CN113185171A - Cement reinforcing agent suitable for deepwater low-temperature environment, preparation method thereof and cement paste system - Google Patents
Cement reinforcing agent suitable for deepwater low-temperature environment, preparation method thereof and cement paste system Download PDFInfo
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- CN113185171A CN113185171A CN202110499006.8A CN202110499006A CN113185171A CN 113185171 A CN113185171 A CN 113185171A CN 202110499006 A CN202110499006 A CN 202110499006A CN 113185171 A CN113185171 A CN 113185171A
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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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
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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
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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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- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/74—Underwater applications
Abstract
The invention discloses a cement reinforcing agent suitable for deepwater low-temperature environment, a preparation method thereof and a cement paste system, wherein the cement reinforcing agent is aluminum-doped calcium silicate hydrate, and the molar ratio of aluminum, silicon and calcium in the aluminum-doped calcium silicate hydrate is as follows: the molar ratio of Ca/Si is 1.5-2.0, and the molar ratio of Al/Si is 0.08-0.15. The method can improve the early strength of the cement stone under the deepwater low-temperature condition, and solve the problems that the strength of the cement stone in the low-temperature environment is slowly developed and the construction safety is influenced. According to the invention, the early strength performance of the C-S-H crystal seed is greatly improved by adding Al ions for improving the C-S-H crystal seed structure. The invention has good effect of improving the low-temperature mechanical compressive strength of the oil well cement paste, is suitable for the deep water low-temperature environment, can effectively improve the early compressive strength of the oil well cement and ensure the safety of operation and construction.
Description
Technical Field
The invention relates to the technical field of cement additives, in particular to a cement reinforcing agent suitable for deep water low-temperature environment, a preparation method thereof and a cement paste system.
Background
With the increasing dependence and demand of human society on energy, oil and gas exploration and development have gradually moved to deep water and ultra-deep water areas, and related researches have become the key points of attention of people at present. In the exploration and development process of deep water and ultra-deep water oil and gas resources, the marine environment has the characteristics of low temperature, shallow laminar flow, low stratum fracture pressure and the like, and particularly, the low-temperature environment in the well cementation process seriously influences the hydration rate of oil well cement, so that the early strength of the set cement is low, the annular set cement cannot reach enough shear stress to support the weight of a casing in a short time, the setting waiting time of well cementation construction is prolonged, and the requirement of well cementation quick setting and early strength cannot be met.
The addition of the reinforcing agent is a main method for shortening the cement paste waiting setting time and improving the early compressive strength of the set cement in low-temperature well cementation. Common reinforcing agents include both inorganic strong electrolytes and water-soluble organic electrolytes: the inorganic strong electrolyte mainly comprises chloride, sulfate, nitrate and carbonate; the water-soluble organic electrolyte includes triethanolamine, calcium formate, etc. However, many commonly used reinforcing agents have problems such as corrosion of the casing pipe or reaction of alkali aggregate when used in deep water and low temperature environment. Research has shown that the addition of the C-S-H crystal seed can improve the mechanical property of the cement-based material due to the crystal nucleus effect, but the reinforcing property of the C-S-H crystal seed at the present stage under the low temperature environment is not enough to meet the deep water well cementation requirement.
In conclusion, based on the current research situation of the reinforcing agent and the urgent need of deepwater oil and gas resource exploration and development on the low-temperature reinforcing agent, the research and development of the seed crystal reinforcing agent which can be suitable for deepwater low-temperature environment are urgent.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a cement reinforcing agent suitable for deep water low-temperature environment, a preparation method thereof and a cement slurry system, wherein the crystal structure and the reinforcing performance of the C-S-H crystal seeds are optimized by doping Al ions, so that the reinforcing effect of the C-S-H crystal seeds is greatly improved, the requirement of deep water operation low-temperature well cementation can be met, the waiting time is shortened, the operation efficiency and the safety are improved, the efficient well cementation construction of a deep water area is realized, and the safe and efficient development of oil and gas resources of the deep water area is ensured.
The technical scheme of the invention is as follows:
in one aspect, a cement reinforcing agent suitable for deepwater low-temperature environment is provided, the cement reinforcing agent is aluminum-doped calcium silicate hydrate, and the molar ratio of aluminum, silicon and calcium in the aluminum-doped calcium silicate hydrate is as follows: the molar ratio of Ca/Si is 1.5-2.0, and the molar ratio of Al/Si is 0.08-0.15.
Preferably, the aluminum-doped calcium silicate hydrate is prepared by the following components: sodium metasilicate, calcium nitrate and aluminum potassium sulfate.
Preferably, the sodium metasilicate is any one of anhydrous sodium metasilicate, sodium metasilicate pentahydrate and sodium metasilicate nonahydrate; the calcium nitrate is any one of anhydrous calcium nitrate, calcium nitrate monohydrate and calcium nitrate tetrahydrate; the aluminum potassium sulfate is anhydrous aluminum potassium sulfate or aluminum potassium sulfate dodecahydrate.
Preferably, when the sodium metasilicate is sodium metasilicate nonahydrate, the calcium nitrate is calcium nitrate tetrahydrate and the potassium aluminum sulfate is potassium aluminum sulfate dodecahydrate, the aluminum-doped calcium silicate hydrate is prepared from the following raw materials in parts by mass: 42-48 parts of sodium metasilicate nonahydrate, 44-50 parts of calcium nitrate tetrahydrate and 8-12 parts of aluminum potassium sulfate dodecahydrate.
Preferably, when the sodium metasilicate is anhydrous sodium metasilicate, the calcium nitrate is anhydrous calcium nitrate, and the potassium aluminum sulfate is anhydrous potassium aluminum sulfate, the aluminum-doped calcium silicate hydrate is prepared from the following raw materials in parts by mass: 32-38 parts of anhydrous sodium metasilicate, 55-65 parts of anhydrous calcium nitrate and 7-11 parts of anhydrous aluminum potassium sulfate.
On the other hand, the preparation method of the cement reinforcing agent suitable for the deepwater low-temperature environment is also provided, the aluminum-doped calcium silicate hydrate is prepared by adopting a coprecipitation method, and the molar ratio of the elements of aluminum, silicon and calcium in the aluminum-doped calcium silicate hydrate is as follows: the molar ratio of Ca/Si is 1.5-2.0, and the molar ratio of Al/Si is 0.08-0.15.
Preferably, when the aluminum-doped calcium silicate hydrate is prepared by adopting a coprecipitation method, the pH value of the solution is adjusted to 11-13, the reaction temperature is set to 60-80 ℃, the reaction time lasts for 5-7d, and the stirring speed is set to 500-1000 r/min.
Preferably, the aluminum-doped calcium silicate hydrate is prepared by the following components: sodium metasilicate, calcium nitrate and aluminum potassium sulfate.
In another aspect, there is provided a cement slurry system suitable for deep water low temperature environment, comprising oil well cement and the cement reinforcing agent described above, or the cement reinforcing agent prepared by the preparation method described above.
Preferably, the cement reinforcing agent has a particle size of less than 300 mesh.
The invention has the beneficial effects that:
(1) the reinforcing agent has excellent low-temperature early strength performance, can meet the requirement of low-temperature well cementation in deepwater operation, reduces the waiting time, and improves the operation efficiency and the safety. (2) The reinforcing agent is a chlorine-free reinforcing agent, has good fluidity in the use process, does not have flash coagulation phenomenon, and does not have corrosion effect on the sleeve. (3) Compared with the C-S-H crystal seed, the reinforcing agent has a more excellent crystal structure and a more excellent low-temperature reinforcing property.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an SEM image of the 12h micro-morphology of a blank set cement in comparative example 1;
FIG. 2 is a SEM image of the 12H micro-morphology of the set cement of comparative example 2 using a C-S-H seed crystal reinforcing agent;
FIG. 3 is A SEM image of 12H microstructure of set cement using A C-S-A-H seed crystal reinforcing agent in example 2 of the present invention;
FIG. 4 is a graph of cement slurry hydration temperature rise for example 2 of the present invention and comparative examples 1-2.
Detailed Description
The invention is further illustrated with reference to the following figures and examples. It should be noted that, in the present application, the embodiments and the technical features of the embodiments may be combined with each other without conflict. It is noted that, unless otherwise indicated, 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 application belongs.
In one aspect, the invention provides a cement reinforcing agent suitable for a deep water low-temperature environment, wherein the cement reinforcing agent is aluminum-doped calcium silicate hydrate, and the molar ratio of aluminum, silicon and calcium in the aluminum-doped calcium silicate hydrate is as follows: the molar ratio of Ca/Si is 1.5-2.0, and the molar ratio of Al/Si is 0.08-0.15.
In a specific embodiment, the aluminum-doped calcium silicate hydrate is prepared by the following components: sodium metasilicate, calcium nitrate and aluminum potassium sulfate. The sodium metasilicate is any one of anhydrous sodium metasilicate, sodium metasilicate pentahydrate and sodium metasilicate nonahydrate; the calcium nitrate is any one of anhydrous calcium nitrate, calcium nitrate monohydrate and calcium nitrate tetrahydrate; the aluminum potassium sulfate is anhydrous aluminum potassium sulfate or aluminum potassium sulfate dodecahydrate.
Optionally, when the sodium metasilicate is sodium metasilicate nonahydrate, the calcium nitrate is calcium nitrate tetrahydrate, and the potassium aluminum sulfate is potassium aluminum sulfate dodecahydrate, the aluminum-doped calcium silicate hydrate is prepared from the following raw materials in parts by mass: 42-48 parts of sodium metasilicate nonahydrate, 44-50 parts of calcium nitrate tetrahydrate and 8-12 parts of aluminum potassium sulfate dodecahydrate.
Optionally, when the sodium metasilicate is anhydrous sodium metasilicate, the calcium nitrate is anhydrous calcium nitrate, and the potassium aluminum sulfate is anhydrous potassium aluminum sulfate, the aluminum-doped calcium silicate hydrate is prepared by the following raw materials in parts by mass: 32-38 parts of anhydrous sodium metasilicate, 55-60 parts of anhydrous calcium nitrate and 7-11 parts of anhydrous aluminum potassium sulfate.
It should be noted that the principle of the invention that is applicable to deep water low temperature environment is as follows: by adopting the method of doping Al ions and adjusting the proportion, the water content and the like of calcium, silicon and aluminum, the crystal structure and the enhanced performance of the C-S-H crystal seed are optimized, the enhanced performance of the C-S-H crystal seed is improved, and the C-S-H crystal seed can be applied in the deep water low-temperature environment. The preferable raw materials of sodium metasilicate, calcium nitrate and potassium aluminum sulfate in the embodiment have proper water solubility, can conveniently adjust the molar ratio of each element, and do not contain chloride ions, so that the obtained cement reinforcing agent has good fluidity in the use process, no flash coagulation phenomenon and no corrosion effect on a sleeve. The aluminum-doped calcium silicate hydrate can also be prepared by adopting other raw materials which have proper dissolving performance and are free of chloride ions.
On the other hand, the invention also provides a preparation method of the cement reinforcing agent suitable for the deepwater low-temperature environment, the aluminum-doped calcium silicate hydrate is prepared by adopting a coprecipitation method, and the molar ratio of the elements of aluminum, silicon and calcium in the aluminum-doped calcium silicate hydrate is as follows: the molar ratio of Ca/Si is 1.5-2.0, and the molar ratio of Al/Si is 0.08-0.15.
In a specific embodiment, when the aluminum-doped calcium silicate hydrate is prepared by adopting a coprecipitation method, the pH value of the solution is adjusted to 11-13, the reaction temperature is set to be 60-80 ℃, the reaction time lasts for 5-7d, and the stirring speed is set to be 500-1000 r/min.
In a specific embodiment, the aluminum-doped calcium silicate hydrate is prepared by the following components: sodium metasilicate, calcium nitrate and aluminum potassium sulfate. The preparation method of the aluminum-doped calcium silicate hydrate specifically comprises the following steps:
s1: dissolving sodium metasilicate in water to prepare 0.5-1.0mol/L sodium metasilicate solution; dissolving calcium nitrate in water to prepare 0.5-1.0mol/L calcium nitrate solution; dissolving aluminum potassium sulfate in water to prepare 0.25-0.5mol/L aluminum potassium sulfate solution;
s2: adding a calcium nitrate solution into a reaction vessel, heating the reaction vessel to 60-80 ℃, starting stirring at the stirring speed of 500-1000r/min, and adjusting the pH value of the calcium nitrate solution to 11-13;
s3: respectively dripping a sodium metasilicate solution and an aluminum potassium sulfate solution into the reaction container, controlling the dripping speed to be 1-2 drops/s, reacting for 5-7d, and periodically adjusting the pH value of the mixed solution to 11-13; the volume ratio of the sodium metasilicate solution to the calcium nitrate solution to the aluminum potassium sulfate solution is as follows: 100-125: 150-200: 15-25;
s4: and after the reaction is finished, repeatedly washing and filtering the product for 3-5 times by using an organic solvent, drying and crushing the washed and filtered solid product to obtain the cement reinforcing agent.
Optionally, when preparing the aqueous solution of each component, deionized water is used for preparation. It should be noted that the use of deionized water enables better control of the ion concentration in the solution, and avoids the introduction of impurity ions such as chloride ions and magnesium ions.
Optionally, the reaction vessel is a three-neck flask. The three-neck flask is only one preferred reaction vessel for preparing the cement reinforcing agent in a laboratory, and is not limited to the reaction vessel of the present invention, and when the preparation method of the present invention is used, the cement reinforcing agent may be prepared using another reaction vessel.
Optionally, during drying, the product is dried in a drying oven at 60-70 deg.C for 2-3 d.
Optionally, during crushing, a high-speed crusher is used for crushing, and a 300-mesh standard sieve is used for screening to obtain the cement reinforcing agent with the particle size of less than 300 meshes.
Optionally, the sodium metasilicate, the calcium nitrate and the potassium aluminum sulfate are in analytical pure specifications.
It should be noted that, the preparation of the aluminum-doped hydrated calcium silicate by the coprecipitation method has the advantages of pure product, short reaction time, simple operation and the like, besides the method, the invention can also adopt the volcanic ash reaction method, the sol-gel method, the calcium silicate hydration method and other methods to prepare the aluminum-doped hydrated calcium silicate.
In another aspect, the present invention further provides a cement slurry system suitable for deep water low temperature environment, comprising oil well cement and the cement reinforcing agent described above, or the cement reinforcing agent prepared by any one of the above preparation methods.
Optionally, the cement reinforcing agent has a particle size of less than 300 mesh. Optionally, the oil well cement is a grade G oil well cement. It should be noted that, in addition to the grade G oil well cement, other grades of oil well cement suitable for deep water low temperature environment, such as grade H oil well cement, may be used in the cement slurry system of the present invention.
Example 1
The cement reinforcing agent suitable for the deep water low-temperature environment is prepared by the following preparation method:
s1: mixing Na2SiO3·9H2Dissolving O in deionized water to prepare 1.0mol/L Na2SiO3A solution; mixing Ca (NO)3)2·4H2Dissolving O in deionized water to prepare Ca (NO) of 1.0mol/L3)2A solution; mixing KAl (SO)4)2·12H2Dissolving O in deionized water to obtain 0.5mol/L KAl (SO)4)2A solution;
s2: mixing the prepared Ca (NO)3)2Adding the solution into a three-neck flask, putting the three-neck flask into a water bath kettle at 60 ℃, inserting a stirring rod, setting the rotating speed at 500r/min, and adjusting the pH value of the solution to 11-13;
s3: mixing Na2SiO3Mixing the solution with KAl (SO)4)2Respectively dripping the solution into a three-neck flask, controlling the dripping speed at 2 drops/s, reacting for 7d, and periodically adjusting the pH value of the mixed solution to 13; the Na is2SiO3Solution, Ca (NO)3)2Solution, KAl (SO)4)2The volume ratio of the solution is 100: 150: 20
S4: after the reaction is finished, repeatedly washing and filtering the product for 3 times by using a common organic solvent, drying the washed and filtered solid product in a drying box at 60 ℃ for 3 days, crushing the dried product by using a high-speed crusher, and sieving the crushed product by using a standard sieve with 300 meshes to obtain the cement reinforcing agent.
Example 2
A cement paste system comprises the following components in parts by weight: 400 parts of G-grade oil well cement, 12 parts of the cement reinforcing agent in example 1, 12 parts of a fluid loss agent, 4.8 parts of a dispersing agent, 2 parts of a defoaming agent and 180 parts of slurry mixing water.
The cement paste system is prepared by the following preparation method: uniformly mixing G-grade oil well cement and a cement reinforcing agent in a dry mode, uniformly mixing liquid additives (a fluid loss agent, a dispersing agent and a defoaming agent) with slurry preparation water, and then preparing cement slurry from the obtained water solution and dry-mixed powder according to GB/T19139 oil well cement test method.
Example 3
A cement paste system comprises the following components in parts by weight: 400 parts of G-grade oil well cement, 20 parts of the cement reinforcing agent in example 1, 12 parts of a fluid loss agent, 4.8 parts of a dispersing agent, 2 parts of a defoaming agent and 182 parts of slurry mixing water.
The cement paste system is prepared by the following preparation method: uniformly mixing G-grade oil well cement and a cement reinforcing agent in a dry mode, uniformly mixing liquid additives (a fluid loss agent, a dispersing agent and a defoaming agent) with slurry preparation water, and then preparing cement slurry from the obtained water solution and dry-mixed powder according to GB/T19139 oil well cement test method.
Comparative example 1
A cement paste system comprises the following components in parts by weight: 400 parts of G-grade oil well cement, 12 parts of fluid loss additive, 4.8 parts of dispersant, 2 parts of defoaming agent and 176 parts of slurry preparation water.
The cement paste system is prepared by the following preparation method: uniformly mixing liquid additives (a fluid loss agent, a dispersing agent and a defoaming agent) with slurry preparation water, and then preparing cement slurry from the obtained aqueous solution and the G-grade oil well cement according to GB/T19139 oil well cement test method.
Comparative example 2
A cement paste system comprises the following components in parts by weight: 400 parts of G-grade oil well cement, 12 parts of C-S-H seed crystal reinforcing agent, 12 parts of fluid loss agent, 4.8 parts of dispersing agent, 2 parts of defoaming agent and 180 parts of slurry preparation water.
The cement paste system is prepared by the following preparation method: the G-grade oil well cement and the traditional C-S-H seed crystal reinforcing agent are dry-mixed uniformly, liquid additives (a fluid loss agent, a dispersing agent and a defoaming agent) and slurry preparation water are mixed uniformly, and then the obtained water solution and dry-mixed powder are prepared into cement slurry according to GB/T19139 oil well cement test method.
The grade G oil well cement of the above examples 2-3 and comparative examples 1-2 was Shandong cement, and the fluid loss agent was AMPS-based polymer; the dispersant is polycarboxylate; the defoaming agent is dimethyl silicone oil; the slurry preparation water is fresh water.
The microscopic morphology of the cement slurry systems of example 2 and comparative examples 1-2 above at age 12h was observed as shown in fig. 1-3. From the figures 1-3, compared with blank set cement and set cement doped with the C-S-H seed crystal reinforcing agent, the set cement added with the Al seed crystal reinforcing agent has a more compact structure at 12H, hydration products of C-S-H, ettringite, calcium hydroxide and the like are spread over the whole visual field, and the lap joint is tight, which shows that the Al seed crystal reinforcing agent can effectively promote the cement hydration reaction in a low-temperature environment of 5 ℃ and improve the early strength of the set cement. The hydration exotherm was monitored for the cement slurry systems of example 2 and comparative examples 1-2 above, and the results are shown in fig. 4. From fig. 4, it can be seen that compared with the blank cement slurry and the cement slurry added with the C-S-H seed crystal reinforcing agent, the heat release peak value of the cement hydration of the Al-doped seed crystal reinforcing agent is higher, and the time for reaching the heat release peak is shorter, which indicates that the promotion effect of the Al-doped seed crystal reinforcing agent on the cement hydration is more obvious, and further the strength development of the set cement is promoted.
The cement slurry systems of example 2 and comparative examples 1-2 were tested for compression strength at low temperatures for short ages and the results are shown in Table 1:
TABLE 1 compression Strength of Cement Stone of various Cement paste systems at 5 ℃ in various ages
As can be seen from Table 1, when the Al-doped cement reinforcing agent (C-S-A-H seed crystal) is applied to A cement paste system, the compressive strength of the set cement can be enhanced, and under the age conditions of 8H, 12H and 24H, the compressive strength is respectively improved by 133.33%, 63.64% and 37.5% compared with that of the C-S-H seed crystal reinforcing agent, and the improvement degree is obvious.
The cement paste system of the above example 3 was subjected to the set cement compressive strength test under different low temperature environments and different curing ages, and the test results are shown in table 2:
table 2 example 3 set of cement in a cement slurry system compressive strength at different low temperatures for different ages
As can be seen from Table 2, when the Al-doped cement reinforcing agent (C-S-A-H seed crystal) is applied to A cement paste system, the compression strength of A set cement reaches 5.2MPA under the conditions of 5 ℃ and 8 hours of age, and the deep water well cementation requirement is met, which shows that the Al-doped cement reinforcing agent can be applied to A low-temperature deep seA environment.
In conclusion, the cement reinforcing agent disclosed by the invention can be suitable for a low-temperature deep water environment, meets the deep water cementing requirement, and has a remarkable progress compared with the prior art.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The cement reinforcing agent suitable for the deepwater low-temperature environment is characterized in that the cement reinforcing agent is aluminum-doped calcium silicate hydrate, and the molar ratio of aluminum, silicon and calcium in the aluminum-doped calcium silicate hydrate is as follows: the molar ratio of Ca/Si is 1.5-2.0, and the molar ratio of Al/Si is 0.08-0.15.
2. The cement reinforcer suitable for deep water low-temperature environment according to claim 1, wherein the aluminum-doped calcium silicate hydrate is prepared from the following components: sodium metasilicate, calcium nitrate and aluminum potassium sulfate.
3. The cement reinforcer suitable for deep water low temperature environment according to claim 2, wherein the sodium metasilicate is any one of anhydrous sodium metasilicate, pentahydrate sodium metasilicate and nonahydrate sodium metasilicate; the calcium nitrate is any one of anhydrous calcium nitrate, calcium nitrate monohydrate and calcium nitrate tetrahydrate; the aluminum potassium sulfate is anhydrous aluminum potassium sulfate or aluminum potassium sulfate dodecahydrate.
4. The cement reinforcer suitable for deep water low-temperature environment according to claim 3, wherein when the sodium metasilicate is sodium metasilicate nonahydrate, the calcium nitrate is calcium nitrate tetrahydrate and the potassium aluminum sulfate is potassium aluminum sulfate dodecahydrate, the aluminum-doped calcium silicate hydrate is prepared by the following raw materials in parts by mass: 42-48 parts of sodium metasilicate nonahydrate, 44-50 parts of calcium nitrate tetrahydrate and 8-12 parts of aluminum potassium sulfate dodecahydrate.
5. The cement reinforcer suitable for deep water low-temperature environment according to claim 3, wherein when the sodium metasilicate is anhydrous sodium metasilicate, the calcium nitrate is anhydrous calcium nitrate, and the potassium aluminum sulfate is anhydrous potassium aluminum sulfate, the aluminum-doped calcium silicate hydrate is prepared by the following raw materials in parts by mass: 32-38 parts of anhydrous sodium metasilicate, 55-60 parts of anhydrous calcium nitrate and 7-11 parts of anhydrous aluminum potassium sulfate.
6. The preparation method of the cement reinforcing agent suitable for the deepwater low-temperature environment is characterized in that aluminum-doped calcium silicate hydrate is prepared by a coprecipitation method, and the molar ratio of aluminum, silicon and calcium in the aluminum-doped calcium silicate hydrate is as follows: the molar ratio of Ca/Si is 1.5-2.0, and the molar ratio of Al/Si is 0.08-0.15.
7. The method for preparing the cement reinforcing agent suitable for the deepwater low-temperature environment as claimed in claim 6, wherein when the aluminum-doped calcium silicate hydrate is prepared by the coprecipitation method, the pH value of the solution is adjusted to 11-13, the reaction temperature is set to 60-80 ℃, the reaction time lasts for 5-7d, and the stirring speed is set to 500-1000 r/min.
8. The method for preparing the cement reinforcing agent applicable to the deepwater low-temperature environment according to claim 6 or 7, wherein the aluminum-doped calcium silicate hydrate is prepared by the following components: sodium metasilicate, calcium nitrate and aluminum potassium sulfate.
9. A cement paste system suitable for deep water low temperature environment, comprising oil well cement and the cement reinforcing agent according to any one of claims 1 to 5, or the cement reinforcing agent prepared by the preparation method according to any one of claims 6 to 8.
10. The cement paste system suitable for deep water low temperature environment according to claim 5, wherein the cement reinforcing agent has a particle size of less than 300 meshes.
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| CN (1) | CN113185171A (en) |
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