CN110013794A - Temperature-resistant and anti-salt type anacardol zwitterionic surfactant and its preparation method and application - Google Patents
Temperature-resistant and anti-salt type anacardol zwitterionic surfactant and its preparation method and application Download PDFInfo
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- CN110013794A CN110013794A CN201810022597.8A CN201810022597A CN110013794A CN 110013794 A CN110013794 A CN 110013794A CN 201810022597 A CN201810022597 A CN 201810022597A CN 110013794 A CN110013794 A CN 110013794A
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Abstract
The present invention provides a kind of temperature-resistant and anti-salt type anacardol zwitterionic surfactants and its preparation method and application, the present invention is using biomass anacardol as raw material, by etherificate, amination and quaternization reaction, a kind of novel anacardol zwitterionic surfactant (I) with special construction is prepared:In the preparation method, by the suitable selection of catalyst system and dicyandiamide solution, to improve the yield of purpose product；The anacardol zwitterionic surfactant has good heat-resistant salt-resistant performance and interfacial activity, and aqueous solution can form ultralow interfacial tension with crude oil, have a good application prospect in the severe oil reservoir of high temperature, high salinity.
Description
Technical field
The present invention relates to surfactant fields, relate more particularly to a kind of temperature-resistant and anti-salt type anacardol amphoteric ion surface
Activating agent and its preparation method and application belongs to organic chemical synthesis technical field.
Background technique
Surfactant with amphiphilic structure can preferably reduce oil water interfacial tension, change the emulsifiability of crude oil,
Residual oil saturation is reduced to improve displacement efficiency, and then improves the recovery ratio of crude oil.Surfactant flooding technology has succeeded
The attention in terms of tertiary oil recovery is caused, gradually from laboratory research gradually to field application transition.
Currently, methods have been developed a variety of surfactants for being used for the displacement of reservoir oil, wherein heavy alkylbenzene sulfonate and
Two anionoid type surfactant of petroleum sulfonate is the most oil displacement surfactant of domestic major field use.However,
Heatproof, the salt tolerance of this kind of anionic surfactant are poor；For severe oil reservoir, not only reservoir temperature is relatively high, and
And formation water salinity is higher, especially calcium and magnesium ion content.Anionic surfactant is easy in high temperature and high salt condition flowering structure
It changes, does not have applications well effect.Amphoteric ionic surfactant has good heatproof, anti-salt property, to height
Warm, high salinity severe oil reservoir has good adaptability, and its interfacial tension is smaller to the dependence of alkali, especially
Betaine type amphoteric ionic surfactant becomes one of research hotspot in recent years.
The patent application of CN105983370A discloses a kind of saturation anacardol beet alkali surface activator (II) and preparation
Methods and applications, for the betaine type amphoteric surfactant at 85 DEG C, the interfacial tension of aqueous solution and oil from Shengli oil field is reachable
To 10-2mN/m。
The patent application of CN10179827413B discloses a kind of zwitterionic surfactant answering in tertiary oil recovery
With the preparation method and application method of the, surfactant, which is being lower than 80 DEG C of condition,
Oil water interfacial tension can be reduced to can reach 10-2mN/m。
The patent application of CN106268494A discloses a kind of efficient zwitterionic ionic surface active agent and its synthetic method, should
The hydrophobic grouping of zwitterionic surfactant is perfluoroalkyl chain.
As described above, although researcher has been developed for a variety of amphoteric ionic surfactants, these surfaces
Activating agent remains many defects, such as the problems such as temperature tolerance and salt tolerance are to be improved, interfacial tension is higher.
In view of this, the present inventor is intended to develop a kind of temperature-resistant anti-salt by the investigation and experimental exploring of existing literature
Type anacardol zwitterionic surfactant and its preparation method and application efficiently against of the existing technology so as to asking
Topic greatly reduces oil water interfacial tension, and has preferable resistance to mild anti-salt property, and then sufficiently meet oil field oil-displacement surface
The widespread demand of activating agent has good industrial applications potentiality and promotional value.
Summary of the invention
For above-mentioned problems, the present inventor is after having paid a large amount of creative experiments and having explored, through too deep
Enter research and propose a kind of temperature-resistant and anti-salt type anacardol zwitterionic surfactant and its preparation method and application, thus complete
At the present invention.Specifically:
The present invention provides a kind of temperature-resistant and anti-salt type anacardol zwitterionic surfactant, in which: the temperature-resistant and anti-salt type
Anacardol zwitterionic surfactant has the structure as shown in formula (I):
The present invention also provides a kind of preparation methods of temperature-resistant and anti-salt type anacardol zwitterionic surfactant, are above-mentioned
The preparation method of temperature-resistant and anti-salt type anacardol zwitterionic surfactant, comprising the following steps:
(1) preparation of anacardol chloropharin ether:
Anacardol, epoxychloropropane and short chain alcohol are added into reactor, at room temperature stirring and dissolving, wherein anacardol and ring
The molar ratio of oxygen chloropropane is 1:1~1:8；Then the short chain alcohol solution of phase transfer catalyst is added, wherein phase transfer catalyst
Dosage be anacardol dosage 1wt%~5wt% phase transfer catalyst short chain alcohol solution, the constant temperature at 60~100 DEG C
Reaction 4~10 hours；End of reaction, vacuum distillation are removed solvent and unreacted epoxychloropropane, are repeatedly washed using distilled water
Product of distillation is washed, phase transfer catalyst is removed, obtains anacardol chloropharin ether；
(2) preparation of anacardol tertiary amine:
Diphenylamines and acid binding agent are dissolved into short chain alcohol, the alcoholic solution of the anacardol chloropharin ether is slowly added dropwise, wherein
The molar ratio of diphenylamines and anacardol chloropharin ether is 1:1~8:1, and the dosage of acid binding agent is the 1wt% of anacardol chloropharin ether dosage
~5wt%；It is added dropwise, increases reaction temperature to 40~80 DEG C, isothermal reaction 5-10 hours；Reaction terminates, with vacuum distillation
Remove solvent；Gained product of distillation uses the saturated common salt water washing of benzene and heat multiple respectively, is then washed with distilled water to again
Property, the water being finally evaporated under reduced pressure in removing system obtains anacardol tertiary amine；
(3) preparation of temperature-resistant and anti-salt type anacardol zwitterionic surfactant:
The short chain alcohol solution of acid binding agent and anacardol tertiary amine is added in reactor, 3- is slowly added dropwise at 30~80 DEG C
The aqueous solution of chlorine-2-hydroxyl propanesulfonate, wherein the molar ratio of 3- chlorine-2-hydroxyl propanesulfonate and anacardol tertiary amine be 1:1~
6:1；It is added dropwise, isothermal reaction 5~12 hours at 50~95 DEG C, end of reaction, vacuum distillation removes solvent, gained distillation
Product is washed repeatedly with ethyl acetate, with ethyl alcohol recrystallization, obtains temperature-resistant and anti-salt type anacardol zwitterionic surfactant.
The preparation method of temperature-resistant and anti-salt type anacardol zwitterionic surfactant of the present invention, in which: described short
Chain alcohol is preferably one or more of methanol, ethyl alcohol, isopropanol and isobutanol.
The preparation method of temperature-resistant and anti-salt type anacardol zwitterionic surfactant of the present invention, in which: the phase
Transfer catalyst is preferably tetrabutylammonium bromide, benzyltriethylammoinium chloride, tetrabutylammonium chloride, trimethyl chlorination
Ammonium or tetradecyl trimethyl ammonium chloride.
The preparation method of temperature-resistant and anti-salt type anacardol zwitterionic surfactant of the present invention, in which: described to tie up
Sour agent is preferably triethylamine, pyridine or sodium hydroxide.
The present invention also provides the temperature-resistant and anti-salt type anacardol zwitterionic surfactants in high temperature, high salinity
Application in severe oil reservoir oil displacement, wherein the temperature-resistant and anti-salt type anacardol zwitterionic surfactant be used alone or with
Additive compound uses, and temperature-resistant and anti-salt type anacardol zwitterionic surfactant aqueous solution and crude oil form ultralow interface
Power.
Application of the present invention, wherein the additive is preferably inorganic salts, sodium bicarbonate, sodium hydroxide and poly- third
One or more of acrylamide.
The present invention can be with details are as follows:
First aspect, it is described resistance to the present invention provides a kind of temperature-resistant and anti-salt type anacardol zwitterionic surfactant
Warm anti-salt type anacardol zwitterionic surfactant has the structure as shown in formula (I).
The second aspect, the present invention provides a kind of preparation sides of temperature-resistant and anti-salt type anacardol zwitterionic surfactant
Method, specifically includes the following steps:
(1) preparation of anacardol chloropharin ether:
The reactional equation of this step is as follows:
Anacardol, epoxychloropropane and short chain alcohol are added into reactor, at room temperature stirring and dissolving, wherein anacardol and ring
The molar ratio of oxygen chloropropane is 1:1~1:8；Then the short chain alcohol that the phase transfer catalyst that mass fraction is 1%~5% is added is molten
Liquid, isothermal reaction 4~10 hours at 60~100 DEG C；End of reaction, vacuum distillation remove solvent and unreacted epoxy chloropropionate
Alkane repeatedly washs product of distillation using distilled water, removes phase transfer catalyst, obtain anacardol chloropharin ether.
(2) preparation of anacardol tertiary amine:
The reactional equation of this step is as follows:
Diphenylamines and acid binding agent are dissolved into short chain alcohol, the alcoholic solution of anacardol chloropharin ether is slowly added dropwise, wherein hexichol
The molar ratio of amine and anacardol chloropharin ether is 1:1~8:1, and the dosage of acid binding agent is 1%~5%；It is added dropwise, increases reaction temperature
Degree is to 40~80 DEG C, isothermal reaction 5-10 hours；Reaction terminates, and removes solvent with vacuum distillation；Gained product of distillation is used respectively
The saturated common salt water washing of benzene and heat is multiple, is then washed with distilled water to neutrality again, is finally evaporated under reduced pressure in removing system
Water obtains anacardol tertiary amine.
(3) preparation of temperature-resistant and anti-salt type anacardol zwitterionic surfactant:
The reactional equation of this step is as follows:
The short chain alcohol solution of acid binding agent and anacardol tertiary amine is added in reactor, 3- is slowly added dropwise at 30~80 DEG C
The aqueous solution of chlorine-2-hydroxyl propanesulfonate, wherein the molar ratio of 3- chlorine-2-hydroxyl propanesulfonate and anacardol tertiary amine be 1:1~
6:1；It is added dropwise, isothermal reaction 5~12 hours at 50~95 DEG C, end of reaction, vacuum distillation removes solvent, gained distillation
Product is washed repeatedly with ethyl acetate, with ethyl alcohol recrystallization, obtains temperature-resistant and anti-salt type anacardol zwitterionic surfactant.
In synthetic method of the present invention, the short chain alcohol is one in methanol, ethyl alcohol, isopropanol and isobutanol
Kind is several.
In synthetic method of the present invention, the phase transfer catalyst is tetrabutylammonium bromide, benzyl triethyl ammonium
One of ammonium chloride, tetrabutylammonium chloride, dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride.
In synthetic method of the present invention, the acid binding agent is one of triethylamine, pyridine, sodium hydroxide.
In synthetic method of the present invention, the molar ratio of the anacardol and epoxychloropropane is 1:1~1:8, example
It such as can be 1:2,1:4,1:6 or 1:8.
In synthetic method of the present invention, the addition phase transfer catalyst mass fraction is 1%~5%, such as
It can be 1.5%, 3%, 4% or 5%.
In synthetic method of the present invention, the reaction temperature of the anacardol and epoxychloropropane is 60~100 DEG C,
It may be, for example, 60 DEG C, 75 DEG C, 85 DEG C or 95 DEG C.
In synthetic method of the present invention, the reaction time of the anacardol and epoxychloropropane is 4~10 hours,
It may be, for example, 4,6,8 or 10.
In synthetic method of the present invention, the molar ratio of the diphenylamines and anacardol chloropharin ether is 1:1~8:1,
It may be, for example, 1:2,1:4,1:6 or 1:8.
In synthetic method of the present invention, the addition acid binding agent mass fraction is 1%~5%, be may be, for example,
1.5%, 3.5%, 4% or 5%.
In synthetic method of the present invention, the reaction temperature of the diphenylamines and anacardol chloropharin ether is 40~80
DEG C, it may be, for example, 40 DEG C, 55 DEG C, 65 DEG C or 80 DEG C.
In synthetic method of the present invention, the reaction time of the diphenylamines and anacardol chloropharin ether is 5~10 small
When, it may be, for example, 5,6,8 or 10.
In synthetic method of the present invention, the molar ratio of the 3- chlorine-2-hydroxyl propanesulfonate and anacardol tertiary amine
For 1:1~6:1,2:1,3:1,5:1 or 6:1 may be, for example,.
In synthetic method of the present invention, the dropping temperature of the aqueous solution of the 3- chlorine-2-hydroxyl propanesulfonate is
At 30~80 DEG C, it may be, for example, 30 DEG C, 50 DEG C, 60 DEG C or 80 DEG C.
In synthetic method of the present invention, the 3- chlorine-2-hydroxyl propanesulfonate reacts temperature with anacardol tertiary amine
Degree is 50~95 DEG C, may be, for example, 50 DEG C, 55 DEG C, 65 DEG C or 90 DEG C.
In synthetic method of the present invention, the 3- chlorine-2-hydroxyl propanesulfonate is with anacardol tertiary amine when reacting
Between be 5~12 hours, may be, for example, 6,8,10 or 12.
In terms of third, the present invention provides a kind of application of temperature-resistant and anti-salt type anacardol zwitterionic surfactant,
The temperature-resistant and anti-salt type anacardol zwitterionic surfactant can be used for the severe oil reservoir oil displacement of high temperature, high salinity；And
The temperature-resistant and anti-salt type anacardol zwitterionic surfactant is used alone or uses with additive compound, and aqueous solution can
Ultralow interfacial tension is formed with crude oil.
In application of the present invention, the additive is inorganic salts, sodium bicarbonate, sodium hydroxide, polyacrylamide
One or more of amine.
In conclusion technical solution of the present invention has many advantages, such as, to have in industrialized production and application aspect
Good application potential and prospect.
Detailed description of the invention
Fig. 1: when temperature is 45 ± 5 DEG C, salinity is 32000mg/L, temperature-resistant and anti-salt type anacardol amphoteric ion surface
Relation curve between activator solution and the static interfaces tension and surfactant concentration of crude oil；
Fig. 2: when temperature is 85 ± 5 DEG C, salinity is 32000mg/L, temperature-resistant and anti-salt type anacardol amphoteric ion surface
Relation curve between activator solution and the static interfaces tension and surfactant concentration of crude oil is shown in；
Fig. 3: when temperature is 65 ± 5 DEG C, salinity is 40000mg/L, temperature-resistant and anti-salt type anacardol amphoteric ion surface
Relation curve between activator solution and the static interfaces tension and surfactant concentration of crude oil；
Fig. 4: when temperature is 45 ± 5 DEG C, naoh concentration 1.2%, salinity are 32000mg/L, temperature-resistant anti-salt
Relationship between type anacardol zwitterionic surfactant solution and the static interfaces tension and surfactant concentration of crude oil
Curve.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
Embodiment 1
The preparation of temperature-resistant and anti-salt type anacardol zwitterionic surfactant:
Step 1: into reactor be added 5.80g (0.02mol) anacardol, 3.70g (0.04mol) epoxychloropropane and
80mL ethyl alcohol, at room temperature stirring and dissolving；Then the ethanol solution for the tetrabutylammonium bromide that 20mL mass fraction is 3% is added,
Isothermal reaction 6 hours at 80 DEG C；End of reaction, vacuum distillation removes solvent and unreacted epoxychloropropane, using distilled water
Repeatedly washing product of distillation removes tetrabutylammonium bromide, obtains anacardol chloropharin ether, yield 95.3%.
Step 2: being added into reactor 13.52g (0.08mol) diphenylamines and 2.02g (0.02mol) triethylamine is molten
The ethanol solution that 20mL contains 7.65g (0.02mol) anacardol chloropharin ether is slowly added dropwise into 50mL ethyl alcohol in solution；It is added dropwise,
Reaction temperature is increased to 65 DEG C, isothermal reaction 8 hours；Reaction terminates, and vacuum distillation removes solvent；Gained product of distillation is used respectively
The saturated common salt water washing of benzene and heat three times, is then washed with distilled water to neutrality again, is finally evaporated under reduced pressure in removing system
Water obtains anacardol tertiary amine, yield 82.2%.
Step 3: 10.30g (0.02mol) anacardol tertiary amine is dissolved into 80mL ethyl alcohol, it is added 2.02g (0.02mol)
The aqueous solution 20mL of 7.86g (0.04mol) 3- chlorine-2-hydroxyl propanesulfonate is slowly added dropwise in triethylamine at 40 DEG C；It drips
Finish, isothermal reaction 10 hours at 65 DEG C, end of reaction, vacuum distillation removes solvent, gained product of distillation 100mL acetic acid second
Ester washing repeatedly, with ethyl alcohol recrystallization, obtains temperature-resistant and anti-salt type anacardol zwitterionic surfactant, yield 80.4%.
When temperature is 45 ± 5 DEG C, salinity is 32000mg/L, temperature-resistant and anti-salt type anacardol amphoteric ion surface-active
Relation curve between agent solution and the static interfaces tension and surfactant concentration of crude oil is shown in Fig. 1.As shown in Figure 1, in height
Under salinity, when concentration is greater than 1g/L, the interface of temperature-resistant and anti-salt type anacardol zwitterionic surfactant solution and crude oil
Tension has reached ultralow interfacial tension (10-3mN/m)。
Embodiment 2
The preparation of temperature-resistant and anti-salt type anacardol zwitterionic surfactant:
Step 1: into reactor be added 5.80g (0.02mol) anacardol, 3.70g (0.04mol) epoxychloropropane and
80mL methanol, at room temperature stirring and dissolving；Then the methanol for the dodecyl trimethyl ammonium chloride that 20mL mass fraction is 3% is added
Solution, isothermal reaction 10 hours at 60 DEG C；End of reaction, vacuum distillation remove solvent and unreacted epoxychloropropane, adopt
Product of distillation is repeatedly washed with distilled water, dodecyl trimethyl ammonium chloride is removed, obtains anacardol chloropharin ether, yield is
93.7%.
Step 2: being added into reactor by 13.52g (0.08mol) diphenylamines and 1.58g (0.02mol) pyridinium dissolution
Into 50mL methanol, the methanol solution that 20mL contains 7.65g (0.02mol) anacardol chloropharin ether is slowly added dropwise；It is added dropwise, rises
High reaction temperature is to 75 DEG C, isothermal reaction 8 hours；Reaction terminates, and vacuum distillation removes solvent；Gained product of distillation uses benzene respectively
Three times with hot saturated common salt water washing, it is then washed with distilled water to neutrality again, the water being finally evaporated under reduced pressure in removing system,
Obtain anacardol tertiary amine, yield 82.9%.
Step 3: 10.30g (0.02mol) anacardol tertiary amine is dissolved into 80mL methanol, it is added 1.58g (0.02mol)
The aqueous solution 20mL of 7.86g (0.04mol) 3- chlorine-2-hydroxyl propanesulfonate is slowly added dropwise in pyridine at 50 DEG C；It is added dropwise,
Isothermal reaction 6 hours at 65 DEG C, end of reaction, vacuum distillation remove solvent, and gained product of distillation is washed with 100mL ethyl acetate
It washs repeatedly, with ethyl alcohol recrystallization, obtains temperature-resistant and anti-salt type anacardol zwitterionic surfactant, yield 81.5%.
When temperature is 85 ± 5 DEG C, salinity is 32000mg/L, temperature-resistant and anti-salt type anacardol amphoteric ion surface-active
Relation curve between agent solution and the static interfaces tension and surfactant concentration of crude oil is shown in Fig. 2.As shown in Figure 2, in height
Under mild high salinity, when concentration is greater than 1g/L, temperature-resistant and anti-salt type anacardol zwitterionic surfactant solution and crude oil
Interfacial tension reached ultralow interfacial tension (10-3MN/m), interfacial tension when and interfacial tension is lower than 45 ± 5 DEG C.
Embodiment 3
The preparation of temperature-resistant and anti-salt type anacardol zwitterionic surfactant:
Step 1: into reactor be added 5.80g (0.02mol) anacardol, 11.10g (0.12mol) epoxychloropropane and
80mL isopropanol, at room temperature stirring and dissolving；Then the different of the tetradecyl trimethyl ammonium chloride that 20mL mass fraction is 2% is added
Propanol solution, isothermal reaction 8 hours at 80 DEG C；End of reaction, vacuum distillation remove solvent and unreacted epoxychloropropane,
Product of distillation is repeatedly washed using distilled water, tetradecyl trimethyl ammonium chloride is removed, obtains anacardol chloropharin ether, yield is
81.5%.
6.76g (0.04mol) diphenylamines and 1.58g (0.02mol) pyridinium dissolution are arrived step 2: being added into reactor
In 50mL isopropanol, the aqueous isopropanol that 20mL contains 7.65g (0.02mol) anacardol chloropharin ether is slowly added dropwise；It is added dropwise,
Reaction temperature is increased to 50 DEG C, isothermal reaction 5 hours；Reaction terminates, and vacuum distillation removes solvent；Gained product of distillation is used respectively
The saturated common salt water washing of benzene and heat three times, is then washed with distilled water to neutrality again, is finally evaporated under reduced pressure in removing system
Water obtains anacardol tertiary amine, yield 78.7%.
Step 3: 10.30g (0.02mol) anacardol tertiary amine is dissolved into 80mL isopropanol, 1.58g is added
The aqueous solution 20mL of 19.66g (0.10mol) 3- chlorine-2-hydroxyl propanesulfonate is slowly added dropwise in (0.02mol) pyridine at 50 DEG C；
It is added dropwise, isothermal reaction 6 hours at 80 DEG C, end of reaction, vacuum distillation removes solvent, gained product of distillation 100mL
Ethyl acetate washing repeatedly, with ethyl alcohol recrystallization, obtains temperature-resistant and anti-salt type anacardol zwitterionic surfactant, yield is
91.5%.
When temperature is 45 ± 5 DEG C, salinity is 32000mg/L, temperature-resistant and anti-salt type anacardol amphoteric ion surface-active
Relation curve between agent solution and the static interfaces tension and surfactant concentration of crude oil is shown in Fig. 1.As shown in Figure 1, in height
Under salinity, when concentration is greater than 1g/L, the interface of temperature-resistant and anti-salt type anacardol zwitterionic surfactant solution and crude oil
Tension has reached ultralow interfacial tension (10-3mN/m)。
Embodiment 4
The preparation of temperature-resistant and anti-salt type anacardol zwitterionic surfactant:
Step 1: into reactor be added 5.80g (0.02mol) anacardol, 9.25g (0.10mol) epoxychloropropane and
80mL ethyl alcohol, at room temperature stirring and dissolving；Then the ethanol solution for the tetrabutylammonium chloride that 20mL mass fraction is 5% is added,
Isothermal reaction 8 hours at 60 DEG C；End of reaction, vacuum distillation removes solvent and unreacted epoxychloropropane, using distilled water
Repeatedly washing product of distillation removes tetrabutylammonium chloride, obtains anacardol chloropharin ether, yield 83.3%.
Step 2: being added into reactor by 13.52g (0.08mol) diphenylamines and 1.58g (0.02mol) pyridinium dissolution
Into 50mL ethyl alcohol, the ethanol solution that 20mL contains 7.65g (0.02mol) anacardol chloropharin ether is slowly added dropwise；It is added dropwise, rises
High reaction temperature is to 60 DEG C, isothermal reaction 6 hours；Reaction terminates, and vacuum distillation removes solvent；Gained product of distillation uses benzene respectively
Three times with hot saturated common salt water washing, it is then washed with distilled water to neutrality again, the water being finally evaporated under reduced pressure in removing system,
Obtain anacardol tertiary amine, yield 82.6%.
Step 3: 10.30g (0.02mol) anacardol tertiary amine is dissolved into 80mL ethyl alcohol, it is added 1.58g (0.02mol)
The aqueous solution 20mL of 15.72g (0.08mol) 3- chlorine-2-hydroxyl propanesulfonate is slowly added dropwise in pyridine at 50 DEG C；It is added dropwise,
Isothermal reaction 8 hours at 80 DEG C, end of reaction, vacuum distillation remove solvent, and gained product of distillation is washed with 100mL ethyl acetate
It washs repeatedly, with ethyl alcohol recrystallization, obtains temperature-resistant and anti-salt type anacardol zwitterionic surfactant, yield 92.9%.
When temperature is 65 ± 5 DEG C, salinity is 40000mg/L, temperature-resistant and anti-salt type anacardol amphoteric ion surface-active
Relation curve between agent solution and the static interfaces tension and surfactant concentration of crude oil is shown in Fig. 3.From the figure 3, it may be seen that in height
Under mild high salinity, when concentration is greater than 1g/L, temperature-resistant and anti-salt type anacardol zwitterionic surfactant solution and crude oil
Interfacial tension reached ultralow interfacial tension (10-3MN/m), and interfacial tension is higher than interface when salinity is 32000mg/L
Tension.
Embodiment 5
The preparation of temperature-resistant and anti-salt type anacardol zwitterionic surfactant:
Step 1: into reactor be added 5.80g (0.02mol) anacardol, 5.45g (0.06mol) epoxychloropropane and
80mL ethyl alcohol, at room temperature stirring and dissolving；Then the isobutanol solution for the tetrabutylammonium bromide that 20mL mass fraction is 3% is added,
Isothermal reaction 8 hours at 70 DEG C；End of reaction, vacuum distillation removes solvent and unreacted epoxychloropropane, using distillation
Water repeatedly washs product of distillation, removes tetrabutylammonium bromide, obtains anacardol chloropharin ether, yield 81.5%.
Step 2: being added into reactor by 13.52g (0.08mol) diphenylamines and 0.80g (0.02mol) sodium hydroxide
It is dissolved into 50mL methanol, the isobutanol solution that 20mL contains 7.65g (0.02mol) anacardol chloropharin ether is slowly added dropwise；It is added dropwise
It finishes, increases reaction temperature to 50 DEG C, isothermal reaction 6 hours；Reaction terminates, and vacuum distillation removes solvent；Gained product of distillation
Respectively three times with the saturated common salt water washing of benzene and heat, it is then washed with distilled water to neutrality again, finally vacuum distillation removes body
Water in system obtains anacardol tertiary amine, yield 82.6%.
Step 3: 10.30g (0.02mol) anacardol tertiary amine is dissolved into isobutanol in 80mL, 1.58g is added
The aqueous solution 20mL of 7.86g (0.04mol) 3- chlorine-2-hydroxyl propanesulfonate is slowly added dropwise in (0.02mol) pyridine at 50 DEG C；
It is added dropwise, isothermal reaction 8 hours at 95 DEG C, end of reaction, vacuum distillation removes solvent, gained product of distillation 100mL
Ethyl acetate washing repeatedly, with ethyl alcohol recrystallization, obtains temperature-resistant and anti-salt type anacardol zwitterionic surfactant, yield is
91.9%.
When temperature is 45 ± 5 DEG C, naoh concentration 1.2%, salinity are 32000mg/L, temperature-resistant and anti-salt type waist
Relation curve between fruit phenol zwitterionic surfactant solution and the static interfaces tension and surfactant concentration of crude oil
See Fig. 4.As shown in Figure 4, under high salinity, when concentration is greater than 1g/L, temperature-resistant and anti-salt type anacardol amphoteric ion surface is living
The interfacial tension of property agent solution and crude oil has reached ultralow interfacial tension (10-3MN/m), the addition of alkali, oil-water interfaces and in system
Tension reduces.
Embodiment 6
The preparation of temperature-resistant and anti-salt type anacardol zwitterionic surfactant:
Step 1: into reactor be added 5.80g (0.02mol) anacardol, 14.80g (0.16mol) epoxychloropropane and
80mL mixed alcohol (isopropanol and ethyl alcohol molar ratio be 1:1), at room temperature stirring and dissolving；Then it is 1% that 20mL mass fraction, which is added,
Tetradecyl trimethyl ammonium chloride mixing alcoholic solution (isopropanol and ethyl alcohol molar ratio be 1:1), the isothermal reaction 6 at 80 DEG C
Hour；End of reaction, vacuum distillation remove solvent and unreacted epoxychloropropane, and distillation is repeatedly washed using distilled water and is produced
Object removes tetradecyl trimethyl ammonium chloride, obtains anacardol chloropharin ether, yield 84.6%.
3.38g (0.02mol) diphenylamines and 1.58g (0.02mol) pyridinium dissolution are arrived step 2: being added into reactor
In 50mL isopropanol, the aqueous isopropanol that 20mL contains 7.65g (0.02mol) anacardol chloropharin ether is slowly added dropwise；It is added dropwise,
Reaction temperature is increased to 50 DEG C, isothermal reaction 5 hours；Reaction terminates, and vacuum distillation removes solvent；Gained product of distillation is used respectively
The saturated common salt water washing of benzene and heat three times, is then washed with distilled water to neutrality again, is finally evaporated under reduced pressure in removing system
Water obtains anacardol tertiary amine, yield 76.4%.
Step 3: 10.30g (0.02mol) anacardol tertiary amine is dissolved into 80mL isopropanol, 1.58g is added
The aqueous solution 20mL of 3.93g (0.02mol) 3- chlorine-2-hydroxyl propanesulfonate is slowly added dropwise in (0.02mol) pyridine at 50 DEG C；
It is added dropwise, isothermal reaction 5 hours at 95 DEG C, end of reaction, vacuum distillation removes solvent, gained product of distillation 100mL
Ethyl acetate washing repeatedly, with ethyl alcohol recrystallization, obtains temperature-resistant and anti-salt type anacardol zwitterionic surfactant, yield is
88.2%.
Temperature-resistant and anti-salt type anacardol zwitterionic surfactant and sodium bicarbonate, sodium hydroxide are re-dubbed oil displacement agent water
Solution, wherein anacardol zwitterionic surfactant dosage is 1wt%, sodium hydroxide 10wt%, and sodium bicarbonate is
5wt%, the solution system can be compounded with the oilfield sewage of salinity 12000mg/L or more, can be substantially reduced the interface of crude oil
Power.
Embodiment 7
The preparation of temperature-resistant and anti-salt type anacardol zwitterionic surfactant:
Step 1: into reactor be added 5.80g (0.02mol) anacardol, 7.40g (0.08mol) epoxychloropropane and
80mL mixed alcohol (methanol and ethyl alcohol molar ratio be 1:1), at room temperature stirring and dissolving；Then it is 5% that 20mL mass fraction, which is added,
The mixing alcoholic solution (methanol and ethyl alcohol molar ratio be 1:1) of tetradecyl trimethyl ammonium chloride, isothermal reaction 10 is small at 80 DEG C
When；End of reaction, vacuum distillation remove solvent and unreacted epoxychloropropane, repeatedly wash product of distillation using distilled water,
Tetradecyl trimethyl ammonium chloride is removed, anacardol chloropharin ether, yield 87.1% are obtained.
3.38g (0.02mol) diphenylamines and 1.58g (0.02mol) pyridinium dissolution are arrived step 2: being added into reactor
In 50mL mixed alcohol (the same to first step), the mixing alcoholic solution that 20mL contains 30.6g (0.08mol) anacardol chloropharin ether is slowly added dropwise
(the same to first step)；It is added dropwise, increases reaction temperature to 50 DEG C, isothermal reaction 5 hours；Reaction terminates, and vacuum distillation removes molten
Agent；Gained product of distillation uses the saturated common salt water washing of benzene and heat to be then washed with distilled water to neutrality again, finally three times respectively
The water being evaporated under reduced pressure in removing system, obtains anacardol tertiary amine, yield 79.7%.
Step 3: 10.30g (0.02mol) anacardol tertiary amine is dissolved into 80mL isopropanol, 1.58g is added
The aqueous solution 20mL of 31.44g (0.16mol) 3- chlorine-2-hydroxyl propanesulfonate is slowly added dropwise in (0.02mol) pyridine at 50 DEG C；
It is added dropwise, isothermal reaction 12 hours at 50 DEG C, end of reaction, vacuum distillation removes solvent, gained product of distillation 100mL
Ethyl acetate washing repeatedly, with ethyl alcohol recrystallization, obtains temperature-resistant and anti-salt type anacardol zwitterionic surfactant, yield is
90.1%.
By temperature-resistant and anti-salt type anacardol zwitterionic surfactant and sodium chloride, that sodium hydroxide is re-dubbed oil displacement agent is water-soluble
Liquid, wherein anacardol zwitterionic surfactant dosage is 0.5wt%, sodium hydroxide 5wt%, sodium chloride 1wt%, is somebody's turn to do
Solution system can be compounded with the oilfield sewage of salinity 12000mg/L or more, can be substantially reduced the interfacial tension of crude oil.
It should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to limit protection model of the invention
It encloses.In addition, it should also be understood that, after reading the technical contents of the present invention, those skilled in the art can make the present invention each
Kind change, modification and/or variation, all these equivalent forms equally fall within guarantor defined by the application the appended claims
Within the scope of shield.
Claims (7)
1. a kind of temperature-resistant and anti-salt type anacardol zwitterionic surfactant, it is characterised in that: the temperature-resistant and anti-salt type anacardol
Zwitterionic surfactant has the structure as shown in formula (I):
2. a kind of preparation method of temperature-resistant and anti-salt type anacardol zwitterionic surfactant, is described in claim 1 resistance to
The preparation method of warm anti-salt type anacardol zwitterionic surfactant, comprising the following steps:
(1) preparation of anacardol chloropharin ether:
Anacardol, epoxychloropropane and short chain alcohol are added into reactor, at room temperature stirring and dissolving, wherein anacardol and epoxy chlorine
The molar ratio of propane is 1:1~1:8；Then the short chain alcohol solution of phase transfer catalyst is added, wherein the use of phase transfer catalyst
Amount is the short chain alcohol solution of the phase transfer catalyst of 1wt%~5wt% of anacardol dosage, the isothermal reaction 4 at 60~100 DEG C
~10 hours；End of reaction, vacuum distillation are removed solvent and unreacted epoxychloropropane, distillation are repeatedly washed using distilled water
Product removes phase transfer catalyst, obtains anacardol chloropharin ether；
(2) preparation of anacardol tertiary amine:
Diphenylamines and acid binding agent are dissolved into short chain alcohol, the alcoholic solution of the anacardol chloropharin ether is slowly added dropwise, wherein hexichol
The molar ratio of amine and anacardol chloropharin ether is 1:1~8:1, the dosage of acid binding agent be the 1wt% of anacardol chloropharin ether dosage~
5wt%；It is added dropwise, increases reaction temperature to 40~80 DEG C, isothermal reaction 5-10 hours；Reaction terminates, and is removed with vacuum distillation
Remove solvent；Gained product of distillation uses the saturated common salt water washing of benzene and heat multiple respectively, is then washed with distilled water to neutrality again,
The water being finally evaporated under reduced pressure in removing system, obtains anacardol tertiary amine；
(3) preparation of temperature-resistant and anti-salt type anacardol zwitterionic surfactant:
The short chain alcohol solution of acid binding agent and anacardol tertiary amine is added in reactor, it is chloro- that 3- is slowly added dropwise at 30~80 DEG C
The aqueous solution of 2- hydroxypropionate sodium, wherein the molar ratio of 3- chlorine-2-hydroxyl propanesulfonate and anacardol tertiary amine is 1:1~6:1；
It is added dropwise, isothermal reaction 5~12 hours at 50~95 DEG C, end of reaction, vacuum distillation removes solvent, gained product of distillation
It is washed repeatedly with ethyl acetate, with ethyl alcohol recrystallization, obtains temperature-resistant and anti-salt type anacardol zwitterionic surfactant.
3. the preparation method of temperature-resistant and anti-salt type anacardol zwitterionic surfactant according to claim 2, feature
Be: the short chain alcohol is one or more of methanol, ethyl alcohol, isopropanol and isobutanol.
4. the preparation method of temperature-resistant and anti-salt type anacardol zwitterionic surfactant according to claim 2, feature
Be: the phase transfer catalyst is tetrabutylammonium bromide, benzyltriethylammoinium chloride, tetrabutylammonium chloride, dodecyl three
Ammonio methacrylate or tetradecyl trimethyl ammonium chloride.
5. the preparation method of temperature-resistant and anti-salt type anacardol zwitterionic surfactant according to claim 2, feature
Be: the acid binding agent is triethylamine, pyridine or sodium hydroxide.
6. temperature-resistant and anti-salt type anacardol zwitterionic surfactant described in claim 1 high temperature, high salinity it is severe
Application in oil reservoir oil displacement, it is characterised in that: the temperature-resistant and anti-salt type anacardol zwitterionic surfactant be used alone or
It is used with additive compound, temperature-resistant and anti-salt type anacardol zwitterionic surfactant aqueous solution and crude oil form ultralow interface
Power.
7. the application according to requiring 6, it is characterised in that: the additive is inorganic salts, sodium bicarbonate, sodium hydroxide and gathers
One or more of acrylamide.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111549351A (en) * | 2020-06-15 | 2020-08-18 | 南通科星化工有限公司 | High-cleaning-ability environment-friendly metal surface oil stain cleaning agent and preparation method thereof |
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| CN114315662A (en) * | 2021-12-13 | 2022-04-12 | 南京工业大学 | Cardanol-based Gemini zwitterionic surfactant and preparation method and application thereof |
| CN114853579A (en) * | 2021-02-04 | 2022-08-05 | 中国石油天然气股份有限公司 | Preparation method and application of cardanol-based chlorohydrin ether |
| CN115477597A (en) * | 2022-09-23 | 2022-12-16 | 山东科洗新材料有限公司 | Preparation method and application of surfactant |
| CN115651777A (en) * | 2022-12-02 | 2023-01-31 | 福建省佑达环保材料有限公司 | Reworking liquid for CF Rework color film process and cleaning process thereof |
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| EP4364852A1 (en) * | 2022-11-04 | 2024-05-08 | Nouryon Chemicals International B.V. | Collector composition and flotation method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044293A (en) * | 2013-01-23 | 2013-04-17 | 中国石油天然气集团公司 | Preparation method and application of phenoxy tertiary amine sulphonate ampholytic surfactant |
| CN103962052A (en) * | 2014-05-09 | 2014-08-06 | 中国科学院理化技术研究所 | Saturated anacardol ether sulfonate surfactant as well as preparation method and application thereof |
| CN105983370A (en) * | 2015-02-12 | 2016-10-05 | 中国科学院理化技术研究所 | Saturated cardanol betaine surfactant, and preparation method and application thereof |
| CN106432684A (en) * | 2016-09-14 | 2017-02-22 | 中国林业科学研究院林产化学工业研究所 | Self-catalytic anacardol/lignin-based polyurethane foam and preparation method thereof |
-
2018
- 2018-01-10 CN CN201810022597.8A patent/CN110013794A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044293A (en) * | 2013-01-23 | 2013-04-17 | 中国石油天然气集团公司 | Preparation method and application of phenoxy tertiary amine sulphonate ampholytic surfactant |
| CN103962052A (en) * | 2014-05-09 | 2014-08-06 | 中国科学院理化技术研究所 | Saturated anacardol ether sulfonate surfactant as well as preparation method and application thereof |
| CN105983370A (en) * | 2015-02-12 | 2016-10-05 | 中国科学院理化技术研究所 | Saturated cardanol betaine surfactant, and preparation method and application thereof |
| CN106432684A (en) * | 2016-09-14 | 2017-02-22 | 中国林业科学研究院林产化学工业研究所 | Self-catalytic anacardol/lignin-based polyurethane foam and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 丁伟等: "腰果酚甜菜碱型表面活性剂的合成与性能评价", 《油田化学》 * |
| 宋东伟等: "《有机化学》", 31 July 2017, 吉林大学出版社 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111549351A (en) * | 2020-06-15 | 2020-08-18 | 南通科星化工有限公司 | High-cleaning-ability environment-friendly metal surface oil stain cleaning agent and preparation method thereof |
| CN112707945A (en) * | 2020-12-11 | 2021-04-27 | 德仕能源科技集团股份有限公司 | Surfactant for anion-cation oil displacement and preparation method and application thereof |
| CN114853579A (en) * | 2021-02-04 | 2022-08-05 | 中国石油天然气股份有限公司 | Preparation method and application of cardanol-based chlorohydrin ether |
| CN113046047A (en) * | 2021-03-12 | 2021-06-29 | 重庆化工职业学院 | Preparation method of temperature-resistant surfactant for oil displacement |
| CN113046047B (en) * | 2021-03-12 | 2022-09-27 | 重庆化工职业学院 | Preparation method of temperature-resistant surfactant for oil displacement |
| CN114315662A (en) * | 2021-12-13 | 2022-04-12 | 南京工业大学 | Cardanol-based Gemini zwitterionic surfactant and preparation method and application thereof |
| CN115477597A (en) * | 2022-09-23 | 2022-12-16 | 山东科洗新材料有限公司 | Preparation method and application of surfactant |
| CN115477597B (en) * | 2022-09-23 | 2023-10-27 | 山东科洗新材料有限公司 | Preparation method and application of surfactant |
| EP4364852A1 (en) * | 2022-11-04 | 2024-05-08 | Nouryon Chemicals International B.V. | Collector composition and flotation method |
| CN115651777A (en) * | 2022-12-02 | 2023-01-31 | 福建省佑达环保材料有限公司 | Reworking liquid for CF Rework color film process and cleaning process thereof |
| CN117185940A (en) * | 2023-11-08 | 2023-12-08 | 成都赛璐石油科技有限公司 | Asymmetric amphoteric Gemini surfactant, preparation method thereof, preparation method of fracturing oil displacement agent and application of fracturing oil displacement agent |
| CN117185940B (en) * | 2023-11-08 | 2024-02-02 | 成都赛璐石油科技有限公司 | Asymmetric amphoteric Gemini surfactant, preparation method thereof, preparation method of fracturing oil displacement agent and application of fracturing oil displacement agent |
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