CN1778460A - Surface activator containing bisphenol, its formula system and use for triple oil extraction - Google Patents
Surface activator containing bisphenol, its formula system and use for triple oil extraction Download PDFInfo
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- CN1778460A CN1778460A CN200410091500.7A CN200410091500A CN1778460A CN 1778460 A CN1778460 A CN 1778460A CN 200410091500 A CN200410091500 A CN 200410091500A CN 1778460 A CN1778460 A CN 1778460A
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Abstract
A surfactant containing biphenol for tertiary recovery of pertroleum with high recovery rate increased by more than 25% is disclosed. Its oil displacing system is prepared from said surfactant, assistant, salt, polymer and water through regulating pH value and mixing.
Description
Technical field
The present invention relates to a kind of surface activator containing bisphenol, contain 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 droplet 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.
The research contents of relevant ternary composite oil-displacing system aspect, existing both at home and abroad a large amount of bibliographical information has all been done detailed introduction as kinds of surfactants, component, concentration and proportioning that CN1272393, CN1277239, GB2232428 etc. use in the oil displacement agent prescription to The field.CN1272393, CN1277239 wherein surfactant mainly with synthetic detergent byproduct---heavy alkyl benzene is a raw material, the heavy alkylbenzene sulfonate that makes through sulfonating reaction and neutralization reaction is with cosurfactant; GB2232428 wherein surfactant mainly carries out composite with dialkyl benzene sulfonate and the poly-alkoxyl ether sulfonate of alkyl phenol, because though the kinds of surfactants of used for tertiary oil recovery is a lot, but price is all higher relatively, and on-the-spot large usage quantity, the alkali concn of Shi Yonging is higher as NaOH, sodium carbonate etc. in addition, not only oil reservoir is produced injury, also increase the consumption of alkali simultaneously, certainly will increase the cost of investment and the producing cost of the chemical agent in the ternary composite driving like this.Therefore, on economy, must solve the cost of reduction surfactant and the consumption of alkaline agent.So press for a kind of novel oil displacement system now, at alkali-free or contain under the situation of ultralow alkali, 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).This just alkali-free of the present invention or contain the novel surfactant and the application of formula system in tertiary oil recovery thereof of ultralow alkali ultralow interfacial tension.
Summary of the invention
The object of the present invention is to provide a kind of surfactant, at alkali-free or contain under the condition of ultralow alkali, still form 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 experiments, we obtain a kind of surface activator containing bisphenol of the present invention, and the molecular formula of this surfactant is:
Wherein: m is any one integer in 1~10;
N is any one integer in 0~10;
R is any one in alkyl, alkylaryl, the alkylaryl alkyl;
R ' is
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, n in 1~6 and be any one integer in 0~4; R is any one in alkyl, alkyl phenyl, dialkyl phenyl organic, naphthyl, alkyl naphthyl, dialkyl group naphthyl, Fluhyzon methylene, the alkylbenzene methylene; Wherein, the alkyl in the alkyl is C
1~C
20In any one, the alkyl in the dialkyl phenyl organic is C
2~C
24In any one, the alkyl in the alkyl phenyl is C
1~C
20In any one, alkyl is C in the dialkyl group naphthyl
2~C
24In any one, the alkyl in the Fluhyzon methylene is C
1~C
20In any one, the alkyl in the alkylbenzene methylene is C
1~C
20In any one; R ' is
-NHCH
2CH
2COOM ,-COOM ,-SO
3Among the M any one; M is any one in sodium, potassium, lithium, monoethanolamine, diethanol amine, the triethanolamine.
In the surfactant molecule formula, more preferably m is that any one integer, n in 4~6 are that any one integer, R in 0~4 is C
9~C
14Alkyl in any one; R ' is
-NHCH
2CH
2COOM ,-among the COOM any one; M is any one in sodium, potassium, lithium, monoethanolamine, diethanol amine, the triethanolamine.Comprising m be 4 and 6, n is that any one integer, R in 0,1,3 is C
9, C
12, C
14Alkyl in any one; R ' is
-NHCH
2CH
2COOM ,-among the COOM any one; M is any one in sodium, potassium, lithium, monoethanolamine, diethanol amine, the triethanolamine.Most preferably be m and be 4, n is 3, R is C
9Alkyl; R ' is
The surfactant formula system that above-mentioned surfactant can be mixed with, this formula system comprise following several composition:
(1) surfactant is 0.001%~0.8% (weight);
(2) polymer is 0~0.5% (weight);
(3) alkali 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 or surfactant and polymer-alkali ternary composite oil-displacing system and underground crude oil can reach 10
-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 can add polymer in formula system, polymer is a water-soluble polyacrylamide, molecular weight 300~50,000,000.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 or alkali; For the saturating oil field of middle and high infiltration, can use surfactant separately, can also be with salt or alkali, 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 alkali in formula system, alkali is any one in NaOH, potassium hydroxide, sodium acid carbonate, sodium carbonate, the sodium metasilicate.
The application of formula system of the present invention in tertiary oil recovery, 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 salt.Here that usefulness is C
1~C
12Monohydric alcohol, ethylene glycol, glycerine, glycol ether, propylene glycol, sodium chloride, any one in potassium chloride, the urea or the multiple auxiliary agent that mixes.
In the application of surfactant formula system of the present invention in tertiary oil recovery, surfactant can be a kind of, also can be several surfactants, can also further add other anion surfactant/non-ionic surface active agents/new formula system and underground crude oil of amphoteric surfactant composition and can reach 10
-3~10
-5The ultralow interfacial tension of mN/m improves oil recovery factor.What emphasize here is, when in tertiary oil recovery, using,---containing surfactant of the present invention in the binary combination flooding oil body system of polymer or surfactant---polymer---the alkali ternary composite oil-displacing system, also is part of the present invention for every displacing surfactant system or surfactant.
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---polymer binary combination flooding oil body system or surfactant---polymer---alkali ternary composite oil-displacing system are to reach best oil displacement efficiency at different reservoir conditions, just can to select various combination, different proportion to make displacing surfactant system or surfactant.
The present invention has the following advantages:
(1) alkali-free or contain among ultralow alkali the present invention surfactant formula system at alkali-free or contain under the ultralow alkali condition still can form 10 with underground crude oil
-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 acidproof, heatproof, alkaline-resisting 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
N, N-dimethyl-4
1-oxygen nonyl-4-oxygen butylamine base bisphenol-A carboxybetaine is newly synthetic
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
Embodiment one: N, N-dimethyl-4
1(m is 4 to-oxygen nonyl-4-oxygen butylamine base bisphenol-A carboxybetaine, n is 3, R is C
9Alkyl; R ' is
Synthetic
Condenser is being housed, add bisphenol-A 300g, solvent paraxylene 300ml, 50% potassium hydroxide aqueous solution 220g in the 1000ml there-necked flask of agitator, temperature rising reflux reaction 3 hours is warmed up to 110 ℃, dripping bromine continues reaction 6 hours for nonane 328g after dripping off.Static layering is removed water layer and inorganic salts, pickling, drying, and rectification under vacuum obtains oxygen bisphenol-A 424g in the ninth of the ten Heavenly Stems.
Condenser is being housed, add oxygen bisphenol-A 300g in the ninth of the ten Heavenly Stems, solvent paraxylene 250ml, the 50% potassium hydroxide aqueous solution 140g that makes above in the 1000ml there-necked flask of agitator, temperature rising reflux reaction 3 hours, be warmed up to 110 ℃ and drip 1,4-dichloroetane 129g continues reaction 6 hours after dripping off.Static layering is removed water layer and inorganic salts, pickling, drying, and rectification under vacuum obtains 4
1-oxygen nonyl-4-oxygen-butyl chlorine bisphenol-A 342g.
With make above 4
1-oxygen nonyl-4-oxygen-butyl chlorine bisphenol-A 342g, dimethylamine 207g and NaOH 37g join in the autoclave that has condensation and stirring, are warmed up to 135 ℃ of reactions 6 hours.Static layering is removed water layer and salt, washes 3~4 times, and drying, rectification under vacuum gets product 285g N, N-dimethyl-4
1-oxygen nonyl-4-oxygen-butyl tertiary amine bisphenol-A.
With the 285g N that makes above, N-dimethyl-4
1Sodium chloroacetate, 200ml water and the 300ml isopropyl alcohol of-oxygen nonyl-4-oxygen-butyl tertiary amine bisphenol-A, 89g join in the 1000ml there-necked flask that has condenser and agitator, be warmed up to 70 ℃ of reactions 10 hours after fully mixing, static heating removes and anhydrates and isopropyl alcohol, with normal propyl alcohol extraction product and unreacted raw material, remove normal propyl alcohol again and use the unreacted raw material of petroleum ether extraction, remove benzinum then and obtain pure product.
Synthesizing of 21 kinds of surfactant formula systems of embodiment
Get oxygen base benzene isopropyl phenoxy group butyl tertiary amine carboxybetaine 0.1g in the ninth of the ten Heavenly Stems, polyacrylamide 0.25g, water 99.65g stirred 30 minutes, adjusted the pH value and was 9~13 and obtain a kind of surfactant formula system.
Embodiment three
N, N-dimethyl-4
1(m is 4 to-oxygen dodecyl-4-oxygen butylamine base Bisphenol F carboxybetaine, n is 1, R is C
12Alkyl; R ' is
The displacing surfactant system that is mixed with when being 0.001~0.3% (weight) and the interfacial tension of underground crude oil are 10
-3~10
-5The ultralow interfacial tension of mN/m, can adjusting pH value, to make the displacing surfactant system that is mixed with and the interfacial tension of underground crude oil be 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
N, N-dimethyl-4
1(m is 4 to-oxygen myristyl-4-oxygen butylamine base Bisphenol F carboxybetaine, n is 1, R is C
14Alkyl; R ' is
The displacing surfactant system that is mixed with when being 0.001~0.3% (weight) and the interfacial tension of underground crude oil are 10
-3~10
-5The ultralow interfacial tension of mN/m, can adjusting pH value, to make the displacing surfactant system that is mixed with and the interfacial tension of underground crude oil be 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 five
N, N-dimethyl-4
1(m is 4 to-oxygen dodecyl-4-oxygen butylamine base xenol carboxybetaine, n is 0, R is C
12Alkyl; R ' is
The displacing surfactant system that is mixed with when being 0.001~0.3% (weight) and the interfacial tension of underground crude oil are 10
-3~10
-5The ultralow interfacial tension of mN/m, can adjusting pH value, to make the displacing surfactant system that is mixed with and the interfacial tension of underground crude oil be 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 six
N, N-dimethyl-4
1(m is 4 to-oxygen nonyl-4-oxygen butylamine base bisphenol-A carboxybetaine, n is 3, R is C
9Alkyl; R ' is
The displacing surfactant system that is mixed with when being 0.001~0.3% (weight) and the interfacial tension of underground crude oil are 10
-3~10
-5The ultralow interfacial tension of mN/m, can adjusting pH value, to make the displacing surfactant system that is mixed with and the interfacial tension of underground crude oil be 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 seven
In perm-plug method is 1000md, injects the binary slug in the core earlier, and it consists of above-mentioned surfactant formula system (N, N-dimethyl-4
1-oxygen nonyl-4-oxygen butylamine base bisphenol-A carboxybetaine) be 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 eight
In perm-plug method is 1000md, injects the binary slug in the core earlier, and it consists of above-mentioned surfactant formula system (N, N-dimethyl-4
1-oxygen dodecyl-4-oxygen butylamine base xenol carboxybetaine) be 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 nine
In perm-plug method is 1000md, injects the binary slug in the core earlier, and it consists of above-mentioned surfactant formula system (N, N-dimethyl-4
1-oxygen myristyl-4-oxygen butylamine base Bisphenol F carboxybetaine) be 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 ten
In perm-plug method is 1000md, injects the binary slug in the core earlier, and it consists of above-mentioned surfactant formula system (N, N-dimethyl-4
1-oxygen dodecyl-4-oxygen butylamine base Bisphenol F carboxybetaine) be 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 11
In perm-plug method is 200md, injects above-mentioned surfactant formula system (N, N-dimethyl-4 in the core earlier
1-oxygen dodecyl-4-oxygen butylamine base bisphenol-A carboxybetaine) the displacing surfactant system 0.38PV (pore volume) that is mixed with can improve more than the recovery ratio 15% (OOIP) of crude oil.
Claims (10)
1, a kind of bis-phenol surfactant that contains, the molecular formula of this surfactant is:
Wherein: m is any one integer in 1~10;
N is any one integer in 0~10;
R is any one in alkyl, alkylaryl, the alkylaryl alkyl;
R ' is
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 that any one integer, the n in 1~6 is any one integer in 0~4; R is any one in alkyl, alkyl phenyl, dialkyl phenyl organic, naphthyl, alkyl naphthyl, dialkyl group naphthyl, Fluhyzon methylene, the alkylbenzene methylene; Wherein, the alkyl in the alkyl is C
1~C
20In any one, the alkyl in the dialkyl phenyl organic is C
2~C
24In any one, the alkyl in the alkyl phenyl is C
1~C
20In any one, alkyl is C in the dialkyl group naphthyl
2~C
24In any one, the alkyl in the Fluhyzon methylene is C
1~C
20In any one, the alkyl in the alkylbenzene methylene is C
1~C
20In any one;
R ' is
-NHCH
2CH
2COOM ,-COOM ,-SO
3Among the M any one; M is any one in sodium, potassium, lithium, monoethanolamine, diethanol amine, the triethanolamine.
3, surfactant according to claim 1 and 2, in the surfactant molecule formula, m is that any one integer, the n in 4~6 is that any one integer, R in 0~4 is C
9~C
14Alkyl in any one;
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 0.001%~0.8% (weight);
(2) polymer is 0~0.5% (weight);
(3) alkali 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 300~5,000 ten thousand.
According to the described surfactant formula system of one of claim 5~6, it is characterized in that 7, alkali is any one in NaOH, potassium hydroxide, sodium acid carbonate, sodium carbonate, the sodium metasilicate.
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 salt.
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 or alkali; For the saturating oil field of middle and high infiltration, can use surfactant separately, can also be with salt or alkali, 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 surfactant/non-ionic surface active agents/new formula system and underground crude oil of amphoteric surfactant composition and can reach 10
-3~10
-5The ultralow interfacial tension of mN/m improves oil recovery factor.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108611189A (en) * | 2016-12-09 | 2018-10-02 | 丰益(上海)生物技术研发中心有限公司 | The refinery practice of bisphenol-A and alkyl phenol in a kind of control grease |
CN116181289A (en) * | 2023-01-30 | 2023-05-30 | 常州大学 | Determination method for foam viscosity reducer and nitrogen synergetic profile control technical parameters |
-
2004
- 2004-11-26 CN CN200410091500.7A patent/CN1778460A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108611189A (en) * | 2016-12-09 | 2018-10-02 | 丰益(上海)生物技术研发中心有限公司 | The refinery practice of bisphenol-A and alkyl phenol in a kind of control grease |
CN108611189B (en) * | 2016-12-09 | 2023-02-21 | 丰益(上海)生物技术研发中心有限公司 | Refining process for controlling bisphenol A and alkylphenol in grease |
CN116181289A (en) * | 2023-01-30 | 2023-05-30 | 常州大学 | Determination method for foam viscosity reducer and nitrogen synergetic profile control technical parameters |
CN116181289B (en) * | 2023-01-30 | 2023-11-24 | 常州大学 | Determination method for foam viscosity reducer and nitrogen synergetic profile control technical parameters |
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