CN115161037A - Novel triple anionic nonionic surfactant and preparation method and application thereof - Google Patents
Novel triple anionic nonionic surfactant and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a novel triple anionic nonionic surfactant, and a preparation method and application thereof, and belongs to the technical field of organic synthesis. The novel triple anionic nonionic surfactant provided by the invention has a structural formula shown as a formula (1). The surfactant provided by the invention has a larger carbon chain length adjustment range, and the product has good alkali resistance, salt resistance, high temperature resistance and excellent interfacial activity, has good compatibility with polymers, and is suitable for application in the field of high-temperature and high-salinity reservoir development.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a novel triple anionic nonionic surfactant as well as a preparation method and application thereof.
Background
CN105312008A discloses a preparation method of a triple anionic-nonionic surfactant, which is characterized in that formaldehyde and alkylphenol polyoxyethylene are utilized to prepare an alkylphenol polyoxyethylene ether hydroxymethyl intermediate, then the intermediate is condensed with two times of alkylphenol polyoxyethylene ether, and an anionic group is connected to the tail end of polyoxyethylene ether of the obtained triple nonionic surfactant to prepare the triple anionic-nonionic surfactant.
CN110229050A discloses a preparation method of a triple anion-nonionic surfactant, which is prepared by preparing an alkylphenol polyoxyethylene ether hydroxymethyl intermediate from formaldehyde and alkylphenol polyoxyethylene ether and then directly condensing with twice the amount of alkylbenzene sulfonic acid.
Compared with the first method, the latter method is simpler, the product structure is exact, the yield is good, the industrial production of the triple anion-nonionic surfactant is realized, and the triple anion-nonionic surfactant is applied to products such as microemulsion oil displacement agents.
However, for the triple anionic-nonionic surfactant mentioned above, the problem of providing raw materials is limited, the adjustment of the carbon chain length is still limited, and the application of the surfactant with a triple structure is limited, so that how to develop a type with a larger adjustment range of the carbon chain length on the basis of the triple anionic-nonionic surfactant to meet the requirement of reservoir development is an important problem to be solved by the application.
Disclosure of Invention
The invention provides a novel triple negative non-ionic surfactant, a preparation method and application thereof, the adjustment range of the carbon chain length of the obtained surfactant is larger, and the product has good alkali resistance, salt resistance, high temperature resistance and excellent interfacial activity, has good compatibility with polymers, and is suitable for application in the field of high-temperature and high-salt reservoir development.
The invention provides a novel triple anion-nonionic surfactant, which has a structural formula shown as a formula (1):
wherein R is 1 Is C8-C20 alkyl, (CH) 2 CH 2 O) n is a polyoxyethylene group, n is an integer of 3 to 15;
R 2 、R 3 is at least one of C8-C20 alkyl, olefin and rosin radical;
y is an anionic group;
m is Na + 、K + Or NH 4 + At least one of (a).
Preferably, the anionic group is at least one selected from the group consisting of ethylcarboxylic acid, ethylsulfonic acid, propylcarboxylic acid, propylsulfonic acid, and hydroxypropanesulfonic acid.
The invention also provides a preparation method of the triple anion-nonionic surfactant, which comprises the steps of reacting alkylphenol polyoxyethylene with formaldehyde under alkaline conditions to form a dimethylol intermediate, then reacting the dimethylol intermediate with organic primary amine to form Mannich base, and reacting the Mannich base with halogenated alkyl carboxylate or halogenated alkyl sulfonate to introduce an anion group to prepare the triple anion-nonionic surfactant.
Preferably, the method comprises the following steps:
adding 1.0mol of alkylphenol polyoxyethylene into a reaction container, adding liquid alkali or solid alkali and an organic solvent, then adding 2.5-3.0 mol of trioxymethylene or dropwise adding 190-230 g of 40% formaldehyde solution, keeping the temperature at 50-60 ℃, stirring for reaction for 4-8h, and removing the organic solvent and unreacted formaldehyde in vacuum to obtain an alkylphenol polyoxyethylene dihydroxymethyl intermediate, wherein the structural formula is shown as formula (2):
continuously adding 2mol of organic primary amine into a reaction container, gradually heating to 90-110 ℃ under the protection of nitrogen, dropwise adding 1mol of alkylphenol polyoxyethylene ether dimethylol intermediate for 1-2 h, heating to 120-140 ℃ after dropwise adding, continuously stirring for reaction for 2-3h, performing vacuum dehydration for 1-2 h, and cooling to 50-60 ℃ to obtain the phenolic Mannich base intermediate, wherein the structural formula of the phenolic Mannich base intermediate is shown as the formula (3):
adding the obtained product into a mixed solution of an organic solvent and water, stirring until the solution is clear, adding 2.5-3.5 mol of halogenated carboxylic acid/sulfonate in batches, continuously adding an alkaline solution during the reaction, keeping the pH value at 8-10, reacting for 5-6 h, cooling to room temperature, adjusting the pH value to be neutral by using hydrochloric acid, and removing inorganic salt at the bottom to obtain the triple anionic-nonionic surfactant.
In the preparation method, the first two steps of reaction belong to the preparation of phenolic Mannich base. Usually, the phenolic aldehyde type Mannich base is prepared by adopting a one-step method, namely, alkylphenol and derivatives thereof, aldehyde and amine are added at one time and condensed at a certain temperature to obtain the Mannich base, and the product can be used as an epoxy curing agent. However, the one-step method has the disadvantages of mixing of the product with unreacted raw materials, low purity, complex components, easiness in self-polymerization, implosion, product agglomeration and the like, and for the one-step method for preparing the surfactant, the exact structure and good performance are difficult to obtain.
According to the scheme, the phenolic Mannich base is prepared by adopting a two-step method, the alkylphenol polyoxyethylene ether is reacted with formaldehyde in the first step under the alkaline condition to prepare the alkylphenol polyoxyethylene ether dimethylol intermediate, the yield of the dimethylol intermediate is high under the alkaline lower temperature condition and the excessive formaldehyde, and the unreacted formaldehyde is removed by vacuumizing, so that the occurrence of subsequent side reactions is reduced. And the second step of the reaction of the dimethylol intermediate and the organic primary amine adopts a charging mode of dripping the dimethylol intermediate into the organic primary amine, thereby avoiding the self-polymerization of the intermediate, controlling the reaction temperature to 90-110 ℃ in the period, rapidly discharging the water generated by condensation, assisting vacuum dehydration, accelerating the completion of the reaction, reducing the occurrence of side reactions and improving the yield of the product. Subsequently, through the reaction of the amine group and the halide, the anion group is connected, which belongs to the more classical substitution reaction, and under the condition of controlling the temperature, the solvent, the pH value and the material proportion, higher yield can be obtained.
In a word, the triple anionic-nonionic surfactant provided by the scheme has a novel structure, takes alkylphenol ethoxylates as a center, is connected with fatty amine type anionic surfactants on two sides, has anionic groups and nonionic groups in molecules, has the temperature resistance and salt resistance of the anionic and nonionic surfactants, has lower CMC (carboxy methyl cellulose) than that of gemini surfactants in a triple structure, and is easy to realize good interfacial activity under low concentration. The method has the advantages of simple preparation process, mild reaction conditions, exact structure of the prepared triple anion-nonionic surfactant, single component and high purity, can realize excellent performance, and is easy to realize industrial production.
Preferably, the alkylphenol ethoxylate is at least one of alkylphenol with a carbon chain length of C8-C20 and a polyoxyethylene chain length of 3-20;
the halogenated carboxylic acid/sulfonate is selected from at least one of sodium chloroacetate, sodium chloroethyl sulfonate, sodium chloropropionate, sodium chloropropyl sulfonate and sodium chlorohydroxypropane sulfonate.
Preferably, the mass ratio of the added alkylphenol polyoxyethylene ether, liquid alkali or solid alkali, formaldehyde and organic primary amine is 1.0 to 0.45, (2.5-3.0) to 2.0.
Preferably, the liquid or solid base is selected from NaOH and/or KOH, preferably NaOH.
Preferably, when a liquid base or a solid base is used, the formaldehyde is used in combination with solid/liquid formaldehyde, and the method includes two modes of adding liquid formaldehyde dropwise when the solid base is used and adding solid formaldehyde when the liquid base is used. It is understood that, in the step of obtaining the alkylphenol ethoxylate dimethylol intermediate, trioxymethylene and liquid formaldehyde may be used in combination as long as the water content of the system can be maintained at an appropriate level.
Preferably, the organic solvent is selected from at least one of methanol, ethanol and isopropanol;
the organic primary amine is selected from at least one of C8-C20 linear alkylamine, unsaturated fatty amine and rosin amine;
the alkaline solution comprises NaOH, KOH or NH 4 At least one of OH solutions.
The invention also provides a method for preparing the sameThe triple negative non-ionic surfactant has a formation temperature of 87 ℃ and a total mineralization degree of formation water of 298446mg/l, wherein Ca 2+ 10664mg/l、Mg 2+ 867mg/l of oil reservoir displacement oil.
Preferably, the surfactant is prepared into 50% sample solution by fatty alcohol-polyoxyethylene ether carboxylate, then the sample solution is further prepared into 0.3% sample solution by formation water, and when the oil deposit is applied, the interfacial tension is less than or equal to 2.6 multiplied by 10 -3 mN/m。
Preferably, the interfacial tension is less than or equal to 3.8X 10 when the oil reservoir is applied after the use concentration is 0.3 percent and the temperature is kept for 30 days at 87 DEG C -3 mN/m。
Compared with the prior art, the invention has the advantages and positive effects that:
1. the fatty amine connected with the two sides of the triple anion-nonionic surfactant provided by the invention has a larger adjustment range of carbon chain length than that of the fatty amine connected with the two sides of the triple anion-nonionic surfactant in the prior patent, and the triple anion-nonionic surfactant has easily available raw materials and can be customized to a more suitable product for specific application.
2. The triple anion-nonionic surfactant provided by the invention has long-chain alkylamine and carboxylic acid/sulfonic acid hydrophilic groups in molecules, so that functional groups in the molecules are enriched, and the diversity and the versatility of products are enhanced.
3. According to the triple anion-nonionic surfactant provided by the invention, the fatty amine connected at two sides is in a tertiary amine structure, and can show cationic property when the pH is lower, but due to the existence of alkylphenol ethoxylates, precipitation cannot be generated when an inner salt is formed at an isoelectric point, and the use in an acidic environment is increased.
4. According to the preparation method provided by the invention, under the condition that organic primary amine is remained in the reaction of the third step, the organic primary amine can be converted into aliphatic amine carboxylic acid or sulfonic acid type surfactant through the reaction of the third step, and purification is not required under most conditions, so that the product application is convenient.
5. The final product of the third step reaction is a solution of a triple anion-nonionic surfactant sulfonate or carboxylate, and the solution with a certain concentration can be directly prepared according to needs, so that the application is convenient.
6. The triple anion-nonionic surfactant obtained by the invention has good alkali resistance, salt resistance, high temperature resistance and excellent interfacial activity, has good compatibility with polymers, and is particularly suitable for application in the field of high-temperature and high-salinity reservoir development.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
EXAMPLE 1 preparation of nonylphenol polyoxyethylene ether-3,5-dimethylene-sodium didodecylamide acetate
Adding 1.0mol of nonylphenol polyoxyethylene ether (3 EO) into a reaction vessel, adding 60g of 30% sodium hydroxide, adding 100mL of methanol, adding 2.5mol of trioxymethylene, keeping the temperature at 50-60 ℃, stirring for reaction for 4 hours, and vacuumizing to remove an organic solvent and unreacted formaldehyde for later use;
adding 2mol of dodecylamine into another reaction container, gradually heating to 90-110 ℃ under the protection of nitrogen, dropwise adding 1.0mol of a nonylphenol polyoxyethylene ether dimethylol intermediate for 1-2 h, heating to 120-140 ℃ after dropwise adding, continuously stirring for reaction for 2h, performing vacuum dehydration for 1h, and cooling to 50-60 ℃;
adding 500mL of ethanol and 100mL of water into the phenolic Mannich base intermediate, stirring until the solution is clear, adding 2.5mol of sodium chloroacetate in batches, continuously adding a sodium hydroxide solution during the reaction, keeping the pH value at 8-10, reacting for 5-6 h, cooling to room temperature, adjusting the pH value to be neutral by using hydrochloric acid, standing to remove inorganic salt at the bottom, and obtaining nonylphenol polyoxyethylene ether-3,5-dimethylene-sodium didodecylamide acetate.
Example 2 preparation of Octylphenol polyoxyethylene Ether-3,5-Dimethylene-Dioctadecylamine Ethyl sodium sulfonate
Adding 1.0mol of octyl phenol polyoxyethylene ether (8 EO) into a reaction vessel, adding 18g of solid sodium hydroxide, adding 100mL of methanol, adding 190g of 40% formaldehyde, keeping the temperature at 50-60 ℃, stirring for reaction for 4h, and vacuumizing to remove the organic solvent and unreacted formaldehyde for later use;
adding 2mol of octadecylamine into another reaction container, gradually heating to 90-110 ℃ under the protection of nitrogen, dropwise adding 1.0mol of octyl phenol polyoxyethylene ether dimethylol intermediate for 1-2 h, heating to 120-140 ℃ after dropwise adding, continuously stirring for reaction for 2h, performing vacuum dehydration for 1h, and cooling to 50-60 ℃;
adding 500mL of ethanol and 100mL of water into the phenolic Mannich base intermediate, stirring until the solution is clear, adding 2.5mol of chloroethyl sodium sulfonate in batches, continuously adding a sodium hydroxide solution during the reaction, keeping the pH value at 10-11, reacting for 5-6 h, cooling to room temperature, adjusting the pH value to be neutral by using hydrochloric acid, standing to remove bottom inorganic salt, and obtaining the octyl phenol polyoxyethylene ether-3,5-dimethylene-dioctadecylamine ethyl sodium sulfonate.
EXAMPLE 3 preparation of nonylphenol polyoxyethylene ether-3,5-dimethylene-bisdodecylamine ammonium hydroxypropanesulfonate
Adding 1.0mol of nonylphenol polyoxyethylene ether (5 EO) into a reaction vessel, adding 60g of 30% sodium hydroxide, adding 100mL of methanol, adding 2.5mol of trioxymethylene, keeping the temperature at 50-60 ℃, stirring for reaction for 4 hours, and vacuumizing to remove an organic solvent and unreacted formaldehyde for later use;
adding 2mol of dodecylamine into another reaction container, gradually heating to 90-110 ℃ under the protection of nitrogen, dropwise adding 1.0mol of a nonylphenol polyoxyethylene ether dimethylol intermediate for 1-2 h, heating to 120-140 ℃ after dropwise adding, continuously stirring for reaction for 2h, performing vacuum dehydration for 1h, and cooling to 50-60 ℃;
adding 500mL of ethanol and 100mL of water into the phenolic Mannich base intermediate, stirring until the solution is clear, adding 2.5mol of 3-chloro-2-hydroxypropanesulfonic acid sodium salt in batches, continuously adding a sodium hydroxide solution during the reaction, keeping the pH value at 8-10, reacting for 5-6 h, cooling to room temperature, adjusting the pH value to be neutral by using hydrochloric acid, standing to remove inorganic salt at the bottom, and obtaining nonylphenol polyoxyethylene ether-3,5-dimethylene-didodecylamine hydroxypropanesulfonic acid sodium salt.
EXAMPLE 4 sodium dodecyl phenol polyoxyethylene ether-3,5-methylene-dicocoamine acetate
Adding 1.0mol of dodecylphenol polyoxyethylene ether (15 EO) into a reaction vessel, adding 63g of 40% potassium hydroxide, adding 100mL of methanol, adding 2.5mol of trioxymethylene, keeping the temperature at 50-60 ℃, stirring for reaction for 4 hours, and vacuumizing to remove an organic solvent and unreacted formaldehyde for later use;
adding 2mol of cocoamine (C8-C14 straight-chain alkane and olefin mixed amine) into another reaction container, gradually heating to 90-110 ℃ under the protection of nitrogen, dropwise adding 1.0mol of a dodecyl phenol polyoxyethylene ether dimethylol intermediate for 1-2 h, heating to 120-140 ℃ after dropwise adding, continuously stirring for reaction for 2h, vacuum dehydrating for 1h, and cooling to 50-60 ℃;
adding 500mL of ethanol and 100mL of water into the phenolic Mannich base intermediate, stirring until the solution is clear, adding 2.5mol of sodium chloroacetate in batches, continuously adding a sodium hydroxide solution during the reaction, keeping the pH value at 8-10, reacting for 5-6 h, cooling to room temperature, adjusting the pH value to be neutral by using hydrochloric acid, standing to remove inorganic salts at the bottom, and obtaining the sodium dodecyl phenol polyoxyethylene ether-3,5-dimethyl methylene-dicocoamine acetate.
Description of the invention: in the structural formula R 2 、R 3 Is coconut oil radical with C8-C14 carbon number.
EXAMPLE 5 preparation of sodium dodecylphenol polyoxyethylene 3,5-methylene-bis (rosin amine) acetate
Adding 1.0mol of dodecyl phenol polyoxyethylene ether (20 EO) into a reaction vessel, adding 60g of 30% sodium hydroxide, adding 100mL of methanol, adding 2.5mol of trioxymethylene, keeping the temperature at 50-60 ℃, stirring for reaction for 4 hours, and vacuumizing to remove an organic solvent and unreacted formaldehyde for later use;
adding 2mol of rosin amine into another reaction container, gradually heating to 90-110 ℃ under the protection of nitrogen, dropwise adding 1.0mol of a dodecyl phenol polyoxyethylene ether dimethylol intermediate for 1-2 h, heating to 120-140 ℃ after dropwise adding, continuously stirring for reacting for 2h, performing vacuum dehydration for 1h, and cooling to 50-60 ℃;
adding 500mL of ethanol and 100mL of water into the phenolic Mannich base intermediate, stirring until the solution is clear, adding 2.5mol of sodium chloroacetate in batches, continuously adding a sodium hydroxide solution during the reaction, keeping the pH value at 8-10, reacting for 5-6 h, cooling to room temperature, adjusting the pH value to be neutral by using hydrochloric acid, standing to remove inorganic salts at the bottom, and obtaining the sodium dodecyl phenol polyoxyethylene ether-3,5-dimethyl methylene-bis-rosin amine acetate.
Description of the drawings: in the structural formula R 2 、R 3 Is a rosin group, and has the following specific structure:
EXAMPLE 6 preparation of Polyoxyethylene nonyl phenol Ether-3,5-methylene-bis tallow amine Hydroxypropylene sodium sulfonate
Adding 1.0mol of nonylphenol polyoxyethylene ether (5 EO) into a reaction vessel, adding 60g of 30% sodium hydroxide, adding 100mL of methanol, adding 2.5mol of trioxymethylene, keeping the temperature at 50-60 ℃, stirring for reaction for 4 hours, and vacuumizing to remove an organic solvent and unreacted formaldehyde for later use;
adding 2mol of tallow amine into another reaction container, gradually heating to 90-110 ℃ under the protection of nitrogen, dropwise adding 1.0mol of nonylphenol polyoxyethylene ether dimethylol intermediate for 1-2 h, heating to 120-140 ℃ after dropwise adding, continuously stirring for reaction for 2h, vacuum dehydrating for 1h, and cooling to 50-60 ℃;
adding 500mL of ethanol and 100mL of water into the phenolic Mannich base intermediate, stirring until the solution is clear, adding 3.0mol of 3-chloro-2-hydroxypropanesulfonic acid sodium salt in batches, continuously adding a sodium hydroxide solution during the reaction, keeping the pH value at 8-10, reacting for 5-6 h, cooling to room temperature, adjusting the pH value to be neutral by using hydrochloric acid, standing to remove inorganic salts at the bottom, and obtaining nonylphenol polyoxyethylene ether-3,5-dimethylene-ditallowamine hydroxypropanesulfonic acid sodium salt.
Performance testing
The products of examples 1-6 were added to a defined amount of water and alcohol to prepare sample solutions having an effective content of 50%, which were numbered as samples 1-6, respectively, and tested for their respective properties.
Salt resistance test
The 1.0% solution of each sample was prepared with a simulated saline solution containing 250000mg/l NaCl, and after stirring uniformly, the presence or absence of precipitation and delamination was observed. The test results are shown in table 1.
TABLE 1 salt resistance test
Adaptability to pH value
1.0 percent solution of each sample is prepared by tap water, hydrochloric acid or sodium hydroxide solution is gradually dripped respectively, the pH is adjusted to be between 3 and 10, and the turbidity and the precipitation are observed. The test results are shown in table 2.
TABLE 2pH Adaptation
Interfacial tension
Selecting samples 1-6, adding a fatty alcohol polyoxyethylene ether carboxylate (AEC-5) surfactant to prepare 50% of oil displacement agent samples, numbering the samples in sequence, and measuring the interfacial tension of the samples. Meanwhile, 50 percent of fatty alcohol-polyoxyethylene ether carboxylate is taken as a reference.
The product is applied to a certain block of the original oilfield, and the total salinity of formation water is 298446mg/l, wherein Ca 2+ 10664mg/l、Mg 2+ 867mg/l, formation temperature 87 ℃.
A0.3% sample solution was prepared with formation water, crude oil was block dehydrated, and interfacial tension was measured at 87 ℃ using a TX-500C interfacial tensiometer.
TABLE 3 interfacial tension
Temperature resistance test
The oil displacement agents prepared from the samples 1 to 6 are respectively prepared into 0.3 percent sample solution by using formation water, the solution is packaged in an ampoule under the protection of nitrogen, the ampoule is placed in a thermostat at 87 ℃ for 30 days, and after the solution is taken out, the interfacial tension is measured, and the test conditions are the same as those of the example 9. Meanwhile, 50 percent of fatty alcohol polyoxyethylene ether carboxylate is taken as a reference.
TABLE 4 temperature resistant back interfacial tension
The data show that the triple negative non-ionic surfactant has the advantages of temperature resistance, salt resistance, acid-base adaptability, good interfacial tension and good compatibility with polymers, and can be effectively applied to the development of high-temperature and high-salinity oil reservoirs.
Claims (12)
1. The novel triple negative nonionic surfactant is characterized by having a structural formula shown as a formula (1):
wherein R is 1 Is C8-C20 alkyl, (CH) 2 CH 2 O) n is a polyoxyethylene group, n is an integer of 3 to 15;
R 2 、R 3 is at least one of C8-C20 alkyl, olefin and rosin;
y is an anionic group;
m is Na + 、K + Or NH 4 + At least one of (1).
2. The triple negative nonionic surfactant according to claim 1, wherein said anionic group is selected from at least one of ethyl carboxylic acid, ethyl sulfonic acid, propyl carboxylic acid, propyl sulfonic acid, hydroxypropane sulfonic acid group.
3. The preparation method of the triple negative nonionic surfactant according to claim 1 or 2, characterized in that alkyl phenol polyoxyethylene ether is reacted with formaldehyde under alkaline conditions to form a dimethylol intermediate, then the dimethylol intermediate is reacted with organic primary amine to form a Mannich base, and the Mannich base is reacted with halogenated alkyl carboxylate or halogenated alkyl sulfonate to introduce an anionic group to prepare the triple negative nonionic surfactant.
4. The method of claim 3, comprising the steps of:
adding 1.0mol of alkylphenol polyoxyethylene into a reaction container, adding liquid alkali or solid alkali and an organic solvent, then adding 2.5-3.0 mol of trioxymethylene or dropwise adding 190-230 g of 40% formaldehyde solution, keeping the temperature at 50-60 ℃, stirring for reaction for 4-8h, and removing the organic solvent and unreacted formaldehyde in vacuum to obtain an alkylphenol polyoxyethylene dihydroxymethyl intermediate;
continuously adding 2mol of organic primary amine into a reaction container, gradually heating to 90-110 ℃ under the protection of nitrogen, dropwise adding 1mol of alkylphenol polyoxyethylene ether dimethylol intermediate for 1-2 h, heating to 120-140 ℃ after dropwise adding, continuously stirring for reaction for 2-3h, performing vacuum dehydration for 1-2 h, and cooling to 50-60 ℃ to obtain a phenolic Mannich base intermediate;
and adding the obtained product into a mixed solution of an organic solvent and water, stirring until the solution is clear, adding 2.5-3.5 mol of halogenated carboxylic acid/sulfonate in batches, continuously adding an alkaline solution during the reaction, keeping the pH value at 8-10, reacting for 5-6 h, cooling to room temperature, adjusting the pH value to be neutral by using hydrochloric acid, and removing inorganic salt at the bottom to obtain the triple anion-nonionic surfactant.
5. The method according to claim 3 or 4, wherein the alkylphenol ethoxylate is at least one of alkylphenol having a carbon chain length of C8-C20 and a polyoxyethylene chain length of 3-20;
the halogenated carboxylic acid/sulfonate is selected from at least one of sodium chloroacetate, sodium chloroethyl sulfonate, sodium chloropropionate, sodium chloropropyl sulfonate and sodium chlorohydroxypropane sulfonate.
6. The preparation method according to claim 4, wherein the mass ratio of the alkylphenol ethoxylates, the liquid or solid base, the formaldehyde and the organic primary amine added is 1.0 to 0.45 (2.5-3.0) to 2.0.
7. The method of claim 6, wherein the liquid or solid base is selected from NaOH and/or KOH.
8. The method of claim 7, wherein the formaldehyde is used in combination with solid/liquid formaldehyde when a liquid base or a solid base is used, and the method comprises adding the liquid formaldehyde dropwise when the solid base is used and adding the solid formaldehyde when the liquid base is used.
9. The production method according to claim 4, wherein the organic solvent is selected from at least one of methanol, ethanol, and isopropanol;
the organic primary amine is selected from at least one of C8-C20 linear alkylamine, unsaturated fatty amine and rosin amine;
the alkaline solution comprises NaOH, KOH or NH 4 At least one of OH solutions.
10. The triple negative nonionic surfactant of claim 1 or 2 wherein Ca is present at a formation temperature of 87 ℃ and a total salinity of formation water of 298446mg/l 2+ 10664mg/l、Mg 2+ 867mg/l of oil reservoir displacement oil.
11. The use of claim 10, wherein the surfactant is formulated with fatty alcohol-polyoxyethylene ether carboxylate as a 50% sample solution and then with formation water as a 0.3% sample solution, and the interfacial tension is 2.6 x 10 or less when the oil reservoir is used -3 mN/m。
12. The use according to claim 10, wherein the interfacial tension is 3.8 x 10 or less when the oil reservoir is used after 30 days at 87 ℃ at a use concentration of 0.3% -3 mN/m。
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| CN111763510A (en) * | 2020-07-07 | 2020-10-13 | 山东新港化工有限公司 | Temperature-resistant salt-resistant surfactant for pressure reduction and injection augmentation and preparation method and application thereof |
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| CN114672296A (en) * | 2022-03-15 | 2022-06-28 | 中国石油大学(华东) | Efficient blocking remover for polymer flooding oilfield composite blockage and preparation method and application thereof |
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| CN101705083A (en) * | 2009-11-16 | 2010-05-12 | 山东德仕化工集团有限公司 | Formulation of surfactant oil displacement system for anionic and nonionic oil displacement |
| CN103540305A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Surfactant composition for chemical displacement of reservoir oil and preparation method thereof |
| CN104232047A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Surface active agent composition for tertiary oil recovery and preparation method and application thereof |
| US20220145164A1 (en) * | 2019-11-20 | 2022-05-12 | Petrochina Company Limited | Permeability-enhancing flooding system for tight oil reservoirs, and preparation and use thereof |
| CN110684519A (en) * | 2019-12-09 | 2020-01-14 | 山东新港化工有限公司 | Stratum adsorption resistant viscosity-reduction oil displacement agent for thick oil and application thereof |
| CN111763510A (en) * | 2020-07-07 | 2020-10-13 | 山东新港化工有限公司 | Temperature-resistant salt-resistant surfactant for pressure reduction and injection augmentation and preparation method and application thereof |
| CN114672296A (en) * | 2022-03-15 | 2022-06-28 | 中国石油大学(华东) | Efficient blocking remover for polymer flooding oilfield composite blockage and preparation method and application thereof |
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