CN116410715A - Crystal phase-modified broad-spectrum ultra-high temperature resistant well cementation cement paste and application thereof - Google Patents

Crystal phase-modified broad-spectrum ultra-high temperature resistant well cementation cement paste and application thereof Download PDF

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CN116410715A
CN116410715A CN202111676357.8A CN202111676357A CN116410715A CN 116410715 A CN116410715 A CN 116410715A CN 202111676357 A CN202111676357 A CN 202111676357A CN 116410715 A CN116410715 A CN 116410715A
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parts
high temperature
ultra
agent
temperature
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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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Petrochina Co Ltd
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Petrochina Co Ltd
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Priority to PCT/CN2022/102990 priority patent/WO2023123976A1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
    • C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C08F220/585—Amides, 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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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers 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
    • C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
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    • C08F222/00—Copolymers 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
    • C08F222/36—Amides or imides
    • C08F222/38—Amides
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08F226/00—Copolymers 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
    • C08F226/06—Copolymers 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
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    • C08F230/00—Copolymers 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
    • C08F230/02—Copolymers 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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    • C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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    • 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

Abstract

The invention provides a crystal phase-modified broad-spectrum ultra-high temperature resistant well cementation cement paste and application thereof. The well cementation cement slurry contains a crystal modification type high Wen Zengjiang agent; the composition of the crystal phase modified high temperature reinforcing agent 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 invention also provides application of the crystal phase modified broad-spectrum ultra-high temperature resistant well cementation cement paste in well cementation operation. The crystal phase modified high-temperature reinforcing agent can participate in hydration reaction of silica powder cement and generate ettringite phase, the ettringite has excellent high-temperature resistance, and can slow down the crystal transformation phenomenon of ultrahigh-temperature cement, so that cement paste has good ultrahigh-temperature strength decay resistance. The cement paste can meet the requirement of the circulating temperature of 110-230 ℃, has a wide temperature application range, is adjustable in density and thickening time, has quick top strength development, and can meet the application requirement of a cross-temperature area.

Description

Crystal phase-modified broad-spectrum ultra-high temperature resistant well cementation cement paste and application thereof
Technical Field
The invention relates to the technical field of well cementation cement paste, in particular to a broad-spectrum ultra-high temperature resistant well cementation cement paste with a modified crystal phase.
Background
With the continuous deep exploration and development of shallow layer easy-to-use resources, high-temperature deep wells, ultra-deep wells, geothermal wells, dry hot rocks and the like gradually become the focus of exploration and development. Under the ultra-high temperature condition, the difficulty and the complexity of the well cementation operation are greatly improved, the performance requirements on well cementation cement paste and cement stones are also greatly improved, and the well cementation cement paste and cement sheath mainly face three problems: firstly, the cement admixture is easy to lose efficacy and denature at high temperature, cement paste is easy to have a series of complex problems of high-temperature sedimentation instability, difficult compromise of rheological property, difficult control of water loss, difficult adjustment of thickening time and the like, and cementing safety accidents and quality problems are extremely easy to cause; secondly, the cement stone strength development is slow and even the super retarding problem is solved under the condition of large temperature difference of long naked eyes. For example, when the static temperature difference between the hanger and the casing shoe is too large and the cement paste density is high, the cement paste at the hanger is extremely easy to cause non-coagulation for a long time, so that the well construction period is prolonged, and the risk of blowby at the bell mouth is increased; thirdly, the strength of the cement stone is reduced under the effect of ultra-high temperature for a long time. When the temperature exceeds 110 ℃, the cement hydration product undergoes crystal transformation, so that the porosity and permeability of the cement paste are increased, the strength is reduced, the mechanical integrity and the structural integrity of the cement sheath are reduced, and the problems of later gas channeling and annulus pressure are caused.
At present, the field develops more ultrahigh temperature well cementation cement slurry system researches from the aspects of research and development of novel additives, high temperature reinforcing materials or high temperature strength decay resistant materials and cement slurry systems, but the problems that the temperature resistant capability of the additives is insufficient, particularly the capability of stabilizing the ultrahigh temperature resistant to the temperature of >180 ℃ is insufficient, the applicable temperature range is narrow, the sensitivity is high, and the means of singly doping silicon powder is difficult to effectively inhibit the great decay of the well cementation cement stone strength under the ultrahigh temperature condition of >180 ℃ and the like still exist.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide the crystal phase modified broad-spectrum ultra-high temperature resistant well cementation cement paste, and the problem of strength decline of a conventional silica powder cement paste system under the condition of long-term ultra-high temperature can be effectively solved by adding the crystal phase modified high Wen Zengjiang agent.
In order to achieve the aim, the invention provides a crystal modification type broad-spectrum ultra-high temperature resistant well cementing slurry, wherein the well cementing slurry contains a crystal modification type high Wen Zengjiang agent;
the composition of the crystal phase modified high-temperature reinforcing agent comprises, by weight, 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.
According to a specific embodiment of the present invention, preferably, the cement slurry has the following composition in parts by weight:
100 parts of oil well cement, 40-50 parts of silica powder, 0-100 parts of weighting agent, 1-3 parts of expanding agent, 3-10 parts of crystal phase modified high-temperature reinforcing agent, 1-2 parts of dispersing agent, 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 agent and 55-65 parts of water.
According to a specific embodiment of the present invention, preferably, in the crystalline phase modification type high temperature enhancer, the purity of the sodium aluminate is >93%.
According to a specific embodiment of the present invention, preferably, in the crystal phase modification type high temperature reinforcing agent, the fineness of the sodium aluminate is 200 to 300 mesh.
According to a specific embodiment of the present invention, preferably, in the crystalline phase modification type high temperature enhancer, the purity of the calcium aluminate is >90%.
According to a specific embodiment of the present invention, preferably, in the crystal phase modification type high temperature reinforcing agent, the fineness of the calcium aluminate is 200 to 300 mesh.
According to a specific embodiment of the present invention, preferably, in the crystal phase modification type high temperature reinforcing agent, the metakaolin has the following chemical index requirements: siO (SiO) 2 The content is less than or equal to 50 percent, al 2 O 3 The content is more than or equal to 40 percent, and the content of free CaO is less than or equal to 1 percent.
According to a specific embodiment of the present invention, preferably, in the crystal phase modification type high temperature reinforcing agent, the inorganic fiber is a surface-treated dispersible carbon fiber or basalt fiber.
According to a specific embodiment of the present invention, preferably, in the crystal phase-modified high temperature reinforcing agent, the length of the inorganic fiber is 3 to 6mm.
According to a specific embodiment of the present invention, the above-mentioned crystal phase modification type high temperature reinforcing agent may be prepared according to the following steps:
step 1: stirring and blending sodium aluminate and micro-silicon to obtain a mixture, wherein the stirring and blending time can be controlled to be 5min;
step 2: and (2) adding calcium aluminate, metakaolin and inorganic fibers into the mixture obtained in the step (1), and stirring and blending to obtain Wen Zengjiang agents with high crystal phase modification degree, wherein the stirring and blending time can be controlled to be 15 minutes.
According to a specific embodiment of the invention, preferably, in the well cementing slurry, the silica fume is a combination of 200-mesh silica fume and 600-mesh silica fume with the silica fume mass content of more than or equal to 97 percent, and the weight ratio of the 200-mesh silica fume to the 600-mesh silica fume is (4-7) to (3-6).
According to a specific embodiment of the present invention, preferably, in the well cementing slurry, the weighting agent has a density of 7.0g/cm or more 3 A kind of electronic device iron ore powder.
According to a specific embodiment of the present invention, preferably, in the well cementing slurry, the expanding agent is a mixture of calcium sulfoaluminate and calcium oxide, and the mixing weight ratio is (1-4): 1.
According to a specific embodiment of the present invention, preferably, in the well cementing slurry, the dispersant is a sulfonated formaldehyde-acetone condensate and/or a polynaphthalenesulfonate.
According to a specific embodiment of the present invention, preferably, in the well cementing slurry, the suspending agent is a 2-acrylamido-2-methylpropanesulfonic Acid (AMPS) polymer tackifying material.
According to a specific embodiment of the present invention, preferably, in the well cementing slurry, the toughening agent is a high temperature resistant rubber powder and/or resin elastomer microsphere.
According to a specific embodiment of the present invention, preferably, in the well cementing slurry, the ultra-high temperature retarder is polymerized from Itaconic Acid (IA), 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), N-Dimethylacrylamide (DMAA), ethylene phosphoric acid.
According to a specific embodiment of the present invention, preferably, the preparation method of the ultra-high temperature retarder comprises the following steps:
(1) According to the mass percentage, the Itaconic Acid (IA) accounting for 20-30 percent of the total feeding amount, the 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) accounting for 38-48 percent and the N, N-Dimethylacrylamide (DMAA) accounting for 20-28 percent are all dissolved in deionized water which is 2-3 times of the total feeding amount, the pH value is regulated to 5.5-6.5 (the pH value is regulated by adopting a sodium hydroxide solution with the concentration of 30 percent), and a mixed solution is formed after uniform stirring;
(2) Placing the mixed solution obtained in the step (1) in a reaction device (preferably a reaction device with a stirrer, a thermometer and nitrogen protection conditions), and introducing a protective gas (preferably inert gas or nitrogen) to exhaust oxygen in the reaction device;
(3) Heating the reaction device to 58-63 ℃; preferably, the reaction device after the oxygen is exhausted in the step (2) is placed in a water bath kettle, and the temperature of the mixed solution is raised to 58-63 ℃ while a stirrer is started;
(4) Dropwise adding an initiator into the mixed solution at a dropwise adding rate of 6-8ml/min under the conditions of stirring speed of 60-80 rpm and nitrogen protection, and reacting for 0.5 hour;
(5) Dissolving ethylene phosphoric acid (VA) with the total dosage of 8-12% in water which is 1-2 times of the mass of the ethylene phosphoric acid (VA), dropwise adding the ethylene phosphoric acid into the mixed solution obtained after the reaction in the step (4) for 0.5 hour at the dropwise adding rate of 10-15ml/min, continuing the reaction for 1.5-2 hours, and cooling to obtain the ultra-high temperature retarder.
According to a specific embodiment of the present invention, preferably, in the well cementing slurry, the ultra-high temperature fluid loss additive is polymerized from 2-acrylamide-2-methylpropanesulfonic Acid (AMPS), acrylic Acid (AA), N-Dimethylacrylamide (DMAA), N-vinyl pyrrolidone (NVP), and microcrystalline cellulose (MCC).
According to a specific embodiment of the present invention, preferably, the preparation method of the ultra-high temperature fluid loss additive includes:
(1) Dissolving 30-60% of 2-acrylamide-2-methylpropanesulfonic Acid (AMPS) and 20-30% of Acrylic Acid (AA) in deionized water which is 4-5 times of the total dosage according to mass fraction, regulating pH to 7-7.5 (regulating pH value by adopting a sodium hydroxide solution with concentration of 30%), and uniformly stirring to form a mixed solution;
(2) Adding 10-15% of total dosage of N, N-Dimethylacrylamide (DMAA), 4-8% of N-vinyl pyrrolidone (NVP) and 0.2% of N, N-Methylenebisacrylamide (MBA) into the mixed solution in the step (1), and uniformly stirring;
(3) Placing the mixed solution obtained in the step (2) in a reaction device (preferably a reaction device with a stirrer, a thermometer and nitrogen protection conditions), and introducing a protective gas (preferably inert gas or nitrogen) to exhaust air in the reaction device;
(4) Heating the mixed solution in the step (3) to 60-65 ℃, preferably placing the reaction device after air is exhausted in a water bath, starting a stirrer and heating the mixed solution to 60-65 ℃;
(5) Dropwise adding an initiator into the mixed solution at a dropwise adding rate of 4-6ml/min under the conditions of stirring speed of 60-80 rpm and nitrogen protection, and reacting for 3 hours;
(6) Adding microcrystalline cellulose (MCC) accounting for 15-20% of the total dosage into water which is 5 times of the total dosage, uniformly stirring, then dripping the mixture into the mixed solution in the step (5) at a dripping rate of 3-4ml/min, continuously reacting for 2 hours, and cooling to obtain the ultrahigh temperature fluid loss agent.
According to a specific embodiment of the present invention, the cementing slurries of the present invention preferably have a suitable density in the range of 1.85 to 2.40g/cm 3 。
According to a specific embodiment of the invention, the broad-spectrum ultra-high temperature resistant cementing slurry with modified crystalline phase provided by the invention can be prepared by the following steps:
according to the weight parts of the components, the oil well cement, the silica powder, the weighting agent, the expanding agent, the crystal phase modification type high Wen Zengjiang agent, the dispersing agent, the suspending agent and the toughening agent are mixed and stirred uniformly to obtain a dry mixed material; according to the weight parts of the components, the ultra-high temperature retarder, the ultra-high temperature fluid loss agent and water are mixed and stirred uniformly to obtain slurry preparation water; and adding the dry blend into the slurry, and uniformly mixing and stirring to obtain the broad-spectrum ultra-high temperature resistant well cementation cement slurry with modified crystalline phase.
The invention also provides application of the crystal phase modified broad-spectrum ultra-high temperature resistant well cementation cement paste in well cementation operation.
According to a specific embodiment of the invention, preferably, the cement slurry forms an ettringite phase after curing.
According to a specific embodiment of the present invention, preferably, the cementing operation refers to a cementing operation of a deep well, an ultra-deep well, a dry hot rock, a geothermal well, and other high-temperature and ultra-high-temperature stratum.
According to a specific embodiment of the present invention, preferably, the applicable circulation temperature range of the broad spectrum ultra-high temperature resistant cement slurry modified by the crystalline phase is 110 ℃ to 230 ℃.
Compared with the prior art, the technical scheme provided by the invention has the following advantages:
(1) The crystal phase modified high-temperature reinforcing agent doped in the well cementation cement slurry can participate in hydration reaction of silica powder cement and generate ettringite phase, the ettringite has excellent high-temperature resistance, and can slow down the crystal transformation phenomenon of ultrahigh-temperature cement, so that the cement slurry system has good ultrahigh-temperature strength decay resistance.
(2) The cement slurry system of the invention can meet the requirement of circulating temperature of 110-230 ℃ by adopting the additive with excellent temperature resistance and low sensitivity, has a wide temperature application range, has adjustable density and thickening time and rapid top strength development, and can meet the application requirement of 'medium-high temperature (110-150 ℃) to high temperature (150-205 ℃) to ultra-high temperature (> 205 ℃) over a temperature region'.
Drawings
FIG. 1 is a graph of a thickening test of the well cementing slurry of example 3.
Fig. 2 is a thickening test chart of the well cementing slurry of example 6.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Material：
Silicon powder: the weight ratio of 200-mesh silicon powder to 600-mesh silicon powder is 4:6;
and (3) an expanding agent: mass ratio 3:1 with calcium oxide;
high Wen Zengjiang agent with modified crystalline phase: 15% of sodium aluminate, 4% of micro silicon, 33% of calcium aluminate, 36% of metakaolin and 2% of inorganic fiber according to mass fraction;
dispersing agent: sulfonated formaldehyde-acetone condensate FS200L, manufacturer is oil gas energy technology Co., ltd., sichuan An Niunuo Si;
suspending agent: SP200S, the manufacturer is Sichuan An Niunuo S oil gas energy technology Co., ltd;
toughening agent: HE-1S, the manufacturer is Sichuan An Niunuo S oil and gas energy technology Co., ltd;
ultra-high temperature retarder: the catalyst is prepared by polymerizing 23% of itaconic acid, 44% of 2-acrylamide-2-methylpropanesulfonic acid, 22% of N, N-dimethylacrylamide and 11% of ethylene phosphoric acid according to mass percentage;
ultra-high temperature fluid loss agent: the polymer is prepared by polymerizing 45% of 2-acrylamide-2-methylpropanesulfonic acid, 23% of acrylic acid, 11% of N, N-dimethylacrylamide, 4%N-vinyl pyrrolidone, 0.2% of N, N-methylenebisacrylamide and 16.8% of microcrystalline cellulose;
weighting agent: density of 7.0g/cm 3 Iron ore powder of (2).
Example 1
This example provides a density of 1.85g/cm 3 The broad-spectrum ultra-high temperature resistant well cementation cement paste modified by the crystal phase at the application temperature of 110 ℃ comprises the following components in parts by weight: 100 parts of oil well cement, 40 parts of silica powder, 1 part of an expanding agent, 3 parts of a crystal phase modification type high-temperature reinforcing agent, 1 part of a dispersing agent, 1 part of a suspending agent, 2 parts of a toughening agent, 2 parts of an ultrahigh-temperature retarder, 3 parts of an ultrahigh-temperature fluid loss agent and 62 parts of water.
Example 2
This example provides a density of 2.40g/cm 3 The broad-spectrum ultra-high temperature resistant well cementation cement paste modified by the crystal phase at the application temperature of 110 ℃ comprises the following components in parts by weight: 100 parts of oil well cement, 40 parts of silica powder, 100 parts of weighting agent, 1 part of expanding agent, 3 parts of crystal phase modified high-temperature reinforcing agent, 2 parts of dispersing agent, 1.5 parts of suspending agent, 1 part of toughening agent, 2 parts of ultra-high temperature retarder, 3 parts of ultra-high temperature fluid loss agent and 58 parts of water.
Example 3
This example provides a density of 1.95g/cm 3 The broad-spectrum ultra-high temperature resistant well cementation cement paste modified by the crystal phase at the application temperature of 150 ℃ comprises the following components in parts by weight: 100 parts of oil well cement, 40 parts of silica powder, 2 parts of an expanding agent, 5 parts of a crystal phase modification type high-temperature reinforcing agent, 1 part of a dispersing agent, 1.5 parts of a suspending agent, 1.5 parts of a toughening agent, 3.5 parts of an ultra-high temperature retarder, 4 parts of an ultra-high temperature fluid loss agent and 62 parts of water.
Example 4
This example provides a density of 1.95g/cm 3 The broad-spectrum ultra-high temperature resistant well cementation cement paste modified by the crystal phase at the application temperature of 180 ℃ comprises the following components in parts by weight: 100 parts of oil well cement, 45 parts of silica powder, 2 parts of an expanding agent, 5 parts of a crystal phase modified high-temperature reinforcing agent, 1 part of a dispersing agent, 1.5 parts of a suspending agent, 1.5 parts of a toughening agent, 4 parts of an ultra-high temperature retarder, 5 parts of an ultra-high temperature fluid loss agent and 62 parts of water.
Example 5
This example provides a density of 2.20g/cm 3 The broad-spectrum ultra-high temperature resistant well cementation cement paste modified by the crystal phase at the application temperature of 180 ℃ comprises the following components in parts by weight: 100 parts of oil well cement, 45 parts of silica powder, 54 parts of weighting agent, 2 parts of expanding agent, 5 parts of crystal phase modified high-temperature reinforcing agent, 2 parts of dispersing agent, 1.5 parts of suspending agent, 2 parts of toughening agent, 3.5 parts of ultra-high temperature retarder, 5.5 parts of ultra-high temperature filtrate reducer and 55 parts of water.
Example 6
This example provides a density of 1.85g/cm 3 The broad-spectrum ultra-high temperature resistant well cementing slurry with the application temperature of 230 ℃ and modified crystal phase comprises the following components in weight percentThe weight ratio is as follows: 100 parts of oil well cement, 50 parts of silica powder, 2 parts of an expanding agent, 7 parts of a crystal phase modified high-temperature reinforcing agent, 1 part of a dispersing agent, 2 parts of a suspending agent, 3 parts of a toughening agent, 5 parts of an ultrahigh-temperature retarder, 7 parts of an ultrahigh-temperature fluid loss agent and 61 parts of water.
Example 7
This example provides a density of 2.40g/cm 3 The broad-spectrum ultra-high temperature resistant well cementation cement paste modified by the crystal phase at the application temperature of 230 ℃ comprises the following components in parts by weight: 100 parts of oil well cement, 50 parts of silica powder, 100 parts of weighting agent, 2 parts of expanding agent, 7 parts of crystal phase modified 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, 7 parts of ultra-high temperature fluid loss agent and 65 parts of water.
Comparative example 1
The comparative example provides a density of 1.85g/cm 3 The cementing slurry without the crystal phase modification type high-temperature reinforcing agent at the application temperature of 230 ℃ comprises the following components in parts by weight: 100 parts of oil well cement, 50 parts of silica powder, 2 parts of an expanding agent, 1 part of a dispersing agent, 2 parts of a suspending agent, 3 parts of a toughening agent, 5 parts of an ultra-high temperature retarder, 7 parts of an ultra-high temperature fluid loss agent and 60 parts of water.
Comparative example 2
The comparative example provides a density of 1.95g/cm 3 The application temperature is 180 ℃ and the retarder is prepared by using the commercially available high temperature resistant retarder (temperature resistant capability)<The cement paste for well cementation at 180 ℃ comprises the following components in parts by weight: 100 parts of oil well cement, 45 parts of silica powder, 2 parts of an expanding agent, 5 parts of a crystal phase modification type high-temperature reinforcing agent, 1 part of a dispersing agent, 1.5 parts of a suspending agent, 1.5 parts of a toughening agent, 4 parts of a commercial retarder, 5 parts of an ultrahigh-temperature fluid loss agent and 62 parts of water.
Comparative example 3
The comparative example provides a density of 2.20g/cm 3 The application temperature is 180 ℃, and the commercial high-temperature-resistant fluid loss agent (temperature resistance<The cement paste for well cementation at 180 ℃ comprises the following components in parts by weight: 100 parts of oil well cement, 45 parts of silicon powder, 54 parts of weighting agent, 2 parts of expanding agent, 5 parts of crystal phase modified high-temperature reinforcing agent, 2 parts of dispersing agent, 1.5 parts of suspending agent, 2 parts of toughening agent and ultrahigh temperature3.5 parts of retarder, 5.5 parts of commercial fluid loss agent and 55 parts of water.
Test example 1
According to GB/T19139 oil well cement test method and GB/T2419 cement mortar fluidity test method, the test example tests the performance of the crystalline phase modified broad-spectrum ultra-high temperature resistant well cementing cement slurry of examples 1-7 and the conventional engineering of comparative examples 1-3, such as density, free fluid, fluidity, API water loss, thickening time and the like, and the results are shown in Table 1.
The parameters for the thickening time test of example 3 were as follows: initial consistency start time 15.0min, initial consistency end time 30.0min; the initial temperature is 25.5 ℃, and the target temperature is 150.0 ℃; initial pressure-1.9 MPa, target pressure 80.0MPa; an initial consistency of 29.2Bc and an alarm consistency of 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 time 05:12:09, thickening time 05:13:30;
the parameters for the thickening time test of example 6 were as follows: initial consistency start time 15.0min, initial consistency end time 30.0min; the initial temperature is 27.6 ℃, and the target temperature is 230.0 ℃; initial pressure 1.6MPa, target pressure 150.0MPa; an initial consistency of 15.7Bc and an alarm consistency of 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 00:00:00, thickening time 05:26:39.
The thickening test curves for example 3 and example 6 are shown in figures 1 and 2, respectively.
From the data in Table 1, the crystalline phase modified broad-spectrum ultra-high temperature resistant well cementing slurries of examples 1-7 have good fluidity, good stability and adjustable thickening time, and can meet the engineering construction operation requirements. As can be seen from fig. 1 and 2, the primary thickening of the broad-spectrum ultra-high temperature resistant cementing slurry with modified crystalline phase is lower, and the curve is normal in the experimental process, so that phenomena such as core swelling and bulge do not occur.
TABLE 1
Figure BDA0003451448900000081
As can be seen from example 6 compared to comparative example 1: the high Wen Zengjiang agent with modified crystalline phase has no adverse effect on the conventional performance of cement paste. As can be seen from example 4 compared to comparative example 2: the ultra-high temperature retarder adopted by the invention has good ultra-high temperature resistance, can effectively adjust the thickening time of cement paste, and ensures safe construction. As can be seen from example 5 compared to comparative example 3: the ultra-high temperature filtrate reducer adopted by the invention has good ultra-high temperature resistance, and can effectively control the cement slurry filtration and keep the slurry stable.
Test example 2
The test examples tested the long-term compressive strength evolution of the cement sets of examples 1 to 7, the permeable crystallization type channeling-preventing cement set formed by cement slurry and the cement set formed by cement slurry of comparative example 1 with a high Wen Zengjiang agent, and the results are shown in Table 2. In practice, the temperature of the densification test is lower than the bottom hole resting temperature, usually 0.8-0.9 times the bottom hole resting temperature, so that in the test, the set cement curing temperature is 20-30 ℃ higher than the densification test temperature.
As can be seen from the data in Table 2, the broad-spectrum ultra-high temperature resistant cementing cements modified in the crystalline phase of examples 1 to 7 not only have higher early strength, but also have smaller reduction in compressive strength after 28d curing.
As can be seen from example 6 compared to comparative example 1: after curing for 28 days, the cement paste of example 6 formed cement paste with strength about 2.42 times that of comparative example 1, which shows that the high-temperature reinforcing agent with modified crystal phase can greatly improve the high-temperature strength decay resistance of cement paste.
TABLE 2
Figure BDA0003451448900000091
The present invention has been disclosed above in terms of preferred embodiments, but it will be understood by those skilled in the art that these embodiments are merely illustrative of the invention and should not be construed as limiting the scope of the invention. It should be noted that all changes and substitutions equivalent to those of the embodiments are intended to be included within the scope of the claims of the present invention.

Claims (19)

1. The broad-spectrum ultra-high temperature resistant well cementation cement paste with the modified crystal phase is characterized in that the well cementation cement paste contains Wen Zengjiang agents with the modified crystal phase;
the composition of the crystal phase modified high-temperature reinforcing agent comprises, by weight, 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.
2. A well cementing slurry according to claim 1, wherein the well cementing slurry has the following composition in parts by weight:
100 parts of oil well cement, 40-50 parts of silica powder, 0-100 parts of weighting agent, 1-3 parts of expanding agent, 3-10 parts of crystal phase modified high-temperature reinforcing agent, 1-2 parts of dispersing agent, 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 agent and 55-65 parts of water.
3. A well cementing slurry according to claim 1 or 2, wherein the purity of the sodium aluminate is >93%;
preferably, the fineness of the sodium aluminate is 200-300 meshes.
4. A well cementing slurry according to claim 1 or 2, wherein the purity of the calcium aluminate is >90%;
preferably, the fineness of the calcium aluminate is 200-300 mesh.
5. A well cementing slurry according to claim 1 or 2, wherein the metakaolin has the following chemical specification requirements: siO (SiO) 2 The content is less than or equal to 50 percent, al 2 O 3 The content is more than or equal to 40 percent, and the content of free CaO is less than or equal to 1 percent.
6. A well cementing slurry according to claim 1 or 2, wherein the inorganic fibres are surface treated dispersible carbon fibres or basalt fibres;
preferably, the inorganic fibers have a length of 3-6mm.
7. A well cementing slurry according to claim 2, wherein the silica fume is a combination of 200 mesh silica fume and 600 mesh silica fume having a silica content of not less than 97% by mass, and the weight ratio of the 200 mesh silica fume to the 600 mesh silica fume is (4-7): 3-6.
8. A well cementing slurry according to claim 2, wherein the weighting agent is of a density of 7.0g/cm or more 3 Iron ore powder of (2).
9. A well cementing slurry according to claim 2, wherein the expansion agent is a mixture of calcium sulfoaluminate and calcium oxide in a mixing weight ratio (1-4): 1.
10. A well cementing slurry according to claim 2, wherein the dispersant is a sulphonated formaldehyde-acetone condensate and/or a polynaphthalenesulphonate.
11. A well cementing slurry according to claim 2, wherein the suspending agent is a 2-acrylamido-2-methylpropanesulfonic acid based polymeric tackifying material.
12. A well cementing slurry according to claim 2, wherein the toughening agent is a high temperature resistant rubber powder and/or resin elastomer microspheres.
13. The well cementing slurry according to claim 2, wherein the ultra-high temperature retarder is polymerized from itaconic acid, 2-acrylamide-2-methylpropanesulfonic acid, N-dimethylacrylamide, ethylene phosphoric acid;
preferably, the preparation method of the ultra-high temperature retarder comprises the following steps:
(1) The itaconic acid with the total dosage of 20-30 percent, the 2-acrylamide-2-methylpropanesulfonic acid with the weight percent of 38-48 percent and the N, N-dimethylacrylamide with the weight percent of 20-28 percent are all dissolved in water with the weight which is 2-3 times of the total weight of the materials, the pH value is regulated to 5.5-6.5, and the materials are stirred uniformly;
(2) Placing the mixed solution obtained in the step (1) into a reaction device, and introducing protective gas to exhaust oxygen in the reaction device;
(3) Heating the reaction device to 58-63 ℃;
(4) Dropwise adding an initiator into the mixed solution at a dropwise adding rate of 6-8ml/min under the conditions of stirring speed of 60-80 rpm and nitrogen protection, and reacting for 0.5 hour;
(5) Dissolving ethylene phosphoric acid with the total dosage of 8-12% in water which is 1-2 times of the mass of the ethylene phosphoric acid, dripping the ethylene phosphoric acid into the reacted mixed solution at the dripping rate of 10-15ml/min, continuing to react for 1.5-2 hours, and cooling to obtain the ultra-high temperature retarder.
14. The well cementing slurry according to claim 2, wherein the ultra-high temperature fluid loss additive is polymerized from 2-acrylamide-2-methylpropanesulfonic acid, acrylic acid, N-dimethylacrylamide, N-vinylpyrrolidone, microcrystalline cellulose;
preferably, the preparation method of the ultra-high temperature fluid loss agent comprises the following steps:
(1) Dissolving 30-60% of 2-acrylamide-2-methylpropanesulfonic acid and 20-30% of acrylic acid in water which is 4-5 times of the total dosage according to mass fraction, regulating pH to 7-7.5, and uniformly stirring to obtain mixed solution;
(2) Adding 10-15% of total N, N-dimethylacrylamide, 4-8% of N-vinyl pyrrolidone and 0.2% of N, N-methylenebisacrylamide into the mixed solution in the step (1), and uniformly stirring;
(3) Placing the mixed solution obtained in the step (2) in a reaction device, and introducing protective gas to exhaust air in the reaction device;
(4) Heating the mixed solution obtained in the step (3) to 60-65 ℃;
(5) Dropwise adding an initiator into the mixed solution at a dropwise adding rate of 4-6ml/min under the conditions of stirring speed of 60-80 rpm and nitrogen protection, and reacting for 3 hours;
(6) Adding microcrystalline cellulose with the total dosage of 15-20% into water with the mass of 5 times of that of the microcrystalline cellulose, uniformly stirring, then dropwise adding the mixture into the mixed solution in the step (5) at the dropwise adding rate of 3-4ml/min, continuously reacting for 2 hours, and cooling to obtain the ultrahigh temperature filtrate reducer.
15. A well cementing slurry according to any one of claims 1 to 14, wherein the density of the well cementing slurry is from 1.85 to 2.40g/cm 3 。
16. Use of a broad spectrum ultra-high temperature resistant cementing slurry of crystalline phase modification type as claimed in any one of claims 1 to 15 in cementing operations.
17. Use according to claim 16, wherein the cement slurry forms an ettringite phase after curing.
18. The use according to claim 16 or 17, wherein the cementing operation is a high temperature ultra high temperature formation cementing operation of a deep well, an ultra deep well, a dry hot rock, a geothermal well.
19. The use according to any one of claims 16 to 18, wherein the broad spectrum ultra-high temperature resistant cement slurry modified in crystalline phase has a suitable circulation temperature in the range 110 ℃ to 230 ℃.
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