CN113549433A - High-temperature-resistant microcapsule lubricant, preparation method and application thereof, and water-based drilling fluid - Google Patents
High-temperature-resistant microcapsule lubricant, preparation method and application thereof, and water-based drilling fluid Download PDFInfo
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
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Abstract
The invention relates to the field of oilfield chemistry, and discloses a preparation method of a high-temperature-resistant microcapsule lubricant, which comprises the following steps: (1) mixing a prepolymer solution prepared from formaldehyde and urea with carbon microspheres to obtain a wall material mixed solution; (2) preparing a compound emulsion from an emulsifier, an ionic liquid, lubricating oil, an extreme pressure antiwear agent and water; (3) and in the presence of a curing agent, reacting the wall material mixed solution and the compound emulsion under an acidic condition, standing, filtering and drying a product to obtain the high-temperature-resistant microcapsule lubricant. The microcapsule lubricant has the elastic modulus not lower than 1550MPa at normal temperature, and has excellent temperature resistance, and the microcapsule lubricant can resist the temperature of 150 ℃; 3% w/v of the microcapsule lubricant is added into the base slurry of the water-based drilling fluid, and the reduction rate of the friction coefficient of the slurry is more than 80% after the slurry is hot rolled for 16 hours at 150 ℃; after the microcapsule lubricant is hot rolled for 16h in a high-temperature water phase at 150 ℃, the mass retention rate is more than 80%.
Description
Technical Field
The invention relates to the technical field of drilling fluid lubricants, in particular to a high-temperature-resistant microcapsule lubricant, a preparation method and application thereof, and a water-based drilling fluid.
Background
The performance of the drilling fluid lubricant has great influence on drilling engineering. When special drilling operations such as extended reach wells, deep wells, ultra-deep wells, horizontal drilling and the like are carried out, the drill string is pulled and rotated, and the friction between the drilling tool and the drilling fluid and between the drilling tool and the well wall can greatly increase the underground torque and the friction resistance. The torque and the friction resistance can increase the abrasion of the drilling tool, reduce the service life of the drilling tool and influence the efficiency and the cost of drilling, and the overhigh torque and the friction resistance can even cause serious underground safety accidents such as drill sticking, drilling tool fracture and the like. In field operation, drilling fluid lubricant is generally added into drilling fluid, a layer of compact protective film is formed on the surface of a friction pair through the drilling fluid lubricant, and the friction pair is separated to achieve the effect of reducing friction resistance. The drilling fluid lubricant can also effectively reduce the adhesion of mud cakes so as to avoid downhole accidents such as drilling blockage and the like. In recent years, with the improvement of lubricating performance and environmental protection requirements of various countries on drilling fluid lubricants, treating agents such as environmental protection lubricants and the like are popularized in succession.
The microcapsule lubricant is used as a novel lubricating material, and has good development prospect due to the advantages of targeting lubricity, simple preparation process, low cost, mild reaction conditions, good lubricating effect and the like. However, microcapsule lubricants also have application drawbacks for particular drilling environments.
Disclosure of Invention
The invention aims to solve the problems that the common microcapsule wall material has poor temperature resistance, is easy to decompose under the action of underground high temperature and cannot adapt to the underground high temperature environment, and provides a high temperature resistant microcapsule lubricant, a preparation method and application thereof and a water-based drilling fluid. The microcapsule lubricant has high temperature stability.
To achieve the above object, a first aspect of the present invention provides a method for preparing a high temperature resistant microcapsule lubricant, the method comprising: (1) mixing a prepolymer solution prepared from formaldehyde and urea with carbon microspheres to obtain a wall material mixed solution;
(2) preparing a compound emulsion from an emulsifier, an ionic liquid, lubricating oil, an extreme pressure antiwear agent and water;
(3) and in the presence of a curing agent, reacting the wall material mixed solution and the compound emulsion under an acidic condition, standing, filtering and drying a product to obtain the high-temperature-resistant microcapsule lubricant.
The second aspect of the invention provides a high-temperature-resistant microcapsule lubricant prepared by the preparation method, wherein the microcapsule lubricant is light yellow black-mixed solid powder, the average particle size is 10-40 mu m, and the temperature resistance is more than or equal to 150 ℃.
In a third aspect, the present invention provides a use of the high temperature resistant microencapsulated lubricant of the present invention in a high temperature drilling environment.
In a fourth aspect, the present invention provides a drilling fluid comprising the high temperature resistant microencapsulated lubricant of the present invention.
Through the technical scheme, the invention provides the high-temperature-resistant microcapsule lubricant with the similar core-shell structure, which is prepared by adopting an in-situ polymerization method. The invention has the following beneficial effects:
(1) the invention wraps the ionic liquid and the extreme pressure antiwear agent in the microcapsule. Through the special 'core-shell' technical characteristics of the microcapsule, the release of the core material lubricant can be controlled in a 'targeted' manner, the lubricating efficiency of the core material lubricant is improved, and the addition and the loss of the core material lubricant are reduced. Compared with the traditional lubricant, the ionic liquid has excellent temperature resistance and lubricity, and can still keep stable chemical properties at a high temperature of about 250 ℃. At a high friction resistance position, the microcapsule is pressed to crack, core materials such as an extreme pressure antiwear agent and the like in the microcapsule are released, and the extreme pressure antiwear agent can form a layer of extreme pressure film on the surface of the metal friction pair, so that the load resistance of the friction pair is improved, and the abrasion of the metal friction pair is reduced.
(2) The invention introduces the carbon microspheres into the microcapsule wall material, improves the load resistance of the microcapsule wall and increases the integral rigidity of the microcapsule. Specifically, the polyurea resin formed by the reaction of formaldehyde and urea through the action of a curing agent is compounded with carbon microspheres to form the composite microcapsule wall. The microcapsule shell is broken by friction among the friction pairs, the shearing force of the drilling fluid and the like under the high-temperature environment in the well. The carbon microspheres will enter the drilling fluid after the wall material has broken. At the high friction resistance position, the carbon microspheres can convert sliding friction between friction pairs into rolling friction with smaller friction area, and the rolling friction and the microcapsule core material liquid lubricant play a role in lubrication in a synergistic manner, so that the effect of lubrication is improved. The carbon microspheres have chemical inertness, excellent heat conduction and lubricating performance and higher surface energy, are not easy to react with other substances underground, can quickly transfer heat to each part of the wall material, enable the wall material to be heated uniformly, delay the time of the urea-formaldehyde resin being heated and decomposed, and improve the high-temperature resistance of the microcapsules.
(3) The invention reduces the loss speed of the ionic liquid, increases the actual lubricating time, effectively reduces the friction coefficient and improves the temperature resistance of the microcapsule.
Drawings
FIG. 1 is a polarizing microscope photograph of a microcapsule lubricant prepared in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of a crushed microencapsulated lubricant prepared in accordance with example 2 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a high-temperature-resistant microcapsule lubricant, which comprises the following steps:
(1) mixing a prepolymer solution prepared from formaldehyde and urea with carbon microspheres to obtain a wall material mixed solution;
(2) preparing a compound emulsion from an emulsifier, an ionic liquid, lubricating oil, an extreme pressure antiwear agent and water;
(3) and in the presence of a curing agent, reacting the wall material mixed solution and the compound emulsion under an acidic condition, standing, filtering and drying a product to obtain the high-temperature-resistant microcapsule lubricant.
In the invention, the carbon microspheres prepared by a hydrothermal reaction method are added into a resin prepolymer obtained by formaldehyde and urea through an in-situ polymerization method, and a modified prepolymer mixed solution is obtained after ultrasonic dispersion. Under the action of a curing agent, emulsion obtained by mechanically stirring an emulsifier, an ionic liquid, an extreme pressure antiwear agent, lubricating oil and water at a certain rotating speed is dripped into the modified prepolymer mixed solution for in-situ polymerization reaction, and the high-temperature resistant microcapsule lubricant is obtained by suction filtration and drying.
In some embodiments of the present invention, in step (1), the prepolymer solution is prepared by: under the alkaline condition, formaldehyde and urea are mixed to carry out water bath reaction, and then the mixture is cooled to room temperature.
In some embodiments of the invention, the water bath temperature is 60-95 ℃ and the time is 0.5-1.5 h; the pH value under the alkaline condition is 8-10. The alkaline condition can be realized by dropwise adding 10% sodium hydroxide solution to adjust the pH value of the water bath reaction system.
In some embodiments of the present invention, it is preferred that the molar ratio of formaldehyde to urea is from 1.5 to 2: 1.
in some embodiments of the present invention, preferably, the weight ratio of the carbon microspheres to formaldehyde is 1: 1-4.
In some embodiments of the present invention, it is preferable that the average particle size of the carbon microsphere is 300-800 nm. The carbon microspheres can be embedded in the urea-formaldehyde resin layer or can be crosslinked with the urea-formaldehyde resin, so that the temperature resistance of the microcapsules is improved.
In some embodiments of the invention, preferably, the mixing is performed under ultrasonic conditions.
In some embodiments of the present invention, preferably, the carbon microsphere is prepared by the following method: the saccharide compound solution is hydrothermally reacted, and the product is refined and filtered.
In some embodiments of the present invention, preferably, the saccharide compound is selected from one or more of glucose, sucrose, maltose, starch, cellulose, cyclodextrin and chitosan.
In some embodiments of the invention, preferably, the saccharide solution is an aqueous solution, and the concentration of the saccharide solution is 5-10% w/v. I.e. 1L of deionized water containing 50-100g of carbohydrate.
In some embodiments of the present invention, it is preferable that the hydrothermal reaction temperature is 180-.
In some embodiments of the present invention, preferably, in step (2), the extreme pressure antiwear agent is selected from one or more of chlorinated paraffin, sulfurized olefin, sulfurized fatty acid ester, sulfurized oil, sulfurized butylene oil ester, and molybdenum disulfide. Specifically, the extreme pressure lubricant is commercially available as an extreme pressure lubricant YD-3015 or 2112 from ZiboHao petrochemical Co., Ltd, an extreme pressure additive 9990A from Shanghai Juncheng industries, Ltd, an extreme pressure treating agent ZH1254 from Zhonghang New materials (Shandong) Co., Ltd, and chlorinated paraffin wax No. 52 from Shuanghong chemical Co., Ltd.
In some embodiments of the present invention, preferably, in the ionic liquid, the cationic structure is one of imidazole ion, pyridine ion, pyrrole ion, alkyl quaternary ammonium salt ion and alkyl quaternary phosphonium salt ion, and the anionic structure is one of halogen ion, hexafluoroborate ion, hexafluorophosphate ion, bis-trifluoromethylsulfonyl imide ion and alkyl sulfonate ion. The ionic liquid has stable performance in a high-temperature environment and an obvious lubricating effect. The ionic liquid is specifically 1-butyl-3-methylimidazolium hexafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium tetrafluoroborate, N-butyl, methylpyrrolidine bis (trifluoromethanesulfonyl) imide salt and the like.
In some embodiments of the present invention, preferably, the lubricant oil is selected from one or more of synthetic grease, vegetable oil, biodiesel and liquid paraffin, specifically, biodiesel commercially available from gaozu chemical limited, Shandong Dizeyi chemical limited 0024 biodiesel, Luhua peanut oil, etc.
In some embodiments of the present invention, preferably, the emulsifier is selected from one or more of tween-80, OP-10, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
In some embodiments of the present invention, preferably, in the compounded emulsion, the mass ratio of the ionic liquid, the lubricating oil, the extreme pressure antiwear agent and the water is 1: 0.1-0.3: 0.01-0.1: 1 to 6; based on the total mass of the ionic liquid, the lubricating oil, the extreme pressure antiwear agent and the water, the mass of the emulsifier is 2-5%. Generally, the ionic liquid has a relatively high viscosity, so that the addition amount of water and the emulsifier needs to be proper when the compound emulsion is prepared. If the addition amount of the water and the emulsifier is less, the viscosity of the obtained emulsion is too high, and further the particle size of emulsion droplets is too large, so that the reaction monomer is difficult to carry out in-situ polymerization at the boundary of the emulsion droplets, and the microcapsules containing core materials have low yield and low coating rate; if the amount of the emulsifier is too large, the microcapsule adhesion phenomenon is severe.
In some embodiments of the present invention, preferably, in step (3), the mass ratio of the ionic liquid in the compound emulsion to the formaldehyde in step (1) is 1: 0.4-1. If the mass ratio of the ionic liquid to the wall material mixed liquid is too large, no enough wall material monomer is coated around the emulsion liquid drop, so that a large amount of ionic liquid is not coated by the wall material, and waste is caused; if the mass ratio of the ionic liquid to the wall material mixed liquid is too small, that is, if the wall material monomer is excessive, a large amount of blank microcapsules without core materials are generated, which affects the microcapsule coating rate.
In some embodiments of the present invention, preferably, the pH under acidic conditions is 3 to 5. The acidic condition can be adjusted by dripping 10 wt% dilute hydrochloric acid solution to adjust the pH value of the reaction system.
In some embodiments of the present invention, preferably, the curing agent is selected from resorcinol and/or ammonium chloride.
In some embodiments of the present invention, it is preferable that the mass of the curing agent is 1 to 2.5% of the mass of formaldehyde.
In some embodiments of the present invention, it is preferred that the reaction temperature is 40 to 75 ℃ and the reaction time is 2.5 to 3.5 hours.
In some embodiments of the present invention, preferably, the reaction can be carried out at a stirring speed of 800-.
Specifically, the preparation method of the high temperature resistant microcapsule lubricant comprises the following steps:
adding a proper amount of carbohydrate into deionized water, heating and stirring until the carbohydrate is completely dissolved or fully dispersed, transferring the mixture into a hydrothermal reaction kettle, carrying out hydrothermal reaction for a period of time, standing the reaction solution, removing supernatant, and carrying out suction filtration and drying on the residual solid to obtain the carbon microspheres;
mixing formaldehyde and urea, carrying out water bath reaction in an alkaline environment for a period of time, cooling to room temperature to obtain a resin prepolymer solution, and adding a proper amount of carbon microspheres into the prepolymer solution under an ultrasonic dispersion condition to obtain a wall material mixed solution;
adding an emulsifier, an ionic liquid lubricant, lubricating oil and an extreme pressure antiwear agent into deionized water, and fully stirring after ultrasonic dispersion to obtain a compound emulsion;
and under the action of a curing agent, mixing the wall material solution and the compound emulsion, carrying out water bath reaction for a certain time in an acidic environment, standing, carrying out suction filtration, and drying to obtain the microcapsule lubricant.
The second aspect of the invention provides a high-temperature-resistant microcapsule lubricant prepared by the preparation method, wherein the microcapsule lubricant is light yellow black-mixed solid powder, the average particle size is 10-40 mu m, and the temperature resistance is more than or equal to 150 ℃.
In some embodiments of the present invention, it is preferred that the reduction in coefficient of friction of the experimental slurry after hot rolling at 150 ℃ is greater than 80% when the microcapsule lubricant is added at 3% w/v. Wherein the experimental pulp can be 3-5% w/v sodium bentonite base pulp prepared from sodium bentonite and water. The friction coefficient can be measured by a limiting pressure lubricator according to the method of SY-T6094-.
In some embodiments of the present invention, it is preferable that the microcapsule lubricant has an elastic modulus at normal temperature of not less than 1550 MPa; after the microcapsule lubricant is hot rolled for 16h in a high-temperature water phase at 150 ℃, the mass retention rate is more than 80%. The modulus of elasticity can be measured by scanning probe microscopy.
In a third aspect, the present invention provides a use of the high temperature resistant microencapsulated lubricant of the present invention in a high temperature drilling environment. The temperature of the environment capable of being applied to drilling is 150 ℃.
In a fourth aspect, the present invention provides a drilling fluid comprising the high temperature resistant microencapsulated lubricant of the present invention.
In some embodiments of the invention, it is preferred that the high temperature resistant microencapsulated lubricant is present in the drilling fluid in an amount of from 3 to 5% w/v based on the total amount of the drilling fluid.
The present invention will be described in detail below by way of examples. In the following examples, comparative examples and test examples,
the particle size of the microencapsulated lubricant was measured by a Bettersize2000 laser particle size Analyzer;
the particle size of the carbon microspheres is measured by an Omni Brukrainen nanometer particle size analyzer;
the friction coefficient was measured by a limiting pressure lubricator according to the method of SY-T6094-1994;
the elastic modulus is measured by a scanning probe microscope;
the manufacturer of the extreme pressure lubrication instrument is Qingdao Senxin electromechanical equipment, Inc., and the model is EP-C;
the manufacturer of the scanning probe microscope system is German Bruk with the model number of MultiMode 8;
the soluble starch is a product sold in the CAS number of 9005-84-9 of national drug group chemical reagent company Limited;
the glucose is a product sold in the CAS number of 50-99-7 of national drug group chemical reagent company Limited;
maltose is a product sold in the CAS number of 6363-53-7 of national drug group chemical reagent company Limited;
the formaldehyde is a commercial product with CAS number of 50-00-0 of national drug group chemical reagent company Limited;
urea is a product sold in the CAS number of 57-13-6 of national drug group chemical reagent Co., Ltd;
tween-80 is a product sold in the CAS number of 9005-65-6 of the national drug group chemical reagent company Limited;
the chlorinated paraffin extreme pressure antiwear agent is chlorinated paraffin 52# of double hong chemical Limited company;
the vulcanized oil extreme pressure antiwear agent is FF-2449 of Guangzhou Fufei chemical Co., Ltd;
the sulfurized olefin extreme pressure antiwear agent is 3049 of Guangzhou Fufei chemical Co.
Example 1
(1) Adding 100g of glucose into 1L of deionized water, heating to 90 ℃, stirring until the glucose is completely dissolved, transferring the solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 8 hours, standing and cooling the product to room temperature, removing supernatant, and carrying out forced air drying on brown precipitate at 100 ℃ for 4 hours to obtain carbon microspheres; the average particle size was determined to be 317 nm;
(2) weighing 45g of 40% formaldehyde water solution and 24g of urea into a three-neck flask, stirring at 800r/min while heating in a water bath to 60 ℃, dropwise adding 10% sodium hydroxide solution during the heating to ensure that the pH of a reaction system is 9, continuously reacting for 1h, cooling to room temperature to obtain a transparent viscous prepolymer solution, adding 14g of carbon microspheres, and ultrasonically dispersing for 30min to obtain a wall material mixed solution;
(3) weighing 1.97g of tween-80 and 48g of deionized water into a beaker, dropwise adding 42g of 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid, 4.2g of biodiesel and 4.2g of chlorinated paraffin extreme pressure antiwear agent under mechanical stirring, and continuously stirring for 60min to obtain a stable oil-in-water compound emulsion;
(4) slowly dripping the compound emulsion into the wall material mixed solution, adding 0.18g of resorcinol into a flask under the stirring condition, dripping 10% hydrochloric acid to ensure that the pH value of the system is 3, slowly heating to 40 ℃, reacting for 3 hours at 800r/min, standing and cooling to room temperature.
And washing the prepared sample with absolute ethyl alcohol for 3 times, performing suction filtration, and performing forced air drying at 50 ℃ for 8 hours to obtain the microcapsule lubricant for the high-temperature-resistant drilling fluid, wherein the mark is J-1, and the average particle size of the J-1 is measured to be 30.3 mu m.
FIG. 1 is a polarizing microscope photograph of a microcapsule J-1 prepared in example 1 of the present invention. As can be seen from figure 1, the microcapsule is in a complete spherical shape, mainly has a single-sphere or double-sphere structure, and has better dispersity and more uniform particle size.
Example 2
(1) Adding 50g of glucose into 1L of deionized water, heating to 90 ℃, stirring until the glucose is completely dissolved, transferring the solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 240 ℃ for 28 hours, standing and cooling the product to room temperature, removing supernatant, and carrying out forced air drying on brown precipitate at 100 ℃ for 4 hours to obtain carbon microspheres; the average particle size is measured to be 676 nm;
(2) weighing 45g of 40% formaldehyde water solution and 18g of urea into a three-neck flask, stirring at 1600r/min while heating in a water bath to 95 ℃, dropwise adding 10% sodium hydroxide solution during the heating to ensure that the pH of a reaction system is 9, continuously reacting for 1h, cooling to room temperature to obtain a transparent viscous prepolymer solution, adding 6g of carbon microspheres, and ultrasonically dispersing for 30min to obtain a wall material mixed solution;
(3) weighing 3.09g of tween-80 and 48g of deionized water into a beaker, dropwise adding 12g of 1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid, 1.2g of liquid paraffin and 0.6g of chlorinated paraffin extreme pressure antiwear agent under mechanical stirring, and continuously stirring for 60min to obtain a stable oil-in-water compound emulsion;
(4) slowly dripping the compound emulsion into the wall material mixed solution, adding 0.45g of resorcinol into a flask under the stirring condition, dripping 10% hydrochloric acid to ensure that the pH value of the system is 3, slowly heating to 75 ℃, reacting for 3 hours at 1600r/min, standing and cooling to room temperature.
And washing the prepared sample with absolute ethyl alcohol for 3 times, performing suction filtration, and performing forced air drying at 50 ℃ for 8 hours to obtain the microcapsule lubricant for the high-temperature-resistant drilling fluid, wherein the mark is J-2, and the average particle size of the J-2 is measured to be 26.1 mu m.
FIG. 2 is a scanning electron microscope image of a microcapsule J-2 prepared in example 2 of the present invention after crushing. As can be seen from FIG. 2, the microcapsule has good sphericity, obvious "core-shell structure", smooth and compact inner surface of the sphere, and rough outer surface due to the resin matrix. The microcapsule wall thickness was about 1.5 μm and the wall thickness was moderate, and a large amount of carbon microsphere particles were clearly seen to be deposited in the shell.
Example 3
(1) Adding 100g of maltose into 1L of deionized water, heating to 90 ℃, stirring until the maltose is completely dissolved, transferring the solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 200 ℃ for 20 hours, standing and cooling the product to room temperature, removing supernatant, and carrying out forced air drying on brown precipitate at 100 ℃ for 4 hours to obtain carbon microspheres; the average particle size was measured to be 391 nm;
(2) weighing 45g of 40% formaldehyde water solution and 22.5g of urea into a three-neck flask, stirring at 1000r/min while heating in a water bath to 70 ℃, dropwise adding 10% sodium hydroxide solution during the heating to ensure that the pH of a reaction system is 9, continuously reacting for 1h, cooling to room temperature to obtain a transparent viscous prepolymer solution, adding 10.13g of carbon microspheres, and ultrasonically dispersing for 30min to obtain a wall material mixed solution;
(3) weighing 3.41g of tween-80 and 60.75g of deionized water into a beaker, dropwise adding 20.25g of 1-ethyl-3-methylimidazolium hexafluorophosphate ionic liquid, 3.04g of peanut oil and 1.22g of vulcanized oil extreme pressure antiwear agent under mechanical stirring, and continuously stirring for 60min to obtain a stable oil-in-water compound emulsion;
(4) slowly dripping the compound emulsion into the wall material mixed solution, adding 0.27g of resorcinol into a flask under the stirring condition, dripping 10% hydrochloric acid to ensure that the pH value of the system is 3, slowly heating to 60 ℃, reacting for 3 hours at 1000r/min, standing and cooling to room temperature.
And washing the prepared sample with absolute ethyl alcohol for 3 times, performing suction filtration, and performing forced air drying at 50 ℃ for 8 hours to obtain the microcapsule lubricant for the high-temperature-resistant drilling fluid, wherein the mark is J-3, and the average grain diameter of the J-3 is measured to be 31.7 mu m.
Example 4
(1) Adding 100g of maltose into 1L of deionized water, heating to 90 ℃, stirring until the maltose is completely dissolved, transferring the solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 220 ℃ for 18 hours, standing and cooling the product to room temperature, removing supernatant, and carrying out forced air drying on brown precipitate at 100 ℃ for 4 hours to obtain carbon microspheres; measuring the average particle size to be 514 nm;
(2) weighing 45g of 40% formaldehyde water solution and 20g of urea into a three-neck flask, stirring at 1200r/min while heating in a water bath to 80 ℃, dropwise adding 10% sodium hydroxide solution during the heating to ensure that the pH of a reaction system is 9, continuously reacting for 1h, cooling to room temperature to obtain a transparent viscous prepolymer solution, adding 7.6g of carbon microspheres, and ultrasonically dispersing for 30min to obtain a wall material mixed solution;
(3) weighing 2.96g of tween-80 and 76g of deionized water into a beaker, dropwise adding 19g of 1-ethyl-3-methylimidazolium hexafluorophosphate ionic liquid, 3.42g of rapeseed oil and 0.19g of olefin sulfide extreme pressure antiwear agent under mechanical stirring, and continuously stirring for 60min to obtain a stable oil-in-water compound emulsion;
(4) slowly dripping the compound emulsion into the wall material mixed solution, adding 0.18g of resorcinol into a flask under the stirring condition, dripping 10% hydrochloric acid to ensure that the pH value of the system is 3, slowly heating to 70 ℃, reacting for 3 hours at 1200r/min, standing and cooling to room temperature.
And washing the prepared sample with absolute ethyl alcohol for 3 times, performing suction filtration, and performing forced air drying at 50 ℃ for 8 hours to obtain the microcapsule lubricant for the high-temperature-resistant drilling fluid, wherein the microcapsule lubricant is marked as J-4, and the average particle size of the J-4 is measured to be 33.2 microns.
Example 5
(1) Adding 100g of soluble starch into 1L of deionized water, heating to 90 ℃, stirring until the soluble starch is uniformly dispersed, transferring the solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 210 ℃ for 16 hours, standing and cooling the product to room temperature, removing supernatant, and carrying out forced air drying on brown precipitate at 100 ℃ for 4 hours to obtain carbon microspheres; measuring the average particle size to be 416 nm;
(2) weighing 45g of 40% formaldehyde water solution and 18g of urea into a three-neck flask, stirring at 1400r/min while heating in a water bath to 90 ℃, dropwise adding 10% sodium hydroxide solution during the heating to ensure that the pH of a reaction system is 9, continuously reacting for 1h, cooling to room temperature to obtain a transparent viscous prepolymer solution, adding 12g of carbon microspheres, and ultrasonically dispersing for 30min to obtain a wall material mixed solution;
(3) weighing 3.77g of tween-80 and 144g of deionized water into a beaker, dropwise adding 36g of 1-ethyl-3-methylimidazolium hexafluorophosphate ionic liquid, 5.40g of peanut oil and 2.88g of olefin sulfide extreme pressure antiwear agent under mechanical stirring, and continuously stirring for 60min to obtain a stable oil-in-water compound emulsion;
(4) slowly dripping the compound emulsion into the wall material mixed solution, adding 0.36g of resorcinol into a flask under the stirring condition, dripping 10% hydrochloric acid to ensure that the pH value of the system is 3, slowly heating to 50 ℃, reacting for 3 hours at 1400r/min, standing and cooling to room temperature.
And washing the prepared sample with absolute ethyl alcohol for 3 times, performing suction filtration, and performing forced air drying at 50 ℃ for 8 hours to obtain the microcapsule lubricant for the high-temperature-resistant drilling fluid, wherein the mark is J-5, and the average grain diameter of the J-5 is measured to be 17.9 mu m.
Comparative example 1
The same procedure as in example 1 was followed, except that no carbon microspheres were added in step (2). The resulting product was designated DJ-1 and the average particle size of DJ-1 was determined to be 9.3. mu.m.
Comparative example 2
The same procedure as in example 2 was followed, except that the hydrothermal reaction time in step (1) was changed to 32 hours, and the average particle diameter of the resulting carbon microspheres was 924 nm. The resulting product was designated DJ-2, and the average particle size of DJ-2 was determined to be 52.6. mu.m.
Comparative example 3
The same procedure as in example 3 was followed, except that the hydrothermal reaction temperature in step (1) was changed to 260 ℃ to obtain carbon microspheres having an average particle diameter of 859 nm. The resulting product was designated DJ-3, and the average particle diameter of DJ-3 was measured to be 41.9. mu.m.
Comparative example 4
The same procedure as in example 4 was followed, except that the temperature in step (4) was slowly raised to 35 ℃. The resulting product was designated DJ-4 and the average particle size of DJ-4 was determined to be 11.7. mu.m.
Test example 1
Preparing bentonite-based slurry: 16g of sodium bentonite for drilling fluid (Shandonghua Weiwei bentonite Co., Ltd.) is added into 400mL of tap water, stirred for 30min at 10000r/min, and sealed and kept stand for 24h to obtain 4% prehydrated bentonite base slurry.
To 400mL of the bentonite-based slurry prepared as described above, 12g (i.e., 3% w/v) of each of J-1 to J-5 obtained in example 1-5 and DJ-1 to DJ-4 obtained in comparative example 1-4 was added, and after stirring at 3000r/min for 20min, the slurry was transferred to an aging tank, and the aging tank was placed in a high-temperature roller heating furnace, hot-rolled at 150 ℃ for 16h, and cooled to room temperature. Stirring at 3000r/min for 10min to test the friction coefficient of the slurry before and after hot rolling. The results are shown in Table 1, which is the effect of the lubricant on the coefficient of friction of the bentonite slurry before and after hot rolling at 150 ℃.
TABLE 1
As can be seen from the results in Table 1, when the high temperature resistant microcapsule lubricants J-1 to J-5 prepared in examples 1 to 5 of the present invention were used as lubricants, the slurry friction coefficient was almost unchanged before hot rolling at 150 ℃ for 16 hours, demonstrating that the ionic liquid was encapsulated in the microcapsules and the ionic liquid adhered to the wall surface of the microcapsules slightly lowered the slurry friction coefficient. After hot rolling at 150 ℃, the reduction rate of the friction coefficient of the slurry is more than 80%, and the lubricating effect of the microcapsule lubricant is good. In the DJ-1 obtained in the comparative example 1, the friction pair always has sliding friction because the microcapsule does not contain carbon microspheres, and the friction coefficient is larger than J-1. In DJ-2 and DJ-3 in the comparative examples 2-3, the particle size of the carbon microspheres is too large, so that the carbon microspheres cannot be effectively coated in the urea resin layer, the microcapsule wall has pores and cannot be dense, and the ionic liquid is continuously leaked. In comparative example 4, although the microcapsule DJ-4 has a certain lubricating effect, the coefficient of friction reduction rate of the present application cannot be achieved after hot rolling at 150 ℃, and during synthesis, the microcapsule curing temperature is too low, and the yield of the microcapsule is extremely low, which is not within the technical scheme provided by the present invention.
Test example 2
Adding 200mL of tap water into a hydrothermal reaction kettle, respectively adding 6.00g of J-1 to J-5 obtained in example 1-5 and DJ-1 to DJ-4 obtained in comparative example 1-4, putting the hydrothermal reaction kettle into an aging furnace, rolling for 16h at 150 ℃, cooling to room temperature, carrying out suction filtration on the mixed solution, washing the residual solid for 3 times by using absolute ethyl alcohol, carrying out vacuum drying for 8h at 50 ℃, weighing the mass of the residual solid and calculating the mass retention rate of the microcapsules. The results are shown in Table 2, Table 2 showing the mass retention of the lubricant after hot rolling at 150 ℃ for 16 h.
TABLE 2
As can be seen from the results in Table 2, the microcapsule lubricants of J-1 to J-5 have the mass retention rate of more than 80% after being hot rolled for 16h at 150 ℃, and the retention rates are all superior to DJ-1 to DJ-4 obtained in comparative examples 1-4.
Test example 3
A small amount of each of J-1 to J-5 obtained in example 1-5 and DJ-1 to DJ-4 obtained in comparative example 1-4 was fixed on a mica sheet with a glue, and the mica sheet was adhered to a round iron sheet with a double-sided tape after drying naturally to prepare a sample. The samples were tested for modulus of elasticity using a brook MultiMode 8 scanning probe microscope, germany.
The results are shown in Table 3. Table 3 shows the elastic modulus of J-1 to J-5, DJ-1 to DJ-4.
TABLE 3
As can be seen from the results in Table 3, the elastic moduli of J-1 to J-5 obtained in examples 1 to 5 were not less than 1550MPa and were all larger than those of DJ-1 to DJ-4 obtained in comparative examples 1 to 4. The higher the elastic modulus is, the smaller the elastic deformation amount of the material is, the higher the rigidity is, and the surface of the material is not easy to deform.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method of preparing a high temperature resistant microencapsulated lubricant, the method comprising:
(1) mixing a prepolymer solution prepared from formaldehyde and urea with carbon microspheres to obtain a wall material mixed solution;
(2) preparing a compound emulsion from an emulsifier, an ionic liquid, lubricating oil, an extreme pressure antiwear agent and water;
(3) and in the presence of a curing agent, reacting the wall material mixed solution and the compound emulsion under an acidic condition, standing, filtering and drying a product to obtain the high-temperature-resistant microcapsule lubricant.
2. The preparation method according to claim 1, wherein in the step (1), the prepolymer solution is prepared by: under the alkaline condition, mixing formaldehyde and urea to carry out water bath reaction, and then cooling to room temperature;
preferably, the temperature of the water bath is 60-95 ℃, and the time is 0.5-1.5 h; the pH value under the alkaline condition is 8-10;
preferably, the molar ratio of formaldehyde to urea is from 1.5 to 2: 1;
preferably, the weight ratio of the carbon microspheres to formaldehyde is 1: 1-4;
preferably, the average particle size of the carbon microspheres is 300-800 nm;
preferably, the mixing is performed under ultrasonic conditions.
3. The preparation method according to claim 1 or 2, wherein in the step (2), the extreme pressure antiwear agent is selected from one or more of chlorinated paraffin, sulfurized olefin, sulfurized fatty acid ester, sulfurized oil, butylene sulfurized oil ester and molybdenum disulfide;
preferably, in the ionic liquid, the cation structure is one of imidazole ion, pyridine ion, pyrrole ion, alkyl quaternary ammonium salt ion and alkyl quaternary phosphonium salt ion, and the anion structure is one of halogen ion, hexafluoroborate ion, hexafluorophosphate ion, bis-trifluoromethyl-sulfonyl-imide ion and alkyl sulfonate ion;
preferably, the lubricating oil is selected from one or more of synthetic grease, vegetable oil, biodiesel and liquid paraffin;
preferably, the emulsifier is selected from one or more of tween-80, OP-10, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate;
preferably, in the compound emulsion, the mass ratio of the ionic liquid to the lubricating oil to the extreme pressure antiwear agent to water is 1: 0.1-0.3: 0.01-0.1: 1 to 6; based on the total mass of the ionic liquid, the lubricating oil, the extreme pressure antiwear agent and the water, the mass of the emulsifier is 2-5%.
4. The preparation method according to any one of claims 1 to 3, wherein in the step (3), the mass ratio of the ionic liquid in the compound emulsion to the formaldehyde in the step (1) is 1: 0.4 to 1;
preferably, the pH under acidic conditions is 3-5;
preferably, the curing agent is selected from resorcinol and/or ammonium chloride;
preferably, the mass of the curing agent is 1-2.5% of the mass of formaldehyde;
preferably, the reaction temperature is 40-75 ℃ and the reaction time is 2.5-3.5 h.
5. The production method according to any one of claims 1 to 4, wherein the carbon microsphere is produced by:
carrying out hydrothermal reaction on the carbohydrate solution, and refining and filtering a product;
preferably, the saccharide compound is selected from one or more of glucose, sucrose, maltose, starch, cellulose, cyclodextrin and chitosan;
preferably, the saccharide solution is an aqueous solution, the concentration of the saccharide solution is 5-10% w/v;
preferably, the hydrothermal reaction temperature is 180-240 ℃, and the hydrothermal reaction time is 8-28 h.
6. The high-temperature-resistant microcapsule lubricant prepared by the preparation method of any one of claims 1 to 5, wherein the microcapsule lubricant is light yellow black-mixed solid powder, the average particle size is 10-40 μm, and the temperature resistance is more than or equal to 150 ℃.
7. The high temperature resistant microcapsule lubricant according to claim 6, wherein the reduction rate of the friction coefficient of the test slurry after hot rolling for 16h at 150 ℃ is more than 80% when the microcapsule lubricant is added at 3% w/v.
8. The high temperature resistant microcapsule lubricant according to claim 6 or 7, wherein the microcapsule lubricant has an elastic modulus at normal temperature of not less than 1550 MPa; after the microcapsule lubricant is hot rolled for 16h in a high-temperature water phase at 150 ℃, the mass retention rate is more than 80%.
9. Use of a high temperature resistant microcapsule lubricant as claimed in any one of claims 6 to 8 in a high temperature drilling environment.
10. An aqueous based drilling fluid comprising the high temperature resistant microencapsulated lubricant of any one of claims 6-8;
preferably, the high temperature resistant microencapsulated lubricant is present in the drilling fluid in an amount of 3 to 5% w/v based on the total amount of the drilling fluid.
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