WO2021093601A1 - 表面活性剂及其制备方法 - Google Patents

表面活性剂及其制备方法 Download PDF

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WO2021093601A1
WO2021093601A1 PCT/CN2020/125017 CN2020125017W WO2021093601A1 WO 2021093601 A1 WO2021093601 A1 WO 2021093601A1 CN 2020125017 W CN2020125017 W CN 2020125017W WO 2021093601 A1 WO2021093601 A1 WO 2021093601A1
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group
reaction
surfactant
poly
surfactant according
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French (fr)
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李应成
张卫东
金军
沈之芹
鲍新宁
沙鸥
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Priority to MX2022005885A priority Critical patent/MX2022005885A/es
Priority to CA3161626A priority patent/CA3161626C/en
Priority to BR112022009327A priority patent/BR112022009327A2/pt
Priority to EP20887203.6A priority patent/EP4059982A4/en
Priority to US17/756,080 priority patent/US20220403225A1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
    • C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2612—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aromatic or arylaliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/325—Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/338—Polymers modified by chemical after-treatment with inorganic and organic compounds

Definitions

  • the invention relates to a surfactant and a preparation method thereof, in particular to a heteroatom-containing alkoxy polyether anionic nonionic surfactant and a preparation method thereof.
  • thermal flooding including steam flooding, fire-burning oil reservoirs, etc.
  • miscible flooding including CO 2 miscible phase, hydrocarbon miscible phase, and other inerts.
  • Gas miscible flooding third is chemical flooding
  • microbial oil recovery including biopolymer and microbial surfactant flooding.
  • Chemical flooding is a very important and large-scale technology in enhanced oil recovery, including polymer flooding, surfactant flooding, alkaline water flooding, concentrated sulfuric acid flooding, etc., as well as a variety of combined technologies of polymer, alkali, and surfactant.
  • the effect of chemical flooding is the result of physical action and chemical action.
  • the physical action refers to the sweeping action of the displacement fluid
  • the chemical action refers to the microscopic oil displacement action of the displacement fluid.
  • the core of the chemical action is to reduce the interfacial tension between the displacement fluid and the crude oil and improve the oil washing efficiency.
  • Surfactants have both lipophilic (hydrophobic) and hydrophilic (oleophobic) properties. When the surfactant is dissolved in water, the molecules are mainly distributed on the oil-water interface, which can significantly reduce the oil-water interfacial tension.
  • the reduction of oil-water interfacial tension means the reduction of adhesion work, that is, crude oil is easily eluted from the surface of the formation, thereby improving the efficiency of oil washing.
  • the oil displacement effect of surfactants is also manifested in the reversal of the wettability of the lipophilic rock surface, the emulsification of crude oil, the increase of surface charge density and the coalescence of oil droplets. This is the pivotal role of surfactants in chemical flooding technology. s reason.
  • anionic nonionic surfactants have attracted attention due to their combination of temperature resistance of anionic surfactants and salt resistance of nonionic surfactants.
  • Anionic nonionic surfactants mainly include alkoxy carboxylates, alkoxy sulfonates, alkoxy sulfates, etc.
  • Zhang Yongmin and Xu Hujun reported the performance of anionic and nonionic surfactants such as sodium nonylphenol polyoxyethylene ether sulfonate and fatty alcohol polyoxyethylene ether sulfonate (see: Fine Petrochemicals, 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 ; CN201210188897.6).
  • the University of Texas at Austin, Oil Chem Technology, BASF, etc. also reported the application of anionic and nonionic surfactants such as alkoxy carboxylates and alkoxy sulfonates in enhanced oil recovery.
  • nonionic nonionic surfactants the nonionic fragments are only ethoxy groups and/or propoxy groups.
  • an anionic nonionic surfactant R 1 -BO x -PO y -EO z -XY a- a/b containing non-ionic fragments of butoxy BO, propoxy PO, and ethoxy EO is also disclosed.
  • M b+ shows better performance.
  • R 1 is obtained by dimerization of C12-C36 linear or branched fatty alcohols through Guerbet reaction.
  • the present invention relates to a novel alkoxy polyether anionic surfactant containing heteroatoms. Its molecular structure also contains heteroatoms N and S, as well as composite polyether functional groups BO, PO, EO. On the one hand, it is conducive to precise control It interacts with crude oil to solve the technical problems of poor emulsification performance and low activity of surfactants in the existing enhanced oil recovery technology. At the same time, its lipophilic base is no longer limited to the traditional C8-C18 lipophilic carbon chain, which greatly broadens the source of raw materials and reduces production costs. In addition, in the selection of lipophilic groups, the present invention is more inclined to include both aliphatic and aromatic lipophilic groups, thereby enhancing its interaction with crude oil and improving oil displacement performance.
  • One of the technical problems to be solved by the present invention is that the surfactants in the prior art have poor emulsification performance and low activity under high temperature and high salt conditions; and the problems of narrow sources of surfactant raw materials and high production costs.
  • a new type of heteroatom-containing alkoxy polyether anionic nonionic surfactant which has good emulsifying ability and high activity, and can contain aliphatic and aromatic lipophilic groups, thereby enhancing its interaction with crude oil. The advantages of improving oil displacement performance.
  • the second technical problem to be solved by the present invention is to provide a method for preparing a heteroatom-containing alkoxy polyether anionic nonionic surfactant.
  • the method has the characteristics of simple process, mild reaction conditions and high product yield.
  • the third technical problem to be solved by the present invention is to provide a method for applying heteroatom-containing alkoxy polyether anionic nonionic surfactants.
  • an alkoxy polyether anionic surfactant containing heteroatoms which has the following general molecular formula:
  • R 1 is any one of C 1 ⁇ C 50 aliphatic group and aromatic group
  • Each group Poly is the same or different from each other, and each is independently selected from the group represented by the formula (Ru-O) m ; among the groups Poly, each group Ru is the same or different from each other, and each is independently selected from C 2 -6 straight chain or branched chain alkylene, provided that: at least a part of the group Poly in the group Ru is selected from butylene, and at least a part of the group Poly has a spacer group L; wherein the L It is a group with 0-30 carbon atoms containing heteroatoms and two free ends;
  • n is a number from 0 to 300 and greater than 0;
  • m is independently a number from 0 to 100 and greater than 0;
  • X is any one of an alkylene group, an alkenylene group, and an arylene group containing 1-10 carbon atoms;
  • Y is an anionic group
  • M is a cationic or cationic group that keeps the general formula in charge balance
  • a is the absolute value of the valence of Y
  • b is the absolute value of the valence of M.
  • the R 1 is preferably any one of C 1 ⁇ C 50 alkyl, alkenyl, aryl, and fused ring aromatic hydrocarbon; more preferably C 1 ⁇ C 30 alkyl, alkenyl , Aryl group, fused ring aromatic hydrocarbon; the heteroatom is preferably N and/or S.
  • L 1 and L 2 are independently preferably selected from at least one of -NR 6 -, -S-, -X 1 -R 5 -X 2 -, wherein X 1 and X 2 are independently preferred From NR 6 or S, R 5 is preferably from C 0 -C 10 alkylene, alkenylene, and arylene, R 6 is preferably from H or C 1 to C 4 alkyl; R 5 is preferably From C 0 , it means -X 1 -X 2 -are directly connected.
  • the R 5 is more preferably selected from any one of C 0 -C 6 alkylene, alkenylene, and arylene, and R 6 is more preferably selected from H.
  • the degree of alkoxy polymerization x, y, and z are independently preferably any number from 1 to 100, and more independently, preferably any number from 1 to 50.
  • the X is preferably any one of an alkylene group, an alkenylene group, and an arylene group containing 1 to 6 carbon atoms.
  • 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.
  • the M is preferably selected from at least one of alkali metal cations, alkaline earth metal cations, and ammonium ions; more preferably selected from Na + , K + , Mg 2+ , Ca 2+ , NH 4 + At least one of them.
  • the formula (I) contains two or more spacer groups L that are the same or different, and at least one group Poly is between the two spacer groups L.
  • At least a part of the group Ru in the group Poly is selected from ethylene, and at least a part of the group Ru in the group Poly is selected from propylene or propylene.
  • Isopropyl group, and at least a part of the group Ru in the group Poly is selected from butylene, sec-butylene, isobutylene or tert-butylene
  • the formula (I) contains at least two spacer groups L, wherein at least a part of the group L contains a heteroatom N, and at least a part of the group L contains a heteroatom S.
  • the group Poly near the R 1 side has more carbon atoms than the group Poly near the X side.
  • the technical solution adopted by the present invention is as follows: a heteroatom-containing alkoxy polyether anionic nonionic surfactant described in any one of the technical solutions for solving one of the above technical problems
  • the preparation method includes the following steps:
  • the initiator, ethylene oxide, propylene oxide, and butylene oxide are subjected to an alkoxylation reaction in the presence of a catalyst to obtain an alkoxy polyether nonionic surfactant; wherein, the initiator
  • the starting agent is any one of C 1 ⁇ C 50 alkyl alcohol, alkenyl alcohol, alkyl phenol, fused ring aromatic hydrocarbon phenol;
  • step b) The alkoxy polyether nonionic surfactant obtained in step a) is reacted with an organic amine reagent or a thiol reagent to obtain an alkoxy polyether nonionic surfactant containing N and/or S heteroatoms ;
  • step b) The heteroatom-containing alkoxy polyether nonionic surfactant obtained in step b) is subjected to sulfonation or carboxylation reaction with a sulfonating agent or a carboxylating agent, and then neutralized to obtain the alkoxy -Based polyether anionic nonionic surfactant.
  • the reaction temperature of the alkoxylation reaction is preferably 140-200°C, and the reaction pressure is preferably 0-5 MPa; the initiator is combined with ethylene oxide, propylene oxide or butylene oxide.
  • the molar ratio of is preferably 1: (1-50); the catalyst is preferably an alkali metal hydroxide, a DMC bimetal polyether catalyst or a phosphazene catalyst, and the amount is preferably 0.001-2.0% of the initiator.
  • the reaction temperature in step b) is preferably 100 to 300°C, and the reaction pressure is preferably 0 to 5 MPa, and the reaction time is preferably 1 to 10 hours.
  • the reaction temperature of the sulfonation reaction or carboxylation reaction is preferably 80-200°C
  • the reaction pressure is preferably 0-3 MPa
  • the reaction time is preferably 1-10 hours.
  • the reaction temperature of the alkoxylation reaction is more preferably 140-200°C, and the pressure is more preferably 0.1-2.0 MPa; the reaction temperature in step b) is more preferably 150-250°C, The reaction pressure is more preferably 0.5 to 3 MPa; the reaction temperature in step c) is more preferably 50 to 100° C., and the reaction time is more preferably 0.5 to 5 hours.
  • the sulfonating reagent may be various sulfonating reagents commonly used in the art, such as halogenated sulfonic acid or/and its salt, such as but not limited to chlorohexylsulfonic acid (sodium), p-chlorobenzene Sulfonic acid (sodium), 3-chloro-2-hydroxy-propanesulfonic acid (sodium), 1-chloro-2-butene-sulfonic acid (sodium), etc.; the carboxylation reagent can be of various types commonly used in the field Carboxylation reagents, such as halogenated carboxylic acids or/and their salts, such as but not limited to chloroacetic acid (sodium).
  • halogenated sulfonic acid or/and its salt such as but not limited to chlorohexylsulfonic acid (sodium), p-chlorobenzene Sulfonic acid (sodium), 3-chloro-2-
  • the technical solution adopted by the present invention is as follows: a heteroatom-containing alkoxy polyether anionic nonionic surfactant described in any one of the technical solutions to the technical problem described above application.
  • the application is not particularly limited, for example, but not limited to, the application of enhanced oil recovery in oil and gas fields, such as injecting an aqueous solution containing the surfactant of the present invention into the ground to increase oil and gas field recovery.
  • the use concentration of the agent may be 0.01 wt% or more, preferably 0.05 wt% or more, and more preferably 0.05 to 1 w.t.%.
  • the heteroatom-containing alkoxy polyether anionic nonionic surfactant of the present invention enhances the interaction between the surfactant and crude oil components by introducing heteroatoms, alkoxy groups, and the segment design,
  • the surfactant has a strong emulsifying ability and can better solubilize crude oil; at the same time, it has a good oil washing ability, thereby increasing the recovery factor.
  • the surfactant has high interfacial activity and strong emulsifying ability. When the concentration is above 0.05%, it can form an ultra-low interfacial tension of 10 -3 ⁇ 10 -4 mN/m with underground crude oil, and the solubilization parameter can reach above 12.
  • R1 connected to the alkoxy group can be any one of C 1 to C 50 aliphatic group and aromatic group, and the surfactant has a wide range of raw materials and low preparation cost.
  • anionic nonionic surfactant refers to a surfactant having both anionic and nonionic fragments in the structure.
  • the obtained heteroatom-containing alkoxy polyether anionic nonionic surfactant has better emulsifying ability than the prior art, and at the same time, it has higher interfacial activity, which is more effective for crude oil.
  • the solubilization parameter can reach more than 18, the interfacial tension can reach 10 -4 mN/m, and the recovery rate can be increased by more than 15%, and good technical effects have been achieved.
  • Fig. 1 is a flowchart of an indoor core displacement experiment used in the present invention.
  • Fig. 2 is an infrared spectrogram of the anion-nonionic surfactant of the heteroatom-containing alkoxy polyether anionic nonionic surfactant prepared according to Example 3 of the present invention.
  • 3285cm -1 NH stretching vibration of a peak
  • 3235cm -1 peak vibration is methyl and methylene stretching
  • 1545cm -1 peak vibration aromatic ring skeleton 1383 and 1442cm -1 for the methyl and methylene
  • the bending vibration peak of 1296cm -1 is the elastic vibration peak of the ether bond
  • 1040cm -1 is the bending vibration peak of the CN bond
  • 700-900cm -1 is the elastic vibration peak on the aromatic ring.
  • Fig. 3 is a proton nuclear magnetic resonance spectrum of a heteroatom-containing alkoxy polyether anion-nonionic surfactant anion-nonionic surfactant prepared according to Example 3 of the present invention. among them,
  • test conditions include:
  • the product contains heteroatom S, N methoxy polyether carboxylate magnesium anion nonionic surfactant.
  • Table 1 The structure is shown in Table 1.
  • solubilization parameter SP that is, the volume or mass of a unit volume or mass of surfactant solubilizes water in oil or solubilizes oil in water.
  • the simulated flooding experiment is carried out at the reservoir temperature. First use water injection to drive to no oil, and then switch to 0.3PV (core pore volume) of the above surfactant, and then water drive to no oil again to calculate the enhanced oil recovery. The results are shown in Tables 2 and 3.
  • the surfactant C 30 H 61 O-(BO) 8 -(PO) 12 -(EO) 30 -SO 3 Na was prepared according to the US20110281779A1 method, and performance evaluation was performed. The results are shown in Tables 2 and 3.
  • the surfactant prepared in Example 3 was formulated into different concentrations, and the interfacial tension between the oil and water of the crude oil was tested. The results are shown in Table 3.
  • the surfactant of the present invention was used again in high-temperature and high-salt heavy oil reservoirs, and the oil-water interfacial tension was tested. The results are shown in Table 4.

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Abstract

表面活性剂及其制备方法，尤其是含杂原子的烷氧基聚醚阴非离子表面活性剂。所述表面活性剂具有如下分子通式： R 1-O-(Poly) n-X-Y a-·a/bM b+； (I) 其中，R 1为C 1～C 50的脂肪基、芳香基中的任意一种；各基团Poly彼此相同或不同，各自独立地选自式(O-Ru-O)m代表的基团；n为0～300且大于0中的数；对于各个类型的基团(Ru-O)，m独立地为0～100且大于0中的数；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。

Description

表面活性剂及其制备方法 技术领域
本发明涉及表面活性剂及其制备方法，具体地涉及一种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。
背景技术
随着世界能源需求的增加，石油的合理开发利用已引起人们的极大重视，对石油的开采量及开采效率的要求也越来越高。实现油气资源的高效开采，对于提高原油产量不仅具有现实意义，更具有重要的战略意义。常规的采油方法(一次和二次法)一般仅采出原油地质储量的1/3，还有约2/3的原油未能采出，因此提高采油率已成为石油开采研究的重大课题。三次采油技术则是一种有效的提高采油率的方法，可分为四大类：一是热力驱，包括蒸汽驱、火烧油层等；二是混相驱，包括CO 2混相、烃混相及其他惰性气体混相驱；三是化学驱；四是微生物采油，包括生物聚合物、微生物表面活性剂驱。化学驱是强化采油中非常重要并大规模实施的技术，包括聚合物驱、表面活性剂驱、碱水驱和注浓硫酸驱等以及聚合物、碱、表面活性剂的多种组合技术。化学驱的效果是物理作用和化学作用的结果，物理作用是指驱替液的波及作用，而化学作用是指驱替液的微观驱油作用。化学作用的核心是降低驱替液与原油的界面张力及提高洗油效率。表面活性剂由于兼具亲油(疏水)和亲水(疏油)性质，当表面活性剂溶于水时，分子主要分布在油水界面上，可以显著降低油水界面张力。油水界面张力的降低意味着粘附功的减小，即原油易从地层表面洗脱下来，从而提高洗油效率。表面活性剂的驱油效果还表现在使亲油的岩石表面润湿性反转、原油乳化、提高表面电荷密度及油滴聚并等作用，这是表面活性剂在化学驱技术中起举足轻重作用的原因。
目前，三次采油表面活性剂应用的最多的还是石油磺酸盐，烷基苯磺酸盐、烯烃磺酸盐等表面活性剂，见CN1203935A、CN1566258A、CN1458219A、CN1426833A、US2010/0282467。上述表面活性剂具有来源广泛、价格低廉等优点。但随着油田开采程度的日益深入，采油地层越来越深，表面活性剂的使用温度越来越高、水质矿化度也越来 越高。然而上述表面活性剂耐盐性能，特别是耐二价阳离子性能较差，导致其不能适用于高温、高矿化度的油田区块。因此开发新型耐温抗盐表面活性剂对于三次采油产业具有极为重要的意义。
近年来，阴非离子表面活性剂由于兼具阴离子表面活性剂的耐温性和非离子表面活性剂的耐盐性，从而备受关注。阴非离子表面活性剂主要包括烷氧基羧酸盐、烷氧基磺酸盐、烷氧基硫酸酯盐等。如张永民、许虎君等分别报道了壬基酚聚氧乙烯醚磺酸钠、脂肪醇聚氧乙烯醚磺酸钠等阴非离子表面活性剂的性能(见：精细石油化工，2009，26(2)，4～7；油田化学，2009，26(1)，72～75；化学研究与应用，2009，21(7)，964～968；日用化学工业，2008，38(4)，253～256；CN201210188897.6)。美国德克萨斯大学奥斯汀分校、美国Oil Chem Technology、BASF等也分别报道了烷氧基羧酸盐、烷氧基磺酸盐等阴非离子表面活性剂在强化采油中的应用。(见SPE 154256；SPE 154261；US 7,629,299；US20120101010；US2011120707A1；US20140116690A1)。上述阴非离子表面活性剂中，非离子片段仅仅为乙氧基和/或丙氧基。而US20110281779中，披露了同时含有丁氧基BO、丙氧基PO、乙氧基EO非离子片段的阴非离子表面活性剂R 1-BO x-PO y-EO z-X-Y a- a/bM b+，并显示了更优的性能。其中R 1由C12-C36的线性或支化脂肪醇通过Guerbet反应二聚得到。
发明内容
本发明涉及一种含杂原子的新型烷氧基聚醚阴非离子表面活性剂，其分子结构中同时包含杂原子N、S，以及复合聚醚官能团BO、PO、EO，一方面利于精确调控其与原油相互作用，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。同时，其亲油基不再局限于传统意义上的C8-C18的亲油碳链，从而大大拓宽原料来源，降低生产成本。另外，在亲油基选择上，本发明更倾向于同时包含脂肪族与芳香族亲油基，从而增强其与原油的相互作用，提高驱油性能。
本发明所要解决的技术问题之一是现有技术中的表面活性剂在高温高盐条件下乳化性能差、活性低的技术问题；以及表面活性剂原料来源窄，生产成本高的问题，提供一种新型含杂原子的烷氧基聚醚阴非离子表面活性剂，该表面活性剂具有乳化能力好、活性高，可包含 脂肪族与芳香族亲油基，从而增强其与原油的相互作用，提高驱油性能的优点。
本发明所要解决的技术问题之二是提供一种含杂原子的烷氧基聚醚阴非离子表面活性剂的制备方法。该方法具有工艺简单、反应条件温和、产品收率高的特点。
本发明所要解决的技术问题之三是提供一种含杂原子的烷氧基聚醚阴非离子表面活性剂的应用方法。
为解决上述技术问题之一，本发明采用的技术方案如下：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：
R 1-O-(Poly) n-X-Y a-·a/bM b+；     (I)
其中：
R 1为C 1～C 50的脂肪基、芳香基中的任意一种；
各基团Poly彼此相同或不同，各自独立地选自式(Ru-O) m代表的基团；在各基团Poly之间，各基团Ru彼此相同或不同，各自独立地选自C 2-6直链或支链亚烷基，前提是：在至少一部分的基团Poly中的基团Ru选自亚丁基，以及至少一部分的基团Poly之间有间隔基团L；其中所述L为具有0-30个碳原子的包含杂原子和两个自由端的基团；
n为0～300且大于0中的数；
对于各个类型的基团(Ru-O)，m独立地为0～100且大于0中的数；
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为使所述通式保持电荷平衡的阳离子或阳离子基团；
a为Y的化合价的绝对值，b为M的化合价的绝对值。
在一个实施方案中，所述R 1优选为C 1～C 50的烷基、烯基、芳基、稠环芳烃中的任意一种；更优选为C 1～C 30的烷基、烯基、芳基、稠环芳烃中的任意一种；所述杂原子优选为N和/或S。
在一个实施方案中，所述L 1、L 2独立优选自-NR 6-、-S-、-X 1-R 5-X 2-中的至少一种，其中，X 1、X 2独立优选自NR 6或S，R 5优选自C 0-C 10亚烷基、亚烯基、亚芳基中的任意一种，R 6优选自H或C 1～C 4的烷基；R 5优选自C 0时，则表示-X 1-X 2-直接相连。
在一个实施方案中，所述R 5更优选选自C 0-C 6的亚烷基、亚烯基、亚芳基中的任意一种，R 6更优选选自H。
在一个实施方案中，所述烷氧基聚合度x、y、z独立优选为1～100中的任意一个数，更独立优选为1～50中的任意一个数。
在一个实施方案中，所述X优选为包含1-6个碳原子的亚烷基、亚烯基、亚芳基中的任意一种。
在一个实施方案中，所述阴离子基团Y优选为羧酸根、磺酸根、硫酸根、磷酸根中的至少一种，更优选为羧酸根、磺酸根中的至少一种。
在一个实施方案中，所述M优选选自碱金属阳离子、碱土金属阳离子、铵根离子中的至少一种；更优选为选自Na +、K +、Mg 2+、Ca 2+、NH 4 +中的至少一种。
在一个实施方案中，式(I)中包含两个或更多个相同或不同的间隔基团L，且其中有至少一个基团Poly处于两个间隔基团L之间。
在一个实施方案中，在所述各基团Poly中，至少一部分的基团Poly中的基团Ru选自亚乙基，至少一部分的基团Poly中的基团Ru选自亚丙基或亚异丙基，以及至少一部分的基团Poly中的基团Ru选自亚丁基、亚仲丁基、亚异丁基或亚叔丁基
在一个实施方案中，式(I)中包含至少两个间隔基团L，其中至少一部分基团L中包含杂原子N，且至少一部分基团L中包含杂原子S。
在一个实施方案中，式(I)中，临近R 1侧的基团Poly具有比临近X侧的基团Poly更多的碳原子。
为解决上述技术问题之二，本发明采用的技术方案如下：一种上述解决技术问题之一所述技术方案中任一所述的含杂原子的烷氧基聚醚阴非离子表面活性剂的制备方法，包括以下步骤：
a)将起始剂和环氧乙烷、环氧丙烷、环氧丁烷，在催化剂存在下，进行烷氧基化反应，得到烷氧基聚醚非离子表面活性剂；其中，所述起始剂为含C 1～C 50的烷基醇、烯基醇、烷基酚、稠环芳烃酚中的任意一种；
b)将步骤a)得到的烷氧基聚醚非离子表面活性剂，与有机胺试剂或硫醇试剂进行反应，得到含N和/或S杂原子的烷氧基聚醚非离子表面活性剂；
c)将步骤b)得到的含杂原子的烷氧基聚醚非离子表面活性剂， 与磺化试剂或羧化试剂进行磺化或羧化反应，后经中和，得到所述的烷氧基聚醚阴非离子表面活性剂。
在一个实施方案中，所述烷氧基化反应的反应温度优选为140～200℃，反应压力优选为0～5MPa；所述起始剂与环氧乙烷、环氧丙烷或环氧丁烷的摩尔比优选为1∶(1～50)；所述催化剂优选为碱金属氢氧化合物、DMC双金属聚醚催化剂或磷腈催化剂，用量优选为起始剂的0.001～2.0％。
在一个实施方案中，所述步骤b)中的反应温度优选为100～300℃，反应压力优选为0～5MPa反应时间优选为1～10小时。
在一个实施方案中，所述磺化反应或羧化反应的反应温度优选为80～200℃，反应压力优选为0～3MPa，反应时间优选1～10小时。
在一个实施方案中，所述烷氧基化反应的反应温度更优选为140～200℃，压力更优选为0.1～2.0MPa；所述步骤b)中的反应温度更优选为150～250℃，反应压力更优选为0.5～3MPa；所述步骤c)中的反应温度更优选为50～100℃，反应时间更优选为0.5～5小时。
在一个实施方案中，所述磺化试剂可以是本领域常用的各类磺化试剂，例如卤代磺酸或/和其盐，例如但不限定为氯己基磺酸(钠)、对氯苯磺酸(钠)、3-氯-2-羟基-丙磺酸(钠)、1-氯-2-丁烯-磺酸(钠)等；所述羧化试剂可以是本领域常用的各类羧化试剂，例如卤代羧酸或/和其盐，例如但不限定为氯乙酸(钠)。
为解决上述技术问题之三，本发明采用的技术方案如下：一种上述解决技术问题之一所述技术方案中任一所述的含杂原子的烷氧基聚醚阴非离子表面活性剂的应用。
在一个实施方案中，所述应用并无特殊限定，例如但不限定在油气田提高采收率中的应用，如将含本发明表面活性剂的水溶液注入地下提高油气田采收率，所述表面活性剂的使用浓度可为0.01w.t.％以上，优选为0.05w.t.％以上，更优选为0.05～1w.t.％。
本发明的含杂原子的烷氧基聚醚阴非离子表面活性剂，通过引入杂原子、烷氧基，以及所述链段设计，增强了表面活性剂与原油组分之间的相互作用，使得表面活性剂具有较强的乳化能力，可以更好地增溶原油；同时具有良好的洗油能力，从而提高采收率。
本发明含杂原子的烷氧基聚醚阴非离子表面活性剂用于三次采油 的表面活性剂组合物中具有以下优点：
(1)表面活性剂界面活性高、乳化能力强。其在浓度0.05％以上时，即可与地下原油形成10 -3～10 -4毫牛/米的超低界面张力，增溶参数达到12以上。
(2)耐温、抗盐能力强。由于其同时含有BO、PO、EO等非离子基团，因而其抗盐能力显著提高；而不同官能团之间通过C-C键或C-O键相连，因而其水热稳定性高。
(3)与烷氧基相连的R1可以是为C 1～C 50的脂肪基、芳香基中的任意一种，表面活性剂原料来源广泛、制备成本低。
在本发明中，如本领域公知的，所述“阴非离子表面活性剂”是指在结构中同时具有阴离子片段和非离子片段的表面活性剂。
采用本发明的技术方案，得到的含杂原子的烷氧基聚醚阴非离子表面活性剂，和现有技术相比，具有更好地乳化能力，同时具有较高的界面活性，对原油的增溶参数可达18以上，界面张力可达10 -4毫牛/米，提高采收率可达15％以上，取得了较好的技术效果。
附图说明
图1为用于本发明的室内岩心驱替实验流程图。
图2为根据本发明实施例3制备的含杂原子的烷氧基聚醚阴非离子表面活性剂阴离子-非离子表面活性剂红外光谱图。其中，3285cm -1为N-H的伸缩震动峰，3235cm -1为甲基和亚甲基的伸缩震动峰，1545cm -1为芳环的骨架震动峰，1383和1442cm -1为甲基和亚甲基的弯曲震动峰，1296cm -1为醚键的伸缩震动峰，1040cm -1为C-N键的弯曲震动峰，700-900cm -1为芳环上的伸缩震动峰。
图3为根据本发明实施例3制备的含杂原子的烷氧基聚醚阴非离子表面活性剂阴离子-非离子表面活性剂核磁共振氢谱。其中，
Figure PCTCN2020125017-appb-000001
图4为根据本发明实施例3制备的含杂原子的烷氧基聚醚阴非离子表面活性剂油-水界面张力曲线。其中，测试条件包括：
表面活性剂浓度：0.3wt％
90℃下的蓝色曲线：矿化度35,000mg/L，二价离子含量1,000mg/L，原油API＝25，
120℃下的红色曲线：矿化度300,000mg/L，二价离子含量10,000mg/L，原油API＝18
具体实施方式
下面通过实施例对本发明作进一步阐述。
【实施例1】含杂原子N的苯酚聚醚羧酸钠阴非离子表面活性剂的合成
在聚合反应釜加入一定量的苯酚和以其质量计1％KOH为催化剂，搅拌下将体系温度加热至80～90℃，开启真空系统，脱水1小时，而后 用氮气吹扫3～4次以除去体系中的空气，然后将反应温度升高到200℃后缓缓通入计量的环氧丁烷，控制反应压力＜2.0MPa进行醚化反应。待该步反应结束后，加入计算量的水合肼，在温度100℃，压力为5MPa下反应1小时。而后升温至180℃，继续缓缓通入计算量的环氧丙烷，反应结束后，再次加入水合肼并于100℃反应10小时。再次升温至150℃，并加入计算量的环氧乙烷，再次进行醚化反应，直至反应结束(反应压力不变)，用氮气吹扫体系，除去未反应的环氧乙烷，得不同聚合度的苯酚聚氧丁烯聚氧丙烯聚氧乙烯醚非离子表面活性剂。
将前述得到的产物及其2倍摩尔量的氢氧化钾置于反应器中，开动搅拌，于60℃碱化2小时，升温至80℃缓缓加入氯乙酸钠，加完后继续反应5小时，经后处理得含杂原子N的苯酚聚醚羧酸钠阴非离子表面活性剂。结构见表1。
【实施例2】含杂原子N的壬基酚聚醚磺酸钙阴非离子表面活性剂的合成
在聚合反应釜加入一定量的壬基酚和以其质量计0.5％KOH为催化剂，搅拌下将体系温度加热至80～90℃，开启真空系统，脱水1小时，而后用氮气吹扫3～4次以除去体系中的空气，然后将反应温度升高到170℃后缓缓通入计量的环氧丙烷，控制反应压力＜0.60MPa进行醚化反应。待该步反应结束后，加入乙二胺，在温度150℃，压力为4MPa下反应8小时。而后缓缓通入计算量的环氧丁烷，反应结束后，再次加入乙二胺，在温度150℃，压力为4MPa下反应8小时；最后加入计算量的环氧乙烷，再次进行醚化反应，直至反应结束(反应压力不变)，用氮气吹扫体系，除去未反应的环氧乙烷，得到含杂原子N的壬基酚聚醚非离子表面活性剂。
将前述得到的产物及其2倍摩尔量的氢氧化钾置于反应器中，开动搅拌，于60℃碱化2小时，升温至90℃缓缓滴加氯己基磺酸钠，加完后继续反应5小时，而后加入氯化钙进行离子交换，得到含杂原子N的壬基酚聚醚磺酸钙阴非离子表面活性剂。结构见表1。
【实施例3】含N杂原子的十二烷基萘聚醚苯磺酸铵阴非离子表面活性剂的合成
在聚合反应釜加入十二烷基萘酚和以其质量计2.0％KOH及30ppm磷腈催化剂，搅拌下将体系温度加热至80～90℃，开启真空系统，脱水1小时，而后用氮气吹扫3～4次以除去体系中的空气，然后将反应温度升高到180℃后缓缓通入计量的环氧丁烷，控制反应压力＜0.60MPa进行醚化反应。待该步反应结束后，加入丙二胺，在温度250℃，压力为2MPa下反应6小时；而后通入计算量的环氧丙烷，反应结束后，再次加入丙二胺进行氨化反应；最后再次加入计算量的环氧乙烷，于150℃再次进行醚化反应，直至反应结束(反应压力不变)，用氮气吹扫体系，除去未反应的环氧乙烷，得到十二烷基萘聚醚非离子表面活性剂。丙二胺
将前述得到的产物及其2倍摩尔量的氢氧化钾置于反应器中，开动搅拌，于60℃碱化2小时，升温至200℃并加入对氯苯磺酸钠，加完后继续反应至原料完全转化，经后处理铵交换，得到含杂原子N的十二烷基萘聚醚苯磺酸铵阴非离子表面活性剂。结构见表1。
【实施例4】含杂原子S、N的甲氧基聚醚羧酸镁阴非离子表面活性剂的合成
在聚合反应釜加入一定量的甲醇和以其质量计0.5％KOH为催化剂，搅拌下将体系温度加热至140℃后，缓缓通入计量的环氧乙烷，控制反应压力＜1.0MPa进行醚化反应。待该步反应结束后，继续缓缓通入1，3-丙二硫醇，在温度180℃，压力为2MPa下反应5小时；而后加入计算量的环氧丙烷反应4小时。反应结束后，加入计算量的对苯二胺，在温度280℃，压力为2MPa下反应6小时；最后加入计算量的环氧丁烷，升温至200℃，再次进行醚化反应，直至反应结束，得到含杂原子的甲氧基聚醚非离子表面活性剂。
将前述得到的产物及其2倍摩尔量的氢氧化钾置于反应器中，开动搅拌，于60℃碱化2小时，升温至90℃缓缓滴加氯乙酸钠，加完后继续反应5小时，并用MgCl 2进行离子交换，得到产品含杂原子S、N的甲氧基聚醚羧酸镁阴非离子表面活性剂。结构见表1。
【实施例5】含杂原子N的2-甲基-苄基聚醚磺酸钠阴非离子表面活性剂的合成
在聚合反应釜加入一定量的2-甲基-苄醇和以其质量计0.5％KOH催化剂，搅拌下将体系温度加热170℃，缓缓通入计量的环氧丙烷，控制反应压力＜1.0MPa进行醚化反应。待该步反应结束后，加入对苯二胺，升温至200℃反应6小时；而后降温至150℃并通入计算量的环氧乙烷，反应结束后，加入乙二胺，再次升温至180℃反应4小时；最后加入计算量的环氧丁烷，再次进行醚化反应，直至反应结束，得到含杂原子N的2-甲基-苄基聚醚非离子表面活性剂。对苯二胺
将前述得到的产物及其2倍摩尔量的氢氧化钾置于反应器中，开动搅拌，于60℃碱化2小时，升温至80℃缓缓滴加3-氯-2-羟基-丙磺酸钠，加完后继续反应5小时，经后处理得含杂原子N的2-甲基-苄基聚醚磺酸钠阴非离子表面活性剂。结构见表1。
【实施例6】含杂原子N的顺-9-十八烯醇氧基聚醚磺酸钠阴非离子表面活性剂的合成
在聚合反应釜加入一定量的油醇(顺-9-十八烯醇)和以其质量计0.5％KOH催化剂，搅拌下将体系温度加热至170℃，而后缓缓通入计量的环氧丁烷，控制反应压力＜1.0MPa进行醚化反应。待该步反应结束后，加入对苯二胺，升温至250℃反应6小时；而后降温至170℃并通入计算量的环氧丙烷反应5小时。反应结束后，加入乙二胺，再次升温至180℃反应4小时；最后再次加入计算量的环氧乙烷，再次进行醚化反应，直至反应结束(反应压力不变)，用氮气吹扫体系，除去未反应的环氧乙烷，得到聚醚非离子表面活性剂。
将前述得到的产物及其2倍摩尔量的氢氧化钾置于反应器中，开动搅拌，于60℃碱化2小时，升温至90℃缓缓滴加2-氯乙基磺酸钠，加完后继续反应5小时，经后处理得含杂原子N的顺-9-十八烯醇氧基聚醚磺酸钠阴非离子表面活性剂。结构见表1。
【实施例7】含杂原子N的长碳链聚醚羧酸钠阴非离子表面活性剂的合成
在聚合反应釜加入一定量的C 30H 61OH和以其质量计0.5％KOH及0.01％双金属聚醚催化剂(DMC)，搅拌下将体系温度加热200℃后缓缓通入计量的环氧丁烷，控制反应压力＜1.0MPa进行醚化反应。待该 步反应结束后，加入对苯二胺，反应6小时；而后降温至170℃并通入计算量的环氧丙烷反应5小时。反应结束后，加入乙二胺，再次升温至180℃反应4小时；最后降温至150℃，并加入计算量的环氧乙烷，再次进行醚化反应，直至反应结束(反应压力不变)，用氮气吹扫体系，除去未反应的环氧乙烷，得到长碳链聚醚非离子表面活性剂。
将前述得到的产物及其2倍摩尔量的氢氧化钾置于反应器中，开动搅拌，于60℃碱化2小时，升温至90℃缓缓滴加氯乙酸钠，加完后继续反应5小时，经后处理得含杂原子N的长碳链聚醚羧酸钠阴非离子表面活性剂。结构见表1。
【实施例8】含N杂原子的十二烷基萘聚醚苯磺酸铵阴非离子表面活性剂的合成
在聚合反应釜加入十二烷基萘酚和以其质量计2.0％KOH及30ppm磷腈催化剂，搅拌下将体系温度加热至80～90℃，开启真空系统，脱水1小时，而后用氮气吹扫3～4次以除去体系中的空气，然后将反应温度升高到160℃后缓缓通入计量的环氧丙烷，控制反应压力＜0.60MPa进行醚化反应。待该步反应结束后，加入丙二胺，在温度250℃，压力为2MPa下反应6小时；而后再通入计算量的环氧丙烷，反应结束后，再次加入丙二胺进行氨化反应；最后再次加入计算量的环氧乙烷，于150℃再次进行醚化反应，直至反应结束(反应压力不变)，用氮气吹扫体系，除去未反应的环氧乙烷，得到十二烷基萘聚醚非离子表面活性剂。丙二胺
将前述得到的产物及其2倍摩尔量的氢氧化钾置于反应器中，开动搅拌，于60℃碱化2小时，升温至200℃并加入对氯苯磺酸钠，加完后继续反应至原料完全转化，得到含杂原子N的十二烷基萘聚醚苯磺酸钠阴非离子表面活性剂。结构见表1。
【实施例9】含杂原子N的顺-9-十八烯醇氧基聚醚磺酸铵阴非离子表面活性剂的合成
在聚合反应釜加入一定量的油醇(顺-9-十八烯醇)和以其质量计0.5％KOH催化剂，搅拌下将体系温度加热至170℃，而后缓缓通入计量的环氧丁烷，控制反应压力＜1.0MPa进行醚化反应。待该步反应结 束后，加入对苯二胺，升温至280℃反应6小时；而后降温至150℃并通入计算量的环氧丁烷反应5小时，再次进行醚化反应，直至反应结束(反应压力不变)，用氮气吹扫体系，除去未反应的环氧丁烷，得到聚醚非离子表面活性剂。
将前述得到的产物及其2倍摩尔量的氢氧化钾置于反应器中，开动搅拌，于60℃碱化2小时，升温至90℃缓缓滴加2-氯乙基磺酸钠，加完后继续反应5小时，经后处理铵交换，得到含杂原子N的顺-9-十八烯醇氧基聚醚磺酸钠阴非离子表面活性剂。结构见表1。
【实施例10】表面活性剂乳化性能评价
按照SPE 113313方法进行相态评价，从而计算乳化能力。主要步骤如下：将所需体积和浓度的表面活性剂水溶液加入到玻璃管中，然后将原油加入到溶液中，水-油体积比(WOR)为～1.0。密封后进行混合。然后将其置于金属浴中，加热到设定温度，定期取出样品混合，以增强各相之间的传质。直至目测界面位置没有变化，就可认为达到平衡。其乳化能力以增溶参数SP表示，即单位体积或质量的表面活性剂在油中增溶水或在水中增溶油的体积或质量。结果见表2、3。
【实施例11】表面活性剂界面性能性能评价
采用TX-500C旋转滴界面张力仪或者Dataphysics SVT20，在油藏温度，转速为5000转/分条件下，测定上述0.3wt％表面活性剂与原油之间的界面张力变化，直至油滴平衡。结果见表2、3。
【实施例12】表面活性剂洗油性能评价
取一定量油砂，按照油∶砂＝1∶4(质量比)在油藏温度下老化10天，每2小时搅拌5分钟；而后取出上述老化后的油砂5g，与0.3wt％的表面活性剂溶液按油砂∶溶液质量比＝1∶10混合均匀，在油藏温度下老化48小时后，用石油醚萃取溶液中的原油，用50ml比色管定容，分光光度计在波长430nm处比色分析。利用标准曲线计算表面活性剂溶液中原油浓度。结果见表2、3。
【实施例13】表面活性剂驱油性能评价
按照SY/T6424-2000复合驱油体系性能测试方法中的复合驱油体系物理模拟驱油效果测试，在油藏温度进行模拟驱油实验。先用注入水水驱至无油，而后转注0.3PV(岩心孔隙体积)上述表面活性剂，然后再次水驱至无油，计算提高原油采收率。结果见表2、3。
【比较例1】
按照CN201210188897.6方法制备C 30H 61O(CH 2CH 2O) 10CH 2CH 2COONa，并进行性能评价，结果见表2、3。
【比较例2】
按照US20110281779A1方法制备表面活性剂C 30H 61O-(BO) 8-(PO) 12-(EO) 30-SO 3Na，并进行性能评价，结果见表2、3。
表1实施例1-7表面活性剂组成及结构
Figure PCTCN2020125017-appb-000002
Figure PCTCN2020125017-appb-000003
表2实施例1-7表面活性剂中高温性能
测试条件：
90℃，矿化度35,000mg/L，二价离子含量1,000mg/L，原油API＝25，岩芯渗透率220mD
Figure PCTCN2020125017-appb-000004
将实施例3制备的表面活性剂配制成不同浓度，测试与上述原油油水界面张力，结果见表3。
表3不同浓度表面活性剂组与原油油水界面张力
表面活性剂用量(wt％) 0.05 0.1 0.2 0.3
界面张力(毫牛/米) 0.00526 0.000999 0.000688 0.000501
上述结果表明，本发明表面活性剂对于测试的稠油具有很高的油水界面活性。
将本发明的表面活性剂，再次用于高温高盐稠油油藏，测试其油水界面张力，结果见表4。
表4实施例1-7表面活性剂高温性能
测试条件：
120℃，矿化度300,000mg/L，二价离子含量10,000mg/L，原油API＝18，岩芯渗透率500mD
Figure PCTCN2020125017-appb-000005
由表2、表3、表4结果可见，本发明制备的表面活性剂，其性能优良，与比较例1、2相比，本发明人惊奇地发现乳化能力和洗油性能均大幅提高，取得了预料不到的提高采收率的效果。

Claims (14)

  1. 一种表面活性剂，具有如下式(I)：
    R 1-O-(Poly) n-X-Y a-·a/bM b+；  (I)
    其中：
    R 1为C 1～C 50的脂肪基、芳香基中的任意一种；
    各基团Poly彼此相同或不同，各自独立地选自式(Ru-O) m代表的基团；在各基团Poly之间，各基团Ru彼此相同或不同，各自独立地选自C 2-6直链或支链亚烷基，前提是：在至少一部分的基团Poly中的基团Ru选自亚丁基，以及至少一部分的基团Poly之间有间隔基团L；其中所述L为具有0-30个碳原子的包含杂原子和两个自由端的基团；
    n为0～300且大于0中的数；
    对于各个类型的基团(Ru-O)，m独立地为0～100且大于0中的数；
    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为使所述通式保持电荷平衡的阳离子或阳离子基团；
    a为Y的化合价的绝对值，b为M的化合价的绝对值。
  2. 根据权利要求1所述的表面活性剂，其特征在于所述R 1为C 1～C 50的烷基、烯基、芳基、稠环芳烃中的任意一种；更优选为C 1～C 30的烷基、烯基、芳基、稠环芳烃中的任意一种；所述杂原子为N和/或S。
  3. 根据权利要求1所述的表面活性剂，其特征在于所述L独立选自-NR 6-、-S-、-X 1-R 5-X 2-中的至少一种，其中，X 1、X 2独立选自NR 6或S，R 5选自C 0-C 10亚烷基、亚烯基、亚芳基中的任意一种，R 6选自H或C 1～C 4的烷基。
  4. 根据权利要求3所述的表面活性剂，其特征在于所述R 5选自C 0-C 6的亚烷基、亚烯基、亚芳基中的任意一种，R 6选自H。
  5. 根据权利要求1所述的表面活性剂，其特征在于m独立地为1～50中的任意一个数。
  6. 根据权利要求1所述的表面活性剂，其特征在于所述X为包含1-6个碳原子的亚烷基、亚烯基、亚芳基中的任意一种。
  7. 根据权利要求1所述的表面活性剂，其特征在于所述阴离子基 团为羧酸根、磺酸根、硫酸根、磷酸根中的至少一种，更优选为羧酸根、磺酸根中的至少一种；所述M选自碱金属阳离子、碱土金属阳离子、铵根离子中的至少一种；更优选为选自Na +、K +、Mg 2+、Ca 2+、NH 4 +中的至少一种。
  8. 根据前述权利要求中任一所述的表面活性剂，其特征在于式(I)中包含两个或更多个相同或不同的间隔基团L，且其中有至少一个基团Poly处于两个间隔基团L之间。
  9. 根据前述权利要求中任一所述的表面活性剂，其特征在于在所述各基团Poly中，至少一部分的基团Poly中的基团Ru选自亚乙基，至少一部分的基团Poly中的基团Ru选自亚丙基或亚异丙基，以及至少一部分的基团Poly中的基团Ru选自亚丁基、亚仲丁基、亚异丁基或亚叔丁基。
  10. 根据前述权利要求中任一所述的表面活性剂，其特征在于式(I)中包含至少两个间隔基团L，其中至少一部分基团L中包含杂原子N，且至少一部分基团L中包含杂原子S。
  11. 根据前述权利要求中任一所述的表面活性剂，其特征在于式(I)中，临近R 1侧的基团Poly具有比临近X侧的基团Poly更多的碳原子。
  12. 一种表面活性剂，具有如下分子通式(II)：
    R 1-O-(R 2O) x-L 1-(R 3O) y-L 2-(R 4O) z-X-Y a-·a/bM b+；  (II)
    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独立选自亚乙基、亚丙基、亚丁基中的至少一种，x、y、z分别独立地为0～100且大于0中的任意一个数；
    L 1、L 2独立地为具有0-30个碳原子的包含杂原子和两个自由端的基团。
    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为使所述通式保持电荷平衡的阳离子或阳离子基团；
    a为Y的化合价的绝对值，b为M的化合价的绝对值。
  13. 制备权利要求1～12中任一所述的表面活性剂的方法，包括以下步骤：
    a)将起始剂和环氧乙烷、环氧丙烷、环氧丁烷，在催化剂存在下，进行烷氧基化反应，得到烷氧基聚醚非离子表面活性剂；其中，所述起始剂为含C 1～C 50的烷基醇、烯基醇、烷基酚、稠环芳烃酚中的任意一种；
    b)将步骤a)得到的烷氧基聚醚非离子表面活性剂，与有机胺试剂或硫醇试剂进行反应，得到含N和/或S杂原子的烷氧基聚醚非离子表面活性剂；
    c)将步骤b)得到的含杂原子的烷氧基聚醚非离子表面活性剂，与磺化试剂或羧化试剂进行磺化或羧化反应，后经中和，得到所述的表面活性剂。
  14. 根据权利要求13所述的表面活性剂的制备方法，其特征在于所述烷氧基化反应的反应温度为140～200℃，反应压力为0～5MPa，所述起始剂与环氧乙烷、环氧丙烷或环氧丁烷的摩尔比为1∶(1～50)；所述催化剂为碱金属氢氧化合物、DMC双金属聚醚催化剂或磷腈催化剂，用量为起始剂重量的0.001～2.0％；所述步骤b)中的反应温度为100～300℃，反应压力为0～5MPa，反应时间为1～10小时；所述磺化反应或羧化反应的反应温度为80～200℃，反应压力为0～3MPa。
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