CN106946743A - Gemini cationic surfactant and preparation method thereof, and fracturing fluid - Google Patents

Gemini cationic surfactant and preparation method thereof, and fracturing fluid Download PDF

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CN106946743A
CN106946743A CN 201710300529 CN201710300529A CN106946743A CN 106946743 A CN106946743 A CN 106946743A CN 201710300529 CN201710300529 CN 201710300529 CN 201710300529 A CN201710300529 A CN 201710300529A CN 106946743 A CN106946743 A CN 106946743A
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formula
fracturing fluid
surfactant
compound
structure
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余瀚森
杨海洋
彭康
谢永军
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中国科学技术大学
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06Esters of carbamic acids
    • C07C271/08Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/12Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60Compositions for stimulating production by acting on the underground formation
    • C09K8/602Compositions for stimulating production by acting on the underground formation containing surfactants
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60Compositions for stimulating production by acting on the underground formation
    • C09K8/62Compositions for forming crevices or fractures
    • C09K8/66Compositions based on water or polar solvents
    • C09K8/68Compositions based on water or polar solvents containing organic compounds
    • C09K8/685Compositions based on water or polar solvents containing organic compounds containing cross-linking agents

Abstract

The invention provides a gemini cationic surfactant. The gemini cationic surfactant has a structure shown in formula I; in the formula I, R is alkyl with a carbon atom number of 10-30, n is 11-17, m is 2-6, X is O or N, and Y is halogen. Compared with the prior art, the gemini cationic surfactant innovatively combines the functions of self-degradation and automatic gas generation by means of ingenious molecular structure design. The invention provides fracturing fluid which has the excellent properties such as low inorganic salt consumption, self-degradation and automatic gas generation at the same time; after the fracturing fluid is degraded, the products are hydrophilic micromolecules and oleophylic molecules which are harmless to stratum, so that the fracturing fluid does not need to be enabled to flow back. The invention also provides a preparation method of the gemini cationic surfactant, and the fracturing fluid.

Description

一种双子阳离子表面活性剂及其制备方法和压裂液 Type gemini cationic surfactants and their preparation and fracturing fluid

技术领域 FIELD

[0001] 本发明涉及水力压裂技术领域,尤其涉及一种双子阳离子表面活性剂及其制备方法和压裂液。 [0001] The present invention relates to hydraulic fracturing, and in particular, to a cationic gemini surfactants and their preparation and fracturing fluid.

背景技术 Background technique

[0002] 目前国内应用的表面活性剂型压裂液由于存在以下问题,使其工业化应用受到了限制:一是单链的表面活性剂头部之间的静电排斥力比较大,需要加入大量的盐以屏蔽,配置压裂液所需盐量比较大;二是目前表面活性剂的碳链长度比较短,所配置的压裂液的耐温能力比较差,一般<60°C;三是为国内老油田较多,地层压力系数降低明显,压裂液返排困难,容易对储层造成二次伤害,同时返排液也容易带来严重的环境污染问题。 [0002] It surfactant-type fracturing fluid domestic applications due to the following problems, so industrial application has been limited: First, the electrostatic repulsion between the head of the single-chain surfactant is relatively large, requires a large amount of salt added to shield disposed relatively large amount of salt required for the fracturing fluid; two carbon chain length is relatively short surfactants, heat capacity of the fracturing fluid disposed relatively poor, generally <60 ° C; three for domestic old oil field more, formation pressure coefficient is reduced significantly, fracturing fluid flowback difficult, likely to cause secondary damage to the reservoir, while the flowback fluid is also likely to result in serious environmental pollution problems.

[0003] 针对以上问题,专利CN103756662公开了一种多功能不返排表面活性剂压裂液。 [0003] To solve the above problem, Patent CN103756662 discloses a multifunctionally flowback surfactant fracturing fluid. 该发明设计合成了一种六亚甲基α-和ω-双油基二甲基氯化铵组成的Gemini表面活性剂,分子中含有两个亲水、亲油基团,通过顺式双键的共价键结构将两个表面活性剂分子的离子头基连接起来,有效地阻止了离子头基之间的电荷排斥作用,只需加入少量的无机盐就可使其形成蠕虫状胶束相互缠结的网络结构,携砂性能优异,实验表明该种压裂液无需返排, 对地层的损伤也较小。 The design of the invention synthesized a hexamethylene α- and ω- bis oleyl dimethyl ammonium chloride Gemini surfactant composition, molecules containing two hydrophilic, lipophilic group, the cis double bond the covalent structure of two ionic head group of the surfactant molecule is connected, effectively prevents the head group charge between the ion repulsion, only a small amount of inorganic salt can each other so as to form wormlike micelles entangled network structure, carrying sand excellent properties, experiments show that this type of fracturing fluid without backflow, damage to the formation is small. 专利US7704926公开了一种主要成分为含酯键或酰胺键的可降解单链阳离子表面活性剂的压裂液。 Patent US7704926 discloses a main component containing an ester bond or an amide bond biodegradable single-chain cationic surfactant fracturing fluid. 该发明通过在普通单链阳离子表面活性剂分子中引入可断裂的酯键或酰胺键,使其可以在一定的PH环境和温度条件下发生降解,失去表面活性。 The invention can be broken by introducing an ester bond or an amide bond in an active single-chain molecules cationic surfactants in general, it may degrade under certain PH and ambient temperature conditions, the loss of surface activity. 从而避免了在压裂过程中表活剂分子遇到原油之后,形成乳液颗粒,对后续的驱油过程造成不利影响。 Thereby avoiding table after fracturing surfactant molecules encounter oil, emulsion particles are formed, adversely affecting the subsequent flooding process.

[0004] 另外,在油田采油技术中,采用自生气体系对油井进行解堵增能处理,可以有效地改善地层渗透性、增加地层能量、调整地层剖面以及提高压裂液返排率,达到提高采油量的目标。 [0004] Further, in the oilfield art, angry self plugging system for oil wells energization process can effectively improve formation permeability, increased formation energy, and adjust the cross-sectional stratum fracturing fluid flowback rate of increase, to improve oil production targets. 目前常见的自生气技术是把一种或两种化学成分以及多种添加剂组成的复合体系, 注入地层后,在催化剂或一定地层温度作用下使生气体系反应产生大量的CO2或碱性气体, 增加地层能量,降低油水界面张力,降低原油粘度,促进压裂液返排。 Current common technique is to anger from one or both of composition and chemical composition of the composite system various additives, injected into the formation after the anger catalyst system under the effect of temperature or a certain formation reaction or a large amount of CO2 gas alkaline, increase formation energy, reduce the interfacial tension to reduce oil viscosity, promote the fracturing fluid flowback. 专利US4178993公开了一种利用亚硝酸钠和氯化铵在一定温度下反应产生大量的氮气进行解堵增能的技术方案。 Patent US4178993 discloses a method of using sodium nitrite and ammonium chloride produce large amounts of nitrogen in the art plugging solutions energization reacted at a certain temperature. 专利CN101671553A将亚硝酸钠和发泡剂作为A剂,氯化铵、乙二胺四乙酸、酸性物质催化剂和稳泡剂作为B剂制成球状,A剂和B剂在地层条件下混合产生气体并放出热量,达到增能的目的。 Patent CN101671553A as sodium nitrite and A foaming agent, ammonium chloride, ethylenediaminetetraacetic acid, an acidic substance as a catalyst and a foam stabilizer B pelletised agent, the A agent and the B agent mixed gas is generated under formation conditions and release heat, achieve the purpose of increasing energy. 然而这些方法在施工过程中气体产生剂和酸液都不能在地面上混合,需要采用隔离液,多段塞注入,施工工艺复杂。 However, these methods and acid gas generating agent can not be mixed during construction on the ground, using the spacer fluid needed, multiple slug, the construction process is complicated.

[0005] 综合看来,现有技术并未报道同时具有无机盐用量低、自降解和自生气功能的压裂液,以满足市场的使用需求。 [0005] Taken together, the prior art also has not reported the amount of inorganic salts, low self-degradation and self fracturing fluid angry features to meet the needs of the market.

发明内容 SUMMARY

[0006] 有鉴于此,本发明的目的在于提供一种双子阳离子表面活性剂及其制备方法和压裂液,本发明提供双子阳离子表面活性剂制得的压裂液同时具有无机盐用量低、自降解和自生气功能。 [0006] In view of this, an object of the present invention is to provide a cationic gemini surfactants and their preparation and fracturing fluids, fracturing fluids of the present invention provides a cationic gemini surfactants prepared while having a low amount of inorganic salts, self-degradation and self angry functions.

[0007] 本发明提供了一种双子阳离子表面活性剂,具有式I结构: [0007] The present invention provides a cationic gemini surfactant of Formula I having the structure:

[0008] [0008]

Figure CN106946743AD00051

[0009] 式I中,R为碳源子数为10〜30的烷基,η为11〜17;m为2〜6;X为0或N;Y为卤素。 [0009] Formula I, R is the number of sub 10~30 carbon alkyl group, η is 11~17; m is 2~6; X is 0 or N; Y is a halogen.

[0010] 本发明提供了一种上述技术方案所述的双子阳离子表面活性剂的制备方法,包括以下步骤: [0010] The present invention provides a method for preparing the above technical solutions of the cationic gemini surfactants, comprising the steps of:

[0011] ⑴将式1结构化合物和双(三氯甲基)碳酸酯进行反应,得到式2结构化合物; [0011] ⑴ the structure of a compound of formula 1 and bis (trichloromethyl) carbonate reacted, to give a compound of Formula 2 structure;

[0012] (2)将式2结构化合物与式3结构化合物进行反应,得到式4结构化合物; 2 Compound 3 The structure of the compound of formula [0012] (2) reacting the formula to afford a compound of structural formula 4;

Figure CN106946743AD00052

[0013] (3)将式4结构化合物与式5结构化合物进行反应,得到式I结构的双子阳离子表面活性剂; [0013] (3) The structure of the compound of formula 4 is reacted with a compound of structural formula 5, to obtain a cationic gemini surfactant of the structure of formula I;

[0014] [0014]

[0015] 其中,式1、式2、式4和式I中的R为碳原子数为10〜30的烷基; [0015] wherein Formula 1, Formula 2, Formula 4 and Formula I is R 10~30 carbon atoms of the alkyl group;

[0016] 式3、式4和式I中的X为0或N,n为11〜17; [0016] Formula 3, Formula 4, and Formula I wherein X is 0 or N, n is 11~17;

[0017] 式5和式I中的m为2〜6,Y为卤素。 [0017] Formula 5 Formula I and m is 2~6, Y is halogen.

[0018] 优选的,所述步骤⑴中反应的温度为35〜150°C,反应的时间为0.5〜10小时。 Temperature [0018] Preferably, the reaction of step ⑴ 35~150 ° C, the reaction time is 0.5~10 hours.

[0019] 优选的,所述步骤⑵中的反应在催化剂的存在下进行。 [0019] Preferably, said step ⑵ the reaction carried out in the presence of a catalyst.

[0020] 本发明提供了一种压裂液,包括上述技术方案所述的双子阳离子表面活性剂。 [0020] The present invention provides a fracturing fluid comprising a cationic surfactant Gemini above technical solutions of the active agent.

[0021] 优选的,所述压裂液包括: [0021] Preferably, said fracturing fluid comprising:

[0022] 上述技术方案所述的双子阳离子表面活性剂; [0022] cationic gemini surfactants according to the above aspect;

[0023]交联剂; [0023] crosslinking agent;

[0024] 水。 [0024] water.

[0025] 优选的,所述交联剂选自氯化钾、氯化铵、氯化钠、溴化钾、溴化铵、溴化钠或水杨酸钠。 [0025] Preferably, the crosslinking agent is selected from potassium chloride, ammonium chloride, sodium chloride, potassium bromide, ammonium bromide, sodium bromide or sodium salicylate.

[0026] 优选的,所述双子阳离子表面活性剂在压裂液中的质量含量为0.5〜3%。 [0026] Preferably, the mass content of the cationic gemini surfactant fracturing fluid is 0.5~3%.

[0027] 优选的,所述交联剂在压裂液中的质量含量为0.5〜3%。 [0027] Preferably, the content of crosslinking agent in the fracturing fluid is 0.5~3%.

[0028] 优选的,所述压裂液还包括pH值调节剂。 [0028] Preferably, the fracturing fluid further comprises a pH adjusting agent.

[0029] 与现有技术相比,本发明通过巧妙的分子结构设计,将自降解、自生气功能创新性的结合在一起,提供了一种同时具有无机盐用量低、可自降解、自生气等性能优越的压裂液,这种压裂液降解后产物为亲水性小分子和亲油分子,对地层无损害,因而无须返排。 [0029] Compared with the prior art, the present invention is the molecular structure through clever design, self degradation, self-binding function together innovative angry, there is provided an inorganic salt having both a low dosage, self degradation, self angry superior performance of the fracturing fluid and the like, such a fracturing fluid after the degradation products of hydrophilic and lipophilic molecules of small molecules, no damage to the formation, thus without flowback. 本发明中压裂液的关键成分在于含有一种特殊结构的双子阳离子表面活性剂: In the present invention, a key component of the fracturing fluid comprising a cationic surfactant comprising a special twin structure:

[0030] 这种表面活性剂在水溶液中能够自组装形成蠕虫状胶束并进一步发生缠结形成网状结构,从而达到增黏的目的以满足压裂液携砂的需求。 [0030] Such surfactants are capable of self-assembly in aqueous solution form wormlike micelles and further entangled network structure is formed, so as to achieve a tackifier in order to meet the needs of carrying sand fracturing fluid. 表面活性剂在水溶液中自组装行为主要由其疏水尾巴和亲水头基的结构所决定,疏水尾巴越长,亲水头基之间的排斥作用越小,越有利于组装形成蠕虫状胶束,但同时溶解性变差。 Surfactant self-assembly mainly by the structure of hydrophobic tail and a hydrophilic head group in the aqueous solution is determined, the long hydrophobic tail, the smaller the repulsion between the hydrophilic head group, more facilitate assembly forming wormlike micelles , but poor solubility. 现有技术中的单链表面活性剂分子因亲水头基之间的电荷排斥作用而导致其在水溶液中更倾向于自组装形成球状胶束, 因而需要加入大量的无机盐以屏蔽亲水头基的电荷,促使其自组装形貌由球状胶束转变为蠕虫状胶束。 Single-chain surfactant molecule by the prior art between the hydrophilic head group charge repulsion resulting in an aqueous solution which prefer self-assembled spherical micelles are formed, thus requiring a large amount of an inorganic salt is added to shield the hydrophilic head base charge, which causes self-assembled spherical micelles of the morphology changed from wormlike micelles. 而具有更长疏水碳链的表面活性剂分子因原料不易得到而成本高昂,且溶解性很差难以实际应用。 The surfactant molecules having a hydrophobic carbon chain longer difficult to obtain because the raw material is expensive and difficult to practice poor solubility. 本发明采用的双子阳离子表面活性剂,在亲水头基之间加入了化学键,同时由于采用了氨基甲酸酯键结构,亲水头基之间可以形成氢键,在化学和物理的共同作用下减少了亲水头基之间的排斥作用,因而可以大大减少无机盐的用量,且进一步提高其增黏效果。 Gemini cationic surfactants employed in the present invention, the hydrophilic head group is added between the bond, urethane bond because the use of the structure, can form hydrogen bonds between the hydrophilic head group, the combined effect of the chemical and physical under reducing the repulsion between the hydrophilic head group, and thus it can greatly reduce the amount of inorganic salt, and further improve the viscosity-increasing effect.

[0031] 现有技术中阳离子表面活性剂压裂液还容易在岩石表面吸附,使原本呈亲水性的岩石表面变得疏水而造成储层损害和破胶不彻底,同时若压裂结束后还继续留存在储层中,在后续采油过程中会和原油一同被采出而造成原油乳化问题,因而必须返排。 [0031] The prior art Cationic surfactants rock fracturing fluid is also easily adsorbed on the surface, so that the original hydrophilic rock surface was made hydrophobic and formation damage caused by incomplete breaking, while the rear end if fracturing also continue to exist in the reservoir, the subsequent oil recovery process will be taken out and oil together caused crude oil emulsion problems, and must flowback. 本发明中的表面活性剂分子在合适的pH和温度的作用下连接疏水链和亲水头基的氨基甲酸酯键可以断裂,使得表活剂分子降解成带电荷的极性小分子和非极性的疏水碳链。 Surfactant molecules of the present invention is connected to a hydrophobic chain and a hydrophilic head group under the action of a suitable pH and temperature of the urethane bond may be broken, so that the surface active agent molecules degrade to uncharged polar and non-small molecule polar hydrophobic carbon chain. 而且在断裂过程中可产生气体,达到增能的目的,极性小分子产物可以吸附在岩石表面,在不改变岩石润湿性的同时充当黏土稳定剂,疏水碳链可以直接溶解到原油中被一同采出而不造成原油乳化,因而既不会损害地层也不会干扰后续采油过程,同时破胶也更加完全,不需返排。 Also during fracturing may generate gas, to achieve the object of increasing energy, small polar molecules adsorbed on the rock surface of the product may, without changing the wettability of rock clay also acts as a stabilizer, a hydrophobic carbon chain may be dissolved directly to the crude oil together without causing recovery of crude oil emulsion, and thus neither damage nor interfere with the subsequent formation oil recovery process, while also breaking more fully, without flowback.

[0032] 因此,本发明提供的双子阳离子表面活性剂制备得到的压裂液同时具有无机盐用量少,可自降解和自生气的功能,携砂效果好,无需返排。 [0032] Accordingly, the present invention provides a fracturing fluid Gemini cationic surface-active agent having both inorganic salts obtained with less, degradation and self-self-angry function, carrying sand effect, without flowback.

附图说明 BRIEF DESCRIPTION

[0033] 为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据提供的附图获得其他的附图。 [0033] In order to more clearly illustrate the technical solutions in the embodiments or the prior art embodiment of the present invention, briefly introduced hereinafter, embodiments are described below in the accompanying drawings or described in the prior art needed to be used in describing the embodiments the drawings are only examples of the present invention, those of ordinary skill in the art is concerned, without creative efforts, can derive other drawings from the accompanying drawings provided.

[0034] 图1为本发明提供的双子阳离子表面活性剂的结构示意图; [0034] FIG. 1 is a schematic cationic gemini surfactants of the present invention to provide a structure;

[0035] 图2为表1中样品1在不同温度下黏度随时间的变化; [0035] FIG. 2 is a sample 1 in Table 1 Change in viscosity at different temperatures over time;

[0036] 图3为表2中样品1在不同温度下黏度随时间的变化; [0036] FIG. 3 is a Table 2 sample 1 changes at different temperature viscosity over time;

[0037] 图4为表3中样品1在不同温度下黏度随时间的变化; [0037] FIG. 4 is a Table 3 Change in viscosity samples at different temperatures over time;

[0038] 图5为实施例7得到的压裂液在90°C不同pH条件下降解不同时间后在25°C测试的黏度变化; [0038] FIG. 5 is a fracturing fluid obtained in Example 7 Viscosity change of 90 ° C in the different pH conditions degrade at different times in the 25 ° C test;

[0039] 图6为实施例8得到的压裂液在90°C不同pH条件下降解不同时间后在25°C测试的黏度变化; [0039] FIG. 6 is a variation in the viscosity of the 25 ° C test fracturing fluid obtained in Example 8 at 90 ° C after the pH conditions different embodiments degrade at different times;

[0040] 图7为实施例9得到的压裂液在90°C不同pH条件下降解不同时间后在25°C测试的黏度变化。 [0040] FIG. 7 is a viscosity at 25 ° C change in the test fracturing fluid obtained in Example 9 after 90 ° C at different pH conditions degrade at different times embodiments.

具体实施方式 detailed description

[0041] 下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,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。 [0041] below in conjunction with the present invention in the accompanying drawings, technical solutions of embodiments of the present invention are clearly and completely described, obviously, the described embodiments are merely part of embodiments of the present invention, but not all embodiments example. 基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。 Based on the embodiments of the present invention, all other embodiments of ordinary skill in the art without any creative effort shall fall within the scope of the present invention.

[0042] 本发明提供了一种双子阳离子表面活性剂,具有式I结构: [0042] The present invention provides a cationic gemini surfactant of Formula I having the structure:

[0043] [0043]

Figure CN106946743AD00071

[0044] 式I中,R为碳原子数为10〜30的烷基,优选为碳原子数为14〜18的直链烷基,更优选为-Cl6H33或-Cl8H37 ; [0044] Formula I, R 10~30 carbon atoms of the alkyl group is preferably a straight-chain carbon atoms of the alkyl group 14~18, more preferably -Cl6H33 or -Cl8H37;

[0045] η为11〜17,优选为12〜16,更优选为13〜15; [0045] η of 11~17, preferably 12~16, more preferably 13~15;

[0046] m为2〜6,优选为2〜4; [0046] m is 2 ~ 6, preferably 2 ~ 4;

[0047] X 为0或N; [0047] X is 0 or N;

[0048] Y为卤素,优选为Cl或Br。 [0048] Y is halogen, preferably Cl or Br.

[0049] 图1为本发明提供的双子阳离子表面活性剂的结构示意图,包括与离子连接的降解基团,尚子之间的间隔基团。 [0049] FIG 1 the present invention provides a twin cationic surfactant is a schematic structural diagram, including the degradation of the ion groups attached, a spacer group between Naoko.

[0050] 本发明提供了一种上述技术方案所述的双子阳离子表面活性剂的制备方法,包括以下步骤: [0050] The present invention provides a method for preparing the above technical solutions of the cationic gemini surfactants, comprising the steps of:

[0051] (1)将式1结构化合物和双(三氯甲基)碳酸酯进行反应,得到式2结构化合物; [0051] (1) The structure of the compound of formula 1 and bis (trichloromethyl) carbonate reacted, to give a compound of Formula 2 structure;

[0052] (2)将式2结构化合物与式3结构化合物进行反应,得到式4结构化合物; 2 Compound 3 The structure of the compound of formula [0052] (2) reacting the formula to afford a compound of structural formula 4;

[0053] (3)将式4结构化合物与式5结构化合物进行反应,得到式I结构的双子阳离子表面活性剂; [0053] (3) The structure of the compound of formula 4 is reacted with a compound of structural formula 5, to obtain a cationic gemini surfactant of the structure of formula I;

[0054] [0054]

Figure CN106946743AD00081

[0055] 其中,式1、式2、式4和式I中的R为碳原子数为10〜30的烷基; [0055] wherein Formula 1, Formula 2, Formula 4 and Formula I is R 10~30 carbon atoms of the alkyl group;

[0056] 式3、式4和式I中的X为0或Ν,η为11〜17; [0056] Formula 3, Formula 4, and Formula I wherein X is 0 or Ν, η is 11~17;

[0057] 式5和式I中的m为2〜6, Y为卤素。 [0057] Formula 5 Formula I and m is 2~6, Y is halogen.

[0058] 在本发明中,式1、式2、式4和式I中的R与上述技术方案所述R—致;式3、式4和式I 中的X和η与上述技术方案所述X和η—致;式5和式I中的m和Y与上述技术方案所述!!!和丫一致;在此不再赘述。 [0058] In the present invention, Formula 1, Formula 2, Formula 4 and Formula I is R and the foregoing technical solution R- actuator; Formula 3, Formula 4, and Formula I and X in the above technical solution η X and η- said actuator; formula 5 and formula I where m and Y are the above technical solutions and Ah! consistent; not repeated here.

[0059] 在本发明中,所述步骤⑴中优选将式1结构的化合物溶液滴加到双(三氯甲基)碳酸酯(BTC)溶液中,所述滴加温度优选为0〜5°C。 [0059] In the present invention, the step is preferably ⑴ the structure of Formula 1 compound solution was added dropwise to bis (trichloromethyl) carbonate (BTC) solution, the temperature is preferably 0~5 ° was added dropwise C. 在本发明中,所述式1结构化合物溶液和双(三氯甲基)碳酸酯(BTC)溶液中的溶剂优选为同种溶剂,优选为甲苯、二甲苯或氯苯。 In the present invention, the structure of the compound of Formula 1 and a solution of bis (trichloromethyl) carbonate (BTC) solvent in the solution is preferably the same solvent, preferably toluene, xylene or chlorobenzene. 在本发明中,所述步骤⑴中的反应优选在搅拌的条件下进行。 Said step ⑴ the reaction is preferably carried out under stirring in the present invention. 在本发明中,所述步骤⑴中反应的温度优选为35〜150°C,更优选为50〜120°C,最优选为80〜100°C。 In the present invention, the temperature in step ⑴ reaction is preferably 35~150 ° C, more preferably 50~120 ° C, and most preferably 80~100 ° C. 在本发明中,所述步骤(1)中反应的时间优选为0.5〜10小时,更优选为1〜8小时,最优选为3〜6小时。 In the present invention, the time (1) the reaction step is preferably 0.5~10 hours, more preferably 1~8 hours, most preferably 3 ~ 6 hours.

[0060] 在本发明中,所述反应完成后,优选将得到的反应产物通氮气以除去氯化氢气体后回收有机溶剂,得到式2结构化合物。 The reaction product [0060] In the present invention, after the completion of the reaction, preferably the nitrogen obtained after removal of the organic solvent to recover the hydrogen chloride gas, to give a compound of Formula 2 structure. 在本发明中,回收有机溶剂的方法优选为蒸馏。 In the present invention, the process for recovering the organic solvent is preferably distilled off.

[0061] 在本发明中,所述步骤(2)中的反应温度优选为20〜30°C;反应时间优选为6〜18 小时,更优选为10〜14小时。 [0061] In the present invention, the step (2) the reaction temperature is preferably 20~30 ° C; the reaction time is preferably 6~18 hours, more preferably 10~14 hours. 在本发明中,所述步骤(2)中的反应优选在催化剂的存在下进行,所述催化剂优选为二丁基锡二月桂酸酯。 Said step (2) the reaction is preferably carried out in the presence of a catalyst in the present invention, the catalyst is dibutyl tin dilaurate is preferred. 在本发明中,所述步骤(2)中的反应优选在高温下进行,所述高温的温度优选为35〜45°C。 Said step (2) is preferably carried out at an elevated temperature in the present invention, the temperature is preferably elevated temperature 35~45 ° C. 本发明步骤(2)中的反应在催化剂和高温条件下进行能够加快反应速度。 Invention, the reaction step (2) in the present and the catalyst is carried out at high temperature to accelerate the reaction rate.

[0062] 在本发明中,所述步骤⑶中反应的温度优选为50〜100°C,更优选为60〜80°C;反应的时间优选为48〜72小时。 [0062] In the present invention, the temperature in step ⑶ reaction is preferably 50~100 ° C, more preferably 60~80 ° C; the reaction time is preferably 48~72 hours. 在本发明中,所述步骤(3)中的反应优选在搅拌的条件下进行。 Said step (3) is preferably carried out under stirring in the present invention. 在本发明中,所述步骤(3)反应完成后优选将得到的反应产物蒸馏除去其中的有机溶剂,得到式I结构的化合物。 In the present invention, the reaction product of the step (3) After completion of the reaction is preferably obtained wherein organic solvent was distilled off, to give a compound of Formula I structure.

[0063] 在本发明中,所述式1结构化合物和双(三氯甲基)碳酸酯的摩尔比优选为1: (0.3 〜0.4),更优选为1:0.35;式2结构化合物和式3结构化合物的摩尔比优选为I: (0.8〜1.2), 更优选为1:1;式4结构化合物和式5结构化合物的摩尔比优选为1: (0.3〜0.7),更优选为1: 0.5。 [0063] In the present invention, the structure of the compound of Formula 1 and bis (trichloromethyl) carbonate molar ratio is preferably 1: (0.3 ~ 0.4), more preferably from 1: 0.35; structure of the compound of Formula 2 and Formula the molar ratio of the structure 3 compound is preferably I: (0.8~1.2), more preferably 1: 1; molar ratio of the compound structure of formula 4 and the structure of the compound of formula 5 is 1: (0.3~0.7), more preferably 1: 0.5. 本发明对所述式1结构化合物、双(三氯甲基)碳酸酯、式3结构化合物和式5结构化合物的来源没有特殊的限制,可采用本领域技术人员熟知的方法合成,也可由市场购买获得。 The present invention of structural formula 1 compound, bis (trichloromethyl) source compounds and structures of the compounds of formula 5 3 a carbonate structure of formula is not particularly limited, and well known to those skilled in the synthesis method, the market may also be buy access.

[0064] 本发明提供了一种压裂液,包括上述技术方案所述的双子阳离子表面活性剂。 [0064] The present invention provides a fracturing fluid comprising a cationic surfactant Gemini above technical solutions of the active agent. 在本发明中,所述压裂液优选包括双子阳离子表面活性剂;交联剂;水。 In the present invention, the fracturing fluid preferably comprises a cationic gemini surfactant; crosslinker; water. 在本发明中,所述双子阳离子表面活性剂为上述技术方案所述的双子阳离子表面活性剂,在此不再赘述。 In the present invention, the cationic gemini surfactant according to the above aspect Gemini cationic surfactants, are not repeated here. 在本发明中,所述双子阳离子表面活性剂在压裂液中的质量含量优选为0.5〜3%,更优选为1〜 2.5 %,最优选为1.5〜2 %。 In the present invention, the mass content of the cationic gemini surfactant fracturing fluid is preferably 0.5~3%, and more preferably 1 ~ 2.5%, and most preferably 1.5~2%. 在本发明中,所述交联剂优选选自氯化钾、氯化铵、氯化钠、溴化钾、溴化铵、溴化钠或水杨酸钠,更优选为氯化铵。 In the present invention, preferably the crosslinking agent is selected from potassium chloride, ammonium chloride, sodium chloride, potassium bromide, ammonium bromide, sodium bromide or sodium salicylate, more preferably chloride. 在本发明中,所述交联剂在压裂液中的质量含量优选为0.5〜3%,更优选为1〜2.5%,最优选为1.5〜2%。 In the present invention, the crosslinking agent in the fracturing fluid content is preferably 0.5~3% by mass, and more preferably 1~2.5%, and most preferably 1.5~2%. 在本发明中,所述水优选为去离子水。 In the present invention, preferably the water is deionized water. 本发明提供的压裂液中优选还包括pH值调节剂,可根据压裂液所应用的储层本身条件(储层本身的pH值、温度等)选择添加pH值调节剂。 Fracturing fluids of the present invention preferably further comprises providing a pH adjusting agent, the condition itself (own reservoir pH, temperature, etc.) to add a pH adjusting agent selected according to the applied fracturing fluid reservoir. 在本发明中,所述pH值调节剂使压裂液的pH值在6.8〜8.5的范围内。 In the present invention, the pH adjusting agent, the pH of the fracturing fluid in the range of 6.8~8.5. 本发明可通过调节压裂液的pH值调节其降解速度。 The present invention can be adjusted by a pH adjusting degradation rate of the fracturing fluid. 在本发明中,所述pH值调节剂优选为碱性化合物,如氢氧化钠、氢氧化钾、三乙胺或碳酸氢钠, 考虑到二氧化碳的溶解平衡优选为碳酸氢钠。 In the present invention, the pH adjusting agent is preferably a basic compound, such as sodium hydroxide, potassium hydroxide, triethylamine or sodium bicarbonate, considering the balance of dissolved carbon dioxide is preferably sodium bicarbonate. 在本发明中,所述压裂液的PH值优选为6.5〜 8.5〇 In the present invention, PH value of the fracturing fluid is preferably 6.5~ 8.5〇

[0065] 本发明对所述压裂液的制备方法没有特殊的限制,采用本领域技术人员熟知的压裂液的制备方法进行制备即可,如可按照下述方法进行制备: [0065] The present invention is not particularly limited to the production method of the fracturing fluid, prepared using methods well known to those skilled in the fracturing fluid can be prepared, as can be prepared by the following method:

[0066] 将双子阳离子表面活性剂、交联剂和水搅拌溶解,得到压裂液。 [0066] The cationic gemini surfactant, a crosslinking agent, and stirred and dissolved water, to give the fracturing fluid. 在必要时添加pH值调节剂。 A pH adjusting agent if necessary.

[0067] 本发明提供的压裂液可以用作水井和油井压裂,所需无机盐用量少,增黏效果好; 且在地层温度下可发生自降解,不改变地层润湿性,对地层无伤害,无需返排;同时伴随降解过程可释放二氧化碳气体补充地层能量。 [0067] The present invention provides a fracturing fluid may be used as well and fracturing, with the required inorganic salts less, good viscosifying effect; and may occur from the degradation at the formation temperature, without changing the wettability of the formation of no formation damage, without flowback; concomitant degradation process can release carbon dioxide gas replenishment formation energy.

[0068] 本发明以下实施例所用到的原料和设备均为市售商品,使用上海安耐吉试剂有限公司生产的十八烷基胺、N,N-二甲基乙醇胺;国药集团化学试剂有限公司生产的双(三氯甲基)碳酸酯、1,2-二溴乙烷、氯化铵、二丁基锡二月桂酸酯、丙酮、二氯甲烷。 [0068] Examples of the materials and equipment used are the following commercially available embodiment of the present invention, using octadecylamine Shanghai Co., Ltd. An agent of Nike, N, N- dimethylethanolamine; Sinopharm Chemical Reagent Co. produced bis (trichloromethyl) carbonate, 1,2-dibromoethane, ammonium chloride, dibutyl tin dilaurate, acetone, methylene chloride.

[0069] 采用北京欣维尔玻璃仪器有限公司生产的四口烧瓶、两口烧瓶和单口烧瓶,采用德国IKA公司生产的EUR0STAR型磁力加热搅拌器进行加热及搅拌,采用美国生产的TAAR-G2 型多功能流变仪对压裂液的黏度以及可降解性能进行测试。 [0069] A four-neck flask Hinwil Beijing Glass Instrument Co., Ltd., two one-necked flask and the flask using a heating magnetic stirrer EUR0STAR type IKA, Germany produced by heating and stirring, using multifunctional U.S. TAAR-G2 produced rheometer viscosity fracturing fluid and degradable properties were tested.

[0070] 实施例1C18-氨基甲酸酯键-二甲基乙胺(表面活性剂1)合成 Synthesis of dimethyl amine (surfactant 1) - [0070] Example 1C18- urethane bond

[0071] C18-氨基甲酸酯键-二甲基乙胺合成的合成路线如下: [0071] C18- urethane bond - dimethylethylamine synthetic scheme is as follows:

[0072] [0072]

Figure CN106946743AD00101

[0073] 在装有机械搅拌器、温度计、恒压滴液漏斗、回流冷凝管的四口烧瓶中加入双(三氯甲基)碳酸酯29.7g (0. Imol)和二氯甲烷(70mL),开启搅拌,冷却至0〜5°C。 [0073] equipped with a mechanical stirrer, a thermometer, constant pressure dropping funnel, a four-neck flask with a reflux condenser was added bis (trichloromethyl) carbonate 29.7g (0. Imol) and dichloromethane (70 mL) , open stirred and cooled to 0~5 ° C. 将十八胺(合成路线中⑴化合物)80.7g (0.3mo 1的二氯甲烷(90mL)溶液经恒压滴液漏斗以1.5mL/min左右的速度滴入反应体系中,滴加完毕后,在室温下搅拌〇. 5h后再升温至50°C回流反应5h。反应结束,通氮气除去氯化氢气体,真空蒸馏回收二氯甲烷后蒸出产品十八烷基异氰酸酯(合成路线中⑵化合物69.4g,产率78.2%)。 The octadecylamine (Compound ⑴ synthetic route) 80.7g (0.3mo 1 in dichloromethane (90 mL) solution was pressure-equalizing dropping funnel at a rate of approximately 1.5mL / min added dropwise to the reaction system, after completion of the dropwise addition, square was stirred at rt. 5h then warmed to 50 ° C the reaction was refluxed for 5h. completion of the reaction, a nitrogen gas to remove hydrogen chloride, the methylene chloride was distilled off in vacuo the product was recovered by distillation octadecyl isocyanate (69.4g synthetic route ⑵ compound , 78.2% yield).

[0074] 在单口烧瓶中加入十八烷基异氰酸酯29.5g(0.1mol),N,N-二甲基乙醇胺8.9g (0. Imol),二丁基锡二月桂酸酯ImL,二氯甲烷IOOmL,开启磁力搅拌,室温反应8h。 [0074] octadecyl isocyanate was added in a single neck flask the ester 29.5g (0.1mol), N, N- dimethylethanolamine 8.9g (0. Imol), dibutyl tin dilaurate ImL, dichloromethane IOOmL, open magnetic stirring, at room temperature the reaction 8h. 反应结束后,反应液用IOOmL水洗,分离出有机相,无水硫酸钠干燥后真空除去二氯甲烷得产物十八烷氨基甲酸二甲氨基乙醇酯(合成路线中⑶化合物)(36.2g,产率94.3%)。 After completion of the reaction, the reaction solution was IOOmL water, the organic phase was separated, dried over anhydrous sodium sulfate and the methylene chloride was removed to give the product octadecyl amino acid esters of dimethylaminoethanol (synthetic route ⑶ compound) in vacuo (36.2 g, yield rate of 94.3%).

[0075] 在装有回流冷凝管的两口烧瓶中加入十八氨基甲酸二甲氨基乙醇酯(38.4g, 0 · Imo 1),1,2-二溴乙烷(I 1 · 3g,0 · 06mo 1),丙酮80mL,开启磁力搅拌,并升温回流反应36h, 过滤,得固体白色粉末状双阳离子表面活性剂产物(合成路线中(4)化合物)(38.2g,产率80%) 〇 [0075] Add eighteen amino acid esters of dimethylaminoethanol in two flask equipped with a reflux condenser (38.4g, 0 · Imo 1), 1,2- dibromoethane (I 1 · 3g, 0 · 06mo 1), 80 mL of acetone, magnetically stirred open, and the reaction heated at reflux for 36h, filtered to obtain a solid white powdery product was the cationic surfactant bis ((4 synthesis scheme) compound) (38.2 g, 80% yield) square

Figure CN106946743AD00102

[0076] 对本发明实施例1制备得到的双阳离子表面活性剂产物进行核磁氢谱检测,检测结果为1H-匪R (500MHz,Chloroform-d)S5.34 (s,lH) ,4.52 (s,2H) ,3.68 (s,2H) ,3.52 (s, 2H),3.14(d,8H) ,1.61 (s,2H) ,1.26 (m,31H) ,0.89 (s,3H),双阳离子表面活性剂具有以下结构: [0076] 1H NMR, for detecting surfactant product prepared in Example 1 was dicationic embodiment of the present invention, the detection result is 1H- bandit R (500MHz, Chloroform-d) S5.34 (s, lH), 4.52 (s, 2H), 3.68 (s, 2H), 3.52 (s, 2H), 3.14 (d, 8H), 1.61 (s, 2H), 1.26 (m, 31H), 0.89 (s, 3H), bis cationic surfactant It has the following structure:

[0077] [0077]

[0078] 实施例2C16-氨基甲酸酯键-二甲基乙胺(表面活性剂2)合成 Dimethylethylamine (surfactant 2) Synthesis - Example 2C16- urethane bond [0078] Embodiment

[0079] 合成路线与实施例1类似,将合成路线中的化合物(1)十八胺替换为十六胺,具体合成方式为: [0079] Scheme Analogously to Example 1, in the synthetic route to compound (1) is replaced octadecylamine hexadecylamine, particularly synthetic way:

[0080] 在装有机械搅拌器、温度计、恒压滴液漏斗、回流冷凝管的四口烧瓶中加入双(三氯甲基)碳酸酯29.7g(0.1mol)和二氯甲烷(70mL),开启搅拌,冷却至0〜5°C。 [0080] equipped with a mechanical stirrer, a thermometer, constant pressure dropping funnel, a four-neck flask with a reflux condenser was added bis (trichloromethyl) carbonate 29.7g (0.1mol) and dichloromethane (70 mL), open stirred and cooled to 0~5 ° C. 将十六胺72.5g (0.3mol)的二氯甲烷(90mL)溶液经恒压滴液漏斗以1.5mL/min左右的速度滴入反应体系中,滴加完毕后,在室温下搅拌0.5h后再升温至50°C回流反应5h。 After hexadecylamine 72.5g (0.3mol) in dichloromethane (90 mL) solution was pressure-equalizing dropping funnel at a rate of approximately 1.5mL / min added dropwise to the reaction system after the addition was complete the mixture was stirred at room temperature for 0.5h then warmed to 50 ° C the reaction was refluxed for 5h. 反应结束,通氮气除去氯化氢气体,真空蒸馏回收二氯甲烷后蒸出产品十六烷基异氰酸酯(65g,产率81%)。 End of the reaction, a nitrogen gas to remove hydrogen chloride, the methylene chloride was distilled off in vacuo The product was recovered by distillation hexadecyl isocyanate (65 g of, 81% yield).

[0081] 在单口烧瓶中加入十六烷基异氰酸酯26.7g(0.1mol),N,N-二甲基乙醇胺8.9g (0. Imol),二丁基锡二月桂酸酯ImL,二氯甲烷IOOmL,开启磁力搅拌,室温反应8h。 [0081] hexadecyl isocyanate was added 26.7g (0.1mol) in a single neck flask, N, N- dimethylethanolamine 8.9g (0. Imol), dibutyl tin dilaurate ImL, dichloromethane IOOmL, open magnetic stirring, at room temperature the reaction 8h. 反应结束后,反应液用IOOmL水洗,分离出有机相,无水硫酸钠干燥后真空除去二氯甲烷得产物十六烷氨基甲酸二甲氨基乙醇酯(34.8g,产率97.6%)。 After completion of the reaction, the reaction solution was IOOmL water, the organic phase was separated, dried over anhydrous sodium sulfate to give the product amino acid hexadecyl ester dimethylaminoethanol (34.8 g of, 97.6% yield) after drying in vacuo to remove methylene chloride.

[0082] 在装有回流冷凝管的两口烧瓶中加入十六烷氨基甲酸二甲氨基乙醇酯(35.7g, 0 · Imo 1),1,2-二溴乙烷(I 1 · 3g,0 · 06mo 1),丙酮80mL,开启磁力搅拌,并升温回流反应36h, 过滤,得固体白色粉末状双阳离子表面活性剂产物(36.5g,产率81 %)。 [0082] hexadecane was added carbamic acid ester in two dimethylaminoethanol flask equipped with a reflux condenser (35.7g, 0 · Imo 1), 1,2- dibromoethane (I 1 · 3g, 0 · 06mo 1), 80 mL of acetone, magnetically stirred open, and the reaction heated at reflux for 36h, filtered to obtain a white powdery solid dicationic surfactant product (36.5 g of, 81% yield).

[0083] 按照实施例1中的方法进行检测,检测结果为,本发明实施例2制备得到的双阳离子表面活性剂具有以下结构: [0083] The detection method according to Example 1, the result of the detection, dicationic surfactant obtained in Production Example 2 embodiment of the present invention has the following structure:

[0084] [0084]

Figure CN106946743AD00111

[0085] 实施例3C18-氨基甲酸酯键-二甲基羟基丙胺(表面活性剂3)合成 [0085] Example 3C18- urethane bond - dimethyl hydroxyl amine (Surfactant 3) Synthesis of

[0086] 合成路线与实施例1类似,将实施例1中的1,2_二溴乙烷替换为环氧氯丙烷,具体合成方式为: [0086] Scheme Analogously to Example 1, in Example 1 is replaced with epichlorohydrin 1,2_-dibromoethane, particularly synthetic way:

[0087] 在装有机械搅拌器、温度计、恒压滴液漏斗、回流冷凝管的四口烧瓶中加入双(三氯甲基)碳酸酯29.7g(0.1mol)和二氯甲烷(70mL),开启搅拌,冷却至0〜5°C。 [0087] equipped with a mechanical stirrer, a thermometer, constant pressure dropping funnel, a four-neck flask with a reflux condenser was added bis (trichloromethyl) carbonate 29.7g (0.1mol) and dichloromethane (70 mL), open stirred and cooled to 0~5 ° C. 将十八胺80.7g (0.3mol)的二氯甲烷(90mL)溶液经恒压滴液漏斗以1.5mL/min左右的速度滴入反应体系中,滴加完毕后,在室温下搅拌0.5h后再升温至50°C回流反应5h。 After octadecylamine 80.7g (0.3mol) in dichloromethane (90 mL) solution was pressure-equalizing dropping funnel at a rate of approximately 1.5mL / min added dropwise to the reaction system after the addition was complete the mixture was stirred at room temperature for 0.5h then warmed to 50 ° C the reaction was refluxed for 5h. 反应结束,通氮气除去氯化氢气体,真空蒸馏回收二氯甲烷后蒸出产品十八烷基异氰酸酯(69.4g,产率78.2%) 〇 End of the reaction, a nitrogen gas to remove hydrogen chloride, the methylene chloride was distilled off in vacuo The product was recovered by distillation octadecyl isocyanate (69.4 g, yield 78.2%) square

[0088] 在单口烧瓶中加入十八烷基异氰酸酯29.5g(0.1mol),N,N-二甲基乙醇胺8.9g (0. Imol),二丁基锡二月桂酸酯ImL,二氯甲烷IOOmL,开启磁力搅拌,室温反应8h。 [0088] octadecyl isocyanate was added in a single neck flask the ester 29.5g (0.1mol), N, N- dimethylethanolamine 8.9g (0. Imol), dibutyl tin dilaurate ImL, dichloromethane IOOmL, open magnetic stirring, at room temperature the reaction 8h. 反应结束后,反应液用IOOmL水洗,分离出有机相,无水硫酸钠干燥后真空除去二氯甲烷得产物十八烷氨基甲酸二甲氨基乙醇酯(36.2g,产率94.3%)。 After completion of the reaction, the reaction solution was IOOmL water, the organic phase was separated, dried over anhydrous sodium sulfate and methylene chloride was removed in vacuo to give the product octadecyl amino acid esters of dimethylaminoethanol (36.2 g, yield 94.3%).

[0089] 在装有回流冷凝管的两口烧瓶中加入十八氨基甲酸二甲氨基乙醇酯(38.4g, O.lmol),环氧氯丙烧(5.6g,0.06mol),丙酮80mL,开启磁力搅拌,并升温回流反应36h,过滤,得固体白色粉末状双阳离子表面活性剂产物(36.2g,产率78%)。 [0089] Add eighteen amino acid esters of dimethylaminoethanol in two flask equipped with a reflux condenser (38.4g, O.lmol), epichlorohydrin burning (5.6g, 0.06mol), acetone 80mL, open magnetic stirred and heated to reflux 36h, filtered to obtain a white powdery solid dicationic surfactant product (36.2 g, 78% yield).

[0090] 按照实施例1所述的方法进行检测,检测结果为,本发明实施例3制备的双阳离子表面活性剂具有以下结构: [0090] carried out as described in Example 1 is detected, the detection result is, dual cationic surfactant Preparation Example 3 of the present invention has the following structure:

[0091] [0091]

Figure CN106946743AD00121

[0092] 实施例4 [0092] Example 4

[0093] 将实施例1制备得到的双阳离子表面活性剂溶解于去离子水中,完全溶解后加入氯化铵和水杨酸钠,制备得到压裂液。 [0093] The Example 1 was prepared dicationic surfactant is dissolved in deionized water, was added after complete dissolution of ammonium chloride and sodium salicylate, prepared by the fracturing fluid.

[0094] 表面活性剂、氯化铵和水杨酸钠的质量含量以及得到的压裂液状态如表1所示。 [0094] surfactant, and the mass content of ammonium chloride and sodium salicylate fracturing fluid state obtained are shown in Table 1. 表1为本发明实施例4得到的压裂液的状态。 Table 1 state of the fracturing fluid obtained in Example 4 of the embodiment of the present invention.

[0095] 表1本发明实施例4得到的压裂液的状态 Fracturing fluid state obtained in Example 4 [0095] Table 1 Invention

[0096] [0096]

Figure CN106946743AD00122

[0097] 图2为表1中样品1在不同温度下黏度随时间的变化,在固定剪切频率下,随着温度升高,压裂液黏度下降,但在短时间内(Ih)保持稳定,而且即便在高温条件下(II(TC),粘度也可达28mPa · s,符合油气田要求。 [0097] FIG. 2 is a sample 1 in Table 1 the viscosity change with time at a fixed shear frequency, as the temperature increases, the viscosity of the fracturing fluid at different temperatures decrease, but remained steady in a short time (Ih is) , and even under high temperature conditions (II (TC), viscosity up to 28mPa · s, meet the requirements of oil and gas fields.

[0098] 由表2和图2可知,加入水杨酸钠可以有效提高表面活性剂溶液的克拉夫点,使其耐温性变好,但会降低其溶解度,因而更适用于高温储层。 [0098] As apparent from Table 2 and Figure 2, sodium salicylate can effectively improve the Krafft point of the surfactant solution, it becomes a good temperature resistance, but its solubility decreases, and thus more suitable for high temperature reservoirs.

[0099] 实施例5 [0099] Example 5

[0100] 与实施例4制备压裂液的方法相同,将实施例1制备的双阳离子表面活性剂替换为实施例2制备的双阳离子表面活性剂。 [0100] A method same as in Example 4 was prepared in the fracturing fluid, dicationic surfactant prepared in Example 1 was replaced with bis cationic surfactant is prepared in the Example 2 embodiment.

[0101] 表面活性剂、氯化铵和水杨酸钠的质量含量以及得到的压裂液状态如表2所示。 [0101] surfactant, and the mass content of ammonium chloride and sodium salicylate fracturing fluid state obtained are shown in Table 2. 表2为本发明实施例5得到的压裂液的状态。 Table 2 fracturing fluid state obtained in Example 5 of the embodiment of the present invention.

[0102] 表2本发明实施例5得到的压裂液的状态 [0102] Table fracturing fluid state obtained in Example 5 of the Embodiment 2 of the present invention

[0103] [0103]

Figure CN106946743AD00123

[0104] [0104]

Figure CN106946743AD00131

[0105] 图3为表2中样品1在不同温度下黏度随时间的变化,在固定剪切频率下,随着温度升高,压裂液黏度下降,但在短时间内(Ih)保持稳定,而且即便在高温条件下(II(TC),黏度也可达31mPa · s,符合油气田要求。 [0105] FIG. 3 is a Table 2 Sample 1 viscosity change with time at a fixed shear frequency, as the temperature increases, the viscosity of the fracturing fluid at different temperatures decrease, but remained steady in a short time (Ih is) and even under high temperature conditions (II (TC), the viscosity is also up 31mPa · s, meet the requirements of oil and gas fields.

[0106] 由表2和图3可知,加入水杨酸钠可以有效提高表面活性剂溶液的克拉夫点,使其耐温性变好,但会降低其溶解度,因而更适用于高温储层。 [0106] As apparent from Table 2 and FIG 3, and sodium salicylate can effectively improve the Krafft point of the surfactant solution, it becomes a good temperature resistance, but its solubility decreases, and thus more suitable for high temperature reservoirs.

[0107] 实施例6 [0107] Example 6

[0108] 与实施例4制备压裂液的方法相同,将实施例1制备的双阳离子表面活性剂替换为实施例3制备的双阳离子表面活性剂。 [0108] A method same as in Example 4 was prepared in the fracturing fluid, dicationic surfactant prepared in Example 1 was replaced with bis cationic surfactant is prepared in Example 3 embodiment.

[0109] 表面活性剂、氯化铵和水杨酸钠的质量含量以及得到的压裂液状态如表3所示。 [0109] surfactant, and the mass content of ammonium chloride and sodium salicylate fracturing fluid state obtained are shown in Table 3. 表3为本发明实施例6得到的压裂液的状态。 Table 3 fracturing fluid state obtained in Example 6 of the embodiment of the present invention.

[0110] 表3本发明实施例6得到的压裂液的状态 Fracturing fluid state obtained in Example 6 of the embodiment of [0110] the present invention Table 3

[0111] [0111]

Figure CN106946743AD00132

[0112] 图4为表3中样品1在不同温度下黏度随时间的变化,在固定剪切频率下,随着温度升高,压裂液黏度下降,但在短时间内(Ih)保持稳定,而且即便在高温条件下(II(TC),黏度也可达25mPa · s,符合油气田要求。 [0112] FIG. 4 Table 3 Sample 1 viscosity change with time at a fixed shear frequency, as the temperature increases, the viscosity of the fracturing fluid at different temperatures decrease, but remained steady in a short time (Ih is) and even under high temperature conditions (II (TC), the viscosity is also up 25mPa · s, meet the requirements of oil and gas fields.

[0113] 由表3和图4可知,加入水杨酸钠可以有效提高表面活性剂溶液的克拉夫点,使其耐温性变好,但会降低其溶解度,因而更适用于高温储层。 [0113] As apparent from Table 3 and FIG. 4, sodium salicylate can effectively improve the Krafft point of the surfactant solution, so that heat resistance becomes better, but its solubility decreases, and thus more suitable for high temperature reservoirs.

[0114] 实施例7 [0114] Example 7

[0115] 将实施例1制备得到的双阳离子表面活性剂、氯化铵和水混合,得到压裂液,双阳离子表面活性剂在压裂液中的含量为2. Owt %,氯化铵在压裂液中的含量为I. Owt %。 [0115] The embodiment dicationic surfactant obtained in Preparation Example 1, ammonium chloride and water were mixed to give a fracturing fluid, dicationic surfactant content in the fracturing fluid is 2. Owt%, ammonium chloride content of fracturing fluid is I. Owt%.

[0116] 通过向压裂液中加入不同含量的碳酸氢钠调节体系pH值,图5显示了实施例7得到的压裂液在90°C不同pH条件下降解不同时间后在25°C测试的黏度变化。 [0116] by the addition of different contents of sodium hydrogencarbonate to the fracturing fluid pH of the system, Figure 5 shows a fracturing fluid obtained in Example 7 at 90 ° C after different pH conditions degrade at different times in 25 ° C test changes in viscosity. 可以看出,一段时间后压裂液体系的黏度从160mPa · s左右降低到了约7mPa · s,化学反应式为: As can be seen, the viscosity of fracturing fluid is reduced after a period of time from about 160mPa · s to about 7mPa · s, a chemical reaction is:

[0117] [0117]

Figure CN106946743AD00141

[0118] —分子双阳离子表面活性剂可释放两分子二氧化碳气体,其他产物分别为油溶性十八胺和水溶性小分子季铵盐,不乳化,对油水分离无影响。 [0118] - bis cationic surfactant molecules releasably two molecules of carbon dioxide gas, other products are oil-soluble and water-soluble small molecule octadecylamine, quaternary ammonium salts, not emulsified oil had no effect on the separation.

[0119] 实施例8 [0119] Example 8

[0120] 将实施例2制备得到的双阳离子表面活性剂、氯化铵和水混合,得到压裂液,双阳离子表面活性剂在压裂液中的含量为3. Owt %,氯化铵在压裂液中的含量为I. Owt %。 [0120] Surfactant mixed ammonium dications, and water will be obtained in Preparation Example 2, thereby obtaining fracturing fluid, dicationic surfactant content in the fracturing fluid to 3. Owt%, ammonium chloride content of fracturing fluid is I. Owt%.

[0121] 通过向压裂液中加入不同含量的碳酸氢钠调节体系pH值,图6显示了实施例8得到的压裂液在90°C不同pH条件下降解不同时间后在25°C测试的黏度变化。 [0121] adjusting the pH of the system by the addition of different contents of sodium bicarbonate to the fracturing fluid, FIG. 6 shows a fracturing fluid obtained in Example 8 at 90 ° C after different pH conditions degrade at different times in 25 ° C test changes in viscosity. 可以看出,一段时间后压裂液体系的黏度从IOOmPa · s左右降低到了约SmPa · s,化学反应式为: As can be seen, the viscosity of fracturing fluid is reduced after a period of time from about IOOmPa · s to about SmPa · s, a chemical reaction is:

[0122] [0122]

Figure CN106946743AD00142

[0123] —分子双阳离子表面活性剂可释放两分子二氧化碳气体,其他产物分别为油溶性十六胺和水溶性小分子季铵盐,不乳化,对油水分离无影响。 [0123] - bis cationic surfactant molecules releasably two molecules of carbon dioxide gas, other products are oil-soluble and water-soluble small molecule hexadecylamine quaternary ammonium salts that are not emulsified, no effect on the separation of oil and water.

[0124] 实施例9 [0124] Example 9

[0125] 将实施例3制备得到的双阳离子表面活性剂、氯化铵和水混合,得到压裂液,双阳离子表面活性剂在压裂液中的含量为2.5wt %,氯化铵在压裂液中的含量为I. Owt %。 [0125] Surfactant mixed ammonium dications, and water will be obtained in Preparation Example 3, thereby obtaining fracturing fluid, dicationic surfactant content in the fracturing fluid in the range 2.5wt%, the press ammonium chloride content of cracked liquid is I. Owt%.

[0126] 通过向压裂液中加入不同含量的碳酸氢钠调节体系pH值,图7显示了实施例9得到的压裂液在90°C不同pH条件下降解不同时间后在25°C测试的黏度变化。 [0126] adjusting the pH of the system by the addition of different contents of sodium bicarbonate to the fracturing fluid, FIG. 7 shows a fracturing fluid obtained in Example 9 after 90 ° C at different pH conditions degrade at different times at 25 ° C test changes in viscosity. 可以看出,一段时间后压裂液体系的黏度从90mPa · s左右降低到了约3mPa · s,化学反应式为: As can be seen, the viscosity of fracturing fluid is reduced after a period of time from about 90mPa · s to about 3mPa · s, a chemical reaction is:

[0127] [0127]

Figure CN106946743AD00151

[0128] —分子双阳离子表面活性剂可释放两分子二氧化碳气体,其他产物分别为油溶性十八胺和水溶性小分子季铵盐,不乳化,对油水分离无影响。 [0128] - bis cationic surfactant molecules releasably two molecules of carbon dioxide gas, other products are oil-soluble and water-soluble small molecule octadecylamine, quaternary ammonium salts, not emulsified oil had no effect on the separation.

[0129] 实施例10 [0129] Example 10

[0130] 采用高温高压装置试验模拟试剂地层情况,研究压力、温度对压裂液生气量、生气速度的影响。 [0130] The case study pressure, high temperature and pressure apparatus reagent test simulates the formation temperature of the amount of fracturing fluid angry, angry speed. 压裂液配方为实施例1制备得到的双阳离子表面活性剂、氯化铵和水,双阳离子表面活性剂在压裂液中含量为2. Owt %,氯化铵在压裂液中含量为I. Owt %,加入碳酸氢钠调节溶液pH值为7.5。 Fracturing fluid formulation prepared in Example 1 was obtained dicationic surfactant, water and ammonium chloride, bis cationic surfactant content in the fracturing fluid is 2. Owt%, ammonium content in the fracturing fluid as the I. Owt%, was added a solution of sodium bicarbonate to a pH of 7.5. 由工作站实时检测反应体系压力随时间的变化规律,由PV = nRT计算产生的气体的量,检测结果如表4所示,表4为本发明实施例10得到的压裂液生气性能检测结果。 The amount of gas detected by the pressure of the reaction system of the workstation in real time variation with time, is generated by the PV = nRT calculation, the detection results shown in Table 4, Table 4 is angry fracturing fluid properties detection result obtained in Example 10 disclosure. (其中空白压力增加是指等体积的水受热蒸发所导致的压力增加,实验压力增加是指压裂液中水蒸发和表活剂受热分解所产生气体导致的总压力变化,生气压力增加是指实验增压减去空白增压) Pressure (pressure increase which means a blank equal volume of water evaporation heat resulting increase in pressure increases the experiment is the total gas pressure changes due to evaporation of water in the fracturing fluid and surface active agent produced by thermal decomposition, pressure increase means angry experimental supercharged boost minus blank)

[0131] 表4本发明实施例10得到的压裂液生气性能检测结果 Angry fracturing fluid properties detection result obtained in Example 10 [0131] Table 4 of the present invention

[0132] [0132]

Figure CN106946743AD00161

[0133] 由表4可知,常温常压,预测IL压裂液生气体积为10.4L。 [0133] As apparent from Table 4, normal temperature and pressure, IL predicted volume of fracturing fluid angry 10.4L.

[0134] 实施例11 [0134] Example 11

[0135] 采用高温高压装置试验模拟试剂地层情况,研究压力、温度对压裂液生气量、生气速度的影响。 [0135] The case study pressure, high temperature and pressure apparatus reagent test simulates the formation temperature of the amount of fracturing fluid angry, angry speed. 压裂液配方为实施例2制备得到的双阳离子表面活性剂、氯化铵和水,双阳离子表面活性剂在压裂液中含量为3. Owt %,氯化铵在压裂液中含量为I. Owt %,加入碳酸氢钠调节溶液pH值为7.5。 Fracturing fluid formulation as dicationic surfactant obtained in Production Example 2, ammonium chloride and water, dicationic surfactant content in the fracturing fluid to 3. Owt%, ammonium content in the fracturing fluid as the I. Owt%, was added a solution of sodium bicarbonate to a pH of 7.5. 由工作站实时检测反应体系压力随时间的变化规律,由PV = nRT计算产生的气体的量,检测结果如表5所示,表5为本发明实施例11得到的压裂液生气性能检测结果。 The amount of gas detected by the pressure of the reaction system of the workstation in real time variation with time, is generated by the PV = nRT calculated detection results shown in Table 5, the results of performance test angry fracturing fluid obtained in Example 11 in Table 5 of the present invention.

[0136] 表5本发明实施例11得到的压裂液生气性能检测结果 Angry fracturing fluid properties detection result obtained in Example 11 [0136] Table 5 of the present invention

[0137] [0137]

Figure CN106946743AD00162

[0138] 由表5可知,常温常压,预测IL压裂液生气体积为16.6L。 [0138] As apparent from Table 5, normal temperature and pressure, IL predicted volume of fracturing fluid angry 16.6L.

[0139] 实施例12 [0139] Example 12

[0140] 采用高温高压装置试验模拟试剂地层情况,研究压力、温度对压裂液生气量、生气速度的影响。 [0140] The case study pressure, high temperature and pressure apparatus reagent test simulates the formation temperature of the amount of fracturing fluid angry, angry speed. 压裂液配方为实施例3制备得到的双阳离子表面活性剂、氯化铵和水,双阳离子表面活性剂在压裂液中含量为2.5wt %,氯化铵在压裂液中含量为I. Owt %,加入碳酸氢钠调节溶液pH值为7.5。 Dicationic surfactant fracturing fluid formulation prepared in Example 3 is obtained, ammonium chloride and water, dicationic surfactant fracturing fluid in an amount of 2.5wt%, the chloride content in the fracturing fluid I . Owt%, was added a solution of sodium bicarbonate to a pH of 7.5. 由工作站实时检测反应体系压力随时间的变化规律,由PV = nRT计算产生的气体的量,检测结果如表6所示,表6为本发明实施例12得到的压裂液生气性能检测结果。 The amount of gas detected by the pressure of the reaction system of the workstation in real time variation with time, is generated by the PV = nRT calculation, the detection results shown in Table 6, fracturing fluid properties detection result angry Example 12 in Table 6 of the present invention.

[0141] 表6本发明实施例12得到的压裂液生气性能检测结果 Angry fracturing fluid properties detection result obtained Example 12 [0141] Table 6 of the present invention

[0142] [0142]

Figure CN106946743AD00171

[0143] 由表6可知,常温常压,预测IL压裂液生气体积为13.0L。 [0143] As apparent from Table 6, temperature and pressure, IL predicted volume of fracturing fluid angry 13.0L.

[0144] 由以上实施例可知,本发明提供了一种双子阳离子表面活性剂,具有式I结构:式I 中,R为碳原子数为10〜30的烷基,η为11〜17 ;m为2〜6; X为0或N; Y为卤素。 [0144] apparent from the above embodiments, the present invention provides a cationic gemini surfactants having a structure of Formula I: Formula I, R 10~30 carbon atoms of the alkyl group, [eta] is 11~17; m of 2~6; X is 0 or N; Y is a halogen. 与现有技术相比,本发明通过巧妙的分子结构设计,将自降解、自生气功能创新性的结合在一起,提供了一种同时具有无机盐用量低、可自降解、自生气等性能优越的压裂液,这种压裂液降解后产物为亲水性小分子和亲油分子,对地层无损害,因而无须返排。 Compared with the prior art, the present invention is the molecular structure through clever design, self degradation, self-binding function together innovative angry, there is provided an inorganic salt having both a low dosage, self degradation, self anger excellent properties the fracturing fluid, the fracturing fluid degradation products such as small molecule hydrophilic and lipophilic molecules, no damage to the formation, thus without flowback.

Claims (10)

  1. 1. 一种双子阳离子表面活性剂,具有式I结构: A Gemini cationic surfactant, having a structure of Formula I:
    Figure CN106946743AC00021
    式I中,R为碳原子数为10〜30的烷基,η为11〜17;m为2〜6;X为O或N;Y为卤素。 Formula I, R is 10~30 carbon atoms in the alkyl group, η is 11~17; m is 2~6; X is O or N; Y is a halogen.
  2. 2. —种权利要求1所述的双子阳离子表面活性剂的制备方法,包括以下步骤: (1)将式1结构化合物和双(三氯甲基)碳酸酯进行反应,得到式2结构化合物; ⑵将式2结构化合物与式3结构化合物进行反应,得到式4结构化合物; (3)将式4结构化合物与式5结构化合物进行反应,得到式I结构的双子阳离子表面活性剂; 2. - The method of producing the cationic gemini surfactant according to one of claims species, comprising the steps of: (1) The structure of the compound of formula 1 and bis (trichloromethyl) carbonate reacted, to give a compound of Formula 2 structure; ⑵ compound of formula 3 with a compound of structural formula 2 is reacted to give a compound of structural formula 4; (3) the structure of formula 4 with a compound of the formula 5 compound is reacted to give Gemini cationic surfactant of formula I of the structure;
    Figure CN106946743AC00022
    其中,式1、式2、式4和式I中的R为碳原子数为10〜30的烷基; 式3、式4和式I中的X为O或N,n为11〜17; 式5和式I中的m为2〜6, Y为卤素。 Wherein Formula 1, Formula 2, Formula 4 and Formula I is R 10~30 carbon atoms of the alkyl group; Formula 3, Formula 4, and Formula I wherein X is O or N, n is 11~17; formula 5 and formula I, m is 2~6, Y is halogen.
  3. 3. 根据权利要求2所述的方法,其特征在于,所述步骤(1)中反应的温度为35〜150°C, 反应的时间为0.5〜10小时。 3. The method according to claim 2, characterized in that the temperature (1) the reaction step is 35~150 ° C, the reaction time is 0.5~10 hours.
  4. 4. 根据权利要求2所述的方法,其特征在于,所述步骤(2)中的反应在催化剂的存在下进行。 4. The method according to claim 2, characterized in that the reaction (2) in said step is carried out in the presence of a catalyst.
  5. 5. —种压裂液,包括权利要求1所述的双子阳离子表面活性剂。 5. - kind of fracturing fluid, comprising a cationic gemini surfactant according to claim 1.
  6. 6. 根据权利要求5所述的压裂液,其特征在于,所述压裂液包括: 权利要求1所述的双子阳离子表面活性剂; 交联剂; 水。 6. The fracturing fluid as claimed in claim 5, wherein said fracturing fluid comprising: a cationic gemini surface active agent according to claim 1; crosslinker; water.
  7. 7. 根据权利要求6所述的压裂液,其特征在于,所述交联剂选自氯化钾、氯化铵、氯化钠、溴化钾、溴化铵、溴化钠或水杨酸钠。 The fracturing fluid according to claim 6, wherein said crosslinking agent is selected from potassium chloride, ammonium chloride, sodium chloride, potassium bromide, ammonium bromide, sodium bromide or salicyl sodium.
  8. 8. 根据权利要求6所述的压裂液,其特征在于,所述双子阳离子表面活性剂在压裂液中的质量含量为0.5〜3%。 8. The fracturing fluid as claimed in claim 6, characterized in that the mass content of the cationic gemini surfactant fracturing fluid is 0.5~3%.
  9. 9. 根据权利要求6所述的压裂液,其特征在于,所述交联剂在压裂液中的质量含量为 9. The fracturing fluid according to claim 6, wherein the content of crosslinking agent in the fracturing fluid is
    0.5 〜3%〇 0.5 ~ 3% billion
  10. 10. 根据权利要求6所述的压裂液,其特征在于,所述压裂液还包括pH值调节剂。 10. A fracturing fluid according to claim 6, wherein the fracturing fluid further comprises a pH adjusting agent.
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Citations (3)

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CN1606654A (en) * 2001-02-13 2005-04-13 索菲技术股份有限公司 Aqueous viscoelastic fluid
CN101671553A (en) * 2009-09-28 2010-03-17 中国石油天然气股份有限公司 Self-gas-production solid-foam liquor drainage ball of watered gas well
CN103756662A (en) * 2013-11-28 2014-04-30 中国石油天然气股份有限公司 Multifunctional flowback-free surfactant fracturing fluid

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Publication number Priority date Publication date Assignee Title
CN1606654A (en) * 2001-02-13 2005-04-13 索菲技术股份有限公司 Aqueous viscoelastic fluid
CN101671553A (en) * 2009-09-28 2010-03-17 中国石油天然气股份有限公司 Self-gas-production solid-foam liquor drainage ball of watered gas well
CN103756662A (en) * 2013-11-28 2014-04-30 中国石油天然气股份有限公司 Multifunctional flowback-free surfactant fracturing fluid

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