CN103965855A - Compound oil displacement agent containing double-long-chain-alkyl sulphobetaine and application thereof - Google Patents
Compound oil displacement agent containing double-long-chain-alkyl sulphobetaine and application thereof Download PDFInfo
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Abstract
The invention discloses a compound oil displacement agent containing double-long-chain-alkyl sulphobetaine and an application thereof, which belong to the technical field of oil displacement in oil exploitation. The double-long-chain-alkyl sulphobetaine in the compound oil displacement agent disclosed by the invention is an ampholytic surfactant which is prepared by reacting double-long-chain-alkyl methyltertiary amine with 3-chloro-2-hydroxypropyl sodium sulfonate or 1,3-phenylacetophenone, and the carbon atom number of each long-chain alkyl is 8-18. The surfactant has good oil solubility, is insoluble in water, and incapable of reducing the interfacial tension of Daqing crude oil/formation water to an order of magnitude of 10<-3>mN/m when used alone. The surfactant is compounded with a specific hydrophilic surfactant serving as solubilizer, wherein the molar fraction of the double-long-chain-alkyl sulphobetaine is 0.1-0.7, the addition of polyacrylamide in a water phase is 1000 mg/L, no alkali or inorganic electrolyte is added, and the interfacial tension of Daqing crude oil/formation water can be reduced to the order of magnitude of 10<-3> mN/m under a condition of total surfactant concentration of 0.25-12.5 mM (the mass fraction is about 0.015-0.75%).
Description
Technical field
The present invention relates to the application of a kind of double long-chain alkyl sultaine tensio-active agent in tertiary oil recovery, belong to the technology of reservoir sweep field in oil production.
Background technology
The Amount of Consumption of Crude Oil of China sharply increases in recent years, and within 2013, the external interdependency of crude oil approaches 60%.But then, the each elephant of China still has huge crude oil reserve, is just difficult to extraction by ordinary method.
Conventional oil production method is so-called one to adopt (blowing) and two and adopt (filled drive), and both totals only can extraction be no more than 40% underground storage.Remaining irreducible oil is caught in the hole of porous rock by circle with the form of oil droplet, due to wicking action, is difficult to flow out under conventional waterflood pressure.Although add polymkeric substance can improve to a certain extent recovery ratio in water, this measure is only the swept volume (sweeping oily efficiency) that increases injected water, can not reduce residual oil saturation.If inject in theory water phase surfactant mixture, make crude oil/water interfacial tension be down to 10
-3the mN/m order of magnitude just can make to be enclosed the oil droplet of catching and overcome wicking action and flow out from porous medium under conventional waterflood pressure.The so-called ultra low interfacial tension displacement of reservoir oil that Here it is, a kind of important chemical flooding tertiary oil recovery technology.
Since the eighties in last century, extensively carry out the research of alkali, surfactant and polymer (ASP) ternary composite driving technology both at home and abroad.By the synergy of alkali and tensio-active agent, crude oil/local water interfacial tension can drop to 10
-3the mN/m order of magnitude therefore can further improve recovery ratio 15%～20% after water drive.But field test in recent years shows, ASP drives and is easy to cause injection device and oil well fouling, and may cause stratum capillary channel to stop up even making oil well scrap.May to be highly basic used have generated due to insoluble substance as NaOH reacts with the mineral substance in rock or local water for this.In order to overcome the side effect of alkali, people attempt to use weak base to replace highly basic, or do not use alkali, replace ASP ternary composite driving with surfactant and polymer binary combination flooding.But under alkali-free condition, ASP drives tensio-active agent used as sulfonated petro-leum, heavy alkylbenzene sulfonate, natural carboxylates, petroleum carboxylate and sulfonated lignin etc. can not be down to crude oil/water interfacial tension ultralow conventionally, need to research and develop new tensio-active agent for this reason.
Although CN103113869A discloses the oil-displacing agent that a kind of double long-chain alkyl hydroxypropyl sultaine and water are hybridly prepared into, can reduce the interfacial tension of Dagang Oilfield/local water, but can not effectively reduce Daqing oil field/local water interfacial tension but only prepare with above-mentioned tensio-active agent and water the oil-displacing agent obtaining, composite oil-displacing agent of the present invention has solved this technical problem well.
Summary of the invention
The object of the invention is to: a kind of oil soluble surfactant based on having double long-chain alkyl structure in renewable raw materials, molecule is proposed as critical surfaces promoting agent, by with specific hydrophilic surfactant active's composite usage in Daqing oil field tertiary oil recovery.
Technical scheme of the present invention: a kind of composite oil-displacing agent containing double long-chain alkyl sultaine and in the application improving in oil recovery, it is characterized in that, described double long-chain alkyl sultaine has lower array structure:
Wherein R
1and R
2for C
8～C
18chain alkyl, comprise straight chain or side chain, saturated or unsaturated;
R
1and R
2carbonatoms equate or unequal;
R
3for C
1～C
5short-chain alkyl;
R
4for containing the group of sulfo group.
More suitably R
1and R
2carbonatoms be C
10-C
14.
More suitably R
1and R
2carbonatoms equate.
More suitably R
3for methyl or ethyl.
More suitably R
4for one of following groups:
-CH
2CH
2SO
3 -，-CH
2CH
2CH
2SO
3 -，-CH
2CH(OH)CH
2SO
3 -。
Owing to having double long-chain alkyl, this sultaine class tensio-active agent belongs to oil soluble surfactant, almost insoluble in water, therefore needs the composite use with specific water soluble surfactant active.Therefore these water soluble surfactant actives are called as solubilizing agent.
Being applicable to the solubilizing agent of above-mentioned sultaine class surfactant compound is amphoterics and nonionogenic tenside.
The amphoterics that is wherein suitable as solubilizing agent is mainly single-long-chain alkyl carboxybetaine and single-long-chain alkyl sultaine, has following general structure:
Wherein R
5for C
8～C
18chain alkyl, comprise straight chain or side chain, saturated or unsaturated;
R
6for-CH
2cOO
-,-CH
2cH
2cOO
-,-CH
2cH
2cH
2cOO
-and-CH
2cH
2sO
3 -,-CH
2cH
2cH
2sO
3 -with-CH
2cH (OH) CH
2sO
3 -in one;
More suitably R
5for C
12-C
16alkyl.
More suitably R
6for-CH
2cOO
-or-CH
2cH (OH) CH
2sO
3 -.
More suitably, amphoterics is to have different alkyl chain length R
5homology mixture.
The nonionogenic tenside that is suitable as solubilizing agent is the alkylolamide ethoxylate with following general structure:
Wherein R
7for C
7～C
17chain alkyl, comprise straight chain or side chain, saturated or unsaturated, m=1～10, are average EO number.
More suitably R
7for C
11～C
15alkyl.
More suitably m=2～5.
More suitably nonionogenic tenside is to have different alkyl chain length R
7homology mixture.
By by composite to double long-chain alkyl sultaine of the present invention (I) and above-mentioned amphoterics (II), or composite with above-mentioned nonionogenic tenside (III), or simultaneously with (II) and (III) composite, wherein above-mentioned all surface promoting agent can be the different homology mixture of one-component or alkyl chain length, the molar fraction of double long-chain alkyl sultaine in total surfactant is 0.1～0.7, mixed surfactant is dissolved in to grand celebration local water, the total mineralization of water is 5335mg/L, Ca
2+and Mg
2+content is about 65mg/L, in water, add polyacrylamide (molecular weight approximately 2,500 ten thousand) 1000mg/L, do not add any alkali or inorganic electrolyte, can in total surfactant concentration 0.25～12.5mM (massfraction approximately 0.01%～0.75%) scope, make Daqing crude oil/local water interfacial tension be down to 10 at 45 DEG C
-3the mN/m order of magnitude.
The preparation method of described double long-chain alkyl sultaine:
(1) react with 3-chlorine-2-hydroxyl propanesulfonate with double long-chain alkyl methyl tertiary amine, double long-chain alkyl methyl tertiary amine and 3-chlorine-2-hydroxyl propanesulfonate mol ratio are 1: 1.1, reaction medium is isopropanol/water mixed solvent, add 1.5% (in tertiary amine) KI to make catalyzer, under reflux temperature, react 24 hours, after reaction finishes, revolve and steam except desolventizing, NaCl and the unreacted 3-chlorine-2-hydroxyl propanesulfonate of generation removed in washing, ethyl alcohol recrystallization is removed unreacted tertiary amine, obtains double long-chain alkyl hydroxypropyl sultaine (diC
nhSB), product purity reaches more than 98%.
(2) react with double long-chain alkyl methyl tertiary amine and 1,3-the third sultone, tertiary amine and 1,3-the third sultone mol ratio are 1: 1.2,, react 12 hours at 80 DEG C for solvent with 1,2-ethylene dichloride.Reaction finishes to regulate reaction mixture pH to weakly alkaline with sodium hydroxide solution afterwards, and suction filtration is collected product, adds acetone heating that reaction mixture is dissolved completely, under room temperature, leave standstill recrystallization, it is unreacted 1 that suction filtration is removed, 3-the third sultone, and precipitate with washing with acetone; The precipitation of collecting is joined to recrystallization in proper amount of acetone, then vacuum-drying 12 hours at 40 DEG C, double long-chain alkyl propyl group sultaine (diC obtained
nsB), product purity reaches more than 98%.
The performance characteristic of described tensio-active agent: the double long-chain alkyl sultaine obtaining through separating-purifying is white powder-like product.Owing to having double long-chain alkyl, their poorly water-soluble, works as R
1+ R
2>=C
24time, their solubleness in water is generally less than its micelle-forming concentration (cmc), therefore cannot obtain cmc by the surface tension of measuring the aqueous solution, but they are soluble in toluene, therefore can obtain its micelle-forming concentration by measuring toluene/water interface tension force.
Beneficial effect of the present invention: raw material double long-chain alkyl tertiary amine of the present invention is natural fats and oils derivative, belongs to renewable product.Owing to having adopted double long-chain alkyl structure, the total carbon atom number in alkyl chain has been broken through natural fats and oils raw material alkyl chain length and has generally been no more than C
18restriction, ensured that tensio-active agent has enough lipophilicities, thereby become a kind of displacement of reservoir oil critical surfaces promoting agent.Although it is water-soluble poor, by with the composite solubilising of specific hydrophilic surfactant active, can under alkali-free condition, make Daqing crude oil/water termination tension force be down to ultralow, be applicable to alkali-free binary combination flooding.
Brief description of the drawings
The two dodecyl methyl hydroxypropyl sultaine (diC of Fig. 1
12hSB) infrared spectrogram of purified product
The two dodecyl methyl hydroxypropyl sultaine (diC of Fig. 2
12hSB) mass spectrum of purified product (positive charge pattern)
The two dodecyl methyl propyl group sultaine (diC of Fig. 3
12sB) infrared spectrogram of purified product
The two dodecyl methyl propyl group sultaine (diC of Fig. 4
12sB) mass spectrum of purified product (positive charge pattern)
DiC at 5 DEG C of Figure 52
12hSB and diC
12toluene solution/water termination tension force of SB purified product is with the variation of concentration
Single diC at 5 DEG C of Figure 62
12hSB and with tetradecyl methyl hydroxypropyl sultaine (C
14hSB) dissolution characteristics of mixture in water and the surface tension of the aqueous solution.
Single diC at 5 DEG C of Figure 72
12sB and with tetradecyl methyl hydroxypropyl sultaine (C
14hSB) dissolution characteristics of mixture in water and the surface tension of the aqueous solution.
Fig. 8 Daqing crude oil/local water dynamic interface tension force.Measure temperature 45 C, mixed surfactant total concn 0.25～7.5mM, as shown in legend, contains 1000mg/L polyacrylamide (molecular weight 25,000,000) in solution.DiC in mixed surfactant
12hSB molar fraction 0.25, all the other are single-long-chain alkyl dimethyl hydroxypropyl sultaine amphoterics (C
14and alkylolamide ethoxylate class nonionogenic tenside (n=16, m=4) HSB).
Fig. 9 Daqing crude oil/local water dynamic interface tension force.Measure temperature 45 C, mixed surfactant total concn 5～12.5mM, as shown in legend, contains 1000mg/L polyacrylamide (molecular weight 25,000,000) in solution.DiC in mixed surfactant
12sB molar fraction 0.27, all the other are single-long-chain alkyl dimethyl carboxybetaine amphoterics (C
16and alkylolamide ethoxylate class nonionogenic tenside (n=16, m=3) B).
Embodiment
1 couple of dodecyl methyl hydroxypropyl sultaine (diC of embodiment
12hSB) preparation
Taking two dodecyl methyl tertiary amines (A) as raw material (Sol dimension Fine Chemical Co., Ltd), react with 3-chlorine-2-hydroxyl propanesulfonate (B) (Sol dimension Fine Chemical Co., Ltd), mol ratio is A: B=1: 1.1, and reaction medium is isopropanol/water (volume ratio=6: 1) mixed solvent.Add a certain amount of sodium carbonate (B: Na
2cO
3=1: 0.05) and 1.5% (in tertiary amine) KI makes catalyzer.In the 500mL there-necked flask that stirrer, thermometer and prolong are housed, add 23.58g3-chlorine-2-hydroxyl propanesulfonate, add 140mL water/isopropyl alcohol mixture, be stirred to completely and dissolve.Add again 0.1mol (36.7g) diC
12the sodium carbonate of A and aequum and potassiumiodide.Be warming up to 85 DEG C, back flow reaction 48 hours, diC
12a transformation efficiency can reach 90.2%.After reaction finishes, revolve and steam except desolventizing, NaCl and the unreacted 3-chlorine-2-hydroxyl propanesulfonate of generation removed in washing, and ethyl alcohol recrystallization is removed unreacted tertiary amine, obtain purity and be 98% with upper product (C).Reaction equation is as follows:
The sign of product: confirm product structure by infrared spectra, mass spectrum and nuclear-magnetism, its middle infrared spectrum and mass spectrum are respectively as depicted in figs. 1 and 2.As seen from Figure 2, under positive charge pattern, product is in conjunction with a H
+or Na
+and positively charged, thereby show positive ion peak.Infer accordingly, two quasi-molecular ion peaks the strongest in Fig. 2, m/z=506.2 and m/z=528.2, correspond respectively to [M+Na]
+[M+H]
+, show molecular weight of product M=505, with target product diC
12the molecular weight of HSB fits like a glove.The quasi-molecular ions of m/z=368.3 is corresponding to [M+H] of two dodecyl methyl tertiary amines
+, the quasi-molecular ions of m/z=780.9 is corresponding to the diploid 2[M+Na of two dodecyl methyl tertiary amines]
+.And the mass spectrum of two dodecyl methyl hydroxypropyl sultaine of announcing in CN103113869A does not conform to molecular structure.
Can prepare alkyl chain length by similar method is C
8～C
18other double long-chain alkyl methyl hydroxypropyl sultaine.
2 couples of dodecyl methyl propyl group sultaine (diC of embodiment
12sB) preparation
Taking two dodecyl methyl tertiary amines (A) as raw material (Sol dimension Fine Chemical Co., Ltd), with 1,3-the third sultone (D) (Jiangsu dream obtains electroplating chemical product company limited) reaction, mol ratio is A: D=1: 1.2, reaction medium is 1,2-ethylene dichloride.In the 250mL there-necked flask that stirrer, thermometer and prolong are housed, add 0.1mol tertiary amine and 40mL1,2-ethylene dichloride, opens and stirs, and is warming up to 50 DEG C.In half an hour, 0.12mol is dissolved in to 40mL1,1 in 2-ethylene dichloride, 3-the third sultone solution is added dropwise in reaction flask.Reacting by heating thing, to 80 DEG C of reflux temperatures, reacts 12 hours, regulates reaction mixture pH to weakly alkaline with sodium hydroxide solution, diC
12the transformation efficiency of A can reach 93%.Cooling rear suction filtration, collects product, adds acetone heating that product is dissolved completely, leaves standstill recrystallization under room temperature, then suction filtration remove unreacted 1,3-the third sultone, then precipitate with washing with acetone; The precipitation obtaining is joined to recrystallization in proper amount of acetone, and suction filtration obtains crystal, and at 40 DEG C, vacuum-drying obtain powdery white solid for 12 hours.Reaction equation is as follows:
The sign of product: confirm product structure by infrared spectra, the coupling of liquid-matter and nuclear-magnetism.Its middle infrared spectrum and mass spectrum are respectively as shown in Figure 3 and Figure 4.As seen from Figure 4, under positive charge pattern, product is in conjunction with a H
+or Na
+and positively charged, thereby show positive ion peak.Infer accordingly, quasi-molecular ion peak the strongest in Fig. 2 is corresponding to [M+H]
+, show molecular weight of product M=489.4, with target product diC
12the molecular weight of SB fits like a glove.
Can prepare alkyl chain length by similar method is C
8～C
18other double long-chain alkyl methyl-propyl sultaine.
The surfactivity of embodiment 3 products
DiC
12hSB and diC
12sB poorly water-soluble, but can be dissolved in toluene, at 25 DEG C, by measuring toluene/water interface tension force (Fig. 5), obtain diC
12the micelle-forming concentration (cmc) of HSB is 1.8 × 10
-5mol/L, saturated extent of adsorption Г
∞be 7.5 × 10
-10mol/cm
2, corresponding molecular area is 0.22nm
2/ molecule.Similarly, obtain diC
12the cmc of SB is 4.5 × 10
-6mol/L, saturated extent of adsorption Г
∞be 1.0 × 10
-9mol/cm
2, corresponding molecular area is 0.17nm
2/ molecule.Visible owing to lacking a hydroxyl, diC
12the wetting ability of SB compares diC
12hSB is also low, thereby tensio-active agent is higher.
Water-soluble and the surfactivity of embodiment 4 products
Under extremely low concentration (≤1 × 10
-5mol/L), diC
12hSB can be dissolved in pure water.At 25 DEG C, measure the variation of surface tension with concentration, result as shown in Figure 6.Be 7.0 × 10 from curve obtained by obtain saturated extent of adsorption with Szyszkowski formula fitting
-10mol/cm
2, with almost identical based on toluene/water interface tension force acquired results.Under high density, by itself and water soluble surfactant active's tetradecyl dimethyl hydroxypropyl sultaine (C
14hSB) within 1: 1 in molar ratio, mix and can obtain clear solution, the surface tension that records mixing solutions is 31.1mN/m.Because both are homologues, according to ideal mixing theory, can judge diC
12the γ of HSB
cmcshould be no more than 31.1mN/m.When the concentration of mixture is less than 1.5 × 10
-4mol/L (C
14the cmc of HSB), owing to there is no micella, diC in system
12hSB is Precipitation again, forms settling region, as shown in Figure 6.These data show, diC
12hSB has very high surfactivity, especially has very high saturated extent of adsorption at oil/water interface, therefore can be used for reducing crude oil/water interfacial tension, is applied to tertiary oil recovery.
Similarly, under extremely low concentration (≤1 × 10
-6mol/L), diC
12sB can be dissolved in pure water.At 25 DEG C, measure the variation of surface tension with concentration, result as shown in Figure 7.Under high density, by itself and water soluble surfactant active's tetradecyl dimethyl hydroxypropyl sultaine (C
14hSB) within 1: 1 in molar ratio, mix and can obtain clear solution, the surface tension that records mixing solutions is 29.8mN/m.Both belong to homologue substantially, according to ideal mixing theory, can judge diC
12the γ of SB
cmcshould be no more than 29.8mN/m.When the concentration of mixture is less than 1.5 × 10
-4mol/L (C
14the cmc of HSB) time, owing to there is no micella, diC in system
12sB is Precipitation again, forms settling region, as shown in Figure 7.These data show, diC
12sB has very high surfactivity, especially has very high saturated extent of adsorption at oil/water interface, therefore can be used for reducing crude oil/water interfacial tension, is applied to tertiary oil recovery.
Embodiment 5 reduces Daqing crude oil/local water interfacial tension
By the diC of preparation
12hSB is as lipophilic surfactant, for example, with hydrophilic surfactant active's single-long-chain alkyl dimethyl hydroxypropyl sultaine (C
14hSB) and alkylolamide ethoxylate class nonionogenic tenside (for example n=16, m=4) mix, be dissolved in Daqing oil field local water, the total mineralization of water is 5335mg/L, Ca
2+and Mg
2+content is about 65mg/L, tensio-active agent total concn be 0.25mM to 7.5mM, wherein diC
12the molar fraction of HSB is 0.25, adds 1000mg/L polyacrylamide (molecular weight 2,500 ten thousand) in water, the interfacial tension of mensuration and Daqing crude oil at 45 DEG C, and result is as shown in Figure 8.Visible within the scope of very wide total concn, crude oil/water equilibrium interfacial tension (120min) can drop to 10
-3the mN/m order of magnitude.
Embodiment 6 reduces Daqing crude oil/local water interfacial tension
By the diC of preparation
12sB is as lipophilic surfactant, for example, with hydrophilic surfactant active's single-long-chain alkyl dimethyl carboxybetaine (hexadecyldimethyl benzyl ammonium carboxybetaine C
16b) and alkylolamide ethoxylate class nonionogenic tenside (for example n=16, m=3) mix, be dissolved in Daqing oil field local water, the total mineralization of water is 5335mg/L, Ca
2+and Mg
2+content is about 65mg/L, and tensio-active agent total concn is 5 to 12.5mM, wherein diC
12the molar fraction of SB is 0.27, adds 1000mg/L polyacrylamide (molecular weight 2,500 ten thousand) in water, the interfacial tension of mensuration and Daqing crude oil at 45 DEG C, and result is as shown in Figure 9.Visible within the scope of very wide total concn, crude oil/water equilibrium interfacial tension (120min) can drop to 10
-3the mN/m order of magnitude.
Can obtain similarly multiple ternary formula or binary formula, its ultimate principle is to work as diC
nhSB or diC
nwhen the alkyl chain length of SB increases, the hydrophilic surfactant active's composite with it chain length should suitably reduce, or m number in nonionogenic tenside suitably increases.Here give an example no longer one by one.
Embodiment 7
By the diC of preparation
12hSB one-component is dissolved in grand celebration local water, and the total mineralization of water is 5335mg/L, Ca
2+and Mg
2+content is about 65mg/L, works as diC
12when HSB concentration is 1～6mM (massfraction approximately 0.05～0.3%), diC at 45 DEG C
12hSB separates out from water, the interfacial tension of Daqing crude oil/local water can not be dropped to 10
-3the mN/m order of magnitude.
Similarly, by the diC of preparation
12sB one-component is dissolved in grand celebration local water, and the total mineralization of water is 5335mg/L, Ca
2+and Mg
2+content is about 65mg/L, works as diC
12when SB concentration is 1～6mM (massfraction approximately 0.05～0.3%), diC at 45 DEG C
12sB separates out from water, the interfacial tension of Daqing crude oil/local water can not be dropped to 10
-3the mN/m order of magnitude.
Claims (6)
1. containing a composite oil-displacing agent for double long-chain alkyl sultaine, it is characterized in that, this double long-chain alkyl sultaine has following molecular structure:
Wherein R
1and R
2for C
8～C
18chain alkyl, comprise straight chain or side chain, saturated or unsaturated;
R
1and R
2carbonatoms equate or unequal;
R
3for C
1～C
5short-chain alkyl;
R
4for one of following groups:
-CH
2CH
2SO
3 -，-CH
2CH
2CH
2SO
3 -，-CH
2CH(OH)CH
2SO
3 -；
Described double long-chain alkyl sultaine is mixed to get to composite oil-displacing agent with specific water soluble surfactant active.Described specific water soluble tensio-active agent is the amphoterics with following general structure:
Wherein R
5for C
8～C
18chain alkyl, comprise straight chain or side chain, saturated or unsaturated;
R
6for-CH
2cOO
-,-CH
2cH
2cOO
-,-CH
2cH
2cH
2cOO
-and-CH
2cH
2sO
3 -,-CH
2cH
2cH
2sO
3 -with-CH
2cH (OH) CH
2sO
3 -in one;
And/or there is the alkylolamide ethoxylate nonionic surfactant of following general structure:
Wherein R
7for C
7～C
17chain alkyl, comprise straight chain or side chain, saturated or unsaturated, average EO counts m=1～10.
2. composite oil-displacing agent as claimed in claim 1, described double long-chain alkyl sultaine tensio-active agent and water soluble surfactant active use with single component or use with the homology mixture with different alkyl chain lengths.
3. composite oil-displacing agent as claimed in claim 1, the molar fraction of described double long-chain alkyl sultaine tensio-active agent in total surfactant is 0.1～0.7.
4. composite oil-displacing agent as claimed in claim 1, is characterized in that, the preparation method of the double long-chain alkyl methyl-propyl sultaine comprising is: taking two dodecyl methyl tertiary amines as raw material, obtain with 1,3-the third sultone reaction; Tertiary amine/1,3-the third sultone mol ratio 1: 1.2, reaction medium is 1,2-ethylene dichloride, and temperature of reaction is 80 DEG C, and the reaction times is 12 hours; Reaction finishes to regulate reaction mixture pH to weakly alkaline with sodium hydroxide solution afterwards, and cooling rear suction filtration is collected product, then is dissolved in recrystallization in acetone, and at 40 DEG C, vacuum-drying obtains; Reaction equation is as follows:
5. the application of the composite oil-displacing agent as described in claim 1-4: improve oil recovery for the alkali-free displacement of reservoir oil, for surfactant and polymer binary combination flooding.
6. application as claimed in claim 5, composite the present invention oil-displacing agent is dissolved in to Daqing oil field local water, tensio-active agent total concn is 0.25mM～12.5mM, in water, add polyacrylamide 1000mg/L, do not add any alkali or inorganic electrolyte, can make Daqing crude oil/local water interfacial tension be down to 10 at 45 DEG C
-3the mN/m order of magnitude.
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| CN104263344A (en) * | 2014-09-12 | 2015-01-07 | 大连东方创新科技有限公司 | Betaine surfactant combination flooding composition and application thereof |
| CN104263341A (en) * | 2014-08-08 | 2015-01-07 | 中国石油天然气股份有限公司 | Positive and negative ion surfactant compound mixture and preparation method thereof |
| CN104263345A (en) * | 2014-09-12 | 2015-01-07 | 大连东方创新科技有限公司 | Betaine surfactant combination flooding system and application thereof |
| CN104312565A (en) * | 2014-09-12 | 2015-01-28 | 大连东方创新科技有限公司 | Block copolymer-reinforced betaine surfactant composite flooding system and use thereof |
| CN104449634A (en) * | 2014-12-11 | 2015-03-25 | 江南大学 | Alkali-free compound oil displacement agent containing amide type double-strand betaine |
| CN104877654A (en) * | 2015-05-08 | 2015-09-02 | 江南大学 | Compound oil-displacing agent containing asymmetric di-long chain alkylmethyl carboxyl betaine and application thereof |
| CN105440203A (en) * | 2014-08-13 | 2016-03-30 | 中国石油化工股份有限公司 | Polymer with surface active function and preparation method thereof |
| CN106478314A (en) * | 2016-12-30 | 2017-03-08 | 定远县文凡米业有限公司 | A kind of slow release increases production Caulis et Folium Chrysanthemi segeti special fertilizer |
| CN106566509A (en) * | 2016-10-31 | 2017-04-19 | 中国石油天然气股份有限公司 | Ternary combination flooding composition and application thereof in high-temperature high-salinity oil reservoir |
| CN106566510A (en) * | 2016-10-31 | 2017-04-19 | 中国石油天然气股份有限公司 | Ternary composite flooding composition and application thereof in chemical flooding |
| CN106566513A (en) * | 2016-10-31 | 2017-04-19 | 中国石油天然气股份有限公司 | Alkali-free binary composite flooding composition and application thereof in chemical flooding |
| CN106566512A (en) * | 2016-10-31 | 2017-04-19 | 中国石油天然气股份有限公司 | Long-short chain betaine surfactant and preparation method thereof |
| CN107259077A (en) * | 2017-07-24 | 2017-10-20 | 宿松县斗山水产养殖专业合作社 | A kind of preparation method of environmental protection cray feed |
| CN107259222A (en) * | 2017-07-24 | 2017-10-20 | 宿松县斗山水产养殖专业合作社 | A kind of preparation method of nutrient health cray feed |
| CN107501135A (en) * | 2017-09-01 | 2017-12-22 | 江南大学 | The preparation and its application of a kind of sulfonate type anion surfactant containing double long-chain alkyl |
| CN114349651A (en) * | 2020-09-28 | 2022-04-15 | 中国科学院理化技术研究所 | Preparation method of double-long-carbon-chain alkyl carboxyl betaine surfactant |
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| CN104263341B (en) * | 2014-08-08 | 2017-07-07 | 中国石油天然气股份有限公司 | Positive and negative ion surfactant compound mixture and preparation method thereof |
| CN104263341A (en) * | 2014-08-08 | 2015-01-07 | 中国石油天然气股份有限公司 | Positive and negative ion surfactant compound mixture and preparation method thereof |
| CN105440203A (en) * | 2014-08-13 | 2016-03-30 | 中国石油化工股份有限公司 | Polymer with surface active function and preparation method thereof |
| CN105440203B (en) * | 2014-08-13 | 2017-08-25 | 中国石油化工股份有限公司 | A kind of polymer with surface active function and preparation method thereof |
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| CN104263345A (en) * | 2014-09-12 | 2015-01-07 | 大连东方创新科技有限公司 | Betaine surfactant combination flooding system and application thereof |
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| CN104877654A (en) * | 2015-05-08 | 2015-09-02 | 江南大学 | Compound oil-displacing agent containing asymmetric di-long chain alkylmethyl carboxyl betaine and application thereof |
| CN106566509A (en) * | 2016-10-31 | 2017-04-19 | 中国石油天然气股份有限公司 | Ternary combination flooding composition and application thereof in high-temperature high-salinity oil reservoir |
| CN106566510B (en) * | 2016-10-31 | 2019-07-09 | 中国石油天然气股份有限公司 | Ternary composite flooding composition and application thereof in chemical flooding |
| CN106566512A (en) * | 2016-10-31 | 2017-04-19 | 中国石油天然气股份有限公司 | Long-short chain betaine surfactant and preparation method thereof |
| CN106566509B (en) * | 2016-10-31 | 2019-07-09 | 中国石油天然气股份有限公司 | Ternary combination flooding composition and application thereof in high-temperature high-salinity oil reservoir |
| CN106566510A (en) * | 2016-10-31 | 2017-04-19 | 中国石油天然气股份有限公司 | Ternary composite flooding composition and application thereof in chemical flooding |
| CN106566513A (en) * | 2016-10-31 | 2017-04-19 | 中国石油天然气股份有限公司 | Alkali-free binary composite flooding composition and application thereof in chemical flooding |
| CN106566513B (en) * | 2016-10-31 | 2019-07-09 | 中国石油天然气股份有限公司 | Alkali-free binary composite flooding composition and application thereof in chemical flooding |
| CN106566512B (en) * | 2016-10-31 | 2019-07-09 | 中国石油天然气股份有限公司 | Long-short chain betaine surfactant and preparation method thereof |
| CN106478314A (en) * | 2016-12-30 | 2017-03-08 | 定远县文凡米业有限公司 | A kind of slow release increases production Caulis et Folium Chrysanthemi segeti special fertilizer |
| CN107259222A (en) * | 2017-07-24 | 2017-10-20 | 宿松县斗山水产养殖专业合作社 | A kind of preparation method of nutrient health cray feed |
| CN107259077A (en) * | 2017-07-24 | 2017-10-20 | 宿松县斗山水产养殖专业合作社 | A kind of preparation method of environmental protection cray feed |
| CN107501135A (en) * | 2017-09-01 | 2017-12-22 | 江南大学 | The preparation and its application of a kind of sulfonate type anion surfactant containing double long-chain alkyl |
| CN107501135B (en) * | 2017-09-01 | 2020-05-08 | 江南大学 | Preparation and application of sulfonate anionic surfactant containing double long-chain alkyl |
| CN114349669A (en) * | 2020-09-28 | 2022-04-15 | 中国科学院理化技术研究所 | Preparation method of sulfobetaine surfactant with double long alkyl chains |
| CN114349651A (en) * | 2020-09-28 | 2022-04-15 | 中国科学院理化技术研究所 | Preparation method of double-long-carbon-chain alkyl carboxyl betaine surfactant |
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