AU2020103311A4 - Hollow polymer microsphere profile control agent and preparation method thereof - Google Patents
Hollow polymer microsphere profile control agent and preparation method thereof Download PDFInfo
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- AU2020103311A4 AU2020103311A4 AU2020103311A AU2020103311A AU2020103311A4 AU 2020103311 A4 AU2020103311 A4 AU 2020103311A4 AU 2020103311 A AU2020103311 A AU 2020103311A AU 2020103311 A AU2020103311 A AU 2020103311A AU 2020103311 A4 AU2020103311 A4 AU 2020103311A4
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/16—Interfacial polymerisation
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- C—CHEMISTRY; METALLURGY
- 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
- C08F2/00—Processes of polymerisation
- C08F2/32—Polymerisation in water-in-oil emulsions
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- C—CHEMISTRY; METALLURGY
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C—CHEMISTRY; METALLURGY
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of amides or imides
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- 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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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- C—CHEMISTRY; METALLURGY
- 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
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- 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
- C08F220/56—Acrylamide; Methacrylamide
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- Oil, Petroleum & Natural Gas (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
The present invention belongs to the field of oil recovery enhancement of petroleum
engineering, and particularly relates to a hollow polymer microsphere profile control agent and a
preparation method thereof. Hollow polymer microspheres are prepared by using acrylamide and
ionic monomers as functional monomers and hydrophobic monomers with double unsaturated
bonds as cross-linking agents through water-in-oil-in-water emulsion polymerization. An
average particle size is 28-42 m. Compared with the prior art, the present invention has the
following advantages: the hollow polymer microsphere profile control agent is used to substitute
the existing solid polymer microsphere profile control agent, so that the utilization rate of raw
materials of the profile control agent can be greatly increased, and the construction cost of the
polymer microspheres can be reduced.
Drawings of Description
Fig. 2
Fig. 2
1
Description
Drawings of Description
Fig. 2
Fig. 2
Description
Technical Field
The present invention belongs to the field of oil recovery enhancement of the petroleum engineering, and particularly relates to a hollow polymer microsphere profile control agent and a preparation method thereof.
Background
In recent years, polymer spherical particles have a good application effect in the field of enhancing oil recovery with oil reservoir profile control, and have attracted more and more attention from major oilfield companies and many scientific researchers in China and abroad. At present, during the on-site construction of oil reservoir profile control in major oilfields in China and abroad, the used polymer spherical particle profile control agents are solid polymer microspheres. Because of huge consumption amount of the profile control agents during the profile control construction, the cost of using the solid polymer microspheres as the profile control agents is relatively high. For this problem, the present invention provides a hollow polymer microsphere profile control agent and a preparation method thereof. The hollow polymer microsphere profile control agent is used to substitute the existing solid polymer microsphere profile control agent, so that the utilization rate of raw materials of the profile control agent can be greatly increased, and the construction cost of the polymer microsphere profile control agent can be reduced. At present, the hollow polymer microspheres have already been widely applied to the industries such as coatings, building materials, chemical industry, paper making, cosmetics and leather, and have good application prospects in the fields such as aerospace, navigation, controlled drug release, gene therapy, protection of bioactive molecules, and catalyst carriers. However, the specific application methods and effects have not been reported, and there are no reports about the research and application of hollow polymer microspheres in the fields such as profile control and oil recovery enhancement in petroleum engineering.
Summary
Description
The purpose of the present invention is to provide a hollow polymer microsphere profile control agent and a preparation method thereof with respect to the problem that the cost of using the existing solid polymer microspheres as the profile control agent is relatively high. The present invention is implemented through the following technical solutions: a hollow polymer microsphere profile control agent is provided. The hollow polymer microspheres are prepared by using acrylamide and ionic monomers as functional monomers and hydrophobic monomers with double unsaturated bonds as cross-linking agents through water-in-oil-in-water emulsion polymerization. An average particle size is 28-42 m. A preparation method of the hollow polymer microsphere profile control agent includes the following steps: (1) dissolving 1-3 g of oil-soluble emulsifier and 0.05-0.2 g of oil-soluble initiator in 8-12 g of cross-linking agent to prepare an oil-phase emulsion; (2) dissolving 1-3 g of acrylamide, 0.5-2 g of ionic monomers and 0.2-0.6 g of water-soluble emulsifier in 100 mL of water to prepare a water-phase emulsion; (3) mixing 3-6 mL of water-phase emulsion prepared in step (2) and the oil-phase emulsion, stirring for 30 min, slowly adding the remaining water solution under the condition that the stirring rate is kept unchanged, increasing the temperature to 65-70 °C, and reacting for 3-5 hours; (4) after the reaction is ended, centrifugally separating the resulting reaction solution at 6000 rpm, wherein the obtained solid is the hollow polymer microsphere profile control agent. As the further improvement of the above solution, the oil-soluble emulsifier is one or any mixture of Span-80, Span-65 and Span-60. As the further improvement of the above solution, the oil-soluble initiator is one of azodiisobutyronitrile and azodiisoheptonitrile. As the further improvement of the above solution, the cross-linking agent is one or any mixture of divinylbenzene and ethylene glycol dimethacrylate. As the further improvement of the above solution, the ionic monomers are one or any mixture of sodium acrylate, 2-acrylamide-2-methylpropanesulfonate, methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride and octadecyl dimethyl allyl ammonium chloride. As the further improvement of the above solution, the water-soluble emulsifier is one or any mixture of OP-10,Tween-60, AES and AOS. As the further improvement of the above solution, the water is deionized water.
Description
As the further improvement of the above solution, the stirring rate in the step (3) is 150-200 rpm. Compared with the prior art, the present invention has the following advantages: the hollow polymer microsphere profile control agent is used to substitute the existing solid polymer microsphere profile control agent, so that the utilization rate of raw materials of the profile control agent can be greatly increased, and the construction cost of the polymer microspheres can be reduced.
Description of Drawings
Fig. 1 is an SEM image of a hollow polymer microsphere profile control agent prepared in embodiment 1 of the present invention; Fig. 2 is an SEM image of the hollow polymer microsphere profile control agent prepared in embodiment 1 of the present invention; Fig. 3 is an SEM image of the hollow polymer microsphere profile control agent prepared in embodiment 1 of the present invention; and Fig. 4 is an SEM image of the hollow polymer microsphere profile control agent prepared in embodiment 1 of the present invention.
Detailed Description
The present invention is further described below in combination with the drawings. Embodiment 1 A preparation method of a hollow polymer microsphere profile control agent includes the following steps: 1.5 g of Span-80 and 0.1 g of azodiisobutyronitrile are dissolved in 10 g of divinyl benzene to prepare an oil-phase emulsion, and 1 g of acrylamide, 0.5 g of sodium acrylate and 0.4 g of AES are dissolved in 100 mL of water to prepare a water-phase emulsion; 5 mL of water-phase emulsion is mixed with the oil-phase emulsion and stirred for 30 min; under the condition that the stirring rate is kept at 150 rpm, the remaining 95 mL of water-phase emulsion is slowly added, and at the same time, the temperature increases to 70°C for reaction for 3 h; and after the reaction is ended, the reaction solution is centrifugally separated at 6000 rpm, and the obtained solid is the hollow polymer microsphere profile control agent. An SEM image of the hollow polymer microsphere profile control agent is shown in Fig. 1. An average particle size is determined as 41.32 tm.
Description Embodiment 2 A preparation method of a hollow polymer microsphere profile control agent includes the following steps: 3 g of Span-60 and 0.2 g of azodiisobutyronitrile are dissolved in 12 g of divinyl benzene to prepare an oil-phase emulsion, and 1.5 g of acrylamide, 1 g of 2-acrylamide-2-methylpropanesulfonate and 0.6 g of AES are dissolved in 100 mL of water to prepare a water-phase emulsion; 3 mL of water-phase emulsion is mixed with the oil-phase emulsion and stirred for 30 min; under the condition that the stirring rate is kept at 200 rpm, the remaining 97 mL of water-phase emulsion is slowly added, and at the same time, the temperature increases to 70°C for reaction for 5 h; and after the reaction is ended, the reaction solution is centrifugally separated at 6000 rpm, and the obtained solid is the hollow polymer microsphere profile control agent. An SEM image of the hollow polymer microsphere profile control agent is shown in Fig. 2. An average particle size is determined as 29.17 [m. Embodiment 3
A preparation method of a hollow polymer microsphere profile control agent includes the following steps: 3 g of Span-80 and 0.1 g of azodiisobutyronitrile are dissolved in 8 g of ethylene glycol dimethacrylate to prepare an oil-phase emulsion, and 2 g of acrylamide, 0.5 g of methacryloyloxyethyl trimethyl ammonium chloride and 0.6 g of AOS are dissolved in 100 mL of water to prepare a water-phase emulsion; 4 mL of water-phase emulsion is mixed with the oil-phase emulsion and stirred for 30 min; under the condition that the stirring rate is kept at 200 rpm, the remaining 96 mL of water-phase emulsion is slowly added, and at the same time, the temperature increases to 70°C for reaction for 3 h; and after the reaction is ended, the reaction solution is centrifugally separated at 6000 rpm, and the obtained solid is the hollow polymer microsphere profile control agent. An SEM image of the hollow polymer microsphere profile control agent is shown in Fig. 3. An average particle size is determined as 32.36 [m. Embodiment 4 A preparation method of a hollow polymer microsphere profile control agent includes the following steps: 3 g of Span-80 and 0.1 g of azobisvaleronitrile are dissolved in 12 g of ethylene glycol dimethacrylate to prepare an oil-phase emulsion, and 1 g of acrylamide, 1 g of acryloyloxyethyl trimethyl ammonium chloride and 0.6 g of OP-10 are dissolved in 100 mL of water to prepare a water-phase emulsion; 6 mL of water-phase emulsion is mixed with the oil-phase emulsion and stirred for 30 min; under the condition that the stirring rate is kept at 200
Description
rpm, the remaining 94 mL of water-phase emulsion is slowly added, and at the same time, the temperature increases to 65°C for reaction for 4 h; and after the reaction is ended, the reaction solution is centrifugally separated at 6000 rpm, and the obtained solid is the hollow polymer microsphere profile control agent. An SEM image of the hollow polymer microsphere profile control agent is shown in Fig. 4. An average particle size is determined as 37.33 tm. The above only describes preferred embodiments of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitution and improvements made within the spirit and principles of the present invention shall be included within the protection scope of the present invention. In addition, it should be noted that various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, various possible combinations are not explained separately in the present invention. Furthermore, various embodiments of the present invention can be combined arbitrarily, which can also be regarded as the disclosure of the present invention as long as they do not violate the concept of the present invention.
Claims (9)
- Claims 1. A hollow polymer microsphere profile control agent, wherein hollow polymer microspheres are prepared by using acrylamide and ionic monomers as functional monomers and hydrophobic monomers with double unsaturated bonds as cross-linking agents through water-in-oil-in-water emulsion polymerization; and an average particle size is 28-42 [m.
- 2. A preparation method of the hollow polymer microsphere profile control agent of claim 1, comprising the following steps: (1) dissolving 1-3 g of oil-soluble emulsifier and 0.05-0.2 g of oil-soluble initiator in 8-12 g of cross-linking agent to prepare an oil-phase emulsion; (2) dissolving 1-3 g of acrylamide, 0.5-2 g of ionic monomers and 0.2-0.6 g of water-soluble emulsifier in 100 mL of water to prepare a water-phase emulsion; (3) mixing 3-6 mL of water-phase emulsion prepared in step (2) and the oil-phase emulsion, stirring for 30 min, slowly adding the remaining water solution under the condition that the stirring rate is kept unchanged, increasing the temperature to 65-70 °C, and reacting for 3-5 hours; (4) after the reaction is ended, centrifugally separating the resulting reaction solution at 6000 rpm, wherein the obtained solid is the hollow polymer microsphere profile control agent.
- 3. The preparation method of the hollow polymer microsphere profile control agent according to claim 2, wherein the oil-soluble emulsifier is one or any mixture of Span-80, Span-65 and Span-60.
- 4. The preparation method of the hollow polymer microsphere profile control agent according to claim 2, wherein the oil-soluble initiator is one of azodiisobutyronitrile and azodiisoheptonitrile.
- 5. The preparation method of the hollow polymer microsphere profile control agent according to claim 2, wherein the cross-linking agent is one or any mixture of divinylbenzene and ethylene glycol dimethacrylate.
- 6. The preparation method of the hollow polymer microsphere profile control agent according to claim 2, wherein the ionic monomers are one or any mixture of sodium acrylate, 2-acrylamide-2-methylpropanesulfonate, methacryloyloxyethyl trimethyl ammonium chloride, acryloyloxyethyl trimethyl ammonium chloride and octadecyl dimethyl allyl ammonium chloride.
- 7. The preparation method of the hollow polymer microsphere profile control agent according to claim 2, wherein the water-soluble emulsifier is one or any mixture of OP-10,Tween-60, AES andAOS.Claims
- 8. The preparation method of the hollow polymer microsphere profile control agent according to any one of claims 2-7, wherein the water is deionized water.
- 9. The preparation method of the hollow polymer microsphere profile control agent according to claim 8, wherein the stirring rate in the step (3) is 150-200 rpm.
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| AU2020103311A AU2020103311A4 (en) | 2020-11-09 | 2020-11-09 | Hollow polymer microsphere profile control agent and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112708033A (en) * | 2021-01-27 | 2021-04-27 | 陕西科技大学 | Coated adjustable polymer profile control agent and preparation method and application thereof |
| CN113018419A (en) * | 2021-04-01 | 2021-06-25 | 南通大学附属医院 | Medical chitosan nano-microsphere for repairing wound surface and inhibiting scar and preparation method thereof |
| CN113855810A (en) * | 2021-09-22 | 2021-12-31 | 西安纳瑞工控科技有限公司 | Pharmaceutic adjuvant sodium polystyrene sulfonate microsphere and preparation method thereof |
| WO2023015730A1 (en) * | 2021-08-09 | 2023-02-16 | 中海油田服务股份有限公司 | Polymeric microsphere with surfactant wrapped therein and preparation method therefor |
| CN115819672A (en) * | 2021-09-16 | 2023-03-21 | 中国石油化工股份有限公司 | Profile control agent, preparation method and application |
| CN115894754A (en) * | 2022-10-12 | 2023-04-04 | 西南石油大学 | Phenyl nano microsphere crosslinking agent for profile control agent and preparation method and application thereof |
-
2020
- 2020-11-09 AU AU2020103311A patent/AU2020103311A4/en not_active Ceased
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112708033A (en) * | 2021-01-27 | 2021-04-27 | 陕西科技大学 | Coated adjustable polymer profile control agent and preparation method and application thereof |
| CN112708033B (en) * | 2021-01-27 | 2023-01-20 | 山东滨州昱诚化工科技有限公司 | Coated adjustable polymer profile control agent and preparation method and application thereof |
| CN113018419A (en) * | 2021-04-01 | 2021-06-25 | 南通大学附属医院 | Medical chitosan nano-microsphere for repairing wound surface and inhibiting scar and preparation method thereof |
| WO2023015730A1 (en) * | 2021-08-09 | 2023-02-16 | 中海油田服务股份有限公司 | Polymeric microsphere with surfactant wrapped therein and preparation method therefor |
| CN115819672A (en) * | 2021-09-16 | 2023-03-21 | 中国石油化工股份有限公司 | Profile control agent, preparation method and application |
| CN115819672B (en) * | 2021-09-16 | 2023-09-01 | 中国石油化工股份有限公司 | Profile control agent and preparation method and application thereof |
| CN113855810A (en) * | 2021-09-22 | 2021-12-31 | 西安纳瑞工控科技有限公司 | Pharmaceutic adjuvant sodium polystyrene sulfonate microsphere and preparation method thereof |
| CN115894754A (en) * | 2022-10-12 | 2023-04-04 | 西南石油大学 | Phenyl nano microsphere crosslinking agent for profile control agent and preparation method and application thereof |
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