CN107057664A - A kind of polymer matrix thixotroping cement mortar - Google Patents
A kind of polymer matrix thixotroping cement mortar Download PDFInfo
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- CN107057664A CN107057664A CN201710356182.XA CN201710356182A CN107057664A CN 107057664 A CN107057664 A CN 107057664A CN 201710356182 A CN201710356182 A CN 201710356182A CN 107057664 A CN107057664 A CN 107057664A
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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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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses a kind of polymer matrix thixotroping cement mortar, belong to technical field of oilfield chemistry.According to weight ratio, the thixotroping cement mortar composition is as follows：100 parts of G class g cements, 3~5 parts of polymeric thixotropic agents, 1~3 part of polymeric surfactant, 2~5 parts of polymer fluid loss agent, 0.3~1.5 part of polymer drag reducer, 34~46 parts of water.The thixotroping cementitious grout structure is formed fast and is more easily damaged, so as to improve the security of construction while the effect such as its leakproof anti-channeling is played, and its thixotropy is affected by temperature smaller, combination property is good, the well cementation available for weak formation, the easy Oil/gas Well such as leakage, easy channelling.
Description
Technical field
The present invention relates to technical field of oilfield chemistry, more particularly to a kind of polymer matrix thixotroping cement mortar.
Background technology
With increasingly sophisticated, the increasingly harshness of operating environment of geological conditions, severe challenge is brought to cementing technology.Well cementation
Leakage and well cementation channelling are the technical barriers of domestic and international oil gas field generally existing at present, are brought to multiple oil-gas field developments huge
Big loss.There is thixotropic cement slurry system jelling structure under shear action to be destroyed and the static fast quick-recovery of rear jelling structure
Characteristic, it is considered to be solve oil gas well cementing operation leakage and fluid communication problem effective means；Other thixotropic cement slurry
System applies also for weak formation well cementation, in terms of remedying squeeze method and repairing rupture or the sleeve pipe that is corroded, with wide
Application prospect.Therefore, research thixotropic cement slurry has great importance.
The research of current thixotroping mortar architecture lacks the thixotroping mortar architecture of function admirable also in the starting stage.
The conventional following problem of thixotroping mortar architecture generally existing：(1) thixotropy and the contradiction of construction safety.Most thixotroping cement mortars are touched
Denaturation is not strong enough, it is impossible to really play a part of leak stopping, anti-channeling；Though some systems can quickly form higher gel strength, because
Structural capacity is relatively strong survivable and easily causes construction risk；(2) sensitiveness of the thixotropic effect to temperature.Most thixotroping cement mortars
Thixotropy is fine under normal temperature, but as temperature rise thixotropy can be decreased obviously, so on the higher Oil/gas Well cementing top of temperature
For its effect cannot be played after in place well；(3) combination property is not good enough.Though some thixotroping cement mortars are with very strong thixotroping
Property, but the problems such as be commonly present low intensity, uncontrollable dehydration and complicated execute-in-place, limit its application.
The content of the invention
It is an object of the invention to provide a kind of polymer matrix thixotroping cement mortar, the thixotroping cementitious grout structure formed it is fast and
It is more easily damaged, so that the security of construction is improved while the effect such as its leakproof anti-channeling is played, and its thixotropy is by temperature
Influence is smaller, and combination property is good.
To achieve the above object, the invention provides a kind of polymer matrix thixotroping cement mortar, by weight, the thixotroping
Cement mortar composition is as follows：100 parts of G class g cements, 3~5 parts of polymeric thixotropic agents, 1~3 part of polymeric surfactant, polymer
2~5 parts of fluid loss agent, 0.3~1.5 part of polymer drag reducer, 34~46 parts of water.
Further, the polymeric thixotropic agents are methacrylic acid, acrylamide, 2- acrylamido -2- methyl-props
The hydrophobic associated polymer that the four kinds of monomer polymerizations of sulfonic acid and higher hydrocarbyl acrylate are obtained, the weight ratio of four kinds of monomers is 5~25:
20~50:30~70:5~25.
Further, the higher hydrocarbyl acrylate is dodecyl acrylate, tetradecyl acrylate or Process Conditions of Cetane Acrylate.
Further, the polymeric thixotropic agents are prepared using emulsifier-free emulsion polymerization method.
Further, the polymeric surfactant is Sodium Polyacrylate, Styrene-acrylic copolymer or maleic acid
Acid anhydride-styrol copolymer.
Further, the polymer fluid loss agent is 2- acrylamide-2-methylpro panesulfonic acid analog copolymers.
Further, the polymer drag reducer is polycarboxylic acid.
One or more of embodiment of the present invention technical scheme, has at least the following technical effects or advantages：
(1) polymer matrix thixotroping cement mortar provided in an embodiment of the present invention, by the polymeric thixotropic agents used are thin
Water association type polymer, due to association, can form " dynamic physical cross-linked network structure ", this structure in mortar architecture
Active force is very weak, is easily broken under shear action, and system viscosity declines, after external force is removed, the cross-linked network between macromolecular
Network is re-formed quickly, so as to show obvious thixotropic behavior；
(2) polymer matrix thixotroping cement mortar provided in an embodiment of the present invention, polymeric surfactant and polymer thixotroping
Agent interacts, and can further form epoxy glue pencil aggregation by the heat resistance and salt tolerance of polymeric thixotropic agents, further
The thixotropy of lifting system；
(3) within the specific limits, with the rise of temperature, the formation of reversible associative structure is conducive to, it is to avoid temperature is to touching
The destruction of structure changes, the thixotropy of system is affected by temperature smaller；
(4) additive used in polymer matrix thixotroping cement mortar is water miscible polymer, and thixotropic performance need not be carried
Preceding prehydration, it is easy to operate, and system can easily be accommodated, combination property is good.
Embodiment
The embodiment of the present invention is by providing a kind of polymer matrix thixotroping cement mortar, and the thixotroping cementitious grout structure is formed soon
And be more easily damaged, so that the security of construction is improved while the effect such as its leakproof anti-channeling is played, and its thixotropy is by temperature
Degree influence is smaller, and combination property is good, the well cementation available for the Oil/gas Well such as weak formation, easy leakage, easy channelling.
To achieve the above object, general thought of the embodiment of the present invention is as follows：
The invention provides a kind of polymer matrix thixotroping cement mortar, by weight, the thixotroping cement mortar composition is as follows：
100 parts of G class g cements, 3~5 parts of polymeric thixotropic agents, 1~3 part of polymeric surfactant, 2~5 parts of polymer fluid loss agent,
0.3~1.5 part of polymer drag reducer, 34~46 parts of water.
Due to the heat resistance and salt tolerance of polymeric thixotropic agents, " dynamic physical cross-linked network can be formed in mortar architecture
The thixotropy of the interaction of structure ", in addition polymeric surfactant and polymeric thixotropic agents, further lifting system, from
And the thixotroping cementitious grout structure is formed fast and is more easily damaged；And the rise of temperature be conducive to the formation of associative structure from
And cement mortar is still kept good thixotropy when temperature is higher, thixotropy is affected by temperature smaller；In the mutual of each component
Under effect, the cement mortar shows good combination property.
In order to be better understood from above-mentioned technical proposal, detailed is done to technical solution of the present invention below by specific embodiment
Explanation, it should be understood that the specific features in the embodiment of the present invention and embodiment be to technical solution of the present invention specifically
It is bright, rather than the restriction to technical solution of the present invention, in the case where not conflicting, the skill in the embodiment of the present invention and embodiment
Art feature can be combined with each other.
The embodiments of the invention provide a kind of polymer matrix thixotroping cement mortar, by weight, the thixotroping cement mortar group
Into as follows：100 parts of G class g cements, 3~5 parts of polymeric thixotropic agents, 1~3 part of polymeric surfactant, polymer fluid loss agent 2
~5 parts, 0.3~1.5 part of polymer drag reducer, 34~46 parts of water.
Polymeric thixotropic agents described in the embodiment of the present invention are methacrylic acid, acrylamide, 2- acrylamido -2- first
The hydrophobic associated polymer that the four kinds of monomer polymerizations of base propane sulfonic acid and higher hydrocarbyl acrylate are obtained, the weight ratio of four kinds of monomers is 5
~25:20~50:30~70:5~25.Wherein, the optional dodecyl acrylate of the higher hydrocarbyl acrylate, tetradecyl acrylate or
Process Conditions of Cetane Acrylate.
Contain hydrophilic monomer and hydrophobic monomer in the polymeric thixotropic agents simultaneously, four kinds of monomers are carried out according to said ratio
Hydrophilic unit and hydrophobic units ratio are suitable in polymerization, obtained polymeric thixotropic agents, form hydrophobic associated polymer, by dredging
Water association can form " dynamic physical cross-linked network structure " in mortar architecture, and the structure is more easily damaged；And
Monomer ratio is in the proportion, as temperature is raised, polymeric thixotropic agents solubility increase, advantageously forms more
Associative structure, it is possible to decrease thixotropic agent is to the sensitiveness of temperature, so as to still have good thixotropy at relatively high temperatures.
In the embodiment of the present invention, the polymeric thixotropic agents are obtained using the method synthesis of emulsifier-free emulsion polymerization.
In specific implementation process, the polymeric thixotropic agents can be prepared via a method which：
Appropriate distilled water is added in reaction vessel, according to said ratio weigh 2- acrylamide-2-methylpro panesulfonic acids,
Methacrylic acid monomer is simultaneously added in the reaction vessel, and stirring dissolves monomer, forms solution；
It is about 7.0 to adjust the solution ph；
Acrylamide and the senior fat of acrylic acid are added into the solution, is uniformly mixed, while being passed through inert gas
Deoxygenation, forms mixed liquor；
The mixed liquor is heated up, initiator is added into the mixed liquor when temperature reaches 50 DEG C, triggers poly-
Reaction is closed, and in 50 DEG C of isothermal reaction 5h, obtains reaction product, the reaction product is the polymeric thixotropic agents.
Specifically, the inert gas is selected from nitrogen or argon gas.The initiator is redox initiation system.
Polymeric surfactant described in the embodiment of the present invention be Sodium Polyacrylate, Styrene-acrylic copolymer or
Maleic anhydride-styrene copolymers.It has synergistic function to polymeric thixotropic agents, is conducive to the shape of hydrophobic association structure
Into the thixotropy for the further lifting system that can be interacted with polymeric thixotropic agents.
Polymer fluid loss agent described in the embodiment of the present invention is 2- acrylamide-2-methylpro panesulfonic acid analog copolymers,
It is preferred that model BXF-200L (AF) or BCG-200L.
Polymer drag reducer described in the embodiment of the present invention is polycarboxylic acid, plays drag reduction, improves cement paste rheological,
It is preferred that model BCD-210L.
In order that those skilled in the art can further understand the scheme of the embodiment of the present invention, it will be based on below
The scheme that the embodiment of the present invention is introduced describes in detail to it.
Embodiment 1
100 parts of G class g cements are weighed first to be placed in lower grey container, then weigh 34 parts of water in the slurry cup for preparing cement mortar,
Then 3 parts of polymeric thixotropic agents, 3 parts of polymeric surfactant (Styrene-acrylic copolymer), polymer drop are weighed respectively
4 parts of dehydration agent (BCG-200L), 0.5 part of polymer drag reducer (BCD-210L) are poured into and are placed with the slurry cup of water.It will claim in slurry cup
After the material taken is mixed evenly with corrugation agitator, according to GB19139-2012《Oil-well cement test method》Specified in water
Slurrying method prepares polymer matrix thixotroping cement mortar of the present invention, labeled as 1# samples.
Polymeric thixotropic agents are methacrylic acid, acrylamide, 2- acrylamide-2-methylpro panesulfonic acids in the present embodiment
With the copolymer of four kinds of monomers of dodecyl acrylate, its mass ratio is 5:40:30:25.
Embodiment 2
100 parts of G class g cements are weighed first to be placed in lower grey container, then weigh 37 parts of water in the slurry cup for preparing cement mortar,
Then 3.5 parts of polymeric thixotropic agents, 2 parts of polymeric surfactant (Styrene-acrylic copolymer), polymer are weighed respectively
5 parts of fluid loss agent (BXF-200L), 1 part of polymer drag reducer (BCD-210L) are poured into and are placed with the slurry cup of water.It will claim in slurry cup
After the material taken is mixed evenly with corrugation agitator, according to GB19139-2012《Oil-well cement test method》Specified in water
Slurrying method prepares polymer matrix thixotroping cement mortar of the present invention, labeled as 2# samples.
Polymeric thixotropic agents are methacrylic acid, acrylamide, 2- acrylamide-2-methylpro panesulfonic acids in the present embodiment
With the copolymer of four kinds of monomers of tetradecyl acrylate, its mass ratio is 10:30:45:15.
Embodiment 3
100 parts of G class g cements are weighed first to be placed in lower grey container, then weigh 40 parts of water in the slurry cup for preparing cement mortar,
Then 5 parts of polymeric thixotropic agents, 2 parts of polymeric surfactant (maleic anhydride-styrene copolymers), polymer are weighed respectively
3 parts of fluid loss agent (BXF-200L), 1.5 parts of polymer drag reducer (BCD-210L) are poured into and are placed with the slurry cup of water.By in slurry cup
After the material weighed is mixed evenly with corrugation agitator, according to GB19139-2012《Oil-well cement test method》Specified in
Cement mortar preparation method prepares polymer matrix thixotroping cement mortar of the present invention, labeled as 3# samples.
Polymeric thixotropic agents are methacrylic acid, acrylamide, 2- acrylamide-2-methylpro panesulfonic acids in the present embodiment
With the copolymer of four kinds of monomers of Process Conditions of Cetane Acrylate, its mass ratio is 15:20:55:10.
Embodiment 4
100 parts of G class g cements are weighed first to be placed in lower grey container, then weigh 46 parts of water in the slurry cup for preparing cement mortar,
Then 3 parts of polymeric thixotropic agents, 1 part of polymeric surfactant (Sodium Polyacrylate), polymer fluid loss agent are weighed respectively
(BXF-200L) 4 parts, 0.3 part of polymer drag reducer (BCD-210L) pours into and is placed with the slurry cup of water.By what is weighed in slurry cup
After material is mixed evenly with corrugation agitator, according to GB19139-2012《Oil-well cement test method》Specified in cement mortar system
Preparation Method prepares polymer matrix thixotroping cement mortar of the present invention, labeled as 4# samples.
Polymeric thixotropic agents are methacrylic acid, acrylamide, 2- acrylamide-2-methylpro panesulfonic acids in the present embodiment
With the copolymer of four kinds of monomers of Process Conditions of Cetane Acrylate, its mass ratio is 5:20:70:5.
Embodiment 5
100 parts of G class g cements are weighed first to be placed in lower grey container, then weigh 40 parts of water in the slurry cup for preparing cement mortar,
Then 4 parts of polymeric thixotropic agents, 1 part of polymeric surfactant (Sodium Polyacrylate), polymer fluid loss agent are weighed respectively
(BXF-200L) 3.5 parts, 0.5 part of polymer drag reducer (BCD-210L) pours into and is placed with the slurry cup of water.It will be weighed in slurry cup
Material be mixed evenly with corrugation agitator after, according to GB19139-2012《Oil-well cement test method》Specified in cement mortar
Preparation method prepares polymer matrix thixotroping cement mortar of the present invention, labeled as 5# samples.
Polymeric thixotropic agents are methacrylic acid, acrylamide, 2- acrylamide-2-methylpro panesulfonic acids in the present embodiment
With the copolymer of four kinds of monomers of Process Conditions of Cetane Acrylate, its mass ratio is 5:25:60:10.
Obtained polymer matrix thixotroping cement mortar properties of sample is evaluated：
According to GB/T 19139-2012《Oil-well cement test method》Specified in cementitious grout Strength Testing Methods,
The gel strength that polymer matrix thixotroping cement slurry samples under different temperatures are stood after 10s, 5min, 10min is commented respectively
Valency.Based on testing gel strength method, using six fast rotation viscometers to polymer matrix thixotroping cement slurry samples thixotroping knot
The invertibity of structure is evaluated.According to GB/T19139-2012《Oil-well cement test method》Specified in test method to poly-
The combination property of compound base thixotroping cement slurry samples is evaluated.
(1) thixotroping cement slurry samples under different temperatures are tested with six fast rotation viscometers to stand after 10s, 5min, 10min
Gel strength, test temperature is respectively 30 DEG C, 60 DEG C, 90 DEG C, and test result is shown in Table 1.In addition, with six fast rotation viscometers to touching
The invertibity for becoming cement slurry samples thixotroping structure is evaluated.Experiment tests the thixotroping cement mortar just configured in 300r/ first
Reading under min, then stands 10min and tests its gel strength, then destroys its glue with 300r/min rotating speed stirring 1min
Concretio and the reading for recording stirring 30s, then standing 10min tests its gel strength again.Test temperature is respectively 30 DEG C, 90
DEG C, test result is shown in Table 2.
Polymer matrix thixotroping cementitious grout strength test results under the different temperatures of table 1
Polymer matrix thixotroping cementitious grout strength test results under the different temperatures of table 2
As shown in Table 1, gel strength increases sharply after the polymer matrix thixotroping cement slurry samples of preparation are stood, glue after 5min
Solidifying intensity will reach high value, and as temperature is raised, its gel strength is barely affected, so that in cement mortar injection well
Its leakproof, the effect of anti-channeling are played behind bottom.As shown in Table 2, its thixotroping structure of polymer matrix thixotroping cement mortar is prepared with fine
Invertibity, thinning quickly can return to original slurry state after stirring after forming jelling structure retrogradation after standing so that
Reduce the risk of construction, then after standing and jelling structure originally can be recovered, show good thixotropic behavior.
(2) combination property of test polymer base thixotroping mortar architecture, test temperature is 60 DEG C, 90 DEG C, test result
Such as table 3.
The polymer matrix thixotroping cement mortar combination property table of table 3
As shown in Table 3, the thickening of polymer matrix thixotroping mortar architecture is normal, and transit time is short, and fluidity of slurry is good, dehydration
Amount is low, and forms cement strength height, and combination property is good, can meet site operation requirement.
Above it is demonstrated experimentally that the polymer matrix thixotroping mortar architecture thixotropy of the embodiment of the present invention is strong, gel strength shape
Into fast and be more easily damaged, thixotropy is affected by temperature small, and its fluid loss is low, compression strength is high, and combination property is good.
It should be noted last that, above embodiment is merely illustrative of the technical solution of the present invention and unrestricted,
Although the present invention is described in detail with reference to example, it will be understood by those within the art that, can be to the present invention
Technical scheme modify or equivalent substitution, without departing from the spirit and scope of technical solution of the present invention, it all should cover
Among scope of the presently claimed invention.
Claims (7)
1. a kind of polymer matrix thixotroping cement mortar, it is characterised in that by weight, the thixotroping cement mortar composition is as follows：G grades
100 parts of cement, 3~5 parts of polymeric thixotropic agents, 1~3 part of polymeric surfactant, 2~5 parts of polymer fluid loss agent, polymerization
0.3~1.5 part of thing drag reducer, 34~46 parts of water.
2. polymer matrix thixotroping cement mortar as claimed in claim 1, it is characterised in that the polymeric thixotropic agents are methyl-prop
What olefin(e) acid, acrylamide, the four kinds of monomers polymerization of 2- acrylamide-2-methylpro panesulfonic acids and higher hydrocarbyl acrylate were obtained hydrophobic forms
Mould assembly polymer, the weight ratio of four kinds of monomers is 5~25:20~50:30~70:5~25.
3. polymer matrix thixotroping cement mortar as claimed in claim 2, it is characterised in that the higher hydrocarbyl acrylate is acrylic acid
Ten diester, tetradecyl acrylate or Process Conditions of Cetane Acrylate.
4. polymer matrix thixotroping cement mortar as claimed in claim 2, it is characterised in that the polymeric thixotropic agents are used without soap
Emulsion polymerisation process is prepared.
5. polymer matrix thixotroping cement mortar as claimed in claim 1, it is characterised in that the polymeric surfactant is poly-
PAA, Styrene-acrylic copolymer or maleic anhydride-styrene copolymers.
6. polymer matrix thixotroping cement mortar as claimed in claim 1, it is characterised in that the polymer fluid loss agent is 2- third
Acrylamide base -2- methyl propane sulfonic acid analog copolymers.
7. polymer matrix thixotroping cement mortar as claimed in claim 1, it is characterised in that the polymer drag reducer is polycarboxylic acids
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111718149A (en) * | 2020-07-28 | 2020-09-29 | 中海石油(中国)有限公司湛江分公司 | Oil well cement low-viscosity thixotropic agent and preparation method thereof |
| 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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2017
- 2017-05-19 CN CN201710356182.XA patent/CN107057664B/en active Active
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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111718149A (en) * | 2020-07-28 | 2020-09-29 | 中海石油(中国)有限公司湛江分公司 | Oil well cement low-viscosity thixotropic agent and preparation method thereof |
| CN111718149B (en) * | 2020-07-28 | 2022-03-04 | 中海石油(中国)有限公司湛江分公司 | Oil well cement low-viscosity thixotropic agent and preparation method thereof |
| 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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