CN112724952A - High-temperature-resistant super-gas-humidity-resistant nano material and preparation method and application thereof - Google Patents
High-temperature-resistant super-gas-humidity-resistant nano material and preparation method and application thereof Download PDFInfo
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- GYXUNDYSSCDRAG-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)OC(=O)C=C GYXUNDYSSCDRAG-UHFFFAOYSA-N 0.000 description 1
- QUKRIOLKOHUUBM-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl prop-2-enoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOC(=O)C=C QUKRIOLKOHUUBM-UHFFFAOYSA-N 0.000 description 1
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- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/16—Enhanced recovery methods for obtaining hydrocarbons
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Abstract
The invention relates to a high temperature resistant super-gas-humidity nano material, a preparation method and application thereof, wherein the general formula is as follows: m (C)7F13CONHCH2CH2CO)n(SiO2) (ii) a Wherein m and n are positive integers; according to the invention, nano silicon dioxide particles are modified by using a modifier, carboxyl in the modifier and hydroxyl on the surface of the nano silicon dioxide are subjected to esterification reaction to obtain a high-temperature-resistant super-gas-humidity nano material, the structure of the nano silicon dioxide nano material is verified by infrared and XPS analysis, the modifier can be subjected to esterification reaction with the nano silicon dioxide instead of simple physical mixing and adsorption, the obtained high-temperature-resistant super-gas-humidity nano material is stable in structure and strong in temperature resistance, the prepared solution only needs water in the application process, and the product is prepared into super-gas-humidity nano solutions with different concentrations, so that the wettability of the surface of a rock core can be converted from liquid-humidity into super-gas-humidity, and the blockage hole is reducedThe probability of the throat improves the gas-phase permeability and obviously improves the fluid flowing capacity in the porous medium.
Description
Technical Field
The invention relates to a high-temperature-resistant super-gas-humidity-resistant nano material as well as a preparation method and application thereof, belonging to the technical field of petrochemical industry.
Background
Petroleum and natural gas are the most important primary energy sources in social development and daily life of people, and are strategic resources which directly influence social progress and economic stability. In a short time, the global demand for oil and gas resources is difficult to be completely replaced. In China, with the rapid development of economy and society, the demand on mineral resources such as oil gas and the like is increasing. At present, domestic energy yield cannot meet the economic and social development requirements, and energy and mineral resources can only be imported from abroad continuously, so that the external dependence of national energy is higher and higher, and particularly, historical records are refreshed continuously by petroleum import quantity, and the national energy safety is seriously threatened.
Therefore, the method has a key strategic significance on the exploration and development of unconventional oil and gas resources. Especially, the condensate gas reservoir with abundant reserves can well cope with the current situation of energy shortage in China. However, the reservoir is mainly developed in a depletion mode, and when the pressure at the bottom of a gas well is lower than the dew point pressure, the reverse condensation phenomenon occurs in the area near a shaft, so that the effective permeability of the gas phase is seriously reduced, and the productivity is reduced. Research shows that if the wettability of the medium in the area near the shaft is changed into gas-wet or neutral gas-wet, the wetting reversal is realized, the seepage capability of the fluid in the area near the shaft is enhanced, and the yield of the condensate gas reservoir can be improved.
Chinese patent document CN2015100559674 discloses a fluorine-containing amphiphilic block polymer gas-moisture reversal agent which is prepared by emulsion polymerization, has obvious water and oil repellency and excellent film forming property, and can be tightly combined with a porous medium of an oil and gas reservoir. However, the air-wet reversal agent has poor solubility, and has no feasibility of mass production and field application, and the air-wet reversal effect is limited. Chinese patent document CN109731526A discloses a fluorine-containing surfactant compound which can be used for the development of condensate gas reservoirs, and has the advantages of small molecular weight, difficult blockage of porous media, strong biodegradability and the like. But the temperature resistance is poor, the synthesis process is complex, and the gas-moisture reversal effect is not ideal.
Chinese patent literature discloses CN104449631A a strong-gas-wettability nano-silica water-unlocking agent, a preparation method thereof and a method for wetting and reversing rock surfaces. The modified nano-silica water-releasing locking agent comprises the following raw materials: 0.1 to 0.5 percent of modified nano silicon dioxide, 0.5 to 1 percent of emulsifier OP-10, 0.5 to 1 percent of sodium dodecyl sulfate, 25 to 50 percent of ethanol and the balance of water; the nano silicon dioxide modified treating fluid is 0.05-0.3% of non-ionic fluorocarbon surfactant aqueous solution. The invention also provides a preparation method and application of the modified nano-silica water-unlocking agent. The modified nano-silica in the invention only realizes strong gas-moisture property and does not realize super gas-moisture state, and the modification between the modifier perfluoroethyl acrylate and the nano-silica is only simple physical adsorption and mixing, does not generate chemical reaction, is easy to fall off when being washed by liquid, has poor mechanical strength and stability, can not realize gas-moisture reversal in the middle and later periods of the field use process, and is not temperature-resistant. In addition, various chemical agents are added into the prepared solution of the modified nano silicon dioxide in the application process, so that the cost is high, and the environment is polluted.
Therefore, the reversal agent merely reverses the wettability of the reservoir surface from the original liquid wettability to neutral gas-wet, gas-wet or strong gas-wet, and does not reach the super gas-wet state, so that the action effect is limited, and the reversal agent cannot be well applied to the development of condensate gas reservoirs.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a high-temperature-resistant super-air-humidity-resistant nano material and a preparation method and application thereof.
The high-temperature-resistant super-gas-humidity-resistant nano material achieves the following aims:
1) the wettability of the reservoir is changed to achieve the purpose of improving the recovery ratio of the condensate gas reservoir.
2) The wettability of the area near the condensate gas reservoir shaft is inverted from liquid-wet state to super-gas-wet state, the probability of blocking the pore throat is reduced, the gas phase permeability is improved, and the fluid flow capacity in the porous medium is obviously improved.
3) Has high temperature resistance.
Description of terms:
1. super-air-wet property: the gas-wet refers to that the core is neither hydrophilic nor oleophilic, and the super gas-wet refers to that the contact angles of the water phase and the oil phase on the solid surface of the core are both more than 150 degrees.
2. Wetting reversal: a phenomenon in which wettability of rock is changed due to adsorption of a surfactant. The wetting ability of liquids to solids is sometimes altered by the addition of a third substance. The hydrophilicity and lipophilicity of a solid surface can both be transformed under certain conditions, and the interconversion of hydrophilicity and lipophilicity of a solid surface is therefore called wet inversion.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
a high temperature and super-air humidity resistant nano material has the following general formula:
m(C7F13CONHCH2CH2CO)n(SiO2)
wherein m and n are positive integers.
According to the invention, m is preferably 5-20, and n is preferably 10-80.
According to the invention, the preparation method of the high temperature and super-gas-humidity resistant nano material comprises the following steps:
(1) adding nano silicon dioxide into a solvent at room temperature, and performing ultrasonic dispersion to obtain a silicon dioxide suspension;
(2) adding a catalyst and a modifier into the silicon dioxide suspension, wherein the modifier is N- (perfluorooctanoic acid) aminopropionic acid sodium; and (3) heating for reaction, and cooling to remove the solvent after the reaction is finished, thereby obtaining the high-temperature-resistant super-air-humidity nano material.
According to the invention, in the step (1), the particle size of the nano silicon dioxide is preferably 30-90 nm.
Preferably, in step (1), the solvent is dichloromethane.
Preferably, in step (1), the ultrasonic dispersion time is 25-35 min.
According to the invention, in the step (1), the mass ratio of the nano silicon dioxide to the solvent is 1 (80-150).
Preferably, in step (2), the sodium N- (perfluorooctanoic acid) aminopropionate is prepared by the following method:
putting beta-aminopropionic acid and catalyst pyridine into ethyl acetate according to the mol ratio of 10:1, slowly dripping perfluorooctanoyl chloride into the system, refluxing for 14-18 hours at 70-90 ℃, wherein the mol ratio of the beta-aminopropionic acid to the perfluorooctanoyl chloride is (1-3): 1; and after the reaction is finished, cooling to remove the solvent to obtain the N- (perfluorooctanoic acid) aminopropionic acid sodium.
More preferably, the mass ratio of the beta-aminopropionic acid to the ethyl acetate is 1 (40-60).
According to the invention, in the step (2), the mass ratio of the modifier to the nano silicon dioxide is 1 (2-8).
Further preferably, in the step (2), the mass ratio of the modifier to the nano silicon dioxide is 1 (2-5).
Most preferably, in the step (2), the mass ratio of the modifier to the nano silicon dioxide is 1: 4.
According to the invention, in the step (2), the catalyst is triethylamine.
According to the invention, in the step (2), the mass ratio of the catalyst to the modifier is 1 (8-12).
Preferably, in the step (2), the temperature is kept between 0 and 5 ℃ during the adding process of the modifier.
According to the invention, in the step (2), the temperature is preferably raised to 55-80 ℃ and the reaction time is preferably 3-5 hours.
Further preferably, the reaction temperature is increased to 65 ℃ for 4 hours.
The reaction raw materials and reagents used in the invention are analytically pure or more. The above reactions were carried out in glass reaction vessels, respectively.
According to the invention, nano silicon dioxide particles are modified by using a modifier, and carboxyl in the modifier and hydroxyl on the surface of the nano silicon dioxide are subjected to esterification reaction to obtain the high-temperature-resistant super-gas-humidity-resistant nano material.
The product is prepared into super-gas-wet nano solutions with different concentrations, the wettability of the surface of the rock core can be converted from liquid-wet to super-gas-wet, the probability of blocking pore throats is reduced, the gas-phase permeability is improved, and the fluid flow capacity in the porous medium is obviously improved.
The nano material has the characteristics of high surface activity and large specific surface area, can be chemically reacted with more modifiers to form the super-air-wetting nano material, when the rock core is soaked in an aqueous solution prepared from the material and is aged, the polar end of the super-air-wetting nano material is adsorbed on the surface of the rock core through hydrogen bonds and van der Waals force, while the non-polar end (namely the hydrophobic and oil-repellent end) is upwards exposed outside, and when water is contacted with oil, the super-air-wetting nano material plays a role in keeping away liquid. As the esterification reaction is carried out between the modifier and the nano-silica, more nonpolar ends in the modifier are firmly present on the surface of the rock core and are exposed outside to play the roles of water and oil repellency, thereby realizing super-air-wetting.
The existing modification of the silicon dioxide is only simple physical mixing, the adsorption quantity of the modifier on the surface of the silicon dioxide is limited and is not firm, and enough nonpolar ends do not exist on the surface of a rock core, so that only gas wetting or strong gas wetting is realized.
The invention also provides application of the high-temperature-resistant super-gas-humidity-resistant nano material.
An application of a high-temperature-resistant super-gas-humidity-resistant nano material is used for converting the wettability of a region near the bottom of a condensate gas reservoir from liquid humidity to super-gas humidity so as to improve the recovery ratio of the condensate gas reservoir.
According to the invention, the preferred specific application method is as follows:
the high-temperature-resistant super-gas-wet nano material is added with water to prepare a super-gas-wet nano solution with the mass fraction of 0.1-1.0%, the reservoir rock core is soaked, the original liquid-wet property of the surface of the reservoir rock core is reversed to super-gas-wet property, the blockage phenomenon of a near-wellbore area is relieved, and the flow resistance of oil/gas in a stratum porous medium is obviously reduced.
The invention has the following excellent effects:
1. the high-temperature-resistant super-gas-humidity-resistant nano material provided by the invention has good temperature resistance and super-hydrophobic and oleophobic characteristics, and can remarkably convert the liquid humidity of a reservoir into super-gas humidity. The viscous resistance between the liquid and the rock core is reduced, so that the speed of the pore medium is improved, the number of the dominant flow guide channels is obviously increased, and the purpose of increasing the yield of the condensate gas reservoir is achieved.
2. The preparation method of the high-temperature super-gas-humidity nano material provided by the invention is simple to operate, mild in reaction condition, almost free of by-products, easy to control, capable of being prepared into an aqueous solution with water in any proportion, good in application effect and beneficial to field popularization.
3. The high-temperature-resistant super-gas-humidity-resistant nano material provided by the invention can be applied to high-temperature reservoirs which cannot be adapted by chemical agents.
Drawings
Fig. 1 is an infrared spectrum of the high temperature and super-moisture resistant nanomaterial prepared in example 1.
Fig. 2 is an XPS spectrum of the high temperature and super-humidity resistant nanomaterial prepared in example 1.
FIG. 3 is a thermogravimetric analysis of the high temperature and super-atmospheric humidity resistant nanomaterial prepared in example 1.
FIG. 4 is an analysis of the super-air-humidity of the high temperature super-air-humidity resistant nanomaterial prepared in example 1.
FIG. 5 shows the gas production rates before and after the super gas wet reversal of the high temperature super gas wet resistant nanomaterial prepared in example 1.
Detailed description of the preferred embodiments
The present invention will be described in more detail with reference to examples, which are not intended to limit the scope of the present invention, but are commercially available. In the examples, "%" is a mass percentage unless otherwise specified.
Example 1
The preparation method of the high temperature resistant super-air-moisture nano material comprises the following steps:
(1) slowly adding 5g of nano silicon dioxide into a reaction kettle with a stirrer and a reflux device at room temperature, taking dichloromethane as a solvent, and performing ultrasonic dispersion for 30min to obtain a silicon dioxide suspension;
(2) 1.25g N- (perfluorooctanoic acid) sodium aminopropionate was added to the silica suspension with stirring, while 0.125g triethylamine was added as a catalyst;
(3) the temperature was raised to 65 ℃ and the reaction was continued for 4 hours.
(4) Cooling and removing the solvent by rotary evaporation to obtain the high-temperature-resistant super-gas-humidity nano material. (infrared see FIG. 3, XPS see FIG. 2, thermogravimetric analysis see FIG. 3).
Measurement of Performance
1. Adding water to the high-temperature-resistant super-gas-wet nano material prepared in the embodiment to prepare a 0.1% solution, soaking and aging the pretreated rock core in the 0.1% super-gas-wet nano material solution for 24 hours, and measuring a contact angle between a water phase and an oil phase on the surface of the rock core, wherein the contact angle between the water phase and the oil phase is 110 degrees and the contact angle between the oil phase and the water phase is 88 degrees. The water phase used was deionized water and the oil phase was n-hexadecane (the same applies below).
2. The super-gas-wet nano material prepared in the example is prepared into a 0.3% solution, the solution is used for soaking the rock core for 24 hours, and the contact angle between the water phase and the oil phase on the surface of the rock core is measured, wherein the contact angle between the water phase and the oil phase is 157 degrees, and the contact angle between the oil phase and the water phase is 154 degrees (as shown in fig. 4).
3. The super-gas-wet nano material prepared in the embodiment is prepared into a 0.5% solution, the solution is used for soaking the rock core for 24 hours, and the contact angle of a water phase and an oil phase on the surface of the rock core is measured, wherein the contact angle of the water phase is 160 degrees, and the contact angle of the oil phase is 155 degrees.
It can be seen from the above performance tests that when the concentration of the super-air-wet nano solution is 0.1%, only air-wet is realized, when the concentration of the super-air-wet nano solution is increased, the super-air-wet effect is achieved, the wetting reversal performance is stronger along with the increase of the concentration of the solution, and when the concentration exceeds 0.3%, the performance change is not large, and the cost problem is considered, so that the concentration of 0.3% is better when the super-air-wet nano solution is applied.
Example 2
The preparation method of the high temperature resistant super-air-moisture nano material comprises the following steps:
(1) slowly adding 5g of nano silicon dioxide into a reaction kettle with a stirrer and a reflux device at room temperature, taking dichloromethane as a solvent, and performing ultrasonic dispersion for 30min to obtain a silicon dioxide suspension;
(2) 2.5g N- (perfluorooctanoic acid) sodium aminopropionate was added to the silica suspension with stirring, while 0.25g triethylamine was added as a catalyst;
(3) the temperature was raised to 65 ℃ and the reaction was continued for 4 hours.
(4) Cooling and removing the solvent by rotary evaporation to obtain the high-temperature-resistant super-gas-humidity nano material.
Measurement of Performance
Adding water to the high-temperature-resistant super-gas-wet nano material prepared in the embodiment to prepare a 0.3% solution, soaking and aging the pretreated rock core in the 0.3% super-gas-wet nano material solution for 24 hours, and measuring the contact angle of a water phase and an oil phase on the surface of the rock core, wherein the contact angle of the water phase is 160 degrees and the contact angle of the oil phase is 156 degrees.
Example 3
The preparation method of the high temperature resistant super-air-moisture nano material comprises the following steps:
(1) slowly adding 5g of nano silicon dioxide into a reaction kettle with a stirrer and a reflux device at room temperature, taking dichloromethane as a solvent, and performing ultrasonic dispersion for 30min to obtain a silicon dioxide suspension;
(2) 1.66g N- (perfluorooctanoic acid) sodium aminopropionate was added to the silica suspension with stirring, while 0.166g triethylamine was added as a catalyst;
(3) the temperature was raised to 65 ℃ and the reaction was continued for 4 hours.
(4) Cooling and removing the solvent by rotary evaporation to obtain the high-temperature-resistant super-gas-humidity nano material.
Measurement of Performance
Adding water to the high-temperature-resistant super-gas-wet nano material prepared in the embodiment to prepare a 0.3% solution, soaking and aging the pretreated rock core in the 0.3% super-gas-wet nano material solution for 24 hours, and measuring a contact angle between a water phase and an oil phase on the surface of the rock core, wherein the contact angle between the water phase and the oil phase is 158 degrees and the contact angle between the oil phase and the water phase is 155 degrees.
Example 4
The preparation method of the high temperature resistant super-air-moisture nano material comprises the following steps:
(1) slowly adding 5g of nano silicon dioxide into a reaction kettle with a stirrer and a reflux device at room temperature, taking dichloromethane as a solvent, and performing ultrasonic dispersion for 30min to obtain a silicon dioxide suspension;
(2) adding 1g of N- (perfluorooctanoic acid) sodium aminopropionate into the silica suspension under the condition of stirring, and simultaneously adding 0.1g of triethylamine as a catalyst;
(3) the temperature was raised to 65 ℃ and the reaction was continued for 4 hours.
(4) Cooling and removing the solvent by rotary evaporation to obtain the high-temperature-resistant super-gas-humidity nano material.
Measurement of Performance
Adding water to the high-temperature-resistant super-gas-wet nano material prepared in the embodiment to prepare a 0.3% solution, soaking and aging the pretreated rock core in the 0.3% super-gas-wet nano material solution for 24 hours, and measuring the contact angle of a water phase and an oil phase on the surface of the rock core, wherein the contact angle of the water phase is 152 degrees and the contact angle of the oil phase is 150 degrees.
The influence of the mass ratio of the modifier to the nanosilica on the super-hygroscopicity was examined in examples 2 to 4, and it was found from the results of the performance measurement in examples 2 to 4 that the reaction was more sufficient when the modifier was excessive, and that the effect was substantially constant when the ratio exceeded 1:4 and the modifier had reached a saturated state.
Example 5
The preparation method of the high temperature resistant super-air-moisture nano material comprises the following steps:
(1) slowly adding 5g of nano silicon dioxide into a reaction kettle with a stirrer and a reflux device at room temperature, taking dichloromethane as a solvent, and performing ultrasonic dispersion for 30min to obtain a silicon dioxide suspension;
(2) 1.25g N- (perfluorooctanoic acid) sodium aminopropionate was added to the silica suspension with stirring, while 0.2g triethylamine was added as a catalyst;
(3) the temperature was raised to 80 ℃ and the reaction was continued for 3 hours.
(4) Cooling and removing the solvent by rotary evaporation to obtain the high-temperature-resistant super-gas-humidity nano material.
Measurement of Performance
Adding water to the high-temperature-resistant super-gas-wet nano material prepared in the embodiment to prepare a 0.3% solution, soaking and aging the pretreated rock core in the 0.3% super-gas-wet nano material solution for 24 hours, and measuring a contact angle between a water phase and an oil phase on the surface of the rock core, wherein the contact angle between the water phase and the oil phase is 158 degrees and the contact angle between the oil phase and the water phase is 156 degrees.
Comparative example 1
The preparation method of the nano material 1 comprises the following steps:
(1) slowly adding 5g of nano silicon dioxide into a reaction kettle with a stirrer and a reflux device at room temperature, taking dichloromethane as a solvent, and performing ultrasonic dispersion for 30min to obtain a silicon dioxide suspension;
(2) adding 1.25g of tridecyl methacrylate into the silicon dioxide suspension under the stirring condition, and simultaneously adding 0.125g of triethylamine as a catalyst;
(3) the temperature was raised to 65 ℃ and the reaction was continued for 4 hours.
(4) Cooling and rotary evaporating to remove the solvent to obtain the nano material 1.
Measurement of Performance
Adding water into the nano material 1 prepared in the comparative example to prepare a 0.3% solution, soaking the pretreated rock core in the 0.3% nano material solution for aging for 24 hours, and measuring the contact angle of a water phase and an oil phase on the surface of the rock core, wherein the contact angle of the water phase is 138 degrees and the contact angle of the oil phase is 122 degrees.
Comparative example 2
The preparation method of the nano material 2 comprises the following steps:
(1) slowly adding 5g of nano silicon dioxide into a reaction kettle with a stirrer and a reflux device at room temperature, taking dichloromethane as a solvent, and performing ultrasonic dispersion for 30min to obtain a silicon dioxide suspension;
(2) adding 1.25g of perfluorooctyl ethyl acrylate into the silicon dioxide suspension under the stirring condition, and simultaneously adding 0.125g of triethylamine as a catalyst;
(3) the temperature was raised to 65 ℃ and the reaction was continued for 4 hours.
(4) Cooling and rotary evaporating to remove the solvent to obtain the nano material 2.
Measurement of Performance
Adding water into the nano material 2 prepared in the comparative example to prepare a 0.3% solution, soaking the pretreated rock core in the 0.3% nano material solution for aging for 24 hours, and measuring the contact angle of a water phase and an oil phase on the surface of the rock core, wherein the contact angle of the water phase is 127 degrees and the contact angle of the oil phase is 111 degrees.
Comparative example 3
The preparation method of the nano material 3 comprises the following steps:
(1) slowly adding 5g of nano silicon dioxide into a reaction kettle with a stirrer and a reflux device at room temperature, taking dichloromethane as a solvent, and performing ultrasonic dispersion for 30min to obtain a silicon dioxide suspension;
(2) adding 1.25g of perfluoroalkyl acrylate into the silicon dioxide suspension under the condition of stirring, and simultaneously adding 0.125g of triethylamine as a catalyst;
(3) the temperature was raised to 65 ℃ and the reaction was continued for 4 hours.
(4) Cooling and rotary evaporating to remove the solvent to obtain the nano material 3.
Measurement of Performance
Adding water into the nano material 3 prepared in the comparative example to prepare a 0.3% solution, soaking the pretreated rock core in the 0.3% nano material solution for aging for 24 hours, and measuring the contact angle of a water phase and an oil phase on the surface of the rock core, wherein the contact angle of the water phase is 114 degrees and the contact angle of the oil phase is 100 degrees.
It can be seen from comparative examples 1 to 3 that the concentration of the nano material is 0.3%, and the contact angle of the water phase and the oil phase of the nano material of comparative examples 1 to 3 on the surface of the rock core is far less than 150 degrees, so that the modification of the nano silicon dioxide by the modifier of comparative examples 1 to 3 only realizes gas humidity or strong gas humidity, but does not reach super gas humidity, and the modification of the nano silicon dioxide by the modifier of the invention can realize super gas humidity, so that the reservoir is obviously converted from liquid humidity to super gas humidity, and the gas yield is improved.
Claims (10)
1. A high temperature and super-air humidity resistant nano material has the following general formula:
m(C7F13CONHCH2CH2CO)n(SiO2)
wherein m and n are positive integers; preferably, m is 5-20, and n is 10-80.
2. A preparation method of a high-temperature-resistant super-air-humidity-resistant nano material comprises the following steps:
(1) adding nano silicon dioxide into a solvent at room temperature, and performing ultrasonic dispersion to obtain a silicon dioxide suspension;
(2) adding a catalyst and a modifier into the silicon dioxide suspension, wherein the modifier is N- (perfluorooctanoic acid) aminopropionic acid sodium; and (3) heating for reaction, and cooling to remove the solvent after the reaction is finished, thereby obtaining the high-temperature-resistant super-air-humidity nano material.
3. The preparation method according to claim 1, wherein in the step (1), the particle size of the nano-silica is 30-90 nm, the solvent is dichloromethane, the ultrasonic dispersion time is 25-35min, and the mass ratio of the nano-silica to the solvent is 1 (80-150).
4. The method according to claim 1, wherein in the step (2), the sodium N- (perfluorooctanoic acid) aminopropionate is prepared by the following method:
putting beta-aminopropionic acid and catalyst pyridine into ethyl acetate according to the mol ratio of 10:1, slowly dripping perfluorooctanoyl chloride into the system, refluxing for 14-18 hours at 70-90 ℃, wherein the mol ratio of the beta-aminopropionic acid to the perfluorooctanoyl chloride is (1-3): 1; after the reaction is finished, cooling and removing the solvent to obtain N- (perfluorooctanoic acid) aminopropionic acid sodium; the mass ratio of the beta-aminopropionic acid to the ethyl acetate is 1 (40-60).
5. The preparation method according to claim 1, wherein in the step (2), the mass ratio of the modifier to the nano-silica is 1 (2-8).
6. The preparation method according to claim 1, wherein in the step (2), the mass ratio of the modifier to the nano-silica is 1 (2-5); most preferably, in the step (2), the mass ratio of the modifier to the nano silicon dioxide is 1: 4.
7. The preparation method according to claim 1, wherein in the step (2), the catalyst is triethylamine, and the mass ratio of the catalyst to the modifier is 1 (8-12).
8. The preparation method according to claim 1, wherein in the step (2), the temperature is kept between 0 and 5 ℃ during the adding process of the modifier; controlling the temperature of the heating reaction to be 55-80 ℃, and controlling the reaction time to be 3-5 hours; preferably, the reaction temperature is increased to 65 ℃ for 4 hours.
9. An application of a high-temperature-resistant super-gas-humidity-resistant nano material is used for converting the wettability of a region near the bottom of a condensate gas reservoir from liquid humidity to super-gas humidity so as to improve the recovery ratio of the condensate gas reservoir.
10. The application of claim 9, wherein the specific application method is as follows:
the high-temperature-resistant super-gas-wet nano material is added with water to prepare a super-gas-wet nano solution with the mass fraction of 0.1-1.0%, and the super-gas-wet nano solution is used for soaking a reservoir core and reversing the original liquid-wet property of the surface of the reservoir core into super-gas-wet property, so that the blocking phenomenon of a near-wellbore area is relieved, and the flow resistance of oil/gas in a stratum porous medium is reduced.
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