阅读说明：本技术 改性树脂及其在封堵剂中的应用、高温封堵剂及其在高温弃置井封堵中的应用 (Modified resin and application thereof in plugging agent, high-temperature plugging agent and application thereof in high-temperature abandoned well plugging ) 是由 耿学礼 苏延辉 史斌 黄毓祥 郑晓斌 徐鸿飞 高波 马西旗 张静 王超 江安 于 2021-08-30 设计创作，主要内容包括：本发明属于石油钻井工程化学剂技术领域,尤其涉及一种改性树脂及其应用、一种高温封堵剂及其应用。本发明提供的改性树脂,包括以下质量份数的组分：环氧树脂混合物95～105份,稀释剂10～20份,乳化剂5～15份,偶联剂4～8份,消泡剂1～3份；所述环氧树脂混合物由环氧树脂和水性环氧树脂组成,所述溶剂型环氧树脂和水性环氧树脂的质量比为(1～3):(1～5)。以本发明提供的改性树脂为关键组分得到的抗高温无固相封堵剂克服了纯树脂体系在超高温条件易出现闪凝现象,稠化时间变短,不能保障封堵体系的稳定性问题。(The invention belongs to the technical field of petroleum drilling engineering chemical agents, and particularly relates to a modified resin and application thereof, and a high-temperature plugging agent and application thereof. The modified resin provided by the invention comprises the following components in parts by mass: 95-105 parts of epoxy resin mixture, 10-20 parts of diluent, 5-15 parts of emulsifier, 4-8 parts of coupling agent and 1-3 parts of defoaming agent; the epoxy resin mixture consists of epoxy resin and water-based epoxy resin, and the mass ratio of the solvent-based epoxy resin to the water-based epoxy resin is (1-3) to (1-5). The high-temperature-resistant solid-free plugging agent obtained by taking the modified resin provided by the invention as a key component solves the problems that a pure resin system is easy to generate a flash coagulation phenomenon under an ultrahigh-temperature condition, the thickening time is shortened, and the stability of the plugging system cannot be guaranteed.)

1. The modified resin is characterized by comprising the following components in parts by mass:

95-105 parts of epoxy resin mixture, 10-20 parts of diluent, 5-15 parts of emulsifier, 4-8 parts of coupling agent and 1-3 parts of defoaming agent; the epoxy resin mixture consists of solvent type epoxy resin and water-based epoxy resin, and the mass ratio of the solvent type epoxy resin to the water-based epoxy resin is (1-3) to (1-5).

2. The modified resin of claim 1, wherein the solvent-based epoxy resin comprises a novolac epoxy resin and/or a bisphenol a epoxy resin; the water-based epoxy resin comprises peracetic acid epoxy resin and/or hydantoin epoxy resin.

3. The modified resin of claim 1, wherein the diluent is one or more of butyl glycidyl ether, ethylene glycol glycidyl ether, ethyl acetate, and dibutyl phthalate.

4. The modified resin as claimed in claim 1, wherein the emulsifier is one or more selected from the group consisting of glycerin fatty acid ester, polyoxyethylene aryl ether and polyvinyl alkyl ester.

5. The modified resin of claim 1, wherein the coupling agent is one or more of a complex coupling agent, a silane coupling agent, and a titanate coupling agent;

the defoaming agent is one or more of emulsified silicone oil, a higher alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene amine ether and polyoxypropylene glycerol ether.

6. Use of the modified resin of any one of claims 1 to 5 in a blocking agent.

7. The high-temperature-resistant solid-free plugging agent comprises the following components in parts by mass:

80-100 parts of modified resin, 5-15 parts of diluent, 10-25 parts of curing agent, 5-15 parts of accelerator, 5-10 parts of toughening agent, 3-10 parts of high-temperature retarder and 1-3 parts of defoaming agent;

the modified resin is the modified resin as claimed in any one of claims 1 to 5.

8. The high temperature resistant solid-free blocking agent according to claim 7, wherein the curing agent is one or more of aromatic amine curing agent, alicyclic amine curing agent, polyamide curing agent and organic acid anhydride curing agent;

the accelerant is one or more of an imidazole accelerant, an aromatic amine accelerant and an alicyclic amine accelerant.

9. The high temperature resistant solid-free blocking agent according to claim 7, wherein the toughening agent is one or more of polyimide, polyvinyl butyral and polyvinyl acetate;

the high-temperature retarder is one or more of 2, 4-pentanedione, alpha-methyl styrene, p-hydroxyanisole and 2-tert-butylhydroquinone.

10. Use of the high temperature resistant solid-free plugging agent of any one of claims 7 to 9 in high temperature abandoned well plugging.

Technical Field

The invention belongs to the technical field of petroleum drilling engineering chemical agents, and particularly relates to a modified resin and application thereof in a plugging agent, a high-temperature plugging agent and application thereof in high-temperature abandoned well plugging.

Background

The abandonment operation becomes the unavoidable work when the offshore oil and gas field enters the middle and later period, the existing abandoned well is sealed by cement paste, the defect exists, and the strength of the set cement is attenuated in a long-term high-temperature and high-pressure environment after abandonment; acid gas corrodes cement stones, so that cracks and gaps are generated on the cement stones, long-term integrity requirements of abandoned shafts cannot be effectively met, particularly, under the conditions of annulus pressure of gas wells, low-permeability hydrocarbon reservoirs, hot production well abandonment and the like, the integrity of the shafts is difficult to guarantee, and conventional cement paste plugging systems contain more solid-phase particles and cannot be normally squeezed into the low-permeability reservoirs.

At present, the solid-phase-free plugging materials which are researched more are mainly resin curing materials, a resin cement slurry plugging system which is mainly prepared from cement slurry and assisted by resin materials is constructed in the plugging system, and compared with a conventional cement slurry system, the high-temperature-resistant and corrosion-resistant resin cement slurry plugging system is improved in high temperature resistance and corrosion resistance, but has certain limitation on the realization of the plugging function of a low-permeability reservoir which is difficult to pump or extrude into a specified plugging position due to high solid-phase content and large particle sizes of cement particles and other additive materials.

The other method is to adopt pure resin and corresponding curing materials to construct a plugging system, and the plugging system has the advantages that the system with low solid phase content or no solid phase can meet the plugging requirement of a low-permeability reservoir stratum or a fractured stratum, but the high temperature resistance can only be 138 ℃, and under the condition that the temperature of some high-temperature wells such as thermal production wells is higher than 150 ℃, the system is easy to generate a flash coagulation phenomenon due to high temperature, the thickening time is shortened and uncontrollable, and the stability of the plugging system cannot be guaranteed.

Chinese patent CN108822815A discloses a cementing pregel, which mainly comprises an epoxy resin solution, a resin curing agent, a retarder, an expanding agent, an emulsifier and a weighting agent, wherein the thickening time is 3 hours when the use temperature is not more than 90 ℃; chinese patent CN109504356A discloses a high-strength low-elasticity water-soluble resin cement slurry system, the thickening time is 2-5 h when the highest use temperature is 90 ℃, and the system is suitable for operations including oil field exploration and development field well cementation, special well section plugging, well abandonment, offshore unconventional well repair and the like in the oil and gas field development process; chinese patent CN110105932B discloses a resin material for oil and gas well casing leak stoppage and a preparation method thereof, wherein the application temperature of the resin material is 45-75 ℃, and the thickening time is 4-25 h.

The resin plugging system related in the patent has good fluidity and long thickening time compared with the conventional cement paste, and the strength and toughness are greatly improved, but the temperature range is studied to be lower, and the applicable temperature is not more than 120 ℃ or even lower.

Disclosure of Invention

In view of the above, the invention provides a modified resin and an application thereof in a plugging agent, and a high-temperature plugging agent and an application thereof in high-temperature abandoned well plugging.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a modified resin which comprises the following components in parts by mass:

95-105 parts of epoxy resin mixture, 10-20 parts of diluent, 5-15 parts of emulsifier, 4-8 parts of coupling agent and 1-3 parts of defoaming agent; the epoxy resin mixture consists of solvent type epoxy resin and water-based epoxy resin, and the mass ratio of the solvent type epoxy resin to the water-based epoxy resin is (1-3) to (1-5).

Preferably, the solvent-type epoxy resin comprises novolac epoxy resin and/or bisphenol A epoxy resin; the water-based epoxy resin comprises peracetic acid epoxy resin and/or hydantoin epoxy resin.

Preferably, the diluent is one or more of butyl glycidyl ether, ethylene glycol glycidyl ether, ethyl acetate and dibutyl phthalate.

Preferably, the emulsifier is one or more of glycerin fatty acid ester, polyoxyethylene aryl ether and polyvinyl alkyl ester.

Preferably, the coupling agent is one or more of a complex coupling agent, a silane coupling agent and a titanate coupling agent; the defoaming agent is one or more of emulsified silicone oil, a higher alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene amine ether and polyoxypropylene glycerol ether.

The invention provides application of the modified resin in the technical scheme in a blocking agent.

The invention provides a high-temperature-resistant solid-free plugging agent which comprises the following components in parts by weight:

80-100 parts of modified resin, 5-15 parts of diluent, 10-25 parts of curing agent, 5-15 parts of accelerator, 5-10 parts of toughening agent, 3-10 parts of high-temperature retarder and 1-3 parts of defoaming agent;

the modified resin is the modified resin in the technical scheme.

Preferably, the curing agent is one or more of aromatic amine curing agent, alicyclic amine curing agent, polyamide curing agent and organic acid anhydride curing agent; the accelerant is one or more of an imidazole accelerant, an aromatic amine accelerant and an alicyclic amine accelerant.

Preferably, the toughening agent is one or more of polyimide, polyvinyl butyral and polyvinyl acetate; the high-temperature retarder is one or more of 2, 4-pentanedione, alpha-methyl styrene, p-hydroxyanisole and 2-tert-butylhydroquinone.

The invention provides an application of the high-temperature-resistant solid-free plugging agent in the technical scheme in high-temperature abandoned well plugging.

The invention provides a modified resin which comprises the following components in parts by mass: 95-105 parts of epoxy resin mixture, 10-20 parts of diluent, 5-15 parts of emulsifier, 4-8 parts of coupling agent and 1-3 parts of defoaming agent; the epoxy resin mixture is composed of solvent type epoxy resin and water-based epoxy resin, and the mass ratio of the solvent type epoxy resin to the water-based epoxy resin is (1-3) to (1-5). The modified resin provided by the invention takes the water-based epoxy resin and the solvent-based epoxy resin as the key components, the water-based epoxy resin and the solvent-based epoxy resin are modified by using the diluent, the emulsifier and the coupling agent by controlling the mass ratio of the two resins, the fluidity of a resin system is improved, the epoxy value of the obtained modified resin is proper, the generation of 'implosion' during high-temperature curing can be effectively avoided, the thickening time is long during high-temperature curing, and the thickening temperature is stable. Therefore, the high-temperature-resistant solid-free plugging agent obtained by taking the modified resin provided by the invention as a key component adopts pure resin to construct a plugging system, and overcomes the limitation that a resin cement slurry system is not suitable for plugging a low-permeability stratum due to high solid-phase content and large particle size in a solid-free plugging mode; and the problems that the pure resin system is easy to generate flash coagulation under the ultra-high temperature condition (150 ℃), the thickening time is shortened, and the stability of the plugging system cannot be guaranteed are solved. The results of the embodiment show that the high-temperature-resistant solid-free plugging agent provided by the invention can resist the temperature of 150 ℃, the thickening temperature time is 265-372 min at 150 ℃, the cementing strength is 64.55-73.82, the permeability is 0mL, the 24-hour compressive strength is 79.3-97.2 MPa, the elastic modulus is 1.9-2.5 GPa, and the strength attenuation rate is 0.5-3.2% after 7-day curing at 150 ℃.

Drawings

FIG. 1 is a graph showing the thickening behavior of the high temperature-resistant solid-free blocking agent prepared in example 1 of the present invention at 150 ℃ and 70 MPa;

FIG. 2 is a graph showing the thickening behavior of the high temperature-resistant solid-free blocking agent prepared in example 2 of the present invention at 150 ℃ and 70 MPa;

FIG. 3 is a graph showing the thickening behavior of the high temperature-resistant solid-free blocking agent prepared in example 3 of the present invention at 150 ℃ and 70 MPa.

Detailed Description

The invention provides a modified resin which comprises the following components in parts by mass:

95-105 parts of epoxy resin mixture, 10-20 parts of diluent, 5-15 parts of emulsifier, 4-8 parts of coupling agent and 1-3 parts of defoaming agent; the epoxy resin mixture consists of solvent type epoxy resin and water-based epoxy resin, and the mass ratio of the solvent type epoxy resin to the water-based epoxy resin is (1-3) to (1-5).

In the present invention, the starting materials are all commercially available products well known to those skilled in the art, unless otherwise specified.

The modified resin provided by the invention comprises 95-105 parts by mass of an epoxy resin mixture, preferably 100 parts by mass, wherein the epoxy resin mixture consists of a solvent type epoxy resin and a water-based epoxy resin, and the solvent type epoxy resin preferably comprises a novolac epoxy resin and/or a bisphenol A epoxy resin; in the invention, the solid content of the solvent type epoxy resin is preferably 98 +/-1%, the epoxy value of the solvent type epoxy resin is preferably 0.44-0.47, the viscosity of the solvent type epoxy resin at 25 ℃ is 12000-15000 mPa.s, and the viscosity of the solvent type epoxy resin is measured by adopting a Brookfield viscometer.

In the present invention, the aqueous epoxy resin preferably includes peracetic acid epoxy resin and/or hydantoin epoxy resin; in the invention, the solid content of the waterborne epoxy resin is preferably 98 +/-1%, the epoxy value of the waterborne epoxy resin is preferably 0.7, the viscosity of the waterborne epoxy resin at 25 ℃ is 2500-5000 mPa & s, and the viscosity of the waterborne epoxy resin is measured by adopting a Brookfield viscometer.

In a specific embodiment of the present invention, the combination relationship between the solvent-based epoxy resin and the water-based epoxy resin is as follows: novolac epoxy resins, bisphenol a epoxy resins, and hydantoin epoxy resins. In the specific implementation of the invention, the solvent type epoxy resin is purchased from the country petrochemical company, llc, respectively; the purchasing source of the waterborne epoxy resin is the Branch petrochemical company, and the type of the hydantoin epoxy resin is CYDW-100.

In the invention, the mass ratio of the solvent type epoxy resin to the water-based epoxy resin is (1-3): 1-5, preferably 2: 1.

In a specific embodiment of the present invention, the mass ratio of the novolac epoxy resin, the bisphenol a epoxy resin, and the hydantoin epoxy resin is preferably 1:1: 1.

The modified resin provided by the invention comprises 10-20 parts of diluent, more preferably 12-15 parts of diluent, based on epoxy resin, wherein the diluent is preferably one or more of butyl glycidyl ether, ethylene glycol glycidyl ether, ethyl acetate and dibutyl phthalate, and more preferably any one of butyl glycidyl ether, ethylene glycol glycidyl ether, ethyl acetate and phthalic acid; in a specific embodiment of the present invention, when the diluent is preferably two of the above substances, the diluent is preferably butyl glycidyl ether and ethyl acetate, ethylene glycol glycidyl ether and ethyl acetate, butyl glycidyl ether and phthalic acid, ethylene glycol glycidyl ether and phthalic acid, and in the present invention, the mass ratio of the two specific substances is preferably 1: 1.

The modified resin provided by the invention comprises 5-15 parts of emulsifier based on epoxy resin, preferably 7-10 parts of emulsifier, in the invention, the emulsifier is preferably one or more of glycerin fatty acid ester, polyoxyethylene aryl ether and polyvinyl alkyl ester, more preferably glycerin fatty acid ester and/or polyoxyethylene aryl ether, in the invention, but when the emulsifier is preferably more than two of the substances, the invention has no special requirement on the mass ratio of the specific substances.

The modified resin provided by the invention comprises 4-8 parts of coupling agent, preferably 5-7 parts of coupling agent based on epoxy resin, wherein the coupling agent is preferably one or more of complex coupling agent, silane coupling agent and titanate coupling agent, the complex coupling agent preferably comprises aluminum-zirconium organic metal complex, the silane coupling agent preferably comprises KH550 (gamma-aminopropyl triethylsilane) and/or KH570 (methacryloxypropyl trimethylsilane), and the titanate coupling agent preferably comprises pyrophosphate type monoalkoxy titanate; in the present invention, the coupling agent is more preferably a silane coupling agent, and in the present invention, when the coupling agent is preferably two or more of the above substances, the mass ratio of the specific substances in the present invention is not particularly limited.

The modified resin provided by the invention comprises 1-3 parts of defoaming agent by taking epoxy resin as a reference, preferably 1.5-2 parts, and in the invention, the defoaming agent is preferably one or a mixture of more of emulsified silicone oil, higher alcohol fatty acid ester compound, polyoxyethylene polyoxypropylene amine ether and polyoxypropylene glycerol ether, and more preferably emulsified silicone oil, higher alcohol fatty acid ester compound or polyoxyethylene polyoxypropylene amine ether; in the present invention, when the defoaming agent is preferably two or more of the above substances, the mass ratio of the specific substances in the present invention is not particularly limited.

The modified resin provided by the invention takes the water-based epoxy resin and the solvent-based epoxy resin as the key components, the water-based epoxy resin and the solvent-based epoxy resin are modified by using the diluent, the emulsifier and the coupling agent by controlling the mass ratio of the two resins, the fluidity of a resin system is improved, the epoxy value of the obtained modified resin is proper, the generation of 'implosion' during high-temperature curing can be effectively avoided, the thickening time is long during high-temperature curing, and the thickening temperature is stable.

In the present invention, the method for preparing the modified resin preferably comprises the steps of:

and mixing and modifying epoxy resin, a diluent, an emulsifier, a coupling agent and a defoaming agent to obtain the modified resin.

In the present invention, the mixing modification preferably comprises the steps of:

carrying out first mixing on the epoxy resin and a diluent to obtain a first mixed material;

carrying out second mixing on the first mixed material and an emulsifier to obtain a second mixed material;

thirdly mixing the second mixed material and a coupling agent to obtain a third mixed material;

and fourthly, mixing the third mixed material and a defoaming agent to obtain the modified resin.

The epoxy resin and the diluent are subjected to first mixing to obtain a first mixed material.

In the invention, the temperature of the first mixing is preferably room temperature, the time of the first mixing is preferably 10-20 min, the first mixing is preferably carried out under the condition of stirring, the rotating speed of the stirring is preferably 500-600 r/min, and the invention has no special requirement on the specific implementation process of the stirring.

After the first mixed material is obtained, the first mixed material and the emulsifier are subjected to second mixing to obtain a second mixed material.

In the invention, the temperature of the second mixing is preferably room temperature, the time of the second mixing is preferably 10-20 min, the second mixing is preferably carried out under the condition of stirring, the rotating speed of the stirring is preferably 500-600 r/min, and the invention has no special requirement on the specific implementation process of the stirring.

After the second mixed material is obtained, the second mixed material and the coupling agent are subjected to third mixing to obtain a third mixed material.

In the invention, the temperature of the third mixing is preferably room temperature, the time of the third mixing is preferably 10-20 min, the third mixing is preferably carried out under the condition of stirring, the rotating speed of the stirring is preferably 1000-1200 r/min, and the invention has no special requirement on the specific implementation process of the stirring.

After the third mixed material is obtained, the third mixed material and the defoaming agent are mixed for the fourth time to obtain the modified resin.

In the invention, the temperature of the fourth mixing is preferably room temperature, the time of the fourth mixing is preferably 5-10 min, the fourth mixing is preferably carried out under the condition of stirring, the rotating speed of the stirring is preferably 500-600 r/min, and the invention has no special requirement on the specific implementation process of the stirring.

The invention provides application of the modified resin in the technical scheme in a blocking agent.

In the invention, the modified resin is preferably used for preparing a solid-free plugging material, and the solid-free plugging material is preferably a cement paste plugging agent or a pure resin plugging agent. In the invention, the amount of the modified resin in the cement paste plugging agent is preferably 15% of the total mass of the cement paste plugging agent.

The invention provides a high-temperature-resistant solid-free plugging agent which comprises the following components in parts by weight:

80-100 parts of modified resin, 5-15 parts of diluent, 10-25 parts of curing agent, 5-15 parts of accelerator, 5-10 parts of toughening agent, 3-10 parts of high-temperature retarder and 1-3 parts of defoaming agent;

the modified resin is the modified resin in the technical scheme.

The high-temperature-resistant solid-free blocking agent comprises, by mass, 80-100 parts of modified resin, preferably 85-95 parts; in the invention, the modified resin is the modified resin in the technical scheme.

Based on the modified resin, the high-temperature-resistant solid-free plugging agent provided by the invention comprises 5-15 parts of diluent, preferably 6-12 parts; in the present invention, the diluent is preferably one or more of butyl glycidyl ether, ethylene glycol glycidyl ether, ethyl acetate and dibutyl phthalate, more preferably any one of butyl glycidyl ether, ethylene glycol glycidyl ether, ethyl acetate and phthalic acid, and most preferably ethylene glycol glycidyl ether and ethyl acetate; in a specific embodiment of the present invention, when the diluent is preferably two of the above substances, the mass ratio of the above specific substances is preferably 1: 1.

Based on the modified resin, the high-temperature-resistant solid-free blocking agent provided by the invention comprises 10-25 parts of a curing agent, preferably 12-20 parts, and more preferably 15-18 parts; in the present invention, the curing agent is preferably one or more of an aromatic amine curing agent, an alicyclic amine curing agent, a polyamide curing agent, and an organic acid anhydride curing agent; in the present invention, the aromatic amine curing agent is preferably one or more of diaminodiphenylmethane, m-phenylenediamine and m-xylylenediamine, the alicyclic amine curing agent is preferably ethylenediamine and/or diethylenetriamine, the polyamide curing agent is preferably polyamide, and the organic acid anhydride curing agent is preferably phthalic anhydride and/or tetrahydrophthalic anhydride; in the present invention, the curing agent is more preferably any one of diaminodiphenylmethane, m-phenylenediamine, diethylenetriamine, and phthalic anhydride, and is more preferably m-phenylenediamine and phthalic anhydride; in the embodiment of the present invention, when the curing agent is preferably two of the above substances, the mass ratio of the specific substances is preferably 1: 1.

Based on the modified resin, the high-temperature-resistant solid-free blocking agent provided by the invention comprises 5-15 parts of an accelerator, preferably 7-12 parts, and more preferably 9-10 parts; in the invention, the accelerant is preferably one or more of an imidazole accelerant, an aromatic amine accelerant and an alicyclic amine accelerant, in the invention, the imidazole accelerant is preferably dimethyl imidazole, the aromatic amine accelerant is preferably m-phenylenediamine, and the alicyclic amine accelerant is preferably ethylene diamine and/or diethylenetriamine; in the present invention, the accelerator is more preferably one or more of m-xylylenediamine, dimethylimidazole and diethylenetriamine, and most preferably m-phenylenediamine and dimethylimidazole; in a specific embodiment of the present invention, when the two kinds of the above-mentioned accelerators are preferable, the mass ratio of the above-mentioned specific substances is preferably 1: 1.

Based on the modified resin, the high-temperature-resistant solid-free blocking agent provided by the invention comprises 5-10 parts of a toughening agent, preferably 6-8 parts, and more preferably 6.5-7 parts; in the present invention, the toughening agent is preferably one or more of polyimide, polyvinyl butyral and polyvinyl acetate, more preferably polyimide and/or polyvinyl butyral; in the embodiment of the present invention, when the toughening agent is preferably two or more of the above substances, the present invention has no special requirement on the mass ratio of the above specific substances.

Based on the modified resin, the high-temperature-resistant solid-free plugging agent provided by the invention comprises 3-10 parts of a high-temperature retarder, preferably 5-8 parts, more preferably 6.5-7 parts; in the invention, the high-temperature retarder is preferably one or more of 2, 4-pentanedione, alpha-methylstyrene and 2-tert-butylhydroquinone, and is more preferably one or more of p-hydroxyanisole, alpha-methylstyrene and 2-tert-butylhydroquinone; in the embodiment of the present invention, when the high temperature retarder is preferably two or more of the above substances, the present invention has no special requirement on the mass ratio of the above specific substances.

Based on the modified resin, the high-temperature-resistant solid-free blocking agent provided by the invention comprises 1-3 parts of defoaming agent, preferably 1.5-2 parts; in the invention, the defoaming agent is preferably one or a mixture of more of emulsified silicone oil, higher alcohol fatty acid ester complex, polyoxyethylene polyoxypropylene amine ether and polyoxypropylene glycerol ether, and more preferably emulsified silicone oil, higher alcohol fatty acid ester complex or polyoxyethylene polyoxypropylene amine ether; in the present invention, when the defoaming agent is preferably two or more of the above substances, the mass ratio of the specific substances in the present invention is not particularly limited.

The high-temperature-resistant solid-free plugging agent provided by the invention takes the modified resin in the technical scheme as a key component to construct a pure resin plugging system, and overcomes the limitation that a resin cement slurry system is not suitable for plugging a low-permeability stratum due to high solid-phase content and large particle size in a solid-free plugging mode; and the problems that the pure resin system is easy to generate flash coagulation under the ultra-high temperature condition (150 ℃), the thickening time is shortened, and the stability of the plugging system cannot be guaranteed are solved.

In the present invention, the preparation method of the high temperature resistant solid-free blocking agent preferably comprises the following steps:

mixing and curing modified resin, a diluent, a curing agent, an accelerator, a toughening agent, a high-temperature retarder and a defoaming agent to obtain the high-temperature-resistant solid-free blocking agent; the modified resin is preferably the modified resin described in the above technical means.

In the present invention, the hybrid curing preferably includes the steps of:

carrying out fifth mixing on the modified resin and the diluent to obtain a fifth mixed material;

carrying out sixth mixing on the fifth mixed material and a curing agent to obtain a sixth mixed material;

seventh mixing is carried out on the sixth mixed material and the accelerant to obtain a seventh mixed material;

eighth mixing is carried out on the seventh mixed material and the toughening agent to obtain an eighth mixed material;

ninth mixing is carried out on the eighth mixed material and the high-temperature retarder to obtain a ninth mixed material;

and tenth mixing is carried out on the ninth mixed material and a defoaming agent to obtain the high-temperature-resistant solid-free plugging agent.

According to the invention, the modified resin and the diluent are mixed for the fifth time to obtain a fifth mixed material.

In the invention, the temperature of the fifth mixing is preferably room temperature, the time of the fifth mixing is preferably 10-20 min, the fifth mixing is preferably carried out under the condition of stirring, the rotating speed of the stirring is preferably 500-600 r/min, and the invention has no special requirement on the specific implementation process of the stirring.

And after the fifth mixed material is obtained, sixth mixing is carried out on the fifth mixed material and the curing agent to obtain a sixth mixed material.

In the invention, the temperature of the sixth mixing is preferably room temperature, the time of the sixth mixing is preferably 10-20 min, the sixth mixing is preferably carried out under the condition of stirring, the rotating speed of the stirring is preferably 1000-1200 r/min, and the invention has no special requirement on the specific implementation process of the stirring.

And after a sixth mixed material is obtained, seventh mixing is carried out on the sixth mixed material and the accelerant to obtain a seventh mixed material.

In the invention, the temperature of the seventh mixing is preferably room temperature, the time of the seventh mixing is preferably 10-20 min, the seventh mixing is preferably carried out under the condition of stirring, the rotating speed of the stirring is preferably 1000-1200 r/min, and the invention has no special requirement on the specific implementation process of the stirring.

And after the seventh mixed material is obtained, carrying out eighth mixing on the seventh mixed material and the toughening agent to obtain an eighth mixed material.

In the invention, the temperature of the eighth mixing is preferably room temperature, the time of the eighth mixing is preferably 10-20 min, the eighth mixing is preferably carried out under the condition of stirring, the rotating speed of the stirring is preferably 1000-1200 r/min, and the invention has no special requirement on the specific implementation process of the stirring.

And after the eighth mixed material is obtained, ninth mixing is carried out on the eighth mixed material and the high-temperature retarder to obtain a ninth mixed material.

In the invention, the ninth mixing temperature is preferably room temperature, the ninth mixing time is preferably 10-20 min, the ninth mixing is preferably carried out under the condition of stirring, the rotation speed of the stirring is preferably 1000-1200 r/min, and the invention has no special requirement on the specific implementation process of the stirring.

And after obtaining a ninth mixed material, tenth mixing the ninth mixed material and a defoaming agent to obtain the high-temperature-resistant solid-free blocking agent.

In the invention, the temperature of the tenth mixing is preferably room temperature, the time of the tenth mixing is preferably 10-20 min, the tenth mixing is preferably carried out under the condition of stirring, the rotation speed of the stirring is preferably 500-600 r/min, and the invention has no special requirement on the specific implementation process of the stirring.

The high-temperature-resistant solid-free plugging agent provided by the invention has the following characteristics:

(1) the high-temperature-resistant solid-free plugging agent provided by the invention belongs to a solid-free formula, has good fluidity, can enter a micropore or low-permeability stratum for filling, and is solidified in a stratum crack or micropore or a shaft, so that high-strength pressure bearing under the shaft stratum condition is realized.

(2) The high-temperature resistant solid-free plugging agent provided by the invention can resist the temperature as high as 150 ℃, can adjust the thickening and curing time of the solid-free plugging agent according to the change of the temperature, and can prevent the occurrence of implosion and flash condensation of the solid-free plugging agent at high temperature.

(3) The high-temperature-resistant solid-free plugging agent provided by the invention has good chemical bonding and cementing properties, can enter micropores of a stratum in a high-pressure extrusion mode to realize more compact interlayer cementing and interface cementing, and can plug microcracks and microcracks of the stratum, so that the problem of gas channeling or sealing failure of a abandoned well can be effectively solved.

The invention provides an application of the high-temperature-resistant solid-free plugging agent in the technical scheme in high-temperature abandoned well plugging.

The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

(1) Preparation of modified resin

Weighing 100 parts of epoxy resin (phenolic epoxy resin, bisphenol A epoxy resin and hydantoin resin prepared according to the mass ratio of 1:1: 1) according to the mass parts, adding 12 parts of ethylene glycol glycidyl ether, mixing, dispersing and stirring for 10min at the rotating speed of 500r/min until the epoxy resin is uniformly dispersed, adding 5 parts of polyoxyethylene aryl ether, stirring for 10min at the rotating speed of 500r/min, adding 6 parts of silane coupling agent, stirring for 10min at the rotating speed of 1000r/min, finally adding 2 parts of polyoxypropylene glycerol ether, and stirring for 5min at the rotating speed of 500r/min to obtain the modified resin.

(2) Preparation of high-temperature-resistant solid-free plugging coagulant

Weighing 80 parts of modified resin according to the mass parts, adding 8 parts of diluent (the mass ratio of ethylene glycol glycidyl ether to ethyl acetate is 1:1), dispersing and stirring for 10min at the rotating speed of 500r/min until the modified resin is uniformly dispersed, adding 12 parts of curing agent (the mass ratio of m-phenylenediamine to p-xylylenediamine is 1:1), stirring for 10min at the rotating speed of 1000r/min, adding 6 parts of promoter (the mass ratio of m-phenylenediamine to dimethylimidazole is 1:1), stirring for 10min at the rotating speed of 1000r/min, then adding 6 parts of polyvinyl butyral, stirring for 10min at the rotating speed of 1000r/min, then adding 5 parts of p-hydroxyanisole, stirring for 10min at the rotating speed of 1000r/min, finally adding 2 parts of emulsified silicone oil, and stirring for 5min at the rotating speed of 500r/min to obtain the high-temperature-resistant solid-phase-free blocking agent.

Example 2

(1) Preparation of modified resin

Weighing 100 parts of epoxy resin (phenolic epoxy resin, bisphenol A epoxy resin and hydantoin resin prepared according to the mass ratio of 1:1: 1) according to the mass parts, adding 15 parts of ethylene glycol glycidyl ether, mixing, dispersing and stirring for 15min at the rotating speed of 500r/min until the epoxy resin is uniformly dispersed, adding 8 parts of polyoxyethylene aryl ether, stirring for 15min at the rotating speed of 500r/min, adding 5 parts of silane coupling agent, stirring for 15min at the rotating speed of 1000r/min, finally adding 2 parts of polyoxypropylene glycerol ether, and stirring for 10min at the rotating speed of 500r/min to obtain the modified resin.

(2) Preparation of high-temperature-resistant solid-free plugging coagulant

Weighing 90 parts of modified resin according to the mass parts, adding 10 parts of diluent (the mass ratio of ethylene glycol glycidyl ether to ethyl acetate is 1:1), dispersing and stirring for 15min at the rotating speed of 500r/min until the modified resin is uniformly dispersed, adding 15 parts of curing agent (the mass ratio of m-phenylenediamine to p-xylylenediamine is 1:1), stirring for 15min at the rotating speed of 1000r/min, adding 8 parts of accelerant (the mass ratio of m-phenylenediamine to dimethylimidazole is 1:1), stirring for 15min at the rotating speed of 1000r/min, then adding 8 parts of polyvinyl butyral, stirring for 20min at the rotating speed of 1000r/min, then adding 5 parts of p-hydroxyanisole, stirring for 20min at the rotating speed of 1000r/min, finally adding 2 parts of emulsified silicone oil, and stirring for 5min at the rotating speed of 500r/min to obtain the high-temperature-resistant solid-phase-free blocking agent.

Example 3

(1) Preparation of modified resin

Weighing 100 parts of epoxy resin (phenolic epoxy resin, bisphenol A epoxy resin and hydantoin resin prepared according to a mass ratio of 1:1: 1) according to the mass parts, adding 18 parts of ethylene glycol glycidyl ether, mixing, dispersing and stirring for 20min at a rotating speed of 500r/min until the epoxy resin is uniformly dispersed, adding 10 parts of polyoxyethylene aryl ether, stirring for 20min at a rotating speed of 500r/min, adding 7 parts of silane coupling agent, stirring for 10min at a rotating speed of 1000r/min, finally adding 2 parts of polyoxypropylene glycerol ether, and stirring for 5min at a rotating speed of 500r/min to obtain the modified resin.

(2) Preparation of high-temperature-resistant solid-free plugging coagulant

Weighing 100 parts of modified resin according to the mass parts, adding 12 parts of diluent (the mass ratio of ethylene glycol glycidyl ether to ethyl acetate is 1:1), dispersing and stirring for 20min at the rotating speed of 500r/min until the modified resin is uniformly dispersed, adding 18 parts of curing agent (the mass ratio of m-phenylenediamine to p-xylylenediamine is 1:1), stirring for 20min at the rotating speed of 1000r/min, adding 10 parts of accelerator (the mass ratio of m-phenylenediamine to dimethylimidazole is 1:1), stirring for 20min at the rotating speed of 1000r/min, then adding 10 parts of polyvinyl butyral, stirring for 20min at the rotating speed of 1000r/min, then adding 5 parts of p-hydroxyanisole, stirring for 20min at the rotating speed of 1000r/min, finally adding 2 parts of emulsified silicone oil, and stirring for 5min at the rotating speed of 500r/min to obtain the high-temperature solid-free blocking agent.

Comparative example 1

Weighing 100 parts of bisphenol A epoxy resin according to the parts by weight, adding 12 parts of diluent (the mass ratio of glycol glycidyl ether to ethyl acetate is 1:1), dispersing and stirring for 20min at the rotating speed of 500r/min until the dispersion is uniform, adding 18 parts of curing agent (the mass ratio of m-phenylenediamine to p-xylylenediamine is 1:1), stirring for 20min at the rotating speed of 1000r/min, adding 10 parts of accelerator (the mass ratio of m-phenylenediamine to dimethyl imidazole is 1:1), stirring for 20min at the rotating speed of 1000r/min, then adding 10 parts of polyvinyl butyral, stirring at 1000r/min for 20min, adding 5 parts of p-hydroxyanisole, stirring for 20min at the rotating speed of 1000r/min, finally adding 2 parts of emulsified silicone oil, stirring for 5min at the rotating speed of 500r/min to obtain the high-temperature resistant solid-free plugging agent.

Comparative example 2

Preparing bisphenol A epoxy resin plugging gel according to a comparative example 1, taking the prepared resin gel as a cement additive for later use, preparing polymer cement slurry commonly used for well cementation according to GB-T19139-2012 oil well cement test method, adding and preparing the bisphenol A epoxy resin plugging gel (namely 100 parts of oil well G-grade cement and 20 parts of resin gel) according to 20 weight parts of cement, and stirring for 10min at the rotating speed of 5000r/min to obtain the bisphenol A epoxy resin cement slurry.

Comparative example 3

(1) Preparation of modified resin

Weighing 100 parts of epoxy resin (novolac epoxy resin) according to the mass parts, adding 12 parts of ethylene glycol glycidyl ether, mixing, dispersing and stirring for 10min at the rotating speed of 500r/min until the epoxy resin is uniformly dispersed, adding 5 parts of polyoxyethylene aryl ether, stirring for 10min at the rotating speed of 500r/min, adding 6 parts of silane coupling agent, stirring for 10min at the rotating speed of 1000r/min, finally adding 2 parts of polyoxypropylene glycerol ether, and stirring for 5min at the rotating speed of 500r/min to obtain the modified resin.

(2) Preparation of high-temperature-resistant solid-free plugging coagulant

Weighing 80 parts of modified resin according to the mass parts, adding 8 parts of diluent (the mass ratio of ethylene glycol glycidyl ether to ethyl acetate is 1:1), dispersing and stirring for 10min at the rotating speed of 500r/min until the modified resin is uniformly dispersed, adding 12 parts of curing agent (the mass ratio of m-phenylenediamine to p-xylylenediamine is 1:1), stirring for 10min at the rotating speed of 1000r/min, adding 6 parts of promoter (the mass ratio of m-phenylenediamine to dimethylimidazole is 1:1), stirring for 10min at the rotating speed of 1000r/min, then adding 6 parts of polyvinyl butyral, stirring for 10min at the rotating speed of 1000r/min, then adding 5 parts of p-hydroxyanisole, stirring for 10min at the rotating speed of 1000r/min, finally adding 2 parts of emulsified silicone oil, and stirring for 5min at the rotating speed of 500r/min to obtain the high-temperature-resistant solid-phase-free blocking agent.

Comparative example 4

(1) Preparation of modified resin

Weighing 100 parts of epoxy resin (hydantoin epoxy resin) according to the mass parts, adding 12 parts of glycol glycidyl ether, mixing, dispersing and stirring for 10min at the rotating speed of 500r/min until the epoxy resin is uniformly dispersed, adding 5 parts of polyoxyethylene aryl ether, stirring for 10min at the rotating speed of 500r/min, adding 6 parts of silane coupling agent, stirring for 10min at the rotating speed of 1000r/min, finally adding 2 parts of polyoxypropylene glycerol ether, and stirring for 5min at the rotating speed of 500r/min to obtain the modified resin.

(2) Preparation of high-temperature-resistant solid-free plugging coagulant

Weighing 80 parts of modified resin according to the mass parts, adding 8 parts of diluent (the mass ratio of ethylene glycol glycidyl ether to ethyl acetate is 1:1), dispersing and stirring for 10min at the rotating speed of 500r/min until the modified resin is uniformly dispersed, adding 12 parts of curing agent (the mass ratio of m-phenylenediamine to p-xylylenediamine is 1:1), stirring for 10min at the rotating speed of 1000r/min, adding 6 parts of promoter (the mass ratio of m-phenylenediamine to dimethylimidazole is 1:1), stirring for 10min at the rotating speed of 1000r/min, then adding 6 parts of polyvinyl butyral, stirring for 10min at the rotating speed of 1000r/min, then adding 5 parts of p-hydroxyanisole, stirring for 10min at the rotating speed of 1000r/min, finally adding 2 parts of emulsified silicone oil, and stirring for 5min at the rotating speed of 500r/min to obtain the high-temperature-resistant solid-phase-free blocking agent.

Test example 1

Testing various performances of the products prepared in the examples 1-3 and the comparative examples 1-4 by using a GB-T19139-2012 oil well cement test method, wherein the performances comprise rheological property, compressive strength, temperature stability, bond strength, elastic modulus and permeability, the rheological properties are respectively tested at room temperature of 25 ℃ and 90 ℃, and the reading of the rheological properties is tested at 300 revolutions by using a flow rate viscometer; testing the compressive strength and the elastic modulus, namely, curing at high temperature and high pressure of 150 ℃, and testing the uniaxial compressive strength and the elastic modulus at room temperature; the temperature resistance stability is tested by maintaining for 7 days under the conditions of high temperature and high pressure; cementing strength, namely curing and cementing by using casing steel, and testing the cementing strength after curing for 24 hours, wherein the results are shown in table 1; the elasticity test adopts the volume change rate of a test sample under the extreme pressure conditions of 70MPa and 100MPa and the recovery condition of the self volume after the pressure is cancelled, and the results are shown in Table 2; FIGS. 1 to 3 are graphs showing the thickening curves of the products prepared in examples 1 to 3 of the present invention at 150 ℃ and 70 MPa.

TABLE 1 results of Performance test of products prepared in examples 1-3 and comparative examples 1 and 2

TABLE 2 results of elasticity test of the products prepared in examples 1 to 3 and comparative examples 1 and 2

Under the high-temperature condition, the resin is easy to be subjected to implosion during curing, and the specific expression in the experiment is as follows: the high-temperature resistant solid-free plugging agent provided by the invention can adjust the reaction process by adding the retarder, so that after the experiment temperature reaches the high temperature (150 ℃), the local reaction is slow, the abnormal rise of the temperature caused by continuous heat release is avoided, the 150 ℃ can be maintained to be constant, the time of an initial curing point is prolonged, and the purpose of controlling can be achieved. In addition, the high-temperature resistant solid-free blocking agent provided by the invention can effectively shorten the time required by final curing strength by adding the accelerator through the retarder.

As can be seen from the above test results shown in tables 1 and 2 and FIGS. 1 to 3, the high temperature resistant solid-free blocking agents provided in examples 1 to 3 of the present invention have fluidity at room temperature of 90 ℃The method has the advantages that the method is good in performance and beneficial to field construction pumping, the thickening time can be adjusted (265-372 min) according to construction requirements under the condition of 150 ℃, the compressive strength can be adjusted according to actual requirements, the strength and toughness can be adjusted according to 79.3-97.2 MPa, the elastic modulus is 2.5-1.9 GPa, after deformation occurs under compression, the volume can be recovered in a short time, the compression is 70MPa, the volume recovery rate can reach 100%, the compression is 100MPa, the volume recovery rate can reach more than 90%, the method has good elasticity, and the method can resist the situation that brittle fracture does not occur under the condition of underground ultimate stress to influence the integrity of a shaft. Meanwhile, the cementing strength with the casing pipe is high (73.82 kgf/cm)²) And the permeability after curing is 0, so that gas channeling can be well prevented, and particularly, the phenomenon of oil gas water leakage at a well mouth can not occur when the whole well barrel of a abandoned well is plugged for a long time. Meanwhile, the high-temperature resistant stability is good, after the high-temperature and high-pressure curing is carried out at 150 ℃ for 7 days, the strength attenuation rate is less than 5%, and the requirement that the well is slightly influenced by underground high temperature and pressure change after the well is abandoned for a long time can be met, so that the integrity of the sealed shaft is effectively guaranteed.

The conventional bisphenol A epoxy resin adopted in the comparative example 1 is prepared into the solid-free plugging gel, the performance of the conventional bisphenol A epoxy resin is poorer than that of the embodiment of the invention in all aspects at the high temperature of 150 ℃, and the main defect is that the high-temperature thickening time is short, the reaction is violent after the temperature is raised to the specified temperature, and the flash coagulation phenomenon rapidly occurs; the comparative example 2 adopts resin cement slurry to prepare a plugging system, although the plugging system can be well controlled in thickening time, the rheological property is poor, the permeability is high after curing, the cementing strength is insufficient, gas channeling is easy to occur, and meanwhile, after the plugging system is maintained for 7 days in a high-temperature environment, the strength attenuation is obvious, and the long-term stability of later-stage shaft plugging is not facilitated. The deformation is generated after the compression of the comparative example 3, the recovery rate after 24 hours is only 86%, and the 7d attenuation is obviously as high as 37% after the comparative example 4 is subjected to the high temperature of 150 ℃, so that the requirement of the long-term integrity of the shaft under the conditions of high temperature and high pressure cannot be met.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.