WO2023083144A1 - Amphiphobic fluorine-containing nanofluid, preparation method therefor and application thereof - Google Patents

Amphiphobic fluorine-containing nanofluid, preparation method therefor and application thereof Download PDF

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WO2023083144A1
WO2023083144A1 PCT/CN2022/130369 CN2022130369W WO2023083144A1 WO 2023083144 A1 WO2023083144 A1 WO 2023083144A1 CN 2022130369 W CN2022130369 W CN 2022130369W WO 2023083144 A1 WO2023083144 A1 WO 2023083144A1
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fluorine
nanofluid
nano
amphobic
preparation
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Chinese (zh)
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王彦玲
史文静
梁雷
刘斌
梁诗南
张传保
李迪
陈孟鑫
许宁
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中国石油大学(华东)
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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
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    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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    • 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
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
    • C09K8/882—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
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    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/10—Nanoparticle-containing well treatment fluids

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  • the invention relates to an amphobic fluorine-containing nanofluid and its preparation method and application, belonging to the technical fields of oil field chemistry and colloid and interface chemistry.
  • CN113308236A discloses a temperature-resistant, high-efficiency waterproof locking agent for fracturing tight gas reservoirs.
  • fluorine Carbon nonionic surfactant 0.3-2.0%; perfluorononyl-enyloxybenzene sulfonate 0.1-1.0%; branched chain dodecylbenzene sulfonate 0.3-1.0%; short-chain alcohol 10-25% ; Organic carboxylate 6-13%; Mineralized water 60-83%. It has the advantages of strong temperature resistance, small solution particle size, excellent surface/interface performance, good wetting performance, low use concentration and strong waterproof locking ability, and has great application prospects in the synergistic mining of tight gas fracturing.
  • the technical problem solved by the present invention is to overcome the problem that the wettability of the reservoir in the prior art can only be transformed into hydrophobicity, and to provide a fluorine-containing polymer nanometer that can transform the wettability of the hydrophilic-oleophilic reservoir into amphiphobic fluid.
  • the invention also provides the application of the fluorine-containing nanofluid.
  • An amphobic fluorine-containing nanofluid that can change the wettability of the reservoir from hydrophilic to amphiphobic, and has a core-shell structure composed of nano-core materials and polymer shell materials; wherein,
  • nano-silica in an acidic environment, disperse nano-silica in ethanol, add a silane coupling agent, heat up to a reaction temperature of 60-80°C, and prepare a nano-core material through a coupling reaction;
  • the nano-silica It is hydrophilic nano silicon dioxide;
  • step (1) Disperse fluorine-containing monomers, emulsifiers and initiators in N,N-dimethylformamide, and add them to the nano-core material prepared in step (1) for polymerization.
  • the polymerization temperature is 60 to 80 °C, an amphobic fluorine-containing nanofluid is obtained.
  • amphobic fluorine-containing nanofluid prepared by the invention can be directly put into use without purification. It can significantly change the wettability of the reservoir, and can change the wettability of the reservoir to amphiphobic.
  • the amphobic fluorine-containing nanofluid prepared by the invention has a core-shell structure; the particle size distribution of nanoparticles in the amphobic fluorine-containing nanofluid is 200-300nm. Stable in nature, simple and easy to operate in the preparation process,
  • the particle size of the hydrophilic nano silicon dioxide is 20-50 nm.
  • the market is available.
  • the surface of hydrophilic silica is rich in hydroxyl groups, which is easy for coupling reaction and subsequent polymerization with fluorine-containing monomers.
  • the fluorine-containing monomer is 1,1,1,3,3,3-hexafluoroisopropyl acrylate, 2-(perfluorobutyl) ethyl acrylate, methacrylic acid One of dodecafluoroheptyl esters.
  • the emulsifier is one of sodium dodecylbenzenesulfonate, sodium dodecylsulfate, dodecyltrimethylammonium bromide, perfluorooctanoic acid and sodium perfluorononenyloxybenzenesulfonate. Further preferably, the emulsifier is sodium perfluorononenyloxybenzenesulfonate.
  • the content of nano-silica dispersed in ethanol is 1.5-2.5 g/L; more preferably, the content of nano-silica is 2 g/L.
  • the amount used here is relative to the volume of ethanol.
  • the mass ratio of nano-silica to silane coupling agent is 1:15 to 20; or the molar ratio of hydroxyl in hydrophilic nano-silica to silane coupling agent is 0.9 ⁇ 1.1:1.
  • the volume ratio of the amount of N,N-dimethylformamide (DMF) used in step (2) to the amount of ethanol used in step (1) is 1-2:1-2. More preferably, the volume ratio of ethanol and N,N-dimethylformamide (DMF) is 1:1.
  • the amount of ethanol and N,N-dimethylformamide solvent in the reaction system is of great significance to the morphology of the product. If the ratio of reaction monomer to solvent is too large or too small, the product will not be able to form a stable core-shell structure, which will affect the appearance of the product. its performance.
  • the dosages of the emulsifier and the initiator in step (2) are both 0.5-1.5 g/L. More preferably, the dosages of the emulsifier and initiator are both 1 g/L.
  • the amount used here is relative to the total volume of ethanol and N,N-dimethylformamide.
  • the step (2) further includes ultrasonic emulsifying the reaction system at room temperature for 20-40 minutes before the polymerization reaction.
  • the application of the fluorine-containing nanofluid prepared by the invention in changing the wettability of the reservoir changes the wettability of the reservoir from hydrophilic and lipophilic to amphiphobic. It is mainly used in the working fluid in the process of oil displacement, such as polymer flooding system, water injection system, etc.
  • the wettability of the reservoir can be changed from hydrophilic and lipophilic to amphiphobic (see Table 1). It can significantly improve the wettability of the formation, and effectively solve the liquid lock effect and Jamin effect caused by the wettability of the reservoir.
  • a working fluid for oil displacement characterized in that the working fluid contains the fluorine-containing nanofluid prepared by the invention.
  • the effective concentration of the fluorine-containing nanofluid in the working fluid is 0.1 wt.%.
  • the liquid phase passes through its surface with strong adhesion force, which increases its migration resistance, which is not conducive to the migration of working fluid and oil and gas components, transforming the reservoir into amphiphobic, reducing the The migration resistance is reduced, so as to achieve the effect of releasing the liquid lock effect and the Jamin effect.
  • the present invention uses hydrophilic silicon dioxide nanomaterials as the core, and has the advantage that the nanomaterials are more rigid, can significantly increase the roughness of the rock core, reduce surface free energy, and make the surface amphibious. Grafting the coupling agent with double bonds to the surface of silica nanoparticles is more conducive to the subsequent polymerization with fluorine-containing monomers.
  • the fluorine-containing substances in the shell have a large bond energy and change the chemical composition of the surface. Therefore, by changing the chemical composition and roughness of the surface, the surface free energy can be reduced more, and the wettability of the reservoir can be transformed into obvious amphiphobic.
  • the fluorine-containing nanofluid prepared by the present invention can change the wettability of the reservoir from hydrophilic and lipophilic to amphiphobic at a concentration of 0.1 wt.%.
  • the contact angles of rock cores with water and n-hexadecane can reach up to 158° and 140° after being treated with 0.1wt.% concentration of fluorine-containing nanofluid of the present invention.
  • the preparation method of the fluorine-containing nanofluid prepared by the present invention is simple, the raw materials are easy to obtain, the preparation conditions are mild, the reaction conditions are easy to control, and the reaction process is safe. Fluorine-containing nanofluid products are stable and can significantly change the wettability of reservoirs.
  • the fluorine-containing nanofluid prepared by the present invention has good compatibility with other oil recovery working fluid systems (such as polymer flooding systems and water injection systems), and can be directly put into use without purification, and does not need to add co-solvents.
  • oil recovery working fluid systems such as polymer flooding systems and water injection systems
  • the fluorine-containing nanofluid prepared by the present invention has extremely strong wetting reversal ability, can be used for reservoir reconstruction, and can effectively solve the liquid lock effect and Jamin effect caused by the wettability of the reservoir.
  • Figure 1 is a transmission electron microscope image of the fluorine-containing nanofluid prepared in Example 5. It can be seen from the figure that the nanoparticles have an obvious core-shell structure, and the particle size distribution is around 300nm.
  • Fig. 2 is the scanning electron micrograph of the core before and after treatment with the fluorine-containing nanofluid prepared in Example 5.
  • a is the untreated core surface
  • b is the core surface treated with 0.1wt.% fluorine-containing nanofluid.
  • Fig. 3 is a picture of the contact angle of the core with water and n-hexadecane after being treated with 0.1wt.% fluorine-containing nanofluid prepared in Example 5.
  • the left droplet is the aqueous solution dyed with methylene blue
  • the right droplet is the n-hexadecane solution dyed with Sudan red.
  • the contact angles of the cores with water and n-hexadecane are 158° and 140°, and the wettability changes to amphiphobic.
  • the nano silicon dioxide used in the embodiment is hydrophilic nano silicon dioxide with a particle size of 30nm. market.
  • a method for preparing an amphobic fluorine-containing nanofluid In a 250mL three-neck flask with a reflux device and electromagnetic stirring, add 0.1g of hydrophilic nano-silicon dioxide and 50mL of absolute ethanol respectively, and adjust the pH with 1mol/L hydrochloric acid To 4, add 0.01mol vinyltrimethoxysilane (1.5g) after ultrasonication at room temperature for 10min, and react at 80°C for 1h to obtain a nano core material; then add 0.01mol 1,1,1,3,3,3 - Hexafluoroisopropyl acrylate (2.2g), 0.1g sodium lauryl sulfate and 0.1g azobisisobutyronitrile were added to 50mL N, N-dimethylformamide, and added at room temperature to the prepared The nano-core material was ultrasonically emulsified for 30 minutes, and then heated to 80° C. for 4 hours. After complete reaction, the obtained light yellow emulsion product is amphiphobic fluorine
  • the preparation method is as described in Example 1, except that the silane coupling agent is vinyltriethoxysilane.
  • the preparation method is as described in Example 1, except that the silane coupling agent is allyltriethoxysilane, and the emulsifier is 0.1 g sodium perfluorononenyloxybenzenesulfonate.
  • the preparation method is as described in Example 3, except that the fluorine-containing monomer is 2-(perfluorobutyl) ethyl acrylate.
  • a method for preparing an amphobic fluorine-containing nanofluid In a 250mL three-neck flask with a reflux device and electromagnetic stirring, add 0.1g of hydrophilic nano-silicon dioxide and 50mL of absolute ethanol respectively, and adjust the pH with 1mol/L hydrochloric acid To 4, add 0.01mol allyltriethoxysilane (2.0g) after ultrasonication at room temperature for 10min, and react at 80°C for 1h to obtain a nano core material; then add 0.01mol dodecafluoroheptyl methacrylate ( 4.0g), 0.1g sodium perfluorononenyloxybenzenesulfonate and 0.1g azobisisobutyronitrile were added to 50mL N,N-dimethylformamide, and added to the prepared nano-core material at room temperature for ultrasonication Emulsify for 30 minutes, then raise the temperature to 80°C for 4 hours.
  • the obtained light yellow emulsion product is an amphobic flu
  • FIG. 2 The scanning electron micrographs of the prepared core before and after treatment with fluorine-containing nanofluid are shown in Figure 2, where a is the surface of the core without treatment, and b is the surface of the core after treatment with 0.1wt.% fluorine-containing nanofluid. It can be seen from Fig. 2 that the surface of the original core is mainly composed of stripes produced by mechanical cutting and structural exfoliation. After treatment with fluoropolymer nanofluid, the nanoparticles are tightly adsorbed on the surface of the core, changing the surface chemistry of the core. structure and roughness.
  • the difference is that the reaction temperature in the two-step reaction is 60°C.
  • the difference is that the molar ratio of the fluorine-containing monomer to the silane coupling agent is 2:1.
  • the selected core is hydrophilic and lipophilic, and its surface wettability changes to amphiphobic after treatment.
  • Comparing Examples 1 and 2 increasing the carbon of the double bond main chain in the silane coupling agent can improve the wettability of the product, and comparing Examples 2 and 3, increasing the carbon of the siloxane substituent in the silane coupling agent , can improve the wettability of the product, and compare Examples 3, 4, and 5, increasing the content of fluorine-substituted alkanes in the fluorine-containing monomer can improve the wettability of the product.
  • Example 5 Comparing Example 5 with Examples 6, 7, and 8, it can be seen that reducing the pH value of the coupling reaction will increase the hydrolysis between nanoparticles, reducing the reaction temperature will reduce the reactivity of the reaction substance, and increase the mole of fluorine-containing monomers.
  • the quality will increase the polymerization between fluorine-containing monomers, which is not conducive to the formation of a regular core-shell structure, so the wettability of the product is reduced.
  • the contact angles of the rock core surface with water and n-hexadecane after the product treatment in Example 5 are 158° and 140° (see Figure 3), reaching the super-hydrophobic effect.
  • the fluorine-containing nanofluid prepared by the present invention has stronger wettability and inversion ability than the fluorine-containing polymer emulsion prepared in Comparative Example 1, and can degrade the core surface at a lower concentration.
  • the wettability changes from hydrophilic-lipophilic to amphiphobic.
  • the core-shell type fluorine-containing nanofluid prepared by the present invention has stronger wetting inversion ability than the core-shell type fluoropolymer emulsion prepared in Comparative Example 2, and can be used at a lower
  • the wettability of the core surface is changed from hydrophilic and lipophilic to amphiphobic at low concentrations.
  • amphiphobic fluorine-containing nanofluid with the core-shell structure prepared by the present invention has a very strong wettability reversal ability, and can change the wettability of the core surface from hydrophilic to lipophilic at a relatively low concentration. Hydrophobicity can effectively improve the problems caused by reservoir wettability in the process of oil and gas resource development.
  • the compatibility test results after 0.1wt.% nanofluid is added to the working solution, the system has no precipitation and no layering phenomenon, and the prepared product has good compatibility with the commonly used working solution.
  • the shell-structured amphiphobic fluorine-containing nanofluid has good compatibility and can be used directly without purification.

Abstract

The present invention relates to an amphiphobic fluorine-containing nanofluid, a preparation method therefor and an application thereof. The amphiphobic fluorine-containing nanofluid is composed of a nanocore material and a polymer shell material. The surface of the nanocore material is grafted with a coupling agent with double bonds, and the polymer shell material contains a fluorine polymer. The present invention further provides a preparation method and application for the amphiphobic fluorine-containing nanofluid. The amphiphobic fluorine-containing nanofluid of the present invention has extremely strong wetting reversal capability, can be used for reservoir reformation of an oil reservoir, can convert reservoir wettability from hydrophilic and oleophylic to remarkable amphiphobic property, and effectively solves the liquid lock effect and the Jamin effect caused by the reservoir wettability.

Description

一种双疏型含氟纳米流体及其制备方法与应用A kind of amphiphobic fluorine-containing nanofluid and its preparation method and application 技术领域technical field
本发明涉及一种双疏型含氟纳米流体及其制备方法与应用，属于油田化学和胶体与界面化学技术领域。The invention relates to an amphobic fluorine-containing nanofluid and its preparation method and application, belonging to the technical fields of oil field chemistry and colloid and interface chemistry.
背景技术Background technique
在钻井、完井、修井等油气开采过程中，液体在多孔介质中的滞留会出现许多问题。在多孔介质中，当另一非混溶相渗入储层或原始非混溶相饱和度增加时，储层相对渗透率会受到损害，储层渗透率和油气相对渗透率会降低，这种现象称为液锁效应。当液－液或气－液两相渗流中的液滴或气泡通过孔喉或狭窄通道时，会产生附加阻力效应，这种现象被称为贾敏效应。这些效应会增加油气资源和地层工作液的运移阻力，使得油气开采和工作液的回流变得极其困难。During oil and gas production such as drilling, well completion, well workover, etc., the stagnation of liquid in porous media will cause many problems. In porous media, when another immiscible phase infiltrates into the reservoir or the saturation of the original immiscible phase increases, the relative permeability of the reservoir will be damaged, and the permeability of the reservoir and the relative permeability of oil and gas will decrease. This phenomenon called the liquid lock effect. When liquid droplets or bubbles in liquid-liquid or gas-liquid two-phase seepage flow through pore throats or narrow channels, additional resistance effects will occur, which is called the Jamin effect. These effects will increase the migration resistance of oil and gas resources and formation working fluid, making oil and gas production and return of working fluid extremely difficult.
针对亲水亲油地层的开采过程中存在的严重液锁问题，储层的润湿性改造对油气的开采和工作液的反排起着至关重要的作用。通常会使用表面活性剂来实现储层的润湿性反转，例如CN113308236A公开了一种耐温、高效致密气藏压裂用防水锁剂，按质量百分含量计，包括如下组分：氟碳类非离子表面活性剂0.3～2.0％；全氟壬基烯氧基苯磺酸盐0.1～1.0％；支链十二烷基苯磺酸盐0.3～1.0％；短链醇10～25％；有机羧酸盐6～13％；矿化水60～83％。其具有耐温能力强、溶液粒径小、表/界面性能优、润湿性能好、使用浓度低和防水锁能力强的优点，在致密气压裂增效开采中具有巨大的应用前景。该专利公开的压裂用防水锁剂，其本质为复合型表面活性剂，依赖于表活剂降低界面张力来实现解除水锁效应。但大量表面活性剂的引入会使采出和返排液体中产生强烈的乳化作用，导致使用成本和后期处理难度的加大。In view of the serious liquid lock problem in the production process of hydrophilic and oil-wet formations, the wettability modification of reservoirs plays a vital role in the production of oil and gas and the reverse flow of working fluid. Surfactants are usually used to achieve the wettability reversal of reservoirs. For example, CN113308236A discloses a temperature-resistant, high-efficiency waterproof locking agent for fracturing tight gas reservoirs. It includes the following components in terms of mass percentage: fluorine Carbon nonionic surfactant 0.3-2.0%; perfluorononyl-enyloxybenzene sulfonate 0.1-1.0%; branched chain dodecylbenzene sulfonate 0.3-1.0%; short-chain alcohol 10-25% ; Organic carboxylate 6-13%; Mineralized water 60-83%. It has the advantages of strong temperature resistance, small solution particle size, excellent surface/interface performance, good wetting performance, low use concentration and strong waterproof locking ability, and has great application prospects in the synergistic mining of tight gas fracturing. The waterproof locking agent for fracturing disclosed in this patent is essentially a composite surfactant, relying on the surfactant to reduce the interfacial tension to achieve the release of the water locking effect. However, the introduction of a large amount of surfactants will cause strong emulsification in the production and flowback liquids, which will increase the cost of use and the difficulty of post-processing.
为了解决所述的水锁问题，有研究将含氟聚合物作为润湿反转剂，并合成了FP-2润湿反转剂，参见王彦玲,金家锋,董红岩,姜令.用于解水锁的气润湿反转剂的合成与性能评价[J].西安石油大学学报(自然科学版),2015,30(05):85-90+11)。该文章还讨论了固-液-气多相作用条件下试剂对于解水锁的相关研究，其适用于将岩芯由强液湿转为气润湿。但该润湿反转剂仅仅针对亲水油藏的润湿性转变，但对于亲油性地层，无法实现润湿性的反转。In order to solve the problem of water locking, some studies have used fluoropolymers as wetting reversal agents, and synthesized FP-2 wetting reversal agents, see Wang Yanling, Jin Jiafeng, Dong Hongyan, Jiang Ling. The gas used to release water locking Synthesis and performance evaluation of wetting reversal agent[J]. Journal of Xi'an Shiyou University (Natural Science Edition), 2015,30(05):85-90+11). This article also discusses the related research of reagents on water lock under the condition of solid-liquid-gas multiphase interaction, which is suitable for changing the core from strong liquid wetting to gas wetting. However, the wettability reversal agent is only aimed at the wettability transformation of hydrophilic reservoirs, but it cannot achieve wettability reversal for lipophilic formations.
而针对复杂的亲水亲油地层的开采过程中存在的严重液锁问题，需要使储层润湿性由亲水亲油性转变为双疏性才能实现解水锁。为此提出本发明。In view of the serious liquid lock problem in the production process of complex hydrophilic and oil-wet formations, it is necessary to change the wettability of the reservoir from hydrophilic and lipophilic to amphiphobic to realize the release of water lock. The present invention is proposed for this reason.
发明内容Contents of the invention
针对复杂的亲水亲油地层的储层润湿性问题，本发明提供了一种能显著改变储层润湿性的含氟纳米流体及其制备方法。Aiming at the reservoir wettability problem of complex hydrophilic and oil-wet formations, the invention provides a fluorine-containing nanofluid capable of significantly changing the wettability of the reservoir and a preparation method thereof.
本发明解决的技术问题是，克服了现有技术储层润湿性仅能转变为疏水性，提供一种可将亲水亲油储层润湿性转变为双疏性的含氟聚合物纳米流体。The technical problem solved by the present invention is to overcome the problem that the wettability of the reservoir in the prior art can only be transformed into hydrophobicity, and to provide a fluorine-containing polymer nanometer that can transform the wettability of the hydrophilic-oleophilic reservoir into amphiphobic fluid.
本发明还提供所述含氟纳米流体的应用。The invention also provides the application of the fluorine-containing nanofluid.
本发明的技术方案如下：Technical scheme of the present invention is as follows:
一种可将储层润湿性由亲水亲油转变为双疏性的双疏型含氟纳米流体，具有由纳米核心材料和聚合物壳层材料构成的核壳结构；其中，An amphobic fluorine-containing nanofluid that can change the wettability of the reservoir from hydrophilic to amphiphobic, and has a core-shell structure composed of nano-core materials and polymer shell materials; wherein,
所述纳米核心材料表面接枝带有双键的偶联剂，是由亲水性纳米二氧化硅与硅烷偶联剂反应制得；The surface of the nano-core material is grafted with a coupling agent with a double bond, which is prepared by reacting hydrophilic nano-silica and a silane coupling agent;
所述聚合物壳层材料含氟聚合物，是含氟单体通过聚合反应包覆在所述纳米核心材料上。The fluorine-containing polymer of the polymer shell material is that the fluorine-containing monomer is coated on the nanometer core material through polymerization reaction.
一种双疏型含氟纳米流体的制备方法，包括步骤：A method for preparing an amphobic fluorine-containing nanofluid, comprising the steps of:
(1)在酸性环境下，将纳米二氧化硅分散在乙醇中，加入硅烷偶联剂，升温至反应温度60-80℃，通过偶联反应制得纳米核心材料；所述的纳米二氧化硅为亲水性纳米二氧化硅；(1) In an acidic environment, disperse nano-silica in ethanol, add a silane coupling agent, heat up to a reaction temperature of 60-80°C, and prepare a nano-core material through a coupling reaction; the nano-silica It is hydrophilic nano silicon dioxide;
(2)将含氟单体、乳化剂和引发剂分散到N，N-二甲基甲酰胺中，加入到步骤(1)制备的纳米核心材料中进行聚合反应，聚合反应温度为60～80℃，得到双疏型含氟纳米流体。(2) Disperse fluorine-containing monomers, emulsifiers and initiators in N,N-dimethylformamide, and add them to the nano-core material prepared in step (1) for polymerization. The polymerization temperature is 60 to 80 °C, an amphobic fluorine-containing nanofluid is obtained.
本发明所制备的双疏型含氟纳米流体不用提纯可直接投入使用。能够显著改变储层的润湿性，可将储层润湿性转变为双疏性。The amphobic fluorine-containing nanofluid prepared by the invention can be directly put into use without purification. It can significantly change the wettability of the reservoir, and can change the wettability of the reservoir to amphiphobic.
本发明所制备的双疏型含氟纳米流体具有核壳结构；所述双疏型含氟纳米流体中纳米颗粒的粒径分布在200～300nm。性质稳定，制备过程简单易操作，The amphobic fluorine-containing nanofluid prepared by the invention has a core-shell structure; the particle size distribution of nanoparticles in the amphobic fluorine-containing nanofluid is 200-300nm. Stable in nature, simple and easy to operate in the preparation process,
根据本发明优选的，所述的亲水性纳米二氧化硅粒径为20～50nm。市场有售。亲水性二氧化硅表面富有羟基，易于偶联反应，并易于与含氟单体进行后续聚合。Preferably according to the present invention, the particle size of the hydrophilic nano silicon dioxide is 20-50 nm. The market is available. The surface of hydrophilic silica is rich in hydroxyl groups, which is easy for coupling reaction and subsequent polymerization with fluorine-containing monomers.
根据本发明优选的，所述的酸性环境pH值为1～4；优选用盐酸溶液调节pH值。进一步优选盐酸溶液浓度1～2mol/L。Preferably according to the present invention, the pH value of the acidic environment is 1-4; the pH value is preferably adjusted with hydrochloric acid solution. More preferably, the concentration of the hydrochloric acid solution is 1-2 mol/L.
所述的硅烷偶联剂为带有双键的硅烷偶联剂，优选自3-(甲基丙烯酰氧)丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、烯丙基三甲氧基硅烷、丙烯酰氧甲基三甲氧基硅烷、烯丙基三乙 氧基硅烷、甲基丙烯酰氧基甲基三乙氧基硅烷、乙烯基三乙氧基硅烷之一。进一步优选的，所述的硅烷偶联剂为乙烯基三甲氧基硅烷，烯丙基三甲氧基硅烷，乙烯基三乙氧基硅烷，烯丙基三乙氧基硅烷中的一种。硅烷偶联剂中硅氧烷和纳米二氧化硅中硅羟基在酸性条件下水解，将带有双键的偶联剂接枝到纳米颗粒表面。The silane coupling agent is a silane coupling agent with a double bond, preferably from 3-(methacryloyloxy)propyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane , Acryloyloxymethyltrimethoxysilane, allyltriethoxysilane, methacryloyloxymethyltriethoxysilane, vinyltriethoxysilane. Further preferably, the silane coupling agent is one of vinyltrimethoxysilane, allyltrimethoxysilane, vinyltriethoxysilane and allyltriethoxysilane. The siloxane in the silane coupling agent and the silicon hydroxyl group in the nano-silicon dioxide are hydrolyzed under acidic conditions, and the coupling agent with double bonds is grafted onto the surface of the nanoparticles.
根据本发明优选的，所述的含氟单体为1,1,1,3,3,3-六氟异丙基丙烯酸酯，2-(全氟丁基)乙基丙烯酸酯，甲基丙烯酸十二氟庚酯中的一种。Preferably according to the present invention, the fluorine-containing monomer is 1,1,1,3,3,3-hexafluoroisopropyl acrylate, 2-(perfluorobutyl) ethyl acrylate, methacrylic acid One of dodecafluoroheptyl esters.
所述乳化剂为十二烷基苯磺酸钠、十二烷基硫酸钠、十二烷基三甲基溴化铵、全氟辛酸、全氟壬烯氧基苯磺酸钠中的一种。进一步优选的，所述乳化剂为全氟壬烯氧基苯磺酸钠。The emulsifier is one of sodium dodecylbenzenesulfonate, sodium dodecylsulfate, dodecyltrimethylammonium bromide, perfluorooctanoic acid and sodium perfluorononenyloxybenzenesulfonate. Further preferably, the emulsifier is sodium perfluorononenyloxybenzenesulfonate.
所述的引发剂为过硫酸铵、过氧化苯甲酰、偶氮二异丁腈中的一种。进一步优选的，所述的引发剂为偶氮二异丁腈。The initiator is one of ammonium persulfate, benzoyl peroxide and azobisisobutyronitrile. Further preferably, the initiator is azobisisobutyronitrile.
根据本发明优选的，步骤(1)中，分散在乙醇中的纳米二氧化硅含量为1.5～2.5g/L；进一步优选纳米二氧化硅含量为2g/L。此处用量是相对于乙醇的体积。Preferably, according to the present invention, in step (1), the content of nano-silica dispersed in ethanol is 1.5-2.5 g/L; more preferably, the content of nano-silica is 2 g/L. The amount used here is relative to the volume of ethanol.
根据本发明优选的，步骤(1)中，纳米二氧化硅与硅烷偶联剂质量比为1:15～20；或者亲水性纳米二氧化硅中的羟基与硅烷偶联剂的摩尔比为0.9～1.1:1。Preferably according to the present invention, in step (1), the mass ratio of nano-silica to silane coupling agent is 1:15 to 20; or the molar ratio of hydroxyl in hydrophilic nano-silica to silane coupling agent is 0.9～1.1:1.
根据本发明优选的，步骤(2)中，含氟单体与硅烷偶联剂摩尔比为1～2:1～2。进一步优选，含氟单体与硅烷偶联剂摩尔比为1:1～2。含氟单体含量不宜过大，过多的话含氟单体与纳米核心聚合反应完成后，游离的含氟单体自聚，会增加核壳结构的粒径，从而使得纳米流体不稳定，增加材料之间的碰撞，严重的还会聚沉。Preferably according to the present invention, in step (2), the molar ratio of the fluorine-containing monomer to the silane coupling agent is 1-2:1-2. More preferably, the molar ratio of the fluorine-containing monomer to the silane coupling agent is 1:1-2. The content of fluorine-containing monomer should not be too large. If it is too much, after the polymerization reaction between fluorine-containing monomer and nano-core is completed, the free fluorine-containing monomer will self-polymerize, which will increase the particle size of the core-shell structure, thereby making the nanofluid unstable and increasing Collision between materials, serious will also cohesion.
根据本发明优选的，步骤(2)中N，N-二甲基甲酰胺(DMF)用量与步骤(1)中乙醇用量体积比为1～2:1～2。更优选的，乙醇和N，N-二甲基甲酰胺(DMF)体积比为1:1。反应体系中乙醇和N，N-二甲基甲酰胺溶剂用量对于产物形貌具有重要意义，反应单体与溶剂的比例过大或过小都会使产物无法形成稳定的核壳结构，进而影响到其性能。Preferably according to the present invention, the volume ratio of the amount of N,N-dimethylformamide (DMF) used in step (2) to the amount of ethanol used in step (1) is 1-2:1-2. More preferably, the volume ratio of ethanol and N,N-dimethylformamide (DMF) is 1:1. The amount of ethanol and N,N-dimethylformamide solvent in the reaction system is of great significance to the morphology of the product. If the ratio of reaction monomer to solvent is too large or too small, the product will not be able to form a stable core-shell structure, which will affect the appearance of the product. its performance.
根据本发明优选的，步骤(2)中所述乳化剂和引发剂用量都是0.5～1.5g/L。更优选的，所述乳化剂和引发剂用量都是1g/L。此处用量是相对于乙醇和N，N-二甲基甲酰胺的总体积。Preferably according to the present invention, the dosages of the emulsifier and the initiator in step (2) are both 0.5-1.5 g/L. More preferably, the dosages of the emulsifier and initiator are both 1 g/L. The amount used here is relative to the total volume of ethanol and N,N-dimethylformamide.
根据本发明优选的，步骤(2)还包括在聚合反应前，将反应体系在常温下进行超声乳化20～40min。Preferably according to the present invention, the step (2) further includes ultrasonic emulsifying the reaction system at room temperature for 20-40 minutes before the polymerization reaction.
根据本发明，一种优选的实施方案如下：According to the present invention, a kind of preferred embodiment is as follows:
于带有回流装置和电磁搅拌的反应容器中，分别加入0.1g亲水纳米二氧化硅和50mL无水乙醇，并用1mol/L盐酸调节pH到4，常温下超声10min后加入0.01mol硅烷偶联剂，并 在80℃下反应1h，得到纳米核心材料；再将0.01mol含氟单体，0.1g乳化剂和0.1g引发剂加入50mL N,N-二甲基甲酰胺中，并在常温下加入制备的纳米核心材料中超声乳化30min，随后升温至80℃反应4h。得到的淡黄色乳状液产品，即为核壳结构的双疏型含氟纳米流体。In a reaction vessel with a reflux device and electromagnetic stirring, add 0.1 g of hydrophilic nano-silica and 50 mL of absolute ethanol, and adjust the pH to 4 with 1 mol/L hydrochloric acid, and then add 0.01 mol of silane coupling agent, and reacted at 80°C for 1 hour to obtain a nano-core material; then add 0.01mol fluorine-containing monomer, 0.1g emulsifier and 0.1g initiator to 50mL N,N-dimethylformamide, and Add it into the prepared nano-core material for ultrasonic emulsification for 30 minutes, and then raise the temperature to 80° C. for 4 hours. The obtained light yellow emulsion product is an amphobic fluorine-containing nanofluid with a core-shell structure.
本发明制备的含氟纳米流体在改变储层润湿性中的应用，使储层润湿性由亲水亲油性转变为双疏性。主要用于驱油过程中的工作液中，如聚合物驱油体系、注水体系等。The application of the fluorine-containing nanofluid prepared by the invention in changing the wettability of the reservoir changes the wettability of the reservoir from hydrophilic and lipophilic to amphiphobic. It is mainly used in the working fluid in the process of oil displacement, such as polymer flooding system, water injection system, etc.
根据该所述的应用，优选的，在0.1wt.％的使用浓度下，能使储层润湿性由亲水亲油性转变为双疏性(参见表1)。能够显著改善地层的润湿性，有效解决由储层润湿性带来的液锁效应和贾敏效应。According to the said application, preferably, at the use concentration of 0.1 wt.%, the wettability of the reservoir can be changed from hydrophilic and lipophilic to amphiphobic (see Table 1). It can significantly improve the wettability of the formation, and effectively solve the liquid lock effect and Jamin effect caused by the wettability of the reservoir.
一种用于驱油的工作液，其特征在于，工作液中含有本发明制备的含氟纳米流体。优选的，所述含氟纳米流体的浓度在工作液中的有效浓度为0.1wt.％。A working fluid for oil displacement, characterized in that the working fluid contains the fluorine-containing nanofluid prepared by the invention. Preferably, the effective concentration of the fluorine-containing nanofluid in the working fluid is 0.1 wt.%.
本发明的技术特点及优良效果：Technical characteristics and excellent effects of the present invention:
在亲水亲油的地层，液相通过其表面时粘附力较大，使得其运移阻力增加，从而不利于工作液和油气组分的运移，将储层改造为双疏性，减小了运移阻力，从而达到解除液锁效应和贾敏效应的效果。本发明选用亲水性二氧化硅纳米材料为核心，优势在于纳米材料刚性更强，能够显著增加岩芯的粗糙度，降低表面自由能，使得表面达到双疏。而将带有双键的偶联剂接枝到二氧化硅纳米颗粒表面，更有利于后续的与含氟单体的聚合，壳层中含氟物质键能大，改变表面化学成分。从而通过改变表面的化学成分和粗糙度两个方面来更多地降低表面自由能，将储层润湿性改造为明显双疏性。In the hydrophilic and oil-wet formations, the liquid phase passes through its surface with strong adhesion force, which increases its migration resistance, which is not conducive to the migration of working fluid and oil and gas components, transforming the reservoir into amphiphobic, reducing the The migration resistance is reduced, so as to achieve the effect of releasing the liquid lock effect and the Jamin effect. The present invention uses hydrophilic silicon dioxide nanomaterials as the core, and has the advantage that the nanomaterials are more rigid, can significantly increase the roughness of the rock core, reduce surface free energy, and make the surface amphibious. Grafting the coupling agent with double bonds to the surface of silica nanoparticles is more conducive to the subsequent polymerization with fluorine-containing monomers. The fluorine-containing substances in the shell have a large bond energy and change the chemical composition of the surface. Therefore, by changing the chemical composition and roughness of the surface, the surface free energy can be reduced more, and the wettability of the reservoir can be transformed into obvious amphiphobic.
1、本发明制备的含氟纳米流体，在0.1wt.％的使用浓度下，可使储层润湿性由亲水亲油性转变为双疏性。实验证明，使用本发明0.1wt.％浓度的含氟纳米流体处理后使岩芯与水和正十六烷的接触角最大可达158°和140°。1. The fluorine-containing nanofluid prepared by the present invention can change the wettability of the reservoir from hydrophilic and lipophilic to amphiphobic at a concentration of 0.1 wt.%. Experiments have proved that the contact angles of rock cores with water and n-hexadecane can reach up to 158° and 140° after being treated with 0.1wt.% concentration of fluorine-containing nanofluid of the present invention.
2、本发明制备的含氟纳米流体制备方法简单，原料容易获得，制备条件温和，反应条件容易控制，反应过程安全。含氟纳米流体产物性质稳定，能够显著改变储层的润湿性。2. The preparation method of the fluorine-containing nanofluid prepared by the present invention is simple, the raw materials are easy to obtain, the preparation conditions are mild, the reaction conditions are easy to control, and the reaction process is safe. Fluorine-containing nanofluid products are stable and can significantly change the wettability of reservoirs.
3、本发明制备的含氟纳米流体与其他采油工作液体系(如聚合物驱油体系、注水体系)有良好的配伍性，可以不用提纯直接投入使用，也不需要添加助溶剂。3. The fluorine-containing nanofluid prepared by the present invention has good compatibility with other oil recovery working fluid systems (such as polymer flooding systems and water injection systems), and can be directly put into use without purification, and does not need to add co-solvents.
4、本发明制备的含氟纳米流体，拥有极强的润湿反转能力，可用于油藏储层改造，有效解决由储层润湿性带来的液锁效应和贾敏效应。4. The fluorine-containing nanofluid prepared by the present invention has extremely strong wetting reversal ability, can be used for reservoir reconstruction, and can effectively solve the liquid lock effect and Jamin effect caused by the wettability of the reservoir.
附图说明Description of drawings
图1为实施例5制备的含氟纳米流体的透射电镜图。从图中可以看出，纳米颗粒具备明 显的核壳结构，且粒径分布在300nm左右。Figure 1 is a transmission electron microscope image of the fluorine-containing nanofluid prepared in Example 5. It can be seen from the figure that the nanoparticles have an obvious core-shell structure, and the particle size distribution is around 300nm.
图2为实施例5制备的含氟纳米流体处理前后岩芯的扫描电镜图。其中a为未处理时的岩芯表面，b为0.1wt.％含氟纳米流体处理后的岩芯表面。Fig. 2 is the scanning electron micrograph of the core before and after treatment with the fluorine-containing nanofluid prepared in Example 5. Wherein a is the untreated core surface, and b is the core surface treated with 0.1wt.% fluorine-containing nanofluid.
图3为实施例5制备的0.1wt.％含氟纳米流体处理后岩芯与水和正十六烷的接触角图片。其中左侧液滴为亚甲基蓝染色后的水溶液，右侧液滴为苏丹红染色后的正十六烷溶液。处理后岩芯与水和正十六烷的接触角为158°和140°，润湿性转变为双疏性。Fig. 3 is a picture of the contact angle of the core with water and n-hexadecane after being treated with 0.1wt.% fluorine-containing nanofluid prepared in Example 5. The left droplet is the aqueous solution dyed with methylene blue, and the right droplet is the n-hexadecane solution dyed with Sudan red. After treatment, the contact angles of the cores with water and n-hexadecane are 158° and 140°, and the wettability changes to amphiphobic.
具体实施方式Detailed ways
下面结合具体实施例对本发明作进一步说明，但本发明保护范围不仅限于此。The present invention will be further described below in conjunction with specific examples, but the protection scope of the present invention is not limited thereto.
实施例中所用的纳米二氧化硅为亲水性纳米二氧化硅，粒径为30nm。市场购得。The nano silicon dioxide used in the embodiment is hydrophilic nano silicon dioxide with a particle size of 30nm. market.
实施例1Example 1
一种双疏型含氟纳米流体的制备方法，于250mL带有回流装置和电磁搅拌的三口烧瓶中，分别加入0.1g亲水纳米二氧化硅和50mL无水乙醇，并用1mol/L盐酸调节pH到4，常温下超声10min后加入0.01mol乙烯基三甲氧基硅烷(1.5g)，并在80℃下反应1h，得到纳米核心材料；再将0.01mol 1,1,1,3,3,3-六氟异丙基丙烯酸酯(2.2g)，0.1g十二烷基硫酸钠和0.1g偶氮二异丁腈加入50mL N，N-二甲基甲酰胺中，并在常温下加入制备的纳米核心材料中超声乳化30min，随后升温至80℃反应4h。完全反应，得到的淡黄色乳状液产品，即为核壳结构的双疏型含氟纳米流体。产率约98％。A method for preparing an amphobic fluorine-containing nanofluid. In a 250mL three-neck flask with a reflux device and electromagnetic stirring, add 0.1g of hydrophilic nano-silicon dioxide and 50mL of absolute ethanol respectively, and adjust the pH with 1mol/L hydrochloric acid To 4, add 0.01mol vinyltrimethoxysilane (1.5g) after ultrasonication at room temperature for 10min, and react at 80°C for 1h to obtain a nano core material; then add 0.01mol 1,1,1,3,3,3 - Hexafluoroisopropyl acrylate (2.2g), 0.1g sodium lauryl sulfate and 0.1g azobisisobutyronitrile were added to 50mL N, N-dimethylformamide, and added at room temperature to the prepared The nano-core material was ultrasonically emulsified for 30 minutes, and then heated to 80° C. for 4 hours. After complete reaction, the obtained light yellow emulsion product is amphiphobic fluorine-containing nanofluid with core-shell structure. Yield about 98%.
实施例2Example 2
如实施例1所述的制备方法，所不同的是所述的硅烷偶联剂为乙烯基三乙氧基硅烷。The preparation method is as described in Example 1, except that the silane coupling agent is vinyltriethoxysilane.
实施例3Example 3
如实施例1所述的制备方法，所不同的是所述的硅烷偶联剂为烯丙基三乙氧基硅烷，所述的乳化剂为0.1g全氟壬烯氧基苯磺酸钠。The preparation method is as described in Example 1, except that the silane coupling agent is allyltriethoxysilane, and the emulsifier is 0.1 g sodium perfluorononenyloxybenzenesulfonate.
实施例4Example 4
如实施例3所述的制备方法，所不同的是：所述的含氟单体为2-(全氟丁基)乙基丙烯酸酯。The preparation method is as described in Example 3, except that the fluorine-containing monomer is 2-(perfluorobutyl) ethyl acrylate.
实施例5Example 5
一种双疏型含氟纳米流体的制备方法，于250mL带有回流装置和电磁搅拌的三口烧瓶中，分别加入0.1g亲水纳米二氧化硅和50mL无水乙醇，并用1mol/L盐酸调节pH到4，常温下超声10min后加入0.01mol烯丙基三乙氧基硅烷(2.0g)，并在80℃下反应1h，得到纳米核心 材料；再将0.01mol甲基丙烯酸十二氟庚酯(4.0g)，0.1g全氟壬烯氧基苯磺酸钠和0.1g偶氮二异丁腈加入50mL N,N-二甲基甲酰胺中，并在常温下加入制备的纳米核心材料中超声乳化30min，随后升温至80℃反应4h。得到的淡黄色乳状液产品，即为核壳结构的双疏型含氟纳米流体。产率约98.5％。A method for preparing an amphobic fluorine-containing nanofluid. In a 250mL three-neck flask with a reflux device and electromagnetic stirring, add 0.1g of hydrophilic nano-silicon dioxide and 50mL of absolute ethanol respectively, and adjust the pH with 1mol/L hydrochloric acid To 4, add 0.01mol allyltriethoxysilane (2.0g) after ultrasonication at room temperature for 10min, and react at 80°C for 1h to obtain a nano core material; then add 0.01mol dodecafluoroheptyl methacrylate ( 4.0g), 0.1g sodium perfluorononenyloxybenzenesulfonate and 0.1g azobisisobutyronitrile were added to 50mL N,N-dimethylformamide, and added to the prepared nano-core material at room temperature for ultrasonication Emulsify for 30 minutes, then raise the temperature to 80°C for 4 hours. The obtained light yellow emulsion product is an amphobic fluorine-containing nanofluid with a core-shell structure. The yield is about 98.5%.
制备的含氟纳米流体处理前后岩芯的扫描电镜图如图2所示，其中a为未处理时的岩芯表面，b为0.1wt.％含氟纳米流体处理后的岩芯表面。从图2中可以看出，原始岩芯表面主要由机械切割和结构剥离产生的条纹组成，用含氟聚合物纳米流体处理后，纳米颗粒紧密吸附在岩芯表面，改变了岩芯的表面化学结构和粗糙度。The scanning electron micrographs of the prepared core before and after treatment with fluorine-containing nanofluid are shown in Figure 2, where a is the surface of the core without treatment, and b is the surface of the core after treatment with 0.1wt.% fluorine-containing nanofluid. It can be seen from Fig. 2 that the surface of the original core is mainly composed of stripes produced by mechanical cutting and structural exfoliation. After treatment with fluoropolymer nanofluid, the nanoparticles are tightly adsorbed on the surface of the core, changing the surface chemistry of the core. structure and roughness.
实施例6Example 6
如实施例5所述的制备方法，所不同的是所述的偶联反应中pH值为1。As in the preparation method described in Example 5, the difference is that the pH value in the coupling reaction is 1.
实施例7Example 7
如实施例5所述的制备方法，所不同的是所述的两步反应中反应温度均为60℃。As in the preparation method described in Example 5, the difference is that the reaction temperature in the two-step reaction is 60°C.
实施例8Example 8
如实施例5所述的制备方法，所不同的是所述的含氟单体和硅烷偶联剂摩尔比为2:1。As in the preparation method described in Example 5, the difference is that the molar ratio of the fluorine-containing monomer to the silane coupling agent is 2:1.
对比例：Comparative example:
文献：王彦玲等.用于解水锁的气润湿反转剂的合成与性能评价[J].西安石油大学学报，2015,30(05):85-90+11。该文献中“1.2实验方法”制备的FP-2润湿反转剂，甲基丙烯酸十二氟庚酯与丙烯酸摩尔比1:2。采用自由基引发共聚反应，得到的产物为含氟聚合物。Literature: Wang Yanling et al. Synthesis and performance evaluation of gas-wetting reversal agent for water lock[J]. Journal of Xi'an Shiyou University, 2015,30(05):85-90+11. For the FP-2 wetting reversal agent prepared in "1.2 Experimental Method" in this document, the molar ratio of dodecafluoroheptyl methacrylate to acrylic acid is 1:2. The free radical is used to initiate the copolymerization reaction, and the obtained product is a fluorine-containing polymer.
实验例1：接触角实验。Experimental example 1: contact angle experiment.
将本实施例1-8合成的产物分别加水配制为0.1wt.％的纳米流体，再将天然岩芯切片浸泡于其中，常温常压下保持12h后取出，在60℃下干燥4h，并以蒸馏水为空白对照组，测量其与水和正十六烷的接触角，实验结果如表1所示。The products synthesized in Examples 1-8 were prepared into 0.1wt.% nanofluids by adding water respectively, and then soaked the natural rock core slices in it, kept it at normal temperature and pressure for 12 hours, took it out, dried it at 60°C for 4 hours, and used Distilled water was used as the blank control group, and its contact angle with water and n-hexadecane was measured. The experimental results are shown in Table 1.
表1 产物处理后岩芯表面的接触角Table 1 Contact angle of core surface after product treatment
Figure PCTCN2022130369-appb-000001
Figure PCTCN2022130369-appb-000001
Figure PCTCN2022130369-appb-000002
Figure PCTCN2022130369-appb-000002
注：对比例的数据源于原文。Note: The data of the comparative example comes from the original text.
结合表1中数据可知，选用的岩芯为亲水亲油性岩芯，处理后其表面润湿性转变为双疏性。对比实施例1、2，增加硅烷偶联剂中双键主链的碳，可以提高产物的润湿反转能力，对比实施例2、3，增加硅烷偶联剂中硅氧烷取代基的碳，可以提高产物的润湿反转能力，对比实施例3、4、5，增加含氟单体中氟取代烷烃的含量，可以提高产物的润湿反转能力。对比实施例5与实施例6、7、8可知，减小偶联反应的pH值会增加纳米颗粒之间的水解作用，降低反应温度会降低反应物质的反应活性，增加含氟单体的摩尔质量会增加含氟单体之间的聚合，从而不利于形成规则的核壳结构，因而产物的润湿反转能力下降。特别的，实施例5中产物处理后岩芯表面与水和正十六烷的接触角为158°和140°(见图3)，达到了超疏水的效果。Combined with the data in Table 1, it can be seen that the selected core is hydrophilic and lipophilic, and its surface wettability changes to amphiphobic after treatment. Comparing Examples 1 and 2, increasing the carbon of the double bond main chain in the silane coupling agent can improve the wettability of the product, and comparing Examples 2 and 3, increasing the carbon of the siloxane substituent in the silane coupling agent , can improve the wettability of the product, and compare Examples 3, 4, and 5, increasing the content of fluorine-substituted alkanes in the fluorine-containing monomer can improve the wettability of the product. Comparing Example 5 with Examples 6, 7, and 8, it can be seen that reducing the pH value of the coupling reaction will increase the hydrolysis between nanoparticles, reducing the reaction temperature will reduce the reactivity of the reaction substance, and increase the mole of fluorine-containing monomers. The quality will increase the polymerization between fluorine-containing monomers, which is not conducive to the formation of a regular core-shell structure, so the wettability of the product is reduced. In particular, the contact angles of the rock core surface with water and n-hexadecane after the product treatment in Example 5 are 158° and 140° (see Figure 3), reaching the super-hydrophobic effect.
对比实施例5与对比例1，本发明制备的含氟纳米流体较对比例1中制备的含氟聚合物乳液有更强的润湿反转能力，可以在较低的浓度下将岩芯表面的润湿性从亲水亲油性转变为双疏性。对比实施例5与对比例2，本发明制备的核壳型含氟纳米流体较对比例2中制备的核壳型含氟聚合物乳液有更强的润湿反转能力，可以在较低的浓度下将岩芯表面的润湿性从亲水亲油性转变为双疏性。因而本发明所制备的核壳结构的双疏型含氟纳米流体拥有极强的润湿反转能力，可以在较低的浓度下将岩芯表面的润湿性从亲水亲油性转变为双疏性，能够有效的改善油气资源开发过程中由于储层润湿性问题所带来的问题。Comparing Example 5 with Comparative Example 1, the fluorine-containing nanofluid prepared by the present invention has stronger wettability and inversion ability than the fluorine-containing polymer emulsion prepared in Comparative Example 1, and can degrade the core surface at a lower concentration. The wettability changes from hydrophilic-lipophilic to amphiphobic. Comparing Example 5 with Comparative Example 2, the core-shell type fluorine-containing nanofluid prepared by the present invention has stronger wetting inversion ability than the core-shell type fluoropolymer emulsion prepared in Comparative Example 2, and can be used at a lower The wettability of the core surface is changed from hydrophilic and lipophilic to amphiphobic at low concentrations. Therefore, the amphiphobic fluorine-containing nanofluid with the core-shell structure prepared by the present invention has a very strong wettability reversal ability, and can change the wettability of the core surface from hydrophilic to lipophilic at a relatively low concentration. Hydrophobicity can effectively improve the problems caused by reservoir wettability in the process of oil and gas resource development.
实验例2：配伍性实验Experimental Example 2: Compatibility Experiment
将实施例5制备的产物配制为0.1wt.％纳米流体，与常用工作液进行配伍性实验，观察配伍体系有无分层和沉淀现象，结果如表2所示，其中：①地层水(矿化度10000)，②季铵盐粘土稳定剂(100mg/L)，③咪唑啉缓蚀剂(100mg/L)，④HPAM(2wt.％)。The product prepared in Example 5 was prepared as 0.1wt.% nanofluid, and a compatibility experiment was carried out with common working fluids to observe whether the compatibility system had delamination and precipitation phenomena. The results are shown in Table 2, wherein: ① formation water (mineral 10000), ② quaternary ammonium salt clay stabilizer (100mg/L), ③ imidazoline corrosion inhibitor (100mg/L), ④ HPAM (2wt.%).
表2 配伍性实验结果Table 2 Compatibility test results
配伍体系Compatibility system 体系状态system state
①① 无沉淀、无分层No precipitation, no stratification
①+②①+② 无沉淀、无分层No precipitation, no stratification
①+②+③①+②+③ 无沉淀、无分层No precipitation, no stratification
①+②+③+④①+②+③+④ 无沉淀、无分层No precipitation, no stratification
从配伍性实验结果可以看出，0.1wt.％纳米流体加入工作液后，体系无沉淀、无分层现象，制备的产物与常用的工作液存在良好的配伍性，因此本发明所制备的核壳结构的双疏型含氟纳米流体有良好的配伍性，可以不用提纯直接投入使用。As can be seen from the compatibility test results, after 0.1wt.% nanofluid is added to the working solution, the system has no precipitation and no layering phenomenon, and the prepared product has good compatibility with the commonly used working solution. The shell-structured amphiphobic fluorine-containing nanofluid has good compatibility and can be used directly without purification.

Claims (10)

  1. 一种可将储层润湿性由亲水亲油转变为双疏性的双疏型含氟纳米流体，具有由纳米核心材料和聚合物壳层材料构成的核壳结构；其中，An amphobic fluorine-containing nanofluid that can change the wettability of the reservoir from hydrophilic to amphiphobic, and has a core-shell structure composed of nano-core materials and polymer shell materials; wherein,
    所述纳米核心材料表面接枝带有双键的偶联剂，是由亲水性纳米二氧化硅与硅烷偶联剂反应制得；The surface of the nano-core material is grafted with a coupling agent with a double bond, which is prepared by reacting hydrophilic nano-silica and a silane coupling agent;
    所述聚合物壳层材料含氟聚合物，是含氟单体通过聚合反应包覆在所述纳米核心材料上。The fluorine-containing polymer of the polymer shell material is that the fluorine-containing monomer is coated on the nanometer core material through polymerization reaction.
  2. 权利要求1所述的双疏型含氟纳米流体的制备方法，包括步骤：The preparation method of the amphobic fluorine-containing nanofluid according to claim 1, comprising the steps of:
    (1)在酸性环境下，将纳米二氧化硅分散在乙醇中，加入硅烷偶联剂，升温至反应温度60-80℃，通过偶联反应制得纳米核心材料；所述的纳米二氧化硅为亲水性纳米二氧化硅；(1) In an acidic environment, disperse nano-silica in ethanol, add a silane coupling agent, heat up to a reaction temperature of 60-80°C, and prepare a nano-core material through a coupling reaction; the nano-silica It is hydrophilic nano silicon dioxide;
    (2)将含氟单体、乳化剂和引发剂分散到N，N-二甲基甲酰胺中，加入到步骤(1)制备的纳米核心材料中进行聚合反应，聚合反应温度为60-80℃，得到双疏型含氟纳米流体。(2) Disperse fluorine-containing monomers, emulsifiers and initiators in N, N-dimethylformamide, and add them to the nano-core material prepared in step (1) for polymerization, and the polymerization temperature is 60-80 °C, an amphobic fluorine-containing nanofluid is obtained.
  3. 如权利要求2所述的双疏型含氟纳米流体的制备方法，其特征在于所述双疏型含氟纳米流体中纳米颗粒的粒径为200-300nm；优选的，所述的亲水性纳米二氧化硅粒径为20-50nm。The preparation method of amphobic fluorine-containing nanofluid as claimed in claim 2, characterized in that the particle diameter of nanoparticles in the amphobic fluorine-containing nanofluid is 200-300nm; preferably, the hydrophilic The particle size of nano silicon dioxide is 20-50nm.
  4. 如权利要求2所述的双疏型含氟纳米流体的制备方法，其特征在于所述的硅烷偶联剂选自3-(甲基丙烯酰氧)丙基三甲氧基硅烷、乙烯基三甲氧基硅烷、烯丙基三甲氧基硅烷、丙烯酰氧甲基三甲氧基硅烷、烯丙基三乙氧基硅烷、甲基丙烯酰氧基甲基三乙氧基硅烷、乙烯基三乙氧基硅烷之一。The preparation method of amphobic type fluorine-containing nanofluid as claimed in claim 2, is characterized in that described silane coupling agent is selected from 3-(methacryloyl oxygen) propyltrimethoxysilane, vinyltrimethoxy Allyl trimethoxysilane, allyltrimethoxysilane, acryloxymethyltrimethoxysilane, allyltriethoxysilane, methacryloxymethyltriethoxysilane, vinyltriethoxy One of the silanes.
  5. 如权利要求2所述的双疏型含氟纳米流体的制备方法，其特征在于步骤(1)所述的反应包括以下条件之一种或多种：The preparation method of amphobic fluorine-containing nanofluid as claimed in claim 2, is characterized in that the reaction described in step (1) comprises one or more of the following conditions:
    a.所述的酸性环境pH值为1～4；a. The pH value of the acidic environment is 1-4;
    b.用盐酸溶液调节pH值；b. adjust the pH value with hydrochloric acid solution;
    c.分散在乙醇中的纳米二氧化硅含量为1.5～2.5g/L；c. The content of nano silicon dioxide dispersed in ethanol is 1.5～2.5g/L;
    d.纳米二氧化硅与硅烷偶联剂质量比为1:15～20。d. The mass ratio of nano-silica to silane coupling agent is 1:15-20.
  6. 如权利要求2所述的双疏型含氟纳米流体的制备方法，其特征在于步骤(2)所述的反应包括以下条件之一种或多种：The preparation method of amphobic fluorine-containing nanofluid as claimed in claim 2, is characterized in that the reaction described in step (2) comprises one or more of the following conditions:
    a.所述的含氟单体为1,1,1,3,3,3-六氟异丙基丙烯酸酯，2-(全氟丁基)乙基丙烯酸酯，甲基丙烯酸十二氟庚酯中的一种；a. The fluorine-containing monomers are 1,1,1,3,3,3-hexafluoroisopropyl acrylate, 2-(perfluorobutyl) ethyl acrylate, dodecafluoroheptyl methacrylate one of the esters;
    b.含氟单体与硅烷偶联剂摩尔比为1～2:1～2；b. The molar ratio of fluorine-containing monomer to silane coupling agent is 1~2:1~2;
    c.所述乳化剂为十二烷基苯磺酸钠、十二烷基硫酸钠、十二烷基三甲基溴化铵、全氟辛 酸、全氟壬烯氧基苯磺酸钠中的一种；c. The emulsifier is one of sodium dodecylbenzenesulfonate, sodium lauryl sulfate, dodecyltrimethylammonium bromide, perfluorooctanoic acid, and sodium perfluorononenyloxybenzenesulfonate ;
    d.所述乳化剂是0.5～1.5g/L；d. The emulsifier is 0.5～1.5g/L;
    e.所述的引发剂为过硫酸铵、过氧化苯甲酰、偶氮二异丁腈中的一种；E. described initiator is the one in ammonium persulfate, benzoyl peroxide, azobisisobutyronitrile;
    f.所述引发剂用量是0.5～1.5g/L；f. The dosage of the initiator is 0.5～1.5g/L;
    g.所述N，N-二甲基甲酰胺用量与步骤(1)中乙醇用量体积比为1～2:1～2。g. The volume ratio of the amount of N,N-dimethylformamide to the amount of ethanol in step (1) is 1-2:1-2.
  7. 如权利要求2所述的双疏型含氟纳米流体的制备方法，其特征在于，步骤(2)还包括在聚合反应前，将反应体系在常温下进行超声乳化20～40min。The preparation method of amphobic fluorine-containing nanofluid according to claim 2, characterized in that step (2) further comprises ultrasonic emulsifying the reaction system at room temperature for 20-40 minutes before the polymerization reaction.
  8. 如权利要求2所述的双疏型含氟纳米流体的制备方法，其特征在于，步骤如下：The preparation method of amphobic fluorine-containing nanofluid as claimed in claim 2, is characterized in that, the steps are as follows:
    于带有回流装置和电磁搅拌的反应容器中，分别加入0.1g亲水纳米二氧化硅和50mL无水乙醇，并用1mol/L盐酸调节pH到4，常温下超声10min后加入0.01mol硅烷偶联剂，并在80℃下反应1h，得到纳米核心材料；再将0.01mol含氟单体，0.1g乳化剂和0.1g引发剂加入50mL N,N-二甲基甲酰胺中，并在常温下加入制备的纳米核心材料中超声乳化30min，随后升温至80℃反应4h；得到的淡黄色乳状液产品，即为核壳结构的双疏型含氟纳米流体。In a reaction vessel with a reflux device and electromagnetic stirring, add 0.1 g of hydrophilic nano-silica and 50 mL of absolute ethanol, and adjust the pH to 4 with 1 mol/L hydrochloric acid, and then add 0.01 mol of silane coupling agent, and reacted at 80°C for 1 hour to obtain a nano-core material; then add 0.01mol fluorine-containing monomer, 0.1g emulsifier and 0.1g initiator to 50mL N,N-dimethylformamide, and Add it into the prepared nano-core material for ultrasonic emulsification for 30 minutes, then raise the temperature to 80° C. and react for 4 hours; the obtained light yellow emulsion product is an amphiphobic fluorine-containing nanofluid with a core-shell structure.
  9. 权利要求1所述的双疏型含氟纳米流体在改变储层润湿性中的应用，使储层润湿性由亲水亲油性转变为双疏性。The application of the amphobic fluorine-containing nanofluid according to claim 1 in changing the wettability of the reservoir makes the wettability of the reservoir change from hydrophilic and lipophilic to amphiphobic.
  10. 一种用于驱油的工作液，所述工作液中含有权利要求1所述的双疏型含氟纳米流体；优选的，所述含氟纳米流体的浓度在工作液中的有效浓度为0.1wt.％。A working fluid for oil displacement, containing the amphobic fluorine-containing nanofluid according to claim 1 in the working fluid; preferably, the effective concentration of the concentration of the fluorine-containing nanofluid in the working fluid is 0.1 wt.%.
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