CN111471447A - Amphoteric gemini surfactant, temperature-resistant salt-resistant nano emulsion, and preparation method and application thereof - Google Patents

Amphoteric gemini surfactant, temperature-resistant salt-resistant nano emulsion, and preparation method and application thereof Download PDF

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CN111471447A
CN111471447A CN202010468936.2A CN202010468936A CN111471447A CN 111471447 A CN111471447 A CN 111471447A CN 202010468936 A CN202010468936 A CN 202010468936A CN 111471447 A CN111471447 A CN 111471447A
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CN111471447B (en
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徐文熙
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Beijing Jiuheng Quality Information Energy Technology Co ltd
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Abstract

The application discloses an amphoteric gemini surfactant, a temperature-resistant and salt-resistant nano emulsion, a preparation method and an application thereof, wherein the temperature-resistant and salt-resistant nano emulsion comprises the following components in percentage by weight: 5-30% of an oil phase, 10-40% of a main surfactant, 5-30% of a secondary surfactant, 3-18% of a cosurfactant and the balance of water, wherein the main surfactant is the amphoteric gemini surfactant disclosed by the application. The nano emulsion has remarkable temperature and salt resistance effects by introducing the amphoteric gemini surfactant with the phenyl linking group, can resist the temperature of 150 ℃ and resist the salt of more than 30% of NaCl, and has the advantages of high surface activity, high flowback efficiency, high oil washing efficiency and the like.

Description

Amphoteric gemini surfactant, temperature-resistant salt-resistant nano emulsion, and preparation method and application thereof
Technical Field
The application belongs to the technical field of oil exploitation, and particularly relates to an amphoteric gemini surfactant, a temperature-resistant salt-resistant nano emulsion, and a preparation method and application thereof.
Background
At present, the development of unconventional oil and gas reservoirs is deeper and more extensive at home and abroad. Particularly, the development of compact oil reservoirs and shale gas is more vigorous. While the hydraulic fracturing technology is a mature and common technical means for increasing the production of unconventional oil and gas. For tight wells, even though the fracturing scheme has designed an approximate fracturing scale for each fracture section per cluster, the in-situ distributed temperature optical fiber testing (DTS) and production logging results tend to show that the extent of development of the clusters varies greatly, with over 70% of the individual well production being from only 20% of the fractures. And (3) carrying out material balance calculation according to the amount of fracturing fluid injected in the fracturing process, the volume of the shaft and the total volume of the designed artificial fracture, and finding that more than 90% of the fracturing fluid enters the unsupported induced fracture. Research shows that due to the fact that the width of the induced fractures is usually in the micron and submicron order, proppant with conventional size cannot enter the induced fractures to achieve effective support, and sufficient flow conductivity cannot be provided for oil and gas flow in the production process.
In hydraulic fracturing construction, tens of thousands of squares of fracturing fluid are injected into a reservoir at high displacement to form an artificial fracture network. In the current fracturing operation, only less than 20-50% of fracturing fluid can be smoothly drained back, so that most of the fracturing fluid enters the stratum, and a water lock phenomenon is easily caused in a near-wellbore area, so that oil gas cannot overflow. A large amount of fracturing fluid contains macromolecular artificially-synthesized polymers and residues of natural macromolecular vegetable gum, which also cause certain damage to the stratum.
In order to solve the above problems, research and development personnel have conducted intensive studies. The nano emulsion can enter deep stratum and fine cracks to exert effect due to the nano scale. Meanwhile, the nano emulsion has the characteristics of good stability and the like, and plays an increasingly large role in the fracturing fluid. However, most of the currently disclosed fracturing nano-emulsions are developed around the effects of expansion prevention and flowback, and although the fracturing fluid products can play a certain role in the near-wellbore zone, the fracturing fluid products do not play a role in the portion of the fracturing fluid which penetrates into the stratum or even remains in the stratum and contacts oil and gas. In addition, the temperature and the mineralization degree of the fracturing fluid are also continuously improved in the continuous advancing and detention process of the fracturing fluid in the deep part of the stratum, and higher requirements are brought to an active agent in the fracturing fluid.
Disclosure of Invention
In view of the above defects or shortcomings in the prior art, the present application is expected to provide an amphoteric gemini surfactant and a temperature-resistant and salt-resistant nanoemulsion for fracturing fluid containing the amphoteric gemini surfactant, wherein the nanoemulsion has a small particle size, can be effectively injected into a tight oil reservoir, and has high surface activity, strong temperature resistance and salt resistance, thereby effectively improving the oil reservoir recovery ratio.
As a first aspect of the present application, the present application provides an amphoteric gemini surfactant.
Preferably, the amphoteric gemini surfactant has the following general structural formula:
Figure BDA0002513644290000021
wherein n is 2-3; r1Is methyl, ethyl or C8～C10Alkyl of R2Is C10～C18Alkyl group of (1).
Preferably, the amphoteric gemini surfactant is an alkyl (R) group1) Substituted p-phenylenediamine with bromoalkyl (R)2) The amine and the bromine alkyl sulfonate are subjected to contact reaction in a solvent of dichloromethane at the temperature of 60-80 ℃.
As a second aspect of the present application, the present application provides an application of the amphoteric gemini surfactant described in the first aspect in preparing a temperature-resistant and salt-resistant nanoemulsion for a fracturing fluid.
As a third aspect of the present application, the present application provides a temperature-resistant and salt-resistant nanoemulsion for a fracturing fluid.
Preferably, the temperature-resistant and salt-resistant nano emulsion for the fracturing fluid comprises the following components in percentage by mass:
Figure BDA0002513644290000022
Figure BDA0002513644290000031
wherein the primary surfactant is an amphoteric gemini surfactant according to the first aspect of the present application.
Preferably, the oil phase is one or a mixture of several of white oil, naphtha, rapeseed oil, olive oil and turpentine.
Preferably, the secondary surfactant is one or a mixture of more of alkyl polyoxyethylene ether, alkylamine polyoxyethylene ether, alkyl betaine and alkylamide propyl betaine; the cosurfactant is one or a mixture of more of ethanol, propanol, isopropanol, butanol, isobutanol, sec-butyl alcohol, amyl alcohol, isoamyl alcohol, hexanol, isohexanol, n-octanol, ethylene glycol and propylene glycol.
Preferably, the alkyl polyoxyethylene ether, the alkylamine polyoxyethylene ether, the alkyl betaine and the alkylamide propyl betaine have alkyl chain length of 10-22.
Preferably, the polyoxyethylene EO number of the alkyl polyoxyethylene ether and the alkylamine polyoxyethylene ether is 3-9.
Preferably, the particle size of the temperature-resistant and salt-resistant nano emulsion for the fracturing fluid is 10-50 nm.
As a fourth aspect of the present application, the present application provides a preparation method of the temperature-resistant and salt-resistant nanoemulsion for a fracturing fluid according to the second aspect.
Preferably, the preparation method comprises the following steps:
dissolving a main surfactant and a secondary surfactant in an oil phase, and uniformly stirring at a stirring speed of 100-400 rpm;
and heating to 40-70 ℃, stirring for reaction for 30-50 min, slowly dripping water and cosurfactant, and continuously stirring for 30-90 min to obtain the temperature-resistant and salt-resistant nano emulsion for the fracturing fluid.
As a fifth aspect of the application, the application provides the application of the temperature-resistant and salt-resistant nano emulsion for the fracturing fluid of the second aspect in oilfield fracturing operation.
The beneficial effect of this application:
1) the amphoteric gemini surfactant disclosed by the application has a phenyl linking group and a sodium sulfonate group, and has excellent temperature resistance, salt resistance and oil-water interfacial tension capacity.
2) According to the nano emulsion, the amphoteric gemini surfactant with the phenyl linking group is introduced, so that the nano emulsion has remarkable heat resistance and salt resistance, can resist the temperature of 150 ℃ and the salt resistance of more than 30% of NaCl, and has the advantages of high surface activity, high flowback efficiency, high oil washing efficiency and the like;
3) the nano emulsion disclosed by the application has the advantages that different oil phase combinations are introduced, the dispersion and the interface fluidity of oil drops in the emulsification process are influenced synergistically by the difference of properties such as molecular weight, polarity, viscosity, density, fatty acid chain length and water solubility of different oil phases and the difference of interface characteristics, so that the nano emulsion is small in particle size, has a good viscosity reduction and pour point depression effect on the extracted crude oil, and is more favorable for the extraction of the crude oil.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the following detailed description of non-limiting embodiments thereof, made with reference to the accompanying drawings in which:
FIG. 1 is an infrared spectrum of a gemini surfactant of example 1 herein.
FIG. 2 is a static wash oil profile of the nanoemulsions of examples 2 and 3 herein with commercial surfactant DBS in 300000TDS brine.
Detailed Description
The present application will be described in further detail with reference to the following drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention. It should be noted that, for convenience of description, only the portions related to the present invention are shown in the drawings.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present application will be described in detail below with reference to the embodiments with reference to the attached drawings.
It is noted that the endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and that such ranges or values are understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Unless otherwise specified, all raw materials referred to in the present application are commercially available raw materials.
Embodiments of the present application provide an amphoteric gemini surfactant having the following general structural formula:
Figure BDA0002513644290000051
wherein n is 2-3; r1Is methyl, ethyl or C8～C10Alkyl of R2Is C10～C18Alkyl group of (1).
The amphoteric gemini surfactant has the phenyl linking group and the sodium sulfonate group, so that the surfactant has excellent temperature resistance and salt tolerance and oil-water interfacial tension capacity, and has the advantages of low critical micelle concentration, small stratum adsorption, small stratum damage and the like compared with a single-seed surfactant and a cationic surfactant.
Wherein the application is based on the carbon chain of crude oil, R of the amphoteric gemini surfactant1And R2The radicals are selected, preferably R1Is methyl, ethyl or C8～C10Alkyl of R2Is C10～C18The alkyl can enable the amphoteric gemini surfactant to have lower interfacial tension and show better performance.
Further, the amphoteric gemini surfactant is an alkyl (R)1) Substituted p-phenylenediamine with bromoalkyl (R)2) Amine and bromine alkyl sulfonate are subjected to contact reaction in a solvent of dichloromethane at the temperature of 60-80 DEG C
The amphoteric gemini surfactant can be applied to preparation of the nano emulsion for the fracturing fluid, and can remarkably reduce the surface tension and the interfacial tension of the nano emulsion for the fracturing fluid, so that the nano emulsion is endowed with extremely high surface activity and remarkable temperature and salt resistance.
Further, embodiments of the present application provide a temperature and salt tolerant nanoemulsion for fracturing fluids, comprising the amphoteric gemini surfactant described above in the present application.
In some preferred embodiments, the temperature-resistant and salt-resistant nanoemulsion for the fracturing fluid comprises the following components in percentage by mass:
Figure BDA0002513644290000052
Figure BDA0002513644290000061
wherein the primary surfactant is an amphoteric gemini surfactant described herein above.
In this embodiment, the oil phase acts as a dispersed phase, spontaneously forming a dispersion in the presence of the primary surfactant, the secondary surfactant, and the co-surfactant; the secondary surfactant plays an auxiliary role, and is used for assisting the primary surfactant to better form stable nano emulsion on one hand and better reducing the surface tension on the other hand; the cosurfactant is used as an auxiliary agent of the surfactant to change the surface activity and the hydrophilic-lipophilic balance of the surfactant.
In some preferred embodiments, the oil phase is one or a mixture of white oil, naphtha, rapeseed oil, olive oil, and turpentine.
Suitable oil phases help to obtain a nano-emulsion with uniform dispersion and smaller particle size, wherein the properties of molecular weight, polarity, viscosity, density, fatty acid chain length, water solubility and the like of different oil phases can influence the particle size, stability and bioavailability of the emulsion; and the interfacial properties of the oil phase also affect the dispersion of oil droplets and the fluidity of the interface during emulsification, and generally emulsion with smaller particle size can be obtained by reducing the interfacial tension.
Preferably, the nano emulsion disclosed by the application adopts two or more of white oil, naphtha, rapeseed oil, olive oil and turpentine to form different oil phase combinations, so that the nano emulsion has a smaller particle size on one hand, and has a better viscosity reduction and pour point depression effect on the extracted crude oil on the other hand, and the nano emulsion is more beneficial to the extraction of the crude oil.
In some preferred embodiments, the secondary surfactant is one or a mixture of alkyl polyoxyethylene ether, alkylamine polyoxyethylene ether, alkyl betaine and alkylamide propyl betaine.
In some preferred embodiments, the alkyl polyoxyethylene ether, alkylamine polyoxyethylene ether, alkyl betaine and alkylamide propyl betaine have an alkyl chain length of 10 to 22.
In the embodiment, the alkyl chain length can influence the interface arrangement and aggregation morphology of the surfactant, so that the wettability of the surfactant is influenced, and the longer the alkyl chain is, the weaker the wettability is, so that the alkyl chain length of the alkyl polyoxyethylene ether, the alkyl amine polyoxyethylene ether, the alkyl betaine and the alkylamide propyl betaine is preferably 10-22.
In some preferred embodiments, the polyoxyethylene EO number of the alkyl polyoxyethylene ether and the alkylamine polyoxyethylene ether is 3-9.
In the embodiment, the EO number can also influence the wettability of the surfactant, and the spreading speed of the nonionic surfactant such as alkyl polyoxyethylene ether and alkylamine polyoxyethylene ether on the hydrophobic surface is reduced as the EO number increases, so that the polyoxyethylene EO number of the alkyl polyoxyethylene ether and alkylamine polyoxyethylene ether is preferably 3 to 9.
In some preferred embodiments, the co-surfactant is one or more selected from ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, pentanol, isopentanol, hexanol, isohexanol, n-octanol, ethylene glycol, and propylene glycol.
In some preferred embodiments, the particle size of the temperature-resistant and salt-resistant nano emulsion for the fracturing fluid is 10-50 nm. The particle size is distributed in a nanometer scale smaller than 50nm, the particle size is easy to enter deep stratum, stratum nanometer holes roar and a plurality of fine gaps, small liquid drops and large specific surface area enable the nanometer emulsion to have strong conveying and transporting capacity, and the integration of fracturing and oil displacement of a compact oil reservoir is realized.
In some preferred embodiments, the preparation method of the temperature-resistant and salt-resistant nanoemulsion for the fracturing fluid comprises the following steps:
dissolving a main surfactant and a secondary surfactant in an oil phase, and uniformly stirring at a stirring speed of 100-400 rpm;
and heating to 40-70 ℃, stirring for reaction for 30-50 min, slowly dripping water and cosurfactant, and continuously stirring for 30-90 min to obtain the temperature-resistant and salt-resistant nano emulsion for the fracturing fluid.
According to the method, the nano emulsion with low nano size and high stability can be prepared by combining various surfactants and adopting a simple synthesis process, and the stability of the prepared nano emulsion exceeds 12 months.
The nano emulsion has smaller grain diameter and small size effect, so that the nano emulsion is easy to inject into a stratum, particularly a low-porosity and low-permeability stratum and fine gaps; the nano emulsion disclosed by the application can rapidly reduce the surface tension and the interfacial tension of the crude oil remained in rock gaps in the oil deposit after being injected into a compact oil deposit, so that oil veins can flow out of the rock gaps and coalesce into an oil zone, and the oil zone is driven to move and be extracted under the action of injected water, thereby achieving the purpose of improving the oil deposit recovery ratio.
Furthermore, the nano emulsion has excellent temperature resistance and salt resistance and can stably exist in a stratum.
The nano emulsion provided by the application can be applied to the fields of fracturing, acidification, chemical flooding and the like, for example, the nano emulsion can be used as a yield increasing synergist, an oil displacement agent or a thickening agent integrating flowback and yield increase in oilfield fracturing operation, so that the crude oil recovery rate is improved.
Example 1
Preparation of amphoteric gemini surfactant
Stirring is started in a reactor, 35.8g of N, N-diethyl-p-phenylenediamine is dissolved in 200m L dichloromethane, 121.2g of bromotetradecylamine is added, the temperature is raised to 60 ℃, after 5 hours of reaction, 82.0g of 2-bromoethyl sodium sulfonate is added, the temperature is raised to 70 ℃, after 6 hours of reaction, the solvent is evaporated, and the amphoteric gemini surfactant is obtained.
Wherein, the infrared identification spectrum of the gemini surfactant prepared in the embodiment is shown in fig. 1, and as can be seen from fig. 1, the FTIR spectrum of the gemini surfactant is 2963.15cm-1And 2838.15cm-1The stretching vibration absorption peak of methyl methylene C-H on an alkyl chain is 693.60cm-1The skeleton vibration peak of long chain methylene with carbon number greater than 4 is 1020.10cm-1In the presence of sulfonic acid groups-SO3Stretching vibration absorption peak of S-O bond in group, 1431.74cm-1And 1477.75cm-1There is a characteristic absorption peak of the benzene ring.
The amphoteric gemini surfactants referred to in the following examples were prepared as described in example 1, except that the corresponding alkyl-substituted p-phenylenediamine, bromoalkylamine, and sodium bromoalkylsulfonate were selected.
Example 2
45.0g of olive oil and 42.5g of turpentine are weighed into a reactor, stirring is switched on, 87.2g of gemini surfactant (n ═ 2, R) are added at 400rpm1Is ethyl, R 214 alkyl), 30.0g of lauryl polyoxyethylene (6) ether, 40.5g of cocamidopropyl betaine, slowly raising the temperature to 60 ℃ with stirring, stirring for reaction for 30min, and then slowly adding dropwise a mixture of 52.5g of isobutanol and 52.0g of water. And after the dropwise addition is finished, stirring and reacting for 60min at 60 ℃ to obtain transparent nano emulsion SD-1.
Example 3
45.0g of white oil and 32.2g of olive oil are weighed into a reactor, stirring is switched on and 85.6g of gemini surfactant (n ═ 2, R) are added at 400rpm1Is ethyl, R 214 alkyl), 42.0g of lauryl polyoxyethylene (9) ether, 31.8g of cocamidopropyl betaine, slowly increasing the temperature to 60 ℃ with stirring, stirring for 30min, and then slowly adding dropwise a mixture of 48.6g of n-pentanol and 64.5g of water. And after the dropwise addition is finished, stirring and reacting for 60min at 60 ℃ to obtain transparent nano emulsion SD-2.
Example 4
78.8g of naphtha were weighed into the reactor, stirring was switched on and 85.5g of gemini surfactant (n-3, R) were added at 400rpm1Is methyl, R 214 alkyl group), 38.2g of lauryl polyoxyethylene (6) ether, 25.8g of myristamidopropyl betaine, slowly raising the temperature to 70 ℃ with stirring, stirring for reaction for 30min, and then slowly adding dropwise a mixture of 61.2g of isopropanol and 60.5g of water. And after the dropwise addition is finished, stirring and reacting for 60min at 70 ℃ to obtain transparent nano emulsion SD-3.
Example 5
67.5g of white oil were weighed into a reactor, stirring was turned on, and 84.0g of gemini surfactant (n-3, R) was added at 400rpm1Is methyl, R216 alkyl), 40.0g of lauryl polyoxyethylene (6) ether, 32.5g of stearamidopropyl betaine, slowly raising the temperature to 70 ℃ with stirring, reacting with stirring for 30min, and then slowly adding dropwise a mixture of 63.0g of n-butanol and 63.0g of water. And after the dropwise addition is finished, stirring and reacting for 60min at 70 ℃ to obtain transparent nano emulsion SD-4.
Example 6
60.5g of white oil are weighed into a reactor, stirring is started, 85.0g of gemini surfactant (n-3, R) is added at 400rpm1Is methyl, R216 alkyl), 38.0g of lauryl polyoxyethylene (9) ether and 35.0g of dodecyl betaine, slowly raising the temperature to 60 ℃ with stirring, reacting with stirring for 30min, and then slowly adding a mixture of 60.0g of n-butanol and 71.0g of water dropwise. And after the dropwise addition is finished, stirring and reacting for 60min at 60 ℃ to obtain transparent nano emulsion SD-5.
Example 7
35.0g rapeseed oil and 45.5g white oil were weighed into a reactor, the stirring was switched on and 82.3g gemini surfactant (n ═ 3, R) was added at 400rpm1Is methyl, R 212 alkyl), 37.0g of lauryl polyoxyethylene (4) ether, 45.5g of cocamidopropyl betaine, slowly raising the temperature to 60 ℃ with stirring, stirring for reaction for 30min, and then slowly adding dropwise a mixture of 55.5g of isohexanol and 50.0g of water. And after the dropwise addition is finished, stirring and reacting for 60min at 60 ℃ to obtain transparent nano emulsion SD-6.
Example 8
25.0g of olive oil, 25.0g of turpentine, 25.0g of rapeseed oil and 30g of naphtha were weighed into a reactor, stirring was switched on, and 35g of gemini surfactant (n ═ 2, R) was added at 400rpm1Is C8 alkyl, R218 alkyl), 35.0g of lauryl polyoxyethylene (6) ether, 35.0g of cocamidopropyl betaine and 35.0g of dodecyl betaine, slowly raising the temperature to 40 ℃ with stirring, stirring for 50min, and then slowly adding dropwise a mixture of 20.0g of ethanol, 15.0g of propanol and 70.0g of water. And after the dropwise addition is finished, stirring and reacting for 30min at 40 ℃ to obtain transparent nano emulsion SD-7.
Example 9
5.0g of white oil, 5.0g of turpentine and 7.5g of naphtha were weighed into a reactor, stirring was switched on, and 140g of gemini surfactant (n ═ 2, R) were added at 400rpm1Is C10 alkyl, R2C10 alkyl) and 17.5g cocamidopropyl betaine, slowly warmed to 50 ℃ with stirring, stirred for 40min, and then slowly added dropwise a mixture of 5.0g ethylene glycol, 5.5g propylene glycol and 164.5g water. And after the dropwise addition is finished, stirring and reacting for 90min at 50 ℃ to obtain transparent nano emulsion SD-8.
Comparative example 1
A nanoemulsion was prepared according to the method of example 2, except that the amphoteric gemini surfactant was not added, yielding a transparent nanoemulsion DB-1.
Comparative example 2
A nanoemulsion was prepared according to the method of example 2, except that no secondary surfactant was added, resulting in a transparent nanoemulsion DB-2.
Performance testing
The nano-emulsions obtained in examples 2 to 9 and comparative examples 1 to 2 were subjected to flowback efficiency, static oil washing efficiency, particle size, surface tension and temperature resistance tests.
Testing the flow-back efficiency:
the nano-emulsions prepared in examples 2 to 9 and comparative examples 1 to 2 were used to prepare a 0.2% solution with 30% NaCl saline. Filling 20-40 mesh quartz sand into a sand filling pipe with the length of 25cm and the diameter of 2.5cm, and shaking on a shaking table for 30min for later use. At room temperature, injecting the nano emulsion to be measured into a sand filling pipe, opening a lower valve to enable the liquid to naturally flow out under the action of gravity, recording the amount of the flowing liquid, and calculating to obtain the flowback rate, wherein the result is shown in table 1.
TABLE 1 Return Rate test results for the nanoemulsions of the examples and comparative examples
Figure BDA0002513644290000111
It can be seen that the flowback rate of the nano-emulsions of examples 2 to 9 of the present application is significantly higher than that of comparative example 1 in which no amphoteric gemini surfactant is added and higher than that of comparative example 2 in which no co-surfactant is added, indicating that the amphoteric gemini surfactant disclosed in the present application has good surface activity, so that the nano-emulsions to which the amphoteric gemini surfactant is added have excellent flowback efficiency.
(II) testing the static oil washing efficiency:
the nanoemulsions prepared in examples 2-9 and comparative examples 1-2 were used with a commercially available surfactant, sodium Dodecylbenzenesulfonate (DBS), formulated as a 0.2% solution with 30% NaCl saline. And (3) saturating the rock core with the permeability of 0.1-0.2 mD with crude oil, putting the rock core into a static oil washing device, statically soaking the rock core in the nano emulsion saline solution prepared in the way for 15 days at the temperature of 60 ℃, recording the volume of the crude oil washed out of the rock core every day, and calculating to obtain the static oil washing rate. The results are shown in Table 2.
TABLE 2 static wash oil Rate test results for the nanoemulsions of the examples and comparative examples
Figure BDA0002513644290000112
It can be seen that the static oil washing rate of the nano-emulsion of examples 2-9 of the present application is significantly higher than that of comparative example 1 and DBS without adding amphoteric gemini surfactant, and higher than that of comparative example 2 without adding a secondary surfactant, which indicates that the amphoteric gemini surfactant disclosed in the present application has good surface activity, and can effectively reduce the oil-water interfacial tension, so that oil droplets in pores are more easily transported out, and the static oil washing efficiency of the nano-emulsion with the amphoteric gemini surfactant is improved. As can be seen from the comparison of example 2 with comparative example 2, the secondary surfactant can help to lower the surface tension and to change the rock surface wettability, so the nano-emulsion without the secondary surfactant has a slightly poor oil washing efficiency.
(III) particle size testing:
the particle size of the droplets of the nanoemulsion was measured using a ZetaPlus instrument from Brookhaven, USA, and the average particle size of the prepared nanoemulsion is shown in Table 3.
Table 3 particle size test results of the nano-emulsions of each example and comparative example
Figure BDA0002513644290000121
It can be seen that the nano-emulsion prepared by the embodiment of the present application has a nano-scale size, and the particle size is less than 50nm, so that the nano-emulsion can more effectively enter the deep part of the stratum and fine gaps.
(IV) surface tension test:
the surface tension of the nanoemulsion was measured using a DCAT25 surface tension meter from dataphysics, germany, and the results are shown in table 4.
And (V) testing temperature resistance:
the nanoemulsions prepared in examples 2 to 9 and comparative examples 1 to 2 were aged in a high temperature aging furnace at 150 ℃ for 5 days, and the surface tension of the nanoemulsions was measured using a DCAT25 surface tension meter of Dataphysics, Germany, and the results are shown in Table 4.
Table 4 surface tension and temperature resistance test results of the nano-emulsions of each example and comparative example
Figure BDA0002513644290000122
The surface tension measurement shows that the surface tension of the nano-emulsion is obviously lower than that of comparative example 1 and lower than that of comparative example 2, which shows that the amphoteric gemini surfactant disclosed by the application has good surface activity and can effectively reduce the surface tension of the nano-emulsion, so that the surface tension value of the nano-emulsion added with the amphoteric gemini surfactant is reduced.
The surface tension measurement after high-temperature aging shows that the surface tension value of the nano emulsion added with the amphoteric gemini surfactant has no change or obvious change after the nano emulsion is subjected to high-temperature treatment at 150 ℃ for 5 days, which indicates that the nano emulsion has good temperature resistance and can stably exist at the high temperature of 150 ℃. The nano emulsion of comparative example 1 has poor temperature resistance because it does not contain the amphoteric gemini surfactant, while the nano emulsion of comparative example 2 also shows excellent temperature resistance because it contains the amphoteric gemini surfactant.
Furthermore, the nano emulsion has excellent oil-washing yield-increasing performance, which can be more clearly illustrated by referring to fig. 2, and after the fracturing fluid enters the deep part of the stratum, particularly enters a microcrack compact oil-gas layer rich in oil gas, the undischarged fracturing fluid can realize the fracturing and oil-washing integrated function, so that the oil-gas recovery rate is greatly improved.
FIG. 2 is a graph showing the static oil washing process of the nano-emulsions SD-1 and SD-2 prepared by the present invention in a compact core for 15 days, and comparing the oil washing performance of the common surfactants with good performance in the market. Core experiment results show that the flow-back rate of the fracturing fluid of the nano emulsion in the addition amount of 0.1-0.3% can reach more than 70%, the static oil washing efficiency reaches more than 60%, and the flow-back rate is obviously higher than that of a commercially available surfactant DBS.
The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.

Claims (10)

1. An amphoteric gemini surfactant, characterized by the following general structural formula:
Figure FDA0002513644280000011
wherein n is 2-3; r1Is methyl, ethyl or C8～C10Alkyl of R2Is C10～C18Alkyl group of (1).
2. The amphoteric gemini surfactant according to claim 1, wherein the amphoteric gemini surfactant is an alkyl (R) group1) Substituted p-phenylenediamine with bromoalkyl (R)2) The amine and the bromine alkyl sulfonate are subjected to contact reaction in a solvent of dichloromethane at the temperature of 60-80 ℃.
3. Use of the amphoteric gemini surfactant according to claim 1 or 2 for the preparation of a temperature and salt tolerant nanoemulsion for fracturing fluids.
4. The temperature-resistant and salt-resistant nanoemulsion for the fracturing fluid is characterized by comprising the following components in percentage by mass:
Figure FDA0002513644280000012
wherein the primary surfactant is the amphoteric gemini surfactant of claim 1 or 2.
5. The temperature-resistant and salt-resistant nanoemulsion for the fracturing fluid as claimed in claim 4, wherein the oil phase is one or a mixture of more of white oil, naphtha, rapeseed oil, olive oil and turpentine.
6. The temperature-resistant and salt-resistant nanoemulsion for the fracturing fluid as claimed in claim 4, wherein the secondary surfactant is one or a mixture of alkyl polyoxyethylene ether, alkylamine polyoxyethylene ether, alkyl betaine and alkylamidopropyl betaine; the cosurfactant is one or a mixture of more of ethanol, propanol, isopropanol, butanol, isobutanol, sec-butyl alcohol, amyl alcohol, isoamyl alcohol, hexanol, isohexanol, n-octanol, ethylene glycol and propylene glycol.
7. The temperature-resistant and salt-resistant nanoemulsion for the fracturing fluid as claimed in claim 6, wherein the alkyl polyoxyethylene ether, alkylamine polyoxyethylene ether, alkyl betaine and alkylamidopropyl betaine have an alkyl chain length of 10-22; the polyoxyethylene EO number of the alkyl polyoxyethylene ether and the alkylamine polyoxyethylene ether is 3-9.
8. The temperature-resistant and salt-resistant nanoemulsion for the fracturing fluid as claimed in claim 4, wherein the particle size of the temperature-resistant and salt-resistant nanoemulsion for the fracturing fluid is 10-50 nm.
9. The preparation method of the temperature-resistant and salt-resistant nanoemulsion for the fracturing fluid as claimed in any one of claims 4 to 8, which is characterized by comprising the following steps:
dissolving a main surfactant and a secondary surfactant in an oil phase, and uniformly stirring at a stirring speed of 100-400 rpm;
and heating to 40-70 ℃, stirring for reaction for 30-50 min, slowly dripping water and cosurfactant, and continuously stirring for 30-90 min to obtain the temperature-resistant and salt-resistant nano emulsion for the fracturing fluid.
10. The use of the temperature and salt resistant nanoemulsion for fracturing fluids of any one of claims 4 to 8 in oilfield fracturing operations.
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