CN109516704B - Thermotropic unfolding device and preparation method - Google Patents
Thermotropic unfolding device and preparation method Download PDFInfo
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- CN109516704B CN109516704B CN201710836656.0A CN201710836656A CN109516704B CN 109516704 B CN109516704 B CN 109516704B CN 201710836656 A CN201710836656 A CN 201710836656A CN 109516704 B CN109516704 B CN 109516704B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1018—Coating or impregnating with organic materials
- C04B20/1029—Macromolecular compounds
- C04B20/1033—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/34—Metals, e.g. ferro-silicon
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/38—Fibrous materials; Whiskers
- C04B14/386—Carbon
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B16/04—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1018—Coating or impregnating with organic materials
- C04B20/1029—Macromolecular compounds
- C04B20/1037—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention discloses a thermotropic unfolding device and a preparation method thereof. The thermally-induced unfolding device is a shape memory particle; the shape memory particles comprise a flexible sheet and a temperature-sensitive shape memory polymer coated by the flexible sheet; the content of the temperature-sensitive shape memory polymer is 20-99.99 wt% of the shape memory particles; the shape memory particles have a particle size of less than or equal to 8 mm. The preparation method comprises the following steps: crushing and heating the temperature-sensitive shape memory polymer to melt, uniformly coating the temperature-sensitive shape memory polymer hot melt liquid on a flexible sheet, rolling the sheet into a roll, and cooling the roll to room temperature for cutting and granulation. The thermally-induced expansion device is added into well cementation cement slurry, is excited by a suitable underground temperature rise environment to expand by multiple times of surface area, and achieves the purpose of blocking rock cracks by utilizing the steric effect in fluid.
Description
Technical Field
The invention relates to the technical field of well cementation, in particular to a thermally-induced expansion device and a preparation method thereof.
Background
The well leakage is one of the common underground complex conditions in the process of well drilling and well cementation. The lost circulation not only consumes the drilling time and loses drilling fluid and cement paste, but also can cause the problems of drill sticking, blowout, well collapse, poor well cementation quality and the like, and even causes the abandonment accident of the well hole, thereby causing great economic loss.
Solving the problem of leakage of oil and gas wells has been the subject of concern in various large oil and gas fields. The conventional well cementation cement paste has no leakage blocking function, but after the inert fiber material is added, a net-shaped structure is easily formed in a leakage passage due to the accumulation and bridging action of the fibers, and the conventional performance of the cement paste is not changed greatly, so that the leakage in the well drilling and well cementation processes can be blocked to a certain degree. And moreover, the addition of the fibers can also improve the toughness of the set cement and ensure that the later perforating operation is better carried out.
The fiber is used as an inert material and is commonly used for preparing fiber cement slurry for well cementation operation. The fiber cement paste is prepared by mixing fiber materials with a certain proportion and length in a cement paste basic formula, the performance of the mixed cement paste is not greatly changed compared with that of primary pulp, and fibers are easy to form a net-shaped structure in a leakage channel through accumulation and bridging. Therefore, the fiber cement slurry can also be used for the lost circulation plugging operation. At present, a fiber plugging cement paste system is mainly formed by changing the addition amount (<5 per thousand, the amount of cement) and the length (1-6mm) of fiber. Such systems typically rely on the operator to add the fibers to the cement truck. It should be noted here that the fibers cannot be dry blended in the cement because of their mass entanglement. Meanwhile, the speed of manually scattering fibers on a cement truck is slow, and the rheological property of cement paste is influenced by excessive addition of the fibers, so that the addition amount is less than 5 per thousand (accounting for the amount of the cement). In addition, the length of the fiber cannot be too long, so that the leakage stoppage effect of the fiber leakage stoppage slurry is limited.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a thermally-induced unfolding device and a preparation method thereof. The thermally-induced expansion device is added into well cementation cement slurry, is excited by a suitable underground temperature rise environment to expand by multiple times of surface area, and achieves the purpose of blocking rock cracks by utilizing the steric effect in fluid.
It is an object of the present invention to provide a thermally-induced deployment device.
The thermally-induced unfolding device is a shape memory particle;
the shape memory particles comprise a flexible sheet and a temperature-sensitive shape memory polymer coated by the flexible sheet;
the content of the temperature-sensitive shape memory polymer is 20-99.99 wt% of the shape memory particles; preferably 30 to 70 wt%; more preferably 40-60 wt%;
the particle size of the shape memory particles is less than or equal to 8mm, preferably greater than or equal to 0.5mm and less than or equal to 5.0 mm; more preferably 0.5mm or more and 3.0mm or less.
The flexible sheet is an organic sheet or a metal sheet; preferably at least one of polypropylene, polyethylene, EVA, iron, copper, stainless steel, aluminum, alloy and carbon fiber sheet;
the deformation temperature range of the temperature-sensitive shape memory polymer is 55-95 ℃, and preferably 60-80 ℃;
the temperature-sensitive shape memory polymer is preferably at least one of styrene-butadiene copolymer, styrene-butyl acrylate copolymer, polyurethane, polyvinyl acetal gel and ethylene-vinyl acetate copolymer.
The second purpose of the invention is to provide a method for preparing a thermally-induced unfolding device.
The method comprises the following steps:
crushing and heating the temperature-sensitive shape memory polymer to melt, uniformly coating the temperature-sensitive shape memory polymer hot melt liquid on a flexible sheet, cooling to room temperature, rolling to prepare a roll, and cutting and granulating.
Among them, it is preferable that,
granulating at a temperature higher than or equal to the lowest value of the deformation temperature of the temperature-sensitive shape memory polymer. More preferably: and granulating at a temperature which is higher than or equal to the maximum deformation temperature of the temperature-sensitive shape memory polymer by 5 ℃ and lower than or equal to the maximum deformation temperature of the temperature-sensitive shape memory polymer by 15 ℃.
At present, in the well cementation process, no good method is available for leak prevention and leak stoppage of oil well cement slurry, and only the fibers are added when the potential leakage risk exists, but the traditional fibers have the defects. Therefore, the shape memory particles are used for forming leakage-proof plugging, particularly used for forming a leakage-proof plugging oil well cement paste system and drilling fluid plugging, and can effectively solve the defects in the prior art. For example, in the present invention, by adding shape memory particles to the plugging slurry, the shape memory particles are granular and generally have small particle size, so that the shape memory particles are easy to mix uniformly and do not agglomerate in the plugging slurry. Meanwhile, the temperature is low and does not reach the deformation temperature of the temperature-sensitive shape memory polymer at the initial stage of injecting into the shaft, so that the viscous expansion structure can not be released. When the plugging slurry enters the well, the temperature of the stratum gradually rises, and when the deformation temperature of the shape memory particles is reached, the adhesion effect is weakened, the original particles are changed into a shape-recovered tough sheet large expansion structure, and the shape-recovered tough sheets are uniformly dispersed into the plugging slurry under the action of flowing shear. And during preparation, the hollow high-elasticity foam sponge structure is cut into different lengths in the co-extrusion molding and shearing granulation processes, so that the lengths of the tough sheet structures released to the bottom of the well are different, and the hollow high-elasticity foam sponge structure is beneficial to the formation of bridging at a missing part and the formation of bridging, and plays a role in leakage prevention and stoppage. Therefore, the invention not only solves the problem that the traditional fiber is easy to agglomerate when being added, but also the shape memory particles can be directly added into the leaking stoppage slurry, thereby avoiding the operation procedure that the difficulty of adding the fiber while injecting is higher in the process of using the fiber, simultaneously avoiding the problem that the leakage prevention and/or leaking stoppage effect cannot be fully shown due to too small adding amount, and the distribution of the shape memory particles in the leaking stoppage liquid is more uniform, thereby effectively preventing the leakage and/or leaking stoppage.
The temperature range of the temperature-sensitive shape memory polymer is 55-95 ℃; the temperature range of the temperature-sensitive shape memory polymer is particularly preferably 60-80 ℃. The shape memory particles for oil well cement based on the temperature-sensitive shape memory polymer can be used in oil well cement paste, and the cement paste prepared by using the shape memory particles has good rheological property and is easy for well cementation construction. Meanwhile, the oil well cement slurry using the shape memory particles has the effects of leakage prevention and leakage stoppage. In addition, by using the shape memory particles, the toughness of the set cement can be effectively increased, and the cement also has higher impact resistance.
The temperature-sensitive shape memory polymer is preferably at least one of styrene-butadiene copolymer, styrene-butyl acrylate copolymer, polyurethane, polyvinyl acetal gel and ethylene-vinyl acetate copolymer.
In choosing to use shape memory particles, the following are considered: (1) the use effect is that the particles are used too much, so that the particles are accumulated after being pumped underground, and are easy to block; (2) the cement paste is finally solidified into the cement stone, the addition of the organic admixture can improve the performances of the cement stone such as elastic modulus, strength, fracture resistance and the like, and the structure of the cement stone can be influenced if the dosage is too much; (3) for economic reasons, the more shape memory particles, in particular shape memory polymers, are used, the higher the cost. Therefore, the above three aspects need to be considered together. Thus, in one particular embodiment, the amount of shape memory particles is 0.5-8 mass% based on the mass of the solid component in the lost circulation slurry; preferably 1 to 5% by mass, particularly preferably 2 to 3% by mass. The plugging slurry generally contains a liquid component and a solid component, and the solid component in the plugging slurry is calculated according to the mass of the solid component in the plugging slurry, for example, when the plugging slurry is cement slurry, the cement slurry is composed of a liquid component, water and a solid component, namely cement, and then the solid component in the plugging slurry is cement according to the mass of the cement. In addition, it should be noted that the amount of the shape memory particles is related to the size of the pores and/or gaps to be sealed, and when the pores and/or gaps are larger, the amount of the shape memory particles is required to be higher; the amount of shape memory particles needed is lower when the pores and/or gaps are smaller.
The shape memory particles further include at least one of a flexible sheet, preferably an organic sheet (e.g., polypropylene, polyethylene, EVA, etc.), a metal sheet (e.g., iron, copper, stainless steel, aluminum, alloys, etc.), and other sheets such as carbon fiber, but not limited thereto.
The content of the shape memory polymer is 20-99.99 wt% based on 100 wt% of the shape memory particles; preferably 30 to 70 wt%; particularly preferably 40 to 60 wt%.
In the present invention, the size of the shape memory particles is not generally sufficient to limit the invention. However, since the particles are too large and are not easily mixed in the plugging slurry, it is necessary to select particles having a small particle size, but if the particles are too small, the shape memory property cannot be exhibited. Thus, in a particular embodiment, the shape memory particles have a particle size of less than or equal to 8mm, preferably greater than or equal to 0.5mm, and less than or equal to 5.0 mm; more preferably 0.5mm or more and 3.0mm or less.
Granulating the shape memory polymer or the composition comprising the shape memory polymer to obtain the shape memory particles; the composition preferably further comprises a flexible sheet, preferably at least one of an organic sheet (such as polypropylene, polyethylene, EVA, etc.), a metal sheet (such as iron, copper, stainless steel, aluminum, alloy, etc.), and other sheets such as carbon fiber, but not limited thereto. The required expandable memory particles are obtained by processing, thereby finally solving the application problem.
Granulating under the condition that the shape memory polymer is deformed; preferably, when the shape memory polymer comprises a temperature-sensitive shape memory polymer, granulating at a temperature higher than or equal to the lowest value of the deformation temperature of the temperature-sensitive shape memory polymer; particularly preferably, when the shape memory polymer comprises a temperature-sensitive shape memory polymer, the granulation is performed at a temperature higher than or equal to 5 ℃ at the maximum value of the deformation temperature of the temperature-sensitive shape memory polymer and lower than or equal to 15 ℃ at the maximum value of the deformation temperature of the temperature-sensitive shape memory polymer. It should be noted that, generally, the deformation temperature of the temperature-sensitive shape memory polymer generally has a certain temperature range, and therefore, the two endpoints in the deformation temperature range are the lowest value of the deformation temperature and the highest value of the deformation temperature, respectively. In the present invention, the temperature range of the granulation may be within the range of the deformation temperature or below the maximum value of the deformation temperature of 15 ℃.
The thermotropic unfolding device can be unfolded from a curled state to be in a kelp shape under the temperature control condition, so that the apparent area is increased, and the fluid resistance is increased. The cement slurry is mixed into well cementing cement, the existing well cementing process can be implemented, and the cement slurry is conveyed to a proper position in the well; when the temperature control condition is reached, the function is triggered and the device is unfolded. And the fluid resistance effect is applied to prevent the loss of cement paste and realize the efficient plugging of rock cracks.
The composition of the well cementation cement slurry is improved. Some of which are replaced by an intelligent thermally-induced deployment device. The device consists of two parts, namely a flexible sheet (1) and a shape memory resin (2) coating layer.
The thermally induced unfolding fold device of the present invention has two states: a rolled state and an unrolled state. The cement paste is mixed into well cementing cement in a coiled state, and can be conveniently conveyed to a proper position in a well along with cement slurry. Along with the gradual rise of the underground temperature, when the temperature control condition is reached, the shape memory function is triggered, and the device is unfolded. The apparent volume can be increased. And by applying the fluid resistance effect, the loss of cement paste from the rock gap is prevented, and the efficient plugging of the rock gap is realized.
Finally, the invention provides the use of a thermally-induced deployment device as described above in the field of oil well drilling.
When the device is in a ground curling state, the surface area can be controlled to be 6mm2(ii) a After the underground temperature is triggered, the volume can be increased by more than 20 times, a fluid resistance effect is generated, and a good plugging effect is achieved. Earlier stage scientific research verifies that the principle is feasible, has good shutoff effect.
Drawings
FIG. 1 is a schematic representation of a thermally-induced deployment device of the present invention in a deployed state;
FIG. 2 is a cross-sectional view of FIG. 1
FIG. 3 is a schematic diagram of the thermally-induced deployment device of the present invention in a crimped state;
FIG. 4 is a cross-sectional view of FIG. 3;
description of reference numerals:
1 is a flexible sheet, 2 a shape memory polymer.
Detailed Description
The present invention will be further described with reference to the following examples.
Comparative example 1
Blank grout and set preparation
500g of oil well cement and 220g of water are weighed. The water was placed in a mixing vessel and the mixer was rotated at low speed (4000. + -. 200 rpm) and the weighed cement was added over 15 seconds, the mixer lid was closed and mixing continued at high speed (12000. + -. 500 rpm) for 35 seconds to produce a blank slurry.
And pouring the blank cement paste into a curing module with the thickness of 4cm multiplied by 16cm, putting the curing module into a water bath with the temperature of 90 ℃ for curing for 24 hours, and taking out the solidified cement to obtain a blank set cement module.
Comparative example 2
Preparation of cement slurries and set cements incorporating fiber particles
500g of oil well cement, fiber particles (1g) accounting for 2 per mill of the mass of the cement and 220g of water are weighed. The water was placed in a mixing vessel and the mixer was rotated at low speed (4000. + -. 200 rpm) and the weighed cement and fiber particles were added over 15 seconds, the mixer lid was closed and mixing continued at high speed (12000. + -. 500 rpm) for 35 seconds to produce a fiber particle slurry.
And pouring the fiber particle cement paste into a curing module with the thickness of 4cm multiplied by 16cm, putting the curing module into a water bath with the temperature of 90 ℃ for curing for 24 hours, and taking out the solidified cement to obtain the fiber particle cement stone module.
Example 1
Styrene-butadiene copolymer based shape memory particles for oil well cement, cement slurry and set cement module preparation
A styrene-butadiene shape memory polymer with the shape memory deformation temperature of 55-60 ℃ is frozen and crushed into shape memory polymer powder with the diameter of 0.16-0.5mm at low temperature.
Heating and melting shape memory polymer powder, and uniformly coating and mixing a copper tough sheet and a shape memory polymer hot-melt liquid, wherein the mass ratio of each material is 50%; cooling the uniformly mixed materials to 55-75 ℃, coiling the materials to prepare a roll, and cooling to room temperature.
And granulating the compressed roll by a cutting granulator, wherein the size of the granules is controlled to be less than 3mm, such as 0.5mm, 1mm, 2mm and 3mm, so as to facilitate mixing.
100 parts by mass of oil well cement, 2% by mass of shape memory particles (i.e., 2 parts by mass) based on the mass of the cement, and 44 parts by mass of water are weighed. The water is placed in a mixing vessel, the mixer is rotated at low speed (4000. + -. 200 rpm) and the weighed cement and addition of cement is completed within 15 secondsShape memory particles, covered with the stirrer and stirred at high speed (12000 + -500 rpm) for 35 s to obtain a cement paste containing shape memory particles with a density of 1.90g/cm3。
Pouring the cement paste containing the shape memory particles into a curing module with the thickness of 4cm multiplied by 16cm, putting the curing module into a water bath with the temperature of 90 ℃ for curing for 24 hours, and taking out the solidified cement to obtain the cement stone module containing the shape memory particles.
Example 2
Polyurethane copolymer based shape memory particles for oil well cement, cement slurry and set cement module preparation
A polyurethane shape memory polymer with the shape memory deformation temperature of 65-70 ℃ is frozen and crushed into shape memory polymer powder with the diameter of 0.07-0.16mm at low temperature.
Heating and melting shape memory polymer powder, and uniformly coating and mixing stainless steel flexible sheets and shape memory polymer hot melt liquid, wherein the stainless steel flexible sheets and the shape memory polymer powder respectively account for 80% and 20% by mass; cooling the uniformly mixed materials to 65-85 ℃, coiling the materials to prepare a roll, and cooling to room temperature.
And granulating the compressed roll by a cutting granulator, wherein the size of the granules is controlled to be less than 3mm, such as 0.5mm, 1mm, 2mm and 3mm, so as to facilitate mixing.
100 parts by mass of oil well cement, 2% by mass of shape memory particles (i.e., 2 parts by mass) based on the mass of the cement, and 44 parts by mass of water are weighed. Placing water in a mixing container, rotating the stirrer at low speed (4000 + -200 rpm), adding the weighed cement and shape memory particles within 15 seconds, covering the cover of the stirrer, and stirring at high speed (12000 + -500 rpm) for 35 seconds to obtain cement paste containing shape memory particles with density of 1.90g/cm3。
Pouring the cement paste containing the shape memory particles into a curing module with the thickness of 4cm multiplied by 16cm, putting the curing module into a water bath with the temperature of 90 ℃ for curing for 24 hours, and taking out the solidified cement to obtain the cement stone module containing the shape memory particles.
Example 3
Preparation of shape memory particles, cement paste and set cement modules for oil well cement based on polyvinyl acetal gel and ethylene-vinyl acetate copolymer
A polyvinyl acetal gel with shape memory deformation temperature of 65-70 deg.C and ethylene-vinyl acetate copolymer are frozen at low temperature and pulverized into 0.05-0.16 mm.
Heating and melting shape memory polymer powder, and uniformly coating and mixing aluminum flexible sheets and shape memory polymer hot-melt liquid, wherein the aluminum flexible sheets and the shape memory polymer powder respectively account for 20% and 80% by mass; cooling the uniformly mixed materials to 65-85 ℃, coiling the materials to prepare a roll, and cooling to room temperature.
And granulating the compressed roll by a cutting granulator, wherein the size of the granules is controlled to be less than 3mm, such as 0.5mm, 1mm, 2mm and 3mm, so as to facilitate mixing.
100 parts by mass of oil well cement, 1% by mass of shape memory particles (i.e., 1 part by mass) based on the mass of the cement, and 44 parts by mass of water are weighed. Placing water in a mixing container, rotating the stirrer at low speed (4000 + -200 rpm), adding the weighed cement and shape memory particles within 15 seconds, covering the cover of the stirrer, and stirring at high speed (12000 + -500 rpm) for 35 seconds to obtain cement paste containing shape memory particles with density of 1.90g/cm3。
Pouring the cement paste containing the shape memory particles into a curing module with the thickness of 4cm multiplied by 16cm, putting the curing module into a water bath with the temperature of 90 ℃ for curing for 24 hours, and taking out the solidified cement to obtain the cement stone module containing the shape memory particles.
Example 4
Shape memory particles for oil well cement based on styrene-butyl acrylate copolymer, cement paste and set cement module preparation
A shape memory polymer of styrene-butyl acrylate copolymer with shape memory deformation temperature of 75-80 deg.C is frozen at low temperature and pulverized into 0.07-0.16 mm.
Heating and melting shape memory polymer powder, and uniformly coating and mixing the EVA tough sheet and the shape memory polymer hot-melt liquid, wherein the EVA tough sheet and the shape memory polymer powder respectively account for 50% by mass; cooling the uniformly mixed materials to 75-95 ℃, coiling the materials to prepare a roll, and cooling to room temperature.
And granulating the compressed roll by a cutting granulator, wherein the size of the granules is controlled to be less than 3mm, such as 0.5mm, 1mm, 2mm and 3mm, so as to facilitate mixing.
100 parts by mass of oil well cement, 3% by mass of shape memory particles (i.e., 3 parts by mass) based on the mass of the cement, and 44 parts by mass of water are weighed. Placing water in a mixing container, rotating the stirrer at low speed (4000 + -200 rpm), adding the weighed cement and shape memory particles within 15 seconds, covering the cover of the stirrer, and stirring at high speed (12000 + -500 rpm) for 35 seconds to obtain cement paste containing shape memory particles with density of 1.90g/cm3。
Pouring the cement paste containing the shape memory particles into a curing module with the thickness of 4cm multiplied by 16cm, putting the curing module into a water bath with the temperature of 90 ℃ for curing for 24 hours, and taking out the solidified cement to obtain the cement stone module containing the shape memory particles.
Example 5
Shape memory particles for oil well cement based on styrene-butyl acrylate copolymer, cement paste and set cement module preparation
A styrene-butyl acrylate copolymer with shape memory deformation temperature of 55-60 ℃ is frozen and crushed into shape memory polymer powder with the diameter of 0.05-0.16mm at low temperature.
Heating and melting shape memory polymer powder, and uniformly coating and mixing a polypropylene tough sheet and a shape memory polymer hot-melt liquid, wherein the polypropylene tough sheet and the shape memory polymer powder respectively account for 40% and 60% in mass ratio; cooling the uniformly mixed materials to 55-75 ℃, coiling the materials to prepare a roll, and cooling to room temperature.
And granulating the compressed roll by a cutting granulator, wherein the size of the granules is controlled to be less than 3mm, such as 0.5mm, 1mm, 2mm and 3mm, so as to facilitate mixing.
100 parts by mass of oil well cement, 8% by mass of shape memory particles (i.e., 8 parts by mass) based on the mass of the cement, and 44 parts by mass of water are weighed. Placing water in a mixing container, rotating the stirrer at low speed (4000 + -200 rpm), adding the weighed cement and shape memory particles within 15 seconds, covering the cover of the stirrer, and stirring at high speed (12000 + -500 rpm) for 35 seconds to obtain cement paste containing shape memory particles with density of 1.90g/cm3。
Pouring the cement paste containing the shape memory particles into a curing module with the thickness of 4cm multiplied by 16cm, putting the curing module into a water bath with the temperature of 90 ℃ for curing for 24 hours, and taking out the solidified cement to obtain the cement stone module containing the shape memory particles.
Example 6
Shape memory particles for oil well cement based on styrene-butyl acrylate copolymer, cement paste and set cement module preparation
The styrene-butyl acrylate copolymer with the shape memory deformation temperature of 65-70 ℃ is frozen and crushed into shape memory polymer powder with the diameter of 0.16-0.5mm at low temperature.
Heating and melting shape memory polymer powder, and uniformly coating and mixing polyethylene toughness sheets and shape memory polymer hot melt liquid, wherein the polyethylene toughness sheets and the shape memory polymer powder respectively account for 40% and 60% by mass; cooling the uniformly mixed materials to 65-85 ℃, coiling the materials to prepare a roll, and cooling to room temperature.
And granulating the compressed roll by a cutting granulator, wherein the size of the granules is controlled to be less than 3mm, such as 0.5mm, 1mm, 2mm and 3mm, so as to facilitate mixing.
100 parts by mass of oil well cement, shape memory particles (i.e., 0.5 part by mass) accounting for 0.5% by mass of the cement, and 44 parts by mass of water are weighed. Placing the water in a mixing container, rotating the stirrer at low speed (4000 + -200 rpm), adding the weighed cement and shape memory particles within 15 seconds, covering the cover of the stirrer, and stirring at high speed (12000 + -500 rpm) for 35 seconds to obtain the product containing shape memory particlesGranulated cement paste, density 1.90g/cm3。
Pouring the cement paste containing the shape memory particles into a curing module with the thickness of 4cm multiplied by 16cm, putting the curing module into a water bath with the temperature of 90 ℃ for curing for 24 hours, and taking out the solidified cement to obtain the cement stone module containing the shape memory particles.
Example 7
Shape memory particles for oil well cement based on styrene-butyl acrylate copolymer, cement paste and set cement module preparation
A styrene-butyl acrylate copolymer with shape memory deformation temperature of 75-80 ℃ is frozen and crushed into shape memory polymer powder with the diameter of 0.4-0.5mm at low temperature.
Heating and melting shape memory polymer powder, and uniformly coating and mixing an organic silicon tough sheet and a shape memory polymer hot-melt liquid, wherein the organic silicon tough sheet and the shape memory polymer powder respectively account for 30% and 70% by mass; cooling the uniformly mixed materials to 75-95 ℃, coiling the materials to prepare a roll, and cooling to room temperature.
And granulating the compressed roll by a cutting granulator, wherein the size of the granules is controlled to be less than 3mm, such as 0.5mm, 1mm, 2mm and 3mm, so as to facilitate mixing.
100 parts by mass of oil well cement, shape memory particles (i.e., 0.5 part by mass) accounting for 0.5% by mass of the cement, and 44 parts by mass of water are weighed. Placing water in a mixing container, rotating the stirrer at low speed (4000 + -200 rpm), adding the weighed cement and shape memory particles within 15 seconds, covering the cover of the stirrer, and stirring at high speed (12000 + -500 rpm) for 35 seconds to obtain cement paste containing shape memory particles with density of 1.90g/cm3。
Pouring the cement paste containing the shape memory particles into a curing module with the thickness of 4cm multiplied by 16cm, putting the curing module into a water bath with the temperature of 90 ℃ for curing for 24 hours, and taking out the solidified cement to obtain the cement stone module containing the shape memory particles.
Example 8
Testing of modulus of elasticity and flexural Strength of Cement Stone
And (3) testing the elastic modulus and the bending strength of the cement stone module at room temperature of 25 ℃ by adopting a German Toni compression and bending tester. The test results are shown in Table 1.
TABLE 1
| Examples | Modulus of elasticity (GPa) | Breaking strength (Mpa) |
| Comparative example 1 | 13.6 | 0.14 |
| Comparative example 2 | 13.6 | 0.20 |
| Example 1 | 8.6 | 0.41 |
| Example 2 | 9.8 | 0.43 |
| Example 3 | 8.0 | 0.42 |
| Example 4 | 8.5 | 0.21 |
| Example 5 | 7.8 | 0.32 |
| Example 6 | 10.0 | 0.19 |
| Example 7 | 10.1 | 0.20 |
It can be seen that the shape memory particles for oil well cement based on the temperature-sensitive shape memory polymer can reduce the elastic modulus of the set cement and can increase the flexural strength of the set cement. The performance favorably ensures the influence of oil and gas yield increase on the well cementation quality after the well cementation of the oil and gas well, and provides favorable support for realizing the integrity of a shaft.
2. Testing of cement slurry leakage stopping effect
The static cement leakage stoppage simulator can be used for simulating an indoor leakage stoppage process and evaluating a leakage stoppage effect, and consists of a top cover, a metal slurry cylinder, a bottom cover, a backing ring and a test piece for simulating holes and seams of 1mm, and is additionally provided with a heating device and a pressurizing device. During the experiment, 85mL of water is filled in the backing ring, and then the water is separated from the test piece by the piston, so that the leaked cement paste is prevented from blocking the controllable flow rate screw of the bottom cover. Under the pressure condition, cement slurry can pass through the holes or the seams on the test piece, then the piston is pushed, water is extruded out from the backing ring, and the volume of the extruded water is the filtration volume after the cement slurry is blocked. The instrument is convenient to operate and simple in structure. Pressurizing with high pressure nitrogen cylinder at 89 deg.C and 0-7 MPa. The working principle of indoor evaluation of the plugging effect is as follows: respectively simulating a porous stratum and a fractured stratum by using pore test pieces with different apertures or gap test pieces with different widths, putting the test pieces into a specified position of a main body device during experiment, then putting a backing ring, wherein the backing ring contains a piston, filling 85mL of water into the backing ring, screwing a bottom cover, and closing a flow-rate-controllable screw; then, 350mL of cement paste prepared according to API (prefabricated bar: 89 ℃, 73min) is injected into the metal kettle body, the cover of the kettle is screwed, and the upper and lower 2 flow-rate-controllable screws are opened; pressurizing according to the specification, sequentially increasing the pressure from 0.3Mpa to 5.0Mpa, bearing for 2min under each pressure difference condition, recording the filtration loss under each pressure difference, and finally determining the total filtration loss, wherein the total bearing time is 14 min. After the experiment is finished, the total filtration volume of the extruded water is measured to examine the plugging capability of the fiber cement slurry, and the smaller the filtration loss is, the better the plugging effect is.
Shape memory particles are mixed in the experiment on the basis of primary pulp, an indoor simulation leakage stoppage experiment is carried out on the porosity leakage loss and the crack leakage loss by using a cement leakage stoppage static simulator, a 4mm pore test piece is selected, and the experimental result is shown in table 2. The evaluation criteria of the leaking stoppage effect are as follows: the total filtration loss is less than or equal to 40mL and is completely blocked; the total filtration loss is basically blocked within the range of 40-70 mL; a total fluid loss greater than 70mL indicates a lost circulation failure. From experimental data, the shape memory particles of examples 1-7 can meet the requirement of leaking stoppage.
TABLE 2
| Examples | Fluid loss (mL) | Leakage stopping effect |
| Comparative example 1 | >70 | Is not blocked |
| Comparative example 2 | >70 | Is not blocked |
| Example 1 | 10 | Is completely blocked |
| Example 2 | 12 | Is completely blocked |
| Example 3 | 25 | Is completely blocked |
| Example 4 | 6 | Is completely blocked |
| Example 5 | 8 | Is completely blocked |
| Example 6 | 27 | Is completely blocked |
| Example 7 | 35 | Is completely blocked |
Claims (8)
1. A thermally-induced deployment device, comprising:
the thermally-induced unfolding device is a shape memory particle;
the shape memory particles comprise a flexible sheet and a temperature-sensitive shape memory polymer coated by the flexible sheet;
the content of the temperature-sensitive shape memory polymer is 20-99.99 wt% of the shape memory particles;
the particle size of the shape memory particles is less than or equal to 8 mm;
the tough sheet is at least one of polypropylene, polyethylene, EVA, iron, copper, stainless steel, aluminum, alloy and carbon fiber sheet;
the shape memory polymer is at least one of styrene-butadiene copolymer, styrene-butyl acrylate copolymer, polyurethane, polyvinyl acetal gel and ethylene-vinyl acetate copolymer;
the thermotropic spreader is prepared by the following method:
crushing and heating the temperature-sensitive shape memory polymer to melt, uniformly coating the temperature-sensitive shape memory polymer hot melt liquid on a flexible sheet, rolling the sheet into a roll, and cooling the roll to room temperature for cutting and granulation.
2. The thermally induced deployment device of claim 1, wherein:
the content of the shape memory polymer is 30-70 wt% of the shape memory particles;
the particle size of the shape memory particles is greater than or equal to 0.5mm and less than or equal to 5.0 mm.
3. The thermally induced deployment device of claim 2, wherein:
the content of the shape memory polymer is 40-60 wt% of the shape memory particles;
the particle size of the shape memory particles is greater than or equal to 0.5mm and less than or equal to 3.0 mm.
4. The thermally induced deployment device of claim 1, wherein:
the flexible sheet is an organic sheet or a metal sheet;
the deformation temperature range of the temperature-sensitive shape memory polymer is 55-95 ℃.
5. The thermally induced deployment device of claim 4, wherein:
the deformation temperature range of the temperature-sensitive shape memory polymer is 60-80 ℃.
6. A method of making a thermally-induced deployment device according to any one of claims 1 to 5, the method comprising:
crushing and heating the temperature-sensitive shape memory polymer to melt, uniformly coating the temperature-sensitive shape memory polymer hot melt liquid on a flexible sheet, rolling the sheet into a roll, and cooling the roll to room temperature for cutting and granulation.
7. The method of making a thermally-deployable device according to claim 6, wherein:
granulating at a temperature higher than or equal to the lowest value of the deformation temperature of the temperature-sensitive shape memory polymer.
8. The preparation method of the temperature-controlled shape memory plugging agent as defined in claim 7, wherein:
and granulating at a temperature which is higher than or equal to the maximum deformation temperature of the temperature-sensitive shape memory polymer by 5 ℃ and lower than or equal to the maximum deformation temperature of the temperature-sensitive shape memory polymer by 15 ℃.
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