Alkoxy polyether anionic and nonionic surfactant containing heteroatom and preparation method thereof
阅读说明：本技术 含杂原子的烷氧基聚醚阴非离子表面活性剂及其制备方法 (Alkoxy polyether anionic and nonionic surfactant containing heteroatom and preparation method thereof ) 是由 李应成 张卫东 金军 沈之芹 鲍新宁 沙鸥 于 2019-11-14 设计创作，主要内容包括：本发明涉及含杂原子的烷氧基聚醚阴非离子表面活性剂及其制备方法,主要解决现有强化采油技术中表面活性剂乳化性能差、活性低的技术问题。通过采用一种含杂原子的烷氧基聚醚阴非离子表面活性剂,具有如下分子通式：其中,R-1为C-1～C-(50)的脂肪基、芳香基中的任意一种；R-2、R-3、R-4独立选自乙基、丙基、丁基中的至少一种,x、y、z为0～100且大于0中的任意一个数；L-1、L-2独立选自含杂原子和两个自由端的连接基；X为包含1-10个碳原子的亚烷基、亚烯基、亚芳基中的任意一种；Y为阴离子基团；M为阳离子或阳离子基团的技术方案,较好地解决了现有表面活性剂乳化能力差的技术问题,可用于油田强化采油过程。R-1─O─(OR-2)-x─L-1─(OR-3)-y─L-2─(OR-4)-z─X─Y～(a-)·a/bM～(b+)。(The invention relates to a heteroatom-containing alkoxy polyether anionic and nonionic surfactant and a preparation method thereof, and mainly solves the technical problems of poor emulsifying property and low activity of the surfactant in the prior enhanced oil recovery technology. By adopting a heteroatom-containing alkoxy polyether anionic nonionic surfactant, the surfactant has the following molecular formula: wherein R is 1 Is C 1 ～C 50 Any one of the aliphatic group and the aromatic group of (1); r 2 、R 3 、R 4 Independently selected from at least one of ethyl, propyl and butyl, x, y and z are 0-100 and are largeAny number from 0; l is 1 、L 2 Independently selected from a heteroatom-containing and two free-end linking groups; x is any one of alkylene, alkenylene and arylene containing 1 to 10 carbon atoms; y is an anionic group; the technical scheme that M is cation or cation group better solves the technical problem that the prior surfactant has poor emulsifying capacity, and can be used for the enhanced oil recovery process of oil fields. R 1 ─O─(OR 2 ) x ─L 1 ─(OR 3 ) y ─L 2 ─(OR 4 ) z ─X─Y a‑ ·a/bM b+ 。)
1. A heteroatom-containing alkoxy polyether anionic nonionic surfactant has the following molecular formula:
R1─O─(OR2)x─L1─(OR3)y─L2─(OR4)z─X─Ya-·a/bMb+；
wherein R is1Is C1～C50Any one of the aliphatic group and the aromatic group of (1); r2、R3、R4Independently selected from at least one of ethyl, propyl and butyl, and any number of x, y and z is 0-100 and more than 0; l is1、L2Independently selected from a heteroatom-containing and two free-end linking groups; x is any one of alkylene, alkenylene and arylene containing 1 to 10 carbon atoms; y is an anionic group; m is a cation or cationic group that maintains the formula in charge balance; a is the absolute value of the valence of Y, and b is the absolute value of the valence of M.
2. The anionic heteroatom containing alkoxy polyether surfactant of claim 1, wherein R is1Is C1～C50Any one of alkyl, alkenyl, aryl and polycyclic aromatic hydrocarbon of (a); more preferably C1～C30Any one of alkyl, alkenyl, aryl and polycyclic aromatic hydrocarbon of (a); the heteroatom is N and/or S.
3. The anionic heteroatom containing alkoxy polyether surfactant of claim 1, wherein L is1、L2Independently selected from-NR6-、-S-、-X1-R5-X2At least one of (A) to (B), wherein X1、X2Independently selected from NR6Or S, R5Is selected from C0-C10Any one of alkylene, alkenylene and arylene, R6Is selected from H or C1～C4Alkyl group of (1).
4. The anionic heteroatom containing alkoxy polyether surfactant of claim 3, wherein R is5Is selected from C0-C6Any one of alkylene, alkenylene and arylene of (1), R6Is selected from H.
5. The anionic and nonionic surfactant of alkoxy polyether containing hetero atom as claimed in claim 1, wherein the polymerization degree x, y, z of alkoxy group is any number of 1 to 50.
6. The anionic heteroatom containing alkoxy polyether surfactant as claimed in claim 1, wherein X is any one of alkylene, alkenylene and arylene radical containing 1-6 carbon atoms.
7. The anionic surfactant of alkoxy polyether containing hetero atom as claimed in claim 1, wherein the anionic group is at least one of carboxylate, sulfonate, sulfate and phosphate, preferably at least one of carboxylate and sulfonate; the M is at least one selected from alkali metal cations, alkaline earth metal cations and ammonium ions; more preferably selected from Na+、K+、Mg2+、Ca2+、NH4 +At least one of (1).
8. A method for preparing the alkoxy polyether anionic and nonionic surfactant as claimed in any one of claims 1 to 7, comprising the following steps:
a) carrying out alkoxylation reaction on an initiator, ethylene oxide, propylene oxide and butylene oxide in the presence of a catalyst to obtain an alkoxy polyether nonionic surfactant; wherein the initiator contains C1～C50Alkyl alcohol, alkenyl alcohol, alkylphenol,Any one of polycyclic aromatic phenols;
b) reacting the alkoxy polyether nonionic surfactant obtained in the step a) with an organic amine reagent or a thiol reagent to obtain an alkoxy polyether nonionic surfactant containing N and/or S heteroatoms;
c) and c) carrying out sulfonation or carboxylation reaction on the alkoxy polyether nonionic surfactant containing the heteroatom obtained in the step b) and a sulfonation reagent or a carboxylation reagent, and then neutralizing to obtain the alkoxy polyether anionic nonionic surfactant.
9. The preparation method of the anionic and nonionic surfactant of the alkoxy polyether as claimed in claim 8, wherein the reaction temperature of the alkoxylation reaction is 140-200 ℃, the reaction pressure is 0-5 MPa, and the molar ratio of the initiator to the ethylene oxide, the propylene oxide or the butylene oxide is 1 (1-50); the catalyst is alkali metal hydroxide, DMC (dimethyl carbonate) double metal polyether catalyst or phosphazene catalyst, and the using amount of the catalyst is 0.001-2.0% of the weight of the initiator; the reaction temperature in the step b) is 100-200 ℃, the reaction pressure is 0-5 MPa, and the reaction time is 1-10 hours; the reaction temperature of the sulfonation reaction or the carboxylation reaction is 80-200 ℃, and the reaction pressure is 0-3 MPa.
10. Use of an alkoxy polyether anionic or nonionic surfactant as claimed in any one of claims 1 to 7.
Technical Field
The invention relates to a heteroatom-containing alkoxy polyether anionic and nonionic surfactant and a preparation method thereof.
Background
With the increase of world energy demand, the reasonable development and utilization of petroleum have attracted great attention of people, and the requirements on the production quantity and the production efficiency of petroleum are higher and higher. The method realizes the efficient exploitation of oil and gas resources, and has practical significance and important strategic significance for improving the yield of crude oil. Conventional oil recovery methods (primary and secondary methods) generally only recover 1/3, which is the geological reserve of crude oil, and also fail to recover about 2/3 of crude oil, and thus enhanced oil recovery has been a significant issue in oil recovery research. The tertiary oil recovery technology is an effective method for improving the oil recovery rate and can be divided into four categories, namely thermal flooding, steam flooding, in-situ combustion and the like; second, miscible flooding, comprising CO2Miscible phase, hydrocarbon miscible phase and other inert gas miscible phase flooding; thirdly, chemical flooding; and fourthly, microbial oil recovery, including biopolymer and microbial surfactant flooding. Chemical flooding is a very important and large-scale technology implemented in enhanced oil recovery, and includes polymer flooding, surfactant flooding, alkali water flooding, concentrated sulfuric acid flooding and the like, as well as various combination technologies of polymer, alkali and surfactant. The chemical flooding effect is the result of physical action, which is the sweeping action of the displacement fluid, and chemical action, which is the microscopic displacement action of the displacement fluid. The key to the chemical action is to reduce the interfacial tension of the displacement fluid and the crude oil and improve the oil washing efficiency. The surfactant has both oleophilic (hydrophobic) and hydrophilic (oleophobic) properties,when the surfactant is dissolved in water, molecules are mainly distributed on an oil-water interface, and the oil-water interface tension can be remarkably reduced. The reduction of the oil-water interfacial tension means the reduction of the work of adhesion, i.e., the crude oil is easily eluted from the surface of the formation, thereby improving the oil washing efficiency. The oil displacement effect of the surfactant is also shown in the effects of reversing the wettability of the oleophilic rock surface, emulsifying crude oil, improving the surface charge density, merging oil drops and the like, which is the reason why the surfactant plays a significant role in the chemical flooding technology.
At present, the most used tertiary oil recovery surfactants at home and abroad are petroleum sulfonate, alkylbenzene sulfonate, olefin sulfonate and other surfactants, and are referred to as CN1203935A, CN1566258A, CN1458219A, CN1426833A and US 2010/0282467. The surfactant has the advantages of wide source, low cost and the like. However, with the increasing depth of the exploitation degree of the oil field and the increasing depth of the oil extraction stratum, the use temperature of the surfactant is higher and higher, and the mineralization degree of water quality is higher and higher. However, the salt tolerance of the surfactant, especially the divalent cation tolerance, is poor, so that the surfactant cannot be applied to high-temperature and high-salinity oil field blocks. Therefore, the development of the novel temperature-resistant salt-resistant surfactant has great significance for the tertiary oil recovery industry.
In recent years, anionic and nonionic surfactants have attracted attention because of their heat resistance of anionic surfactants and salt resistance of nonionic surfactants. The anionic nonionic surfactant mainly comprises alkoxy carboxylate, alkoxy sulfonate, alkoxy sulfate salt and the like. For example, Zhang Yongmin and Zhang Hujun respectively report the performances of anionic and nonionic surfactants such as sodium nonylphenol polyoxyethylene ether sulfonate and sodium fatty alcohol polyoxyethylene ether sulfonate (see: 2009, 26(2), 4-7; oilfield chemistry, 2009, 26(1), 72-75; chemical research and application, 2009, 21(7), 964-968; daily chemical industry, 2008, 38(4), 253-256; CN 201210188897.6). The use of anionic and nonionic surfactants such as alkoxy carboxylates and alkoxy sulfonates in enhanced Oil recovery has also been reported by the university of Texas, Austin division, USA, Oil Chem Technology, BASF, respectively. (see SPE 154256; SPE 154261;US 7,629,299; US 20120101010; US2011120707a 1; US20140116690a 1). In the above anionic nonionic surfactants, the nonionic moiety is solely ethoxy and/or propoxy. In US20110281779, however, anionic nonionic surfactants R containing a non-ionic segment of butoxy BO, propoxy PO and ethoxy EO are disclosed1-BOx-POy-EOz-X-Ya- a/b Mb+And shows better performance. Wherein R is1Is obtained by dimerization of linear or branched fatty alcohol of C12-C36 through Guerbet reaction.
Disclosure of Invention
The invention relates to a novel alkoxy polyether anionic and nonionic surfactant containing heteroatoms, which simultaneously contains the heteroatoms N, S and composite polyether functional groups BO, PO and EO in the molecular structure, is favorable for accurately regulating and controlling the interaction of the surfactant and crude oil on one hand, and solves the technical problems of poor emulsifying property and low activity of the surfactant in the prior enhanced oil recovery technology. Meanwhile, the lipophilic group is not limited to the lipophilic carbon chain of C8-C18 in the traditional sense, thereby greatly widening the source of raw materials and reducing the production cost. In addition, in terms of selection of the lipophilic group, the lipophilic group is more prone to simultaneously contain the aliphatic lipophilic group and the aromatic lipophilic group, so that the interaction between the lipophilic group and the crude oil is enhanced, and the oil displacement performance is improved.
One of the technical problems to be solved by the invention is the technical problems of poor emulsifying property and low activity of the surfactant under the conditions of high temperature and high salt in the prior art; and the surfactant has the problems of narrow raw material source and high production cost, and provides a novel alkoxy polyether anionic and nonionic surfactant containing heteroatoms, which has the advantages of good emulsifying capacity and high activity, and can contain aliphatic and aromatic lipophilic groups, so that the interaction between the surfactant and crude oil is enhanced, and the oil displacement performance is improved.
The second technical problem to be solved by the invention is to provide a preparation method of alkoxy polyether anionic and nonionic surfactant containing hetero atoms. The method has the characteristics of simple process, mild reaction conditions and high product yield.
The invention also provides an application method of the alkoxy polyether anionic surfactant containing the heteroatom.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a heteroatom-containing alkoxy polyether anionic nonionic surfactant has the following molecular formula:
R1─O─(OR2)x─L1─(OR3)y─L2─(OR4)z─X─Ya-·a/bMb+
wherein R is1Is C1～C50Any one of the aliphatic group and the aromatic group of (1); r2、R3、R4Independently selected from at least one of ethyl, propyl and butyl, and any number of x, y and z is 0-100 and more than 0; l is1、L2Independently selected from a heteroatom-containing and two free-end linking groups; x is any one of alkylene, alkenylene and arylene containing 1 to 10 carbon atoms; y is an anionic group; m is a cation or cationic group that maintains the formula in charge balance; a is the absolute value of the valence of Y, and b is the absolute value of the valence of M.
In the above technical scheme, R1Preferably C1～C50Any one of alkyl, alkenyl, aryl and polycyclic aromatic hydrocarbon of (a); more preferably C1～C30Any one of alkyl, alkenyl, aryl and polycyclic aromatic hydrocarbon of (a); the heteroatom is preferably N and/or S.
In the above technical solution, L1、L2Independently is preferably selected from the group consisting of-NR6-、-S-、-X1-R5-X2At least one of (A) to (B), wherein X1、X2Independently preferably selected from NR6Or S, R5Preferably selected from C0-C10Any one of alkylene, alkenylene and arylene, R6Preferably selected from H or C1～C4Alkyl groups of (a); r5Preferably selected from C0When it is, then it represents-X1-X2-directly connected.
In the above technical scheme, R5More preferablyIs selected from C0-C6Any one of alkylene, alkenylene and arylene of (1), R6More preferably selected from H.
In the above technical solution, the alkoxy polymerization degrees x, y, and z are independently preferably any number of 1 to 100, and more independently preferably any number of 1 to 50.
In the above technical solution, X is preferably any one of an alkylene group, an alkenylene group, and an arylene group containing 1 to 6 carbon atoms.
In the above technical solution, the anionic group Y is preferably at least one of carboxylate, sulfonate, sulfate, and phosphate, and more preferably at least one of carboxylate and sulfonate.
In the above technical solution, M is preferably at least one selected from alkali metal cations, alkaline earth metal cations, and ammonium ions; more preferably selected from Na+、K+、Mg2+、Ca2+、NH4 +At least one of (1).
To solve the second technical problem, the invention adopts the following technical scheme: a method for preparing the anionic and nonionic surfactant containing the heteroatom alkoxy polyether, which is described in any one of the technical schemes for solving the technical problems, comprises the following steps:
a) carrying out alkoxylation reaction on an initiator, ethylene oxide, propylene oxide and butylene oxide in the presence of a catalyst to obtain an alkoxy polyether nonionic surfactant; wherein the initiator contains C1～C50Any one of the alkyl alcohol, alkenyl alcohol, alkylphenol and polycyclic aromatic phenol;
b) reacting the alkoxy polyether nonionic surfactant obtained in the step a) with an organic amine reagent or a thiol reagent to obtain an alkoxy polyether nonionic surfactant containing N and/or S heteroatoms;
c) and c) carrying out sulfonation or carboxylation reaction on the alkoxy polyether nonionic surfactant containing the heteroatom obtained in the step b) and a sulfonation reagent or a carboxylation reagent, and then neutralizing to obtain the alkoxy polyether anionic nonionic surfactant.
In the technical scheme, the reaction temperature of the alkoxylation reaction is preferably 140-200 ℃, and the reaction pressure is preferably 0-5 MPa; the molar ratio of the initiator to the ethylene oxide, the propylene oxide or the butylene oxide is preferably 1 (1-50); the catalyst is preferably an alkali metal hydroxide, a DMC (double metal polyether) catalyst or a phosphazene catalyst, and the using amount of the catalyst is preferably 0.001-2.0% of that of the initiator.
In the technical scheme, the reaction temperature in the step b) is preferably 100-200 ℃, the reaction pressure is preferably 0-5 MPa, and the reaction time is preferably 1-10 hours.
In the technical scheme, the reaction temperature of the sulfonation reaction or the carboxylation reaction is preferably 80-200 ℃, the reaction pressure is preferably 0-3 MPa, and the reaction time is preferably 1-10 hours.
In the technical scheme, the reaction temperature of the alkoxylation reaction is more preferably 140-200 ℃, and the pressure is more preferably 0.1-2.0 MPa; the reaction temperature in the step b) is more preferably 100-150 ℃, and the reaction pressure is more preferably 0.5-3 MPa; the reaction temperature in the step c) is more preferably 50-100 ℃, and the reaction time is more preferably 0.5-5 hours.
In the above technical scheme, the sulfonating agent can be various sulfonating agents commonly used in the art, such as halogenated sulfonic acid or/and salts thereof, such as but not limited to chlorohexylsulfonic acid (sodium), p-chlorobenzenesulfonic acid (sodium), 3-chloro-2-hydroxy-propanesulfonic acid (sodium), 1-chloro-2-butene-sulfonic acid (sodium), and the like; the carboxylation agent may be any of the various carboxylation agents commonly used in the art, such as halogenated carboxylic acids or/and salts thereof, such as, but not limited to, chloroacetic acid (sodium).
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: the use of a nonionic surfactant of the type described in any of the preceding technical solutions to solve any of the above problems.
In the above technical solution, the application is not particularly limited, for example, but not limited to the application in oil and gas field enhanced oil recovery, for example, when the aqueous solution containing the surfactant of the present invention is injected into the underground for enhancing oil and gas field enhanced oil recovery, the use concentration of the surfactant may be 0.01 w.t.% or more, preferably 0.05 w.t.% or more, and more preferably 0.05 to 1 w.t.%.
According to the alkoxy polyether anionic and nonionic surfactant containing the heteroatom, through introducing the heteroatom, the alkoxy and the chain segment design, the interaction between the surfactant and the crude oil components is enhanced, so that the surfactant has stronger emulsifying capacity and can better solubilize the crude oil; meanwhile, the oil washing capacity is good, so that the recovery ratio is improved.
The alkoxy polyether anionic nonionic surfactant containing the heteroatom has the following advantages when being used in a surfactant composition for tertiary oil recovery:
(1) the surfactant has high interfacial activity and strong emulsifying capacity. When the concentration is more than 0.05 percent, 10 can be formed with underground crude oil-3～10-4The ultra-low interfacial tension of milli-Newton/m, the solubilization parameter reaches more than 12.
(2) High heat resistance and high salt resistance. Because the salt-resistant agent contains non-ionic groups such as BO, PO, EO and the like, the salt-resistant capability of the salt-resistant agent is obviously improved; different functional groups are connected through C-C bonds or C-O bonds, so that the hydrothermal stability is high.
(3) R bound to alkoxy1May be C1～C50The surfactant has wide raw material source and low preparation cost.
Compared with the prior art, the alkoxy polyether anionic and nonionic surfactant containing the heteroatom has better emulsifying capacity and higher interfacial activity, the solubilization parameter of crude oil can reach more than 18, and the interfacial tension can reach 10-4Milli-newton per meter, the recovery ratio can be increased by more than 15 percent, and a better technical effect is obtained.
The invention is further illustrated by the following examples.
Detailed Description
Example 1 Synthesis of sodium Phenolpolyether carboxylate anionic surfactant containing heteroatom N
Adding a certain amount of phenol and 1% KOH (potassium hydroxide) by mass as a catalyst into a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, purging with nitrogen for 3-4 times to remove air in the system, raising the reaction temperature to 200 ℃, slowly introducing metered butylene oxide, and controlling the reaction pressure to be less than 2.0MPa to carry out etherification reaction. After the reaction is finished, adding hydrazine hydrate in calculated amount, and reacting for 1 hour at the temperature of 100 ℃ and the pressure of 5 MPa. Then heating to 180 ℃, continuously and slowly introducing the calculated amount of propylene oxide, after the reaction is finished, adding hydrazine hydrate again and reacting for 10 hours at 100 ℃. And (3) heating to 150 ℃ again, adding a calculated amount of ethylene oxide, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), purging the system by using nitrogen, and removing unreacted ethylene oxide to obtain the phenol polyoxybutylene polyoxypropylenepolyoxyethylene ether nonionic surfactant with different polymerization degrees.
And (3) putting the obtained product and 2 times of molar weight of potassium hydroxide into a reactor, starting stirring, alkalizing for 2 hours at 60 ℃, heating to 80 ℃, slowly adding sodium chloroacetate, continuing to react for 5 hours after the addition is finished, and performing post-treatment to obtain the phenol polyether sodium carboxylate anionic nonionic surfactant containing heteroatom N. The structure is shown in table 1.
Example 2 Synthesis of calcium nonylphenol polyether sulfonate anionic nonionic surfactant containing heteroatom N
Adding a certain amount of nonyl phenol and 0.5% KOH (potassium hydroxide) by mass as a catalyst into a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, purging with nitrogen for 3-4 times to remove air in the system, raising the reaction temperature to 170 ℃, slowly introducing metered propylene oxide, and controlling the reaction pressure to be less than 0.60MPa to carry out etherification reaction. After the reaction is finished, adding ethylenediamine, and reacting for 8 hours at the temperature of 150 ℃ and the pressure of 4 MPa. Then slowly introducing the calculated amount of butylene oxide, after the reaction is finished, adding ethylenediamine again, and reacting for 8 hours at the temperature of 150 ℃ and the pressure of 4 MPa; and finally, adding a calculated amount of ethylene oxide, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), and purging the system by using nitrogen to remove unreacted ethylene oxide to obtain the nonyl phenol polyether nonionic surfactant containing heteroatom N.
And (3) putting the obtained product and 2 times of molar weight of potassium hydroxide into a reactor, stirring, alkalizing for 2 hours at 60 ℃, heating to 90 ℃, slowly dropwise adding sodium chlorohexyl sulfonate, continuing to react for 5 hours after the addition, and then adding calcium chloride for ion exchange to obtain the heteroatom N-containing calcium nonylphenol polyether sulfonate anionic and nonionic surfactant. The structure is shown in table 1.
Example 3 Synthesis of N heteroatom containing ammonium dodecylnaphthalene polyether benzenesulfonate anionic nonionic surfactant
Adding dodecyl naphthol, 2.0% of KOH and 30ppm of phosphazene catalyst by mass into a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, purging with nitrogen for 3-4 times to remove air in the system, raising the reaction temperature to 180 ℃, slowly introducing metered butylene oxide, and controlling the reaction pressure to be less than 0.60MPa to carry out etherification reaction. After the reaction is finished, adding propane diamine, and reacting for 6 hours at the temperature of 200 ℃ and the pressure of 2 MPa; then introducing propylene oxide with calculated amount, and after the reaction is finished, adding propane diamine again to carry out ammoniation reaction; finally, adding the calculated amount of ethylene oxide again, carrying out etherification reaction again at 150 ℃ until the reaction is finished (the reaction pressure is unchanged), and purging the system by using nitrogen to remove the unreacted ethylene oxide to obtain the dodecyl naphthalene polyether nonionic surfactant. Propane diamine
And (2) placing the obtained product and potassium hydroxide with 2 times of molar weight into a reactor, starting stirring, alkalizing for 2 hours at 60 ℃, heating to 200 ℃, adding sodium p-chlorobenzenesulfonate, continuing to react until the raw materials are completely converted after the sodium p-chlorobenzenesulfonate is added, and performing post-treatment ammonium exchange to obtain the dodecyl naphthalene polyether ammonium benzenesulfonate anionic and nonionic surfactant containing heteroatom N. The structure is shown in table 1.
Example 4 Synthesis of magnesium Methoxypolyethercarboxylate anionic nonionic surfactant containing heteroatom S, N
Adding a certain amount of methanol and 0.5 percent KOH (potassium hydroxide) by mass as a catalyst into a polymerization reaction kettle, heating the system to 140 ℃ under stirring, slowly introducing metered ethylene oxide, and controlling the reaction pressure to be less than 1.0MPa to carry out etherification reaction. After the reaction in the step is finished, continuously and slowly introducing 1, 3-propanedithiol, and reacting for 5 hours at the temperature of 180 ℃ and the pressure of 2 MPa; then the calculated amount of propylene oxide was added and reacted for 4 hours. After the reaction is finished, adding p-phenylenediamine in a calculated amount, and reacting for 6 hours at the temperature of 180 ℃ and the pressure of 2 MPa; and finally, adding a calculated amount of butylene oxide, heating to 200 ℃, and carrying out etherification reaction again until the reaction is finished to obtain the heteroatom-containing methoxy polyether nonionic surfactant.
Putting the obtained product and 2 times of molar weight of potassium hydroxide into a reactor, starting stirring, alkalizing for 2 hours at 60 ℃, heating to 90 ℃, slowly dropwise adding sodium chloroacetate, continuing to react for 5 hours after the addition is finished, and using MgCl2Ion exchange is carried out to obtain the product of the methoxy polyether carboxylic acid magnesium anionic surfactant containing the heteroatom S, N. The structure is shown in table 1.
Example 5 Synthesis of heteroatom N containing 2-methyl-benzyl polyether sodium sulfonate anionic surfactant
Adding a certain amount of 2-methyl-benzyl alcohol and 0.5% KOH catalyst by mass into a polymerization reaction kettle, heating the system to 170 ℃ under stirring, slowly introducing metered propylene oxide, and controlling the reaction pressure to be less than 1.0MPa to carry out etherification reaction. After the reaction is finished, adding p-phenylenediamine, and heating to 200 ℃ to react for 6 hours; then cooling to 150 ℃, introducing a calculated amount of ethylene oxide, adding ethylenediamine after the reaction is finished, and heating to 180 ℃ again for reaction for 4 hours; and finally, adding the calculated amount of butylene oxide, and carrying out etherification reaction again until the reaction is finished to obtain the heteroatom N-containing 2-methyl-benzyl polyether nonionic surfactant. P-phenylenediamine
And (2) putting the obtained product and potassium hydroxide with 2 times of molar weight into a reactor, starting stirring, alkalizing for 2 hours at 60 ℃, heating to 80 ℃, slowly dropwise adding 3-chloro-2-hydroxy-sodium propanesulfonate, continuing to react for 5 hours after the addition, and performing post-treatment to obtain the heteroatom N-containing 2-methyl-benzyl polyether sodium sulfonate anionic surfactant. The structure is shown in table 1.
[ example 6 ] Synthesis of hetero atom N-containing cis-9-octadecenyloxy polyether sodium sulfonate anionic nonionic surfactant
Adding a certain amount of oleyl alcohol (cis-9-octadecenol) and 0.5% of KOH catalyst by mass into a polymerization reaction kettle, heating the system to 170 ℃ under stirring, slowly introducing metered butylene oxide, and controlling the reaction pressure to be less than 1.0MPa to carry out etherification reaction. After the reaction is finished, adding p-phenylenediamine, and heating to 200 ℃ to react for 6 hours; then the temperature is reduced to 170 ℃ and propylene oxide with calculated amount is introduced for reaction for 5 hours. After the reaction is finished, adding ethylenediamine, and heating to 180 ℃ again for reaction for 4 hours; and finally, adding the calculated amount of ethylene oxide again, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), and purging the system by using nitrogen to remove the unreacted ethylene oxide to obtain the polyether nonionic surfactant.
And (2) putting the obtained product and potassium hydroxide with 2 times of molar weight into a reactor, starting stirring, alkalizing for 2 hours at 60 ℃, heating to 90 ℃, slowly dropwise adding 1-chloro-2-butene-sodium sulfonate, continuing to react for 5 hours after the addition, and performing post-treatment to obtain the cis-9-octadecenol oxy polyether sodium sulfonate anionic surfactant containing heteroatom N. The structure is shown in table 1.
Example 7 Synthesis of Long carbon chain sodium Polyethercarboxylate anionic surfactant containing heteroatom N
Adding a certain amount of C into a polymerization reaction kettle30H61OH, 0.5 percent of KOH and 0.01 percent of bimetallic polyether catalyst (DMC) calculated by the mass of the OH, heating the system to 200 ℃ under stirring, slowly introducing metered butylene oxide, and controlling the reaction pressure<Etherification reaction is carried out under 1.0 MPa. After the reaction is finished, adding p-phenylenediamine and reacting for 6 hours; then the temperature is reduced to 170 ℃ and propylene oxide with calculated amount is introduced for reaction for 5 hours. After the reaction is finished, adding ethylenediamine, and heating to 180 ℃ again for reaction for 4 hours; finally, cooling to 150 ℃, adding a calculated amount of ethylene oxide, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), purging the system by using nitrogen, and removing unreacted ethylene oxide to obtain the productLong carbon chain polyether nonionic surfactants.
And (3) putting the obtained product and 2 times of molar weight of potassium hydroxide into a reactor, stirring, alkalizing for 2 hours at 60 ℃, heating to 90 ℃, slowly dropwise adding sodium chloroacetate, continuing to react for 5 hours after the addition, and performing post-treatment to obtain the long-carbon-chain polyether sodium carboxylate anionic nonionic surfactant containing heteroatom N. The structure is shown in table 1.
[ example 8 ] evaluation of emulsifying Properties of surfactants
The phase evaluation was performed according to the SPE 113313 method to calculate the emulsifying capacity. The method mainly comprises the following steps: the desired volume and concentration of aqueous surfactant solution was added to the glass tube, and then crude oil was added to the solution, with a water-to-oil volume ratio (WOR) of 1.0. Sealing and mixing. It was then placed in a metal bath, heated to a set temperature, and periodically mixed to enhance mass transfer between the phases. Equilibrium is considered to be reached until the visual interface position does not change. Its emulsifying capacity is expressed by the solubilization parameter SP, i.e. the volume or mass of surfactant per unit volume or mass that solubilizes water in oil or oil in water. The results are shown in tables 2 and 3.
[ example 9 ] evaluation of surfactant interfacial Property
And measuring the interfacial tension change between the 0.3 wt% of surfactant and the crude oil by using a TX-500C rotary drop interfacial tension meter or a Dataphysics SVT20 under the conditions of reservoir temperature and rotating speed of 5000 r/min until oil drops are balanced. The results are shown in tables 2 and 3.
[ example 10 ] evaluation of oil-washing Performance of surfactant
Taking a certain amount of oil sand, according to the oil: sand 1: 4 (mass ratio) aging at the oil reservoir temperature for 10 days, and stirring for 5 minutes every 2 hours; the aged oil sand, 5g, was then removed, along with a 0.3 wt% surfactant solution as an oil sand: the mass ratio of the solution is 1: 10, mixing uniformly, aging for 48 hours at the oil reservoir temperature, extracting crude oil in the solution by using petroleum ether, fixing the volume by using a 50ml colorimetric tube, and carrying out colorimetric analysis by using a spectrophotometer at the wavelength of 430 nm. The crude oil concentration in the surfactant solution was calculated using a standard curve. The results are shown in tables 2 and 3.
[ example 11 ] evaluation of oil repellency of surfactant
According to the test of the physical simulated oil displacement effect of the composite oil displacement system in the SY/T6424-2000 composite oil displacement system performance test method, a simulated oil displacement experiment is carried out at the oil reservoir temperature. Firstly, using injected water to drive oil-free, then transferring 0.3PV (core pore volume) of the above-mentioned surfactant, then water-driving again to oil-free so as to raise crude oil recovery ratio. The results are shown in tables 2 and 3.
[ COMPARATIVE EXAMPLE 1 ]
Preparation of C according to CN201210188897.630H61O(CH2CH2O)10CH2CH2COONa, and the results of the performance evaluation are shown in tables 2 and 3.
[ COMPARATIVE EXAMPLE 2 ]
Surfactant C was prepared according to the method of US20110281779A130H61O-(BO)8-(PO)12-(EO)30-SO3Na, and the performance was evaluated, and the results are shown in tables 2 and 3.
Table 1 examples 1-7 surfactant compositions and structures
Table 2 high temperature performance of examples 1-7 surfactants
And (3) testing conditions are as follows:
90 ℃, the degree of mineralization of 35,000mg/L, the content of divalent ions of 1,000mg/L, crude oil API 25 and the permeability of a rock core of 220mD
Examples
Solubilization parameter
Interfacial tension (mN/m)
Wash oil Performance (%)
Enhanced recovery (%)
1
12.5
0.00178
63
8.9
2
13.3
0.000997
68
9.2
3
17.2
0.000501
79
14.3
4
12.8
0.00160
62
9.3
5
14.1
0.00103
65
11.1
6
16.0
0.000611
73
13.3
7
13.3
0.000965
69
12.2
Comparative example 1
6.8
0.0135
35
4.6
Comparative example 2
8.0
0.00446
51
7.0
The surfactant prepared in example 3 was formulated at various concentrations and tested for oil-water interfacial tension with the crude oil described above, and the results are shown in table 3.
TABLE 3 oil-water interfacial tension between surfactant groups of different concentrations and crude oil
The results show that the surfactant disclosed by the invention has high oil-water interfacial activity on the tested thickened oil.
The surfactant of the invention is used for high-temperature high-salinity heavy oil reservoir again, and the oil-water interfacial tension of the surfactant is tested, and the result is shown in table 4.
Table 4 examples 1-7 high temperature performance of surfactants
And (3) testing conditions are as follows:
the mineralization degree is 300,000mg/L at 120 ℃, the content of divalent ions is 10,000mg/L, crude oil API is 18, and the permeability of a rock core is 500mD
Examples
Solubilization parameter
Interfacial tension (mN/m)
Wash oil Performance (%)
Enhanced recovery (%)
1
14.1
0.00100
65
8.8
2
13.3
0.00203
67
9.3
3
18.0
0.000379
82
15.1
4
12.7
0.00343
66
8.4
5
16.4
0.00266
72
12.2
6
18.1
0.000421
74
14.9
7
15.2
0.00388
64
9.3
Comparative example 1
5.6
0.0422
34
3.7
Comparative example 2
9.1
0.00518
52
7.3
As is clear from the results in tables 2, 3 and 4, the surfactants prepared according to the present invention are excellent in performance, and the present inventors have surprisingly found that both the emulsifying ability and the oil-washing performance are significantly improved as compared with those of comparative examples 1 and 2, and an unexpected effect of improving the recovery efficiency is obtained.