CN115161037B - 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 application 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 application has a structural formula shown in a formula (1). The surfactant provided by the application has a larger adjustment range of carbon chain length, 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 oil reservoir development.
Description
Technical Field
The application belongs to the technical field of organic synthesis, and particularly relates to a novel triple anionic nonionic surfactant, and a preparation method and application thereof.
Background
CN105312008A discloses a preparation method of a trigeminy anionic-nonionic surfactant, which is prepared by preparing alkylphenol polyoxyethylene ether hydroxymethyl intermediate from formaldehyde and alkylphenol polyoxyethylene ether, condensing with twice alkylphenol polyoxyethylene ether, and connecting anionic groups at the polyoxyethylene ether end of the obtained trigeminy nonionic surfactant.
CN110229050a discloses a preparation method of a triple anionic-nonionic surfactant, which is prepared by preparing alkylphenol polyoxyethylene ether hydroxymethyl intermediate from formaldehyde and alkylphenol polyoxyethylene, and then directly condensing with twice of alkylbenzenesulfonic acid.
Compared with the first method, the latter method is simpler, the product structure is exact, the yield is good, the industrialized production of the triple anionic-nonionic surfactant is realized, and the method is applied to products such as microemulsion oil displacement agent and the like.
However, the above mentioned tri-anionic-nonionic surfactant is limited to the problem of providing raw materials, and the adjustment of the carbon chain length is still limited, which limits the application of the tri-anionic surfactant, so how to develop the type with a larger adjustment range of the carbon chain length based on the tri-anionic-nonionic surfactant to adapt to the requirement of oil reservoir development is an important problem to be solved by the application.
Disclosure of Invention
The application provides a novel triple anionic nonionic surfactant, a preparation method and application thereof, the carbon chain length of the obtained surfactant is larger in 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 development of high-temperature and high-salt oil reservoirs.
The application provides a novel triple anionic-nonionic surfactant, which has a structural formula shown in 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 from 3 to 15;
R 2 、R 3 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 them.
Preferably, the anionic group is at least one selected from the group consisting of ethyl carboxylic acid, ethyl sulfonic acid, propyl carboxylic acid, propyl sulfonic acid, and hydroxy propane sulfonic acid.
The application also provides a preparation method of the triple anionic-nonionic surfactant, which comprises the steps of reacting alkylphenol ethoxylates with formaldehyde under an alkaline condition to form a dihydroxymethyl intermediate, then reacting with organic primary amine to form Mannich base, and then reacting with halogenated alkyl carboxylate or halogenated alkyl sulfonate to introduce an anionic group.
Preferably, the method comprises the following steps:
adding 1.0mol of alkylphenol ethoxylate into a reaction vessel, 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 and reacting for 4-8h, and vacuum pumping the organic solvent and unreacted formaldehyde to obtain alkylphenol ethoxylate dihydroxymethyl intermediate, wherein the structural formula is shown in 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 ethoxylate dimethylol intermediate, dropwise adding for 1-2 h, heating to 120-140 ℃ after dripping, continuously stirring for reacting for 2-3h, vacuum dehydrating for 1-2 h, and cooling to 50-60 ℃ to obtain the phenolic aldehyde type Mannich base intermediate, wherein the structural formula is shown in 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 period, keeping the pH value to 8-10, reacting for 5-6 h, cooling to room temperature, adjusting the pH value to be neutral by hydrochloric acid, and removing the inorganic salt at the bottom to obtain the triple anionic-nonionic surfactant.
In the preparation method, the first two steps of reactions belong to the preparation of phenolic mannich bases. Generally, phenolic type Mannich base is prepared by a one-step method, namely alkylphenol and derivatives thereof, aldehyde and amine are added at one time, 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 defects of mixing unreacted raw materials, low purity, complex components, easy self-polymerization, bursting polymerization, product caking and the like, and has difficulty in obtaining exact structure and good performance for preparing the surfactant by adopting the one-step method.
According to the scheme, the phenolic type Mannich base is prepared by a two-step method, the alkylphenol polyoxyethylene ether reacts with formaldehyde under an alkaline condition to prepare the alkylphenol polyoxyethylene ether dihydroxymethyl intermediate, the yield of the dihydroxymethyl intermediate is high under a lower alkaline temperature condition and an excessive formaldehyde condition, unreacted formaldehyde is removed through vacuumizing, and the occurrence of subsequent side reactions is reduced. And in the second step, the dihydroxymethyl intermediate reacts with the organic primary amine, and a charging mode of dripping the dihydroxymethyl intermediate into the organic primary amine is adopted, so that self-polymerization of the intermediate is avoided, the reaction temperature is controlled to 90-110 ℃ in the period, water generated by condensation can be rapidly discharged, vacuum dehydration is assisted, the reaction is accelerated, the occurrence of side reaction is reduced, and the product yield is improved. Subsequently, the amino group reacts with the halogenide, and the anionic group is connected, which belongs to a more classical substitution reaction, and higher yield can be obtained under the condition of controlling temperature, solvent, pH value and material proportion.
In a word, the triple anionic-nonionic surfactant provided by the scheme has a novel structure, takes alkylphenol ethoxylates as the center, is connected with fatty amine type anionic surfactants at two sides, has anionic groups and nonionic groups in molecules, has the temperature resistance and salt resistance of the anionic nonionic surfactant, has lower CMC than the gemini surfactant, and is easy to realize good interfacial activity at low concentration. The preparation method is simple in preparation process, mild in reaction condition, definite in structure, single in component and high in purity, and the prepared triple anionic-nonionic surfactant can realize excellent performance and is easy to realize industrial production.
Preferably, the alkylphenol ethoxylates are at least one of alkylphenols with carbon chain length of C8-C20 and polyoxyethylene chain number of 3-20;
the halogenated carboxylic acid/sulfonate is at least one selected from sodium chloroacetate, sodium chloroethyl sulfonate, sodium chloropropionate, sodium chloropropylsulfonate and sodium chlorohydroxy propane sulfonate.
Preferably, the ratio of the amounts of alkylphenol ethoxylates, liquid or solid base, formaldehyde, and organic primary amine added is 1.0:0.45 (2.5-3.0): 2.0.
Preferably, the liquid or solid base is selected from NaOH and/or KOH, preferably NaOH.
Preferably, when liquid alkali or solid alkali is used, the liquid alkali or solid alkali is used in combination with solid/liquid formaldehyde, and the method comprises the steps of dripping liquid formaldehyde when the solid alkali is used and adding the solid formaldehyde when the liquid alkali 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 system water content 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 at least one of linear alkylamine, unsaturated fatty amine and rosin amine of C8-C20;
the alkaline solution comprises NaOH, KOH or NH 4 At least one of the OH solutions.
The application also provides a triple anionic nonionic surfactant with the technical proposal, which has the total mineralization of 298446mg/l of formation water at the formation temperature of 87 ℃, wherein Ca 2+ 10664mg/l、Mg 2+ Application of 867mg/l in reservoir flooding.
Preferably, the surfactant is prepared into a 50% sample solution by using fatty alcohol polyoxyethylene ether carboxylate, and then is further prepared into a 0.3% sample solution by using formation water, and the interfacial tension is less than or equal to 2.6X10 when the oil reservoir is applied -3 mN/m。
Preferably, the interfacial tension is less than or equal to 3.8X10 when the reservoir is applied after the reservoir is maintained at 87℃for 30 days at a concentration of 0.3% used -3 mN/m。
Compared with the prior art, the application has the advantages and positive effects that:
1. the adjustment range of the carbon chain length of the fatty amine connected with the two sides of the trigeminy anionic-nonionic surfactant is larger than that of the prior patent, the raw materials are easy to obtain, and a more suitable product can be customized according to specific application.
2. The trigeminy anion-nonionic surfactant provided by the application 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. The triple anionic-nonionic surfactant provided by the application has the advantages that fatty amine connected to two sides is of a tertiary amine structure, and can show cationic property when the pH value is low, but due to the existence of alkylphenol ethoxylates, precipitation can not be generated when inner salt is formed at the isoelectric point, and the application in an acidic environment is increased.
4. According to the preparation method provided by the application, under the condition that organic primary amine remains in the second-step reaction, the organic primary amine can be converted into aliphatic amine carboxylic acid or sulfonic acid type surfactant through the third-step reaction, and purification is not needed in most cases, so that the product application is facilitated.
5. The final product of the third step reaction is the solution of the tri-anionic-nonionic surfactant sulfonate or carboxylate, and the solution with a certain concentration can be directly prepared according to the requirement, so that the application is convenient.
6. The ternary anionic-nonionic surfactant obtained by the application 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 development of high-temperature and high-salt oil reservoirs.
Detailed Description
The following description of the technical solutions in the embodiments of the present application will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
EXAMPLE 1 preparation of sodium nonylphenol polyoxyethylene ether-3, 5-dimethyl-didodecyl 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 and reacting for 4 hours, and vacuum pumping to remove an organic solvent and unreacted formaldehyde for later use;
adding 2mol of dodecaprimary amine into another reaction container, gradually heating to 90-110 ℃ under the protection of nitrogen, dropwise adding 1.0mol of polyoxyethylene nonylphenol ether dihydroxymethyl intermediate for 1-2 h, heating to 120-140 ℃ after dripping, continuously stirring for reacting for 2h, vacuum dehydrating for 1h, and cooling to 50-60 ℃;
adding 500mL of ethanol and 100mL of water into the phenolic aldehyde type Mannich base intermediate, stirring until the solution is clear, adding 2.5mol of sodium chloroacetate in batches, continuously adding sodium hydroxide solution during the period, keeping the pH value to 8-10, reacting for 5-6 h, cooling to room temperature, adjusting the pH value to be neutral by hydrochloric acid, and standing to remove inorganic salt at the bottom to obtain the nonylphenol polyoxyethylene ether-3, 5-dimethyl-sodium didodecylacetate.
EXAMPLE 2 preparation of octyl phenol polyoxyethylene ether-3, 5-dimethyl-dioctadecylamine sodium ethyl 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 and reacting for 4 hours, and vacuum pumping 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 dripping, continuously stirring for reacting for 2h, vacuum dehydrating for 1h, and cooling to 50-60 ℃;
adding 500mL of ethanol and 100mL of water into the phenolic aldehyde type Mannich base intermediate, stirring until the solution is clear, adding 2.5mol of sodium chloroethyl sulfonate in batches, continuously adding a sodium hydroxide solution during the period, keeping the pH value to be 10-11, reacting for 5-6 h, cooling to room temperature, adjusting the pH value to be neutral by hydrochloric acid, and standing to remove inorganic salt at the bottom to obtain octyl phenol polyoxyethylene ether-3, 5-dimethyl-dioctadecylamine sodium ethyl sulfonate.
EXAMPLE 3 preparation of Polyoxyethylene nonyl phenyl ether-3, 5-dimethyl-didodecyl amino hydroxypropyl sulfonate
Adding 1.0mol of polyoxyethylene nonylphenol 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 and reacting for 4 hours, and vacuum pumping to remove an organic solvent and unreacted formaldehyde for later use;
adding 2mol of dodecaprimary amine into another reaction container, gradually heating to 90-110 ℃ under the protection of nitrogen, dropwise adding 1.0mol of polyoxyethylene nonylphenol ether dihydroxymethyl intermediate for 1-2 h, heating to 120-140 ℃ after dripping, continuously stirring for reacting for 2h, vacuum dehydrating for 1h, and cooling to 50-60 ℃;
adding 500mL of ethanol and 100mL of water into the phenolic aldehyde type Mannich base intermediate, stirring until the solution is clear, adding 2.5mol of 3-chloro-2-hydroxy sodium propane sulfonate in batches, continuously adding a sodium hydroxide solution during the period, keeping the pH value at 8-10, reacting for 5-6 h, cooling to room temperature, adjusting the pH value to be neutral by hydrochloric acid, standing to remove inorganic salt at the bottom, and obtaining the nonylphenol polyoxyethylene ether-3, 5-dimethyl-didodecyl hydroxy sodium propane sulfonate.
EXAMPLE 4 dodecylphenol polyoxyethylene ether-3, 5-dimethyl-bicarbon acid sodium salt
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 and reacting for 4 hours, and vacuum pumping to remove an organic solvent and unreacted formaldehyde for later use;
adding 2mol of cocoamine (mixed amine of C8-C14 linear alkane and alkene) into another reaction container, gradually heating to 90-110 ℃ under the protection of nitrogen, dropwise adding 1.0mol of dodecyl phenol polyoxyethylene ether dihydroxymethyl intermediate for 1-2 h, heating to 120-140 ℃ after dropwise adding, continuously stirring for reacting for 2h, vacuum dehydrating for 1h, and cooling to 50-60 ℃;
adding 500mL of ethanol and 100mL of water into the phenolic aldehyde type Mannich base intermediate, stirring until the solution is clear, adding 2.5mol of sodium chloroacetate in batches, continuously adding sodium hydroxide solution during the period, keeping the pH value to 8-10, reacting for 5-6 h, cooling to room temperature, adjusting the pH value to be neutral by hydrochloric acid, and standing to remove inorganic salt at the bottom to obtain dodecyl phenol polyoxyethylene ether-3, 5-dimethyl-sodium bicarbonate.
Description: r in the structural formula 2 、R 3 Is coco base with corresponding carbon number C8-C14 in the raw materials.
EXAMPLE 5 preparation of dodecylphenol polyoxyethylene ether-3, 5-dimethyl-bis-rosin amine sodium acetate
Adding 1.0mol of dodecylphenol 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 and reacting for 4 hours, and vacuum pumping to remove the 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 dodecyl phenol polyoxyethylene ether dihydroxymethyl intermediate for 1-2 h, heating to 120-140 ℃ after dripping, continuously stirring for reacting for 2h, vacuum dehydrating for 1h, and cooling to 50-60 ℃;
adding 500mL of ethanol and 100mL of water into the phenolic aldehyde type Mannich base intermediate, stirring until the solution is clear, adding 2.5mol of sodium chloroacetate in batches, continuously adding sodium hydroxide solution during the period, keeping the pH value to 8-10, reacting for 5-6 h, cooling to room temperature, adjusting the pH value to be neutral by hydrochloric acid, and standing to remove inorganic salt at the bottom to obtain dodecyl phenol polyoxyethylene ether-3, 5-dimethyl-sodium bisrosin amine acetate.
Description: r in the structural formula 2 、R 3 Is rosin group, and has the following specific structure:
EXAMPLE 6 preparation of sodium nonylphenol polyoxyethylene ether-3, 5-dimethyl-bis (tallow amine) hydroxy propane sulfonate
Adding 1.0mol of polyoxyethylene nonylphenol 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 and reacting for 4 hours, and vacuum pumping to remove the organic solvent and unreacted formaldehyde for later use;
2mol of tallow amine is added into another reaction vessel, the temperature is gradually increased to 90-110 ℃ under the protection of nitrogen, 1.0mol of polyoxyethylene nonylphenol ether dihydroxymethyl intermediate is dripped for 1-2 h, the temperature is increased to 120-140 ℃ after dripping, the stirring reaction is continued for 2h, the vacuum dehydration is carried out for 1h, and the temperature is reduced to 50-60 ℃;
adding 500mL of ethanol and 100mL of water into the phenolic aldehyde type Mannich base intermediate, stirring until the solution is clear, adding 3.0mol of 3-chloro-2-hydroxy propane sodium sulfonate in batches, continuously adding a sodium hydroxide solution during the period, keeping the pH value at 8-10, reacting for 5-6 hours, cooling to room temperature, adjusting the pH value to be neutral by hydrochloric acid, standing to remove inorganic salt at the bottom, and obtaining the nonylphenol polyoxyethylene ether-3, 5-dimethyl-bis (tallow amine) hydroxy propane sodium sulfonate.
Performance testing
The products of examples 1-6 were added with a certain amount of water and alcohol to prepare sample solutions with an effective content of 50%, respectively numbered samples 1-6, and tested for various properties.
Salt tolerance test
A1.0% solution of each sample was prepared with simulated saline containing 250000mg/l NaCl, and after stirring well, the presence or absence of precipitation and delamination were observed. The test results are shown in Table 1.
TABLE 1 salt tolerance test
pH adaptation
Preparing 1.0% solution of each sample by tap water, gradually dripping hydrochloric acid or sodium hydroxide solution respectively, adjusting the pH value to 3-10, and observing the turbidity and precipitation phenomena. The test results are shown in Table 2.
TABLE 2pH adaptation
Interfacial tension
Samples 1-6 were selected, and an aliphatic alcohol polyoxyethylene ether carboxylate (AEC-5) surfactant was added to prepare 50% oil-displacing agent samples, which were numbered sequentially, and their interfacial tension was measured. And simultaneously, 50% of fatty alcohol polyoxyethylene ether carboxylate is used as a reference.
The product is applied to a certain block of an original oil field, the total mineralization degree of stratum 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 dehydrated in blocks, and interfacial tension was measured at 87℃with a TX-500C interfacial tensiometer.
TABLE 3 interfacial tension
Temperature resistance test
The oil displacement agent prepared by samples 1-6 is prepared into 0.3% sample solution by using stratum water respectively, the sample solution is packaged in an ampoule under the protection of nitrogen, the ampoule is placed in an incubator at 87 ℃ for 30 days, the oil displacement agent is taken out, and the interfacial tension is measured, and the test conditions are the same as in example 9. And simultaneously, 50% of fatty alcohol polyoxyethylene ether carboxylate is used as a reference.
TABLE 4 interfacial tension after temperature resistance
From the data, the triple anionic nonionic surfactant has the advantages of temperature resistance, salt resistance and acid-base adaptability, good interfacial tension and good compatibility with polymers, and can be effectively applied to the development of high-temperature and high-salt oil reservoirs.
Claims (12)
1. A triple anionic nonionic surfactant is characterized by having a structural formula shown in 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 from 3 to 15;
R 2 、R 3 at least one of alkyl, alkenyl and rosin radical with 8-20 carbon atoms;
y is an anionic group;
m is Na + 、K + Or NH 4 + At least one of them.
2. The triple anionic nonionic surfactant according to claim 1, wherein the anionic group is selected from at least one of ethyl carboxylic acid, ethyl sulfonic acid, propyl carboxylic acid, propyl sulfonic acid, hydroxy propane sulfonic acid groups.
3. The preparation method of the triple anionic nonionic surfactant according to claim 1 or 2, wherein 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 then the Mannich base is reacted with halogenated alkyl carboxylate or halogenated alkyl sulfonate to introduce an anionic group, so that the triple anionic nonionic surfactant is prepared.
4. A method of preparation according to claim 3, comprising the steps of:
adding 1.0mol of alkylphenol ethoxylate into a reaction vessel, 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 and reacting for 4-8h, and vacuum pumping out the organic solvent and unreacted formaldehyde to obtain an alkylphenol ethoxylate 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 ethoxylate dimethylol intermediate, dropwise adding for 1-2 h, heating to 120-140 ℃ after dripping, continuously stirring for reacting for 2-3h, vacuum dehydrating for 1-2 h, and cooling to 50-60 ℃ to obtain a phenolic aldehyde type Mannich base intermediate;
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 period, keeping the pH value to 8-10, reacting for 5-6 h, cooling to room temperature, adjusting the pH value to be neutral by hydrochloric acid, and removing the inorganic salt at the bottom to obtain the triple anionic nonionic surfactant.
5. The method according to claim 4, wherein the alkylphenol ethoxylate is at least one of alkylphenols having a carbon chain length of C8 to C20 and a polyoxyethylene chain number of 3 to 15;
the halogenated carboxylic acid/sulfonate is at least one selected from sodium chloroacetate, sodium chloroethyl sulfonate, sodium chloropropionate, sodium chloropropylsulfonate and sodium chlorohydroxy propane sulfonate.
6. The process according to claim 4, wherein the ratio of the amounts of alkylphenol ethoxylates, liquid or solid bases, formaldehyde and organic primary amine is 1.0:0.45 (2.5-3.0): 2.0.
7. The method according to claim 6, wherein the liquid or solid base is selected from NaOH and/or KOH.
8. The method according to claim 7, wherein the liquid base or the solid base is used in combination with the solid/liquid formaldehyde, and the method comprises the steps of adding the liquid formaldehyde dropwise when the solid base is used and adding the solid formaldehyde when the liquid base is used.
9. The method according to claim 4, wherein the organic solvent is at least one selected from the group consisting of methanol, ethanol and isopropanol;
the organic primary amine is at least one of linear alkylamine, unsaturated fatty amine and rosin amine of C8-C20;
the alkaline solution is NaOH, KOH or NH 4 At least one of the OH solutions.
10. The triple anionic nonionic surfactant of claim 1 or 2, wherein Ca has a total formation water mineralization of 298446mg/L at a formation temperature of 87 ℃ and 2+ 10664mg/L、Mg 2+ application of 867mg/L in oil reservoir flooding.
11. The use according to claim 10, wherein the surfactant is formulated with fatty alcohol polyoxyethylene ether carboxylate to a 50% sample solution, and then with formation water to a 0.3% sample solution, the interfacial tension of the surfactant being less than or equal to 2.6x10 when applied to a reservoir -3 mN/m。
12. The use according to claim 10, wherein, at a use concentration of 0.3%,after being kept at 87 ℃ for 30 days, the interfacial tension of the oil deposit is less than or equal to 3.8X10 when the oil deposit is applied -3 mN/m。
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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 |
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