CN112456878B - CO2-EGS mode high-temperature corrosion-resistant well cementation cement for hot and dry rock - Google Patents
CO2-EGS mode high-temperature corrosion-resistant well cementation cement for hot and dry rock Download PDFInfo
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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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- 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
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/26—Corrosion of reinforcement resistance
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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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Abstract
The invention discloses a novel CO2An EGS-mode high-temperature corrosion-resistant well cementation cement system for hot dry rock belongs to the technical field of oil and gas well cementation, and comprises the following raw materials in percentage by weight: 75-88% of low hydration heat cement or low calcium-silicon ratio cement; 11-20% of high-temperature strength reinforcing agent; CO resistance21 to 5 percent of corrosive material, provides a high-temperature corrosion-resistant well cementation cement system for hot dry rock with corrosion resistance, high-temperature resistance and heat preservation performance, and can meet the requirements of novel CO2And the dry hot rock production well in the EGS mode is sealed for a long time, the requirement on energy consumption is reduced, and the guarantee is provided for exploration and development, efficient production and environmental protection.
Description
Technical Field
The invention relates to the technical field of oil and gas well cementation, in particular to CO2-EGS-mode hot dry rock cementing cement with high temperature corrosion resistance.
Background
With the rapid development of economy in China, the problems of energy shortage and environmental pollution are increasingly remarkable, and the demand for clean energy is sharply increased. The hot dry rock is an existing form of geothermal energy, and refers to a dense high-temperature rock body which is buried deeper and has no fluid or only a small amount of fluid in the interior. The dry hot rock contains huge heat energy, is a high-efficiency clean energy accepted by international society, and has great competitiveness due to the advantages of large storage capacity, cleanness, low carbon, safety, reliability and the like. The reasonable development and utilization of geothermal energy can effectively relieve the current pressure of excessive dependence on fossil energy and environmental pollution, and improve the national energy safety.
An Enhanced Geothermal System (EGS) is formed by modifying a reservoir in a hot dry rock area, and is an artificial system for efficiently exploiting the geothermal energy of the hot dry rock, namely, geothermal energy is extracted to the ground by utilizing the circulation of a heat transfer medium for utilization. At present, the heat recovery media of the hot dry rock are 2 types, namely water and carbon dioxide. Water injection circulation heat exchange (H)2O-EGS) and carbon dioxide injection cycle heatExchange (CO)2EGS), the two heat collecting principles are consistent, but the effects are obviously different. And conventional H2Novel CO compared with O-EGS mode2The EGS mode has obvious advantages.
By using novel CO2EGS mode during production implementation, the production well will be exposed to high temperature, high stress, high concentration CO2The complex environment of erosion and the low heat conductivity coefficient of the cement sheath are needed, so that the heat loss in the shaft can be effectively reduced. Thus, novel CO2The EGS mode dry hot rock production well needs to have good high temperature resistance, carbonization resistance, low thermal conductivity and other composite properties.
At present against novel CO2The research on a well cementation cement slurry system adopted by the EGS mode is less, and mainly relates to the research on single performance of high temperature resistance or carbonization resistance. CN201610053575.9 introduces a high-temperature well cementation cement slurry for hot dry rock and a preparation method thereof, wherein the cement slurry contains the following components: oil well grade G cement; based on the mass of the oil well G-grade cement as 100 percent: 40-60% strength treating agent; 3-5% of retarder; 3-5% drag reducing agent; 3-5% of fluid loss additive; 0.05-0.1% of defoaming agent; 63-72% of water. Li quansha et al in the article of research on high-temperature-resistant and high-strength cement slurry system suitable for cementing hot dry rock improves the high-temperature strength of the set cement by an indoor evaluation method of preferably selecting a silicon-rich aluminum active material SCM and matching a high-temperature retarder and a toughening agent so as to construct a high-temperature-resistant and high-strength cement slurry system suitable for the geological working condition characteristics of the hot dry rock stratum. The research result is primarily applied to the ultra-deep high-temperature high-pressure well of the Qinghai dry hot rock, and a better result is obtained. CN200810008061.7 introduces a high temperature resistant cement paste system, which comprises the following components in parts by weight: 100 parts of cement, 55-65 parts of water, 6-15 parts of fluid loss additive, 4.8-7.2 parts of retarder, 20-40 parts of drag reducer, 3-5 parts of filler and 1-3 parts of stabilizer.
CN201110297635.9 introduces a CO-resistant2A corrosive cement for well cementing, the cement comprising: 1 part by weight of aluminate cement or sulphoaluminate cement, 0.1 to 0.5 part by weight of phosphateAnd 0-2 parts by weight of a filler. CN201310030129.2 introduces an aluminate cement-based carbon dioxide corrosion resistant cement system for well cementation; the weight portions of the components are as follows: 100 parts of aluminate cement, 40 parts of water, 8-12 parts of sodium phosphate, 0.4-0.6 part of oil well cement defoaming agent and 0-3.5 parts of retarder.
Due to the adoption of novel CO2The dry hot rock production well in an EGS mode requires a well cementation cement sheath with high temperature strength stability and CO resistance2The corrosion and the low thermal conductivity of the cement system can not effectively meet the requirement of novel CO2-performance requirements of hot dry rock high temperature cementing cement in EGS mode.
Disclosure of Invention
The present invention has been made to solve the above problems, and the present invention provides a novel CO2High temperature corrosion resistant cementing cement system for hot dry rock in EGS mode, with set cement at high temperature, high pressure and high CO concentration2Has excellent corrosion resistance, high temperature resistance and heat preservation performance under the condition, and can meet the requirement of novel CO2And the dry hot rock production well in the EGS mode is sealed for a long time, the requirement on energy consumption is reduced, and the guarantee is provided for exploration and development, efficient production and environmental protection.
The invention is realized by the following technical scheme:
novel CO2The high-temperature corrosion-resistant well cementation cement system for the dry hot rock in the EGS mode comprises the following raw materials in percentage by weight:
75-88% of low hydration heat cement or low calcium-silicon ratio cement;
11-20% of high-temperature strength reinforcing agent;
CO resistance21 to 5 percent of corrosive materials.
Preferably, C of the low hydration heat cement2The S content is more than or equal to 40 percent, and the specific surface area is 280-330m2The hydration heat is less than or equal to 240kJ/Kg after 7 days.
Preferably, the low calcium silicon ratio cement has a chemical composition with a calcium oxide/silicon oxide molar ratio of 1.8-2.2.
Preferably, the high-temperature strength stabilizer is waste concrete, and SiO of the waste concrete2The content is more than or equal to 70 percent, and the powder is fineThe degree is more than or equal to 300 meshes.
Preferably, the anti-CO is2The corrosive material is one or more of mica powder and polyether-ether-ketone resin ultrafine powder.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) according to the invention, the well cementation material has good high-temperature additive adaptability and high compressive strength: the low-heat cement or the low-calcium-silicon ratio cement has better compressive strength stability and admixture adaptability under the condition of high-temperature hydrothermal environment, and the mechanism of the method is as follows: on one hand, during the hydration reaction of the cement with high calcium-silicon ratio, calcium-silicon ions in hydration products are not in an ideal uniform distribution state due to the problem of slow speed of a quartz sand solution, and the non-uniform distribution state causes the generation of the hydration products with high calcium-silicon ratio in partial areas, which causes the problem of the high-temperature strength decline of the set cement. The low-heat cement and the low-calcium-silicon cement are lower than the calcium hydroxide content in a cement hydration product, the required high-temperature strength stabilizer and high-temperature strength reinforcing agent are less in dosage, the uniformity of the cement hydration product is improved, and the high-temperature strength stability of the high-temperature cementing cement can be effectively improved by improving the microscopic and mesoscopic structure distribution of the cement high-temperature hydration product; on the other hand, the low-heat cement and the low-calcium-silicon ratio cement have high content of dicalcium silicate, small specific surface area of the cement, slower hydration speed under the high-temperature condition, and better doping amount and adaptability of the required high-temperature retarder and the water loss reducer.
(2) In the invention, the well cementing material has the characteristics of environmental protection and low cost: the waste concrete mainly comprises cement, sand and aggregate, wherein the chemical components in the sand and stone aggregate in part of the concrete mainly comprise silicon dioxide, and the waste concrete serving as a high-temperature strength stabilizer has the following characteristics that:
a. green and environment-friendly: waste concrete is common solid waste in urban construction, becomes an important environmental pollution source, and becomes one of effective ways for treating the waste after being ground as a strength stabilizer of high-temperature well cementation cement;
b. low cost and wide source: after the low-heat cement or the cement with low calcium-silicon ratio is adopted as a main material, the requirements on the components of the high-temperature strength stabilizer are reduced, the requirements on the content of silicon dioxide in a siliceous material are relaxed, the sources of the high-temperature strength stabilizer are expanded, and the cost of the high-temperature well cementation cement is reduced;
c. the added high-temperature strength reinforcing agent contains an active aluminum tetrahedron structure which can play two roles in high-temperature well cementation cement, namely, calcium ions released in the hydration process of the cement are quickly adsorbed, and the nucleation-crystallization-growth process of a cement hydration product is reduced, so that the hydration speed of the cement under the high-temperature condition is reduced; and secondly, the alundum tetrahedron finally enters a cement hydration product structure to play a role in stabilizing the trabecite structure, so that the high-temperature resistance of the well cementation cement stone is improved.
(3) In the invention, the cementing material has good CO resistance2Corrosion performance: the added CO2 corrosion-resistant material and free calcium hydroxide in the set cement undergo a chemical reaction to generate a new-phase calcium silicate hydrate gel, so that effective cementing components reduced by corrosion are further compensated, reaction sources of corrosive ions are reduced, and the cementing performance of the set cement is effectively improved; in addition, the cement can form good gradation with cement particles, so that the compactness of the set cement is improved, and the permeability of the set cement is reduced; and a network structure which is intertwined and woven with each other can be formed in a cement system, so that the cement structure can be obviously improved, and the corrosion of corrosive media to cement components is hindered. The material also has a lower heat conductivity coefficient, can play a role in heat preservation and heat insulation to a certain extent, and reduces the heat loss of the production well.
Drawings
FIG. 1 is the 1# densification experiment profile of example 5.
FIG. 2 is the 2# densification experiment profile of example 5.
FIG. 3 is the 3# densification experiment profile of example 5.
FIG. 4 is a thermogram of the sample of example 6 after corrosion for 14d in a given environment.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. The invention is further illustrated by reference to the following examples, which include, but are not limited to, the following. The low hydration heat cement and the low calcium-silicon ratio cement are provided by Jiahua special cement limited, the high-temperature strength stabilizer, the high-temperature strength reinforcing agent and the CO2 corrosion-resistant material are commercially available products, and the high-temperature retarder and the high-temperature fluid loss reducer are provided by Sichuan Asahi Genechen new material limited. The examples are not specifically indicated, but are in weight percent.
Example 1
Novel CO2An EGS-mode high-temperature corrosion-resistant well cementation cement system for hot dry rock relates to the technical field of oil and gas well cementing, and adopts cement with low calcium-silicon ratio as basic cement and C2The S content is 50.2 percent, and the specific surface area is 283m2The hydration heat is less than or equal to 182kJ/Kg after 7 days; crushing and grinding waste concrete, and controlling the fineness of powder to 300 meshes, wherein SiO in the powder2The content is 73.4%; CO resistance2The corrosive material is mica powder, and comprises the following components:
taking the raw materials according to the specific component proportion in the table, mixing, preparing cement paste according to GB/T19139, and obtaining the well cementation cement system with the water cement ratio of 0.45.
Example 2
In the embodiment, the cement with low calcium-silicon ratio is used as basic cement, and the concrete components are as follows:
taking the raw materials according to the specific component proportion in the table, mixing, preparing cement slurry according to GB/T19139, and obtaining the well cementation cement slurry with the water cement ratio of 0.45.
Example 3
This embodiment uses lowUsing hydrated hot cement as basic cement, using low hydrated hot cement as basic cement, C2The S content is 44.5 percent, and the specific surface area is 325m2The hydration heat is less than or equal to 216kJ/Kg after 7 days, and the concrete composition is as follows:
taking the raw materials according to the specific component proportion in the table, mixing, preparing cement slurry according to GB/T19139, and obtaining the well cementation cement slurry with the water cement ratio of 0.45.
Comparative example 1
The scheme is conventional high-temperature well cementation cement, which specifically comprises the following components: 65% of G-level high-resistance oil well cement, 35% of high-temperature strength stabilizer and 0.45% of water-cement ratio.
Example 4
The cement paste samples obtained in the above examples 1-3 and comparative example 1 were poured into a copper mold to be molded, and then placed into a high-temperature curing kettle to be cured at 240 ℃ for 2d, 7d and 14 d. The compression strength test is carried out by adopting an NYSQ-2017 compression tester, and the permeability measurement is carried out on the cured products of the high-temperature well cementation cement examples 1-3 and the comparative example 1 according to a standard SY/T6466-2000 oil well cement stone high temperature resistance performance evaluation method, and the detection results are shown in the following table 1-1.
Tables 1 to 1:
as can be seen from the data in Table 1-1, the compressive strength of examples 1-3 did not deteriorate when cured at 240 ℃ for a certain period of time, whereas the strength of comparative example 1 deteriorated. While in examples 1-3, the permeability decreased at 240 ℃, although the increase was less; but the permeability of comparative example 1 was greatly increased. The compactness is a key intrinsic factor influencing the acid gas corrosion resistance of the set cement. The cement paste system provided by the technical scheme of the invention has higher internal structure compactness, so that the high temperature resistance is better.
Example 5
This example is a study of the cement slurry thickening time obtained in example 1.
3 parts of the cement slurry samples in example 1 were subjected to a 220 ℃ high temperature thickening test, wherein the thickening time is shown in tables 1-2, and the thickening test curve is shown in figures 1-3.
Tables 1-2:
from the experimental data in tables 1-2, it can be seen that:
the resulting cement paste of example 1 is high temperature resistant, CO resistant2The thickening time of the corroded well cementation cement system is adjustable, which shows that the cement has high temperature resistance and CO resistance2The corrosion cementing cement system has good compatibility of each component substance with a high-temperature retarder, a fluid loss agent and the like, has controllable working time, and is beneficial to improving the construction safety of high-temperature cementing operation.
Example 6
This example is a CO-resistant cement paste obtained in example 12And (5) inspecting the corrosion performance.
The experimental theoretical basis in this example is: considering that the product after the cement stone is corroded is calcium carbonate, and the decomposition temperature range of the calcium carbonate is 600-770 ℃, the weight loss amount of the cement stone at the temperature of 600-770 ℃ is the decomposition quality of the corrosion product calcium carbonate, so that the weight loss amount of the cement stone in the temperature range can be measured by a thermogravimetric analysis means to represent the corrosion condition of the cement stone under given conditions, and the larger the weight loss amount of the sample in the temperature range is, the more easily corroded the sample is, otherwise, the more corrosion-resistant the sample is.
In this example, the raw materials were prepared according to the component ratios of example 1-3 and comparative example 1, mixed, and the cement paste was prepared according to the GB/T19139 standard, and then poured into a copper mold to be molded and placed in a high temperature curing kettle for curing at 180 ℃ for a curing period of 3 days. The cured products of the high-temperature well cementation cement slurry obtained in the previous examples 1-3 and the comparative example 1 are subjected to thermogravimetric analysis measurement, and CO is introduced in comparison2Weight loss after corrosion of the sample. Wherein the total pressure is 30MPa, and CO is introduced2The partial pressure was 6 MPa.
The set of cement curing, corrosion conditions, and thermogravimetric analysis data used in the tests are shown in tables 1-4 below, and fig. 4 is a weight loss curve of corrosion 14d for samples of examples 1-3 and comparative example 1. Wherein the sample thermogravimetric test is carried out on a thermal analyzer produced by Mettle Toledo company, the heating rate is 10 ℃/min, and the nitrogen protection is carried out.
Combining tables 1-4, fig. 4, it can be seen that: CO resistance of the Cement paste-cured product samples obtained in examples 1 to 3 according to the technical solution of the present invention2The corrosion resistance is far greater than that of the existing cement paste sample of comparative example 1.
According to the above cases, by adopting the technical scheme of the invention, the high-temperature strength stability and the corrosion resistance of the well cementation cement are effectively improved by utilizing the low hydration heat cement and the low calcium-silicon ratio cement and adding the specific high-temperature strength stabilizer, the high-temperature strength reinforcing agent and the corrosion resistant material, and the obtained product after the cement slurry is solidified is subjected to high-temperature, high-pressure and high-concentration CO2Under the condition, the material has excellent corrosion resistance, high temperature resistance and heat preservation performance, and can meet the requirements of novel CO2-performance requirements for cementing engineering of hot dry rock production wells in EGS mode.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiments according to the technical spirit of the present invention are included in the scope of the present invention.
Claims (1)
1. CO (carbon monoxide)2The high-temperature corrosion-resistant well cementation cement for the hot dry rock in the EGS mode is characterized by comprising the following raw materials in percentage by weight:
75-88% of low hydration heat cement or low calcium-silicon ratio cement;
11-20% of high-temperature strength reinforcing agent;
CO resistance21-5% of corrosive material;
c of the low hydration heat cement2The S content is more than or equal to 40 percent, and the specific surface area is 280-330m2The hydration heat is less than or equal to 240kJ/kg after 7 days;
the low calcium silicon ratio cement has the chemical components that the molar ratio of calcium oxide to silicon oxide is 1.8-2.2;
the high-temperature strength stabilizer is waste concrete, and SiO of the waste concrete2The content is more than or equal to 70 percent, and the powder fineness is more than or equal to 300 meshes;
the anti-CO2The corrosive material is one or more of mica powder and polyether-ether-ketone resin ultrafine powder.
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| CN114350334B (en) * | 2022-01-20 | 2022-12-16 | 嘉华特种水泥股份有限公司 | High-temperature-resistant tough well cementation cement slurry system |
| CN115432958B (en) * | 2022-08-25 | 2023-04-14 | 嘉华特种水泥股份有限公司 | Is suitable for CO 2 Well cementation cement slurry system of enhanced geothermal system |
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| CN102559161A (en) * | 2011-12-16 | 2012-07-11 | 中国石油大学(华东) | Carbon dioxide corrosion resisting cement system for oil-gas well cementation |
| WO2016082188A1 (en) * | 2014-11-28 | 2016-06-02 | 吉林大学 | Hot dry rock multi-cycle heating system and production method therefor |
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| CN109250972A (en) * | 2018-11-26 | 2019-01-22 | 中国海洋石油集团有限公司 | A kind of thick oil thermal extraction high temperature resistant Elastic well cementation cement paste system and preparation method thereof |
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Patent Citations (5)
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| CN102559161A (en) * | 2011-12-16 | 2012-07-11 | 中国石油大学(华东) | Carbon dioxide corrosion resisting cement system for oil-gas well cementation |
| WO2016082188A1 (en) * | 2014-11-28 | 2016-06-02 | 吉林大学 | Hot dry rock multi-cycle heating system and production method therefor |
| CN108947344A (en) * | 2018-07-23 | 2018-12-07 | 中国石油集团川庆钻探工程有限公司 | The anti-H of oil gas well cementing operation2S gas attack mortar architecture |
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