CN1730149A - Surface active agent synthesized from alkyl benzene, its formula system and its application in tertiary oil extraction - Google Patents
Surface active agent synthesized from alkyl benzene, its formula system and its application in tertiary oil extraction Download PDFInfo
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- CN1730149A CN1730149A CN200410070469.9A CN200410070469A CN1730149A CN 1730149 A CN1730149 A CN 1730149A CN 200410070469 A CN200410070469 A CN 200410070469A CN 1730149 A CN1730149 A CN 1730149A
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Abstract
The invention relates to a surface active agent synthesized from alkyl benzene as the raw material, and the use of the formulation system of the surface active agent. The formulation system can also comprise right content of auxiliary agent, salt, polymeric compounds and water through mixing homogeneously. The surface active agent oil-dispelling system or surface active agent formulated from the surface active agent formulation system, i.e. polymer dual compound oil-dispelling system and the underground crude oil can produce an ultralow interfacial tension up to 0.003-0.00001mN/m, thus can effectively dispel the residual oil in the oil reservoir, and the crude oil recovery factor can be increased by over 25%.
Description
Technical field
The present invention relates to a kind of is the synthetic novel surfactant of raw material with the alkylbenzene, contains this kind surfactant formula system and the application in tertiary oil recovery thereof.
Background technology
The application surface activating agent recovers the oil to study and originates in earlier 1930s in oil exploitation technology, and the history in more than 70 year is arranged so far.Seven during the last ten years, all obtained very big development in the theory and practice, at present, formed following several injection systems basically.(1) active water drive, (2) micellar solution flooding, the displacement of reservoir oil of (3) low interfacial tension system, (4) ternary composite driving.Wherein ternary composite driving (alkali-polymer-surfactant) is a kind of new method that improves oil recovery factor that just grows up the 1980s, because this method still can obtain higher oil displacement efficiency under the situation of low surfactant consumption, therefore, it has become the new technology at economic and technical all very successful raising oil recovery factor.
After the oil field enters high water-cut stage, remaining oil with discontinuous oil film by trap in the hole of reservoir rocks, two main power that act on the oil droplet are viscaps.If use suitable surfactant system, reduce the interfacial tension between profit, just reduced the resistance that the oil droplet distortion was brought when residual oil was moved, thus oil recovery factor improved.
Yet, in the existing ternary composite oil-displacing system, the alkali that contains high concentration, as NaOH, sodium carbonate etc., in use, huge injury has been brought on stratum and oil well etc., so press for a kind of novel oil displacement system now, under the situation of alkali-free, still can form 10 with underground crude oil
-3～10
-4The ultralow interfacial tension of mN/m improves more than the oil recovery factor 20% (OOIP).The application in tertiary oil recovery of the novel surfactant of this just alkali-free ultralow interfacial tension of the present invention and formula system thereof.
Summary of the invention
The object of the present invention is to provide a kind of is the synthetic surfactant of raw material with the alkylbenzene, under the condition of alkali-free, still forms 10 with crude oil
-3～10
-5The ultralow interfacial tension of mN/m.
Another object of the present invention provides the application of above-mentioned surfactant formula system in tertiary oil recovery.
Through a large amount of experiment, we obtain of the present invention a kind of be the synthetic surfactant of raw material with the alkylbenzene, the molecular formula of this surfactant is:
Wherein: m is any one integer in 1～18;
Z is any one integer in 1～6;
P is any one integer in 0～10;
J is any one integer in 0～12;
I is any one integer in 0～1;
R ' is
-CH
2NHCH
2CH
2COOM、
-COOM ,-SO
3Among the M any one;
M is any one in alkali metal, monoethanolamine, diethanol amine, the triethanolamine.
In the surfactant molecule formula, be preferably m and be any one integer in 9～16; Z is any one integer in 1～3; P is any one integer in 0～4; J is any one integer in 0～3; I is any one integer in 0～1;
R ' is
-CH
2NHCH
2CH
2COOM ,-among the COOM any one; M is any one in sodium, potassium, lithium, monoethanolamine, diethanol amine, the triethanolamine.
In the surfactant molecule formula, further preferred m is any one integer in appointing in 9～12; Z is any one integer in 1～3; P is any one integer in 0～4; J is 0; I is 0; R ' is
-CH
2NHCH
2CH
2Among the COOM any one; M is any one in sodium, the potassium.
Most preferably be m and be 12, z is 3, p is 0, j is 0, i is 0, R ' is-CH
2NHCH
2CH
2COOM, M are potassium.
Above-mentioned surfactant can be mixed with surfactant formula system, application that can be in tertiary oil recovery, and this formula system comprises following several composition:
(1) surfactant is 0.02%～0.8% (weight);
(2) polymer is 0～0.3% (weight);
(3) salt is 0～2.0% (weight);
(4) surplus is that clear water or sewage are injected in the oil field;
Displacing surfactant system that above-mentioned surfactant formula system is mixed with or surfactant---polymer binary combination flooding oil body system can reach 10 with underground crude oil
-3～10
-5The ultralow interfacial tension of mN/m, the remaining oil in the displacement oil reservoir improves more than the oil recovery factor 25% (OOIP) effectively.
The application of formula system of the present invention in tertiary oil recovery in formula system, can add polymer, and polymer is a water-soluble polyacrylamide, molecular weight 300～30,000,000.It has the effect of control viscosity.A kind of used for tertiary oil recovery surfactant formula system that is used for of the present invention when the oil field is homogeneous formation or low permeability oil field, does not just need to add polymer in practical application, can use surfactant separately, can also be with salt; For the saturating oil field of middle and high infiltration, can use surfactant separately, can also be with salt, further the addition polymerization compound can both reach best oil displacement efficiency.
The application of formula system of the present invention in tertiary oil recovery can add salt in formula system, salt is sodium chloride, potassium chloride, urea.
The application of formula system of the present invention in tertiary oil recovery, it is characterized in that, in surfactant formula system, can also add auxiliary agent, be used for improving the flowability and the solubility of surfactant formula system, described auxiliary agent is any one or the multiple auxiliary agent that mixes in alcohols, ethers, the bases.Here that usefulness is C
1～C
12Monohydric alcohol, ethylene glycol, glycerine, glycol ether, propylene glycol, sodium carbonate, sodium acid carbonate, sodium metasilicate in any one or the multiple auxiliary agent that mixes.
Surfactant can be a kind of in the surfactant formula system of the present invention, also can be several surfactants, can also further add other anion surfactants/new formula system and underground crude oil of non-ionic surface active agent composition and can reach 10
-3～10
-5The ultralow interfacial tension of mN/m improves oil recovery factor.What emphasize here is that when using in tertiary oil recovery, the binary combination flooding oil body of every displacing surfactant system or surfactant---polymer contains carboxylate surface active agent of the present invention in being, also is part of the present invention.
In sum, in actual applications, because the difference of oil field block, reservoir condition is inconsistent, the composition difference of crude oil, underground water, clay mineral, therefore at different reservoir conditions, just can select various combination, different proportion to make displacing surfactant system or surfactant---polymer binary combination flooding oil body system, to reach best oil displacement efficiency.
The present invention has the following advantages:
(1) surfactant formula system still can form 10 with underground crude oil among alkali-free the present invention under the alkali-free condition
-3～10
-5The ultralow interfacial tension of mN/m has not only overcome when using at the scene high concentration alkali to the huge injury of stratum and oil well, and compliance with environmental protection requirements, and equipment is not had injury, can reach best oil displacement efficiency;
(2) have good acid and alkali resistance and electrolyte performance and be easy to biodegradable characteristic;
(3) can improve more than the oil recovery factor 25% (OOIP), and cost is very low, can brings huge economic benefit for the oil field.
The present invention is elaborated with the following examples, and these embodiment only are used for description effect, rather than limit the scope of the invention.
If no special instructions, reagent that uses among the embodiment and tester are as follows:
One, uses reagent
Detergent alkylate butyl tertiary amine carboxybetaine Daqing High-tech Park Sinno Fine Chemical Co., Ltd produces
Water-soluble polyacrylamide Daqing oil field auxiliary reagent factory produces (salt-resistant polymer)
Experiment water Daqing oil field recover the oil four factory's clear water, four factory's sewage
Crude oil Daqing oil field dewatered oil
Two, tester
The production of interfacial tensimeter Texas ,Usa university is dripped in the rotation of 500 types
45 ℃ of experimental temperatures
Embodiment
The preparation of a pair of detergent alkylate butyl of embodiment tertiary amine carboxybetaine
2460g detergent alkylate and aluminum trichloride (anhydrous) 160g are joined in the there-necked flask, be warming up to 80 ℃, begin to drip 4-chlorobutyronitrile 103.5g then, dripped 30 minutes, reacted 3 hours, extremely neutral with the frozen water washing that has watery hydrochloric acid, drying, rectification under vacuum must be to detergent alkylate butyronitrile 286g.
Get detergent alkylate butyronitrile 260g is joined in the 2000ml autoclave, add 25% NaOH ethanolic solution 350g simultaneously, thunder niobium Raney nickel 52g, with air in the nitrogen replacement still, to 3MPa, be warming up to 120 ℃ with pressurized with hydrogen, reacted 2 hours, remaining hydrogen is discharged in cooling then.The elimination Raney nickel, decompression distillation gets 243g.
With 200g to detergent alkylate fourth primary amine, 117.4g industrial alcohol and 41.6g formaldehyde (37%) join in the 2000ml there-necked flask, are warming up to 60 ℃, slowly drip 130.6g formic acid, continue after dripping to react a few minutes, be warming up to 80 ℃ then and continue reaction 2 hours.Static layering is removed water layer, and rectification under vacuum gets N, and the N-dimethyl is to detergent alkylate fourth tertiary amine 187g.
N with 200g, the N-dimethyl joins in the 1000ml there-necked flask that has condenser and agitator sodium chloroacetate, 200ml water and the 300ml isopropyl alcohol of detergent alkylate fourth tertiary amine, 81g, be warmed up to 70 ℃ of reactions 10 hours after fully mixing, thereby obtain detergent alkylate fourth tertiary amine carboxybetaine 186g.
Synthesizing of 21 kinds of surfactant formula systems of embodiment
Get detergent alkylate butyl tertiary amine carboxybetaine 0.3g, sodium chloride 0.8g, water 98.65g stirred 30 minutes, obtained a kind of surfactant formula system.
Embodiment three
The displacing surfactant system that detergent alkylate butyl tertiary amine carboxybetaine is mixed with when being 0.05～0.3% (weight) and the interfacial tension of underground crude oil are 10
-3～10
-5The ultralow interfacial tension of mN/m can add salt, and the displacing surfactant system that salt is mixed with when being sodium chloride 0.1～0.8% (weight) and the interfacial tension of underground crude oil are 10
-3～10
-5The ultralow interfacial tension of mN/m, experiment water is the Daqing oil field four factory's sewage that recover the oil, crude oil is the Daqing oil field dewatered oil.What emphasize here is that when oil property changed, interfacial tension can change.
Embodiment four
The displacing surfactant system that is mixed with when detergent alkylate butyl primary amine alanine potassium surfactant is 0.05～0.3% (weight) and the interfacial tension of underground crude oil are 10
-4～10
-5The ultralow interfacial tension of mN/m can add salt, and the displacing surfactant system that salt is mixed with when being sodium chloride 0.1～0.8% (weight) and the interfacial tension of underground crude oil are 10
-4～10
-5The ultralow interfacial tension of mN/m, experiment water is the Daqing oil field four factory's sewage that recover the oil, crude oil is the Daqing oil field dewatered oil.What emphasize here is that when oil property changed, interfacial tension can change.
Embodiment five
The displacing surfactant system that is mixed with when the detergent alkylate potassium butyrate is 0.05～0.3% (weight) and the interfacial tension of underground crude oil are 10
-3～10
-4The ultralow interfacial tension of mN/m can add salt, and the displacing surfactant system that salt is mixed with when being sodium chloride 0.1～0.8% (weight) and the interfacial tension of underground crude oil are 10
-3～10
-4The ultralow interfacial tension of mN/m, experiment water is the Daqing oil field four factory's sewage that recover the oil, crude oil is the Daqing oil field dewatered oil.What emphasize here is that when oil property changed, interfacial tension can change.
Embodiment six
In perm-plug method is 1000md, inject the binary slug in the core earlier, its consist of that above-mentioned surfactant (to dodecyl phenoxy group butyl primary amine alanine potassium surfactant) is mixed with surfactant---polymer binary combination flooding oil body is 0.38PV (pore volume), follow-up slug 0.1PV (pore volume) polymer that reinjects can improve more than the recovery ratio 25% (OOIP) of crude oil.
Embodiment seven
In perm-plug method is 1000md, inject the binary slug in the core earlier, its consist of that above-mentioned surfactant formula system (to detergent alkylate butyl tertiary amine carboxybetaine) is mixed with surfactant---polymer binary combination flooding oil body is 0.38PV (pore volume), follow-up slug 0.1PV (pore volume) polymer that reinjects can improve more than the recovery ratio 25% (OOIP) of crude oil.
Claims (10)
1, a kind of is the synthetic surfactant of raw material with the alkylbenzene, and the molecular formula of this surfactant is:
Wherein: m is any one integer in 1～18;
Z is any one integer in 1～6;
P is any one integer in 0～10;
J is any one integer in 0～12;
I is any one integer in 0～1;
R ' is
-CH
2NHCH
2COOM、
-CH
2NHCH
2CH
2COOM、
-COOM ,-SO
3Among the M any one; M is any one in alkali metal, monoethanolamine, diethanol amine, the triethanolamine.
2, surfactant according to claim 1, in the surfactant molecule formula, m is any one integer in 9～16; Z is any one integer in 1～3; P is any one integer in 0～4; J is any one integer in 0～3; I is any one integer in 0～1;
R ' is
-CH
2NHCH
2CH
2COOM ,-among the COOM any one; M is any one in sodium, potassium, lithium, monoethanolamine, diethanol amine, the triethanolamine.
3, surfactant according to claim 1 and 2, m is any one integer in 9～12 in the surfactant molecule formula; Z is any one integer in 1～3; P is any one integer in 0～4; J is 0; I is 0; R ' is
-CH
2NHCH
2CH
2Among the COOM any one; M is any one in sodium, the potassium.
4, according to the described surfactant of one of claim 1～3, in the surfactant molecule formula, m is 12, z is 3, p is 0, j is 0; I is 0; R ' is-CH
2NHCH
2CH
2COOM, M are potassium.
5, the surfactant formula system that is mixed with of the described surfactant of one of claim 1～4, this formula system comprises following several composition:
(1) surfactant is 0.02%～0.8% (weight);
(2) polymer is 0～0.3% (weight);
(3) salt is 0～2.0% (weight);
(4) surplus is that clear water or sewage are injected in the oil field.
6, surfactant formula system according to claim 5 is characterized in that, can add polymer, and polymer is a water-soluble polyacrylamide, molecular weight 300～3,000 ten thousand.
7, according to claim 5 or 6 described surfactant formula systems, it is characterized in that salt is sodium chloride, potassium chloride, any one in the urea.
8, according to the described surfactant formula system of one of claim 5～7, it is characterized in that, can also add auxiliary agent in surfactant formula system, described auxiliary agent is any one or the multiple auxiliary agent that mixes in alcohols, ethers, the bases.
9, according to the application of the described surfactant formula system of one of claim 5～8 in tertiary oil recovery, it is characterized in that,, can use surfactant separately for low permeability oil field, can also be with salt; For the saturating oil field of middle and high infiltration, can use surfactant separately, can also be with salt, all right further addition polymerization compound.
10, the application of claim 9, surfactant can be a kind of in the surfactant formula system, also can be several surfactants, can also further add other anion surfactants/new formula system and underground crude oil of non-ionic surface active agent composition and can reach 10
-3～10
-5The ultralow interfacial tension of mN/m improves oil recovery factor.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410070469.9A CN1730149A (en) | 2004-08-04 | 2004-08-04 | Surface active agent synthesized from alkyl benzene, its formula system and its application in tertiary oil extraction |
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|---|---|---|---|
| CN200410070469.9A CN1730149A (en) | 2004-08-04 | 2004-08-04 | Surface active agent synthesized from alkyl benzene, its formula system and its application in tertiary oil extraction |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618244A (en) * | 2011-03-11 | 2012-08-01 | 中国石油天然气股份有限公司 | Betaine surfactant and preparation method and application thereof |
| WO2012122667A1 (en) * | 2011-03-11 | 2012-09-20 | 中国石油天然气股份有限公司 | Betaine surfactants and preparation methods and uses thereof |
-
2004
- 2004-08-04 CN CN200410070469.9A patent/CN1730149A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102618244A (en) * | 2011-03-11 | 2012-08-01 | 中国石油天然气股份有限公司 | Betaine surfactant and preparation method and application thereof |
| WO2012122667A1 (en) * | 2011-03-11 | 2012-09-20 | 中国石油天然气股份有限公司 | Betaine surfactants and preparation methods and uses thereof |
| US9540559B2 (en) | 2011-03-11 | 2017-01-10 | Petrochina Company Limited | Betaine surfactants and preparation methods and uses thereof |
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