CN119823300B - Surfactant, preparation method thereof and imbibition agent - Google Patents
Surfactant, preparation method thereof and imbibition agent Download PDFInfo
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Abstract
本公开提供了一种表面活性剂及其制备方法和渗吸剂，表面活性剂包括式（1）和式（2）所示的结构，式（1）式（2）式（1）中连接处#连接氢原子和式（2）中的一种或多种，其中，式（1）中至少有一个连接处#与式（2）中至少有一个连接处#连接，n为正整数，n为8至16。表面活性剂兼具分散性好和粒径小的特点，在使用过程中可解决传统表面活性剂及天然生物表面活性剂胶束聚集问题，在低渗透储层采油过程中提高了小孔隙储油的采收率。
The present disclosure provides a surfactant and a preparation method thereof and an imbibing agent. The surfactant includes structures shown in formula (1) and formula (2). Formula (1) Formula (2) The connection # in formula (1) connects the hydrogen atom and one or more of formula (2), wherein at least one connection # in formula (1) is connected to at least one connection # in formula (2), and n is a positive integer, and n is 8 to 16. The surfactant has the characteristics of good dispersibility and small particle size. During use, it can solve the aggregation problem of micelles of traditional surfactants and natural biosurfactants, and improve the recovery rate of small pore oil storage during oil production in low permeability reservoirs.
Description
Technical Field
The present disclosure relates to a surfactant, a method of preparing the same, and a imbibition agent.
Background
The low permeability oil field has the characteristics of low porosity and low permeability, and has quite optimistic development prospect. However, the complexity of this type of reservoir has determined that it is difficult to develop. The development of technological innovation and environment-friendly strategies is complied with, and nanotechnology and microbial enhanced oil recovery technology are expected to become new breakthrough points.
Biologically produced nanoscale surfactants play an important role in low-permeability oil recovery, particularly in enhanced oil recovery. However, the traditional surfactant and biosurfactant are seriously adsorbed in the reservoir, and the surfactant is easy to form micelle in the use process, so that the size is enlarged, the channel is blocked, and the exploitation efficiency is directly affected. Therefore, how to further improve the development efficiency of low permeability reservoirs is of great importance.
Disclosure of Invention
The invention discloses a surfactant, a preparation method thereof and a imbibition agent, wherein the surfactant has the characteristics of good dispersibility and small particle size, and can prevent aggregation of polymer molecules by intermolecular charge repulsive force in the use process, solve the aggregation problem of traditional surfactant and natural biosurfactant micelles, and improve the recovery ratio of small-pore oil storage in the low-permeability reservoir oil extraction process.
In a first aspect, the present disclosure provides a surfactant comprising a structure represented by formula (1) and formula (2),
(1)
(2)
The connection part # in the formula (1) is connected with one or more of the hydrogen atoms and the formula (2), wherein at least one connection part # in the formula (1) is connected with at least one connection part # in the formula (2), n is a positive integer, and n is 8 to 16.
In some alternative embodiments, the surfactant is of the structure shown in formula (3):
(3)
Wherein n is a positive integer, and n is 8 to 16.
In some alternative embodiments, the surfactant is a nano-supermolecule, and the amount of the nano-supermolecule in the surfactant having a particle size of 10nm to 30nm is greater than 90%.
In some alternative embodiments, the interfacial tension of the surfactant with water is less than 0.1 mN/m and the surface tension value of the surfactant with water is less than 20 mN/m.
In a second aspect, the present disclosure provides a method of preparing a surfactant of the first aspect, the method comprising:
(4)
Mixing a compound shown in a formula (4) with cyclodextrin in an organic solution to obtain a mixed solution;
and (3) reacting the compound shown in the formula (4) in the mixed solution with cyclodextrin to prepare the surfactant.
In some alternative embodiments, the cyclodextrin is beta-cyclodextrin and the mass ratio of the compound of formula (4) to cyclodextrin is (50-200): 1.
In some alternative embodiments, the compound of formula (4) in the mixture is reacted with cyclodextrin to produce a surfactant comprising:
the mixed solution is stirred at a rotation speed of 400-600 rpm at 20-30 ℃ to enable the compound shown in the formula (4) in the mixed solution to react with cyclodextrin.
In some alternative embodiments, the organic solution comprises 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine and the organic solvent, the mass ratio of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to 4-dimethylaminopyridine being (2:1) to (10:1).
In a third aspect, the present disclosure provides a imbibition agent for oil exploitation, the imbibition agent comprising the surfactant of the first aspect or the surfactant prepared by the preparation method of the second aspect and water, wherein the mass content of the surfactant in the imbibition agent is from 0.1% to 10%.
The technical scheme of the embodiment of the application has at least the following beneficial effects:
The structure of the surfactant disclosed by the application adopts a unique structure shown in a formula (1) with inner hydrophobicity and outer hydrophilicity, namely a cyclodextrin structure, and can effectively wrap oil substances, so that the solubility and stability of the oil substances in water are improved, the structure of the surfactant is combined with the structure shown in a formula (2) through chemical bonds, the material is stable in structure, has the characteristics of good dispersibility and small particle size, and the intermolecular charge repulsive force of the surfactant can prevent aggregation of polymer molecules, so that the aggregation problem of traditional surfactants and natural biosurfactants can be solved in the use process. In the process of recovering crude oil in a low-permeability reservoir, the nano surfactant can increase the fluidity of mixed substances and enter the small-pore shale for storing petroleum, so that the recovery ratio of the small-pore shale for storing the petroleum is improved.
Therefore, with the continuous development of nano-pore shale oil exploitation, the appearance and application of the surfactant have very important practical significance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the following will briefly describe the drawings that are required to be used in the embodiments of the present disclosure. It will be apparent to those of ordinary skill in the art that the drawings described below are merely some embodiments of the present disclosure and that other drawings may be made from the drawings without the exercise of inventive effort.
Fig. 1 illustrates a schematic diagram of a microscopic model provided by some embodiments of the present disclosure.
In the drawings, the drawings are not necessarily to scale.
Detailed Description
Hereinafter, embodiments of the surfactant of the present disclosure, and methods for preparing and using the same are specifically disclosed, with reference to the accompanying drawings as appropriate. However, unnecessary detailed description may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of the actual same structure may be omitted. This is to avoid that the following description becomes unnecessarily lengthy, facilitating the understanding of those skilled in the art. Furthermore, the drawings and the following description are provided for a full understanding of the present disclosure by those skilled in the art, and are not intended to limit the subject matter recited in the claims.
The "range" disclosed in this disclosure is defined in terms of lower and upper limits, with the given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if minimum range values 1 and 2 are listed, and if maximum range values 3,4, and 5 are listed, then the following ranges are all contemplated as 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this disclosure, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12 or the like.
All embodiments of the disclosure, as well as alternative embodiments, may be combined with each other to form new solutions, and such solutions should be considered to be included in the disclosure of the present disclosure, unless specifically stated otherwise.
All technical features of the present disclosure as well as optional technical features may be combined with each other to form new technical solutions unless specifically stated, and such technical solutions should be considered as included in the disclosure of the present disclosure.
All steps of the present disclosure may be performed sequentially, or may be performed randomly, preferably sequentially, unless otherwise indicated. For example, the method may include steps (a) and (b), and the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially. For example, it is mentioned that the method may further comprise step (c), meaning that step (c) may be added to the method in any order, e.g. the method may comprise steps (a), (b) and (c), may also comprise steps (a), (c) and (b), may also comprise steps (c), (a) and (b), etc.
The present disclosure provides a surfactant comprising structures represented by formula (1) and formula (2),
(1)
(2)
The connection part # in the formula (1) is connected with one or more of the hydrogen atoms and the formula (2), wherein at least one connection part # in the formula (1) is connected with at least one connection part # in the formula (2), n is a positive integer, and n is 8 to 16.
According to the embodiment of the application, the hydroxyl on the surface of the structure shown in the formula (1) in the surfactant has hydrophilic performance, the alkyl or alkylene structure inside has lipophilicity, and can effectively wrap oil substances, so that the solubility and stability of the oil substances in water are improved, the structure shown in the formula (1) and the structure shown in the formula (2) are combined through chemical bonds, the particle size is uniform, the good dispersibility is achieved, and the micelle aggregation problem of the traditional surfactant can be solved when the surfactant is used due to intermolecular charge repulsive force of the surfactant. The surfactant has strong wettability in the process of recovering crude oil in a low-permeability reservoir, and can enter into small pores in the process of petroleum exploitation, so that the recovery ratio of the small-pore oil storage is improved.
In some alternative embodiments, the surfactant is of the structure shown in formula (3):
(3)
Wherein n is a positive integer, and n is 8 to 16. Therefore, the fluidity of the mixed substances is further improved, the mixed substances can better enter into small pores in small pore oil exploitation, and the recovery ratio of the small pore oil storage is further improved.
N may be calculated as an average value.
In some alternative embodiments, the surfactant is a nano-supermolecule, and the amount of the nano-supermolecule in the surfactant having a particle size of 10nm to 30nm is greater than 90%. Alternatively, the amount of the nano supermolecules having a particle size of 10nm to 30nm may be 95% to 100%, and further alternatively 96% to 98%. Thus, the method is beneficial to entering the rock with small pores for storing crude oil in a low permeability way, and oil exploitation is realized.
The surfactant has an average particle size of 10 to 50 nm, optionally 20 to 30 nm.
Surfactant particle size detection of such nano supermolecules can be determined using Dynamic Light Scattering (DLS).
In some alternative embodiments, the contact angle of the surfactant with the oil is 9.8 ° to 10.2 °, alternatively 10 ° to 10.1 °.
The contact angle refers to the angle formed by a liquid on the surface of a solid, reflecting the degree of wetting of the solid by the liquid. The small contact angle indicates that the liquid wets the solid surface more easily.
The contact angle is in the range, so that the solution containing the surfactant is easier to spread on the surface of the rock, the wettability of the rock is improved, the interfacial tension is reduced, the surfactant solution can be promoted to uniformly permeate into an oil layer, oil drops are stripped and dispersed, emulsion or foam is formed, and the flow channel of the oil is increased, so that the oil displacement efficiency is improved.
In addition, the contact angle of the surfactant and the oil in the range can reduce the flow resistance of the surfactant in the porous medium, reduce the injection pressure, improve the swept volume of the displacement fluid, cover more unexplored oil areas and improve the recovery ratio.
In some alternative embodiments, the interfacial tension of the surfactant with water is less than 0.1 mN/m and the surface tension value of the surfactant with water is less than 20 mN/m. Alternatively, the interfacial tension of the surfactant and water is 0.06+ -0.01 mN/m, and the surface tension value of the surfactant and water is 18.8+ -0.2 mN/m.
Interfacial tension means that surfactants can better reduce the interfacial tension between oil and water, and low interfacial tension may allow water to penetrate into the oil layer more easily.
The interfacial tension of the surfactant and water and the surface tension value of the surfactant and water are in the above ranges, so that the constraint of capillary force on oil drops can be weakened, the oil is more easily displaced from rock pores, the oil displacement efficiency is improved, the injection resistance is also reduced, more unexplored oil areas can be covered, and the recovery ratio is improved.
In a second aspect, the present disclosure provides a method of preparing the surfactant of the first aspect, the method comprising steps 100 to 200.
(4)
Step 100, mixing the compound represented by formula (4) with cyclodextrin in an organic solution to obtain a mixed solution.
In this step, the cyclodextrin may be α -cyclodextrin, β -cyclodextrin, or γ -cyclodextrin, and has hydroxyl groups on the surface thereof, and may undergo esterification reaction with the compound represented by formula (4).
The compound represented by formula (4) and cyclodextrin may be mixed in an organic solution. The organic solution may be a mixed solution comprising 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDCI) and 4-Dimethylaminopyridine (DMAP), a mixed solution comprising N, N '-dicyclohexylcarbodiimide and 4-dimethylaminopyridine (DCC/DMAP solution system), and a mixed solution comprising N, N' -diisopropylcarbodiimide and 4-dimethylaminopyridine (DIC/DMAP solution system).
The organic solvent in the organic solution can be ethanol, N-dimethylformamide, dimethyl sulfoxide, etc.
In some alternative embodiments, the cyclodextrin is beta-cyclodextrin and the mass ratio of the compound of formula (4) to cyclodextrin is (50-200): 1, alternatively (60-150): 1, further alternatively (80-120): 1.
Step 200, reacting the compound shown in the formula (4) in the mixed solution with cyclodextrin to prepare the surfactant.
In this step, the compound represented by the formula (4) is derived from a metabolite of the microorganism.
In some alternative embodiments, in step 200, the compound of formula (4) in the mixed solution is reacted with cyclodextrin to produce a surfactant, comprising:
The mixture is stirred at a rotational speed of 400-600 rpm at 20-30 ℃ to react the compound represented by formula (4) in the mixture with cyclodextrin.
Alternatively, the temperature may be 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, and the like. Alternatively, the stirring speed may be 400rpm、410rpm、420rpm、430rpm、440rpm、450rpm、460rpm、470rpm、480rpm、490rpm、500rpm、510rpm、520rpm、530rpm、540rpm、550rpm、560rpm、570rpm、580rpm、590rpm、600rpm or the like.
These reaction conditions can promote the reaction of the compound represented by formula (4) with cyclodextrin, so that the compound represented by formula (4) reacts more with the hydroxyl groups on the surface of cyclodextrin, and the comprehensive performance of the surfactant is improved.
In some alternative embodiments, the stirring time may be 8-12 hours in step 200.
In some alternative embodiments, in step 200, the organic solution comprises 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine and the organic solvent, the mass ratio of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to 4-dimethylaminopyridine is (2:1) to (10:1), optionally 5:1, 6:1, 7:1, 8:1, 9:1, etc. The solution is favorable for the esterification reaction of the compound shown in the formula (4) and cyclodextrin, and the comprehensive performance of the surfactant is further improved on the basis of considering the reaction efficiency.
In a third aspect, the present disclosure provides a imbibition agent for oil exploitation, the imbibition agent comprising the surfactant of the first aspect or the surfactant prepared by the preparation method of the second aspect and water, wherein the mass content of the surfactant in the imbibition agent is from 0.1% to 10%. The surfactant in the seepage and absorption agent can enter small pores in an oil storage layer, so that oil can be more easily displaced from the rock pores, the oil displacement efficiency is improved, the injection resistance is further reduced, more unexplored oil areas can be covered, and the recovery ratio is further improved.
Examples
The present disclosure is more particularly described in the following examples that are intended as illustrations only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages and ratios reported in the examples below are on a mass basis, and all reagents used in the examples are commercially available or were obtained synthetically according to conventional methods and can be used directly without further treatment, as well as the instruments used in the examples.
Example 1 preparation of surfactants
Reference is Wang M, yu H, li X, et al Metabolic Engineering, 2020, 62:235-248. Synthesis. 3 kinds of compounds shown in the formula (4) are prepared, wherein n is 10,13 and 14 respectively, and the compound raw materials shown in the formula (4) are prepared from microbial fermentation metabolites.
(4) A step of,
Wherein n is 10, 13, 14.
The above 3 kinds of compounds represented by the formula (4) were respectively dissolved in EDCI/DMAP mixed solution of volume 80 mL in mass ratio of 60:1, 75:1, 80:1 with beta-cyclodextrin, the EDCI/DMAP mixed solution was prepared by mixing 1.8g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDCI) and 0.9g of 4-Dimethylaminopyridine (DMAP) and adding ethanol as a solvent, and the compound represented by the formula (4) was reacted with beta-cyclodextrin at 25 ℃ with stirring at 500rpm for 12 hours, wherein the molecular weight of beta-cyclodextrin was 1134.984, and the excess unreacted material was removed by ultrafiltration with a centrifuge tube having a cutoff of 2 kDa, to obtain the surfactant represented by the formula (3). The final yields of the surfactant shown in the formula (3) are 62.4%, 71.8% and 73.2%, respectively, calculated by liquid chromatography and mass spectrometry tests and calculation formulas.
Performance testing
(1) Particle size test of surfactant
A sample of the 10 mg surfactant prepared in example 1 (n=14) was taken and diluted with ultrapure water to a mass fraction of 0.1% aqueous solution to ensure that the sample concentration was within the instrument detection range. The measurement was performed using a Dynamic Light Scattering (DLS). Setting detection parameters according to sample characteristics, setting the detection temperature to 25 ℃, adding the filtered sample into a sample cell with the scattering angle of 90 ℃, and ensuring that the height of the sample solution in the sample cell is about 2/3 of the total height of the cell body, wherein each sample is collected for 30s. The results of table 1 were obtained by performing data analysis using the control method.
TABLE 1
As shown in Table 1, the particle size of the surfactant is mainly 10-30 nm.
(2) Zeta potential detection method of surfactant
The surfactant 10 mg prepared in example 1 (n=14) was diluted with ultrapure water to 0.1% aqueous solution, the diluted sample was thoroughly mixed to ensure uniform dispersion of particles, the diluted sample was injected into a sample cell of a Zeta potential analyzer for measurement, and the result showed that the Zeta potential of the surfactant 0.1% was-35 mV, and the surfactant had better stable dispersibility when the absolute value of the Zeta potential was greater than 30 mV according to the general standard of the Zeta potential, so that the conventional micelle aggregation problem could be solved.
(3) Surfactant surface tension determination
The surfactant (n=14) prepared in example 1 and the compound represented by formula (4) prepared in example 1 were each prepared into a sample aqueous solution having a mass concentration of 0.1% with distilled water.
The instrument used for the test is QBZY-2 type full-automatic surface tensiometer, and the surface tension (measuring range is 0-400N/m) is tested based on the platinum plate method (WILHELMY PLATE method) technology, and the indoor temperature is 25+/-2 ℃.
The specific procedure is that when the instrument starts to test, the surface tension of pure water is tested first, about 72 mN/m. The surface tension of the two sample solutions with the mass concentration of 0.1% was then measured in the same way, and the average value of the three groups was measured in parallel and recorded as the final surface tension value of the aqueous sample solution at that concentration.
The surface tension value of the surfactant was 18.8.+ -. 0.2 mN/m, and the surface tension value of the compound sample represented by formula (4) was 29.8.+ -. 0.5 mN/m. Demonstrating that the surfactant of the present application exhibits a stronger surface activity than the compound sample represented by formula (4).
(4) Interfacial tension measurement of surfactants
The surfactant (n=14) prepared in example 1 and the compound represented by formula (4) prepared in example 1 were each prepared into a sample aqueous solution having a mass concentration of 0.1% with distilled water.
The measurement was performed by using a TX500C type rotary drop interfacial tensiometer. The density of the internal phase crude oil in the test system is 0.84 g/cm 3, the instrument temperature is set to 25 ℃, the spinning drop rotating speed during the test is 5000 rpm, the tension value of the spinning drop interface is recorded every 30 min, and the test is carried out until the interface tension value is stable.
The interfacial tension of the surfactant was 0.06.+ -. 0.01 mN/m, and the interfacial tension of the compound represented by the formula (4) obtained in example 1 was 3.34.+ -. 0.05 mN/m. It was demonstrated that the surfactant of the present application exhibited a stronger surface activity than the compound sample represented by formula (4) with a lower surface tension value.
(5) Contact angle measurement of surfactant
The clean slide was placed in an aging oil, which was formulated from crude oil and kerosene at a 2:5 mass ratio, the viscosity of the aging oil was about 180 mPa s, the bottle mouth was sealed, and aged at 60 ℃ for more than one month for measuring the contact angle of the surfactant to evaluate its wettability. The surfactant (n=14) prepared in example 1 and the compound represented by formula (4) prepared in example 1 were each prepared into a sample aqueous solution having a mass concentration of 0.1% with distilled water. Before the experiment, the superfluous crude oil on the surface of the aged glass slide is treated, and the glass slide is dried after being soaked in the two aqueous solution samples for 10 min.
The measurement was carried out by a sitting drop method using a SCI6000E contact angle measuring instrument, the drop volume was 2 μl during the test, and the contact angle of the drop in steady state was obtained by the instrument built-in camera in combination with angle measurement software. In order to ensure the accuracy and reliability of the obtained experimental test results, each sample is at least tested for three groups of contact angles, and the average value of the groups of data is taken as the contact angle value of the surfactant.
The contact angle of the surfactant with the aged oil was 10±0.2°, and the contact angle of the compound represented by formula (4) prepared in example 1 with the aged oil was 25±0.3°. It was demonstrated that the surfactant of the present application showed more excellent wet reversal performance by decreasing the contact angle to 10±0.2° compared to the compound sample represented by formula (4).
(6) Detection of high temperature resistance of surfactant
The surfactant sample (n=14) prepared in example 1 was prepared into a working solution with a mass concentration of 0.1% with distilled water, the bottle mouth was closed, and the solution was placed in an oven at 121 ℃ for heat preservation of 2 h, and then the surface tension value of the aqueous solution at 25±2 ℃ was tested, and the specific test procedure was referred to the above test method.
The surface tension value of the surfactant after high temperature treatment is 19.2+/-0.5 mN/m, which is similar to the surface tension value of the surfactant without temperature resistance treatment of 18.8+/-0.2 mN/m. The results indicate that the surfactant works stably at 120 ℃.
(7) Detection of salt tolerance of surfactant
The prepared surfactant sample (n=14) and the compound of formula (4) of unmodified cyclodextrin in example 1 were each formulated into a working solution with a mass concentration of 0.1% with mineralized water, the mass concentration of CaCl 2、MgCl2 in mineralized water being 2g/L, the mass concentration of NaCl being 6g/L, and the surface tension values of the aqueous solutions were measured at 25±2 ℃, and specific test procedures were referred to above.
As a result of the test, the surfactant of example 1 of the present application had a surface tension value as low as 25.2.+ -. 0.4mN/m, and a mineralization degree of not less than 1X 10 5 mg/L. The surface tension value of the compound represented by the following formula (4) at the same concentration was 29.4.+ -. 0.6 mN/m.
This result shows that the surfactant of example 1 of the present application has enhanced high salt resistance compared with the compound represented by formula (4).
(8) Capillary self-priming height detection of surfactant
The preparation of the lipophilic capillary comprises sequentially treating the capillary (inner diameter 0.35 mm) with carbon tetrachloride and benzene to acetone (ethanol=7:1.5:1.5 (volume ratio) to remove organic substances on the surface of the capillary by ultrasonic treatment for 30 min, sequentially treating the capillary with dilute hydrochloric acid solution (1:10) and hydrofluoric acid solution (10%) by ultrasonic treatment for roughening the surface of the capillary, activating for 30 min, finally ultrasonically cleaning with deionized water to remove residual acid until the pH is more than 6.5,105 ℃, and drying;
Preparing ageing oil, namely preparing crude oil, aviation kerosene and asphalt according to a mass ratio of 2:5:3, fully immersing the treated capillary tube in the ageing oil, and ageing for 2-4 weeks at a temperature of 60 ℃ to obtain the treated capillary tube;
Soaking the treated capillary tube with kerosene 2 min to clean asphalt deposited on the inner and outer walls of the capillary tube, drying the kerosene outside the capillary tube with nitrogen gas, and drying in a 60 ℃ closed environment to obtain an oil-wet capillary tube, and preserving for later use.
Preparing 1 g/L of the surfactant (n=10, 13, 14) prepared in the embodiment 1 and the compound shown in the formula (4), adding carmine indicator, keeping the temperature of the solution at 25+/-0.2 ℃, pouring the solution to be tested into a cuvette until the boundary of the top end, attaching a scale to the rear wall and standing at the rear, vertically placing the treated oil-wet capillary in the cuvette, keeping the inclination angles of all the capillaries for testing consistent by using a glass slide, reading the height difference between the liquid level height in a recording tube and the height of the cuvette, and recording the liquid level height when the capillary is immersed into the liquid level 10 min.
As a result of the test, the capillary self-absorption heights of the surfactants (n=10, 13, 14) obtained in example 1 were 23mm, 26mm, 28 mm in this order, and the capillary self-absorption height of the compound represented by formula (4) was 13mm, which was 10mm, 13mm, 15mm more than the capillary self-absorption height of the surfactant obtained in example 1, indicating a better imbibition effect.
(9) Application of surfactant nano new molecules as osmotic agent in low-osmotic oilfield exploitation
The surfactant (n=10, 13, 14) prepared in example 1 and the compound sample represented by formula (4) prepared in example 1 were prepared with distilled water to prepare a sample aqueous solution having a mass concentration of 0.1%, respectively.
And (3) detecting the permeability of the surfactant in low-permeability oilfield exploitation:
1. taking a natural core of a low permeability oilfield, and drying the core in an oven at 60 ℃ for later use, wherein the air permeability (10-50) of the core is multiplied by 10 -3 μm2.
2. Placing the core in a displacement flow, setting proper pressure, and respectively saturating the core with filtered kerosene and KCl brine at a fixed flow rate and a temperature of 60 ℃;
3. the core is placed in the process again, and the inlet pressure of the core is recorded when the core flow pressure is stable and unchanged;
4. performing reverse water locking treatment with KCl brine after filtration, and performing balance stabilization treatment;
5. Repeating the steps (3) and (4), and calculating a permeability value k 1;
6. Reversely introducing the prepared aqueous solution (n=10, 13, 14) of the surfactant prepared in the example 1 and the compound sample solution shown in the formula (4) at a fixed flow rate respectively, introducing kerosene at a forward flow rate after balancing and stabilizing until the core flow pressure is stable and unchanged, recording the core inlet pressure, and calculating the permeability value k 2;
the method for calculating the permeability improvement rate of the core comprises the following steps:
TABLE 2 permeability improvement test results for osmotic agent
As shown in table 2, the permeability improvement rate of the surfactant was 25% or more, and the permeability improvement rate of the compound represented by formula (4) was 13% to 15%, so that the permeability improvement rate of the surfactant of example 1 was improved with respect to the compound represented by formula (4), and thus the permeability was improved by about 12%, and thus the oilfield exploitation effect was greatly improved, and the resource utilization rate was improved.
(10) Microscopic displacement experimental evaluation of surfactant
The surfactant (n=10, 13, 14) prepared in example 1 and the compound sample represented by formula (4) prepared in example 1 were prepared with distilled water to prepare a sample aqueous solution having a mass concentration of 0.1%, respectively.
Fig. 1 illustrates a schematic diagram of a microscopic model provided by some embodiments of the present disclosure. Specifically, the micro model is a commercially available 4cm×4cm glass sheet with a thickness of 3mm, and the micro model having the above-mentioned pores is obtained by etching treatment by a photolithography machine, and a plurality of pores are present in the micro model. The pores in the microscopic model can allow particles with specific particle size to pass through, the particle size of the particles is 40 mm, the pore volume of the microscopic model is 27 mu L, the porosity is 42.5%, and the pore diameter is 20-100 mu m.
Reference Journal of Petroleum SCIENCE AND ENGINEERING 210 (2022) 110084 prepares a microscopic displacement model. And (3) injecting saturated simulated oil into the micro-displacement model, wherein the saturated simulated oil is prepared from crude oil and kerosene according to a mass ratio of 3:5, the viscosity of the saturated simulated oil is about 180 mPa & s, and the oil is aged for 24h in a 90 ℃ incubator, so that the aged micro-displacement model is obtained.
The microscopic displacement experimental device is built and comprises an aged microscopic displacement model, a water injection system and an image acquisition system, wherein the water injection system consists of a constant-speed constant-pressure pump, a microsyringe and a model support, the image acquisition system comprises a microscope, a camera and a computer, and injection pressure is measured by an electronic pressure gauge (0-50 kPa, senex, USA). And setting parameters of a constant flow pump to perform water flooding, wherein the water injection speed is 50 mu L/min, and the flooding time is 10min. Then, the compound sample solution shown in the formula (4) is respectively used for displacement, wherein the mass concentration of the compound sample solution is 0.1%, the injection speed is 25 mu L/min, and the displacement is 30min. After the set time is over, the displacement device is kept stand for 12h, then the compound sample solution shown in the formula (4) of the surfactant aqueous solution (the mass concentration is 0.1%) is respectively used for displacement for 15min at the speed of 120 mu L/min, and after the completion, the saturation corresponding to the set phase is calculated by utilizing a MATLAB program.
Calculation of recovery ratio after the original image is sharpened, the water, gas, oil and glass phases are distinguished by a given pixel intensity threshold. The saturation of the given facies was then calculated using MATLAB program based on the ratio of the area of the given facies to the total pore area, recovery = (1-saturation) ×100%.
The results of the test show that the recovery ratio of the surfactant prepared in example 1 after micro-displacement is 50% or more, and the recovery ratio of the compound represented by the formula (4) of unmodified cyclodextrin after micro-displacement is about 30%. The recovery ratio of the surfactant prepared in example 1 was improved by about 18% (n=10), 22% (n=13) and 20% (n=14) respectively, and the oil film stripping effect was improved, compared with the recovery ratio after micro-displacement of the compound represented by the formula (4).
The present disclosure is not limited to the above embodiments. The above embodiments are merely examples, and embodiments having substantially the same configuration and exhibiting the same effects as those of the technical idea within the scope of the present disclosure are included in the technical scope of the present disclosure. It is to be noted that, within a range not departing from the gist of the present disclosure, various modifications which can be conceived by those skilled in the art are also included in the scope of the present disclosure, as well as other modes of constructing a combination of some of the constituent elements in the embodiments.
Claims (8)
1. A surfactant, characterized in that the surfactant has a structure represented by formula (3):
(3)
Wherein n is a positive integer, and n is 8 to 16.
2. The surfactant according to claim 1, wherein the surfactant is a nano supermolecule, and the amount of the nano supermolecule having a particle size of 10nm to 30nm in the surfactant is more than 90%.
3. The surfactant of claim 1, wherein the surfactant has an interfacial tension with water of less than 0.1 mN/m and a surface tension value with water of less than 20 mN/m.
4. A process for preparing a surfactant according to any one of claims 1 to 3, comprising:
mixing a compound shown in a formula (4) with cyclodextrin in an organic solution to obtain a mixed solution;
(4)
And (3) reacting the compound shown in the formula (4) in the mixed solution with cyclodextrin to prepare the surfactant.
5. The method according to claim 4, wherein the cyclodextrin is β -cyclodextrin, and the mass ratio of the compound represented by the formula (4) to cyclodextrin is (50-200): 1.
6. The method according to claim 4, wherein the step of reacting the compound represented by the formula (4) in the mixed solution with cyclodextrin to obtain the surfactant comprises:
stirring the mixed solution at a rotating speed of 400-600 rpm at 20-30 ℃ to enable the compound shown in the formula (4) in the mixed solution to react with cyclodextrin.
7. The production method according to claim 4, wherein the organic solution comprises 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-dimethylaminopyridine and an organic solvent, and the mass ratio of the 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride to the 4-dimethylaminopyridine is (2:1) to (10:1).
8. A imbibition agent for oil exploitation, characterized in that the imbibition agent comprises the surfactant of any one of claims 1 to 3 or the surfactant prepared by the preparation method of any one of claims 4 to 7 and water, wherein the mass content of the surfactant in the imbibition agent is 0.1 to 10%.
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