阅读说明：本技术 适用于水基钻井液用高效携屑剂Al2O3/SiO2复合材料 (High-efficiency chip carrying agent Al suitable for water-based drilling fluid2O3/SiO2Composite material ) 是由 蒋官澄 倪晓骁 彭春耀 贺垠博 杨丽丽 骆小虎 罗绪武 梁兴 谭宾 冉启发 刘小 于 2021-08-26 设计创作，主要内容包括：本发明涉及石油工业的油田化学领域,具体涉及适用于水基钻井液用高效携屑剂Al-(2)O-(3)/SiO-(2)复合材料。Al-(2)O-(3)/SiO-(2)复合材料包括含有Al-(2)O-(3)和SiO-(2)的固体颗粒,以及在固体颗粒表面修饰的聚丙烯酰胺类聚合物；其中,所述聚丙烯酰胺类聚合物含有式(1)和式(2)所示的结构单元。本发明的Al-(2)O-(3)/SiO-(2)复合材料作为高效携屑剂能够有效改善岩屑表面润湿性能,将岩屑表面亲水亲油的润湿性转变成疏水疏油的气润湿性能,从而降低岩屑的相对密度,同时通过聚合物的流变性能提高体系的携屑效果。(The invention relates to the field of oilfield chemistry in the petroleum industry, in particular to an efficient chip carrying agent Al suitable for water-based drilling fluid 2 O 3 /SiO 2 A composite material. Al (Al) 2 O 3 /SiO 2 The composite material comprises Al 2 O 3 And SiO 2 The solid particles of (1), and a polyacrylamide-based polymer modified on the surface of the solid particles; wherein the polyacrylamide-based polymerThe compound contains structural units represented by the formulae (1) and (2). Al of the invention 2 O 3 /SiO 2 The composite material as an efficient chip carrying agent can effectively improve the wettability of the surface of rock debris, and converts the hydrophilic and oleophilic wettability of the surface of the rock debris into hydrophobic and oleophobic air wettability, so that the relative density of the rock debris is reduced, and the chip carrying effect of a system is improved through the rheological property of a polymer.)

1. Al (aluminum)₂O₃/SiO₂Composite material, characterized in that it comprises a material containing Al₂O₃And SiO₂The solid particles of (1), and a polyacrylamide-based polymer modified on the surface of the solid particles; wherein the polyacrylamide polymer contains structural units shown in formula (1) and formula (2):

formula (1)

Formula (2)

Wherein R is₁-R₆Each independently selected from H or C1-C6 alkyl; l is selected from C0-C6 alkylene; r₇Selected from the group consisting of C6-C20 alkyl substituted with halogen.

2. The composite of claim 1, wherein R₁-R₆Each independently selected from H or C1-C4 alkyl; l is selected from C0-C4 alkylene; r₇Selected from the group consisting of C4-C16 alkyl substituted with halogen;

preferably, R₁-R₆Each independently selected from H, methyl, ethyl or n-propyl; l is absent, -CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂-or-CH₂CH₂CH₂CH₂-；R₇Selected from C6-C12 alkyl substituted with fluorine, chlorine or bromine;

preferably, R₇Selected from the group consisting of perfluoro substituted C6 alkyl, undecafluoro substituted C6 alkyl, nonafluoro substituted C6 alkyl, perfluoro substituted C8 alkyl, pentadecafluoro substituted C8 alkyl, tridecafluoro substituted C8 alkyl, undecafluoro substituted C8 alkyl, nonafluoro substituted C8 alkyl, perfluoro substituted C10 alkyl, nonafluoro substituted C10 alkyl, heptadecafluoro substituted C10 alkyl, pentadecafluoro substituted C10 alkyl, tridecafluoro substituted C10 alkyl, undecafluoro substituted C10 alkyl, nonafluoro substituted C10 alkylPerfluoro substituted C12 alkyl, icosyl-trifluoro-substituted C12 alkyl, heneicosyl-fluoro-substituted C12 alkyl, nonadecyl-substituted C12 alkyl, heptadecyl-fluoro-substituted C12 alkyl, pentadecyl-substituted C12 alkyl, tridecyl-substituted C12 alkyl, undecyl-substituted C12 alkyl, or nonafluoro-substituted C12 alkyl;

preferably, the structural unit represented by formula (1) is provided by acrylamide and/or methacrylamide; the structural unit shown in the formula (2) is provided by one or more of nonafluorohexyl acrylate, nonafluorohexyl methacrylate, perfluorohexyl acrylate, perfluorohexyl methacrylate, tridecafluorooctyl acrylate, tridecafluorooctyl methacrylate, perfluorooctyl acrylate, perfluorooctyl methacrylate, heptadecafluorodecyl acrylate, heptadecafluorodecyl methacrylate, perfluorodecyl acrylate and perfluorodecyl methacrylate.

3. The composite material according to claim 1 or 2, wherein the molar ratio of the structural units represented by formula (1) and formula (2) in the polyacrylamide-based polymer is 1:0.2 to 5, preferably 1:0.4 to 1, more preferably 1:0.5 to 0.8;

or, in the composite material, Al is used₂O₃The molar ratio of the solid particles to the structural units represented by the formulae (1) and (2) in the polyacrylamide-based polymer is 1: (1-15): (0.5-10), preferably 1: (2-10): (1-5), more preferably 1: (2-8): (1-3);

preferably, the molecular weight of the polyacrylamide polymer is 20000-97000 g/mol, preferably 30000-97000g/mol, more preferably 40000-90000 g/mol.

4. The composite material according to any one of claims 1 to 3, wherein Al is present in the solid particles₂O₃And SiO₂In a molar ratio of 1:1 to 5, preferably 1:2 to 4;

or the solid particles contain Al₂O₃Preferably kaolin, more preferably nano kaolin.

5. The composite material according to any one of claims 1 to 4, wherein the solid particles and the polyacrylamide-based polymer are bonded by a silane coupling agent, preferably the silane coupling agent is a silane coupling agent containing an unsaturated carbon-carbon double bond, more preferably the silane coupling agent containing an unsaturated carbon-carbon double bond is one or more of an acryloxy C1-C8 alkyltrialkoxysilane, methacryloxy C1-C8 alkyltrialkoxysilane, acrylamido C1-C8 alkyltrialkoxysilane, methacrylamido C1-C8 alkyltrialkoxysilane, vinyltrialkoxysilane and propenyltrialkoxysilane.

6. Al (aluminum)₂O₃/SiO₂A method of making a composite material, the method comprising:

(1) adopting silane coupling agent to contain Al₂O₃And SiO₂The solid particles of (2) are surface-modified;

(2) polymerizing the surface-modified product obtained in the step (1) with compounds represented by the formulae (1 ') and (2');

formula (1')Formula (2')

Wherein R is₁-R₆Each independently selected from H or C1-C6 alkyl; l is selected from C0-C6 alkylene; r₇Selected from the group consisting of C6-C20 alkyl substituted with halogen.

7. The method of claim 6, wherein R₁-R₆Each independently selected from H or C1-C4 alkyl; l is selected from C0-C4 alkylene; r₇Selected from the group consisting of C4-C16 alkyl substituted with halogen;

preferably, R₁-R₆Each independently selected from H, methyl, ethyl or n-propyl; l is absent,-CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂-or-CH₂CH₂CH₂CH₂-；R₇Selected from C6-C12 alkyl substituted with fluorine, chlorine or bromine;

preferably, R₇Selected from perfluoro-substituted C6 alkyl, undecafluoro-substituted C6 alkyl, nonafluoro-substituted C6 alkyl, perfluoro-substituted C8 alkyl, pentadecafluoro-substituted C8 alkyl, tridecafluoro-substituted C8 alkyl, undecafluoro-substituted C8 alkyl, nonafluoro-substituted C8 alkyl, perfluoro-substituted C10 alkyl, nonafluoro-substituted C10 alkyl, heptadecafluoro-substituted C10 alkyl, pentadecafluoro-substituted C10 alkyl, tridecafluoro-substituted C10 alkyl, undecafluoro-substituted C10 alkyl, nonafluoro-substituted C10 alkyl, perfluoro-substituted C12 alkyl, icosa-trifluoro-substituted C12 alkyl, heneicosa-fluoro-substituted C12 alkyl, nonafluoro-substituted C12 alkyl, heptadecafluoro-substituted C12 alkyl, pentadecafluoro-substituted C12 alkyl, tridecafluoro-substituted C12 alkyl, undecafluoro-substituted C12 alkyl, or nonafluoro-substituted C12 alkyl;

preferably, the compound represented by formula (1') is selected from acrylamide and/or methacrylamide; the compound shown in the formula (2') is selected from one or more of nonafluorohexyl acrylate, nonafluorohexyl methacrylate, perfluorohexyl acrylate, perfluorohexyl methacrylate, tridecyl acrylate, tridecyl octyl methacrylate, perfluorooctyl acrylate, perfluorooctyl methacrylate, heptadecafluorodecyl acrylate, heptadecafluorodecyl methacrylate, perfluorodecyl acrylate and perfluorodecyl methacrylate;

preferably, the silane coupling agent is a silane coupling agent containing an unsaturated carbon-carbon double bond, more preferably, the silane coupling agent containing the unsaturated carbon-carbon double bond is one or more of alkyl trialkoxysilane of acryloxy C1-C8, alkyl trialkoxysilane of methacryloxy C1-C8, alkyl trialkoxysilane of acrylamide C1-C8, alkyl trialkoxysilane of methacrylamide C1-C8, vinyl trialkoxysilane and propenyl trialkoxysilane.

8. The process according to claim 6 or 7, wherein in step (2), the molar ratio of the compound represented by formula (1 ') to the compound represented by formula (2') is 1:0.2 to 5, preferably 1:0.4 to 1, more preferably 1:0.5 to 0.8;

or, with Al₂O₃The molar ratio of the solid particles to the compound represented by the formula (1 ') and the compound represented by the formula (2') is 1: (1-15): (0.5-10), preferably 1: (2-10): (1-5), more preferably 1: (2-8): (1-3).

9. The method according to any one of claims 6-8, wherein Al is present in the solid particles₂O₃And SiO₂In a molar ratio of 1:1 to 5, preferably 1:2 to 4;

or the solid particles contain Al₂O₃Preferably kaolin, more preferably nano kaolin.

10. The method according to any one of claims 6 to 9, wherein in step (1), the surface modification conditions comprise: the temperature is 40-80 deg.C, and the time is 25-100 min;

in the step (2), the polymerization conditions include: the temperature is 40-80 ℃ and the time is 1.5-8 h.

11. Al obtainable by the process according to any of claims 6 to 10₂O₃/SiO₂A composite material.

12. Al according to any of claims 1 to 5 and 11₂O₃/SiO₂The composite material is applied to drilling fluid as a chip carrier.

13. Containing Al according to any of claims 1 to 5 and 11₂O₃/SiO₂The composite material is used as a water-based drilling fluid of a chip carrying agent.

14. Use of the water-based drilling fluid of claim 13 in oil and gas drilling.

Technical Field

The invention relates to the field of oilfield chemistry in the petroleum industry, in particular to an efficient chip carrying agent Al suitable for water-based drilling fluid₂O₃/SiO₂A composite material.

Background

Along with the basic development of conventional oil fields in China in the middle and later stages, the oil reservoir conditions for exploration and development are more and more rigorous, and wells with unconventional complex structures such as deep wells, horizontal wells and the like become development modes of unconventional oil and gas fields more and more. The development of complex structure well has proposed higher requirement to the performance of drilling fluid, carries the detritus difficulty to boring high difficulty well in-process and often meets, easily forms the detritus bed in the pit, further causes the increase of grinding resistance, moment of torsion, forms the sticking of drill even more, causes huge drilling accident, influences final holistic drilling efficiency, causes huge cost consumption. Therefore, conventional water-based drilling fluids must have good chip-carrying properties, which in turn places high demands on the rheological properties of the water-based drilling fluids. The water-based drilling fluid is widely used due to the characteristics of environmental protection and low cost, and mainly comprises bentonite, various polymers and weighting materials. In order to achieve a good chip carrying effect, a large amount of bentonite and polymer materials are usually added into the water-based drilling fluid to improve the viscosity of the whole system, and the drilling speed of the well drilling is reduced, a thicker filter cake is formed, and accidents such as sticking and sticking of the drill bit are caused. Therefore, the development of the high-efficiency chip-carrying water-based drilling fluid treating agent for improving the drilling speed and solving the problem of carrying rocks of wells with complex structures such as deep wells, horizontal wells and the like is necessary, and the high-efficiency chip-carrying agent developed by the invention is a key component of the water-based drilling fluid system.

At present, most of water-based drilling fluid chip carrying agents researched and developed at home and abroad are modified by using vegetable gum molecules to synthesize polymers with special functionality, but the materials have the problems of poor temperature resistance, unstable high-temperature rheological property, complex polymer synthesis process, high product cost, difficulty in large-scale application and the like.

Disclosure of Invention

The invention aims to effectively improve the wettability of the surface of rock debris, convert the hydrophilic and oleophilic wettability of the surface of the rock debris into hydrophobic and oleophobic gas wettability so as to reduce the relative density of the rock debris and improve the debris carrying effect of a system through the rheological property of a polymer₂O₃/SiO₂A composite material comprising Al₂O₃And SiO₂The solid particles of (1), and a polyacrylamide-based polymer modified on the surface of the solid particles; wherein the polyacrylamide polymer contains structural units shown in formula (1) and formula (2):

formula (1)

Formula (2)

Wherein R is₁-R₆Each independently selected from H or C1-C6 alkyl; l is selected from C0-C6 alkylene; r₇Selected from the group consisting of C6-C20 alkyl substituted with halogen.

In a second aspect, the present invention provides an Al₂O₃/SiO₂A method of making a composite material, the method comprising:

(1) adopting silane coupling agent to contain Al₂O₃And SiO₂The solid particles of (2) are surface-modified;

(2) polymerizing the surface-modified product obtained in the step (1) with compounds represented by the formulae (1 ') and (2');

formula (1')Formula (2')

Wherein R is₁-R₆Each independently selected from H or C1-C6 alkyl; l is selected from C0-C6 alkylene; r₇Selected from the group consisting of C6-C20 alkyl substituted with halogen.

In a third aspect, the present invention provides Al obtained by the above method₂O₃/SiO₂A composite material.

The fourth aspect of the present invention provides the above-mentioned Al₂O₃/SiO₂The composite material is applied to drilling fluid as a chip carrier.

The fifth aspect of the present invention provides the above Al₂O₃/SiO₂The composite material is used as a water-based drilling fluid of a chip carrying agent.

In a sixth aspect the present invention provides the use of the above water-based drilling fluid in oil and gas drilling.

Al of the invention₂O₃/SiO₂The composite material as an efficient chip carrying agent can effectively improve the wettability of the surface of rock debris, and converts the hydrophilic and oleophilic wettability of the surface of the rock debris into hydrophobic and oleophobic air wettability, so that the relative density of the rock debris is reduced, and the chip carrying effect of a system is improved through the rheological property of a polymer. And a set of high-efficiency chip-carrying water-based drilling fluid system is formed by taking the chip carrying agent as a core, so that the drilling speed of a complex well and the purification efficiency of a well bore are improved, and the 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.

One aspect of the present invention provides an Al₂O₃/SiO₂A composite material comprising Al₂O₃And SiO₂The solid particles of (1), and a polyacrylamide-based polymer modified on the surface of the solid particles; wherein the polyacrylamide polymer contains structural units shown in formula (1) and formula (2):

formula (1)

Formula (2)

Wherein R is₁-R₆Each independently selected from H or C1-C6 alkyl; l is selected from C0-C6 alkylene; r₇Selected from the group consisting of C6-C20 alkyl substituted with halogen. Wherein C0 alkylene represents the absence or attachment of a bond, the radicals at the two ends of which are directly attached.

Preferably, R₁-R₆Each independently selected from H or C1-C4 alkyl; l is selected from C0-C4 alkylene; r₇Selected from the group consisting of C4-C16 alkyl substituted with halogen.

Preferably, R₁-R₆Each independently selected from H, methyl, ethyl or n-propyl; l is absent, -CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂-or-CH₂CH₂CH₂CH₂-；R₇Selected from C6-C12 alkyl substituted by fluorine, chlorine or bromine.

Preferably, R₇Selected from the group consisting of perfluoro-substituted C6 alkyl, undecafluoro-substituted C6 alkyl, nonafluoro-substituted C6 alkyl, perfluoro-substituted C8 alkyl, pentadecafluoro-substituted C8 alkyl, tridecafluoro-substituted C8 alkyl, undecafluoro-substituted C8 alkyl, nonafluoro-substituted C8 alkyl, perfluoro-substituted C10 alkyl, nonafluoro-substituted C10 alkyl, heptadecafluoro-substituted C10 alkyl, pentadecafluoro-substituted C10 alkyl, tridecafluoro-substituted C10 alkyl, undecafluoro-substituted C10 alkyl, nonafluoro-substituted C10 alkyl, perfluoro-substituted C12 alkyl, icosyl-trifluoro-substituted C12 alkyl, heneicosyl-fluoro-substituted C12 alkyl, nonafluoro-substituted C12 alkyl, heptadecafluoro-substituted C12 alkylPentadecafluoro substituted C12 alkyl, tridecafluoro substituted C12 alkyl, undecafluoro substituted C12 alkyl or nonafluoro substituted C12 alkyl.

Preferably, the structural unit represented by formula (1) is provided by acrylamide and/or methacrylamide; the structural unit shown in the formula (2) is provided by one or more of nonafluorohexyl acrylate, nonafluorohexyl methacrylate, perfluorohexyl acrylate, perfluorohexyl methacrylate, tridecafluorooctyl acrylate, tridecafluorooctyl methacrylate, perfluorooctyl acrylate, perfluorooctyl methacrylate, heptadecafluorodecyl acrylate, heptadecafluorodecyl methacrylate, perfluorodecyl acrylate and perfluorodecyl methacrylate. Preferably, in the polyacrylamide polymer, the molar ratio of the structural units represented by the formula (1) to the structural units represented by the formula (2) is 1:0.2 to 5, preferably 1:0.4 to 1, and more preferably 1:0.5 to 0.8.

Or, in the composite material, Al is used₂O₃The molar ratio of the solid particles to the structural units represented by the formulae (1) and (2) in the polyacrylamide-based polymer is 1: (1-15): (0.5-10), preferably 1: (2-10): (1-5), more preferably 1: (2-8): (1-3).

Preferably, the molecular weight of the polyacrylamide polymer is 20000-97000 g/mol, preferably 30000-97000g/mol, more preferably 40000-90000 g/mol.

Preferably, in the solid particles, Al₂O₃And SiO₂In a molar ratio of 1:1 to 5, preferably 1:2 to 4.

Or the solid particles contain Al₂O₃The silicate of (b) is preferably kaolin, more preferably nano-kaolin, the particle size of which may be, for example, 50-2000nm, preferably 100-1000nm, for example 100-500 nm.

Preferably, the solid particles are bonded to the polyacrylamide polymer by a silane coupling agent. Preferably, the silane coupling agent is a silane coupling agent containing an unsaturated carbon-carbon double bond, more preferably, the silane coupling agent containing the unsaturated carbon-carbon double bond is one or more of alkyl trialkoxysilane of acryloxy C1-C8, alkyl trialkoxysilane of methacryloxy C1-C8, alkyl trialkoxysilane of acrylamide C1-C8, alkyl trialkoxysilane of methacrylamide C1-C8, vinyl trialkoxysilane and propenyl trialkoxysilane.

Among them, the alkyltrialkoxysilane of acryloxy C1-C8 may be specifically selected from acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane, acryloxymethyltri-n-propoxysilane, 2-acryloxyethyltrimethoxysilane, 2-acryloxyethyltriethoxysilane, 2-acryloxyethyltri-n-propoxysilane, gamma-acryloxypropyltrimethoxysilane, gamma-acryloxypropyltriethoxysilane, and gamma-acryloxypropyltri-n-propoxysilane.

The alkyltrialkoxysilane of methacryloxy C1-C8 may be specifically selected from the group consisting of methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, methacryloxymethyltri-n-propoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-methacryloxyethyltri-n-propoxysilane, γ -methacryloxypropyltrimethoxysilane, γ -methacryloxypropyltriethoxysilane, γ -methacryloxypropyltri-n-propoxysilane.

The alkyltrialkoxysilane of acrylamide group C1-C8 can be specifically selected from acrylamidomethyltrimethoxysilane, acrylamidomethyltriethoxysilane, acrylamidomethyltri-n-propoxysilane, 2-acrylamidoethyltrimethoxysilane, 2-acrylamidoethyltriethoxysilane, 2-acrylamidoethyltri-n-propoxysilane, gamma-acrylamidopropyltrimethoxysilane, gamma-acrylamidopropyltriethoxysilane, gamma-acrylamidopropyltri-n-propoxysilane.

The alkyltrialkoxysilane of methacrylamide group C1-C8 can be chosen in particular from methacrylaminomethyltrimethoxysilane, methacrylaminomethyltriethoxysilane, methacrylaminomethyltri-n-propoxysilane, 2-methacrylaminoethyltrimethoxysilane, 2-methacrylaminoethyltriethoxysilane, 2-methacrylaminoethyltri-n-propoxysilane, gamma-methacrylamidopropyltrimethoxysilane, gamma-methacrylamidopropyltriethoxysilane, gamma-methacrylamidopropyltri-n-propoxysilane.

The vinyltrialkoxysilane can be selected from vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane.

The allyltrialkoxysilane can be specifically selected from the group consisting of allyltrimethoxysilane, allyltriethoxysilane, and allyltri-n-propoxysilane.

In a preferred embodiment of the present invention, the silane coupling agent is preferably gamma-methacryloxypropyltrimethoxysilane (KH-570).

In a second aspect, the present invention provides an Al₂O₃/SiO₂A method of making a composite material, the method comprising:

(1) adopting silane coupling agent to contain Al₂O₃And SiO₂The solid particles of (2) are surface-modified;

(2) polymerizing the surface-modified product obtained in the step (1) with compounds represented by the formulae (1 ') and (2');

formula (1')Formula (2')

Wherein R is₁-R₆Each independently selected from H or C1-C6 alkyl; l is selected from C0-C6 alkylene; r₇Selected from the group consisting of C6-C20 alkyl substituted with halogen.

The above compounds were selected and proportioned as described above.

In a preferred embodiment of the present invention, the compound represented by formula (1') is selected from acrylamide and/or methacrylamide; the compound shown in the formula (2') is selected from one or more of nonafluorohexyl acrylate, nonafluorohexyl methacrylate, perfluorohexyl acrylate, perfluorohexyl methacrylate, tridecyl acrylate, tridecyl octyl methacrylate, perfluorooctyl acrylate, perfluorooctyl methacrylate, heptadecafluorodecyl acrylate, heptadecafluorodecyl methacrylate, perfluorodecyl acrylate and perfluorodecyl methacrylate.

Preferably, in step (1), the surface modification conditions include: the temperature is 40-80 deg.C, and the time is 25-100 min. In the step (2), the polymerization conditions include: the temperature is 40-80 ℃ and the time is 1.5-8 h.

More preferably, the conditions for the surface modification include: the temperature is 45-65 deg.C, and the time is 30-90 min.

More preferably, the polymerization conditions include: the temperature is 45-65 ℃ and the time is 2-6 h.

In the present invention, in step (1), the solid particles and the silane coupling agent may be dispersed and mixed in a solvent, wherein the solvent may be an alcohol solvent, particularly an alcohol-water mixed solvent (the volume ratio of alcohol/water may be 1: 1-3, preferably 1: 1-1.5), and the alcohol may be selected from methanol, ethanol, ethylene glycol, and the like. The amount may vary within wide limits, for example, so that the solid particles are present in the solvent in an amount of from 0.01 to 10g/mL, preferably from 0.05 to 2g/mL, more preferably from 0.05 to 0.2 g/mL.

In the present invention, in the step (2), the polymerization reaction may be carried out in the presence of an initiator, and the initiator may be selected from a variety of initiators capable of initiating the polymerization reaction of the monomer of the present invention, and may be, for example, one or more of potassium persulfate, ammonium persulfate, and the like. The amount can be adjusted according to the needs of the polymerization reaction. In the present invention, in order to modify the surface of the solid particles with more suitable polymer chains to obtain more excellent chip-carrying effect, it is preferable that the initiator is used in an amount of 0.1 to 3% by weight, preferably 0.5 to 1.5% by weight, relative to the total weight of the compounds represented by the formulae (1 ') and (2').

In a third aspect, the present invention provides Al obtained by the above method₂O₃/SiO₂Composite materialAnd (5) feeding.

The fourth aspect of the present invention provides the above-mentioned Al₂O₃/SiO₂The composite material is applied to drilling fluid as a chip carrier.

The fifth aspect of the present invention provides the above Al₂O₃/SiO₂The composite material is used as a water-based drilling fluid of a chip carrying agent.

In a sixth aspect the present invention provides the use of the above water-based drilling fluid in oil and gas drilling.

The Al provided by the invention₂O₃/SiO₂The composite material can effectively improve the wettability of the surface of rock debris and simultaneously improve the rheological effect of the system, the debris carrying agent can effectively improve the drilling speed and the well hole purification efficiency of a well with a complex structure, and a water-based drilling fluid system consisting of the debris carrying agent has a great promotion effect on the acceleration and the efficiency improvement of the drilling of the well with the complex structure in future, and has important practical value and economic benefit for further promoting the exploration and development of unconventional oil and gas reservoirs in China.

The present invention will be described in detail below by way of examples.

High-efficiency chip carrier example 1

This example serves to illustrate the highly effective chip carrier of the present invention and the method of preparation thereof.

(1) Adding 10g of nano kaolin (Al) into 100mL of ethanol-water mixed solution (the volume ratio of ethanol to water is 1: 1)₂O₃/SiO₂1:2, particle size 200nm) and ultrasonically dispersed for 30 min. Then according to the nano kaolin (with Al)₂O₃Meter): KH570 was added at a molar ratio of 1:1, and the temperature was raised to 55 ℃ for 30 min.

(2) Then according to the nano kaolin (Al) in the solution₂O₃Meter): tridecafluorooctyl methacrylate: adding tridecyl methacrylate and acrylamide in a molar ratio of acrylamide to acrylamide of 1:3:4, adding 1 wt% of initiator potassium persulfate (based on the total mass of tridecyl fluorooctyl methacrylate and acrylamide), continuously reacting for 4h at 55 ℃, cooling to room temperature to obtain a reaction product, namely, an dandruff carrying agent HEX-1, and carrying out a reaction on the mixture to obtain the dandruff carrying agent HEX-1The chip carrying agent HEX-1 is identified to have a polyacrylamide polymer with the molecular weight of 45000 g/mol.

High-efficiency chip carrier example 2

This example serves to illustrate the highly effective chip carrier of the present invention and the method of preparation thereof.

(1) Adding 5g of nano kaolin (Al) into 100mL of ethanol-water mixed solution (the volume ratio of ethanol to water is 1: 2)₂O₃/SiO₂1:2, particle size 400nm) and ultrasonically dispersed for 30 min. Then according to the nano kaolin (with Al)₂O₃Meter): acryloxypropyltriethoxysilane was added at a molar ratio of 1:1.5 and the temperature was raised to 65 ℃ for 40 min.

(2) Then according to the nano kaolin (Al) in the solution₂O₃Meter): tridecafluorooctyl methacrylate: adding tridecyl methacrylate and methacrylamide according to the molar ratio of 1:3:6, adding 0.8 wt% of initiator potassium persulfate (based on the total mass of tridecyl fluorooctyl methacrylate and methacrylamide), continuously reacting for 5 hours at 65 ℃, cooling to room temperature to obtain a reaction product, namely, a chip carrying agent HEX-2, and identifying that the chip carrying agent HEX-2 is a polyacrylamide polymer with the molecular weight of 85000 g/mol.

High-efficiency chip carrier example 3

This example serves to illustrate the highly effective chip carrier of the present invention and the method of preparation thereof.

The process of example 1 was followed except that, in step (2), the nano kaolin (as Al) was used₂O₃Meter): tridecafluorooctyl methacrylate: adding tridecafluorooctyl methacrylate and acrylamide in the molar ratio of acrylamide to 1:1:5, and finally obtaining a reaction product, namely the scrap carrying agent HEX-3 through the whole reaction.

High-efficiency chip carrier example 4

This example serves to illustrate the highly effective chip carrier of the present invention and the method of preparation thereof.

The method of example 1, except that(2) In the specification, according to nano kaolin (with Al)₂O₃Meter): tridecafluorooctyl methacrylate: adding tridecafluorooctyl methacrylate and acrylamide in the molar ratio of acrylamide to 1:3:3, and finally obtaining a reaction product, namely the scrap carrying agent HEX-4 through the whole reaction.

Examples 5 to 6 of high-efficiency chip-carrying agent

This example serves to illustrate the highly effective chip carrier of the present invention and the method of preparation thereof.

The method of embodiment 1, except that:

example 5: the method adopts equimolar nonafluorohexyl acrylate to replace tridecafluorooctyl methacrylate, and a reaction product, namely the scrap carrying agent HEX-5, is finally obtained through the whole reaction.

Example 6: replacing tridecafluorooctyl methacrylate with heptadecafluorodecyl methacrylate in equimolar amount, and finally obtaining a reaction product, namely the dandruff carrying agent HEX-6 through the whole reaction.

Comparative example 1

According to the method described in example 1, except that the same molar amount of n-octyl methacrylate is used instead of tridecafluorooctyl methacrylate, the whole reaction is carried out to obtain the final reaction product, namely the dandruff carrying agent DHEX-1.

Comparative example 2

According to the method described in example 1, except that acrylamide in equimolar amount is used to replace tridecafluorooctyl methacrylate, the reaction product obtained after the whole reaction is the dandruff-carrying agent DHEX-2.

Surface tension and interfacial tension test example 1

Surface tension: dispersing the chip carrying agent in the water solution to prepare chip carrying agent solutions with different concentrations, and measuring the surface tension of the prepared chip carrying agent with different concentrations at 25 ℃ by adopting a platinum gold plate method, wherein the test result is shown in the following table, wherein the surface tension of pure water with the content of 0 weight percent is 72.8/mN m^-1。

Interfacial tension: dispersing the chip carrying agent in deionized water with different amounts to prepare chip carrying agent solutions with different concentrations as water phase, and paraffin oil as paraffin oilOil phase, oil-water interfacial tension measurements were performed using a spinning drop interfacial tension apparatus, and the results are shown in the following table, wherein the pure water-paraffin oil interfacial tension at 0 wt% level is 32.74/mN x m^-1。

TABLE 1

As can be seen from Table 1, the high-efficiency chip carrying agent can effectively reduce the surface tension and the oil-water interfacial tension of deionized water.

Wetting Property test example 2

Dispersing the chip carrying agent in an aqueous solution to prepare chip carrying agent solutions with different concentrations, immersing the core in the solution, soaking and aging for 2 hours, taking out and drying; placing the dried core piece on a contact angle measuring instrument for surface wettability evaluation, and the results are shown in the following table; wherein the contact angle of the water phase on the rock surface is 32.6 degrees at 0 weight percent, and the contact angle of the oil phase on the rock surface is 10.2 degrees at 0 weight percent.

TABLE 2

The table shows that the efficient chip carrying agent has better capability of improving the wettability of the rock surface and can effectively improve the water phase contact angle and the oil phase contact angle of the surface of the rock core.

High temperature resistance and wetting Property test example 3

The test method comprises the following steps: the chip carrier was dispersed in an aqueous solution to prepare a chip carrier solution having a concentration of 5% by weight, and aged at different temperatures for 16 hours to obtain a chip carrier solution after high-temperature aging, and the surface wettability was evaluated in accordance with the procedure in test example 2, with the results shown in the following table.

TABLE 3

As can be seen from the table above, the high-efficiency chip carrying agent has better temperature resistance, can resist the temperature up to 220 ℃, and is favorable for application in high-temperature deep wells.

Drilling fluid rheology and fluid loss performance test example 4

Adding borehole wall stabilizers with different concentrations into base slurry (the base slurry comprises 2 wt% of bentonite, 0.1 wt% of sodium carbonate, 0.02 wt% of sodium hydroxide and the balance of water) to form drilling fluid systems with different concentrations, measuring the rheological property of the drilling fluid systems by using a six-speed viscometer, and testing results are shown in the following table, wherein the testing method comprises the following specific steps:

"PV" refers to the plastic viscosity in mpa · s as measured by a van-type six-speed viscometer;

PV＝θ₆₀₀-θ₃₀₀

"AV" refers to the apparent viscosity, as measured by a van-type six-speed viscometer, in mpa · s;

"YP" means dynamic shear force, calculated from data measured with a normal six-speed viscometer, in Pa;

YP＝0.511(θ₃₀₀-PV)

“φ₆/φ₃"means low shear rate viscosity, as measured by a van-mode six-speed viscometer, dimensionless;

“FL_API"refers to the medium pressure filtration loss, measured by a medium pressure filtration loss apparatus, in mL;

TABLE 4

The data in the table show that the high-efficiency chip carrying agent not only improves the dynamic shear force of a drilling fluid system, but also improves the viscosity at a low shear rate, is beneficial to carrying and suspending rock debris, has the function of reducing the fluid loss, and is more beneficial to the fluid loss wall building property and the reservoir protection performance of the drilling fluid.

Drilling fluid base slurry chip-carrying effect test example 5

Adding different amounts of the high-efficiency chip carrying agent into base slurry (the composition is described above) to form drilling fluid systems with different concentrations, adding 5 wt% of shale chips, evaluating the chip carrying effect of the high-efficiency chip carrying agent by using a shaft simulation device, and calculating the chip carrying efficiency, wherein the results are shown in the following table.

Wherein the cleaning efficiency is 100% of the amount of the carried-out rock debris/the mass of the added rock debris.

TABLE 5

Formulation of	Cleaning efficiency/%)
		Base pulp	39.7
Base stock + 1% by weight HEX-1	54.1
		Base stock + 2% by weight HEX-1	62.4
Base stock + 3% by weight HEX-1	94.6
		Base stock + 4% by weight HEX-1	96.2
Base stock + 5% by weight HEX-1	96.4
		Base stock + 3% by weight HEX-2	96.6
Base stock + 3% by weight HEX-3	81.2
		Base stock + 3% by weight HEX-4	83.3
Base stock + 3% by weight HEX-5	86.5
		Base stock + 3% by weight HEX-6	84.2
Base stock + 3% by weight DHEX-1	62.1
		Base stock + 3% by weight DHEX-2	75.5

The efficient chip carrying agent disclosed by the invention can effectively improve the capacity of carrying rock chips of drilling fluid under the conditions of lower dosage and through the effects of wetting and reversing the surfaces of the rock chips and improving the shearing force of the drilling fluid, is beneficial to cleaning a well hole, and has the cleaning efficiency of over 95%.

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.