CN110734754A - Plugging agent composition, plugging agent, preparation method and application thereof - Google Patents
Plugging agent composition, plugging agent, preparation method and application thereof Download PDFInfo
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- 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
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Abstract
The invention relates to the field of leakage prevention and leakage stoppage of drilling fluid, and discloses leakage stoppage agent compositions, a leakage stoppage agent, a preparation method and an application thereof.
Description
Technical Field
The invention relates to the field of leakage prevention and plugging of drilling fluid, in particular to leakage plugging agent compositions, a leakage plugging agent, a preparation method and application thereof.
Background
The well leakage problem is a difficult problem which puzzles global field engineers, the well leakage happens generally has the condition that the working fluid pressure in a shaft is larger than the pore pressure of the liquid in the pores, cracks or caverns of the stratum, and a leakage passage and a larger space for containing the liquid exist in the stratum, the conventional leakage stoppage materials are generally divided into four types, namely particles, sheets, fibers and a mixture of the two materials, the common leakage stoppage methods are divided into eight types, namely (1) adjusting the performance of the drilling fluid, (2) a static leakage stoppage method, (3) a bridging material leakage stoppage method, (4) a high-filtration slurry leakage stoppage method, (5) a temporary stoppage method, (6) a chemical leakage stoppage method, (7) an inorganic gel leakage stoppage method, (8) a composite leakage stoppage method, most of the chemical leakage stoppage method is to inject the screened chemical leakage stoppage agent into a leakage layer to form gel so as to block the leakage passage, and the common chemical leakage stoppage is adapted to the conventional drilling process.
The drilling stopping and leaking stoppage work means that the drilling is stopped when a leaking layer is met, the drill bit is lifted upwards, the leaking stoppage slurry is injected, and the pump is held to stop and block the stratum. The process consumes a large amount of non-production time, the plugging agent injected with the plugging agent is required to be incapable of being gelled in a shaft, and construction can be carried out only by good pumpability, so that the process is mostly used for solving the malignant leakage or partial leakage condition. The process of plugging while drilling is that plugging materials are added into drilling fluid when a leaking layer is encountered or is about to be drilled when the leaking layer is encountered, and the plugging materials are drilled while drilling well fluid while plugging the leaking layer. The process does not affect drilling, but is mostly used for solving the microminiature leakage condition.
The permeable leakage is a complex condition frequently encountered in the drilling process, and the main reason is that the stratum has high sand content, large porosity and high permeability, the drilling fluid is easy to permeate into the stratum, secondly, natural cracks or induced cracks exist in the stratum, and the drilling fluid is easy to enter the cracks and lose the drilling fluid when encountering the stratum containing the cracks.
At present, polymer gel while-drilling plugging agents mainly comprise cross-linked polyacrylamide gel, polyacrylic acid gel, urea-formaldehyde resin, acrylic resin and the like, and field application shows that the materials have the effect of , but have the problems of , such as insufficient pressure bearing capacity, low success rate of times of plugging and the like.
Disclosure of Invention
The invention aims to overcome the problems of insufficient adhesive capacity, low pressure bearing capacity and poor plugging effect of the plugging agent in the prior art, and provides plugging agent compositions, the plugging agent prepared from the plugging agent compositions and the application of the plugging agent in the aspects of well drilling, leakage prevention and plugging, wherein the plugging agent prepared from the plugging agent composition is bionic mussel strong adhesion supermolecule gel plugging agents which have excellent underwater adhesion capacity and strong pollution resistance, pressure bearing resistance and high temperature resistance.
In order to overcome the problems, the inventor of the invention has conducted intensive research and finds that polymer gel plugging agents with excellent underwater adhesion capability and strong pollution resistance, pressure resistance and high temperature resistance can be obtained by selecting a bionic mussel adhesive and nanoclay and synthesizing crosslinked polyacrylamide composite gel through self-based polymerization, thereby completing the invention.
The reason why the polymer gel plugging agent has the excellent effects is presumed that the adhesion capability of the plugging agent while drilling in the drilling fluid is enhanced by introducing the bionic mussel adhesive rich in catechol functional groups into the polymer gel plugging agent, the plugging agent can be firmly adhered to the wall surface of a leaking layer after entering the leaking layer, the anti-scouring capability is enhanced in the aspect of , in addition, the surface of the plugging agent prepared by the plugging agent composition in the aspect of contains a large number of hydrogen bonds, a supermolecular structure can be formed between the plugging agents, the plugging capability is enhanced in the step , and the pressure bearing capability of a stratum is improved.
Thus, in , the present invention provides types of plugging agent compositions comprising a biomimetic mussel adhesive, nanoclay, a vinyl-based monomer, a cross-linking agent and water.
Preferably, the biomimetic mussel adhesive is 0.3-3 parts by weight, the nanoclay is 1-8 parts by weight, the vinyl monomer is 3-15 parts by weight, and the cross-linking agent is 0.05-8 parts by weight, relative to 100 parts by weight of water.
Preferably, the biomimetic mussel adhesive is or more of gallic acid, dopamine, catechol, and tannic acid.
Preferably, the nanoclay is magnesium aluminum silicate.
Preferably, the nanoclay is or more of nanoclay laponite RDS, nanoclay laponite SL25, nanoclay laponite js, and nanoclay laponite RD.
Preferably, the vinyl monomer is or more of acrylic monomers and acrylamide monomers.
Preferably, the vinyl monomer is or more of acrylamide, acrylic acid, methacrylamide, methacrylic acid and N-vinyl pyrrolidone.
Preferably, the cross-linking agent is or more of N, N-dimethyl bisacrylamide, ethylene glycol dimethacrylate, 1, 4-butanediol diacrylate and tetraisocyanate.
According to a second aspect of the present invention, there is provided a method for preparing lost circulation additives, which comprises the steps of mixing the components of the lost circulation additive composition of the present invention and carrying out a polymerization crosslinking reaction.
Preferably, the biomimetic mussel adhesive, the nanoclay and water are subjected to th mixing, followed by a second mixing with the vinyl-based monomer and the cross-linking agent.
Preferably, the mixing conditions include a temperature of 10-40 deg.C and a time of 10-24 hours.
Preferably, the conditions of the second mixing include: the temperature is 10-40 deg.C, and the time is 5-30 min.
Preferably, the conditions of the polymeric crosslinking reaction include: the reaction temperature is 50-70 ℃, and the reaction time is 4-8 h.
Preferably, the polymeric crosslinking reaction is carried out in the presence of an initiator.
Preferably, the initiator is an oxidation-reduction initiator or an azo-type initiator.
Preferably, the initiator is or more of azobisisobutyramidine hydrochloride, azobisformamide, azobisisobutylimidazoline hydrochloride, azobisisobutyronitrile formamide, azobiscyclohexylcarbonitrile, azobiscyanovaleric acid, azobisdiisopropylimidazoline, azobisisobutyronitrile, azobisisovaleronitrile, and azobisisoheptonitrile.
Preferably, the initiator is used in an amount of 2 to 30 parts by weight, relative to 100 parts by weight of the vinyl-based monomer.
Preferably, the method further comprises the step of drying the polymerized cross-linked reaction product.
According to a third aspect of the present invention, there is provided a plugging agent prepared by the preparation method of the present invention.
According to a fourth aspect of the invention, the plugging agent composition and the application of the plugging agent prepared by the preparation method in the aspect of leak protection and plugging of a drilling well are provided.
Through the technical scheme, the invention has the following advantages.
1) The polymer gel plugging agent has excellent underwater adhesion capability and can effectively plug lost pores.
2) The polymer gel plugging agent has the advantages of low toxicity, environmental protection, simple production process and low cost.
3) The polymer gel plugging agent has good compatibility and strong pollution resistance.
4) The polymer gel plugging agent has strong high temperature resistance of 180 ℃.
5) The polymer gel plugging agent can effectively plug a sand tray leaking layer with the maximum pore radius of 50-100mD, and has the pressure bearing capacity of more than 4MPa and stronger pressure bearing capacity.
Detailed Description
For numerical ranges, between the endpoints of each range and the individual points, and between the individual points may be combined with each other to yield new numerical ranges or ranges, which should be considered as specifically disclosed herein.
In , the invention provides kinds of plugging agent compositions, which comprise bionic mussel adhesive, nano clay, vinyl monomer, cross-linking agent and water.
According to the present invention, from the viewpoint of improving the underwater adhesion, contamination resistance, pressure resistance and high temperature resistance in step , it is preferable that the biomimetic mussel adhesive is 0.3 to 3 parts by weight, the nanoclay is 1 to 8 parts by weight, the vinyl-based monomer is 3 to 15 parts by weight, and the cross-linking agent is 0.05 to 8 parts by weight, with respect to 100 parts by weight of water, and it is more preferable that the biomimetic mussel adhesive is 0.5 to 2 parts by weight, the nanoclay is 2 to 5 parts by weight, the vinyl-based monomer is 5 to 10 parts by weight, and the cross-linking agent is 0.1 to 5 parts by weight, with respect to 100 parts by weight of water.
Preferably, the biomimetic mussel adhesive is or more of gallic acid, dopamine, catechol, and tannic acid, more preferably, the biomimetic mussel adhesive is or more of dopamine, catechol, and tannic acid.
According to the invention, preferably the nanoclay is magnesium aluminum silicate, more preferably the nanoclay is or more of nanoclay laponite RDS, nanoclay laponite SL25, nanoclay laponite JS and nanoclay laponite RD, more preferably the nanoclay is nanoclay laponite RD. as the nanoclay laponite RD (Veegum Ultra) is available, for example, from Sigma-Aldrich.
According to the present invention, the vinyl monomer is preferably or more of acrylic monomers and acrylamide monomers, and more preferably C0-6Alkyl acrylic acid and C0-6 or more of the alkyl acrylamides.
Examples of the vinyl monomer include: acrylic acid, methacrylic acid, ethyl acrylic acid, propyl acrylic acid, butyl acrylic acidC of pentylacrylic acid or hexylacrylic acid0-6Alkyl acrylic acid; c of acrylamide, methacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, pentylacrylamide or hexylacrylamide0-6And N-vinylpyrrolidone, among them, or more of acrylamide, acrylic acid, methacrylamide, methacrylic acid and N-vinylpyrrolidone are preferable.
According to the present invention, preferably, the crosslinking agent is or more of N, N-dimethyl bisacrylamide, ethylene glycol dimethacrylate, 1, 4-butanediol diacrylate and tetraisocyanate.
According to a second aspect of the present invention, there is provided a method for preparing lost circulation additives, which comprises the steps of mixing the components of the lost circulation additive composition of the present invention and carrying out a polymerization crosslinking reaction.
The method of the present invention for mixing the components of the plugging agent composition of the present invention is not particularly limited, and for example, may be mixed together and then the polymerization crosslinking reaction may be performed, or water may be mixed with any or two components first, and then or other components may be mixed separately, and preferably, the biomimetic mussel adhesive, the nanoclay and water are mixed th and then the second mixing is performed with the vinyl-based monomer and the crosslinking agent.
The mixing is preferably performed by mixing water with the biomimetic mussel adhesive and then mixing with the nanoclay, preferably, the mixing conditions include a temperature of 10-40 ℃ for 10-24 hours, and more preferably, the mixing conditions include a temperature of 15-40 ℃ for 15-22 hours.
The conditions for the second mixing are not particularly limited as long as the vinyl-based monomer and the crosslinking agent can be sufficiently dissolved. Preferably, the conditions of the second mixing include: the temperature is 10-40 deg.C, and the time is 5-30 min; more preferably, the conditions of the second mixing include: the temperature is 15-40 deg.C, and the time is 15-20 min.
According to the method of the present invention, preferably, the conditions of the polymerization crosslinking reaction include: the reaction temperature is 45-85 ℃, and the reaction time is 2-20 h; more preferably, the conditions of the polymeric crosslinking reaction include: the reaction temperature is 50-70 ℃, and the reaction time is 4-8 h.
The oxidation-reduction initiator may be suitably selected from a variety of oxidation-reduction initiator systems capable of initiating radical polymerization, for example, the oxidizing agent of the oxidation-reduction initiator may be or more of persulfate (sodium persulfate, potassium persulfate, ammonium persulfate, etc.), hydrogen peroxide, hydroperoxide (cumene hydroperoxide), etc., and the reducing agent of the oxidation-reduction initiator may be or more of ferrite (ferrous sulfate, ferrous chloride, etc.), sulfite (sodium sulfite, sodium bisulfite, potassium sulfite, etc.), thiosulfate (sodium thiosulfate, etc.), etc., wherein, preferably, the molar ratio of the oxidizing agent and the reducing agent of the oxidation-reduction initiator is preferably 1: 1 to 1.5.
The azo initiator may be or more of azobisisobutyric acid dimethyl ester (trade name AIBME, V601), azobisisobutyramidine hydrochloride (trade name AIBA, V50), azobisformamide (trade name ADC blowing agent), azobisisobutylimidazoline hydrochloride (trade name AIBI, VA044), azobisisobutyronitrile formamide (trade name CABN, V30), azobiscyclohexylcarbonitrile (trade name ACCN, V40), azobiscyanovaleric acid (trade name ACVA, V501), azobisisopropylimidazoline (trade name AIP, VA061), azobisisobutyronitrile (trade name AIBN, V60), azobisisovaleronitrile (trade name AMBN, V59), and azobisisoheptonitrile (trade name ABVN, V65).
According to the present invention, the amount of the initiator may be selected according to the amount of the vinyl-based monomer, and is generally 0.1 to 35 parts by weight per 100 parts by weight of the vinyl-based monomer; preferably, the initiator is used in an amount of 2 to 30 parts by weight, relative to 100 parts by weight of the vinyl-based monomer.
According to the method of the present invention, the polymerization crosslinking reaction is generally carried out under an inert atmosphere, which may be provided, for example, by or more in nitrogen, helium, neon, argon, and the like.
According to the present invention, preferably, the method further comprises a step of drying the polymerized crosslinking reaction product. The drying is not particularly limited, and various methods generally used in the art may be employed, for example, drying at 60 to 80 ℃ for 16 to 48 hours may be employed.
According to a third aspect of the present invention, there is provided a plugging agent prepared by the method of the present invention.
According to a fourth aspect of the invention, the plugging agent composition and the application of the plugging agent prepared by the preparation method in the aspect of leak protection and plugging of a drilling well are provided.
The plugging agent has excellent underwater adhesion capability, and has strong pollution resistance, pressure resistance and high temperature resistance, is particularly suitable for being used as a plugging agent while drilling, and can be used for leakage prevention and plugging of a drilling well in a deepwater development well.
The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples.
In the following examples and comparative examples, "parts" means "parts by weight"; dopamine and catechol were purchased from Sigma-Aldrich; tannic acid was purchased from Suzhou Huafeng chemical science and technology, Inc.; gallic acid was purchased from sunshine honesty name Biotechnology Ltd; nanoclay laponite RD (Veegum Ultra) was purchased from Sigma-Aldrich.
Example 1
Adding 0.5 part of dopamine into 100 parts of distilled water at 25 ℃, stirring for 10min by using a magnetic stirrer, adding 2 parts of nanoclay laponite RD, stirring for 16h at 25 ℃ by using the magnetic stirrer, adding 5 parts of vinyl monomer (specifically acrylamide) and 0.1 part of cross-linking agent (specifically N, N-dimethyl bisacrylamide) into the mixture, and stirring for 10min at 25 ℃ until the monomer and the cross-linking agent are fully dissolved. And then pouring the mixture into a three-neck flask, introducing nitrogen for 30min, heating to 60 ℃ by using a water bath kettle, heating while stirring by using an electric stirrer, adding 0.1 part of an initiator (specifically azodiisobutymidine hydrochloride) after the temperature of the mixture reaches 60 ℃, and reacting for 8h to obtain a white gel product. And after cooling, taking out the gel, washing, placing the gel in an oven, drying for 16h at 70 ℃ to obtain a white solid product, and crushing the solid product into particles to obtain the bionic mussel polymer gel plugging agent A1.
Example 2
Adding 1 part of dopamine into 100 parts of distilled water at 25 ℃, stirring for 12min by using a magnetic stirrer, adding 2.5 parts of nanoclay laponite RD, stirring for 18h at 25 ℃ by using the magnetic stirrer, adding 7.5 parts of vinyl monomer (specifically acrylamide) and 2.5 parts of cross-linking agent (specifically N, N-dimethyl bisacrylamide) into the mixture, and stirring for 15min at 25 ℃ until the monomer and the cross-linking agent are fully dissolved. And then pouring the mixture into a three-neck flask, introducing nitrogen for 30min, heating to 60 ℃ by using a water bath kettle, heating while stirring by using an electric stirrer, adding 1 part of an initiator (specifically azodiisobutymidine hydrochloride) after the temperature of the mixture reaches 60 ℃, and reacting for 8h to obtain a white gel product. And after cooling, taking out the gel, washing, placing the gel in an oven, drying for 16h at 70 ℃ to obtain a white solid product, and crushing the solid product into particles to obtain the bionic mussel polymer gel plugging agent A2.
Example 3
Adding 5 parts of dopamine into 100 parts of distilled water at 25 ℃, stirring for 15min by using a magnetic stirrer, adding 5 parts of nanoclay laponite RD, stirring for 20h at 25 ℃ by using the magnetic stirrer, adding 10 parts of vinyl monomer (specifically acrylamide) and 5 parts of cross-linking agent (specifically N, N-dimethyl bisacrylamide) into the mixture, and stirring for 20min at 25 ℃ until the monomer and the cross-linking agent are fully dissolved. And then pouring the mixture into a three-neck flask, introducing nitrogen for 30min, heating to 60 ℃ by using a water bath kettle, heating while stirring by using an electric stirrer, adding 3 parts of an initiator (specifically azodiisobutymidine hydrochloride) after the temperature of the mixture reaches 60 ℃, and reacting for 8h to obtain a white gel product. And after cooling, taking out the gel, washing, placing the gel in an oven, drying for 16h at 70 ℃ to obtain a white solid product, and crushing the solid product into particles to obtain the bionic mussel polymer gel plugging agent A3.
Example 4
Adding 0.5 part of tea phenol into 100 parts of distilled water at 25 ℃, stirring for 10min by using a magnetic stirrer, adding 2 parts of nano-clay laponite RD, stirring for 16h at 25 ℃ by using the magnetic stirrer, adding 5 parts of vinyl monomer (specifically acrylamide) and 0.1 part of cross-linking agent (specifically N, N-dimethyl bisacrylamide) into the mixture, and stirring for 10min at 25 ℃ until the monomer and the cross-linking agent are fully dissolved. And then pouring the mixture into a three-neck flask, introducing nitrogen for 30min, heating to 60 ℃ by using a water bath kettle, heating while stirring by using an electric stirrer, adding 0.1 part of an initiator (specifically azodiisobutymidine hydrochloride) after the temperature of the mixture reaches 60 ℃, and reacting for 8h to obtain a white gel product. And after cooling, taking out the gel, washing, placing the gel in an oven, drying for 16h at 70 ℃ to obtain a white solid product, and crushing the solid product into particles to obtain the bionic mussel polymer gel plugging agent A4.
Example 5
Adding 1 part of tea phenol into 100 parts of distilled water at 25 ℃, stirring for 12min by using a magnetic stirrer, adding 2.5 parts of nano clay laponite RD, stirring for 18h at 25 ℃ by using the magnetic stirrer, adding 7.5 parts of vinyl monomer (specifically acrylamide) and 2.5 parts of cross-linking agent (specifically N, N-dimethyl bisacrylamide) into the mixture, and stirring for 15min at 25 ℃ until the monomer and the cross-linking agent are fully dissolved. And then pouring the mixture into a three-neck flask, introducing nitrogen for 30min, heating to 60 ℃ by using a water bath kettle, heating while stirring by using an electric stirrer, adding 1 part of an initiator (specifically azodiisobutymidine hydrochloride) after the temperature of the mixture reaches 60 ℃, and reacting for 8h to obtain a white gel product. And after cooling, taking out the gel, washing, placing the gel in an oven, drying for 16h at 70 ℃ to obtain a white solid product, and crushing the solid product into particles to obtain the bionic mussel polymer gel plugging agent A5.
Example 6
Adding 5 parts of theaphenol into 100 parts of distilled water at 25 ℃, stirring for 15min by using a magnetic stirrer, adding 5 parts of nanoclay laponite RD, stirring for 20h at 25 ℃ by using the magnetic stirrer, adding 10 parts of vinyl monomer (specifically acrylamide) and 5 parts of cross-linking agent (specifically N, N-dimethyl bisacrylamide) into the mixture, and stirring for 20min at 25 ℃ until the monomer and the cross-linking agent are fully dissolved. And then pouring the mixture into a three-neck flask, introducing nitrogen for 30min, heating to 60 ℃ by using a water bath kettle, heating while stirring by using an electric stirrer, adding 3 parts of an initiator (specifically azodiisobutymidine hydrochloride) after the temperature of the mixture reaches 60 ℃, and reacting for 8h to obtain a white gel product. And after cooling, taking out the gel, washing, placing the gel in an oven, drying for 16h at 70 ℃ to obtain a white solid product, and crushing the solid product into particles to obtain the bionic mussel polymer gel plugging agent A6.
Example 7
Adding 0.5 part of tannic acid into 100 parts of distilled water at 25 ℃, stirring for 10min by using a magnetic stirrer, adding 2 parts of nanoclay laponite RD, stirring for 16h at 25 ℃ by using the magnetic stirrer, adding 5 parts of vinyl monomer (specifically acrylamide) and 0.1 part of cross-linking agent (specifically N, N-dimethyl bisacrylamide) into the mixture, and stirring for 10min at 25 ℃ until the monomer and the cross-linking agent are fully dissolved. And then pouring the mixture into a three-neck flask, introducing nitrogen for 30min, heating to 60 ℃ by using a water bath kettle, heating while stirring by using an electric stirrer, adding 0.1 part of an initiator (specifically azodiisobutymidine hydrochloride) after the temperature of the mixture reaches 60 ℃, and reacting for 8h to obtain a white gel product. And after cooling, taking out the gel, washing, placing the gel in an oven, drying for 16h at 70 ℃ to obtain a white solid product, and crushing the solid product into particles to obtain the bionic mussel polymer gel plugging agent A7.
Example 8
Adding 1 part of tannic acid into 100 parts of distilled water at 25 ℃, stirring for 12min by using a magnetic stirrer, adding 2.5 parts of nanoclay laponite RD, stirring for 18h at 25 ℃ by using the magnetic stirrer, adding 7.5 parts of vinyl monomer (specifically acrylamide) and 2.5 parts of cross-linking agent (specifically N, N-dimethyl bisacrylamide) into the mixture, and stirring for 15min at 25 ℃ until the monomer and the cross-linking agent are fully dissolved. And then pouring the mixture into a three-neck flask, introducing nitrogen for 30min, heating to 60 ℃ by using a water bath kettle, heating while stirring by using an electric stirrer, adding 1 part of an initiator (specifically azodiisobutymidine hydrochloride) after the temperature of the mixture reaches 60 ℃, and reacting for 8h to obtain a white gel product. And after cooling, taking out the gel, washing, placing the gel in an oven, drying for 16h at 70 ℃ to obtain a white solid product, and crushing the solid product into particles to obtain the bionic mussel polymer gel plugging agent A8.
Example 9
Adding 5 parts of tannic acid into 100 parts of distilled water at 25 ℃, stirring for 15min by using a magnetic stirrer, adding 5 parts of nanoclay laponite RD, stirring for 20h at 25 ℃ by using the magnetic stirrer, adding 10 parts of vinyl monomer (specifically acrylamide) and 5 parts of cross-linking agent (specifically N, N-dimethyl bisacrylamide) into the mixture, and stirring for 20min at 25 ℃ until the monomer and the cross-linking agent are fully dissolved. And then pouring the mixture into a three-neck flask, introducing nitrogen for 30min, heating to 60 ℃ by using a water bath kettle, heating while stirring by using an electric stirrer, adding 3 parts of an initiator (specifically azodiisobutymidine hydrochloride) after the temperature of the mixture reaches 60 ℃, and reacting for 8h to obtain a white gel product. And after cooling, taking out the gel, washing, placing the gel in an oven, drying for 16h at 70 ℃ to obtain a white solid product, and crushing the solid product into particles to obtain the bionic mussel polymer gel plugging agent A9.
Example 10
Adding 0.5 part of gallic acid into 100 parts of distilled water at 25 ℃, stirring for 10min by using a magnetic stirrer, adding 2 parts of nano clay laponite RD, stirring for 16h at 25 ℃ by using the magnetic stirrer, adding 5 parts of vinyl monomer (specifically acrylamide) and 0.1 part of cross-linking agent (specifically N, N-dimethyl bisacrylamide) into the mixture, and stirring for 10min at 25 ℃ until the monomer and the cross-linking agent are fully dissolved. And then pouring the mixture into a three-neck flask, introducing nitrogen for 30min, heating to 60 ℃ by using a water bath kettle, heating while stirring by using an electric stirrer, adding 0.1 part of an initiator (specifically azodiisobutymidine hydrochloride) after the temperature of the mixture reaches 60 ℃, and reacting for 8h to obtain a white gel product. And after cooling, taking out the gel, washing, placing the gel in an oven, drying for 16h at 70 ℃ to obtain a white solid product, and crushing the solid product into particles to obtain the bionic mussel polymer gel plugging agent A10.
Example 11
Adding 1 part of gallic acid into 100 parts of distilled water at 25 ℃, stirring for 12min by using a magnetic stirrer, adding 2.5 parts of nano clay laponite RD, stirring for 18h at 25 ℃ by using the magnetic stirrer, adding 7.5 parts of vinyl monomer (specifically acrylamide) and 2.5 parts of cross-linking agent (specifically N, N-dimethyl bisacrylamide) into the mixture, and stirring for 15min at 25 ℃ until the monomer and the cross-linking agent are fully dissolved. And then pouring the mixture into a three-neck flask, introducing nitrogen for 30min, heating to 60 ℃ by using a water bath kettle, heating while stirring by using an electric stirrer, adding 1 part of an initiator (specifically azodiisobutymidine hydrochloride) after the temperature of the mixture reaches 60 ℃, and reacting for 8h to obtain a white gel product. And after cooling, taking out the gel, washing, placing the gel in an oven, drying for 16h at 70 ℃ to obtain a white solid product, and crushing the solid product into particles to obtain the bionic mussel polymer gel plugging agent A11.
Example 12
Adding 5 parts of gallic acid into 100 parts of distilled water at 25 ℃, stirring for 15min by using a magnetic stirrer, adding 5 parts of nano clay laponite RD, stirring for 20h at 25 ℃ by using the magnetic stirrer, adding 10 parts of vinyl monomer (specifically acrylamide) and 5 parts of cross-linking agent (specifically N, N-dimethyl bisacrylamide) into the mixture, and stirring for 20min at 25 ℃ until the monomer and the cross-linking agent are fully dissolved. And then pouring the mixture into a three-neck flask, introducing nitrogen for 30min, heating to 60 ℃ by using a water bath kettle, heating while stirring by using an electric stirrer, adding 3 parts of an initiator (specifically azodiisobutymidine hydrochloride) after the temperature of the mixture reaches 60 ℃, and reacting for 8h to obtain a white gel product. And after cooling, taking out the gel, washing, placing the gel in an oven, drying for 16h at 70 ℃ to obtain a white solid product, and crushing the solid product into particles to obtain the bionic mussel polymer gel plugging agent A12.
Comparative example 1
After 2.5 parts of the nanoclay laponite RD was stirred at 25 ℃ for 18 hours using a magnetic stirrer, 7.5 parts of a vinyl monomer (specifically acrylamide) and 2.5 parts of a crosslinking agent (specifically N, N-dimethyl bisacrylamide) were added to the above mixture, and stirred at 25 ℃ for 15 minutes until the monomer and the crosslinking agent were sufficiently dissolved. And then pouring the mixture into a three-neck flask, introducing nitrogen for 30min, heating to 60 ℃ by using a water bath kettle, heating while stirring by using an electric stirrer, adding 1 part of an initiator (specifically azodiisobutymidine hydrochloride) after the temperature of the mixture reaches 60 ℃, and reacting for 8h to obtain a white gel product. And after cooling, taking out the gel, washing, placing the gel in an oven, drying for 16h at 70 ℃ to obtain a white solid product, and crushing the solid product into particles to obtain the plugging agent D1.
Comparative example 2
Adding 0.5 part of dopamine into 100 parts of distilled water at 25 ℃, stirring for 10min by using a magnetic stirrer, adding 5 parts of vinyl monomer (specifically N, N-dimethyl bisacrylamide) and 0.1 part of cross-linking agent (specifically acrylamide), and stirring for 10min at 25 ℃ until the monomer and the cross-linking agent are fully dissolved. And then pouring the mixture into a three-neck flask, introducing nitrogen for 30min, heating to 60 ℃ by using a water bath kettle, heating while stirring by using an electric stirrer, adding 0.1 part of an initiator (specifically azodiisobutymidine hydrochloride) after the temperature of the mixture reaches 60 ℃, and reacting for 8h to obtain a white gel product. And after cooling, taking out the gel, washing, placing the gel in an oven, drying for 16h at 70 ℃ to obtain a white solid product, and crushing the solid product into particles to obtain the bionic mussel polymer gel plugging agent A2.
Test example 1
The method is implemented by combining a high-temperature high-pressure water loss instrument with a sand tray, wherein the high-temperature high-pressure water loss instrument mainly comprises a nitrogen cylinder, a kettle body, the sand tray and a collecting barrel. And the upper part of the kettle body is provided with a rotary air inlet valve, the lower part of the kettle body is provided with a rotary liquid discharge valve, and the upper air inlet valve is connected with a nitrogen bottle.
The sand table forming process is as follows: a core with known permeability (the permeability is specifically 1000mD) is cut into a cylindrical sand disc with the diameter of 61 +/-0.5 mm and the length of 5 +/-0.5 mm by using a lathe.
The evaluation of the seepage leakage stoppage effect of the deepwater drilling by using the seepage sand tray sequentially comprises the following steps:
(1) a sand disc with known permeability is arranged in the kettle body, and the lower cover and the lower valve rod are screwed;
(2) the kettle body is inverted, the prepared drilling fluid and plugging agent are poured from the upper part, and the upper cover and the upper valve rod are screwed and arranged in a heating sleeve of a high-temperature high-pressure water loss instrument;
(3) a nitrogen inlet valve is installed. Opening a main valve of the nitrogen cylinder, adjusting the pressure reducing valve to 100psi, and opening an air inlet valve of an upper valve rod;
(4) opening a lower rotary liquid discharge valve, immediately pressing a stopwatch to record time and instantaneous leakage, then increasing pressure at the speed of 100psi/2min (100 psi is used as a pressurizing step length, and stabilizing the pressure for 2min after pressurization), recording the accumulated leakage under different pressures, stabilizing the pressure for 2min after the pressure reaches 700psi, and recording the total leakage;
(5) after the plugging is finished, the rotary liquid discharging valve is closed, then the nitrogen cylinder valve is closed, the pressure reducing valve is loosened, the pressure reducing valve on the top cover of the plugging instrument is opened to release air, the kettle body is disassembled, the top cover is unscrewed, the drilling fluid and the plugging agent in the kettle body are taken out, the sand tray is taken out, and the plugging test device is cleaned.
Wherein, the instantaneous leakage amount refers to the amount of the mud instantaneously leaked by opening the lower rotary liquid discharge valve under the pressure of 100 psi. The accumulated leakage is the accumulated leakage after the ball valve is opened, the pressure is increased to 700psi at 100psi/2min, and then the pressure is stabilized for 2 min. The pressure-bearing capacity of the plugging layer is that the pressure-bearing capacity is not larger than 700psi when the leakage quantity is not suddenly amplified in the pressure boosting process from 100psi to 700psi and the pressure stabilizing period of 700 psi; and in the boosting process, when a certain pressure leakage quantity is suddenly amplified, the pressure is regarded as the bearing pressure of the plugging layer.
Plugging effect evaluation was performed according to the above method using the plugging agents obtained in examples 1 to 12 and comparative examples 1 to 2, wherein the drilling fluid formulation: 4% by weight of a base slurry + 0.5% by weight of a tackifier + 1% by weight of a shear strength improver + 1% by weight of a fluid loss additive + barite (density 1.4 g/cm)3). Wherein 4 wt% bentonite and 0.5 wt% carbonic acidAdding sodium into deionized water, stirring and aging for 16h to obtain base slurry, wherein the tackifier is polyacrylamide, the shear strength improver is modified starch, the filtrate loss reducer is polyanionic cellulose, and the barite is barium sulfate. In addition, the addition amount of the plugging agent in the test is 3 wt% of the drilling fluid, and the test results are shown in table 1.
TABLE 1
| Instantaneous leakage/mL | Cumulative leakage/mL | Bearing pressure/MPa | |
| Example 1 | 2 | 5 | 6 |
| Comparative example 1 | 15 | 35 | 2 |
| Comparative example 2 | 10 | 22 | 3 |
| Example 2 | 2 | 4 | 6.4 |
| Example 3 | 1 | 4 | 6.8 |
| Example 4 | 5 | 15 | 5 |
| Example 5 | 5 | 14 | 5 |
| Example 6 | 4 | 12 | 5 |
| Example 7 | 4.8 | 14 | 5 |
| Example 8 | 4.6 | 13 | 5 |
| Example 9 | 4.6 | 13 | 5 |
| Example 10 | 6.4 | 16 | 4 |
| Example 11 | 6 | 15 | 4 |
| Example 12 | 6 | 14 | 4 |
As can be seen from Table 1, examples 1-12 are plugging agents prepared using the plugging agent composition of the present invention, which have significantly better plugging effect and pressure resistance than comparative example 1, which does not contain biomimetic mussel adhesive, and comparative example 2, which does not contain nanoclay laponite RD. In addition, in all tests, the plugging effect of comparative example 1 was the worst, mainly because no biomimetic mussel adhesive was added in the synthesis process, the synthesized product did not have strong adhesion, and a strong adhesion plugging layer could not be formed in the leakage channel.
Test example 2
The plugging agents obtained in example 1, example 4, example 7 and comparative examples 1 to 2 were added to the drilling fluid (the amount of the plugging agent added was 3 wt% of the drilling fluid), and then aged at different temperatures for 16 hours, and the evaluation of the plugging effect of the sand table was performed in the same manner as in test example 1, and the results are shown in table 2. The drilling fluid formulation was otherwise the same as in test example 1.
TABLE 2
As can be seen from Table 2, the plugging agent prepared by using the plugging agent composition of the invention can resist 180 ℃ and has good plugging effect. In addition, the nano clay is added into the plugging agent, so that the temperature resistance of the plugging agent can be effectively improved, and the supermolecular structure can be formed between the hydroxyl on the surface of the nano clay and a plurality of hydroxyl of the bionic mussel adhesive, so that the temperature resistance of the plugging agent is improved.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (13)
1, kinds of plugging agent composition, characterized in that, the composition contains bionic mussel adhesive, nano clay, vinyl monomer, cross-linking agent and water.
2. The composition as in claim 1, wherein the biomimetic mussel adhesive is 0.3-3 parts by weight, the nanoclay is 1-8 parts by weight, the vinyl monomer is 3-15 parts by weight, and the cross-linking agent is 0.05-8 parts by weight, relative to 100 parts by weight of water.
3. The composition of claim 1, wherein the biomimetic mussel adhesive is or more of gallic acid, dopamine, catechol, and tannic acid.
4. The composition of any of claims 1-3, wherein the nanoclay is magnesium aluminum silicate;
preferably, the nanoclay is or more of nanoclay laponite RDS, nanoclay laponite SL25, nanoclay laponite js, and nanoclay laponite RD.
5. The composition of any of claims 1-3, wherein the vinylic monomer is or more of an acrylic monomer and an acrylamide monomer;
preferably, the vinyl monomer is or more of acrylamide, acrylic acid, methacrylamide, methacrylic acid and N-vinyl pyrrolidone.
6. The composition of any of claims 1-3, wherein the crosslinker is one or more of N, N-dimethylbisacrylamide, ethylene glycol dimethacrylate, 1, 4-butanediol diacrylate, and tetraisocyanate .
A process for preparing kinds of leak stopping agent, which comprises mixing the components of the leak stopping agent composition as claimed in any of claims 1-6 and carrying out polymerization crosslinking reaction.
8. The method of claim 7, wherein the biomimetic mussel adhesive, the nanoclay and water are mixed before being mixed with the vinyl-based monomer and cross-linking agent for a second time;
preferably, the mixing conditions include a temperature of 10-40 deg.C and a time of 10-24 hours;
preferably, the conditions of the second mixing include: the temperature is 10-40 deg.C, and the time is 5-30 min.
9. The method of claim 7, wherein the conditions of the polymeric crosslinking reaction comprise: the reaction temperature is 50-70 ℃, and the reaction time is 4-8 h.
10. The method of claim 7, wherein the polymeric crosslinking reaction is carried out in the presence of an initiator;
preferably, the initiator is an oxidation-reduction initiator or an azo-type initiator;
preferably, the initiator is or more of azobisisobutyramidine hydrochloride, azobisformamide, azobisisobutylimidazoline hydrochloride, azobisisobutyronitrile formamide, azobiscyclohexylcarbonitrile, azobiscyanovaleric acid, azobisdiisopropylimidazoline, azobisisobutyronitrile, azobisisovaleronitrile, and azobisisoheptonitrile;
preferably, the initiator is used in an amount of 2 to 30 parts by weight, relative to 100 parts by weight of the vinyl-based monomer.
11. The method of claim 7, further comprising the step of drying the polymerized cross-linked reaction product.
12, kinds of plugging agents, which is characterized by being prepared by the preparation method of any of claims 7-11.
13. A plugging agent composition as defined in any of claims 1-6 and a plugging agent prepared by the preparation method as defined in any of claims 7-11, which are applied to leak-proof and plugging of a drilling well.
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