CN109679623A - Displacement composition and preparation method and applications comprising sulfobetaine type surfactant - Google Patents

Displacement composition and preparation method and applications comprising sulfobetaine type surfactant Download PDF

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CN109679623A
CN109679623A CN201710974671.1A CN201710974671A CN109679623A CN 109679623 A CN109679623 A CN 109679623A CN 201710974671 A CN201710974671 A CN 201710974671A CN 109679623 A CN109679623 A CN 109679623A
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surfactant
displacement
oil
reagent
alkylidene
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CN109679623B (en
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王辉辉
沙鸥
虞辰敏
李斌
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • C09K8/584—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
    • 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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
    • 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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/84—Compositions based on water or polar solvents
    • C09K8/86—Compositions based on water or polar solvents containing organic compounds
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH DRILLING; MINING
    • E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/16—Enhanced recovery methods for obtaining hydrocarbons

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Abstract

The present invention relates to a kind of displacement composition and preparation method and applications comprising sulfobetaine type surfactant.The macromolecule polyalcohol mainly solved in current production technology combination flooding be easy to cause formation blockage in middle LOW PERMEABILITY RESERVOIR, injects difficult problem.The present invention is by using a kind of displacement composition, including betaine type amphoteric surfac-tant and inorganic salts；Wherein, shown in betaine type amphoteric surfac-tant's structure such as formula (I), R1Selected from C6~C29Alkyl, any one in alkenyl, R3And R4Selected from C1~C12Alkylidene, any one in hydroxyl substituted alkylene, m+n=0~100, x+y=0~100；The molar ratio of the betaine type amphoteric surfac-tant and inorganic salts is the technical solution of 1:0.01~1:100, preferably resolves the technical problem, be can be used in the displacement of reservoir oil production in oil field.

Description

Displacement composition and preparation method comprising sulfobetaine type surfactant and its Using
Technical field
The present invention relates to a kind of displacement composition comprising sulfobetaine type surfactant and preparation method and its answer With.
Background technique
Chemical flooding is the main method of tertiary oil recovery, and surfactant flooding is considered as that can improve harvesting by a relatively large margin Rate, a kind of chemical agent applied widely, most with prospects.Surfactant is either used as host agent still auxiliary agent to be used as to drive Oil, to increase substantially recovery ratio play the role of it is immeasurable.
It is using the dominant mechanism that surfactant can improve oil recovery factor: remaining after oil field enters high water-cut stage Oil with discontinuous oil film by trap in the hole of reservoir rocks, the main power of two acted on oil droplet is viscous force and hair Tubule power reduces the interfacial tension between grease, makes the interface between oil reservoirs grease if selecting suitable surfactant system Tension is down to lower or ultralow value (10 from 20~30mN/m-3~10-4MN/m), just can be reduced oil droplet when keeping remaining oil mobile to become Resistance brought by shape, to greatly improve oil displacement efficiency.Surfactant flooding improves oil recovery factor and depends mainly on surface Sweep efficiency and oil displacement efficiency of the activating agent in oil reservoir.
That is Er=E υ Ed
In formula: Er indicates recovery ratio, %；E υ indicates sweep efficiency, %；Ed indicates oil displacement efficiency, %.
Therefore, improving Er must start with from Ev and Ed is improved.Activating agent (including surfactant and alkali) is due to having drop The effects of low oil water interfacial tension, can be improved Ed (oil displacement efficiency).This effect can by comprehensive effect parameter capillary number (N) Lai Description:
Ed∝N
N=driving force/viscous force ∝ μ υ/Yow
In formula: μ indicates injection phase viscosity；υ indicates injection phase flow stream velocity；YowIndicate interfacial tension between oil and water.
It has been proven in practice that, to be effectively reduced residual oil saturation, it is necessary to which capillary number is improved into 3~4 orders of magnitude.Both may be used Viscosity is improved so that phase viscosity μ will be injected, it can also be by oil water interfacial tension Yow3 or the higher order of magnitude are reduced, thus significantly It improves capillary number and significantly improves Ed (oil displacement efficiency), this is also the main mechanism of oil displacement of activating agent.And it to improve and involve effect Rate, main method are the mobilities for reducing displacing fluid, and it is viscous that this point can increase displacing fluid by the way that the biggish substance of viscosity is added Degree is to realize.And viscoelastic surfactant can reduce oil water interfacial tension, reduce the hollow billet resistance of oleophylic oil reservoir, increase hair Pipe number and raising oil displacement efficiency, in addition have certain viscosity, improve oil-water seepage ratio, expand sweep efficiency, improve harvesting Rate.Therefore, there are the research and development of viscoelasticity betaine type amphoteric surfactant to have obtained people more and more to pay attention to and pay close attention to, Have become one of the hot spot of tertiary oil recovery field research.
For this purpose, a kind of surface activator composition provided by the invention does not contain macromolecule polyalcohol, by surface-active The condensate that agent and inorganic salts are formed carrys out the viscosity of regulation composition, and the mesh of increasing injection is reached while improving sweep efficiency , and oil water interfacial tension can be reduced, so that the cohesive force between overcoming crude oil, improves washing oil ability, and then significantly provide Oil displacement efficiency.
Summary of the invention
The first technical problem to be solved by the present invention is polymer in the current production technology combination flooding hypotonic oil in It is easy to cause formation blockage in hiding, injects difficult problem, a kind of displacement of reservoir oil comprising sulfobetaine type surfactant is provided Composition, the surfactant have the characteristics that ultralow interfacial tension, system are simple, oil displacement efficiency is high.
The second technical problem to be solved by the present invention is to provide the corresponding displacement of reservoir oil of one of one kind and solution technical problem The preparation method of composition of surfactant.
The third technical problem to be solved by the present invention is to provide the corresponding displacement of reservoir oil of one of one kind and solution technical problem Application of the composition in the displacement of reservoir oil of oil field.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: a kind of displacement composition, including sweet tea Dish alkaline amphoteric surfactant and inorganic salts；Wherein, betaine type amphoteric surfac-tant's structure such as formula (I) institute Show:
(I), R in formula1Selected from C6~C29Alkyl, any one in alkenyl, the R2And R5It is independently chosen from C1~ C22Alkylidene, any one in hydroxyl substituted alkylene, R3And R4Selected from C1~C12Alkylidene, hydroxyl substituted alkylene In any one, m+n=0~100, x+y=0~100；
Stating inorganic salts is at least one of halide, carbonate, bicarbonate, sulfate, sulphite and nitrate； The molar ratio of the betaine type amphoteric surfac-tant and inorganic salts is 1:0.01~1:100.
Preferred R in above-mentioned technical proposal1For C8~C25Alkyl or alkenyl in any one, R2For C2~C22Alkylene Base, R5For C1~C5Alkylidene or hydroxyl substituted alkylene in any one, R3And R4For C1~C3Alkylidene, m+n=0 ~30, x+y=0~10.
The most preferred technique scheme from the angle for improving recovery ratio, above-mentioned technical proposal: R1For C12~C22Alkyl Or any one in alkenyl, R2For C2~C9Alkylidene, R5For C2~C3Alkylidene or hydroxyl substituted alkylene in appoint It anticipates one kind；Inorganic salts are selected from halide, carbonate, bicarbonate, sulfate, the sulphite of alkali metal and/or alkaline-earth metal At least one of with nitrate.
In above-mentioned technical proposal, the inorganic salts preferably are selected from NaCl, MgCl2、CaCl2、Na2CO3、NaHCO3In at least One or more kinds of compositions.
In above-mentioned technical proposal, betaine type amphoteric surfac-tant described in formula (I) is preferably made by following methods:
By R1COOH or R1COOCH3It is reacted 3~20 hours with required amidation reagent in 100~160 DEG C；It obtains Aequum ethylene oxide, propylene oxide is added in 80~180 DEG C, 0~0.80MPa of pressure (gauge pressure) in intermediate, the reaction time 1 Obtain alkyl Polyoxyalkylene ethers within~10 hours；Carboxylating reagent is then added, and the reaction was continued 2~20 hours in 50~100 DEG C, obtains formula (I) the Long carbon chain betaine type amphoteric surfac-tant described in；Wherein, R1COOH or R1COOCH3: amidation reagent: carboxylation The molar ratio of reagent is 1:(1~3): (1~4).
In above-mentioned technical proposal, the molar ratios of the betaine type amphoteric surfac-tant and inorganic salts be preferably (1: 0.1)~(1:10).
To solve above-mentioned technical problem two, The technical solution adopted by the invention is as follows: described in one of above-mentioned technical problem The preparation method of the composition of oil displacement surfactant, comprising the following steps:
A) by R1COOH or R1COOCH3It is reacted 3~20 hours with required amidation reagent in 100~160 DEG C；It obtains Intermediate aequum ethylene oxide, propylene oxide is added in 80~180 DEG C, 0~0.80MPa of pressure (gauge pressure), the reaction time Alkyl Polyoxyalkylene ethers were obtained for 1~10 hour；Carboxylating reagent or sulfonated reagent is then added, and the reaction was continued 2 in 50~100 DEG C ~20 hours, obtain Long carbon chain beet alkali surface activator described in formula (I)；Wherein, Long carbon chain fatty acid methyl ester: amidation examination Agent: the molar ratio of sulfonated reagent is 1:(1~3): (1~4)；
B) it is dissolved in water by anionic surfactant and according to the amphoteric surfactant that step a) is obtained, and It is uniformly mixed afterwards according to molar ratio for (1:0.1)~(1:10), obtains the displacement composition.
In above-mentioned technical proposal, the preferred general molecular formula of step a) amidation reagent isStep It is rapid b) in amphoteric surfactant and inorganic salts molar ratio preferred scope be (1:0.1)~(1:10).
For solve present invention problem three The technical solution adopted by the invention is as follows: a kind of solution above-mentioned technical problem One of corresponding displacement composition the application in the displacement of reservoir oil of oil field.
The technical solution adopted by the invention is as follows: in above-mentioned technical proposal, the application method, have no it is specifically limited, Those skilled in the art can be applied to displacement composition of the present invention according to prior art technology.Such as it but does not limit described The reservoir temperature of application is preferably 60~100 DEG C.The permeability amount in oil reservoir is not particularly limited in the oil displacement system, This field faces technical difficulty outstanding when middle-low permeability to reach preferable oil displacement efficiency, but in oil reservoir, from this angle Degree sets out, and present invention is particularly suitable for high temperature middle and low permeable reservoirs, such as reservoir temperature is 85 DEG C in oil reservoir, and permeability is 30 millis Darcy.
Using technical solution of the present invention, displacement composition interfacial activity is high: under the conditions of dosage is 0.01~0.6%, In salinity in 30000mg/l, the water of calcium ions and magnesium ions content 400mg/l, remain to form 10 with underground crude oil-3~10-4In the least N/m ultralow interfacial tension；Washing oil ability is strong；Have many advantages, such as that surface activator composition system is simple, achieves preferably Technical effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
1. prepared by surfactant
(1) palmitic amide sulfonic group beet alkali surface activator (R1=C15,R2=C2,R3\R4=C2,R5=C3H6O) Preparation
A) bis- (2- ethoxy) ethylenediamines of Long carbon chain methyl palmitate and the desired amount of amidation reagent N, N- are added anti- It answers in kettle, is reacted 6 hours at 130 DEG C, open vacuum pump, extract excessive N, bis- (2- ethoxy) ethylenediamines of N-, then to being equipped with When being heated to 150 DEG C in logical nitrogen in the reactor of condensing unit and agitating device, ethylene oxide is added in heating after forty minutes (2 moles), temperature maintain 150 DEG C and are stirred to react 1 hour.80 DEG C are cooled to, barium hydroxide is added as catalyst, is heated to 140 DEG C, vacuum system is opened, is dehydrated under a high vacuum 1 hour, then purges 4 times with the air in removing system, so with nitrogen System reaction temperature is adjusted to 165 DEG C afterwards to be slowly passed through ethylene oxide (4 moles), control pressure < 0.80MPa carries out alkoxylate Reaction to reaction terminates, and purges system with nitrogen, neutralizes, dehydration after cooling, obtain cetyl polyoxy alkene (m+n=6) ether tertiary amine, It adds the desired amount of 3- chlorine-2-hydroxyl propanesulfonate to react 12 hours in 85 DEG C, be obtained after being purified with dehydrated alcohol recrystallization Long carbon chain beet alkali ampholytic surface active agent；Wherein, methyl palmitate: bis- (2- ethoxy) ethylenediamines of N, N-: 3- chlorine-2-hydroxyl The molar ratio of propanesulfonate is 1:1.5:1.6.
B) palmitic amide carboxylic sulfo group base beet alkali ampholytic surface active agent prepared by the present invention and inorganic salts NaCl are rubbed You are dissolved in the water than being uniformly mixed for 1:0.5, stir 30 minutes, be configured to aqueous solution, obtain the group of oil displacement surfactant Close object.
2. surfactant properties are evaluated
A) micella dimension measurement
Using Malvern dynamic light scattering particle instrument Nano ZS90, the oil displacement agent of above-mentioned 0.3% concentration is measured at 25 DEG C Its micella size formed the results are shown in Table 2.
B) viscosity measurement
Using III type viscosmeter of U.S. Brookfield DV-, at 85 DEG C, revolving speed 7.34S-1Under the conditions of, it measures above-mentioned The viscosity of the oil displacement agent of 0.3% concentration the results are shown in Table 2.
C) interfacial tension is evaluated
TX-500C rotating interfacial tensimeter, at 85 DEG C, revolving speed 6000 are produced using Texas ,Usa university Under the conditions of rev/min, the interfacial tension measured between the oil displacement agent and dewatered oil of above-mentioned 0.1% concentration the results are shown in Table 2.
D) oil displacement experiment is evaluated
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 87 DEG C, length 30cm, diameter 2.5cm, permeability be 30 millidarcies rock core on carry out imitation oil displacement experiment Experiment.Water drive is first carried out to aqueous 98%, after water drive, the drive of above-mentioned 0.3% concentration of metaideophone 0.3pv (rock pore volume) After finish, then water drive to aqueous 100%, raising oil recovery factor the results are shown in Table 2.
[embodiment 2]
1. prepared by surfactant
(1) erucyl amide sulfobetaine surfactant (R1=C21,R2=C2,R 3\R4=C2,R5=C2) preparation
A) bis- (2- ethoxy) ethylenediamines of methyl erucate and the desired amount of amidation reagent N, N- are added in reaction kettle, 145 DEG C are reacted 7 hours, and vacuum pump is opened, and extract excessive N, and bis- (2- ethoxy) ethylenediamines of N- obtain the production of erucic acid acyl group tertiary amine Product, then when being heated to 150 DEG C in logical nitrogen into the reactor equipped with condensing unit and agitating device, heating after forty minutes plus Enter ethylene oxide (2 moles), temperature maintains 150 DEG C and is stirred to react 1 hour.80 DEG C are cooled to, addition barium hydroxide, which is used as, urges Agent is heated to 140 DEG C, opens vacuum system, is dehydrated 1 hour under a high vacuum, then purges 4 times with nitrogen to remove system In air, system reaction temperature is then adjusted to 165 DEG C and is slowly passed through ethylene oxide (2 moles), control pressure < 0.80MPa Carrying out alkoxylation to reaction terminates, and purges system with nitrogen, neutralizes, dehydration after cooling, obtain docosyl polyoxy alkene (m+n=4) ether tertiary amine adds the desired amount of 2- chloroethyl sodium sulfonate, reacts 10 hours in 85 DEG C, recrystallizes through dehydrated alcohol Long carbon chain beet alkali surface activator is obtained after purification；Wherein, methyl erucate: bis- (2- ethoxy) ethylenediamines of N, N-: 2- chloroethene The molar ratio of base sodium sulfonate is 1:1.5:1.5.
B) by erucyl amide sulfobetaines amphoteric surfactant prepared by the present invention and inorganic salts MgCl2Molar ratio is 1:0.3 is uniformly mixed, and is dissolved in the water, and is stirred 30 minutes, is configured to aqueous solution, obtains the composition of oil displacement surfactant.
2. surfactant properties are evaluated
Other than oil displacement agent composition is different, method of evaluating performance is the same as embodiment 1.For convenient for comparing the composition of oil displacement agent It is listed in table 1, evaluation result is listed in table 2.
[embodiment 3]
1. prepared by surfactant
(1) triacontanoic acid amide sulfo betaine surfactant (R1=C29,R2=C3,R 3\R4=C2,R5=C2) system It is standby
A) bis- (2- ethoxy) propane diamine of Long carbon chain triacontanoic acid methyl esters and the desired amount of amidation reagent N, N- are added anti- It answers in kettle, is reacted 8 hours at 150 DEG C, open vacuum pump, extract anti-excessive N, bis- (2- ethoxy) propane diamine of N- obtain three Ten sour acyl group tertiary amine products, then when being heated to 150 DEG C in logical nitrogen into the reactor equipped with condensing unit and agitating device, Ethylene oxide (2 moles) are added after forty minutes in heating, and temperature maintains 150 DEG C and is stirred to react 1 hour.80 DEG C are cooled to, is added Barium hydroxide is heated to 140 DEG C as catalyst, opens vacuum system, is dehydrated 1 hour, is then blown with nitrogen under a high vacuum 4 times are swept with the air in removing system, then by system reaction temperature be adjusted to 165 DEG C be slowly passed through ethylene oxide (2 moles) and Propylene oxide (2 moles), control pressure < 0.80MPa progress alkoxylation to reaction terminate, and purge system with nitrogen, cold But it neutralizes, be dehydrated afterwards, obtain melissyl polyoxy alkene (m+n=4, x+y=2) ether tertiary amine, add the desired amount of 2- chloroethyl sulphur Sour sodium reacts 16 hours in 85 DEG C, obtains Long carbon chain beet alkali surface activator after dehydrated alcohol recrystallization purification；Wherein, Triacontanoic acid methyl esters: bis- (2- ethoxy) propane diamine of N, N-: the molar ratio of 2- chloroethyl sodium sulfonate is 1:1.5:1.6.
B) by triacontanoic acid amide sulfo betaine amphoteric surfactant prepared by the present invention and CaCl2Molar ratio is 1: 0.3 is uniformly mixed, and is dissolved in the water, and stirs 30 minutes, is configured to aqueous solution, obtains the composition of oil displacement surfactant.
2. surfactant properties are evaluated
Other than oil displacement agent composition is different, method of evaluating performance is the same as embodiment 1.For convenient for comparing the composition of oil displacement agent It is listed in table 1, evaluation result is listed in table 2.
[embodiment 4]
1. prepared by surfactant
(1) n-nonanoic acid amide sulfo betaine surfactant (R1=C7,R2=C2,R3\R4=C2,R5=C2) preparation
A) bis- (2- ethoxy) ethylenediamines of methyl pelargonate and the desired amount of amidation reagent N, N- are added in reaction kettle, 150 DEG C are reacted 8 hours, and vacuum pump is opened, and extract anti-excessive N, and bis- (2- ethoxy) ethylenediamines of N- obtain n-nonanoic acid acyl group tertiary amine Product, then when being heated to 150 DEG C in logical nitrogen into the reactor equipped with condensing unit and agitating device, heating is after forty minutes It is added ethylene oxide (2 moles), temperature maintains 150 DEG C and is stirred to react 1 hour.80 DEG C are cooled to, barium hydroxide conduct is added Catalyst is heated to 140 DEG C, opens vacuum system, is dehydrated 1 hour under a high vacuum, then purges 4 times with nitrogen to remove body Then system reaction temperature is adjusted to 165 DEG C and is slowly passed through ethylene oxide (2 moles) by the air in system, and control pressure < 0.80MPa, which carries out alkoxylation to reaction, to be terminated, and is purged system with nitrogen, is neutralized, dehydration after cooling, obtain nonyl polyoxy alkene (m+n=4) ether tertiary amine adds the desired amount of 2- chloroethyl sodium sulfonate, reacts 16 hours in 85 DEG C, recrystallizes through dehydrated alcohol Long carbon chain beet alkali surface activator is obtained after purification；Wherein, methyl pelargonate: bis- (2- ethoxy) ethylenediamines of N, N-: 2- chloroethene The molar ratio of base sodium sulfonate is 1:1.5:1.6.
B) by n-nonanoic acid amide sulfo betaine surfactant and inorganic salts NaHCO3Molar ratio is uniformly mixed for 1:0.5, It is dissolved in the water, stirs 30 minutes, be configured to aqueous solution, obtain the composition of oil displacement surfactant.
2. surfactant properties are evaluated
Other than oil displacement agent composition is different, method of evaluating performance is the same as embodiment 1.For convenient for comparing the composition of oil displacement agent It is listed in table 1, evaluation result is listed in table 2.
[embodiment 5]
1. prepared by surfactant
(1) stearic acid amide sulfo betaine surfactant (R1=C17,R2=C2,R3\R4=C2,R5=C3H6O it) prepares
A) bis- (2- ethoxy) ethylenediamines of Methyl Stearate and the desired amount of amidation reagent N, N- are added in reaction kettle, It is reacted 8 hours at 150 DEG C, opens vacuum pump, extract anti-excessive N, bis- (2- ethoxy) ethylenediamines of N- obtain n-nonanoic acid acyl group uncle Amine product, then when being heated to 150 DEG C in logical nitrogen into the reactor equipped with condensing unit and agitating device, heat 40 minutes Ethylene oxide (2 moles) are added afterwards, temperature maintains 150 DEG C and is stirred to react 1 hour.80 DEG C are cooled to, barium hydroxide is added and makees For catalyst, 140 DEG C are heated to, opens vacuum system, is dehydrated under a high vacuum 1 hour, then purges 4 times with nitrogen to remove Then system reaction temperature is adjusted to 165 DEG C and is slowly passed through ethylene oxide (4 moles) by the air in system, and control pressure < 0.80MPa, which carries out alkoxylation to reaction, to be terminated, and is purged system with nitrogen, is neutralized, dehydration after cooling, it is poly- to obtain octadecyl Oxygen alkene (m+n=6) ether tertiary amine, adds the desired amount of 3- chlorine-2-hydroxyl propanesulfonate, reacts 16 hours in 85 DEG C, through anhydrous Long carbon chain beet alkali surface activator is obtained after ethyl alcohol recrystallization purification；Wherein, methyl pelargonate: bis- (2- ethoxy) second two of N, N- Amine: the molar ratio of 3- chlorine-2-hydroxyl propanesulfonate is 1:1.5:1.6.
B) stearic acid amide sulfo betaine surfactant and inorganic salts NaCl molar ratio are uniformly mixed for 1:0.5, It is dissolved in the water, stirs 30 minutes, be configured to aqueous solution, obtain the composition of oil displacement surfactant.
2. surfactant properties are evaluated
Other than oil displacement agent composition is different, method of evaluating performance is the same as embodiment 1.For convenient for comparing the composition of oil displacement agent It is listed in table 1, evaluation result is listed in table 2.
[comparative example 1]
1. prepared by surfactant
According to method described in patent CN 201410037604.3, synthesize such as the surfactant of flowering structure: by synthesis Surfactant C21H43N(CH3)2-C3H6SO3It is uniformly mixed with inorganic salts NaCl molar ratio for 1:0.5, is dissolved in the water, stirs 30 minutes, it is configured to aqueous solution, obtains the composition of oil displacement surfactant.
2. surfactant properties are evaluated
Other than oil displacement agent composition is different, method of evaluating performance is the same as embodiment 1.For convenient for comparing the composition of oil displacement agent It is listed in table 1, evaluation result is listed in table 2.
[comparative example 2]
1. prepared by surfactant
According to method described in patent CN103242816B, the surfactant of synthesis such as flowering structure: C11H23CON (CH2CH2OH)2, the surfactant of synthesis and inorganic salts NaCl molar ratio are uniformly mixed for 1:0.5, is dissolved in the water, stirs It mixes 30 minutes, is configured to aqueous solution, obtain the composition of oil displacement surfactant.
2. surfactant properties are evaluated
Other than oil displacement agent composition is different, method of evaluating performance is the same as embodiment 1.For convenient for comparing the composition of oil displacement agent It is listed in table 1, evaluation result is listed in table 2.
[comparative example 3]
1. prepared by surfactant
According to method described in patent CN102276822A, the surfactant such as flowering structure is synthesized:
Nonyl pheno (n= 10) surfactant of synthesis and inorganic salts NaCl molar ratio are uniformly mixed by ether hydroxyl sulfoacid betaine salt for 1:0.5, molten In Xie Yushui, stirs 30 minutes, be configured to aqueous solution, obtain the composition of oil displacement surfactant.
2. surfactant properties are evaluated
Other than oil displacement agent composition is different, method of evaluating performance is the same as embodiment 1.For convenient for comparing the composition of oil displacement agent It is listed in table 1, evaluation result is listed in table 2.
[comparative example 4]
1. prepared by surfactant
Triacontanoic acid amide sulfo betaine amphoteric surfactant in embodiment 3 is dissolved in the water, is stirred 30 minutes, It is configured to aqueous solution, obtains the composition of oil displacement surfactant.
2. surfactant properties are evaluated
Other than oil displacement agent composition is different, method of evaluating performance is the same as embodiment 1.For convenient for comparing the composition of oil displacement agent It is listed in table 1, evaluation result is listed in table 2.
[comparative example 5]
1. prepared by surfactant
Betaine type amphoteric surfac-tant is prepared according to embodiment 3, only without alkoxylation, is made 30 Sour amide sulfo betaine amphoteric surfactant, by triacontanoic acid amide sulfo betaine amphoteric surfactant obtained with CaCl2Molar ratio is uniformly mixed for 1:0.3, is dissolved in the water, and stirs 30 minutes, is configured to aqueous solution, and it is living to obtain oil-displacement surface The composition of property agent.
2. surfactant properties are evaluated
Other than oil displacement agent composition is different, method of evaluating performance is the same as embodiment 1.For convenient for comparing the composition of oil displacement agent It is listed in table 1, evaluation result is listed in table 2.
Surface activator composition composition in 1 embodiment of table and comparative example
Oil displacement agent performance evaluation in 2 embodiment of table and comparative example
Particle diameter (nm) Viscosity (mPa.s) Interfacial tension (mN/m) Improve recovery ratio %
Embodiment 1 120 15.4 0.0075 12.0
Embodiment 2 117 15.2 0.0060 11.5
Embodiment 3 136 15.9 0.0041 12.0
Embodiment 4 109 14.9 0.0086 10.8
Embodiment 5 122 17.6 0.0033 13.0
Comparative example 1 85 5.8 0.0090 6.2
Comparative example 2 56 4.6 0.0171 6.3
Comparative example 3 85 5.3 0.0085 7.1
Comparative example 4 87 8.9 0.0073 9.2
Comparative example 5 58 5.6 0.0092 6.0

Claims (10)

1. a kind of displacement composition comprising sulfobetaine type surfactant, including betaine type amphoteric surfac-tant with And inorganic salts；Wherein, shown in betaine type amphoteric surfac-tant's structure such as formula (I):
In formula (I), R1Selected from C6~C29Alkyl, any one in alkenyl, the R2And R5It is independently chosen from C1~C22's Any one in alkylidene, hydroxyl substituted alkylene, R3And R4Selected from C1~C12Alkylidene, in hydroxyl substituted alkylene Any one, m+n=0~100, x+y=0~100；
The inorganic salts are at least one of halide, carbonate, bicarbonate, sulfate, sulphite and nitrate；Institute The molar ratio for stating betaine type amphoteric surfac-tant and inorganic salts is 1:0.01~1:100.
2. displacement composition according to claim 1, it is characterised in that R in the amphoteric surfactant1For C8~C25 Alkyl or alkenyl in any one, R2For C2~C22Alkylidene, R5For C1~C5Alkylidene or hydroxyl substituted alkylene In any one, R3And R4For C1~C3Alkylidene, m+n=0~30, x+y=0~10.
3. displacement composition according to claim 2, it is characterised in that R in the amphoteric surfactant1For C12~ C22Alkyl or alkenyl in any one, R2For C2~C9Alkylidene, R5For C1~C3Alkylidene or hydroxyl replace alkylene Any one in base.
4. displacement composition according to claim 1, it is characterised in that the inorganic salts are selected from alkali metal and/or alkaline earth At least one of halide, carbonate, bicarbonate, sulfate, sulphite and nitrate of metal.
5. displacement composition according to claim 4, it is characterised in that the inorganic salts are selected from NaCl, MgCl2、 CaCl2、Na2CO3、NaHCO3At least one of or two or more compositions.
6. displacement composition described in -5 according to claim 1, it is characterised in that betaine type amphoteric surface described in formula (I) is living Property agent is made by following methods:
By R1COOH or R1COOCH3It is reacted 3~20 hours with required amidation reagent in 100~160 DEG C；Obtained centre Aequum ethylene oxide, propylene oxide is added in 80~180 DEG C, 0~0.80MPa of pressure (gauge pressure) in body, and the reaction time is 1~10 Hour obtains alkyl Polyoxyalkylene ethers；Carboxylating reagent is then added, and the reaction was continued 2~20 hours in 50~100 DEG C, obtains formula (I) institute The Long carbon chain betaine type amphoteric surfac-tant stated；Wherein, R1COOH or R1COOCH3: amidation reagent: carboxylating reagent Molar ratio is 1:(1~3): (1~4).
7. the composition of displacement of reservoir oil oil displacement surfactant described in claim 6, it is characterised in that the amidation reagent General molecular formula be
8. displacement composition according to claim 1, it is characterised in that the betaine type amphoteric surfac-tant and nothing The molar ratio of machine salt is (1:0.1)~(1:10).
9. the preparation method of any displacement composition of claim 1~8, comprising the following steps:
A) by R1COOH or R1COOCH3It is reacted 3~20 hours with required amidation reagent in 100~160 DEG C；In obtaining Aequum ethylene oxide, propylene oxide is added in 80~180 DEG C, 0~0.80MPa of pressure (gauge pressure) in mesosome, and the reaction time is 1~ Obtain alkyl polyoxyethylene ether within 10 hours；Carboxylating reagent or sulfonated reagent is then added, and the reaction was continued 2~20 in 50~100 DEG C Hour, obtain Long carbon chain beet alkali surface activator described in formula (I)；Wherein, Long carbon chain fatty acid methyl ester: amidation reagent: The molar ratio of sulfonated reagent is 1:(1~3): (1~4)；
B) it is dissolved in water by anionic surfactant and according to the amphoteric surfactant that step a) is obtained, then presses It is uniformly mixed according to molar ratio for (1:0.1)~(1:10), obtains the surface activator composition.
10. the displacement composition described in any item of the claim 1 to 8 comprising sulfobetaine type surfactant is in oil field Application in the displacement of reservoir oil.
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