CN109134781B - Preparation method and application of dual-crosslinking micron-sized microsphere profile control agent - Google Patents
Preparation method and application of dual-crosslinking micron-sized microsphere profile control agent Download PDFInfo
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- CN109134781B CN109134781B CN201810761829.1A CN201810761829A CN109134781B CN 109134781 B CN109134781 B CN 109134781B CN 201810761829 A CN201810761829 A CN 201810761829A CN 109134781 B CN109134781 B CN 109134781B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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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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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
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Abstract
The invention discloses a preparation method of a double-crosslinking micron-sized microsphere profile control agent, which comprises the following steps: fully dissolving acrylamide monomers, stable cross-linking agents and unstable cross-linking agent regulators into deionized water, and slowly dripping the mixture into an oil solvent while stirring to obtain a miniemulsion; and adding an oxidant and a reducing agent into the miniemulsion to initiate polymerization to obtain the double-crosslinked micron-sized microsphere profile control agent. The invention also discloses application of the double-crosslinked micron-sized microsphere profile control agent in oil field profile control and flooding. The double-crosslinked micron-sized microsphere profile control and flooding agent prepared by the invention can effectively solve the problem of difficult injection caused by too fast expansion of the microspheres when meeting water, and achieves the purposes of plugging the dominant water flow channel of the oil reservoir, expanding swept volume and improving recovery ratio.
Description
Technical Field
The invention relates to a preparation method and application of a double-crosslinking micron-sized microsphere profile control agent, and belongs to the field of water shutoff and profile control of oil fields.
Background
Most oil fields in China adopt water injection development, stratum heterogeneity is aggravated due to long-term water injection development, oil wells are drained or flooded, the yield of the oil fields is seriously reduced, and oil increase is very limited by means of single injection and production regulation measures. Therefore, the water shutoff and profile control technology is widely applied to the oil field oil increasing and water reducing processes, wherein the polymer microsphere deep profile control technology is a novel enhanced oil recovery technology which is rapidly developed in recent years.
The initial particle size of the polymer microspheres is nano-micron grade, the polymer microspheres are dispersed in an aqueous solution, under the action of formation water and temperature, the microspheres expand in volume to form a larger elastomer, and the flow direction of subsequently injected water can be changed, so that the swept volume is enlarged, and the recovery ratio is improved.
Because the microspheres have small size and large specific surface area, the microspheres can expand rapidly when meeting water, can expand for tens of times within several hours, and are difficult to enter the deep part of the stratum to realize deep profile control. Aiming at the problem, the invention aims to prepare the double-crosslinking agent micron-sized microsphere profile control agent by adopting the combined action of the stable crosslinking agent and the unstable crosslinking agent, so that the microspheres hardly expand in low-temperature environments such as liquid preparation, injection and the like, and after entering the deep part of a stratum, the unstable crosslinking agent is dissociated to lose efficacy under the action of high temperature of the stratum, the microspheres are rapidly expanded, and the purposes of deep profile control, expanded swept volume and improved recovery ratio are achieved.
Disclosure of Invention
The invention aims to provide a preparation method of a double-crosslinking micron-sized microsphere profile control agent, which is used for solving the problems that the existing polymer microspheres have high swelling speed and are difficult to realize deep profile control operation.
On the other hand, the invention also provides application of the double cross-linked micron-sized microsphere profile control agent prepared by the method in oil field profile control and flooding.
The invention provides a preparation method of a double-crosslinking micron-sized microsphere profile control agent, which comprises the following steps:
(1) according to the mass ratio, acrylamide monomers accounting for 10-20% of the total reaction system, a stable cross-linking agent accounting for 0.2-0.5%, an unstable cross-linking agent accounting for 0.2-0.5% and a pH regulator accounting for 1.0-5.0% are fully dissolved in deionized water;
(2) slowly dripping the solution into an oil solvent which accounts for 20-30% of the total reaction system under the stirring condition of 3000-10000 r/min to obtain miniemulsion;
(3) and (2) adding an oxidant accounting for 0.02-0.05% of the total reaction system and a reducing agent accounting for 0.02-0.05% of the total reaction system into the miniemulsion at the temperature of 25-35 ℃ to initiate polymerization, continuously keeping the reaction for 4-5 hours, and cooling to room temperature after the reaction is finished to obtain the double-crosslinked micron-sized microsphere profile control agent.
According to the preparation method of the double-crosslinking micron-sized microsphere profile control agent, the acrylamide monomer is one or two of acrylamide and 2-acrylamide-2-methylpropanesulfonic acid.
According to the preparation method of the double-crosslinking micron-sized microsphere profile control agent, the stable crosslinking agent is N, N-methylene bisacrylamide serving as a crosslinking agent.
According to the preparation method of the double-crosslinking micron-sized microsphere profile control agent, the unstable crosslinking agent is one or two of polyethylene glycol diacrylate and polyoxyethylene acrylate.
According to the preparation method of the double-crosslinking micron-sized microsphere profile control agent, the pH regulator is NaOH, and the pH of an aqueous solution is regulated to 7-8.
According to the preparation method of the double-crosslinking micron-sized microsphere profile control agent, the oil solvent is one or more of Span-80, Span-83, Tween-80 and OP-10.
According to the preparation method of the double-crosslinking micron-sized microsphere profile control agent, the oxidant is one or more of ammonium persulfate, sodium persulfate and potassium persulfate.
According to the preparation method of the double-crosslinking micron-sized microsphere profile control agent, the reducing agent is one or two of sodium bisulfite and sodium metabisulfite.
According to the preparation method of the double-crosslinking micron-sized microsphere profile control agent, the particle size distribution range of the prepared double-crosslinking micron-sized microsphere profile control agent is 10-50 mu m.
According to the preparation method of the double-crosslinking micron-sized microsphere profile control agent, the swelling multiple of the prepared double-crosslinking micron-sized microsphere profile control agent in one day is less than or equal to 15, and the swelling multiple in 10 days is more than or equal to 20.
On the other hand, the dual cross-linked micron-sized microsphere profile control agent prepared by the method disclosed by the invention is applied to profile control and flooding of an oil field. When in use, the dual cross-linked micron-sized microsphere profile control agent can be directly prepared by adopting clear water or produced water.
The double-crosslinking micron-sized microsphere profile control and flooding agent prepared by the method can effectively solve the problem of difficult injection caused by too fast expansion of the microspheres when meeting water, and achieves the purposes of plugging the dominant water flow channel of the oil reservoir, expanding swept volume and improving recovery ratio.
Drawings
FIG. 1 is a microsphere particle size distribution diagram of a dual cross-linked micron-sized microsphere profile control agent prepared by the method of the present invention.
FIG. 2 is a graph showing the relationship between the swelling factor and time of a dual cross-linked micron-sized microsphere profile control agent prepared by the method of the present invention.
Detailed Description
In order to better understand the technical solutions, the technical solutions of the present application are described in detail with specific embodiments below, and it should be understood that the specific features in the embodiments and examples of the present application are detailed descriptions of the technical solutions of the present application, but not limitations of the technical solutions of the present application, and the technical features in the embodiments and examples of the present application may be combined with each other without conflict.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, 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. If there is a conflict, the present specification will control.
Example 1
Fully dissolving acrylamide accounting for 10 percent of the total reaction system, N-methylene-bisacrylamide accounting for 0.2 percent of the total reaction system, polyethylene glycol diacrylate accounting for 0.2 percent of the total reaction system and NaOH accounting for 1.0 percent of the total reaction system in deionized water; slowly dropwise adding the solution into Span80 accounting for 20% of the total reaction system under the stirring condition of 3000 r/min to obtain miniemulsion; and (3) adding ammonium persulfate accounting for 0.02 percent of the total reaction system and 0.02 percent of sodium bisulfite into the miniemulsion at the temperature of 25 ℃ to initiate polymerization, continuously keeping the reaction for 4 hours, and cooling to room temperature after the reaction is finished to obtain the double-crosslinked micron-sized microsphere profile control agent.
The median particle size of the double-crosslinking micron-sized microsphere profile control agent is 11 μm.
Example 2
Fully dissolving acrylamide monomers (acrylamide: 2-acrylamide-2-methylpropanesulfonic acid: 1) accounting for 20% of the total reaction system, 0.5% of N, N-methylene bisacrylamide, 0.5% of polyethylene glycol diacrylate and 5.0% of NaOH in deionized water; slowly dripping the solution into Tween-80 accounting for 30 percent of the total reaction system under the stirring condition of 3000 revolutions per minute to obtain miniemulsion; and (3) adding sodium persulfate accounting for 0.05 percent of the total reaction system and 0.05 percent of sodium metabisulfite into the miniemulsion at the temperature of 25 ℃ to initiate polymerization, continuously keeping the reaction for 4 hours, and cooling to room temperature after the reaction is finished to obtain the double-crosslinked micron-sized microsphere profile control agent.
The median particle size of the double-crosslinking micron-sized microsphere profile control agent is 48 mu m.
Example 3
Fully dissolving 2-acrylamide-2-methylpropanesulfonic acid accounting for 15% of the total reaction system, 0.2% of N, N-methylene bisacrylamide, 0.2% of unstable crosslinking agent (polyoxyethylene acrylate: polyethylene glycol diacrylate ═ 1:1) and 2.0% of NaOH in deionized water; slowly dripping the solution into OP-10 accounting for 20 percent of the total reaction system under the stirring condition of 3000 revolutions per minute to obtain miniemulsion; and (3) adding potassium persulfate accounting for 0.03% of the total reaction system and 0.03% of sodium bisulfite into the miniemulsion at 25 ℃ to initiate polymerization, continuously keeping the reaction for 4 hours, and cooling to room temperature after the reaction is finished to obtain the double-crosslinked micron-sized microsphere profile control agent.
The median particle size of the double-crosslinking micron-sized microsphere profile control agent is 34 mu m.
Example 4
Fully dissolving acrylamide accounting for 20% of the total reaction system, N-methylene-bisacrylamide accounting for 0.3%, polyethylene glycol diacrylate accounting for 0.3% and a pH regulator accounting for 1.0% in deionized water; slowly dropwise adding the solution into an oil solvent (Span-80: Span-83 ═ 1:1) accounting for 20% of the total reaction system under the stirring condition of 3000 revolutions per minute to obtain a miniemulsion; and (3) adding sodium persulfate accounting for 0.03 percent of the total reaction system and 0.03 percent of sodium metabisulfite into the miniemulsion at the temperature of 25 ℃ to initiate polymerization, continuously keeping the reaction for 4 hours, and cooling to room temperature after the reaction is finished to obtain the double-crosslinked micron-sized microsphere profile control agent.
The median particle size of the double-crosslinking micron-sized microsphere profile control agent is 21 mu m.
Microsphere profile control agent detection
The invention uses a laser particle size analyzer (Zetasizer, Malvern) to detect the particle size of the dual cross-linked micron-sized microsphere profile control agent prepared in example 1, the microspheres are fully dispersed in deionized water by ultrasound, a small amount of microsphere aqueous solution is extracted by a dropper and added to the laser particle size analyzer, the particle size and distribution of the microspheres are measured, the distribution is shown in figure 1, the particle size distribution of the microspheres is seen from figure 1 to be centralized, and the initial median particle size in the aqueous solution is about 17 μm.
The swelling performance of the double-crosslinking micron-sized microsphere profile control agent prepared in example 1 is detected by a laser particle sizer (Zetasizer, Malvern), the dispersion system is placed at a constant temperature of 90 ℃, and the double-crosslinking micron-sized microsphere profile control agent is respectively placed in an aqueous dispersion system with NaCl concentration of 0mg/L and 5000 mg/L. And measuring the median particle diameters of the double-crosslinked polymer microspheres at 0h, 24h, 3d, 7d and 10d by using a laser particle size analyzer, and calculating the volume swelling times. As shown in FIG. 2, when the NaCl concentration was 0mg/L, the swelling ratio was 6.2 in 1 day and 30 in 10 days; when the NaCl concentration was 5000mg/L, the swelling factor was 5.5 in 1 day and 27.6 in 10 days.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention. It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (2)
1. A preparation method of a double-crosslinked micron-sized microsphere profile control agent comprises the following steps:
(1) according to the mass ratio, acrylamide monomers accounting for 10-20% of the total reaction system, 0.2-0.5% of stable cross-linking agent, 0.1% of polyoxyethylene acrylate, 0.1% of polyethylene glycol diacrylate and 1.0-5.0% of pH regulator are fully dissolved in deionized water;
(2) slowly dripping the solution into an oil solvent which accounts for 20-30% of the total reaction system under the stirring condition of 3000-10000 r/min to obtain miniemulsion;
(3) adding an oxidant accounting for 0.02-0.05% of the total reaction system and a reducing agent accounting for 0.02-0.05% of the total reaction system into the miniemulsion at the temperature of 25-35 ℃ to initiate polymerization, continuously keeping the reaction for 4-5 hours, and cooling to room temperature after the reaction is finished to obtain the double-crosslinked micron-sized microsphere profile control agent;
the acrylamide monomer is one or two of acrylamide or 2-acrylamide-2-methylpropanesulfonic acid;
the stable cross-linking agent is a cross-linking agent N, N-methylene bisacrylamide;
the pH regulator is NaOH, and the pH of the aqueous solution is regulated to 7-8;
the oil solvent is one or more of Span-80, Span-83, Tween-80 or OP-10;
the oxidant is one or more of ammonium persulfate, sodium persulfate or potassium persulfate;
the reducing agent is one or two of sodium bisulfite and sodium metabisulfite;
the particle size distribution range of the double-crosslinking micron-sized microsphere profile control agent is 10-50 microns, the swelling multiple per day is less than or equal to 15, and the swelling multiple per 10 days is more than or equal to 20.
2. Use of a dual cross-linked micron-sized microsphere profile control agent prepared by the method of claim 1 in oilfield profile control.
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| CN110776608B (en) * | 2019-11-13 | 2021-02-26 | 西南石油大学 | Hydroxylated multidimensional nanomaterial hybrid dispersion glue and application thereof |
| CN112169719B (en) * | 2020-09-23 | 2022-03-15 | 中国石油大学(北京) | AM/PF microsphere with multiple cross-linked structure and preparation method and application thereof |
| CN112480891B (en) * | 2020-11-30 | 2021-08-24 | 三智鼎业(北京)能源技术有限公司 | Fracture-cavity type oil reservoir flow channel profile control agent system and preparation method thereof |
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| US20080021171A1 (en) * | 2004-03-22 | 2008-01-24 | Steinar Pedersen | Storage Stable Polymer-Oligomer Particles And Their Use In Seed Polymerisation |
| CN102850488A (en) * | 2012-09-25 | 2013-01-02 | 西南石油大学 | Low-density double expansion gel particle |
| CN103073679A (en) * | 2012-12-25 | 2013-05-01 | 北京希涛技术开发有限公司 | Method for producing polyacrylamide microsphere water shutoff agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20080021171A1 (en) * | 2004-03-22 | 2008-01-24 | Steinar Pedersen | Storage Stable Polymer-Oligomer Particles And Their Use In Seed Polymerisation |
| CN102850488A (en) * | 2012-09-25 | 2013-01-02 | 西南石油大学 | Low-density double expansion gel particle |
| CN103073679A (en) * | 2012-12-25 | 2013-05-01 | 北京希涛技术开发有限公司 | Method for producing polyacrylamide microsphere water shutoff agent |
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