CN114368932A - Oil well cement modifier - Google Patents
Oil well cement modifier Download PDFInfo
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- CN114368932A CN114368932A CN202210107423.8A CN202210107423A CN114368932A CN 114368932 A CN114368932 A CN 114368932A CN 202210107423 A CN202210107423 A CN 202210107423A CN 114368932 A CN114368932 A CN 114368932A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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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
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
- C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
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- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to an oil well cement modifier, which is an inorganic-organic composite particle with a core-shell structure, and the preparation method comprises the following steps: a) SiO 22Modification of nanoparticles: b) preparing inorganic-organic composite particles: 1-10 g of SiO2-BSA is ultrasonically dispersed in 100 ml of absolute ethanol for 30 minutes, 5-30 g of polyethylene glycol methyl methacrylate, 1-10 g of acrylic acid and 0.01-0.05 g of azobisisobutyronitrile are added to the dispersion, mixed in nitrogen at 40-70 ℃ for 4 hours, rinsed with ethanol several times after centrifugation, and vacuum-dried at 60 ℃ for 12 hours to obtain inorganic-organic composite particles, which are inorganic-organic composite particles having a core-shell structure; the mass ratio of the polyethylene glycol methyl methacrylate to the acrylic acid is 3:1-5: 1. The invention can not only improve the fluidity of oil well cement paste, but also improve the mechanical properties of oil well cement.
Description
The technical field is as follows:
the invention relates to oil well cement used for well cementation in the process of oil and gas well development, in particular to an oil well cement modifier.
Secondly, background art:
in the process of oil-gas well development, oil well cement used for well cementation has inherent defects of low tensile strength, poor crack resistance and the like, and double images of underground cement sheath damage are severeThe productivity, production life and safety of oil and gas wells are affected. SiO 22The nano particles not only can play a role in physical filling in cement paste, but also can react with calcium hydroxide generated in a hydration process to generate hydrated calcium silicate gel, so that the hydration reaction of the cement paste is promoted, the microstructure of set cement is compacted, and the performance of the cement paste is improved. However, SiO2The nano particles have larger specific surface area and strong agglomeration tendency, and the agglomerated nano SiO2The particles are easy to form weak zones in the cement paste, so that the mechanical property of the cured cement is reduced. The SiO content can be improved by adding the high-efficiency water reducing agent into the well cementation cement slurry2Dispersion stability of nanoparticles in cement slurry. However, SiO2The interaction between the nano particles and the high-efficiency water reducing agent is weak, and SiO can not be changed fundamentally2The strong agglomeration tendency of the nano particles can not realize SiO2Nano-scale uniform dispersion of nano-particles in cement slurry. Thus, SiO2The use of nanoparticles in well cementing slurries has been limited.
Thirdly, the invention content:
the invention aims to provide an oil well cement modifier which is used for solving the problem of SiO in the prior art2The application of the nano-particles in well cementing cement slurry is limited.
The technical scheme adopted by the invention for solving the technical problems is as follows: the oil well cement modifier is an inorganic-organic composite particle with a core-shell structure, and the preparation method comprises the following steps:
a）SiO2modification of nanoparticles:
1-10 g of SiO2Adding the nano particles into 100 ml of ethanol solution with the mass percentage concentration of 10%, and carrying out ultrasonic treatment for 15 minutes to obtain uniform suspension; adding 2-8 g of N, O-bis (trimethylsilyl) acetamide BSA into the suspension, stirring for 6 hours at 50 ℃ in a nitrogen atmosphere, cooling to normal temperature, centrifuging the dispersion for multiple times, washing with ethanol, and removing unreacted BSA to obtain modified SiO2Nanoparticle SiO2-BSA; then, the modified SiO2Nanoparticle SiO2-BSA dried at 60 ℃ under vacuum for 12 hours;
b) preparing inorganic-organic composite particles:
1-10 g of SiO2-BSA was ultrasonically dispersed in 100 ml of absolute ethanol for 30 minutes, 5-30 g of polyethylene glycol methyl methacrylate PEGMA, 1-10 g of acrylic acid AA and 0.01-0.05 g of azobisisobutyronitrile were added to the dispersion, mixed at 40-70 ℃ under nitrogen for 4 hours, centrifuged, rinsed with ethanol several times, and vacuum-dried at 60 ℃ for 12 hours to obtain inorganic-organic composite particles SiO2PEGMA/AA, which is inorganic-organic composite particles with a core-shell structure; the mass ratio of the polyethylene glycol methyl methacrylate PEGMA to the acrylic acid AA is 3:1-5: 1.
The inorganic-organic composite particles were prepared in the above scheme:
2 g of SiO2-BSA was ultrasonically dispersed in 100 ml of absolute ethanol for 30 minutes, 10 g of polyethylene glycol methyl methacrylate PEGMA, 2 g of acrylic acid AA and 0.025 g of azobisisobutyronitrile were added to the dispersion, mixed at 60 ℃ under nitrogen for 4 hours, centrifuged, rinsed with ethanol several times, and vacuum-dried at 60 ℃ for 12 hours to obtain inorganic-organic composite particles SiO2PerGMA/AA, which is inorganic-organic composite particles with a core-shell structure.
When the inorganic-organic composite particles are prepared in the scheme, the concentration and the proportion of polyethylene glycol methyl methacrylate PEGMA and acrylic acid AA are adjusted, so that the influence of the inorganic-organic composite particles on the fluidity of oil well cement paste is controlled according to the well cementation construction requirements.
Has the advantages that:
1. the invention is firstly on SiO2Grafting polyethylene glycol methyl methacrylate (PEGMA) and Acrylic Acid (AA) on the surface of the nano-particles to prepare inorganic-organic composite particles (SiO) with a core-shell structure2PEGMA/AA), the modification method is simple and convenient, the cost is low, and the repeatability is good.
2. SiO prepared by the invention2the/PEGMA/AA composite particles combine a high-efficiency water reducing agent (PEGMA/AA) and SiO2The advantages of the particles can not only improve the fluidity of oil well cement paste, but also improve the mechanical properties of the oil well cement, and can greatly improve the fluidity of the oil well cement pasteAnd the application of the composite particles in well cementation engineering is promoted.
3. The invention grafts the active components (PEGMA and AA) of the water reducing agent to SiO2Surface of nanoparticles incorporating SiO2The nano particles and the water reducing agent have double properties and are more efficient than the physical blending property of the nano particles and the water reducing agent.
4. The invention grafts polyethylene glycol methyl methacrylate (PEGMA) and Acrylic Acid (AA) to SiO2The core-shell structure on the surface of the nano-particles endows the inorganic-organic composite particles with multiple functions, and can improve the hydration and densification microstructure of cement through the pozzolanic activity and the nucleation effect.
Fourthly, explanation of the attached drawings:
FIG. 1 is a flow chart of the preparation of inorganic-organic composite particles;
FIG. 2 is an infrared spectrum of an inorganic-organic composite particle;
FIG. 3 is a scanning electron microscope photograph of set cement for four oil well cement systems;
FIG. 4 is a graph of compressive strength of four well cement systems at different curing times;
FIG. 5 is a graph of shear stress as a function of shear rate for four oil well cement systems.
The fifth embodiment is as follows:
example 1:
the oil well cement modifier is an inorganic-organic composite particle with a core-shell structure, and the preparation method comprises the following steps:
a）SiO2modification of nanoparticles
2 g of SiO2Adding the nano particles into an ethanol solution with the mass percentage concentration of 10%, and carrying out ultrasonic treatment for 15 minutes to obtain a uniform suspension. To the above dispersion was added 3 g of N, O-bistrimethylsilyl acetamide (BSA), and the mixture was stirred at 50 ℃ under nitrogen for 6 hours. After cooling to room temperature, the dispersion was centrifuged several times and washed with ethanol to remove unreacted BSA. Subsequently, the modified SiO2Nanoparticles (SiO)2-BSA) at 60 ℃ for 12 hours under vacuum.
b) Preparing inorganic-organic composite particles:
2 g of SiO2-ultrasonic dispersing BSA in absolute ethanol for 30 min. Adding 10 g of polyethylene glycol methyl methacrylate (PEGMA), 2 g of Acrylic Acid (AA) and 0.025 g of azobisisobutyronitrile into the dispersion, mixing for 4 hours at 60 ℃ in nitrogen, centrifuging, rinsing with ethanol for multiple times, and vacuum-drying at 60 ℃ for 12 hours to obtain inorganic-organic composite particles (SiO) with a core-shell structure2PerGMA/AA). The preparation flow chart and the infrared spectrum of the inorganic-organic composite particle are respectively shown in fig. 1 and fig. 2.
Example 2:
the oil well cement modifier is an inorganic-organic composite particle with a core-shell structure, and the preparation method comprises the following steps:
a）SiO2modification of nanoparticles
5 g of SiO2Adding the nano particles into an ethanol solution with the mass percentage concentration of 10%, and carrying out ultrasonic treatment for 15 minutes to obtain a uniform suspension. 6.5 g of N, O-bistrimethylsilyl acetamide (BSA) was added to the above dispersion, and the mixture was stirred at 50 ℃ under a nitrogen atmosphere for 6 hours. After cooling to room temperature, the dispersion was centrifuged several times and washed with ethanol to remove unreacted BSA. Subsequently, the modified SiO2Nanoparticles (SiO)2-BSA) at 60 ℃ for 12 hours under vacuum.
b) Preparing inorganic-organic composite particles:
4 g of SiO2-ultrasonic dispersing BSA in absolute ethanol for 30 min. 20 g of polyethylene glycol methyl methacrylate (PEGMA), 5 g of Acrylic Acid (AA) and 0.03 g of azobisisobutyronitrile were added to the dispersion, mixed at 40 ℃ for 4 hours in nitrogen, centrifuged, rinsed with ethanol several times, and vacuum-dried at 60 ℃ for 12 hours to obtain inorganic-organic composite particles (SiO) having a core-shell structure2PerGMA/AA). The preparation flow chart and the infrared spectrum of the inorganic-organic composite particle are respectively shown in fig. 1 and fig. 2.
Example 3:
the oil well cement modifier is an inorganic-organic composite particle with a core-shell structure, and the preparation method comprises the following steps:
a）SiO2modification of nanoparticles
Mixing 10 g of SiO2Adding the nano particles into an ethanol solution with the mass percentage concentration of 10%, and carrying out ultrasonic treatment for 15 minutes to obtain a uniform suspension. To the above dispersion was added 8 g of N, O-bistrimethylsilyl acetamide (BSA), and the mixture was stirred at 50 ℃ under nitrogen for 6 hours. After cooling to room temperature, the dispersion was centrifuged several times and washed with ethanol to remove unreacted BSA. Subsequently, the modified SiO2Nanoparticles (SiO)2-BSA) at 60 ℃ for 12 hours under vacuum.
b) Preparing inorganic-organic composite particles:
mixing 8 g of SiO2-ultrasonic dispersing BSA in absolute ethanol for 30 min. 30 g of polyethylene glycol methyl methacrylate (PEGMA), 10 g of Acrylic Acid (AA) and 0.04 g of azobisisobutyronitrile were added to the dispersion, mixed for 4 hours at 70 ℃ under nitrogen, centrifuged, rinsed with ethanol several times, and vacuum-dried at 60 ℃ for 12 hours to obtain inorganic-organic composite particles (SiO) having a core-shell structure2PerGMA/AA). The preparation flow chart and the infrared spectrum of the inorganic-organic composite particle are respectively shown in fig. 1 and fig. 2.
Comparative example 1:
and (4) comparing and inspecting microstructures of the oil well cement systems after solidification. (a) Group (b) is blank oil well cement system, and SiO is added2Oil well cement system of nano particles, group (c) is added with SiO2Oil well cement system of nano particles and high efficiency water reducing agent (PEGMA/AA), and (d) group is added with inorganic-organic composite particles (SiO)2PEGMA/AA). The scanning electron micrograph of the set of cement obtained for the 4 oil-well cement systems is shown in FIG. 3.
Comparative example 2:
and (4) comparing and inspecting the mechanical properties of the oil well cement systems at different curing times. Blank stands for Blank oil well cement system, SiO2Represents the addition of SiO2Oil well cement system of nanoparticles, SiO2+ P stands for SiO addition2Oil well cement system of nanoparticles and superplasticizer (PEGMA/AA), SiO2PerGMA/AA stands for the addition of inorganic-organic composite particles (SiO)2PEGMA/AA). The compressive strengths of the 4 resulting oil well cement systems at different curing times are shown in FIG. 4.
Comparative example 3:
the fluidity of 4 oil well cement systems was comparatively examined. Blank stands for Blank oil well cement system, SiO2Represents the addition of SiO2Oil well cement system of nanoparticles, SiO2+ P stands for SiO addition2Oil well cement system of nanoparticles and superplasticizer (PEGMA/AA), SiO2PerGMA/AA stands for the addition of inorganic-organic composite particles (SiO)2PEGMA/AA). The shear stress of the 4 oil well cement systems obtained is shown in the graph of FIG. 5 according to the change of the shear rate.
The invention and the addition of SiO2Compared with a cementing slurry system physically mixed by nano particles and a high-efficiency water reducing agent (PEGMA/AA), the SiO solid cement slurry system of the invention2The PEGMA/AA can effectively improve the mechanical property and the fluidity of cement paste. The inorganic-organic composite particles prepared by the method not only can improve the cement hydration and compact cement microstructure through the volcanic ash activity and the nucleation effect, but also can efficiently improve the fluidity of cement paste, and can greatly promote the application of the nanoparticles in well cementation engineering; in view of the SiO raw material2The method has the characteristics of low price, mature modification method, easy operation, high repeatability and the like, and can realize industrial application.
Claims (3)
1. An oil well cement modifier is characterized in that: the oil well cement modifier is an inorganic-organic composite particle with a core-shell structure, and the preparation method comprises the following steps:
a）SiO2modification of nanoparticles:
1-10 g of SiO2Adding the nano particles into 100 ml of ethanol solution with the mass percentage concentration of 10%, and carrying out ultrasonic treatment for 15 minutes to obtain uniform suspension; adding 2-8 g of N, O-bis (trimethylsilyl) acetamide BSA into the suspension, stirring for 6 hours at 50 ℃ in a nitrogen atmosphere, cooling to normal temperature, centrifuging the dispersion for multiple times, washing with ethanol, and removing the unreacted partBSA to obtain modified SiO2Nanoparticle SiO2-BSA; then, the modified SiO2Nanoparticle SiO2-BSA dried at 60 ℃ under vacuum for 12 hours;
b) preparing inorganic-organic composite particles:
1-10 g of SiO2-BSA was ultrasonically dispersed in 100 ml of absolute ethanol for 30 minutes, 5-30 g of polyethylene glycol methyl methacrylate PEGMA, 1-10 g of acrylic acid AA and 0.01-0.05 g of azobisisobutyronitrile were added to the dispersion, mixed at 40-70 ℃ under nitrogen for 4 hours, centrifuged, rinsed with ethanol several times, and vacuum-dried at 60 ℃ for 12 hours to obtain inorganic-organic composite particles SiO2PEGMA/AA, which is inorganic-organic composite particles with a core-shell structure; the mass ratio of the polyethylene glycol methyl methacrylate PEGMA to the acrylic acid AA is 3:1-5: 1.
2. An oil well cement modifier according to claim 1, characterized in that: when the inorganic-organic composite particles are prepared, the concentration and the proportion of polyethylene glycol methyl methacrylate PEGMA and acrylic acid AA are adjusted, and the influence of the inorganic-organic composite particles on the fluidity of oil well cement paste is controlled according to the well cementation construction requirements.
3. An oil well cement modifier according to claim 1, characterized in that: when the inorganic-organic composite particles are prepared: 2 g of SiO2-BSA was ultrasonically dispersed in 100 ml of absolute ethanol for 30 minutes, 10 g of polyethylene glycol methyl methacrylate PEGMA, 2 g of acrylic acid AA and 0.025 g of azobisisobutyronitrile were added to the dispersion, mixed at 60 ℃ under nitrogen for 4 hours, centrifuged, rinsed with ethanol several times, and vacuum-dried at 60 ℃ for 12 hours to obtain inorganic-organic composite particles SiO2/PEGMA/AA。
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210107423.8A CN114368932A (en) | 2022-01-28 | 2022-01-28 | Oil well cement modifier |
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| CN202210107423.8A CN114368932A (en) | 2022-01-28 | 2022-01-28 | Oil well cement modifier |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101124177A (en) * | 2004-12-02 | 2008-02-13 | 日本西卡株式会社 | Powdery polycarboxylic-acid cement dispersant and dispersant composition containing the dispersant |
| CN108947290A (en) * | 2018-07-20 | 2018-12-07 | 东南大学 | Improve the method for cement-based material pore structure using high-dispersibility nanometer silicon dioxide |
-
2022
- 2022-01-28 CN CN202210107423.8A patent/CN114368932A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101124177A (en) * | 2004-12-02 | 2008-02-13 | 日本西卡株式会社 | Powdery polycarboxylic-acid cement dispersant and dispersant composition containing the dispersant |
| CN108947290A (en) * | 2018-07-20 | 2018-12-07 | 东南大学 | Improve the method for cement-based material pore structure using high-dispersibility nanometer silicon dioxide |
Non-Patent Citations (3)
| Title |
|---|
| 任春蓉等: "纳米二氧化硅改性聚羧酸减水剂及其对水泥净浆流变性能的影响", 《西南科技大学学报》 * |
| 王国富等: "《预拌混凝土绿色制造技术》", 30 November 2017, 中国城市出版社 * |
| 黄培强等: "《有机合成》", 28 February 2005, 高等教育出版社 * |
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Application publication date: 20220419 |