CN107088385B - A kind of high temperature resistant overlength chain viscoelastic surfactant and the preparation method and application thereof - Google Patents

A kind of high temperature resistant overlength chain viscoelastic surfactant and the preparation method and application thereof Download PDF

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CN107088385B
CN107088385B CN201710331244.1A CN201710331244A CN107088385B CN 107088385 B CN107088385 B CN 107088385B CN 201710331244 A CN201710331244 A CN 201710331244A CN 107088385 B CN107088385 B CN 107088385B
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viscoelastic surfactant
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CN107088385A (en
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冯玉军
王骥
殷鸿尧
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Sichuan University
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    • C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
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    • 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
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Abstract

High temperature resistant overlength chain viscoelastic surfactant of the present invention, structural formula are as follows:In structural formula, R1For saturation or unsaturation alkane with 18~22 carbon atoms, R2For H atom, or the saturated alkane with 2~4 carbon atoms, R3For H atom or the saturated alkane with 2~4 carbon atoms, X—For Cl‑、Br‑、F‑、CO3 2‑、SO4 2‑、HCOO‑And CH3COO‑One of.The present invention also provides the preparation method of above-mentioned overlength chain viscoelastic surfactant and as the application for becoming glutinous gelling agent for acid fluid.Overlength chain viscoelastic surfactant of the present invention is able to satisfy the requirement under the adverse circumstances such as high temperature, highly acid as thickening agent, has stable structure, high temperature resistant and excellent acid solution thickening properties.

Description

A kind of high temperature resistant overlength chain viscoelastic surfactant and the preparation method and application thereof
Technical field
The invention belongs to oil-gas mining fields, and in particular to a kind of viscoelastic surfactant and preparation method with as change The application of glutinous gelling agent for acid fluid.
Background technique
Acidification, ACID FRACTURING TECHNOLOGY are to restore and improve the effective way of hypotonic oil gas well production, but for a long time, be acidified, acid Following Railway Project: (1) acid-rock reaction excessive velocities is always existed in pressure work progress, rock stratum deep acidification is caused to be difficult to reality It is existing；(2) during matrix acidifying, since reservoir longitudinal permeability difference is big, acid solution preferentially flows into hypertonic interval, causes hypertonic The excessive corrosion of interval, and the low permeability formation section being transformed is needed to be hardly obtained processing；(3) acid during fracture acidizing (acid fracturing) Liquid leak-off is serious, and is difficult to control.The acid fluid system that becomes sticky of petroleum industrial circle research provides new think of in order to solve the above problem Road.The acid solution that becomes sticky is by three parts such as acid solution, thickening agent, acid additives (clay stabilizer, corrosion inhibiter, ferrous stability) Composition, acid liquid viscosity changes with pH during acidification, acid fracturing, can preferably balance acid solution flowing, make the ground of different permeabilities Layer can reach acidification purpose.According to the type of thickening agent, the acid solution that becomes sticky can be divided into two types: based on polymer thickening agent Acid solution and (VES class becomes sticky based on the acid solution of viscoelastic surfactant (viscoelastic surfactant, VES) thickening agent Acid).Wherein the mechanism of action of the acid solution that becomes sticky based on VES is: acid solution is pumped into stratum and initially enters hypertonic stratum and send out with rock Raw reaction, with the consumption of acid solution, pH value is increased, and acid, rock reaction generate metal ion (Ca2+、Mg2+), surface-active in acid solution The microscopic aggregates structure of agent changes, and is changed into vermiculate glues from globular micelle, vermiculate glues is then mutually wound Three-dimensional space net structure is formed, acid fluid system viscosity is made to increase severely, realizes the process that becomes sticky.High viscosity acid fluid system blocks high permeability formation Duan Hou, the subsequent hypotonic interval of acid solution auto-steering, to realize that the shunting to acid solution turns to；It is high to target zone after treatment Viscosity acid solution encounters the hydrocarbon in reservoir and breaks glue automatically.It becomes sticky compared with acid with polymerization species, the VES class acid solution that becomes sticky has The advantages such as easy configuration, fragile glue, low to formation damage, and metal cation crosslinking agent is not contained in acid fluid system, avoid acid PH value increases and leads to the problem of and generate metal sulfide precipitating in precipitate metal hydroxides and sour well after liquid consumption.And it is right It becomes sticky acid solution in VES class, the type and performance of VES class thickening agent have very important shadow to the construction effect for the acid solution that becomes sticky It rings.
Currently used VES class thickening agent is mainly amphoteric surfactant (such as two class surface of glycine betaine and tertiary amine oxide Activating agent) or cationic quaternary ammonium salt surfactant (such as long chain alkyl ammonium salt and chain alkyl pyridinium halide).With mesh The continuous improvement of preceding oil gas development technology and mining requirement, well depth are continuously increased, and temperature is higher and higher, existing VES class thickening agent Temperature tolerance be difficult to meet application requirement, decline rapidly in 120 DEG C or so acid liquid viscosities.And existing VES class thickening agent is strong Chemical structure is unstable in acid environment, and the VES thickening agent difficulty or ease containing the weak bonds such as facile hydrolysis (amido bond, ester bond) are kept for a long time Stable chemical structure, to lose Efficient Adhesive Promotion.
Zhao Mengyun etc. (Zhao Mengyun, Zhao Zhongyang, Zhao Qing become sticky acid with turn to thickening agent VCA development oilfield chemistry, 2005,22 (2): 133-136) it is prepared for a kind of cationic surfactant based on long-chain fatty acid derivative, it is thick with it Though the acid solution initial viscosity that becomes sticky that agent is prepared is very low, after hydrochloric acid is reacted with carbonate rock in acid fluid system, Ca in acid solution2+ Concentration increases, and causes the viscoplasticity of system to sharply increase, but in 90 DEG C, 170s–1After lower constant temperature shearing 1h, viscosity is only 20mPas illustrates that the thickening agent temperature tolerance is bad.Dong Jing cutting edge of a knife or a sword et al. (Dong Jingfeng, Ah not all Ka Deera is not all warm, and west mentions, Li Xiaoyan, Gu Li Ghana mention A Zha and mention a kind of new type amphoteric surfactant self-diverting acid system Drilling and completion fluids of, 2016, (01): 102-106) VES that thickener concentration is 5% acid solution that becomes sticky is prepared by thickening agent of amphoteric surfactant exists In 25~85 DEG C of temperature range, acid solution viscosity kept stable, but when temperature is higher than 90 DEG C, acid liquid viscosity is with temperature Raising, that is, rapid decrease.
In addition, in the existing acid solution that becomes sticky the mass fraction of VES thickening agent need to reach 5% or more just can guarantee acid solution have compared with High viscosity, economic cost are higher.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of high temperature resistant viscoplasticity overlength chain surface-active Agent and the preparation method and application thereof, the super Longer-chain surfactants of the viscoplasticity have excellent acid solution as glutinous gelling agent for acid fluid is become Thickening capabilities and good temperature tolerance, and steady chemical structure, meet the application of the adverse circumstances such as strong acid, high temperature.
The super Longer-chain surfactants of viscoplasticity of the present invention, structural formula are as follows:
In structural formula, R1For saturation or unsaturation alkane with 18~22 carbon atoms, R2For H atom, or have 2~4 The saturated alkane of a carbon atom, R3For H atom or the saturated alkane with 2~4 carbon atoms, R2、R3It may be the same or different, X— For Cl-、Br-、F-、CO3 2-、SO4 2-、HCOO-And CH3COO-One of.
The preparation method of the above-mentioned super Longer-chain surfactants of high temperature resistant viscoplasticity provided by the invention, steps are as follows:
(1) fatty acid is dissolved in methylene chloride, adds organic amine, carbonyl activation agent, be added urge until completely dissolved Agent 4-dimethylaminopyridine is stirred to react 24~36h at room temperature, and reacting terminates to be added methylene chloride dilute reaction solution, then according to The secondary HCl solution for being 0.1%~0.5% with mass concentration, saturation NaHCO3Solution, saturation NaCl solution are washed respectively, then Organic phase is collected, by organic phase through anhydrous MgSO4It is filtered after drying, filtrate removing solvent is obtained into fatty acid amide；
Wherein, the dosage of methylene chloride should make fatty acid, organic amine, carbonyl-activating reagent and catalyst completely molten before reacting Solution；The molar ratio of organic amine and fatty acid is (1.1~1.5): 1；The molar ratio of catalyst 4-dimethylaminopyridine and fatty acid For (0.2~0.5): 1；The molar ratio of carbonyl activation agent and fatty acid is (2~2.5): 1；
(2) gained fatty acid amide is dissolved in tetrahydrofuran, the tetrahydrofuran that metal hydride is instilled at 0~5 DEG C is molten Liquid forms reaction solution, and the infusion volume of the tetrahydrofuran solution of metal hydride should make fatty acid amide and metal hydride in reaction solution Molar ratio be 1:(3.0~3.5), 70~150 DEG C of 24~36h of reaction are warming up to after being added dropwise, after reaction to gained It sequentially adds deionized water, the NaOH solution of mass concentration 10%~20%, deionized water in reaction solution reaction is quenched, then Filtering, gained filtrate is with anhydrous MgSO4It is filtered again after drying, gained filtrate removing solvent will be filtered again and obtain fatty uncle Amine；
(3) it is mixed and stirred for the acid solution of fat tertiary amine and mass concentration 10%~20% uniformly, to make fat tertiary amine proton Change, that is, form overlength chain viscoelastic surfactant thickening agent, the dosage of the acid solution is hydrogen ion in fat tertiary amine and acid solution Molar ratio be 1:1.
In the above method, the fatty acid is in saturation or unsaturated alkyl fatty acid with 18~22 carbon atoms It is at least one.
In the above method, the organic amine is at least one of the saturated alkyl organic amine with 4~8 carbon atoms.
In the above method, the carbonyl activation agent is 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (EDCHCl), dicyclohexylcarbodiimide (DCC), N, at least one of N- diisopropylcarbodiimide (DIC).
In the above method, the metal hydride is LiAlH4Or NaBH4。
In the above method, the acid solution is HCl solution, HBr solution, HF solution, H2SO4Solution, H2CO3Solution, HCOOH Solution, CH3At least one of COOH solution.
In the above method, in step (3), the acid solution of fat tertiary amine and mass concentration 10%~20% is mixed and stirred for It is even preferably to be carried out at 50~80 DEG C.
The dosage of methylene chloride is generally reacted when methylene chloride dilute reaction solution being added in the above method, in step (1) 2~5 times of liquid product, tetrahydrofuran can at least make corresponding solute fatty acid amide and gold as the dosage of solvent in step (2) Belong to hydride to be completely dissolved.
When overlength chain viscoelastic surfactant of the present invention is applied to become mucic acid liquid as thickening agent, with mass concentration The change mucic acid liquid based on the overlength chain viscoelastic surfactant thickening agent, institute can be obtained for 10%~20% acid solution mixing Stating the acid solution that mass concentration is 10%~20% is HCl solution, HBr solution, HF solution, H2SO4Solution, H2CO3Solution, HCOOH Solution, CH3At least one of COOH solution, acid solution dosage are viscoplasticity overlength chain surface-active in the change mucic acid liquid made The mass concentration of agent is 3%~5%.
Compared with prior art, the invention has the following advantages:
1, overlength chain viscoelastic surfactant of the present invention not only has excellent acid solution thickening property as thickening agent Can, and temperature tolerance is preferable, and when temperature is up to 150 DEG C, the viscosity of the change mucic acid liquid system based on the thickening agent is relatively stable And it is greater than 20mPas, meet the application demand of the adverse circumstances such as strong acid, high temperature.
2, the super Longer-chain surfactants of viscoplasticity of the present invention are good (see implementation as thickening agent steady chemical structure Example 3), it will not degrade being chronically under the adverse circumstances such as high-temperature strong acid, meet the adverse circumstances such as strong acid, high temperature Application demand.
3. overlength chain viscoelastic surfactant of the present invention is applied to become mucic acid liquid as thickening agent, quality is added It is that can reach preferable Efficient Adhesive Promotion, therefore economy is high that concentration, which is 3%, conducive to using in production.
4, the super Longer-chain surfactants preparation method of viscoplasticity of the present invention can be by changing fatty acid, fatty amine and acid The type etc. of liquid realizes the adjusting for surpassing Longer-chain surfactants thickening agent performance to viscoplasticity.
Detailed description of the invention
Fig. 1 is N- (cis- 22 carbon -9- alkenyl)-N, N- diethylamide1H NMR spectra.
Fig. 2 is N- (cis- 22 carbon -9- alkenyl)-N, N- diethyl tertiary amine1H NMR spectra.
Fig. 3 is 3.0%N- (cis- 22 carbon -9- alkenyl)-N, and N- diethyl Amine from Tertiary Amine Hydrochloride is in 20%HCl solution Rheological behaviour.
Fig. 4 is 3.5%N- (cis- 22 carbon -9- alkenyl)-N, and N- diethyl Amine from Tertiary Amine Hydrochloride is in 20%HCl solution Rheological behaviour.
Fig. 5 is N- (cis- 22 carbon -9- alkenyl)-N after rheometer test, N- diethyl Amine from Tertiary Amine Hydrochloride1H H NMR spectroscopy Figure.
Fig. 6 is N, N- diethyl-N- n-docosane base amide1H NMR spectra.
Fig. 7 is N, N- diethyl-N- n-docosane base tertiary amine1H NMR spectra.
Fig. 8 is 3.0%N, rheology row of the N- diethyl-N- n-docosane base Amine from Tertiary Amine Hydrochloride in 20%HCl solution For figure.
Fig. 9 is N after rheometer test, N- diethyl-N- n-docosane base Amine from Tertiary Amine Hydrochloride1H NMR spectra.
Figure 10 is N, N- diethyl-N- n-octadecane base amide1H NMR spectra.
Figure 11 is N, N- diethyl-N- n-octadecane base tertiary amine1H NMR spectra.
Figure 12 is 3.0%N, rheological behaviour figure of positive 18 Amine from Tertiary Amine Hydrochloride of N- diethyl-N- in 20%HCl solution.
Figure 13 is N after rheometer test, N- diethyl-N- n-octadecane base Amine from Tertiary Amine Hydrochloride1H NMR spectra.
Specific embodiment
Below by specific embodiment to high temperature resistant overlength chain viscoelastic surfactant of the present invention and its preparation Method is described further with application.
In following embodiment, concentration and percentage composition are mass percent.
Embodiment 1
(1) it weighs 16.92g (0.05mol) Erucic Acid (popular name " erucic acid ") and is dissolved in methylene chloride, successively Be added 4.02g (0.055mol) diethylamide, 19.1g (0.1mol) EDCHCl, it is to be dissolved completely after add 1.22g (0.01mol) DMAP, reacts for 24 hours at room temperature.After reaction, it with 250mL methylene chloride dilute reaction solution, then successively uses 0.1% HCl solution is saturated NaHCO3Solution and saturation NaCl solution are washed three times respectively, are collected organic phase, are added anhydrous MgSO4Filtrate rotary evaporation is removed solvent by dry 2h, filtering, is dried in vacuo to get N, N- diethyl-N- positive 22 is arrived Alkylamide, structural characterization are shown in1H NMR spectra (Fig. 1), the chemical shift of each proton peak is found in spectrogram in compound Ownership, and coincide preferably between each proton resonance peak integral area ratio and theoretical value, show that the compound successfully synthesizes.
(2) by gained N, N- diethyl-N- n-docosane base amide is added in 500mL round-bottomed flask, and 100mL is added Tetrahydrofuran dissolution, is cooled to 2 DEG C until completely dissolved, LiAlH is added dropwise4Tetrahydrofuran solution, wherein fatty acid amide Molar ratio with metal hydride is 1:3.0, and 75 DEG C of reactions are warming up to after being added dropwise for 24 hours, are reacted after reaction to gained It sequentially adds deionized water, 10%NaOH solution, deionized water in liquid reaction is quenched, then filtering reacting liquid, filtrate nothing Water MgSO4It dries, filters, filtrate rotary evaporation is removed into solvent, obtains N- (cis- 22 carbon -9- alkenyl)-N, N- diethyl Tertiary amine, structural characterization are shown in1H NMR spectra (Fig. 2), the chemical shift of each proton peak is found in spectrogram in compound returns Belong to, and coincide preferably between each proton resonance peak integral area ratio and theoretical value, shows that the compound successfully synthesizes.
(3) by N- (cis- 22 carbon -9- alkenyl)-N, N- diethyl tertiary amine is mixed with mass concentration 15%HCl solution, The dosage of HCl solution is to make N- (cis- 22 carbon -9- alkenyl)-N, hydrionic mole in N- diethyl tertiary amine and HCl solution Than for 1:1,50 DEG C of stirrings obtain N- (cis- 22 carbon -9- alkenyl)-N for 24 hours to uniform, N- diethyl Amine from Tertiary Amine Hydrochloride, i.e., Surpass Longer-chain surfactants for viscoplasticity.
(4) by N- (cis- 22 carbon -9- alkenyl)-N, N- diethyl Amine from Tertiary Amine Hydrochloride and mass concentration 15%HCl solution Mixing, that is, obtain the acid solution that becomes sticky, and the dosage of HCl solution is to make N- (cis- 22 carbon -9- alkenyl)-N, N- diethyl tertiary ammonium salt Hydrochlorate is in the mass concentration become in mucic acid liquid into 3%.Pass through the matched PZ39 rotor/rotating cylinder system of Haake torque rheometer and its institute System is tested, and is 100s in shear rate-1Become mucic acid liquid viscosity obtained by lower measurement with temperature, the variation relation of time, as a result See Fig. 3.From figure 3, it can be seen that the viscosity of solution performance is relatively stable and is greater than 20mPas when temperature is stablized at 150 DEG C, Show that the super Longer-chain surfactants of viscoplasticity obtained by the present embodiment have good temperature tolerance as thickening agent.
After test, acid solution is cooled to room temperature, rotates, N- (cis- 22 carbon -9- alkene is obtained after freeze-drying Base)-N, N- diethyl Amine from Tertiary Amine Hydrochloride, structural characterization is shown in1H NMR spectra (Fig. 5), the chemical potential of each proton peak in compound Ownership is found in shifting in spectrogram, and is coincide preferably between each proton resonance peak integral area ratio and theoretical value, shows the change It closes object degradation occurs under high-temperature strong acid environment, goes bad, illustrates that its steady chemical structure is preferable, meet high temperature, strong acid Application requirement under the adverse circumstances such as property.
Embodiment 2
This implementation difference from example 1 is that, in step (4), the dosage of HCl solution is to make N- (cis- 22 Carbon -9- alkenyl)-N, N- diethyl Amine from Tertiary Amine Hydrochloride is in the mass concentration become in mucic acid liquid into 3.5%.
It is 100s in shear rate-1Become mucic acid liquid viscosity obtained by lower measurement with temperature, the variation relation of time, as a result sees figure 4.From fig. 4, it can be seen that the viscosity of solution performance is relatively stable and is greater than 20mPas when temperature is stablized at 150 DEG C, show The super Longer-chain surfactants of viscoplasticity obtained by the present embodiment have good temperature tolerance as thickening agent.
Embodiment 3
(1) it weighs the positive behenic acid (popular name " arachidic acid ") of 17.03g (0.05mol) and is dissolved in methylene chloride, sequentially add 4.75g (0.065mol) diethylamide, 21.01g (0.11mol) EDCHCl, it is to be dissolved completely after add 1.83g (0.015mol) DMAP, reacts 30h at room temperature.After reaction, it with 250mL methylene chloride dilute reaction solution, then successively uses 0.2% HCl solution is saturated NaHCO3Solution and saturation NaCl solution are washed three times respectively, are collected organic phase, are added anhydrous MgSO4It dries, filters, filtrate rotary evaporation is removed into solvent, vacuum drying obtains N, N- diethyl-N- n-docosane base Amide, structural characterization are shown in1H NMR spectra (Fig. 5), the chemical shift of each proton peak is found in spectrogram in compound returns Belong to, and coincide preferably between each proton resonance peak integral area ratio and theoretical value, shows that the compound successfully synthesizes.
(2) by gained N, N- diethyl-N- n-docosane base amide is added in 500mL round-bottomed flask, and 100mL is added Tetrahydrofuran dissolution, is cooled to 0~5 DEG C until completely dissolved, LiAlH is then added dropwise4Tetrahydrofuran solution, wherein rouge The molar ratio of fat amide and metal hydride is 1:3.3, and 75 DEG C of reaction 30h are warming up to after being added dropwise.After reaction gradually Deionized water, 15%NaOH aqueous solution, deionized water is added reaction is quenched.Then filtering reacting liquid, filtrate is with anhydrous MgSO4 Dry, filtering, rotary evaporation remove solvent and obtain N, N- diethyl docosyl tertiary amine.Its structural characterization is shown in1HNMR spectrogram (Fig. 6), ownership, and each proton resonance peak integral area ratio are found in the chemical shift of each proton peak in spectrogram in compound It coincide preferably between theoretical value, shows that the compound successfully synthesizes.
(3) by N, N- diethyl docosyl tertiary amine is that 15%HCl solution mixes with mass concentration, the use of HCl solution Amount is makes N, and hydrionic molar ratio is 1:1 in N- diethyl docosyl tertiary amine and HCl solution, and 50 DEG C of stirrings are for 24 hours to equal It is even, obtain N, N- diethyl docosyl Amine from Tertiary Amine Hydrochloride, the as super Longer-chain surfactants of viscoplasticity.
(4) by N, N- diethyl docosyl Amine from Tertiary Amine Hydrochloride mixes with mass concentration 15%HCl solution, that is, is become Glactaric acid liquid, the dosage of HCl solution are to make N, and N- diethyl docosyl Amine from Tertiary Amine Hydrochloride is in the mass concentration become in mucic acid liquid It is 3%.It is tested by the matched PZ39 rotor/rotating cylinder system of Haake torque rheometer and its institute, is in shear rate 100s-1Test gained becomes mucic acid liquid viscosity with temperature, the variation relation of time, as a result sees Fig. 7.From figure 7 it can be seen that working as temperature Stablize at 150 DEG C, the viscosity of solution performance is relatively stable and is greater than 30mPas, shows surfactant obtained by the present embodiment With preferable temperature tolerance.
After test, acid solution is cooled to room temperature, there is white solid precipitation, filters, N, N- bis- is obtained after freeze-drying Ethyl docosyl Amine from Tertiary Amine Hydrochloride, structural characterization are shown in1H NMR spectra (Fig. 8).Pass through analysis of spectra 8, it is known that N, N- bis- Degradation occurs under high-temperature strong acid environment, goes bad for ethyl docosyl Amine from Tertiary Amine Hydrochloride, illustrates its steady chemical structure Property is preferable, meets the application requirement under the adverse circumstances such as high temperature, highly acid.
Embodiment 4
This implementation and embodiment 3 the difference is that, it is 10% that acid solution, which is mass concentration, in step (3) and step (4) Acetic acid solution, the dosage of acetic acid solution is to make N in step (4), and N- diethyl docosyl tertiary amine acetate is becoming mucic acid Mass concentration in liquid is 4%.
Embodiment 5
(1) it weighs 14.24g (0.05mol) n-octadecanoic acid (popular name " stearic acid ") and is dissolved in methylene chloride, sequentially add 5.48g (0.075mol) diethylamide, 23.87g (0.125mol) EDCHCl, it is to be dissolved completely after add 3.02g (0.025mol) DMAP, reacts 36h at room temperature.After reaction, it with 250mL methylene chloride dilute reaction solution, then successively uses 0.5% HCl solution is saturated NaHCO3Solution and saturation NaCl solution are washed three times respectively, are collected organic phase, are added anhydrous MgSO4It dries, filters, filtrate rotary evaporation is removed into solvent, be dried in vacuo to get N, N- diethyl-N- n-octadecane base is arrived Amide, structural characterization are shown in1H NMR spectra (Fig. 8), the chemical shift of each proton peak is found in spectrogram in compound returns Belong to, and coincide preferably between each proton resonance peak integral area ratio and theoretical value, shows that the compound successfully synthesizes.
(2) by gained N, N- diethyl-N- n-octadecane base amide is added in 500mL round-bottomed flask, and 100mL tetra- is added The dissolution of hydrogen furans, is cooled to 0~5 DEG C until completely dissolved, LiAlH is added dropwise4Tetrahydrofuran solution, wherein fatty acid amide Molar ratio with metal hydride is 1:3.5, and 75 DEG C of reaction 36h are warming up to after being added dropwise.It is gradually added after reaction Reaction is quenched for ionized water, 20%NaOH aqueous solution, deionized water.Then filtering reacting liquid, filtrate is dry with anhydrous MgSO4, Filtrate rotary evaporation removing solvent is obtained N, positive 18 tertiary amine of N- diethyl by filtering, and structural characterization is shown in1H NMR spectra (figure 9), ownership is found in the chemical shift of each proton peak in spectrogram in compound, and each proton resonance peak integral area ratio with It coincide preferably between theoretical value, shows that the compound successfully synthesizes.
(3) by N, positive 18 tertiary amine of N- diethyl is that 15%HCl solution mixes with the concentration of quality, the dosage of HCl solution To make N, hydrionic molar ratio is 1:1 in positive 18 tertiary amine of N- diethyl and HCl solution, and 50 DEG C of stirrings obtain for 24 hours to uniform Positive 18 Amine from Tertiary Amine Hydrochloride of N, N- diethyl, the as super Longer-chain surfactants of viscoplasticity.
(4) by N, positive 18 Amine from Tertiary Amine Hydrochloride of N- diethyl is uniformly mixed with mass concentration 15%HCl solution, that is, is become Glactaric acid liquid, the dosage of HCl solution are to make N, positive 18 Amine from Tertiary Amine Hydrochloride of N- diethyl the mass concentration become in mucic acid liquid into 3%.It is tested by the matched PZ39 rotor/rotating cylinder system of Haake torque rheometer and its institute, is 100s in shear rate-1 Measurement gained becomes the viscosity of mucic acid liquid with temperature, the variation relation of time, the result is shown in Figure 11.It can be seen from figure 11 that working as temperature Stablize at 150 DEG C, the viscosity of solution performance is relatively stable and is greater than 20mPas.
After test, acid solution is cooled to room temperature, there is white solid precipitation, filters, N, N- bis- is obtained after freeze-drying Positive 18 Amine from Tertiary Amine Hydrochloride of ethyl, structural characterization are shown in1H NMR spectra (Figure 12).By analysis of spectra it is found that N, N- diethyl Degradation occurs under high-temperature strong acid environment, goes bad for positive 18 Amine from Tertiary Amine Hydrochloride, shows that its steady chemical structure is preferable, full Application requirement under the adverse circumstances such as sufficient high temperature, highly acid.
Embodiment 6
This implementation and embodiment 5 the difference is that, it is 20% that acid solution, which is mass concentration, in step (3) and step (4) Sulfuric acid solution, the dosage of sulfuric acid solution is to make N in step (4), and positive 18 tertiary ammonium salt of N- diethyl is in the matter become in mucic acid liquid Measuring concentration is 5%.

Claims (10)

1. a kind of high temperature resistant overlength chain viscoelastic surfactant, it is characterised in that structural formula is as follows:
In structural formula, R1For saturation or unsaturation alkane with 18~22 carbon atoms, R2It is full with 2~4 carbon atoms And alkane, R3For the saturated alkane with 2~4 carbon atoms, R2、R3It may be the same or different, X—For Cl-、Br-、F-、CO3 2-、 SO4 2-、HCOO-、CH3COO-One of.
2. the preparation method of high temperature resistant overlength chain viscoelastic surfactant described in claim 1, it is characterised in that steps are as follows:
(1) fatty acid is dissolved in methylene chloride, adds organic amine, carbonyl activation agent, catalyst is added until completely dissolved 4-dimethylaminopyridine is stirred to react 24~36h at room temperature, and reaction terminates that methylene chloride dilute reaction solution is added, then successively uses HCl solution, saturation NaHCO of the mass concentration for 0.1%~0.5%3Solution, saturation NaCl solution are washed respectively, are then collected Organic phase, by organic phase through anhydrous MgSO4It is filtered after drying, filtrate removing solvent is obtained into fatty acid amide；
Wherein, the dosage of methylene chloride should be such that fatty acid, organic amine, carbonyl-activating reagent and catalyst is completely dissolved before reacting； The molar ratio of organic amine and fatty acid is (1.1~1.5): 1；Catalyst 4-dimethylaminopyridine and the molar ratio of fatty acid are (0.2~0.5): 1；The molar ratio of carbonyl activation agent and fatty acid is (2~2.5): 1；
(2) gained fatty acid amide is dissolved in tetrahydrofuran, the tetrahydrofuran solution shape of metal hydride is instilled at 0~5 DEG C At reaction solution, the infusion volume of the tetrahydrofuran solution of metal hydride should make rubbing for fatty acid amide and metal hydride in reaction solution You are than being 1:(3.0~3.5), it is warming up to 70~150 DEG C of 24~36h of reaction after being added dropwise, is reacted after reaction to gained It sequentially adds deionized water, the NaOH solution of mass concentration 10%~20%, deionized water in liquid reaction is quenched, then mistake Filter, gained filtrate is with anhydrous MgSO4It is filtered again after drying, gained filtrate removing solvent will be filtered again and obtain fat tertiary amine；
(3) it is mixed and stirred for the acid solution of fat tertiary amine and mass concentration 10%~20% uniformly, protonate fat tertiary amine, i.e., Overlength chain viscoelastic surfactant is formed, the dosage of the acid solution is that hydrionic molar ratio is 1 in fat tertiary amine and acid solution: 1。
3. the preparation method of high temperature resistant overlength chain viscoelastic surfactant according to claim 2, it is characterised in that described Fatty acid is at least one of saturation or unsaturated alkyl fatty acid with 18~22 carbon atoms.
4. the preparation method of high temperature resistant overlength chain viscoelastic surfactant according to Claims 2 or 3, it is characterised in that institute Stating organic amine is at least one of the saturated alkyl organic amine with 4~8 carbon atoms.
5. the preparation method of high temperature resistant overlength chain viscoelastic surfactant according to Claims 2 or 3, it is characterised in that institute Stating carbonyl activation agent is 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate, dicyclohexylcarbodiimide, N, N- At least one of diisopropylcarbodiimide.
6. the preparation method of high temperature resistant overlength chain viscoelastic surfactant according to Claims 2 or 3, it is characterised in that institute Stating metal hydride is LiAlH4Or NaBH4。
7. the preparation method of high temperature resistant overlength chain viscoelastic surfactant according to Claims 2 or 3, it is characterised in that institute Stating acid solution is HCl solution, HBr solution, HF solution, H2SO4Solution, H2CO3Solution, HCOOH solution, CH3In COOH solution extremely Few one kind.
8. the preparation method of high temperature resistant overlength chain viscoelastic surfactant according to Claims 2 or 3, it is characterised in that step Suddenly in (3), the acid solution of fat tertiary amine and mass concentration 10%~20% is mixed and stirred for uniformly carrying out at 50~80 DEG C.
9. high temperature resistant overlength chain viscoelastic surfactant described in claim 1 is as the application for becoming glutinous gelling agent for acid fluid.
10. applying according to claim 9, it is characterised in that by the high temperature resistant overlength chain viscoelastic surfactant and matter Measure concentration be 10%~20% acid solution mix, the acid solution that the mass concentration is 10%~20% be HCl solution, HBr solution, HF solution, H2SO4Solution, H2CO3Solution, HCOOH solution, CH3At least one of COOH solution, acid solution dosage make to obtain Become the mass concentration of high temperature resistant overlength chain viscoelastic surfactant in mucic acid liquid as 3%~5%.
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