CN116023594A - CO (carbon monoxide) 2 Leakage-proof agent for geological storage and preparation method thereof - Google Patents
CO (carbon monoxide) 2 Leakage-proof agent for geological storage and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a CO 2 The leakproof agent for geological storage has the structural formula:
r is a hydrophilic graft copolymer monomer; a is more than or equal to 5 and less than or equal to 15, b is more than or equal to 10 and less than or equal to 20. CO (carbon monoxide) 2 Preparation of leakproof agent for geological storageThe preparation method comprises the following steps of S1: adding polyvinyl alcohol and water into a reaction container, heating until the polyvinyl alcohol is completely dissolved, cooling to room temperature, adding an emulsifier, heating, adding an ammonium persulfate aqueous solution, heating, slowly dropwise adding vinyl acetate, carrying out heat preservation reaction, adding the ammonium persulfate aqueous solution, heating, carrying out reflux reaction, and regulating the pH value to 5-6 after the reaction is finished to obtain an intermediate I; s2: adding the intermediate I into another reaction vessel, heating, adding ammonium persulfate aqueous solution, slowly dropwise adding hydrophilic graft copolymer monomer, heating, preserving heat for reaction, and stirring and steaming to obtain a product II; s3: adding a compound emulsifier into water, then adding a product II and tetraethoxysilane into the water, and obtaining CO after the reaction is finished 2 Leak-proof agent for geological storage.
Description
Technical Field
The invention belongs to the field of plugging agents, and in particular relates to a CO 2 A leakproof agent for geological storage and a preparation method thereof.
Background
In the development process of oil field, water is injected into oil reservoir through special injection well to maintain or restore oil reservoir pressure, so that oil reservoir has strong driving force to raise oil reservoir exploitation speed and recovery ratio.
Because of the problems of rapid formation energy failure, insufficient natural capacity supply and the like of the low-permeability oil reservoir, the problems of low water injection exploitation efficiency, no injection and no production are increasingly remarkable.
In order to solve such problems, some oil fields perform CO by injecting carbon dioxide at high temperature and high pressure 2 Oil displacement and oil recovery rate are improved. But at present CO is sequestered by formation cement 2 Because of the cracks in the formation, the cement is exposed to moisture and CO 2 Corrosion decomposition of (C) leads to reduced sealing effect and even leakage, thus severely affecting CO 2 Is effective in sealing.
Disclosure of Invention
The invention aims to: to increase CO 2 Flooding and CO 2 CO in the process of enhanced imbibition oil extraction 2 Sealing efficiency of (C) to realize CO 2 The invention discloses a CO 2 A leakproof agent for geological storage and a preparation method thereof.
The technical scheme is as follows: CO (carbon monoxide) 2 The leakproof agent for geological storage has the structural formula:
wherein R is a hydrophilic graft copolymer monomer;
a and b are integers, a is more than or equal to 5 and less than or equal to 15, and b is more than or equal to 10 and less than or equal to 20.
Further, the hydrophilic graft copolymer monomer is one of acrylic acid, methyl acrylate and ethyl acrylate.
CO (carbon monoxide) 2 The preparation method of the leak-proof agent for geological storage comprises the following steps:
s1: adding polyvinyl alcohol and water into a reaction container, heating to 90-95 ℃, cooling to room temperature after the polyvinyl alcohol is completely dissolved, then adding an emulsifying agent, heating to 60-65 ℃, adding a proper amount of ammonium persulfate aqueous solution, heating to 68-70 ℃ after the addition is finished, slowly dropwise adding vinyl acetate, carrying out heat preservation reaction for 15-20 min after the dropwise addition is finished, adding a proper amount of ammonium persulfate aqueous solution again, heating to 80-85 ℃, carrying out reflux reaction for 2-3 h, and adding a certain amount of sodium bicarbonate aqueous solution to adjust the pH to 5-6 after the reaction is finished to obtain an intermediate I;
s2: adding the intermediate I obtained in the step S1 into another reaction container, then heating to 50-55 ℃, adding a proper amount of ammonium persulfate aqueous solution, slowly dripping hydrophilic graft copolymer monomer into the reaction container after the completion of the reaction, heating to 60-65 ℃, preserving heat, reacting for 1-2 h, stirring, and steaming to obtain a product II;
s3: adding a compound emulsifier into water, then adding a product II obtained by S2 and tetraethoxysilane into water according to a certain proportion to obtain a reaction system, and obtaining CO after the reaction is finished 2 Leak-proof agent for geological storage.
The reaction vessel is a reaction vessel commonly used in laboratories, such as a three-neck flask and a four-neck flask.
Preferably, the hydrophilic graft copolymer monomer in step S2 is one of acrylic acid, methyl acrylate and ethyl acrylate.
Preferably, the addition amount of the polyvinyl alcohol in the step S1 is 8-10% of the total mass of the polyvinyl alcohol and water.
Preferably, the emulsifier in the step S1 is a compound emulsifier of sodium dodecyl benzene sulfonate and OP-10 in equal mass ratio, and the addition amount of the compound emulsifier is 4-7% of the addition amount of vinyl acetate.
Preferably, the concentration of the ammonium persulfate aqueous solution in the step S1 is 20wt%, the addition amount of the ammonium persulfate aqueous solution in the step S1 is 4-6% of the addition amount of the hydrophilic graft copolymer monomer in the step S2, wherein the first addition amount of the ammonium persulfate aqueous solution is 1/3 of the total addition amount of the ammonium persulfate aqueous solution, and the second addition amount is the rest of the ammonium persulfate aqueous solution.
Preferably, the addition amount of the vinyl acetate in the step S1 is 30% of the total mass of the polyvinyl alcohol and the water.
Further, step S1 adjusts the pH to 5-6 by adding sodium bicarbonate aqueous solution.
Further, the mass concentration of the sodium bicarbonate aqueous solution in the step S1 is 10-30wt%.
Preferably, the hydrophilic graft copolymer monomer in step S2 is added in an amount of 2 to 3 times the amount of vinyl acetate added.
Preferably, the mass concentration of the ammonium persulfate aqueous solution of step S2 is 20wt%, and the addition amount of the ammonium persulfate aqueous solution of step S2 is 4-6% of the addition amount of the hydrophilic graft copolymer monomer of step S2.
Preferably, the compound emulsifier in the step S3 is a compound emulsifier of an emulsifier SP-60 and an emulsifier TW60, the HLB value of the compound emulsifier is 10-12, and the addition amount of the compound emulsifier is 1-2% of the total mass of the compound emulsifier and water.
Preferably, the mass ratio of the product II obtained in the step S2 to the tetraethoxysilane in the step S3 is 2: (1-1.1).
Preferably, the water added in the step S3 accounts for 60-70% of the mass of the reaction system in the step S3.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method is simple and easy to implement, the reaction mechanism is clear, the hydrophilicity of the polymerized product is improved by grafting hydrophilic copolymer monomer on polyvinyl acetate, a uniform emulsion is formed by compounding an emulsifier and ethyl orthosilicate, after the emulsion enters a stratum, the emulsion is influenced by the temperature rise of the stratum, the polyvinyl acetate structure of the copolymer in the emulsion is dehydrated and decomposed by heating to expose hydroxyl, meanwhile, the ethyl orthosilicate is subjected to the stratum environment (high temperature and low pH environment) to promote hydrolysis to generate silicic acid, the silicic acid reacts with the exposed hydroxyl structure of the copolymer to generate high-polymerization solid gel, so that the blockage of cracks and pores is realized, and the CO is improved 2 Is provided. The method has good plugging effect, and can realize the effect of plugging CO 2 Is embedded with high efficiency.
2. The invention provides a CO 2 The preparation process of leakproof agent for geological embedding includes the first polymerization of vinyl acetate to form polyvinyl acetate, subsequent polymerization with hydrophilic graft copolymer monomer to raise its hydrophilicity, and final compounding of emulsifier and tetraethoxysilane to form homogeneous emulsionThe application is performed. The CO 2 The leakproof agent for geological storage can form solid gel with high strength, thereby realizing CO sealing 2 Plugging of formation cracks and pores to enhance CO 2 Is prevented from escaping.
Drawings
FIG. 1 is a schematic diagram of an experimental set-up for characterizing plugging properties.
Wherein:
| 1-computer acquisition system | 2-pressure sensor |
| 3-intermediate tank | 4-advection pump |
| 5-liquid storage tank | 6-constant temperature bath |
| 7-sand filling pipe |
The specific embodiment is as follows:
the following detailed description of specific embodiments of the invention.
The invention provides a CO 2 The preparation method of the leakproof agent for geological storage comprises the steps of firstly, carrying out polymerization reaction on vinyl acetate to form polyvinyl acetate, then, carrying out polymerization on the polyvinyl acetate and hydrophilic graft copolymer monomer to improve the hydrophilicity of the polyvinyl acetate, and finally, forming uniform emulsion with tetraethoxysilane through compounding an emulsifier for application. The CO 2 The leakproof agent for geological storage can form solid gel with high strength, thereby realizing CO sealing 2 Plugging of formation cracks and pores to enhance CO 2 Is prevented from escaping.
The invention discloses a CO 2 The preparation method of the leakproof agent for geological storage comprises the following synthetic routes:
the mechanism of hydrolysis of tetraethyl orthosilicate to silicic acid is as follows:
CO 2 the mechanism of the leakproof agent for geological storage forming solid gel is as follows:
example 1
CO (carbon monoxide) 2 The preparation method of the leak-proof agent for geological storage comprises the following steps:
s1, weighing 6.4g of polyvinyl alcohol and 80g of water, pouring the polyvinyl alcohol and the 80g of water into a reaction container (for example, a 500mL three-neck flask with a stirrer), heating to 90 ℃, fully stirring until the polyvinyl alcohol is completely dissolved, cooling to room temperature, then adding 0.52g of OP-10 and 0.52g of sodium dodecyl benzene sulfonate respectively, and heating to 60 ℃ after adding. 1g of ammonium persulfate was weighed into a small 25mL beaker and dissolved in 5g of water, and the solution was sufficiently dissolved to obtain an ammonium persulfate solution. Adding a 1/3 ammonium persulfate solution into a reaction vessel, heating to 68 ℃, slowly dropwise adding 26g of vinyl acetate, carrying out heat preservation reaction for 15min after dropwise adding, then adding the rest 2/3 ammonium persulfate solution, heating to 80 ℃, and carrying out reflux reaction for 2h. After the completion of the reaction, 10wt% sodium hydrogencarbonate aqueous solution was added to adjust the pH to 5 to obtain intermediate I.
S2, adding the intermediate I obtained in the step S1 into another reaction container (such as a three-neck flask), then heating to 50 ℃, weighing 2g of ammonium persulfate in a small 25mL beaker, dissolving the ammonium persulfate in 10g of water, adding the ammonium persulfate solution into the reaction container after the ammonium persulfate solution is fully dissolved, slowly adding 52g of acrylic acid after the ammonium persulfate solution is added, heating to 60 ℃, keeping the temperature for reaction for 1h, and stirring and steaming to obtain a product II.
S3, adding 1g of compound emulsifier into 60g of water, then adding 26.7g of the product obtained in the step S2 and 13.3g of ethyl orthosilicate, and fully and uniformly stirring to obtain the CO 2 Leak-proof agent for geological storage.
Further, the compound emulsifier in the step S3 is a compound emulsifier of an emulsifier SP-60 and an emulsifier TW60, and the HLB value of the compound emulsifier is 10.
Example 2
CO (carbon monoxide) 2 The preparation method of the leak-proof agent for geological storage comprises the following steps:
s1, weighing 8g of polyvinyl alcohol and 80g of water, pouring the polyvinyl alcohol and the 80g of water into a reaction container (for example, a 500mL three-neck flask with a stirrer), heating to 95 ℃, fully stirring until the polyvinyl alcohol is completely dissolved, cooling to room temperature, then adding 0.91g of OP-10 and 0.91g of sodium dodecyl benzene sulfonate respectively, and heating to 65 ℃ after adding. 1g of ammonium persulfate was weighed into a small 25mL beaker and dissolved in 5g of water, and the solution was sufficiently dissolved to obtain an ammonium persulfate solution. Adding a 1/3 ammonium persulfate solution into a reaction vessel, heating to 70 ℃, slowly dropwise adding 26g of vinyl acetate, carrying out heat preservation reaction for 20min after dropwise adding, then adding the rest 2/3 ammonium persulfate solution, heating to 85 ℃, and carrying out reflux reaction for 3h. After the reaction, 30wt% sodium bicarbonate aqueous solution was added to adjust the pH to 6 to obtain intermediate I.
S2, adding the intermediate I obtained in the step S1 into another reaction container (such as a three-neck flask), and then heating to 55 ℃.3g of ammonium persulfate is weighed in a small 25mL beaker and dissolved in 15g of water, the ammonium persulfate solution is fully dissolved to obtain the ammonium persulfate solution, then the ammonium persulfate solution is added into a reaction vessel, after the addition is finished, 78g of acrylic acid is slowly added, the temperature is raised to 65 ℃, the reaction is carried out for 2 hours under heat preservation, and the product II is obtained after stirring and rotary evaporation.
S3, adding 2g of compound emulsifier into 60g of water26.4g of the product II of the step S2 and 13.6g of ethyl orthosilicate are then added and stirred fully and uniformly to obtain the CO 2 Leak-proof agent for geological storage.
Example 3
CO (carbon monoxide) 2 The preparation method of the leak-proof agent for geological storage comprises the following steps:
s1, weighing 6.4g of polyvinyl alcohol and 80g of water, pouring the polyvinyl alcohol and the 80g of water into a reaction container (for example, a 500mL three-neck flask with a stirrer), heating to 94 ℃, fully stirring until the polyvinyl alcohol is completely dissolved, cooling to room temperature, then adding 0.8g of OP-10 and 0.8g of sodium dodecyl benzene sulfonate respectively, and heating to 62 ℃ after adding. 1g of ammonium persulfate was weighed into a small 25mL beaker and dissolved in 5g of water, and the solution was sufficiently dissolved to obtain an ammonium persulfate solution. Adding a 1/3 ammonium persulfate solution into a reaction vessel, heating to 69 ℃, slowly dropwise adding 26g of vinyl acetate, carrying out heat preservation reaction for 18min after dropwise adding, then adding the rest 2/3 ammonium persulfate solution, heating to 82 ℃, and carrying out reflux reaction for 2.5h. After the completion of the reaction, a 20wt% aqueous sodium hydrogencarbonate solution was added to adjust the pH to 5.5 to obtain intermediate I.
S2, adding the intermediate I obtained in the step S1 into another reaction container (such as a three-neck flask), and then heating to 55 ℃. 2g of ammonium persulfate is weighed in a small 25mL beaker and dissolved in 10g of water, the ammonium persulfate solution is fully dissolved to obtain the ammonium persulfate solution, the ammonium persulfate solution is added into a three-neck flask, after the ammonium persulfate solution is added, 78g of methyl acrylate is slowly added, the temperature is raised to 60 ℃, the temperature is kept for 2h of reaction, and the product II is obtained after stirring and rotary steaming.
S3, adding 2g of compound emulsifier into 60g of water, then adding 26.7g of the product II obtained in the step S2 and 13.3g of tetraethoxysilane, and fully and uniformly stirring to obtain the CO 2 Leak-proof agent for geological storage.
Example 4
CO (carbon monoxide) 2 The preparation method of the leak-proof agent for geological storage comprises the following steps:
s1, weighing 8g of polyvinyl alcohol and 80g of water, pouring the polyvinyl alcohol and the 80g of water into a reaction container (for example, a 500mL three-neck flask with a stirrer), heating to 90 ℃, fully stirring until the polyvinyl alcohol is completely dissolved, cooling to room temperature, then adding 0.65g of OP-10 and 0.65g of sodium dodecyl benzene sulfonate respectively, and heating to 60 ℃ after adding. 1g of ammonium persulfate was weighed into a small 25mL beaker and dissolved in 5g of water, and the solution was sufficiently dissolved to obtain an ammonium persulfate solution. Adding a 1/3 ammonium persulfate solution into a reaction vessel, heating to 70 ℃, slowly dropwise adding 26g of vinyl acetate, carrying out heat preservation reaction for 20min after dropwise adding, then adding the rest 2/3 ammonium persulfate solution, heating to 85 ℃, and carrying out reflux reaction for 3h. After the reaction, 15wt% sodium bicarbonate aqueous solution was added to adjust the pH to 6 to obtain intermediate I.
S2, adding the intermediate I obtained in the step S1 into another reaction container (such as a three-neck flask), and then heating to 60 ℃. 2g of ammonium persulfate is weighed in a small 25mL beaker and dissolved in 10g of water, the ammonium persulfate solution is fully dissolved to obtain the ammonium persulfate solution, the ammonium persulfate solution is added into a reaction vessel, 52g of methyl acrylate is slowly added after the ammonium persulfate solution is added, the temperature is raised to 65 ℃, the temperature is kept for 2h, and the product II is obtained after stirring and rotary evaporation.
S3, adding 1g of compound emulsifier into 60g of water, then adding 26.1g of product II of step S2 and 13.9g of ethyl orthosilicate, and fully and uniformly stirring to obtain the CO 2 Leak-proof agent for geological storage.
Example 5
CO (carbon monoxide) 2 The preparation method of the leak-proof agent for geological storage comprises the following steps:
s1, weighing 6.4g of polyvinyl alcohol and 80g of water, pouring the polyvinyl alcohol and the 80g of water into a reaction container (for example, a 500mL three-neck flask with a stirrer), heating to 90 ℃, fully stirring until the polyvinyl alcohol is completely dissolved, cooling to room temperature, then adding 0.6g of OP-10 and 0.6g of sodium dodecyl benzene sulfonate respectively, and heating to 65 ℃ after adding. 1g of ammonium persulfate was weighed into a small 25mL beaker and dissolved in 5g of water, and the solution was sufficiently dissolved to obtain an ammonium persulfate solution. Adding a 1/3 ammonium persulfate solution into a reaction vessel, heating to 68 ℃, slowly dropwise adding 26g of vinyl acetate, carrying out heat preservation reaction for 20min after dropwise adding, then adding the rest 2/3 ammonium persulfate solution, heating to 80 ℃, and carrying out reflux reaction for 3h. After the reaction, 10wt% sodium bicarbonate aqueous solution was added to adjust the pH to 5-6 to obtain intermediate I.
S2, adding the intermediate I obtained in the step S1 into another reaction container (such as a three-neck flask), and then heating to 60 ℃. 2g of ammonium persulfate is weighed in a small 25mL beaker and dissolved in 10g of water, the ammonium persulfate solution is fully dissolved to obtain the ammonium persulfate solution, the ammonium persulfate solution is added into a reaction vessel, after the addition is finished, 52g of ethyl acrylate is slowly added, the temperature is raised to 65 ℃, the reaction is carried out for 2h under heat preservation, and the product II is obtained after stirring and rotary evaporation.
S3, adding 1g of compound emulsifier into 60g of water, then adding 26.7g of the product II obtained in the step S2 and 13.3g of ethyl orthosilicate, and fully and uniformly stirring to obtain the CO 2 Leak-proof agent for geological storage.
Example 6
CO (carbon monoxide) 2 The preparation method of the leak-proof agent for geological storage comprises the following steps:
s1, weighing 8g of polyvinyl alcohol and 80g of water, pouring the polyvinyl alcohol and the 80g of water into a reaction container (for example, a 500mL three-neck flask with a stirrer), heating to 90 ℃, fully stirring until the polyvinyl alcohol is completely dissolved, cooling to room temperature, then adding 0.9g of OP-10 and 0.9g of sodium dodecyl benzene sulfonate respectively, and heating to 60 ℃ after adding. 1g of ammonium persulfate was weighed into a small 25mL beaker and dissolved in 5g of water, and the solution was sufficiently dissolved to obtain an ammonium persulfate solution. Adding a 1/3 ammonium persulfate solution into a three-neck flask, heating to 68 ℃, slowly dropwise adding 26g of vinyl acetate, carrying out heat preservation reaction for 20min after dropwise adding, then adding the rest 2/3 ammonium persulfate solution, heating to 80 ℃, and carrying out reflux reaction for 3h. After the completion of the reaction, 25wt% sodium hydrogencarbonate aqueous solution was added to adjust the pH to 6 to obtain intermediate I.
S2, adding the intermediate I obtained in the step S1 into a three-neck flask, and then heating to 60 ℃.3g of ammonium persulfate is weighed in a small 25mL beaker and dissolved in 15g of water, the ammonium persulfate solution is fully dissolved to obtain the ammonium persulfate solution, the ammonium persulfate solution is added into a three-neck flask, after the addition is finished, 78g of ethyl acrylate is slowly added, the temperature is raised to 65 ℃, the temperature is kept for 2h of reaction, and the product II is obtained after stirring and rotary steaming.
S3, adding 1g of compound emulsifier into 60g of water, and then adding 26.7g of compound emulsifierStep S2, the product II and 13.3g of tetraethoxysilane are fully and uniformly stirred to obtain the CO 2 Leak-proof agent for geological storage.
Characterization of Performance
1. Temperature for CO 2 Influence of leakage-preventing agent for geological storage
To characterize a CO 2 The temperature of the leakproof agent for geological storage has an influence on the generation of solid gel, and the CO obtained in example 2 2 Placing the leakproof agent for geological storage in a glass bottle, adding acid to adjust the pH value to 6, and heating to observe the solid precipitation condition.
From the experimental results, it can be seen that the CO 2 The leakproof agent for geological storage can not separate out solid gel at normal temperature, when the temperature is increased to 80 ℃, the solid gel is separated out, meanwhile, along with the continuous increase of the temperature, the solid separation amount is not changed, the temperature only affects the separation speed of the solid gel, the solid gel is not affected, and the temperature is not changed 2 The plugging efficiency of the leakproof agent for geological storage.
2. Plugging property
In order to characterize the plugging performance of a leak-proof agent for CO2 geological storage, a plugging test experiment was performed using the apparatus shown in fig. 1.
As shown in fig. 1, the liquid storage tank 5, the advection pump 4, the intermediate container tank 3 and the constant temperature tank 6 are sequentially connected, a sand filling pipe 7 is arranged in the constant temperature tank 6, a pressure sensor 2 is arranged in a pipeline connecting the intermediate container tank 3 and the constant temperature tank 6, and the output end of the pressure sensor 2 is connected with the input end of the computer acquisition system 1.
The sand filling pipe 7 with different permeabilities was manufactured by wet filling method, the porosities were calculated, then water was injected at a rate of 0.5mL/min, the water phase permeabilities of the sand filling pipe 7 were calculated, then the leak-proof agent for CO2 geological storage obtained in example 2 of 1.0PV was respectively injected into the sand filling pipe, the valves at both ends of the sand filling pipe were closed, the thermostatic bath 6 was kept at 80 degrees centigrade as solid gel, then water was injected at a rate of 0.5mL/min, the injection end pressure was recorded, and the plugging rate was calculated. The experimental results are shown in tables 1 and 2.
TABLE 1 basic parameters of sand filling pipe
TABLE 2 Sand filling pipe plugging effect
As can be seen from Table 2, the plugging rates of the leakage preventive for CO2 geological storage obtained by the method are all above 95%, which indicates that the leakage preventive for CO2 geological storage has excellent plugging effect on cracks and pores in stratum, and can prevent CO 2 Is not limited.
3. Thermal stability
In order to characterize the thermal stability of the leakage preventing agent for CO2 geological storage, the thermal stability test is carried out by using the sand filling pipe in the table 1, the leakage preventing agent for CO2 geological storage obtained in the example 2 is respectively added into the sand filling pipe, the example 2 is put into a baking oven at 150 ℃ for sealing storage by using the sand filling pipe of 1-1, and the sealing rate of different ageing times is respectively calculated by using the testing method of the device and the sealing performance test in the figure 1 after 10 days, 30 days and 90 days. The experimental results are shown in table 3.
TABLE 3 Sand filling pipe plugging effects at different aging times
As can be seen from Table 3, the blocking pressure difference gradually decreased with the increase of the aging time, but the blocking rate decreased slightly, and the blocking rate was 0.16% lower after 90 days than that of the initial one, but the blocking rate was still more than 95%. Therefore, the plugging agent has good thermal stability.
Example 7
CO (carbon monoxide) 2 The leakproof agent for geological storage has the structural formula:
wherein R is a hydrophilic graft copolymer monomer;
a, b are integers, a=5, b=10.
Further, the hydrophilic graft copolymer monomer is acrylic acid.
Example 8
CO (carbon monoxide) 2 The leakproof agent for geological storage has the structural formula:
wherein R is a hydrophilic graft copolymer monomer;
a, b are integers, a=10, b=15.
Further, the hydrophilic graft copolymer monomer is methyl acrylate.
Example 9
CO (carbon monoxide) 2 The leakproof agent for geological storage has the structural formula:
wherein R is a hydrophilic graft copolymer monomer;
a, b are integers, a=15, b=20.
Further, the hydrophilic graft copolymer monomer is ethyl acrylate.
Example 10
CO (carbon monoxide) 2 The preparation method of the leak-proof agent for geological storage comprises the following steps:
s1: adding polyvinyl alcohol and water into a reaction container, heating to 90 ℃, cooling to room temperature after the polyvinyl alcohol is completely dissolved, then adding an emulsifier, heating to 60 ℃, adding a proper amount of ammonium persulfate aqueous solution, heating to 68 ℃ after the addition is finished, slowly dropwise adding vinyl acetate, carrying out heat preservation reaction for 15min after the dropwise addition is finished, adding a proper amount of ammonium persulfate aqueous solution again, heating to 80 ℃, carrying out reflux reaction for 3h, and adding a certain amount of sodium bicarbonate aqueous solution to adjust the pH to 5 after the reaction is finished to obtain an intermediate I;
s2: adding the intermediate I obtained in the step S1 into another reaction container, then heating to 50 ℃, adding a proper amount of ammonium persulfate aqueous solution, slowly dripping hydrophilic graft copolymer monomer into the reaction container after the completion of the reaction, heating to 60 ℃, preserving heat for 2 hours, stirring, and steaming to obtain a product II;
s3: adding a compound emulsifier into water, then adding a product II obtained by S2 and tetraethoxysilane into water according to a certain proportion to obtain a reaction system, and obtaining CO after the reaction is finished 2 Leak-proof agent for geological storage.
The reaction vessel is a reaction vessel commonly used in laboratories, such as a three-neck flask.
Preferably, the hydrophilic graft copolymer monomer described in step S2 is acrylic acid.
Preferably, the addition amount of the polyvinyl alcohol in the step S1 is 8% of the total mass of the polyvinyl alcohol and water.
Preferably, the emulsifier in the step S1 is a compound emulsifier of sodium dodecyl benzene sulfonate and OP-10 in equal mass ratio, and the addition amount of the compound emulsifier is 4% of the addition amount of vinyl acetate.
Preferably, the concentration of the ammonium persulfate aqueous solution in the step S1 is 20wt%, and the addition amount of the ammonium persulfate aqueous solution in the step S1 is 4% of the addition amount of the hydrophilic graft copolymer monomer in the step S2, wherein the first addition amount of the ammonium persulfate aqueous solution is 1/3 of the total addition amount of the ammonium persulfate aqueous solution, and the second addition amount is the rest of the ammonium persulfate aqueous solution.
Preferably, the addition amount of the vinyl acetate in the step S1 is 30% of the total mass of the polyvinyl alcohol and the water.
Further, step S1 adjusts the pH to 5 by adding an aqueous sodium bicarbonate solution.
Further, the sodium bicarbonate aqueous solution in the step S1 has a mass concentration of 10wt%.
Preferably, the hydrophilic graft copolymer monomer described in step S2 is added in an amount of 2 times the amount of vinyl acetate added.
Preferably, the mass concentration of the ammonium persulfate aqueous solution of step S2 is 20wt%, and the addition amount of the ammonium persulfate aqueous solution of step S2 is 4wt% of the addition amount of the hydrophilic graft copolymer monomer of step S2.
Preferably, the compound emulsifier in the step S3 is a compound emulsifier of an emulsifier SP-60 and an emulsifier TW60, the HLB value of the compound emulsifier is 10, and the addition amount of the compound emulsifier is 1wt% of the mass sum of the compound emulsifier and water.
Preferably, the mass ratio of the product II obtained in the step S2 to the tetraethoxysilane in the step S3 is 2:1.
preferably, the water added in step S3 is 60wt% of the mass of the reaction system in step S3.
Example 11
CO (carbon monoxide) 2 The preparation method of the leak-proof agent for geological storage comprises the following steps:
s1: adding polyvinyl alcohol and water into a reaction container, heating to 95 ℃, cooling to room temperature after the polyvinyl alcohol is completely dissolved, then adding an emulsifier, heating to 65 ℃, adding a proper amount of ammonium persulfate aqueous solution, heating to 70 ℃ after the addition is finished, slowly dropwise adding vinyl acetate, carrying out heat preservation reaction for 20min after the dropwise addition is finished, adding a proper amount of ammonium persulfate aqueous solution again, heating to 85 ℃, carrying out reflux reaction for 2h, and adding a certain amount of sodium bicarbonate aqueous solution to adjust the pH to 6 after the reaction is finished to obtain an intermediate I;
s2: adding the intermediate I obtained in the step S1 into another reaction container, then heating to 55 ℃, adding a proper amount of ammonium persulfate aqueous solution, slowly dripping hydrophilic graft copolymer monomer into the reaction container after the completion of the reaction, heating to 65 ℃, preserving heat for reaction for 1h, stirring, and steaming to obtain a product II;
s3: adding a compound emulsifier into water, then adding a product II obtained by S2 and tetraethoxysilane into water according to a certain proportion to obtain a reaction system, and obtaining CO after the reaction is finished 2 Leak-proof agent for geological storage.
The reaction vessel is a reaction vessel commonly used in laboratories, such as a four-necked flask.
Preferably, the hydrophilic graft copolymer monomer described in step S2 is methyl acrylate.
Preferably, the addition amount of the polyvinyl alcohol in the step S1 is 10% of the total mass of the polyvinyl alcohol and water.
Preferably, the emulsifier in the step S1 is a compound emulsifier of sodium dodecyl benzene sulfonate and OP-10 in equal mass ratio, and the addition amount of the compound emulsifier is 7% of the addition amount of vinyl acetate.
Preferably, the concentration of the ammonium persulfate aqueous solution in the step S1 is 20wt%, the addition amount of the ammonium persulfate aqueous solution in the step S1 is 6% of the addition amount of the hydrophilic graft copolymer monomer in the step S2, wherein the first addition amount of the ammonium persulfate aqueous solution is 1/3 of the total addition amount of the ammonium persulfate aqueous solution, and the second addition amount is the rest of the ammonium persulfate aqueous solution.
Preferably, the addition amount of the vinyl acetate in the step S1 is 30% of the total mass of the polyvinyl alcohol and the water.
Further, step S1 adjusts the pH to 6 by adding an aqueous sodium bicarbonate solution.
Further, the sodium bicarbonate aqueous solution in the step S1 has a mass concentration of 30wt%.
Preferably, the hydrophilic graft copolymer monomer described in step S2 is added in an amount 3 times the amount of vinyl acetate added.
Preferably, the mass concentration of the ammonium persulfate aqueous solution of step S2 is 20wt%, and the addition amount of the ammonium persulfate aqueous solution of step S2 is 6wt% of the addition amount of the hydrophilic graft copolymer monomer of step S2.
Preferably, the compound emulsifier in the step S3 is a compound emulsifier of an emulsifier SP-60 and an emulsifier TW60, the HLB value of the compound emulsifier is 12, and the addition amount of the compound emulsifier is 2wt% of the mass sum of the compound emulsifier and water.
Preferably, the mass ratio of the product II obtained in the step S2 to the tetraethoxysilane in the step S3 is 2: 1.1.
Preferably, the water added in step S3 is 70wt% of the mass of the reaction system in step S3.
Example 12
CO (carbon monoxide) 2 The preparation method of the leak-proof agent for geological storage comprises the following steps:
s1: adding polyvinyl alcohol and water into a reaction container, heating to 93 ℃, cooling to room temperature after the polyvinyl alcohol is completely dissolved, then adding an emulsifier, heating to 62 ℃, adding a proper amount of ammonium persulfate aqueous solution, heating to 69 ℃ after the addition is finished, slowly dropwise adding vinyl acetate, carrying out heat preservation reaction for 18min after the dropwise addition is finished, adding a proper amount of ammonium persulfate aqueous solution again, heating to 82 ℃, carrying out reflux reaction for 2-3 h, and adding a certain amount of sodium bicarbonate aqueous solution to adjust the pH to 5.5 after the reaction is finished to obtain an intermediate I;
s2: adding the intermediate I obtained in the step S1 into another reaction container, then heating to 52 ℃, adding a proper amount of ammonium persulfate aqueous solution, slowly dripping hydrophilic graft copolymer monomer into the reaction container after the completion of the reaction, heating to 62 ℃, preserving heat, reacting for 1.5h, stirring, and steaming to obtain a product II;
s3: adding a compound emulsifier into water, then adding a product II obtained by S2 and tetraethoxysilane into water according to a certain proportion to obtain a reaction system, and obtaining CO after the reaction is finished 2 Leak-proof agent for geological storage.
The reaction vessel is a reaction vessel commonly used in laboratories, such as a three-neck flask.
Preferably, the hydrophilic graft copolymer monomer described in step S2 is ethyl acrylate.
Preferably, the addition amount of the polyvinyl alcohol in the step S1 is 9% of the total mass of the polyvinyl alcohol and water.
Preferably, the emulsifier in the step S1 is a compound emulsifier of sodium dodecyl benzene sulfonate and OP-10 in equal mass ratio, and the addition amount of the compound emulsifier is 5% of the addition amount of vinyl acetate.
Preferably, the concentration of the ammonium persulfate aqueous solution in the step S1 is 20wt%, and the addition amount of the ammonium persulfate aqueous solution in the step S1 is 5% of the addition amount of the hydrophilic graft copolymer monomer in the step S2, wherein the first addition amount of the ammonium persulfate aqueous solution is 1/3 of the total addition amount of the ammonium persulfate aqueous solution, and the second addition amount is the rest of the ammonium persulfate aqueous solution.
Preferably, the addition amount of the vinyl acetate in the step S1 is 30% of the total mass of the polyvinyl alcohol and the water.
Further, step S1 adjusts the pH to 5.5 by adding aqueous sodium bicarbonate.
Further, the sodium bicarbonate aqueous solution in the step S1 has a mass concentration of 20wt%.
Preferably, the hydrophilic graft copolymer monomer described in step S2 is added in an amount of 2.5 times the amount of vinyl acetate added.
Preferably, the mass concentration of the ammonium persulfate aqueous solution of step S2 is 20wt%, and the addition amount of the ammonium persulfate aqueous solution of step S2 is 5% of the addition amount of the hydrophilic graft copolymer monomer of step S2.
Preferably, the compound emulsifier in the step S3 is a compound emulsifier of an emulsifier SP-60 and an emulsifier TW60, the HLB value of the compound emulsifier is 10-12, and the addition amount of the compound emulsifier is 1.5 weight percent of the total mass of the compound emulsifier and water.
Preferably, the mass ratio of the product II obtained in the step S2 to the tetraethoxysilane in the step S3 is 2: 1.05.
Preferably, the water added in step S3 is 65% of the mass of the reaction system in step S3.
The embodiments of the present invention have been described in detail. However, the present invention is not limited to the above-described embodiments, and various modifications may be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (13)
1. CO (carbon monoxide) 2 The leakproof agent for geological storage is characterized by comprising the following structural formula:
wherein R is a hydrophilic graft copolymer monomer;
a and b are integers, a is more than or equal to 5 and less than or equal to 15, and b is more than or equal to 10 and less than or equal to 20.
2. A CO according to claim 1 2 The leakproof agent for geological storage is characterized in that the hydrophilic graft copolymer monomer is one of acrylic acid, methyl acrylate and ethyl acrylate.
3. CO (carbon monoxide) 2 The preparation method of the leak-proof agent for geological storage is characterized by comprising the following steps of:
s1: adding polyvinyl alcohol and water into a reaction container, heating to 90-95 ℃, cooling to room temperature after the polyvinyl alcohol is completely dissolved, then adding an emulsifying agent, heating to 60-65 ℃, adding a proper amount of ammonium persulfate aqueous solution, heating to 68-70 ℃ after the addition is finished, slowly dropwise adding vinyl acetate, carrying out heat preservation reaction for 15-20 min after the dropwise addition is finished, adding a proper amount of ammonium persulfate aqueous solution again, heating to 80-85 ℃, carrying out reflux reaction for 2-3 h, and adding a certain amount of sodium bicarbonate aqueous solution to adjust the pH to 5-6 after the reaction is finished to obtain an intermediate I;
s2: adding the intermediate I obtained in the step S1 into another reaction container, then heating to 50-55 ℃, adding a proper amount of ammonium persulfate aqueous solution, slowly dripping hydrophilic graft copolymer monomer into the reaction container after the completion of the reaction, heating to 60-65 ℃, preserving heat, reacting for 1-2 h, stirring, and steaming to obtain a product II;
s3: adding a compound emulsifier into water, then adding a product II obtained by S2 and tetraethoxysilane into water according to a certain proportion to obtain a reaction system, and obtaining CO after the reaction is finished 2 Leak-proof agent for geological storage.
4. A CO according to claim 3 2 The preparation method of the leakproof agent for geological storage is characterized in that the hydrophilic graft copolymer monomer in the step S2 is acrylic acid and methyl acrylateOne of ethyl acrylate.
5. A CO according to claim 3 2 The preparation method of the leakproof agent for geological storage is characterized in that the addition amount of the polyvinyl alcohol in the step S1 is 8-10% of the total mass of the polyvinyl alcohol and water.
6. A CO according to claim 3 2 The preparation method of the leakproof agent for geological storage is characterized in that the emulsifier in the step S1 is a compound emulsifier of sodium dodecyl benzene sulfonate and OP-10 in equal mass ratio, and the addition amount of the compound emulsifier is 4-7% of the addition amount of vinyl acetate.
7. A CO according to claim 3 2 The preparation method of the leak-proof agent for geological storage is characterized in that the concentration of the ammonium persulfate aqueous solution in the step S1 is 20 weight percent, the addition amount of the ammonium persulfate aqueous solution in the step S1 is 4-6% of the addition amount of the hydrophilic graft copolymer monomer in the step S2, wherein the addition amount of the ammonium persulfate aqueous solution is 1/3 of the total addition amount of the ammonium persulfate aqueous solution for the first time, and the addition amount of the ammonium persulfate aqueous solution for the second time is the rest of the ammonium persulfate aqueous solution.
8. A CO according to claim 3 2 The preparation method of the leakproof agent for geological storage is characterized in that the adding amount of the vinyl acetate in the step S1 is 30% of the total mass of the polyvinyl alcohol and the water.
9. A CO according to claim 3 2 The preparation method of the leak-proof agent for geological storage is characterized in that the step S1 is to adjust the pH value to 5-6 by adding sodium bicarbonate aqueous solution;
the mass concentration of the sodium bicarbonate aqueous solution in the step S1 is 10-30wt%.
10. A CO according to claim 3 2 The preparation method of the leakproof agent for geological storage is characterized in that the hydrophilic graft copolymer monomer in the step S2The addition amount of (2) to (3) times of the addition amount of vinyl acetate.
11. A CO according to claim 3 2 The preparation method of the leak-proof agent for geological storage is characterized in that the mass concentration of the ammonium persulfate aqueous solution in the step S2 is 20wt%, and the addition amount of the ammonium persulfate aqueous solution in the step S2 is 4-6% of the addition amount of the hydrophilic graft copolymer monomer in the step S2.
12. A CO according to claim 3 2 The preparation method of the leakproof agent for geological storage is characterized in that the compound emulsifier in the step S3 is the compound emulsifier of the emulsifier SP-60 and the emulsifier TW60, the HLB value of the compound emulsifier is 10-12, and the addition amount of the compound emulsifier is 1-2% of the sum of the mass of the compound emulsifier and the mass of water.
13. A CO according to claim 3 2 The preparation method of the leak-proof agent for geological storage is characterized in that the mass ratio of the product II obtained in the step S2 to the tetraethoxysilane in the step S3 is 2: (1-1.1);
preferably, the water added in the step S3 accounts for 60-70% of the mass of the reaction system in the step S3.
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