CN111072869A - Preparation method of supramolecular polymer gel microspheres for deep profile control and flooding - Google Patents
Preparation method of supramolecular polymer gel microspheres for deep profile control and flooding Download PDFInfo
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- CN111072869A CN111072869A CN201911402637.2A CN201911402637A CN111072869A CN 111072869 A CN111072869 A CN 111072869A CN 201911402637 A CN201911402637 A CN 201911402637A CN 111072869 A CN111072869 A CN 111072869A
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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
- 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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- 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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- 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
Abstract
The invention belongs to the field of improving the petroleum recovery ratio in petroleum engineering, is used in profile control, oil increasing and water controlling operation in petroleum development and oil displacement, and particularly relates to a preparation method of a supermolecule polymer gel microsphere for deep displacement, wherein the preparation method of the supermolecule polymer gel microsphere adopts a reverse emulsion polymerization method, and forms a stable polymer gel microsphere which is a copolymer of acrylamide, a hydroxyl-containing unsaturated monomer and a hydroxyl-containing macromonomer under the action of a large number of hydrogen bonds among monomers without adding a cross-linking agent. Compared with the prior art, the method does not use a cross-linking agent or cross-link chemical bonds, the supermolecule polymer gel microspheres form a linear polymer with certain viscosity after being decomposed, and are finally decomposed into small molecular compounds without solid-phase residues, so that the risk that the lamellar residues generated by the degradation of the chemical bond cross-linked microspheres block the nano-micron scale pore channels of the stratum is reduced.
Description
Technical Field
The invention belongs to the technical field of petroleum engineering for improving petroleum recovery ratio, and particularly relates to a preparation method of a supramolecular polymer gel microsphere for deep profile control and flooding.
Background
With the development of unconventional oil and gas reservoirs, the deep profile control and flooding technology presents good potential for improving the recovery ratio of crude oil, and becomes a research hotspot of various large petroleum companies and scientific research institutes in recent decades. In the deep profile control and flooding technology, the measure effect of the polymer microspheres is far better than that of a polyacrylamide solution, cross-linked flowable gel, pre-cross-linked bulk swelling particles and the like, and the polymer microspheres are suitable for different oil and gas reservoir conditions and achieve the purpose of greatly improving the crude oil exploitation efficiency.
The original size of the polymer microsphere is nano-scale to micro-scale, after entering the stratum, the polymer microsphere is captured at the pore throat matched with the polymer microsphere after swelling in water, or plugging is realized through a bridging theory, resistance is generated on fluid in a channel, the direction of the fluid flow is changed, and the plugging effect is achieved. Under high injection pressure, the polymer microspheres can deform, so that the capturing effect of the stratum is broken through, the polymer microspheres are pushed forward and moved, the effect of blocking the stratum deeper is achieved for multiple times, and the technical advantage of blocking without death is achieved, so that the effect of deep profile control and flooding is achieved.
According to different polymerization mechanisms, the preparation method of the polymer microspheres comprises an inverse emulsion polymerization method, an inverse microemulsion polymerization method, an inverse suspension polymerization method and the like, and the obtained microspheres mainly comprise homogeneous solid spheres, hollow spheres, core-shell structure microspheres and multilayer structure microspheres. The Chinese patent CN106589259A discloses a reported preparation method of temperature-resistant and salt-resistant polymeric microspheres, which is to prepare the temperature-resistant and salt-resistant polymeric microspheres by using at least one of divinylbenzene, methylenebisacrylamide, polyethylene glycol diacrylate vinegar and pentaerythritol triacrylate vinegar as a cross-linking agent by adopting an inverse microemulsion polymerization method. Chinese patent CN107098999A discloses a 'hollow polymeric microsphere profile control agent and a preparation method thereof', the method takes a hydrophobic monomer with double unsaturated double bonds as a cross-linking agent, and prepares hollow polymeric microspheres by water-in-oil double emulsion polymerization, and the method has the characteristics of less dosage and low cost. The 'polydisperse polyacrylamide microsphere system and the preparation method thereof' disclosed and reported in Chinese patent CN106866880A adopts a multi-step polymerization method to initiate polymerization for three times, and prepares the polydisperse polyacrylamide microsphere system by taking one or more than two of methylene bisacrylamide, divinylbenzene, polyethylene glycol diacrylate vinegar, pentaerythritol triacrylate vinegar and the like as a cross-linking agent, contains nano, micron and millimeter polymer microspheres, and can meet the requirements of profile control, profile control and flooding of severely heterogeneous strata. The 'degradable polymer microsphere deep profile control and flooding agent and the preparation method thereof' disclosed and reported in Chinese patent CN104829784A, the method for oil recovery reversed phase suspension polymerization, is formed by copolymerizing acrylamide monomer, temperature-resistant and salt-tolerant monomer and polyethylene glycol diacrylate degradable crosslinking monomer. The early stage of water absorption and expansion plays a role in deep profile control; under the oil reservoir temperature, the linear polymer can be decomposed in the later period, and the deep oil displacement is realized. The prior publicly reported microsphere preparation technologies are large in quantity, and the swept volume is improved to a certain extent, but in the preparation process, a cross-linking agent is used for chemical cross-linking, also called as 'hard cross-linking', most of decomposition products are residue fragments, and the risk of pollution and stratum plugging exists.
The invention relates to a supermolecule polymer gel microsphere for deep profile control, which is formed by copolymerization reaction of acrylamide, hydroxyl-containing unsaturated monomer and hydroxyl-containing macromonomer under the condition of not adding a cross-linking agent and under the action of a large number of hydrogen bonds among molecules. The microspheres are decomposed to form a linear polymer with certain viscosity, so that the aim of deep profile control and flooding can be fulfilled.
Disclosure of Invention
The invention aims to provide a preparation method of a supramolecular polymer gel microsphere for deep profile control and flooding. The polymer gel microsphere prepared by the method is formed by a large amount of hydrogen bonds among molecules after monomer copolymerization in the absence of a cross-linking agent. The polymer with viscosity is formed by opening the hydrogen bonds in the polymer gel microspheres, and the method is suitable for deep profile control and flooding of oil reservoirs and profile control and oil and water increasing operations of oil development and profile control and flooding; meanwhile, the microspheres have no solid-phase residue after decomposition, and cannot pollute the stratum.
The invention relates to a preparation method of a supramolecular polymer gel microsphere for deep profile control and flooding, which is characterized by comprising the following steps of: the supermolecule polymer gel microsphere is formed by copolymerizing acrylamide, hydroxyl-containing unsaturated monomer and hydroxyl-containing macromonomer through a large amount of intermolecular hydrogen bond actions by adopting an inverse emulsion polymerization method, and is dispersed in an emulsion formed by an oil phase and an emulsifier.
A preparation method of a supramolecular polymer gel microsphere for deep profile control and flooding comprises the following steps:
(1) 1-5 g of acrylamide, 1-5 g of hydroxyl-containing unsaturated monomer and 0.1-10 g of hydroxyl-containing macromonomer are dissolved in 23-100 g of deionized water to form a clear and uniform water phase, wherein the mass ratio of the micromolecular monomer to the hydroxyl-containing macromonomer is 1 (0.05-1);
(2) adding 0.5-40 g of emulsifier into 11-160 g of nonpolar medium, and uniformly stirring to form an oil phase;
(3) heating the oil phase to 30-70 ℃, dropwise adding the water phase at a stirring speed of 100-500 r/min to form an inverse emulsion of a transparent or semitransparent or milky emulsion, replacing air with nitrogen for 0.3-1 h, adding a sodium bisulfite aqueous solution and an ammonium persulfate aqueous solution to initiate polymerization reaction for 2-3 h, and obtaining the supramolecular polymer gel microspheres.
As a further improvement to the above process, the hydroxyl group-containing unsaturated monomer is at least two of methylolacrylamide, hydroxyethyl acrylamide, glycerol acrylate, ethylene glycol acrylate monoester, pentaerythritol acrylate monoester, and triethanolamine acrylate monoester.
As a further improvement of the method, the hydroxyl-containing macromonomer is at least one of acrylic polyethylene glycol monoester, propenyl phenol polyoxyethylene ether, vinyl phenol polyoxyethylene ether, propenyl alcohol polyoxypropylene ether and propenyl alcohol polyoxyethylene (propenyl) ether.
As a further improvement of the method, the emulsifier is composed of at least one of sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, alkylphenol ethoxylate, fatty alcohol polyoxyethylene ether and sodium diisooctyl succinate sulfonate, and the mass ratio of the sorbitan fatty acid ester to the polyoxyethylene sorbitan fatty acid ester is (0.3-3): 1.
as a further improvement of the method, the nonpolar medium is one of white oil, normal hexane, diesel oil and kerosene.
The invention has the beneficial effects that: the cross-linking agent is not added in the synthesis process of the supermolecule polymer gel microsphere, so that the synthesis steps are simplified; meanwhile, the microspheres can play a role in plugging at the early stage, and a viscous polymer is formed after hydrogen bonds are opened, so that the polymer flooding is realized, and the deep profile control and flooding function is realized; the degradation process of the microspheres is the breakage of hydrogen bonds and chemical bonds, and the final decomposed residues exist in a micromolecular form, have no solid phase residues and have no pollution to the stratum.
Detailed Description
Example 1
Adding 5g of acrylamide, 2g of hydroxymethyl acrylamide, 3g of glycerol acrylate and 10g of ethylene acid polyethylene glycol monoester into 100g of deionized water in sequence, and dissolving uniformly to form a water phase; adding 10g of sorbitan fatty acid ester (Span-60) and 10g of polyoxyethylene sorbitan fatty acid ester (Tween-80) into 100g of white oil, and uniformly stirring to form an oil phase. Heating the oil phase to 40 ℃, dropwise adding the water phase to the oil phase at the stirring speed of 200r/min to obtain transparent or semitransparent or milky emulsion, replacing air with nitrogen for 15min, adding 2mL of 2% ammonium persulfate aqueous solution and 2mL of 2% sodium bisulfite, and initiating polymerization reaction at 40 ℃ for 2h to obtain the supramolecular polymer gel microspheres.
Example 2
Adding 3g of acrylamide, 2g of hydroxymethyl acrylamide, 3g of hydroxyethyl acrylamide and 5g of ethylene acid polyethylene glycol monoester into 80g of deionized water in sequence, and dissolving uniformly to form a water phase; adding 8g of sorbitan fatty acid ester (Span-80) and 10g of alkylphenol polyoxyethylene ether (OP-10) into 100g of white oil, and uniformly stirring to form an oil phase. Heating the oil phase to 60 ℃, dropwise adding the water phase to the oil phase at the stirring speed of 300r/min to obtain transparent or semitransparent or milky emulsion, replacing air with nitrogen for 15min, adding 2mL of 2% ammonium persulfate aqueous solution and 2mL of 2% sodium bisulfite, and initiating polymerization reaction at 60 ℃ for 2h to obtain the supramolecular polymer gel microspheres.
Example 3
Sequentially adding 2g of acrylamide, 1g of ethylene glycol acrylate, 3g of hydroxyethyl acrylamide and 5g of propenyl phenol polyoxyethylene ether into 50g of deionized water, and uniformly dissolving to form a water phase; 5g of sorbitan fatty acid ester (Span-85) and 8g of alkylphenol polyoxyethylene ether (OP-10) are added into 80g of white oil and stirred uniformly to form an oil phase. Heating the oil phase to 50 ℃, dropwise adding the water phase to the oil phase at the stirring speed of 400r/min to obtain transparent or semitransparent or milky emulsion, replacing air with nitrogen for 15min, adding 2mL of 2% ammonium persulfate aqueous solution and 2mL of 2% sodium bisulfite, and initiating polymerization reaction at 50 ℃ for 2h to obtain the supramolecular polymer gel microspheres.
Example 4
Adding 4g of acrylamide, 3g of pentaerythritol acrylate monoester, 2g of hydroxyethyl acrylamide and 9g of propenol polyoxyethylene ether into 100g of deionized water in sequence, and uniformly dissolving to form a water phase; adding 8g of sorbitan fatty acid ester (Span-85) and 10g of fatty alcohol-polyoxyethylene ether (AEO-9) into 120g of white oil, and uniformly stirring to form an oil phase. Heating the oil phase to 70 ℃, dropwise adding the water phase to the oil phase at the stirring speed of 500r/min to obtain transparent or semitransparent or milky emulsion, replacing air with nitrogen for 15min, adding 2mL of 2% ammonium persulfate aqueous solution and 2mL of 2% sodium bisulfite, and initiating polymerization reaction at 70 ℃ for 2h to obtain the supramolecular polymer gel microspheres.
The cross-linking agent is not added in the synthesis process of the supermolecule polymer gel microsphere, so that the synthesis steps are simplified; meanwhile, the microspheres can play a role in plugging at the early stage, and a viscous polymer is formed after hydrogen bonds are opened, so that the polymer flooding is realized, and the deep profile control and flooding function is realized; the degradation process of the microspheres is the breakage of hydrogen bonds and chemical bonds, and the final decomposed residues exist in a micromolecular form, have no solid phase residues and have no pollution to the stratum.
Claims (5)
1. A preparation method of a supramolecular polymer gel microsphere for deep profile control and flooding is characterized by comprising the following steps: the supermolecule polymer gel microsphere is formed by copolymerizing acrylamide, hydroxyl-containing unsaturated monomer and hydroxyl-containing macromonomer through a large amount of intermolecular hydrogen bond actions by adopting an inverse emulsion polymerization method, and is dispersed in an emulsion formed by an oil phase and an emulsifier, and the method comprises the following steps:
dissolving 1-5 g of acrylamide, 1-5 g of hydroxyl-containing unsaturated monomer and 0.1-10 g of hydroxyl-containing macromonomer in 23-100 g of deionized water to form a clear and uniform water phase, wherein the mass ratio of the small molecular monomer to the hydroxyl-containing macromonomer is 1 (0.05-1);
adding 0.5-40 g of emulsifier into 11-160 g of nonpolar medium, and uniformly stirring to form an oil phase;
and step three, heating the oil phase to 30-70 ℃, dropwise adding the water phase at a stirring speed of 100-500 r/min to form an inverse emulsion of the transparent or semitransparent or milky emulsion, replacing air with nitrogen for 0.3-1 h, adding the sodium bisulfite aqueous solution and the ammonium persulfate aqueous solution to initiate polymerization reaction for 2-3 h, and obtaining the supramolecular polymer gel microspheres.
2. The preparation method of the supramolecular polymer gel microsphere for deep profile control and flooding according to claim 1, which is characterized in that: the hydroxyl-containing unsaturated monomer is at least two of hydroxymethyl acrylamide, hydroxyethyl acrylamide, glycerol acrylate, ethylene glycol acrylate monoester, pentaerythritol acrylate monoester and triethanolamine acrylate monoester.
3. The preparation method of the supramolecular polymer gel microsphere for deep profile control and flooding according to claim 1, which is characterized in that: the hydroxyl-containing macromonomer is at least one of acrylic acid polyethylene glycol monoester, propenyl phenol polyoxyethylene ether, vinyl phenol polyoxyethylene ether, propenyl alcohol polyoxypropylene ether and propenyl alcohol polyoxyethylene (propenyl) ether.
4. The preparation method of the supramolecular polymer gel microsphere for deep profile control and flooding according to claim 1, which is characterized in that: the emulsifier is composed of at least one of sorbitan fatty acid ester and polyoxyethylene sorbitan fatty acid ester, alkylphenol polyoxyethylene, fatty alcohol polyoxyethylene ether and sodium diisooctyl succinate sulfonate, and the mass ratio of the sorbitan fatty acid ester to the polyoxyethylene sorbitan fatty acid ester is (0.3-3): 1.
5. the preparation method of the supramolecular polymer gel microsphere for deep profile control and flooding according to claim 1, which is characterized in that: the nonpolar medium is one of white oil, n-hexane, diesel oil and kerosene.
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Citations (3)
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|---|---|---|---|---|
| EP1400538A1 (en) * | 2002-09-11 | 2004-03-24 | L'oreal | Method of producing synthetic polymer gel |
| CN102603966A (en) * | 2012-03-12 | 2012-07-25 | 里群 | Cross-linked polymer microsphere for oil displacement of oilfield and preparation method for cross-linked polymer microsphere |
| CN104017131A (en) * | 2014-05-30 | 2014-09-03 | 北京石大万嘉新材料科技有限公司 | Polymer microgel oil-displacing agent, preparing method thereof and applications thereof |
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- 2019-12-31 CN CN201911402637.2A patent/CN111072869A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1400538A1 (en) * | 2002-09-11 | 2004-03-24 | L'oreal | Method of producing synthetic polymer gel |
| CN102603966A (en) * | 2012-03-12 | 2012-07-25 | 里群 | Cross-linked polymer microsphere for oil displacement of oilfield and preparation method for cross-linked polymer microsphere |
| CN104017131A (en) * | 2014-05-30 | 2014-09-03 | 北京石大万嘉新材料科技有限公司 | Polymer microgel oil-displacing agent, preparing method thereof and applications thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王永鹤: "水溶性聚合物反相乳液聚合及性能评价", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
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