CN104861946A - Flexible controlled-release microsphere disperse system formed by natural water-soluble polymer and preparation thereof and application of system in reinforcement of oil extraction - Google Patents
Flexible controlled-release microsphere disperse system formed by natural water-soluble polymer and preparation thereof and application of system in reinforcement of oil extraction Download PDFInfo
- Publication number
- CN104861946A CN104861946A CN201510144174.XA CN201510144174A CN104861946A CN 104861946 A CN104861946 A CN 104861946A CN 201510144174 A CN201510144174 A CN 201510144174A CN 104861946 A CN104861946 A CN 104861946A
- Authority
- CN
- China
- Prior art keywords
- release microsphere
- octane
- flexible control
- natural water
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/514—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
-
- C—CHEMISTRY; METALLURGY
- 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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/516—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls characterised by their form or by the form of their components, e.g. encapsulated material
-
- C—CHEMISTRY; METALLURGY
- 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
- C09K8/584—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 surfactants
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Colloid Chemistry (AREA)
- Medicinal Preparation (AREA)
Abstract
The invention relates to a flexible controlled-release microsphere disperse system formed by a natural water-soluble polymer and preparation thereof and application of the system in reinforcement of oil extraction. The disperse system comprises an aqueous solution of the natural water-soluble polymer containing carboxyl and hydroxyl groups, an aqueous solution of an inorganic salt and a surfactant-dispersed octane emulsion, wherein the surfactant-dispersed octane emulsion is prepared by adding octane into an aqueous surfactant solution and carrying out uniform dispersion. According to the invention, the natural water-soluble polymer used in the invention is widely available, regenerable and environment-friendly, contains a great number of hydroxyl groups and a proper amount of carboxyl groups in the molecular chains and can form a flexible controlled-release microsphere with proper chain density and a flexible core-shell structure in the presence of multivalent inorganic salt ions. The flexible controlled-release microsphere migrates in holes in strata and can plug large holes, improve injection pressure and adjust injection profile.
Description
Technical field
The present invention relates to a kind of microballoon dispersion system formed by natural water-soluble copolymer, can be used in oilfield water extraction, playing plugging and profile con-trol effect, and high-efficient oil-displacing agent can be carried go deep into reservoir Co ntrolled release, reduce crude oil interfacial tension, disposablely increase substantially recovery ratio, belong to field of oilfield chemistry.
Background technology
Oil is as strategic resource, and it is effectively exploited and utilizes very important.Because oil is nonrenewable resource, along with improving constantly of the level of the productive forces, society sharply rises to petroleum demand, and find that the opportunity of larger reserves oil reservoir reduces again, the recovery ratio of raising developed field is got most of the attention, and taking technique means to improve recovery ratio has become the necessary production measure had a high potential.
The flooding system channelling problem caused by Reservoir Heterogeneity is the principal contradiction that restriction oil recovery factor improves, and along with the expansion of exploitation scale, this contradiction, is on the rise on the impact of output.Current water flooding mainly adopts profile control technique to improve intake profile, as injected high density pill high viscosity copolymer solution to oil reservoir, reservoir fluid being altered course, improving the sweep efficiency injecting water.But existing plugging and profile con-trol system, as polyacrylamide (HPAM) polymers soln or colloidal dispersed gel profile control shutoff system (CDG) all exist not dilution-resistant, chemistry or biological degradation, mechanical shearing viscosity reduction fast, adjust stifled weak effect or the problem such as reservoir damage is large.
Polymer microballoon is the deep profile controlling shutoff type material that development in recent years is got up.Laboratory experiment and field test result show, injection of polymer microballoon can lifting injection pressure well, improve well group oil-producing capacity.Its mechanism mainly by entering earth formation deep shutoff height penetrating passage, causes liquid stream to alter course, and reaches the object expanding water drive swept volume.The microballoon that research shows to have favorable elasticity can meet amendment note enter, stifled the requirement of living, migrating, can effective plugging high permeable zone, raising oil-producing capacity.
Currently reported polymer microballoon adopts chemical process synthesis, and biodegradability is poor, and its application exists certain hidden danger.In addition, polymer microballoon is injected earth formation deep, only plugging and profile con-trol, effectiveness comparison is single, if can carry oil-displacing agent to enter stratum and Co ntrolled release, can improve effect of gathering further, disposablely increases substantially recovery ratio.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of flexible control-release microsphere dispersion system of being formed by natural water-soluble copolymer and preparation thereof and the application in intensified oil reduction, this flexible control-release microsphere dispersion system not only has plugging and profile con-trol performance, and oil-displacing agent can be carried go deep into reservoir Co ntrolled release, improve effect of gathering further.
Term illustrates:
PV: injection pore volume multiple, namely injects the fluid volume of core sample and the ratio of core sample volume of voids.Such as: namely 1PV represents that injection rock injects the fluid volume of core sample and the ratio of core sample volume of voids is 1.
Technical scheme of the present invention is as follows:
The flexible control-release microsphere dispersion system formed by natural water-soluble copolymer, comprises the octane emulsion of the natural water-soluble copolymer aqueous solution containing carboxyl and hydroxyl, inorganic salt solution and surfactant-dispersed;
The octane emulsion of described surfactant-dispersed in water phase surfactant mixture, adds octane and be uniformly dispersed to obtain;
The mass ratio of the octane emulsion of described the natural water-soluble copolymer aqueous solution containing carboxyl and hydroxyl, inorganic salt solution and surfactant-dispersed is (12-35): (50-100): (1-3);
The mass concentration of the described natural water-soluble copolymer aqueous solution is 0.05%-1.0%, the concentration of described inorganic salt solution is 50ppm-10000ppm, the mass concentration of described water phase surfactant mixture is 0.05%-0.6%, and described water phase surfactant mixture and the mass ratio of octane are (2-10): (1-2).
According to the present invention, preferably, the diameter of described flexible control-release microsphere is 0.01-5.0 micron.
According to the present invention, preferably, the described natural water-soluble copolymer containing carboxyl and hydroxyl is modified-cellulose, treated starch, gelatin, chitosan and/or alginates; Preferred further, the described molecular weight ranges containing the natural water-soluble copolymer of carboxyl and hydroxyl is 20000 ~ 1500000.
According to the present invention, preferably, described inorganic salt comprise bariumchloride, aluminum chloride, iron(ic) chloride, ferric sulfate, cupric chloride, zinc chloride, zinc sulfate and/or calcium chloride.
According to the present invention, preferably, described tensio-active agent is one or more mixing in alkylolamide, sulfonated petro-leum, fatty-acid ethyl ester sulfonate, alkyl carboxylate, sultaine and carboxybetaine; In the octane emulsion of described surfactant-dispersed, the distribution of sizes of emulsion particle is 0.1-0.5 micron.
According to the present invention, preferably, the tolerated salinity range of described flexible control-release microsphere is: total mineralization 50ppm-100000ppm, calcium ions and magnesium ions total concn 50ppm-10000ppm.
According to the present invention, the preparation method of above-mentioned flexible control-release microsphere dispersion system, comprises step as follows:
(1) by soluble in water for the natural water-soluble copolymer containing carboxyl and hydroxyl, continue stirring until whole dissolving, obtained mass concentration is the natural water-soluble copolymer aqueous solution of 0.05%-1.0%;
(2) be mixed with soluble in water for tensio-active agent the solution that mass concentration is 0.05%-0.6%, be (2-10) by the mass ratio of water phase surfactant mixture and octane: (1-2) adds octane, stir, ultrasonic disperse, obtains the octane emulsion of surfactant-dispersed;
(3) the octane emulsion of surfactant-dispersed step (2) obtained joins the natural water-soluble copolymer aqueous solution that step (1) obtains, and stirs, obtains mixing solutions;
(4) inorganic salt are mixed with the inorganic salt solution that concentration is 50ppm-10000ppm, the mixing solutions that step (3) obtains is added drop-wise in inorganic salt solution with the speed of 20ml/h-100ml/h, obtain flexible control-release microsphere dispersion system.
According to the inventive method, preferably, in step (2), the time of ultrasonic disperse is 1-3h.
According to the present invention, above-mentioned flexible control-release microsphere dispersion system has plugging and profile con-trol and controlled release properties, can be used as plugging agent or amendment is applied in oil recovery process;
Preferably, to comprise step as follows for embody rule method:
It is 0.05%-0.3% that flexible control-release microsphere dispersion system is diluted with water to mass concentration, to metaideophone water after injecting 0.3-0.6PV in oil recovery Tibetan.
According to the application of the flexible control-release microsphere dispersion system of the present invention, preferably, after flexible control-release microsphere dispersion system is diluted by water, tensio-active agent is released gradually as oil-displacing agent, and it is 0.1-0.3% that flexible control-release microsphere dispersion system is diluted to mass concentration.Dilute the down-hole production water that water used can be local water or the rear reuse of process.
Flexible control-release microsphere dispersion system of the present invention can be applicable to slit formation carbonate oil reservoir and conventional sandstone oil reservoir, can improve recovery ratio.
Principle of the present invention:
Containing great amount of hydroxy group and appropriate carboxyl in natural water-soluble copolymer, sequestering action can be there is in the polyvalent cation of proper concn with appropriate hydroxyl and carboxyl (polymkeric substance), each bar chain of this water-soluble polymers is intertwined mutually, forms the flexible microballoon with flexible nucleocapsid structure that chain density is suitable.Water phase surfactant mixture and octane are (2-10) at mass ratio: time (1-2), can be formed and be uniformly dispersed and stable emulsion system, but the octane emulsion prepared when octane add-on too high (exceeding aforementioned proportion) is extremely unstable and affect the preparation of next step mixing solutions.With shell portion in the core that the octane emulsion of surfactant-dispersed can be dispersed in the flexible microballoon of nucleocapsid structure.In dilution, hydration swelling can be there is and discharged gradually by the surfactant in flexible microballoon in flexible microballoon.Flexible microballoon can degraded completely after 300 days.
Technical characterstic of the present invention and excellent results as follows:
1, the natural water-soluble copolymer that the present invention adopts is originated wide, renewable, there is great amount of hydroxy group and appropriate carboxyl in environmental friendliness in molecular chain, can deposit in case at polyvalent mineral salt ion, form the flexible control-release microsphere with flexible nucleocapsid structure that chain density is suitable.Flexible control-release microsphere is migrated in formation pore, can shout by shutoff macropore, improves injection pressure, adjustment input profile.
2, flexible control-release microsphere dispersion stability of the present invention is good, in underground through migration after a while, degrades, can not bring pollution to environment.
3, oil-displacing agent can be wrapped in flexible control-release microsphere inside by the present invention, carries to earth formation deep slow releasing oil-displacing agent, sustainable reduction oil water interfacial tension, improves oil displacement efficiency.
4, the methods for making and using same of the flexible control-release microsphere dispersion system of the present invention is simple, and the cost of material is low, and this flexible control-release microsphere dispersion system is to the strong adaptability of polyvalent inorganic cation, does not have secondary pollution to environment.
5, the flexible control-release microsphere dispersion system environmental protection that the present invention relates to, both can realize deep profile controlling, can reduce oil water interfacial tension by controlled release tensio-active agent again, therefore have important application prospect in intensified oil reduction field.
Accompanying drawing explanation
Fig. 1 is the size curve over time of the flexible control-release microsphere of the embodiment of the present invention 1.
Fig. 2 breaks and degraded condition diagram with the flexible control-release microsphere of microscopic examination in the embodiment of the present invention 1.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but be not limited only to this.
Raw materials usedly in embodiment be convenient source, commercial products.
Embodiment 1:
The flexible control-release microsphere dispersion system formed by natural water-soluble copolymer, comprises the octane emulsion of the natural water-soluble copolymer aqueous solution containing carboxyl and hydroxyl, inorganic salt solution and surfactant-dispersed;
The octane emulsion of described surfactant-dispersed in water phase surfactant mixture, adds octane and be uniformly dispersed to obtain;
The mass ratio of the octane emulsion of described the natural water-soluble copolymer aqueous solution containing carboxyl and hydroxyl, inorganic salt solution and surfactant-dispersed is 12:50:2.4;
The mass concentration of the described natural water-soluble copolymer aqueous solution is 0.6%, the concentration of described inorganic salt solution is 8000ppm, the mass concentration of described water phase surfactant mixture is 0.1%, and described water phase surfactant mixture and the mass ratio of octane are 2:1;
Described natural water-soluble copolymer is alginates, and described inorganic salt are cupric chloride and calcium chloride, and described tensio-active agent is alkylolamide.
It is as follows that preparation method comprises step:
(1) mixed with 100g water by 0.6g alginates, mechanical stirring at 25 DEG C, until alginates dissolves completely, obtained mass concentration is the natural water-soluble copolymer aqueous solution of 0.6%;
(2) 0.1g alkylolamide is mixed with 100g water, mechanical stirring at 25 DEG C is until dissolve completely, form the solution of homogeneous transparent, octane is added by the mass ratio 2:1 of the alkylolamide aqueous solution and octane, stir, ultrasonic 1 hour, obtain the octane emulsion that distribution of sizes is the stable surfactant-dispersed of 0.1-0.5 micron;
(3) the octane emulsion of step (1) the natural water-soluble copolymer aqueous solution with step (2) surfactant-dispersed mixed and stir, obtaining mixing solutions;
(4) cupric chloride and calcium chloride are mixed with the inorganic salt solution that total concn is 8000ppm, are placed in Water Tank with Temp.-controlled, steady temperature is 40 DEG C; Be the kapillary of 20 μm by diameter with microsyringe, be injected in inorganic salt solution with the injection speed of 50ml/h by mixing solutions, obtained diameter is the flexible control-release microsphere dispersion system of 0.01-1.0 micron.
In this process, utilize the hole of the aperture simulated formation of kapillary, by adjusting the injection speed of microsyringe, the pressure of simulated injection water.
Experimental example 1:
The salinity flexible control-release microsphere obtained for embodiment 1 being placed in flowing is the mineralized water solution of 2000ppm, and the temperature of constant mineralized water is 40 DEG C, simulated formation environment, observes dimensional change and the degraded situation of flexible control-release microsphere.
Utilize microscope to monitor the hydration swelling rule of flexible control-release microsphere in the free migration process in stratum, the size of flexible control-release microsphere over time as shown in Figure 1.As can be seen from Figure 1, along with the increase of time, flexible control-release microsphere expands gradually.Therefore in the migration process of stratum, until there is plugging action in flexible control-release microsphere meeting hydration swelling.
After 300 days, flexible control-release microsphere breaks degraded completely.Known, this flexible control-release microsphere can be degraded in the migration process of stratum, does not pollute the environment.
Experimental example 2:
In experimental example 1, in flexible control-release microsphere expansion process, tensio-active agent can be discharged gradually.The flexible control-release microsphere external solution of leaching, utilizes rotation to drip interfacial tensimeter and measures the ability that the tensio-active agent discharged reduces interfacial tension.The model of the interfacial tensimeter used is TEXAS-500, experimental temperature is regulated to be 50 DEG C, the oil phase used is the outer oil transportation of victory Tuo Kou, and adjusting rotary speed is 6000r/min, found that oil water interfacial tension can be reduced to 10 by the tensio-active agent that flexible control-release microsphere discharges in 15min
-2mN.m
-1.
Embodiment 2:
The flexible control-release microsphere dispersion system formed by natural water-soluble copolymer, comprises the octane emulsion of the natural water-soluble copolymer aqueous solution containing carboxyl and hydroxyl, inorganic salt solution and surfactant-dispersed;
The octane emulsion of described surfactant-dispersed in water phase surfactant mixture, adds octane and be uniformly dispersed to obtain;
The mass ratio of the octane emulsion of described the natural water-soluble copolymer aqueous solution containing carboxyl and hydroxyl, inorganic salt solution and surfactant-dispersed is 35:100:3;
The mass concentration of the described natural water-soluble copolymer aqueous solution is 0.8%, the concentration of described inorganic salt solution is 100ppm, the mass concentration of described water phase surfactant mixture is 0.1%, and described water phase surfactant mixture and the mass ratio of octane are 1:1;
Described natural water-soluble copolymer is chitosan, and described inorganic salt are calcium chloride, and described tensio-active agent is carboxybetaine.
It is as follows that preparation method comprises step:
(1) mixed with 100g water by 0.8g chitosan, mechanical stirring at 25 DEG C, until chitosan dissolves completely, obtained mass concentration is the natural water-soluble copolymer aqueous solution of 0.8%;
(2) 0.1g carboxybetaine is mixed with 100g water, mechanical stirring at 25 DEG C is until dissolve completely, form the solution of homogeneous transparent, octane is added by the mass ratio 1:1 of the carboxybetaine aqueous solution and octane, stir, ultrasonic 1 hour, obtain the octane emulsion that distribution of sizes is the stable surfactant-dispersed of 0.1-0.5 micron;
(3) step (1) the natural water-soluble copolymer aqueous solution mixed with the octane emulsion of step (2) surfactant-dispersed and be stirred to evenly, obtaining mixing solutions;
(4) calcium chloride is mixed with the inorganic salt solution that total concn is 100ppm, the inorganic salt solution configured is placed in Water Tank with Temp.-controlled, steady temperature is 40 DEG C; Be the kapillary of 10 μm by diameter with microsyringe, be injected in inorganic salt solution with the injection speed of 80ml/h by mixing solutions, obtained diameter is the flexible control-release microsphere dispersion system of 0.1-5.0 micron.
When the flexible control-release microsphere that the present embodiment obtains injects stratum, tensio-active agent can be come out, remaining natural water-soluble copolymer also can continue to react with the polyvalent metal ion that contains in stratum, the flexible control-release microsphere of further formation, shutoff pore throat, concrete rule and experimental example 1,2 similar.After measured, the reduction interfacial tension of crude oil and water can be down to 10 by the tensio-active agent discharged
-2mN.m
-1.
Embodiment 3:
The flexible control-release microsphere dispersion system formed by natural water-soluble copolymer, comprises the octane emulsion of the natural water-soluble copolymer aqueous solution containing carboxyl and hydroxyl, inorganic salt solution and surfactant-dispersed;
The octane emulsion of described surfactant-dispersed in water phase surfactant mixture, adds octane and be uniformly dispersed to obtain;
The mass ratio of the octane emulsion of described the natural water-soluble copolymer aqueous solution containing carboxyl and hydroxyl, inorganic salt solution and surfactant-dispersed is 20:80:3;
The mass concentration of the described natural water-soluble copolymer aqueous solution is 1.0%, the concentration of described inorganic salt solution is 2000ppm, the mass concentration of described water phase surfactant mixture is 0.2%, and described water phase surfactant mixture and the mass ratio of octane are 3:1;
Described natural water-soluble copolymer is treated starch, and described inorganic salt are iron(ic) chloride, calcium chloride, zinc sulfate and bariumchloride, and described tensio-active agent is sulfonated petro-leum.
It is as follows that preparation method comprises step:
(1) mixed with 100g water by 1g treated starch, mechanical stirring at 25 DEG C, until treated starch dissolves completely, obtained mass concentration is the natural water-soluble copolymer aqueous solution of 1%;
(2) 0.2g sulfonated petro-leum is mixed with 100g water, mechanical stirring at 25 DEG C is until dissolve completely, form the solution of homogeneous transparent, octane is added by the mass ratio 3:1 of mahogany acid salt brine solution and octane, stir, ultrasonic 1 hour, obtain the octane emulsion that distribution of sizes is the stable surfactant-dispersed of 0.1-0.5 micron;
(3) step (1) the natural water-soluble copolymer aqueous solution mixed with the octane emulsion of step (2) surfactant-dispersed and be stirred to evenly, obtaining mixing solutions;
(4) iron(ic) chloride, calcium chloride, zinc sulfate and bariumchloride are mixed with the mineralized water that total mineralization is 2000ppm, the mineralized water configured is placed in Water Tank with Temp.-controlled, steady temperature is 40 DEG C; Be the kapillary of 10 μm by diameter with microsyringe, be injected in inorganic salt solution with the injection speed of 20ml/h by mixing solutions, obtained diameter is the flexible control-release microsphere dispersion system of 0.1-5.0 micron.
When the obtained flexible control-release microsphere of the present embodiment injects stratum, can hydration swelling shutoff pore throat, and gradually tensio-active agent is come out, concrete rule and experimental example 1,2 similar.After measured, the reduction interfacial tension of crude oil and water can be down to 10 by the tensio-active agent discharged
-2mN.m
-1.
Embodiment 4:
The flexible control-release microsphere dispersion system formed by natural water-soluble copolymer, comprises the octane emulsion of the natural water-soluble copolymer aqueous solution containing carboxyl and hydroxyl, inorganic salt solution and surfactant-dispersed;
The octane emulsion of described surfactant-dispersed in water phase surfactant mixture, adds octane and be uniformly dispersed to obtain;
The mass ratio of the octane emulsion of described the natural water-soluble copolymer aqueous solution containing carboxyl and hydroxyl, inorganic salt solution and surfactant-dispersed is 15:75:3;
The mass concentration of the described natural water-soluble copolymer aqueous solution is 0.1%, the concentration of described inorganic salt solution is 10000ppm, the mass concentration of described water phase surfactant mixture is 0.1%, and described water phase surfactant mixture and the mass ratio of octane are 1:1;
Described natural water-soluble copolymer is modified-cellulose, and described inorganic salt are aluminum chloride, calcium chloride, zinc chloride and bariumchloride, and described tensio-active agent is fatty-acid ethyl ester sulfonate.
It is as follows that preparation method comprises step:
(1) mixed with 100g water by 0.1g modified-cellulose, mechanical stirring at 25 DEG C, until modified-cellulose dissolves completely, obtained mass concentration is the natural water-soluble copolymer aqueous solution of 0.1%;
(2) 0.1g fatty-acid ethyl ester sulfonate is mixed with 100g water, mechanical stirring at 25 DEG C is until dissolve completely, form the solution of homogeneous transparent, octane is added by the mass ratio 1:1 of the fatty-acid ethyl ester sulfonate aqueous solution and octane, stir, ultrasonic 1 hour, obtain the octane emulsion that distribution of sizes is the stable surfactant-dispersed of 0.1-0.5 micron;
(3) step (1) natural water-soluble copolymer solution mixed with the octane emulsion of step (2) surfactant-dispersed and be stirred to evenly, obtaining mixing solutions;
(4) aluminum chloride, calcium chloride, zinc chloride and bariumchloride are mixed with the inorganic salt solution that concentration is 10000ppm, the inorganic salt solution configured is placed in Water Tank with Temp.-controlled, steady temperature is 40 DEG C; Be the kapillary of 20 μm by diameter with microsyringe, be injected in inorganic salt solution with the injection speed of 100ml/h by mixing solutions, obtained diameter is the flexible control-release microsphere dispersion system of 0.1-5.0 micron.
Claims (10)
1. the flexible control-release microsphere dispersion system formed by natural water-soluble copolymer, it is characterized in that, this flexible control-release microsphere dispersion system comprises the octane emulsion of the natural water-soluble copolymer aqueous solution, inorganic salt solution and surfactant-dispersed containing carboxyl and hydroxyl;
The octane emulsion of described surfactant-dispersed in water phase surfactant mixture, adds octane and be uniformly dispersed to obtain;
The mass ratio of the octane emulsion of described the natural water-soluble copolymer aqueous solution containing carboxyl and hydroxyl, inorganic salt solution and surfactant-dispersed is (12-35): (50-100): (1-3);
The mass concentration of the described natural water-soluble copolymer aqueous solution is 0.05%-1.0%, the concentration of described inorganic salt solution is 50ppm-10000ppm, the mass concentration of described water phase surfactant mixture is 0.05%-0.6%, and described water phase surfactant mixture and the mass ratio of octane are (2-10): (1-2).
2. flexible control-release microsphere dispersion system according to claim 1, is characterized in that, the diameter of described flexible control-release microsphere is 0.01-5.0 micron.
3. flexible control-release microsphere dispersion system according to claim 1, is characterized in that, the described natural water-soluble copolymer containing carboxyl and hydroxyl is modified-cellulose, treated starch, gelatin, chitosan and/or alginates.
4. flexible control-release microsphere dispersion system according to claim 1, is characterized in that, the described molecular weight ranges containing the natural water-soluble copolymer of carboxyl and hydroxyl is 20000 ~ 1500000.
5. flexible control-release microsphere dispersion system according to claim 1, it is characterized in that, described inorganic salt comprise bariumchloride, aluminum chloride, iron(ic) chloride, ferric sulfate, cupric chloride, zinc chloride, zinc sulfate and/or calcium chloride.
6. flexible control-release microsphere dispersion system according to claim 1, it is characterized in that, described tensio-active agent is one or more mixing in alkylolamide, sulfonated petro-leum, fatty-acid ethyl ester sulfonate, alkyl carboxylate, sultaine and carboxybetaine; Preferably, in the octane emulsion of described surfactant-dispersed, the distribution of sizes of emulsion particle is 0.1-0.5 micron.
7. a preparation method for the flexible control-release microsphere dispersion system described in any one of claim 1-6, comprises step as follows:
(1) by soluble in water for the natural water-soluble copolymer containing carboxyl and hydroxyl, continue stirring until whole dissolving, obtained mass concentration is the natural water-soluble copolymer aqueous solution of 0.05%-1.0%;
(2) be mixed with soluble in water for tensio-active agent the solution that mass concentration is 0.05%-0.6%, be (2-10) by the mass ratio of water phase surfactant mixture and octane: (1-2) adds octane, stir, ultrasonic disperse, obtains the octane emulsion of surfactant-dispersed;
(3) the octane emulsion of surfactant-dispersed step (2) obtained joins the natural water-soluble copolymer aqueous solution that step (1) obtains, and stirs, obtains mixing solutions;
(4) inorganic salt are mixed with the inorganic salt solution that concentration is 50ppm-10000ppm, the mixing solutions that step (3) obtains is added drop-wise in inorganic salt solution with the speed of 20ml/h-100ml/h, obtain flexible control-release microsphere dispersion system.
8. the preparation method of flexible control-release microsphere dispersion system according to claim 7, is characterized in that, in step (2), the time of ultrasonic disperse is 1-3h.
9. the application in oil recovery process as plugging agent or amendment of the flexible control-release microsphere dispersion system described in any one of claim 1-6.
10. application according to claim 9, is characterized in that, it is as follows that embody rule method comprises step:
It is 0.05%-0.3% that flexible control-release microsphere dispersion system is diluted with water to mass concentration, to metaideophone water after injecting 0.3-0.6PV in oil recovery Tibetan.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510144174.XA CN104861946B (en) | 2015-03-30 | 2015-03-30 | A kind of flexible control-release microsphere dispersion formed by natural water-soluble copolymer and its preparation and the application in intensified oil reduction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510144174.XA CN104861946B (en) | 2015-03-30 | 2015-03-30 | A kind of flexible control-release microsphere dispersion formed by natural water-soluble copolymer and its preparation and the application in intensified oil reduction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104861946A true CN104861946A (en) | 2015-08-26 |
| CN104861946B CN104861946B (en) | 2017-06-23 |
Family
ID=53908139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510144174.XA Active CN104861946B (en) | 2015-03-30 | 2015-03-30 | A kind of flexible control-release microsphere dispersion formed by natural water-soluble copolymer and its preparation and the application in intensified oil reduction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104861946B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461860A (en) * | 2016-01-07 | 2016-04-06 | 武汉工程大学 | Preparation method of temperature resistance and salt tolerance biopolymer gel profile control agent |
| CN106883832A (en) * | 2017-04-01 | 2017-06-23 | 武汉理工大学 | A kind of controllable diverting agent of environment-friendly type and preparation method thereof |
| CN107513380A (en) * | 2017-08-15 | 2017-12-26 | 泰州克罗米德机械设备有限公司 | For blocking and repairing the liquid composite of well |
| CN107513379A (en) * | 2017-08-15 | 2017-12-26 | 泰州克罗米德机械设备有限公司 | For blocking and repairing the liquid composite of well |
| CN112300767A (en) * | 2020-09-22 | 2021-02-02 | 山东大学 | Green targeted microcapsule, preparation system, preparation method and application |
| CN112480895A (en) * | 2020-11-27 | 2021-03-12 | 中国石油大学(北京) | PH-responsive oil displacement agent composition, oil displacement agent, and preparation method and application thereof |
| CN112625660A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Reactive plugging agent for water-based drilling fluid and preparation method thereof |
| CN113176180A (en) * | 2021-03-09 | 2021-07-27 | 济南雅歌新材料科技有限公司 | Method for measuring stability of profile control and flooding microsphere aqueous solution |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101564558A (en) * | 2009-05-18 | 2009-10-28 | 中国人民解放军第二军医大学 | Alginate-barium sulfate microsphere, preparation method and application thereof |
| CN102631680A (en) * | 2012-04-19 | 2012-08-15 | 浙江大学 | Method of regulating microsphere drug-load rate by treating calcium alginate microspheres with sodium chloride solution |
| CN103289135A (en) * | 2013-06-20 | 2013-09-11 | 上海应用技术学院 | Starch microsphere and preparation method thereof |
-
2015
- 2015-03-30 CN CN201510144174.XA patent/CN104861946B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101564558A (en) * | 2009-05-18 | 2009-10-28 | 中国人民解放军第二军医大学 | Alginate-barium sulfate microsphere, preparation method and application thereof |
| CN102631680A (en) * | 2012-04-19 | 2012-08-15 | 浙江大学 | Method of regulating microsphere drug-load rate by treating calcium alginate microspheres with sodium chloride solution |
| CN103289135A (en) * | 2013-06-20 | 2013-09-11 | 上海应用技术学院 | Starch microsphere and preparation method thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461860A (en) * | 2016-01-07 | 2016-04-06 | 武汉工程大学 | Preparation method of temperature resistance and salt tolerance biopolymer gel profile control agent |
| CN106883832A (en) * | 2017-04-01 | 2017-06-23 | 武汉理工大学 | A kind of controllable diverting agent of environment-friendly type and preparation method thereof |
| CN107513380A (en) * | 2017-08-15 | 2017-12-26 | 泰州克罗米德机械设备有限公司 | For blocking and repairing the liquid composite of well |
| CN107513379A (en) * | 2017-08-15 | 2017-12-26 | 泰州克罗米德机械设备有限公司 | For blocking and repairing the liquid composite of well |
| CN112625660A (en) * | 2019-09-24 | 2021-04-09 | 中国石油化工股份有限公司 | Reactive plugging agent for water-based drilling fluid and preparation method thereof |
| CN112625660B (en) * | 2019-09-24 | 2023-01-31 | 中国石油化工股份有限公司 | Reactive plugging agent for water-based drilling fluid and preparation method thereof |
| CN112300767A (en) * | 2020-09-22 | 2021-02-02 | 山东大学 | Green targeted microcapsule, preparation system, preparation method and application |
| CN112480895A (en) * | 2020-11-27 | 2021-03-12 | 中国石油大学(北京) | PH-responsive oil displacement agent composition, oil displacement agent, and preparation method and application thereof |
| CN112480895B (en) * | 2020-11-27 | 2022-02-01 | 中国石油大学(北京) | PH-responsive oil displacement agent composition, oil displacement agent, and preparation method and application thereof |
| CN113176180A (en) * | 2021-03-09 | 2021-07-27 | 济南雅歌新材料科技有限公司 | Method for measuring stability of profile control and flooding microsphere aqueous solution |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104861946B (en) | 2017-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104861946A (en) | Flexible controlled-release microsphere disperse system formed by natural water-soluble polymer and preparation thereof and application of system in reinforcement of oil extraction | |
| Ghosh et al. | ASP flooding in tight carbonate rocks | |
| CA2870904C (en) | Biodegradable activators to gel silica sol for blocking permeability | |
| CN103525387B (en) | Foamed cement slurry system and composition | |
| US20150275644A1 (en) | Well treatment | |
| CA2821146C (en) | Improved fluid loss compositions and methods of use for subterranean operations | |
| CN104087275B (en) | A kind of high-temperature-resistant high-salt tiny gels granular profile control agent and its preparation method and application | |
| US10421897B2 (en) | Method of treating a well with the formation of proppant structures (variants) | |
| US20200199442A1 (en) | Heavy oil activator and preparation method and use thereof | |
| CN106795750A (en) | For the steering of well treatment operation | |
| CN104650828B (en) | Reverse wetting agent and preparation method thereof and container horizon protective agent composition and for the drilling fluid of hyposmosis ultra-low permeability reservoir and application | |
| CN102587858B (en) | Method for blocking water for fracture and hole type reservoir | |
| CN104109518A (en) | Oil displacement composition used for low permeability oil reservoirs, and preparation method thereof | |
| CA2972431A1 (en) | Emulsions containing alkyl ether sulfates and uses thereof | |
| CN104119853A (en) | A preparing method of a high-strength high-temperature-resistance air foam fracturing fluid | |
| CN110242265A (en) | Original position receive-microballoon improve oil recovery factor filed application method | |
| Zhang et al. | Degradable preformed particle gel as temporary plugging agent for low-temperature unconventional petroleum reservoirs: Effect of molecular weight of the cross-linking agent | |
| Chen et al. | Experimental Study on Fiber Balls for Bridging in Fractured-Vuggy Reservoir | |
| CN104927005B (en) | A kind of alkaline-resisting profile control agent of pre-crosslinked gel volume expansion grain and preparation method thereof and purposes | |
| Nurmi et al. | Improving Alkali Polymer Flooding Economics by Capitalizing on Polymer Solution Property Evolution at High pH | |
| CN103541683B (en) | Preposition leak stopping frozen glue grout in hot pursuit carries out the method for leak stopping | |
| CN102618232B (en) | Plugging agent for fractured-vuggy oil reservoir | |
| Li et al. | Novel chemical flood combination of CSA particles and strong emulsifying surfactant in heterogeneous reservoirs | |
| Zhang et al. | Research on property of multicomponent thickening water fracturing fluid and application in low permeability oil reservoirs | |
| Li et al. | A novel profile modification HPF-Co gel satisfied with fractured low permeability reservoirs in high temperature and high salinity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |