CN109370549B - Super-amphiphobic Janus particle of silicon dioxide suitable for chip carrying agent for oil-based drilling fluid and preparation method and application thereof - Google Patents
Super-amphiphobic Janus particle of silicon dioxide suitable for chip carrying agent for oil-based drilling fluid and preparation method and application thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/10—Nanoparticle-containing well treatment fluids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
Abstract
The invention relates to the field of oil and gas drilling, in particular to a super-amphiphobic Janus particle of silicon dioxide suitable for a chip carrying agent for an oil-based drilling fluid, and a preparation method and application thereof. The Janus particle is a silica nanoparticle with the surface asymmetrically modified, wherein a part of the surface of the Janus particle is modified with a first modifying group provided by silane shown in a formula (1), and at least a part of the rest surface of the Janus particle is modified with a second modifying group provided by silane shown in a formula (2). The invention combines the particularity of asymmetric Janus particle structure and performance, and realizes the foaming and foam stabilizing effects in the emulsified oil-based drilling fluid. And the super-amphiphobic Janus particle chip carrying agent is used as a core treating agent to form a high-efficiency chip carrying oil-based drilling fluid system, so that the drilling speed of a complex well and the well hole purification efficiency are improved, and the continuous exploration and development of unconventional oil and gas reservoirs are further promoted.
Description
Technical Field
The invention relates to the field of oil and gas drilling, in particular to a super-amphiphobic Janus particle of silicon dioxide suitable for a chip carrying agent for an oil-based drilling fluid, and a preparation method and application thereof.
Background
With the development of exploration and development of China to deeper strata, higher requirements are put forward on the drilling technology and more severe requirements are put forward on the performance of the drilling fluid. In the drilling process of large-displacement wells and complex wells, the formation of a rock debris bed caused by the migration of water-wet rock debris along with the oil-based drilling fluid is difficult, and particularly serious potential safety hazards are easily caused in the soilless-phase oil-based drilling fluid with weak gel strength.
At present, oil-based drilling fluid chip carrying agents researched and developed at home and abroad are mainly flow pattern regulators by changing the rheological property of the oil-based drilling fluid, conventional flow pattern regulators mainly comprise two types of organic soil and polymers, the organic soil is a chip carrying agent with chip carrying property obtained by modifying bentonite through an organic modifier, but the chip carrying agent has large using amount and high cost; the polymer mainly achieves the effect of chip carrying and speed increasing by improving the rheological property of the drilling fluid and increasing the viscosity increasing and cutting increasing effect of the drilling fluid, but the chip carrying agent has the problems of strict requirement on the solubility, complex production process of oil-soluble polymers and the like.
Disclosure of Invention
The invention aims to provide a super-amphiphobic Janus particle of silicon dioxide suitable for a chip carrying agent for an oil-based drilling fluid, which can improve the foaming effect, foam stabilizing effect and chip carrying efficiency of the drilling fluid on the basis of not influencing the rheological property of the oil-based drilling fluid, and a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a Janus particle of silicon dioxide, the Janus particle being a silicon dioxide nanoparticle having an asymmetrically modified surface, wherein a part of the surface of the Janus particle is modified with a first modifying group provided by a silane represented by formula (1), and at least a part of the remaining surface of the Janus particle is modified with a second modifying group provided by a silane represented by formula (2);
formula (1)
Formula (2)
Wherein R is1-R6Each independently selected from C1-C6 alkyl and C1-C6 alkoxy; l is1Alkylene selected from C1-C8; r7Selected from C6-C20 alkyl groups.
In a second aspect, the present invention provides a method for preparing a Janus particle of silica, the method comprising:
(1) protecting partial surface of the silica nano particle;
(2) in a first solvent, carrying out a first contact reaction on the protected silica nanoparticles and silane shown in the formula (1), and then removing the solvent to obtain silica nanoparticles of which the surfaces are partially modified with first modifying groups provided by the silane shown in the formula (1); the first solvent is a mixed solvent containing alcohol and water;
(3) exposing the remaining surface of the protected silica nanoparticles;
(4) performing a second contact reaction of the remaining surface-exposed silica nanoparticles with the silane represented by formula (2) in a second solvent to modify at least a portion of the remaining surface of the silica nanoparticles with a second modifying group provided by the silane represented by formula (2); the second solvent is a mixed solvent containing alcohol and water;
formula (1)
Formula (2)
Wherein R is1-R6Each independently selected from C1-C6 alkyl and C1-C6 alkoxy; l is1Alkylene selected from C1-C8; r7Selected from C6-C20 alkyl group.
In a third aspect, the present invention provides Janus particles of silica produced by the above process.
In a fourth aspect, the present invention provides the use of the above-described Janus particles of silica as an cuttings carrier in an oil-based drilling fluid.
In a fifth aspect of the invention, there is provided an oil-based drilling fluid comprising Janus particles of the above-described silica.
In a sixth aspect, the invention provides the use of the oil-based drilling fluid described above in oil and gas drilling.
Part of the surface of the super-amphiphobic Janus particle of the silicon dioxide provided by the invention is provided with hydrophobic groups, and part of the surface is distributed with oleophobic groups, so that the super-amphiphobic performance is shown, the wettability of the solid surface can be reversed, and meanwhile, the super-amphiphobic Janus particle has good foaming effect and foam stabilizing effect due to the characteristics of the solid surfactant, so that bubbles are stably adsorbed on the surface of drill cuttings, the rock cuttings are taken out of a shaft, and the purpose of improving the cuttings carrying efficiency is achieved.
The invention combines the particularity of asymmetric Janus particle structure and performance, and realizes the foaming and foam stabilizing effects in the emulsified oil-based drilling fluid. And the super-amphiphobic Janus particle chip carrying agent is used as a core treating agent to form a high-efficiency chip carrying oil-based drilling fluid system, so that the drilling speed of a complex well and the well hole purification efficiency are improved, and the continuous exploration and development of unconventional oil and gas reservoirs are further promoted.
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 Janus particle of silicon dioxide, which is a silicon dioxide nano particle with an asymmetrically modified surface, wherein part of the surface of the Janus particle is modified with a first modified group provided by silane shown in a formula (1), and at least part of the rest surface of the Janus particle is modified with a second modified group provided by silane shown in a formula (2);
formula (1)
Formula (2)
Wherein R is1-R6Each independently selected from C1-C6 alkyl and C1-C6 alkoxy; l is1Alkylene selected from C1-C8; r7Selected from C6-C20 alkyl groups.
The silicon dioxide super-amphiphobic Janus particle chip carrying agent with asymmetric structure and performance can be adsorbed on a gas-liquid interface of the milky oil-based drilling fluid, so that the foam stability is enhanced, and the technical problem that the foam of the oil-based drilling fluid is difficult to stabilize is solved; meanwhile, the floating type rock debris adsorption bed is adsorbed on rock debris, so that the surface of the rock debris is inverted to be super-amphiphobic and then adsorbs bubbles, the buoyancy on the rock debris is enhanced, and the formation of a rock debris bed is avoided.
According to the present invention, the alkyl group having 1 to 6 may be, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a n-hexyl group, etc.
According to the present invention, among them, the alkoxy group having C1 to C6 may be, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentoxy, n-hexoxy, etc.
Wherein the alkylene group having C1 to C8 may be, for example, -CH2-、-CH2-CH2-、-CH2-CH2-CH2-、-CH(CH3)-CH2-、-CH2-CH(CH3)-、-CH2-(CH2)2-CH2-、-CH2-CH(CH3)-CH2-、-C(CH3)2-CH2-or-CH2-C(CH3)2-and the like.
Specific examples of the above-mentioned alkyl group having C6 to C20 may include, for example, a C6 alkyl group (for example, n-hexyl group), a C7 alkyl group (for example, n-heptyl group), a C8 alkyl group (for example, n-octyl group), a C9 alkyl group (for example, n-nonyl group), a C10 alkyl group (for example, n-decyl group), a C11 alkyl group (for example, n-undecyl group), a C12 alkyl group (for example, n-dodecyl group), a C14 alkyl group (for example, n-tetradecyl group), a C16 alkyl group (for example, n-hexadecyl group), a C18 alkyl group (for example, n-octadecyl group), a C20 alkyl group (for example, n-eicosyl group), and the like.
According to the invention, in order to obtain the super-amphiphobic chip carrier with more excellent chip carrying capacity and more suitable for the oil-based drilling fluid, R is preferably selected1-R6Each independently selected from C1-C4 alkyl and C1-C4 alkoxy; l is1Alkylene selected from C1-C6; r7Selected from C6-C16 alkyl groups.
More preferably, R1-R6Each independently selected from methyl, ethyl, n-propyl, methoxy, ethoxy and n-propoxy; l is1Is selected from-CH2-、-CH2-CH2-、-CH2-CH2-CH2-、-CH(CH3)-CH2-、-CH2-CH(CH3) -or-CH2-(CH2)2-CH2-；R7Selected from n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl or n-hexadecyl.
Among them, specific examples of the silane represented by the formula (1) are preferably one or more of silanes represented by the following formulae:
formula (1-1): in the formula (1), R1-R3Are each methoxy, L1is-CH2- (may be referred to as aminomethyltrimethoxysilane);
formula (1-2): in the formula (1), R1-R3Are each methoxy, L1is-CH2-CH2- (referred to as 2-aminoethyl trimethoxysilane);
formula (1-3): in the formula (1), R1-R3All of which are methoxy groups,L1is-CH2-CH2-CH2- (which may be referred to as 3-aminopropyltrimethoxysilane);
formula (1-4): in the formula (1), R1-R3Are each ethoxy, L1is-CH2- (may be referred to as aminomethyl triethoxysilane);
formula (1-5): in the formula (1), R1-R3Are each ethoxy, L1is-CH2-CH2- (referred to as 2-aminoethyltriethoxysilane);
formula (1-6): in the formula (1), R1-R3Are each ethoxy, L1is-CH2-CH2-CH2- (which may be referred to as 3-aminopropyltriethoxysilane);
formula (1-7): in the formula (1), R1-R3Are each methyl, L1is-CH2- (may be referred to as aminomethyl trimethylsilane);
formula (1-8): in the formula (1), R1-R3Are each methyl, L1is-CH2-CH2- (referred to as 2-aminoethyltrimethylsilane);
formula (1-9): in the formula (1), R1-R3Are each methyl, L1is-CH2-CH2-CH2- (which may be referred to as 3-aminopropyltrimethylsilane);
formula (1-10): in the formula (1), R1-R3Are all ethyl, L1is-CH2- (may be referred to as aminomethyltriethylsilane);
formula (1-11): in the formula (1), R1-R3Are all ethyl, L1is-CH2-CH2- (which may be referred to as 2-aminoethyltriethylsilane);
formula (1-12): in the formula (1), R1-R3Are all ethyl, L1is-CH2-CH2-CH2- (which may be referred to as 3-aminopropyltriethylsilane).
Among them, specific examples of the silane represented by the formula (2) are preferably one or more of silanes represented by the following formulae:
formula (2-1): in the formula (2), R1-R3Are all methoxyRadical, R7Is n-hexyl (which may be referred to as n-hexyltrimethoxysilane);
formula (2-2): in the formula (2), R1-R3Are all methoxy radicals, R7Is n-octyl (may be referred to as n-octyltrimethoxysilane);
formula (2-3): in the formula (2), R1-R3Are all methoxy radicals, R7Is n-decyl (may be referred to as n-decyltrimethoxysilane);
formula (2-4): in the formula (2), R1-R3Are all methoxy radicals, R7Is n-dodecyl (may be referred to as n-dodecyltrimethoxysilane);
formula (2-5): in the formula (2), R1-R3Are all methoxy radicals, R7Is n-tetradecyl (which can be referred to as n-tetradecyltrimethoxysilane);
formula (2-6): in the formula (2), R1-R3Are all methoxy radicals, R7Is n-hexadecyl (which can be referred to as n-hexadecyltrimethoxysilane);
formula (2-7): in the formula (2), R1-R3Are all ethoxy, R7Is n-hexyl (which may be referred to as n-hexyltriethoxysilane);
formula (2-8): in the formula (2), R1-R3Are all ethoxy, R7Is n-octyl (may be referred to as n-octyltriethoxysilane);
formula (2-9): in the formula (2), R1-R3Are all ethoxy, R7Is n-decyl (which may be referred to as n-decyltriethoxysilane);
formula (2-10): in the formula (2), R1-R3Are all ethoxy, R7Is n-dodecyl (may be referred to as n-dodecyltriethoxysilane);
formula (2-11): in the formula (2), R1-R3Are all ethoxy, R7Is n-tetradecyl (which can be referred to as n-tetradecyltriethoxysilane);
formula (2-12): in the formula (2), R1-R3Are all ethoxy, R7Is n-hexadecyl (which can be referred to as n-hexadecyltriethoxy silane);
formula (2-13): in the formula (2), R1-R3Are each methyl, R7Is n-hexyl (which may be referred to as n-hexyltrimethylsilane);
formula (2-14): in the formula (2), R1-R3Are each methyl, R7Is n-octyl (may be referred to as n-octyltrimethylsilane);
formula (2-15): in the formula (2), R1-R3Are each methyl, R7Is n-decyl (may be referred to as n-decyltrimethylsilane);
formula (2-16): in the formula (2), R1-R3Are each methyl, R7N-dodecyl (which may be referred to as n-dodecyltrimethylsilane);
formula (2-17): in the formula (2), R1-R3Are each methyl, R7N-tetradecyl (which can be referred to as n-tetradecyltrimethylsilane);
formula (2-18): in the formula (2), R1-R3Are each methyl, R7N-hexadecyl (which can be referred to as n-hexadecyltrimethylsilane);
formula (2-19): in the formula (2), R1-R3Are all ethyl radicals, R7Is n-hexyl (which may be referred to as n-hexyltriethylsilane);
formula (2-20): in the formula (2), R1-R3Are all ethyl radicals, R7Is n-octyl (may be referred to as n-octyltriethylsilane);
formula (2-21): in the formula (2), R1-R3Are all ethyl radicals, R7Is n-decyl (which may be referred to as n-decyltriethylsilane);
formula (2-22): in the formula (2), R1-R3Are all ethyl radicals, R7Is n-dodecyl (may be referred to as n-dodecyltriethylsilane);
formula (2-23): in the formula (2), R1-R3Are all ethyl radicals, R7Is n-tetradecyl (which can be referred to as n-tetradecyltriethylsilane);
formula (2-24): in the formula (2), R1-R3Are all ethyl radicals, R7Is n-hexadecyl (which can be referred to as n-hexadecyltriethyl silane).
According to the invention, the first modifying group provided by the silane of formula (1) above is primarily R in the silane of formula (1)1-R3At least one of the silicon hydroxyl groups formed after hydrolysis to hydroxyl groups reacts with active groups (e.g., hydroxyl groups) on the surface of the silica nanoparticles, so that the silane represented by formula (1) is bonded to the surface of the silica nanoparticles in the form of a modified group; likewise, R in the silane of the formula (2)4-R6The silicon hydroxyl group formed after hydrolysis of at least one of them into a hydroxyl group reacts with an active group (e.g., hydroxyl group) on the surface of the silica nanoparticle, so that the silane represented by formula (2) is bonded to the surface of the silica nanoparticle in the form of a modified group.
According to the invention, the size of the silica nanoparticles should be suitable for the cuttings carrying agent of the oil-based drilling fluid, and for this reason, the particle size of the silica nanoparticles is preferably 100-1000nm, preferably 200-800nm, and more preferably 300-600 nm.
According to the invention, in order to enable the Janus particles of the invention to show better chip carrying performance and better compatibility with oil-based drilling fluid, the weight ratio of the silica nanoparticles to the first modifying groups provided by the silane shown in the formula (1) is preferably 100: 10-150, preferably 100: 40-120, preferably 100: 50-100, more preferably 100: 80-100.
Preferably, the weight ratio of the silica nanoparticles to the second modifying groups provided by the silane represented by formula (2) is 100: 5-100, preferably 100: 5-80, preferably 100: 10-60, more preferably 100: 30-50.
In a second aspect, the present invention provides a method for preparing a Janus particle of silicon dioxide, the method comprising:
(1) protecting partial surface of the silica nano particle;
(2) in a first solvent, carrying out a first contact reaction on the protected silica nanoparticles and silane shown in the formula (1), and then removing the solvent to obtain silica nanoparticles of which the surfaces are partially modified with first modifying groups provided by the silane shown in the formula (1); the first solvent is a mixed solvent containing alcohol and water;
(3) exposing the remaining surface of the protected silica nanoparticles;
(4) performing a second contact reaction of the remaining surface-exposed silica nanoparticles with the silane represented by formula (2) in a second solvent to modify at least a portion of the remaining surface of the silica nanoparticles with a second modifying group provided by the silane represented by formula (2); the second solvent is a mixed solvent containing alcohol and water;
formula (1)
Formula (2)
Wherein R is1-R6Each independently selected from C1-C6 alkyl and C1-C6 alkoxy; l is1Alkylene selected from C1-C8; r7Selected from C6-C20 alkyl groups.
Wherein, the silane shown in the formula (1) and the silane shown in the formula (2) are described above, and the description thereof will not be repeated herein.
According to the present invention, a portion of the surface of the silica nanoparticles is protected in step (1) such that a portion of the surface of the silica nanoparticles is exposed for a first contact reaction with the silane represented by formula (1) and the remaining portion of the protected surface is left for a subsequent second contact reaction with the silane represented by formula (2).
Among them, the manner of protecting a part of the surface of the silica nanoparticles may be variously selected as long as the above object can be achieved, and for the sake of more convenient operation, the present invention preferably adopts a manner of protecting by adhering the silica nanoparticles to the wax particles, and for this reason, preferably, the step (1) includes adhering the silica nanoparticles to the wax particles to protect a part of the surface of the silica nanoparticles. Specifically, the process of adhering silica nanoparticles to wax particles includes: the silica nanoparticles and the wax particles are mixed at a temperature of 60 to 85 deg.C (preferably 70 to 80 deg.C), and then subjected to a cooling treatment (e.g., cooling to 10 to 30 deg.C) and a washing treatment (e.g., washing with one or more solvents selected from ethanol, methanol, water, etc., and the cooling washing process may be washing with the above-mentioned washing solvent at 10 to 30 deg.C while cooling). Thus, during the mixing process, the surfaces of the wax particles soften or even melt at a relatively high temperature, so that the silica nanoparticles adhere to the surfaces of the wax particles, even partially embed the silica nanoparticles into the surfaces of the wax particles, whereby part of the surfaces of the silica nanoparticles is exposed, while part of the surfaces in contact with the wax particles or the surfaces of the silica nanoparticles masked by contact with the wax particles are protected. Wherein, the mixing time is preferably 20-150min, preferably 30-120 min.
Wherein the size of the wax particle is larger than that of the silica nano particle, preferably, the wax particle is a wax ball with the particle diameter of 0.01-0.1mm, preferably 0.05-0.1 mm. The wax may be paraffin wax or the like.
Wherein the size of the silica nanoparticles is suitable for the cuttings carrying agent of the oil-based drilling fluid, and preferably, the particle size of the silica nanoparticles is 100-1000nm, preferably 200-800nm, and more preferably 300-600 nm.
According to the present invention, the above-mentioned mixing of the silica nanoparticles and the wax particles may be carried out in the presence of a surfactant, wherein the surfactant may be, for example, didecyl dimethyl ammonium bromide, didecyl dimethyl ammonium chloride, didodecyl dimethyl ammonium bromide, didodecyl dimethyl ammonium chloride, ditetradecyl dimethyl ammonium bromide, ditetradecyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium bromide, dihexadecyl dimethyl ammonium chloride, dioctadecyl dimethyl ammonium chloride, n-decyl trimethyl ammonium bromide, n-decyl trimethyl ammonium chloride, n-dodecyl trimethyl ammonium bromide, n-dodecyl trimethyl ammonium chloride, n-tetradecyl trimethyl ammonium bromide, n-tetradecyl trimethyl ammonium chloride, n-hexadecyl trimethyl ammonium bromide, n-hexadecyl trimethyl ammonium chloride, n-tetradecyl trimethyl ammonium chloride, One or more of n-octadecyl trimethyl ammonium bromide, n-octadecyl trimethyl ammonium chloride, etc. The surfactant may be provided in the form of an aqueous solution thereof, the concentration of the surfactant solution preferably being 0.1-1 mg/mL.
According to the present invention, in the step (2), the surface of the non-protected silica nanoparticles may be modified with the first modifying group provided by the silane represented by the above formula (1) by subjecting the partially surface-protected silica nanoparticles obtained in the step (1) to a first contact reaction with the silane represented by the above formula (1).
Among them, in order to obtain a chip carrier having a better chip carrier effect, it is preferable that the weight ratio of the amount of the silica nanoparticles to the amount of the silane represented by formula (1) is 100: 10-150, preferably 100: 40-120, preferably 100: 50-100, more preferably 100: 80-100.
The first contact reaction is carried out in a first solvent which is a mixed solvent comprising alcohol and water, wherein the amount of the first solvent can vary within a wide range, preferably the amount of the first solvent is 20 to 200mL, preferably 50 to 100mL, relative to 1g of the silica nanoparticles. The alcohol solvent in the mixed solvent containing alcohol and water may be selected from a variety of alcohol solvents, and is preferably one or more of ethanol, methanol, n-propanol, and isopropanol. Wherein, in the mixed solvent containing alcohol and water, the content of the alcohol solvent is preferably 1-5 wt%.
According to the present invention, preferably, the conditions of the first contact reaction include: the temperature is 10-30 ℃ and the time is 30-70 h. More preferably, the conditions of the first contact reaction include: the temperature is 20-25 ℃ and the time is 36-60 h.
Although solid-liquid separation may be performed after the first contact reaction in order to extract silica nanoparticles, and washing of the extracted solid phase with a mixed solvent containing alcohol and water may be continued in order to remove unreacted silane represented by formula (1) and the like.
According to the present invention, the remaining surface of the silica nanoparticles to be protected will be exposed by the treatment of step (3), and when step (1) employs a method of adhering silica nanoparticles to wax particles to protect a part of the surface of the silica nanoparticles as described above, then step (3) may employ a method of dissolving the wax particles to remove the wax particles to expose the remaining part of the surface of the silica nanoparticles to be shielded by the wax. Thus, preferably, the step (3) comprises mixing the solid-phase product obtained in the step (2) after the first contact reaction with an organic solvent capable of dissolving wax to remove wax particles. Among them, such an organic solvent is preferably one or more of dichloromethane, dichloroethane, xylene, gasoline, and the like. The amount of the organic solvent used may be, for example, 50 to 500mL relative to 10g of the wax. In order to be able to promote the dissolution of the wax particles, the above-mentioned dissolution process may be carried out at elevated temperatures, for example at 40-50 ℃.
According to the present invention, after the completion of the above-mentioned dissolution process, the solid phase is extracted by solid-liquid separation, and the solid phase may be washed (for example, with the above-mentioned organic solvent).
According to the present invention, in step (4), the second modifying group provided by the silane represented by formula (2) above is modified on at least a part of the surface of the remaining surface exposed by the silica nanoparticles by subjecting the remaining surface-exposed silica nanoparticles to a second contact reaction with the silane represented by formula (2). It is understood that the silane represented by formula (2) in step (4) will be more selectively combined by contact reaction on the exposed remaining surface, but it is not excluded that a small amount of silane represented by formula (2) will be combined with the surface of the silica nanoparticles obtained in step (2) modified with the first modifying group provided by the silane represented by formula (1), and such cases are also included in the scope of the present invention.
The silica nanoparticles obtained in step (3) may be dried and then used in the reaction in step (4), but the present invention is not particularly limited thereto.
Among them, in order to obtain a chip carrier having a better chip carrier effect, it is preferable that the weight ratio of the amount of the silica nanoparticles to the amount of the silane represented by formula (2) is 100: 5-100, preferably 100: 5-80, preferably 100: 10-60, more preferably 100: 30-50.
According to the present invention, the amount of the second solvent may vary within a wide range, and preferably, the amount of the second solvent is 20 to 200mL, preferably 50 to 100mL, with respect to 1g of the silica nanoparticles. The second solvent herein is a mixed solvent comprising alcohol and water, and the mixed solvent comprising alcohol and water may be as described above, although it is understood that the second solvent may be the same as or different from the first solvent.
According to the present invention, preferably, the conditions of the second contact reaction include: the temperature is 45-80 ℃ and the time is 6-20 h. More preferably, the conditions of the second contact reaction include: the temperature is 50-70 ℃ and the time is 8-16 h.
According to the present invention, the product after the second contact reaction may be subjected to a certain purification treatment, for example, the product of the second contact reaction may be subjected to solid-liquid separation (for example, centrifugal separation) to separate a solid phase, and then washed with water or a mixed solvent containing alcohol and water (the mixed solvent containing alcohol and water described above may be used), and then dried to obtain the Janus particles of silica.
In a third aspect, the present invention provides Janus particles of silica produced by the above process.
The Janus particles of silica provided by the third aspect of the invention may have the structural features described hereinbefore for the first aspect, but it will be appreciated that the Janus particles of silica of this aspect are directly obtainable by the process of the second aspect of the invention, provided that the corresponding desired silica product obtainable by the process of the second aspect is within the scope of the invention according to the third aspect.
In a fourth aspect, the present invention provides the use of the above-described Janus particles of silica as an cuttings carrier in an oil-based drilling fluid.
In a fifth aspect of the invention, there is provided an oil-based drilling fluid comprising Janus particles of the above-described silica.
According to the invention, the oil-based drilling fluid added with the Janus particles of the silicon dioxide as the chip carrier can obtain high-efficiency chip carrier effect, wherein the dosage of the Janus particles of the silicon dioxide can be changed in a wide range, and the content of the Janus particles of the silicon dioxide is preferably 1-5 wt%, preferably 2-5 wt% based on the total weight of the oil-based drilling fluid.
The oil phase in the drilling fluid according to the invention may be any oil phase conventional in the art, such as diesel oil and white oil (e.g. 3# white oil (having a flash point of 220 ℃ C., a kinematic viscosity of 3mm at 40 ℃ C.) such as20.85 specific gravity/s), 5# white oil (flash point 220 deg.C, kinematic viscosity at 40 deg.C 3.5mm2/s, specific gravity of 0.85). A certain amount of CaCl is also added into the oil-based drilling fluid2Preferably with CaCl2CaCl with a concentration of 20 to 40 wt%2Aqueous solution of (a) such as CaCl relative to 100 parts by weight of the oil phase in the drilling fluid2The amount of the aqueous solution of (a) is 10 to 40 parts by weight.
According to the present invention, the oil-based drilling fluid may further contain conventional additives in oil-based drilling fluids, preferably, the oil-based drilling fluid contains one or more of wetting agents, fluid loss additives, alkalinity regulators, emulsifiers, and the like.
The wetting agent can improve the wetting property of the drilling fluid and prevent the downhole complex conditions such as sticking, for example, one or more of modified phospholipid (such as modified phospholipid sold under the trademark FHGT-G of Shanghai Yokogaku company) and fatty glyceride and surfactant mixture (such as modified phospholipid sold under the trademark FK-1), preferably FHGT-G modified phospholipid. More preferably, the lubricant is used in an amount of 0.5 to 2 wt.%, based on the total weight of the oil-based drilling fluid.
The fluid loss additive can improve the wall building property of drilling fluid, and can be one or more of oxidized asphalt, modified humic acid and polymer oil-based fluid loss additive (such as sulfonated polystyrene), and is preferably modified humic acid and/or polymer oil-based fluid loss additive. Preferably, the fluid loss additive is used in an amount of 1 to 3 wt% based on the total weight of the oil-based drilling fluid.
The alkalinity regulator has the functions of stabilizing the emulsion and increasing the breaking voltage, and can be CaO, for example. Preferably, the alkalinity regulator is used in an amount of 2 to 5 wt% based on the total weight of the oil-based drilling fluid.
Among them, as the emulsifier, an emulsifier described in patent document CN105647489B can be cited.
The above additives may be commercially available or prepared by conventional methods in the art, and are not described herein.
In a sixth aspect, the invention provides the use of the oil-based drilling fluid described above in oil and gas drilling.
On the basis of not influencing the rheological property of the oil-based drilling fluid, the super-amphiphobic Janus particle chip carrying agent disclosed by the invention can reduce the oil-water interfacial tension by changing the surface wettability of rock chips, and greatly improve the foaming effect, foam stabilizing effect and chip carrying efficiency of the drilling fluid. The oil-based drilling fluid system containing the chip carrying agent can effectively promote the oil-based drilling fluid to be widely applied to wells with complex structures, greatly reduces the probability of well wall collapse, can play a good reservoir protection effect, and has important practical value and economic benefit for further promoting the exploration and development of unconventional oil and gas reservoirs.
The present invention will be described in detail below by way of examples.
Emulsifier preparation example 1
(1) Mixing reactants according to a molar ratio of tetraethylenepentamine to linoleic acid of 1:2.2 (namely, the molar ratio of the dosage of the tetraethylenepentamine to the dosage of the linoleic acid is 1:1.1 in terms of primary amine groups) and stirring at 250r/min for 40min, then adjusting the pH value of the obtained mixture to 9, then reacting at 230 ℃ for 3 hours, simultaneously adopting a water separator to separate water, and then cooling to room temperature;
(2) mixing the reaction product of the step (1) with malonic acid (the molar ratio of the amount of tetraethylenepentamine to the amount of malonic acid is 1:0.6), adjusting the pH value of the obtained mixture to 8, and then stirring and reacting at 90 ℃ and 400r/min for 6h to obtain an emulsifier A1. Through the analysis and detection of infrared and nuclear magnetic resonance hydrogen spectrums and carbon spectrums, the emulsifier A1 contains amide groups, unsaturated double bonds and carboxyl groups and has a comb-shaped structure.
Example 1
This example illustrates the super-amphiphobic Janus particles of silica of the present invention and a method for preparing the same.
(1) 1g of SiO2Adding nanoparticles (500 nm in diameter) and 20g of paraffin spheres (0.05 mm in diameter) into 100mL of aqueous solution of didodecyldimethylammonium bromide (1 mg/mL) at 75 deg.C, stirring for 60min, cooling to room temperature (about 25 deg.C), and filtering to repeatedly flush out the paraffin spheres on the filter cake with water;
(2) adding the paraffin ball obtained in the step (1) into 50mL of 2 wt% ethanol water solution, adding 0.8g of 3-aminopropyltriethoxysilane, reacting for 48h at 25 ℃, filtering, and repeatedly flushing the paraffin ball on a filter cake with water and ethanol;
(3) adding the paraffin ball obtained in the step (2) into 200mL of dichloromethane, dissolving the paraffin ball at 40 ℃, centrifuging and collecting SiO2Washing the nano particles with dichloromethane and then drying;
(4) drying the SiO2Adding the nano particles into 50mL of 2 wt% ethanol water solution, adding 0.4g of n-octyl triethoxysilane, reacting at 60 ℃ for 12h, and centrifugally separating to obtain SiO2And (3) repeatedly washing the nano particles with water, and drying to obtain the silicon dioxide super-amphiphobic Janus particles SAJ-1.
Example 2
This example illustrates the super-amphiphobic Janus particles of silica of the present invention and a method for preparing the same.
(1) 1g of SiO2Adding nanoparticles (particle size of 500nm) and 20g of paraffin spheres (particle size of 0.8mm) into 150mL of an aqueous solution of n-hexadecyltrimethylammonium bromide (concentration of 0.5mg/mL) under stirring at 70 ℃ for 50min, then cooling to room temperature (about 25 ℃), and filtering to repeatedly flush the paraffin spheres on the filter cake with water;
(2) adding the paraffin ball obtained in the step (1) into 80mL of 5 wt% methanol aqueous solution, adding 1g of 3-aminopropyltrimethoxysilane, reacting for 60h at 25 ℃, filtering, and repeatedly flushing the paraffin ball on a filter cake with water and ethanol;
(3) adding the paraffin ball obtained in the step (2) into 200mL of dichloromethane, dissolving the paraffin ball at 40 ℃, centrifuging and collecting SiO2Washing the nano particles with dichloromethane and then drying;
(4) drying the SiO2Adding the nano particles into 80mL of 5 weight percent methanol aqueous solution, adding 0.4g of n-decyl triethoxysilane, reacting for 16h at 70 ℃, and centrifugally separating to obtain SiO2And (3) repeatedly washing the nano particles with water, and drying to obtain the silicon dioxide super-amphiphobic Janus particles SAJ-2.
Example 3
This example illustrates the super-amphiphobic Janus particles of silica of the present invention and a method for preparing the same.
(1) 1g of SiO2Adding nanoparticles (500 nm in diameter) and 20g of paraffin spheres (0.1 mm in diameter) into 100mL of aqueous solution of didodecyldimethylammonium bromide (0.1 g/mL) at 75 deg.C, stirring for 120min, cooling to room temperature (about 25 deg.C), and filtering to repeatedly flush out the paraffin spheres from the filter cake with water;
(2) adding the paraffin ball obtained in the step (1) into 50mL of 2 wt% ethanol water solution, adding 1g of 3-aminopropyltriethoxysilane, reacting for 60h at 25 ℃, filtering, and repeatedly flushing the paraffin ball on a filter cake with water and ethanol;
(3) adding the paraffin ball obtained in the step (2) into 200mL of dichloromethane, dissolving the paraffin ball at 40 ℃, centrifuging and collecting SiO2Washing the nano particles with dichloromethane and then drying;
(4) drying the SiO2Adding the nano particles into 50mL of 2 wt% ethanol water solution, adding 0.5g of n-octyl triethoxysilane, reacting at 70 ℃ for 16h, and centrifugally separating to obtain SiO2And (3) repeatedly washing the nano particles with water, and drying to obtain the silicon dioxide super-amphiphobic Janus particles SAJ-3.
Example 4
This example illustrates the super-amphiphobic Janus particles of silica of the present invention and a method for preparing the same.
The process as described in example 1, except that 3-aminopropyltriethoxysilane was used in an amount of 1.2g and n-octyltriethoxysilane was used in an amount of 0.1 g; finally, the super-amphiphobic Janus particles SAJ-4 of the silicon dioxide are obtained.
Example 5
This example illustrates the super-amphiphobic Janus particles of silica of the present invention and a method for preparing the same.
The process as described in example 1, except that 3-aminopropyltriethoxysilane was used in an amount of 0.4g and n-octyltriethoxysilane was used in an amount of 0.8 g; finally, the super-amphiphobic Janus particles SAJ-5 of the silicon dioxide are obtained.
Example 6
This example illustrates the super-amphiphobic Janus particles of silica of the present invention and a method for preparing the same.
The process as described in example 1, except that 3-aminopropyltriethoxysilane was used in an amount of 1.5g and n-octyltriethoxysilane was used in an amount of 0.05 g; finally, the super-amphiphobic Janus particles SAJ-6 of the silicon dioxide are obtained.
Example 7
This example illustrates the super-amphiphobic Janus particles of silica of the present invention and a method for preparing the same.
The process as described in example 1, except that 3-aminopropyltriethoxysilane was used in an amount of 0.1g and n-octyltriethoxysilane was used in an amount of 1 g; finally, the super-amphiphobic Janus particles SAJ-7 of the silicon dioxide are obtained.
Comparative example 1
Directly mixing 1g of SiO2Adding the nano particles into 50mL of 2 wt% ethanol aqueous solution, adding 1.2g of 3-aminopropyltriethoxysilane, reacting for 48h at 25 ℃, filtering, repeatedly washing with water, and drying to obtain the modified silicon dioxide nano particles DS-1.
Comparative example 2
Directly mixing 1g of SiO2Adding the nano particles into 50mL of 2 wt% ethanol aqueous solution, adding 1.2g of n-octyl triethoxysilane, reacting for 12h at 60 ℃, filtering, repeatedly washing with water, and drying to obtain the modified silicon dioxide nano particles DS-1.
Test example 1
Evaluation of surface tension: preparing the silicon dioxide nano particle dispersion water into anti-dandruff agent solutions with different concentrations, and measuring the surface tension of n-hexadecane by using the anti-dandruff agent with different concentrations prepared by the platinum plate method (specifically, the method described in GB/T18396-2001 standard) at 25 ℃; the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the silica Janus particles of the present invention have a good solution surface improving effect, and can effectively reduce the surface tension of n-hexadecane, and particularly, the modified silica material prepared by the preferred method can obtain a lower surface tension at the same concentration, and the surface tension can be reduced to below 11.5mN/m at a concentration of 3 wt%.
Test example 2
Measuring the hydrophobic and oleophobic performance of the rock surface: preparing 3 wt% ethanol of the silica nanoparticles as a solution to be tested, and preparing 5 concentrations of the solution to be tested (1 wt%, 2 wt%, 3 wt%, 4 wt% and 5 wt%) from the super-amphiphobic Janus particles SAJ-1 of the silica; placing the artificial rock core into the artificial rock core, and soaking for 2 hours at 160 ℃; taking out the core, cooling and air drying under natural conditions, and measuring contact angle theta of two phases of oil and water on the surface of the core by using a contact angle measuring instrument (JC 2000D3 contact angle measuring instrument of Shanghai Zhongchen digital technology equipment Co., Ltd.)oAnd thetawThe results are shown in Table 2, in which the oil phase test solution was n-hexadecane and the water phase test solution was distilled water.
TABLE 2
As can be seen from the data in Table 2, the super-amphiphobic Janus particle of the silicon dioxide provided by the invention can enable the rock surface to be super-hydrophobic and super-oleophobic, and the surface super-amphiphobic effect is realized.
Test example 3
The super-amphiphobic Janus particles SAJ-1 of the silicon dioxide are dispersed in water to prepare the anti-dandruff solution with different concentrations, and the solution is added into a rotating drop interfacial tensiometer to carry out oil-water interfacial tension measurement (see the method described in SY/T5370-1999 standard in detail), and the results are shown in Table 3.
TABLE 3
The data in table 3 show that a small amount of super-amphiphobic Janus particles of silicon dioxide can effectively reduce the oil-water interfacial tension, contribute to the formation of bubbles in an oil-water drilling fluid system, and have a better promotion effect on the cuttings carrying of the oil-water drilling fluid system.
Test example 4
Evaluation of foaming and foam stabilizing Properties: the silica nanoparticle chip carrier was prepared into a 3 wt% aqueous dispersion, and stirred and foamed for 2min with a high-speed stirrer, and the half-life of foaming, the foaming volume and the foam stabilizing time were measured (the specific measurement method is described in SY-T6465-2000 standard), and the results are shown in Table 4.
TABLE 4
As can be seen from the data in table 4, the super-amphiphobic Janus particles of the silica of the present invention have excellent bubble and bubble stabilizing properties.
Test example 5
Composition of oil-based drilling fluid Y0: 3% by weight of emulsifier A1, 2% by weight of polymer oil-based fluid loss additive (HFLO type oil-based fluid loss additive available from Honghua, Sichuan), and the balance of a mixture of 3# white oil and water (weight ratio of 3# white oil to water is 9:1), and the density was controlled to 0.87g/cm3。
The oil-based drilling fluid Y1-Y7 comprises the following components: the oil-based drilling fluid Y0 is prepared by adopting the composition, except that 0.3 weight percent of silica nano particles SAJ-1 to SAJ-7 are respectively added as chip carrying agents.
The oil-based drilling fluid DY1-DY2 comprises the following components: the oil-based drilling fluid Y0 is prepared by adopting the composition, except that 0.3 weight percent of silicon dioxide nano particles DS-1 and DS-2 are respectively added as chip carrying agents.
The rheology and fluid loss performance of such oil-based drilling fluids before aging were tested and the results are shown in table 5, wherein:
AV is an apparent viscosity measured by a van-type six-speed viscometer in mPas,
PV is a plastic viscosity measured by a van-type six-speed viscometer and has a unit of mPa · s, PV ═ θ600-θ300；
YP is dynamic shear force calculated from data measured with a normal six-speed viscometer, and has a unit Pa of 0.511(θ)300-PV)；
API refers to medium pressure fluid loss, measured by a medium pressure fluid loss gauge, in mL.
TABLE 5
The data in table 5 show that the drilling fluid with the super-amphiphobic Janus particles added with the silicon dioxide as the chip carrying agent not only improves the dynamic shear force of the system, but also reduces the filtration loss of the system, is beneficial to enhancing the chip carrying effect of the oil-based drilling fluid system, and is more beneficial to protecting a reservoir stratum.
Test example 6
50g of rock debris is added into 350mL of the drilling fluid Y0-Y7 and DY1-DY2 respectively, the debris carrying effect of each drilling fluid is evaluated by adopting a shaft simulation device, the debris carrying efficiency is calculated, and the result is shown in Table 6.
Wherein, the chip carrying efficiency is the percentage of the mass of the carried rock chips in the mass of the added rock chips.
TABLE 6
It can be seen from the data in table 6 that drilling fluids containing the super-amphiphobic Janus particles of the silica of the present invention as chip carriers can achieve higher chip carrying effect at lower addition levels.
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 (30)
1. The application of Janus particles of silica as a chip carrier in an oil-based drilling fluid is characterized in that the Janus particles are silica nanoparticles with asymmetric modification on the surfaces, wherein part of the surfaces of the Janus particles are modified with first modification groups provided by silane shown in a formula (1), and at least part of the rest surfaces of the Janus particles are modified with second modification groups provided by silane shown in a formula (2);
formula (1)
Formula (2)
Wherein R is1-R6Each independently selected from C1-C6 alkoxy; l is1Alkylene selected from C1-C8; r7Selected from C6-C20 alkyl groups.
2. Use according to claim 1, wherein R1-R6Each independently selected from C1-C4 alkoxy; l is1Alkylene selected from C1-C6; r7Selected from C6-C16 alkyl groups.
3. Use according to claim 2, wherein R1-R6Each independently selected from methoxy, ethoxy and n-propoxy; l is1Is selected from-CH2-、-CH2-CH2-、-CH2-CH2-CH2-、-CH(CH3)-CH2-、-CH2-CH(CH3) -or-CH2-(CH2)2-CH2-；R7Selected from n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl or n-hexadecyl.
4. The use according to any one of claims 1 to 3, wherein the silica nanoparticles have a particle size of 100-1000 nm.
5. The use according to claim 4, wherein the silica nanoparticles have a particle size of 200-800 nm.
6. Use according to any one of claims 1 to 3, wherein the silica nanoparticles and the silane of formula (1) provide a first modifying group weight ratio of 100: 10-150.
7. The use according to claim 6, wherein the weight ratio of silica nanoparticles to the first modifying group provided by the silane of formula (1) is 100: 40-120.
8. The use according to claim 7, wherein the weight ratio of silica nanoparticles to the first modifying group provided by the silane of formula (1) is 100: 50-100.
9. The use according to claim 8, wherein the weight ratio of silica nanoparticles to the first modifying group provided by the silane of formula (1) is 100: 80-100.
10. The use according to claim 6, wherein the weight ratio of silica nanoparticles to the second modifying groups provided by the silane of formula (2) is 100: 5-100.
11. The use according to claim 10, wherein the weight ratio of silica nanoparticles to the second modifying groups provided by the silane of formula (2) is 100: 5-80.
12. The use according to claim 11, wherein the weight ratio of silica nanoparticles to the second modifying group provided by the silane of formula (2) is 100: 10-60.
13. The use according to claim 12, wherein the weight ratio of silica nanoparticles to the second modifying groups provided by the silane of formula (2) is 100: 30-50.
14. The application of Janus particles of silicon dioxide as an cuttings carrier in oil-based drilling fluid, wherein the Janus particles of the silicon dioxide are prepared by the following preparation method, and the preparation method comprises the following steps:
(1) protecting partial surface of the silica nano particle;
(2) in a first solvent, carrying out a first contact reaction on the protected silica nanoparticles and silane shown in the formula (1), and then removing the solvent to obtain silica nanoparticles of which the surfaces are partially modified with first modifying groups provided by the silane shown in the formula (1); the first solvent is a mixed solvent containing alcohol and water;
(3) exposing the remaining surface of the protected silica nanoparticles;
(4) performing a second contact reaction of the remaining surface-exposed silica nanoparticles with the silane represented by formula (2) in a second solvent to modify at least a portion of the remaining surface of the silica nanoparticles with a second modifying group provided by the silane represented by formula (2); the second solvent is a mixed solvent containing alcohol and water;
formula (1)
Formula (2)
Wherein R is1-R6Each independently selected from C1-C6 alkoxy; l is1Alkylene selected from C1-C8; r7Selected from C6-C20 alkyl groups.
15. Use according to claim 14, wherein R1-R6Each independently selected from C1-C4 alkoxy; l is1Alkylene selected from C1-C6; r7Selected from C6-C16 alkyl groups.
16. Use according to claim 15, wherein R1-R6Each independently selected from methoxy, ethoxy and n-propoxy; l is1Is selected from-CH2-、-CH2-CH2-、-CH2-CH2-CH2-、-CH(CH3)-CH2-、-CH2-CH(CH3) -or-CH2-(CH2)2-CH2-；R7Selected from n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl or n-hexadecyl.
17. Use according to any one of claims 14 to 16, wherein the silica nanoparticles are used in a weight ratio to the silane of formula (1) of 100: 10-150.
18. The use according to claim 17, wherein the weight ratio of silica nanoparticles to the amount of silane of formula (1) is 100: 40-120.
19. The use according to claim 18, wherein the weight ratio of silica nanoparticles to the amount of silane of formula (1) is 100: 50-100.
20. The use according to claim 19, wherein the weight ratio of silica nanoparticles to the amount of silane of formula (1) is 100: 80-100.
21. Use according to any one of claims 14 to 16, wherein the silica nanoparticles are used in a weight ratio to the silane of formula (2) of 100: 5-100.
22. The use according to claim 21, wherein the weight ratio of silica nanoparticles to the amount of silane of formula (2) is 100: 10-80.
23. The use according to claim 22, wherein the weight ratio of silica nanoparticles to the amount of silane of formula (2) is 100: 20-60.
24. The use according to claim 23, wherein the weight ratio of silica nanoparticles to the amount of silane of formula (2) is 100: 30-50.
25. Use according to any one of claims 14 to 16, wherein step (1) comprises adhering silica nanoparticles to wax particles to protect a portion of the surface of the silica nanoparticles.
26. Use according to claim 25, wherein the wax particles are wax spheres having a particle size of 0.01-0.1 mm; the particle size of the silica nano-particles is 100-1000 nm.
27. The use as claimed in claim 26, wherein the silica nanoparticles have a particle size of 200-800 nm.
28. The use according to any one of claims 14 to 16, wherein the first solvent is used in an amount of 20 to 200mL and the second solvent is used in an amount of 20 to 200mL, relative to 1g of silica nanoparticles.
29. The use according to claim 28, wherein the mixed solvent containing alcohol and water contains 1-5 wt% of alcohol solvent;
the alcohol solvent in the mixed solvent containing alcohol and water is one or more of ethanol, methanol, n-propanol and isopropanol.
30. The use of any one of claims 14-16, wherein the conditions of the first contact reaction comprise: the temperature is 10-30 ℃, and the time is 30-70 h;
the conditions of the second contact reaction include: the temperature is 45-80 ℃ and the time is 6-20 h.
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