High temperature acidified mutual solvent
Technical field:
The present invention relates to a kind of chemical agent that is used for acidification of oil field, especially high temperature acidified mutual solvent.
Background technology:
Acidified mutual solvent is meant the chemical agent that acid solution and crude oil are dissolved each other.Acidification of oil field uses the reason of mutual solvent to be:
(1) because active ingredient in the crude oil or heavy component in absorption, the deposition of rock surface, cause the rock surface oleophylic to stop contacting and reaction of acid and rock surface, increased the resistance to flow of crude oil in porous medium.
(2) inhibiter isoreactivity component is adsorbable in rock surface in the acid solution, makes hydrophilic rock surface be reversed to oil-wetted surface, has stoped acid to contact with the further of rock surface, has reduced permeability to oil.Simultaneously, inhibiter isoreactivity component makes tensio-active agent can not play effects such as the protection against corrosion of expection, anti-breast, breakdown of emulsion after rock surface absorption.
(3) solia particle that produces in the acidization plays stabilization to the emulsification of acid solution and crude oil, and the formation of acid-oil emulsion can cause formation damage, and hinders the row of returning of residual acid.
If Gidley discovery sandstone formation was made subsequent fluid with the diesel oil that contains 10% (EGMBE) in 1971, the oil well output after the processing is six to seven times that regular mud acid is handled.In the same year, the article that Gidley and Humble deliver shows that EGMBE has the performance that keeps the rock surface water-wet.Sutton and Lasater had studied the effect that contains mutual solvent in tensio-active agent or the inhibiter working fluid in 1972, find that mutual solvent can reduce the adsorption of formation solids to tensio-active agent, reduce the stability that causes the milk sap that forms by the absorption of tensio-active agent simultaneously, play the effect of anti-emulsion, breakdown of emulsion.Hall added mutual solvent in the tensio-active agent working fluid in 1975, found that mutual solvent can increase the penetration depth of tensio-active agent to rock sample.King in 1988 and Lee have studied a kind of adsorption property of pure ethers mixture mutual solvent, mixture as ethanol, Virahol, isopropylcarbinol and EGMBE, this mixture can change rock wettability, and stronger demulsification is arranged, and acid and the acid sludge that crude oil forms are obviously reduced.The domestic and international present Research of comprehensive acidified mutual solvent is thought, low molecular solvent (alcohol, ether and alcohol ether) is the important component of acidified mutual solvent all the time, is the main direction of mutual solvent development by adding in low molecular solvent that other component strengthens the effect of acidified mutual solvent and reduce mutual solvent to the negative impact of inhibiter effect, and the present invention just is based on that this trend forms.
Summary of the invention:
The objective of the invention is to develop a kind of high temperature resistance, high performance acidified mutual solvent.
The objective of the invention is to realize by following prescription.High temperature acidified mutual solvent is by dipropylene glycol mono-methyl, polyoxyethylene polyoxypropylene tetraethylene pentamine, 2,4 kinds of components of 3 epoxypropyl trimethylammonium chloride ammoniums and water constitute, the mass content of each component is respectively the dipropylene glycol mono-methyl: polyoxyethylene polyoxypropylene tetraethylene pentamine 29%~54%: 26%~48%, 2,3 epoxypropyl trimethylammonium chloride ammoniums: water 2.5%~7.6%: 15%~40%, each composition sum is 100% in the high temperature acidified mutual solvent.
The acting as of main component in the high temperature acidified mutual solvent:
(1) dipropylene glycol mono-methyl
The dipropylene glycol mono-methyl is one of high temperature acidified main component of using the clay mutual solvent, and structural formula is:
The dipropylene glycol mono-methyl is the low molecular solvent of excellent performance, the ethylene glycol monobutyl ether that the effect in acidified mutual solvent is better than using always (seeing Table 1).Table 1 explanation dipropylene glycol mono-methyl can significantly reduce the negative impact of ethylene glycol monobutyl ether class mutual solvent to the inhibiter effect, reason is that the formic acid that produces behind the ester linkage hydrolyzing in the dipropylene glycol mono-methyl is the synergistic agent of high temperature inhibition, and this is a main innovate point of the present invention.
The performance of two kinds of low molecular solvent of table 1 relatively
Solvent | The solubilising oil mass
1)(ml oil/ml acid solution)
| Wetting angle
2)(°)
| Erosion rate
3)(g/m
2H)
|
The dipropylene glycol mono-methyl | 0.31 | 36 | 1.83 |
Ethylene glycol monobutyl ether | 0.17 | 45 | 5.79 |
1) meltage of kerosene in 20% hydrochloric acid+10% solvent+2% inhibiter acid fluid system, test temperature is 90 ℃; 2) soak the wetting angle of 4h back glass sheet to water in 20% hydrochloric acid+10% solvent+2% inhibiter acid fluid system, test temperature is 90 ℃; 3) 20% hydrochloric acid+10% solvent+2% inhibiter acid fluid system is to the corrosion speed rate of N80 steel disc, 90 ℃ of test temperatures. |
(2) 2,3 epoxypropyl trimethylammonium chloride ammoniums
2,3 epoxypropyl trimethylammonium chloride ammoniums are one of main components of high temperature acidified mutual solvent, 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 surface by competitive adsorption, can replace the petroleum acids active substance that is adsorbed on the rock surface again, therefore, the main effect of 2,3 epoxypropyl trimethylammonium chloride ammoniums is slightly water-wets of keeping rock surface.
(3) polyoxyethylene polyoxypropylene tetraethylene pentamine
The polyoxyethylene polyoxypropylene tetraethylene pentamine is one of main component of high temperature acidified mutual solvent, and structural formula is:
The polyoxyethylene polyoxypropylene tetraethylene pentamine is the emulsion splitter of oil field water-in-oil emulsion commonly used, and it has two effects in mutual solvent.One for preventing the generation of the sour milk sap of oil bag, the 2nd, and form by micellar crude oil is played solublization.
Embodiment:
Describe composition of the present invention and preparation process and performance perameter in detail below in conjunction with embodiment.
(1) material property requirement
Dipropylene glycol mono-methyl effective content is greater than 96%;
2,3 epoxypropyl trimethylammonium chloride ammonium effective contents are greater than 96%;
Polyoxyethylene polyoxypropylene tetraethylene pentamine effective content is greater than 93%.
(2) high temperature acidified mutual solvent prepares example and performance perameter
To the 1m that has started
3Add 220kg water, 460kg dipropylene glycol mono-methyl and 280kg polyoxyethylene polyoxypropylene tetraethylene pentamine in the emulsor, be warming up to 50 ℃, be stirred to dissolving fully.Add 40kg2 then while stirring, 3 epoxypropyl trimethylammonium chloride ammoniums are stirred to and form homogeneous transparent solution, are exactly high temperature acidified mutual solvent of the present invention.The performance perameter of embodiment product sees Table 2~table 4.
The performance perameter of table 2 embodiment product in 20% hydrochloric acid
1) Working concentration, % | 0.0 | 2.5 | 5.0 | 10 | 20 |
Demulsification efficiency, % | 76.4 | 91.8 | 96.7 | 100 | 100 |
The solubilising oil mass, ml oil/ml acid solution | 0.00 | 0.05 | 0.13 | 0.31 | 0.84 |
Sheet glass and acid solution wetting angle, ° | 131 | 84 | 76 | 63 | 62 |
Erosion rate, g/m
2·h
| 2.33 | 2.07 | 1.67 | 1.83 | 2.64 |
1) test temperature is 90 ℃; |
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The heat resistance of table 4 embodiment product in 20% hydrochloric acid acid solution
1) Test temperature, ℃ | 120 | 150 | 210 |
Demulsification efficiency, % | 100 | 100 | 98 |
The solubilising oil mass, ml oil/ml acid solution | 0.30 | 0.28 | 0.25 |
Sheet glass and acid solution wetting angle, ° | 62 | 57 | 56 |
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 high temperature acidified mutual solvent
High temperature acidified mutual solvent working conditions provided by the present invention is:
Reservoir temperature: 0 ℃~210 ℃;
Acid solution type: hydrochloric acid, mud acid, nitric acid;
Acid solution total concn: smaller or equal to 30%;
High temperature acidified mutual solvent working concentration: 5%~10%.
(4) high temperature acidified mutual solvent using method
High temperature acidified mutual solvent is to be dissolved in the acid solution to use, and high temperature acidified mutual solvent and acid solution are dissolved each other.