Thermosetting resin composition for well cementation and preparation method thereof

Abstract

The invention relates to the technical field of preparation of thermosetting resin for well cementation, in particular to a thermosetting resin composition for well cementation and a preparation method thereof.The thermosetting resin composition for well cementation is prepared from thermosetting resin, a resin curing agent, porous aluminum oxide ceramic balls, phase change silicone grease, metal oxide, phosphate, a fluid loss agent, a cooling retarder and water. The preparation method comprises the following steps: preparing curing agent slow-release particles from porous alumina ceramic balls, a resin curing agent, phase-change silicone grease and a part of metal oxide, then sequentially adding a required amount of thermosetting resin, phosphate, a fluid loss agent, a cooling retarder and the balance of metal oxide and water into the curing agent slow-release particles, and mixing to obtain the curing agent. According to the thermosetting resin composition for well cementation, the resin curing agent is slowly released, the initial setting time of the composition is longer than 4 h, the composition begins to solidify after being pumped to a target position, and the final setting time is within 24 h.

Description

Technical Field

[0001] The invention relates to the technical field of preparation of thermosetting resin for cementing, and is a thermosetting resin composition for cementing and a preparation method thereof. Background Art

[0002] After geological surveys and geophysical explorations, the most favorable drilling locations for oil and gas accumulation are selected, and drilling technology is used to drill through the oil and gas layers in order to test geophysical data, understand downhole oil and gas geological exploration data, calculate oil and gas reserves, and provide development prospects. This drilling project is referred to as oil and gas drilling.

[0003] In the field of oil drilling, the high strength characteristics of thermosetting resin after curing are often used to form a section of resin tube at the expanded part of the well wall underground, which serves as a temporary casing. The thermosetting resin gel system used in this process needs to be mixed on the surface, and then pumped to the corresponding position underground through the drill pipe, and then start to cure after being pumped into the corresponding position. However, the existing thermosetting resin cures quickly, and generally thickens and solidifies 30 minutes to 1 hour after mixing. It usually takes 4 to 6 hours for the drill pipe to pump the thermosetting resin gel system to the response position underground. This causes the thermosetting resin to solidify before reaching the target position during the pumping process, affecting the final solidification effect. Summary of the invention

[0004] The present invention provides a thermosetting resin composition for cementing and a preparation method thereof, which overcomes the deficiencies of the above-mentioned prior art and can effectively solve the problem that the existing thermosetting resin composition for cementing begins to solidify before reaching the target position, thus affecting the final solidification effect.

[0005] One of the technical solutions of the present invention is achieved through the following measures: a thermosetting resin composition for cementing, wherein the raw materials include, by weight, 15 to 60 parts of thermosetting resin, 5 to 10 parts of resin curing agent, 4 to 7 parts of porous alumina ceramic balls, 3 to 5 parts of phase change silicone grease, 70 to 115 parts of metal oxides, 35 to 55 parts of phosphates, 1 to 5 parts of fluid loss reducer, 15 to 25 parts of cooling retarder and 30 to 130 parts of water.

[0006] The following is a further optimization and / or improvement of one of the above-mentioned technical solutions: The thermosetting resin is two or more selected from epoxy resin, phenolic epoxy resin, polybutylene resin, silicone resin and furan resin.

[0007] The resin curing agent is one or more of an acid anhydride, aliphatic amines, alicyclic amines, phenolic compounds and polyols.

[0008] The metal oxide is one or more of dead-burned magnesium oxide, aluminum oxide, iron oxide, dicalcium oxide, and metakaolin.

[0009] The phosphate is one or more of sodium monohydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and polyphosphate.

[0010] The above-mentioned fluid loss additive is an AMPS multi-polymer fluid loss additive.

[0011] The cooling and retarding agent is one or more of magnesium nitrate, magnesium chloride and zeolite powder.

[0012] The above-mentioned thermosetting resin composition for cementing is obtained by the following method: In the first step, a required amount of porous alumina ceramic balls, a resin curing agent, a phase change silicone grease and a portion of metal oxides are prepared to obtain curing agent slow-release particles; In the second step, the required amount of thermosetting resin, phosphate, fluid loss reducer, cooling retarder, the remaining amount of metal oxide and the required amount of water are sequentially added to the curing agent slow-release particles, mixed and stirred for 20 to 60 minutes to obtain a thermosetting resin composition for cementing.

[0013] In the first step above, the specific preparation process of the curing agent slow-release particles is as follows: S1, mixing the required amount of resin curing agent and porous alumina ceramic balls and stirring for 15 to 30 minutes to obtain a mixture 1; S2, heating a required amount of phase change silicone grease to 60° C. to 80° C. to melt the phase change silicone grease to obtain a phase change silicone grease melt, adding the mixture to the phase change silicone grease melt and stirring for 10 to 15 minutes, and then adding a portion of the metal oxide and stirring for 10 to 15 minutes to obtain a solidified liquid; S3, cooling the solidifying liquid to room temperature to solidify it, and breaking the solidified solidifying liquid into pieces of 3 mm to 6 mm to obtain curing agent slow-release particles.

[0014] The second technical solution of the present invention is achieved by the following measures: A method for preparing a thermosetting resin composition for cementing is carried out according to the following method: the first step is to prepare a required amount of porous alumina ceramic balls, a resin curing agent, a phase change silicone grease and a part of metal oxide to obtain curing agent slow-release particles; In the second step, the required amount of thermosetting resin, phosphate, fluid loss reducer, cooling retarder, the remaining amount of metal oxide and the required amount of water are sequentially added to the curing agent slow-release particles, mixed and stirred for 20 to 60 minutes to obtain a thermosetting resin composition for cementing.

[0015] The following is a further optimization and / or improvement of the second technical solution of the above invention: In the first step above, the specific preparation process of the curing agent slow-release particles is as follows: S1, mixing the required amount of resin curing agent and porous alumina ceramic balls and stirring for 15 to 30 minutes to obtain a mixture 1; S2, heating a required amount of phase change silicone grease to 60° C. to 80° C. to melt the phase change silicone grease to obtain a phase change silicone grease melt, adding the mixture to the phase change silicone grease melt and stirring for 10 to 15 minutes, and then adding a portion of the metal oxide and stirring for 10 to 15 minutes to obtain a solidified liquid; S3, cooling the solidifying liquid to room temperature to solidify it, and breaking the solidified solidifying liquid into pieces of 3 mm to 6 mm to obtain curing agent slow-release particles.

[0016] The resin curing agent in the thermosetting resin composition for cementing of the present invention is slowly released, the initial setting time of the composition is greater than 4 hours, it starts to solidify after being pumped to the target position, and the final setting time is within 24 hours. DETAILED DESCRIPTION

[0017] The present invention is not limited by the following embodiments, and the specific implementation method can be determined according to the technical scheme of the present invention and the actual situation. Unless otherwise specified, the various chemical reagents and chemicals mentioned in the present invention are all chemical reagents and chemicals known and used in the prior art; unless otherwise specified, the percentages in the present invention are all mass percentages; unless otherwise specified, the solutions in the present invention are all aqueous solutions with water as the solvent, for example, hydrochloric acid solution is a hydrochloric acid aqueous solution; the normal temperature and room temperature in the present invention generally refer to a temperature of 15°C to 25°C, and are generally defined as 25°C.

[0018] The present invention will be further described below in conjunction with embodiments: Embodiment 1: The thermosetting resin composition for cementing comprises, by weight, 15 to 60 parts of thermosetting resin, 5 to 10 parts of resin curing agent, 4 to 7 parts of porous alumina ceramic balls, 3 to 5 parts of phase change silicone grease, 70 to 115 parts of metal oxides, 35 to 55 parts of phosphates, 1 to 5 parts of fluid loss reducer, 15 to 25 parts of cooling retarder and 30 to 130 parts of water.

[0019] In the present invention, the diameter of the porous alumina ceramic ball is 1 mm to 3 mm, and the porosity is 20% to 50%.

[0020] Embodiment 2: As an optimization of the above embodiment, the thermosetting resin is two or more of epoxy resin, phenolic epoxy resin, polybutylene resin, silicone resin and furan resin.

[0021] Embodiment 3: As an optimization of the above embodiment, the resin curing agent is one or more of acid anhydrides, aliphatic amines, alicyclic amines, phenols and polyol compounds.

[0022] In the present invention, the acid anhydride is one of phthalic anhydride, tung oil anhydride and hexahydrophthalic anhydride; the aliphatic amine is triethylenetetramine; the alicyclic amine is 2215 alicyclic amine modified curing agent; the phenol is one of phenol, o-cresol and m-cresol; the polyol is one of pentaerythritol, ethylene glycol, 1,2-propylene glycol and 1,4-butanediol.

[0023] Example 4: As an optimization of the above example, the metal oxide is one or more of dead-burned magnesium oxide, aluminum oxide, iron oxide, dicalcium oxide, and kaolin.

[0024] Embodiment 5: As an optimization of the above embodiment, the phosphate is one or more of sodium monohydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and polyphosphate.

[0025] Example 6: As an optimization of the above example, the fluid loss additive is an AMPS multipolymer fluid loss additive.

[0026] Example 7: As an optimization of the above example, the cooling and retarding agent is one or more of magnesium nitrate, magnesium chloride and zeolite powder.

[0027] Embodiment 8: As an optimization of the above embodiment, the thermosetting resin composition for cementing is obtained by the following method: In the first step, a required amount of porous alumina ceramic balls, a resin curing agent, a phase change silicone grease and a portion of metal oxides are prepared to obtain curing agent slow-release particles; In the second step, the required amount of thermosetting resin, phosphate, fluid loss reducer, cooling retarder, the remaining amount of metal oxide and the required amount of water are sequentially added to the curing agent slow-release particles, mixed and stirred for 20 to 60 minutes to obtain a thermosetting resin composition for cementing.

[0028] Example 9: As an optimization of the above example, in the thermosetting resin composition for cementing, in the first step, the specific preparation process of the curing agent slow-release particles is as follows: S1, mixing the required amount of resin curing agent and porous alumina ceramic balls and stirring for 15 to 30 minutes to obtain a mixture 1; S2, heating a required amount of phase change silicone grease to 60° C. to 80° C. to melt the phase change silicone grease to obtain a phase change silicone grease melt, adding the mixture to the phase change silicone grease melt and stirring for 10 to 15 minutes, and then adding a portion of the metal oxide and stirring for 10 to 15 minutes to obtain a solidified liquid; S3, cooling the solidifying liquid to room temperature to solidify it, and breaking the solidified solidifying liquid into pieces of 3 mm to 6 mm to obtain curing agent slow-release particles.

[0029] Compared with the prior art, the present invention has the following beneficial effects: The thermosetting resin composition for cementing of the present invention is prepared in advance from raw materials porous alumina ceramic balls, resin curing agent, phase change silicone grease and a small amount of metal oxide into curing agent slow-release particles, the resin curing agent can be filled in the gaps of the porous alumina ceramic balls, and the phase change silicone grease is used to soften at above 50°C and solidify at room temperature. Under the condition of 60°C to 80°C, the mixture of the porous alumina ceramic balls and the resin curing agent is mixed with the phase change silicone grease, the phase change silicone grease enters the pores of the porous alumina ceramic balls, the phase change silicone grease is coated on the outer surface of the porous alumina ceramic balls, and continues to mix with a small amount of metal oxide, the metal oxide is also attached to the surface of the porous alumina ceramic balls, and after cooling to room temperature, the curing agent slow-release particles are obtained; then, thermosetting resin, phosphate, fluid loss reducer, cooling retarder, the remaining amount of metal oxide and water are added to the curing agent slow-release particles, and the mixture is mixed and stirred to obtain the thermosetting resin composition for cementing.

[0030] The temperature of the thermosetting resin composition for cementing of the present invention gradually increases during the process of being pumped to the target location. During the pipeline transmission process, the slow-release particles of the curing agent are squeezed. Under the friction of the metal oxide, a part of the resin curing agent originally coated on the outer wall of the porous alumina ceramic ball is separated and begins to play a curing role. As the pumping well section goes deeper, the temperature rises to above 50°C, the phase change silicone grease begins to melt, and the amount of the resin curing agent released increases due to the squeezing during the material transmission process and the friction of the metal oxide, and gradually begins to play a role. After the porous alumina ceramic ball is exposed, it itself has a certain cooling effect. The above factors combined make the initial setting time of the thermosetting resin composition for cementing of the present invention between 4h and 6h, and the final setting time within 24h.

[0031] Embodiment 10: The thermosetting resin composition for cementing comprises, by weight, 32 parts of thermosetting resin (compounded with epoxy resin, phenolic epoxy resin and silicone resin in a weight ratio of 3:1:1), 8 parts of resin curing agent (acid anhydride, specifically phthalic anhydride), 5 parts of porous alumina ceramic balls, 4 parts of phase change silicone grease, 92 parts of metal oxide (dead-burned magnesium oxide), 45 parts of phosphate (compounded with sodium monohydrogen phosphate and potassium dihydrogen phosphate in a weight ratio of 1:1), 3 parts of fluid loss additive (AMPS multi-polymer fluid loss additive, specifically SCF180 multi-polymer fluid loss additive), 20 parts of cooling retarder (magnesium nitrate) and 88 parts of water, and is obtained by the following method: In the first step, the required amount of porous alumina ceramic balls, resin curing agent, phase change silicone grease and a portion of metal oxide (2 parts) are prepared to obtain curing agent slow-release particles; wherein the specific preparation process of the curing agent slow-release particles is as follows: S1, mixing the required amount of resin curing agent and porous alumina ceramic balls and stirring for 20 minutes to obtain a mixture 1; S2, heating a required amount of phase change silicone grease to 70°C to melt it, obtaining a phase change silicone grease melt, adding the mixture to the phase change silicone grease melt and stirring for 12 minutes, and then adding a portion of the metal oxide and stirring for 15 minutes to obtain a solidified liquid; S3, cooling the solidifying liquid to room temperature to solidify it, and breaking the solidified solidifying liquid into pieces of 3 mm to 6 mm to obtain curing agent slow-release particles; In the second step, the required amount of thermosetting resin, phosphate, fluid loss reducer, cooling retarder, the remaining amount of metal oxide and the required amount of water are sequentially added to the curing agent slow-release particles, mixed and stirred for 45 minutes to obtain a thermosetting resin composition for cementing.

[0032] Embodiment 11: The thermosetting resin composition for cementing comprises, by weight, 20 parts of thermosetting resin (compounded with epoxy resin, phenolic epoxy resin and polybutene resin in a weight ratio of 3:1:1), 5 parts of resin curing agent (compounded with acid anhydride and aliphatic amine compound in a weight ratio of 4:1, the acid anhydride is specifically tung oil anhydride, and the aliphatic amine compound is triethylenetetramine), 4 parts of porous alumina ceramic balls, 3 parts of phase change silicone grease, 70 parts of metal oxide (compounded with dicalcium oxide and metakaolin in a weight ratio of 1:1), 35 parts of phosphate (compounded with sodium monohydrogen phosphate and diammonium hydrogen phosphate in a weight ratio of 2:1), 1 part of fluid loss reducer (AMPS multi-polymer fluid loss reducer, specifically M-89L salt-resistant fluid loss reducer), 15 parts of cooling retarder (zeolite powder) and 40 parts of water, and is obtained by the following method: In the first step, the required amount of porous alumina ceramic balls, resin curing agent, phase change silicone grease and a portion of metal oxide (1 part) are prepared to obtain curing agent slow-release particles; wherein the specific preparation process of the curing agent slow-release particles is as follows: S1, mixing the required amount of resin curing agent and porous alumina ceramic balls and stirring for 15 minutes to obtain a mixture 1; S2, heating a required amount of phase change silicone grease to 60° C. to 80° C. to melt the phase change silicone grease to obtain a phase change silicone grease melt, adding the mixture to the phase change silicone grease melt and stirring for 10 minutes, and then adding a portion of the metal oxide and stirring for 10 minutes to obtain a solidified liquid; S3, cooling the solidifying liquid to room temperature to solidify it, and breaking the solidified solidifying liquid into pieces of 3 mm to 6 mm to obtain curing agent slow-release particles; In the second step, the required amount of thermosetting resin, phosphate, fluid loss reducer, cooling retarder, the remaining amount of metal oxide and the required amount of water are sequentially added to the curing agent slow-release particles, mixed and stirred for 20 minutes to obtain a thermosetting resin composition for cementing.

[0033] Embodiment 12: The thermosetting resin composition for cementing comprises, by weight, 60 parts of thermosetting resin (formed by epoxy resin and phenolic epoxy resin in a weight ratio of 3:1), 10 parts of resin curing agent (formed by acid anhydride and alicyclic amine compound in a weight ratio of 4:1), 7 parts of porous alumina ceramic balls, 5 parts of phase change silicone grease, 115 parts of metal oxide (formed by dead-burned magnesium oxide and metakaolin in a weight ratio of 1:1), 55 parts of phosphate (formed by sodium dihydrogen phosphate and diammonium hydrogen phosphate in a weight ratio of 2:1), 5 parts of fluid loss additive (AMPS multi-polymer fluid loss additive, specifically SCF180 multi-polymer fluid loss additive), 25 parts of cooling retarder (formed by magnesium nitrate, magnesium chloride and zeolite powder in a weight ratio of 1:1:1) and 130 parts of water, and is obtained by the following method: In the first step, the required amount of porous alumina ceramic balls, resin curing agent, phase change silicone grease and a portion of metal oxide (3 parts) are prepared to obtain curing agent slow-release particles; wherein the specific preparation process of the curing agent slow-release particles is as follows: S1, mixing the required amount of resin curing agent and porous alumina ceramic balls and stirring for 30 minutes to obtain a mixture 1; S2, heating a required amount of phase change silicone grease to 80°C to melt it, obtaining a phase change silicone grease melt, adding the mixture to the phase change silicone grease melt and stirring for 15 minutes, and then adding a portion of the metal oxide and stirring for 15 minutes to obtain a solidified liquid; S3, cooling the solidifying liquid to room temperature to solidify it, and breaking the solidified solidifying liquid into pieces of 3 mm to 6 mm to obtain curing agent slow-release particles; In the second step, the required amount of thermosetting resin, phosphate, fluid loss reducer, cooling retarder, the remaining amount of metal oxide and the required amount of water are sequentially added to the curing agent slow-release particles, mixed and stirred for 60 minutes to obtain a thermosetting resin composition for cementing.

[0034] Comparative Example 1: The difference from Example 10 is that in the preparation method of Comparative Example 1, the curing agent sustained-release particles are not prepared in advance, and all the raw materials are mixed at one time, and the mixture is stirred for 90 minutes to 100 minutes to obtain the particles.

[0035] Comparative Example 2: The difference from Example 10 is that the raw material porous alumina ceramic balls are replaced with solid alumina ceramic balls.

[0036] Example 13: The performance of the thermosetting resin compositions for cementing obtained in Examples 10 to 12 of the present invention was tested, and at the same time, the thermosetting resin compositions for cementing obtained in Comparative Examples 1 to 2 of the present invention were used as a comparison.

[0037] The test results are shown in Table 1. It can be seen from Table 1 that the initial setting time of the thermosetting resin composition for cementing obtained in Examples 10 to 12 of the present invention is within 4.9h to 6h under 80°C environment, and the final setting time is within 24h, which can meet the needs of underground construction, and the compressive strength of the solidified body is good, up to 22.71MPa / 48h. In Comparative Example 1 of the present invention, since the curing agent slow-release particles are not prepared in advance, all materials are weighed and stirred uniformly, resulting in them not reaching the target position and starting to solidify, which is not conducive to underground construction; and in Comparative Example 2 of the present invention, since porous alumina ceramic balls are not used, the curing agent slow-release particles prepared by solid alumina ceramic balls are not effective and do not play a big role in slow setting.

[0038] In summary, the resin curing agent in the thermosetting resin composition for cementing of the present invention is slowly released, the initial setting time of the composition is greater than 4 hours, it starts to solidify after being pumped to the target position, and the final setting time is within 24 hours.

[0039] The above technical features constitute the embodiments of the present invention, which have strong adaptability and implementation effect. Non-essential technical features can be added or reduced according to actual needs to meet the requirements of different situations.

Claims

1. A thermosetting resin composition for cementing, characterized in that The raw materials include, by weight, 15 to 60 parts of thermosetting resin, 5 to 10 parts of resin curing agent, 4 to 7 parts of porous alumina ceramic balls, 3 to 5 parts of phase change silicone grease, 70 to 115 parts of metal oxides, 35 to 55 parts of phosphates, 1 to 5 parts of fluid loss reducer, 15 to 25 parts of cooling retarder and 30 to 130 parts of water.

2. The thermosetting resin composition for cementing according to claim 1, characterized in that The thermosetting resin is two or more of epoxy resin, novolac epoxy resin, polybutylene resin, silicone resin and furan resin.

3. The thermosetting resin composition for cementing according to claim 1 or 2, characterized in that The resin curing agent is one or more of an acid anhydride, aliphatic amines, alicyclic amines, phenolic compounds and polyols.

4. The thermosetting resin composition for cementing according to any one of claims 1 to 3, characterized in that The metal oxide is one or more of dead-burned magnesium oxide, aluminum oxide, iron oxide, dicalcium oxide, and metakaolin.

5. The thermosetting resin composition for cementing according to any one of claims 1 to 4, characterized in that The phosphate is one or more of sodium monohydrogen phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and polyphosphate.

6. The thermosetting resin composition for cementing according to any one of claims 1 to 5, characterized in that The fluid loss reducer is an AMPS multipolymer type fluid loss reducer.

7. The thermosetting resin composition for cementing according to any one of claims 1 to 6, characterized in that The cooling and retarding agent is one or more of magnesium nitrate, magnesium chloride and zeolite powder.

8. The thermosetting resin composition for cementing according to any one of claims 1 to 7, characterized in that Obtained as follows: In the first step, a required amount of porous alumina ceramic balls, a resin curing agent, a phase change silicone grease and a portion of metal oxides are prepared to obtain curing agent slow-release particles; In the second step, the required amount of thermosetting resin, phosphate, fluid loss reducer, cooling retarder, the remaining amount of metal oxide and the required amount of water are sequentially added to the curing agent slow-release particles, mixed and stirred for 20 to 60 minutes to obtain a thermosetting resin composition for cementing.

9. The thermosetting resin composition for cementing according to claim 8, characterized in that In the first step, the specific preparation process of the curing agent slow-release particles is as follows: S1, mixing the required amount of resin curing agent and porous alumina ceramic balls and stirring for 15 to 30 minutes to obtain a mixture 1; S2, heating a required amount of phase change silicone grease to 60° C. to 80° C. to melt the phase change silicone grease to obtain a phase change silicone grease melt, adding the mixture to the phase change silicone grease melt and stirring for 10 to 15 minutes, and then adding a portion of the metal oxide and stirring for 10 to 15 minutes to obtain a solidified liquid; S3, cooling the solidifying liquid to room temperature to solidify it, and breaking the solidified solidifying liquid into pieces of 3 mm to 6 mm to obtain curing agent slow-release particles.

10. A method for preparing a thermosetting resin composition for cementing according to any one of claims 1 to 7 and 9, characterized in that Proceed as follows: In the first step, a required amount of porous alumina ceramic balls, a resin curing agent, a phase change silicone grease and a portion of metal oxides are prepared to obtain curing agent slow-release particles; In the second step, the required amount of thermosetting resin, phosphate, fluid loss reducer, cooling retarder, the remaining amount of metal oxide and the required amount of water are sequentially added to the curing agent slow-release particles, mixed and stirred for 20 to 60 minutes to obtain a thermosetting resin composition for cementing.

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