CN110790959A - Water-soluble phenolic resin crosslinking agent low-temperature rapid gelling and crosslinking promoting agent and preparation method and application thereof - Google Patents
Water-soluble phenolic resin crosslinking agent low-temperature rapid gelling and crosslinking promoting agent and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of oil-water well profile control and water shutoff in oil exploitation, and particularly relates to a water-soluble phenolic resin cross-linking agent which is quickly gelled at a low temperature and a cross-linking promoter, and a preparation method and application thereof; the crosslinking promoter comprises the following components in percentage by weight: 1.0-5.0% of cationic imine copolymer, 1.0-5.0% of weak base, 0-20.0% of mineralization degree regulator and the balance of tap water; the addition amount of the mineralization degree regulator meets the requirement that the final content of the applied gel profile control agent is more than 0.3 per mill. The invention provides a crosslinking promoter, which can control the gelling time of partial hydrolyzed anionic polyacrylamide at low temperature of an oil reservoir within 12-120 h, the initial viscosity within 700-1200 mPa.s, the final setting strength within 20000-80000 mPa.s, and is suitable for the profile control and water shutoff operation of a large dominant cross flow channel of a stratum below 60 ℃.
Description
Technical Field
The invention belongs to the technical field of oil-water well profile control and water shutoff in oil exploitation, and particularly relates to a water-soluble phenolic resin crosslinking agent low-temperature rapid gelling and crosslinking promoter, and a preparation method and application thereof.
Background
The gel profile control agent is one of the most extensive profile control agents for profile control and water shutoff of oil-water wells, mainly comprises polyacrylamide and a cross-linking agent, and is prepared into polymer gel with a three-dimensional network structure through cross-linking reaction of the polyacrylamide and the cross-linking agent. The cross-linking agent is generally divided into a low-temperature cross-linking agent at a temperature of less than 60 ℃, a medium-temperature cross-linking agent at a temperature of 60-90 ℃ and a high-temperature cross-linking agent at a temperature of more than 90 ℃ according to the temperature of the profile control stratum.
Wherein the polyvalent metal ion crosslinking agent is the most used low-temperature crosslinking agent, and is generally Al3+、Cr3+And the like. The multi-valent metal ions generate multi-core hydroxyl bridge complex ions through hydrolysis and hydroxyl bridge action, and the multi-valent metal ions and carboxyl in polyacrylamide molecules form coordinate bonds to generate cross-linking reaction[1]. The crosslinking agent is easy to absorb and lose polyvalent metal ions by stratum in mineral tests and has poor salt tolerance. In addition, Cr3+Has higher toxicity and is gradually limited to use.
Polyethyleneimine crosslinkers are commonly used as high temperature crosslinkers, only jaguar et al[2]Studies have reported the use of polyethyleneimine as a low temperature crosslinking agent. The report shows that the gel forming time of the polyethyleneimine crosslinked polyacrylamide at the low temperature of 40 ℃ can be controlled within 15h-9d, and the formed gel has high strength. Wherein the concentration of polyethyleneimine used as a crosslinking agent is 0.3-0.8 wt%. However, the mechanism of crosslinking polyethyleneimine at low temperature is not reported in detail. In addition, polyethyleneimine is relatively high in cost (higher than 15 ten thousand yuan/ton), and is not suitable for large-dose deep profile control of unconsolidated sandstone formations at the temperature of less than 60 ℃.
Similarly, water soluble phenolic resin crosslinkers are also present in low temperature applicationsLimitations; the water-soluble phenolic resin belongs to a first-stage product of thermosetting phenolic resin, a hydroxymethyl functional group of the water-soluble phenolic resin has strong reactivity and can form covalent bond crosslinking with dehydration condensation crosslinking reaction between an amide group of polyacrylamide at the temperature of more than 90 ℃, and a crosslinked product is jelly for profile control. Because the condensation reaction needs higher reaction activation energy, the phenolic resin crosslinking agent is usually used as a high-temperature crosslinking agent, but the water-soluble phenolic resin crosslinking agent is slowly gelled with a polymer in a low-temperature environment of less than 60 ℃, generally 10 days or longer, and even can not be crosslinked[3]。
Chinese patent CN102766449A reports a low-temperature crosslinking promoter for polyacrylamide and water-soluble phenolic resin, because the crosslinking promoter is added with a polyacrylamide/water-soluble phenolic resin weak gel system, the crosslinking time is 30-8 h and is adjustable under the condition of 30-60 ℃, the formula of the crosslinking promoter is as follows: 20-25% of ammonium chloride; 2-3% of m-benzenediol; 0-2% of oxalic acid; 1-2% of sodium thiosulfate; the balance being clear water.
Chinese patent CN104877653A reports that 'a phenolic aldehyde weak gel profile control and flooding agent for quick gel formation of low-temperature oil reservoirs' takes a polyacrylamide/phenolic aldehyde crosslinking agent as a main body, and polyhydric phenol and a coagulant are added, and the gel formation time can be controlled within 5-24 hours at the normal temperature of 25 ℃. The coagulant is one or a mixture of two or more of ammonium salts such as ammonium sulfate, ammonium acetate and the like. The modifying and flooding agent needs to be used together with a polyhydric phenol and a coagulant for realizing low-temperature quick crosslinking, the coagulant mainly comprising inorganic salt reduces the initial viscosity (20-60 mPa.s) of a profile control system, and the formation water dilution resistance is poor.
Chinese patent CN105860946A reports a profile control and water shutoff system with controllable low-temperature gelling, a preparation method thereof and a profile control and water shutoff method, wherein hydrolyzed polyacrylamide, paraformaldehyde and m-dihydroxybenzene in the profile control and water shutoff system can slowly perform a crosslinking reaction at a low temperature of 20-40 ℃, the crosslinking reaction speed is accelerated after a coagulant, namely m-phenylenediamine, is added, and the gelling time and the gel strength can be adjusted by changing the concentration of the m-phenylenediamine. The procoagulant metaphenylene diamine is a toxic chemical and a high carcinogen.
Chinese patent CN106317352A newspaperThe crosslinking agent and the preparation method and application thereof are characterized in that the water-soluble phenolic resin accounts for 15-25%, the crosslinking promoter accounts for 1.0-2.0%, the antifreeze agent accounts for 10-25%, and the balance is water. The crosslinking promoter is an organic chromium system. Similar methods are reported in[4]. The crosslinking accelerator is actually part of the crosslinking agent, and the low-temperature crosslinking agent participates in crosslinking reaction. In addition, a gel system prepared by the composite cross-linking agent is very sensitive to temperature and is easy to hydrolyze and dehydrate.
Chinese patent CN14342100A reports "a weak gel profile control agent and its preparation and application", its component weight part is 0.1-0.3 part polyacrylamide, 0.05-0.2 part urotropine, 0.005-0.03 part m-benzenediol, 0.05-0.2 part ammonium chloride, 0.01-0.05 part sodium bicarbonate, 0.05-0.15 part glacial acetic acid, 100 parts water; the weak gel can be generated by reaction at the temperature of 60-90 ℃, and the viscosity of the gel is 700-4000 mPa.s. The gel strength of the system is weak, and whether the oil reservoir can be gelled at the temperature of below 60 ℃ is unknown.
In the research of the low-temperature crosslinking (coagulating) promoting agents of the various water-soluble phenolic resin crosslinking agents, due to the addition of the crosslinking promoting agents, the crosslinking reaction speed of the water-soluble phenolic resin crosslinking agents and polymers is too high, the gelling time is short, the jelly strength is low (11000 mPa & s at most), and the technical requirement of deep profile control cannot be met (the gelling time is required to be adjustable for 24-120 h, and the jelly strength is greater than 20000mPa & s). Meanwhile, partial crosslinking promoters have the problems of high toxicity, high carcinogenicity, easy dilution by formation water and the like.
Reference documents: [1] tangerine et AL, "27 AL NMR study of the reaction of HPAM/ALCit systems with crosslinked polymers", Vol.6, 2000, J.SPECTROSCOPY, Vol.17,;
[2] "Research on the diagnosis Performance of Low ToxicPEI Cross-Linking PHPAM GelSystems as Waters of Agents in Low temperature protocols", proceedings of the American Chemical Society (ACS) of the book "Industrial and Engineering chemistry Research", 2010, volume 49, No. 20 ";
[3] the research on the deep profile control oil displacement crosslinking agent in the No. 8 of volume 4 of fine petrochemical engineering 2003 and the research on the low-temperature zirconium weak gel profile control agent in the No. 2 of volume 28 of Natural science edition of the Western-An university of Petroleum 2013;
[4] "development of composite crosslinked polymer plugging agent" in the stage 07 of fine petrochemical engineering in 2008 ".
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a water-soluble phenolic resin crosslinking agent capable of quickly gelling at low temperature and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a water-soluble phenolic resin cross-linking agent is a low-temperature quick-gelling crosslinking promoter, which comprises the following components in percentage by weight: 1.0-5.0% of cationic imine copolymer, 1.0-5.0% of weak base, 0-20.0% of mineralization degree regulator and the balance of tap water; the addition amount of the mineralization degree regulator meets the requirement that the final content of the mineralization degree regulator in the applied gel profile control agent is more than or equal to 0.3 per thousand.
The molecular weight of the cationic imine copolymer is 3000-5000, and the cationic imine copolymer is one or a mixture of polyethyleneimine and polyvinylamine.
The weak base is one or mixture of sodium carbonate and sodium bicarbonate.
The mineralization degree regulator is one or a mixture of sodium chloride, sodium sulfate and calcium chloride.
The application also comprises a method for preparing the water-soluble phenolic resin crosslinking agent for quickly forming gel at low temperature, which comprises the following steps: and sequentially adding the cationic imine copolymer, the weak base, the mineralization degree regulator and tap water into the stirring container, and uniformly stirring to obtain the product.
The application also comprises an application of the water-soluble phenolic resin crosslinking agent in low-temperature quick gelling and crosslinking promotion, which is applied to a gel profile control agent for profile control at the formation temperature of 35-60 ℃, and specifically comprises the following steps: sequentially adding a water-soluble phenolic resin cross-linking agent and partially hydrolyzed anionic polyacrylamide according to the mass ratio of the prepared solution of the gel profile control agent, stirring for 10 minutes, adding the water-soluble phenolic resin cross-linking agent to quickly form a gel cross-linking promoter at a low temperature, and continuously stirring for 60 minutes to obtain the gel profile control agent;
the water-soluble phenolic resin cross-linking agent and the low-temperature rapid gelling accelerator are respectively used in a gel profile control agent system at a concentration of 0.15-0.45 wt%, and the weight ratio of the water-soluble phenolic resin cross-linking agent to the gel profile control agent is 1: 1. The weight ratio of the partially hydrolyzed anionic polyacrylamide to the water-soluble phenolic resin cross-linking agent is 3: 1.5-4.5.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a low-temperature water-soluble phenolic resin crosslinking promoter, which can be used for controlling the gelling time of partially hydrolyzed anionic polyacrylamide at the oil reservoir temperature of 35-60 ℃ to be 12-120 h, controlling the initial viscosity of 700-1200 mPa.s and controlling the final setting strength of 20000-80000 mPa.s, and is suitable for the profile control and water plugging operation of a dominant channeling channel of a stratum below 60 ℃.
The technological advancement is as follows:
1) the crosslinking promoter is a liquid with low toxicity, no chromium, stable property and long-term storage, the components of the finished product are simple and easy to prepare, and the crosslinking promoter is mixed with a crosslinking agent and a polymer, is easy to dissolve, can be pumped and the like, and is convenient to construct.
2) Compared with the traditional promoter, the promoter has a great innovation. The cross-linking promoter has an improvement effect on the cross-linking reaction of a polyacrylamide polymer and a water-soluble phenolic resin cross-linking agent, and avoids the defects that the cross-linking system of the polymer is cross-linked prematurely and the gel strength is weak because the reaction activity of the water-soluble phenolic resin cross-linking agent is enhanced only one side by one side in the traditional cross-linking promoter.
3) In the early stage of 1-48 h of the crosslinking reaction of the crosslinking promoter, the polyacrylamide polymer and the water-soluble phenolic resin crosslinking agent, the crosslinking promoter forms a micro-crosslinking structure in the early stage of a reaction system by adsorbing anionic polyacrylamide, the water-soluble phenolic resin crosslinking agent mono/di-hydroxymethyl phenol and free aldehyde, and has the water-resistant dilution performance, the initial viscosity of 700-1200 mPa & s and strong selectivity on a dominant cross flow channel. By adjusting the addition concentration of the crosslinking accelerator, the gelling time of the crosslinking reaction can be controlled within 12-120 h.
4) In the middle and later stages of 24-120 h of the crosslinking reaction of the crosslinking promoter, the polyacrylamide polymer and the water-soluble phenolic resin crosslinking agent, active reaction groups of primary amine and secondary amine in the crosslinking promoter are replaced with partial acylamino of polyacrylamide, and simultaneously, weak base is further catalyzed, so that the crosslinking reaction of the water-soluble phenolic resin crosslinking agent and the anionic polyacrylamide is accelerated under the low-temperature environment by the aid of the reactive groups and the weak base. By adjusting the addition concentration of the crosslinking accelerator, curing for 60 days at 35-60 ℃, the final jelly strength can be 20000-80000 mPa & s controllable.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the following detailed description of the present invention is provided with reference to the best embodiments.
Example 1 (1) promoter raw materials (all commercial industrial products): 83.3g of tap water, 5.0g of polyethyleneimine, 5.0g of sodium carbonate and 6.7g of sodium chloride. All the components are uniformly mixed according to the preparation method described above strictly, and the water-soluble phenolic resin crosslinking agent of the product is a low-temperature quick-gelling crosslinking promoter.
(2) Preparing a gel profile control agent: taking 500mL of tap water, sequentially adding 4.5 per thousand of water-soluble phenolic cross-linking agent and 3 per thousand of hydrolyzable polyacrylamide according to the mass ratio of the prepared solution, stirring for 10 minutes, adding 4.5 per thousand of crosslinking promoter, continuously stirring for 60 minutes, and using DV-II+The initial viscosity of the gel profile control agent aqueous solution was measured by Pro Brookfield rotational viscometer at 5# spindle 5rpm and 1200 mPas.
(3) Pouring 100mL of the aqueous solution of the gel profile control agent obtained in the step (2) into a closed storage tank, placing a UFE500 constant temperature box, maintaining for 3 days at the constant temperature of 35 ℃, and measuring the viscosity of the gel profile control agent subjected to polymer crosslinking to be 45000mPa & s by using a DV-II + Pro type BROOKFIELD rotational viscometer and the rotation speed of a 5# rotor at 5 rpm; maintaining at constant temperature of 35 deg.C for 30 days, and measuring viscosity of the gel profile control agent to be 85000mPa & s; and continuously maintaining for 60 days at the constant temperature of 35 ℃, and measuring the viscosity of the gel profile control agent to be 80000 mPas without dehydration.
(4) Pouring 100mL of the aqueous solution of the gel profile control agent obtained in the step (2) into a closed storage tank, placing a UFE500 constant temperature box, maintaining at the constant temperature of 60 ℃ for 3 days, and measuring the viscosity of the gel profile control agent subjected to polymer crosslinking by using a DV-II + Pro type BROOKFIELD rotational viscometer and the rotation speed of 5# rotor at 5 rpm; maintaining at 60 deg.C for 30 days, and measuring the viscosity of the gel profile control agent to 87000 mPas; maintaining at constant temperature of 60 deg.C for 60 days to obtain gel profile control agent with viscosity of 83000 mPas, without dehydration.
The water-soluble phenolic aldehyde crosslinking agent used in the above examples was synthesized by laboratory self (obtained by reacting phenol and formaldehyde at a molar ratio of 1:3 at 50 ℃ for 1 hour, heating to 80 ℃ for 1 hour, continuing the reaction, and cooling to room temperature); the polyacrylamide used in the examples was produced by the harbour group of the great port oil field, with a degree of hydrolysis of 25% and a molecular weight of 2500 ten thousand. The same applies below.
Example 2:
(1) the cross-linking promoter raw materials (all commercial industrial products): 78.0g of tap water, 1.0g of polyethyleneimine, 1g of sodium carbonate and 20.0g of sodium chloride. The components are uniformly mixed according to the preparation method described above strictly, and the water-soluble phenolic resin crosslinking agent of the product is the low-temperature quick-gelling crosslinking promoter. Wherein the molecular weight of the cationic imine copolymer is 3000-5000, and the following are the same.
(2) Preparing a gel profile control agent: taking 500mL of tap water, sequentially adding 1.5 per thousand of water-soluble phenolic cross-linking agent and 3 per thousand of hydrolyzable polyacrylamide according to the mass ratio of the prepared solution, stirring for 10 minutes, adding 1.5 per thousand of crosslinking promoter, continuously stirring for 60 minutes, and using DV-II+The initial viscosity of the gel profile control agent aqueous solution was measured by Pro Brookfield rotational viscometer at 5# spindle 5rpm and was 700 mPas.
(3) Pouring 100mL of the aqueous solution of the gel profile control agent obtained in the step (2) into a closed storage tank, placing the storage tank in a UFE500 constant temperature cabinet, maintaining the storage tank at the constant temperature of 35 ℃ for 3 days, and measuring the viscosity of the gel profile control agent subjected to polymer crosslinking by using a DV-II + Pro type BROOKFIELD rotational viscometer and the rotation speed of a 5# rotor at 5 rpm; maintaining at constant temperature of 35 deg.C for 30 days, and measuring the viscosity of the gel profile control agent to be 22000mPa & s; maintaining at constant temperature of 35 deg.c for 60 days to obtain the gel profile control agent with viscosity 24000mPa · s and without dewatering.
(4) Pouring 100mL of the aqueous solution of the gel profile control agent obtained in the step (2) into a closed storage tank, placing a UFE500 constant temperature box, maintaining at the constant temperature of 60 ℃ for 3 days, and measuring the viscosity of the gel profile control agent subjected to polymer crosslinking to 10000mPa & s by using a DV-II + Pro type BROOKFIELD rotational viscometer and the rotation speed of a 5# rotor at 5 rpm; maintaining at constant temperature of 60 deg.C for 30 days, and measuring viscosity of the gel profile control agent to be 21000mPa & s; maintaining at constant temperature of 60 deg.C for 60 days, and measuring the viscosity of the gel profile control agent to be 20000 mPas without dehydration.
Example 3: 1) the cross-linking promoter raw materials (all commercial industrial products): 85.0g of tap water, 2.5g of polyethyleneimine, 2.5g of sodium carbonate and 10g of sodium chloride. All the components are uniformly mixed according to the preparation method described above strictly, and the water-soluble phenolic resin crosslinking agent of the product is the low-temperature quick-gelling crosslinking promoter. Wherein the molecular weight of the cationic imine copolymer is 3000-5000, and the following are the same.
(2) Preparing a gel profile control agent: taking 500mL of tap water, sequentially adding 3 per thousand of water-soluble phenolic cross-linking agent and 3 per thousand of hydrolyzable polyacrylamide according to the mass ratio of the prepared solution, stirring for 10 minutes, adding 3 per thousand of crosslinking promoter, continuously stirring for 60 minutes, and using DV-II+And measuring the initial viscosity 1050mPa & s of the gel profile control agent aqueous solution by using a Pro BROOKFIELD rotational viscometer and a 5# rotor at the rotating speed of 5 rpm.
(3) Pouring 100mL of the aqueous solution of the gel profile control agent obtained in the step (2) into a closed storage tank, placing the storage tank in a UFE500 constant temperature cabinet, maintaining the storage tank at the constant temperature of 35 ℃ for 3 days, and measuring the viscosity of the gel profile control agent subjected to polymer crosslinking by using a DV-II + Pro type BROOKFIELD rotational viscometer and the rotation speed of a 5# rotor at 5 rpm; maintaining at 35 deg.C for 30 days, and measuring the viscosity of the gel profile control agent to 48000 mPas; maintaining at 35 deg.c for 60 days to obtain gel profile control agent with viscosity of 50000 mPas and no dewatering.
(4) Pouring 100mL of the aqueous solution of the gel profile control agent obtained in the step (2) into a closed storage tank, placing a UFE500 constant temperature box, maintaining at the constant temperature of 60 ℃ for 3 days, and measuring the viscosity of the gel profile control agent subjected to polymer crosslinking to be 45000mPa & s by using a DV-II + Pro type BROOKFIELD rotational viscometer and the rotation speed of a 5# rotor at 5 rpm; maintaining at 60 deg.c for 30 days to obtain gel profile regulating agent viscosity of 47000 mPas; maintaining at constant temperature of 60 deg.c for 60 days to obtain viscosity 43000mPa · s of the gel profile control agent without dewatering.
The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.
Claims (7)
1. The water-soluble phenolic resin crosslinking agent is characterized by comprising the following components in percentage by weight: 1.0-5.0% of cationic imine copolymer, 1.0-5.0% of weak base, 0-20.0% of mineralization degree regulator and the balance of tap water; the addition amount of the mineralization degree regulator meets the requirement that the final content of the mineralization degree regulator in the applied gel profile control agent is more than or equal to 0.3 per thousand.
2. The water-soluble phenolic resin crosslinking agent low-temperature rapid gelling accelerator according to claim 1, wherein the cationic imine copolymer has a molecular weight of 3000-5000, and is one or a mixture of polyethyleneimine and polyvinylamine.
3. The low-temperature fast-gelling crosslinking accelerator for water-soluble phenolic resin crosslinking agent according to claim 1, wherein the weak base is one or a mixture of sodium carbonate and sodium bicarbonate.
4. The low-temperature fast-gelling crosslinking accelerator for the water-soluble phenolic resin crosslinking agent according to claim 1, wherein the mineralization regulator is one or a mixture of sodium chloride, sodium sulfate and calcium chloride.
5. A method for preparing the water-soluble phenolic resin crosslinking agent of any one of claims 1 to 4, which is a low-temperature quick-gelling crosslinking promoter and is characterized by comprising the following steps: and sequentially adding the cationic imine copolymer, the weak base, the mineralization degree regulator and tap water into the stirring container, and uniformly stirring to obtain the product.
6. The application of the water-soluble phenolic resin crosslinking agent of any one of claims 1 to 4 in low-temperature rapid gelling and crosslinking promotion is characterized in that the gel profile control agent applied to profile control at the formation temperature of 35-60 ℃ specifically comprises the following steps: sequentially adding a water-soluble phenolic resin cross-linking agent and partially hydrolyzed anionic polyacrylamide according to the mass ratio of the prepared solution of the gel profile control agent, stirring for 10 minutes, adding the water-soluble phenolic resin cross-linking agent to quickly form the gel cross-linking agent at a low temperature, and continuously stirring for 60 minutes to obtain the gel profile control agent.
7. The application of the water-soluble phenolic resin cross-linking agent in low-temperature rapid gelling and crosslinking promotion according to claim 6, wherein the water-soluble phenolic resin cross-linking agent and the water-soluble phenolic resin cross-linking agent of the low-temperature rapid gelling and crosslinking promotion are respectively used in a jelly profile control agent system at a concentration of 0.15-0.45 wt%, and the weight ratio of the water-soluble phenolic resin cross-linking agent to the water-soluble phenolic resin cross-linking agent is 1: 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110317591A (en) * | 2019-06-05 | 2019-10-11 | 大庆油田有限责任公司 | A kind of cardanol-aldehyde resin gel profile control agent and preparation method thereof |
| CN113429957A (en) * | 2021-08-10 | 2021-09-24 | 中海油田服务股份有限公司 | Particle size and strength controllable polymer particles and preparation method thereof |
| CN115819910A (en) * | 2022-12-01 | 2023-03-21 | 中国石油大学(华东) | Solid-free gel composition, solid-free gel system, preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102559159A (en) * | 2011-12-14 | 2012-07-11 | 中国石油天然气股份有限公司 | High-temperature-resistant phenolic resin weak gel profile control water plugging agent |
| CN103614123A (en) * | 2013-10-21 | 2014-03-05 | 中国石油大学(华东) | Polyethyleneimine jelly profile-control water-blocking agent |
| CN104877653A (en) * | 2015-05-08 | 2015-09-02 | 西南石油大学 | Phenolic aldehyde weak gel control and flooding agent for rapid gelling of low temperature oil reservoirs |
| CN106634907A (en) * | 2016-09-19 | 2017-05-10 | 中国石油化工股份有限公司 | Polyethyleneimine water shut-off and profile control agent as well as preparation method thereof |
-
2019
- 2019-05-30 CN CN201910462052.3A patent/CN110790959A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102559159A (en) * | 2011-12-14 | 2012-07-11 | 中国石油天然气股份有限公司 | High-temperature-resistant phenolic resin weak gel profile control water plugging agent |
| CN103614123A (en) * | 2013-10-21 | 2014-03-05 | 中国石油大学(华东) | Polyethyleneimine jelly profile-control water-blocking agent |
| CN104877653A (en) * | 2015-05-08 | 2015-09-02 | 西南石油大学 | Phenolic aldehyde weak gel control and flooding agent for rapid gelling of low temperature oil reservoirs |
| CN106634907A (en) * | 2016-09-19 | 2017-05-10 | 中国石油化工股份有限公司 | Polyethyleneimine water shut-off and profile control agent as well as preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JIA HU ET AL.: "Research on the Gelation Performance of Low Toxic PEI Cross-Linking PHPAM Gel Systems as Water Shutoff Agents in Low Temperature Reservoirs", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》 * |
| 贾艳平 等: "堵剂聚乙烯亚胺冻胶成冻影响因素研究", 《油田化学》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110317591A (en) * | 2019-06-05 | 2019-10-11 | 大庆油田有限责任公司 | A kind of cardanol-aldehyde resin gel profile control agent and preparation method thereof |
| CN113429957A (en) * | 2021-08-10 | 2021-09-24 | 中海油田服务股份有限公司 | Particle size and strength controllable polymer particles and preparation method thereof |
| CN113429957B (en) * | 2021-08-10 | 2022-12-02 | 中海油田服务股份有限公司 | Polymer particles with controllable granularity and strength and preparation method thereof |
| CN115819910A (en) * | 2022-12-01 | 2023-03-21 | 中国石油大学(华东) | Solid-free gel composition, solid-free gel system, preparation method and application thereof |
| CN115819910B (en) * | 2022-12-01 | 2023-08-11 | 中国石油大学(华东) | Solid-free gel composition, solid-free gel system, preparation method and application thereof |
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