CN111793481A - Resin cementing material for oil-gas well as preparation method and application thereof - Google Patents

Resin cementing material for oil-gas well as preparation method and application thereof Download PDF

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Publication number
CN111793481A
CN111793481A CN202010539604.9A CN202010539604A CN111793481A CN 111793481 A CN111793481 A CN 111793481A CN 202010539604 A CN202010539604 A CN 202010539604A CN 111793481 A CN111793481 A CN 111793481A
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epoxy resin
oil
resin
curing agent
bisphenol
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刘崇高
赵宝辉
涂思琪
邹双
曾建国
冯明慧
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Tianjin Petrochina Boxing Engineering Technology Co ltd
China National Petroleum Corp
CNPC Offshore Engineering Co Ltd
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Tianjin Petrochina Boxing Engineering Technology Co ltd
China National Petroleum Corp
CNPC Offshore Engineering Co Ltd
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Priority to CN202010539604.9A priority Critical patent/CN111793481A/en
Publication of CN111793481A publication Critical patent/CN111793481A/en
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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
    • C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/44—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing organic binders only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5033—Amines aromatic
    • 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
    • C09K8/422—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells specially adapted for sealing expandable pipes, e.g. of the non-hardening type
    • 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
    • C09K8/424—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells using "spacer" 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
    • C09K8/426—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells for plugging

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention specifically relates to a resin cementing material for an oil-gas well as a preparation method and application thereof, belonging to the technical field of oil-gas well engineering, and the resin cementing material for the oil-gas well provided by the embodiment of the invention comprises the following components: bisphenol F epoxy resin and a curing agent; the bisphenol F epoxy resin comprises at least one of the following components: epoxy resin NPEF-170, epoxy resin NPEF-175, epoxy resin NPEF-185 and epoxy resin NPEF-198; the curing agent comprises at least one of the following components: amine curing agents and anhydride curing agents. Under the high-temperature environment of an oil gas well underground, the amido or carboxyl in the amine curing agent or the anhydride curing agent opens the ring of the epoxy group in the epoxy resin, takes the curing agent molecule as the center to form a four-arm star structure, microscopically makes the linear epoxy resin molecule cross-link into a three-dimensional network structure, macroscopically shows that the liquid resin gelled material is solidified into a solid state with certain mechanical strength after a period of time under the high-temperature environment underground, and plays roles of gelling and packing.

Description

Resin cementing material for oil-gas well as preparation method and application thereof
Technical Field
The invention belongs to the technical field of oil-gas well engineering, and particularly relates to a resin cementing material for an oil-gas well as a preparation method and application thereof.
Background
Cementitious materials, also known as cements. Under the physical and chemical action, it can be changed into firm stone-like body from slurry, and can be used for cementing other materials, so that it can be made into the composite solid matter with a certain mechanical strength. Wherein, asphalt, natural or synthetic resin and the like belong to organic gelled materials.
Along with the expansion of exploration and development of oil and gas resources from a shallow layer to a deep layer, the exploitation difficulty is continuously increased, the underground environment is more and more complex, the proportion of unconventional oil and gas resources is more and more large, more requirements are provided for cementing materials for oil and gas wells, and the traditional ordinary Portland cement is difficult to comprehensively meet the requirements of various complex well conditions. Ordinary portland cement has been a cementing material mainly used for oil and gas well development in the past decades due to its low cost and easy control of pumping, displacement and thickening, and related additives have also been fully researched. But the inherent defects of the ordinary portland cement, such as high brittleness, corrosion resistance and the like, cannot be completely changed only by adding the additive into the ordinary portland cement. Therefore, it is necessary to develop a new cement material to make up for the disadvantages of ordinary portland cement.
Disclosure of Invention
In view of the above problems, the present invention has been made to provide a resin cement for oil and gas wells, a method for preparing the same, and applications thereof, which overcome the above problems or at least partially solve the above problems.
The embodiment of the invention provides a resin cementing material for an oil-gas well, which comprises the following components:
bisphenol F epoxy resin and a curing agent;
the bisphenol F epoxy resin comprises at least one of the following components: epoxy resin NPEF-170, epoxy resin NPEF-175, epoxy resin NPEF-185 and epoxy resin NPEF-198;
the curing agent comprises at least one of the following components: amine curing agents and anhydride curing agents.
Optionally, the weight ratio of the bisphenol F epoxy resin to the curing agent is 9-11: 4-10.
Optionally, the amine curing agent comprises at least one of the following: isophorone diamine, 3-diethylaminopropylamine, m-phenylenediamine and 3, 3 '-diethyl-4, 4' -diaminodiphenylmethane, and the anhydride curing agent comprises at least one of the following components: maleic anhydride, methyl nadic anhydride, methyl tetrahydrophthalic anhydride and methyl hexahydrophthalic anhydride.
Optionally, the resin cementing material for oil and gas wells further comprises the following components: a diluent, the diluent comprising: small molecular epoxy group-containing compound, wherein the molecular weight is less than or equal to 300.
Optionally, the small-molecule epoxy-group-containing compound includes at least one of: butyl glycidyl ether, propylene oxide phenyl ether, dodecyl-tetradecyl glycidyl ether.
Optionally, the weight of the diluent is 10-20% of the weight of the bisphenol F epoxy resin.
Optionally, the resin cementing material for oil and gas wells further comprises the following components: a set point control agent comprising at least one of: triethanolamine, N-dimethylaniline and 2-ethyl-4-methylimidazole.
Optionally, the weight of the coagulation regulator is less than or equal to 9% of the weight of the bisphenol F epoxy resin.
Based on the same inventive concept, the embodiment of the invention also provides a preparation method of the resin cementing material for the oil-gas well, which comprises the following steps:
preparing bisphenol F epoxy resin and a curing agent according to the weight ratio of 9-11: 4-10, preparing a diluent according to the weight of less than or equal to 10-20% of the weight of the bisphenol F epoxy resin, and preparing a coagulation regulator according to the weight of less than or equal to 9% of the weight of the bisphenol F epoxy resin;
uniformly mixing the bisphenol F epoxy resin and the diluent to obtain a first mixture;
and uniformly mixing the first mixture, the curing agent and the setting regulator to obtain the oil-gas well resin cementing material.
Based on the same inventive concept, the embodiment of the invention also provides an application of the resin cementing material for the oil-gas well, and the resin cementing material for the oil-gas well is used as a curing material for downhole sealing of the oil-gas well.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
the resin cementing material for the oil-gas well provided by the embodiment of the invention comprises the following components: bisphenol F epoxy resin and a curing agent; the bisphenol F epoxy resin comprises at least one of the following components: epoxy resin NPEF-170, epoxy resin NPEF-175, epoxy resin NPEF-185 and epoxy resin NPEF-198; the curing agent comprises at least one of the following components: amine curing agents and anhydride curing agents.
Under the high-temperature environment of an oil gas well underground, the amido or carboxyl in the amine curing agent or the anhydride curing agent opens the ring of the epoxy group in the epoxy resin, takes the curing agent molecule as the center to form a four-arm star structure, microscopically makes the linear epoxy resin molecule cross-link into a three-dimensional network structure, macroscopically shows that the liquid resin gelled material is solidified into a solid state with certain mechanical strength after a period of time under the high-temperature environment underground, and plays roles of gelling and packing.
The resin cementing material for the oil-gas well provided by the embodiment of the invention has excellent mechanical properties after being cured, the compressive strength can reach more than 60MPa, the elastic modulus can reach about 3GPa, the Poisson ratio can reach 0.4-0.5, and the elongation at break can reach about 3% -4%.
The above description is only an overview of the technical solutions of the present invention, and is intended to provide a clear understanding of the technical means of the present invention, and can be implemented in accordance with the content of the description, and the above and other objects, features, and advantages of the present invention will be more clearly understood, and the following detailed description of the present invention will be made.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a flow chart of a method for preparing a resin cement for oil and gas wells according to an embodiment of the present invention;
FIG. 2 is a graph showing the relationship between the curing time of the resin cement for oil and gas wells and the amount of the setting control agent used at 80 ℃ and 40MPa in examples 1 to 6 of the present invention;
FIG. 3 is a graph showing the curing profile of the resin cement for oil and gas wells according to example 3 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood to have meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The technical scheme of the embodiment of the application is to solve the technical problems, and the general idea is as follows:
in one aspect, the embodiment of the invention provides a resin cementing material for an oil-gas well, wherein the resin cementing material comprises bisphenol F epoxy resin and a curing agent;
the bisphenol F epoxy resin comprises at least one of the following components: epoxy resin NPEF-170, epoxy resin NPEF-175, epoxy resin NPEF-185 and epoxy resin NPEF-198;
the curing agent comprises at least one of the following components: amine curing agents and anhydride curing agents.
The inventor researches and discovers that the bisphenol F epoxy resin and the curing agent are combined to realize the curing reaction under the high-temperature condition, so that the gelation process is synergistically completed.
The bisphenol F epoxy resin has low viscosity and moderate epoxy value, can ensure that the prepared epoxy resin cementing material has good fluidity, is convenient for construction operation, and ensures that a resin solidified body obtained by heating and curing has certain crosslinking degree and certain strength.
The curing agent can cure liquid bisphenol F epoxy resin into a solid state under the condition of a wide range of temperature, and has excellent strength after curing, so that the curing agent plays a role in gelling.
As some alternative embodiments, the weight ratio of the bisphenol F epoxy resin, the diluent and the curing agent is 9-11: 4-10.
The weight ratio of the bisphenol F epoxy resin, the diluent and the curing agent is limited in the range, so that the resin cementing material can exert the optimal cementing effect, namely, the change process from liquid state to solid state can be completed after a period of time at a certain temperature, and the formed cured body has excellent mechanical property.
If the amount of the curing agent is too large, the curing agent may not sufficiently react with the epoxy resin in a ring-opening manner, a tight network structure may not be formed, the strength is low, and if the amount is too small, the epoxy resin may not be completely cured, the curing time is prolonged, and the gelling effect cannot be exerted.
The amine curing agent comprises at least one of the following components: isophorone diamine, 3-diethylaminopropylamine, m-phenylenediamine and 3, 3 '-diethyl-4, 4' -diaminodiphenylmethane, and the anhydride curing agent comprises at least one of the following components: maleic anhydride, methyl nadic anhydride, methyl tetrahydrophthalic anhydride and methyl hexahydrophthalic anhydride.
The reason why isophoronediamine, 3-diethylaminopropylamine, m-phenylenediamine and 3, 3 '-diethyl-4, 4' -diaminodiphenylmethane are preferred from the amine-based curing agents is that: the activity is moderate, and the epoxy resin can be subjected to curing reaction at a moderate speed at a lower temperature to form a cured body, so that the problems that the activity of other types of amine curing agents is strong, the curing reaction is rapidly completed, and the reaction is uncontrollable are solved.
The reason why maleic anhydride, methylnadic anhydride, methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride are preferred among the anhydride curing agents is that: has lower melting point, is easy to be uniformly mixed with the epoxy resin at room temperature, has higher reaction activity and better compatibility with the epoxy resin.
As some optional embodiments, the resin cementing material for oil and gas wells further comprises the following components: a diluent, the diluent comprising: small molecular epoxy group-containing compound, wherein the molecular weight is less than or equal to 300.
The thinner with smaller molecular weight is selected, the viscosity is lower, the viscosity of an epoxy resin cementing material system can be effectively reduced, the fluidity is improved, the construction operation is convenient, and meanwhile, the thinner is lower in cost, small in volatility and beneficial to environmental protection.
As some alternative embodiments, the small molecule epoxy-containing compound comprises at least one of: butyl glycidyl ether, propylene oxide phenyl ether, dodecyl-tetradecyl glycidyl ether.
The reason why butyl glycidyl ether, propylene oxide phenyl ether and dodecyl-tetradecyl glycidyl ether are preferred from among the small-molecule epoxy group-containing compounds is that: the epoxy resin binding material has low viscosity, can effectively reduce the viscosity of an epoxy resin binding material system, has low volatility, is convenient to use, and is beneficial to environmental protection.
As some alternative embodiments, the weight of the diluent is 10-20% of the weight of the bisphenol F epoxy resin.
The diluent with the weight ratio can reduce the viscosity of an epoxy resin cementing material system in a proper range, if the diluent is used in an excessive amount, the curing is slow, the strength of a cured body is not enough, if the diluent is used in an insufficient amount, the viscosity of the system can not be effectively reduced, and the construction operation is not utilized.
As some optional embodiments, the resin cementing material for oil and gas wells further comprises the following components: a set point control agent comprising at least one of: triethanolamine, N-dimethylaniline and 2-ethyl-4-methylimidazole.
The reasons why triethanolamine, N-dimethylaniline and 2-ethyl-4-methylimidazole are preferred from the set control agent are: the activity is moderate, the curing reaction rate can be effectively accelerated by adding a small amount of the coagulant, the curing time of the resin is shortened, the curing time is shortened by adding more coagulant, if other coagulant with stronger activity is used, the reaction can be vigorously carried out by adding a trace amount of the coagulant, and the curing time can not be controlled as required.
In some alternative embodiments, the weight of the set control agent is less than or equal to 9% of the weight of the bisphenol F epoxy resin.
As some optional embodiments, the resin cementing material for oil and gas wells further comprises the following components: a set point control agent comprising at least one of: triethanolamine, N-dimethylaniline and 2-ethyl-4-methylimidazole.
The bisphenol F epoxy resin has low viscosity, the viscosity of the bisphenol F epoxy resin can be further reduced by adding the coagulation regulator, the bisphenol F epoxy resin is convenient to pump into an underground environment for construction operation, and meanwhile, the curing rate of the resin cementing material for the oil-gas well can be controlled by regulating the viscosity of the resin cementing material for the oil-gas well;
in some alternative embodiments, the weight of the set control agent is less than or equal to 9% of the weight of the bisphenol F epoxy resin.
On the other hand, as shown in fig. 1, an embodiment of the present invention further provides a method for preparing a resin cement for oil and gas wells, the method including:
s1, preparing bisphenol F epoxy resin and a curing agent according to the weight ratio of 9-11: 4-10, preparing a diluent according to the weight of the bisphenol F epoxy resin being not more than 10-20%, and preparing a pour point regulator according to the weight of the bisphenol F epoxy resin being not more than 9%;
s2, uniformly mixing the bisphenol F epoxy resin and the diluent to obtain a first mixture;
s3, uniformly mixing the first mixture, the curing agent and the setting regulator to obtain the oil-gas well resin cementing material.
The reason why the curing agent and the setting regulator are added after the bisphenol F epoxy resin and the diluent are mixed is that the curing reaction is not initiated by simply mixing the resin and the diluent, and the mixture obtained by mixing the resin and the diluent can be stored at normal temperature for a long time, and the curing reaction is initiated once the curing agent or the setting regulator is introduced.
In the preparation method, after the oil-gas well resin cementing material is obtained, the oil-gas well resin cementing material is heated to a target temperature, and can be cured to generate a cementing effect.
In a third aspect, the embodiment of the invention also provides an application of the resin cementing material for the oil and gas well, which is characterized in that the resin cementing material for the oil and gas well is used as a curing material for downhole sealing of the oil and gas well.
When in application, the selectable use method is as follows:
pumping the prepared uncured resin cementing material for the oil-gas well into a gap between a casing and a well wall of the oil-gas well or other sealing target areas, and completing the sealing of the oil-gas well after curing.
The oil and gas well sealed by the resin cementing material for the oil and gas well can be used in the following extreme environments: the downhole temperature is 120 ℃, and the formation pressure is 60 MPa.
The resin cement for oil and gas wells according to the present application will be described in detail with reference to examples, comparative examples and experimental data.
Example 1
At room temperature, 100 parts of bisphenol F epoxy resin NPEF-170 is added into a beaker, 20 parts of diluent dodecyl glycidyl ether is added, the mixture is stirred uniformly and is kept stand for 5 minutes. 40 parts of curing agent 3, 3 '-diethyl-4, 4' -diaminodiphenylmethane is added into the beaker and stirred uniformly.
Example 2
This example differs from example 1 in that: adding curing agent, stirring uniformly, and adding 0.5 part of coagulation regulator N, N-dimethylaniline. The performance test method was the same as in example 1.
Example 3
This example differs from example 1 in that: adding a curing agent, stirring uniformly, and adding 1.5 parts of coagulation regulator N, N-dimethylaniline. The performance test method was the same as in example 1.
Example 4
This example differs from example 1 in that: adding a curing agent, stirring uniformly, and adding 3 parts of coagulation regulator N, N-dimethylaniline. The performance test method was the same as in example 1.
Example 5
This example differs from example 1 in that: adding a curing agent, stirring uniformly, and adding 4.5 parts of coagulation regulator N, N-dimethylaniline. The performance test method was the same as in example 1.
Example 6
This example differs from example 1 in that: adding a curing agent, uniformly stirring, and adding 6 parts of coagulation regulator N, N-dimethylaniline. The performance test method was the same as in example 1.
Example 7
This example differs from example 1 in that: adding a curing agent, stirring uniformly, and adding 7.5 parts of coagulation regulator N, N-dimethylaniline. The performance test method is the same as that of example 1, except that the curing time test conditions are 50 ℃ and 25 MPa.
Example 8
This example differs from example 1 in that: the curing agent is 100 parts of methyl hexahydrophthalic anhydride, and 0.36 part of thickening time control agent triethanolamine is added after the mixture is evenly stirred. The performance test method is the same as that of example 1, except that the curing time test conditions are 100 ℃ and 50 MPa.
Comparative example 1
This example differs from example 1 in that: the curing agent is diethylenetriamine.
Comparative example 2
This example differs from example 1 in that: no curing agent is contained.
Comparative example 3
Ordinary silicate cement is used as the sealing material of oil and gas well.
The experimental effect is as follows:
the resin gelled materials for oil and gas wells prepared in examples 1 to 8 and comparative examples 1 to 3 were subjected to performance tests, and the test results are shown in table 1.
The test method comprises the following steps:
curing time: the assay was described in GB/T19139-2012.
Compressive strength and elastic modulus: the determination method is tested at room temperature according to GB/T2567-2008.
TABLE 1
Curing time/min Curing temperature/. degree.C Compressive strength/MPa Modulus of elasticity/GPa Poisson ratio
Example 1 360 80 85.7 3.09 0.488
Example 2 300 80 90.3 3.19 0.486
Example 3 230 80 91.1 3.23 0.482
Example 4 160 80 91.7 3.25 0.475
Example 5 130 80 91.6 3.25 0.479
Example 6 90 80 92.5 3.20 0.471
Example 7 215 50 68.6 2.39 0.502
Example 8 250 100 94.3 3.03 0.436
Comparative example 1 10 80 —— —— ——
Comparative example 2 —— 80 —— —— ——
Comparative example 3 90 80 23.5 11.5 0.238
In table 1, the curing time refers to the time required for the resin cementing material for oil and gas wells to be completely cured at a certain temperature, and the over-long or over-short curing time indicates that the curing performance of the resin cementing material is poor;
the compressive strength refers to the pressure which can be borne by the cured oil-gas well resin cementing material, and the higher the compressive strength value is, the better the mechanical property of the oil-gas well resin cementing material is;
the elastic modulus is the ratio of stress to corresponding strain when the cured oil-gas well resin cementing material deforms under pressure, and the smaller the elastic modulus is, the better the toughness of the oil-gas well resin cementing material is;
the poisson ratio is that the solidified oil-gas well resin cementing material generates elongation (or contraction) deformation along the load direction and generates contraction (or elongation) deformation in the direction perpendicular to the load direction, and the negative value of the ratio of the strain in the perpendicular direction to the strain in the load direction is the poisson ratio.
From the data in examples 1-8, it can be seen that:
when the temperature is not changed, the curing time of the resin cementing material for the oil-gas well can be adjusted by adjusting the dosage of the setting regulator so as to meet the requirements of downhole operation under different conditions as in examples 1-6.
From the data of the curing time and the curing temperature, it can be known that at a lower temperature, the activity of the curing agent is reduced, the curing time is greatly prolonged, and even incomplete curing occurs, at this time, the curing reaction can be promoted by increasing the dosage of the setting regulator, the curing time is shortened, the oil-gas well resin cementing material is completely cured, and higher strength is obtained, as in example 7. At higher temperatures, the activity of the curing agent increases, causing the curing reaction to occur rapidly and become uncontrollable, resulting in a shorter window time for use, at which point a less active anhydride curing agent may be used to neutralize the acceleration of the curing reaction by the high temperature, as in example 8.
Regarding mechanical properties, the oil-gas well resin cementing materials with different formulas have higher compressive strength and stronger toughness after being cured in different environments; wherein, the compressive strength of the resin cementing material solidified at the temperature of more than 80 ℃ can reach about 90MPa, the compressive strength solidified at the temperature of 50 ℃ can also exceed 60MPa, the elastic modulus can reach about 3GPa, and the Poisson ratio is between 0.4 and 0.5.
From the data in comparative examples 1-3, it can be seen that:
from the data of comparative example 1, it is understood that the use of a highly reactive aliphatic amine-based curing agent (diethylenetriamine) causes rapid progress of the curing reaction, and the reaction is not controlled, and thus it is not practical.
As can be seen from the data of comparative example 2, the curing agent is the core component of the system, and the resin cement cannot be cured without the curing agent, and thus cannot be practically used.
From the data of comparative example 3, it can be seen that the conventional portland cement has a shorter setting time under the same conditions and has inferior set strength and toughness.
Detailed description of the drawings:
as shown in FIG. 2, when the oil-gas well resin cementing material provided by the invention is cured, under the condition of constant temperature, the curing time can be shortened by increasing the dosage of a coagulation regulator;
as shown in fig. 3, the curing process of the resin cementing material for oil and gas wells provided by the invention is depicted. Line 1 represents the temperature change during the curing process of the resin cementing material for oil and gas wells provided by the invention, line 2 represents the pressure change during the curing process, and line 3 represents the consistency change during the curing process, wherein the higher the consistency, the higher the curing degree.
One or more technical solutions in the embodiments of the present invention at least have the following technical effects or advantages:
(1) in the embodiment of the invention, the combination of different curing agents and coagulation regulators can meet the requirements of different underground temperatures, controllable curing can be realized by adjusting the formula of the resin cementing material for the oil-gas well within the temperature range of room temperature to 120 ℃, the curing time can be adjusted within the range of 90-360min, and the application range is wide;
(2) the resin cementing material for the oil-gas well is in a homogeneous low-viscosity liquid state before being cured, can easily enter a tiny gap or an annulus and directly reach a sealing area, and achieves the purpose of blocking;
(3) the resin cementing material for the oil-gas well, provided by the embodiment of the invention, has excellent mechanical properties after being cured, the compressive strength can reach more than 60MPa, the elastic modulus is about 3GPa, the Poisson ratio is between 0.4 and 0.5, the elongation at break is about 3 to 4 percent, and the properties are superior to those of common silicate cement;
(4) the resin cementing material for oil and gas wells provided by the embodiment of the invention does not emit harmful volatile matters after being cured, and is beneficial to environmental protection.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.

Claims (10)

1. The resin cementing material for the oil-gas well is characterized by comprising the following components: bisphenol F epoxy resin and a curing agent;
the bisphenol F epoxy resin comprises at least one of the following components: epoxy resin NPEF-170, epoxy resin NPEF-175, epoxy resin NPEF-185 and epoxy resin NPEF-198;
the curing agent comprises at least one of the following components: amine curing agents and anhydride curing agents.
2. The resin cement for oil and gas wells according to claim 1, wherein the weight ratio of the bisphenol F epoxy resin to the curing agent is 9-11: 4-10.
3. The resin cement for oil and gas wells according to claim 1, wherein the amine curing agent comprises at least one of: isophorone diamine, 3-diethylaminopropylamine, m-phenylenediamine and 3, 3 '-diethyl-4, 4' -diaminodiphenylmethane, and the anhydride curing agent comprises at least one of the following components: maleic anhydride, methyl nadic anhydride, methyl tetrahydrophthalic anhydride and methyl hexahydrophthalic anhydride.
4. The resin cement for oil and gas wells according to claim 1, further comprising the following components: a diluent, the diluent comprising: small molecular epoxy group-containing compound, wherein the molecular weight is less than or equal to 300.
5. The resin cement for oil and gas wells according to claim 4, wherein the small molecule epoxy group-containing compound comprises at least one of: butyl glycidyl ether, propylene oxide phenyl ether, dodecyl-tetradecyl glycidyl ether.
6. The resin cement for oil and gas wells according to claim 4 or 5, wherein the weight of the diluent is 10-20% of the weight of the bisphenol F epoxy resin.
7. The resin cement for oil and gas wells according to claim 1 or 4, further comprising the following components: a set point control agent comprising at least one of: triethanolamine, N-dimethylaniline and 2-ethyl-4-methylimidazole.
8. The resin cementing material for oil and gas wells as claimed in claim 7, wherein the weight of the setting regulator is less than or equal to 9% of the weight of the bisphenol F epoxy resin.
9. A method of preparing the resin cement for oil and gas wells according to any one of claims 1 to 8, comprising:
preparing bisphenol F epoxy resin and a curing agent according to the weight ratio of 9-11: 4-10, preparing a diluent according to the weight of less than or equal to 10-20% of the weight of the bisphenol F epoxy resin, and preparing a coagulation regulator according to the weight of less than or equal to 9% of the weight of the bisphenol F epoxy resin;
uniformly mixing the bisphenol F epoxy resin and the diluent to obtain a first mixture;
and uniformly mixing the first mixture, the curing agent and the setting regulator to obtain the oil-gas well resin cementing material.
10. Use of the resin cement for oil and gas wells according to any one of claims 1 to 8 as a setting material for downhole setting of oil and gas wells.
CN202010539604.9A 2020-06-12 2020-06-12 Resin cementing material for oil-gas well as preparation method and application thereof Pending CN111793481A (en)

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Application publication date: 20201020