CN111704898A - Temporary plugging agent for shallow well and preparation method thereof - Google Patents
Temporary plugging agent for shallow well and preparation method thereof Download PDFInfo
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- CN111704898A CN111704898A CN202010494246.4A CN202010494246A CN111704898A CN 111704898 A CN111704898 A CN 111704898A CN 202010494246 A CN202010494246 A CN 202010494246A CN 111704898 A CN111704898 A CN 111704898A
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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
- C09K8/50—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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/516—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls characterised by their form or by the form of their components, e.g. encapsulated material
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Abstract
The invention provides a temporary plugging agent for a shallow well and a preparation method thereof, wherein the temporary plugging agent comprises the following components in parts by weight: 15-20% of temperature-sensitive monomer, 1-10% of ionic monomer, 0.1-1% of cross-linking agent, 20-50% of water, 1-3% of dispersing agent, 20-60% of oil phase and 0.2-0.8% of water-soluble initiator. The construction process is simple, and can be applied to temporary plugging fracturing and temporary plugging acidification. The temporary plugging agent provided by the invention enters a stratum along with injected water, and due to the temperature effect of the temperature-sensitive monomer N-isopropyl acrylamide, the temporary plugging agent has a high water absorption expansion rate and a large expansion multiple at a critical temperature of below 45 ℃, and can preferentially enter a dominant channel to effectively plug the dominant channel. When the temperature is higher than the critical temperature, the temperature-sensitive monomer is changed into a hydrophobic state from a hydrophilic state, and the volume of the temporary plugging agent is shrunk. The temporary plugging agent provided by the invention can intelligently regulate and control the water absorption expansion times along with the temperature, and can expand at low temperature and contract at high temperature. The invention improves the production efficiency of the temporary plugging agent and correspondingly reduces the production cost.
Description
Technical Field
The invention belongs to the field of oilfield chemistry, and particularly relates to a temporary plugging agent for a shallow well and a preparation method thereof.
Background
In the process of low-permeability reservoir transformation, acidification is a main technological measure for increasing production and injection, but after multiple times of acidification, the problem of oil increase and great increase of water content of an oil well occurs. Through analysis, the main reason is that a large amount of acid liquor enters the oil layer of the high-permeability zone in the acidification process, but rarely enters the low-permeability zone or the blocked and polluted oil outlet pore channel, so that the physical property of the oil layer of the high-permeability zone is improved, the physical property of the low-permeability oil layer cannot be correspondingly improved, and the interlayer heterogeneity is intensified.
And further to the complication that the water discharge from the relatively high permeability layer is severe, while the oil from the relatively low permeability layer is seldom used. Aiming at the problem, a thought of temporary blocking acidification is provided, namely a high-permeability stratum is blocked by a temporary blocking agent, and acid liquor is forced to flow to a low-permeability stratum, so that more strata are acidified by using a certain volume of acid liquor. After the acidification operation is finished, the temporary plugging agents of the closed reservoirs are automatically degraded and disappear, and the oil-gas reservoir is opened again for production. However, most of the existing acidified temporary plugging agents are acid-soluble solid particles, and field practice shows that the temporary plugging agents are brittle in property, difficult to deform and poor in plugging effect.
In addition, the construction process of acidizing and plug removal is complex, the cost is high, and secondary pollution is easily caused to a reservoir stratum, so that the application in the field is limited. Therefore, it is needed to develop a novel temporary plugging material to reduce the damage of the temporary plugging agent to the reservoir and improve the temporary plugging acidification reconstruction effect.
Disclosure of Invention
The temporary plugging agent for the shallow well and the preparation method thereof are simple in construction process, and the water absorption expansion multiple of the temporary plugging agent can be intelligently regulated and controlled along with temperature, expand at low temperature and contract at high temperature. The invention improves the production efficiency of the temporary plugging agent and correspondingly reduces the production cost.
The technical scheme adopted by the invention is as follows:
a temporary plugging agent for shallow wells comprises the following components in parts by weight:
15-20% of temperature-sensitive monomer
1-10% of ionic monomer
0.1 to 1 percent of cross-linking agent
20 to 50 percent of water
1 to 3 percent of dispersant
20 to 60 percent of oil phase
0.2 to 0.8 percent of water-soluble initiator.
The temperature-sensitive monomer is N-isopropyl acrylamide.
The ionic monomer is acrylic acid, diethylaminoethyl methacrylate or glycidyl methacrylate.
The cross-linking agent is N, N methylene bisacrylamide.
The oil phase is one or two of cyclohexane, kerosene, white oil and vegetable oil.
The water-soluble initiator is one of ammonium persulfate, potassium persulfate, sodium thiosulfate, ammonium persulfate and sodium bisulfite.
A preparation method of a temporary plugging agent for a shallow well comprises the following preparation steps: weighing 15-20% of temperature-sensitive monomer, 1-10% of ionic monomer and 0.1-1% of cross-linking agent in sequence, adding into 20-50% of distilled water, and mixing uniformly to form a water phase; weighing 1-3% of dispersant, and dissolving in 20-60% of oil phase to form oil phase; mixing and dispersing the water phase and the oil phase to form a stable dispersion system; and transferring the dispersion system into a three-neck flask, introducing nitrogen to remove oxygen for 1h, adding 0.2-0.8% of water-soluble initiator, and initiating reaction at 30-55 ℃ to obtain a primary temporary plugging agent product.
The water phase and the oil phase are mixed and dispersed by ultrasonic to form a stable dispersion system.
After the temporary plugging agent primary product is obtained, purifying the primary product by using ethanol, and drying to obtain the powdery temporary plugging agent.
The invention has the beneficial effects that:
the temporary plugging agent provided by the invention enters a stratum along with injected water, and due to the temperature effect of the temperature-sensitive monomer N-isopropyl acrylamide, the temporary plugging agent has a high water absorption expansion rate and a large expansion multiple at a critical temperature of below 45 ℃, and can preferentially enter a dominant channel to effectively plug the dominant channel. When the temperature is higher than the critical temperature, the temperature-sensitive monomer is changed into a hydrophobic state from a hydrophilic state, and the volume of the temporary plugging agent is shrunk.
The construction process is simple, and the water absorption expansion multiple of the temporary plugging agent can be intelligently regulated and controlled along with the temperature, and the temporary plugging agent can expand at low temperature and contract at high temperature.
The invention improves the production efficiency of the temporary plugging agent and correspondingly reduces the production cost.
Detailed Description
Example 1:
the temporary plugging agent for the shallow well and the preparation method thereof are simple in construction process, and the water absorption expansion multiple of the temporary plugging agent can be intelligently regulated and controlled along with temperature, expand at low temperature and contract at high temperature. The invention improves the production efficiency of the temporary plugging agent and correspondingly reduces the production cost.
A temporary plugging agent for shallow wells comprises the following components in parts by weight:
15-20% of temperature-sensitive monomer
1-10% of ionic monomer
0.1 to 1 percent of cross-linking agent
20 to 50 percent of water
1 to 3 percent of dispersant
20 to 60 percent of oil phase
0.2 to 0.8 percent of water-soluble initiator.
Preferably, the temperature-sensitive monomer is N-isopropylacrylamide.
Preferably, the ionic monomer is acrylic acid, diethylaminoethyl methacrylate or glycidyl methacrylate.
Preferably, the crosslinking agent is N, N methylene bisacrylamide.
Preferably, the oil phase is one or two of cyclohexane, kerosene, white oil and vegetable oil.
Preferably, the water-soluble initiator is one of ammonium persulfate, potassium persulfate, sodium thiosulfate, ammonium persulfate and sodium bisulfite.
Preferably, the dispersant is one of Span80, Span60, Span20 and Span 40.
The temporary plugging agent provided by the invention enters a stratum along with injected water, and due to the temperature effect of the temperature-sensitive monomer N-isopropyl acrylamide, the temporary plugging agent has a high water absorption expansion rate and a large expansion multiple at a critical temperature of below 45 ℃, and can preferentially enter a dominant channel to effectively plug the dominant channel. When the temperature is higher than the critical temperature, the temperature-sensitive monomer is changed into a hydrophobic state from a hydrophilic state, and the volume of the temporary plugging agent is shrunk. The invention has the advantage of self-regulation of temperature and can simplify the subsequent blockage removal process. The invention can improve the production efficiency of the temporary plugging agent and correspondingly reduce the production cost.
Example 2:
based on the embodiment 1, the temporary plugging agent for shallow wells in the embodiment is composed of the following components in parts by weight:
17 percent of temperature-sensitive monomer
1% of ionic monomer
0.5 percent of cross-linking agent
2 percent of dispersant
46 percent of oil phase
0.5 percent of water-soluble initiator
33% of water.
In this embodiment, preferably, the temperature-sensitive monomer is N-isopropylacrylamide, the ionic monomer is acrylic acid, the crosslinking agent is N, N-methylene bisacrylamide, the oil phase is cyclohexane, the water-soluble initiator is ammonium persulfate, and the dispersant is Span 80.
A preparation method of the temporary plugging agent for the shallow well comprises the following steps:
weighing a main monomer, an ionic monomer and a cross-linking agent in sequence according to a proportion, adding the main monomer, the ionic monomer and the cross-linking agent into distilled water weighed according to the proportion, and uniformly mixing to form a water phase; weighing the dispersing agent according to the proportion, and dissolving the dispersing agent in the oil phase weighed according to the proportion to form an oil phase; mixing and dispersing the water phase and the oil phase to form a stable dispersion system; and transferring the dispersion system into a three-neck flask, introducing nitrogen to remove oxygen for 1h, adding a water-soluble initiator in proportion, and initiating reaction at 30-55 ℃ to obtain a primary temporary plugging agent product. The water phase and the oil phase are mixed and dispersed by ultrasonic to form a stable dispersion system. After the temporary plugging agent primary product is obtained, purifying the primary product by using ethanol, and drying to obtain the powdery temporary plugging agent.
The temporary plugging agent provided by the invention can intelligently regulate and control the water absorption expansion times along with the temperature, and can expand at low temperature and contract at high temperature. In addition, the construction process is simple, and the method can be applied to temporary plugging fracturing and temporary plugging acidification. The temporary plugging agent provided by the invention enters a stratum along with injected water, and due to the temperature effect of N-isopropyl acrylamide, the temporary plugging agent has a high water absorption expansion rate and a large expansion multiple at a critical temperature of below 45 ℃, can preferentially enter a dominant channel to effectively plug the dominant channel. When the temperature is higher than the critical temperature, the N-isopropyl acrylamide is changed from a hydrophilic state to a hydrophobic state, and the volume of the temporary plugging agent is shrunk.
Example 3:
based on embodiment 1, this embodiment provides a temporary plugging agent for shallow wells, which is composed of the following components in parts by weight:
17.5 percent of temperature-sensitive monomer
4% of ionic monomer
0.5 percent of cross-linking agent
1.7 percent of dispersant
Oil phase 43%
0.3 percent of water-soluble initiator
33% of water.
In this embodiment, preferably, the temperature-sensitive monomer is N-isopropyl acrylamide, the ionic monomer is glycidyl methacrylate, and the crosslinking agent is N, N methylene bisacrylamide. The oil phase is vegetable oil, the water-soluble initiator is ammonium persulfate, and the dispersing agent is Span 40.
A preparation method of the temporary plugging agent for the shallow well comprises the following steps:
weighing a main monomer N-isopropyl acrylamide, an ionic monomer and a cross-linking agent in sequence according to a proportion, adding the main monomer N-isopropyl acrylamide, the ionic monomer and the cross-linking agent into the distilled water weighed according to the proportion, and uniformly mixing to form a water phase; weighing the dispersing agent according to the proportion, and dissolving the dispersing agent in the oil phase weighed according to the proportion to form an oil phase; mixing and dispersing the water phase and the oil phase to form a stable dispersion system; and transferring the dispersion system into a three-neck flask, introducing nitrogen to remove oxygen for 1h, adding a water-soluble initiator in proportion, and initiating reaction at 30-55 ℃ to obtain a primary temporary plugging agent product. After the temporary plugging agent primary product is obtained, purifying the primary product by using ethanol, and drying to obtain the powdery temporary plugging agent. The temporary plugging agent provided by the invention enters a stratum along with injected water, and due to the temperature effect of the temperature-sensitive monomer N-isopropyl acrylamide, the temporary plugging agent has a high water absorption expansion rate and a large expansion multiple at a critical temperature of below 45 ℃, and can preferentially enter a dominant channel to effectively plug the dominant channel. When the temperature is higher than the critical temperature, the temperature-sensitive monomer is changed into a hydrophobic state from a hydrophilic state, and the volume of the temporary plugging agent is shrunk. The temporary plugging agent provided by the invention can intelligently regulate and control the water absorption expansion times along with the temperature, and can expand at low temperature and contract at high temperature. In addition, the construction process is simple, and the method can be applied to temporary plugging fracturing and temporary plugging acidification.
Example 4:
based on embodiment 1, this embodiment provides a temporary plugging agent for shallow wells, which is composed of the following components in parts by weight:
19 percent of temperature-sensitive monomer
Ionic monomer 7.6%
0.9 percent of cross-linking agent
2 percent of dispersant
Oil phase 42%
0.5 percent of water-soluble initiator
28 percent of water.
In this embodiment, preferably, the temperature-sensitive monomer is N-isopropylacrylamide,
preferably, the ionic monomer is glycidyl methacrylate.
Preferably, the crosslinking agent is N, N methylene bisacrylamide.
Preferably, the oil phase is cyclohexane.
Preferably, the water-soluble initiator is ammonium persulfate.
Preferably, the dispersant is Span 80.
The temporary plugging agent provided by the invention enters a stratum along with injected water, and due to the temperature effect of the temperature-sensitive monomer N-isopropyl acrylamide, the temporary plugging agent has a high water absorption expansion rate and a large expansion multiple at a critical temperature of below 45 ℃, and can preferentially enter a dominant channel to effectively plug the dominant channel. When the temperature is higher than the critical temperature, the temperature-sensitive monomer is changed into a hydrophobic state from a hydrophilic state, and the volume of the temporary plugging agent is shrunk.
The temporary plugging agent provided by the invention can intelligently regulate and control the water absorption expansion times along with the temperature, and can expand at low temperature and contract at high temperature. In addition, the construction process is simple, and the method can be applied to temporary plugging fracturing and temporary plugging acidification.
Example 5:
based on example 1, this embodiment provides a preparation method of a temporary plugging agent for shallow wells, which includes the following steps: weighing a main monomer, an ionic monomer and a cross-linking agent in sequence according to a proportion, adding the main monomer, the ionic monomer and the cross-linking agent into distilled water weighed according to the proportion, and uniformly mixing to form a water phase; weighing the dispersing agent according to the proportion, and dissolving the dispersing agent in the oil phase weighed according to the proportion to form an oil phase; mixing and dispersing the water phase and the oil phase to form a stable dispersion system; and transferring the dispersion system into a three-neck flask, introducing nitrogen to remove oxygen for 1h, adding a water-soluble initiator in proportion, and initiating reaction at 30-55 ℃ to obtain a primary temporary plugging agent product.
The water phase and the oil phase are mixed and dispersed by ultrasonic to form a stable dispersion system.
After the temporary plugging agent primary product is obtained, purifying the primary product by using ethanol, and drying to obtain the powdery temporary plugging agent.
The invention adopts an inverse suspension polymerization method, which is characterized in that: the temporary plugging agent provided by the invention enters a stratum along with injected water, and due to the temperature effect of a temperature-sensitive monomer N-isopropyl acrylamide, the temporary plugging agent has a high water absorption expansion rate and a large expansion multiple at a critical temperature of below 45 ℃, can preferentially enter a dominant channel to effectively plug the dominant channel. When the temperature is higher than the critical temperature, the temperature-sensitive monomer is changed into a hydrophobic state from a hydrophilic state, and the volume of the temporary plugging agent is shrunk. The invention has the advantage of self-regulation of temperature and can simplify the subsequent blockage removal process. The invention can improve the production efficiency of the temporary plugging agent and correspondingly reduce the production cost.
In this embodiment, a preparation process of the temporary plugging agent for shallow wells is as follows: 16g of N-isopropylacrylamide, 3g of sodium acrylate and 0.5g of N, N-methylenebisacrylamide were weighed in this order and dissolved in 35ml of deionized water to form an aqueous phase. Span 802 g was weighed out and dissolved in 43ml cyclohexane to form an oil phase. Mixing the water phase and the oil phase, ultrasonically treating to form a homogeneous system, transferring the mixed homogeneous system into a three-neck flask, introducing nitrogen to remove oxygen for 1h, adding 0.5g of ammonium persulfate, and initiating reaction at 30-55 ℃ for 3 h to obtain a primary product. Purifying the primary product and drying. With a median particle size of about 100 microns.
Swelling property of temporary plugging agent at different temperatures
Preparing a temporary plugging agent dispersion system with the mass fraction of 0.3% by using deionized water, aging the dispersion system at different temperatures (20 ℃, 30 ℃, 40 ℃, 50 ℃ and 60 ℃) for 24 hours, and measuring the water absorption expansion times of the temporary plugging agent at the aging temperatures. The results are shown in Table 1.
TABLE 1 Effect of aging temperature on temporary plugging agent swelling Properties
| Temperature (. degree.C.) | 20 | 30 | 40 | 50 | 60 |
| Expansion factor | 3.0 | 2.7 | 2.5 | 2 | 0.1 |
From Table 1, the swelling times of the temporary plugging agents gradually decreased with increasing temperature, and swelling behavior was exhibited at 50 ℃ or lower. When the temperature exceeds 50 ℃, the temporary plugging agent has deswelling behavior.
The temporary plugging agent provided by the invention enters a stratum along with injected water, and due to the temperature effect of the temperature-sensitive monomer N-isopropyl acrylamide, the temporary plugging agent has a high water absorption expansion rate and a large expansion multiple at a critical temperature of below 45 ℃, and can preferentially enter a dominant channel to effectively plug the dominant channel. When the temperature is higher than the critical temperature, the temperature-sensitive monomer is changed into a hydrophobic state from a hydrophilic state, and the volume of the temporary plugging agent is shrunk.
The temporary plugging agent provided by the invention can intelligently regulate and control the water absorption expansion times along with the temperature, and can expand at low temperature and contract at high temperature. In addition, the construction process is simple, and the method can be applied to temporary plugging fracturing and temporary plugging acidification.
The above examples are only specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution of the present invention and its inventive concept within the technical scope of the present invention. Reagents and processes for preparing the same, which are not described in detail in the present invention, are prior art and will not be further described in the present invention.
Claims (9)
1. A temporary plugging agent for shallow wells is characterized in that: the composition comprises the following components in percentage by weight:
15-20% of temperature-sensitive monomer
1-10% of ionic monomer
0.1 to 1 percent of cross-linking agent
20 to 50 percent of water
1 to 3 percent of dispersant
20 to 60 percent of oil phase
0.2 to 0.8 percent of water-soluble initiator.
2. The temporary plugging agent for shallow wells according to claim 1, wherein: the temperature-sensitive monomer is N-isopropyl acrylamide.
3. The temporary plugging agent for shallow wells according to claim 1, wherein: the ionic monomer is acrylic acid, diethylaminoethyl methacrylate or glycidyl methacrylate.
4. The temporary plugging agent for shallow wells according to claim 1, wherein: the cross-linking agent is N, N methylene bisacrylamide.
5. The temporary plugging agent for shallow wells according to claim 1, wherein: the oil phase is one or two of cyclohexane, kerosene, white oil and vegetable oil.
6. The temporary plugging agent for shallow wells according to claim 1, wherein: the water-soluble initiator is one of ammonium persulfate, potassium persulfate, sodium thiosulfate, ammonium persulfate and sodium bisulfite.
7. The method for preparing the temporary plugging agent for the shallow well according to any one of claims 1 to 6, wherein: the preparation steps are as follows: weighing 15-20% of temperature-sensitive monomer, 1-10% of ionic monomer and 0.1-1% of cross-linking agent in sequence, adding into 20-50% of distilled water, and mixing uniformly to form a water phase; weighing 1-3% of dispersant, and dissolving in 20-60% of oil phase to form oil phase; mixing and dispersing the water phase and the oil phase to form a stable dispersion system; and transferring the dispersion system into a three-neck flask, introducing nitrogen to remove oxygen for 1h, adding 0.2-0.8% of water-soluble initiator, and initiating reaction at 30-55 ℃ to obtain a primary temporary plugging agent product.
8. The method for preparing the temporary plugging agent for the shallow well according to claim 7, wherein the method comprises the following steps: the water phase and the oil phase are mixed and dispersed by ultrasonic to form a stable dispersion system.
9. The method for preparing the temporary plugging agent for the shallow well according to claim 7, wherein the method comprises the following steps: after the temporary plugging agent primary product is obtained, purifying the primary product by using ethanol, and drying to obtain the powdery temporary plugging agent.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140076565A1 (en) * | 2012-09-18 | 2014-03-20 | Halliburton Energy Services, Inc. | Thermally-Activated, High Temperature Particulate Suspending Agents and Methods Relating Thereto |
| CN104449613A (en) * | 2014-10-31 | 2015-03-25 | 中国石油化工集团公司 | Water-absorbent resin temporary plugging agent and preparation method thereof |
| CN108329420A (en) * | 2017-01-17 | 2018-07-27 | 中国石油化工股份有限公司 | Low-tension polymer microballoon profile control agent and its preparation method and application |
| CN110819325A (en) * | 2019-10-24 | 2020-02-21 | 北京大德广源石油技术服务有限公司 | Repeated fracturing temporary plugging agent and preparation method thereof |
-
2020
- 2020-06-03 CN CN202010494246.4A patent/CN111704898A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140076565A1 (en) * | 2012-09-18 | 2014-03-20 | Halliburton Energy Services, Inc. | Thermally-Activated, High Temperature Particulate Suspending Agents and Methods Relating Thereto |
| CN104449613A (en) * | 2014-10-31 | 2015-03-25 | 中国石油化工集团公司 | Water-absorbent resin temporary plugging agent and preparation method thereof |
| CN108329420A (en) * | 2017-01-17 | 2018-07-27 | 中国石油化工股份有限公司 | Low-tension polymer microballoon profile control agent and its preparation method and application |
| CN110819325A (en) * | 2019-10-24 | 2020-02-21 | 北京大德广源石油技术服务有限公司 | Repeated fracturing temporary plugging agent and preparation method thereof |
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Application publication date: 20200925 |