CN109837075B - High-temperature thermal response bentonite and high-temperature thermal response bentonite drilling fluid - Google Patents
High-temperature thermal response bentonite and high-temperature thermal response bentonite drilling fluid Download PDFInfo
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Abstract
The invention provides high-temperature thermal response bentonite, a preparation method thereof and high-temperature thermal response bentonite drilling fluid. The core of the high-temperature thermal response bentonite is rigid bentonite particles, and the exterior of the high-temperature thermal response bentonite particles is provided with flexible high-temperature thermal response molecular brushes. The preparation method comprises the steps of activating the bentonite acid, drying, performing ATRP modification, rinsing and drying to obtain the high-temperature thermal response bentonite. The modification method comprises the steps of mixing activated bentonite, (3-aminopropyl) trimethoxy silane (ATMS) and methanol, mixing by magnetic stirring to provide modified activated sites, adding dichloromethane (containing (v/v) pyridine) and 2-bromoisobutyryl bromide to carry out ATRP modification, simultaneously adding phenyl methacrylate and p-xylene (containing copper bromide and N, N, N' -pentamethyl divinyl triamine), and stirring under the protection of nitrogen. The high-temperature thermal response bentonite has strong temperature sensitivity, has high-temperature self-healing capacity, and enhances the high-temperature plugging property of mud cakes. The drilling fluid has the advantages of good self-repairing performance, stable rheology, excellent thermal response and excellent plugging property.
Description
Technical Field
The invention relates to high-temperature thermal response bentonite and a high-temperature thermal response bentonite drilling fluid, and belongs to the technical field of drilling.
Background
Bentonite is an important industrial raw material with economic and environmental protection, the main clay mineral component of the bentonite is montmorillonite, and the crystal structure of the bentonite is mainly composed of silicon-oxygen tetrahedron and aluminum-oxygen octahedron. The clay particles have large specific surface area, are rich in hydroxyl polar adsorption groups and have strong adsorbability on chemical treatment agents and water molecules. Therefore, in recent years, scholars at home and abroad take bentonite as a main raw material to be widely applied to film forming, and play roles in protection, seepage prevention and pollution prevention. The geomembrane is constructed by taking natural sodium bentonite as a main material by Heshichong, is used as an anti-seepage liner of the refuse landfill, has the advantages of low permeability coefficient, ageing resistance, self-healing property and the like, and effectively inhibits the percolation of pollutants in the refuse landfill. Bai et al prepared LMSH/NIPAM adsorption membranes from bentonite as a crosslinker, aluminum silicate complex (LMSH) and N-isopropylamide monomer (NIPAM), and effectively removed anionic pollutants from printing and dyeing materials. Particularly, in the process of drilling and production of petroleum and natural gas, bentonite is usually used as a main raw material to prepare drilling fluid on site, and a mud cake protective layer is constructed on the surface of a well hole by utilizing the stratum pressure difference, so that the well hole and surrounding rock strata are prevented from hydration collapse due to the loss of the drilling fluid in the well hole, and the well wall is stabilized.
However, as the well is drilled deeply, the conventional bentonite-based film forming technology cannot effectively prevent the leakage of drilling fluid under the influence of the high-temperature and high-pressure environment of the stratum, and the microcosmically shows that mud cake holes are enlarged, and filling and blocking polymers are degraded. Therefore, the thermal response polymer molecular brush is constructed on the clay surface, and when the stratum temperature is higher than the phase transition temperature of the polymer, the polymer molecular brush can be self-polymerized, so that the high-temperature blocking property of the mud cake is enhanced.
Disclosure of Invention
Aiming at the problem that the conventional bentonite-based film forming technology cannot effectively prevent the leakage of drilling fluid, the invention constructs the thermal response polymer molecular brush on the surface of the bentonite, and when the stratum temperature is higher than the phase transition temperature of the polymer, the polymer molecular brush can self-polymerize, thereby enhancing the high-temperature plugging property of the mud cake.
The present invention adopts the technical objects as described above and adopts the following technical solutions.
The invention provides high-temperature thermal response bentonite, which is based on an Atom Transfer Radical Polymerization (ATRP) method and is used for carrying out graft modification on a calibration activation site of the bentonite to construct a star-shaped bentonite-based response agent, wherein the core is rigid bentonite particles, and the outer part is a flexible high-temperature thermal response molecular brush, more specifically, the thermal response molecular brush is poly (benzyl methacrylate), the molecular weight Mn is 5000-60000, preferably 5000-25000.
The preparation method of the high-temperature thermal response bentonite comprises the following steps:
activating bentonite acid to construct an activation site.
Mixing 1-3 g of bentonite with 100mL of 10-15 wt% hydrochloric acid aqueous solution to dredge clay pore channels, constructing hydroxyl adsorption point positions and improving the adsorbability of the bentonite.
And step two, drying the bentonite.
Drying the bentonite at 120-150 ℃ for 10-24 h to remove hydrochloric acid and water in the bentonite.
And step three, ATRP modification.
Mixing activated bentonite with 0.5-1 mL (3-Aminopropyl) Trimethoxysilane (ATMS) and 10-40 mL of methanol, and magnetically stirring at 35-45 ℃ for 12-16 h to provide ATRP modified activated sites.
Then, 10-20 mL of dichloromethane (containing 3-5% (v/v) of pyridine) and 5-10 mL of 2-bromoisobutyryl bromide are added for ATRP modification. Adding 5-10 g of phenyl methacrylate and 5-10 mL of p-xylene (containing 0.5-1 g of copper bromide and 0.3-0.5 mL of N, N, N' -pentamethyl divinyl triamine) during ATRP modification, and stirring for 8-10 hours under the protection of nitrogen at 80-100 ℃ to complete ATRP modification.
And step four, rinsing and drying.
After modification, the bentonite was rinsed 3 more times with dichloromethane and ethanol. Then, drying under the protection of nitrogen to prepare the high-temperature thermal response bentonite.
The bentonite prepared by the method has the advantages that the thermal response polymer molecular brush is constructed on the surface of the bentonite, when the stratum temperature is higher than the phase transition temperature of the polymer, the polymer molecular brush can self-polymerize to enhance the high-temperature blocking property of the mud cake, and the principle is shown in figure 1. Specifically, the thermal response molecular brush is poly (benzyl methacrylate), and the molecular weight Mn is 5000-60000, preferably 5000-25000.
Based on excellent self-healing capability of the thermal response bentonite in a high-temperature environment, the thermal response bentonite is further applied to prepare a high-performance water-based drilling fluid, and particularly, the high-performance water-based drilling fluid is used for preparing a high-temperature thermal response bentonite drilling fluid containing the high-temperature thermal response bentonite.
The high-temperature thermal response bentonite drilling fluid comprises:
300mL of water;
8-12 g of high-temperature thermal response bentonite;
3-4.5 g of sodium chloride;
2-3 g of anionic carboxymethyl cellulose (Lv-PAC);
the zwitterionic polymer FA 3671-2 g;
10-15 g of superfine calcium carbonate powder (the particle size is 2000 meshes);
the weighting material (barite powder, 200 mesh) was adjusted to the desired density.
The preparation method of the high-temperature thermal response bentonite drilling fluid comprises the following steps:
first, a high temperature thermally responsive bentonite is pre-hydrated.
Mixing 8-12 g of high-temperature thermal response bentonite with 300mL of pure water, and stirring at 30-50 ℃ for 4-5 h to form soil slurry.
Then, 3-4.5 g of sodium chloride is added into the soil slurry, and the mixture is stirred for 7-9 hours at the temperature of 30-50 ℃ to enhance the hydration dispersion of the high-temperature thermal response bentonite.
Then, 2-3 g of anionic carboxymethyl cellulose (Lv-PAC) and 1-2 g of amphoteric ion polymer FA367 are added to be stirred for 7-10 hours in a microwave oscillation mode, and the stability and the suspensoid performance of the drilling fluid are enhanced.
Further adding 10-15 g of common inert plugging material superfine calcium carbonate powder (the particle size is 2000 meshes), and fully mixing and stirring for 12-16 h at the stirring speed of 500-700 r/min.
Finally, slowly adding a weighting material (barite powder, 200 meshes) into the prepared base liquid, and simultaneously adding strong mechanical stirring at the stirring speed of 500-800 r/min until the density of the drilling fluid reaches 2.1g/cm3Until now. Obtaining the high-temperature thermal response bentonite drilling fluid.
By adopting the technical scheme, the invention achieves the following technical effects.
1. The high-temperature thermal response bentonite has strong temperature sensitivity, and the polymer molecular brush plugging and packing performance is strong and stable.
2. The high-temperature thermal response bentonite provided by the invention has high-temperature self-healing capacity, and the high-temperature plugging property of mud cakes is enhanced.
3. The high-temperature thermal response bentonite drilling fluid disclosed by the invention is good in self-repairing performance, stable in rheology, and excellent in thermal response and plugging property.
Drawings
FIG. 1 is a high temperature plugging mechanism diagram of high temperature thermal response bentonite;
FIG. 2 is a graph of the effect of temperature on high temperature thermally responsive bentonite slurry percolation;
FIG. 3 is a graph showing the plugging property and shale hydration expansion change of high-temperature thermal response bentonite in a high-temperature environment;
FIG. 4 is a graph of the apparent viscosity change of a conventional bentonite drilling fluid and a high temperature thermally responsive bentonite drilling fluid at different temperatures;
figure 5 is a graph comparing the high temperature plugging performance of a conventional bentonite drilling fluid with a high temperature thermally responsive bentonite drilling fluid.
Detailed Description
The following further describes the technical solutions of the present invention with reference to specific embodiments, so that those skilled in the art can better understand the present invention and can implement the present invention.
Examples 1 to 4 are methods for preparing high temperature thermally responsive bentonite
Example 1
The preparation method of the high-temperature thermal response bentonite comprises the following steps:
activating bentonite acid to construct an activation site.
3g of bentonite is mixed with 100mL of 7 wt% hydrochloric acid aqueous solution to dredge clay pore channels, construct hydroxyl adsorption point positions and improve the adsorbability of the bentonite.
And step two, drying the bentonite.
Drying the bentonite at 120-150 ℃ for 10-24 h to remove hydrochloric acid and water in the bentonite.
And step three, ATRP modification.
Mixing activated bentonite with 0.5mL (3-Aminopropyl) Trimethoxysilane (ATMS) and 10mL of methanol, and magnetically stirring at 42 ℃ for 12-16 h to provide ATRP modified activated sites.
Then, 10mL of methylene chloride (containing 2% (v/v) pyridine) and 5mL of 2-bromoisobutyryl bromide were added to perform ATRP modification. During the ATRP modification, 5g of phenyl methacrylate and 5mL of p-xylene (containing 5mL of ketone bromide and 0.14mL of N, N, N' -pentamethyldivinyltriamine) were added and stirred at 90 ℃ for 6 hours under a nitrogen blanket to complete the ATRP modification.
And step four, rinsing and drying.
After polymerization, the bentonite was rinsed 3 more times with dichloromethane and ethanol. Then, drying under the protection of nitrogen to prepare the high-temperature thermal response bentonite. The core of the high-temperature thermal response molecular brush is rigid bentonite particles, and the exterior of the high-temperature thermal response molecular brush is a poly (benzyl methacrylate) flexible high-temperature thermal response molecular brush with the molecular weight Mn of 5000-10000.
Example 2
The preparation method of the high-temperature thermal response bentonite comprises the following steps:
activating bentonite acid to construct an activation site.
1g of bentonite is mixed with 100mL of 10 wt% hydrochloric acid aqueous solution to dredge clay pore channels, construct hydroxyl adsorption point positions and improve the adsorbability of the bentonite.
And step two, drying the bentonite.
Drying the bentonite at 120-150 ℃ for 10-24 h to remove hydrochloric acid and water in the bentonite.
And step three, ATRP modification.
Activated bentonite was miscible with 0.5mL (3-Aminopropyl) Trimethoxysilane (ATMS) and 10mL methanol and magnetically stirred at 35 ℃ for 12h to provide ATRP modified activation sites.
Then, 10mL of dichloromethane (containing 3% (v/v) pyridine) and 5mL of 2-bromoisobutyryl bromide were added to perform ATRP modification. During the ATRP modification, 5g of phenyl methacrylate and 5-10 mL of p-xylene (containing 0.5g of copper bromide and 0.3mL of N, N, N' -pentamethyldivinyltriamine) are added, and the ATRP modification is completed under the protection of nitrogen and stirring for 8 hours at the temperature of 80 ℃.
And step four, rinsing and drying.
After modification, the bentonite was rinsed 3 more times with dichloromethane and ethanol. Then, drying under the protection of nitrogen to prepare the high-temperature thermal response bentonite. The core of the high-temperature thermal response molecular brush is rigid bentonite particles, and the outside of the high-temperature thermal response molecular brush is a poly (benzyl methacrylate) flexible high-temperature thermal response molecular brush with the molecular weight Mn of 10000-15000.
Example 3
The preparation method of the high-temperature thermal response bentonite comprises the following steps:
activating bentonite acid to construct an activation site.
3g of bentonite is mixed with 100mL of 15wt% hydrochloric acid aqueous solution to dredge clay pore channels, construct hydroxyl adsorption point positions and improve the adsorbability of the bentonite.
And step two, drying the bentonite.
Drying the bentonite at 120-150 ℃ for 10-24 h to remove hydrochloric acid and water in the bentonite.
And step three, ATRP modification.
Activated bentonite was miscible with 1mL (3-Aminopropyl) Trimethoxysilane (ATMS) and 40mL of methanol and magnetically stirred at 45 ℃ for 16h to provide ATRP modified activation sites.
Then, 20mL of methylene chloride (containing 5% (v/v) pyridine) and 10mL of 2-bromoisobutyryl bromide were added to perform ATRP modification. During the ATRP modification, 10g of phenyl methacrylate and 10mL of p-xylene (containing 1g of copper bromide and 0.5mL of N, N, N' -pentamethyldivinyltriamine) were added and stirred at 90 ℃ for 10 hours under nitrogen protection to complete the ATRP modification.
And step four, rinsing and drying.
After modification, the bentonite was rinsed 3 more times with dichloromethane and ethanol. Then, drying under the protection of nitrogen to prepare the high-temperature thermal response bentonite. The core of the high-temperature-response molecular brush is rigid bentonite particles, and the exterior of the high-temperature-response molecular brush is a poly (benzyl methacrylate) flexible high-temperature-response molecular brush with the molecular weight Mn of 20000-25000.
Example 4
The preparation method of the high-temperature thermal response bentonite comprises the following steps:
activating bentonite acid to construct an activation site.
2g of bentonite is mixed with 100mL of 12 wt% hydrochloric acid aqueous solution to dredge clay pore channels, construct hydroxyl adsorption point positions and improve the adsorbability of the bentonite.
And step two, drying the bentonite.
Drying the bentonite at 120-150 ℃ for 10-24 h to remove hydrochloric acid and water in the bentonite.
And step three, ATRP modification.
Activated bentonite was miscible with 0.7mL (3-Aminopropyl) Trimethoxysilane (ATMS) and 25mL of methanol and magnetically stirred at 40 ℃ for 14h to provide ATRP modified activation sites.
Then, 15mL of dichloromethane (containing 4% (v/v) pyridine) and 7mL of 2-bromoisobutyryl bromide were added to perform ATRP modification. During the ATRP modification, a mixture containing 7g of phenyl methacrylate and 8mL of p-xylene (containing 0.7g of copper bromide and 0.4mL of N, N, N' -pentamethyldivinyltriamine) was added and stirred at 100 ℃ for 9 hours under a nitrogen blanket to complete the ATRP modification.
And step four, rinsing and drying.
After modification, the bentonite was rinsed 3 more times with dichloromethane and ethanol. Then, drying under the protection of nitrogen to prepare the high-temperature thermal response bentonite. The core of the high-temperature-response molecular brush is rigid bentonite particles, and the outside of the high-temperature-response molecular brush is a poly (benzyl methacrylate) flexible high-temperature-response molecular brush with the molecular weight Mn of 15000-20000.
Examples 5 to 8 are formulations of high temperature thermally responsive bentonite drilling fluids
Example 5
A high-temperature thermal response bentonite drilling fluid is prepared by the following steps:
the method comprises the steps of prehydrating high-temperature thermal response bentonite, mixing 12g of the high-temperature thermal response bentonite with 300mL of pure water, and stirring for 4-5 hours at 30-50 ℃ to form soil slurry.
And then, adding 4.5g of sodium chloride particles into the soil slurry, and stirring for 7-9 h at the temperature of 30-50 ℃ to enhance the hydration dispersion of the high-temperature thermal response bentonite.
Then, 3g of anionic carboxymethyl cellulose (Lv-PAC) and 1.5g of amphoteric ion polymer FA367 are added to be stirred for 7-10 hours in a microwave oscillation mode, and the stability and the suspensoid performance of the drilling fluid are enhanced. Further adding 10g of common inert plugging material superfine calcium carbonate powder (the particle size is 2000 meshes), fully mixing and stirring for 12-16 h at the stirring speed of 500-700 r/min.
Finally, adding a weighting material (barite powder, 200 meshes) into the prepared base fluid gradually, and simultaneously adding strong mechanical stirring at the stirring speed of 500-800 r/min until the density of the drilling fluid reaches 2.1g/cm3Until now. Obtaining the high-temperature thermal response bentonite drilling fluid.
Example 6
A high-temperature thermal response bentonite drilling fluid is prepared by the following steps:
firstly, prehydrating high-temperature thermal response bentonite, mixing 8g of the high-temperature thermal response bentonite with 300mL of pure water, and stirring for 4-5 h at 30-50 ℃ to form soil slurry.
And then, adding 3g of sodium chloride into the soil slurry, and stirring for 7-9 h at the temperature of 30-50 ℃ to enhance the hydration dispersion of the high-temperature thermal response bentonite.
Then, 2g of anionic carboxymethyl cellulose (Lv-PAC) and 1g of zwitterionic polymer FA367 are added to be stirred for 7-10 hours in a microwave oscillation mode, so that the stability and the suspensoid performance of the drilling fluid are enhanced.
Further adding 10g of common inert plugging material superfine calcium carbonate powder (the particle size is 2000 meshes), fully mixing and stirring for 12-16 h at the stirring speed of 500-700 r/min.
Finally, slowly adding a weighting material (barite powder, 200 meshes) into the prepared base liquid, and simultaneously adding strong mechanical stirring at the stirring speed of 500-800 r/min until the density of the drilling fluid reaches 2.1g/cm3Until now. Obtaining the high-temperature thermal response bentonite drilling fluid.
Example 7
A high-temperature thermal response bentonite drilling fluid is prepared by the following steps:
first, a high temperature thermally responsive bentonite is pre-hydrated.
Mixing 12g of high-temperature thermal response bentonite with 300mL of pure water, and stirring for 4-5 h at 30-50 ℃ to form soil slurry.
And then, adding 4.5g of sodium chloride into the soil slurry, and stirring for 7-9 hours at the temperature of 30-50 ℃ to enhance the hydration dispersion of the high-temperature thermal response bentonite.
Then, 3g of anionic carboxymethyl cellulose (Lv-PAC) and 2g of amphoteric ion polymer FA367 are added to be stirred for 7-10 hours in a microwave oscillation mode, so that the stability and the suspensoid performance of the drilling fluid are enhanced.
Further adding 5g of common inert plugging material superfine calcium carbonate powder (the particle size is 2000 meshes), fully mixing and stirring for 12-16 h at the stirring speed of 500-700 r/min.
Finally, slowly adding a weighting material (barite powder, 200 meshes) into the prepared base liquid, and simultaneously adding strong mechanical stirring at the stirring speed of 500-800 r/min until the density of the drilling fluid reaches 2.1g/cm3Until now. Obtaining the high-temperature thermal response bentonite drilling fluid.
Example 8
A high-temperature thermal response bentonite drilling fluid is prepared by the following steps:
first, a high temperature thermally responsive bentonite is pre-hydrated.
Mixing 10g of high-temperature thermal response bentonite with 300mL of pure water, and stirring for 4-5 h at 30-50 ℃ to form soil slurry.
And then, adding 4g of sodium chloride into the soil slurry, and stirring for 7-9 h at the temperature of 30-50 ℃ to enhance the hydration dispersion of the high-temperature thermal response bentonite.
Then, 2.5g of anionic carboxymethyl cellulose (Lv-PAC) and 1.5g of amphoteric ion polymer FA367 are added to be stirred for 7-10 hours in a microwave oscillation mode, so that the stability and the suspensoid performance of the drilling fluid are enhanced.
Further adding 12g of common inert plugging material superfine calcium carbonate powder (the particle size is 2000 meshes), fully mixing and stirring for 12-16 h at the stirring speed of 500-700 r/min.
Finally, slowly adding a weighting material (barite powder, 200 meshes) into the prepared base liquid, and simultaneously adding strong mechanical stirring at the stirring speed of 500-800 r/min until the density of the drilling fluid reaches 2.1g/cm3Until now. Obtaining the high-temperature thermal response bentonite drilling fluid.
Comparative example 1
Firstly, prehydrating common bentonite, mixing 12g of the common bentonite with 300mL of pure water, and stirring for 4-5 h at 30-50 ℃ to form soil slurry.
And then, adding 4.5g of sodium chloride particles into the soil slurry, and stirring for 7-9 h at 30-50 ℃ to enhance the hydration dispersion of the common bentonite.
Then, 3g of anionic carboxymethyl cellulose (Lv-PAC) and 1.5g of amphoteric ion polymer FA367 are added to be stirred for 7-10 hours in a microwave oscillation mode, and the stability and the suspensoid performance of the drilling fluid are enhanced.
And further adding 9g of common inert plugging material superfine calcium carbonate powder (the particle size is 2000 meshes), and fully mixing and stirring for 12-16 h at the stirring speed of 500-700 r/min.
Finally, adding a weighting material (barite powder, 200 meshes) into the prepared base fluid gradually, and simultaneously adding strong mechanical stirring at the stirring speed of 500-800 r/min until the density of the drilling fluid reaches 2.1g/cm3Until now. Obtaining the common bentonite drilling fluid.
The starting materials for the examples and comparative examples were from: sodium bentonite purchased from Nan deg.C or company, mud cake film-forming main raw material with particle size of 200 mesh, Cation Exchange Capacity (CEC) of 145meq/100g, mineral component of 13.22% Al2O3，71.30％SiO2，7.10％MgO，4.79％Na2O and 3.59% Fe2O3(ii) a Hydrochloric acid, (3-Aminopropyl) Trimethoxysilane (ATMS) and methanol activated bentonite, both chemically pure and purchased from shanghai aladine reagents; methylene dichloride and 2-bromoisobutyryl bromide are used for modifying bentonite surface Atom Transfer Radical Polymerization (ATRP), and both are chemically pure and purchased from Shanghai Allantin reagent company. Phenyl methacrylate, p-xylene (p-xylene), ketone bromide (CuBr) and N, N, N' -pentamethyl divinyl triamine (PMDETA) are all chemically pure, are used for temperature-sensitive modification of bentonite and are all purchased from Shanghai avastin reagents; anionic carboxymethyl cellulose (Lv-PAC), zwitterionic polymer (FA367), superfine calcium carbonate powder and barite powder for preparing drilling fluid are purchased from Chengdu Kelong chemical reagent factories.
Examples of the experiments
Experimental example 1 high-temperature high-pressure percolation experiment
In order to simulate the high-temperature and high-pressure environment of the stratum, a high-temperature and high-pressure filtration loss tester is adopted to test the influence of the high-temperature thermal response bentonite on the water seepage in the kettle body under different high-temperature environments (120 ℃, 140 ℃, 150 ℃, 160 ℃ and 170 ℃). 12g of the thermal response bentonite in the embodiment 1 is mixed with 300mL of deionized water, and mechanically stirred for 30min at a speed of 400-600 r/min to prepare high-temperature thermal response bentonite slurry (referred to as soil slurry for short). Then, the prepared soil slurry is poured into a high-temperature high-pressure dehydration instrument, and 3.5MPa of nitrogen is injected and pressed, and meanwhile, the experimental infiltration temperature is designed. And when the temperature in the kettle reaches the experimental temperature, opening a seepage channel valve, and recording the filtration loss of the fluid in the kettle in different time so as to calculate the seepage velocity of the soil slurry, wherein the calculation is shown in the following formula.
vHTHPThe average percolation speed in t time under the high-temperature and high-pressure environment of the soil slurry is cm3/min；
QHTHPThe percolation volume of the soil slurry in the high-temperature and high-pressure environment within t time is cm3；
t is the diafiltration time, min.
The change in percolation rate of a high temperature thermally responsive bentonite-based slurry is shown in figure 2, which illustrates the effect of temperature on the percolation of a high temperature thermally responsive bentonite slurry. As can be seen from the figure, the experimental temperature (120 ℃) did not reach the modified bentonite response temperature, the instantaneous percolation rate of the slurry (average percolation rate within 1 min) was greater than 6mL/min, and the API percolation rate (average percolation rate within 30 min) was greater than 3 mL/min. However, at the experimental temperature of 140 ℃, the instantaneous percolation rate of the slurry was significantly reduced to 2.1mL/min and the API percolation rate was also significantly reduced to 1.2mL/min, indicating that the temperature reached the phase transition temperature of the polymer molecular brush, beginning to pack and block the mudcake pores. As the temperature increased, the slurry percolation rate further decreased, indicating the self-healing behavior of the modified bentonite. When the temperature reaches 160 ℃, the percolation speed of the soil slurry tends to be a straight line along the time variation rule, and the instantaneous percolation speed of the soil slurry is close to the API percolation speed, which shows that the modified bentonite has strong temperature sensitivity and the polymer molecular brush plugging and packing performance is strong and stable.
Experimental example 2 high-temperature high-pressure shale linear expansion experiment
Currently, borehole wall instability often occurs in water-sensitive shale formations. Therefore, the water-sensitive shale of the Longmaxi group is taken as a research object, and the blocking performance of the high-temperature thermal response bentonite in a high-temperature environment and the influence of the high-temperature thermal response bentonite on the hydration of the shale are further tested. The shale used in the experiment was taken from the stratums of the Longmaxi group, Yibin, Sichuan province. First, a part of shale is chiseled and crushed to powder (particle size of 200 mesh) using a solid crusher. Then, 5g of shale powder is placed in a core pressing device, and an experimental core is prepared by pressing for 10min, wherein the experimental pressure is 10 MPa. Then, the experimental core was placed in a core cup of a high-temperature high-pressure dilatometer (purchased from Qingdao Tongchun petroleum instruments and factories), 10mL of slurry of experimental example 1 was injected, the change of the linear expansion rate of the core in 16 hours at different temperatures (experimental pressure of 3.5MPa) was recorded, and the calculation formula of the linear expansion rate was shown as the following formula.
ω＝(Rt-R0)/H×100％
Omega is the linear expansion rate of the core,%;
Rtthe height reading of the core t time is mm;
Rothe initial height reading of the core is mm;
h is the initial length of the core, mm.
The experimental results are shown in fig. 3, and it can be seen that the linear expansion rate of shale decreases with the increase of temperature. When the temperature is 140 ℃, the linear expansion rate of the shale is obviously reduced, the expansion amplitude is obviously reduced within 16 hours, the shale is consistent with the result of a soil slurry percolation experiment, and the high-temperature healing capacity of the polymer molecular brush of the thermal response bentonite is reflected. When the test temperature is higher than 150 ℃, the test result shows that the plugging property of the mud cake tends to be stable, the shale expansion rate is small, and the variation amplitude is small. This is because the high temperature self-healing ability of the thermally responsive bentonite enhances the high temperature plugging properties of the mud cake.
Experimental example 3 drilling fluid Performance test
Drilling fluid performance test, the high-temperature thermal response bentonite drilling fluid of example 5 and the ordinary bentonite drilling fluid of comparative example 1 are placed in an aging tank for hot rolling aging, then the rheological change of the drilling fluid is measured by a rotary viscometer, and the test result is shown in fig. 4. Fig. 4 reflects viscosity change curves of two types of drilling fluids along with temperature change, wherein SSDWX represents a high-temperature thermal response bentonite drilling fluid, DWX represents a common bentonite drilling fluid, and it can be seen from the figure that the conventional bentonite-based drilling fluid gradually decreases in viscosity along with temperature increase and is unstable in rheological properties of the drilling fluid. Although the viscosity of the high-temperature thermal response bentonite drilling fluid is reduced along with the temperature rise, the viscosity of the drilling fluid is gradually increased after the temperature is higher than 120 ℃, the self-repairing performance is shown, and the drilling fluid is stable in rheology.
Then, the high temperature thermal response bentonite drilling fluid of example 5 and the ordinary bentonite drilling fluid of comparative example 1 were placed in a 150 ℃ high temperature and high pressure dilatometer and a 150 ℃ high temperature and high pressure percolator, respectively, and the high temperature plugging property of the drilling fluid was measured, and the experimental results are shown in fig. 5. In the figure, SSDWX represents a high-temperature thermal response bentonite drilling fluid, DWX represents a common bentonite drilling fluid, and fig. 5 shows that, under a high-temperature environment (150 ℃), the plugging property of the high-temperature thermal response bentonite drilling fluid is obviously better than that of the bentonite drilling fluid, the linear expansion rate of shale is reduced from 6.3% to 2.3%, and the API filtrate loss is reduced from 7.2mL to 1.4 mL. The experimental result verifies the thermal responsiveness of the high-temperature thermal response bentonite drilling fluid.
The technical solution provided by the present invention is not limited by the above embodiments, and all technical solutions formed by utilizing the structure and the mode of the present invention through conversion and substitution are within the protection scope of the present invention.
Claims (6)
1. A high-temperature thermal response bentonite is characterized in that: the core of the high-temperature thermal response bentonite is rigid bentonite particles, the outer part of the high-temperature thermal response bentonite particles is a flexible high-temperature thermal response molecular brush, and the flexible high-temperature thermal response molecular brush is poly (benzyl methacrylate);
the high-temperature thermal response bentonite is prepared by the following method:
step one, activating the bentonite acid to construct an activation site
Mixing bentonite with hydrochloric acid aqueous solution, dredging clay pore channels, constructing hydroxyl adsorption point positions, and improving the adsorbability of the bentonite;
step two, drying treatment
Drying the bentonite in the first step to remove hydrochloric acid and moisture in the bentonite;
step three, ATRP modification
Mixing activated bentonite with 0.5-1 mL (3-aminopropyl) trimethoxy silicon (ATMS) and 10-40 mL methanol, and stirring by a magnetic stirrer at 35-45 ℃ for 12-16 h to provide ATRP modified activated sites;
then, adding 10-20 mL of dichloromethane (containing 3-5% (v/v) of pyridine) and 5-10 mL of 2-bromoisobutyryl bromide to perform ATRP modification, adding 5-1L of 0g phenyl methacrylate and 5-10 mL of p-xylene (containing 0.5-1 g of copper bromide and 0.3-0.5 mL of N, N, N' -pentamethyl divinyl triamine) during ATRP modification, and stirring for 8-10 hours under the protection of nitrogen at 80-100 ℃ to complete ATRP modification;
step four, rinsing and drying
After modification, rinsing and drying to prepare high-temperature thermal response bentonite;
wherein the molecular weight Mn of the thermal response polymer molecular brush is 5000-6000.
2. The high temperature thermally responsive bentonite according to claim 1, wherein: the molecular weight Mn of the thermal response polymer molecular brush is 5000-25000.
3. The high temperature thermally responsive bentonite according to claim 1, wherein: the high-temperature thermal response bentonite is prepared by the following method:
step one, activating bentonite acid to construct an activation site
Mixing 1-3 g of bentonite with 100mL of 10-15 wt% hydrochloric acid aqueous solution, dredging clay pore channels, constructing hydroxyl adsorption point positions, and improving the adsorbability of the bentonite;
step two, drying treatment
Drying the bentonite obtained in the first step at 120-150 ℃ for 10-24 hours to remove hydrochloric acid and water in the bentonite;
step three, ATRP modification
Mixing activated bentonite with 0.5-1 mL (3-Aminopropyl) Trimethoxysilane (ATMS) and 10-40 mL of methanol, and magnetically stirring at 35-45 ℃ for 12-16 h to provide ATRP modified activated sites;
then, adding 10-20 mL of dichloromethane (containing 3-5% (v/v) pyridine) and 5-10 mL of 2-bromoisobutyryl bromide to perform ATRP modification, adding 5-10 g of phenyl methacrylate and 5-10 mL of p-xylene (containing 0.5-1 g of copper bromide and 0.3-0.5 mL of N, N, N' -pentamethyl divinyl triamine) during ATRP modification, and stirring for 8-10 hours under the protection of nitrogen at 80-100 ℃ to complete ATRP modification;
step four, rinsing and drying
After modification, the bentonite is rinsed for more than 3 times by using dichloromethane and ethanol, and then the bentonite is dried under the protection of nitrogen to prepare the high-temperature thermal response bentonite.
4. Use of a high temperature thermally responsive bentonite as claimed in any of claims 1 to 3 in drilling fluids, wherein: for the preparation of a high temperature thermally responsive bentonite drilling fluid comprising a high temperature thermally responsive bentonite according to any of claims 1 to 3.
5. The use of a high temperature thermally responsive bentonite as claimed in claim 4 in drilling fluids, wherein: the high-temperature thermal response bentonite drilling fluid comprises the following components in percentage by weight,
8-12 g of high-temperature thermal response bentonite;
3-4.5 g of sodium chloride;
2-3 g of anionic carboxymethyl cellulose (Lv-PAC);
the zwitterionic polymer FA 3671-2 g;
10-15 g of superfine calcium carbonate powder (the particle size is 2000 meshes);
300mL of water;
the weighting material (barite powder, 200 mesh) was adjusted to the desired density.
6. A high temperature thermally responsive bentonite drilling fluid comprising the high temperature thermally responsive bentonite of any one of claims 1 to 3, wherein: the high-temperature thermal response bentonite drilling fluid comprises the following components in proportion
8-l 2g of high-temperature thermal response bentonite;
3-4.5 g of sodium chloride;
2-3 g of anionic carboxymethyl cellulose (Lv-PAC);
the zwitterionic polymer FA 3671-2 g;
10-15 g of superfine calcium carbonate powder (the particle size is 2000 meshes);
300mL of water;
the weighting material (barite powder, 200 mesh) was adjusted to the desired density.
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