CN112625667B - Hydrophobic modified core-shell structure environment-friendly slow/controlled release temporary plugging agent and preparation method thereof - Google Patents
Hydrophobic modified core-shell structure environment-friendly slow/controlled release temporary plugging agent and preparation method thereof Download PDFInfo
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- CN112625667B CN112625667B CN202011506782.8A CN202011506782A CN112625667B CN 112625667 B CN112625667 B CN 112625667B CN 202011506782 A CN202011506782 A CN 202011506782A CN 112625667 B CN112625667 B CN 112625667B
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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
- C09K8/50—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
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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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
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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
- C09K8/50—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
- C09K8/5083—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C09K8/50—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
- C09K8/5086—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
Abstract
The invention relates to the technical field of petroleum plugging, and particularly discloses an environment-friendly slow/controlled release temporary plugging agent with a hydrophobic modified core-shell structure and a preparation method thereof. Preheating water-soluble temporary plugging particles, uniformly stirring and mixing toluene diisocyanate, polyether polyol, chitosan, diethyl toluene diamine and epoxy resin, and spraying the mixture on the surfaces of the water-soluble temporary plugging particles to form a degradable framework layer; and spraying molten paraffin on the surface of the degradable skeleton, and forming a shell structure comprising the degradable skeleton and the paraffin outside the water-soluble temporary plugging particle core. The slow/controlled release temporary plugging agent prepared by the patent can be adjusted in a large range, so that the effect of adjustable slow release performance is achieved, and meanwhile, the mechanical property of the temporary plugging agent is greatly improved due to the core-shell structure.
Description
Technical Field
The invention relates to the technical field of petroleum plugging, in particular to an environment-friendly slow/controlled release temporary plugging agent with a hydrophobic modified core-shell structure and a preparation method thereof.
Background
When drilling and production of petroleum and natural gas, the gas well not only needs to effectively protect the wall and stop the leakage, but also needs to prevent the damage to a production layer caused by the gas well, and for a voidage low-pressure sandstone gas reservoir, the permeability is low, and the damage to the stratum needs to be reduced, so that the effective wall protection and leakage stopping are needed in the drilling and production process.
The temporary plugging techniques currently in use include: foam temporary plugging kill-job technology: the foam generation needs special equipment, the process is complex, the cost is high, the foam stabilization period is short, the requirement of overhaul operation cannot be met, in addition, the foam emission has great pollution to the environment, the higher requirements on the foam strength and stability are provided due to the large span range of the formation pressure coefficient of a work area, and the high-performance foam temporary plugging kill-well technology needs to be further developed.
Secondly, oil-soluble temporary plugging kill technique: although the oil-soluble temporary plugging agent has certain application effect in the field of well killing and leakage prevention, the temporary plugging agent has larger construction risk, and if the temporary plugging agent is difficult to contact condensate oil and dissolve, additional resistance is caused, so that induced spraying is difficult.
Thirdly, a super absorbent resin temporary plugging kill technique: at present, clear water or fresh water is mainly adopted to prepare a super absorbent resin particle temporary plugging agent, but the salt resistance of the temporary plugging agent is poor, and in addition, the temporary plugging agent is easy to move and float upwards due to pressure change in the underground, so that the air tightness is seriously influenced, and potential safety hazards are caused;
gel and composite gel temporary plugging kill technique: the polymer gel has good application potential in the aspect of repairing well temporary plugging, the gel has the dual properties of liquid and solid, not only has the viscosity of the liquid, but also has the hardness of the solid, but the reported gel has to be improved in temperature resistance, pressure resistance and flowback plugging removal performance, and the technical requirement of temporary plugging well killing under the complex pressure coefficient of a work area is difficult to meet. Therefore, several temporary plugging technologies commonly used at present have certain defects, and the temporary plugging needs temporary plugging materials to enter a stratum, a temporary plugging layer is formed at a gap to realize temporary plugging, and temporary plugging failure is easily caused if large pores are met.
Disclosure of Invention
The invention provides an environment-friendly slow/controlled release temporary plugging agent with a hydrophobic modified core-shell structure and a preparation method thereof, and aims to solve the problems that the dissolution process of the temporary plugging agent is difficult to control, the pressure-bearing strength in the plugging process is low, and the temporary plugging is easy to fail in the conventional temporary plugging technology.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the hydrophobic modified environment-friendly sustained/controlled release temporary plugging agent with the core-shell structure comprises a shell and a water-soluble temporary plugging particle core, wherein the shell is coated on the surface of the water-soluble temporary plugging particle core, the shell comprises a degradable framework and a hydrophobic wall material, the hydrophobic wall material is coated outside the degradable framework, the degradable framework comprises modified polyurethane, and the hydrophobic wall material comprises paraffin.
The technical principle and the effect of the technical scheme are as follows:
1. in the scheme, the paraffin has hydrophobicity, and the water slowly permeates through the hydrophobic shell and dissolves the water-soluble temporary plugging particle core for a certain time, so that the slow release time of the temporary plugging agent is effectively adjusted, the mechanical property of the temporary plugging agent can be improved by coating a layer of paraffin outside the degradable framework, and meanwhile, the slow release time of the temporary plugging agent can be adjusted in a large range, so that the application range of the slow/controlled release temporary plugging agent is wider.
2. The degradable framework in the scheme mainly plays a role in supporting and protecting the water-soluble temporary plugging particle core, the slow release performance of the temporary plugging agent is further improved while the particle strength of the temporary plugging agent is improved, the temporary plugging agent obtained in the scheme can meet the temporary plugging requirement in a larger dissolution time range and temperature range, and the temporary plugging agent has the advantages of cheap and easily available raw materials, environmental friendliness, degradability, simplicity and easiness in operation, controllable slow release time of the temporary plugging agent, good slow release performance and the like, and has a wide market prospect.
Further, the water-soluble temporary blocking particle core is a water-soluble degradable resin particle core such as polyvinyl alcohol or an inorganic salt particle core.
Has the advantages that: the water-soluble degradable resin such as polyvinyl alcohol is an environment-friendly water-soluble high polymer material, and inorganic salts such as sodium salt, potassium salt, calcium salt and the like are common water-soluble inorganic substances with low cost on the market, and cannot cause any damage to the environment.
Further, the weight ratio of the degradable skeleton to the hydrophobic wall material is 3: 1-12: 1.
Has the advantages that: the sustained-release time can be regulated and controlled by controlling the weight ratio of the degradable framework to the hydrophobic wall material according to specific use requirements.
Further, the weight percentage of the shell is 10-40%, and the weight percentage of the water-soluble temporary plugging particle core is 60-90%.
Has the advantages that: the slow-release time of the required slow/controlled release temporary plugging agent can be adjusted in a larger range by controlling the coating amount of the shell according to specific use requirements, the slow-release time of the slow/controlled release temporary plugging agent obtained according to the proportion is 5 h-15 d, and the adjustment mode is simple and easy.
The invention also discloses a preparation method of the hydrophobic modified core-shell structure environment-friendly slow/controlled release temporary plugging agent, which comprises the following steps:
step 1: preheating water-soluble temporary plugging particle cores at the temperature of 50-80 ℃;
step 2: weighing toluene diisocyanate, polyether polyol, chitosan, diethyl toluene diamine and epoxy resin, stirring and mixing uniformly, and spraying the mixture on the surface of the water-soluble temporary plugging particle core in the step (1) to form a layer of degradable framework;
and step 3: and (3) spraying molten paraffin on the surface of the degradable skeleton in the step (2), and finally forming a shell comprising the degradable skeleton and the hydrophobic paraffin on the outside of the water-soluble temporary plugging particle core.
Has the advantages that: by adopting the preparation method, the water-soluble temporary plugging particle core is preheated before being coated, the preheating temperature is 50-80 ℃, the preheating temperature is in the range of preheating, a layer of modified polyurethane degradable skeleton which is uniformly distributed on the surface of the water-soluble temporary plugging particle core can be formed, and meanwhile, the water-soluble temporary plugging particle core is preheated before being coated, so that active groups on the surface of the particles can fully react with the modified polyurethane to form the skeleton with certain strength on the surface of the particles during coating, and the bearing strength of the temporary plugging agent is improved; in addition, because the coating, polymerization and hydrophobic coating treatment are simultaneously completed on the surface of the particle core, the time required for preparation is greatly shortened.
Detailed Description
The following is further detailed by way of specific embodiments:
example 1:
the environment-friendly slow/controlled release temporary plugging agent with the hydrophobic modified core-shell structure comprises a shell and a water-soluble temporary plugging particle core, wherein the shell is coated outside the water-soluble temporary plugging particle core, one or more water-soluble temporary plugging particle cores are provided, the water-soluble temporary plugging particle cores are provided in a plurality of embodiments, the shell comprises a degradable framework and a hydrophobic wall material, the hydrophobic wall material is coated outside the degradable framework, the main component of the degradable framework is modified polyurethane, and the main component of the hydrophobic wall material is paraffin.
In this example 1, the water-soluble temporary plugging particle core is made of water-soluble degradable resin such as polyvinyl alcohol, wherein the weight ratio of the degradable skeleton to the hydrophobic wall material is 12:1, the weight percentage of the shell is 10%, and the weight percentage of the water-soluble temporary plugging particle core is 90%.
The preparation method of the hydrophobic modified core-shell structure environment-friendly slow/controlled release temporary plugging agent comprises the following steps:
step 1: placing the core of the water-soluble degradable resin particles such as polyvinyl alcohol in a drum-type coating machine, and heating the water-soluble degradable resin particles such as polyvinyl alcohol to 50 ℃.
And 2, step: weighing toluene diisocyanate, polyether polyol, chitosan, diethyl toluene diamine and epoxy resin according to the weight ratio of 2:2:2:2:1, uniformly stirring and mixing, and slowly spraying the mixture on the surface of the preheated water-soluble degradable resin particle cores of polyvinyl alcohol and the like in the step 1, so that a layer of degradable skeleton is formed on the surface of the water-soluble degradable resin particle cores of polyvinyl alcohol and the like.
And step 3: weighing molten paraffin, spraying the molten paraffin on the surface of the degradable skeleton in the step 2, and forming a shell comprising the paraffin and the degradable skeleton on the surface of a water-soluble degradable resin particle core such as polyvinyl alcohol, wherein the weight percentage of the shell is 10%, and the slow release time of the hydrophobic modified environment-friendly slow/controlled release temporary plugging agent with the core-shell structure obtained in the embodiment 1 is 5 hours measured by a water dissolution method.
Example 2:
the difference from example 1 is that in example 2, the coating amount of the shell, i.e., the weight percentage, is 30%, and the sustained-release time of the obtained sustained/controlled-release temporary plugging agent is 10 days as measured by a water-soluble method.
Example 3:
the difference from the example 1 is that the coating amount of the shell in the example 2, namely the weight percentage is 40%, the slow release time of the obtained slow/controlled release temporary plugging agent is 15 days measured by a water solution method; by combining the examples 1 to 3, it can be known that the time of the slow release of the temporary plugging agent is prolonged along with the increase of the weight percentage of the shell, which indicates that the time of the slow release of the temporary plugging agent can be regulated and controlled by adjusting the weight percentage of the shell under the condition that other conditions are not changed.
Example 4:
the difference from example 1 is that the weight ratio of the degradable skeleton to the hydrophobic wall material in example 4 is 3: 1; the sustained/controlled release temporary plugging agent prepared in this example has a sustained release time of 1 day. Therefore, under the condition that other conditions are not changed, the slow release time is greatly prolonged along with the increase of the content of the paraffin in the hydrophobic wall material, and under the condition that other conditions are not changed, the slow release time of the temporary plugging agent can be controlled by adjusting the content of the paraffin in the hydrophobic wall material.
Example 5:
the difference from example 1 is that in example 5, the component of the water-soluble temporary blocking particle core is an inorganic salt particle core, and the component of the inorganic salt particle core is an inorganic salt such as sodium salt, potassium salt, calcium salt, or the like. The sustained/controlled release temporary plugging agent prepared in this example has a sustained release time similar to that of example 1, which is about 3 hours.
Example 6:
the difference from example 1 is that in step 1 of the method for producing a temporary plugging agent in example 6, the heating temperature of the core of the water-soluble degradable resin particles such as polyvinyl alcohol is 80 ℃. The time for sustained release of the temporary plugging agent prepared in this example is similar to that of example 1, and is about 5 hours.
Comparative example 1:
the difference from example 1 is that in step 1 of the method for preparing the temporary plugging agent in comparative example 1, the core of the water-soluble degradable resin particles such as polyvinyl alcohol is not subjected to the preheating treatment before being coated, and the time for the sustained release of the temporary plugging agent obtained in comparative example 1 is shortened to about 2 hours compared with example 1; the reason is that the toluene diisocyanate, the polyether glycol, the chitosan, the diethyl toluene diamine and the epoxy resin have undergone partial cross-linking curing reaction at high temperature, and a uniform and complete degradable skeleton cannot be formed on the surface of the core, so that the slow release time is short.
Comparative example 2:
the difference from example 1 is that in step 1 of the method for preparing the temporary plugging agent in comparative example 1, the temperature for preheating the core of the water-soluble degradable resin particles such as polyvinyl alcohol before coating is 100 ℃, compared with example 1, the time for releasing the temporary plugging agent obtained in comparative example 1 is shortened to about 3 hours; the reason is that the preheating temperature is too high, so that the synthesis reaction is too fast, the synthesized modified polyurethane is unevenly distributed on the surface of the particle core, namely the thickness of the degradable framework is uneven, on one hand, the slow release time is shortened, and on the other hand, the thickness of the degradable framework is not controllable, so that the slow release time cannot be well controlled.
The foregoing is merely an example of the present invention and common general knowledge of the known specific materials and characteristics thereof has not been described herein in any greater extent. It should be noted that, for those skilled in the art, without departing from the present invention, several changes and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (1)
1. The hydrophobic modified core-shell structure environment-friendly slow/controlled release temporary plugging agent is characterized in that: the shell is coated outside the water-soluble temporary plugging particle core and comprises a degradable framework and a hydrophobic wall material, the hydrophobic wall material is coated outside the degradable framework, the degradable framework comprises modified polyurethane, and the hydrophobic wall material comprises paraffin;
the water-soluble temporary plugging particle core is polyvinyl alcohol resin particles or inorganic salt particles; the weight ratio of the degradable skeleton to the hydrophobic wall material is 3: 1-12: 1; the weight percentage of the shell is 10-40%, and the weight percentage of the water-soluble temporary plugging particle core is 60-90%;
the preparation method of the hydrophobic modified core-shell structure environment-friendly slow/controlled release temporary plugging agent comprises the following steps:
step 1: preheating water-soluble temporary plugging particle cores at the preheating temperature of 50-80 ℃;
step 2: weighing toluene diisocyanate, polyether polyol, chitosan, diethyl toluene diamine and epoxy resin, stirring and mixing uniformly, spraying the mixture on the surface of the water-soluble temporary plugging particle core in the step (1), and performing full reaction to form a degradable framework;
and step 3: and (3) spraying molten paraffin on the surface of the degradable framework in the step (2) to form a hydrophobic shell on the surface of the water-soluble temporary plugging particle core.
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| CN113755145B (en) * | 2021-09-08 | 2022-10-21 | 中国石油天然气股份有限公司 | Preparation for plugging compact oil gas perforation hole and preparation method thereof |
| CN113736027A (en) * | 2021-09-26 | 2021-12-03 | 兰州理工大学 | Polymer gel temporary plugging agent, multistage structure gel temporary plugging agent obtained by using same and preparation method of multistage structure gel temporary plugging agent |
| CN114774094A (en) * | 2022-04-22 | 2022-07-22 | 中国海洋石油集团有限公司 | Permanent type blast hole plugging material used after screen pipe perforation and preparation method |
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| US4741401A (en) * | 1987-01-16 | 1988-05-03 | The Dow Chemical Company | Method for treating subterranean formations |
| US5628813A (en) * | 1992-12-21 | 1997-05-13 | Exxon Chemical Patents Inc. | Abrasion resistant topcoats for control release coatings |
| US7642223B2 (en) * | 2004-10-18 | 2010-01-05 | Halliburton Energy Services, Inc. | Methods of generating a gas in a plugging composition to improve its sealing ability in a downhole permeable zone |
| US8720562B2 (en) * | 2010-10-19 | 2014-05-13 | Halliburton Energy Services, Inc. | Wellbore cementing compositions and methods of making and using same |
| US9410076B2 (en) * | 2012-10-25 | 2016-08-09 | Halliburton Energy Services, Inc. | Wellbore servicing methods and compositions comprising degradable polymers |
| US9429005B2 (en) * | 2012-11-28 | 2016-08-30 | Halliburton Energy Services, Inc. | Methods for hindering the settling of proppant in a subterranean formation |
| US10428264B2 (en) * | 2014-12-12 | 2019-10-01 | Halliburton Energy Services, Inc. | Breaker coated particulates for use in subterranean formation operations |
| CN108102622B (en) * | 2017-11-23 | 2020-10-23 | 中国石油大学(华东) | Shielding temporary plugging protective agent and preparation method thereof |
| CN110776888A (en) * | 2018-07-30 | 2020-02-11 | 中国石油化工股份有限公司 | Composite water-soluble temporary plugging agent for oilfield turning fracturing construction |
| CN110452672A (en) * | 2019-07-19 | 2019-11-15 | 中国石油天然气股份有限公司 | A kind of oil gas well shaft temporarily stifled soluble capsules diverting agent and preparation and construction method |
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