WO2024259914A1 - 用于水泥浆的防腐蚀材料、抗二氧化碳腐蚀水泥浆及其制备方法和应用 - Google Patents

用于水泥浆的防腐蚀材料、抗二氧化碳腐蚀水泥浆及其制备方法和应用 Download PDF

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Publication number
WO2024259914A1
WO2024259914A1 PCT/CN2023/138201 CN2023138201W WO2024259914A1 WO 2024259914 A1 WO2024259914 A1 WO 2024259914A1 CN 2023138201 W CN2023138201 W CN 2023138201W WO 2024259914 A1 WO2024259914 A1 WO 2024259914A1
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Prior art keywords
corrosion
parts
cement slurry
mixture
component
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PCT/CN2023/138201
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English (en)
French (fr)
Inventor
张弛
张晓兵
靳建洲
于永金
曲从锋
张华�
齐奉忠
刘慧婷
夏修建
张佳滢
翟显治
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China National Petroleum Corp
CNPC Engineering Technology R&D Co Ltd
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China National Petroleum Corp
CNPC Engineering Technology R&D Co Ltd
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Priority claimed from CN202310740303.6A external-priority patent/CN119176686B/zh
Application filed by China National Petroleum Corp, CNPC Engineering Technology R&D Co Ltd filed Critical China National Petroleum Corp
Priority to EP23942180.3A priority Critical patent/EP4711347A1/en
Publication of WO2024259914A1 publication Critical patent/WO2024259914A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • 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 or shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • 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
    • 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
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B33/00—Sealing or packing boreholes or wells
    • E21B33/10—Sealing or packing boreholes or wells in the borehole
    • E21B33/13—Methods or devices for cementing, for plugging holes, crevices or the like
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/60—Agents for protection against chemical, physical or biological attack
    • C04B2103/61—Corrosion inhibitors
    • 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
    • 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
    • C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
    • 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
    • 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
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/32—Anticorrosion additives
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the invention relates to the technical field of cement slurry for cementing oil and gas wells, and in particular to an anti-corrosion material for cement slurry, carbon dioxide corrosion resistant cement slurry, and a preparation method and application thereof.
  • Carbon capture, utilization and storage is currently the only feasible technology that can significantly reduce CO2 emissions.
  • the integrity of the cement sheath is a key technology that determines whether the CO2 geological storage project can be successfully implemented and ultimately achieve long-term storage.
  • CO2 exists in the state of supercritical CO2 underground, with characteristics such as low viscosity and strong permeability.
  • the silicate cement system is strongly alkaline and CO2 is an acidic gas.
  • the cement sheath Under the long-term erosion of CO2 , the cement sheath is very likely to be over-carbonated and decalcified, causing changes in composition, strength attenuation, and increased porosity and permeability, resulting in the destruction of the overall structure of the cement sheath, endangering the long-term effective sealing of the wellbore.
  • the CO2 anti-corrosion materials for oil well cement mainly use ultra-fine inert materials and active siliceous materials, such as the addition of inert ultra-fine barite and other materials by the Sinopec Dezhou Research Institute and the addition of fly ash, silica powder and other active materials by Li Guanying of National Cheng Kung University in Taiwan.
  • the permeability of cement paste should be reduced and the alkalinity of cement paste should be reduced by reacting with cement minerals to improve the anti- CO2 corrosion performance of cement paste.
  • CN114133172A discloses a carbon dioxide corrosion resistant cement slurry in cementing and a preparation method thereof.
  • the invention adopts silicate cement, nano-silicon dioxide, UF cellulose fiber, a fluid loss reducer and a dispersant to obtain a CO2 corrosion resistant cement slurry.
  • the nano-silicon dioxide fills and plugs the micropores inside the cement stone, participates in the hydration reaction to increase the Si/Ca of the hydration product, and improves the corrosion resistance of the hydration product.
  • the UF cellulose improves the mechanical properties of the cement stone.
  • the applicable temperature range is not given. The temperature in the embodiment is 60°C, the applicable temperature range is small, and the system adaptability is insufficient.
  • the purpose of the present invention is to overcome the problem that cement stone cannot be continuously protected against corrosion after being invaded by CO2 corrosive medium in the prior art, and to provide an anti-corrosion material for cement slurry, carbon dioxide corrosion resistant cement slurry, and a preparation method and application thereof.
  • the carbon dioxide corrosion resistant cement slurry prepared by the anti-corrosion material of the present invention has the characteristics of high compressive strength, low permeability, good sedimentation stability, good rheology, and a wide applicable temperature range after corrosion under the corrosion conditions of CO2 geological storage wells, thereby ensuring long-term effective sealing of CO2 geological storage wells.
  • the present invention provides a first aspect of an anti-corrosion material for cement slurry.
  • the anti-corrosion material comprises a mixture A and a mixture B; wherein the mixture A comprises activated carbon, nano-silicon dioxide and nano-alumina; the mixture B comprises a component C and a component D; the component C is selected from diatomaceous earth and/or fly ash; and the component D is selected from one or more of metakaolin, pumice and coal gangue.
  • the mass ratio of activated carbon, nano-silicon dioxide and nano-alumina is 1:0.05-0.1:0.05-0.1.
  • the mass ratio of component C to component D is 1-2:1.
  • the mass ratio of mixture A to mixture B is 1:2-4.
  • the average particle size of the activated carbon is 40-60 ⁇ m.
  • the SiO 2 content of the nano-silicon dioxide is greater than 99%, and the average particle size is 30-40 nm.
  • the Al 2 O 3 content of the nano-alumina is greater than 99%, and the average particle size is 10-30 nm.
  • the average particle size of component C is 10-20 ⁇ m.
  • the average particle size of component D is 20-40 ⁇ m.
  • component C Mixing component C and component D to obtain a mixture B; wherein the component C is selected from diatomaceous earth and/or fly ash; and the component D is selected from one or more of metakaolin, pumice and coal gangue;
  • the mixture A and the mixture B are mixed under a low stirring rate condition and then stirred at a high speed to obtain the anti-corrosion material.
  • the low stirring rate is 3800-4200 r/min
  • the high-speed stirring rate is 11500-12500 r/min.
  • the third aspect of the present invention provides the use of the anti-corrosion material described in the first aspect or the anti-corrosion material prepared by the preparation method described in the second aspect in cement slurry, preferably in cement slurry resistant to carbon dioxide corrosion.
  • the fourth aspect of the present invention provides a carbon dioxide corrosion resistant cement slurry, which is made of the following raw materials in parts by weight: 100 parts of G-grade oil well cement, 2-6 parts of anti-corrosion material, 2-5 parts of microsilicon, 3-6 parts of reinforcing material, 3-5 parts of expansion toughening material, 1-3 parts of latex powder, 0-2 parts of stabilizer, 0.3-2 parts of dispersant, 2-5 parts of fluid loss reducer, 0.1-2 parts of retarder, 0.2-0.5 parts of defoaming agent and 48-56 parts of water, wherein the anti-corrosion material is the anti-corrosion material described in the first aspect above or the anti-corrosion material prepared by the preparation method described in the second aspect above.
  • the dry mix and the wet mix are mixed to obtain carbon dioxide corrosion resistant cement slurry.
  • the sixth aspect of the present invention provides the use of the carbon dioxide corrosion resistant cement slurry described in the fourth aspect or the carbon dioxide corrosion resistant cement slurry prepared by the preparation method described in the fifth aspect in cementing operations of oil and gas wells.
  • the use temperature of the carbon dioxide corrosion resistant cement slurry is 30-150°C.
  • the applicable temperature range of cement slurry prepared by using the anti-corrosion material for cement slurry provided by the present invention is 30-150°C, the compressive strength of cement stone after corrosion is greater than 20MPa, and the permeability is less than 0.1mD, or even less than 0.05mD, significantly improves the ability of cement paste to resist CO2 corrosion, while having no adverse effects on other engineering properties of cement slurry, and can ensure long-term effective sealing of the cement ring under CCUS corrosion conditions.
  • the carbon dioxide corrosion resistant cement slurry of the present invention has good corrosion resistance in a CO2 corrosion environment. Before corrosion, the cement stone has high compressive strength and dense structure. After corrosion, the cement stone has no obvious decline in compressive strength, low permeability, good mechanical properties, good sedimentation stability, good rheological properties and other comprehensive properties. It is suitable for CO2 corrosion resistant cement slurry systems with temperatures of 30-150°C and below, ensuring the cementing quality of CCUS wells, and ensuring the long-term effective sealing performance of the cement ring under CCUS corrosion conditions, thereby achieving efficient CO2 storage.
  • a first aspect of the present invention provides an anti-corrosion material for cement slurry, the anti-corrosion material comprising a mixture A and a mixture B; wherein the mixture A comprises activated carbon, nano-silicon dioxide and nano-alumina; the mixture B comprises a component C and a component D; the component C is selected from diatomaceous earth and/or fly ash; the component D is selected from one or more of kaolin, pumice and coal gangue.
  • the mixture A comprises activated carbon, nano silicon dioxide and nano aluminum oxide.
  • Silica and nano-alumina are adsorbed in the pores of activated carbon and can be slowly released for long-lasting and repairing effects.
  • Mixture A mainly works in the later stage.
  • the mixture B has a strong volcanic ash activity, and the volcanic ash reaction occurs first, consuming Ca(OH) 2 in the cement stone, generating dense substances such as hydrated calcium silicate and hydrated calcium aluminate, and adhering to the outside of the cement stone to play a protective role, preventing CO2 from continuing to penetrate into the cement stone, that is, a protective film is initially formed outside the cement stone, and as the hydration reaction continues, the hydration products such as hydrated calcium silicate and hydrated calcium aluminate are continuously consumed, and the protective film is destroyed, resulting in signs of damage to the cement stone microstructure again.
  • the mixture A slowly releases the nano-silicon dioxide and nano-alumina therein, plays a filling and plugging role, and forms a dense protective film outside the cement stone.
  • the nano-silicon dioxide continues to react with the Ca(OH) 2 in the cement stone, preventing the acidic gas from continuing to enter the cement stone, that is, the mixture A can play a role in reinforcing and encrypting the outer cement stone protective film, thereby achieving long-term and effective anti-corrosion of the cement stone.
  • the present invention achieves long-term anti-corrosion by optimizing the formula of the anti-corrosion material, and the long-term anti-corrosion effect is good.
  • the invention mixes the mixture A and the mixture B, so the operation is simple and convenient and the feasibility is strong.
  • the mass ratio of activated carbon, nano-silicon dioxide and nano-alumina is 1:0.05-0.1:0.05-0.1.
  • the mass ratio of component C to component D is 1-2:1.
  • the mass ratio of mixture A to mixture B is 1:2-4.
  • the carbon dioxide corrosion resistant cement slurry made from the above raw materials has good corrosion resistance in a CO2 corrosion environment.
  • the cement stone has a high compressive strength and a dense structure before corrosion. After corrosion, the compressive strength of the cement stone has no obvious decline (the strength decline rate is less than 20%), and the permeability is less than 0.1mD, even less than 0.05mD.
  • the cement slurry containing the above anti-corrosion materials has an applicable temperature range of 30-150°C, which can significantly improve the anti- CO2 corrosion ability of cement stone. After corrosion, the compressive strength of cement stone is greater than 20MPa, and the permeability is small. At the same time, it has no adverse effect on other properties of cement stone, and can ensure the long-term effective sealing performance of cement ring under CCUS corrosion conditions.
  • the average particle size of the activated carbon is 40-60 ⁇ m.
  • the SiO 2 content of the nano-silicon dioxide is greater than 99%, and the average particle size is 30-40 nm.
  • the Al 2 O 3 content of the nano-alumina is greater than 99%, and the average particle size is 10-30 nm.
  • the average particle size of component C is 10-20 ⁇ m.
  • the average particle size of component D is 20-40 ⁇ m.
  • a second aspect of the present invention provides a method for preparing an anti-corrosion material for cement slurry, the preparation method comprising:
  • component C Mixing component C and component D to obtain a mixture B; wherein the component C is selected from diatomaceous earth and/or fly ash; and the component D is selected from one or more of metakaolin, pumice and coal gangue;
  • the mixture A and the mixture B are mixed under a low stirring rate condition and then stirred at a high speed to obtain the anti-corrosion material.
  • the low stirring rate is 3800-4200 r/min
  • the high-speed stirring rate is 11500-12500 r/min.
  • the mixture A activated carbon, nano dioxide
  • the mass ratio of silicon to nano-alumina is 1:0.05-0.1:0.05-0.1.
  • the mass ratio of component C to component D is 1-2:1.
  • the mass ratio of mixture A to mixture B is 1:2-4.
  • the activated carbon has a particle size of 40-60 ⁇ m.
  • the SiO 2 content of the nano-silicon dioxide is greater than 99%, and the average particle size is 30-40 nm.
  • the Al 2 O 3 content of the nano-alumina is greater than 99%, and the average particle size is 10-30 nm.
  • the average particle size of component C is 10-20 ⁇ m.
  • the average particle size of component D is 20-40 ⁇ m.
  • the third aspect of the present invention provides the use of the anti-corrosion material described in the first aspect or the anti-corrosion material prepared by the preparation method described in the second aspect in cement slurry, preferably in cement slurry resistant to carbon dioxide corrosion.
  • the anti-corrosion material of the present invention is used to prepare carbon dioxide corrosion resistant cement slurry, which can be implemented simply and conveniently.
  • the mixture B undergoes a volcanic ash reaction, consumes Ca(OH) 2 in the cement stone, produces hydrated calcium silicate, hydrated calcium aluminate and other substances, protects the cement stone from carbon dioxide corrosion, and initially forms a protective film.
  • the hydration product is continuously consumed, resulting in signs of damage to the microstructure of the cement stone.
  • the mixture A slowly releases the nano silicon dioxide and nano aluminum oxide therein, plays a filling and plugging role, forms a dense protective film outside the cement stone, and at the same time, the nano silicon dioxide continues to react with the Ca(OH) 2 in the cement stone, preventing the acidic gas from continuing to enter the cement stone. Therefore, the prepared cement slurry can play a role of lasting carbon dioxide corrosion resistance.
  • the fourth aspect of the present invention provides a carbon dioxide corrosion resistant cement slurry, which is made of the following raw materials in parts by weight: 100 parts of G-grade oil well cement, 2-6 parts of anti-corrosion material, 2-5 parts of microsilicon, 3-6 parts of reinforcing material, 3-5 parts of expansion toughening material, 1-3 parts of latex powder, 0-2 parts of stabilizer, 0.3-2 parts of dispersant, 2-5 parts of fluid loss reducer, 0.1-2 parts of retarder, 0.2-0.5 parts of defoaming agent and 48-56 parts of water, wherein the anti-corrosion material is the anti-corrosion material described in the first aspect above or the anti-corrosion material prepared by the preparation method described in the second aspect above.
  • the carbon dioxide corrosion-resistant cement slurry prepared by the above raw materials has good corrosion resistance in a CO2 corrosion environment.
  • the cement stone has high compressive strength and dense structure before corrosion. After corrosion, the compressive strength of the cement stone does not decline significantly, the permeability is small, and the mechanical properties are good. At the same time, the comprehensive properties such as sedimentation stability and rheology are good. It can be used in a CO2 corrosion-resistant cement slurry system with a temperature of 30-150°C and below, to ensure the cementing quality of CCUS wells and realize efficient CO2 storage.
  • the SiO 2 content of the micro-silicon is not less than 90%, the average particle size is 5-10 ⁇ m, and the 45 ⁇ m sieve residue is ⁇ 5%.
  • the reinforcing material is selected from reinforcing materials for cementing oil well cement.
  • the reinforcing material is selected from inorganic mineral powder materials, preferably mineral powder DRB-1S produced by China National Petroleum Corporation Engineering Technology Research Institute Co., Ltd.
  • the expansion toughening material is selected from the expansion toughening material for cementing oil well cement.
  • the expansion toughening material is selected from rubber materials, preferably rubber DRE-3S.
  • the latex powder is selected from latex powder for cementing oil well cement.
  • the latex powder is selected from polymers, preferably polymer DRT-1S.
  • the stabilizer is selected from stabilizers for cementing oil well cement.
  • the stabilizer is selected from attapulgite materials, preferably ore powder DRK-2S.
  • the dispersant is selected from polystyrene sulfonate compounds and/or condensation products of formaldehyde and acetone.
  • the fluid loss agent is selected from polyacrylamide compounds.
  • the retarder is selected from acrylamide compounds.
  • the defoaming agent is selected from one or more of tributyl phosphate, polyoxypropylene glycerol and polydimethylsiloxane.
  • a fifth aspect of the present invention provides a method for preparing carbon dioxide corrosion resistant cement slurry, the preparation method comprising:
  • the dry mix and the wet mix are mixed to obtain carbon dioxide corrosion resistant cement slurry.
  • the sixth aspect of the present invention provides the use of the carbon dioxide corrosion resistant cement slurry described in the fourth aspect or the carbon dioxide corrosion resistant cement slurry prepared by the preparation method described in the fifth aspect in cementing operations of oil and gas wells.
  • the use temperature of the carbon dioxide corrosion resistant cement slurry is 30-150°C.
  • the method for preparing carbon dioxide corrosion resistant cement slurry specifically comprises the following steps:
  • Activated carbon, nano-silicon dioxide and nano-alumina are mixed uniformly in a mass ratio of 1:0.05-0.1:0.05-0.1 to obtain a mixture A; at least one of diatomaceous earth and fly ash is mixed uniformly with at least one of metakaolin, pumice and coal gangue in a mass ratio of 1-2:1 to obtain a mixture B; the mixture A and the mixture B are mixed uniformly in a mass ratio of 1:2-4 to obtain an anti-corrosion material;
  • G-grade oil well cement is high sulfate resistance (HSR) G-grade oil well cement, produced by Dalian Cement Group Co., Ltd.
  • Microsilicon Its SiO2 content is 95%, the average particle size is 8 ⁇ m, and the 45 ⁇ m sieve residue is 4.2%.
  • the reinforcing material is the ore powder DRB-1S for cementing oil well cement, China National Petroleum Corporation Produced by Engineering Technology Research Institute Co., Ltd.
  • the expansion toughening material is DRE-3S, a toughening material rubber for oil well cementing, produced by China National Petroleum Corporation Engineering Technology Research Institute Co., Ltd.
  • the latex powder is latex powder polymer DRT-1S for oil well cementing, produced by China National Petroleum Corporation Engineering Technology Research Institute Co., Ltd.
  • the stabilizer is high temperature stabilizer ore powder DRK-2S for cementing oil well cement, produced by China National Petroleum Corporation Engineering Technology Research Institute Co., Ltd.
  • the dispersant is an aldehyde-ketone polycondensate type DRS-1S for oil well cementing, produced by China National Petroleum Corporation Engineering Technology Research Institute Co., Ltd.
  • the fluid loss reducer is acrylamide type DRF-1S for cementing oil well cement, produced by China National Petroleum Corporation Engineering Technology Research Institute Co., Ltd.
  • the retarder is an organic acid retarder DRH-1L for oil well cementing, produced by China National Petroleum Corporation Engineering Technology Research Institute Co., Ltd.
  • the defoaming agent is an organic ester defoaming agent DRX-1L for oil well cementing, produced by China National Petroleum Corporation Engineering Technology Research Institute Co., Ltd.
  • the experiment was carried out to evaluate the conventional engineering properties (density, fluidity, API water loss) of the cement slurry system as well as the compressive strength and permeability before and after corrosion.
  • the main experimental instruments are: 30-60 type tile edge mixer; TG7370D type booster curing kettle, Shenyang Tiger Petroleum Instrument and Equipment Manufacturing Co., Ltd.; HH-420 type constant temperature digital display water tank, Changzhou Yineng Experimental Instrument Factory; YAW-300B hydraulic pressure testing machine, Jinan Xinshijin Testing Machine Co., Ltd.; CO2 corrosion environment simulation system, a product of China National Petroleum Corporation Engineering Technology Research Institute Co., Ltd.
  • Fluidity Tested in accordance with national standard GB/T 19139-2012 “Test methods for oil well cement”.
  • API water loss Tested in accordance with national standard GB/T 19139-2012 "Test methods for oil well cement”.
  • Cement stone corrosion is cured by using the " CO2 corrosion environment simulation system" invented by China National Petroleum Corporation Engineering Technology Co., Ltd. or a device capable of pressurized curing in a CO2 gas/liquid environment.
  • Strength loss rate (T2-T1)/T1, where T1 is the compressive strength of cement paste before corrosion and T2 is the compressive strength of cement paste after corrosion.
  • a method for preparing an anti-corrosion material comprises the following steps:
  • Activated carbon, nano-silicon dioxide and nano-alumina are fully mixed and uniformly mixed in a mass ratio of 1:0.05:0.05.
  • the activated carbon is commercially available and has a mesh size of 325.
  • the nano-silicon dioxide is commercially available and has a SiO2 content of 99.5% and an average particle size of 30 nm.
  • the nano-alumina is commercially available and has an average particle size of 30 nm and an Al2O3 content of 99.3%.
  • the three substances are uniformly mixed to obtain a mixture A.
  • a method for preparing an anti-corrosion material comprises the following steps:
  • Activated carbon, nano-silicon dioxide and nano-alumina are fully mixed and uniformly mixed in a mass ratio of 1:0.1:0.1.
  • the nano-silicon dioxide is commercially available, with a SiO2 content of 99.9% and an average particle size of 40 nm;
  • the nano-alumina is commercially available, with an average particle size of 20 nm and an Al2O3 content of 99.9%.
  • the above three substances are uniformly mixed to obtain a mixture A;
  • a method for preparing an anti-corrosion material comprises the following steps:
  • Activated carbon, nano silicon dioxide and nano aluminum oxide are fully mixed and uniformly mixed in a mass ratio of 1:0.2:0.1.
  • the activated carbon is commercially available and has a mesh size of 325.
  • the nano silicon dioxide is commercially available and has a SiO2 content of 99.8% and an average particle size of 30 nm.
  • the nano aluminum oxide is commercially available and has an average particle size of 30 nm and an Al2O3 content of 99.5%.
  • the three substances are uniformly mixed to obtain a mixture A.
  • the diatomaceous earth and coal gangue are mixed and stirred evenly in a mass ratio of 2:1 to obtain an anti-corrosion material.
  • nano-silicon dioxide and nano-alumina thoroughly in a mass ratio of 1:1.
  • the nano silicon dioxide is commercially available, with a SiO2 content of 99.5% and an average particle size of 30 nm;
  • the nano aluminum oxide is commercially available, with an average particle size of 30 nm and an Al2O3 content of 99.3%.
  • the two substances are uniformly mixed to obtain a mixture A;
  • the cement slurry formula is as follows by weight percentage: 100 parts of G-grade oil well cement, 3 parts of anticorrosive material obtained in Preparation Example 1, 3 parts of microsilicon, 5 parts of reinforcing material, 4 parts of expansion toughening material, 2 parts of latex powder, 1 part of stabilizer, 1 part of dispersant, 3 parts of fluid loss reducer, 0.5 parts of retarder, 0.2 parts of defoamer and 53 parts of water.
  • the cement slurry density is 1.88 g/cm 3 , and the experimental results are shown in Table 1.
  • the cement slurry formula is as follows by weight percentage: 100 parts of G-grade oil well cement, 3 parts of anticorrosive material obtained in Preparation Example 2, 3 parts of microsilicon, 5 parts of reinforcing material, 4 parts of expansion toughening material, 2 parts of latex powder, 1 part of stabilizer, 1 part of dispersant, 3 parts of fluid loss reducer, 0.5 parts of retarder, 0.2 parts of defoamer and 53 parts of water.
  • the cement slurry density is 1.88 g/cm 3 .
  • the experimental results are shown in Table 1.
  • the cement slurry formula was as follows by weight percentage: 100 parts of G-grade oil well cement, 5 parts of anticorrosion materials obtained in Preparation Example 2, 3 parts of microsilicon, 5 parts of reinforcing materials, 4 parts of expansion toughening materials, 2 parts of latex powder, 1 part of stabilizer, 1 part of dispersant, 3 parts of fluid loss additives, 0.5 parts of retarder, 0.2 parts of defoamer and 53 parts of water.
  • the cement slurry density was 1.88 g/cm 3 .
  • the experimental results are shown in Table 1.
  • the cement slurry formula is as follows by weight percentage: 100 parts of G-grade oil well cement, 6 parts of the anticorrosive material obtained in Preparation Example 2, 2 parts of microsilicon, 6 parts of reinforcing material, 3 parts of expansion toughening material, 1 part of latex powder, 2 parts of stabilizer, 2 parts of dispersant, 2 parts of fluid loss reducer, 2 parts of retarder, 0.2 parts of defoamer and 56 parts of water.
  • the density of the cement slurry is 1.88 g/cm 3 .
  • the experimental results are shown in Table 1.
  • the cement slurry formula is as follows by weight percentage: 100 parts of G-grade oil well cement, 2 parts of the anticorrosive material obtained in Preparation Example 2, 5 parts of microsilicon, 3 parts of reinforcing material, 6 parts of expansion toughening material, 3 parts of latex powder, 0.4 parts of stabilizer, 1 part of dispersant, 5 parts of fluid loss reducer, 0.1 parts of retarder, 0.2 parts of defoamer and 48 parts of water.
  • the density of the cement slurry is 1.88 g/cm 3 .
  • the experimental results are shown in Table 1.
  • the cement slurry formula is as follows by weight percentage: 100 parts of G-grade oil well cement, 3 parts of anti-corrosion materials obtained in Preparation 3, 3 parts of micro-silicon, 5 parts of reinforcing materials, 4 parts of expansion toughening materials, 2 parts of latex powder, 1 part of stabilizer, 1 part of dispersant, 3 parts of fluid loss reducer, 0.5 parts of retarder, 0.2 parts of defoamer and 53 parts of water.
  • the cement slurry density is 1.88 g/cm 3 , and the experimental results are shown in Table 1.
  • the cement slurry formula is as follows by weight percentage: 100 parts of G-grade oil well cement, 3 parts of anti-corrosion materials obtained in Preparation Comparative Example 1, 3 parts of micro-silicon, 5 parts of reinforcing materials, 4 parts of expansion toughening materials, 2 parts of latex powder, 1 part of stabilizer, 1 part of dispersant, 3 parts of fluid loss reducer, 0.5 parts of retarder, 0.2 parts of defoamer and 53 parts of water.
  • the cement slurry density is 1.88 g/cm 3 , and the experimental results are shown in Table 1.
  • the cement slurry formula is as follows by weight percentage: 100 parts of G-grade oil well cement, 3 parts of anti-corrosion materials obtained in Comparative Example 2, 3 parts of micro-silicon, 5 parts of reinforcing materials, 4 parts of expansion toughening materials, 2 parts of latex powder, 1 part of stabilizer, 1 part of dispersant, 3 parts of fluid loss reducer, 0.5 parts of retarder, 0.2 parts of defoamer and 53 parts of water.
  • the cement slurry density is 1.88 g/cm 3 , and the experimental results are shown in Table 1.
  • the cement slurry formula is as follows by weight percentage: 100 parts of G-grade oil well cement, 3 parts of microsilicon, 5 parts of reinforcing material, 4 parts of expansion toughening material, 2 parts of latex powder, 1 part of stabilizer, 1 part of dispersant, 3 parts of fluid loss reducer, 0.5 parts of retarder, 0.2 parts of defoamer and 53 parts of water.
  • the density of the cement slurry is 1.88 g/cm 3 .
  • the experimental results are shown in Table 1.
  • the fluidity of all embodiments is greater than 20cm, and the API water loss is less than 50mL, which meets the requirements of cementing construction.
  • the compressive strength of all embodiments after corrosion is greater than 20MPa, the strength loss rate is less than 20%, and the permeability is less than 0.1mD, with good performance, meeting the requirements of cementing sealing.
  • Example 2 From the experimental data of Example 2 and Examples 4 and 5, it can be seen that after the temperature changes, according to the needs The amount of different admixtures needs to be adjusted so that the resulting cement slurry system has good engineering performance. At the same time, after curing under corrosive conditions, the compressive strength is greater than 20MPa, the permeability is less than 0.05mD, and the anti-corrosion performance is good. That is, within the range of the amount of each material added, adjustments can be made according to different temperatures to meet the use requirements at different temperatures.
  • the cement slurry of the present invention has an applicable temperature range of 30-150°C, the compressive strength of the cement stone after corrosion is greater than 20MPa, and the permeability is less than 0.05mD, which significantly improves the anti- CO2 corrosion ability of the cement stone. At the same time, it has no adverse effect on other engineering properties of the cement slurry, and can ensure long-term effective sealing of the cement ring under CCUS corrosion conditions.

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Abstract

用于水泥浆的防腐蚀材料、抗二氧化碳腐蚀水泥浆及其制备方法和应用。该防腐蚀材料包括混合物A和混合物B；其中，所述混合物A包括活性炭、纳米二氧化硅和纳米氧化铝；所述混合物B包括组分C和组分D；所述组分C选自硅藻土和/或粉煤灰；所述组分D选自偏高岭土、浮石和煤矸石中的一种或多种。采用该防腐蚀材料制成的抗二氧化碳腐蚀水泥浆在CO 2腐蚀环境下具有良好的防腐蚀能力，腐蚀前水泥石抗压强度较高、结构致密，腐蚀后水泥石抗压强度无明显衰退、渗透率小、力学性能良好、沉降稳定性好、流变性好等综合性能，保障CCUS井固井质量，实现CO 2高效封存。

Description

用于水泥浆的防腐蚀材料、抗二氧化碳腐蚀水泥浆及其制备方法和应用
相关申请的交叉引用
本申请要求2023年06月21日提交的中国专利申请202310740303.6的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明涉及油气井固井水泥浆技术领域，具体涉及用于水泥浆的防腐蚀材料、抗二氧化碳腐蚀水泥浆及其制备方法和应用。
背景技术
碳捕获、利用与封存(CCUS)作为目前唯一能够大幅减少CO2排放的可行技术，固井水泥环完整性是决定CO2地质封存工程能否顺利实施并最终实现长期封存的关键技术。众所周知，CO2在井下以超临界CO2的状态存在，具有低粘度强渗透性等特点。与此同时，硅酸盐水泥体系呈强碱性而CO2是一种酸性气体，在CO2长龄期的侵蚀下，固井水泥环极易过度碳化脱钙，引起组分改变、强度衰减，孔隙度及渗透率增大，导致水泥环整体结构被破坏，危及井筒长期有效密封。
目前，针对CO2等酸性气体对固井水泥环的腐蚀问题，国内外普遍采用防腐蚀水泥浆体系。油井水泥CO2防腐材料主要采用超细惰性材料及活性硅质类材料，如中石化德州研究所加入惰性超细重晶石等材料和台湾成功大学的李冠颖等通过加入飞灰、硅粉等活性材料，通过物理紧密堆积效 应来降低水泥石的渗透率及与水泥矿物反应降低水泥石碱性来提高水泥石的抗CO2腐蚀性能，这种方式只是削弱溶蚀离子的交换源，尽量减缓CO2腐蚀介质的渗入速率，一旦腐蚀介质进入水泥石内部，将会对水泥石的凝胶结构继续造成破坏，无法继续发挥其抗腐蚀的作用，因此，抗腐蚀效果不是很理想。
CN114133172A公开一种固井中抗二氧化碳腐蚀水泥浆及其制备方法，采用硅酸盐水泥、纳米二氧化硅、UF纤维素纤维、降失水剂、分散剂，得到了抗CO2腐蚀水泥浆，纳米二氧化硅对水泥石内部微孔隙起到充填堵孔作用，参与水化反应提高水化产物Si/Ca，改善水化产物的防腐蚀能力，UF纤维素改善水泥石力学性能的，但是适用温度范围未给出，实施例中温度60℃，适用温度范围较小，体系适应性不足。
因此，亟需开发一种在CO2腐蚀环境下具有良好的防腐蚀能力的水泥浆，以保障CCUS井固井质量，实现CO2高效封存。
发明内容
本发明的目的是为了克服现有技术存在的水泥石被CO2腐蚀介质侵入后无法持续防腐问题，提供用于水泥浆的防腐蚀材料、抗二氧化碳腐蚀水泥浆及其制备方法和应用。采用本发明的防腐蚀材料制得的抗二氧化碳腐蚀水泥浆在CO2地质封存井腐蚀条件下，腐蚀后，水泥石具有抗压强度大、渗透率小、沉降稳定性好、流变性好、适用温度范围广等特点，保证CO2地质封存井长期有效密封。
为了实现上述目的，本发明第一方面提供一种用于水泥浆的防腐蚀材 料，所述防腐蚀材料包括混合物A和混合物B；其中，所述混合物A包括活性炭、纳米二氧化硅和纳米氧化铝；所述混合物B包括组分C和组分D；所述组分C选自硅藻土和/或粉煤灰；所述组分D选自偏高岭土、浮石和煤矸石中的一种或多种。
优选地，所述混合物A中，活性炭、纳米二氧化硅和纳米氧化铝的质量比为1:0.05-0.1:0.05-0.1。
优选地，所述组分C和组分D的质量比为1-2:1。
优选地，所述混合物A和混合物B的质量比为1:2-4。
优选地，所述活性炭的平均粒径为40-60μm。
优选地，所述纳米二氧化硅的SiO2含量大于99％，平均粒径为30-40nm。
优选地，所述纳米氧化铝的Al2O3含量大于99％，平均粒径为10-30nm。
优选地，所述组分C的平均粒径为10-20μm。
优选地，所述组分D平均粒径为20-40μm。
本发明第二方面提供一种用于水泥浆的防腐蚀材料的制备方法，所述制备方法包括：
将活性炭、纳米二氧化硅和纳米氧化铝混合，得到混合物A；
将组分C和组分D混合，得到混合物B；其中，所述组分C选自硅藻土和/或粉煤灰；所述组分D选自偏高岭土、浮石和煤矸石中的一种或多种；
在低搅拌速率条件下，将所述混合物A和混合物B混合，然后进行高速搅拌，得到所述防腐蚀材料。
优选地，所述低搅拌速率为3800-4200r/min，所述高速搅拌的速率为11500-12500r/min。
本发明第三方面提供前述第一方面所述的防腐蚀材料或前述第二方面所述的制备方法制得的防腐蚀材料在水泥浆中的应用，优选在抗二氧化碳腐蚀水泥浆中的应用。
本发明第四方面提供一种抗二氧化碳腐蚀水泥浆，所述水泥浆由以下重量份的原料制成：G级油井水泥100份、防腐蚀材料2-6份、微硅2-5份、增强材料3-6份、膨胀增韧材料3-5份、乳胶粉1-3份、稳定剂0-2份、分散剂0.3-2份、降失水剂2-5份、缓凝剂0.1-2份、消泡剂0.2-0.5份和水48-56份，其中，所述防腐蚀材料为前述第一方面所述的防腐蚀材料或前述第二方面所述的制备方法制得的防腐蚀材料。
本发明第五方面提供一种抗二氧化碳腐蚀水泥浆的制备方法，所述制备方法包括：
将G级油井水泥与防腐蚀材料、微硅、增强材料、膨胀增韧材料、乳胶粉、稳定剂和分散剂混合，得到干混料；
将降失水剂与缓凝剂、消泡剂和水混合，得到湿混料；
将所述干混料和所述湿混料混合，得到抗二氧化碳腐蚀水泥浆。
本发明第六方面提供前述第四方面所述的抗二氧化碳腐蚀水泥浆或前述第五方面所述的制备方法制得的抗二氧化碳腐蚀水泥浆在油气井固井作业中的应用。
优选地，所述抗二氧化碳腐蚀水泥浆的使用温度为30-150℃。
通过上述技术方案，本发明所取得的有益技术效果如下：
(1)采用本发明提供的用于水泥浆的防腐蚀材料制得的水泥浆适用温度范围为30-150℃，腐蚀后水泥石抗压强度均大于20MPa，渗透率均小于 0.1mD，甚至小于0.05mD，显著提升了水泥石防CO2腐蚀能力，同时对水泥浆其他工程性能无不良影响，可保障CCUS腐蚀工况条件下，水泥环长期有效密封。
(2)本发明用于抗二氧化碳腐蚀水泥浆在CO2腐蚀环境下具有良好的防腐蚀能力，腐蚀前水泥石抗压强度较高、结构致密，腐蚀后水泥石抗压强度无明显衰退、渗透率小、力学性能良好、沉降稳定性好、流变性好等综合性能，适用温度30-150℃及以下的防CO2腐蚀水泥浆体系，保障CCUS井固井质量，并保障在CCUS腐蚀工况条件下，水泥环长期有效密封性能，实现CO2高效封存。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明第一方面提供一种用于水泥浆的防腐蚀材料，所述防腐蚀材料包括混合物A和混合物B；其中，所述混合物A包括活性炭、纳米二氧化硅和纳米氧化铝；所述混合物B包括组分C和组分D；所述组分C选自硅藻土和/或粉煤灰；所述组分D选自偏高岭土、浮石和煤矸石中的一种或多种。
本发明中，混合物A包括活性炭、纳米二氧化硅和纳米氧化铝，纳米 二氧化硅和纳米氧化铝被吸附在活性炭的孔道内，可以缓慢释放，持久、修复。混合物A主要在后期起作用。
本发明中，水泥石接触到二氧化碳后，混合物B具有较强的火山灰活性，率先发生火山灰反应，消耗水泥石中的Ca(OH)2，生成水化硅酸钙、水化铝酸钙等致密的物质，附着在水泥石外侧起到保护作用，阻止CO2继续深入水泥石，即在水泥石外部初步形成了一个保护膜，随着水化反应继续进行，水化硅酸钙、水化铝酸钙等水化产物被不断消耗，保护膜被破坏，导致水泥石微结构再次出现破坏的迹象。混合物A缓慢释放出其中的纳米二氧化硅、和纳米氧化铝，起到充填堵作用，在水泥石外部形成致密保护膜，同时纳米二氧化硅与水泥石中的Ca(OH)2继续反应，阻止酸性气体继续进入水泥石，即混合物A可起到加固加密外围水泥石保护膜的作用，从而实现水泥石长期有效的防腐蚀。本发明通过优化防腐蚀材料的配方，实现长期防腐蚀，且长期防腐效果好。
本发明通过将混合物A和混合物B混合，操作简单方便、可实施性强。
在本发明的一些实施方式中，所述混合物A中，活性炭、纳米二氧化硅和纳米氧化铝的质量比为1:0.05-0.1:0.05-0.1。
在本发明的一些实施方式中，所述组分C和组分D的质量比为1-2:1。
在本发明的一些实施方式中，所述混合物A和混合物B的质量比为1:2-4。
通过以上原料制成的抗二氧化碳腐蚀水泥浆在CO2腐蚀环境下具有良好的防腐蚀能力，腐蚀前水泥石抗压强度较高、结构致密，腐蚀后水泥石抗压强度无明显衰退(强度衰退率小于20％)、渗透率小于渗透率均小于 0.1mD，甚至小于0.05mD。
含有以上防腐蚀材料的水泥浆，适用温度范围为30-150℃，可显著提升水泥石防CO2腐蚀能力，腐蚀后水泥石抗压强度大于20MPa，渗透率小，同时对水泥石其他性能无不良影响，可保障CCUS腐蚀工况条件下，水泥环长期有效密封性能。
在本发明的一些实施方式中，所述活性炭的平均粒径为40-60μm。
在本发明的一些实施方式中，所述纳米二氧化硅的SiO2含量大于99％，平均粒径为30-40nm。
在本发明的一些实施方式中，所述纳米氧化铝的Al2O3含量大于99％，平均粒径为10-30nm。
在本发明的一些实施方式中，所述组分C的平均粒径为10-20μm。
在本发明的一些实施方式中，所述组分D平均粒径为20-40μm。
本发明第二方面提供一种用于水泥浆的防腐蚀材料的制备方法，所述制备方法包括：
将活性炭、纳米二氧化硅和纳米氧化铝混合，得到混合物A；
将组分C和组分D混合，得到混合物B；其中，所述组分C选自硅藻土和/或粉煤灰；所述组分D选自偏高岭土、浮石和煤矸石中的一种或多种；
在低搅拌速率条件下，将所述混合物A和混合物B混合，然后进行高速搅拌，得到所述防腐蚀材料。
在本发明的一些实施方式中，所述低搅拌速率为3800-4200r/min，所述高速搅拌的速率为11500-12500r/min。
在本发明的一些实施方式中，所述混合物A中，活性炭、纳米二氧化 硅和纳米氧化铝的质量比为1:0.05-0.1:0.05-0.1。
在本发明的一些实施方式中，所述组分C和组分D的质量比为1-2:1。
在本发明的一些实施方式中，所述混合物A和混合物B的质量比为1:2-4。
在本发明的一些实施方式中，所述活性炭的40-60μm。
在本发明的一些实施方式中，所述纳米二氧化硅的SiO2含量大于99％，平均粒径为30-40nm。
在本发明的一些实施方式中，所述纳米氧化铝的Al2O3含量大于99％，平均粒径为10-30nm。
在本发明的一些实施方式中，所述组分C的平均粒径为10-20μm。
在本发明的一些实施方式中，所述组分D平均粒径为20-40μm。
本发明第三方面提供前述第一方面所述的防腐蚀材料或前述第二方面所述的制备方法制得的防腐蚀材料在水泥浆中的应用，优选在抗二氧化碳腐蚀水泥浆中的应用。
本发明的防腐蚀材料用于制备抗二氧化碳腐蚀水泥浆，可实施简单方便，水泥石接触到二氧化碳后，混合物B发生火山灰反应，消耗水泥石中的Ca(OH)2，产生水化硅酸钙、水化铝酸钙等物质，保护水泥石免受二氧化碳腐蚀，初步形成保护膜，随着水化反应继续进行，水化产物被继续消耗，导致水泥石微结构出现破坏的迹象，这时混合物A缓慢释放出其中的纳米二氧化硅和纳米氧化铝，起到充填堵作用，在水泥石外部形成致密保护膜，同时纳米二氧化硅与水泥石中的Ca(OH)2继续反应，阻止酸性气体继续进入水泥石。因此，制备得到的水泥浆能够起到持久抗二氧化碳腐蚀的作用。
本发明第四方面提供一种抗二氧化碳腐蚀水泥浆，所述水泥浆由以下重量份的原料制成：G级油井水泥100份、防腐蚀材料2-6份、微硅2-5份、增强材料3-6份、膨胀增韧材料3-5份、乳胶粉1-3份、稳定剂0-2份、分散剂0.3-2份、降失水剂2-5份、缓凝剂0.1-2份、消泡剂0.2-0.5份和水48-56份，其中，所述防腐蚀材料为前述第一方面所述的防腐蚀材料或前述第二方面所述的制备方法制得的防腐蚀材料。
本发明中，通过以上原料制成的抗二氧化碳腐蚀水泥浆在CO2腐蚀环境下具有良好的防腐蚀能力，腐蚀前水泥石抗压强度较高、结构致密，腐蚀后水泥石抗压强度无明显衰退，渗透率小，力学性能良好，同时沉降稳定性、流变性等综合性能良好，可适用温度30-150℃及以下的防CO2腐蚀水泥浆体系，保障CCUS井固井质量，实现CO2高效封存。
在本发明的一些实施方式中，所述微硅的SiO2含量不低于90％，平均粒径为5-10μm，45μm筛余≤5％。
本发明中，增强材料选自固井油井水泥用增强材料。
在本发明的一些实施方式中，所述增强材料选自无机矿石粉类材料，优选为中国石油集团工程技术研究院有限公司生产的矿石粉DRB-1S。
本发明中，膨胀增韧材料选自固井油井水泥用膨胀增韧材料。
在本发明的一些实施方式中，所述膨胀增韧材料选自橡胶类材料，优选为橡胶DRE-3S。
本发明中，乳胶粉选自固井油井水泥用乳胶粉。
在本发明的一些实施方式中，所述乳胶粉选自聚合物，优选为聚合物DRT-1S。
本发明中，稳定剂选自固井油井水泥用稳定剂。
在本发明的一些实施方式中，所述稳定剂选自凹凸棒土类材料，优选为矿石粉DRK-2S。
在本发明的一些实施方式中，所述分散剂选自聚苯乙烯磺酸盐类化合物和/或甲醛和丙酮的缩聚物。
在本发明的一些实施方式中，所述降失水剂选自聚丙烯酰胺类化合物。
在本发明的一些实施方式中，所述缓凝剂选自丙烯酰胺类化合物。
在本发明的一些实施方式中，所述消泡剂选自磷酸三丁酯、聚氧丙烯甘油和聚二甲基硅氧烷中的一种或多种。
本发明第五方面提供一种抗二氧化碳腐蚀水泥浆的制备方法，所述制备方法包括：
将G级油井水泥与防腐蚀材料、微硅、增强材料、膨胀增韧材料、乳胶粉、稳定剂和分散剂混合，得到干混料；
将降失水剂与缓凝剂、消泡剂和水混合，得到湿混料；
将所述干混料和所述湿混料混合，得到抗二氧化碳腐蚀水泥浆。
以上G级油井水泥、防腐蚀材料、微硅、增强材料、膨胀增韧材料、乳胶粉、稳定剂、分散剂、降失水剂、缓凝剂和消泡剂与第四方面中的相同，具体请参见前面的描述，在此不再赘述。
本发明第六方面提供前述第四方面所述的抗二氧化碳腐蚀水泥浆或前述第五方面所述的制备方法制得的抗二氧化碳腐蚀水泥浆在油气井固井作业中的应用。
在本发明的一些实施方式中，所述抗二氧化碳腐蚀水泥浆的使用温度 为30-150℃。
根据本发明一种特别优选的实施方式，抗二氧化碳腐蚀水泥浆的制备方法具体包括如下步骤：
(1)防腐蚀材料的制备：将活性炭与纳米二氧化硅、纳米氧化铝按照1:0.05-0.1:0.05-0.1的质量比充分混拌均匀，得到混合物A；将硅藻土和粉煤灰中的至少一种与偏高岭土、浮石和煤矸石中的至少一种按照1-2:1的质量比混合均匀，得到混合物B；将所述混合物A和混合物B按照1:2-4的质量比均匀混拌，得到防腐蚀材料；
(2)按配方量称取油井水泥、防腐蚀材料、微硅、增强材料、膨胀增韧材料、乳胶粉、稳定剂和分散剂，均匀掺混，得到干混料；按配方量称取称取降失水剂、缓凝剂和消泡剂，搅拌均匀，得到湿混料；在4000±200r/min的转速下，将干混料均匀倒入湿混料中，待干混料完全加入到湿混料中之后，盖上搅拌杯杯盖，将搅拌器转速调整至12000±500r/min，继续搅拌30-40s，优选为35s，得到抗二氧化碳腐蚀水泥浆。
以下将通过实施例对本发明进行详细描述。
以下实施例和对比例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购途径获得的常规产品。
G级油井水泥为高抗硫酸盐型(HSR)G级油井水泥，大连水泥集团有限公司生产。
微硅：其SiO2含量为95％，平均粒径为8μm，45μm筛余为4.2％。
增强材料为固井油井水泥用增强材料矿石粉DRB-1S，中国石油集团 工程技术研究院有限公司生产。
膨胀增韧材料为固井油井水泥用增韧材料橡胶DRE-3S，中国石油集团工程技术研究院有限公司生产。
乳胶粉为固井油井水泥用乳胶粉聚合物DRT-1S，中国石油集团工程技术研究院有限公司生产。
稳定剂为固井油井水泥用高温稳定剂矿石粉DRK-2S，中国石油集团工程技术研究院有限公司生产。
分散剂为固井油井水泥用分散剂醛酮缩聚物类DRS-1S，中国石油集团工程技术研究院有限公司生产。
降失水剂为固井油井水泥用降失水剂丙烯酰胺类DRF-1S，中国石油集团工程技术研究院有限公司生产。
缓凝剂为固井油井水泥用缓凝剂有机酸类DRH-1L，中国石油集团工程技术研究院有限公司生产。
消泡剂为固井油井水泥用消泡剂有机酯类DRX-1L，中国石油集团工程技术研究院有限公司生产。
按照国家标准GB/T 19139-2012《油井水泥试验方法》开展实验，对水泥浆体系的常规工程性能(密度、流动度、API失水量)以及腐蚀前后的抗压强度及渗透率进行评价。主要实验仪器有：30-60型瓦棱搅拌器；TG7370D型增压养护釜，沈阳泰格石油仪器设备制造有限公司；HH-420型恒温数显水箱，常州市亿能实验仪器厂；YAW-300B液压式压力试验机，济南新试金试验机有限公司；CO2腐蚀环境模拟系统，中国石油集团工程技术研究院有限公司产品。
流动度：按照国家标准GB/T 19139-2012《油井水泥试验方法》进行测试。
API失水量：按照国家标准GB/T 19139-2012《油井水泥试验方法》进行测试。
水泥石腐蚀采用中国石油集团工程技术有限公司发明的“CO2腐蚀环境模拟系统”或者具备在CO2气体/液体环境中加压养护的装置中进行腐蚀养护。
腐蚀前后的抗压强度：按照国家标准GB/T 19139-2012《油井水泥试验方法》进行测试。
强度损失率：强度损失率＝(T2-T1)/T1，其中，T1为腐蚀前水泥石抗压强度，T2为腐蚀后水泥石抗压强度。
渗透率：按照国家标准GB/T 19139-2012《油井水泥试验方法》进行测试。
制备例1
一种防腐蚀材料的制备方法，具体包括如下步骤：
(1)将活性炭与纳米二氧化硅、纳米氧化铝充分混拌均匀，质量比为1:0.05:0.05，所述活性炭为市售，325目；所述纳米二氧化硅为市售，SiO2含量为99.5％，平均粒径30nm；所述纳米氧化铝为市售，平均粒径30nm，Al2O3含量为99.3％，上述3种物质均匀混合后得到混合物A；
(2)将硅藻土和偏高岭土混合均匀，质量比为1:1，得到混合物B；
(3)将所述混合物A和混合物B均匀混拌，质量比为1:2，得到防腐蚀材料。
制备例2
一种防腐蚀材料的制备方法，具体包括如下步骤：
(1)将活性炭与纳米二氧化硅、纳米氧化铝充分混拌均匀，质量比为1:0.1:0.1，所述纳米二氧化硅为市售，SiO2含量为99.9％，平均粒径40nm；所述纳米氧化铝为市售，平均粒径20nm，Al2O3含量为99.9％，上述3种物质均匀混合后得到混合物A；
(2)将粉煤灰和煤矸石混合均匀，质量比为2:1，得到混合物B；
(3)将所述混合物A和混合物B均匀混拌，质量比为1:3，得到防腐蚀材料。
制备例3
一种防腐蚀材料的制备方法，具体包括如下步骤：
(1)将活性炭与纳米二氧化硅、纳米氧化铝充分混拌均匀，质量比为1:0.2:0.1，所述活性炭为市售，325目；所述纳米二氧化硅为市售，SiO2含量为99.8％，平均粒径30nm；所述纳米氧化铝为市售，平均粒径30nm，Al2O3含量为99.5％，上述3种物质均匀混合后得到混合物A；
(2)将粉煤灰和浮石混合均匀，质量比为3:1，得到混合物B；
(3)将所述混合物A和混合物B均匀混拌，质量比为1:5，得到防腐蚀材料。
制备对比例1
将硅藻土和煤矸石混合搅拌均匀，质量比为2:1，得到防腐蚀材料。
制备对比例2
(1)将纳米二氧化硅、纳米氧化铝充分混拌均匀，质量比为1:1，所 述纳米二氧化硅为市售，SiO2含量为99.5％，平均粒径30nm；所述纳米氧化铝为市售，平均粒径30nm，Al2O3含量为99.3％，上述2种物质均匀混合后得到混合物A；
(2)将硅藻土和偏高岭土混合均匀，质量比为1:1，得到混合物B；
(3)将所述混合物A和混合物B均匀混拌，质量比为1:3，得到防腐蚀材料。
实施例1
水泥浆配方按重量百分比如下：100份G级油井水泥、3份制备例1得到的防腐蚀材料、3份微硅、5份增强材料、4份膨胀增韧材料、2份乳胶粉、1份稳定剂、1份分散剂、3份降失水剂、0.5份缓凝剂、0.2份消泡剂和53份水。水泥浆密度为1.88g/cm3，实验结果见表1。
实施例2
水泥浆配方按重量百分比如下：100份G级油井水泥、3份制备例2得到的防腐蚀材料、3份微硅、5份增强材料、4份膨胀增韧材料、2份乳胶粉、1份稳定剂、1份分散剂、3份降失水剂、0.5份缓凝剂、0.2份消泡剂和53份水。水泥浆密度为1.88g/cm3，实验结果见表1。
实施例3
与实施例2相比，添加不同量的防腐蚀材料。水泥浆配方按重量百分比如下：100份G级油井水泥、5份制备例2得到的防腐蚀材料、3份微硅、5份增强材料、4份膨胀增韧材料、2份乳胶粉、1份稳定剂、1份分散剂、3份降失水剂、0.5份缓凝剂、0.2份消泡剂和53份水。水泥浆密度为1.88g/cm3，实验结果见表1。
实施例4
水泥浆配方按重量百分比如下：100份G级油井水泥、6份制备例2得到的防腐蚀材料、2份微硅、6份增强材料、3份膨胀增韧材料、1份乳胶粉、2份稳定剂、2份分散剂、2份降失水剂、2份缓凝剂、0.2份消泡剂和56份水。水泥浆密度为1.88g/cm3，实验结果见表1。
实施例5
水泥浆配方按重量百分比如下：100份G级油井水泥、2份制备例2得到的防腐蚀材料、5份微硅、3份增强材料、6份膨胀增韧材料、3份乳胶粉、0.4份稳定剂、1份分散剂、5份降失水剂、0.1份缓凝剂、0.2份消泡剂和48份水。水泥浆密度为1.88g/cm3，实验结果见表1。
实施例6
与实施例2相比，添加不同的防腐蚀材料。水泥浆配方按重量百分比如下：100份G级油井水泥、3份制备3得到的防腐蚀材料、3份微硅、5份增强材料、4份膨胀增韧材料、2份乳胶粉、1份稳定剂、1份分散剂、3份降失水剂、0.5份缓凝剂、0.2份消泡剂和53份水。水泥浆密度为1.88g/cm3，实验结果见表1。
对比例1
与实施例2相比，添加不同的防腐蚀材料。水泥浆配方按重量百分比如下：100份G级油井水泥、3份制备对比例1得到的防腐蚀材料、3份微硅、5份增强材料、4份膨胀增韧材料、2份乳胶粉、1份稳定剂、1份分散剂、3份降失水剂、0.5份缓凝剂、0.2份消泡剂和53份水。水泥浆密度为1.88g/cm3，实验结果见表1。
对比例2
与实施例2相比，添加不同的防腐蚀材料。水泥浆配方按重量百分比如下：100份G级油井水泥、3份制备对比例2得到的防腐蚀材料、3份微硅、5份增强材料、4份膨胀增韧材料、2份乳胶粉、1份稳定剂、1份分散剂、3份降失水剂、0.5份缓凝剂、0.2份消泡剂和53份水。水泥浆密度为1.88g/cm3，实验结果见表1。
对比例3
与实施例2相比，不添加防腐蚀材料。水泥浆配方按重量百分比如下：100份G级油井水泥，3份微硅、5份增强材料、4份膨胀增韧材料、2份乳胶粉、1份稳定剂、1份分散剂、3份降失水剂、0.5份缓凝剂、0.2份消泡剂和53份水。水泥浆密度为1.88g/cm3，实验结果见表1。
表1实施例及对比例实验结果
表1实施例及对比例实验结果(续)
从表1数据可见，全部实施例流动度均大于20cm，API失水量小于50mL，满足固井施工要求。全部实施例腐蚀后抗压强度大于20MPa，强度损失率均小于20％，渗透率小于0.1mD，性能良好，满足固井密封要求。
从实施例1-3的实验数据可见，使用实施例1的水泥浆，腐蚀60天以后，抗压强度由32.6MPa衰退至27.9MPa，腐蚀过后抗压强度大于20MPa，且渗透率小于0.05mD，腐蚀后水泥石力学性能良好，满足封固要求。在本发明限定的范围内，调整防腐蚀材料中各组分比例、防腐蚀材料加量，对水泥浆体系的密度、流动度、API失水量等均无不良影响，同时腐蚀过后水泥石抗压强度均大于20MPa，渗透率小于0.05mD，水泥石防腐蚀性能良好。
从实施例2以及实施例4和5的实验数据可见，温度变化后，根据需 要调整不同外加剂的量，得到的水泥浆体系工程性能良好，同时在腐蚀条件下养护后，抗压强度均大于20MPa，渗透率小于0.05mD，防腐蚀性能良好，即在各材料加量范围内，根据不同温度进行调整，可满足不同温度下的使用要求。
从实施例2以及对比例1-2的数据可见，腐蚀过后，对比例1-2的抗压强度出现了明显的下降，均不足20MPa，渗透率也明细增加，甚至均大于0.1mD，并且对比例2的流动度为17cm，流动性出现了劣化现象。
从对比例4的数据可知，水泥浆中不加入防腐蚀材料时，腐蚀前水泥石强度31.5MPa，但是腐蚀60天后，抗压强度衰退至15.6MPa，衰退50.48％，渗透率由0.049mD增长至0.203mD，强度衰退明显，渗透率显著增大。
综上，本发明的水泥浆，适用温度范围为30-150℃，腐蚀后水泥石抗压强度均大于20MPa，渗透率均小于0.05mD，显著提升了水泥石防CO2腐蚀能力，同时对水泥浆其他工程性能无不良影响，可保障CCUS腐蚀工况条件下，水泥环长期有效密封。
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (14)

  1. 一种用于水泥浆的防腐蚀材料，其特征在于，所述防腐蚀材料包括混合物A和混合物B；其中，所述混合物A包括活性炭、纳米二氧化硅和纳米氧化铝；所述混合物B包括组分C和组分D；所述组分C选自硅藻土和/或粉煤灰；所述组分D选自偏高岭土、浮石和煤矸石中的一种或多种。
  2. 根据权利要求1所述的防腐蚀材料，其中，所述混合物A中，活性炭、纳米二氧化硅和纳米氧化铝的质量比为1:0.05-0.1:0.05-0.1；
    和/或，所述组分C和组分D的质量比为1-2:1；
    和/或，所述混合物A和混合物B的质量比为1:2-4。
  3. 根据权利要求1或2所述的防腐蚀材料，其中，所述活性炭的平均粒径为40-60μm；
    和/或，所述纳米二氧化硅的SiO2含量大于99％，平均粒径为30-40nm；
    和/或，所述纳米氧化铝的Al2O3含量大于99％，平均粒径为10-30nm；
    和/或，所述组分C的平均粒径为10-20μm；
    和/或，所述组分D的平均粒径为20-40μm。
  4. 一种用于水泥浆的防腐蚀材料的制备方法，其特征在于，所述制备方法包括：
    将活性炭、纳米二氧化硅和纳米氧化铝混合，得到混合物A；
    将组分C和组分D混合，得到混合物B；其中，所述组分C选自硅藻土和/或粉煤灰；所述组分D选自偏高岭土、浮石和煤矸石中的一种或多种；
    在低搅拌速率条件下，将所述混合物A和混合物B混合，然后进行高 速搅拌，得到所述防腐蚀材料；
    优选地，所述低搅拌速率为3800-4200r/min，所述高速搅拌的速率为11500-12500r/min。
  5. 根据权利要求6所述的制备方法，其中，所述混合物A中，活性炭、纳米二氧化硅和纳米氧化铝的质量比为1:0.05-0.1:0.05-0.1；
    和/或，所述组分C和组分D的质量比为1-2:1；
    和/或，所述混合物A和混合物B的质量比为1:2-4。
  6. 根据权利要求4或5所述的制备方法，其中，所述活性炭的平均粒径为40-60μm；
    和/或，所述纳米二氧化硅的SiO2含量大于99％，平均粒径为30-40nm；
    和/或，所述纳米氧化铝的Al2O3含量大于99％，平均粒径为10-30nm；
    和/或，所述组分C的平均粒径为10-20μm；
    和/或，所述组分D的平均粒径为20-40μm。
  7. 权利要求1-3中任意一项所述的防腐蚀材料或权利要求4-6中任意一项所述的制备方法制得的防腐蚀材料在水泥浆中的应用，优选在抗二氧化碳腐蚀水泥浆中的应用。
  8. 一种用于抗二氧化碳腐蚀水泥浆，其特征在于，所述水泥浆由以下重量份的原料制成：G级油井水泥100份、防腐蚀材料2-6份、微硅2-5份、增强材料3-6份、膨胀增韧材料3-5份、乳胶粉1-3份、稳定剂0-2份、分散剂0.3-2份、降失水剂2-5份、缓凝剂0.1-2份、消泡剂0.2-0.5份和水48-56份；其中，所述防腐蚀材料为权利要求1-3中任意一项所述的防腐蚀材料或权利要求4-6中任意一项所述的制备方法制得的防腐蚀材料。
  9. 根据权利要求8所述的水泥浆，其中，所述微硅的SiO2含量不低于90％，平均粒径为5-10μm，45μm筛余≤5％。
  10. 根据权利要求8或9所述的水泥浆，其中，所述增强材料选自无机矿石粉类材料，优选为矿石粉DRB-1S；
    和/或，所述膨胀增韧材料选自橡胶类材料，优选为橡胶DRE-3S；
    和/或，所述乳胶粉选自聚合物，优选为聚合物DRT-1S；
    和/或，所述稳定剂选自凹凸棒土类材料，优选为矿石粉DRK-2S。
  11. 根据权利要求8-10中任意一项所述的水泥浆，其中，所述分散剂选自聚苯乙烯磺酸盐类化合物和/或甲醛和丙酮的缩聚物；
    和/或，所述降失水剂选自聚丙烯酰胺类化合物；
    和/或，所述缓凝剂选自丙烯酰胺类化合物；
    和/或，所述消泡剂选自磷酸三丁酯、聚氧丙烯甘油和聚二甲基硅氧烷中的一种或多种。
  12. 一种抗二氧化碳腐蚀水泥浆的制备方法，其特征在于，所述制备方法包括：
    将G级油井水泥与防腐蚀材料、微硅、增强材料、膨胀增韧材料、乳胶粉、稳定剂和分散剂混合，得到干混料；其中，所述防腐蚀材料为权利要求1-3中任意一项所述的防腐蚀材料或权利要求4-6中任意一项所述的制备方法制得的防腐蚀材料；
    将降失水剂与缓凝剂、消泡剂和水混合，得到湿混料；
    将所述干混料和所述湿混料混合，得到抗二氧化碳腐蚀水泥浆。
  13. 权利要求8-11中任意一项所述的抗二氧化碳腐蚀水泥浆或权利要 求12所述的制备方法制得的抗二氧化碳腐蚀水泥浆在油气井固井作业中的应用。
  14. 根据权利要求13所述的应用，其中，所述抗二氧化碳腐蚀水泥浆的使用温度为30-150℃。
PCT/CN2023/138201 2023-06-21 2023-12-12 用于水泥浆的防腐蚀材料、抗二氧化碳腐蚀水泥浆及其制备方法和应用 Ceased WO2024259914A1 (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119822734A (zh) * 2025-01-10 2025-04-15 湖北工业大学 一种由海水、纳米二氧化硅与聚乙烯醇纤维配制的复合水泥土及其制备方法
CN121085601A (zh) * 2025-11-06 2025-12-09 山东五和建筑科技有限公司 一种高性能铝酸盐无机防腐砂浆及其制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102010702A (zh) * 2009-09-04 2011-04-13 中国石油化工股份有限公司 一种防止二氧化碳腐蚀的油井水泥外加剂及其制备方法和应用
CN102464973A (zh) * 2010-11-18 2012-05-23 中国石油天然气集团公司 一种注油井水泥的抗co2腐蚀材料
US20150260009A1 (en) * 2013-05-13 2015-09-17 King Fahd University Of Petroleum And Minerals Portland cement type-g with nanosilica additive for high pressure-high temperature applications
KR101617723B1 (ko) * 2015-12-11 2016-05-04 장산씨엠주식회사 콘크리트 혼입용 구체방청·방수재 조성물
CN105778875A (zh) * 2014-12-26 2016-07-20 嘉华特种水泥股份有限公司 一种地聚物油井水泥
CN112645647A (zh) * 2020-12-30 2021-04-13 同济大学 一种纳米二氧化硅改性地聚合物防腐砂浆及其制备方法
CN114133172A (zh) 2021-12-09 2022-03-04 中海石油(中国)有限公司 一种固井中抗二氧化碳腐蚀水泥浆及其制备方法
CN115703674A (zh) * 2021-08-06 2023-02-17 中国石油天然气集团有限公司 一种高含co2气井固井用防腐蚀水泥浆体系及其制备方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102010702A (zh) * 2009-09-04 2011-04-13 中国石油化工股份有限公司 一种防止二氧化碳腐蚀的油井水泥外加剂及其制备方法和应用
CN102464973A (zh) * 2010-11-18 2012-05-23 中国石油天然气集团公司 一种注油井水泥的抗co2腐蚀材料
US20150260009A1 (en) * 2013-05-13 2015-09-17 King Fahd University Of Petroleum And Minerals Portland cement type-g with nanosilica additive for high pressure-high temperature applications
CN105778875A (zh) * 2014-12-26 2016-07-20 嘉华特种水泥股份有限公司 一种地聚物油井水泥
KR101617723B1 (ko) * 2015-12-11 2016-05-04 장산씨엠주식회사 콘크리트 혼입용 구체방청·방수재 조성물
CN112645647A (zh) * 2020-12-30 2021-04-13 同济大学 一种纳米二氧化硅改性地聚合物防腐砂浆及其制备方法
CN115703674A (zh) * 2021-08-06 2023-02-17 中国石油天然气集团有限公司 一种高含co2气井固井用防腐蚀水泥浆体系及其制备方法
CN114133172A (zh) 2021-12-09 2022-03-04 中海石油(中国)有限公司 一种固井中抗二氧化碳腐蚀水泥浆及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HUAJUN ZHU, XIAO YAO, ZUHUA ZHANG, LIXIN LIANG, YUXIN HE: "Anti-carbonation Property of Metakaolin-slag Geopolymer at Hydrothermal Condition", NON-METALLIC MINES, vol. 34, no. 3, 1 May 2011 (2011-05-01), XP093251808 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119822734A (zh) * 2025-01-10 2025-04-15 湖北工业大学 一种由海水、纳米二氧化硅与聚乙烯醇纤维配制的复合水泥土及其制备方法
CN121085601A (zh) * 2025-11-06 2025-12-09 山东五和建筑科技有限公司 一种高性能铝酸盐无机防腐砂浆及其制备方法

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