CN102757775A - Oil displacement composition containing betaine type surfactant and application thereof - Google Patents
Oil displacement composition containing betaine type surfactant and application thereof Download PDFInfo
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- CN102757775A CN102757775A CN2012101903745A CN201210190374A CN102757775A CN 102757775 A CN102757775 A CN 102757775A CN 2012101903745 A CN2012101903745 A CN 2012101903745A CN 201210190374 A CN201210190374 A CN 201210190374A CN 102757775 A CN102757775 A CN 102757775A
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Abstract
The invention provides an oil displacement composition containing a betaine type surfactant and application thereof, particularly application thereof in tertiary oil recovery. The oil displacement composition is composed of the following components: 1-30 parts by weight of a composite surfactant and 0-25 parts by weight of a polymer, wherein the composite surfactant is a combination of the betaine type surfactant (I) and an non-ionic surfactant (II) in a weight ratio of (10-90):(90-10): formula (I), wherein in the formula (I), m and n are integers from 0 to 19 but are equal to 0 asynchronously, R1 is H, C1-8 alkyl, phenyl or C1-8 alkyl phenyl, R3 is C1-8 alkyl, and R4 is C1-8 alkyl, and X is shown in the specification; and in the formula (II), R is H, C1-8 alkyl, phenyl or C1-8 alkyl phenyl, x and y are integers from 0 to 19 and are equal to 0 asynchronously, and z is an integer from 3 to 25.
Description
Technical field
The invention relates to chemical flooding formula system used in a kind of TOR, specifically is to comprise the displacement of reservoir oil compsn of betaine type amphoteric surfactant and the application in TOR thereof about a kind of.
Background technology
In recent years; Along with the intensification of east oilfields recovery percent, China waterflooding main force oil field majority has been in the high moisture and high recovery percent of reserves stage, and the difficulty of old liberated area adjustment increase workable reserve is increasing; The newly-increased then workable reserve in oil field is lower than oil offtake; Storage is adopted unbalance, but the oil field average recovery ratio is merely 32%, is badly in need of TOR and improves the RF new technology to keep increasing and stablizing of crude production rate.
It is the tertiary oil recovery technology that is fit to China's oil reservoir characteristics that proof chemical flooding technology is used in the industrialization promotion of grand celebration polymer flooding.Wherein technique of polymer flooding is mainly utilized the mobility control effect of polymkeric substance, reaches the purpose that improves RF through improving swept volume, improves the RF amplitude and reaches more than 10%.Ternary composite driving mainly utilizes the mobility control of polymkeric substance and the synergy of tensio-active agent and alkali to reduce IT; Reach the purpose that improves RF; Be to improve the maximum chemical flooding technology of RF amplitude at present; The multinomial field test that grand celebration is carried out shows that highly basic combination flooding technology improves RF and can reach 20%, adopts the weak base system to improve RF and also can reach 18%.
It is another raising recovery efficiency technique behind polymer flooding and ternary composite driving that polymkeric substance/tensio-active agent (SP) binary is driven; Its main oil increasing machine reason is in water, to add polymkeric substance and tensio-active agent; Utilize the mobility control ability of polymkeric substance and the characteristic that tensio-active agent reduces oil water interfacial tension significantly, reach the purpose that not only improves sweep efficiency but also improve oil displacement efficiency.Polymkeric substance/table agent the binary combination flooding of living is compared favorable factor with ternary composite driving and is mainly comprised: reduce the frequent operation that the existence owing to alkali causes oil pipe and surface pipeline fouling to cause; Reduce because burn into corrosion and the fouling that the existence of alkali causes; Reduce the breakdown of emulsion difficulty of extraction liquid; Binary system viscosity and elasticity are higher than ternary system, can reduce polymer loading; Binary system low interfacial tension and fluidic elasticity dual function improve oil displacement efficiency; On-the-spot preparation, injection device and technology are simpler than ternary system; Cost is lower than ternary system, and corresponding cost of investment reduces.But binary combination flooding also has tangible unfavorable factor, comprising: binary is driven the amplitude that improves RF and is driven less than ternary; Flooding system is strict to tensio-active agent, must under the salt-free condition of alkali-free, make system reach low (ultralow) IT, and system need have absorption and stability preferably; It is less that successful binary is driven field test, and the Technological Economy risk is still bigger; The binary combination flooding fundamental research has to be strengthened.
Summary of the invention
Main purpose of the present invention is to the defective in the above-mentioned tertiary oil recovery technology field; A kind of new displacement of reservoir oil compsn is provided, realizes that no alkali systems oil water interfacial tension is ultralow, promote displacement of reservoir oil performance; Improve RF, with the TOR industrial applications process that advances binary to drive.
At first; The invention provides a kind of displacement of reservoir oil compsn, it is a kind of composite reactive agent prescription system that comprises betaine type amphoteric surfactant and non-ionics, and betaine type and non-ionic type complexed surfactant that through performance is excellent have realized that no alkali systems oil water interfacial tension is ultralow; And this formula system has absorption and stability preferably; Displacement of reservoir oil excellent performance can improve RF by a relatively large margin, with the TOR industrial applications process that advances binary to drive greatly.
Trimethyl-glycine active agent formulation system provided by the invention (displacement of reservoir oil compsn that comprises betaine type amphoteric surfactant), form by following ingredients:
Wherein said complexed surfactant is the combination of betaine type amphoteric surfactant and nonionogenic tenside, and the weight ratio of said betaine type amphoteric surfactant and nonionogenic tenside is 10～90: 90～10,
Said betaine type amphoteric surfactant is the combination of one or more in the compound shown in the formula (I):
In the formula (I), m, n are respectively the integer that is selected from 0-19, and m and n are not 0 simultaneously;
R
1Be the alkyl phenyl of alkyl, phenyl or C1～8 of H, C1～8, R
3Be the alkyl of C1～8, R
4Alkyl for C1～8;
X is
perhaps
Said nonionogenic tenside is an alkyl alcohol Soxylat A 25-7 compounds, and this compound structure is suc as formula shown in (II):
In the formula (II), R is the alkyl phenyl of alkyl, phenyl or C1～8 of H, C1～8;
X, y are respectively and are selected from 0～19 integer and x, y is not 0 simultaneously;
Z is selected from 3～25 integer.
According to preferred specific embodiments of the present invention, in the displacement of reservoir oil compsn that comprises betaine type amphoteric surfactant of the present invention, the weight ratio of said trimethyl-glycine and nonionogenic tenside is 30～70: 70～30.
According to preferred specific embodiments of the present invention, in the displacement of reservoir oil compsn that comprises betaine type amphoteric surfactant of the present invention, in the said betaine type amphoteric surfactant (in the formula (I)), m, n are respectively and are selected from 0～19 integer, and m+n=5～19, R
1Be the alkyl phenyl of alkyl, phenyl or C1～4 of H, C1～4, R
4Be the alkyl of C1～4, R
4Alkyl for C1～4; Preferably, m, n are respectively and are selected from 0～19 integer, and m+n=9～19, R
1Be H, methyl, ethyl, phenyl, tolyl, xylyl or ethylphenyl, R
2Be H or methyl or ethyl, R
3Be H or methyl or ethyl; X does
Perhaps
According to preferred specific embodiments of the present invention; In the displacement of reservoir oil compsn that comprises betaine type amphoteric surfactant of the present invention; In the said nonionogenic tenside (in the formula (II)), R is alkyl, phenyl, tolyl, xylyl or the ethylphenyl of H, C1～4; X, y are respectively and are selected from 0～19 integer and x+y=9～19; Z is selected from 3～25 integer.
According to preferred specific embodiments of the present invention, in the displacement of reservoir oil compsn that comprises betaine type amphoteric surfactant of the present invention, said betaine type amphoteric surfactant is selected from one or more in the following compound:
Said betaine type amphoteric surfactant is selected from one or more in the following compound:
Wherein, m, n are respectively and are selected from 0～19 integer and m+n=9～19, preferred m+n=9,15 or 19; Said alkyl alcohol Soxylat A 25-7 compounds is selected from one or more in the following compound:
CH
3(CH
2)
xCH
2(CH
2)
yCH
2O(CH
2CH
2O)
zH
Wherein, x, y are respectively and are selected from 0～19 integer and x+y=9～19, preferred x+y=9,15 or 19; Z is 5,7,10,15 or 20.
According to specific embodiments of the present invention, used betaine type amphoteric surfactant can be purchased acquisition (for example, the compound the when R1 in the formula (I) is H) among the present invention, or prepares with reference to the method for prior art.Betaine type amphoteric surfactant when for example, the R1 in the formula (I) is aryl (alkyl phenyls of phenyl or C1～8) can be the reaction product for preparing according to following method:
Friedel-crafts alkylation reaction: make olefin(e) acid or olefin(e) acid ester and korenyl or benzene that friedel-crafts alkylation reaction take place under the catalysis of protonic acid, obtain arylalkyl carboxylic acid or arylalkyl carboxylicesters;
Hydrogenation reduction: make arylalkyl carboxylic acid or arylalkyl carboxylicesters generation shortening de-esterification, generate aryl alcohols;
Amination reaction: make aryl alcohols and secondary amine that amination reaction take place under the catalysis of Cu and Ni composite catalyst, generate the aryl fat tertiary amine;
Quaterisation: with methyl alcohol is solvent, makes aryl fat tertiary amine and chlorine hydroxypropyl azochlorosulfonate acid sodium or sodium chloroacetate generation quaterisation, obtains title product.
According to concrete technical scheme of the present invention, preferably, the olefin(e) acid that is adopted among the above-mentioned preparation method is an oleic acid etc., and the olefin(e) acid ester is an olefin(e) acid methyl esters etc., and korenyl is toluene, YLENE or ethylbenzene etc., and secondary amine is n n dimetylaniline or diethylamine etc.
According to concrete technical scheme of the present invention; Preferably; Above-mentioned friedel-crafts alkylation reaction is: under 110-130 ℃ condition, korenyl or benzene and olefin(e) acid or olefin(e) acid methyl esters are reacted under the katalysis of protonic acid, generate the arylalkyl carboxylate methyl ester; Wherein, the mol ratio of korenyl or benzene and olefin(e) acid or olefin(e) acid methyl esters may be controlled to 3: 1.In above-mentioned friedel-crafts alkylation reaction, preferably, the protonic acid that is adopted can be methylsulfonic acid, phosphoric acid, sulfuric acid or hydrofluoric acid etc.
According to concrete technical scheme of the present invention, preferably, above-mentioned hydrogenation reduction is: under 200-350 ℃, the condition of 25-30MPa, make arylalkyl carboxylic acid or arylalkyl carboxylate methyl ester at hydrogenation catalyst CuO-ZnO-TiO
2Katalysis under react, generate aryl alcohols.At above-mentioned hydrogenation catalyst CuO-ZnO-TiO
2In, preferably, CuO, ZnO and TiO
2Mass ratio be 7.5: 2.5: 50.
According to concrete technical scheme of the present invention, preferably, above-mentioned amination reaction is: under 180-250 ℃, aryl alcohols and gaseous state secondary amine (being preferably n n dimetylaniline) are reacted under the catalysis of Cu-Ni composite catalyst, generate the aryl fat tertiary amine.Wherein, above-mentioned Cu-Ni composite catalyst preferably has following mass ratio composition: Cu: Zn: Mg: Ni=1: (0.1-0.3): (0.1-0.3): (0.01-0.06).In above-mentioned amination reaction, continue to feed gaseous state secondary amine, itself and aryl alcohols are reacted, therefore, the addition of gaseous state secondary amine is excessive with respect to aryl alcohols.
According to concrete technical scheme of the present invention; Preferably, above-mentioned quaterisation is: be solvent with methyl alcohol, under 110 ℃-130 ℃, the condition of 0.4MPa-0.6MPa; Aryl fat tertiary amine and chlorine hydroxypropyl azochlorosulfonate acid sodium or sodium chloroacetate are reacted, generate title product.In above-mentioned quaterisation, the mol ratio of aryl fat tertiary amine and chlorine hydroxypropyl azochlorosulfonate acid sodium or sodium chloroacetate may be controlled to 1: 1.1.
The present invention adopts olefin(e) acid or olefin(e) acid ester and benzene or korenyl generation friedel-crafts alkylation reaction back end hydrogenation to obtain fragrant Fatty Alcohol(C12-C14 and C12-C18); Obtain fragrant fat tertiary amine with the secondary amine reaction then, obtain betaine type amphoteric surfactant of the present invention with chlorine hydroxypropyl azochlorosulfonate acid sodium or sodium chloroacetate reaction again.
In the preparation process, the olefin(e) acid that is adopted can be CH
3(CH
2)
mCH=CH (CH
2)
nCOOH; The structure of olefin(e) acid or olefin(e) acid ester can be 8-22 carbon, 12-20 carbon more preferably, and most preferably carbon chain length is 18 carbon (m+n=15; Be that said olefin(e) acid is an oleic acid); Because the reaction conditions of arylalkyl carboxylic acid when hydrogenation that oleic acid forms is comparatively harsh, oleic acid can carry out esterification earlier before reaction, and (its structure can be CH particularly to obtain Witconol 2301
3(CH
2)
mCH=CH (CH
2)
nCOOCH
3), hydrogenation is carried out more easily like this;
The korenyl that is adopted is to have one or two substituted alkyl on the phenyl ring, i.e. a korenyl or dialkyl benzene, and, the preferred 1-8 of the carbon chain lengths of a substituted alkyl carbon, more preferably 1-4 carbon most preferably is 1-2 carbon;
The secondary amine that is adopted is R
2NR
3, substituted alkyl R wherein
2, R
3Be preferably the alkyl of 1-4 carbon, because of reaction adopts gaseous state secondary amine better, above-mentioned substituted alkyl R
2, R
3The alkyl of 1-2 carbon more preferably, most preferably two alkyl substituents are methyl or ethyl simultaneously, promptly secondary amine is diethylamine or n n dimetylaniline.
Among the preparation method of betaine type amphoteric surfactant of the present invention; Described friedel-crafts alkylation reaction, hydrogenation reduction, amination reaction, quaterisation also can carry out according to the routine operation in affiliated field; This preparing method's key is to select different reaction raw materials among the present invention, to obtain different said title products.
According to a more particular embodiment of the present invention, betaine type amphoteric surfactant provided by the present invention can be the reaction product according to following synthetic route preparation:
In the said synthesis route, n1, n2 are respectively and are selected from 0～18 positive integer, and n1+n2=m+n-1.M, n, R
2, R
3Such as preamble definition.R
4, R
5The independent separately alkyl for H or C1～8 (being preferably C1～4) is preferably methyl or ethyl.
According to specific embodiments of the present invention, the used nonionogenic tenside of the present invention can be to be purchased acquisition (for example, the compound the when R in the formula (II) is H), or prepares with reference to the method for prior art.Arylalkyl polyoxyethylenated alcohol compounds when for example, the R in the formula (II) is aryl (alkyl phenyls of phenyl or C1～8) can be the reaction product for preparing according to following method:
Friedel-crafts alkylation reaction: make Witconol 2301 and korenyl that friedel-crafts alkylation reaction take place under the catalysis of protonic acid, obtain arylalkyl carboxylic acid or arylalkyl carboxylicesters;
Hydrogenation reduction: make arylalkyl carboxylicesters generation shortening de-esterification, generate aryl alcohols; Perhaps, make arylalkyl acid carry out esterification, make arylalkyl carboxylicesters generation shortening de-esterification again, generate aryl alcohols;
Ethoxylation: make at first activation under the condition of one-level catalyzer of aryl alcohols, under the second catalyst condition, react then, produce the arylalkyl polyoxyethylenated alcohol of narrow distribution with oxyethane.
Among the preparation method of arylalkyl polyoxyethylenated alcohol compounds of the present invention, described friedel-crafts alkylation reaction, hydrogenation reduction, ethoxylation all can carry out according to the routine operation in affiliated field.Aforesaid method mainly is through selecting suitable reaction raw materials generating needed reaction product, and concrete reaction conditions comprises that temperature, pressure, selection of catalysts etc. can confirm according to its prior art knowledge of grasping for a person skilled in the art.
According to a more particular embodiment of the present invention, arylalkyl polyoxyethylenated alcohol compounds provided by the present invention can be the reaction product for preparing according to following synthetic route:
In the said synthesis route, m1, m2 are respectively and are selected from 0～18 positive integer, and m1+m2=x+y-1.X, y, z such as preamble definition.R
4, R
5The independent separately alkyl for H or C1～8 (being preferably C1～4), preferably independent separately is H, methyl or ethyl.
In such scheme, x+y=15 preferably, R
4, R
5The methyl of position between being respectively on the phenyl ring; That is be to utilize cheap industrial raw material such as Witconol 2301 and m-xylene,, successively through Fu Shi alkylation, hydrogenating reduction and ethoxylation; Generate the alkyl alcohol Soxylat A 25-7 that side chain contains aromatic group at last; Its synthesis route, not only the prices of raw and semifnished materials are cheap, and route matured product yield is high.
According to preferred specific embodiments of the present invention; In the displacement of reservoir oil compsn that comprises betaine type amphoteric surfactant of the present invention, said polymkeric substance for example can be HPAM for displacement of reservoir oil field polymkeric substance commonly used; Salt-resistant polymer KYPAM etc., molecular weight is generally 300～3,500 ten thousand.When selecting partially hydrolyzed polyacrylamide for use, degree of hydrolysis 10～30%, molecular-weight average are 300～35,000,000.Other performance index to polymkeric substance do not have particular requirement.
The displacement of reservoir oil compsn that comprises betaine type amphoteric surfactant of the present invention; The betaine type amphoteric surfactant wherein and the combination of nonionogenic tenside; For the emulsifying property of profit, keep the water-oil interface aspect of performance and played synergy, can be used in the alkali-free compound petroleum driving and recovering.
According to specific embodiments of the present invention, the displacement of reservoir oil compsn that comprises betaine type amphoteric surfactant of the present invention as the displacement of reservoir oil purposes time, is that itself and water are re-dubbed mixed solution, uses as required.Thereby on the other hand, the present invention also provides a kind of displacement of reservoir oil compsn mixed solution, and it comprises aforesaid displacement of reservoir oil compsn and the water that comprises betaine type amphoteric surfactant of the present invention.According to specific embodiments of the present invention, in this displacement of reservoir oil compsn mixed solution, the mass concentration of complexed surfactant is 0.01%～0.3% (correspondingly, the mass concentration of polymkeric substance is 0～0.25%).
According to preferred specific embodiments of the present invention, in the displacement of reservoir oil compsn mixed solution of the present invention, complexed surfactant concentration is 0.05%～0.25%.
According to preferred specific embodiments of the present invention, in the displacement of reservoir oil compsn mixed solution that comprises betaine type amphoteric surfactant of the present invention, polymer concentration is 0.1%～0.2%.
According to preferred specific embodiments of the present invention, in the displacement of reservoir oil compsn that comprises betaine type amphoteric surfactant of the present invention, said water is oilfield injection water.
The present invention also provides described displacement of reservoir oil compsn and the application of described displacement of reservoir oil compsn mixed solution in TOR that comprises betaine type amphoteric surfactant.
The present invention also provides a kind of flooding method; Utilize displacement of reservoir oil compsn or the described displacement of reservoir oil compsn mixed solution that comprises betaine type amphoteric surfactant of the present invention to carry out the displacement of reservoir oil in this method; Specifically can be according to conventional displacement of reservoir oil operation; In water drive or gather and drive the back and inject displacement of reservoir oil compsn or the described displacement of reservoir oil compsn mixed solution that comprises betaine type amphoteric surfactant of the present invention and carry out the displacement of reservoir oil, can improve swept volume and oil displacement efficiency.
The present invention also provides a kind of TOR method, has utilized displacement of reservoir oil compsn or the described displacement of reservoir oil compsn mixed solution that comprises betaine type amphoteric surfactant of the present invention in this method.Particularly, be to utilize the described displacement of reservoir oil compsn that comprises betaine type amphoteric surfactant to carry out TOR in this method as the main slug that injects, can increase substantially oil recovery.
Among the present invention, it is composite to adopt novel beet alkali surface activator and nonionogenic tenside to carry out, and has realized the alkali-free compound petroleum driving and recovering.Experiment showed, that this system has suit property to profit, surfactant concentration reaches ultralow with oil field oil water ITs such as grand celebration, Xinjiang and long celebratings in 0.025%～0.3% scope, have excellent interface performance; The system good stability, anti-absorption property is excellent, and grand celebration natural core oil displacement experiment shows, on two types of reservoir waterflood recovery efficiency factors about 40% bases, can improve RF more than 18%, has favorable industrial application prospect.
Description of drawings
The infrared figure of Fig. 1 embodiment 1 YLENE α stearyl alcohol.
The nuclear-magnetism figure of Fig. 2 embodiment 1 YLENE α stearyl alcohol.
The infrared figure of Fig. 3 embodiment 1 YLENE α 18 tertiary amines.
The nuclear-magnetism figure of Fig. 4 embodiment 1 YLENE α 18 tertiary amines.
The infrared figure of Fig. 5 embodiment 1 synthesizing betaine tensio-active agent.
The nuclear-magnetism figure of Fig. 6 embodiment 1 synthesizing betaine tensio-active agent.
The flight time mass spectrum figure of Fig. 7 A-Fig. 7 E embodiment 1 synthetic nonionogenic tenside EB5EO, EB7EO, EB10EO, EB15EO, EB20EO.
The dynamic interface tension detection of Fig. 8 embodiment 2 (grand celebration one factory's profit).
The emulsifying property of Fig. 9 embodiment 3 is measured (grand celebration one factory, six factory's profits).
The dynamic interface tension detection of Figure 10 embodiment 4 (grand celebration six factory's profits).
The dynamic interface tension detection of Figure 11 embodiment 5 (Xinjiang Qi Zhongqu profit).
The nuclear-magnetism figure of the betaine type amphoteric surfactant of Figure 12 embodiment 6; As shown in the figure; Multimodal ownership straight chain methyl and methylene radical hydrogen near the displacement 1.0-2.0, near the peak of displacement 2.7-3.0 belong to aromatic ring methyl hydrogen and the continuous methyne hydrogen of phenyl ring, continuous methyl hydrogen of peak ownership nitrogen and the continuous methylene radical hydrogen of nitrogen near the displacement 3.3-3.5; Near carboxyl peak ownership aromatic ring hydrogen methylene radical hydrogen, the displacement 7.0-7.2 that links to each other is returned at peaks near the displacement 4.3, and confirmation obtains said title product.
The dynamic interface tension detection of Figure 13 embodiment 6 (long celebrating two factory's profits).
Stability mensuration-the IT of Figure 14 a embodiment 7 (grand celebration one factory).
Stability mensuration-the viscosity of Figure 14 b embodiment 7 (grand celebration one factory).
Stability mensuration-the IT of Figure 15 a embodiment 8 (grand celebration six factories).
Stability mensuration-the viscosity of Figure 15 b embodiment 8 (grand celebration six factories).
The absorption property of Figure 16 embodiment 9 is measured.
Embodiment
In order more to be expressly understood the present invention, further describe the present invention with reference to the following example and accompanying drawing at present.Embodiment only is used for explaining and does not limit the present invention in any way.
Synthetic and the evaluation of embodiment 1 betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside
The reactions step that betaine type amphoteric surfactant is detailed is following:
(1) esterification: oleic acid and methyl alcohol (methyl alcohol is excessive) are mixed, add the catalyzer vitriol oil or tosic acid, reflux 10h.Cooling, using sodium methylate to be neutralized to the pH value is 8～9, water is washed till neutrality, after the Calcium Chloride Powder Anhydrous drying, carries out underpressure distillation, promptly gets Witconol 2301;
(2) Fu Shi alkylation: in the 2.5L sealed reactor, add m-xylene and etc. organic bronsted acid catalyst (for example methylsulfonic acid) of amount of substance; The resultant of reaction Witconol 2301 that under 115～120 ℃, 0.2MPa, dropwise adds the step (1) of 5 times of amount of substances; The dropping time is controlled at 6h; After dropwising, continue reaction 3h.Static layering, lower floor's catalyzer decolorizing and refining recycles, and the supernatant liquid cooling is fed in the frozen water; Water washing three times, under 100MPa, 220 ℃, rectifying goes out the m-xylene Witconol 2301; Adopt gas chromatography mass spectrometry chromatogram external standard method to detect the transformation efficiency of Witconol 2301, can reach more than 98%;
(3) hydrogenating reduction: the resultant of reaction m-xylene Witconol 2301 of step (2) is at hydrogenation catalyst CuO-ZnO-Cr
20
3(mass ratio of CuO, ZnO and Ti02 is 7.5: 2.5: 50) effect down; 200～350 ℃, during 25～30MPa; Hydrogenating reduction is a YLENE α stearyl alcohol: structural identification collection of illustrative plates such as Fig. 1, (because isomers is arranged, so can't confirm the accurate position of m-xylene) shown in Figure 2.
Infared spectrum: in Fig. 1, can see 3362.64cm
-1There is the association O-H stretching vibration of a bigger alcohol at the place; 1055.93cm
-1Place's (flexible absorption of C-O key) proves the existence of primary alconol.3008.96cm
-1Be the Ar-H stretching vibration; 1608.60cm
-1, 1501.96cm
-1Skeletal vibration for phenyl ring; 817.48cm
-1Be the outer formation vibration of the Ar-H face of a disubstituted benzenes; 2925.49cm
-1, 2853.67cm
-1Be the saturated C-H stretching vibration of methyl; 1461.45cm
-1, 1375.93cm
-1Be methyl C-H flexural vibration.
1HNMR: as shown in Figure 2; Near displacement 1.5 three peaks belong to straight chain methyl and methylene radical hydrogen, near the peaks ownership aromatic ring methyl hydrogen displacement 2.2, near ownership phenyl ring continuous methyne hydrogen in the peaks displacement 2.7; Near ownership hydroxyl continuous methylene radical hydrogen in the peak displacement 3.6, near the peaks ownership aromatic ring hydrogen displacement 7.0.
Infrared and nuclear-magnetism detects and shows that synthetic product conforms to object construction.
(4) amination reaction: the resultant of reaction YLENE α stearyl alcohol of step (3) under 180～250 ℃, 0.3MPa, with the gas phase n n dimetylaniline through Cu and Ni composite catalyst, generation YLENE α 18 tertiary amines; Structural identification collection of illustrative plates such as Fig. 3, shown in Figure 4.
Infared spectrum: in Fig. 3, can see at 3018.15cm
-1Be the Ar-H stretching vibration; 1607.34cm
-1, 1512.95cm
-1Skeletal vibration for phenyl ring; 815.33cm
-1Be the outer formation vibration of the Ar-H face of para-orientation benzene.2926.35cm
-1, 2854.16cm
-1Be the saturated C-H stretching vibration of methyl; 1461.95cm
-1, 1376.25cm
-1Be methyl C-H flexural vibration.
1HNMR: as shown in Figure 4, displacement 1.5 near three peaks ownership straight chain methyl and methylene radical hydrogen, peak ownership aromatic ring methyl hydrogen, nitrogen methyl hydrogen and the continuous methyne hydrogen of phenyl ring near the displacement 2.2-2.4, near the peak ownership aromatic ring hydrogen displacement 7.0.
Infrared and nuclear-magnetism detects and shows that synthetic product conforms to object construction.
(5) quaterisation: with resultant of reaction YLENE α 18 tertiary amines of step (4), with the chlorine hydroxypropyl azochlorosulfonate acid sodium, be solvent with methyl alcohol, reaction under 130 ℃, 0.3MPa generates target betaines tensio-active agent.Structural identification collection of illustrative plates such as Fig. 5, shown in Figure 6.
Infared spectrum: in Fig. 5, can see at 3421.18cm
-1There is the association O-H stretching vibration of a bigger alcohol at the place.3008.96cm
-1Be the Ar-H stretching vibration; 1637.63cm
-1, 1463.22cm
-1Skeletal vibration for phenyl ring; 816.42cm
-1Be the outer formation vibration of the Ar-H face of a disubstituted benzenes.2925.30cm
-1, 2853.57cm
-1Be the saturated C-H stretching vibration of methyl.1199.82cm
-1Be SO
3Antisymmetric stretching vibration.1042.35cm
-1Near be the C-N stretching vibration of tertiary amine.629.49cm
-1Be SO
3Out-of-plane deformation vibration.
1HNMR: as shown in Figure 6; Multimodal ownership straight chain methyl and methylene radical hydrogen near the displacement 1.0-2.0; Near the peak ownership aromatic ring methyl hydrogen displacement 2.5; Near the ownership phenyl ring methyne hydrogen that links to each other in the peaks displacement 2.7, near ownership nitrogen methyl hydrogen, nitrogen methylene radical hydrogen and the sulfonic group methylene radical that links to each other that links to each other that links to each other in the peak displacement 3.3-3.5, near the displacement 3.9 peaks return hydroxyl to link to each other peaks belong to the aromatic ring hydrogen near methyne hydrogen, the displacement 7.0.
Infrared and nuclear-magnetism detects and shows that synthetic product conforms to object construction.
Above-mentioned oleic acid can be substituted by other olefin(e) acid, and the chlorine hydroxypropyl azochlorosulfonate acid sodium can replace with sodium chloroacetate, and YLENE can replace with benzene or korenyl, and the compound method step is identical, and empirical tests all can obtain described title product.
The reactions step that arylalkyl polyoxyethylenated alcohol class nonionogenic tenside is detailed is following:
The YLENE α stearyl alcohol that above-mentioned steps (3) obtains directly is used for following reaction.
Ethoxylation:, add in the potheater according to mol ratio (1: 1) with m-xylene α octadecyl raw polyol and KOH.After airtight, a spot of oxyethane is passed through N
2Pressure is pressed into the metered charge jar by basin, and reactive system is carried out nitrogen replacement.Stir down in 80 ℃, found time under the 30mmHg 30 minutes, to remove water and other low-boiling point material in the reaction system, release and add a certain amount of second catalyst then is mainly with Ca (OEt)
2/ H
3PO
4Be main, repeat above-mentioned work subsequently.When treating still temperature rise to temperature of reaction; At pressure is under 0.3～0.4MPa; Continous-stable drips oxyethane to institute required amount (press EO=5,7,10,15,20 respectively and calculate, in each reaction, obtain the product that difference adds and counts respectively through the proportioning of control reaction raw materials).Be incubated 1 hour postcooling, under low vacuum, remove unreacted oxyethane in the reaction mass, release, weighing products.
The flight time mass spectrum figure of product is shown in Fig. 7 A-7E, because oxyethane addition characteristic has determined that this reaction product is to possess certain distribution, present embodiment mainly is the arylalkyl alcohol polyvinyl ether product that has obtained possessing narrow distribution.As can be seen from the figure; The molecular weight of 5 kinds of products matches basically; And. each mass spectra peak differs 44, explains that synthetic product is consistent with title product, wherein the dispersion index of EB5EO, EB7EO, EB10EO (n-2 is to five components contents percentage ratio of n+2 sum)) lower; And the dispersion index of EB15EO and EB20EO is higher, explains that reaction scheme becomes the alkyl alcohol Soxylat A 25-7 nonionogenic tenside of narrow distribution with the symphysis of processing condition comparison operators.
Above-mentioned oleic acid can be substituted by other olefin(e) acid, and YLENE can replace with benzene or korenyl, and the compound method step is identical, and empirical tests all can obtain described title product.
Below among each embodiment used each trimethyl-glycine and nonionogenic tenside all through checking.
SEPIGEL 305 HPAM, Daqing Refinery company produce, and degree of hydrolysis is about 20%, and molecular-weight average is 1,900 ten thousand.
The IT test adopts the TEXAS-500C rotation to drip interfacial tensimeter, and the IT probe temperature is 45 ℃, and the IT test duration is 2 hours, grand celebration one factory's crude oil.
The formula system that contains betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside: complexed surfactant 0.025%～0.3%, polymkeric substance HPAM 0.15%, all the other inject water for grand celebration one factory;
Wherein in the complexed surfactant,
Betaine type amphoteric surfactant does
Arylalkyl polyoxyethylenated alcohol class nonionogenic tenside does
The weight ratio of betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside is 30: 70.
The result is as shown in Figure 8 for the dynamic interface tension detection.
SEPIGEL 305 HPAM, Daqing Refinery company produce, and degree of hydrolysis is about 20%, and molecular-weight average is 1,900 ten thousand.
Emulsifying property testing method: binary system to be measured and 1: 1 volume ratio of crude oil are placed tool plug test tube; After adopting homogenizing appearance emulsification (rotating speed 10000rpm) 1min; Measure final bleed rate as estimating the preliminary index of emulsifying property, estimate emulsifying property in conjunction with the actual emulsifying effectiveness of Berea core oil displacement experiment.
The formula system that contains betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside: complexed surfactant 0.025%～0.3%, polymkeric substance HPAM 0.15%, all the other inject water for grand celebration one factory;
Wherein in the complexed surfactant,
Betaine type amphoteric surfactant does
Arylalkyl polyoxyethylenated alcohol class nonionogenic tenside does
The weight ratio of betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside is 50: 50.
Daqing oil field natural core Physical simulation experiment shows that the emulsification of ternary composite driving exit end does not improve the high 5%-6% of RF than emulsification occurring.There is research to think that it is the principal mode that ternary composite driving improves oil displacement efficiency that the emulsive oil droplet produces.The ASP FLOODING IN DAQING OIL FIELD field test shows that emulsification is favourable to the oil displacement efficiency that improves ternary composite driving.This shows that whether the alkali-free binary system possesses certain emulsifying capacity has great importance to the raising of oil displacement efficiency.
At first adopt the profit of a factory, six factories; Utilize the bleed rate that the emulsifying property of the displacement of reservoir oil compsn binary system that comprises betaine type amphoteric surfactant and non-ionics of present embodiment has been carried out preliminary assessment, (polymkeric substance 1,900 ten thousand 2000ppm) are as shown in Figure 9 for the binary system bleed rate of different activities agent concentration.As can beappreciated from fig. 9, along with the increase of displacement of reservoir oil composition concentration of the present invention, the bleed rate reduces, and emulsifying property strengthens; The bleed rate has emulsifying property preferably between 60%-95%, suitable with the strong base ternary system basically.
Salt-resistant polymer KYPAM, the permanent dimerization plant produced in Beijing, degree of hydrolysis is about 25%, and molecular-weight average is 2,500 ten thousand.
The IT test adopts the TEXAS-500C rotation to drip interfacial tensimeter, and the IT probe temperature is 45 ℃, and the IT test duration is 2 hours, grand celebration six factory's crude oil.
The formula system that contains betaine type amphoteric surfactant and alkyl alcohol polyethenoxy ether class nonionogenic tenside: complexed surfactant 0.025%～0.3%, polymkeric substance 0.00%, all the other are grand celebration six factory's oilfield injection waters;
Wherein in the complexed surfactant,
Betaine type amphoteric surfactant does
Alkyl alcohol polyethenoxy ether class nonionogenic tenside does
CH
3(CH
2)
9CH
2(CH
2)
10CH
2O(CH
2CH
2O)
15H；
The weight ratio of betaine type amphoteric surfactant and alkyl alcohol polyethenoxy ether class nonionogenic tenside is 70: 30.
The result is shown in figure 10 for the dynamic interface tension detection.
Salt-resistant polymer KYPAM, the permanent dimerization plant produced in Beijing, degree of hydrolysis is about 20%, and molecular-weight average is 1,900 ten thousand.
The IT test adopts the TEXAS-500C rotation to drip interfacial tensimeter, and the IT probe temperature is 35 ℃, and the IT test duration is 2 hours, Xinjiang Qi Zhongqu crude oil.
The formula system that contains betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside: complexed surfactant 0.025%～0.3%, polymkeric substance KYPAM 0.15%, all the other are big Xinjiang Qi Zhongqu oilfield injection water;
Wherein in the complexed surfactant,
Betaine type amphoteric surfactant does
Arylalkyl polyoxyethylenated alcohol class nonionogenic tenside does
x+y＝15；
The weight ratio of betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside is 60: 40.
The result is shown in figure 11 for the dynamic interface tension detection.
SEPIGEL 305 HPAM, Daqing Refinery company produce, and degree of hydrolysis is about 15%, and molecular-weight average is 2,500 ten thousand.
The IT test adopts the TEXAS-500C rotation to drip interfacial tensimeter, and the IT probe temperature is 55 ℃, and the IT test duration is 2 hours, long celebrating two factory's crude oil.
The formula system that contains betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside: complexed surfactant 0.025%～0.3%, polymkeric substance HPAM 0.2%, all the other are long celebrating two factory's oilfield injection waters;
Wherein in the complexed surfactant,
Betaine type amphoteric surfactant does
m+n=15, its nuclear-magnetism figure is referring to Figure 12;
Arylalkyl polyoxyethylenated alcohol class nonionogenic tenside does
x+y=15, it is to substitute the reaction product that YLENE prepares according to the method for embodiment 1 with toluene;
The weight ratio of betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside is 55: 45.
The result is shown in figure 13 for the dynamic interface tension detection.
Visible from Fig. 8, Figure 10, Figure 11, Figure 13; The formula system that contains betaine type amphoteric surfactant and alkyl alcohol polyethenoxy ether class nonionogenic tenside of the present invention reaches ultralow to grand celebration, Xinjiang, long IT of celebrating oil field oil water in 0.025%～0.3% scope, interface performance is excellent.
SEPIGEL 305 HPAM, Daqing Refinery company produce, and degree of hydrolysis is about 20%, and molecular-weight average is 2,500 ten thousand.
The IT test adopts the TEXAS-500C rotation to drip interfacial tensimeter, and the IT probe temperature is 45 ℃, and the IT test duration is 2 hours, grand celebration one factory's crude oil.
Cloth formula viscometer determining, rotating speed 6r/min are adopted in viscosimetric analysis.
The formula system that contains betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside: complexed surfactant 0.2%, polymkeric substance HPAM 0.2%, all the other are grand celebration one factory's oilfield injection water;
Wherein in the complexed surfactant,
Betaine type amphoteric surfactant is the said compound of formula (I-1) and the combination of mass ratio such as (I-2) said compound:
formula (I-1) with (I-2) in, m+n=15;
Arylalkyl polyoxyethylenated alcohol class nonionogenic tenside does
The weight ratio of betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside is 60: 40.
Binary system and polymer blank monobasic system with above-mentioned formulated; In 45 ℃ of baking ovens; Period sampling measuring IT and viscosity; Sign contains the formula system stability of betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside, and the result is shown in Figure 14 a and Figure 14 b.
Experimental example 8 contains the formula system stability mensuration of betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside
SEPIGEL 305 HPAM, Daqing Refinery company produce, and degree of hydrolysis is about 20%, and molecular-weight average is 1,900 ten thousand.
The IT test adopts the TEXAS-500C rotation to drip interfacial tensimeter, and the IT probe temperature is 45 ℃, and the IT test duration is 2 hours, grand celebration six factory's crude oil.
Cloth formula viscometer determining, rotating speed 6r/min are adopted in viscosimetric analysis.
The formula system that contains betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside: complexed surfactant 0.2%, polymkeric substance HPAM 0.15%, all the other are grand celebration six factory's oilfield injection waters;
Wherein in the complexed surfactant,
Betaine type amphoteric surfactant does
Arylalkyl polyoxyethylenated alcohol class nonionogenic tenside does
The weight ratio of betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside is 70: 30.
Binary system and polymer blank monobasic system with above-mentioned formulated; In 45 ℃ of baking ovens; Period sampling measuring IT and viscosity; Sign contains the formula system stability of betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside, and the result is shown in Figure 15 a and Figure 15 b.
Visible from Figure 14 a, Figure 14 b, Figure 15 a and Figure 15 b; The formula system that contains betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside of the present invention is kept ultralow at 90 inner boundary tension force; Viscosity free of losses (more blank reference has certain increase), the system stability is excellent.
Experimental example 9 contains the formula system absorption property mensuration of betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside
SEPIGEL 305 HPAM, Daqing Refinery company produce, and degree of hydrolysis is about 20%, and molecular-weight average is 1,900 ten thousand.
The IT test adopts the TEXAS-500C rotation to drip interfacial tensimeter, and the IT probe temperature is 45 ℃, and the IT test duration is 2 hours, grand celebration one factory, six factory's crude oil.
The formula system that contains betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside: complexed surfactant 0.2%, polymkeric substance HPAM 0.2%, all the other are grand celebration one factory, six factory's oilfield injection waters;
Wherein in the complexed surfactant,
Betaine type amphoteric surfactant does
Arylalkyl polyoxyethylenated alcohol class nonionogenic tenside is the said compound of formula (III) and the combination of mass ratio such as (IV) said compound
The weight ratio of betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside is 30: 70.
By solid-to-liquid ratio 1: 9 60～100 order grand celebration oil-sands and trimethyl-glycine formula system are added in the ground Erlenmeyer flask of band plug; After will placing 0.50 ℃ of 45 scholar's (grand celebration reservoir temperature) constant-temperature shaking water bath to vibrate 24 hours with the plug Erlenmeyer flask behind the good seal; Take out Erlenmeyer flask; Measure upper solution IT continued and adsorb with new oil-sand, repetition like this, until IT can not reach ultralow till.The result is shown in figure 16.Can find out; The formula system that contains betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside to grand celebration one factory profit absorption ten once, grand celebration six factory's profit systems adsorb ten secondary rear interface tension force and still reach ultralow, absorption property is excellent.
Experimental example 10 contains the formula system displacement of reservoir oil performance evaluation of betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside
SEPIGEL 305 HPAM, Daqing Refinery company produce, and degree of hydrolysis is about 20%, and molecular-weight average is 1,900 ten thousand.
Grand celebration one factory's simulated oil (joint station oil and kerosene preparation, viscosity 10mPas), water injects in grand celebration one factory.
The grand celebration natural core.
The oil displacement experiment step: the rock core saturated oil adopts 0.05ml/min displacing velocity saturated oil earlier, adopts 0.1ml/min, 0.2ml/min, the further saturated oil of 0.4ml/min displacing velocity after the oil breakthrough.Carry out the water drive displacement of reservoir oil then; Water drive reaches at 98% o'clock to moisture; Change and annotate formula system and the polymkeric substance protection slug that contains betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside, the follow-up water drive of reinjecting to moisture reaching more than 99%.Flow out the water yield, former oil mass and pressure change in the record displacement process.Reference is according to petroleum industry standard SY/T 6424-2000 composite oil-displacing system performance test methods.
The formula system one that contains betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside:
Complexed surfactant 0.2%, polymkeric substance 0.2%, all the other are grand celebration one factory's oilfield injection water;
Wherein in the complexed surfactant,
Betaine type amphoteric surfactant does
Arylalkyl polyoxyethylenated alcohol class nonionogenic tenside does
The weight ratio of betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside is 70: 30.
The formula system two that contains betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside:
Complexed surfactant 0.2%, polymkeric substance 0.15%, all the other are grand celebration one factory's oilfield injection water;
Wherein in the complexed surfactant,
Betaine type amphoteric surfactant does
Arylalkyl polyoxyethylenated alcohol class nonionogenic tenside does
The weight ratio of betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside is 55: 45.
The oil displacement experiment result sees table 1.It is thus clear that; This formula system that contains betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class nonionogenic tenside can improve RF more than 18% on waterflood recovery efficiency factor about 40% bases; This system dimension has the ability of good raising crude oil oil displacement efficiency, has favorable industrial application prospect.
Table 1 contains betaine type amphoteric surfactant and arylalkyl polyoxyethylenated alcohol class
The formula system displacement of reservoir oil performance test result of nonionogenic tenside
Annotate: the total consumption≤900mg/LPV of tensio-active agent, the total consumption≤1000mg/LPV of polymkeric substance.
Claims (10)
1. the displacement of reservoir oil compsn that comprises betaine type amphoteric surfactant, this displacement of reservoir oil compsn is made up of following ingredients:
Complexed surfactant 1～30 weight part, and
Polymkeric substance 0～25 weight part;
Wherein said complexed surfactant is the combination of betaine type amphoteric surfactant and nonionogenic tenside, and the weight ratio of said betaine type amphoteric surfactant and nonionogenic tenside is 10～90: 90～10,
Said betaine type amphoteric surfactant is the combination of one or more in the compound shown in the formula (I):
In the formula (I), m, n are respectively and are selected from 0～19 integer, and m and n are not 0 simultaneously;
R
1Be the alkyl phenyl of alkyl, phenyl or C1～8 of H, C1～8, R
3Be the alkyl of C1～8, R
4Alkyl for C1～8;
X is
or
Said nonionogenic tenside is an alkyl alcohol Soxylat A 25-7 compounds, and this compound structure is suc as formula shown in (II):
In the formula (II), R is the alkyl phenyl of alkyl, phenyl or C1～8 of H, C1～8;
X, y are respectively and are selected from 0～19 integer and x, y is not 0 simultaneously;
Z is selected from 3～25 integer.
2. the displacement of reservoir oil compsn that comprises betaine type amphoteric surfactant according to claim 1, wherein, the weight ratio of betaine type amphoteric surfactant and nonionogenic tenside is 30～70: 70～30.
3. the displacement of reservoir oil compsn that comprises betaine type amphoteric surfactant according to claim 1, wherein,
In the formula (I), m, n are respectively and are selected from 0～19 integer, and m+n=5～19, R
1Be the alkyl phenyl of alkyl, phenyl or C1～4 of H, C1～4, R
3Be the alkyl of C1～4, R
4Alkyl for C1～4; Preferably, m, n are respectively and are selected from 0～19 integer, and m+n=9～19, R
1Be H, methyl, ethyl, phenyl, tolyl, xylyl or ethylphenyl, R
2Be H or methyl or ethyl, R
3Be H or methyl or ethyl; X does
Perhaps
In the formula (II), R is alkyl, phenyl, tolyl, xylyl or the ethylphenyl of H, C1～4; X, y are respectively and are selected from 0～19 integer and x+y=9～19; Z is selected from 3～25 integer.
4. the displacement of reservoir oil compsn that comprises betaine type amphoteric surfactant according to claim 1, wherein,
Said betaine type amphoteric surfactant is selected from one or more in the following compound:
Wherein, m, n are respectively and are selected from 0～19 integer and m+n=9～19, preferred m+n=9,15 or 19; Said alkyl alcohol Soxylat A 25-7 compounds is selected from one or more in the following compound:
CH
3(CH
2)
xCH
2(CH
2)
yCH
2O(CH
2CH
2O)
zH
Wherein, x, y are respectively and are selected from 0～19 integer and x+y=9～19, preferred x+y=9,15 or 19; Z is 5,7,10,15 or 20.
5. the displacement of reservoir oil compsn that comprises betaine type amphoteric surfactant according to claim 1, said polymkeric substance is a partially hydrolyzed polyacrylamide, degree of hydrolysis 10～30%, molecular-weight average are 300～3,500 ten thousand.
6. displacement of reservoir oil compsn mixed solution, it comprises each described displacement of reservoir oil compsn and water that comprises betaine type amphoteric surfactant of claim 1～5, in this displacement of reservoir oil compsn mixed solution, the mass concentration of complexed surfactant is 0.01%～0.3%; Preferably, in this displacement of reservoir oil compsn mixed solution, said complexed surfactant concentration is 0.05%～0.25%, and said polymer concentration is 0.1%～0.2%.
7. displacement of reservoir oil compsn mixed solution according to claim 6, wherein, said water is oilfield injection water.
8. each described displacement of reservoir oil compsn or claim 6 or 7 described displacement of reservoir oil compsn mixed solution application in TOR that comprise betaine type amphoteric surfactant of claim 1～5.
9. flooding method utilizes each described displacement of reservoir oil compsn that comprises betaine type amphoteric surfactant of claim 1～5 or claim 6 or 7 described displacement of reservoir oil compsn mixed solutions to carry out the displacement of reservoir oil in this method.
10. a TOR method has been utilized each described displacement of reservoir oil compsn or claim 6 or 7 described displacement of reservoir oil compsn mixed solutions that comprise betaine type amphoteric surfactant of claim 1～5 in this method.
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