CN104109519B - Betaine polymer displacement composition and preparation method - Google Patents
Betaine polymer displacement composition and preparation method Download PDFInfo
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- CN104109519B CN104109519B CN201310129871.9A CN201310129871A CN104109519B CN 104109519 B CN104109519 B CN 104109519B CN 201310129871 A CN201310129871 A CN 201310129871A CN 104109519 B CN104109519 B CN 104109519B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
Abstract
The present invention relates to alkyl betaine surface activator composition used for tertiary oil recovery and preparation method, mainly solve the displacement composition containing conventional surfactants in the prior art and particularly contain HCO in high temperature and high salt oil reservoir3 ‑Oil displacement efficiency in the water of stratum is poor, concentration is high and ternary composite driving in the corrosion that is brought to stratum and oil well of alkali and incrustation the problem of injure.The present invention is by displacement composition used for tertiary oil recovery, by weight percentage including following component：（1）1 part of beet alkali surface activator；（2）0.01~10 part of polymer；Wherein component（1）General molecular formula be：In formula, R is C8~C30Alkyl, R ' be C1~C6Alkylidene, n+m=2~100；A kind of technical scheme of the polymer in super high molecular weight polyacrylamide, Heat Resistant and Salt Tolerant Polymer A or xanthans, preferably solves the problem, available in the tertiary oil recovery production in oil field.
Description
Technical field
The present invention relates to glycine betaine-polymer composition used for tertiary oil recovery and preparation method.
Background technology
China's main oilfield comes into high water-cut stage after primary and secondary exploitation, how to improve oil recovery factor,
Remaining reserves are developed to greatest extent, and tertiary oil recovery technology has played very important work in terms of oilfield stable production high yield is ensured
With.In tertiary oil recovery new technology, chemical combined flooding is still one of very promising method of tool.
Oil field enter high water-cut stage after, remaining oil with discontinuous oil film by trap in the hole of reservoir rockses, make
Two main power on oil droplet be it is viscous from and capillary force.If using appropriate surfactant system, reduction oil
Interfacial tension between water, oil droplet deforms brought resistance when just reducing residual oil movement, so as to improve oil recovery factor.
In recent years, it has been found that betaine type surface-active has good table, interfacial activity, can be in oil-water interfaces
Formed compared with low interfacial tension.Simultaneously as its Stability Analysis of Structures, having metal ion chelant effect, thus it can attempt to be used for high ore deposit
The oil reservoir displacement of reservoir oil of change degree, higher temperature.In addition, another feature of betaine type amphoteric surfactant be its performance by salinity and
The pH influences of medium are little, thus can be higher in salinity or be used for combination flooding in the range of extensive pH, so as to cause pole
Big concern.Betaine type amphoteric surfactant with interface performance and rheological characteristic, is expected to replace the alkali in ternary composite driving formula,
Under rational formula system, binary displacement system is finally realized, is that the chemical flooding in oil field opens up new approach.
In addition, in existing ternary composite oil-displacing system, the alkali containing high concentration, such as sodium hydroxide, sodium carbonate make
During, huge injury is brought to stratum and oil well etc., used surfactant is difficult to be biodegradable, and to people
Body also has certain harmfulness, such as：1991, Zhao Guoxi existed《Surfactant physical chemistry》P495；, Liu Cheng in 1994
《Surfactant is complete works of》Content disclosed in P35.So for those harsh oil reservoirs, we ought to seek one kind in nothing
Alkali, high temperature（Formation temperature is more than 85 DEG C）, under the conditions of Stability Analysis of Structures, and can with crude oil formation 10-3-10-4The ultralow interfaces of mN/m
Power, effectively improves the displacing surfactant system of oil recovery factor.
The content of the invention
One of technical problems to be solved by the invention be in the prior art the displacement composition containing surfactant in height
Temperature, oil displacement efficiency is poor under the conditions of high salinity, simultaneously because contain alkali, brings injury to stratum and oil well, and etching apparatus and defeated
There is provided a kind of glycine betaine-polymer flooding fluid composition for the problem of sending pipeline.The surface activator composition has in alkali-free, height
Under warm high salt conditions, remain to and crude oil formation 10-3MN/m ultralow interfacial tension, with improve recovery ratio the characteristics of.
The two of technical problem solved by the invention are to provide one of above-mentioned technical problem glycine betaine-polymer displacement of reservoir oil
The preparation method of composition.
The three of the technical problems to be solved by the invention are two obtained glycine betaine-polymer using above-mentioned technical problem
Application of the displacement composition in the displacement of reservoir oil of oil field.
One of in order to solve the above-mentioned technical problem, technical scheme is as follows：Glycine betaine-polymer displacement of reservoir oil combination
Thing, described composition includes following component in parts by weight：
（1）1 part of beet alkali surface activator；
（2）0.01~10 part of polymer；
Wherein component（1）General molecular formula be：
In formula：R is C8~C30Alkyl, R ' be C1~C6Alkylidene, n+m=2 ~ 100；Described polymer is selected from polypropylene
One kind in acid amides, Heat Resistant and Salt Tolerant Polymer A or xanthans；The viscosity average molecular weigh molecular weight of the polyacrylamide be 2,000,000 ~
9000000；Described Heat Resistant and Salt Tolerant Polymer A is by by acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, 2- acryloyls
Four kinds of monomer copolymerizations of amido dodecyl sodium sulfonate and pi-allyl oleyl ether are formed, and the mol ratio of four kinds of monomers is（76-83）:（7-
18）:（5-8）:1.
Preferred n+m=2~20 in above-mentioned technical proposal；The preferred C of alkyl R10~C25Alkyl, more preferably C14~C20's
Alkyl；R ' preferably C1~C5Alkylidene.Most have preferably：R is C16~C18Alkyl, m+n=12 ~ 16, R ' be C1~C2Alkylene
Base.
In above-mentioned technical proposal, in order to reduce transport and storage cost described in composition can be by component（1）And component（2）
The form supply of the composition of composition, in order to which onsite application facilitates the composition to include 100 ~ 2000 in parts by weight
The water of part.The water that described water can be used can be deionized water, river, underground water, seawater, preferably total salinity scope
For 10000~35000mg/L, Ca2++Mg2+For 500~2000mg/L, HCO- 3For 0-6000mg/L water, for easy construction,
The Jiangsu that consideration in terms of saving water resource, more preferably oilfield injection water or sewage, such as embodiment of the present invention are used is husky
Seven oilfield injection waters.In order to increase oil displacement efficiency, mobility and the dissolving of glycine betaine-polymer composition oil displacement system are improved
Degree, auxiliary agent can also include appointing in small molecule alcohol commonly used in the art, ethers, salt, DMSO, diethanol amine, CTAC etc.
Meaning one or more are mixed.
In order to solve the above-mentioned technical problem two, technical scheme is as follows：Beet described in one of above mentioned problem
The preparation method of alkali-polymer flooding fluid composition, is comprised the steps of：
a）Primary hydrocarbyl amine is 80~180 DEG C in reaction temperature with aequum oxirane, and pressure is 0~0.80MPa（Table
Pressure）, react 1~10 hour, obtain alkyl APEO tertiary amine.
B) step a) alkyl APEOs tertiary amine, aldehyde, sodium sulfite and sodium hydrogensulfite mixture and solvent are added
Reactor, 40~160oC react 2~20 hours generation beet alkali surface activator, wherein alkyl APEO tertiary amine with
The mol ratio of aldehyde, sodium sulfite and sodium hydrogensulfite mixture is 1：(1.05~2):(1~3).
C) the desired amount of beet alkali surface activator, described Heat Resistant and Salt Tolerant Polymer A and water are uniformly mixed, obtains institute
The glycine betaine stated-polymer flooding fluid composition, in terms of parts by weight, beet alkali surface activator, above-mentioned temperature-resistant anti-salt polymerization
The weight part ratio of thing A and water is 1 part：0.01~10 part: 100 ~ 2000 part.
In above-mentioned technical proposal, step a) reaction can be reacted in the presence of conventional base catalyst；But it is excellent
Choosing：As n+m=2, reaction does not obtain alkyl APEO tertiary amine to the step a) in the case of extra catalyst, as n+m ＞ 2
Shi Suoshu steps a) every mole of primary hydrocarbyl amine and 2 moles of ethylene oxide first in the case of not extra catalyst are reacted, then
Obtain alkyl APEO tertiary amine with the reacting ethylene oxide of required surplus in the presence of base catalyst again.The alkalescence
At least one of catalyst preferred alkali metal hydroxide, alkaline earth metal hydroxide, more preferably magnesium hydroxide, calcium hydroxide
At least one of or barium hydroxide；The consumption of step a) neutral and alkali catalyst is preferably primary hydrocarbyl amine and oxirane gross weight
0.05~3wt%.
Step a) the reaction temperatures are 150 ~ 170oC, the reaction time is 8 ~ 10 hours.Step b）The middle preferred C of solvent1~C5
Alcohol in any one.Step b) the alkyl APEO tertiary amines and aldehyde, sodium sulfite and sodium hydrogensulfite mixture
Mol ratio be preferably 1：(1.05~1.5):(1~2).
In order to solve the above-mentioned technical problem three, technical scheme is as follows：A kind of method for strengthening the displacement of reservoir oil, will be upper
The aqueous solution injection oil bearing bed of one of technical problem glycine betaine-polymer flooding fluid composition is stated by crude oil from oil bearing bed
Middle displacement comes out；Wherein, the weight part ratio of beet alkali surface activator and water described in the aqueous solution is 1 part:100~4000
Part.
Glycine betaine-polymer flooding fluid composition of the present invention shows in water through physical analogy displacement experiment Lab-evaluation result
Oil recovery factor is improved on the basis of drive up to 15%, preferable technique effect is achieved.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
1st, prepared by beet alkali surface activator
a）Octadecyl primary amine is added into the reactor equipped with condensing unit and agitating device（1 mole）, side leads to nitrogen
While when being heated to 150 DEG C, heating adds oxirane after 40 minutes（2 moles）, temperature maintains 155 DEG C of stirring reactions 1 hour.
80 DEG C are cooled to, barium hydroxide is added as catalyst, is heated to 140 DEG C, open vacuum system, 1 is dehydrated under a high vacuum small
When, 4 times then are purged with the air in removing system with nitrogen, and system reaction temperature is then adjusted to 165 DEG C and is slowly passed through ring
Oxidative ethane（4 moles）, control pressure<0.80MPa, which carries out alkoxylation to reaction, to be terminated, and is neutralized after cooling with oxalic acid, mistake
Filter, dehydration, obtain octadecyl polyoxyethylene（n+m=6）Ether tertiary amine.Wherein the consumption of barium hydroxide is octadecyl primary amine and ring
The 0.5wt% of oxidative ethane weight.
b）By octadecyl polyoxyethylene（n+m=6）Ether tertiary amine（1 mole）, 30wt% formalin（In terms of formaldehyde
1.5 mole）The ethanol for being dissolved in 400ml is stirring evenly and then adding into reactor, and 10% sodium sulfite and sodium hydrogensulfite is slowly added dropwise
The aqueous solution of mixture（2 moles in terms of mixture）, at 40 DEG C react 2 hours after, be warming up to 60 DEG C at reflux after
Continuous reaction 6 hours, during which adds 20gNaOH to ensure that two-phase is sufficiently mixed.After reaction terminates, hydrochloric acid is added dropwise and adjusts the pH of system
To neutrality, it is extracted with ethyl acetate, ethyl acetate, second alcohol and water in oil phase is evaporated off, is then recrystallized in acetone solvent
To alkyl APEO sulfobetaine surfactant.
C) parts by weight of alkyl APEO sulfobetaine surfactant 1 of step b) synthesis, temperature-resistant anti-salt are gathered
Compound A（Viscosity average molecular weigh 6,500,000, acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, 2- acrylamido dodecyls
Four kinds of monomer copolymerizations of sulfonic acid and pi-allyl oleyl ether, four kinds of monomer mole ratios are 78:16:7:1）3 parts by weight and 1000
The stratum water of parts by weight Jiangsu sand seven is mixed 2 hours, obtains a kind of displacement composition of homogeneous transparent.
2nd, glycine betaine-polymer displacement of reservoir oil composition properties are evaluated
Above-mentioned transparent glycine betaine-polymer flooding fluid composition is used for interfacial tension evaluation, apparent viscosity and the displacement of reservoir oil real
Test.The composition of husky seven oilfield injection water used is shown in Table 1 wherein in all embodiments of the invention and comparative example.It will be driven for ease of comparing
The composition of fluid composition is listed in table 2.
A) interfacial tension evaluation
TX-500C rotating interfacial tensimeters are produced using Texas ,Usa university, at 83 DEG C, rotating speed is 4500
Under the conditions of rev/min, the interfacial tension determined between above-mentioned displacement composition and husky seven oil field produced dewatered oils the results are shown in Table
3。
B) apparent viscosity
Using the BROODFIELD of Brookfield companies of the U.S.Type viscosimeter, at 83 DEG C, mixing time is 30min
Under the conditions of point, the apparent viscosity for determining above-mentioned displacement composition the results are shown in Table 4.
C) oil displacement experiment evaluation
According to the composite oil-displacing system physical simulation flooding test in SY/T6424-2000 composite oil-displacing system performance test methods
Measure of merit, at 83 DEG C, length is 30cm, a diameter of 2.5cm, and permeability is 1.5 m2Rock core on to carry out imitation oil displacement experiment real
Test.The salinity for injecting water is 25830mg/L, and the total content of magnesium and calcium is 374mg/L；Carbonic acid hydrogen amount is 5125 mg/L saturation crude oil
Viscosity is 10mpa.s.First with injection water drive to aqueous 92 %, after water drive terminates, metaideophone 0.3PV（PV is injection pore volume）On
State after displacement composition, water drive to aqueous 98%.Improve oil recovery factor and the results are shown in Table 5.
【Embodiment 2】
1st, prepared by beet alkali surface activator
a）Octadecyl primary amine is added into the reactor equipped with condensing unit and agitating device（1 mole）, side leads to nitrogen
While when being heated to 150 DEG C, heating adds oxirane after 40 minutes（2 moles）, temperature maintains 155 DEG C of stirring reactions 1 hour.
80 DEG C are cooled to, barium hydroxide is added as catalyst, is heated to 140 DEG C, open vacuum system, 1 is dehydrated under a high vacuum small
When, 4 times then are purged with the air in removing system with nitrogen, and system reaction temperature is then adjusted to 165 DEG C and is slowly passed through ring
Oxidative ethane（1 mole）, control pressure<0.80MPa, which carries out alkoxylation to reaction, to be terminated, and is neutralized after cooling with oxalic acid, mistake
Filter, dehydration, obtain octadecyl polyoxyethylene（n+m=3）Ether tertiary amine.Wherein the consumption of barium hydroxide is octadecyl primary amine and ring
The 0.5wt% of oxidative ethane weight.
b）By octadecyl polyoxyethylene（n+m=3）Ether tertiary amine（1 mole）, 30wt% formalin（In terms of formaldehyde
1.5 mole）The ethanol for being dissolved in 400ml is stirring evenly and then adding into reactor, and 10% sodium sulfite and sodium hydrogensulfite is slowly added dropwise
The aqueous solution of mixture（2 moles in terms of mixture）, at 40 DEG C react 2 hours after, be warming up to 60 DEG C at reflux after
Continuous reaction 6 hours, during which adds 20gNaOH to ensure that two-phase is sufficiently mixed.After reaction terminates, hydrochloric acid is added dropwise and adjusts the pH of system
To neutrality, it is extracted with ethyl acetate, ethyl acetate, second alcohol and water in oil phase is evaporated off, is then recrystallized in acetone solvent
To alkyl APEO sulfobetaine surfactant.
C) parts by weight of alkyl APEO sulfobetaine surfactant 1 of step b) synthesis, temperature-resistant anti-salt are gathered
The parts by weight of compound 3（Viscosity average molecular weigh 6,500,000, by acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, 2- acrylamidos
Four kinds of monomer copolymerizations of dodecyl sodium sulfonate and pi-allyl oleyl ether are formed, and the mol ratio of four kinds of monomers is 78:16:7:1）With 1000
The stratum water of parts by weight Jiangsu sand seven is mixed 2 hours, obtains a kind of composition of the displacement of reservoir oil of homogeneous transparent.
2nd, glycine betaine-polymer displacement of reservoir oil composition properties are evaluated
In addition to displacement composition composition is different, method of evaluating performance be the same as Example 1.The displacement of reservoir oil is combined for ease of comparing
The composition of thing is listed in table 2, and evaluation result is listed in into table 3, table 4 and table 5.
【Embodiment 3】
1st, prepared by beet alkali surface activator
a）Octadecyl primary amine is added into the reactor equipped with condensing unit and agitating device（1 mole）, side leads to nitrogen
While when being heated to 150 DEG C, heating adds oxirane after 40 minutes（2 moles）, temperature maintains 155 DEG C of stirring reactions 1 hour.
80 DEG C are cooled to, barium hydroxide is added as catalyst, is heated to 140 DEG C, open vacuum system, 1 is dehydrated under a high vacuum small
When, 4 times then are purged with the air in removing system with nitrogen, and system reaction temperature is then adjusted to 165 DEG C and is slowly passed through ring
Oxidative ethane（6 moles）, control pressure<0.80MPa, which carries out alkoxylation to reaction, to be terminated, and is neutralized after cooling with oxalic acid, mistake
Filter, dehydration, obtain octadecyl polyoxyethylene（n+m=8）Ether tertiary amine.Wherein the consumption of barium hydroxide is octadecyl primary amine and ring
The 0.5wt% of oxidative ethane weight.
b）By octadecyl polyoxyethylene（n+m=8）Ether tertiary amine（1 mole）, 30wt% formalin（In terms of formaldehyde
1.5 mole）The ethanol for being dissolved in 400ml is stirring evenly and then adding into reactor, and 10% sodium sulfite and sodium hydrogensulfite is slowly added dropwise
The aqueous solution of mixture（2 moles in terms of mixture）, at 40 DEG C react 2 hours after, be warming up to 60 DEG C at reflux after
Continuous reaction 6 hours, during which adds 20gNaOH to ensure that two-phase is sufficiently mixed.After reaction terminates, hydrochloric acid is added dropwise and adjusts the pH of system
To neutrality, it is extracted with ethyl acetate, ethyl acetate, second alcohol and water in oil phase is evaporated off, is then recrystallized in acetone solvent
To alkyl APEO sulfobetaines.
C) parts by weight of alkyl APEO sulfobetaine surfactant 1 of step b) synthesis, temperature-resistant anti-salt are gathered
The parts by weight of compound 3（Viscosity average molecular weigh 6,500,000, by acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, 2- acrylamidos
Four kinds of monomer copolymerizations of dodecyl sodium sulfonate and pi-allyl oleyl ether are formed, and the mol ratio of four kinds of monomers is 78:16:7:1）With 1000
The stratum water of parts by weight Jiangsu sand seven is mixed 2 hours, obtains a kind of composition of the displacement of reservoir oil of homogeneous transparent.
2nd, glycine betaine-polymer displacement of reservoir oil composition properties are evaluated
In addition to displacement composition composition is different, method of evaluating performance be the same as Example 1.The displacement of reservoir oil is combined for ease of comparing
The composition of thing is listed in table 2, and evaluation result is listed in into table 3, table 4 and table 5.
【Embodiment 4】
1st, prepared by beet alkali surface activator
a）Octadecyl primary amine is added into the reactor equipped with condensing unit and agitating device（1 mole）, side leads to nitrogen
While when being heated to 150 DEG C, heating adds oxirane after 40 minutes（2 moles）, temperature maintains 155 DEG C of stirring reactions 1 hour.
80 DEG C are cooled to, barium hydroxide is added as catalyst, is heated to 140 DEG C, open vacuum system, 1 is dehydrated under a high vacuum small
When, 4 times then are purged with the air in removing system with nitrogen, and system reaction temperature is then adjusted to 165 DEG C and is slowly passed through ring
Oxidative ethane（7 moles）, control pressure<0.80MPa, which carries out alkoxylation to reaction, to be terminated, and is neutralized after cooling with oxalic acid, mistake
Filter, dehydration, obtain octadecyl polyoxyethylene（n+m=9）Ether tertiary amine.Wherein the consumption of barium hydroxide is octadecyl primary amine and ring
The 0.5wt% of oxidative ethane weight.
b）By octadecyl polyoxyethylene（n+m=9）Ether tertiary amine（1 mole）, 30wt% formalin（In terms of formaldehyde
1.5 mole）The ethanol for being dissolved in 400ml is stirring evenly and then adding into reactor, and 10% sodium sulfite and sodium hydrogensulfite is slowly added dropwise
The aqueous solution of mixture（2 moles in terms of mixture）, at 40 DEG C react 2 hours after, be warming up to 60 DEG C at reflux after
Continuous reaction 6 hours, during which adds 20gNaOH to ensure that two-phase is sufficiently mixed.After reaction terminates, hydrochloric acid is added dropwise and adjusts the pH of system
To neutrality, it is extracted with ethyl acetate, ethyl acetate, second alcohol and water in oil phase is evaporated off, is then recrystallized in acetone solvent
To alkyl APEO sulfobetaine surfactant.
C) parts by weight of alkyl APEO sulfobetaine surfactant 1 of step b) synthesis, temperature-resistant anti-salt are gathered
The parts by weight of compound 3（Viscosity average molecular weigh 6,500,000, by acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, 2- acrylamidos
Four kinds of monomer copolymerizations of dodecyl sodium sulfonate and pi-allyl oleyl ether are formed, and the mol ratio of four kinds of monomers is 78:16:7:1）With 1000
The stratum water of parts by weight Jiangsu sand seven is mixed 2 hours, obtains a kind of composition of the displacement of reservoir oil of homogeneous transparent.
2nd, glycine betaine-polymer displacement of reservoir oil composition properties are evaluated
In addition to displacement composition composition is different, method of evaluating performance be the same as Example 1.The displacement of reservoir oil is combined for ease of comparing
The composition of thing is listed in table 2, and evaluation result is listed in into table 3, table 4 and table 5.
【Embodiment 5】
1st, prepared by beet alkali surface activator
a）Octadecyl primary amine is added into the reactor equipped with condensing unit and agitating device（1 mole）, side leads to nitrogen
While when being heated to 150 DEG C, heating adds oxirane after 40 minutes（2 moles）, temperature maintains 155 DEG C of stirring reactions 1 hour.
80 DEG C are cooled to, barium hydroxide is added as catalyst, is heated to 140 DEG C, open vacuum system, 1 is dehydrated under a high vacuum small
When, 4 times then are purged with the air in removing system with nitrogen, and system reaction temperature is then adjusted to 165 DEG C and is slowly passed through ring
Oxidative ethane（10 moles）, control pressure<0.80MPa, which carries out alkoxylation to reaction, to be terminated, and is neutralized after cooling with oxalic acid, mistake
Filter, dehydration, obtain octadecyl polyoxyethylene（n+m=12）Ether tertiary amine.Wherein the consumption of barium hydroxide is octadecyl primary amine and ring
The 0.5wt% of oxidative ethane weight.
b）By octadecyl polyoxyethylene（n+m=12）Ether tertiary amine（1 mole）, 30wt% formalin（In terms of formaldehyde
1.5 mole）The ethanol for being dissolved in 400ml is stirring evenly and then adding into reactor, and 10% sodium sulfite and sodium hydrogensulfite is slowly added dropwise
The aqueous solution of mixture（2 moles in terms of mixture）, at 40 DEG C react 2 hours after, be warming up to 60 DEG C at reflux after
Continuous reaction 6 hours, during which adds 20gNaOH to ensure that two-phase is sufficiently mixed.After reaction terminates, hydrochloric acid is added dropwise and adjusts the pH of system
To neutrality, it is extracted with ethyl acetate, ethyl acetate, second alcohol and water in oil phase is evaporated off, is then recrystallized in acetone solvent
To alkyl APEO sulfobetaine surfactant.
C) parts by weight of alkyl APEO sulfobetaine surfactant 1 of step b) synthesis, temperature-resistant anti-salt are gathered
The parts by weight of compound 3（Viscosity average molecular weigh 6,500,000, by acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, 2- acrylamidos
Four kinds of monomer copolymerizations of dodecyl sodium sulfonate and pi-allyl oleyl ether are formed, and the mol ratio of four kinds of monomers is 78:16:7:1）With 1000
The stratum water of parts by weight Jiangsu sand seven is mixed 2 hours, obtains a kind of composition of the displacement of reservoir oil of homogeneous transparent.
2nd, glycine betaine-polymer displacement of reservoir oil composition properties are evaluated
In addition to displacement composition composition is different, method of evaluating performance be the same as Example 1.The displacement of reservoir oil is combined for ease of comparing
The composition of thing is listed in table 2, and evaluation result is listed in into table 3, table 4 and table 5.
【Embodiment 6】
1st, prepared by beet alkali surface activator
a）Octadecyl primary amine is added into the reactor equipped with condensing unit and agitating device（1 mole）, side leads to nitrogen
While when being heated to 150 DEG C, heating adds oxirane after 40 minutes（2 moles）, temperature maintains 155 DEG C of stirring reactions 1 hour.
80 DEG C are cooled to, barium hydroxide is added as catalyst, is heated to 140 DEG C, open vacuum system, 1 is dehydrated under a high vacuum small
When, 4 times then are purged with the air in removing system with nitrogen, and system reaction temperature is then adjusted to 165 DEG C and is slowly passed through ring
Oxidative ethane（14 moles）, control pressure<0.80MPa, which carries out alkoxylation to reaction, to be terminated, and is neutralized after cooling with oxalic acid, mistake
Filter, dehydration, obtain octadecyl polyoxyethylene（n+m=16）Ether tertiary amine.Wherein the consumption of barium hydroxide is octadecyl primary amine and ring
The 0.5wt% of oxidative ethane weight.
b）By octadecyl polyoxyethylene（n+m=16）Ether tertiary amine（1 mole）, 30wt% formalin（In terms of formaldehyde
1.5 mole）The ethanol for being dissolved in 400ml is stirring evenly and then adding into reactor, and 10% sodium sulfite and sodium hydrogensulfite is slowly added dropwise
The aqueous solution of mixture（2 moles in terms of mixture）, at 40 DEG C react 2 hours after, be warming up to 60 DEG C at reflux after
Continuous reaction 6 hours, during which adds 20gNaOH to ensure that two-phase is sufficiently mixed.After reaction terminates, hydrochloric acid is added dropwise and adjusts the pH of system
To neutrality, it is extracted with ethyl acetate, ethyl acetate, second alcohol and water in oil phase is evaporated off, is then recrystallized in acetone solvent
To alkyl APEO sulfobetaine surfactant.
C) parts by weight of alkyl APEO sulfobetaine surfactant 1 of step b) synthesis, temperature-resistant anti-salt are gathered
The parts by weight of compound 3（Viscosity average molecular weigh 6,500,000, by acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, 2- acrylamidos
Four kinds of monomer copolymerizations of dodecyl sodium sulfonate and pi-allyl oleyl ether are formed, and the mol ratio of four kinds of monomers is 78:16:7:1）With 1000
The stratum water of parts by weight Jiangsu sand seven is mixed 2 hours, obtains a kind of composition of the displacement of reservoir oil of homogeneous transparent.
2nd, glycine betaine-polymer displacement of reservoir oil composition properties are evaluated
In addition to displacement composition composition is different, method of evaluating performance be the same as Example 1.The displacement of reservoir oil is combined for ease of comparing
The composition of thing is listed in table 2, and evaluation result is listed in into table 3, table 4 and table 5.
【Embodiment 7】
1st, prepared by beet alkali surface activator
a）Octadecyl primary amine is added into the reactor equipped with condensing unit and agitating device（1 mole）, side leads to nitrogen
While when being heated to 150 DEG C, heating adds oxirane after 40 minutes（2 moles）, temperature maintains 155 DEG C of stirring reactions 1 hour.
80 DEG C are cooled to, barium hydroxide is added as catalyst, is heated to 140 DEG C, open vacuum system, 1 is dehydrated under a high vacuum small
When, 4 times then are purged with the air in removing system with nitrogen, and system reaction temperature is then adjusted to 165 DEG C and is slowly passed through ring
Oxidative ethane（16 moles）, control pressure<0.80MPa, which carries out alkoxylation to reaction, to be terminated, and is neutralized after cooling with oxalic acid, mistake
Filter, dehydration, obtain octadecyl polyoxyethylene（n+m=18）Ether tertiary amine.Wherein the consumption of barium hydroxide is octadecyl primary amine and ring
The 0.5wt% of oxidative ethane weight.
b）By octadecyl polyoxyethylene（n+m=18）Ether tertiary amine（1 mole）, 30wt% formalin（In terms of formaldehyde
1.5 mole）The ethanol for being dissolved in 400ml is stirring evenly and then adding into reactor, and 10% sodium sulfite and sodium hydrogensulfite is slowly added dropwise
The aqueous solution of mixture（2 moles in terms of mixture）, at 40 DEG C react 2 hours after, be warming up to 60 DEG C at reflux after
Continuous reaction 6 hours, during which adds 20gNaOH to ensure that two-phase is sufficiently mixed.After reaction terminates, hydrochloric acid is added dropwise and adjusts the pH of system
To neutrality, it is extracted with ethyl acetate, ethyl acetate, second alcohol and water in oil phase is evaporated off, is then recrystallized in acetone solvent
To alkyl APEO sulfobetaine surfactant.
C) parts by weight of alkyl APEO sulfobetaine surfactant 1 of step b) synthesis, temperature-resistant anti-salt are gathered
The parts by weight of compound 3（Viscosity average molecular weigh 6,500,000, by acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, 2- acrylamidos
Four kinds of monomer copolymerizations of dodecyl sodium sulfonate and pi-allyl oleyl ether are formed, and the mol ratio of four kinds of monomers is 78:16:7:1）With 1000
The stratum water of parts by weight Jiangsu sand seven is mixed 2 hours, obtains a kind of composition of the displacement of reservoir oil of homogeneous transparent.
2nd, glycine betaine-polymer displacement of reservoir oil composition properties are evaluated
In addition to displacement composition composition is different, method of evaluating performance be the same as Example 1.The displacement of reservoir oil is combined for ease of comparing
The composition of thing is listed in table 2, and evaluation result is listed in into table 3, table 4 and table 5.
【Embodiment 8】
1st, prepared by beet alkali surface activator
a）Octadecyl primary amine is added into the reactor equipped with condensing unit and agitating device（1 mole）, side leads to nitrogen
While when being heated to 150 DEG C, heating adds oxirane after 40 minutes（2 moles）, temperature maintains 155 DEG C of stirring reactions 1 hour.
80 DEG C are cooled to, barium hydroxide is added as catalyst, is heated to 140 DEG C, open vacuum system, 1 is dehydrated under a high vacuum small
When, 4 times then are purged with the air in removing system with nitrogen, and system reaction temperature is then adjusted to 165 DEG C and is slowly passed through ring
Oxidative ethane（3 moles）, control pressure<0.80MPa, which carries out alkoxylation to reaction, to be terminated, and is neutralized after cooling with oxalic acid, mistake
Filter, dehydration, obtain octadecyl polyoxyethylene（n+m=5）Ether tertiary amine.Wherein the consumption of barium hydroxide is octadecyl primary amine and ring
The 0.5wt% of oxidative ethane weight.
b）By octadecyl polyoxyethylene（n+m=5）Ether tertiary amine（1 mole）, 25wt% acetaldehyde solution（In terms of acetaldehyde
1.5 mole）The ethanol for being dissolved in 400ml is stirring evenly and then adding into reactor, and 10% sodium sulfite and sodium hydrogensulfite is slowly added dropwise
The aqueous solution of mixture（2 moles in terms of mixture）, at 40 DEG C react 2 hours after, be warming up to 60 DEG C at reflux after
Continuous reaction 6 hours, during which adds 20gNaOH to ensure that two-phase is sufficiently mixed.After reaction terminates, hydrochloric acid is added dropwise and adjusts the pH of system
To neutrality, it is extracted with ethyl acetate, ethyl acetate, second alcohol and water in oil phase is evaporated off, is then recrystallized in acetone solvent
To alkyl APEO sulfobetaine surfactant.
C) parts by weight of alkyl APEO sulfobetaine surfactant 1 of step b) synthesis, temperature-resistant anti-salt are gathered
The parts by weight of compound 3（Viscosity average molecular weigh 6,500,000, by acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, 2- acrylamidos
Four kinds of monomer copolymerizations of dodecyl sodium sulfonate and pi-allyl oleyl ether are formed, and the mol ratio of four kinds of monomers is 78:16:7:1）With 1000
The stratum water of parts by weight Jiangsu sand seven is mixed 2 hours, obtains a kind of composition of the displacement of reservoir oil of homogeneous transparent.
2nd, glycine betaine-polymer displacement of reservoir oil composition properties are evaluated
In addition to displacement composition composition is different, method of evaluating performance be the same as Example 1.The displacement of reservoir oil is combined for ease of comparing
The composition of thing is listed in table 2, and evaluation result is listed in into table 3, table 4 and table 5.
【Embodiment 9】
1st, prepared by beet alkali surface activator
a）Cetyl primary amine is added into the reactor equipped with condensing unit and agitating device（1 mole）, side leads to nitrogen
While when being heated to 150 DEG C, heating adds oxirane after 40 minutes（2 moles）, temperature maintains 155 DEG C of stirring reactions 1 hour.
80 DEG C are cooled to, barium hydroxide is added as catalyst, is heated to 140 DEG C, open vacuum system, 1 is dehydrated under a high vacuum small
When, 4 times then are purged with the air in removing system with nitrogen, and system reaction temperature is then adjusted to 165 DEG C and is slowly passed through ring
Oxidative ethane（14 moles）, control pressure<0.80MPa, which carries out alkoxylation to reaction, to be terminated, and is neutralized after cooling with oxalic acid, mistake
Filter, dehydration, obtain cetyl polyoxyethylene（n+m=16）Ether tertiary amine.Wherein the consumption of barium hydroxide is cetyl primary amine and ring
The 0.5wt% of oxidative ethane weight.
b）By cetyl polyoxyethylene（n+m=16）Ether tertiary amine（1 mole）, 30wt% formalin（In terms of formaldehyde
1.5 mole）The ethanol for being dissolved in 400ml is stirring evenly and then adding into reactor, and 10% sodium sulfite and sodium hydrogensulfite is slowly added dropwise
The aqueous solution of mixture（2 moles in terms of mixture）, at 40 DEG C react 2 hours after, be warming up to 60 DEG C at reflux after
Continuous reaction 6 hours, during which adds 20gNaOH to ensure that two-phase is sufficiently mixed.After reaction terminates, hydrochloric acid is added dropwise and adjusts the pH of system
To neutrality, it is extracted with ethyl acetate, ethyl acetate, second alcohol and water in oil phase is evaporated off, is then recrystallized in acetone solvent
To alkyl APEO sulfobetaine surfactant.
C) parts by weight of alkyl APEO sulfobetaine surfactant 1 of step b) synthesis, temperature-resistant anti-salt are gathered
The parts by weight of compound 3（Viscosity average molecular weigh 6,500,000, by acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, 2- acrylamidos
Four kinds of monomer copolymerizations of dodecyl sodium sulfonate and pi-allyl oleyl ether are formed, and the mol ratio of four kinds of monomers is 78:16:7:1）With 1000
The stratum water of parts by weight Jiangsu sand seven is mixed 2 hours, obtains a kind of composition of the displacement of reservoir oil of homogeneous transparent.
2nd, glycine betaine-polymer displacement of reservoir oil composition properties are evaluated
In addition to displacement composition composition is different, method of evaluating performance be the same as Example 1.The displacement of reservoir oil is combined for ease of comparing
The composition of thing is listed in table 2, and evaluation result is listed in into table 3, table 4 and table 5.
【Embodiment 10】
1st, prepared by beet alkali surface activator
a）Dodecyl primary amine is added into the reactor equipped with condensing unit and agitating device（1 mole）, side leads to nitrogen
While when being heated to 150 DEG C, heating adds oxirane after 40 minutes（2 moles）, temperature maintains 155 DEG C of stirring reactions 1 hour.
80 DEG C are cooled to, barium hydroxide is added as catalyst, is heated to 140 DEG C, open vacuum system, 1 is dehydrated under a high vacuum small
When, 4 times then are purged with the air in removing system with nitrogen, and system reaction temperature is then adjusted to 165 DEG C and is slowly passed through ring
Oxidative ethane（6 moles）, control pressure<0.80MPa, which carries out alkoxylation to reaction, to be terminated, and is neutralized after cooling with oxalic acid, mistake
Filter, dehydration, obtain dodecyl polyoxyethylene（n+m=8）Ether tertiary amine.Wherein the consumption of barium hydroxide is dodecyl primary amine and ring
The 0.5wt% of oxidative ethane weight.
b）By dodecyl polyoxyethylene（n+m=8）Ether tertiary amine（1 mole）, 30wt% formalins（In terms of formaldehyde 1.5
Mole）The ethanol for being dissolved in 400ml is stirring evenly and then adding into reactor, and 10% sodium sulfite is slowly added dropwise and sodium hydrogensulfite is mixed
The aqueous solution of compound（2 moles in terms of mixture）, after being reacted 2 hours at 40 DEG C, it is warming up to 60 DEG C and continues at reflux
Reaction 6 hours, during which adds 20gNaOH to ensure that two-phase is sufficiently mixed.After reaction terminates, hydrochloric acid is added dropwise and is transferred to the pH of system
Neutrality, is extracted with ethyl acetate, and ethyl acetate, second alcohol and water in oil phase is evaporated off, is then recrystallized to give in acetone solvent
Alkyl APEO sulfobetaine surfactant.
C) parts by weight of alkyl APEO sulfobetaine surfactant 1 of step b) synthesis, temperature-resistant anti-salt are gathered
The parts by weight of compound 3（Viscosity average molecular weigh 6,500,000, by acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, 2- acrylamidos
Four kinds of monomer copolymerizations of dodecyl sodium sulfonate and pi-allyl oleyl ether are formed, and the mol ratio of four kinds of monomers is 78:16:7:1）With 1000
The stratum water of parts by weight Jiangsu sand seven is mixed 2 hours, obtains a kind of composition of the displacement of reservoir oil of homogeneous transparent.
2nd, glycine betaine-polymer displacement of reservoir oil composition properties are evaluated
In addition to displacement composition composition is different, method of evaluating performance be the same as Example 1.The displacement of reservoir oil is combined for ease of comparing
The composition of thing is listed in table 2, and evaluation result is listed in into table 3, table 4 and table 5.
【Embodiment 11】
1st, prepared by beet alkali surface activator
a）Dodecyl primary amine is added into the reactor equipped with condensing unit and agitating device（1 mole）, side leads to nitrogen
While when being heated to 150 DEG C, heating adds oxirane after 40 minutes（2 moles）, temperature maintains 155 DEG C of stirring reactions 1 hour.
80 DEG C are cooled to, barium hydroxide is added as catalyst, is heated to 140 DEG C, open vacuum system, 1 is dehydrated under a high vacuum small
When, 4 times then are purged with the air in removing system with nitrogen, and system reaction temperature is then adjusted to 165 DEG C and is slowly passed through ring
Oxidative ethane（7 moles）, control pressure<0.80MPa, which carries out alkoxylation to reaction, to be terminated, and is neutralized after cooling with oxalic acid, mistake
Filter, dehydration, obtain dodecyl polyoxyethylene（n+m=9）Ether tertiary amine.Wherein the consumption of barium hydroxide is dodecyl primary amine and ring
The 0.5wt% of oxidative ethane weight.
b）By dodecyl polyoxyethylene（n+m=9）Ether tertiary amine（1 mole）, 25wt% acetaldehyde solutions（In terms of acetaldehyde 1.5
Mole）The ethanol for being dissolved in 400ml is stirring evenly and then adding into reactor, and 10% sodium sulfite is slowly added dropwise and sodium hydrogensulfite is mixed
The aqueous solution of compound（2 moles in terms of mixture）, after being reacted 2 hours at 40 DEG C, it is warming up to 60 DEG C and continues at reflux
Reaction 6 hours, during which adds 20gNaOH to ensure that two-phase is sufficiently mixed.After reaction terminates, hydrochloric acid is added dropwise and is transferred to the pH of system
Neutrality, is extracted with ethyl acetate, and ethyl acetate, second alcohol and water in oil phase is evaporated off, is then recrystallized to give in acetone solvent
Alkyl APEO sulfobetaine surfactant.
C) parts by weight of alkyl APEO sulfobetaine surfactant 1 of step b) synthesis, temperature-resistant anti-salt are gathered
The parts by weight of compound 3（Viscosity average molecular weigh 6,500,000, by acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, 2- acrylamidos
Four kinds of monomer copolymerizations of dodecyl sodium sulfonate and pi-allyl oleyl ether are formed, and the mol ratio of four kinds of monomers is 78:16:7:1）With 1000
The stratum water of parts by weight Jiangsu sand seven is mixed 2 hours, obtains a kind of composition of the displacement of reservoir oil of homogeneous transparent.
2nd, glycine betaine-polymer displacement of reservoir oil composition properties are evaluated
In addition to displacement composition composition is different, method of evaluating performance be the same as Example 1.The displacement of reservoir oil is combined for ease of comparing
The composition of thing is listed in table 2, and evaluation result is listed in into table 3, table 4 and table 5.
【Embodiment 12】
1st, prepared by beet alkali surface activator
a）Dodecyl primary amine is added into the reactor equipped with condensing unit and agitating device（1 mole）, side leads to nitrogen
While when being heated to 150 DEG C, heating adds oxirane after 40 minutes（2 moles）, temperature maintains 155 DEG C of stirring reactions 1 hour.
80 DEG C are cooled to, barium hydroxide is added as catalyst, is heated to 140 DEG C, open vacuum system, 1 is dehydrated under a high vacuum small
When, 4 times then are purged with the air in removing system with nitrogen, and system reaction temperature is then adjusted to 165 DEG C and is slowly passed through ring
Oxidative ethane（14 moles）, control pressure<0.80MPa, which carries out alkoxylation to reaction, to be terminated, and is neutralized after cooling with oxalic acid, mistake
Filter, dehydration, obtain dodecyl polyoxyethylene（n+m=16）Ether tertiary amine.Wherein the consumption of barium hydroxide is dodecyl primary amine and ring
The 0.5wt% of oxidative ethane weight.
b）By dodecyl polyoxyethylene（n+m=16）Ether tertiary amine（1 mole）, 25wt% acetaldehyde solutions（In terms of acetaldehyde 1.5
Mole）The ethanol for being dissolved in 400ml is stirring evenly and then adding into reactor, and 10% sodium sulfite is slowly added dropwise and sodium hydrogensulfite is mixed
The aqueous solution of compound（2 moles in terms of mixture）, after being reacted 2 hours at 40 DEG C, it is warming up to 60 DEG C and continues at reflux
Reaction 6 hours, during which adds 20gNaOH to ensure that two-phase is sufficiently mixed.After reaction terminates, hydrochloric acid is added dropwise and is transferred to the pH of system
Neutrality, is extracted with ethyl acetate, and ethyl acetate, second alcohol and water in oil phase is evaporated off, is then recrystallized to give in acetone solvent
Alkyl APEO sulfobetaine surfactant.
C) parts by weight of alkyl APEO sulfobetaine surfactant 1 of step b) synthesis, temperature-resistant anti-salt are gathered
The parts by weight of compound 3（Viscosity average molecular weigh 6,500,000, by acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, 2- acrylamidos
Four kinds of monomer copolymerizations of dodecyl sodium sulfonate and pi-allyl oleyl ether are formed, and the mol ratio of four kinds of monomers is 78:16:7:1）With 1000
The stratum water of parts by weight Jiangsu sand seven is mixed 2 hours, obtains a kind of composition of the displacement of reservoir oil of homogeneous transparent.
2nd, glycine betaine-polymer displacement of reservoir oil composition properties are evaluated
In addition to displacement composition composition is different, method of evaluating performance be the same as Example 1.The displacement of reservoir oil is combined for ease of comparing
The composition of thing is listed in table 2, and evaluation result is listed in into table 3, table 4 and table 5.
【Embodiment 13】
1st, prepared by beet alkali surface activator
a）Aniline is added into the reactor equipped with condensing unit and agitating device（1 mole）, it is heated in logical nitrogen
At 150 DEG C, heating adds oxirane after 40 minutes（2 moles）, temperature maintains 155 DEG C of stirring reactions 1 hour.It is cooled to 80
DEG C, barium hydroxide is added as catalyst, 140 DEG C are heated to, vacuum system is opened, and is dehydrated 1 hour under a high vacuum, Ran Houyong
Nitrogen purges 4 times with the air in removing system, and system reaction temperature then is adjusted into 165 DEG C and is slowly passed through oxirane（6 rub
You）, control pressure<0.80MPa, which carries out alkoxylation to reaction, to be terminated, and is neutralized, filtered, is dehydrated with oxalic acid after cooling, obtained
Aniline polyoxyethylene（n+m=8）Ether tertiary amine.Wherein the consumption of barium hydroxide is the 0.5wt% of aniline and ethylene oxide weight.
b）By aniline polyoxyethylene（n+m=8）Ether tertiary amine（1 mole）, 30wt% formalins（1.5 moles in terms of formaldehyde）
The ethanol for being dissolved in 400ml is stirring evenly and then adding into reactor, and 10% sodium sulfite and sodium hydrogensulfite mixture is slowly added dropwise
The aqueous solution（2 moles in terms of mixture）, after being reacted 2 hours at 40 DEG C, it is warming up to 60 DEG C and continues to react 6 small at reflux
When, 20gNaOH is during which added to ensure that two-phase is sufficiently mixed.After reaction terminates, hydrochloric acid is added dropwise the pH of system is transferred to neutrality, use
Ethyl acetate is extracted, and ethyl acetate, second alcohol and water in oil phase is evaporated off, alkyl polyoxy is then recrystallized to give in acetone solvent
Vinethene sulfobetaine surfactant.
C) parts by weight of alkyl APEO sulfobetaine surfactant 1 of step b) synthesis, temperature-resistant anti-salt are gathered
The parts by weight of compound 3（Viscosity average molecular weigh 6,500,000, by acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, 2- acrylamidos
Four kinds of monomer copolymerizations of dodecyl sodium sulfonate and pi-allyl oleyl ether are formed, and the mol ratio of four kinds of monomers is 78:16:7:1）With 1000
The stratum water of parts by weight Jiangsu sand seven is mixed 2 hours, obtains a kind of composition of the displacement of reservoir oil of homogeneous transparent.
2nd, glycine betaine-polymer displacement of reservoir oil composition properties are evaluated
In addition to displacement composition composition is different, method of evaluating performance be the same as Example 1.The displacement of reservoir oil is combined for ease of comparing
The composition of thing is listed in table 2, and evaluation result is listed in into table 3, table 4 and table 5.
【Embodiment 14】
1st, prepared by beet alkali surface activator
a）Aniline is added into the reactor equipped with condensing unit and agitating device（1 mole）, it is heated in logical nitrogen
At 150 DEG C, heating adds oxirane after 40 minutes（2 moles）, temperature maintains 155 DEG C of stirring reactions 1 hour.It is cooled to 80
DEG C, barium hydroxide is added as catalyst, 140 DEG C are heated to, vacuum system is opened, and is dehydrated 1 hour under a high vacuum, Ran Houyong
Nitrogen purges 4 times with the air in removing system, and system reaction temperature then is adjusted into 165 DEG C and is slowly passed through oxirane（4 rub
You）, control pressure<0.80MPa, which carries out alkoxylation to reaction, to be terminated, and is neutralized, filtered, is dehydrated with oxalic acid after cooling, obtained
Aniline polyoxyethylene（n+m=6）Ether tertiary amine.Wherein the consumption of barium hydroxide is the 0.5wt% of aniline and ethylene oxide weight.
b）By aniline polyoxyethylene（n+m=6）Ether tertiary amine（1 mole）, 30wt% formalins（1.5 moles in terms of formaldehyde）
The ethanol for being dissolved in 400ml is stirring evenly and then adding into reactor, and 10% sodium sulfite and sodium hydrogensulfite mixture is slowly added dropwise
The aqueous solution（2 moles in terms of mixture）, after being reacted 2 hours at 40 DEG C, it is warming up to 60 DEG C and continues to react 6 small at reflux
When, 20gNaOH is during which added to ensure that two-phase is sufficiently mixed.After reaction terminates, hydrochloric acid is added dropwise the pH of system is transferred to neutrality, use
Ethyl acetate is extracted, and ethyl acetate, second alcohol and water in oil phase is evaporated off, alkyl polyoxy is then recrystallized to give in acetone solvent
Vinethene sulfobetaine surfactant.
C) parts by weight of alkyl APEO sulfobetaine surfactant 1 of step b) synthesis, temperature-resistant anti-salt are gathered
The parts by weight of compound 3（Viscosity average molecular weigh 6,500,000, by acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, 2- acrylamidos
Four kinds of monomer copolymerizations of dodecyl sodium sulfonate and pi-allyl oleyl ether are formed, and the mol ratio of four kinds of monomers is 78:16:7:1）With 1000
The stratum water of parts by weight Jiangsu sand seven is mixed 2 hours, obtains a kind of composition of the displacement of reservoir oil of homogeneous transparent.
2nd, glycine betaine-polymer displacement of reservoir oil composition properties are evaluated
In addition to displacement composition composition is different, method of evaluating performance be the same as Example 1.The displacement of reservoir oil is combined for ease of comparing
The composition of thing is listed in table 2, and evaluation result is listed in into table 3, table 4 and table 5.
【Embodiment 15】
1st, prepared by beet alkali surface activator
a）CH is added into the reactor equipped with condensing unit and agitating device3(CH2)7CH=CH(CH2)8NH2（1 mole）,
When being heated to 150 DEG C in logical nitrogen, heating adds oxirane after 40 minutes（2 moles）, it is anti-that temperature maintains 155 DEG C of stirrings
Answer 1 hour.80 DEG C are cooled to, barium hydroxide is added as catalyst, is heated to 140 DEG C, open vacuum system, under a high vacuum
Dehydration 1 hour, then purges 4 times with the air in removing system with nitrogen, system reaction temperature then is adjusted into 165 DEG C slowly
It is passed through oxirane（3 moles）, control pressure<0.80MPa, which carries out alkoxylation to reaction, to be terminated, and is used after cooling in oxalic acid
With, filtering, dehydration, obtain octadecylene base polyoxyethylene（n+m=5）Ether tertiary amine.Wherein the consumption of barium hydroxide is octadecylene base primary amine
With the 0.5wt% of ethylene oxide weight.
b）By octadecylene base polyoxyethylene（n+m=5）Ether tertiary amine（1 mole）, 25wt% acetaldehyde solutions（In terms of acetaldehyde 1.5
Mole）The ethanol for being dissolved in 400ml is stirring evenly and then adding into reactor, and 10% sodium sulfite is slowly added dropwise and sodium hydrogensulfite is mixed
The aqueous solution of compound（2 moles in terms of mixture）, after being reacted 2 hours at 40 DEG C, it is warming up to 60 DEG C and continues at reflux
Reaction 6 hours, during which adds 20gNaOH to ensure that two-phase is sufficiently mixed.After reaction terminates, hydrochloric acid is added dropwise and is transferred to the pH of system
Neutrality, is extracted with ethyl acetate, and ethyl acetate, second alcohol and water in oil phase is evaporated off, is then recrystallized to give in acetone solvent
Alkyl APEO sulfobetaines.
C) parts by weight of alkyl APEO sulfobetaine surfactant 1 of step b) synthesis, temperature-resistant anti-salt are gathered
The parts by weight of compound 3（Viscosity average molecular weigh 6,500,000, by acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, 2- acrylamidos
Four kinds of monomer copolymerizations of dodecyl sodium sulfonate and pi-allyl oleyl ether are formed, and the mol ratio of four kinds of monomers is 78:16:7:1）With 1000
The stratum water of parts by weight Jiangsu sand seven is mixed 2 hours, obtains a kind of composition of the displacement of reservoir oil of homogeneous transparent.
2nd, glycine betaine-polymer displacement of reservoir oil composition properties are evaluated
In addition to displacement composition composition is different, method of evaluating performance be the same as Example 1.The displacement of reservoir oil is combined for ease of comparing
The composition of thing is listed in table 2, and evaluation result is listed in into table 3, table 4 and table 5.
【Embodiment 16】
1st, prepared by beet alkali surface activator
a）CH is added into the reactor equipped with condensing unit and agitating device3(CH2)7CH=CH(CH2)8NH2（1 mole）,
When being heated to 150 DEG C in logical nitrogen, heating adds oxirane after 40 minutes（2 moles）, it is anti-that temperature maintains 155 DEG C of stirrings
Answer 1 hour.80 DEG C are cooled to, barium hydroxide is added as catalyst, is heated to 140 DEG C, open vacuum system, under a high vacuum
Dehydration 1 hour, then purges 4 times with the air in removing system with nitrogen, system reaction temperature then is adjusted into 165 DEG C slowly
It is passed through oxirane（14 moles）, control pressure<0.80MPa, which carries out alkoxylation to reaction, to be terminated, and oxalic acid is used after cooling
Neutralize, filter, be dehydrated, obtain octadecylene base polyoxyethylene（n+m=16）Ether tertiary amine.Wherein the consumption of barium hydroxide is octadecylene base
The 0.5wt% of primary amine and ethylene oxide weight.
b）By octadecylene base polyoxyethylene（n+m=16）Ether tertiary amine（1 mole）, 30wt% formalins（In terms of formaldehyde 1.5
Mole）The ethanol for being dissolved in 400ml is stirring evenly and then adding into reactor, and 10% sodium sulfite is slowly added dropwise and sodium hydrogensulfite is mixed
The aqueous solution of compound（2 moles in terms of mixture）, after being reacted 2 hours at 40 DEG C, it is warming up to 60 DEG C and continues at reflux
Reaction 6 hours, during which adds 20gNaOH to ensure that two-phase is sufficiently mixed.After reaction terminates, hydrochloric acid is added dropwise and is transferred to the pH of system
Neutrality, is extracted with ethyl acetate, and ethyl acetate, second alcohol and water in oil phase is evaporated off, is then recrystallized to give in acetone solvent
Alkyl APEO sulfobetaines.
C) parts by weight of alkyl APEO sulfobetaine surfactant 1 of step b) synthesis, temperature-resistant anti-salt are gathered
The parts by weight of compound 3（Viscosity average molecular weigh 6,500,000, by acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, 2- acrylamidos
Four kinds of monomer copolymerizations of dodecyl sodium sulfonate and pi-allyl oleyl ether are formed, and the mol ratio of four kinds of monomers is 78:16:7:1）With 1000
The stratum water of parts by weight Jiangsu sand seven is mixed 2 hours, obtains a kind of composition of the displacement of reservoir oil of homogeneous transparent.
2nd, glycine betaine-polymer displacement of reservoir oil composition properties are evaluated
In addition to displacement composition composition is different, method of evaluating performance be the same as Example 1.The displacement of reservoir oil is combined for ease of comparing
The composition of thing is listed in table 2, and evaluation result is listed in into table 3, table 4 and table 5.
【Embodiment 17】
1st, prepared by beet alkali surface activator
a）Octadecyl primary amine is added into the reactor equipped with condensing unit and agitating device（1 mole）, barium hydroxide,
When being heated to 150 DEG C in logical nitrogen, temperature is improved to 165 DEG C and is slowly passed through 16 moles in this temperature by heating after 40 minutes
Oxirane, control pressure<0.80MPa, which carries out alkoxylation to reaction, to be terminated, and is neutralized, filtered, taken off with oxalic acid after cooling
Water, obtains octadecyl polyoxyethylene（n+m=16）Ether tertiary amine.Wherein the consumption of barium hydroxide is octadecyl primary amine and epoxy second
The 0.5wt% of alkane weight.
b）By octadecyl polyoxyethylene（n+m=16）Ether tertiary amine（1 mole）, 30wt% formalin（In terms of formaldehyde
1.5 mole）The ethanol for being dissolved in 400ml is stirring evenly and then adding into reactor, and 10% sodium sulfite and sodium hydrogensulfite is slowly added dropwise
The aqueous solution of mixture（2 moles in terms of mixture）, at 40 DEG C react 2 hours after, be warming up to 60 DEG C at reflux after
Continuous reaction 6 hours, during which adds 20gNaOH to ensure that two-phase is sufficiently mixed.After reaction terminates, hydrochloric acid is added dropwise and adjusts the pH of system
To neutrality, it is extracted with ethyl acetate, ethyl acetate, second alcohol and water in oil phase is evaporated off, is then recrystallized in acetone solvent
To alkyl APEO sulfobetaines.
C) parts by weight of alkyl APEO sulfobetaine surfactant 1 of step b) synthesis, temperature-resistant anti-salt are gathered
The parts by weight of compound 3（Viscosity average molecular weigh 6,500,000, by acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, 2- acrylamidos
Four kinds of monomer copolymerizations of dodecyl sodium sulfonate and pi-allyl oleyl ether are formed, and the mol ratio of four kinds of monomers is 78:16:7:1）With 1000
The stratum water of parts by weight Jiangsu sand seven is mixed 2 hours, obtains a kind of composition of the displacement of reservoir oil of homogeneous transparent.
2nd, glycine betaine-polymer displacement of reservoir oil composition properties are evaluated
In addition to displacement composition composition is different, method of evaluating performance be the same as Example 1.The displacement of reservoir oil is combined for ease of comparing
The composition of thing is listed in table 2, and evaluation result is listed in into table 3, table 4 and table 5.
Husky seven oilfield injection water of table 1
The embodiment 1-16 displacement compositions of table 2 are constituted
☆：Viscosity average molecular weigh 6,500,000, by monomeric acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, 2- acryloyls
Four kinds of monomer copolymerizations of amido dodecyl sodium sulfonate and pi-allyl oleyl ether, molar percentage=78 of four kinds of monomers:16:
7:1。
The embodiment 1-16 displacement composition interfacial tension performances of table 3
The embodiment 1-16 displacement composition apparent viscosities of table 4
The embodiment 1-16 oil displacement experiment results of table 5
Claims (7)
1. betaine polymer displacement composition, the composition includes following components in parts by weight：
(1) 1 part of beet alkali surface activator；
(2) 0.01~10 parts of polymer；
(3) 100~2000 parts of water；
The general molecular formula of wherein component (1) is：
In formula：R is C8~C30Alkyl, R ' be C1~C6Alkylidene, n+m=2~100；Described polymer is temperature-resistant anti-salt
Polymer A；Described Heat Resistant and Salt Tolerant Polymer A is by acrylamide, 2- acrylamide-2-methylpro panesulfonic acids, 2- acryloyls
Four kinds of monomer copolymerizations of amido dodecyl sodium sulfonate and pi-allyl oleyl ether are formed, and the mol ratio of four kinds of monomers is (76-83):(7-
18):(5-8):1；
The preparation method of described glycine betaine-polymer flooding fluid composition, is comprised the steps of：
A) primary hydrocarbyl amine is 80~180 DEG C in reaction temperature with aequum oxirane, and pressure is 0~0.80MPa (gauge pressure), instead
Answer 1~10 hour, obtain alkyl APEO tertiary amine；
B) step a) alkyl APEOs tertiary amine, aldehyde, sodium sulfite and sodium hydrogensulfite mixture and solvent are added and reacted
Kettle, in 40~160 DEG C of reactions, 2~20 hours generation beet alkali surface activators, wherein alkyl APEO tertiary amine and aldehyde, Asia
The mol ratio of sodium sulphate and sodium hydrogensulfite mixture is 1：(1.05~2):(1~3)；
C) the desired amount of beet alkali surface activator, Heat Resistant and Salt Tolerant Polymer A and water are uniformly mixed, obtains described beet
Alkali-polymer flooding fluid composition, in terms of parts by weight, beet alkali surface activator, above-mentioned Heat Resistant and Salt Tolerant Polymer A and water
Weight part ratio is 1 part：0.01~10 part: 100~2000 part；
The preparation method of described glycine betaine-polymer flooding fluid composition, it is characterised in that the step a) is not as n+m=2
Reaction obtains alkyl APEO tertiary amine in the case of extra catalyst；As n+m ＞ 2, the step a) is not first additional
Every mole of primary hydrocarbyl amine and 2 moles of ethylene oxide are reacted in the case of catalyst, then again in the presence of base catalyst with
The reacting ethylene oxide of required surplus obtains alkyl APEO tertiary amine.
2. glycine betaine according to claim 1-polymer flooding fluid composition, it is characterised in that the R ' is C1~C5Asia
Alkyl.
3. glycine betaine according to claim 1-polymer flooding fluid composition, it is characterised in that n+m=2~20.
4. glycine betaine according to claim 1-polymer flooding fluid composition, it is characterised in that the water is oil field injection
Water or sewage.
5. glycine betaine according to claim 1-polymer flooding fluid composition, it is characterised in that the step a) reactions
Temperature is 150~170 DEG C, and the reaction time is 8~10 hours.
6. glycine betaine according to claim 1-polymer flooding fluid composition, it is characterised in that described step b) solvents are
C1~C5Alcohol in any one.
7. a kind of method for strengthening the displacement of reservoir oil, by the glycine betaine any one of claim 1 to 6-polymer flooding fluid composition
The aqueous solution injection oil bearing bed by crude oil, the displacement from oil bearing bed comes out；Wherein, glycine betaine table described in the aqueous solution
The weight part ratio of face activating agent and water is 1 part:100~4000 parts.
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| CN106590597A (en) * | 2015-10-20 | 2017-04-26 | 中国石油化工股份有限公司 | High-temperature high-mineralization-degree oil displacement agent composition for oil reservoirs and preparation method thereof |
| CN107286920B (en) * | 2016-04-13 | 2020-02-14 | 中国石油天然气股份有限公司 | Microspheric double-comb block polymer profile control and flooding agent and preparation method thereof |
| CN109679627B (en) * | 2017-10-19 | 2021-03-30 | 中国石油化工股份有限公司 | Oil displacement composition containing carboxyl betaine surfactant, preparation method and application thereof |
| CN109679622B (en) * | 2017-10-19 | 2021-06-22 | 中国石油化工股份有限公司 | Polyether sulfonate-containing surfactant composition, preparation method and application |
| CN109679629B (en) * | 2017-10-19 | 2021-03-30 | 中国石油化工股份有限公司 | Alkali-free viscoelastic surfactant composition, and preparation method and application thereof |
| CN109679625B (en) * | 2017-10-19 | 2021-06-22 | 中国石油化工股份有限公司 | Composition of viscoelastic surfactant for oil displacement, preparation method and application |
| CN109679626B (en) * | 2017-10-19 | 2021-03-30 | 中国石油化工股份有限公司 | Alkali-free viscoelastic surfactant composition containing polyether carboxylate, preparation method and application |
| CN109679623B (en) * | 2017-10-19 | 2021-05-11 | 中国石油化工股份有限公司 | Oil displacement composition containing sulfobetaine type surfactant, preparation method and application thereof |
| CN110358518B (en) * | 2019-07-09 | 2021-09-07 | 合肥全景泰益新材料科技有限公司 | ASP ternary composite oil displacement agent |
| CN112538343A (en) * | 2020-12-02 | 2021-03-23 | 西安石油大油气科技有限公司 | Preparation method of oil displacement and pressure reduction type betaine surfactant |
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