An oil production aid and its preparation method

Abstract

The present invention discloses an oil production aid and a preparation method thereof, relating to the technical field of oil production aids. The oil production aid comprises the following raw materials in parts by weight: 30-40 parts of a modified carboxylate surfactant, 15-20 parts of a non-ionic surfactant, 5-6 parts of a co-solvent, 4-6 parts of a stabilizer, 3-5 parts of a scale inhibitor, and 140-160 parts of deionized water; first, 1-(dodec-11-en-1-yl(pentyl)carbamoyl)-2-naphthoic acid sodium is obtained by a ring-opening acylation reaction and an alkylation reaction using n-hexylamine, 1,8-naphthalic anhydride, and 12-bromo-1-dodecene as raw materials, and then it reacts with a first-generation polymer prepared from hexamine and p-aminophenol to finally obtain the modified carboxylate surfactant. The oil production aid prepared by the present invention has the effects of changing the wettability of the core and preventing clay swelling, and improves the oil recovery rate of low-permeability oil reservoirs.

Description

Technical Field

[0001] The present invention relates to the technical field of petroleum production aids, and specifically relates to a petroleum production aid 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 reservoirs has become increasingly prominent. Low-permeability reservoirs are mostly distributed in strongly heterogeneous carbonate rock fractures and caves, with low permeability and complex pore-throat structures. Therefore, the exploitation is difficult and the recovery rate is low. By changing the wettability of the rock surface, increasing the water-phase permeability, reducing the injection pressure, and increasing the injection volume are the commonly pursued methods for the development of low-permeability reservoirs. Using petroleum production aids in low-permeability reservoirs to improve the wettability of the rock interface, inhibit clay swelling and migration, and thus achieve the purpose of reducing pressure and increasing injection has become the main research direction in the current development work of low-permeability oilfields.

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

[0004] Aiming at the deficiencies of the existing technology, the purpose of the present invention is to provide a petroleum production aid and a preparation method thereof.

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

[0006] A petroleum production aid, comprising the following raw materials in parts by weight:

[0007] Carboxylate surfactant: 30 - 40 parts,

[0008] Non-ionic surfactant: 15 - 20 parts,

[0009] Cosolvent: 5 - 6 parts,

[0010] Stabilizer: 4 - 6 parts,

[0011] Scale inhibitor: 3 - 5 parts,

[0012] Deionized water: 140 - 160 parts;

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

[0014] S1: Add DMSO, n-hexylamine, 1,8-naphthalic anhydride, and catalyst aluminum chloride into the reactor in sequence, stir, heat up to 60 - 70 °C, and react for 16 - 20 h to obtain 1-(hexylamino)-2-naphthoic acid. The reaction equation is shown as follows:

[0015]

[0016] S2: Add 1-(hexylamino)-2-naphthoic acid into absolute ethanol, mix evenly, heat up to 55 - 65 °C, and slowly dropwise add the ethanol solution of 12-bromo-1-dodecene into the reactor, react for 6 - 10 h to obtain sodium 1-(dodec-11-ene-1-yl(pentyl)carbamoyl)-2-naphthoate. The reaction equation is shown as follows:

[0017]

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

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

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

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

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

[0023] The scale inhibitor is one of ethylenediaminetetra(methylene phosphonic acid) and methylbenzotriazole.

[0024] A preparation method of an oil recovery aid includes the following steps:

[0025] (1) Weigh by weight parts: carboxylate surfactant, non-ionic surfactant, cosolvent, stabilizer, scale inhibitor, deionized water;

[0026] (2) Add deionized water, carboxylate surfactant, non-ionic surfactant, cosolvent, stabilizer, and scale inhibitor into the reactor in sequence, stir, heat up to 30 - 50 °C, and keep warm for 3 - 5 h to obtain the oil recovery aid.

[0027] An oil recovery aid, characterized in that it comprises the following raw materials in weight parts:

[0028] Modified carboxylate surfactant: 30 - 40 parts

[0029] Non - ionic surfactant: 15 - 20 parts

[0030] Cosolvent: 5 - 6 parts

[0031] Stabilizer: 4 - 6 parts

[0032] Scale inhibitor: 3 - 5 parts

[0033] Deionized water: 140 - 160 parts

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

[0035] S3: Add deionized water, hexamethylenetetramine, p - aminophenol, and glacial acetic acid into the reactor in sequence, stir to dissolve, heat up to 60 - 70 °C, and react for 2 - 3 h. After the reaction, a first - generation polymer is obtained. The reaction equation is shown as follows:

[0036]

[0037] S4: Add DMF into the reactor, stir, heat up to 95 - 105 °C, and add the first - generation polymer, 1 - (dodec - 11 - en - 1 - yl(pentyl)carbamoyl)-2 - naphthalenesulfonate, catalyst C - 94, and 1 - butyl - 3 - methylimidazolium methanesulfonate ionic liquid in sequence. React under nitrogen protection for 3 - 4 h. After the reaction, a modified carboxylate surfactant is obtained. The reaction equation is shown as follows:

[0038]

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

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

[0041] The feeding 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 feeding mass ratio of the DMF, first - generation polymer, 1 - (dodec - 11 - en - 1 - yl(pentyl)carbamoyl)-2 - naphthalenesulfonate, 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 non-ionic 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 scale inhibitor is one of ethylenediaminetetra(methylene phosphonic acid) and methylbenzotriazole.

[0047] A preparation method of an oil recovery aid includes the following steps:

[0048] S1: Weigh by parts by weight: modified carboxylate surfactant, non-ionic surfactant, co-solvent, stabilizer, scale inhibitor, and deionized water;

[0049] S2: Add deionized water, modified carboxylate surfactant, non-ionic surfactant, co-solvent, stabilizer, and scale inhibitor into the reactor in sequence, stir, heat up to 30 - 50 °C, and keep warm for 3 - 5 h to obtain the oil recovery aid.

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

[0051] (1) In the present invention, 1-(hexylamino)-2-naphthoic acid is prepared from hexylamine and 1,8-naphthalic anhydride, and then 1-(dodec-11-en-1-yl(amyl)carbamoyl)-2-naphthoic acid sodium salt is obtained by reacting 1-(hexylamino)-2-naphthoic acid, 12-bromo-1-dodecene, and NaOH; then a first-generation polymer is prepared from hexamine and p-aminophenol, and finally the modified carboxylate surfactant is obtained by reacting the first-generation polymer with 1-(dodec-11-en-1-yl(amyl)carbamoyl)-2-naphthoic acid sodium salt.

[0052] (2) For the carboxylate surfactant prepared in the present invention, the hydrophilic group and the hydrophobic carbon chain are connected 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 reaction, so that the molecular structure contains a large number of carboxylic acid hydrophilic groups, which can form more hydrogen bonds in water, thus 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, further reduces the flow resistance of the injected water, improves the fluidity of the crude oil, achieves the effect of reducing the injection pressure, and improves the oil recovery rate of low-permeability oil reservoirs. Specific Embodiments

[0053] The following further illustrates with embodiments, but the present invention is not limited to these embodiments.

[0054] Example 1 Carboxylate Surfactant:

[0055] S1: Add 300 g of DMSO, 10 g of n-hexylamine, 50 g of 1,8-naphthalic anhydride, and 2 g of catalyst aluminum chloride into the reactor in sequence, stir, heat up to 60 °C, react for 20 h, and carry out vacuum distillation at 50 °C for 1 h to obtain a concentrated solution of 1-(hexylamino)-2-naphthoic acid;

[0056] S2: Add 10 g of the concentrated solution of 1-(hexylamino)-2-naphthoic acid into 400 g of absolute ethanol, mix evenly, seal the reaction system, heat up to 55 °C, slowly dropwise add an ethanol solution (10 wt%) of 400 g of 12-bromo-1-dodecene (CAS No.: 99828-63-4), the dropping time is 10 min, react for 10 h, adjust the pH to 7 with NaOH solution (1.5 mol / L), carry out vacuum distillation at 50 °C for 1 h, add 200 g of absolute ethanol, filter, wash with 60 g of absolute ethanol, and carry out vacuum drying at 40 °C for 6 h to obtain sodium 1-(dodec-11-en-1-yl(pentyl)carbamoyl)-2-naphthoate.

[0057] Example 2 Carboxylate Surfactant:

[0058] S1: Add 300 g of DMSO, 20 g of n-hexylamine, 60 g of 1,8-naphthalic anhydride, and 4 g of catalyst aluminum chloride into the reactor in sequence, stir, heat up to 65 °C, react for 18 h, and carry out vacuum distillation at 50 °C for 1.5 h to obtain a concentrated solution of 1-(hexylamino)-2-naphthoic acid;

[0059] S2: Add 20 g of the concentrated solution of 1-(hexylamino)-2-naphthoic acid into 400 g of absolute ethanol, mix evenly, seal the reaction system, heat up to 60 °C, slowly dropwise add an ethanol solution (10 wt%) of 500 g of 12-bromo-1-dodecene, the dropping time is 15 min, react for 8 h, adjust the pH to 7.5 with NaOH solution (1 mol / L), carry out vacuum distillation at 50 °C for 1.5 h, add 200 g of absolute ethanol, filter, wash with 60 g of absolute ethanol, and carry out vacuum drying at 55 °C for 5.5 h to obtain sodium 1-(dodec-11-en-1-yl(pentyl)carbamoyl)-2-naphthoate, and the data of its nuclear magnetic resonance hydrogen spectrum are as follows: 11H NMR (300 MHz, DMSO-d6) δ 8.36–8.14 (m, 1H), 7.91–7.87 (m, 1H), 7.82 (d, J = 8.3 Hz, 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, 1.3 Hz, 1H), 3.30 (t, J = 6.1 Hz, 4H), 2.03 (tdt, J = 8.1, 6.7, 1.4 Hz, 2H), 1.71–1.42 (m, 4H), 1.47–1.13 (m, 21H), 1.01–0.75 (m, 3H).

[0060] Example 3 Carboxylate Surfactant:

[0061] S1: Add 300 g of DMSO, 30 g of n-hexylamine, 70 g of 1,8-naphthalic anhydride, and 6 g of catalyst aluminum chloride into the reactor in sequence, stir, heat up to 70 °C, react for 16 h, and carry out vacuum distillation at 50 °C for 1.5 h to obtain a concentrated solution of 1-(hexylamino)-2-naphthoic acid;

[0062] S2: Add 30 g of the concentrated solution of 1-(hexylamino)-2-naphthoic acid into 400 g of absolute ethanol, mix evenly, seal the reaction system, heat up to 65 °C, slowly dropwise add an ethanol solution (10 wt%) of 600 g of 12-bromo-1-dodecene over 20 min, react for 6 h, adjust the pH to 8 with NaOH solution (1.5 mol / L), carry out vacuum distillation at 50 °C for 1.5 h, add 200 g of absolute ethanol, filter, wash with 60 g of absolute ethanol, and vacuum dry at 60 °C for 5 h to obtain sodium 1-(dodec-11-en-1-yl(pentyl)carbamoyl)-2-naphthoate.

[0063] Example 4 Modified Carboxylate Surfactant:

[0064] S3: Add 100 g of deionized water, 25 g of hexamine, 10 g of p-aminophenol, and 8 g of glacial acetic acid into the reactor in sequence, stir and dissolve, heat up to 60 °C, react for 3 h, cool to room temperature and separate layers, remove the aqueous layer, and wash with deionized water three times (60 g of deionized water each time) to obtain the first-generation polymer;

[0065] S4: Add 250 g of DMF into the reactor, stir, heat up to 95 °C, and sequentially add 60 g of the first-generation polymer, 20 g of sodium 1-(dodec-11-en-1-yl(pentyl)carbamoyl)-2-naphthoate (prepared in Example 1), 0.4 g of catalyst C-94, and 0.5 g of 1-butyl-3-methylimidazolium methanesulfonate ionic liquid. React for 4 h under nitrogen protection, cool to room temperature, add 500 g of deionized water and stir evenly. After centrifugal filtration, obtain a polymer cake, wash it with 60 g of absolute ethanol and then with 60 g of deionized water. Dry it in vacuum at 50 °C for 10 h to obtain a modified carboxylate surfactant with a number-average molecular weight of 9160.

[0066] Example 5 Modified Carboxylate Surfactant:

[0067] S3: Sequentially add 100 g of deionized water, 25 g of hexamethylenetetramine, 11 g of p-aminophenol, and 9 g of glacial acetic acid into the reactor, stir to dissolve, heat up to 65 °C, react for 2.5 h, cool to room temperature and separate layers. Remove the aqueous layer and wash it 3 times with deionized water (60 g of deionized water each time) to obtain the first-generation polymer;

[0068] S4: Add 250 g of DMF into the reactor, stir, heat up to 100 °C, and sequentially add 60 g of the first-generation polymer, 25 g of sodium 1-(dodec-11-en-1-yl(pentyl)carbamoyl)-2-naphthoate (prepared in Example 2), 0.6 g of catalyst C-94, and 0.6 g of 1-butyl-3-methylimidazolium methanesulfonate ionic liquid. React for 3.5 h under nitrogen protection, cool to room temperature, add 500 g of deionized water and stir evenly. After centrifugal filtration, obtain a polymer cake, wash it with 60 g of absolute ethanol and then with 60 g of deionized water. Dry it in vacuum at 55 °C for 9 h to obtain a modified carboxylate surfactant with a number-average molecular weight of 11130.

[0069] Example 6 Modified Carboxylate Surfactant:

[0070] S3: Sequentially add 100 g of deionized water, 25 g of hexamethylenetetramine, 12 g of p-aminophenol, and 10 g of glacial acetic acid into the reactor, stir to dissolve, heat up to 70 °C, react for 2 h, cool to room temperature and separate layers. Remove the aqueous layer and wash it 3 times with deionized water (60 g of deionized water each time) to obtain the first-generation polymer;

[0071] S4: Add 250 g of DMF to the reactor, stir, heat up to 105 °C, and sequentially add 60 g of the first-generation polymer, 30 g of sodium 1-(dodec-11-en-1-yl(pentyl)carbamoyl)-2-naphthoate (prepared in Example 3), 0.8 g of catalyst C-94, and 0.7 g of 1-butyl-3-methylimidazolium methanesulfonate ionic liquid. React under nitrogen protection for 3 h, cool to room temperature, add 500 g of deionized water and stir evenly. After centrifugal filtration, obtain a polymer cake, wash it with 60 g of absolute ethanol and then with 60 g of deionized water. Dry the polymer cake in vacuum at 60 °C for 8 h to obtain a modified carboxylate surfactant with a number-average molecular weight of 12,790.

[0072] Preparation of the petroleum recovery aid in Example 7:

[0073] (1) Weigh the carboxylate surfactant (prepared in Example 1): 300 g, non-ionic surfactant (octylphenol polyoxyethylene ether): 150 g, co-solvent (n-butanol): 50 g, stabilizer (ammonium chloride): 40 g, scale inhibitor (ethylenediaminetetra(methylenephosphonic acid)): 30 g, and deionized water: 1400 g;

[0074] (2) Sequentially add deionized water, carboxylate surfactant, non-ionic surfactant, co-solvent, stabilizer, and scale inhibitor to the reactor, stir, and slowly heat up to 30 °C, and keep it warm for 5 h to obtain the petroleum recovery aid.

[0075] Preparation of the petroleum recovery aid in Example 8:

[0076] (1) Weigh the carboxylate surfactant (prepared in Example 2): 350 g, non-ionic surfactant (lauryl alcohol polyoxyethylene ether): 175 g, co-solvent (isopropanol): 55 g, stabilizer (aluminum chloride): 50 g, scale inhibitor (ethylenediaminetetra(methylenephosphonic acid)): 40 g, and deionized water: 1500 g;

[0077] (2) Sequentially add deionized water, carboxylate surfactant, non-ionic surfactant, co-solvent, stabilizer, and scale inhibitor to the reactor, stir, and slowly heat up to 40 °C, and keep it warm for 4 h to obtain the petroleum recovery aid.

[0078] Preparation of the petroleum recovery aid in Example 9:

[0079] (1) Weigh the carboxylate surfactant (prepared in Example 3): 400 g, non-ionic surfactant (nonylphenol polyoxyethylene ether): 200 g, co-solvent (glycerol): 60 g, stabilizer (calcium chloride): 60 g, scale inhibitor (methylbenzotriazole): 50 g, and deionized water: 1600 g;

[0080] (2) Add deionized water, carboxylate surfactant, non-ionic surfactant, co-solvent, stabilizer, and scale inhibitor into the reactor in sequence, stir, slowly heat up to 50 °C, and keep warm for 3 h to obtain the petroleum recovery aid.

[0081] Preparation of petroleum recovery aid in Example 10:

[0082] (1) Weigh the modified carboxylate surfactant (prepared in Example 4): 300 g, non-ionic surfactant (octylphenol polyoxyethylene ether): 150 g, co-solvent (n-butanol): 50 g, stabilizer (ammonium chloride): 40 g, scale inhibitor (ethylenediaminetetra(methylene phosphonic acid)): 30 g, and deionized water: 1400 g;

[0083] (2) Add deionized water, modified carboxylate surfactant, non-ionic surfactant, co-solvent, stabilizer, and scale inhibitor into the reactor in sequence, stir, slowly heat up to 30 °C, and keep warm for 5 h to obtain the petroleum recovery aid.

[0084] Preparation of petroleum recovery aid in Example 11:

[0085] (1) Weigh the modified carboxylate surfactant (prepared in Example 5): 350 g, non-ionic surfactant (lauryl alcohol polyoxyethylene ether): 175 g, co-solvent (isopropanol): 55 g, stabilizer (aluminum chloride): 50 g, scale inhibitor (ethylenediaminetetra(methylene phosphonic acid)): 40 g, and deionized water: 1500 g;

[0086] (2) Add deionized water, modified carboxylate surfactant, non-ionic surfactant, co-solvent, stabilizer, and scale inhibitor into the reactor in sequence, stir, slowly heat up to 40 °C, and keep warm for 4 h to obtain the petroleum recovery aid.

[0087] Preparation of petroleum recovery aid in Example 12:

[0088] (1) Weigh the modified carboxylate surfactant (prepared in Example 6): 400 g, non-ionic surfactant (nonylphenol polyoxyethylene ether): 200 g, co-solvent (glycerol): 60 g, stabilizer (calcium chloride): 60 g, scale inhibitor (methylbenzotriazole): 50 g, and deionized water: 1600 g;

[0089] (2) Add deionized water, modified carboxylate surfactant, non-ionic surfactant, co-solvent, stabilizer, and scale inhibitor into the reactor in sequence, stir, slowly heat up to 50 °C, and keep warm for 3 h to obtain the petroleum recovery aid.

[0090] Comparative Example 1

[0091] A petroleum recovery aid, comprising the following raw materials:

[0092] Modified carboxylate surfactant (number-average molecular weight: 8,250): 350 g, non-ionic surfactant (lauryl alcohol polyoxyethylene ether): 175 g, co-solvent (isopropyl alcohol): 55 g, stabilizer (aluminum chloride): 50 g, scale inhibitor (ethylenediaminetetra(methylenephosphonic acid)): 40 g, deionized water: 1,500 g;

[0093] Add deionized water, modified carboxylate surfactant, non-ionic surfactant, co-solvent, stabilizer, and scale inhibitor to the reactor in sequence, stir, and slowly heat up to 40 °C, then keep the temperature for 4 h to obtain the petroleum recovery aid.

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

[0095] S3: Add 100 g of deionized water, 25 g of hexamethylenetetramine, 11 g of p-aminophenol, and 9 g of glacial acetic acid to the reactor in sequence, stir to dissolve, heat up to 65 °C, react for 2 h, cool to room temperature and separate layers, remove the aqueous layer, wash with deionized water 3 times (60 g of deionized water each time) to obtain the first-generation polymer;

[0096] S4: Add 250 g of DMF to the reactor, stir, heat up to 90 °C, and add 50 g of the first-generation polymer, 20 g of 1-(dodec-11-en-1-yl(pentyl)carbamoyl)-2-naphthoate (prepared in Example 2), 0.5 g of catalyst C-94, and 0.5 g of 1-butyl-3-methylimidazolium methanesulfonate ionic liquid in sequence. React under nitrogen protection for 3 h, cool to room temperature, add 500 g of deionized water and stir evenly. After centrifugal filtration, obtain the polymer cake, wash it with 60 g of absolute ethanol and then with 60 g of deionized water. Dry in vacuum at 55 °C for 9 h to obtain a modified carboxylate surfactant with a number-average molecular weight of 8,250.

[0097] Comparative Example 2

[0098] A petroleum recovery aid, comprising the following raw materials:

[0099] Modified carboxylate surfactant (number-average molecular weight: 14,030): 350 g, non-ionic surfactant (lauryl alcohol polyoxyethylene ether): 175 g, co-solvent (isopropyl alcohol): 55 g, stabilizer (aluminum chloride): 50 g, scale inhibitor (ethylenediaminetetra(methylenephosphonic acid)): 40 g, deionized water: 1,500 g;

[0100] Add deionized water, modified carboxylate surfactant, non-ionic surfactant, co-solvent, stabilizer, and scale inhibitor to the reactor in sequence, stir, and slowly heat up to 40 °C, then keep the temperature for 4 h to obtain the petroleum recovery aid.

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

[0102] S3: Add 100 g of deionized water, 25 g of hexamethylenetetramine, 12 g of p-aminophenol, and 10 g of glacial acetic acid into the reactor in sequence, stir to dissolve, heat up to 70 °C, react for 2.5 h, cool to room temperature and layer, remove the aqueous layer, wash with deionized water 3 times (60 g of deionized water each time) to obtain the first-generation polymer;

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

[0104] Comparative Example 3

[0105] The preparation method of an oil recovery aid is basically the same as that of Example 11, except that in step (2), the modified carboxylate surfactant is not added.

[0106] Comparative Example 4

[0107] The preparation method of an oil recovery aid is basically the same as that of Example 11, except that the modified carboxylate surfactant added in step (2) is replaced with 1-(hexylamino)-2-naphthoic acid prepared in step S1 of Example 2 with the same weight.

[0108] Comparative Example 5

[0109] The preparation method of an oil recovery aid is basically the same as that of Example 11, except that the modified carboxylate surfactant added in step (2) is replaced with sodium N,N-dialkylethylenediaminedibenzoate with the same weight.

[0110] Comparative Example 6

[0111] An oil recovery aid prepared by using the raw materials and method of Example 2 in the publication No. CN117903774A.

[0112] The models of octylphenol polyoxyethylene ether used in the comparative examples and examples of this application are OP-10, produced by Nantong Yongle Chemical Co., Ltd.; the model of lauryl alcohol polyoxyethylene ether is AEO-9, produced by Jiangsu Haian Petrochemical Factory; the model of nonylphenol polyoxyethylene ether is TX-10, produced by Shandong Yuke Chemical Co., Ltd.

[0113] The wetting performance, anti-swelling performance, and core flooding experiment tests were carried out on the petroleum recovery aids prepared in the examples and comparative examples, and the test results are shown in Table 1.

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

[0115] Anti-swelling performance test: According to the regulations in SY / T5971-2016 "Performance Evaluation Method for Clay Stabilizers Used in Oil and Gas Field Fracturing Acidizing and Water Injection", the anti-swelling effect of the surfactant pressure reduction and injection increase system on the cuttings of the reservoir section in the target block was determined. The experimental instrument was a KC-GDP1 high-temperature dynamic linear dilatometer.

[0116] Core flooding experiment:

[0117] Select natural cores with a permeability of 0.15×10 -3 μm 2 After washing the cores with oil, washing with salt, and drying, saturate them with simulated oil (prepared by mixing kerosene and dehydrated crude oil at 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 displace the cores with water (viscosity of 0.58 mPa·s (70 °C)) 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 P0; continue to inject 0.5 PV of the petroleum recovery aids prepared in the examples and comparative examples into the cores, then close the valves at both ends of the displacement device, place them at 70 °C for 6 h, and continue to displace the cores with water at the same flow rate. Record the pressure changes during the displacement process until the pressure stabilizes, and record the pressure value P1. Calculate the pressure reduction rate of the cores after displacement with the petroleum recovery aids.

[0118] Table 1

[0119]

[0120]

[0121] It can be seen from Table 1 that the anti-swelling rate of the petroleum recovery aids prepared in this application with carboxylate surfactants added reaches more than 85%, and the pressure reduction rate reaches more than 38%. The anti-swelling rate of the petroleum recovery aids with modified carboxylate surfactants added reaches more than 90%, and the pressure reduction rate reaches more than 42%. This shows that the petroleum recovery aids prepared in this application have good oil recovery efficiency.

[0122] In Example 11 of this application, the contact angle of the oil recovery aid prepared 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 injection pressure and increasing the water-phase permeability.

[0123] Comparative Example 1 and Comparative Example 2 are comparative examples of oil recovery aids prepared using modified carboxylate surfactants with a number-average molecular weight lower than 9000 and higher than 13000. 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 aid prepared without using a modified carboxylate surfactant. It can be seen from Table 1 that its pressure reduction rate is only 16.30%, and the pressure reduction effect is not obvious.

[0125] Comparative Example 4 is a comparative example different from Example 11. The difference is that the modified carboxylate surfactant used is replaced with 1-(hexylamino)-2-naphthoic acid prepared in Step S1 of Example 2 with the same weight. It can be seen from the data in Table 1 that the pressure reduction rate is 20.16%, and the pressure reduction and injection-increasing effect is poor.

[0126] Comparative Example 5 is a comparative example different from Example 11. The difference is that the modified carboxylate surfactant used is replaced with sodium N,N-dialkylethylenediaminedibenzoate with the same weight. It can be seen from the data in Table 1 that the pressure reduction rate is 32.06%, and the pressure reduction and injection-increasing effect is poor.

[0127] Comparative Example 6 is a pressure reduction and injection-increasing surfactant prepared using the raw materials and methods of Example 1 in Publication No. CN117903774A. It can be seen from the data in Table 1 that the pressure reduction rate is 36.12%, and the pressure reduction and injection-increasing effect is poor.

[0128] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. However, for those of ordinary skill in the art, without departing from the scope of the technical solution of the present invention, any equivalent changes such as slight modifications, decorations, and evolutions made using the above-disclosed technical content are 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 still fall 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, naphtho[1,2-c]furan-1,3-dione, and catalyst aluminum chloride are added to a 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 dropwise add 12-bromo-1-dodecene ethanol solution, react for 6-10 hours, and adjust the pH to 7, 7.5 or 8 with NaOH solution to obtain sodium 1-(dodec-11-ene-1-yl (pentyl)carbamoyl)-2-naphthoate, which is a carboxylate surfactant; In step S1, the feed mass ratio of DMSO, n-hexylamine, naphtho[1,2-c]furan-1,3-dione, and catalyst aluminum chloride is 30:(1-3):(5-7):(0.2-0.6); 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).

2. 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: DMF is added to the reactor, stirred, and heated to 95-105°C, and the 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 are added in sequence, and the reaction is carried out for 3-4 hours under nitrogen protection to obtain a modified carboxylate surfactant; The number average molecular weight of the modified carboxylate surfactant is 9000-13000; In step S3, the mass ratio of deionized water, hexamethylenetetramine, p-aminophenol and glacial acetic acid is 10:2.5:(1.0-1.2):(0.8-1.0); 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).

3. An oil recovery aid according to claim 1 or 2, 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.

4. A method for preparing the oil recovery additive according to claim 1, characterized in that: The following steps are involved: (1) Weigh the following by weight: carboxylate surfactant, nonionic surfactant, cosolvent, stabilizer, antiscalant, and deionized water; (2) Add deionized water, carboxylate surfactant, nonionic surfactant, cosolvent, stabilizer and antiscalant into the reactor in sequence, stir, raise the temperature to 30-50°C, and keep the temperature for 3-5 hours to obtain the oil recovery additive.

5. A method for preparing the oil recovery aid according to claim 2, characterized in that: The following steps are involved: (1) Weigh the following by weight: modified carboxylate surfactant, nonionic surfactant, cosolvent, stabilizer, antiscalant, and deionized water; (2) Add deionized water, modified carboxylate surfactant, nonionic surfactant, cosolvent, stabilizer and antiscalant into the reactor in sequence, stir, raise the temperature to 30-50°C, and keep the temperature for 3-5 hours to obtain the oil recovery additive.

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