Oil exploitation auxiliary agent and preparation method thereof

Abstract

The invention discloses an oil exploitation aid and a preparation method thereof, and relates to the technical field of oil exploitation aids. The oil exploitation aid comprises the following raw materials in parts by weight: 30-40 parts of a modified carboxylate surfactant, 15-20 parts of a nonionic surfactant, 5-6 parts of a cosolvent, 4-6 parts of a stabilizer, 3-5 parts of an anti-scaling agent and 140-160 parts of deionized water. The preparation method comprises the following steps: firstly, carrying out a ring-opening acylation reaction by taking n-hexylamine, 1, 8-naphthalic anhydride and 12-bromo-1-dodecene as raw materials, carrying out an alkylation reaction to obtain 1-(dodecyl-11-ene-1-yl (amyl) carbamoyl)-2-sodium naphthoate, then carrying out a reaction with a first-generation polymer prepared from urotropine and p-aminophenol, and carrying out a reaction to obtain the 1-(dodecyl-11-ene-1-yl (amyl) carbamoyl)-2-sodium naphthoate. Finally, the modified carboxylate type surfactant is obtained. The oil exploitation auxiliary agent prepared by the invention has the effects of changing the wettability of a rock core and preventing swelling of clay, and the recovery rate of oil displacement of a low-permeability reservoir is improved.

Description

Technical Field

[0001] The invention relates to the technical field of oil production additives, and in particular to an oil production additive and a preparation method thereof. Background Art

[0002] With the continuous increase in energy demand and the continuous decrease in crude oil reserves, the development status of low-permeability oil reservoirs has become increasingly prominent. Low-permeability oil reservoirs are mostly distributed in highly heterogeneous carbonate fractures and caves, with low permeability and complex pore throat structure, so they are difficult to exploit and have low recovery rates. Changing the wettability of the rock surface, increasing the permeability of the water phase, reducing the injection pressure, and increasing the water injection volume are the methods generally pursued in the development of low-permeability reservoirs. Using oil extraction additives in low-permeability oil reservoirs to improve the wettability of the rock interface, inhibit clay expansion and migration, and then achieve the purpose of reducing pressure and increasing injection has become the main direction of research on the development of low-permeability oil fields.

[0003] The Chinese invention patent with publication number CN117903774A discloses a pressure-reducing and injection-increasing active agent and its preparation method and application. The pressure-reducing and injection-increasing active agent includes the following components: hydrophilic nanoparticles, hydrophobic nanoparticles, composite surfactants, alcohol solvents and water. The pressure-reducing and injection-increasing active agent has good dispersibility and stability, but the pressure reduction rate needs to be improved. Summary of the invention

[0004] In view of the shortcomings of the prior art, the object of the present invention is to provide an oil recovery additive and a preparation method thereof.

[0005] To achieve the above object, the present invention is implemented through the following technical solutions:

[0006] An oil extraction additive comprises the following raw materials in parts by weight:

[0007] Carboxylate surfactant: 30-40 parts,

[0008] Nonionic surfactant: 15-20 parts,

[0009] Solvent: 5-6 parts,

[0010] Stabilizer: 4-6 parts,

[0011] Anti-scaling agent: 3-5 parts,

[0012] Deionized water: 140-160 parts;

[0013] The carboxylate surfactant is prepared by the following method:

[0014] S1: DMSO, n-hexylamine, 1,8-naphthalene dicarboxylic anhydride, and catalyst aluminum chloride are added to the reactor in sequence, stirred, heated to 60-70°C, and reacted for 16-20h to obtain 1-(hexylamino)-2-naphthoic acid. The reaction equation is as follows:

[0015]

[0016] S2: Add 1-(hexylamino)-2-naphthoic acid to anhydrous ethanol, mix well, heat to 55-65° C., slowly dropwise add 12-bromo-1-dodecene ethanol solution to the reactor, react for 6-10 hours, and obtain 1-(dodec-11-en-1-yl(pentyl)carbamoyl)-2-naphthoic acid sodium. The reaction equation is as follows:

[0017]

[0018] The feed mass ratio of DMSO, n-hexylamine, 1,8-naphthalene dicarboxylic anhydride and catalyst aluminum chloride is 30:(1-3):(5-7):(0.2-0.6).

[0019] The mass ratio of the anhydrous ethanol, 1-(hexylamino)-2-naphthoic acid and 12-bromo-1-dodecene ethanol solution is 40:(1-3):(40-60).

[0020] The nonionic surfactant is one of octylphenol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether and nonylphenol polyoxyethylene ether.

[0021] The co-solvent is one of n-butanol, isopropanol and glycerol.

[0022] The stabilizer is one of ammonium chloride, aluminum chloride and calcium chloride.

[0023] The anti-scaling agent is one of ethylenediaminetetramethylenephosphonic acid and toluenetriazole.

[0024] A method for preparing an oil extraction additive comprises the following steps:

[0025] (1) Weighing by weight: carboxylate surfactant, nonionic surfactant, cosolvent, stabilizer, antiscalant, and deionized water;

[0026] (2) Deionized water, carboxylate surfactant, nonionic surfactant, cosolvent, stabilizer and antiscalant are sequentially added into the reactor, stirred, heated to 30-50° C., and kept warm for 3-5 hours to obtain an oil recovery additive.

[0027] An oil extraction additive, characterized in that it comprises the following raw materials in parts by weight:

[0028] Modified carboxylate surfactant: 30-40 parts,

[0029] Nonionic surfactant: 15-20 parts,

[0030] Solvent: 5-6 parts,

[0031] Stabilizer: 4-6 parts,

[0032] Anti-scaling agent: 3-5 parts,

[0033] Deionized water: 140-160 parts;

[0034] The modified carboxylate surfactant is prepared by the following method:

[0035] S3: Deionized water, hexamethylenetetramine, p-aminophenol and glacial acetic acid are added to the reactor in sequence, stirred and dissolved, heated to 60-70°C, and reacted for 2-3h. After the reaction is completed, a first-generation polymer is obtained, and its reaction equation is shown as follows:

[0036]

[0037] S4: DMF is added to the reactor, stirred, and heated to 95-105°C, and the first-generation polymer, 1-(dodec-11-en-1-yl(pentyl)carbamoyl)-2-naphthoic acid sodium, catalyst C-94, and 1-butyl-3-methylimidazolium methanesulfonate ionic liquid are added in sequence, and the reaction is carried out under nitrogen protection for 3-4 hours. After the reaction is completed, a modified carboxylate surfactant is obtained, and the reaction equation is shown as follows:

[0038]

[0039] Among them, m=o+p, m, o, p are natural numbers.

[0040] The number average molecular weight of the modified carboxylate surfactant is 9000-13000.

[0041] The mass ratio of the deionized water, hexamethylenetetramine, p-aminophenol and glacial acetic acid is 10:2.5:(1.0-1.2):(0.8-1.0).

[0042] The feed mass ratio of DMF, first-generation polymer, sodium 1-(dodec-11-en-1-yl(pentyl)carbamoyl)-2-naphthoate, catalyst C-94, and 1-butyl-3-methylimidazolium methanesulfonate ionic liquid is 25:6:(2-3):(0.04-0.08):(0.05-0.07).

[0043] The nonionic surfactant is one of octylphenol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether and nonylphenol polyoxyethylene ether.

[0044] The co-solvent is one of n-butanol, isopropanol and glycerol.

[0045] The stabilizer is one of ammonium chloride, aluminum chloride and calcium chloride.

[0046] The anti-scaling agent is one of ethylenediaminetetramethylenephosphonic acid and toluenetriazole.

[0047] A method for preparing an oil extraction additive comprises the following steps:

[0048] S1: Weigh by weight: modified carboxylate surfactant, nonionic surfactant, cosolvent, stabilizer, antiscalant, deionized water;

[0049] S2: Add deionized water, modified carboxylate surfactant, nonionic surfactant, cosolvent, stabilizer and antiscalant into the reactor in sequence, stir, heat to 30-50°C, and keep warm for 3-5h to obtain oil extraction additive.

[0050] Due to the adoption of the above technical solution, the beneficial effects of the present invention include:

[0051] (1) The present invention prepares 1-(hexylamino)-2-naphthoic acid through n-hexylamine and 1,8-naphthalene dicarboxylic anhydride, and then reacts 1-(hexylamino)-2-naphthoic acid, 12-bromo-1-dodecene and NaOH to obtain 1-(dodec-11-ene-1-yl (pentyl)carbamoyl)-2-naphthoic acid sodium; then prepares a first-generation polymer through urotropine and p-aminophenol, and the last-generation polymer reacts with 1-(dodec-11-ene-1-yl (pentyl)carbamoyl)-2-naphthoic acid sodium to obtain a modified carboxylate-type surfactant.

[0052] (2) The carboxylate surfactant prepared by the present invention connects the hydrophilic group and the hydrophobic carbon chain together through ring-opening acylation and alkylation reactions, so that the prepared surfactant has both hydrophobicity and hydrophilicity; and the modified carboxylate surfactant is obtained through graft polymerization, so that the molecular structure contains a large number of carboxylic acid hydrophilic groups, which can form more hydrogen bonds in water, thereby significantly enhancing the surface activity of the surfactant. Therefore, the prepared modified carboxylate surfactant has better water solubility and higher surface activity than traditional amphoteric surfactants, effectively reduces the interfacial tension of the solution, improves the wettability of the rock surface, and then reduces the flow resistance of the injected water, improves the fluidity of the crude oil, achieves the effect of reducing the water injection pressure, and improves the recovery rate of low-permeability oil reservoir displacement. DETAILED DESCRIPTION

[0053] The invention will be further described below with reference to the embodiments, but the invention is not limited to these embodiments.

[0054] Example 1 Carboxylate type surfactant:

[0055] S1: 300 g DMSO, 10 g n-hexylamine, 50 g 1,8-naphthalene dicarboxylic anhydride, and 2 g catalyst aluminum chloride were added to the reactor in sequence, stirred, heated to 60° C., reacted for 20 h, and distilled under reduced pressure at 50° C. for 1 h to obtain a concentrated solution of 1-(hexylamino)-2-naphthoic acid;

[0056] S2: Add 10g of 1-(hexylamino)-2-naphthoic acid concentrate to 400g of anhydrous ethanol, mix well, seal the reaction system, heat to 55°C, slowly drop 400g of 12-bromo-1-dodecene (CAS No.: 99828-63-4) ethanol solution (10wt%), the dropping time is 10min, react for 10h, adjust the pH to 7 with NaOH solution (1.5mol / L), distill at 50°C under reduced pressure for 1h, add 200g of anhydrous ethanol, filter, wash with 60g of anhydrous ethanol, and vacuum dry at 40°C for 6h to obtain 1-(dodec-11-ene-1-yl(pentyl)carbamoyl)-2-naphthoic acid sodium.

[0057] Example 2 Carboxylate type surfactant:

[0058] S1: 300 g DMSO, 20 g n-hexylamine, 60 g 1,8-naphthalene dicarboxylic anhydride, and 4 g catalyst aluminum chloride were added to the reactor in sequence, stirred, heated to 65° C., reacted for 18 h, and distilled at 50° C. under reduced pressure for 1.5 h to obtain a concentrated solution of 1-(hexylamino)-2-naphthoic acid;

[0059] S2: Add 20g of 1-(hexylamino)-2-naphthoic acid concentrate to 400g of anhydrous ethanol, mix well, seal the reaction system, heat to 60°C, slowly dropwise add 500g of 12-bromo-1-dodecene ethanol solution (10wt%), the dropping time is 15min, react for 8h, adjust the pH to 7.5 with NaOH solution (1mol / L), distill under reduced pressure at 50°C for 1.5h, add 200g of anhydrous ethanol, filter, wash with 60g of anhydrous ethanol, and vacuum dry at 55°C for 5.5h to obtain 1-(dodec-11-ene-1-yl (pentyl)carbamoyl)-2-naphthoic acid sodium, the hydrogen nuclear magnetic resonance spectrum data of which are as follows: 1 H NMR (300 MHz, DMSO-d 6)δ8.36–8.14(m,1H),7.91–7.87(m,1H),7.82(d,J=8.3Hz,1H),7.55–7.25(m,2H),5.85–5.63(m,1H),5.17–4.90(m,3H),4.96(ddt,J=17 .2,2.4,1.3Hz,1H),3.30(t,J=6.1Hz,4H),2.03(tdt,J=8.1,6.7,1.4Hz,2H),1.71–1.42(m,4H),1.47–1.13(m,21H),1.01–0.75(m,3H).

[0060] Example 3 Carboxylate type surfactant:

[0061] S1: 300 g DMSO, 30 g n-hexylamine, 70 g 1,8-naphthalene dicarboxylic anhydride, and 6 g catalyst aluminum chloride were added to the reactor in sequence, stirred, heated to 70°C, reacted for 16 h, and distilled at 50°C under reduced pressure for 1.5 h to obtain a 1-(hexylamino)-2-naphthoic acid concentrate;

[0062] S2: Add 30g of 1-(hexylamino)-2-naphthoic acid concentrate to 400g of anhydrous ethanol, mix well, seal the reaction system, heat to 65°C, slowly drop 600g of 12-bromo-1-dodecene ethanol solution (10wt%), the dropping time is 20min, react for 6h, adjust the pH to 8 with NaOH solution (1.5mol / L), distill under reduced pressure at 50°C for 1.5h, add 200g of anhydrous ethanol, filter, wash with 60g of anhydrous ethanol, and vacuum dry at 60°C for 5h to obtain sodium 1-(dodec-11-ene-1-yl(pentyl)carbamoyl)-2-naphthoate.

[0063] Example 4 Modified carboxylate type surfactant:

[0064] S3: 100 g of deionized water, 25 g of urotropine, 10 g of p-aminophenol, and 8 g of glacial acetic acid were added to the reactor in sequence, stirred and dissolved, heated to 60°C, reacted for 3 h, cooled to room temperature to separate the layers, removed the water layer, and washed with deionized water for 3 times (60 g of deionized water each time) to obtain a first-generation polymer;

[0065] S4: Add 250g of DMF to the reactor, stir, raise the temperature to 95°C, add 60g of the first-generation polymer, 20g of 1-(dodec-11-en-1-yl(pentyl)carbamoyl)-2-naphthoic acid sodium (prepared in Example 1), 0.4g of catalyst C-94, and 0.5g of 1-butyl-3-methylimidazolium methane sulfonate ionic liquid in sequence, react for 4h under nitrogen protection, cool to room temperature, add 500g of deionized water and stir evenly, obtain a polymer filter cake after centrifugal filtration, wash with 60g of anhydrous ethanol and then with 60g of deionized water, and dry in vacuo at 50°C for 10h to obtain a modified carboxylate surfactant with a number average molecular weight of 9160.

[0066] Example 5 Modified carboxylate type surfactant:

[0067] S3: 100 g of deionized water, 25 g of urotropine, 11 g of p-aminophenol, and 9 g of glacial acetic acid were added to the reactor in sequence, stirred and dissolved, heated to 65°C, reacted for 2.5 h, cooled to room temperature to separate the layers, removed the water layer, and washed with deionized water for 3 times (60 g of deionized water each time) to obtain a first-generation polymer;

[0068] S4: Add 250g of DMF to the reactor, stir, raise the temperature to 100°C, add 60g of the first-generation polymer, 25g of 1-(dodec-11-en-1-yl(pentyl)carbamoyl)-2-naphthoic acid sodium (prepared in Example 2), 0.6g of catalyst C-94, and 0.6g of 1-butyl-3-methylimidazolium methane sulfonate ionic liquid in sequence, react for 3.5h under nitrogen protection, cool to room temperature, add 500g of deionized water and stir evenly, obtain a polymer filter cake after centrifugal filtration, wash with 60g of anhydrous ethanol and then with 60g of deionized water, and dry in vacuo at 55°C for 9h to obtain a modified carboxylate surfactant with a number average molecular weight of 11130.

[0069] Example 6 Modified carboxylate type surfactant:

[0070] S3: 100 g of deionized water, 25 g of urotropine, 12 g of p-aminophenol, and 10 g of glacial acetic acid were added to the reactor in sequence, stirred and dissolved, heated to 70°C, reacted for 2 h, cooled to room temperature to separate the layers, removed the water layer, and washed with deionized water for 3 times (60 g of deionized water each time) to obtain a first-generation polymer;

[0071] S4: Add 250g of DMF to the reactor, stir, raise the temperature to 105°C, add 60g of the first-generation polymer, 30g of 1-(dodec-11-en-1-yl(pentyl)carbamoyl)-2-naphthoic acid sodium (prepared in Example 3), 0.8g of catalyst C-94, and 0.7g of 1-butyl-3-methylimidazolium methane sulfonate ionic liquid in sequence, react for 3h under nitrogen protection, cool to room temperature, add 500g of deionized water and stir evenly, obtain a polymer filter cake after centrifugal filtration, wash with 60g of anhydrous ethanol and then with 60g of deionized water, and dry in vacuo at 60°C for 8h to obtain a modified carboxylate surfactant with a number average molecular weight of 12790.

[0072] Example 7 Preparation of oil production aids:

[0073] (1) Weigh 300 g of a carboxylate surfactant (prepared in Example 1), 150 g of a nonionic surfactant (octylphenol polyoxyethylene ether), 50 g of a cosolvent (n-butanol), 40 g of a stabilizer (ammonium chloride), 30 g of an antiscalant (ethylenediaminetetramethylenephosphonic acid), and 1400 g of deionized water;

[0074] (2) Deionized water, carboxylate surfactant, nonionic surfactant, cosolvent, stabilizer and antiscalant are sequentially added into the reactor, stirred, and slowly heated to 30° C., and kept warm for 5 hours to obtain an oil recovery additive.

[0075] Example 8 Preparation of oil recovery additives:

[0076] (1) Weigh 350 g of a carboxylate surfactant (prepared in Example 2), 175 g of a nonionic surfactant (lauryl alcohol polyoxyethylene ether), 55 g of a cosolvent (isopropyl alcohol), 50 g of a stabilizer (aluminum chloride), 40 g of an antiscalant (ethylenediaminetetramethylenephosphonic acid), and 1500 g of deionized water;

[0077] (2) Deionized water, carboxylate surfactant, nonionic surfactant, cosolvent, stabilizer, and antiscalant are sequentially added to the reactor, stirred, and slowly heated to 40° C., and kept warm for 4 hours to obtain an oil recovery additive.

[0078] Example 9 Preparation of oil production aids:

[0079] (1) Weigh 400 g of a carboxylate surfactant (prepared in Example 3), 200 g of a nonionic surfactant (nonylphenol polyoxyethylene ether), 60 g of a cosolvent (glycerol), 60 g of a stabilizer (calcium chloride), 50 g of an antiscalant (methylbenzotriazole), and 1,600 g of deionized water;

[0080] (2) Deionized water, carboxylate surfactant, nonionic surfactant, cosolvent, stabilizer and antiscalant are sequentially added into the reactor, stirred, and slowly heated to 50° C., and kept warm for 3 hours to obtain an oil recovery additive.

[0081] Example 10 Preparation of oil production aids:

[0082] (1) Weigh 300 g of a modified carboxylate surfactant (prepared in Example 4), 150 g of a nonionic surfactant (octylphenol polyoxyethylene ether), 50 g of a cosolvent (n-butanol), 40 g of a stabilizer (ammonium chloride), 30 g of an antiscalant (ethylenediaminetetramethylenephosphonic acid), and 1400 g of deionized water;

[0083] (2) Deionized water, modified carboxylate surfactant, nonionic surfactant, cosolvent, stabilizer and antiscalant are sequentially added into the reactor, stirred, and slowly heated to 30° C., and kept warm for 5 hours to obtain an oil recovery additive.

[0084] Example 11 Preparation of oil production aids:

[0085] (1) Weigh 350 g of a modified carboxylate surfactant (prepared in Example 5), 175 g of a nonionic surfactant (lauryl alcohol polyoxyethylene ether), 55 g of a cosolvent (isopropyl alcohol), 50 g of a stabilizer (aluminum chloride), 40 g of an antiscalant (ethylenediaminetetramethylenephosphonic acid), and 1500 g of deionized water;

[0086] (2) Deionized water, modified carboxylate surfactant, nonionic surfactant, cosolvent, stabilizer and antiscalant are sequentially added into the reactor, stirred, and slowly heated to 40° C., and kept warm for 4 hours to obtain an oil recovery additive.

[0087] Example 12 Preparation of oil production aids:

[0088] (1) Weigh 400 g of a modified carboxylate surfactant (prepared in Example 6), 200 g of a nonionic surfactant (nonylphenol polyoxyethylene ether), 60 g of a cosolvent (glycerol), 60 g of a stabilizer (calcium chloride), 50 g of an antiscalant (methylbenzotriazole), and 1,600 g of deionized water;

[0089] (2) Deionized water, modified carboxylate surfactant, nonionic surfactant, cosolvent, stabilizer and antiscalant are sequentially added into the reactor, stirred, and slowly heated to 50° C., and kept warm for 3 hours to obtain an oil recovery additive.

[0090] Comparative Example 1

[0091] An oil extraction auxiliary agent, comprising the following raw materials:

[0092] Modified carboxylate surfactant (number average molecular weight 8250): 350g, nonionic surfactant (lauryl alcohol polyoxyethylene ether): 175g, cosolvent (isopropanol): 55g, stabilizer (aluminum chloride): 50g, antiscalant (ethylenediaminetetramethylenephosphonic acid): 40g, deionized water: 1500g;

[0093] Deionized water, modified carboxylate surfactant, nonionic surfactant, cosolvent, stabilizer and antiscalant were added to the reactor in sequence, stirred, slowly heated to 40°C, and kept warm for 4 hours to obtain the oil extraction additive.

[0094] The modified carboxylate surfactant in this comparative example was prepared by the following method:

[0095] S3: 100 g of deionized water, 25 g of urotropine, 11 g of p-aminophenol, and 9 g of glacial acetic acid were added to the reactor in sequence, stirred and dissolved, heated to 65°C, reacted for 2 h, cooled to room temperature to separate the layers, removed the water layer, and washed with deionized water for 3 times (60 g of deionized water each time) to obtain a first-generation polymer;

[0096] S4: Add 250g of DMF to the reactor, stir, raise the temperature to 90°C, add 50g of the first-generation polymer, 20g of 1-(dodec-11-en-1-yl(pentyl)carbamoyl)-2-naphthoic acid sodium (prepared in Example 2), 0.5g of catalyst C-94, and 0.5g of 1-butyl-3-methylimidazolium methane sulfonate ionic liquid in sequence, react for 3h under nitrogen protection, cool to room temperature, add 500g of deionized water and stir evenly, obtain a polymer filter cake after centrifugal filtration, wash with 60g of anhydrous ethanol and then with 60g of deionized water, and dry in vacuo at 55°C for 9h to obtain a modified carboxylate surfactant with a number average molecular weight of 8250.

[0097] Comparative Example 2

[0098] An oil extraction auxiliary agent, comprising the following raw materials:

[0099] Modified carboxylate surfactant (number average molecular weight 14030): 350g, nonionic surfactant (lauryl alcohol polyoxyethylene ether): 175g, cosolvent (isopropanol): 55g, stabilizer (aluminum chloride): 50g, antiscalant (ethylenediaminetetramethylenephosphonic acid): 40g, deionized water: 1500g;

[0100] Deionized water, modified carboxylate surfactant, nonionic surfactant, cosolvent, stabilizer and antiscalant were added to the reactor in sequence, stirred, slowly heated to 40°C, and kept warm for 4 hours to obtain the oil extraction additive.

[0101] The modified carboxylate surfactant in this comparative example was prepared by the following method:

[0102] S3: 100 g of deionized water, 25 g of urotropine, 12 g of p-aminophenol, and 10 g of glacial acetic acid were added to the reactor in sequence, stirred and dissolved, heated to 70°C, reacted for 2.5 h, cooled to room temperature to separate the layers, removed the water layer, and washed with deionized water for 3 times (60 g of deionized water each time) to obtain a first-generation polymer;

[0103] S4: Add 250g of DMF to the reactor, stir, raise the temperature to 115°C, add 65g of the first-generation polymer, 35g of 1-(dodec-11-en-1-yl(pentyl)carbamoyl)-2-naphthoic acid sodium (prepared in Example 3), 0.9g of catalyst C-94, and 0.8g of 1-butyl-3-methylimidazolium methane sulfonate ionic liquid in sequence, react for 3.5h under nitrogen protection, cool to room temperature, add 500g of deionized water and stir evenly, obtain a polymer filter cake after centrifugal filtration, wash with 60g of anhydrous ethanol and then with 60g of deionized water, and dry in vacuo at 60°C for 8h to obtain a modified carboxylate surfactant with a number average molecular weight of 14030.

[0104] Comparative Example 3

[0105] The preparation method of a petroleum extraction auxiliary agent is basically the same as that of Example 11, except that no modified carboxylate surfactant is added in step (2).

[0106] Comparative Example 4

[0107] A method for preparing an oil recovery additive is basically the same as that of Example 11, except that the modified carboxylate surfactant added in step (2) is replaced by an equal weight of 1-(hexylamino)-2-naphthoic acid prepared in step S1 of Example 2.

[0108] Comparative Example 5

[0109] A method for preparing a petroleum extraction additive is substantially the same as that of Example 11, except that the modified carboxylate surfactant added in step (2) is replaced by an equal weight of sodium N,N-dialkylethylenediaminedibenzoate.

[0110] Comparative Example 6

[0111] A petroleum extraction auxiliary agent is prepared by using the raw materials and method of Example 2 in publication number CN117903774A.

[0112] The model of octylphenol polyoxyethylene ether used in the comparative examples and embodiments of the present application is OP-10, produced by Nantong Yongle Chemical Co., Ltd.; the model of lauryl alcohol polyoxyethylene ether is AEO-9, produced by Hai'an Petrochemical Plant in Jiangsu Province; the model of nonylphenol polyoxyethylene ether is TX-10, produced by Shandong Yuke Chemical Co., Ltd.

[0113] The oil recovery additives prepared in the examples and comparative examples were tested for wettability, anti-swelling performance, and core displacement experiments. The test results are shown in Table 1.

[0114] Wettability (wetting angle) test: The test is carried out according to the contact angle method in SY / T5153-2007 "Method for Determination of Wettability of Reservoir Rocks".

[0115] Anti-swelling performance test: According to the provisions of SY / T5971-2016 "Performance Evaluation Method of Clay Stabilizer for Fracturing, Acidizing and Water Injection in Oil and Gas Fields", the anti-swelling effect of the surfactant depressurization and injection system on the cuttings in the reservoir section of the target block was determined. The experimental instrument was KC-GDP1 high-temperature dynamic linear expansion instrument.

[0116] Core flooding experiment:

[0117] The selective permeability is 0.15×10 -3 μm 2 For natural cores, wash the oil and salt, dry the cores, saturate them with simulated oil (kerosene and dehydrated crude oil in a mass ratio of 7:1, with a viscosity of 2 mPa·s (70°C)), place them at 70°C for 12 h, and then use water (viscosity of 0.58 mPa·s (70°C)) to displace the cores at a flow rate of 0.3 mL / min. Record the pressure changes during the displacement process until the pressure stabilizes, and record the pressure value P 0 ; Continue to inject 0.5 PV of the oil recovery additive prepared in the embodiment and the comparative example into the core, then close the valves at both ends of the displacement device, place it at 70°C for 6 hours, continue to use water to displace the core at the same flow rate, record the pressure change during the displacement process, until the pressure stabilizes, and record the pressure value P 1 , calculate the pressure reduction rate of the core after oil recovery additive displacement.

[0118] Table 1

[0119]

[0120]

[0121] It can be seen from Table 1 that the anti-swelling rate of the oil extraction additive prepared by the present application with the addition of carboxylate type surfactants reaches more than 85%, and the pressure reduction rate reaches more than 38%. The anti-swelling rate of the oil extraction additive with the addition of modified carboxylate type surfactants reaches more than 90%, and the pressure reduction rate reaches more than 42%, indicating that the oil extraction additive prepared by the present application has a good oil recovery rate.

[0122] The contact angle of the oil recovery additive prepared in Example 11 of the present application is relatively high, reaching 79.5°. It can be seen that the wettability changes from hydrophilicity to intermediate wettability, which is beneficial to reducing the water injection pressure and improving the water phase permeability.

[0123] Comparative Examples 1 and 2 are comparative examples of oil recovery additives prepared using modified carboxylate surfactants with number average molecular weights lower than 9,000 and higher than 13,000. It can be seen from Table 1 that the pressure reduction rates of the two comparative examples are reduced to less than 38%.

[0124] Comparative Example 3 is a comparative example of an oil recovery additive prepared without using a modified carboxylate surfactant. As can be seen from Table 1, its pressure reduction rate is only 16.30%, and the pressure reduction effect is not obvious.

[0125] Comparative Example 4 is different from Example 11, and the difference is that the modified carboxylate surfactant used is replaced by an equal weight of 1-(hexylamino)-2-naphthoic acid prepared in step S1 of Example 2. It can be seen from the data in Table 1 that the pressure reduction rate is 20.16%, and the pressure reduction and injection increase effect is poor.

[0126] Comparative Example 5 is different from Example 11, and the difference is that the modified carboxylate surfactant used is replaced with an equal weight of N,N-dialkylethylenediamine sodium dibenzoate. It can be seen from the data in Table 1 that the pressure reduction rate is 32.06%, and the pressure reduction and injection increase effect is poor.

[0127] Comparative Example 6 is a pressure-reducing and injection-increasing active agent prepared using the raw materials and method of Example 1 in Publication No. CN117903774A. From the data in Table 1, it can be seen that the pressure reduction rate is 36.12%, and the pressure-reducing and injection-increasing effect is poor.

[0128] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. However, any equivalent changes, modifications and evolutions made by ordinary technicians in the field without departing from the scope of the technical solution of the present invention by using the technical content disclosed above are all equivalent embodiments of the present invention. At the same time, any equivalent changes, modifications and evolutions made to the above embodiments based on the essential technology of the present invention are still within the protection scope of the technical solution of the present invention.

Claims

1. A petroleum extraction aid, characterized in that: The invention comprises the following raw materials in parts by weight: Carboxylate surfactant: 30-40 parts, Nonionic surfactant: 15-20 parts, Solvent: 5-6 parts, Stabilizer: 4-6 parts, Anti-scaling agent: 3-5 parts, Deionized water: 140-160 parts; The carboxylate surfactant is prepared by the following method: S1: DMSO, n-hexylamine, 1,8-naphthalene dicarboxylic anhydride, and catalyst aluminum chloride are added to the reactor in sequence, stirred, heated to 60-70° C., and reacted for 16-20 hours to obtain 1-(hexylamino)-2-naphthoic acid; S2: Add 1-(hexylamino)-2-naphthoic acid to anhydrous ethanol, mix well, heat to 55-65°C, slowly drop 12-bromo-1-dodecene ethanol solution, react for 6-10 hours, and obtain sodium 1-(dodec-11-en-1-yl(pentyl)carbamoyl)-2-naphthoate, which is a carboxylate surfactant.

2. The oil recovery aid according to claim 1, characterized in that: In step S1, the feed mass ratio of DMSO, n-hexylamine, 1,8-naphthalene dicarboxylic anhydride and catalyst aluminum chloride is 30:(1-3):(5-7):(0.2-0.6).

3. The oil recovery aid according to claim 1, characterized in that: In step S2, the mass ratio of the anhydrous ethanol, 1-(hexylamino)-2-naphthoic acid, and 12-bromo-1-dodecene ethanol solution is 40:(1-3):(40-60).

4. A petroleum extraction aid, characterized in that: The invention comprises the following raw materials in parts by weight: Modified carboxylate surfactant: 30-40 parts, Nonionic surfactant: 15-20 parts, Solvent: 5-6 parts, Stabilizer: 4-6 parts, Anti-scaling agent: 3-5 parts, Deionized water: 140-160 parts; The modified carboxylate surfactant is prepared by the following method: S3: Deionized water, hexamethylenetetramine, p-aminophenol and glacial acetic acid are added into the reactor in sequence, stirred and dissolved, heated to 60-70°C, reacted for 2-3h, and a first-generation polymer is obtained; S4: Add DMF to the reactor, stir, raise the temperature to 95-105°C, add the first-generation polymer, 1-(dodec-11-en-1-yl(pentyl)carbamoyl)-2-naphthoic acid sodium, catalyst C-94, and 1-butyl-3-methylimidazolium methane sulfonate ionic liquid in sequence, react for 3-4 hours under nitrogen protection to obtain a modified carboxylate type surfactant.

5. The oil recovery aid according to claim 4, characterized in that: The number average molecular weight of the modified carboxylate surfactant is 9000-13000.

6. The oil recovery aid according to claim 4, characterized in that: In step S3, the mass ratio of the deionized water, hexamethylenetetramine, p-aminophenol and glacial acetic acid is 10:2.5:(1.0-1.2):(0.8-1.0).

7. The oil recovery aid according to claim 4, characterized in that: In step S4, the feed mass ratio of DMF, first-generation polymer, sodium 1-(dodec-11-en-1-yl(pentyl)carbamoyl)-2-naphthoate, catalyst C-94, and 1-butyl-3-methylimidazolium methanesulfonate ionic liquid is 25:6:(2-3):(0.04-0.08):(0.05-0.07).

8. An oil recovery aid according to claim 1 or 4, characterized in that: The nonionic surfactant is one of octylphenol polyoxyethylene ether, lauryl alcohol polyoxyethylene ether, and nonylphenol polyoxyethylene ether; the cosolvent is one of n-butanol, isopropanol, and glycerol; the stabilizer is one of ammonium chloride, aluminum chloride, and calcium chloride; and the anti-scaling agent is one of ethylenediaminetetramethylenephosphonic acid and methylbenzotriazole.

9. A method for preparing the oil recovery aid according to any one of claims 1, 2 and 3, characterized in that: The following steps are involved: (1) Weighing by weight: carboxylate surfactant, nonionic surfactant, cosolvent, stabilizer, antiscalant, and deionized water; (2) Deionized water, carboxylate surfactant, nonionic surfactant, cosolvent, stabilizer and antiscalant are sequentially added into the reactor, stirred, heated to 30-50° C., and kept warm for 3-5 hours to obtain an oil recovery additive.

10. A method for preparing the oil recovery aid according to any one of claims 4, 5, 6 and 7, characterized in that: The following steps are involved: (1) Weighing by weight: modified carboxylate surfactant, nonionic surfactant, cosolvent, stabilizer, antiscalant, and deionized water; (2) Deionized water, modified carboxylate surfactant, nonionic surfactant, cosolvent, stabilizer and antiscalant are sequentially added into the reactor, stirred, heated to 30-50° C., and kept warm for 3-5 hours to obtain an oil recovery additive.

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