CN110540830A - water-based modified synthetic resin cementing material and preparation method and application thereof - Google Patents
water-based modified synthetic resin cementing material and preparation method and application thereof Download PDFInfo
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- CN110540830A CN110540830A CN201910829948.0A CN201910829948A CN110540830A CN 110540830 A CN110540830 A CN 110540830A CN 201910829948 A CN201910829948 A CN 201910829948A CN 110540830 A CN110540830 A CN 110540830A
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- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 67
- 239000000057 synthetic resin Substances 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003822 epoxy resin Substances 0.000 claims abstract description 37
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 239000012745 toughening agent Substances 0.000 claims abstract description 19
- VMSIYTPWZLSMOH-UHFFFAOYSA-N 2-(dodecoxymethyl)oxirane Chemical compound CCCCCCCCCCCCOCC1CO1 VMSIYTPWZLSMOH-UHFFFAOYSA-N 0.000 claims abstract description 18
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 18
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000015271 coagulation Effects 0.000 claims abstract description 15
- 238000005345 coagulation Methods 0.000 claims abstract description 15
- 239000004568 cement Substances 0.000 claims description 28
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 10
- 229920000768 polyamine Polymers 0.000 claims description 10
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 9
- 125000002723 alicyclic group Chemical group 0.000 claims description 8
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 239000004034 viscosity adjusting agent Substances 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 15
- 239000002904 solvent Substances 0.000 abstract description 7
- 238000004140 cleaning Methods 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract description 3
- 230000003670 easy-to-clean Effects 0.000 abstract description 3
- 230000008719 thickening Effects 0.000 description 25
- 238000012360 testing method Methods 0.000 description 18
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 239000011398 Portland cement Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 239000003129 oil well Substances 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000005465 channeling Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000013035 waterborne resin Substances 0.000 description 2
- 229920006313 waterborne resin Polymers 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—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
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Sealing Material Composition (AREA)
- Epoxy Resins (AREA)
Abstract
the invention relates to a water-based modified synthetic resin cementing material, a preparation method and application thereof, wherein the water-based modified synthetic resin cementing material comprises the following components in parts by weight: 100 parts of water-based modified epoxy resin, 10-15 parts of viscosity regulator, 70-100 parts of curing agent, 0-6 parts of coagulation regulator and 1-5 parts of toughening agent; wherein the viscosity regulator comprises micromolecular epoxy compounds of dodecyl glycidyl ether and epoxypropane benzyl ether; wherein the weight ratio of the small molecular epoxy compound dodecyl glycidyl ether to the epoxypropane benzyl ether is 2: 3-3: 2. Because the epoxy resin is modified by water, the gelled system has certain hydrophilicity, and the pipeline is easy to clean by water after the construction of the gelled system is finished, does not need special solvent for cleaning, and is more environment-friendly and easy to operate.
Description
Technical Field
the invention belongs to the technical field of drilling and completion of oil and gas wells and underground maintenance, and particularly relates to a water-based modified synthetic resin cementing material as well as a preparation method and application thereof.
Background
With the gradual deepening of exploration and development, the complex environment is more and more, oil and gas resources such as deep layer, low permeability, ocean, unconventional and the like become the main resource replacing field, and more serious challenges are brought to the cementing material for the oil and gas well. Ordinary portland cement has been a main cementing material for oil and gas well development due to its low cost and easy control of pumping, displacement and setting. However, the common portland cement stone is a brittle material with inherent microscopic defects, a cement sheath is easily damaged under the underground working condition, and portland cement often has the problems of serious shrinkage, poor corrosion resistance and the like, so that the long-term packing performance of the cement sheath is seriously influenced. The problems of annular cross flow of oil and gas wells, annular pressure after oil well development and the like become technical problems often faced by various large oil fields, and the problems are difficult to fundamentally solve by adopting conventional cementing materials.
the synthetic resin cementing material is a polymer-based material, can avoid fluid channeling caused by weight loss due to the change of a base material, can easily pass through a micropore structure of compact sandstone, has the characteristics of high strength, high elasticity, low shrinkage, corrosion resistance and the like after being cured, overcomes the inherent defects of the conventional cement cementing material, and is an ideal cementing material for oil-gas wells. However, at present, domestic synthetic resin gelled materials are mostly used in the industries of coatings, adhesives, plastics and the like, and the environment under oil and gas wells is complex and different from the requirement of common resin, so that the existing synthetic resin system is difficult to meet the requirement under the well condition.
The patent application with the publication number of CN110016327 discloses an oil and gas well plugging material and a preparation method thereof, and although the plugging material can be basically used for downhole plugging, the environmental protection property cannot be improved on the basis of ensuring the comprehensive performance of the material.
Disclosure of Invention
In view of the above problems, the present invention has been made in order to provide an aqueous modified synthetic resin cement, a method for preparing the same, and applications thereof, which overcome the above problems or at least partially solve the same.
The embodiment of the invention provides a water-based modified synthetic resin cementing material, which comprises the following components in parts by weight:
100 parts of waterborne modified epoxy resin
10-15 parts of viscosity regulator
70-100 parts of curing agent
0-6 parts of a coagulation regulator
1-5 parts of a toughening agent;
Wherein the viscosity regulator comprises dodecyl glycidyl ether and/or propylene oxide benzyl ether; wherein the weight ratio of the dodecyl glycidyl ether to the epoxypropane benzyl ether is 2: 3-3: 2;
the waterborne modified epoxy resin is obtained by grafting a waterborne group sulfonic acid group on the position of epoxy resin methine.
Optionally, the composition comprises the following components in parts by weight:
100 parts of waterborne modified epoxy resin
12 portions of viscosity regulator
90 portions of curing agent
3 portions of coagulation regulator
3 parts of a toughening agent.
optionally, the viscosity regulator comprises a small molecular epoxy compound dodecyl glycidyl ether and/or propylene oxide benzyl ether; wherein the weight ratio of the small molecular epoxy compound dodecyl glycidyl ether to the epoxypropane benzyl ether is 1: 1.
optionally, the curing agent comprises a cycloaliphatic polyamine and/or an anhydride; wherein the weight ratio of the alicyclic polyamine to the acid anhydride is 3: 2-4: 1.
Optionally, the set point regulator comprises 2, 4, 6-tris (dimethylaminomethyl) phenol and/or tetraethylammonium bromide; wherein the weight ratio of the 2, 4, 6-tris (dimethylaminomethyl) phenol to the tetraethylammonium bromide is 5: 2-6: 1.
Optionally, the toughening agent comprises nano zinc oxide and/or aluminum oxide; wherein the weight ratio of the nano zinc oxide to the aluminum oxide is 1: 1-3: 1.
Based on the same inventive concept, the embodiment of the invention also provides a preparation method of the water-based modified synthetic resin gelled material, which is used for preparing the water-based modified synthetic resin gelled material;
The method comprises the following steps:
Preparing raw materials according to the weight parts of the water-based modified synthetic resin cementing material;
Uniformly mixing the water-based modified epoxy resin, the viscosity regulator and the toughening agent in the raw materials to obtain a first mixture;
and uniformly mixing the first mixture with the curing agent and the coagulation regulator in the raw materials to obtain the water-based modified synthetic resin cementing material.
Based on the same inventive concept, the embodiment of the invention also provides an application of the water-based modified synthetic resin cementing material, and the water-based modified synthetic resin cementing material is used for downhole operation of an oil-gas well.
Optionally, the aqueous modified synthetic resin cementing material is used for downhole sealing of oil and gas wells.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
The water-based modified synthetic resin cementing material provided by the embodiment of the invention comprises the following components in parts by weight: 100 parts of water-based modified epoxy resin, 10-15 parts of viscosity regulator, 70-100 parts of curing agent, 0-6 parts of coagulation regulator and 1-5 parts of toughening agent; wherein the viscosity regulator comprises micromolecular epoxy compounds of dodecyl glycidyl ether and epoxypropane benzyl ether; wherein the weight ratio of the small molecular epoxy compound dodecyl glycidyl ether to the epoxypropane benzyl ether is 2: 3-3: 2; the waterborne modified epoxy resin is obtained by grafting a waterborne group sulfonic acid group on the position of epoxy resin methine. Because the epoxy resin is modified by water, the gelling system has certain hydrophilicity, and the pipeline is easy to clean by water after the construction of the gelling system is finished, does not need special solvent for cleaning, and is more environment-friendly and easy to operate; meanwhile, the viscosity of the system is controlled by adopting a small-molecular-weight epoxy compound viscosity regulator which can participate in a curing reaction, the system can be cured without volatilization, the system can be kept at a certain viscosity and is easy to pump, the curing of the system in a well condition closed environment can be ensured, and the environmental pollution caused by solvent volatilization can be avoided; in addition, no water is added in the aqueous modified resin system as a solvent, a reactive viscosity regulator is adopted, and a corresponding curing agent and a coagulation regulator are matched for synergistic action, so that the contradiction that the strength and the thickening time of the conventional aqueous resin are difficult to regulate is avoided, and therefore, the strength and the thickening time are also ensured on the premise of improving the environmental protection property, so that the gelling system can be used for underground sealing; therefore, the technical problem that the underground plugging material in the prior art is poor in environmental protection performance is solved.
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 graph showing the thickening time of a hydraulic modified synthetic resin cement at 90 ℃ in accordance with an embodiment of the present invention, as a function of the amount of a thickening agent added;
FIG. 2 is a graph showing the thickening time of an aqueous modified synthetic resin cement as a function of the amount of a thickening agent added at a temperature of 60 ℃ in an example of the present invention;
FIG. 3 is a graph showing the thickening time of an aqueous modified synthetic resin cement as a function of the amount of a thickening agent added at a temperature of 30 ℃ in an example 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 as having 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 common synthetic resin is mainly used in the industries of coatings, adhesives, plastics and the like, the environment and the requirements under oil and gas wells are different from the requirements of common resin, and the common synthetic resin system is difficult to meet the requirements under the well condition conditions. Analysis shows that the conventional synthetic resin gelled material system mainly has the following problems: (1) the system has high viscosity and is difficult to pump and construct; (2) the thickening time of the system at different temperatures is difficult to control, and the requirements of oil and gas wells at different temperatures cannot be met; (3) the contradiction between thickening time and strength is difficult to adjust, especially for an aqueous system, when the thickening time at a higher temperature meets the requirement, the aqueous system has no strength for a long time, and the thickening time with strength is very short; (4) many resin systems contain more volatile organic compounds and the like, which cause serious pollution to the atmosphere and are difficult to meet the environmental protection requirement; (5) some resins exhibit greater brittleness after curing, which affects their long-term sealing performance.
The synthetic resin cementing material is a polymer-based material, can avoid fluid channeling caused by weight loss due to the change of a base material, can easily pass through a micropore structure of compact sandstone, has the characteristics of high strength, high elasticity, low shrinkage, corrosion resistance and the like after being cured, overcomes the inherent defects of the conventional cement cementing material, and is an ideal cementing material for oil-gas wells.
The existing gelling system for underground sealing can affect curing due to the existence of underground water, and hydrophilic water-based epoxy resin is not used, so that the environmental protection property is poor. However, when the thickening time of the existing aqueous gelling system at a higher temperature meets the requirement, the existing aqueous gelling system has no strength for a long time, the thickening time with strength is very short, and the contradiction between the thickening time and the strength is difficult to adjust, so the aqueous modified epoxy resin is used in the invention, so that the system has certain hydrophilicity, the pipeline is easy to clean with water after the construction of the system is finished, special solvent is not needed for cleaning, and the aqueous modified epoxy resin is more environment-friendly and easy to operate. The viscosity of the system is controlled by adopting the epoxy compound viscosity regulator with small molecular weight which can participate in the curing reaction, the epoxy compound viscosity regulator can be cured without volatilization, the system can be kept at a certain viscosity and is easy to pump, the curing of the system in a well condition closed environment can be ensured, and the environmental pollution caused by solvent volatilization can be avoided. Meanwhile, in order to reconcile the contradiction between the strength and the thickening time of the conventional waterborne resin, no water is added into a waterborne modified resin system as a solvent, but a reactive viscosity regulator is adopted, and a corresponding curing agent and a thickening time regulator are matched to realize a synergistic effect, so that the contradiction that the strength and the thickening time of the conventional waterborne resin are difficult to reconcile is avoided, and the environmental protection property is improved on the basis of improving the performance of a gelling system.
In addition, according to the curing mechanism, the gelling system disclosed by the invention organically combines the thickening time of the system with the curing agent and the waterborne modified resin through the thickening time control agent, so that the thickening time of the system can be adjusted within a large temperature range, and the requirements of well conditions at different temperatures are met.
As an alternative embodiment, the gelling system of the present invention employs nanocomposite reinforcement techniques to provide high strength while maintaining good toughness in the synthetic resin system.
The aqueous modified synthetic resin cement of the present application, and the preparation method and application thereof will be described in detail with reference to specific examples.
Example 1
the preparation method of the aqueous modified synthetic resin binding material comprises the following steps of:
the method comprises the following steps:
step 1, preparing raw materials in parts by weight;
The raw materials comprise: 100 parts of waterborne modified epoxy resin, 10 parts of viscosity regulator, 70 parts of curing agent, 1 part of toughening agent and 0-6 parts of coagulation regulator;
wherein,
The waterborne modified epoxy resin is a waterborne modified epoxy resin with sulfonic groups; the water-based modified epoxy resin is obtained by grafting a water-based group sulfonic group on a methine position of the epoxy resin by a grafting reaction modification method.
The viscosity regulator comprises micromolecular epoxy compound dodecyl glycidyl ether and epoxypropane benzyl ether; wherein the weight ratio of the small molecular epoxy compound dodecyl glycidyl ether to the epoxypropane benzyl ether is 2: 3;
The curing agent comprises alicyclic polyamine and acid anhydride; wherein the weight ratio of the alicyclic polyamine to the acid anhydride is 3: 2;
The coagulation regulator comprises 2, 4, 6-tri (dimethylaminomethyl) phenol and tetraethylammonium bromide; wherein the weight ratio of the 2, 4, 6-tri (dimethylaminomethyl) phenol to the tetraethylammonium bromide is 5: 2;
the toughening agent comprises nano zinc oxide and aluminum oxide; wherein the weight ratio of the nano zinc oxide to the aluminum oxide is 1: 1.
Step 2, uniformly mixing the water-based modified epoxy resin, the viscosity regulator and the toughening agent in the raw materials to obtain a first mixture;
and 3, uniformly mixing the first mixture with the curing agent and the setting regulator in the raw materials to obtain the No. 1 waterborne modified synthetic resin gelled material (1 # system for short).
Wherein the recommended rotating speed for mixing and stirring is 2000 r/min.
the properties such as thickening time, initial consistency, compressive strength and the like of the synthetic resin gel system for oil and gas wells were evaluated according to the experimental methods specified in GB/T19139-2012 "oil well cement test methods" for the # 1 aqueous modified synthetic resin gel material prepared in example 1. And (3) testing the viscosity of the synthetic resin gelling system by adopting a six-speed rotational viscometer, wherein the testing temperature is 25 ℃, and the testing rotating speed is 100 r/min. And testing the elastic modulus of the test block of the synthetic resin gel system maintained for 7d at the corresponding temperature by using a rock triaxial testing machine. Table 1 shows the comprehensive performance evaluation table of the No. 1 aqueous modified synthetic resin cement.
TABLE 11 comprehensive performance evaluation table for # aqueous modified synthetic resin binding material
example 2
the preparation method of the aqueous modified synthetic resin binding material comprises the following steps of:
The method comprises the following steps:
Step 1, preparing raw materials in parts by weight;
The raw materials comprise: 100 parts of waterborne modified epoxy resin, 12 parts of viscosity regulator, 90 parts of curing agent, 3 parts of toughening agent and 0-6 parts of coagulation regulator;
wherein,
The waterborne modified epoxy resin is a waterborne modified epoxy resin with sulfonic groups; the water-based modified epoxy resin is obtained by grafting a water-based group sulfonic group on a methine position of the epoxy resin by a grafting reaction modification method.
the viscosity regulator comprises micromolecular epoxy compound dodecyl glycidyl ether and epoxypropane benzyl ether; wherein the weight ratio of the small molecular epoxy compound dodecyl glycidyl ether to the epoxypropane benzyl ether is 1: 1;
the curing agent comprises alicyclic polyamine and acid anhydride; wherein the weight ratio of the alicyclic polyamine to the acid anhydride is 3: 1;
The coagulation regulator comprises 2, 4, 6-tri (dimethylaminomethyl) phenol and tetraethylammonium bromide; wherein the weight ratio of the 2, 4, 6-tri (dimethylaminomethyl) phenol to the tetraethylammonium bromide is 5: 1;
The toughening agent comprises nano zinc oxide and aluminum oxide; wherein the weight ratio of the nano zinc oxide to the aluminum oxide is 2: 1.
step 2, uniformly mixing the water-based modified epoxy resin, the viscosity regulator and the toughening agent in the raw materials to obtain a first mixture;
And 3, uniformly mixing the first mixture with the curing agent and the setting regulator in the raw materials to obtain the 2# aqueous modified synthetic resin gelled material (2 # system for short).
wherein the recommended rotating speed for mixing and stirring is 2000 r/min.
The 2# aqueous modified synthetic resin gelled material prepared in example 2 was evaluated for properties such as thickening time, initial consistency, compressive strength and the like of a synthetic resin gelled system for an oil and gas well according to the experimental method specified in GB/T19139-. And (3) testing the viscosity of the synthetic resin gelling system by adopting a six-speed rotational viscometer, wherein the testing temperature is 25 ℃, and the testing rotating speed is 100 r/min. And testing the elastic modulus of the test block of the synthetic resin gel system maintained for 7d at the corresponding temperature by using a rock triaxial testing machine. Table 2 is a comprehensive performance evaluation table of No. 2 aqueous modified synthetic resin cement.
TABLE 22 comprehensive performance evaluation table for # aqueous modified synthetic resin binding material
Example 3
The preparation method of the aqueous modified synthetic resin binding material comprises the following steps of:
The method comprises the following steps:
Step 1, preparing raw materials in parts by weight;
The raw materials comprise: 100 parts of waterborne modified epoxy resin, 15 parts of viscosity regulator, 100 parts of curing agent, 5 parts of toughening agent and 0-6 parts of coagulation regulator;
wherein,
The waterborne modified epoxy resin is a waterborne modified epoxy resin with sulfonic groups; the water-based modified epoxy resin is obtained by grafting a water-based group sulfonic group on a methine position of the epoxy resin by a grafting reaction modification method.
The viscosity regulator comprises micromolecular epoxy compound dodecyl glycidyl ether and epoxypropane benzyl ether; wherein the weight ratio of the small molecular epoxy compound dodecyl glycidyl ether to the epoxypropane benzyl ether is 3: 2;
the curing agent comprises alicyclic polyamine and acid anhydride; wherein the weight ratio of the alicyclic polyamine to the acid anhydride is 4: 1;
The coagulation regulator comprises 2, 4, 6-tri (dimethylaminomethyl) phenol and tetraethylammonium bromide; wherein the weight ratio of the 2, 4, 6-tri (dimethylaminomethyl) phenol to the tetraethylammonium bromide is 6: 1;
the toughening agent comprises nano zinc oxide and aluminum oxide; wherein the weight ratio of the nano zinc oxide to the aluminum oxide is 3: 1.
Step 2, uniformly mixing the water-based modified epoxy resin, the viscosity regulator and the toughening agent in the raw materials to obtain a first mixture;
And 3, uniformly mixing the first mixture with the curing agent and the setting regulator in the raw materials to obtain a 3# aqueous modified synthetic resin gelled material (a 3# system for short).
wherein the recommended rotating speed for mixing and stirring is 2000 r/min.
The properties such as thickening time, initial consistency, compressive strength and the like of the synthetic resin gel system for oil and gas wells were evaluated according to the experimental method specified in GB/T19139-2012 "oil well cement test method" for the # 3 aqueous modified synthetic resin gel material prepared in example 3. And (3) testing the viscosity of the synthetic resin gelling system by adopting a six-speed rotational viscometer, wherein the testing temperature is 25 ℃, and the testing rotating speed is 100 r/min. And testing the elastic modulus of the test block of the synthetic resin gel system maintained for 7d at the corresponding temperature by using a rock triaxial testing machine. Table 3 is a comprehensive performance evaluation table of No. 3 aqueous modified synthetic resin cement.
TABLE 33 comprehensive performance evaluation table for water-based modified synthetic resin binding material
In addition, see FIGS. 1, 2 and 3, which are graphs of the thickening time and the addition of the thickening time control agent at 90 ℃, 60 ℃ and 30 ℃ for systems # 1, # 2 and # 3, respectively.
as can be seen from the tables 1, 2 and 3 and the figures 1, 2 and 3, the water-based modified synthetic resin cementing material disclosed by the invention is low in viscosity and consistency, good in pumpability, controllable in thickening time within the temperature range of 30-90 ℃, good in thickening time adjustability, fast in strength development and good in toughness, the compressive strength of 48h at different temperatures is greater than 40MPa, and the Young modulus of 7d is less than 4.0GPa, so that the requirement of different well conditions can be met, and the water-based modified synthetic resin cementing material is a synthetic resin cementing system for the underground oil and gas well with good comprehensive performance.
when the cement plugging agent is applied to downhole operation, the cement plugging agent can be used for downhole operation needing cement, such as well cementation, downhole plugging and the like, and has excellent performance and better environmental protection property.
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 (9)
1. the water-based modified synthetic resin cementing material is characterized by comprising the following components in parts by weight:
100 parts of waterborne modified epoxy resin
10-15 parts of viscosity regulator
70-100 parts of curing agent
0-6 parts of a coagulation regulator
1-5 parts of a toughening agent;
wherein the viscosity regulator comprises dodecyl glycidyl ether and/or propylene oxide benzyl ether; wherein the weight ratio of the dodecyl glycidyl ether to the epoxypropane benzyl ether is 2: 3-3: 2;
The waterborne modified epoxy resin is obtained by grafting a waterborne group sulfonic acid group on the position of epoxy resin methine.
2. the aqueous modified synthetic resin cement according to claim 1, comprising, in parts by weight:
100 parts of waterborne modified epoxy resin
12 portions of viscosity regulator
90 portions of curing agent
3 portions of coagulation regulator
3 parts of a toughening agent.
3. The aqueous modified synthetic resin cement according to claim 1 or 2, wherein the viscosity modifier comprises dodecyl glycidyl ether and propylene oxide benzyl ether; wherein the weight ratio of the dodecyl glycidyl ether to the propylene oxide benzyl ether is 1: 1.
4. The aqueous modified synthetic resin cement according to claim 1 or 2, wherein the curing agent comprises a cycloaliphatic polyamine and/or an acid anhydride; wherein the weight ratio of the alicyclic polyamine to the acid anhydride is 3: 2-4: 1.
5. The aqueous modified synthetic resin cement according to any of claims 1 or 2, wherein the set control agent comprises 2, 4, 6-tris (dimethylaminomethyl) phenol and/or tetraethylammonium bromide; wherein the weight ratio of the 2, 4, 6-tris (dimethylaminomethyl) phenol to the tetraethylammonium bromide is 5: 2-6: 1.
6. The aqueous modified synthetic resin cement according to any of claims 1 or 2, wherein the toughening agent comprises nano zinc oxide and nano aluminum oxide; wherein the weight ratio of the nano zinc oxide to the aluminum oxide is 1: 1-3: 1.
7. A process for the preparation of an aqueous modified synthetic resin cement, characterized in that it is used for the preparation of an aqueous modified synthetic resin cement according to any one of claims 1 to 6;
The method comprises the following steps:
preparing raw materials in parts by weight of the aqueous modified synthetic resin cement according to any one of claims 1 to 6;
uniformly mixing the water-based modified epoxy resin, the viscosity regulator and the toughening agent in the raw materials to obtain a first mixture;
And uniformly mixing the first mixture with the curing agent and the coagulation regulator in the raw materials to obtain the water-based modified synthetic resin cementing material.
8. use of an aqueous modified synthetic resin cement according to any of claims 1 to 7 for downhole operations in oil and gas wells.
9. the use of an aqueous modified synthetic resin cement according to claim 8, wherein the aqueous modified synthetic resin cement is used for downhole sealing of oil and gas wells.
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