CN110606684B - Foam stabilizer composition, foam cement slurry additive and foam cement slurry - Google Patents

Foam stabilizer composition, foam cement slurry additive and foam cement slurry Download PDF

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CN110606684B
CN110606684B CN201810615999.9A CN201810615999A CN110606684B CN 110606684 B CN110606684 B CN 110606684B CN 201810615999 A CN201810615999 A CN 201810615999A CN 110606684 B CN110606684 B CN 110606684B
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foam
parts
cement slurry
stabilizer composition
amine oxide
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CN110606684A (en
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王翔
邓红琳
王成文
张辉
王星星
陈晓华
牛似成
王智洪
李大雷
刘颖
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China Petroleum and Chemical Corp
Sinopec North China Oil and Gas Co
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Sinopec North China Oil and Gas Co
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/48—Foam stabilisers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00017—Aspects relating to the protection of the environment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/40—Porous or lightweight materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density

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Abstract

The invention relates to a foam stabilizer composition, a foam cement slurry additive and a foam cement slurry. The foam stabilizer composition mainly comprises the following components in parts by weight: 100 parts of C12-C22 alkylamide propyl betaine, 150 parts of animal keratin hydrolysate, 75-120 parts of C8-C14 sodium alkyl benzene sulfonate and 60-100 parts of C6-C20 alkylamide alkyl amine oxide; the animal cutin protein hydrolysate is obtained by hydrolyzing animal hoof and horn powder, and has a mass concentration of 25-40%. The foam stabilizer composition can realize uniform adhesion on a foam liquid film on the basis of ensuring the stability of foam, so that the foam in a foam cement slurry system is fine and uniform, the defect of a pore structure of foam set cement is reduced, and the permeability and the compressive strength of the foam set cement at lower density are improved.

Description

Foam stabilizer composition, foam cement slurry additive and foam cement slurry
Technical Field
The invention belongs to the field of cement slurry for well cementation, and particularly relates to a foam stabilizer composition, a foam cement slurry additive and foam cement slurry.
Background
During the exploration and development of petroleum and natural gas, low-pressure and easily-leaked stratum is often faced. When the well cementation operation is carried out on a low-pressure and easily-leaked stratum, the problems of cement slurry leakage and insufficient height return are often faced. In order to prevent the loss of well cementation, foam low-density cement slurry is often used for well cementation to ensure the return height of the cement slurry and the quality of well cementation.
The foam cement slurry is prepared by filling gas into the cement slurry and improving the foam stability by surfactant substances and the like, so that the low-density three-phase viscous fluid is prepared, has the characteristics of low density, low permeability, low water loss, low thermal conductivity, compressibility, high efficiency of replacing slurry, good leakage-proof effect, higher strength and the like, and is an important technical means for solving the problem of well cementation and leakage of low-pressure easy-leakage stratum, fracture stratum, high-permeability stratum and karst cave stratum. The adoption of the foam cement slurry can effectively solve the difficult problem of well cementation and channeling in the deep water surface section, can also be applied to thermal production wells and hydraulic fracturing wells to improve the packing integrity of a cement sheath, and becomes an important technology for solving the difficult problem of complex well cementation along with the continuous deep understanding of people on the foam cement slurry and the increasingly wide application range of the foam cement slurry.
In 1979, foam cement slurry was used for the first time for in situ cementing. Then, a series of foam cement slurries with excellent performances are prepared by improving a foam generator, preferably a surfactant. In 1987-1988, 4-port technical casing well cementation and 12-port oil layer casing foam well cementation tests are performed in Xinjiang oil-burning mountain oil fields in China, and the difficult problem of well cementation of low-pressure oil-prone oil-gas wells, particularly oil-gas wells with the formation pressure coefficient smaller than 1.0, is solved. At present, the foam cement technology is continuously developed and perfected, and the foam cement is widely applied to the fields of low-pressure easily-leaked stratum well cementation, fractured lost stratum well cementation, deep water channeling-prevention well cementation and the like.
The method for preparing foam cement on site mainly comprises the following two methods: one is mechanical aeration and the other is chemical aeration (mainly nitrogen). The mechanical inflation method needs nitrogen production equipment or nitrogen vehicles, flow measurement and control equipment and the like, the equipment is more in type and quantity, the process is complex, elaborate design, computer automatic control and the like are needed, the field construction difficulty is high, and the cost is high. In contrast, the chemical aeration method does not need a plurality of devices and complex process flows, only chemical substances capable of generating nitrogen are directly added into oil well cement materials or cement paste, the nitrogen is generated through chemical reaction of the chemical substances and is filled into the cement paste to prepare the foam cement paste, the production process of the foam cement is greatly simplified, and the production cost is reduced.
The cement slurry is in an alkaline medium environment, many substances are difficult to generate a reaction of generating nitrogen in the alkaline medium, for example, sodium nitrite and ammonium chloride can only generate nitrogen in an acidic environment, the reaction generates nitrogen and is accompanied with larger heat emission, and the cement slurry is widely applied to self-generating fracturing fluid, thermochemical flooding oil and the like. However, sodium nitrite and ammonium chloride cannot generate nitrogen in the cement slurry alkaline medium.
In addition, some azo-based substances can generate nitrogen by self-decomposition reaction when the temperature reaches its decomposition temperature under heating, such as azodicarbonamide, azodiisobutyronitrile, dinitrosopentamethylenetetramine, 4' -oxybis-benzenesulfonylhydrazide, p-toluenesulfonylhydrazide, 5-phenyltetrazole, trihydrazinotriazine, and the like. However, these substances are not only expensive, but also flammable and explosive, have certain potential safety hazard, and are not suitable for ground preparation environment and conditions of the foamed cement slurry.
An ultra-low density foam cement slurry (drilling fluid and completion fluid, 1997, 14, 4, 27-28) suitable for cementing in Changqing oil field is developed in the province of construction, and chemical gas generators FCA and FCB are adopted to perform chemical reaction in the cement slurry to generate nitrogen, and meanwhile, a stabilizing agent is addedFoam FCF, produced to a density as low as 1.20g/cm3The foamed cement slurry of (1). The application of a novel foam cement slurry system in the Laizhou bay area of the Shengli oil field (drilling process, 2009, 32 vol, 6 th, 113 th and 115 th pages) is researched, wherein floating beads are firstly utilized to reduce the density of cement slurry to 1.33g/cm3The density is then further reduced by means of chemical gassing.
The lower the density of the foamed cement slurry is, the lower the required construction pressure is, and the better the construction effect on low-pressure and easily-leaked stratum is. The density of the foamed cement paste is reduced to 1.20g/cm3On the other hand, it is difficult to further reduce the density, because the foamed cement slurry belongs to a thermodynamically unstable system, and the foam stability is poor in the absence of a foam stabilizer or under the condition of poor performance of the foam stabilizer, so that the foamed cement slurry with lower density cannot be prepared.
The patent application with publication number CN106431052A discloses a foam stabilizer composition and application thereof, and foamed cement slurry and an additive composition and application thereof, wherein the foam stabilizer composition contains C6-C20 alkylamide alkyl amine oxide, C6-C20 alkylamide alkyl betaine and triterpenoid saponin compounds. The foam stabilizer can reduce the density of the foam cement slurry to 1g/cm3However, the uneven size of the foam can cause uneven pore structure of the foam cement stone, and further cause problems of high permeability, low compressive strength and the like.
Disclosure of Invention
The invention aims to provide a foam stabilizer composition, so as to solve the problems of poor foam stabilizing performance and uneven foam size when the existing foam stabilizer is applied to a foam cement slurry system. The invention also provides a foam cement slurry additive containing the foam stabilizer composition and a foam cement slurry.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a foam stabilizer composition mainly comprises the following components in parts by weight: 100 parts of C12-C22 alkylamide propyl betaine, 150 parts of animal keratin hydrolysate, 75-120 parts of C8-C14 sodium alkyl benzene sulfonate and 60-100 parts of C6-C20 alkylamide alkyl amine oxide; the animal cutin protein hydrolysate is obtained by hydrolyzing animal hoof and horn powder, and has a mass concentration of 25-40%.
The foam stabilizer composition provided by the invention is mainly prepared by compounding C12-C22 alkyl amide propyl betaine, animal keratin protein hydrolysate, C8-C14 sodium alkyl benzene sulfonate and C6-C20 alkyl amide alkyl amine oxide according to a certain proportion, and in an alkaline medium environment provided by cement paste, the combination of the components can effectively improve the mechanical strength and viscosity of a foam liquid film and improve the stability of foam; meanwhile, the foam stabilizer composition can realize uniform adhesion on a foam liquid film on the basis of ensuring the stability of foam, so that the foam in a foam cement slurry system is fine and uniform, the defect of a pore structure of foam set cement is reduced, and the permeability and the compressive strength of the foam set cement at lower density are improved.
The foam stabilizer composition can be provided in the form of an aqueous solution, and the mass concentration can be controlled within the range of 20-40%, preferably 25-35%.
The structural formula of the C12-C22 alkyl amidopropyl betaine is shown as the formula (1):
Figure BDA0001696923200000031
in the formula (1), R is C12-C22 alkyl. Preferably, the C12-C22 alkylamidopropyl betaine is one or more of cocamidopropyl betaine, lauramidopropyl betaine, palmitoamidopropyl betaine, n-tetradecylamidopropyl betaine, n-hexadecylamidopropyl betaine, n-octadecyl amidopropyl betaine, more preferably lauramidopropyl betaine (LAB) and/or cocamidopropyl betaine. The C12-C22 alkyl amidopropyl betaine can be obtained through a conventional market channel, so that the cost of the foam stabilizer composition can be reduced, and the comprehensive performance of the foam stabilizer composition can be improved.
The structural formula of the C8-C14 sodium alkyl benzene sulfonate is R' -C6H4-SO3Na, wherein R' is C8-C14 alkyl. From the viewpoint of improving the overall performance of the resulting foam stabilizer composition and facilitating the availability thereof, it is preferable that,the sodium C8-C14 alkylbenzene sulfonate is sodium dodecyl benzene sulfonate.
The structural formula of the C6-C20 alkylamide alkylamine oxide is shown as a formula (2):
Figure BDA0001696923200000041
in the formula (2), R2And R3Each independently selected from C1-C6 alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; r1Alkylene radicals having a meaning of C1-C10, e.g. -CH2-、-CH2-CH2-、-CH2-CH2-CH2-、-CH(CH3)-CH2-、-CH2-CH(CH3)-、-CH2-(CH2)2-CH2-、-CH2-(CH2)3-CH2-、-CH2-(CH2)4-CH2-、-CH2-(CH2)5-CH2-、-CH2-(CH2)6-CH2-、-CH2-(CH2)7-CH2-or-CH2-(CH2)8-CH2-；R4Is C6-C20 alkyl. Preferably, the C6-C20 alkylamidoalkylamine oxide is one or more of cocamidopropyl amine oxide, lauramidopropyl amine oxide, octylamidopropyl amine oxide, nonylamidopropyl amine oxide, decylamidopropyl amine oxide, n-undecylamidopropyl amine oxide, n-tetradecylamidopropyl amine oxide, n-hexadecylamidopropyl amine oxide, n-octadecyl amidopropyl amine oxide, more preferably Cocamidopropyl Amine Oxide (CAO) and/or lauramidopropyl amine oxide. Wherein, in the specific compounds enumerated above, R2And R3The site of (2) is methyl.
The animal keratin hydrolysate is prepared by the method comprising the following steps: reflux-reacting animal hoof and horn powder, calcium hydroxide and water at 95-100 deg.C for 7-9 hr, separating solid and liquid, and adjusting pH of the obtained liquid phase to 7.0. Preferably, the weight ratio of the animal hoof and horn powder to the calcium hydroxide to the water is 100: (16-25): (70-98).
The invention also provides application of the foam stabilizer composition as a foam stabilizer in foamed cement slurry.
The foam stabilizer composition provided by the invention replaces the components of the foam stabilizer in the conventional foam cement slurry, so that the effects of reducing the density of the foam cement slurry, improving the foam stability, reducing the permeability of the foam set cement and improving the compressive strength of the foam set cement can be achieved, and the foam stabilizer composition can be conveniently applied to the well cementation operation of low-pressure easily-permeable stratum.
A foam cement slurry additive mainly comprises a gas former I, a gas former II, the foam stabilizer composition and a nano sol reinforcing agent, wherein the gas former I is one or more of chlorate, perchlorate and chlorite; the gas former II is one or more of hydrazine compounds, hydroxylamine compounds and amide compounds.
The gas generating agent I has oxidability, and can be chlorate of potassium, sodium, ammonium, lithium, magnesium, calcium, perchlorate or chlorite, preferably one or more of potassium chlorate, magnesium chlorate, sodium chlorate, calcium chlorate, sodium perchlorate, ammonium perchlorate, potassium perchlorate, lithium perchlorate, sodium chlorite, potassium chlorite and calcium chlorite, more preferably one or more of potassium chlorite, sodium chlorite, potassium perchlorate and sodium perchlorate.
The gas former II has reducibility and can react with the gas former I to generate nitrogen, thereby forming a nitrogen source for preparing the foam cement slurry by a chemical inflation method. Preferably, the gas former II is one or more of N, N '-diformylhydrazine, carbamyl hydrazine, carbonic acid dihydrazide, ammonium chloride, hydroxylamine hydrochloride, formylhydrazine, oxalyl hydrazine, N' -diacetylhydrazide, formamide and hydroxylamine sulfate, and more preferably carbonic acid dihydrazide, ammonium chloride and/or hydroxylamine sulfate.
The nano sol reinforcing agent is nano titanium dioxide hydrosol. The mass concentration of the nano titanium dioxide hydrosol is 20-30%. The particle size of the nano titanium dioxide hydrosol is 25-30 nm.
The weight ratio of the gas former I, the gas former II, the foam stabilizer composition and the nano sol reinforcing agent is 100: (30-85): (120-300): (150-350), preferably 100: (35-75): (150-280): (175-290), more preferably 100: (40-60): (170-240): (200-260). As described above, the foam stabilizer composition may be in the form of an aqueous solution having a mass concentration of 20 to 40%. The gas generating agent II may also be provided in the form of an aqueous solution, which may be, for example, a 35-65% by weight aqueous solution. The active ingredient content of each component can be conveniently obtained by conversion according to the weight and the mass concentration of the aqueous solution.
The foam cement slurry additive and the foam stabilizer composition can be cooperated with the nano sol reinforcing agent to play a role in enhancing the structural strength of a foam film, so that the foam quality and the stability are improved. When the additive is applied to the preparation of foam cement, the addition amount is small, and the production cost of the foam cement can be effectively reduced.
The invention also provides foamed cement slurry using the foamed cement slurry additive.
The foam cement slurry containing the foam cement slurry additive composition has higher foam stability, fine and uniform foam, low permeability of cured foam cement stone, high compressive strength and density of 0.75-1.37g/cm3Is adjusted within the range of (1).
The foamed cement slurry comprises cement and a foamed cement additive, wherein the addition amount of the foamed cement additive is 2-12 parts by weight per 100 parts by weight of the cement. Preferably, the foam cement additive is added in an amount of 2.5 to 8.6 parts by weight, more preferably 2.7 to 6.5 parts by weight. In the charging proportion, the weight parts of the foam cement additive are calculated by active ingredients.
The cement used for the foamed cement slurry can be the conventional cement variety used for the foamed cement slurry, such as one or more of API oil well G-grade cement, H-grade cement and A-grade cement.
In addition, the foamed cement slurry can also contain other auxiliary substances commonly used for foamed cement slurry. Preferably, the foamed cement slurry also contains a fluid loss agent, a dispersing agent and an early strength agent. In order to obtain foam cement slurry with better performance, the addition amount of the corresponding fluid loss additive is preferably 1.0 to 2.6 parts by weight, the addition amount of the corresponding dispersant is preferably 0.1 to 0.6 part by weight, and the addition amount of the corresponding early strength agent is preferably 1.2 to 3.5 parts by weight, per 100 parts by weight of cement. More preferably, the addition amount of the fluid loss additive, the dispersant and the early strength agent is 1.2 to 2.0 parts by weight, 0.3 to 0.4 part by weight and 1.8 to 3.2 parts by weight respectively per 100 parts by weight of cement. The charging proportions of the raw materials are all calculated by dry weight.
The fluid loss agent has the function of reducing the water loss of foam cement slurry, and can select polyvinyl alcohol fluid loss agents, poly (acrylamide/2-acrylamide-2-methylpropanesulfonic acid) (AM/AMPS, namely a copolymer of acrylamide and 2-acrylamide-2-methylpropanesulfonic acid) and other varieties.
The dispersant has the function of improving the fluidity of the foam cement slurry, and specifically, sulfonated acetone-formaldehyde polycondensate dispersant, polynaphthalene sulfonate dispersant and the like can be selected.
The early strength agent has the functions of adjusting the thickening time of the foamed cement slurry and improving the strength of the foamed cement paste, and can be one or more of potassium chloride, sodium metaaluminate, lithium chloride, calcium formate, calcium lactate, calcium chloride, lithium hydroxide and potassium silicate.
The foamed cement slurry also contains water. The water may be provided in the form of an aqueous solvent. Preferably, the aqueous solvent is added in an amount of 42 to 72 parts by weight, preferably 45 to 65 parts by weight, more preferably 48 to 60 parts by weight, per 100 parts by weight of cement. The aqueous solvent may be water, or may be an aqueous solution containing a small amount of other solutes which do not affect the properties of the foamed cement slurry of the present invention, such as one or more of sodium chloride solution, potassium chloride solution, magnesium chloride solution, and calcium chloride solution.
In a preferred embodiment of the present invention, the foamed cement slurry of the present invention consists of water and the following components in parts by weight, provided that the above ranges of amounts are met: 100 parts of cement, 0.4-2.2 parts of gas former I, 0.2-1.2 parts of gas former II, 0.8-2.0 parts of foam stabilizer composition, 1-4 parts of nano sol reinforcing agent, 1.0-2.6 parts of fluid loss agent, 0.1-0.6 part of dispersing agent and 1.2-3.5 parts of early strength agent. Further preferably, the foamed cement slurry consists of water and the following components in parts by weight: 100 parts of cement, 0.48-1.0 part of gas former I, 0.2-0.5 part of gas former II, 0.9-1.8 parts of foam stabilizer composition, 1.2-2 parts of nano sol reinforcing agent, 1.2-2 parts of fluid loss agent, 0.3-0.4 part of dispersing agent and 1.8-3.2 parts of early strength agent.
When the foam cement slurry is prepared, firstly, dry-mixing cement, a gas former I, a fluid loss agent and a dispersing agent to obtain a dry-mixed mixture; and (3) premixing water, the foam stabilizer composition, the nano titanium dioxide hydrosol and the early strength agent, then adding the dry mixture, and uniformly mixing under a closed condition to obtain the composite material. Preferably, the premixing is carried out by stirring and mixing at 3500-. The mixing is carried out for 30-40s under the conditions of 11000 and 13000 rpm.
The foamed cement slurry prepared by the technical scheme has lower density (which can be as low as 0.75 g/cm)3) The foam has the characteristics of high foam stability, low permeability, high compressive strength and the like, and can meet the well cementation requirements of low-pressure and easily permeable stratum. Moreover, the foamed cement slurry is environment-friendly, has good foaming and foam stabilizing effects, can meet the requirement of well cementation compressive strength of a sealing production layer, and has wide application prospect.
Drawings
FIG. 1 is a comparison of the appearance properties of the foamed cement slurries of example 9 and comparative example 7.
Detailed Description
The following further describes embodiments of the present invention with reference to the drawings. In the following examples, the G-grade oil well cement was a high sulfur-resistant G-grade oil well cement purchased from Shandong Lin \26384victoryWeichai specialty Cement Ltd. Lauramidopropyl betaine, available under the trademark LAB-35, was purchased from Shanghai Asian Chemicals, Inc. Cocamidopropyl amine oxide, available under the trademark CAO-35, is available from Shanghai Asian Chemicals, Inc. Sodium dodecylbenzenesulfonate was purchased from Shanghai national drug group chemical Co., Ltd. Cocamidopropyl betaine, available from Shanghai Asia Chemicals, Inc., is available under the CAB-35 trademark. Lauramidopropylamine oxide is available under the trademark LAO-30 from Shanghai Asian Chemicals, Inc. The nano titanium dioxide hydrosol is purchased from Xuancheng crystal new material Co., Ltd, the active matter content is 20 wt%, the particle size is 25-30nm, and the pH value is 6-8.
The polyvinyl alcohol fluid loss agent has the brand number of G60S, and the sulfonated formaldehyde-acetone polycondensate dispersant has the brand number of CF40, which are all purchased from engineering science and technology Limited company Bohai star in Tianjin.
The animal keratin hydrolysate is prepared by the following method: crushing animal hoof and horns (of cattle and sheep) into fine powder of 80-120 meshes, sequentially adding 100 parts by weight of animal hoof and horns powder, 20 parts by weight of calcium hydroxide and 84 parts by weight of water into a three-necked bottle with a stirrer, a thermometer and a condenser, heating to 95-100 ℃, stirring, condensing, refluxing for 8 hours, stopping heating, naturally cooling, performing suction filtration, collecting filtrate, and neutralizing the filtrate with hydrochloric acid until the pH value is 7.0 to obtain the animal keratin hydrolysate with the active matter content of 30 wt%.
Example 1
The foam stabilizer composition of this example is composed of water and the following components in parts by weight: 100 parts of cocamidopropyl betaine, 130 parts of animal keratin hydrolysate, 80 parts of sodium dodecyl benzene sulfonate and 60 parts of cocamidopropyl amine oxide; the foam stabilizer composition is in the form of an aqueous solution, and the mass concentration of the foam stabilizer composition is 35%.
And uniformly mixing water with cocamidopropyl betaine, animal keratin hydrolysate, sodium dodecyl benzene sulfonate and cocamidopropyl amine oxide, and dissolving into a transparent uniform solution to obtain the foam stabilizer composition F1.
Examples 2 to 6
The formulation of the foam stabilizer compositions of examples 2-6 are shown in Table 1, and the foam stabilizer compositions were prepared according to the method described in example 1.
TABLE 1 formulation composition of foam stabilizer compositions of examples 2-6
Figure BDA0001696923200000081
Example 7
The foamed cement slurry of the embodiment comprises the following components in parts by weight: 100 parts of G-grade oil well cement, 0.90 part of gas former I, 0.40 part of gas former II, 11.6 parts of foam stabilizer composition F, 2.0 parts of nano titanium dioxide hydrosol, 1.6 parts of fluid loss additive, 0.35 part of dispersing agent, 3.0 parts of early strength agent and 60 parts of water. The gas former I is sodium chlorite, the gas former II is carbolic acid dihydrazide, the early strength agent is potassium chloride, and the dosage of the components is calculated by the weight of active matters without solvent.
The preparation method of the foamed cement slurry of the embodiment adopts the following steps:
1) dry-mixing G-grade oil well cement, a gas former I, a polyvinyl alcohol fluid loss agent and a sulfonated formaldehyde-acetone polycondensate dispersant to obtain a dry mixture;
2) stirring and mixing water, a foam stabilizer F1, a nano titanium dioxide hydrosol and a potassium chloride early strength agent at 4000rpm for 15S, adding the dry mixture obtained in the step 1), adding a carbonic acid dihydrazide gas former II (in the form of an aqueous solution with the mass concentration of 46 wt%) under a closed condition, and stirring at 12000rpm for 35S to obtain foam cement slurry S1 with the density of 0.75g/cm3。
Example 8
The foamed cement slurry of the embodiment comprises the following components in parts by weight: 100 parts of G-grade oil well cement, 0.85 part of gas former I, 0.38 part of gas former II, 21.6 parts of foam stabilizer composition F, 2.0 parts of nano titanium dioxide hydrosol, 1.55 parts of fluid loss agent, 0.3 part of dispersing agent, 3.0 parts of early strength agent and 56 parts of water. The gas former I is potassium chlorite, the gas former II is hydroxylamine sulfate, the early strength agent is potassium chloride, and the dosage of the components is calculated by the weight of the active matter without solvent.
A foamed cement slurry S2 having a density of 0.90g/cm was prepared by the method of reference example 73。
Example 9
The foamed cement slurry of the embodiment comprises the following components in parts by weight: 100 parts of G-grade oil well cement, 0.75 part of gas former I, 0.36 part of gas former II, 31.45 parts of foam stabilizer composition, 1.8 parts of nano titanium dioxide hydrosol, 1.5 parts of fluid loss additive, 0.3 part of dispersing agent, 2.0 parts of early strength agent and 52 parts of water. The gas former I is potassium perchlorate, the gas former II is hydroxylamine sulfate, the early strength agent is calcium chloride, and the dosage of the components is calculated by the weight of the active matter without solvent.
A foamed cement slurry S3 was prepared according to the method of reference example 7, and had a density of 1.12g/cm3。
Example 10
The foamed cement slurry of the embodiment comprises the following components in parts by weight: 100 parts of G-grade oil well cement, 0.61 part of gas former I, 0.3 part of gas former II, 11.4 parts of foam stabilizer composition F, 1.4 parts of nano titanium dioxide hydrosol, 1.5 parts of fluid loss additive, 0.32 part of dispersing agent, 2.5 parts of early strength agent and 50 parts of water. The gas former I is sodium chlorite, the gas former II is carbolic acid dihydrazide, the early strength agent is potassium chloride, and the dosage of the components is calculated by the weight of active matters without solvent.
A foamed cement slurry S4 was prepared according to the method of reference example 7, and had a density of 1.23g/cm3。
Example 11
The foamed cement slurry of the embodiment comprises the following components in parts by weight: 100 parts of G-grade oil well cement, 0.5 part of gas former I, 0.22 part of gas former II, 10.92 parts of foam stabilizer composition F, 1.2 parts of nano titanium dioxide hydrosol, 1.5 parts of fluid loss additive, 0.36 part of dispersing agent, 2.5 parts of early strength agent and 48 parts of water. The gas former I is sodium chlorite, the gas former II is carbolic acid dihydrazide, the early strength agent is potassium chloride, and the dosage of the components is calculated by the weight of active matters without solvent.
Reference example 7A foamed cement slurry S5 was prepared with a density of 1.37g/cm3。
Examples 12 to 14
The foamed cement slurries of examples 12 to 14 had the same formulation as in example 1 except that F1 was replaced with foam stabilizer composition F4, foam stabilizer composition F5 and foam stabilizer composition F6, respectively, to give foamed cement slurries S6, S7 and S8, respectively, and the densities thereof were 0.80g/cm3、0.82g/cm3、0.83g/cm3。
Comparative examples 1 to 3
The formulation compositions of the foam stabilizers of comparative examples 1 to 3 are shown in Table 2.
TABLE 2 formulation composition of foam stabilizers for comparative examples 1-3
Figure BDA0001696923200000101
(Note: "-" represents no addition.)
Comparative examples 4 to 6
The foamed grouts of comparative examples 4 to 6, having the same formulation as in example 1, differ only in that the foam stabilizer composition F1 was replaced with the foam stabilizers DF1, DF2 and DF3, respectively, to give foamed grouts DS1, DS2 and DS3, respectively, having densities of 0.93g/cm3、0.90g/cm3、1.15g/cm3. (different densities due to different foam stabilizing effects.)
Comparative example 7
The foamed cement slurry of comparative example 7 was prepared to have a density of 1.15g/cm as described in example 1 of patent application publication No. CN106431052A3The foamed cement slurry of (1).
Test example 1
The measurements of the ambient and atmospheric water loss (API) and thickening time for foamed cement slurries S1-S8 and DS1-DS3 were made according to the American Petroleum institute standard (API RP 10B-4-2004) and are shown in Table 3.
TABLE 3 API fluid loss and thickening time for different foamed cement slurries
Figure BDA0001696923200000111
The results in table 3 show that in the foamed cement slurry prepared by the invention, the API water loss is effectively controlled, the water loss is small, the cement slurry thickening time is kept in a reasonable range of 172-one 251 minutes, the well cementation construction requirements can be met, and the gas former substance, the foam stabilizer, the nano sol reinforcing agent substance, the fluid loss agent, the dispersing agent and the early strength agent have good compatibility. The foam cement slurry of the comparative example has a large API water loss, which indicates that the compatibility of the foam stabilizer and the cement slurry system is poor, while the compatibility of the comparative example 3 is the worst, and has a large adverse effect on the API water loss and the thickening time.
Test example 2
The compressive strength and permeability of the foamed cement formed from the foamed cement slurries S1-S8 and DS1-DS3 were measured according to the American Petroleum institute standard (API RP 10B-4-2004) and the results are shown in Table 4.
TABLE 4 compressive Strength and Permeability of foamed Cement Panels formed from respective foamed Cement slurries
Figure BDA0001696923200000112
Figure BDA0001696923200000121
In the formula compositions of the cement slurries S1, DS1, DS2 and DS3, the difference is only that the foam stabilizers are different in type, but the density of the cement slurry S1 is lower than that of the cement slurries DS1, DS2 and DS3 due to the difference of foam stabilizing capability, the compressive strength of the foamed cement stone is still higher than that of the foamed cement slurry of the comparative example under low density due to the uniform and fine characteristics of foam, the permeability is still lower than that of the foamed cement slurry of the comparative example, and good comprehensive performance is reflected.
Test example 3
The foamed cement slurries S1-S8 and DS1-DS3 were left to stand at room temperature (25 ℃) and the density and density change rate of the foamed cement slurries were tested every 10min, with the results shown in Table 5.
TABLE 5 Density and Density Change Rate data of different foamed cement slurries
Figure BDA0001696923200000122
Figure BDA0001696923200000131
(Note: density change rate ═ density60min-density0min) Density/density0min×100％)
From the results in Table 5, it is understood that the foamed cement slurries of the examples are 0.7 to 1.4g/cm3Density of (2)Within the range, the density change rate is obviously lower than that of a comparative example, so that good foam stabilizing performance is reflected, and the improvement of the foam stabilizing performance is also beneficial to improving the construction performance of the foam cement slurry and improving the well cementation quality of low-pressure and easily permeable stratum.
Test example 4
The pictures of the appearance of the foamed cement paste of example 9 and the foamed cement paste of comparative example 7 are shown in fig. 1, and it can be seen that the foam of the cement paste prepared in example 9 (fig. 1 (a)) is finer and more uniform, while the foam size distribution of the cement paste prepared in comparative example 7 (fig. 1 (b)) is uneven. Example 7 further reflects the superior properties of the foam stabilizer compositions and cement slurry additives of the present invention in terms of additive usage, by allowing the preparation of lower density foamed cement slurries with lower additive usage.

Claims (8)

1. The foam stabilizer composition is characterized by comprising the following components in parts by weight: 100 parts of C12-C22 alkylamide propyl betaine, 150 parts of animal keratin hydrolysate, 75-120 parts of C8-C14 sodium alkyl benzene sulfonate and 60-100 parts of C6-C20 alkylamide alkyl amine oxide; the animal cutin protein hydrolysate is obtained by hydrolyzing animal hoof and horn powder, and has a mass concentration of 25-40%;
the animal keratin hydrolysate is prepared by the method comprising the following steps: reflux-reacting animal hoof and horn powder, calcium hydroxide and water at 95-100 deg.C for 7-9 hr, separating solid and liquid, and adjusting pH of the obtained liquid phase to 7.0 to obtain final product;
the weight ratio of the animal hoof and horn powder to the calcium hydroxide to the water is 100: (16-25): (70-98).
2. The foam stabilizer composition of claim 1, wherein the C12-C22 alkylamidopropyl betaine is one or more of cocamidopropyl betaine, lauramidopropyl betaine, palmamidopropyl betaine, n-tetradecylamidopropyl betaine, n-hexadecylamidopropyl betaine, and n-octadecyl amidopropyl betaine.
3. The foam stabilizer composition of claim 1, wherein the C6-C20 alkylamidoalkylamine oxide is one or more of cocamidopropyl amine oxide, lauramidopropyl amine oxide, octylamidopropyl amine oxide, nonylamidopropyl amine oxide, decylamidopropyl amine oxide, n-undecylamidopropyl amine oxide, n-tetradecylamidopropyl amine oxide, n-hexadecylamidopropyl amine oxide, and n-octadecyl amidopropyl amine oxide.
4. The foam stabilizer composition of any one of claims 1-3, wherein the sodium C8-C14 alkylbenzene sulfonate is sodium dodecylbenzene sulfonate.
5. The foam cement slurry additive adopting the foam stabilizer composition as claimed in claim 1, which mainly comprises an air forming agent I, an air forming agent II, the foam stabilizer composition and a nano sol reinforcing agent, wherein the air forming agent I is one or more of chlorate, perchlorate and chlorite; the gas former II is one or more of hydrazine compounds, hydroxylamine compounds and amide compounds.
6. The foamed cement slurry additive of claim 5, wherein the weight ratio of air-generating agent I, air-generating agent II, foam stabilizer composition and nanosol reinforcement agent is 100: (30-85): (120-300): (150-350).
7. The foamed cement slurry additive of claim 5 or 6, wherein said nanosol reinforcing agent is a nanosol of titanium dioxide hydrosol.
8. A foamed cement slurry using the foamed cement slurry additive of claim 5.
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CN105294821A (en) * 2015-09-22 2016-02-03 河南永立建材有限公司 Preparation method of animal toenail type surfactant
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