CN115286750A - Self-degradation temporary plugging agent and preparation method and application thereof - Google Patents
Self-degradation temporary plugging agent and preparation method and application thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/5045—Compositions based on water or polar solvents containing inorganic compounds
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
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- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
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Abstract
The invention discloses a self-degradation temporary plugging agent and a preparation method and application thereof, and the self-degradation temporary plugging agent comprises the following raw materials in parts by weight based on 100 parts of total mass: 19.4 to 20 portions of hydrophilic polymerization monomer, 10.5 to 1 portion of modified nano particle NP-1, 0.1 to 0.5 portion of hydrophobic monomer,0.12-0.2 part of cross-linking agent, 0.8-1 part of initiator and the balance of water; the hydrophilic polymerization monomer is acrylamide and/or acrylic acid; the hydrophobic monomer is selected from one or more of hexadecyl dimethyl allyl ammonium chloride, dimethyl diallyl ammonium chloride and methacryloyloxyethyl trimethyl ammonium chloride; the cross-linking agent is polyethylene glycol diacrylate; the modified nano-particle NP-1 is nano SiO hydrophobically modified by silane coupling agent 2 . The temporary plugging agent can have certain plugging strength under the condition of high pressure difference, and can be automatically degraded into a low-viscosity solution within a wider temperature range (40-120 ℃), and a preparation method and application thereof.
Description
Technical Field
The invention relates to the field of oilfield chemistry, in particular to a self-degradation temporary plugging agent, a preparation method and application thereof, and more particularly relates to a multifunctional self-degradation temporary plugging agent which has certain plugging strength under oil reservoir conditions and can be automatically degraded into a low-viscosity solution within a wider temperature range (40-120 ℃), and a preparation method and application thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
After the oil is hidden in water injection and exploitation for a period of time, crude oil controlled by old cracks is nearly completely exploited, the cracks form a main water outlet channel, development benefits are reduced, and a large amount of residual oil still exists in the matrix. In order to further control water and increase oil, the productivity of the oil well is fully exerted, and a repeated fracturing technology for plugging old joints and opening new joints is gradually formed. The essence of repeated fracturing is to selectively access and seal old fractures with a sealant and then fracture new fractures to provide a seepage path for the remaining unused oil. The implementation of this process requires a temporary blocking agent with excellent properties.
The most common water-soluble temporary plugging agent is common gel particles at present, and the plugging removal is usually performed by adopting a gel breaker. This approach has the following disadvantages: the plugging strength is small, the gel breaking is not uniform, a large rubber plug is easy to form, and potential damage is caused to an oil layer. In recent years, a self-degradation temporary plugging agent is proposed, which can be well dispersed in water or fracturing fluid, has certain plugging strength under the condition of high pressure difference, and can be automatically degraded into a low-viscosity solution under the condition of an oil reservoir after a period of time, so that stratum pollution and residue damage are reduced. However, the existing self-degradation temporary plugging agent still has the defects of difficult regulation and control of expansion time and degradation time, uncontrollable temporary plugging strength and the like.
Disclosure of Invention
In order to solve the problems, the invention provides a self-degradation temporary plugging agent, a preparation method and application thereof, and the temporary plugging agent can have certain plugging strength under the condition of high pressure difference and can be automatically degraded into a low-viscosity solution within a wider temperature range (40-120 ℃), and the preparation method and application thereof.
In order to realize the purpose, the invention is realized by the following technical scheme:
in a first aspect, the invention provides a self-degradation temporary plugging agent, which comprises the following raw materials in parts by weight based on 100 parts of total mass: 19.4 to 20 portions of hydrophilic polymerization monomer, 0.5 to 1 portion of modified nano particle NP-, 0.1 to 0.5 portion of hydrophobic monomer, 0.12 to 0.2 portion of cross linker, 0.8 to 1 portion of initiator and the balance of water;
the hydrophilic polymerization monomer is acrylamide and/or acrylic acid;
the hydrophobic monomer is selected from one or more of hexadecyl dimethyl allyl ammonium chloride, dimethyl diallyl ammonium chloride and methacryloyloxyethyl trimethyl ammonium chloride;
the cross-linking agent is polyethylene glycol diacrylate;
the modified nano-particle NP-1 is nano SiO hydrophobically modified by a silane coupling agent 2 。
In a second aspect, the invention provides a preparation method of a self-degradation temporary plugging agent, which comprises the following steps:
dissolving a hydrophilic polymerization monomer in water, and adjusting the solution to be alkalescent to obtain a hydrophilic polymerization monomer solution;
sequentially adding a hydrophobic monomer, the modified nano-particle NP-1 and a cross-linking agent into the hydrophilic polymerization monomer solution, and mixing and dissolving to obtain a mixed solution;
and adding an initiator into the mixed solution, and heating for reaction to obtain a product.
In a third aspect, the invention provides the use of the temporary plugging agent in repeated fracturing of an oil reservoir.
The beneficial effects achieved by one or more of the embodiments of the invention are as follows:
screening temporary plugging agent particles with proper particle sizes according to oil reservoir fracture parameters, dispersing the temporary plugging agent particles in injection fluid according to an injection scheme, quickly stirring to form stable suspension, injecting the suspension into an oil-water well through an operation pipe column, allowing the temporary plugging agent particles to enter a plugging target layer, continuously absorbing water and expanding to quickly form a high-strength temporary plugging layer, and after a certain period of time, finishing repeated fracturing to realize self degradation. The injection speed is determined according to the injection pressure, and the oil deposit temperature range suitable for the temporary plugging agent is 40-120 ℃.
In the invention, the self-degradation temperature of the temporary plugging agent is 40-120 ℃, the self-degradation temperature range is wide, and the applicable oil reservoir range is wide. According to the invention, the self-degradation temporary plugging agent absorbs water and expands at the oil reservoir temperature and maintains the strength for a period of time, then, the crosslinking agent is subjected to crosslinking failure at the oil reservoir temperature along with the passage of time, the temporary plugging agent is degraded into a linear polymer, the final viscosity is reduced, and the self-degradation of the temporary plugging agent is realized.
In the invention, the swelling and degradation time of the temporary plugging agent can be controlled. In the invention, the temporary plugging agent particles are subjected to water absorption expansion after being added into water, and the hydrophobic monomer contains hydrophobic groups, so that the water absorption rate and water absorption capacity of the temporary plugging agent are reduced, and the expansion capacity of the temporary plugging agent is further reduced. Therefore, the swelling property and swelling rate of the temporary plugging agent can be adjusted by adjusting the addition amount of the hydrophobic monomer. According to the invention, the used crosslinking agent is polyethylene glycol diacrylate containing ester bonds, the ester bonds are broken at a certain temperature, the three-dimensional network structure of the temporary plugging agent is destroyed, and finally the temporary plugging agent becomes a low-viscosity solution, so that the crosslinking density of the temporary plugging agent can be adjusted by adjusting the addition of the crosslinking agent, and the self-degradation time of the temporary plugging agent can be further adjusted.
In the invention, the temporary plugging strength of the temporary plugging agent is controllable. In the invention, the surface of the modified nano-particles is rich in double bonds, and can be connected to a skeleton structure of the temporary plugging agent through free radical polymerization reaction, so that the stability of a three-dimensional network structure of the temporary plugging agent is improved, the strength of the temporary plugging agent is improved, and the double bonds on the modified nano-particles are increased along with the increase of the modification degree, so that the modified nano-particles can be used as a cross-linking agent to connect polymer chains, and the strength of the temporary plugging agent is further increased. Therefore, the temporary plugging strength of the temporary plugging agent can be regulated and controlled by regulating and controlling the addition and the modification degree of the modified nanoparticles.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are included to illustrate an exemplary embodiment of the invention and not to limit the invention.
FIG. 1 shows the results of the swelling property test of the self-degradable temporary plugging agents prepared in examples 1 to 4;
FIG. 2 is a graph comparing the elastic modulus of the self-degrading temporary plugging agents prepared in examples 1-4;
FIG. 3 is a flow chart of the experimental apparatus for plugging and unplugging the temporary plugging agent prepared in examples 1-4;
FIG. 4 is a pressure change curve of the plugging process of the temporary plugging agent prepared in examples 1 to 4;
FIG. 5 is a pressure profile of the deblocking process of the temporary plugging agents prepared in examples 1-4;
FIG. 6 is a schematic structural view of the temporary plugging agent prepared in example 4.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In a first aspect, the invention provides a self-degradation temporary plugging agent, which comprises the following raw materials in parts by weight based on 100 parts of total mass: 19.4 to 20 portions of hydrophilic polymerization monomer, 0.5 to 1 portion of modified nano particle NP-1, 0.1 to 0.5 portion of hydrophobic monomer, 0.12 to 0.2 portion of cross linker, 0.8 to 1 portion of initiator and the balance of water;
the hydrophilic polymerization monomer is acrylamide and/or acrylic acid;
the hydrophobic monomer is selected from one or more of hexadecyl dimethyl allyl ammonium chloride, dimethyl diallyl ammonium chloride and methacryloyloxyethyl trimethyl ammonium chloride;
the cross-linking agent is polyethylene glycol diacrylate;
the modified nano-particle NP-1 is nano SiO hydrophobically modified by silane coupling agent 2 。
Hydrophilic groups in the hydrophilic polymeric monomer are used for absorbing water to enable the temporary plugging agent to absorb water and swell, and hydrophobic groups in the hydrophobic monomer are used for reducing the water absorption rate and the water absorption capacity of the temporary plugging agent so as to inhibit the water absorption and swelling of the temporary plugging agent. The hydrophilic group and the hydrophobic group cooperate with each other to adjust the swelling property and the swelling rate of the temporary plugging agent.
The crosslinking agent contains ester bonds, the ester bonds are broken at a certain temperature, the three-dimensional network structure of the temporary plugging agent is destroyed, and finally the temporary plugging agent becomes a low-viscosity solution, so that the crosslinking density of the temporary plugging agent can be adjusted by adjusting the addition of the crosslinking agent, and the self-degradation time of the temporary plugging agent can be further adjusted.
The main structure of the particle skeleton is an acrylamide structure, and the purpose of adding the acrylic acid is to increase the water absorption and improve the expansion performance.
The salt tolerance of the monomers of hexadecyl dimethyl allyl ammonium chloride, dimethyl diallyl ammonium chloride and methyl acryloyl oxyethyl trimethyl ammonium chloride is better.
The strength of the temporary plugging agent is regulated and controlled in the following way: the regulation and control of the nano particles are most obvious, and mainly the addition and modification degree of the particles are regulated and controlled. Secondly, the addition amount of the hydrophilic monomer, the addition amount of the cross-linking agent, the addition amount of the hydrophobic monomer, the addition amount of the initiator, the reaction temperature, the reaction time and the like can also be changed. Modified nano SiO 2 The surface is rich in double bonds, and can be connected to a skeleton structure of the temporary plugging agent through free radical polymerization reaction, so that the stability of a three-dimensional network structure of the temporary plugging agent is improved, the strength of the temporary plugging agent is improved, and the double bonds on the modified nanoparticles are increased along with the increase of the modification degree, so that the modified nanoparticles can be used as a cross-linking agent to connect a polymer chain, and the strength of the temporary plugging agent is further improved. Therefore, the dosage of the crosslinking agent can be increased by regulating and controlling the addition and the modification degree of the modified nano particles and further regulating and controlling the temporary blocking strength of the temporary blocking agent, the crosslinking density of a polymer chain can be increased, and the strength of the temporary blocking agent particles is increased.
The polyethylene glycol diacrylate serving as a cross-linking agent not only contains ester bonds, but also contains double bonds at two ends of a molecular chain, and polymer chains can be connected to two ends of the cross-linking agent through free radical polymerization reaction to form a three-dimensional space network structure. The ester crosslinking efficiency is high, a stable crosslinking structure can be obtained only by adding a small amount of the ester crosslinking agent, the crosslinking speed is proper, the ester crosslinking agent is stable in the process treatment and storage period, and harmful reaction and condensation are avoided. No toxicity, no irritation and no environmental pollution.
In some embodiments, the hydrophilic polymeric monomer is a combination of acrylamide and acrylic acid in a mass ratio of 1:0.8-1.2.
In some embodiments, the silane coupling agent hydrophobically modified nano-SiO 2 The modification degree of (A) is 20 to 70 percent. The purpose of the modification is to prepare nano SiO 2 Double bonds are introduced to enable the nano SiO to participate in reaction, or be connected to a polymer chain, or be used as a cross-linking agent to be connected with the polymer chain, and the nano SiO can be obtained by excessively low modification degree 2 The efficiency of the reaction is reduced, and most of nano SiO can be generated by excessively high modification degree 2 The crosslinking agent participates in the reaction, and the self-degradation capability of the temporary plugging agent is reduced. Through optimization and selectionSelecting nano SiO with the modification degree of 20-70% 2 。
In some embodiments, the hydrophobic monomer is cetyl dimethyl allyl ammonium chloride. The hydrophobic monomer has stronger hydrophobicity, can provide a hydrophobic side group for a polymer chain, ensures that the polymer chain has certain hydrophobic property, and hydrophobic groups are aggregated due to hydrophobic effect in water to form a space network structure, thereby providing necessary viscoelasticity. And the long-chain alkyl has antibacterial property, so that the condition that the long-chain alkyl is degraded by microorganisms underground can be effectively avoided.
In some embodiments, the initiator is selected from one or more of potassium persulfate, sodium thiosulfate, ammonium persulfate, and sodium bisulfite.
Preferably, the initiator is ammonium persulfate.
In a second aspect, the invention provides a preparation method of a self-degradation temporary plugging agent, which comprises the following steps:
dissolving a hydrophilic polymerization monomer in water, and adjusting the solution to be alkalescent to obtain a hydrophilic polymerization monomer solution;
sequentially adding a hydrophobic monomer, the modified nano-particle NP-1 and a cross-linking agent into the hydrophilic polymerization monomer solution, and mixing and dissolving to obtain a mixed solution;
and adding an initiator into the mixed solution, and heating for reaction to obtain a product.
In some embodiments, the pH of the hydrophilic polymeric monomer is adjusted to a value of 7.2 to 8, preferably 7.4 to 7.8, and more preferably 7.5.
Preferably, the base is sodium hydroxide solution. The concentration of the sodium hydroxide solution is 10-20%, preferably 15%.
In some embodiments, the polymerization temperature is 40-60 ℃ and the reaction time is 3-6h.
In some embodiments, the method further comprises the steps of drying, grinding and crushing the prepared product.
In a third aspect, the invention provides the use of the temporary plugging agent in repeated fracturing of an oil reservoir.
In some embodiments, the method for temporarily plugging the oil layer fracture by using the temporary plugging agent comprises the following steps: screening the temporary plugging agent particles with a set particle size range, uniformly dispersing the temporary plugging agent particles in water to form stable suspension,
and injecting the suspension into an oil-water well, so that the temporary plugging agent particles enter a plugging target layer, continuously absorbing water and expanding to form a high-strength temporary plugging layer, and plugging cracks.
The self-degradation temporary plugging agent provided by the invention is powdery in appearance, forms a heterogeneous system with low viscosity and good fluidity after being dissolved in water and is easy to pump, absorbs water to expand under the condition of a stratum after being injected into the stratum, keeps the strength within a period of time, plugs cracks, can be automatically degraded into a linear polymer at the oil reservoir temperature after the operation is finished, finally reduces the viscosity, has the self-degradation temperature of 40-120 ℃, does not need to add a gel breaker, has simple process flow and causes little damage to the stratum.
The present invention will be further described with reference to the following specific examples.
Example 1
The embodiment provides a preparation method of a multifunctional self-degradation temporary plugging agent, which comprises the following steps:
and 3, adding 0.8 part of initiator-ammonium persulfate into the solution, heating to 40 ℃, and reacting for 5 hours.
And 4, drying the reaction product, grinding and crushing to prepare temporary plugging agent particles with different meshes, which are named as SD-TPA-1.
Example 2
The embodiment provides a preparation method of a multifunctional self-degradation temporary plugging agent, which comprises the following steps:
and 3, adding 0.8 part of initiator-ammonium persulfate into the solution, heating to 40 ℃, and reacting for 5 hours.
And 4, drying the reaction product, grinding and crushing to prepare temporary plugging agent particles with different meshes, which are named as SD-TPA-2.
Example 3
The embodiment provides a preparation method of a multifunctional self-degradation temporary plugging agent, which comprises the following steps:
and 3, adding 0.8 part of initiator-ammonium persulfate into the solution, heating to 40 ℃, and reacting for 5 hours.
And 4, drying the reaction product, grinding and crushing to prepare temporary plugging agent particles with different meshes, which are named as SD-TPA-3.
Example 4
The embodiment provides a preparation method of a multifunctional self-degradation temporary plugging agent, which comprises the following steps:
and 3, adding 0.8 part of initiator-ammonium persulfate into the solution, heating to 40 ℃, and reacting for 5 hours.
And 4, drying the reaction product, grinding and crushing to prepare temporary plugging agent particles with different meshes, which are named as SD-TPA-4.
Performance testing
The test example is to select the multifunctional self-degradation temporary plugging agent prepared in the example to carry out expansion and self-degradation performance tests.
0.5 part of dried and ground four kinds of temporary plugging agent particle powder are respectively added into a prepared 25mL colorimetric tube with a plug, then 20 parts of stratum water with the mineralization degree of 21276.87mg/L are added into the colorimetric tube, the ion composition of the stratum water is shown in Table 1, and the colorimetric tube is fully and uniformly shaken after being sealed. Finally, the particles are respectively placed in a constant temperature box at 80 ℃, the expansion volume of the temporary plugging agent particles in the colorimetric tube is recorded at regular intervals, and the expansion times of the particles are calculated according to the following formula.
In the formula alpha V Expansion factor, V 1 Maximum expansion volume, V 0 -an initial volume.
0.5 part of dried and ground four kinds of temporary plugging agent particle powder are respectively added into a prepared 25mL colorimetric tube with a plug, then 20 parts of stratum water with the mineralization degree of 21276.87mg/L are added into the colorimetric tube, and the colorimetric tube is fully and uniformly shaken after being sealed. And finally, respectively placing the particles in a constant temperature box at 80 ℃, recording the expansion volume of the temporary plugging agent particles in the colorimetric tube at regular intervals, recording the time for complete degradation, and calculating the degradation rate according to the following formula after complete degradation.
In the formula, the alpha-degradation rate, m 1 Mass after complete degradation, m 0 -an initial mass.
Table 1 is the formation water ion composition.
TABLE 1
Table 2 is the self-degradation performance test results for the self-degrading temporary plugging agent.
TABLE 2
| Formulation of | Complete degradation time/h | Percent degradation rate/%) |
| SD-TPA-1 | 240 | 97.14 |
| SD-TPA-2 | 412 | 86.91 |
| SD-TPA-3 | 288 | 92.13 |
| SD-TPA-4 | 492 | 88.13 |
The synthesized temporary plugging agent particles are of a three-dimensional network structure formed by chemical crosslinking of polymer chains and winding of macromolecules. Its expansion in water can be divided into two main stages: the first stage is the hydration of solvent molecules to hydrophilic groups in the particles to form hydrogen bonds after they have been contacted with the particles. This phase is short, fast and accompanied by thermal effects. The second stage is due to the expansion of the three-dimensional polymer network, wherein the hydrophilic ionic groups are hydrolyzed to form free ions. The presence of these ions causes differences in the ion concentration inside and outside the particle, which in turn creates an osmotic pressure differential. Under the action of osmotic pressure, free water enters a polymer network structure of the particles and continuously interacts with hydrophilic groups in the particles to form hydrogen bonds, so that the generation of hydrolysis and the formation of osmotic pressure difference are further promoted, water molecules continuously enter the particles, and the particle size is increased. The osmotic pressure difference between the inside and the outside of the particles is large in the initial stage, and the water absorption expansion rate is high; after a period of time, the osmotic pressure difference decreases, the rate of particle expansion slows, and equilibrium is eventually reached.
FIG. 1 is the result of the swelling property test of the temporary plugging agent, and Table 2 is the result of the self-degradation property test of the temporary plugging agent. The expansion factor and the degradation time can be regulated, but the higher the expansion factor is, the better the expansion factor is, or the shorter the degradation time is, the better the degradation time is, the higher the plugging strength is, the better the plugging strength is. The temporary plugging agent has the core that the regulation of expansion multiple, expansion rate, degradation rate and the like can be realized on the premise of not influencing the plugging strength.
FIG. 1 shows the maximum expansion times and expansion rates of four temporary plugging agents, which are regularly compared, and it can be seen that the expansion times are reduced after the modified nanoparticles are added, because the nano SiO hydrophobically modified by the silane coupling agent 2 The surface is rich in double bonds, and can be connected to a skeleton structure of the temporary plugging agent through free radical polymerization reaction, so that the stability of a three-dimensional network structure of the temporary plugging agent is improved, and the water-absorbing expansion capacity of the temporary plugging agent is weakened. After the hydrophobic monomer is added, the hydration capability is weakened, the water absorption capability is reduced, and further the expansion rate and the expansion multiple are reduced, which is beneficial toAnd entering the deep part of the oil reservoir.
Table 2 compares the rules of four temporary plugging agents, and modified nano SiO is added 2 The complete degradation time of the formula is longer than that of the nano SiO without adding modification 2 The degradation rate is less than that of the nano SiO which is not added with modification 2 Due to the modified nano SiO 2 Can be connected on the polymer chain or used as a cross-linking agent to connect the polymer chain, thereby increasing the stability of the three-dimensional network structure of the temporary plugging agent and increasing the strength of the temporary plugging agent.
Comparing the plugging strength and the permeability after plugging removal of the four temporary plugging agents in the table 3, modified nano SiO is added 2 The plugging capability of the temporary plugging agent is far better than that of the temporary plugging agent without addition, and the permeability recovery rate is not influenced basically. This indicates the addition of modified nano-SiO 2 The plugging strength can be obviously increased, and on the basis, the adjustment and control of expansion multiple, expansion rate, degradation rate and the like can be realized by changing the addition of the hydrophobic monomer.
The test example is a rheological experiment of the functional self-degradation temporary plugging agent.
The viscoelasticity and yield stress of the transient plugging agent particles were measured using a plate system of an MCR301 rheometer. The specific experimental operating steps are as follows: placing the synthesized 4 different temporary plugging agent particles in formation water with the mineralization degree of 21276.87mg/L at 80 ℃ for water absorption and expansion, taking solid particles at the bottoms of test tubes of different samples at different times by using a rubber head dropper, placing the solid particles on a flat plate system, and keeping the wettability of the particles in the test process. The rheology of the temporary plugging agent particles was determined on an MCR301 rheometer using a dynamic oscillation method. The experimental temperature was set at 80 ℃. The shear rate was set at 7.74s -1 。
The experimental results show that: the elastic modulus of SD-TPA-1, SD-TPA-2, SD-TPA-3 and SD-TPA-4 is respectively 27Pa, 28Pa, 27Pa and 113Pa, wherein the elastic modulus of the temporary plugging agent particles SD-TPA-4 is the largest, and the elastic modulus is 113Pa.
FIG. 2 is a graph showing the comparison of the elastic modulus of the SD-TPA-1, SD-TPA-2 and SD-TPA-4 samples when they reach full expansion, and it can be seen that the elastic modulus of the SD-TPA-4 particles is the largest and the elastic modulus of the SD-TPA-1 particles is the smallest under the same oscillation frequency. This is because the strength of the particles of the temporary plugging agent is increased after the modified nanoparticles are added.
The embodiment is the result of the plugging and deblocking experiment of the multifunctional self-degradation temporary plugging agent.
And evaluating the plugging and unplugging performance of the self-degradation temporary plugging agent in a porous medium by adopting a rock core displacement experiment. A fractured core of 2.5cm × 10cm was placed in a core holder, and the confining pressure was set to 10MPa.
(1) Putting the core into an oven at 80 ℃ for drying for 24h, after completely drying, accurately weighing the dry weight of the core by a balance, and recording the dry weight as m 0 Then, accurately weighing the wet weight of the core by using the core saturated water for 24h, recording the wet weight as m, measuring the radius r and the length l of the core, and calculating the porosity of the core, wherein the calculation formula is as follows:
(2) A shim with a thickness of 0.03mm was placed on the core section, simulating a fracture of 0.03mm, the core was placed in a core holder and the instrument was connected as shown in fig. 3.
(3) Injecting formation water into the rock core at a constant flow rate of 0.5mL/min by using a constant flow pump, reading the pressure at the injection end, recording the pressure at the moment when the displacement pressure is stable, and calculating the permeability, wherein the calculation formula is as follows:
(4) Injecting a temporary plugging agent with the concentration of 0.5wt.% after complete expansion into the rock core at a constant flow rate of 0.5mL/min, wherein the injection amount is 0.5FV;
(5) After the temporary plugging agent is injected, injecting formation water into the rock core again at a constant flow rate of 0.5mL/min until the injection pressure is stable again; in the whole displacement process, recording the real-time change of pressure in the experimental process, and calculating the plugging rate, wherein the plugging rate calculation formula is as follows:
(6) Aging the core holder with the residual temporary plugging agent in an oven at 80 ℃ for 72h, injecting formation water again until the injection pressure is stable after the temporary plugging agent is completely degraded, testing the permeability recovery rate of the core, and calculating according to the following formula:
wherein phi 0 In terms of initial permeability, μm 2 Phi' is permeability after deblocking, mu m 2 。
TABLE 3 plugging and unplugging Performance
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A self-degradation temporary plugging agent is characterized in that: the raw materials comprise the following components in parts by weight based on 100 parts of the total mass: 19.4 to 20 portions of hydrophilic polymerization monomer, 0.5 to 1 portion of modified nano particle NP-, 0.1 to 0.5 portion of hydrophobic monomer, 0.12 to 0.2 portion of cross linker, 0.8 to 1 portion of initiator and the balance of water;
the hydrophilic polymerization monomer is acrylamide and/or acrylic acid;
the hydrophobic monomer is selected from one or more of hexadecyl dimethyl allyl ammonium chloride, dimethyl diallyl ammonium chloride and methacryloyloxyethyl trimethyl ammonium chloride;
the cross-linking agent is polyethylene glycol diacrylate;
the modified nano-particle NP-1 is nano SiO hydrophobically modified by silane coupling agent 2 。
2. The self-degrading temporary plugging agent according to claim 1, wherein: the hydrophilic polymerization monomer is a combination of acrylamide and acrylic acid, and the mass ratio of the acrylamide to the acrylic acid is 1:0.8-1.2.
3. The self-degrading temporary plugging agent according to claim 1, wherein: nano SiO hydrophobically modified by silane coupling agent 2 The degree of modification of (a) is 20 to 70%.
4. The self-degrading temporary plugging agent according to claim 1, wherein: the hydrophobic monomer is hexadecyl dimethyl allyl ammonium chloride.
5. The self-degrading temporary plugging agent according to claim 1, wherein: the initiator is selected from one or more of potassium persulfate, sodium thiosulfate, ammonium persulfate and sodium bisulfite.
6. The self-degrading temporary plugging agent according to claim 5, wherein: the initiator is ammonium persulfate.
7. The process for preparing a self-degradable temporary plugging agent according to any one of claims 1 to 6, wherein: the method comprises the following steps:
dissolving a hydrophilic polymerization monomer in water, and adjusting the solution to be alkalescent to obtain a hydrophilic polymerization monomer solution;
sequentially adding a hydrophobic monomer, the modified nano-particle NP-1 and a cross-linking agent into the hydrophilic polymerization monomer solution, and mixing and dissolving to obtain a mixed solution;
and adding an initiator into the mixed solution, and heating for reaction to obtain a product.
8. The method for preparing a self-degrading temporary plugging agent according to claim 7, wherein: adjusting the pH value of the hydrophilic polymerization monomer to 7.2 to 8, preferably 7.4 to 7.8, and more preferably 7.5;
preferably, the base is sodium hydroxide solution, the concentration of which is 10-20%, preferably 15%.
9. The method for preparing a self-degrading temporary plugging agent according to claim 7, wherein: the temperature of the polymerization reaction is 40-60 ℃, and the reaction time is 3-6h.
10. Use of the temporary plugging agent of any one of claims 1 to 6 in repeated fracturing of a reservoir;
preferably, the method for temporarily blocking the oil layer fracture by using the temporary blocking agent comprises the following steps: screening the temporary plugging agent particles with a set particle size range, uniformly dispersing the temporary plugging agent particles in water to form a stable suspension,
and injecting the suspension into an oil-water well, so that the temporary plugging agent particles enter a plugging target layer, continuously absorbing water and expanding to form a high-strength temporary plugging layer, and plugging cracks.
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| CN117720698A (en) * | 2023-12-14 | 2024-03-19 | 山东聚星石油科技有限公司 | Temperature-resistant salt-resistant nano-crosslinked polymer microsphere and preparation method and application thereof |
| CN117964854A (en) * | 2024-04-02 | 2024-05-03 | 西南石油大学 | Gel particle for profile control and water shutoff as well as preparation method and application thereof |
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| CN113185656A (en) * | 2021-04-15 | 2021-07-30 | 长江大学 | Temperature response type self-degradation temporary plugging agent and well repairing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117964854A (en) * | 2024-04-02 | 2024-05-03 | 西南石油大学 | Gel particle for profile control and water shutoff as well as preparation method and application thereof |
| CN117964854B (en) * | 2024-04-02 | 2024-05-28 | 西南石油大学 | Gel particle for profile control and water shutoff as well as preparation method and application thereof |
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