CH3, or -SO3(M). n .

[0020] The heavy oil displacement agent of hydrocarbon-based naphthalene polyether sulfonate provided by the present invention, wherein, in formula (I), x1 and y1 are not both 0, and x2 and y2 are not both 0.

[0021] In some implementations, in equation (I), z1 and z2 are zero, x1+x2 = 0 to 12, and y1+y2 = 4 to 20; in some implementations, z1 and z2 are zero, x1+x2 = 0 to 8, and y1+y2 = 4 to 12; and in some implementations, z1 and z2 are zero, x1+x2 = 0 to 4, and y1+y2 = 4 to 8.

[0022] The heavy oil displacement agent of hydrocarbon-based naphthalene polyether sulfonate provided according to the present invention, wherein in formula (I), z1 and z2 are zero, x1+x2+y1+y2=1~50, preferably 5~20, more preferably 5~15.

[0023] According to the hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent of the present invention, examples of alkali metal ions for M include, but are not limited to, lithium ions, sodium ions, and potassium ions. Similarly, examples of alkaline earth metal ions for M include, but are not limited to, beryllium ions, magnesium ions, and calcium ions.

[0024] In some preferred embodiments, M is selected from any one of sodium ions, potassium ions, calcium ions, and magnesium ions.

[0025] The heavy oil displacement agent of the present invention is a hydrocarbon-based naphthalene polyether sulfonate, wherein the present invention relates to -SO3(M) on the naphthalene ring. n and There are no special requirements for the location.

[0026] For example, -SO3(M) n It can be located at position 5, 6, 7, or 8 of the naphthalene ring; and It can be located on the naphthalene ring, different from -SO3(M). n The position is 5, 6, 7 or 8 digits.

[0027] Secondly, the present invention provides a method for preparing a hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent, wherein the preparation method includes the following steps:

[0028] S100, react the hydrocarbon naphthalene shown in formula (II) with a nitrifying agent to obtain hydrocarbon nitronaphthalene;

[0029]

[0030] In equation (II), R1 is C6~C 30 Hydrocarbon group, R2 is H or C1~C 30 hydrocarbon group;

[0031] S200: Hydrogenation treatment is performed on the hydrocarbon nitronaphthalene obtained in step S100 to obtain alkylnaphthaleneamine;

[0032] S300: React the hydrocarbon-based naphthylamine obtained in step S200 with one or more of ethylene oxide, propylene oxide and butane oxide to obtain hydrocarbon-based naphthylamine polyether.

[0033] S400: React the hydrocarbon-based naphthylamine polyether obtained in step S300 with a sulfonating agent to obtain a sulfonated product. The sulfonated product is then hydrolyzed to obtain a hydrocarbon-based naphthylamine polyether sulfonate heavy oil displacement agent.

[0034] According to the preparation method provided by the present invention, there are no special requirements for the nitrating reagent, and any known nitrating reagent in the art can be used. In some embodiments, the nitrating reagent in step S100 is at least one of nitric acid and dinitrogen pentoxide, or a mixed acid composed of at least one of nitric acid and dinitrogen pentoxide and at least one selected from concentrated sulfuric acid, glacial acetic acid, acetic anhydride and phosphorus pentoxide.

[0035] In this invention, when a mixed acid is used as the digestion reagent, the molar ratio of at least one of nitric acid and dinitrogen pentoxide to at least one selected from concentrated sulfuric acid, glacial acetic acid, acetic anhydride and phosphorus pentoxide is 2 to 6:1.

[0036] According to the preparation method provided by the present invention, in step S100, the molar ratio of the hydrocarbon naphthalene to the nitrating agent is 1:1 to 3, the reaction temperature is preferably 0 to 80°C, and the reaction time is preferably 1 to 10 hours. In some embodiments, the reaction temperature in step S100 is 20 to 60°C, and the reaction time is 1 to 3 hours.

[0037] According to the preparation method provided by the present invention, step S200 includes: reacting the hydrocarbon nitronaphthalene obtained in step S100 with hydrogen in the presence of a hydrogenation catalyst to obtain hydrocarbon nitronaphthaleneamine.

[0038] Examples of hydrogenation catalysts suitable for use in this invention include, but are not limited to, palladium on carbon catalysts and Raney nickel catalysts.

[0039] In some embodiments, the amount of the hydrogenation catalyst is 0.01% to 10% of the full weight of the hydrocarbon-nitronaphthalene, preferably 0.1% to 5%.

[0040] According to the preparation method provided by the present invention, the hydrogenation treatment in step S200 is carried out at a temperature of 20–150°C and a pressure of less than 4 MPa. In some embodiments, the hydrogenation treatment in step S200 is carried out at a temperature of 50–70°C and a pressure of 1–3 MPa.

[0041] According to the preparation method provided by the present invention, in step S300, the amounts of propylene oxide and ethylene oxide can be determined according to the target structure of the hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent.

[0042] In some embodiments, the molar ratio of propylene oxide to alkylnaphthylamine in step S300 is 0 to 30:1, the molar ratio of ethylene oxide to alkylnaphthylamine is 1 to 30:1, and the molar ratio of butane oxide to alkylnaphthylamine is 0 to 30:1.

[0043] In some embodiments, the amount of butylene oxide is zero, the molar ratio of propylene oxide to alkylnaphthylamine is 0–12:1, and the molar ratio of ethylene oxide to alkylnaphthylamine is 4–20:1; in some embodiments, the molar ratio of propylene oxide to alkylnaphthylamine is 0–8:1, and the molar ratio of ethylene oxide to alkylnaphthylamine is 4–12:1; and in some embodiments, the molar ratio of propylene oxide to alkylnaphthylamine is 0–4:1, and the molar ratio of ethylene oxide to alkylnaphthylamine is 4–8:1.

[0044] In some preferred embodiments, the amount of butylene oxide used in step S300 is zero, and the molar ratio of the total amount of propylene oxide and ethylene oxide to the alkylnaphthylamine is 1 to 50:1, preferably 5 to 20:1, and more preferably 5 to 15:1.

[0045] According to the preparation method provided by the present invention, the reaction of alkylnaphthylamine with ethylene oxide and optionally propylene oxide in step S300 is carried out in the presence of a basic catalyst.

[0046] Examples of alkaline catalysts suitable for use in this invention include, but are not limited to, alkali metals, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alkoxides, and alkali metal oxides. In some embodiments, the alkaline catalyst is selected from at least one of alkali metal hydroxides and alkaline earth metal hydroxides; and in some embodiments, the alkaline catalyst is sodium hydroxide and / or potassium hydroxide.

[0047] In some embodiments, the amount of the basic catalyst is 0.005 to 2% by weight, preferably 0.05 to 1% by weight, based on the weight of the alkylnaphthylamine.

[0048] According to the preparation method provided by the present invention, the reaction temperature in step S300 is 135–200°C and the pressure is 0–5 MPa. In some embodiments, the reaction temperature in step S300 is 140–180°C and the pressure is 0–3 MPa; and in some embodiments, the reaction temperature in step S300 is 140–160°C and the pressure is 0–0.4 MPa.

[0049] According to the preparation method provided by the present invention, step S300 further includes: after reacting the alkylnaphthylamine with ethylene oxide and optionally propylene oxide, a removal treatment is performed at a temperature of 80–110°C. In the present invention, the removal treatment can be performed under vacuum or nitrogen bubbling.

[0050] According to the preparation method provided by the present invention, the sulfonating agent in step S400 is at least one of concentrated sulfuric acid, fuming sulfuric acid, or sulfur trioxide.

[0051] According to the preparation method provided by the present invention, step S400 includes:

[0052] S401. A hydrocarbon-based naphthylamine polyether in a molar ratio of 1:1 to 5 and the sulfonating agent are reacted at a temperature of 20 to 80°C for 0.5 to 10 hours to obtain a sulfonated product.

[0053] S402. Adjust the pH value of the sulfonated product obtained in step S401 to 10-14, and hydrolyze for 0.5-5 hours to obtain a hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent.

[0054] In this invention, in step S402, an alkali can be used to adjust the pH value of the sulfonation product. In this invention, the alkali is selected from at least one of alkali metal hydroxides and alkaline earth metal hydroxides. In some specific embodiments, the alkali is sodium hydroxide and / or potassium hydroxide.

[0055] Thirdly, the present invention provides a hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent prepared by the aforementioned preparation method.

[0056] Fourthly, the present invention also provides an oil displacement composition, wherein the oil displacement composition comprises the hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent and water.

[0057] According to the oil displacement composition provided by the present invention, the weight ratio of the hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent to water is 1:(50-2000), preferably 1:(100-1000).

[0058] In this invention, a wide range of water types can be selected. The water can be deionized water or mineral-containing water. In some embodiments, the total mineral content of the mineral-containing water is 0–150,000 mg / L; and in other embodiments, it is 10,000–100,000 mg / L.

[0059] Examples of mineral-containing water suitable for use in this invention include, but are not limited to: mineralized water, oilfield injection water, formation water, seawater, rainwater, and river water.

[0060] In some specific implementation schemes, oilfield injection water is preferred for reasons such as ease of construction and water conservation. For example, the Shengli Oilfield injection water used in the embodiments of this invention has the following composition as shown in Table 1.

[0061] The oil displacement agent composition provided by the present invention may further include, in order to increase the oil displacement effect, at least one of commonly used additives in the art, such as polyacrylamide, C1-C6 small molecule alcohols, dimethyl sulfoxide (DMSO), diethanolamine and hexadecyltrimethylammonium chloride (CTAC).

[0062] All of the above-mentioned raw materials used in this invention can be prepared in-house or purchased commercially; this invention does not impose any particular limitations on them.

[0063] Fifthly, the present invention provides the application of hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent or oil displacement agent composition in oil reservoir development, especially in high-temperature and high-salinity oil reservoir development.

[0064] The present invention has the following advantages: The hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent of the present invention is a novel anionic nonionic sulfonate surfactant with the advantages of strong temperature and salt resistance, low adsorption capacity, good affinity with crude oil, and high surface activity. It can form a low interfacial tension at the oil-water interface and is used for chemical flooding enhanced oil recovery. In particular, it can be applied to high temperature and high salt reservoirs, effectively improving the recovery rate of crude oil. It has broad application prospects and practical significance. Detailed Implementation

[0065] The present invention will be further described below with reference to specific embodiments, but this does not constitute any limitation on the present invention.

[0066] Unless otherwise specified, the raw materials used in the examples and comparative examples are all disclosed in the prior art, such as those that can be directly purchased or prepared according to the preparation methods disclosed in the prior art.

[0067] Example 1

[0068] Synthesis of 1,1-octylnaphthalene-5-aminopolyoxypropylene(30)polyoxyethylene(16) ether-7-sulfonate sodium salt

[0069] a) Add 1.0 mol of 1-octylnaphthalene to a reactor equipped with a condenser and a stirrer, and add 2.1 mol of fuming nitric acid dropwise. Control the reaction temperature at 55±5℃. After the addition is complete, continue the reaction for 2 hours, let it stand and separate the liquid to obtain 1-octyl-5-nitronaphthalene.

[0070] b) Add 1-octyl-5-nitronaphthalene to a high-pressure reactor, and add 0.5% (by weight of the substrate) of 10% palladium catalyst on carbon. Seal the reactor. Purge with nitrogen five times, then purge with hydrogen five times. Raise the temperature to 60°C, begin hydrogenation, and control the system pressure at 3 MPa. React for 6 hours to obtain 1-octylnaphthalene-5-amine.

[0071] c) Add 1-octylnaphthalene-5-amine and 1% sodium hydroxide by mass to a reactor equipped with a condenser, a stirrer and a gas disperser. Heat to 85°C while passing nitrogen gas and stir for 1 hour. Turn on the vacuum system, raise the temperature to 90°C, and dehydrate under vacuum for 1 hour. Then purge the system with nitrogen gas 4 times to remove air from the system. Then adjust the system reaction temperature to 150°C and slowly introduce propylene oxide and ethylene oxide in sequence, controlling the pressure ≤0.40MPa to carry out the etherification reaction. After the reaction is completed, purge the system with nitrogen gas, cool and neutralize and dehydrate to obtain 1-octylnaphthalene-5-amine polyoxypropylene (30) polyoxyethylene (16) ether.

[0072] d) The octylnaphthalene-5-aminopolyoxypropylene (30)polyoxyethylene (16) ether synthesized in step c) was added to a reactor equipped with a condenser, a dropping device and a stirring device. 20% fuming sulfuric acid was added dropwise at a molar ratio of 1:3. The reaction temperature was controlled at 50°C. After the addition was completed, the reaction continued for 1 hour. The excess acid was removed by washing with water and extraction. Sodium hydroxide was added to the organic phase to adjust the pH to 9, and 0.75 mol of 1-octylnaphthalene-5-aminopolyoxypropylene (30)polyoxyethylene (16) ether-7-sulfonate sodium was obtained.

[0073] 2. Performance Evaluation

[0074] Preparation of oil displacement agent composition:

[0075] One part by weight of 1-octylnaphthalene-5-aminopolyoxypropylene (30)polyoxyethylene (16) ether-7-sulfonate sodium was mixed with 1000 parts by weight of Zhongyuan Oilfield injection water to obtain an oil displacement agent composition, which was used for interfacial tension evaluation and oil displacement experiments. The composition of the Zhongyuan Oilfield injection water used is shown in Table 1. For ease of comparison, the composition of the oil displacement agent composition is listed in Table 2.

[0076] Interfacial tension evaluation:

[0077] The interfacial tension between the above-mentioned oil displacement agent composition and dehydrated crude oil from Zhongyuan Oilfield was measured using a TX-500C rotating drop interfacial tensiometer manufactured by the University of Texas at 80°C and a rotation speed of 4500 rpm. The results are shown in Table 3.

[0078] Example 2

[0079] Synthesis of 1,1-dodecylnaphthalene-5-aminopolyoxyethylene(6)ether-7-sulfonate sodium salt

[0080] a) Add 1.0 mol of 1-dodecylnaphthalene to a reactor equipped with a condenser and a stirrer. Add 1.1 equivalents of 65% nitric acid and 50 g of 98% concentrated sulfuric acid dropwise at a molar ratio. Control the reaction temperature at 20°C. After the addition is complete, continue the reaction for 1 hour. Allow the mixture to stand and separate the contents to obtain 1-dodecyl-5-nitronaphthalene.

[0081] b) Add 1-dodecyl-5-nitronaphthalene to a high-pressure reactor, and add 0.5% (by weight of the substrate) of 10% palladium on carbon. Seal the reactor. Purge with nitrogen five times, then purge with hydrogen five times. Raise the temperature to 60°C, begin hydrogenation, and control the system pressure at 3 MPa. React for 6 hours to obtain 1-dodecyl-5-naphthaleneamine.

[0082] c) Add 1-dodecyl-5-naphthylamine to a reactor equipped with a condenser, a stirrer, and a gas disperser. Add sodium hydroxide at a mass ratio of 1%. Heat the reactor to 85°C while passing nitrogen gas through it, and stir for 1 hour. Turn on the vacuum system, raise the temperature to 90°C, and dehydrate under vacuum for 1 hour. Then purge the system with nitrogen gas 4 times to remove air from the system. Then adjust the reaction temperature of the system to 150°C and slowly introduce ethylene oxide. Control the pressure to ≤0.40MPa to carry out the etherification reaction. After the reaction is completed, purge the system with nitrogen gas, cool it, neutralize and dehydrate it to obtain 1-dodecylnaphthyl-5-amine polyoxyethylene (6) ether.

[0083] d) The 1-dodecylnaphthalene-5-amine polyoxyethylene (6) ether synthesized in step c) was added to a reactor equipped with a condenser, a dropping device and a stirring device. Fuming sulfuric acid of 3 equivalents of 20% was added dropwise according to the molar ratio. The reaction temperature was controlled at 50°C. After the addition was completed, the reaction continued for 1 hour. Then sodium hydroxide was added to adjust the pH to 13. The hydrolysis reaction was carried out for 2 hours to obtain 0.78 mol of 1-dodecylnaphthalene-5-amine polyoxyethylene (6) ether-7-sulfonate sodium.

[0084] 2. Performance Evaluation

[0085] The oil displacement agent composition was prepared using the method described in Example 1, and the interfacial tension was measured. For ease of comparison, the composition of the oil displacement agent composition is listed in Table 2, and the evaluation results are listed in Table 3.

[0086] Example 3

[0087] Synthesis of 1,1-dodecyl-4-octylnaphthyl-5-amine polyoxypropylene(4)polyoxyethylene(8) ether-7-sulfonate sodium salt

[0088] a) Add 1.0 mol of 1-dodecyl-4-octylnaphthalene to a reactor equipped with a condenser and a stirrer. Add 1.2 equivalents of 65% nitric acid and 0.3 equivalents of 98% concentrated sulfuric acid dropwise at a molar ratio. Control the reaction temperature at 20°C. After the addition is complete, continue the reaction for 1 hour. Allow the mixture to stand and separate the contents to obtain 1-dodecyl-4-octyl-5-nitronaphthalene.

[0089] b) 1-Dodecyl-4-octyl-5-nitronaphthalene was added to a high-pressure reactor, and 10% palladium on carbon (1.0% by weight of the substrate) was added. The reactor was then sealed. Nitrogen was purged five times, followed by hydrogen purging five times. The temperature was raised to 60°C, and hydrogen was added. The system pressure was controlled at 3 MPa, and the reaction was carried out for 6 hours to obtain 1-dodecyl-4-octylnaphthalene-5-amine.

[0090] c) Add 1-dodecyl-4-octylnaphthalene-5-amine to a reactor equipped with a condenser, a stirrer, and a gas disperser. Add sodium hydroxide at a mass ratio of 1%. While purging with nitrogen, heat to 85°C and stir for 1 hour. Turn on the vacuum system, raise the temperature to 90°C, and dehydrate under vacuum for 1 hour. Then purge with nitrogen 4 times to remove air from the system. Then adjust the reaction temperature of the system to 150°C and slowly introduce propylene oxide and ethylene oxide in sequence, controlling the pressure ≤0.40MPa for etherification reaction. After the reaction is completed, purge the system with nitrogen, cool, neutralize, and dehydrate to obtain 1-dodecyl-4-octylnaphthalene-5-amine polyoxypropylene (4) polyoxyethylene (8) ether.

[0091] d) The 1-dodecyl-4-octylnaphthalene-5-amine polyoxypropylene (4) polyoxyethylene (8) ether synthesized in step c) was added to a reactor equipped with a condenser, a dropping device and a stirring device. Fuming sulfuric acid of 4 equivalents of 50% was added dropwise according to the molar ratio. The reaction temperature was controlled at 20°C. After the addition was completed, the reaction continued for 1 hour. Then sodium hydroxide was added to adjust the pH to 13. The hydrolysis reaction was carried out for 2 hours to obtain 0.83 mol of 1-dodecyl-4-octylnaphthalene-5-amine polyoxypropylene (4) polyoxyethylene (8) ether-7-sulfonate sodium.

[0092] 2. Performance Evaluation

[0093] The oil displacement agent composition was prepared using the method described in Example 1, and the interfacial tension was measured. For ease of comparison, the composition of the oil displacement agent composition and our composition are listed in Table 2, and the evaluation results are listed in Table 3.

[0094] Example 4

[0095] Synthesis of sodium 1,1-trianediylnaphthalene-5-amine polyoxypropylene (10) polyoxyethylene ether (20)-7-sulfonate

[0096] a) Add 1.0 mol of 1-trianediylnaphthalene to a reactor equipped with a condenser and a stirrer. Add 1.1 equivalents of 65% nitric acid and 0.2 equivalents of 98% concentrated sulfuric acid dropwise at a molar ratio. Control the reaction temperature at 20°C. After the addition is complete, continue the reaction for 1 hour. Allow the mixture to stand and separate the contents to obtain 1-trianediyl-5-nitronaphthalene.

[0097] b) Add 1-triacontane-5-nitronaphthalene to a high-pressure reactor, and add 10% palladium on carbon at 5.0% of the weight of the reactant. Seal the reactor. Purge with nitrogen five times, then purge with hydrogen five times. Raise the temperature to 60°C, start adding hydrogen, control the system pressure at 3 MPa, and react for 6 hours to obtain 1-triacontane-5-amine.

[0098] c) Add 1-trianediylnaphthalene-5-amine to a reactor equipped with a condenser, a stirrer, and a gas disperser. Add sodium hydroxide at a mass ratio of 1% to the substrate. Heat to 85°C while purging with nitrogen and stir for 1 hour. Turn on the vacuum system, raise the temperature to 90°C, and dehydrate under vacuum for 1 hour. Then purge the system with nitrogen 4 times to remove air from the system. Then adjust the system reaction temperature to 150°C and slowly introduce propylene oxide and ethylene oxide sequentially, controlling the pressure to ≤0.40MPa for etherification reaction. After the reaction is completed, purge the system with nitrogen, cool, neutralize, and dehydrate to obtain 1-trianediylnaphthalene-5-amine polyoxypropylene (10) polyoxyethylene (20) ether.

[0099] d) The 1-trianediylnaphthalene-5-amine polyoxypropylene (10) polyoxyethylene (20) ether synthesized in step c) was added to a reactor equipped with a condenser, a dropper and a stirrer. 5 equivalents of 98% sulfuric acid were added dropwise at a molar ratio. The reaction temperature was controlled at 50°C. After the dropwise addition was completed, the reaction continued for 1 hour. Then, sodium hydroxide was added to adjust the pH to 13. The hydrolysis reaction was carried out for 2 hours to obtain 0.79 mol of 1-trianediylnaphthalene-5-amine polyoxypropylene (10) polyoxyethylene (20) ether-7-naphthalene sulfonate sodium.

[0100] 2. Performance Evaluation

[0101] The oil displacement agent composition was prepared using the method described in Example 1, and the interfacial tension was measured. For ease of comparison, the composition of the oil displacement agent composition is listed in Table 2, and the evaluation results are listed in Table 3.

[0102] Example 5

[0103] Using the surfactant synthesized in Example 3, oil displacement compositions were formulated according to the method in Example 1, and interfacial tension was measured. For ease of comparison, the composition of the oil displacement compositions is listed in Table 2, and the evaluation results are listed in Table 3.

[0104] Table 1 Composition of Injected Water in Zhongyuan Oilfield

[0105]

[0106] Table 2. Composition of the oil displacement agent compositions in Examples 1-5

[0107]

[0108] Table 3. Interfacial tension properties of the oil displacement agent compositions in Examples 1-5

[0109]

[0110]

[0111] Oil displacement effect test

[0112] According to the physical simulation oil displacement effect test of the composite oil displacement system in the SY / T6424-2000 composite oil displacement system performance test method, at 80℃, the length is 30cm, the diameter is 2.5cm, and the permeability is 1.5m. 2 Simulated oil displacement experiments were conducted on core samples. First, water was injected from the Zhongyuan Oilfield to a water cut of 98%. After the water drive was completed, 0.3 pv (core pore volume) of the aforementioned oil displacement agent was injected, and then water was driven to a water cut of 98% to calculate the enhanced oil recovery rate.

[0113] The oil displacement agents prepared in Examples 3 and 5 were evaluated using the above method, and the results showed that they increased the crude oil recovery rate by 7.8% and 9.7%, respectively.

[0114] Comparative Example 1

[0115] A displacement agent composition was formulated using sodium petroleum sulfonate (Shengli Refinery) as a substitute for the 1-dodecyl-4-octylnaphthalene-5-amine polyoxypropylene (4) polyoxyethylene (8) ether-7-sulfonate surfactant in Example 3, and the interfacial tension was measured. The interfacial tension between the displacement agent composition of Comparative Example 1 and the crude oil from Zhongyuan Oilfield was 0.23 mN / m.

[0116] The oil displacement effect test described above was used to measure the increase in oil recovery of the oil displacement agent composition of Comparative Example 1, which increased the oil recovery rate by 2.7%.

[0117] Therefore, the hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent of the present invention has high surface activity and can improve the recovery rate of crude oil.

[0118] Any numerical value mentioned in this invention, if there is only a two-unit interval between any minimum and any maximum value, includes all values ​​that increase by one unit each time from the minimum to the maximum value. For example, if the amount of a component, or the value of a process variable such as temperature, pressure, or time, is stated as 50-90, in this specification it means specifically listing values ​​such as 51-89, 52-88… and 69-71 and 70-71, etc. For non-integer values, it may be appropriately considered that a unit is 0.1, 0.01, 0.001, or 0.0001. These are merely some specifically specified examples. In this application, in a similar manner, all possible combinations of numerical values ​​between the listed minimum and maximum values ​​are considered to have been disclosed.

[0119] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. Hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent, wherein, The hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent is shown in formula (I). Formula (I) In equation (I), R1 is C6~C 30 Hydrocarbon group, R2 is H or C1~C 30 The hydrocarbon group, R3 and R4, are independently selected from H or -SO3(M). n ,-(Polyoxyalkylene1)-for-(PO) x1 -、-(EO) y1 -and-(BO) z1 - or more of the following, -(Polyoxyalkylene2)- is -(PO x2 -、-(EO) y2 -and-(BO) z2 - One or more of the following; x1+x2=0~30, y1+y2=1~30, z1+z2=0~30, M is selected from any one of alkali metal ions and alkaline earth metal ions. When M is an alkali metal ion, n is 1, and when M is an alkaline earth metal ion, n is 0.

5.

2. The hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent according to claim 1, characterized in that, In equation (I), R1 is C6~C 30 Hydrocarbon group; and / or R2 is H or C1~C 12 alkyl.

3. The hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent according to claim 2, characterized in that, In equation (I), R1 is C8~C 16 Alkyl groups; and / or R2 is H or a C1~C8 alkyl group.

4. The hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent according to claim 3, characterized in that, In equation (I), R1 is C8~C 12 alkyl.

5. The hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent according to any one of claims 1-4, characterized in that, z1 and z2 are zero, x1 + x2 = 0~12, y1 + y2 = 4~20; and / or z1 and z2 are zero, x1+x2+y1+y2=1~50; and / or M is selected from any one of sodium ions, potassium ions, calcium ions, and magnesium ions.

6. The hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent according to claim 5, characterized in that, z1 and z2 are zero, x1 + x2 = 0~8, y1 + y2 = 4~12; and / or z1 and z2 are zero, x1+x2+y1+y2=5~20.

7. The hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent according to claim 6, characterized in that, z1 and z2 are zero, x1 + x2 = 0~4, y1 + y2 = 4~8; and / or z1 and z2 are zero, and x1+x2+y1+y2=5~15.

8. A method for preparing a hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent, characterized in that, The preparation method includes the following steps: S100, react the hydrocarbon naphthalene shown in formula (II) with a nitrifying agent to obtain hydrocarbon nitronaphthalene; Equation (II) In equation (II), R1 is C6~C 30 Hydrocarbon group, R2 is H or C1~C 30 hydrocarbon group; S200: Hydrogenation treatment is performed on the hydrocarbon nitronaphthalene obtained in step S100 to obtain hydrocarbon naphthaleneamine; S300: React the hydrocarbon-based naphthylamine obtained in step S200 with one or more of ethylene oxide, propylene oxide and butane oxide to obtain hydrocarbon-based naphthylamine polyether. S400: React the hydrocarbon-based naphthylamine polyether obtained in step S300 with a sulfonating agent to obtain a sulfonated product. The sulfonated product is then hydrolyzed to obtain a hydrocarbon-based naphthylamine polyether sulfonate heavy oil displacement agent.

9. The preparation method according to claim 8, characterized in that, The nitrifying agent in step S100 is at least one of nitric acid and dinitrogen pentoxide, or a mixed acid composed of at least one of nitric acid and dinitrogen pentoxide and at least one selected from concentrated sulfuric acid, glacial acetic acid, acetic anhydride, and phosphorus pentoxide; and / or The hydrogenation process described in step S200 is carried out at a temperature of 20~150°C and a pressure of less than 4 MPa.

10. The preparation method according to claim 9, characterized in that, In step S100, the molar ratio of the hydrocarbon naphthalene to the nitrating agent is 1:1~3; and / or The reaction temperature in step S100 is 0~80℃, and the reaction time is 1~10 hours; and / or The hydrogenation process described in step S200 is carried out at a temperature of 50~70°C and a pressure of 1~3 MPa.

11. The preparation method according to claim 10, characterized in that, The reaction temperature in step S100 is 20~60℃, and the reaction time is 1~3 hours.

12. The preparation method according to any one of claims 8-11, characterized in that, In step S300, the molar ratio of propylene oxide to alkylnaphthylamine is 0-30:1; the molar ratio of ethylene oxide to alkylnaphthylamine is 1-30:1; the molar ratio of butane oxide to alkylnaphthylamine is 0-30:1; and / or In step S300, the amount of butylene oxide used is zero, and the molar ratio of the total amount of propylene oxide and ethylene oxide to the alkylnaphthylamine is 1~50:1; and / or The reaction temperature in step S300 is 135~200℃; the pressure is 0~5 MPa.

13. The preparation method according to claim 12, characterized in that, In step S300, the molar ratio of propylene oxide to the alkylnaphthylamine is 0~12:1; and / or The molar ratio of ethylene oxide to the hydrocarbon-based naphthylamine is 4~20:1; and / or The molar ratio of the epoxide butane to the hydrocarbon naphthylamine is 0; and / or In step S300, the amount of butylene oxide used is zero, and the molar ratio of the total amount of propylene oxide and ethylene oxide to the alkylnaphthylamine is 5~20:1; and / or The reaction temperature in step S300 is 140~180℃; the pressure is 0~3 MPa.

14. The preparation method according to claim 13, characterized in that, In step S300, the molar ratio of propylene oxide to the alkylnaphthylamine is 0~8:1; and / or The molar ratio of ethylene oxide to the hydrocarbon-based naphthylamine is 4~12:1; and / or In step S300, the amount of butylene oxide used is zero, and the molar ratio of the total amount of propylene oxide and ethylene oxide to the alkylnaphthylamine is 5~15:1; and / or The reaction temperature in step S300 is 140~160℃; the pressure is 0~0.4 MPa.

15. The preparation method according to claim 14, characterized in that, In step S300, the molar ratio of propylene oxide to the alkylnaphthylamine is 0~4:1; and / or The molar ratio of ethylene oxide to the hydrocarbon-based naphthylamine is 4~8:

1.

16. The preparation method according to any one of claims 8-11, characterized in that, Step S400 includes: S401. A hydrocarbon-based naphthylamine polyether with a molar ratio of 1:1~5 and the sulfonating agent are reacted at a temperature of 20~80°C for 0.5~10 hours to obtain a sulfonated product. S402. Adjust the pH value of the sulfonated product obtained in step S401 to 10-14, and hydrolyze for 0.5-5 hours to obtain a hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent.

17. A hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent prepared by any one of claims 8-16.

18. An oil displacement agent composition, characterized in that, The oil displacement agent composition comprises the hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent according to any one of claims 1 to 7 and 17 and water.

19. The oil displacement composition according to claim 18, characterized in that, The weight ratio of the hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent to water is 1:(50~2000).

20. The oil displacement agent composition according to claim 19, characterized in that, The weight ratio of the hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent to water is 1:(100~1000).

21. The use of the hydrocarbon-based naphthalene polyether sulfonate heavy oil displacement agent according to any one of claims 1-7 and 17, or the displacement agent composition according to any one of claims 18-20, in oil reservoir development.

22. The application according to claim 21, characterized in that, The application is in the exploitation of high-temperature and high-salinity oil reservoirs.

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