CN102863948A - Hydroxysulfobetaine amphoteric surfactant for flooding and preparation method of hydroxysulfobetaine amphoteric surfactant - Google Patents
Hydroxysulfobetaine amphoteric surfactant for flooding and preparation method of hydroxysulfobetaine amphoteric surfactant Download PDFInfo
- Publication number
- CN102863948A CN102863948A CN2012103866558A CN201210386655A CN102863948A CN 102863948 A CN102863948 A CN 102863948A CN 2012103866558 A CN2012103866558 A CN 2012103866558A CN 201210386655 A CN201210386655 A CN 201210386655A CN 102863948 A CN102863948 A CN 102863948A
- Authority
- CN
- China
- Prior art keywords
- aryl
- displacement
- amphoterics
- reaction
- reservoir oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a hydroxysulfobetaine amphoteric surfactant for flooding and a preparation method of the hydroxysulfobetaine amphoteric surfactant, wherein the hydroxysulfobetaine amphoteric surfactant for flooding has a structural formula shown in the specification, in which R is selected from one of C6H5 phenyl, C7H7 tolyl, C8H9 o-xylyl, m-xylyl, p-xylyl, ethylphenyl, mixed xylyl, and C9H11 isopropylphenyl. The hydroxysulfobetaine amphoteric surfactant for flooding provided by the invention has good thermal stability and preferable resistance to high temperature and salt, can generate super low interfacial tension at a high temperature, can be suitable to be used at a large formation temperature range, specially for high-temperature high-salt oil fields, and has a good application prospect.
Description
One, technical field:
What the present invention relates to is the tensio-active agent that uses in the tertiary oil production in oil field, and what be specifically related to is a kind of displacement of reservoir oil hydroxy sulfo lycine amphoterics and preparation method thereof.
Two, background technology:
The inner salt structure of betaine type amphoteric surfactant makes it have preferably heatproof and salt resistance, and it all has good interfacial characteristics in wider pH range in addition, and this also is the prerequisite that trimethyl-glycine is used in alkali-free and weak base composite displacement system.At present less about the document of the application of trimethyl-glycine on the oil field.The mechanism of action that reduces interfacial tension performance tensio-active agent raising recovery ratio is to reduce oil water interfacial tension, reduces the starting resistance of irreducible oil, improves microscopic oil displacement efficiency.So the research of the interfacial characteristics of Surfactant is the emphasis that the screening chemical combined flooding is used tensio-active agent always.
The tertiary oil production in oil field tensio-active agent such as petroleum carboxylate, because the bond energy of molecule is relatively little, at high temperature unstable, causes the tensio-active agent inactivation to sensitive at present; In addition, high salinity particularly high contents of calcium and magnesium ion condition easily form precipitation, the salt sensitivity is caused the loss of tensio-active agent, these are all had higher requirement to tensio-active agent technically and economically.So the anti-salt property of research tensio-active agent plays a very important role to its applicable scope.
Three, summary of the invention:
An object of the present invention is to provide a kind of displacement of reservoir oil hydroxy sulfo lycine amphoterics, it is used for solving existing such as the bad problem of the anti-anti-salt property of the surfactivitys such as petroleum carboxylate; Another object of the present invention is the preparation method that the hydroxy sulfo lycine amphoterics is used in this displacement of reservoir oil.
The technical solution adopted for the present invention to solve the technical problems is: this displacement of reservoir oil with the structural formula of hydroxy sulfo lycine amphoterics is:
Wherein: R takes from C
6H
5Phenyl, C
7H
7Tolyl, C
8H
9O-Xylol base, m-xylene base, p-Xylol base, ethylbenzene, xylol base, C
9H
11In the cumyl any one.
The above-mentioned displacement of reservoir oil preparation method of hydroxy sulfo lycine amphoterics:
The first step prepares the aryl Witconol 2301 by Witconol 2301 and alkylating aromatic hydrocarbon;
Second step prepares the aryl oleyl alcohol by aryl Witconol 2301 hydrogenating reduction;
In the 3rd step, prepare aryl oleyl alcohol glycidyl ether by aryl oleyl alcohol and epoxy chloropropane through etherification reaction;
In the 4th step, aryl oleyl alcohol glycidyl ether and amination reagent are carried out amination reaction obtain tertiary amine;
In the 5th step, tertiary amine and quaternary ammonium reagent are carried out quaternary ammonium reaction obtain described displacement of reservoir oil hydroxy sulfo lycine amphoterics.
Amination reagent is dimethylamine or diethylamine or diethanolamine or n-Butyl Amine 99 or N in the such scheme, N-dimethyl-1,3-propylene diamine.
Witconol 2301 and alkylating aromatic hydrocarbon prepare the process of aryl Witconol 2301 and are in the such scheme: take methylsulfonic acid as catalyzer, with Witconol 2301 and aromatic hydrocarbons and methylsulfonic acid, drop into reactor, pass into N
230min, 80 ℃ of lower reaction 10h, unreacted aromatic hydrocarbons is gone out in underpressure distillation, can obtain the aryl Witconol 2301 for three times with the dehydrated alcohol recrystallization, and wherein aromatic hydrocarbons is selected from any one in benzene,toluene,xylene, ethylbenzene, the isopropyl benzene.
Aryl Witconol 2301 hydrogenating reduction prepares the process of aryl oleyl alcohol and is in the such scheme, and 500g aryl Witconol 2301,2.5g catalyzer are dropped into reactor, uses first N
2H is used in displacement again
2Stir after the displacement and heat up pressure 0.1MPa, mixing speed 500r/min; Temperature rises to 1.1MPa with system pressure after arriving 230 ℃, the beginning timing, and sampling and measuring iodine value at regular intervals, until till iodine value no longer descends, the cooling decompression discharging.
Aryl oleyl alcohol and epoxy chloropropane through the process that etherification reaction prepares aryl oleyl alcohol glycidyl ether are in the such scheme, molar ratio by 1:1 takes by weighing aryl oleyl alcohol and epoxy chloropropane, be that 30% sodium hydroxide solution, Tetrabutyl amonium bromide place the four-hole bottle that electric blender, condensing works are housed with the aryl oleyl alcohol after taking by weighing and epoxy chloropropane, mass percent concentration, drip epoxy chloropropane, temperature is controlled at 40-70 ℃, and time for adding is 5-10h; Be warmed up to 80-100 ℃, reaction 5-8h; The cooling suction filtration to neutral, is collected the upper strata adopting dark liquid with 70-80 ℃ of distilled water wash behind the separatory; Use anhydrous sodium sulfate drying, vacuum rotary steam is removed excessive epoxy chloropropane, a small amount of water and solvent toluene.
The process of in the such scheme aryl oleyl alcohol glycidyl ether and amination reagent being carried out amination reaction is, take by weighing aryl oleyl alcohol glycidyl ether and amination reagent according to mol ratio 1:1, amination reagent and ethanolic soln put into condensing works is housed, in the four-hole bottle of whipping appts and thermometer, holding temperature is at 40-80 ℃, beginning slowly drips arylolycidyl ethers, dropwise, temperature is elevated to 50-80 ℃, kept this thermotonus 4-10 hour, finish reaction, revolve to steam and remove unreacted ethanol and amination reagent, get the product tertiary amine after the drying.
Tertiary amine and quaternary ammonium reagent carry out the process of quaternary ammonium reaction and are in the such scheme, quaternary ammonium reagent is 3-chlorine 2-hydroxyl-propanesulfonate, take by weighing tertiary amine and 3-chlorine 2-hydroxyl-propanesulfonate, the mol ratio of tertiary amine and 3-chlorine 2-hydroxyl-propanesulfonate is 1.2:1.0, quaternary ammonium reagent placed electric mixer is housed, in the four-hole boiling flask of condensing works, be that 70% ethanolic soln makes its dissolving with volume ratio, be warming up to 70-80 ℃, beginning slowly drips tertiary amine, dropwises, holding temperature is at 80-90 ℃, pH reacted 9-12 hour at 8-9, finished reaction; Have solid to occur in the cooling afterreaction thing, suction filtration is removed unreacted tertiary amine with petroleum ether extraction, and recovering liquid is revolved to steam and removed the second alcohol and water, obtains yellow thick product; Wash product with ethyl acetate, suction filtration, drying obtains displacement of reservoir oil hydroxy sulfo lycine amphoterics, carries out recrystallization with ethanol, the dry white powder solid phase prod that gets.
Tertiary amine and quaternary ammonium reagent carry out the process of quaternary ammonium reaction and are in the such scheme, quaternary ammonium reagent is propane sultone or butane sultone, take by weighing tertiary amine and quaternary ammonium reagent, the mol ratio of tertiary amine and quaternary ammonium reagent is 1:1, reflux condensing tube is being housed, magnetic stirring apparatus, constant pressure funnel, add the 0.1mol tertiary amine in the four-hole bottle of thermometer, be dissolved in the 100-200ml acetone, take by weighing and slowly be added drop-wise in the four-hole bottle under the sultone room temperature of 0.1mol (propane sultone or butane sultone), 0-15 ℃ of lower slowly dropping, be warming up to back flow reaction 24-48h after dropwising, after reaction finishes, system is cooled to room temperature, filter out solid matter, repeatedly wash with acetone, then obtain white crystal with acetone and methyl alcohol mixed liquor recrystallization, 60-80 ℃ of lower vacuum-drying gets the white powder solid, displacement of reservoir oil hydroxy sulfo lycine amphoterics.
The displacement of reservoir oil of the present invention is as follows with hydroxy sulfo lycine amphoterics composition principle:
1, the aryl Witconol 2301 is synthetic:
R=C
6H
6(benzene); R=C
7H
8(toluene); R=C
8H
10(o-Xylol, m-xylene, p-Xylol, ethylbenzene, xylol); R=C
9H
12(isopropyl benzene)
2, the aryl oleyl alcohol is synthetic:
3, aryl oleyl alcohol glycidyl ether is synthetic:
4, amination reaction:
5, quaternary ammonium reaction:
Beneficial effect:
1, the displacement of reservoir oil provided by the invention hydroxy sulfo lycine amphoterics Heat stability is good, possesses preferably high temperature resistant anti-salt property, under comparatively high temps, can produce ultra low interfacial tension, applicable formation temperature a wider range, be particularly useful for the high temperature and high salt oil field, have good application prospect.
2, the displacement of reservoir oil provided by the invention is little with the loss of hydroxy sulfo lycine amphoterics Static Adsorption, is not easy inactivation.
3, the method for preparing displacement of reservoir oil usefulness hydroxy sulfo lycine amphoterics provided by the invention, synthesis technique is simple, and product is nontoxic.
Four, description of drawings:
Fig. 1 is the displacement of reservoir oil of the present invention hydroxy sulfo lycine amphoterics INTERFACIAL TENSION CURVES figure;
Fig. 2 is that alkali is to the displacement of reservoir oil of the present invention hydroxy sulfo lycine amphoterics interface performance influence curve figure;
Fig. 3 is that temperature is to the influence curve of the displacement of reservoir oil of the present invention with hydroxy sulfo lycine amphoterics absorption property.
Five, embodiment:
The present invention is described further below in conjunction with accompanying drawing:
Embodiment 1:
One, with the 296g Witconol 2301,117g benzene, 1g methylsulfonic acid are catalyzer, drop into reactor, pass into N
230min, 80 ℃ of lower reaction 10h, unreacted aromatic hydrocarbons is gone out in underpressure distillation, can obtain the aryl Witconol 2301 for three times with the dehydrated alcohol recrystallization, yield 91.3%.
Two, 250g aryl Witconol 2301,2.5g palladium catalyst carbon are dropped into reactor, use first N
2H is used in displacement again
2Stir after the displacement and heat up pressure 0.1MPa, mixing speed 500r/min.Temperature rises to 1.1MPa with system pressure after arriving 230 ℃, the beginning timing, and sampling and measuring iodine value at regular intervals, until till iodine value no longer descends, cooling decompression discharging, yield 97.3%.
Three, routine 1:1 takes by weighing aryl oleyl alcohol and epoxy chloropropane in molar ratio, 30% sodium hydroxide solution 134g, Tetrabutyl amonium bromide 1g place the four-hole bottle that electric blender, condensing works are housed, drip the 92.5g epoxy chloropropane, temperature is controlled at 60 ℃, and time for adding is 8h; Be warmed up to 80 degrees centigrade, reaction 6h; The cooling suction filtration, 80 ℃ of distilled water washs are collected the upper strata adopting dark liquid to neutral behind the separatory; Use anhydrous sodium sulfate drying, vacuum rotary steam is removed excessive epoxy chloropropane, a small amount of water and solvent toluene yield 78.6%.
Four, take by weighing dimethylamine agueous solution 112.5g according to ether amine mol ratio 1:1, ethanol 100ml puts into condensing works is housed, in the four-hole bottle of whipping appts and thermometer, holding temperature is at 70 ℃, beginning slowly drips arylolycidyl ethers (1mol), dropwises, and temperature is elevated to 80 ℃, keep this thermotonus 8 hours, and finished reaction.Revolve to steam and remove unreacted ethanol and amination reagent, dry weighing product calculates productive rate 91.5%.
Five, the molar feed ratio of getting tertiary amine and 3-chlorine 2-hydroxyl-propanesulfonate is 1.2:1.0,196.5g3-chlorine 2-hydroxyl-propanesulfonate placed electric mixer is housed, in the four-hole boiling flask of condensing works, the ethanolic soln 100ml with 70% makes its dissolving, is warming up to 80 ℃, beginning slowly drips the tertiary amine of 1.2mol, dropwise, holding temperature is at 90 ℃, and pH is at 8-9, reacted 12 hours, and finished reaction.Have solid to occur in the cooling afterreaction thing, suction filtration is removed unreacted tertiary amine with petroleum ether extraction, and recovering liquid is revolved to steam and removed the second alcohol and water, obtains yellow thick product.Wash product with ethyl acetate, suction filtration, drying obtains product.Carry out recrystallization with ethanol, the dry rear productive rate 78.2% that calculates.
Embodiment 2:
One, with the 296g Witconol 2301,158g xylol, 1g methylsulfonic acid are catalyzer, drop into reactor, pass into N
230min, 80 ℃ of lower reaction 10h, unreacted aromatic hydrocarbons is gone out in underpressure distillation, can obtain the aryl Witconol 2301 for three times with the dehydrated alcohol recrystallization, yield 92.5%.
Two, 250g aryl Witconol 2301,2.5g catalyzer are dropped into reactor, use first N
2H is used in displacement again
2Stir after the displacement and heat up pressure 0.1MPa, mixing speed 500r/min.Temperature rises to 1.1MPa with system pressure after arriving 230 ℃, the beginning timing, and sampling and measuring iodine value at regular intervals, until till iodine value no longer descends, cooling decompression discharging, yield 98.1%.
Three, routine 1:1 takes by weighing aryl oleyl alcohol and epoxy chloropropane in molar ratio, 30% sodium hydroxide solution 134g, Tetrabutyl amonium bromide 1g place the four-hole bottle that electric blender, condensing works are housed, drip the 92.5g epoxy chloropropane, temperature is controlled at 60 ℃, and time for adding is 8h; Be warmed up to 80 degrees centigrade, reaction 6h; The cooling suction filtration, 80 ℃ of distilled water washs are collected the upper strata adopting dark liquid to neutral behind the separatory; Use anhydrous sodium sulfate drying, vacuum rotary steam is removed excessive epoxy chloropropane, a small amount of water and solvent toluene, yield 78.5%.
Four, take by weighing diethylamine aqueous solution 73g according to ether amine mol ratio 1:1, ethanol 100ml puts into condensing works is housed, in the four-hole bottle of whipping appts and thermometer, holding temperature is at 70 ℃, beginning slowly drips arylolycidyl ethers (1mol), dropwises, and temperature is elevated to 80 ℃, keep this thermotonus 8 hours, and finished reaction.Revolve to steam and remove unreacted ethanol and amination reagent, dry weighing product calculates productive rate 91.2%.
Five, in the four-hole bottle that reflux condensing tube, magnetic stirring apparatus, constant pressure funnel, thermometer are housed, add the 0.1mol tertiary amine, be dissolved in the 100ml acetone, take by weighing and slowly be added drop-wise in the four-hole bottle under the 0.1mol propane sultone 12.214g room temperature, 0 ℃ of lower slowly dropping, be warming up to back flow reaction 24h after dropwising, after reaction finishes, system is cooled to room temperature, filter out solid matter, repeatedly wash with acetone, then obtain white crystal with acetone and methyl alcohol mixed liquor recrystallization, 60 ℃ of lower vacuum-dryings get the white powder solid, the dry rear productive rate 71.6% that calculates.
Embodiment 3:
One, with the 296g Witconol 2301,138g toluene, 1g methylsulfonic acid are catalyzer, drop into reactor, pass into N
230min, 80 ℃ of lower reaction 10h, unreacted aromatic hydrocarbons is gone out in underpressure distillation, can obtain the aryl Witconol 2301 three times with the dehydrated alcohol recrystallization.
Two, 500g aryl Witconol 2301,2.5g catalyzer are dropped into reactor, use first N
2H is used in displacement again
2Stir after the displacement and heat up pressure 0.1MPa, mixing speed 500r/min.Temperature rises to 1.1MPa with system pressure after arriving 230 ℃, the beginning timing, and sampling and measuring iodine value at regular intervals, until till iodine value no longer descends, the cooling decompression discharging.
Three, routine 1:1 takes by weighing aryl oleyl alcohol and epoxy chloropropane in molar ratio, 30% sodium hydroxide solution 134g, Tetrabutyl amonium bromide 1g place the four-hole bottle that electric blender, condensing works are housed, drip the 92.5g epoxy chloropropane, temperature is controlled at 40 ℃, and time for adding is 5h; Be warmed up to 90 degrees centigrade, reaction 5h; The cooling suction filtration, 70 ℃ of distilled water washs are collected the upper strata adopting dark liquid to neutral behind the separatory; Use anhydrous sodium sulfate drying, vacuum rotary steam is removed excessive epoxy chloropropane, a small amount of water and solvent toluene yield 78.8%.
Four, take by weighing diethylamine aqueous solution 73g according to ether amine mol ratio 1:1, ethanol 100ml puts into condensing works is housed, in the four-hole bottle of whipping appts and thermometer, holding temperature is at 40 ℃, beginning slowly drips arylolycidyl ethers (1mol), dropwises, and temperature is elevated to 50 ℃, keep this thermotonus 4 hours, and finished reaction.Revolve to steam and remove unreacted ethanol and amination reagent, dry weighing product calculates productive rate 91.2%.
Five, the molar feed ratio of getting tertiary amine and 3-chlorine 2-hydroxyl-propanesulfonate is 1.2:1.0,196.5g3-chlorine 2-hydroxyl-propanesulfonate placed electric mixer is housed, in the four-hole boiling flask of condensing works, the ethanolic soln 100ml with 70% makes its dissolving, is warming up to 70 ℃, beginning slowly drips the tertiary amine of 1.2mol, dropwise, holding temperature is at 80 ℃, and pH is 8, reacted 9 hours, and finished reaction.Have solid to occur in the cooling afterreaction thing, suction filtration is removed unreacted tertiary amine with petroleum ether extraction, and recovering liquid is revolved to steam and removed the second alcohol and water, obtains yellow thick product.Wash product with ethyl acetate, suction filtration, drying obtains product.Carry out recrystallization with ethanol, the dry rear productive rate 78.6% that calculates.
Embodiment 4:
One, with the 296g Witconol 2301,159g ethylbenzene, 1g methylsulfonic acid are catalyzer, drop into reactor, pass into N
230min, 80 ℃ of lower reaction 10h, unreacted aromatic hydrocarbons is gone out in underpressure distillation, can obtain the aryl Witconol 2301 three times with the dehydrated alcohol recrystallization.
Two, 500g aryl Witconol 2301,2.5g catalyzer are dropped into reactor, use first N
2H is used in displacement again
2Stir after the displacement and heat up pressure 0.1MPa, mixing speed 500r/min.Temperature rises to 1.1MPa with system pressure after arriving 230 ℃, the beginning timing, and sampling and measuring iodine value at regular intervals, until till iodine value no longer descends, the cooling decompression discharging.
Three, routine 1:1 takes by weighing aryl oleyl alcohol and epoxy chloropropane in molar ratio, 30% sodium hydroxide solution 134g, Tetrabutyl amonium bromide 1g place the four-hole bottle that electric blender, condensing works are housed, drip the 92.5g epoxy chloropropane, temperature is controlled at 70 ℃, and time for adding is 10h; Be warmed up to 100 degrees centigrade, reaction 85h; The cooling suction filtration, 75 ℃ of distilled water washs are collected the upper strata adopting dark liquid to neutral behind the separatory; Use anhydrous sodium sulfate drying, vacuum rotary steam is removed excessive epoxy chloropropane, a small amount of water and solvent toluene yield 79.1%.
Four, take by weighing diethylamine aqueous solution 73g according to ether amine mol ratio 1:1, ethanol 100ml puts into condensing works is housed, in the four-hole bottle of whipping appts and thermometer, holding temperature is at 60 ℃, beginning slowly drips arylolycidyl ethers (1mol), dropwises, and temperature is elevated to 70 ℃, keep this thermotonus 10 hours, and finished reaction.Revolve to steam and remove unreacted ethanol and amination reagent, dry weighing product calculates productive rate 91%.
Five, the molar feed ratio of getting tertiary amine and 3-chlorine 2-hydroxyl-propanesulfonate is 1.2:1.0,196.5g3-chlorine 2-hydroxyl-propanesulfonate placed electric mixer is housed, in the four-hole boiling flask of condensing works, the ethanolic soln 100ml with 70% makes its dissolving, is warming up to 80 ℃, beginning slowly drips the tertiary amine of 1.2mol, dropwise, holding temperature is at 90 ℃, and pH is 9, reacted 10 hours, and finished reaction.Have solid to occur in the cooling afterreaction thing, suction filtration is removed unreacted tertiary amine with petroleum ether extraction, and recovering liquid is revolved to steam and removed the second alcohol and water, obtains yellow thick product.Wash product with ethyl acetate, suction filtration, drying obtains product.Carry out recrystallization with ethanol, the dry rear productive rate 79.2% that calculates.
Embodiment 5:
One, with the 296g Witconol 2301,159g dimethylbenzene, 1g methylsulfonic acid are catalyzer, drop into reactor, pass into N
230min, 80 ℃ of lower reaction 10h, unreacted aromatic hydrocarbons is gone out in underpressure distillation, can obtain the aryl Witconol 2301 for three times with the dehydrated alcohol recrystallization, yield 91.6%.
Two, 250g aryl Witconol 2301,2.5g palladium catalyst carbon are dropped into reactor, use first N
2H is used in displacement again
2Stir after the displacement and heat up pressure 0.1MPa, mixing speed 500r/min.Temperature rises to 1.1MPa with system pressure after arriving 230 ℃, the beginning timing, and sampling and measuring iodine value at regular intervals, until till iodine value no longer descends, cooling decompression discharging, yield 97.5%.
Three, routine 1:1 takes by weighing aryl oleyl alcohol and epoxy chloropropane in molar ratio, 30% sodium hydroxide solution 134g, Tetrabutyl amonium bromide 1g place the four-hole bottle that electric blender, condensing works are housed, drip the 92.5g epoxy chloropropane, temperature is controlled at 60 ℃, and time for adding is 8h; Be warmed up to 80 degrees centigrade, reaction 6h; The cooling suction filtration, 80 ℃ of distilled water washs are collected the upper strata adopting dark liquid to neutral behind the separatory; Use anhydrous sodium sulfate drying, vacuum rotary steam is removed excessive epoxy chloropropane, a small amount of water and solvent toluene yield 78.4%.
Four, take by weighing dimethylamine agueous solution 112.5g according to ether amine mol ratio 1:1, ethanol 100ml puts into condensing works is housed, in the four-hole bottle of whipping appts and thermometer, holding temperature is at 70 ℃, beginning slowly drips arylolycidyl ethers (1mol), dropwises, and temperature is elevated to 80 ℃, keep this thermotonus 8 hours, and finished reaction.Revolve to steam and remove unreacted ethanol and amination reagent, dry weighing product calculates productive rate 91.5%.
Five, the molar feed ratio of getting tertiary amine and 3-chlorine 2-hydroxyl-propanesulfonate is 1.2:1.0,196.5g3-chlorine 2-hydroxyl-propanesulfonate placed electric mixer is housed, in the four-hole boiling flask of condensing works, the ethanolic soln 100ml with 70% makes its dissolving, is warming up to 80 ℃, beginning slowly drips the tertiary amine of 1.2mol, dropwise, holding temperature is at 90 ℃, and pH is at 8-9, reacted 12 hours, and finished reaction.Have solid to occur in the cooling afterreaction thing, suction filtration is removed unreacted tertiary amine with petroleum ether extraction, and recovering liquid is revolved to steam and removed the second alcohol and water, obtains yellow thick product.Wash product with ethyl acetate, suction filtration, drying obtains product.Carry out recrystallization with ethanol, the dry rear productive rate 74.7% that calculates.
Embodiment 6:
One, with the 296g Witconol 2301,180g isopropyl benzene, 1g methylsulfonic acid are catalyzer, drop into reactor, pass into N
230min, 80 ℃ of lower reaction 10h, unreacted aromatic hydrocarbons is gone out in underpressure distillation, can obtain the aryl Witconol 2301 for three times with the dehydrated alcohol recrystallization, yield 91 %.
Two, 250g aryl Witconol 2301,2.5g palladium catalyst carbon are dropped into reactor, use first N
2H is used in displacement again
2Stir after the displacement and heat up pressure 0.1MPa, mixing speed 500r/min.Temperature rises to 1.1MPa with system pressure after arriving 230 ℃, the beginning timing, and sampling and measuring iodine value at regular intervals, until till iodine value no longer descends, cooling decompression discharging, yield 97.1%.
Three, routine 1:1 takes by weighing aryl oleyl alcohol and epoxy chloropropane in molar ratio, 30% sodium hydroxide solution 134g, Tetrabutyl amonium bromide 1g place the four-hole bottle that electric blender, condensing works are housed, drip the 92.5g epoxy chloropropane, temperature is controlled at 60 ℃, and time for adding is 8h; Be warmed up to 80 degrees centigrade, reaction 6h; The cooling suction filtration, 80 ℃ of distilled water washs are collected the upper strata adopting dark liquid to neutral behind the separatory; Use anhydrous sodium sulfate drying, vacuum rotary steam is removed excessive epoxy chloropropane, a small amount of water and solvent toluene yield 78.2%.
Four, take by weighing dimethylamine agueous solution 112.5g according to ether amine mol ratio 1:1, ethanol 100ml puts into condensing works is housed, in the four-hole bottle of whipping appts and thermometer, holding temperature is at 70 ℃, beginning slowly drips arylolycidyl ethers (1mol), dropwises, and temperature is elevated to 80 ℃, keep this thermotonus 8 hours, and finished reaction.Revolve to steam and remove unreacted ethanol and amination reagent, dry weighing product calculates productive rate 91.8%.
Five, the molar feed ratio of getting tertiary amine and 3-chlorine 2-hydroxyl-propanesulfonate is 1.2:1.0,196.5g3-chlorine 2-hydroxyl-propanesulfonate placed electric mixer is housed, in the four-hole boiling flask of condensing works, the ethanolic soln 100ml with 70% makes its dissolving, is warming up to 80 ℃, beginning slowly drips the tertiary amine of 1.2mol, dropwise, holding temperature is at 90 ℃, and pH is at 8-9, reacted 12 hours, and finished reaction.Have solid to occur in the cooling afterreaction thing, suction filtration is removed unreacted tertiary amine with petroleum ether extraction, and recovering liquid is revolved to steam and removed the second alcohol and water, obtains yellow thick product.Wash product with ethyl acetate, suction filtration, drying obtains product.Carry out recrystallization with ethanol, the dry rear productive rate 75.% that calculates.
Embodiment 7:
One, with the 296g Witconol 2301,158g xylol, 1g methylsulfonic acid are catalyzer, drop into reactor, pass into N
230min, 80 ℃ of lower reaction 10h, unreacted aromatic hydrocarbons is gone out in underpressure distillation, can obtain the aryl Witconol 2301 for three times with the dehydrated alcohol recrystallization, yield 92.5%.
Two, 250g aryl Witconol 2301,2.5g catalyzer are dropped into reactor, use first N
2H is used in displacement again
2Stir after the displacement and heat up pressure 0.1MPa, mixing speed 500r/min.Temperature rises to 1.1MPa with system pressure after arriving 230 ℃, the beginning timing, and sampling and measuring iodine value at regular intervals, until till iodine value no longer descends, cooling decompression discharging, yield 98.1%.
Three, routine 1:1 takes by weighing aryl oleyl alcohol and epoxy chloropropane in molar ratio, 30% sodium hydroxide solution 134g, Tetrabutyl amonium bromide 1g place the four-hole bottle that electric blender, condensing works are housed, drip the 92.5g epoxy chloropropane, temperature is controlled at 60 ℃, and time for adding is 8h; Be warmed up to 80 degrees centigrade, reaction 6h; The cooling suction filtration, 80 ℃ of distilled water washs are collected the upper strata adopting dark liquid to neutral behind the separatory; Use anhydrous sodium sulfate drying, vacuum rotary steam is removed excessive epoxy chloropropane, a small amount of water and solvent toluene, yield 78.5%.
Four, take by weighing diethylamine aqueous solution 73g according to ether amine mol ratio 1:1, ethanol 100ml puts into condensing works is housed, in the four-hole bottle of whipping appts and thermometer, holding temperature is at 70 ℃, beginning slowly drips arylolycidyl ethers (1mol), dropwises, and temperature is elevated to 80 ℃, keep this thermotonus 8 hours, and finished reaction.Revolve to steam and remove unreacted ethanol and amination reagent, dry weighing product calculates productive rate 91.2%.
Five, reflux condensing tube is being housed, magnetic stirring apparatus, constant pressure funnel, add the 0.1mol tertiary amine in the four-hole bottle of thermometer, be dissolved in the 200ml acetone, take by weighing and slowly be added drop-wise in the four-hole bottle under the 0.1mol butane sultone 13.617g room temperature, 15 ℃ of lower slowly droppings, be warming up to back flow reaction 48h after dropwising, after reaction finishes, system is cooled to room temperature, filter out solid matter, repeatedly wash with acetone, then obtain white crystal with acetone and methyl alcohol mixed liquor recrystallization, 80 ℃ of lower vacuum-dryings get the white powder solid, the dry rear productive rate 71.6% that calculates.
Utilizing above-described embodiment to carry out the displacement of reservoir oil tests with hydroxy sulfo lycine amphoterics interfacial tension, obtain the displacement of reservoir oil with hydroxy sulfo lycine amphoterics INTERFACIAL TENSION CURVES as shown in Figure 1, Fig. 1 reflects that this displacement of reservoir oil can produce ultra low interfacial tension with the hydroxy sulfo lycine amphoterics under comparatively high temps.
Utilizing simultaneously above-described embodiment to carry out alkali tests with the impact of hydroxy sulfo lycine amphoterics interface performance the displacement of reservoir oil, obtain alkali to the displacement of reservoir oil with hydroxy sulfo lycine amphoterics interface performance influence curve as shown in Figure 2, Fig. 2 reflects that alkali is little with the impact of hydroxy sulfo lycine amphoterics interface performance on this displacement of reservoir oil.
Utilize in addition above-described embodiment to carry out temperature to the impact test of the displacement of reservoir oil with hydroxy sulfo lycine amphoterics absorption property, obtain temperature to the displacement of reservoir oil with the influence curve of hydroxy sulfo lycine amphoterics absorption property as shown in Figure 3, can find out, this displacement of reservoir oil possesses preferably high temperature resistant anti-salt property with the Heat stability is good that affects of hydroxy sulfo lycine amphoterics absorption property.
In addition, utilize above-described embodiment also to carry out the displacement of reservoir oil and test with the oil displacement efficiency that affects of hydroxy sulfo lycine amphoterics absorption property, test result sees Table 1.
Table 1 displacement of reservoir oil is estimated with the displacement of reservoir oil of hydroxy sulfo lycine amphoterics
Claims (9)
1. displacement of reservoir oil hydroxy sulfo lycine amphoterics, it is characterized in that: this displacement of reservoir oil with the structural formula of hydroxy sulfo lycine amphoterics is:
Wherein: R takes from C
6H
5Phenyl, C
7H
7Tolyl, C
8H
9O-Xylol base, m-xylene base, p-Xylol base, ethylbenzene, xylol base, C
9H
11In the cumyl any one.
2. the displacement of reservoir oil claimed in claim 1 is characterized in that with the preparation method of hydroxy sulfo lycine amphoterics: the described displacement of reservoir oil is with the preparation method of hydroxy sulfo lycine amphoterics:
The first step prepares the aryl Witconol 2301 by Witconol 2301 and alkylating aromatic hydrocarbon;
Second step prepares the aryl oleyl alcohol by aryl Witconol 2301 hydrogenating reduction;
In the 3rd step, prepare aryl oleyl alcohol glycidyl ether by aryl oleyl alcohol and epoxy chloropropane through etherification reaction;
In the 4th step, aryl oleyl alcohol glycidyl ether and amination reagent are carried out amination reaction obtain tertiary amine;
In the 5th step, tertiary amine and quaternary ammonium reagent are carried out quaternary ammonium reaction obtain described displacement of reservoir oil hydroxy sulfo lycine amphoterics.
3. the displacement of reservoir oil according to claim 2 is with the preparation method of hydroxy sulfo lycine amphoterics, it is characterized in that: the process that described Witconol 2301 and alkylating aromatic hydrocarbon prepare the aryl Witconol 2301 is: take methylsulfonic acid as catalyzer, with Witconol 2301 and aromatic hydrocarbons and methylsulfonic acid, drop into reactor, pass into N
230min, 80 ℃ of lower reaction 10h, unreacted aromatic hydrocarbons is gone out in underpressure distillation, can obtain the aryl Witconol 2301 for three times with the dehydrated alcohol recrystallization, and wherein aromatic hydrocarbons is selected from any one in benzene,toluene,xylene, ethylbenzene, the isopropyl benzene.
4. the displacement of reservoir oil according to claim 2 is with the preparation method of hydroxy sulfo lycine amphoterics, it is characterized in that: the process that described aryl Witconol 2301 hydrogenating reduction prepares the aryl oleyl alcohol is, 500g aryl Witconol 2301,2.5g catalyzer are dropped into reactor, use first N
2H is used in displacement again
2Stir after the displacement and heat up pressure 0.1MPa, mixing speed 500r/min; Temperature rises to 1.1MPa with system pressure after arriving 230 ℃, the beginning timing, and sampling and measuring iodine value at regular intervals, until till iodine value no longer descends, the cooling decompression discharging.
5. the displacement of reservoir oil according to claim 2 is with the preparation method of hydroxy sulfo lycine amphoterics, it is characterized in that: described aryl oleyl alcohol and epoxy chloropropane through the process that etherification reaction prepares aryl oleyl alcohol glycidyl ether are, molar ratio by 1:1 takes by weighing aryl oleyl alcohol and epoxy chloropropane, with aryl oleyl alcohol and the epoxy chloropropane after taking by weighing, mass percent concentration is 30% sodium hydroxide solution, Tetrabutyl amonium bromide places electric blender is housed, in the four-hole bottle of condensing works, drip epoxy chloropropane, temperature is controlled at 40-70 ℃, and time for adding is 5-10h; Be warmed up to 80-100 ℃, reaction 5-8h; The cooling suction filtration to neutral, is collected the upper strata adopting dark liquid with 70-80 ℃ of distilled water wash behind the separatory; Use anhydrous sodium sulfate drying, vacuum rotary steam is removed excessive epoxy chloropropane, a small amount of water and solvent toluene.
6. the displacement of reservoir oil according to claim 5 is with the preparation method of hydroxy sulfo lycine amphoterics, it is characterized in that: the described process that aryl oleyl alcohol glycidyl ether and amination reagent are carried out amination reaction is, take by weighing aryl oleyl alcohol glycidyl ether and amination reagent according to mol ratio 1:1, amination reagent and ethanolic soln put into condensing works is housed, in the four-hole bottle of whipping appts and thermometer, holding temperature is at 40-80 ℃, beginning slowly drips arylolycidyl ethers, dropwise, temperature is elevated to 50-80 ℃, kept this thermotonus 4-10 hour, finish reaction, revolve to steam and remove unreacted ethanol and amination reagent, get the product tertiary amine after the drying.
7. the displacement of reservoir oil according to claim 6 is with the preparation method of hydroxy sulfo lycine amphoterics, it is characterized in that: the process that described tertiary amine and quaternary ammonium reagent carry out quaternary ammonium reaction is, quaternary ammonium reagent is 3-chlorine 2-hydroxyl-propanesulfonate, take by weighing tertiary amine and 3-chlorine 2-hydroxyl-propanesulfonate, the mol ratio of tertiary amine and 3-chlorine 2-hydroxyl-propanesulfonate is 1.2:1.0, quaternary ammonium reagent placed electric mixer is housed, in the four-hole boiling flask of condensing works, be that 70% ethanolic soln makes its dissolving with volume ratio, be warming up to 70-80 ℃, beginning slowly drips tertiary amine, dropwise, holding temperature is at 80-90 ℃, and pH is at 8-9, reacted 9-12 hour, and finished reaction; Have solid to occur in the cooling afterreaction thing, suction filtration is removed unreacted tertiary amine with petroleum ether extraction, and recovering liquid is revolved to steam and removed the second alcohol and water, obtains yellow thick product; Wash product with ethyl acetate, suction filtration, drying obtains displacement of reservoir oil hydroxy sulfo lycine amphoterics, carries out recrystallization with ethanol, dry white powder solid phase prod.
8. the displacement of reservoir oil according to claim 6 is with the preparation method of hydroxy sulfo lycine amphoterics, it is characterized in that: the process that described tertiary amine and quaternary ammonium reagent carry out quaternary ammonium reaction is, quaternary ammonium reagent is propane sultone or butane sultone, take by weighing tertiary amine and quaternary ammonium reagent, the mol ratio of tertiary amine and quaternary ammonium reagent is 1:1, reflux condensing tube is being housed, magnetic stirring apparatus, constant pressure funnel, add the 0.1mol tertiary amine in the four-hole bottle of thermometer, be dissolved in the 100-200ml acetone, take by weighing and slowly be added drop-wise in the four-hole bottle under the sultone room temperature of 0.1mol (propane sultone or butane sultone), 0-15 ℃ of lower slowly dropping, be warming up to back flow reaction 24-48h after dropwising, after reaction finishes, system is cooled to room temperature, filter out solid matter, repeatedly wash with acetone, then obtain white crystal with acetone and methyl alcohol mixed liquor recrystallization, 60-80 ℃ of lower vacuum-drying gets the white powder solid, displacement of reservoir oil hydroxy sulfo lycine amphoterics.
9. the displacement of reservoir oil according to claim 2 is with the preparation method of hydroxy sulfo lycine amphoterics, and it is characterized in that: described amination reagent is dimethylamine or diethylamine or diethanolamine or n-Butyl Amine 99 or N, N-dimethyl-1,3-propylene diamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210386655.8A CN102863948B (en) | 2012-10-14 | 2012-10-14 | Hydroxysulfobetaine amphoteric surfactant for flooding and preparation method of hydroxysulfobetaine amphoteric surfactant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210386655.8A CN102863948B (en) | 2012-10-14 | 2012-10-14 | Hydroxysulfobetaine amphoteric surfactant for flooding and preparation method of hydroxysulfobetaine amphoteric surfactant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102863948A true CN102863948A (en) | 2013-01-09 |
| CN102863948B CN102863948B (en) | 2014-08-13 |
Family
ID=47443081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210386655.8A Expired - Fee Related CN102863948B (en) | 2012-10-14 | 2012-10-14 | Hydroxysulfobetaine amphoteric surfactant for flooding and preparation method of hydroxysulfobetaine amphoteric surfactant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102863948B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103992247A (en) * | 2014-05-15 | 2014-08-20 | 中国石油天然气股份有限公司 | Fatty alcohol polyoxypropylene ether sulphobetaine and alkali-free composite combination for displacing oil |
| WO2015161812A1 (en) * | 2014-04-23 | 2015-10-29 | Jiangnan University | Compounds, compositions thereof and methods for hydrocarbon extraction using the same |
| CN108948342A (en) * | 2018-08-07 | 2018-12-07 | 江苏四新界面剂科技有限公司 | A kind of preparation method of the chain of oxyethylene group containing poly amphoteric surfactant |
| CN110835522A (en) * | 2018-08-17 | 2020-02-25 | 中国石油化工股份有限公司 | Temperature-resistant and salt-resistant type super-thick oil emulsifying viscosity reducer and preparation method thereof |
| CN111607381A (en) * | 2019-02-25 | 2020-09-01 | 中国石油天然气股份有限公司 | High-temperature diverting acid composition and preparation method thereof |
| CN111607380A (en) * | 2019-02-25 | 2020-09-01 | 中国石油天然气股份有限公司 | Surfactant for reservoir transformation and preparation method thereof |
| CN113135846A (en) * | 2021-04-07 | 2021-07-20 | 吉和昌新材料(荆门)有限公司 | Preparation method of sulfobetaine type waterborne polyurethane chain extender |
| CN115044425A (en) * | 2022-06-09 | 2022-09-13 | 中海油天津化工研究设计院有限公司 | Oil stain cleaning agent and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105331351B (en) * | 2015-07-15 | 2018-08-21 | 华中科技大学 | A kind of degradable water base clean fracturing fluid thickening agent in oil gas field |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1566256A (en) * | 2003-07-04 | 2005-01-19 | 大庆高新区鑫诺精细化工有限公司 | Alkyl aryl alkylbetaine surfactant composition and its application in tertiary oil recovery |
| CN101654421A (en) * | 2009-08-27 | 2010-02-24 | 浙江合诚化学有限公司 | Synthesis method of cocoamidopropyl-2-hydroxyl-3-sulfopropyl betaine |
| CN101891655A (en) * | 2010-06-23 | 2010-11-24 | 程玉桥 | Method for preparing modified betaine type amphoteric surfactant used for tertiary oil recovery |
| US20110166128A1 (en) * | 2010-01-07 | 2011-07-07 | Alkermes, Inc. | Diaryldiazepine Prodrugs for the Treatment of Neurological and Psychological Disorders |
| CN102159204A (en) * | 2008-09-19 | 2011-08-17 | 辉瑞公司 | Stable liquid antibody formulation |
| CN102205215A (en) * | 2011-04-28 | 2011-10-05 | 孙安顺 | Crude oil emulsifying agent |
| CN102618244A (en) * | 2011-03-11 | 2012-08-01 | 中国石油天然气股份有限公司 | Betaine surfactant and preparation method and application thereof |
| US20120196776A1 (en) * | 2011-02-02 | 2012-08-02 | Gupta D V Satyanarayana | Oil Field Treatment Fluids |
-
2012
- 2012-10-14 CN CN201210386655.8A patent/CN102863948B/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1566256A (en) * | 2003-07-04 | 2005-01-19 | 大庆高新区鑫诺精细化工有限公司 | Alkyl aryl alkylbetaine surfactant composition and its application in tertiary oil recovery |
| CN102159204A (en) * | 2008-09-19 | 2011-08-17 | 辉瑞公司 | Stable liquid antibody formulation |
| CN101654421A (en) * | 2009-08-27 | 2010-02-24 | 浙江合诚化学有限公司 | Synthesis method of cocoamidopropyl-2-hydroxyl-3-sulfopropyl betaine |
| US20110166128A1 (en) * | 2010-01-07 | 2011-07-07 | Alkermes, Inc. | Diaryldiazepine Prodrugs for the Treatment of Neurological and Psychological Disorders |
| CN101891655A (en) * | 2010-06-23 | 2010-11-24 | 程玉桥 | Method for preparing modified betaine type amphoteric surfactant used for tertiary oil recovery |
| US20120196776A1 (en) * | 2011-02-02 | 2012-08-02 | Gupta D V Satyanarayana | Oil Field Treatment Fluids |
| WO2012106336A2 (en) * | 2011-02-02 | 2012-08-09 | Baker Hughes Incorporated | Oil field treatment fluids |
| CN102618244A (en) * | 2011-03-11 | 2012-08-01 | 中国石油天然气股份有限公司 | Betaine surfactant and preparation method and application thereof |
| CN102205215A (en) * | 2011-04-28 | 2011-10-05 | 孙安顺 | Crude oil emulsifying agent |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015161812A1 (en) * | 2014-04-23 | 2015-10-29 | Jiangnan University | Compounds, compositions thereof and methods for hydrocarbon extraction using the same |
| CN107075355A (en) * | 2014-04-23 | 2017-08-18 | 江南大学 | Compound, its composition and the method for extracting oil gas using the compound |
| CN107075355B (en) * | 2014-04-23 | 2019-10-25 | 江南大学 | Compound, its composition and the method for using the compound to extract oil gas |
| CN103992247A (en) * | 2014-05-15 | 2014-08-20 | 中国石油天然气股份有限公司 | Fatty alcohol polyoxypropylene ether sulphobetaine and alkali-free composite combination for displacing oil |
| CN103992247B (en) * | 2014-05-15 | 2016-08-03 | 中国石油天然气股份有限公司 | Fatty alcohol polyoxypropylene ether sulfobetaines and alkali-free compound flooding oil compositions |
| CN108948342A (en) * | 2018-08-07 | 2018-12-07 | 江苏四新界面剂科技有限公司 | A kind of preparation method of the chain of oxyethylene group containing poly amphoteric surfactant |
| CN110835522A (en) * | 2018-08-17 | 2020-02-25 | 中国石油化工股份有限公司 | Temperature-resistant and salt-resistant type super-thick oil emulsifying viscosity reducer and preparation method thereof |
| CN110835522B (en) * | 2018-08-17 | 2022-02-15 | 中国石油化工股份有限公司 | Temperature-resistant and salt-resistant type super-thick oil emulsifying viscosity reducer and preparation method thereof |
| CN111607381A (en) * | 2019-02-25 | 2020-09-01 | 中国石油天然气股份有限公司 | High-temperature diverting acid composition and preparation method thereof |
| CN111607380A (en) * | 2019-02-25 | 2020-09-01 | 中国石油天然气股份有限公司 | Surfactant for reservoir transformation and preparation method thereof |
| CN111607380B (en) * | 2019-02-25 | 2022-07-05 | 中国石油天然气股份有限公司 | Surfactant for reservoir transformation and preparation method thereof |
| CN113135846A (en) * | 2021-04-07 | 2021-07-20 | 吉和昌新材料(荆门)有限公司 | Preparation method of sulfobetaine type waterborne polyurethane chain extender |
| CN115044425A (en) * | 2022-06-09 | 2022-09-13 | 中海油天津化工研究设计院有限公司 | Oil stain cleaning agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102863948B (en) | 2014-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102863948B (en) | Hydroxysulfobetaine amphoteric surfactant for flooding and preparation method of hydroxysulfobetaine amphoteric surfactant | |
| Guo et al. | Separation of phenol from model oils with quaternary ammonium salts via forming deep eutectic solvents | |
| CN102304069B (en) | Method for synthesizing saturated cardanol sulfonate surfactant for oil displacement | |
| CN109134882B (en) | Carbazolyl hydrogen bond organic framework material and preparation method and application thereof | |
| CN102688722B (en) | Hydrogenated rosin-based quaternary ammonium salt gemini surfactant and preparation method thereof | |
| CN105344327A (en) | Preparation method of MOFs graphene composite material | |
| Ji et al. | Separation of phenolic compounds from oil mixtures using environmentally benign biological reagents based on Brønsted acid-Lewis base interaction | |
| CN100374192C (en) | Surface activator with double-ether bisbensulfosalt and double molecule | |
| CN103145568A (en) | Cardanol cationoid quaternary ammonium salt and preparation method thereof | |
| CN102851016B (en) | Carboxy-lycine amphoteric surfactant for oil displacement and preparation method thereof | |
| CN101966437A (en) | Sulphobetaine ampholytic gemini surfactant and synthesis method thereof | |
| WO2015101355A1 (en) | Sulfonate-type biomass surfactant and synthesis method thereof | |
| CN106631912A (en) | Hydroxysulfobetaine surfactant and preparation method and application thereof | |
| CN105037176A (en) | Preparation method for quaternary ammonium salt dimeric surfactant containing hydroxyl group and application of quaternary ammonium salt dimeric surfactant containing hydroxyl group in tertiary oil recovery | |
| CN103923015A (en) | Two selective ionic liquids and synthesis method thereof | |
| CN102140115B (en) | Flame-retardant plasticizer of methyl silicate trichloroethyl ester compound and preparation method thereof | |
| CN104927823A (en) | Dianionic surfactant oil displacement agent and preparation method therefor and application thereof | |
| CN104262127B (en) | Brush-type two fluorine monomer and synthetic method thereof | |
| CN104326893B (en) | Side chain type two fluorine monomers and synthetic method thereof | |
| CN101935522A (en) | Preparation of long-chain alkyl acyl benzene sulfonic acid sodium salt and application thereof in enhancing oil recovery rate | |
| CN103288693B (en) | A kind of method preparing 1-sulfydryl pyrene and midbody compound thereof | |
| CN102728272A (en) | Cashew-based quaternary ammonium salt cationic surfactant and its preparation method | |
| CN109879806A (en) | A kind of isoquinolin indenes ether derivant and preparation method thereof | |
| CN102010317A (en) | Method for synthesizing felbinac and derivatives thereof | |
| CN105085320B (en) | Synthesis method of dicyano substituted biphenyl compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140813 Termination date: 20161014 |