CN101857661A - Micro-emulsion polymer for in-depth profile control and oil displacement of reservoirs and preparation method thereof - Google Patents
Micro-emulsion polymer for in-depth profile control and oil displacement of reservoirs and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a micro-emulsion polymer for in-depth profile control and oil displacement of reservoirs and a preparation method thereof. On the basis of a method for preparing a polymer by adopting a photopolymerization reaction, water-solubility anion monomers are added into aqueous solution containing acrylamide monomers, a dispersing agent and a cross-linking agent are added, an oil-water mixed emulsion is formed in a mixed medium of a surfactant and a solvent, and after an imitating agent is decomposed by ultraviolet light in a mode of photopolymerization reaction at the controlled temperature, the emulsion polymerization is initiated so as to form the micro-emulsion polymer. The micro-emulsion polymer prepared by the invention is suitable for reactions under the condition of multiple environments, and has the characteristics of safe and stable reaction systems, simple, easy and convenient operation, flexible adjustment of reaction process and reaction time, high production efficiency, low energy consumption, no pollution and the like. The micro-emulsion polymer of the invention can be dispersed into injection water at any concentration and can enter deep strata to form gel under the action of the cross-linking agent, so that the capability of blocking pore throats is formed gradually, high-permeability stripes of the strata are blocked effectively, the swept volume of the water is enlarged, and the crude recovery ratio of developing the reservoirs through water flooding is improved obviously.
Description
Technical field
The present invention relates to the oil production chemical materials and the preparation method of high molecular polymerization, the oil deposit deep part transfer drive that specifically is a kind of suitable oil reservoir is with micro-emulsion polymer and preparation method.
Background technology
In oilfield development process, waterflooding is to replenish producing energy, improves the most economical and effective means of oil recovery factor.Because China's oil reservoir major part belongs to nonmarine deposit, oil saturation is relatively low, reservoir disperses, and the oil reservoir nonuniformity is serious, therefore, tend to form high infiltration strip in the waterflooding process, injecting water can not drive crude oil effectively at oil reservoir, and flows out from oil well soon, forms invalid circulation, it is fast to cause well water to rise, and causes water logging.Existing profile control (transfer drive) material and technology or can not enter earth formation deep just form shutoff, or have problems such as stability and poor reliability, cost height in the immediate vicinity of wellbore.
Micro-emulsion polymer is used for waterflooding reservoir deep transfer drive material step by step, its use principle is a dispersiveness of utilizing micro-emulsion polymer good, can enter earth formation deep smoothly with injecting water, constantly migration forward in the stratum, under the linking agent effect, form frozen glue gradually, form shutoff at penetrating passage pore throat place, cause the changed course of liquid stream, realize enlarging ripples and volume, improve the purpose of oil recovery factor.The realization of this thought is based on the solution of following two key issues: the technology of a large amount of cheap stably manufactured micro-emulsion polymers; Micro-emulsion polymer and linking agent form frozen glue time and intensity may command technology.Micro-emulsion polymer by the present invention development deep transfer drive material has step by step satisfied the requirement of above-mentioned two aspects fully.
Summary of the invention
The present invention is by analyzing the various contradictions that influence the water drive development effectiveness in the waterflooding process, use for reference the reasonable part of existing profile control technique, according to the chemical reaction on basis, micro emulsion polyradical present principles, a kind of efficient, safe, stable oil deposit deep part transfer drive is with micro-emulsion polymer and preparation method.
The technical scheme of this invention comprises:
Oil deposit deep part transfer drive micro-emulsion polymer, comprise that acrylamide monomer, soluble anionic monomers, dispersion agent, tensio-active agent, solvent, deionized water and light trigger pass through the photopolymerization reaction mode under the temperature controllable condition, form micro-emulsion polymer, the mass percent of the consumption of each composition is: acrylamide 15～35%, soluble anionic monomers 5～30%, dispersion agent 1～15%, tensio-active agent 10～40%, solvent 20～60%, deionized water 10～20%, light trigger 0.1～3.0%; Wherein: soluble anionic monomers is one or more the mixture in vinylformic acid, vinylformic acid hydroxy butyl ester, methacrylic acid, 2-acrylamido-2-methyl propane sulfonic acid, the vinylformic acid methoxyl group ethyl ester; Tensio-active agent is one or more the mixture in sapn, soil temperature, sodium laurylsulfonate, the cetyl trimethylammonium bromide; Dispersion agent is one or more the mixture in N-vinyl pyrrolidone, the polyvinylpyrrolidone; Solvent is one or more the mixture in solvent oil, aliphatic hydrocarbon or the aromatic hydrocarbons; Light trigger is the acetophenone derivs that replaces of benzoin ether analog derivative, hydroxyl or amido, one or more the mixture in the tetrazo initiator.
Described sapn (Span) is one or more the mixture among Span-60, Span-65, Span-80, the Span-85; Described tween is one or more the mixture in tween 20, Tween-40, Tween-60, tween-80, Tween-65, the tween 85.
Described aliphatic hydrocarbon is one or both the mixture in octane, the hexanaphthene; Described solvent oil is one or more the mixture in kerosene, white oil, diesel oil, the gasoline; Described aromatic hydrocarbons is one or more the mixture in the benzene,toluene,xylene.
Described benzoin ether analog derivative is one or more the mixture in benzoin methyl ether, Benzoin ethyl ether, the benzoin dimethylether; The acetophenone derivs that described hydroxyl or amido replace is 1-hydroxy-cyclohexyl phenyl ketone, the 2-methyl isophthalic acid-[mixture of one or more in 4-(methyl thio-phenyl)-2-morpholino acetone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxy-2-methyl propyl group) ketone, the 2-hydroxy-2-methyl-1-phenyl-acetone; Described tetrazo initiator is one or both the mixture in Diisopropyl azodicarboxylate or the azo-bis-isobutyrate hydrochloride.
Oil deposit deep part transfer drive of the present invention one of preparation method of micro-emulsion polymer comprises:
(1) aqueous solution preparation: soluble anionic monomers is dissolved in the deionized water, add dispersion agent and stir, add acrylamide monomer again and be stirred well to the no solid insoluble of solution clarification, use alkali (NaOH) aqueous solution that solution is adjusted to pH=7 again after, add linking agent, stirred 1～2 hour;
(2) emulsion system preparation: tensio-active agent is dissolved in the solvent, treat fully dissolving evenly after, the aqueous solution of step (1) is progressively added, fully stir, promptly obtain transparent or semitransparent emulsion polymerization system;
(3) photopolymerization reaction: with light trigger with dissolution with solvents after, join in the emulsion system of step (2), after stirring, in reactor, feed rare gas element, oxygen with the replacement(metathesis)reaction system, emulsion system is under the deoxygenation conditions, uses UV-irradiation again, make it to finish by photopolymerization reaction.
The preparation method's of oil deposit deep part transfer drive usefulness micro-emulsion polymer of the present invention two comprises:
(1) aqueous solution preparation: soluble anionic monomers is dissolved in the deionized water, adding dispersion agent stirs, add acrylamide monomer again and be stirred well to the no solid insoluble of solution clarification, with alkali aqueous solution solution is adjusted to pH=7 again after, stirred 1～2 hour;
(2) emulsion system preparation: the part surface promoting agent is dissolved in the partial solvent, treat fully dissolving evenly after, the aqueous solution of step (1) is progressively added, fully stir, promptly obtain transparent or semitransparent emulsion polymerization system;
(3) photopolymerization reaction: with light trigger with dissolution with solvents after, join in the emulsion system of step (2), after stirring, in reactor, feed rare gas element, oxygen with the replacement(metathesis)reaction system, emulsion system is under the deoxygenation conditions, uses UV-irradiation again, make it to finish by photopolymerization reaction;
(4) in effusive emulsion from the illumination reaction device, can finish whole process after fully stirring behind the solvent of adding 2～6% and 3～8% the tensio-active agent, this micro-emulsion polymer system is the transparent emulsion state, splashes in the water and can directly disperse fast.
Described rare gas element is helium, argon gas or nitrogen.
The present invention adopts photopolymerization reaction to prepare the method for micro-emulsion polymer, by adopting the soluble anionic monomers and the acrylamide monomer aqueous solution, add dispersion agent and linking agent, in tensio-active agent and solvent medium, form the profit mixed emulsion, under the temperature controllable condition, pass through the photopolymerization reaction mode, initiator is decomposed the back by UV-light and causes letex polymerization, forms the micro-emulsion polymer that outward appearance is transparent or semitransparent emulsion state.
The micro-emulsion polymer material of the present invention's preparation is adapted at reacting under the multiple envrionment conditions, having reaction system safety and stability, simple and easy convenient, the reaction process of operation and time can adjust flexibly, characteristics such as the high and low energy consumption of production efficiency is pollution-free, the present invention utilize micro-emulsion polymer arbitrarily being dispersed in of concentration pore throat is formed the ability of shutoff, the effective height infiltration band on shutoff stratum forming frozen glue gradually after injecting water and can entering earth formation deep, enlarge the swept volume of water, significantly improve the oil recovery factor of water drive exploitation oil reservoir.
Embodiment
Embodiment 1
(1) aqueous solution preparation: 18% soluble anionic monomers dissolved in 10% the deionized water, the dispersion agent of adding 3% stirs, add 20% acrylamide monomer again and be stirred well to the no solid insoluble of solution clarification, after with the NaOH aqueous solution solution being adjusted to pH=7 again, stirred 1～2 hour;
(2) emulsion system preparation: the tensio-active agent with 15% dissolves in 20% the solvent, treat fully dissolving evenly after, the aqueous solution of step (1) is progressively added, fully stir, promptly obtain transparent or semitransparent emulsion polymerization system;
(3) photopolymerization reaction: the light trigger with 1.5% with 5% dissolution with solvents after, join in the emulsion system of step (2), after stirring, in reactor, feed rare gas element, oxygen with the replacement(metathesis)reaction system, emulsion system is under the deoxygenation conditions, with volume pump emulsion is at the uniform velocity imported in the pipeline of ultraviolet lighting device again, make it fully to react by photopolymerization in the reactor;
(4) in effusive emulsion from the illumination reaction device, can finish whole process after fully stirring after adding the solvent account for reaction system 2% and accounting for 3% tensio-active agent, this micro-emulsion polymer system is the transparent emulsion state, splashes in the water and can directly disperse fast.
Embodiment 2
(1) aqueous solution preparation: 10% soluble anionic monomers dissolved in 12% the deionized water, the dispersion agent of adding 2.5% stirs, add the acrylamide monomer that accounts for reaction system 31% again and be stirred well to the no solid insoluble of solution clarification, after with the NaOH aqueous solution solution being adjusted to pH=7 again, stirred 1～2 hour;
(2) emulsion system preparation: the tensio-active agent with 10% dissolves in 22% the solvent, treat fully dissolving evenly after, the aqueous solution of step (1) is progressively added, fully stir, promptly obtain transparent or semitransparent emulsion polymerization system;
(3) photopolymerization reaction: the light trigger with 1% with 1.75% dissolution with solvents after, join in the emulsion system of step (2), after stirring, in reactor, feed rare gas element, oxygen with the replacement(metathesis)reaction system, emulsion system is under the deoxygenation conditions, with volume pump emulsion is at the uniform velocity imported in the pipeline of ultraviolet lighting device again, make it fully to react by photopolymerization in the reactor;
(4) in effusive emulsion from the illumination reaction device, can finish whole process after fully stirring behind the solvent of adding 2.5% and 7% the tensio-active agent, this micro-emulsion polymer system is the transparent emulsion state, splashes in the water and can directly disperse fast.
Embodiment 3
(1) aqueous solution preparation: 15% soluble anionic monomers dissolved in 9% the deionized water, the dispersion agent of adding 1% stirs, add 27% acrylamide monomer again and be stirred well to the no solid insoluble of solution clarification, after with the NaOH aqueous solution solution being adjusted to pH=7 again, stirred 1～2 hour;
(2) emulsion system preparation: the tensio-active agent with 20% dissolves in 22% the solvent, treat fully dissolving evenly after, the aqueous solution of step (1) is progressively added, fully stir, promptly obtain transparent or semitransparent emulsion polymerization system;
(3) photopolymerization reaction: the light trigger with 1% with 3% dissolution with solvents after, join in the emulsion system of step (2), after stirring, in reactor, feed rare gas element, oxygen with the replacement(metathesis)reaction system, emulsion system is under the deoxygenation conditions, with volume pump emulsion is at the uniform velocity imported in the pipeline of ultraviolet lighting device again, make it fully to react by photopolymerization in the reactor.
Above-mentionedly enumerated the exemplary embodiments that several products combine with method, adopt prior preparation method can obtain product of the present invention equally at the technical scheme of product, but the product effect of existing method preparation has been better not as preparation method of the present invention.
The present invention has enumerated many substitutes, for those skilled in the art, according to prompting of the present invention, all can implement, and no longer does to illustrate one by one and enumerate.
Experiment showed, that by a large amount of indoor shutoff and transfer drive such material can effectively improve the stratum nonuniformity, enlarge the water swept volume, under different geologic conditions, improve oil recovery 10～15%.The temperature and the salinity that are characterized in injecting water and local water are less to its influence, are applicable to all kinds of waterflooding reservoirs; The stratum nonuniformity is serious more, and the transfer drive effect is obvious more; Because shutoff is the stratum pore throat, consumption is few, and cost is low; It is controlled to enter earth formation deep, can effectively improve mining-employed reserves, and validity period is long; Injection device is simple, and is convenient.The prospective oil of the existing waterflooding of China has more than 8,000,000,000 tons, and present technique is fit to 90% water drive exploitation oil reservoir use, and its realistic meaning and social benefit are apparent.
Claims (7)
1. oil deposit deep part transfer drive micro-emulsion polymer, it is characterized in that acrylamide monomer, soluble anionic monomers, dispersion agent, tensio-active agent, solvent, deionized water and light trigger are passed through the photopolymerization reaction mode under the temperature controllable condition, form micro-emulsion polymer, the mass percent of each composition consumption: acrylamide 15～35%, soluble anionic monomers 5～30%, dispersion agent 1～15%, tensio-active agent 10～40%, solvent 20～60%, deionized water 10～20%, light trigger 0.1～3.0%; Wherein:
Soluble anionic monomers is one or more the mixture in vinylformic acid, vinylformic acid hydroxy butyl ester, methacrylic acid, 2-acrylamido-2-methyl propane sulfonic acid, the vinylformic acid methoxyl group ethyl ester;
Tensio-active agent is one or more the mixture in sapn, soil temperature, sodium laurylsulfonate, the cetyl trimethylammonium bromide;
Dispersion agent is one or more the mixture in N-vinyl pyrrolidone, the polyvinylpyrrolidone;
Solvent is one or more the mixture in solvent oil, aliphatic hydrocarbon or the aromatic hydrocarbons;
Light trigger is the acetophenone derivs that replaces of benzoin ether analog derivative, hydroxyl or amido, one or more the mixture in the tetrazo initiator.
2. oil deposit deep part transfer drive micro-emulsion polymer according to claim 1 is characterized in that, described sapn is one or more the mixture in Arlacel-60, Arlacel-65, Arlacel-80, the Arlacel-85; Described tween is one or more the mixture in tween 20, Tween-40, Tween-60, tween-80, Tween-65, the tween 85.
3. oil deposit deep part transfer drive micro-emulsion polymer according to claim 1 is characterized in that, described aliphatic hydrocarbon is one or both the mixture in octane, the hexanaphthene; Described solvent oil is one or more the mixture in kerosene, white oil, diesel oil, the gasoline; Described aromatic hydrocarbons is one or more the mixture in the benzene,toluene,xylene.
4. oil deposit deep part transfer drive micro-emulsion polymer according to claim 1 is characterized in that, described benzoin ether analog derivative is one or more the mixture in benzoin methyl ether, Benzoin ethyl ether, the benzoin dimethylether; The acetophenone derivs that described hydroxyl or amido replace is 1-hydroxy-cyclohexyl phenyl ketone, the 2-methyl isophthalic acid-[mixture of one or more in 4-(methyl thio-phenyl)-2-morpholino acetone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxy-2-methyl propyl group) ketone, the 2-hydroxy-2-methyl-1-phenyl-acetone; Described tetrazo initiator is one or both the mixture in Diisopropyl azodicarboxylate or the azo-bis-isobutyrate hydrochloride.
5. according to the preparation method of each described oil deposit deep part transfer drive of claim 1～4, it is characterized in that comprising with micro-emulsion polymer:
(1) aqueous solution preparation: soluble anionic monomers is dissolved in the deionized water, adding dispersion agent stirs, add acrylamide monomer again and be stirred well to the no solid insoluble of solution clarification, with alkali aqueous solution solution is adjusted to pH=7 again after, stirred 1～2 hour;
(2) emulsion system preparation: tensio-active agent is dissolved in the solvent, treat fully dissolving evenly after, the aqueous solution of step (1) is progressively added, fully stir, promptly obtain transparent or semitransparent emulsion polymerization system;
(3) photopolymerization reaction: with light trigger with dissolution with solvents after, join in the emulsion system of step (2), after stirring, in reactor, feed rare gas element, oxygen with the replacement(metathesis)reaction system, emulsion system is under the deoxygenation conditions, uses UV-irradiation again, make it to finish by photopolymerization reaction.
6. according to the preparation method of each described oil deposit deep part transfer drive of claim 1～4, it is characterized in that comprising with micro-emulsion polymer:
(1) aqueous solution preparation: soluble anionic monomers is dissolved in the deionized water, adding dispersion agent stirs, add acrylamide monomer again and be stirred well to the no solid insoluble of solution clarification, with alkali aqueous solution solution is adjusted to pH=7 again after, stirred 1～2 hour;
(2) emulsion system preparation: the part surface promoting agent is dissolved in the partial solvent, treat fully dissolving evenly after, the aqueous solution of step (1) is progressively added, fully stir, promptly obtain transparent or semitransparent emulsion polymerization system;
(3) photopolymerization reaction: with light trigger with dissolution with solvents after, join in the emulsion system of step (2), after stirring, in reactor, feed rare gas element, oxygen with the replacement(metathesis)reaction system, emulsion system is under the deoxygenation conditions, uses UV-irradiation again, make it to finish by photopolymerization reaction;
(4) in effusive emulsion from the illumination reaction device, can finish whole process after fully stirring behind the solvent of adding 2～6% and 3～8% the tensio-active agent, this micro-emulsion polymer system is the transparent emulsion state, splashes in the water and can directly disperse fast.
7. according to the preparation method of claim 5 or 6 described oil deposit deep part transfer drives usefulness micro-emulsion polymers, it is characterized in that described rare gas element is helium, argon gas or nitrogen.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111369A (en) * | 2015-10-16 | 2015-12-02 | 山东石大油田技术服务股份有限公司 | Elastic microspheres applicable to deep profile control of oil field and preparation method of elastic microspheres |
| CN106402660A (en) * | 2016-09-05 | 2017-02-15 | 路殿勋 | Preparation method for emulsion suspension system of poly-alpha-olefin oil drag reducer |
| CN117143579A (en) * | 2023-09-04 | 2023-12-01 | 中国石油大学(华东) | Formula and construction method of in-situ porous polymer gel |
-
2010
- 2010-05-14 CN CN201010181918A patent/CN101857661A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111369A (en) * | 2015-10-16 | 2015-12-02 | 山东石大油田技术服务股份有限公司 | Elastic microspheres applicable to deep profile control of oil field and preparation method of elastic microspheres |
| CN105111369B (en) * | 2015-10-16 | 2022-03-08 | 山东石大油田技术服务股份有限公司 | Elastic microsphere suitable for deep profile control and flooding of oil field and preparation method |
| CN106402660A (en) * | 2016-09-05 | 2017-02-15 | 路殿勋 | Preparation method for emulsion suspension system of poly-alpha-olefin oil drag reducer |
| CN117143579A (en) * | 2023-09-04 | 2023-12-01 | 中国石油大学(华东) | Formula and construction method of in-situ porous polymer gel |
| CN117143579B (en) * | 2023-09-04 | 2024-05-14 | 中国石油大学(华东) | Formula and construction method of in-situ porous polymer gel |
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