CN1400276A - Surfactant for tertiary oil recovery and its application - Google Patents
Surfactant for tertiary oil recovery and its application Download PDFInfo
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- CN1400276A CN1400276A CN 01123547 CN01123547A CN1400276A CN 1400276 A CN1400276 A CN 1400276A CN 01123547 CN01123547 CN 01123547 CN 01123547 A CN01123547 A CN 01123547A CN 1400276 A CN1400276 A CN 1400276A
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- Prior art keywords
- tensio
- active agent
- alkyl
- surfactant
- oil recovery
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Abstract
The present invention relates to a surfactant for tertiary oil recovery and its application. Said surfactant is dialkyl benzene sulfonate. Said invention relates to a surfactant oil displacement system prepared by using said surfactant, and said system is an alkaline aqueous solution of surfactant for tertiary oil recovery, its use alkali is NaOH or Na2CO3 or NaHCO3, and the use range of said alkali is 0.1%-0.6% (weight), and between said surfactant oil displacement system and crude an ultra-low interfacial tension of 10 to the minus third mN/m can be formed.
Description
Technical field
The present invention relates to a kind of used for tertiary oil recovery tensio-active agent and application thereof.This tensio-active agent is a dialkyl benzene sulfonate.The present invention relates to displacing surfactant system with this tensio-active agent preparation.This displacing surfactant system is the alkaline aqueous solution of described used for tertiary oil recovery tensio-active agent, and the alkali of use is NaOH or Na
2CO
3Or NaHCO
3, the use range of alkali is 0.1%～0.6% (weight).Can form 10 between this displacing surfactant system and the crude oil
-3The ultra low interfacial tension of mN/m.
Background technology
Through the oil production in more than 100 years, most of in the world at present oil fields all entered the exploitation middle and later periods, after oil reservoir has experienced primary oil recovery and secondary oil recovery, still had the petroleum-in-place above 60% to remain in the blowhole of oil reservoir.Because oil belongs to Nonrenewable resources, so how to satisfy under the prerequisite of economic benefit, fully the recover petroleum resource becomes problem eternal in the oilfield development process.At present, the tertiary oil recovery method is a lot, as heat extraction by steam injection, fireflood, notes CO
2With chemical injection such as water-soluble polymers etc.Another kind of tertiary oil recovery method is to use tensio-active agent, because the use tensio-active agent can reduce the interfacial tension between profit, reduce the retention force of irreducible oil in the kapillary, thereby oil displacement efficiency being higher, also is a kind of comparatively widely novel oil production method of using in the present tertiary oil recovery.
Though the kind of tensio-active agent is very many, because crude oil composition complexity is considered the stratum adsorption losses, again so really the tensio-active agent that can be applied in the tertiary oil recovery is few.At present, though sulfonated petro-leum is widely used, because the ratio of its effective ingredient aromatics is very little, so working concentration is higher, chromatographic separation is serious.Other used for tertiary oil recovery tensio-active agents also more adopts compound systems, because the stratum is to the absorption difference of its each component, thereby is easy to destroy the best proportioning of its surfactant blend, is difficult to reach effective oil displacement efficiency.
Summary of the invention
The present invention relates to a kind of used for tertiary oil recovery tensio-active agent, this tensio-active agent is a dialkyl benzene sulfonate, and its molecular formula is as follows:
And/or
And/or
And/or
In the formula, R
1, R
2Be identical or different C
1～C
24Alkyl
M is a basic metal, ammonium or amine
Preferred R
1Be C
9～C
24Alkyl, R
2Be C
1～C
12Alkyl, further preferred R
1Be C
9～C
24Alkyl, R
2Be C
9～C
12Alkyl, further preferred again R
1Be C
9～C
12Alkyl, R
2Be C
9～C
12Alkyl, R most preferably
1Be C
12Alkyl, R
2Be C
9Alkyl.M is alkali metallic sodium or potassium or lithium, can also be ammonium or amine.
The production technique of dialkyl benzene sulfonate mainly contains two kinds: first kind is a step alkylation process, promptly under catalyst action, alkylation directly takes place and generates dialkyl benzene in the alkene of technical grade or haloalkane and toluene, ethylbenzene, propyl benzene etc., and sulfonation, neutralization obtain dialkyl benzene sulfonate.Second kind is two step alkylation process, promptly under catalyst action, the alkene of technical grade or haloalkane generate monoalkylated benzenes with benzene generation alkylation earlier, the monoalkylated benzenes that generates is under catalyst action, generate dialkyl benzene with technical grade alkene or haloalkane generation alkylation again, sulfonation, neutralization obtain dialkyl benzene sulfonate.Obtain and technical grade alkene here or haloalkane are the following technology that by present mature production technology, realizes suitability for industrialized production: normal paraffin dehydrogenation, wax cracking, propylene are superimposed, normal paraffin chlorination-dehydrochlorination etc.
The molecular weight of the dialkyl benzene sulfonic acids that the present invention relates to preferably between 400～510, is preferably between 440～470 between 390～520.The dialkyl benzene sulfonate that the present invention relates to has dialkyl benzene sulfonic acids sodium, dialkyl benzene sulfonic acids potassium, dialkyl benzene sulfonic acids lithium, dialkyl benzene sulfonic acids ammonium, dialkyl benzene sulfonic acids amine, preferably dialkyl benzene sulfonic acids sodium.The dialkyl benzene sulfonate that the present invention relates to mainly contains two nonylbenzene sulfonates, dodecyl nonylbenzene sulfonates, two dodecylbenzene sulfonate, octadecyl tosylate, octadecyl ethyl benzene sulfonate, octadecyl propyl benzene sulfonate, eicosyl tosylate etc.Preferably octadecyl tosylate and dodecyl nonylbenzene sulfonates.
The present invention relates to displacing surfactant system with this tensio-active agent preparation.This displacing surfactant system is the alkaline aqueous solution of described used for tertiary oil recovery tensio-active agent, and the alkali of use is NaOH or Na
2CO
3Or NaHCO
3, the use range of alkali is 0.1%～0.6% (weight).Can form 10 between this displacing surfactant system and the crude oil
-3The ultra low interfacial tension of mN/m.Why can and crude oil between form 10
-3The mN low interfacial tension is because the alkyl process on the phenyl ring is preferred, its synthetic tensio-active agent oil recovery base can closely be attracted each other with former oil molecule better, in addition, the hydrophile-lyophile balance HLB value of this tensio-active agent forms 10 greater than more than 13 thereby make between profit
-3The ultra low interfacial tension of mN/m.Tensio-active agent of the present invention is an one-component, thereby stratum absorption can not influence its oil displacement efficiency, does not have the chromatographic separation phenomenon.
This flooding system can also add partially hydrolyzed polyacrylamide, can also further add NaCL, can also further add cosurfactant C again
1～C
8Alcohol.Cosurfactant can improve the solubleness of tensio-active agent, improves the flowability of solution.Therefore, the suitable cosurfactant of adding helps to improve the action effect of tensio-active agent.The cosurfactant that the present invention uses is one or more C
1～C
8Alcohol, generally be methyl alcohol, ethanol, Virahol, isopropylcarbinol, propyl carbinol, primary isoamyl alcohol, amylalcohol, hexanol, octanol and composition thereof, preferably Virahol, isopropylcarbinol, primary isoamyl alcohol and composition thereof.
Further describe the present invention with the embodiment that has illustrative and can not limit protection domain of the present invention below.
The preparation of embodiment embodiment 1 dialkyl benzene sulfonate
This example has been described a kind of dialkyl benzene sulfonate---the preparation process of sodium p-octadecyl toluene sulfonate.
(1) alkylated reaction
Add toluene 300g, catalyzer aluminum chloride 3.47g in reactor, the 82.2g octadecylene is added drop-wise in the reactor slowly, 50 ± 5 ℃ of temperature controls are stirred, and drip half an hour, restir 1 hour.
(2) alkylation liquid sedimentation, liquefied ammonia neutralization, washing process.
The sedimentation of alkyl liquid with the liquefied ammonia neutralization, was got rid of waste residue after 12 hours, and washing is more than 3 times, and standing demix is discharged waste water.
(3) fractionation process
The alkylate fractionation of washing back, normal pressure piptonychia benzene, decompression obtains octadecyl toluene.
(4) dialkyl benzene sulfonation reaction
Octadecyl toluene is at SO
3Sulfonation in the film reactor, 40 ℃ of temperature of reaction.
(5) in the dialkyl benzene sulfonic acids and salify
The octadecyl toluenesulphonic acids is dripped in the aqueous sodium hydroxide solution slowly, generate sodium p-octadecyl toluene sulfonate.
Embodiment 2
This example has described that a kind of used for tertiary oil recovery tensio-active agent of the present invention---a kind of sodium p-octadecyl toluene sulfonate in the dialkyl benzene sulfonate is at Na
2CO
3Under the situation of 0.1%～0.6% (weight), and the interfacial tension between the crude oil sees Table 1.
Table 1
Annotate: remove sodium p-octadecyl toluene sulfonate, Na
2CO
3Outward, surplus is a water.
IFT (mN/m) is the interfacial tension value
In the table 1, laboratory apparatus is a U.S. Texas-500 type interfacial tensimeter, and oil is Daqing crude oil, and water is the grand celebration local water.As seen from Table 1, a kind of used for tertiary oil recovery tensio-active agent of the present invention---a kind of sodium p-octadecyl toluene sulfonate in the dialkyl benzene sulfonate is at Na
2CO
3Under the situation of 0.1%～0.6% (weight), and can form 10 between the crude oil
-3The ultra low interfacial tension of mN/m.
Embodiment 3
This example has been described a kind of used for tertiary oil recovery tensio-active agent of the present invention---and a kind of dodecyl nonyl benzene sodium sulfonate in the dialkyl benzene sulfonate is at Na
2CO
3Under the situation of 0.1%～0.6% (weight), and the interfacial tension between the crude oil sees Table 2.Table 2
Annotate: remove dodecyl nonyl benzene sodium sulfonate, Na
2CO
3Outward, surplus is a water.
In the table 2, laboratory apparatus is a U.S. Texas-500 type interfacial tensimeter, and oil is Daqing crude oil, and water is the grand celebration local water.As seen from Table 2, a kind of used for tertiary oil recovery tensio-active agent of the present invention---a kind of dodecyl nonyl benzene sodium sulfonate in the dialkyl benzene sulfonate is at Na
2CO
3Under the situation of 0.1%～0.6% (weight), and can form 10 between the crude oil
-3The ultra low interfacial tension of mN/m.Embodiment 4
This example has described that a kind of used for tertiary oil recovery tensio-active agent of the present invention---a kind of pair of Sodium dodecylbenzene sulfonate in the dialkyl benzene sulfonate is under the situation of NaOH 0.1%～0.6% (weight), and the interfacial tension between the crude oil sees Table 3.
Table 3
Annotate: remove two Sodium dodecylbenzene sulfonatees, outside the NaOH, surplus is a water.
In the table 3, laboratory apparatus is a U.S. Texas-500 type interfacial tensimeter, and oil is Daqing crude oil, and water is the grand celebration local water.As seen from Table 3, a kind of used for tertiary oil recovery tensio-active agent of the present invention---a kind of pair of Sodium dodecylbenzene sulfonate in the dialkyl benzene sulfonate and can form 10 between the crude oil under the situation of NaOH 0.1%～0.6% (weight)
-3The ultra low interfacial tension of mN/m.
Claims (10)
1, a kind of used for tertiary oil recovery tensio-active agent, this tensio-active agent is a dialkyl benzene sulfonate, its molecular formula is as follows:
And/or
And/or
And/or
In the formula, R
1, R
2Be identical or different C
1～C
24Alkyl
M is a basic metal, ammonium or amine
2, tensio-active agent according to claim 1 is characterized in that, R in the molecular formula
1Be C
9～C
24Alkyl, R
2Be C
1～C
12Alkyl.
3, tensio-active agent according to claim 1 is characterized in that, M is alkali metallic sodium or potassium or lithium in the molecular formula.
4, tensio-active agent according to claim 1 is characterized in that, M can also be ammonium or amine in the molecular formula.
5, tensio-active agent according to claim 2 is characterized in that, R in the molecular formula
1Be C
9～C
24Alkyl, R
2Be C
9～C
12Alkyl.
6, tensio-active agent according to claim 5 is characterized in that, R in the molecular formula
1Be C
9～C
12Alkyl, R
2Be C
9～C
12Alkyl.
7, tensio-active agent according to claim 6 is characterized in that, R in the molecular formula
1Be C
12Alkyl, R
2Be C
9Alkyl.
8, contain the flooding system of each the described tensio-active agent among the claim 1-7, it is characterized in that, this displacing surfactant system is the alkaline aqueous solution of described tensio-active agent.
9, displacing surfactant system according to claim 8 is characterized in that, the alkali that uses in this displacing surfactant system is NaOH or Na
2CO
3Or NaHCO
3, the concentration range of alkali is 0.1%～0.6% (weight).
10, according to Claim 8 or 9 described displacing surfactant systems, it is characterized in that the alkali that uses in this displacing surfactant system is Na
2CO
3, the concentration range of alkali is 0.1%～0.6% (weight).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01123547 CN1400276A (en) | 2001-08-01 | 2001-08-01 | Surfactant for tertiary oil recovery and its application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01123547 CN1400276A (en) | 2001-08-01 | 2001-08-01 | Surfactant for tertiary oil recovery and its application |
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| Publication Number | Publication Date |
|---|---|
| CN1400276A true CN1400276A (en) | 2003-03-05 |
Family
ID=4665143
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104232047A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Surface active agent composition for tertiary oil recovery and preparation method and application thereof |
-
2001
- 2001-08-01 CN CN 01123547 patent/CN1400276A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104232047A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Surface active agent composition for tertiary oil recovery and preparation method and application thereof |
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