Geopolymer materials, methods of making and use thereof

Abstract

The present application provides a geopolymer material and a preparation method and application thereof. The geopolymer material contains modified silica-alumina, the content of aluminum in the modified silica-alumina is 35 wt% or more and the content of silicon is 40 wt% or more, based on the total amount of the modified silica-alumina and in terms of oxides, and the geopolymer material has an initial setting time of 5-10 hours and a final setting time of 7-12 hours at at least one temperature in the range of 70-300 DEG C. The geopolymer material of the present application has appropriate initial setting time and final setting time under the activation of an activator, and can realize well cementation at a higher temperature even without the cooperation of a retarder.

Description

[0001] Cross-references to related applications

[0002] This application claims the benefit of Chinese Patent Application No. 202110947865.9, filed on August 18, 2021, the contents of which are incorporated herein by reference. Technical Field

[0003] This invention belongs to the field of geopolymer technology, specifically relating to a geopolymer material, its preparation method, and its application. Background Technology

[0004] The concept of geopolymers was proposed by Professor Davidovits of France in 1978. It refers to a type of alkaline-active aluminosilicate material, such as metakaolinite, which, under the action of an alkaline activator, transforms from [SiO4]... 4- With [AlO4] 5- Geopolymers are three-dimensional, network-structured silica-alumina cementitious materials composed of structural units. Compared to other commonly used hydraulic materials, geopolymers offer significant advantages. Their preparation process can reduce energy consumption by over 70% and carbon emissions by over 80% compared to traditional cement, with no sulfur or nitrogen oxide emissions. Geopolymers are also known as "green cement." Their three-dimensional network structure endows them with a series of excellent physicochemical properties, including high-temperature stability, mechanical properties, corrosion resistance, and durability. They are a highly promising non-traditional cementitious material with the potential to replace traditional silicate cement. Therefore, geopolymers are attracting increasing attention from researchers.

[0005] However, although geopolymers have better physical and chemical properties than silicate cement, their excessively fast curing speed is the biggest obstacle to their application. Geopolymers require strong alkali treatment to achieve better performance, but their setting time is short (<0.5h at 80℃ with retarders), which does not meet the requirements for operation and construction, seriously affecting their widespread use, especially in oilfield cementing projects.

[0006] Currently, research in this area mainly focuses on selecting high-performance geopolymer retarders to control their curing time. CN201910426647.3 discloses a suitable retarder for geopolymers, composed of 30-40 wt% potassium dihydrogen phosphate, 30-50 wt% borax, and 20-30 wt% calcium chloride. CN201810851330.X describes how lignin sulfonate water-reducing agents and phosphate retarders enable concrete to achieve good workability. CN201810770099.1 discloses a carbohydrate-based geopolymer retarder, comprising 0%-80% carbohydrate compounds, 0%-80% sugar alcohol compounds, and 10%-90% water. The literature "Influence of Different Admixtures on the Setting and Hardening Properties of Geopolymers" proposes the use of boric acid to retard the setting and control the fluidity of slag powder-based geopolymers. Experiments show that within the dosage range of 0-4%, the setting time of geopolymers increases significantly with the increase of boric acid dosage, while the fluidity loss decreases over time and the compressive strength increases slightly.

[0007] However, the aforementioned patents and literature all control the curing time of geopolymer materials by adding admixtures. This method has a limited applicable temperature range, and adding admixtures inevitably increases cost and operational complexity. Therefore, there is an urgent need to develop a new method for controlling the curing time of geopolymers and a corresponding geopolymer. Summary of the Invention

[0008] Currently, the oil and gas well cementing industry faces significant limitations in improving the high-temperature stability, mechanical properties, corrosion resistance, and durability of traditional silicate cement materials. While geopolymers have outstanding advantages in these areas, their curing time is too fast. Although adding admixtures can optimize the curing time to some extent, it increases costs and operational complexity, and the optimization effect and stability of the curing time are limited.

[0009] This invention addresses the aforementioned problems in cementing technology by providing a geopolymer material with suitable curing properties, its preparation method, and its applications. The geopolymer material of this invention, when activated by an activator, exhibits appropriate initial and final setting times, enabling cementing at higher temperatures even without the use of a retarder. By adjusting the types and proportions of different active geopolymers in the geopolymer material, the curing time (also known as setting time) can be controlled within 5-10 hours, allowing the geopolymer material of this invention to leverage its performance advantages while overcoming the drawbacks of excessively rapid curing.

[0010] To achieve the above objectives, the present invention provides a geopolymer material containing modified aluminosilicate, wherein the modified aluminosilicate contains at least 35% by weight of aluminum and at least 40% by weight of silicon, based on the total amount of modified aluminosilicate and calculated as oxides, and the geopolymer material has an initial setting time of 5-10 hours and a final setting time of 7-12 hours at at least one temperature in the range of 70-300°C.

[0011] Preferably, the geopolymer material has an initial setting time of 5-10 hours and a final setting time of 7-12 hours at at least one temperature in the range of 70-100℃, 100-150℃, 150-200℃, 200-250℃, or 250-300℃.

[0012] Preferably, the difference between the final setting time and the initial setting time of the geopolymer material is 1-5 hours.

[0013] Preferably, the geopolymer material does not contain a retarder, wherein the retarder is one or more of the following: lignin sulfonate and its derivatives, sugars and their derivatives, boric acid and its salts, phosphoric acid and its salts, phosphonic acid and its salts, acrylic polymers, citric acid and its salts, tartaric acid and its salts, zinc salts, alkaline earth metal salts, and inorganic sulfates.

[0014] Preferably, the modified aluminosilicate content in the geopolymer material is 55% by weight or more, and more preferably 55-80% by weight.

[0015] Preferably, the XRD spectrum of the geopolymer material contains crystalline and amorphous characteristic peaks within the range of 2θ of 15-30°.

[0016] Preferably, the Si dissolution ratio of the geopolymer material is greater than 0.2, more preferably 0.5-1, and even more preferably 0.5-0.8.

[0017] Preferably, the geopolymer material includes at least two of a first geopolymer, a second geopolymer, a third geopolymer, and a fourth geopolymer; wherein, under activation conditions at 50°C using an aqueous solution containing 4 mol / L sodium hydroxide and 3 mol / L sodium silicate as an activator, and the weight ratio of the activator to the geopolymer material being 0.5, the initial setting time of the first geopolymer is 32 hours or more or unmeasurable, and the final setting time is unmeasurable; the initial setting time of the second geopolymer is 25 hours or more and less than 32 hours, and the final setting time is 60 hours or more or unmeasurable; the initial setting time of the third geopolymer is 8 hours or more and less than 25 hours, and the final setting time is 15 hours or more and less than 60 hours; the initial setting time of the fourth geopolymer is 2.5 hours or more and less than 8 hours, and the final setting time is 3 hours or more and less than 15 hours.

[0018] Preferably, the first geopolymer, the second geopolymer, the third geopolymer, and the fourth geopolymer are kaolins calcined at different temperatures.

[0019] Preferably, the calcination temperatures of the various geological polymers are as follows:

[0020] First-level geopolymer: not higher than 600℃ or higher than 950℃;

[0021] Second geological polymer: above 600℃ and not higher than 650℃ or above 850℃ and not higher than 950℃;

[0022] Third geological polymer: above 650℃ and not higher than 700℃ or above 750℃ and not higher than 850℃;

[0023] Fourth geopolymer: above 700℃ and not higher than 750℃;

[0024] Preferably, the calcination time is 1.5-2.5 hours, and more preferably 1.8-2.2 hours.

[0025] Preferably, the geopolymer material contains any one of the following, by weight parts:

[0026] (1) 70-80 parts of the third geopolymer and 70-80 parts of the fourth geopolymer;

[0027] (2) 40-60 parts of the second geopolymer, 90-110 parts of the third geopolymer and 8-12 parts of the fourth geopolymer;

[0028] (3) 40-60 parts of the first geopolymer and 90-110 parts of the third geopolymer;

[0029] (4) 40-60 parts of the second geopolymer and 70-90 parts of the third geopolymer;

[0030] (5) 90-110 parts of the first geopolymer and 8-12 parts of the third geopolymer;

[0031] (6) 90-110 parts of the second geopolymer and 15-25 parts of the third geopolymer;

[0032] (7) 40-60 parts by weight of the second geopolymer and 90-110 parts by weight of the third geopolymer;

[0033] (8) 40-60 parts by weight of the first geopolymer and 90-110 parts by weight of the fourth geopolymer.

[0034] Preferably, the geopolymer material further contains an activator, which contains one or more of soluble hydroxides, soluble silicates, soluble carbonates, and soluble polyphosphates. More preferably, it contains one or more of sodium hydroxide, potassium hydroxide, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium polyphosphate, and potassium polyphosphate. More preferably, it contains sodium hydroxide and sodium silicate, or sodium silicate and sodium polyphosphate. The activator is stored separately from the modified aluminosilicate and is mixed with it when used.

[0035] Preferably, the activator is mixed with the modified aluminosilicate in the form of an aqueous solution with a concentration of 0.5-10 mol / L; more preferably, in the solution of the activator, the concentration of soluble hydroxide is 2-6 mol / L, preferably 3-5 mol / L; and / or the concentration of soluble silicate is 1-6 mol / L, preferably 2-4 mol / L; and / or the concentration of soluble polyphosphate is 3-7 mol / L, preferably 4-6 mol / L.

[0036] Preferably, the weight ratio of the activator solution to the modified aluminosilicate is 0.3-0.8, more preferably 0.4-0.6.

[0037] The second aspect of the present invention provides a method for preparing a geopolymer material, the method comprising: calcining kaolin at different temperatures to obtain at least two modified aluminosilicates, and then mixing the at least two modified aluminosilicates to obtain the geopolymer material.

[0038] Preferably, the at least two modified silica-alumina are at least two of a first geopolymer, a second geopolymer, a third geopolymer, and a fourth geopolymer; wherein the calcination temperatures of each geopolymer are as follows:

[0039] First-level geopolymer: not higher than 600℃ or higher than 950℃;

[0040] Second geological polymer: above 600℃ and not higher than 650℃ or above 850℃ and not higher than 950℃;

[0041] Third geological polymer: above 650℃ and not higher than 700℃ or above 750℃ and not higher than 850℃;

[0042] Fourth geopolymer: above 700℃ and not higher than 750℃.

[0043] Preferably, the calcination time is 1.5-2.5 hours, and more preferably 1.8-2.2 hours.

[0044] Preferably, the preparation method does not include the step of adding a retarder, wherein the retarder is one or more of the following: lignin sulfonate and its derivatives, sugars and their derivatives, boric acid and its salts, phosphoric acid and its salts, phosphonic acid and its salts, acrylic polymers, citric acid and its salts, tartaric acid and its salts, zinc salts, alkaline earth metal salts, and inorganic sulfates.

[0045] Preferably, the preparation method further includes a step of mixing an activator, wherein the activator contains one or more of soluble hydroxides, soluble silicates, soluble carbonates and soluble polyphosphates, preferably containing one or more of sodium hydroxide, potassium hydroxide, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium polyphosphate and potassium polyphosphate, more preferably containing sodium hydroxide and sodium silicate, or sodium silicate and sodium polyphosphate.

[0046] Preferably, the activator is mixed with the modified aluminosilicate in the form of an aqueous solution with a concentration of 0.5-10 mol / L; more preferably, in the solution of the activator, the concentration of soluble hydroxide is 2-6 mol / L, preferably 3-5 mol / L; and / or the concentration of soluble silicate is 1-6 mol / L, preferably 2-4 mol / L; and / or the concentration of soluble polyphosphate is 3-7 mol / L, preferably 4-6 mol / L.

[0047] Preferably, the weight ratio of the activator solution to the modified aluminosilicate is 0.3-0.8, more preferably 0.4-0.6.

[0048] A third aspect of the present invention provides a geopolymer material prepared according to the preparation method of the second aspect of the present invention described above.

[0049] The fourth aspect of the present invention provides the application of the geopolymer materials described in the first or third aspect of the present invention in oilfield cementing.

[0050] Through the above technical solution, the beneficial effects of the present invention are as follows: The geopolymer material of the present invention, under the activation of the activator, has appropriate initial and final setting times, and can achieve cementing at higher temperatures even without the use of a retarder. Furthermore, the geopolymer material of the present invention, through the combination of geopolymers with different activities, allows for the control of the curing performance, such as the curing time, simply by adjusting the types and proportions of different active geopolymers. This enables the geopolymer of the present invention to overcome the hazards caused by its excessively rapid curing speed while leveraging the performance advantages of geopolymer materials. Specifically, the geopolymer material of the present invention has an initial setting time of 5-10 hours and a final setting time of 7-12 hours at the curing temperature. Its strength after 1 day of curing can reach over 10 MPa, and its strength after 7 days can reach over 21 MPa. Attached Figure Description

[0051] Figure 1 XRD pattern of the geopolymer material in Example 1

[0052] Figure 2 The image shows the XRD pattern of uncalcined kaolin.

[0053] Figure 3 The XRD pattern of the product of calcined kaolin at 600℃ is shown.

[0054] Figure 4 The XRD pattern of the product of calcined kaolin at 750℃ is shown.

[0055] Figure 5 The XRD pattern of the product of calcined kaolin at 850℃ is shown.

[0056] Figure 6 The XRD pattern of the product of calcined kaolin at 900℃ is shown. Detailed Implementation

[0057] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0058] The geopolymer material provided by the present invention contains modified aluminosilicate, wherein the modified aluminosilicate contains at least 35% by weight of aluminum and at least 40% by weight of silicon, based on the total amount of modified aluminosilicate and calculated as oxides. The geopolymer material has an initial setting time of 5-10 hours and a final setting time of 7-12 hours at at least one temperature in the range of 70-300°C.

[0059] In this invention, "the geopolymer material has an initial setting time of 5-10 hours and a final setting time of 7-12 hours at at least one temperature in the range of 70-300°C" means that the geopolymer material can be cured at at least one temperature in the range of 70-300°C with an initial setting time of 5-10 hours and a final setting time of 7-12 hours.

[0060] In the process of determining the initial setting time and final setting time, the activator and activation temperature can be appropriately selected as needed. As long as the required initial setting time and final setting time can be obtained, the requirements of this invention can be met. As a preferred activator in this invention, for example, it can be an aqueous solution containing 4 mol / L sodium hydroxide and 3 mol / L sodium silicate, or an aqueous solution containing 6 mol / L sodium silicate and 5 mol / L sodium tripolyphosphate.

[0061] In some preferred embodiments of the present invention, the geopolymer material has an initial setting time of 5-10 hours and a final setting time of 7-12 hours at at least one temperature within the ranges of 50-100°C, 100-150°C, 150-200°C, 200-250°C, or 250-300°C. The temperature range having an initial setting time of 5-10 hours and a final setting time of 7-12 hours can be above 50°C, above 60°C, above 70°C, above 80°C, above 90°C, above 100°C, above 110°C, or above 120°C, and can be below 300°C.

[0062] According to the present invention, preferably, based on the total amount of modified aluminosilicate and calculated in terms of oxides, the modified aluminosilicate contains 35-47% by weight, more preferably 40-46% by weight, and 40-55% by weight, more preferably 45-54% by weight, of aluminum. The aluminum content can be, for example, 35% by weight, 38% by weight, 40% by weight, 42% by weight, 45% by weight, or 46% by weight; the silicon content can be, for example, 40% by weight, 42% by weight, 45% by weight, 47% by weight, 50% by weight, 52% by weight, or 55% by weight.

[0063] According to the present invention, preferably, the difference between the final setting time and the initial setting time of the geopolymer material is 1-5 hours, more preferably 1-4 hours.

[0064] According to the present invention, preferably, the content of modified aluminosilicate in the geopolymer material is 55% by weight or more, more preferably 55-80% by weight. The modified aluminosilicate can be, for example, calcined kaolin. Furthermore, according to some preferred embodiments of the present invention, the geopolymer material may consist solely of modified aluminosilicate and may be used in conjunction with an activator as needed. According to other preferred embodiments of the present invention, the geopolymer material may consist of modified aluminosilicate and an activator, wherein the activator and modified aluminosilicate are stored separately and mixed before use.

[0065] According to the present invention, the strength of the geopolymer material after curing for 7 days is 20 MPa or more, preferably 20-50 MPa.

[0066] In some preferred embodiments of the present invention, the geopolymer material includes at least two of a first geopolymer, a second geopolymer, a third geopolymer, and a fourth geopolymer. Under the action of the activator, the curing time required for the first geopolymer, the second geopolymer, the third geopolymer, and the fourth geopolymer decreases sequentially. Therefore, in the present invention, the above-mentioned geopolymers are also referred to as latently active geopolymers, low-activity geopolymers, medium-activity geopolymers, and high-activity geopolymers, respectively.

[0067] In some embodiments of the present invention, the curing properties of the geopolymer can be controlled by adjusting the type and content of the geopolymer in the geopolymer material; preferably, the curing properties include the initial setting time, the final setting time, and the mechanical properties of the product obtained after curing.

[0068] Specifically, under activation conditions at 50°C using an aqueous solution containing 4 mol / L sodium hydroxide and 3 mol / L sodium silicate as the activator, and a weight ratio of the activator to the geopolymer material of 0.5, the initial setting time of the first geopolymer is 32 hours or more or unmeasurable, and the final setting time is unmeasurable; the initial setting time of the second geopolymer is 25 hours or more and less than 32 hours, and the final setting time is 60 hours or more or unmeasurable; the initial setting time of the third geopolymer is 8 hours or more and less than 25 hours, and the final setting time is 15 hours or more and less than 60 hours; the initial setting time of the fourth geopolymer is 2.5 hours or more and less than 8 hours, and the final setting time is 3 hours or more and less than 15 hours.

[0069] In this invention, "initial setting time cannot be measured" means that the geopolymer cannot solidify to a consistency of 100 Bc under the corresponding activation conditions; "final setting time cannot be measured" means that the geopolymer cannot solidify to a strength of 3.5 MPa under the corresponding activation conditions. The specific methods for determining the above-mentioned initial and final setting times are as described in the examples below.

[0070] In some preferred embodiments of the present invention, the first geopolymer, the second geopolymer, the third geopolymer and the fourth geopolymer are kaolins calcined at different temperatures.

[0071] Kaolin has a layered silicate structure, with layers bonded by van der Waals bonds, where OH- ions are firmly bound. Its crystal building blocks consist of silicon-oxygen tetrahedra and aluminum-oxygen octahedra, stacked in a specific ratio by sharing oxygen atoms. In this crystal structure, silicon and aluminum atoms are confined within the crystal lattice, lacking chemical reactivity, not participating in hydration reactions, and exhibiting no cementing properties. However, when kaolin is heated in air, it undergoes several structural changes. At approximately 600°C, the layered structure of kaolin breaks down due to dehydration, forming a poorly crystallized, cementing transition phase—metakaolin. Metakaolin formed from kaolin calcined at different temperatures exhibits varying degrees of molecular irregularity and displays different thermodynamic metastable states, making it an ideal raw material for achieving stepwise solidification reactions in geopolymers.

[0072] The kaolin used in this invention, by weight percentage, may contain, for example, the following composition: Al2O3 ≥ 35%, 40% ≤ SiO2 ≤ 49%, Fe2O3 ≤ 1%, K2O + Na2O ≤ 0.70%. The balance is mainly structural water.

[0073] In a preferred embodiment, the calcination temperatures for different geological polymers can be as follows:

[0074] (i) First geopolymer: not higher than 600°C or higher than 950°C. In some specific embodiments, the calcination temperature of the first geopolymer can be 100°C, 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 980°C, or 1100°C, etc.

[0075] (ii) Second geopolymer: calcined at a temperature above 600°C and not exceeding 650°C, or above 850°C and not exceeding 950°C. In some specific embodiments, the calcination temperature of the second geopolymer may be 620°C, 650°C, 880°C, 900°C, or 950°C, etc.

[0076] (iii) Third geopolymer: calcined at a temperature above 650°C and not exceeding 700°C, or above 750°C and not exceeding 850°C. In some specific embodiments, the calcination temperature of the third geopolymer can be 680°C, 700°C, 780°C, 800°C, or 850°C, etc.

[0077] (iv) Fourth geopolymer: above 700°C and not higher than 750°C. In some specific embodiments, the calcination temperature of the fourth geopolymer can be 710°C, 720°C, 730°C, 740°C, or 750°C, etc.

[0078] In some preferred embodiments of the present invention, the calcination time is 1.5-2.5 hours, preferably 1.8-2.2 hours, for example, 2 hours.

[0079] By combining the aforementioned geopolymers, the geopolymer material of this invention exhibits a reasonable and controllable curing time and a clear sequence of reactions. The components are well-matched, with lower-activity components ensuring later strength development and higher-activity components providing early strength support. The components are uniformly distributed within the geopolymer system, enabling uniform curing.

[0080] In some specific embodiments of the present invention, the geopolymer material has an initial setting time of 5-10 hours and a final setting time of 7-12 hours at a temperature of 70-300°C, and the difference between the final setting time and the initial setting time is 1-4 hours. The geopolymer material may contain any one of the following (1) to (8) by weight:

[0081] (1) 70-80 parts by weight of a third geopolymer and 70-80 parts by weight of a fourth geopolymer. With the above composition (1), the geopolymer material has an initial setting time of 5-7 hours and a final setting time of 7-10 hours at a temperature of 70-100°C.

[0082] (2) 40-60 parts by weight of the second geopolymer, 90-110 parts by weight of the third geopolymer and 8-12 parts by weight of the fourth geopolymer. With the above composition (2), the geopolymer material has an initial setting time of 6-9 hours and a final setting time of 7-11 hours at a temperature of 70-200℃.

[0083] (3) 40-60 parts by weight of the first geopolymer and 90-110 parts by weight of the third geopolymer. With the above composition (3), the geopolymer material has an initial setting time of 9-10 hours and a final setting time of 10-12 hours at a temperature above 200°C and not above 300°C.

[0084] (4) 40-60 parts by weight of a second geopolymer and 70-90 parts by weight of a third geopolymer. With the composition of (4) above, the geopolymer has an initial setting time of 7-10 hours and a final setting time of 10-12 hours at a temperature above 200°C and not higher than 300°C.

[0085] (5) 90-110 parts by weight of the first geopolymer and 8-12 parts by weight of the third geopolymer.

[0086] (6) 90-110 parts by weight of the second geopolymer and 15-25 parts by weight of the third geopolymer.

[0087] With the composition of (5) or (6) above, the geopolymer material has an initial setting time of 6-9 hours and a final setting time of 7-12 hours at a temperature above 200°C and not above 300°C.

[0088] (7) 40-60 parts by weight of the second geopolymer and 90-110 parts by weight of the third geopolymer.

[0089] (8) 40-60 parts by weight of the first geopolymer and 90-110 parts by weight of the fourth geopolymer.

[0090] With the composition of (7) or (8) above, the geopolymer material has an initial setting time of 5-9 hours and a final setting time of 7-1.1 hours at a temperature of 70-200℃.

[0091] In some preferred embodiments of the present invention, the XRD spectrum of the geopolymer material contains crystalline and amorphous characteristic peaks in the range of 2θ of 15-30°. For example... Figure 1 As shown, the XRD pattern of the geopolymer material of this invention contains crystalline and amorphous characteristic peaks within the range of 2θ of 15-30°. In this invention, modified aluminosilicate is defined relative to unmodified aluminosilicate (e.g., uncalcined kaolin). Figure 2 Peaks with θ in the range of 15-30° are characteristic peaks of the crystalline state, such as... Figure 2 As shown, all are sharp peaks.

[0092] After calcination, the Si dissolution ratios of different geopolymers can be as follows: the Si dissolution ratio of the first geopolymer is below 0.2, the Si dissolution ratio of the second geopolymer is greater than 0.2 and below 0.51, the Si dissolution ratio of the third geopolymer is greater than 0.51 and below 0.82, and the Si dissolution ratio of the fourth geopolymer is greater than 0.82 and below 1.

[0093] According to the present invention, the Si leaching ratio of the geopolymer material is greater than 0.2, preferably 0.5-1, for example, it can be 0.5-0.8, 0.6-0.95, or 0.8-1, etc. However, for unmodified aluminosilicate (uncalcined kaolin), the Si leaching ratio is only about 0.005.

[0094] In some preferred embodiments of the present invention, the geopolymer material further comprises an activator, which may contain one or more of soluble hydroxides, soluble silicates, soluble carbonates, and soluble polyphosphates, such as sodium hydroxide, potassium hydroxide, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium polyphosphate, and potassium polyphosphate. The activator is stored separately from the modified aluminosilicate and mixed with it before use. The soluble polyphosphate may be tripolyphosphate and / or pentapolyphosphate. In some preferred embodiments of the present invention, the activator contains hydroxides (preferably sodium hydroxide) and silicates (preferably sodium silicate). In other preferred embodiments of the present invention, the activator contains silicates (preferably sodium silicate) and polyphosphates (preferably sodium polyphosphate).

[0095] In some preferred embodiments of the present invention, the activator is mixed with modified aluminosilicate in the form of an aqueous solution with a concentration of 0.5-10 mol / L, preferably 1-8 mol / L. As an activator containing soluble hydroxide, soluble silicate, and / or polyphosphate, preferably, the concentration of the soluble hydroxide in the activator solution is 2-6 mol / L, preferably 3-5 mol / L, for example 4 mol / L; and / or the concentration of the soluble silicate is 1-6 mol / L, preferably 2-4 mol / L, for example 3 mol / L; and / or the concentration of the polyphosphate is 3-7 mol / L, preferably 4-6 mol / L, for example 5 mol / L.

[0096] In some preferred embodiments of the present invention, the weight ratio of the activator solution to the modified aluminosilicate is 0.3-0.8, preferably 0.4-0.6.

[0097] According to some preferred embodiments of the present invention, the geopolymer material may be composed of modified aluminosilicate and an activator. The activator and the modified aluminosilicate are stored separately and mixed together before use.

[0098] Because the geopolymer material provided by this invention can achieve the required curing time (including initial and final setting times) and cured strength by adjusting the type and ratio of the geopolymer, it can meet application requirements without the need for additional retarders. In this invention, a retarder refers to an additive used to extend the curing time of the geopolymer material. However, existing geopolymer materials typically require the addition of a retarder at a weight of 10-20% relative to the total amount of the geopolymer material to inhibit and delay curing, in order to meet construction application requirements. But even with this method of adding retarders, it usually only meets the construction requirements at temperatures below 60°C.

[0099] In this invention, the geopolymer material does not contain a retarder. The retarder is one or more of the following: lignin sulfonate and its derivatives, sugars and their derivatives, boric acid and its salts, phosphoric acid and its salts, phosphonic acid and its salts, acrylic polymers, citric acid and its salts, tartaric acid and its salts, zinc salts, alkaline earth metal salts, and inorganic sulfates. Specifically, sugars and their derivatives can be calcium glycosyl, gluconate, cellulose and its derivatives (such as carboxymethyl hydroxyethyl cellulose), etc.; boric acid and its salts can be boric acid, borax, etc.; phosphonic acid and its salts can be hydroxyethylidene diphosphonic acid, etc.; and acrylic polymers can be 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and 2-acrylamido-2-methylpropanesulfonic acid / acrylic acid (AMPS / AA), etc.

[0100] The second aspect of the present invention relates to a method for preparing a geopolymer material, the method comprising: calcining kaolin at different temperatures to obtain at least two modified aluminosilicates, and then mixing the at least two modified aluminosilicates to obtain a geopolymer material.

[0101] In some preferred embodiments of the present invention, the at least two modified silica-alumina are at least two of a first geopolymer, a second geopolymer, a third geopolymer, and a fourth geopolymer.

[0102] Here, the calcination temperature, calcination time, and mixing ratio of the first, second, third, and fourth geopolymers are the same as in the first aspect, and will not be repeated here. The preparation method of the second aspect of the present invention can be used to prepare the geopolymer material of the first aspect.

[0103] In some preferred embodiments of the present invention, the preparation method further includes a step of mixing an activator, wherein the activator may contain one or more of soluble hydroxides, soluble silicates, soluble carbonates, and soluble polyphosphates, preferably one or more of sodium hydroxide, potassium hydroxide, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium polyphosphate, and potassium polyphosphate. The soluble polyphosphate may be tripolyphosphate and / or pentapolyphosphate. In some preferred embodiments of the present invention, the activator contains hydroxides (preferably sodium hydroxide) and silicates (preferably sodium silicate). In other preferred embodiments of the present invention, the activator contains silicates (preferably sodium silicate) and polyphosphates (preferably sodium polyphosphate).

[0104] In some preferred embodiments of the present invention, the activator is mixed with modified aluminosilicate in the form of an aqueous solution with a concentration of 0.5-10 mol / L, preferably 1-8 mol / L. As an activator containing soluble hydroxide, soluble silicate, and / or polyphosphate, preferably, the concentration of the soluble hydroxide in the activator solution is 2-6 mol / L, preferably 3-5 mol / L, for example 4 mol / L; and / or the concentration of the soluble silicate is 1-6 mol / L, preferably 2-4 mol / L, for example 3 mol / L; and / or the concentration of the polyphosphate is 3-7 mol / L, preferably 4-6 mol / L, for example 5 mol / L.

[0105] In some preferred embodiments of the present invention, the weight ratio of the activator solution to the modified aluminosilicate is 0.3-0.8, preferably 0.4-0.6.

[0106] In some preferred embodiments of the present invention, the method does not include the step of adding a retarder. The retarder is one or more of the following: lignin sulfonate and its derivatives, sugars and their derivatives, boric acid and its salts, phosphoric acid and its salts, phosphonic acid and its salts, acrylic polymers, citric acid and its salts, tartaric acid and its salts, zinc salts, alkaline earth metal salts, and inorganic sulfates. Among these, sugars and their derivatives can be calcium glycosyl, gluconate, cellulose and its derivatives (such as carboxymethyl hydroxyethyl cellulose), etc.; boric acid and its salts can be boric acid, borax, etc.; phosphonic acid and its salts can be hydroxyethylidene diphosphonic acid, etc.; and acrylic polymers can be 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and 2-acrylamido-2-methylpropanesulfonic acid / acrylic acid (AMPS / AA), etc.

[0107] The third aspect of the present invention provides a geopolymer material obtained by the preparation method of the second aspect described above.

[0108] The fourth aspect of the present invention provides the application of the geopolymer material described in the first aspect of the present invention or the geopolymer material prepared according to the preparation method of the second aspect in oilfield cementing.

[0109] By using the geopolymer material of the present invention, the initial setting time at the curing temperature is 5-10 hours and the final setting time is 7-12 hours. The strength after 1 day of curing can reach more than 12 MPa and the strength after 7 days can reach more than 21 MPa. It can be widely used in oilfield cementing.

[0110] The present invention will be described in detail below through embodiments. In the above and following embodiments of the present invention, unless otherwise stated, "parts" refers to parts by weight.

[0111] In this invention, the compressive strength was tested according to the method of GB / T 19139-2012.

[0112] Method for determining initial setting time: Under normal pressure and corresponding temperature test conditions, the test is conducted using a high-temperature and high-pressure thickener (Chandler 8240 high-temperature and high-pressure thickener from Chandler Corporation, USA). The time required from the start of solidification of the geopolymer (i.e., when the activator is added) to the point where the consistency of the API standard thickening curve reaches 100 Bc is the initial setting time.

[0113] Method for determining final setting time: Under normal pressure and corresponding temperature test conditions, the test is conducted using an ultrasonic strength tester (Chandler 5265 static gel strength analyzer from the start of geopolymer curing to the point where the measured ultrasonic strength reaches 3.5 MPa, which is the final setting time.

[0114] The Si dissolution rate was determined using the ion dissolution method, specifically as follows.

[0115] Weigh 41.667g of analytical grade sodium hydroxide granules and place them in a polytetrafluoroethylene beaker. Dissolve them in water and bring the volume to 500ml to prepare a sodium hydroxide solution with a concentration of 2mol / L. Let it stand for 24 hours before use.

[0116] Before the test, the prepared sodium hydroxide solution was kept at 80℃. During the test, 0.1g of the test material and 100g of the kept sodium hydroxide solution were weighed and placed in a polytetrafluoroethylene beaker. The beaker was placed in an 80℃ water bath and stirred for 3 hours. The mouth of the beaker should be covered with a film to prevent moisture loss.

[0117] When the solution is stirred and kept warm for 3 hours, the reaction solution is extracted, filtered through a 0.22 μm filter membrane, and the filtrate is diluted 50 times with 2% dilute nitric acid solution. The silicon concentration in the diluted solution is tested using an ICP-OES instrument. The Si dissolution rate of the test material is equal to the dissolution rate at the corresponding calcination temperature / the dissolution rate at 750℃.

[0118] Preparation examples: Preparation of different active geopolymers

[0119] Kaolin (weight composition: Al₂O₃ 36%, SiO₂ 43%, Fe₂O₃ 0.5%, K₂O 0.13%, Na₂O 0.01%, balance mainly structural water) was calcined and activated at different temperatures in a high-temperature tube furnace to form geopolymers with different activities. The calcination method involved calcination in air for two hours followed by cooling. The calcination temperature, Si dissolution rate, and activity classification are shown in Table 1. The weight loss after calcination was evaluated by thermogravimetric analysis and balance weighing, as shown in Table 1.

[0120] Table 1

[0121] Condition 1 Condition 2 Condition 3 Condition 4 Condition 5 Condition 6 Condition 7 Condition 8 Calcination temperature, °C 600 650 700 750 800 840 900 960 Weight loss rate, % 10.6 11.2 14.5 15.7 16.8 18.5 19.3 20.1 Si dissolution rate 0.20 0.51 0.82 1.00 0.63 0.53 0.33 0.17 Activity grading Potential activity Low activity Medium active High activity Medium active Medium active Low activity Potential activity

[0122] The activity grading criteria for geopolymers in Table 1 above are shown in Table 2 below.

[0123] Table 2

[0124] Activity grading Calcination temperature Potential activity Calcination temperature ≤600℃ or >950℃ Low activity 600℃ < calcination temperature ≤ 650℃ or 850℃ < calcination temperature ≤ 950℃ Medium active 650℃ < calcination temperature ≤ 700℃ or 750℃ < calcination temperature ≤ 850℃ High activity 700℃ < Calcination temperature ≤ 750℃

[0125] Example 1

[0126] 75 parts of the medium-activity geopolymer (condition 3) and 75 parts of the high-activity geopolymer (condition 4) prepared in the preparation example were weighed according to the proportions and mixed uniformly to obtain the geopolymer material. The XRD pattern of the geopolymer material is shown below. Figure 1 As shown, the Si dissolution rate is 0.9. Furthermore, the XRD patterns of uncalcined kaolin and kaolin products calcined at 600℃, 750℃, 800℃, and 900℃ are shown below. Figure 2-6 As shown.

[0127] Activation experiments were conducted using an aqueous solution containing 4 mol / L sodium hydroxide and 3 mol / L sodium silicate as the activator. The weight ratio of the activator to the geopolymer material was 0.5. The initial and final setting times of the geopolymer material at different curing temperatures are shown in Table 3. The strength test was conducted under the set temperature for 7 days. The strength test results of the geopolymer material at 1 day and 7 days are shown in Table 4.

[0128] Example 2

[0129] Weigh out 50 parts of the low-activity geopolymer (condition 2), 100 parts of the medium-activity geopolymer (condition 3), and 10 parts of the high-activity geopolymer prepared in the preparation example according to the proportions, and mix them evenly to obtain the geopolymer material.

[0130] The initial / final setting time and the strength at 1 day and 7 days of the geopolymer material were determined according to the method in Example 1, and the results are shown in Tables 3 and 4, respectively.

[0131] Example 3

[0132] Weigh 100 parts of the latently active geopolymer (condition 1) and 10 parts of the moderately active geopolymer (condition 3) prepared in the preparation example according to the proportion, and mix them evenly to obtain the geopolymer material.

[0133] The initial / final setting time and the strength at 1 day and 7 days of the geopolymer material were determined according to the method in Example 1, and the results are shown in Tables 3 and 4, respectively.

[0134] Example 4

[0135] Weigh 50 parts of the latently active geopolymer (condition 1) and 100 parts of the moderately active geopolymer (condition 3) prepared in the preparation example according to the proportion, and mix them evenly to obtain the geopolymer material.

[0136] The initial / final setting time and the strength at 1 day and 7 days of the geopolymer material were determined according to the method in Example 1, and the results are shown in Tables 3 and 4, respectively.

[0137] Example 5

[0138] Weigh 50 parts of the low-activity geopolymer (condition 2) and 80 parts of the medium-activity geopolymer (condition 3) prepared in the preparation example according to the proportion, and mix them evenly to obtain the geopolymer material.

[0139] The initial / final setting time and the strength at 1 day and 7 days of the geopolymer material were determined according to the method in Example 1, and the results are shown in Tables 3 and 4, respectively.

[0140] Example 6

[0141] Weigh 100 parts of the low-activity geopolymer (condition 2) and 20 parts of the medium-activity geopolymer (condition 3) prepared in the preparation example according to the proportion, and mix them evenly to obtain the geopolymer material.

[0142] The initial / final setting time and the strength at 1 day and 7 days of the geopolymer material were determined according to the method in Example 1, and the results are shown in Tables 3 and 4, respectively.

[0143] Example 7

[0144] Weigh 50 parts of the low-activity geopolymer (condition 2) and 100 parts of the medium-activity geopolymer (condition 3) prepared in the preparation example according to the proportion, and mix them evenly to obtain the geopolymer material.

[0145] In addition to using an aqueous solution containing 6 mol / L sodium silicate and 5 mol / L sodium tripolyphosphate as an activator, the initial / final setting time and the strength at 1 day and 7 days of the geopolymer material were determined according to the method in Example 1. The results are shown in Tables 3 and 4, respectively.

[0146] Example 8

[0147] Weigh 50 parts of the latently active geopolymer (condition 1) and 100 parts of the highly active geopolymer (condition 4) prepared in the preparation example according to the proportions, and mix them evenly to obtain the geopolymer material.

[0148] The initial / final setting time and the strength at 1 day and 7 days of the geopolymer material were determined according to the method in Example 7, and the results are shown in Tables 3 and 4, respectively.

[0149] Comparative Example 1

[0150] Weigh 150 portions of the latently active geopolymer (condition 1) prepared in Example 1. Determine the initial / final setting time and the strength at 1 day and 7 days of the geopolymer according to the method in Example 1. The results are shown in Tables 3 and 4, respectively.

[0151] Comparative Example 2

[0152] Weigh 150 portions of the low-activity geopolymer (condition 2) prepared in Example 1. Determine the initial / final setting time and the strength at 1 day and 7 days of the geopolymer according to the method in Example 1. The results are shown in Tables 3 and 4, respectively.

[0153] Comparative Example 3

[0154] Weigh 150 portions of the moderately reactive geopolymer (condition 3) prepared in Example 1. Determine the initial / final setting time and the strength at 1 day and 7 days of the geopolymer according to the method in Example 1. The results are shown in Tables 3 and 4, respectively.

[0155] Comparative Example 4

[0156] Weigh 150 portions of the highly reactive geopolymer (condition 4) prepared in Example 1. The initial / final setting time and the strength at 1 day and 7 days of the geopolymer were determined according to the method in Example 1. The results are shown in Tables 3 and 4, respectively.

[0157] Comparative Example 5

[0158] Geopolymer materials were prepared according to the method of Example 2. Except that the weight ratio of activator to geopolymer material was 1, the initial / final setting time and the strength at 1 day and 7 days of the geopolymer material were determined according to the method of Example 2, and the results are shown in Tables 3 and 4, respectively.

[0159] Table 3: Initial / Final Setting Time (h) of Geopolymers at Different Temperatures

[0160]

[0161] In the table, "-" indicates not measured (the same applies below), and "*" indicates that it cannot be measured.

[0162] As can be seen from the experimental results in Table 3, the geopolymer materials in Examples 1-8, through the combination of different active components, can achieve a stepwise curing reaction, thereby controlling the curing time. This allows for a curing temperature range of 70-300℃, meeting the requirements for cementing operations with an initial setting time of 5-10 hours and a final setting time of 7-12 hours. Examples 1-2, 4, 5, and 7-8 are suitable for medium-high temperature cementing (70 ≤ temperature ≤ 200℃); Examples 3, 5, and 6 are suitable for high-temperature and ultra-high-temperature cementing (200℃ < temperature ≤ 300℃). In Comparative Examples 1-4, the geopolymers contain only one active ingredient, resulting in a limited curing time (too fast or too slow), making the curing time uncontrollable during construction. In Comparative Example 5, the excessive amount of activator led to an excessively fast curing time, causing inconvenience during construction.

[0163] Table 4

[0164]

[0165] Table 5

[0166]

[0167] As shown in Tables 4 and 5, the geopolymers obtained in Examples 1-8 can all achieve a strength of over 10 MPa after 1 day, with a maximum of 25.2 MPa, and a strength of over 21 MPa after 7 days, with a maximum of 49 MPa. Moreover, the strength not only does not decline under high-temperature conditions, but can also increase within a certain range. This is a performance that conventional silicate cementing materials rarely possess.

Claims

1. A geopolymer material, characterised in that, The geopolymer material contains modified aluminosilicate, and based on the total amount of modified aluminosilicate and calculated as oxides, the modified aluminosilicate contains more than 35% by weight of aluminum and more than 40% by weight of silicon. The geopolymer material has an initial setting time of 5-10 hours and a final setting time of 7-12 hours at at least one temperature in the range of 70-300°C. The geopolymer material includes at least two of a first geopolymer, a second geopolymer, a third geopolymer, and a fourth geopolymer; wherein, under activation conditions at 50°C using an aqueous solution containing 4 mol / L sodium hydroxide and 3 mol / L sodium silicate as an activator, and the weight ratio of the activator to the geopolymer material being 0.5, the initial setting time of the first geopolymer is 32 hours or more or unmeasurable, and the final setting time is unmeasurable; the initial setting time of the second geopolymer is 25 hours or more and less than 32 hours, and the final setting time is 60 hours or more or unmeasurable; the initial setting time of the third geopolymer is 8 hours or more and less than 25 hours, and the final setting time is 15 hours or more and less than 60 hours; the initial setting time of the fourth geopolymer is 2.5 hours or more and less than 8 hours, and the final setting time is 3 hours or more and less than 15 hours. The first geopolymer, the second geopolymer, the third geopolymer, and the fourth geopolymer are kaolins calcined at different temperatures.

2. Geopolymer material according to claim 1, wherein, The geopolymer material has an initial setting time of 5-10 hours and a final setting time of 7-12 hours at at least one temperature in the range of 70-100℃, 100-150℃, 150-200℃, 200-250℃, or 250-300℃.

3. Geopolymer material according to claim 2, wherein, The difference between the final setting time and the initial setting time of the geopolymer material is 1-5 hours.

4. Geopolymer material according to claim 1 or 2, wherein, The geopolymer material does not contain a retarder, which is one or more of the following: lignin sulfonate and its derivatives, sugars and their derivatives, boric acid and its salts, phosphoric acid and its salts, phosphonic acid and its salts, acrylic polymers, citric acid and its salts, tartaric acid and its salts, zinc salts, alkaline earth metal salts, and inorganic sulfates.

5. Geopolymer material according to claim 1 or 2, wherein, The modified silica-alumina content in the geopolymer material is 55% by weight or more.

6. Geopolymer material according to claim 5, wherein, The modified silica-alumina content in the geopolymer material is 55-80% by weight.

7. Geopolymer material according to claim 1 or 2, wherein, The XRD spectrum of the geopolymer material contains crystalline and amorphous characteristic peaks in the range of 2θ of 15-30°.

8. Geopolymer material according to claim 1 or 2, wherein, The Si dissolution rate of the geopolymer material is greater than 0.

2.

9. Geopolymer material according to claim 8, wherein, The Si dissolution rate of the geopolymer material is 0.5-1.

10. Geopolymer material according to claim 1, wherein, The calcination temperatures for different geological polymers are as follows: First-level geopolymer: not higher than 600℃ or higher than 950℃; Second geological polymer: above 600℃ and not higher than 650℃ or above 850℃ and not higher than 950℃; Third geological polymer: above 650℃ and not higher than 700℃ or above 750℃ and not higher than 850℃; Fourth geopolymer: above 700℃ and not higher than 750℃.

11. Geopolymer material according to claim 10, wherein, The calcination time is 1.5-2.5 hours.

12. Geopolymer material according to claim 11, wherein, The calcination time is 1.8-2.2 hours.

13. Geopolymer material according to claim 1, wherein, The geopolymer material contains any one of the following by weight: (1) 70-80 parts of the third geopolymer and 70-80 parts of the fourth geopolymer; (2) 40-60 parts of the second geopolymer, 90-110 parts of the third geopolymer and 8-12 parts of the fourth geopolymer; (3) 40-60 parts of the first geopolymer and 90-110 parts of the third geopolymer; (4) 40-60 parts of the second geopolymer and 70-90 parts of the third geopolymer; (5) 90-110 parts of the first geopolymer and 8-12 parts of the third geopolymer; (6) 90-110 parts of the second geopolymer and 15-25 parts of the third geopolymer; (7) 40-60 parts by weight of the second geopolymer and 90-110 parts by weight of the third geopolymer; (8) 40-60 parts by weight of the first geopolymer and 90-110 parts by weight of the fourth geopolymer.

14. Geopolymer material according to claim 1, wherein, The geopolymer material also contains an activator, which contains one or more of a soluble hydroxide, a soluble silicate, a soluble carbonate, and a soluble polyphosphate.

15. Geopolymer material according to claim 14, wherein, The activator contains one or more of sodium hydroxide, potassium hydroxide, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium polyphosphate, and potassium polyphosphate.

16. Geopolymer material according to claim 15, wherein, The activator contains sodium hydroxide and sodium silicate, or sodium silicate and sodium polyphosphate. The activator is stored separately from the modified aluminosilicate and is mixed together before use.

17. Geopolymer material according to any one of claims 14-16, wherein, The activator is mixed with the modified aluminosilicate in the form of an aqueous solution with a concentration of 0.5-10 mol / L.

18. Geopolymer material according to claim 17, wherein, In the solution of the activator, the concentration of soluble hydroxide is 2-6 mol / L, and / or the concentration of soluble silicate is 1-6 mol / L; and / or the concentration of soluble polyphosphate is 3-7 mol / L.

19. The geopolymer material according to claim 17, wherein, The weight ratio of the activator solution to the modified aluminosilicate is 0.3-0.

8.

20. Geopolymer material according to claim 19, wherein, The weight ratio of the activator solution to the modified aluminosilicate is 0.4-0.

6.

21. A process for the production of a geopolymer material according to any one of claims 1 to 20, characterised in that, The preparation method includes the following steps: calcining kaolin at different temperatures to obtain at least two types of modified aluminosilicates, and then mixing the at least two types of modified aluminosilicates to obtain a geopolymer material.

22. The method of making according to claim 21, wherein, The at least two modified silica-alumina are at least two of the following: a first geopolymer, a second geopolymer, a third geopolymer, and a fourth geopolymer. The calcination temperatures for the various geological polymers are as follows: First-level geopolymer: not higher than 600℃ or higher than 950℃; Second geological polymer: above 600℃ and not higher than 650℃ or above 850℃ and not higher than 950℃; Third geological polymer: above 650℃ and not higher than 700℃ or above 750℃ and not higher than 850℃; Fourth geopolymer: above 700℃ and not higher than 750℃.

23. The method of making according to claim 22, wherein, The calcination time is 1.5-2.5 hours.

24. The method of manufacturing according to claim 23, wherein, The calcination time is 1.8-2.2 hours.

25. The method of manufacturing according to claim 21, wherein, The preparation method does not include the step of adding a retarder, wherein the retarder is one or more of the following: lignin sulfonate and its derivatives, sugars and their derivatives, boric acid and its salts, phosphoric acid and its salts, phosphonic acid and its salts, acrylic polymers, citric acid and its salts, tartaric acid and its salts, zinc salts, alkaline earth metal salts, and inorganic sulfates.

26. The method of manufacturing according to claim 21, wherein, The preparation method further includes a step of mixing an activator, wherein the activator contains one or more of a soluble hydroxide, a soluble silicate, a soluble carbonate, and a soluble polyphosphate.

27. The method of manufacturing according to claim 26, wherein, The activator contains one or more of sodium hydroxide, potassium hydroxide, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate, sodium polyphosphate, and potassium polyphosphate.

28. The method of manufacturing according to claim 27, wherein, The activator contains sodium hydroxide and sodium silicate, or sodium silicate and sodium polyphosphate.

29. The method of manufacturing according to claim 26, wherein, The activator is mixed with the modified aluminosilicate in the form of an aqueous solution with a concentration of 0.5-10 mol / L.

30. The method of manufacturing according to claim 29, wherein, In the solution of the activator, the concentration of soluble hydroxide is 2-6 mol / L, and / or the concentration of soluble silicate is 1-6 mol / L; and / or the concentration of soluble polyphosphate is 3-7 mol / L.

31. The method of manufacturing according to claim 29 or 30, wherein, The weight ratio of the activator solution to the modified aluminosilicate is 0.3-0.

8.

32. The method of manufacturing according to claim 31, wherein, The weight ratio of the activator solution to the modified aluminosilicate is 0.4-0.

6.

33. The application of the geopolymer material according to any one of claims 1-20 in oilfield cementing.

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