CN111154468B - Selective water shutoff agent for oilfield water shutoff - Google Patents
Selective water shutoff agent for oilfield water shutoff Download PDFInfo
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- CN111154468B CN111154468B CN202010010191.5A CN202010010191A CN111154468B CN 111154468 B CN111154468 B CN 111154468B CN 202010010191 A CN202010010191 A CN 202010010191A CN 111154468 B CN111154468 B CN 111154468B
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- C09K8/506—Compositions based on water or polar solvents containing organic compounds
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Abstract
The invention discloses a selective water shutoff agent for oilfield water shutoff, which comprises ionic liquid synthesized by the reaction of tertiary amine and long-chain fatty acid; the tertiary amine is one of diethylenetriamine, triethylamine, tri-N-propylamine, triethanolamine, N-dimethylbutylamine and N, N-dimethylcyclohexylamine; the long-chain fatty acid is one of capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, arachidic acid and erucic acid; the ionic liquid is prepared by mixing tertiary amine and long-chain fatty acid, stirring, and reacting at 60-100 deg.C for 24 hr. The water shutoff agent also comprises one or at least two of component ionic liquid, synergist, cosurfactant and stabilizer. The synergist is one of a first synergist and a second synergist, wherein the first synergist is organic acid, and the second synergist is one of m-phenylenediamine, ethylenediamine, 1, 8-octanediamine, 1, 2-propanediamine and the like. The water plugging agent disclosed by the invention is subjected to self-assembly in a water phase, so that the viscosity is rapidly increased, and a water layer is plugged, and the effect of plugging water and not plugging oil is finally achieved.
Description
Technical Field
The invention relates to the technical field of oilfield development, in particular to the technical field of oil-water well production increase and injection increase such as oil-water well plugging regulation and profile control, water plugging and channeling sealing and the like, and specifically relates to a water plugging non-plugging oil type ionic liquid water plugging agent.
Background
Oil well water production is a serious problem facing water injection wells. According to statistics, the comprehensive water content of main oil fields in China is as high as 83%, and the comprehensive water content of main oil fields in the east is over 90%. For an oil field developed by long-term water injection, due to the heterogeneity of the oil reservoir plane and the longitudinal direction and the difference of oil-water viscosity, the injected water is forced to rush into and flow through a production well along a high permeability zone, so that the low-efficiency or ineffective circulation of the injected water is caused, the produced amount of crude oil is influenced, energy is consumed, the treatment cost of the produced liquid is increased, the corrosion of pipelines is caused, and the like, and the crude oil production cost is increased and the environmental pollution is caused. Therefore, how to effectively find and block water becomes a serious problem in the development of oil fields.
With the increasing difficulty of oil field exploitation, the existing water plugging process of the oil field is difficult to accurately judge the water cone path and the mode, and is difficult to comprehensively know the shape, the distribution, the liquid property and the geology of an oil layer, so that the water plugging operation is difficult to achieve an ideal effect. Common problems are: 1) water and oil are blocked together; 2) water is blocked, but the oil yield is obviously reduced, and the oil layer is seriously damaged; 3) the water plugging duration is short, namely the water plugging agent has low strength and is easy to be drained back by water; 4) poor temperature resistance, weak corrosion resistance and short aging period, namely, the water shutoff agent is quickly out of service under the stratum condition; 5) the water cone inside the oil layer, the water finger-feed, or the water in the same oil-water layer or the interlayer water in the oil layer are dare not to block, are afraid of blocking the oil-gas channel, and the like. Therefore, a new method or process is sought for preparing the effective water-plugging oil-plugging-free water plugging agent, so that the crude oil recovery rate is further improved, and the method has extremely important research and application values.
Disclosure of Invention
The invention aims to solve the problem that the water and the oil are blocked together in the existing water blocking agent, and provides a selective water blocking agent which can not block the water and the oil.
The main agent of the selective water shutoff agent for oilfield water shutoff is ionic liquid, and the ionic liquid is ionic liquid synthesized by the reaction of tertiary amine and long-chain fatty acid; the tertiary amine is one of diethylenetriamine, triethylamine, tri-N-propylamine, triethanolamine, N-dimethylbutylamine and N, N-dimethylcyclohexylamine; the long-chain fatty acid is one of capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, arachidic acid and erucic acid. The ionic liquid is prepared by mixing and stirring tertiary amine and long-chain fatty acid according to the molar ratio of 1 (1-1.5) and reacting for 24 hours at the temperature of 60-100 ℃. The ionic liquid can be independently used as a water shutoff agent. Can also be matched with other auxiliary agents for use, thereby achieving better water shutoff effect.
The adjuvant is one or at least two of a synergist, a cosurfactant and a stabilizer.
The synergist is an organic acid or a diamine compound, and the organic acid is one of citric acid, oxalic acid, maleic acid, phthalic acid, succinic acid, tartaric acid and glutamic acid; the diamine compound is one of m-phenylenediamine, ethylenediamine, 1, 8-octanediamine, 1, 2-propanediamine, cis-1, 2-cyclohexanediamine and N, N-diisopropyl ethylenediamine, and is used for adjusting a colloid structure.
The cosurfactant is one of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, 1-hexanol, 2-hexanol, 1-octanol, 2-octanol, fusel oil and paranonyl phenol and is used for adjusting the gel forming strength.
The stabilizer is one of methylcellulose, cellulose acetate butyrate, hydroxypropyl methylcellulose, cellulose acetate phthalate, xanthan gum, gelatin, guar gum and carrageenan, and is used for adjusting the colloid strength.
Preferably, the selective water shutoff agent for oilfield water shutoff is prepared by mixing and compounding ionic liquid and a synergist, wherein the ionic liquid and the synergist are in mass percentage as follows: 80-90% of ionic liquid and 10-20% of synergist.
Preferably, the selective water shutoff agent for oilfield water shutoff is prepared by mixing and compounding ionic liquid, a synergist and a cosurfactant, and the mass percentages of the components are as follows: 80-90% of ionic liquid, 8-18% of synergist and 2-5% of cosurfactant.
Preferably, the selective water shutoff agent for oil field water shutoff is prepared by mixing and compounding ionic liquid, a synergist, a cosurfactant and a stabilizer; the mass percentages of the components are as follows: 80-90% of ionic liquid, 8-15% of synergist, 1-5% of cosurfactant and 1-3% of stabilizer.
Compared with the prior art, the invention has the advantages that:
the water shutoff agent mainly adopts the ionic liquid, the ionic liquid is a molten salt system which is composed of specific cations and anions and is in a liquid state at room temperature or nearly room temperature, and the water shutoff agent has the characteristics of higher thermal stability, extremely low vapor pressure, low melting point, difficult volatilization, difficult combustion and the like. The formed water shutoff agent has water shutoff and oil non-shutoff type water shutoff agent, has good amphipathy, and can be dissolved in oil or water. After entering an oil layer, the water shutoff agent is dissolved in oil, and the viscosity is not increased; when the water plugging agent enters the water layer, the viscosity of the water plugging agent is rapidly increased through self-assembly in the water layer. The water layer is blocked, and the effect of blocking water and not blocking oil is finally achieved.
In addition, the preparation method of the water shutoff agent is simple, convenient and feasible, not only reduces the production cost and realizes environmental protection, but also has the property of effectively blocking water and oil, and is a novel water shutoff agent which is worth popularizing.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
Fig. 1 is a graph showing the results of a gelling experiment of the water shutoff agent prepared in example 1.
Figure 2 is a graph of shear viscosity versus shear rate for the gel formed by the water shutoff agent of example 1.
FIG. 3 shows the storage modulus (G ') and loss modulus (G') of the gel formed by the water shutoff agent of example 1 as a function of frequency.
FIG. 4 is a graph of shear viscosity versus shear rate for gels formed by the water shutoff agent of example 2.
The storage modulus (G ') and loss modulus (G') of the gel formed by the water shutoff agent of example 2 are plotted against frequency in FIG. 5.
Fig. 6 is a graph showing the relationship between the shear viscosity and the shear rate of the gel formed by the water-plugging agent of example 3.
Storage modulus (G '), loss modulus (G') of the gel formed by the water shutoff agent of FIG. 7 and example 3, as a function of frequency.
Fig. 8 is a graph of shear viscosity versus shear rate for gels formed with the water shutoff agent of example 4.
FIG. 9, storage modulus (G ') and loss modulus (G') of the gel formed by the water-plugging agent of example 4, as a function of frequency.
Fig. 10 is a graph showing the relationship between the shear viscosity and the shear rate of the gel formed by the water-plugging agent of example 5.
FIG. 11, storage modulus (G ') and loss modulus (G') of the gel formed by the water-plugging agent of example 5, as a function of frequency.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example 1
The selective water shutoff agent for oil field water shutoff is an ionic liquid prepared by mixing triethylamine and oleic acid for reaction.
The preparation method of the ionic liquid comprises the following steps: mixing N, N-dimethylcyclohexylamine and oleic acid according to the weight ratio of 1:1.03, magnetically stirring, and reacting at 80 ℃ for 24h to form the water-plugging oil-free water plugging agent based on the ionic liquid.
The performance test of the water shutoff agent is as follows:
(1) and (3) testing a gelling experiment: taking 45 parts of distilled water, 10 parts of a water plugging agent and 45 parts of n-hexane in 100 parts by weight; dissolving a water plugging agent in oil-phase n-hexane at room temperature; then slowly adding the prepared n-hexane solution into a cylindrical experimental bottle filled with pure water, sealing by a cover, standing for 30min, and beginning to form a high-strength gel at an oil-water interface; the experimental bottle was then inverted and it was seen that the oil phase dropped under gravity to the bottle cap portion while the water phase remained in the bottle bottom unchanged in position due to the high strength gel formed at the oil-water interface sealing the water phase at the bottle bottom. The experimental phenomenon is shown in figure 1. After the oil phase and the water phase are contacted, gel with high strength can be generated at the oil-water interface within 30 minutes to 6 hours, and the water phase is effectively blocked.
(2) The gel formed at the oil-water interface was subjected to rheological testing. And (3) testing conditions are as follows: the test was carried out at a test temperature of 25 ℃ using an HAAKE MARSIII rheometer (Thermo Fisher, usa) with a test gap of 1mm under constant stress τ of 1Pa and time t of 10 min. The test results are shown in FIG. 2.As can be seen from FIG. 2, the temperature is 0.01s -1 The viscosity is close to 1000000 mPas. As can be seen from FIG. 3, with the increase of the shearing time, the storage modulus G ' is basically unchanged, G ' floats around 3000Pa, and the dissipation modulus G ' is stabilized within the range of 400-900 Pa. Under the condition, the viscoelasticity of the gel is not changed, and the gel structure is not damaged.
Example 2
The selective water shutoff agent for oil field water shutoff is an ionic liquid prepared by mixing triethylamine and oleic acid for reaction.
The preparation method of the ionic liquid comprises the following steps: mixing triethylamine and oleic acid according to the weight ratio of 1:1.05, magnetically stirring, and reacting at 90 ℃ for 24 hours to form the water-plugging oil-free water plugging agent based on the ionic liquid.
The performance test of the water shutoff agent is as follows:
(1) testing a gelling experiment: test results the phenomenon was the same as that of the water shutoff agent of example 1.
(2) The gel formed at the oil-water interface was subjected to rheological testing. And (3) testing conditions are as follows: the test was carried out at a test temperature of 25 ℃ using an HAAKE MARSIII rheometer (Thermo Fisher, usa) with a test gap of 1mm under constant stress τ of 1Pa and time t of 10 min. The test results are shown in fig. 4 and 5. As can be seen from the figure, it is at 0.01s -1 When the viscosity of the gel is about 300000 mPas. With the increase of the shearing time, the storage modulus G ' is basically unchanged, G ' floats at about 10Pa, and the dissipation modulus G ' is stabilized at about 3 Pa. Under the condition, the viscoelasticity of the gel is not changed, and the gel structure is not damaged.
Example 3
A selective water shutoff agent for oilfield water shutoff consists of ionic liquid and citric acid as synergist. The ionic liquid is prepared by mixing and reacting triethanolamine and stearic acid. The mass percentages of the ionic liquid and the synergist are as follows: 90% of ionic liquid and 10% of synergist.
The preparation method of the ionic liquid comprises the following steps: mixing triethanolamine and stearic acid at a weight ratio of 1:1.5, magnetically stirring, and reacting at 90 deg.C for 24h to form ionic liquid. Mixing the ionic liquid and the citric acid according to the mass percentage to prepare the water-plugging oil-free water plugging agent.
The performance test of the water shutoff agent is as follows:
(1) and (3) testing a gelling experiment: the test procedure is as in example 1, except that n-hexane is simply replaced by n-heptane; the phenomenon was the same as that of the water-plugging agent of example 1.
(2) The gel formed at the oil-water interface was subjected to rheological testing. And (3) testing conditions are as follows: the test was carried out at a test temperature of 25 ℃ using an HAAKE MARSIII rheometer (Thermo Fisher, usa) with a test gap of 1mm under constant stress τ of 1Pa and time t of 10 min. The test results are shown in fig. 6 and 7. As can be seen from the figure, the same is true at 0.01s -1 The gel viscosity is close to 1000000 mPas. With the increase of the shearing time, the storage modulus G ' is basically unchanged, G ' floats around 1000Pa, and the dissipation modulus G ' is stabilized around 150 Pa. Under the condition, the viscoelasticity of the gel is not changed, and the gel structure is not damaged. Experiments of the inventor show that the performance test result of the gel obtained by replacing citric acid with other acidic synergists such as oxalic acid, maleic acid, phthalic acid and the like is similar to the performance test result of the gel obtained by using citric acid.
Example 4
A selective water shutoff agent for oil field water shutoff consists of ionic liquid, synergist cis-1, 2-cyclohexanediamine and cosurfactant p-nonyl phenol. The ionic liquid is prepared by mixing and reacting triethanolamine with stearic acid. The mass percentages of the ionic liquid and the synergist are as follows: 80% of ionic liquid, 16% of synergist and 4% of p-nonyl phenol.
The preparation method of the ionic liquid comprises the following steps: mixing tri-n-propylamine with arachidic acid according to the weight ratio of 1:1.05, magnetically stirring, and reacting at 60 ℃ for 24h to form ionic liquid. Mixing the ionic liquid, cis-1, 2-cyclohexanediamine and p-nonyl phenol according to the mass percentage to prepare the water-plugging oil-free water plugging agent.
The performance test of the water shutoff agent is as follows:
(1) and (3) testing a gelling experiment: 45 parts of pure water, 5 parts of a water shutoff agent and 50 parts of n-heptane are taken based on 100 parts by weight. The experiment was carried out in accordance with the procedure of example 1, and the resulting phenomenon was the same as that of the water-plugging agent of example 1.
(2) The gel formed at the oil-water interface was subjected to rheological testing. And (3) testing conditions are as follows: the test was carried out at a test temperature of 25 ℃ using an HAAKE MARSIII rheometer (Thermo Fisher, usa) with a test gap of 1mm under constant stress τ of 1Pa and time t of 10 min. The test results are shown in fig. 8 and 9. As can be seen from the figure, it is at 0.01s -1 When the viscosity is close to 2000000 mPas. Along with the increase of the shearing time, the storage modulus G ' is basically unchanged, G ' floats around 2200Pa, and the dissipation modulus G ' is stabilized in the range of 30-300 Pa. Under the condition, the viscoelasticity of the gel is not changed, and the gel structure is not damaged.
Example 5
A selective water shutoff agent for oilfield water shutoff consists of ionic liquid, synergist m-phenylenediamine, co-surfactant n-propanol and stabilizer methylcellulose. The ionic liquid is prepared by mixing and reacting N, N-dimethylcyclohexylamine and erucic acid. The mass percentages of the ionic liquid and the synergist are as follows: 90% of ionic liquid, 8% of synergist, 1% of cosurfactant and 1% of stabilizer.
The preparation method of the ionic liquid comprises the following steps: mixing N, N-dimethylcyclohexylamine and erucic acid according to the weight ratio of 1:1.1, magnetically stirring, and reacting for 24 hours at 100 ℃ to form the ionic liquid. Mixing the ionic liquid, the m-phenylenediamine, the n-propanol and the methylcellulose according to the mass percentage to prepare the water-plugging oil-free water plugging agent.
The performance test of the water shutoff agent is as follows:
(1) testing a gelling experiment: based on 100 parts by weight, 40 parts of pure water, 5 parts of a water shutoff agent and 55 parts of n-heptane are taken. The experiment was carried out in accordance with the procedure of example 1, and the resulting phenomenon was the same as that of the water-plugging agent of example 1.
(2) The gel formed at the oil-water interface was subjected to rheological testing. And (3) testing conditions are as follows: the test was carried out at a test temperature of 25 ℃ using an HAAKE MARSIII rheometer (Thermo Fisher, usa) with a test gap of 1mm under constant stress τ of 1Pa and time t of 10 min. The test results are shown in fig. 10 and 11. As can be seen from the figure, it is at 0.01s -1 The gel viscosity is close to 1000000 mPas. Along with the increase of the shearing time, the storage modulus G ' is basically unchanged, G ' floats around 2200Pa, and the dissipation modulus G ' is stabilized in the range of 100-200 Pa. Under the condition, the viscoelasticity of the gel is not changed, and the gel structure is not damaged.
In conclusion, the selective water shutoff agent with water shutoff and oil non-shutoff functions is prepared by taking the specific ionic liquid as the main component. After entering an oil layer, the water shutoff agent is dissolved in oil, and the viscosity is not increased; when the water plugging agent enters the water layer, the viscosity of the water plugging agent is rapidly increased through self-assembly in the water layer. The water layer is blocked, and the effect of blocking water and oil without blocking oil is finally achieved. The preparation method is simple, convenient and feasible, has low production cost, realizes environmental friendliness, and is a novel water shutoff agent which is worth popularizing.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (7)
1. A selective water shutoff agent for oil field water shutoff is characterized by comprising ionic liquid synthesized by the reaction of tertiary amine and long-chain fatty acid; the ionic liquid is prepared by mixing and stirring tertiary amine and long-chain fatty acid according to the molar ratio of 1 (1-1.5) and reacting for 24 hours at the temperature of 60-100 ℃; the tertiary amine is one of triethylamine, tri-N-propylamine, triethanolamine, N-dimethylbutylamine and N, N-dimethylcyclohexylamine; the long-chain fatty acid is one of capric acid, lauric acid, myristic acid, palmitic acid, oleic acid, stearic acid, arachidic acid and erucic acid.
2. The selective water shutoff for water shutoff in oil fields of claim 1 further comprising a synergist; the synergist is organic acid or diamine compound, and the organic acid is one of citric acid, oxalic acid, maleic acid, phthalic acid, succinic acid, tartaric acid and glutamic acid; the diamine compound is one of m-phenylenediamine, ethylenediamine, 1, 8-octanediamine, 1, 2-propanediamine, cis-1, 2-cyclohexanediamine and N, N-diisopropyl ethylenediamine.
3. The selective water shutoff agent for oilfield water shutoff according to claim 2, wherein the ionic liquid and the synergist are in the following mass percentages: 80-90% of ionic liquid and 10-20% of synergist.
4. The selective water shutoff agent for oil field water shutoff of claim 2 further comprising a co-surfactant, wherein the co-surfactant is one of an alcohol having no more than 8 carbon atoms, fusel oil, and paranonyl phenol.
5. The selective water shutoff agent for oilfield water shutoff according to claim 4, wherein the mass percentages of the components are as follows: 80-90% of ionic liquid, 8-18% of synergist and 2-5% of cosurfactant.
6. The selective water shutoff agent for oilfield water shutoff according to claim 4 further comprising a stabilizer, wherein the stabilizer is one of methylcellulose, cellulose acetate butyrate, hydroxypropyl methylcellulose, cellulose acetate phthalate, xanthan gum, gelatin, guar gum, and carrageenan.
7. The selective water shutoff agent for oilfield water shutoff according to claim 6, wherein the mass percentages of the components are as follows: 80-90% of ionic liquid, 8-15% of synergist, 1-5% of cosurfactant and 1-3% of stabilizer.
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