WO2020098240A1 - 一种用于高温自转向酸的黏弹性表面活性剂、制备方法及应用 - Google Patents

一种用于高温自转向酸的黏弹性表面活性剂、制备方法及应用 Download PDF

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WO2020098240A1
WO2020098240A1 PCT/CN2019/087290 CN2019087290W WO2020098240A1 WO 2020098240 A1 WO2020098240 A1 WO 2020098240A1 CN 2019087290 W CN2019087290 W CN 2019087290W WO 2020098240 A1 WO2020098240 A1 WO 2020098240A1
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solution
acid
reaction
surfactant
fatty
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冯玉军
王骥
殷鸿尧
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四川大学
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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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
    • C07C209/50—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • 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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/72—Eroding chemicals, e.g. acids
    • C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
    • 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
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/30—Viscoelastic surfactants [VES]

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  • the invention relates to the field of oil and gas exploitation, in particular to a viscoelastic surfactant for high-temperature self-turning acid, preparation method and application.
  • acid fluid usually 20% concentration of hydrochloric acid
  • acid cement is used to rock cement (mostly carbonates and clay) or formation pores
  • the dissolution and dissolution of plugs in fractures, etc. restore the permeability of the reservoir, and expand the oil and gas seepage channels (KMBartko, FFChang, LAbehrmann, ICWalton.Effective matrix, acidizing in carbonate, reserve-does, perforating, matter? Paper, presented at SPE) Middle, East, Oil, Gas, Show, Conference, MEOS, Proceedings,oane, 250-259, 2007).
  • the conventional acid system has always had two problems: (1) The reaction speed with the reservoir rock is fast, which results in the acidification distance being too short, and it is difficult to achieve deep acidification. (2) Due to the heterogeneity of the reservoir, after being injected into the formation, the acid fluid follows the principle of least resistance and preferentially enters the high permeability area rather than the low permeability area that needs the most acidification treatment; and, the subsequent injection The acid will flow along the reacted large pores with less resistance, making the hyper-permeable area excessively acidified, while the medium-low permeability area will not be effectively improved by plugging, which eventually leads to a further increase in interlayer heterogeneity (F. Chang, Q. Qu, W. Frenier. A novel self-diverting-aciddeveloped for matrix stimulation of carbonate reservoirs.Paper SPE65033 presented at the SPE International Symposium on Oilfield Chemistry held in Houston, Texas, 13–16 February).
  • VES viscoelastic surfactant
  • This high-viscosity acid can not only further reduce the acid rock reaction rate, but also temporarily block the high permeability area, forcing the subsequently injected acid to enter the low-permeability area, to achieve the diversion of acid, to achieve deep acidification and deep reservoir
  • VDA viscoelastic surfactant self-diverting acid
  • VDA system Compared with other turning acid, especially cross-linked polymer acid solution system, VDA system has two significant advantages: (1) does not contain Fe3 + or Zr4 + and other high-valent metal ion cross-linking agent, to avoid the increase of pH value after acid consumption The problem of metal hydroxide precipitation and metal sulfide precipitation in sulfur-containing wells (Liu Yi, Chen Fu, Wang Dayong, Zhang Qigen. VDA self-turning acid mechanism. Natural Gas Industry, 2008, 11, 88).
  • the current VES is not resistant to high temperatures and is only suitable for reservoirs below 120 ° C.
  • Liu Jing and others Liu Jing, Xu Jianhua, Qiao Xuanwei, Luo Cheng, Yu Menghong, Yan Fei. Development and performance evaluation of clean self-turning acid solution.
  • US Patent US4695389 discloses a VDA system based on N, N-dihydroxyethyl fatty amine acetate surfactant, the initial viscosity of the system is low, but as the acid rock reaction progresses, the viscosity of the system increases, making it The increased flow resistance forces the subsequent acid to enter the low-permeability area, which can achieve the purpose of uniform acidification, but the viscosity of the system is as low as 5mPa ⁇ s at 80 ° C, making it difficult to reduce the acid rock reaction rate.
  • U.S. Patent US7119050 discloses a VDA system based on amphoteric surfactants of alkyl betaine.
  • the viscosity As the acid-rock reaction progresses, the viscosity first increases and then decreases.
  • the viscosity is as high as 100 mPa ⁇ s at 150 ° C, but the surface of the alkyl betaine
  • the amount of active agent is as high as 8%, which results in high operating costs.
  • VES cationic and zwitterionic surfactants
  • alkyl betaine amphoteric surfactants especially alkyl betaine amphoteric surfactants, amine oxide amphoteric surfactants, etc.
  • Most of these VES molecular structures contain easy hydrolysis The weak bonds (amide bonds, ester bonds, ether bonds, etc.) are easily broken in a high temperature and strong acid environment, so it is difficult for VES to maintain a stable chemical structure during acidification operations, and it is easy to deteriorate and decompose (ZYZhao, GC Lv, YHZhang, SJLian, N.Tian.PerformanceofEDAB-HClacquiredblendedsystemasfracturingfluidsinoilsfields.ChineseJ.Chem.Engin., 2014,22,202).
  • the purpose of the present invention is to overcome the shortcomings of the prior art, to provide a viscoelastic surfactant for high temperature self-turning acid, preparation method and application, such viscoelastic surfactant can maintain stable chemistry in strong acid and high temperature environment Structure, with excellent acid thickening ability and good temperature resistance, to meet the application requirements of harsh environments such as strong acid and high temperature.
  • a viscoelastic surfactant for high temperature self-turning acid the structural formula of the viscoelastic surfactant is:
  • n is a saturated alkane with 2 to 8 carbon atoms
  • R 1 is a saturated or unsaturated alkane with 18 to 28 carbon atoms
  • R 2 and R 3 are each independently a methyl group, an ethyl group, a hydrogen atom, R 2.
  • R 3 may be the same or different
  • X — is any one of Cl — , Br — , F — , CO 3 2- , SO 4 2- , HCOO — , CH 3 COO — .
  • the preparation method of the viscoelastic surfactant for high temperature self-turning acid includes the following steps:
  • S3 Mix the fatty amine with an acid solution with a mass concentration of 10% to 20% and stir it evenly to protonate the fatty tertiary amine, that is, to form an ultra-long-chain viscoelastic surfactant.
  • the dosage of the acid solution is fatty amine and acid
  • the molar ratio of hydrogen ions in the liquid is 1: 2.
  • the fatty acid is a combination of at least one or more of saturated or unsaturated alkyl fatty acids having 18 to 28 carbon atoms.
  • the organic amine includes N, N-dimethylethylenediamine, N, N-dimethyl-1,3-propanediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethylethylenediamine, N, N-diethyl-1,3-propanediamine, ethylenediamine, propylenediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octyl A combination of one or more diamines.
  • the metal hydride includes one or more of LiAlH 4 , LiBH 4 or NaBH 4 .
  • the acid solution includes one or a combination of HCl solution, HBr solution, HF solution, H 2 SO 4 solution, H 2 CO 3 solution, HCOOH solution, and CH 3 COOH solution.
  • the viscoelastic surfactant is mixed with an acid solution with a mass concentration of 10% to 20%, and the acid solution with a mass concentration of 10% to 20% includes an HCl solution, an HBr solution, an HF solution, and an H 2 SO 4 solution , H 2 CO 3 solution, HCOOH solution, CH 3 COOH solution of one or more combinations, the amount of the 10% to 20% acid solution is to make the viscoelastic ultra-long chain in the obtained viscous acid solution
  • the mass concentration of the surfactant thickener is 1% to 3%.
  • the viscoelastic surfactant as a thickening steering agent not only has excellent acid thickening performance, but also has good temperature resistance.
  • the temperature is as high as 150 °C
  • the viscosity of the self-turning acid based on the surfactant is relatively stable and greater than 80mPa ⁇ s, which can meet the application requirements of harsh environments such as strong acids and high temperatures.
  • the viscoelastic surfactant has a stable chemical structure as a thickening steering agent, and does not decompose even under harsh environments such as high temperature and strong acidity, and satisfies the application requirements of harsh environments such as strong acid and high temperature.
  • the viscoelastic surfactant as a thickening and diverting agent can significantly reduce the reaction rate of the acid liquid and the reservoir rock to achieve the purpose of extending the acidizing distance, increasing the acidizing operation time and uniform acidizing.
  • the preparation of the viscoelastic surfactant can adjust the performance of the viscoelastic ultra-long-chain surfactant thickener by changing the type of fatty acid, fatty amine and acid solution.
  • Fig. 1 is a nuclear magnetic resonance hydrogen spectrum spectrum of N- (cis-docosa-9-alkenyl-amidopropyl) -N, N-dimethyl tertiary amine.
  • FIG. 2 is a nuclear magnetic resonance hydrogen spectrum spectrum of N- (cis-docosa-9-alkenyl-aminopropyl) -N, N-dimethyl tertiary amine.
  • FIG. 3 is a nuclear magnetic resonance hydrogen spectrum spectrum of N- (cis-docosa-9-alkenyl-aminopropyl) -N, N-dimethyl tertiary amine hydrochloride.
  • FIG. 4 is a mass spectrum of N- (cis-docosa-9-alkenyl-aminopropyl) -N, N-dimethyl tertiary amine hydrochloride.
  • Figure 5 is 3.0% N- (cis-docosa-9-alkenyl-aminopropyl) -N, N-dimethyl tertiary amine sulfate in 10% H 2 SO 4 solution at 150 ° C Rheological behavior.
  • Figure 6 is the flow of 1.0% N- (cis-docosa-9-alkenyl-aminopropyl) -N, N-dimethyl tertiary amine hydrochloride in 150% HCl solution at 150 ° C Behaving.
  • Fig. 7 is a mass spectrum of N- (cis-docosa-9-alkenyl-aminopropyl) -N, N-dimethyl tertiary amine hydrochloride after testing the viscosity at 150 ° C.
  • Figure 8 is the acid rock of 3.0% N- (cis-docosa-9-alkenyl-aminopropyl) -N, N-dimethyl tertiary amine hydrochloride in 20% HCl solution at 150 ° C Reaction kinetics curve.
  • Fig. 9 is a comparison chart before and after the acid rock reaction of the outcrop core in Xinjiang.
  • Figure 10 is the viscosity of N- (cis-docosa-9-alkenyl-aminopropyl) -N, N-dimethyl tertiary amine hydrochloride at 150 °C with the content of HCl and CaCl2 in the acid solution Curve.
  • Fig. 11 is a nuclear magnetic resonance hydrogen spectrum spectrum of N- (octadecylaminopropyl) -N, N-dimethyl tertiary amine.
  • Fig. 12 is the rheological behavior of 3.0% N- (octadecylaminopropyl) -N, N-dimethyl tertiary amine hydrochloride in a 10% HCl solution at 150 ° C.
  • a viscoelastic surfactant for high temperature self-turning acid the structural formula of the viscoelastic surfactant is:
  • n is a saturated alkane with 2 to 8 carbon atoms
  • R 1 is a saturated or unsaturated alkane with 18 to 28 carbon atoms
  • R 2 and R 3 are each independently a methyl group, an ethyl group, a hydrogen atom, R 2.
  • R 3 may be the same or different
  • X — is any one of Cl — , Br — , F — , CO 3 2- , SO 4 2- , HCOO — , CH 3 COO — .
  • the preparation method of the viscoelastic surfactant for high temperature self-turning acid includes the following steps:
  • the fatty acid is a combination of at least one or more of saturated or unsaturated alkyl fatty acids having 18 to 28 carbon atoms
  • the organic amine includes N, N-dimethylethylenediamine, N, N- Dimethyl-1,3-propanediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethylethylenediamine, N, N-diethyl-1,3 -A combination of one or more of propylenediamine, ethylenediamine, propylenediamine, butanediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine.
  • the role of adding deionized water for the first time is to quench the metal hydride, then add NaOH solution to remove metal ions, and then add deionized water to ensure that the metal hydride is completely quenched, and then filter, the resulting filtrate is dried and filtered again, will be again The resulting filtrate is filtered to remove the solvent to obtain fatty amines, and the metal hydride includes one or more of LiAlH 4 , LiBH 4 or NaBH 4 .
  • S3 Mix the fatty amine with an acid solution with a mass concentration of 10% to 20% and stir it evenly to protonate the fatty tertiary amine, that is, to form an ultra-long-chain viscoelastic surfactant.
  • the dosage of the acid solution is fatty amine and acid
  • the molar ratio of hydrogen ions (H + ) in the liquid is 1: 2, and the acid liquid includes HCl solution, HBr solution, HF solution, H 2 SO 4 solution, H 2 CO 3 solution, HCOOH solution, CH 3 COOH solution One or more combinations.
  • the method for preparing the viscoelastic surfactant can adjust the performance of the thickener of the viscoelastic ultra-long-chain surfactant by changing the types of fatty acids, organic amines and acid liquids.
  • the viscoelastic surfactant is mixed with an acid solution with a mass concentration of 10% to 20%, and the acid solution with a mass concentration of 10% to 20% includes an HCl solution, an HBr solution, an HF solution, and an H 2 SO 4 solution , H 2 CO 3 solution, HCOOH solution, CH 3 COOH solution one or more of the combination, so that the viscosity concentration of the viscoelastic ultra-long-chain surfactant thickener in the viscosity-changing acid solution is 1% ⁇ 3%.
  • the viscoelastic surfactant When used as a thickener for self-turning acid, a good viscosity increase effect can be achieved by adding a mass concentration of 1%, so the economic cost is low and it is advantageous for large-scale use.
  • the viscoelastic surfactant as a thickening turning agent not only has excellent acid thickening performance, but also has good temperature resistance.
  • the temperature is up to 150 ° C, the viscosity of the self-turning acid based on the surfactant is more stable and More than 80mPa ⁇ s, it can meet the application requirements of harsh environments such as strong acid and high temperature.
  • N- (cis-docosa-9-alkenyl-aminopropyl) -N, N-dimethyl tertiary amine and mass concentration 10% H 2 SO 4 and 20% HCl solution are mixed.
  • the N + (octadecylaminopropyl) -N, N-dimethyl tertiary amine and 10% H 2 SO 4 , 20% HCl H + molar ratio is 1: 2.
  • N- (cis-docosa-9-alkenyl) -N, N-dimethyl tertiary amine sulfate N- (cis-docosa-9-alkenyl) -N, N-
  • the structure of N- (cis-docosa-9-alkenyl) -N, N-dimethyl tertiary amine hydrochloride is shown in the nuclear magnetic resonance spectrum of Figure 3 Spectrogram and mass spectrum of Figure 4).
  • Acid rock reaction kinetics test mix N- (cis-docosa-9-alkenyl-aminopropyl) -N, N-dimethyl tertiary amine with a mass concentration of 20% HCl solution, Stir at 50 ° C for 24h until uniform, to obtain the self-turning acid of N- (cis-docosa-9-alkenyl) -N, N-dimethyl tertiary amine hydrochloride.
  • the Xinjiang outcrop core with a cross-sectional area of 4.9 cm 2 was selected and the acid-rock reaction kinetics were tested by a rotating disk reactor.
  • the set temperature is 150 °C
  • the pressure is 7.5MPa
  • the rotation speed is 500r / min.
  • the reaction rate constant of self-turning acid K 7.4 ⁇ 10 -6 (mol ⁇ L) -m ⁇ mol / (cm 2 ⁇ s)
  • the reaction rate constant K 3.5 of the control group (20% HCl) ⁇ 10 -5 (mol ⁇ L) -m ⁇ mol / (cm 2 ⁇ s) (Figure 8)
  • the self-turning acid acid solution with viscoelastic ultra-long chain surfactant as thickening turning agent in this example has Good retarding performance can effectively extend the time of acidification.
  • the viscoelastic ultra-long-chain surfactant obtained in this example is used as a thickening steering agent.
  • the self-steering acid acid core has a uniform and smooth appearance, without obvious pits. Erosion, proving its uniform acidification ability.
  • A is the core before the test and B is the N- (cis-docosa-9-alkenyl-aminopropyl) -N, N-dimethyl tertiary amine hydrochloride
  • the core after the reaction of the salt 20% HCl solution, C is the core after the reaction with 20% HCl.
  • Turning ability test In order to measure the changing trend of turning acid viscosity in the reservoir, the concentrations of HCl and CaCl 2 in acid rock reaction at different times were calculated. A series of mixed solutions of HCl and CaCl 2 were prepared, and N- (cis-docosa-9-alkenyl-aminopropyl) -N, N-dimethyl tertiary amine was added to the above HCl and CaCl 2 solution Mix and stir at 50 ° C for 24h until uniform. The steering ability was tested by Anton Paar rheometer and its supporting PR170 / XL rotor / rotor system.
  • the set temperature was 150 °C, the shear rate was 170s -1 and the pressure was 1MPa.
  • Self-turning acid viscosity value It was found that the self-turning acid viscosity based on N- (cis-docosa-9-alkenyl) -N, N-dimethyl tertiary amine hydrochloride decreased with the decrease of HCl concentration value, Ca 2+ ion concentration
  • the increase shows a trend of increasing first and then decreasing (Figure 10), indicating that the self-steering acidic acid liquid using the ultra-long-chain viscoelastic surfactant as the thickening steering agent in this embodiment has good steering performance and can achieve the target storage The purpose of layer uniform acidification.
  • the surfactant has a stable chemical structure as a thick liquid diverting agent, and does not decompose even in harsh environments such as high temperature and strong acidity, and can meet the application requirements of harsh environments such as strong acid and high temperature;
  • the surface As a thick liquid turning agent the active agent can significantly reduce the reaction rate of the acid liquid and the formation rock, achieve the purpose of prolonging the acidification distance, increasing the acidizing operation time and uniform acidizing.
  • N can be obtained -(Octadecylaminopropyl) -N, N-diethyl tertiary amine sulfate, N- (octadecylaminopropyl) -N, N-diethyl tertiary amine hydrochloric acid salt.
  • N- (cis-twenty-four carbon-15-alkenyl-aminooctyl) amine with a mass concentration of 10% CH 3 COOH solution, in which N- (cis-twenty-four carbon-15-ene Base-aminooctyl) amine and 10% CH 3 COOH H + molar ratio is 1: 2. 50 °C stirring 24h until uniform, you can get N- (cis-twenty-four carbon-15-alkenyl-amine Octyl) amine acetate. Then, it is mixed with a 10% mass concentration CH 3 COOH solution to obtain a self-turning acid based on N- (cis-twenty four carbon-15-alkenyl-aminooctyl) amine acetate.

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Abstract

本发明公开了一种用于高温自转向酸的黏弹性表面活性剂，其结构式如下 (I) 其中，n为具有2～8个碳原子的饱和烷烃，R1为具有18～28个碳原子的饱和或不饱和烷烃，R2、R3均独立为甲基、乙基、氢原子，R2、R3可相同或不同，X—为Cl—、Br—、F—、CO3 2-、SO4 2-、HCOO —、CH 3COO —中的任意一种。该表面活性剂的制备方法为：其由脂肪酸与有机胺通过酸胺缩合反应生成中间产物，继而与金属氢化物反应生成脂肪胺，再加入酸液将其质子化，即可得到超长链黏弹性阳离子表面活性剂。本发明还提供了以该表面活性剂作为自转向酸的稠化转向剂的应用。本发明的表面活性剂作为稠化转向剂的自转向酸能够在150℃高温下使用，具有结构稳定、酸液增稠、均匀酸化和自动转向等优点。

Description

一种用于高温自转向酸的黏弹性表面活性剂、制备方法及应用 技术领域
本发明涉及油气开采领域，特别是涉及一种用于高温自转向酸的黏弹性表面活性剂、制备方法及应用。
背景技术
为了恢复和提高低渗油气井产量，常将酸液(通常为20％浓度的盐酸)注入储层，通过酸液对岩石胶结物(胶结物多为有碳酸盐类和粘土)或地层孔隙、裂缝内堵塞物等的溶解和溶蚀作用，恢复储层的渗透性，扩大油气渗流通道(K.M.Bartko,F.F.Chang,L.A.Behrmann,I.C.Walton.Effective matrix acidizing in carbonate reservoir-Does perforating matter？Paper presented at SPE Middle East Oil and Gas Showand Conference,MEOS,Proceedings,Bahrain,250-259,2007)。但长期以来，常规酸体系一直存在着两个问题：(1)与储层岩石反应速度快，导致酸化距离过短，难以实现深部酸化。(2)由于储层的非均质性，酸液在注入进地层后，遵循阻力最小的原则，优先进入高渗透率区域，而不是进入最需要酸化处理的低渗透区；而且，后续注入的酸液将沿阻力较小的已反应的大孔道流动，使高渗区域过度酸化，而中低渗区域则得不到有效解堵改善，最终导致层间非均质性进一步增大(F.Chang,Q.Qu,W.Frenier.A novel self-diverting-aciddeveloped for matrix stimulation of carbonate reservoirs.Paper SPE65033presented at the SPE International Symposium on Oilfield Chemistry heldin Houston,Texas,13–16February 2001)。
为了解决上述问题，2000年斯伦贝谢公司将黏弹性表面活性剂(viscoelasticsurfactant，VES)作为稠化转向剂引入常规酸液体系中，用于碳酸岩储层的酸化作业。当此稠化酸液泵入储层后，由于其黏度高，可延缓氢离子(H+)向岩石表面的扩散速度，降低酸岩反应速率，延长酸液在储层的作业时间。且随着酸岩反应的进行(CaCO3+2HCl＝CaCl2+H2O+CO2↑)，HCl浓度不断降低，pH值升高，金属离子(Ca2+)不断产生，使酸液体系黏度进一步增加。此高黏度酸液不仅可进一步降低酸岩反应速率，而且还可暂时封堵高渗透率区域，迫使后续注入的酸液进入中低渗区，实现酸液的分流转向，达到储层深部酸化和均匀酸化的双重目的。这种仅由自身pH值变化就可实现酸液自动转向的酸液体系被称之为黏弹性表面活性剂自转向酸(viscoelastic self-diverting acid，VDA)。
较之于其它转向酸尤其是交联聚合物酸液体系，VDA体系具有两个显著优点：(1)不含有Fe3+或Zr4+等高价金属离子交联剂，避免了酸液消耗后pH值升高而产生金属氢氧化物的沉淀及含硫井中产生金属硫化物沉淀的问题(刘彝,陈馥,王大勇,张启根.VDA自转向酸机理.天然气工业,2008,11,88)。(2)当VDA体系遇到储层中烃类物质后，蠕虫状胶束的疏水内核被破坏，使三维网络状结构崩解而转变为球形胶束，使体系黏度迅速降低，有利于返排，可避免对储层造成二次伤害和污染(陈大钧,陈馥,李建波.油气田应用化学.石油工业出版社,2006,148)。VDA体系自问世以来，以其优越的转向性能、降滤失性能和对储层的无伤害性而成为酸化或酸压领域的研究热点之一，已在中东、南美、墨西哥湾等地区的增产作业中得到成功应用。
尽管如此，VDA体系仍存在着一些问题：
(1)目前的VES不耐高温，仅适用于120℃以下的储层。例如，刘京等人(刘京,徐建华,乔煊威,罗成,于梦红,颜菲.清洁自转向酸液的研制及性能评价.石油天然气学报,2009,31,302)使用5％甜菜碱类表面活性剂与0.8％季铵盐类表面活性剂复配制备的自转向酸液体系，黏度随pH值升高呈现先增大后减小的趋势，具有自转向功能，但此自转向酸在95℃时黏度仅为110mPa·s，只适合中温油藏地层的酸化作用。又如CN106995692A公开了一种基于VES和纳米颗粒(TiO2、SiO2)复合的自转向酸，该酸液虽具有自转向、缓速和低滤失等优点，且无需交联剂和破胶剂、返排彻底，不会对地层产生伤害，但室内研究发现其在80℃、170s-1剪切1h后，黏度仅有30mPa·s。美国专利US4695389公开了一种基于N,N-二羟乙基脂肪胺醋酸盐表面活性剂的VDA体系，体系初始黏度较低，但随着酸岩反应的进行，体系黏度增大，使其流动阻力加大，迫使后续酸液进入低渗区域，可实现均匀酸化的目的，但是该体系在80℃时黏度低达5mPa·s，难以实现降低酸岩反应速率的功能。美国专利US7119050公开了一种基于烷基甜菜碱两性表面活性剂的VDA体系，随着酸岩反应的进行，黏度先增后减，在150℃时黏度高达100mPa·s，但烷基甜菜碱表面活性剂用量高达8％，导致作业费用高昂。
(2)现用VDA体系中所用VES多为阳离子型和两性离子表面活性剂特别是烷基甜菜碱类两性表面活性剂、氧化胺类两性表面活性剂等，这些VES分子结构中多含有易水解的弱键(酰胺键、酯键、醚键等)，在高温强酸环境中易断裂，因此在酸化作业时，VES难以保持稳定的化学结构，易变质分解(Z.Y.Zhao,G.C  Lv,Y.H.Zhang,S.J.Lian,N.Tian.Performanceof EDAB-HCl acid blended system as fracturing fluids in oil fields.ChineseJ.Chem.Engin.,2014,22,202)。
在上述背景下，急需研制一种能在高温环境下能保持一定黏度且结构稳定的VES作为VDA的稠化转向剂。
发明内容
本发明的目的在于克服现有技术的不足，提供一种用于高温自转向酸的黏弹性表面活性剂、制备方法及应用，该类黏弹性表面活性剂能在强酸高温环境中保持稳定的化学结构，具有优异的酸液增稠能力和良好的耐温性，满足强酸、高温等恶劣环境的应用要求。
本发明的目的是通过以下技术方案来实现的，一种用于高温自转向酸的黏弹性表面活性剂，所述黏弹性表面活性剂的结构式为：
Figure PCTCN2019087290-appb-000001
其中，n为具有2～8个碳原子的饱和烷烃，R 1为具有18～28个碳原子的饱和或不饱和烷烃，R 2、R 3均独立为甲基、乙基、氢原子，R 2、R 3可相同或不同，X —为Cl —、Br —、F —、CO 3 2-、SO 4 2-、HCOO —、CH 3COO —中的任意一种。
所述的一种用于高温自转向酸的黏弹性表面活性剂的制备方法，包括以下步骤：
S1：将脂肪酸与有机胺加入反应器中，升温至160～170℃反应11～13h停止反应，待反应液冷却至25～35℃后，将其倾倒入冷的丙酮溶液，搅拌并过滤，再用丙酮洗涤过滤固体2～3次，冷冻干燥后得到白色固体中间体，其中，有机胺与脂肪酸的摩尔比为(1.1～1.5)：1；
S2：将所得中间体溶于四氢呋喃中，在0～5℃下滴入金属氢化物的四氢呋喃溶液形成反应液，中间体与金属氢化物的摩尔比为1：(2.0～2.5)，滴加完毕后升温至65～85℃反应24～36h，反应结束后向所得反应液中依次加入去离子水、质量浓度10％～20％的NaOH溶液、去离子水，第一次加入去离子水的作用为使金属氢化物淬灭，然后加NaOH 溶液除去金属离子，再加去离子水保证金属氢化物完全淬灭，然后过滤，所得滤液干燥后再次过滤，将再次过滤所得滤液除去溶剂得到脂肪胺；
S3：将脂肪胺与质量浓度10％～20％的酸液混合并搅拌均匀，使脂肪叔胺质子化，即形成超长链黏弹性表面活性剂，所述酸液的用量为脂肪胺与酸液中氢离子的摩尔比为1：2。
所述脂肪酸为具有18～28个碳原子的饱和或不饱和烷基脂肪酸中的至少一种或多种的组合。
所述有机胺包括N,N-二甲基乙二胺、N,N-二甲基-1,3-丙二胺、N,N-二甲基-1,4-丁二胺、N,N-二乙基乙二胺、N,N-二乙基-1,3-丙二胺、乙二胺、丙二胺、丁二胺、戊二胺、己二胺、庚二胺、辛二胺中的一种或多种的组合。
所述金属氢化物包括LiAlH 4、LiBH 4或NaBH 4中的一种或多种的组合。
所述酸液包括HCl溶液、HBr溶液、HF溶液、H 2SO 4溶液、H 2CO 3溶液、HCOOH溶液、CH 3COOH溶液中的一种或多种的组合。
所述反应过程中保持循环水冷却使有机胺回流。
所述的一种用于高温自转向酸的黏弹性表面活性剂在稠化转向剂中的应用。
将所述黏弹性表面活性剂与质量浓度为10％～20％的酸液混合，所述质量浓度为10％～20％的酸液包括HCl溶液、HBr溶液、HF溶液、H 2SO 4溶液、H 2CO 3溶液、HCOOH溶液、CH 3COOH溶液中的一种或多种的组合，所述10％～20％的酸液的用量为使得到的变黏酸液中黏弹性超长链表面活性剂稠化剂的质量浓度为1％～3％。
本发明的有益效果是：
(1)所述黏弹性表面活性剂作为稠化转向剂不仅具有优异的酸液增稠性能，且耐温性较好。在温度高达150℃时，基于该表面活性剂的自转向酸的黏度较为稳定且大于80mPa·s，满足强酸、高温等恶劣环境的应用需求。
(2)所述黏弹性表面活性剂作为稠化转向剂化学结构稳定，即使处于高温强酸性等恶劣环境下也不会发生分解，满足强酸、高温等恶劣环境的应用需求。
(3)所述黏弹性表面活性剂作为稠化转向剂能明显降低酸液与储层岩石的反应速率，达到延长酸化距离、提高酸化作业时间及均匀酸化的目的。
(4)本所述黏弹性表面活性剂作为稠化剂应用于自转向酸时，添加质量浓度为1％即可达到较好的增黏效果，因此经济成本低，利于大规模使用。
(5)所述黏弹性表面活性剂的制备可通过改变脂肪酸、脂肪胺和酸液的种类等实现对黏弹性超长链表面活性剂稠化剂性能的调节。
附图说明
图1是N-(顺-二十二碳-9-烯基-酰胺基丙基)-N,N-二甲基叔胺的核磁共振氢谱谱图。
图2是N-(顺-二十二碳-9-烯基-胺基丙基)-N,N-二甲基叔胺的核磁共振氢谱谱图。
图3是N-(顺-二十二碳-9-烯基-胺基丙基)-N,N-二甲基叔胺盐酸盐的核磁共振氢谱谱图。
图4是N-(顺-二十二碳-9-烯基-胺基丙基)-N,N-二甲基叔胺盐酸盐的质谱谱图。
图5是3.0％N-(顺-二十二碳-9-烯基-胺基丙基)-N,N-二甲基叔胺硫酸盐在10％H 2SO 4溶液中在150℃下的流变行为。
图6是1.0％N-(顺-二十二碳-9-烯基-胺基丙基)-N,N-二甲基叔胺盐酸盐在20％HCl溶液中在150℃下的流变行为。
图7是N-(顺-二十二碳-9-烯基-胺基丙基)-N,N-二甲基叔胺盐酸盐在150℃下测试黏度后的质谱谱图。
图8是3.0％N-(顺-二十二碳-9-烯基-胺基丙基)-N,N-二甲基叔胺盐酸盐在20％HCl溶液在150℃下的酸岩反应动力学曲线。
图9是新疆露头岩心进行酸岩反应前后对照图。
图10是N-(顺-二十二碳-9-烯基-胺基丙基)-N,N-二甲基叔胺盐酸盐的黏度在150℃下随酸液中HCl和CaCl2含量变化曲线。
图11是N-(十八烷基胺基丙基)-N,N-二甲基叔胺的核磁共振氢谱谱图。
图12是3.0％N-(十八烷基胺基丙基)-N,N-二甲基叔胺盐酸盐在10％HCl溶液中在150℃下的流变行为。
具体实施方式
下面将结合实施例，对本发明的技术方案进行清楚、完整的描述。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本 领域技术人员在没有付出创造性劳动的前提下所获得的所有其它实施例，都属于本发明保护的范围。
参阅图1-12，一种用于高温自转向酸的黏弹性表面活性剂，所述黏弹性表面活性剂的结构式为：
Figure PCTCN2019087290-appb-000002
其中，n为具有2～8个碳原子的饱和烷烃，R 1为具有18～28个碳原子的饱和或不饱和烷烃，R 2、R 3均独立为甲基、乙基、氢原子，R 2、R 3可相同或不同，X —为Cl —、Br —、F —、CO 3 2-、SO 4 2-、HCOO —、CH 3COO —中的任意一种。
所述的一种用于高温自转向酸的黏弹性表面活性剂的制备方法，包括以下步骤：
S1：将脂肪酸与有机胺加入反应器中，升温至160～170℃反应11～13h停止反应，所述反应过程中保持循环水冷却使有机胺回流，待反应液冷却至25～35℃后，将其倾倒入冷的丙酮溶液，搅拌并过滤，再用丙酮洗涤过滤固体2～3次，冷冻干燥后得到白色固体中间体。其中，有机胺与脂肪酸的摩尔比为(1.1～1.5)：1。
所述脂肪酸为具有18～28个碳原子的饱和或不饱和烷基脂肪酸中的至少一种或多种的组合，所述有机胺包括N,N-二甲基乙二胺、N,N-二甲基-1,3-丙二胺、N,N-二甲基-1,4-丁二胺、N,N-二乙基乙二胺、N,N-二乙基-1,3-丙二胺、乙二胺、丙二胺、丁二胺、戊二胺、己二胺、庚二胺、辛二胺中的一种或多种的组合。
S2：将所得中间体溶于四氢呋喃中，在0～5℃下滴入金属氢化物的四氢呋喃溶液形成反应液，中间体与金属氢化物的摩尔比为1：(2.0～2.5)，滴加完毕后升温至65～85℃反应24～36h，反应结束后向所得反应液中依次加入去离子水、质量浓度10％～20％的NaOH溶液、去离子水。第一次加入去离子水的作用为使金属氢化物淬灭，然后加NaOH溶液除去金属离子，再加去离子水保证金属氢化物完全淬灭，然后过滤，所得滤液干燥后再次过滤，将再次过滤所得滤液除去溶剂得到脂肪胺，所述金属氢化物包括LiAlH 4、LiBH 4或NaBH 4中的一种或多种的组合。
S3：将脂肪胺与质量浓度10％～20％的酸液混合并搅拌均匀，使脂肪叔胺质子化，即形成超长链黏弹性表面活性剂，所述酸液的用量为脂肪胺与酸液中氢离子(H +)的摩尔比为1：2，所述酸液包括HCl溶液、HBr溶液、HF溶液、H 2SO 4溶液、H 2CO 3溶液、HCOOH溶液、CH 3COOH溶液中的一种或多种的组合。
所述黏弹性表面活性剂的制备方法可通过改变脂肪酸、有机胺和酸液的种类等，实现对黏弹性超长链表面活性剂稠化剂性能的调节。
所述的一种用于高温自转向酸的黏弹性表面活性剂在稠化转向剂中的应用。
将所述黏弹性表面活性剂与质量浓度为10％～20％的酸液混合，所述质量浓度为10％～20％的酸液包括HCl溶液、HBr溶液、HF溶液、H 2SO 4溶液、H 2CO 3溶液、HCOOH溶液、CH 3COOH溶液中的一种或多种的组合，使得到的变黏酸液中黏弹性超长链表面活性剂稠化剂的质量浓度为1％～3％。
所述黏弹性表面活性剂作为稠化剂应用于自转向酸时，添加质量浓度为1％即可达到较好的增黏效果，因此经济成本低，利于大规模使用。
所述黏弹性表面活性剂作为稠化转向剂不仅具有优异的酸液增稠性能，且耐温性较好，在温度高达150℃时，基于该表面活性剂的自转向酸的黏度较为稳定且大于80mPa·s，可满足强酸、高温等恶劣环境的应用需求。
以下结合典型实施例分析该黏弹性表面活性剂作为稠化转向剂的耐强酸、耐高温等性能：
实施例一
(1)称取16.92g(0.05mol)顺二十二碳-13-烯酸(俗名“芥酸”)和7.66g(0.075mol)N,N-二甲基丙二胺(n＝2，R 2，R 3为甲基)加入三口反应烧瓶，逐渐升温至160℃。反应11h后停止反应，待溶液冷却至室温将其转移至丙酮溶液中，搅拌并过滤，冷冻干燥，即得到白色粉末固体，即为N-(顺-二十二碳-9-烯基-酰胺基丙基)-N,N-二甲基叔胺，其结构表征见核磁氢谱谱图(图1)，化合物中各质子峰的化学位移已在谱图中找到归属，且各质子共振峰积分面积比值与理论值之间吻合较好，表明该化合物已成功合成。
(2)将所得N-(顺-二十二碳-9-烯基-酰胺基丙基)-N,N-二甲基叔胺加入到500mL圆底烧瓶中，加入100mL四氢呋喃溶解，待完全溶解后降温至0℃，逐滴加入LiAlH 4的四氢呋喃溶液，其中N-(顺-二十二碳-9-烯基-酰胺基丙基)-N,N-二甲基叔胺与金属氢化物的 摩尔比为1：2.5，滴加完毕后升温至85℃反应24h，反应结束后向所得反应液中依次加入去离子水、10％NaOH溶液、去离子水将反应淬灭，然后过滤反应液，滤液用无水MgSO 4干燥，过滤，将滤液旋转蒸发除去溶剂，得到N-(顺-二十二碳-9-烯基-胺基丙基)-N,N-二甲基叔胺，其结构表征见核磁共振氢谱谱图(图2)，化合物中各质子峰的化学位移已在谱图中找到归属，且各质子共振峰积分面积比值与理论值之间吻合较好，表明该化合物已成功合成。
(3)耐温及耐剪切性能测试：将N-(顺-二十二碳-9-烯基-胺基丙基)-N,N-二甲基叔胺分别与质量浓度10％H 2SO 4、20％HCl溶液混合。其中N-(二十八烷基胺基丙基)-N,N-二甲基叔胺与10％H 2SO 4、20％HCl中H+摩尔比为1：2。50℃搅拌24h至均匀，得到N-(顺-二十二碳-9-烯基)-N,N-二甲基叔胺硫酸盐、N-(顺-二十二碳-9-烯基)-N,N-二甲基叔胺盐酸盐(其中，N-(顺-二十二碳-9-烯基)-N,N-二甲基叔胺盐酸盐的结构表征见图3的核磁共振氢谱谱图和图4的质谱谱图)。再将其别与质量浓度15％H 2SO 4、10％HCl溶液混合，即可分别得到N-(顺-二十二碳-9-烯基)-N,N-二甲基叔胺硫酸盐和N-(顺-二十二碳-9-烯基)-N,N-二甲基叔胺盐酸盐的自转向酸，其中酸液用量使得N-(二十八烷基胺基丙基)-N,N-二甲基叔胺硫酸盐、N-(二十八烷基胺基丙基)-N,N-二甲基叔胺盐酸盐的浓度分别为3％和1％。通过哈克流变仪及其所配套的PZ39转子/转筒***进行测试酸液体系在不同温度下的黏度。在剪切速率为170s -1下测量所得自转向酸液黏度随温度、时间的变化关系，结果见图5和图6。可以发现，当温度稳定在150℃时，酸液黏度较为稳定且均大于80mPa·s，表明本实施例所得超长链黏弹性表面活性剂作为稠化剂具有良好的耐温性、耐剪切性。测试结束后将酸液回收，所得酸液与测试前外观一致，均为无色透明，冷冻干燥后对其进行质谱表征(图7)，谱图中找到m/z＝409.47(M+H +)，理论值为409.45，证明本实施例所制备的超长链表面活性剂在高温强酸环境下化学结构稳定，未发生分解变质。
(4)酸岩反应动力学测试：将N-(顺-二十二碳-9-烯基-胺基丙基)-N,N-二甲基叔胺与质量浓度20％HCl溶液混合，50℃搅拌24h至均匀，得到N-(顺-二十二碳-9-烯基)-N,N-二甲基叔胺盐酸盐的自转向酸。选取横截面积为4.9cm 2的新疆露头岩心，通过旋转圆盘反应仪测试酸岩反应动力学。设定温度为150℃，压力7.5MPa，转速500r/min。结果发现，自转向酸的反应速率常数K＝7.4×10 -6(mol·L) -m·mol/(cm 2·s)，低于对照组(20％ HCl)的反应速率常数K＝3.5×10 -5(mol·L) -m·mol/(cm 2·s)(图8)，表明本实施例以黏弹性超长链表面活性剂为稠化转向剂的自转向酸酸液具有良好的缓速性能，能有效延长酸化作用时间。观测测试后的岩心样品，相比于20％HCl腐蚀的岩心，本实施例所得黏弹性超长链表面活性剂作为稠化转向剂的自转向酸酸液酸化岩心外观均匀、平整，无明显坑蚀，证明其具有均匀酸化能力。具体如图9所示，其中A为测试前的岩心，B为与N-(顺-二十二碳-9-烯基-胺基丙基)-N,N-二甲基叔胺盐酸盐的20％HCl溶液反应后的岩心，C为与20％HCl反应后的岩心。
(5)转向能力测试：为了测量转向酸在储层内黏度变化趋势，计算了不同时刻酸岩反应中HCl和CaCl 2的浓度。配制了一系列HCl和CaCl 2的混合溶液，将N-(顺-二十二碳-9-烯基-胺基丙基)-N,N-二甲基叔胺与上述HCl和CaCl 2溶液混合，50℃搅拌24h至均匀。通过安东帕流变仪及其所配套的PR170/XL转子/转筒***对其转向能力进行测试，设定温度为150℃，剪切速率为170s -1，压力为1MPa，测试不同时刻的自转向酸黏度值。结果发现，基于N-(顺-二十二碳-9-烯基)-N,N-二甲基叔胺盐酸盐的自转向酸黏度随着HCl浓度值的减少、Ca 2+离子浓度增加呈现先增大后减小的趋势(图10)，表明本实施例以超长链黏弹性表面活性剂为稠化转向剂的自转向酸酸液具有良好的转向性能，能实现对目标储层均匀酸化的目的。
由实施例一可知，所述表面活性剂作为稠液转向剂化学结构稳定，即使处于高温强酸性等恶劣环境下也不会发生分解，可满足强酸、高温等恶劣环境的应用需求；所述表面活性剂作为稠液转向剂能明显降低酸液与地层岩石的反应速率，达到延长酸化距离，提高酸化作业时间及均匀酸化的目的。
实施例二
(1)称取14.22g(0.05mol)十八烷酸(俗名“硬脂酸”)和5.61g(0.055mol)N,N-二甲基丙二胺(n＝2，R 2，R 3为甲基)加入三口反应烧瓶，逐渐升温至170℃。反应13h后停止反应，待溶液冷却至室温将其转移至丙酮溶液中，搅拌并过滤，冷冻干燥，即得到白色粉末固体，即为N-(十八烷基酰胺基丙基)-N,N-二甲基叔胺。
(2)将所得N-(十八烷基酰胺基丙基)-N,N-二甲基叔胺加入到500mL圆底烧瓶中，加入100mL四氢呋喃溶解，待完全溶解后降温至5℃，逐滴加入LiAlH 4的四氢呋喃溶液，其中N-(十八烷基酰胺基丙基)-N,N-二甲基叔胺与金属氢化物的摩尔比为1：2，滴加完 毕后升温至65℃反应36h，反应结束后向所得反应液中依次加入去离子水、10％NaOH溶液、去离子水将反应淬灭，然后过滤反应液，滤液用无水MgSO 4干燥，过滤，将滤液旋转蒸发除去溶剂，得到N-(十八烷基胺基丙基)-N,N-二甲基叔胺，其结构表征见核磁共振氢谱谱图(图11)，化合物中各质子峰的化学位移已在谱图中找到归属，且各质子共振峰积分面积比值与理论值之间吻合较好，表明该化合物已成功合成。
(3)将N-(十八烷基胺基丙基)-N,N-二甲基叔胺与质量浓度10％HCl溶液混合，其中N-(十八烷基胺基丙基)-N,N-二甲基叔胺与10％HCl中H +摩尔比为1：2，50℃搅拌24h至均匀，得到N-(十八烷基胺基丙基)-N,N-二甲基叔胺盐酸盐。再将其与质量浓度10％HCl溶液混合，即可得到N-(十八烷基胺基丙基)-N,N-二甲基叔胺盐酸盐的自转向酸，其中酸液用量使得N-(十八烷基胺基丙基)-N,N-二甲基叔胺盐酸盐的浓度为3％。通过安东帕流变仪及其所配套的PR170/XL转子/转筒***进行测试酸液体系在不同温度下的黏度。在剪切速率为170s -1下测量所得自转向酸液黏度随温度、时间的变化关系，结果见图12。可以发现，当温度稳定在150℃时，酸液的黏度较为稳定且均大于20mPa·s，表明本实施例所得黏弹性超长链表面活性剂作为稠化剂具有良好的耐温性。
实施例三
(1)称取21.23g(0.05mol)正二十八酸(俗名“褐煤酸”)和9.76g(0.075mol)N,N-二乙基丙二胺(n＝2，R 2，R 3为乙基)加入三口反应烧瓶，逐渐升温至160℃。反应11h后停止反应，待溶液冷却至室温将其转移至丙酮溶液中，搅拌并过滤，冷冻干燥，即得到白色粉末固体，即为N-(二十八烷基酰胺基丙基)-N,N-二乙基叔胺。
(2)将所得N-(二十八烷基酰胺基丙基)-N,N-二乙基叔胺加入到500mL圆底烧瓶中，加入100mL四氢呋喃溶解，待完全溶解后降温至0℃，逐滴加入NaBH 4的四氢呋喃溶液，其中N-(二十八烷基酰胺基丙基)-N,N-二乙基叔胺与NaBH 4的摩尔比为1：2，滴加完毕后升温至80℃反应36h，反应结束后向所得反应液中依次加入去离子水、质量浓度15％NaOH溶液、去离子水将反应淬灭，然后过滤反应液，滤液用无水MgSO 4干燥，过滤，将滤液旋转蒸发除去溶剂，得到N-(二十八烷基胺基丙基)-N,N-二乙基叔胺。
(3)将N-(二十八烷基胺基丙基)-N,N-二乙基叔胺分别与质量浓度15％H 2SO 4、10％HCl溶液混合，其中N-(二十八烷基胺基丙基)-N,N-二乙基叔胺与15％H 2SO 4、10％HCl中H +摩尔比为1：2。50℃搅拌24h至均匀，即可得到N-(二十八烷基胺基丙基)-N,N- 二乙基叔胺硫酸盐、N-(二十八烷基胺基丙基)-N,N-二乙基叔胺盐酸盐。再将其别与质量浓度15％H 2SO 4、10％HCl溶液混合，即可分别得到基于N-(二十八烷基胺基丙基)-N,N-二乙基叔胺硫酸盐、N-(二十八烷基胺基丙基)-N,N-二乙基叔胺盐酸盐自转向酸。
实施例四
(1)称取18.33g(0.05mol)顺-15-二十四碳烯酸(俗名“神经酸”)和7.21g(0.055mol)辛二胺(n＝8，R 2，R 3为氢原子)加入三口反应烧瓶，逐渐升温至165℃。反应12h后停止反应，待溶液冷却至室温将其转移至丙酮溶液中，搅拌并过滤，冷冻干燥，即得到白色粉末固体，即为N-(顺-二十四碳-15-烯基-酰胺基辛基)胺。
(2)将所得N-(顺-二十四碳-15-烯基-酰胺基辛基)胺加入到500mL圆底烧瓶中，加入100mL四氢呋喃溶解，待完全溶解后降温至0℃，逐滴加入LiBH 4的四氢呋喃溶液，其中N-(顺-二十四碳-15-烯基-酰胺基辛基)胺与LiBH 4的摩尔比为1：2，滴加完毕后升温至80℃反应36h，反应结束后向所得反应液中依次加入去离子水、15％NaOH溶液、去离子水将反应淬灭，然后过滤反应液，滤液用无水MgSO 4干燥，过滤，将滤液旋转蒸发除去溶剂，得到N-(顺-二十四碳-15-烯基-胺基辛基)胺。
(3)将N-(顺-二十四碳-15-烯基-胺基辛基)胺与质量浓度10％CH 3COOH溶液混合，其中N-(顺-二十四碳-15-烯基-胺基辛基)胺与10％CH 3COOH中H +摩尔比为1：2。50℃搅拌24h至均匀，即可得到N-(顺-二十四碳-15-烯基-胺基辛基)胺醋酸盐。再将其与质量浓度10％CH 3COOH溶液混合，即可得到基于N-(顺-二十四碳-15-烯基-胺基辛基)胺醋酸盐的自转向酸。
以上所述仅是本发明的优选实施方式，应当理解本发明并非局限于本文所披露的形式，不应看作是对其他实施例的排除，而可用于各种其它组合、修改和环境，并能够在本文所述构想范围内，通过上述教导或相关领域的技术或知识进行改动。而本领域人员所进行的改动和变化不脱离本发明的精神和范围，则都应在本发明所附权利要求的保护范围内。

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  1. 一种用于高温自转向酸的黏弹性表面活性剂，其特征在于，所述黏弹性表面活性剂的结构式为：
    Figure PCTCN2019087290-appb-100001
    其中，n为具有2～8个碳原子的饱和烷烃，R1为具有18～28个碳原子的饱和或不饱和烷烃，R 2、R 3均独立为甲基、乙基、氢原子，R 2、R 3可相同或不同，X —为Cl —、Br —、F —、CO 3 2-、SO 4 2-、HCOO —、CH 3COO —中的任意一种。
  2. 根据权利要求1所述的一种用于高温自转向酸的黏弹性表面活性剂的制备方法，其特征在于，包括以下步骤：
    S1：将脂肪酸与有机胺加入反应器中，升温至160～170℃反应11～13h停止反应，待反应液冷却至25～35℃后，将其倾倒入冷的丙酮溶液，搅拌并过滤，再用丙酮洗涤过滤固体2～3次，冷冻干燥后得到白色固体中间体；其中，有机胺与脂肪酸的摩尔比为(1.1～1.5)：1；
    S2：将所得中间体溶于四氢呋喃中，在0～5℃下滴入金属氢化物的四氢呋喃溶液，中间体与金属氢化物的摩尔比为1：(2.0～2.5)，滴加完毕后升温至65～85℃反应24～36h，反应结束后向所得反应液中依次加入去离子水、质量浓度10％～20％的NaOH溶液、去离子水；第一次加入去离子水使金属氢化物淬灭，然后加所述的NaOH溶液除去金属离子，再加入去离子水保证金属氢化物完全淬灭，然后过滤，所得滤液干燥后再次过滤，将再次过滤所得滤液除去溶剂得到脂肪胺；
    S3：将脂肪胺与质量浓度10％～20％的酸液混合并搅拌均匀，使脂肪叔胺质子化，即形成超长链黏弹性表面活性剂，所述酸液的用量为脂肪胺与酸液中氢离子的摩尔比为1：2。
  3. 根据权利要求2所述的制备方法，其特征在于：所述脂肪酸为具有18～28个碳原子的饱和或不饱和烷基脂肪酸中的至少一种或多种的组合。
  4. 根据权利要求2所述的制备方法，其特征在于：所述有机胺包括N,N-二甲基乙二胺、N,N-二甲基-1,3-丙二胺、N,N-二甲基-1,4-丁二胺、N,N-二乙基乙二胺、N,N-二乙 基-1,3-丙二胺、乙二胺、丙二胺、丁二胺、戊二胺、己二胺、庚二胺、辛二胺中的一种或多种的组合。
  5. 根据权利要求2所述的制备方法，其特征在于：所述金属氢化物包括LiAlH 4、LiBH 4或NaBH 4中的一种或多种的组合。
  6. 根据权利要求2所述的制备方法，其特征在于：所述酸液包括HCl溶液、HBr溶液、HF溶液、H 2SO 4溶液、H 2CO 3溶液、HCOOH溶液、CH 3COOH溶液中的一种或多种的组合。
  7. 根据权利要求2所述的制备方法，其特征在于：所述反应过程中保持循环水冷却使有机胺回流。
  8. 根据权利要求1所述的一种用于高温自转向酸的黏弹性表面活性剂在稠化转向剂中的应用。
  9. 根据权利要求8所述的应用，其特征在于：将所述黏弹性表面活性剂与质量浓度为10％～20％的酸液混合，所述质量浓度为10％～20％的酸液包括HCl溶液、HBr溶液、HF溶液、H 2SO 4溶液、H 2CO 3溶液、HCOOH溶液、CH 3COOH溶液中的一种或多种的组合，所述10％～20％的酸液的用量为使得到的变黏酸液中黏弹性超长链表面活性剂稠化剂的质量浓度为1％～3％。
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