Method for preparing high-temperature-resistant anti-degradation well cementing material by using high-aluminum and silicon solid waste

Abstract

The application discloses a method for preparing high-temperature-resistant and anti-degradation well cementing material by using high-aluminum and high-silicon solid wastes, and the content of each component in the raw material is calculated according to the total mass of 100%, and the content of glass is 32-48%, the content of waste ceramic is 30-45%, the content of aluminum oxide is 15-25%, the content of boron trioxide is 1.1-4.8%, the content of alkaline earth metal oxide is 1.6-4.6%, the content of alkali metal oxide is 0.7-4.6%, the content of zirconium oxide is 0.8-5%, the content of zinc oxide is 0.4-2%, and the content of phosphorus pentoxide is 0.4-2%. The raw material is crushed, ground and grinded, the high-silicon aluminum precursor particles prepared by physical methods, chemical methods or the combination of both are pretreated, high-temperature spheroidized and surface-coated, so that the high-temperature-resistant and anti-degradation spherical additive product is prepared. The product has the excellent performances of high sphericity, good fluidity, small friction resistance, easy mixing, simple use and the like; the high-temperature resistance and anti-degradation are obvious under the well condition that the bottom hole static temperature is 150-300 DEG C, and the cement stone strength is obviously improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of functional materials, and particularly relates to a preparation method of a high-temperature-resistant anti-degradation well cementing material for oil and gas resource exploitation, which is particularly suitable for high-temperature well cementing operation of deep layer, ultra-deep layer (more than 10,000 meters) and complex reservoir oil and gas resources with a well bottom static temperature of 150-300 DEG C. BACKGROUND

[0002] At present, oil and gas resource exploration and development gradually develops in the direction of "deep, low, sea and non", the number of deep wells and ultra-deep wells gradually increases, the geological conditions become more and more complex, and the well cementing difficulty is more and more high. Well cementing is an important part of oil and gas resource exploitation, and well cementing additives play an important role. China is relatively rich in oil and gas resources, which are mainly concentrated in Tarim Basin, Sichuan Basin, Songliao Basin, Junggar Basin, Qaidam Basin and Bohai Bay, among which more than 34% are in deep layer, ultra-deep layer and complex reservoir, and the downhole environment is in high temperature and high pressure state, which puts forward higher requirements for well cementing technology and materials.

[0003] As the most commonly used cementing material in domestic and foreign well cementing process, the silicate cement system has the advantages of low cost and wide applicability. However, when the curing temperature of the conventional silicate cement stone is above 110 DEG C, the hydration product is transformed from amorphous C-S-H gel to alpha-C2SH crystal, resulting in strength decay. With the exploitation of deep layer and ultra-deep layer reservoir oil and gas resources, the strength decay, poor high-temperature stability, cracking shrinkage and other problems of the cement stone are more and more obvious when the well bottom static temperature is above 150 DEG C, especially when the temperature is above 200 DEG C, and the curing time is 2 days, 7 days, 14 days, 28 days and above, thereby leading to the failure of the interlayer sealing of the well cementing cement ring and becoming a big problem restricting the exploitation of oil and gas resources.

[0004] At present, the domestic polymer retarder generally has the defects of poor high-temperature retardation effect, strong dispersibility, slow development of mechanical properties under large temperature difference and causing abnormal cementing of cement slurry, and the fluid loss additive has the problems of poor high-temperature resistance and salt resistance and strong high-temperature dilution. In order to solve the above problems, the Chinese doctoral thesis "Research on Polymer / Nano-SiO2 Composite Additive for High-Temperature Deep Well Cementing" published in May 2017 prepared a high-temperature retarder ADNIOS by in-situ polymerization method with 2-acrylamide-2-methylpropanesulfonic acid (AMPS), dimethyl-diallyl ammonium chloride, N,N-dimethyl acrylamide (NNDMA), itaconic acid, dimethyl octadecyl allyl ammonium chloride (ODAAC) and modified nano-SiO2 (VN) as raw materials, which can be applied to low-density, conventional-density and high-density cement slurry systems, has a temperature resistance of up to 210 DEG C, and has good comprehensive performance of cement slurry, which can meet the requirements of well cementing engineering. However, the production cost of this high-temperature retarder is extremely high, which is difficult to be applied on a large scale in well cementing engineering.

[0005] In order to solve the problem caused by high temperature at the bottom of the well such as strength recession, the current technical personnel introduces silica sand (or microsilica, silicon powder, etc.) as the main high-temperature recession prevention material, which improves the high-temperature stability of the cement stone to a certain extent, but the cement stone still has obvious recession phenomenon. When the bottom hole temperature is higher than 150℃, the effect of slowing down the recession of the cement stone is continuously weakened, especially when the temperature is higher than 200℃, the recession prevention effect is almost lost. In the article "Deep Ultra-high Temperature Cement Slurry Formulation and Strength Recession Mechanism" published in Natural Gas Industry, Vol. 43, No. 7, July 2023, it is found that high silica sand ratio will produce more amorphous C-S-H gel hydration products at 200℃ curing temperature, which helps to improve the short-term strength of the cement stone, but will lead to accelerated long-term strength recession.

[0006] At present, the oil and gas resource exploitation site requires that the cement stone should have high temperature resistance under high temperature conditions. Chinese patent CN108751753B discloses "High-temperature cementing cement and high-temperature cementing cement slurry", the mineral composition of the cement clinker includes tricalcium silicate, dicalcium silicate, tricalcium aluminate, tetracalcium aluminoferrite and other components, and the strength recession phenomenon occurs after 7d curing at 150-300℃, and the recession prevention phenomenon is not obvious.

[0007] In view of the above problems, the present application uses materials or minerals containing components such as silicon, aluminum, calcium, magnesium, boron, lithium, sodium, potassium, zinc, phosphorus and zirconium as main raw materials, and prepares a high-temperature resistant recession prevention spherical additive for oil and gas resource exploitation by high-temperature melting and spheroidizing technology, and the surface is coated with a high-temperature modifier, and finally applied to the cementing cement slurry system. The prepared high-temperature resistant recession prevention spherical additive has high sphericity, good fluidity, small friction resistance, easy mixing uniformity, simple use and other excellent properties; under the well condition of bottom hole static temperature of 150-300℃, the cement stone has no strength recession, and the strength of the cement stone is significantly improved. SUMMARY

[0008] The purpose of the present application is to solve the technical problems of the existing oil and gas resource exploitation cementing material, such as serious high-temperature strength recession, accelerated long-term strength recession, poor high-temperature stability, cracking shrinkage, poor use convenience, high use cost and difficult large-scale application in engineering, etc., and to provide a method for preparing a high-temperature resistant recession prevention cementing material from high aluminum and silicon solid waste, so as to solve the problem of long-term strength recession of the cement stone in the high-temperature well cementing operation process under the condition of bottom hole static temperature of 150-300℃, and to meet the needs of deep and ultra-deep reservoir oil and gas resource exploitation.

[0009] In order to achieve the above purpose, the method for preparing a high-temperature resistant recession prevention cementing material from high aluminum and silicon solid waste is implemented by the following steps:

[0010] S1: Preparation of precursor particles

[0011] The raw materials are accurately weighed according to the raw material formula composition, crushed, ground to a particle size of less than 30 μm, then pre-mixed and granulated to obtain high-silicon aluminum precursor particles with a particle size of ≤200 μm and a porosity of ≤2%, thereby ensuring that the subsequent steps can produce high-temperature resistant anti-degradation spherical additives that meet the particle size and density requirements; the granulation can be performed by one of the methods such as wet granulation, dry granulation, adhesive granulation, fluidized bed granulation, and dry granulation; if the particles are too large, they can be sorted out by a vibrating screen, a classifier, or the like, and the material can be re-granulated; if the porosity does not meet the requirements, the material can also be re-crushed, ground, and then granulated to improve the utilization rate of raw materials and reduce waste. The reasonable particle size range after granulation is preferably between 2 and 200 μm.

[0012] When the sum of the mass of each component in the raw material is calculated as 100%, the content of each component is: waste glass 32-48%, waste ceramic 30-45%, aluminum oxide 15-25%, boron trioxide 1.1-4.8%, alkaline earth metal oxide 1.6-4.6%, alkali metal oxide 0.7-4.6%, zirconium oxide 0.8-5%, zinc oxide 0.4-2%, and phosphorus pentoxide 0.4-2%.

[0013] S2: Pretreatment of precursor particles

[0014] The high-silicon aluminum precursor particles prepared in step S1 are pretreated by a physical method, a chemical method, or a combination of both, to achieve the best flowability, so that they can be uniformly dispersed in the subsequent high-temperature spheroidization step, and form individual particles after high-temperature vitrification, while improving the efficiency of heat transfer in the furnace.

[0015] S3: High-temperature spheroidization of precursor particles

[0016] After the high-silicon aluminum precursor particles prepared in step S2 are thoroughly mixed with a combustion-supporting gas, the material is fed into a high-temperature vitrification furnace with a temperature of 1300-1600°C by pneumatic conveying, and the high-silicon aluminum precursor particles are melted into a glass melt after high-temperature melting, and then rapidly cooled to form spherical additives with a particle size of ≤200 μm, a strength of 50-150 MPa, and a density of 2.0-2.8 g / cm 3 The prepared spherical additives, being high-silicon aluminum glassy substances, can slowly react with cement stone, avoiding the phenomenon of high early strength and weak late strength or growth caused by the violent reaction of ordinary anti-degradation agents or anti-strength degradation agents.

[0017] S4: Surface coating treatment of spherical additives

[0018] The spherical aid obtained in S3 is coated with a high-temperature resistant surface treatment agent resistant to high-temperature conditions of 150-300 DEG C to obtain a product with a particle size of 200 microns or less, a compressive strength of 50-150 MPa, and a density of 2.0-2.8 g / cm 3 , a high-temperature resistant anti-decay spherical aid product capable of preventing the strength decay of cement stone under conditions of 150-300 DEG C. Through surface coating treatment, the combination ability with cement slurry is improved, and the reaction speed with cement slurry or cement stone under high-temperature environment is delayed.

[0019] Further, the waste glass is preferably waste borosilicate glass, and the mass percentage of each component is: 80-86% of SiO2, 3-7% of B2O3, 3-7% of alkaline earth metal oxide, 3-7% of alkali metal oxide, and ≤1% of the balance.

[0020] Further, the waste ceramic has a mass percentage of each component of: 35-45% of SiO2, 35-45% of Al2O3, 8-12% of alkaline earth metal oxide, 8-12% of alkali metal oxide, and ≤1% of the balance.

[0021] Further, in S2, the physical method is to sufficiently remove the water on the surface of the high-silicon aluminum precursor particles under conditions of 80-150 DEG C, or to impart the same charge to the surface of the high-silicon aluminum precursor particles by electrodes to achieve the effect of mutual repulsion between particles; or a combination of the above two methods and other physical treatment methods that can achieve the best state of fluidity. The chemical method is to modify or coat the high-silicon aluminum precursor particles with a selected surface treatment agent.

[0022] Of course, in S2, to achieve the best state of fluidity of the high-silicon aluminum precursor particles, the physical method and the chemical method can also be used in combination.

[0023] In S2, the chemical method is to modify or coat the high-silicon aluminum precursor particles with a selected surface treatment agent, and then use a drying device to dry at 80-150 DEG C to achieve sufficient coating, so that the particles have good fluidity. The selected surface treatment agent is one or more of silane coupling agent, titanate coupling agent, aluminate coupling agent, zirconium aluminate coupling agent, surfactant, organosilicon, unsaturated organic acid and organic oligomer, superdispersant, water-soluble polymer, and inorganic surface modifier, and the addition amount is 0.25%-0.6% of the mass of the high-silicon aluminum precursor particles.

[0024] Further, the silica is selected from mineral materials with a silica content of ≥90% in schistose quartz, cristobalite, or quartz sand, or silica sol and white carbon black materials prepared by chemical methods and meeting the corresponding national standards.

[0025] Further, the di-aluminum trioxide is selected from bauxite, bauxite, hard water aluminum stone, high aluminum mineral material, or artificial synthesis of aluminum oxide material in accordance with the corresponding national standards; the di-boron trioxide is one, two or three of any combination of borax, boric acid, boron sand in accordance with the corresponding national standards.

[0026] Further, the alkali earth metal oxide is one, two or three of any combination of calcium oxide, magnesium oxide, strontium oxide; the alkali metal oxide is one, two or three of any combination of lithium oxide, sodium oxide, potassium oxide and other components.

[0027] Further, in S1, the crushing mill is one of a roller mill, a ball mill, or a combination of a jaw crusher or a cone crusher with one of a ball mill or a roller mill; the grinding is one or a combination of a cage mill, a roller mill, a rod mill or a Raymond mill.

[0028] Further, in S3, the combustion-supporting gas is air, oxygen or a mixture of the two required for fuel combustion, and the fuel is one or a combination of coal powder, coal gas, natural gas or petroleum gas, which is mixed and combusted with the combustion-supporting gas to generate high temperature and provide heat energy; in S4, the high-temperature-resistant surface treatment agent is one or a mixture of two or more of aluminate coupling agent, zirconium aluminate coupling agent, surfactant, unsaturated organic acid and organic oligomer, superdispersant, water-soluble polymer and inorganic surface modifier, with a suitable temperature of 150-300°C. The use of the above surface treatment agent can improve the interfacial bonding force between the spherical additive and the cement paste or cement stone, increase the early strength of the cement stone, delay the direct contact between the cement paste or cement stone and the spherical additive, and slow down the release of ions on the surface of the spherical additive.

[0029] In S3, the combustion-supporting gas can be used as a carrier for pneumatic conveying, in the form of suction or pressure, or a combination of the two, to fully mix the high-silicon aluminum precursor particles with the combustion-supporting gas to ensure heat transfer of the precursor particles and rapid melting to form a glass melt.

[0030] In S3, the rapid cooling refers to rapidly reducing the temperature of the glass melt below the glass softening point, which can be calculated according to the composition of the spherical additive, and can be determined by referring to related glass preparation technology or laboratory test.

[0031] The addition of waste glass (waste borosilicate glass), alkali metal oxide, alkali earth metal oxide, zinc oxide, zirconium oxide and phosphorus pentoxide in the raw materials respectively plays the following roles:

[0032] Borosilicate glass: Borosilicate glass is based on SiO2, B2O3 and alkali metal oxides. It has the advantages of good thermal stability, chemical stability and mechanical strength. It is widely used because of its wide source of raw materials, strong element tolerance and easy formability.

[0033] Boron trioxide: It forms a three-dimensional tetrahedral or trihedral boron-oxygen network, lowering the melting temperature of glass and forming a borosilicate glass network. Its high "BO" bond strength also enhances the mechanical strength, impact resistance, and crack resistance of borosilicate glass.

[0034] Alkali metal oxides are common components in borosilicate glass. They offer excellent fluxing properties. The presence of alkaline earth metal cations balances negative charges, reducing defects in the glass. Furthermore, a mixed-base effect exists between two alkaline earth metal oxides. The simultaneous use of two or more alkaline earth metal oxides can maximize the physical properties of the glass.

[0035] Alkaline earth metal oxides: are common components in borosilicate glass. They have excellent fluxing characteristics, avoid phase separation of glass melt, reduce glass viscosity and melting point, thereby reducing energy consumption in the borosilicate glass preparation process and improving its molding efficiency.

[0036] Zinc oxide: A small amount of zinc oxide is introduced into borosilicate glass to form zinc-oxygen octahedral coordination, making the glass structure denser, thereby improving the wear resistance, high temperature stability and other physical properties of the glass material.

[0037] Zirconia: Introducing a small amount of zirconium oxide into borosilicate glass can significantly enhance the physical properties of the glass, such as strength and hardness.

[0038] Phosphorus pentoxide: It can form a phosphorus-oxygen tetrahedral structure. Introducing a small amount of phosphorus pentoxide into borosilicate glass can significantly improve the compatibility of other components in the borosilicate glass and reduce the phase separation phenomenon of the glass melt.

[0039] More importantly, the synergistic effect brought about by the superposition and fusion of the above components enables the high-temperature resistant and anti-recession spherical additive prepared by the method of the present invention to completely solve the technical problem of long-term strength decline of cement stone during cementing operations in high-temperature oil and gas wells with a bottom hole static temperature of 150-300°C, and meet the needs of deep and ultra-deep reservoir oil and gas resource exploitation.

[0040] Compared with the prior art, the method of preparing high-temperature resistant and anti-decay cementing materials using high-aluminum and silicon content solid waste has the following beneficial effects:

[0041] (1) The main raw materials are waste glass and waste ceramic, and the amount of solid waste accounts for more than 64% of the total amount of raw materials, and the highest can reach 87%; other raw materials used are low-cost and widely available industrial products and mineral materials, which have the advantages of environmental friendliness, wide sources and low cost, greatly reducing the production cost of the product, and realizing the high value-added utilization of solid waste such as waste glass and waste ceramic, which is conducive to the large-scale promotion and use of the material in the field of oil and gas resource exploitation engineering.

[0042] (2) The prepared high-temperature-resistant anti-degradation spherical additive product contains 32-48% of waste glass, 30-45% of waste ceramic, 15-25% of aluminum oxide, 1.1-4.8% of boron trioxide, 1.6-4.6% of alkaline earth metal oxide, 0.7-4.6% of alkali metal oxide, 0.8-5% of zirconium oxide, 0.4-2% of zinc oxide, and 0.4-2% of phosphorus pentoxide. Through formula optimization, the spherical additive forms a micro glass network structure with silicon dioxide and aluminum trioxide as the skeleton, improving the structural density and high-temperature stability of the spherical additive; at the same time, the spherical additive contains a large amount of aluminum trioxide, and the proportion of calcium oxide is controlled within 5%, which can form hydrated products such as tobermorite and xonotlite with high thermal stability at high temperature, significantly reducing the amount of amorphous C-S-H gel produced due to the increase of calcium-silicon ratio in the hydration reaction, thereby reducing the generation of α-C2SH crystals with large voids and poor strength from amorphous C-S-H gel, and solving the problem of long-term strength degradation of cement stone at high temperature of 150-300℃.

[0043] (3) The precursor particles are pretreated by physical or chemical methods to achieve the best flowability. Due to the small particle size and large specific surface area of the precursor particles, the particle surface is in an unstable energy state and is prone to agglomeration. This method reduces the proportion of easily water-absorbing groups such as hydroxyl groups on the surface by physical or chemical methods, or reduces the contact area and time of hydroxyl groups and water molecules in the form of surface coating, or gives the same charge to the surface to generate electrostatic repulsion, so that the particles have excellent flowability and dispersibility, avoiding the adhesion between particles; compared with untreated particles, the processing amount of precursor particles per unit time is greatly improved during the high-temperature spheroidization process, saving the time cost of industrialization.

[0044] (4) In the high-temperature spheroidization process of the precursor particles, the particles are prepared into spherical glassy micron-sized spherical particles. Compared with ordinary anti-degradation agents or anti-strength degradation agents, the spherical additives belong to glass material, have low surface activity, and have more stable physicochemical properties. Under high-temperature conditions of 150-300°C, the spherical additives can continuously and slowly react with cement stone, solve the phenomenon that the early strength is high and the later strength is degraded due to the violent reaction of ordinary anti-degradation agents or anti-strength degradation agents, and continuously improve the long-term strength of the cement stone. The particles are fused at high temperature to form perfect micron-sized spherical particles. Compared with anti-degradation agents such as different particle size microsilica, the spherical additives have good fluidity, easy cement mixing, good cement paste fluidity, small frictional resistance, low casing wear, excellent anti-gas channeling performance, effective zonal isolation, easy plugging of small pores on the surface of filter cake, and low fluid loss.

[0045] (5) The high-temperature surface treatment agent is selected, and the prepared spherical additives are surface treated. Through specific surface functional groups, the effective components of cement and the spherical additives are better combined, the interfacial bonding force of the spherical additives and the cement paste or cement stone is significantly improved, and the early strength of the cement stone is increased by 20-45% compared with that without surface treatment. At the same time, the high-temperature surface treatment agent can withstand high temperature above 300°C, can delay the direct contact between the cement paste or cement stone and the surface of the spherical additives, thereby reducing the speed of the hydration reaction between the cement paste or cement stone and the surface of the spherical additives; finally, the surface treatment method can slow down the ion precipitation speed on the surface of the spherical additives, and further slow down the degree of cement hydration reaction caused by ion precipitation. DETAILED DESCRIPTION

[0046] In order to describe the present application, the method for preparing high-temperature-resistant anti-degradation well cementing material from high-aluminum and silicon solid waste is further described in detail in combination with examples. However, the present application is not limited to the examples.

[0047] In the examples, the raw waste glass contains 85% of silicon dioxide, 5% of boron oxide, 5% of alkaline earth metal oxide, and 5% of alkali metal oxide; and the raw waste ceramic contains 40% of silicon dioxide, 40% of aluminum oxide, 10% of alkaline earth metal oxide, and 10% of alkali metal oxide. Example 1

[0048] The specific implementation process is as follows:

[0049] Preparation of high-silicon aluminum precursor particles: according to the formula 1 in Table 1, each raw material is weighed, a jaw crusher is used to crush each material, and then each material is mixed and put into a rod mill for grinding to obtain a mixture with a particle size D 100 of 27 μm; a dry granulator is used to granulate the mixture to obtain precursor particles with a particle size D 100 of 170 μm and a porosity of 1.4%.

[0050] Pre-treatment of precursor particles: the precursor particles prepared in step (1) were surface treated with methyl triethoxysilane at a dosage of 0.5% of the mass of the precursor particles, heated in a rotary kiln for 2 h at a temperature of 120°C, and pre-treated.

[0051] High-temperature spheroidization of precursor particles: the precursor particles prepared in step (2) were placed in a premixing tank, mixed with conventional air as a combustion-supporting gas and a gas for pneumatic conveying, and then fed into a high-temperature vitrification furnace at a temperature of 1300°C, so that the precursor particles were rapidly heated and melted into a glass melt, which was then rapidly cooled to form spherical additives with a particle size D 100 of 170 μm, a compressive strength of 101 MPa, and a density of 2.3 g / cm 3 .

[0052] Surface high-temperature resistant treatment: an aluminum ester coupling agent was selected, and the spherical additives prepared in step (3) were modified by wet treatment to coat the surface with a layer of the aluminum ester coupling agent at a dosage of 0.8% of the mass of the spherical additives. After drying at 80°C using a drying device, spherical additives with a particle size D 100 of 170 μm, a compressive strength of 93 MPa, and a density of 2.3 g / cm 3 were obtained. Example 2

[0053] The specific implementation process is as follows:

[0054] Preparation of high-silicon aluminum precursor particles: the raw materials were weighed according to the formulation 2 in Table 1, and each material was crushed using a roller crusher. The materials were then mixed and ground in a ball mill to obtain a mixture with a particle size D 100 of 24 μm. The mixture was granulated by a wet granulation method to obtain precursor particles with a particle size D 100 of 160 μm and a porosity of 1.2%.

[0055] Pre-treatment of precursor particles: the precursor particles prepared in step (1) were surface treated with isopropyl tri-titanate at a dosage of 0.3% of the mass of the precursor particles, heated in an oven for 3 h at a temperature of 90°C, and pre-treated.

[0056] High-temperature spheroidization of precursor particles: the precursor particles prepared in step (2) were placed in a premixing tank, mixed with 90% conventional air and 10% pure oxygen as a combustion-supporting gas and a gas for pneumatic conveying, and then fed into a high-temperature vitrification furnace at a temperature of 1400°C, so that the precursor particles were rapidly heated and melted into a glass melt, which was then rapidly cooled to form spherical additives with a particle size D 100 of 155 μm, a compressive strength of 129 MPa, and a density of 2.4 g / cm 3 .

[0057] Surface high temperature resistant treatment: select commercially available aluminum zirconium coupling agent, take 0.7% of the mass of the spherical auxiliary, the spherical auxiliary prepared in step (3) is modified by dry method to coat a layer of aluminum zirconium coupling agent on the surface, and after drying at 95℃ using drying equipment, a high temperature resistant anti-degradation spherical auxiliary with particle size D 100 of 155μm, compressive strength of 123MPa, and density of 2.4g / cm 3 is prepared. Example 3

[0058] The specific implementation process is as follows:

[0059] Preparation of high-silicon aluminum precursor particles: according to formula 3 in table 1, weigh each raw material, crush each material using a ball mill, and then mix the materials and put them into the ball mill for grinding to prepare a mixture with particle size D 100 of 11μm; the mixture is granulated by dry granulation method to prepare precursor particles with particle size D 100 of 95μm and porosity of 0.7%.

[0060] Pre-treatment of precursor particles: the precursor particles prepared in step (1) are treated by low temperature plasma equipment to make the surface have the same charge and generate electrostatic repulsion, thereby obtaining precursor particles with excellent fluidity.

[0061] High temperature spheroidization of precursor particles: the precursor particles prepared in step (2) are placed in a premixing tank, and 70% conventional air and 30% pure oxygen are fully mixed as combustion-supporting gas and gas for pneumatic conveying, and then sent into a high temperature vitrification furnace with a temperature of 1500℃, the precursor particles are rapidly heated and melted into a glass melt, and then rapidly cooled to form spherical auxiliary with particle size D 100 of 95μm, compressive strength of 136MPa, and density of 2.7g / cm 3 .

[0062] Surface high temperature resistant treatment: select commercially available polybutene diacid, take 0.5% of the mass of the spherical auxiliary, modify the spherical auxiliary prepared in step (3) by dry method to coat a layer of polybutene diacid on the surface, and after drying at 110℃ using drying equipment, a high temperature resistant anti-degradation spherical auxiliary with particle size D 100 of 95μm, compressive strength of 135MPa, and density of 2.65g / cm 3 is prepared. Example 4

[0063] The specific implementation process is as follows:

[0064] Preparation of high-silicon aluminum precursor particles: each raw material was weighed according to formula 3 in table 1, each material was crushed by a roll crusher, and then each material was mixed and sequentially put into a rod mill and a ball mill for grinding to obtain a mixture with a particle size D 100 of 6 μm; the mixture was granulated by a dry granulation method to obtain a precursor particle with a particle size D 100 of 70 μm and a porosity of 0.45%.

[0065] Pre-treatment of precursor particles: the precursor particles prepared in step (1) were surface treated with 0.5% of the mass of the precursor particles of polydimethylsiloxane, heated in an oven for 2 h, and the temperature was set to 130°C to complete the pre-treatment.

[0066] High-temperature spheroidization of precursor particles: the precursor particles prepared in step (2) were placed in a premixing tank, and 50% of conventional air and 50% of pure oxygen were fully mixed as combustion-supporting gas and gas for pneumatic conveying and then sent into a high-temperature spheroidization furnace with a temperature of 1600°C, the precursor particles were rapidly heated and melted into a glass melt, and then rapidly cooled to form a spherical additive with a particle size D 100 of 70 μm, a compressive strength of 145 MPa, and a density of 2.7 g / cm 3 .

[0067] Surface high-temperature resistant treatment: a commercially available graft copolymer superdispersant was selected, 0.6% of the mass of the spherical additive was weighed, and the spherical additive prepared in step (3) was wet modified to coat a layer of graft copolymer superdispersant on the surface, and then dried at 150°C by using a drying device to obtain a high-temperature resistant anti-fading spherical additive with a particle size D 100 of 70 μm, a compressive strength of 145 MPa, and a density of 2.7 g / cm 3 . Example 5

[0068] The specific implementation process is as follows:

[0069] Preparation of high-silicon aluminum precursor particles: each raw material was weighed according to formula 3 in table 1, each material was crushed by a roll crusher, and then each material was mixed and sequentially put into a rod mill and a ball mill for grinding to obtain a mixture with a particle size D 100 of 5 μm; the mixture was granulated by an adhesive granulation method to obtain a precursor particle with a particle size D 100 of 160 μm and a porosity of 0.65%.

[0070] Pre-treatment of precursor particles: the precursor particles prepared in step (1) were surface treated with 0.5% of the mass of the precursor particles of polydimethylsiloxane, heated in an oven for 2 h, and the temperature was set to 130°C to complete the pre-treatment.

[0071] High temperature spheroidization of precursor particles: the precursor particles prepared in step (2) were put into a premixing tank, mixed with pure oxygen as combustion-supporting gas and gas for pneumatic conveying, and then sent into a high temperature spheroidization furnace at 1600℃. The precursor particles were rapidly heated and melted into a glass melt, and then rapidly cooled to form spherical additives with particle size D 100 of 160 μm, compressive strength of 150 MPa, and density of 2.7 g / cm 3 .

[0072] Surface high temperature resistance treatment: a commercially available graft copolymer type super dispersant was selected, and 0.6% of the mass of the spherical additives was weighed out. The spherical additives prepared in step (3) were modified by wet method to coat a layer of graft copolymer type super dispersant on the surface. After drying at 150℃ using a drying device, high temperature resistant anti-fading spherical additives with particle size D 100 of 160 μm, compressive strength of 150 MPa, and density of 2.7 g / cm 3 were prepared.

[0073] The process steps of Example 6 were the same as those of Example 1, and high temperature resistant anti-fading spherical additives with particle size D 100 of 150 μm, compressive strength of 105 MPa, and density of 2.5 g / cm 3 were finally prepared.

[0074] The process steps of Example 7 were the same as those of Example 3, and high temperature resistant anti-fading spherical additives with particle size D 100 of 100 μm, compressive strength of 125 MPa, and density of 2.6 g / cm 3 were finally prepared.

[0075] The process steps of Example 8 were the same as those of Example 4, and high temperature resistant anti-fading spherical additives with particle size D 100 of 80 μm, compressive strength of 140 MPa, and density of 2.7 g / cm 3 were finally prepared.

[0076] The high-temperature-resistant anti-degradation spherical adjuvant prepared by the method has been tested in the cementing operation of a super-deep oil and gas resource exploitation high-temperature well with a bottom hole static temperature of 230-300 DEG C. The test research shows that the high-temperature-resistant anti-degradation spherical adjuvant prepared by the method has the advantages of high sphericity, good fluidity, small friction resistance, easy mixing, simple use and the like; the strength degradation is less than 1% when the bottom hole static temperature is 150-300 DEG C and the curing time is 7 days, 28 days or more, the high-temperature-resistant anti-degradation is obvious, the cement stone strength is obviously improved, and the long-term strength degradation of the cement stone is completely solved; and the use cost is reduced by more than 25% compared with the use of industrial products and mineral materials as raw materials (i.e., using silica and alumina instead of waste glass and waste ceramic).

[0077] Table 1 mass fraction of each component of examples 1-7

[0078]

Claims

1. A method for preparing high temperature resistant and anti-decay cementing materials using high aluminum and silicon content solid waste, characterized in that Use the following steps to implement: S1: Preparation of precursor particles The raw materials are accurately weighed according to the raw material formula, crushed and ground to a particle size of less than 30 μm, and then premixed and granulated to obtain high-silicon-aluminum precursor particles with a particle size of ≤200 μm and a porosity of ≤2%; The contents of each component in the raw materials when the sum of the masses of each component is calculated as 100% are as follows: waste glass 32-48%, waste ceramics 30-45%, aluminum oxide 15-25%, boron trioxide 1.1-4.8%, alkaline earth metal oxides 1.6-4.6%, alkali metal oxides 0.7-4.6%, zirconium oxide 0.8-5%, zinc oxide 0.4-2%, and phosphorus pentoxide 0.4-2%. S2: Precursor particle pretreatment Pre-treating the high-silicon-aluminum precursor particles prepared in step S1 by physical methods, chemical methods, or a combination of both, to achieve optimal fluidity; S3: High temperature spheroidization of precursor particles After the high-silicon-aluminum precursor particles prepared in step S2 are fully mixed with the combustion-supporting gas, the materials are pneumatically conveyed into a high-temperature vitrification furnace at a temperature of 1300~1600℃. After the high-silicon-aluminum precursor particles are melted into a glass melt at high temperature, they are rapidly cooled to form a glass with a particle size of ≤200μm, a strength of 50~150MPa, and a density of 2.0~2.8g / cm 3 Spherical additives; S4: Surface coating treatment of spherical additives The spherical additive obtained in step S3 is coated with a high temperature resistant surface treatment agent that can withstand high temperature conditions of 150-300°C to obtain a particle size of ≤200μm, a compressive strength of 50-150MPa, and a density of 2.0-2.8g / cm 3 , a high-temperature resistant and anti-recession spherical additive product that can prevent the strength decline of cement stone at 150~300℃.

2. The method for preparing high-temperature resistant and anti-decay cementing materials using solid waste with high aluminum and silicon content according to claim 1, characterized in that: The waste glass is waste borosilicate glass, and the mass percentage of each component when calculated as 100% is: silicon dioxide 80-86%, boron oxide 3-7%, alkaline earth metal oxide 3-7%, alkali metal oxide 3-7%, and the remainder ≤1%.

3. The method for preparing high-temperature resistant and anti-decay cementing materials using solid wastes high in aluminum and silicon content according to claim 1, characterized in that: The mass percentage of each component in the waste ceramics, calculated based on 100%, is as follows: silicon dioxide 35-45%, aluminum oxide 35-45%, alkaline earth metal oxide 8-12%, alkali metal oxide 8-12%, and the remainder is ≤1%.

4. The method for preparing high-temperature resistant and anti-decay cementing materials using solid wastes high in aluminum and silicon content according to claim 2 or 3, characterized in that: In step S2, the physical method is to fully remove the moisture on the surface of the high-silicon-aluminum precursor particles under the conditions of 80~150℃, or to give the same charge to the surface of the high-silicon-aluminum precursor particles through electrodes to achieve the effect of mutual repulsion between particles; the chemical method is to select a surface treatment agent to perform surface modification or coating treatment on the high-silicon-aluminum precursor particles.

5. The method for preparing high-temperature resistant and anti-decay cementing materials using solid wastes high in aluminum and silicon content as claimed in claim 4, characterized in that: The selected surface treatment agent is one or more of silane coupling agent, titanate coupling agent, aluminate coupling agent, zirconium aluminate coupling agent, surfactant, organosilicon, unsaturated organic acid and organic oligomer, hyperdispersant, water-soluble polymer, and inorganic surface modifier, and the added amount is 0.25% to 0.6% of the mass of the high-silicon-aluminum precursor particles.

6. The method for preparing high-temperature resistant and anti-decay cementing materials using solid wastes high in aluminum and silicon content as claimed in claim 5, characterized in that: The silicon dioxide is selected from mineral materials with a silicon dioxide content of ≥90% in tridymite, cristobalite or quartz sand, or silica sol and white carbon black materials prepared by chemical methods and meeting corresponding national standards.

7. The method for preparing high-temperature resistant and anti-decay cementing materials using solid wastes high in aluminum and silicon content as claimed in claim 6, characterized in that: The aluminum oxide is selected from bauxite, bauxite, diaspore and other high-aluminum mineral materials that meet the corresponding national standards, or artificially synthesized alumina materials that meet the corresponding national standards; the boron trioxide is one, two or any combination of three of borax, boric acid and boron ore that meet the corresponding national standards.

8. The method for preparing high-temperature resistant and anti-decay cementing materials using solid wastes high in aluminum and silicon content as claimed in claim 7, characterized in that: The alkaline earth metal oxide is one, two or three of calcium oxide, magnesium oxide and strontium oxide; the alkali metal oxide composition is one, two or three of lithium oxide, sodium oxide and potassium oxide.

9. The method for preparing high-temperature resistant and anti-decay cementing materials using solid wastes high in aluminum and silicon content as claimed in claim 8, characterized in that: In step S1, the crushing is performed by using one of a roller mill and a ball mill, or a jaw or cone crusher in combination with one of a ball mill and a roller mill; the grinding is performed by using one of a cage mill, a roller mill, a rod mill or a Raymond mill, or a combination of any two of them.

10. The method for preparing high-temperature resistant and anti-decay cementing materials using solid wastes high in aluminum and silicon content as claimed in claim 9, characterized in that: In step S3, the combustion-supporting gas is air, oxygen, or a mixture of the two required for fuel combustion; in step S4, the high-temperature resistant surface treatment agent is one or a mixture of two or more of aluminate coupling agent, zirconium aluminate coupling agent, surfactant, unsaturated organic acid and organic oligomer, hyperdispersant, water-soluble polymer, and inorganic surface modifier, and the applicable temperature is 150~300℃.

Images