CN101549265B - Preparation of surface active agent of double long-chain alkyl amine oxide and applications thereof - Google Patents
Preparation of surface active agent of double long-chain alkyl amine oxide and applications thereof Download PDFInfo
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- CN101549265B CN101549265B CN2009100304720A CN200910030472A CN101549265B CN 101549265 B CN101549265 B CN 101549265B CN 2009100304720 A CN2009100304720 A CN 2009100304720A CN 200910030472 A CN200910030472 A CN 200910030472A CN 101549265 B CN101549265 B CN 101549265B
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- chain alkyl
- active agent
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Abstract
The invention relates to preparation of a surface active agent of double long-chain alkyl amine oxide and applications thereof, belonging to the field of colloid and interface chemistry. The surface active agent is prepared by reaction of double long-chain alkyl methyl tertiary amine and hydrogen peroxide (H2O2) and is a nonionic surface active agent and the number of carbon atoms of the long-chain alkyl is 8 to 18. By being used by combination with other surface active agents, the surface active agent can be used as an alkali-free oil-displacing agent; under the conditions that the molar fraction of the surface active agent of double long-chain alkyl lycine is 0.1 to 0.6, the total mass concentration of the active surface agent is 0.05 percent to 0.3 percent, 1000mg/L (ppm) of polyacrylamide is added, alkali is not added and the temperature is 45 DEG C, the surface active agent of double long-chain alkyl amine oxide can reduce the interfacial tension of Daqing crude oil/formation water interface to 10<-3>mN/m order of magnitude.
Description
Technical field
A kind of preparation of surface active agent of double long-chain alkyl amine oxide and application thereof belong to colloid and surface chemistry field.The surface active agent of double long-chain alkyl amine oxide that the present invention relates to is made by double long-chain alkyl methyl tertiary amine and hydrogen peroxide reaction, and the carbon number of chain alkyl is 8～18.By with other surfactant compound, can be used as non-base oil-displacing agent.Under 45 ℃, total surfactant mass fraction 0.05%～0.3% condition, need not to add alkali and can make Daqing crude oil/formation water interfacial tension be reduced to 10
-3The mN/m order of magnitude.
Background technology
Along with improving constantly of China's rapid economy development and living standards of the people, the oil consumption amount of China sharply increases, and domestic petroleum output far can not satisfy the demands.The China's oil import volume was nearly 200,000,000 tons in 2007, and externally interdependency breaks through 50%.Expect the year two thousand twenty, the China's oil insufficiency of supply-demand will reach 400,000,000 tons.On the other hand, China still has huge petroleum reserves, but is difficult to extraction with conventional method.
Usually with one of routine (blowing) and two (water filling is driven) method of adopting of adopting only can extraction underground petroleum reserves about 40%.Remaining residual oil is caught in the hole of porous rock by circle, because capillarity is difficult to flow out under conventional waterflooding pressure.Need adopt new technology, i.e. tertiary oil recovery technology in order to exploit out these residual oils.
In theory, that the crude oil/water interfacial tension is reduced to is ultralow if inject aqueous surfactant solution, and promptly 10
-3The mN/m order of magnitude then just can make the oil droplet of being caught by circle flow out from porous media under conventional waterflooding pressure.The so-called ultralow interfacial tension displacement of reservoir oil that Here it is is the dominant mechanism of surfactant flooding.
In in the past one, 20 year, extensively carried out alkali, surfactant and polymer ternary composite driving Study on Technology both at home and abroad.The result shows that ternary composite driving can reduce to 10 with crude oil/formation water interfacial tension
-3The mN/m order of magnitude improves recovery ratio 15%～20% on the water drive basis.Desk research shows, the most of oil fields of China all are suitable for ternary composite driving, yet some field tests that carry out in recent years show, in the ternary composite driving used alkali may by with rock or formation water in the mineral matter reaction, generate insoluble substance, cause oil well fouling and capillary channel to stop up, destroy the cellular structure on stratum, the serious oil well that may cause is scrapped.Use alkali easily to cause the injection device corrosive pipeline in addition, polymer-thickened effect is reduced, therefore need to improve polymer concentration, and often the high 2-5 of specific surface activating agent times of the working concentration of alkali itself, these factors make the actual integrated cost of ternary composite driving significantly raise.For the side effect that overcomes alkali and the defective of ternary composite driving, need research to replace ternary composite driving with the surfactant and polymer binary combination flooding.
Yet the common, inexpensive surfactant that is used for ternary composite driving, as petroleum sulfonate, heavy alkylbenzene sulfonate, natural carboxylic acid's salt, petroleum carboxylate and lignosulfonates etc., under the alkali-free condition, the crude oil/water interfacial tension can not be reduced to ultralowly usually, need the development of new surfactant for this reason.
Summary of the invention
The present invention seeks to propose a kind of based on renewable raw materials, the preparation of non-ionic surface active agent and the application in tertiary oil recovery thereof with double long-chain alkyl.
Technical scheme of the present invention: a kind of surface active agent of double long-chain alkyl amine oxide, this surfactant is made by double long-chain alkyl methyl tertiary amine and hydrogen peroxide reaction, is a kind of non-ionic surface active agent, and the structural formula of surface active agent of double long-chain alkyl amine oxide is:
n＝6，8，10，12，14，16
Wherein the carbon number of each chain alkyl equates, is 8～18, is the best with 10～14; Its preparation raw material double long-chain alkyl methyl tertiary amine is the natural oil derivative.
The preparation method of described surfactant, in the presence of the catalyst sodium ethylene diamine tetracetate, with double long-chain alkyl methyl tertiary amine and hydrogen peroxide reaction, the mol ratio of hydrogen peroxide and tertiary amine is (1.0～1.3): 1, catalyst amount is the 0.5%-3% of tertiary amine consumption, reaction medium is a water, 80～95 ℃ of reaction temperatures, 5～8 hours reaction time, conversion ratio 〉=80%, reaction finishes and tells water, and the upper strata is a product, contains a small amount of unreacted tertiary amine.
The application of described surfactant, by itself and other surfactant compound is used, as non-base oil-displacing agent, wherein the molar fraction of double long-chain alkyl amine oxide is 0.10～0.60, at total surfactant mass concentration 0.05%～0.3%, adding polyacrylamide 1000mg/L, do not add under alkali, the 45 ℃ of conditions, can make Daqing crude oil/formation water interfacial tension reduce to 10
-3The mN/m order of magnitude.
Double long-chain alkyl methyl tertiary amine is the chemical industry Co., Ltd product that circles in the air.
Obtain purified product through separating to purify.Through mass spectrum (Fig. 2) and infrared (Fig. 3) analytical proof product molecular structure shown in having.
Performance characteristic: the product behind the purifying is dissolved in ultra-pure water, measures surface tension and critical micelle concentration, the result shows, when concentration is no more than 1 * 10
-4Mol/L obtains transparent aqueous solution, and its critical micelle concentration is about 10
-6The mol/L order of magnitude (Fig. 3).
Application mode: with synthetic surface active agent of double long-chain alkyl amine oxide and other surfactant compound, be dissolved in the Daqing oil field formation water, wherein the molar fraction of surface active agent of double long-chain alkyl amine oxide is 0.1～0.6 in the mixed surfactant, surfactant gross mass mark is 0.05%～0.3%, add polymer (polyacrylamide) 1000ppm, 45 ℃, do not add under the condition of any alkali or alkaline matter and inorganic salts, can make Daqing crude oil/formation water interfacial tension drop to 10
-3The mN/m order of magnitude.
Beneficial effect of the present invention: the raw material of double long-chain alkyl non-ionic surface active agent of the present invention is a double long-chain alkyl methyl tertiary amine, is the derivative of natural oil.Owing to adopted the double long-chain alkyl structure, made the total carbon atom number in the alkyl chain break through the natural oil raw material smaller or equal to C
18Restriction, guaranteed that surfactant has enough lipophilies, thereby be suitable as oil displacement agent.When with other surfactant compound, it is ultralow under the alkali-free condition crude oil/water interfacial tension to be reduced to, and is applicable to that the surfactant and polymer binary combination flooding improves oil recovery factor.
Description of drawings
The mass spectrogram (positive charge pattern) of the two dodecyl methyl amine oxides of Fig. 1.Lotus/matter is than being that 384.6 material is corresponding to target product among the figure.
The infrared spectrogram of the two dodecyl methyl amine oxides of Fig. 2.Show N-O absworption peak (960cm in two dodecyl methyl amine oxide infared spectrums
-1).
The surface tension of the two dodecyl methyl amine oxide aqueous solutions of Fig. 3 is with the variation of concentration.Measure 25 ℃ of temperature.
Fig. 4 crude oil/formation water interfacial tension is with the variation of equilibration time.Condition determination: grand celebration four factory's crude oil, 45 ℃, mixed surfactant gross mass mark 0.1% and 0.3%, two ten alkyl methyl amine oxide molar fractions 0.5 in the mixed surfactant.
Fig. 5 crude oil/formation water interfacial tension is with the variation of equilibration time.Condition determination: grand celebration four factory's crude oil, 45 ℃, mixed surfactant gross mass mark 0.3%, two dodecyl methyl amine oxide molar fractions 0.20 in the mixed surfactant.
Fig. 6 crude oil/formation water interfacial tension is with the variation of equilibration time.Condition determination: grand celebration four factory's crude oil, 45 ℃, mixed surfactant gross mass mark 0.3%, two ten alkyl methyl amine oxide molar fractions 0.10 in the mixed surfactant.
The specific embodiment
The preparation of two ten alkyl methyl amine oxides: react in the presence of the catalyst sodium ethylene diamine tetracetate with hydrogen peroxide with two ten alkyl methyl tertiary amines (chemical industry Co., Ltd product circles in the air), reaction medium is a water, reaction temperature is 90 ℃, hydrogen peroxide: the tertiary amine mol ratio is (1.1): 1, catalyst amount is 1% (with respect to tertiary amine), 6 hours reaction time, tertiary amine conversion ratio 80.5%.Reaction finishes and tells water, and the upper strata is a product, contains a small amount of unreacted tertiary amine.
The preparation of two dodecyl methyl amine oxides: react in the presence of the catalyst sodium ethylene diamine tetracetate with hydrogen peroxide with two dodecyl methyl tertiary amines (chemical industry Co., Ltd product circles in the air), reaction medium is a water, reaction temperature is 95 ℃, hydrogen peroxide: the tertiary amine mol ratio is (1.2): 1, catalyst amount is 1.2% (with respect to tertiary amine), 7 hours reaction time, tertiary amine conversion ratio 82%.Reaction finishes and tells water, and the upper strata is a product, contains a small amount of unreacted tertiary amine.
Product carries out mass spectral analysis after initial gross separation is purified, the result as shown in Figure 1.Owing to adopt the positive charge pattern, lotus/matter is than being the molecular weight of target product+1, so lotus/matter is more in full accord with target product than 384.6.
Product is done infrared spectrum analysis after further purifying, the result as shown in Figure 2.Compare with corresponding raw material tertiary amine, in the infared spectrum of product at 960cm
-1The N-O absworption peak has appearred in the place.
The surface-active of product: the product behind the purifying is dissolved in ultra-pure water, measures surface tension and critical micelle concentration under 25 ℃, the result as shown in Figure 3.Fig. 3 shows that two dodecyl methyl amine oxide critical micelle concentrations (cmc) are about 8 * 10
-6Mol/L, γ
Cmc＜30mN/m, promptly product has very high surface-active.
Can prepare corresponding two 12/myristyl methyl oxidation amine with two 12/myristyl methyl tertiary amines (mixing tertiary amine) similarly.
Embodiment 2
Two ten alkyl methyl amine oxides and sulfonate type anion surfactant with preparation are composite, and the molar fraction of two ten alkyl methyl amine oxides is 0.5.Mixed surfactant is dissolved in the grand celebration formation water that contains the 1000ppm polyacrylamide, and total surfactant concentration (mass fraction) is respectively 0.1% and 0.3%, measures the interfacial tension with Daqing crude oil under 45 ℃.At alkali-free, do not add under the electrolytical condition, equilibrium interfacial tension can drop to 10
-3The mN/m order of magnitude, as shown in Figure 4.
Embodiment 3
Two dodecyl methyl amine oxides and sulfonate type anion surfactant with preparation are composite, and the molar fraction of two dodecyl methyl amine oxides is 0.2.Mixed surfactant is dissolved in the grand celebration formation water that contains the 1000ppm polyacrylamide, and the total surfactant mass fraction is 0.3%, measures the interfacial tension with Daqing crude oil under 45 ℃.At alkali-free, do not add under the electrolytical condition, equilibrium interfacial tension can drop to 10
-3The mN/m order of magnitude, as shown in Figure 5.
Embodiment 4
Two ten alkyl methyl amine oxides and alkylolamides class non-ionic surface active agent with preparation are composite, and the molar fraction of two ten alkyl methyl amine oxides is 0.1.Mixed surfactant is dissolved in the grand celebration formation water that contains the 1000ppm polyacrylamide, and total surfactant mass fraction 0.3% is measured the interfacial tension with Daqing crude oil under 45 ℃.At alkali-free, do not add under the electrolytical condition, equilibrium interfacial tension can drop to 10
-3The mN/m order of magnitude, as shown in Figure 6.
Claims (1)
1. the application of a surface active agent of double long-chain alkyl amine oxide, it is characterized in that by itself and other surfactant compound is used, as non-base oil-displacing agent, wherein the molar fraction of surface active agent of double long-chain alkyl amine oxide is 0.10～0.60, in total surfactant mass concentration 0.05%～0.3%, add polyacrylamide 1000mg/L, do not add under alkali, the 45 ℃ of conditions, can make Daqing crude oil/formation water interfacial tension reduce to 10
-3The mN/m order of magnitude;
Above-mentioned double long-chain alkyl amine oxide has following array structure:
n＝6，8，10，12，14，16；
Described other surfactant is sulfonate type anion surfactant or alkylolamides class non-ionic surface active agent.
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| CN103215018B (en) * | 2012-12-17 | 2016-08-03 | 江南大学 | The preparation of the double long-chain non-ionic type alkali-free surfactant oil displacement of one class and application |
| CN103113869A (en) * | 2013-02-25 | 2013-05-22 | 中国石油天然气股份有限公司 | Double-long-chain alkyl hydroxy sulfobetaine surfactant and oil-displacing agent |
| CN107001923B (en) * | 2014-04-23 | 2019-08-20 | 索尔维（张家港）精细化工有限公司 | Compound, its composition and the method for being used for hydrocarbon extraction using it |
| CN105567205B (en) * | 2014-10-11 | 2019-03-15 | 中国石油天然气股份有限公司 | A kind of synthetic method of oil displacement agent and mustard base oxidation amine surfactants |
| CN106634925A (en) * | 2015-10-29 | 2017-05-10 | 中国石油天然气股份有限公司 | Amine oxide surfactant, preparation method and applications thereof |
| CN106832335B (en) * | 2017-03-03 | 2019-01-18 | 祺农化工科技(上海)有限公司 | A kind of application of the Y type hydrophilic group amphiphile, amphiphilic molecule compound of low molecular weight in terms of improving asphalt emulsion viscosity and stability |
| CN106832336B (en) * | 2017-03-03 | 2019-01-18 | 祺农化工科技(上海)有限公司 | A kind of application of the Y type hydrophilic group amphiphile, amphiphilic molecule compound of low molecular weight in terms of improving asphalt emulsion viscosity and stability |
| CN107338037A (en) * | 2017-07-20 | 2017-11-10 | 陕西森瑞石油技术开发有限公司 | A kind of low permeability oil field oil displacement agent and preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5866718A (en) * | 1997-03-20 | 1999-02-02 | General Electric Company | Synthesis of tertiary amine oxides |
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| US5866718A (en) * | 1997-03-20 | 1999-02-02 | General Electric Company | Synthesis of tertiary amine oxides |
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