WO2023116389A1 - Microemulsion multifunctional nano oil displacing agent and preparation method therefor and application thereof - Google Patents

Microemulsion multifunctional nano oil displacing agent and preparation method therefor and application thereof Download PDF

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WO2023116389A1
WO2023116389A1 PCT/CN2022/136096 CN2022136096W WO2023116389A1 WO 2023116389 A1 WO2023116389 A1 WO 2023116389A1 CN 2022136096 W CN2022136096 W CN 2022136096W WO 2023116389 A1 WO2023116389 A1 WO 2023116389A1
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microemulsion
oil
multifunctional nano
displacing agent
parts
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French (fr)
Chinese (zh)
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蒋其辉
杨向同
王永红
叶禹
黄波
刘建全
张奎
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中国石油天然气集团有限公司
中国石油集团工程技术研究院有限公司
西安康布尔石油技术发展有限公司
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Publication of WO2023116389A1 publication Critical patent/WO2023116389A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C08G65/3324—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic
    • C08G65/3326—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof cyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
    • C09K8/604—Polymeric surfactants
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/10—Nanoparticle-containing well treatment fluids
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/20—Controlling water pollution; Waste water treatment
    • Y02A20/204—Keeping clear the surface of open water from oil spills

Definitions

  • the invention relates to a microemulsion multifunctional nanometer oil displacement agent and its preparation method and application, belonging to the technical field of oil exploitation and oilfield chemical material preparation.
  • Nano-silica is a component commonly used in existing oil displacement agents in this field, wherein the size of nano-silica particles is nanoscale, and there are unsaturated residual bonds and hydroxyl groups in different bonding states on the surface. Deviating from the stable silicon-oxygen structure, it has high activity and strong adsorption characteristics; due to its high activity, it has an effect before reaching the predetermined position during use. To solve this problem, it is necessary to increase its On the other hand, it needs to be released slowly to improve the oil displacement effect of the oil displacement agent.
  • an object of the present invention is to provide a microemulsion multifunctional nano-oil displacing agent, that is, a nano-microemulsion dialysis oil displacing agent.
  • Another object of the present invention is to provide the preparation method of the above-mentioned microemulsion multifunctional nano oil displacing agent.
  • Yet another object of the present invention is to provide the application of the above-mentioned microemulsion multifunctional nano oil displacement agent in the development of tight oil reservoirs.
  • the microemulsion multifunctional nanometer oil displacement agent provided by the invention has very high permeability enhancement and oil displacement ability and excellent stability.
  • the present invention provides a kind of microemulsion multifunctional nano oil displacing agent, wherein, said microemulsion multifunctional nano oil displacing agent comprises:
  • the diphenyl ether gemini surfactant is (octylphenol polyoxyethylene ether disubstituted) diphenyl ether dicarboxylate surface active agent.
  • the diphenyl ether-based gemini surfactant is first obtained by subjecting 4,4'-dicarboxylic acid diphenyl ether to an acyl chloride reaction. 4,4'-diformyl chloride diphenyl ether, and then make 4,4'-diformyl chloride diphenyl ether and octylphenol polyoxyethylene ether (OP-10) for esterification.
  • 4,4'-dicarboxylic acid diphenyl ether to an acyl chloride reaction.
  • 4,4'-diformyl chloride diphenyl ether 4,4'-diformyl chloride diphenyl ether, and then make 4,4'-diformyl chloride diphenyl ether and octylphenol polyoxyethylene ether (OP-10) for esterification.
  • OP-10 octylphenol polyoxyethylene ether
  • the diphenyl ether gemini surfactant used in the present invention is an existing conventional substance (see characteristics of tight oil nanofluid enhanced permeability flooding system and enhanced recovery mechanism, Ding Bin, etc., Petroleum Exploration and Development, 2020 August, pages 756-763), which can be prepared by the existing preparation method shown above, and can also be obtained commercially.
  • the isothiazolinone derivative is first made of NaH, N,N-dimethylformamide and isothiazoline-3 -
  • the ketone is reacted under a nitrogen protective atmosphere, and then ⁇ -chloropropyltriethoxysilane is added to the resulting reaction system, and the reaction is carried out under ice bath conditions for 20-40min, and then reacted at 70-100°C for 2-4h. obtained after solvent separation.
  • the isothiazolinone derivative used in the present invention is an existing conventional substance, which can be prepared by the above-mentioned existing preparation method (see Chinese patent CN102191684A), or can be obtained commercially.
  • the penetration enhancer includes a hyperbranched emulsifying wetting and dispersing agent.
  • the hyperbranched emulsifying wetting and dispersing agent can be a model 31818 product produced by Henan Daochun Chemical Technology Co., Ltd.
  • the stabilizer includes polyvinyl alcohol.
  • the microemulsion multifunctional nano oil displacing agent further includes 1-5 parts of an organic anti-swelling agent.
  • the organic anti-swelling agent includes organic anti-swelling agent HJZ-100.
  • the organic anti-swelling agent HJZ-100 can be a product produced by Kaifeng Hengju Biotechnology Co., Ltd.
  • the microemulsion multifunctional nano oil displacement agent provided by the present invention is added with hyperbranched emulsifying wetting and dispersing agent, polyvinyl alcohol, dodecane and tetradecane, wherein the hyperbranching emulsifying wetting and dispersing agent is mainly used to enhance Enhanced penetration displacement performance, the polyvinyl alcohol is used to improve the stability of the system, and the addition of dodecane and tetradecane is mainly to use its long-chain structure to improve stability, while also considering the cost and feasibility of industrialization, namely The cost of the two is lower, and the industrialization feasibility is higher.
  • the present invention also provides the preparation method of above-mentioned microemulsion multifunctional nano oil displacement agent, wherein, described preparation method comprises:
  • step (3) Add a penetration enhancer, a stabilizer and water to the mixture obtained in step (2), and mix uniformly to obtain the microemulsion multifunctional nano-oil displacing agent.
  • step (1) wherein the homogeneous mixing in step (1) is realized by stirring, and the stirring is 3-5 min under the condition of 2000-3000 r/min.
  • step (2) slow stirring is required after adding dodecane and tetradecane to obtain a product with excellent stability
  • the homogeneous mixing in step (2) is achieved by stirring, and the stirring is 2-4 hours under the condition of 100-300 r/min.
  • step (3) wherein the homogeneous mixing in step (3) is achieved by stirring, and the stirring is 500-1000 r/min for 0.5-2 h.
  • the present invention also provides the application of the above-mentioned microemulsion multifunctional nano oil displacement agent in the development of tight oil reservoirs.
  • the tight oil reservoir is an ultra-low permeability reservoir.
  • the amount of the microemulsion multifunctional nano-oil displacing agent is 0.1%-1% of the mass of the washing oil.
  • the microemulsion multifunctional nano-oil displacing agent provided by the present invention is added with diphenyl ether gemini surfactant, which has good wetting and turning ability, and can be combined with isothiazolinone derivatives, dodecane and tetradecane , can form the main body of oil-soluble crude oil displacement agent, improve the stability of the oil displacement agent in the oil reservoir, so that the oil displacement agent has good penetration and diffusion capabilities; in addition, adding diphenyl ether gemini surfactants can also The principle of similar compatibility can be well used to make the main body of the oil-soluble crude oil displacement agent eliminate the molecular association between various components of crude oil, break up the crude oil into small-sized oils of smaller sizes, and further improve The extraction rate of crude oil.
  • ranges are given in terms of lower limits and upper limits. There can be one or more lower bounds, and one or more upper bounds, respectively.
  • a given range is defined by selecting a lower limit and an upper limit. Selected lower and upper limits define the boundaries of a particular range. All ranges defined in this manner are combinable, ie, any lower limit can be combined with any upper limit to form a range. For example, ranges of 60-120 and 80-110 are listed for a particular parameter, with the understanding that ranges of 60-110 and 80-120 are also contemplated. Additionally, if the minimum range values listed are 1 and 2, and the maximum range values listed are 3, 4, and 5, the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
  • the numerical range “a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
  • the numerical range “0-5" indicates that all real numbers between "0-5" have been listed in the present invention, and "0-5" is only an abbreviated representation of these numerical combinations.
  • microemulsion multifunctional nano oil displacing agent includes:
  • the diphenyl ether-based gemini surfactant is (octylphenol polyoxyethylene ether disubstituted) diphenyl ether diformate surfactant, which firstly makes 4,4'-diphenyl ether dicarboxylate carry out acyl chloride The reaction is to obtain 4,4'-diformyl chloride diphenyl ether, and then the esterification reaction of 4,4'-diformyl chloride diphenyl ether with octylphenol polyoxyethylene ether is obtained.
  • the structural formula of the isothiazolinone derivative is It is first to make NaH, N,N-dimethylformamide and isothiazolin-3-one react under nitrogen protection atmosphere, then add ⁇ -chloropropyltriethoxysilane to the obtained reaction system, It can be obtained by reacting in ice bath for 20-40min, then reacting at 70-100°C for 2-4h, and then separated by solvent.
  • microemulsion multifunctional nano-oil displacing agent is prepared by a preparation method comprising the following steps:
  • microemulsion multifunctional nano oil displacing agent includes:
  • the diphenyl ether-based gemini surfactant is (octylphenol polyoxyethylene ether disubstituted) diphenyl ether diformate surfactant, which firstly makes 4,4'-diphenyl ether dicarboxylate carry out acyl chloride The reaction is to obtain 4,4'-diformyl chloride diphenyl ether, and then the esterification reaction of 4,4'-diformyl chloride diphenyl ether with octylphenol polyoxyethylene ether is obtained.
  • the structural formula of the isothiazolinone derivative is It is first to make NaH, N,N-dimethylformamide and isothiazolin-3-one react under nitrogen protection atmosphere, then add ⁇ -chloropropyltriethoxysilane to the obtained reaction system, It can be obtained by reacting in ice bath for 20-40min, then reacting at 70-100°C for 2-4h, and then separated by solvent.
  • microemulsion multifunctional nano-oil displacing agent is prepared by a preparation method comprising the following steps:
  • microemulsion multifunctional nano oil displacing agent includes:
  • the diphenyl ether-based gemini surfactant is (octylphenol polyoxyethylene ether disubstituted) diphenyl ether diformate surfactant, which firstly makes 4,4'-diphenyl ether dicarboxylate carry out acyl chloride The reaction is to obtain 4,4'-diformyl chloride diphenyl ether, and then the esterification reaction of 4,4'-diformyl chloride diphenyl ether with octylphenol polyoxyethylene ether is obtained.
  • the structural formula of the isothiazolinone derivative is It is first to make NaH, N,N-dimethylformamide and isothiazolin-3-one react under nitrogen protection atmosphere, then add ⁇ -chloropropyltriethoxysilane to the obtained reaction system, It can be obtained by reacting in ice bath for 20-40min, then reacting at 70-100°C for 2-4h, and then separated by solvent.
  • microemulsion multifunctional nano-oil displacing agent is prepared by a preparation method comprising the following steps:
  • This embodiment provides a microemulsion multifunctional nano oil displacing agent, which differs from the microemulsion multifunctional nano oil displacing agent provided in Example 1 only in that:
  • organic anti-swelling agent which is the organic anti-swelling agent of the model HJZ-100 produced by Kaifeng Hengju Biotechnology Co., Ltd.
  • This embodiment provides a microemulsion multifunctional nano oil displacing agent, which differs from the microemulsion multifunctional nano oil displacing agent provided in Example 2 only in that:
  • organic anti-swelling agent which is the organic anti-swelling agent of the model HJZ-100 produced by Kaifeng Hengju Biotechnology Co., Ltd.
  • This embodiment provides a microemulsion multifunctional nano oil displacing agent, which differs from the microemulsion multifunctional nano oil displacing agent provided in Example 2 only in that:
  • organic anti-swelling agent which is the organic anti-swelling agent of the model HJZ-100 produced by Kaifeng Hengju Biotechnology Co., Ltd.
  • This comparative example provides a kind of oil displacing agent, and the difference of it and the microemulsion multifunctional nano oil displacing agent that embodiment 1 provides is only:
  • the isothiazolinone derivative was not used and replaced with an equivalent amount of water.
  • This comparative example provides a kind of oil displacing agent, and the difference of it and the microemulsion multifunctional nano oil displacing agent that embodiment 1 provides is only:
  • the diphenyl ether gemini surfactant is not used, and the diphenyl ether gemini surfactant is replaced with an equal amount of water.
  • This comparative example provides a kind of oil displacing agent, and the difference of it and the microemulsion multifunctional nano oil displacing agent that embodiment 1 provides is only:
  • the hyperbranched emulsified wetting and dispersing agent was not used, and the same amount of water was used to replace the hyperbranched emulsifying wetting and dispersing agent.
  • This comparative example provides a kind of oil displacing agent, and the difference of it and the microemulsion multifunctional nano oil displacing agent that embodiment 1 provides is only:
  • Polyvinyl alcohol was not used and replaced with an equivalent amount of water.
  • This comparative example provides a kind of oil displacing agent, and the difference of it and the microemulsion multifunctional nano oil displacing agent that embodiment 1 provides is only:
  • Example 1-Example 6 were also measured with reference to the centrifugation method in SY/T591-2016 "Evaluation Method of Clay Stabilizer Performance for Fracturing Acidification and Water Injection in Oil and Gas Fields" under the experimental temperature condition of 100°C Multifunctional nano oil displacing agent and the anti-swelling ratio of the oil displacing agent provided by Comparative Example 1-Comparative Example 5.
  • Example 1 The oil washing efficiency is above 98%, and the anti-swelling rate is above 50%.
  • Example 2 The oil washing efficiency is above 98%, and the anti-swelling rate is above 50%.
  • Example 3 The oil washing efficiency is above 98%, and the anti-swelling rate is above 50%.
  • Example 4 The oil washing efficiency is above 98%, and the anti-swelling rate is above 85%
  • Example 5 The oil washing efficiency is above 98%, and the anti-swelling rate is above 75%
  • Example 6 The oil washing efficiency is above 98%, and the anti-swelling rate is above 80% Comparative example 1
  • the oil washing efficiency is 30-35%, and the anti-swelling rate is less than 50% Comparative example 2
  • the oil washing efficiency is 40-55%, and the anti-swelling rate is less than 50% Comparative example 3
  • the oil washing efficiency is 70-80%, and the anti-swelling rate is less than 50% Comparative example 4 ⁇ , the anti-expansion rate is below 50% Comparative example 5
  • the oil washing efficiency is 75-83%, and the anti-swelling rate is more than 50%
  • the oil washing efficiency can reach More than 98%, it shows that the microemulsion multifunctional nano oil displacement agent provided by the embodiment of the present invention has a very high permeability enhancement ability.
  • the oil displacement ability of the above-mentioned oil displacement agent has a relatively significant impact, and stirring under the slow speed condition of 100-300r/min after adding dodecane and tetradecane helps to improve the penetration enhancement of the oil displacement agent Oil displacement ability.
  • This test example carries out stability evaluation to the microemulsion multifunctional nano-oil displacing agent that embodiment 1-embodiment 3 provides and the oil displacing agent that comparative example 4-comparative example 5 provides respectively, and described stability evaluation process comprises: normal temperature 25 Under the condition of °C, the samples to be tested were divided into groups and stood still for 30 days, 90 days and 180 days to observe whether they were delaminated, and to judge the stability of the samples to be tested.
  • microemulsion multifunctional nano-oil displacing agents provided by Examples 1 to 3 of the present invention were left standing for 30 days, 90 days and 180 days in groups, and there was no obvious stratification phenomenon, indicating that the microemulsions provided by the embodiments of the present invention
  • the emulsion multifunctional nano oil displacing agent has good stability.
  • the oil-displacing agent provided by Comparative Example 4 appears delamination approximately in about 40-60 days, indicating that its stability is relatively poor;
  • the results of the stability of the agent show that the addition of polyvinyl alcohol can improve the stability of the oil-displacing agent.
  • the microemulsion multifunctional nano oil displacement agent provided in Example 1-Example 3 is respectively used in a tight oil reservoir, such as an ultra-low permeability reservoir oil field development test process, and the actual product obtained is a single agent washing oil
  • the efficiency can reach more than 90%, and the anti-expansion rate can reach more than 50%.
  • the microemulsion multifunctional nano oil displacement agent provided in Example 4-Example 6 is respectively used in a certain tight oil reservoir, such as an ultra-low permeability reservoir oilfield development test process, the actual product obtained is a single agent wash oil
  • the efficiency can reach more than 90%, and the anti-expansion rate can reach more than 75%, and the highest can reach more than 85%.

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Abstract

A microemulsion multifunctional nano oil displacing agent and a preparation method therefor and an application thereof. The microemulsion multifunctional nano oil displacing agent comprises: in parts by weight, 10-35 parts of nano silicon dioxide, 30-50 parts of a diphenyl ether gemini surfactant, 10-20 parts of an isothiazolinone derivative, 1-5 parts of a permeability increasing agent, 1-3 parts of a stabilizer, 30-40 parts of dodecane, 20-35 parts of tetradecane, and 50-80 parts of water. The microemulsion multifunctional nano oil displacing agent provided by the present invention has very high permeability increasing and oil displacing capabilities and excellent stability.

Description

一种微乳液多功能纳米驱油剂及其制备方法与应用A kind of microemulsion multifunctional nano oil displacement agent and its preparation method and application 技术领域technical field
本发明涉及一种微乳液多功能纳米驱油剂及其制备方法与应用，属于石油开采和油田化学材料制备技术领域。The invention relates to a microemulsion multifunctional nanometer oil displacement agent and its preparation method and application, belonging to the technical field of oil exploitation and oilfield chemical material preparation.
背景技术Background technique
随着石油开发的深入，对于致密油储集层，往往需要通过压裂驱油的方式进行增产，提高原油采收率。尤其是对于低饱和压力异常高温高压特低渗透油藏，处理技术难度更高，而原油采收率的高低，往往与驱油剂的效果有着密不可分的关系。With the deepening of petroleum development, for tight oil reservoirs, it is often necessary to increase production through fracturing and flooding to enhance oil recovery. Especially for ultra-low permeability reservoirs with low saturation pressure, abnormal high temperature, high pressure, and ultra-low permeability, the treatment technology is more difficult, and the level of oil recovery is often inseparable from the effect of oil displacement agents.
现有的驱油剂往往达不到想要的效果，而且对于一部分复合配方形式的驱油剂而言，经常存在着长时间储存稳定性差，实际使用过程中在储层中效果不理想等问题。Existing oil displacement agents often fail to achieve the desired effect, and for some oil displacement agents in the form of compound formulations, there are often problems such as poor long-term storage stability and unsatisfactory effects in the reservoir during actual use. .
纳米二氧化硅为本领域现有驱油剂常规使用的组分，其中，纳米二氧化硅颗粒的尺寸为纳米级别，其表面存在不饱和残键以及不同键合状态的羟基，因缺氧而偏离了稳定的硅氧结构，活性很高，具有较强的吸附特性；由于其活性高，导致其在使用过程中在达到预定位置之前就发生了作用，为解决此问题一方面需要增大其用量，另一方面需要对其进行缓释，以提高驱油剂的增渗驱油效果。Nano-silica is a component commonly used in existing oil displacement agents in this field, wherein the size of nano-silica particles is nanoscale, and there are unsaturated residual bonds and hydroxyl groups in different bonding states on the surface. Deviating from the stable silicon-oxygen structure, it has high activity and strong adsorption characteristics; due to its high activity, it has an effect before reaching the predetermined position during use. To solve this problem, it is necessary to increase its On the other hand, it needs to be released slowly to improve the oil displacement effect of the oil displacement agent.
因此，开发一种具有良好的增渗驱油效果、可以长期稳定储存的驱油剂，已经成为本领域亟需解决的技术问题。Therefore, it has become a technical problem urgently to be solved in this field to develop a kind of oil displacement agent which has good permeability enhancement effect and can be stored stably for a long time.
发明内容Contents of the invention
为了解决上述的缺点和不足，本发明的一个目的在于提供一种微乳液多功能纳米驱油剂，即纳米微乳液渗析驱油剂。In order to solve the above-mentioned shortcomings and deficiencies, an object of the present invention is to provide a microemulsion multifunctional nano-oil displacing agent, that is, a nano-microemulsion dialysis oil displacing agent.
本发明的另一个目的还在于提供以上所述微乳液多功能纳米驱油剂的制备方法。Another object of the present invention is to provide the preparation method of the above-mentioned microemulsion multifunctional nano oil displacing agent.
本发明的又一个目的还在于提供以上所述微乳液多功能纳米驱油剂在致密油储集层开发中的应用。本发明提供的微乳液多功能纳米驱油剂具有非常高的增渗驱油能力以及优异的稳定性。Yet another object of the present invention is to provide the application of the above-mentioned microemulsion multifunctional nano oil displacement agent in the development of tight oil reservoirs. The microemulsion multifunctional nanometer oil displacement agent provided by the invention has very high permeability enhancement and oil displacement ability and excellent stability.
为了实现以上目的，一方面，本发明提供了一种微乳液多功能纳米驱油剂，其中，所述微乳液多功能纳米驱油剂包括：In order to achieve the above object, on the one hand, the present invention provides a kind of microemulsion multifunctional nano oil displacing agent, wherein, said microemulsion multifunctional nano oil displacing agent comprises:
纳米二氧化硅10-35份、二苯醚类双子表面活性剂30-50份、异噻唑啉酮衍生物10-20份、增渗剂1-5份、稳定剂1-3份、十二烷30-40份、十四烷20-35份和水50-80份。10-35 parts of nano-silica, 30-50 parts of diphenyl ether gemini surfactant, 10-20 parts of isothiazolinone derivatives, 1-5 parts of penetration enhancer, 1-3 parts of stabilizer, twelve 30-40 parts of alkane, 20-35 parts of tetradecane and 50-80 parts of water.
作为本发明以上所述微乳液多功能纳米驱油剂的一具体实施方式，其中，所述二苯醚类双子表面活性剂为(辛基苯酚聚氧乙烯醚双取代)二甲酸二苯醚表面活性剂。As a specific embodiment of the microemulsion multifunctional nano-oil displacing agent described above in the present invention, wherein the diphenyl ether gemini surfactant is (octylphenol polyoxyethylene ether disubstituted) diphenyl ether dicarboxylate surface active agent.
作为本发明以上所述微乳液多功能纳米驱油剂的一具体实施方式，其中，所述二苯醚类双子表面活性剂是先使4,4’-二甲酸二苯醚进行酰氯化反应得到4,4’-二甲酰氯二苯醚，再使4,4’-二甲酰氯二苯醚与辛基苯酚聚氧乙烯醚(OP-10)发生酯化反应制得的。As a specific embodiment of the microemulsion multifunctional nano-oil displacing agent described above in the present invention, the diphenyl ether-based gemini surfactant is first obtained by subjecting 4,4'-dicarboxylic acid diphenyl ether to an acyl chloride reaction. 4,4'-diformyl chloride diphenyl ether, and then make 4,4'-diformyl chloride diphenyl ether and octylphenol polyoxyethylene ether (OP-10) for esterification.
其中，本发明所用的二苯醚类双子表面活性剂为现有常规物质(可参见致密油纳米流体增渗驱油体系特征及提高采收率机理，丁彬等，石油勘探与开发，2020年8月，第756-763页)，其可以通过如上所示的现有制备方法制得，也可以通过商购获得。Wherein, the diphenyl ether gemini surfactant used in the present invention is an existing conventional substance (see characteristics of tight oil nanofluid enhanced permeability flooding system and enhanced recovery mechanism, Ding Bin, etc., Petroleum Exploration and Development, 2020 August, pages 756-763), which can be prepared by the existing preparation method shown above, and can also be obtained commercially.
作为本发明以上所述微乳液多功能纳米驱油剂的一具体实施方式，其中，所述异噻唑啉酮衍生物的结构式为
Figure PCTCN2022136096-appb-000001
As a specific embodiment of the microemulsion multifunctional nano oil displacing agent described above in the present invention, wherein, the structural formula of the isothiazolinone derivative is
Figure PCTCN2022136096-appb-000001
作为本发明以上所述微乳液多功能纳米驱油剂的一具体实施方式，其中，所述异噻唑啉酮衍生物是先使NaH、N,N-二甲基甲酰胺和异噻唑啉-3-酮在氮气保护气氛下进行反应，然后向所得反应体系中加入γ-氯丙基三乙氧基硅烷，在冰浴条件下反应20-40min，再于70-100℃反应2-4h后经溶剂分离后制得。As a specific embodiment of the above-mentioned microemulsion multifunctional nano-oil displacing agent of the present invention, wherein, the isothiazolinone derivative is first made of NaH, N,N-dimethylformamide and isothiazoline-3 - The ketone is reacted under a nitrogen protective atmosphere, and then γ-chloropropyltriethoxysilane is added to the resulting reaction system, and the reaction is carried out under ice bath conditions for 20-40min, and then reacted at 70-100°C for 2-4h. obtained after solvent separation.
其中，本发明所用的异噻唑啉酮衍生物为现有常规物质，其可以通过如上所示的现有制备方法制得(可参见中国专利CN102191684A)，也可以通过商购获得。Among them, the isothiazolinone derivative used in the present invention is an existing conventional substance, which can be prepared by the above-mentioned existing preparation method (see Chinese patent CN102191684A), or can be obtained commercially.
作为本发明以上所述微乳液多功能纳米驱油剂的一具体实施方式，其中，所述增渗剂包括超支化乳化润湿分散剂。在本发明的一些实施例中，所述超支化乳化润湿分散剂可为河南省道纯化工技术有限公司生产的型号为31818的产品。As a specific embodiment of the microemulsion multifunctional nano-oil displacing agent mentioned above in the present invention, the penetration enhancer includes a hyperbranched emulsifying wetting and dispersing agent. In some embodiments of the present invention, the hyperbranched emulsifying wetting and dispersing agent can be a model 31818 product produced by Henan Daochun Chemical Technology Co., Ltd.
作为本发明以上所述微乳液多功能纳米驱油剂的一具体实施方式，其中，所述稳定剂包括聚乙烯醇。As a specific embodiment of the microemulsion multifunctional nano-oil displacing agent mentioned above in the present invention, the stabilizer includes polyvinyl alcohol.
作为本发明以上所述微乳液多功能纳米驱油剂的一具体实施方式，其中，所述微乳液多功能纳米驱油剂还包括1-5份的有机防膨剂。As a specific embodiment of the microemulsion multifunctional nano oil displacing agent described above in the present invention, the microemulsion multifunctional nano oil displacing agent further includes 1-5 parts of an organic anti-swelling agent.
作为本发明以上所述微乳液多功能纳米驱油剂的一具体实施方式，其中，所述有机防膨剂包括有机防膨剂HJZ-100。在本发明的一些实施例中，所述有机防膨剂HJZ-100可为开封市恒聚生物科技有限公司生产的产品。As a specific embodiment of the microemulsion multifunctional nano-oil displacing agent mentioned above in the present invention, the organic anti-swelling agent includes organic anti-swelling agent HJZ-100. In some embodiments of the present invention, the organic anti-swelling agent HJZ-100 can be a product produced by Kaifeng Hengju Biotechnology Co., Ltd.
本发明所提供的微乳液多功能纳米驱油剂添加有超支化乳化润湿分散剂、聚乙烯醇以及十二烷和十四烷，其中，所述超支化乳化润湿分散剂主要用于提升增渗驱油性能，所述聚乙烯醇用于提升体系的稳定性，添加十二烷和十四烷主要是利用其长链结构提升 稳定性，同时还考虑了成本、工业化的可行性，即二者成本较低，工业化可行性较高。The microemulsion multifunctional nano oil displacement agent provided by the present invention is added with hyperbranched emulsifying wetting and dispersing agent, polyvinyl alcohol, dodecane and tetradecane, wherein the hyperbranching emulsifying wetting and dispersing agent is mainly used to enhance Enhanced penetration displacement performance, the polyvinyl alcohol is used to improve the stability of the system, and the addition of dodecane and tetradecane is mainly to use its long-chain structure to improve stability, while also considering the cost and feasibility of industrialization, namely The cost of the two is lower, and the industrialization feasibility is higher.
另一方面，本发明还提供了以上所述微乳液多功能纳米驱油剂的制备方法，其中，所述制备方法包括：On the other hand, the present invention also provides the preparation method of above-mentioned microemulsion multifunctional nano oil displacement agent, wherein, described preparation method comprises:
(1)将纳米二氧化硅、二苯醚类双子表面活性剂、异噻唑啉酮衍生物混合均匀；(1) Mix nano silicon dioxide, diphenyl ether gemini surfactant, and isothiazolinone derivatives evenly;
(2)向步骤(1)所得混合物中加入十二烷和十四烷，并于慢速条件下混合均匀；(2) Add dodecane and tetradecane to the mixture obtained in step (1), and mix uniformly under slow conditions;
(3)向步骤(2)所得混合物中加入增渗剂、稳定剂和水，混合均匀后即得到所述微乳液多功能纳米驱油剂。(3) Add a penetration enhancer, a stabilizer and water to the mixture obtained in step (2), and mix uniformly to obtain the microemulsion multifunctional nano-oil displacing agent.
作为本发明以上所述制备方法的一具体实施方式，其中，步骤(1)中所述混合均匀通过搅拌实现，所述搅拌为2000-3000r/min条件下搅拌3-5min。As a specific embodiment of the above-mentioned preparation method of the present invention, wherein the homogeneous mixing in step (1) is realized by stirring, and the stirring is 3-5 min under the condition of 2000-3000 r/min.
作为本发明以上所述制备方法的一具体实施方式，其中，步骤(2)中，加入十二烷和十四烷后需要进行慢速搅拌，才能够得到稳定性优异的产品；As a specific embodiment of the above-mentioned preparation method of the present invention, wherein, in step (2), slow stirring is required after adding dodecane and tetradecane to obtain a product with excellent stability;
优选地，步骤(2)中所述混合均匀通过搅拌实现，所述搅拌为100-300r/min条件下搅拌2-4h。Preferably, the homogeneous mixing in step (2) is achieved by stirring, and the stirring is 2-4 hours under the condition of 100-300 r/min.
作为本发明以上所述制备方法的一具体实施方式，其中，步骤(3)中所述混合均匀通过搅拌实现，所述搅拌为500-1000r/min条件下搅拌0.5-2h。As a specific embodiment of the above-mentioned preparation method of the present invention, wherein the homogeneous mixing in step (3) is achieved by stirring, and the stirring is 500-1000 r/min for 0.5-2 h.
作为本发明以上所述制备方法的一具体实施方式，其中，所述制备方法于常温下进行。As a specific embodiment of the above-mentioned preparation method of the present invention, wherein the preparation method is carried out at normal temperature.
又一方面，本发明还提供了以上所述微乳液多功能纳米驱油剂在致密油储集层开发中的应用。In another aspect, the present invention also provides the application of the above-mentioned microemulsion multifunctional nano oil displacement agent in the development of tight oil reservoirs.
作为本发明以上所述应用的一具体实施方式，其中，所述致密油储集层为特低渗透油藏。As a specific embodiment of the above application of the present invention, the tight oil reservoir is an ultra-low permeability reservoir.
作为本发明以上所述应用的一具体实施方式，其中，所述微乳液多功能纳米驱油剂的用量为洗油质量的0.1％-1％。As a specific embodiment of the application described above in the present invention, the amount of the microemulsion multifunctional nano-oil displacing agent is 0.1%-1% of the mass of the washing oil.
本发明所提供的微乳液多功能纳米驱油剂添加有二苯醚类双子表面活性剂，其具有很好的润湿翻转能力，与异噻唑啉酮衍生物、十二烷和十四烷配合，可形成油溶性的原油驱油剂主体，提升驱油剂在储油层的稳定性，使得所述驱油剂具有很好的渗透、扩散能力；另外，添加二苯醚类双子表面活性剂还可以很好地利用相似相容原理，使所述油溶性的原油驱油剂主体消除原油各组分之间的分子缔合作用，将原油打散成为较小尺寸的小尺寸油，从而进一步提升原油的析出率。The microemulsion multifunctional nano-oil displacing agent provided by the present invention is added with diphenyl ether gemini surfactant, which has good wetting and turning ability, and can be combined with isothiazolinone derivatives, dodecane and tetradecane , can form the main body of oil-soluble crude oil displacement agent, improve the stability of the oil displacement agent in the oil reservoir, so that the oil displacement agent has good penetration and diffusion capabilities; in addition, adding diphenyl ether gemini surfactants can also The principle of similar compatibility can be well used to make the main body of the oil-soluble crude oil displacement agent eliminate the molecular association between various components of crude oil, break up the crude oil into small-sized oils of smaller sizes, and further improve The extraction rate of crude oil.
具体实施方式Detailed ways
需要说明的是，本发明的说明书和权利要求书中的术语“包括”以及其任何变形，意图在于覆盖不排他的包含，例如，包含了一系列步骤或单元的过程、方法、系统、产品或设备不必限于清楚地列出的那些步骤或单元，而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。It should be noted that the term "comprising" and any variations thereof in the specification and claims of the present invention are intended to cover non-exclusive inclusion, for example, a process, method, system, product or process that includes a series of steps or units. The apparatus is not necessarily limited to those steps or units explicitly listed, but may include other steps or units not explicitly listed or inherent to the process, method, product or apparatus.
本发明所公开的“范围”以下限和上限的形式给出。可以分别为一个或多个下限，和一个或多个上限。给定的范围是通过选定一个下限和一个上限进行限定的。选定的下限和上限限定了特别范围的边界。所有以这种方式进行限定的范围是可组合的，即任何下限可以与任何上限组合形成一个范围。例如，针对特定参数列出了60-120和80-110的范围，理解为60-110和80-120的范围也是可以预料到的。此外，如果列出的最小范围值为1和2，列出的最大范围值为3，4和5，则下面的范围可全部预料到：1-3、1-4、1-5、2-3、2-4和2-5。The "ranges" disclosed herein are given in terms of lower limits and upper limits. There can be one or more lower bounds, and one or more upper bounds, respectively. A given range is defined by selecting a lower limit and an upper limit. Selected lower and upper limits define the boundaries of a particular range. All ranges defined in this manner are combinable, ie, any lower limit can be combined with any upper limit to form a range. For example, ranges of 60-120 and 80-110 are listed for a particular parameter, with the understanding that ranges of 60-110 and 80-120 are also contemplated. Additionally, if the minimum range values listed are 1 and 2, and the maximum range values listed are 3, 4, and 5, the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
在本发明中，除非有其他说明，数值范围“a-b”表示a到b之间的任意实数组合的缩略表示，其中a和b都是实数。例如数值范围“0-5”表示本发明中已经全部列出了“0-5”之间的全部实数，“0-5”只是这些数值组合的缩略表示。In the present invention, unless otherwise stated, the numerical range "a-b" represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0-5" have been listed in the present invention, and "0-5" is only an abbreviated representation of these numerical combinations.
在本发明中，如果没有特别的说明，本发明所提到的所有实施方式以及优选实施方式可以相互组合形成新的技术方案。In the present invention, if there is no special description, all the embodiments and preferred embodiments mentioned in the present invention can be combined with each other to form a new technical solution.
在本发明中，如果没有特别的说明，本发明所提到的所有技术特征以及优选特征可以相互组合形成新的技术方案。In the present invention, if there is no special description, all the technical features and preferred features mentioned in the present invention can be combined with each other to form a new technical solution.
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。下列所描述的实施例是本发明一部分实施例，而不是全部的实施例，仅用于说明本发明，而不应视为限制本发明的范围。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。In order to make the object, technical solution and advantages of the present invention more clear, the present invention will be further described in detail below in conjunction with the examples. The following described embodiments are some embodiments of the present invention, but not all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention. Those who do not indicate the specific conditions in the examples are carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used were not indicated by the manufacturer, and they were all conventional products that could be purchased from the market.
实施例1Example 1
本实施例提供了一种微乳液多功能纳米驱油剂，其中，所述微乳液多功能纳米驱油剂包括：This embodiment provides a microemulsion multifunctional nano oil displacing agent, wherein the microemulsion multifunctional nano oil displacing agent includes:
纳米二氧化硅10kg、二苯醚类双子表面活性剂50kg、异噻唑啉酮衍生物10kg、超支化乳化润湿分散剂(河南省道纯化工技术有限公司生产的型号为31818的产品)5kg、聚乙烯醇1kg、十二烷40kg、十四烷20kg和水80kg。Nano silicon dioxide 10kg, diphenyl ether gemini surfactant 50kg, isothiazolinone derivatives 10kg, hyperbranched emulsified wetting and dispersing agent (model 31818 produced by Henan Daochun Chemical Technology Co., Ltd.) 5kg, Polyvinyl alcohol 1kg, dodecane 40kg, tetradecane 20kg and water 80kg.
其中，所述二苯醚类双子表面活性剂为(辛基苯酚聚氧乙烯醚双取代)二甲酸二苯醚 表面活性剂，其是先使4,4’-二甲酸二苯醚进行酰氯化反应得到4,4’-二甲酰氯二苯醚，再使4,4’-二甲酰氯二苯醚与辛基苯酚聚氧乙烯醚发生酯化反应制得的。Wherein, the diphenyl ether-based gemini surfactant is (octylphenol polyoxyethylene ether disubstituted) diphenyl ether diformate surfactant, which firstly makes 4,4'-diphenyl ether dicarboxylate carry out acyl chloride The reaction is to obtain 4,4'-diformyl chloride diphenyl ether, and then the esterification reaction of 4,4'-diformyl chloride diphenyl ether with octylphenol polyoxyethylene ether is obtained.
其中，所述异噻唑啉酮衍生物的结构式为
Figure PCTCN2022136096-appb-000002
其是先使NaH、N,N-二甲基甲酰胺和异噻唑啉-3-酮在氮气保护气氛下进行反应，然后向所得反应体系中加入γ-氯丙基三乙氧基硅烷，在冰浴条件下反应20-40min，再于70-100℃反应2-4h后经溶剂分离后制得。 Wherein, the structural formula of the isothiazolinone derivative is
Figure PCTCN2022136096-appb-000002
It is first to make NaH, N,N-dimethylformamide and isothiazolin-3-one react under nitrogen protection atmosphere, then add γ-chloropropyltriethoxysilane to the obtained reaction system, It can be obtained by reacting in ice bath for 20-40min, then reacting at 70-100℃ for 2-4h, and then separated by solvent.
本实施例中，所述微乳液多功能纳米驱油剂是采用包括如下步骤的制备方法制得的：In this embodiment, the microemulsion multifunctional nano-oil displacing agent is prepared by a preparation method comprising the following steps:
首先将纳米二氧化硅、二苯醚类双子表面活性剂、异噻唑啉酮衍生物混合，并于2000r/min转速条件下搅拌3-5min，然后向所得均匀混合物中加入十二烷和十四烷，并于300r/min转速条件下搅拌2-4h，再向所述均匀混合物中加入超支化乳化润湿分散剂、聚乙烯醇和水，并于500r/min转速条件下搅拌0.5-2h，即得到微乳液多功能纳米驱油剂。First, mix nano-silica, diphenyl ether gemini surfactants, and isothiazolinone derivatives, and stir at 2000r/min for 3-5min, then add dodecane and tetradecane to the resulting homogeneous mixture alkane, and stirred at 300r/min for 2-4h, then added hyperbranched emulsified wetting and dispersing agent, polyvinyl alcohol and water into the homogeneous mixture, and stirred at 500r/min for 0.5-2h, that is A microemulsion multifunctional nano oil displacing agent is obtained.
实施例2Example 2
本实施例提供了一种微乳液多功能纳米驱油剂，其中，所述微乳液多功能纳米驱油剂包括：This embodiment provides a microemulsion multifunctional nano oil displacing agent, wherein the microemulsion multifunctional nano oil displacing agent includes:
纳米二氧化硅35kg、二苯醚类双子表面活性剂30kg、异噻唑啉酮衍生物20kg、超支化乳化润湿分散剂(河南省道纯化工技术有限公司生产的型号为31818的产品)1kg、聚乙烯醇3kg、十二烷30kg、十四烷35kg和水50kg。Nano silicon dioxide 35kg, diphenyl ether gemini surfactant 30kg, isothiazolinone derivatives 20kg, hyperbranched emulsified wetting and dispersing agent (model 31818 produced by Henan Daochun Chemical Technology Co., Ltd.) 1kg, Polyvinyl alcohol 3kg, dodecane 30kg, tetradecane 35kg and water 50kg.
其中，所述二苯醚类双子表面活性剂为(辛基苯酚聚氧乙烯醚双取代)二甲酸二苯醚表面活性剂，其是先使4,4’-二甲酸二苯醚进行酰氯化反应得到4,4’-二甲酰氯二苯醚，再使4,4’-二甲酰氯二苯醚与辛基苯酚聚氧乙烯醚发生酯化反应制得的。Wherein, the diphenyl ether-based gemini surfactant is (octylphenol polyoxyethylene ether disubstituted) diphenyl ether diformate surfactant, which firstly makes 4,4'-diphenyl ether dicarboxylate carry out acyl chloride The reaction is to obtain 4,4'-diformyl chloride diphenyl ether, and then the esterification reaction of 4,4'-diformyl chloride diphenyl ether with octylphenol polyoxyethylene ether is obtained.
其中，所述异噻唑啉酮衍生物的结构式为
Figure PCTCN2022136096-appb-000003
其是先使NaH、N,N-二甲基甲酰胺和异噻唑啉-3-酮在氮气保护气氛下进行反应，然后向所得反应体系中加入γ-氯丙基三乙氧基硅烷，在冰浴条件下反应20-40min，再于70-100℃反应2-4h后经溶剂分离后制得。 Wherein, the structural formula of the isothiazolinone derivative is
Figure PCTCN2022136096-appb-000003
It is first to make NaH, N,N-dimethylformamide and isothiazolin-3-one react under nitrogen protection atmosphere, then add γ-chloropropyltriethoxysilane to the obtained reaction system, It can be obtained by reacting in ice bath for 20-40min, then reacting at 70-100℃ for 2-4h, and then separated by solvent.
本实施例中，所述微乳液多功能纳米驱油剂是采用包括如下步骤的制备方法制得的：In this embodiment, the microemulsion multifunctional nano-oil displacing agent is prepared by a preparation method comprising the following steps:
首先将纳米二氧化硅、二苯醚类双子表面活性剂、异噻唑啉酮衍生物混合，并于2500r/min转速条件下搅拌3-5min，然后向所得均匀混合物中加入十二烷和十四烷，并于100r/min转速条件下搅拌2-4h，再向所述均匀混合物中加入超支化乳化润湿分散剂、聚乙烯醇和水，并于800r/min转速条件下搅拌0.5-2h，即得到微乳液多功能纳米驱油剂。First, mix nano-silica, diphenyl ether gemini surfactants, and isothiazolinone derivatives, and stir at 2500r/min for 3-5min, then add dodecane and tetradecane to the resulting homogeneous mixture alkane, and stirred at 100r/min for 2-4h, then added hyperbranched emulsified wetting and dispersing agent, polyvinyl alcohol and water into the homogeneous mixture, and stirred at 800r/min for 0.5-2h, that is A microemulsion multifunctional nano oil displacing agent is obtained.
实施例3Example 3
本实施例提供了一种微乳液多功能纳米驱油剂，其中，所述微乳液多功能纳米驱油剂包括：This embodiment provides a microemulsion multifunctional nano oil displacing agent, wherein the microemulsion multifunctional nano oil displacing agent includes:
纳米二氧化硅20kg、二苯醚类双子表面活性剂40kg、异噻唑啉酮衍生物15kg、超支化乳化润湿分散剂(河南省道纯化工技术有限公司生产的型号为31818的产品)3kg、聚乙烯醇2kg、十二烷35kg、十四烷30kg和水65kg。Nano-silica 20kg, diphenyl ether gemini surfactant 40kg, isothiazolinone derivatives 15kg, hyperbranched emulsified wetting and dispersing agent (model 31818 produced by Henan Daochun Chemical Technology Co., Ltd.) 3kg, Polyvinyl alcohol 2kg, dodecane 35kg, tetradecane 30kg and water 65kg.
其中，所述二苯醚类双子表面活性剂为(辛基苯酚聚氧乙烯醚双取代)二甲酸二苯醚表面活性剂，其是先使4,4’-二甲酸二苯醚进行酰氯化反应得到4,4’-二甲酰氯二苯醚，再使4,4’-二甲酰氯二苯醚与辛基苯酚聚氧乙烯醚发生酯化反应制得的。Wherein, the diphenyl ether-based gemini surfactant is (octylphenol polyoxyethylene ether disubstituted) diphenyl ether diformate surfactant, which firstly makes 4,4'-diphenyl ether dicarboxylate carry out acyl chloride The reaction is to obtain 4,4'-diformyl chloride diphenyl ether, and then the esterification reaction of 4,4'-diformyl chloride diphenyl ether with octylphenol polyoxyethylene ether is obtained.
其中，所述异噻唑啉酮衍生物的结构式为
Figure PCTCN2022136096-appb-000004
其是先使NaH、N,N-二甲基甲酰胺和异噻唑啉-3-酮在氮气保护气氛下进行反应，然后向所得反应体系中加入γ-氯丙基三乙氧基硅烷，在冰浴条件下反应20-40min，再于70-100℃反应2-4h后经溶剂分离后制得。 Wherein, the structural formula of the isothiazolinone derivative is
Figure PCTCN2022136096-appb-000004
It is first to make NaH, N,N-dimethylformamide and isothiazolin-3-one react under nitrogen protection atmosphere, then add γ-chloropropyltriethoxysilane to the obtained reaction system, It can be obtained by reacting in ice bath for 20-40min, then reacting at 70-100℃ for 2-4h, and then separated by solvent.
本实施例中，所述微乳液多功能纳米驱油剂是采用包括如下步骤的制备方法制得的：In this embodiment, the microemulsion multifunctional nano-oil displacing agent is prepared by a preparation method comprising the following steps:
首先将纳米二氧化硅、二苯醚类双子表面活性剂、异噻唑啉酮衍生物混合，并于3000r/min转速条件下搅拌3-5min，然后向所得均匀混合物中加入十二烷和十四烷，并于300r/min转速条件下搅拌2-4h，再向所述均匀混合物中加入超支化乳化润湿分散剂、聚乙烯醇和水，并于1000r/min转速条件下搅拌0.5-2h，即得到微乳液多功能纳米驱油剂。First, mix nano-silica, diphenyl ether gemini surfactants, and isothiazolinone derivatives, and stir at 3000r/min for 3-5min, then add dodecane and tetradecane to the resulting homogeneous mixture alkane, and stirred at 300r/min for 2-4h, then added hyperbranched emulsified wetting and dispersing agent, polyvinyl alcohol and water into the homogeneous mixture, and stirred at 1000r/min for 0.5-2h, that is A microemulsion multifunctional nano oil displacing agent is obtained.
实施例4Example 4
本实施例提供了一种微乳液多功能纳米驱油剂，其与实施例1提供的微乳液多功能纳米驱油剂的区别仅在于：This embodiment provides a microemulsion multifunctional nano oil displacing agent, which differs from the microemulsion multifunctional nano oil displacing agent provided in Example 1 only in that:
还包括5kg的有机防膨剂，其为开封市恒聚生物科技有限公司生产的型号为HJZ-100的有机防膨剂。It also includes 5kg of organic anti-swelling agent, which is the organic anti-swelling agent of the model HJZ-100 produced by Kaifeng Hengju Biotechnology Co., Ltd.
实施例5Example 5
本实施例提供了一种微乳液多功能纳米驱油剂，其与实施例2提供的微乳液多功能纳米驱油剂的区别仅在于：This embodiment provides a microemulsion multifunctional nano oil displacing agent, which differs from the microemulsion multifunctional nano oil displacing agent provided in Example 2 only in that:
还包括1kg的有机防膨剂，其为开封市恒聚生物科技有限公司生产的型号为HJZ-100的有机防膨剂。It also includes 1 kg of organic anti-swelling agent, which is the organic anti-swelling agent of the model HJZ-100 produced by Kaifeng Hengju Biotechnology Co., Ltd.
实施例6Example 6
本实施例提供了一种微乳液多功能纳米驱油剂，其与实施例2提供的微乳液多功能纳米驱油剂的区别仅在于：This embodiment provides a microemulsion multifunctional nano oil displacing agent, which differs from the microemulsion multifunctional nano oil displacing agent provided in Example 2 only in that:
还包括3kg的有机防膨剂，其为开封市恒聚生物科技有限公司生产的型号为HJZ-100的有机防膨剂。It also includes 3kg of organic anti-swelling agent, which is the organic anti-swelling agent of the model HJZ-100 produced by Kaifeng Hengju Biotechnology Co., Ltd.
对比例1Comparative example 1
本对比例提供了一种驱油剂，其与实施例1提供的微乳液多功能纳米驱油剂的区别仅在于：This comparative example provides a kind of oil displacing agent, and the difference of it and the microemulsion multifunctional nano oil displacing agent that embodiment 1 provides is only:
不使用异噻唑啉酮衍生物，并用等量的水替代所述异噻唑啉酮衍生物。The isothiazolinone derivative was not used and replaced with an equivalent amount of water.
对比例2Comparative example 2
本对比例提供了一种驱油剂，其与实施例1提供的微乳液多功能纳米驱油剂的区别仅在于：This comparative example provides a kind of oil displacing agent, and the difference of it and the microemulsion multifunctional nano oil displacing agent that embodiment 1 provides is only:
不使用二苯醚类双子表面活性剂，并用等量的水替代所述二苯醚类双子表面活性剂。The diphenyl ether gemini surfactant is not used, and the diphenyl ether gemini surfactant is replaced with an equal amount of water.
对比例3Comparative example 3
本对比例提供了一种驱油剂，其与实施例1提供的微乳液多功能纳米驱油剂的区别仅在于：This comparative example provides a kind of oil displacing agent, and the difference of it and the microemulsion multifunctional nano oil displacing agent that embodiment 1 provides is only:
不使用超支化乳化润湿分散剂，并用等量的水替代所述超支化乳化润湿分散剂。The hyperbranched emulsified wetting and dispersing agent was not used, and the same amount of water was used to replace the hyperbranched emulsifying wetting and dispersing agent.
对比例4Comparative example 4
本对比例提供了一种驱油剂，其与实施例1提供的微乳液多功能纳米驱油剂的区别仅在于：This comparative example provides a kind of oil displacing agent, and the difference of it and the microemulsion multifunctional nano oil displacing agent that embodiment 1 provides is only:
不使用聚乙烯醇，并用等量的水替代所述聚乙烯醇。Polyvinyl alcohol was not used and replaced with an equivalent amount of water.
对比例5Comparative example 5
本对比例提供了一种驱油剂，其与实施例1提供的微乳液多功能纳米驱油剂的区别仅在于：This comparative example provides a kind of oil displacing agent, and the difference of it and the microemulsion multifunctional nano oil displacing agent that embodiment 1 provides is only:
加入十二烷和十四烷后，仍然在2500r/min的较高转速条件下搅拌2-4h。After adding dodecane and tetradecane, stir for 2-4 hours at a relatively high rotational speed of 2500r/min.
测试例1test case 1
本测试例使用参考文献，即“致密油纳米流体增渗驱油体系特征及提高采收率机理”，丁彬等，《石油勘探与开发》2020年8月，第759页，公开的“小尺寸油”特征评价方法分别对实施例1-实施例6提供的微乳液多功能纳米驱油剂以及对比例1-对比例3及对比例5提供的驱油剂进行增渗驱油效果评价；This test example uses references, namely "Characteristics of Tight Oil Nanofluid Enhanced Permeability Flooding System and Mechanism of Enhanced Recovery", Ding Bin et al., "Petroleum Exploration and Development", August 2020, p. 759, published "Small Dimensional oil" characteristic evaluation method is carried out to the microemulsion multifunctional nanometer oil displacement agent provided by embodiment 1-embodiment 6 and the oil displacement agent provided by comparative example 1-comparative example 3 and comparative example 5 to carry out the oil displacement effect evaluation of enhanced permeability;
本测试例还于100℃的实验温度条件下参照SY/T591-2016《油气田压裂酸化及注水用粘土稳定剂性能评价方法》中的离心法分别测定实施例1-实施例6提供的微乳液多功能纳米驱油剂以及对比例1-对比例5提供的驱油剂的防膨率。In this test example, the microemulsions provided in Example 1-Example 6 were also measured with reference to the centrifugation method in SY/T591-2016 "Evaluation Method of Clay Stabilizer Performance for Fracturing Acidification and Water Injection in Oil and Gas Fields" under the experimental temperature condition of 100°C Multifunctional nano oil displacing agent and the anti-swelling ratio of the oil displacing agent provided by Comparative Example 1-Comparative Example 5.
其中，本测试例中所得增渗驱油能力数据及防膨率数据见如下表1所示。Among them, the enhanced permeability displacement data and anti-swelling ratio data obtained in this test example are shown in Table 1 below.
表1Table 1
样品sample 洗油效率和防膨率/％Oil washing efficiency and anti-swelling rate/%
实施例1Example 1 洗油效率为98％以上，防膨率为50％以上The oil washing efficiency is above 98%, and the anti-swelling rate is above 50%.
实施例2Example 2 洗油效率为98％以上，防膨率为50％以上The oil washing efficiency is above 98%, and the anti-swelling rate is above 50%.
实施例3Example 3 洗油效率为98％以上，防膨率为50％以上The oil washing efficiency is above 98%, and the anti-swelling rate is above 50%.
实施例4Example 4 洗油效率为98％以上，防膨率为85％以上The oil washing efficiency is above 98%, and the anti-swelling rate is above 85%
实施例5Example 5 洗油效率为98％以上，防膨率为75％以上The oil washing efficiency is above 98%, and the anti-swelling rate is above 75%
实施例6Example 6 洗油效率为98％以上，防膨率为80％以上The oil washing efficiency is above 98%, and the anti-swelling rate is above 80%
对比例1Comparative example 1 洗油效率为30-35％，防膨率为50％以下The oil washing efficiency is 30-35%, and the anti-swelling rate is less than 50%
对比例2Comparative example 2 洗油效率为40-55％，防膨率为50％以下The oil washing efficiency is 40-55%, and the anti-swelling rate is less than 50%
对比例3Comparative example 3 洗油效率为70-80％，防膨率为50％以下The oil washing efficiency is 70-80%, and the anti-swelling rate is less than 50%
对比例4Comparative example 4 ～，防膨率为50％以下~, the anti-expansion rate is below 50%
对比例5Comparative example 5 洗油效率为75-83％，防膨率为50％以上The oil washing efficiency is 75-83%, and the anti-swelling rate is more than 50%
从以上表1中可以看出，相较于对比例中提供的驱油剂，注入本发明实施例1-实施例3提供的微乳液多功能纳米驱油剂后，其洗油效率均可达到98％以上，表明本发明实施例提供的微乳液多功能纳米驱油剂具有非常高的增渗驱油能力。As can be seen from the above table 1, compared with the oil displacing agent provided in the comparative example, after injecting the microemulsion multifunctional nano oil displacing agent provided by the embodiment 1-embodiment 3 of the present invention, the oil washing efficiency can reach More than 98%, it shows that the microemulsion multifunctional nano oil displacement agent provided by the embodiment of the present invention has a very high permeability enhancement ability.
综合对比实施例1提供的微乳液多功能纳米驱油剂、对比例1和对比例2提供的驱油剂的洗油效率结果可知，本发明实施例1提供的微乳液多功能纳米驱油剂的洗油效率明显优于对比例1和对比例2提供的驱油剂的洗油效率，这表明本发明实施例提供的微乳液多功能纳米驱油剂中使用的二苯醚类双子表面活性剂和异噻唑啉酮衍生物之间具有协同作用，使得所述微乳液多功能纳米驱油剂具有优异的洗油效率。Comprehensive comparison of the oil washing efficiency results of the microemulsion multifunctional nano oil displacing agent provided in Example 1, and the oil displacing agents provided in Comparative Example 1 and Comparative Example 2 shows that the microemulsion multifunctional nano oil displacing agent provided in Example 1 of the present invention The oil washing efficiency of is obviously better than the oil washing efficiency of the oil displacing agent provided in Comparative Example 1 and Comparative Example 2, which shows that the diphenyl ether gemini surfactant used in the microemulsion multifunctional nano oil displacing agent provided by the embodiment of the present invention There is a synergistic effect between the agent and the isothiazolinone derivative, so that the microemulsion multifunctional nano oil displacing agent has excellent oil washing efficiency.
综合对比实施例1提供的微乳液多功能纳米驱油剂、对比例3提供的驱油剂的洗油效率结果可知，本发明实施例1提供的微乳液多功能纳米驱油剂的洗油效率明显优于对比例3提供的驱油剂的洗油效率，这表明本发明实施例提供的微乳液多功能纳米驱油剂中使用的超支化乳化润湿分散剂具有增效作用，即采用超支化乳化润湿分散剂可以提高所述驱油剂的增渗驱油能力。另，对比例4提供的产品分层，无法作为驱油剂使用，也无法进行增渗驱油效果评价。Comprehensive comparison of the oil washing efficiency results of the microemulsion multifunctional nano oil displacing agent provided in Example 1 and the oil displacing agent provided in Comparative Example 3 shows that the oil washing efficiency of the microemulsion multifunctional nano oil displacing agent provided in Example 1 of the present invention Obviously better than the oil washing efficiency of the oil displacement agent provided in Comparative Example 3, this shows that the hyperbranched emulsification wetting and dispersing agent used in the microemulsion multifunctional nano oil displacement agent provided by the embodiment of the present invention has a synergistic effect, that is, using hyperbranched The emulsified wetting and dispersing agent can improve the oil displacement ability of the oil displacement agent. In addition, the product provided in Comparative Example 4 is stratified and cannot be used as an oil displacement agent, nor can it be evaluated for enhanced penetration displacement.
综合对比实施例1提供的微乳液多功能纳米驱油剂、对比例5提供的驱油剂的洗油效率结果可知，本发明实施例1提供的微乳液多功能纳米驱油剂的洗油效率明显优于对比例5提供的驱油剂的洗油效率，这表明制备本发明实施例提供的微乳液多功能纳米驱油剂过程中，加入十二烷和十四烷后的搅拌速度对所述驱油剂的增渗驱油能力存在较为显著的影响，加入十二烷和十四烷后于100-300r/min的慢速条件下进行搅拌有助于提高所述驱油剂的增渗驱油能力。Comprehensive comparison of the oil washing efficiency results of the microemulsion multifunctional nano oil displacing agent provided in Example 1 and the oil displacing agent provided in Comparative Example 5 shows that the oil washing efficiency of the microemulsion multifunctional nano oil displacing agent provided in Example 1 of the present invention Obviously better than the oil washing efficiency of the oil displacement agent provided in Comparative Example 5, this shows that in the process of preparing the microemulsion multifunctional nano oil displacement agent provided by the embodiments of the present invention, the stirring speed after adding dodecane and tetradecane has a great influence on the oil displacement agent. The oil displacement ability of the above-mentioned oil displacement agent has a relatively significant impact, and stirring under the slow speed condition of 100-300r/min after adding dodecane and tetradecane helps to improve the penetration enhancement of the oil displacement agent Oil displacement ability.
综合对比实施例1-实施例3提供的微乳液多功能纳米驱油剂和实施例4-实施例6提供的微乳液多功能纳米驱油剂的防膨性能结果可知，相较于实施例1-实施例3提供的微乳液多功能纳米驱油剂，实施例4-实施例6提供的微乳液多功能纳米驱油剂中添加有机防膨剂，其防膨率数据显著提高，这表明于本发明实施例提供的微乳液多功能纳米驱油剂中添加有机防膨剂，可显著提高该微乳液多功能纳米驱油剂的防膨性能。Comprehensive comparison of the anti-swelling properties of the microemulsion multifunctional nano oil displacing agent provided in Examples 1-Example 3 and the microemulsion multifunctional nano oil displacing agent provided in Example 4-Example 6 shows that, compared with Example 1 -The microemulsion multifunctional nanometer oil displacement agent that embodiment 3 provides, adds organic antiswelling agent in the microemulsion multifunctional nanometer oil displacement agent that embodiment 4-embodiment 6 provides, and its antiswelling rate data significantly improves, and this shows that in Adding an organic anti-swelling agent to the microemulsion multifunctional nano oil displacing agent provided in the embodiment of the present invention can significantly improve the antiswelling performance of the microemulsion multifunctional nano oil displacing agent.
测试例2test case 2
本测试例分别对实施例1-实施例3提供的微乳液多功能纳米驱油剂以及对比例4-对比例5提供的驱油剂进行稳定性评价，所述稳定性评价过程包括：常温25℃条件下将待测样品分组静置30天、90天和180天后观察其是否分层，并以此判断待测样品的稳定性。This test example carries out stability evaluation to the microemulsion multifunctional nano-oil displacing agent that embodiment 1-embodiment 3 provides and the oil displacing agent that comparative example 4-comparative example 5 provides respectively, and described stability evaluation process comprises: normal temperature 25 Under the condition of ℃, the samples to be tested were divided into groups and stood still for 30 days, 90 days and 180 days to observe whether they were delaminated, and to judge the stability of the samples to be tested.
其中，本发明实施例1-实施例3提供的微乳液多功能纳米驱油剂分组静置30天、90天和180天，均无明显的分层现象，表明本发明实施例所提供的微乳液多功能纳米驱油剂具有良好的稳定性。Among them, the microemulsion multifunctional nano-oil displacing agents provided by Examples 1 to 3 of the present invention were left standing for 30 days, 90 days and 180 days in groups, and there was no obvious stratification phenomenon, indicating that the microemulsions provided by the embodiments of the present invention The emulsion multifunctional nano oil displacing agent has good stability.
对比例4提供的驱油剂大约在40-60天左右出现分层现象，表明其稳定性较差；综合对比实施例1提供的微乳液多功能纳米驱油剂、对比例4提供的驱油剂的稳定性结果可知，聚乙烯醇的加入可以提高所述驱油剂的稳定性。The oil-displacing agent provided by Comparative Example 4 appears delamination approximately in about 40-60 days, indicating that its stability is relatively poor; The results of the stability of the agent show that the addition of polyvinyl alcohol can improve the stability of the oil-displacing agent.
另外，对比例5提供的驱油剂大约在30-50天左右出现分层现象，表明其稳定性也较差；综合对比实施例1提供的微乳液多功能纳米驱油剂、对比例5提供的驱油剂的稳定性结果可知，加入十二烷和十四烷后的搅拌速度对所述驱油剂的稳定性存在显著的影 响，加入十二烷和十四烷后于100-300r/min的慢速条件下进行搅拌有助于提高所述驱油剂的稳定性。In addition, the oil-displacing agent provided in Comparative Example 5 appeared delamination about 30-50 days, indicating that its stability was also relatively poor; The results of the stability of the oil-displacing agent show that the stirring speed after adding dodecane and tetradecane has a significant impact on the stability of the described oil-displacing agent. Stirring at a slow speed of 1 min helps to improve the stability of the oil-displacing agent.
应用例1Application example 1
本应用例将实施例1-实施例3提供的微乳液多功能纳米驱油剂分别用于某致密油储集层，如特低渗透油藏油田开发试验过程中，所得实际产品单剂洗油效率均可达到90％以上，防膨率均可达到50％以上。In this application example, the microemulsion multifunctional nano oil displacement agent provided in Example 1-Example 3 is respectively used in a tight oil reservoir, such as an ultra-low permeability reservoir oil field development test process, and the actual product obtained is a single agent washing oil The efficiency can reach more than 90%, and the anti-expansion rate can reach more than 50%.
应用例2Application example 2
本应用例将实施例4-实施例6提供的微乳液多功能纳米驱油剂分别用于某致密油储集层，如特低渗透油藏油田开发试验过程中，所得实际产品单剂洗油效率均可达到90％以上，防膨率均可达到75％以上，最高可达85％以上。In this application example, the microemulsion multifunctional nano oil displacement agent provided in Example 4-Example 6 is respectively used in a certain tight oil reservoir, such as an ultra-low permeability reservoir oilfield development test process, the actual product obtained is a single agent wash oil The efficiency can reach more than 90%, and the anti-expansion rate can reach more than 75%, and the highest can reach more than 85%.
以上所述，仅为本发明的具体实施例，不能以其限定发明实施的范围，所以其等同组件的置换，或依本发明专利保护范围所作的等同变化与修饰，都应仍属于本专利涵盖的范畴。另外，本发明中的技术特征与技术特征之间、技术特征与技术发明之间、技术发明与技术发明之间均可以自由组合使用。The above is only a specific embodiment of the present invention, and cannot limit the scope of the invention, so the replacement of its equivalent components, or the equivalent changes and modifications made according to the patent protection scope of the present invention, should still fall within the scope of this patent. category. In addition, the technical features and technical features, technical features and technical inventions, and technical inventions and technical inventions in the present invention can be used in free combination.

Claims (16)

  1. 一种微乳液多功能纳米驱油剂，其中，以重量份数计，所述微乳液多功能纳米驱油剂包括：A microemulsion multifunctional nano oil displacing agent, wherein, in parts by weight, the microemulsion multifunctional nano oil displacing agent comprises:
    纳米二氧化硅10-35份、二苯醚类双子表面活性剂30-50份、异噻唑啉酮衍生物10-20份、增渗剂1-5份、稳定剂1-3份、十二烷30-40份、十四烷20-35份和水50-80份。10-35 parts of nano-silica, 30-50 parts of diphenyl ether gemini surfactant, 10-20 parts of isothiazolinone derivatives, 1-5 parts of penetration enhancer, 1-3 parts of stabilizer, twelve 30-40 parts of alkane, 20-35 parts of tetradecane and 50-80 parts of water.
  2. 根据权利要求1所述的微乳液多功能纳米驱油剂，其中，所述二苯醚类双子表面活性剂为(辛基苯酚聚氧乙烯醚双取代)二甲酸二苯醚表面活性剂。The microemulsion multifunctional nano-oil displacing agent according to claim 1, wherein the diphenyl ether gemini surfactant is (octylphenol polyoxyethylene ether disubstituted) dicarboxylic acid diphenyl ether surfactant.
  3. 根据权利要求1或2所述的微乳液多功能纳米驱油剂，其中，所述二苯醚类双子表面活性剂是先使4,4’-二甲酸二苯醚进行酰氯化反应得到4,4’-二甲酰氯二苯醚，再使4,4’-二甲酰氯二苯醚与辛基苯酚聚氧乙烯醚发生酯化反应制得的。The microemulsion multifunctional nano-oil displacing agent according to claim 1 or 2, wherein, the diphenyl ether gemini surfactant first makes 4,4'-dicarboxylic acid diphenyl ether carry out acyl chloride reaction to obtain 4, 4'-diformyl chloride diphenyl ether, and then make 4,4'-diformyl chloride diphenyl ether and octylphenol polyoxyethylene ether for esterification.
  4. 根据权利要求1所述的微乳液多功能纳米驱油剂，其中，所述异噻唑啉酮衍生物的结构式为
    Figure PCTCN2022136096-appb-100001
    microemulsion multifunctional nano oil displacing agent according to claim 1, wherein, the structural formula of described isothiazolinone derivatives is
    Figure PCTCN2022136096-appb-100001
  5. 根据权利要求1或4所述的微乳液多功能纳米驱油剂，其中，所述异噻唑啉酮衍生物是先使NaH、N,N-二甲基甲酰胺和异噻唑啉-3-酮在氮气保护气氛下进行反应，然后向所得反应体系中加入γ-氯丙基三乙氧基硅烷，在冰浴条件下反应20-40min，再于70-100℃反应2-4h后经溶剂分离后制得。The microemulsion multifunctional nano-oil displacing agent according to claim 1 or 4, wherein, the isothiazolinone derivative is first made of NaH, N,N-dimethylformamide and isothiazolin-3-ketone Carry out the reaction under a nitrogen protective atmosphere, then add γ-chloropropyltriethoxysilane to the resulting reaction system, react under ice bath conditions for 20-40min, and then react at 70-100°C for 2-4h and then separate by solvent made later.
  6. 根据权利要求1所述的微乳液多功能纳米驱油剂，其中，所述增渗剂包括超支化乳化润湿分散剂。The microemulsion multifunctional nano-oil displacing agent according to claim 1, wherein the penetration enhancer comprises a hyperbranched emulsifying wetting and dispersing agent.
  7. 根据权利要求1所述的微乳液多功能纳米驱油剂，其中，所述稳定剂包括聚乙烯醇。The microemulsion multifunctional nano oil displacing agent according to claim 1, wherein said stabilizer comprises polyvinyl alcohol.
  8. 根据权利要求1所述的微乳液多功能纳米驱油剂，其中，所述微乳液多功能纳米驱油剂还包括1-5份的有机防膨剂。The microemulsion multifunctional nano oil displacing agent according to claim 1, wherein the microemulsion multifunctional nano oil displacing agent further comprises 1-5 parts of organic anti-swelling agent.
  9. 根据权利要求8所述的微乳液多功能纳米驱油剂，其中，所述有机防膨剂包括有机防膨剂HJZ-100。The microemulsion multifunctional nano-oil displacing agent according to claim 8, wherein the organic anti-swelling agent comprises organic anti-swelling agent HJZ-100.
  10. 权利要求1-9任一项所述的微乳液多功能纳米驱油剂的制备方法，其中，包括：The preparation method of the microemulsion multifunctional nano oil displacement agent described in any one of claims 1-9, wherein, comprising:
    (1)将纳米二氧化硅、二苯醚类双子表面活性剂、异噻唑啉酮衍生物混合均匀；(1) Mix nano silicon dioxide, diphenyl ether gemini surfactant, and isothiazolinone derivatives evenly;
    (2)向步骤(1)所得混合物中加入十二烷和十四烷，并于慢速条件下混合均匀；(2) Add dodecane and tetradecane to the mixture obtained in step (1), and mix uniformly under slow conditions;
    (3)向步骤(2)所得混合物中加入增渗剂、稳定剂和水，混合均匀后即得到所述微乳液多功能纳米驱油剂。(3) Add a penetration enhancer, a stabilizer and water to the mixture obtained in step (2), and mix uniformly to obtain the microemulsion multifunctional nano-oil displacing agent.
  11. 根据权利要求10所述的制备方法，其中，步骤(1)中所述混合均匀通过搅拌实现，所述搅拌为2000-3000r/min条件下搅拌3-5min。The preparation method according to claim 10, wherein the homogeneous mixing in step (1) is realized by stirring, and the stirring is 3-5min under the condition of 2000-3000r/min.
  12. 根据权利要求10所述的制备方法，其中，步骤(2)中所述混合均匀通过搅拌实现，所述搅拌为100-300r/min条件下搅拌2-4h。The preparation method according to claim 10, wherein the homogeneous mixing in step (2) is realized by stirring, and the stirring is 2-4h under the condition of 100-300r/min.
  13. 根据权利要求10所述的制备方法，其中，步骤(3)中所述混合均匀通过搅拌实现，所述搅拌为500-1000r/min条件下搅拌0.5-2h。The preparation method according to claim 10, wherein the uniform mixing in step (3) is realized by stirring, and the stirring is 0.5-2h under the condition of 500-1000r/min.
  14. 权利要求1-9任一项所述微乳液多功能纳米驱油剂在致密油储集层开发中的应用。The application of the microemulsion multifunctional nano oil displacement agent described in any one of claims 1-9 in the development of tight oil reservoirs.
  15. 根据权利要求14所述的应用，其中，所述致密油储集层为特低渗透油藏。The application according to claim 14, wherein the tight oil reservoir is an ultra-low permeability reservoir.
  16. 根据权利要求14或15所述的应用，其中，所述微乳液多功能纳米驱油剂的用量为洗油质量的0.1％-1％。The application according to claim 14 or 15, wherein the dosage of the microemulsion multifunctional nano oil displacing agent is 0.1%-1% of the washing oil mass.
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