CN1760319A - Cleanup additive in use for acidification in high temperature - Google Patents
Cleanup additive in use for acidification in high temperature Download PDFInfo
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- CN1760319A CN1760319A CN 200510044934 CN200510044934A CN1760319A CN 1760319 A CN1760319 A CN 1760319A CN 200510044934 CN200510044934 CN 200510044934 CN 200510044934 A CN200510044934 A CN 200510044934A CN 1760319 A CN1760319 A CN 1760319A
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- acidification
- high temperature
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Abstract
A draining aid for high-temp acidifying is proportionally prepared from dodecyldimethyl betaine, polyoxyvinyl perfluorooctylether-14,2, 3-epoxypropyltrimethyl ammonium chloride, methanol and water. When it is proportionally added to hydrochloric acid solution, the surface tension of acid solution is decreased to that less than 22 mN/m.
Description
Technical field:
The present invention relates to a kind of chemical agent that is used for acidification of oil field, especially cleanup additive in use for acidification in high temperature.
Background technology:
In the acidization, along with the acid of carrying out of sour rock reaction is consumed gradually, the pH value of residual acid raises with its prolongation in the stratum residence time, when the pH of residual acid value greater than 2.2 the time, the Fe in the sour molten product
3+To begin to produce Fe (OH)
3Precipitation, and precipitation capacity increases with the rising of pH; When pH reaches 3.2, Fe
3+Basically all form gel Fe (OH)
3Precipitation, gel Fe (OH)
3Can cause serious harm to reservoir permeability.In addition, the water saturation that the stratum can increase the stratum is invaded in residual acid, reduces oil, the gas-phase permeation rate of invaded zone, directly influences acidizing effect.For avoiding residual acid to be detained secondary pollution and the injury that reservoir is caused, the oil of invaded zone, gas phase oil impregnate rate are restored, must be with the residual acid of the invaded zone row of returning rapidly and thoroughly.
The acidifying cleanup additive is the acidizing additive that residual acid is easily discharged from oil reservoir.The acidifying cleanup additive is divided into by the mechanism of action: energizer, tensio-active agent and low mass molecule alcohol 3 classes.Grubb in 1963, W.E. and Martin, F.G. have proposed to improve the method that row's ability is returned in residual acid with hydrocarbon-surfactant first.C.F.Smith in 1974 and D.L.Murphy find that a kind of water-soluble fluorochemical surfactant can be reduced to the surface tension of acid solution below the 20mN/m, add the discharge capacity of returning that this fluorine-containing promoting agent can significantly reduce the row's of returning time and increase working fluid in acid solution.The main composite use of present surfactant-based cleanup additive is extensive use of in conventional acidifying and fracture acidizing.
According to the Laplace equation:
P
c＝2σcosθ/R
m
In the formula, P
cThe capillary force of-profit or air-water interface (mPa);
The interfacial tension of σ--profit or air-water interface (mN/m);
The contact angle at θ-water, oil, rock or water, gas, rock three phase boundary place (°);
R
m-capillary radius (m).It is the process that crude oil in the stratum or gas are displaced residual acid that row is returned in residual acid, is the resistance of oil (gas) expelling water on the water-wet stratum by Laplace equation capillary force.Therefore, present surfactant-based cleanup additive mainly reduces the capillary resistance that row is returned in residual acid by reducing surface tension.But ignored the effect of rock wettability variation in the cleanup additive research to the row of returning of residual acid, when wetting angle when 30 ° rise to 85 °, the capillary resistance that row is returned in residual acid can reduce 10 times, and the present invention will reduce the result of capillary tensio-active agent and the composite use of wetting conditioning agent.
Summary of the invention:
The objective of the invention is to develop a kind of high temperature resistance, high performance acidifying cleanup additive.
The objective of the invention is to realize by following prescription.Cleanup additive in use for acidification in high temperature is by Varion CDG-K, polyoxyethylene perfluoro capryl ether-14,2,3 epoxypropyl trimethylammonium chloride ammoniums, 5 kinds of components of first alcohol and water constitute, the mass content of each component is respectively Varion CDG-K: polyoxyethylene perfluoro capryl ether-14:0.1%～1.0%, 2 27%～37%,, 3 epoxypropyl trimethylammonium chloride ammoniums: methyl alcohol 1.5%～4.0%: water 30%～40%: 30%～40%, each composition sum is 100% in the cleanup additive in use for acidification in high temperature.
The acting as of main component in the cleanup additive in use for acidification in high temperature:
(1) Varion CDG-K
Varion CDG-K is one of main component of cleanup additive in use for acidification in high temperature, and structural formula is:
Varion CDG-K has good solubility in acid solution, it mainly acts on is to reduce the acid solution surface tension.
(2) polyoxyethylene perfluoro capryl ether-14
Polyoxyethylene perfluoro capryl ether-the 14th, one of main component of cleanup additive in use for acidification in high temperature, structural formula is:
Polyoxyethylene perfluoro capryl ether-14 has good solubility and excellent interfacial activity in acid solution, it mainly acts on is to reduce the acid solution surface tension.
(3) 2,3 epoxypropyl trimethylammonium chloride ammoniums
2,3 epoxypropyl trimethylammonium chloride ammoniums are one of main components of cleanup additive in use for acidification in high temperature, and structural formula is:
2,3 epoxypropyl trimethylammonium chloride ammoniums are dissociated into organic cation in acid, this positively charged ion can be adsorbed in clay particle surface by electrostatic interaction, make rock interface keep slightly water-wet.Because electrostatic attraction is significantly higher than intermolecular attraction, 2,3 epoxypropyl trimethylammonium chloride ammoniums both can reduce in the acid solution inhibiter etc. in the adsorptive capacity of rock interface by competitive adsorption, can replace the petroleum acids active substance that is adsorbed on the interface again, therefore, the main effect of 2,3 epoxypropyl trimethylammonium chloride ammoniums is slightly water-wets of keeping rock surface.
(4) methyl alcohol
Methyl alcohol is one of ancillary component of cleanup additive in use for acidification in high temperature, and its main effect has:
The first, the hydrotropy effect, methyl alcohol can make each component in the cleanup additive dissolve each other;
The second, the auxiliary row of helping acts on, and methyl alcohol makes rock interface keep water-wet by the active substance that competitive adsorption and solubilising are adsorbed on rock interface, simultaneously because the vapour pressure of methyl alcohol apparently higher than water, also can improve the pressure difference that row is returned in residual acid to a certain extent.
Embodiment:
Describe composition of the present invention, preparation process and performance perameter in detail below in conjunction with embodiment.
(1) material property requirement
The Varion CDG-K effective content is greater than 96%;
Polyoxyethylene perfluoro capryl ether-14 effective content is greater than 98%;
2,3 epoxypropyl trimethylammonium chloride ammonium effective contents are greater than 96%;
The methyl alcohol effective content is greater than 90%.
(2) cleanup additive in use for acidification in high temperature prepares example and performance perameter
In the 1m3 emulsor that has started, add 340kg water, 340kg methyl alcohol, be warming up to 30 ℃, add 28kg2 while stirring, 3 epoxypropyl trimethylammonium chloride ammoniums, 2kg polyoxyethylene perfluoro capryl ether-14 and 310kg Varion CDG-K, be stirred to and form homogeneous transparent solution, packing with the 200kg plastic tank, is exactly cleanup additive in use for acidification in high temperature of the present invention.The performance perameter of embodiment product sees Table 1～table 3.
The performance perameter of table 1 embodiment product in 20% hydrochloric acid
1)
| Working concentration, % | 0.0 | 0.25 | 0.5 | 1.0 | 2.0 |
| Surface tension, mN/m | 77.3 | 26.4 | 21.3 | 20.5 | 19.7 |
| Sheet glass and acid solution wetting angle 2), ° | 131 | 108 | 86 | 85 | 85 |
| 1) test temperature is 90 ℃, 20% hydrochloric acid+embodiment product+2% inhibiter acid fluid system: 2) soak the wetting angle of 4h back glass sheet to water in 20% hydrochloric acid+embodiment product+2% inhibiter acid fluid system. | |||||
The performance perameter of table 2 embodiment product in different acid solutions
1)
| Acid solution | Hydrochloric acid | Mud acid 2) | ||||
| 10% | 20% | 30% | 10% | 20% | 30% | |
| Surface tension, mN/m | 19.8 | 20.5 | 20.8 | 18.9 | 19.5 | 20.1 |
| Sheet glass and acid solution wetting angle, ° | 85 | 85 | 84 | 87 | 86 | 87 |
| 1) testing temperature is 90 ℃, 15%HCl+5%HF+1% embodiment product+2% inhibiter acid fluid system; 2) soak the wetting angle of 4h back glass sheet in 15%HCl+5%HF+1% embodiment product+2% inhibiter acid fluid system to water. | ||||||
The heat resistance of table 3 embodiment product in 20% hydrochloric acid acid solution
1)
| Test temperature, ℃ | 120 | 150 | 210 |
| Surface tension, mN/m | 20.5 | 21.4 | 27.6 |
| Sheet glass and acid solution wetting angle, ° | 85 | 84 | 86 |
| 1) behind the constant temperature 12h, 90 ℃ of conditions are measured each index to 20% hydrochloric acid+10% embodiment product+2% inhibiter acid fluid system under hot conditions. | |||
(3) working conditions of cleanup additive in use for acidification in high temperature
Cleanup additive in use for acidification in high temperature working conditions provided by the present invention is:
Reservoir temperature: 0 ℃～210 ℃;
Acid solution type: hydrochloric acid, mud acid;
Acid solution total concn: smaller or equal to 30%;
Cleanup additive in use for acidification in high temperature working concentration: 0.5%～2.0%.
(4) cleanup additive in use for acidification in high temperature using method
Cleanup additive in use for acidification in high temperature is to be dissolved in the acid solution to use, and cleanup additive in use for acidification in high temperature and acid solution are dissolved each other.
Claims (1)
1. cleanup additive in use for acidification in high temperature, it is characterized in that, by Varion CDG-K, polyoxyethylene perfluoro capryl ether-14,2,3 epoxypropyl trimethylammonium chloride ammoniums, 5 kinds of components of first alcohol and water constitute, the heavy amount content of each component is respectively Varion CDG-K: polyoxyethylene perfluoro capryl ether-14:0.1%～1.0%, 2 27%～37%,, 3 epoxypropyl trimethylammonium chloride ammoniums: methyl alcohol 1.5%～4.0%: water 30%～40%: 30%～40%, each composition sum is 100% in the cleanup additive in use for acidification in high temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100449346A CN100358969C (en) | 2005-10-18 | 2005-10-18 | Cleanup additive in use for acidification in high temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100449346A CN100358969C (en) | 2005-10-18 | 2005-10-18 | Cleanup additive in use for acidification in high temperature |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1760319A true CN1760319A (en) | 2006-04-19 |
| CN100358969C CN100358969C (en) | 2008-01-02 |
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|---|---|---|---|
| CNB2005100449346A Expired - Fee Related CN100358969C (en) | 2005-10-18 | 2005-10-18 | Cleanup additive in use for acidification in high temperature |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102002354A (en) * | 2010-11-02 | 2011-04-06 | 上海大学 | Oil displacement agent with ultra-low oil-water interfacial tension and application thereof |
| CN102295919A (en) * | 2011-05-30 | 2011-12-28 | 西南石油大学 | High efficient fluoride-free cleanup additive used for acidifying |
| CN102373054A (en) * | 2010-08-12 | 2012-03-14 | 中国石油天然气股份有限公司 | Visco-elastic surfactant acidizing liquid |
| CN102533243A (en) * | 2010-12-10 | 2012-07-04 | 中国石油化工股份有限公司 | Fracture acidizing cleanup additive of fluorine-containing carbon chain Gemini surfactant and preparation method thereof |
| CN103215020A (en) * | 2012-01-18 | 2013-07-24 | 中国石油天然气股份有限公司 | Preparation method of wetting improving agent for gas well fracturing |
| CN103820096A (en) * | 2012-11-16 | 2014-05-28 | 中国石油天然气股份有限公司 | Efficient cleanup additive for gas well and preparing method of efficient cleanup additive |
| CN108239532A (en) * | 2016-12-26 | 2018-07-03 | 中国石油化工股份有限公司 | A kind of shale pressure break slippery water cleanup additive, preparation method and application |
| CN115261010A (en) * | 2022-08-09 | 2022-11-01 | 郑州市新郑梅久实业有限公司 | Petroleum fracturing cleanup additive and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067945A (en) * | 1991-06-15 | 1993-01-13 | 四川石油管理局天然气研究所 | Acidifying and fracturing technology cleanup additive |
| CN1313562C (en) * | 2004-06-22 | 2007-05-02 | 梁利平 | High performance cleanup additive for oil and gas well and method for making same |
-
2005
- 2005-10-18 CN CNB2005100449346A patent/CN100358969C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102373054A (en) * | 2010-08-12 | 2012-03-14 | 中国石油天然气股份有限公司 | Visco-elastic surfactant acidizing liquid |
| CN102373054B (en) * | 2010-08-12 | 2013-07-31 | 中国石油天然气股份有限公司 | Visco-elastic surfactant acidizing liquid |
| CN102002354A (en) * | 2010-11-02 | 2011-04-06 | 上海大学 | Oil displacement agent with ultra-low oil-water interfacial tension and application thereof |
| CN102533243A (en) * | 2010-12-10 | 2012-07-04 | 中国石油化工股份有限公司 | Fracture acidizing cleanup additive of fluorine-containing carbon chain Gemini surfactant and preparation method thereof |
| CN102533243B (en) * | 2010-12-10 | 2014-04-02 | 中国石油化工股份有限公司 | Fracture acidizing cleanup additive of fluorine-containing carbon chain Gemini surfactant and preparation method thereof |
| CN102295919A (en) * | 2011-05-30 | 2011-12-28 | 西南石油大学 | High efficient fluoride-free cleanup additive used for acidifying |
| CN102295919B (en) * | 2011-05-30 | 2012-09-12 | 西南石油大学 | Fluoride-free cleanup additive used for acidifying |
| CN103215020A (en) * | 2012-01-18 | 2013-07-24 | 中国石油天然气股份有限公司 | Preparation method of wetting improving agent for gas well fracturing |
| CN103820096A (en) * | 2012-11-16 | 2014-05-28 | 中国石油天然气股份有限公司 | Efficient cleanup additive for gas well and preparing method of efficient cleanup additive |
| CN108239532A (en) * | 2016-12-26 | 2018-07-03 | 中国石油化工股份有限公司 | A kind of shale pressure break slippery water cleanup additive, preparation method and application |
| CN115261010A (en) * | 2022-08-09 | 2022-11-01 | 郑州市新郑梅久实业有限公司 | Petroleum fracturing cleanup additive and preparation method and application thereof |
| CN115261010B (en) * | 2022-08-09 | 2023-09-08 | 郑州市新郑梅久实业有限公司 | Petroleum fracturing cleanup additive and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN100358969C (en) | 2008-01-02 |
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| C06 | Publication | ||
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: PetroKMS Co., Ltd. Assignor: China Petroleum University (East China) Contract record no.: 2011990000546 Denomination of invention: Cleanup additive in use for acidification in high temperature Granted publication date: 20080102 License type: Exclusive License Open date: 20060419 Record date: 20110705 |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080102 Termination date: 20111018 |