Hybrid modified multi-dimensional oil displacement agent and preparation method thereof

Abstract

The present application relates to a kind of oil displacement agent, in particular to a kind of hybrid modified multi-dimensional biological oil displacement agent and its preparation method.The hybrid polymeric biological surfactant of the present application is the product of esterification reaction of biological surfactant and polycarboxylic compound;The biological surfactant is at least one of lipopeptide, sophorolipid, rhamnolipid, sophorolipid modified derivative and rhamnolipid modified derivative;The polycarboxylic compound is at least one of oxalic acid, 1,3-propane dicarboxylic acid, butane tetracarboxylic acid, 1,3-butane dicarboxylic acid and polycarboxylic compound containing saturated alkyl chain with 18 carbon atoms or less between two carboxyl groups.The oil displacement agent provided by the present application has excellent temperature resistance, salt resistance, oil washing efficiency and imbibition oil displacement capacity.In particular, the oil displacement agent can be applied to extreme low permeability reservoir environment below 200 DEG C and below 200 g / L of salinity, and still maintain good chemical stability and interfacial activity under such harsh conditions.

Description

Technical Field

[0001] This invention relates to an oil displacement agent, and more particularly to a hybrid modified multidimensional biological oil displacement agent and its preparation method. Background Technology

[0002] Chemical flooding is one of the important technical means to improve crude oil recovery. Among them, surfactant flooding is currently the most widely used chemical flooding technology.

[0003] Surfactant flooding improves oil washing efficiency by reducing oil-water interfacial tension and emulsifying crude oil. Biosurfactants, due to their unique molecular structure, possess excellent interfacial activity, significantly reducing oil-water interfacial tension. Simultaneously, their superior emulsifying ability effectively drives residual oil in the formation, improving micro-level oil washing efficiency. Compared to traditional chemical surfactants, biosurfactants also possess environmentally friendly characteristics such as non-toxicity and easy biodegradability, showing promising application prospects in oilfield development. However, they still face the following two challenges: First, as oilfields enter the ultra-high water-cut development stage, the contradictions such as oil viscosity and reservoir heterogeneity become increasingly prominent, placing higher demands on the performance of oil displacement agents. However, using only one or a small amount of biosurfactants in combination is insufficient to effectively address the multiple technical challenges in complex reservoir development. Second, in recent years, the application of enhanced oil recovery technologies has gradually shifted towards reservoir conditions with higher temperatures, higher salinity, and lower permeability, urgently requiring the development of biosurfactants with superior performance.

[0004] In summary, the existing technology lacks a biosurfactant with temperature and salt resistance, making it difficult to meet the needs of efficient development of complex reservoirs with medium to low permeability, high temperature and high salt content. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a hybrid modified multidimensional bio-oil displacement agent that is resistant to temperature and salt and has high percolation oil displacement efficiency.

[0006] This invention provides a hybrid polybiosurfactant, wherein the hybrid polybiosurfactant is the product of an esterification reaction between a biosurfactant and a polycarboxylic acid compound; the biosurfactant is at least one of lipopeptides, sophorolipids, rhamnolipids, modified sophorolipid derivatives, and modified rhamnolipid derivatives; the polycarboxylic acid compound is at least one of oxalic acid, 1,3-propanedicarboxylic acid, butanetetracarboxylic acid, 1,3-butanedicarboxylic acid, and polycarboxylic acid compounds containing a saturated alkyl chain with fewer than 18 carbon atoms between the carboxyl groups at both ends.

[0007] This invention differs from conventional polymer flooding agents and small-molecule surfactant flooding agents; its molecules, after esterification, exhibit significant steric hindrance, resulting in a molecular configuration with a multidimensional structure and variable chain lengths. This molecular configuration facilitates multidimensional oil displacement. The flooding agent overcomes the shortcomings of both polymer flooding and small-molecule surfactant flooding, significantly reducing oil-water interfacial tension and capillary forces, achieving highly efficient crude oil stripping. This invention has significant practical implications and substantial economic value for improving the development efficiency of low-to-medium permeability reservoirs.

[0008] Furthermore, the sophorolipid modified derivative is at least one of the following: a nonionic modified derivative of sophorolipid, anionic modified derivative of sophorolipid, cationic modified derivative of sophorolipid, and zwitterionic modified derivative of sophorolipid; the rhamnolipid modified derivative is at least one of the following: a nonionic modified derivative of rhamnolipid, anionic modified derivative of rhamnolipid, cationic modified derivative of rhamnolipid, and zwitterionic modified derivative of rhamnolipid.

[0009] Furthermore, the chemical structural formula of the sophorolipid nonionic modified derivative is shown in general formula I or general formula II below; General Formula I General Formula II The chemical structural formula of the sophorolipid anionic modified derivative is shown in general formula III or general formula IV below; General Formula III General Formula IV The chemical structural formula of the cationic modified sophorolipid derivative is shown in general formula V below; Formula V The chemical structural formula of the zwitterionic modified sophorolipid derivative is shown in the following general formula VI; Formula VI The chemical structural formula of the nonionic modified rhamnolipin derivative is shown in general formula VII or general formula VIII below; Formula VII Formula VIII The chemical structural formula of the rhamnolipin anionic modified derivative is shown in general formula IX or general formula X below; Formula IX Formula X The chemical structural formula of the rhamnolipin cationic modified derivative is shown in the following general formula XI; General Formula XI The chemical structural formula of the zwitterionic modified rhamnolipin derivative is shown in the following general formula XII. Formula XII In the above general formulas, R1, R2, and R3 are each independently selected from hydrogen atoms, and C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 Saturated chain alkyl, phenyl, benzoyl, naphthyl, halophenyl, methyl formate, ethyl formate, methoxyphenyl, nitrophenyl, methylphenyl, C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 Unsaturated chain alkyl groups, C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 Saturated cyclic alkyl groups; R4 is selected from C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 Saturated chain alkyl groups, C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 Unsaturated chain alkyl; X is selected from halogens; Y is selected from hydrogen atoms, halogens, hydroxyl groups, and methoxy groups.

[0010] Another objective of this invention is to provide a method for preparing the above-mentioned hybrid polybiosurfactant, wherein the method comprises: passing a biosurfactant and a polycarboxylic compound through a cation exchange resin-filled column to carry out an esterification reaction to obtain a hybrid polybiosurfactant; or catalytically esterifying a biosurfactant and a polycarboxylic compound to obtain a hybrid polybiosurfactant.

[0011] Further, the mass ratio of the biosurfactant to the polycarboxylic compound is 3-10:1; the catalyst is at least one of dicyclohexylcarbodiimide and 4-dimethylaminopyridine, and the amount of catalyst used is 0.1-5% of the total mass of the biosurfactant and the polycarboxylic compound.

[0012] Another object of the present invention is to provide a hybrid modified multidimensional bio-displacement agent, said oil displacement agent comprising the following components by mass percentage: The above-mentioned hybrid polymeric biosurfactants account for 1-75%; Reinforcing agent 0.2-20%; Water balance.

[0013] Furthermore, the reinforcing agent is at least one of sodium olefin sulfonate, tetradecyltrimethylammonium bromide, and cocamidopropyl betaine.

[0014] Another objective of this invention is to provide a method for preparing the above-mentioned hybrid modified multidimensional bio-oil displacement agent. The method comprises: passing a biosurfactant and a polycarboxylic acid compound through a cation exchange resin-filled column to perform an esterification reaction to obtain a hybrid polybiosurfactant; adding a reinforcing agent, mixing well, and evaporating some water to obtain the hybrid modified multidimensional bio-oil displacement agent; or catalytically esterifying a biosurfactant and a polycarboxylic acid compound to obtain a hybrid polybiosurfactant; adding a reinforcing agent, mixing well, and evaporating some water to obtain the hybrid modified multidimensional bio-oil displacement agent.

[0015] Further, the mass ratio of the biosurfactant to the polycarboxylic compound is 3-10:1; the catalyst is at least one of dicyclohexylcarbodiimide and 4-dimethylaminopyridine, and the amount of catalyst used is 0.1-5% of the total mass of the biosurfactant and the polycarboxylic compound.

[0016] The beneficial effects of this invention are as follows: The oil displacement agent provided by this invention has excellent temperature and salt resistance, oil washing efficiency, and percolation displacement ability. Specifically, this oil displacement agent is suitable for extremely low-permeability reservoir environments below 200°C and with a salinity below 200 g / L, and can still maintain good chemical stability and interfacial activity under such harsh conditions. Attached Figure Description

[0017] This invention appendix Figure 3 width, Figure 1 A comparison of the effects of tap water before and after oil displacement in an oil displacement effect test; Figure 2 A comparison of the effects of the oil displacement agent prepared in Comparative Example 1 before and after oil displacement in the test of the oil displacement effect by permeation; Figure 3 A comparison diagram of the effects of the oil displacement agent prepared in Example 3 before and after oil displacement in the test of the oil displacement effect; in: Figure 1 Image a shows the effect before using tap water to displace oil. Figure 1 b is the effect diagram after oil removal using tap water. Figure 2 a is a diagram showing the effect of the oil displacement agent prepared in Comparative Example 1 before oil displacement. Figure 2 b is a diagram showing the effect of the oil displacement agent prepared in Comparative Example 1 after oil displacement. Figure 3 a is an image showing the effect of the oil displacement agent prepared in Example 3 before oil displacement. Figure 3 b is a diagram showing the effect of the oil displacement agent prepared in Example 3 after oil displacement. Detailed Implementation

[0018] The following non-limiting embodiments are intended to enable those skilled in the art to more fully understand the invention, but do not limit the invention in any way.

[0019] The following lipopeptide biosurfactants are abbreviated as LPT; The following sophorolipid biosurfactant is abbreviated as SPP; The following rhamnolipid biosurfactants are abbreviated as RNP; The following nonionic modified derivatives of sophorolipids (general formula I) are abbreviated as SPP-R; The following nonionic modified derivatives of sophorolipids (general formula II) are abbreviated as SPP-NR; The following anionic modified derivative of sophorolipid (general formula III) is abbreviated as SPP-1A; The following anionic modified derivative of sophorolipid (general formula IV) is abbreviated as SPP-2A; The following cationic modified derivatives of sophorolipids (general formula V) are abbreviated as SPP-C; The following zwitterionic modified derivatives of sophorolipids (general formula VI) are abbreviated as SPP-Z; The following nonionic modified rhamnolipin derivatives (general formula VII) are abbreviated as RNP-R; The following nonionic modified rhamnolipin derivatives (general formula VIII) are abbreviated as RNP-NR; The following rhamnolipid anionic modified derivatives (general formula IX) are abbreviated as RNP-1A; The following rhamnolipid anionic modified derivatives (general formula X) are abbreviated as RNP-2A; The following cationic modified derivatives of rhamnolipin (general formula XI) are abbreviated as RNP-C; The following zwitterionic modified derivatives of rhamnolipin (general formula XII) are abbreviated as RNP-Z.

[0020] The preparation method of the hybrid modified multidimensional bio-oil flooding agent is as follows: A biosurfactant and a polycarboxylic acid compound are passed through a cation exchange resin packed column at 20-100℃, with each milliliter of solution passing through the cation exchange resin packed column for 10-1200 s to carry out an esterification reaction, resulting in a hybrid polybiosurfactant. An enhancing agent is then added, the mixture is homogenized, and some water is evaporated to obtain the hybrid modified multidimensional bio-oil flooding agent. Alternatively, a biosurfactant and a polycarboxylic acid compound are reacted at 50-150℃ for 2-48 h under the action of a catalyst to obtain a hybrid polybiosurfactant. An enhancing agent is then added, the mixture is homogenized, and some water is evaporated to obtain the hybrid modified multidimensional bio-oil flooding agent.

[0021] Example 1 Method 1: Combine 15g SPP, 15g RNP, 10g SPP-R (R1 selected from H, R2 selected from methyl), 10g SPP-NR (R1 selected from H, R2 selected from n-propyl, Y selected from Cl), 10g SPP-C (R1 selected from methyl, R2 selected from n-butyl, R3 selected from methyl, R4 selected from -CH2-, X selected from Cl), 5g RNP-R (R1 selected from H, R2 selected from methyl), 5g RNP-NR (R1 selected from H, R2 selected from methyl, Y selected from Cl), 5g RNP-C (R1 selected from H, R2 selected from methyl, R3 selected from n-propyl, X selected from Cl), 3g 1,3-propanedicarboxylic acid, 3g butanetetracarboxylic acid, 5g 1,8,18-octadecanetricarboxylic acid, 5g 1,4-butanedicarboxylic acid, 5g 1,18-octadecanedicarboxylic acid, 4g... 1,4,8,12-dodecanetetracarboxylic acid and 300 mL of water were mixed to obtain a solution, which was then passed through a cation exchange resin packed with sulfonic acid groups (-SO3H) at 20 °C. The time for each mL of solution to pass through the cation exchange resin packed column was 10 s. Then, 0.1 g of olefinic sodium sulfonate and 0.2 g of tetradecyltrimethylammonium bromide were added, mixed, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil flooding agent.

[0022] Method 2: Combine 15g SPP, 15g RNP, 10g SPP-R (R1 selected from H, R2 selected from methyl), 10g SPP-NR (R1 selected from H, R2 selected from n-propyl, Y selected from Cl), 10g SPP-C (R1 selected from methyl, R2 selected from n-butyl, R3 selected from methyl, R4 selected from -CH2-, X selected from Cl), 5g RNP-R (R1 selected from H, R2 selected from methyl), 5g RNP-NR (R1 selected from H, R2 selected from methyl, Y selected from Cl), 5g RNP-C (R1 selected from H, R2 selected from methyl, R3 selected from n-propyl, X selected from Cl), 3g 1,3-propanedicarboxylic acid, 3g butanetetracarboxylic acid, 5g 1,8,18-octadecanetricarboxylic acid, 5g 1,4-butanedicarboxylic acid, 5g 1,18-octadecanedicarboxylic acid, 4g... 1,4,8,12-dodecanetetracarboxylic acid, 300 mL of water, and 2 g of DCC were stirred at 50 °C for 2 h to catalyze esterification. Then, 0.1 g of sodium olefin sulfonate and 0.2 g of tetradecyltrimethylammonium bromide were added, mixed well, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil displacement agent.

[0023] Example 2 Method 1: Combine 20g RNP, 20g SPP-R (R1 selected from methyl, R2 selected from n-octadecyl), 10g SPP-NR (R1 selected from methyl, R2 selected from n-octadecyl, Y selected from H), 10g SPP-2A (R1 selected from methyl, R2 selected from n-octadecyl), 10g RNP-R (R1 selected from methyl, R2 selected from n-octadecyl), 15g RNP-NR (R1 selected from methyl, R2 selected from n-octadecyl, Y selected from H), 15g RNP-2A (R1 selected from n-hexadecyl), 5g 1,8,18-octadecanetricarboxylic acid, 5g 1,4-butanedicarboxylic acid, 5g 1,8,18-octadecanetricarboxylic acid, and 10g... 1,4,8,12-dodecanetetracarboxylic acid and 330 mL of water were mixed to obtain a solution, which was then passed through a cation exchange resin packed with sulfonic acid groups (-SO3H) at 40 °C. The time for each mL of solution to pass through the cation exchange resin packed column was 50 s. Then, 1 g of olefin sulfonate sodium and 1 g of tetradecyltrimethylammonium bromide were added, mixed, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil flooding agent.

[0024] Method 2: Combine 20g RNP, 20g SPP-R (R1 selected from methyl, R2 selected from n-octadecyl), 10g SPP-NR (R1 selected from methyl, R2 selected from n-octadecyl, Y selected from H), 10g SPP-2A (R1 selected from methyl, R2 selected from n-octadecyl), 10g RNP-R (R1 selected from methyl, R2 selected from n-octadecyl), 15g RNP-NR (R1 selected from methyl, R2 selected from n-octadecyl, Y selected from H), 15g RNP-2A (R1 selected from n-hexadecyl), 5g 1,8,18-octadecanetricarboxylic acid, 5g 1,4-butanedicarboxylic acid, 5g 1,8,18-octadecanetricarboxylic acid, 10g 1,4,8,12-dodecanetetracarboxylic acid, 330mL water, and 3g... DCC was stirred and catalyzed for esterification at 75°C for 4 hours. Then, 1g of sodium olefin sulfonate and 1g of tetradecyltrimethylammonium bromide were added, mixed well, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil displacement agent.

[0025] Example 3 Method 1: Combine 15g SPP, 15g RNP, 15g SPP-R (R1 selected from n-hexyl, R2 selected from benzoyl), 20g SPP-1A (R1 selected from n-propyl, R2 selected from n-propyl, R3 selected from phenyl), 20g SPP-2A (R1 selected from H, R2 selected from ethyl), 20g RNP-R (R1 selected from methyl formate, R2 selected from nitrophenyl), 10g RNP-1A (R1 selected from n-decyl), 10g RNP-2A (R1 selected from n-decyl), 5g butanetetracarboxylic acid, 10g 1,8,18-octadecanetricarboxylic acid, and 10g... A solution was prepared by mixing 1,4-butanedicarboxylic acid and 360 mL of water. The solution was then passed through a cation exchange resin column containing sulfonic acid groups (-SO3H) at 60 °C. The time for each mL of solution to pass through the cation exchange resin column was 100 s. Then, 4 g of sodium olefin sulfonate, 3 g of cocamidopropyl betaine, and 3 g of tetradecyltrimethylammonium bromide were added and mixed. Part of the water was evaporated to make the water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil flooding agent.

[0026] Method 2: Combine 15g SPP, 15g RNP, 15g SPP-R (R1 selected from n-hexyl, R2 selected from benzoyl), 20g SPP-1A (R1 selected from n-propyl, R2 selected from n-propyl, R3 selected from phenyl), 20g SPP-2A (R1 selected from H, R2 selected from ethyl), 20g RNP-R (R1 selected from methyl formate, R2 selected from nitrophenyl), 10g RNP-1A (R1 selected from n-decyl), 10g RNP-2A (R1 selected from n-decyl), 5g butanetetracarboxylic acid, 10g 1,8,18-octadecanetricarboxylic acid, 10g 1,4-butanedicarboxylic acid, 360mL water, 6g DCC, and 1g... DMAP was stirred and catalyzed for esterification at 100℃ for 8 hours. Then, 4g of sodium olefin sulfonate, 3g of cocamidopropyl betaine, and 3g of tetradecyltrimethylammonium bromide were added, mixed well, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil displacement agent.

[0027] Example 4 Method 1: Combine 25g RNP, 25g SPP-1A (R1 selected from isopentyl, R2 from isopentyl, R3 from phenyl), 15g SPP-2A (R1 selected from H, R2 from n-decyl), 25g SPP-Z (R1 selected from n-hexadecyl, R2 from 15-hexadecenyl, R4 from -(CH2)8-), 20g RNP-1A (R1 selected from 4-pentenyl), 20g RNP-2A (R1 selected from 4-pentenyl), 20g RNP-Z (R1 selected from n-hexadecyl, R2 from 15-hexadecenyl, R4 from -(CH2)8-), 8g butanetetracarboxylic acid, 8g 1,8,18-octadecanetricarboxylic acid, and 9g... 1,4,8,12-dodecanetetracarboxylic acid and 390 mL of water were mixed to obtain a solution, which was then passed through a cation exchange resin packed with sulfonic acid groups (-SO3H) at 80 °C. The time for each milliliter of solution to pass through the cation exchange resin packed column was 200 s. Then, 30 g of tetradecyltrimethylammonium bromide was added, mixed, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil flooding agent.

[0028] Method 2: Combine 25g RNP, 25g SPP-1A (R1 selected from isopentyl, R2 from isopentyl, R3 from phenyl), 15g SPP-2A (R1 selected from H, R2 from n-decyl), 25g SPP-Z (R1 selected from n-hexadecyl, R2 from 15-hexadecenyl, R4 from -(CH2)8-), 20g RNP-1A (R1 selected from 4-pentenyl), 20g RNP-2A (R1 selected from 4-pentenyl), 20g RNP-Z (R1 selected from n-hexadecyl, R2 from 15-hexadecenyl, R4 from -(CH2)8-), 8g butanetetracarboxylic acid, 8g 1,8,18-octadecanetricarboxylic acid, 9g 1,4,8,12-dodecanetetracarboxylic acid, 390mL water, 5g DCC, and 3g... DMAP was stirred and catalyzed for esterification at 125°C for 12 hours. Then, 30g of tetradecyltrimethylammonium bromide was added, mixed well, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil displacement agent.

[0029] Example 5 Method 1: Mix 35g RNP, 25g SPP-1A (R1 selected from H, R2 selected from n-pentyl, R3 selected from naphthyl), 25g SPP-2A (R1 selected from ethyl, R2 selected from n-pentyl), and 25g SPP-Z (R1 selected from phenyl, R2 selected from 12-hexadecenyl, R4 selected from -(CH2)). 18 -), 30g RNP-1A (R1 selected from p-methoxyphenyl), 5g RNP-2A (R1 selected from n-octyl), 30g RNP-Z (R1 selected from H, R2 selected from chlorophenyl, R4 selected from -(CH2)). 18- 5g butanetetracarboxylic acid, 5g 1,8,12,18-octadecanetetracarboxylic acid, 5g 1,9,18-octadecanetricarboxylic acid, 10g 1,12-dodecanedicarboxylic acid, and 420mL of water were mixed to obtain a solution. The solution was then passed through a cation exchange resin column containing sulfonic acid groups (-SO3H) at 100℃. The time for each milliliter of solution to pass through the cation exchange resin column was 400s. Then, 60g of olefinic sodium sulfonate was added, mixed, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil flooding agent.

[0030] Method 2: Mix 35g RNP, 25g SPP-1A (R1 selected from H, R2 selected from n-pentyl, R3 selected from naphthyl), 25g SPP-2A (R1 selected from ethyl, R2 selected from n-pentyl), and 25g SPP-Z (R1 selected from phenyl, R2 selected from 12-hexadecenyl, R4 selected from -(CH2)). 18 -), 30g RNP-1A (R1 selected from p-methoxyphenyl), 5g RNP-2A (R1 selected from n-octyl), 30g RNP-Z (R1 selected from H, R2 selected from chlorophenyl, R4 selected from -(CH2)). 18 1) 5g butanetetracarboxylic acid, 5g 1,8,12,18-octadecanetetracarboxylic acid, 5g 1,9,18-octadecanetricarboxylic acid, 10g 1,12-dodecanedicarboxylic acid, 420mL water, 2g DCC, and 5g DMAP were stirred at 150℃ for 20h to catalyze esterification. Then, 60g of olefin sulfonate sodium was added, mixed well, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil displacement agent.

[0031] Example 6 Method 1: Combine 40g SPP-2A (R1 selected from methyl, R2 selected from n-hexadecyl), 40g SPP-C (R1 selected from benzoyl, R2 selected from n-pentyl, R3 selected from H, R4 selected from n-pentyl, X selected from Cl), 40g SPP-Z (R1 selected from 2-propenyl, R2 selected from methyl formate, R4 selected from -CH=CH-(CH2)7-), 35g RNP-R (R1 selected from methyl formate, R2 selected from n-hexadecyl), 35g RNP-C (R1 selected from n-hexadecyl, R2 selected from 6-heptenyl, R3 selected from 15-hexadecenyl, X selected from F), and 10g RNP-Z (R1 selected from 15-hexadecenyl, R2 selected from n-hexyl, R4 selected from -CH=CH-(CH2)). 18- 4g of 1,10-decanedicarboxylic acid, 5g of 1,8,12,18-octadecanetetracarboxylic acid, 8g of 1,12-dodecanedicarboxylic acid, 8g of 1,6,12-dodecanetricarboxylic acid, and 450mL of water were mixed to obtain a solution. The solution was then passed through a cation exchange resin column containing sulfonic acid groups (-SO3H) at 100℃, with each milliliter of solution passing through the cation exchange resin column for 800s. Then, 40g of sodium olefin sulfonate, 30g of cocamidopropyl betaine, and 30g of tetradecyltrimethylammonium bromide were added, mixed, and some water was evaporated to make water account for 50% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil flooding agent.

[0032] Method 2: Combine 40g SPP-2A (R1 selected from methyl, R2 selected from n-hexadecyl), 40g SPP-C (R1 selected from benzoyl, R2 selected from n-pentyl, R3 selected from H, R4 selected from n-pentyl, X selected from Cl), 40g SPP-Z (R1 selected from 2-propenyl, R2 selected from methyl formate, R4 selected from -CH=CH-(CH2)7-), 35g RNP-R (R1 selected from methyl formate, R2 selected from n-hexadecyl), 35g RNP-C (R1 selected from n-hexadecyl, R2 selected from 6-heptenyl, R3 selected from 15-hexadecenyl, X selected from F), and 10g RNP-Z (R1 selected from 15-hexadecenyl, R2 selected from n-hexyl, R4 selected from -CH=CH-(CH2)). 18 - 4g 1,10-decanedicarboxylic acid, 5g 1,8,12,18-octadecanetetracarboxylic acid, 8g 1,12-dodecanedicarboxylic acid, 8g 1,6,12-dodecanetricarboxylic acid, 450mL water, 4g DCC, and 3g DMAP were stirred at 150℃ for 32h to catalyze esterification. Then, 40g sodium olefin sulfonate, 30g cocamidopropyl betaine, and 30g tetradecyltrimethylammonium bromide were added, mixed well, and some water was evaporated to make water account for 50% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil flooding agent.

[0033] Example 7 Method 1: Combine 15g LPT, 35g SPP-R (R1 selected from ethyl, R2 selected from naphthyl), 45g SPP-1A (R1 selected from isopropyl, R2 selected from n-propyl, R3 selected from H), and 35g SPP-Z (R1 selected from 11-dodecenyl, R2 selected from naphthyl, R4 selected from -CH=CH-(CH2)). 13 -), 25g RNP-1A (R1 selected from ethyl), 5g RNP-2A (R1 selected from 11-dodecenyl), 45g RNP-Z (R1 selected from 11-dodecenyl, R2 selected from H, R4 selected from -CH=CH-(CH2)). 13- 8g of 1,5,10-decanetricarboxylic acid, 8g of 1,9,18-octadecanetricarboxylic acid, 3g of 1,12-dodecanedicarboxylic acid, 6g of 1,8,12,18-octadecanetetracarboxylic acid, and 480mL of water were mixed to obtain a solution. The solution was then passed through a cation exchange resin column containing sulfonic acid groups (-SO3H) at 80℃. The time for each milliliter of solution to pass through the cation exchange resin column was 1200s. Then, 30g of olefin sulfonate sodium, 25g of cocamidopropyl betaine, and 25g of tetradecyltrimethylammonium bromide were added, mixed, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil flooding agent.

[0034] Method 2: Combine 15g LPT, 35g SPP-R (R1 selected from ethyl, R2 selected from naphthyl), 45g SPP-1A (R1 selected from isopropyl, R2 selected from n-propyl, R3 selected from H), and 35g SPP-Z (R1 selected from 11-dodecenyl, R2 selected from naphthyl, R4 selected from -CH=CH-(CH2)). 13 -), 25g RNP-1A (R1 selected from ethyl), 5g RNP-2A (R1 selected from 11-dodecenyl), 45g RNP-Z (R1 selected from 11-dodecenyl, R2 selected from H, R4 selected from -CH=CH-(CH2)). 13 - 8g of 1,5,10-decanetricarboxylic acid, 8g of 1,9,18-octadecanetricarboxylic acid, 3g of 1,12-dodecanedicarboxylic acid, 6g of 1,8,12,18-octadecanetetracarboxylic acid, 480mL of water, 5g of DCC, and 10g of DMAP were stirred at 125℃ for 48h to catalyze esterification. Then, 30g of sodium olefin sulfonate, 25g of cocamidopropyl betaine, and 25g of tetradecyltrimethylammonium bromide were added, mixed well, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil displacement agent.

[0035] Example 8 Method 1: Combine 75g LPT, 75g SPP-R (R1 selected from p-methylphenyl, R2 selected from 4-hexenyl), 15g SPP-NR (R1 selected from 4-hexenyl, R2 selected from n-dodecyl, Y selected from -OH), 15g SPP-C (R1 selected from methyl, R2 selected from methyl, R3 selected from H, R4 selected from n-pentyl, X selected from Br), 20g RNP-1A (R1 selected from n-tetrazyl), 15g RNP-C (R1 selected from p-methylphenyl, R2 selected from 4-hexenyl, R3 selected from n-dodecyl, X selected from Br), 35g RNP-Z (R1 selected from 4-hexenyl, R2 selected from n-dodecyl, R4 selected from -(CH2)9-), 10g 1,5,10-decanetricarboxylic acid, 10g 1,9,18-octadecanetricarboxylic acid, and 5g... A solution was prepared by mixing 1,6,12-dodecanetricarboxylic acid and 510 mL of water. The solution was then passed through a cation exchange resin column containing sulfonic acid groups (-SO3H) at 60 °C. The time for each mL of solution to pass through the cation exchange resin column was 1200 s. 40 g of cocamidopropyl betaine and 40 g of tetradecyltrimethylammonium bromide were then added and mixed. Some of the water was evaporated to make the water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil flooding agent.

[0036] Method 2: Combine 75g LPT, 75g SPP-R (R1 selected from p-methylphenyl, R2 selected from 4-hexenyl), 15g SPP-NR (R1 selected from 4-hexenyl, R2 selected from n-dodecyl, Y selected from -OH), 15g SPP-C (R1 selected from methyl, R2 selected from methyl, R3 selected from H, R4 selected from n-pentyl, X selected from Br), 20g RNP-1A (R1 selected from n-tetrazyl), 15g RNP-C (R1 selected from p-methylphenyl, R2 selected from 4-hexenyl, R3 selected from n-dodecyl, X selected from Br), 35g RNP-Z (R1 selected from 4-hexenyl, R2 selected from n-dodecyl, R4 selected from -(CH2)9-), 10g 1,5,10-decanetricarboxylic acid, 10g 1,9,18-octadecanetricarboxylic acid, 5g 1,6,12-dodecanetricarboxylic acid, 510mL water, and 10g... DMAP was stirred and catalyzed for esterification at 100℃ for 48 hours. Then, 40g of cocamidopropyl betaine and 40g of tetradecyltrimethylammonium bromide were added, mixed well, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil displacement agent.

[0037] Example 9 Method 1: Combine 35g LPT, 35g RNP, 35g SPP-R (R1 selected from methyl, R2 selected from n-tetradecyl), 55g SPP-NR (R1 selected from n-tetradecyl, R2 selected from n-tetradecyl, Y selected from methoxy), 45g RNP-C (R1 selected from methyl, R2 selected from ethyl acetate, R3 selected from n-tetradecyl, X selected from I), 45g RNP-Z (R1 selected from n-octadecyl, R2 selected from methyl, R4 selected from -CH=CH-(CH2)9-), 5g 1,5,10-decanetricarboxylic acid, 5g 1,9,18-octadecanetricarboxylic acid, and 10g... A solution was prepared by mixing 1,6,12-dodecanetricarboxylic acid, 5g butanetetracarboxylic acid, and 510mL of water. The solution was then passed through a cation exchange resin column containing sulfonic acid groups (-SO3H) at 40℃. The time for each milliliter of solution to pass through the cation exchange resin column was 800s. 25g of cocamidopropyl betaine and 35g of tetradecyltrimethylammonium bromide were then added and mixed. Some of the water was evaporated to make the water content 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil flooding agent.

[0038] Method 2: Combine 35g LPT, 35g RNP, 35g SPP-R (R1 selected from methyl, R2 selected from n-tetradecyl), 55g SPP-NR (R1 selected from n-tetradecyl, R2 selected from n-tetradecyl, Y selected from methoxy), 45g RNP-C (R1 selected from methyl, R2 selected from ethyl acetate, R3 selected from n-tetradecyl, X selected from I), 45g RNP-Z (R1 selected from n-octadecyl, R2 selected from methyl, R4 selected from -CH=CH-(CH2)9-), 5g 1,5,10-decanetricarboxylic acid, 5g 1,9,18-octadecanetricarboxylic acid, 10g 1,6,12-dodecanetricarboxylic acid, 5g butanetetracarboxylic acid, 510mL water, and 6g... DMAP was stirred and catalyzed for esterification at 75°C for 32 hours. Then, 25g of cocamidopropyl betaine and 35g of tetradecyltrimethylammonium bromide were added, mixed well, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil displacement agent.

[0039] Example 10 Method 1: Combine 55g LPT, 35g SPP-R (R1 selected from 6-heptenyl, R2 selected from n-dodecyl), 35g SPP-NR (R1 selected from n-dodecyl, R2 selected from methyl, Y selected from F), 35g SPP-C (R1 selected from methyl, R2 selected from H, R3 selected from H, R4 selected from n-dodecyl, X selected from F), 25g SPP-Z (R1 selected from 12-hexadecenyl, R2 selected from methyl, R4 selected from -(CH2)6-), 25g RNP-1A (R1 selected from 12-hexadecenyl), 25g RNP-Z (R1 selected from 6-heptenyl, R2 selected from 12-hexadecenyl, R4 selected from -CH=CH-(CH2)6-), 8g 1,10-decanedicarboxylic acid, 8g 1,9,18-octadecanetricarboxylic acid, and 4g... A solution was prepared by mixing 1,12-dodecanedicarboxylic acid, 5g butanetetracarboxylic acid, and 480mL of water. The solution was then passed through a cation exchange resin column containing sulfonic acid groups (-SO3H) at 20℃. The time for each milliliter of solution to pass through the cation exchange resin column was 400s. Then, 20g of olefin sulfonate sodium and 20g of tetradecyltrimethylammonium bromide were added, mixed, and some water was evaporated to make water account for 30% of the total weight. This yielded the hybrid modified multidimensional bio-oil flooding agent.

[0040] Method 2: Combine 55g LPT, 35g SPP-R (R1 selected from 6-heptenyl, R2 selected from n-dodecyl), 35g SPP-NR (R1 selected from n-dodecyl, R2 selected from methyl, Y selected from F), 35g SPP-C (R1 selected from methyl, R2 selected from H, R3 selected from H, R4 selected from n-dodecyl, X selected from F), 25g SPP-Z (R1 selected from 12-hexadecenyl, R2 selected from methyl, R4 selected from -(CH2)6-), 25g RNP-1A (R1 selected from 12-hexadecenyl), 25g RNP-Z (R1 selected from 6-heptenyl, R2 selected from 12-hexadecenyl, R4 selected from -CH=CH-(CH2)6-), 8g 1,10-decanedicarboxylic acid, 8g 1,9,18-octadecanetricarboxylic acid, 4g 1,12-dodecanedicarboxylic acid, 5g butanetetracarboxylic acid, 480mL water, and 3g... DCC and 2g DMAP were stirred at 50℃ for 20h to catalyze esterification. Then, 20g sodium olefin sulfonate and 20g tetradecyltrimethylammonium bromide were added, mixed well, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil displacement agent.

[0041] Example 11 Method 1: Mix 35g RNP, 35g SPP-1A (R1 selected from n-propyl, R2 selected from n-propyl, R3 selected from H), and 35g SPP-Z (R1 selected from H, R2 selected from n-hexyl, R4 selected from -CH=CH-(CH2)). 10-), 30g RNP-1A (R1 selected from n-dodecyl), 30g RNP-2A (R1 selected from H), 35g RNP-Z (R1 selected from n-hexyl, R2 selected from n-hexyl, R4 selected from -(CH2)). 10 - 10g of 1,10-decanedicarboxylic acid, 10g of 1,9,18-octadecanetricarboxylic acid, 5g of 1,12-dodecanedicarboxylic acid, and 450mL of water were mixed to obtain a solution. The solution was then passed through a cation exchange resin column containing sulfonic acid groups (-SO3H) at 20℃. The time for each milliliter of solution to pass through the cation exchange resin column was 200s. Then, 5g of cocamidopropyl betaine and 15g of tetradecyltrimethylammonium bromide were added, mixed, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil flooding agent.

[0042] Method 2: Mix 35g RNP, 35g SPP-1A (R1 selected from n-propyl, R2 selected from n-propyl, R3 selected from H), and 35g SPP-Z (R1 selected from H, R2 selected from n-hexyl, R4 selected from -CH=CH-(CH2)). 10 -), 30g RNP-1A (R1 selected from n-dodecyl), 30g RNP-2A (R1 selected from H), 35g RNP-Z (R1 selected from n-hexyl, R2 selected from n-hexyl, R4 selected from -(CH2)). 10 - 10g of 1,10-decanedicarboxylic acid, 10g of 1,9,18-octadecanetricarboxylic acid, 5g of 1,12-dodecanedicarboxylic acid, 450mL of water, 1g of DCC, and 4g of DMAP were stirred at 150℃ for 12h to catalyze esterification. Then, 5g of cocamidopropyl betaine and 15g of tetradecyltrimethylammonium bromide were added, mixed well, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil displacement agent.

[0043] Example 12 Method 1: Combine 20g SPP, 35g SPP-1A (R1 selected from n-hexyl, R2 selected from n-hexyl, R3 selected from H), 35g SPP-2A (R1 selected from methyl, R2 selected from n-tetrazyl), 20g SPP-C (R1 selected from H, R2 selected from H, R3 selected from n-tetrazyl, R4 selected from n-dodecyl, X selected from F), 35g SPP-Z (R1 selected from n-tetradecyl, R2 selected from benzoyl, R4 selected from -(CH2)4-), 10g RNP-R (R1 selected from n-tetradecyl, R2 selected from n-tetradecyl), 10g RNP-NR (R1 selected from benzoyl, R2 selected from n-decyl, Y selected from I), 10g RNP-2A (R1 selected from n-tetradecyl), 10g 1,10-decanedicarboxylic acid, 10g 1,8,12,18-octadecanetetracarboxylic acid, and 5g... 1,12-Dodecanedicarboxylic acid and 420 mL of water were mixed to obtain a solution, which was then passed through a cation exchange resin packed with sulfonic acid groups (-SO3H) at 40 °C. The time for each milliliter of solution to pass through the cation exchange resin packed column was 100 s. Then, 10 g of olefin sulfonate sodium and 10 g of tetradecyltrimethylammonium bromide were added, mixed, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil flooding agent.

[0044] Method 2: Combine 20g SPP, 35g SPP-1A (R1 selected from n-hexyl, R2 selected from n-hexyl, R3 selected from H), 35g SPP-2A (R1 selected from methyl, R2 selected from n-tetrazyl), 20g SPP-C (R1 selected from H, R2 selected from H, R3 selected from n-tetrazyl, R4 selected from n-dodecyl, X selected from F), 35g SPP-Z (R1 selected from n-tetradecyl, R2 selected from benzoyl, R4 selected from -(CH2)4-), 10g RNP-R (R1 selected from n-tetradecyl, R2 selected from n-tetradecyl), 10g RNP-NR (R1 selected from benzoyl, R2 selected from n-decyl, Y selected from I), 10g RNP-2A (R1 selected from n-tetradecyl), 10g 1,10-decanedicarboxylic acid, 10g 1,8,12,18-octadecanetetracarboxylic acid, and 5g... 1,12-dodecanedicarboxylic acid, 420 mL of water, 6 g of DCC, and 8 g of DMAP were stirred at 125 °C for catalytic esterification for 8 h. Then, 10 g of sodium olefin sulfonate and 10 g of tetradecyltrimethylammonium bromide were added, mixed well, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil displacement agent.

[0045] Example 13 Method 1: Combine 25g LPT, 25g RNP, 25g SPP-R (R1 selected from 6-nonenyl, R2 selected from n-nonyl), 15g SPP-1A (R1 selected from n-hexyl, R2 selected from H, R3 selected from H), 15g SPP-2A (R1 selected from methyl, R2 selected from n-dodecyl), and 25g SPP-Z (R1 selected from n-nonyl, R2 selected from n-nonyl, R4 selected from -CH=CH-(CH2)). 15 -), 10g RNP-C (R1 selected from 6-nonenyl, R2 selected from 6-nonenyl, R3 selected from n-nonyl, X selected from F), 10g RNP-Z (R1 selected from n-nonyl, R2 selected from phenyl, R4 selected from -(CH2)). 14 - 5g of 1,10-decanedicarboxylic acid, 5g of 1,8,12,18-octadecanetetracarboxylic acid, 10g of 1,12-dodecanedicarboxylic acid, 5g of oxalic acid, and 390mL of water were mixed to obtain a solution. The solution was then passed through a cation exchange resin column containing sulfonic acid groups (-SO3H) at 60℃, with each milliliter of solution passing through the cation exchange resin column for 50 seconds. Then, 1g of cocamidopropyl betaine and 8g of tetradecyltrimethylammonium bromide were added, mixed, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil flooding agent.

[0046] Method 2: Combine 25g LPT, 25g RNP, 25g SPP-R (R1 selected from 6-nonenyl, R2 selected from n-nonyl), 15g SPP-1A (R1 selected from n-hexyl, R2 selected from H, R3 selected from H), 15g SPP-2A (R1 selected from methyl, R2 selected from n-dodecyl), and 25g SPP-Z (R1 selected from n-nonyl, R2 selected from n-nonyl, R4 selected from -CH=CH-(CH2)). 15 -), 10g RNP-C (R1 selected from 6-nonenyl, R2 selected from 6-nonenyl, R3 selected from n-nonyl, X selected from F), 10g RNP-Z (R1 selected from n-nonyl, R2 selected from phenyl, R4 selected from -(CH2)). 14 - 5g 1,10-decanedicarboxylic acid, 5g 1,8,12,18-octadecanetetracarboxylic acid, 10g 1,12-dodecanedicarboxylic acid, 5g oxalic acid, 390mL water, 1g DCC, and 3g DMAP were stirred at 100℃ for 4 hours to catalyze esterification. Then, 1g cocamidopropyl betaine and 8g tetradecyltrimethylammonium bromide were added, mixed well, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil displacement agent.

[0047] Example 14 Method 1: Mix 15g RNP, 15g SPP-NR (R1 selected from 8-hexadecenyl, R2 selected from 8-hexadecenyl, Y selected from Br), 15g SPP-C (R1 selected from n-hexadecyl, R2 selected from n-hexadecyl, R3 selected from H, R4 selected from n-hexadecyl, X selected from F), and 15g SPP-Z (R1 selected from n-octadecyl, R2 selected from n-octadecyl, R4 selected from -(CH2)). 10 25g RNP-R (R1 selected from n-tetradecyl, R2 selected from n-tetradecyl), 25g RNP-NR (R1 selected from 8-hexadecenyl, R2 selected from 8-hexadecenyl, Y selected from Br), 10g RNP-1A (R1 selected from n-octadecyl), 5g 1,2-propanedicarboxylic acid, 5g 1,10-decanedicarboxylic acid, 4g 1,8,12,18-octadecanetetracarboxylic acid, 6g 1,12-dodecanedicarboxylic acid, 5g oxalic acid, and 360mL of water were mixed to obtain a solution. The solution was passed through a cation exchange resin packed with sulfonic acid groups (-SO3H) at 80℃, with each milliliter of solution passing through the cation exchange resin packed column for 10s. Then, 2g of olefin sulfonate sodium and 2g of tetradecyltrimethylammonium bromide were added, mixed, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil flooding agent.

[0048] Method 2: Mix 15g RNP, 15g SPP-NR (R1 selected from 8-hexadecenyl, R2 selected from 8-hexadecenyl, Y selected from Br), 15g SPP-C (R1 selected from n-hexadecyl, R2 selected from n-hexadecyl, R3 selected from H, R4 selected from n-hexadecyl, X selected from F), and 15g SPP-Z (R1 selected from n-octadecyl, R2 selected from n-octadecyl, R4 selected from -(CH2)). 10 25g RNP-R (R1 selected from n-tetradecyl, R2 selected from n-tetradecyl), 25g RNP-NR (R1 selected from 8-hexadecenyl, R2 selected from 8-hexadecenyl, Y selected from Br), 10g RNP-1A (R1 selected from n-octadecyl), 5g 1,2-propanedicarboxylic acid, 5g 1,10-decanedicarboxylic acid, 4g 1,8,12,18-octadecanetetracarboxylic acid, 6g 1,12-dodecanedicarboxylic acid, 5g oxalic acid, 360mL water, 2g DCC, 7g DMAP. The mixture was stirred at 75℃ for 2 hours to catalyze esterification. Then, 2g sodium olefin sulfonate and 2g tetradecyltrimethylammonium bromide were added, mixed well, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil flooding agent.

[0049] Example 15 Method 1: Mix 25g RNP, 25g SPP-NR (R1 selected from H, R2 selected from n-octyl, Y selected from Cl), and 10g SPP-Z (R1 selected from n-octyl, R2 selected from ethyl acetate, R4 selected from -CH=CH-(CH2)). 11 10g RNP-R (R1 selected from H, R2 selected from n-octyl), 15g RNP-NR (R1 selected from H, R2 selected from ethyl acetate, Y selected from Cl), 15g RNP-1A (R1 selected from methyl), 3g 1,2-propanedicarboxylic acid, 3g 1,6-hexanedicarboxylic acid, 5g 1,8,12,18-octadecanetetracarboxylic acid, 9g 1,12-dodecanedicarboxylic acid, 5g oxalic acid, and 330mL water were mixed to obtain a solution. The solution was passed through a cation exchange resin column containing sulfonic acid groups (-SO3H) at 100℃, with each milliliter of solution passing through the cation exchange resin column for 100s. Then, 8g of olefin sulfonate sodium and 8g of tetradecyltrimethylammonium bromide were added, mixed, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil flooding agent.

[0050] Method 2: Mix 25g RNP, 25g SPP-NR (R1 selected from H, R2 selected from n-octyl, Y selected from Cl), and 10g SPP-Z (R1 selected from n-octyl, R2 selected from ethyl acetate, R4 selected from -CH=CH-(CH2)). 11 10g RNP-R (R1 selected from H, R2 selected from n-octyl), 15g RNP-NR (R1 selected from H, R2 selected from ethyl acetate, Y selected from Cl), 15g RNP-1A (R1 selected from methyl), 3g 1,2-propanedicarboxylic acid, 3g 1,6-hexanedicarboxylic acid, 5g 1,8,12,18-octadecanetetracarboxylic acid, 9g 1,12-dodecanedicarboxylic acid, 5g oxalic acid, 330mL water, and 6g DCC were stirred at 50℃ for catalytic esterification reaction for 8h. Then, 8g sodium olefin sulfonate and 8g tetradecyltrimethylammonium bromide were added, mixed well, and some water was evaporated to make water account for 30% of the total weight, thus obtaining the hybrid modified multidimensional bio-oil flooding agent.

[0051] Comparative Example 1 A solution was prepared by mixing 15g SPP, 15g RNP, 15g SPP-R (R1 selected from n-hexyl, R2 selected from benzoyl), 20g SPP-1A (R1 selected from n-propyl, R2 selected from n-propyl, R3 selected from phenyl), 20g SPP-2A (R1 selected from H, R2 selected from ethyl), 20g RNP-R (R1 selected from methyl formate, R2 selected from nitrophenyl), 10g RNP-1A (R1 selected from n-decyl), 10g RNP-2A (R1 selected from n-decyl), and 360mL of water. Then, 4g sodium olefin sulfonate, 3g cocamidopropyl betaine, and 3g tetradecyltrimethylammonium bromide were added and mixed well to obtain the oil displacement agent.

[0052] Oil-water interfacial tension test The oil displacement agents prepared in each embodiment and comparative example were prepared into aqueous solutions at an effective content concentration of 0.3 wt%. The solutions were tested using a rotating droplet interfacial tensiometer with kerosene as the simulated oil at 45°C and a rotation speed of 5500 rpm. The experimental results are shown in Tables 1 and 2.

[0053] Preparation of temperature resistance test samples: The oil displacement agents prepared in each example and comparative example were prepared into aqueous solutions at an effective content concentration of 0.3wt%, and aged at different temperatures of 90℃, 120℃, 150℃, 180℃ and 200℃ for 48h.

[0054] Preparation of salt tolerance test samples: The oil displacement agents prepared in each example and comparative example were prepared into aqueous solutions with an effective content of 0.3 wt% using simulated mineralized water with different mineralization degrees.

[0055] Table 1 Unit: ×10 -3 mN / m Table 2 Unit: ×10 -3 mN / m From Tables 1 and 2, it can be seen that the oil displacement agent prepared by this invention achieves a yield of 10. -3 It has a mN / m rating, good temperature and salt resistance, and is expected to have excellent oil displacement capability.

[0056] Oil displacement effect test The principle of the mass method: A columnar core of saturated crude oil from a good formation is completely immersed in an oil displacement agent solution. Due to the effects of wetting and capillary forces, the oil displacement agent solution will spontaneously seep into the pores of the core, thus discharging oil. The total pore volume remains unchanged throughout the process, but the mass of the core in the oil displacement agent solution will increase due to the oil displacement effect. According to Archimedes' principle of buoyancy, the oil recovery rate is calculated according to equation (1).

[0057] (1) In formula (1): R - spontaneous adsorption recovery rate, decimal; V0 - total saturated oil content in the core, mL; Δm - mass difference of the core in the displacement agent solution, g; ρ w ρ0 - Density of the oil displacement agent solution, oil density, g / cm³ 3 .

[0058] Test materials: oil displacement agent solutions aged at different temperatures in each example and comparative example, oil displacement agent solutions prepared with water of different salinity in each example and comparative example, formation crude oil taken from the oilfield (obtained after high-temperature dehydration separation), and natural core columns with a diameter of 25 mm taken from the oilfield.

[0059] Test conditions: Experimental temperature 90℃, experimental pressure atmospheric pressure.

[0060] Test steps: 1) Saturated crude oil: Vacuum pressurize the core to saturate the formation crude oil. After saturation, age it in a 90℃ constant temperature chamber for more than 24 hours. 2) After saturation, suspend the core on the hook directly below the balance of the percolation test device. Place beakers containing different water samples on the lifting platform below the core. Adjust the position to ensure that the core is in the middle of the liquid in the beaker and does not contact the beaker wall during the experiment. 3) Adjust the height of the beaker to a suitable height so that the core is completely immersed in the liquid and start the self-absorption experiment. Record the self-absorption time and core mass change during the experiment until no more oil is separated, indicating that the core mass is constant, and the experiment ends. Calculate the percolation recovery rate R of the core according to formula (1). Test each sample 3 times and take the average value.

[0061] The experimental results are shown in Tables 3 and 4.

[0062] Table 3 unit:% Table 4 unit:% Note: The initial crude oil saturation of the core samples used was 69.0-71.0%, and the water permeability was 1.80-1.90×10⁻⁶.-3 μm 2 The porosity is 12.5-13.5%, and the error is negligible.

[0063] As shown in Tables 3 and 4, the oil recovery rate of the examples at 90℃ reached over 65%, which is more than 60% higher than that of the control group and more than four times that of waterflooding. Furthermore, the performance remained stable below 200℃ and at a salinity of 200 g / L, with negligible impact from temperature variations. Therefore, the hybrid modification of the oil displacement agent prepared in this invention exhibits superior comprehensive performance, making it easier to enter the pore throat and emulsify the oil in the core, thus improving the oil recovery rate.

[0064] In summary, the hybrid modified multidimensional bio-nano oil displacement agent of the present invention has the characteristics of ultra-low interfacial tension, good temperature and salt resistance, and high oil displacement rate.

[0065] The above embodiments only selected a few sophorolipid modified derivatives and rhamnolipid modified derivatives with specific structures. Those skilled in the art should know that any compound or combination thereof in the general formula of sophorolipid modified derivatives and rhamnolipid modified derivatives can achieve similar implementation effects.

[0066] The above embodiments only selected a few specific polycarboxylic compounds. Those skilled in the art should know that one or more combinations of all polycarboxylic compounds containing a saturated alkyl chain with fewer than 18 carbon atoms between the carboxyl groups at both ends can achieve similar implementation effects.

Claims

1. A hybrid polymeric biosurfactant, characterized in that: The hybrid polybiosurfactant is the product of the esterification reaction between a biosurfactant and a polycarboxylic acid compound; The biosurfactant is at least one of lipopeptides, sophorolipids, rhamnolipids, modified sophorolipid derivatives, and modified rhamnolipid derivatives; The polycarboxylic acid compound is at least one of oxalic acid, 1,3-propanedicarboxylic acid, butanetetracarboxylic acid, 1,3-butanedicarboxylic acid, and polycarboxylic acid compounds containing a saturated alkyl chain with fewer than 18 carbon atoms between the two end carboxyl groups.

2. The hybrid polymeric biosurfactant according to claim 1, characterized in that: The modified sophorolipid derivative is at least one of the following: nonionic modified sophorolipid derivative, anionic modified sophorolipid derivative, cationic modified sophorolipid derivative, and zwitterionic modified sophorolipid derivative. The rhamnolipin modified derivative is at least one of the following: nonionic modified rhamnolipin, anionic modified rhamnolipin, cationic modified rhamnolipin, and zwitterionic modified rhamnolipin.

3. The hybrid polymeric biosurfactant according to claim 2, characterized in that: The chemical structural formula of the nonionic modified sophorolipid derivative is shown in general formula I or general formula II below; General Formula I General Formula II The chemical structural formula of the sophorolipid anionic modified derivative is shown in general formula III or general formula IV below; General Formula III General Formula IV The chemical structural formula of the cationic modified sophorolipid derivative is shown in general formula V below; Formula V The chemical structural formula of the zwitterionic modified sophorolipid derivative is shown in the following general formula VI; Formula VI The chemical structural formula of the nonionic modified rhamnolipin derivative is shown in general formula VII or general formula VIII below; Formula VII Formula VIII The chemical structural formula of the rhamnolipin anionic modified derivative is shown in general formula IX or general formula X below; Formula IX Formula X The chemical structural formula of the rhamnolipin cationic modified derivative is shown in the following general formula XI; General Formula XI The chemical structural formula of the rhamnolipin zwitterionic modified derivative is shown in the following general formula XII; Formula XII In the above general formulas, R1, R2, and R3 are each independently selected from hydrogen atoms, and C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 Saturated chain alkyl, phenyl, benzoyl, naphthyl, halophenyl, methyl formate, ethyl formate, methoxyphenyl, nitrophenyl, methylphenyl, C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 Unsaturated chain alkyl groups, C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 saturated cyclic alkyl groups; R4 is selected from C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 Saturated chain alkyl groups, C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 Unsaturated chain alkyl groups; X is selected from halogens; Y is selected from hydrogen atom, halogen, hydroxyl, and methoxy.

4. The method for preparing the hybrid polymeric biosurfactant according to claim 1, 2 or 3, characterized in that: The preparation method is as follows: Biosurfactants and polycarboxylic compounds were esterified by passing them through a cation exchange resin-packed column to obtain hybrid polybiosurfactants. Alternatively, a hybrid polybiosurfactant can be obtained by catalytic esterification of biosurfactants with polycarboxylic compounds.

5. The method for preparing the hybrid polymeric biosurfactant according to claim 4, characterized in that: The mass ratio of the biosurfactant to the polycarboxylic compound is 3-10:1; The catalyst is at least one of dicyclohexylcarbodiimide and 4-dimethylaminopyridine, and the amount of catalyst used is 0.1-5% of the total mass of the biosurfactant and the polycarboxylic compound.

6. A hybrid modified multidimensional bio-oil flooding agent, characterized in that: The oil displacement agent comprises the following components by weight percentage: The hybrid polymeric biosurfactant of claim 1, 2 or 3 comprises 1-75%; Reinforcing agent 0.2-20%; Water balance.

7. The hybrid modified multidimensional bio-oil flooding agent according to claim 6, characterized in that: The reinforcing agent is at least one of sodium olefin sulfonate, tetradecyltrimethylammonium bromide, and cocamidopropyl betaine.

8. The method for preparing the hybrid modified multidimensional bio-oil flooding agent according to claim 6 or 7, characterized in that: The preparation method is as follows: Biosurfactants and polycarboxylic compounds are esterified by passing them through a cation exchange resin-packed column to obtain hybrid polybiosurfactants. Then, an enhancer is added, the mixture is stirred, and some water is evaporated to obtain a hybrid modified multidimensional bio-oil displacement agent. Alternatively, a biosurfactant can be catalytically esterified with a polycarboxylic acid compound to obtain a hybrid polybiosurfactant. Then, an enhancer can be added, the mixture can be stirred, and some water can be evaporated to obtain a hybrid modified multidimensional bio-oil displacement agent.

9. The preparation method of the hybrid modified multidimensional bio-explosive agent according to claim 8, characterized in that: The mass ratio of the biosurfactant to the polycarboxylic compound is 3-10:1; The catalyst is at least one of dicyclohexylcarbodiimide and 4-dimethylaminopyridine, and the amount of catalyst used is 0.1-5% of the total mass of the biosurfactant and the polycarboxylic compound.

Images