CN107057664B - Polymer-based thixotropic cement paste - Google Patents
Polymer-based thixotropic cement paste Download PDFInfo
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- CN107057664B CN107057664B CN201710356182.XA CN201710356182A CN107057664B CN 107057664 B CN107057664 B CN 107057664B CN 201710356182 A CN201710356182 A CN 201710356182A CN 107057664 B CN107057664 B CN 107057664B
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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses polymer-based thixotropic cement slurry, and belongs to the technical field of oilfield chemistry. The thixotropic cement paste comprises the following components in percentage by weight: 100 parts of G-grade cement, 3-5 parts of a polymer thixotropic agent, 1-3 parts of a polymer surfactant, 2-5 parts of a polymer fluid loss agent, 0.3-1.5 parts of a polymer drag reducer and 34-46 parts of water. The thixotropic cement slurry gel structure is fast in formation and easy to damage, so that the construction safety is improved while the effects of leakage prevention, channeling prevention and the like are exerted, the thixotropy is less influenced by temperature, the comprehensive performance is good, and the thixotropic cement slurry gel structure can be used for well cementation of oil and gas wells with weak stratums, easy leakage and channeling and the like.
Description
Technical Field
The invention relates to the technical field of oilfield chemistry, in particular to polymer-based thixotropic cement slurry.
Background
With the increasing complexity of geological conditions and the increasingly harsh operating environment, serious challenges are brought to the well cementation technology. Well cementation leakage and well cementation channeling are technical problems commonly existing in oil and gas fields at home and abroad at present, and bring huge loss to the development of a plurality of oil and gas fields. The thixotropic cement slurry system has the characteristics that a coagulation structure is damaged under the shearing action and a gel structure is quickly recovered after the thixotropic cement slurry system is static, and is considered as an effective means for solving the difficult problems of oil-gas well cementing leakage and fluid channeling; in addition, the thixotropic cement slurry system is also suitable for weak stratum well cementation, cement squeezing remediation, broken or corroded casing repairing and the like, and has wide application prospect. Therefore, the research on the thixotropic cement paste is of great significance.
At present, the research on the thixotropic cement paste system is still in the initial stage, and a thixotropic cement paste system with excellent performance is lacked. The following problems are common to conventional thixotropic cement paste systems: (1) the thixotropy is contradictory to the construction safety. Most thixotropic cement paste has insufficient thixotropy and cannot really play the roles of leaking stoppage and channeling prevention; some systems can quickly form higher gel strength, but are not easy to damage due to stronger structural force, so that construction risks are easily caused; (2) the sensitivity of the thixotropic effect to temperature. Most thixotropic cement paste has good thixotropy at normal temperature, but the thixotropy can be obviously reduced along with the temperature rise, so that the effect of the thixotropic cement paste can not be well played after the thixotropic cement paste is replaced in place in an oil-gas well with higher temperature; (3) the comprehensive performance is not good enough. Although some thixotropic cement paste has strong thixotropy, the problems of low strength, uncontrollable water loss, complex field operation and the like exist, and the application of the thixotropic cement paste is limited.
Disclosure of Invention
The invention aims to provide polymer-based thixotropic cement paste, which has a quick gel structure and is easy to damage, so that the construction safety is improved while the effects of leakage prevention, channeling prevention and the like are exerted, the thixotropy is less influenced by temperature, and the comprehensive performance is good.
In order to achieve the purpose, the invention provides polymer-based thixotropic cement paste which comprises the following components in parts by weight: 100 parts of G-grade cement, 3-5 parts of a polymer thixotropic agent, 1-3 parts of a polymer surfactant, 2-5 parts of a polymer fluid loss agent, 0.3-1.5 parts of a polymer drag reducer and 34-46 parts of water.
Further, the polymer thixotropic agent is a hydrophobic association polymer obtained by polymerizing four monomers, namely methacrylic acid, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid higher ester, and the weight ratio of the four monomers is 5-25: 20-50: 30-70: 5-25.
Further, the higher acrylate is lauryl acrylate, myristyl acrylate, or cetyl acrylate.
Further, the polymer thixotropic agent is prepared by a soap-free emulsion polymerization method.
Further, the polymer surfactant is sodium polyacrylate, styrene-acrylic acid copolymer or maleic anhydride-styrene copolymer.
Further, the polymer fluid loss agent is a 2-acrylamide-2-methylpropanesulfonic acid copolymer.
Further, the polymer drag reducer is a polycarboxylic acid.
One or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
(1) according to the polymer-based thixotropic cement paste provided by the embodiment of the invention, as the adopted polymer thixotropic agent is a hydrophobic association type polymer, a dynamic physical cross-linked network structure can be formed in a cement paste system due to association, the structural acting force is very weak, the polymer-based thixotropic cement paste can be easily damaged under the shearing action, the viscosity of the system is reduced, and after external force is removed, the cross-linked network among macromolecules is quickly reformed, so that the obvious thixotropic property is shown;
(2) according to the polymer-based thixotropic cement paste provided by the embodiment of the invention, the polymer surfactant and the polymer thixotropic agent interact with each other, and a mixed micelle-shaped aggregate can be further formed through the hydrophobic association effect of the polymer thixotropic agent, so that the thixotropy of a system is further improved;
(3) within a certain range, the formation of a reversible association structure is facilitated along with the rise of temperature, the damage of the temperature to a thixotropic structure is avoided, and the thixotropy of the system is less influenced by the temperature;
(4) the additives used in the polymer-based thixotropic cement paste are all water-soluble polymers, the thixotropy is exerted without pre-hydration in advance, the operation is convenient, the system is easy to adjust, and the comprehensive performance is good.
Detailed Description
The embodiment of the invention provides the polymer-based thixotropic cement slurry, the gel structure of the thixotropic cement slurry is formed quickly and is easy to damage, so that the construction safety is improved while the effects of leakage prevention, channeling prevention and the like are exerted, the thixotropy is less influenced by temperature, the comprehensive performance is good, and the polymer-based thixotropic cement slurry can be used for well cementation of oil and gas wells such as weak stratums, easy leakage and channeling.
To achieve the above purpose, the general idea of the embodiment of the present invention is as follows:
the invention provides polymer-based thixotropic cement paste which comprises the following components in parts by weight: 100 parts of G-grade cement, 3-5 parts of a polymer thixotropic agent, 1-3 parts of a polymer surfactant, 2-5 parts of a polymer fluid loss agent, 0.3-1.5 parts of a polymer drag reducer and 34-46 parts of water.
Due to the hydrophobic association effect of the polymer thixotropic agent, a dynamic physical cross-linked network structure can be formed in a cement paste system, and the thixotropy of the system is further improved by the interaction of the polymer surfactant and the polymer thixotropic agent, so that the gel structure of the thixotropic cement paste is formed quickly and is easy to damage; the temperature rise is beneficial to the formation of an association structure, so that the cement paste still keeps good thixotropy at higher temperature, and the thixotropy is less influenced by the temperature; under the interaction of the components, the cement paste shows good comprehensive performance.
In order to better understand the technical solutions, the technical solutions of the present invention are described in detail with specific embodiments, and it should be understood that the specific features in the embodiments and examples of the present invention are detailed descriptions of the technical solutions of the present invention, but not limitations of the technical solutions of the present invention, and the technical features in the embodiments and examples of the present invention may be combined with each other without conflict.
The embodiment of the invention provides polymer-based thixotropic cement paste which comprises the following components in parts by weight: 100 parts of G-grade cement, 3-5 parts of a polymer thixotropic agent, 1-3 parts of a polymer surfactant, 2-5 parts of a polymer fluid loss agent, 0.3-1.5 parts of a polymer drag reducer and 34-46 parts of water.
The polymer thixotropic agent in the embodiment of the invention is a hydrophobic association polymer obtained by polymerizing four monomers, namely methacrylic acid, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid higher ester, and the weight ratio of the four monomers is 5-25: 20-50: 30-70: 5-25. Wherein, the higher acrylate can be lauryl acrylate, myristyl acrylate or cetyl acrylate.
The polymer thixotropic agent simultaneously contains hydrophilic monomers and hydrophobic monomers, the four monomers are polymerized according to the proportion, the hydrophilic units and the hydrophobic units in the obtained polymer thixotropic agent have proper proportion to form hydrophobic association polymers, a dynamic physical crosslinking network structure can be formed in a cement paste system through hydrophobic association, and the structure is easy to damage; and the monomer ratio is in the range of the ratio, the solubility of the polymer thixotropic agent is increased along with the increase of the temperature, more association structures are favorably formed, the sensitivity of the thixotropic agent to the temperature can be reduced, and the thixotropic agent still has good thixotropy at higher temperature.
In the embodiment of the invention, the polymer thixotropic agent is synthesized by a soap-free emulsion polymerization method.
In a specific embodiment, the polymeric thixotropic agent may be prepared by:
adding a proper amount of distilled water into a reaction vessel, weighing 2-acrylamide-2-methylpropanesulfonic acid and methacrylic acid monomers according to the proportion, adding the monomers into the reaction vessel, and stirring to dissolve the monomers to form a solution;
adjusting the pH of said solution to about 7.0;
adding acrylamide and acrylic acid high-grade ester into the solution, stirring and mixing uniformly, and simultaneously introducing inert gas to remove oxygen to form mixed solution;
and heating the mixed solution, adding an initiator into the mixed solution when the temperature reaches 50 ℃ to initiate polymerization, and reacting at the constant temperature of 50 ℃ for 5 hours to obtain a reaction product, wherein the reaction product is the polymer thixotropic agent.
Specifically, the inert gas is selected from nitrogen or argon. The initiator is a redox initiation system.
The polymer surfactant in the embodiment of the invention is sodium polyacrylate, styrene-acrylic acid copolymer or maleic anhydride-styrene copolymer. The compound has a synergistic interaction effect on the polymer thixotropic agent, is beneficial to the formation of a hydrophobic association structure, and can interact with the polymer thixotropic agent to further improve the thixotropy of a system.
The polymer fluid loss agent in the embodiment of the invention is a 2-acrylamide-2-methylpropanesulfonic acid copolymer, and the preferred type is BXF-200L (AF) or BCG-200L.
The polymer drag reducer in the embodiment of the invention is polycarboxylic acid, has the drag reduction effect, improves the rheological property of cement paste, and is preferably BCD-210L.
In order to enable those skilled in the art to further understand the scheme of the embodiment of the present invention, the following detailed description will be given based on the scheme described in the embodiment of the present invention.
Example 1
Firstly weighing 100 parts of G-grade cement, placing the G-grade cement into an ash discharging container, weighing 34 parts of water in a slurry cup for preparing cement slurry, and then respectively weighing 3 parts of polymer thixotropic agent, 3 parts of polymer surfactant (styrene-acrylic acid copolymer), 4 parts of polymer water loss reducer (BCG-200L) and 0.5 part of polymer drag reducer (BCD-210L) and pouring into the slurry cup with the water. After the weighed substances in the slurry cup are uniformly mixed by a corrugated mixer, the polymer-based thixotropic cement slurry is prepared according to a cement slurry preparation method specified in GB19139-2012 oil well cement test method and is marked as a No. 1 sample.
The polymer thixotropic agent in the embodiment is a copolymer of four monomers, namely methacrylic acid, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and lauryl acrylate, and the mass ratio of the copolymer to the lauryl acrylate is 5:40:30: 25.
Example 2
Firstly weighing 100 parts of G-grade cement, placing the G-grade cement in an ash discharging container, weighing 37 parts of water in a slurry cup for preparing cement slurry, then respectively weighing 3.5 parts of polymer thixotropic agent, 2 parts of polymer surfactant (styrene-acrylic acid copolymer), 5 parts of polymer fluid loss additive (BXF-200L) and 1 part of polymer drag reducer (BCD-210L), and pouring the mixture into the slurry cup with the water. After the weighed substances in the slurry cup are uniformly mixed by a corrugated mixer, the polymer-based thixotropic cement slurry is prepared according to a cement slurry preparation method specified in GB19139-2012 oil well cement test method and is marked as a No. 2 sample.
In the embodiment, the polymer thixotropic agent is a copolymer of four monomers, namely methacrylic acid, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and tetradecyl acrylate, and the mass ratio of the copolymer to the tetradecyl acrylate is 10:30:45: 15.
Example 3
Firstly weighing 100 parts of G-grade cement, placing the G-grade cement in an ash discharging container, weighing 40 parts of water in a slurry cup for preparing cement slurry, then respectively weighing 5 parts of polymer thixotropic agent, 2 parts of polymer surfactant (maleic anhydride-styrene copolymer), 3 parts of polymer fluid loss additive (BXF-200L) and 1.5 parts of polymer drag reducer (BCD-210L), and pouring the mixture into the slurry cup with the water. After the weighed substances in the slurry cup are uniformly mixed by a corrugated mixer, the polymer-based thixotropic cement slurry is prepared according to a cement slurry preparation method specified in GB19139-2012 oil well cement test method and is marked as a No. 3 sample.
In the embodiment, the polymer thixotropic agent is a copolymer of four monomers, namely methacrylic acid, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and hexadecyl acrylate, and the mass ratio of the polymer thixotropic agent to the hexadecyl acrylate is 15:20:55: 10.
Example 4
Firstly weighing 100 parts of G-grade cement, placing the G-grade cement in an ash discharging container, weighing 46 parts of water in a slurry cup for preparing cement slurry, and then respectively weighing 3 parts of polymer thixotropic agent, 1 part of polymer surfactant (sodium polyacrylate), 4 parts of polymer fluid loss additive (BXF-200L) and 0.3 part of polymer drag reducer (BCD-210L) and pouring the mixture into the slurry cup with the water. After the weighed substances in the slurry cup are uniformly mixed by a corrugated mixer, the polymer-based thixotropic cement slurry is prepared according to a cement slurry preparation method specified in GB19139-2012 oil well cement test method and is marked as a No. 4 sample.
In the embodiment, the polymer thixotropic agent is a copolymer of four monomers, namely methacrylic acid, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and hexadecyl acrylate, and the mass ratio of the polymer thixotropic agent to the hexadecyl acrylate is 5:20:70: 5.
Example 5
Firstly weighing 100 parts of G-grade cement, placing the G-grade cement in an ash discharging container, weighing 40 parts of water in a slurry cup for preparing cement slurry, then respectively weighing 4 parts of polymer thixotropic agent, 1 part of polymer surfactant (sodium polyacrylate), 3.5 parts of polymer fluid loss additive (BXF-200L) and 0.5 part of polymer drag reducer (BCD-210L), and pouring the mixture into the slurry cup with the water. After the weighed substances in the slurry cup are uniformly mixed by a corrugated mixer, the polymer-based thixotropic cement slurry is prepared according to a cement slurry preparation method specified in GB19139-2012 oil well cement test method and is marked as a No. 5 sample.
In the embodiment, the polymer thixotropic agent is a copolymer of four monomers, namely methacrylic acid, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and hexadecyl acrylate, and the mass ratio of the polymer thixotropic agent to the hexadecyl acrylate is 5:25:60: 10.
The properties of the prepared polymer-based thixotropic cement paste sample are evaluated:
according to the cement paste gel strength test method specified in GB/T19139-2012 oil well cement test method, the gel strength of the polymer-based thixotropic cement paste sample after standing for 10s, 5min and 10min at different temperatures is evaluated. Based on the method for testing the gel strength, the reversibility of the thixotropic structure of the polymer-based thixotropic cement paste sample is evaluated by adopting a six-speed rotational viscometer. The comprehensive properties of the polymer-based thixotropic cement paste samples were evaluated according to the test method specified in GB/T19139-2012 "oil well cement test methods".
(1) The six-speed rotational viscometer is used for testing the gel strength of thixotropic cement paste samples which are kept still for 10s, 5min and 10min at different temperatures, the testing temperatures are respectively 30 ℃, 60 ℃ and 90 ℃, and the testing results are shown in table 1. In addition, the reversibility of the thixotropic structure of the thixotropic cement paste sample was evaluated by a six-speed rotational viscometer. In the experiment, the reading of the just prepared thixotropic cement paste at 300r/min is firstly tested, then the thixotropic cement paste is stood for 10min to test the gel strength of the thixotropic cement paste, then the thixotropic cement paste is stirred for 1min at the rotating speed of 300r/min to destroy the gel structure of the thixotropic cement paste, the reading of stirring for 30s is recorded, and then the thixotropic cement paste is stood for 10min again to test the gel strength of the thixotropic cement paste. The test temperatures were 30 ℃ and 90 ℃ respectively, and the test results are shown in Table 2.
TABLE 1 results of gel strength test of polymer-based thixotropic cement slurries at different temperatures
TABLE 2 results of gel strength test of polymer-based thixotropic cement slurries at different temperatures
As can be seen from Table 1, the prepared polymer-based thixotropic cement slurry sample rapidly increases in gel strength after standing, reaches a high value after 5min, and hardly influences the gel strength along with the temperature rise, so that the cement slurry plays roles of leakage prevention and channeling prevention after being injected into the bottom of a well. As can be seen from Table 2, the thixotropic structure of the prepared polymer-based thixotropic cement paste has good reversibility, and the gel structure formed after standing is thickened and can be quickly thinned and restored to the original paste state after being stirred, so that the construction risk is reduced, the original gel structure can be restored after standing, and the thixotropic property is shown.
(2) The comprehensive performance of the polymer-based thixotropic cement slurry system was tested at 60 ℃ and 90 ℃ with the test results shown in Table 3.
TABLE 3 comprehensive Properties of Polymer-based thixotropic Cement slurries
As can be seen from Table 3, the polymer-based thixotropic cement slurry system has normal thickening, short transition time, good slurry fluidity, low water loss, high strength of formed set cement, good comprehensive performance and can meet the requirements of site construction.
The experiments prove that the polymer-based thixotropic cement paste system disclosed by the embodiment of the invention has the advantages of strong thixotropy, quick gel strength formation, easiness in damage, small influence on thixotropy by temperature, low water loss, high compressive strength and good comprehensive performance.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (6)
1. The polymer-based thixotropic cement paste is characterized by comprising the following components in parts by weight: 100 parts of G-grade cement, 3-5 parts of a polymer thixotropic agent, 1-3 parts of a polymer surfactant, 2-5 parts of a polymer fluid loss agent, 0.3-1.5 parts of a polymer drag reducer and 34-46 parts of water;
the polymer thixotropic agent is a hydrophobic association polymer obtained by polymerizing four monomers, namely methacrylic acid, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid higher ester, and the weight ratio of the four monomers is 5-25: 20-50: 30-70: 5-25.
2. The polymer-based thixotropic cement slurry of claim 1, wherein the higher acrylate is lauryl acrylate, myristyl acrylate, or cetyl acrylate.
3. The polymer-based thixotropic cement slurry of claim 1, wherein the polymeric thixotropic agent is prepared by a soap-free emulsion polymerization process.
4. The polymer-based thixotropic cement slurry of claim 1, wherein the polymeric surfactant is sodium polyacrylate, a styrene-acrylic acid copolymer, or a maleic anhydride-styrene copolymer.
5. The polymer-based thixotropic cement slurry of claim 1, wherein the polymer fluid loss additive is a 2-acrylamido-2-methylpropane sulfonic acid copolymer.
6. The polymer-based thixotropic cement slurry of claim 1, wherein the polymer drag reducing agent is a polycarboxylic acid.
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| CN112457829A (en) * | 2020-12-08 | 2021-03-09 | 中国石油天然气集团有限公司 | Retarded thermosetting resin gelling composition and preparation method thereof |
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| CN102212352A (en) * | 2010-04-12 | 2011-10-12 | 长江大学 | Anti-gas channeling impermeable latex cementing slurry |
| CN103739255A (en) * | 2014-01-09 | 2014-04-23 | 江苏苏博特新材料股份有限公司 | High-thixotropy cement-based grouting material |
| CN105018055A (en) * | 2015-07-29 | 2015-11-04 | 天津中油渤星工程科技有限公司 | Oil well cement thixotropic agent and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212352A (en) * | 2010-04-12 | 2011-10-12 | 长江大学 | Anti-gas channeling impermeable latex cementing slurry |
| CN103739255A (en) * | 2014-01-09 | 2014-04-23 | 江苏苏博特新材料股份有限公司 | High-thixotropy cement-based grouting material |
| CN105018055A (en) * | 2015-07-29 | 2015-11-04 | 天津中油渤星工程科技有限公司 | Oil well cement thixotropic agent and preparation method thereof |
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