Multifunctional biological osmosis agent, its preparation method and application

Abstract

The application discloses a multifunctional biological imbibition agent and a preparation method and application thereof. The preparation method of the multifunctional biological imbibition agent comprises the following steps: (S1), alkylization reaction to obtain alkyl naphthalene; (S2), chloromethylation reaction to obtain halomethyl alkyl naphthalene; (S3), halogen alkyl nucleophilic substitution reaction to obtain hydroxymethyl alkyl naphthalene; and (S4), esterification reaction to obtain the multifunctional biological imbibition agent. The application further discloses application of the multifunctional biological imbibition agent as an imbibition agent in shale oil reservoir oil extraction. The application has the following advantages: (1) the reservoir adsorption amount is small, but the good wetting reversal characteristic is still maintained, and the emulsification is weak; (2) the high-temperature resistance is strong, and the temperature resistance reaches above 200 DEG C; (3) the preparation process is simple, and the yield is high; (4) the dosage is small, the cost is low, and the economic benefit is remarkable.

Description

Technical Field

[0001] This invention belongs to the field of petroleum extraction, specifically relating to a multifunctional bio-absorbent, its preparation method, and its application. Background Technology

[0002] Petroleum is the "lifeblood of modern industry" and a strategic resource for national survival and development. However, as China's old oilfields have entered the later stages of high water-cut development, the main focus of oilfield extraction is shifting towards unconventional oil reservoir types (such as shale oil).

[0003] The physical properties of shale reservoirs differ significantly from conventional reservoirs, exhibiting characteristics of low porosity and low permeability. Their porosity is generally less than 10%, with an average pore size of around 100 nm. China has high geological reserves of shale oil, with the Shengli Oilfield's shale oil characterized by deep burial, low organic matter evolution, and high crude oil density, making large-scale, efficient development even more challenging.

[0004] Shale oil development primarily relies on hydraulic fracturing, supplemented by chemical percolators to displace crude oil from pores. For example, Chinese invention patent CN112694885A describes a high-activity drag reducer, a self-percolating, energy-enhancing slickwater fracturing fluid system suitable for shale oil reservoirs, and its preparation method and application. This slickwater fracturing fluid system contains a high-activity drag reducer and a swelling inhibitor, with a mass fraction of 0.08%–0.12% high-activity drag reducer, 0.3%–0.5% swelling inhibitor, and the balance being water. However, this type of oil displacement agent is costly, has high adsorption capacity, and causes significant pollution. Therefore, there is an urgent need to develop a multifunctional, high-efficiency bio-percolator for green and efficient shale oil development.

[0005] Biosurfactants are surface-active products produced by specific microorganisms during their growth. Common biosurfactants include lipopeptides, rhamnolipids, sophorolipids, and other lipid derivatives. Biosurfactant molecules have a hydrophilic group at one end and a hydrophobic group at the other. Compared to traditional chemically synthesized surfactants, biosurfactants exhibit diverse molecular structures, rich functions, and flexible properties, making them highly promising for unconventional oil reservoir development.

[0006] Chinese invention patent CN 112832726B discloses a tertiary oil recovery method for inter-stage oil displacement in a horizontal well of tight shale oil. This method includes screening the intervention well, the target formation, and the infeed and outfeed stages. An injection fluid containing a microbial oil displacement agent is injected from the infeed stage, causing the displaced crude oil to migrate to the outfeed stage. This significantly increases the reach of the bio-displacement agent, connects the remaining oil zones near and far of the well, reduces the oil-water interfacial tension and crude oil viscosity, and achieves enhanced production through tertiary oil recovery. However, it still has the following shortcomings: This invention mainly provides a tertiary oil recovery method for inter-stage oil displacement in a horizontal well of tight shale oil, and its applicability is relatively narrow.

[0007] Chinese invention patent application CN113698922A provides a biological shearing agent for improving the oil recovery efficiency of shale oil reservoirs, its preparation method, and its application. This invention mixes biological shearing enzyme powder with stabilizers and surfactants to obtain a biological shearing agent, which modifies the rock surface to an underwater superoleophobic state, thereby removing crude oil. However, there are still some shortcomings: (1) The biological shearing enzyme powder provided by this invention transforms the rock surface into a superoleophobic state, which is different from the research purpose of this invention, which uses a high-temperature resistant, weakly emulsified, multifunctional, and highly efficient biological permeabilizer to transform the core into a hydrophilic state; (2) This invention mainly focuses on solving the technical problems of long construction cycle, complex construction process, small coverage of oil displacement agent, and easy occurrence of water lock effect and water channeling in the existing microbial flooding tertiary oil recovery process. This invention mainly provides a multifunctional biological permeabilizer to improve the permeation efficiency of shale oil reservoirs after fracturing, and further improve the recovery rate.

[0008] Chinese patent application CN112892394A provides a sulfonic acid-based anionic gemini surfactant, its preparation, and its application as a shale oil reservoir percolation displacement agent. Compound II is prepared by reacting 2,3-diphenylmaleic anhydride with 7-ethyl-2-methyl-4-undecanol. Compound II is then reacted with hydroxyethylsulfonic acid to prepare compound III. Compound III is then reacted with an alkali to prepare the sulfonic acid-based anionic gemini surfactant compound shown in formula I. However, this invention still has the following shortcomings: (1) The alkyl chain in the hydrophobic group of the percolation displacement agent provided by this invention is too long, resulting in poor temperature resistance. (2) The percolation displacement agent provided by this invention has strong emulsifying properties, easily enhancing the Jamin effect, leading to increased displacement pressure, and serious demulsification problems in the subsequent produced fluid.

[0009] In addition, previous studies have also been conducted on the role of microorganisms in shale oil reservoir extraction. For example, Malik Sy Hadadin et al. reported the effect of a biosurfactant produced by Rhodococcus metabolism on non-species (EI-Lajjun) oil shale in their paper "Kinetics of hydrocarbon extraction from oil shale using bio-surfactant producing bacteria, Energy Conversion and Management" (2009). They found that the biosurfactant could significantly improve the solubility of hydrocarbons by forming micelles and effectively reduce surface tension and interfacial tension. Although this type of biosurfactant has shown the ability to improve oil displacement efficiency, its action condition is room temperature, and the oil recovery mechanism is only to change the properties of the oil-water interface, so the improvement in recovery rate is limited. Summary of the Invention

[0010] Purpose of the invention: To address the problems of strong pollution and poor reservoir adaptability of existing shale oil permeation agents, this invention provides a multifunctional bio-permeation agent, its preparation method, and its application.

[0011] This invention uses lipopeptides as raw materials and prepares a novel modified lipopeptide through a chemical reaction. The aim of this invention is to increase the hydrocarbon group length and geometric size of the hydrophobic chain of the lipopeptide through chemical modification, reduce the adsorption capacity of the lipopeptide on the rock surface, enhance its adaptability to crude oil in different blocks while ensuring strong wetting modification, significantly improve its ability to reduce oil-water interfacial tension, and enrich the structural diversity of biosurfactants. This preparation method features low raw material consumption and high product yield, and its application method is characterized by wide applicability, strong operability, low cost, and significant oil enhancement effect. Furthermore, based on different reservoir conditions, an oil displacement system is constructed mainly using modified lipopeptide bio-permeable agents with wetting modification and low interfacial tension characteristics to achieve the goal of reducing the amount of chemical oil displacement agents used and improving oil displacement efficiency.

[0012] Technical solution: A multifunctional bio-osmotic agent, the molecular structure of which is shown in formula (1):

[0013]

[0014] in:

[0015] R1 and R2 are independent.

[0016] R3 is C1-C 15 Alkyl groups.

[0017] Furthermore, R1 and R2 are both

[0018] R3 is C1-C 10 Alkyl groups.

[0019] A method for preparing any one of the above-mentioned multifunctional bio-osmotic agent, on a molar basis, comprises the following steps:

[0020] (S1) Alkylation reaction:

[0021] One part of the compound shown in formula (X) and 0.8-1.2 parts of the compound shown in formula (Y) were reacted in an appropriate amount of a first solvent under the catalysis of 0.02-0.08 parts of an alkylation catalyst. After the reaction was completed, a reaction solution was obtained, cooled to room temperature, and then the reaction solution was subjected to a first post-treatment to obtain alkylnaphthalene.

[0022] (S2), Chloromethylation reaction:

[0023] The alkyl naphthalene obtained in step (S1) is reacted with 0.9-1.1 parts of formaldehyde and 2-2.3 parts of hydrohalic acid in an appropriate amount of second solvent under the catalysis of 0.02-0.08 parts of chloromethylation catalyst. After the reaction is completed, a reaction solution is obtained, cooled to room temperature, and then the reaction solution is subjected to a second post-treatment to obtain halomethylalkyl naphthalene.

[0024] (S3), nucleophilic substitution reaction of haloalkane:

[0025] The halomethylalkylnaphthalene obtained in step (S2) is reacted with 0.8-1.2 parts of base in an appropriate amount of third solvent under the condition of 0.12-0.18 parts of haloalkyl nucleophilic substitution catalyst. After the reaction is completed, the reaction solution is cooled to room temperature, and then the reaction solution is subjected to a second post-treatment to obtain hydroxymethylalkylnaphthalene.

[0026] (S4) Esterification reaction:

[0027] The hydroxymethylalkylnaphthalene obtained in step (S3) was reacted with 0.4-0.5 parts of the compound shown in formula (Z) in an appropriate amount of a fourth solvent under the catalysis of 0.02-0.08 parts of an esterification catalyst. After the reaction was completed, a reaction solution was obtained, cooled to room temperature, and then subjected to a fourth post-treatment to obtain a multifunctional bio-osmotic agent, wherein:

[0028]

[0029] R3 is C1-C 15 Alkyl groups, preferably C1-C 10 Alkyl groups.

[0030] Further, the alkylation catalyst in step (S1) is one of AlCl3, FeCl3, SbCl5, SnCl4, BF3, TiCl4, and ZnCl2.

[0031] Furthermore, the alkylation reaction in step (S1) is carried out at a temperature of 80-150°C for a reaction time of 10-120 min.

[0032] Further, in step (S1), the first solvent is one of hexane, cyclohexane, and heptane.

[0033] Further, in step (S1), the amount of the first solvent used, expressed as the molar amount of the compound shown in formula (X), is 200-1000 mL / mol.

[0034] Furthermore, the specific steps of the first post-processing in step (S1) are as follows: first, filter and retain the liquid, and then distill under reduced pressure.

[0035] Furthermore, the chloromethylation catalyst in step (S2) is ZnCl2.

[0036] Furthermore, in step (S2), the chloromethylation reaction is carried out at a temperature of 50-100°C for 4-11 hours.

[0037] Further, the hydrohalic acid mentioned in step (S2) is hydrochloric acid or hydrobromic acid.

[0038] Further, in step (S2), the second solvent is water, and the mass ratio of the amount of the second solvent to the mass of the hydrohalic acid is (5-10):2.

[0039] Furthermore, the specific steps of the second post-processing in step (S2) and step (S3) are as follows:

[0040] S21. Extract with chloroform, ethyl acetate, or butyl acetate, retaining the organic phase;

[0041] S22. Neutralize the organic phase with a saturated sodium bicarbonate aqueous solution or a saturated sodium carbonate aqueous solution, wash with deionized water until neutral, and dry with a desiccant. Wherein:

[0042] The desiccant is one of anhydrous calcium chloride, anhydrous magnesium sulfate, and anhydrous sodium sulfate.

[0043] Furthermore, in step (S3), the nucleophilic substitution catalyst of the haloalkane is one or more of tetrabutylammonium bromide, methyltrioctylammonium chloride, phenyltrimethylammonium chloride, and polyethylene glycol.

[0044] Further, the base mentioned in step (S3) is NaOH or KOH.

[0045] Furthermore, in step (S3), the nucleophilic substitution reaction of the haloalkane is carried out at a temperature of 50-120°C for a time of 2-13 hours.

[0046] Further, in step (S3), the third solvent is deionized water, and the amount of the third solvent used, based on the mass of the alkali, is 15-25 mL / g.

[0047] Furthermore, the esterification catalyst in step (S4) is one or more of organic acids and inorganic acids.

[0048] Furthermore, the inorganic acid is one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and boric acid; the organic acid is one or more of p-toluenesulfonic acid, naphthenic acid, and methanesulfonic acid.

[0049] Furthermore, the esterification reaction in step (S4) is carried out at a temperature of 100-150°C for 5-10 hours.

[0050] Further, the fourth solvent mentioned in step (S4) is one of benzene, toluene, xylene, and dichloromethane.

[0051] Further, the amount of the fourth solvent used in step (S4) is 1-3 mL / g, based on the mass of the compound shown in formula (Z).

[0052] Further, the specific steps of the fourth post-processing described in step (S4) are as follows: first, filter and retain the liquid phase; then, distill under reduced pressure; and finally, purify using silica gel column chromatography, wherein:

[0053] The specific process parameters for purification by silica gel column chromatography are as follows:

[0054] 200-300 mesh silicone;

[0055] m 硅胶 :m 待分离组分 =(30~50):1, wet packing of column, wet loading of sample;

[0056] The developing solvent was 20 v / v% methanol + 80 v / v% dichloromethane, and separation was performed under pressure.

[0057] The multifunctional bio-osmotic agent is prepared by any of the preparation methods described above.

[0058] The application of any of the above-mentioned multifunctional bio-permeabilizers as permeabilizers in shale oil reservoir production.

[0059] Furthermore, the specific steps of the above application are as follows: inject the proppant and any of the above-mentioned multifunctional bio-absorbents into the target shale oil layer, and shut in the well for at least 2 days after fracturing.

[0060] To address the problems of high cost, high adsorption capacity, strong pollution, and poor reservoir adaptability of existing shale oil permeating agents, this invention provides a multifunctional bio-permeating agent. This agent uses a lipopeptide as a raw material, forming a hydroxymethylalkylnaphthalene through a three-step reaction. Subsequently, an esterification reaction is used to react the hydroxymethylalkylnaphthalene with the lipopeptide to generate the multifunctional bio-permeating agent. This multifunctional bio-permeating agent features high temperature resistance, weak emulsification, strong wetting modification, and low adsorption capacity.

[0061] Specifically, the multifunctional bio-permeable agent aims to increase the hydrocarbon length and geometric size of the hydrophobic chain of the lipopeptide, thereby significantly reducing its adsorption capacity on the rock surface while ensuring its strong wetting reversal function. In addition, the introduced alkyl naphthalene groups have strong temperature resistance.

[0062] In addition, this multifunctional bio-permeable agent has weak emulsification properties, which significantly reduces the Jamin effect of crude oil in the pores of shale reservoirs and avoids the problem of difficult demulsification of produced fluid.

[0063] Beneficial effects: Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0064] (1) The multifunctional bio-permeable agent of the present invention has a low reservoir adsorption capacity, but still maintains good wetting reversal characteristics and weak emulsification. When the dosage exceeds 2000ppm, the wettability of the oleophilic core reaches 0.60 or higher, the emulsification capacity is less than 25%, the static permeability recovery value is >80%, and the permeation replacement rate is about 20%.

[0065] (2) The multifunctional bio-permeable agent of the present invention has good high temperature resistance, with a temperature resistance of over 200℃;

[0066] (3) The preparation process of the multifunctional bio-osmotic agent of the present invention is simple and has a high yield;

[0067] (4) The multifunctional bio-osmotic agent of the present invention has the characteristics of low dosage and low cost, and has significant economic benefits. Attached Figure Description

[0068] Figure 1 This is a flowchart of the preparation method of the multifunctional bio-osmotic agent disclosed in this invention. Detailed Implementation

[0069] The present invention will now be described in further detail with reference to specific embodiments and data. It should be understood that these embodiments are merely illustrative of the invention and are not intended to limit the scope of the invention in any way.

[0070] The preparation route of the multifunctional bio-osmotic agent of the present invention is as follows:

[0071]

[0072] R1 and R2 are independent.

[0073] R3 is C1-C 15 Alkyl groups;

[0074] X is one of Cl or Br.

[0075] Example 1

[0076] A multifunctional bio-osmotic agent, the molecular structure of which is shown in formula (1):

[0077] in:

[0078] R1 is

[0079] R2 is

[0080] R3 is a methyl group.

[0081] Example 2

[0082] A multifunctional bio-osmotic agent, the molecular structure of which is shown in formula (1):

[0083]

[0084]

[0085] in:

[0086] R1 and R2 are both for

[0087] R3 is a normal decyl group.

[0088] Example 3

[0089] A multifunctional bio-osmotic agent, the molecular structure of which is shown in formula (1):

[0090] in:

[0091] R1 and R2 are both

[0092] R3 is a pentadecyl group.

[0093] Example 4

[0094] A multifunctional bio-osmotic agent, the molecular structure of which is shown in formula (1):

[0095] in:

[0096] R1 and R2 are both

[0097] R3 is cyclobutyl.

[0098] Example 5

[0099] A method for preparing a multifunctional bio-osmotic agent, the steps of which are as follows (in molar amounts):

[0100] (S1) Alkylation reaction:

[0101] One part of the compound shown in formula (X) and one part of the compound shown in formula (Y) were reacted in an appropriate amount of the first solvent under the catalysis of 0.04 parts of alkylation catalyst. After the reaction was completed, a reaction solution was obtained, cooled to room temperature, and then the reaction solution was subjected to a first post-treatment to obtain alkylnaphthalene.

[0102] (S2), Chloromethylation reaction:

[0103] The alkyl naphthalene obtained in step (S1) is reacted with 1 part formaldehyde and 2.1 parts hydrohalic acid in an appropriate amount of second solvent under the catalysis of 0.04 parts chloromethylation catalyst. After the reaction is completed, a reaction solution is obtained, cooled to room temperature, and then the reaction solution is subjected to a second post-treatment to obtain halomethylalkyl naphthalene.

[0104] (S3), nucleophilic substitution reaction of haloalkane:

[0105] The halomethylalkylnaphthalene obtained in step (S2) was reacted with 1 part of base in an appropriate amount of third solvent under the condition of 0.15 parts of haloalkyl nucleophilic substitution catalyst. After the reaction was completed, the reaction solution was cooled to room temperature, and then the reaction solution was subjected to a second post-treatment to obtain hydroxymethylalkylnaphthalene.

[0106] (S4) Esterification reaction:

[0107] The hydroxymethylalkylnaphthalene obtained in step (S3) was reacted with 0.45 parts of the compound shown in formula (Z) in an appropriate amount of a fourth solvent under the catalysis of 0.06 parts of an esterification catalyst. After the reaction was completed, a reaction solution was obtained, cooled to room temperature, and then subjected to a fourth post-treatment to obtain a multifunctional bio-osmotic agent, wherein:

[0108]

[0109] R3 is an ethyl group.

[0110] Furthermore, the alkylation catalyst in step (S1) is AlCl3.

[0111] Furthermore, the alkylation reaction in step (S1) is carried out at a temperature of 100°C for a time of 100 min.

[0112] Furthermore, in step (S1), the first solvent is heptane.

[0113] Further, in step (S1), the amount of the first solvent used, expressed as the molar amount of the compound shown in formula (X), is 500 mL / mol.

[0114] Furthermore, the specific steps of the first post-processing in step (S1) are as follows: first, filter and retain the liquid, and then distill under reduced pressure.

[0115] Furthermore, the chloromethylation catalyst in step (S2) is ZnCl2.

[0116] Furthermore, in step (S2), the chloromethylation reaction is carried out at a temperature of 60°C for 7 hours.

[0117] Further, the hydrohalic acid mentioned in step (S2) is hydrochloric acid.

[0118] Further, in step (S2), the second solvent is water, and the mass ratio of the amount of the second solvent to the mass of the hydrohalic acid is 8:2.

[0119] Furthermore, the specific steps of the second post-processing in step (S2) and step (S3) are as follows:

[0120] S21. Extract with chloroform, retaining the organic phase;

[0121] S22. Neutralize the organic phase with a saturated sodium bicarbonate aqueous solution, wash with deionized water until neutral, and dry with a desiccant. Wherein:

[0122] The desiccant is anhydrous calcium chloride.

[0123] Furthermore, in step (S3), the nucleophilic substitution catalyst for the haloalkane is methyltrioctylammonium chloride.

[0124] Further, the base mentioned in step (S3) is NaOH.

[0125] Furthermore, in step (S3), the nucleophilic substitution reaction of the haloalkane is carried out at a temperature of 70°C for 4 hours.

[0126] Further, in step (S3), the third solvent is deionized water, and the amount of the third solvent used, based on the mass of the alkali, is 20 mL / g.

[0127] Furthermore, the esterification catalyst in step (S4) is an organic acid.

[0128] Furthermore, the organic acid is p-toluenesulfonic acid.

[0129] Furthermore, the esterification reaction in step (S4) is carried out at a temperature of 120°C for 7 hours.

[0130] Furthermore, the fourth solvent mentioned in step (S4) is toluene.

[0131] Further, the amount of the fourth solvent used in step (S4) is 2 mL / g, based on the mass of the compound shown in formula (Z).

[0132] Further, the specific steps of the fourth post-processing described in step (S4) are as follows: first, filter and retain the liquid phase; then, distill under reduced pressure; and finally, purify using silica gel column chromatography, wherein:

[0133] The specific process parameters for purification by silica gel column chromatography are as follows:

[0134] 250 mesh silicone;

[0135] m 硅胶 :m 待分离组分=40:1, wet packing, wet loading;

[0136] The developing solvent was 20 v / v% methanol + 80 v / v% dichloromethane, and separation was performed under pressure.

[0137] The multifunctional bio-osmotic agent is prepared by any of the preparation methods described above.

[0138] The application of any of the above-mentioned multifunctional bio-permeabilizers as permeabilizers in shale oil reservoir production.

[0139] Furthermore, the specific steps of the above application are as follows: inject the proppant and any of the above-mentioned multifunctional bio-absorbents into the target shale oil layer, and shut in the well for 2 days after fracturing.

[0140] Example 6

[0141] A method for preparing a multifunctional bio-osmotic agent, the steps of which are as follows (in molar amounts):

[0142] (S1) Alkylation reaction:

[0143] One part of the compound shown in formula (X) and 0.8 parts of the compound shown in formula (Y) were reacted in an appropriate amount of the first solvent under the catalysis of 0.02 parts of alkylation catalyst. After the reaction was completed, a reaction solution was obtained, cooled to room temperature, and then the reaction solution was subjected to a first post-treatment to obtain alkylnaphthalene.

[0144] (S2), Chloromethylation reaction:

[0145] The alkyl naphthalene obtained in step (S1) is reacted with 0.9 parts of formaldehyde and 2 parts of hydrohalic acid in an appropriate amount of second solvent under the catalysis of 0.02 parts of chloromethylation catalyst. After the reaction is completed, a reaction solution is obtained, cooled to room temperature, and then the reaction solution is subjected to a second post-treatment to obtain halomethylalkyl naphthalene.

[0146] (S3), nucleophilic substitution reaction of haloalkane:

[0147] The halomethylalkylnaphthalene obtained in step (S2) was reacted with 0.8 parts of base in an appropriate amount of third solvent under the condition of 0.12 parts of haloalkyl nucleophilic substitution catalyst. After the reaction was completed, the reaction solution was cooled to room temperature, and then the reaction solution was subjected to a second post-treatment to obtain hydroxymethylalkylnaphthalene.

[0148] (S4) Esterification reaction:

[0149] The hydroxymethylalkylnaphthalene obtained in step (S3) was reacted with 0.4 parts of the compound shown in formula (Z) in an appropriate amount of a fourth solvent under the catalysis of 0.02 parts of an esterification catalyst. After the reaction was completed, a reaction solution was obtained, cooled to room temperature, and then subjected to a fourth post-treatment to obtain a multifunctional bio-osmotic agent, wherein:

[0150]

[0151] R3 is a methyl group.

[0152] Further, the alkylation catalyst in step (S1) is FeCl3.

[0153] Furthermore, the alkylation reaction in step (S1) is carried out at a temperature of 80°C for a time of 120 min.

[0154] Furthermore, in step (S1), the first solvent is hexane.

[0155] Further, in step (S1), the amount of the first solvent used, expressed as the molar amount of the compound shown in formula (X), is 200 mL / mol.

[0156] Furthermore, the specific steps of the first post-processing in step (S1) are as follows: first, filter and retain the liquid, and then distill under reduced pressure.

[0157] Furthermore, the chloromethylation catalyst in step (S2) is ZnCl2.

[0158] Furthermore, in step (S2), the chloromethylation reaction is carried out at a temperature of 50°C for 11 hours.

[0159] Further, the hydrohalic acid mentioned in step (S2) is hydrochloric acid or hydrobromic acid.

[0160] Further, in step (S2), the second solvent is water, and the mass ratio of the amount of the second solvent to the mass of the hydrohalic acid is 5:2.

[0161] Furthermore, the specific steps of the second post-processing in step (S2) and step (S3) are as follows:

[0162] S21. Extract with ethyl acetate, retaining the organic phase;

[0163] S22. Neutralize the organic phase with a saturated sodium carbonate aqueous solution, wash with deionized water until neutral, and dry with a desiccant. Wherein:

[0164] The desiccant is anhydrous magnesium sulfate.

[0165] Furthermore, in step (S3), the nucleophilic substitution catalyst for the haloalkane is tetrabutylammonium bromide.

[0166] Further, the base mentioned in step (S3) is KOH.

[0167] Furthermore, in step (S3), the nucleophilic substitution reaction of the haloalkane is carried out at a temperature of 50°C for 13 hours.

[0168] Further, in step (S3), the third solvent is deionized water, and the amount of the third solvent used, based on the mass of the alkali, is 15 mL / g.

[0169] Furthermore, the esterification catalyst in step (S4) is an inorganic acid.

[0170] Furthermore, the inorganic acid is sulfuric acid.

[0171] Furthermore, the esterification reaction in step (S4) is carried out at a temperature of 100°C for a reaction time of 10 hours.

[0172] Furthermore, the fourth solvent mentioned in step (S4) is toluene.

[0173] Furthermore, the amount of the fourth solvent used in step (S4) is 1 mL / g, based on the mass of the compound shown in formula (Z).

[0174] Further, the specific steps of the fourth post-processing described in step (S4) are as follows: first, filter and retain the liquid phase; then, distill under reduced pressure; and finally, purify using silica gel column chromatography, wherein:

[0175] The specific process parameters for purification by silica gel column chromatography are as follows:

[0176] 200 mesh silicone;

[0177] m 硅胶 :m 待分离组分 =30:1, wet column packing, wet sample loading;

[0178] The developing solvent was 20 v / v% methanol + 80 v / v% dichloromethane, and separation was performed under pressure.

[0179] The multifunctional bio-osmotic agent is prepared by any of the preparation methods described above.

[0180] The application of any of the above-mentioned multifunctional bio-permeabilizers as permeabilizers in shale oil reservoir production.

[0181] Furthermore, the specific steps of the above application are as follows: inject the proppant and any of the above-mentioned multifunctional bio-absorbents into the target shale oil layer, and shut in the well for 3 days after fracturing.

[0182] Example 7

[0183] A method for preparing a multifunctional bio-osmotic agent, the steps of which are as follows (in molar amounts):

[0184] (S1) Alkylation reaction:

[0185] One part of the compound shown in formula (X) and 1.2 parts of the compound shown in formula (Y) were reacted in an appropriate amount of the first solvent under the catalysis of 0.08 parts of alkylation catalyst. After the reaction was completed, a reaction solution was obtained, cooled to room temperature, and then the reaction solution was subjected to a first post-treatment to obtain alkylnaphthalene.

[0186] (S2), Chloromethylation reaction:

[0187] The alkyl naphthalene obtained in step (S1) is reacted with 1.1 parts of formaldehyde and 2.3 parts of hydrohalic acid in an appropriate amount of second solvent under the catalysis of 0.08 parts of chloromethylation catalyst. After the reaction is completed, a reaction solution is obtained, cooled to room temperature, and then the reaction solution is subjected to a second post-treatment to obtain halomethylalkyl naphthalene.

[0188] (S3), nucleophilic substitution reaction of haloalkane:

[0189] The halomethylalkylnaphthalene obtained in step (S2) was reacted with 1.2 parts of base in an appropriate amount of third solvent under the condition of 0.18 parts of haloalkyl nucleophilic substitution catalyst. After the reaction was completed, the reaction solution was cooled to room temperature, and then the reaction solution was subjected to a second post-treatment to obtain hydroxymethylalkylnaphthalene.

[0190] (S4) Esterification reaction:

[0191] The hydroxymethylalkylnaphthalene obtained in step (S3) was reacted with 0.5 parts of the compound shown in formula (Z) in an appropriate amount of a fourth solvent under the catalysis of 0.08 parts of an esterification catalyst. After the reaction was completed, a reaction solution was obtained, cooled to room temperature, and then subjected to a fourth post-treatment to obtain a multifunctional bio-osmotic agent, wherein:

[0192]

[0193]

[0194] R3 is a normal decyl group.

[0195] Further, the alkylation catalyst in step (S1) is AlCl3. In another embodiment, the alkylation catalyst in step (S1) is SbCl5. In another embodiment, the alkylation catalyst in step (S1) is SnCl4. In another embodiment, the alkylation catalyst in step (S1) is BF3. In another embodiment, the alkylation catalyst in step (S1) is TiCl4. In another embodiment, the alkylation catalyst in step (S1) is ZnCl2.

[0196] Furthermore, the alkylation reaction in step (S1) is carried out at a temperature of 150°C for a reaction time of 10 min.

[0197] Furthermore, in step (S1), the first solvent is cyclohexane.

[0198] Further, in step (S1), the amount of the first solvent used, expressed as the molar amount of the compound shown in formula (X), is 1000 mL / mol.

[0199] Furthermore, the specific steps of the first post-processing in step (S1) are as follows: first, filter and retain the liquid, and then distill under reduced pressure.

[0200] Furthermore, the chloromethylation catalyst in step (S2) is ZnCl2.

[0201] Furthermore, in step (S2), the chloromethylation reaction is carried out at a temperature of 100°C for 4 hours.

[0202] Furthermore, the hydrohalic acid mentioned in step (S2) is hydrobromic acid.

[0203] Further, in step (S2), the second solvent is water, and the mass ratio of the amount of the second solvent to the mass of the hydrohalic acid is 10:2.

[0204] Furthermore, the specific steps of the second post-processing in step (S2) and step (S3) are as follows:

[0205] S21. Extract with butyl acetate, retaining the organic phase;

[0206] S22. Neutralize the organic phase with a saturated sodium bicarbonate aqueous solution, wash with deionized water until neutral, and dry with a desiccant. Wherein:

[0207] The desiccant is anhydrous sodium sulfate.

[0208] Further, in step (S3), the nucleophilic substitution catalyst for the haloalkane is tetrabutylammonium bromide. In another embodiment, in step (S3), the nucleophilic substitution catalyst for the haloalkane is a mixture of tetrabutylammonium bromide, methyltrioctylammonium chloride, phenyltrimethylammonium chloride, and polyethylene glycol in an equimolar ratio. In another embodiment, in step (S3), the nucleophilic substitution catalyst for the haloalkane is methyltrioctylammonium chloride. In another embodiment, in step (S3), the nucleophilic substitution catalyst for the haloalkane is phenyltrimethylammonium chloride. In another embodiment, in step (S3), the nucleophilic substitution catalyst for the haloalkane is polyethylene glycol.

[0209] Further, the base mentioned in step (S3) is KOH.

[0210] Furthermore, in step (S3), the nucleophilic substitution reaction of the haloalkane is carried out at a temperature of 120°C for 2 hours.

[0211] Further, in step (S3), the third solvent is deionized water, and the amount of the third solvent used, based on the mass of the alkali, is 25 mL / g.

[0212] Furthermore, the esterification catalyst in step (S4) is an organic acid.

[0213] Furthermore, the organic acid is p-toluenesulfonic acid.

[0214] Furthermore, the esterification reaction in step (S4) is carried out at a temperature of 150°C for 5 hours.

[0215] Further, the fourth solvent in step (S4) is toluene. In another embodiment, the fourth solvent in step (S4) is benzene. In another embodiment, the fourth solvent in step (S4) is xylene. In yet another embodiment, the fourth solvent in step (S4) is dichloromethane.

[0216] Further, the amount of the fourth solvent used in step (S4) is 3 mL / g, based on the mass of the compound shown in formula (Z).

[0217] Further, the specific steps of the fourth post-processing described in step (S4) are as follows: first, filter and retain the liquid phase; then, distill under reduced pressure; and finally, purify using silica gel column chromatography, wherein:

[0218] The specific process parameters for purification by silica gel column chromatography are as follows:

[0219] 300 mesh silicone;

[0220] m 硅胶 :m 待分离组分 =50:1, wet packing column, wet sample loading;

[0221] The developing solvent was 20 v / v% methanol + 80 v / v% dichloromethane, and separation was performed under pressure.

[0222] The multifunctional bio-osmotic agent is prepared by any of the preparation methods described above.

[0223] The application of any of the above-mentioned multifunctional bio-permeabilizers as permeabilizers in shale oil reservoir production.

[0224] Furthermore, the specific steps of the above application are as follows: inject the proppant and any of the above-mentioned multifunctional bio-absorbents into the target shale oil layer, and shut in the well for 4 days after fracturing.

[0225] Examples 8-15

[0226] Similar to Example 5, except that the esterification catalyst used in step (S4) is different.

[0227]

[0228]

[0229] Example 16

[0230] The multifunctional bio-permeable agent prepared in Example 5 was applied in Block A1 of a shale oil reservoir in Shengli Oilfield. This well group had 1 injection and 5 production.

[0231] Oil well overview: Formation temperature 150℃, formation water salinity 57336 mg / L, effective target layer thickness 10.5 m, porosity 4.65%, permeability 0.21 × 10⁻⁶. -3 μm 2 The target formation of this well consists of alternating layers of marl, mudstone, limestone and dolomite, with a formation pressure of 48.9 MPa. The average daily oil production increase per well after fracturing is 0.12 t / d.

[0232] After analysis, it was decided to optimize the application of the multifunctional bio-permeable agent prepared in Example 5 to well group A1 in a shale oil reservoir of Shengli Oilfield. The specific steps are as follows:

[0233] Under conditions exceeding the fracture pressure, proppant and multifunctional bio-absorbent are injected into the target shale oil layer, followed by well shut-in for 2 days.

[0234] Furthermore, the multifunctional bio-osmotic agent is injected at a concentration of 2000 ppm and an injection volume of 47000 m³. 3 .

[0235] Furthermore, if the pressure change in the fractured well is ≤0.15MPa after 2 days of shut-in, the well can be opened to release the blowout.

[0236] Test results: After injecting the multifunctional bio-absorption agent, the average daily oil increase per well reached 3.7t, and the effective period reached 60 days. The field test results were good.

[0237] Performance testing:

[0238] Test Example 1

[0239] Core wettability determination: Following method 3 in SY / T5153-2007, natural cores, corresponding crude oil, formation water, and the multifunctional bio-absorbent prepared in Example 5 were selected from three different shale oil reservoir blocks in the Shengli Oilfield.

[0240] First, natural shale oil cores were prepared according to the treatment method shown in Section 7 of SY / T 6540-2021. Then, the effect of the multifunctional bio-permeable agent obtained in Example 5 (prepared using formation water from each block) at 2000 ppm on the wettability of the oleophilic natural shale cores was evaluated using the self-absorption method.

[0241] The test temperature was 85℃. The results of the core wettability test are shown in Table 1.

[0242] Table 1. Effects of multifunctional bio-permeable agents on the wettability of natural cores from shale oil reservoirs.

[0243]

[0244] The wettability test results show that the multifunctional bio-permeable agent provided by the present invention has the function of significantly changing the wettability of oleophilic reservoirs. After the action, the oleophilic core becomes a hydrophilic or strongly hydrophilic core.

[0245] Determination of emulsifying properties: The emulsifying ability of the multifunctional bio-permeabilizer obtained in Example 5 was evaluated by measuring the optical density value of the extract, in accordance with the method of GB / T 6369-2008.

[0246] The test temperature was 85℃, and the oil phases used were three types of crude oil taken from different shale oil reservoirs. The emulsification performance results are shown in Table 2.

[0247] Table 2. Effect of multifunctional bio-permeable agent concentration on crude oil emulsification properties in shale oil reservoirs.

[0248]

[0249] The emulsification performance results show that the multifunctional bio-permeable agent of the present invention has weak emulsification performance. After the action of 2000 ppm of the multifunctional bio-permeable agent, the emulsification force is only less than 25%, which greatly reduces the Jamin effect of crude oil in the pores of shale oil reservoirs and makes it easier to improve the recovery rate of shale oil reservoirs.

[0250] Test Example 2

[0251] High-temperature stability evaluation method: Natural cores, corresponding crude oil, formation water, and the multifunctional bio-absorbent prepared in Example 5 were selected from four different shale oil reservoir blocks in Shengli Oilfield.

[0252] First, natural shale oil cores were prepared according to Section 7 of SY / T 6540-2021. Then, experiments were conducted according to Method 3 of SY / T5153-2007. The effect of 2000 ppm of the multifunctional bio-permeable agent prepared in Example 5 (prepared using formation water from each block) on the wettability of the oleophilic natural shale cores was evaluated using the self-absorption method.

[0253] The test temperatures were 60℃, 80℃, 100℃, 150℃, and 180℃. The results of the core wettability test are shown in Table 3.

[0254] Table 3 High-Temperature Stability of Multifunctional Bioabsorption Agent's Wetting Modification Performance

[0255]

[0256] Experimental results confirm that the multifunctional bio-permeable agent provided by this invention still exhibits good wetting reversal stability under high temperature conditions (200℃). After action, it can transform oleophilic cores into hydrophilic or strongly hydrophilic cores, making it suitable for the development of high-temperature shale oil reservoirs.

[0257] Test Example 3

[0258] Reservoir damage rate evaluation method: Natural cores, corresponding crude oil, formation water, and the multifunctional bio-absorbent prepared in Example 5 were selected from three different shale oil reservoir blocks in Shengli Oilfield.

[0259] First, the natural core of shale oil was prepared according to the treatment shown in Section 7 of SY / T 6540-2021. Then, the static evaluation experiment of shale oil layer bio-permeable agent damage was carried out using the method shown in Section 11 of SY / T 6540-2021. The concentration of the multifunctional bio-permeable agent was selected as 2000 ppm; the reservoir temperature was 150℃; the static permeability recovery value of the shale oil layer before and after the bio-permeable agent damage was calculated according to formula (3) in SY / T 6540-2021. The reservoir damage rate (static permeability recovery value) measurement results are shown in Table 4. The permeable agent used was the multifunctional bio-permeable agent prepared in Example 5.

[0260] Table 4 Static permeability recovery values ​​of shale oil reservoirs using multifunctional bio-absorbents

[0261]

[0262]

[0263] Experimental results confirm that the multifunctional bio-absorbent provided by this invention has a low adsorption amount in shale oil layers, a static permeability recovery value of >80%, and causes less damage to rock permeability, thus avoiding potential water lock and water-sensitive damage.

[0264] Test Example 4

[0265] Evaluation method of permeation replacement rate: Natural cores, corresponding crude oil, formation water, and multifunctional bio-permeation agent prepared in Example 5 were selected from three different shale oil reservoir blocks in Shengli Oilfield.

[0266] First, prepare shale oil cores according to the method described in Section 7 of SY / T 6540-2021. Then, saturate the cores with formation water and crude oil, and then age them at reservoir temperature for 7 days.

[0267] A 2000 ppm biowetting regulator solution was prepared using water samples from the block and poured into the inhalation apparatus. The aged core samples were then placed in the inhalation apparatus containing the biowetting regulator solution, sealed, and allowed to stand at the block's reservoir temperature. During the inhalation process, the amount of oil extracted was recorded every 6 hours until the amount of oil extracted stabilized. Specific experimental results are shown in Table 5.

[0268] Table 5 Evaluation of the Immersion Replacement Rate of Multifunctional Bio-Immersion Agents

[0269]

[0270]

[0271] Experimental results confirm that the multifunctional bio-osmotic agent prepared in Example 5 of this invention reaches osmotic equilibrium within 48 hours, with an osmotic replacement rate of about 20%, and exhibits good osmotic effect.

[0272] The embodiments of the present invention have been described in detail above. However, the present invention is not limited to the above embodiments, and various changes can be made within the scope of knowledge possessed by those skilled in the art without departing from the spirit of the present invention.

Claims

1. A multifunctional bio-osmotic agent, characterized in that, Its molecular structure is shown in formula (1): in: R1 and R2 are independent. R3 is C1-C 15 Alkyl groups.

2. The multifunctional bio-osmotic agent as described in claim 1, characterized in that, In equation (1), R1 and R2 are both R3 is C1-C 10 Alkyl groups.

3. A method for preparing the multifunctional bio-osmotic agent according to claim 1 or 2, characterized in that, In molars, the steps are as follows: (S1) Alkylation reaction: One part of the compound shown in formula (X) and 0.8-1.2 parts of the compound shown in formula (Y) were reacted in an appropriate amount of a first solvent under the catalysis of 0.02-0.08 parts of an alkylation catalyst. After the reaction was completed, a reaction solution was obtained, cooled to room temperature, and then the reaction solution was subjected to a first post-treatment to obtain alkylnaphthalene. (S2), Chloromethylation reaction: The alkyl naphthalene obtained in step (S1) is reacted with 0.9-1.1 parts of formaldehyde and 2-2.3 parts of hydrohalic acid in an appropriate amount of second solvent under the catalysis of 0.02-0.08 parts of chloromethylation catalyst. After the reaction is completed, a reaction solution is obtained, cooled to room temperature, and then the reaction solution is subjected to a second post-treatment to obtain halomethylalkyl naphthalene. (S3), nucleophilic substitution reaction of haloalkane: The halomethylalkylnaphthalene obtained in step (S2) is reacted with 0.8-1.2 parts of base in an appropriate amount of third solvent under the condition of 0.12-0.18 parts of haloalkyl nucleophilic substitution catalyst. After the reaction is completed, the reaction solution is cooled to room temperature, and then the reaction solution is subjected to a second post-treatment to obtain hydroxymethylalkylnaphthalene. (S4) Esterification reaction: The hydroxymethylalkylnaphthalene obtained in step (S3) was reacted with 0.4-0.5 parts of the compound shown in formula (Z) in an appropriate amount of a fourth solvent under the catalysis of 0.02-0.08 parts of an esterification catalyst. After the reaction was completed, a reaction solution was obtained, cooled to room temperature, and then subjected to a fourth post-treatment to obtain a multifunctional bio-osmotic agent, wherein: R3 is C1-C 15 Alkyl groups.

4. The preparation method of the multifunctional bio-osmotic agent as described in claim 3, characterized in that, In step (S1), the substituent R3 of the compound shown in formula (Y) is C1-C. 10 Alkyl groups.

5. The preparation method of the multifunctional bio-osmotic agent as described in claim 3, characterized in that, The alkylation catalyst in step (S1) is one of AlCl3, FeCl3, SbCl5, SnCl4, BF3, TiCl4, and ZnCl2.

6. The method for preparing a multifunctional bio-osmotic agent as described in claim 3, characterized in that, The alkylation reaction in step (S1) is carried out at a temperature of 80-150℃ for a time of 10-120 min.

7. The preparation method of the multifunctional bio-osmotic agent as described in claim 3, characterized in that, In step (S1), the first solvent is one of hexane, cyclohexane, and heptane.

8. The preparation method of the multifunctional bio-osmotic agent as described in claim 3, characterized in that, In step (S1), the amount of the first solvent used, expressed as the molar amount of the compound represented by formula (X), is 200-1000 mL / mol.

9. The method for preparing a multifunctional bio-osmotic agent as described in claim 3, characterized in that, The specific steps of the first post-processing in step (S1) are as follows: first, filter and retain the liquid, and then distill under reduced pressure.

10. The method for preparing a multifunctional bio-osmotic agent as described in claim 3, characterized in that, The chloromethylation catalyst in step (S2) is ZnCl2; The hydrohalic acid mentioned in step (S2) is hydrochloric acid or hydrobromic acid.

11. The method for preparing a multifunctional bio-osmotic agent as described in claim 3, characterized in that, The reaction temperature for the chloromethylation reaction in step (S2) is 50-100℃, and the reaction time is 4-11h.

12. The method for preparing a multifunctional bio-osmotic agent as described in claim 3, characterized in that, In step (S2), the second solvent is water, and the mass ratio of the amount of the second solvent to the mass of the hydrohalic acid is (5-10):

2.

13. The method for preparing a multifunctional bio-osmotic agent as described in claim 3, characterized in that, The specific steps of the second post-processing in steps (S2) and (S3) are as follows: S21. Extract with chloroform, ethyl acetate, or butyl acetate, retaining the organic phase; S22. Neutralize the organic phase with a saturated sodium bicarbonate aqueous solution or a saturated sodium carbonate aqueous solution, wash with deionized water until neutral, and dry with a desiccant. Wherein: The desiccant is one of anhydrous calcium chloride, anhydrous magnesium sulfate, and anhydrous sodium sulfate.

14. The method for preparing a multifunctional bio-osmotic agent as described in claim 3, characterized in that, In step (S3), the nucleophilic substitution catalyst of the haloalkane is one or more of tetrabutylammonium bromide, methyltrioctylammonium chloride, phenyltrimethylammonium chloride, and polyethylene glycol.

15. The method for preparing a multifunctional bio-osmotic agent as described in claim 3, characterized in that, The base mentioned in step (S3) is NaOH or KOH.

16. The method for preparing a multifunctional bio-osmotic agent as described in claim 3, characterized in that, In step (S3), the nucleophilic substitution reaction of haloalkane is carried out at a temperature of 50-120℃ for 2-13 hours.

17. The method for preparing a multifunctional bio-osmotic agent as described in claim 3, characterized in that, In step (S3), the third solvent is deionized water, and the amount of the third solvent used is 15-25 mL / g based on the mass of the alkali.

18. The method for preparing a multifunctional bio-osmotic agent as described in claim 3, characterized in that, The esterification catalyst in step (S4) is one or more of organic acids and inorganic acids.

19. The method for preparing a multifunctional bio-osmotic agent as described in claim 18, characterized in that, The inorganic acid is one or more of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and boric acid; the organic acid is one or more of p-toluenesulfonic acid, naphthenic acid, and methanesulfonic acid.

20. The method for preparing a multifunctional bio-osmotic agent as described in claim 3, characterized in that, The esterification reaction in step (S4) is carried out at a temperature of 100-150℃ for 5-10 hours.

21. The method for preparing a multifunctional bio-osmotic agent as described in claim 3, characterized in that, The fourth solvent mentioned in step (S4) is one of benzene, toluene, xylene, and dichloromethane.

22. The method for preparing a multifunctional bio-osmotic agent as described in claim 3, characterized in that, The amount of the fourth solvent used in step (S4) is 1-3 mL / g, based on the mass of the compound shown in formula (Z).

23. The method for preparing a multifunctional bio-osmotic agent as described in claim 3, characterized in that, The specific steps of the fourth post-processing described in step (S4) are as follows: first, filter and retain the liquid phase; then, distill under reduced pressure; and finally, purify using silica gel column chromatography, wherein: The specific process parameters for purification by silica gel column chromatography are as follows: 200-300 mesh silicone; m 硅胶 :m 待分离组分 =(30~50):1, wet packing of column, wet loading of sample; The developing solvent was 20 v / v% methanol + 80 v / v% dichloromethane, and separation was performed under pressure.

24. A multifunctional bio-osmotic agent, characterized in that, Prepared by the preparation method described in any one of claims 3-23.

25. The application of the multifunctional bio-permeabilizer according to any one of claims 1, 2 and 24 as a permeabilizer in shale oil reservoir production.

26. The application as described in claim 25, characterized in that, The specific steps for the above application are as follows: inject the proppant and any of the above-mentioned multifunctional bio-absorbents into the target shale oil layer, and shut in the well for at least 2 days after fracturing.

Images