WO2024088444A1 - Middle-phase microemulsion, and preparation method therefor and use thereof - Google Patents

Middle-phase microemulsion, and preparation method therefor and use thereof Download PDF

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Publication number
WO2024088444A1
WO2024088444A1 PCT/CN2023/141024 CN2023141024W WO2024088444A1 WO 2024088444 A1 WO2024088444 A1 WO 2024088444A1 CN 2023141024 W CN2023141024 W CN 2023141024W WO 2024088444 A1 WO2024088444 A1 WO 2024088444A1
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surfactant
oil
phase microemulsion
middle phase
water
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PCT/CN2023/141024
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French (fr)
Chinese (zh)
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彭宝亮
刘卫东
侯庆锋
仪晓玲
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中国石油天然气股份有限公司
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Publication of WO2024088444A1 publication Critical patent/WO2024088444A1/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
    • C09K8/02—Well-drilling compositions
    • C09K8/03—Specific additives for general use in well-drilling compositions
    • C09K8/035—Organic additives
    • 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
    • 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
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16—Enhanced recovery methods for obtaining hydrocarbons

Definitions

  • the invention relates to the technical field of tertiary oil recovery in oil fields, and in particular to a middle-phase microemulsion and a preparation method and application thereof.
  • crude oil production can be divided into three stages: in the early stage of oil field development, self-flowing production is carried out through oil layer energy, and the recovery rate is only 15% to 20%.
  • This stage is called primary oil production; in order to supplement the insufficient formation energy, artificial water injection or gas injection is used to supplement the reservoir energy to produce oil, and the recovery rate can reach 25% to 40%.
  • This stage is called secondary oil production; in order to produce most of the remaining crude oil, new technologies such as physics, chemistry and biology are used to continue to produce residual oil on the basis of secondary oil production.
  • Such production methods are collectively called tertiary oil production.
  • Tertiary oil production mainly includes chemical drive, gas drive and thermal drive.
  • Microemulsion is a thermodynamically stable, isotropic, low-viscosity transparent or translucent dispersion system spontaneously formed by oil and water under certain conditions under the action of surfactants and co-surfactants.
  • Two or more immiscible liquids in the microemulsion are mixed and emulsified to form a droplet system with a diameter between 5 and 100 nm.
  • the main principle is that in the process of oil extraction, by first adding The process of injecting water after surfactant and some polymer compounds to drive oil. In the oil well, the surfactant aqueous solution and the original solution form a double continuous phase microemulsion.
  • the microemulsion coexists with excess water and excess oil, greatly reducing the interfacial tension between crude oil and water.
  • microemulsions are divided into multiphase microemulsions (Winsor I, Winsor II, Winsor III microemulsions) and single-phase microemulsions (Winsor IV microemulsions).
  • Winsor I microemulsions are in which excess oil components coexist with O/W type microemulsions.
  • Winsor I microemulsions are also called lower phase microemulsions, in which surfactants are mainly dissolved in the microemulsion phase at the bottom of the system, and the upper oil component also contains a lower concentration of surfactant monomers.
  • Winsor II microemulsions are in which W/O type microemulsions coexist with excess water components.
  • Winsor II microemulsions are also called upper phase microemulsions, in which surfactants are mainly dissolved in the upper part of the system, and the lower water component also contains a lower concentration of surfactants.
  • Winsor III microemulsions are in which microemulsions coexist with excess water components and oil components, that is, middle phase microemulsions.
  • Winsor type III microemulsion is an intermediate structure in the continuous transformation path of Winsor type I microemulsion and Winsor type II microemulsion.
  • the system contains two interfaces and three phases, consisting of a bicontinuous phase rich in surfactant, an oil phase containing a small amount of surfactant at the top of the system, and an aqueous phase containing a small amount of surfactant at the bottom of the system.
  • the intermediate phase of Winsor type III microemulsion is actually a bicontinuous microemulsion.
  • middle phase microemulsion requires a high surfactant concentration (>1%) and a variety of additives, and the middle phase microemulsion needs to be constructed by adding alkali in the formula.
  • the formation of such middle phase microemulsion results in high costs, and the addition of alkali will cause problems such as pipeline corrosion or scaling.
  • the purpose of the present invention is to overcome the problems of the existing middle phase microemulsion, and to provide a middle phase microemulsion and its preparation method and application.
  • the middle phase microemulsion of the present invention is used for oil displacement, which can significantly reduce the interfacial tension and improve the crude oil recovery rate.
  • the middle phase microemulsion of the present invention does not need to add alkali, and only needs a small amount of auxiliary agent.
  • the main agent used has a low concentration and high economic benefit, and can significantly improve the recovery rate. It can be used to further improve the recovery rate after chemical flooding such as polymer flooding.
  • the present invention provides a middle phase microemulsion on one hand, comprising 0.4-1.6wt% of a main surfactant, 0.1-0.5wt% of a co-surfactant, 7-14wt% of an inorganic salt, 45-55wt% of an oil phase and 35-45wt% of water, wherein the main surfactant is selected from at least one of monoalkylbenzene sulfonate and dialkylbenzene sulfonate with an alkyl chain of C11-C22, and the co-surfactant is sodium dodecyl polyoxypropylene sulfate.
  • the primary surfactant is selected from one or a mixture of at least two of monoalkylbenzene sulfonates and dialkylbenzene sulfonates having an alkyl chain of C14, C16, or C18.
  • the structural formula of the co-surfactant is as shown in formula (I),
  • n is an integer from 3 to 6.
  • the inorganic salt is sodium chloride and/or potassium chloride.
  • the oil phase is a straight-chain alkane or a mixture of normal alkane and isoalkane.
  • the straight-chain alkane is n-tetradecane.
  • the mixture of normal alkanes and isoalkanes is white oil.
  • the water is deionized water.
  • the middle phase microemulsion is a transparent or translucent liquid.
  • the second aspect of the present invention provides a method for preparing the above-mentioned middle phase microemulsion, which comprises: mixing a main surfactant, a co-surfactant, an inorganic salt, an oil phase and water.
  • the mixing process comprises: stirring and mixing the main surfactant, the co-surfactant, the inorganic salt, the oil phase and water, and then letting them stand.
  • the third aspect of the present invention provides the use of the above-mentioned middle phase microemulsion as an oil displacement agent.
  • the middle phase microemulsion of the present invention can significantly reduce interfacial tension and improve crude oil recovery when used for oil flooding.
  • the middle phase microemulsion does not require the addition of other additives such as alkali, and the concentration of the used agent is low, with high economic benefits. It can be used to further improve the recovery rate after chemical flooding.
  • the preparation process of the medium-phase microemulsion of the invention is simple and can be obtained by directly mixing the components evenly, which is conducive to large-scale production.
  • FIG1 is a small angle X-ray image of the middle phase microemulsion prepared in Example 1;
  • FIG2 is a cryo-scanning electron micrograph of the middle phase microemulsion prepared in Example 1;
  • FIG3 is a small angle X-ray image of the middle phase microemulsion prepared in Example 2.
  • FIG. 4 is a cryo-scanning electron micrograph of the middle phase microemulsion prepared in Example 2.
  • the endpoints of the ranges and any values disclosed herein are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values.
  • the endpoint values, the endpoint values of each range and the individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.
  • the middle phase microemulsion of the present invention contains a main surfactant, a co-surfactant, an inorganic salt, an oil phase and water, but does not contain other auxiliary agents such as alkali.
  • the primary surfactant is selected from at least one of monoalkylbenzene sulfonate and dialkylbenzene sulfonate with alkyl chains of C11-C22. Specifically, the primary surfactant is selected from one or a mixture of at least two of monoalkylbenzene sulfonate and dialkylbenzene sulfonate with alkyl chains of C14, C16, and C18.
  • the total amount of the middle phase microemulsion is 100wt%
  • the content of the main surfactant is 0.4-1.6wt%
  • the content of the cosurfactant is 0.1-0.5wt%
  • the content of the inorganic salt is 7-14wt%
  • the content of the oil phase is 45-55wt%
  • the content of water is 35-45wt%.
  • the content of the main surfactant is 0.4-1.2wt%
  • the content of the cosurfactant is 0.1-0.3wt%
  • the content of the inorganic salt is 8-12wt%
  • the content of the oil phase is 48-52wt%
  • the content of water is 38-42wt%.
  • the cosurfactant is sodium dodecyl polyoxypropylene sulfate.
  • the structural formula of the cosurfactant is as shown in formula (I):
  • n is an integer of 3-6, and specifically can be 3, 4, 5 or 6, for example.
  • the inorganic salt may be sodium chloride and/or potassium chloride, preferably sodium chloride.
  • the oil phase can be a straight-chain alkane or a mixture of normal alkane and isoalkane.
  • the straight-chain alkane is preferably n-tetradecane.
  • the mixture of normal alkane and isoalkane is preferably white oil.
  • the water is preferably deionized water.
  • the middle phase microemulsion is a transparent or translucent liquid.
  • the method for preparing the middle phase microemulsion may include: mixing a main surfactant, a co-surfactant, an inorganic salt, an oil phase and water.
  • the mixing process comprises: stirring and mixing the main surfactant, the co-surfactant, the inorganic salt, the oil phase and water, and then standing. Further preferably, the mixing process comprises: dissolving the main surfactant, the co-surfactant and the inorganic salt in water to obtain an aqueous phase, stirring and mixing the aqueous phase and the oil phase, and then standing.
  • the stirring can be mechanical stirring, the stirring speed can be 50-200 rpm, and the stirring time is 5-30 minutes.
  • the present invention also provides the use of the middle phase microemulsion as an oil displacement agent.
  • the middle phase microemulsion is used as an oil displacement agent for oil displacement, which can significantly reduce interfacial tension and improve crude oil recovery, and can be used to further improve recovery after chemical flooding such as polymer flooding.
  • weight percentage 0.4% of heavy alkylbenzene sulfonate (mainly monoalkylbenzene sulfonate with an alkyl chain of C16), 0.2% of sodium dodecyl polyoxypropylene sulfate (compound shown in formula (I), n is 3), 10% of sodium chloride, 50% of n-tetradecane and 39.4% of deionized water are weighed.
  • heavy alkylbenzene sulfonate mainly monoalkylbenzene sulfonate with an alkyl chain of C16
  • sodium dodecyl polyoxypropylene sulfate compound shown in formula (I)
  • n is 3
  • 10% of sodium chloride 50% of n-tetradecane and 39.4% of deionized water are weighed.
  • the weighed surfactant and sodium chloride are dissolved in deionized water to obtain an aqueous phase; the weighed oil phase and the obtained aqueous phase are mixed evenly, added to a beaker, stirred at a speed of 100 rpm for 10 minutes at room temperature, and then allowed to stand to obtain a middle phase microemulsion A1.
  • heavy alkylbenzene sulfonate was provided by PetroChina Xinjiang Oilfield Branch, sodium dodecyl polyoxypropylene sulfate was purchased from Sasol (Sandton, South Africa), n-tetradecane (99%) was purchased from Adamas-Beta (Shanghai), and NaCl (AR) was purchased from Kelon Reagent Company (Chengdu).
  • Deionized water resistivity of 18.25 M ⁇ cm
  • CDUPT- ⁇ Chengdu Ultrapure Technology Co., Ltd., China.
  • the "Teubner-Strey” model was used to fit the SAXS curve to obtain the correlation length ⁇ and the periodicity d of the bicontinuous domains. The relevant results are shown in Figure 1.
  • the relationship between the scattering intensity and the scattering vector of this component conforms to the T-S model, verifying that the intermediate phase is indeed a middle phase microemulsion with a bicontinuous structure.
  • the prepared middle phase microemulsion A1 was subjected to Cryo-SEM testing using a FEI-Helios G5 cryo-microscope (FEI, USA). Before sample preparation, it was stabilized at 40°C for 30 min, then dropped into a copper holder with conductive glue and mounted on a cryo-holder. The sample was then quenched in liquid nitrogen (-196°C) for 10 s. Then, two tweezers were used to bend, break and expose a new cross-section. The frozen sample was then moved into the sample chamber, sublimated at -90°C for 10 min, sputtered with gold at 10 mA, and moved into the observation chamber. The temperature of the observation chamber was The images were captured at -140°C and vacuum pressure down to 1 ⁇ 10 -5 Pa using secondary or backscattered electrons (2 keV, 60 pA). The relevant results are shown in Figure 2.
  • weight percentage 0.8% heavy alkylbenzene sulfonate (mainly monoalkylbenzene sulfonate with an alkyl chain of C16), 0.2% sodium dodecyl polyoxypropylene sulfate (compound shown in formula (I), n is 3), 10% sodium chloride, 50% white oil and 39% deionized water are weighed.
  • the weighed surfactant and sodium chloride are dissolved in deionized water to obtain an aqueous phase; the weighed oil phase and the obtained aqueous phase are mixed evenly, added to a beaker, stirred at a speed of 100 rpm for 10 minutes at room temperature, and then allowed to stand to obtain a middle phase microemulsion A2.
  • heavy alkylbenzene sulfonate was provided by PetroChina Xinjiang Oilfield Branch, sodium dodecyl polyoxypropylene sulfate was purchased from Sasol (Sandton, South Africa), white oil (15#) was purchased from Lingzhong Lubricating Oil Co., Ltd. (Chengdu), and NaCl (AR) was purchased from Kelon Reagent Co., Ltd. (Chengdu).
  • Deionized water resistivity of 18.25 M ⁇ cm
  • CDUPT- ⁇ Chengdu Ultrapure Technology Co., Ltd., China.
  • the "Teubner-Strey" model was used to fit the SAXS curve to obtain the correlation length ⁇ and the periodicity d of the bicontinuous domains. The relevant results are shown in Figure 3.
  • the relationship between the scattering intensity and the scattering vector of this component conforms to the TS model, verifying that the intermediate phase is indeed a middle phase microemulsion with a bicontinuous structure.
  • the prepared middle phase microemulsion A2 was subjected to Cryo-SEM testing using a FEI-Helios G5 cryo microscope (FEI, USA). Before sample preparation, it was stabilized at 40°C for 30 min, then dropped into a copper holder with conductive glue and mounted on a cryo holder. The sample was then quenched in liquid nitrogen (-196°C) for 10 s. Then, the sample was bent, broken and a new cross section was exposed using two tweezers.
  • the frozen sample was then moved into the sample chamber, sublimated at -90°C for 10 min, sputtered with gold at 10 mA, and moved into the observation chamber, the temperature of the observation chamber was -140°C, and the image was captured using secondary or backscattered electrons (2 keV, 60 pA) under a vacuum pressure of 1 ⁇ 10 -5 Pa.
  • the relevant results are shown in Figure 4.
  • weight percentage 1.2% of heavy alkylbenzene sulfonate (mainly monoalkylbenzene sulfonate with an alkyl chain of C16), 0.4% of sodium dodecyl polyoxypropylene sulfate (compound shown in formula (I), n is 6), 10% of sodium chloride, 52% of n-tetradecane and 36.4% of deionized water are weighed.
  • heavy alkylbenzene sulfonate mainly monoalkylbenzene sulfonate with an alkyl chain of C16
  • sodium dodecyl polyoxypropylene sulfate compound shown in formula (I)
  • n is 6
  • 10% of sodium chloride 52% of n-tetradecane and 36.4% of deionized water are weighed.
  • the weighed surfactant and sodium chloride are dissolved in deionized water to obtain an aqueous phase; the weighed oil phase and the obtained aqueous phase are mixed evenly, added to a beaker, stirred at a speed of 100 rpm for 10 minutes at room temperature, and then allowed to stand to obtain a middle phase microemulsion A3.
  • weight percentage 0.8% of heavy alkylbenzene sulfonate (monoalkylbenzene sulfonate with an alkyl chain of C18), 0.2% of sodium dodecyl polyoxypropylene sulfate (compound represented by formula (I), n is 5), 12% of potassium chloride, 50% of n-tetradecane and 37% of deionized water are weighed.
  • the weighed surfactant and sodium chloride are dissolved in deionized water to obtain an aqueous phase; the weighed oil phase and the obtained aqueous phase are mixed evenly, added to a beaker, stirred at a speed of 100 rpm for 10 minutes at room temperature, and then allowed to stand to obtain a middle phase microemulsion A5.
  • a middle phase microemulsion was prepared according to the method of Example 1, except that the heavy alkylbenzene sulfonate was replaced by the same weight of cycloalkyl aryl sulfonate to obtain a middle phase microemulsion D1.
  • a middle phase microemulsion was prepared according to the method of Example 1, except that the sodium dodecylbenzene sulfonate was used in place of the sodium dodecyl polyoxypropylene sulfate by the same weight to obtain a middle phase microemulsion D2.
  • the surfactant system selected from the above embodiments and comparative examples was used to carry out oil displacement test, and the specific test process was as follows:
  • the experiment was conducted using natural cores obtained from the target formation: first, the cores were cleaned and dried, and their basic physical properties were measured; the cores were saturated with simulated brine using a core vacuum saturation device, and then soaked in The core flooding experiment was carried out at a specific reservoir temperature of 40°C and was divided into three processes: saturated oil, water flooding, surfactant flooding and post-water flooding. The specific steps are as follows:
  • Oil saturation Take the above cores in a holder and displace them with crude oil in a pressure pipeline until the outlet stops discharging water and steadily discharging oil. Collect and record the water output V o to obtain the oil saturated cores. After saturation, place them at high temperature for 1 to 2 days to make the crude oil evenly distributed in the cores and simulate the crude oil distribution in real reservoirs as much as possible.
  • the surfactant flooding system of the present invention can significantly improve the recovery rate after water flooding, and the recovery rate increases with the increase of the main agent concentration. Compared with the formula of the present invention, after changing the main agent and the auxiliary agent, the recovery rate is significantly reduced, which proves the superiority of the system of the present invention.

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Abstract

The present invention relates to the technical field of tertiary oil recovery in oil fields. Disclosed are a middle-phase microemulsion, and a preparation method therefor and the use thereof. The middle-phase microemulsion contains 0.4-1.6 wt% of a main surfactant, 0.1-0.5 wt% of a co-surfactant, 7-14 wt% of an inorganic salt, 45-55 wt% of an oil phase and 35-45 wt% of water, wherein the main surfactant is selected from at least one of monoalkyl benzene sulfonate and dialkyl benzene sulfonate which have a C11-C22 alkyl chain, and the co-surfactant is sodium lauryl polyoxypropylene sulfate. When used for oil displacement, the middle-phase microemulsion of the present invention can greatly reduce the interfacial tension, and improve the recovery rate of crude oil; moreover, the middle-phase microemulsion does not require the addition of other auxiliaries such as an alkali, such that the concentration of the reagent used is low and the economic benefits are high. The middle-phase microemulsion can be used after chemical flooding to further increase the recovery rate.

Description

一种中相微乳液及其制备方法和应用A medium phase microemulsion and its preparation method and application
相关申请的交叉引用CROSS-REFERENCE TO RELATED APPLICATIONS
本申请要求2022年10月27日提交的中国专利申请202211329487.9的权益，该申请的内容通过引用被合并于本文。This application claims the benefit of Chinese patent application 202211329487.9 filed on October 27, 2022, the contents of which are incorporated herein by reference.
技术领域Technical Field
本发明涉及油田三次采油技术领域，具体涉及一种中相微乳液及其制备方法和应用。The invention relates to the technical field of tertiary oil recovery in oil fields, and in particular to a middle-phase microemulsion and a preparation method and application thereof.
背景技术Background technique
根据采油阶段和技术手段分类，原油开采可以分为三个阶段：在油田开发初期，通过油层能量进行自喷开采，采收率只有15％～20％，这一阶段被称为一次采油；为了补充地层能量不足时，用人工注水或注气补充油藏能量开采石油，采收率能达25％～40％，这一阶段被称为二次采油；为了采出剩余的大部分原油，利用物理、化学和生物等新技术在二次采油的基础上继续开采残余油，这样的开采手段统称为三次采油。三次采油主要包括化学驱、气驱和热力驱等方式。According to the classification of oil production stages and technical means, crude oil production can be divided into three stages: in the early stage of oil field development, self-flowing production is carried out through oil layer energy, and the recovery rate is only 15% to 20%. This stage is called primary oil production; in order to supplement the insufficient formation energy, artificial water injection or gas injection is used to supplement the reservoir energy to produce oil, and the recovery rate can reach 25% to 40%. This stage is called secondary oil production; in order to produce most of the remaining crude oil, new technologies such as physics, chemistry and biology are used to continue to produce residual oil on the basis of secondary oil production. Such production methods are collectively called tertiary oil production. Tertiary oil production mainly includes chemical drive, gas drive and thermal drive.
在化学驱油中，微乳液驱油在低渗透油藏的三次采油中取得了突破性成果，原油采收率得到了大幅度提高。微乳液是油和水在表面活性剂和助表面活性剂的作用下，在一定条件下自发形成的热力学稳定、各向同性、低粘度的透明或半透明的分散体系。微乳液中两种或两种以上不相溶的液体经混合乳化后，形成直径在5 100nm之间的液滴体系，其主要原理是在石油开采过程中，通过首先加入 表面活性剂和部分高分子化合物后再注入水的过程进行驱油。在油井中，表面活性剂水溶液与原溶液形成双连续相微乳液。微乳液与过量的水和过量的油共存，大大降低了原油和水的界面张力。In chemical flooding, microemulsion flooding has achieved breakthrough results in tertiary oil recovery of low permeability reservoirs, and the crude oil recovery rate has been greatly improved. Microemulsion is a thermodynamically stable, isotropic, low-viscosity transparent or translucent dispersion system spontaneously formed by oil and water under certain conditions under the action of surfactants and co-surfactants. Two or more immiscible liquids in the microemulsion are mixed and emulsified to form a droplet system with a diameter between 5 and 100 nm. The main principle is that in the process of oil extraction, by first adding The process of injecting water after surfactant and some polymer compounds to drive oil. In the oil well, the surfactant aqueous solution and the original solution form a double continuous phase microemulsion. The microemulsion coexists with excess water and excess oil, greatly reducing the interfacial tension between crude oil and water.
根据微乳液相数，微乳液分为多相微乳液(Winsor I、Winsor Ⅱ、Winsor Ⅲ微乳液)和单相微乳液(Winsor Ⅳ型微乳液)两种，其中，Winsor I型微乳液是过量的油组分与O/W型微乳液共存，Winsor I型微乳液也称为下相微乳液，其中表面活性剂主要溶解在体系下发的微乳相中，上方油组分中也含有较低浓度的表面活性剂单体。Winsor Ⅱ型微乳液是W/O型微乳液与过量的水组分共存，Winsor Ⅱ型微乳液也称为上相微乳液，其中表面活性剂主要溶解在体系上方，下方水组分中也含有较低浓度的表面活性剂。Winsor Ⅲ型微乳液是微乳液与过量的水组分和油组分共存，即中相微乳液。Winsor Ⅲ型微乳液是Winsor I型微乳液、Winsor Ⅱ型微乳液连续转变途径中的中间结构，体系含有两个界面，共三相，由富含表面活性剂的双连续相、处于体系上方含有少量表面活性剂的油相以及处于体系下方的含有少量表面活性剂的水相组成，Winsor Ⅲ型微乳液中间相实际上是双连续型微乳液。According to the number of microemulsion phases, microemulsions are divided into multiphase microemulsions (Winsor I, Winsor II, Winsor III microemulsions) and single-phase microemulsions (Winsor IV microemulsions). Among them, Winsor I microemulsions are in which excess oil components coexist with O/W type microemulsions. Winsor I microemulsions are also called lower phase microemulsions, in which surfactants are mainly dissolved in the microemulsion phase at the bottom of the system, and the upper oil component also contains a lower concentration of surfactant monomers. Winsor II microemulsions are in which W/O type microemulsions coexist with excess water components. Winsor II microemulsions are also called upper phase microemulsions, in which surfactants are mainly dissolved in the upper part of the system, and the lower water component also contains a lower concentration of surfactants. Winsor III microemulsions are in which microemulsions coexist with excess water components and oil components, that is, middle phase microemulsions. Winsor type III microemulsion is an intermediate structure in the continuous transformation path of Winsor type I microemulsion and Winsor type II microemulsion. The system contains two interfaces and three phases, consisting of a bicontinuous phase rich in surfactant, an oil phase containing a small amount of surfactant at the top of the system, and an aqueous phase containing a small amount of surfactant at the bottom of the system. The intermediate phase of Winsor type III microemulsion is actually a bicontinuous microemulsion.
一般情况下，构筑中相微乳液需要较高的表面活性剂浓度(>1％)以及多种助剂，且配方中需要通过加入碱构筑出中相微乳液。这种中相微乳液的形成造成成本偏高，由于碱的加入会造成管道腐蚀或结垢等问题。Generally, the construction of middle phase microemulsion requires a high surfactant concentration (>1%) and a variety of additives, and the middle phase microemulsion needs to be constructed by adding alkali in the formula. The formation of such middle phase microemulsion results in high costs, and the addition of alkali will cause problems such as pipeline corrosion or scaling.
因此，开发一种能解决上述技术问题的中相微乳液及其制备工艺与应用是非常必要的。Therefore, it is very necessary to develop a medium-phase microemulsion and its preparation process and application that can solve the above-mentioned technical problems.
发明内容 Summary of the invention
本发明的目的是为了克服现有的中相微乳液存在的问题，提供一种中相微乳液及其制备方法和应用。本发明所述的中相微乳液用于驱油，可以大幅度降低界面张力，提高原油采收率，且本发明的中相微乳液不需要再添加碱，且仅需少量助剂，所用的主剂浓度低，经济效益高，可大幅度提高采收率，可用于聚合物驱等化学驱后进一步提高采收率。The purpose of the present invention is to overcome the problems of the existing middle phase microemulsion, and to provide a middle phase microemulsion and its preparation method and application. The middle phase microemulsion of the present invention is used for oil displacement, which can significantly reduce the interfacial tension and improve the crude oil recovery rate. The middle phase microemulsion of the present invention does not need to add alkali, and only needs a small amount of auxiliary agent. The main agent used has a low concentration and high economic benefit, and can significantly improve the recovery rate. It can be used to further improve the recovery rate after chemical flooding such as polymer flooding.
为了实现上述目的，本发明一方面提供一种中相微乳液，含有0.4-1.6wt％的主表面活性剂、0.1-0.5wt％的助表面活性剂、7-14wt％的无机盐、45-55wt％的油相和35-45wt％的水，其中，所述主表面活性剂选自烷基链为C11-C22的单烷基苯磺酸盐和二烷基苯磺酸盐中的至少一种，所述助表面活性剂为十二烷基聚氧丙烯硫酸钠。In order to achieve the above-mentioned object, the present invention provides a middle phase microemulsion on one hand, comprising 0.4-1.6wt% of a main surfactant, 0.1-0.5wt% of a co-surfactant, 7-14wt% of an inorganic salt, 45-55wt% of an oil phase and 35-45wt% of water, wherein the main surfactant is selected from at least one of monoalkylbenzene sulfonate and dialkylbenzene sulfonate with an alkyl chain of C11-C22, and the co-surfactant is sodium dodecyl polyoxypropylene sulfate.
优选地，所述主表面活性剂选自烷基链为C14、烷基链为C16、烷基链为C18的单烷基苯磺酸盐和双烷基苯磺酸盐中的一种或至少两种以上的混合物。Preferably, the primary surfactant is selected from one or a mixture of at least two of monoalkylbenzene sulfonates and dialkylbenzene sulfonates having an alkyl chain of C14, C16, or C18.
优选地，所述助表面活性剂的结构式如式(I)所示，
Preferably, the structural formula of the co-surfactant is as shown in formula (I),
其中，n为3-6的整数。Here, n is an integer from 3 to 6.
优选地，所述无机盐为氯化钠和/或氯化钾。Preferably, the inorganic salt is sodium chloride and/or potassium chloride.
优选地，所述油相为直链烷烃或者正构烷烃与异构烷烃的混合物。Preferably, the oil phase is a straight-chain alkane or a mixture of normal alkane and isoalkane.
进一步优选地，所述直链烷烃为正十四烷。More preferably, the straight-chain alkane is n-tetradecane.
进一步优选地，所述正构烷烃与异构烷烃的混合物为白油。Further preferably, the mixture of normal alkanes and isoalkanes is white oil.
优选地，所述水为去离子水。Preferably, the water is deionized water.
优选地，所述中相微乳液为透明或半透明液体。 Preferably, the middle phase microemulsion is a transparent or translucent liquid.
本发明第二方面提供了一种制备上述中相微乳液的方法，该方法包括：将主表面活性剂、助表面活性剂、无机盐、油相和水混合。The second aspect of the present invention provides a method for preparing the above-mentioned middle phase microemulsion, which comprises: mixing a main surfactant, a co-surfactant, an inorganic salt, an oil phase and water.
优选地，所述混合的过程包括：将主表面活性剂、助表面活性剂、无机盐、油相和水搅拌混合，然后静置。Preferably, the mixing process comprises: stirring and mixing the main surfactant, the co-surfactant, the inorganic salt, the oil phase and water, and then letting them stand.
本发明第三方面提供了上述中相微乳液作为驱油剂的应用。The third aspect of the present invention provides the use of the above-mentioned middle phase microemulsion as an oil displacement agent.
本发明所述的中相微乳液用于驱油可大幅度降低界面张力，提高原油采收率，且所述中相微乳液不需要添加碱等其它助剂，所用药剂浓度较低，经济效益高，可用于化学驱后进一步提高采收率。The middle phase microemulsion of the present invention can significantly reduce interfacial tension and improve crude oil recovery when used for oil flooding. The middle phase microemulsion does not require the addition of other additives such as alkali, and the concentration of the used agent is low, with high economic benefits. It can be used to further improve the recovery rate after chemical flooding.
本发明的中相微乳液制备工艺简单，各组分直接混合均匀后即可制得，利于大规模生产。The preparation process of the medium-phase microemulsion of the invention is simple and can be obtained by directly mixing the components evenly, which is conducive to large-scale production.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1是实施例1制备的中相微乳液的小角X射线图；FIG1 is a small angle X-ray image of the middle phase microemulsion prepared in Example 1;
图2是实施例1制备的中相微乳液的冷冻扫描电镜图；FIG2 is a cryo-scanning electron micrograph of the middle phase microemulsion prepared in Example 1;
图3是实施例2制备的中相微乳液的小角X射线图；FIG3 is a small angle X-ray image of the middle phase microemulsion prepared in Example 2;
图4是实施例2制备的中相微乳液的冷冻扫描电镜图。FIG. 4 is a cryo-scanning electron micrograph of the middle phase microemulsion prepared in Example 2.
具体实施方式Detailed ways
以下结合附图对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。The specific implementation of the present invention is described in detail below in conjunction with the accompanying drawings. It should be understood that the specific implementation described herein is only used to illustrate and explain the present invention, and is not used to limit the present invention.
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的 端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。The endpoints of the ranges and any values disclosed herein are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. The endpoint values, the endpoint values of each range and the individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.
本发明所述的中相微乳液含有主表面活性剂、助表面活性剂、无机盐、油相和水，不包含碱等其他助剂。The middle phase microemulsion of the present invention contains a main surfactant, a co-surfactant, an inorganic salt, an oil phase and water, but does not contain other auxiliary agents such as alkali.
在本发明所述的中相微乳液中，所述主表面活性剂选自烷基链为C11-C22的单烷基苯磺酸盐和二烷基苯磺酸盐中的至少一种。具体的，所述主表面活性剂选自烷基链为C14、烷基链为C16、烷基链为C18的单烷基苯磺酸盐和双烷基苯磺酸盐中的一种或至少两种以上的混合物。In the middle phase microemulsion of the present invention, the primary surfactant is selected from at least one of monoalkylbenzene sulfonate and dialkylbenzene sulfonate with alkyl chains of C11-C22. Specifically, the primary surfactant is selected from one or a mixture of at least two of monoalkylbenzene sulfonate and dialkylbenzene sulfonate with alkyl chains of C14, C16, and C18.
在本发明所述的中相微乳液中，以所述中相微乳液的总量为100wt％，所述主表面活性剂的含量为0.4-1.6wt％，所述助表面活性剂的含量为0.1-0.5wt％，所述无机盐的含量为7-14wt％，所述油相的含量为45-55wt％，水的含量为35-45wt％。在优选情况下，所述主表面活性剂的含量为0.4-1.2wt％，所述助表面活性剂的含量为0.1-0.3wt％，所述无机盐的含量为8-12wt％，所述油相的含量为48-52wt％，水的含量为38-42wt％。In the middle phase microemulsion of the present invention, the total amount of the middle phase microemulsion is 100wt%, the content of the main surfactant is 0.4-1.6wt%, the content of the cosurfactant is 0.1-0.5wt%, the content of the inorganic salt is 7-14wt%, the content of the oil phase is 45-55wt%, and the content of water is 35-45wt%. In a preferred case, the content of the main surfactant is 0.4-1.2wt%, the content of the cosurfactant is 0.1-0.3wt%, the content of the inorganic salt is 8-12wt%, the content of the oil phase is 48-52wt%, and the content of water is 38-42wt%.
在本发明所述的中相微乳液中，所述助表面活性剂为十二烷基聚氧丙烯硫酸钠。在优选情况下，所述助表面活性剂的结构式如式(I)所示，
In the middle phase microemulsion of the present invention, the cosurfactant is sodium dodecyl polyoxypropylene sulfate. In a preferred embodiment, the structural formula of the cosurfactant is as shown in formula (I):
其中，n为3-6的整数，具体例如可以为3、4、5或6。Herein, n is an integer of 3-6, and specifically can be 3, 4, 5 or 6, for example.
在本发明所述的中相微乳液中，所述无机盐可以为氯化钠和/或氯化钾，优选为氯化钠。 In the middle phase microemulsion of the present invention, the inorganic salt may be sodium chloride and/or potassium chloride, preferably sodium chloride.
在本发明所述的中相微乳液中，所述油相可以为直链烷烃或者正构烷烃与异构烷烃的混合物。所述直链烷烃优选为正十四烷。所述正构烷烃与异构烷烃的混合物优选为白油。In the middle phase microemulsion of the present invention, the oil phase can be a straight-chain alkane or a mixture of normal alkane and isoalkane. The straight-chain alkane is preferably n-tetradecane. The mixture of normal alkane and isoalkane is preferably white oil.
在本发明所述的中相微乳液中，所述水优选为去离子水。In the middle phase microemulsion of the present invention, the water is preferably deionized water.
在本发明中，所述中相微乳液为透明或半透明液体。In the present invention, the middle phase microemulsion is a transparent or translucent liquid.
所述中相微乳液的制备方法可以包括：将主表面活性剂、助表面活性剂、无机盐、油相和水混合。The method for preparing the middle phase microemulsion may include: mixing a main surfactant, a co-surfactant, an inorganic salt, an oil phase and water.
在优选情况下，所述混合的过程包括：将主表面活性剂、助表面活性剂、无机盐、油相和水搅拌混合，然后静置。进一步优选地，所述混合的过程包括：将主表面活性剂、助表面活性剂和无机盐溶于水中得到水相，将所述水相与所述油相搅拌混合，然后静置。所述搅拌可以为机械搅拌，搅拌的速度可以为50-200转/分钟，搅拌的时间为5-30分钟。In a preferred case, the mixing process comprises: stirring and mixing the main surfactant, the co-surfactant, the inorganic salt, the oil phase and water, and then standing. Further preferably, the mixing process comprises: dissolving the main surfactant, the co-surfactant and the inorganic salt in water to obtain an aqueous phase, stirring and mixing the aqueous phase and the oil phase, and then standing. The stirring can be mechanical stirring, the stirring speed can be 50-200 rpm, and the stirring time is 5-30 minutes.
本发明还提供了上述中相微乳液作为驱油剂的应用。所述中相微乳液作为驱油剂用于驱油，可以大幅度降低界面张力，提高原油采收率，可用于聚合物驱等化学驱后进一步提高采收率。The present invention also provides the use of the middle phase microemulsion as an oil displacement agent. The middle phase microemulsion is used as an oil displacement agent for oil displacement, which can significantly reduce interfacial tension and improve crude oil recovery, and can be used to further improve recovery after chemical flooding such as polymer flooding.
下面通过实施例来进一步说明本发明所述的中相微乳液及其制备方法和应用。实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体操作过程，但本发明的保护范围不限于下述实施例。The following examples further illustrate the middle phase microemulsion and its preparation method and application of the present invention. The examples are implemented based on the technical solution of the present invention, and provide detailed implementation methods and specific operation processes, but the protection scope of the present invention is not limited to the following examples.
以下实施例中的实验方法，如无特殊说明，均为本领域常规方法。下述实施例中所用的实验材料，如无特殊说明，均可商购得到。The experimental methods in the following examples, unless otherwise specified, are all conventional methods in the art. The experimental materials used in the following examples, unless otherwise specified, are all commercially available.
实施例1 Example 1
按照重量百分数计，称取0.4％的重烷基苯磺酸盐(主要是烷基链为C16的单烷基苯磺酸盐)、0.2％十二烷基聚氧丙烯硫酸钠(式(I)所示化合物，n为3)、10％氯化钠、50％正十四烷和39.4％的去离子水。将称取的表活剂和氯化钠一起溶于去离子水中，得到水相；将称取的油相与制得的水相混合均匀，并加入烧杯中，在常温下以100转/分钟的转速下搅拌10分钟，然后静置，得到中相微乳液A1。According to the weight percentage, 0.4% of heavy alkylbenzene sulfonate (mainly monoalkylbenzene sulfonate with an alkyl chain of C16), 0.2% of sodium dodecyl polyoxypropylene sulfate (compound shown in formula (I), n is 3), 10% of sodium chloride, 50% of n-tetradecane and 39.4% of deionized water are weighed. The weighed surfactant and sodium chloride are dissolved in deionized water to obtain an aqueous phase; the weighed oil phase and the obtained aqueous phase are mixed evenly, added to a beaker, stirred at a speed of 100 rpm for 10 minutes at room temperature, and then allowed to stand to obtain a middle phase microemulsion A1.
其中，重烷基苯磺酸盐由中国石油新疆油田分公司提供，十二烷基聚氧丙烯硫酸钠购自Sasol公司(Sandton，南非)，正十四烷(99％)购自Adamas-Beta(上海)，NaCl(AR)购自科龙试剂公司(成都)。去离子水(电阻率为18.25MΩ·cm)用超纯水净化装置CDUPT-Ш(成都超纯科技有限公司，中国)实验室自制。Among them, heavy alkylbenzene sulfonate was provided by PetroChina Xinjiang Oilfield Branch, sodium dodecyl polyoxypropylene sulfate was purchased from Sasol (Sandton, South Africa), n-tetradecane (99%) was purchased from Adamas-Beta (Shanghai), and NaCl (AR) was purchased from Kelon Reagent Company (Chengdu). Deionized water (resistivity of 18.25 MΩ·cm) was prepared in the laboratory using an ultrapure water purification device CDUPT-Ш (Chengdu Ultrapure Technology Co., Ltd., China).
将制备的中相微乳液A1封装于石英毛细管中，然后置于SAXSpace(Anton Paar，奥地利，Cu-Ka，λ＝0.154nm)进行SAXS测量，得到散射强度和散射矢量的关系，利用“Teubner-Strey”模型拟合SAXS曲线，得到相关长度ξ和双连续结构域周期性d，相关结果见附图1。The prepared middle phase microemulsion A1 was encapsulated in a quartz capillary and then placed in SAXSpace (Anton Paar, Austria, Cu-Ka, λ=0.154 nm) for SAXS measurement to obtain the relationship between the scattering intensity and the scattering vector. The "Teubner-Strey" model was used to fit the SAXS curve to obtain the correlation length ξ and the periodicity d of the bicontinuous domains. The relevant results are shown in Figure 1.
如图1所示，该组分散射强度与散射矢量的关系符合T-S模型，验证了该中间相确为具有双连续结构的中相微乳液。As shown in Figure 1, the relationship between the scattering intensity and the scattering vector of this component conforms to the T-S model, verifying that the intermediate phase is indeed a middle phase microemulsion with a bicontinuous structure.
将制备的中相微乳液A1使用FEI-Helios G5冷冻显微镜(FEI，美国)进行Cryo-SEM测试。样品制备前，先在40℃下稳定30min，然后滴入带导电胶的铜支架中，并安装在冷冻支架上。然后将试样在液氮(-196℃)中淬冷10s。然后，用两个镊子将样品弯曲，折断并露出一个新的横截面。随后将冷冻的样品移入样品室，在-90℃下升华10min，在10mA下溅射喷金，移入观察室，观察室温度为 -140℃，在真空至1×10-5Pa的压力下，利用二次或背散射电子(2keV，60pA)捕获图像，相关结果见附图2。The prepared middle phase microemulsion A1 was subjected to Cryo-SEM testing using a FEI-Helios G5 cryo-microscope (FEI, USA). Before sample preparation, it was stabilized at 40°C for 30 min, then dropped into a copper holder with conductive glue and mounted on a cryo-holder. The sample was then quenched in liquid nitrogen (-196°C) for 10 s. Then, two tweezers were used to bend, break and expose a new cross-section. The frozen sample was then moved into the sample chamber, sublimated at -90°C for 10 min, sputtered with gold at 10 mA, and moved into the observation chamber. The temperature of the observation chamber was The images were captured at -140°C and vacuum pressure down to 1×10 -5 Pa using secondary or backscattered electrons (2 keV, 60 pA). The relevant results are shown in Figure 2.
图2可以看出，电镜结果中出现了典型的双连续结构，证明了该中间相确为中相微乳液。As can be seen from Figure 2, a typical bicontinuous structure appeared in the electron microscopy results, proving that the intermediate phase is indeed a middle phase microemulsion.
实施例2Example 2
按照重量百分数计，称取0.8％重烷基苯磺酸盐(主要是烷基链为C16的单烷基苯磺酸盐)、0.2％十二烷基聚氧丙烯硫酸钠(式(I)所示化合物，n为3)、10％氯化钠、50％白油和39％的去离子水。将称取的表活剂和氯化钠一起溶于去离子水中，得到水相；将称取的油相与制得的水相混合均匀，并加入烧杯中，在常温下以100转/分钟的转速搅拌10分钟，然后静置，得到中相微乳液A2。According to the weight percentage, 0.8% heavy alkylbenzene sulfonate (mainly monoalkylbenzene sulfonate with an alkyl chain of C16), 0.2% sodium dodecyl polyoxypropylene sulfate (compound shown in formula (I), n is 3), 10% sodium chloride, 50% white oil and 39% deionized water are weighed. The weighed surfactant and sodium chloride are dissolved in deionized water to obtain an aqueous phase; the weighed oil phase and the obtained aqueous phase are mixed evenly, added to a beaker, stirred at a speed of 100 rpm for 10 minutes at room temperature, and then allowed to stand to obtain a middle phase microemulsion A2.
其中，重烷基苯磺酸盐由中国石油新疆油田分公司提供，十二烷基聚氧丙烯硫酸钠购自Sasol公司(Sandton，南非)，白油(15#)购自凌众润滑油有限公司(成都)，NaCl(AR)购自科龙试剂公司(成都)。去离子水(电阻率为18.25MΩ·cm)用超纯水净化装置CDUPT-Ш(成都超纯科技有限公司，中国)实验室自制。Among them, heavy alkylbenzene sulfonate was provided by PetroChina Xinjiang Oilfield Branch, sodium dodecyl polyoxypropylene sulfate was purchased from Sasol (Sandton, South Africa), white oil (15#) was purchased from Lingzhong Lubricating Oil Co., Ltd. (Chengdu), and NaCl (AR) was purchased from Kelon Reagent Co., Ltd. (Chengdu). Deionized water (resistivity of 18.25 MΩ·cm) was prepared in the laboratory using an ultrapure water purification device CDUPT-Ш (Chengdu Ultrapure Technology Co., Ltd., China).
将制备的中相微乳液A2封装于石英毛细管中，然后置于SAXSpace(Anton Paar，奥地利，Cu-Ka，λ＝0.154nm)进行SAXS测量，得到散射强度和散射矢量的关系，利用“Teubner-Strey”模型拟合SAXS曲线，得到相关长度ξ和双连续结构域周期性d，相关结果见附图3。The prepared middle phase microemulsion A2 was encapsulated in a quartz capillary and then placed in SAXSpace (Anton Paar, Austria, Cu-Ka, λ=0.154 nm) for SAXS measurement to obtain the relationship between the scattering intensity and the scattering vector. The "Teubner-Strey" model was used to fit the SAXS curve to obtain the correlation length ξ and the periodicity d of the bicontinuous domains. The relevant results are shown in Figure 3.
如图3所示，该组分散射强度与散射矢量的关系符合T-S模型，验证了该中间相确为具有双连续结构的中相微乳液。 As shown in Figure 3, the relationship between the scattering intensity and the scattering vector of this component conforms to the TS model, verifying that the intermediate phase is indeed a middle phase microemulsion with a bicontinuous structure.
将制备的中相微乳液A2使用FEI-Helios G5冷冻显微镜(FEI，美国)进行Cryo-SEM测试。样品制备前，先在40℃下稳定30min，然后滴入带导电胶的铜支架中，并安装在冷冻支架上。然后将试样在液氮(-196℃)中淬冷10s。然后，用两个镊子将样品弯曲，折断并露出一个新的横截面。随后将冷冻的样品移入样品室，在-90℃下升华10min，在10mA下溅射喷金，移入观察室，观察室温度为-140℃，在真空至1×10-5Pa的压力下，利用二次或背散射电子(2keV，60pA)捕获图像，相关结果见附图4。The prepared middle phase microemulsion A2 was subjected to Cryo-SEM testing using a FEI-Helios G5 cryo microscope (FEI, USA). Before sample preparation, it was stabilized at 40°C for 30 min, then dropped into a copper holder with conductive glue and mounted on a cryo holder. The sample was then quenched in liquid nitrogen (-196°C) for 10 s. Then, the sample was bent, broken and a new cross section was exposed using two tweezers. The frozen sample was then moved into the sample chamber, sublimated at -90°C for 10 min, sputtered with gold at 10 mA, and moved into the observation chamber, the temperature of the observation chamber was -140°C, and the image was captured using secondary or backscattered electrons (2 keV, 60 pA) under a vacuum pressure of 1×10 -5 Pa. The relevant results are shown in Figure 4.
图4可以看出，电镜结果中出现了典型的双连续结构，证明了该中间相确为中相微乳液。As can be seen from Figure 4, a typical bicontinuous structure appeared in the electron microscopy results, proving that the intermediate phase is indeed a middle phase microemulsion.
实施例3Example 3
按照重量百分数计，称取1.2％的重烷基苯磺酸盐(主要是烷基链为C16的单烷基苯磺酸盐)、0.4％十二烷基聚氧丙烯硫酸钠(式(I)所示化合物，n为6)、10％氯化钠、52％正十四烷和36.4％的去离子水。将称取的表活剂和氯化钠一起溶于去离子水中，得到水相；将称取的油相与制得的水相混合均匀，并加入烧杯中，在常温下以100转/分钟的转速下搅拌10分钟，然后静置，得到中相微乳液A3。According to the weight percentage, 1.2% of heavy alkylbenzene sulfonate (mainly monoalkylbenzene sulfonate with an alkyl chain of C16), 0.4% of sodium dodecyl polyoxypropylene sulfate (compound shown in formula (I), n is 6), 10% of sodium chloride, 52% of n-tetradecane and 36.4% of deionized water are weighed. The weighed surfactant and sodium chloride are dissolved in deionized water to obtain an aqueous phase; the weighed oil phase and the obtained aqueous phase are mixed evenly, added to a beaker, stirred at a speed of 100 rpm for 10 minutes at room temperature, and then allowed to stand to obtain a middle phase microemulsion A3.
实施例4Example 4
按照重量百分数计，称取1.6％重烷基苯磺酸盐(主要是烷基链为C16的单烷基苯磺酸盐)、0.4％十二烷基聚氧丙烯硫酸钠(式(I)所示化合物，n为4)、10％氯化钠、50％白油和38％的去离子水。将称取的表活剂和氯化钠一起溶于去 离子水中，得到水相；将称取的油相与制得的水相混合均匀，并加入烧杯中，在常温下以100转/分钟的转速搅拌10分钟，然后静置，得到中相微乳液A4。According to the weight percentage, 1.6% heavy alkylbenzene sulfonate (mainly monoalkylbenzene sulfonate with an alkyl chain of C16), 0.4% sodium dodecyl polyoxypropylene sulfate (compound represented by formula (I), n is 4), 10% sodium chloride, 50% white oil and 38% deionized water are weighed. The weighed surfactant and sodium chloride are dissolved in deionized water. The weighed oil phase was mixed with the prepared water phase, and added into a beaker. The mixture was stirred at 100 rpm for 10 minutes at room temperature, and then allowed to stand to obtain a middle phase microemulsion A4.
实施例5Example 5
按照重量百分数计，称取0.8％的重烷基苯磺酸盐(烷基链为C18的单烷基苯磺酸盐)、0.2％十二烷基聚氧丙烯硫酸钠(式(I)所示化合物，n为5)、12％氯化钾、50％正十四烷和37％的去离子水。将称取的表活剂和氯化钠一起溶于去离子水中，得到水相；将称取的油相与制得的水相混合均匀，并加入烧杯中，在常温下以100转/分钟的转速下搅拌10分钟，然后静置，得到中相微乳液A5。According to the weight percentage, 0.8% of heavy alkylbenzene sulfonate (monoalkylbenzene sulfonate with an alkyl chain of C18), 0.2% of sodium dodecyl polyoxypropylene sulfate (compound represented by formula (I), n is 5), 12% of potassium chloride, 50% of n-tetradecane and 37% of deionized water are weighed. The weighed surfactant and sodium chloride are dissolved in deionized water to obtain an aqueous phase; the weighed oil phase and the obtained aqueous phase are mixed evenly, added to a beaker, stirred at a speed of 100 rpm for 10 minutes at room temperature, and then allowed to stand to obtain a middle phase microemulsion A5.
对比例1Comparative Example 1
按照实施例1的方法制备中相微乳液，所不同的是，用相同重量的环烷基芳基磺酸盐代替所述重烷基苯磺酸盐，得到中相微乳液D1。A middle phase microemulsion was prepared according to the method of Example 1, except that the heavy alkylbenzene sulfonate was replaced by the same weight of cycloalkyl aryl sulfonate to obtain a middle phase microemulsion D1.
对比例2Comparative Example 2
按照实施例1的方法制备中相微乳液，所不同的是，用相同重量的十二烷基苯磺酸钠代替所述十二烷基聚氧丙烯硫酸钠，得到中相微乳液D2。A middle phase microemulsion was prepared according to the method of Example 1, except that the sodium dodecylbenzene sulfonate was used in place of the sodium dodecyl polyoxypropylene sulfate by the same weight to obtain a middle phase microemulsion D2.
测试例Test Case
用上述实施例和对比例筛选的表活剂体系进行驱油测试，具体测试过程为：The surfactant system selected from the above embodiments and comparative examples was used to carry out oil displacement test, and the specific test process was as follows:
使用从目标地层中取得的天然岩心进行实验：首先将岩心洗净干燥，并测定其基本物性参数；利用岩心抽真空饱和装置将岩心饱和模拟盐水，取出后应浸泡 于模拟盐水中待用。岩心驱替实验在特定油藏温度40℃下进行，分为饱和油、水驱、表活剂驱和后水驱三个过程，具体步骤如下：The experiment was conducted using natural cores obtained from the target formation: first, the cores were cleaned and dried, and their basic physical properties were measured; the cores were saturated with simulated brine using a core vacuum saturation device, and then soaked in The core flooding experiment was carried out at a specific reservoir temperature of 40°C and was divided into three processes: saturated oil, water flooding, surfactant flooding and post-water flooding. The specific steps are as follows:
1)饱和油：取上述岩心于夹持器中，并在压力管线中利用原油进行驱替，直至出口端不再出水而稳定出油，收集并记录驱出水量Vo，得到饱和油的岩心；饱和完后，放置高温下保持1～2d，其目的是让原油均匀分布在岩心中，尽量模拟真实油藏的原油分布；1) Oil saturation: Take the above cores in a holder and displace them with crude oil in a pressure pipeline until the outlet stops discharging water and steadily discharging oil. Collect and record the water output V o to obtain the oil saturated cores. After saturation, place them at high temperature for 1 to 2 days to make the crude oil evenly distributed in the cores and simulate the crude oil distribution in real reservoirs as much as possible.
2)水驱：以1mL·min-1向岩心中注入模拟盐水，直至产出液含水98％以上，记录驱出的油体积Vw，按下式计算水驱采收率Ew：
2) Water flooding: Inject simulated brine into the core at 1 mL·min -1 until the water content of the produced fluid is above 98%. Record the volume of oil driven out V w , and calculate the water flooding recovery factor E w as follows:
3)表活剂驱和后续水驱：以1mL·min-1定量注入1PV表活剂溶液后，继续用以1mL·min-1注入模拟盐水，当含水率达再次达到98％以上，结束后续水驱。记录水驱、表活剂驱、以及后续水驱过程中驱出油的累计总体积V，按下式计算原油总采收率E及表活剂驱提高采收率：

Es＝E-Ew           (4)3) Surfactant flooding and subsequent water flooding: After quantitatively injecting 1 PV of surfactant solution at 1 mL·min -1 , continue to inject simulated brine at 1 mL·min -1 . When the water content reaches more than 98% again, the subsequent water flooding is terminated. The cumulative total volume V of oil driven out during water flooding, surfactant flooding, and subsequent water flooding is recorded, and the total crude oil recovery E and the enhanced recovery of surfactant flooding are calculated according to the following formula:

E s = EE w (4)
岩心参数及测试结果如下表1所示，表中，l为岩心长度，h为yanxin直径，PV为孔隙体积，φ为孔隙度，Ke为渗透率，Ew为水驱采收率，Es为表活剂驱。 The core parameters and test results are shown in Table 1 below, where l is the core length, h is the core diameter, PV is the pore volume, φ is the porosity, Ke is the permeability, Ew is the water drive recovery factor, and Es is the surfactant drive.
表1
Table 1
通过表1的结果可以看出，本发明所述表活剂驱油体系可在水驱后较大幅度提高采收率，且提采幅度随主剂浓度增大而升高。与本发明所述的配方相比，在改变主剂和助剂后，提采幅度明显降低，证明了本发明所述体系的优越性。From the results in Table 1, it can be seen that the surfactant flooding system of the present invention can significantly improve the recovery rate after water flooding, and the recovery rate increases with the increase of the main agent concentration. Compared with the formula of the present invention, after changing the main agent and the auxiliary agent, the recovery rate is significantly reduced, which proves the superiority of the system of the present invention.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。 The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims (12)

  1. 一种中相微乳液，其特征在于，含有0.4-1.6wt％的主表面活性剂、0.1-0.5wt％的助表面活性剂、7-14wt％的无机盐、45-55wt％的油相和35-45wt％的水，其中，所述主表面活性剂选自烷基链为C11-C22的单烷基苯磺酸盐和二烷基苯磺酸盐中的至少一种，所述助表面活性剂为十二烷基聚氧丙烯硫酸钠。A middle phase microemulsion, characterized in that it contains 0.4-1.6wt% of a main surfactant, 0.1-0.5wt% of a co-surfactant, 7-14wt% of an inorganic salt, 45-55wt% of an oil phase and 35-45wt% of water, wherein the main surfactant is selected from at least one of monoalkylbenzene sulfonate and dialkylbenzene sulfonate with an alkyl chain of C11-C22, and the co-surfactant is sodium dodecyl polyoxypropylene sulfate.
  2. 根据权利要求1所述的中相微乳液，其特征在于，所述主表面活性剂选自烷基链为C14、烷基链为C16、烷基链为C18的单烷基苯磺酸盐和双烷基苯磺酸盐中的一种或至少两种以上的混合物。The middle phase microemulsion according to claim 1, characterized in that the main surfactant is selected from one or a mixture of at least two or more of monoalkylbenzene sulfonates and dialkylbenzene sulfonates with an alkyl chain of C14, C16, or C18.
  3. 根据权利要求1所述的中相微乳液，其特征在于，所述助表面活性剂的结构式如式(I)所示，
    The middle phase microemulsion according to claim 1, characterized in that the structural formula of the co-surfactant is as shown in formula (I),
    其中，n为3-6的整数。Here, n is an integer from 3 to 6.
  4. 根据权利要求1所述的中相微乳液，其特征在于，所述无机盐为氯化钠和/或氯化钾。The middle phase microemulsion according to claim 1, characterized in that the inorganic salt is sodium chloride and/or potassium chloride.
  5. 根据权利要求1所述的中相微乳液，其特征在于，所述油相为直链烷烃或者正构烷烃与异构烷烃的混合物。 The middle phase microemulsion according to claim 1, characterized in that the oil phase is a straight-chain alkane or a mixture of normal alkanes and isoalkanes.
  6. 根据权利要求5所述的中相微乳液，其特征在于，所述直链烷烃为正十四烷。The middle phase microemulsion according to claim 5, characterized in that the straight-chain alkane is n-tetradecane.
  7. 根据权利要求5所述的中相微乳液，其特征在于，所述正构烷烃与异构烷烃的混合物为白油。The middle phase microemulsion according to claim 5, characterized in that the mixture of normal alkanes and isoalkanes is white oil.
  8. 根据权利要求1所述的中相微乳液，其特征在于，所述水为去离子水。The middle phase microemulsion according to claim 1, characterized in that the water is deionized water.
  9. 根据权利要求1-8中任意一项所述的中相微乳液，其特征在于，所述中相微乳液为透明或半透明液体。The middle phase microemulsion according to any one of claims 1 to 8, characterized in that the middle phase microemulsion is a transparent or translucent liquid.
  10. 一种制备权利要求1-9中任意一项所述的中相微乳液的方法，其特征在于，该方法包括：将主表面活性剂、助表面活性剂、无机盐、油相和水混合。A method for preparing the middle phase microemulsion according to any one of claims 1 to 9, characterized in that the method comprises: mixing a main surfactant, a co-surfactant, an inorganic salt, an oil phase and water.
  11. 根据权利要求10所述的方法，其特征在于，所述混合的过程包括：将主表面活性剂、助表面活性剂、无机盐、油相和水搅拌混合，然后静置。The method according to claim 10 is characterized in that the mixing process comprises: stirring and mixing the main surfactant, the co-surfactant, the inorganic salt, the oil phase and the water, and then letting them stand.
  12. 权利要求1-9中任意一项所述的中相微乳液作为驱油剂的应用。 Use of the middle phase microemulsion described in any one of claims 1 to 9 as an oil displacing agent.
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