CN114105835B - Anionic nonionic gemini surfactant as well as preparation method and application thereof - Google Patents
Anionic nonionic gemini surfactant as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a negative nonionic gemini surfactant as well as a preparation method and application thereof, belonging to the technical field of surfactants. The anionic and nonionic gemini surfactant provided by the invention has the following structural formula (1):formula (1) wherein Y represents a linking group selected from O or N. When Y is O, R1、R2Represents any one of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether and fatty acid amide polyoxyethylene ether; when Y is N, R1‑Y、R2Y represents one of the fatty acid amide polyetheramines. The anion-nonionic gemini provided by the invention has good surface activity and water solubility, excellent surface activity, simple synthetic route, high yield and controllable price, and is suitable for industrial production and high-temperature and high-salinity oil reservoir oil displacement exploitation.
Description
Technical Field
The invention belongs to the technical field of surfactants, and particularly relates to a negative nonionic gemini surfactant as well as a preparation method and application thereof.
Background
The anionic and nonionic surfactant has both anionic groups and nonionic groups in the same molecule, has the advantages of the anionic surfactant and the nonionic surfactant, such as temperature resistance, salt resistance, no cloud point and stratum adsorption resistance, has good application performance in the aspects of reducing interfacial tension, foaming, wetting, emulsifying and the like, has good synergistic effect with other surfactants, and is suitable for high-temperature and high-salinity oil reservoir exploitation.
The gemini surfactant is formed by connecting two common surfactant molecules through a linking group by chemical bonds, has more excellent performance than the traditional single-chain surfactant, such as easy adsorption on a solution interface, easy formation of micelles, lower Kraff point, good synergistic effect of compounding with other surfactants, good calcium soap dispersing performance and the like, and therefore, the traditional anionic and nonionic surfactant is gemini and the performance of the surfactant can be further improved.
At present, the synthesis of gemini surfactants is a research hotspot, but mainly adopts more cations and amphiprotics, is not resistant to stratum adsorption, has less anionic gemini surfactants, mostly contains ester groups easy to hydrolyze, and is not suitable for being used in high-temperature and high-salt environments. In the anionic surfactant, sulfonate, carboxylate, phosphate and sulfate are mainly used as anionic groups, wherein the sulfonate and the carboxylate are most practical for high-temperature and high-salt reservoir oil displacement.
Zana and the like synthesize the carboxylate gemini surfactant by taking long-chain fatty alcohol, diepoxy propyl ether with different chain lengths, bromoacetic acid and the like as raw materials. In summer, spring and the like, lauric acid, tartaric acid, thionyl chloride and the like are used as raw materials, and lauroyl chloride and tartaric acid are subjected to esterification reaction under an alkaline condition to generate 2, 3-bisdodecanoate sodium tartrate. However, the carboxylate gemini surfactant has a disadvantage in that it is poor in solubility and hard water resistance and requires a long time for dissolution by heating.
The Zhaosha takes diphenylethane and long-carbon-chain fatty acyl chloride as raw materials, and the gemini sulfonic acid surfactant is synthesized by Friedel-crafts acylation reaction, Huang Minlon reduction reaction, sulfonation, neutralization and other reactions, compared with sodium dodecyl benzene sulfonate, the pC20 value of the gemini surfactant with corresponding carbon chain length is reduced by 94.4%, and the CMC value is reduced by 91.3%; the gemini surfactant is easier to form micelles than the single-chain surfactant, and the efficiency of reducing the surface tension is high.
Liu chemical peng and the like use fatty acid, phenol and polyethylene glycol as raw materials, and a series of long-chain sodium alkyl benzene sulfonate gemini surfactants containing polyoxyethylene ether intermediate connecting groups with different lengths are synthesized through the steps of acylation reaction, esterification reaction, Fries rearrangement, hydrogenation reduction reaction, sulfonation, neutralization reaction and the like. Liuxiang and the like take alpha-olefin, diphenyl ether, chlorosulfonic acid and the like as raw materials, and the dialkyl diphenyl ether sulfonate gemini surfactant is synthesized through alkylation, sulfonation, neutralization and other reactions and has good surface performance.
Guolimei and the like synthesize anionic gemini surfactant sodium didodecyl ethoxy disulfate by using dodecanol, ethylene glycol diglycidyl ether, chlorosulfonic acid and the like as raw materials and boron trifluoride-ethyl ether as a catalyst through ring-opening reaction, acidification and neutralization reaction.
In a word, although the current research draws a conclusion that the gemini surfactant has excellent performance, the synthesis route for preparing the gemini surfactant is long, difficult, low in yield and high in price, and is basically not suitable for industrial production, and the field application is limited. Therefore, the development of a gemini surfactant with good performance, simple synthesis process, moderate price and industrial prospect is needed.
Disclosure of Invention
The invention provides a negative non-ionic gemini surfactant as well as a preparation method and application thereof, and the obtained gemini surfactant is simple in synthetic route, high in yield, controllable in price, good in water solubility and excellent in surface activity, and is suitable for industrial production and high-temperature and high-salinity oil reservoir oil displacement exploitation.
In order to achieve the above object, the present invention provides a anionic and nonionic gemini surfactant having the following structural formula (1):
formula (1)
Wherein Y represents a linking group selected from O or N; when Y is O, R1、R2Represents any one of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether and fatty acid amide polyoxyethylene ether; when Y is N, R1-Y、R2Y represents a fatty acid amide polyetheramine.
Preferably, the corresponding hydrocarbon group in the fatty alcohol-polyoxyethylene ether is selected from at least one of linear alkane, branched alkane and linear alkene of C10-C18; the corresponding alkylphenol in the alkylphenol polyoxyethylene ether is selected from at least one of alkylphenol of C8-C12; the fatty acid amide polyoxyethylene ether is a product obtained by condensing fatty acid and monoethanolamine in a ratio of 1:1 and then adding ethylene oxide, and the corresponding fatty acid is selected from at least one of C10-C22 fatty acids; the fatty acid amide polyether amine is a 1:1 condensation product of fatty acid and double-ended polyether amine, and the corresponding fatty acid is at least one selected from C10-C22 fatty acids.
Preferably, the number of polyoxyethylene ether chain segments in the fatty alcohol-polyoxyethylene ether, the alkylphenol polyoxyethylene ether and the fatty acid amide polyether is 2-15, and preferably 3-10. It is understood that in the present embodiment, the number of polyoxyethylene ether links in each component may be any of 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 and 15.
Preferably, the fatty acid amide polyether amine is a 1:1 condensation product of fatty acid and double-end polyether amine, the corresponding fatty acid is at least one selected from C10-C22 fatty acid, and the double-end polyether amine is at least one selected from double-end polyether amine with the molecular weight of 230-600.
The invention also provides a preparation method of the anionic and nonionic gemini surfactant according to any one technical scheme, which is prepared by firstly ring opening reaction and then sulfonation reaction of fatty alcohol-polyoxyethylene ether, alkylphenol ethoxylate, fatty acid amide ethoxylate or fatty acid amide polyether amine and bisphenol A diglycidyl ether.
Preferably, the method comprises the following two steps:
adding 1.0mol of fatty alcohol-polyoxyethylene ether/alkylphenol polyoxyethylene ether/fatty acid amide polyether amine into a four-necked flask reaction kettle, heating to 50-70 ℃, after nitrogen replacement, adding a catalyst, removing water and a solvent brought by the catalyst in vacuum if necessary, adding or not adding an organic solvent, dropwise adding 0.5-0.6mol of bisphenol A diglycidyl ether, completely dropping within 0.5-3h, keeping a certain temperature, and continuously reacting for 2-8h to obtain a nonionic gemini surfactant intermediate;
and (3) removing the organic solvent from the obtained intermediate at 70-80 ℃ in vacuum, cooling to 30-50 ℃, slowly dripping 2.0-3.0mol of sulfonating agent under rapid stirring, reacting for 3-5 hours at the temperature of 30-50 ℃ continuously, hydrolyzing the product by using alkaline solution, and adjusting the pH value to be neutral to obtain the anionic/nonionic gemini surfactant sulfonate.
It can be understood that the molar ratio of fatty alcohol-polyoxyethylene ether/alkylphenol ethoxylate/fatty acid amide-polyoxyethylene ether/fatty acid amide polyether amine to bisphenol a diglycidyl ether is limited in the above scheme because when the molar ratio is too high, the bisphenol a diglycidyl ether is relatively insufficient and cannot sufficiently form a gemini structure, a large amount of fatty alcohol/alkylphenol/fatty acid amide-polyoxyethylene ether sulfate is generated after sulfonation, and the content of the target product is low; when the molar ratio is too low, a large amount of bisphenol A diglycidyl ether remains, and a self-condensation reaction of bisphenol A diglycidyl ether is liable to occur, resulting in insoluble impurities and a sulfonated product of bisphenol A diglycidyl ether having no hydrophobic group. Meanwhile, the molar ratio of the sulfonating agent to the sulfonating agent is limited because when the sulfonating agent is insufficient, sulfonation is insufficient, the anion content of the final product is low, and the water solubility is poor; when the sulfonating agent is excessive, a large amount of inorganic salt and other impurities are generated in the subsequent treatment of the excessive sulfonating agent, particularly when alkylphenol polyoxyethylene ether is used as a raw material, sulfonation can also occur at the benzene ring part of the alkylphenol polyoxyethylene ether, and excessive sulfonating agent can cause over sulfonation, so that the proper amount of the sulfonating agent needs to be controlled.
It is worth noting that when the bisphenol A diglycidyl ether is added, the temperature can be raised to a certain temperature so as to enable the two materials to react in time. Particularly, when fatty alcohol-polyoxyethylene ether/alkylphenol ethoxylate/fatty acid amide ethoxylate are used as raw materials and an alkaline catalyst is used, if the temperature is not raised in time, the bisphenol A diglycidyl ether is excessively added before the target reaction occurs, and the self-polymerization reaction occurs.
Preferably, fatty alcohol-polyoxyethylene ether/alkylphenol polyoxyethylene ether/fatty acid amide polyoxyethylene ether is used as a raw material, and when a Lewis acid catalyst is adopted, the reaction temperature is controlled to be 70-90 ℃;
fatty alcohol polyoxyethylene ether/alkylphenol polyoxyethylene ether/fatty acid amide polyoxyethylene ether are used as raw materials, and when an alkaline catalyst is adopted, the temperature is controlled at 140-;
when fatty acid amide polyether amine is used as a raw material, one of alkaline catalysts sodium hydroxide or potassium hydroxide is adopted and matched with one of phase transfer catalysts for use, and the temperature is controlled to be 50-80 ℃.
It can be understood that when the fatty alcohol-polyoxyethylene ether, the alkylphenol ethoxylate and the fatty acid amide ethoxylate are used as raw materials, the tail end of the raw materials is alcoholic hydroxyl, and the reaction of the alcoholic hydroxyl and the bisphenol A diglycidyl ether is etherification reaction, when a Lewis acid catalyst is adopted, the temperature can be controlled to be 70-90 ℃ because the boron trifluoride diethyl etherate complex has high catalytic activity, and when an alkaline catalyst is adopted, the temperature can be controlled to be 140-160 ℃, the catalytic performance is insufficient when the temperature is too low, the side reactions are more when the temperature is too high, and the product is complex. Meanwhile, the vacuum removal of water and the solvent brought by the catalyst is beneficial to the reaction without adding other solvents.
When fatty acid amide polyether amine is used as a raw material, the terminal of the raw material is primary amine, the addition reaction of the primary amine and bisphenol A diglycidyl ether is easy to occur, and the temperature is controlled to be 50-80 ℃ under the alkaline condition, in the presence of a phase transfer catalyst and a solvent.
Preferably, the catalyst comprises at least one of a lewis acid catalyst, a basic catalyst, and a phase transfer catalyst;
the Lewis acid catalyst is selected from boron trifluoride diethyl etherate;
the alkaline catalyst is selected from at least one of sodium hydroxide, potassium hydroxide, sodium methoxide and sodium ethoxide;
the phase transfer catalyst is selected from at least one of tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate and hexadecyltrimethylammonium bromide;
the dosage of the catalyst is 0.2-3% of the mass of the reaction substrate. It is understood that the catalyst may also be used in the present embodiment in an amount of 0.5%, 1%, 1.5%, 2.0%, 2.5% or any value within the above range.
Preferably, the organic solvent is selected from anhydrous methanol, ethanol, isopropanol or a mixture thereof with water;
the organic solvent is only added when the fatty acid amide polyether amine is used as a raw material;
the dosage of the organic solvent is 100ml-500ml/mol of raw materials.
Preferably, the sulfonating agent is selected from concentrated H2SO4H for fuming2SO4、SO3And chlorosulfonic acid;
the alkaline solution is at least one selected from sodium hydroxide, potassium hydroxide and ammonia water.
The invention also provides application of the composition containing the anionic and nonionic gemini surfactant prepared according to any one technical scheme as a temperature-resistant and salt-resistant oil displacement agent in a certain block of a crude oil field with the temperature of 85 ℃ and the total mineralization of 250000 mg/L.
Preferably, the interfacial tension of 0.05-0.3% solution of temperature-resistant and salt-resistant oil displacement agent containing the anionic and nonionic gemini surfactant is less than 8.64 multiplied by 10 under the conditions of formation water with the total mineralization degree of 250000mg/L and 85 DEG C-3mN/m。
Compared with the prior art, the invention has the advantages and positive effects that:
1. the anionic and nonionic gemini surfactant provided by the invention has two types of hydrophilic groups of anions and nonionic, the carbon chain length and the number of polyoxyethylene ether can be adjusted within a large range according to needs, and the anionic and nonionic gemini surfactant has advantages in structure and performance and is particularly suitable for oil displacement needs.
2. In the anionic and nonionic gemini surfactant provided by the invention, sulfonic acid, hydroxyl and amide groups are strong hydrophilic groups, are easy to dissolve in water, resist temperature and salt, can effectively reduce interfacial tension, and are suitable for high-temperature and high-salt oil displacement products.
3. The anionic and nonionic gemini surfactant provided by the invention can obtain good interfacial activity at a low concentration.
4. The hydrophilic group of the anionic and nonionic gemini surfactant provided by the invention is electronegative as a whole, and the adsorption consumption of the stratum can be obviously reduced.
5. The anionic and nonionic gemini surfactant provided by the invention has a heat-resistant and salt-resistant polyoxyethylene ether group, the general applicable temperature can reach 130 ℃, and the product has the advantages of heat resistance and hydrolysis resistance, and can be suitable for exploitation of high-temperature, high-salt and high-salinity oil reservoirs.
6. The anionic and nonionic gemini surfactant provided by the invention has a remarkable synergistic effect with alkylphenol polyoxyethylene ether carboxylate and fatty alcohol polyoxyethylene ether carboxylate, and is beneficial to development and application of a temperature-resistant and salt-resistant oil displacement agent.
7. The raw materials adopted by the invention are easy to obtain in large quantity, the price is relatively low, the preparation method is classical and reliable, the synthesis process is simple, the reaction condition is mild, and the method has an industrial production prospect.
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 derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The following examples do not contain SO due to laboratory conditions limitations3The sulfonation process, however, according to the known knowledge, the nonionic gemini surfactant intermediate containing the phenol benzene ring prepared in the step 1 is easier to sulfonate than alkylbenzene substances, and SO can be adopted in theory3The membrane reactor and the corresponding process are used for sulfonation, which is also the basis for judging that the method has industrial production prospect.
Example 1: synthesis of bis (octadecyl polyoxyethylene ether (5) -hydroxypropyl) -bisphenol A-sodium disulfonate surfactant
Adding 1.0mol of octadecyl alcohol polyoxyethylene ether (5 EO) into a 2000mL four-necked flask reaction kettle, heating to 50-70 ℃, after nitrogen replacement, adding a catalyst boron trifluoride diethyl etherate complex accounting for 1% of the mass of the raw material, dropwise adding 0.5-0.6mol of bisphenol A diglycidyl ether, completing dropwise addition within 0.5-1.5h, keeping the temperature of 80 ℃, and continuing to react for 8h to obtain a nonionic gemini surfactant intermediate;
and (3) cooling the product to 30-50 ℃, slowly dripping 3.0mol of concentrated sulfuric acid sulfonating agent under rapid stirring, finishing dripping within 1.5-2.5h, continuously controlling the temperature to 30-50 ℃ to react for 3-5h, and hydrolyzing the product by using a sodium hydroxide solution and adjusting the pH value to be neutral to obtain the anionic and nonionic gemini surfactant sulfonate. The total yield is 88%.
Example 2: synthesis of bis (dodecylphenol polyoxyethylene ether (8) -hydroxypropyl) -bisphenol A-sodium disulfonate surfactant
Adding 1.0mol of dodecylphenol polyoxyethylene ether (8 EO) into a 2000mL four-necked bottle reaction kettle, heating to 50-70 ℃, replacing nitrogen, adding a sodium methoxide solution with the content of 10 percent of the mass of the raw material being 2 percent as a catalyst, removing a methanol solvent brought by the catalyst in vacuum, dropwise adding 0.5-0.6mol of bisphenol A diglycidyl ether, completing dropwise adding within 1.5-3.0h, heating and keeping the temperature at 150 ℃ for continuous reaction for 5h to obtain a nonionic gemini surfactant intermediate;
and (3) cooling the product to 30-40 ℃, slowly dripping 2.5mol of fuming sulfuric acid sulfonating agent under rapid stirring, finishing dripping within 1.5-2.5h, continuously controlling the temperature to 30-40 ℃ to react for 3-5h, and hydrolyzing the product by using a potassium hydroxide solution and adjusting the pH value to be neutral to obtain the anionic and nonionic gemini surfactant sulfonate. The total yield is 86%.
Example 3: synthesis of bis (oleamide polyoxyethylene ether (7) -hydroxypropyl) -bisphenol A-sodium disulfonate surfactant
Adding 1.0mol of oleamide polyoxyethylene ether (7 EO) into a 2000mL four-necked bottle reaction kettle, heating to 50-70 ℃, after nitrogen replacement, adding a sodium hydroxide ethanol solution with the content of 10 percent of the mass of the raw material as a catalyst, removing an ethanol solvent brought by the catalyst in vacuum, dropwise adding 0.5-0.6mol of bisphenol A diglycidyl ether, completing dropwise adding within 1.5-3.0h, heating and keeping at 150 ℃ for continuous reaction for 3h to obtain a nonionic gemini surfactant intermediate;
and (3) cooling the product to 30 ℃, slowly dripping 2.0mol of chlorosulfonic acid sulfonating agent under rapid stirring, finishing dripping within 1.5-2.5h, continuously controlling the temperature to 30-50 ℃ to react for 3-5h, hydrolyzing the product by using concentrated ammonia water, and adjusting the pH value to be neutral to obtain the anionic and nonionic gemini surfactant sulfonate. The total yield is 84%.
Example 4: synthesis of bis (oleamide polyoxyethylene ether (6) amine-hydroxypropyl) -bisphenol A-sodium disulfonate surfactant
Adding 1.0mol of oleamide polyether (6 EO) amine into a 2000mL four-necked bottle reaction kettle, heating to 50-70 ℃, adding sodium hydroxide accounting for 2% of the mass of the raw materials and tetrabutylammonium bromide accounting for 0.5% of the mass of the raw materials as catalysts, adding 200mL of absolute ethyl alcohol, adding 30mL of water, dropwise adding 0.5-0.6mol of bisphenol A diglycidyl ether, completing dropwise adding within 0.5-1.5h, keeping 65 ℃ and continuing to react for 8h to obtain a nonionic gemini surfactant intermediate;
and (3) removing water and an ethanol solvent from the product in vacuum, cooling to 30 ℃, slowly dripping 3.0mol of concentrated sulfuric acid sulfonating agent under rapid stirring, finishing dripping within 1.5-2.5h, continuously controlling the temperature to 30-50 ℃ to react for 3-5h, and hydrolyzing the product by using a sodium hydroxide solution and adjusting the pH value to be neutral to obtain the anionic and nonionic gemini surfactant sulfonate. The total yield is 87%.
The anionic nonionic gemini surfactants synthesized in examples 1-4 were formulated into 50% solutions containing 10-15% methanol/ethanol/isopropanol, with the balance being water, and the sample solutions were clear and free of precipitation or delamination.
Performance test-Single agent salt resistance test
A50% sample of the anionic nonionic gemini surfactant synthesized in examples 1-4 was formulated with a total degree of mineralization of 250000mg/L, Ca2++Mg2+And preparing a 1.0% sample solution by using 2500mg/L simulated water, and uniformly stirring to observe whether precipitation and delamination occur. The test results are shown in table 1.
TABLE 1 Single agent salt tolerance test
Note: the comparative examples consisted of: the sodium dodecyl benzene sulfonate and 6501 surfactant compound comprise 50 percent of effective content of the two, 20 percent of isopropanol and the balance of water.
Performance test-Single agent interfacial tension Performance test
A50% sample of the anionic nonionic gemini surfactant synthesized in examples 1-4 was formulated with a total degree of mineralization of 250000mg/L, Ca2++Mg2+Preparing a 0.05-0.3% sample solution from 2500mg/L simulated water, dehydrating crude oil in a certain block of a central oil field, and testing the interfacial tension of the sample solution by using a TX-500C interfacial tension instrument at the temperature of 85 ℃ and at the speed of 5000r/min, wherein the test results are shown in Table 2.
Table 2 interfacial tension units for 50% samples of anionic nonionic gemini surfactants: 10-3mN/m
Note: the composition of the comparative sample was: the sodium dodecyl benzene sulfonate and 6501 surfactant are compounded, the effective content of the two is 50%, the isopropanol is 20%, and the balance is water.
As can be seen from Table 2, the interfacial tension of 50% of the anionic and nonionic gemini surfactant sample can reach 10% under the concentration of 0.05-0.3% of the sample-3mN/m order of magnitude.
Performance test-Single agent temperature test
A50% sample of the anionic nonionic gemini surfactant synthesized in examples 1-4 was formulated with a total degree of mineralization of 250000mg/L, Ca2++Mg2+Preparing a 0.3% sample solution from 2500mg/L simulated water, packaging in a stainless steel pressure-resistant container under the protection of nitrogen, placing in a thermostat at 130 ℃ for 30 days, cooling, taking out the solution, dehydrating crude oil in a certain block of the original oilfield, and testing the interfacial tension of the sample solution by using a TX-500C interfacial tension instrument at 85 ℃ and 5000r/min, wherein the test results are shown in Table 3.
TABLE 3 interfacial tension after 50% sample thermal stabilization of anionic nonionic gemini surfactants
Unit: 10-3mN/m
As can be seen from Table 3, the interfacial tension of 50% of the samples of the anionic/nonionic gemini surfactant can still reach 10 after being heated at 130 ℃ for 30 days-3mN/m order of magnitude.
The anionic and nonionic gemini surfactant provided by the invention can be directly used as a surfactant for oil displacement, but the anionic and nonionic gemini surfactant is preferably compounded and used in consideration of cost factors and the surface performance of the anionic and nonionic gemini surfactant.
In another embodiment, the present invention provides a surfactant composition for flooding comprising a anionic gemini surfactant, comprising the anionic gemini surfactant, an alkylphenol ethoxylate carboxylate and a fatty alcohol ethoxylate carboxylate, water and a solvent. Wherein the mass percentage of the anionic and nonionic gemini surfactant, the alkylphenol polyoxyethylene ether carboxylate and the fatty alcohol polyoxyethylene ether carboxylate is 1:2:2, the total content of the anionic and nonionic gemini surfactant, the alkylphenol polyoxyethylene ether carboxylate and the fatty alcohol polyoxyethylene ether carboxylate accounts for 50%, the solvent is methanol/ethanol/isopropanol and accounts for 15%, and the balance is water. The use concentration of the temperature-resistant and salt-resistant oil displacement agent is 0.05-0.3%.
Performance test-interfacial tension Performance test of compounded samples
Using the produced water of a certain block of the original oilfield (total mineralization degree 41097mg/L, Cl)-Ion 23985 mg/L, Ca2++Mg2+Ion 1650 mg/L) preparing 0.05-0.3% solution of surfactant composition for oil displacement containing anionic and nonionic gemini surfactant, dehydrating crude oil in a block of the original oilfield, and testing interfacial tension of the sample with TX-500C interfacial tension instrument at 85 deg.C and 5000r/min, wherein the reference value of interfacial tension is less than 0.1mN/m, i.e. 10-2Order of magnitude, the test results are shown in table 4:
table 4 interfacial tension units for anionic nonionic gemini surfactant compounded samples: 10-3mN/m
Note: the composition of the comparative sample was: the alkylphenol polyoxyethylene ether carboxylate and the fatty alcohol polyoxyethylene ether carboxylate are compounded in a ratio of 1:1, the effective content of the alkylphenol polyoxyethylene ether carboxylate and the fatty alcohol polyoxyethylene ether carboxylate is 50%, isopropanol is 20%, and the balance is water.
The types of alkylphenol ethoxylate carboxylates and fatty alcohol ethoxylate carboxylates in the comparative examples were the same as those used in the examples.
As can be seen by combining the data in the table 4, the interfacial tension of the anionic and nonionic gemini surfactant compound sample provided by the invention is as low as 10 within the concentration range of 0.05-0.3%-3The magnitude of mN/m is obviously superior to the interfacial tension of a comparative sample.
The alkylphenol polyoxyethylene ether carboxylate and the fatty alcohol polyoxyethylene ether carboxylate are used as temperature-resistant and salt-resistant surfactants, and the anionic and nonionic gemini surfactant provided by the invention has a remarkable reduction on the interfacial tension of the combination of the surfactants, and shows a remarkable synergistic effect. This is mainly because the gemini structure of the anionic and nonionic surfactant is more likely to form micelles, and is related to anionic and nonionic structures similar to alkylphenol polyoxyethylene ether carboxylate and fatty alcohol polyoxyethylene ether carboxylate, so that the synergistic effect between them is more significant.
Claims (6)
1. A anionic nonionic gemini surfactant characterized by having the following structural formula (1):
formula (1)
Wherein Y represents a linking group selected from O or N; when Y is O, R1、R2Represents any one of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether and fatty acid amide polyoxyethylene ether; when Y is N, R1-Y、R2-Y represents a fatty acid amide polyetheramine;
the corresponding alkyl in the fatty alcohol-polyoxyethylene ether is selected from at least one of straight-chain alkane, branched-chain alkane and straight-chain alkene of C10-C18; the corresponding alkylphenol in the alkylphenol polyoxyethylene ether is selected from at least one of alkylphenol of C8-C12; the fatty acid amide polyoxyethylene ether is a product obtained by condensing fatty acid and monoethanolamine in a ratio of 1:1 and then adding ethylene oxide, and the corresponding fatty acid is selected from at least one of C10-C22 fatty acids; the fatty acid amide polyether amine is a 1:1 condensation product of fatty acid and double-ended polyether amine, and the corresponding fatty acid is at least one selected from C10-C22 fatty acid;
the number of polyoxyethylene ether chain joints in the fatty alcohol-polyoxyethylene ether, the alkylphenol ethoxylates and the fatty acid amide polyether is 2-15, and the double-end polyether amine corresponding to the fatty acid amide polyether amine is the double-end polyether amine with the molecular weight of 230-600;
the preparation method of the anionic and nonionic gemini surfactant comprises the following two steps:
adding 1.0mol of fatty alcohol-polyoxyethylene ether/alkylphenol polyoxyethylene ether/fatty acid amide polyether amine into a four-necked flask reaction kettle, heating to 50-70 ℃, after nitrogen replacement, adding a catalyst, removing water and a solvent brought by the catalyst in vacuum, adding or not adding an organic solvent, dropwise adding 0.5-0.6mol of bisphenol A diglycidyl ether, completing dropwise adding within 0.5-3h, and keeping a certain temperature to continue reacting for 2-8h to obtain a nonionic gemini surfactant intermediate;
removing the organic solvent from the obtained intermediate at 70-80 ℃ in vacuum, cooling to 30-50 ℃, slowly dripping 2.0-3.0mol of sulfonating agent under rapid stirring, reacting for 3-5h at the temperature of 30-50 ℃ continuously, hydrolyzing the product with alkaline solution, and adjusting the pH value to be neutral to obtain the anionic/nonionic gemini surfactant sulfonate;
fatty alcohol-polyoxyethylene ether/alkylphenol polyoxyethylene ether/fatty acid amide polyoxyethylene ether are used as raw materials, and when a Lewis acid catalyst is adopted, the reaction temperature is controlled to be 70-90 ℃;
fatty alcohol polyoxyethylene ether/alkylphenol polyoxyethylene ether/fatty acid amide polyoxyethylene ether are used as raw materials, and when an alkaline catalyst is adopted, the temperature is controlled at 140-;
when fatty acid amide polyether amine is used as a raw material, one of alkaline catalysts sodium hydroxide or potassium hydroxide is adopted and matched with one of phase transfer catalysts for use, and the temperature is controlled to be 50-80 ℃.
2. The anionic nonionic gemini surfactant according to claim 1, wherein said catalyst comprises at least one of a lewis acid catalyst, a basic catalyst and a phase transfer catalyst;
the Lewis acid catalyst is selected from boron trifluoride diethyl etherate;
the alkaline catalyst is selected from at least one of sodium hydroxide, potassium hydroxide, sodium methoxide and sodium ethoxide;
the phase transfer catalyst is selected from at least one of tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate and hexadecyltrimethylammonium bromide;
the dosage of the catalyst is 0.2-3% of the mass of the reaction substrate.
3. The anionic nonionic gemini surfactant according to claim 1, wherein said organic solvent is selected from the group consisting of anhydrous methanol, ethanol, isopropanol or mixtures thereof with water;
the organic solvent is only added when the fatty acid amide polyether amine is used as a raw material;
the dosage of the organic solvent is 100ml-500ml/mol of raw materials.
4. The anionic nonionic gemini surfactant according to claim 1, wherein said sulfonating agent is selected from concentrated H2SO4H for fuming2SO4、SO3And chlorosulfonic acid;
the alkaline solution is at least one selected from sodium hydroxide, potassium hydroxide and ammonia water.
5. The use of the anionic/nonionic gemini surfactant composition of claim 1 as a temperature-resistant and salt-tolerant oil displacement agent for a block of a virgin oil field having a temperature of 85 ℃ and a total salinity of 250000 mg/L.
6. Use according to claim 5, in total mineralizationThe interfacial tension of 0.05-0.3% solution of temperature-resistant and salt-resistant oil displacement agent containing 50% anionic and nonionic gemini surfactant is less than 8.64 multiplied by 10 under the conditions of formation water with the temperature of 250000mg/L and 85 DEG C-3mN/m。
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