CN115851281A - Naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant and preparation method thereof - Google Patents
Naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant and a preparation method thereof, which takes naphthenic acid and ethylenediamine as raw materials and generates naphthenic acid amide by dehydration of a water-carrying agent at a certain temperature; naphthenic acid amide and ethylene carbonate are subjected to ring-opening polymerization under the action of a catalyst to generate naphthenic acid amide polyether ester; the naphthenic acid amide polyether ester is sulfonated by 3-chlorine-2-hydroxy propane sodium sulfonate to prepare the naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant. The synthesis method has the characteristics of rich raw material resources, simple and controllable synthesis process, excellent product performance, wide adaptability and the like. The binary oil displacement system composed of the surfactant and polyacrylamide can keep ultralow interfacial tension in a wider concentration range, and has good oil-water compatibility and stable interfacial performance. The binary system has good salt resistance, hard water resistance, viscosity retention rate and long-term stability, and strong adsorption resistance, and can realize the improvement of the recovery ratio by more than 20% after water flooding.
Description
Technical Field
The invention belongs to a novel surfactant, and particularly relates to an ultra-low interfacial tension surfactant of naphthenic acid amide polyether ester sulfonate and a preparation method thereof.
Background
Most of the developments of domestic oil fields are in the middle and later stages, the water content in part of oil well produced liquid reaches over 90 percent, and all major oil fields are in full development of tertiary oil recovery technology. The chemical oil displacement technology is one of the technologies with the most development potential for improving the recovery efficiency, and the injection swept volume is enlarged by increasing the viscosity of an injection system, improving the fluidity ratio; the aim of improving the recovery ratio is finally fulfilled by means of reducing the oil-water interfacial tension, improving the oil washing capacity of a displacement system and the like. At present, the chemical oil displacement technology is applied to Daqing oil fields, liaohe oil fields, shengli oil fields, xinjiang oil fields and the like in a large area, and becomes a necessary way for the development of late and middle development stages of oil fields and old oil fields to develop the aftereffect.
The chemical oil displacement technology represented by the ASP technology is widely researched and applied in recent years, such as a ternary strong base complex oil displacement system with publication number CN1344776A and name of ternary complex oil displacement system and application of plant carboxylic acid surfactant, and a ternary weak base complex oil displacement system with publication number CN105505366A and name of weak base ternary complex oil displacement agent containing hydroxyl substituted aryl alkyl sulfonate surfactant. Although ASP (ASP-ASP) which is a three-element combination flooding technology popularized in Daqing oil fields is stable to a certain extent and increases the yield of crude oil, the measures cannot be comprehensively popularized all the time due to the factors of high exploitation cost, high subsequent treatment difficulty and the like. For ASP (surfactant + polymer + alkali), alkali in a ternary system is a double-edged sword, which is helpful for greatly improving the recovery efficiency, but also brings many engineering difficulties. In the process of an ASP flooding field test, it is found that strong base (sodium hydroxide) in an ASP-ASP flooding system can cause the dispersion and migration of stratum clay, so that the stratum permeability is reduced, and alkali reacts with oil layer fluid and rock minerals to form alkali scale, such as carbonate scale and aluminosilicate scale, which damages the stratum and causes corrosion scale in a shaft; weak base (sodium carbonate) in the ternary weak base compound oil displacement system is sensitive to divalent ions in prepared sewage, and scaling of a ground injection system is easily caused; and the ternary combination flooding produced liquid is seriously emulsified by oil and water, and the difficulty and the cost of gathering, transporting and dehydrating treatment are greatly improved. The base also greatly reduces the viscoelasticity of the polymer, and the unfavorable fluidity ratio also leads to a viscous fingering phenomenon, greatly reducing swept volume.
In order to eliminate the adverse factors brought by alkali in a ternary composite oil displacement system, the ultra-low interfacial tension surfactant required by an alkali-free binary composite oil displacement system is developed and has ten advantagesThe method is of practical significance. The binary complex oil displacement system SP (surfactant + polymer) can exert the viscoelasticity of the polymer to the maximum extent; the corrosion and scaling phenomena caused by the existence of alkali are weakened, the ultralow interfacial tension and swept volume of a displacement system are maintained, the oil displacement effect is close to that of the ternary combination flooding, and the environmental protection performance of the chemical oil displacement technology is improved. According to the property of the target reservoir crude oil, a binary system which is directly formed with the polymer without adding alkali is developed by adjusting the molecular structure of the surfactant, and the aim of being less than 1 multiplied by 10 with the target reservoir crude oil can be achieved -2 The surfactant with ultra-low interface tension value of mN/m has gradually become a new research direction for tertiary oil recovery.
Along with the continuous deep exploitation of crude oil, the heavy components in the crude oil have higher and higher specific gravity, and most notably, the content of naphthenic acid in the crude oil is higher and higher. Wherein the Liaohe oil field, the Xinjiang oil field and the Shengli oil field are reservoirs with high naphthenic acid content in crude oil in China. Naphthenic acid is an organic acid present in petroleum, also known as petroleum acid. Naphthenic acid is widely used as a byproduct and a fine chemical raw material in the petroleum processing process. The naphthenic acid rich in crude oil is used as a raw material to produce the ultra-low interfacial tension surfactant required by a binary composite oil displacement system for crude oil exploitation, and the surfactant has more outstanding technical significance and application prospect.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant and a preparation method thereof.
The invention relates to a naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant which has the following structural formula:
in the above structural formula: m represents the degree of polymerization of a carbonate group in the structural formula, and m is any integer of 0-15;
in the above structural formula: n represents the polymerization degree of an ethoxy group in a structural formula, and is any integer from 0 to 15;
in the above structural formula: the sum of m and n is any integer of 5 to 15;
in the above structural formula: r represents a cycloalkyl group in the structural formula.
The preparation method of the naphthenic acid amide polyether ester sulfonate ultralow interfacial tension surfactant is realized by the following steps:
a. amidation reaction
Naphthenic acid and ethylenediamine are dehydrated under the action of water-carrying agent petroleum ether according to the mol ratio of 1-1.5 to prepare naphthenic acid amide, wherein the acid value of the naphthenic acid is 80-220 mgKOH/g;
b. ring opening polymerization
And c, under the action of a catalyst potassium hydroxide, performing ring-opening polymerization reaction on the naphthenic acid amide prepared in the step a and ethylene carbonate, wherein the molar ratio of the naphthenic acid amide to the ethylene carbonate is 1:5 to 15, preparing naphthenic acid amide polyether ester;
c. sulfonation reaction
And c, reacting the naphthenic acid amide polyether ester prepared in the step b with sodium hydroxide and 3-chloro-2-hydroxy propane sodium sulfonate under the condition that petroleum ether is used as a solvent to prepare the naphthenic acid amide polyether ester sulfonate.
As a further improvement of the invention, the step a amidation reaction is specifically carried out as follows: mixing naphthenic acid, ethylenediamine and water-carrying agent petroleum ether, stirring, heating, refluxing and dehydrating at 80-90 ℃, wherein the refluxing and dehydrating time is controlled to be 1-4 hours, and refluxing and dehydrating to obtain water with equimolar amount of naphthenic acid, namely, the dehydration is finished; then removing the water-carrying agent petroleum ether, controlling the end point temperature to be not more than 100 ℃, and completely removing the water-carrying agent petroleum ether to obtain naphthenic acid amide; the boiling range of the water-carrying agent petroleum ether is 60-90 ℃; the addition of the water-carrying agent petroleum ether is one time of the total mass of the naphthenic acid and the ethylenediamine; the molar ratio of naphthenic acid to ethylenediamine was 1.05.
As a further improvement of the invention, the acid value of the naphthenic acid is 160-180 mgKOH/g.
As a further improvement of the invention, the ring-opening polymerization reaction in the step b is specifically carried out by the following steps: b, adding a catalyst potassium hydroxide into the naphthenic acid amide prepared in the step a, fully replacing the inside of the reaction container with nitrogen, and completely replacing air in the reaction system; heating again, and adding ethylene carbonate when the temperature reaches 80 ℃; after the ethylene carbonate feeding is finished, raising the temperature to 145-150 ℃ for ring-opening polymerization reaction for 8-10 hours; after the reaction is finished, the temperature is reduced to 20-30 ℃, and the product is naphthenic acid amide polyether ester.
As a further improvement of the invention, the molar ratio of naphthenic acid amide to ethylene carbonate is 1; the addition of the catalyst potassium hydroxide is 5-10 per mill of the total mass of the naphthenic acid amide and the ethylene carbonate.
As a further improvement of the invention, the specific method of the sulfonation reaction in the step c is as follows: adding the naphthenic acid amide polyether ester prepared in the step b and solvent petroleum ether into a sulfonation reaction kettle, starting stirring, then adding sodium hydroxide, heating the sulfonation reaction kettle to 80-90 ℃, and carrying out alkalization reaction for 1-2 hours under a reflux state; after the alkalization is finished, the temperature of the sulfonation reaction kettle is reduced to 60-70 ℃, 40% of 3-chloro-2-hydroxy propane sodium sulfonate aqueous solution is dripped, the dripping time is controlled to be 0.5-1 hour, and the continuous reaction is carried out for 4-6 hours at the temperature of 60-70 ℃ after the dripping is finished; after the reaction is finished, removing the solvent petroleum ether under negative pressure in a stirring state; after the solvent petroleum ether is removed, adding deionized water into the reaction kettle to prepare an aqueous solution, stirring for 0.5-1 hour, and taking out a product to obtain a naphthenic acid amide polyether ester sulfonate ultralow interfacial tension surfactant product;
the boiling range of the solvent petroleum ether is 60-90 ℃, and the addition of the petroleum ether solvent is 50% of the mass of the naphthenic acid amide polyether ester; the naphthenic acid amide polyether ester and sodium hydroxide are mixed according to the mol ratio of 1:1 to 1.5; the mol ratio of the naphthenic acid amide polyether ester to the 3-chlorine-2-hydroxy propane sodium sulfonate is 1:1 to 1.5; the addition amount of the deionized water is one time of the total mass of the naphthenic acid amide polyether ester and the 3-chlorine-2-hydroxy propane sodium sulfonate.
As a further improvement of the invention, the mol ratio of the naphthenic acid amide polyether ester to the sodium hydroxide is 1; the mol ratio of the naphthenic acid amide polyether ester to the 3-chlorine-2-hydroxy propane sodium sulfonate is 1.
The surfactant with ultralow interfacial tension of the naphthenic acid amide polyether ester sulfonate disclosed by the invention and polyacrylamide form a binary oil displacement system, the ultralow interfacial tension can be kept in a wider concentration range (the effective concentration is 0.05-0.5%, the mineralization degree is 1000-8000 mg/L and the temperature is 45 ℃), and the surfactant is good in oil-water compatibility and stable in interfacial performance. The binary system has better salt resistance, hard water resistance, viscosity retention rate and long-term stability, and stronger adsorption resistance. By means of a binary system oil displacement experiment of the artificial rock core, the recovery ratio can be improved by more than 20% after water displacement.
Detailed Description
Example 1
The preparation method of the naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant is realized by the following steps:
a. amidation reaction
Sequentially adding naphthenic acid, ethylenediamine and water-carrying agent petroleum ether into a dehydration kettle, starting stirring, heating, refluxing and dehydrating at the temperature of 80-90 ℃, controlling the refluxing and dehydrating time to be 1-4 hours, refluxing and dehydrating to remove equimolar water of naphthenic acid, namely, after dehydration is finished, removing the water-carrying agent petroleum ether under negative pressure, controlling the end point temperature to be not more than 100 ℃, and completely removing the water-carrying agent petroleum ether to obtain naphthenic acid amide;
the reaction formula is as follows:
the boiling range of the water-carrying agent petroleum ether is 60-90 ℃; the addition of the water-carrying agent petroleum ether is one time of the total mass of the naphthenic acid and the ethylenediamine; the molar ratio of naphthenic acid to ethylenediamine is 1; the acid value of the naphthenic acid is (80-220) mgKOH/g;
b. ring opening polymerization
And c, accurately metering the naphthenic acid amide prepared in the step a, transferring the naphthenic acid amide into a polymerization kettle, and adding a catalyst potassium hydroxide into the polymerization kettle. And starting a stirring and reflux condensing system of the polymerization kettle, fully replacing the reaction kettle with nitrogen, and completely replacing air in the reaction system. Starting a polymerization kettle temperature rising system, and starting to add the ethylene carbonate when the temperature of the polymerization kettle reaches 80 ℃. After the ethylene carbonate feeding is finished, the temperature of the polymerization kettle is raised to 145-150 ℃ for ring-opening polymerization reaction for 8-10 hours. After the reaction is finished, the temperature is reduced to 20-30 ℃, and the product is naphthenic acid amide polyether ester;
the reaction formula is as follows:
the mol ratio of naphthenic acid amide to ethylene carbonate is 1:5 to 15 percent; the addition amount of the catalyst potassium hydroxide is 5-10 per mill of the total mass of the naphthenic acid amide and the ethylene carbonate;
c. sulfonation reaction
And c, adding the naphthenic acid amide polyether ester prepared in the step b and solvent petroleum ether into a sulfonation reaction kettle, and starting stirring. Then adding sodium hydroxide, heating the sulfonation reaction kettle to 80-90 ℃, and carrying out alkalization reaction for 1-2 hours under a reflux state. After the alkalization is finished, the temperature of the sulfonation reaction kettle is reduced to 60-70 ℃, 40% of 3-chloro-2-hydroxypropanesulfonic acid sodium water solution is dripped, the dripping time is controlled to be 0.5-1 hour, and the reaction is continued for 4-6 hours at 60-70 ℃ after the dripping is finished. After the reaction is finished, the solvent petroleum ether is removed under negative pressure in a stirring state. After the solvent petroleum ether is removed, adding deionized water (one time of the total mass of the naphthenic acid amide polyether ester and the 3-chlorine-2-hydroxy propane sodium sulfonate) into a reaction kettle to prepare a water solution, stirring for 0.5 to 1 hour, and taking out a product to obtain the naphthenic acid amide polyether ester sulfonate ultralow interfacial tension surfactant;
the reaction formula is as follows:
the addition amount of the petroleum ether solvent is 50 percent of the mass of the naphthenic acid amide polyether ester; the naphthenic acid amide polyether ester and sodium hydroxide are mixed according to a molar ratio of 1: 1-1.5, wherein the mol ratio of the naphthenic acid amide polyether ester to the 3-chlorine-2-hydroxy propane sodium sulfonate is 1:1 to 1.5.
Example 2
The preparation method of the naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant is realized by the following steps:
a. amidation reaction: sequentially adding 1mol of naphthenic acid, 1.05mol of ethylenediamine and petroleum ether with a water-carrying agent into a dehydration kettle, wherein the addition amount of the petroleum ether is one time of the total mass of the naphthenic acid and the ethylenediamine, and starting stirring and heating. Controlling the temperature to be 80-90 ℃ for reflux dehydration, controlling the reflux dehydration time to be 4 hours, refluxing and removing equimolar amount of water (1 mol) of naphthenic acid, namely, after dehydration is finished, removing the petroleum ether with the water-carrying agent under negative pressure, controlling the end point temperature to be not more than 100 ℃, and completely removing the petroleum ether with the water-carrying agent to obtain the naphthenic acid amide; the acid value of the naphthenic acid is 160-180 mgKOH/g;
b. ring-opening polymerization: taking 1mol of naphthenic acid amide prepared by the amidation reaction, transferring the naphthenic acid amide into a polymerization kettle, adding potassium hydroxide catalyst into the polymerization kettle, closing the polymerization kettle, starting a stirring and reflux condensing system of the polymerization kettle, fully replacing the reaction kettle with nitrogen, completely replacing air in the reaction system, starting a heating system of the polymerization kettle, starting adding 10mol of ethylene carbonate when the temperature of the polymerization kettle reaches 80 ℃, and after the feeding of the ethylene carbonate is finished, raising the temperature of the polymerization kettle to 145-150 ℃ to perform ring-opening polymerization for 10 hours; after the reaction is finished, the temperature is reduced to 20 to 30 ℃, and the product is the naphthenic acid amide polyether ester. Wherein, the addition of the catalyst potassium hydroxide is 5 per mill of the total mass of the naphthenic acid amide and the ethylene carbonate;
c. sulfonation reaction: adding 1mol of naphthenic acid amide polyether ester prepared by the ring-opening polymerization reaction and solvent petroleum ether (boiling range is 60-90 ℃) into a sulfonation reaction kettle, starting stirring, and then adding 1.05mol of sodium hydroxide. Heating the sulfonation reaction kettle to 80-90 ℃, and carrying out alkalization reaction for 2 hours in a reflux state. After the alkalization is finished, the temperature of the sulfonation reaction kettle is reduced to 60-70 ℃, 40 percent of 3-chloro-2-hydroxy propane sodium sulfonate aqueous solution in 1.05mol is dripped, the dripping time is controlled to be 1 hour, and the reaction is continued for 6 hours at the temperature of 60-70 ℃ after the dripping is finished. After the reaction is finished, the solvent petroleum ether is removed under negative pressure in a stirring state. After the solvent petroleum ether is removed, deionized water (one time of the total mass of the naphthenic acid amide polyether ester and the 3-chlorine-2-hydroxy propane sodium sulfonate) is added into a reaction kettle to prepare a water solution, and the water solution is stirred for 1 hour to take out a product, so that the naphthenic acid amide polyether ester sulfonate ultralow interfacial tension surfactant is obtained.
The performance of the naphthenic acid amide polyether ester sulfonate prepared in example 2 is further illustrated below:
1. evaluation of interfacial tension of binary system of surfactants with different concentrations
According to the determination method of 6.3 in Q/SY1583-2013, a binary system solution with the concentrations of 0.05%,0.1%,0.2%,0.3%,0.4% and 0.5% and the concentration of 1000ppm of polyacrylamide is prepared from dehydrated crude oil of a south 7-1 united station in the ninth operation area of a Daqing oil field oil extraction second factory and 2500 ten thousand of polyacrylamide for oil displacement of Daqing refining company by adopting simulated saline water. And measuring the interfacial tension between the surfactant solution with different concentrations and the crude oil by adopting a TX-500C rotary drop interfacial tension instrument at the temperature of 45 ℃ and at the rotating speed of 5000 r/min. The results are shown in the following table:
as can be seen from the data in the table above, the binary oil displacement system consisting of the naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant and the polyacrylamide can be kept less than 1 multiplied by 10 within a wider range of 0.05 to 0.5 percent of effective concentration -2 Ultra-low interfacial tension requirement of mN/m.
2. Evaluation of viscosity and interfacial tension stability of binary System
According to the determination method of 6.9 in Q/SY1583-2013, a binary system solution of 0.2% naphthenate amide polyether ester sulfonate ultralow interfacial tension surfactant is prepared under the condition that the concentration of polyacrylamide is 1000ppm, the binary system solution is placed in an oven under the anaerobic condition of 45 ℃, the binary system solution is placed for 0 day, 1 day, 3 days, 7 days, 15 days, 30 days and 60 days respectively, the viscosity of the binary system solution is determined, and the interfacial tension between the binary system solution and crude oil is determined at the same time. The results are shown in the following table:
as can be seen from the data in the table, the binary oil displacement system consisting of the naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant and the polyacrylamide still maintains the interfacial tension of less than 1 multiplied by 10 within 60 days -2 The mN/m is in an ultra-low interfacial tension range, and the viscosity retention rate is still at a higher level. The viscosity retention rate within 30 days which is completely satisfied with the specification of Q/SY1583-2013 standard is more than or equal to 90 percent, and the interfacial tension is less than 1 multiplied by 10 -2 Ultra-low interfacial tension requirement of mN/m.
3. Evaluation of salt resistance of binary System
Preparing sodium chloride solutions with different degrees of mineralization by using distilled water, and preparing a binary system solution of 0.2 percent naphthenic acid amide polyether ester sulfonate ultralow interfacial tension surfactant by using water with different degrees of mineralization under the condition of polyacrylamide concentration of 1000 ppm. The interfacial tension between the crude oil and the crude oil was measured at 45 ℃ at a rotation speed of 5000 rpm. The results are shown in the following table:
as can be seen from the data in the table above, the binary oil displacement system consisting of the naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant and the polyacrylamide still maintains the interfacial tension less than 1 multiplied by 10 within the mineralization range of 1000-8000 mg/L -2 The ultra-low range of mN/m and good salt resistance.
4. Hard water resistance test of binary system
Preparing Ca-containing solutions with different concentrations by using distilled water 2+ +Mg 2+ Simulating hard water solution, polymerizationAt a compound concentration of 1000ppm, ca is used in different concentrations 2+ +Mg 2+ The solution is prepared into a binary system solution of 0.2 percent naphthenate amide polyether ester sulfonate ultralow interfacial tension surfactant. The interfacial tension between the crude oil and the crude oil was measured at 45 ℃ at a rotation speed of 5000 rpm. The results are shown in the following table:
as can be seen from the data in the table above, the binary oil displacement system consisting of the naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant and polyacrylamide is characterized in that Ca is used as the surfactant 2+ +Mg 2+ The interfacial tension is still kept less than 1 x 10 within the range of 10-50 mg/L - 2 The ultra-low range of mN/m and the hard water resistance are good.
5. Multiple adsorption experiment in binary system
According to a determination method of 6.4 in Q/SY1583-2013, preparing an ultralow interfacial tension surfactant solution of naphthenamide polyether ester sulfonate with the concentration of 0.2%, oscillating for 12 hours at 45 ℃ and oscillation frequency of 90 times/min according to a solid-to-liquid ratio of oil sand to the surfactant solution of 1. According to the experimental conditions, the adsorbed surfactant solution is taken to repeat the steps until the interfacial tension of the adsorbed surfactant solution is more than 1 x 10 -2 mN/m, the experiment was stopped and the interfacial tension at different adsorption times was recorded. The results are shown in the following table:
as can be seen from the data in the table above, after three adsorption experiments, the interfacial tension of the binary oil displacement system consisting of the naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant and polyacrylamide is still kept less than 1 multiplied by 10 -2 The ultra-low range of mN/m completely meets the requirements specified by Q/SY1583-2013 standard, and the adsorption resistance is good.
6. Binary system oil displacement experiment
The oil displacement effect of a binary system (S surfactant + P polymer) on an artificial rock core is tested according to a determination method in chapter 9 of Standard SY/T6424-2014 of composite oil displacement system performance test method.
6.1 Experimental conditions
(1) Core: homogeneous artificial physical cores were used, the core dimensions were 4.0cm × 4.0cm × 30cm, and the core gas logging permeability and porosity were as follows:
(2) Water for experiment: the water used for water flooding and binary system is standard simulated brine for Daqing oil field, and the formula of the simulated brine is shown in the following table:
| composition (A) | An addition (m/m)% |
| NaCl | 0.1249 |
| NaHCO 3 | 0.2929 |
| Na 2 CO 3 | 0.0191 |
| Na 2 SO 4 | 0.0006 |
| CaCl 2 | 0.0033 |
| MgCl 2 ·6H 2 O | 0.0059 |
(3) Chemical agents used in the experiment: the polymer adopts polyacrylamide with molecular weight of 2500 ten thousand for oil displacement of Daqing refining company, and the surfactant adopts the naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant.
(4) Experimental oil: the south 7-1 united station of the ninth operation area of Daqing oil field second plant dehydrates crude oil.
(5) Experiment temperature: all at 45 ℃.
(6) Injection speed: 20ml/h.
6.2 Experimental procedures
(1) After the core is pumped out for 4 hours, saturated simulated brine is used, and porosity is measured;
(2) Placing the rock core saturated with the simulated saline water in a constant temperature box, and keeping the temperature for more than 4 hours (45 ℃);
(3) Saturating the simulated crude oil, placing the core in a constant temperature box for more than 12 hours (45 ℃), and requiring that the crude oil saturation of the core is as close to the original oil saturation of the reservoir as possible;
(4) And (4) simulating oil displacement according to a standard specified flow of SY/T6424-2014 composite oil displacement system performance test method, and calculating the recovery ratio.
6.3 Experimental protocol
Scheme 1:
(1) simulating saline water flooding until the water content is 98%, and calculating the water flooding recovery ratio;
(2) injection of binary system 0.3pv: polyacrylamide with the concentration of 1500mg/L and the molecular weight of 2500 ten thousand, and the concentration of a surfactant is 0.3 percent;
(3) then injecting simulated saline water to drive until the water content is 98 percent, and calculating the total recovery ratio.
Scheme 2:
(1) simulating saline flooding until the water content is 98%, and calculating the water flooding recovery ratio;
(2) injection of binary system 0.3pv: the concentration of polyacrylamide with the molecular weight of 1500mg/L and 2500 ten thousand and the concentration of surfactant are 0.2 percent;
(3) then injecting simulated saline water to drive until the water content is 98 percent, and calculating the total recovery ratio.
Scheme 3:
(1) simulating saline flooding until the water content is 98%, and calculating the water flooding recovery ratio;
(2) injection of binary system 0.3pv: polyacrylamide with the concentration of 1000mg/L and the molecular weight of 2500 ten thousand, and the concentration of a surfactant is 0.3 percent;
(3) then injecting simulated saline water to drive until the water content is 98 percent, and calculating the total recovery ratio.
Scheme 4:
(1) simulating saline flooding until the water content is 98%, and calculating the water flooding recovery ratio;
(2) injection of binary system 0.3pv: polyacrylamide with the concentration of 1000mg/L and the molecular weight of 2500 ten thousand and the concentration of a surfactant of 0.2 percent;
(3) then injecting simulated saline water to drive until the water content is 98 percent, and calculating the total recovery ratio.
6.4 oil displacement experiment result data
The data in the table show that the naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant can improve the recovery ratio by more than 20% after water flooding in a binary system flooding experiment of the artificial rock core.
The experimental data are combined to show that the binary oil displacement system consisting of the naphthenic acid amide polyether ester sulfonate surfactant with ultra-low interfacial tension and the polyacrylamide can keep the ultra-low interfacial tension in a wider concentration range (the effective concentration is 0.05-0.5 percent, the mineralization degree is 1000-8000 mg/L, and the temperature is 45 ℃), and the binary oil displacement system has good oil-water compatibility and stable interfacial performance. The binary system has better salt resistance, hard water resistance, viscosity retention rate and long-term stability, and stronger adsorption resistance.
Claims (8)
1. The surfactant is characterized in that the surfactant has the following structural formula:
in the above structural formula: m represents the degree of polymerization of a carbonate group in the structural formula, and m is any integer of 0-15;
in the above structural formula: n represents the polymerization degree of an ethoxy group in the structural formula, and is any integer from 0 to 15;
in the above structural formula: the sum of m and n is any integer of 5 to 15;
in the above structural formula: r represents a cycloalkyl group in the structural formula.
2. A preparation method of a naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant is realized by the following steps:
a. amidation reaction
Naphthenic acid and ethylenediamine are dehydrated to prepare naphthenic acid amide under the action of petroleum ether with a water carrying agent according to the mol ratio of 1-1.5, and the acid value of the naphthenic acid is 80-220 mgKOH/g;
b. ring opening polymerization
And c, under the action of a catalyst potassium hydroxide, performing ring-opening polymerization reaction on the naphthenic acid amide prepared in the step a and ethylene carbonate, wherein the molar ratio of the naphthenic acid amide to the ethylene carbonate is 1:5 to 15, preparing naphthenic acid amide polyether ester;
c. sulfonation reaction
And c, reacting the naphthenic acid amide polyether ester prepared in the step b with sodium hydroxide and 3-chlorine-2-hydroxy propane sodium sulfonate under the condition that petroleum ether is used as a solvent to prepare the naphthenic acid amide polyether ester sulfonate.
3. The method for preparing the naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant as claimed in claim 2, wherein the amidation reaction in the step a is as follows:
mixing naphthenic acid, ethylenediamine and water-carrying agent petroleum ether, stirring, heating, refluxing and dehydrating at 80-90 ℃, wherein the refluxing and dehydrating time is controlled to be 1-4 hours, and refluxing and dehydrating to obtain water with equimolar amount of naphthenic acid, namely, the dehydration is finished; then removing the petroleum ether with the water-carrying agent, controlling the end point temperature to be not more than 100 ℃, and completely removing the petroleum ether with the water-carrying agent to obtain the naphthenic acid amide;
the reaction formula is as follows:
the boiling range of the water-carrying agent petroleum ether is 60-90 ℃; the addition of the water-carrying agent petroleum ether is one time of the total mass of the naphthenic acid and the ethylenediamine; the molar ratio of naphthenic acid to ethylenediamine was 1.05.
4. The method for preparing the naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant as claimed in claim 3, wherein the acid value of the naphthenic acid is 160-180 mgKOH/g.
5. The method for preparing the naphthenic acid amide polyether ester sulfonate ultralow interfacial tension surfactant according to claim 2, wherein the ring-opening polymerization reaction in the step b is as follows:
b, adding a catalyst potassium hydroxide into the naphthenic acid amide prepared in the step a, fully replacing the inside of the reaction container with nitrogen, and completely replacing oxygen in the reaction system; heating again, and adding ethylene carbonate when the temperature reaches 80 ℃; after the ethylene carbonate feeding is finished, raising the temperature to 145-150 ℃ for ring-opening polymerization reaction for 8-10 hours; after the reaction is finished, the temperature is reduced to 20-30 ℃, and the product is naphthenic acid amide polyether ester;
the reaction formula is as follows:
6. the method for preparing the naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant as claimed in claim 5, wherein the molar ratio of naphthenic acid amide to ethylene carbonate is 1; the addition of the catalyst potassium hydroxide is 5-10 per mill of the total mass of the naphthenic acid amide and the ethylene carbonate.
7. The method for preparing the naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant as claimed in claim 2, wherein the specific method of the sulfonation reaction in the step c is as follows:
adding the naphthenic acid amide polyether ester prepared in the step b and solvent petroleum ether into a sulfonation reaction kettle, starting stirring, then adding sodium hydroxide, heating the sulfonation reaction kettle to 80-90 ℃, and carrying out alkalization reaction for 1-2 hours under a reflux state; after the alkalization is finished, the temperature of the sulfonation reaction kettle is reduced to 60-70 ℃, 40% of 3-chloro-2-hydroxypropanesulfonic acid sodium water solution is dripped, the dripping time is controlled to be 0.5-1 hour, and the reaction is continued for 4-6 hours at 60-70 ℃ after the dripping is finished; after the reaction is finished, removing the solvent petroleum ether under negative pressure in a stirring state; after the solvent petroleum ether is removed, adding deionized water into a reaction kettle to prepare an aqueous solution, stirring for 0.5-1 hour, and taking out a product to obtain a naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant product;
the reaction formula is as follows:
the boiling range of the solvent petroleum ether is 60-90 ℃, and the addition of the petroleum ether solvent is 50% of the mass of the naphthenic acid amide polyether ester; the naphthenic acid amide polyether ester and sodium hydroxide are mixed according to a molar ratio of 1:1 to 1.5; the mol ratio of the naphthenic acid amide polyether ester to the 3-chlorine-2-hydroxy propane sodium sulfonate is 1:1 to 1.5; the addition amount of the deionized water is one time of the total mass of the naphthenic acid amide polyether ester and the 3-chlorine-2-hydroxy propane sodium sulfonate.
8. The method for preparing the naphthenic acid amide polyether ester sulfonate ultra-low interfacial tension surfactant as claimed in claim 7, wherein the molar ratio of the naphthenic acid amide polyether ester to the sodium hydroxide is 1; the mol ratio of the naphthenic acid amide polyether ester to the 3-chlorine-2-hydroxy propane sodium sulfonate is 1.
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| CN116410453B (en) * | 2023-04-14 | 2023-11-07 | 东北石油大学 | Oilfield transition layer treating agent and preparation method and application thereof |
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