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WO2023123976A1 - Crystalline phase modified broad-spectrum ultrahigh-temperature-resistant well cementing slurry and application thereof - Google Patents

Crystalline phase modified broad-spectrum ultrahigh-temperature-resistant well cementing slurry and application thereof Download PDF

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WO2023123976A1
WO2023123976A1 PCT/CN2022/102990 CN2022102990W WO2023123976A1 WO 2023123976 A1 WO2023123976 A1 WO 2023123976A1 CN 2022102990 W CN2022102990 W CN 2022102990W WO 2023123976 A1 WO2023123976 A1 WO 2023123976A1
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cement slurry
parts
high temperature
ultra
cementing
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PCT/CN2022/102990
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French (fr)
Chinese (zh)
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郑友志
范宇
辜涛
郑有成
张华礼
余江
张占武
何雨
赵军
夏宏伟
胡锡辉
赵彬凌
王福云
杨涛
焦利宾
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中国石油天然气股份有限公司
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Publication of WO2023123976A1 publication Critical patent/WO2023123976A1/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/46Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
    • C09K8/467Compositions 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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    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52Amides or imides
    • C08F220/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52Amides or imides
    • C08F220/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C08F220/585Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine and containing other heteroatoms, e.g. 2-acrylamido-2-methylpropane sulfonic acid [AMPS]
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    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/02Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36Amides or imides
    • C08F222/38Amides
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/10N-Vinyl-pyrrolidone
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/02Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • C08F251/02Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete

Definitions

  • the invention relates to the technical field of cementing cement slurry, in particular to a crystal phase modified broad-spectrum ultra-high temperature resistant cementing slurry.
  • the cement slurry and cement sheath mainly face three problems: First, high temperature It is easy to cause the failure and denaturation of cement admixture, and the cement slurry is prone to high-temperature settlement instability, difficult to balance rheology, difficult to control water loss, difficult to adjust thickening time and other complex problems, which can easily cause cementing safety accidents and quality problems; Under the condition of long open hole and large temperature difference, the strength of cement stone develops slowly or even super retarded.
  • the static temperature difference between the hanger and the casing shoe is too large and the cement slurry density is high, it is very easy to cause the cement slurry at the hanger position to not condense for a long time, which will not only prolong the well construction period, but also cause the risk of gas blow-by at the bell mouth
  • the third is the strength decline of cement stone under the action of long-term ultra-high temperature.
  • the temperature exceeds 110 °C, the crystal transformation of cement hydration products will increase the porosity and permeability of the cement stone, and the strength will decline, resulting in a decrease in the mechanical integrity and structural integrity of the cement annulus, causing gas channeling and annular pressure in the later stage question.
  • the object of the present invention is to provide a crystal phase modified broad-spectrum ultra-high temperature resistant cementing cement slurry, which can effectively overcome the long-term ultra-high temperature resistance of the conventional silica fume cement slurry system by adding a crystal phase modified high-temperature reinforcing agent.
  • the problem of strength decline under high temperature conditions.
  • the present invention provides a crystal phase transformation type broad-spectrum ultra-high temperature resistant cementing cement slurry, wherein the cementing cement slurry contains a crystal transformation type high temperature enhancer;
  • the composition of the crystal phase transformation type high-temperature reinforcing agent includes 10-30% sodium aluminate, 2-10% micro-silicon, 30-50% calcium aluminate, 30-50% metakaolin, 1-5% % inorganic fibers.
  • the cementing slurry has the following composition:
  • oil well cement 100 parts of oil well cement, 40-50 parts of silicon powder, 0-100 parts of weighting agent, 1-3 parts of expansion agent, 3-10 parts of crystal phase modification high-temperature reinforcing agent, 1-2 parts of dispersant, 1-2 parts of suspending agent 1-3 parts of toughening agent, 2-6 parts of ultra-high temperature retarder, 3-7 parts of ultra-high temperature fluid loss reducer, and 55-65 parts of water.
  • the purity of the sodium aluminate is >93%.
  • the fineness of the sodium aluminate is 200-300 mesh.
  • the purity of the calcium aluminate is >90%.
  • the fineness of the calcium aluminate is 200-300 mesh.
  • the metakaolin has the following chemical index requirements: SiO 2 content ⁇ 50%, Al 2 O 3 content ⁇ 40%, free CaO content ⁇ 1%.
  • the inorganic fiber is a surface-treated dispersible carbon fiber or basalt fiber.
  • the length of the inorganic fibers is 3-6 mm.
  • the above-mentioned crystal phase transformation type high-temperature reinforcing agent can be prepared according to the following steps:
  • Step 1 Stir and blend sodium aluminate and microsilicon to obtain a mixture, and the time of stirring and blending can be controlled to 5 minutes;
  • Step 2 Add calcium aluminate, metakaolin, and inorganic fibers to the mixture obtained in step 1, and stir and blend to obtain a crystal phase modification type high-temperature reinforcing agent.
  • the time of stirring and blending can be controlled to 15 minutes.
  • the silica fume is a combination of 200 mesh silica fume and 600 mesh silica fume with a silica mass content ⁇ 97%, and the The weight ratio of 200 mesh silicon powder to 600 mesh silicon powder is (4-7):(3-6).
  • the weighting agent is iron ore powder with a density ⁇ 7.0 g/cm 3 .
  • the expansion agent is a mixture of calcium sulfoaluminate and calcium oxide, and the mixing weight ratio is (1-4):1.
  • the dispersant is sulfonated formaldehyde-acetone condensate and/or polynaphthalene sulfonate.
  • the suspending agent is 2-acrylamide-2-methylpropanesulfonic acid (AMPS) polymer viscosity-increasing material.
  • AMPS 2-acrylamide-2-methylpropanesulfonic acid
  • the toughening agent is high temperature resistant rubber powder and/or resin elastomer microspheres.
  • the ultra-high temperature retarder consists of itaconic acid (IA), 2-acrylamide-2-methylpropanesulfonic acid (AMPS), N,N-dimethylacrylamide (DMAA), vinyl phosphoric acid polymerized.
  • the preparation method of the ultra-high temperature retarder comprises:
  • step (2) Place the mixed solution obtained in step (1) in a reaction device (preferably a reaction device with a stirrer, a thermometer and a nitrogen protection condition), and pass into a protective gas (preferably an inert gas or nitrogen) to exhaust the reaction device of oxygen;
  • a reaction device preferably a reaction device with a stirrer, a thermometer and a nitrogen protection condition
  • a protective gas preferably an inert gas or nitrogen
  • step (3) Warm up the reaction device to 58-63°C; preferably place the reaction device after exhausting oxygen in step (2) in a water bath, and heat the mixed solution to 58-63°C while starting the stirrer;
  • step (4) Dissolve vinyl phosphoric acid (VA) with a total dosage of 8-12% in water 1-2 times its mass, and add it dropwise to step (4) after 0.5 hours of reaction at a rate of 10-15ml/min. In the mixed solution, continue to react for 1.5-2 hours and then cool to obtain an ultra-high temperature retarder.
  • VA vinyl phosphoric acid
  • the ultra-high temperature fluid loss reducer is composed of 2-acrylamide-2-methylpropanesulfonic acid (AMPS), acrylic acid (AA), N,N-dimethylacrylamide (DMAA), N-vinylpyrrolidone (NVP), and microcrystalline cellulose (MCC) are polymerized.
  • AMPS 2-acrylamide-2-methylpropanesulfonic acid
  • acrylic acid AA
  • DMAA N,N-dimethylacrylamide
  • MMC microcrystalline cellulose
  • the preparation method of the ultra-high temperature fluid loss reducing agent comprises:
  • step (1) Add 10-15% of N,N-dimethylacrylamide (DMAA), 4-8% of N-vinylpyrrolidone (NVP), 0.2% of N,N-methylenebis Add acrylamide (MBA) into the mixed solution of step (1), and stir evenly;
  • DMAA N,N-dimethylacrylamide
  • NDP N-vinylpyrrolidone
  • MSA N,N-methylenebis
  • step (3) the mixed solution of step (2) is placed in the reaction device (preferably the reaction device with agitator, thermometer and nitrogen protection conditions), feeds protective gas (preferably inert gas or nitrogen) to exhaust the reaction device Air;
  • the reaction device preferably the reaction device with agitator, thermometer and nitrogen protection conditions
  • protective gas preferably inert gas or nitrogen
  • step (3) Warm up the mixed solution in step (3) to 60-65°C, preferably place the reaction device after exhausting the air in a water bath, and turn on the stirrer while heating the mixed solution to 60-65°C;
  • step (6) Add microcrystalline cellulose (MCC) with a total dosage of 15-20% into water with 5 times its mass, stir it and add it dropwise to the mixed solution of step (5) at a rate of 3-4ml/min, Continue to react for 2 hours and then cool to obtain an ultra-high temperature dehydration agent.
  • MMC microcrystalline cellulose
  • the applicable density range of the cement slurry of the present invention is 1.85-2.40 g/cm 3 .
  • the crystal phase modification type broad-spectrum ultra-high temperature resistant cementing cement slurry provided by the present invention can be prepared through the following steps:
  • the oil well cement, silica fume, weighting agent, expansion agent, crystal phase transformation type high-temperature reinforcing agent, dispersant, suspending agent, and toughening agent are mixed and stirred evenly to obtain a dry blend; parts by weight, mix and stir the ultra-high temperature retarder, ultra-high temperature fluid loss reducer and water evenly to obtain slurry preparation water; add the dry blend to the slurry preparation water, mix and stir evenly to obtain the crystal phase Modified broad-spectrum ultra-high temperature resistant cementing cement slurry.
  • the present invention also provides the application of the crystal phase reformed broad-spectrum ultra-high temperature resistant well cementing cement slurry in well cementing operations.
  • the anorthite phase is formed after the cement slurry is cured.
  • the cementing operation refers to the cementing operation in high-temperature and ultra-high-temperature formations such as deep wells and ultra-deep wells, hot dry rocks, and geothermal wells.
  • the applicable circulation temperature range of the crystal phase modified broad-spectrum ultra-high temperature resistant cement slurry is 110°C-230°C.
  • the crystal phase transformation type high-temperature reinforcing agent mixed in the cement slurry of the present invention can participate in the hydration reaction of silica fume cement and generate anorthite phase.
  • Anorthite has excellent high temperature resistance and can slow down super
  • the crystallization phenomenon of high-temperature cement stone further makes the cement slurry system of the present invention have good resistance to ultra-high temperature strength decline.
  • the cement slurry system of the present invention adopts an admixture with excellent temperature resistance and low sensitivity, which can meet the requirement of a cycle temperature of 110°C-230°C, has a wide range of temperature applications, and can adjust the density and thickening time at the same time.
  • the strength of the top develops rapidly, which can meet the application requirements of "medium-high temperature (110-150°C)-high temperature (150-205°C)-ultra-high temperature (>205°C)" across temperature zones.
  • Fig. 1 is a thickening test curve of the cementing slurry of Example 3.
  • Fig. 2 is a thickening test curve of the cement slurry of Example 6.
  • Silicon powder the weight ratio of 200 mesh silicon powder to 600 mesh silicon powder is 4:6;
  • Expansion agent a mixture of calcium sulfoaluminate and calcium oxide with a mass ratio of 3:1;
  • Crystal phase modified high-temperature reinforcing agent a mixture of 15% sodium aluminate, 4% microsilicon, 33% calcium aluminate, 36% metakaolin, and 2% inorganic fiber by mass fraction;
  • Dispersant sulfonated formaldehyde-acetone condensate FS200L, the manufacturer is Sichuan Annuosi Oil and Gas Energy Technology Co., Ltd.;
  • Toughener HE-1S, the manufacturer is Sichuan Annuosi Oil and Gas Energy Technology Co., Ltd.;
  • Ultra-high temperature retarder made by polymerizing 23% itaconic acid, 44% 2-acrylamide-2-methylpropanesulfonic acid, 22% N,N-dimethylacrylamide, and 11% ethylene phosphoric acid in terms of mass percentage ;
  • Ultra-high temperature fluid loss reducer 45% 2-acrylamide-2-methylpropanesulfonic acid, 23% acrylic acid, 11% N,N-dimethylacrylamide, 4% N-vinylpyrrolidone according to mass percentage, Made of 0.2% N,N-methylenebisacrylamide and 16.8% microcrystalline cellulose;
  • Weighting agent iron ore powder with a density of 7.0g/cm 3 .
  • This example provides a crystal phase reformed broad-spectrum ultra-high temperature resistant well cementing cement slurry with a density of 1.85g/cm 3 and an application temperature of 110°C, which is composed of the following components in proportion by weight: 100 parts of oil well cement, 40 parts of silicon powder, 1 part of expansion agent, 3 parts of crystal phase reforming high-temperature strengthening agent, 1 part of dispersing agent, 1 part of suspending agent, 2 parts of toughening agent, 2 parts of ultra-high temperature retarder, and ultra-high temperature fluid loss reducer 3 parts, 62 parts of water.
  • This example provides a crystal phase reformed broad-spectrum ultra-high temperature resistant well cementing cement slurry with a density of 2.40g/cm 3 and an application temperature of 110°C, which is composed of the following components in proportion by weight: 100 parts of oil well cement, 40 parts of silicon powder, 100 parts of weighting agent, 1 part of expansion agent, 3 parts of crystal phase modification high temperature reinforcing agent, 2 parts of dispersing agent, 1.5 parts of suspending agent, 1 part of toughening agent, 2 parts of super high temperature retarder, super 3 parts of high temperature fluid loss reducer, 58 parts of water.
  • This example provides a crystal phase reformed broad-spectrum ultra-high temperature resistant well cementing cement slurry with a density of 1.95g/cm 3 and an application temperature of 150°C, which is composed of the following components in proportion by weight: 100 parts of oil well cement, 40 parts of silicon powder, 2 parts of expansion agent, 5 parts of crystal phase reforming high temperature reinforcing agent, 1 part of dispersing agent, 1.5 parts of suspending agent, 1.5 parts of toughening agent, 3.5 parts of super high temperature retarder, super high temperature fluid loss reducer 4 parts, 62 parts of water.
  • This example provides a crystal phase reformed broad-spectrum ultra-high temperature resistant well cementing cement slurry with a density of 1.95g/cm 3 and an application temperature of 180°C, which is composed of the following components in proportion by weight: 100 parts of oil well cement, 45 parts of silicon powder, 2 parts of expansion agent, 5 parts of crystal phase reforming high-temperature strengthening agent, 1 part of dispersing agent, 1.5 parts of suspending agent, 1.5 parts of toughening agent, 4 parts of ultra-high temperature retarder, and ultra-high temperature fluid loss reducer 5 parts, 62 parts of water.
  • This example provides a crystal phase reformed broad-spectrum ultra-high temperature resistant well cementing cement slurry with a density of 2.20g/cm 3 and an application temperature of 180°C, which is composed of the following components in proportion by weight: 100 parts of oil well cement, 45 parts of silicon powder, 54 parts of weighting agent, 2 parts of expansion agent, 5 parts of crystal phase reforming high temperature reinforcing agent, 2 parts of dispersing agent, 1.5 parts of suspending agent, 2 parts of toughening agent, 3.5 parts of super high temperature retarder, super 5.5 parts of high temperature fluid loss reducer, 55 parts of water.
  • This example provides a crystal phase reformed broad-spectrum ultra-high temperature resistant well cementing cement slurry with a density of 1.85g/cm 3 and an application temperature of 230°C, which is composed of the following components in proportion by weight: 100 parts of oil well cement, 50 parts of silicon powder, 2 parts of expansion agent, 7 parts of crystal phase reforming high-temperature strengthening agent, 1 part of dispersing agent, 2 parts of suspending agent, 3 parts of toughening agent, 5 parts of ultra-high temperature retarder, and ultra-high temperature fluid loss reducer 7 parts, 61 parts of water.
  • This example provides a crystal phase reformed broad-spectrum ultra-high temperature resistant well cementing cement slurry with a density of 2.40g/cm 3 and an application temperature of 230°C, which is composed of the following components in proportion by weight: 100 parts of oil well cement, 50 parts of silicon powder, 100 parts of weighting agent, 2 parts of expansion agent, 7 parts of crystal phase transformation high-temperature reinforcing agent, 2 parts of dispersing agent, 2 parts of suspending agent, 2 parts of toughening agent, 6 parts of ultra-high temperature retarder, super 7 parts of high temperature fluid loss reducer, 65 parts of water.
  • This comparative example provides a cementing slurry with a density of 1.85g/cm 3 and an application temperature of 230°C that does not contain a crystal-phase modified high-temperature reinforcing agent, which is composed of the following components in proportion by weight: 100 parts of oil well cement , 50 parts of silicon powder, 2 parts of expansion agent, 1 part of dispersant, 2 parts of suspending agent, 3 parts of toughening agent, 5 parts of ultra-high temperature retarder, 7 parts of ultra-high temperature fluid loss reducer, and 60 parts of water.
  • a crystal-phase modified high-temperature reinforcing agent which is composed of the following components in proportion by weight: 100 parts of oil well cement , 50 parts of silicon powder, 2 parts of expansion agent, 1 part of dispersant, 2 parts of suspending agent, 3 parts of toughening agent, 5 parts of ultra-high temperature retarder, 7 parts of ultra-high temperature fluid loss reducer, and 60 parts of water.
  • This comparative example provides a cementing cement slurry with a density of 1.95g/cm 3 , an application temperature of 180°C, and a commercially available anti-high temperature retarder (temperature resistance ⁇ 180°C), which consists of the following components in parts by weight Proportion composition: 100 parts of oil well cement, 45 parts of silica fume, 2 parts of expansion agent, 5 parts of crystal phase reforming high-temperature reinforcing agent, 1 part of dispersant, 1.5 parts of suspending agent, 1.5 parts of toughening agent, commercially available retarder 4 parts, 5 parts of ultra-high temperature fluid loss reducer, and 62 parts of water.
  • a commercially available anti-high temperature retarder temperature resistance ⁇ 180°C
  • This comparative example provides a cementing cement slurry with a density of 2.20g/cm 3 and an application temperature of 180°C, using a commercially available anti-high temperature fluid loss reducing agent (temperature resistance ⁇ 180°C), which consists of the following components by weight Proportion composition: 100 parts of oil well cement, 45 parts of silicon fume, 54 parts of weighting agent, 2 parts of expansion agent, 5 parts of crystal phase modification high temperature reinforcing agent, 2 parts of dispersant, 1.5 parts of suspending agent, 2 parts of toughening agent , 3.5 parts of ultra-high temperature retarder, 5.5 parts of commercially available fluid loss reducer, and 55 parts of water.
  • a commercially available anti-high temperature fluid loss reducing agent temperature resistance ⁇ 180°C
  • this test example is for the crystal phase transformation type broad-spectrum anti-ultra-high temperature cementing cement slurry of embodiment 1-7 and Performance tests were performed on conventional projects such as density, free liquid, fluidity, API dehydration, and thickening time of Examples 1-3, and the results are shown in Table 1.
  • the parameter conditions of the thickening time test in Example 3 are as follows: initial consistency start time 15.0min, initial consistency end time 30.0min; initial temperature 25.5°C, target temperature 150.0°C; initial pressure -1.9MPa, target pressure 80.0MPa; initial consistency 29.2Bc, alarm consistency 100.0Bc; 30Bc thickening time 05:03:38, 40Bc thickening time 05:08:39, 50Bc thickening time 05:09:39, 60Bc thickening time 05:10:39, 70Bc thickening Thickening time 05:12:09, thickening time 05:13:30;
  • the parameter conditions of the thickening time test in Example 6 are as follows: initial consistency start time 15.0min, initial consistency end time 30.0min; initial temperature 27.6°C, target temperature 230.0°C; initial pressure 1.6MPa, target pressure 150.0MPa; initial consistency 15.7 Bc, alarm consistency 100.0Bc; 30Bc thickening time 05:26:39, 40Bc thickening time 05:26:39, 50Bc thickening time 05:26:39, 60Bc thickening time 05:26:39, 70Bc thickening time Time 00:00:00, thickening time 05:26:39.
  • the crystal phase reformed broad-spectrum ultra-high temperature resistant cementing cement slurry of Examples 1-7 has good fluidity and good stability, and the thickening time is adjustable, which can meet the requirements of engineering construction operations. It can be seen from Figures 1 and 2 that the initial viscosity of the crystal-phase reformed broad-spectrum ultra-high temperature resistant cement slurry is relatively low, and the shape of the curve is normal during the experiment, and there are no phenomena such as cores or bulges.
  • Example 6 From the comparison between Example 6 and Comparative Example 1, it can be seen that the crystal phase transformation type high-temperature reinforcing agent has no adverse effect on the conventional performance of the cement slurry.
  • Example 4 By comparing Example 4 with Comparative Example 2, it can be seen that the ultra-high temperature retarder used in the present invention has good ultra-high temperature resistance, can effectively adjust the thickening time of cement slurry, and ensure safe construction.
  • Comparing Example 5 with Comparative Example 3 it can be seen that the ultra-high temperature fluid loss reducer used in the present invention has good ultra-high temperature resistance, can effectively control cement slurry fluid loss and maintain slurry stability.
  • This test example is to the long-term compressive strength evolution situation of the cement stone formed by the crystal phase transformation type high temperature reinforcing agent of embodiment 1-7 to the permeable crystallization type anti-channeling cement stone formed by cement slurry and the cement stone formed by the cement slurry of comparative example 1
  • the test was carried out and the results are shown in Table 2.
  • the temperature of the thickening test is lower than the static temperature at the bottom of the well, usually 0.8-0.9 times of the static temperature at the bottom of the well. Therefore, in the test, the curing temperature of cement stone is 20-30°C higher than the temperature of the thickening test.
  • Example 6 By comparing Example 6 with Comparative Example 1, it can be seen that after 28 days of curing, the strength of the cement stone formed by the cement slurry in Example 6 is about 2.42 times that of Comparative Example 1, indicating that the crystal phase transformation type high-temperature reinforcing agent can greatly improve The high temperature strength decline performance of cement stone.

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Abstract

A crystalline phase modified broad-spectrum ultrahigh-temperature-resistant well cementing slurry and an application thereof. The well cementing slurry contains a crystalline phase modified high-temperature enhancer. The crystalline phase modified high-temperature enhancer comprises: 10-30% of sodium aluminate, 2-10% of micro-silicon, 30-50% of calcium aluminate, 30-50% of metakaolin, and 1-5% of inorganic fibers. The crystalline phase modified high-temperature enhancer can participate in the hydration reaction of silica cement and generate the anorthite phase, the anorthite has excellent high-temperature resistance, the crystal transformation phenomenon of the ultra-high temperature cement stone can be slowed down, and then the cement slurry has good ultra-high temperature strength decay resistance.

Description

一种晶相改造型广谱抗超高温固井水泥浆及其应用A crystal phase modified broad-spectrum ultra-high temperature resistant cementing cement slurry and its application 技术领域technical field
本发明涉及固井水泥浆技术领域,尤其涉及一种晶相改造型广谱抗超高温固井水泥浆。The invention relates to the technical field of cementing cement slurry, in particular to a crystal phase modified broad-spectrum ultra-high temperature resistant cementing slurry.
背景技术Background technique
随着浅层易动用资源的减少及油田勘探开发的不断深入,高温深井超深井、地热井、干热岩等逐渐成为勘探开发的焦点。在超高温条件下,固井作业难度和复杂程度将大幅提高,对固井水泥浆、水泥石的性能要求也将大幅提高,固井水泥浆与水泥环主要面临三个方面问题:一是高温易导致水泥外加剂失效变性,水泥浆易出现高温沉降失稳、流变性难以兼顾、失水难以控制、稠化时间难以调整等系列复杂问题,极易造成固井安全事故和质量问题;二是长裸眼大温差条件下水泥石强度发展缓慢甚至超缓凝问题。例如当悬挂器和套管鞋处静止温差过大且水泥浆密度较高时,极易导致悬挂器位置水泥浆长期不凝,不仅会使得建井周期延长,还使得喇叭口处窜气的风险增大;三是长期超高温作用下水泥石强度衰退问题。温度超过110℃时水泥水化产物发生晶体转型,会使得水泥石孔隙度和渗透率升高、强度发生衰退,导致水泥环力学完整性和结构完整性降低,引发后期气窜与环空带压问题。With the reduction of easy-to-produce resources in shallow layers and the continuous deepening of oilfield exploration and development, high-temperature deep wells and ultra-deep wells, geothermal wells, and hot dry rocks have gradually become the focus of exploration and development. Under ultra-high temperature conditions, the difficulty and complexity of cementing operations will be greatly increased, and the performance requirements for cement slurry and cement stone will also be greatly increased. The cement slurry and cement sheath mainly face three problems: First, high temperature It is easy to cause the failure and denaturation of cement admixture, and the cement slurry is prone to high-temperature settlement instability, difficult to balance rheology, difficult to control water loss, difficult to adjust thickening time and other complex problems, which can easily cause cementing safety accidents and quality problems; Under the condition of long open hole and large temperature difference, the strength of cement stone develops slowly or even super retarded. For example, when the static temperature difference between the hanger and the casing shoe is too large and the cement slurry density is high, it is very easy to cause the cement slurry at the hanger position to not condense for a long time, which will not only prolong the well construction period, but also cause the risk of gas blow-by at the bell mouth The third is the strength decline of cement stone under the action of long-term ultra-high temperature. When the temperature exceeds 110 °C, the crystal transformation of cement hydration products will increase the porosity and permeability of the cement stone, and the strength will decline, resulting in a decrease in the mechanical integrity and structural integrity of the cement annulus, causing gas channeling and annular pressure in the later stage question.
目前,本领域从新型外加剂研发、高温增强材料或抗高温强度衰退材料及水泥浆系方面开展了较多的超高温固井水泥浆体系研究,但仍存在外加剂抗温能力不足,特别是稳定抗>180℃超高温的能力不足,适用温度区间窄、敏感性大以及单一掺入硅粉的手段难以有效抑制>180℃超高温条件下固井水泥石强度大幅衰退等问题。At present, a lot of research on ultra-high temperature cementing cement slurry system has been carried out in this field from the research and development of new admixtures, high-temperature reinforcing materials or high-temperature strength decay-resistant materials, and cement slurry systems, but there are still insufficient temperature resistance capabilities of admixtures, especially The ability to stably resist ultra-high temperatures >180°C is insufficient, the applicable temperature range is narrow, the sensitivity is high, and the single method of adding silica fume is difficult to effectively suppress the significant decline in the strength of cement cement under ultra-high temperatures >180°C.
发明内容Contents of the invention
为解决上述技术问题,本发明的目的在于提供一种晶相改造型广谱抗超高温固井水泥浆,通过添加晶相改造型高温增强剂,能够有效克服常规硅粉水泥浆体系在长期超高温条件下强度衰退的问题。In order to solve the above-mentioned technical problems, the object of the present invention is to provide a crystal phase modified broad-spectrum ultra-high temperature resistant cementing cement slurry, which can effectively overcome the long-term ultra-high temperature resistance of the conventional silica fume cement slurry system by adding a crystal phase modified high-temperature reinforcing agent. The problem of strength decline under high temperature conditions.
为达到上述目的,本发明提供了一种晶相改造型广谱抗超高温固井水泥浆,其中,该固井水泥浆含有晶型改造型高温增强剂;In order to achieve the above object, the present invention provides a crystal phase transformation type broad-spectrum ultra-high temperature resistant cementing cement slurry, wherein the cementing cement slurry contains a crystal transformation type high temperature enhancer;
以重量百分比计,所述晶相改造型高温增强剂的组成包括10-30%铝酸钠、2-10%微硅、30-50%铝酸钙、30-50%偏高岭土、1-5%无机纤维。In terms of weight percent, the composition of the crystal phase transformation type high-temperature reinforcing agent includes 10-30% sodium aluminate, 2-10% micro-silicon, 30-50% calcium aluminate, 30-50% metakaolin, 1-5% % inorganic fibers.
根据本发明的具体实施方案,优选地,以重量份计,该固井水泥浆具有以下成分组 成:According to a specific embodiment of the present invention, preferably, in parts by weight, the cementing slurry has the following composition:
油井水泥100份、硅粉40-50份、加重剂0-100份、膨胀剂1-3份、晶相改造型高温增强剂3-10份、分散剂1-2份、悬浮剂1-2份、增韧剂1-3份、超高温缓凝剂2-6份、超高温降失水剂3-7份、水55-65份。100 parts of oil well cement, 40-50 parts of silicon powder, 0-100 parts of weighting agent, 1-3 parts of expansion agent, 3-10 parts of crystal phase modification high-temperature reinforcing agent, 1-2 parts of dispersant, 1-2 parts of suspending agent 1-3 parts of toughening agent, 2-6 parts of ultra-high temperature retarder, 3-7 parts of ultra-high temperature fluid loss reducer, and 55-65 parts of water.
根据本发明的具体实施方案,优选地,在所述晶相改造型高温增强剂中,所述铝酸钠的纯度>93%。According to a specific embodiment of the present invention, preferably, in the crystal phase transformation type high-temperature reinforcing agent, the purity of the sodium aluminate is >93%.
根据本发明的具体实施方案,优选地,在所述晶相改造型高温增强剂中,所述铝酸钠的细度为200-300目。According to a specific embodiment of the present invention, preferably, in the crystal phase transformation type high-temperature reinforcing agent, the fineness of the sodium aluminate is 200-300 mesh.
根据本发明的具体实施方案,优选地,在所述晶相改造型高温增强剂中,所述铝酸钙的纯度>90%。According to a specific embodiment of the present invention, preferably, in the crystal phase transformation type high-temperature reinforcing agent, the purity of the calcium aluminate is >90%.
根据本发明的具体实施方案,优选地,在所述晶相改造型高温增强剂中,所述铝酸钙的细度为200-300目。According to a specific embodiment of the present invention, preferably, in the crystal phase transformation type high-temperature reinforcing agent, the fineness of the calcium aluminate is 200-300 mesh.
根据本发明的具体实施方案,优选地,在所述晶相改造型高温增强剂中,所述偏高岭土具有以下化学指标要求:SiO 2含量≤50%、Al 2O 3含量≥40%、游离CaO含量≤1%。 According to a specific embodiment of the present invention, preferably, in the crystal phase transformation type high-temperature reinforcing agent, the metakaolin has the following chemical index requirements: SiO 2 content ≤ 50%, Al 2 O 3 content ≥ 40%, free CaO content ≤ 1%.
根据本发明的具体实施方案,优选地,在所述晶相改造型高温增强剂中,所述无机纤维为经过表面处理的可分散性碳纤维或玄武岩纤维。According to a specific embodiment of the present invention, preferably, in the crystal phase transformation type high-temperature reinforcing agent, the inorganic fiber is a surface-treated dispersible carbon fiber or basalt fiber.
根据本发明的具体实施方案,优选地,在所述晶相改造型高温增强剂中,所述无机纤维的长度为3-6mm。According to a specific embodiment of the present invention, preferably, in the crystal phase transformation type high-temperature reinforcing agent, the length of the inorganic fibers is 3-6 mm.
根据本发明的具体实施方案,上述晶相改造型高温增强剂可以是按照以下步骤制备的:According to a specific embodiment of the present invention, the above-mentioned crystal phase transformation type high-temperature reinforcing agent can be prepared according to the following steps:
步骤1:将铝酸钠与微硅搅拌共混,得到混合物,搅拌共混的时间可以控制为5min;Step 1: Stir and blend sodium aluminate and microsilicon to obtain a mixture, and the time of stirring and blending can be controlled to 5 minutes;
步骤2:将铝酸钙、偏高岭土、无机纤维加入到步骤1所得到的混合物中,搅拌共混,得到晶相改造型高温增强剂,搅拌共混的时间可以控制为15min。Step 2: Add calcium aluminate, metakaolin, and inorganic fibers to the mixture obtained in step 1, and stir and blend to obtain a crystal phase modification type high-temperature reinforcing agent. The time of stirring and blending can be controlled to 15 minutes.
根据本发明的具体实施方案,优选地,在所述固井水泥浆中,所述硅粉为二氧化硅质量含量≥97%的200目硅粉和600目硅粉的组合,并且,所述200目硅粉与600目硅粉的重量比为(4-7):(3-6)。According to a specific embodiment of the present invention, preferably, in the cementing cement slurry, the silica fume is a combination of 200 mesh silica fume and 600 mesh silica fume with a silica mass content ≥ 97%, and the The weight ratio of 200 mesh silicon powder to 600 mesh silicon powder is (4-7):(3-6).
根据本发明的具体实施方案,优选地,在所述固井水泥浆中,所述加重剂为密度≥7.0g/cm 3的铁矿粉。 According to a specific embodiment of the present invention, preferably, in the cement slurry, the weighting agent is iron ore powder with a density ≥ 7.0 g/cm 3 .
根据本发明的具体实施方案,优选地,在所述固井水泥浆中,所述膨胀剂为硫铝酸钙与氧化钙的混合物,混合重量比例(1-4):1。According to a specific embodiment of the present invention, preferably, in the cementing cement slurry, the expansion agent is a mixture of calcium sulfoaluminate and calcium oxide, and the mixing weight ratio is (1-4):1.
根据本发明的具体实施方案,优选地,在所述固井水泥浆中,所述分散剂为磺化甲醛-丙酮缩合物和/或聚萘磺酸盐。According to a specific embodiment of the present invention, preferably, in the cement slurry, the dispersant is sulfonated formaldehyde-acetone condensate and/or polynaphthalene sulfonate.
根据本发明的具体实施方案,优选地,在所述固井水泥浆中,所述悬浮剂为2-丙烯酰胺-2-甲基丙磺酸类(AMPS)聚合物增粘材料。According to a specific embodiment of the present invention, preferably, in the cement slurry, the suspending agent is 2-acrylamide-2-methylpropanesulfonic acid (AMPS) polymer viscosity-increasing material.
根据本发明的具体实施方案,优选地,在所述固井水泥浆中,所述增韧剂为耐高温橡胶粉和/或树脂弹性体微球。According to a specific embodiment of the present invention, preferably, in the cement slurry, the toughening agent is high temperature resistant rubber powder and/or resin elastomer microspheres.
根据本发明的具体实施方案,优选地,在所述固井水泥浆中,所述超高温缓凝剂由衣康酸(IA)、2-丙烯酰胺-2-甲基丙磺酸(AMPS)、N,N-二甲基丙烯酰胺(DMAA)、乙烯磷酸聚合而成。According to a specific embodiment of the present invention, preferably, in the cement slurry, the ultra-high temperature retarder consists of itaconic acid (IA), 2-acrylamide-2-methylpropanesulfonic acid (AMPS), N,N-dimethylacrylamide (DMAA), vinyl phosphoric acid polymerized.
根据本发明的具体实施方案,优选地,该超高温缓凝剂的制备方法包括:According to a specific embodiment of the present invention, preferably, the preparation method of the ultra-high temperature retarder comprises:
(1)按质量百分比将总投量20-30%的衣康酸(IA)、38-48%的2-丙烯酰胺-2-甲基丙磺酸(AMPS)、20-28%的N,N-二甲基丙烯酰胺(DMAA)全部溶于以上投料总质量2-3倍的去离子水中,调节pH至5.5-6.5(采用浓度为30%的氢氧化钠溶液调节pH值),搅拌均匀后形成混合液;(1) Add the itaconic acid (IA) of 20-30% total dosage, the 2-acrylamide-2-methylpropanesulfonic acid (AMPS) of 38-48%, the N of 20-28% by mass percentage, N-dimethylacrylamide (DMAA) is all dissolved in deionized water 2-3 times the total mass of the above feed, and the pH is adjusted to 5.5-6.5 (the pH value is adjusted by using a 30% sodium hydroxide solution), and stirred evenly After forming a mixture;
(2)将步骤(1)中所得混合液置于反应装置(优选带有搅拌器、温度计和氮气保护条件的反应装置)中,通入保护气体(优选惰性气体或氮气)排尽反应装置中的氧气;(2) Place the mixed solution obtained in step (1) in a reaction device (preferably a reaction device with a stirrer, a thermometer and a nitrogen protection condition), and pass into a protective gas (preferably an inert gas or nitrogen) to exhaust the reaction device of oxygen;
(3)将反应装置升温至58-63℃;优选将步骤(2)中排尽氧气后的反应装置置于水浴锅中,开启搅拌器的同时将混合液升温至58-63℃;(3) Warm up the reaction device to 58-63°C; preferably place the reaction device after exhausting oxygen in step (2) in a water bath, and heat the mixed solution to 58-63°C while starting the stirrer;
(4)在搅拌速率60-80转/分钟、氮气保护条件下,将引发剂以6-8ml/min的滴加速率滴加至混合液中,反应0.5小时;(4) Add the initiator dropwise to the mixed solution at a rate of 6-8ml/min under the conditions of a stirring rate of 60-80 rpm and nitrogen protection, and react for 0.5 hours;
(5)将总投量8-12%的乙烯磷酸(VA)溶于其质量的1-2倍的水中,以10-15ml/min滴加速率滴加至步骤(4)反应0.5小时后的混合液中,继续反应1.5-2小时后冷却,获得超高温缓凝剂。(5) Dissolve vinyl phosphoric acid (VA) with a total dosage of 8-12% in water 1-2 times its mass, and add it dropwise to step (4) after 0.5 hours of reaction at a rate of 10-15ml/min. In the mixed solution, continue to react for 1.5-2 hours and then cool to obtain an ultra-high temperature retarder.
根据本发明的具体实施方案,优选地,在所述固井水泥浆中,所述超高温降失水剂由2-丙烯酰胺-2-甲基丙磺酸(AMPS)、丙烯酸(AA)、N,N-二甲基丙烯酰胺(DMAA)、N-乙烯基吡咯烷酮(NVP)、微晶纤维素(MCC)聚合而成。According to a specific embodiment of the present invention, preferably, in the cement slurry, the ultra-high temperature fluid loss reducer is composed of 2-acrylamide-2-methylpropanesulfonic acid (AMPS), acrylic acid (AA), N,N-dimethylacrylamide (DMAA), N-vinylpyrrolidone (NVP), and microcrystalline cellulose (MCC) are polymerized.
根据本发明的具体实施方案,优选地,该超高温降失水剂的制备方法包括:According to a specific embodiment of the present invention, preferably, the preparation method of the ultra-high temperature fluid loss reducing agent comprises:
(1)按质量分数将总投量30-60%的2-丙烯酰胺-2-甲基丙磺酸(AMPS)、20-30%的丙烯酸(AA)溶于相当于总投量4-5倍的去离子水中,调节pH至7-7.5(采用浓度为30%的氢氧化钠溶液调节pH值),搅拌均匀后形成混合液;(1) Dissolve the 2-acrylamide-2-methylpropanesulfonic acid (AMPS) and the acrylic acid (AA) of 20-30% of the total dosage of 30-60% in the amount equivalent to the total dosage of 4-5 times the deionized water, adjust the pH to 7-7.5 (using a 30% sodium hydroxide solution to adjust the pH value), stir to form a mixed solution;
(2)将总投量10-15%的N,N-二甲基丙烯酰胺(DMAA)、4-8%的N-乙烯基吡咯烷酮(NVP)、0.2%的N,N-亚甲基双丙烯酰胺(MBA)加入步骤(1)的混合液中,搅拌均匀;(2) Add 10-15% of N,N-dimethylacrylamide (DMAA), 4-8% of N-vinylpyrrolidone (NVP), 0.2% of N,N-methylenebis Add acrylamide (MBA) into the mixed solution of step (1), and stir evenly;
(3)将步骤(2)的混合液置于反应装置(优选带有搅拌器、温度计和氮气保护条件的反应装置)中,通入保护气体(优选惰性气体或氮气)排尽反应装置中的空气;(3) the mixed solution of step (2) is placed in the reaction device (preferably the reaction device with agitator, thermometer and nitrogen protection conditions), feeds protective gas (preferably inert gas or nitrogen) to exhaust the reaction device Air;
(4)将步骤(3)的混合液升温至60-65℃,优选将排尽空气后的反应装置置于水浴锅中,开启搅拌器的同时将混合液升温至60-65℃;(4) Warm up the mixed solution in step (3) to 60-65°C, preferably place the reaction device after exhausting the air in a water bath, and turn on the stirrer while heating the mixed solution to 60-65°C;
(5)在搅拌速率60-80转/分钟、氮气保护条件下,将引发剂以4-6ml/min的滴加速率滴加至混合液中,反应3小时;(5) Add the initiator dropwise to the mixture at a rate of 4-6ml/min at a stirring rate of 60-80 rpm and nitrogen protection, and react for 3 hours;
(6)将总投量15-20%的微晶纤维素(MCC)加入其质量5倍的水中,搅拌均匀后以3-4ml/min滴加速率滴加至步骤(5)的混合液,继续反应2小时后冷却,获得超高温降失水剂。(6) Add microcrystalline cellulose (MCC) with a total dosage of 15-20% into water with 5 times its mass, stir it and add it dropwise to the mixed solution of step (5) at a rate of 3-4ml/min, Continue to react for 2 hours and then cool to obtain an ultra-high temperature dehydration agent.
根据本发明的具体实施方案,优选地,本发明的固井水泥浆的适用密度范围为1.85-2.40g/cm 3According to a specific embodiment of the present invention, preferably, the applicable density range of the cement slurry of the present invention is 1.85-2.40 g/cm 3 .
根据本发明的具体实施方案,本发明提供的晶相改造型广谱抗超高温固井水泥浆可以是通过以下步骤制备的:According to a specific embodiment of the present invention, the crystal phase modification type broad-spectrum ultra-high temperature resistant cementing cement slurry provided by the present invention can be prepared through the following steps:
按各组分的重量份将油井水泥、硅粉、加重剂、膨胀剂、晶相改造型高温增强剂、分散剂、悬浮剂、增韧剂混合搅拌均匀,得到干混料;按照各组分的重量份,将超高温缓凝剂、超高温降失水剂及水混合搅拌均匀,得到配浆水;将所述干混料加入到所述配浆水中,混合搅拌均匀得到所述晶相改造型广谱抗超高温固井水泥浆。According to the parts by weight of each component, the oil well cement, silica fume, weighting agent, expansion agent, crystal phase transformation type high-temperature reinforcing agent, dispersant, suspending agent, and toughening agent are mixed and stirred evenly to obtain a dry blend; parts by weight, mix and stir the ultra-high temperature retarder, ultra-high temperature fluid loss reducer and water evenly to obtain slurry preparation water; add the dry blend to the slurry preparation water, mix and stir evenly to obtain the crystal phase Modified broad-spectrum ultra-high temperature resistant cementing cement slurry.
本发明还提供了上述晶相改造型广谱抗超高温固井水泥浆在固井作业中的应用。The present invention also provides the application of the crystal phase reformed broad-spectrum ultra-high temperature resistant well cementing cement slurry in well cementing operations.
根据本发明的具体实施方案,优选地,所述水泥浆固化之后形成钙长石物相。According to a specific embodiment of the present invention, preferably, the anorthite phase is formed after the cement slurry is cured.
根据本发明的具体实施方案,优选地,所述固井作业是指深井超深井、干热岩、地热井等高温超高温地层的固井作业。According to a specific embodiment of the present invention, preferably, the cementing operation refers to the cementing operation in high-temperature and ultra-high-temperature formations such as deep wells and ultra-deep wells, hot dry rocks, and geothermal wells.
根据本发明的具体实施方案,优选地,该晶相改造型广谱抗超高温固井水泥浆的适用循环温度范围为110℃-230℃。According to a specific embodiment of the present invention, preferably, the applicable circulation temperature range of the crystal phase modified broad-spectrum ultra-high temperature resistant cement slurry is 110°C-230°C.
与现有技术相比,本发明的上述技术方案具有如下优点:Compared with the prior art, the above-mentioned technical solution of the present invention has the following advantages:
(1)本发明的固井水泥浆中掺入的晶相改造型高温增强剂可参与硅粉水泥水化反应并生成钙长石物相,钙长石具有优异的抗高温能力,可减缓超高温水泥石的转晶现象,进而使得本发明水泥浆体系具有良好的抗超高温强度衰退性能。(1) The crystal phase transformation type high-temperature reinforcing agent mixed in the cement slurry of the present invention can participate in the hydration reaction of silica fume cement and generate anorthite phase. Anorthite has excellent high temperature resistance and can slow down super The crystallization phenomenon of high-temperature cement stone further makes the cement slurry system of the present invention have good resistance to ultra-high temperature strength decline.
(2)本发明水泥浆体系通过采用抗温性能优良且敏感性低的外加剂,可满足循环温度110℃-230℃要求,具有很宽的温度适用范围,同时密度与稠化时间可调,顶部强度发展快,能够满足“中高温(110-150℃)-高温(150-205℃)-超高温(>205℃)”跨温区应用要求。(2) The cement slurry system of the present invention adopts an admixture with excellent temperature resistance and low sensitivity, which can meet the requirement of a cycle temperature of 110°C-230°C, has a wide range of temperature applications, and can adjust the density and thickening time at the same time. The strength of the top develops rapidly, which can meet the application requirements of "medium-high temperature (110-150°C)-high temperature (150-205°C)-ultra-high temperature (>205°C)" across temperature zones.
附图说明Description of drawings
图1为实施例3的固井水泥浆的稠化测试曲线图。Fig. 1 is a thickening test curve of the cementing slurry of Example 3.
图2为实施例6的固井水泥浆的稠化测试曲线图。Fig. 2 is a thickening test curve of the cement slurry of Example 6.
具体实施方式Detailed ways
为了对本发明的技术特征、目的和有益效果有更加清楚的理解,现对本发明的技术方案进行以下详细说明,但不能理解为对本发明的可实施范围的限定。In order to have a clearer understanding of the technical features, purposes and beneficial effects of the present invention, the technical solution of the present invention is described in detail below, but it should not be construed as limiting the scope of implementation of the present invention.
材料 Material :
硅粉:200目硅粉与600目硅粉的重量比为4:6;Silicon powder: the weight ratio of 200 mesh silicon powder to 600 mesh silicon powder is 4:6;
膨胀剂:质量比3:1的硫铝酸钙与氧化钙的混合物;Expansion agent: a mixture of calcium sulfoaluminate and calcium oxide with a mass ratio of 3:1;
晶相改造型高温增强剂:按质量分数15%铝酸钠、4%微硅、33%铝酸钙、36%偏高岭土、2%无机纤维的混合物;Crystal phase modified high-temperature reinforcing agent: a mixture of 15% sodium aluminate, 4% microsilicon, 33% calcium aluminate, 36% metakaolin, and 2% inorganic fiber by mass fraction;
分散剂:磺化甲醛-丙酮缩合物FS200L,生产厂家为四川安钮诺斯油气能源技术有限公司;Dispersant: sulfonated formaldehyde-acetone condensate FS200L, the manufacturer is Sichuan Annuosi Oil and Gas Energy Technology Co., Ltd.;
悬浮剂:SP200S,生产厂家为四川安钮诺斯油气能源技术有限公司;Suspending agent: SP200S, the manufacturer is Sichuan Annuox Oil and Gas Energy Technology Co., Ltd.;
增韧剂:HE-1S,生产厂家为四川安钮诺斯油气能源技术有限公司;Toughener: HE-1S, the manufacturer is Sichuan Annuosi Oil and Gas Energy Technology Co., Ltd.;
超高温缓凝剂:按照质量百分比为23%衣康酸、44%2-丙烯酰胺-2-甲基丙磺酸、22%N,N-二甲基丙烯酰胺、11%乙烯磷酸聚合制成;Ultra-high temperature retarder: made by polymerizing 23% itaconic acid, 44% 2-acrylamide-2-methylpropanesulfonic acid, 22% N,N-dimethylacrylamide, and 11% ethylene phosphoric acid in terms of mass percentage ;
超高温降失水剂:按照质量百分比为45%2-丙烯酰胺-2-甲基丙磺酸、23%丙烯酸、11%N,N-二甲基丙烯酰胺、4%N-乙烯基吡咯烷酮,0.2%的N,N-亚甲基双丙烯酰胺、16.8%微晶纤维素聚合制成;Ultra-high temperature fluid loss reducer: 45% 2-acrylamide-2-methylpropanesulfonic acid, 23% acrylic acid, 11% N,N-dimethylacrylamide, 4% N-vinylpyrrolidone according to mass percentage, Made of 0.2% N,N-methylenebisacrylamide and 16.8% microcrystalline cellulose;
加重剂:密度为7.0g/cm 3的铁矿粉。 Weighting agent: iron ore powder with a density of 7.0g/cm 3 .
实施例1Example 1
本实施例提供了一种密度1.85g/cm 3、应用温度110℃的晶相改造型广谱抗超高温固井水泥浆,其由以下组分按重量份配比组成:油井水泥100份、硅粉40份、膨胀剂1份、晶相改造型高温增强剂3份、分散剂1份、悬浮剂1份、增韧剂2份、超高温缓凝剂2份、超高温降失水剂3份、水62份。 This example provides a crystal phase reformed broad-spectrum ultra-high temperature resistant well cementing cement slurry with a density of 1.85g/cm 3 and an application temperature of 110°C, which is composed of the following components in proportion by weight: 100 parts of oil well cement, 40 parts of silicon powder, 1 part of expansion agent, 3 parts of crystal phase reforming high-temperature strengthening agent, 1 part of dispersing agent, 1 part of suspending agent, 2 parts of toughening agent, 2 parts of ultra-high temperature retarder, and ultra-high temperature fluid loss reducer 3 parts, 62 parts of water.
实施例2Example 2
本实施例提供了一种密度2.40g/cm 3、应用温度110℃的晶相改造型广谱抗超高温固井水泥浆,其由以下组分按重量份配比组成:油井水泥100份、硅粉40份、加重剂100份、膨胀剂1份、晶相改造型高温增强剂3份、分散剂2份、悬浮剂1.5份、增韧剂1份、超高温缓凝剂2份、超高温降失水剂3份、水58份。 This example provides a crystal phase reformed broad-spectrum ultra-high temperature resistant well cementing cement slurry with a density of 2.40g/cm 3 and an application temperature of 110°C, which is composed of the following components in proportion by weight: 100 parts of oil well cement, 40 parts of silicon powder, 100 parts of weighting agent, 1 part of expansion agent, 3 parts of crystal phase modification high temperature reinforcing agent, 2 parts of dispersing agent, 1.5 parts of suspending agent, 1 part of toughening agent, 2 parts of super high temperature retarder, super 3 parts of high temperature fluid loss reducer, 58 parts of water.
实施例3Example 3
本实施例提供了一种密度1.95g/cm 3、应用温度150℃的晶相改造型广谱抗超高温固井水泥浆,其由以下组分按重量份配比组成:油井水泥100份、硅粉40份、膨胀剂2份、晶相改造型高温增强剂5份、分散剂1份、悬浮剂1.5份、增韧剂1.5份、超高温缓凝剂3.5份、超高温降失水剂4份、水62份。 This example provides a crystal phase reformed broad-spectrum ultra-high temperature resistant well cementing cement slurry with a density of 1.95g/cm 3 and an application temperature of 150°C, which is composed of the following components in proportion by weight: 100 parts of oil well cement, 40 parts of silicon powder, 2 parts of expansion agent, 5 parts of crystal phase reforming high temperature reinforcing agent, 1 part of dispersing agent, 1.5 parts of suspending agent, 1.5 parts of toughening agent, 3.5 parts of super high temperature retarder, super high temperature fluid loss reducer 4 parts, 62 parts of water.
实施例4Example 4
本实施例提供了一种密度1.95g/cm 3、应用温度180℃的晶相改造型广谱抗超高温固井水泥浆,其由以下组分按重量份配比组成:油井水泥100份、硅粉45份、膨胀剂2份、晶相改造型高温增强剂5份、分散剂1份、悬浮剂1.5份、增韧剂1.5份、超高温缓凝剂4份、超高温降失水剂5份、水62份。 This example provides a crystal phase reformed broad-spectrum ultra-high temperature resistant well cementing cement slurry with a density of 1.95g/cm 3 and an application temperature of 180°C, which is composed of the following components in proportion by weight: 100 parts of oil well cement, 45 parts of silicon powder, 2 parts of expansion agent, 5 parts of crystal phase reforming high-temperature strengthening agent, 1 part of dispersing agent, 1.5 parts of suspending agent, 1.5 parts of toughening agent, 4 parts of ultra-high temperature retarder, and ultra-high temperature fluid loss reducer 5 parts, 62 parts of water.
实施例5Example 5
本实施例提供了一种密度2.20g/cm 3、应用温度180℃的晶相改造型广谱抗超高温固井水泥浆,其由以下组分按重量份配比组成:油井水泥100份、硅粉45份、加重剂54份、膨胀剂2份、晶相改造型高温增强剂5份、分散剂2份、悬浮剂1.5份、增韧剂2份、超高温缓凝剂3.5份、超高温降失水剂5.5份、水55份。 This example provides a crystal phase reformed broad-spectrum ultra-high temperature resistant well cementing cement slurry with a density of 2.20g/cm 3 and an application temperature of 180°C, which is composed of the following components in proportion by weight: 100 parts of oil well cement, 45 parts of silicon powder, 54 parts of weighting agent, 2 parts of expansion agent, 5 parts of crystal phase reforming high temperature reinforcing agent, 2 parts of dispersing agent, 1.5 parts of suspending agent, 2 parts of toughening agent, 3.5 parts of super high temperature retarder, super 5.5 parts of high temperature fluid loss reducer, 55 parts of water.
实施例6Example 6
本实施例提供了一种密度1.85g/cm 3、应用温度230℃的晶相改造型广谱抗超高温固井水泥浆,其由以下组分按重量份配比组成:油井水泥100份、硅粉50份、膨胀剂2份、晶相改造型高温增强剂7份、分散剂1份、悬浮剂2份、增韧剂3份、超高温缓凝剂5份、超高温降失水剂7份、水61份。 This example provides a crystal phase reformed broad-spectrum ultra-high temperature resistant well cementing cement slurry with a density of 1.85g/cm 3 and an application temperature of 230°C, which is composed of the following components in proportion by weight: 100 parts of oil well cement, 50 parts of silicon powder, 2 parts of expansion agent, 7 parts of crystal phase reforming high-temperature strengthening agent, 1 part of dispersing agent, 2 parts of suspending agent, 3 parts of toughening agent, 5 parts of ultra-high temperature retarder, and ultra-high temperature fluid loss reducer 7 parts, 61 parts of water.
实施例7Example 7
本实施例提供了一种密度2.40g/cm 3、应用温度230℃的晶相改造型广谱抗超高温固井水泥浆,其由以下组分按重量份配比组成:油井水泥100份、硅粉50份、加重剂100份、膨胀剂2份、晶相改造型高温增强剂7份、分散剂2份、悬浮剂2份、增韧剂2份、超高温缓凝剂6份、超高温降失水剂7份、水65份。 This example provides a crystal phase reformed broad-spectrum ultra-high temperature resistant well cementing cement slurry with a density of 2.40g/cm 3 and an application temperature of 230°C, which is composed of the following components in proportion by weight: 100 parts of oil well cement, 50 parts of silicon powder, 100 parts of weighting agent, 2 parts of expansion agent, 7 parts of crystal phase transformation high-temperature reinforcing agent, 2 parts of dispersing agent, 2 parts of suspending agent, 2 parts of toughening agent, 6 parts of ultra-high temperature retarder, super 7 parts of high temperature fluid loss reducer, 65 parts of water.
对比例1Comparative example 1
本对比例提供了一种密度1.85g/cm 3、应用温度230℃的不含晶相改造型高温增强剂的固井水泥浆,其由以下组分按重量份配比组成:油井水泥100份、硅粉50份、膨胀剂2份、分散剂1份、悬浮剂2份、增韧剂3份、超高温缓凝剂5份、超高温降失水剂7份、水60份。 This comparative example provides a cementing slurry with a density of 1.85g/cm 3 and an application temperature of 230°C that does not contain a crystal-phase modified high-temperature reinforcing agent, which is composed of the following components in proportion by weight: 100 parts of oil well cement , 50 parts of silicon powder, 2 parts of expansion agent, 1 part of dispersant, 2 parts of suspending agent, 3 parts of toughening agent, 5 parts of ultra-high temperature retarder, 7 parts of ultra-high temperature fluid loss reducer, and 60 parts of water.
对比例2Comparative example 2
本对比例提供了一种密度1.95g/cm 3、应用温度180℃,采用市售抗高温缓凝剂配制(抗温能力<180℃)的固井水泥浆,其由以下组分按重量份配比组成:油井水泥100份、硅粉45份、膨胀剂2份、晶相改造型高温增强剂5份、分散剂1份、悬浮剂1.5份、增韧剂1.5份、市售缓凝剂4份、超高温降失水剂5份、水62份。 This comparative example provides a cementing cement slurry with a density of 1.95g/cm 3 , an application temperature of 180°C, and a commercially available anti-high temperature retarder (temperature resistance <180°C), which consists of the following components in parts by weight Proportion composition: 100 parts of oil well cement, 45 parts of silica fume, 2 parts of expansion agent, 5 parts of crystal phase reforming high-temperature reinforcing agent, 1 part of dispersant, 1.5 parts of suspending agent, 1.5 parts of toughening agent, commercially available retarder 4 parts, 5 parts of ultra-high temperature fluid loss reducer, and 62 parts of water.
对比例3Comparative example 3
本对比例提供了一种密度2.20g/cm 3、应用温度180℃的,采用市售抗高温降失水剂(抗温能力<180℃)的固井水泥浆,其由以下组分按重量份配比组成:油井水泥100份、硅粉45份、加重剂54份、膨胀剂2份、晶相改造型高温增强剂5份、分散剂2份、悬浮剂1.5份、增韧剂2份、超高温缓凝剂3.5份、市售降失水剂5.5份、水55份。 This comparative example provides a cementing cement slurry with a density of 2.20g/cm 3 and an application temperature of 180°C, using a commercially available anti-high temperature fluid loss reducing agent (temperature resistance <180°C), which consists of the following components by weight Proportion composition: 100 parts of oil well cement, 45 parts of silicon fume, 54 parts of weighting agent, 2 parts of expansion agent, 5 parts of crystal phase modification high temperature reinforcing agent, 2 parts of dispersant, 1.5 parts of suspending agent, 2 parts of toughening agent , 3.5 parts of ultra-high temperature retarder, 5.5 parts of commercially available fluid loss reducer, and 55 parts of water.
测试例1test case 1
按照GB/T 19139《油井水泥试验方法》和GB/T 2419《水泥胶砂流动度测定方法》,本测试例对实施例1-7的晶相改造型广谱抗超高温固井水泥浆与对比例1-3的密度、游离液、流动度、API失水、稠化时间等常规工程进行性能测试,结果如表1所示。According to GB/T 19139 "Oil Well Cement Test Method" and GB/T 2419 "Measurement Method for Fluidity of Cement Mortar Sand", this test example is for the crystal phase transformation type broad-spectrum anti-ultra-high temperature cementing cement slurry of embodiment 1-7 and Performance tests were performed on conventional projects such as density, free liquid, fluidity, API dehydration, and thickening time of Examples 1-3, and the results are shown in Table 1.
实施例3的稠化时间测试的参数条件如下:初始稠度开始时间15.0min,初始稠度结束时间30.0min;初始温度25.5℃,目标温度150.0℃;初始压力-1.9MPa,目标压力80.0MPa;初始稠度29.2Bc,报警稠度100.0Bc;30Bc稠化时间05:03:38,40Bc稠化时间05:08:39,50Bc稠化时间05:09:39,60Bc稠化时间05:10:39,70Bc稠化时间05:12:09,稠化时间05:13:30;The parameter conditions of the thickening time test in Example 3 are as follows: initial consistency start time 15.0min, initial consistency end time 30.0min; initial temperature 25.5°C, target temperature 150.0°C; initial pressure -1.9MPa, target pressure 80.0MPa; initial consistency 29.2Bc, alarm consistency 100.0Bc; 30Bc thickening time 05:03:38, 40Bc thickening time 05:08:39, 50Bc thickening time 05:09:39, 60Bc thickening time 05:10:39, 70Bc thickening Thickening time 05:12:09, thickening time 05:13:30;
实施例6的稠化时间测试的参数条件如下:初始稠度开始时间15.0min,初始稠度结束时间30.0min;初始温度27.6℃,目标温度230.0℃;初始压力1.6MPa,目标压力150.0MPa;初始稠度15.7Bc,报警稠度100.0Bc;30Bc稠化时间05:26:39,40Bc稠化时间05:26:39,50Bc稠化时间05:26:39,60Bc稠化时间05:26:39,70Bc稠化时间00:00:00,稠化时间05:26:39。The parameter conditions of the thickening time test in Example 6 are as follows: initial consistency start time 15.0min, initial consistency end time 30.0min; initial temperature 27.6°C, target temperature 230.0°C; initial pressure 1.6MPa, target pressure 150.0MPa; initial consistency 15.7 Bc, alarm consistency 100.0Bc; 30Bc thickening time 05:26:39, 40Bc thickening time 05:26:39, 50Bc thickening time 05:26:39, 60Bc thickening time 05:26:39, 70Bc thickening time Time 00:00:00, thickening time 05:26:39.
实施例3与实施例6的稠化测试曲线分别如图1和图2所示。The thickening test curves of Example 3 and Example 6 are shown in Figure 1 and Figure 2 respectively.
从表1中数据可知,实施例1-7的晶相改造型广谱抗超高温固井水泥浆流动性好、具有好的稳定性,稠化时间可调,能够满足工程施工作业要求。从图1和图2可以看出,晶相改造型广谱抗超高温固井水泥浆的初稠较低,实验过程中曲线形态正常,没有出现包心、鼓包等等现象。From the data in Table 1, it can be known that the crystal phase reformed broad-spectrum ultra-high temperature resistant cementing cement slurry of Examples 1-7 has good fluidity and good stability, and the thickening time is adjustable, which can meet the requirements of engineering construction operations. It can be seen from Figures 1 and 2 that the initial viscosity of the crystal-phase reformed broad-spectrum ultra-high temperature resistant cement slurry is relatively low, and the shape of the curve is normal during the experiment, and there are no phenomena such as cores or bulges.
表1Table 1
Figure PCTCN2022102990-appb-000001
Figure PCTCN2022102990-appb-000001
通过实施例6与对比例1相比可以看出:晶相改造型高温增强剂对水泥浆的常规性能没有受到不良影响。通过实施例4与对比例2相比可以看出:本发明采用的超高温缓凝剂具有良好抗超高温能力,能有效地调节水泥浆稠化时间,保证安全施工。通过实施例5与对比例3相比可以看出:本发明采用的超高温降失水剂具有良好的抗超高温能力,能够有效控制水泥浆滤失以及保持浆体稳定。From the comparison between Example 6 and Comparative Example 1, it can be seen that the crystal phase transformation type high-temperature reinforcing agent has no adverse effect on the conventional performance of the cement slurry. By comparing Example 4 with Comparative Example 2, it can be seen that the ultra-high temperature retarder used in the present invention has good ultra-high temperature resistance, can effectively adjust the thickening time of cement slurry, and ensure safe construction. Comparing Example 5 with Comparative Example 3, it can be seen that the ultra-high temperature fluid loss reducer used in the present invention has good ultra-high temperature resistance, can effectively control cement slurry fluid loss and maintain slurry stability.
测试例2test case 2
本测试例对实施例1-7的晶相改造型高温增强剂对水泥浆所形成的渗透结晶型防窜固井水泥石和对比例1的水泥浆所形成的水泥石的长期抗压强度演变情况进行了测试,结果如表2所示。在实际中,稠化实验温度要比井底静止温度低,通常为井底静止温度的0.8-0.9倍,因此在测试中,水泥石养护温度比稠化实验温度高20-30℃。This test example is to the long-term compressive strength evolution situation of the cement stone formed by the crystal phase transformation type high temperature reinforcing agent of embodiment 1-7 to the permeable crystallization type anti-channeling cement stone formed by cement slurry and the cement stone formed by the cement slurry of comparative example 1 The test was carried out and the results are shown in Table 2. In practice, the temperature of the thickening test is lower than the static temperature at the bottom of the well, usually 0.8-0.9 times of the static temperature at the bottom of the well. Therefore, in the test, the curing temperature of cement stone is 20-30°C higher than the temperature of the thickening test.
从表2中数据可知,实施例1-7晶相改造型广谱抗超高温固井水泥不但具有较高的早期强度,而且在养护28d后,抗压强度下降幅度也比较小。From the data in Table 2, it can be seen that the modified broad-spectrum ultra-high temperature cementing cement of Examples 1-7 not only has higher early strength, but also has a relatively small decline in compressive strength after 28 days of curing.
通过实施例6与对比例1相比可以看出:在养护28天后,实施例6的水泥浆形成的水泥石强度约是对比例1的2.42倍,表明晶相改造型高温增强剂能够大幅改善水泥石的抗高温强度衰退性能。By comparing Example 6 with Comparative Example 1, it can be seen that after 28 days of curing, the strength of the cement stone formed by the cement slurry in Example 6 is about 2.42 times that of Comparative Example 1, indicating that the crystal phase transformation type high-temperature reinforcing agent can greatly improve The high temperature strength decline performance of cement stone.
表2Table 2
Figure PCTCN2022102990-appb-000002
Figure PCTCN2022102990-appb-000002
本发明在上文中己以优选实施例公开,但是本领域的技术人员应理解的是,这些实施例仅用于描绘本发明,而不应理解为限制本发明的范围。应注意的是,凡是与这些实施例等效的变化与置换,均应设为涵盖于本发明的权利要求范围内。The present invention has been disclosed above with preferred embodiments, but those skilled in the art should understand that these embodiments are only used to describe the present invention, and should not be construed as limiting the scope of the present invention. It should be noted that all changes and replacements equivalent to these embodiments should be included in the scope of the claims of the present invention.

Claims (24)

  1. 一种晶相改造型广谱抗超高温固井水泥浆,其中,该固井水泥浆含有晶型改造型高温增强剂;A crystal phase modified broad-spectrum ultra-high temperature resistant cement slurry, wherein the cement slurry contains a crystal modified high temperature enhancer;
    以重量百分比计,所述晶相改造型高温增强剂的组成包括10-30%铝酸钠、2-10%微硅、30-50%铝酸钙、30-50%偏高岭土、1-5%无机纤维。In terms of weight percent, the composition of the crystal phase transformation type high-temperature reinforcing agent includes 10-30% sodium aluminate, 2-10% micro-silicon, 30-50% calcium aluminate, 30-50% metakaolin, 1-5% % inorganic fibers.
  2. 根据权利要求1所述的固井水泥浆,其中,以重量份计,该固井水泥浆具有以下成分组成:The cement slurry according to claim 1, wherein, in parts by weight, the cement slurry has the following components:
    油井水泥100份、硅粉40-50份、加重剂0-100份、膨胀剂1-3份、晶相改造型高温增强剂3-10份、分散剂1-2份、悬浮剂1-2份、增韧剂1-3份、超高温缓凝剂2-6份、超高温降失水剂3-7份、水55-65份。100 parts of oil well cement, 40-50 parts of silicon powder, 0-100 parts of weighting agent, 1-3 parts of expansion agent, 3-10 parts of crystal phase modification high-temperature reinforcing agent, 1-2 parts of dispersant, 1-2 parts of suspending agent 1-3 parts of toughening agent, 2-6 parts of ultra-high temperature retarder, 3-7 parts of ultra-high temperature fluid loss reducer, and 55-65 parts of water.
  3. 根据权利要求1或2所述的固井水泥浆,其中,所述铝酸钠的纯度>93%。The cementing cement slurry according to claim 1 or 2, wherein the purity of the sodium aluminate is >93%.
  4. 根据权利要求1或2所述的固井水泥浆,其中,所述铝酸钠的细度为200-300目。The cementing cement slurry according to claim 1 or 2, wherein the fineness of the sodium aluminate is 200-300 mesh.
  5. 根据权利要求1或2所述的固井水泥浆,其中,所述铝酸钙的纯度>90%。The cementing cement slurry according to claim 1 or 2, wherein the purity of the calcium aluminate is >90%.
  6. 根据权利要求1或2所述的固井水泥浆,其中,所述铝酸钙的细度为200-300目。The cementing cement slurry according to claim 1 or 2, wherein the fineness of the calcium aluminate is 200-300 mesh.
  7. 根据权利要求1或2所述的固井水泥浆,其中,所述偏高岭土具有以下化学指标要求:SiO 2含量≤50%、Al 2O 3含量≥40%、游离CaO含量≤1%。 The cement slurry according to claim 1 or 2, wherein the metakaolin has the following chemical index requirements: SiO 2 content ≤ 50%, Al 2 O 3 content ≥ 40%, free CaO content ≤ 1%.
  8. 根据权利要求1或2所述的固井水泥浆,其中,所述无机纤维为经过表面处理的可分散性碳纤维或玄武岩纤维。The cementing slurry according to claim 1 or 2, wherein the inorganic fibers are surface-treated dispersible carbon fibers or basalt fibers.
  9. 根据权利要求1或2所述的固井水泥浆,其中,所述无机纤维的长度为3-6mm。The cement slurry according to claim 1 or 2, wherein the length of the inorganic fibers is 3-6mm.
  10. 根据权利要求2所述的固井水泥浆,其中,所述硅粉为二氧化硅质量含量≥97%的200目硅粉和600目硅粉的组合,并且,所述200目硅粉与600目硅粉的重量比为(4-7):(3-6)。The cementing cement slurry according to claim 2, wherein the silicon powder is a combination of 200 mesh silicon powder and 600 mesh silicon powder with a silica mass content ≥ 97%, and the 200 mesh silicon powder and 600 mesh silicon powder The weight ratio of the mesh silicon powder is (4-7):(3-6).
  11. 根据权利要求2所述的固井水泥浆,其中,所述加重剂为密度≥7.0g/cm 3的铁矿粉。 The cement slurry according to claim 2, wherein the weighting agent is iron ore powder with a density ≥ 7.0 g/cm 3 .
  12. 根据权利要求2所述的固井水泥浆,其中,所述膨胀剂为硫铝酸钙与氧化钙的混合物,混合重量比例(1-4):1。The cement slurry according to claim 2, wherein the expansion agent is a mixture of calcium sulfoaluminate and calcium oxide, and the mixing weight ratio is (1-4):1.
  13. 根据权利要求2所述的固井水泥浆,其中,所述分散剂为磺化甲醛-丙酮缩合物和/或聚萘磺酸盐。The cementing slurry according to claim 2, wherein the dispersant is sulfonated formaldehyde-acetone condensate and/or polynaphthalene sulfonate.
  14. 根据权利要求2所述的固井水泥浆,其中,所述悬浮剂为2-丙烯酰胺-2-甲基丙磺酸类聚合物增粘材料。The cementing cement slurry according to claim 2, wherein the suspending agent is a 2-acrylamide-2-methylpropanesulfonic acid polymer viscosity-increasing material.
  15. 根据权利要求2所述的固井水泥浆,其中,所述增韧剂为耐高温橡胶粉和/或树脂弹性体微球。The cement slurry according to claim 2, wherein the toughening agent is high temperature resistant rubber powder and/or resin elastomer microspheres.
  16. 根据权利要求2所述的固井水泥浆,其中,所述超高温缓凝剂由衣康酸、2-丙烯酰胺-2-甲基丙磺酸、N,N-二甲基丙烯酰胺、乙烯磷酸聚合而成。The cementing cement slurry according to claim 2, wherein the ultra-high temperature retarder is composed of itaconic acid, 2-acrylamide-2-methylpropanesulfonic acid, N,N-dimethylacrylamide, ethylene phosphoric acid aggregated.
  17. 根据权利要求2或16所述的固井水泥浆,其中,所述超高温缓凝剂的制备方法包括:The cement slurry according to claim 2 or 16, wherein the preparation method of the ultra-high temperature retarder comprises:
    (1)按质量百分比将总投量20-30%的衣康酸、38-48%的2-丙烯酰胺-2-甲基丙磺酸、20-28%的N,N-二甲基丙烯酰胺全部溶于以上投料总质量2-3倍的水中,调节pH至5.5-6.5,搅拌均匀;(1) According to the mass percentage, add the itaconic acid of 20-30% total dosage, the 2-acrylamide-2-methylpropanesulfonic acid of 38-48%, the N,N-dimethylpropene of 20-28% Dissolve all the amides in water that is 2-3 times the total mass of the above materials, adjust the pH to 5.5-6.5, and stir evenly;
    (2)将步骤(1)中所得混合液置于反应装置中,通入保护气体排尽反应装置中的氧气;(2) placing the mixed solution obtained in the step (1) in the reaction device, and feeding the protective gas to exhaust the oxygen in the reaction device;
    (3)将反应装置升温至58-63℃;(3) heating up the reaction device to 58-63°C;
    (4)在搅拌速率60-80转/分钟、氮气保护条件下,将引发剂以6-8ml/min的滴加速率滴加至混合液中,反应0.5小时;(4) Add the initiator dropwise to the mixed solution at a rate of 6-8ml/min under the conditions of a stirring rate of 60-80 rpm and nitrogen protection, and react for 0.5 hours;
    (5)将总投量8-12%的乙烯磷酸溶于其质量的1-2倍的水中,以10-15ml/min滴加速率滴加至反应后的混合液,继续反应1.5-2小时后冷却,获得所述超高温缓凝剂。(5) Dissolve ethylene phosphoric acid with a total dosage of 8-12% in water 1-2 times its mass, add it dropwise to the reacted mixed solution at a rate of 10-15ml/min, and continue to react for 1.5-2 hours After cooling, the super high temperature retarder is obtained.
  18. 根据权利要求2所述的固井水泥浆,其中,所述超高温降失水剂由2-丙烯酰胺-2-甲基丙磺酸、丙烯酸、N,N-二甲基丙烯酰胺、N-乙烯基吡咯烷酮、微晶纤维素聚合而成。The cement slurry according to claim 2, wherein the ultra-high temperature fluid loss reducer is composed of 2-acrylamide-2-methylpropanesulfonic acid, acrylic acid, N,N-dimethylacrylamide, N- Polymerized from vinylpyrrolidone and microcrystalline cellulose.
  19. 根据权利要求2或18所述的固井水泥浆,其中,该超高温降失水剂的制备方法包括:The cementing cement slurry according to claim 2 or 18, wherein the preparation method of the ultra-high temperature fluid loss reducing agent comprises:
    (1)按质量分数将总投量30-60%的2-丙烯酰胺-2-甲基丙磺酸、20-30%的丙烯酸溶于相当于总投量4-5倍的水中,调节pH至7-7.5,搅拌均匀,得到混合液;(1) Dissolve 2-acrylamide-2-methylpropanesulfonic acid and 20-30% acrylic acid in 2-acrylamide-2-methylpropanesulfonic acid and 20-30% of the total dosage by mass fraction in water equivalent to 4-5 times the total dosage, and adjust the pH To 7-7.5, stir evenly to obtain a mixed solution;
    (2)将总投量10-15%的N,N-二甲基丙烯酰胺、4-8%的N-乙烯基吡咯烷酮、0.2%的N,N-亚甲基双丙烯酰胺加入步骤(1)的混合液中,搅拌均匀;(2) Add 10-15% of N,N-dimethylacrylamide, 4-8% of N-vinylpyrrolidone, and 0.2% of N,N-methylenebisacrylamide into step (1) ) in the mixture, stir evenly;
    (3)将步骤(2)的混合液置于反应装置中,通入保护气体排尽反应装置中的空气;(3) The mixed solution of step (2) is placed in the reaction device, and the air in the reaction device is exhausted by feeding protective gas;
    (4)将步骤(3)的混合液升温至60-65℃;(4) The mixed solution of step (3) is warmed up to 60-65°C;
    (5)在搅拌速率60-80转/分钟、氮气保护条件下,将引发剂以4-6ml/min的滴加速率滴加至混合液中,反应3小时;(5) Add the initiator dropwise to the mixture at a rate of 4-6ml/min at a stirring rate of 60-80 rpm and nitrogen protection, and react for 3 hours;
    (6)将总投量15-20%的微晶纤维素加入其质量5倍的水中,搅拌均匀后以 3-4ml/min滴加速率滴加至步骤(5)的混合液,继续反应2小时后冷却,获得所述超高温降失水剂。(6) Add microcrystalline cellulose with a total dosage of 15-20% into water with 5 times its mass, stir evenly and then add it dropwise to the mixed solution of step (5) at a rate of 3-4ml/min, and continue to react for 2 After cooling for one hour, the ultra-high temperature fluid loss reducing agent was obtained.
  20. 根据权利要求1-19任一项所述的固井水泥浆,其中,该固井水泥浆的密度为1.85-2.40g/cm 3The cement slurry according to any one of claims 1-19, wherein the cement slurry has a density of 1.85-2.40 g/cm 3 .
  21. 权利要求1-20任一项所述的晶相改造型广谱抗超高温固井水泥浆在固井作业中的应用。The application of the crystal phase modification type broad-spectrum ultra-high temperature resistant cementing cement slurry described in any one of claims 1-20 in well cementing operations.
  22. 根据权利要求21所述的应用,其中,所述水泥浆固化之后形成钙长石物相。The use according to claim 21, wherein the anorthite phase is formed after the cement slurry solidifies.
  23. 根据权利要求21或22所述的应用,其中,所述固井作业是指深井、超深井、干热岩、地热井的高温超高温地层固井作业。The application according to claim 21 or 22, wherein the cementing operation refers to high-temperature and ultra-high-temperature formation cementing operations for deep wells, ultra-deep wells, hot dry rocks, and geothermal wells.
  24. 根据权利要求21-23任一项所述的应用,其中,该晶相改造型广谱抗超高温固井水泥浆的适用循环温度范围为110℃-230℃。The application according to any one of claims 21-23, wherein the applicable circulation temperature range of the crystal phase modified broad-spectrum ultra-high temperature resistant cementing cement slurry is 110°C-230°C.
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