CN116042204A - Antihypertensive injection and preparation method thereof - Google Patents
Antihypertensive injection and preparation method thereof Download PDFInfo
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Abstract
The invention provides a pressure-reducing injection-increasing agent and a preparation method thereof, and belongs to the technical field of oil fields. Comprises hydrophobic nano particles, a composite surfactant, an auxiliary agent and water; the hydrophobic nano particles are silica nano hollow spheres with surfaces loaded with fluorine-containing groups and long-chain alkyl chains; the auxiliary agent is at least one selected from polyethylene glycol, methanol, ethanol and glycerol. The method can solve the problem of injectability of the low-permeability reservoir, has simple preparation process, small dosage, good stability, strong timeliness and small adsorption capacity, has good recovery efficiency improving effect and thick oil viscosity reducing function, and has important economic value for development of the low-permeability reservoir and recovery efficiency improving technology.
Description
Technical Field
The invention relates to the technical field of oil fields, in particular to a pressure-reducing injection-increasing agent and a preparation method thereof.
Background
In recent years, with the increasing demand of energy, the development of low permeability oil fields has attracted more and more attention as the continuous reduction of crude oil reserves. The development of the low permeability oil field has very important significance for the sustainable and stable development of petroleum industry in China in future. Because the low permeability reservoir deposit granule is thin, and mud quality is high, and compaction effect is strong, has physical properties characteristics such as hole throat is tiny, capillary force effect is showing, and the water injection well often appears the water injection pressure height in the water injection development process, and the water injection is difficult, even stops the problem such as annotating, and stratum energy can not be supplied, seriously influences the normal production of oil field.
In this regard, it is common in China to add chemical compositions to injected water to improve water flooding. The surfactant has interfacial activity, can obviously reduce oil-water interfacial tension, increase capillary number, promote crude oil to be desorbed from rock and effectively dispersed, and realize effective driving of residual oil, thereby improving recovery ratio, and therefore, the surfactant is the most commonly used oil displacement agent. The oil-water interfacial tension is reduced to 10 < -3 > mN/m, which is an important index for screening the surfactant as a chemical oil displacement agent. However, in the practical application process, because the mineralization degree of the injected water and the formation water used in water injection development is greatly different, the existing oil displacement agent system is difficult to simultaneously have good capability of reducing the oil-water interfacial tension under the conditions of low-mineralization degree injected water and high-mineralization degree formation water. Meanwhile, because the surfactant is adsorbed on the surface of the stratum, an ideal water flooding effect is difficult to obtain in the practical application process. When the interfacial tension of oil and water is reduced to ultra low, emulsification is easy to cause, and although the emulsification is favorable for oil displacement, a large amount of emulsification easily forms small particles to block pore throats so as to easily cause the increase of water injection pressure, and is very unfavorable for a long-term high-pressure underinjection well.
There are also many patent literature reports on pressure-reducing and injection-increasing surfactant compositions, such as: the Chinese patent application CN105154051A discloses a pressure-reducing and injection-increasing surfactant compound composition, a preparation method and application thereof, wherein the raw material components of the pressure-reducing and injection-increasing surfactant compound composition comprise 0.05-0.2 part of amphoteric surfactant, 0.05-0.15 part of clay stabilizer, 0.005-0.012 part of antiscaling agent and 100 parts of water. The method can be used for reducing pressure and increasing injection of a water injection well of long-term high-pressure underinjection of an ultralow-permeability oil reservoir with the permeability of less than 5mD, can effectively reduce the water injection pressure of the water injection well, and reduces the oil-water interfacial tension to 10 by changing the wettability -1 -10 -2 mN/m, which is not only beneficial to the starting of residual oil, but also can avoidThe compound composition can emulsify crude oil to raise water injection pressure and raise water injection capacity of under-injected well, and can prevent clay expansion and inhibit damage of carbonate deposit, such as calcium carbonate, to stratum. The Chinese patent application CN104371689A discloses an ultralow interfacial tension surfactant compound system and a preparation method thereof, wherein the ultralow interfacial tension surfactant compound system comprises, by mass, 10% -33% of a main agent, 7% -23% of a synergistic agent, 1% -4% of a stabilizer and the balance of water; wherein the main agent is an amphoteric surfactant, the synergist is a nonionic surfactant, and the stabilizer is an anionic surfactant. The ultra-low interfacial tension surfactant compound system can enable the oil-water interfacial tension to reach the order of magnitude of 10 < -4 > mN/m or lower in a short time under a lower dosage, is suitable for tertiary oil recovery of a low-permeability or ultra-low-permeability reservoir to improve the recovery ratio of crude oil, can also be used for depressurization and injection increase of a water well and viscosity reduction of thick oil, does not contain alkali, and does not cause damage to stratum in use.
However, the pressure-reducing and injection-increasing surfactant compound composition mainly has the pressure-reducing and injection-increasing effects by the amphoteric surfactant, and has poor adaptability to highly mineralized formation water.
Therefore, aiming at the problem that the existing depressurization and injection-increasing agent has poor adaptability to water quality with different mineralization degrees, a depressurization and injection-increasing agent system which has good capability of reducing the interfacial tension of oil and water under the conditions of low-mineralization-degree injected water and high-mineralization-degree stratum water and has moderate emulsifying capability is required to be developed, and the injection pressure is prevented from being increased due to the fact that a large amount of crude oil is emulsified.
Disclosure of Invention
The invention aims to provide a depressurization and injection increasing agent and a preparation method thereof, which can solve the problem of injectability of a low-permeability oil reservoir, and has the advantages of simple preparation process, small dosage, good stability, strong timeliness, small adsorption capacity, good recovery efficiency improving effect and thick oil viscosity reduction function, and has important economic value for development of the low-permeability oil reservoir and improvement of recovery efficiency technology.
The technical scheme of the invention is realized as follows:
the invention provides a depressurization and injection increasing agent, which comprises hydrophobic nano particles, a composite surfactant, an auxiliary agent and water;
the hydrophobic nano particles are silica nano hollow spheres with surfaces loaded with fluorine-containing groups and long-chain alkyl chains;
the auxiliary agent is at least one selected from polyethylene glycol, methanol, ethanol and glycerol.
As a further improvement of the invention, the invention is prepared from the following raw materials in parts by weight: 2-3 parts of hydrophobic nano particles, 10-15 parts of composite surfactant, 0.5-5 parts of auxiliary agent and 40-50 parts of water.
As a further improvement of the present invention, the complex surfactant includes an anionic surfactant and a cationic surfactant.
As a further improvement of the present invention, the anionic surfactant is at least one selected from the group consisting of sodium dodecylbenzenesulfonate, sodium dodecylsulfonate, sodium dodecylsulfate, sodium tetradecyl sulfide, sodium tetradecyl sulfonate, sodium tetradecyl benzenesulfonate, sodium hexadecyl sulfonate, sodium hexadecyl sulfate, sodium octadecyl sulfonate, sodium octadecyl benzenesulfonate, sodium octadecyl sulfate; the cationic surfactant is at least one selected from cetyltrimethylammonium bromide, dodecyltrimethylammonium chloride, cetyltrimethylammonium chloride, cetyldimethylbenzyl ammonium chloride and octadecyltrimethylammonium bromide.
As a further improvement of the invention, the composite surfactant is sodium stearyl sulfate and cetyltrimethylammonium bromide, and the mass ratio is 2:5-10.
As a further improvement of the present invention, the preparation method of the hydrophobic nanoparticle is as follows:
s1, adding aminosilane, fluorine-containing silane and long-chain alkylsilane into an organic solvent to obtain an oil phase;
s2, adding the aqueous solution containing the surfactant into the oil phase in the step S1, emulsifying, stirring for reaction, centrifuging, washing and drying to obtain the hydrophobic nano particles.
As a further improvement of the present invention, the aminosilane is selected from at least one of γ -aminopropyl trimethoxysilane, γ -aminopropyl triethoxysilane, N- β (aminoethyl) - γ -aminopropyl trimethoxysilane, N- β (aminoethyl) - γ -aminopropyl triethoxysilane, N- β (aminoethyl) - γ -aminopropyl methyldimethoxysilane, N- β (aminoethyl) - γ -aminopropyl methyldiethoxysilane, diethylenetriaminopropyl trimethoxysilane; the fluorine-containing silane is selected from 1H, 2H-perfluoro decyl triethoxysilane, 1H, 2H-perfluoro decyl trimethoxysilane, dodecafluoro heptyl propyl methyl dimethoxy silane 3, 3-trifluoropropyl methyl dimethoxy silane, 3-trifluoropropyl trimethoxy silane at least one of 1h,2 h-perfluorooctyltriethoxysilane or 1h,2 h-perfluorooctyltrimethoxysilane; the long-chain alkyl silane is at least one selected from hexadecyl dimethyl chlorosilane, octadecyl silane and dodecyl silane; the surfactant is at least one selected from Tween-20, tween-40, tween-60 and Tween-80; the organic solvent is at least one selected from dichloromethane, chloroform, petroleum ether, ethyl acetate, methyl acetate, butyl acetate, cyclohexane and toluene.
As a further improvement of the invention, the mass ratio of the aminosilane, the fluorine-containing silane and the long-chain alkylsilane in the step S1 is 10-15:3-5:4-7.
As a further improvement of the invention, the concentration of the aqueous solution containing the surfactant in the step S2 is 3-5wt%, the mass ratio of the aqueous solution containing the surfactant to the oil phase is 2-4:5-7, and the stirring reaction time is 3-5h.
The invention further provides a preparation method of the pressure-reducing injection-increasing agent, which comprises the following steps: dissolving the composite surfactant and the auxiliary agent in water, heating to 40-45 ℃, adding the hydrophobic nano particles, and performing 1000-1200W ultrasonic dispersion for 10-15min to prepare the pressure-reducing injection-increasing agent.
The invention has the following beneficial effects: in the preparation process of the hydrophobic nano particles, amino silane, fluorine-containing silane and long-chain alkyl silane are dissolved in an organic solvent in the preparation process of the nano hollow spheres, and the amino silane, fluorine-containing silane and long-chain alkyl silane are added into water, can not be dissolved in water at first, but are dispersed into water-in-oil droplets in the emulsification process, wherein the amino group faces to the inside, and the fluorine-containing group and long-chain alkyl chain faces to the outside. As the reaction proceeds, the amino groups become protonated and become amphiphilic molecules, which can further stabilize the silane droplets. At the same time, the amino group protonation can provide an alkaline environment to catalyze the silane to generate a sol-gel process. With the consumption of internal silane, a hollow structure is obtained, so that the silica nano hollow sphere with the surface loaded with fluorine-containing groups and long-chain alkyl chains is prepared.
Due to the strong hydrophobic and oleophylic capacity and adsorption capacity of the hydrophobic nano particles, one or more layers of nano film structures can be formed on the surfaces of rock pores or throats when the hydrophobic nano particles are used in a water injection well, so that the tension of an oil-water interface is reduced, the wettability of the rock surface is changed, the contact between the rock and water is blocked, hydration expansion and diffusion of clay and the like are avoided, the flow resistance of water in a stratum is weakened, the problem of high-pressure underinjection of a low-permeability compact oil-gas reservoir is finally effectively solved, and the secondary development of the oil-gas reservoir is ensured.
The pressure-reducing injection-increasing agent prepared by the invention can solve the problem of injectability of a low-permeability reservoir, has simple preparation process, small dosage, good stability, strong timeliness and small adsorption quantity, has good recovery efficiency-improving effect and thick oil viscosity-reducing function, and has important economic value for development of the low-permeability reservoir and improvement of recovery efficiency technology.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a blood pressure reducing and injection increasing agent.
The raw materials (weight portions) comprise 2 portions of hydrophobic nano particles, 10 portions of composite surfactant, 0.5 portion of glycol and 40 portions of water. The composite surfactant is sodium octadecyl sulfate and cetyltrimethylammonium bromide, and the mass ratio is 2:5.
The preparation method of the hydrophobic nano-particles comprises the following steps:
s1, adding 10 parts by weight of gamma-aminopropyl trimethoxy silane, 3 parts by weight of dodecafluoro heptyl propyl methyl dimethoxy silane and 4 parts by weight of dodecyl silane into 100 parts by weight of petroleum ether to obtain an oil phase;
s2, adding 20 parts by weight of aqueous solution containing 3wt% of Tween-20 into 50 parts by weight of the oil phase in the step S1, emulsifying for 15min at 12000r/min, stirring for reaction for 3h, centrifuging, washing and drying to obtain the hydrophobic nano particles.
The preparation method comprises the following steps: and (3) dissolving the composite surfactant and glycol in water, heating to 40 ℃, adding the hydrophobic nano particles, and performing 1000W ultrasonic dispersion for 10min to prepare the pressure-reducing injection-increasing agent.
Example 2
The embodiment provides a blood pressure reducing and injection increasing agent.
The raw materials comprise (by weight parts) 3 parts of hydrophobic nano particles, 15 parts of composite surfactant, 5 parts of glycerol and 50 parts of water. The composite surfactant is sodium octadecyl sulfate and cetyltrimethylammonium bromide, and the mass ratio is 2:10.
The preparation method of the hydrophobic nano-particles comprises the following steps:
s1, adding 15 parts by weight of N-beta (aminoethyl) -gamma-aminopropyl methyl dimethoxy silane, 5 parts by weight of 1H, 2H-perfluoro octyl triethoxy silane and 7 parts by weight of octadecyl silane into 100 parts by weight of methyl acetate to obtain an oil phase;
s2, adding 40 parts by weight of an aqueous solution containing 5wt% of Tween-40 into 70 parts by weight of the oil phase in the step S1, emulsifying for 15min at 12000r/min, stirring and reacting for 5h, centrifuging, washing and drying to obtain the hydrophobic nano particles.
The preparation method comprises the following steps: and (3) dissolving the composite surfactant and the glycerol in water, heating to 45 ℃, adding the hydrophobic nano particles, and performing ultrasonic dispersion for 15min at 1200W to prepare the pressure-reducing injection-increasing agent.
Example 3
The embodiment provides a blood pressure reducing and injection increasing agent.
The raw materials comprise (by weight parts) hydrophobic nano-particles 2.5 parts, composite surfactant 12 parts, methanol 2 parts and water 45 parts. The composite surfactant is sodium octadecyl sulfate and cetyltrimethylammonium bromide, and the mass ratio is 2:7.
The preparation method of the hydrophobic nano-particles comprises the following steps:
s1, adding 12 parts by weight of N-beta (aminoethyl) -gamma-aminopropyl methyl diethoxy silane, 4 parts by weight of 1H, 2H-perfluoro octyl trimethoxy silane and 5.5 parts by weight of hexadecyl dimethyl chlorosilane into 100 parts by weight of butyl acetate to obtain an oil phase;
s2, adding 30 parts by weight of aqueous solution containing 4wt% of Tween-80 into 60 parts by weight of the oil phase in the step S1, emulsifying for 15min at 12000r/min, stirring for reaction for 4h, centrifuging, washing and drying to obtain the hydrophobic nano particles.
The preparation method comprises the following steps: and (3) dissolving the composite surfactant and methanol in water, heating to 42 ℃, adding the hydrophobic nano particles, and performing ultrasonic dispersion for 12min at 1100W to obtain the pressure-reducing injection-increasing agent.
Comparative example 1
In comparison with example 3, the difference is that no N-. Beta. -aminoethyl-. Gamma. -aminopropyl methyldiethoxysilane is added in step S1.
Comparative example 2
In comparison with example 3, the difference is that 1H, 2H-perfluorooctyl trimethoxysilane was not added in step S1.
Comparative example 3
In comparison with example 3, the difference is that N-. Beta. -aminoethyl-. Gamma. -aminopropyl methyldiethoxysilane and 1H, 2H-perfluorooctyl trimethoxysilane are not added in step S1.
Test example 1
200g of quartz sand with 200 meshes is taken, 5wt% hydrochloric acid is added for acidification for 1h, and suction filtration is carried out; 50mL of NH with a mass fraction of 5wt% was added 4 Filtering Cl solution; 50mL of the depressurization injection enhancer prepared in examples 1 to 3 and comparative examples 1 to 3 was added, and the mixture was subjected to static adsorption at 80℃for 48 hours, followed by washing, drying and tabletting. The contact angle of water on the quartz sand surface was measured on a DM-500 type optical contact angle meter, and the results are shown in table 1.
TABLE 1
| Group of | Water contact angle (°) |
| Blank group | 24 |
| Example 1 | 152 |
| Example 2 | 157 |
| Example 3 | 161 |
| Comparative example 1 | 132 |
| Comparative example 2 | 127 |
| Comparative example 3 | 101 |
As can be seen from the above table, the pressure-reducing and injection-increasing agents prepared in examples 1 to 3 of the present invention significantly improve the hydrophobic properties of the base material.
Test example 2 field application
The pressure-reducing and injection-increasing agents prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to pressure-reducing and injection-increasing tests.
The method comprises the following specific steps: (1) by 5wAcidizing and impurity removing are carried out on the near wellbore zone by t% hydrochloric acid; (2) injecting 5wt% NH 4 Cl solution is subjected to anti-swelling treatment, and NH is carried out simultaneously 4 Cl is also an inducer for separating the super-hydrophobic nano polysilicone core from the water-based nano polysilicone; (3) injecting a proper amount of clear water slugs to prevent high concentration NH 4 Direct contact of Cl with water-based nano-polysilicates; (4) injecting water-based nano polysilicone dispersion liquid with the injection amount of V=pi r 2 X h x phi, r is the treatment radius, h is the thickness of the oil layer, phi is the average porosity; (5) and (3) closing the well and carrying out static adsorption for more than 48 hours, and opening the well to normally inject water for oil displacement.
The results are shown in Table 2.
TABLE 2
| Group of | Effective rate (%) | Expiration date |
| Before measures | 24.2 | / |
| Example 1 | 96.7 | For 1 year |
| Example 2 | 97.1 | 1.5 years |
| Example 3 | 97.5 | 1.5 years |
| Comparative example 1 | 80.2 | For 10 months |
| Comparative example 2 | 78.4 | For 9 months |
| Comparative example 3 | 56.2 | 6 months of |
As shown in the table above, the antihypertensive injection-increasing agent prepared in the embodiment 1-3 of the invention obviously improves the effective rate, and the effective period is longer than 1 year.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. The pressure-reducing injection-increasing agent is characterized by comprising hydrophobic nano particles, a composite surfactant, an auxiliary agent and water;
the hydrophobic nano particles are silica nano hollow spheres with surfaces loaded with fluorine-containing groups and long-chain alkyl chains;
the auxiliary agent is at least one selected from polyethylene glycol, methanol, ethanol and glycerol.
2. The pressure reducing and injection increasing agent according to claim 1 is characterized by being prepared from the following raw materials in parts by weight: 2-3 parts of hydrophobic nano particles, 10-15 parts of composite surfactant, 0.5-5 parts of auxiliary agent and 40-50 parts of water.
3. The pressure reducing and injection increasing agent according to claim 1, wherein said complex surfactant comprises an anionic surfactant and a cationic surfactant.
4. The pressure reducing and injection increasing agent according to claim 3, wherein the anionic surfactant is at least one selected from the group consisting of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium tetradecyl sulfide, sodium tetradecyl sulfonate, sodium tetradecyl benzene sulfonate, sodium hexadecyl sulfate, sodium octadecyl sulfonate, sodium octadecyl benzene sulfonate, and sodium octadecyl sulfate; the cationic surfactant is at least one selected from cetyltrimethylammonium bromide, dodecyltrimethylammonium chloride, cetyltrimethylammonium chloride, cetyldimethylbenzyl ammonium chloride and octadecyltrimethylammonium bromide.
5. The pressure-reducing and injection-increasing agent according to claim 3, wherein the composite surfactant is sodium octadecyl sulfate and cetyltrimethylammonium bromide, and the mass ratio is 2:5-10.
6. The pressure reducing and injection increasing agent according to claim 1, wherein the hydrophobic nano-particles are prepared by the following steps:
s1, adding aminosilane, fluorine-containing silane and long-chain alkylsilane into an organic solvent to obtain an oil phase;
s2, adding the aqueous solution containing the surfactant into the oil phase in the step S1, emulsifying, stirring for reaction, centrifuging, washing and drying to obtain the hydrophobic nano particles.
7. The pressure reducing and injection increasing agent according to claim 6, wherein the aminosilane is at least one selected from the group consisting of gamma-aminopropyl trimethoxysilane, gamma-aminopropyl triethoxysilane, N-beta (aminoethyl) -gamma-aminopropyl trimethoxysilane, N-beta (aminoethyl) -gamma-aminopropyl triethoxysilane, N-beta (aminoethyl) -gamma-aminopropyl methyldimethoxysilane, N-beta (aminoethyl) -gamma-aminopropyl methyldiethoxysilane, diethylenetriaminopropyl trimethoxysilane; the fluorine-containing silane is selected from 1H, 2H-perfluoro decyl triethoxysilane, 1H, 2H-perfluoro decyl trimethoxysilane, dodecafluoro heptyl propyl methyl dimethoxy silane 3, 3-trifluoropropyl methyl dimethoxy silane, 3-trifluoropropyl trimethoxy silane at least one of 1h,2 h-perfluorooctyltriethoxysilane or 1h,2 h-perfluorooctyltrimethoxysilane; the long-chain alkyl silane is at least one selected from hexadecyl dimethyl chlorosilane, octadecyl silane and dodecyl silane; the surfactant is at least one selected from Tween-20, tween-40, tween-60 and Tween-80; the organic solvent is at least one selected from dichloromethane, chloroform, petroleum ether, ethyl acetate, methyl acetate, butyl acetate, cyclohexane and toluene.
8. The pressure reducing and injection increasing agent according to claim 6, wherein in the step S1, the mass ratio of the aminosilane, the fluorine-containing silane and the long-chain alkylsilane is 10-15:3-5:4-7.
9. The pressure-reducing and injection-increasing agent according to claim 6, wherein the concentration of the aqueous solution containing the surfactant in the step S2 is 3-5wt%, the mass ratio of the aqueous solution containing the surfactant to the oil phase is 2-4:5-7, and the stirring reaction time is 3-5 hours.
10. A method for preparing the antihypertensive injection-increasing agent as claimed in any one of claims 1 to 9, comprising the steps of: dissolving the composite surfactant and the auxiliary agent in water, heating to 40-45 ℃, adding the hydrophobic nano particles, and performing 1000-1200W ultrasonic dispersion for 10-15min to prepare the pressure-reducing injection-increasing agent.
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Cited By (2)
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| CN117903774A (en) * | 2024-03-18 | 2024-04-19 | 山东海嘉石油化工有限公司 | Antihypertensive injection-increasing active agent and preparation method and application thereof |
| CN117903774B (en) * | 2024-03-18 | 2024-05-24 | 山东海嘉石油化工有限公司 | Antihypertensive injection-increasing active agent and preparation method and application thereof |
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| CN111944506A (en) * | 2020-09-01 | 2020-11-17 | 宁波锋成先进能源材料研究院有限公司 | Blood pressure-reducing injection-increasing active agent and preparation method thereof |
| CN112852395A (en) * | 2021-01-19 | 2021-05-28 | 中海油田服务股份有限公司 | Liquid for increasing injection, preparation method and application thereof |
| CN113150763A (en) * | 2021-04-26 | 2021-07-23 | 北京富达鑫辉能源科技有限公司 | Nano emulsion injection-increasing agent for water injection and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117903774A (en) * | 2024-03-18 | 2024-04-19 | 山东海嘉石油化工有限公司 | Antihypertensive injection-increasing active agent and preparation method and application thereof |
| CN117903774B (en) * | 2024-03-18 | 2024-05-24 | 山东海嘉石油化工有限公司 | Antihypertensive injection-increasing active agent and preparation method and application thereof |
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