CN109251737B - Epoxy-phenolic aldehyde system water plugging agent for oil and gas field exploitation - Google Patents
Epoxy-phenolic aldehyde system water plugging agent for oil and gas field exploitation Download PDFInfo
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- CN109251737B CN109251737B CN201811134758.9A CN201811134758A CN109251737B CN 109251737 B CN109251737 B CN 109251737B CN 201811134758 A CN201811134758 A CN 201811134758A CN 109251737 B CN109251737 B CN 109251737B
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Abstract
The invention discloses an epoxy-phenolic aldehyde system water shutoff agent used for oil-gas field exploitation, which adopts a novel water shutoff agent consisting of epoxy resin as a resin matrix, linear phenolic aldehyde resin as a curing agent, imidazole type accelerant and alcohols and ketones as migratory diluents. The migratory diluent can greatly reduce the viscosity of the water shutoff agent and ensure the transportability of the water shutoff agent; upon contact with formation water, the migratable diluent migrates into the aqueous phase, while the other components of the system settle to the bottom of the aqueous phase, achieving effective solidification. The addition of the migratable diluent can reduce the adverse effect of the diluent on the curing process and the performance of the cured product, thereby realizing the adjustable curing time and ensuring the mechanical strength of the cured product. The water plugging agent disclosed by the invention has the characteristics of low viscosity, good pouring fluidity, wide application temperature range, adjustable curing speed and high strength after curing, and still has excellent plugging performance in high-temperature, high-salt, acidic and alkaline environments.
Description
Technical Field
The invention relates to a water shutoff agent used in the process of oil and gas field exploitation, in particular to an epoxy-phenolic aldehyde system water shutoff agent used in the severe underground environment of oil and gas field exploitation.
Background
In the process of exploiting oil and gas fields, some oil and gas wells are exposed to water or flooded by water in advance due to water layer channeling, bottom water coning or water injection and edge water inrush. In order to remove or reduce flooding, control the flow of water in the producing zone and enhance oil and gas recovery, water plugging agents are typically used to plug the water producing interval of a producing well or an injection well. The water produced by oil and gas field is a ubiquitous problem, and the water shutoff agent is a main means for solving the problem at present and is an important means for improving the oil and gas recovery rate and the economic benefit. The water shutoff agent used in the early stage, namely the traditional water shutoff agent mainly comprises a cement water shutoff agent and a precipitation water shutoff agent, and the cement water shutoff agent is easy to be diluted by water and difficult to be solidified and molded; the sediment water shutoff agent has poor mobility and is not easy to enter a water outlet crack to block water outlet, so that the improvement of the oil gas recovery ratio through water injection is restricted. In order to overcome the defects of cement water shutoff agents and precipitation water shutoff agents, polymer gel water shutoff agents are developed later. Although the polymer gel water shutoff agent can overcome the defects of cement water shutoff agents and precipitation water shutoff agents, the strength of the polymer gel water shutoff agent is low, and an ideal water shutoff effect is difficult to realize in a severe underground environment. Therefore, the oil and gas field exploitation and production practice needs to provide a water plugging agent which has good heat resistance, high strength, large performance adjustable space and good water plugging effect in severe underground environment so as to solve the problem of plugging the water outlet interval of the water-bearing oil and gas well.
Disclosure of Invention
Aiming at the defects of the water shutoff agent used in the exploitation of oil and gas fields in the prior art, the invention aims to provide a novel epoxy-phenolic aldehyde system water shutoff agent applicable to severe underground environment so as to solve the problem of plugging the water outlet layer section of the water-bearing oil and gas well.
Aiming at the problem of plugging a water outlet layer of a production well in oil and gas exploitation, the novel epoxy-based resin plugging agent provided by the invention adopts epoxy resin as a resin matrix, linear phenolic resin as a curing agent, imidazoles as an accelerator and alcohols and ketones as diluents to form an epoxy-phenolic curing system, so that the obtained plugging agent has the properties of low viscosity, wide application temperature range, adjustable curing speed, high strength after curing, good perfusion fluidity and wider applicability, and still has an excellent plugging effect under complex and harsh conditions such as high temperature, high salt content, acidity and alkalinity.
The epoxy-phenolic aldehyde system water shutoff agent for oil and gas field exploitation provided by the invention comprises the following raw material components, by mass, 45-80 parts of bisphenol F or/and bisphenol A epoxy resin, 10-50 parts of novolac resin, 0.01-0.05 part of imidazole accelerator, and 10-60 parts of migratable diluent.
In the epoxy-phenolic aldehyde system water shutoff agent, the content of the bisphenol F or/and bisphenol A epoxy resin is related to the time for injecting the water shutoff agent into the gel, the gel time of the water shutoff agent is related to the downhole temperature, the higher the temperature is, the faster the gel is, and vice versa, so that the content of the bisphenol F or/and bisphenol A epoxy resin is adjusted according to the downhole environment temperature, and when the downhole environment temperature is higher, the content of the bisphenol F or/and bisphenol A epoxy resin can be less, and vice versa, the content of the bisphenol F or/and bisphenol A epoxy resin can be higher. As the component epoxy resin, bisphenol F epoxy resin or bisphenol A epoxy resin may be used alone, or bisphenol F epoxy resin and bisphenol A epoxy resin may be used simultaneously. For the latter, the bisphenol F epoxy resin and the bisphenol a epoxy resin may be in any ratio, but preferably, the bisphenol F epoxy resin is used in an amount of not more than 45 parts and the bisphenol a epoxy resin is used in an amount of not more than 65 parts. The bisphenol F epoxy resin and the bisphenol A epoxy resin are preferably bisphenol F epoxy resin and bisphenol A epoxy resin with the epoxy equivalent of 150-230 g/mol.
In the epoxy-phenolic aldehyde system water shutoff agent used for oil and gas field exploitation, the content of the migratable diluent is related to the viscosity of the water shutoff agent, the higher the content of the migratable diluent is, the lower the viscosity of the water shutoff agent is, so that the filling of the water shutoff agent is facilitated, meanwhile, the viscosity of the water shutoff agent is related to the filling environment temperature of the water shutoff agent, the filling environment temperature is high, the viscosity of the water shutoff agent is low, otherwise, the filling environment temperature is low, and the viscosity of the water shutoff agent is high. Therefore, the content of the migratable diluent is adjusted according to the temperature of the environment for pouring the water shutoff agent. The migratable diluent is preferably methanol, ethanol, acetone, butanone, and n-butanol.
The epoxy-phenolic aldehyde system water shutoff agent for oil and gas field exploitation provided by the invention has the advantages that the migratable diluent can greatly reduce the viscosity of the system, and the epoxy-phenolic aldehyde resin system water shutoff agent has good transportability; and after the water shutoff agent contacts the formation water, the migratable diluent can migrate to the water phase, and other components in the system can settle to the bottom of the water phase, so that effective solidification is realized. The addition of the migratable diluent can reduce the adverse effect of the diluent on the curing process and the performance of the cured product, thereby realizing the adjustable curing time and ensuring the mechanical strength of the cured product.
In order to prove that the epoxy-phenolic aldehyde system water plugging agent for oil and gas field exploitation provided by the invention has excellent performance, an inventor conducts an underground environment simulation experiment on the water plugging agent, namely resin slurry obtained by fully mixing all components of the water plugging agent is poured into a hydrothermal kettle filled with water, and a curing experiment is conducted at different temperature points within the range of 100-150 ℃ after sealing, gel curing can be realized, the gel time can be adjusted within 0.5-9 hours, and the water plugging agent is suitable for plugging of an oil and gas well water outlet section layer with the underground environment temperature within the range of 100-150 ℃.
The water shutoff agent system provided by the invention has the characteristics of low viscosity, wide application temperature range, adjustable curing speed, high strength after curing, good perfusion fluidity, wide applicability, and excellent performance under complex and harsh conditions such as high temperature, high salinity, acidity and alkalinity, and has the following outstanding advantages and technical effects compared with the water shutoff agent in the prior art in summary:
1. the water plugging agent disclosed by the invention is very low in viscosity before solidification, has excellent fluidity, is beneficial to pouring and conveying of the water plugging agent, and can meet the requirement of plugging water discharged from a deep well layer.
2. The water shutoff agent can be cured at the temperature of 100-150 ℃, has the characteristic of adjustable gel time within 0.5-9 hours, and has wide applicability.
3. The water plugging agent can well complete solidification under the harsh conditions of high salt, high water content, acidity, alkalinity and the like, and a condensate has high compressive strength and excellent mechanical property.
Drawings
FIG. 1 is a curve showing the change of the viscosity of the water shutoff agent of the resin system according to the present invention with the types and amounts of the diluents under the conditions that the amounts of the bisphenol A epoxy resin and the phenolic resin are 45 parts and 30 parts, respectively.
FIG. 2 is a curve showing the change of the viscosity of the resin system water shutoff agent according to the invention with the types and amounts of the diluents under the condition that the amounts of the bisphenol F epoxy resin and the phenolic resin are 45 parts and 30 parts, respectively.
FIG. 3 is a curve showing the change of the viscosity of the water shutoff agent of the resin system according to the present invention with the addition of the phenolic resin under the conditions that the addition amounts of the bisphenol A epoxy resin and the diluent methanol are 45 parts and 30 parts, respectively.
FIG. 4 is a curve showing the change of the viscosity of the water shutoff agent of the resin system according to the present invention with the addition of the phenolic resin under the conditions that the addition amounts of the bisphenol F epoxy resin and the diluent methanol are 45 parts and 30 parts, respectively.
As can be seen from fig. 1 to 4, the viscosity of the system increases with the addition amount of the phenol resin regardless of the use of the bisphenol a type or bisphenol F type epoxy resin. However, by adding a diluent, the viscosity of the system can be greatly reduced. Among them, methanol and acetone have more excellent diluting effect than other alcohol and ketone diluents because of their extremely low viscosity and excellent solubility in epoxy systems. By adjusting the viscosity of the slurry, the viscosity of the slurry can be reduced to 50mpa.s or less, and excellent fluidity of the resin system can be exhibited.
Figure 5 is a graph of the change of the curing time of water shutoff agent formulations at different temperatures with different amounts of accelerator added.
As shown in FIG. 5, at 110-130 ℃, the amount of accelerator required to reach the same curing time is gradually reduced with the temperature rise, but the difference is not large; when the temperature is increased to 140 ℃ and 150 ℃, the amount of the accelerator required for reaching the same curing time is reduced sharply, and the difference between the amounts of the accelerators required for different curing times is smaller and smaller, which shows that the difficulty in accurately regulating and controlling the curing time is greatly increased at the high temperature of 150 ℃, but the curing can still be ensured to be completed within 3-7 h.
FIG. 6-1 is a graph showing the change of the setting time of the water shutoff agent in different brines; FIG. 6-2 is a curve showing the change of the curing time of the water shutoff agent of the present invention at different pH values.
As shown in FIGS. 6-1 and 6-2, in CaCl2、MgCl2、MgSO4In the saturated solution, the curing time of the water plugging agent of the invention is not obviously changed compared with that of pure water. This result indicates that the above-mentioned brine does not have a significant effect on the setting time of the water shutoff agent, indicating that the water shutoff agent can still be effectively cured in brine. And saturated NaHCO3The solution is alkaline, the epoxy ring opening is easier to carry out, and the curing time of the system is shortened to a certain extent.
The influence of the pH value on the curing time of the water plugging agent is obvious. When the pH value is 5-7, the curing time of the system is not obviously changed; when the pH is lowered to 4-5, the curing time of the system is significantly prolonged. This is because the acidic environment will weaken the accelerating effect of the imidazole compounds on the curing reaction, which in turn will result in a prolonged curing time. When the pH is 7-8, the curing time of the system is obviously shortened because the ring opening of the epoxy resin is more likely to occur under the alkaline condition.
Fig. 7 is a DMA test chart of cured water shutoff agent samples with bisphenol F epoxy resin as the matrix and different amounts of phenolic resin added.
Fig. 8 is a DMA test chart of cured water shutoff agent samples with bisphenol F epoxy resin as the matrix and different amounts of methanol diluent added.
As shown in fig. 7, the glass transition temperature of the resin water shutoff agent tends to increase and then decrease as the amount of the added phenol resin increases. The glass transition temperature of the resin sample reached the highest when the ratio of the epoxy resin to the phenolic resin was 45:30 parts added. The adding part ratio of the epoxy resin to the phenolic resin is lower than 45:30, and the dosage of the phenolic resin is excessive; otherwise, the epoxy resin is excessive. In both cases, the crosslink density of the cured resin product is reduced to some extent, which in turn leads to a reduction in the glass transition temperature.
As shown in FIG. 8, the more diluent is added, the lower the glass transition temperature of the resin sample. This is because in the presence of a large amount of diluent, although a part of the diluent is extracted by water after the system is mixed with water, in the presence of a large amount of diluent, a part of the diluent remains in the resin crosslinked network, resulting in a decrease in the density of the resin crosslinked network, resulting in a decrease in the glass transition temperature.
FIG. 9-1 is a compression curve of the plugging agent of the present invention under different brines; fig. 9-2 is a compression curve of the plugging agent of the present invention at different pH values.
FIG. 10 is a compression curve of a resin after curing in an environment with different water contents.
As shown in FIGS. 9-1 and 9-2, the compressive strength of the samples cured in different brines did not change significantly from the samples cured in pure water, indicating the excellent salt resistance of the resin system. The properties of the samples cured in a weak acid environment (pH 5-7) did not change significantly compared to the samples cured in pure water. When the pH is lowered to 4-5, a certain reduction in resin strength occurs. The acidic environment can weaken the accelerating effect of the imidazole compound on the curing reaction, and the epoxy resin can be incompletely cured while the curing reaction time is prolonged, so that the performance of the cured resin is reduced; the compressive strength of the sample after curing in a weakly alkaline environment is increased to some extent. This is because the alkaline environment can promote the epoxy curing, which improves the reaction degree and further improves the mechanical properties of the cured product.
As shown in fig. 10, the mechanical properties of the samples cured in the environments with different water contents showed a large difference. The compressive strength of the resin increases with increasing water content in the curing environment. After the water content reaches a certain value, the compressive strength is stabilized at a certain value and does not rise any more. Since the diluent in the system is miscible with water. After the resin system is mixed with water, a portion of the diluent is extracted by the water. In contrast, the epoxy and phenolic moieties of the resin system are insoluble in water and sink to the lower layer of the mixed liquor. When the water content is low, only a small portion of the diluent is extracted into the water. Most of the diluent remains in the epoxy novolac system, which in turn causes a decrease in the cross-linked network density after curing, resulting in a decrease in material strength. When the water content is higher, most of the diluent is extracted into water, so that the epoxy phenolic system can form a compact cross-linked network, and the high strength is realized.
FIG. 11 is a resin compression curve after curing and aging for one month in an aqueous environment with a 15% volume fraction of hydrogen sulfide.
As shown in fig. 11, the compression curve of the resin after curing and aging for one month in an aqueous environment with a 15% volume fraction of hydrogen sulfide has a significant difference compared to the compression curve of the sample that did not age. This is due to the increased brittleness of the resin samples after aging in high temperature, high sulfur and aqueous environments. Some fragmentation at the edge occurs during compression, but the sample body remains intact, resulting in the appearance of irregular compression curves. Nevertheless, the final complete fracture strength of the system can still reach 70MPa, and excellent ageing resistance is shown.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the examples are only for the purpose of further illustration, and are not to be construed as limiting the scope of the present invention, and that those skilled in the art can make insubstantial modifications and adaptations of the present invention based on the above disclosure.
The following tests were carried out on the samples of the resin water shutoff agents prepared in the following examples in the following manner:
1. viscosity measurement
The viscosity of the slurry was tested at 20-50 ℃ using an AR2000 torque rheometer.
2. Curing time test
The curing time of the plugging agent formulations with different accelerator addition amounts at different temperatures was tested: pouring the resin slurry into 6 hydrothermal kettles respectively, curing at the temperature of 100-150 ℃, opening one hydrothermal kettle every hour to observe the curing condition of the slurry, and determining that the resin is cured when the resin cannot flow.
3. Dynamic mechanical testing
The samples were subjected to dynamic mechanical testing in three-point bending mode using DMA Q800(TA instruments). The frequency was set at 1Hz and the temperature rise rate was 3 ℃/min.
4. Mechanical Property test
The samples were tested for compressibility using an universal mechanical testing machine (Instron 5567, US). The test method refers to GBT 1041-.
In the following examples, the parts and percentages of the respective constituent components are, unless otherwise specified, parts by mass and percentages by mass.
Example 1
45 parts of bisphenol F epoxy resin and 30 parts of novolac resin are melted and mixed, 0.03 part of imidazole accelerator and 30 parts of methanol are added, and the mixture is fully and uniformly stirred. To simulate an underground curing environment, a hydrothermal kettle was used as a reaction vessel. Pouring the resin slurry into a hydrothermal kettle filled with distilled water, sealing and curing at 130 ℃.
And (3) performance testing: the epoxy resin slurry obtained in example 1 had a viscosity of 48.5mPa.s measured at 25 ℃, a curing time of 5h and a compressive strength of 85 MPa.
Example 2
45 parts of bisphenol F epoxy resin and 30 parts of novolac resin are melted and mixed, 0.01 part of imidazole accelerator and 30 parts of methanol are added, and the mixture is fully and uniformly stirred. To simulate an underground curing environment, a hydrothermal kettle was used as a reaction vessel. Pouring the resin slurry into a hydrothermal kettle filled with distilled water, sealing and curing at 130 ℃.
And (3) performance testing: the epoxy resin slurry obtained in example 2 had a viscosity of 48.5mPa.s measured at 25 ℃, a curing time of 7h and a compressive strength of 82 MPa.
Example 3
45 parts of bisphenol F epoxy resin and 30 parts of novolac resin are melted and mixed, 0.05 part of imidazole accelerator and 30 parts of methanol are added, and the mixture is fully and uniformly stirred. To simulate an underground curing environment, a hydrothermal kettle was used as a reaction vessel. Pouring the resin slurry into a hydrothermal kettle filled with distilled water, sealing and curing at 130 ℃.
And (3) performance testing: the epoxy resin slurry obtained in example 3 had a viscosity of 48.5mPa.s measured at 25 ℃, a curing time of 3h and a compressive strength of 90 MPa.
Example 4
45 parts of bisphenol F epoxy resin and 30 parts of novolac resin are melted and mixed, 0.03 part of imidazole accelerator and 30 parts of methanol are added, and the mixture is fully and uniformly stirred. To simulate an underground curing environment, a hydrothermal kettle was used as a reaction vessel. Pouring the resin slurry into a hydrothermal kettle filled with distilled water, sealing and curing at 110 ℃.
And (3) performance testing: the epoxy resin slurry obtained in example 4 had a viscosity of 48.5.mPa.s, a curing time of 7 hours and a compressive strength of 72MPa measured at 25 ℃.
Example 5
45 parts of bisphenol F epoxy resin and 30 parts of novolac resin are melted and mixed, 0.01 part of imidazole accelerator and 30 parts of methanol are added, and the mixture is fully and uniformly stirred. To simulate an underground curing environment, a hydrothermal kettle was used as a reaction vessel. Pouring the resin slurry into a hydrothermal kettle filled with distilled water, sealing and curing at 150 ℃.
And (3) performance testing: the epoxy resin slurry obtained in example 5 had a viscosity of 48.5 mPas measured at 25 ℃, a curing time of 3 hours and a compressive strength of 88 MPa.
Example 6
45 parts of bisphenol F epoxy resin and 30 parts of novolac resin are melted and mixed, 0.03 part of imidazole accelerator and 10 parts of methanol are added, and the mixture is fully and uniformly stirred. To simulate an underground curing environment, a hydrothermal kettle was used as a reaction vessel. Pouring the resin slurry into a hydrothermal kettle filled with distilled water, sealing and curing at 130 ℃.
And (3) performance testing: the epoxy resin slurry obtained in example 6 had a viscosity of 118.4mPa.s measured at 25 ℃, a curing time of 4h and a compressive strength of 90 MPa.
Example 7
45 parts of bisphenol F epoxy resin and 30 parts of novolac resin are melted and mixed, 0.03 part of imidazole accelerator and 50 parts of methanol are added, and the mixture is fully and uniformly stirred. To simulate an underground curing environment, a hydrothermal kettle was used as a reaction vessel. Pouring the resin slurry into a hydrothermal kettle filled with distilled water, sealing and curing at 130 ℃.
And (3) performance testing: the epoxy resin slurry obtained in example 7 had a viscosity of 28.1mPa.s measured at 25 ℃, a curing time of 6 hours and a compressive strength of 76 MPa.
Example 8
45 parts of bisphenol F epoxy resin and 15 parts of novolac resin are melted and mixed, 0.03 part of imidazole accelerator and 30 parts of methanol are added, and the mixture is fully and uniformly stirred. To simulate an underground curing environment, a hydrothermal kettle was used as a reaction vessel. Pouring the resin slurry into a hydrothermal kettle filled with distilled water, sealing and curing at 130 ℃.
And (3) performance testing: the epoxy resin slurry obtained in example 8 had a viscosity of 27.0mPa.s measured at 25 ℃, a curing time of 6 hours and a compressive strength of 69 MPa.
Example 9
45 parts of bisphenol F epoxy resin and 40 parts of novolac resin are melted and mixed, 0.03 part of imidazole accelerator and 30 parts of methanol are added, and the mixture is fully and uniformly stirred. To simulate an underground curing environment, a hydrothermal kettle was used as a reaction vessel. Pouring the resin slurry into a hydrothermal kettle filled with distilled water, sealing and curing at 130 ℃.
And (3) performance testing: the epoxy resin slurry obtained in example 9 had a viscosity of 78.0mPa.s measured at 25 ℃, a curing time of 5 hours and a compressive strength of 71 MPa.
Example 10
45 parts of bisphenol F epoxy resin and 30 parts of novolac resin are melted and mixed, 0.03 part of imidazole accelerator and 30 parts of acetone are added, and the mixture is fully and uniformly stirred. To simulate an underground curing environment, a hydrothermal kettle was used as a reaction vessel. Pouring the resin slurry into a hydrothermal kettle filled with distilled water, sealing and curing at 130 ℃.
And (3) performance testing: the epoxy resin slurry obtained in example 10 had a viscosity of 40.7mPa.s measured at 25 ℃, a curing time of 5 hours and a compressive strength of 65 MPa.
Example 11
45 parts of bisphenol F epoxy resin and 30 parts of novolac resin are melted and mixed, 0.03 part of imidazole accelerator and 30 parts of methanol are added, and the mixture is fully and uniformly stirred. To simulate an underground curing environment, a hydrothermal kettle was used as a reaction vessel. Pouring the resin slurry into a hydrothermal kettle filled with distilled water, adjusting the Ph of the system to be 4-5, and curing at 130 ℃ after sealing.
And (3) performance testing: the epoxy resin slurry obtained in example 11 had a viscosity of 48.5mPa.s measured at 25 ℃, a curing time of 7 hours and a compressive strength of 73 MPa.
Example 12
45 parts of bisphenol F epoxy resin and 30 parts of novolac resin are melted and mixed, 0.03 part of imidazole accelerator and 30 parts of methanol are added, and the mixture is fully and uniformly stirred. To simulate an underground curing environment, a hydrothermal kettle was used as a reaction vessel. Pouring the resin slurry into a hydrothermal kettle filled with distilled water, adjusting the Ph of the system to be 5-6, and curing at 130 ℃ after sealing.
And (3) performance testing: the epoxy resin slurry obtained in example 12 had a viscosity of 48.5mPa.s measured at 25 ℃, a curing time of 5 hours and a compressive strength of 88 MPa.
Example 13
45 parts of bisphenol F epoxy resin and 30 parts of novolac resin are melted and mixed, 0.03 part of imidazole accelerator and 30 parts of methanol are added, and the mixture is fully and uniformly stirred. To simulate an underground curing environment, a hydrothermal kettle was used as a reaction vessel. Pouring the resin slurry into a hydrothermal kettle filled with distilled water, adjusting the Ph of the system to be 6-7, and curing at 130 ℃ after sealing.
And (3) performance testing: the epoxy resin slurry obtained in example 13 had a viscosity of 48.5mPa.s measured at 25 ℃, a curing time of 5 hours and a compressive strength of 90 MPa.
Example 14
45 parts of bisphenol F epoxy resin and 30 parts of novolac resin are melted and mixed, 0.03 part of imidazole accelerator and 30 parts of methanol are added, and the mixture is fully and uniformly stirred. To simulate an underground curing environment, a hydrothermal kettle was used as a reaction vessel. Pouring the resin slurry into a hydrothermal kettle filled with distilled water, adjusting the Ph of the system to be 7-8, and curing at 130 ℃ after sealing.
And (3) performance testing: the epoxy resin slurry obtained in example 14 had a viscosity of 48.5mPa.s measured at 25 ℃, a curing time of 3 hours and a compressive strength of 98 MPa.
Example 15
45 parts of bisphenol F epoxy resin and 30 parts of novolac resin are melted and mixed, 0.03 part of imidazole accelerator and 30 parts of methanol are added, and the mixture is fully and uniformly stirred. To simulate an underground curing environment, a hydrothermal kettle was used as a reaction vessel. Pouring the resin slurry into a hydrothermal kettle filled with saturated magnesium chloride solution, sealing and curing at 130 ℃.
And (3) performance testing: the epoxy resin slurry obtained in example 15 had a viscosity of 48.5mPa.s measured at 25 ℃, a curing time of 6 hours and a compressive strength of 82 MPa.
Example 16
45 parts of bisphenol F epoxy resin and 30 parts of novolac resin are melted and mixed, 0.03 part of imidazole accelerator and 30 parts of methanol are added, and the mixture is fully and uniformly stirred. To simulate an underground curing environment, a hydrothermal kettle was used as a reaction vessel. The resin slurry was poured into a hydrothermal kettle containing a saturated magnesium sulfate solution, sealed and cured at 130 ℃.
And (3) performance testing: the epoxy resin slurry obtained in example 16 had a viscosity of 48.5mPa.s measured at 25 ℃, a curing time of 5 hours and a compressive strength of 83 MPa.
Example 17
45 parts of bisphenol F epoxy resin and 30 parts of novolac resin are melted and mixed, 0.03 part of imidazole accelerator and 30 parts of methanol are added, and the mixture is fully and uniformly stirred. To simulate an underground curing environment, a hydrothermal kettle was used as a reaction vessel. Pouring the resin slurry into a hydrothermal kettle filled with saturated sodium bicarbonate solution, sealing, and curing at 130 ℃.
And (3) performance testing: the epoxy resin slurry obtained in example 17 had a viscosity of 48.5mPa.s measured at 25 ℃, a curing time of 3 hours and a compressive strength of 93 MPa.
Example 18
45 parts of bisphenol F epoxy resin and 30 parts of novolac resin are melted and mixed, 0.03 part of imidazole accelerator and 30 parts of methanol are added, and the mixture is fully and uniformly stirred. To simulate an underground curing environment, a hydrothermal kettle was used as a reaction vessel. Pouring the resin slurry into a hydrothermal kettle filled with saturated calcium chloride solution, sealing and curing at 130 ℃.
And (3) performance testing: the epoxy resin slurry obtained in example 18 had a viscosity of 48.5mPa.s as measured at 25 ℃, a curing time of 6 hours and a compressive strength of 91 MPa.
Example 19
25 parts of bisphenol F epoxy resin, 27 parts of bisphenol A epoxy resin and 30 parts of novolac resin are melted and mixed, 0.03 part of imidazole accelerator and 30 parts of methanol are added, and the mixture is fully and uniformly stirred. To simulate an underground curing environment, a hydrothermal kettle was used as a reaction vessel. Pouring the resin slurry into a hydrothermal kettle filled with distilled water, sealing and curing at 130 ℃.
And (3) performance testing: the epoxy resin slurry obtained in example 19 had a viscosity of 60.8mPa.s as measured at 25 ℃, a curing time of 5 hours and a compressive strength of 97 MPa.
Example 20
60 parts of bisphenol A epoxy resin and 30 parts of novolac resin are melted and mixed, 0.03 part of imidazole accelerator and 30 parts of methanol are added, and the mixture is fully and uniformly stirred. To simulate an underground curing environment, a hydrothermal kettle was used as a reaction vessel. Pouring the resin slurry into a hydrothermal kettle filled with distilled water, sealing and curing at 130 ℃.
And (3) performance testing: the epoxy resin slurry obtained in example 20 had a viscosity of 105.7mPa.s as measured at 25 ℃, a curing time of 5 hours and a compressive strength of 117 MPa.
Claims (5)
1. The application of the epoxy-phenolic aldehyde system in the water shutoff agent for oil and gas field exploitation is characterized in that the epoxy-phenolic aldehyde system comprises the following raw material components in parts by mass: 45-80 parts of bisphenol F or/and bisphenol A epoxy resin, 10-50 parts of novolac resin, 0.01-0.05 part of imidazole accelerator and 10-60 parts of migratory diluent; the migratable diluent is selected from the group consisting of methanol, ethanol, acetone, butanone, and n-butanol.
2. The use of the epoxy-phenolic aldehyde system in the water shutoff agent for oil and gas field exploitation according to claim 1, wherein when the epoxy resin is a combination of bisphenol F epoxy resin and bisphenol A epoxy resin, the amount of the bisphenol F epoxy resin is not more than 45 parts, and the amount of the bisphenol A epoxy resin is not more than 65 parts.
3. The use of the epoxy-phenolic aldehyde system in the production of water shutoff agents in oil and gas fields as claimed in claim 1 or 2, wherein the epoxy equivalent weight of the bisphenol F and bisphenol A epoxy resin is 150-230 g/mol.
4. Use of the epoxy-phenolic system according to claim 1 or 2 in oil and gas field production water shutoff agents, characterized in that the phenolic resin has a hydroxyl equivalent weight of 90-130 g/mol.
5. The use of the epoxy-phenolic system of claim 3 in oil and gas field production water shutoff agents wherein the phenolic resin has a hydroxyl equivalent weight of 90 to 130 g/mol.
Priority Applications (1)
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| CN110003864A (en) * | 2019-04-03 | 2019-07-12 | 新疆格瑞迪斯石油技术股份有限公司 | Leak stopping sealing agent and preparation method thereof in a kind of drilling fluid |
| CN110295034B (en) * | 2019-06-18 | 2021-03-09 | 西南石油大学 | Gas injection channeling-preventing agent for deep part of carbonate karst cave or hole oil reservoir and application method thereof |
| CN111500270A (en) * | 2019-12-30 | 2020-08-07 | 大庆石油管理局有限公司 | Efficient resin plugging liquid for underground well repair of oil-water well |
| CN114836182A (en) * | 2021-02-02 | 2022-08-02 | 中国石油天然气股份有限公司 | Water plugging and channeling sealing system and preparation method thereof |
| CN113025293B (en) * | 2021-05-20 | 2022-06-17 | 天津硕泽工程技术有限公司 | Epoxy resin self-generated particle profile adjusting system and application thereof |
| CN115873568A (en) * | 2021-09-27 | 2023-03-31 | 中国石油化工股份有限公司 | Water shutoff agent and water shutoff composition |
| CN116265563A (en) * | 2021-12-17 | 2023-06-20 | 中国石油天然气股份有限公司 | Binary composite resin sealing agent and preparation method and application thereof |
| CN115109571B (en) * | 2022-05-23 | 2023-10-24 | 四川捷贝通能源科技有限公司 | Temperature-control phase-change water shutoff agent and preparation method thereof |
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| WO2005085592A1 (en) * | 2004-03-03 | 2005-09-15 | Halliburton Energy Services, Inc. | Resin compositions and methods of using such resin compositions in subterranean applications |
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| CN102516963B (en) * | 2011-10-17 | 2013-07-31 | 中国石油天然气股份有限公司 | Chemical composite resin mounting agent for oil-water well casing restoration |
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