CN109517588A - A kind of temperature control shape memory sealing agent and preparation method - Google Patents
A kind of temperature control shape memory sealing agent and preparation method Download PDFInfo
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- CN109517588A CN109517588A CN201710836652.2A CN201710836652A CN109517588A CN 109517588 A CN109517588 A CN 109517588A CN 201710836652 A CN201710836652 A CN 201710836652A CN 109517588 A CN109517588 A CN 109517588A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/426—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells for plugging
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
- C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
Abstract
The invention discloses a kind of temperature control shape memory sealing agent and preparation methods.Sealing agent is shape memory particle；Shape memory particle includes: the temperature sensitive type shape-memory polymer of hollow elastomeric foam sponge and its coating；The content of temperature sensitive type shape-memory polymer is the 20-99.99wt% of shape memory particle；The partial size of shape memory particle is less than or equal to 8mm.Preparation method includes: that temperature sensitive type shape-memory polymer pulverizing heating melts, and temperature sensitive type shape-memory polymer heat is melted liquid and uniformly coats uncompressed hollow elastomeric foam sponge, and compression tablet is made in compression, is cooled to room temperature cutting and is granulated.The present invention is used temperature sensitive shape-memory polymer and is carried out bonded pelleting with organic hollow elastomeric foam sponge composite construction.It is added in cementing slurry or drilling mud, the downhole temperature for being suitable for increases environment excitation, expands several times volume, using volume steric effect, plays the purpose for blocking rock fracture.
Description
Technical field
The present invention relates to leak-proof leak-stopping technical fields, further say, be related to a kind of temperature control shape memory sealing agent and
Preparation method.
Background technique
Leakage is one of drilling well, down hole problem common in well cementing process.Leakage can not only expend drilling time, leakage
The problems such as losing drilling fluid, cement slurry, but also may cause bit freezing, blowout, well slough, poor cementing quality, even results in wellbore report
Useless accident, causes heavy economic losses.
The leakage for solving the problems, such as oil/gas well is always the project of each major oil and gas field concern.Conventional cementing cement slurry does not have stifled
Function is leaked, but after inert fibrous material is added, accumulation and bridging action due to fiber are easy to form net in leakage channel
Shape structure, and too big variation will not occur for the traditional performance of cement slurry, therefore can carry out one to the leakage in drilling well, well cementing process
Determine the closure of degree.Also, the addition of fiber can also improve the toughness of Behavior of Hardened Cement Paste, it is ensured that later period perforating job preferably carries out.
Fiber is commonly used to prepare fibrous cement paste for well cementing operation as a kind of inert material.Fibrous cement paste is exactly
The fibrous material of certain proportion and length is mixed into cement slurry basic components, mixed cement slurry property does not have compared with magma
There is too big variation, and fiber is easy in leakage channel through accumulation, building bridge forms reticular structure.Therefore, fibre cement
Slurry can also be used for leakage and block operation.Currently, dosage (< 5 ‰, account for the amount of cement) and length mainly by changing fiber
(1-6mm) forms fiber leak-stopping cement mortar system.Usually fiber is added by operator in this system on cementing truck.This
In it should be noted that because fiber have agglomerate prehensile, cannot be dry-mixed in cement.Meanwhile manually in cementing truck
On be sprinkled into that fiber speed is slower, and the rheological equationm of state that excessively will affect cement slurry is added in fiber, so general additional amount < 5 ‰ (account for
The amount of cement).In addition the length of fiber cannot be too long, and which has limited the plugging effects of fiber leak stopping slurry.
For this reason, it may be necessary to develop the novel blocking agent of one kind to overcome disadvantages mentioned above.
Summary of the invention
To solve the problem in the prior art, the invention discloses a kind of temperature control shape memory sealing agent and preparation sides
Method.The present invention is with organic hollow elastomeric foam sponge composite construction, the expanded granular with temperature control shape memory function of formation
Manufacturing method.The expanded granular is different from traditional plugging fiber material, but uses temperature sensitive shape-memory polymer and carry out
Bonded pelleting.It is added in cementing slurry or drilling mud, the downhole temperature for being suitable for increases environment excitation, expands several times body
Product plays the purpose for blocking rock fracture using volume steric effect.
An object of the present invention is to provide a kind of temperature control shape memory sealing agent.
The sealing agent is shape memory particle；
The shape memory particle includes: the temperature sensitive type shape-memory polymer of hollow elastomeric foam sponge and its coating；
The content of the temperature sensitive type shape-memory polymer is the 20-99.99wt% of shape memory particle；Preferably 30-
70wt%；More preferably 40-60wt%；
The partial size of the shape memory particle is less than or equal to 8mm, preferably greater than or equal to 0.5mm, and is less than or waits
In 5.0mm；More preferably greater than or equal to 0.5mm, and it is less than or equal to 3.0mm.
The deformation temperature range of temperature sensitive type shape-memory polymer is 55-95 DEG C；Preferably 60-80 DEG C.
The hollow elastomeric foam sponge be preferably polyurethane foam, polyether foam, rubbery foam, in silicon foams
It is at least one.
The temperature sensitive type shape-memory polymer is preferably that styrene-butadiene copolymer, Styrene And Butyl-acrylate are total
At least one of polymers, polyurethane, Pioloform, polyvinyl acetal gel and ethylene-vinyl acetate copolymer.
The second object of the present invention is to provide a kind of preparation method of temperature control shape memory sealing agent.
Include:
Temperature sensitive type shape-memory polymer pulverizing heating melts, and temperature sensitive type shape-memory polymer heat is melted liquid and is uniformly coated
Uncompressed hollow elastomeric foam sponge, is cooled to room temperature compression, and compression tablet is made, and cutting is granulated, and the temperature control shape is made
Shape remembers sealing agent.
Wherein,
Be greater than or equal to temperature sensitive type shape-memory polymer deformation temperature minimum at a temperature of be granulated；More
It is preferred that: at 5 DEG C of peak of the deformation temperature for being greater than or equal to temperature sensitive type shape-memory polymer, and it is less than or equal to temperature sensitive type
It is granulated at a temperature of 15 DEG C of peak of the deformation temperature of shape-memory polymer.
Currently, the leak-proof leak-stopping of oil well cement paste does not have good method in well cementing process, only there is potential leakage
Be added fiber when risk, and traditional fibre have the shortcomings that it is as above.Therefore, shape memory particle is used in the present invention
Formed leak-proof leak-stopping, be especially used to form in leak-proof leak-stopping oil-well cement slurry system and drilling fluid leak stopping in, can be effective
Solve disadvantage existing in the prior art.For example, in the present invention, by the way that shape memory particle is added into leak stopping slurries,
Since shape memory particle is granular substance, and general grain diameter is smaller, therefore convenient for being uniformly mixed, will not be in leak stopping slurries
It is middle to reunite.Meanwhile injection pit shaft initial stage due to temperature it is low not up to temperature sensitive shape-memory polymer deformation temperature,
So the expansion structure for releasing viscous connection will not be dismissed.As leak stopping slurries enter in well, formation temperature is gradually risen, when reaching
When the deformation temperature of shape memory particle, connection declines are glued, are become restoring the hollow of shape from original granular substance shape
The big expansion structure of elastomeric foam sponge, and it is evenly spread in leak stopping slurries in the case where flowing shear action.And it is preparing
When, since hollow elastomeric foam sponge structure is cut into different length during coextrusion mold and shear granulation, so
Reach the hollow elastomeric foam sponge structure length that releases of shaft bottom be also it is different in size, this is advantageous for straggly at leakage take
Bridge forms bridge blinding, plays leak-proof leak-stopping effect.Therefore, the present invention, which not only solves, is easy asking for agglomerate when traditional fibre is added
Topic, and shape memory particle can be added directly into leak stopping slurries, avoided and needed marginal not to enter side in the process using fiber
Be added fiber the higher operational sequence of difficulty, while also avoid additional amount it is very few and cannot sufficiently show its leakproof and/or
The problem of plugging effect, and distribution of the shape memory particle in leakage-stop liquid is more uniform, therefore, can effective leakproof and/
Or leak stopping.
The temperature range of the temperature sensitive type shape-memory polymer is 55-95 DEG C；The particularly preferably described temperature sensitive type shape note
The temperature range for recalling polymer is 60-80 DEG C.Oil-well cement shape memory particle based on temperature sensitive type shape-memory polymer
It can be used in oil well cement paste, the cement paste rheological configured using shape memory particle is good, is easy to cementing operation.Meanwhile
There is leak-proof leak-stopping effect using the oil well cement paste of shape memory particle.In addition, by using shape memory particle, it can be effective
Increase Toughness of Harden Cement, cement impact resistance also with higher.
In a specific embodiment, the shape-memory polymer includes styrene-butadiene copolymer, benzene second
At least one of alkene-butyl acrylate copolymer, polyurethane, Pioloform, polyvinyl acetal gel and ethylene-vinyl acetate copolymer.
When selection is using shape memory particle, to consider the following: (1) using effect, particulate matter use excessive, meeting
Accumulation is generated behind underground after leading to pumping, thus is easy blocking；(2) cement slurry is finally Behavior of Hardened Cement Paste to be frozen into, organically
The addition of extra material can improve the performances such as elasticity modulus, intensity and the anti-folding of Behavior of Hardened Cement Paste, moreover, will affect if dosage is excessive
Water mudrock structure；(3) economic factor, under the usage amount of permission, due to shape memory particle, especially shape-memory polymer
Dosage it is more, then its cost is also higher.Comprehensively consider in terms of therefore, it is necessary to take into account three above.Therefore, it is starched with leak stopping
The quality meter of solid component in liquid, the amount of the shape memory particle are 0.5-8 mass %；Preferably 1-5 mass %, especially
Preferably 2-3 mass %.Wherein, leak stopping slurries generally comprise liquid component and solid component, with the solid group in leak stopping slurries
The quality meter divided is meant, for example, when leak stopping slurries are cement slurry, cement slurry is by liquid component --- water and solid
Component --- cement composition, then, the solid component in leak stopping slurries is exactly cement, i.e., in terms of the quality of cement.In addition, also needing
It is noted that the dosage of the shape memory particle is related with the size of hole and/or gap that needs block, in hole
And/or gap it is larger when, need the dosage of the shape memory particle higher；In hole and/or smaller gap, need described
The dosage of shape memory particle is lower.
It further include hollow elastomeric foam sponge, preferably polyurethane foam, polyether foam, rubber in the shape memory particle
At least one of quality material such as foam, silicon foams, but not limited to this.
In terms of the quality of the shape memory particle, the content of the shape-memory polymer is 20-99.99 mass %；
It is preferred that 30-70 mass %；Particularly preferred 40-60 mass %.
In the present invention, the size of shape memory particle is generally not enough at limitation of the present invention.However its particle is excessive,
It is not easy to mix in leak stopping slurries, therefore, it is necessary to the lesser particle of partial size is selected, but particle is too small, then cannot play
The performance of its shape memory.Therefore, in a specific embodiment, the partial size of the shape memory particle is less than or equal to
8mm, preferably greater than or equal to 0.5mm, and it is less than or equal to 5.0mm；More preferably equal to or greater than 0.5mm, and be less than or equal to
3.0mm。
In a specific embodiment, the structure of the shape-memory polymer is entirely or partly hollow high-elastic bubble
Foam sponge.Shape-memory polymer can be prepared into shape memory expanded granular for blocking agent after certain process
In, it can very easy be interpreted.But at present, since its material is inherently relatively expensive, it is being prepared into shape memory in addition
The process of expanded granular even more increases its cost, therefore, in the undiminished situation of cost, shape memory is swollen
Swollen particle is for being not preferred technical solution in blocking agent.
The shape-memory polymer or the composition including the shape-memory polymer are granulated to obtain described
Shape memory particle；Wherein, further include hollow elastomeric foam sponge in preferred composition, preferably polyurethane foam, polyether foam,
At least one of quality material such as rubbery foam, silicon foams, but not limited to this.It is needed by processing inflatable
Memory particle, to finally solve application problem.
It is granulated under conditions of the shape-memory polymer deformation；It is preferred that including in the shape-memory polymer
When temperature sensitive type shape-memory polymer, in the temperature of the minimum for the deformation temperature for being greater than or equal to temperature sensitive type shape-memory polymer
It is granulated under degree；Particularly preferably when the shape-memory polymer includes temperature sensitive type shape-memory polymer, being higher than or
Equal to 5 DEG C of peak of the deformation temperature of temperature sensitive type shape-memory polymer, and it is less than or equal to temperature sensitive type shape memory polymers
It is granulated at a temperature of 15 DEG C of peak of the deformation temperature of object.It should be pointed out that in general, temperature sensitive type shape memory
The deformation temperature of polymer generally has certain temperature range, therefore, two endpoint values in the range of its deformation temperature
The respectively peak of the minimum of deformation temperature and deformation temperature.In the present invention, in the range of deformation temperature or higher than shape
15 DEG C of the peak of temperature is hereinafter, can be the temperature range of granulation.
Particle of the present invention is made of hollow elastomeric foam sponge (1) and two part of shape-memory polymer (2) filled layer.Tool
There is the expanded granular of temperature control shape memory function, is blended into cementing concrete under squeezed state, it is convenient to be transported with cement slurry
To underground appropriate location.As downhole temperature is stepped up, when reaching temperature-controlled conditions, shape memory function triggering, volume expansion.
Apparent volume can be increased.Using bulk effect, stops cement slurry to be lost from rock crevice, realize the efficient envelope of rock fracture
It is stifled.Meet efficient well shaft fixing technology requirement, while increasing Toughness of Harden Cement, intensity and service life.
Finally, the application the present invention provides a kind of blocking agent as described above in oilwell drilling field.
When shape memory particle of the invention is in ground compressive state, volume be can control, such as in 1mm3, downhole temperature
After setting out, volume can increase 10 times or more, generate volume steric effect, have good plugging effect.Hollow elastomeric foam
Sponge is solidificated in Behavior of Hardened Cement Paste, can effectively improve toughness and intensity.It is verified by scientific research early period, it was demonstrated that principle is feasible, has good
Good plugging effect.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated.
Comparative example 1
Blank cement slurry and Behavior of Hardened Cement Paste preparation
Weigh 500g oil-well cement, 220g water.Water is put in the mixing container, with blender with low speed (4000 ± 200
Rev/min) rotation, and add weighed cement in 15 seconds, cover the lid of blender, and high speed (12000 ± 500 turns/
Point) under continue stirring 35 seconds, be made blank cement slurry.
By above-mentioned blank cement slurry, pours into 4cm × 4cm × 16cm maintenance module, be put into 90 DEG C of water-bath and conserve
24 hours, the cement solidified is taken out, blank Behavior of Hardened Cement Paste module is obtained.
Comparative example 2
Cement slurry and the Behavior of Hardened Cement Paste preparation of fibrous particle is added
500g oil-well cement is weighed, the fibrous particle (1g) of cement quality 2 ‰, 220g water are accounted for.Water is placed on mixing vessel
In, it is rotated, and add weighed cement and fibrous particle in 15 seconds, is covered with (4000 ± 200 revs/min) of low speed with blender
The lid of blender, and continue stirring 35 seconds under high speed (12000 ± 500 revs/min), fibrous particle cement slurry is made.
By above-mentioned fibrous particle cement slurry, pours into 4cm × 4cm × 16cm maintenance module, be put into 90 DEG C of water-bath
Maintenance 24 hours takes out the cement solidified, obtains fibrous particle Behavior of Hardened Cement Paste module.
Embodiment 1
Styrene-based-butadiene copolymer oil-well cement shape memory particle, cement slurry and Behavior of Hardened Cement Paste module system
It is standby
A kind of styrene-butadiene shape-memory polymer for being 55-60 DEG C by shape memory deformation temperature, using low temperature
Freezing smashing is the shape-memory polymer powder of 0.16-0.5mm.
Hollow elastomeric foam sponge is polyurethane foam sponge.
By temperature sensitive type shape-memory polymer powder heating and melting, temperature sensitive type shape-memory polymer heat is melted into liquid and is uniformly applied
Uncompressed hollow elastomeric foam sponge is covered, mass ratio 50% is respectively accounted for；Material after mixing is cooled to 55-75 DEG C, is carried out
Compression, is made compression tablet, cooling temperature to room temperature.
It is granulated with cutting pelletizer for compressed tablet, the size control of granulation is respectively less than in diameter and length
3mm, such as 0.5mm, 1mm, 2mm, 3mm are not, in order to mixture.
100 mass parts oil-well cements are weighed, the shape memory particle (i.e. 2 mass parts) of cement quality 2%, 44 mass parts are accounted for
Water.Water is put in the mixing container, blender is rotated with (4000 ± 200 revs/min) of low speed, and weighed water is added in 15 seconds
Mud and shape memory particle cover the lid of blender, and continue stirring 35 seconds under high speed (12000 ± 500 revs/min), system
Obtain the cement slurry containing shape memory particle, density 1.90g/cm3。
By the above-mentioned cement slurry containing shape memory particle, pours into 4cm × 4cm × 16cm maintenance module, be put into 90
DEG C water-bath in conserve 24 hours, take out the cement that has solidified, obtain the Behavior of Hardened Cement Paste module containing shape memory particle.
Embodiment 2
It is prepared based on the oil-well cement of polyurethane copolymer shape memory particle, cement slurry and Behavior of Hardened Cement Paste module
A kind of polyurethane shape memory polymer for being 65-70 DEG C by shape memory deformation temperature, using low temperature cold agar
The broken shape-memory polymer powder for 0.07-0.16mm.
Hollow elastomeric foam sponge is polyether foam sponge.
By temperature sensitive type shape-memory polymer powder heating and melting, temperature sensitive type shape-memory polymer heat is melted into liquid and is uniformly applied
Uncompressed hollow elastomeric foam sponge is covered, hollow elastomeric foam sponge and shape-memory polymer powder account for mass ratio and be respectively
80% and 20%；Material after mixing is cooled to 65-85 DEG C, is compressed, compression tablet is made, cooling temperature is extremely
Room temperature.
It is granulated with cutting pelletizer for compressed tablet, the size control of granulation is respectively less than in diameter and length
3mm, such as 0.5mm, 1mm, 2mm, 3mm are not, in order to mixture.
100 mass parts oil-well cements are weighed, 2% shape memory particle of cement quality (i.e. 2 mass parts), 44 mass parts are accounted for
Water.Water is put in the mixing container, blender is rotated with (4000 ± 200 revs/min) of low speed, and weighed water is added in 15 seconds
Mud and shape memory particle cover the lid of blender, and continue stirring 35 seconds under high speed (12000 ± 500 revs/min), system
Obtain the cement slurry containing shape memory particle, density 1.90g/cm3。
By the above-mentioned cement slurry containing shape memory particle, pours into 4cm × 4cm × 16cm maintenance module, be put into 90
DEG C water-bath in conserve 24 hours, take out the cement that has solidified, obtain the Behavior of Hardened Cement Paste module containing shape memory particle.
Embodiment 3
Oil-well cement shape memory particle, water based on Pioloform, polyvinyl acetal gel and ethylene-vinyl acetate copolymer
Mud and the preparation of Behavior of Hardened Cement Paste module
By shape memory deformation temperature be 65-70 DEG C a kind of Pioloform, polyvinyl acetal gel and ethene-vinyl acetate copolymerization
Object uses cryogenic freezing to crush as 0.05-0.16mm.
Hollow elastomeric foam sponge is rubbery foam sponge.
By temperature sensitive type shape-memory polymer powder heating and melting, temperature sensitive type shape-memory polymer heat is melted into liquid and is uniformly applied
Uncompressed hollow elastomeric foam sponge is covered, hollow elastomeric foam sponge and shape-memory polymer powder account for mass ratio and be respectively
20% and 80%；Material after mixing is cooled to 65-85 DEG C, is compressed, compression tablet is made, cooling temperature is extremely
Room temperature.
It is granulated with cutting pelletizer for compressed tablet, the size control of granulation is respectively less than in diameter and length
3mm, such as 0.5mm, 1mm, 2mm, 3mm are not, in order to mixture.
100 mass parts oil-well cements are weighed, 1% shape memory particle of cement quality (i.e. 1 mass parts), 44 mass parts are accounted for
Water.Water is put in the mixing container, blender is rotated with (4000 ± 200 revs/min) of low speed, and weighed water is added in 15 seconds
Mud and shape memory particle cover the lid of blender, and continue stirring 35 seconds under high speed (12000 ± 500 revs/min), system
Obtain the cement slurry containing shape memory particle, density 1.90g/cm3。
By the above-mentioned cement slurry containing shape memory particle, pours into 4cm × 4cm × 16cm maintenance module, be put into 90
DEG C water-bath in conserve 24 hours, take out the cement that has solidified, obtain the Behavior of Hardened Cement Paste module containing shape memory particle.
Embodiment 4
Styrene-based-butyl acrylate copolymer oil-well cement shape memory particle, cement slurry and Behavior of Hardened Cement Paste mould
Block preparation
Shape memory by shape memory deformation temperature for a kind of 75-80 DEG C of Styrene And Butyl-acrylate copolymer gathers
Object is closed, cryogenic freezing is used to crush as 0.07-0.16mm.
Hollow elastomeric foam sponge is silicon foams sponge.
By temperature sensitive type shape-memory polymer powder heating and melting, temperature sensitive type shape-memory polymer heat is melted into liquid and is uniformly applied
Uncompressed hollow elastomeric foam sponge is covered, mass ratio 50% is respectively accounted for；Material after mixing is cooled to 75-95 DEG C, is carried out
Compression, is made compression tablet, cooling temperature to room temperature.
It is granulated with cutting pelletizer for compressed tablet, the size control of granulation is respectively less than in diameter and length
3mm, such as 0.5mm, 1mm, 2mm, 3mm are not, in order to mixture.
100 mass parts oil-well cements are weighed, 3% shape memory particle of cement quality (i.e. 3 mass parts), 44 mass parts are accounted for
Water.Water is put in the mixing container, blender is rotated with (4000 ± 200 revs/min) of low speed, and weighed water is added in 15 seconds
Mud and shape memory particle cover the lid of blender, and continue stirring 35 seconds under high speed (12000 ± 500 revs/min), system
Obtain the cement slurry containing shape memory particle, density 1.90g/cm3。
By the above-mentioned cement slurry containing shape memory particle, pours into 4cm × 4cm × 16cm maintenance module, be put into 90
DEG C water-bath in conserve 24 hours, take out the cement that has solidified, obtain the Behavior of Hardened Cement Paste module containing shape memory particle.
Embodiment 5
Styrene-based-butyl acrylate copolymer oil-well cement shape memory particle, cement slurry and Behavior of Hardened Cement Paste mould
Block preparation
A kind of Styrene And Butyl-acrylate copolymer for being 55-60 DEG C by shape memory deformation temperature, using cryogenic freezing
Crush the shape-memory polymer powder for being 0.05-0.16mm.
Hollow elastomeric foam sponge is silicon foams sponge.
By temperature sensitive type shape-memory polymer powder heating and melting, temperature sensitive type shape-memory polymer heat is melted into liquid and is uniformly applied
Uncompressed hollow elastomeric foam sponge is covered, hollow elastomeric foam sponge and shape-memory polymer powder account for mass ratio and be respectively
40% and 60%；Material after mixing is cooled to 55-75 DEG C, is compressed, compression tablet is made, cooling temperature is extremely
Room temperature.
It is granulated with cutting pelletizer for compressed tablet, the size control of granulation is respectively less than in diameter and length
3mm, such as 0.5mm, 1mm, 2mm, 3mm are not, in order to mixture.
100 mass parts oil-well cements are weighed, the shape memory particle (i.e. 8 mass parts) of cement quality 8%, 44 mass parts are accounted for
Water.Water is put in the mixing container, blender is rotated with (4000 ± 200 revs/min) of low speed, and weighed water is added in 15 seconds
Mud and shape memory particle cover the lid of blender, and continue stirring 35 seconds under high speed (12000 ± 500 revs/min), system
Obtain the cement slurry containing shape memory particle, density 1.90g/cm3。
By the above-mentioned cement slurry containing shape memory particle, pours into 4cm × 4cm × 16cm maintenance module, be put into 90
DEG C water-bath in conserve 24 hours, take out the cement that has solidified, obtain the Behavior of Hardened Cement Paste module containing shape memory particle.
Embodiment 6
Styrene-based-butyl acrylate copolymer oil-well cement shape memory particle, cement slurry and Behavior of Hardened Cement Paste mould
Block preparation
The Styrene And Butyl-acrylate copolymer for being 65-70 DEG C by shape memory deformation temperature, is crushed using cryogenic freezing
For the shape-memory polymer powder of 0.17-0.5mm.
Hollow elastomeric foam sponge is silicon foams sponge.
By temperature sensitive type shape-memory polymer powder heating and melting, temperature sensitive type shape-memory polymer heat is melted into liquid and is uniformly applied
Uncompressed hollow elastomeric foam sponge is covered, hollow elastomeric foam sponge and shape-memory polymer powder account for mass ratio and be respectively
40% and 60%；Material after mixing is cooled to 65-85 DEG C, is compressed, compression tablet is made, cooling temperature is extremely
Room temperature.
It is granulated with cutting pelletizer for compressed tablet, the size control of granulation is respectively less than in diameter and length
3mm, such as 0.5mm, 1mm, 2mm, 3mm are not, in order to mixture.
100 mass parts oil-well cements are weighed, the shape memory particle (i.e. 0.5 mass parts) of cement quality 0.5%, 44 matter are accounted for
Measure part water.Water is put in the mixing container, blender is rotated with (4000 ± 200 revs/min) of low speed, and is added and weighed in 15 seconds
Cement and shape memory particle, cover the lid of blender, and continue stirring 35 under high speed (12000 ± 500 revs/min)
Second, the cement slurry containing shape memory particle, density 1.90g/cm is made3。
By the above-mentioned cement slurry containing shape memory particle, pours into 4cm × 4cm × 16cm maintenance module, be put into 90
DEG C water-bath in conserve 24 hours, take out the cement that has solidified, obtain the Behavior of Hardened Cement Paste module containing shape memory particle.
Embodiment 7
Styrene-based-butyl acrylate copolymer oil-well cement shape memory particle, cement slurry and Behavior of Hardened Cement Paste mould
Block preparation
A kind of Styrene And Butyl-acrylate copolymer for being 75-80 DEG C by shape memory deformation temperature, using cryogenic freezing
Crush the shape-memory polymer powder for being 0.4-0.5mm.
Hollow elastomeric foam sponge is silicon foams sponge.
By temperature sensitive type shape-memory polymer powder heating and melting, temperature sensitive type shape-memory polymer heat is melted into liquid and is uniformly applied
Uncompressed hollow elastomeric foam sponge is covered, hollow elastomeric foam sponge and shape-memory polymer powder account for mass ratio and be respectively
30% and 70%；Material after mixing is cooled to 75-95 DEG C, is compressed, compression tablet is made, cooling temperature is extremely
Room temperature.
It is granulated with cutting pelletizer for compressed tablet, the size control of granulation is respectively less than in diameter and length
3mm, such as 0.5mm, 1mm, 2mm, 3mm are not, in order to mixture.
100 mass parts oil-well cements are weighed, the shape memory particle (i.e. 0.5 mass parts) of cement quality 0.5%, 44 matter are accounted for
Measure part water.Water is put in the mixing container, blender is rotated with (4000 ± 200 revs/min) of low speed, and is added and weighed in 15 seconds
Cement and shape memory particle, cover the lid of blender, and continue stirring 35 under high speed (12000 ± 500 revs/min)
Second, the cement slurry containing shape memory particle, density 1.90g/cm is made3。
By the above-mentioned cement slurry containing shape memory particle, pours into 4cm × 4cm × 16cm maintenance module, be put into 90
DEG C water-bath in conserve 24 hours, take out the cement that has solidified, obtain the Behavior of Hardened Cement Paste module containing shape memory particle.
Embodiment 8
Behavior of Hardened Cement Paste elasticity modulus and flexural strength test
Using German Toni pressure-proof and snap-resistent tester, at 25 DEG C of room temperature, Behavior of Hardened Cement Paste module elasticity modulus and anti-folding are tested
Intensity.Test result such as table 1.
Table 1
| Embodiment | Elasticity modulus (GPa) | Flexural strength (Mpa) |
| Comparative example 1 | 13.6 | 0.14 |
| Comparative example 2 | 13.6 | 0.20 |
| Embodiment 1 | 8.5 | 0.19 |
| Embodiment 2 | 9.7 | 0.16 |
| Embodiment 3 | 8.2 | 0.18 |
| Embodiment 4 | 8.3 | 0.19 |
| Embodiment 5 | 7.6 | 0.23 |
| Embodiment 6 | 10.3 | 0.16 |
| Embodiment 7 | 10.4 | 0.15 |
As can be seen that the oil-well cement shape memory particle based on temperature sensitive type shape-memory polymer can reduce Behavior of Hardened Cement Paste
Elasticity modulus, and can increase the flexural strength of Behavior of Hardened Cement Paste.Frscturing is to solid after this performance advantageously ensures oil gas well cementing operation
The influence of well quality, to realize that wellbore integrity provides advantageous support.
2. cement slurry plugging effect is tested
Cement leak stopping static simulation instrument just can be used in simulating chamber Process of Leaking Stoppage and evaluation plugging effect, in the present invention with
Top cover, metal pulp cylinder, bottom cover, gasket ring and the test specimen composition for simulating the hole of 1mm, seam, are in addition also attached to heating apparatus and pressurization dress
It sets.It will be full of 85mL water in gasket ring when experiment, then separated water and test specimen with piston, prevents the cement slurry blocking bottom cover of leakage
Controllable flow rate screw.Under stress, cement slurry may pass through the hole on test specimen or seam, then push piston, by water from gasket ring
Interior extrusion, the volume for the water being extruded at this time are exactly the filtrate volume after cement slurry leak stopping.The instrumentation is convenient, structure letter
It is single.Indoor high-pressure nitrogen bottle pressurization, pressure limit are 0-7Mpa, and temperature is 89 DEG C.The work of Lab-evaluation plugging effect is former
Reason is: pore formation and fractured reservoir are simulated respectively with the gap test specimen of the hole test specimen of different pore size or different in width,
Test specimen is put into agent set specified position when experiment, is then placed in gasket ring, gasket ring includes piston, gasket ring is full of 85mL water,
Bottom cover is screwed, controllable flow rate screw is closed；Then the 350mL cement slurry for providing to prepare (preform strip: 89 DEG C, 73min) by API
Metal autoclave body is injected, cover is screwed, opens 2 controllable flow rate screws up and down；It pressurizes by regulation, pressure is incremented by successively from 0.3Mpa
To 5.0Mpa, and the pressure-bearing 2min under each pressure differential, total pressure-bearing time is 14min, the filter loss under each pressure difference is recorded,
Finally determine total filter loss.Measurement is squeezed total filtrate volume of water outlet to investigate the leak stopping energy of fibrous cement paste after the completion of experiment
Power, filter loss is smaller, and plugging effect is better.
Experiment is mixed into shape memory particle on the basis of magma, using cement leak stopping static simulation instrument to porous leakage and
Fractured leakage has carried out indoor simulation leaking stoppage experiment, selects the hole test specimen of 4mm, and experiment the results are shown in Table 2.Plugging effect
Evaluation criterion is: it is to block completely that total filter loss, which is less than or equal to 40mL,；Total filter loss is blocked substantially within the scope of 40-70mL；
Total filter loss is greater than 70mL and shows that leak stopping fails.From experimental data, the shape memory particle of embodiment 1-7 is able to satisfy
It is required that having played leak stopping effect.
Table 2
Claims (9)
1. a kind of temperature control shape memory sealing agent, it is characterised in that:
The sealing agent is shape memory particle；
The shape memory particle includes: the temperature sensitive type shape-memory polymer of hollow elastomeric foam sponge and its coating；
The content of the temperature sensitive type shape-memory polymer is the 20-99.99wt% of shape memory particle；
The partial size of the shape memory particle is less than or equal to 8mm.
2. temperature control shape memory sealing agent as described in claim 1, it is characterised in that:
The content of the temperature sensitive type shape-memory polymer is the 30-70wt% of shape memory particle；
The partial size of the shape memory particle is greater than or equal to 0.5mm, and is less than or equal to 5.0mm.
3. temperature control shape memory sealing agent as claimed in claim 2, it is characterised in that:
The content of the temperature sensitive type shape-memory polymer is the 40-60wt% of shape memory particle；
The partial size of the shape memory particle is greater than or equal to 0.5mm, and is less than or equal to 3.0mm.
4. temperature control shape memory sealing agent as described in claim 1, it is characterised in that:
The deformation temperature range of the temperature sensitive type shape-memory polymer is 55-95 DEG C.
5. temperature control shape memory sealing agent as claimed in claim 4, it is characterised in that:
The deformation temperature range of the temperature sensitive type shape-memory polymer is 60-80 DEG C.
6. temperature control shape memory sealing agent as described in claim 1, it is characterised in that:
The hollow elastomeric foam sponge is polyurethane foam, polyether foam, rubbery foam, at least one in silicon foams
Kind；
The temperature sensitive type shape-memory polymer is styrene-butadiene copolymer, Styrene And Butyl-acrylate copolymer, gathers
At least one of urethane, Pioloform, polyvinyl acetal gel and ethylene-vinyl acetate copolymer.
7. a kind of preparation method of the temperature control shape memory sealing agent as described in one of claim 1~6, it is characterised in that described
Method includes:
Temperature sensitive type shape-memory polymer pulverizing heating melts, and temperature sensitive type shape-memory polymer heat is melted liquid uniformly coats and do not press
Contract hollow elastomeric foam sponge, and compression tablet is made in compression, is cooled to room temperature cutting and is granulated, the temperature control shape memory is made
Sealing agent.
8. the preparation method of temperature control shape memory sealing agent as claimed in claim 7, it is characterised in that:
Be greater than or equal to temperature sensitive type shape-memory polymer deformation temperature minimum at a temperature of be granulated.
9. the preparation method of temperature control shape memory sealing agent as claimed in claim 8, it is characterised in that:
At 5 DEG C of peak of the deformation temperature for being greater than or equal to temperature sensitive type shape-memory polymer, and it is less than or equal to temperature sensitive type
It is granulated at a temperature of 15 DEG C of peak of the deformation temperature of shape-memory polymer.
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