CN107088385A - A kind of high temperature resistant overlength chain viscoelastic surfactant and preparation method and application - Google Patents

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

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CN107088385A
CN107088385A CN201710331244.1A CN201710331244A CN107088385A CN 107088385 A CN107088385 A CN 107088385A CN 201710331244 A CN201710331244 A CN 201710331244A CN 107088385 A CN107088385 A CN 107088385A
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solution
acid
viscoelastic surfactant
high temperature
temperature resistant
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CN107088385B (en
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冯玉军
王骥
殷鸿尧
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Sichuan University
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    • C07C209/50—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of carboxylic acid amides
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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, its structural formula is as follows：In structural formula, R1For the saturation with 18~22 carbon atoms or unsaturated alkane, 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‑In one kind.Present invention also offers the preparation method of above-mentioned overlength chain viscoelastic surfactant and it is used as the application for becoming glutinous gelling agent for acid fluid.Overlength chain viscoelastic surfactant of the present invention can meet the use requirement under the adverse circumstances such as high temperature, highly acid as thickening agent, with Stability Analysis of Structures, high temperature resistant and excellent acid solution thickening properties.

Description

A kind of high temperature resistant overlength chain viscoelastic surfactant and preparation method and application
Technical field
The invention belongs to oil-gas mining field, and in particular to a kind of viscoelastic surfactant and preparation method are with being used as change The application of glutinous gelling agent for acid fluid.
Background technology
Acidifying, ACID FRACTURING TECHNOLOGY are the effective ways of recovery and the hypotonic oil gas well production of raising, but for a long time, acidifying, acid There is following Railway Project always in pressure work progress：(1) acid-rock reaction excessive velocities, cause rock stratum deep acidification to be difficult to reality It is existing；(2) during matrix acidifying, because reservoir longitudinal permeability difference is big, acid solution preferentially flows into hypertonic interval, causes hypertonic The excessive corrosion of interval, and need the low permeability formation transformed section to be hardly obtained processing；(3) it is sour during fracture acidizing (acid fracturing) Liquid leak-off is serious, and is difficult to control to.The acid fluid system that becomes sticky of petroleum industrial circle research is to solve the above problems there is provided new think of 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 acidifying, acid fracturing, can preferably balance acid solution flowing, make the ground of different permeabilities Layer can reach acidifying 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 (VES classes become sticky for acid solution and acid solution based on viscoelastic surfactant (viscoelastic surfactant, VES) thickening agent Acid).The mechanism of action of the acid solution that becomes sticky wherein based on VES is：Acid solution is pumped into stratum and initially enters hypertonic stratum and sent out with rock Raw reaction, with the consumption of acid solution, pH value rise, acid, rock reaction produce metal ion (Ca2+、Mg2+), surface-active in acid solution The microscopic aggregates structure of agent is changed, and vermiculate glues is changed into from globular micelle, and vermiculate glues is then mutually wound Three-dimensional space net structure is formed, acid fluid system viscosity is increased severely, the process that becomes sticky is realized.High viscosity acid fluid system blocks high permeability formation Duan Hou, the follow-up hypotonic interval of acid solution auto-steering, so as to realize that the shunting to acid solution is turned to；It is high after terminating to target zone processing The hydrocarbon that viscosity acid solution is run into reservoir breaks glue automatically.Become sticky with polymerization species compared with acid, the VES classes acid solution that becomes sticky has Easy configuration, fragile glue, to the low advantage of formation damage, and metal cation crosslinking agent is not contained in acid fluid system, it is to avoid acid PH value raises and produces and the problem of metal sulfide is precipitated is produced in precipitate metal hydroxides and sour well after liquid consumption.And it is right Become sticky acid solution in VES classes, the type and performance of VES class thickening agents have very important shadow to the construction effect for the acid solution that becomes sticky Ring.
Conventional VES class thickening agents are mainly amphoteric surfactant (such as glycine betaine and the class surface of tertiary amine oxide two at present 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 is continuously increased, temperature more and more higher, existing VES classes thickening agent Temperature tolerance be difficult to meet application requirement, decline rapidly in 120 DEG C or so acid liquid viscosities.And existing VES classes thickening agent is strong Chemical constitution is unstable in acid environment, and the VES thickening agents difficulty or ease containing the weak bonds such as facile hydrolysis (amido link, ester bond) are kept for a long time Stable chemical constitution, so as to lose Efficient Adhesive Promotion.
Zhao Mengyun etc. (Zhao Mengyun, Zhao Zhongyang, Zhao Qing become the glactaric acid development oilfield chemistries for turning to thickening agent VCA, 2005,22(2):A kind of cationic surfactant based on long-chain fatty acid derivative 133-136) is prepared for, using it to be thick Though the acid solution initial viscosity that becomes sticky that agent is prepared is very low, after hydrochloric acid reacts with carbonate rock in acid fluid system, Ca in acid solution2+ Concentration increase, 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 edges of a knife or a sword et al. (Dong Jingfeng, Ah not all Ka Deera is not all warm, and west is carried, Li Xiaoyan, Gu Li Ghana carry A Zha and carry a kind of new type amphoteric surfactant self-diverting acid system Drilling and completion fluids of, 2016,(01):The VES acid solutions that become sticky that thickener concentration is 5% 102-106) are prepared by thickening agent of amphoteric surfactant to exist 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 Rise be rapid decrease.
In addition, in the existing acid solution that becomes sticky the mass fraction of VES thickening agents need to reach more than 5% just can guarantee that acid solution have compared with High viscosity, financial cost is higher.
The content 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 preparation method and application, 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, its structural formula is as follows：
In structural formula, R1For the saturation with 18~22 carbon atoms or unsaturated alkane, R2For H atom, or with 2~4 The saturated alkane of individual 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-In one kind.
The preparation method for the above-mentioned super Longer-chain surfactants of high temperature resistant viscoplasticity that the present invention is provided, step is as follows：
(1) aliphatic acid is dissolved in dichloromethane, adds organic amine, carbonyl activation agent, added urge until completely dissolved Agent DMAP 24~36h of stirring reaction at room temperature, reaction terminates to add dchloromethane reaction solution, then according to HCl solution, saturation NaHCO of the secondary use mass concentration for 0.1%~0.5%3Solution, saturation NaCl solution are washed respectively, then Organic phase is collected, by organic phase through anhydrous MgSO4Filtered after drying, filtrate removing solvent is obtained into fatty acid amide；
Wherein, the consumption of dichloromethane should make aliphatic acid, organic amine, carbonyl-activating reagent and catalyst completely molten before reacting Solution；The mol ratio of organic amine and aliphatic acid is (1.1~1.5)：1；The mol ratio of catalyst DMAP and aliphatic acid For (0.2~0.5)：1；The mol ratio of carbonyl activation agent and aliphatic 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 formation reaction solution, the infusion volume of the tetrahydrofuran solution of metal hydride should make fatty acid amide and metal hydride in reaction solution Mol ratio be 1：70~150 DEG C of 24~36h of reaction are warming up to after (3.0~3.5), completion of dropping, reaction terminates backward gained Sequentially add deionized water, the NaOH solution of mass concentration 10%~20%, deionized water in reaction solution reaction is quenched, then Filtering, gained filtrate uses anhydrous MgSO4Filtered again after drying, gained filtrate removing solvent will be filtered again and obtains fatty uncle Amine；
(3) acid solution of fat tertiary amine and mass concentration 10%~20% is mixed and stirred for uniformly, making fat tertiary amine proton Change, that is, form overlength chain viscoelastic surfactant thickening agent, the consumption of the acid solution is fat tertiary amine and hydrogen ion in acid solution Mol ratio be 1：1.
In the above method, during the aliphatic acid is saturation or unsaturated alkyl aliphatic acid with 18~22 carbon atoms It is at least one.
In the above method, the organic amine is at least one of saturated alkyl organic amine with 4~8 carbon atoms.
In the above method, the carbonyl activation agent is 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate (EDCHCl) at least one of, dicyclohexylcarbodiimide (DCC), N, N- DICs (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 to be carried out preferably at 50~80 DEG C.
The consumption of dichloromethane is generally reaction when dchloromethane reaction solution is added in the above method, in step (1) Tetrahydrofuran can at least make corresponding solute fatty acid amide and gold as the consumption of solvent in 2~5 times of liquid product, step (2) Category hydride is 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 It is HCl solution, HBr solution, HF solution, H to state the acid solution that mass concentration is 10%~20%2SO4Solution, H2CO3Solution, HCOOH Solution, CH3At least one of COOH solution, acid solution consumption is to make viscoplasticity overlength chain surface-active in obtained change mucic acid liquid The mass concentration of agent is 3%~5%.
Compared with prior art, the invention has the advantages that：
1st, overlength chain viscoelastic surfactant of the present invention not only has excellent acid solution thickening property as thickening agent Can, and temperature tolerance is preferably, 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 more than 20mPas, meet the application demand of the adverse circumstances such as strong acid, high temperature.
2nd, 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 also be degraded even if 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 Concentration is that 3% can reach preferable Efficient Adhesive Promotion, therefore economy is high, beneficial to being used in production.
4th, the super Longer-chain surfactants preparation method of viscoplasticity of the present invention can be by changing aliphatic acid, fatty amine and acid Species of liquid etc., realizes the regulation to the super Longer-chain surfactants thickening agent performance of viscoplasticity.
Brief description of the drawings
Fig. 1 is N- (cis- 22 carbon -9- alkenyls)-N, N- diethylamides1H NMR spectras.
Fig. 2 is N- (cis- 22 carbon -9- alkenyls)-N, N- diethyl tertiary amines1H NMR spectras.
Fig. 3 is 3.0%N- (cis- 22 carbon -9- alkenyls)-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- alkenyls)-N, and N- diethyl Amine from Tertiary Amine Hydrochloride is in 20%HCl solution Rheological behaviour.
Fig. 5 is N- (cis- 22 carbon -9- alkenyls)-N after rheometer test, N- diethyl Amine from Tertiary Amine Hydrochloride1H H NMR spectroscopies Figure.
Fig. 6 is N, N- diethyl-N- n-docosane base acid amides1H NMR spectras.
Fig. 7 is N, N- diethyl-N- n-docosane base tertiary amines1H NMR spectras.
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 spectras.
Figure 10 is N, N- diethyl-N- n-octadecane base acid amides1H NMR spectras.
Figure 11 is N, N- diethyl-N- n-octadecane base tertiary amines1H NMR spectras.
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 spectras.
Embodiment
Below by embodiment to high temperature resistant overlength chain viscoelastic surfactant of the present invention and its preparation Method is described further with application.
In following examples, concentration and percentage composition are mass percent.
Embodiment 1
(1) weigh 16.92g (0.05mol) Erucic Acid (popular name " erucic acid ") and be dissolved in dichloromethane, successively Add 4.02g (0.055mol) diethylamide, 19.1g (0.1mol) EDCHCl, it is to be dissolved completely after add 1.22g (0.01mol) DMAP, reacts 24h at room temperature.After reaction terminates, with 250mL dchloromethane reaction solutions, then use successively 0.1% HCl solution, saturation NaHCO3Solution and saturation NaCl solution are washed three times respectively, collect organic phase, are added anhydrous MgSO42h is dried, filtrate rotary evaporation is removed solvent by filtering, and vacuum drying obtains N, N- diethyl-N- positive 22 Alkylamide, its structural characterization is shown in1The chemical shift of each proton peak is found in spectrogram in H NMR spectras (Fig. 1), compound Ownership, and it is preferable to be coincide between each proton resonance peak integral area ratio and theoretical value, shows that the compound is successfully synthesized.
(2) by gained N, N- diethyl-N- n-docosane base acid amides is added in 500mL round-bottomed flasks, adds 100mL Tetrahydrofuran is dissolved, and 2 DEG C are cooled to until completely dissolved, LiAlH is added dropwise4Tetrahydrofuran solution, wherein fatty acid amide Mol ratio with metal hydride is 1：3.0,75 DEG C of reaction 24h are warming up to after completion of dropping, reaction terminates backward gained and reacted Sequentially add deionized water, 10%NaOH solution, deionized water in liquid reaction is quenched, then filtering reacting liquid, filtrate nothing Water MgSO4Dry, filtrate rotary evaporation is removed solvent, obtains N- (cis- 22 carbon -9- alkenyls)-N, N- diethyl by filtering Tertiary amine, its structural characterization is shown in1The chemical shift of each proton peak is found in spectrogram in H NMR spectras (Fig. 2), compound returns Category, and it is preferable to be coincide between each proton resonance peak integral area ratio and theoretical value, shows that the compound is successfully synthesized.
(3) by N- (cis- 22 carbon -9- alkenyls)-N, N- diethyl tertiary amine is mixed with mass concentration 15%HCl solution, The consumption of HCl solution is to make N- (cis- 22 carbon -9- alkenyls)-N, hydrionic mole in N- diethyl tertiary amine and HCl solution Than for 1：1,50 DEG C of stirring 24h obtains N- (cis- 22 carbon -9- alkenyls)-N to uniform, N- diethyl Amine from Tertiary Amine Hydrochloride, i.e., For the super Longer-chain surfactants of viscoplasticity.
(4) by N- (cis- 22 carbon -9- alkenyls)-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 consumption of HCl solution is to make N- (cis- 22 carbon -9- alkenyls)-N, N- diethyl tertiary ammonium salts Mass concentration of the hydrochlorate in mucic acid liquid is become is 3%.Pass through Haake torque rheometer and its supporting PZ39 rotors/rotating cylinder system 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 when temperature stabilization is at 150 DEG C, the viscosity of solutions display is relatively stable and more than 20mPas, The super Longer-chain surfactants of viscoplasticity obtained by showing the present embodiment have good temperature tolerance as thickening agent.
After test terminates, 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, its structural characterization is shown in1The chemical potential of each proton peak in H NMR spectras (Fig. 5), compound Shifting is found in spectrogram to coincide preferably between ownership, and each proton resonance peak integral area ratio and theoretical value, shows the change Degraded occurs under high-temperature strong acid environment, goes bad for compound, illustrates that its steady chemical structure preferably, meets high temperature, strong acid Application requirement under the adverse circumstances such as property.
Embodiment 2
This implementation and the difference of embodiment 1 are, in step (4), and the consumption of HCl solution is to make N- (cis- 22 Carbon -9- alkenyls)-N, mass concentration of the N- diethyl Amine from Tertiary Amine Hydrochloride in mucic acid liquid is become is 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 see figure 4.From fig. 4, it can be seen that when temperature stabilization is at 150 DEG C, the viscosity of solutions display is relatively stable and more than 20mPas, shows The super Longer-chain surfactants of viscoplasticity obtained by the present embodiment have good temperature tolerance as thickening agent.
Embodiment 3
(1) the positive behenic acids (popular name " arachidic acid ") of 17.03g (0.05mol) are weighed and are dissolved in dichloromethane, are sequentially added 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 terminates, with 250mL dchloromethane reaction solutions, then use successively 0.2% HCl solution, saturation NaHCO3Solution and saturation NaCl solution are washed three times respectively, collect organic phase, are added anhydrous MgSO4Dry, filtering, filtrate rotary evaporation is removed into solvent, vacuum drying obtains N, N- diethyl-N- n-docosane bases Acid amides, its structural characterization is shown in1The chemical shift of each proton peak is found in spectrogram in H NMR spectras (Fig. 5), compound returns Category, and it is preferable to be coincide between each proton resonance peak integral area ratio and theoretical value, shows that the compound is successfully synthesized.
(2) by gained N, N- diethyl-N- n-docosane base acid amides is added in 500mL round-bottomed flasks, adds 100mL Tetrahydrofuran is dissolved, and 0~5 DEG C is cooled to until completely dissolved, LiAlH is then added dropwise4Tetrahydrofuran solution, wherein fat The mol ratio of fat acid amides and metal hydride is 1：3.3,75 DEG C of reaction 30h are warming up to after completion of dropping.React after terminating progressively Add deionized water, the 15%NaOH aqueous solution, deionized water reaction is quenched.Then filtering reacting liquid, filtrate uses anhydrous MgSO4 Dry, filter, rotary evaporation removes solvent and obtains N, N- diethyl docosyl tertiary amines.Its structural characterization is shown in1HNMR spectrograms Ownership, and each proton resonance peak integral area ratio are found in the chemical shift of each proton peak in spectrogram in (Fig. 6), compound It is coincide between theoretical value preferable, shows that the compound is successfully synthesized.
(3) by N, N- diethyl docosyl tertiary amines are that 15%HCl solution is mixed with mass concentration, the use of HCl solution Measure to make N, N- diethyl docosyl tertiary amines are 1 with hydrionic mol ratio in HCl solution：1,50 DEG C of stirring 24h is to equal It is even, obtain N, as N- diethyl docosyl Amine from Tertiary Amine Hydrochloride, the super Longer-chain surfactants of viscoplasticity.
(4) by N, N- diethyl docosyl Amine from Tertiary Amine Hydrochloride is mixed with mass concentration 15%HCl solution, that is, is become Glactaric acid liquid, the consumption of HCl solution is to make N, mass concentration of the N- diethyl docosyl Amine from Tertiary Amine Hydrochloride in mucic acid liquid is become For 3%.Tested by Haake torque rheometer and its supporting PZ39 rotors/rotating cylinder system, be 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 Stable at 150 DEG C, the viscosity of solutions display is relatively stable and more than 30mPas, shows the present embodiment gained surfactant With preferable temperature tolerance.
After test terminates, acid solution is cooled to room temperature, there is white solid precipitation, filtered, N, N- bis- are obtained after freeze-drying Ethyl docosyl Amine from Tertiary Amine Hydrochloride, its structural characterization is shown in1H NMR spectras (Fig. 8).Pass through analysis of spectra 8, it is known that N, N- bis- Degraded occurs under high-temperature strong acid environment, goes bad for ethyl docosyl Amine from Tertiary Amine Hydrochloride, illustrates its steady chemical structure Property preferably, meet the application requirement under the adverse circumstances such as high temperature, highly acid.
Embodiment 4
This implementation and the difference of embodiment 3 are that acid solution is that mass concentration is 10% in step (3) and step (4) Acetic acid solution, the consumption of acetic acid solution is makes N in step (4), and N- diethyl docosyl tertiary amine acetate is becoming mucic acid Mass concentration in liquid is 4%.
Embodiment 5
(1) weigh 14.24g (0.05mol) n-octadecanoic acid (popular name " stearic acid ") and be dissolved in dichloromethane, 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 terminates, with 250mL dchloromethane reaction solutions, then use successively 0.5% HCl solution, saturation NaHCO3Solution and saturation NaCl solution are washed three times respectively, collect organic phase, are added anhydrous MgSO4Dry, filtering, filtrate rotary evaporation is removed into solvent, vacuum drying obtains N, N- diethyl-N- n-octadecane bases Acid amides, its structural characterization is shown in1The chemical shift of each proton peak is found in spectrogram in H NMR spectras (Fig. 8), compound returns Category, and it is preferable to be coincide between each proton resonance peak integral area ratio and theoretical value, shows that the compound is successfully synthesized.
(2) by gained N, N- diethyl-N- n-octadecane base acid amides is added in 500mL round-bottomed flasks, adds 100mL tetra- Hydrogen furans is dissolved, and 0~5 DEG C is cooled to until completely dissolved, LiAlH is added dropwise4Tetrahydrofuran solution, wherein fatty acid amide Mol ratio with metal hydride is 1：3.5,75 DEG C of reaction 36h are warming up to after completion of dropping.Reaction is gradually added after terminating Reaction is quenched for ionized water, the 20%NaOH aqueous solution, deionized water.Then filtering reacting liquid, filtrate is dried with anhydrous MgSO4, Filtering, obtains N, positive 18 tertiary amine of N- diethyl, its structural characterization is shown in by filtrate rotary evaporation removing solvent1H NMR spectras (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 is coincide between theoretical value preferable, shows that the compound is successfully synthesized.
(3) by N, positive 18 tertiary amine of N- diethyl is mixed with the concentration of quality for 15%HCl solution, the consumption of HCl solution To make N, positive 18 tertiary amine of N- diethyl is 1 with hydrionic mol ratio in HCl solution:1,50 DEG C of stirring 24h is obtained 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 well mixed with mass concentration 15%HCl solution, that is, is become Glactaric acid liquid, the consumption of HCl solution to make N, mass concentration of positive 18 Amine from Tertiary Amine Hydrochloride of N- diethyl in mucic acid liquid is become into 3%.Tested by Haake torque rheometer and its supporting PZ39 rotors/rotating cylinder system, be 100s in shear rate-1 As a result the viscosity that measurement gained becomes mucic acid liquid is shown in Figure 11 with temperature, the variation relation of time.It can be seen from figure 11 that working as temperature Stabilization is at 150 DEG C, and the viscosity of solutions display is relatively stable and more than 20mPas.
After test terminates, acid solution is cooled to room temperature, there is white solid precipitation, filtered, N, N- bis- are obtained after freeze-drying Positive 18 Amine from Tertiary Amine Hydrochloride of ethyl, its structural characterization is shown in1H NMR spectras (Figure 12).Pass through analysis of spectra, N, N- diethyl Degraded occurs under high-temperature strong acid environment, goes bad for positive 18 Amine from Tertiary Amine Hydrochloride, shows its steady chemical structure preferably, full Application requirement under the adverse circumstances such as sufficient high temperature, highly acid.
Embodiment 6
This implementation and the difference of embodiment 5 are that acid solution is that mass concentration is 20% in step (3) and step (4) Sulfuric acid solution, the consumption of sulfuric acid solution is makes N, matter of positive 18 tertiary ammonium salt of N- diethyl in mucic acid liquid is become in step (4) It is 5% to measure concentration.

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 the saturation with 18~22 carbon atoms or unsaturated alkane, R2For H atom, or with 2~4 carbon The saturated alkane of 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-、CH3COO-In one kind.
2. the preparation method of overlength chain viscoelastic surfactant described in claim 1, it is characterised in that step is as follows：
(1) aliphatic acid is dissolved in dichloromethane, adds organic amine, carbonyl activation agent, catalyst is added until completely dissolved DMAP 24~36h of stirring reaction, reaction end addition dchloromethane reaction solution, then use successively at room temperature 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 MgSO4Filtered after drying, filtrate removing solvent is obtained into fatty acid amide；
Wherein, the consumption of dichloromethane should be completely dissolved aliphatic acid, organic amine, carbonyl-activating reagent and catalyst before reacting； The mol ratio of organic amine and aliphatic acid is (1.1~1.5)：1；The mol ratio of catalyst DMAP and aliphatic acid is (0.2~0.5)：1；The mol ratio of carbonyl activation agent and aliphatic 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 Into 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 1：70~150 DEG C of 24~36h of reaction are warming up to after (3.0~3.5), completion of dropping, reaction terminates backward gained and reacted Sequentially add deionized water, the NaOH solution of mass concentration 10%~20%, deionized water in liquid reaction is quenched, then mistake Filter, gained filtrate uses anhydrous MgSO4Filtered again after drying, gained filtrate removing solvent will be filtered again and obtains fat tertiary amine；
(3) acid solution of fat tertiary amine and mass concentration 10%~20% is mixed and stirred for uniformly, protonating fat tertiary amine, i.e., Form overlength chain viscoelastic surfactant, the consumption of the acid solution is fat tertiary amine and hydrionic mol ratio in acid solution is 1： 1。
3. the preparation method of high temperature resistant overlength chain viscoelastic surfactant according to claim 2, it is characterised in that described Aliphatic acid is at least one of saturation or unsaturated alkyl aliphatic 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 It is at least one of saturated alkyl organic amine with 4~8 carbon atoms to state organic amine.
5. the preparation method of high temperature resistant overlength chain viscoelastic surfactant according to Claims 2 or 3, it is characterised in that institute Carbonyl activation agent is stated for 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt hydrochlorate, dicyclohexylcarbodiimide, N, N- At least one of DIC.
6. the preparation method of high temperature resistant overlength chain viscoelastic surfactant according to Claims 2 or 3, it is characterised in that institute Metal hydride is stated for 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 Acid solution is stated for 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 the uniform progress at 50~80 DEG C.
9. high temperature resistant overlength chain viscoelastic surfactant described in claim 1 is used as the application for becoming glutinous gelling agent for acid fluid.
10. apply according to claim 9, it is characterised in that by the high temperature resistant overlength chain viscoelastic surfactant and matter Measure concentration for 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 consumption makes to obtain Become the mass concentration of the super Longer-chain surfactants of viscoplasticity in mucic acid liquid into 3%~5%.
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