Viscoelastic surfactant composition and preparation method and application thereof
阅读说明：本技术 一种黏弹性表面活性剂组合物及其制备方法和应用 (Viscoelastic surfactant composition and preparation method and application thereof ) 是由 沈之芹 李应成 虞辰敏 裘鋆 于 2020-06-09 设计创作，主要内容包括：本发明公开了一种黏弹性表面活性剂组合物及其制备方法和应用,所述组合物包括式(I)所示多亲水头基阴离子表面活性剂和两性离子型表面活性剂：在式(I)中,R-(1)和R-(2)各自独立选自氢、C-(6)～C-(36)的烃基、C-(6)～C-(36)的取代烃基或磺酸基,且R-(1)和R-(2)不同时为氢或磺酸基；a和b各自独立地选自0或1、且不同时为0；c选自1或2；x为使体系呈电中性的阳离子基团个数,x＝2～5中的任一整数,n～(+)是阳离子或阳离子基团的电荷数；M选自氢、碱金属、碱土金属或铵。本发明所述组合物,由于组分之间的协同效应,表现在高的表观黏度,界面活性的增加、临界胶束浓度的下降、增溶原油能力的提升等方面。(The invention discloses a viscoelastic surfactant composition, a preparation method and application thereof, wherein the composition comprises a multi-hydrophilic head group anionic surfactant shown in a formula (I) and a zwitterionic surfactant: in the formula (I), R 1 And R 2 Each independently selected from hydrogen and C 6 ～C 36 A hydrocarbon group of 6 ～C 36 A substituted hydrocarbon group or a sulfonic acid group of (A), and R 1 And R 2 Not hydrogen or sulfonic acid group at the same time; a and b are each independently selected from 0 or 1 and are not 0 at the same time; c is selected from 1 or 2; x is the number of cationic groups which make the system electrically neutral, x is any integer of 2-5, and n + Is the charge number of the cation or cationic group; m is selected from hydrogen, alkali metal, alkaline earth metal or ammonium. The composition of the invention shows high apparent viscosity, increase of interface activity, reduction of critical micelle concentration, improvement of crude oil solubilizing capability and the like due to synergistic effect among components.)
1. a viscoelastic surfactant composition comprising a polyhydrophilic headgroup anionic surfactant of formula (I):
in the formula (I), R1And R2Each independently selected from hydrogen and C6～C36A hydrocarbon group of6～C36A substituted hydrocarbon group or a sulfonic acid group of (A), and R1And R2Not hydrogen or sulfonic acid group at the same time; and/or, a and b are each independently selected from 0 or 1 and are not both 0; and/or, c is selected from 1 or 2; and/or, x is the number of cationic groups which make the system neutral, x is any integer of 2-5, and n+Is the charge number of the cation or cationic group; and/or, M is selected from hydrogen, alkali metal, alkaline earth metal or ammonium.
2. The composition according to claim 1, wherein in formula (I), R is1And R2Each independently selected from hydrogen and C12～C28A hydrocarbon group of12～C28A substituted hydrocarbon group or a sulfonic acid group of (A), and R1And R2Not hydrogen or sulfonic acid group at the same time; and/or, x ═ 2 or 3; and/or, M is selected from hydrogen, alkali metal or ammonium.
3. The composition of claim 1, wherein the zwitterionic surfactant is of formula (II):
in the formula (II), R3、R4And R5Each independently selected from C1～C36A hydrocarbon group of1～C36Substituted hydrocarbyl of (a) or R' COXR "; r' is selected from C1～C35Or C is a hydrocarbon group1～C35Said R' is selected from C1～C5The alkylene or substituted alkylene of (a), said X is O or NH; and/or, R6Is selected from C1～C36Alkylene or C1～C36Substituted hydrocarbylene groups of (a); and/or, A-Selected from anionic or anionic groups which render the molecule of formula (II) electrically neutral;
preferably, R3Is selected from C6～C28A hydrocarbon group of6～C28Substituted hydrocarbyl of (a) or R' COXR "; r' is selected from C5～C27Or C is a hydrocarbon group5～C27R' is selected from C1～C3X is NH; and/or, R4And R5Each independently selected from C1～C5Or C is a hydrocarbon group1～C5Substituted hydrocarbyl groups of (a); and/or, R6Is selected from C1～C5Alkylene or C1～C5A substituted alkylene group; and/or, A-Selected from anionic or anionic groups which render the molecule of formula (II) electrically neutral.
4. The composition of claim 3, wherein in formula (II), R3Is selected from C10～C24A hydrocarbon group of10～C24Substituted hydrocarbyl of (a) or R' COXR "; r' is selected from C9～C23A hydrocarbon group of9～C23R' is selected from C2～C3X is NH; and/or, R4And R5Each independently selected from C1～C3Or C is a hydrocarbon group1～C3Substituted hydrocarbyl groups of (a); and/or, R6Is selected from C1～C3Alkylene or substituted alkylene of (a); and/or, A-Selected from anionic or anionic groups which render the molecule of formula (II) electrically neutral.
5. Composition according to claim 1, characterized in that the composition optionally further comprises a small molecule salt, preferably selected from at least one of the group consisting of metal halides, metal dicarboxylates, metal nitrates, metal silicates, metal phosphates, metal carboxylates and metal sulfonates, preferably from metal halides and/or metal dicarboxylates.
6. The composition of claim 5,
the metal halide is an alkali metal halide, preferably at least one of sodium bromide, potassium bromide, sodium chloride and potassium chloride; and/or
The metal dicarboxylates are selected from sodium malonate and/or potassium malonate; and/or the metal nitrate is selected from at least one of sodium nitrate, potassium nitrate and ammonium nitrate; and/or
The metal silicate is selected from at least one of sodium silicate, sodium metasilicate, potassium silicate and potassium metasilicate; and/or the metal phosphate is selected from at least one of sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium polyphosphate and potassium polyphosphate; and/or
The metal carboxylate is selected from at least one of sodium acetate, sodium glycolate, potassium acetate, potassium glycolate, sodium benzoate, sodium methyl benzoate, sodium hydroxy benzoate, potassium methyl benzoate, potassium hydroxy benzoate, sodium citrate, potassium citrate, sodium EDTA salt, tartrate, oxalate and sodium gluconate; and/or
The metal sulfonate is at least one selected from sodium ethanesulfonate, potassium ethanesulfonate, sodium benzenesulfonate, potassium benzenesulfonate, sodium methylbenzenesulfonate, potassium methylbenzenesulfonate, sodium hydroxybenzenesulfonate, potassium hydroxybenzenesulfonate, sodium naphthalenesulfonate and potassium naphthalenesulfonate.
7. The composition according to claim 1 to 6, wherein, in the composition,
the molar ratio of the multi-hydrophilic head group anionic surfactant to the zwitterionic surfactant is 1: 0.01-10, preferably 1: 0.05-2.5; and/or
The molar ratio of the multi-hydrophilic head group anionic surfactant to the small molecular salt is 1: 1-10, preferably 1: 1-5.
8. A process for preparing a viscoelastic surfactant composition as claimed in any one of claims 1 to 7, which comprises: mixing said multi-hydrophilic head-based anionic surfactant, said zwitterionic surfactant, and optionally said small molecule salt to provide said composition;
wherein the multi-hydrophilic head group anionic surfactant is obtained by:
step 1, in the presence of a catalyst, selecting from R0CHYCOOR′0Or R0CH2Reactant one of Y and selected from CH2(COOR″0)2Or CH (COOR ″)0)(SO3R″′0) Reacting the reactant II to obtain ester-based compounds respectively R0CH(COOR′0)[CH(COOR″0)2]、R0CH2CH(COOR″0)2、R0CH(COOR′0)[CH(COOR″0)(SO3R″′0)]Or R0CH2[CH(COOR″0)(SO3R″′0)]；
Step 2, putting the ester-based compound obtained in the step 1 into a strong alkaline solution to obtain a multi-hydrophilic head group anionic surfactant I, namely R0CH(COOM)[CH(COOM)2]、R0CH2CH(COOM)2、R0CH(COOM)CH(COOM)(SO3M) or R0CH2[CH(COOM)(SO3M)]；
Optionally performing step 3, adding R in the surfactant I0CH(COOM)[CH(COOM)2]AcidificationThen R is obtained0CH(COOH)[CH(COOH)2]Heating to react, and then neutralizing by alkali to obtain a poly-hydrophilic head group anionic surfactant II which is R0CH(COOM)CH2(COOM)。
9. The method according to claim 8,
R0is selected from C4～C34Or C is a hydrocarbon group4～C34Substituted hydrocarbon radicals of, preferably from C10～C26Or C is a hydrocarbon group10～C26Substituted hydrocarbyl groups of (a); and/or
R′0、R″0And R'0Are each independently selected from C1～C10Alkyl or C1～C10Substituted alkyl of, preferably from C1～C5Alkyl or C1～C5More preferably from methyl, ethyl or propyl; and/or
Y is selected from halogen, preferably from chlorine, bromine or iodine, more preferably from chlorine or bromine.
10. The method according to claim 8,
in step 1, the catalyst is selected from at least one of a metal compound, a metal alkyl compound and a metal amino compound, preferably, the catalyst is selected from an alkali metal compound and/or an alkali metal alkyl compound; and/or
In step 2, the strong alkali solution is selected from an aqueous solution of strong alkali or an aqueous alcohol solution of strong alkali; preferably, the weight concentration of the alkali in the alkaline solution is 5-60 wt%, preferably 10-40 wt%; and/or
Optionally post-treating after the reaction described in step 2, comprising: acid neutralization, alcohol solvent removal, extraction, saturated brine washing and drying; and/or
In step 3, the reaction is carried out at 100 to 400 ℃, preferably at 150 to 250 ℃.
11. The method according to any one of claims 8 to 10, wherein the molar ratio of the hydrophilic-head-group anionic surfactant to the zwitterionic surfactant is 1: 0.01 to 10, preferably 1: 0.05 to 2.5.
12. The method of claim 11, wherein the small molecule salt is selected from at least one of a metal halide, a metal dicarboxylate, a metal nitrate, a metal silicate, a metal phosphate, a metal carboxylate, and a metal sulfonate, preferably at least one of a metal halide and/or a metal dicarboxylate.
13. The preparation method of claim 12, wherein the molar ratio of the multi-hydrophilic head group anionic surfactant to the small molecular salt is 1: 0-10, preferably 1: 1-5.
14. A viscoelastic surfactant composition obtained by the production method according to any one of claims 8 to 13.
15. Use of the viscoelastic surfactant composition according to any one of claims 1 to 7 or the viscoelastic surfactant composition obtained by the preparation method according to any one of claims 8 to 13 or for increasing the production of sandstone oil reservoirs.
16. A method for increasing the production of a sandstone reservoir, comprising the steps of:
(1) mixing the viscoelastic surfactant composition of any one of claims 1 to 7 or the viscoelastic surfactant composition obtained by the preparation method of any one of claims 8 to 13 with water to obtain an oil displacing system;
(2) and injecting the oil displacement system into the oil-bearing stratum to displace the crude oil in the oil-bearing stratum.
17. The method of claim 16, wherein,
in the oil displacing component, the weight concentration of the viscoelastic surfactant composition is 0.1-5.0 wt%, based on the total mass of the multi-hydrophilic head group anionic surfactant shown in the formula (I) and the zwitterionic surfactant shown in the formula (II); and/or
The temperature of the oil-bearing stratum is 30-120 ℃, the water mineralization of the stratum is 100-20, 0000 mg/L, preferably, the oil-bearing stratum is a sandstone oil reservoir, the temperature of the stratum is 40-100 ℃, and the water mineralization of the stratum is 1000-100,000 mg/L; and/or
The viscosity of the crude oil is 1-1000 mPa · s.
Technical Field
The invention relates to a surfactant composition, in particular to a viscoelastic surfactant composition, and a preparation method and application thereof.
Background
Unlike common surfactants, viscoelastic surfactants (VES) form spherical micelles first when the concentration reaches the critical micelle concentration; as the concentration is increased, the spherical micelles begin to be converted into the wormlike micelles, the wormlike micelles rapidly generate, grow and form flexible long rod-shaped micelles, and the rod-shaped micelles are mutually adhered and wound to form a supermolecular network structure similar to the associative polymer.
The viscoelastic surfactant is used as a special surfactant, and the main application field of the viscoelastic surfactant is in the aspect of cleaning fracturing fluid (VES fluid and CFRAC for short), and the research of the viscoelastic surfactant in the aspect of tertiary oil recovery is also reported. VES fracturing fluid has been successfully used by many oil companies at home and abroad3000 times of fracturing construction operation, and good fracturing yield-increasing effect is obtained. For example, Lungwitz, Bernhard et al, by Schlumberger corporation, developed a VES system synthesized from 1, 3-docosenoic acid (erucic acid) with an applicable temperature range of 90-135 deg.C, whose host agent (VESHT) was a quaternary ammonium salt type cationic surfactant, which has been successfully applied to several wells in the Argentina San Jorge basin at temperatures up to 145 deg.C; daniel Patrick Vollmer et al developed a zwitterionic viscoelastic surfactant system, which was mainly compounded from an amphoteric surfactant, lecithin, a non-aqueous solvent, and an organic acid. The highest temperature resistance can reach 150 ℃, and the system has good correspondence to the pH value. Patent US4370243 of meifu petroleum company reports an oil displacement system composed of oil-soluble alcohol, betaine sulfonate and quaternary ammonium salt, which can function as both a surfactant and a fluidity control agent, wherein the quaternary ammonium salt is a cationic surfactant with a carbon chain length of 16-20, 2 wt% of octadecyl dihydroxyethyl propyl betaine sulfonate and 1.0% of n-hexanol are used as an oil displacement composition, after 1.9PV is injected, crude oil can be 100% expelled, but the adsorption loss of the surfactant is as large as 6mg/g, and 2.0% of tetraethylammonium bromide with relatively low price is added as a sacrificial agent to reduce the adsorption amount of the surfactant. The VES reported in SPE 153969 published by Basf is a tris (hydroxyphenyl) methane derivative (TPM), a restricted hydrophobic head group and a flexible hydrophilic tail, and in contrast to conventional viscoelastic surfactants, has an interfacial tension of 1.2mN/m (55 ℃, TDS 18.6% NaCl), and has no significant reduction in viscosity when 0.2% TMP-101-10 is stirred with Bockstedt crude oil at 25 ℃ for 1 hour. The surfactant is synthesized in a laboratory by Chenfu and the like, and the main synthesis process is as follows: mixing octadecanol and phosphorus tribromide, heating to 100 ℃, carrying out reflux reaction for 2 hours, introducing nitrogen to remove redundant phosphorus bromide to obtain bromooctadecane, carrying out reflux reaction on the bromooctadecane and N-methyldiethanolamine for several hours to obtain N-alkyl-N, N-bis (2-hydroxyethyl) octadecyl ammonium bromide (VES-J), carrying out a fracturing fluid formula experiment, and carrying out a fracturing fluid formula experiment at 70 ℃ for 170s-1The viscosity can reach 100mPa.s under the shearing condition.
The viscoelastic surfactant main agent is a cationic or zwitterionic surfactant, although the viscoelastic surfactant main agent has high viscosity, the viscoelastic surfactant main agent has high use concentration and large adsorption capacity on sandstone; the synthesis route of the anion TPM is complex and the preparation cost is high.
Disclosure of Invention
In order to solve the problems of large adsorption capacity and low concentration apparent viscosity of a viscoelastic surfactant in a sandstone reservoir in the prior art, the invention provides a novel viscoelastic surfactant composition. The aqueous solution of the surfactant composition can keep higher viscosity at lower concentration, has strong swept effect on crude oil, and can strip emulsified solubilized crude oil, thereby effectively improving the oil displacement efficiency, and the surfactant composition has the advantages of good thermal stability, low adsorption capacity and the like in sandstone oil reservoirs.
One object of the present invention is to provide a viscoelastic surfactant composition comprising a multi-hydrophilic head group anionic surfactant represented by the formula (I):
in the formula (I), R1And R2Each independently selected from hydrogen and C6～C36A hydrocarbon group of6～C36A substituted hydrocarbon group or a sulfonic acid group of (A), and R1And R2Not hydrogen or sulfonic acid group at the same time; and/or, a and b are each independently selected from 0 or 1 and are not both 0; and/or, c is selected from 1 or 2; and/or, x is the number of cationic groups which make the system neutral, x is any integer of 2-5, and n+Is the charge number of the cation or cationic group; and/or, M is selected from hydrogen, alkali metal, alkaline earth metal or ammonium.
The hydrocarbon group in the present invention includes aliphatic hydrocarbon groups and aromatic hydrocarbon groups.
In a preferred embodiment, in formula (I), R1And R2Each independently selected from hydrogen and C12～C28A hydrocarbon group of12～C28Substituted hydrocarbyl or sulfonic acid ofAnd R is1And R2Not hydrogen or sulfonic acid group at the same time; and/or, x ═ 2 or 3; and/or, M is selected from hydrogen, alkali metal or ammonium.
In a preferred embodiment, the zwitterionic surfactant is of formula (II):
in the formula (II), R3、R4And R5Each independently selected from C1～C36A hydrocarbon group of1～C36Substituted hydrocarbyl of (a) or R' COXR "; r' is selected from C1～C35Or C is a hydrocarbon group1～C35Said R' is selected from C1～C5The alkylene or substituted alkylene of (a), said X is O or NH; and/or, R6Is selected from C1～C36Alkylene or C1～C36Substituted hydrocarbylene groups of (a); and/or, A-Selected from anionic or anionic groups which render the molecule of formula (II) electrically neutral.
In a further preferred embodiment, in formula (II), R3Is selected from C6～C28A hydrocarbon group of6～C28Substituted hydrocarbyl of (a) or R' COXR "; r' is selected from C5～C27Or C is a hydrocarbon group5～C27R' is selected from C1～C3X is NH; and/or, R4And R5Each independently selected from C1～C5Or C is a hydrocarbon group1～C5Substituted hydrocarbyl groups of (a); and/or, R6Is selected from C1～C5Alkylene or C1～C5A substituted alkylene group; and/or, A-Selected from anionic or anionic groups which render the molecule of formula (II) electrically neutral.
In a still further preferred embodiment, in formula (II), R3Is selected from C10～C24A hydrocarbon group of10～C24Substituted hydrocarbyl of (A) or (B)R' COXR "; r' is selected from C9～C23A hydrocarbon group of9～C23R' is selected from C2～C3X is NH; and/or, R4And R5Each independently selected from C1～C3Or C is a hydrocarbon group1～C3Substituted hydrocarbyl groups of (a); and/or, R6Is selected from C1～C3Alkylene or substituted alkylene of (a); and/or, A-Selected from anionic or anionic groups which render the molecule of formula (II) electrically neutral.
The viscoelastic surfactant composition is represented by high apparent viscosity, increase of surface activity, reduction of critical micelle concentration, improvement of crude oil solubilizing capability and the like due to a synergistic effect among components. Especially, the electrostatic action of the surfactants with opposite electric properties promotes the association between two surfactant ions with different charges, and the hydrophobic hydrocarbon chains of the two have certain hydrophobic action, so that a supermolecular network structure is easily formed, therefore, the surfactant composition has higher viscosity, excellent crude oil emulsifying capacity and interface efficiency, and can simultaneously improve the sweep and wash efficiency in the oil displacement process. The molecular structure of the surfactant can be free of high-temperature easily-hydrolyzed groups, so that the surfactant can be used for oil displacement of high-temperature oil reservoirs.
In a preferred embodiment, the composition optionally further comprises a small molecule salt.
In a further preferred embodiment, the small molecule salt is selected from at least one of a metal halide, a metal dicarboxylate, a metal nitrate, a metal silicate, a metal phosphate, a metal carboxylate and a metal sulfonate, preferably from a metal halide and/or a metal dicarboxylate.
Wherein the metal halide and the metal dicarboxylate are small molecule salts generated by reaction during preparation of the composition or are separately added, and the metal nitrate, metal silicate, metal phosphate, metal carboxylate and metal sulfonate are small molecule salts separately added.
In a further preferred embodiment, the metal halide is an alkali metal halide, preferably at least one selected from the group consisting of sodium bromide, potassium bromide, sodium chloride and potassium chloride; and/or, the metal dicarboxylate is selected from sodium malonate and/or potassium malonate; and/or the metal nitrate is selected from at least one of sodium nitrate, potassium nitrate and ammonium nitrate; and/or, the metal silicate is selected from at least one of sodium silicate, sodium metasilicate, potassium silicate and potassium metasilicate; and/or the metal phosphate is selected from at least one of sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium polyphosphate and potassium polyphosphate; and/or the metal carboxylate is selected from at least one of sodium acetate, sodium glycolate, potassium acetate, potassium glycolate, sodium benzoate, sodium methyl benzoate, sodium hydroxy benzoate, potassium methyl benzoate, potassium hydroxy benzoate, sodium citrate, potassium citrate, EDTA sodium salt, tartrate, oxalate and sodium gluconate; and/or the metal sulfonate is at least one selected from sodium ethanesulfonate, potassium ethanesulfonate, sodium benzenesulfonate, potassium benzenesulfonate, sodium methyl benzenesulfonate, potassium methyl benzenesulfonate, sodium hydroxybenzenesulfonate, potassium hydroxybenzenesulfonate, sodium naphthalenesulfonate and potassium naphthalenesulfonate.
The hydrophobic chain of the surfactant is more extended due to the electrostatic effect of the small molecular salt, so that the viscosity of a system can be effectively improved, and the adsorption of the surfactant on a stratum can be reduced.
In a preferred embodiment, the molar ratio of the multi-hydrophilic head group anionic surfactant to the zwitterionic surfactant in the composition is 1 to (0.01-10), preferably 1 to (0.05-2.5).
In a preferred embodiment, the molar ratio of the multi-hydrophilic head group anionic surfactant to the small molecular salt in the composition is 1 to (1-10), preferably 1 to (1-5).
Wherein the molar weight is based on the molar weight of the molecule.
In a preferred embodiment, the composition further comprises a polymer for oil displacement, a foaming agent for oil displacement, a mineral substance for oil displacement (selected from sodium chloride and/or potassium chloride), an alkaline substance (selected from at least one of small-molecule organic amines such as sodium hydroxide, sodium carbonate, sodium bicarbonate, diethanolamine and triethanolamine), an organic small-molecule auxiliary agent (selected from at least one of short-chain fatty alcohol, low-carbon-chain ketone and DMSO), and the like.
Wherein the composition further comprises a flooding component commonly used in the art.
In the composition of the present invention, the multi-hydrophilic head group anionic surfactant of formula (I) and the zwitterionic surfactant of formula (II) are the most effective components, and may be supplied in various forms, such as non-aqueous solid form, aqueous paste form, or aqueous solution form, for convenience of transportation and storage or on-site use; the aqueous solution form comprises a form of preparing a concentrated solution by water and a form of directly preparing a solution with concentration required by on-site oil displacement, for example, a solution with the key active ingredient content of 0.1-5.0 wt% by weight is a form suitable for on-site oil displacement; the water is not particularly required, and can be deionized water or water containing inorganic mineral substances, and the water containing the inorganic mineral substances can be tap water, oil field formation water or oil field injection water.
It is a further object of the present invention to provide a process for the preparation of the viscoelastic surfactant composition of the first object of the present invention, which comprises: mixing said multi-hydrophilic head-based anionic surfactant, said zwitterionic surfactant, and optionally said small molecule salt to provide said composition;
wherein the multi-hydrophilic head group anionic surfactant is obtained by:
step 1, in the presence of a catalyst, selecting from R0CHYCOOR′0Or R0CH2Reactant one of Y and selected from CH2(COOR″0)2Or CH (COOR ″)0)(SO3R″′0) Reacting the reactant II to obtain ester-based compounds respectively R0CH(COOR′0)[CH(COOR″0)2]、R0CH2CH(COOR″0)2、R0CH(COOR′0)[CH(COOR″0)(SO3R″′0)]Or R0CH2[CH(COOR″0)(SO3R″′0)]；
Wherein when R is1Or R2When it is a hydrocarbyl or substituted hydrocarbyl group: r0CHYCOOR′0And CH2(COOR″0)2Condensation reaction is carried out to obtain ester-based compound R0CH(COOR′0)[CH(COOR″0)2]，R0CH2Y and CH2(COOR″0)2Condensation reaction is carried out to obtain ester-based compound R0CH2CH(COOR″0)2. When R is1Or R2In the case of a sulfonic acid group: r0CHYCOOR′0And CH (COOR ″)0)(SO3R″′0) Condensation reaction is carried out to obtain ester-based compound R0CH(COOR′0)[CH(COOR″0)(SO3R″′0)]；R0CH2Y and CH (COOR ″)0)(SO3R″′0) Condensation reaction is carried out to obtain ester-based compound R0CH2[CH(COOR″0)(SO3R″′0)]。
Step 2, putting the ester-based compound obtained in the step 1 into a strong alkaline solution to obtain a multi-hydrophilic head group anionic surfactant I, namely R0CH(COOM)[CH(COOM)2]、R0CH2CH(COOM)2、R0CH(COOM)CH(COOM)(SO3M) or R0CH2[CH(COOM)(SO3M)]。
Wherein R is0CH(COOR′0)[CH(COOR″0)2]Obtaining R through the reaction of step 20CH(COOM)[CH(COOM)2]，R0CH2CH(COOM)2Obtaining R through the reaction of step 20CH2CH(COOR″0)2、R0CH(COOM)CH(COOM)(SO3M) obtaining R by the reaction of step 20CH(COOR′0)[CH(COOR″0)(SO3R″′0)]，R0CH2[CH(COOM)(SO3M)]Obtaining R through the reaction of step 20CH2[CH(COOR″0)(SO3R″′0)]。
Optionally performing step 3, adding R in the surfactant I0CH(COOM)[CH(COOM)2]After acidification R is obtained0CH(COOH)[CH(COOH)2]Heating to react, and then neutralizing by alkali to obtain a poly-hydrophilic head group anionic surfactant II which is R0CH(COOM)CH2(COOM)。
Wherein, the decarboxylation reaction at high temperature is only carried out on the surfactant I containing 3 carboxyl groups in the step 3, and the decarboxylation reaction is also optional and not necessary.
In a preferred embodiment, R0Is selected from C4～C34Or C is a hydrocarbon group4～C34Substituted hydrocarbyl of (A), R'0、R″0And R'0Are each independently selected from C1～C10Alkyl or C1～C10A substituted alkyl group; y is selected from halogen, preferably from chlorine, bromine or iodine.
In a further preferred embodiment, R0Is selected from C10～C26Or C is a hydrocarbon group10～C26Substituted hydrocarbyl groups of (a); and/or, R'0、R″0And R'0Are each independently selected from C1～C5Alkyl or C1～C5Substituted alkyl of (a), preferably from methyl, ethyl or propyl; y is selected from chlorine or bromine.
In a preferred embodiment, in step 1, the catalyst is at least one selected from the group consisting of a metal compound, a metal alkyl compound, and a metal amino compound.
In a further preferred embodiment, in step 1, the catalyst is selected from an alkali metal compound and/or an alkali metal alkyl compound.
In a still further preferred embodiment, in step 1, the catalyst is selected from the group consisting of sodium metal, n-butyllithium, t-butyllithium.
In a preferred embodiment, in step 2, the strong base solution is selected from an aqueous solution of a strong base or an aqueous alcoholic solution of a strong base.
In a further preferred embodiment, in step 2, the weight concentration of the alkali in the alkaline solution is 5 to 60 wt%, preferably 10 to 40 wt%.
In a preferred embodiment, the reaction of step 2 is optionally followed by a post-treatment comprising: acid neutralization, alcohol solvent removal, extraction, saturated brine washing and drying.
In a preferred embodiment, in step 3, the reaction is carried out at 100 to 400 ℃, preferably at 150 to 250 ℃.
The zwitterionic surfactant adopted by the invention can be purchased directly or prepared by a method disclosed by the prior art.
In a preferred embodiment, the molar ratio of the multi-hydrophilic head group anionic surfactant to the zwitterionic surfactant is 1 to (0.01-10), preferably 1 to (0.05-2.5).
In a preferred embodiment, the small molecule salt is selected from at least one of a metal halide, a metal dicarboxylate, a metal nitrate, a metal silicate, a metal phosphate, a metal carboxylate, and a metal sulfonate.
In a further preferred embodiment, the small molecule salt is selected from at least one of a metal halide and/or a metal dicarboxylate.
Among them, metal halide and metal dicarboxylate may be generated during the preparation of the multi-hydrophilic head group anionic surfactant, and thus, these two may not be added separately.
In a preferred embodiment, the molar ratio of the multi-hydrophilic head group anionic surfactant to the small molecular salt is 1: 0-10, preferably 1: 1-5.
The occasion of the mole number of the surfactant and the micromolecular salt in the invention refers to the mole number of the effective substances in the molecular general formula (I) or the molecular general formula (II) or the micromolecular salt in the technical scheme; when the content or concentration of the surfactant composition is referred to, the total concentration of the components of the molecular general formula (I) and the molecular general formula (II) in the above technical scheme is referred to.
The third object of the present invention is to provide a viscoelastic surfactant composition obtained by the second object of the present invention.
The fourth object of the present invention is to provide the use of the viscoelastic surfactant composition of the first object of the present invention or the viscoelastic surfactant composition obtained by the preparation method of the second object of the present invention for improving the yield of sandstone reservoirs.
The fifth purpose of the invention is to provide a method for improving the yield of a sandstone reservoir, which comprises the following steps:
(1) mixing the viscoelastic surfactant composition of the first aspect of the invention or the viscoelastic surfactant composition obtained by the preparation method of the second aspect of the invention with water to obtain an oil displacement system;
(2) and injecting the oil displacement system into the oil-bearing stratum to displace the crude oil in the oil-bearing stratum.
In a preferred embodiment, in the flooding component, the weight concentration of the viscoelastic surfactant composition is 0.1 to 5.0 wt%, based on the total mass of the multi-hydrophilic head group anionic surfactant represented by the formula (I) and the zwitterionic surfactant represented by the formula (II).
In a preferred embodiment, the temperature of the oil-bearing stratum is 30-120 ℃, and the water mineralization of the stratum is 100-20, 0000 mg/L.
In a further preferred embodiment, the oil-bearing stratum is a sandstone reservoir, the temperature of the stratum is 40-100 ℃, and the mineralization degree of the stratum water is 1000-100,000 mg/L.
In a preferred embodiment, the crude oil has a viscosity of 1 to 1000 mPas.
In the present invention, the viscoelastic surfactant composition may be applied according to the prior art, either alone or in combination with a conventional oilfield adjuvant.
The surfactant composition is used for sandstone oil reservoirs, and the surfactant composition accounts for 0.2 wt% of the sandstone oil reservoirs in percentage by mass, and the apparent viscosity is up to 21.4mPa & s; 0.5 wt% of a surfactant composition having an apparent viscosity of up to 132.3 mPas; 1.0 wt% of a surfactant composition having an apparent viscosity of up to 421.2mPa · s; the static adsorption capacity on 100-200 meshes of quartz sand is 0.45mg/g at the lowest, and the static adsorption capacity on clay-containing quartz sand (10 wt% of kaolin and 90 wt% of 100-200 meshes of quartz sand) is 1.13mg/g at the lowest; the dynamic interfacial tension value between the surfactant composition with the use amount of 0.02 wt% and the oil field dehydrated crude oil can reach 0.03518-0.00034 mN/m, the dynamic interfacial tension value between the surfactant composition with the use amount of 0.2 wt% and the oil field dehydrated crude oil can reach 0.00434-0.00023 mN/m, and a better technical effect is achieved.
Compared with the prior art, the invention has the following beneficial effects:
(1) the viscoelastic surfactant composition shows high apparent viscosity, increased surface activity, reduced critical micelle concentration, improved crude oil solubilizing capability and the like due to the synergistic effect among the components;
(2) especially, the electrostatic action of the surfactants with opposite electric properties promotes the association between two surfactant ions with different charges, and the hydrophobic hydrocarbon chains of the two have certain hydrophobic action, so that a supermolecular network structure is easily formed, therefore, the surfactant composition has higher viscosity, excellent crude oil emulsifying capacity and interface efficiency, and can simultaneously improve the sweep and wash efficiency in the oil displacement process;
(3) the viscoelastic surfactant does not contain high-temperature easily-hydrolyzed groups such as ester groups and the like in a molecular structure, so that the viscoelastic surfactant can be used for oil displacement of high-temperature oil reservoirs;
(4) the aqueous solution of the surfactant composition can keep higher viscosity at lower concentration, has strong swept effect on crude oil, and can strip emulsified solubilized crude oil, thereby effectively improving the oil displacement efficiency, and the surfactant composition has the advantages of good thermal stability, low adsorption capacity and the like in sandstone oil reservoirs.
Drawings
The anion of the multi-hydrophilic head group prepared by the inventionThe surfactant can be applied to American Nicolet-5700 spectrometer, and infrared spectrum analysis (scan range 4000-400 cm) is performed by total reflection infrared spectroscopy (ATR) and tabletting method (KBr)-1) And determining the chemical structure of the tested sample so as to achieve infrared characterization of the compound.
FIG. 1 is an infrared spectrum (ATR) of 1,1, 2-octadecyltriphatic acid prepared in example 1. Wherein, 2916.7cm-1And 2850.9cm-1Is a characteristic peak of C-H stretching of methyl and methylene, 1700.3cm-1Is C ═ O stretching vibration absorption peak, 1296.4cm-1Is C-O bond stretching vibration peak, 1467.7cm-1Is OH in-plane bending vibration peak, 949.6cm-1Is the OH out-of-plane bending vibration peak.
FIG. 2 is an infrared spectrum (KBr) of 1,1, 2-octadecyltriphatic acid prepared in example 1. Wherein, 3430.4cm-1Is the characteristic peak of O-H stretching vibration, 2912.4cm-1And 2846.5cm-1Is a characteristic peak of C-H stretching of methyl and methylene, 1695.9cm-1Is C ═ O stretching vibration absorption peak, 1292.0cm-1Is C-O bond stretching vibration peak, 1467.6cm-1Is OH in-plane bending vibration peak, 940.8cm-1Is the OH out-of-plane bending vibration peak.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
The method for testing the content of the multi-hydrophilic head group anionic surfactant comprises the following steps: an analytical method for determining the end point of titration by indicating the change of potential difference (or electrode potential) during titration analysis with a potential measuring device. The measurement is performed by using the relationship between the electrode potential of the electrode and the activity of the component to be measured.
Halmin cation solution as titrant
S－+Hyamine＝S-Hyamine
Under alkaline conditions (pH 11), both carboxylate and sulfonate surfactants exist in salt form and are able to react with hallisin cations, and the surfactant content can be measured using hallisin cation solution as a titrant. Accurately weighing 5.0g of surfactant sample solution to be measured, sampling 3-4 parts in parallel each time, recording the weighed weight WS(g) Respectively adding 40mL of distilled water, and adjusting the pH value of each parallel sample to be about 11.00 by using 0.2M NaOH standard solution; adding 10mL of ethanol and 10mL of methyl isobutyl ketone (MIBK) into the solution with the adjusted pH value in sequence, titrating by adopting a standard solution of Cs and hamming 1622, and recording the volume V of the consumed halminH(mL). The content of the surfactant sample was calculated using formula (1). Where Mw is the molecular weight of the surfactant sample to be tested.
The method for testing the static adsorption capacity comprises the following steps: fully mixing a simulated saline solution of a surfactant and an adsorbate according to a certain liquid-solid ratio, oscillating for a certain time at a set temperature and frequency, cooling, performing centrifugal separation, taking supernatant, measuring the concentration of effective components of the surfactant, and calculating the adsorption capacity of the surfactant, wherein the formula (2) is shown:
Γ ═ W (Co-Ce)/m formula (2);
wherein Γ is the static adsorption capacity (mg/g), W is the weight (g) of the surfactant solution, Co is the initial concentration (mg/g) of the surfactant solution, the post-adsorption concentration (mg/g) of the Ce surfactant solution, and m is the mass (g) of the adsorbent.
The method for testing the apparent viscosity comprises the following steps: preparing a viscoelastic surfactant into a solution with a certain concentration, placing the solution in an oven with a temperature to be measured, stabilizing the solution for 24 hours, and measuring the solution by a barrel method. The water bath of the viscometer is set to the temperature to be measured, and the No. 0 rotor is connected with the viscometerApproximately 16mL of the solution to be measured is transferred to the measurement, kept at the constant temperature for 10 minutes at 7.34-1And (5) measuring the apparent viscosity of the solution under the condition.
The method for testing the interfacial tension comprises the following steps: (1) presetting the temperature to the temperature required by the measurement, and waiting for the temperature to be stable; (2) injecting external phase liquid, filling the centrifuge tube, injecting internal phase liquid, removing bubbles, and tightly covering; (3) the centrifuge tube is arranged in a rotating shaft of the instrument, the rotating speed is set, and a microscope is adjusted to enable inner phase liquid drops or bubbles in the visual field to be very clear; (4) reading and calculating, and calculating the interfacial tension according to the formula (3):
wherein the content of the first and second substances,is interfacial tension (mN. m)-1) Δ ρ is the two-phase density difference (Kg. m)-3) Omega is angular velocity (rad · s)-1) R is the minor axis radius (m) of the droplet, L is the major axis (centrifuge tube axial) diameter, and D is the minor axis (centrifuge tube radial) diameter.
[ example 1 ]
(a) Preparation of potassium 1,1, 2-octadecyl tricarboxylate:
under the protection of nitrogen, 16.1 g (0.7 mol) of fresh sodium metal is cut into threads, carefully added into 150 ml of absolute ethyl alcohol, after the sodium metal reaction is finished, 112.2 g (0.7 mol, M is 160) of diethyl malonate and 195.6 g (0.5 mol, M is 391) of alpha-bromo ethyl stearate are sequentially added, heated to reflux, and when the pH of the reaction solution is nearly neutral, the heating is stopped, and the reaction solution is cooled to room temperature.
And secondly, adding 750 grams of 15 wt% potassium hydroxide ethanol aqueous solution (ethanol-water volume ratio is 4: 6) into the reaction solution, and heating and refluxing for 5-6 hours to obtain the ethanol aqueous solution of the 1,1, 2-octadecyl potassium tricarboxylate. 20 g of the homogeneous reaction solution was acidified with 10 wt% hydrochloric acid, ethanol was distilled off, 50 g of benzene was added, the water layer was separated, the reaction solution was washed with saturated brine for 3 times, benzene was distilled off, and the obtained product was subjected to a merteler T90 autopotentiometric titrator using halmin cation solution as a titrant, whereby the content of 1,1, 2-octadecanetricarboxylic acid was 94.8%. Samples were taken for infrared spectroscopy analysis, see FIG. 1.
(b) Preparation method of viscoelastic surfactant composition VES-01:
adding the ethanol aqueous solution of the potassium 1,1, 2-octadecyl tricarboxylate obtained in the step (a) (calculated by the molar amount of the potassium 1,1, 2-octadecyl tricarboxylate), the octadecyl dihydroxyethyl hydroxypropyl sulfonate betaine and the sodium naphthalenesulfonate into the mixture at about 70 ℃ according to the molar ratio of 1:0.4:0.4, adding water until the system is in a uniform phase, and evaporating the ethanol under reduced pressure to obtain the viscoelastic surfactant composition VES-01 with the content of about 30%.
[ example 2 ]
(a) Preparation of potassium 1,1, 2-docosyltriacarboxylate:
under the protection of nitrogen, 23.0 g (1.0 mol) of fresh sodium metal is cut into threads, carefully added into 200 ml of absolute ethyl alcohol, after the sodium metal reaction is finished, 160.1 g (1.0 mol, M is 160) of diethyl malonate and 223.5 g (0.5 mol, M is 447) of alpha-bromoeicosanoic acid ethyl ester are sequentially added, the mixture is heated to reflux, the heating is stopped when the pH of the reaction solution is nearly neutral, and the reaction solution is cooled to room temperature.
Adding 750 g of 20 wt% potassium hydroxide ethanol aqueous solution (ethanol water volume ratio is 4: 6) into the reaction solution, and heating and refluxing for 7 hours to obtain the ethanol aqueous solution of the 1,1, 2-docosyltriac potassium. 20 g of the homogeneous reaction solution was acidified with 10 wt% hydrochloric acid, ethanol was distilled off, 50 g of benzene was added, the water layer was separated, the reaction solution was washed with saturated brine for 3 times, benzene was distilled off, and the obtained product was subjected to a merteler T90 autopotentiometric titrator using halmin cation solution as a titrant, whereby the content of 1,1, 2-docosyltetricarboxylic acid was 89.3%.
(b) The preparation method of the viscoelastic surfactant composition VES-02 comprises the following steps:
adding the ethanol water solution of the 1,1, 2-docosyltriarboxylic acid potassium obtained in the step (a) and dodecyl dimethyl carboxylic acid betaine into the mixture at about 70 ℃ according to the molar ratio of 1:0.1, adding water until the system is in a uniform phase, and evaporating the ethanol under reduced pressure to obtain the viscoelastic surfactant composition VES-02 with the content of about 30%.
[ example 3 ]
(a) Preparation of potassium 1,1,2- (9-octadecenyl) tricarboxylate:
13.8 g (0.6 mol) of fresh sodium metal is cut into threads under the protection of nitrogen, carefully added into 120 ml of absolute ethyl alcohol for many times, 96.1 g (0.6 mol, M is 160) of diethyl malonate and 194.6 g (0.5 mol, M is 389) of alpha-bromo-9-ene ethyl octadecanoate are sequentially added after the sodium metal reacts, heated to reflux, stopped heating when the pH of the reaction solution is nearly neutral, and cooled to room temperature.
② adding 1000 g of 10 wt% potassium hydroxide ethanol aqueous solution (ethanol water volume ratio is 5: 5) into the reaction solution, heating and refluxing for 5 hours to obtain the ethanol aqueous solution of 1,1,2- (9-ene octadecyl) potassium tricarboxylate. Acidifying 20 g of the homogeneous reaction solution with 10 wt% hydrochloric acid, evaporating ethanol, adding 50 g of benzene, removing a water layer, washing with saturated brine for 3 times, evaporating benzene, and obtaining a product, wherein the content of 1,1,2- (9-octadecenyl) tricarboxylic acid is 91.1% by using a Halmin cation solution as a titrant and adopting a Mettler T90 automatic potentiometric titrator.
(b) The preparation method of the viscoelastic surfactant composition VES-03 comprises the following steps:
adding the ethanol water solution of the potassium 1,1,2- (9-ene octadecyl) tricarboxylate obtained in the step (a), octadecyl dihydroxyethyl hydroxypropyl sulfonate betaine and sodium benzoate into the mixture at the temperature of about 70 ℃ according to the mol ratio of 1:0.6:2, adding water until the system is in a uniform phase, and evaporating the ethanol under reduced pressure to obtain the viscoelastic surfactant composition VES-03 with the content of about 30%.
[ example 4 ]
(a) Preparation of decyl-substituted diammonium succinate:
13.8 g (0.6 mol) of fresh sodium metal is cut into threads under the protection of nitrogen, carefully added into 120 ml of absolute ethyl alcohol for many times, 96.1 g (0.6 mol, M is 160) of diethyl malonate and 146.5 g (0.5 mol, M is 293) of alpha-bromododecanoic acid methyl ester are sequentially added after the sodium metal reacts, heated to reflux, stopped heating when the pH of a reaction solution is nearly neutral, and cooled to room temperature.
② adding 1000 g of 10 wt% potassium hydroxide ethanol water solution (ethanol water volume ratio is 5: 5) into the reaction solution, heating and refluxing for 5 hours to obtain the ethanol water solution of the 1,1, 2-dodecyl potassium tricarboxylate. Distilling off ethanol under reduced pressure, adding the residue into water, acidifying with 10 wt% hydrochloric acid to pH of about 1, adding benzene, extracting, removing water layer, washing with saturated saline solution for 3 times, and distilling off benzene under reduced pressure to obtain 1,1, 2-dodecyl tricarboxylic acid. The content of 1,1, 2-dodecyltricarboxylic acid was 91.7% as measured by using a mertler T90 autopotentiometric titrator and halmin cation solution as a titrant.
Thirdly, heating the 1,1, 2-dodecyl tricarboxylic acid obtained in the step II to 180 ℃ for decarboxylation reaction to obtain decyl substituted succinic acid, and neutralizing with 10 wt% ammonia water until the pH value is 10-11 to obtain decyl substituted diammonium succinate.
(b) Preparation method of viscoelastic surfactant composition VES-04:
adding the decyl-substituted diammonium succinate, the docosyldimethylcarboxyl betaine and the potassium citrate obtained in the step (a) into the mixture at about 40 ℃ according to a molar ratio of 1:0.7:0.2, and adding water until the system is in a uniform phase to obtain the viscoelastic surfactant composition VES-04 with the content of about 30%.
[ example 5 ]
(a) Preparation of potassium octadecyl-1, 2-dicarboxylate-1-sulfonate:
under the protection of nitrogen, 20.8 g (0.9 mol) of fresh sodium metal is cut into threads, carefully added into 150 ml of absolute ethyl alcohol for many times, and after the reaction of the sodium metal is finished, C is added in sequence2H5OCOCH2SO2OC2H5176.4 g (0.9 mol, M ═ 196) and 195.6 g (0.5 mol, M ═ 391) of ethyl α -bromostearate were heated to reflux, and the heating was stopped when the pH of the reaction solution was near neutral, and the reaction solution was cooled to room temperature.
② adding 700 g of 25 wt% potassium hydroxide ethanol aqueous solution (ethanol water volume ratio is 5: 6) into the reaction solution, heating and refluxing for 8 hours to obtain ethanol aqueous solution of octadecyl-1, 2-potassium dicarboxylates-1-potassium sulfonate. Acidifying 20 g of the homogeneous reaction solution with 10 wt% hydrochloric acid, distilling off ethanol, adding 50 g of benzene, removing a water layer, washing with saturated salt solution for 3 times, distilling off benzene, and measuring the content of octadecyl-1, 2-dicarboxylic acid-1-sulfonic acid to be 85.5% by using a Helminum cation solution as a titrant and adopting a Mettler T90 automatic potentiometric titrator.
(b) Preparation method of viscoelastic surfactant composition VES-05:
adding the ethanol water solution of potassium octadecyl-1, 2-dicarboxylate-1-sulfonate obtained in the step (a), octadecyl dimethyl sulfonate betaine and EDTA-tetrasodium into the mixture at the temperature of about 70 ℃ according to the molar ratio of 1:0.9:0.05, adding water until the system is in a uniform phase, and evaporating ethanol under reduced pressure to obtain the viscoelastic surfactant composition VES-05 with the content of about 30%.
[ example 6 ]
(a) Preparation of hexyl substituted disodium succinate:
under the protection of nitrogen, 11.5 g (0.5 mol) of fresh sodium metal is cut into threads, carefully added into 100 ml of absolute ethyl alcohol for many times, after the sodium metal reaction is finished, 80.1 g (0.5 mol, M is 160) of diethyl malonate and 118.4 g (0.5 mol, M is 237) of alpha-bromomethyl octanoate are sequentially added, the mixture is heated to reflux, the heating is stopped when the pH of the reaction liquid is nearly neutral, and the reaction liquid is cooled to room temperature.
② adding 900 g of 10 wt% potassium hydroxide ethanol water solution (ethanol water volume ratio is 5: 5) into the reaction solution, heating and refluxing for 5 hours to obtain the ethanol water solution of 1,1, 2-octyl potassium tricarboxylate. Removing ethanol under reduced pressure, adding the residue into water, acidifying with 10 wt% hydrochloric acid to pH of about 1, extracting with benzene, removing water layer, washing with saturated saline solution for 3 times, and removing benzene under reduced pressure to obtain 1,1, 2-octyl tricarboxylic acid. The content of 1,1, 2-octyl tricarboxylic acid was 96.8% as measured by using a Mettler T90 automatic potentiometric titrator and Heimemin cation solution as a titrant.
Thirdly, heating the 1,1, 2-octyl tricarboxylic acid obtained in the step II to 160 ℃, performing decarboxylation reaction to obtain hexyl substituted succinic acid, and neutralizing the hexyl substituted succinic acid with 40 wt% of sodium hydroxide until the pH value is 11-12 to obtain hexyl substituted disodium succinate.
(b) Preparation method of viscoelastic surfactant composition VES-06:
adding the hexyl-substituted disodium succinate, the docosyl dihydroxyethyl hydroxypropyl sulfonate betaine, the sodium polyphosphate and the potassium nitrate obtained in the step (a) into the mixture at the temperature of about 40 ℃ in a molar ratio of 1:2:0.1:3, and adding water until the system is in a uniform phase to obtain the viscoelastic surfactant composition VES-06 with the content of about 30%.
[ example 7 ]
Viscoelastic surfactant composition VES-07 was prepared in the same manner as in example 1.
(a) Preparation of potassium 1,1, 2-octadecyl tricarboxylate:
under the protection of nitrogen, 16.1 g (0.7 mol) of fresh sodium metal is cut into threads, carefully added into 150 ml of absolute ethyl alcohol, after the sodium metal reaction is finished, 112.2 g (0.7 mol, M is 160) of diethyl malonate and 195.6 g (0.5 mol, M is 391) of alpha-bromo ethyl stearate are sequentially added, heated to reflux, and when the pH of the reaction solution is nearly neutral, the heating is stopped, and the reaction solution is cooled to room temperature.
And secondly, adding 750 grams of 15 wt% potassium hydroxide ethanol aqueous solution (ethanol-water volume ratio is 4: 6) into the reaction solution, and heating and refluxing for 5-6 hours to obtain the ethanol aqueous solution of the 1,1, 2-octadecyl potassium tricarboxylate. 20 g of the homogeneous reaction solution was acidified with 10 wt% hydrochloric acid, ethanol was distilled off, 50 g of benzene was added, the water layer was separated, the reaction solution was washed with saturated brine for 3 times, benzene was distilled off, and the obtained product was subjected to a merteler T90 autopotentiometric titrator using halmin cation solution as a titrant, whereby the content of 1,1, 2-octadecanetricarboxylic acid was 94.8%. Samples were taken for infrared spectroscopy analysis, see FIG. 1.
(b) Preparation method of viscoelastic surfactant composition VES-07:
adding the ethanol aqueous solution of the 1,1, 2-octadecyl potassium tricarboxylate obtained in the step (a) (calculated by the molar amount of the 1,1, 2-octadecyl potassium tricarboxylate), octadecyl dihydroxyethyl hydroxypropyl betaine sulfonate and sodium naphthalenesulfonate into the mixture at about 70 ℃ according to the mol ratio of 1:5:0.4, adding water until the system is in a uniform phase, and evaporating ethanol under reduced pressure to obtain the viscoelastic surfactant composition VES-07 with the content of about 30%.
[ example 8 ]
A viscoelastic surfactant composition VES-08 was prepared in the same manner as in example 1.
(a) Preparation of potassium 1,1, 2-octadecyl tricarboxylate:
under the protection of nitrogen, 16.1 g (0.7 mol) of fresh sodium metal is cut into threads, carefully added into 150 ml of absolute ethyl alcohol, after the sodium metal reaction is finished, 112.2 g (0.7 mol, M is 160) of diethyl malonate and 195.6 g (0.5 mol, M is 391) of alpha-bromo ethyl stearate are sequentially added, heated to reflux, and when the pH of the reaction solution is nearly neutral, the heating is stopped, and the reaction solution is cooled to room temperature.
And secondly, adding 750 grams of 15 wt% potassium hydroxide ethanol aqueous solution (ethanol-water volume ratio is 4: 6) into the reaction solution, and heating and refluxing for 5-6 hours to obtain the ethanol aqueous solution of the 1,1, 2-octadecyl potassium tricarboxylate. 20 g of the homogeneous reaction solution was acidified with 10 wt% hydrochloric acid, ethanol was distilled off, 50 g of benzene was added, the water layer was separated, the reaction solution was washed with saturated brine for 3 times, benzene was distilled off, and the obtained product was subjected to a merteler T90 autopotentiometric titrator using halmin cation solution as a titrant, whereby the content of 1,1, 2-octadecanetricarboxylic acid was 94.8%. Samples were taken for infrared spectroscopy analysis, see FIG. 1.
(b) The preparation method of the viscoelastic surfactant composition VES-08 comprises the following steps:
adding the ethanol aqueous solution of the 1,1, 2-octadecyl potassium tricarboxylate obtained in the step (a) (calculated by the molar amount of the 1,1, 2-octadecyl potassium tricarboxylate), octadecyl dihydroxyethyl hydroxypropyl betaine sulfonate and sodium naphthalenesulfonate into the mixture at about 70 ℃ according to the mol ratio of 1:0.4:8, adding water until the system is in a uniform phase, and evaporating ethanol under reduced pressure to obtain the viscoelastic surfactant composition VES-08 with the content of about 30%.
[ example 9 ]
Water with different salt contents is prepared, the viscoelastic surfactant composition VES-01 is dissolved in corresponding water, and the Apparent Viscosity (AV) is measured, and the results are shown in Table 1. Viscoelastic surfactant compositions VES-02-VES-06 were dissolved in the corresponding water, and the apparent viscosities were measured and shown in Table 2. The apparent viscosity was measured by a Brookfield FILED model III rotational viscometer, Bohler fly, USA, 7.34s-1。
[ example 10 ]
Preparation of HCO3 -Is 1500mg/L, TDS is simulated saline at 15000mg/L to prepare a viscoelastic surfactant aqueous solution. The static adsorption experiment process is as follows: mixing 10g of simulated saline solution of the surfactant and 1g of adsorbent, oscillating for 24h at 50 ℃, cooling, performing centrifugal separation, taking supernatant, measuring the concentration of effective components of the surfactant by using a TOC method, and calculating the adsorption amount of the surfactant in unit mg/g, wherein the results are shown in Table 3. Wherein the adsorbent A is 100-200 mesh quartz sand, and the adsorbent B is clay-containing quartz sand (10 wt% of kaolin and 90 wt% of 100-200 mesh quartz sand).
[ example 11 ]
The crude oil for the experiment comes from an oil field, the viscosity of the crude oil is shown in table 4, and the crude oil is used after dehydration and is the viscosity of the ground crude oil.
The surfactant composition was dissolved in the corresponding simulated water, and the oil-water interfacial tension of the surfactant solution on crude oil was measured, and the results are shown in Table 4. The oil-water interfacial tension (IFT) was measured by a model TX500 spinning drop interfacial tensiometer, produced by Texas university, USA.
[ COMPARATIVE EXAMPLE 1 ]
The procedure of example 1 was repeated except that in step (b):
replacing 1,1, 2-octadecyl tricarboxylic acid potassium with equal amount of octadecyl dihydroxyethyl hydroxypropyl sulfonic acid betaine, adding ethanol and water until the system is in a uniform phase, and evaporating the ethanol under reduced pressure to obtain the viscoelastic surfactant composition VES-D1 with the content of about 30%. The results of the performance tests conducted in the same manner as in examples 9, 10 and 11 are shown in tables 1,3 and 4.
[ COMPARATIVE EXAMPLE 2 ]
The procedure of example 1 was repeated except that in step (b):
and (b) replacing octadecyl dihydroxyethyl hydroxypropyl sulfonic betaine with 1,1, 2-octadecyl tricarboxylic acid potassium by equivalent amount of 1,1, 2-octadecyl tricarboxylic acid potassium, adding the ethanol water solution of the 1,1, 2-octadecyl tricarboxylic acid potassium obtained in the step (a) and sodium naphthalenesulfonate, adding water until the system is in a uniform phase, and evaporating ethanol under reduced pressure to obtain the viscoelastic surfactant composition VES-D2 with the content of about 30%. The results of the performance tests conducted in the same manner as in examples 9, 10 and 11 are shown in tables 1,3 and 4.
[ COMPARATIVE EXAMPLE 3 ]
The procedure of example 1 was repeated except that in step (b):
adding potassium stearate, octadecyl dihydroxyethyl hydroxypropyl sulfonate betaine and sodium naphthalenesulfonate into the mixture at the temperature of about 70 ℃ and the mol ratio of 1:0.4:0.4, adding ethanol and water until the system is in a uniform phase, and evaporating the ethanol under reduced pressure to obtain the viscoelastic surfactant composition VES-D3 with the content of about 30%. The results of the performance tests conducted in the same manner as in examples 9, 10 and 11 are shown in tables 1,3 and 4.
[ COMPARATIVE EXAMPLE 4 ]
The procedure of example 1 was repeated except that sodium naphthalenesulfonate was not added in step (b):
mixing ethanol water solution of 1,1, 2-octadecyl potassium tricarboxylate and octadecyl dihydroxyethyl hydroxypropyl sulfobetaine with ethanol and water at the molar ratio of 1:0.4 at about 70 ℃ until the system is in a uniform phase, and evaporating the ethanol under reduced pressure to obtain the viscoelastic surfactant composition VES-D4 with the content of about 30%. Performance tests were conducted as in example 9, example 10, and example 11, using the same amount of VES-D4 in place of VES-01, and the results are shown in tables 1,3, and 4.
[ COMPARATIVE EXAMPLE 5 ]
The procedure of example 1 was repeated except that in step (b):
adding gemini cationic surfactant C at about 70 deg.C according to the molar ratio of 1:0.4:0.416H33N+(CH3)2(CH2)4N+(CH3)2C16H33.2Cl-(16-4-16.2Cl-) Octadecyl dihydroxyethyl hydroxypropyl sulfonic acid betaine and sodium naphthalene sulfonate are added with ethanol and water until the system presents a uniform phase, and the ethanol is distilled off under reduced pressure to obtain the viscoelastic surfactant composition VES-D5 with the content of about 30 percent. The results of the performance tests conducted in the same manner as in examples 9, 10 and 11 are shown in tables 1,3 and 4.
Table 1:
table 2:
table 3:
serial number
Surfactant composition
Adsorbent and process for producing the same
Static adsorption capacity (mg/g)
1
VES-01
A
0.64
2
VES-02
A
1.03
3
VES-03
A
0.78
4
VES-04
A
0.45
5
VES-05
A
0.99
6
VES-06
A
1.79
7
VES-07
A
1.22
8
VES-08
A
0.54
9
VES-01
B
1.49
10
VES-02
B
1.72
11
VES-03
B
1.63
12
VES-04
B
1.23
13
VES-05
B
1.71
14
VES-06
B
2.33
15
VES-07
B
2.45
16
VES-08
B
1.13
17
VES-D1
A
1.89
18
VES-D1
B
3.97
19
VES-D2
A
0.54
20
VES-D2
B
1.33
21
VES-D3
A
1.23
22
VES-D3
B
2.56
23
VES-D4
A
0.82
24
VES-D4
B
1.77
25
VES-D5
A
3.87
26
VES-D5
B
5.02
Table 4:
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