Multifunctional biological imbibition agent as well as preparation method and application thereof

Abstract

The invention discloses a multifunctional biological imbibition agent as well as a preparation method and application thereof. The preparation method of the multifunctional biological imbibition agent comprises the following steps: (S1) carrying out alkylation reaction to obtain alkyl naphthalene; (S2) carrying out chloromethylation reaction to obtain halomethyl alkyl naphthalene; (S3) carrying out nucleophilic substitution reaction on alkyl halide to obtain hydroxymethyl alkyl naphthalene; and (S4) carrying out esterification reaction to obtain the multifunctional biological imbibition agent. The invention also discloses an application of the multifunctional biological imbibition agent as an imbibition agent in shale oil reservoir oil extraction. The invention has the following advantages: (1) the reservoir adsorption capacity is low, but the good wetting reversal characteristic is still maintained, and the emulsification is weak; (2) the high temperature resistance is high, and the temperature resistance reaches 200 DEG C or above; (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] The present invention belongs to the field of oil exploitation, and particularly relates to a multifunctional biological imbibition agent and a preparation method and application thereof. Background Art

[0002] Oil is the "blood of modern industry" and a strategic resource for the survival and development of a country. However, as China's old oilfields have entered the late stage of high water cut development, the main battlefield of oilfield exploitation has also shifted to unconventional reservoir types (such as shale oil).

[0003] The physical properties of rock reservoirs are significantly different from those of conventional reservoirs, showing characteristics of low porosity and low permeability. Their porosity is generally less than 10%, and the average pore diameter is about 100 nm. China has a high geological reserve of shale oil. The shale oil in Shengli Oilfield is characterized by deep burial, low degree of organic matter evolution, and high crude oil density. Therefore, it is more difficult to develop on a large scale with economic benefits.

[0004] The development of shale oil mainly relies on fracturing, and chemical imbibition agents are also injected to displace the crude oil in the pores. For example, in Chinese invention patent CN112694885A, a high-activity drag reducer, a self-imbibition energy-increasing and oil-production-enhancing slickwater fracturing fluid system applicable to shale oil reservoirs, and a preparation method and application thereof are disclosed. The high-activity drag reducer and anti-swelling agent in the slickwater fracturing fluid system, in terms of mass fraction, the high-activity drag reducer is 0.08% - 0.12%, and the anti-swelling agent is 0.3% - 0.5%, with the balance being water. However, the use cost of such oil displacement agents is high, the adsorption is large, and the pollution is strong. Therefore, there is an urgent need to develop a multifunctional and efficient biological imbibition agent to greenly and efficiently develop shale oil.

[0005] Biosurfactants are surface-active products metabolized by specific microorganisms during growth. Common biosurfactants include lipopeptides, rhamnolipids, sophorolipids, and other lipid derivatives. One end of the molecular structure of biosurfactants is a hydrophilic group, and the other end is a hydrophobic group. Compared with traditional chemically synthesized surfactants, biosurfactants have diverse molecular structures, rich functions, and plastic properties, and have great potential in the exploitation of unconventional reservoirs.

[0006] Chinese invention patent CN 112832726B discloses a tertiary oil recovery method for single-well huff and puff inter-well displacement of tight oil shale oil in horizontal wells. The method includes screening measure wells, target intervals, injection intervals, and production intervals, and injecting an injection fluid containing a microbial oil displacement agent from the injection interval, and making the displaced and driven crude oil migrate to the production interval, greatly improving the swept range of the microbial oil displacement agent, connecting the remaining oil areas in the near-well and far-well zones, reducing the interfacial tension between oil and water and the viscosity of crude oil, and achieving the effect of increasing oil production in tertiary oil recovery. However, there are still the following deficiencies: This invention mainly focuses on providing a tertiary oil recovery method for single-well huff and puff inter-well displacement of tight oil shale oil in horizontal wells, and its applicable range is relatively narrow.

[0007] Chinese Patent Application CN113698922A provides a biological shear agent for improving the oil production efficiency of shale oil reservoirs, its preparation method and application. In this invention, a biological shear agent is obtained by mixing a biological shear enzyme powder with a stabilizer and a surfactant, which modifies the rock surface into an underwater superoleophobic state so that the crude oil detaches. However, there are still the following deficiencies: (1) The biological shear enzyme powder provided by this invention changes the rock surface into a superoleophobic state, which is different from the research purpose of this invention to transform the core into hydrophilic by using a multifunctional and highly efficient biological imbibition agent with high temperature resistance and weak emulsification. (2) This invention mainly aims to solve the technical problems existing in the existing microbial enhanced oil recovery process, such as long construction period, complex construction process, small sweep area of the flooding agent, and easy occurrence of water lock effect and water channeling phenomenon. This invention mainly provides a multifunctional biological imbibition agent for improving the imbibition efficiency after fracturing of shale oil reservoirs and further enhancing the recovery rate.

[0008] Chinese Patent Application CN112892394A provides a sulfonic acid-based anionic gemini surfactant, its preparation, an imbibition flooding agent for shale oil reservoirs and its application. Compound II is prepared by reacting 2,3-diphenylmaleic anhydride with 7-ethyl-2-methyl-4-undecanol. Compound III is prepared by reacting Compound II with hydroxyethylsulfonic acid. The sulfonic acid-based anionic gemini surfactant compound shown in Formula I is prepared by reacting Compound III with a base. However, this invention still has the following deficiencies: (1) The alkyl chain in the hydrophobic group of the imbibition flooding agent provided by this invention is too long, resulting in poor temperature resistance. (2) The imbibition flooding agent provided by this invention has strong emulsification performance, which is likely to intensify the Jamin effect, leading to an increase in the displacement pressure and serious demulsification problems of the subsequent produced fluid.

[0009] In addition, previous studies have also been carried out on the role of microorganisms in the process of shale oil reservoir exploitation. For example, Malik S.Y. Haddadin et al. reported the effect of a biosurfactant produced by Rhodococcus metabolism on the EI-Lajjun oil shale in the literature "Kinetics of hydrocarbon extraction from oil shale using bio-surfactant producing bacteria, Energy Conversion and Management, 2009". It was found that it could significantly improve the solubility of hydrocarbons by forming micelles and effectively reduce the surface tension and interfacial tension. Although this type of biosurfactant shows the ability to improve the oil displacement efficiency, its working condition is room temperature, and the oil production mechanism is only to change the properties of the oil-water interface. Therefore, the increase in the recovery rate is limited. Summary of the Invention

[0010] Object of the Invention: A multifunctional biological imbibition agent, a preparation method thereof and an application thereof are provided for solving the problems of strong pollution and poor reservoir adaptability existing in the existing shale oil imbibition agent.

[0011] In the present invention, lipopeptide is used as a raw material, and through a chemical reaction, a novel modified lipopeptide is prepared. The present invention aims to improve the hydrocarbon group length and geometric size of the hydrophobic chain of the lipopeptide after chemical modification, reduce the adsorption capacity of the lipopeptide on the rock surface, enhance its adaptability to crude oil in different blocks on the basis of ensuring strong wetting modification, greatly improve its ability to reduce the oil-water interfacial tension, and enrich the structural diversity of the biosurfactant. The preparation method has the characteristics of less raw material consumption and high product yield, and the application method has the characteristics of wide adaptability, strong operability, low cost and obvious oil increment effect. In addition, according to different reservoir conditions, a displacement system mainly composed of a modified lipopeptide biological imbibition agent with the characteristics of wetting modification and low interfacial tension is constructed to achieve the purpose of reducing the dosage of chemical displacement agents and improving the displacement efficiency.

[0012] Technical Solution: A multifunctional biological imbibition agent, the molecular structural formula of which is shown in formula (1):

[0013]

[0014] Wherein:

[0015] R 1 、R 2 are independently

[0016] R 3 is an alkyl group of C 1 -C 15 .

[0017] Furthermore, R 1 、R 2 are both

[0018] R 3 is an alkyl group of C 1 -C 10 .

[0019] A preparation method of the multifunctional biological imbibition agent according to any one of the above, in terms of mole parts, the steps are as follows:

[0020] (S1) Alkylation reaction:

[0021] 1 part of the compound represented by formula (X) and 0.8 - 1.2 parts of the compound represented by formula (Y) react in an appropriate amount of a first solvent under the catalysis of 0.02 - 0.08 parts of an alkylation catalyst. After the reaction is completed, a reaction solution is obtained. It is cooled to room temperature, and then the reaction solution is subjected to a first post-treatment to obtain alkylnaphthalene;

[0022] (S2) Chloromethylation reaction:

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

[0024] (S3) Nucleophilic substitution reaction of haloalkane:

[0025] The halomethylalkylnaphthalene obtained in step (S2) reacts with 0.8 - 1.2 parts of a base in an appropriate amount of a third solvent under 0.12 - 0.18 parts of a nucleophilic substitution catalyst for haloalkane. After the reaction is completed, a reaction solution is obtained. It 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) reacts with 0.4 - 0.5 parts of the compound represented by formula (Z) in an appropriate amount of a fourth solvent under the catalysis of 0.02 - 0.08 parts of an esterification reaction catalyst. After the reaction is completed, a reaction solution is obtained. It is cooled to room temperature, and then the reaction solution is subjected to a fourth post-treatment to obtain a multifunctional biological osmotic agent, where:

[0028]

[0029] R 3 is an alkyl group of C 1 -C 15 , preferably an alkyl group of C 1 -C 10 .

[0030] Furthermore, the alkylation catalyst in step (S1) is one of AlCl 3 , FeCl 3 , SbCl 5 , SnCl 4 , BF 3 , TiCl 4 , ZnCl 2 .

[0031] Further, the reaction temperature of the alkylation reaction in step (S1) is 80 - 150 °C, and the reaction time is 10 - 120 min.

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

[0033] Further, the dosage of the first solvent in step (S1), based on the molar amount of the compound represented by formula (X), is 200 - 1000 mL / mol.

[0034] Further, the specific steps of the first post-treatment in step (S1) are: first, filter by suction to retain the liquid, and then perform vacuum distillation.

[0035] Further, the chloromethylation catalyst in step (S2) is ZnCl 2 .

[0036] Further, the reaction temperature of the chloromethylation reaction in step (S2) is 50 - 100 °C, and the reaction time is 4 - 11 h.

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

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

[0039] Further, the specific steps of the second post-treatment in step (S2) and step (S3) are:

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

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

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

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

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

[0045] Further, the reaction temperature of the haloalkane nucleophilic substitution reaction in step (S3) is 50 - 120 °C, and the reaction time is 2 - 13 h.

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

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

[0048] Still further, 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] Further, in step (S4), the reaction temperature of the esterification reaction is 100 - 150 °C, and the reaction time is 5 - 10 h.

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

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

[0052] Further, the specific steps of the fourth post-treatment in step (S4) are as follows: first, filter by suction to retain the liquid phase, then perform vacuum distillation, and finally purify by silica gel column chromatography, where:

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

[0054] The silica gel is 200 - 300 mesh;

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

[0056] The eluent is 20 v / v% methanol + 80 v / v% dichloromethane, and separation is carried out under pressure.

[0057] The multifunctional biological imbibition agent is prepared by the preparation method described in any one of the above.

[0058] Application of the multifunctional biological imbibition agent described in any one of the above as an imbibition agent in shale oil reservoir oil production.

[0059] Further, the specific steps of the above application are as follows: Inject the proppant and the multifunctional biological imbibition agent described in any one of the above into the target shale oil layer, and shut in the well for at least 2 days after fracturing.

[0060] Aiming at the problems of high use cost, large adsorption, strong pollution, poor reservoir adaptability, etc. existing in the existing shale oil imbibition agents, the multifunctional biological imbibition agent provided by the present invention uses the lipopeptide shown by formula (Z) as a raw material, forms hydroxymethylalkylnaphthalene through three-step reactions, and then uses an esterification reaction to make the hydroxymethylalkylnaphthalene react with the lipopeptide to generate the multifunctional biological imbibition agent. This multifunctional biological imbibition agent has the characteristics of high temperature resistance, weak emulsification, strong wetting modification, and small adsorption amount.

[0061] Specifically, the multifunctional biological imbibition agent aims to increase the hydrocarbon group length and geometric size of the hydrophobic chain of the lipopeptide. While ensuring its own function of strong wetting inversion, it greatly reduces its adsorption ability on the rock surface, and the introduced alkylnaphthalene group has strong heat resistance.

[0062] In addition, the multifunctional biological imbibition agent has weak emulsification performance, which greatly reduces the Jamin effect of crude oil in the pores of the shale reservoir and avoids the problem of difficult demulsification of the produced fluid.

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

[0064] (1) The multifunctional biological imbibition agent of the present invention has a small reservoir adsorption amount, but still maintains good wetting inversion characteristics and weak emulsification - when the dosage exceeds 2000 ppm, the wettability of the oil-wet core reaches above 0.60, the emulsification ability is below 25%, the static permeability recovery value > 80%, and the imbibition displacement rate is about 20%;

[0065] (2) The multifunctional biological imbibition agent of the present invention has good high temperature resistance and can withstand temperatures above 200 °C;

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

[0067] (4) The multifunctional biological imbibition agent of the present invention has the characteristics of small dosage and low cost, and has significant economic benefits. Description of the Drawings

[0068] Figure 1 It is a flowchart of the preparation method of the multifunctional biological imbibition agent disclosed by the present invention. Specific Embodiments

[0069] The following combines specific embodiments and further describes the present invention in detail with reference to data. It should be understood that these embodiments are only for illustrating the present invention and do not limit the scope of the present invention in any way.

[0070] The preparation route of the multifunctional biological imbibition agent of the present invention is as follows:

[0071]

[0072] R1 , R 2 independently is

[0073] R 3 is C 1 -C 15 alkyl group of

[0074] X is one of Cl and Br.

[0075] Example 1

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

[0077] Wherein:

[0078] R 1 , is

[0079] R 2 is

[0080] R 3 is methyl.

[0081] Example 2

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

[0083]

[0084]

[0085] Wherein:

[0086] R 1 , R 2 both are

[0087] R 3 is n-decyl.

[0088] Example 3

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

[0090] Wherein:

[0091] R 1 , R 2 both are

[0092] R 3 is pentadecyl.

[0093] Example 4

[0094] A multifunctional biological osmotic agent, whose molecular structural formula is shown in formula (1):

[0095] Wherein:

[0096] R 1 and R 2 are both

[0097] R 3 is cyclobutyl.

[0098] Example 5

[0099] A preparation method of a multifunctional biological osmotic agent, in terms of mole parts, the steps are as follows:

[0100] (S1) Alkylation reaction:

[0101] 1 part of the compound shown in formula (X) and 1 part of the compound shown in formula (Y) are reacted in an appropriate amount of a first solvent under the catalysis of 0.04 parts of an alkylation catalyst. After the reaction is completed, a reaction solution is obtained, cooled to room temperature, and then the reaction solution is subjected to a first post-treatment to obtain alkylnaphthalene;

[0102] (S2) Chloromethylation reaction:

[0103] The alkylnaphthalene obtained in step (S1) is reacted with 1 part of formaldehyde and 2.1 parts of hydrohalic acid in an appropriate amount of a second solvent under the catalysis of 0.04 parts of a 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 halomethylalkylnaphthalene;

[0104] (S3) Haloalkane nucleophilic substitution reaction:

[0105] The halomethylalkylnaphthalene obtained in step (S2) is reacted with 1 part of a base in an appropriate amount of a third solvent under 0.15 parts of a haloalkane nucleophilic substitution 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 hydroxymethylalkylnaphthalene;

[0106] (S4) Esterification reaction:

[0107] The hydroxymethylalkylnaphthalene obtained in step (S3) is 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 reaction catalyst. After the reaction is completed, a reaction solution is obtained, cooled to room temperature, and then the reaction solution is subjected to a fourth post-treatment to obtain a multifunctional biological osmotic agent, wherein:

[0108]

[0109] R 3 is ethyl.

[0110] Furthermore, the alkylation catalyst in step (S1) is AlCl 3 .

[0111] Furthermore, the reaction temperature of the alkylation reaction in step (S1) is 100 °C, and the reaction time is 100 min.

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

[0113] Furthermore, the amount of the first solvent in step (S1) is 500 mL / mol based on the molar amount of the compound represented by formula (X).

[0114] Furthermore, the specific steps of the first post-treatment in step (S1) are: first, filter by suction to retain the liquid, and then perform vacuum distillation.

[0115] Furthermore, the chloromethylation catalyst in step (S2) is ZnCl 2 .

[0116] Furthermore, the reaction temperature of the chloromethylation reaction in step (S2) is 60 °C, and the reaction time is 7 h.

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

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

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

[0120] S21: Extract with chloroform and retain the organic phase;

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

[0122] The desiccant is anhydrous calcium chloride.

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

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

[0125] Furthermore, the reaction temperature of the nucleophilic substitution reaction of haloalkane in step (S3) is 70 °C, and the reaction time is 4 h.

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

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

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

[0129] Further, in step (S4), the reaction temperature of the esterification reaction is 120 °C, and the reaction time is 7 h.

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

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

[0132] Further, the specific steps of the fourth post-treatment in step (S4) are as follows: first, filter by suction to retain the liquid phase, then perform vacuum distillation, and finally purify by silica gel column chromatography, where:

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

[0134] Silica gel 250 mesh;

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

[0136] The eluent is 20 v / v% methanol + 80 v / v% dichloromethane, and separation is carried out under pressure.

[0137] The multifunctional biological imbibition agent is prepared by the preparation method described in any one of the above.

[0138] Application of the multifunctional biological imbibition agent described in any one of the above as an imbibition agent in shale oil reservoir oil production.

[0139] Further, the specific steps of the above application are as follows: injecting a proppant and the multifunctional biological imbibition agent described in any one of the above into the target shale oil layer, and shutting in the well for 2 days after fracturing.

[0140] Example 6

[0141] A preparation method of a multifunctional biological imbibition agent, in terms of mole parts, the steps are as follows:

[0142] (S1), Alkylation reaction:

[0143] 1 part of the compound represented by formula (X) and 0.8 part of the compound represented by formula (Y) are reacted in an appropriate amount of a first solvent under the catalysis of 0.02 part of an alkylation catalyst. After the reaction is completed, a reaction solution is obtained, cooled to room temperature, and then the reaction solution is subjected to a first post-treatment to obtain alkylnaphthalene;

[0144] (S2), Chloromethylation reaction:

[0145] The alkylnaphthalene obtained in step (S1) is reacted with 0.9 part of formaldehyde and 2 parts of hydrohalic acid in an appropriate amount of a second solvent under the catalysis of 0.02 part of a 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 halomethylalkylnaphthalene;

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

[0147] The halomethylalkylnaphthalene obtained in step (S2) is reacted with 0.8 part of a base in an appropriate amount of a third solvent under 0.12 part of a nucleophilic substitution catalyst for haloalkane. 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 hydroxymethylalkylnaphthalene;

[0148] (S4), Esterification reaction:

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

[0150]

[0151] R 3 is methyl.

[0152] Furthermore, the alkylation catalyst in step (S1) is FeCl 3 .

[0153] Furthermore, the reaction temperature of the alkylation reaction in step (S1) is 80 °C and the reaction time is 120 min.

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

[0155] Furthermore, the amount of the first solvent in step (S1) is 200 mL / mol based on the molar amount of the compound represented by formula (X).

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

[0157] Further, the chloromethylation catalyst in step (S2) is ZnCl 2 .

[0158] Further, the reaction temperature of the chloromethylation reaction in step (S2) is 50 °C, and the reaction time is 11 h.

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

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

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

[0162] S21. Extract with ethyl acetate and retain the organic phase;

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

[0164] The desiccant is anhydrous magnesium sulfate.

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

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

[0167] Further, the reaction temperature of the haloalkane nucleophilic substitution reaction in step (S3) is 50 °C, and the reaction time is 13 h.

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

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

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

[0171] Further, the reaction temperature of the esterification reaction in step (S4) is 100 °C, and the reaction time is 10 h.

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

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

[0174] Further, the specific steps of the fourth post-treatment in step (S4) are as follows: first, filter by suction to retain the liquid phase, then perform vacuum distillation, and finally purify by silica gel column chromatography, where:

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

[0176] 200-mesh silica gel;

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

[0178] The developing agent is 20 v / v% methanol + 80 v / v% dichloromethane, and separation is carried out under pressure.

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

[0180] Application of the multifunctional bio-osmotic agent described in any one of the above as an osmotic agent in shale oil reservoir oil production.

[0181] Further, the specific steps of the above application are as follows: Inject the proppant and the multifunctional bio-osmotic agent described in any one of the above into the target shale oil layer, and shut in the well for 3 days after fracturing.

[0182] Example 7

[0183] A preparation method of a multifunctional bio-osmotic agent, in terms of mole parts, the steps are as follows:

[0184] (S1), Alkylation reaction:

[0185] 1 part of the compound shown by formula (X), 1.2 parts of the compound shown by formula (Y) in an appropriate amount of the first solvent, react under the catalysis of 0.08 parts of an alkylation catalyst, after the reaction is completed, obtain a reaction solution, cool to room temperature, and then perform the first post-treatment on the reaction solution to obtain alkylnaphthalene;

[0186] (S2), Chloromethylation reaction:

[0187] React the alkylnaphthalene obtained in step (S1) with 1.1 parts of formaldehyde and 2.3 parts of hydrohalic acid in an appropriate amount of the second solvent under the catalysis of 0.08 parts of a chloromethylation catalyst, after the reaction is completed, obtain a reaction solution, cool to room temperature, and then perform the second post-treatment on the reaction solution to obtain halomethylalkylnaphthalene;

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

[0189] React the halogenomethylalkylnaphthalene obtained in step (S2) with 1.2 parts of base in an appropriate amount of a third solvent under 0.18 part of a nucleophilic substitution catalyst for halogenoalkane to obtain a reaction solution after the reaction is completed. Cool the reaction solution to room temperature, and then perform a second post-treatment on the reaction solution to obtain hydroxymethylalkylnaphthalene;

[0190] (S4) Esterification reaction:

[0191] React the hydroxymethylalkylnaphthalene obtained in step (S3) with 0.5 part of the compound represented by formula (Z) in an appropriate amount of a fourth solvent under the catalysis of 0.08 part of an esterification reaction catalyst to obtain a reaction solution after the reaction is completed. Cool the reaction solution to room temperature, and then perform a fourth post-treatment on the reaction solution to obtain a multifunctional biological osmotic agent, where:

[0192]

[0193]

[0194] R 3 is n-decyl.

[0195] Further, the alkylation catalyst in step (S1) is AlCl 3 . In another embodiment, the alkylation catalyst in step (S1) is SbCl 5 . In another embodiment, the alkylation catalyst in step (S1) is SnCl 4 . In another embodiment, the alkylation catalyst in step (S1) is BF 3 . In another embodiment, the alkylation catalyst in step (S1) is TiCl 4 . In another embodiment, the alkylation catalyst in step (S1) is ZnCl 2 .

[0196] Further, the reaction temperature of the alkylation reaction in step (S1) is 150 °C and the reaction time is 10 min.

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

[0198] Further, the amount of the first solvent in step (S1) is 1000 mL / mol based on the molar amount of the compound represented by formula (X).

[0199] Further, the specific steps of the first post-treatment in step (S1) are: first filter by suction to retain the liquid, and then perform vacuum distillation.

[0200] Further, the chloromethylation catalyst in step (S2) is ZnCl 2 .

[0201] Further, in step (S2), the reaction temperature of the chloromethylation reaction is 100 °C, and the reaction time is 4 h.

[0202] Further, in step (S2), the hydrohalic acid 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] Further, the specific steps of the second post-treatment in step (S2) and step (S3) are as follows:

[0205] S21. Extract with butyl acetate and retain the organic phase;

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

[0207] The desiccant is anhydrous sodium sulfate.

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

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

[0210] Further, in step (S3), the reaction temperature of the nucleophilic substitution reaction of alkyl halide is 120 °C, and the reaction time is 2 h.

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

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

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

[0214] Further, in step (S4), the reaction temperature of the esterification reaction is 150 °C, and the reaction time is 5 h.

[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 another embodiment, the fourth solvent in step (S4) is dichloromethane.

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

[0217] Further, the specific steps of the fourth post-treatment in step (S4) are as follows: first, filter by suction to retain the liquid phase, then perform vacuum distillation, and finally purify by silica gel column chromatography, where:

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

[0219] 300-mesh silica gel;

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

[0221] The eluent is 20 v / v% methanol + 80 v / v% dichloromethane, and separation is carried out under pressure.

[0222] The multifunctional biological imbibition agent is prepared by the preparation method described in any one of the above.

[0223] Application of the multifunctional biological imbibition agent described in any one of the above as an imbibition agent in shale oil reservoir production.

[0224] Further, the specific steps of the above application are as follows: Inject the proppant and the multifunctional biological imbibition agent described in any one of the above into the target shale oil layer, and shut in the well for 4 days after fracturing.

[0225] Examples 8 - 15

[0226] It is substantially the same as Example 5, except that: the esterification catalyst in step (S4) is different:

[0227]

[0228]

[0229] Example 16

[0230] Application of the multifunctional biological imbibition agent prepared in Example 5 in shale oil reservoir block A1 of a certain well group in Shengli Oilfield, with 1 injection well and 5 production wells in this well group.

[0231] Well overview: formation temperature is 150°C, formation water salinity is 57336 mg / L, effective thickness of the target layer is 10.5 m, porosity is 4.65%, and permeability is 0.21×10 -3 μm 2 . The target layer of this well is an interbedded layer of marl, mudstone, limestone and dolomite, the formation pressure is 48.9 MPa, and the average daily oil increment per well after fracturing is 0.12 t / d.

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

[0233] Under the condition of higher than the fracture pressure, inject the proppant and the multifunctional bio-infiltration agent into the target shale oil layer, and shut in the well for 2 days after fracturing.

[0234] Furthermore, the injection concentration of the multifunctional bio-infiltration agent is 2000 ppm, and the injection volume is 47000 m 3 .

[0235] Furthermore, after shutting in the well for 2 days, when the pressure change of the fractured well ≤ 0.15 MPa, the well can be opened for blowout.

[0236] Test results: After injecting the multifunctional bio-infiltration agent, the average daily oil increment per well reached 3.7 t, and the effective period reached 60 days, and the on-site test effect was good.

[0237] Performance test:

[0238] Test Example 1

[0239] Determination of core wettability: Refer to Method 3 in SY / T5153-2007 for experiments, and select natural cores, corresponding crude oil, formation water and the multifunctional bio-infiltration agent prepared in Example 5 from 3 different shale oil reservoir blocks in Shengli Oilfield

[0240] First, refer to the treatment in Section 7 of SY / T 6540-2021 to prepare the natural core of shale oil, and then use the self-absorption method to evaluate the change in the wettability of the oil-wet natural shale core by the multifunctional bio-infiltration agent obtained in Example 5 at 2000 ppm (using the formation water of each block for solution preparation).

[0241] The test temperature is 85°C. The results of core wettability determination are shown in Table 1.

[0242] Table 1 Influence of multifunctional bio-infiltration agent on wettability of natural core in shale oil reservoir

[0243]

[0244] From the wettability measurement results, it can be seen that the multifunctional biological imbibition agent provided by the present invention has the function of significantly changing the wettability of oil-wet reservoirs. After the action, the oil-wet core becomes a water-wet or strongly water-wet core.

[0245] Determination of emulsifying performance: Referring to the method in GB / T 6369-2008, using a visible light spectrophotometer, the emulsifying ability of the multifunctional biological imbibition agent obtained in Example 5 was evaluated by measuring the optical density value of the extraction solution.

[0246] The test temperature was 85 °C, and the oil phases used were 3 kinds of crude oils from different shale oil reservoirs. The emulsifying performance results are shown in Table 2.

[0247] Table 2 Influence of the concentration of the multifunctional biological imbibition agent on the emulsifying performance of crude oil in shale oil reservoirs

[0248]

[0249] The emulsifying performance results show that the multifunctional biological imbibition agent of the present invention has weak emulsifying performance. After the action of 2000 ppm of the multifunctional biological imbibition agent, the emulsifying power is only below 25%, which greatly reduces the Jamin effect of crude oil in the pores of shale oil reservoirs and is more conducive to improving the recovery rate of shale oil reservoirs.

[0250] Test Example 2

[0251] High-temperature stability evaluation method: Select natural cores from 4 different shale oil reservoir blocks in Shengli Oilfield, the corresponding crude oil, formation water, and the multifunctional biological imbibition agent prepared in Example 5.

[0252] First, refer to the treatment in Section 7 of SY / T 6540-2021 to prepare the natural core of shale oil, and then refer to the method in 3 of SY / T5153-2007 for the experiment. The change in the wettability of the oil-wet natural shale core by the multifunctional biological imbibition agent prepared in Example 5 at 2000 ppm (using the formation water of each block for solution preparation) was evaluated by the self-imbibition method.

[0253] The test temperatures were 60 °C, 80 °C, 100 °C, 150 °C, and 180 °C. The core wettability measurement results are shown in Table 3.

[0254] Table 3 High-temperature stability of the wetting modification ability of the multifunctional biological imbibition agent

[0255]

[0256] The experimental results confirmed that the multifunctional biological imbibition agent provided by the present invention still exhibited good wetting reversal stability under high-temperature conditions (200 °C). After the action, it could transform the oil-wet core into a water-wet or strongly water-wet core, which was suitable for the development of high-temperature shale oil reservoirs.

[0257] Test Example 3

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

[0259] First, prepare the shale oil natural core with reference to Section 7 of SY / T 6540-2021. Subsequently, use the static evaluation experiment of shale oil reservoir bio-osmotic agent damage shown in Section 11 of SY / T6540-2021 to select the concentration of the multifunctional bio-osmotic agent: 2000 ppm; reservoir temperature: 150 °C; the static permeability recovery value of the shale oil reservoir before and after the bio-osmotic agent damages the core is calculated with reference to Formula (3) in SY / T 6540-2021: The measurement results of the reservoir damage rate (static permeability recovery value) are shown in Table 4, and the osmotic agent used is the multifunctional bio-osmotic agent prepared in Example 5.

[0260] Table 4 Static permeability recovery value of shale oil reservoir of multifunctional bio-osmotic agent

[0261]

[0262]

[0263] The experimental results confirm that the multifunctional bio-osmotic agent provided by the present invention has a small adsorption amount in the shale oil reservoir, the static permeability recovery value > 80%, has less damage to the rock permeability, and can avoid potential water lock and water sensitivity damage.

[0264] Test Example 4

[0265] Osmotic displacement rate evaluation method: Select natural cores, corresponding crude oil, formation water, and the multifunctional bio-osmotic agent prepared in Example 5 from three different shale oil reservoir blocks in Shengli Oilfield.

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

[0267] Prepare a 2000 ppm biological wetting regulator solution with the block water sample and pour it into the suction instrument. Subsequently, place the aged core in the suction instrument filled with the biological wetting regulator solution and seal it, and let it stand at the block reservoir temperature. During the osmotic process, record the osmotic oil production every 6 h until the osmotic oil production tends to be stable. The specific experimental results are shown in Table 5.

[0268] Table 5 Evaluation of osmotic displacement rate of multifunctional bio-osmotic agent

[0269]

[0270]

[0271] The experimental results confirm that the multifunctional biological imbibition agent prepared in Example 5 provided by the present invention reaches the imbibition equilibrium within 48 h, and the imbibition displacement rate is about 20%, and the imbibition effect is good.

[0272] The above has made a detailed description of the implementation manner of the present invention. However, the present invention is not limited to the above implementation manner, and various changes can be made without departing from the gist of the present invention within the scope of knowledge possessed by those of ordinary skill in the art.

Claims

1. A multifunctional biological osmotic agent, characterized in that, Its molecular structural formula is as shown in Formula (1): wherein: R 1 、R 2 are independently R 3 is C 1 -C 15 alkyl group.

2. A multifunctional biological osmotic agent according to claim 1, characterized in that, R in formula (1) 1 and R 2 are both R 3 is C 1 -C 10 alkyl group.

3. A preparation method of the multifunctional biological osmotic agent according to claim 1 or 2, characterized in that, in terms of molar parts, the steps are as follows: (S1) Alkylation reaction: 1 part of the compound shown by formula (X), 0.8 - 1.2 parts of the compound shown by formula (Y) are 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 is completed, a reaction solution is obtained, cooled to room temperature, and then the reaction solution is subjected to a first post-treatment to obtain alkylnaphthalene; (S2) Chloromethylation reaction: The alkylnaphthalene 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 a second solvent under the catalysis of 0.02 - 0.08 parts of a 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 halomethylalkylnaphthalene; (S3) Haloalkane nucleophilic substitution reaction: The halomethylalkylnaphthalene obtained in step (S2) is reacted with 0.8 - 1.2 parts of a base in an appropriate amount of a third solvent under 0.12 - 0.18 parts of a haloalkane nucleophilic substitution 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 hydroxymethylalkylnaphthalene; (S4) Esterification reaction: The hydroxymethylalkylnaphthalene obtained in step (S3) is reacted with 0.4 - 0.5 parts of the compound shown by formula (Z) in an appropriate amount of a fourth solvent under the catalysis of 0.02 - 0.08 parts of an esterification reaction catalyst. After the reaction is completed, a reaction solution is obtained, cooled to room temperature, and then the reaction solution is subjected to a fourth post-treatment to obtain the multifunctional biological osmotic agent, wherein: R 3 is C 1 -C 15 alkyl, preferably C 1 -C 10 alkyl.

4. A preparation method of a multifunctional biological osmotic agent according to claim 3, characterized in that, The alkylation catalyst in step (S1) is one of AlCl 3 , FeCl 3 , SbCl 5 , SnCl 4 , BF 3 , TiCl 4 , ZnCl 2 .

5. A preparation method of a multifunctional biological osmotic agent according to claim 3, characterized in that, The reaction temperature of the alkylation reaction in step (S1) is 80 - 150 °C, and the reaction time is 10 - 120 min.

6. A preparation method of a multifunctional biological osmotic agent according to claim 3, characterized in that, The first solvent in step (S1) is one of hexane, cyclohexane, and heptane.

7. A preparation method of a multifunctional biological osmotic agent according to claim 3, characterized in that, The dosage of the first solvent in step (S1) is 200 - 1000 mL / mol based on the molar amount of the compound shown by formula (X).

8. A preparation method of a multifunctional biological osmotic agent according to claim 3, characterized in that, The specific steps of the first post-treatment in step (S1) are: first filter by suction to retain the liquid, and then perform vacuum distillation.

9. A preparation method of a multifunctional biological osmotic agent according to claim 3, characterized in that, The chloromethylation catalyst in step (S2) is ZnCl 2 ; The hydrohalic acid in step (S2) is hydrochloric acid or hydrobromic acid.

10. A preparation method of a multifunctional biological osmotic agent according to claim 3, characterized in that, In step (S2), the reaction temperature of the chloromethylation reaction is 50-100 °C, and the reaction time is 4-11 h.

11. A method for preparing a multifunctional biological 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.

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

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

14. A method for preparing a multifunctional biological osmotic agent as described in claim 3, characterized in that the base in step (S3) is NaOH or KOH.

15. A method for preparing a multifunctional biological osmotic agent as described in claim 3, characterized in that in step (S3), the reaction temperature of the haloalkane nucleophilic substitution reaction is 50-120 °C, and the reaction time is 2-13 h.

16. A method for preparing a multifunctional biological 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 is 15-25 mL / g based on the mass of the base.

17. A method for preparing a multifunctional biological 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.

18. A method for preparing a multifunctional biological osmotic agent as described in claim 17, 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.

19. A method for preparing a multifunctional biological osmotic agent as described in claim 3, characterized in that in step (S4), the reaction temperature of the esterification reaction is 100-150 °C, and the reaction time is 5-10 h.

20. A method for preparing a multifunctional biological osmotic agent as described in claim 3, characterized in that in step (S4), the fourth solvent is one of benzene, toluene, xylene, and dichloromethane.

21. A method for preparing a multifunctional biological osmotic agent as described in claim 3, characterized in that in step (S4), the amount of the fourth solvent is 1-3 mL / g based on the mass of the compound represented by formula (Z).

22. A method for preparing a multifunctional biological osmotic agent as described in claim 3, characterized in that The specific steps of the fourth post-treatment described in step (S4) are as follows: first, filter by suction to retain the liquid phase, then perform vacuum distillation, and finally purify by silica gel column chromatography, where: The specific process parameters for purification by silica gel column chromatography are: Silica gel, 200 - 300 mesh; m 硅胶 : m 待分离组分 =(30 - 50):1, column packing by wet method, sample loading by wet method; The eluent is 20 v / v% methanol + 80 v / v% dichloromethane, and separation is carried out under pressure.

23. Multifunctional biological imbibition agent, which is characterized in that it is prepared by the preparation method described in any one of claims 3 - 22.

24. Use of the multifunctional biological imbibition agent described in any one of claims 1, 2 or 23 as an imbibition agent in oil production from shale reservoirs.

25. The use according to claim 24, which is characterized in that the specific steps of the above use are as follows: inject a proppant and the multifunctional biological imbibition agent described in any one of the above into the target shale oil layer, and shut in the well for at least 2 days after fracturing.

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