CN1400275A - Composite for raising recovery efficiency of crude - Google Patents
Composite for raising recovery efficiency of crude Download PDFInfo
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- CN1400275A CN1400275A CN 01123546 CN01123546A CN1400275A CN 1400275 A CN1400275 A CN 1400275A CN 01123546 CN01123546 CN 01123546 CN 01123546 A CN01123546 A CN 01123546A CN 1400275 A CN1400275 A CN 1400275A
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- propylene
- alkyl
- tensio
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Abstract
The present invention relates to a surfactant-containing compound for raising producible oil index in tertiary oil recovery. Said surfactant is made of long-chain olefine obtained by propylene oligomerization and making it undergo the processes of alkylation, sulfonation and neutralization. Under the condition of low alkali it can form ultra-low interfacial tension of 10 to the minus third mN/m between oil and water, and possesses strong adaptability for various alkalies.
Description
Technical field
The present invention relates to a kind ofly in tertiary oil recovery, be used to improve the composition that contains tensio-active agent of oil recovery factor.This tensio-active agent can make to form 10 between profit under low alkali situation
-3The ultra low interfacial tension of mN/m, and have the adaptive faculty of extremely strong various alkali.
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 oil above 60% to remain in the stratum.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 to use a kind of comparatively widely new oil production method 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 utilizes catalyst action to obtain alkylbenzene sulfonate in certain long-chain olefin, can obtain to reduce the surfactant slug component of oil water interfacial tension.Because long-chain olefin can closely attract each other the oleophilic group of its synthetic tensio-active agent through preferred better with former oil molecule, 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.
At present the used alkylating agent of suitability for industrialized production alkylbenzene sulfonate is haloalkane, alkene, various alcohols etc., technologies such as the alkylbenzene main production has that normal paraffin dehydrogenation, chlorination, wax cracking, propylene are superimposed, normal paraffin chlorination, dehydrochlorination and ethylene oligomerization.
Tensio-active agent of the present invention, its molecular formula is
, in the formula, R is C
18～C
24Alkyl, M is basic metal, ammonium or amine.Alkylating agent adopts two kinds, a kind of octadecylene, two tetradecenes, two hendecenes that to be union alkene dimerization or laurylene dimerization or nonene be formed by stacking with laurylene, and wherein, nonene, laurylene are gathered by propylene trimerization, four and obtain.Another kind is six poly-, seven poly-or eight poly-product, i.e. octadecylene, two hendecenes, two tetradecenes that directly produced by propylene polymerization.
Tensio-active agent of the present invention, its major ingredient can be octadecyl benzene sulfonate, heneicosyl benzene sulfonate, tetracosyl benzene sulfonate.Alkylbenzene sulfonate can be sodium alkyl benzene sulfonate, alkyl benzene sulphonate (ABS) potassium, alkyl benzene sulphonate (ABS) lithium, alkyl benzene sulphonate (ABS) ammonium, benzene sulfonamide acid amide, better is heneicosyl benzene sulfonic acid sodium salt and heneicosyl Phenylsulfonic acid amine, preferably heneicosyl benzene sulfonic acid sodium salt.
Tensio-active agent of the present invention belongs to aniorfic surfactant, therefore mixes with small amount of alkali when concrete the application, can reach splendid oil displacement efficiency, and these alkali are: NaOH, Na
2CO
3, NaHCO
3, Na
2SiO
3, NH
4OH, wherein preferred Na
2CO
3, Na
2SiO
3Tensio-active agent of the present invention shows and Na simultaneously
2SiO
3Fabulous compatibleness, in this system, Na
2SiO
3Content is 0.1%～2.0% (weight).Tensio-active agent of the present invention all can make and form 10 between profit
-3The ultra low interfacial tension of mN/m, the mixture composition general range and the preferred range of aqueous components is as shown in table 1 among the present invention:
Table 1
| Composition | General range (weight) | Preferred range (weight) |
| Tensio-active agent | ????0.01％～1.0％ | ????0.05％～0.5％ |
| NaOH、Na 2CO 3、NaHCO 3、NH 4OH | ????0.05％～2.0％ | ????0.1％～0.6％ |
| ????Na 2SiO 3 | ????0.05％～2.0％ | ????0.1％～1.8％ |
| Water | Surplus | Surplus |
In the table 1, the aqueous composition of tensio-active agent of the present invention, its advantage not only shows as the ultra low interfacial tension value, and promptly 10
-3Below the mN/m, and it can just can make about 10 minutes and forms 10 between profit
-3The ultra low interfacial tension value that mN/m is following, such benefit is, when composition injects oil well, along with flowing of composition, just can be rapidly with attached to the emulsification of crude oil on the rock surface, thereby reach the purpose that improves oil recovery factor, also meet simultaneously now requirements such as low value, the speed of action of used for tertiary oil recovery tensio-active agent are fast.
Further describe the present invention with the embodiment that has illustrative and can not limit protection domain of the present invention below.
Embodiment
Embodiment 1
Present embodiment has specifically described the preparation method by nonene and the synthetic side chain heneicosyl benzene sulfonic acid sodium salt of laurylene.
(1) superimposed: add the 300g laurylene in reactor, be warming up to 60 ℃, the 20g vitriol oil and 225g nonene are mixed, slowly splash into reactor, controlled temperature is no more than 65 ℃, dropwises aging 1 hour.
(2) rectifying: 100 ℃～170 ℃ (5KPa) cuts of decompression are extracted in rectifying.
(3) alkylation: in reactor, add 300g benzene, 4.11g alchlor, under 50 ℃ of still temperature, splash into 113g side chain two hendecenes slowly, dropping half an hour, reacted again a hour.
(4) sedimentation, layering, neutralization: with alkylated reaction liquid sedimentation 12 hours, remove sub-cloud impurity, add the ammoniacal liquor neutralization in the reaction solution of upper strata, remove precipitation, washing is more than three times.
(5) normal pressure takes off benzene
(6) decompression deolefination, distill out side chain heneicosyl benzene
(7) sulfonation: by the benzoic acid ratio is that 1: 1.1 (weight ratio) splashes into 20% oleum slowly, and 30 ℃ of temperature drip half an hour, aging one hour again.
(8) in the side chain heneicosyl Phenylsulfonic acid and salify
Side chain heneicosyl Phenylsulfonic acid is dripped in 20% sodium hydroxide solution slowly, stir, controlled temperature is 60 ± 10 ℃, is 7 get final product generation side chain heneicosyl benzene sulfonic acid sodium salt to the mixture pH value.
Embodiment 2
Present embodiment has specifically described side chain heneicosyl benzene sulfonic acid sodium salt and Na
2CO
3Interfacial tension value when being made into different concns solution and between the crude oil.See table 2 for details:
Table 2
Annotate: remove side chain heneicosyl benzene sulfonic acid sodium salt, Na
2CO
3Outward, surplus is a water.IFT is the interfacial tension value.
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 tensio-active agent-side chain heneicosyl benzene sulfonic acid sodium salt of oil recovery factor that improves of the present invention 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
Present embodiment has specifically described side chain heneicosyl benzene sulfonic acid sodium salt and Na
2SiO
3Interfacial tension value when being made into different concns solution and between the crude oil.See table 3 for details
Table 3
Annotate: remove side chain heneicosyl benzene sulfonic acid sodium salt, Na
2SiO
3Outward, surplus is a water.IFT is the interfacial tension value.
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, improve containing in the surfactant composition of oil recovery factor in the present invention, side chain heneicosyl benzene sulfonic acid sodium salt is at Na
2SiO
3Under the situation of 0.1%～1.4% (weight), and can form 10 between the crude oil
-3The ultra low interfacial tension of mN/m, even can form 10 with crude oil in some concentration
-4The ultra low interfacial tension of mN/m.
Embodiment 4
Present embodiment has specifically described side chain heneicosyl benzene sulfonic acid sodium salt and NaHCO
3Interfacial tension value when being made into different concns solution and between the crude oil.See table 4 for details
Table 4
Annotate: remove side chain heneicosyl benzene sulfonic acid sodium salt, NaHCO
3Outward, surplus is a water.IFT is the interfacial tension value.
In the table 4, 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 4, improve containing in the surfactant composition of oil recovery factor in the present invention, side chain heneicosyl benzene sulfonic acid sodium salt is at NaHCO
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 5
Present embodiment has specifically described side chain octadecyl benzene sulfonic acid sodium salt and Na
2CO
3Interfacial tension value when being made into different concns solution and between the crude oil.See table 5 for details
Table 5
Annotate: remove side chain heneicosyl benzene sulfonic acid sodium salt, Na
2CO
3Outward, surplus is a water.IFT is the interfacial tension value.
In the table 5, laboratory apparatus is a U.S. Texas-500 type interfacial tensimeter, and oil is Zhongyuan Oil Field crude oil, and water is the Zhongyuan Oil Field local water.As seen from Table 5, improve containing in the surfactant composition of oil recovery factor in the present invention, side chain octadecyl benzene sulfonic acid sodium salt 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 6
Present embodiment has specifically described a kind of-side chain heneicosyl benzene sulfonic acid sodium salt and the Na in the surfactant composition of containing that the present invention improves oil recovery factor
2SiO
3Interfacial tension value when being made into different concns solution and between the crude oil is less than 10
-3The needed time of mN/m.See table 6 for details
Table 6
Annotate: remove side chain heneicosyl benzene sulfonic acid sodium salt, Na
2SiO
3Outward, surplus is a water.
In the table 6, 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 6, improve containing in the surfactant composition of oil recovery factor in the present invention, side chain heneicosyl benzene sulfonic acid sodium salt is at Na
2SiO
3Under the situation of 0.1%～1.8% (weight), just form 10 between energy and the crude oil within a short period of time
-3The ultra low interfacial tension of mN/m.
Claims (10)
1, a kind of composition that is used to improve oil recovery factor, it is as follows specifically to fill a prescription:
The alkali of (1) 0.05%～2.0% (weight);
The tensio-active agent of (2) 0.05%～1.0% (weight), this tensio-active agent are that long-chain olefin is through alkylation, sulfonation, neutralization
Resultant, its molecular formula is as follows:
In the formula, R is C
18～C
24Alkyl
M is basic metal, ammonium or amine
(3) surplus is a water;
2, composition according to claim 1 is characterized in that, said R is the alkyl that obtains by behind the long-chain olefin of oligomerization of propene gained and the benzene alkylation.
3, composition according to claim 1 is characterized in that, said R is the C of union alkene dimerization or propylene six poly-gained
18The alkyl that obtains behind alkene and the benzene alkylation.
4, composition according to claim 1 is characterized in that, said R is the C by laurylene dimerization or propylene eight poly-gained
24The alkyl that obtains behind alkene and the benzene alkylation.
5, composition according to claim 1 is characterized in that, said R is the C of union alkene and laurylene polymerization or propylene seven poly-gained
21The alkyl that obtains behind alkene and the benzene alkylation.
According to claim 3 or 5 described compositions, it is characterized in that 6, nonene is resulting by the propylene trimerization.
According to claim 4 or 5 described compositions, it is characterized in that 7, laurylene is poly-resulting by propylene four.
8, composition according to claim 1 is characterized in that, said basic metal is sodium or potassium or lithium.
9, composition according to claim 1 is characterized in that, said alkali is NaOH or Na
2CO
3Or NaHCO
3, the concentration of alkali is 0.1%～0.6% (weight).
10, composition according to claim 1 is characterized in that, said alkali is Na
2SiO
3, its concentration is 0.1%～2.0% (weight).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01123546 CN1400275A (en) | 2001-08-01 | 2001-08-01 | Composite for raising recovery efficiency of crude |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01123546 CN1400275A (en) | 2001-08-01 | 2001-08-01 | Composite for raising recovery efficiency of crude |
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| Publication Number | Publication Date |
|---|---|
| CN1400275A true CN1400275A (en) | 2003-03-05 |
Family
ID=4665142
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01123546 Pending CN1400275A (en) | 2001-08-01 | 2001-08-01 | Composite for raising recovery efficiency of crude |
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|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210487B (en) * | 2006-12-28 | 2012-03-21 | 中国石油化工股份有限公司 | Design method for increasing recovery efficiency technique |
| 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 |
-
2001
- 2001-08-01 CN CN 01123546 patent/CN1400275A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210487B (en) * | 2006-12-28 | 2012-03-21 | 中国石油化工股份有限公司 | Design method for increasing recovery efficiency technique |
| 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 |
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