CN111961450B - Capsule gel breaker and preparation method thereof - Google Patents
Capsule gel breaker and preparation method thereof Download PDFInfo
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- CN111961450B CN111961450B CN201910418898.7A CN201910418898A CN111961450B CN 111961450 B CN111961450 B CN 111961450B CN 201910418898 A CN201910418898 A CN 201910418898A CN 111961450 B CN111961450 B CN 111961450B
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
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- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
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- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
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Images
Classifications
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- 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
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
-
- 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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
-
- 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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
- C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
-
- 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
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/24—Bacteria or enzyme containing gel breakers
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- 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)
- Inorganic Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention provides a capsule gel breaker and a preparation method thereof, wherein the preparation method comprises the following steps: mixing the organic solution with an emulsifier aqueous solution to obtain an emulsion; heating the emulsion to 25-90 ℃ in a protective atmosphere, and preserving heat for 6-12h to obtain polymer emulsion; encapsulating the solid gel breaker by using the polymer emulsion, and drying to obtain the capsule gel breaker; the organic solution is obtained by dissolving amphiphilic modified starch or amphiphilic modified cellulose derivative, acrylate monomer, vinyl monomer containing halogen and initiator in organic solvent. The capsule gel breaker takes amphiphilic modified starch or amphiphilic modified cellulose derivative grafted acrylic resin-ethylene copolymer as a capsule coat to encapsulate the solid gel breaker, so that the slow release time can be prolonged remarkably, the slow release time of the capsule gel breaker can be controlled, and finally the self gel breaking of gel is realized at the target time to finish the flowback of the gel.
Description
Technical Field
The invention relates to a gel breaker, in particular to a capsule gel breaker and a preparation method thereof, and belongs to the technical field of petroleum and natural gas exploration and development.
Background
With the depth of oil and gas exploration and development, the stratum encountered in the drilling process is more and more complex, and the well leakage problem is very prominent when drilling pressure failure stratum, broken or cemented stratum, fracture development stratum and the like. The problems of borehole instability, collapse, blowout and the like induced by lost circulation are worldwide problems in the oil and gas exploration and development process for a long time, and are main technical bottlenecks for restricting the exploration and development speed. Meanwhile, the lost circulation causes great drilling fluid loss and great damage to the reservoir.
In addition, in the process of oil-gas well cementing construction, if cement slurry is leaked, the annular cement sealing height is not enough, and if the cement slurry sealing section does not meet the design requirement, an oil-gas water layer is leaked and sealed, so that gas-water channeling in the cementing waiting period is caused, the cementing quality is greatly reduced, and even a well control dangerous case is caused due to leakage, and cementing accidents occur.
In order to avoid the above-mentioned damage caused by leakage, at present, plugging by using gel is an effective operation mode. Specifically, gel molecular chains form a space grid structure with extremely strong performance through intermolecular hydrogen bond action and chemical bond action of different treating agents, and the gel molecular chains are retained and blocked at a leakage position by utilizing the adhesive force between the gel molecular chains and the stratum and the self structural force. However, after drilling or cementing, gel needs to be broken and drained, otherwise, the remaining gel can cause secondary damage to the reservoir, and even reduce the later-stage flow conductivity of the fracture.
At present, gel breaking of the gel is mostly realized by adding a gel breaker, but the gel breaking time of the current gel breaker is short, so that the gel cannot maintain long-acting stability within required time, gel breaking is performed in advance, and effective plugging of the gel on cracks is not facilitated.
Disclosure of Invention
The invention provides a capsule gel breaker and a preparation method thereof, the capsule gel breaker encapsulates a solid gel breaker by taking amphiphilic modified starch or amphiphilic modified cellulose derivative grafted acrylic resin-ethylene copolymer as a capsule coat, the special composition of the capsule coat can obviously enhance the stability of the capsule coat, prolong the slow release time, enable the slow release time of the capsule gel breaker to be controllable, and finally realize the self-breaking of gel in the target time to finish the flowback of the gel.
The invention provides a preparation method of a capsule gel breaker, which comprises the following steps:
mixing the organic solution with an emulsifier aqueous solution to obtain an emulsion;
heating the emulsion to 25-90 ℃ in a protective atmosphere, and preserving heat for 6-12h to obtain polymer emulsion;
encapsulating the solid gel breaker by using the polymer emulsion, and drying to obtain the capsule gel breaker;
the organic solution is obtained by dissolving amphiphilic modified starch or amphiphilic modified cellulose derivative, acrylate monomer, vinyl monomer containing halogen and initiator in organic solvent.
The preparation method of the capsule breaker comprises the following steps:
adding the amphiphilic modified starch or amphiphilic modified cellulose derivative, an acrylate monomer and a vinyl monomer containing halogen into an organic solvent, and stirring until the mixture is dissolved to obtain a first reaction solution;
and adding an initiator into the first reaction solution to obtain the organic solution.
The preparation method of the capsule breaker comprises the following steps of (15-30) in the first reaction liquid, wherein the mass ratio of the amphiphilic modified starch or the amphiphilic modified cellulose derivative to the acrylate monomer to the halogen-containing vinyl monomer is: (50-80): (15-20).
The preparation method of the capsule breaker comprises the following steps of (20-25) in the first reaction liquid, wherein the mass ratio of the amphiphilic modified starch or the amphiphilic modified cellulose derivative to the acrylate monomer to the halogen-containing vinyl monomer is: (60-70): (10-15).
The preparation method of the capsule gel breaker is characterized in that the mass fraction of the first reaction liquid is 5-60%.
The preparation method of the capsule gel breaker comprises the following steps of (0.1-2) by mass: 100, respectively;
the monomer is the amphiphilic modified starch or the amphiphilic modified cellulose derivative, an acrylate monomer and a halogen-containing vinyl monomer.
The preparation method of the capsule breaker comprises the step of dissolving an emulsifier in water to obtain an emulsifier aqueous solution, wherein the mass fraction of the emulsifier aqueous solution is 0.1-1%.
The preparation method of the capsule gel breaker comprises the step of mixing the polymer emulsion and the solid gel breaker according to a mass ratio of (95-50) to (5-50).
The preparation method of the capsule gel breaker comprises the steps of drying at 40-70 ℃ for 60-360 min.
The invention also provides a capsule gel breaker, which is obtained by any one of the preparation methods.
The implementation of the invention has at least the following advantages:
1. the capsule gel breaker can obviously prolong the slow release time and finally realize the self-breaking of the gel, thereby being beneficial to the efficient blocking of the gel;
2. the capsule gel breaker has controllable particle size and slow release, so the capsule gel breaker is suitable for various construction links such as oil gas recovery, well repair, sealing and the like, and has good application prospect;
3. the effective content of the solid gel breaker in the capsule gel breaker is high, the utilization rate of the solid gel breaker is improved, and the high-efficiency gel breaking of gel is facilitated;
4. the capsule gel breaker has high sphericity and uniform particle size, not only has high bonding degree with gel, but also has certain auxiliary effect on the gel strength, thereby further ensuring the effectiveness of gel plugging;
5. the capsule gel breaker can reduce the viscosity of a solution after gel breaking, is beneficial to the flowback of the solution after gel breaking, and avoids secondary pollution to a reservoir;
6. the preparation method of the capsule gel breaker has simple process and mild conditions, does not need large-scale or complex processing equipment for assistance, and can be used for mass production on a construction site to ensure the smooth construction;
7. the preparation method of the capsule gel breaker has lower raw material cost and processing cost, so that the capsule gel breaker can be produced and popularized on a large scale.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a flow diagram of one embodiment of a method of preparing the capsule breaker of the present invention;
FIG. 2 is a flow chart of an embodiment of the method for preparing an organic solution according to the present invention;
FIG. 3 is a scanning electron micrograph of the capsule breaker of example 1 of the present invention at a magnification of 74;
fig. 4 is a partially enlarged scanning electron micrograph of fig. 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It can be appreciated that the capsule breaker of the present invention comprises a capsule shell and a capsule core. Wherein, the capsule core is an effective component of gel breaking, and is generally a solid gel breaker; and the capsule coat is a material for coating the capsule core. Specifically, in the application process, the capsule coat can be broken after maintaining stability for a certain time, so that the solid gel breaker in the capsule coat is released, the released solid gel breaker acts on the gel, and the strength of the gel is gradually reduced until the gel is broken into a liquid state.
Fig. 1 is a flow chart of an embodiment of the preparation method of the capsule breaker of the present invention, and as shown in fig. 1, the preparation method of the capsule breaker of the present invention comprises the following steps:
s101: mixing the organic solution with an emulsifier aqueous solution to obtain an emulsion;
the organic solution contains the main raw material of the capsule coat of the capsule breaker of the invention. Specifically, the organic solution of the present invention is obtained by dissolving all of an amphiphatically modified starch or an amphiphatically modified cellulose derivative, an acrylate monomer, a halogen-containing vinyl monomer, and an initiator in an organic solvent. Wherein, the amphipathy modified starch or the amphipathy modified cellulose derivative can be used alternatively. Specifically, amphiphilic modified starch or amphiphilic modified cellulose derivative, acrylate monomer and vinyl monomer containing halogen are used as capsule coating materials, and an initiator is used for initiating the capsule coating materials to carry out polymerization reaction.
Through long-term research of the inventor, when the capsule coating material is formed by polymerizing the amphiphilic modified starch or the amphiphilic modified cellulose derivative, the acrylate monomer and the vinyl monomer containing halogen, the tightness of the capsule coating can be enhanced, the capsule core is prevented from contacting with the outside in advance, the capsule core can be easily released under specific environment and time, the targeted release performance is enhanced, and the utilization rate of the capsule core is improved, in particular, the capsule coating raw material can be favorable for forming a membrane-shaped object with good sealing performance, the membrane-shaped object can contain and wrap the capsule core, the surface area of the membrane-shaped object is controllable, so that the embedding effect can be effectively improved, the composition of the capsule coating raw material can remarkably prolong the slow release time of the capsule coating to ensure the effective blocking of gel, and when the proportion among the three raw materials is adjusted, the slow release time can be controlled within a certain range, therefore, the effective plugging of gel is ensured, and the plugging can be quickly removed when the gel plugging is not needed, so that the construction efficiency is obviously improved.
Further, the aqueous emulsifier solution is obtained by dissolving an emulsifier in water. Mixing the aqueous emulsifier solution with the organic solution helps to form a uniform emulsion, thereby ensuring effective and balanced encapsulation of the capsule coat by the solid breaker.
In the invention, the volume ratio of the organic solution to the emulsifier aqueous solution is (1-9): (9-1).
In order to further ensure that the emulsion becomes a uniform and stable dispersion system, the emulsion can be made to be oil-in-water (O/W) by selecting the kind of the emulsifier or controlling the ratio between the components.
S102: heating the emulsion to 25-90 ℃ in a protective atmosphere, and preserving heat for 6-12h to obtain polymer emulsion;
before heating, protective gas is introduced into the system to form an oxygen-free environment, and then the system is heated. Wherein the shielding gas may be, but is not limited to, nitrogen.
And heating the emulsion according to the parameters to enable the amphiphilic modified starch or the amphiphilic modified cellulose derivative, the acrylate monomer and the vinyl monomer containing halogen to perform polymerization reaction under the action of the initiator to generate the polymer emulsion.
The polymer emulsion is amphiphilic modified starch or amphiphilic modified cellulose derivative grafted acrylic resin-ethylene copolymer, the capsule core is wrapped by the copolymer, the stability of the capsule coat can be obviously enhanced, the slow release time is prolonged, the slow release time of the capsule gel breaker is controllable, and finally the self-breaking of the gel is realized at the target time to finish the flowback of the gel.
The particle size and capsule shell material composition of the capsule gel breaker can be finally influenced by adjusting the heating temperature and time, so that the controllability of the sustained-release time of the capsule gel breaker is realized.
S103: and encapsulating the solid gel breaker by using the polymer emulsion, and drying to obtain the capsule gel breaker.
The solid gel breaker is encapsulated by the polymer emulsion, and the invention is not limited to the specific encapsulation process, and the encapsulation can be completed by physical means such as spray encapsulation, hot air convection or rotary drum.
After encapsulation, the encapsulated particles may be dried to provide the capsule breakers of the present invention. Wherein, the drying treatment can be carried out by heating, for example, the drying temperature is 40-70 ℃, and the drying time is 60-360min, which not only facilitates the volatilization of the organic solvent, but also can remove the water therein to avoid the agglomeration of the particles.
The present invention is not limited to a specific manner of heating and drying, and any drying means that is advantageous for maintaining the integrity of the final product may be used as the manner of drying in the present invention. In a specific embodiment, hot air drying may be used.
The invention takes amphiphilic modified starch or amphiphilic modified cellulose derivative, acrylate monomer and vinyl monomer containing halogen as main raw materials, and carries out polymerization reaction at certain temperature and time to obtain the capsule coat emulsion; the capsule gel breaker formed by encapsulating the solid gel breaker by the capsule shell emulsion not only realizes tight encapsulation of the solid gel breaker, but also has controllable slow-release time, can release the solid gel breaker to break gel when necessary, and ensures the effectiveness of plugging and the high efficiency and thoroughness of deblocking.
In the preparation process of the capsule breaker, the amphiphilic modified starch can be selected from one or more of acetic acid-octenyl succinic acid modified starch, octenyl succinic acid modified starch and acetic acid modified starch;
the amphiphilic modified cellulose derivative can be selected from one or more of octenyl succinic acid modified cellulose, acetic acid modified cellulose and acetic acid-octenyl succinic acid modified fiber;
the acrylate monomer can be selected from one or more of methyl acrylate, butyl acrylate, methyl methacrylate and butyl methacrylate;
among the halogen-containing vinyl monomers, preferred are vinyl monomers containing fluorine and chlorine, such as one or more of vinyl chloride and vinylidene fluoride;
the initiator can be one or more of azodiisobutyronitrile, ultraviolet initiator 615 and dibenzoyl peroxide;
the organic solvent can be one or more selected from dichloromethane, trichloromethane, carbon tetrachloride, n-hexane, cyclohexane, benzene, toluene, n-octanol, n-undecanol, oleic acid and dimethyl sulfoxide;
the emulsifier may be a nonionic surfactant, for example, one or more selected from alkylphenol polyoxyethylene ether type, polyol fatty acid ester type;
the capsule core in the invention can adopt a solid gel breaker which is commonly used at present, and can be selected from one or more of ammonium persulfate, potassium persulfate and sodium percarbonate.
When the capsule gel breaker is prepared, the control of the sustained-release time of the capsule gel breaker can be realized by selecting the specific composition of the emulsion in the range, namely the specific composition of various raw materials in the emulsion can be selected in a targeted manner according to the target sustained-release time.
When the above-mentioned respective raw materials are a mixture of at least two substances, the present invention does not limit the ratio between the respective substances.
FIG. 2 is a flow chart of an embodiment of the method for preparing an organic solution according to the present invention. As shown in fig. 2, the organic solution of the present invention is prepared according to the following method:
s201: adding amphiphilic modified starch or amphiphilic modified cellulose derivative, acrylate monomer and vinyl monomer containing halogen into an organic solvent, and stirring until the mixture is dissolved to obtain a first reaction solution;
the present invention does not limit the order of adding the above three raw materials, and the three raw materials may be added to the organic solvent simultaneously or may be added to the organic solvent separately. Preferably, the three raw materials are added into the organic solvent respectively, and another solvent is added after each raw material is stirred and dissolved.
In one embodiment, in the first reaction solution, the mass ratio of the amphiphatically modified starch or the amphiphatically modified cellulose derivative, the acrylate monomer and the halogen-containing vinyl monomer is (15-30): (50-80): (15-20).
Through the research of the inventor, when the mass ratio of the amphipathy modified starch or the amphipathy modified cellulose derivative to the acrylate monomer to the vinyl monomer containing halogen is (15-30): (50-80): (15-20), the film-forming integrity of the capsule coat can be enhanced, the wrapping force on the capsule core is optimized, the slow-release time of the capsule gel breaker is prolonged, and the efficient blocking of the gel is ensured.
Preferably, the mass ratio of the amphipathy modified starch or the amphipathy modified cellulose derivative to the acrylate monomer to the vinyl monomer containing halogen is (20-25): (60-70): (10-15), the encapsulation efficiency of the solid breaker can be further improved, and the sphericity of the capsule breaker of the present invention can be improved and the particle size can be made uniform.
S202: and adding an initiator into the first reaction solution to obtain an organic solution.
And adding the initiator into the first reaction liquid, and stirring until the initiator is dissolved to obtain an organic solution.
In order to enable the sustained-release time of the capsule gel breaker to meet the requirements of various construction conditions, the sustained-release time can be controlled by selecting the types of raw materials, a polymerization reaction process and adjusting the proportion of the raw materials, and the sustained-release time can be further controlled by adjusting the mass fraction of the polymer emulsion.
Specifically, the mass fraction of the polymer emulsion has a certain relationship with the particle size and the compactness of the capsule gel breaker, and under different mass fractions of the polymer emulsion, the capsule shell thickness and the compactness of the encapsulated capsule gel breaker are different, and the larger the capsule shell thickness is, the larger the particle size of the capsule gel breaker is, and the longer the sustained-release time is; the smaller the thickness of the capsule coat is, the smaller the particle size of the capsule gel breaker is, and the shorter the sustained-release time is; the more compact the capsule coat is, the longer the slow release time is, the less compact the capsule coat is, and the shorter the slow release time is.
In the invention, the sustained-release time of the capsule gel breaker at about 70 ℃ can be realized for 6-14h by controlling the mass fraction of the polymer emulsion to be 10-30%.
In the specific operation, the polymer emulsion is a polymerization reaction system of the emulsion, so that the controllable operation of the slow release time can be realized by controlling the concentration of the emulsion and the proportion of the organic solution and the emulsifier aqueous solution. The emulsion consists of an organic solution and an aqueous solution of an emulsifier, the organic solution consists of a first reaction liquid and an initiator, and the aqueous solution of the emulsifier is formed by mixing the emulsifier and water. The results show that when the mass fraction of the first reaction liquid is 5 to 60% (i.e., the mass fraction of the total mass of the amphiphilic modified starch or the amphiphilic modified cellulose derivative, the acrylate monomer, and the halogen-containing vinyl monomer in the first reaction liquid), the mass ratio of the initiator to the monomer is (0.1 to 2): 100 (the monomer is a set of amphiphilic modified starch or amphiphilic modified cellulose derivative, acrylate monomer and vinyl monomer containing halogen), the mass fraction of the emulsifier aqueous solution is 0.1-1% (namely the mass fraction of the mass of the emulsifier in the emulsifier aqueous solution), and the volume ratio of the organic solution to the emulsifier aqueous solution is (1-9): (9-1), the capsule gel breaker can be slowly released for 6-14h at about 70 ℃.
Further, in the encapsulation process, the mass ratio of the polymer emulsion to the solid gel breaker is (95-50): (5-50).
In the specific implementation process of the invention, the dosage of the polymer emulsion is controlled to be not less than the dosage of the solid gel breaker, and the mass percentages of the polymer emulsion and the solid gel breaker are generally controlled to be (85-65): (15-35) to achieve complete encapsulation of the solid breaker and further avoid agglomeration between capsule breakers.
The invention also provides a capsule gel breaker, which is prepared by the preparation method.
The capsule gel breaker is of a structure that a capsule coat wraps a capsule core, and due to the special composition of the capsule coat, the capsule gel breaker has good stability, long slow release time and controllable slow release time, the capsule coat can be broken at a target moment and release the capsule core, and gel is broken and degraded after the capsule core is bonded with gel to complete deblocking of the gel; and the solution after gel breaking has lower viscosity, is favorable for being discharged back to the stratum, and avoids secondary pollution to the stratum.
The capsule gel breaker can be applied to construction links such as oil field recovery, well repair, sealing and the like. In application, it can be mixed with a gel and injected into a target site for plugging.
At the beginning of injection, the capsule gel breaker can be uniformly distributed in the gel and block a target position along with the gel, along with the blocking, the capsule gel breaker can be broken after the self slow-release time is reached, a capsule coat is released from the solid gel breaker, and the solid gel breaker can be in contact reaction with the gel to complete gel breaking.
The capsule gel breaker provided by the invention has a special capsule coat composition, so that the slow release time of the capsule gel breaker can be obviously prolonged, the controllability of the slow release time is improved, the efficient implementation of construction projects such as effective blocking of gel and oil and gas exploitation is further ensured, and different construction requirements can be met; in addition, the preparation method has lower raw material cost and simple preparation process, so that the large-scale production on a construction site is facilitated; in addition, the spherical particle has the advantages of high sphericity, uniform particle size and high effective content, so that the spherical particle can be widely applied to exploitation of different oil and gas reservoirs, and has a good application prospect.
Hereinafter, the capsule breaker and the preparation method thereof according to the present invention will be described in detail by way of specific examples.
Example 1
The capsule breaker of this example was prepared as follows:
1) preparation of organic solutions
Dissolving acetic acid-octenyl succinic acid modified starch, butyl acrylate and vinylidene fluoride in DMSO to generate a first reaction solution;
in the first reaction liquid, the mass ratio of the acetic acid-octenyl succinic acid modified starch to the butyl acrylate to the vinylidene fluoride is 20: 65: 15, and the mass fraction of the first reaction liquid is 50%;
adding azodiisobutyronitrile into the first reaction liquid, and controlling the mass ratio of the azodiisobutyronitrile to the total amount of the monomers (acetic acid-octenyl succinic acid modified starch, butyl acrylate and vinylidene fluoride) to be 0.5: 100, stirring uniformly to obtain an organic solution;
2) preparation of aqueous emulsifier solutions
Dissolving alkylphenol polyoxyethylene in water, and controlling the mass fraction of the emulsifier to be 0.6% to obtain an emulsifier aqueous solution;
3) preparation of the emulsion
Mixing the organic solution with an emulsifier aqueous solution and stirring until complete emulsification to obtain a stable O/W type emulsion; wherein the volume ratio of the organic solution to the emulsifier aqueous solution is 4: 6;
4) preparation of the polymerization emulsion
Transferring the emulsion into a reactor, introducing nitrogen to remove oxygen, heating to the reaction temperature of 70 ℃, and reacting for 12 hours to obtain uniform and stable polymer emulsion with the mass fraction of 20%;
5) encapsulation
Encapsulating the ammonium persulfate by the prepared polymer emulsion in a spray encapsulation physical mode, wherein the mass ratio of the polymer emulsion to the ammonium persulfate is 70: 30, drying for 4 hours at the temperature of 50 ℃ after encapsulation to obtain the capsule gel breaker of the embodiment.
Example 2
The capsule breaker of this example was prepared as follows:
1) preparation of organic solutions
Dissolving acetic acid-octenyl succinic acid modified cellulose, butyl methacrylate and vinylidene fluoride in dichloromethane to generate a first reaction liquid;
in the first reaction liquid, the mass ratio of the acetic acid-octenyl succinic acid modified cellulose to the butyl methacrylate to the vinylidene fluoride is 15:65:20, and the mass fraction of the first reaction liquid is 60%;
adding dibenzoyl peroxide into the first reaction liquid, and controlling the mass ratio of dibenzoyl peroxide to the total amount of monomers (acetic acid-octenyl succinic acid modified cellulose, butyl methacrylate and vinylidene fluoride) to be 1: 100, stirring uniformly to obtain an organic solution;
2) preparation of aqueous emulsifier solutions
Dissolving polyalcohol fatty acid ester in water, and controlling the mass fraction of the emulsifier to be 0.6% to obtain an emulsifier aqueous solution;
3) preparation of the emulsion
Mixing the organic solution with an emulsifier aqueous solution and stirring until complete emulsification to obtain a stable O/W type emulsion; wherein the volume ratio of the organic solution to the emulsifier aqueous solution is 1: 1;
4) preparation of the polymerization emulsion
Transferring the emulsion into a reactor, introducing nitrogen to remove oxygen, heating to the reaction temperature of 65 ℃, and reacting for 8 hours to obtain uniform and stable polymer emulsion with the mass fraction of 30%;
5) encapsulation
Encapsulating the ammonium persulfate by the prepared polymer emulsion in a spray encapsulation physical mode, wherein the mass ratio of the polymer emulsion to the ammonium persulfate is 90: 10, drying for 6 hours at 60 ℃ after encapsulation to obtain the capsule breaker of the present example.
Example 3
The capsule breaker of this example was prepared as follows:
1) preparation of organic solutions
Dissolving carboxymethyl hydroxyethyl modified cellulose, octadecyl methacrylate and vinylidene fluoride in cyclohexane to generate a first reaction solution;
in the first reaction solution, the mass ratio of the carboxymethyl hydroxyethyl modified cellulose to the stearyl methacrylate to the vinylidene fluoride is 15: 70: 15, and the mass fraction of the first reaction liquid is 60%;
adding dibenzoyl peroxide into the first reaction liquid, and controlling the mass ratio of the dibenzoyl peroxide to the total amount of the monomers (carboxymethyl hydroxyethyl modified cellulose, stearyl methacrylate and vinylidene fluoride) to be 0.8: 100, stirring uniformly to obtain an organic solution;
2) preparation of aqueous emulsifier solutions
Dissolving a compound emulsifying system of polyol fatty acid ester and alkylphenol polyoxyethylene in water, wherein the mass ratio of the polyol fatty acid ester to the alkylphenol polyoxyethylene is 70: 30, and controlling the mass fraction of the emulsifier to be 1.2% to obtain an emulsifier aqueous solution;
3) preparation of the emulsion
Mixing the organic solution with an emulsifier aqueous solution and stirring until complete emulsification to obtain a stable O/W type emulsion; wherein the volume ratio of the organic solution to the emulsifier aqueous solution is 7: 3;
4) preparation of the polymerization emulsion
Transferring the emulsion into a reactor, introducing nitrogen to remove oxygen, heating to the reaction temperature of 60 ℃, and reacting for 6 hours to obtain uniform and stable polymer emulsion with the mass fraction of 25%;
5) encapsulation
Encapsulating the ammonium persulfate by the prepared polymer emulsion in a spray encapsulation physical mode, wherein the mass ratio of the polymer emulsion to the ammonium persulfate is 80: after encapsulation, the gel was dried with hot air at a temperature of 70 ℃ for 8 hours to obtain the capsule breaker of this example.
The capsule gel breaker obtained in the above embodiment is characterized and tested, including appearance, effective content, sustained release and liquid viscosity after gel breaking, specifically as follows:
1. appearance and appearance
The capsule breakers in the examples were observed using a JSM-IT500 scanning electron microscope. Fig. 3 is a scanning electron microscope image with a magnification of 74 times of the capsule breaker according to example 1 of the present invention, and fig. 4 is a partial scanning electron microscope image with a magnification of 2432 times of the fig. 3.
The appearance of the encapsulated breaker sample is clearly seen in fig. 3, and the multiphase film formed after the polymer emulsion is dried can uniformly cover the outside of the solid breaker, and no naked solid breaker can be observed.
Fig. 4 is a magnified partial photograph of the photograph of fig. 3, and from fig. 4 the film that may be coated on the outside of the solid breaker exhibits two different states, one white dense and the other darker contrast, indicating that the film material contains both hydrophilic and lipophilic components. Not only can ensure that the capsule gel breaker has good water resistance and prolongs the release time, but also can induce the membrane to break when the internal pressure is enough to complete the release.
As can be seen from fig. 3 and 4, the capsule shell of the capsule breaker prepared in the above embodiment can efficiently wrap the capsule core, and the capsule breaker has high dispersity and no adhesion phenomenon; and the surface has an obvious phase separation structure, so that a good gel breaking effect can be ensured.
2. Effective content
The effective content of the capsule breakers of examples 1-3 were tested separately, wherein,
effective content-mass of solid breaker actually encapsulated/mass of capsule breaker,
the mass of the capsule gel breaker is directly obtained by weighing, and the mass of the actually encapsulated solid gel breaker is measured by adopting an ultraviolet spectrophotometer method, wherein the specific method comprises the following steps:
first, standard working curve determination is performed: and (3) taking a certain amount of polyvinyl alcohol aqueous solution, dropwise adding 2-3 drops of iodine solution, mixing, and then adding a certain amount of gel breaker standard solution. The maximum absorption wavelength (570-610 nm) is fixedly selected, a polyvinyl alcohol iodine solution is used as a reference, the absorbance (or light transmittance) of a developing solution is measured by a 721 type spectrophotometer, and a working curve is drawn. The concentration of the aqueous polyvinyl alcohol solution and the concentration of iodine and the amount of the mixture thereof are properly selected to prevent the precipitation of gel. The working curve may be linear in absorbance versus breaker content of 0-1.0 wt.%. Because the PVA content which does not produce gel has a certain limit, the acid liquor of the gel breaker with higher content needs to be quantitatively diluted and then measured.
Then, the concentration of the actual encapsulated solid gel breaker is determined: the concentration of the core material in the solution was measured as follows: and (2) dropwise adding 2-3 drops of iodine solution into a certain amount of polyvinyl alcohol aqueous solution, mixing, adding a certain amount of solution to be detected of the gel breaker, and measuring the absorbance (or light transmittance) of the developing solution by using a 721 type spectrophotometer. The wavelength is referenced to a standard working curve, and the concentration of the gel breaker can be determined within the standard curve.
And finally, calculating the mass of the solid gel breaker according to the concentration of the solid gel breaker.
The results are shown in Table 1.
3. Sustained release property
When the anion polyacrylamide gels were subjected to gel breaking at 55 ℃ by using the capsule breakers of examples 1 to 3, respectively, and a change in system color was observed, it was confirmed that the solid breakers in the capsule breakers began to be released to obtain a zero release time, i.e., a sustained release time, and the results are shown in table 1.
4. Viscosity of liquid before gel formation and viscosity of liquid after gel breaking
The viscosity of the above anionic polyacrylamide gel before gel formation was measured by a viscometer and the results are shown in Table 1. (since the viscosity of the anionic polyacrylamide gel after gelling is greater than 50000mPa.s, the viscosity cannot be determined in the solid state)
The viscosity of the solution after breaking was measured by a viscometer and the results are shown in Table 1.
TABLE 1
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (11)
1. The preparation method of the capsule gel breaker is characterized by comprising the following steps:
mixing the organic solution with an emulsifier aqueous solution to obtain an emulsion;
heating the emulsion to 25-90 ℃ in a protective atmosphere, and preserving heat for 6-12h to obtain polymer emulsion;
encapsulating the solid gel breaker by using the polymer emulsion, and drying to obtain the capsule gel breaker;
wherein the organic solution is obtained by dissolving amphiphilic modified starch or amphiphilic modified cellulose derivative, acrylate monomer, vinyl monomer containing halogen and initiator in organic solvent;
the polymer emulsion is amphiphilic modified starch or amphiphilic modified cellulose derivative grafted acrylic resin-ethylene copolymer;
the mass fraction of the polymer emulsion is 10-30%.
2. The method of preparing the capsule breaker of claim 1, wherein the organic solution is prepared according to the following method:
adding the amphiphilic modified starch or amphiphilic modified cellulose derivative, an acrylate monomer and a vinyl monomer containing halogen into an organic solvent, and stirring until the mixture is dissolved to obtain a first reaction solution;
and adding the initiator into the first reaction solution to obtain the organic solution.
3. The method for preparing the capsule breaker according to claim 2, wherein the mass ratio of the amphiphilic modified starch or the amphiphilic modified cellulose derivative, the acrylate monomer and the halogen-containing vinyl monomer in the first reaction liquid is (15-30): (50-80): (15-20).
4. The method for preparing the capsule breaker according to claim 3, wherein the mass ratio of the amphiphilic modified starch or the amphiphilic modified cellulose derivative, the acrylate monomer and the halogen-containing vinyl monomer in the first reaction liquid is (20-25): (60-70): (10-15).
5. The method for preparing the capsule breaker according to any one of claims 2 to 4, wherein the mass fraction of the first reaction solution is 5 to 60%.
6. The method for preparing the capsule breaker according to claim 5, wherein the mass ratio of the initiator to the monomer is (0.1-2): 100, respectively;
the monomer is the amphiphilic modified starch or the amphiphilic modified cellulose derivative, an acrylate monomer and a halogen-containing vinyl monomer.
7. The method for preparing the capsule breaker according to any one of claims 1, 2, 3, 4 and 6, wherein the aqueous emulsifier solution is obtained by dissolving an emulsifier in water, and the mass fraction of the aqueous emulsifier solution is 0.1-1%.
8. The method for preparing the capsule breaker according to claim 5, wherein the aqueous emulsifier solution is obtained by dissolving an emulsifier in water, wherein the mass fraction of the aqueous emulsifier solution is 0.1-1%.
9. The method of claim 1, wherein the mass ratio of the polymer emulsion to the solid breaker is (95-50) to (5-50).
10. The method of preparing the capsule breaker of claim 1, wherein the drying is at a drying temperature of 40-70 ℃ for a drying time of 60-360 min.
11. A capsule breaker obtained by the production method according to any one of claims 1 to 10.
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| CN106432576A (en) * | 2016-09-18 | 2017-02-22 | 海南必凯水性涂料有限公司 | Polyvinylidene chloride emulsion used as gel breaker capsule coating material and preparation method thereof |
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| CN106432576A (en) * | 2016-09-18 | 2017-02-22 | 海南必凯水性涂料有限公司 | Polyvinylidene chloride emulsion used as gel breaker capsule coating material and preparation method thereof |
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